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www.appleacademicpress.com
PROCESS ADVANCEMENT IN
CHEMISTRY AND CHEMICAL
ENGINEERING RESEARCH
PROCESS ADVANCEMENT IN
CHEMISTRY AND CHEMICAL
ENGINEERING RESEARCH

Edited by
Gennady E. Zaikov, DSc
Vladimir A. Babkin, DSc
CRC Press Apple Academic Press, Inc
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ABOUT THE EDITORS

Gennady E. Zaikov, DSc

Head of the Polymer Division, N. M. Emanuel Institute of Biochemical Physics,
Russian Academy of Sciences, Moscow, Russia
Professor, Moscow State Academy of Fine Chemical Technology, Russia Professor,
Kazan National Research Technological University, Kazan, Russia
Gennady E. Zaikov, DSc, is Head of the Polymer Division at the N. M. Emanuel
Institute of Biochemical Physics, Russian Academy of Sciences, Moscow, Russia,
and professor at Moscow State Academy of Fine Chemical Technology, Russia, as
well as Professor at Kazan National Research Technological University, Kazan,
Russia. He is also a prolific author, researcher, and lecturer. He has received several
awards for his work, including the the Russian Federation Scholarship for Outstand-
ing Scientists. He has been a member of many professional organizations and on the
editorial boards of many international science journals.

Vladimir A. Babkin, DSc

Professor and Head, Research Department, Volgograd State University of Architec-
ture and Engineering, Sebryakovsky Branch, Volgograd, Russia
Vladimir Aleksandrovich Babkin, DSc, is Professor and Head of the Research
Department at Volgograd State University of Architecture and Engineering, Se-
bryakovsky Branch in Volgograd, Russia. Professor Babkin graduated from Bashkir
State University in 1976 (Ufa, Russia) as a physicist, specializing in the field of
applied quantum chemistry. He is the author of more than 1,200 scientific papers
(including 14 monographs.)
CONTENTS

List of Contributors...........................................................................................ix
List of Abbreviations ....................................................................................... xv
Preface........................................................................................................... xvii
1. Bioactive Nitrogen-Containing Compounds with Spatial Carbocyclic
Groups: Synthesis, Modeling of Physical Properties and Use for Creation
of Inorganic-Organic Hybrid Materials with Specific Properties...............1
N. Lekishvili, Kh. Barbakadze, D. Zurabishvili, G. Lekishvili, B. Arziani, A. Fainleib,
O. Grigorieva, W. Brostow, and T. Datashvili

2. Relationship Between the Structure, Molecular Dynamics and

Thermo-Oxidative Stability of Low Density Polyethylene and Butyl
Rubber Blends................................................................................................21
T. V. Monakhova, L. S. Shibryaeva , N. N. Kolesnikova, A. I. Sergeev, S. G. Karpova, and
A. A. Popov

3. A Study on Possibilities for Cellulose-Based Textile Waste Treatment

into Powder-Like Fillers for Emulsion Rubbers.........................................37
V. M. Misin

4. Theoretical Estimation of Acid Force of Molecule P-Dimethoxy-

Trans-Stilbene by Method Ab Initio.............................................................55
V. A. Babkin, D. S. Andreev, Yu. A. Prochukhan, K. Yu. Prochukhan, and G. E. Zaikov

5. Modification of Polyamide- 6 by N, N'-Bis-Maleamidoacid.......................61

N. R. Prokopchuk, E. T. Krut'ko, and M. V. Zhuravleva

6. Protective Properties of Modified Epoxy Coatings.....................................71

N. R. Prokopchuk, M. V. Zhuravleva, T. A Zharskaya, and E. T Krut'ko

7. Chemical Transformation of Syndiotactic 1,2-Polybutadiene...................81

M. I. Abdullin, A. B. Glazyrin, O. S. Kukovinets, A. A. Basyrov, and G. E. Zaikov

8. Normalization of the Maintenance of Metals in Objects

of an Environment in View of Complex Receipt in an Organism of the
Person..............................................................................................................99
J. A. Tunakova, S. V.Novikova, R. A. Shagidullina, and M. I. Artsis

9. Influence of Hydrolysis on Diffusion of Electrolytes................................. 111

Ana C. F. Ribeiro, Luís M. P. Veríssimo, Artur J. M. Valente, Ana M. T. D. P. V. Cabralb,
and Victor M. M. Lobo
viii Contents

10. Ozone Decomposition..................................................................................121

T. Batakliev, V. Georgiev, M. Anachkov, S. Rakovsky, and G. E. Zaikov

11. Ozone Decomposition on the Surface of Metal Oxide Catalyst...............149

T. Batakliev, V. Georgiev, M. Anachkov, S. Rakovsky, A. Berlin, and G. Zaikov

12. Synthesis of O-Including Compounds by Catalytic Conversation of

Olefins...........................................................................................................163
G. Z. Raskildina, N. G. Grigor’eva, B. I. Kutepov, S. S. Zlotsky, and G. E. Zaikov

13. Stress Birefringence of Highly Cross-Linked Polymers of Optoelectronic

Application in the Context of Heredity Theory.........................................175
Nikolai V. Ulitin, Ilshat I. Nasyrov, Rafit R. Nabiev, Daria A. Shiyan, Nail K. Nuriev, and
Gennady E. Zaikov

14. Investigation of Various Method for Steel Surface Modification............191

Igor Novák, Ivan Michalec, Marian Valentin, Milan Marônek, Ladislav Šoltés,
Ján Matyašovský, and Peter Jurkovič

15. Sorbtion of Industrial Dyes by Inorganic Rocks from

Aqueous Solutions........................................................................................203
F. F. Niyazi and A. V. Sazonova

16. Some Coordination Compounds of Arsenic and Stibium........................ 211

N. Lekishvili, M. Rusia, L. Arabuli, Kh. Barbakadze, I. Didbaridze, M. Samkharadze,
G. Jioshvili, K. Giorgadze, and N. Sagaradze

17. Surface-Modified Magnetic Nanoparticles for Cell Labeling..................275

Beata A. Zasonska,Vitalii Patsula,Rostyslav Stoika, and Daniel Horák

18. The Reinforcement of Particulate-Filled Polymer Nanocomposites by

Nano-Particles Aggregates..........................................................................289
G. E. Zaikov. G. V. Kozlov, and A. K. Mikitaev

19. A New xf Photosynthesis..............................................................................303

Gennady G. Komissarov
20. Application Able Radicals for Study of Behavior of Biological
Systems..........................................................................................................329
M. D. Goldfein, and E. G. Rozantsev

21. Quantum-Chemical Calculation of the Models of Dekacene and Eicosa-

cene by Method MNDO Within the Framework of Molecular Graphene
Model.............................................................................................................345
V. A. Babkin, V. V. Trifonov, A. P. Knyazev, V. Yu. Dmitriev, D. S. Andreev, A. V. Ignatov,
E. S.Titova, O. V. Stoyanov, and G. E. Zaikov
Index..............................................................................................................359
LIST OF CONTRIBUTORS

M. I. Abdullin
Bashkir State University, Ufa 450077, Russia.E-mail: [email protected]

M. Anachkov
Institute of Catalysis, Bulgarian Academy of Sciences, Bonchev St. #11, Sofia 1113, Bulgaria

D. S. Andreev
Sebrykov Department, Volgograd State Architect-build University, Akademicheskaya ul., 1, Volgograd
400074, Volgograd Oblast, Russia

L. Arabuli
Faculty of Exact and Natural Sciences, Institute of Inorganic–Organic Hybrid Compounds and Non-
traditional Materials, Ivane Javakhishvili Tbilisi State University, 1 Ilia Chavchavadze Avenue, Tbilisi
0179, Georgia

M. I. Artsis
N.M.Emanuel Institute of Biochemical Physics, Russian Academy of Sciences,4 Kosygin str., Moscow
119334, Russia. E-mail:[email protected]

B. Arziani
Tbilisi State Medical University, Tbilisi, Georgia

V. A. Babkin
Sebrykov Department, Volgograd State Architect-build University, Akademicheskaya ul., 1, Volgograd
400074, Volgograd Oblast, Russia

Kh. Barbakadze
Faculty of Exact and Natural Sciences, Institute of Inorganic–Organic Hybrid Compounds and Non-
traditional Materials, Ivane Javakhishvili Tbilisi State University, 1 Ilia Chavchavadze Avenue, Tbilisi
0179, Georgia

A. A. Basyrov
Bashkir State University, Ufa 450077, Russia

T. Batakliev
Institute of Catalysis, Bulgarian Academy of Sciences, Bonchev St. #11, Sofia 1113, Bulgaria.
E-mail: [email protected]

A. Berlin
N.N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 4 Kosygin str., Moscow
119991, Russia. E-mail:[email protected]

W. Brostow
Laboratory of Advanced Polymers & Optimized Materials (LAPOM), Department of Materials Science
and Engineering, University of North Texas, 1150 Union Circle No.305310, Denton, TX 76203-5017,
USA.E-mail: [email protected]

A. M. T. D. P. V. Cabral
Faculty of Pharmacy, University of Coimbra, 3000-295 Coimbra, Portugal. E-mail:[email protected]
x List of Contributors

T. Datashvili
Laboratory of Advanced Polymers & Optimized Materials (LAPOM), Department of Materials Science
and Engineering, University of North Texas, 1150 Union Circle No.305310, Denton, TX 76203-5017,
USA

I. Didbaridze
Kutaisi Akaki Cereteli State University, 59, Tamar Mephe st., 59, Kutaisi 4600, Georgia
V. Yu. Dmitriev
Sebrykov Department, Volgograd State Architect-build University, Akademicheskaya ul., 1, Volgograd
400074, Volgograd Oblast, Russia

A. Fainleib
Institute of Macromolecular Chemistry, National Academy of Science of Ukraine, Kiev, Ukraine.
E-mail:[email protected]

V. Georgiev
Institute of Catalysis, Bulgarian Academy of Sciences, Bonchev St. #11, Sofia 1113, Bulgaria

K. Giorgadze
Faculty of Exact and Natural Sciences, Institute of Inorganic–Organic Hybrid Compounds and Non-
traditional Materials, Ivane Javakhishvili Tbilisi State University, 1 Ilia Chavchavadze Avenue, Tbilisi
0179, Georgia

A. B. Glazyrin
Bashkir State University, Ufa 450077, Russia

M. D. Goldfein
Saratov State University, Saratov, Russia.E-mail: [email protected]

N. G. Grigor’eva
Institute of Petrochemistry and Catalysis of RAS, 141 pr. Oktyabria,450075 Ufa, Russia

O. Grigorieva
Institute of Macromolecular Chemistry, National Academy of Science of Ukraine, Kiev, Ukraine

D. Horák
Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovskeho Sq.
2, 162 06 Prague 6, Czech Republic

A.V. Ignatov
Sebrykov Department, Volgograd State Architect-build University, Akademicheskaya ul., 1, Volgograd
400074, Volgograd Oblast, Russia

N. P. Ivanova
Belarusian State Technological University, Sverdlova Str. 13a, Minsk, Republic of Belarus
G. Jioshvili
Faculty of Exact and Natural Sciences, Institute of Inorganic–Organic Hybrid Compounds and Non-
traditional Materials, Ivane Javakhishvili Tbilisi State University, 1 Ilia Chavchavadze Avenue, Tbilisi
0179, Georgia

P. Jurkovič
VIPO, Partizánske, Slovakia

S. G. Karpova
Institute of the Russian Academy of Sciences, N.M. Emanuel Institute of Biochemical Physics, Russian
Academy of Sciences, Moscow, Russia
List of Contributors  

A. P. Knyazev
Sebrykov Department, Volgograd State Architect-build University, Akademicheskaya ul., 1, Volgograd
400074, Volgograd Oblast, Russia

N. N. Kolesnikova
Institute of the Russian Academy of Sciences, N.M. Emanuel Institute of Biochemical Physics, Russian
Academy of Sciences, Moscow, Russia
G. G. Komissarov
N.N.Semenov Institute for Chemical Physics, Russian Academy of Sciences, Kosygin St. 4, Moscow
119991, Russia.E-mail: [email protected]; [email protected]

G. V. Kozlov
Kh.M. Berbekov Kabardino-Balkarian State University, Chernyshevsky st., 173, Nal’chik 360004,
Russian Federation

E. T. Krut'ko
Belarusian State Technological University, Sverdlova Str. 13a, Minsk, Republic of Belarus

O. S. Kukovinets
Bashkir State University, Ufa 450077, Russia

B. I. Kutepov
Institute of Petrochemistry and Catalysis of RAS, 141 pr. Oktyabria,450075 Ufa, Russia

G. Lekishvili
Tbilisi State Medical University, Tbilisi, Georgia. E-mail: [email protected]

N. Lekishvili
Faculty of Exact and Natural Sciences, Institute of Inorganic–Organic Hybrid Compounds and Non-
traditional Materials, Ivane Javakhishvili Tbilisi State University, 1 Ilia Chavchavadze Avenue, Tbilisi
0179, Georgia.E-mail: [email protected]; [email protected]

V. M. M. Lobo
Department of Chemistry, University of Coimbra, 3004–535 Coimbra, Portugal. E-mail: [email protected]

M. Marônek
Slovak Academy of Sciences, Polymer Institute of the Slovak Academy of Sciences, 845 41 Bratislava,
Slovakia

J. Matyašovský
VIPO, Partizánske, Slovakia. E-mail: [email protected]

I. Michalec
Slovak Academy of Sciences, Polymer Institute of the Slovak Academy of Sciences, 845 41 Bratislava,
Slovakia
V. M. Misin
N. M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Moscow, Russia

A. K. Mikitaev
Kh.M. Berbekov Kabardino-Balkarian State University, Chernyshevsky st., 173, Nal’chik 360004,
Russian Federation

T. V. Monakhova
Institute of the Russian Academy of Sciences, N.M. Emanuel Institute of Biochemical Physics, Russian
Academy of Sciences, Moscow, Russia
xii List of Contributors

R. R. Nabiev
Kazan National Research Technological University, 68 Karl Marx Street, 420015 Kazan, Republic of
Tatarstan, Russian Federation

I. I. Nasyrov
Kazan National Research Technological University, 68 Karl Marx Street, 420015 Kazan, Republic of
Tatarstan, Russian Federation
S. S. Nikulin
Voronezh State University of the Engineering Technologies, Voronezh, Russia

F. F. Niyazi
Fundamental chemistry and chemical technology, South-West State University, 305040 Kursk, street
October 50, 94, Russia. E-mail: [email protected]

I. Novák
Department of Welding and Foundry, Faculty of Materials Science and Technology in Trnava, 917 24
Trnava, Slovakia

S. V. Novikova
Kazan National Research Technological University, 65 Karl Marx str., Kazan 420015, Tatarstan, Russia

N. K. Nuriev
Kazan National Research Technological University, 68 Karl Marx Street, 420015 Kazan, Republic of
Tatarstan, Russian Federation

V. Patsula
Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovskeho Sq.
2, 162 06 Prague 6, Czech Republic

A. A. Popov
Institute of the Russian Academy of Sciences, N.M. Emanuel Institute of Biochemical Physics, Russian
Academy of Sciences, Moscow, Russia

K. Y. Prochukhan
Bashkir State University, Kommunisticheskaya ul., 19, Ufa 450076, Republic of Bashkortostan, Russia

N. R. Prokopchuk
Belarusian State Technological University, Sverdlova Str. 13a, Minsk, Republic of Belarus

Yu. A. Prochukhan
Bashkir State University, Kommunisticheskaya ul., 19, Ufa 450076, Republic of Bashkortostan, Russia

I. N. Pugacheva
Voronezh State University of the Engineering Technologies, Voronezh, Russia

S. Rakovsky
Institute of Catalysis, Bulgarian Academy of Sciences, Bonchev St. #11, Sofia 1113, Bulgaria

Z. Raskildina
Ufa State Petroleum Technological University, 1 Kosmonavtov Str.,450062 Ufa, Russia

A. C. F. Ribeiro
Department of Chemistry, University of Coimbra, 3004–535 Coimbra, Portugal.
E-mail: [email protected]

E. G. Rozantsev
Saratov State University,Saratov, Russia
List of Contributors  

M. Rusia
Faculty of Exact and Natural Sciences, Institute of Inorganic–Organic Hybrid Compounds and Non-
traditional Materials, Ivane Javakhishvili Tbilisi State University, 1 Ilia Chavchavadze Avenue, Tbilisi
0179, Georgia

N. Sagaradze
Faculty of Exact and Natural Sciences, Institute of Inorganic–Organic Hybrid Compounds and Non-
traditional Materials, Ivane Javakhishvili Tbilisi State University, 1 Ilia Chavchavadze Avenue, Tbilisi
0179, Georgia

M. Samkharadze
Kutaisi Akaki Cereteli State University, 59, Tamar Mephe st., 59, Kutaisi 4600, Georgia

A. V. Sazonova
Fundamental chemistry and chemical technology, South-West State University, 305040 Kursk, street
October 50, 94, Russia. E-mail:[email protected]

A. I. Sergeev
Institute of the Russian Academy of Sciences, N.N. Semenov Institute of Сhemical Physics, Russian
Academy of Sciences, Moscow, Russia

R. A. Shagidullina
Kazan National Research Technological University, 65 Karl Marx str., Kazan 420015, Tatarstan, Russia

L. S. Shibryaeva
Institute of the Russian Academy of Sciences, N.M. Emanuel Institute of Biochemical Physics, Russian
Academy of Sciences, Moscow, Russia

D. A. Shiyan
Kazan National Research Technological University, 68 Karl Marx Street, 420015 Kazan, Republic of
Tatarstan, Russian Federation

L. Šoltés
Institute of Experimental Pharmacology of the Slovak Academy of Sciences, 845 41 Bratislava, Slovakia

R. Stoika
Institute of Cell Biology, National Academy of Science of Ukraine, Drahomanov St. 14/16, 79005 Lviv,
Ukraine

O. V. Stoyanov
Kazan State Technological University, Kazan, Tatarstan, Russia

E. S. Titova
Volgograd State Technical University, Volgograd, Russia

V. V. Trifonov
Sebrykov Department, Volgograd State Architect-build University, Akademicheskaya ul., 1, Volgograd
400074, Volgograd Oblast, Russia

J. A. Tunakova
Kazan National Research Technological University, 65 Karl Marx str., Kazan 420015, Tatarstan, Russia.
E-mail: [email protected]

N. V. Ulitin
Kazan National Research Technological University, 68 Karl Marx Street, 420015 Kazan, Republic of
Tatarstan, Russian Federation. E-mail: [email protected]
xiv List of Contributors

A. J. M. Valente
Department of Chemistry, University of Coimbra, 3004–535 Coimbra, Portugal.
E-mail: [email protected]

M. Valentin
Department of Welding and Foundry, Faculty of Materials Science and Technology in Trnava, 917 24
Trnava, Slovakia
L. M. P. Veríssimo
Department of Chemistry, University of Coimbra, 3004–535 Coimbra, Portugal.
E-mail: [email protected]

G. E. Zaikov
Bashkir State University, Ufa 450076, Russia

G. E. Zaikov
N.M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, 4, Kosygin St., Moscow
119334, Russian Federation. E-mail: [email protected]

B. A. Zasonska
Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovskeho Sq.
2, 162 06 Prague 6, Czech Republic

T. A. Zharskaya
Belarusian State Technological University, Sverdlova Str. 13a, Minsk, Republic of Belarus

M. V. Zhuravleva
Belarusian State Technological University, Sverdlova Str. 13a, Minsk, Republic of Belarus

S. S. Zlotsky
Ufa State Petroleum Technological University, 1 Kosmonavtov Str.,450062 Ufa, Russia

D. Zurabishvili
Faculty of Exact and Natural Sciences, Institute of Inorganic–Organic Hybrid Compounds and Non-
traditional Materials, Ivane Javakhishvili Tbilisi State University, 0179 Tbilisi, Georgia
LIST OF ABBREVIATION

AAS Atomic absorption spectroscopy

AMPA 2,2'-Azobis(2-methylpropionamidine)
APC Acid powder-like cellulose
APTES Aminopropyl triethoxysilane
ATR–FTIR Attenuated total reflectance–Fourier transform infrared spectroscopy
BD Beginning of the decay
BR Butyl rubber
CMC Critical micelle concentration
CPMG Carr–Purcell–Meiboom–Gill
DLS Dynamic light scattering
DMEM Dulbecco’s modified Eagle’s medium
DGEBA Diglycidyl ether of bisphenol-A
DSC Differential scanning calorimetry
DTA Differential-thermal analysis
DVM Digital voltmeter
ED End of the decay
EPC Epoxy polymer coating
EPR Electron paramagnetic resonance
ETP Electron transport particles
FID Free induction decay
GLC Gas–liquid chromatography
GNC Globular nanocarbon
HA Hexylamine
HA-mPEG Hydroxamic acid methoxy polyethylene glycol
HMDA Hexamethylenediamine
LDPE Low-density polyethylene
MCC Microcrystalline cellulose
MCPBA Meta-chloroperbenzoic acid
MFI Melt flow index
MP Melting points
mPEG Methoxy polyethylene glycol
MRA Mechanical-rubber articles
MRI Magnetic resonance imaging
MST Micro-scratch tester
NPC Neutral powder-like cellulose
NS Number of scans
PA Polyamide
xvi List of Abbreviation

PA-mPEG Phosphonicmethoxy polyethylene glycol

pAPh p-aminophenol
PB Polybutadiene
PCA Principal components analysis
PDMAAm Poly(N,N-dimethylacrylamide)
PE Polyethylene
PEG Polyethylene glycol
PLS Partial least squares
PP Polypropylene
PU Polyester urethane
PUS Sulfur-containing polyester urethane
PUSI Ionomer of sulfur-containing polyester urethane
QSRR/QSAR Quantitative structure–property relationship
RD Recycle delay
RDF Radial distribution functions
SEM Scanning electron microscopy
TEM Transmission electron microscopy
TEOS Tetraethyl orthosilicate
ТFPA Trifluoroperacetic acid
TGA Thermogravimetricanalysis
TMOS Tetramethylorthosilicate
XRD X-ray diffraction
PREFACE

This volume contains peer-reviewed chapters and is devoted to the publication of

original research works from chemistry and their broad range of applications in
chemical engineering. It covers theoretical and practical application of modern
chemistry.
This book deals with different aspects of chemistry and chemical engineering.
The book includes the most significant new research papers and other original con-
tributions in the form of reviews and reports on new concepts and research being
done in the world, thus ensuring its scientific priority and significance.
This is a multidisciplinary book dealing with many structural aspects of modern
chemistry and chemical engineering. This volume will be of interest to research-
ers because it explores the principles of chemical bonding and matter organiza-
tion, the impact of structural aspects on a chemical property or transformation, and
the application of the newest physical methods in chemical structure research. The
volume covers studies on the structure of single molecules and radicals, molecular
assemblies, gases, liquids (including water and solutions), amorphous and crystal-
line solids, surfaces, films and nanoparticles (including inorganic, organic and or-
ganometallic compounds), molecular and polymeric materials, and single crystals
and minerals.
CHAPTER 1

BIOACTIVE NITROGEN-CONTAINING
COMPOUNDS WITH SPATIAL
CARBOCYCLIC GROUPS: SYNTHESIS,
MODELING OF PHYSICAL PROPERTIES,
AND USE FOR CREATION OF
INORGANIC–ORGANIC HYBRID
MATERIALS WITH SPECIFIC PROPERTIES
N. LEKISHVILI1, KH. BARBAKADZE1, D. ZURABISHVILI1,
G. LEKISHVILI2, B. ARZIANI2, A. FAINLEIB3, O. GRIGORIEVA3,
W. BROSTOW4, and T. DATASHVILI4
1
Faculty of Exact and Natural Sciences, Institute of Inorganic–Organic Hybrid
Compounds and Non-traditional Materials, Ivane Javakhishvili Tbilisi State University,
0179, Tbilisi, Georgia, [email protected]
2
Tbilisi State Medical University, [email protected]
3
Institute of Macromolecular Chemistry, National Academy of Science of Ukraine,
Kiev, Ukraine, [email protected]
4
Laboratory of Advanced Polymers & Optimized Materials (LAPOM), Department of
Materials Science and Engineering, University of North Texas, 1150 Union Circle
No.305310, Denton, TX 76203-5017, USA, [email protected]

CONTENTS
Abstract......................................................................................................................2
1.1 Introduction.......................................................................................................2
1.2  Experimental Details.........................................................................................3
1.3  Results and Discussion.....................................................................................4
1.4 Conclusion......................................................................................................17
Acknowledgment.....................................................................................................17
Keywords.................................................................................................................18
References................................................................................................................18
2 Process Advancement in Chemistry and Chemical Engineering Research

ABSTRACT
Quantitative “structure–properties” relationships (QSRR/QSAR) based on experi-
mental data for the construction of models of dependences of the physical proper-
ties of bioactive nitrogen-containing compounds with bioactive spatial carbocyclic
groups on molecular structures were studied. Several sets of molecular descriptors
were used. The presence of the dataset outliers was controlled by using Principal
Components Analysis (PCA); to ascertain the quality of models cross-validation
was used. Virtual bioscreening and activity toward various microorganisms of the
obtained compounds were established. Inorganic–organic hybrid materials with spe-
cific properties based on organic heterochain polymers and coordination compounds
of some transition metals based on bioactive nitrogen-containing compounds were
obtained and studied. Tribological properties and stability toward various factors
(e.g., O2, CO2, and moisture complex action), photochemical stability (toward, e.g.,
ultraviolet and visible light), and isothermal aging of the created composite materi-
als were studied. From preliminary investigations, it was established that the created
bioactive composites could be used for prevention of materials from biodeteriora-
tion and noncontrolled biodegradation, inhibition of growth and expansion of mi-
croorganisms, which are causal factors of infectious diseases, and for prophylaxis
and treatment of the above-mentioned diseases.

1.1 INTRODUCTION
Biodegradation of synthetic and natural materials by various microorganisms af-
fects a wide range of industries and techniques. According to the existing statisti-
cal data, more than several hundred kinds of such aggressive microorganisms are
known,1–3 which damage especially carbon-containing polymers and materials. The
actions of microorganisms on polymers are influenced by two different processes:
(a) deterioration and degradation of polymers, which serve as a native substance
for growth of the microorganisms (direct action), and (b) the influence of metabolic
products of the microorganisms (indirect action). Losses caused by destruction of
natural and synthetic materials with micromycets reach enormous amounts and con-
stitute annually milliards of dollars.4, 5
Historical buildings, archeological artifacts (made of metals and their alloys,
leather, and/or wood), museum exhibits, and collections of artwork all need protec-
tion from the influence of various aggressive microorganisms. So the protection of
cultural heritage and various synthetic and natural materials is a global problem.6
One of the ways to protect synthetic materials from the action of microorgan-
isms is the creation of novel polymer coatings with high bioactivity by modification
of various polyfunctional adhesive polymer matrices with biologically active com-
pounds.7 Therefore, synthesis of compounds for bioactive composites and created
Bioactive Nitrogen-Containing Compounds with Spatial Carbocyclic Groups 3

antibiocorrosive coatings based on them for various natural, synthetic, and artificial
materials is extremely significant and requires further developments.8
For the time being in the various spheres of science and technique, scientists
are focusing special attention on asymmetric carbocyclic compounds (such as ada-
mantane and its derivatives). Modification of various bioactive compounds by im-
munotropic and membranotropic adamantane groups has a great potential because
of improvement in their hydrolytic stability and the increase in their biological ac-
tivity.9–12

1.2  EXPERIMENTAL DETAILS

Nitrogen-containing compounds with spatial (adamantane) carbocyclic groups and
adamantane-containing hydrazide coordination compounds of transition metals
were synthesized by us earlier.13

Polyester urethane “PU”

(1) The mixture of 50 g (0.1 mole) polyoxypropylenglycole, 2.6 g (0.05 mole)
diethylenglicole, and 26.1 g (0.3 mole) toluylendiisocyanate (the mixture of
2,4- and 2,6-isomers with ratio 65:35 wt.%) was stirred for 1 h at 80–90°C
until formation of hexamethylendiisocyanate. The monitoring of the reac-
tion was carried out by the content of the NCO group (the optimum content
of the NCO group for the above-mentioned polyester urethane is ~7.6%).
(2) To hexamethylendiisocyanate, 0.05 mole hydrazine hydrate (the 1% solu-
tion of hydrazine hydrate in dimethyl formamide) was added for the purpose
of chain lengthening. The mixture was stirred for 24 h. The monitoring of
the reaction was carried out by infrared spectroscopy, in particular, by dis-
appearance of the characteristic absorption bands of the NCO group in the
IR spectra of the research sample (2273 cm–1). It was established that for
polyester urethane Mw ≈ 50,300.

Sulfur-containing polyester urethane “PUS”

For fuctionalization of hexamethylendiisocyanate, its sulfurization was carried out
with 98% sulfuric acid (5 wt.% of hexamethylendiisocyanate). To the mixture drop-
wise sulfuric acid was added for 20 min until 6.5–6.8% content of the NCO group.
The reaction was carried out under the stirring condition at 80–90°C for 5 h. The
degree of sulfurization of the obtained polyester urethane was ~3 wt.% (the degree
of sulfurization was determined by titration of sulfo-groups). It was established that
for sulfur-containing polyester urethane Mw ≈ 97,400.

Ionomer of sulfur-containing polyester urethane “PUSI”

The sulfurized hexamethylendiisocyanate (Mw ≈ 118,000) was cooled at 40–45°C
and then the transfer of the SO3H group was carried out from acid to salt form by
4 Process Advancement in Chemistry and Chemical Engineering Research

the addition of equimolar (in relation to sulfuric acid) triethylamine. To the obtained
ion-containing hexamethylendiisocyanate was added 0.05 mole 1% water solution
of hydrazine hydrate under the stirring condition for 24 h for the purpose of chain
lengthening.
The antibiocorrosive coatings were prepared in the following way: to the cyclo-
hexanone solution of the polymeric matrix definite quantity of modifier (3 wt.%)
and bioactive coordination compound (3–5 wt.%) was gradually added under the
stirring condition until the formation of light color homogeneous mass. Later, the
obtained composition was laid in the form of a thin layer on the surface of the select-
ed various materials (wood, plastic, Teflon, etc.) for protection and was delayed in
the air for 24–48 h at room temperature. After hardening, a homogeneous, smooth,
mechanically stable protective layer was produced.

Methods of analysis
Standard methods for obtaining and purifying bioactive compounds were used.
The tribological properties of the polymeric matrices were determined using
a Spanish Nanovea pin-on-disk tribometer (Micro Photonics Inc., 4972 Medical
Center Cir # 4, Allentown, PA 18106, United States), micro-scratch tester (MST)
(CSM, Neuchatel, Switzerland), and a Nicon Eclipse ME 600 Microscope. Standard
microbiological methods were used for the study of the bactericidal and fungicidal
properties of synthesized compounds.

1.3  RESULTS AND DISCUSSION

To establish the correlation between the structure of the possible bioactive com-
pound and some of its fundamental properties, we synthesized and studied some
anilides and nitroanilides14 containing spatial carbocyclic groups (adamantane) with
various organic radicals in the benzene ring (Scheme 1.1, Table 1.1). In order to
select these compounds, we considered the availability of their synthesis and pos-
sibility of their perspective wide commercialization.

SCHEME 1.1  Nitrogen-containing derivatives of adamantane.

Bioactive Nitrogen-Containing Compounds with Spatial Carbocyclic Groups 5

TABLE 1.1  Experimental Components Studied.

Compounda R R¢ R² Compound R R¢ R²
1 H CH3 Adb 8 Cl 4-ClC6H4 Ad
2 H CH3 Ad 9 H C2H5 Ad
3 H C2H5 Ad 10 H Ad CH3
4 H Ad CH3 11 H Ad CH2C6H5
5 H Ad C6H5 12 H Ad C6H5
6 H Ad CH2C6H5 13 H Ad Ad
7 H Ad Ad 14 Cl 4-ClC6H4 Ad

Scheme 1.1; Ad: adamantyl.

a b

The techniques of the quantitative structure–property relationship (QSRR/

QSAR) are used for establishing reliable models of biological activities and the
physical–chemical properties of organic and element-organic molecules. The afore-
mentioned approach is based on the representation of molecular structures with nu-
meric quantities. They are calculated via straightforward algorithms and are known
as molecular descriptors. Among the latter, considerable attention is granted to the
autocorrelation-based descriptors.14
Let us give a brief outline of the approach. Suppose s1, s2, …, sn are variables,
which present various molecular substructures. Most often, the paths of the corre-
sponding molecular graphs are considered. As is clear, n, that is, the number of the
paths depends on the number of atoms, or, in the graph-theoretical context, on the
number of vertices. However, to build statistically reasonable models, one needs to
represent molecules with vectors (i.e., series of molecular descriptors) of the same
length. Therefore, we introduce a set of the template variables, t1, t2, … tm, where m
remains constant, that is, is independent of the size of molecules of the dataset in
question. The aforementioned substructures are characterized by special functions.
An example is the product of numeric values of a physical property of the atoms of
the substructure. That is, if we consider only paths as substructures, we have

f ( si ) = pi0 pi1 .
Here, p0 is a physical property of the origin of the ith path and p1 is that of the ter-
minal vertex (atom) of the path. Examples of the physical property are sigma- and
pi-charges, electro negativities, etc. Therefore, we arrive at a vector of the products
of the physical properties of the paths, f, which has dimensionality equal to n.
Autocorrelation vectors are defined as linear transforms of the f vectors of the
dimensionality n to the vectors a of the dimensionality m. The transform is given by
kernel matrices (K):
6 Process Advancement in Chemistry and Chemical Engineering Research

a = fK , or in the functional form: a (t ) = ∫ K (t , s ) f ( s )ds

The kernel matrix (K) has dimensionality (n,m). The vector a will always be of
size m, and therefore, independent of the size of the molecule. The kernels are given
by various functions. The kernel of the 3D-MoRSE descriptor, for example, is given
as follows:

sin tr ( s )
K (t , s ) =
tr ( s )
Here, r(s) is the Euclidean distance.
QSPR calculations: We used MDL Isis Draw 2.5 SP4 to build molecular mod-
els. Afterward, we concatenated the models into the dataset by use of EdiSDF 5.02.
The textual format of the dataset was SDF. We used the VCC-Lab e-Dragon web
application for the calculation of molecular descriptors. Statistic 6.0 was a tool of
our choice for building PCA and Partial Least Squares (PLS) models.
Among many available molecular descriptors at our disposal, we selected Ra-
dial Distribution Functions (RDF),15 Crystal Structure Codes (MoRSE),16 WHIM,17
GETAWAY,18 and traditional topological indices.19 Our dataset20 contained 16 com-
pounds.
In order to detect outliers, that is, the compounds, which did not belong to the
modeling population, we performed PCA.21 However, unlike our previous contribu-
tion,22 we did not identify any of the investigating compounds as outliers.
As one can see (Fig. 1.1), compounds 7, 8, 13–1612 are situated somehow far-
ther than the main group. This alone does not allow for their removal. For ex-
ample, the Burden eigenvalues reveal that only compound 8 is an outlier (Fig.
1.2). When we used Randič-type invariants, none of the compounds left the main
group (Fig. 1.3). Therefore, we decided to keep all of the compounds in the train-
ing dataset. It is noteworthy that the Randič-type invariants clearly output several
clusters of compounds.
Our final step was establishment of relationships between these descriptors and
the retention factors measured experimentally. Our studies show that the best model
was achieved by employing, again, the GETAWAY descriptors. We used PLS23 as
the number of predictors was much higher than that of cases. We used cross-vali-
dation to define the optimal number of latent variables. In our study, we used 13
compounds in the training set and 3 for the cross-validation tests. Of course, the
prediction power was lower in the case of cross-validation. We modeled both melt-
ing points (mp) and retention factors (Rf) within the same model, which, therefore,
had two responses.
Bioactive Nitrogen-Containing Compounds with Spatial Carbocyclic Groups 7

FIGURE 1.1  The outlier detection by means of PCA. The descriptor used is GETAWAY.

FIGURE 1.2  The outlier detection by means of PCA. The descriptors used are the Burden
eigenvalues.
8 Process Advancement in Chemistry and Chemical Engineering Research

FIGURE 1.3  The outlier detection by means of PCA. The descriptors used are the Randič-
type invariants.

The results of modeling look impressive as the square of the average correlation
coefficient was as high as 0.92. The PRESS was also good enough (Table 1.2). One
can examine the experimental and calculated values (Table 1.3). A reader should
take into account that compounds 4, 13, 16 produced the test (validation) set.

TABLE 1.2  The Statistical Parameters of the Model.

Latent Increase Average Increase Average R2 for mp R2 for Rf Sc. Press, Sc. Press, Average
Var R2 on Y R2 on Y R2 on X R2 on X mp Rf Sc. Press
No.

1 0.391833 0.391833 0.286528 0.286528 0.577891 0.205776 2.254355 1.727976 1.991166

2 0.286881 0.678714 0.275862 0.562390 0.611797 0.745632 2.094057 1.922039 2.008048

3 0.033169 0.711883 0.206076 0.768466 0.666069 0.757697 1.780881 1.833227 1.807054

4 0.041860 0.753743 0.109336 0.877802 0.670454 0.837033 1.763578 1.837925 1.800751

5 0.121957 0.875700 0.023599 0.901401 0.886302 0.865099 1.268438 1.445234 1.356836

6 0.028227 0.903927 0.048229 0.949629 0.910597 0.897258 1.211559 1.240578 1.226068

7 0.025273 0.929201 0.030173 0.979802 0.912324 0.946077 1.198989 1.180627 1.189808

8 0.023788 0.952989 0.004540 0.984342 0.939416 0.966562 1.389769 1.137673 1.263721

Bioactive Nitrogen-Containing Compounds with Spatial Carbocyclic Groups 9

TABLE 1.3  Experimental vs. Calculated R/s.

Compound mp, calc Rf, calc mp, exp Rf, exp
1 184.9834 0.518455 178.5 0.60
2 126.5095 0.704182 134.5 0.65
3 142.8738 0.705937 134.5 0.73
4 102.3756 0.591046 121.5 0.42
5 154.5519 0.776873 152 0.80
6 128.6926 0.633454 128.5 0.65
7 171.7885 0.867685 173 0.86
8 167.9010 0.917788 169 0.91
9 193.2231 0.447994 206.5 0.40
10 166.1550 0.486902 166.5 0.50
11 178.3934 0.473237 160 0.41
12 170.2936 0.525245 181.5 0.53
13 198.3374 0.549713 240.5 0.77
14 175.8185 0.426382 176.5 0.45
15 226.3155 0.555867 226.5 0.55
16 183.8285 0.146642 194.5 0.17

1.3.1  STUDY OF THE BIOACTIVE PROPERTIES OF

ADAMANTANE-CONTAINING ANILIDES AND NITROANILIDES
The modeling of the dependence of the structures of used nitrogen-containing ada-
mantane derivatives on their fundamental properties (melting point and Rf) allows
carrying out the theoretical evaluation of the possible bioactivity of the same struc-
tures. We carried out the preliminary virtual bioscreening of the obtained compounds
by using the internet-system program PASS C&T.24 The estimation of the probable
bioactivity of chosen compounds was carried out via parameters Pa (active) and Pi
(inactive); when Pa > 05, the compound could also show bioactivity experimen-
tally. From the above-mentioned virtual bioscreening, based on the analysis of the
obtained results, the synthesized compounds with experimentally high probability
(Table 1.4) (Pa > 0.5) possibly will show the following bioactivity: antibacterial, anti-
bacterial activity enhancer, anthelminthic, antiviral (Arbovirus, Influenza, Picorna-
virus), lipid metabolism regulator, and urologic disorders treatment.
Herewith, in the halogenated nitrogen-containing adamantane (15, 16) deriva-
tives, an increase in antiviral (Influenza) activity was observed. The synthesized
compounds with experimentally high probability (Table 1.5) possibly will show
the following bioactivity: anti-infective, dopamine release stimulant, anthelminthic,
antiparasitic.
TABLE 1.4  Relative Bioactivity of Some Nitrogen-Containing Adamantane Derivatives (1–14).
10
Pa/Pi
Lipid 5 Urologic Antiviral Membrane Dependence Antibacterial Activity enhancer
metabolism Hydroxytryptamine disorders Antiviral Antiviral (arbovirus) integrity treatment
Compound
regulator release inhibitor treatment (influenza) (picornavirus) agonist

1 _ 0.900/0.004 0.872/0.010 0.791/0.004 0.705/0.004 _ 0.703/0.101 0.741/0.014 _

2 _ 0.834/0.004 0.813/0.022 0.782/0.004 0.673/0.013 0.869/0.003 _ 0.545/0.056 0.436/0.239

3 _ 0.823/0.004 0.797/0.027 0.816/0.004 0.689/0.010 0.899/0.003 0.312/0.170 0.389/0.174 0.371/0.311

5 _ 0.371/0.087 _ 0.450/0.052 0.572/0.053 0.762/0.010 0.548/0.155 0.350/0.218 0.550/0.113

6 0.388/0.213 0.256/0.179 0.327/0.315 0.269/0.205 0.509/0.097 0.613/0.108 _ _ 0.663/0.022

7 0.344/0.241 0.778/0.005 0.745/0.049 0.638/0.011 0.679/0.012 0.803/0.005 _ 0.404/0.160 0.498/0.172

8 _ 0.746/0.005 0.755/0.044 0.549/0.023 0.724/0.005 0.820/0.004 0.549/0.154 0.543/0.057 0.593/0.070

9 _ 0.891/0.004 0.855/0.013 0.781/0.004 _ _ 0.752/0.083 _ _

10 0.973/0.003 _ _ _ _ _ 0.770/0.075 _ _

11 0.966/0.004 _ _ _ _ _ _ _ _

12 0.970/0.003 _ _ _ _ _ 0.838/0.043 _ _

13 0.971/0.003 0.876/0.005 0.818/0.021 0.775/0.005 0.705/0.004 _ _ _ _

14 _ 0.843/0.005 0.788/0.030 0.752/0.005 _ _ 0.792/0.065 0.720/0.017 _

Process Advancement in Chemistry and Chemical Engineering Research
Bioactive Nitrogen-Containing Compounds with Spatial Carbocyclic Groups 11

We tested the bactericidal and fungicidal activity of synthesized compounds ac-

cording to the method described in Ref. 25. To this target we applied the test micro-
organisms—Pectobacterium aroideae, Fusarium arenaceum, Autinomyces Griseus,
and Fusarium proliferate. The test results showed that synthesized compounds have
revealed selected bactericidal properties and have suppressed the development of
research cultures. The microbiological study of the investigated compounds con-
firmed the evaluated virtual concepts.

1.3.2  INORGANIC–ORGANIC HYBRID MATERIALS WITH

SPECIFIC PROPERTIES BASED ON SYNTHESIZED COMPOUNDS
One of the modern ways to protect the synthetic and natural materials from the ac-
tion of microorganisms is a creation of novel antibiocorrosive coatings with high
bioactivity and multivectorial and directional action based on inorganic–organic
hybrid composites.8 Antibiocorrosive coatings mainly contain two components—
biologically active compound and polymer matrix, where the bioactive compound
dropped. Some polyfunctional hetero-chained organic polymers, such as polyure-
thane elastomers, polyurethane acrylates and ionomers, have been successfully used
as a matrix for creation of antibiocorrosive coatings. In this regard, special interest
has been developed in many respects in bioactive, including bactericide and fungi-
cide polyurethanes.26, 27
At the first stage of the research, for the preparation of “short-term” action
polymeric composites, the following polyurethanes were selected:
1. Polyester urethane “PU”:
O O O O O O

* (OR)n OCNH Ar NHC 2

*OR /
OCNH Ar NHC* NHNHCNH Ar NHC 3
* ,
where R = –CH2CH(CH3)–; R/ = –(CH2)2O(CH2)2–.
2. Sulfur-containing polyester urethane “PUS”:
O O O O O O

* (OR)n OCNH Ar NHC 2

*OR/ OCNH Ar NHC* NHNHCNH Ar NHC 3
*
,
CH3 CH3

; ;
where Ar = R = -CH2CH(CH3)-; R/ = -( CH2)2O(CH2)2-.

HO3S SO3H

3. Ionomer of sulfur-containing polyester urethane “PUSI”:
O O O O O O

* (OR)n OCNH Ar NHC 2

*OR/ OCNH Ar NHC* NHNHCNH Ar NHC 3
* ,
12 Process Advancement in Chemistry and Chemical Engineering Research

CH3 CH3

where Ar = ; ; R = -CH2CH(CH3)-; R/ = -(CH2)2O(CH2)2-.

+_
_ +
(C2H5)3HNO3S SO3NH(C2H5)3

4. Polyester urethane “BUTYP T-261” based on 4,4-dimethylmethanediisoci-

anate and oligobuthyleneglicoladipinate.
Some adverse effects, in particular, low scratch and wear resistance and envi-
ronmental degradation, have hindered many important applications of polymers.28,
29
Thus, for physical and/or chemical modification of the above-mentioned polyure-
thanes for the purpose of improving tribological properties, silicon-organic oligo-
mers were used, which will be able to improve several properties of the initial poly-
mer systems including mechanical (elastic, adhesive strength) and thermophysical
(frost- and thermal-resistant) and hydrophobicity:
(a) bis(hydroxyalkyl)polydimethylsiloxane:

(b) α,ω-dihydroxymethylvinyloligoorganosiloxane:

HO{[Si(CH3)2O]98.5[Si(CH3)(CH=CH2)O]1.5}xH, where x = 3–5.

As bioactive compounds for antibiocorrosive coatings we used other nitrogen-
containing adamantane derivatives13, 30–32 such as transition metals coordination
compounds of adamantane-1-carboxylic acid hydrazide synthesized by us30,13 con-
sidering their stability and ability to form dipole–dipole and hydride bonds with
the polymeric matrix. It was expected that hydrazide metal complexes will show
various applications in the fields such as fungicidal, bactericidal, antiparasitic, anti-
oxidative, and cytotoxic studies.31, 32, 33, 34
The most probable structures of the obtained coordination compounds13 are
given in Scheme 1.2.
By using obtained polymeric matrices and coordination compounds (3–5 wt.%)
new effective and stable inorganic–organic antibiocorrosive coatings were obtained
(Table 1.6).
Bioactive Nitrogen-Containing Compounds with Spatial Carbocyclic Groups 13

SCHEME 1.2  Adamantane-containing hydrazide coordination compounds of some

transition metals.

TABLE 1.5  Relative Bioactivity of 1-(N-3,5-Dibromobenzoyl)aminoadamantane (15) and

4¢-(1-Adamantyl)-2-hydroxy-3,5-dibromobenzoylanilide (16).
Compound Pa/Pi

Anthelmintic (nematodes)
Dopamine release stimu-
Antiviral (picornavirus)
Antiviral (arbovirus)
Antiviral (influenza)

Antiviral denovirus)

Antiparasitic
ntiinfective

lant

15 0.857/ – 0.548/ 0.778/ 0.848/ 0.478/ 0.422/

0.003 0.005 0.005 0.009 0.057 0.035
–
16 0.903/ 0.731/ 0.617/ 0.520/ 0.807/ 0.749/ 0.544/ 0.512/
0.002 0.020 0.004 0.088 0.005 0.029 0.030 0.017

TABLE 1.6  Polymeric Composites and Antibiocorrosive Coatings Based on Polyurethanes

and Coordination Compounds.
1 Polyester urethane “PU”
2 Sulfur-containing polyester urethane “PUS”
3 Sulfur-containing polyester urethane “PUS”/3% α,ω-dihydroxymethylvinyloligoor
ganosiloxane
4 Ionomer of sulfur-containing polyester urethane “PUSI”
5 Polyester urethane “BUTYP T-261”
6 Polyester urethane “BUTYP T-261”/3% coordination compound
7 Polyester urethane “BUTYP T-261”/5% coordination compound
8 Polyester urethane “BUTYP T-261”/3% bis(hydroxyalkyl)polydimethylsiloxane
14 Process Advancement in Chemistry and Chemical Engineering Research

9 Polyester urethane “BUTYP T-261”/3% α,ω-dihydroxymethyl-

vinyloligoorganosiloxane
10 Polyester urethane “BUTYP T-261”/3% α,ω-dihydroxymethylvinyl oligoorganosi-
loxane/3% coordination compounds

The tribological properties of the polymeric matrices and antibiocorrosive coat-

ings were studied by using a Nanovea pin-on-disk tribometer from Micro Photonics
Inc. The tribometer provides dynamic friction results under rotation conditions.35 A
total of 440 steel balls each with a diameter of 3.2 mm made by Salem Specialty
Balls were used. The tests were performed under the following conditions: tempera-
ture 20 ± 2°C, speed 100 rpm, radius 2.0 mm, load 5.0 N. The number of revolutions
was 3000.
As shown in Figures 1.4 and 1.5, the dynamic friction for polyurethane matrices
mainly depends on their structure and the structure of the modifier. By the analysis
of curves of dynamic friction variation for nonmodified and modified polyurethanes
and antibiocorrosive coatings based on them (Figs. 1.4 and 1.5), it was established
that the value of dynamic friction is high for nonmodified polyurethane matrices
and coatings based on them. The addition of silicon-organic oligomers (3–5 wt.%)
to polyurethane matrices leads to a decrease in the above-mentioned parameter (Fig.
1.6).
By the doping of bioactive coordination compounds in the polyester urethane
matrix based on 4,4-dimethylmethanediisocyanate and olygobuthylenglycole adipi-
nate, the value the coefficient of dynamic friction is increased. This fact could be
explained by the influence of their spatial structure. It was shown that the modifica-
tion of polyester urethanes by silicon-organic oligomers the dynamical friction was
reduced (Fig. 1.6), and is conditioned by high plasticized ability of flexible siloxane
oligomers.

FIGURE 1.4  Dependence of the dynamic friction on the distance of sliding for polyurethane
matrices and antibiocorrosive coating films based on them (1–5, Table 1.6).
Bioactive Nitrogen-Containing Compounds with Spatial Carbocyclic Groups 15

FIGURE 1.5  Dependence of the dynamic friction on the distance of sliding for the matrix
based on polyester urethane (“BUTYP T-261”) and corresponding antibiocorrosive coatings
(5–10, Table 1.6), nonmodified and modified with silicon–organic oligomers.

FIGURE 1.6  The comparison of the values of average dynamic friction for polymer
matrices and antibiocorrosive coatings based on them (Table 1.6).
16 Process Advancement in Chemistry and Chemical Engineering Research

The obtained results were also confirmed by studying surface morphology (scan-
ning electron microscopy) of the films from modified and nonmodified polymeric
matrices for the purpose of creating antibiocorrosive coatings (Fig. 1.7). Plastic de-
formation of the corresponding films under the constant load equal to 5 N showed
that split behavior of sulfur-containing polyester urethane “PUS,” modified by α,ω-
dihydroxymethylvinyloligoorganosiloxane, characterized with less crack nucleation
in comparison with non-modified “PUS” (Table 1.6). It must be noted that polyes-
ter urethane “BUTYP T-261,” modified by bis(hydroxyalkyl)polydimethylsiloxane
(Table 1.6), demonstrated least crack nucleation among the tested polymeric matri-
ces.

FIGURE 1.7  The surface morphology of the polymeric films for antibiocorrosive coatings
based on nonmodified and modified polyurethanes (Table 1.6).

The hydrophobility of the obtained antibiocorrosive coatings by the gravimetric

method was determined. It was established that for 300 h their water absorption abil-
ity for modified matrices by silicon–organic oligomers did not exceed 0.1%.
The influence of isothermal aging (40 and 60°C), the so-called weather ability
(stability toward O2, CO2, and moisture complex action) and photochemical stabil-
ity (stability toward ultraviolet and visible light), was studied. It was shown that for
more than 3 months (at room temperature) the initial appearance (state), color, opti-
cal transparency, and mechanical properties (surface homogeneity without of split
formation) of antibiocorrosive coatings (Table 1.6, 8–10) did not worsen.
By preliminary investigations, it was established that the created antibiocorro-
sive composites could be used for the prevention of materials from biodeteriora-
tion and noncontrolled biodegradation; the inhibition of growth and expansion of
Bioactive Nitrogen-Containing Compounds with Spatial Carbocyclic Groups 17

microorganisms, which are causal factors of infectious diseases; prophylaxis; and

treatment of above-mentioned diseases.
The created composites can also be recommended for the preparation of protec-
tive covers with multivectorial application (film materials and impregnating com-
positions) stable for biocorrosion; materials with antimycotic properties for prophy-
laxis and treatment of mycosis; biologically active polymer composite materials for
the protection of museum exhibits; and for human protection during their contact
with microorganisms.36

1.4 CONCLUSION
1. Quantitative “structure–properties” relationships (QSRR/QSAR) based
on experimental data for the construction of models of dependences of
the physical properties of biologically active 16 nitrogen-containing com-
pounds with bioactive spatial carbocyclic (adamantane) groups, synthesized
by us, on molecular structures were studied.
2. Several sets of molecular descriptors were used. The presence of the dataset
outliers was controlled by using PCA; to ascertain the quality of models,
cross-validation was used.
3. Based on the performed research, one concludes that the best models have
been acquired by the use of the GETWAY description of the obtained com-
pounds.
4. Virtual bioscreening and activity toward various microorganisms of the ob-
tained compounds were studied. The area of their application was estab-
lished. The microbiological study of the investigated compounds confirmed
the evaluated virtual concepts.
5. Polyurethanes with various structures as a polymeric matrix for antibiocor-
rosive coatings were chosen and used. This is mainly due to the tribological
properties improvement in silicon–organic oligomers used, photochemical
stable and “Short-time” active inorganic–organic antibiocorrosive coatings
were obtained. The tribological properties of the obtained polymeric com-
posites and antibiocorrosive coatings were determined. It was established
that the modification process could used to improve the tribological proper-
ties of polyurethanes.

ACKNOWLEDGMENT
The authors thank Shota Rustaveli National Science Foundation for financial sup-
port.
18 Process Advancement in Chemistry and Chemical Engineering Research

KEYWORDS

•• QSRR/QSAR
•• models
•• descriptor
•• calculation
•• bioactive
•• bioscreening
•• antibiocorrosive
•• tribology
•• composite

REFERENCES
1. Lekishvili, N.; Barbakadze, Kh.; Zurabishvili, D.; Lekishvili, G.; Arziani, B.; Fainleib, A.;
Grigorieva, O.; Brostow, W.; Datashvili, T. Oxid. Commun. (Int. J.) 2012, 35 (4), 746–761.
2. Gu Ji-Dong. Int. Bioterior. Biodegr. 2003, 52 (1), 69–91.
3. Kurdina, M. I.; Malikov, V. E.; Zarikova, N. E.; et al. Bull. Dermatol. Venerol. 2002, 5, 49–52.
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lia, Z.; Lomtatidze, Z. Antibiocorrosive Covers and Conservators Based On New Carbofunc-
tional Oligosiloxanes and Biologically Active Compounds. Oxid. Commun. (Int. J.) 2010, 33
(1), 104–124.
5. Howard G. T. Int. Bioterior. Biodegr. 2002, 49 (4), 242–252.
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9. Morozov, I. S.; Petrov, V. I.; Sergeeva, S. A. In Pharmacology of Adamantanes. Volgograd
Medical Academy: Volgograd, 2001.
10. Arcimanovich, N. G.; Galushina, T. S.; Fadeeva, T. A. Adamantanes—Medicines of the XXI
Century. Int. J. Immunorehab. 2000, 2 (1), 55–60.
11. Kovtun, V. Y.; Plakhotnik, V. M. Using of Adamantane Carbonilic Acids for Modification of
Drugs Properties and Biologically Active Compounds. Chem. Pharm. J. 1987, 8, 931–940.
12. Barbakadze, Kh.; Lekishvili N., Pachulia, Z. Adamantane-Containing Biological Active Com-
pounds: Synthesis, Properties and Use. Asian J. Chem. 2009, 21 (9), 7012–7024.
13. Lekishvili N. and Kh. Barbakadze. Asian J. Chem., 2012, 24 (6), 2637–2642.
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17. R. Todeschini, M.; Lesagni, E.; Marengo. J. Chemom. 1994, 8, 263–273.
18. V. Consonni, R.; Todeschini, L.; Pavan. J. Chem. Inf. Comput. Sci. 2002, 42, 682–692.
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19. Todeschini, R.; Consonni V. In Handbook of Molecular Descriptors; Wiley-VCH: Weinheim,

2001.
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Tbilisi, Georgia, 2010, p. 20.
CHAPTER 2

RELATIONSHIP BETWEEN THE

STRUCTURE, MOLECULAR DYNAMICS,
AND THERMO-OXIDATIVE STABILITY
OF LOW-DENSITY POLYETHYLENE
AND BUTYL RUBBER BLENDS
T. V. MONAKHOVA1, L. S. SHIBRYAEVA1, N. N. KOLESNIKOVA1,
A. I. SERGEEV2, S. G. KARPOVA1, and A. A. POPOV1
1
Institute of the Russian Academy of Sciences, N.M. Emanuel Institute of Biochemical
Physics, Russian Academy of Sciences, Moscow, Russia
2
Institute of the Russian Academy of Sciences, N.N. Semenov Institute of Сhemical
Physics, Russian Academy of Sciences, Moscow, Russia

CONTENTS
Abstract....................................................................................................................22
2.1 Introduction....................................................................................................22
2.2 Experimental Details......................................................................................22
2.3 Results and Discussion..................................................................................23
Keywords.................................................................................................................34
References................................................................................................................34
22 Process Advancement in Chemistry and Chemical Engineering Research

ABSTRACT
The binary blends of butyl rubber (BR) and low-density polyethylene (PE) contain-
ing 0, 10, 20, 30, 40, 60, 70, 80, and 100 mass% of PE were investigated. Thermo-
physical parameters, such as the structure of PE and BR polymer chains, segmental
mobility of the chains in the amorphous regions, proton transverse magnetic re-
laxation, and kinetic of oxidation, were determined. The relationship between the
structure, molecular dynamics, and thermo-oxidative stability of low-density PE
and BR blends was established.

2.1 INTRODUCTION
Studies aimed at developing new polymeric composites consisting of plastic and
rubber, which do not require vulcanization and reinforcement, attract a significant
interest nowadays. These studies are mainly based on the fact that the introduction
of polyethylene in elastomers (butyl rubber, ethylene propylene diene rubbers, and
others) makes it possible to receive the systems with a sufficiently high cohesive
strength.1–3 The method for creating these materials—mechanical melt mixing—
makes their resistance to thermal and thermo-oxidative destruction an important
problem. The same property is needed for processing and use of the products made
of polymer composites. The main challenge facing the researchers and manufactur-
ers engaged in the field of developing polymeric materials is to increase their ther-
mo-oxidative stability. The study was aimed at establishing a relationship between
the structure, molecular dynamics, and thermo-oxidative stability of low-density
polyethylene (LDPE) and butyl rubber (BR) blends.

2.2  EXPERIMENTAL DETAILS

Binary blends of BR and LDPE were investigated. We used butyl rubber 1675N
(hereinafter BR) and polymer LDPE 273-76. The blends containing 0, 10, 20, 30,
40, 60, 70, 80, and 100 mass% of PE were prepared in a Brabender-type mixer at a
temperature of 170°C. The rotor speed was 60 rpm. The mixing time was 15 min.
Film samples were obtained by compressing on a laboratory press at a temperature
of 170°C, followed by rapid cooling to room temperature.
Thermophysical parameters were determined by differential scanning calorim-
etry (DSC), using the microcalorimeter DCM-10. Indium was used as a standard
(Tm = 156.5°C; specific enthalpy is 28.4419 J/g). The thermal melting effect of the
samples was determined by the peak area between the DSC curve and the baseline.
We calculated the enthalpy of melting, based on the obtained thermograms. To de-
termine the degree of crystallinity of LDPE, the value of the specific melting heat of
PE crystallites was assumed to be 288 J/g. The error in the determination of melting
point did not exceed 1°C, the melting heat 10%.
Relationship Between the Structure, Molecular Dynamics 23

The structure of PE and BR polymer chains was determined by IR spectroscopy.

The error in the determination of structural parameters did not exceed 15%.
We used the paramagnetic probe method to determine the segmental mobility of
the chains in the amorphous regions of blends. A stable nitroxyl radical 2,2,6,6-tetra-
methylpiperidin-1-oxyl was used as a paramagnetic probe, which was injected in the
polymeric film of saturated vapor. The spectra of nitroxyl radicals introduced in the
sample were obtained by Electron paramagnetic resonance EPR. The radical probe
correlation time (τc) was calculated from the spectrum by the formula4

τ = DH + (√ ( I + / I − ) – 1) 6.65 × 10 –10 ,
where ∆H+ is the width of the spectral components, located in the weak field, and
(√(I+/I−) – 1) is the intensity component in the weak and strong field, respectively.
Error in the determination of τ was within 5%.
Proton transverse magnetic relaxation of PE–BK samples was performed on a
Bruker Minispek PC-120 spectrometer. This spectrometer operates at a proton reso-
nance frequency of 20 MHz. The length of the 90° pulse is 2.7 µs and dead time is
7 µs. Two different pulse sequences were used for the measurement of T2 relaxation
time and the amount of rigid (crystalline) and soft (amorphous) phase components.
To evaluate the spin–spin relaxation time T2 and the fraction of protons with differ-
ent degrees of mobility, we used techniques for studying induced signal decay after
a 90° pulse (FID, free induction decay) and CPMG (Carr–Purcell–Meiboom–Gill).
The error in the determination of parameters did not exceed 5%.
Kinetic oxidation curves of the mixtures were obtained using a manometric de-
vice with a circulating pump and by freezing volatile oxidation products at a tem-
perature of 180°C and an oxygen pressure of 300 mm Hg (40 kPa). The error in the
determination of kinetic parameters did not exceed 10%.

2.3  RESULTS AND DISCUSSION

The purpose of the research was to study binary blends of BR and LDPE, contain-
ing 0, 10, 20, 30, 40, 60, 70, 80, and 100 mass% of PE. The DSC method was used
to determine the structural parameters for the crystalline regions of the sample of
blends. Thermal parameters were determined by the same method. The results of
research are presented in Table 2.1 for all the mixtures. The melting endotherms
of the sample of mixtures have a single melting peak of PE. As seen from the table
data, the temperature at the maximum PE melting peaks is insignificantly shifted
toward low temperatures with a decrease in the PE content of the mixture, which
may be associated with the formation of defective or smaller crystalline structures
in the LDPE phase. At the same time, the degree of crystallinity of polyethylene (χ)
decreases only in the samples with a high rubber content (70 mass%). This is most
likely to be associated with the changes in the phase structure of the mixture, phase
24 Process Advancement in Chemistry and Chemical Engineering Research

inversion. Rubber forms a dispersion medium in the samples of this composition,

where PE is distributed in the form of small particles of the dispersed phase.

TABLE 2.1  Thermal Parameters of BR–PE Blends.

Composition of the BR/PE sample 0/100 20/80 40/60 60/40 70/30 80/20
Тm max (°С) 129.0 129.0 128.0 128.0 127.0 127.0
∆Нm of the blends 180.0 143.0 111.0 72.0 48.0 30.0
(J/g) 180.0 179.0 185.0 180.0 160.0 150.0
∆Нm PE (J/g) 61.0 61.0 63.0 61.0 54.0 51.0
χPE (%)

The changes in the structure of amorphous regions were determined by the IR

spectroscopy method. The content of straightened and coiled conformers in the
amorphous regions of the PE component was defined by the changes in the intensity
of the bands responsible for deformation vibrations of the chains in straightened
and folded conformations. The concentration of the former in PE was determined
by the intensity of the band at 720 cm–1 and the D720/D730 ratio. The band at 720
cm–1 is responsible for the fluctuations of methylene sequences, –(CH2)n, n > 5, in
a trans-zigzag conformation in the amorphous regions of PE. The content of folded
conformers of the TGT and GG types was determined according to the intensities of
the bands at 1080 and 1306 cm–1, respectively. The obtained data on the changes in
the structure of PE chains depending on the composition of the PE–BR blends are
shown in Table 2.2. As seen from the table, the content of straightened conformers
T-T in the PE component increases, whereas the content of the coiled GG conform-
ers decreases with the increased addition of rubber in PE.

TABLE 2.2  The Data on Changes in the Structure of PE and BR Chains Depending on the
Composition of PE–BR Blends.
PE D1305 D1080 D720 D1230 D853
(mass%) D2740 D2740 D730 D2740 D2740
0 – – – 26.4 0.764
30 – – 1.263 42.0 0.979
40 0.062 – 1.22 48.7 1.254
60 0.750 0.520 1.19 65.4 1.838
80 0.875 0.417 1.18 96.6 2.720
100 1.229 0.312 1.11 – –
Relationship Between the Structure, Molecular Dynamics 25

The nature of changes in the intensities of the above-mentioned bands in the

PE component suggests the presence of structural rearrangements by the type of
conformational transitions GG → TGT → TT; the mechanism of this transition
was previously established for the PE subjected to orientation drawing. Tension
generated in the transduction chains under the influence of deformations as a result
of mixing components may lead to similar changes in the conformational composi-
tion of chains in the volume of a polymer. Another reason for the enrichment of PE
transduction chains with straightened conformers is implementation of the inter-
phase phenomenon, in other words, the emergence of tension as a consequence of
intermolecular interactions at the phase separation border.
The character of the changes in the BR structure can be established from the
changes in the intensity of the bands at 1230 and 853 cm–1. They grow monotoni-
cally with the increased content of BR, which apparently points to an increase in the
size of its particles and, hence, the length of the PE–BR phase separation border.
This leads to a speculation that the enrichment of PE matrix chains by straightened
conformers with a decrease in its content in the mixture occurs on the boundary with
the surface of the rubber particles. Changes in the structure of components and their
chains must lead to a change in the molecular dynamics of polymers.
Changes in the structure of components and their chains should result in the
alterations of the molecular dynamics of polymers. To determine the segmental mo-
bility of the chains in the amorphous regions of blends, we used the paramagnetic
probe method. A stable nitroxyl radical was used as a paramagnetic probe, which
was injected in the polymeric film of saturated vapor. The spectra of nitroxyl radi-
cals introduced in the sample were obtained by EPR. The radical correlation time
(τc) was calculated from the spectrum. Segmental mobility is characterized by the
value reciprocal to τc. The curve showing the change in τc of the blend is shown
in Figure 2.1. As can be seen, the curve of the relationship between τc and the BR
content in the mixture has a complex shape. With the increase in the content of BR
in the mixture up to 40%, increase in the correlation time of the radical probe, i.e., a
drop of the segmental mobility, is observed in the sample with 40% BR. The correla-
tion time of the probe decreases with the growth of the rubber content in the mixture,
thus increasing the mobility of the chains. Analysis of the data on the solubility of
radical in mixtures shows that the highest concentration of the nitroxyl radical at the
highest correlation time is observed in the region of the phase inversion (Fig. 2.2). It
is speculated that the rearrangement of the conformational structure of the polymer
chains in the PE matrix provides an increase in the free volume and simultaneously
reduces the segmental mobility of the chains. Rubber fills the elements in the free
volume of the blend and forms its own phase with the growth of its content. This
leads to the reduction of the solubility of the nitroxyl radical, but decreases the
radical correlation time. Given that the intermolecular interactions are absent, the
radical correlation time characterizing the chain mobility will be determined by the
flexibility of PE chains and its changes under the influence of the rubber introduced
26 Process Advancement in Chemistry and Chemical Engineering Research

in polyethylene. Obviously, the maximum concentration of the radical corresponds

to the phase inversion.

FIGURE 2.1  Dependence of the correlation time on the PE content.

FIGURE 2.2  Dependence of the concentration probe on the PE content.

Molecular dynamics of PE–BR sample blends studied by the proton magnetic

relaxation method on NMR was performed on a Bruker Minispek PC-120 spectrom-
eter. This spectrometer operates at a proton resonance frequency of 20 MHz. The
Relationship Between the Structure, Molecular Dynamics 27

length of the 90° pulse is 2.7 µs and dead time is 7 µs. Two different pulse sequences
were used to measure the relaxation time T2 and amount of firm (crystalline) and
soft (amorphous) phase components:
1. FID after a single pulse (90°) excitation;
2. CPMG—multiple-echo pulse sequence 90°–(τ–180°–τ)n.
The FID pulse sequence5,6 was used to register a quickly decaying part of the
slow-moving protons (solid phase). The time of relaxation of these protons is a few
microseconds and the duration of the collapse heavily depends on the inhomogene-
ity of the magnetic field Bo in the sample. It is not possible to use this method for the
precise determination of T2, which lasted for more than 100 µs. The CPMG method
removes the effect of the inhomogeneity of the magnetic field, but it can be used
only for the registration of the slow part of collapse.
Our experiments were performed under the following conditions:
FID
• The temperature (t) 40°C
• The recycle delay between scans (RD) 1 s
• The beginning of the decay measurement (BD) 10 µs
• The end of the decay measurement (ED) 100 µs
• The number of experimental points (n) 50
• The number of scans (NS) 25
CPMG
• t = 40°C, RD = 1 s, n = 30, BD = 48 µs, ED = 1440 µs
• NS: 25–144
• Time between 90 and 180° pulses (τ) 12 µs
Our results of FID and CPMG experiments are presented in Table 2.3. The
FID experiment for pure PE and PE–BR compositions (80 and 20 wt.% PE) dem-
onstrated low mobile proton fraction for all samples (T2 = 4–5 ms). The relative
amount of these protons was 90–95%. When the part of BK in composition in-
creased up to 80 mass%, the amount of mobile protons decreased to 47%. This
fact is likely to indicate the increase in the segmental mobility of the chains in the
mixtures as compared with pure PE and PE matrix. Since PE crystallites can serve
as clamps for transition chains and, hence, inhibit the relaxation of protons, one of
the reasons for the growing mobility of the chains in the blend may be reduction
in the crystalline regions of polyethylene due to dilution of the polymer mass by
an amorphous rubber.
28 Process Advancement in Chemistry and Chemical Engineering Research

TABLE 2.3  Magnetic Relaxation Characteristics of PE–BR Blends.

Composition of χ of PE, SIS CPMG
the BR/PE sample χof the
Proton spin–spin Relative con- Proton Relative
Blend
relaxation time tent (%) spin–spin content
%
T2 (µs) relaxation (%)
time T2 (µs)
0/100 61 5.2 92.0 1357 49.0
61 194 8.0 147 51.0

20/80 61 3.3 95.0 1010 60.0

50 128 5.0 150 40.0

40/60 63 – – 689 74.0

38 151 26.0

60/40 61 – – 636 61.0

25 240 39.0

70/30 54 5.2 – 651 80.0

16 214 239 20

80/20 51 – 47.0 649 85.0

10 53.0 230 15.0

100/0 0 – – 653 100

The crystallinity of PE for the samples with its different content (from 40 up to
100 mass%) did not change, but the volume of the crystalline phase in PE–BK com-
positions decreased more than twice. The molecular mobility of polymer chains also
depends on the structural amorphous phase of composition and on a crystal–amor-
phous interface, which can be detected either as crystalline or as amorphous fraction
depending on the method used. The deconvolution of proton transverse relaxation
curves for different polymers (polyethylene, polypropylene, and their composition)
reveals several components, which can be attributed to the crystalline, amorphous
phases and crystal–amorphous interface.7,8 It is possible to suggest that the less mo-
bile proton fraction in our experiment (T2 = 5 µs) is the fraction of the crystalline
Relationship Between the Structure, Molecular Dynamics 29

phase in the PE–BK composition. CPMG investigations of the PE–BR composition

demonstrated two exponential components of the experimental relaxation curves—
slow (S) and fast (F) decay components. The S-component could characterize the
amorphous phase and the F-component (as a slow part of decay in the FID experi-
ment) intermediate phase. When BR content in samples increased, the contribution
of the S-component in experimental curves of decay increased too (Fig. 2.3). It is
possible that the S-component and F-component reflect the rubber and polyethylene
proton mobility, respectively. S-component relaxation times T2 for BR samples (40,
60, 70, and 80 mass% BR) are close to T2 of pure BR (T2 = 650 µs) and it confirms
our assumption. The growth BR fraction in the composition led to an increase in T2
of the F-component and it suggested an increase in proton mobility in this interme-
diate phase. Obviously, this fact points to the formation of amorphous regions in
the blends enriched with rubber, in which intermolecular interactions between PE
and BR are manifested. The regions such as these represent interphase layers. The
decline in the crystallinity degree of the polyethylene component also says about the
formation of interphase layers. PE crystallites in these samples are surrounded by
the amorphous regions containing rubber macrochains, which prevents formation
of crystallites and reduces the degree of crystallinity of the polymer. Changes in the
molecular mobility of chains have an impact on the thermo-oxidative resistance of
PE–BR sample blends.

FIGURE 2.3  Proton relaxation time T2 (microseconds) of the slow (S) component depending
on the content of the amorphous phase in the PE–BR blend.
30 Process Advancement in Chemistry and Chemical Engineering Research

Figure 2.4 shows the kinetic curves of oxygen absorption by the tested samples.
As seen from the figure, mixing polyolefin and rubber leads to the changes in the ki-
netics of oxygen absorption. Moreover, depending on the composition of the blend,
the reaction rates not only vary but also correlate with the changes in the segmental
mobility of the chains. For example, the nature of the curve showing the relationship
between the radical probe correlation time τc and the composition of the blend corre-
sponds to the changes in the rate of polymer oxidation. The introduction of rubber in
PE leads to a slower oxidation process of the PE component in all the blends and of
the BR component in the blends containing 30 and 40 mass% of PE. The oxidation
reaction for PE starts with a delay—the induction period was about 50 min, while
for a mixture containing 80% of PE, it was 20 min, and for 60%, 13 min. Other
blends, as well as BR, are oxidized without an induction period. The dependence
of the maximum rates of oxidation (Wo2) of the samples on their composition has
a complex nature (Table 2.4). Figure 2.5 (curve 1) shows the dependence of the
maximum oxidation rate on the composition of the samples, which was obtained
from the experiment, taking into consideration the oxidation of amorphous regions
of oxygen absorption. The two regions can be distinguished on the curve (compare
with the correlation time of the radical). The first region corresponds to the change
in the composition from 5 to 40 mass% of PE. Moreover, a clear drop in the maxi-
mum rate of oxygen absorption is observed with increase in the content of PE. In
the second region of the curve, Wo2 monotonously increases with the increase of the
PE content up to 40 mass% or more. We used three models to describe the kinetics
of oxygen absorption by the PE–BR sample blends. The first model was based on
the following approach: since the rate of BR oxidation is lower than the rate of PE
oxidation, the first value was neglected. We assumed that the kinetic curves describ-
ing the absorption of oxygen by sample blends of different composition could be
considered the curves of PE component oxidation. A kinetic curve for each blend
was transformed into a curve, which took into account oxidation of PE, that is, was
calculated per 100% of its content. The dependence of the values of oxidation rates
obtained from the transformed curves on the content of PE is shown in Figure 2.5
(curve 2). Another approach took into consideration independent oxidation of PE
and BR. At the same time, the oxidation rate of the sample was determined on the
basis of the additive dependence as the sum of the rates of oxygen consumption by
its components. Theoretical curves of oxygen absorption by pure polymers taking
into account the reactivity of the amorphous phase of PE and BR and the composi-
tion of the mixture were obtained in the study. Based on the curves, gross values
of the rates were defined, and the dependence of these rates on the composition of
the samples was obtained (Fig. 2.5, curve 3). The comparison of the theoretical
curves (2 and 3) and the experimental curve (1) shows significant differences in
their shapes. The curve describing the localization of oxidation in the PE compo-
nent has the form of the exponent. Moreover, a sharp increase in the rate of oxygen
absorption is observed for the samples with a low content of the polyethylene com-
Relationship Between the Structure, Molecular Dynamics 31

ponent. All this fundamentally distinguishes curve 2 from the experimental curve. In
accordance with curve 3, which takes into account the additive contribution of the
components in the oxidation of the blend, the oxidation rate of the samples should
increase monotonously with the increase in the PE content. This also contradicts the
observed experimental dependence.

FIGURE 2.4  Kinetic oxidation curves for different films: PE (1), BR (2), blends of BR/PE
(70/30) (3), and BR/PE (60/40) (4) at 180°C; the oxygen pressure is 300 mm Hg.

FIGURE 2.5 Relationships of the oxidation maximum rate and the composition of sample
blends obtained from the experiment, taking into account the oxidation of the amorphous
regions (1), and theoretical ones, obtained from PE oxidation conditions (2), and from
participation in the oxidation of both components according to the additive scheme (3).
32 Process Advancement in Chemistry and Chemical Engineering Research

TABLE 2.4  Dependence of the Rate of Oxidation at 180°C Blends PE and BR on the
Composition.
Composition
of the BR/PE 0/100 20/80 40/60 60/40 70/30 80/20 90/10 95/5 100/0
sample
The rate of
oxidation 2.0 1.5 1.4 0.5 0.6 0.9 1.2 1.1 0.9
(×*104 mol/
kg s)

Data presented in Figure 2.5 show that a model which takes into account cross-
radical reactions between components is needed to describe the kinetics of oxidation
of PE–BR mixtures. In this case, the oxidation of PE–BR mixtures can be described,
taking into account the oxidation peculiarities of rubbers, by the following kinetic
scheme:
Initiation of the kinetic oxidation chain:
RpeH → Rpe*
RbrH → Rbr*
Development of the kinetic chain:
For PE:

k11
Rpe* + O2 → RpeO2 * (2.1)

kp11
RpeO2* + RpeH → RpeOOH + Rpe* (2.2)

For BR:

k22
Rbr* + O2 → RbrO2 * (2.3)

kp22
RbrO2* + RbrH → RbrOOH + Rbr* (2.4)

RbrO2* →R1brCHO + R2brO* (2.5)

R2brO* + RH → R2brOH + R* (2.6)

BR chain transfer reactions:

Relationship Between the Structure, Molecular Dynamics 33

R2brO* + –CH=CH– → –CH–C*H– (2.7)

OR2br
Secondary reactions of BR:

R2brOH + O2 → aldehydes (2.8)

R1brCHO + O2 →acids (2.9)

Cross-reactions of the chain development:

kp12
RpeO2* + RbrH → RpeOOH + Rbr* (2.10)

kp21
RbrO2* + RpeH → RbrOOH + Rpe* (2.11)

Chain termination (a quadratic break on peroxide radicals takes place at high

oxygen pressure; alkyl and alkoxide radicals may participate in the break in the
rubber):
kt11
2RpeO2* → products (2.12)
kt22
2RbrO2*(R*BR, RO*br) → inactive products or cross-links (2.13)

Cross-termination reaction:
kt12
RpeO2* + RbrO2*(R*br, RO*br) → inactive products or cross-links (2.14)

Free valence, which emerged in the PE component of the blend, was released
from the “cell” and localized in the interphase layer or at the interphase boundary,
can participate in the BR component in the processes that are competitive to oxida-
tion of hydrocarbon radicals, for example, in the destruction by reaction (2.5) or
cross-linking of polymer chains by reaction (2.14). Moreover, this chain process of
hydrocarbon oxidation may be blocked, which can be represented as a linear break:
k′t12
RpeOO* (Rpe*) + RbrH → inactive products (2.15)

or
k′t12
RpeOO* + RbrH → [Rbr* + RpeOOH] → Rbr–O–Rpe (2.16)
34 Process Advancement in Chemistry and Chemical Engineering Research

Intermolecular interactions are necessary for cross-reactions. They can be real-

ized through the contact of different polymer chains at the interphase boundary or
interphase layer. One might speculate that the complex (bimodal) dependence of the
oxidation rate on the blend composition, which we observed in the study, is due to
the peculiar features of the structure of PE–BR sample blends. The slowdown of the
oxidation rate of the sample mixtures is associated with the formation of interphase
boundaries and layers, that is, transition of molecules between the polyethylene
phase and elastomeric matrix, thus creating a structure to ensure the development
of cross-reactions.
The authors speculate that the radicals arising from cross-reactions lead to the
transfer of the free valence of macromolecules from rigid-chain PE to flexible-chain
BR; for this reason, they can pass into an inactive form, or die in the reaction of
rubber destruction or cross-linking. Obviously, the greatest contribution of cross-
reactions leading to a decrease in the oxidation activity of the blends is made in the
samples enriched with rubber. In blends with a high content of PE, the contribution
of cross-reactions decreases, chain reactions of polyethylene oxidation in its phase
dominate, and the total rate of the blend oxidation starts to increase up to the oxida-
tion rate of a pure polymer. Thus, the oxidation ability of PE–BR blends depends on
the contribution of cross-reactions, the mechanism for the reaction of the free va-
lence transfer from one component to another, whose implementation is determined
by intermolecular contacts of PE and BR macromolecules in the interphase layers,
or at the interphase boundaries.

KEYWORDS

•• low-density polyethylene
•• butyl rubber
•• blends
•• thermal oxidation
•• molecular dynamics

REFERENCES
1. Zakharchenko, P. I.; Yashunskaya, F. I.; Evstratov, V. F.; Orlovsky, P. N. In Spravochnik Rez-
inshchika; Chemistry: Moscow, RU, 1971; pp 342–395.
2. Schwartz, A. G.; Dinzburg, B. N. In The Combination of Rubbers with Plastics; Khimiya:
Moscow, RU, 1972; p 224.
3. Xakimulin, Yu. N; Volfson, S. I.; Kimel´blat, B. I. Caoutchouc Rubber 2007, 28, p 32.
4. Piotrovsky, K. B.; Tarasova, Z. N. In Aging and Stabilization of Synthetic Rubbers and of
Vulcanizates; Khimiya: Moscow, RU, 1980.
5. Carr, H. Y.; Purcell, E. M. Phys. Rev. 1954, 94, 630.
Relationship Between the Structure, Molecular Dynamics 35

6. Meiboom, S.; Gill, D. Rev. Sci. Instrum. 1958, 29, 688.

7. Hedesiu, C.; Dan, E.; Demco, D. E.; Kleppinger, R.; Buda, A. A.; Blümich, B.; Remerie, K.;
Victor, M.; Litvinov, V. M. Polymer 2007; 48. 3, 763.
8. Blom, Н.P.; the, J.W.; Bremner, T.; Rudin, A. Polymer 1998. 39 (17), 4011.
CHAPTER 3

A STUDY ON POSSIBILITIES FOR

CELLULOSE-BASED TEXTILE WASTE
TREATMENT INTO POWDER-LIKE
FILLERS FOR EMULSION RUBBERS
V. M. MISIN1, S. S. NIKULIN2, and I. N. PUGACHEVA2
1
N. M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences,
Moscow, Russia
2
Voronezh State University of the Engineering Technologies, Voronezh, Russia

CONTENTS
Abstract....................................................................................................................38
3.1 Introduction....................................................................................................38
3.2 Experimental Section.....................................................................................39
3.3 Results and Discussion..................................................................................40
3.4 Conclusion.....................................................................................................52
Keywords.................................................................................................................53
References................................................................................................................53
38 Process Advancement in Chemistry and Chemical Engineering Research

ABSTRACT
The main objective of this chapter is to review the possibility of filling butadiene-
styrene rubber of SKS-30 ARK grade with powder-like fillers made of cotton fiber.
Another objective of this chapter is incorporation of the rubber at the stage of latex
as well as the estimation of the effect of fillers on the process of coagulation and the
properties of the composites. This chapter will investigate the properties of compos-
ite materials on the basis of rubbеr latexes and fibrous materials.

3.1 INTRODUCTION
Fiberfills have a wide diverse raw material base that is practically unlimited. Various
fiberfill waste products are formed at textile enterprises, garment workshops, and so
on. Therefore, an important and actual practical task is to search for most perspec-
tive directions of their usage.1
In some of the published works, it was shown that fiberfills can be applied in
composite structures of different intended purposes. Special attention is paid to the
use of fiberfills in polymer composites. They are used in the production of mechan-
ical-rubber articles (MRA). Incorporation of fiberfills and additives into MRA are
performed with rolling mills in the process of producing rubber compounds. This
way of incorporation does not allow attaining their uniform distribution in the bulk
of rubber compound that will further have a negative effect on the properties of the
obtained vulcanizates. A uniform distribution of fiberfills in the bulk of polymer
matrix can be obtained by the change of the way of their incorporation. For example,
incorporation of fiberfills into the latex of butadiene-styrene rubber before its sup-
ply to coagulation allows us to attain their uniform distribution in the obtained rub-
ber crumb, and this results in an increase of such quality factors of vulcanizates as
their immunity to the thermal-oxidation effect, multiple deformations, and so on.2,3
Results of the investigations of the influence of small doses of fiberfills (up to 1
mass% in a rubber) on the process of rubber extraction from latex and the properties
of the obtained composites are presented in Refs. 2 and 3. In Ref. 4, a technological
difficulty was noted that was related to the incorporation of fiberfills into the process
in the dosage of more than 1 mass% in the rubber.
In this situation, it would be interesting to transform fiberfills into the powder
state. This will make possible to incorporate a greater amount of filler into the rub-
ber just at the stage of its production, and thus to attain its uniform distribution in
the rubber matrix.
Powder-like fillers have rather wide application in the production of tires and in
mechanical rubber industry.5 The overwhelming amounts of the used powder-like
fillers are of inorganic nature and they are incorporated into rubber compounds with
the use of rolling mills during their production. This way of incorporation, just as
in the case of fibers, does not make it possible to attain a uniform distribution of the
A Study on Possibilities for Cellulose-Based Textile Waste Treatment 39

filler in the rubber compound that further affects the properties of produced articles.
Therefore, the elaboration of the new ways of incorporation of fillers into polymer
composites in order to obtain the articles having a set of new properties is necessary
both from scientific and practical viewpoints.
The aim of this work is to study the possibility of filling butadiene-styrene rub-
ber of SKS-30 ARK grade with powder-like fillers made of cotton fiber. Another
aim is the choice of the way of incorporation of the rubber at the stage of latex as
well as the estimation of the effect of fillers on the process of coagulation and the
properties of the composites.

3.2  EXPERIMENTAL SECTION

At first, we elaborated the technique of obtaining powder-like cellulose fillers from
fibrous materials from cellulose-containing textile waste products.
For this, cotton fiber was subjected to rough crumbling and treated with sul-
furic acid according to the following technique. Fibers of 0.5–3.0 cm in size were
treated with 1.5–2.0 parts of sulfuric acid under stirring (acid concentration 20–30
mass%). Next, the pasty mass (fibers + sulfuric acid solution) was filtrated. The ob-
tained powder-like filler was dried for 1–2 h. After the final drying, the powder-like
mass was subjected to the additional crumbling up to a more highly dispersed state.
Thus, the acid powder-like cellulose (APC) filler was obtained. To obtain the neutral
powder-like cellulose (NPC) filler, APC was neutralized with the aqueous solution
of sodium hydroxide with the concentration of 1.0–2.0 mass%.
At the second stage of investigations, some ways of incorporation of powder-
like cellulose fillers into butadiene-styrene rubber were estimated and proposed for
the use.
Thereto APC, NPC, and microcrystalline cellulose (MCC) were applied with
the dosage for every sample (1, 3, 5, 10 mass%) in the rubber. In one of the studied
ways of incorporation, the powder-like fillers were incorporated into the latex of
butadiene-styrene rubber just before its supply to coagulation. An aqueous solution
of NaCl (24 mass%), MgCl2 (12 mass%), or AlCl3 (10 mass%) was applied as a co-
agulant, and an aqueous solution of sulfuric acid with a concentration of 1–2 mass%
was used as an acidifying agent. Powder-like cellulose fillers were incorporated in
the following ways:
• in the dry form just into latex immediately before its supply for coagulation;
• in the dry form into latex, involving coagulant;
• simultaneously with the aqueous solution of coagulant in latex;
• with serum at the completion phase of extraction of rubber from latex.
At the third stage, we studied the influence of powder-like cellulose fillers on
the process of coagulation.
The coagulation process was performed in the following way. Latex SKS-30
ARK (20 ml; dry residue of ~18%) was loaded into a coagulator, which was made
40 Process Advancement in Chemistry and Chemical Engineering Research

in the form of a capacitance provided with a stirring device, and then it was ther-
mally stabilized for 15–20 min at a temperature of 60°C. After that, 24% aqueous
solution of coagulant (NaCl, MgCl2, AlCl3) was supplied. The coagulation process
was completed by the addition of 1–2% aqueous solution of sulfuric acid to the mix-
ture up to рН ≈2.0–2.5. The formed rubber crump was separated from the aqueous
phase by filtration, washed up with water, dried in a desiccator at a temperature of
80–85°C, and then weighed. The mass of the formed rubber crump was calculated
based on the dry residue of the original latex. After sedimentation of filtrate (or as
it is named in the industry of synthetic rubber—“serum”), a possible presence of
high-dispersive rubber crump in the sample was determined visually. Powder-like
cellulose fillers were incorporated into the latex of butadiene-styrene rubber using
all of the above-mentioned ways.
At the fourth stage, the influence of powder-like cellulose fillers on the proper-
ties of obtained rubbers, rubber compounds, and vulcanizates was estimated. To
make the estimations, first rubber compounds were prepared with the use of con-
ventional ingredients with their further vulcanization at the standard facilities.6,7 The
produced vulcanizates were subjected to physical–mechanical tests and the simulta-
neous study of vulcanization kinetics and swelling ability kinetics.
Swelling kinetics ability of vulcanizates filled with different fibers was studied
in solvents of different polarities according to the following technique. Samples
of vulcanizates were cut in the form of squares of size 1 × 1 cm and weighed. The
number of samples for each series of measurements was 5. The samples were put
into solvents for 8 h. Every hour when they were extracted from the solvents, their
sizes were measured and they were weighed. The size and mass of a sample were
measured until 24 h. After that we processed the obtained data:
• in order to determine the swelling degree a (mass%), we subtracted the mass
of the original sample from that of the swollen sample: the obtained solvent
mass was divided by the mass of the original sample and the result was mul-
tiplied by 100%; from the five obtained results for each of the samples, the
greatest (equilibrium) value amax was chosen;
• swelling constant rate was determined as

k = (1/t) (ln[amax/(amax - at)]),

where t is time (h) and at is the value of the current swelling degree at the time
t.

3.3  RESULTS AND DISCUSSION

The obtained APC involved the rest of sulfuric acid. However, this disadvantage is
transformed into an advantage in the case of the use of this filler in the production of
emulsion rubbers where acidification of the system takes place at the stage of rubber
extraction from latex.
A Study on Possibilities for Cellulose-Based Textile Waste Treatment 41

One can expect that the use of APC fillers in the technological process of buta-
diene-styrene rubber production should reduce a total consumption of sulfuric acid
and stabilize the coagulation stage. It should be noted that the process performed in
the real industrial scale the separation stage of the obtained powder-like filler from
sulfuric acid solution and its drying can be eliminated since extraction of butadiene-
styrene rubber from the latex is accompanied by acidification of the system by a so-
lution of sulfuric acid. Therefore, the obtained pasty mixture composed of a sulfuric
acid solution and a powder-like filler on the basis of cellulose is reasonable to dilute
with water in order to decrease the sulfuric acid concentration up to 1–2 mass%
and to perform incorporation of the obtained dispersed mass into the coagulated
latex instead of the “pure” solution of sulfuric acid. In order to make more overall
estimate of the influence of powder-like cellulose fillers on the coagulation process
and the properties of the obtained composites, comparative tests with the samples
of MCC were performed.
The fractional composition of APC, NPC, and MCC fillers is presented in Figure
3.1. On the basis of the fractional composition of the powder-like fillers, the weight–
average size of their particles was determined: APC ≈ 0.57 mm; NPC ≈ 0.14 mm;
MCC ≈ 0.15 mm. The calculated specific surface of the particles in these powder-
like fillers was of 70, 286, and 267 cm2/g, respectively, accounting for the cellulose
density ρ = 1.5 g/cm3.

FIGURE 3.1  Fractional composition of the powder-like cellulose fillers: APC (1), NPC (2),
MCC (3).
42 Process Advancement in Chemistry and Chemical Engineering Research

The images of the powder-like cellulose fillers obtained with the use of scanning
electron microscopy JSM-6380 LV (magnification by 220–250 times) are presented
in Figure 3.2.

FIGURE 3.2  Electron microphotographs of APC (1), NPC (2), MCC (3).

These images were obtained in the secondary-electron emission mode. In or-

der to prevent thermal destruction of the samples and their electrical charging
under the impact of the electron beam, a gold layer with a thickness of 10 nm
was deposited on the samples. The particles of cellulose powders were mainly
presented by crystals with the shape factor l/d (the ratio of length l to the diameter
d) varying within the interval of 1–9 for APC, 1–25 for NPC, and 1–8 for MCC.
This was also confirmed indirectly by the value of packed density for the fillers:
MCC = 0.79, NPC = 0.44, and APC = 0.68 g/cm3. In the presence of such needle-
like fillers, it is possible to observe the anisotropy effect of elastic-strengthening
factors for vulcanizates.
In turn, the analysis of the particle elemental composition demonstrated the
presence of sulfate groups in APC and their absence in NPC and MCC (Table
3.1).
A Study on Possibilities for Cellulose-Based Textile Waste Treatment 43

TABLE 3.1  Elemental Composition of Cellulose Powder-Like Fillers.

Name of the element Content of the elements (mass%)
NPC APC MCC
С 43.76 39.02 44.53
О 53.80 53.47 55.47
Na 0.62 0 0
S 0 5.49 0
Other 1.82 2.02 0

Comparing the possible ways of incorporation of powder-like cellulose fillers

into butadiene-styrene rubber with the account of their properties, one can make
a conclusion that incorporation of APC is appropriate to perform with a coagulant
while MCC and NPC are reasonable to incorporate in the form of dry powders into
latex just before its supply to coagulation.8,9 However, since incorporation of the fill-
ers in a dry form is connected with certain technological problems, in what follows,
NPC and MCC are incorporated jointly with a coagulant.
Tables 3.2–3.4 present the results of the study of the influence of powder-like
cellulose fillers on the yield of rubber crump obtained from latex in the presence of
different coagulants: NaCl, MgCl2, and AlCl3. The analysis of the obtained results
demonstrated that incorporation of all the above-mentioned powder-like cellulose
fillers resulted in an increase in the yield of the formed rubber crump.

TABLE 3.2  Influence of Coagulant (NaCl) Consumption on the Yield of the Formed Rubber
Crump for Different Amounts of Investigated Powder-Like Fillers
NaCl Yield of the formed rubber crump (mass%)
consump-
tion (kg/ With- Amount of APC Amount of NPC Amount of MCC
ton of out (mass% per rubber) (mass% per rubber) (mass% per rubber)
rubber) filler 1 3 5 10 1 3 5 10 1 3 5 10

1 35.2 52.5 48.2 52.7 49.2 45.4 44.7 50.1 48.0 41.3 48.1 49.2 45.1

5 45.9 59.8 58.4 61.4 61.7 56.9 59.0 58.5 68.6 58.6 60.9 56.5 57.9

10 56.8 69.8 71.1 79.6 77.5 78.1 78.6 76.3 79.0 76.4 77.5 78.2 72.6

25 80.0 87.2 85.6 92.3 90.5 90.7 91.8 94.9 90.8 92.5 93.6 91.3 89.2

50 92.8 93.1 92.9 95.7 92.7 95.5 95.8 97.9 92.3 95.9 96.5 94.9 92.7

75 95.3 98.7 98.6 98.1 96.4 97.3 97.9 98.1 96.0 98.0 98.4 98.5 95.6

100 97.8 98.9 99.0 99.2 97.5 97.9 99.2 99.2 98.2 99.1 99.0 99.2 98.2
44 Process Advancement in Chemistry and Chemical Engineering Research

TABLE 3.3  Influence of Coagulant (MgCl2) Consumption on the Yield of the Formed
Rubber Crump for Different Amounts of Investigated Powder-Like Fillers.

MgCl2 Yield of the formed rubber crump (mass%)

consump-
tion (kg/ Without Amount of APC Amount of NPC Amount of MCC
ton of filler (mass% per rubber) (mass% per rubber) (mass% per rubber)
rubber)
1 3 5 10 1 3 5 10 1 3 5 10

1 37.9 50.1 60.7 62.8 60.3 44.2 45.7 48.8 49.1 45.2 44.5 43.2 47.6

2 48.9 54.5 70.2 70.1 73.3 50.7 54.9 51.7 52.3 52.4 50.3 51.4 59.5

3 61.7 62.5 76.7 85.6 83.8 66.4 61.1 64.9 65.3 60.8 61.3 60.4 61.4

6 75.2 88.5 87.6 90.9 97.1 79.4 77.9 80.1 83.1 80.5 81.5 83.9 83.0

9 80.4 91.2 97.5 98.2 97.5 84.1 82.3 86.3 92.9 91.6 91.0 89.9 91.7

10 89.6 95.6 98.5 98.6 98.3 90.3 95.2 95.8 95.9 98.6 95.9 96.4 97.5

15 92.8 98.2 99.1 99.0 98.9 96.1 98.2 97.8 98.2 98.9 97.4 98.5 98.6

20 95.7 99.2 99.2 99.2 99.1 96.2 98.9 98.9 98.9 99.0 98.6 98.9 99.2

TABLE 3.4  Influence of Coagulant (AlCl3) Consumption on the Yield of the Formed Rubber
Crump for Different Amounts of the Investigated Powder-Like Fillers.
AlCl3 con- Yield of the formed rubber crump (mass%)
sumption Without Amount of APC Amount of NPC Amount of MCC
(kg/ton of filler (mass% per rubber) (mass% per rubber) (mass% per rubber)
rubber)
1 3 5 10 1 3 5 10 1 3 5 10
0.3 43.0 57.9 68.9 66.0 74.3 56.7 54.6 56.1 55.3 57.1 56.8 59.7 55.0
0.7 52.3 79.9 82.7 82.8 83.4 74.0 70.9 72.0 75.1 70.0 69.3 69.3 65.1
1 71.2 92.3 93.7 92.7 91.1 83.0 82.2 80.8 81.9 81.4 80.1 81.2 81.7
2 90.4 95.0 97.1 96.3 95.3 94.1 92.1 93.3 90.9 92.8 91.8 91.2 91.5
3 93.5 98.6 98.2 97.5 96.2 97.5 98.1 97.2 97.3 97.7 94.0 95.7 93.7
4 96.5 99.1 98.6 99.2 99.1 98.2 99.2 98.2 99.2 98.2 98.3 97.3 95.9

This can be connected with a decrease of rubber losses in the form of highly dis-
persed crump with serum and rinsing water. Incorporation of powder-like cellulose
fillers allowed us to reduce the consumption of the coagulant and acidifying reagent
required for a complete separation of the rubber from latex. In case of the applica-
tion of APC filler with a dosage of more than 7 mass% in the rubber, complete co-
agulation of latex can be attained without additional incorporation of the acidifying
reagent—sulfuric acid solution—into the process. At the same time, powder-like
A Study on Possibilities for Cellulose-Based Textile Waste Treatment 45

cellulose fillers can absorb surface active materials on their surface as well as co-
agulant and the components of the emulsion system, thus facilitating a decrease of
environmental pollution by sewage water, for example, APC (Table 3.5). Similar
data were obtained both for NPC and MCC.

TABLE 3.5  Elemental Composition of APC Before and After Its Application in the Process
of Rubber Separation from Latex.

Name of the Content (mass%)

element
APC composition APC composition treated with the components
before coagulation of emulsion system in the presence of different
process electrolytes
NaCl MgCl2 AlCl3
С 39.02 54.98 50.28 52.09
О 53.47 34.44 44.63 44.34
S 5.49 0.48 0.45 0.41
Cl 0 5.75 3.37 2.16
Na 0 4.06 0 0
Mg 0 0 0.97 0
Al 0 0 0 0.84
K 0 0.16 0.29 0.15
Additives 2.02 0.13 0.01 0.01

Proposals on the changes in any technological parameters of the rubber coagula-

tion process should not have any negative effects on the properties of the rubber and
its vulcanizates. Therefore, we investigated the process of vulcanization for the rub-
ber samples separated with the application of different amounts of the studied fillers
(3, 5, 10 mass% in the rubber). Results of these investigations are presented in Table
3.6. The properties of the rubber compounds and physical–mechanical factors for
the filled vulcanizates are given in Table 3.7.
46 Process Advancement in Chemistry and Chemical Engineering Research

TABLE 3.6  Characteristics of the Vulcanization Process of the Rubber Compounds

Involving Fillers.
Factor Reference Value of the factor for the rubbers with different fillers
sample
Content of APC Content of NPC Content of MCC
(without a
(mass% in a rub- (mass% in a rub- (mass% in a rubber)
filler)
ber) ber)
3 5 10 3 5 10 3 5 10
МL (dN 7.5 6.5 7.0 7.5 7.0 7.3 7.7 7.0 6.9 7.5
m)
МН (dN 32.8 31.5 32.9 33.0 34.0 34.3 37.5 33.0 34.8 36.7
m)
tS (min) 3.0 4.3 3.8 3.0 4.0 3.9 2.3 4.4 4.4 4.0
tС(25) 9.9 8.3 8.9 8.7 10.0 10.0 8.7 8.8 8.1 8.3
(min) 12.6 10.7 11.4 11.4 12.6 12.7 11.4 11.9 10.8 10.8
tС (50) 22.0 22.0 22.5 21.8 22.8 23.1 21.9 22.8 22.1 21.4
(min)
tС(90)
(min)
Rʋ 5.3 5.6 5.3 5.3 5.3 5.2 5.1 5.4 5.6 5.7
(min–1)

Note: МL, minimal torsion moment; МН, conditional maximal torsion moment; tS, time of
vulcanization start; tС(25), time of attaining 25% vulcanization; tС(50), time of attaining 50%
vulcanization; tС(90), time of attaining 90% vulcanization; Rʋ, vulcanization rate.

TABLE 3.7  Properties of the Rubber Compounds and Vulcanizates Involving Fillers.
Factor Reference Value of the factor for the rubbers with different fillers
sample Content of APC (mass% Content of NPC (mass% Content of MCC
(without in a rubber) in a rubber) (mass% in a rubber)
a filler)
1 3 5 10 1 3 5 10 1 3 5 10
Mooney 57.0 52.0 53.0 54.0 57.0 54.0 54.0 52.0 58.6 54.0 54.0 54.0 55.0
viscosity
MB 1 + 4
(100°C)
(a.u.)
Plasticity 0.40 0.40 0.40 0.40 0.40 0.35 0.35 0.32 0.35 0.28 0.29 0.28 0.29
(a.u.)
Elastic 1.10 0.80 0.70 0.70 1.10 1.50 1.40 1.60 1.29 1.88 1.97 1.86 1.82
recovery
(mm)
A Study on Possibilities for Cellulose-Based Textile Waste Treatment 47

TABLE 3.7  (Continued)

Factor Reference Value of the factor for the rubbers with different fillers
sample Content of APC (mass% Content of NPC (mass% Content of MCC
(without in a rubber) in a rubber) (mass% in a rubber)
a filler)
1 3 5 10 1 3 5 10 1 3 5 10
М300 8.1 8.0 8.1 8.0 7.8 8.0 7.9 8.5 9.2 8.8 8.6 8.8 8.6
(MPa)
fp (MPa) 22.8 20.5 22.0 24.4 21.9 24.0 23.6 22.7 21.7 20.0 20.0 20.3 22.3
εp (%) 620 620 620 670 623 630 637 620 570 500 520 544 562
εост (%) 14 14 14 16 14 14 14 15 17 12 13 14 16
Ball drop 38 42 42 41 38 40 40 40 38 40 42 38 39
resilience
(%)
Shore 57 57 57 55 57 58 57 57 62 58 59 60 61
hardness
A (a.u.)
Note: М300, elongation stress 300%; fp, conditional disruption strength; εp, relative elongation
under disruption; εост, relative residual deformation after disruption.

With an increase of content of all cellulose fillers from 3 to 10 mass% in rubber,

the rise of the minimal (МL) and conditional maximal (Мn) torsion moments was
observed in the rubber compound under vulcanization. The presence of powder-like
cellulose fillers increased the time of the vulcanization start for the rubber com-
pounds but actually did not have an effect on the time of vulcanization ending (Table
3.6).
The presence of NPC and MCC in the amount 1–10 mass% in the rubber in-
creased the hardness of vulcanizates due to the effect of the presence of fillers as
a result of their large shape factor (1–25 for NPC), as well as their large specific
surface (83 cm3/100 g for MCC).10 However, the presence of NPC and MCC did not
influence the rubber ball drop resilience.
The reinforcing effect in the polymer matrix provided a linear increase of M300
for rubbers with an increase of content of NPC with a large shape factor (1–25). In
turn, the increase of the content of the defect centers in the polymer matrix due to
the accumulation of the coarse grains of particles (Fig. 3.1) reduced the strength and
relative elongation of vulcanizates under disruption. An increase of MCC content in
vulcanizates provided the rise of stress under 300% elongation (М300), with a simul-
taneous decrease of the swelling rate of vulcanizates in solvents (Table 3.8). More-
over, an increase of MCC content multiplied the concentration of the transverse
bonds and increased vulcanization rate along with a decrease of the strength and
relative elongation at the disruption due to the accumulation of the defect centers
in the polymer matrix, which can be explained by the absence of wetting for MCC
particles with a rubber (Table 3.7).
48 Process Advancement in Chemistry and Chemical Engineering Research

TABLE 3.8  Influence of the Amount of Fillers and Nature of a Solution on the Ability to
Vulcanizates Swelling.
Solvent Swelling rate of vulcanizates in solvents (0–10% wt. on rubber)
Without fillers 3% 5% 10%
b а b а b а B А
APC
Toluene (1) −0.62 2.4 −0.54 2.3 −0.61 2.4 −0.58 2.4
Nefrac (2) −0.38 1.9 −0.67 1.9 −0.89 1.9 −0.84 1.9
1/Qmaxtl × 103 4.3 4.1 4.5 4.8
NPC
Toluene (1) −0.62 2.4 −0.82 2.4 −0.80 2.4 −0.58 2.4
Nefrac (2) −0.38 1.9 −0.77 1.8 −0.64 1.9 −0.54 2.0
1/Qmaxtl × 103 4.3 4.6 4.0 3.9
MCC
Toluene (1) −0.62 2.4 −0.34 2.4 −0.31 2.3 −0.30 2.3
Nefrac (2) −0.38 1.9 −0.27 1.8 −0.27 1.7 −0.27 1.7
1/Q max
tl
× 10
3
4.3 4.2 4.0 3.9
Note: b, swelling rate (h ); а, lgQmax, equilibrium swelling rate (%); 1/Qmaxtl × 103—
−1

concentration of transverse bonds.

The swelling process of the obtained vulcanizates was investigated in Ref. 11

in different environments allowing us to simulate real service conditions of vulca-
nizates. Aromatic toluene and aliphatic nefrac (benzene) were taken as solvents as
mostly widespread coupling media.
Analysis of the reference literature sources12 showed that for all of the solvents,
swelling kinetics of vulcanizates in the presence of the fillers could be described
in semilogarithmic coordinates of the descending direct line (Fig. 3.3) of the form

lg(Qmax - Qτ) = lgQmax – bτ.

A Study on Possibilities for Cellulose-Based Textile Waste Treatment 49

FIGURE 3.3  Swelling kinetics of vulcanizates in organic solvents.

By changing lg(Qmax - Qτ) = Y, and lgQmax = a, the original equation can be

written as

Y= a – bτ,

where b is the swelling rate (h−1); τ is the duration of swelling (h); Qmax is an equilib-
rium swelling degree (%); Qτ is the current swelling rate (%).
Equilibrium swelling degree of vulcanizates, involving 3–10 mass%, in nefrac
(Qnfmcc,max) was reduced up to 46–52% as compared with 84% for vulcanizate with-
out MCC (Fig. 3.4, straight line 2). The swelling rate of vulcanizates in nefrac in
the presence of 3–10 mass% of MCC was bnfmcc = -0.27 h−1; it did not depend on
the value of MCC content but was less than the swelling rate of vulcanizate without
MCC (−0.38 h−1) (Table 3.8).
In turn, the swelling rate of vulcanizates in toluene, btlmcc, involving 3–10 mass%
of MCC was 0.30–0.34 h−1, and it was two times lower than that for vulcanizate
without the filler (−0.62 h−1) (Table 3.8). An increase of MCC content within the
investigated interval reduced as the equilibrium swelling degree Qtlmcc,max from 250
to 209% (Fig. 3.4, straight line 1), as swelling rate from −0.34 to−0.30 h−1.
50 Process Advancement in Chemistry and Chemical Engineering Research

FIGURE 3.4  Influence of MCC content (mass%) and the nature of a solvent on the
equilibrium swelling degree of vulcanizates (Qmcc,max, %) in toluene (1) and nefrac (2).

Similar regularity is the characteristic of vulcanizates involving active fillers

(e.g., technical carbon).10
The value of equilibrium swelling degree of vulcanizates involving 1–10 mass%
of NPC (Qnfnpc,max) in nefrac was 80–96% and actually did not differ (84%) from that
in vulcanizates without the filler (Fig. 3.5, straight line 2).
The swelling rate of vulcanizates in nefrac (bnfnpc) in the presence of 1–10 mass%
of NPC increased up to the value of 0.48–0.77 h−1 as compared with the value of
-0.38 h−1 for vulcanizate without the filler (Table 3.7). The dependence of the swell-
ing rate btlnpc on the NPC content within the interval of 3–5 mass% was -0.80 to
−0.82 h−1. These values were higher than the swelling rate of vulcanizate without
the filler, -0.62 h−1.
An increase of Qtlnpc,max in toluene was observed with the rise of NPC content
within the interval of 1–10 mass% (Fig. 3.5, straight line 1). Equilibrium swelling
degree of vulcanizates in toluene, Qtlnpc,max, with an increase of NPC content was
grown up to 262% as compared with a vulcanizate without the filler (235%). The
increase of Qtlnpc,max can be explained by the decrease of the density of transverse
bonds in vulcanizate at the boundary between the phases of “polymer filler” and the
greater value of the shape factor for NPC.
A Study on Possibilities for Cellulose-Based Textile Waste Treatment 51

FIGURE 3.5  Influence of NPC content (mass%) and the nature of solvent on the equilibrium
swelling degree of vulcanizate (Qnpc,max, %). 1—toluene; 2—nefrac.

For vulcanizates involving 1–10 mass% of APC in nefrac, the value of Qnfapc,max
was of 79–85% as compared with 84% for vulcanizates without the additives (Fig.
3.6, straight line 1), that is, it did not actually change.

FIGURE 3.6  Influence of APC content (mass%) and the nature of solvent on the equilibrium
swelling degree of vulcanizate (Qapc,max, %). 1—toluene; 2—nefrac.
52 Process Advancement in Chemistry and Chemical Engineering Research

An increase of bnfapc values for vulcanizates involving APC up to −0.89 h−1 was
observed as compared with the value of −0.38 h−1 for vulcanizates without the filler
(Table 3.7) because of a bad wettability of the large APC particles with the rubber
and occurrence of the tunnel effect. The equilibrium swelling degree of vulcanizates
with 3–10 mass% of APC in toluene, Qtlapc,max = 240–252%, was greater than that for
vulcanizates without the additives (235%) (Fig. 3.6, straight line 1). This can be ex-
plained by a decrease of the density of transverse bonds in vulcanizate (1/Qtlapc,max)
at the boundary of “polymer filler” due to a bad wettability of the particles of the
acid powder-like filler.

3.4 CONCLUSION
1. Textile waste products can be used not only as fiberfills but also as powder-
like fillers.
2. Differences in sizes, shape factor, specific surface, and fractional and chem-
ical composition of the particles of powder-like cellulose fillers obtained in
different ways were found in the work. Powders of the neutral and MCC are
characterized by the higher specific surface (267–286 cm2/g). The largest
scattering interval of the shape factor was the characteristic of the neutral
cellulose (l/d = 1–25). Greater content of sulfate groups was determined in
the particles of the APC (5.49 mass% accounting for the bound sulfur).
3. Incorporation of powder-like cellulose fillers into SKS-30 ARK rubber does
not have a negative effect on the physical–mechanical quality factors of
vulcanizates. Thus, it is possible to get a considerable improvement of elas-
tic-strength quality factors of butadiene-styrene rubber in the presence of
these additives due to the choice of the required reactants for the interphase
combination of cellulose with the rubber matrix.
4. The linear dependence of the equilibrium swelling degree for vulcanizates
in the aliphatic and aromatic solvents on the content of powder-like cel-
lulose fillers was found as a result of the work. With an increase of MCC
content equilibrium swelling degree reduced, and for NPC and APC it was,
on the contrary, enhanced.
5. Certain difference was found in swelling kinetics of vulcanizates in nefrac
and toluene in the presence of MCC, APC, and NPC. In the presence of
3–10 mass% of MCC, the swelling rate of vulcanizates in solvents reduced
by 1.25–2.0 times that is the characteristic for the rubbers with active fillers.
Incorporation of 1–10 mass% of NPC increased the swelling rate of vulca-
nizate in nefrac by 1.25–2.0 times.
6. Diverse ways of incorporation of powder-like cellulose fillers into rubber
emulsion before its coagulation with the use of different coagulants make
it possible to improve the distribution of the additives in the rubber matrix,
to reduce coagulant consumption, and in case of APC application—to de-
A Study on Possibilities for Cellulose-Based Textile Waste Treatment 53

crease the consumption of the acidifying reactant up to its complete elimina-

tion from the coagulation process.

KEY WORDS

•• waste
•• composite material
•• rubbеr latex
•• fibrous filling material
•• physicomechanical properties

REFERENCES
1. Nikulin, S. S.; Pugacheva, I. N.; Chernykh, O.N. In Composite Materials on the Basis of
Butadiene-Styrene Rubbers; Academy of Natural Sciences, 2008; p 145.
2. Nikulin, S. S.; Akatova, I. N. Influence of Capron Fiber on Coagulation, Rubber Properties,
Rubber Compounds and Vulcanizates. Zhurnal Prikladnoi Khimii, 2004, 77 (4), 696–698.
3. Nikulin, S. S.; Akatova, I. N. Influence of the Flax and Viscose Fiber on the Process of Separa-
tion of Butadiene-Styrene Rubber from the Latex. Adv. Mod. Nat. Sci. 2003, 6, 10–13.
4. Akatova, I. N.; Nikulin, S. S. Influence of Fiberfill with High Dosages on the Process of
Separation of Butadiene-Styrene Rubber from the Latex. Product Usage Elastomers, 2003, 6,
13–16.
5. Mikhailin Yu. A. In Constructional Polymer Composite Materials; Scientific Foundations and
Technologies, 2008; p 822.
6. Zakharov, N. D., Ed. In Laboratory Practice in Rubber Technology; Khimia, 1988; p 237.
7. Nikulin, S. GOST 15627-79. Synthetic Rubbers—Butadiene-Methylstyrene SKMS-30 ARK
and Butadiene-Styrene SKS-30 ARK, 2007.
8. Pugacheva, I. N.; Nikulin, S. S. Application of Powder-Like Filler on the Basis of Cellulose in
the Production of Emulsion Rubbers. Mod. High-End Technol. 2010, 5, 52–56.
9. Pugacheva, I. N.; Nikulin, S. S. Application of Powder-Like Fillers in the Production Emul-
sion Rubbers. Indust. Product. Use Elastomers, 2010, 1, 25–28.
10. Koshelev, F. F.; Korneev, A. F.; Bukanov, A. M. In General Rubber Technology; Khimia,
1978; p 528.
11. Zakharov, N. D.; Usachov, S. V.; Zakharkin, O. A.; Drovenikova, M. P.; Bolotov, V. S. In
Laboratory Practice in Rubber Technology. Basic Processes of Rubber Production and Meth-
ods of Their Control; Khimia, 1977; p 168.
12. Tager, A. A. In Physics and Chemistry of Polymers; Scientific World, 2007; p 573.
CHAPTER 4

THEORETICAL ESTIMATION OF ACID

FORCE OF MOLECULE P-DIMETHOXY-
TRANS-STILBENE BY METHOD
AB INITIO
V. A. BABKIN1, D. S. ANDREEV1, YU. A. PROCHUKHAN3,
K. Y. PROCHUKHAN3, and G. E. ZAIKOV2
1
Sebrykov Department, Volgograd State Architect-build University
2
N.M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, 4,
Kosygin St., Moscow 119334, Russian Federation
3
Bashkir State University, Kommunisticheskayaul., 19, Ufa 450076, Republic of
Bashkortostan, Russia

CONTENTS
Abstract....................................................................................................................56
4.1 Aims and Backgrounds..................................................................................56
4.2 Methodical Part..............................................................................................56
Keywords.................................................................................................................59
References................................................................................................................59
56 Process Advancement in Chemistry and Chemical Engineering Research

ABSTRACT
For the first time,quantum chemical calculation of a molecule of p-dimethoxy-
trans-stilbene is executed by method ab initio with optimization of geometry on all
parameters. The optimized geometrical and electronic structures of this compound
areobtained. The acid power of p-dimethoxy-trans-stilbene is theoretically appreci-
ated. As a result, it to relates to a class of very weak H-acids (pKa=+36, where pKa-
universal index of acidity).

4.1  AIMS AND BACKGROUNDS

The aim of this work is to study the electronic structure of the molecule p-dime-
thoxy-trans-stilbene1and theoretical estimation of its acid power by the quantum-
chemical method ab initioin base 6-311G**. The calculation was performed with
the optimization of all parameters by the built-in standard gradient method in PC
GAMES.2 The calculation was executed in approach the insulated molecule in gas
phase.The program MacMolPlt was used for the visual presentation of the model of
the molecule.3

4.2  METHODICAL PART

Geometric and electronic structures, and general and electronic energies of the
molecule p-dimethoxy-trans-stilbenewere obtained by the method ab initio in base
6-311G**and are shown in Figure 4.1 and in Table 4.1. The universal factor of
acidity was calculated by the formulapKa=49.04−134.6qmaxH+4,5 (whereqmaxH+ is a
maximum positive charge on the atom of hydrogen;qmaxH+=+0.10 (for p-dimethoxy-
trans-stilbeneqmaxH+ alike Table 4.1)). This same formula is used in Ref. 6;pKa=36.
The quantum-chemical calculation of p-dimethoxy-trans-stilbene by the method
ab initio in base 6-311G** was executed for the first time. The optimized geomet-
ric and electronic structures of this compound wereobtained. The acid power of
p-dimethoxy-trans-stilbene was theoretically evaluated (pKa=36). This compound
pertains to a class of very weak H-acids (рKа>14).
Theoretical Estimation of Acid Force of Molecule 57

FIGURE 4.1  Geometric and electronic molecule structure of p-dimethoxy-trans-

stilbene(Е0= 2005.131 kDg/mol, Еel= −4981.689 kDg/mol).

TABLE 4.1  Optimized Bond Lengths, Valence Corners, and Charges on the Atoms of the
Molecule p-dimethoxy-trans-stilbene.

Bond lengths RA Valence corners Grad Atom Charges on atoms

C(2)–C(1) 1.40 C(5)–C(6)–C(1) 122 C(1) −0.05
C(3)–C(2) 1.38 C(1)–C(2)–C(3) 121 C(2) −0.07
C(4)–C(3) 1.39 C(2)–C(3)–C(4) 120 C(3) −0.09
C(5)–C(4) 1.38 C(3)–C(4)–C(5) 120 C(4) +0.21
C(6)–C(5) 1.38 O(11)–C(4)–C(5) 120 C(5) −0.09
C(6)–C(1) 1.39 C(4)–C(5)–C(6) 120 C(6) −0.07
H(7)–C(2) 1.07 C(2)–C(1)–C(6) 118 H(7) +0.09
58 Process Advancement in Chemistry and Chemical Engineering Research

C(8)–C(1) 1.48 C(1)–C(2)–H(7) 120 C(8) −0.08

H(9)–C(6) 1.08 C(2)–C(1)–C(8) 123 H(9) +0.09
H(10)–C(5) 1.07 C(14)–C(13)–C(8) 127 H(10) +0.10
O(11)–C(4) 1.36 C(5)–C(6)–H(9) 119 O(11) −0.49
H(12)–C(3) 1.08 C(4)–C(5)–H(10) 119 H(12) +0.10
C(13)–C(8) 1.33 C(3)–C(4)–O(11) 120 C(13) −0.08
C(13)–C(14) 1.48 C(2)–C(3)–H(12) 121 C(14) −0.06
C(14)–C(19) 1.39 C(1)–C(8)–C(13) 126 C(15) −0.06
C(15)–C(14) 1.40 C(19)–C(14)–C(13) 119 C(16) −0.09
C(16)–C(15) 1.38 C(15)–C(14)–C(13) 124 C(17) +0.21
C(17)–C(16) 1.39 C(18)–C(19)–C(14) 122 C(18) −0.09
C(18)–C(17) 1.38 C(19)–C(14)–C(15) 118 C(19) −0.07
C(19)–C(18) 1.38 C(14)–C(15)–C(16) 121 H(20) +0.09
H(20)–C(15) 1.07 C(15)–C(16)–C(17) 120 H(21) +0.10
H(21)–C(16) 1.08 C(16)–C(17)–C(18) 120 O(22) −0.49
O(22)–C(17) 1.36 O(22)–C(17)–C(18) 120 H(23) +0.10
H(23)–C(18) 1.08 C(17)–C(18)–C(19) 120 H(24) +0.09
H(24)–C(19) 1.08 C(14)–C(15)–H(20) 120 H(25) +0.09
H(25)–C(13) 1.08 C(15)–C(16)–H(21) 121 H(26) +0.09
H(26)–C(8) 1.08 C(16)–C(17)–O(22) 120 C(27) 0.00
C(27)–O(22) 1.41 C(17)–C(18)–H(23) 119 H(28) +0.08
H(28)–C(27) 1.09 C(18)–C(19)–H(24) 119 H(29) +0.08
H(29)–C(27) 1.09 C(8)–C(13)–H(25) 119 H(30) +0.10
H(30)–C(27) 1.08 C(1)–C(8)–H(26) 114 C(31) 0.00
C(31)–O(11) 1.41 C(17)–O(22)–C(27) 116 H(32) +0.08
H(32)–C(31) 1.09 O(22)–C(27)–H(28) 111 H(33) +0.10
H(33)–C(31) 1.08 O(22)–C(27)–H(29) 111 H(34) +0.08
H(34)–C(31) 1.09 O(22)–C(27)–H(30) 107
C(4)–O(11)–C(31) 116
O(11)–C(31)–H(32) 111
O(11)–C(31)–H(33) 107
O(11)–C(31)–H(34) 111
Theoretical Estimation of Acid Force of Molecule 59

KEYWORDS

•• quantum chemical calculation

•• method ab initio
•• p-dimethoxy-trans-stilbene
•• acid power

REFERENCES
1. Kennedy, J. In Cationic Polymerization of Olefins;Mir Publisher: Moscow,RU, 1978;p 431.
2. Schmidt, M. W.;Baldridge, K. K.; Boatz, J. A., Elbert, S. T.; Gordon, M. S.; Jensen, J. H.;
Koseki, S.; Matsunaga, N.; Nguyen, K. A.; Su,S.J.; et al. J. Comput. Chem.1993, 14, 1347–
1363.
3. Bode, B. M.; Gordon, M. S. J. Mol. Graphics Mod.1998, 16, 133–138.
4. Babkin, V. A.; Fedunov, R. G.; Minsker, K. S.; et al. OxidationCommun.2002, 25(1), 21–47.
5. Babkin, V. A. et al. Oxidation Commun.1998,21(4), 454–460.
6. Вabkin, V. A.; Zaikov, G. E. InNobel Laureates and Nanotechnology of the Applied Quantum
Chemistry;Nova Science Publisher: New York, USA, 2010; р 351.
CHAPTER 5

MODIFICATION OF POLYAMIDE 6 BY
N,N’–BIS-MALEAMIDE ACID
N. R. PROKOPCHUK, E. T. KRUT’KO, and M. V. ZHURAVLEVA
Belarusian State Technological University, Sverdlova Str.13a , Minsk, Republic of
Belarus. E-mail: [email protected]

CONTENTS
Abstract....................................................................................................................62
5.1 Introduction ...................................................................................................62
5.2 Main Part........................................................................................................63
5.3 Conclusion.....................................................................................................68
Keywords.................................................................................................................69
References................................................................................................................69
62 Process Advancement in Chemistry and Chemical Engineering Research

ABSTRACT
This chapter is based on receiving and researching of compositions on the basis
of industrially made polyamide 6 modified by N,N’-bis-maleamide acid of meta-
phenylenediamine. Existence in macromolecules of polyamides reactive carboxyl,
amide and amino groups, capable to interact with multifunctional monomeric and
oligomeric modifiers, gives the chance of receiving the materials possessing prop-
erties of sewed polymers. As a result, the use of bis-amino acid as a modifying ad-
ditive in the system of aliphatic polyamide 6 provides an improvement in strength
properties and thermal characteristics of a polymeric material.

5.1 INTRODUCTION
Due to the ever increasing demands of engineering industries of new techniques
to polymeric materials, including created on the base of aliphatic polyamides, an
urgent task of improving performance properties of these polymers, including high
heat and heat resistance, resistance to thermal-oxidative and aggressive media, and
adhesion characteristics to various substrates remains actual. Physical properties of
aliphatic polyamides are mainly conditioned by strong intermolecular interactions at
the expense of hydrogen bonds that are formed between the amide groups of neigh-
boring macromolecules. In the preparation of polyamides, it is necessary to enter
regulators (stabilizers) of molecular weight, in this case, acetic, adipic acids (as the
cheapest and most available) and amines, salts of monocarboxylic acids and mono-
amines, or N-alkyl amides of monocarboxylic acids are used.1 Polyamides as well as
other polymers are polydispersed. In the polymer composition, there are large mac-
romolecules and low molecular weight amides with a small number of elementary
units in the molecules (oligomers). They contain terminal amino groups and car-
boxyl groups. Furthermore, the oligomers of amides may also exist in a cyclic form.
The mechanism of their formation is still not clear. However, it is experimentally
proved that in the absence of water, cyclic oligomers are not capable of polymeriza-
tion, but they are easily converted into a polyamide in the presence of water. In this
regard, the use of additives, which at processing of polyamides may release small
amounts of moisture, can be very useful for improving the performance properties
of materials, products, and coatings based on polyamides. One of the effective ways
of targeted regulation of properties of commercially available polyamides is their
chemical modification by polyfunctional reactive compounds.2–5 Presence in the
macromolecules of polyamides reactive carboxyl, amide and amino groups that are
capable to react with monomeric and oligomeric polyfunctional modifiers enables
the production of materials having the properties of cross-linked polymers. Thus, it
was found that imido compounds, in particular N,N’–bis-maleimides, are effective
modifiers of many polymers, also including polyamides.6 Information about the use
Modification of Polyamide 6 By N,N’–Bis-Maleamide Acid 63

of N,N’–bis-maleinamido acids, as the modifiers in their synthesis of intermediates

in the scientific literature, was not found.

5.2  MAIN PART

The aim of this work is to study and research the compositions based on polyamide
6 (PA 6), industrially produced by JSC “Grodno Azot” (Grodno, Belarus) (OST
6-06-09-93), intermediate product in the synthesis of modified –N,N’–m-phenylene
bis-maleimide (FBMI) –N,N’–bis-maleamido metaphenylenediamine (FBMAK ).
The modifying reagent was injected into the PA 6 at doses of 5–10 wt.%. FB-
MAK choice, as previous FBMI,6 due to their high reactivity associated with the
content of the reactant molecules of double bonds that can be disclosed under ther-
mal or photographic processing to form a spatial cross-linked polymer structure.6
Physical and mechanical properties of PA 6 are shown in Table 5.1.

TABLE 5.1  Physical and Mechanical Properties of PA 6.

Index name Norm on the highest quality category

Color From white color to light yellow color
Number of point inclusions per 100 g of Not more than 8
product units
Size of crumbs msm, 1.5–4.0
Moisture content (%) 0.03–2.00
Relative viscosity, dl/g 2.20–3.50
Mass fraction of extractables (%) 1.0–3.0
Melting point, °C 214–220

Receiving of FBMAK was performed by reaction of equimolar amounts of

metaphenylenediamine with maleic anhydride at 20–25°C by gradual addition to a
solution of diamine in a minimum amount of solvent—dimethylformamide stoichio-
metric amounts of maleic anhydride. To obtain the corresponding bis-maleimide,
the second step (imidization) of bis-amino acid by heating it in a mixture of acetic
anhydride and sodium acetate in the ratio 2.5:0.5 moles per mole of bis–amino acid
at 70–90°C was performed. Upon completion of imidization (about 2.5 h of heat-
ing), FBMI was isolated and recrystallized from a mixture of ethyl and n-propyl
alcohol, in the ratio 1:1. It should be noted that the yield of the intermediate product,
FBMAK, in the first synthesis step is 85–90% while the final product after imidiza-
tion (FBMI) is only 50–60%.
The melting point of the synthesized N,N’–m-phenylene-bis-maleimide was
203°C, which corresponded to the literature data.7 FBMAK, when heated in the
64 Process Advancement in Chemistry and Chemical Engineering Research

process of determining the melting point, becomes FBMI and the melting point of
this compound is not clearly fixed.
Receiving of FBMAK and FBMI is performed according to Scheme 5.1. It is
important to note that the perspective of use of polyamide 6 FBMAK as a modi-
fier component instead of FBMI allows to exclude out the process of synthesizing
FBMI, which is the step of high-cost chemical cyclodehydration (imidization) of
FBMAK; moreover, the loss of the product during its conversion to the bis-imide
of the final step of synthesis is eliminated, and during imidizing process, extracted
water promotes destruction of cyclic structures in the system of the polyamide.

SCHEME 5.1

To study the structure of polyamide 6, the processes occurring in the polymer

system, as well as assessing the completeness of spending FBMAK reactive groups
by reacting with amine and amide functional groups of PA 6 during formation of
three-dimensional structure when heated samples were performed IR spectroscopic
study using FTIR spectrometer Nicolet 7101 (USA) in the range of 4000–300 cm−1
(resolution 1 cm−1).8 Furthermore, the possibility of formation of intermolecular
cross-linking was confirmed by electron paramagnetic resonance (EPR).9, 10 EPR
spectra are recorded using the modified RE-1306 spectrometer with computer soft-
ware. The heating process of polyamide compositions of modified FBMAK was
carried out in the cavity of the spectrometer in the temperature range of 20–250°C.
Before recording the spectra, the samples were cooled to room temperature. MnO
containing ions of Mn was used as an external standard9 and nitroxyl radicals were
used as markers.
For example, evidence of more efficient structuring system in polyamide com-
positions containing as builders FBMAK compared with FBMI is that the time of
correlation of stable nitroxyl radicals introduced into FBMAK modified PA 6 in-
creased from 23∙(source unmodified P6) to 50∙10−10 s with polyamide 6, modified
Modification of Polyamide 6 By N,N’–Bis-Maleamide Acid 65

by 5 wt.% FBMAK. For PA 6, modified with the same amount of MFBI, correlation
time of nitroxide was significantly shorter period from 40−10 s.
Comparative analysis of the IR absorption spectra obtained in an airless en-
vironment of PA 6 compositions and FBMAK different composition (5–10 wt.%
FBMAK builder) in the polymer melt, followed by heating of the samples at 150–
210°C showed, for the modified polymer systems, absorbance decrease of absorp-
tion bands in the 1647 cm−1, characteristic of the amide groups is observed.
It appears that at the process of chemical modification of PA 6 by bis-amino
acid, as well as modifying it by its corresponding bis-imide reactions, an increase in
the molecular weight of PA 6 take place. It occurs by the interaction of the carboxyl
groups of the bis-amino acid modifier with amine-terminated polyamide groups
(Scheme 5.2) and by the formation of interchain cross-links (Scheme 5.3) by open-
ing the double bonds formed during the heat treatment at 150–200°C samples of
polyamide compositions. This does not prevent homopolymerization of FBMI and
that is due to the ability of the double bonds in FBMI to be activated by adjacent
carbonyl groups of the imide cycle and disclosed by reacting with compounds con-
taining labile hydrogen atom.

SCHEME 5.2

SCHEME 5.3
66 Process Advancement in Chemistry and Chemical Engineering Research

These processes all together result in a change of the supramolecular structure of

the PA 6, causing the improvement of mechanical, thermal, and adhesive properties
of the polymer.6
In practical use of FBMI, their thermochemical characteristics can have essen-
tial significance. In this connection, it is necessary and appropriate to examine the
thermochemical characteristics of a number of different structures of BMI by dif-
ferential scanning calorimetry.
DSC curves (Fig. 5.1) of all studied BMI, taken in the temperature range of
20–400°C at the rate of temperature rise of 10°C/min are clearly played two peaks
endothermic, the melting process of BMI and exothermic corresponding to the pro-
cess of disclosure of the double bonds.

FIGURE 5.1  DSC curves of BMI. (1) N,N’-diphenylmethane-bis-maleimide; (2) N,N’-

diphenyloxide-bis-maleimide; and (3) N,N’-m-phenylene-bis-maleimide (FBMI).

The position of the peaks in the respective process on the temperature scale
depends on the chemical structure of the compounds. According to the value of
enthalpy disclosure of double bonds, studied compounds in their thermochemical
characteristics and probably related to reactivity in the reactions occurring with the
opening of the double bonds are not significantly different. In this connection, the
use of aliphatic polyamides FBMAK, FBMI is justified as modifying component.
This component (MFBI), and accordingly MFBAK as its intermediate are produced
in industrial conditions and are widely used for the production of a large range of
heat-resistant composite materials. They are used to improve the adhesion of the
cord to rubber mass in the manufacture of various kinds of tires for the automotive
industry.
Effectiveness of modifying action of FBMAK in thermo-oxidative degradation
processes of PA 6 compositions was evaluated on samples of three types: model-
modified FBMAK powder compositions, films, and molded samples.
Modification of Polyamide 6 By N,N’–Bis-Maleamide Acid 67

Model-modified powder compositions of PA 6 were prepared for the rapid

analysis of possible stabilizing action FBMAK to the polymeric matrix. They were
prepared as follows: PA 6 unstabilized granules were placed in a mixer, where nitro-
gen was supplied to provide oxygen-free environment. The temperature was raised
to 240°C and a stirrer was switched on. With continuous stirring, the calculated
amount of FBMAK was injected into the polymer melt. The mixture was being
stirred for 5 min. Then it was poured into a mold and cooled. After curing, the
sample was removed from the mold and crushed at a cryogenic temperature (after
soaking for 10 min in liquid nitrogen at −180°C) to a fine powder. Investigation of
the thermal stability was carried out by differential thermal and thermogravimetric
analysis. The sample weight was 10 mg, a heating rate in the range of 20–500°C was
5°C/min. The activation energy of thermal oxidative degradation of the polymer Ed
was calculated from the Broido method11–13 according to dynamic thermogravim-
etry obtained by thermo-setting—module TA-400 of the Mettler Toledo company
(Switzerland) in the temperature range of 330–400°C. Instrument calibration was
performed on indium standard.
Laboratory samples of the polyamide films of 15–20 microns thick were cast
from solutions of PA 6 with formic acid. To obtain solutions, a sample of the poly-
mer (2 g) with a relative viscosity of 2.8 (determining in a solution of concentrated
sulfuric acid) was dissolved in 28 ml of formic acid at room temperature. After that,
the estimated quantity of FBMAK was injected into the solution and mixed thor-
oughly. Then degreased and dried on glass plates by pouring through a nozzle with
an adjustable gap, the layer of film-forming composition was deposited. The glass
plates were placed horizontally in a vacuum-drying oven, where at a residual pres-
sure of 2 mm Hg. Art. and a temperature not above 30°C for 4.5 h, the solvent was
removed. Formed on a glass substrate, polyamide film was removed and subjected
to research.
Samples were also prepared by injection molding as follows: FBMAK modifier
in an amount of 5–10 wt.% by weight of PA 6 was applied to the polymer granules
without the heat stabilizer with a relative viscosity of 2.8 by dusting. Powdered pel-
lets were peppered through the hopper to the injection molding machine, where they
were melted. From the molten mass, bilateral blades with working part 50 × 10 × 3
mm were cast. Experimental samples, 1 day after their manufacturing, were placed
in a heat chamber with a free circulation of air. They were maintained at 150°C for
predetermined time (30–210 h). Determination of the breaking strength of the sam-
ples was performed by stretching according to GOST 112-80 using the tensile test-
ing machine T 2020 DS 10 SH (Alpha Technologies UK, USA) at room temperature
and velocity of the gripper 100 mm/min. Judging by the results of measurements of
the tensile strength of the samples given in Table 5.2 generated in the step of heat
treating of polyamide compositions meshwork of aliphatic polyamide 6 at the ex-
pense of the reactive groups of FBMAK (content in the composition of 5–10 wt.%)
and functional groups of PA 6 predetermines the higher rates of heat resistance (tem-
68 Process Advancement in Chemistry and Chemical Engineering Research

perature of thermo-oxidative degradation increases by 10–15°C) and deformation-

strength properties (tensile strength increases by almost 10 MPa at initial modified
samples, amounting 64.0–68.0 MPa) as compared to the unmodified polyamide 6
(59.0 MPa) and is comparable with PA 6 modified by the bis-maleimide (FBMI).

TABLE 5.2  Tensile Strength of PA 6 and Modified by MFBI MFBAK Samples of PA 6 after
Thermal Oxidation in Air at 150°C for 30–210 h.
Tensile strength, MPa
After thermal oxidation in air for, h Ed, kJ/
Td, mol
Material
Initial °C
30 60 90 120 150 180 210 30

PA 6 59.0 50.0 49.0 41.0 35.5 30.5 23.0 18.6 275 120
PA 6 + 5 wt.%
64.0 66.5 64.0 61.4 61.0 61.5 61.0 60.0 285 135
FBMAK
PA 6 + 10
wt.% FB- 68.0 69.0 69.5 62.4 62.0 63.4 63.0 61.0 290 148
MAK
PA 6 + 5
63.4 64.6 63.0 62.6 62.0 62.0 61.4 60.7 287 141
wt.% FBMI6

Importantly, FBMAK as well as FBMI, provide a thermally stabilizing effect

on polyamide 6 at various temperature and time of exposure of samples of polymer
compositions. Calculation of the activation energy of thermal oxidative degradation
of the samples (Ed) also indicates the formation of cross-links in a matrix structure
of polyamide 6 at the expense of additives of MFBAM and MFBI, increasing de-
pending on the modifier content of FBMAK from 135 to 148 kJ/mol.
As seen from Table 5.2, polyamide 6 modified with bis-maleamidoacid has not
only improved strength characteristics as compared with the original PA 6, but is
also more resistant to high temperature and time fields.

5.3 CONCLUSION
Thus, the use of bis-amino acid (FBMAK) as a builder in the system of aliphatic
polyamide 6 improves strength properties and thermal characteristics of a polymeric
material based on PA 6 virtually in the same range as the previously used for the
same purpose FBMI.6
Modification of Polyamide 6 By N,N’–Bis-Maleamide Acid 69

KEY WORDS

•• polyamide 6
•• N,N’-diphenylmethane-bis-maleimide
•• N,N’-diphenyloxide-bis-maleimide
•• N,N’-m-phenylene-bis-maleimide
•• modification
•• energy activation

REFERENCES
1. Kudryavtsev, G. I.; Noskov, M. P.; Volokhina, A.V. Polyamide Fibers. Chemistry 1976, 259.
2. Hapugalle, G.; Prokopchuk, N. R.; Prakapovich, V. P.; Klimovtsova, I. A. New Thermostabi-
lizers Polyamide 6 NASB Vestsі. Ser. Hіm. Navuk. 1999, 1, 114–119.
3. Vygodskii, Y. S. et al. The Anionic Polymerization of ε-Caprolactam and its Copolymerization
with ω-Dodekalaktamom in the Presence of Aromatic Polyimides Polym. Comp. Ser. A. 2006,
1 (6), 885–891.
4. Vygodskii, Y. S. et al. The Anionic Polymerization of ε-Karolaktama in the Presence of Aro-
matic Polyimides as Macromolecular Activators. Polym. Comp. Ser. A. 2003, 45 (2), 188–195.
5. Vygodskii, Y. S. et al. The Anionic Polymerization of ε-Caprolactam in the Presence of Aro-
matic Diimides Polym. Comp. Ser. A. 2005, 47 (7), 1077.
6. Biran, V. et al. About Modifying the Action of N,N’-bis-imides of Unsaturated Dicarboxylic
Acids, Aliphatic Polyamides; Reports of the Academy of Sciences: Byelorussian SSR, 1983;
Vol. 27 (8), pp 717–719.
7. Volozhin, A. I. et al. Synthesis of N, N’-Bis-Imides of Unsaturated Dicarboxylic Acids, Cyclo-
aliphatic. Vestsі BSSR. Ser. Hіm. Navuka. 1974, 1, 98–100.
8. Nakanishi, K. Infrared Spectra and Structure of Organic Compounds, Wiley: New York,
1965; p 216.
9. Boldyrev, A. G. et al. The Study by EPR of Free Radicals in Polyimides; Report of the Acad-
emy of Sciences: USSR, 1965; T. 163 (5), pp 1143–1146.
10. Ingram, D. In Electron Paramagnetic Resonance in Biology; Agip, Y. I.; Kayushin, L. P., Eds.;
Wiley: New York, 1972; p 296.
11. Broido, A.; Semple, A. Sensitive Graphical Method of Treating Thermogravimetric Analysis
Date I. Polym. Sci. 1969, Part A. 2, 7 (10), 1761–1773.
12. Prokopchuk, N. R. Study the Thermal Stability of Polymers by Derivatography Vestsі BSSR.
Ser. Hіm. Navuka. 1984, 4, 119–121.
13. Polymer Construction. Method for Determining the Durability of the Activation Energy for
Thermal Oxidative Degradation of Polymeric Materials; STB 13330-2002, Enter. 28.06.2002,
Technical Committee on Technical Regulation and Standardization in Construction: the Min-
istry of Architecture and Construction of Belarus: Minsk, BY, 2002; p 8.
CHAPTER 6

PROTECTIVE PROPERTIES OF
MODIFIED EPOXY COATINGS
N. R. PROKOPCHUK, M. V. ZHURAVLEVA, N. P. IVANOVA,
T. A. ZHARSKAYA, and E. T. KRUT’KO
Belarusian State Technological University, Sverdlova Str.13a, Minsk, Republic of
Belarus

CONTENTS
Abstract....................................................................................................................72
6.1 Introduction....................................................................................................72
6.2 Main Part........................................................................................................72
6.3 Conclusion.....................................................................................................78
Keywords.................................................................................................................79
References................................................................................................................79
72 Process Advancement in Chemistry and Chemical Engineering Research

ABSTRACT
This chapter is devoted to the development and research of new film materials based
on epoxy resins with improved properties. Evaluation of protective properties is
done by electrochemical and physicomechanical methods of research that provide
the most complete picture of the corrosion processes occurring under the paint film.
These studies allowed adjusting the coating composition to the individual applica-
tions in order to achieve a high degree of protection of metal surfaces.

6.1 INTRODUCTION
Epoxy materials have superior performance properties, so they have been used to
produce high-quality coatings. Coating materials based on epoxy oligomers are used
to prepare coatings for various purposes, chemical-resistant, water-resistant, heat-
resistant, and insulating coatings. They are characterized by high adhesion to metal-
lic and nonmetallic surfaces, resistance to water, alkalis, acids, ionizing radiation,
low porosity, small moisture absorbability, and high dielectric properties.1 How-
ever, there are a number of outstanding issues to improve the barrier properties of
paints based on epoxy resins, which limit their wider use in aeronautical engineer-
ing as well as in engineering and shipbuilding.2 Chemical structure of epoxy resins
provides ample opportunities to control their properties by introducing modifying
additives to achieve maximum compliance with the requirements of the resulting
material.

6.2  MAIN PART

The aim of this study was to develop and research new film materials based on ep-
oxy diane resin with improved barrier properties.
The object of the study was commercially produced epoxy resin E-41 in
solution (E-41s) (TU 6-10-607-78), which is a solution of the resin E-41 with
a mass fraction 66 ± 2% in xylene (GOST 9410-78, GOST 9949-76) with ac-
etone (GOST 2768-84) at a ratio of 4:3 by weight. Resin solution E-41 in a
mixture of xylene and acetone (resin E-41s) is used for the manufacture of
paints for various purposes. Resin E-41s refers to medium molecular weight
(MW 900–2000) epoxy diane resin. Its density is 1.03–1.06 g/m3. Product of
copolycondensation of low molecular epoxy resin E-41 with difenidol propane
is represented by the formula shown in Scheme 6.1.
Protective Properties of Modified Epoxy Coatings 73

Physicochemical characteristics of the resins E-41s are shown in Table 6.1.

TABLE 6.1  Physicochemical Characteristics of the Resin E-41s.

Index name Norm on the highest quality category

Appearance of the resin solution Homogeneous transparent liquid

Appearance of the film Poured on glass is clean. Slight rash

Color on iodometric scale, mg I2/100 cm3, not

darker than 30

Viscosity by viscometer VZ-246 (OT-4) with

a nozzle diameter of 4 mm at a temperature of
20.0 ± 0.5°C, c 80–130

Volume of solids, % 66 ± 2

Mass fraction of epoxy groups in terms of dry

resin 6.8–8.3

Mass fraction of chloride ion (in terms of dry

resin), %, not more than 0.0045

Mass fraction of saponifiable chlorine (in terms

of dry resin), %, not more than 0.25

As a modifying component, p-aminophenol (pAPh) was used. It is known that

aminophenols are corrosive inhibitors. The presence of the aromatic ring and the
amide and hydroxyl functional groups in the molecule of p-aminophenol dictates
the fundamental possibility of using this compound as a modifier of epoxy oligomer,
allowing to increase the corrosion resistance of the coating.
The film-forming composition was prepared by introducing into E-41s 10% so-
lution of p-aminophenol in dimethylformamide at a concentration range of 0.5–5.0
wt.%, followed by stirring until smooth. Hardener of brand E-45 (TU 6-10-1429-79
with changing No 2), low molecular weight polyamide resin solution in xylene, in
the amount of 14% by weight of resin solids was used. Films on various substrates
were cast from the above solutions. Curing of modified epoxy diane compositions
were carried out at a temperature of 110°C for 140 min.
74 Process Advancement in Chemistry and Chemical Engineering Research

Adhesive strength of the formed coatings was determined by the standard meth-
od in accordance with ISO 2409 and GOST 15140-78 by the cross-cut incision with
the kickback. The essence of the method in the application of cross-cut incisions on
the finished coatings with the tool “Adhesion RN” and a visual assessment of the
condition of the coatings after the impact action of the device “Kick Tester” exerted
on the opposite side of the plate at the site of incision. Coating condition is com-
pared with standard classification and measured in points.
Impact resistance of coating samples were evaluated using the device “Kick
Tester” in accordance with ISO 6272 and GOST 4765-73.
The method for determining the impact strength of films (measured in centi-
meters) is based on the instantaneous deformation of the metal plate coated with
the paint by the free fall of load on the sample and is realized through the device
“Impact Tester,” which is intended to control the impact strength of the polymer,
powder, and paint coatings.
The hardness of paint coatings was determined with a pendulum device (ISO
1522). The essence of the method consists in determining the decay time (number
of oscillations) of the pendulum in its contact with the painted coating. Hardness
is determined by the ratio of the number of oscillations of the coated sample to the
number of oscillations of the sample without coating.
Flexural strength of the coatings was determined by a device SHG1 (ISO 1519
GOST 6806-73) by bending of the coated sample around test cylinders since larg-
er diameters at an angle of 180°. On one of the cylinder diameters, coating either
cracks or breaks or peels. In this case, the paint has an elasticity of previous diameter
test cylinder of the device in which it is not destroyed. Viewed count is in the radii
of curvature in millimeters.
As can be seen from Table 6.2, at a curing temperature of 110°C of the obtained
modified compositions with the modifier content of 0.5–2.0% hardness of the coat-
ing and adhesion is improving and impact strength is increasing.

TABLE 6.2  Adhesion and Strength Properties of Epoxy Diane Coatings on Steel Substrates
(Warming up to 110°C, 140 min).
pAPh content, (%) Hardness, rel. u. Adhesion to steel, points Tensile impact, cm
0.0 0.66 1 2.5
0.5 0.69 0 5.0
1.0 0.73 0 10.5
2.0 0.70 0 7.5
3.0 0.67 1 3.0
4.0 0.63 2 6.0
5.0 0.47 2 1.0
Protective Properties of Modified Epoxy Coatings 75

Protective properties of coatings are determined by the sum of physical and

chemical properties, which can be reduced to four basic characteristics:
• Electrochemical and insulation properties of coatings;
• The ability of films to retard diffusion and carrying corrosive agents to a metal
surface;
• The ability of coatings containing a film-forming, pigments or inhibitors, pas-
sivate, or electrochemically protect metal;
• Adhesion and mechanical properties of the coatings.
All these properties are interrelated and influence each other mutually. Dete-
rioration of properties of the film as a diffusion barrier will immediately lead to a
reduction in adhesion due to the development of the corrosion process under the
film. Therefore, adhesion itself, how high it may be, cannot provide long-lasting
protection from corrosion. Likewise, coatings with high diffusion limitations, but
with poor adhesion cannot provide long-lasting protection.3
Paint application is one of the most common and reliable ways to protect metal
surfaces from corrosion and give a decorative surface finish. It is known that the
testing of protective properties of the coating in an operational environment takes
a lot of time, which does not comply with any developers or manufacturers. Rapid
tests provide information about the resistance of the coating under its compulsory
destruction simulating natural mechanism of aging in a short trial time. Electro-
chemical methods are used as these accelerate the test methods.
Electrochemical methods are based on measurement of electrical parameters of
the electrochemical phenomena occurring in the test solution. This measurement
was performed using an electrochemical cell, which is a container with the test so-
lution in which electrodes are placed. Electrochemical processes are accompanied
by the appearance in the solution or changing of the potential difference between
the electrodes or changing of the magnitude of current flowing through a solution.4
To assess the protective properties and select the modifier concentration in the
polymer coating, the study of the time dependence of the stationary potential of the
metal coating and removal of the anodic polarization curves was used. Potential
measurement of the metal coating was being performed in 0.5% HCl at a tempera-
ture of 20 ± 2°C in the scale of silver chloride reference electrode for 24 h, then
values were converted to a scale of the standard hydrogen electrode.
Removal of anodic polarization curves in a 0.5% HCl was being performed
using a potentiostat 50 PI-1, and a driving voltage programmer 8 in potentiostatic
mode. Tests were carried out in a three-electrode electrochemical cell. Before re-
moving the anode polarization curve, value of the equilibrium potential of the metal
cover was being measured for 5 min. Anodic polarization was carried out in po-
tentiostatic mode at a potential step change in 20 mV with delayed current at each
potential for 1 min.
By the slope of the Tafel plot of the polarization curve in the coordinates E–lgi
(Fig. 6.1) value of the coefficient b was determined5:
76 Process Advancement in Chemistry and Chemical Engineering Research

2.303 × R × T
b= .
a ×n×F
Corrosion current density in the metal coating was determined graphically by
the intersection of stationary potential measured for 24 h (E24) in 0.5% HCI, and
the straight portion of the anode polarization curve, which if necessary, was extrapo-
lated. It was experimentally established that offset values of stationary potential of
corrosive base covering systems in electronegative side over time may be due to
relief of the anode ionization of the metal due to the coating moisture permeability
and increase of its conductivity.
For samples with an epoxy polymer coating (EPC), stationary potential takes
more electropositive value compared to carbon steel. With increasing concentration
of modifying additive in the p-aminophenol coating, displacement capacity reaches
30 mV.
For samples with EPC with modifier content of 0.5–5.0% in the potential range
−0.2 to 0.3 b, Tafel slopes of all areas of the anode curves are approximately the
same (Table 6.3). This suggests that the mechanism of active dissolution of iron in
the pores of the polymer coating does not change, and inhibition is due to the de-
crease of the effective surface of the dissolving metal.
Organic modifier p-aminophenol introduced into the coating has two functional
groups of atoms containing lone pair electrons, facilitating its adsorption on iron,
which applies to transition metals with a free d orbitals. The presence of p-amino-
phenol in the polymer coating decreases the effective surface of the dissolving metal
and inhibits the anodic process.
Extrapolation of the linear portions of the polarization curves (Fig. 6.1) to the
measured stationary capacity allows to determine the corrosion rate.

FIGURE 6.1  Anodic polarizat curve. Example: Steel 08 kp: EPC + 1% modifier. Е24 =
−0.275 V; iкор = 1.62 mA/cm2, t = 19°C.
Protective Properties of Modified Epoxy Coatings 77

Table 6.3 shows the stationary potentials and the corrosion rate of the metal-
covering systems.

TABLE 6.3  Stationary Potentials and the Corrosion Rate of the Steel 08 kp—Epoxy Coating
in 0.5% HCl.

Tested sample E, B lgi i, mA/cm2 b, B Percentage

of modifier

Carbon steel 08 kp −0.288 0.29 1.95 0.1346 –

Carbon steel 08 kp: LPC + 0.5 M −0.28 0.24 1.74 0.1130 0.5

Carbon steel 08 kp: LPC + 1.0 M −0.275 0.21 1.62 0.0978 1

Carbon steel 08 kp: LPC + 2.0 M −0.266 0.18 1.51 0.0911 2

Carbon steel 08 kp: LPC + 3.0 M −0.26 0.15 1.41 0.0572 3

Carbon steel 08 kp: LPC + 4.0 M −0.252 0.11 1.29 0.0434 4

Carbon steel 08 kp: LPC + 5.0 M −0.238 −0.05 0.89 0.0328 5

Tested sample E, B lgi, i, mA/cm2 b, B Percentage

mA/ of modifier
cm2

From these data, one can conclude that the polymer coatings inhibit corrosion of
carbon steel 08 kp , which corrodes in 0.5% HCl at a speed of 1.95 mA/cm2 . Appli-
cation of epoxy polymer coating containing modifier of n-aminophenol 0.5−5.0%,
reduces the corrosion rate of steel in 1.1−2.2 times.
With increasing concentration of n-aminophenol modifier in the polymer coat-
ing corrosion resistance at the system increases, whereas the corrosion current
density decreases (Fig. 6.2), and the polarization curves are shifted to lower cur-
rents. Basing on the obtained results, it can be concluded that the polymer coatings
based on epoxy resins with modifier inhibit corrosion of carbon steel better than
without it.
78 Process Advancement in Chemistry and Chemical Engineering Research

FIGURE 6.2  The dependence of the corrosion current on the percentage of modifier.

6.3 CONCLUSION
Introduction of n-aminophenol modifier at a concentration of 0.5–5.0 wt.% into a
polymeric epoxy resin coating improves the corrosion resistance of the system to
0.5% HCl, while the current density of steel corrosion 08 kp decreases from 1.95 to
0.89 mA/cm2 and the polarization curves are shifted to lower currents. Application
of the epoxy polymer coating modifier in an amount of 5% reduces the corrosion
rate of carbon steel in 08 kp 0.5% HCl 2.2 times. Addition of 0.5–2.0% modifier
also improves physical and mechanical characteristics (improved strength, hard-
ness, and adhesion of coatings).
Experimental studies have shown that additional evaluation of protective prop-
erties of coatings by electrochemical methods in conjunction with conventional for
the paint industry methods of research yielded a better understanding of corrosion
processes under cover, and allowed to assess their impact on the course of the con-
centrations of the modifier. These studies allowed to adjust the coating composition
to the individual applications in order to achieve a high degree of protection of metal
surfaces.
Protective Properties of Modified Epoxy Coatings 79

KEYWORDS

•• oligoepoxide
•• aminophenol
•• electrochemical method
•• epoxy polymer
•• coatings
•• corrosion
•• mechanical properties

REFERENCES
1. Lee, H.; Neville, K. Handbook of Epoxy Resins; Energiya: Moscow, RU, 1973; p 268.
2. Kireyeva, V. G. Coating Materials Based on Epoxy Resins; NIITEKHIM: Moscow, RU, 1992;
p 48 (Survey information/Ser “Paint industry”).
3. Rosenfeld, I. L. Corrosion Inhibitors; Khimiya: Moscow, RU, 1977; p 352.
4. Semenova, I. V. In Corrosion and Corrosion Protection; Florianovich, G. M.; Khoroshilov, A.
V., Eds.; Fizmatlit: Moscow, RU, 2006; p 328.
5. Damascus, B. B.; Peter, O. Electrochemistry: A Textbook for Chem. Faculty. Universities;
Higher School: Moscow, RU, 1987; p 295.
CHAPTER 7

CHEMICAL MODIFICATION OF
SYNDIOTACTIC 1,2-POLYBUTADIENE
M. I. ABDULLIN, A. B. GLAZYRIN, O. S. KUKOVINETS,
A. A. BASYROV, and G. E. ZAIKOV

CONTENTS
Abstract....................................................................................................................82
7.1 Ozonation.......................................................................................................83
7.2 Epoxidation....................................................................................................85
7.3 Hydrochlorination..........................................................................................87
7.4 Halogenation..................................................................................................89
7.5 Dichlorocyclopropanation..............................................................................90
7.6 Interaction with Methyl Diazoacetate............................................................91
7.7 Interaction with Aromatic Amines.................................................................93
7.8 Interaction with Maleic Anhydride................................................................94
Keywords.................................................................................................................96
References ...............................................................................................................96
82 Process Advancement in Chemistry and Chemical Engineering Research

ABSTRACT
Results of chemical modification of syndiotactic 1,2-polybutadiene under various
chemical reagents are presented. Influence of the reagent nature, both on the reactiv-
ity of >С═С< double bonds in syndiotactic 1,2-polybutadiene macromolecules at its
chemical modification and on the composition of the modified polymer products,
is considered basing on the analysis of literature and the authors’ own researches.
Obtaining polymer materials of novel or improved properties is considered a
major direction in modern macromolecular chemistry.1 Researches aimed at obtain-
ing polymers via chemical modification methods have been quite prominent along
with traditional synthesis methods of new polymer products by polymerization or
polycondensation of monomers.
Polymers with unsaturated macrochains hold much promise for modification.
The activity of carbon–carbon double bonds as related to many.
Syndiotactic 1,2-polybutadiene obtained reagents allow introducing substituents
of different chemical nature in the polymer chain (including heteroatoms). Such
modification helps to vary within wide range of physical and chemical properties
of the polymer and render it new and useful features. By stereospecific butadiene
polymerization in complex catalyst solutions2–7 provides much interest for chemical
modification.
In contrast to 1,4-polybutadiens and 1,2-polybutadiens of the atactic structure,
the syndiotactic 1,2-polybutadiene exhibit thermoplastic properties combining elas-
ticity of vulcanized rubber and ability to move to the viscous state at high tempera-
tures and be processed like thermoplastic polymers.8–11
The presence of unsaturated >С═С< bonds in the syndiotactic 1,2-PB macro-
molecules creates prerequisites for including this polymer into various chemical re-
actions resulting in new polymer products. Unlike 1,4-polybutadiens, the chemical
modification of syndiotactic 1,2-PB is insufficiently studied, though there are some
data available.12–15
A peculiarity of the syndiotactic 1,2-PB produced nowadays is the presence of
statistically distributed cis-and trans- units of 1,4-diene polymerization16,17 in mac-
romolecules along with the order of 1,2- units at polymerization of 1,3-butadiene.
Their content amounts to 10–16%. Thus, by its chemical structure, syndiotactic
1,2-polybutadiene can be considered as a copolymer product containing an orderly
arrangement of 1,2-units and statistically distributed 1,4-polymerization units of
1,3-butadiene:
Chemical Modification of Syndiotactic 1,2-Polybutadiene 83

Taking into account, syndiotactic 1,2-PB microstructures and the presence of

>С═С< various bonds in the polydiene macromolecules, the influence of some
factors on the polymer chemical transformations has been of interest. The factors
in question are determined both by the double bond nature in the polymer and the
nature of the substituent in the macromolecules.
In the paper, the interaction of the syndiotactic 1,2-PB and the reagents of dif-
ferent chemical nature such as ozone, peroxy compounds, halogens, carbenes, aro-
matic amines, and maleic anhydride are considered.
A syndiotactic 1,2-PB with the molecular weight Mn = (53–72) × 103; Mw/Mn =
1.8–2.2; 84–86% of 1,2-butadiene units (the rest being 1,4-polymerization units);
syndiotacticity degree 53–86% and crystallinity degree 14–22% were used for mod-
ification.

7.1 OZONATION
At interaction of syndiotactic 1,2-PB and ozone, the influence of the inductive ef-
fect of the alkyl substituents at the carbon–carbon double bond on the reactivity of
double bonds in 1,2- and 1,4-units of butadiene polymerization is vividly displayed.
Ozone first attacks the most electron-saturated inner double bond of the polymer
chain. The process is accompanied by the break in the >С═С< bonds of the main
chain of macromolecules and a noticeable decrease in the intrinsic viscosity and
molecular weight of the polymer (Fig. 7.1) at the initial stage of the reaction (func-
tionalization degree α < 10%).17–20 Due to the ozone high reactivity, partial splitting
of the vinyl groups is accompanied by spending double bonds in the main polydiene
chain.
84 Process Advancement in Chemistry and Chemical Engineering Research

FIGURE 7.1  Dependence of the intrinsic viscosity [h] (1) and the average molecular weight
Mn (2) of the formyl derivative of the syndiotactic 1,2-PB from the functionalization degree
of the α-polymer (with chloroform as a solvent, 25°С).

However, it does not affect the average molecular weight of the polymer up to
the functionalization degree of 15% (Fig. 7.1). Depending on the chemical nature
of the reagent used for the decomposition of the syndiotactic 1,2-PB ozonolysis
products (dimethyl sulfide or lithium aluminum hydride),17–20 the polymer products
containing aldehyde or hydroxyl groups are obtained (Scheme 7.1).

SCHEME 7.1

The structure of the modified polymers is set using IR and NMR spectroscopy.17
The presence of C-atom characteristic signals connected with aldehyde (201.0–
Chemical Modification of Syndiotactic 1,2-Polybutadiene 85

201.5 ppm) or hydroxyl (56.0–65.5 ppm) groups in 13С NMR spectra allows identi-
fying the reaction products.
Thus, the syndiotactic 1,2-PB derivatives with oxygen-contained groupings in
the macromolecules may be obtained via ozonation. Modified 1,2-PB with differ-
ent molecular weight and functionalization degrees containing hydroxi or carbonyl
groups are possible to obtain by regulating the ozonation degree and varying the
reagent nature used for decomposing the products of the polymer ozonation.

7.2 EPOXIDATION
Influence of the double bond polymer nature in the reaction direction and the poly-
mer modification degree is vividly revealed in the epoxidation reaction of the syn-
diotactic 1,2-PB, which is carried out under peracids (performic, peracetic, meta-
chloroperbenzoic, and trifluoroperacetic ones),21–27 tert-butyl hydroperoxide,21–23
and other reagents28–30 (Table 7.1).

TABLE 7.1  Influence of the Epoxidizing Agent on the Functionalization Degree α of

Syndiotactic 1,2-PB and the Composition of the Modified Polymer*.
Content in the modified polymer, mol.%

Epoxidizing agent α, mol. (%) Epoxy groups >С═С<bonds

1,2-units 1,4-units 1,2-units 1,4-units

**R1COOH/H2O2 11.0–16.0 – 11.0–16.0 84.0 0–5.0

**R COOOH
2
32.1 16.1 16.0 67.9 –
**R COOOH
3
34.6 18.6 16.0 65.4 –
Na2WO4 /H2O2 31.0 15.0 16.0 69.0 –
Na2MoO4 /H2O2 23.7 7.7 16.0 76.3 –
Mo(CO)6/t-BuOOH 18.0 18.0 – 66.0 16.0
NaClO 16.0 – 16.0 84.0 –
NaHCO3/H2O2 16.0 – 16.0 84.0 –
* The polymer with the content of 1,2- and 1,4-units with 84 and 16%, respectively;
** where R1–H–, Ме–, Еt–, CH3CH(OH)–; R2–м–СlС6Н4; R3–CF3–.

Depending on the nature of the epoxidated agent and conditions of the reac-
tion,21–27 polymer products of different composition and functionalization degree
can be obtained (Table 7.1).
86 Process Advancement in Chemistry and Chemical Engineering Research

As established earlier,21–24,26 at interaction of syndiotactic 1,2-PB and aliphat-

ic peracids obtained in situ under hydroperoxide on the corresponding acid, the
>С═С< double bonds in 1,4-units of macromolecules are mainly subjected to ep-
oxidation (Scheme 7.2). Higher activity of the double bonds of 1,4-polymerization
units in the epoxidation reaction is revealed at interacting syndiotactic 1,2-PB and
sodium hypochlorite as well as percarbonic acid salts obtained in situ through the
appropriate carbonate and hydroperoxide.31–35

SCHEME 7.2

It should be noted that the syndiotactic 1,2-PB epoxidation by the sodium hypo-
chlorite and percarbonic acid salts carried out in the alkaline enables to prevent the
disclosure reactions of the epoxy groups and a gelation process of the reaction mass
observed at polydiene epoxidation by aliphatic peracids.31–32 The functionalization
degree of 1,2-PB in the reactions with the stated epoxidizing agents (α ≤ 16%, Table
7.1) is determined by the content of inner double bonds in the polymer.
To obtain the syndiotactic 1,2-PB modifiers of a higher degree of functional-
ization (up to 35%) containing oxirane groups, both in the main and side chain of
macromolecules (Scheme 7.2), it is necessary to use only active epoxidizing agents
meta-chloroperbenzoic (MCPBA), trifluoroperacetic acids (ТFPA),23 and metal
complexes of molybdenum and tungsten, obtained by reacting the corresponding
salts with hydroperoxide25 (Table 7.1). From the epoxidizing agents given, a trifluo-
roperacetic acid is the most active (Fig. 7.2).23,26
However, at the syndiotactic 1,2-PB epoxidation by the trifluoroperacetic acid, a
number of special conditions is required to prevent the gelation of the reaction mass,
namely usage of the base (Na2HPO4, Na2CO3) and low temperature (less than 5°С).23
Chemical Modification of Syndiotactic 1,2-Polybutadiene 87

FIGURE 7.2  Influence of the peracid nature on the kinetics of oxirane groups accumulation
at the syndiotactic 1,2-PB epoxidation: 1—ТFPA ([Na2HPO4]/[ТFPA] = 2; 0°С); 2—MCPBA
(50°С); 3—Na2MoO4 /H2O2 (55°С); 4—HCOOH/H2O2 (50°С).

At reacting the syndiotactic 1,2-PB and the catalyst complex [t-BuООН–

Мо(СО)6], a steric control at approaching the reagents to the double polymer bond
is carried out.21–24 This results in participation of less active but more available vinyl
groups of macromolecules in the reaction (Table 7.1, Scheme 7.2).
Thus, modified polymer products with different functionalization degrees (up to
35%) may be obtained on the syndiotactic 1,2-PB basis according to the epoxidiz-
ing agent nature. The products in question contain oxirane groups in the main chain
(with aliphatic peracids, percarbonic acid salts, and NaClO as epoxidizing agents),
in the side units of macromolecules [t-BuООН–Мо(СО)6] or in 1,2- and 1,4-units
(ТFPA, MCPBA, and metal complexes of molybdenum and tungsten).

7.3 HYDROCHLORINATION
In adding hydrogen halides and halogens to the >С═С< double bond of 1,2-PB, the
functionalization degree of the polymer is mostly determined by the reactivity of the
electrophilic agent. Relatively low degree of polydiene hydrochlorination (10–15%)
at interaction of HCl and syndiotactic 1,2-PB16,36,37 is caused by insufficient reactiv-
ity of hydrogen chloride in the electrophilic addition reaction by the double bond
(Table 7.2). Due to this, more electron-saturated >С═С< bonds in 1,4-units of bu-
tadiene polymerization are subjected to modification.
88 Process Advancement in Chemistry and Chemical Engineering Research

The process is intensified at polydiene hydrochlorination under АlСl3 due to a

harder electrophile Н+[AlCl4]¯ formation at its interaction with HCl.37 In this case,
double bonds of both 1,2- and 1,4-polidiene units take part in the reaction (Scheme
7.3):

SCHEME 7.3

Usage of the catalyst АlСl3 and a polar solvent medium (dichloroethane) al-
lows speeding up the hydrochlorination process (Table 7.2) and obtaining polymer
products with chlorine contained up to 28 mass% and the functionalization degree
α up to 71%.37
By the 13C NMR spectroscopy method,37 it is established that the >С═С< dou-
ble bond in the main chain of macromolecules is more active at 1,2-PB catalytic
hydrochlorination. Its interaction with HCl results in the formation of the structure
(a) (Scheme 7.4). At hydrochlorination of double bonds in the side chain, the chlo-
rine atom addition is controlled by formation of the most stable carbocation at the
intermediate stage. This results in the structure (b) with the chlorine atom at carbon
β-atom of the vinyl group (Scheme 7.4):

SCHEME 7.4
Chemical Modification of Syndiotactic 1,2-Polybutadiene 89

7.4 HALOGENATION
Effective electrophilic agents like chlorine and bromine easily join double carbon–
carbon bonds,16,38–40 both in the main chain of syndiotactic 1,2-PB and in the side
chains of macromolecules (Scheme 7.5):

SCHEME 7.5

The reaction proceeds quantitatively: syndiotactic 1,2-PB chlorine derivatives

with chlorine w(Cl) up to 56 mass% (α ~98%) (Fig. 7.3) and syndiotactic 1,2-PB
bromo-derivatives with bromine up to 70 mass% (α ~94%) are obtained.
According to the 13C NMR spectroscopy, polymer molecules with dihalogen
structural units (Scheme 7.6) and their statistic distribution in the macro chain serve
as the main products of syndiotactic 1,2-PB halogenation.16,40

FIGURE 7.3  Kinetics of syndiotactic 1,2-PB chlorination. Chlorine consumption: 1—1

mol/h per mol of syndiotactic 1,2-PB; 2—2 mol/h per mol of syndiotactic 1,2-PB; 20°С, with
CHCl3 as a solvent.
90 Process Advancement in Chemistry and Chemical Engineering Research

SCHEME 7.6

7.5 DICHLOROCYCLOPROPANATION
There is an alternative method for introducing chlorine atoms into the 1,2-PB mac-
romolecule structure, namely a dichlorocyclopropanation reaction. It is based on
generating an active electrophile agent in the reaction mass at dichlorocarbene mod-
ification, which is able to interact with double carbon–carbon polymer bonds.41–43
The syndiotactic 1,2-PB dichlorocyclopropanation is quite effective at dichloro-
carbene generating by Macoshi by the chloroform reacting with an aqueous solu-
tion of an alkali metal hydroxide. The reaction is carried out at the presence of a
phase transfer catalyst and dichlorocarbene addition in situ to the double polydiene
links44–46 according to Scheme 7.7:

SCHEME 7.7

The 13C NMR spectroscopy results testify the double bonds dichlorocyclo-
propanation, both in the main chain and side chains of polydiene macromolecules
(Scheme 7.8).
Chemical Modification of Syndiotactic 1,2-Polybutadiene 91

SCHEME 7.8

Cis-and trans-double bonds in the 1,4-addition units45 are more active in the
dichlorocarbene reaction.
The polymer products obtained contain chlorine up to 50 mass%, which cor-
responds to the syndiotactic 1,2-PB functionalization degree ~97%, that is, in the
reaction by the Makoshi method, full dichlorocarbenation of unsaturated >С═С<
polydiene bonds is achieved.23,45

7.6  INTERACTION WITH METHYL DIAZOACETATE

Modified polymers with methoxycarbonyl substituted cyclopropane groups47–51 are
obtained by interaction of syndiotactic 1,2-PB and carb methoxycarbonyl generated
at a catalytic methyl diazoacetate decomposition in the organic solvent medium
(Scheme 7.9):

SCHEME 7.9

The catalytic decomposition of alkyl diazoacetates comprises the formation of

the intermediate complex of alkyl diazoacetate and the catalyst.51,52 The generated
(alcoxicarbonyl)carbene at further nitrogen splitting is stabilized by the catalyst
with the carbine complex formation,51,52 interaction of which with the alkene results
in the cyclopropanation products (Scheme 7.10):
92 Process Advancement in Chemistry and Chemical Engineering Research

SCHEME 7.10

The output of the cyclopropanation products is determined by the reactivity of

the >С═С< double bond in the alkene as well as the stability and reactivity of the
carbine complex LnM═CH(O)R1, which fully depend on the catalyst used.52
The catalysts applied in the syndiotactic 1,2-PB cyclopropanation range as fol-
lows: Rh2(OAc)4 (α = 38%) > [Cu OTf]·0,5 C6H6 (α = 28%) > Cu(OTf)2 (α = 22%).51
By the 13C NMR spectroscopy methods, it is established that in the presence of
copper (I), (II) compounds, double bonds, both of the main chain and in the side
units of syndiotactic 1,2-PB macromolecules are subjected to cyclopropanation,
whereas at rhodium acetate Rh2(OAc)4, mostly the >С═С< bonds in the 1,4-addi-
tion units undergo it.51
Thus, catalytic cyclopropanation of syndiotactic 1,2-PB under methyl diazoace-
tate allows obtaining polymer products with the functionalization degree up to 38%
and their macromolecules containing cyclopropane groups with an ester substitu-
ent. The determining factor influencing the cyclopropanation direction and the syn-
diotactic 1,2-PB functionalization degree is the catalyst nature. By using catalysts
of different chemical nature, it is possible to purposefully obtain the syndiotactic
1,2-PB derivatives containing cyclopropane groups in the main chain (with rho-
dium acetate as a catalyst) or in 1,2- and 1,4-polydiene units (copper compounds),
respectively.
Along with the electronic factors determined by different electron saturation
of the >С═С< bonds in 1,2- and 1,4-units of polydiene addition and the catalyst
nature used in modification, the steric factors may also influence the reaction and
the syndiotactic 1,2-PB functionalization degree. The examples of the steric con-
Chemical Modification of Syndiotactic 1,2-Polybutadiene 93

trol may serve the polydiene reactions with aromatic amines and maleic anhydride
apart from the above-mentioned epoxidation reactions of syndiotactic 1,2-PB by
tеrt-butyl hydroperoxide.

7.7  INTERACTION WITH AROMATIC AMINES

Steric difficulties prevent the interaction of double bonds of the main chain of syn-
diotactic 1,2-PB macromolecules and aromatic amines (aniline, N, N-dimethylani-
line, and acetanilide). In the reaction with amines17,20,23 catalyzed by Na[AlCl4], the
vinyl groups of the polymer enter the reaction and form the corresponding syndio-
tactic 1,2-PB arylamino derivatives (Scheme 7.11):

SCHEME 7.11

From the NMR spectra analysis, it is seen that the polymer functionalization is
held through the β-atom of carbon vinyl groups.17
Introduction of arylamino groups in the syndiotactic 1,2-PB macromolecules
leads to increasing the molecular weight Mw (Fig. 7.4) and the size of macromolecu-
lar coils characterized by the mean-square radius of gyration (R 2 )1 / 2 .17,20

FIGURE 7.4  Influence of the aromatic amine nature on the molecular weight (Mw) of the
polymer modified by: 1—acetanilide; 2—N,N-dimethylaniline; and 3—aniline.
94 Process Advancement in Chemistry and Chemical Engineering Research

The results obtained indicate the intramolecular interaction of monomer units

modified by aromatic amines with vinyl groups of polydiene macromolecules at
syndiotactic 1,2-PB modification. This leads to the formation of macromolecules of
the branched and linear structure (Scheme 7.12):

SCHEME 7.12

Steric difficulties determined by the introduction of bulky substituents in the

polydiene units (“a neighbor effect”53,54) does not allow to obtain polymer products
with high functionalization degree as the arylamino groups in the modified polymer
does not exceed 8 mol.%. At the same time, secondary intermolecular reactions are
induced in the synthesis process involving arylamino groups of the modified mac-
romolecules and result in the formation of linear or branched polymer products with
high molecular weight.

7.8  INTERACTION WITH MALEIC ANHYDRIDE

The polymer products with anhydride groups are synthesized by thermal addition
(190°С) of the maleic anhydride to the syndiotactic 1,2-PB23,24 (Scheme 7.13):
Chemical Modification of Syndiotactic 1,2-Polybutadiene 95

SCHEME 7.13

The 13C NMR spectroscopy results show that the maleic anhydride addition
is carried out as an ene-reaction55 by the vinyl bonds of the polymer without the
cycle disclosure and the double bond is moved to the β-carbon atom of the vinyl
bond.23,24 The maleic anhydride addition to the >С═С< double bonds of 1,4-units
of polydiene macromolecules does not take place. As in synthesis of the arylamino
derivatives of syndiotactic 1,2-PB, it is connected with steric difficulties preventing
the interaction of bulk molecules of the maleic anhydride with inner double bonds
of the polymer chain.23
At syndiotactic 1,2-PB modification by the maleic anhydride, the so-called
“neighbor effect” is observed, that is, the introduction of bulk substituents into the
polymer chain prevents the functionalization of the neighboring polymer units due
to steric difficulties. For this reason, the content of anhydride groups in the modified
polymer molecules do not exceed ~15 mol. %.
Thus, >С═С< double bonds in 1,2- and 1,4-units of syndiotactic 1,2-PB mac-
romolecules considerably differ in the reactivity due to the polydiene structure. The
inductive effect of the alkyl substituents resulting in the increase of the electron
density of the inner double bonds of macromolecules determines their high activity
in the considered reactions with different electrophilic agents.
At interaction of syndiotactic 1,2-PB with strong electrophiles (ozone, halogens,
and dichlorocarbene), both inner double bonds and side vinyl groups of polydiene
macromolecules are involved in the reaction. It results in polymer products forma-
tion with quite a high functionalization degree. In the case when the used reagent
does not display enough activity (interaction of syndiotactic 1,2-PB and hydrogen
chloride and aliphatic peracids), the process is controlled by electronic factors: more
active double bonds in 1,4-units of the polymer chain are subjected to modification,
whereas the formed polymer products are characterized by a relatively low func-
tionalization degree.
Polymer modification reactions are mostly carried out through vinyl groups at
appearance of steric difficulties. They are connected with formation of a bulky in-
termediate complex or usage of reagents of big-sized molecules (reactions with aro-
matic amines, maleic anhydride, t-ВuООН/Мо(СО)6). Such reactions are controlled
by steric factors. The predominant course of the reaction by the side vinyl groups of
polymer macromolecules is determined by their more accessibility to the reagent at-
96 Process Advancement in Chemistry and Chemical Engineering Research

tack. However, in such reactions, high functionalization degree of syndiotactic 1,2-

PB cannot be achieved due to steric difficulties arousing through the introduction of
bulky substituents into the polymer chain. They limit the reagent approaching to the
reactive polydiene bonds.
Thus, a targeted chemical modification of the polydiene accompanied by obtain-
ing polymer products of different content and novel properties can be carried out
using differences in the reactivity of >С═С< double bonds of syndiotactic 1,2-PB.
Various polymer products with a set of complex properties is possible to obtain on
the syndiotactic 1,2-PB basis varying the nature of the modifying agent, a function-
alization degree of the polymer, and synthesis conditions.

KEYWORDS

•• syndiotactic 1,2-polybutadiene
•• chemical modification
•• functionalization degree
•• polymer products

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CHAPTER 8

NORMALIZATION OF THE
MAINTENANCE OF METALS IN
OBJECTS OF AN ENVIRONMENT
J.A. TUNAKOVA, S.V. NOVIKOVA, R.A. SHAGIDULLINA, and
M.I. ARTSIS1
Kazan National Research Technological University, 65 Karl Marx str., Kazan 420015,
Tatarstan, Russia. E-mail: [email protected]
1
N.M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, 4
Kosygin str., Moscow 119334, Russia. E-mail: [email protected]

CONTENTS
Abstract..................................................................................................................100
8.1 Introduction..................................................................................................100
8.2 Settlement—Experimental Part...................................................................100
8.3 Conclusion...................................................................................................109
Keywords...............................................................................................................110
References..............................................................................................................110
100 Process Advancement in Chemistry and Chemical Engineering Research

ABSTRACT
Results of modeling of the maintenance of the basic polluting substances (metals)
in hair of the person are examined depending on their maintenance in objects of an
environment. On the basis of the constructed models, normalization of the main-
tenance of metals in objects of an environment is carried out in view of receipt of
metals in an organism, both air and by a waterway.

8.1 INTRODUCTION
The system of sanitary and hygienic normalization working in territory of the Rus-
sian Federation takes into account the combined action (simultaneous action of sev-
eral substances at the same way of receipt) at calculation of summing effect at their
simultaneous receipt in atmospheric air. But in any way, it does not take into account
the effects of complex receipt of harmful substances in an organism in various ways
and with various environments with air, water, food, etc.
Metals concern to priority polluting substances, supervision for which are oblig-
atory in all environments due to their high risk to health of the person in rather low
concentration, and also ability to bioaccumulaytion. Danger of constant receipt of
metals is caused by impossibility their independent removing from an organism.
Metals act in an organism with water, the foodstuff, inhaled air.1–3

8.2  SETTLEMENT—EXPERIMENTAL PART

We develop methodology of normalization which basis were levels of accumulation
of metals in an organism of the person - basic protected object in territory of city, in
relation to the established4 regional specifications of the maintenance in bioenviron-
ments of the population of city.
We had led the analysis of amounts of receipt of metals by air and water—food
way on the materials stated in Ref. 5. It has been established that for metals such as
iron, copper, and lead is characteristic both air and water–food ways of receipt to
an organism with domination of the last. For other metals—the water—food way of
receipt or an air way of receipt considerably prevails is not estimated.
Basis of construction of models were results of long-term experimental re-
searches of the maintenance of metals in hair of children in the territory of Kazan,
potable water (the characteristic a waterway of receipt), snow, and soil covers (the
characteristic of an air way of receipt, in view of existential restrictions of regular
supervision over the maintenance of metals in atmospheric air). Nonlinear meth-
ods of plural regress were applied to modeling on the basis of criterion of the least
squares.
Normalization of the Maintenance of Metals 101

At the first stage, the maintenance of lead in an organism of the person (hair)
was investigated at air (ground) and water (potable water) ways of receipt to an
organism.
A linear regress model of dependence of the maintenance of lead in hair was
used from the maintenance of lead in ground and potable water:

Pb_v = 254,880 + 3,669,371*Pb_vod + 0.03691*Pb_p (1)

Factor of plural correlation R = 0.1406; factor of determination R2 = 0.01976

(about 2% of an explained dispersion). The resulted factors of regress: Pb_vod =
0.022928; Pb_p = 0.153831.
The model specifies direct dependence of the maintenance of lead in hair from
his maintenance in potable water and in ground. The degree of influence of variabil-
ity of the maintenance of lead in ground is seven times than in water. Small values
of factors of plural correlation and determination speak about small efficiency of
model. In this connection, there is a task of construction nonlinear plural regress
models.
Then a series of experiments on modeling nonlinear regress models of depen-
dence Lead in hair (Lead in potable water - Lead in ground) has been lead. A poly-
nom model was examined:
Polynom models have shown results close among themselves (factors of plural
correlation about 0.47 and factors of determination about 0.22), and have allowed
to raise factor of determination more than 10 times in comparison with linear mod-
el. Only the models were effective, including the maximal degrees of independent
variables (except for linear members). Among the considered models of the most
adequate, it is necessary to count square-law polynom model of plural regress with
factor of determination 0.235.
Efficiency constructed not polynom models is comparable to efficiency poly-
nom: the maximal factor of determination (0.236597) parabolic models not on sur-
passes the best result for square-law polynom models (0.234906) many.
Summary results are resulted in Table 8.1.

TABLE 8.1  Results of Modeling for Lead.

The name of model Model Factor of de-
terminations
Square law Z = 5549 − 7968*X + 0.61*Y + 264,014*X2 − 0.235
0.009*Y2
Cubic Z = 3981 − 4154*X + 0.32*Y – 6,020,931*X3 0.229
− 0.0001*Y3
A polynom fourth Z = 3195 − 28,83,836,474*X + 0.229273*Y + 0.222
203,319,032*X4 − 0.000001*Y4
102 Process Advancement in Chemistry and Chemical Engineering Research

TABLE 8.1  (Continued)

The name of model Model Factor of de-

terminations
A polynom of the fifth Z = 27,267,639 − 2,258,425*X + 0.181962*Y 0.215
degree + 8,144,045,245*X5 – 2.39 – 0.8*Y5
Parabolic Z = 19,478 + 14,809*X – 1.11*Y−3627* X + 0.236
11.99* Y
Logarithmic Z = −590,466 + 7,190,986*X – 0.539*Y − 0.234115
107,638*ln(X) + 15.188*ln(Y)
Hyperbolic 1 0.224212
Z = −8198 + 3361*X – 0.251*Y + 0.748* X −
1
178.273* Y
Cubic-hyperbolic model Z = −6,043,589 – 1,344,461,912*X + 0.231261
0.117143*Y + 3,790,787,976,566*X3 –
1 1
0.000066*Y3 + 0.282468* − 67,768,974* Y
X

Square-law-logarithmic Z = −28,496,762 + 12,549,000,68,251*X2 0.235711

model (without linear – 0.004610*Y2 − 56,696,124*ln(X) +
members) 8,157,432*ln(Y)

Square-law-parabolic Z = 104,104,117 + 171,775,113,216*X2 0.236

model (without linear – 0.006323*Y2 – 1,269,670,921* X +
members) 4,275,894* Y

Logarithmic-parabolic Z = −1329 − 208*ln(X) + 29.25*ln(Y) + 3417* 0.231

model X − 11.17* Y

The models containing three and more various elementary function in structure,
mattered F-statistics of less significance value that speaks about their notorious in-
efficiency. Thus, by results of the lead experiments carried out by us, it is estab-
lished that all nonlinear (polynom, not polynom, and mixed) models have shown
approximately equal efficiency; however, the most adequate should be counted the
as parabolic nonlinear model, allowed to reach the maximal value of factor of de-
termination 0.236597:

Pb_v = 194,78 + 14809,24 ⋅ Pb_vod - 1,11 ⋅ Pb_p -

(2)
- 3627,04 ⋅ Pb_vod + 11,99 ⋅ Pb_p
Normalization of the Maintenance of Metals 103

On the basis of the received most adequate model, specifications of the mainte-
nance of lead in objects of an environment are established. The regional specifica-
tion of the maintenance of lead in hair makes 10 gramme.4. The normative mainte-
nance of lead established by us in ground makes 27.5 mg/kg.6
Thus, the equation for definition of the maximal marginal level of the mainte-
nance of lead in potable water becomes:

10 = 194,78+14809,24 ⋅ Pb_vod -1,11⋅ 27,5-

(3)
-3627,04 ⋅ Pb_vod +11,99 ⋅ 27,5
The decision of the given equation is received numerically. To the decision, it
was applied two-step algorithm of definition of intervals by a graphic method and
specifications of roots by a method of Bolzano. In result, two valid positive roots
are received:

Pb_vod1 = 0.0110 mg / liter, Pb_vod2 = 0.0200 mg / liter

Thus, according to model (2), the maintenance of lead in drinking water should
not exceed value of 0.02 mg/liter provided that lead also acts in an organism and
airway. Further, the maintenance of iron in an organism of the person (hair) was
investigated at air (a snow cover) and water (potable water) ways of receipt to an
organism.
For check of a hypothesis about absence of linear connection between the main-
tenance of iron in hair and its maintenance in potable water and a snow (about zero
values of factors of regress) Fisher’s F-statistics was used. Value of F-statistics =
0.65641 at a significance value p < 0.52535, that is, a hypothesis about absence of
linear connection deviates.
We applied linear regress model of dependence of the maintenance of iron in
hair from the maintenance of iron in a snow cover and potable water (on a method
of the least squares):

Fe_v=189,401 + 1.275.608*Fe_vod + 437.879*Fe_s/l (3-a)

Factor of plural correlation R = 0.195; factor of determination R2=0.04 (4% of an

explained dispersion). The resulted factors of regress: Fe_vod = 0.04; Fe_s/l = 0.2.
Thus, direct influence of the maintenance of iron in atmospheric air (determined
under the analysis of tests of a snow cover) on accumulation of iron in hair of chil-
dren is revealed. The degree of influence of variability of the maintenance of iron in
a snow cover is five times stronger than in potable water. Small values of factors of
plural correlation and determination speak about small efficiency of model. In this
connection, there is a task of construction nonlinear plural regress models. A series
of experiments on modeling nonlinear regress models of dependence has been car-
104 Process Advancement in Chemistry and Chemical Engineering Research

ried out: Iron in hair (Iron in potable water - Iron in a snow cover). Summary results
are shown in Table 8.2.

TABLE 8.2  Results of Modeling for Iron.

The name of model Model Factor of determinations

Square-law Z=12,48+110,2*X+15,3*Y−688,58*X 0.071

2
−6,64*Y2
Cubic Z = 1 5 , 3 7 + 3 7 , 3 1 * X + 1 1 , 6 5 * Y- 0.073
2001,18*X3 −2,84*Y3
A polynom fourth Z = - 6 0 , 8 + 3 1 5 2 , 7 * X − 5 , 3 * Y- 0.157
31948,7*X2+838375,7*X4
+18,4*Y2−5,6*Y4

A polynom of the Z=−26+1295*X+0*Y−152968*X3+68 0.162

fifth degree 12171*X5
+14*Y3−5*Y5
Parabolic Z = - 1 2 , 5 3 1 − 3 1 0 * X - 0.064
8,685*Y+175,990* X +21,004*
Y
Logarithmic Z=72,832−167,392*X−0,997*Y+13,4 0.061
*ln(X)+
+3,1*ln(Y)
Indicative Z=1298+1384*X+18,73*Y−1279*eX− 0.073
5,76*eY

Hyperbolic Z=36,96−92,36*X+2,41*Y−0,57 0.059

1 −0,41 1Y
X
Polynom-arabolic Z=−359,94−8176*X+35,93*Y+91 0.148
model of the third 118*X3
degree
−6,18*Y3+3512* X

−28,95* Y
Polynom-parabol- Z=−242−4772*X+25*Y 0.156
ic model of the +2624639*X5−2*Y5
fifth degree
+2262* X −20* Y
Normalization of the Maintenance of Metals 105

TABLE 8.2  (Continued)

The name of model Model Factor of determinations

Polynom-Logarith- Z=528−2352*X 0.154

mic model +16*Y+2294509*X5
−1*Y5+132*ln(X) −3*ln(Y)

Polynom-Hyperbol- Z=166,2−1395,6*X 0.147

ic model +12,7*Y+276475,7*X4

−2,3*Y4−4,0* 1 X +0,3* 1Y

Designations: Z—the Maintenance of iron in hair (Fe_v); Х—the Maintenance of iron in

potable water (Fe_vod); Y—the Maintenance of iron in a snow cover (Fe_s/l).

Polynom models have allowed the increasing factor of determination up to four

times in comparison with linear regress model. The most effective should recognize
model “a polynom of the fifth degree” with factor of plural correlation 0.402374 and
factor of determination 0.161905. Also, it is possible to note that everything, except
for square-law, polynom models appeared effective (mattered F-statistics above a
significance value) at presence of zero factors in structure of a polynom (for cubic
model—square-law factors; for a polynom of the fourth degree—cubic; for a poly-
nom of the fifth degree—cubic and the fourth degree).
The mixed models containing three and more various elementary function in
structure, mattered F-statistics of less significance value that speaks about their no-
torious inefficiency. All nonlinear mixed models have similar characteristics (factor
of plural correlation at a level 0.38–0.4 and factor of determination at level 0.14–
0.16). The most effective model of regress is the polynom–parabolic model of the
fifth degree with factor of determination 0.156. However, the maximal plural cor-
relation and as consequence, determination, provides polynom model of the fifth
degree, which should be used for normalization of the maintenance of iron in objects
of an environment.
Based on results of the lead experiments of the most effective appeared nonlin-
ear mixed polynom model of regress of a kind:

Fe_v = −26 + 1295* Fe_vod − 15968* Fe_vod 3 +

(4)
+ 6,812,171* Fe_vod 5 + 14* Fe_s/l3 − 5* Fe_s/l5
With factor of determination 0.16. The model can be recommended to use with
a view of normalization of the maintenance of iron in an environment.
106 Process Advancement in Chemistry and Chemical Engineering Research

The regional specification of the maintenance of iron in hair makes 55 mkg/

gramme4. The normative maintenance of iron received by us earlier in potable water
makes 0.56 mg/liter.6.
Thus, the equation for definition of the maximal marginal level of the mainte-
nance of iron in a snow cover becomes:

55 = −26 + 1295*0.56 + 152,968*0.563 + 6,812,171*0.565

(5)
+ 14* Fe_s/l3 − 5* Fe_s/l5
The equation was solved numerically in two stages on the basis of transfor-
mation of the eq 5 to a task of minimization of square-law function: definition of
intervals of a presence of roots by a graphic method, and specification of roots by a
method of Bolzano. In result, the unique root of the eq 5 is received:

Fe_s/l = 9357 mg/liter.

Hence, according to model (4), the maintenance of iron in a snow cover should
not exceed value of 9357 mg/liter provided that iron also acts in an organism with
potable water. High value of the received parameter can be interpreted as weak in-
fluence of the maintenance of iron in a snow cover on its accumulation in hair. The
same position is illustrated with absolute values of the resulted factors of regress for
polynom–parabolic model: Fe_vod = 394,778; Fe_s/l = 001,735.
It is obvious, that influence of receipt of iron by a waterway on its accumulation
in hair more than in 200 times is higher than influence of the maintenance of iron
in a snow cover.
Further variability, the maintenance of copper in an organism, the person (hair)
was investigated at air (a snow cover) and waterways (potable water) of receipt to
an organism. For check of a hypothesis about absence of linear connection between
the maintenance of copper in hair and its maintenance in potable water and a snow
(about zero values of factors of regress) Fisher’s F-statistics was used. Value of F-
statistics = 19,197 at a significance value p < 0.15821, that is, a hypothesis about
absence of linear connection deviates. It has been received linear regress model of
dependence of the maintenance of copper in hair from the maintenance of copper in
a snow cover and potable water (on a method of the least squares).

Cu_v = 1985–440,827*Cu_vod + 1,32*Cu_s/l (6)

Factor of plural correlation R = 0.277555; factor of determination R2=0.077037

(about 8% of an explained dispersion); the resulted factors of regress:

Cu_vod = −0.274142; Cu_s/l = 0.0178092.

Thus, we establish direct influence of receipt of copper by airway on accumula-

tion of copper in hair of children. A degree of influence of variability of the main-
Normalization of the Maintenance of Metals 107

tenance of copper in potable water on the maintenance of copper in hair negative.

Also, small values of factors of plural correlation and determination speak about
small efficiency of model. In this connection, there is a task of constructing non-
linear plural regress models. A series of experiments on modeling nonlinear regress
models of dependence Copper in hair (Copper in potable water - Copper in a snow
cover) has been lead. Summary results are resulted in Table 8.2 (Z: the maintenance
of copper in hair (Cu_v); Х: the maintenance of copper in potable water (Cu_vod);
Y: the Maintenance of copper in a snow cover (Cu_s/l)). Summary results are re-
sulted in Table 8.3.

TABLE 8.3  Results of Modeling for Copper.

The name of model Model Factor of deter-

minations

Square-law Z=8+12060*X−26*Y−4946586*X2−77*Y2 0.116

Cubic Z=12+3488*X−18*Y−910344854*X 3
0.123
+144*Y3

A polynom fourth Z=−45,673+96010,14*X+75,66*Y−4,22E+0 0.177

7*X2+1,97E+12*X4−69,02*Y2+2186,72*Y4

A polynom of the fifth Z=−38,4+80317,82*X+ +65,05*Y−3,21E+0 0.177

degree 7*X2+4,68E+14*X5−465,13*Y2+3985,8*Y5

Parabolic 0.121
Z=−32,3−29878,5*X−70*Y++2236,2* X
+29,8* Y

Logarithmic Z=203,3−17162,8*X−43,1*Y 0.128

+55,6*log(X)+4,2*log(Y)

Indicative Z=870,8−851*10X- 0.077

−4,639*10 Y

Hyperbolic 0.130
Z=43,63−10281*X−26,54*Y−0,02 1 X
1
−0,03047 Y

Polynom – Logarithmic Z=382−32395*X 0.205

model of the fourth de- −141*Y +1,015+11*X4
gree
+8724*Y4 +105*log(X)
+11,72*log(Y)
108 Process Advancement in Chemistry and Chemical Engineering Research

TABLE 8.3  (Continued)

The name of model Model Factor of deter-

minations

Polynom – Logarith- Z=389,380286 0.212

mic model of the fifth −32889*X−126*Y
degree
+4,01E+13*X5
+39131*Y5+108*log(X)+10,9*log(Y)

Polynom – Hyperbolic Z=49,29−11170*X 0.174

model −57,59*Y−4,7E+12*X5
1
−0,024*Y5 −0,024* X
1
−0,024* Y

Polynom -parabolic Z=-99,80 −72106*X 0.226

model −261,60*Y+6,49E+13*X 5

+49416,88*Y5+5434,97* X +106,46* Y

Polynom models have allowed to increase factor of determination by the order

in comparison with linear regress model. The most effective should recognize model
“a polynom of the fourth degree “ with factor of plural correlation 0.421484 and
factor of determination 0.177648. Also, it is possible to note that everything except
for square-law, polynom models appeared effective (mattered F-statistics above a
significance value) at presence of zero factors in structure of a polynom (for cubic
model - square-law factors; for a polynom of the fourth degree - cubic; for a poly-
nom of the fifth degree - cubic and the fourth degree).
However, the received values, nevertheless, are insufficient for the recommen-
dation polynom models to practical application. Unfortunately, polynom regress
models have not allowed factor of determination to increase. Therefore, was ac-
cepted decision to build mixed nonlinear regress models. In Table 8.3 models, which
factor of determination has exceeded factor of determination polynom models of the
fourth degree (0.177) are resulted only.
The mixed models containing three and more various elementary function in
structure, mattered F-statistics of less significance value that speaks about their no-
torious inefficiency. All 4 nonlinear mixed models have similar characteristics (fac-
tor of plural correlation at a level 0.41–0.47 and factor of determination at a level
0.17–0.23). The most effective model of regress is the polynom–parabolic model.
This model can be recommended for practical application.
Normalization of the Maintenance of Metals 109

By results of the lead experiments of the most effective, there was a nonlinear
mixed polynom–parabolic model of regress of a kind:

Cu _ v = −99,81 − 72106, 43* Cu _ vod − 261, 60* Cu _ s / l +
+ (6,5 E + 13) * Cu _ vod 5 + 49416,9* Cu _ s / l 5 +
+ 5434,97 * Cu _ vod + 106,5* Cu _ s / l (6-a)

With factors of determination 0.226555. The model can be recommended to use

with a view of normalization of the maintenance of copper in an environment.
The regional specification of the maintenance of copper in hair has made 25
mkg/gramme.4 The normative maintenance (contents) of copper in the snow cover,
determined by us, has made 0.154 mg/liter.6
Thus, the equation for definition of the normative maintenance of copper in a
snow cover becomes:

25 = −99,81 − 72106, 43* Cu _ vod − 261, 60*0,154 +

+ (6,5 E + 13) * Cu _ vod 5 + 49416,9*0,1545 +
+ 5434,97 * Cu _ vod + 106,5* 0,154 (7)

The equation was solved numerically in two stages on the basis of transfor-
mation of the eq 7 to a task of minimization of square-law function: definition of
intervals of a presence of roots by a graphic method, and specification of roots by
a method of Bolzano. In result, the unique root of the eq 7 is received: Cu_vod =
0.314 mg/liter.
Hence, according to model (7), the maintenance of copper in potable water
should not exceed value of 0.314 mg/liter provided that copper also acts in an or-
ganism and air way.

8.3 CONCLUSION
Thus, we establish quantitative characteristics of distribution of metals in the con-
nected environments and scientifically proved specifications of the maintenance of
metals in objects of the environment, taking into account joint receipt of metals in
an organism of the person air and are received by a waterway.
110 Process Advancement in Chemistry and Chemical Engineering Research

KEYWORDS

•• multivariate regress nonlinear models

•• metals
•• normalization
•• organism
•• person
•• complex
•• environment
•• objects

REFERENCES
1. Levich, A. P.; Bulgakov, N. G.; Maxims, C. N. Theoretical and Methodical Bases of Technol-
ogy of the Regional Control of the Natural Environment According to Ecological Monitoring;
РЭФИА: Moscow, RU, 2004; p 271.
2. Maximov, V. N.; Bulgakov, N. G.; and Levich, A. P. Environmental Indices: Systems Analysis
Approach; EOL SS Publishers: London, UK, 1999; pp 363–381.
3. Р 2.1.10.1920-04 Management according to risk for health of the population at influence of
the chemical substances polluting an environment.
4. Maltsev, S. V.; Valiev, V. S.; Zingareeva, G. G.; Valiev, В. С.; Ganeeva, L. A. 1 International
Symposium “Modern problems of geochemical ecology of illnesses” materials. The first in-
ternational symposium (Cheboksary, 17-20 сент. 2001) Cheboksary, 2001. With. 71.
5. Rocky, A. V. Chemical Element in Physiology and Ecologies of Person, the World, 2004, 215
with.
6. Tunakova, J. A.; Fajzullina, R. A.; Shmakov, J. U. Magazine of the Kazan Technological
University 2012, 16 (12) 71–73.
CHAPTER 9

INFLUENCE OF HYDROLYSIS ON
DIFFUSION OFELECTROLYTES
A. C. F. RIBEIRO1*, L. M. P. VERÍSSIMO1, A. J. M. VALENTE1,
A. M. T. D. P. V. CABRAL2, and V. M. M. LOBO1
1
Department of Chemistry, University of Coimbra, 3004–535 Coimbra, Portugal;
Tel: +351-239-854460; fax: +351-239-827703;
*e-mail (corresponding author): [email protected];
[email protected]; [email protected]; [email protected]
2
Faculty of Pharmacy, University of Coimbra, 3000-295 Coimbra, Portugal;
E-mail: [email protected]

CONTENTS
Abstract..................................................................................................................112
9.1 Theoretical Aspects......................................................................................112
9.2 Experimental Aspects ..................................................................................114
9.3 Experimental Results and Discussion..........................................................116
9.4 Conclusion...................................................................................................117
Acknowledgment...................................................................................................117
Keywords...............................................................................................................118
References..............................................................................................................118
112 Process Advancement in Chemistry and Chemical Engineering Research

ABSTRACT
The experimental mutual diffusion coefficients of potassium chloride, magnesium
nitrate, cobalt chloride, and beryllium sulfate in aqueous solutions have been com-
pared with those estimated by Onsager and Fuoss.From the observed deviations, we
are proposing a model that allows to estimate thepercentage of H3O+ (aq) resulting
inhydrolysis of some ions (i.e., beryllium, cobalt, potassium, and magnesium ions),
contributing in this way to a better knowledge of the structure of these systems.
The diffusion of beryllium sulfate is clearlymost affected by the beryllium ion
hydrolysis.

9.1  THEORETICAL ASPECTS

9.1.1  CONCEPTS OF DIFFUSION

Diffusion data of electrolytes in aqueous solutions are of great interest not only
for fundamental purposes (providing a detailed comprehensive information—both
kinetic and thermodynamic), but also for many technical fields such as corrosion
studies.1–3The gradient of chemical potential in the solution is the force producing
the irreversible process which we call diffusion.1–3However, in most solutions, that
force may be attributed to the gradient of the concentration at constant temperature.
Thus, the diffusion coefficient, D, in a binary system, may be defined in terms of
the concentration gradient by a phenomenological relationship known as Fick’s first
law,

J = − D gradc (1.1)

or, considering only one dimension for practical reasons,

∂c
J = −D
∂x (1.2)

where J represents the flow of matter across a suitable chosen reference plane per
unit area and per unittime, in a one-dimensional system, and c is the concentration
of solute in moles per volume unit at the point considered; eq 1.1 may be used to
measure D. The diffusion coefficientmay also be measured by considering Fick’s
second law, in one-dimensional system,

∂c ∂  ∂c 
=  D  (1.3)
∂t ∂x  ∂x 
Influence of Hydrolysis on Diffusion Ofelectrolytes 113

In general, the available methods are grouped into two groups: steady and un-
steady-state methods, according to eqs1.2 and 1.3. Diffusion is a three-dimensional
phenomenon, but many of the experimental methods used to analyze diffusion re-
strict it to a one-dimensional process.1–4
The resolution of eq1.2 is much easier if we consider D as a constant. This ap-
proximation is applicable only when there are small differences of concentration,
which is the case in our open-ended conductometric technique,3,5 and in the Taylor
technique.3,6,7 In these conditions, it is legitimate to consider that our measurements
of differential diffusion coefficients obtained by the above techniques are param-
eters with a well-defined thermodynamic meaning.3–7

9.1.2  EFFECT OF THE HYDROLYSIS ON DIFFUSION OF

ELECTROLYTES IN AQUEOUS SOLUTIONS
A theory of mutual diffusion of electrolytes in aqueous solutions capable of ac-
curately predicting diffusion coefficients has not yet been successfully devel-
oped, due to the complex nature of these systems. However, Onsager and Fuoss
(eq1.4)8hasallowed the estimation of diffusion coefficients with a good approxima-
tion for dilute solutions and symmetrical electrolytes of the type 1:1. This equation
may be expressed by


D = 1 + c

∂ln y ±  0
∂c 
( )
D + ∑ D n (1.4)

where D is the mutual diffusion coefficient of the electrolyte, the first term in paren-
thesis is the activity factor, y is the mean molar activity coefficient, c is the con-
±
centration in moldm−3, D0 is the Nernst limiting value of the diffusion coefficient
(eq1.4), and D n are the electrophoretic terms given by

(z t + z n2t10 )
n 0 2
1 2
D n = kBTAn
z z an
1 2
(1.5)

where kB is the Boltzmann’s constant; T is the absolute temperature; An are func-

tions of the dielectric constant, of the solvent viscosity, of the temperature, and of
the dimensionless concentration-dependent quantity (ka), k being the reciprocal of
average radius of the ionic atmosphere; t10 and t20 are the limiting transport numbers
of the cation and anion, respectively.
Since the expression for the electrophoretic effect has been derived on the basis
of the expansion of the exponential Boltzmann function, because that function is
consistent with the Poisson equation, we only would have to take the electrophoretic
114 Process Advancement in Chemistry and Chemical Engineering Research

term of the first and the second order (n = 1 and n = 2) into account. Thus, the ex-
perimental data Dexp can be compared with the calculated DOF on the basis of eq1.6

 ∂ln y ±  0
D = 1 + c
 ∂c 
(
D + D1 + D 2 (1.6) )
A good agreement between the observedvalues and those calculatedby eq1.6for
potassium chloride9 and magnesium nitrate10 was observed and reported in the
literature,but for cobalt chloride11 and beryllium sulfate,12 they are definitely higher
than theory predicts. This is not surprising if we take into account the change with
concentration of parameters, such as viscosity, hydration, and hydrolysis, factors not
taken into account in Onsager–Fuoss model.8 In fact, those differences may possibly
be due to hydrolysis of the cations (eq 1.7),13–15 which would be more pronounce-
din cobalt chloride and beryllium sulfate than potassium chloride and magnesium
nitrate.

←
M(H 2 O) nx + (aq) → M(H 2 O) x − 1 (OH)( n − 1) + (aq) + H + (aq) (1.7)

We areproposing a model in order to allow the estimation of the amount of ion

H+(aq) produced in each of the systems studied usingexperimental diffusion coef-
ficients determined by our conductometric method and the respective predictive by
that theory.
That is, having in mind the acidic character of some cations,14,15 the percentag-
esof ion H+(aq) produced (or the amount of acid that would be necessary to add a
given electrolyte solution in the absence of hydrolysis in order to simulate a more
real system) are determined by the following system (eqs1.8 and 1.9),

Dacidz + Delectrolyte y = Dexp, (1.8)

z + y = 1 (1.9)
where z× 100 and y × 100 are the percentages of acid and electrolyte, respectively,
and Dexp is the valueof the diffusion coefficients of electrolytes in aqueous solutions,
and Dacid and Delectrolyte are the Onsager and Fuoss values of the diffusion coefficients
for the acids and electrolytes, respectively, in aqueous solutions.

9.2  EXPERIMENTAL ASPECTS

CONDUCTOMETRIC TECHNIQUE
An open-ended capillary cell (Fig. 9.1),5 which has been used to obtain mutual dif-
fusion coefficients for a wide variety of electrolytes,5,9–13,16–19 has been described
Influence of Hydrolysis on Diffusion Ofelectrolytes 115

in great detail5. Basically, it consists of two vertical capillaries, each closed at one
end by a platinum electrode, and positioned one above the other with the open ends
separated by a distance of about 14 mm. The upper and lower tubes, initially filled
with solutions of concentrations 0.75 and 1.25 c, respectively, are surrounded with a
solution of concentration c. This ambient solution is contained in a glass tank (200
× 140 × 60 mm) immersed in a thermostat bath at 25°C. Perspex sheets divide the
tank internally and a glass stirrer creates a slow lateral flow of ambient solution
across the open ends of the capillaries. The experimental conditions are such that the
concentration at each of the open ends is equal to the ambient solution value c, that
is, the physical length of the capillary tube coincides with the diffusion path. This
means that the required boundary conditions described in the literature5 to solve
Fick’s second law of diffusion are applicable. Therefore, the so-called Dl effect5 is
reduced to negligible proportions. In our manually operated apparatus, diffusion is
followed by measuring the ratio w=Rt/Rb of resistances Rt and Rb of the upper and
lower tubes by an alternating current transformer bridge. In our automatic appara-
tus, w is measured by a Solartron digital voltmeter (DVM) 7061 with 6 1/2 digits. A
power source (Bradley Electronic Model 232) supplies a 30 V sinusoidal signal at 4
kHz (stable to within 0.1 mV) to a potential divider that applies a 250 mV signal to
the platinum electrodes in the top and bottom capillaries. By measuring the voltages
Vʹ and Vʺ from top and bottom electrodes to a central electrode at ground potential
in a fraction of a second, the DVM calculates w.

FIGURE 9.1  TS, BS: support capillaries; TC, BC: top and bottom diffusion capillaries;
CE: central electrode; PT: platinum electrodes; D1, D2: perspex sheets; S: glass stirrer; P:
perspex block; G1, G2: perforations in perspex sheets; A, B: sections of the tank; L1, L2:
small diameter coaxial leads.5
116 Process Advancement in Chemistry and Chemical Engineering Research

In order to measure the differential diffusion coefficient D at a given concen-

tration c, the bulk solution of concentration c is prepared by mixing 1 L of “top”
solution with 1 L of “bottom” solution, accurately measured. The glass tank and the
two capillaries are filled with c solution, immersed in the thermostat, and allowed
to come to thermal equilibrium. The resistance ratio w = w∞ measured under these
conditions (with solutions in both capillaries at concentration c accurately gives the
quantity τ∞ = 104/(1 +w∞).
The capillaries are filled with the “top” and “bottom” solutions, which are then
allowed to diffuse into the “bulk” solution. Resistance ratio readings are taken at
various recorded times, beginning 1000 min after the start of the experiment, to
determine the quantity τ = 104/(1+w) asτ approaches τ∞. The diffusion coefficient
is evaluated using a linear least-squares procedure to fit the data and, finally, an
iterative process is applied using 20 terms of the expansion series of Fick’s second
law for the present boundary conditions. The theory developed for the cell has been
described previously.5
Interdiffusion coefficients of potassium chloride,9 magnesium nitrate,10 cobalt
chloride,11 and beryllium sulfate12 in water at 298.15 K and at concentrations from
0.001 to 0.01 mol dm−3 have been measured using a conductometric cell and an au-
tomatic apparatus to follow diffusion. The cell uses an open-ended capillary method
and a conductometric technique is used to follow the diffusion process by measuring
the resistance of a solution inside the capillaries at recorded times.

9.3  EXPERIMENTAL RESULTS AND DISCUSSION

Table 9.1 shows the estimatedpercentage of hydrogen ions, z, resulting from the
hydrolysis of different ions at different concentrationsat 298.15 K by using the eqs
1.8–1.9.

TABLE 9.1  Estimated Percentage of Hydrogen Ions, z, Resulting From the Hydrolysis of
Some Cations in Aqueous Solutions at Different Concentrations,c, and at 298.15 KUsing Eqs
1.8 and 1.9.
c/ z% z% z% z%
moldm−3 (KCl) (Mg(NO3)2) (CoCl2) (BeSO4)
1 × 10−3 2 – 5 –
3 × 10−3 3 1 6 69
5 × 10−3 2 2 8 48

8 × 10−3 3 1 6 26
3 1 6 34
1 × 10−2
Influence of Hydrolysis on Diffusion Ofelectrolytes 117

From theanalysis of this table, we see that the diffusion of cobalt ion and mainly
berylliumion arethe most clearly affected bytheir hydrolysis. At the lowest Be2+ion
concentration (3 × 10−3 mol dm−3), the effect of the hydrogen ions on the whole
diffusion process has an important and main role(z = 69%, Table 9.1). However, we
can, toa good approximation, describe thesesystemsas binaryif we considercertain-
facts. For example, in the case of solutions ofberylliumsulfate, several studies12in-
dicated thatthe predominant species present arethe solvent,Be2+, SO42−,and H+ions, as
well as indicatedin the following schemeresulting fromhydrolysis of theBe2+ion.

[Be(H2O)4]2+ ↔[Be(H2O)3(OH)]−+ H+
[Be(H2O)3(OH)]−+ [Be(H2O)4]2+ ↔ [(H2O)3 Be–OH–Be (H2O)3]3+

However, based on pH measurements (i.e., 2.9 ≤ pH ≤3.9) for various BeSO4so-

lutions at concentrations ranging from 3 × 10−3to1× 10−2 mol dm−3, and from the low
equilibrium constantsrelative to the hydrolysis of theBe2+ion,15 we can then treat this
system as being a binary system. Moreover, given the uniformity of the concentra-
tion gradient imposed by our method, it is considered that the value of the diffusion
coefficient, which is given to the scientific community, is a quantitative measure of
all existing species that diffuse.
Concerning the other electrolytes (KCl and Mg(NO3)2),9,10 the reasonable agree-
ment obtained between the calculated and the experimental values of diffusion coef-
ficient, should result in negligible percentages for the hydronium ion (Table 9.1).

9.4 CONCLUSION

We have estimated thepercentage of H3O+ (aq) resulting from the hydrolysis

of some ions (i.e., beryllium, cobalt, potassium, and magnesium ions), using a new
model and the experimental and calculated mutual diffusion coefficients for potas-
sium chloride, magnesium nitrate, cobalt chloride, and beryllium sulfate in aqueous
solutions, contributing in this way for a better knowledge of the structure of these
systems.
Among the cited systems, we concluded that the diffusion of beryllium sulfate is
clearly the most affected by the beryllium ion hydrolysis.

ACKNOWLEDGMENT
Financial support of the Coimbra Chemistry Centre from the FCT through project
Pest-OE/QUI/UI0313/2014 is gratefully acknowledged.
118 Process Advancement in Chemistry and Chemical Engineering Research

KEYWORDS

•• diffusion coefficients
•• aqueous solutions
•• electrolytes
•• hydration

REFERENCES
1. Robinson, R.A.; Stokes, R.H. Electrolyte Solutions; 2nd ed., Butterworths: London, 1959.
2. Harned, H.S.; Owen, B.B. The Physical Chemistry of Electrolytic Solutions; 3rd ed., Reinhold
Pub. Corp.: New York, 1964.
3. Tyrrell, H.J.V.; Harris, K.R. Diffusion in Liquids: A Theoretical and Experimental Study; But-
terworths: London, 1984.
4. Lobo, V.M.M. Handbook of Electrolyte Solutions; Elsevier: Amsterdam, 1990.
5. Agar, J.N.; Lobo, V.M.M. Measurement of Diffusion Coefficients of Electrolytes by a Modi-
fied Open-Ended Capillary Method.J. Chem. Soc.Faraday Trans.1975;71, 1659–1666.
6. Callendar, R.; Leaist, D.G. Diffusion Coefficients for Binary, Ternary, and Polydisperse Solu-
tions from Peak-Width Analysis of Taylor Dispersion Profiles.J. Sol. Chem. 2006;35, 353–
379.
7. Barthel, J.; Feuerlein, F.; Neuder, R.; Wachter, R. Calibration of Conductance Cells at Various
Temperatures. J. Sol. Chem.1980;9, 209–212 .
8. Onsager, L.; Fuoss, R.M. Irreversible Processes in Electrolytes. Diffusion. Conductance and
Viscous Flow in Arbitrary Mixtures of Strong Electrolytes. J. Phys. Chem.1932;36, 2689–
2778.
9. Lobo, V.M.M.; Ribeiro, A.C.F.; Verissimo, L.M.P. Diffusion Coefficients in Aqueous Solu-
tions of Potassium Chloride at High and Low Concentrations. J.Mol.Liq. 2001;94, 61–66.
10. Lobo, V.M.M.; Ribeiro, A.C.F.; Veríssimo, L.M.P. Diffusion Coefficients in Aqueous Solu-
tions of Magnesium Nitrate. Ber. Bunsen Gesells. Phys. Chem. Chem. Phys.1994;98, 205–
208.
11. Ribeiro, A.C.F.; Lobo,V.M.M.; Natividade, J.J.S. Diffusion Coefficients in Aqueous Solutions
of Cobalt Chloride at 298.15 K. J. Chem. Eng. Data 2002;47, 539–541.
12. Lobo, V.M.M.; Ribeiro, A.C.F.; Veríssimo, L.M.P. Diffusion Coefficients in Aqueous Solu-
tions of Beryllium Sulphate at 298 K. J. Chem. Eng. Data 1994;39, 726–728.
13. Valente, A.J.M.; Ribeiro, A.C.F.; Lobo, V.M.M.; Jiménez A. Diffusion Coefficients of Lead(II)
Nitrate in Nitric Acid Aqueous Solutions at 298.15 K. J. Mol. Liq. 2004;111, 33–38.
14. Baes, C.F.; Mesmer, R.E. The Hydrolysis of Cations; John Wiley & Sons: NewYork, 1976.
15. Burgess, J. Metal Ions in Solution; John Wiley & Sons, Chichester, Sussex: England, 1978.
16. Ribeiro, A.C.F.; Lobo, V.M.M.; Oliveira, L.R.C.; Burrows, H.D.; Azevedo, E.F.G.; Fangaia,
S.I.G.; Nicolau, P.M.G.; Fernando, A.D.R.A. Diffusion Coefficients of Chromium Chloride in
Aqueous Solutions at 298.15 and 303.15 K. J. Chem. Eng. Data 2005;50, 1014–1017.
17. Ribeiro, A.C.F.; Esteso, M.A.; Lobo,V.M.M.; Valente, A.J.M.; Sobral, A.J.F.N.; Burrows,
H.D. Diffusion Coefficients of Aluminium Chloride in Aqueous Solutions at 298.15 K, 303.15
K and 310.15 K. Electrochim. Acta. 2007,52, 6450–6455.
18. Veríssimo, A.L.M.P.; Ribeiro, A.C.F.; Lobo, V.M.M.; Esteso, M.A. Effect of Hydrolysis on
Diffusion of Ferric Sulphate in Aqueous Solutions. J. Chem. Thermodyn.2012;55, 56–59.
Influence of Hydrolysis on Diffusion Ofelectrolytes 119

19. Ribeiro, A. A.C.F.; Gomes, J.C.S.; Veríssimo, L.M.P.; Romero L.H. Blanco, C.; Esteso, M.A.
Diffusion of Cadmium Chloride in Aqueous Solutions at Physiological Temperature 310.15 K.
J. Chem.Thermodyn.2013;57, 404–407.
CHAPTER 10

OZONE DECOMPOSITION
T. BATAKLIEV, V. GEORGIEV, M. ANACHKOV, S. RAKOVSKY, and
G.E. ZAIKOV*
Institute of Catalysis, Bulgarian Academy of Sciences, Bonchev St. #11, Sofia 1113,
Bulgaria
*N. M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, 4,
Kosigina St., Moscow119334, Russian Federation

CONTENTS
Abstract..................................................................................................................122
10.1 Introduction.................................................................................................122
10.2  Some Physicochemical Properties of Ozone..............................................123
10.3  Ozone Synthesis and Analysis....................................................................125
10.4  Ozone Decomposition.................................................................................127
Keywords...............................................................................................................143
References..............................................................................................................143
122 Process Advancement in Chemistry and Chemical Engineering Research

ABSTRACT
Catalytic ozone decomposition is of great significance because ozone is toxic sub-
stance commonly found or generated in human environments (aircraft cabins, of-
fices with photocopiers, laser printers, sterilizers). Considerable work has been done
on ozone decomposition reported in the literature. This review provides a compre-
hensive summary of this literature, concentrating on analysis of the physicochemi-
cal properties, synthesis, and catalytic decomposition of the ozone. This is supple-
mented by review on kinetics and catalyst characterization, which ties together
the previously reported results. It has been found that noble metals and oxides of
transition metals are the most active substances for ozone decomposition. The high
price of precious metals stimulated the use of metal oxide catalyst and particularly
the catalysts based on manganese oxide. The kinetics of ozone decomposition has
been determined to be offirst order. A mechanism of the reaction of catalytic ozone
decomposition was discussed based on detailed spectroscopic investigations of the
catalytic surface, showing the existence of peroxide and superoxide surface inter-
mediates.

10.1 INTRODUCTION
In recent years, the scientific research in all leading countries of the world is aimed
primarily at solving the deep environmental problems on the planet, including air
pollution and global warming. One of the factors affecting these processes nega-
tively is the presence of ozone in ground atmospheric layers. This is a result of the
wide use of ozone in lot of important industrial processes such as cleaning of potable
water and soil, disinfection of plant and animal products, textile bleaching, complete
oxidation of waste gases from the production of various organic chemicals, steriliza-
tion of medical supplies, and so on.1
The history of ozone chemistry as a research field began immediately after its
discovery from Schönbein in 1840.2The atmospheric ozone is focused mainly on the
so-called “ozone layer” at a height of 15–30 km above the earth surface wherein the
ozone concentration ranges from 1 to 10 ppm.3 The ozone synthesis at that altitude
runs photochemically through the influence of solar radiation on molecular oxygen.
The atmospheric ozone is invaluable to all living organisms because it absorbs the
harmful ultraviolet radiation from the sun. The study of the kinetics and mechanism
of ozone reactions in modern science is closely related to solving the ozone holes
problem that reflect the trend of recent decades to the depletion of the atmospheric
ozone layer.
Ozone has oxidation, antibacteriological, and antiviral properties that make it
widely used in the treatment of natural, industrial, and polluted waters; swimming
pools; contaminated gases; for medical use; and so on. Catalytic decomposition of
Ozone Decomposition 123

residual ozone is imperative because from environmental point of view, the release
of ozone in the lower atmosphere has negative consequences.
The presence of ozone in the surrounding human environment (airplane cabins,
copiers, laser printers, sterilizers, etc.) also raises the issue of its catalytic decompo-
sition as ozone is highly toxic above concentrations of 0.1 mg/m34,5 and can damage
human health. The use of catalysts based on transition metal oxides are emerging as
very effective from an environmental perspective and at the same time practical and
inexpensive method applied in the decomposition of residual ozone.

10.2  SOME PHYSICOCHEMICAL PROPERTIES OF OZONE

Ozone is an allotropic modification of oxygen that can exist in all three physical
conditions. In normal conditions, ozone is colorless gas with a pungent odor while
at very low concentrations (up to 0.04 ppm) it can feel like a pleasant freshness. A
characteristic property of ozone odor is the fact that it is easily addictive and at the
same time hazardous for men who work with ozone in view of its high toxicity at
concentrations above the limit (>0.1 mg/m3).
When the ozone concentration is more than 15–20%, it has blue color. At at-
mospheric pressure and temperature of 161.3 K, the ozone becomes fluid in deep
blue color. It cures at 80.6 K by acquiring dark purple color.6Ozone is explosive in
all three physical conditions. The work with ozone concentrations of 0–15% can be
considered safe.4 The danger of ozone explosion is a function of its thermodynamic
instability (ΔG°298=−163 kJ/mol) and ozone decomposition to diatomic oxygen
is a thermodynamically favorable process with heat of reaction ΔH°298=−138 kJ/
mol.7 The ozone molecule consists of three oxygen atoms located at the vertices of
obtuse-angled triangle with a central angle of 116°8’±5’ and length of О–О-bond:
ρо–о = 0.1278±0.0003 nm (Fig. 10.1).

FIGURE 10.1  Structure of ozone molecule.

124 Process Advancement in Chemistry and Chemical Engineering Research

In gas phase, the ozone molecule is a singlet biradical while in liquid phase it
reacts generally as a dipolar ion. The homogeneous reaction of pure gaseous ozone
decomposition is characterized by certain velocity at sufficiently high tempera-
tures. The kinetics study of the ozone thermal decomposition is also complicated
by the fact that above a certain critical temperature, the steady kinetic decomposi-
tion is transformed into explosion, subsequently passing to detonation.1 According
to Thorpe,8 the detonation of ozone is observed above 105°C. The gaseous ozone
is characterized by different time of half-life depending on the temperature (Table
10.1):

TABLE 10.1  Half-Life of Ozone.

Temp. (°C) Half-life

−50 3 months

−35 18 days

−25 8 days

20 3 days

120 1.5h

250 1.5s

The ozone structure is resonance stabilized, which is one of the reasons for its
resistance against decomposition at low temperatures (Fig.10.2).

FIGURE 10.2  Resonance structures of ozone.

In most reactions of ozone with inorganic compounds, it reacts with partici-

pation of one oxygen atom and the other two are separated as O2. Typically, the
elements are oxidized to their highest oxidation states. For example, manganese is
oxidized to [MnO]4−, halogen oxides to metals (ClO2, Br2O5), ammoniato NH4NO3,
and nitrogen oxides pass into N2O5.9–11
Ozone has spectral characteristics from the IR-region to the vacuum UV-region,
which are present in a significant number of works, such as the majority of them are
Ozone Decomposition 125

carried out with gaseous ozone.12–18 It should be noted that most researchers, who
use the spectrophotometric method for analysis of ozone, work in the main area of
the spectrum 200–310 nm, where is the wide band with maximum at ~255 nm for
gaseous ozone.13,15–17 That maximum is characterized with high value of the coef-
ficient of extinction (Table 10.2):

TABLE 10.2  Coefficient of Extinction (ε, l.mol-1.cm-1) of Gaseous Ozone in UV-Region.19

λ, nm [35] [33] [36] [47] λ, nm [35] [33] [36]
253.6* 2981 3024 2952 3316 296.7** 150.5 153.4 156.8
270 – – – 2302 302.2 74.4 – 74.4
289.4 383 337.5 387.5 – 334.2 1.50 – 1.46
*The values of rare 1830 l.mol−1.cm−1at 254.0 nm4and3020 l.mol−1.cm−1 at 253.6 nm.14
** ε = 160 l.mol−1.cm−1 at 295 nm.18

10.3  OZONE SYNTHESIS AND ANALYSIS

Ozone for industrial aims is synthesized from pure oxygen by thermal, photochemi-
cal, chemical, and electrochemical methods, in all forms of electrical discharge and
under the action of a particles stream. 1The synthesis of ozone is carried out by the
following reactions shown in the scheme:

O2 + (e−, hν, T) → 2O (O2*) (1)

O2 + O + M ↔ O3 + M (2)

O2* + O2→ O3 + O (3)

where М is every third particle.

At low temperatures, the gas consists essentially of molecular oxygen and
at higher,by atomic oxygen. There is no area of temperatures at normal pressure
wherein the partial pressure of ozone is significant. The maximum steady-state pres-
sure, which is observed at temperature of 350 K, is only 9.10−7 bar. The values of
the equilibrium constant of reaction (2) at different temperatures are presented in
Table 10.3.20

TABLE 10.3  Equilibrium Constant (Ke) of Reaction (2) Depending on the Temperature.

Т, К 1500 2000 3000 4000 5000 6000

Ke, М 1662.10 −11
4413.10 −7
1264.10−2
2.104 48.37 382.9
126 Process Advancement in Chemistry and Chemical Engineering Research

At high temperatures, when the concentration of atomic oxygen is high, the

equilibrium of reaction (2) is moved to the left and the ozone concentration is low.
At low temperatures, the equilibrium is shifted to the right, but through the low con-
centration of atomic oxygen, the ozone content is negligible. For synthesis of signif-
icant concentrations of ozone, it is necessary to combine two following conditions:
(1) low temperature and (2) the formation of superequilibrium concentrations of
atomic oxygen.It is possible to synthesizeupper equilibrium atomic concentrations
of oxygen at low temperatures by using nonthermal processes, such as dissociation
of oxygen with particles flow, electrons, hν, electrochemical, and chemical influ-
ences.Ozone will always be formed at low temperatures, when there is a process
of oxygen dissociation. Higher concentrations of ozone may be obtained by ther-
mal methods providing storage (“quenching”) of superequilibrium concentrations
of atomic oxygen at low temperatures. Photochemical synthesis of ozone occurs
upon irradiation of gaseous or liquid oxygen by UV radiation with wavelength of
λ<210 nm.21 It is assumed22 that the formation of ozone in the presence of radiation
with wavelength in the range of 175<λ<210 may be associated with the formation
of excited oxygen molecules:

О2 + hν → (O2*) (4)

O2* + O2 → O3 + O (5)

O2 + O + M ↔ O3 + M (6)

The photochemical generation of ozone has an important role in atmospheric

processes, but it is hard to apply for industrial applicationbecause of the high energy
costs (32 kWh/kg ozone) for the preparation of high-energy shortwave radiation.
Nowadays, the industrial synthesis of ozone happens mainly by any of the electric
discharge methods by passing oxygen containing gas through high-voltage (8–10
kV) electrodes. The aim is creation of conditions in which oxygen is dissociated
into atoms. This is possible in all forms of electrical discharges: smoldering, silent,
crown, arc, barrier, and so on. The main reason for the dissociation is the hit of mo-
lecular oxygen with the acceleration in electric field electrons,1,6 when part of the
kinetic energy is transformed in energy of dissociation of the bond O–O and excita-
tion of oxygen molecules. In general, molecular oxygen dissociates in two oxygen
atoms, then on final stage, two molecules of oxygen form one oxygen atom and one
ozone molecule:

О2 + e → 2O (O2*) (7)

O2 + O + M → O3 + M (8)

O2* + O2 ↔ O3 + O (9)
Ozone Decomposition 127

Technically, the synthesis of ozone is carried out in discharge tubes—ozonators.

One of the most commonly used type ozonators are Siemens (Fig.10.3).

FIGURE 10.3  Principal scheme of ozonator Siemens.

This ozonator represents two brazed, one to another coaxial pipes with sup-
ported inside of the inner side and outside of the outer side electrically conductive
coating of aluminum, silver, copper, and the like.A high voltage up to 20 kV is sup-
plied to it, and dry and pure oxygen is left to pass through the ozonator. The ozone
is synthesized on the other end of the ozonator.The ozone concentration depends on
current parameters—voltage, frequency, and power, on the ozonator properties—
thickness, length, and type of glass tube;on distance between the electrodes; and it
alsodepends on temperature.
The analysis of the ozone concentration is developed by various physical and
chemical methods discussed in details in monograph.23 It should be noted the pref-
erence for the spectrophotometric method compared withthe iodometric method,
which is determined by the lack of need of continuouspH monitoring during the
ozone analysis and also by the possibility of direct observation of the inlet and outlet
ozone concentrationsin the system, allowing precisefixingof the experimental time
and its parameters.For determination of the ozone, amount can be used, not absolute
values of concentration but the ratios of the proportional values of optical densities,
which excludes the error influence atexpense of the inaccuracy in calibration of the
instrument.

10.4  OZONE DECOMPOSITION

The reaction of ozone on the surface of solids is of interest from different points of
view.Along with the known gas cycles depleting the atmospheric ozone, a definitive
role playsits decomposition on aerosols that quantity already is growing at expense
128 Process Advancement in Chemistry and Chemical Engineering Research

of the anthropogenic factor. The growth of ozone used in chemical industries set up
the task for decomposition of the residual ozone on heterogeneous, environmental
friendly catalysts.In humid environments and under certain temperatures and gas
flow rates, this subject has not been yet entirely understood.

10.4.1  STRATOSPHERIC OZONE

The importance of the stratospheric ozone is determined by its optical properties—
its ability to absorb the UV solar radiation with a wavelength of 220–300 nm. The
absorption spectrum of ozone in the ultraviolet and visible region is given in Figure
10.4.

FIGURE 10.4  UV-absorption spectrum of ozone with maximum at 254 nm.

The main absorption band in the name of Hartley is in the range 200–300 nm
with maximum at a wavelength of 254 nm. Stratospheric ozone layer has a thickness
of 3 mm and its ability to absorb UV rays protects the earth’s surface of biologically
active solar radiation, which destroys the most important biological components,
proteins, and nucleic acids.
The fundamentals of the photochemical theory of stratospheric ozone have been
made by the English chemist Chapman,24,25 according to whom the photochemical
decomposition of ozone occurs to the following reactions:

О3 + O → O2 + O2 (10)
Ozone Decomposition 129

O3 + hν → O2 + O (3P) (11)

O3 + hν → O2 + O (1D) (12)

The proposed mechanism leads to formation of oxygen atoms in ground and

excited state. This cycle of decomposition is called the cycle of “residual oxygen.”
The photodissociation of ozone (11, 12) takes place under the action of solar radia-
tion with wavelength less than 1134 nm. Decomposition of ozone following these
reactions (11, 12) can be observed at any altitude near to ground level. The photo-
chemical synthesis of ozone in the stratosphere requires its degradation in reaction
(10). It was found that 20% of the stratospheric ozone decomposes following this
reaction.26The effect of ozone layer on climate changes is related to the absorption
of radiation, which occurs not only in the UV-region, but also in the IR-region of
the spectrum. Absorbing IR rays from theEarth’s surface, ozone enhances the green-
house effect in the atmosphere.27,28The connection of this problem with climate is
extremely complicated due to the variety of physical and chemical factors that influ-
ence the amount of atmospheric ozone.29
The destruction of ozone in the atmosphere is linked to catalytic cycles of the
type:

X + O3 → XO + O2 X + O3 → XO + O2

XO + O → X + O2 XO + O3 → X + 2O2
O3 + O → O2 + O2 2O3 → 3O2

where: X is OH, NO, or Cl, formed by dissociation of freons in the atmosphere.30

The stratospheric cycles of ozone decomposition are discussed in a lot of works
but fundamental contributions have most26 and.31 The effective action of the mo-
lecularcatalysts in the cycles of ozone decomposition is determined by their con-
centrations in the atmosphere, which depends on the rates of regeneration and exit
from the respective cycle.32 The ratio between the rate of decomposition of residual
oxygen and the rate of catalyst outgoing from the cycle determines the length of the
chain reaction and corresponds to the number of O3 molecules destructed by one
catalytic molecule. The number of stages of ozone decomposition in a single cata-
lytic center can reach 106.1 The reduction of the ozone amount over Antarctica, that
is, the thinning of ozone layer is mainly due to the action of the chlorine cycle.33–35
During this catalytic cycle, the presence of one chlorine atom in the stratosphere can
cause the decomposition of 100,000 ozone molecules.

10.4.2  CATALYSTS FOR DECOMPOSITION OF OZONE

The use of ozone for industrial aims is related with the application of effective cata-
lysts for its decomposition, as it was already mentioned, the release of ozone in the
130 Process Advancement in Chemistry and Chemical Engineering Research

atmosphere near the ground level is dangerous and contaminates the air.1,36–37 The
ozone has a great number of advantages as oxidizing agent and, in that capacity, it
has been used in different scientific investigationswith neutralization of the organic
contaminants,38,39 asthe ozonation efficiency increases in presence of the catalyst.40,41
Due to its antibacterial and antiviral properties, ozone is one of most used agents
in water treatment.42 This facts result in considerable interest fromthe researchers in
study of homogeneous and heterogeneous reactions of ozone decomposition, as well
as in participationof ozone in multiple oxidation processes.

10.4.3  OZONE DECOMPOSITION ON THE SURFACE OF

METALS AND METAL OXIDES
The first studies on the catalytic decomposition of gaseous ozone43 showed that
the degradation of the ozone is accelerated in the presence of Pt, Pd, Ru, Cu, W,
and so on. Catalytic activity of metals in the decomposition of ozone is studied by
Kashtanov et al.,44 which highlight that the silver (Ag) show higher catalytic activity,
compared to copper (Cu), palladium (Pd), and tin (Sn). It should be noted,from ear-
lier works on decomposition of ozone, that the study of Schwab and Hartmann45has
investigated catalysts based on metals from I to IV group and their oxides in dif-
ferent oxidation levels, and found out that the catalytic activity of these oxides in-
creases with increase in the oxidation state of the metal. Below is presented the
relationship between the catalytic activity degree of a number of elements and their
oxides, in the reaction of the catalytic decomposition of ozone:

Cu<Cu2O<CuO; Ag<Ag2O<AgO; Ni<Ni2O3; Fe<Fe2O3; Au<Au2O3;

Pt<colloidal Pt
These results can be explained by the higher activity of the ions of the respec-
tive elements relative to the activity of the elements themselves, as well as the im-
portance of ionic charge in the catalytic reaction. Other earlier studies have been
presented in several articles by Emelyanov et al.,46–48 which discussed catalytic de-
composition of gaseous ozone at temperatures from −80 to +80°C and ozone con-
centration of 8.8 vol.%. For Catalysis,elements of the platinum group such as Pt,
colloidal Pt, Pd, Ir and colloidal Ru, NiO, and Ni2O3have been used. Experiments
have been carried out in a tube reactor at gas velocity of 5 l/h. Studies indicate
identical activity of the nickel oxide and colloidal platinum at temperatures from
20 to 80°C. At −80°C, the activity of the nickel oxide falls to zero, while the plati-
num remains active. This is related to the low activation energy of decomposition
of O3 on the metal surface (~1 kcal/mol). It was also found out that the process of
decomposition of the ozone in the presence of colloidal Rh and Ir at +3 and +20°C
slowed down after 4 h, and the catalysts lost its activity. Sudak and Volfson’s silver–
manganese catalyst49 for the decomposition of ozone was used at low temperatures
Ozone Decomposition 131

in different gas mixtures. Commercial reactors operating with this catalyst have a
long life of performance and maintain a constant catalytic activity. The preparation
of other high-performance metal catalyst for the decomposition of ozone, including
the development of special technology for synthesis, determination of the chemical
composition, the experimental conditions, and the catalytic activity have been noted
in a number of studies in Japanese authors published in the patent literature.50–60 The
main metals used are Pt, Pd, Rh, and Ce, as well as metals and metal oxides of Mn,
Co, Fe, Ni, Zn, Ag, and Cu. The high price of precious metals stimulates the use
of metal oxide catalyst supporters with a highly specific surface such as γ-Al2O3,
SiO2, TiO2, ZrO2, and charcoal. Hata et al.50 have synthesized a catalyst containing
2% Pt as active component on a supporter composed of a mixture of 5% SiO2 and
95% γ-Al2O3 having a specific surface area 120 m2/g. They have impregnated chlo-
roplatinic acid onto the carrier at 80°C then the sample has been dried successively
at 120 and 400°C and atmospheric pressure. At operating temperature of 20°C, gas
velocity of 20,000 h−1 and 10 ppm initial concentration of ozone in the fed gas, this
catalyst shows 95% catalytic activity. Another catalyst comprising TiO2, SiO2, and
Pt52 degrades 94, 97, and 99% of the ozone in the air stream at temperatures of 20,
50, and 100°C respectively. Therui et al.54 have deposited metals Mn, Co, Fe, Ni,
Zn, Ag, or their oxides in the weight ratio in regard to carrier in the range of 0–60%,
as well as Pt, Pd, and Rh of the 0–10 wt.%, and also mixed oxides such as TiO2–
SiO2; TiO2–ZrO2, and TiO2–SiO2–ZrO2, supported on colloidal polyurethane with
400 m2/g specific surface. The catalysts have been placed in tube reactors and their
catalytic activity measured in the decomposition of ozone at a concentration of 0.2
ppm has been 99%. In published patents,it may be noted that for catalysts with iden-
tical chemical composition various precursors and methods for synthesishave been
used. For example, TiO2 and MnO256 are obtained from aqueous solutions of H2SO4
+ TiOSO4 and Mn (NO3).6H2O, while in another case,57 TiO2 was purchased from
the manufacturer, and the MnO2 is prepared by precipitation of aqueous solutions of
MnSO4 and NH3 in an atmosphere of oxygen followed by calcination. The applica-
tion of the proposed system conditions makes it possible to assess the effectiveness
of the catalysts and may be used for development of new catalytic systems. It can
be seen that many of the catalysts operate at ambient temperatures (293–323 K),
high-space velocities (>20,000 h−1), and exhibit high catalytic activity (conversion
95%). In recent years, more and more researchers are focused on the development,
study, and application of catalysts for decomposition of ozone based on supported
or native metal oxides, in regard with the already mentioned fact—the high price of
metals of the platinum group. In this regard, the most widely used are the oxides of
Mn, Co, Cu, Fe, Ni, Si, Ti, Zr, Ag, and Al.61–69 It has been found that the high cata-
lytic activity in the decomposition of ozone exhibit the oxides of transition metals,70
and particularly the catalysts based on manganese oxide.71 The manganese oxide is
used as a catalyst for various chemical reactions including the decomposition of ni-
trous oxide72–74 and isopropanol,74,75 oxidation of methanol,76 ethanol,77 benzene,78, 79
132 Process Advancement in Chemistry and Chemical Engineering Research

CO,74,75,80and propane81 as well as for reduction of nitric oxide82 and nitrobenzene.83

In terms of technology for the control of air pollution, manganese oxides are used
both in the decomposition of residual ozone, and the degradation of volatile organic
compounds.84,85 Oxides of Mn, Co, Ni, Cr, Ag, Cu, Ce, Fe, V, and Mo supported on
γ-Al2O3 on cordierite foam (60 pores/cm2 and geometry 5.1 × 5.1 × 1.3 cm) have
been prepared and tested in the reaction of decomposition of ozone.71 Experiments
have been carried out at a temperature of 313 K, a linear velocity of 0.7 m/s, inlet
ozone concentration of 2 ppm, relative humidity of 40%, and total gas flow rate of
1800 cm3/s. It has been found out that the catalyst activity decreases over time and
the measurements are made only when the speed of decomposition is stabilized.
After comparison of the conversion degree of ozone, conclusions on their catalyt-
ic activity have been drawn, according to which they have been arranged as fol-
lows: MnO2 (42%)>Co3O4 (39%)> NiO (35%)>Fe2O3 (24%)>Ag2O (21%)>Cr2O3
(18%)>CeO2 (11%)>MgO (8%)>V2O5 (8%)>CuO (5%)>MoO3 (4%). The high dis-
persibility of the material is confirmed by X-ray diffraction analysis. TPR profile
(spectrum) of supported and unsupported MnO2 has been done. It has been found
that the reduction temperature of the supported MnO2, Co3O4, NiO, MoO3, V2O5,
and Fe2O3 were in the range of 611–735 K, while that of CeO2 was above 1000 K.
It has turned out that from all examined metal oxide samples, MnO2 had the lowest
reduction temperature because it exhibited a higher reduction ability in comparison
with the others. On the basis of experiments, it has been proposed that the mecha-
nism of decomposition of ozone on the catalytic surface which includes formation
of intermediate ionic particles possessing either superoxide or peroxide features:

О3 + 2* ↔ *О2 + О* (13)

*О2 + * → 2O* (14)

2O* → O2 + 2* (15)

where * denotes active center.

A distinguishing peculiarity of the proposed scheme is the assumption that the
key intermediate particle *O2 is not desorbed immediately. This could happen if it
has partial ionic character (O2−, O22−). The catalytic activity of iron oxide Fe2O3 in
decomposition of ozone has alsobeen studied in earlier works of Rubashov et al.86,87
It was found that Fe2O3 showed a catalytic activity only when it has been used in
the form of particles with small diameter while catalyst that consisted aggregated
particles which was not efficient. Furthermore, the stability of the catalyst is not
high and its poisoning is due to the formation of oxygen directly associated with the
surface. Reactivation of the catalyst is accomplished by its subjecting to the vacuum
thermal treatment to remove oxygen. The same catalyst was also studied in terms of
the fluidized bed, wherein the rate constant for the catalytic reaction is higher than
the normal gas flow. By determining the constant of the decomposition of ozone on
Ozone Decomposition 133

the surface of Fe2O3 at various temperatures,activation energy of the processcan be

calculated: E = (12.5 ± 1) kcal/mole. This value differs from theactivation energy of
ozone decomposition on compact sample of iron oxide, calculated by Schwab45that
is in the order of 2–3 kcal/mol. The difference can be explained with the regime in
which the kinetic process is carried out, in the first case, and diffusion in the second.
Ellis et al.88 have investigated the activity of 35 different materials with respect to
decomposition of ozone as the best catalysts have turned out nickel oxide and char-
coal. Measurements have been carried out at room temperature, the gas velocities
between 250 and 2000 l/h, atmospheric pressure and ozone concentrations (1.1–25)
× 1012 molecules/cm3. The measured rate of decomposition of ozone corresponds to
a first-order reaction. The authors ignoring the decomposition of ozone in the bulk
have proposed a homogeneous decomposition on the surface:

O3 + M O2 + O + M (16)

О3 + О → 2О2 (17)

In this case, “M” is an active center on the surface, which reduces the energy
of activation of the reaction and accelerates the decomposition. Assuming that the
portion of the surface area occupied by ozone,θ is proportional to the partial pres-
sure of ozone in the volume, the kinetic region of ozone leaving from the gas phase
is equal to:

−dpo3 / dt = kθ = k ' po3 (18)

It is obvious that the firstorder of reaction with respect to the decomposition of
ozone have been established, which has been confirmed experimentally. The de-
composition of ozone in gradient-free reactor is considered in work,89as thin film
of nickel oxide coated on the walls of the reactor was used as a catalyst has used.
Turbulence of gas flow in such type of reactor would avoid the physical transfer and
will provide conditions for studying the kinetics only on the catalytic surface. In
this case, the turbulent diffusion is superior to the rate of reaction and the process is
conducted in the kinetic regime. It has been found that the rate constant in the range
10–40°C is calculated by the expression:

K=102.54p−0.5exp (−1250/T) cm/s (19)

wherep is in atm.
The experiments that have been made with different pressures of the oxygen
and ozone–helium mixtures have shown that the rate constant changes depending
on the total pressure and not by the partial pressure of ozone. Hence, the authors
have concluded that the catalyst operates in inner diffusion mode, that is, the reac-
tion rate is limited by molecular diffusion in the pores of the catalyst. These and
134 Process Advancement in Chemistry and Chemical Engineering Research

other assumptions made it possible to explain the resulting experimental depen-

dence of the rate constant on the total pressure of the mixture in the gas phase. The
kinetics of decomposition of ozone in gradient-free reactor was investigated in the
work.90Activities of γ-Al2O3, hopkalite (MnO2, CuO, bentonite), silver–manganese
oxide, alumina–palladium, and alumina–platinum catalysts are measured. The ex-
periments have been conducted at 60°C and initial ozone concentration of 2.7×10−5
mol/l. Silver–manganese oxide and hopkaliteare the most active of the tested cata-
lysts. Kinetics of decomposition of ozone is determined to be of first order. It have
also been defined the rate constants and energies of activation, as the latter be-
ing fluctuated in the range of 6–10 kcal/mol. Conclusions of authors on the active
surface of the catalyst are of interest. It has been found that the activation energy
does not depend on the dispersibility, but influences the catalytic activity. On the
other hand, dispersibility does not increase the inner surface of the porous material.
Hence, it has been concluded that the decomposition of ozone occurs in the outer
kinetic region, that is, the heterogeneous reaction is limited mainly by the outer sur-
face of the catalyst. During the study of the decomposition of ozone in the presence
of nickel oxide91 is established that the reaction to be first order. It has been proposed
that the limiting stage appear to be adsorption of ozone to the catalytic surface. The
EPR spectra revealed the presence of ozonide ion radical O3−.92,93 The formation of
O3− is explained by the process of electron transfer from the catalyst to the ozone,
so that the surface Ni2+ ions are oxidized to the Ni3+. Further studies of the authors
have shown that approximately 5% of the total reaction takes place in this way. The
remaining amount of the ozone has been decomposed by molecular mechanism:
O3

2O3 + NiO NiO NiO + 3O2

O3 (20)

In some cases, the ozone does not remain in the molecular state and dissociate
to atomic or diatomic oxygen species. Ozonide particles on catalytic surface are
generated by the reaction:

О− + О2 → О3− (21)

Figure 10.5 shows the characteristic bands of the EPR spectrum at g1 = 2.0147,
g2 = 2.0120, and g3 = 2.0018, due to the formation of the ionradical O3−.
Ozone Decomposition 135

FIGURE 10.5  EPR spectrum of O3− at temperature 77 K.

Martynov et al.94 have studied the influence of the CuO, CoO, and NiO on the
process of ozone decomposition. The catalysts have been prepared using aqueous
solutions of the respective nitrates and have supported on the walls of the tubular
reactor (l=25 cm, D=1.6 cm). The reactor has been heated to 370°C for 5 h, after
which each of the catalysts was treated with ozone at a concentration of 0.5 vol.%
for 6 h at a gas velocity of 100 l/h. After solving the diffusion-kinetic equation of
the ozone decomposition reaction, the diffusion and the kinetic constants as well as
the coefficients of ozone decompositioncan be defined. The recent ones character-
ize the decomposition rate of ozone molecules on the catalyst surface toward the
rate of the hits of molecules with the surface. The results of these calculations for
different samples are presented in Table 10.4 wherein ω is space velocity, γ is co-
efficient of ozone decomposition, and kexpkkin are experimental and theoretical rate
constants,respectively.

TABLE 10.4  Kinetic Parameters of the Reaction of Ozone Decomposition on Some Oxides.
Catalyst ω, l/h kexp, s−1 γ.10−5 kkin, s−1
CuO 20 1.0 4.8 2.8
CoO 100 0.9 4.1 2.4
CoO 200 1.3 6.3 3.6
NiO 20 0.9 4.4 2.6
NiO 100 1.0 4.8 2.8
NiO 200 1.7 8.1 4.4
136 Process Advancement in Chemistry and Chemical Engineering Research

It is evident that the catalysts activity increases at ω =200 l/h. This is explained
by the flow of catalytic reaction between kinetic and diffusion regions. Furthermore,
the values of the rate constants of ozone decomposition in kinetic mode are almost
three times higher than the experimental.
Radhakrishnan et al.68 have used manganese oxide catalysts supported on Al2O3,
ZrO2, TiO2, and SiO2 for study of the support influence on the kinetics of decom-
position of ozone. By using different physical methods of analysis such as “in situ”
laser Raman spectroscopy, temperature-programmed desorption of oxygen, and
measuring of specific surface area (BET), it is shown that the manganese oxide is
highly dispersed on the support surface. The Raman spectra of the supported cata-
lysts reveal the presence of Mn–O bands as a result from well-dispersed manganese
oxide particles on the Al2O3- and SiO2-supported catalysts. During the process of
ozone decomposition on the catalytic surface, a signal from adsorbed particles ap-
pears at Raman spectra in the region of 876–880 cm−1. These particles were identi-
fied as oxygen particles from peroxide type (O22−), which disappear upon catalysts
heating to 500 K. Using temperature-programmed desorptionof oxygen, the number
of active manganese centers on the catalyst surface is calculated. After integration
of the TPD peaks area corresponding to desorption of adsorbed oxygen, besides
the density of active sites, the corresponding dispersion values of the catalysts are
also identified. These resultsof the calculated specific surface areas of the catalytic
samples are shown in Table 10.5. The catalysts were tested in reaction of ozone de-
composition to determine their activity, and it has been found that the rate of decom-
position increases with increasing the ozone partial pressure and the temperature. It
has calculated the kinetic parameters of the reaction. It has been found that the acti-
vation energy is in the rangeof 3–15 kJ/mol, depending on the catalyst sample, as it
is lower (3 kJ/mol) in the case of ozone decomposition on MnOx/Al2O3. It was sug-
gested that this is related to the structure of this catalyst, which is the only one of the
tested samples that has mononuclear manganese center coordinated by five oxygen
atoms. This was demonstrated using absorption fine-structure X-ray spectroscopy.
Using this method, it was also found that the other three supported catalysts possess
multi-core active manganese centers surrounded as well by five oxygen atoms.

TABLE 10.5  Densities of Active Centers and Specific Surfaces.

Density, mmol g−1
Catalyst Sg, m2 g−1 Dispersion, (%)
(O2/O3 TPD)
MnOx/Al2O3 92 40 12
MnOx/ZrO2 45 163 47
MnOx/TiO2 47 31 9
MnOx/SiO2 88 13 4
Ozone Decomposition 137

A mechanism of ozone decomposition on MnOx/Al2O3 catalyst has been pro-

posed:

O3 + Mnn+ → O2− + Mn(n+2)+ + O2 (22)

O3 + O2− + Mn(n+2)+ → O22− + Mn(n+2)+ + O2 (23)

O22− + Mn(n+2)+ → Mnn+ + O2 (24)

The presented mechanism consists of electron transfer from the manganese cen-
ter to ozone, wherethe manganese is reduced by desorption of peroxide particles to
form oxygen (O22−→O2 + 2e−).
Study of MnOx/Al2O3 with absorption of fine-structure X-ray spectroscopy is
also presented in publication.95 The aim of the work is to receive important infor-
mation on the catalytic properties of the supported manganese oxides in oxidation
reactions using ozone. The structural changes in the manganese oxide supported on
alumina have been detected in the process of catalytic ozone decomposition at room
temperature. It has been found that during the ozone decomposition in presence
of water vapor, the manganese is oxidized to higher oxidation state. At the same
time, the water molecule combines to manganese active center due to cleavage of
Mn–O–Al bond. The catalyst is completely regenerated after calcination in oxygen
at 723 K.
In article,96 the influence of nickel oxide in addition to the activity of cement-
containing catalyst for ozone decomposition has been studied. The activity of the
samples was measured by calculating the rate of decomposition γ that shows the
degree of active interactions (leading to decomposition) of ozone molecules with
catalytic surface. According toLunin, et al,6 the expression for γ is:

4ω .ln (Co / C )
γ= (25)
Vt S
whereVt—specific heat velocity of ozone molecules, S—geometric surface of the
catalyst, ω—space velocity of the gas stream, C0 and C—inlet and outlet ozone
concentrations.
It has been found that the addition of nickel oxide in the catalyst composition
improves its catalytic properties. Upon decomposition of wet ozone is observed; a
decrease in the activity of all tested samples, as the calculated values for γ are 2−3
times lower compared with the value obtained after decomposition of dry ozone. On
the basis of the measured values for energy of activation (Ea = 5.9 ± 0.3 kJ/mol) of
ozone decomposition in the region of high temperatures (300–400 K), and the cor-
responding values of Ea (15.2 ± 0.4 kJ/mol) in the region of low temperatures, it has
been made a conclusion that in the first case, the process goes to the outer diffusion
138 Process Advancement in Chemistry and Chemical Engineering Research

region, whereas in the second,into the inner diffusion region. The factor of diffusion
suspension or the accessible part of the surface is estimated to make clear the role of
the internal catalytic surface.This has permitted to perform calculation that at room
temperature the molecules of ozone enter into the pores of the catalyst at a distance
not more than ~10−4 cm.
Lin et al.97 have studied the activity of a series oxide supports and supported
metal catalysts with respect to decomposition of ozone in water. From the tested re-
action conditions,the activated carbon has showed relatively high activity, while the
zeolite support (HY and modernite), Al2O3, SiO2, SiO2.Al2O3,and TiO2 have showed
zero or negligible activity. From all supported metal catalysts that aresubmitted to
ozone dissolved in water, the noble metals have highest activity in ozone decomposi-
tion excepting gold. The metals are deposited on four types of supports (Al2O3, SiO2,
SiO2.Al2O3, and TiO2). Highest activity was measured for the catalysts deposited on
silica. It has been found that the catalyst containing 3% Pd/SiO2 is most effective in
the reaction of ozone decomposition from all tested samples. A comparison of some
indicators for Pd catalysts deposited on different supports is presented in Table 10.6.

TABLE 10.6  Comparison of the Specific Surface Areas, the Size of Metal Particles and
the Average Rates of Ozone Decomposition in Water Over Palladium-Containing Catalysts.
Specific surface area Size of metal Average rate (mg(O )
Catalyst 3
(m2 g−1) particle (Å) min−1 g−1(cat.))
Pd/SiO2 206 90 0.77
Pd/SiO2.Al2O3 221 70 0.54
Pd/Al2O3 139 75 0.39
Pd/TiO2 34 109 0.35

The first-order reaction of ozone decomposition on 3% Pd/SiO2with respect to-

concentration of ozonehas been determined. In the presence of the same catalyst, the
calculated activation energy is about 3 kcal mol−1 and is assumed that the reaction
occurs in the diffusion region. The proposed mechanism of catalytic decomposition
of ozone in water is similar to the mechanism of decomposition of gaseous ozone.
In Table 10.7, two possible reaction paths of ozone decomposition on metals or
oxidesare shown, depending on the fact thatthe oxygen is adsorbed on the catalytic
surface.

TABLE 10.7  Possible Mechanisms of Catalytic Ozone Decomposition in Water.97

Case of O2 not adsorbed on metal Case of O2 adsorbed on metal
O3 → O3(a) O3 → O3(a)
O3(a) → O(a) + O2 O3(a) → O(a) + O2(a)
O(a) + O3 → O2 + O2(a)
O(a) + O3 → 2O2
O2(a) → O2
Ozone Decomposition 139

In the literature,data are there too for the study of ozone decomposition in water
in presence of aluminum (hydroxyl) oxide.98 It has been suggested that the surface
hydroxyl groups and the acid–base properties of aluminum (hydroxyl) oxides play
important role in catalytic decomposition of ozone.
The environmental application of ozone in catalysis has been demonstrated in
article,99 devoted to the ozonation of naproxen and carbamazepine on titanium di-
oxide. The experiments were carried out in aqueous solution at T = 25°C and in pH
range of 3–7. The results have been indicated that naproxen and carbamazepine are
completely destructed in the first few minutes of the reaction. The degree of min-
eralization during the non-catalytic reaction flow is measured up to about 50% and
is formed primarily in the first 10–20 min. The presence of the catalyst is increased
to more than 75% the degree of mineralization of the initial hydrocarbon. Further-
more, it has been found that the catalyst increases the mineralization in both acid
and neutral solution, as the best results are obtained at slightly acidic media. This
effect is related with possible adsorption of intermediate reaction products on Lewis
acidic catalytic sites. It is also reflected that the titanium dioxide catalyzes the ozone
decomposition in acidic media, whereas in neutral solution the ozone destruction
is inhibited. This has precluded the flow of mechanism based on surface formation
of hydroxyl radicals followed by their migration and complete reaction with the or-
ganic compounds. The variation of the total organic carbon is modeled as a function
of the integral of the applied amount of ozone. On this basis, it is assumed that the
reaction between organic compounds and ozone is of second order. For naproxen
and carbamazepine,the calculated pseudo-homogeneous catalytic rate constants at
pH 5 and catalyst amount of 1 g/l are 7.76 × 10−3 ± 3.9 × 10−4 and 4.25 × 10−3 ± 9.7
× 10−4l mmol−1 s−1, respectively. The products of ozonation are investigated with a
specific ultraviolet absorption at 254 nm. The wide application of metal oxide cata-
lysts in ozone decomposition necessitated the use of different instrumental methods
for analysis. Based on the results of X-ray diffraction, X-ray photoelectron spectros-
copy, EPR, and TPD, it has been found that during the destruction of ozone on silver
catalyst supported on silica, the silver is oxidized to complex mixture of Ag2O3 and
AgO.100 This investigation of catalytic ozone decomposition on Ag/SiO2 is carried
out in the temperature range of−40°C to +25°C, it is determined as firstorder of
reaction, and the calculated activation energy is 65 kJ/mol. X-ray diffraction has
also been used to determine the phase composition of manganese oxide catalysts
supported on γ-Al2O3 and SiO2.101 Moreover, the samples are characterized by Ra-
man and IR spectroscopy. The supported catalysts are prepared by nitrate precursors
using the impregnation method. In addition to the Raman spectral bands of β-MnO2
and α-Mn2O3 phases, other signals are also registered and attributed to isolated Mn2+
ions present in tetraedrical vacations on the support surface, and in some epitaxial
layerson γ−Mn2O3 and manganese silicate, respectively. The data from the IR spec-
tra was not so much useful due to the fact that the supporter band overlaps the bands
of manganese particles formed on the surface, and make it difficult to identify them.
140 Process Advancement in Chemistry and Chemical Engineering Research

Eynaga et al.102 carried out catalytic oxidation of cyclohexane with ozone on

manganese oxide supported on aluminum oxide at the temperature of 295 K. “In
situ” IR studies have been performed for taking information on the intermediates
formed on the catalytic surface at the time of oxidation. It has been found that the
intermediates are partially oxidized to alcohols, ketones, acid anhydrides, and car-
boxylic acids. These compounds are subsequently decomposed by ozone. In the
beginning, the activity of the catalyst gradually decreases whereit reaches a steady
state with mole fractions of CO and CO2,90 and 10%, respectively. It has been found
that high-resistant particles, containing C=O, COO–,and CH groups, remain on the
catalyst surface that caused the slow deactivation of the catalyst. The C=O groups
are decomposed at relatively low temperatures (<473 K), while the COO–and CH
groups are dissociated at temperatures>473 K.
The kinetics of gas-phase ozone decomposition was studied by heterogeneous
interactions of ozone with aluminum thin films.103 The ozone concentrations were
monitored in real time using UV absorption spectroscopy at 254 nm. The films
were prepared by dispersion of fine alumina powder in methanol, and their specific
surface areas are determined by “in situ” adsorption of krypton at 77 K. It has been
found that the reactivity of alumina decreases with increasing the ozone concentra-
tion. As consequence of multiple exposures to ozone of one film, it has been found
that the number of active sites is greater than 1.4 × 1014 per cm2 surface or it is com-
parable with the total number of active sites. The coefficients of ozone decomposi-
tion are calculated (γ) depending on the initial concentration of ozone in the reaction
cell, using the expression:

γ = (4×kI×V)/(c×SA) (26)

wherec is the average velocity of gas-phase molecules of ozone, kI is the observed

initial rate constant of ozone decomposition from first order (for the first 10 s), SA
is the total surface area of the aluminum film, and V is volume of the reactor. From
the results, it was concluded that the coefficients of ozone decomposition on fresh
films depend inversely on ozone concentration, ranging from 10−6 to 1014 molecules/
cm3 to 10−5to 1013 molecules/cm3 ozone. It has also been observed that the coeffi-
cients of ozone decomposition do not depend on the relative humidity of gas stream.
A mechanism of the reaction of catalytic ozone decomposition, based on detailed
spectroscopic investigations of the catalytic surface,104,105 where there is evidence for
the formation of peroxide particles on the surfacewas discussed:

→ O 2 + O* (27)
O3 + O* 

O3 + O* 
→ O*2 + O 2 (28)

O*2 
→ O 2 + * (29)
Ozone Decomposition 141

It has been suggested that molecular oxygen could also be initiated by the reac-
tion:

О* + О* → 2* + О2 (30)

It has been found that the reactivity of the oxidized aluminum film can be par-
tially restored after being placed for certain period in a medium free of ozone, water
vapor, and carbon dioxide.

10.4.3.1  DECOMPOSITION OF OZONE ON THE SURFACE OF

THE CARBON FIBER AND INERT MATERIALS
The use of carbon material in adsorption and catalysis is related to their structural
properties and surface chemical groups. Their structural properties are determined
by the specific surface area and porosity, while the chemical groups on the sur-
face of the catalyst are mainly composed of oxygen-containing functional groups.
Ozone reacts with various carbon materials such as activated carbon, carbon black,
graphite, carbon fiber, and so on. The character of these interactions depends both
on the nature of the carbon surface and temperature.106Two types of interactions
such as the complete oxidation leading to formation of gaseous carbon oxides and
partial oxidation, producing surface oxygen-containing functional groupshas been
tested.106,107 With increase inthe temperature, the ratio between these two processes
is displaced in the direction of complete oxidation. The latter is accompanied by an
oxidative destruction on the surface with formation of gaseous carbon oxides. In
addition, on the surface of the carbon,catalytic decomposition of ozonetakes place.
The physicochemical properties of activated carbon treated with ozone, as well as
the kinetics of the process related to the release of CO and CO2have been studiedin
a number of publications.108–111 Subrahmanyam et al.112 have examined the catalytic
decomposition of ozone to molecular oxygen on active carbon in the form of gran-
ules and fibers at room temperature. It was found that the dynamics of the activity
of the carbons is characterized by two distinct zones. The first one is the observed
high activity with respect to the decomposition of ozone, which is mainly due to the
chemical reaction of ozone with carbon. As a result of this interaction on the car-
bons, oxygen-containing surface groups are formed. Then sharp drop the conversion
is registered and transition of the catalyst to a low active zone takes place. In this
zone, the decomposition of the ozone to molecular oxygen takes place in a catalytic
way. The activities of the carbons in dry environment on one hand and in presence of
water vapor and NOx on the other have been compared. The presence of water vapor
has reduced catalytic activity, while the presence of the NOx has improved activity,
due to the change in the carbon surface functional groups. They can be modified
in two ways: boiling in dilute nitric acid or thermal treatment at 1273 K in helium
media. Positive results were obtained only in the first treatment. The decomposition
142 Process Advancement in Chemistry and Chemical Engineering Research

of ozone with respect to the gasification of carbon with formation of COx proceeds
with a selectivity of less than 25%. The catalysts were characterized by means of
temperature-programmed decomposition of surface functional groups, IR, and X-
ray photoelectron spectroscopy. Mechanism of decomposition of ozone on activated
carbon has been proposed (Fig.10.6).

FIGURE 10.6  Simplified scheme of ozone decomposition on carbon.

In ozone decomposition process, it is difficult to draw a line between relatively

inert materials and heterogeneous catalysts. However, the separation can be made
on the basis of two evident signs: (1) the catalysts for ozone decomposition are
specifically synthesized and (2) they have higher catalytic activity (higher values
for the coefficient of decomposition γ) compared to the inert materials. In the lit-
erature, there are investigations on the reaction of ozone destruction on the surface
of silica,113 glass,114 volcanic aerosols,115,116 and ammonium hydrogen sulfate.117 The
published values for the coefficient of ozone decomposition γ for quartz and glass
are in the order of (1–2) × 10−11, and those for aerosols and ammonium sulfatefrom
1.61 × 10−6 to 7.71 × 10−8. It is interesting to mark the studies of ozone decomposi-
tion on the surface of Saharan dust118 as well as the application of slurry-treated
water as catalyst for ozone destruction in aqueous medium.119
The heterogeneous reaction between O3 and authentic Saharan dust surfaces118
was investigated in a Knudsen reactor at ~296 K. O3 was destroyed on the dust sur-
face and O2 was formed with conversion efficiencies of 1.0 and 1.3 molecules; O2
per O3 molecule was destroyed for unheated and heated samples, respectively. No
O3 desorbed from exposed dust samples, showing that the uptake was irreversible.
The uptake coefficients for the irreversible destruction of O3 on (unheated) Saharan
dust surfaces depended on the O3 concentration and varied between 4.8×10−5and
Ozone Decomposition 143

2.2×10−6 for the steady-state uptake coefficient. At very high O3 concentrations, the
surface was deactivated, and O3 uptake ceased after a certain exposure period.
New, effective and stable ecological catalyst based on slurry119 has been used
in the process of ozone decomposition in water acidic medium. The catalyst was
characterized by X-ray fluorescence, transmission electron microscopy, scanning
electron microscopy, and X-ray diffraction. The sludge is essentially composed of
different metallic and nonmetallic oxides. It has been investigated the effect of vari-
ous experimental parameters such as catalyst amount, initial ozone concentration,
and application of different metal oxide catalysts. The decomposition of dissolved
ozone is significantly increased with the enhancement of the initial ozone concentra-
tion and the increment of catalyst amount from 125 to 750 mg. The order of activity
of the tested catalysts such asZnO≈sludge>TiO2>SiO2>Al2O3≈Fe2O3has been estab-
lished. It has been found that ozone does not affect the catalyst morphology and
its composition, and it is concluded that the sludge is promising catalyst for ozone
decomposition in water.
In the end of the literature review, it can be concluded that except for the metals
of platinum group, characterized by its high price, the metal oxide catalysts contain-
ing manganese oxide have the highest activity in decomposition of gaseous ozone
and also in catalytic oxidation of pollutants. It is important to mention that unlike
the inert materials for the oxide catalysts, there is nostrong dependence of catalytic
activity from ozone concentration in gas phase. It should be emphasized that despite
the great number of publications on the subject, the kinetics and the mechanism of
ozone decomposition on the surface of heterogeneous metal oxide catalysts are not
cleared up sufficiently.

KEYWORDS

•• catalysts
•• synthesis
•• kinetics
•• mechanism

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CHAPTER 11

OZONE DECOMPOSITION ON THE

SURFACE OF METAL OXIDE CATALYST
T. BATAKLIEV, V. GEORGIEV, M. ANACHKOV, S. RAKOVSKY,
A. BERLIN1, and G. E. ZAIKOV2
Institute of Catalysis, Bulgarian Academy of Sciences, Bonchev Str., bl.11, #218, 1113
Sofia, Bulgaria. E-mail: [email protected]
1
N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 4
Kosygin str., Moscow 119991, Russia. E-mail: [email protected]
2
N. M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, 4,
Kosygin str., Moscow 119334, Russian Federation. E-mail: [email protected]

CONTENTS
Abstract..................................................................................................................150
11.1 Introduction..................................................................................................150
11.2 Experimental................................................................................................150
11.3 Results..........................................................................................................151
11.4 Discussion....................................................................................................153
11.5 Conclusion...................................................................................................161
Keywords...............................................................................................................161
References..............................................................................................................161
150 Process Advancement in Chemistry and Chemical Engineering Research

ABSTRACT
The catalytic decomposition of ozone to molecular oxygen over catalytic mixture
containing manganese, copper, and nickel oxides was investigated in the present
work. The catalytic activity was evaluated on the basis of the decomposition coef-
ficient γ, which is proportional to ozone decomposition rate and has been already
used in other studies for catalytic activity estimation. The reaction was studied in the
presence of thermally modified catalytic samples operating at different temperatures
and ozone flow rates. The catalyst changes were followed by kinetic methods, sur-
face measurements, temperature programmed reduction, and IR-spectroscopy. The
phase composition of the metal oxide catalyst was determined by X-ray diffraction.
The catalyst mixture has shown high activity in ozone decomposition at wet and dry
O3/O2 gas mixtures.

11.1 INTRODUCTION
Ozone finds wide application in such important industrial processes like: purifica-
tion of drinking water, bleaching of textiles, oxidation of sulfurous gas, complete
oxidation of exhaust gases from production of nitric acid, and production of many
organic compounds.1 Ozone in the atmosphere protects the Earth’s surface against
UV-radiation, but on the ground level it is an air contaminant.1–3 At this level, ozone
can be removed by adsorption, absorption, thermal, and catalytic decomposition.
The most effective catalysts for ozone decomposition are based on manganese ox-
ide.4–7 The main method for purification of waste gases containing residual ozone is
the heterogeneous catalytic decomposition. Noble metals like Pt, Ag, Pd, and transi-
tion metal oxides including Co, Cu, and Ni supported on γ-Al2O3, SiO2, and TiO2
also are effective catalysts in this reaction,8–14 as it can be mentioned for activated
carbon fibers.15
The decomposition of ozone is a thermodynamically favored process with a heat
of reaction of ∆H0298 = −138 kJ/mol and free energy of reaction of ∆G0298 = −163 kJ/
mol.16 The ozone structure is resonance stabilized, which is the reason for its rela-
tive stability. The coefficient of ozone decomposition γ was used in other studies for
investigation of NiO addition influence over cement-containing catalysts activity,17
and for the study of thermal treatment influence over oxide catalyst activity.18
The aim of present study is to apply mixed metal oxide catalyst for ozone de-
composition to investigate its behavior at different conditions and to determine its
composition and surface properties using different physical methods for analysis.

11.2 EXPERIMENTAL
The basic copper, manganese, nickel carbonates, and clay-bearing cement are
milled in advance, then carefully mixed, crushed, and compressed under pressure
Ozone Decomposition on the Surface of Metal Oxide Catalyst 151

4 t/cm2. The resulting tablets were treated hydrothermally at temperature of 80°C

for 6 h, dried at 120°C for 6 h, and calcinated at 420°C for 6 h. The metal oxide
catalyst based on the mixture of manganese oxide (20 wt%), copper oxide (10 wt%),
nickel oxide (30 wt%), and clay-bearing cement (40 wt%) was thermally modified
at 500°C for 2 h and finally was applied in our investigation as catalyst for ozone
decomposition in dry and water-enriched gas flows. The catalyst was granulated and
contained cylindrical grains with a diameter of about 5 mm and thickness of 3 mm.
The reactor for kinetic measurements was a glass tube (6 × 150 mm) filled in
with 0.08–0.12 g of catalyst. Figure 11.1 shows the schematic of the experimental
set-up for all kinetics.
The kinetic measurements of ozone degradation were performed at flow rates
ranging from 6.0 to 24 l h−1 and ozone concentration from 1.0 to 1.2 mM. Ozone
was generated by passing dry oxygen through a high-voltage silent-discharge ozone
generator. About 1 mM ozone concentration was achieved at 15–20 kV. The inlet
and outlet ozone concentrations were monitored using an UV absorption-type ozone
analyzer at 300 nm.
The specific surface area of the catalyst (72 m2/g) was measured by N2 adsorp-
tion–desorption isotherms at 77 K using BET method in a FlowSorb 2300 instru-
ment (Micromeritics Instrument Corporation). IR studies were performed in the
transmittance mode using a Nicolet 6700 FT-IR spectrometer (Thermo Electron
Corporation). A mixture of KBr and manganese oxide catalyst (100:1) was milled
in an agate mortar manually before the preparation of pellets. The spectra were ob-
tained by averaging 50 scans with 0.4 cm−1 resolution.
A typical TPR experiment is done by passing a H2 stream over a catalyst while it
is heated linearly and monitoring the consumption of H2 with a thermal conductivity
detector or mass spectrometer. In our study, a 10% H2/Ar mixture was used and the
consumption of H2 was monitored using a thermal conductivity detector. A linear
heating rate of 0.17 K s−1 was used for the experiment. X-ray diffraction (XRD)
analysis was used to determine the crystalline metal oxide phases for the supported
catalyst. A Bruker D8 Advance powder diffractometer with Cu Kα radiation source
and SolX detector was used. The samples were scanned from 2θ angles of 10–80° at
a rate of 0.04° s−1. The X-ray power operated with a current of 40 mA and a voltage
of 45 kV.

11.3 RESULTS
The catalytic activity was evaluated on the basis of the coefficient 19 that is propor-
tional to ozone decomposition rate and to catalyst efficiency. It has been already
used in other studies.17,18
4ω ln [O3]0
γ= VtS [O3]
,
152 Process Advancement in Chemistry and Chemical Engineering Research

where ω is the flow rate, Vt—specific heat rate of ozone molecules, S—geometrical
surface of catalyst sample, and [O3]0 and [O3]—inlet and outlet ozone concentra-
tions, respectively.
In general, there exists no precise estimation of γ by solving the diffusion-kinetic
equation. This is possible in some special cases, for example, to find γ using the ap-
proximate method of Frank-Kamenetsky (method of equally accessible surface).20
Equally accessible surface is that surface where, in each section, the molecules fall
with equal probability. The rate of the chemical reaction on the surface is expressed
by concentration of reacting molecules in the volume near the surface. For reactions
of first order:

Ws = K sCs = KC ' .

The parameters dimension is as follows: ws—(molecules/cm2.s), кs

и к—(s−1) и (cm/s), сs и с′—(molecules/cm2) и (molecules/cm3). It has
been suggested that the molecular flow from volume to surface does
not depend on the reaction rate, and with approximation it is defined
of the equation:

J = β (C - C ') ,
where β—coefficient of mass transfer, having dimension as the rate constant k,
equal to cm s−1, c and c'—concentration in the regions of the volume, where the
flow is passing through.
The distance between the surface and the region with concentration c', the ozone
molecules pass without collisions with average specific heat rate vT. The number of
hits on unit of surface per unit of time z = vT c′ and taking into account the definition
of coefficient of ozone decomposition, it has been found that:

kc' 4k
γ= z =
vT .
Thus, the coefficient γ is related to the rate constant k. Now we could consider
the case when the surface, where the reaction takes place, is located in an unlimited
volume of gas. In stationary conditions, the molecular flow toward the surface is
equal to the chemical reaction rate:

β kc
ws= = keff c ,
k+β
Ozone Decomposition on the Surface of Metal Oxide Catalyst 153

where c—concentration of actives molecules standing to great distance from the

catalytic surface.
Thus, the rate of reaction on the surface is expressed by the concentration in the
volume and the effective rate constant that depends on the rate constant k and the
coefficient of mass transfer β, obviously:

1 1 1 .
= +
keff k β

If β >> k, then c '= c and keff = k: the total reaction rate is limited by the no hits
stage with constant k. In this case, the reaction proceeds in the kinetic region. If β
<< k, c' << c, and keff = β, the reaction rate is determined by the rate of mass transfer
and the reaction occurs in the diffusion region.
On the other hand,19 when operating in stationary conditions, the relationship
between the rate constant of the reaction of heterogeneous ozone decomposition and
the coefficient of ozone decomposition γ is given by the formula:
4ω ln [O3]0
γ=
SvT [O3]
,
where V—volume of reactor, S—geometric surface of catalyst, and vT—specific
heat rate of ozone molecules.
Taking into account, the dependence of the gas flow rate from the reactor radius,
and considering the concentration of active ozone molecules and the reaction time
of ozone decomposition, after complex mathematical transformations, the latter for-
mula passes into the expression:

4ω ln [O3]0
γ=
SvT [O3]
.

where ω—gas flow rate, [O3]0 и [O3]—inlet and outlet ozone concentrations.
This formula is applicable for tubular type reactor, when the catalyst is sup-
ported as thin layer on the walls in the inner side of the tube. The expression is also
convenient for calculation of catalytic activity in the case when the reactor is filled
with granulated catalytic samples having specific geometric surface. Therefore, this
method has been used by us for calculation of the catalysts activity in the process of
ozone decomposition.

11.4 DISCUSSION
Figure 11.1 shows the changes occurring in catalytic activity of the cement-contain-
ing catalyst, when the calcination temperature of the samples is different.
154 Process Advancement in Chemistry and Chemical Engineering Research

All the experiments were made in dry conditions and ozone flow rate of 6 l
h−1. The MnOx/CuO/NiO catalyst has catalytic activity in ozone decomposition that
does not change dramatically with an increase in calcination temperature. However,
we can see that the catalyst is more active when the calcination temperature is in
the range of 400–500°C. In Figure 11.2, changes of γ are shown at two different
flow rates in temperature range of 258–323 K. The calculated activation energy is
5 kJ/mol. In these experiments, the reactor was kept up at constant temperature for
enough time to get the necessary value. The duration of the decomposition reaction
and the reaction time were much smaller than the time of cooling or heating the
reactor. This means that the temperature inside the reactor was maintained constant
during the measurement of ozone decomposition rate. The difference between the
values of γ at different flow rates is due to the low loading of catalyst. The low
values of Ea are directly connected with the fact that limited stage of reaction is the
adsorption of ozone on catalytic surface.

FIGURE 11.1  Experimental set-up of reaction system for catalytic decomposition of

ozone: 1—oxygen; 2—flow controller; 3—ozone generator; 4—transformer; 5—three way
turn cock; 6—reactor charged with catalyst sample; 7—ozone analyzer; 8—reactor for
decomposition of residual ozone; 9—current stabilizer; 10—autotransformer; 11—voltmeter.

FIGURE 11.2  Dependence of the catalytic activity in ozone decomposition on calcination

temperature.
Ozone Decomposition on the Surface of Metal Oxide Catalyst 155

In Figure 11.3, changes of γ are presented depending on temperature and humid-

ity of the gas flow. The measured activation energy was also 5 kJ/mol. It was found
out that the humidity of the gas flow decreases the catalytic activity by 10%, but the
catalyst does not disturb its stability in the time of ozonation.

FIGURE 11.3  Dependence of the catalytic activity in ozone decomposition on reaction

temperature at two different flow rates.

Figure 11.4 presents the changes of γ at different flow rates at two temperatures,
−258 and 298 K. It can be seen that γ is proportional to the flow rate at both tem-
peratures. The coefficient of decomposition depends on temperature, but at 258 K,
the steady state of the curve is reached faster. The obtained values of γ are close to
the coefficients reported in literature.17 Therefore, it could be concluded that at low
values of gas flow rate, a reason for the dependence of the catalytic activity from gas
flow rate is the influence of the external diffusion over the kinetics of the process of
heterogeneous catalytic ozone decomposition on catalyst surface, that is, the process
takes place mainly in the outer diffusion region or in the transition diffusion-kinetic
region.
156 Process Advancement in Chemistry and Chemical Engineering Research

FIGURE 11.4  Temperature dependence of catalytic activity at dry and humid conditions,
temperature range 273–323 K, ozone flow rate 8 l h−1.

Figure 11.5 shows the dependence of γ on gas flow humidity at 298 K. The val-
ues of γ decrease with increase in the humidity, but nevertheless these values remain
relatively high. The effect of water vapor may be result of thin film formation on the
catalytic surface that makes the diffusion of ozone to catalytic centers more difficult.
The humidity of O3/O2 gas flow was measured to be 50%.

FIGURE 11.5  Flow rate dependence of catalytic activity at 258 and 298 K, ozone flow rate
range 5–25 l h−1.
Ozone Decomposition on the Surface of Metal Oxide Catalyst 157

A popular technique used to characterize manganese oxide containing catalyst

and to determine the identity of the manganese oxide phase at high loadings (>6%)
has been X-ray diffraction (XRD).21,22 The X-ray diffraction results for the cement-
containing metal oxide catalyst are presented in Figure 11.6. The diffractogram for
the catalyst sample showed peaks with a certain number of large intensities at dif-
ferent 2θ values. The peaks at 39 and 35.5° correspond to copper oxide (CuO).
The diffraction features for the catalyst at 33 and 55.1° are indicative of bixbyite-ο
(Mn2O3). The metal oxide catalyst sample peaks at 43, 37.2, and 62.9° are due to
nickel oxide (NiO). The catalyst diffraction peaks at 36.1, 32.4, and 59.9° corre-
spond to hausmannite (Mn3O4). Finally, the cement diffraction peaks at 20, 25.5°
and 29.5, 47.5° are due to grossite (CaAl4O7) and calcite (CaCO3), respectively. In
conclusion, the information that can be deduced from the X-ray diffractogram for
this catalyst is that there are three metal oxides as the manganese oxide is present in
two forms—Mn2O3 and Mn3O4. It could be also seen that the cement support of the
catalyst is built mainly by two components—CaAl4O7 and CaCO3.

FIGURE 11.6  Flow rate dependence of catalytic activity at dry and humid conditions,
ozone flow rate range 4–26 l h−1.

The TPR experiment was carried out for the supported cement metal oxide cata-
lyst (Fig. 11.7). The H2 consumption was monitored by thermal conductivity detec-
tor in the course of time. Manganese-containing catalyst was already studied using
TPR.23 The peak temperatures of reduction in Figure 11.7 are 527, 596, 643, and 976
K or the reduction temperature of the catalyst was in the range of 527–976 K. The
bulk reduction peaks at 596 and 643 K can be identified for the manganese oxide in
158 Process Advancement in Chemistry and Chemical Engineering Research

the cement-containing metal oxide mixture while the peak at 976 K can be related
with reduction of the nickel oxide.8,23

FIGURE 11.7  XRD of MnOx/CuO/NiO catalyst supported on cement.

The most possible mechanism6,7 of catalytic ozone decomposition can be pre-

sented as follows:

O3 + * O2 + O* (1)

O3 + O* O2* + O2 (2)

O2* O2 + * (3)

where the symbol * was used to denote surface sites. In step (1), ozone decays
and the finding that the adsorbed ozone that does not desorb, ascertains the irrevers-
ibility of steps (1) and (2). Further, peroxide particles are formed in accordance
with step (2) and then oxygen is desorbed from the catalytic surface in step (3). The
Ozone Decomposition on the Surface of Metal Oxide Catalyst 159

finding that the peroxide species could not be formed from molecular oxygen at any
conditions shows the irreversibility of step (3).
The FT-IR spectra of the catalyst before and after ozone decomposition are
shown in Figure 11.8. The two similar spectra indicate that the catalyst does not
change practically during the reaction. A broad band at 3415–3425 cm−1 and also the
band at 1410–1430 cm−1 are associated with the vibrations of water molecules.15,24
The intensive bands at 515–530 cm−1 in accordance with literature25 were assigned
to the stretching vibration of the surface metal–oxygen bond.

FIGURE 11.8  TPR of MnOx/CuO/NiO catalyst supported on cement.

The FT-IR spectra of cement–oxide catalyst after dry ozone decomposition (a)
and after humid ozone decomposition (b) are presented in Figures 11.9 and 11.10.
The spectra are almost identical, showing that the catalyst structure is not altered
during the humid catalytic reaction. The broad adsorption band at 3430 cm−1 appears
from the stretching vibration of hydrogen-bonded hydroxyl groups.15 The adsorp-
tion band at 1635 cm−1 is due to vibrations of water molecules.14 The intensive band
at 520–530 cm−1 appears at higher manganese concentrations and, in accordance
with literature, can be attributed to well-defined Mn2O3 phase.22
160 Process Advancement in Chemistry and Chemical Engineering Research

FIGURE 11.9  FT-IR spectra of MnOx/CuO/NiO catalytic samples obtained before ozone
decomposition (a) and after ozone decomposition for 8 h (b).

FIGURE 11.10  FT-IR spectra of cement-oxide catalyst after dry ozone decomposition (a)
and after humid ozone decomposition (b).
Ozone Decomposition on the Surface of Metal Oxide Catalyst 161

11.5 CONCLUSION
1. The catalyst based on MnOx/CuO/NiO has high efficiency in the reaction of
ozone decomposition both at dry and wet conditions.
2. The catalyst work is stable and its activity does not change dramatically by
varying temperature, O3/O2 flow rate, and humidity.
3. XRD analysis has proven to be a useful tool for the identification of all met-
al oxide phases in catalyst mixture. The temperature-programmed reduction
of the catalyst denotes its high reducibility.
4. The FT-IR spectral band at 526 cm−1 shows that the catalyst stays unchange-
able during the ozone decomposition for about 8 h.
5. The FT-IR spectra after humid ozone decomposition indicates that even af-
ter decomposing ozone in humid conditions, the catalyst structure does not
change practically during the reaction.

KEYWORDS

•• ozone
•• catalyst
•• decomposition
•• synthesis
•• kinetics
•• mechanism

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2. Heisig, C.; Zhang, W.; Oyama ,S. T. Decomposition of Ozone using Carbon Supported Metal
Oxide Catalysts. Appl. Catal. B: Environ. 1997, 14, 117.
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Fibrous-Material-Supported Base Catalysts of Ozone Decomposition. Micro. Meso. Mater.
2001, 43, 153.
4. Radhakrishnan, R.; Oyama, S. T.; Ohminami, Y.; Asakura, K. Structure of MnOx/Al2O3 Cata-
lyst: A Study Using EXAFS, In Situ Laser Raman spectroscopy and Ab Initio Calculations. J.
Phys. Chem. 2001, 105, p 9067.
5. Radhakrishnan, R.; Oyama, S. T.; Chen, J.; Asakura, A. Electron Transfer Effects in Ozone
Decomposition on Supported Manganese Oxide. J. Phys. Chem. B. 2001, 105 (19), 4245.
6. Li, W.; Gibbs, G. V.; Oyama, S. T. Mechanism of Ozone Decomposition on Manganese Ox-
ide: 1. In situ Laser Raman Spectroscopy and ab initio Molecular Orbital Calculations. J. Am.
Chem. Soc. 1998, 120, 9041.
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7. Li, W.; Oyama, S. T. The Mechanism of Ozone Decomposition on Manganese Oxide: 2.

Steady-state and Transient Kinetic Studies. J. Am. Chem. Soc. 1998, 120, 9047.
8. Dhandapani, B.; Oyama, S. T. Gas Phase Ozone Decomposition Catalysts. J. Appl. Catal. B:
Environ. 1997, 11, 129.
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10. Einaga, H.; Futamura, C. S. Comparative Study on the Catalytic Activities of Alumina-sup-
ported Metal Oxides for Oxidation of Benzene and Cyclohexane with Ozone. React. Kinet.
Catal. Lett. 2004, 81, 121.
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Gen. 2006, 298, 109.
14. Stoyanova, M.; Konova, P.; Nikolov, P.; Naydenov, A.; Christoskova, S. T.; Mehandjiev, D.
Alumina-Supported Nickel Oxide for Ozone Decomposition and Catalytic Ozonation of CO
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CHAPTER 12

SYNTHESIS OF O-INCLUDING
COMPOUNDS BY CATALYTIC
CONVERSATION OF OLEFINS
G. Z. RASKILDINA1, N. G. GRIGOR’EVA2, B. I. KUTEPOV2,
S. S. ZLOTSKY1, and G. E. ZAIKOV3
1
Ufa State Petroleum Technological University, 1 Kosmonavtov Str.,450062 Ufa,
Russia; Phone (347) 2420854. E-mail: [email protected]
2
Institute of Petrochemistry and Catalysis of RAS, 141 pr. Oktyabria,
450075 Ufa, Russia
3
N. M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, 4,
Kosygin str., Moscow 119334, Russian Federation. E-mail: [email protected]

CONTENTS
Abstarct..................................................................................................................164
12.1 Introduction..................................................................................................164
12.2 Results and Discussion................................................................................164
12.3 Experimental................................................................................................168
12.4 Conclusion...................................................................................................173
Keywords...............................................................................................................174
References..............................................................................................................174
164 Process Advancement in Chemistry and Chemical Engineering Research

ABSTARCT
By studying the reactions of hydratation of norbornene and 2-vinyl-2-methil-gem-
dichlorocyclopropane and the reactions of styrene and norbornene with different
alcohols and carbonic acids in presence of heterogenic catalyst, it was found that
the selected zeolite H-Beta is active and is selective catalyst for these reactions. Al-
cohol, ethers, esters, and diesters of norbornene have exo-configuration. It has been
established that reaction of norbornene with diols, catalyzing by zeolite Beta, leads
to the formation of esters, which did not find before.

12.1 INTRODUCTION
We have been investigating the reactions of commercially available alkenes (nor-
bornene and 2-vinyl-2-methil-gem-dichlorocyclopropane) with water in the pres-
ence of zeolite catalyst H-Beta, which is successfully used in petrochemical pro-
cesses such as alkylation, isomerization, and so on.1,2 The results of this reactions
are formation of corresponding alcohols. It was determined that norbornene is hy-
drated easier (T = 10°C, under atmospheric pressure) than 2-vinyl-2-methil-gem-
dichlorocyclopropane (T = 150°C, 6 bar gauge autoclave pressure). The results have
reported that the heterogeneous catalytic joining of water to olefins is of interest,
being an effective and cheap method for obtaining corresponding alcohols. Further-
more, we investigated additional reaction of alcohols and ethers to norbornene and
styrene. Addition of O-including compounds to the multiple carbon–carbon bonds
in presence of homogeneous and heterogeneous catalysts finds a wide application in
synthesis of ethers and esters.3 The use of homogeneous (mineral acids) and hetero-
geneous (cationite) catalysts has some drawbacks and do not provide required high
yields and selectivity of products.

12.2  RESULTS AND DISCUSSION

The alcohols obtained by hydratation of olefins is widespread in petrochemical
synthesis.4–6 Recently, hydratation over mineral (sulfuric, phosphoric) and organic
(toluene sulfonic) acids and over a cationite KU-2-8 in H+-form was shown.7–10
We investigated the hydratation of model alkenes (norbornene 2 and 2-vinyl-
2-methil-gem-dichlorocyclopropane 3 over zeolite catalyst H-Beta, which is widely
used on industrial scale.8–10
The corresponding alcohols (4, 5) are obtained at 10°С (under atmospheric pres-
sure) in water solvent. Conversion of more active norbornene 2 is 90% for 2 h (yield
of alcohol is 50%), while less active 2-vinyl-2-methil-gem-dichlorocyclopropane 3
gives alcohol 5 (yield 24%) in an autoclave at 150°С, 6 bar gauge autoclave pressure
for 4 h is shown in (Table 12.1) (Scheme 12.1).
Synthesis of O-Including Compounds by Catalytic 165

TABLE 12.1  The Interaction of Olefins 2, 3 with Water 1 (Molar Ratio Olefins:Water =
1:24; 20 wt% Catalyst).
Reagents Temperature (°C) Time (h) Ка, % Selectivity (%)
2 10 2 90 4 (50)
1 80 24 26 5 (24)
3
150* 2 48 5 (25)
К —conversion of olefin.
a а

*Autoclave.
b

SCHEME 12.1  Hydratation of olefins.

In the present work, we found (Scheme 12.2) that monohydric alcohols (7–9) of
various structures (butyl, allylic, benzyl) are connected to styrene (6) and norborn-
ene (2) selectively with formation of corresponding ethers (10–15).

SCHEME 12.2  Formation of ethers (10–15) by reaction of alcohols and olefins 2, 6.

166 Process Advancement in Chemistry and Chemical Engineering Research

In the studied conditions (Table 12.2), there is total conversion of olefin; and
selectivity of formation of target ethers is 85% more, which is weakly dependent on
the structure of reagents.

TABLE 12.2  Reaction of Olefins 6, 2 with Alcohols 7–9 in Presence Zeolite H-Beta (Molar
Ratio Olefin: Alcohol = 1:3, 20 wt% Catalyst, Т=80°С, 5 h).
Olefin Alcohol Selectivity, (%)

6 7 10 (92)

2 7 13 (93)

6 8 11 (89)

2 8 14 (90)

6 9 12 (92)

2 9 15 (95)

In the case reaction of diols (16, 17) with norbornene, the reaction proceeds by
consistent formation of mono- (18, 19) and diethers (20, 21) in presence of zeolite
H-Beta (Scheme 12.3).

SCHEME 12.3  Formation of mono- and diethers of norbornene over zeolite H-Beta.

By increasing the temperature from 50 to 80°С, conversion of norbornene 2

changes slightly. However, selectivity of diethers’ formation increases from 4 to
32%. Moreover, increasing the molar ratio olefin:diol from 1:3 to 3:1, selectivity of
diethers’ formation increases more than twice (Table 12.3).
Synthesis of O-Including Compounds by Catalytic 167

TABLE 12.3  Reaction of Norbornene with Diols 16, 17 (Molar Ratio 2:diol = А:В, 20 wt.%
Catalyst H-Beta, 5 h).
Selectivity, (%)
Diol А:В T, °C
Monoether Diether
50 18 (92) 19 (4)
16 1:3 60 18 (84) 19 (12)
80 18 (58) 19 (32)
3:1 20 (25) 21 (68)
17 1:1 80 20 (46) 21 (41)
1:3 20 (60) 21 (30)

In the studied conditions, activities of ethylene glycol (16) and cis-2-butene-1,4-

diol (17) are similar. Bicyclic olefin 2 reacts quantitatively with monohydric acids
(22–25) producing appropriate esters. These yields are 80–99% (a four-fold molar
excess of acid) and depend on identity of acids (Scheme 12.4).

SCHEME 12.4  Formation of esters (26–29) by reacting monobasic carboxylic acids (22–
25) with norbornene 2.

At the same time, judging from yield of monoethers, monochloracetic 24, and
methacrylic 25 acids are six times lesser active than acetic acid 22.
The reaction of olefin 2 and dicarbonic acids is going with the formation of
mono- and diethers appropriately (Scheme 12.5).
168 Process Advancement in Chemistry and Chemical Engineering Research

SCHEME 12.5  Formation esters (33–35) by react monocarbonic acids (30–32) with
norbornene 2.

Spatial structure of diesters of norbornene (36–38) identified by methods of

homo- (СOSY, NOESY) and heteronuclear (HSQC, HMBC) two-dimensional 1Н,
13
С NMR spectroscopy. So, in 13С NMR spectra of target esters (36–38), signals
of atoms С-7 of bicyclic fragment are situated in the range of 35.6–36.2 ppm area,
indicating that exo-configuration is because signals endo-isomers are located in the
weaker field (~40 ppm area).
Exo–exo-configuration of dibicyclo[2.2.1]hept-2-yl diester of malonic acid 37
is confirmed by interaction of protons of atoms С-2 and С-12 with protons of atoms
С-6 and С-16. In case of endo– endo isomer, protons of atoms С-2 and С-12 corre-
late with protons of atoms С-7 and С-17, that is not found in our case. Esters by exo-,
endo-configuration are not have in the products of reactions from NMR-spectrums.

12.3 EXPERIMENTAL
An HRGS 5300 Mega Series “Carlo Erba” chromatograph with a flame ionization
detector was used for the qualitative and quantitative analysis of starting material
and reaction products. The chromatograph was equipped with a thermo-conduc-
tivity were registered using the «Bruker AVANCE-400» spectrometer (400.13 and
100.62 MHz, respectively) in CDCl3 solvent, where benzene-d6, toluene-d8 were
used as internal standards. High-resolution mass spectra were measured on a Fisons
Trio 1000 instrument, whose chromatograph was equipped with a DB-560 quarts
column (50 m); the temperature of the column was increased from 50 to 320°C with
a programmed heating rate of 4°C min−1; the electron impact (70 eV).
In order to carry out the reactions, zeolite BEA (Beta) (mole ratio SiO2/Al2O3 =
18.0), synthesized in the JSC “Angarsk Catalysts and Organic Synthesis” in NH4-
form, was used as catalyst. Zeolite Beta was converted H-form by heated in air at
540°С for 3 h. Before experiments, the catalyst sample was dried in air for 4 h at
350°С.

12.3.1 CATALYST
Synthesis of O-Including Compounds by Catalytic 169

Zeolite NH4-Beta was produced by the public corporation Angarsk Factory of Cata-
lysts and Organic Synthesis. Zeolite NH4-Beta was transferred into H-Beta form by
calcinations at 540°C for 4 h before all experiments.

12.3.2  THE INTERACTION OF NORBORNENE 2 WITH WATER

OVER H-BETA ZEOLITE
The zeolite H-Beta (0.28 g) was added to a mixture of norbornene 2 (1.22 g, 0.013
mmol) and water 1 (50 g, 3.13 mmol) at 10°C and stirred for 2 h. After the catalyst
was filtered and the reaction mass was extracted with ether, the latter was removed
at the reduced pressure. The alcohol 4 (72°С/20 mm Hg) was isolated under vacu-
um. The mixture of exo-2-norborneol 4 and di-norbornyl ether of this mixture was
(% w/w): 50/50% accordingly. Compounds were identified by NMR spectroscopy.

EXO-2-NORBORNEOL (4)
1
H NMR, δ: 1.02–1.05 (m, 3Н, C6Ha, C7Ha, C5Ha), 1.12–1.18 (m, 2 H, C3Ha, C5Hb),
1.36–1.51 (m, 2Н, C7Hb, C6Hb), 1.62–1.67 (m, 1H, C3Hb), 2.12–2.35 (m, 2Н, C4H,
C1H), 3.68 (d, 1Н, C2H). 13C NMR, δ: 24.39 C6, 29.27 C5, 34.38 C7, 35.40 C4, 42.37
C3, 44.34 C1, 74.95 C2. IR spectrum: 2851–2954 (С–Н, СН2), 3437 (–ОН); m/z:
122 М+ (30), 107 (100), 79 (93), 77 (52), 43 (30), 51 (21), 105 (10), 50 (10), 80 (7);
Kovaẻ index Ik 1065.

12.3.3  THE INTERACTION OF 2-VINYL-2-METHIL-GEM-

DICHLOROCYCLOPROPANE 3 WITH WATER OVER H-BETA
ZEOLITE
The zeolite H-Beta (0.43 g) was added to a mixture of 2-vinyl-2-methil-gem-
dichlorocyclopropane 3 (1.96 g, 0.013 mmol) and water 1 (50 g, 3.13 mmol) at
80°C/150°C* and stirred for 24/2*h. After the catalyst was filtered and the reac-
tion mass was extracted with ether, the latter was removed at the reduced pres-
sure. The alcohol 5 (95°С/25 mm Hg) was isolated under vacuum. The mixture of
1,1-dichloro-2-methyl-2-(hydroxyethyl-1)cyclopropane 5 of this mixture was 24%.
Compound was identified by NMR spectroscopy.
After the completion of the reaction, mass was separated from the catalyst by
filtration. The conversion of initial olefins and the quantitative composition of the
alcohol fraction were determined using gas–liquid chromatography (GLC). The
chemical stricter of alcohols (4, 5) was established by means of GC/MS spectrom-
etry and NMR spectroscopy.
170 Process Advancement in Chemistry and Chemical Engineering Research

1,1-DICHLORO-2-METHYL-2-(HYDROXYETHYL-1)CYCLOPROPANE
(5)
1
H NMR, δ: 1.23–1.24 2H (d, cyclC3H2), 1.42 3H (s, C5H3), 1.70 1H (s, ОH), 1.92
3Н (s, C6H3), 4.01–4.06 1Н (m, C4H 2J = 12.8, 3J = 6). 13C NMR, δ: 20.71 C6,
23.39 C5, 34.66 C3, 44.70 C2, 66.39 C4, 77.26 C1. IR spectrum: 2877-2972 (С–Н,
СН2), 3418 (-ОН); m/z: 169 М+ (0.6), 45 (100), 124/126/128 (35/22/4), 87/89/91
(6/35/11), 53 (14), 53 (14), 43 (13), 51 (11). Kovaẻ index Ik = 1123.
* Autoclave

12.3.4  METHOD OF REACTION OF OLEFINS (2) WITH

ALCOHOLS (7–9)
A mixture of 0.255 M alcohol 7 (or 0.255 M alcohol 8, or 0.255 M alcohols 9) and
0.085 M norbornene 2, 20 wt.% catalyst Н-Beta was carried out at 80°С and mixed
intensively for 5 h. The reaction mass was separated from the catalyst by filter-
ing the reaction termination and unreacted alcohol was removed at a low pressure.
Ethers were isolated by vacuum distillation for calibration.
1-n-butyl-1-phenylethan (10): b.p. 95–96°С (10 mm Hg). 1H-NMR (CDCl3, d
ppm, JHz): 0.86 (t, 3H, CH3), 1.33 (m, 2H, CH2), 1.35 (m, 2H, CH2), 1.45 (d, 3H,
CH3), 3.42 (q, 2H, OCH2), 4.30 (q, 1H, CH), 7.3 (m, 5H, ArH). 13С-NMR (CDCl3,
d ppm): 13.78 C6, 18.90 C5, 21.15 C2, 32.65 C4, 69.75 C3, 72.86 C1, 124.97–127.04
Ar, 143.03 C1’.
1-allyloxy-1-phenylethan (11): b.p. 68°С (5 mm Hg): 1H-NMR (CDCl3, d ppm,
JHz): 1.5 (d, 3Н, CH3), 3.85 (dddd., 1Н, СНа, 2J 12.8, 3J 5.8), 3.94 (dddd., 1H, CHb,
2
J 12.8, 3J 5.2), 4.51 (dd., 1H, CH, 3J 6.4), 5.19 (dd., 1H, CHa, 2J 1.6, 3J 10.4), 5.29
(dd., 1H, CHb, 2J 1.6, 3J 17.2), 5.95 (dddd., 1H, CH, 3J 5.2, 3J 5.8, 3J 10.4, 3J 17.2),
7.28–7.40 (m., 5H, Ar).
1-cyclohexyloxy-1-phenylethan (12): b.p. 91–92°С (9 mm Hg): 1H-NMR
(CDCl3, d ppm, JHz): 1.46 (d, 3H, CH3), 1.12–1.20 (m, 6H, CH2), 1.78–1.94 (m,
4H, CH2), 3.40 (m, 1H, CH), 4.64 (q, 1H, ArCH), 7.23–7.33 (m, 5H, ArH).
Exo-2-(butoxy)bicyclo[2.2.1]heptane (13): b.p. 77°С (27 mm Hg). 1H-NMR
(CDCl3, d ppm, JHz): 0.91 (m, 3H, CH3), 0.96–1.07 (m, 3H, CH2), 1.32–1.41 (m,
3H, CH2), 1.46–1.55 (m, 4H, CH2), 2.20 (s, 1H, CH), 2.29 (d, 1Н, CH, 2J = 4),
3.24–3.40 (m, 1H, CH), 3.24–3.40 (m, 2H, CH2). MS (70eV), m/z (J., %): 168 [М-
1]+ (≤1), 94 (100); 66 (74); 79 (65); 67 (56), 41 (49), 95 (39), 57 (28), 83 (19), 55
(17), 68 (16), 56 (13), 112 (12).
2-(alliloxy)bicyclo[2.2.1]heptane (14): b.p. 78°C (10 mm Hg). 1H-NMR
(CDCl3, d ppm, JHz): 0.95–1.12 (m, 3H, CH2), 1.37–1.60 (m, 5H, CH2), 2.25 (s,
1H, CH), 2.33 (d, 1H, CH), 3.89–4.00 (m, 2H, CH2), 5.10–5.18 (d, 1H, CHa, 2J =
Synthesis of O-Including Compounds by Catalytic 171

1.6, 3J = 10.4), 5.22–5.32 (d, 1H, CHb, 2J = 1.6, 3J = 17.2), 5.83–5.99 (m, 1Н, СН).
MS (70eV), m/z (J., %): 152 [М-1]+ (1), 67 (100); 41 (56); 94 (51); 95 (41), 66 (34),
79 (29), 55 (27), 93 (23), 91 (11), 81 (11), 77 (11).
2-(benzyloxy)bicyclo[2.2.1]heptane (15): b.p. 70°С (20 mm Hg). 1H-NMR
(CDCl3, d ppm, JHz): 0.92–1.05 (m, 3H, CH2), 1.25–1.40 (m, 2H, CH2), 1.51–1.56
(m, 3H, CH2), 2.19 (s, 1H, CH), 2.28 (s, 1Н, CH), 3.64–4.51 (m, 1H, CH), 3.64–4.51
(m, 2H, CH2), 7.00–7.05 (m, 5H, Аr).
2-(bicyclo[2.2.1]heptyl-2-oxy)ethanol (18): b.p. 130°С (10 mm Hg). 1H-NMR
(CDCl3, d ppm, JHz): 0.95–1.10 (m, 3H, CH2), 1.38–1.59 (m, 5H, CH2), 2.23 (m,
1H, CH), 2.33 (m, 1H, CH), 2.55 (1H, OH), 3.39 (d, 1H, CH), 3.49–3.57 (m, 2H,
CH2), 3.70–3.77 (m, 2H, CH2). 13С–NMR (CDCl3, d ppm): 24.61 C6, 28.55 C5, 34.77
C7, 35.17 C4, 39.56 C3, 40.36 C1, 63.71 C9, 67.66 C8, 83.0 C2. MS (70eV), m/z (J.,
%): 156 [М-1]+ (2), 95 (100); 67 (49); 155 (19), 111 (18), 94 (16), 94 (15), 66 (15),
41 (15).
2,2’-[ethane-1,2-diylbis(oxy)]bicyclo[2.2.1]heptane (19): b.p. 158°С (5 mm
Hg). 1H-NMR (CDCl3, d ppm, JHz): 0.86–1.26 (m, 8H, CH2), 1.32–1.40 (m, 8H,
CH2), 1.55–1.58 (m, 2H, CH2), 1.63 (m, 1H, CH), 1.73 (m, 2H, CH2), 2.04 (m, 2H,
CH, CH), 3.20 (m, 2H, CH2), 3.42 (m, 2H, CH2), 3.57 (d, 1H, CH). MS (70eV), m/z
(J., %): 250 [М-1]+ (1), 95 (100); 94 (95); 66 (87), 79 (77), 67 (52), 45 (47), 41 (33),
55 (19), 57 (18); 83 (17); 44 (16); 77 (13); 65 (13); 43 (14); 53 (11).
Exo-4-(bicyclo[2.2.1]hept-2-yloxy)but-2-en-1-ol (20): b.p. 141°С (2 mm Hg).
1
H-NMR (CDCl3, d ppm, JHz): 0.95–1.03 (m, 2H, C6Hb, C3Ha), 1.03–1.14 (m, 2Н,
C6Ha, C3Hb), 1.37–1.48 (m, 1H, C5Hb), 1.50–1.60 (m, 1Н, C5Ha), 2.17 (s, 1H, C1H),
2.25 (s, 1Н, –ОН), 2.34 (d, 1H, C4H), 3.40 (d, 1H, C2H), 3.95–4.09 (m, 1H, C8Ha),
4.19(m, 1H, C8Hb, 2J = 6.4, 3J = 18.8), 4.22 (d, 2H, C11Ha, C11Hb, 2J = 4.4 3J = 16.8),
5.67–5.75 (m, 1H, C9H), 5.76–5.85 (m, 1Н, C10H). 13С-NMR (CDCl3, d ppm): 24.58
C6, 28.40 C5, 35.14 C4, 39.51 C3, 40.28 C1, 58.53 C11, 64.03 C8, 82.67 C2, 128.82 C10,
131.82 C9. MS (70eV), m/z (J., %): 182 [М-1]+ (2), 164 (7), 138 (12), 109 (12), 95
(100), 94 (22), 81(18), 79 (46), 77 (10), 71 (17), 70 (27), 67 (90), 66 (40), 57 (10),
55 (27), 53 (18), 43 (40).
Exo-exo-[(2Z)-but-2-en-1,4-diylbis(oxy)]bisbicyclo[2.2.1]heptane (21): b.p.
183°С (2 mm Hg). 1H-NMR (CDCl3, d ppm, JHz): 0.97–1.12 (m, 6H, C6Ha, C14Ha,
C5Ha, C17Ha, C7Ha, C18Ha), 1.34–1.48 (m, 6H, C3Ha, C14Ha, C5Hb, C16Hb, C6Hb, C17Hb),
1.49–1.58 (m, 4Н, C7Hb, C18Hb, C3Hb, C14Hb), 2.23 (s, 2H, C4H, C15H), 2.30–2.34
(d, 2H, C1H, C12H), 3.35–3.40 (dd, 2H, C2H, C13H), 3.95–4.05 (m, 2H, C8Ha, C8Hb),
4.09 (dd, 1Н, С11Нa), 4.19 (dd, 1Н, С11Нb), 5.63–5.74 (m, 1H, C10H), 5.75–5.88 (m,
1H, C9H). 13С-NMR (CDCl3, d ppm): 23.75 C6, 27.62 C5, 33.93 C7, 34.27 C4, 38.71
C3, 39.42 C1, 57.54 C11, 63.04 C8, 81.25 C2, 129.41 C10, 131.96 C9. MS (70eV), m/z
(J., %): 276 [М-1]+ (<1), 164 (6), 96 (10), 95 (100), 93 (6), 79 (6), 70 (10), 67 (42),
41 (13).
172 Process Advancement in Chemistry and Chemical Engineering Research

12.3.5  METHOD OF REACTION OF NORBORNENE (2) WITH

MONOCARBOXYLIC ACIDS (22-25)
A mixture of 0.34 M acetic acid 22 (or 0.34 M n-butyric acid 23, or 0.34 M chlorace-
tic acid 24, or 0.34 M methacrylic acid 25), 0.085 M of norbornene, 20 wt.% catalyst
Н-Beta was carried out at 90°С and mixed intensively for 4 h. For homogenization
of initial compounds (24, 25), nonane was used as a solvent. The reaction mass was
separated from the catalyst by filtering after the reaction termination and unreacted
acid was removed at a low pressure. Esters were isolated by vacuum distillation for
calibration.
Exo-bicyclo[2.2.1]hept-2-yl ester of acetic acid (26): b.p. 95°С (20 mm Hg).
1
H-NMR (CDCl3, d ppm, JHz): 1.08–1.18 (m, 4Н, C3Ha, C6Ha, C6Hb, C3Hb), 1.42–
1.54 (m, 3Н, C4Hb, C7Ha, C7Hb), 1.73 (m, 1H, C4Ha), 2.02 (s, 3Н, C9H3), 2.30 (m,
2H, C2H, C5H), 4.61 (d, 1H, C1H). 13С-NMR (CDCl3, d ppm): 21.42 C9, 24.33 C3,
28.13 C4, 35.24 C5, 35.37 C7, 39.60 C6, 41.40 С2, 77.60 C1, 170.82 C8. MS (70eV),
m/z (J., %): [M-1].+ 154 (6), 43 (100), 66/67 (70/68), 94/95 (68/52), 79 (65), 111/112
(64/51), 41 (53), 71 (52).
Exo-bicyclo[2.2.1]hept-2-yl ester of n-butyric acid (27): b.p. 106°С (10 mm
Hg). 1H-NMR (CDCl3, d ppm, JHz): 0.96 3 (t, 3Н, C11H3), 1.17–1.20 (m, 3Н, C3Ha,
C7Ha, C4Ha), 1.39–1.49 (m, 2 H, C6Ha, C4Hb), 1.50–1.58 (m, 2Н, C7Hb, C3Hb), 1.65
(m, 2H, C10H2), 1.69–1.78 (m, 1H, C6Hb), 2.25 (t, 2Н, C9Ha, C9Hb), 2.27–2.32 (m,
2Н, C5H, C2H), 4.62 (d, 1Н, C1H). 13С-NMR (CDCl3, d ppm): 13.66 C11, 18.54 C10,
24.31 C3, 28.85 C4, 35.26 C7, 35.38 C9, 36.59 C5, 39.65 C6, 41.45 С2, 77.29 C1,
173.40 C8. MS (70eV), m/z (J., %): [M-1]+ 182 (2), 71 (100), 95 (52), 43 (40), 139
(31), 111 (30), 154 (15), 79 (12).
Exo-bicyclo[2.2.1]hept-2-yl ester of chloracetic acid (28): b.p. 95°С (6 mm
Hg). 1H-NMR (CDCl3, d ppm, JHz): 1.09–1.22 (m, 3Н, C3Hb, C7Hb, C4Hb), 1.44–
1.57 (m, 4Н, C3Ha, C4Ha, C7Ha, C6Ha), 1.75–1.80 (m, 1H, C6Hb), 2.32 (m, 1Н, C5H),
2.36 (d, 1H, C2H), 4.04 (s, 2H, C9Ha, C9Hb), 4.72 (d, 2Н, C1H). 13С-NMR (CDCl3, d
ppm): 24.13 C6, 28.03 C5, 35.23 C7, 35.35 C4, 39.38 C3, 41.20 C9, 41.39 C1, 79.71 C2,
167.01 С8. MS (70eV), m/z (J., %): [M-1]+ 188 (<1), 66/67/68 (100/78/29), 94/95
(56/64), 77/79 (38/87), 41 (40), 49 (20), 55 (17), 42 (13), 53 (10).
Exo-bicyclo[2.2.1]hept-2-yl ester of methacrylic acid (29): b.p. 90°С (6 mm
Hg). 1H-NMR (CDCl3, d ppm, JHz): 1.12–1.20 (m, 3Н, C3Ha, C4Ha, C7Ha), 1.43–
1.57 (m, 4Н, C3Hb, C4Hb, C6Ha, C7Ha), 1.74–1.79 (m, 1H, C6Hb), 1.93 (s, 3Н, C11H3),
2.31 (m, 1H, C5H), 2.35 (m, 1H, C2H), 4.68 (m, 1H, C1H), 5.52 (s, 1Н, C10Ha), 6.07
(s, 1Н, C10Hb). 13С-NMR (CDCl3, d ppm): 18.26 C11, 24.24 C3, 28.17 C4, 35.33
C7, 35.37 C5, 39.57 C6, 41.45 C2, 77.74 C1, 124.81 С10, 136.90 С9, 167.09 С8. MS
(70eV), m/z (J., %): [M-1]+ 180 (<1), 69 (100), 41 (84), 66 (71), 94 (56), 95 (40), 79
(19), 70 (19), 109 (11), 97 (11), 55 (10), 124 (10), 137 (10).
Synthesis of O-Including Compounds by Catalytic 173

12.3.6  METHOD OF REACTION OF NORBORNENE (2) WITH

DICARBOXYLIC ACIDS (30–32)
A mixture of 0.34 M oxalic acid 30 (or 0.34 M malonic acid 31, or 0.34 M succinic
acid 32), 0.085 M of norbornene, 20 wt.% catalyst Н-Beta was carried out 90°С and
mixed intensively for 4 h. For homogenization of initial compounds (30–32) nonane
was used as a solvent. The reaction mass was separated from the catalyst by filter-
ing after the reaction termination and unreacted acid was removed at a low pressure.
Esters were isolated by vacuum distillation for calibration.
The resulting physicochemical properties, NMR-spectra, and mass-spectra of
compounds 33–35 correspond to literature data.11
Exo-dibicyclo[2.2.1]hept-2-yl ester of oxalic acid (36): b.p. 122°С (7 mm Hg).
1
H-NMR (CDCl3, d ppm, JHz): 1.12–1.23 (m, 6H, C6Ha, C5Ha, С7Нa, C15Ha, C14Ha,
C16Ha), 1.44–1.62 (m, 8H, C6Hb, C5Hb, C3Ha, C7Hb, C15Hb, C14Hb, C12Ha, C16Hb),
1.76–1.82 (dddd, 2Н, C3Hb, C12Hb), 2.33 (s, 2H, C4H, С13Н), 2.43 (d, 2H, C1H,
C10H), 4.75 (d, 2H, C2H, C11H). 13С-NMR (CDCl3, d ppm): 24.11 C3, C15, 28.03 C5,
C14, 35.29 C7, C16, 35.37 C4, C13, 39.26 C3,C12, 41.30 C1, C10, 80.46 C2, C11, 158.05
C8, C9. MS (70eV), m/z (J., %): [M-1]+ 278 (0.1), 95/96 (100/8), 66/67/68 (8/24/2),
41 (9), 77/79 (3/4), 93 (4), 53/55 (2/4), 65 (3).
Exo-dibicyclo[2.2.1]hept-2-yl ester of malonic acid (37): b.p. 172°С (2 mm
Hg). 1H-NMR (CDCl3, d ppm, JHz): 1.08–1.19 (m, 6H, C5Ha, С15Нa, C6Ha, C16Ha,
C7Ha, C17Ha), 1.43–1.59 (m, 8H, C3Ha, C13Ha, C7Hb, C17Hb, C5Hb, C15Hb, C6Hb, C16Hb),
1.72–1.77 (m, 2Н, C3Hb, C13Hb), 2.30 (s, 2H, C4H, C14H), 2.35 (s, 2H, C1H, C11H),
3.29 (s, 2H, C9Ha, C9Hb), 4.67 (d, 2H, C2H, C12H). 13С-NMR (CDCl3, d ppm): 24.18
C6, C16, 28.10 C5, C15, 35.24 C7, C17, 35.34 C4, C14, 39.34 C3, C13, 41.33 C1, C11, 42.26
C9, 78.79 C2, C12, 166.34 C8, C10. MS (70eV), m/z (J., %): [M-1]+ 292 (0.2), 95 (100),
67 (13), 111 (10), 199 (8).
Exo-dibicyclo[2.2.1]hept-2-yl ester of succinic acid (38)L: b.p. 180°С (1
mm Hg). 1H-NMR (CDCl3, d ppm, JHz): 1.12–1.24 (m, 6H, C7Ha, С5Нa, C16Ha,
C6Ha, C17Ha, C18Ha), 1.42–1.53 (m, 8H, C14Ha, C3Ha, C5Hb, C16Hb, C7Ha, C18Hb, C6Hb,
C17Hb), 1.70–1.75 (m, 2Н, C3Hb, C14Hb), 2.29 (m, 4H, C4H, C15H, С1Н, C12H), 2.57
(m, 4H, C9Ha, C9Hb, C10Ha, C10Hb), 4.63 (d, 2H, C2H, C13H). 13С-NMR (CDCl3, d
ppm): 24.25 C6, C17, 28.13 C5, C16, 29.58 C9, C10, 35.25 C7, C18, 35.36 C4,C15, 39.52
C3, C14, 41.39 C1, C12, 77.89 C2, C13, 171.93 C8, C11. MS (70eV), m/z (J., %): [M-1]+
306 (0.1), 95 (100), 67 (24), 195 (18), 55 (9), 79 (9), 111 (9), 213 (9), 41 (7), 162 (7).

12.4 CONCLUSION
The obtained results indicate that the zeolite H-Beta is active and selective catalyst
for synthesis of alcohols, ethers, and esters from olefins with acids and alcohols.
 It should be noted that offered methods are simple compared to methods based
on the use of traditional acid catalysts. In this case, products of reactions are sepa-
rated from the catalyst by filtering and zeolite H-Beta can be recovered for use later.
Besides high activity and selectivity, zeolite catalyst H-Beta makes it possible to
obtain new structure compounds, which were not obtained based on homogeneous
acidic catalysts.12

KEYWORDS

•• heterogenic catalyst
•• norbornene
•• styrene
•• 2-vinyl-2-methil-gem-dichlorocyclopropane
•• zeolite H-Beta
•• alcohols
•• ethers
•• esters
•• diesters

REFERENCES
1. Valencia, S.; Corma, A.; Cambor, M. Micropor. Mesopor. Mat. 1998, 25, 59–74.
2. Minchayev, C. M., Kondratyev, D. A. Uspehi Khimii («Successes of Chemistry», in Rus.), 1983;
52(12), 21–73.
3. Reutov, O. A.; Kurts, A. L.; Butin, K. P. Organic Chemistry (in Rus.). Part 2, 1999; 624.
4. Patent 2,345,573, US Herman A. Bruson http://www.freepatentsonline.com/2345573.html.
1944.- #4.
5. Yang, X.; Chatterjee, S.; Zhang, Z.; Zhu, X.; and Charles U. P. Jr. Ind. Eng. Chem. Res. 2010,
49, 2003.
6. Brown, H.; Kawakami, J. J. Amer. Chem. Soc. 1990, 92, 1970.
7. Butlerov, A. M. Selected Works in Organic Chemistry; Publishing House of the Academy of
Sciences of the USSR: Moscow, RU, 1951; p 333.
8. Azinger, Ph. Chemistry and Technology of Monoolefins; Gostoptehidat: Moscow, RU, 1960;
p.467.
9. Sumio, A. Chem. Eng. 1973, 56, 80.
10. Menjajlo, A. T. Synthesis of Alcohols and Organic Compounds from Oils. Tr. NIISa. Goschi-
mizdat: Moscow, Ru, 1960; pp 226.
11. Mamedov, M. K. J. Org. Chem. (in Rus.), 2006, 42 (8), 1159–1162.
12. Gasanov, A. G.; Nagiev, A. V. J. Org. Chem. (in Rus.), 1994, 30 (5), 707–709.
CHAPTER 13

STRESS BIREFRINGENCE OF HIGHLY

CROSS-LINKED POLYMERS OF
OPTOELECTRONIC APPLICATION IN
THE CONTEXT OF HEREDITY THEORY
N. V. ULITIN1, I. I. NASYROV1, R. R. NABIEV1, D. A. SHIYAN1,
N. K. NURIEV1, G. E. ZAIKOV2
1
Kazan National Research Technological University, 68 Karl Marx Street, 420015
Kazan, Republic of Tatarstan, Russian Federation. Fax: +7 (843) 231-41-56.
E-mail: [email protected]
2
N. M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, 4,
Kosygina st., Moscow 119334, Russian Federation. Fax: +7(499)137-41-01.
E-mail: [email protected]

CONTENTS
Abstract..................................................................................................................176
13.1 Introduction..................................................................................................176
13.2 Mathematical Model....................................................................................176
13.3 Experimental Part.........................................................................................179
13.4 Modeling of Topological Structure of Experimental Objects......................181
13.5 Theoretical Assessment of Constants for Stress Birefringence Model.......184
13.6 Conclusion...................................................................................................189
Keywords...............................................................................................................190
References..............................................................................................................190
176 Process Advancement in Chemistry and Chemical Engineering Research

ABSTRACT
Aiming to control by stress birefringence, the radiotransparent fiberglass plastic
products based on highly cross-linked polymer matrices, theoretical regularities
for mathematical description of this property were developed. Computer physical
modeling of topological structure of experimental objects was carried out on epoxy–
amine polymers with different cross-link density taken as an example. And con-
stants of this model were specified. The adequacy of the model was demonstrated
by comparison of the model-calculated against experimental approach to thermal
polarization curves.

13.1 INTRODUCTION
To manufacture protective domes for radar installations, radiotransparent fiberglass
plastics are used, that is, polymer composite materials consisting of highly cross-
linked polymer matrix reinforced by glass fiber. When in use, radiotransparent prod-
ucts are subject to static (in particular, by its own weight) or dynamic loads, and
highly cross-linked polymer matrix demonstrates an effect of stress birefringence.
The actual challenge that arises during application of radiotransparent fiberglass
plastics is reduction of stress birefringence. Therefore, the aim of this work is to
develop a mathematical model for describing stress birefringence of highly cross-
linked polymer matrices in all physical states of the ones (glassy state, rubbery state,
and transition state between them).

13.2  MATHEMATICAL MODEL

We can define relative deformation of polymer solid body of free shape in the form
of tensor as follows1:

1 1
uik = Jτ ik − B∞ pd ik , (13.1)
2 3
where B∞ is balanced bulk creep compliance, (MPa–1); J is relaxation operator of
shear compliance (MPa–1), τik is tensor of shear stress (MPa); p is pressure, which
is compressing any volume element without changing its shape (MPa); δik is Kro-
necker symbol.
Contributions B∞ in uik for highly cross-linked polymer matrices are very small
and are basically ignored.1 If the deformation of cross-linked polymer matrix is not
accompanied by destruction of its chemical structure, then:

J = J ∞ J N , (13.2)
Stress Birefringence of Highly Cross-Linked Polymers 177

where J∞ is balanced shear compliance at the given temperature (MPa–1); JN is a

normalized to 1 relaxation Volterra operator.
In this paper, all the discussions were made for highly cross-linked polymer ma-
trices, whose topological structure is spatially uniform. Highly cross-linked polymer
matrices on supramolecular level of the structure is characterized by micro-hetero-
phasicity: apart from gel fraction formed by globules and their aggregates, micro-
dispersed formations (sol fraction) are also present here, which are formed of linear
and/or branched macromolecules of low molecular weight. Since different topolo-
gies of cross-linked macromolecules forming microgel supramolecular formations
are found in the ones equally often over the entire volume, they are considered
statistically equivalent, and highly cross-linked polymer matrices are considered
spatially uniform, owing to their topological structure. An important experimental
proof of that is only inversely proportional dependence of balanced shear compli-
ance J∞ (MPa–1) verses temperature (T, K):

J ∞ = A∞ T , (13.3)

where A∞ is independent of T constant of rubbery state, K/МPа.

Since relaxation spectrum of shear compliance consists of β- and α-branches1,
therefore, for highly cross-linked polymer matrices with spatially uniform topologi-
cal structure, operator JN is as following:

J N = wJ ,β + (1- wJ ,β ) J N ,a , (13.4)
where wJ,∞ is weighting coefficient, independent of T, and reflecting contribution of
β-transitions in J∞; JN,α is fractional exponential operator connected to distribution
of α-relaxation time LJ,α(θ):
∞
J N,a = ∫ LJ,a (θ )[1 − exp( −t / θ )]d ln θ (13.5)
-∞

In eq13.5, θ is relaxation time, t is current time.

Normalized to 1 α-mode has been described using distribution developed by Yu.
N. Rabotnov2:

LJ ,a (θ ) = sin[π (1- Ξ J ,a )] / [2π {ch[(1- Ξ J ,a ) ln(θ / Θ J ,a )] + cos[π (1- Ξ J ,a )]}] (13.6)

where ΘJ,α is average α-relaxation time; ΞJ,α is independent of T distribution width

(0 ≤ ΞJ,α ≤1).
Operator JN,α in glassy state takes on the value equal to 0, in rubbery state equal
to 1, and in transition state between these physical states it is equal to 0–1. That is
why eqs 13.1 through 13.6 will describe J of highly cross-linked polymer matrices
with spatially uniform topological structure in all their physical states.
178 Process Advancement in Chemistry and Chemical Engineering Research

Stress birefringence was reduced to J, considering that ordered orientation of

solid body molecules2 is occurring by deformational shear. The point of departure
for our discussions was the equation linking dielectric permittivity of the deformed
polymer dielectric with independent components of relative deformation tensor3:

1
ε ik = ε 0d ik + a1γ ik + ( a1 + 3a2 ) ulld ik , (13.7)
3
here ε0 is dielectric permittivity of the nondeformed solid body; γik is deformation
shear tensor; a1, a2 are polarization coefficients; and ull is volumetric compression
deformation tensor.
1
α-branch reflects cooperative mobility of network nodes, which are not partici-
pating in local movements; β-branch is connected with local conformation mobility;
2
this orientation is the purpose of polarization anisotropy.
From eq 13.7, equation of Brewster-Wertheim law can be obtained:

Dn = ξ ∞ Dγ = C∞ Dτ , (13.8)

where Δn is stress birefringence; Δγ and Δτ are differences of main shear deforma-

tions and stresses in the given point; C∞ is balanced electromagnetic susceptibility
(МPа–1) connected with J∞ equation:

C∞ = 0.5ξ ∞ J ∞ , (13.9)

here ξ∞ is balanced elastic coefficient of electromagnetic susceptibility.

Let us introduce the relaxation operators for electromagnetic susceptibility C
(МPа–1) and for elastic coefficient of electromagnetic susceptibility ξ, assuming that
they are connected with J in the form of equation below:

C = 0.5 ξ J (13.10)

The importance of eq 13.10 lies in the fact that we get a result of coincidence of
relaxation spectra ξ and shear module. Operator ξ is as follows:

ξ = ξ∞ ( wξ ,β + (1- wξ ,β )GN ,a ), (13.11)

where wξ,∞ is weighting coefficient, independent of T, and reflecting contribution of
β-transitions in ξ∞; GN,α is fractional exponential operator, reverse to JN,α.
Based on the rule of multiplication of the fractional exponential operators2 from
eq 13.10, we get:

C = C∞ ( wC ,β + ( 1- wC ,β ) J N ,a ) , (13.12)
Stress Birefringence of Highly Cross-Linked Polymers 179

where wC,β is weighting coefficient independent of T and reflecting contribution of

β-transitions in С∞.
The result of eq 13.12 shows coincidence of relaxation spectra J and С, hereby
C, as well as J, will cover all physical states of highly cross-linked polymer matri-
ces. To apply the obtained regularities in practice, we must know the temperature
dependence of α-relaxation time:

a g , T < Tg
( )
lg(Θ J ,a (T ) / Θ J ,a (Tg )) = 40 ( f g / ( f g + a (1- f g )(T - Tg )) -1) , a = 
a ∞ , T > Tg , (13.13)

where Tg is glass transition temperature, K; αg, α∞ are coefficients of thermal expan-

sion in glassy and rubbery states, K–1; fg is fractional free volume at Tg.
Equation 13.13 is obtained analytically from equation below:

lg(Θ J ,a (T ) / Θ J ,a (Tg )) = ( f g/ + 0.025a ∞ (1- f g ) f g  (T - Tg ))-1 - ( f g/ )-1 ,

suggested by Ferry4 to describe relaxation of linear, branched, and lightly cross-
linked polymers at higher than Tg temperatures, taking into account the known tem-
perature function fg of highly cross-linked polymer matrices.5 It is to be noted that
/
value f g = 0.025, which Ferry identified with fractional free volume at Tg, is not
the same in reality, and for highly cross-linked polymer matrices, it is included in
coefficient 40.
So, theoretical regularities of stress birefringence of highly cross-linked poly-
mer matrices, forming under the influence of temperature fields and mechanical
stresses, are fully described by an aggregate of eqs 13.2 through 13.6, 13.8, 13.10
through 13.13. According to these equations, stress birefringence can be assessed
based on parameters such as: Tg, αg, α∞, A∞, ξ∞, wC,∞, wJ,∞, ΘJ,α, and ΞJ,α. In this con-
nection, theoretical and experimental assessment of these values were carried out to
demonstrate adequacy of the introduced theoretical representations and their oper-
ability for evaluation of stress birefringence for highly cross-linked epoxy–amine
polymers at different conditions.

13.3  EXPERIMENTAL PART

13.3.1  EXPERIMENTAL OBJECTS

Experimental objects became highly cross-linked polymer matrices with a various
cross-link density on the basis of diglycidyl ether of bisphenol-A (DGEBA—Fig.
13.1(a)), cured by mixtures of hexylamine (HA—Fig. 13.1(b)) and hexamethyl-
enediamine (HMDA—Fig. 13.1(c)) at a variation of a molar ratio of the ones x = n
(HA)/n (HMDA) from 0 to 2 (step 0.5) taking into account a stoichiometry of epoxy
groups and hydrogen of the amine group.
180 Process Advancement in Chemistry and Chemical Engineering Research

FIGURE 13.1  Initial substances.

Preparation of epoxy–amine compositions: DGEBA and HMDA weighted on

scales METTLER TOLEDO AB304-S/FACT (up to 0.0001 g) and heated to 315 K,
then molt of HMDA and required amount of HA were mixed with DGEBA; then the
mixture was stirred to form a homogeneous mass and was poured into an ampoule
and vacuumized for 1 h in the “freeze–thaw” conditions; ampoule filled with argon
and sealed. Curing conditions: at 293 K for 72 h, at 323 K for 72 h, at 353 K for 72
h, and at 393 K for 72 h (chosen on the basis of the representations set forth in6).

13.3.2  EXPERIMENTS BY PHOTOELASTIC METHOD

One of the methods of experimental determination of stress birefringence is a pho-
toelastic method. The tests of the experimental objects were conducted on the test
facilities7 designed to measure the relative stress birefringence in the center of the
disk and the horizontal diameter relative deformation of the disk. Disc is made of the
test material and 18 mm in diameter and 3 mm in thickness. At the test, the disc was
compressed by the concentrated forces on the vertical diameter. Measurement error
of the relative deformation and the stress birefringence does not exceed 3 and 1%,
respectively. To determine the Tg, αg, and α∞, test facilities were used as a dilatom-
eter. Dilatometric curves u(T) are temperature dependences of the relative deforma-
tion of unloaded samples, when cooling of the ones with a constant average speed
of 0.4 K/min were averaged in the results over four measurements. The Tg, αg, and
α∞ were determined by the method of ordinary least squares according to eq 13.9:

a g , T < Tg

u (T ) =
1
3
( ) ( )
a ∞ Tg − T0 + a T − Tg  , a = 

a ∞ , T > Tg ,
where T0 is initial temperature of the sample (rubbery state), K.
Stress Birefringence of Highly Cross-Linked Polymers 181

J∞ and C∞ are dependent of T, and therefore, were determined on the basis of

measurements of the relative deformation and stress birefringence with four loads
for a series of temperatures above Tg + 30 K followed by averaging the results of
four tests for each load. Substituting the obtained values of J∞ and C∞ in eqs 13.3 and
13.9, allows determining the experimental A∞ and ξ∞.
C and J in glassy state has been calculated in terms of measuring results of rela-
tive deformations and stress birefringence using four loads at 298 K with subsequent
averaging of results of four tests for each load. Experimental values wJ,β and wС,β
were defined by substitution of J, С values (in glassy state), and A∞, ξ∞ in eqs 13.2,
13.4, and 13.12, on condition that in the glassy state JN,α = 0. Creep and photo creep
curves are the development of relative deformation and stress birefringence into
time at constant T under the influence of constant stress. They were taken for several
T of transit state between glassy and rubbery states, Tg ± 15 K, and were averaged
over the results of four measurements. Empirical values of creep and photo creep
functions were calculated by eq 13.8.8

13.4  MODELING OF TOPOLOGICAL STRUCTURE OF

EXPERIMENTAL OBJECTS
Modeling of topological structure of experimental objects was carried out in two
ways: using computer modeling and graphs theory.

13.4.1  COMPUTER MODELING

The topological structure of highly cross-linked polymer matrices in the length in-
terval of 0.25–2 nm is a random fractal.9 Models of topological structure (Fig. 13.2)
of experimental objects were arranged in the Bullet Physics Library (www.bullet-
physics.org) with use of known values of Van-der-Waals volume of the atoms and
link lengths between them,5 plus fractal dimension (df) (Table 13.1) defined by the
Bullet Physics Library from the following expression9:
d
Nst ∞Rwf ,
where Nst is a number of random segments within the sphere radius Rw.
 182

TABLE 13.1  The Theoretical and Experimental Values of Glass Transition Temperature, the Constant of Rubbery State, the Balanced Elastic
Coefficient of Electromagnetic Susceptibility and Weighting Coefficients.

Tg, K A∞, К/МПа ξ∞ wJ,β wC,β

x <l> n3f df
theor. exp. ε,% theor. exp. ε,% theor. exp. ε,% theor. exp. ε,% theor. exp. ε,%

0.0 1.00 0.4000 2.63 380 382 2 33.5 35.0 4 0.0240 0.0263 9 0.0231 0.0180 28 0.0407 0.0280 45

0.5 1.25 0.3333 2.65 373 372 1 47.3 53.0 11 0.0230 0.0235 2 0.0164 0.0150 9 0.0298 0.0260 15

1.0 1.50 0.2857 2.69 360 361 1 62.1 69.3 10 0.0220 0.0224 2 0.0125 0.0140 11 0.0232 0.0230 1

1.5 1.75 0.2500 2.72 350 350 0 77.7 81.6 5 0.0220 0.0207 6 0.0100 0.0120 17 0.0188 0.0200 6

2.0 2.0 0.2222 2.74 344 344 0 93.9 93.5 4 0.0220 0.0192 15 0.0083 0.0080 4 0.0160 0.0180 11

* The relative difference of the theoretical value versus the experimental value was calculated by formula ε = |(exp.value − thеоr.value)/exp.
value|∙100, %.
Process Advancement in Chemistry and Chemical Engineering Research
Stress Birefringence of Highly Cross-Linked Polymers 183

FIGURE 13.2  The model of topological structure of the experimental object composed of
the composition x = 2.0.

The nature of modeling was in polyaddition imitation. For each experimental

object, the model was arranged in such a way that the topological structure was spa-
tially uniform and the total number of elastically effective nodes comprised mini-
mum 10,000.

13.4.2  MODELING ON THE BASIS OF GRAPHS THEORY

Figure 13.3 shows a structure of the repeating fragment common to all polymer
series. If we designate the numbers of HА fragments with two methylene groups
attached to nitrogen atom as N2f, the elastically effective nodes as N3f, the tetrameth-
ylene fragments as Nσ, and DGEBA fragments as Nπ, and Ntot being the total number
of links, then, according to stoichiometry, we work out as follows:

N 2 f = xn ( HMDA), N 3 f = 2 n ( HMDA), Ns = n ( HMDA),

N π = (2 + x) n ( HMDA), N tot = (5 + 2 x ) n ( HMDA) .

184 Process Advancement in Chemistry and Chemical Engineering Research

FIGURE 13.3  The repeating fragment of the topological structure covering all experimental
objects.

In this case, random parameter representing the number of elastically effective

nodes n3f (Table 13.1), and the number average degree of polymerization of the in-
termodal chain < l > (Table 13.1) are as follows:
n3 f = N 3 f / N tot = 2 / (5 + 2 x ), < l > = Nπ / N 3 f = 1 + 0.5 x

13.5  THEORETICAL ASSESSMENT OF CONSTANTS FOR STRESS

BIREFRINGENCE MODEL

13.5.1  GLASS TRANSITION TEMPERATURE

Glass transition temperature9 (Table 13.1):
d −d
Tg = Clstf , K

where С = 270 K is a constant, d is Euclidean dimension, and lst is an average size

of a random segment, nm.
The difference between theoretical and experimental values Tg is maximum 2%.

13.5.2  COEFFICIENTS OF THERMAL EXPANSION

Calculated frombelow equations,9 values of αg and α∞ for all experimental objects
turned out to be approximately equal, and in average were 3.2·10–4 K–1 and 6.1·10–4
K–1, respectively. These values agree with experimental values: 4.3·10–4 K–1 and
Stress Birefringence of Highly Cross-Linked Polymers 185

7.0·10–4 K–1, the relative difference between the theory and the experiment is 26 and
13%, respectively.

−3(Tg × 10-4 − 2d f + 5) − 9(Tg × 10-4 − 2d f + 5) 2 − 12Tg2 × 10-8

ag = , K–1,
2Tg2 × 10-4

0.106 + a g Tg 0.106
a∞ = = + a g , K–1.
Tg Tg

13.5.3  CONSTANT OF RUBBERY STATE AND BALANCED

ELASTIC COEFFICIENT OF ELECTROMAGNETIC SUSCEPTIBILITY
Constant of rubbery state is as follows5:

A∞ = (0.5 f Ctot n3f RF ) −1 , (13.14)

where f is functionality of the network nodes; F: front-coefficient; R: gas constant
(8.314 J/(mol×К)); Ctot: concentration of elemental links of the topological structure
at Tg, mol/сm3.
By definition, we have:

Ctot = N tot / Vtot (Tg ),

where Vtot(Tg) is volume of elemental links at Tg (сm3):

Vtot (Tg ) = Ns Vs (Tg ) + N3 f V3 f (Tg ) + N 2 f V2 f (Tg ) + NπVπ (Tg ) ,

here, Vσ(Tg), V3f(Tg), V2f(Tg), and Vπ(Tg) are molar volumes of elemental links at Tg,
cm3/mol. Then:

Ctot = (5 + 2 x)d (Tg ) / ( M s + 2 M 3 f + xM 2 f + (2 + x) M π ), (13.15)

where Mσ, M3f, M2f, and Mπ are molar mass of elemental links, g/mol; d(Tg) is poly-
mer density at Tg, g/сm3.
For highly cross-linked polymer matrices temperature dependence of density is
as follows5:

   a g , T < Tg
 ( )

d (T ) = k g M r . f . / 10-24 1 + a T - Tg  N A  ∑ DVi   , a = 
i  r. f .  a ∞ , T > Tg
 ,
here, d(T) is polymer density at T, g/cm3; kg is molecular packing coefficient at Tg;
Mr.f. is molar mass of the repeating fragment of network, g/mol; 10–24 is conversion
186 Process Advancement in Chemistry and Chemical Engineering Research

 
coefficient, from Å3 to cm3; NA is Avogadro constant; and  ∑ DVi  is Van-der-
i r.f .
Waals volume of the repeating fragment of network.
The molar mass of the repeating fragment of network is Mr.f. = 441 < l >−43 g/
mol.
Taking into account that for highly cross-linked polymer matrices at Tg, the
kg ≈ 0.681,5 we work out:

a g , T < Tg
( ( ) )
d (T ) = 1.13 ( 441 < l > - 43) / 1 + a T - Tg  ( 458.9 < l > - 57.4) , a = 
 
a ∞ , T > Tg

Thus, substitution of Tg, αg, and α∞ allows finding the d(T) values at any T val-
ues. The molar masses of the elemental links are as follows: Мσ = 56 g/mol, М3f =
56 g/mol, М2f = 127 g/mol, and Мπ = 314 g/mol.
Substitution of resultant expression for Ctot

( (
C tot = 1.13 5 + 2 x

)( 441 < l > − 43)) / (( 796 + 441x )( 458.9 < l > − 57.4))
in eq 13.14 yields:

(
A = ( 796 + 441x )( 458.9 < l > −57.4 ) / 1.695 FR ( 5 + 2 x )( 441 < l > −43) n3f
∞ .
)
The F values for highly cross-linked polymer matrices with spatially uniform to-
pological structure are within the range of 0.65–0.85 and should increase in a linear
fashion as the network density grows up.10 On this basis we receive:

F = 1.125n3f + 0.4

(
A∞ = 796 + 441x )( 458.9 < l > −57.4) / (1.695 (1.125n3f + 0.4) R (5 + 2 x )( 441 < l > −43) n3f ) (13.16)

Experimental values of A∞ (Table 13.1) can be determined by way of approxima-

tion of empirical J∞ values (2). Small difference between theory and experiment for
A∞ (4–11%) prove the adequacy of the eq 13.16. Experimental values of F can be
determined from A∞ values, for that, on the basis of experimental polymer density
values, preliminary calculation of concentration of elemental links should be found
by eq 13.15.
To assess ξ∞, the following equation was established:

ξ∞ = −3 K (∂dε ∂T ) / (a ∞ ε 0 ) , (13.17)
Stress Birefringence of Highly Cross-Linked Polymers 187

where ε0 is dielectric permittivity of the unstressed polymer at Tg, K is constant,

depending on polymer topological structure; ∂δε/∂T is one of the components of the
derivative ε0 in T, which relates to electromagnetic anisotropy in stressed polymer,
K–1; ε0 and ∂δε/∂T were calculated incrementally according to standard methods.5
Constant К was determined by the method described in the work,3 its value for ex-
perimental objects is 15.7 (Figure 13.4).

FIGURE 13.4  Temperature dependence of balanced shear compliance (cross: experiment,

line: approximation).

Finally (Table 13.1):

 212.7362 < l > +5.309  186.860314 < l > −24.388346

ξ ∞ = 0.07
 458.9 < l > −57.4  455.465782 < l > −54.939368 .
The difference between theoretical and experimental values, ξ∞, was maximum
15%.

13.5.4  WEIGHTING COEFFICIENTS

Weighting coefficients (Table 13.1):

J β ,∞ Cβ ,∞
wJ ,β = T, wC ,β = T,
A∞ 0.5ξ∞ A∞
188 Process Advancement in Chemistry and Chemical Engineering Research

J β ,∞ a1 2 1 + µ β ,∞ df
where Cβ ,∞ = ; J β ,∞ = × B∞ ; µβ ,∞ = − 1.
4n0 3 1 − 2 µ β ,∞ d −1
Here a1 is coefficient (refer to eq 13.7); n0 is a refractive index of the nonde-
formed polymer dielectric, which is in glassy state. The a1 and n0 are calculated
incrementally according to standard methods at 298 K.5 Table 13.1 shows a com-
parison of experimental and theoretical determination of the weighting coefficients.

13.5.5  PARAMETERS OF THE RELAXATION SPECTRUM

Parameters of the relaxation spectrum theoretically cannot be assessed neither with-
in the framework of the increments method, nor within the framework of the frac-
tal approach. Empirical values of ΘJ,α (T) and ΞJ,α were determined from the creep
and photo creep curves (method of least squares with regularization of solutions by
singular decomposition11). It was revealed that for the highly cross-linked polymer
matrices with spatially uniform topological structure ΞJ,α is determined by network
topology and is independent of temperature (no splitting of α-transition). The ex-
perimentally found value ΞJ,α increases linearly from 0.4 to 0.65 with an increase <
l > (for a priori prediction, the value of 0.5 can be used). Example of ΘJ,α (T) depen-
dence of temperature is shown in Figure 13.5: the eq 13.13 describes both branches
of the experimental curve lgΘJ,α (T) with high accuracy. The obtained value of the
share of the fluctuation free volume was averaged over all experimental objects, the
average value was fg = 0.095. This result is consistent with the currently accepted
value for the highly cross-linked polymer matrices −0.09.

FIGURE 13.5  The dependence of lgΘJ,α on T for the object of the composition x = 0 (dots:
experiment, line: approximation).
Stress Birefringence of Highly Cross-Linked Polymers 189

13.5.6  ADEQUACY OF THE MODEL

The adequacy of the model of stress birefringence of highly cross-linked polymer
matrices was experimentally demonstrated by comparing of the predicted and the
actual course of the thermal polarization curves (Fig. 13.6).

FIGURE 13.6  Thermal polarization curve for the experimental object of the composition x
= 1.5 (1: experiment, 2: calculation based on the proposed model).

13.6 CONCLUSION
Thus, the stress birefringence model and the fractal-incremental approach allow as-
sessing the stress birefringence to be done, even before the experiment starts. So, a
priori, we can assess the maximum ultimate value of stress birefringence for which
highly cross-linked polymer matrix is capable in the given operating conditions of
radiotransparent fiberglass. Knowing the value of stress birefringence of highly
cross-linked polymer matrices, one can assess the change of fiberglass radiotrans-
parency coefficient applicationwise. Hence, the possibility of highly cross-linked
polymer matrix application for fiberglass is being justified.
190 Process Advancement in Chemistry and Chemical Engineering Research

KEYWORDS

•• highly cross-linked epoxy–amine polymers

•• modeling
•• heredity theory
•• fractal analysis of macromolecules

REFERENCES
1. Davide, S. A.; De Focatiis, C. P. B.. Prediction of Frozen-In Birefringence in Oriented Glassy
Polymers Using a Molecularly Aware Constitutive Model Allowing for Finite Molecular Ex-
tensibility. Macromolecules 2011, 44 (8), 3085–3095.
2. Rabotnov, Y. N. Mechanics of a Deformable Solid Body; Nauka: Moscow, RU, 1979; p 744 (in
rus).
3. Blythe, T.; Bloor, D. Electrical Properties of Polymers; Cambridge University Press: Cam-
bridge, UK, 2005; p 492.
4. Ferry, J. D. Viscoelastic Properties of Polymers, 3rded.; John Wiley & Sons, Inc.: New York,
Chichester, Brisbane, Toronto, Singapore, 1980; p 641.
5. Askadskii, A. A. Computational Materials Science of Polymers; Cambridge International Sci-
ence Publish: Cambridge, UK, 2003; p 650.
6. Irzhak, V. I.; Mezhikovskii, S. M. Structural Aspects of Polymer Network Formation Upon
Curing of Oligomer Systems. Russ. Chem. Rev. 2009, 78 (2), 165–194.
7. Zuev, B. M.; Arkhireev, O. S. The Initial Stage in the Fracture of Stressed Dense-Cross-Linked
Polymer Systems. Polym. Sci. U.S.S.R. 1990, 32 (5), 941–947.
8. Handbook of Thermal Analysis and Calorimetry; Cheng, S. Z. D., Ed.; Applications to Poly-
mers and Plastics, Vol. 3; Elsevier Science B.V.: Amsterdam, 2002; pp 1–45.
9. Novikov, V. U.; Kozlov, G. V. Structure and Properties of Polymers in Terms of the Radical
Approach. Rus. Chem. Rev. 2000, 69 (6), 523–549.
10. Irzhak, V. I. Topological Structure and Relaxation Properties of Polymers, Russ. Chem. Rev.
2005, 74, 937.
11. Tihonov, A. N.; Arsenin, V. Ja. Methods of Decission of Incorrect Problems, 3rd ed.; Nauka:
Moscow, RU, 1986; p 287 (in rus).
CHAPTER 14

INVESTIGATION OF VARIOUS
METHOD FOR STEEL SURFACE
MODIFICATION
I. NOVÁK1, I. MICHALEC1, M. VALENTIN1, M. MARÔNEK2,
L. ŠOLTÉS3, J. MATYAŠOVSKÝ4, P. JURKOVIČ4
1
Department of Welding and Foundry, Faculty of Materials Science and Technology
in Trnava, 917 24 Trnava, Slovakia
2
Slovak Academy of Sciences, Polymer Institute of the Slovak Academy of Sciences,
845 41 Bratislava, Slovakia
3
Institute of Experimental Pharmacology of the Slovak Academy of Sciences, 845 41
Bratislava, Slovakia
4
VIPO, Partizánske, Slovakia. E-mail: [email protected]

CONTENTS
14.1 Introduction.................................................................................................192
14.2 Experimental...............................................................................................192
14.3  Results and Discussion...............................................................................194
14.4 Conclusion..................................................................................................200
Acknowledgments..................................................................................................201
Keywords...............................................................................................................202
References..............................................................................................................202
192 Process Advancement in Chemistry and Chemical Engineering Research

14.1 INTRODUCTION
The surface treatment of steel surface is often used, especially in an automotive
industry, which creates the motive power for research, design, and production. New
methods of surface treatment are also developed having major influence on im-
provement of the surface properties of steel sheets while keeping the price at reason-
able level.1–3
The nitrooxidation is one of the nonconventional surface treatment methods,
which combine the advantages of nitridation and oxidation processes. The improve-
ment of the mechanical properties (tensile strength, yield strength) together with the
corrosion resistance (up to level 10) can be achieved.4–7 The fatigue characteristics
of the nitrooxidized material can be also raised.5
Steel sheets with surface treatment are more often used, especially in an auto-
motive industry that creates the motive power for research, design, and production.
New methods of surface treatment are also developed having major influence on
improvement of the surface properties of steel sheets while keeping the price at
reasonable level.
Previous outcomes1,3,8,4,10 dealt with the welding of steel sheets treated by the
process of nitrooxidation by various arc and beam welding methods. Due to high
oxygen and nitrogen content in the surface layer, problems with high level of poros-
ity had occurred in every method. The best results were achieved by the solid-state
laser beam welding, by which the defect-free joints were created. Due to high initial
cost of the laser equipment, further research was directed to the joining method that
has not been tested. Therefore, the adhesive bonding was chosen, because the joints
are not thermally affected, they have uniform stress distribution and good corrosion
resistance.
The goal of the paper is to review the adhesive bonding of steel sheets treated by
nitrooxidation and to compare the acquired results to the nontreated steel.

14.2 EXPERIMENTAL
For the experiments, low-carbon deep-drawing steel DC 01 EN 10130/91 of 1 mm
in thickness was used. The chemical composition of steel DC 01 is documented in
Table 14.1.

TABLE 14.1  Chemical Composition of Steel DC 01 EN 10130/91.

EN designation C Mn P S Si Al
(%) (%) (%) (%) (%) (%)

DC 01 10130/91 0.10 0.45 0.03 0.03 0.01 –

Investigation of Various Method for Steel Surface Modification 193

14.2.1  CHEMICAL MODIFICATION

The base material was consequently treated by the process of nitrooxidation in flu-
idized bed. The nitridation fluid environment consisted of the Al2O3 with granular-
ity of 120 μm. The fluid environment was wafted by the gaseous ammonia. After
the process of nitridation, the oxidation process started immediately. The oxidation
itself was performed in the vapors of distilled water. Processes parameters are re-
ferred in Table 14.2.

TABLE 14.2  Process of Nitrooxidation Parameters.

Nitridation Oxidation

Time (min) 45 5

Temperature (°C) 580 380

14.2.2 ADHESIVES
In the experiments, four types of two-component epoxy adhesives made by Loctite
Company (Hysol 9466, Hysol 9455, Hysol 9492, and Hysol 9497) were used. The
properties of the adhesives are documented in Table 14.3.

TABLE 14.3  The Characterization of the Adhesives.

Hysol 9466 Hysol 9455 Hysol 9492 Hysol 9497

Resin type Epoxy Epoxy Epoxy Epoxy

Hardener type Amin Methanethiol Modified amin

Mixing ratio 2:1 1:1 2:1 2:1

(resin:hardener)

Elongation (%) 3 80 0.8 2.9

Shore hardness 60 50 80 83

14.2.3 METHODS
The experiments were done at the Faculty of Materials Science and Technology,
Department of Welding and Foundry in Trnava. The adhesive bonding was applied
on the grinded as well as non-grinded surfaces of the material to determine the
grinding effect on total adhesion of the material so as on ultimate shear strength
of the joints. The grinded material was prepared by grinding with silicone carbide
paper up to 240 grit.
194 Process Advancement in Chemistry and Chemical Engineering Research

Before the adhesive bonding, the bonding surfaces (both grinded as well as non-
grinded) were decreased with aerosol cleaner. The overlap area was 30 mm. To
ensure the maximum strength of the joints, the continuous layer of the adhesive was
coated on the overlap area of both bonded materials. The thickness of the adhesive
layer was 0.1 mm and was measured by a calliper. The joints were cured under fixed
stress for 48 h at the room temperature. The dimensions of the joints are referred in
Figure 14.1.

FIGURE 14.1  The dimension of the bonded joints.

The mechanical properties of the joints were examined by the static shear tests. As
a device, the LaborTech LabTest SP1 was used. The conditions of the tests were
set in accordance with STN EN 10002-1. The static shear tests were repeated on
three separate samples and an average value was calculated.
The fracture areas were observed in order to obtain the fracture character of
the joints. The JEOL JSM-7600F scanning electron microscope was used as a
measuring device.
The differential scanning calorimetry (DSC) was performed on Netzsch STA 409
C/CD equipment. As the shielding gas, Helium with purity of 99.999% was used.
The heating process starts at the room temperature and continued up to 400°C with
heating rate 10°C/min. The DSC analysis on Hysol 9455 was done on Diamond
DSC Perkin Elmer, capable of doing analyses from −70°C.

14.3  RESULTS AND DISCUSSION

The material analysis represents the first step of evaluation. There are many factors
having an influence on the joint quality. The properties of the nitrooxidized material
Investigation of Various Method for Steel Surface Modification 195

depends on the treatment process parameters. For the adhesive bonding, the surface
layer properties are important because of that, the high adhesion is needed to ensure
the high strength of the joint.
The overall view on the microstructure of the nitrooxidized material surface
layer is referred in Figure 14.2a. On the top of the surface, the oxide layer (Fig.
14.2b) was created. This layer had a thickness of ~700 μm. Beneath the oxide layer,
the continous layer of ε-phase, consisting of nitrides Fe2-3N and with the thickness
of 8–10 μm was observed.

FIGURE 14.2  The microstructure of the surface layer. (a) Overall view and (b) detail view
on the oxide layer.

The surface energy measurements were performed due to obtain the properties
of the material, which are important for adhesive bonding. For observing the grind-
ing effect on the total surface energy, the measurements were done on the base as
well as on the grinded material.
To determine the surface energy, the portable computer-based instrument See-
System was used. Four different liquids (distilled water, formamide, diiodomethan,
and ethylene glycol) were instilled on the material surface and contact angle was
measured. The Owens–Wendt regression model was used for the surface energy cal-
culation. The total amount of six droplets were analyzed of each liquid. The results
(Table 14.4) proved that the nitrooxidation treatment had a strong effect on mate-
rial surface energy, where the decrease by 28% in comparison to non-nitrooxidized
material had occurred. The surface energies of grinded and non-grinded material
without nitrooxidation were very similar, while the increase of surface energy of
grinded nitrooxidized material by 35% in comparison to non-grinded material was
observed. In the case of barrier plasma-modified steel, the surface energy is higher
than that of unmodified material and namely its polar component is significantly
higher than polar component of surface energy for unmodified sample as well as for
sample modified by nitrooxidation.
196 Process Advancement in Chemistry and Chemical Engineering Research

TABLE 14.4  The Surface Energy of Materials.

Material type Total surface Dispersion compo- Acid–base component

energy (mJ/m2) nent (mJ/m2) (mJ/m2)

DC 01 38.20 35.62 2.58

DC 01 grinded 38.80 33.66 5.14

Nitrooxidized 27.60 25.79 1.80

Nitrooxidized
37.31 32.54 4.77
grinded

Barrier plasma
39.99 33.69 6.30
treated

The mechanical properties of the material were obtained by the static tensile
test. Total amount of three measurements were done and the average values are
documented in Table 14.5. Based on the results, it can be stated that after the process
of nitrooxidation, the increase of yield strength by 55% and tensile strength by 40%
were observed. The barrier plasma did not influence the mechanical properties after
surface modification of steel, which remained the same as for unmodified sample.

TABLE 14.5  Mechanical Properties of the Base Materials.

Yield strength (MPa) Tensile strength (MPa)
DC 01 200 270
Nitrooxidized 310 380
Barrier plasma 200 270
Treated

The tensile test of the adhesives were carried out on the specimens, which were
created by curing of the adhesives in special designed polyethylene forms for 48 h.
The results are shown in Table 14.6. In three of the adhesives (Hysol 9466, Hysol
9492, and Hysol 9497), very similar values were observed while in case of Hysol
9455, only tensile strength of 1 MPa was observed.

TABLE 14.6  The Mechanical Properties of the Adhesives.

Hysol 9466 Hysol 9455 Hysol 9492 Hysol 9497

Tensile strength (MPa) 60 1 58 65
Investigation of Various Method for Steel Surface Modification 197

The differential scanning calorimetry was performed due to obtain the glass
transition temperature as well as the melting points of the adhesives. The results are
shown in Table 14.7. To measure the glass transition temperature of Hysol 9455, the
measurements had to be started from the cryogenic temperatures. The results of such
a low glass transition temperature explained the low tensile strength of the Hysol
9455, where at the room temperature, the mechanical behavior changed from rigid
to rubbery state. The results of DSC analyses are given in Figure 14.3–14.6.

TABLE 14.7  The Glass Transition Temperatures of Adhesives.

Hysol 9466 Hysol 9455 Hysol 9492 Hysol 9497

Glass transition temperature (°C) 52.6 5.0 61.2 62.4
Melting point (°C) 315.7 337.0 351.8 327.3

FIGURE 14.3  The DSC analysis of the Hysol 9466.

FIGURE 14.4  The DSC analysis of the Hysol 9455.

198 Process Advancement in Chemistry and Chemical Engineering Research

FIGURE 14.5  The DSC analysis of the Hysol 9492.

FIGURE 14.6  The DSC analysis of the Hysol 9497.

The adhesive joint evaluation consisted of observing the mechanical properties

and fracture surface, respectively.
In order to obtain mechanical properties of the joints, the static shear tests were
carried out. Results (Table 14.8) showed that the highest shear strength was ob-
served in grinded nitrooxidized joints. The Hysol 9466 provided joints with the
highest shear strength
Investigation of Various Method for Steel Surface Modification 199

TABLE 14.8  The Results of Shear Test of the Joints.

Material Shear strength (MPa)

Hysol 9466 Hysol 9455 Hysol 9492 Hysol 9497

DC 01 9.0 2.8 7.1 6.0

DC 01 grinded 8.9 2.9 7.2 6.1

Nitrooxidized 12.9 3.1 7.8 5.4

Nitrooxidized
12.9 5.9 12.7 7.0
grinded

Barier plasma
13.8 6.1 14.2 7.8
treated

The mechanical properties of the joints made on non-nitrooxidized material did

not depend on the surface grinding. The mechanical properties of the joints made
on nitrooxidized material, in comparison to DC 01, were higher by 43% in case of
Hysol 9466, 11% in case of Hysol 9455, and 10% in case of Hysol 9492. In the case
of adhesive Hysol 9497, the decrease of the shear strength had occurred. The joints
produced on grinded nitrooxidized material, in comparison to DC 01, had a higher
shear strength by 43% in case of Hysol 9466, 110% in case of Hysol 9455, 79% in
case of Hysol 9492, and 15% in case of Hysol 9497. The shear strength of adhesive
joint was for barrier plasma-modified steel for all kinds of adhesive Hysol higher
than unmodified and nitrooxidized steel.
Results of fracture morphology of the joints made of non-nitrooxidized mate-
rial are shown in Figure 14.7a. Only the adhesive type of fracture morphology (Fig.
14.7b) was observed in every type of the adhesive. Cohesive and combined fracture
type were not observed. It can be stated that the adhesion forces were not strong
enough, hence, the joints were fractured between the material and adhesive.

FIGURE 14.7  The fractographic analysis of the fractured adhesive joint of non-nitrooxidized
material. (a) Overall view and (b) close-up view.
200 Process Advancement in Chemistry and Chemical Engineering Research

The results of the fractographic analysis of the non-grinded nitrooxidized steel

are documented in Figure 14.8. No oxide layer peeling was observed. The cleavage
fracture pattern as well as adhesive fracture morphology was observed. The close-
up view on the cleavage fracture is shown in Figure 14.8b.

FIGURE 14.8  The fractographic analysis of the fractured adhesive joint of nitrooxidized
material. (a) Overall view and (b) close-up view.

Differential scanning calorimetry revealed that three of the adhesives had a very
similar glass transition temperature, so the meshing of the adhesives will start in the
same way.
The results of mechanical properties evaluation of the joints proved that the ma-
terial after the nitrooxidation process had a better adhesion to the epoxy adhesives
than plain material DC01. Due to this fact, the higher shear strength was achieved.
It can be explained by the surface oxide layer porosity, which helped the adhesive
to leak in.
On the other hand, increase of mechanical properties of joints prepared from
grinded nitrooxidized material can be explained by removing the surface oxide lay-
er, and thus resulting into rapid increase of surface energy.
Only adhesive type of fracture was observed and the fractographic analysis
showed that only cleavage type of fractures has been created. It can be stated that the
surface energy of the materials was not appropriate for the cohesive fracture pattern.

14.4 CONCLUSION
Joining of steel sheets treated by the process of nitrooxidation represents an interest-
ing technical as well as technological problem. The fusion welding methods with
high-energy concentration, for example, laser beam welding are one of the possible
options; however, even with high effort of minimizing the surface layer deteriora-
tion, it is not possible to completely avoid it.
Investigation of Various Method for Steel Surface Modification 201

Adhesive bonding of nitrooxidized steels presents, thus the second alternative,

when the surface layer is not damaged and the adhesive joint keeps its properties af-
ter it has been cured. Adhesive bonding of metallic substrates often requires remov-
ing the surface oxide layer from the areas to be bonded. In case of materials treated
by nitrooxidation, this is possible, however, the damage of the formed surface layer
will occur. The goal of this paper was to review the effect of surface layer, created by
the process of nitrooxidation and or by barrier discharge plasma treatment, on final
mechanical properties of the joints, evaluation of fracture morphology, and results
comparison for both treated and untreated material.
The acquired results have revealed that the presence of nitrooxidation surface
layer caused decrease of free surface energy by 28%. The surface energy and name-
ly its polar component were for barrier plasma-modified steel higher than for un-
modified and nitrooxidized steel. On the other hand, this surface layer brings, on the
joints, shear strength increase by 10–43% in dependence of the adhesive used. In
case of Hysol 9497, the decrease of the joint shear strength by 10% was observed. In
the case of barrier plasma-modified steel, the strength of adhesive joint were higher
than unmodified and nitrooxidized material. We can presume that the increase of
the shear strength was mainly due to porous structure of the surface layer, which
enabled the adhesive to leak in.
The adhesive type of fracture morphology was observed during fractographic
analysis. Regarding the characteristics of used adhesives, the cleavage fracture mor-
phology of the joints had occurred.
Based on received results, it can be concluded that the epoxy adhesive bonding
represents the suitable alternative of creating the high-quality joints of steel sheets
treated by nitrooxidation as well as treated by barrier discharge plasma.

ACKNOWLEDGMENTS
This paper was prepared within the support of Slovak Research and Develop-
ment Agency, grant No. 0057-07 and Scientific Grant Agency VEGA, grant No.
1/0203/11 and 2/0199/14.
This publication was prepared as an output of the project 2013-14547/39694:1-
11 “Research and Development of Hi-Tech Integrated Technological and Machinery
Systems for Tyre Production—PROTYRE” co-funded by the Ministry of Educa-
tion, Science, Research and Sport of the Slovak Republic pursuant to Stimuli for
Research and Development Act No. 185/2009 Coll.
202 Process Advancement in Chemistry and Chemical Engineering Research

KEYWORDS

•• steel surface
•• fracture character
•• nitrooxidation
•• adhesive bonding
•• differential scanning calorimetry

REFERENCES
1. Michalec, I. CMT Technology Exploitation for Welding of Steel Sheets Treated by Nitrooxi-
dation. Diploma thesis, Trnava, SK, 2010.
2. Konjatić, P.; Kozak, D.; Gubeljak, N. The Influence of the Weld Width on Fracture Behaviour
of the Heterogeneous Welded Joint. Key Eng. Mat. 2012, 488–489, 367–370.
3. Bárta, J. Welding of Special Treated Thin Steel Sheets: Dissertation thesis, Trnava, SK, 2010.
4. Lazar, R.; Marônek, M.; Dománková, M. Low Carbon Steel Sheets Treated by Nitrooxidation
Process, Eng. Extra 2007, 4, 86.
5. Palček, P et al. Change of Fatigue Characteristics of Deep-Drawing Sheets by Nitrooxidation.
In: Chemické Listy; ISSN 0009-2770; Master Journal List, Scopus, 2011; Vol. 105, Iss. 16, pp
539–541.
6. Bárta, J. et al. Joining of Thin Steel Sheets Treated by Nitrooxidation. Proceeding of Lectures
of 15th Seminary of ESAB + MTF-STU in the Scope of Seminars about Welding and Weld-
ability; Alumni Press: Trnava, SK, 2011; pp 57–67.
7. Marônek, M. et al. Welding of Steel Sheets Treated by Nitrooxidation, JOM-16, 16th Interna-
tional Conference On the Joining of Materials & 7th International Conference on Education in
Welding ICEW-7, Tisvildeleje, DK, May 10–13, ISBN 87-89582-19-5.
8 Viňáš, J. Quality Evaluation of Laser Welded Sheets for Cars Body. In Mat/tech automobi-
lového priemyslu: Zborník prác vt-seminára s medzinárodnou účasťou; Košice, SK, 2005; pp
119–124, ISBN 80-8073-400-3.
9. Marônek, M. et al. Laser Beam Welding of Steel Sheets Treated by Nitrooxidation, 61st Annual
Assembly and International Conference of the International Institute of Welding, Graz, AT,
July 6–11, 2008.
10. Michalec, I. et al. Resistance Welding of Steel Sheets Treated by Nitrooxidation. In TEAM
2011, Proceedings of the 3rd International Scientific and Expert Conference with Simultane-
ously Organised 17th International Scientific Conference CO-MAT-TECH 2011, Oct 19–21,
2011; University of Applied Sciences of Slavonski Brod: Trnava, SK, 2011; pp 47–50, ISBN
978-953-55970-4-9.
CHAPTER 15

SORBTION OF INDUSTRIAL DYES BY

INORGANIC ROCKS FROM AQUEOUS
SOLUTIONS
F. F. NIYAZI1 and A. V. SAZONOVA2
1
Fundamental chemistry and chemical technology, South-West State University,
305040 Kursk, street October 50, 94, Russia. E-mail: [email protected]
2
Fundamental chemistry and chemical technology, South-West State University,
305040 Kursk, street October 50, 94, Russia. E-mail: [email protected]

CONTENTS
Abstract..................................................................................................................204
Keywords...............................................................................................................209
References..............................................................................................................209
204 Process Advancement in Chemistry and Chemical Engineering Research

ABSTRACT
The authors of this work have defined chemical composition of inorganic polymeric
rocks. They have also studied kinetics of industrial dyes sorption from aqueous so-
lutions by the rocks under investigation. Kinetic curves of the sorption have been
stated. This work also considers possibilities to use kinetic equation of pseudo-first
and second orders for the description of the sorption process.
Production and use of dyes is connected with the use of huge quantity of water,
a great part of which is released in a polluted state.
On an average, about 225 tons of water is spent per 1 ton of dye. During produc-
tion of each ton of dyes together with industrial sewage, enterprises release dozens
and hundreds tons of different mineral and organic compounds in the form of waste.1
At present, different types of dyes are widely used for the production of paper,
paints, and pigments in textile, shoe-manufacturing, and printing industries. Dur-
ing production processes, 10–40% of dyes being used are released into the sewage,
which, in turn, is released into natural pools, thus causing serious violation of bio-
cenose in them.2
Once into the water pools, these dyes have a negative effect on the associations
of water organisms and also violate their oxygen regime. Most of the organic dyes
are highly toxic and have an allergic effect. Besides, as a rule, cationic dyes are more
toxic for water ecosystems than anionic ones.3 Thus, it is imperative to search for
new approaches to the problem of sewage treatment containing dyes.
Existing methods of sewage treatment from industrial dyes can be divided into
regenerating, destructive, and biological methods. Among them, regenerating meth-
ods are better since they allow for the extraction of substances, being constrained in
sewage, for their further use. This problem may be solved by using such methods of
concentration as extraction, ionic replacement, sorption, and others.
Adsorption on mesoporous activated coals is one of the effective methods of
sewage treatment contaminated by dyes.4 However, such coals are expensive adsor-
bents and are produced in small quantities. Perspective direction cheaper is utiliza-
tion, on the one hand, cheap, and, on the other hand, available sorption materials as
adsorbents.5
Thick chalkbeet stretches through European continent, including the north of
France, south part of England, Poland, goes through the Ukraine, Russia, and is
displaced into Asia—Syria and Libyan Desert.
Kursk region possesses exceptional variety of natural resources that are able
to provide adequate amount of carbonate rocks. That is why inorganic polymeric
rocks of Kursk region have been used as sorption material because they are high-
dispersion systems.
Carbonate rocks, under investigation, were analyzed for their calcium and mag-
nesium carbonates content—by complexonometric methods such as sulfate ions,
ferrous and aluminum oxides; by gravimetric method such as chloride ions; and by
methods of turbidimetry. The content of insoluble residue in hydrochloric acid has
Sorbtion of Industrial Dyes by Inorganic Rocks 205

been discovered, and the electric conduction of carbonate rocks saturated with aque-
ous solution has been also measured. Electric conduction was defined with the help
of conductivity apparatus KSL-101. Received results of the chemical composition
of carbonate rocks are given in Table 15.1.

TABLE 15.1  Chemical Composition of Carbonate Rocks.

Deposits of Kursk region Area of sampling
Konyshovka Medvenka

Granulometric composition (%) (0.2–0.06) 73,37–68,49 88,13–79,84

Moisture content (%) 9.6225 6.3125
Content of CaCO3 и MgCO3 in terms of CaCO3 (%) 49.50 41.95
Insoluble residue in HCI 1.075 13.566
Sesquilateral content ferrous and aluminum oxides 0.273 1.530
Water-soluble substances (%) 3.1823 2.15997
Electric conduction (мкСм/см) 79.04 88.26
Salt content in terms of NaCl (mg/L) 37.22 41.59
Sulfate ions (%) 0.00445 0.01403
Chloride ions (мг/л) 0.005 0.0015

The analysis of sorbent shows that calcites form a great share of the systems
being studied. Deposits of carbonate rocks in Kursk region differ by low content of
insoluble residue and high content of carbonates.
Structural and microscopic characteristic of polymeric rocks were different as
determined by the method of homogeneous field with the help of polarizing-in-
terference microscope BIOLAR. The investigation has shown that original rocks
consist of dolomite trigonal and rhombic crystals.6
The aim of this work is to study the process of industrial dyes of different sorp-
tion nature by carbonate rocks.
Dyes (cationic blue, cationic red, acidic brightly green, and antraquinone blue)
widely used in industry were used as an adsorptive.
Experiments in sewage treatment from industrial dyes were carried out using
model aqueous solutions of industrial dyes and sewage from a dye-finishing shop
of knitted fabric incorporation «Seim» (Kursk). Dyes of «pure-for-analysis» quali-
fication without additional cleaning were used for preparation of aqueous solutions.
Aqueous solutions of dyes with concentration of 0.01 g/l at 298°C with a solution
volume V = 50 ml were investigated.
206 Process Advancement in Chemistry and Chemical Engineering Research

Effects of sorbent mass on dyes sorption and kinetics of the process of sewage
treatment from industrial dyes have been studied in order to find optimal param-
eters of sorption and also to state sorption properties of carbonate rocks. Method of
one-step static sorption was used in this work. Sorption was carried out by adding
carbonate rocks samples, grinded to granules to a size of 0.06–2.0 mm, to the dyes
solution being studied. Then all this was stirred by a magnetic mixer and after defi-
nite intervals, samples were taken and the defined residual concentration of dyes by
spectrophotometric method was carried out.
Readings of absorption spectra on coordinates: optical density (A) and wave
length (λ) on the device СФ-26 have been taken; wavelengths of maximum light
absorption for cationic blue (610 nm), cationic red (490 nm), acid brightly green
(670 nm), antraquinone blue (590 nm) were chosen. Subordination bound of dyes
solution to the main law of light absorption—Beer–Lambert–Bonguer law—has
also been found.
Data on carbonate rocks mass affect on the sorption of industrial dyes are given
in Table 15.2.

TABLE 15.2  Effect of Carbonate Rocks Mass on the Sorption of Industrial Dyes at Phase’s
Relation: t = 30 min, V = 50 ml, and C = 0.01 g/L.

Mass (g) Dye 0.05 0.1 0.25 0.5 1.0 2.0

Cationic blue 93.0 99.0 99.5 100 100 100
Cationic red 66.0 84.4 95.98 100 100 100
Antraquinone blue 76.0 88.0 100 100 100 100
Acid brightly green 0 20.0 38.6 40.2 46.6 49.6

Data of the given researches helped us in finding sorption capacitance of carbon-

ate rocks: for cationic dyes—1 mg/g of sorbent, for antraquinone blue dye—2 mg/g
of sorbent, for acid brightly green dye—0.1 mg/g of sorbent.
Cleaning efficiency (CO, %) shows the share of absolute substance quantity,
which is caught by sorbent, and gives rather a complete notion of the process and its
character.7 This factor is an important criterion while defining optimal condition of
the sorption process and is calculated by the following formula:

(C0 − C ) × 100% ,
CO =
C0
where С0 is the initial concentration in g/l and С is the residual concentration in g/l.
These data allow choosing optimal mass of sorbent for definition of industrial
dyes kinetics by carbonate rocks. Results of these studies are given by kinetic curves
in Figure 15.1.
Sorbtion of Industrial Dyes by Inorganic Rocks 207

FIGURE 15.1  Kinetic curves of industrial dyes sorption by carbonate rocks.

Sorption lasts for the first 2–3 min after the beginning of contact phases re-
gardless of the dye nature at the first section of the stepped kinetic curve. But this
sorption quickly increases at the second section during the following 3–30 min.
Complete (100%) sorption of dyes takes place after 30 min of interaction and there
is sorption equilibrium. Further increase of contact time is pointless.
Comparison of studied literature data allows us to come to a conclusion that the
stepped character of sorption kinetic cures is the result of the fact that adsorption of
large ions takes place on microporous carbonate rocks. Mass transfer on the phase’s
boundary and interaction of dyes with carbonate rock surface play an important role
at the first stage of sorption, and at the second stage there is internal diffusion of
dye into sorbent pores of accessible size, allowing the dye to be sorbet again on the
external surface of sorbent.8
It is stated that for all stepped kinetic curves, the first section can be described by
the equation of pseudo-first order; but the second section is not described by integral
equation of kinetic models neither of the pseudo-first, nor pseudo-second order.9
It is known that hydrogen index of environment (pH) has a great influence on
the process of sorption and selection of sorbent for sewage treatment. It is connected
with the fact that functional groups on the sorbent surface and functional groups of
dye molecules may change depending on environmental pH.10 Change of pH after
208 Process Advancement in Chemistry and Chemical Engineering Research

the process of sorption depending on the time of the contact of sorbents, being stud-
ied, and industrial dyes is given in Table 15.3.

TABLE 15.3  Change of pH Depending on the Time of Contact of Carbonate Rocks and
Industrial Dyes.
Industrial dye рНо Time of contact (min)
1 5 10 20 25 30
Blank test 6.5 7.25 7.67 7.92 8.10 8.54 8.83
Cationic red 4.26 7.29 7.08 7.55 7.17 7.18 7.00
Cationic blue 3.41 7.57 7.60 7.64 7.67 7.44 7.38
Antraquinone blue 5.67 7.45 7.33 7.45 7.38 7.36 7.32
Acid brightly green 5.38 7.32 7.20 7.18 7.05 6.95 6.82

Increase of pH value is observed when carbonate rocks are mixed with water
and this is because of hydrolysis of calcium and magnesium carbonates. On the con-
trary, decrease of pH values is observed during the process of industrial dyes sorp-
tion and this may be explained by chemical interaction of carbonate rocks and dyes.
This can be very important when we choose a sorbent for sewage neutralization
during the process of acid sewage treatment. Results of the research showed high
adsorption ability of carbonate rocks regarding industrial dyes of different classes.
The suggested method of sewage sorption treatment from dyes increases the
variety of sorbents being used during treatment, and allows using local carbonate
rocks as sorbents.
It is necessary to note that kinetic curves differ from each other to a small extent
while comparing sorption ability of carbonate rocks in relation to dyes. However,
consumption of carbonate sorbent is decreasing for cationic and antraquinone dyes
at the same phase’s relation and efficiency of aqueous solution treatment.
As to technological execution, it is necessary to carry out the process of sorption
in contact absorbers, equipped by mechanical mixers of batch action. Separation of
solid and liquid phases is carried out by decantation and filtration. It is economically
pointless to recover waste sorbent that is why it is necessary to utilize it.
One of the ways to utilize this sorbent is to use it as a filling agent. This is con-
nected with the fact that calcium carbonate is a widely used material in the world
industry today. Development of the branches of rubber engineering, electric power,
glass, paper, polymeric, paint and varnish, and other industries requires an increase
in production of high-quality filling agents, and at the first place is chalk. Charac-
teristic feature of this natural material is connected with the fact that it is easier to
quarry and process it at rather small expenditures. Its quarrying and processing do
not cause serious ecological violations, and its reserves are practically unlimited in
many European countries, countries of former UIS, and in Russia.
Sorbtion of Industrial Dyes by Inorganic Rocks 209

KEYWORDS

•• inorganic rocks
•• dye
•• sorption
•• kinetic curve
•• pH
•• utilization

REFERENCES
1. Stepanov, B. I. Introduction in chemistry and technology of organic dyes; Chemistry: Mos-
cow, RU, 1977; p 488.
2. Ramesh, D. D.; Parande, A. K.; Raghu, S., Prem Kumar, T. J. Cotton Sci. 2007, 11, 141–153.
3. Hao, O. J.; Chiang, P. C. Crit. Rev. Environ. Sci. Technol. 2000, 30, 141–153.
4. Soldatkina, L. M.; Sagajdak, E. V.; Menchuk, V. V. Adsorption of Cationic Dyes from Water
Solutions on Sunflower. Chem. Technol. Water 2009, 31 (4), 417–426.
5. Litvina, T. M.; Kushnir, I. G. Problem of reset, processing and waste recyclings. Odessa, 2000,
258.
6. Niyazi. F. F.; Maltsevf, V. S.; Burykina, O. V.; Sazonov, A. V. Kinetics of sorption of ions of
copper by cretaceous breeds. News of Kursk State Technical University, (4), Kursk, 2010,
28–33.
7. Gocharuk, V. V; Puzyrnaja, L. N.; Pshinko, G. N; Bogolepov, A. A.; Demchenko, V. J. Re-
moval of Heavy Metals from Water Solutions Montmorillonite, Modified Polyethyleneimine.
Chem. Technol. Water 2010, 32 (2), 125–134.
8. Soldatkina, L. M; Sagajdak, E. V. Kinetics of Adsorption of Water-Soluble Dyes on the Active
Coals. Chem. Technol. Water 2010, 32 (4), 388–398.
9. Janos, P.; Buchtova, H.; Ryznarova, M. Water Res. 2003, 37 (20), 4938–4944.
10. Bagrovskaja, N. A.; Nikiforova, T. E.; Kozlov, V. A. Influence Acidities of the Environment
on Equilibrium Sorption of Ions Zn (II) and Cd (II) Polymers on the Basis of Cellulose. Mag.
Gen. Chem. 2002, 72 (3), 373–376.
CHAPTER 16

SOME COORDINATION
COMPOUNDS OF ARSENIC AND
STIBIUM
N. LEKISHVILI1*, M. RUSIA1, L. ARABULI1, KH. BARBAKADZE1,
I. DIDBARIDZE2, M. SAMKHARADZE2, G. JIOSHVILI1,
K. GIORGADZE1, and N. SAGARADZE1
1
Faculty of Exact and Natural Sciences, Institute of Inorganic–Organic Hybrid
Compounds and Non-traditional Materials, Ivane Javakhishvili Tbilisi State University,
1 Ilia Chavchavadze Avenue, Tbilisi 0179, Georgia. E-mail: *[email protected]
2
Kutaisi Akaki Cereteli State University, 59, Tamar Mephe st., 59, Kutaisi 4600, Georgia

CONTENTS
Abstract..................................................................................................................212
16.1 Introduction .................................................................................................212
16.2 Georgian Regional Natural Secondary Resources of Arsenic Industry.......214
16.3 Novel Bioactive Hybrid Coordination Compounds of Some Tertiary
Arsines with Mercury (II) Halides...............................................................224
16.4 Coordination Compounds of Mercury (II) Nitrate with Triaryl-and
Diaryl-Alkylarsineoxides ............................................................................227
16.5 Coordination Compounds of Some D-Metal Tetrathioarsenates (V)
with Pyridine ...............................................................................................232
16.6 Synthesis and Study of [(I-Pr)2(Et)4As2(Ph)][Co(Ncs)4] Using
X-Ray Diffraction and Ir Spectroscopy Analyses........................................239
16.7 Stibum-Containing Bioactive Complex Compounds Based on D-Metals
and Some Nitrogen-Containing Ligands: Synthesis, Structure, and
Properties.....................................................................................................244
16.8 Obtaining and Study of Arsenic-Containing Borates Based on
Transformation Products of Industrial Waste .............................................262
Keywords...............................................................................................................268
References..............................................................................................................268
*
The paper is dedicated to 75th anniversary of our teacher and senior friend Prof. Dr. Roman Gigauri.
212 Process Advancement in Chemistry and Chemical Engineering Research

ABSTRACT
Based on arsenic compounds obtained by transformation of arsenic industrial
waste and natural resources, [arsenic(III) oxide, arsenic(III) chlorides, alkoxides,
stibium(III) oxide], we obtained and studied new coordination compounds, “white
arsenic,” hyperpure metallic arsenic and various materials with specific properties.
By using obtained nonvolatile inorganic–organic complexes, we created and
tested new cheap anti-microbe means and fungicides for protection of archeological
items and museum exhibits and biological stuffed. Based on the organic hetero-
chain polymers modified by carbon-functional siliconorganic oligomers, we cre-
ated antibiocorrosive covers for woodwork, goods from plastics and leather. In the
monograph, the possibility of obtaining siloxane–arsenic oligomeric additions for
underwater hydrophobic bioactive dye composites is discussed. It showed real per-
spective to manufacture pharmaceutical preparates, anthelmintes, semiconductors,
optical glass fibers, and biomedical nanocomposites based on Georgian region’s
arsenic industrial waste and natural resources.

16.1 INTRODUCTION
The problem in creation of a system that guarantees protection to human and envi-
ronment from microorganisms attack for increasing the quality of human life has to
be solved by
• proccessing of new effective preparates;
• prevention of materials from biodeterioration and noncontrolled biodegrada-
tion;
• inhibition of growth and expansion of microorganisms, which are causal fac-
tors of infection—inflammatory sickness of human;
• prophylaxis and treatment of human diseases, provoked by microorganisms
and crop’s protection against diseases, caused by some microorganisms, and
human protection during a contact with them;
• obtaining biologically active compounds and composites with the aim of their
inclusion into polymer matrix using different methods of their fixation in the
latter;
• study of biological activity of synthesized compounds and screening
of biologically active compounds BAC of natural derivation in rela-
tion to test cultures of various microorganism genera—biodestructors
of polymer materials, etiological factors of the mycosis, plant patho-
gens: Aspergillus, Penicillium, Cladosporium, Candida, Fusarium, etc.;
creation of polymer matrices by structural and chemical modification of
industrial polymers.
The perspective sources for obtaining various bioactive compounds are Geor-
gian natural resources.
Some Coordination Compounds of Arsenic and Stibium 213

Three main tendencies are well defined while using production waste of Geor-
gian chemical plants:
1. Regeneration of valuable compounds having noteworthy functions from
production waste.1–5
2. Recycling of so-called thrown-out and unused accumulated production
waste and elaboration of technology of production of various useful cheap
compounds from them.6
3. Use of production waste for production of various compounds and materials
having peculiar properties.7,8
Arsenic is among the relatively less widespread elements.9 Its deposits are lo-
cated at the Georgian region, in general, such as arsenic industrial waste and real-
gar–auripigment and arsenic pyrite (As2S2–As2S3–FeAsS) natural sources. Pyrite,
antimonite, nickel, gallium, manganese, titanium, copper etc. contain arsenic in a
small amount and are considered as second-rate mineral sources of arsenic.
Realgar (As4S4)–auripigment (As4S6) ore is world’s only one and unique pre-
dominant raw material of arsenic. Dominant’s content in this ore is especially high
and reaches 10–12%.9 Besides, it is very important that this ore doesn’t contain
admixtures of other elements and has bright prospects of receipt of not only metallic
arsenic and As2O3 of high purity, but also of other interesting products (Fig. 16.1).11
Despite the fact that for extraction of arsenic and its products from realgar (As4S4)–
auripigment (As4S6) ore, first of all it is necessary to burn concentrate in special
furnace so that environment pollution with sulfur dioxide and aerosol containing
2–3% of white arsenic cannot be eliminated,12 in case a revival of corresponding en-
terprise makes topical manufacturing and putting into operation of catching devices
with appropriate design.

FIGURE 16.1  The samples of arsenopyrite (a), realgar (b), and auripigment (c).

Arsenic is also the natural associated element of variety of nonferrous and noble
metals after pyrometallurgical processing of arsenic ore, which is one of the indis-
pensable conditions of recovery of individual conditions of these metals. Indus-
trial waste due to current technological processes contains arsenic in good supply
(8–60%).13 At the same time, they contain commercially significant amount of noble
metals. In order to get rid of environmental pollution, the residues are buried in
214 Process Advancement in Chemistry and Chemical Engineering Research

special ground disposals that are associated with considerable material and financial
expenses.
During production of chemically pure arsenic sulfide from realgar–auripigment
ore using vacuum thermal method14 along with desired product, coproducts, which
contain desired product in significant amount, are originated. Despite the above-
mentioned process, neither the technology of extraction of arsenic and its satellite
elements (e.g., stibium) from realgar–auripigment ore processing products, nor the
application areas for products received from waste are not assimilated to the full ex-
tent today and require further development from the viewpoint of creation of cheap
raw materials base on their basis.
In the represented article, production waste of former mining and chemical
plants of Georgian arsenic production are considered as secondary resources for
receipt of important arsenic-containing compounds.

16.2  GEORGIAN REGIONAL NATURAL SECONDARY

RESOURCES OF ARSENIC INDUSTRY
There are considerable reserves in Georgia for extraction of arsenic in its various
forms (e.g., sulfides, oxides) from arsenic production waste (arsenic pyrite and real-
gar–auripigment processing waste and waste of pyrometallurgical production) and
for production of relatively cheap important compounds and materials with peculiar
properties, for example, pharmaceutical preparations, anthelmintics, antimicrobial
and parasiticide compounds, conserving agents, as well as industrial use (for techni-
cal purposes) and bioactive synthetic compositions and materials.4,15–17 There is a
real prospect of production of arsenic-containing nontraditional advanced materials,
antibiocorrosive coatings, nanocomposites and nanomaterials of biomedicine, and
microelectronic purposes on the basis of arsenic production waste.18,19
We have established that arsenic-containing production waste may be used as
starting material for production of gold, barium hydrous arsenate, strontium hydrous
arsenate, magnum–ammonium arsenate, sodium monoselenoarsenate, cyclic esters
of arsenic acid etc. Among them, barium hydrous arsenate is the best anthelmintic.
Strontium hydrous arsenate is used in homeopathy, while it is used as anthelmin-
tic in veterinary. Magnum–ammonium arsenate is used in production of special-
purpose glasses, sodium monoselenoarsenate as insecticide, while cyclic esters of
arsenic acid are used for production of insecticides, as inhibitors of lubricants’ oxi-
dation, as antioxidant for synthetic rubber, for production of some copolymers, etc.
Homeopathy,20 as one of the most interesting directions of therapy, has attracted
a serious attention in the last years, in which, the possibilities of application of some
arsenic compounds received on the basis of production waste seem to be very pro-
spective.
Some Coordination Compounds of Arsenic and Stibium 215

Development of above-mentioned directions will promote creation of cheap raw

materials base that will make accessible production of well-known and new arsenic-
containing compounds having a lot of interesting properties and will simplify their
practical implementation (Fig. 16.2).

FIGURE 16.2  The scheme of obtaining and use some of important arsenic-and stibium-
containing compounds from arsenic industrial waste.

Esters of arsenic acids received from production waste may be used for produc-
tion of a variety of new arsenic-containing preparations, which have found mani-
fold uses. First of all, the most important is the possibility of gold extraction from
pyrometallurgical waste, as well as receipt of barium hydrous arsenate, strontium
hydrous arsenate (used in medicine, namely, in homeopathy, while as anthelmintic
in veterinary), sodium monoselenarsenate, cyclic esters of arsenic acid, and other
substances. Magnum–ammonium arsenate (V) is widely used in production of spe-
cial-purpose glasses. Demand for this preparation increased day by day in the last
years. That’s why elaboration of upgraded method of its production21 is of great
practical importance.
The structure of some important inorganic and organic arsenic compounds is
given below (Table 16.1).
 216

TABLE 16.1  Basic Physical–Chemical Properties of Coordination Compounds of Some Tertiary Arsines with Mercury (II) Halides
(HgHal2As(R)Ar2).

Molar electric
No Melting conductivity in Found, Calculated, (%)
Ar R Hlg
point, dimethylformamide (%) Brutto
°C at 25°C, As Hlg As Hlg
formula
om-1cm2 mol-1
1 m-CH3C6H4 m-CH3C6H4 Cl 173–174 24.6 11.70 11.52 C21H21AsHgCl2 12.09 11.45
2 m-CH3C6H4 C2H5 Cl 137–139 25.7 13.15 13.64 C16H19As HgCl2 13.44 12.72
3 m-CH3C6H4 iso-C4H9 Cl 143–144 25.4 12.45 12.02 C18H23As HgCl2 12.79 12.12
4 C6H5 n-C4H9 Cl 122–123 23.1 13.40 12.72 C16H19As HgCl2 13.44 12.72
5 C6H5 iso-C3H7 Cl 150–151 28.4 13.28 13.10 C15H17As HgCl2
13.79 13.05
6 C6H5 C6H5 Br 180–181 22.6 11.17 23.89 C18H15As HgBr2
11.24 23.99
7 m-CH3C6H4 m-CH3C6H4 Br 164–165 25.4 10.20 22.33 C21H21As2HgBr2
10.57 22.57
8 m-CH3C6H4 C2H5 BrBr 131–139 27.7 11.49 24.72 C16H19As HgBr2
11.59 24.73
9 C6H5 n-C4H9 Br 147–148 22.4 11.32 24.66 C16H19As HgBr2
10 m-CH3C6H4 iso-C4H9 Br 145–148 26.9 11.09 23.42 C18H23As HgBr2
11.59 24.73
11 C6H5 iso-C3H7 158–159 29.5 11.36 24.98 C15H17As HgBr2 11.11 23.70
11.84 25.28
Process Advancement in Chemistry and Chemical Engineering Research
Some Coordination Compounds of Arsenic and Stibium 217

In marketable condition, it can be used as intermediate product. Namely, prod-

ucts of interaction of this compounds and monoatomic spirits of saturated row (ROH,
where R = С5Н11 or iso-С5Н11) during chemical reactions manifest such behavior as
if we have arsenic oxide (III) of high purity. As we already have mentioned earlier,
interaction of spirits and white arsenic, including arsenic anhydride contained in
mixtures, represents well-defined selective reaction, as a result of which, the ester
of arsenic acid of high condition is received. The latter in his turn, as all compound
esters easily experience hydrolyzation in water solutions, with formation of white
arsenic and corresponding spirit. Arsenic oxide (IV) manifests the same properties.
This circumstance can be successfully used not only for production of well known
and widely used compounds, but also for synthesis of novel compounds. Use of es-
ter of arsenic acid as source raw material eliminates carrying out of such hazardous
and complex processes as the receipt of high-toxicity arsenic compounds (AsH3,
AsCl3), their purification and reduction up to metallic arsenic or transformation into
compounds with peculiar properties.22
We established that there is no necessity for burying so-called “tails” of arse-
nic production in appropriate ground disposals, if there is no arsenic in the form
of oxide in them. They can be used as intermediate product. Their processing by
monoatomic spirits ROH of saturated row, where R = С4Н9, С5Н11, iso-С5Н11, or by
С6Н13 using the method of azeotropic dehydration, is possible. This process is based
on well-defined selective reaction, since among residues, only arsenic oxides or
corresponding acids undergo a reaction with spirits, while coproducts remain on the
bottom of reactor in form of slugs. High-purity esters of arsenic acids are received as
a result of reaction. They, as all compound esters, are easily hydrolyzed in the water
solutions with formation of white arsenic and corresponding spirit. Obtained spirit
can be used again as extragent, so this process takes continuous character and at the
same time, cyclical pattern. It is clear that there will be a negligible loss of spirit
anyway, which is consumed for soaking of spirit. Obtained spirit extracts can be
successfully used once more for receipt of both inorganic and organic compounds.
Methods of receipt of very important arsenic compounds—arsenic oxides (e.g.,
“white arsenic”), arsenic sulfides, metallic arsenic of high purity, and other com-
pounds on the basis of waste of hydro- and pyrometallurgical production are de-
scribed in the literature.4,22–26 Mentioned compounds represent basic/starting sub-
stances for production of arsenic-containing compounds.27,28
Among arsenic products, the receipt of one of the most valuable substances,
metallic arsenic of high purity, is of special importance. This production is based
on the preliminary treatment of some of the arsenic-containing compound and af-
terwards on its chemical transformation.12 Elaboration of intensive technology of
metallic arsenic production is one of the most topical problems of arsenic chemistry
and technology, all the more if we use production waste transformation products as
starting substances.
218 Process Advancement in Chemistry and Chemical Engineering Research

Use of ester of arsenic acid as source raw material eliminates carrying out of
such hazardous and complex processes as are the receipt of high-toxicity com-
pounds (AsH3, AsCl3), their purification and reduction up to metallic arsenic (Fig.
16.2) or transformation into compounds with peculiar properties.22
Thus, in above-mentioned direction, chemists, researchers, and entrepreneurs
pay a lot of attention to the development of such progressive and economically sub-
stantiated technologies, where:
• amount of operations for receipt of ester of arsenic acid obtained from arse-
nic-contained waste is reduced to minimum, which considerably simplifies
the quality control of obtainable product;
• extraction of highly explosive (e.g., H2) and toxic coproducts (e.g., HCl, etc.)
have to be eliminated.
Use of compounds received in agriculture from arsenic-contained waste (mostly
in the form of alkali salts (Na3AsO4)) in relation with escalation of fighting with
environmental pollution decreasing more and more, while areas of metallic arsenic
application are extended. Namely, it is used in up-to-date technologies,28,29 while
Ga2As3 and InAs (arsenides) are used for manufacturing of luminescent and laser,
microwave and switching diodes, detectors, transistors, solar batteries, integrated
circuits, and microelectronic devices.
Ultraclean metallic arsenic is used in semiconductors production, as well as for
manufacturing of various alloys.30
Arsenic (III) extracted from production waste may be used as intermediate prod-
uct for receipt of various compounds with reacting capacity. For example, products
of interaction of this compounds and saturated monoatomic spirits (R > Bu) mani-
fest such behavior in chemical reactions as arsenic oxides of high quality of purity.31
We established that interaction of spirits and white arsenic represents well-defined
selective reaction, as result of which, the ester of arsenic acid of high condition
is received. The latter, in its turn, as all compound esters, easily experience hy-
drolyzation in water solutions, with formation of white arsenic and corresponding
spirit. Obtained spirits can be used again as extragents. This means that process has
continuous and at the same time cyclic nature. It is clear that there will be a negli-
gible loss of spirit anyway, which is consumed for soaking of solid phase. Obtained
spirit extracts can be successfully used once more for receipt of both inorganic and
organic compounds. As it turns out, products of transformation are considerably of
high quality than it is accomplished directly on the basis of “white arsenic.” Above-
mentioned researches have been further developed during last 5–6 years, which was
reflected in numerous articles and abstracts of international reports.
Among arsenic-containing compounds, the most interesting are tertiary arsines
and their salts.31–35 As it turns out from the review of corresponding scientific lit-
erature, tertiary arsines easily alkylate via “inclusion” into chemical bond of 4s2-
electrons of central atom, and form arsonium salts of polyfunctional composition.
Organic iodine derivatives play the role of electrophile for the most part, since in
Some Coordination Compounds of Arsenic and Stibium 219

contradistinction from other halogen derivatives, they easily enter into reaction of
nucleophilic addition.
Thus, arsonium salts with general formula [R4As]X, where R = organic radi-
cal (alkyl, alkylene or aromatic), while X = Hal–, NO3–, CH3COO–, etc., should be
considered as cationic complexes, since they experience electrolytic dissociation in
water or other polar solvents according to the following equation:
[R4As]X [R4As]+ + X–
It should be noted that there are no similar radicals among all 4R’s. Moreover,
the most difficult of receipt, and therefore, of study, is the case when we deal with
asymmetric arsonium halogenides. The latter substances are received by alkylation
of tertiary arsines:
R3As + R–Hal → [R4As]Hal
Also, noteworthy is the fact that tetraalkyl(aryl)arsonium salts represent the best
precipitators for a variety of complex anions.36
Receipt of cationic–anionic complexes of tetra-substituted arsenic (arsonium)
is possible not only by exchange and addition reactions, but also by substitution
reaction.37
Proceeding from above-mentioned information and also with the use of arsenic
chemical raw materials and other kinds of waste available in Georgia, from the
practical viewpoint (biological activity), the coordination compounds on the basis
of tertiary alkyl(aryl)arsines are very prospective.38–40
Impact of arsenic as toxic element on flora and fauna of Racha and Svaneti
(Georgia) is considerable as it makes a recycling of accumulated waste of its pro-
duction even more topical.
At this moment, in above-mentioned direction, chemists, researchers, and entre-
preneurs pay a lot of attention to development of such progressive and economically
substantiated technologies, where:
• amount of operations for receipt of ester of arsenic acid obtained from arse-
nic-contained waste is reduced to minimum, which considerably simplifies
the quality control of obtainable product;
• extraction of highly explosive (e.g., H2) and toxic coproducts (e.g., HCl, etc.)
has to be eliminated;
• possibility of formation of toxic intermediate products or waste (which re-
quires neutralization of burying) should be reduced to the minimum in the
whole treatment cycle;
• environment should be protected from pollution and poisoning with high-
toxic substances.
Processing and transformation of stibium-containing production waste into sta-
ble coordination compounds of peculiar properties is important with the purpose of
its further use that ranges among topical problems of modern applied and coordina-
tion chemistry. Successful solution of this problem not only will create new raw
materials base but also will solve important ecological problem, will protect envi-
220 Process Advancement in Chemistry and Chemical Engineering Research

ronment from pollution with stibium-containing waste. Certain positive results are
obtained by Georgian scientists–chemists in this direction, who carry out a synthesis
and study a lot of interesting stibium compounds (Prof. R. Gigauri and colleagues).
There is elaborated by our method of possible separation of arsenic (III) and
stibium (III) oxides from each other.4 Azeotrope effective for this process is selected.
The used method is based on the fact that arsenic oxide quantitatively com-
pletely interacts with spirits, for example, with butyl spirit with formation of tributyl
arsenite, and as a result of its hydrolysis, white arsenic of high purity is received;
arsenic and stibium oxides, which are not included into reaction, turn out to be
constituent component of pyrometallurgical waste of many polyelement ores, that’s
why elaboration of low-temperature methods of their removal and separation from
waste is interesting issue for production processes.
Above-mentioned method is rather economically viable compared with other
current methods.
Among stibium compounds, stibium (III) oxide and stibium (III) sulfide (Fig.
16.3) are also important from the practical viewpoint. Stibium (III) oxide is used for
production of modern fireproof dyes and enamels, brand new functional materials,
and composites.41–47

FIGURE 16.3  The crystal of As(III) sulfide.

Stibium (III) sulfide is used in match production, as well as in military industry.

Stibium compounds are widely used in pharmaceutical, textile, and other technolo-
gies. Stibium is also produced in Georgia in the form of sulfide minerals, which are
Some Coordination Compounds of Arsenic and Stibium 221

known under the label of antimonites (Sb2S3). Content of basic metal in commercial
brands of metal stibium, which are available at world market, reaches 99.95%.
Among stibium (V) compounds, one of the most important is sodium thios-
tibiate Na3SbS4, which is good complex former.41–43 Due to it, from the economic
viewpoint, receipt of stibium compounds (as of arsenic satellite elements) on the
basis of arsenic production waste is of special importance, which will make cheaper
corresponding final compounds and as a result, coordination compounds derived
from them.
Among works published in the area of stibium chemistry, we consider Kanatzi-
dis’ work as classical one.44 Author investigates the possibility of receipt of stibiates
(III) with metal triethylenediamines under the action of alkali metals dithioantimo-
nites on coordination compounds of Co (II) and Ni (II). The synthesis of a variety
of coordination compounds occurs in a same way, only with the difference that
tetrathiostibiates (V) are used as precipitators.45–47
In the era of the violent technical progress, wide assortments of synthetic and
natural polymeric materials have produced. At the same time, various aggressive
microorganisms (more than several hundred) appeared, which can destruct these
materials, especially carbon containing. Losses caused by this mean reach enormous
amounts and constitute milliards of dollars annually.
Together with above-mentioned information, protection of historical buildings,
archeological examples, museum exhibits, and collections is global problem and
this topic is actually all over the world. Many Congresses and symposiums are dedi-
cated to this topic. Substantial funds are allocated for solving this problem.
One of the ways to protect from aggressive microorganisms and fungi of wide
range of synthetic and natural materials is creation of direct action multifunctional
synthetic antibiocorrosive coatings based on various inorganic–organic hybrid com-
posites.
We have developed new antibiocorrosive coatings,48,49 where bioactive compo-
nents used are stable, nonvolatile organometallic complexes, safe for human life in
conditions of certain concentrations, also highly dispersed bioactive inorganic (pos-
sibly nanoparticles) (Fig.-s 1.3-1.5) obtained by transformation of the secondary
raw material. Bioactive compounds dropped into the polymeric carriers modified
with industrial functional polymers, which are distinguished with good compatibil-
ity.
Obtained antibiocorrosive coatings:
• are characterized by a good fixation on various synthetic and natural materi-
als, as well as on museum exhibits and archeological samples;
• do not violate wholeness of samples during hardening of the cover compos-
ites;
• are transparent (Fig.-s 1-3) and almost do not change the color during their
aging;
222 Process Advancement in Chemistry and Chemical Engineering Research

• have enough strength, elasticity, and stable mechanical characteristics (they

do not scratched easily and do not change relief of the surface) and high hy-
drophobility (<0.1%), typical for such materials (Fig. 16.3);
• are not dangerous for human; during long time of exploitation, do not produce
harmful gases;
• and are relatively cheap and available.
Their thermal stability (in air, isothermal aging at 40 and 60°C), on action of
so-called “light weather” (complex action of moisture and of air oxygen, of sun-
scattered ultraviolet radiation, and CO2) showed that during the long period, the ini-
tial expression, color, optical transparency, and mechanical properties (homogeneity
of the surface without formation of splits), antibiocorrosive coatings did not worsen.
Instead of easily swillable tin- and arsenic-organic low molecular antibacterial
additives to dye composition with specific properties, industrial silicon polymer
modified by bioactive fragment (Fig. 16.4) were used.

FIGURE 16.4  Industrial silicon polymer modified by bioactive fragment.

In case of necessity, it is possible to obtain antibiocorrosive coatings with dif-

ferent color (Figs. 16.5–16.7), which can be adjusted by selecting of appropriate
bioactive components.

FIGURE 16.5  Antibiocorrosive coatings containing inorganic–organic bioactive structures

obtained by transformation of the arsenic industrial waste (I and II samples: leader, III: wood).
Some Coordination Compounds of Arsenic and Stibium 223

FIGURE 16.6  Antibiocorrosive coatings (first two samples) and due composite contained
bioactive silicon polymer: first sample from left—antibiocorrosive coatings for polycarbonate
plate based on high dispersed stibium(III) oxide and polyepoxide modified by industrial
silicon polymer; second sample from left: optically transparent antibiocorrosive coatings for
organic glass plate based on high dispersed stibium(III) oxide and polyepoxide modified by
siliconorganic oligomer; third sample from left: dye composite, contained bioactive silicon
polymer for protection of underwater part of the ship.

FIGURE 16.7  Left column: first and second samples from the top: optically transparent
antibiocorrosive coatings based on high dispersed stibium(III) oxide and copolymer of
perfluoro methacrylate and ethyl methacrylate covered on the polycarbonate plate. Right
column: optically transparent antibiocorrosive coatings based on high dispersed stibium(III)
oxide and copolymer of perfluoro methacrylate and ethyl methacrylate covered on the organic
glass plate.

The potential spheres of using of obtained bioactive composites are:

• prevention of materials from biodeterioration, noncontrolled biodegradation,
various branches of industry, and human protection during contact with this
materials;
224 Process Advancement in Chemistry and Chemical Engineering Research

• inhibition of growth and expansion of microorganisms, which are causal fac-

tors of infection—inflammatory sickness of human and animals; for prophy-
laxis of above-mentioned diseases provoked by microorganisms;
• protection of museum exhibits and some of cultural heritage;
• for obtaining dye composition for protection of underwater part of the ship
toward aggressive microorganisms excreted by some algae.
It must be noted that, in case of need, it will be possible to remove some of the
antibiocorrosive covers from the surface without damaging it, which is especially
important during the restoration of museum exhibits and archeological samples.
According to the information obtained from scientific literature of last decade,
the interest toward stibium and its traditional compounds seems to be reduced rela-
tively worldwide. More attention is switched to arsenic and its compounds.48,49 This
fact can be caused by the circumstance that best efforts are focused on removal from
environment and desired use of arsenic as one of the most undesirable pollutant,
while stibium is easily removed from almost all satellite elements.
At present, special attention is paid to synthesis and research of hybrid arsenic
compounds having biocide properties, since some of them may be successfully used
for receipt of bioactive additives, biostable polymers, dyes etc., and part of them is
used against phytopathogenic bacteria.49 Based on this position, it is clear that syn-
thesis of arsenic-containing compounds and study of their biocide properties carries
out intensively.50–54
In the recent years, the ministry of environment protection and natural resources
of Georgia is vitally interested in solution of this problem. For this purpose, a spe-
cial 6-year program named “Recycling and decontamination of production waste of
arsenic mining and chemical plants of Georgia” has been elaborated by the ministry
last year. This program is in full compliance with project represented by us. In case
of winning of this project, the focuses of environmental pollution with the waste
obtained as a result of arsenic ore processing will be deactivated (Fig. 16.6). Their
harmful impact on human’s health will be maximally decreased, and tourism devel-
opment and production of ecologically clean agriculture product in the Georgian
region (Svaneti and Racha) will be promoted.

16.3  NOVEL BIOACTIVE HYBRID COORDINATION

COMPOUNDS OF SOME TERTIARY ARSINES WITH MERCURY (II)
HALIDES
We have synthesized39 two types of coordination compounds: Ar2AsR•HgCl2 and
Ar3As•HgX2 (X = Cl, Br) (Table 16.1 Asymmetry tertiary arsines complexes type of
Ar2AsR•HgCl2 (where Ar is aryl and R is alkyl) were formed according to the fol-
lowing reaction (Scheme 16.1):
Some Coordination Compounds of Arsenic and Stibium 225

Ar2AsR + HgCl2 → Ar2(As)R•HgCl2

SCHEME 16.1

It was shown that symmetric trialkyl arsines could not form crystalline com-
pounds with mercury (II) chlorides:

R3As + HgCl2 R3As . HgCl2 ,

where R = n-C3H7, iso-C5H11, or C7H25.

Symmetric triaryl arsines have formed with mercury (II) halides crystalline
products:
Ar3As + HgX2 → Ar3As•HgX2, where Ar = C6H5 or m-CH3–C6H4, X = Cl or Br.
It was established that the change of the ratio of initial reagents (in wide limits)
did not influence on the chemical composition of the products, it was always equal
to 1:1. The assumption that the obtained products are identical was confirmed by
the fact that their melting point did not change. Thus, based on numerous experi-
ments, optimal conditions for this process were elaborated. All synthesized products
are white crystalline, stable compound. It was established that the yield in case of
triarylarsines is far less than in case of diaryl(alkyl)arsines. The rate of formation
of adducts of triphenylarsine with mercury (II) chloride and bromide prevails over
the rate of formation of the product of addition of tri-m-tolylarsines. This fact can
be explained by the spatial factor and by electronegativity of β-substituent. It must
be noted that (m-CH3–C6H4)3 As•HgCl2 is more coarse crystalline than other synthe-
sized compounds. In aqueous solution, (all the more in organic solvents) mercury
(II) halides are weakly ionized and the concentration of Hg2+ ions, for example, in
extracted solution of sublimate is not more than 10−8. It means that it is non-elec-
trolyte (αHgCl2 < αH2O) and when HgCl2 undergoes dissociation, it will stop at the first
stage: HgCl2 ↔ HgCl+ + Cl−
The addition of triaryl- and diarylalkyle arsines to mercury (II) halides can be
considered as nucleophilic process:

Ar3As + HgHal2 [Ar3As HgHal]Hal

The molecular electroconductivity of the obtained compounds was determined

in dimethylformamide. The data of the molecular electroconductivity (less than 30
cm−1 cm2) confirmed that these compounds are non-electrolytes. IR spectra of the
obtained compounds showed that the absorption band in the region 560–580 (cor-
responding to As–Calk.), disappears, thus the absorption band at 620 cm−1 appears,
which is characteristic to As–Calk., when As is in sp3 hybridization state. Based on the
data of molar electroconductivity and IR spectra, we can propose that the compound
is dimmer bridge complex:
226 Process Advancement in Chemistry and Chemical Engineering Research

Hal Hal AsAr2R

Hg Hg
, (Hal = Cl or Br)
RAr2As Hal Hal

We carried out the thermographic analysis of the synthesized compounds. The

thermolysis of each synthesized compounds is similar. The process of thermal de-
composition can be represented according to the Scheme 16.2:

Br Br As(C6H5)2C4H9-n
200-2500C
Hg Hg (C6H5)2AsHg2Br3
-C4H9Br;
Br Br -As(C6H5)2C4H9
n-C4H9(C6H5)2As
250-2800C 280-3100C
Hg2Br2 HgBr2 ...
-(C6H5)2AsBr -Hg

SCHEME 16.2

We have elaborated the method of the algebraic–chemical characterization of

typical structures (main characterizing structure) of synthesized compounds R2AsR,
where R = m-CH3C6H5; R′ = m-CH3C6H5; iso-C4H9; C2H5. For creation of the bank
of data for these chemical structures, we have used the fragmentation matrix (F-
matrix) method. We constructed the F-matrix for our systems and use lg(∆F) (F
called as fragmentation matrix)—effective topologic index for construction and
investigation of fragmentation “structure–properties” type correlation equations.
As the synthesized compounds are crystalline, we have constructed the correlation
equation and it has the form:
Tmelt = 78•lg(∆F) − 123 (A); Tmelt. = 72•lg(∆F) − 110 (B),
where A: for the complex of HgCl2, B: for the complex of HgBr2.
The values of the Tmelt. and lg(∆F) for these compounds are presented in the
Table 16.2

TABLE 16.2  The Values of the Tmelt. and lg(∆F) for Tested Compounds.
No Coordination compounds* lg(∆F) Tmelt., °C
I (CH3C6H4)2AsC2H5·HgCl2 3.35 137
II (CH3C6H4)2AsC4H9·HgCl2 3.62 143
III (CH3C6H4)3As HgCl2 3.81 173
IV (CH3C6H4)2AsC2H5·HgBr2 3.35 131

V (CH3C6H4)2AsC4H9·HgBr2 3.62 145

VI (CH3C6H4)3As HgBr2 3.81 164
*Correlation coefficient r = 0.921519; k = 72.4423; b = −111.476.
Some Coordination Compounds of Arsenic and Stibium 227

We have carried out the preliminary virtual (theoretical) bioscreening of ob-

tained structures (using the above-mentioned characterizing of arsenic-containing
fragments) by using Internet-system program PASS C&T.50 The estimation of prob-
ability of activity of compounds was carried out via determination of parameters
Pa (active) and Pi (inactive). Based on virtual bioscreening, the synthesized com-
pounds (Table 16.2, I–VI), with experimentally high probability (Pa = 0.55–0.80),
showed virtually antibacterial, antifungal, anthelmintic, antiviral, and anticarcino-
genic activity. Preliminary microbiologically study of the investigated compounds
confirmed the virtual concepts (anticarcinogenic activity was not tested).
By using synthesized bioactive compounds (1–3–5%) and selected polymer ma-
trix (polyurethanes and polyester urethanes non-modified and modified by silicon-
organic oligomers), we prepared novel inorganic–organic antibiocorrosion covers.51
We studied tribological properties52 of polymer matrices and antibiocorrosion cov-
ers based on them. It was established that the friction of polyurethane and polyester
urethane matrices modified by siliconorganic oligomers and antibiocorrosion cov-
ers, is higher for non-modified polyurethanes. So, the modification can be used for
improvement of tribological properties of antibiocorrosive covers. By using gravi-
metric method, the water absorption ability of obtained antibiocorrosive covers was
determined. It was established that during 720 h, their water absorption ability was
0.01–0.03%. Their testing on photochemical and thermal stability (in air, isothermal
aging at 40 and 60°C), on action (on definite time) of “light weather” (complex ac-
tion of moisture and of air oxygen, of ultraviolet eradiation of sun or of “scattered”
sunlight, CO2) showed that during 1200 h, the initial expression, color, optical trans-
parency, and mechanical properties (homogeneity of the surface without formation
of splits) of antibiocorrosive covers has not deteriorated.

16.4  COORDINATION COMPOUNDS OF MERCURY (II) NITRATE

WITH TRIARYL-AND DIARYL-ALKYLARSINEOXIDES
One of the most important properties of oxides of tertiary arsines is a formation of
coordination compounds with salts of transition metals (d elements). It should be
emphasized that this kind of compounds is well studied in case of phosphorus-con-
taining ligands. As to arsenic-containing compounds, like arenes, they are almost
unstudied, if we didn’t take into account several researches, which have fragmen-
tary character and are not carried out on regular basis at all, in order to make some
substantial conclusion. It is noteworthy too that complex compounds, which contain
arsenal group As–O from the very beginning, have been widely used in practice as
the best extragents of different metals. It seems we have to seek the cause in good
capabilities of d-metals to attach oxides of tertiary arsines with formation of quite
stable compounds. In all cases of extragents R3As = O, where R = organic radical,
complex formation occurs according to electron donor–acceptor interaction mecha-
nism,249 at that donor function is performed by oxygen atom which is entered into ar-
228 Process Advancement in Chemistry and Chemical Engineering Research

sinal group, while acceptor is represented by complex former (metal) along with its
vacant (unoccupied) orbitals. As it is supposed,250 properties of mentioned ligands
should be caused by the quality of As–O bond order, which, in its turn, is caused
by the possibility of transition of two nonbonding electrons of negatively charged
substituent (O) to the vacant 4d-orbital of arsenic.
Taking above-mentioned information into account, at this time, we have tried to
study the complex formation ability of mercury (II) salts with oxides of triaryl- and
diaryl-alkylarsines. If test will prove its value, of course we also study synthesized
coordination compounds by means of accessible physical and chemical methods.
The well-known technique of triaryl(alkyl)arsine oxidation in the medium of
hydrogen peroxide acetone was used in order to receive oxides of resulting tertiary
arsines.251 Reaction runs according to the following equation:

Ar3As + H2O2 → Ar3As=O + H2O

Azeotrope-former—benzol is removed from water of reaction mixture using the

method of azeotropic dehydration.
The tertiary arsines are received using the action of Grignard reagent with esters
of arsenic acid57:

(RO)3As + 3ArMgBr → Ar3As + 3ROMgBr,

where R = n-C5H11 or iso-C5H11, while diarylalkylarsines have been received by fol-

lowing method:

Ar2AsCl + RMgBr → Ar2AsR + MgClBr

On the basis of many experiments, it was established that possibility of mercury

(II) ion complex formation from oxides of tertiary oxides is considerably depended
on the nature of ions entering into salt composition. Namely, most parts of cor-
responding halogenides are either insoluble in water and spirit or slightly soluble.
Among soluble salts, mercury (II) acetate also have not came up to our expecta-
tions—complex compounds are formed, but goal will be achieved only after gradual
drying of reaction mass that eliminates the possibility of receipt of basic product in
chemically pure condition.
Thus, all our attempts to separate in individual condition, the products of mer-
cury (II) salts interaction with arsinal compounds has ended without result.
Positive results have been obtained in the experiment only in case of mercury
(II) nitrate’s use as original substance. Regardless of ratio between reacting sub-
stances, right from the beginning of mixtures interaction, the addition products are
precipitated almost in one and the same quantitative content.
It is known that oxides of tertiary arsines are monodentate ligands,53 while co-
ordination number 4 is characteristic for mercury (II) ions. That’s why, as far as we
Some Coordination Compounds of Arsenic and Stibium 229

assured ourselves of possibility of desired product’s receipt due to action of tertiary

arsine oxide on mercury (II) nitrate, we have carried out basic experiments by taking
into account following molar ratio: Hg(NO3)2:Ar3As=O = 1:4
Reaction has been carried out in non-aqueous solutions (spirit solutions). It turns
out that in all cases, coordination number is equal to 4. Formation of desired prod-
ucts has to be explained according to the Scheme 16.3:
Ar2AsCl + RMgBr → Ar2AsR + MgClBr

SCHEME 16.3

Composition and structure of synthesized compounds was determined by meth-

ods of both chemical and physical–chemical analysis. Results of element analysis
are given in Table 16.3. Formulas of obtained coordination compounds were deter-
mined via study of molar electrical conductivity of samples dissolved in dimethyl-
formamide. As it turns out from table 2.9, μ is changed within the limits of 112–123
Ohm−1 cm2 mole−1, which is characteristic for three-ionic electrolytes.58 This fact
unequivocally points at the circumstance that investigated coordination compounds
experience this kind of electrolytic dissociation in dimethylformamide:

[Hg(O–AsAr3)4](NO3)2 → [Hg(O–AsAr3)4]2+ + 2NO3−

As to coordination rule of ligands, with the purpose of solution of this problem,

we have studied the IR spectra of synthesized compounds. Their analysis shows
that, as it was expected, a ligand is coordinated with mercury (II) ion via oxygen
atom of arsinal group. For instance, intensive absorption band in 880–900 cm−1 area,
which is referred to valence vibrations (VAs=O) of As–O bond is manifested on all
spectrograms of initial oxides of tertiary arsines. 254,55 Presence of phenyl groups
in the composition of synthesized compounds is confirmed by existence of absorp-
tion bands in 1590, 1490, 1440, 1170, 1156, 1080, 1030, 1000, 745, and 690 cm−1
areas. As–Calk bond is confirmed by existence of absorption bands in 475 cm−1 area.
It should be noted that all above-mentioned bands, except of arsinal group, are ba-
sically kept in spectra of interaction of oxides of tertiary arsines and mercury (II)
nitrate. It is not surprising, since, namely, by means of oxygen atom of arsinal group,
a ligand bounds with complex former. In particular, frequency of valence vibrations
of As–O bonds in resulting complexes’ spectra is decreased by 20–50 cm-1. This
fact, in its turn, points at the circumstance that ligands are monodentate.
 230
TABLE 16.3  Some Physical Constants and Data of Element Analysis of [Hg(OAs(R)Ar2)4](NO3)2.

No Ar R Melting Molar electro­ Found, (%) Brutto formula Calculated, (%)

point, °C conductivity in di-
methylformamide
at 25°C, As Hlg As Hlg
omi−1sm2 mol−1

1 m-CH3C6H4 n-C4H9 95–96 112.5 18.05 12.20 C72H92As4HgN2O10 18.23 12.21

2 m-CH3C6H4 iso-C3H7 121–122 114.7 18.66 12.65 C68H84 As4HgN2O10 18.87 12.64

3 p-CH3C6H4 n-C4H9 87–88 118.5 18.11 12.18 C72H92 As4HgN2O10 18.23 12.21

4 p-CH3C6H4 iso-C4H9 118–119 116.9 18.14 12.18 C72H92As4HgN2O10 18.23 12.21

5 C6H5 C6H5 128–129 120.4 18.41 12.44 C72H60 As4HgN2O10 18.59 12.46

6 m-CH3C6H4 C2H5 108–109 122.6 19.23 13.14 C64H71 As4HgN2O10 19.56 13.11
Process Advancement in Chemistry and Chemical Engineering Research
Some Coordination Compounds of Arsenic and Stibium 231

While considering absorption IR spectra, we make sure that in [Hg(O=AsAr3)4]

(NO3)2 and [Hg(O=As(ROAr2)4](NO3)2 compounds, a nitrate-ion (NO3)− is locat-
ed in second sphere of complex (see Fig. 2.14), which is determined by means of
IR spectral data and points at the splitting of absorption band in 1300–1500 cm−1
area, while V(NO3) absorption band in 840 cm−1 is singlet. The fact that bond between
complex former and ligand is strengthened by means of oxygen atom of arsinal of
arsenic-containing compounds is confirmed by availability of absorption band in
~930 cm−1 area of IR spectra.
All above-mentioned information gives us an opportunity to make an univo-
cal conclusion that synthesized coordination compounds represent three-ionic com-
plexes that, along with molar electric conductivity, are confirmed by spectral analy-
sis of researched substances.
Behavior of synthesized compounds during heating was also studied. Tetra (di-
m-tolyl-buthylarsinoxymercury (II) nitrate thermograph is given by us as a sample
(Fig. 2.15). As it turned out from this figure, thermolysis occurs quite difficult and
contains no more than five exothermal effects and four endothermic effects. Using
detailed analysis, we make sure that exothermal effect indicated at the DTA, as a
rule, is not in compliance with weight gain. Therefore, the mentioned effect cannot
be caused by addition reaction, for example, by involvement of air oxygen in chemi-
cal reaction. We guess that, in this case, we deal with even more complicated trans-
formations that, maybe, should be caused by intramolecular regrouping into ther-
modynamically advantageous condition. This fact in our opinion can be explained
by retro–Arbuzov regrouping53 in ligand molecule subsequent to which takes place
complex melting during compound’s heating up to high temperature.
It is not impossible that diphenyl ester of arsenic acid would be received by
further oxidation of Ar2AsOR-type compound, but in this case, the role of oxidiz-
ing agent may be played not by air oxygen but nitrate-ion oxygen according to the
general pattern:
Ar3As + H2O2 → Ar3As=O + H2O

As it was mentioned earlier, we have an opportunity to make such conclusion

due to the fact that weight gain doesn’t occur, though there is a pronounced exo-
effect at DTA curve. Besides, it is well known from literature59 that such transforma-
tions are quite allowable and are caused by system’s transition to so-called energeti-
cally “advantageous condition.”
Taking into account this consideration, we can represent the thermolysis of,
for example, tetra(di-m-tolyl-n-buthylarsinoxide) mercury (II) nitrate as follows:
sample decomposition begins at 90°C and gradually continues up to 600°C. Weight
loss in the range of 90–445°C is 21.66% that corresponds with breakaway (theoreti-
cally 23.70%) of N2O3 and tertiary arsines (m-CH3C6H4)2AsC4H9 from the sample.
In the same range, especially from 220°C, “intramolecular transformations” takes
place, which, as we mentioned, have to be explained by retro–Arbuzov regrouping.
232 Process Advancement in Chemistry and Chemical Engineering Research

Separation of organic fragment takes place under 465–600°C conditions. At that,

mercury (II) oxide also experiences final decomposition that is succeeded by com-
plete “vaporization” of residue. Thus, at the last stage, not only ligand’s removal
occur, but also the decomposition and vaporization of inorganic residue itself: HgO
→ Hg + 1/2O2, which is one of the basic distinctive features of mercury (II) complex
compounds in contradistinction from similar compounds of all other d-elements.
Hence, taking into account the above-mentioned information, the most likely
pattern of thermolysis of considered complex compound can be represented as fol-
lows:

[Hg(O=As(C6H4–CH3-m)2C4H9-n)4](NO3)2 → −N2O3; (m-CH3C6H4)2AsC4H9-n

465–6000°C

HgO(m-CH3C6H4As-OC4H9CH3-m)3 → Hg + 3(m-CH3C6H4O)2AsOC4H9-n

Thus, as a result of our research, it was established that products of interaction

of mercury (II) nitrate and oxides of tertiary arsines are corresponding complex
compounds.
Composition and structure of synthesized substances were determined using
methods of IR spectroscopy, element analysis, and molar electric conductivity (Ta-
ble 16.3). It is shown that bond between complex former and ligand is strengthened
by means of oxygen atoms of arsinal group. Nitrate-ion is located at the second
sphere of complex.

16.5  COORDINATION COMPOUNDS OF SOME D-METAL

TETRATHIOARSENATES (V) WITH PYRIDINE
As we have mentioned in the introduction to the article, searching and creation of
new cheap raw materials base becomes more and more topical at the modern stage
of chemical science’s development. Under the conditions of deficit, the use of prod-
ucts obtained as a result of transformation of arsenic production waste, for receipt
of coordination compounds having peculiar properties, will promote not only an
elaboration of commercially interesting forms of appropriate compounds, but also
will solve important problem, will protect environment from pollution with arsenic-
containing residues. One of the most interesting ways of solution of this problem
is the receipt of new bioactive coordination compounds from arsenic-containing
production waste.
As is known from literature, polyelement coordination compounds manifest a
lot of interesting properties that gives us an opportunity of their wide practical ap-
plication. In recent years, among this type of compounds, the complex formers gen-
erate special interest, which contain tetrathioarsenate groups along with nitrogen
and d-metals.56–58
Some Coordination Compounds of Arsenic and Stibium 233

Goal of our research is a receipt and study of coordination compounds of zinc,

mercury (II), copper (II), and nickel (II) with pyridine—one of the most prospective
and accessible nitrogen-containing ligand received on the basis of products obtained
via transformation of above-mentioned production waste. These compounds may
manifest high bioactivity.
As the initial compounds, we have used zinc acetate, mercury (II) nitrate, cop-
per (II) sulfate, and nickel (II) chloride, that is, salts soluble in water with above-
mentioned metals. Among arsenic-containing compounds, we have used sodium
tetrathioarsenate Na3AsS4·8H2O, which we received using processing of arsenic
production waste59–60: AsCl3 ↑ + (AsCl3, H2S) + (NaOH, H2O) (Industrial waste) As2O3
→ (RO)3As → As2S3 → Na3AsS4·8H2O
IR spectra have been obtained on the spectrometer “SPECORD IR-75” in Vase-
line oil. X-ray studies were carried out on diffractometer “DRON-3М”, thermo-
graphic studies were carried out on derivatograph “Q-1500” (“F. Paulik, J. Paulik,
L. Erdey”, Hungary), by heating of test specimen in the air up to 1000°C with the
10°C/min rate. Reference substance is corundum.
Synthesis of d-metal pyridinates occurs according to exchange reaction via ac-
tion of equivalent quantity of sodium tetrathioarsenate saturated solution on the pyr-
idinates of salts of transition metals:
a) MX2 + nC5H5N → [M(C5H5N)n]X2
b) 3[M(C5H5N)n]X2 + 2Na3AsS4·8H2O → [M(C5H5N) n]3(AsS4)2↓ + 6NaX +
16H2O
or summarily:
3MX2 + 3nC5H5N + 2Na3AsS4·8H2O → [M(C5H5N)n]3(AsS4)2↓ + 6NaX +
16H2O,
Obtained complex compounds represent solid, colored, finely crystalline sub-
stances, which are dissolved in dimethylformamide, are not dissolved in water, al-
kali, ethyl spirits and liquid saturated hydrocarbons, and are disintegrated at high
temperatures up to melting. During acid treatment, they experience transformation
with formation of arsenic (V) sulfide, for example (Table 16.4):
[Zn(Py)4]3(AsS4)2 + 6HCl → 3[Zn(Py)4]Cl2 + 2H3AsS4
2H3AsS4 → As2S5 + 3H2S
Or summarily:
[Zn(Py)4]3(AsS4)2 + 6HCl → 3[Zn(Py)4]Cl2 + As2S5 + 3H2S
Composition and structure of obtained compounds was established by means
of data of element analysis (Table 16.5), infrared spectroscopy, and X-ray phase
studies.
234 Process Advancement in Chemistry and Chemical Engineering Research

TABLE 16.4  Element Analysis Data and Output of Synthesized Complex Compounds of
[M(Py)n]3(AsS4)2-Type.

Date of elemental analysis

Formula complex calculated/found, (%) The
# Color
compounds yield,
M As N S
(%)
I [Cu(C5H5N)4]3(AsS4)2 Grey 12.33/ 9.71/ 10.87/ 16.57/ 93.4
12.11 9.94 10.64 16.71
II [Zn(C5H5N)4]3(AsS4)2 Light 12.64/ 9.67/ 10.83/ 16.51/ 96.5
yellow 12.77 9.49 10.58 16.69
III [Cd(C5H5N)4]3(AsS4)2 Carroty 19.22/ 8.87/ 9.93/ 15.13/ 95.3
20.02 8.81 9.84 15.26
[Hg(C5H5N)4]3(AsS4)2 Grey 30.77/ 7.66/ 8.58/ 13.08/ 95.2
IV 29.89 7.85 8.23 13.02
[Ni(C5H5N)6]3(AsS4)2 Black 8.82/ 7.48/ 12.56/ 12.76/ 92.8
V 9.19 7.71 12.32 12.51

As is seen from IR spectra of synthesized compounds, valence vibration absorp-

tion bands, which are characteristic for AsS34− group, are manifested in them at
420 cm−1, while absorption bands of deformation vibration at 470 cm−1 area.62 Be-
sides, as is known,64 value of absorption band during free ligand’s coordination with
central atom experiences shift by ~8–30 s m−1. Absorption band of uncoordinated
pyridine u(C=N) is located in 1580 cm−1 area,64 while the same absorption band in
spectra of compounds synthesized by us is manifested in 1600–1610 cm−1 area that
unequivocally confirms the existence of pyridine coordinated with metal ions in
these compounds.
Very close agreement of tetrathioarsenate-ions absorption bands with the ab-
sorption bands of sodium tetrathioarsenate-ions indicates the fact that mentioned
anion creates second sphere of coordination compound. Data of X-ray phase
analysis of synthesized substances (Table 16.5), based on classification given in
the literature,65 testifies that obtained compounds according to their structural na-
ture belong to the subgroup of sulfosalts. Cations’ impact on ordering of crystal
structure deserves special attention. For example, copper (II) and mercury (II)
promotes formation of finely crystalline phase, which approaches to X-ray amor-
phous state.66
Some Coordination Compounds of Arsenic and Stibium 235

TABLE 16.5  Data of Roentgen phase Analysis Tetrathioarsenates (V) of Pyridine Complex
Some d-Metal (Table16.5a and Table 16.5b).
Table 16.5a Table 16.5b
[Cu(Py)4]3(AsS4)2 [Cd (Py)4]3(AsS4)2
I/I0 d α/n I/I0 d α/n
20 11.33 20 13.0
100 8.19 15 9.07
20 7.23 10
7.0
20 6.56 25
6.41
10 5.71 15
10 5.33 10 5.96
10 5.07 35 4.,33
20 4.38 25 3.90
20 4.04 15 3.27
15 3.87 15
3.17
5 3.24 20
3.05
5 3.16 20
5 3.00 15 2.98
5 2.95 30 2.94
5 2.75 30 2.43
8 2.53 20 2.23
5 2.44 10
2.19
10 2.11 15
2.15
10 1.97 15
10 1.92 40
2.08
100 1.97
1.94
1.83
1.77
236 Process Advancement in Chemistry and Chemical Engineering Research

Zn(Py)4]3(AsS4)2 [Hg(Py)4]3(AsS4)2
I/I0 I/I0 I/I0 d α/n
20 20 4 11.6
15 15 2 7.69
10 10 2
7.26
25 25 5
6.10
15 15 5
10 10 6 5.62
35 35 8 5.00
25 25 10 4.73
15 15 7 4,62
15 15 9
4.33
20 20 3
3.92
20 20 3
15 15 3 3.75
30 30 2 2.82
30 30 2 2.46
20 20 3 2.18
10 10 3
2.04
15 15
1.93
15 15
40 40
1.86
100 100

At the initial stage, breakaway of ligand from complex compound’s molecule

takes place, and afterwards, stage-by-stage thermal decomposition of tetrathioarse-
nate (V) continues.56
As is seen from results of thermographical study, processes of thermal decom-
position (thermolysis) of complex compounds of copper and zinc are almost similar
(Fig. 16.8).
Some Coordination Compounds of Arsenic and Stibium 237

FIGURE 16.8  Thermogravimetric graphs of synthesized compounds: (a) [Zn(Py)4]3(AsS4)2;

(b) [Hg(Py)4]3(AsS4)2; and (c) [Ni(Py)6]3(AsS4)2
238 Process Advancement in Chemistry and Chemical Engineering Research

There is a possibility to differ from each other, two types of complex compounds’
decomposition are obtained: thermolysis of nickel tetrathioarsenate (V) pyridine
complex (Scheme 16.4) and of mercury (II) tetrathioarsenate (V) pyridine complex:

SCHEME 16.4

Thermolysis of [Ni(Py)6]3(AsS4)2 sample (Fig. 16.8) begins from 100°C. Gravi-

metric analysis showed that first 6 moles of ligand breakaway at 200° that corre-
sponds with 23.0% of weight loss (theoretically 23.6%). Very important endother-
mal effect is observed in the range of 200–250°C, with minimum at 235°C. The
rest 12 moles of ligand breakaway in this interval. Therefore, sample’s weight loss
is 46% (theoretically 47.28%). Since then, thermal decomposition of the sample
continues in a way as that in case of corresponding neutral salt.
As is seen from comparison of Diagram 4.3 and Diagram 4.4, thermal decompo-
sition of pyridine complex of g(II) tetrathioarsenate (V) {[Hg(Py)4]3(AsS4)2} must
occur in different way. Ligand breakaway can also be represented step-by-step here:
at the first step, in the range of 100–200°C, complex loses 6 moles of pyridine, while
loses other 6 moles, in the range of 200–240°C. Weight loss at both the stages is
equal to 31% (theoretically 30.77%). After ligand’s breakaway, the process of ther-
mal decomposition continues in a way as that in case of corresponding neutral salt.56
Along with thermogravimetric analysis, data obtained results are confirmed by
the processes of thermal decomposition of intermediate products, which is described
in literature, as well as by analysis of composition of residues formed at the various
stages.56,61–65
Using the method of density functional theory, total energy of tetrahedral com-
plex ions [Zn(C5H5N)4]2+, [Cd(C5H5N)4]2+, [Hg(C5H5N)4]2+, [Cu(C5H5N)4]2+, and
rows of metal–nitrogen bonds in them was calculated (Table 16.6). For calculation,
a basis with pseudopotential (only valent electrons) that implies relativistic correc-
tions was used.
Some Coordination Compounds of Arsenic and Stibium 239

TABLE 16.6  Metal–Nitrogen Bonds.

Bond order
Ion Full energy, kJ/mol
N1 N2 N3 N4
Zn2+ −1026272.49 0.47 0.47 0.47 0.47

Cd2+ −870624.67 0.35 0.35 0.35 0.35

Hg2+ −836100.01 0.36 0.36 0.36 0.36

Cu 2+
−948390.59 0.54 0.54 0.54 0.54

Theoretical estimation of bioactivity of metal–pyridine fragments of obtained

coordination compounds has been carried out using computer program PASS
C&T,66 which is performed by Pa (act.) and Pi (inact.) parameters. Prior to that, Na3AsS4
was calculated, which manifested Pa = 0.507–0.898 antiprotozoal (amoeba) and an-
tihelmintic (nematodes, Fasciola) activity. Calculations show that metal–pyridine
fragment of synthesized coordination compound, presumably, also manifests high
bioactivity. Selected structures with high probability (Pa = 0.570–0.900) (Table 16.7)
may manifest the following kinds of biological activity: atherosclerosis treatment,
antineoplastic, antiseborrheic, antiviral picornavirus, cytoprotectant, etc. Conjuga-
tion of above-mentioned fragments apparently makes prospective creation of wide
range of coordination compounds with antimicrobial and antihelmintic properties.

16.6  SYNTHESIS AND STUDY OF [(I-PR)2(ET)4AS2(PH)][CO(NCS)4]

USING X-RAY DIFFRACTION AND IR SPECTROSCOPY ANALYSES

16.6.1  AIM OBJECTIVE AND BACKGROUND:

Many inorganic/organic arsenic compounds are used as therapeutic agents against
variable diseases, especially as antitumor drugs,67 biological active substances,68 in
material science,69,70 as auxiliaries in asymmetric synthesis,71–75 as catalysts,76 etc.
Compounds containing lone pairs can be considered electron-rich and
trialkyl(aryl)arsines (AsR3) act as nucleophilic toward haloalkanes to produce
tetraalkyl(aryl)arsonium salts (AsR4+), which contain As(V).77
Chemically active (with high toxicity) three-coordinated organoarsenic com-
pounds (e.g., arsines) can be stabilized by forming fourth bond with electrophilic
substituents and four-coordinated arsenic compounds are chemical stable and less
toxic. Arsonium yields with four-coordinated arsenic atom are successfully used in
synthetic inorganic chemistry as bulky cations to stabilize bulky anions.78
In compounds, arsenic atoms have the following electronic configurations: p3,
sp , sp3d, and sp3d2. Tetracoordinate arsenic derivatives—sulfides, oxides, and ar-
3

sonium compounds have a tetrahedral configuration and it has been suggested that
240 Process Advancement in Chemistry and Chemical Engineering Research

pπ-dπ conjugation is characteristic of the corresponding compounds.79 Nevertheless,

the aryl- and (E(CH3)3), alkylarsines such as trimethylarsane, are encountered as
ligands in d-metal complexes.
The order of affinity of these soft Lewis bases for a d-metal ion generally follows
the order: PR3 > AsR3 > SbR3 >BiR3.78 Because of soft-donor nature, many aryl and
alkylarsane complexes of the soft species Rh(II), Ir(I), Pd(II), and Pt(II) have been
prepared and studied.78 The series of tri- and four-coordinated arsenic compounds
were studied,80,81 for example, in trimethylarsine (CH3)3As, As–C bond lengths are
equal 1.98 Å and C–As–C angles around 96°, the geometry is pyramidal, respective-
ly. Among the trivalent arsenicorganic compounds, the bisarsines (RAs(R)AsR) are
important as useful bidentate ligands, especially o-phenylenebis(dimethylarsine) or
1,2-(arsino)benzene (C6H4(As(CH3)2)2), known as diars is very often used in com-
plexes.82–85
Me2
As

As
Me2

1,2-Bis(dimethylarsino)benzene or o-phenylenebis[(dimethyl)arsine]
Numerous complexes are studied with o-phenylenebisarsines with different sub-
stituents.86–89
It must be noted that (p-phenylene) derivatives of arsenicorganic compound do
not show complexing ability, but at that time they could be converted easily into +5
species such as R3AsO and [R4As]+ due to their basicity and nucleophilicity. In addi-
tion, most arsenic compounds have four substituents located in tetrahedron apexes
around the central atom. In this case, the fourth bond is formed by coordination of
nonbonding 4s2 electrons of the trivalent arsenic atom with a Lewis acid. Neverthe-
less, electrophilic addition of alkyl halides to tertiary arsines still remains one of
the main methods for preparing tetraalkyl- and alkylarylarsonium salts [R4As]+X−
(X=halg).90 The effect of the nature of the halogen in alkyl halides on their addi-
tion to trialkyl(aryl)arsines is poorly studied, but it is established that alkyl iodides
are the most active then alkyl chlorides.90 As a result of alkylation of arsines or
bisarsines cationic complexes- arsonium yields form which are stable than trivalent
arsines. Due to this fact, first we obtained cationic bisarsonium diiodides and then
converted into cationic–anionic complex, containing Co(II) and NCS-pseudohalide
group.90
Some Coordination Compounds of Arsenic and Stibium 241

Br MgBr As(C2H5)2

+ 2Mg + 2(C2H5)2AsCl + MgCl2 + MgBr2

Br MgBr As(C2H5)2

Et i-Pr Et

As(C2H5)2 As

+ 2izo-C3H7I I I

As(C2H5)2 As
Et Et
i-Pr

i-Pr
Et Et
Et i-Pr Et
As
+ As +

I I + 4KSCN +CoCl2 6H2O

[Co(NCS)4]2- + 2KCl + 2KI
As
Et Et As
i-Pr Et Et
i-Pr

Bis(diethyl)arsine was synthesized by common Grignard reaction,91 in diethyl

ether environment and under cooling, the product was purified by distillation (liq-
uid) under a reduced pressure. Diethylchlorarsine was synthesized according to lit-
erary,92 through the following consecutive reactions:

R3As + Cl2 → R3AsCl2 toC

 → R2AsCl + RCl
Chlorine was obtained and dried according to the methodic,93 in synthesized
compounds, arsenic was determined quantitatively by Evins’ method,94 nitrogen by
Duma’s method,95 cobalt by complexonometry, 96 iodine by mercurymetry,97 and
sulfur by gravimetric method.98 Required solvents, ethanol and diethylether, were
purified and dried according to the procedure described in Ref 99.
Dark blue single crystals of the complexes selected from the bulk before filtra-
tion were used for data collection. The cell determination and data collection were
carried out on a Nonius Kappa CCD diffractometer using graphite monochromated
MoKa radiation (l = 0.71070 Å). The phase problem was solved by SIR-97100 and
the structure refinement was carried with full-matrix least-squares on F2 using the
SHELXL-97101 program. All non-hydrogen atoms were refined anisotropically.
242 Process Advancement in Chemistry and Chemical Engineering Research

16.6.2  GENERAL RESULTS:

IR SPECTROSCOPIC STUDY
In the IR spectrum of [(Ph3AsCH2I]I3, the aromatic C–H stretching bands appear
in the 3047 cm−1 and the aliphatic C–H, in the 2877 (asym.) and 2946 (sym.) cm−1
regions. Skeletal vibrations, representing aromatic C=C absorb in the 1581–1434
cm−1 range. The C–Har bending bands appear in the regions 1241–1025 cm−1 (in
plane bending) and 833–686 cm−1(out-of plane bending).102 The week and medium
stretching bands appear at the 462–481 cm−1 (As–Car.) and 685 cm−1 (As–Caliph.),
characterized for As–C4 bonds in tetrahedral position.

X-RAY STUDY:
The structures of cation and anion of the obtained complexes are shown in Figures
16.9 and 16.10.
Compound crystallizes in the monoclinic, space group P21/n (No. 14) with a =
10.197 (1) Å, b = 13.152 (1) Å, c = 16.882 (1) Å, β = 93.01 (1)o, and four formula
units per unit cell. The crystal structure was solved via the Patterson method. For
refinement, full-matrix least-squares methods were applied.
Despite the identification of various arsonium cations, few examples have been
comprehensively studied and rarely mentioned in the literature.103–112 The well-
known and studied cation is tetraphenylarsonium, in which four independent arsenic
atoms with As–C distances in the range 1.910–1.921 and angles at arsenic between
106.1 and 110.7 assigned to the tetrahedral geometry. Tetrahedral configuration is
also observed in arsonium cations carrying benzyl, methyl, 4-methyl-phenyl, and
naphthalen-1-yl groups with As–C bond lengths 1.889–1.949 and C–As–C angles
106.9–112.5. A variety of complexes has been isolated with structures based on a
hydrogen bonded (Ph3AsO)2H]+ cation with I3, BF4, and AlCl4 counterions. The
cation–anion contacts (3.363 and 3.58 Å) in 1,3-dimethyldiaza-2-arsenanium tetra-
chlorogallate are within the sum of the Van der Waal’s radii for As and Cl (As, 2.0
Å; Cl, 1.7 Å). Recently, we have isolated [R3AsCH2I][I3] (a) and [R2(R’)AsCH2I]
[I3] (b) (R = Pr, iPr, Bu, iBu, Ph, am; R’ = Bu, Ph) arsonium compounds in As–C
interatomic distances range in the 1.906–1.924 Å and C–As–C angles of the cation:
105.3–109.8°(a) as well as the As–C interatomic distances range in the 1.921–1.953
Å and C–As–C angles of the cation: 106.8– 114.7° (b). The As–C bond lengths of
Ph-substituted compound are shorter than izo-Bu-substituted compound. The anion
(in contrast of comp. a) has symmetric linear structure: [I-2.91–I-2.91–I]−, as it is in
[As(C6H5)4]+ [I-2.90–I-2.90–I].
For some transition complexes containing ortho-phenylenebis(dimethylarsine)
and its phenyl analogues, as chelates, the octahedral arrangement dominates,
[Rh(diars)2Cl(CO2)] has an octahedral geometry, containing a molecule of carbon
Some Coordination Compounds of Arsenic and Stibium 243

dioxide coordinated via carbon atom, as well as cobalt complex [Co(diars)3][BF4]3

2H2O, with As–Co distances ranging between 2.365 and 2.395 Å and the platinum
complex [Pt(diars)2I2][BF4]2, which has trans-octahedral geometry (As–Pt 2.45 Å).
The arsenic–carbon bond lengths and angles of the synthesized bisarsonium tet-
ra-izo-thiocyanatocobaltate (II) complex are corresponding to the tetrahedral con-
figuration, therefore, the As–C bond lengths range in the 1.911–1.959 Å and angles
107.4–110.2°; as well as, in the counterion, Co–N bond lengths are equal 1.964 Å
and angles 105.4°, respectively. The crystal packing is due to the cation–anion con-
tacts and week intra-or intermolecular interaction forces.
The structures of +[(i-C3H7)(C2H5)2As(C6H5)As(C2H5)2(i-C3H7)]+ cation
and [Co(NCS)4]2−anion and crystal packing of [(i-Pr)(Et)2As(Ph)As(Et)2(i-Pr)]
[Co(NCS)4] are given below (Fig. 16.9, Fig. 16.10)

FIGURE 16.9  Structures of +[(i-C3H7)(C2H5)2As(C6H5)As(C2H5)2(i-C3H7)]+ cation and

[Co(NCS)4]2− anion.

FIGURE 16.10  Crystal packing of [(i-Pr)(Et)2As(Ph)As(Et)2(i-Pr)][Co(NCS)4].

244 Process Advancement in Chemistry and Chemical Engineering Research

The preliminary researches showed that the synthesized compounds have bacte-
ricide properties. They may be used against some phytopathogenic microorganisms.
Synthesized arsenic–manganese complexes, dropped into the several functional
polymer matrixes, may serve as a basis to prepare new bioactive materials with
regular duration of the action: antibiocorrosion coatings for multifunctional purpose
foamed polyurethane materials and various dipping compounds.
The preliminary researches showed that the synthesized compounds have bacte-
ricide properties. They may be used against some phytopathogenic microorganisms.
Synthesized arsenic–manganese complexes, dropped into the several functional
polymer matrixes, may serve as a basis to prepare new bioactive materials with
regular duration of the action: antibiocorrosion coatings for multifunctional purpose
foamed polyurethane materials and various dipping compounds.

16.7  STIBUM-CONTAINING BIOACTIVE COMPLEX COMPOUNDS

BASED ON D-METALS AND SOME NITROGEN-CONTAINING
LIGANDS: SYNTHESIS, STRUCTURE, AND PROPERTIES

16.7.1  AIMS AND BACKGROUND:

Transformation of stibium containing industrial waste into stable coordination com-
pound with specific properties with the purpose of their further application belongs
to a variety of topical issues of applied and coordination chemistry. Successful solu-
tion of this problem will not only create new raw materials resource base, but also
will solve important ecological problem, will protect environment from pollution by
stibium containing waste. The presented work is devoted to this problem, in which,
reaction–responsive stibium compounds extracted from arsenic production waste
are considered, on the basis of which new nitrogen-containing bioactive coordina-
tion compounds are received.
2,2’-dipyridyl as a ligand, for a great while is studied during the synthesis of
coordination compounds.113 The reason of this study is nonuniform and contains
both pure chemical and applied aspects. The ample opportunities of 2,2’-dipyridyl
for creation of coordination compounds of different types and behavior should be
sought in its structure:

N N
Because of the fact that nitrogen atoms hold such a position in molecule that
optimum conditions are created for formation of five-member cycle, 2,2’-dipyridyl
from the very beginning became the focus of scientists interest, and due to this fact,
coordination compounds with metal halogenides, nitrates, sulfates, and almost ev-
ery other soluble salt containing it are studied in details.
Some Coordination Compounds of Arsenic and Stibium 245

Sodium tetrathioarsenates (V) water solutions action with the products of inter-
action of d-metals soluble salts with bidentate ligand 2,2’-dipyridyl leads us to the
formation of appropriate coordination compound2. Having used the same method,
we implemented the synthesis of coordination compounds tetrathiostibiates (V)
with 2,2’-dipyridyl.
Salts dissolved in d-metals water are used as basic substances: Ag(I) and Hg(II)
nitrates, Zn, Fe(II) and Cu(II) sulfates, Mn(II), Cd(II), Ni(II), and Co(II) chlo-
rides; sodium tetrathiostibiate is used as precipitator, while 2,2-dipyridyl (C5H4N)2
(shortly dipy) is used as nitrogen-containing ligand. We also used ethylenediamine
(H2N–CH2–CH2–NH2), one of the best bidentate ligand, for obtaining of complex
compounds of d-metals (II).

16.7.2  RESULTS AND DISCUSSION:

For preliminary estimation of relative complex-forming ability of the selected or-
ganic ligands and study of their electronic structure, we have carried out their quan-
tum-chemical investigation. Quantum-chemical calculations were performed on PC
with an AMD processor with the built-in coprocessor by using Mopac 2000 and
CS Chem3D Ultra, v8.114 We gave the following key words to guide each computa-
tion: EF GNORM = 0.100 MMOK GEO-OK AM1 MULLIK LET DDMIN = 0.0
GNORM = 0.1 GEO-OK.
We have calculated energetical and geometrical parameters, effective charges on
atoms, and electron occupation of atomic orbitals (electronic density) in 2,2’-dipyri-
dyl and ethylenediamine molecules.
In the molecule of 2,2’-dipyridyl (Fig. 16.11), the bond lengths and valence
bond angles of nitrogen atoms N1 and N12 with neighbor atoms ( ∠ C2–N1–C6 =
118.1° and ∠ C7–N12–C11 = 118.1°) indicate mainly their sp2 hybridized position.

FIGURE 16.11  3-D model of 2,2’-dipyridyl.

246 Process Advancement in Chemistry and Chemical Engineering Research

Analysis of values of effective charges on atoms (Table 16.8) shows that poten-
tially electron donor atoms are N1 (q1 = −0.105052), C3 (q3 = −0.177231), C5 (q5 =
−0.167740), C8 (q8 = −0.167764), C10 (q10 = −0.177228), and N12 (q12 = −0.104952).
But electron occupation of atomic orbitals (Table 16.9) shows that in spite of com-
paratively high negative relative charge of carbon atoms (C3, C5, C8, C10), in com-
parison with nitrogen atoms, are unable to form s-bond with metal atom by donor-
acceptor mechanism as they don’t have an electron pair on the second energetical
level. The electron pairs of nitrogen atoms is located on 2s orbital (electron oc-
cupation 1.71732 (N1) and 1.71738 (N12)) and only they have the capacity to form
s-bond with metal atom by donor–acceptor mechanism.

TABLE 16.7  The Results of Calculated Virtual Bioactivity of Metal-Pyridine Fragments of

Tetrathioarsenates (V) Some of d-Metals.

Antiviral (picorna-
Atherosclerosis

Cytoprotectant
Antiseborrheic
Antineoplastic

Antineurotic
sideroblastic
treatment

promoter
Anemia,

Insulin
virus)

Compound

Pa/Pi
[Cu(C5H5N)4]3(AsS4)2 – – 0.874/ 0.870/ 0.666/ 0.655/ 0.679/ 0.625/
0.002 0.007 0.009 0.013 0.046 0.012
0.991/ 0.892/ 0.859/ 0.852/ 0.639/ 0.637/ 0.624/ 0.570/
[Zn(C5H5N)4]3(AsS4)2 0.002 0.005 0.003 0.010 0.012 0.018 0.063 0.018
0.987/ 0.953/ 0.822/ 0.852/ 0.583/ 0.598/ 0.624/ 0.570/
[Cd(C5H5N)4]3(AsS4)2 0.002 0.004 0.004 0.010 0.023 0.031 0.063 0.018
0.987/ 0.953/ 0.852/ 0.852/ 0.563/ 0.578/ 0.624/ 0.563/
 [Hg(C5H5N)4]3(AsS4)2 0.002 0.004 0.010 0.010 0.023 0.031 0.063 0.018
 [Ni(C5H5N)6]3(AsS4)2  – 0.945/ 0.867/ 0.839/ 0.574/ 0.602/ 0.601/ 0.579/
0.004 0.003 0.012 0.025 0.030 0.071 0.025
[Co(C5H5N)6]3(AsS4)2 – – 0.859/ 0.886/ 0.645/ 0.640/ 0.725/ 0.673/
0.003 0.005 0.011 0.017 0.034 0.008
Some Coordination Compounds of Arsenic and Stibium 247

TABLE 16.8  Relative Charges and Electronic Density on the Dipyridyl Atoms.

Relative Electronic Electronic

Relative charges
Atom (i) charges on density Atom (i) density (qi
on atoms (qi)
atoms (qi) (qi (d)) (d))
N1 −0.105052 5.1051 C11 −0.071521 4.0715
C2 −0.071475 4.0715 N12 −0.104952 5.1050
C3 −0.177231 4.1772 H13 0.161749 0.8383
C4 −0.095118 4.0951 H14 0.144233 0.8558
C5 −0.167740 4.1677 H15 0.139053 0.8609
C6 0.025459 3.9745 H16 0.146123 0.8539
C7 0.025459 3.9745 H17 0.146118 0.8539
C8 −0.167764 4.1678 H18 0.139062 0.8609
C9 −0.095095 4.0951 H19 0.144225 0.8558
C10 −0.177228 4.1772 H20 0.161696 0.8383

Thus, the molecule contains two potential electron donor atom, N1 and N12, be-
cause of that it represent as a bidentate ligand and is capable to form coordination
compounds with d-metals in the form of five-member cycle:

N N

n+
M

In the molecule of ethylenediamine (Fig. 16.12), the bond lengths and valence
bond angles of nitrogen atoms N3 and N4 with neighbor atoms ( ∠ C1–N3–H9 =
109.5°, ∠ C1–N3–H10 = 109.5°, ∠ H9–N3–H10 = 110.6°, ∠ C2–N4–H11 = 110.3°,
∠ C2–N4–H12 = 111.3°, and ∠ H11–N4–H12 = 109.3°) indicate mainly theirs sp3 hy-
bridized position.

FIGURE 16.12  3-D model of ethylenediamine.

248 Process Advancement in Chemistry and Chemical Engineering Research

Analysis of values of effective charges on atoms (Table 16.10) shows that poten-
tially electron-donor atoms are N3 (q3 = −0.349295) and N4 (q4 = −0.349288).

TABLE 16.9  Electron Occupation of Atomic Orbitals.

Atom 2s 2px 2py 2pz
N1 1.71732 1.06728 1.22193 1.09853
C3 1.22757 1.00124 0.92718 1.02123
C5 1.22712 0.94049 0.97761 1.02252
C8 1.22715 0.94466 1.00769 0.98827
C10 1.22752 1.00113 0.99355 0.95502
N12 1.71738 1.05008 1.13945 1.19804

TABLE 16.10  Relative Charges and Electronic Density on the Ethylenediamine Atoms.

Electronic Electronic
Relative charges Relative charges
Atom (i) density (qi Atom (i) density (qi
on atoms (qi) on atoms (qi)
(d)) (d))

C1 −0.080091 4.0801 H7 0.105135 0.8949

C2 −0.080043 4.0800 H8 0.035121 0.9649

N3 −0.349295 5.3493 H9 0.149137 0.8509

N4 −0.349288 5.3493 H10 0.140076 0.8599

H5 0.035061 0.9649 H11 0.149103 0.8509

H6 0.105054 0.8949 H12 0.140031 0.8600

Electron occupation of atomic orbital (Table 16.11) shows that the electron pairs
of nitrogen atoms are located on 2s and 2pz orbitals (electron occupation for N3
atom is 1.58211 (2s) and 1.49979 (2pz), but for N4 atom is 1.58220 (2s) and 1.52119
(2pz). Nitrogen atoms, N3 and N4, have capacity to form s-bond with metal atom by
donor–acceptor mechanism.
Thus, the molecule contains two potential electron-donor atoms, N3 and N4, be-
cause of that it represents as a bidentate ligand and is capable to form coordination
compounds with d-metal ion in the form of five-member cycle:
Some Coordination Compounds of Arsenic and Stibium 249

H2C CH2

H2N NH2
M n+

For comparison of the complex formation ability for selected ligands, we cal-
culated their complexes with Cu2+. The Ni–Cu2+ bond orders for dipyridyl PCu1 -N 2
= 0.333011 and PCu1 -N13 = 0.335304, the correspond charges: q1 = 0.633404, q2
= −0.184639, and q3 = −0.184586. For ethylenediamine, PCu1 -N 2 = 0.566363-ob
and PCu1 -N3 = 0.566054, the charges: q1 = 0.775783, q2 = −0.191420, and q3 =
−0.190861. The above-mentioned information allowed us to conclude that the com-
plex of Cu+-ion with ethylenediamine is more stable than with dipyridyl.

Synthesis of d-metals tetrathiostibiate coordination compound with 2,2’-di-

pyridyl was carried out by exchange reaction, as result of which tetrathiostibiate
complexes of corresponding d-metals are precipitated, formation of which can be
explained by the unity of the following consecutive reactions:

AgNO3 + dipy →  Ag ( dipy )  NO3 (a)

250 Process Advancement in Chemistry and Chemical Engineering Research

3  Ag ( dipy )  NO3 + Na 3SbS4 ⋅ 9H 2 O →  Ag ( dipy )  3 SbS4 ↓ + 3NaNO3 + 9H 2 O (b)

or in total:

3AgNO3 + 3dipy + Na 3SbS4 ⋅ 9H 2 O →  Ag ( dipy )  3 SbS4 ↓ + 3NaNO3 + 9H 2 O

As to other metals (II) dipyridylates, in particular when M = Fe, Co, Ni, Zn, Cd,
Hg, Cu, and Mn:

MX 2 +ndipy →  M ( dipy )n  X 2 (a)

3  M ( dipy )n  X 2 + 2Na 3SbS4 9H 2 O → 6NaX +  M ( dipy )n  ( SbS4 )2 ↓ + 18H 2 O (b)

3

or in total:
3MX 2 + 3ndipy + 2Na 3SbS4 ⋅ 9H 2 O →  M ( dipy )n  ( SbS4 )2 ↓ + 6NaX + 18H 2 O
3

The essence of this method comprises in the fact that nitrates, chlorides, and
sulfates of the mentioned metals form stable, but water-soluble coordination com-
pounds with 2,2’-dipyridyl. That is why their extraction from mother solution in
chemically pure form for thio stibiates (V) of some d-metals
The obtained coordination compounds represent finely dispersed substances,
insoluble in differently colored water and ethanol (Tables 16.12 and 16.13). All
of them are extracted without crystallization water, except of Fe(II) dipyridylates,
which adds to three molecules of water. They have no certain melting temperature,
since they resolve before melting.

TABLE 16.11  Electron Occupation of Atomic Orbitals.

Atom 2s 2px 2py 2pz

N3 1.58211 1.12209 1.14530 1.49979
N4 1.58220 1.12078 1.12511 1.52119

TABLE 16.12  Some Basic Characteristics of the Synthesized Ethylenediamine Complexes

of Tetrathiostibiates (V) of Some d-Metals.
No Elemental analysis data (%)
Compound Yield(%) Color Found Calc.
M Sb N S M Sb N S
1 [Ag(en)]3SbS4 94.1 Black 42.94 16.16 11.15 17.02 43.07 16.21 10.90 16.81

2 [Zn(en)2]3(SbS4)2 88.7 Yellow 18.57 23.06 15.91 24.29 18.68 22.99 15.79 24.19
Some Coordination Compounds of Arsenic and Stibium 251

TABLE 16.11  (Continued)

3 [Cd(en)2]3(SbS4)2 93.9 Orange 28.17 20.34 14.03 21.42 28.09 20.40 14.15 21.25

4 [Hg(en)2]3(SbS4)2 95.2 Brown 41.17 16.66 11.49 17.55 41.21 16.54 11.70 17.34

5 [Cu(en)2]3(SbS4)2 94.6 Grey 18.14 23.18 15.99 24.41 18.07 23.27 15.82 24.69

6 [Co(en)3]3(SbS4)2 89.7 Black 14.53 20.01 20.71 21.08 14.67 20.16 20.48 21.45
7 [Ni(en)3]3(SbS4)2 91.5 Black 14.51 20.02 20.72 21.08 14.59 19.96 20.69 20.84

The composition of the synthesized complexes was established by elemental

analysis: stibium was determined by the Evins method, sulfur by gravimetric meth-
od, metal by volumetric method, and nitrogen by the Duma’ micromethod.
The composition and structure of the synthesized complexes, except of elemen-
tal analyses, was determined by physicochemical research methods. Study of IR
spectra of these complexes adsorption shows that SbS34− group in the studied sub-
stances represents exteriorly spherical tetrathiostibiate (V) ion. In the long wave,
380 and 384 cm−1 spectral region absorption band is observed, which correspond to
ν3 oscillation of SbS34− ion.
The obtained dipyridyl coordination compounds are finely divided into vari-
ous color compounds dissolved in water, ethanol, and other usual organic solvents.
All these compounds, besides dipyridylates of Fe(II), separated without crystalliza-
tion water. They have distinct melting temperature because they are dismissed until
melting.
Comparison of free (incoordinate) ligand: 2,2’-dipyridyl spectrum with d-metals
(Fe, Zn, Mn) tetrathiostibiate (V) dipyridylates spectra shows displacement of high-
frequency absorption bands (Fig. 6.3). Free ligands absorption band is at 1584 cm−1,
while in the complexes it is displaced to 1600–1610 cm−1, which is related to hetero-
cyclic nitrogen coordination with metals atoms 5–7.115
By taking into account the above-mentioned information, we come to a conclu-
sion that the formulas of the synthesized coordination compounds can be presented
as follows:

For Fe(II) complex, as for crystalline hydrate, absorption bands are observed in
1630 cm−1 region (Fig. 16.13) that points to the presence of crystallization water in
the compounds.
252 Process Advancement in Chemistry and Chemical Engineering Research

FIGURE 16.13  IR spectra of the synthesized compounds. (a)  Fe ( dipy )3  3 ( SbS4 )2 ⋅ 3H 2O ; (b)
 Zn ( dipy )2  ( SbS4 )2 ; and (c)  Mn ( dipy )3  3 ( SbS4 )2 .
3

Individuality of investigated substance is testified by the results of X-ray phase

studies (Table 6.7).
Thermal studies of the synthesized compounds assured us that dipyridyl com-
plexes do not contain crystallization water, except of dipyridylate of Fe(II) tetra-
thiostibiates, which is testified by the IR spectroscopic data (Fig. 16.13), too.
The thermal behavior of these compounds is almost similar. Thermolysis of
Fe(II) tetrathiostibiate(V) dipyridylates [Fe(dipy)3]3(SbS4)2.3H2O was considered as
an example (Fig. 16.14a). The destructive process began at 80°C; in the temperature
interval 80–150°C of the corresponding DTA curve, one can observe the exothermic
peak with maximum The mass loss equal to 3.57% hat corresponds to 3 moles crys-
tallization water (theoretically: 2.54%). The next stage of the thermolysis process in
the temperature interval 150–380°C proceeds with difficultly. On the DTA, one can
observe three exothermic peaks with maximum at 210, 250, and 360°C. The mass
loss at this moment is about 45.00% that corresponds to the removal of 6 mole crys-
tallization water (theoretically: 44.03%). In the temperature interval 380–530°C,
one can observe an exothermal effect with maximum at 480°C with mass loss of
27.57%. Based on the theoretical evaluation (25.03%), the corresponding peak may
belong to the loss of 3 moles ligands and 2 moles sulfur. After this process, the mass
loss of the investigated sample comprises 1%, which is equal to the removal of 1
mole sulfur (theoretically 1.5%).
Some Coordination Compounds of Arsenic and Stibium 253

FIGURE 16.14  DTA and TGA curves of the synthesized coordination compounds. (a)
 Fe ( dipy )3  ( SbS4 )2 ⋅ 3H 2 O ; (b)  Zn ( dipy )2  3 ( SbS4 )2 .
3

Foreseen from the above-mentioned information, the thermolysis of dipyridylate

of Fe(II) tetrathiostibiate may be represented by the following approximate(Table
16.14) Scheme 16.5:
80 −1500 C 150 − 3800 C
 Fe ( dipy )3  ( SbS 4 )2 ⋅ 3H 2O →  Fe ( dipy )3  ( SbS 4 )2 →
3 −3 H 2O 3 −6 dipy
380 − 5300 C > 5300 C
→  Fe ( dipy ) 3 ( SbS 4 )2 → Fe3 Sb2 S6 → ...
−3 dipy ; −2 S −S

SCHEME 16.5
 254

TABLE 16.13  Some Basic Characteristics of the Synthesized Dipyridyl Complexes of Tetrathiostibiates (V) of Some d-Metals.

No Compound Yield Color Elemental analysis data (%)

(%)
Found Calc.

M Sb N S H2O M Sb N S H2O

1 [Ag(dipy)]3SbS4 88.7 Black 31.07 11.69 8.06 12.31 – 30.83 11.92 8.03 12.46 –

2 [Zn(dipy)2]3(SbS4)2 93.3 Yellow 12.02 14.92 10.29 15.71 – 11.77 15.05 10.36 15.87 –

3 [Cd(dipy)2]3(SbS4)2 86.3 Orange 19.02 13.73 9.47 14.46 – 18.81 13.49 9.27 14.30 –

4 [Hg(dipy)2]3(SbS4)2 96.6 Brown 29.53 11.95 8.24 12.59 – 29.71 12.07 8.02 12.44 –

5 [Cu(dipy)2]3(SbS4)2 95.8 Black 11.72 14.97 10.33 15.77 – 11.85 15.01 10.11 15.65 –

6 [Mn(dipy)3]3(SbS4)2 95.6 Brown 7.97 11.77 12.18 12.40 – 8.02 11.98 12.01 12.27 –

7 [Fe(dipy) 3] 3(SbS 4) 2 89.8 Red 7.88 11.46 11.86 12.07 2.54 7.66 11.37 11.73 11.91 2.59
•3H2O

8 [Co(dipy)]3SbS4 90.2 Black 8.50 11.70 12.11 12.33 – 8.43 11.53 11.86 12.14 –

9 [Ni(dipy)3]3(SbS4)2 85.7 Black 8.47 11.71 12.12 12.33 – 8.32 11.84 12.32 12.18 –
Process Advancement in Chemistry and Chemical Engineering Research
Some Coordination Compounds of Arsenic and Stibium 255

TABLE 16.14  Results of X-ray Analysis of the Synthesized Dipyridyl Complexes of

Tetrathiostibiates (V) of Some d-Metals (F, Ni, Hg, and Ag).

Only exception is presented by Hg(II) complex, thermolysis begins on relatively

low (100°C) temperature and completes by total decay (Figs. 16.15a and 16.16a).
This fact is caused by instability of Hg(II)-containing compounds at high tempera-
tures.
Thus, the obtained results allow to make a conclusion that molecules of 2,2’-di-
pyridyl are coordinated with d-metals atoms by means of nitrogen atoms, while
SbS34− group is located in the external (second) sphere of the complex.
Since ethylenediamine (H2N–CH2–CH2–NH2) is one of the best bidentate li-
gand, we have set, as a goal, the reception of complex compounds of d-metals tetra-
thiostibiates in the system M +2 − SbS4−3 − en − H 2 0. Sodium tetrathiostibiate Na 3SbS4 ⋅ 9H 2O ,
ethylenediamine (50% water solution) and salts of water-soluble d-metals have been
used by us as a mother (basic) substances.
Coordination compounds of d-metal tetrathiostibiates with ethylenediamine
have been received by means of exchange reaction by the action of sodium tetra-
thiostibiate with the products of interaction of 50% ethylenediamine and d-metals
salts, without extraction of the latter in individual status. Ag(I), Cd, Zn, Hg(II), Cu,
Co, and Ni(II) complexes with ethylenediamine have been synthesized according to
the following reactions:

AgNO3 + en →  Ag ( en )  NO3
h
256 Process Advancement in Chemistry and Chemical Engineering Research

3  Ag ( en )  NO3 + Na 3SbSu ⋅ 9H 2 O →  Ag ( en )  3 SbS4 ↓ +3NaNO3 + 9H 2 O

(a)

MX 2 + nen →  M ( en )n  X 2

3  M ( en )n  X 2 + 2Na 3SbS4 ⋅ 9H 2 O →  M ( en )n  ( SbS4 )4 ↓ + 6NaX + 18H 2 O

3 (b)

where M = Zn , Cd, Hg, Cu, Ag, Co , Ni ; X = CI , 1/ 2SO24− or NO3− .

−

Since the Fe(II) ethylenediamine complex is extracted from water solution in

the form of precipitate, while received precipitate is insoluble in the sodium tetra-
thiostibiates, we were not able to receive Fe(II) tetrathiostibiate complex by means
of exchange reaction with ethylenediamine, as it was achieved during synthesis of
other d-metals aminates.
The synthesized complexes are finely crystalline compounds of various color-
ing; they are insoluble in the water, spirit, and other ordinary organic solvents.
Synthesized compounds, except of elemental analysis, have been studied by IR
spectroscopy, X-ray graphical studies, and thermogravimetric analysis.
Study of the IR spectra of the synthesized compounds (Fig. 16.17) shows that
the NH2 group absorption bands are significantly shifted in comparison with unco-
ordinated ligand. For free, uncoordinated ethylenediamine absorption bands in 1595
and 3510 cm−1 regions are characteristic, while in coordination compound under
investigation, the absorption bands of this group are located in 1620 and 3370 cm−1
region113 that is characteristic for valence vibration of H2N → M+ bond. And since
silver(I) coordination number is equal to 2, while in case of other d-metals, proceed-
ing from the quality of their oxidation, this number increases up to 4, we can draw
a conclusion that ethylenediamine plays the role of cyclic bidentate ligand, and the
synthesized complexes have the following structure:
Individuality of obtained products has been checked by means of X-ray phase
analysis. Cu(II), Ni(II), and Ag(I) compounds show sufficiently defined X-ray pat-
tern, while as to Hg(II), Zn(II), and Co(II) tetrathiostibiates of ethylenediamine
(Table 16.8), they turn out to be X-ray amorphous.116
Some Coordination Compounds of Arsenic and Stibium 257

FIGURE 16.15  DTA and TGA curves of the synthesized coordination compounds. (a)
 Hg ( dipy )2  ( SbS4 )2 ; (b)  Ni ( dipy )3  ( SbS )2 .
3
258 Process Advancement in Chemistry and Chemical Engineering Research

FIGURE 16.16  DTA and TGA curves of the synthesized coordination

compounds. (a)  Hg ( dipy )  ( SbS4 ) ; (b)  Ni ( dipy )  (SbS4 ) .
 2 3 2  3 3 2

FIGURE 16.17  IR spectra of the synthesized compounds: (a)  Zn ( en )2  3 ( SbS4 )2 ; (b)

Co ( en )3  ( SbS4 )2 .
3
Some Coordination Compounds of Arsenic and Stibium 259

X-ray diagram of the American card-catalogue ASTM 20-1692 (C5H8N2.2HCl

pure ligand) has been used with the purpose of study of received X-ray diagrams. It
turns out that, in our case, correlation takes place, but the certain amount of X-ray
reflections is not deciphered (decoded), and for this purpose, the method of homol-
ogy has been used. More perfect X-ray diagram existing in the American card-cat-
alogue ASTM 24-1670 partially filled the gap and gave us the picture that is almost
similar to Ni(II) and Cu(II) tetrathiostibiate complexes with ethylenediamine. It may
be noted that the samples are virtually similar to the compared references and repre-
sent ethylenediamine complexes.
The thermolysis of Co (en )3  3 ( SbS4 )2 as a sample (Fig. 16.18a) is also consid-
ered below. Removal of 9 mol of ligand occurs at 100–280°C temperature range
in three stages: at 100–130, 130–180, and 180–280°C. At the first stage, the mass
decreases by 15.00% (theoretically 14.79%); at the second, by 16.42%; and at the
third, by 15.01%.

FIGURE 16.18  DTA and TGA curves of the synthesized coordination

compounds. (a) Co ( en )3  ( SbS4 )2 ; (b)  Zn ( en )2  ( SbS4 )2 .
3 3
260 Process Advancement in Chemistry and Chemical Engineering Research

It may be noted that the removal of 3 moles of ligand corresponds with each
of these stages. After 280°С, as it was mentioned, the process of thermolysis pro-
ceeds as well as in case of normal (neutral) salts. In 280–560°C temperature range,
the mass decreases by 7.14% that corresponds to the removal of 3 moles of sulfur
(theoretically 7.89%). At DTA curve, two exothermic effect are observed within this
range, with peaks at 340 and 520°C.
Further decay of the samples continues above 520°C, endothermic effect is ob-
served at DTA curve with peak at 820°C, the mass loss comprises of 24.28% that
should be caused by removal of stibium sulfide form (theoretically 25.27%).
On the assumption of above-mentioned information, the probable Scheme 16.6
of thermolysis of Co(II) tetrathiostibiates (V) of ethylenediamine can be presented
as follows:
100 −1300 C 180 − 2800 C

Co (en )3  3 ( SbS 4 )2 →

−3en Co (en )2  3 ( SbS 4 )2 →
−3en
0 0
280 − 560 C 560 −860 C
Co3 ( SbS 4 )2 → 3CoS ⋅ Sb2 S 2 → 3CoS
−3 S − Sb2 S2

SCHEME 16.6

As well as in other cases, here, the process of  Hg ( en )2  3 ( SbS4 )2 thermolysis

(Fig. 16.19a) differs from the corresponding processes of other ethylenediamine
complexes that during heating experiences total decay without any residue.

Decay of  Hg ( en )2  3 ( SbS4 )2 sample begins from 120°C and becomes especially

intense in the 210–270°C temperature range. At that time, the mass loss is equal to
9.33% (theoretically 8.21%) that corresponds to the removal of 2 moles of ethyl-
enediamine.
In the 270–450°C temperature range, the exothermic peak has several maxima
at DTA curve that points out that complex process runs on. During this process, total
loss of remained mass takes place.
Study of the synthesized complexes [Cu(II), Cd, and Ag(I) (ethylenediaminate
tetrathiostibiates] thermographs shows that removal of ethylenediamine in all com-
pounds occurs in two or three stages. For these complexes with ethylenediamine (as
well as in case of normal salts) mass increase is observed in the process of thermoly-
sis (Table 16.15).
Some Coordination Compounds of Arsenic and Stibium 261

FIGURE 16.19  DTA and TGA curves of the synthesized coordination compounds. (a)
 Hg ( en )2  ( SbS4 )2 ; (b) Cu ( en )  ( SbS ) .
3  2 3 4 2

Thus, the investigations show that in case of d-metal ethylenediamine complex-

es treatment by sodium tetrathiostibiates water solution corresponding compounds

 Ag ( en )  3 SbS4 and  M ( en )n  3 ( SbS4 )2 are received in the form of precipitate (where

n = 2, 3).
We have carried out preliminary virtual (theoretical) bioscreening of obtained
structures by using Internet-system program PASS C&T.50 The estimation of proba-
bility of activity of compounds is carried out via parameters Pa (active) and Pi (inac-
262 Process Advancement in Chemistry and Chemical Engineering Research

tive); when Pa > 0.5–0.7, the compound also will show activity experimentally and
probably will be analog of known pharmaceutical agents too. Evaluated relative bio-
activities of some synthesized compounds are given in Table 16.16. Microbiological
study of the investigated compounds confirmed the evaluated virtual concepts.117

16.8  OBTAINING AND STUDY OF ARSENIC-CONTAINING

BORATES BASED ON TRANSFORMATION PRODUCTS OF
INDUSTRIAL WASTE
In the chemistry of boron, great place takes of important representatives of boron–
organic compounds: alkyl(aryl)borates (RO)2BR/ and ROB(OR/)2 (R = alk., R/ =
aryl, R = R/, R ≠ R/). Synthesis and study of properties of these compounds have
begun from XIX century and did not lose actuality up to day. They have not only
preparative, but also theoretical and practical significance. They are used in many
organic synthesis as borating agents and Lewis acids—for obtaining the boronhy-
drids of potassium and sodium trimethoksiborokcol—and also as gaseous flux at the
welding of metals.118–121
By standpoint of bioactivity, special interest provokes borates containing other
elements, privately arsenic.122,123 We synthesized arsenic-containing borates based
on ethylene glycol, pyrocatechin, 2,3-dihydroxynaphthalene, p-oxyphenylarsonic
acid, and salicylic acid. The synthesis carried out in the presence of toluene azeo-
trop generated azeotrop with water, for removing of isolated water at the boiling of
reaction mixture, and for carrying out process in the set direction.
The reaction may be expressed by the following general Scheme 16.7:

HO O
C OH C
+ B OH + HO R OR + 3H2O
C OH HO C O

I II

SCHEME 16.7

All obtained compounds are solid amorphous substance (Table 16.17), insoluble
in nonpolar and low polar solvents (benzene, toluene), well dissoluble in dimethyl
formamide and dimethyl sulfoxide, moderately in ethanol. They are hydrolyzed in
water by heating and products of hydrolysis supposedly must be a mixture of the
initial products.
Some Coordination Compounds of Arsenic and Stibium 263

TABLE 16.15  Results of X-ray Analysis of the Synthesized Ethylenediamine

Tetrathiostibiates (V) of Some d-Metals (Cu, Ni, and Ag).

TABLE 16.16  Virtual Relative Bioactivity of Some Synthesized Coordination Compounds.

Antihelmintic
Urethanase inhibi-

Antibacterial  ac-

Compound
Cytoprotectant
Antineurotoxic
tivity enhancer
Antiseborrheic

Antineoplastic
(brain cancer)
(nematodes)

(arbovirus)
Neurotoxin
Antiviral
tor

Pa/Pi
[Fe(dipy)3]3(SbS4)2 0.865/ 0.820/ 0.586/ 0.687/ 0.719/ 0.695/ 0.672/ 0.661/ 0.637/
.
3H2O 0.021 0.005 0.053 0.046 0.029 0.010 0.041 0.035 0.047
264 Process Advancement in Chemistry and Chemical Engineering Research

TABLE 16.16  (Continued)

[Ag(dipy)]3(SbS4)2 0.824/ 0.766/ 0.496/ 0.636/ 0.670/ 0.657/ 0.581/ 0.615/ 0.522/
0.041 0.011 0.105 0.089 0.065 0.025 0.071 0.063 0.084
[Mn(dipy)3]3(SbS4)2 0.865/ 0.820/ 0.586/ 0.687/ 0.719/ 0.695/ 0.672/ 0.661/ 0.637/
0.021 0.005 0.053 0.046 0.029 0.010 0.041 0.035 0.047
[Ag(en)]3(SbS4)2 0.768/ 0.651/ 0.543/ 0.681/ 0.663/ 0.640/ 0.636/ 0.650/
0.066 0.034 0.075 0.049 0.070 0.034 0.052 0.041 –

TABLE 16.17  Mass Spectral Data of Arsenic-Containing Borates.

Compound Mass spectral data, m/z (Irel., %)
I 288.0 [M+] (4.71), 243.9 (17.36), 227.9 (51.42), 167.9 (100.0), 133.8 (67.49)
II 384.0 [M+] (3.63), 275.9 (100.0), 182.9 (24.53), 167.9 (25.48), 139.9 (7.36),
135.9 (3.11)

We show one of the possible scheme of obtaining boron and arsenic-containing

compounds from industrial waste below (Scheme 16.8):
O

HO As OH ROH H O HNO C H OH
2 3 6 5
OH
(industrial waste -As2O3) → 2As(OR)3 → As2O3 → 2H3AsO4 →
The composition and structure of the synthesized compounds that we have es-
tablished by chemical (Bfound/Bcalc: I-3.61/3.81; II-3.23/3.27; III-2.73/2.84; Asfound/
Ascalc: I-25.75/26.04; II-21.18/19.43), infrared (IR), NMR, and Mass spectral analy-
ses (Table 16.17).

SCHEME 16.8
Some Coordination Compounds of Arsenic and Stibium 265

In the IR spectra of ethylene glycol(p-oxyphenylarsonic acid) borate, we have

observed intensive absorption band 1344–1345 cm−1 related to boron (III) valence
wave. The absorption band 1520 cm−1 characterized for 1.4-substituted benzene
ring. In the IR spectra, we also observed the characteristic absorption bands for the
CH-groups (848 cm−1); middle intensive absorption band 832 cm−1, which must be
related to frequency wave of oxoarsenate ions. The absorption bands 416–420 cm−1
are also related to oxoarsenate ions.
Mutual comparison of the IR spectra of the borates shows some likeness and
difference among them, for example, in the IR spectra of the compound I (Table
16.17), we have observed absorption band 2880–2890 cm−1 related to CH2-groups
valency wave, which are also characterized with deformation vibration (1460 cm−1).
Mentioned absorption bands are provoked by existence of ethylene glycol fragment
and was not observed in other spectra of borates.
In the 1H NMR spectra of ethylene glycol(p-oxyphenylarsonic acid) borate,
one can observe signal with chemical shift 3.98–4.04 ppm for the protons in the
CH2 groups of the ethylene glycol fragment; signals with chemical shifts at 6.86–
7.67 ppm related to the protons of CH groups of benzene, the resonance signal in
the range chemical shift 2.46–2.49 ppm for the protons of the As–OH. In the 13C
NMR spectra, one can observe a signal with four chemical shifts within the range
59.22–62.56 ppm typical for the carbon atoms of CH2 of the ethylene glycol frag-
ment. In the 13C NMR spectra, we also observe chemical shifts within the range
161.50–161.83 and 123.84 ppm related to carbon atoms and 115.20–116.53 and
130.51–131.18 ppm related to CH groups of benzene ring.
In the 13H NMR spectra of pyrocatechin(p-oxyphenylarsonic acid) borate, one
can observe a signal with chemical shifts within the range 6.45–6.53 and 6.72–6.99
ppm typical for the carbon atoms of twice substituent benzene ring; signals with
chemical shifts at 6.88–6.79 and 7.01–7.38 ppm related to the protons of CH groups
of benzene, the resonance signal in the chemical shift within the range 2.39–2.42
ppm for the protons of the As–OH. In the 13C NMR spectra, we also observe chemi-
cal shifts within the range 118.25–118.92, 121.72, and 144.45–145.15 ppm related
to carbon atom of twice substituent benzene group, the chemical shifts within the
range 162.34–162.34, 123.89, 115.54–116.92, and 130.04–132.37 ppm related to
carbon atoms of benzene ring.
In the 13H NMR spectra of 2.3-dihydroxynaphthalene(p-oxyphenylarsonic acid)
borate, one can observe a signal with chemical shifts within the range 6.81–6.96
and 7.45–7.48 ppm, typical for the carbon atoms of naphthalene group; signals
with chemical shifts at 6.68–6.74 and 7.01–7.03 ppm related to the protons of CH
groups of benzene, the resonance signal in the range chemical shift 2.40–2.54 ppm
for the protons of the As–OH. In the 13C NMR spectra, we also observe chemical
shifts within the range 110.85–111.15, 124.52–126.27, 129.25–130.08, and 147.86–
148.89 ppm related to carbon atom of naphthalene group, the chemical shifts within
266 Process Advancement in Chemistry and Chemical Engineering Research

the range 160.94–161.73, 124.09, 116.07–116.35, and 131.48–131.86 ppm related

to carbon atoms of benzene ring.
The important data have given mass spectral analysis method of synthesized
compounds too. Privately, the mass-spectrogram data of synthesized compounds
(I–IV) show that the mass of molecular (M+) and fragmental ions correspond with
obtained structures of above-mentioned compounds and clearly represents succes-
sion of splitting of different atoms or groups of atoms (Table 16.17).
Additional information about structure and composition of arsenic-containing
borates gives us quantum-chemical semiempirical AM1 method. By means of this
method, we have calculated energetical (formation enthalpy ∆Hf, ionized poten-
tial) and geometrical parameters (angles between the atoms, valence, and dihedral
angles) effective charges on atoms (q), dipole moment (M), and bond number be-
tween the atoms. Quantum-chemical calculations were performed by CS MOPAC
(Chem3D Ultra-version 8.03).115 In benzene ring of ethylene glycol(p-oxyphenylar-
sonic acid) borate, distances between C–C atoms (1.39–1.40), valence bond angles
of C–C–C (119–121°C) and bond number (1.30–1.40) corresponds to the sp3 hy-
bridized position of carbon atoms. The quantum-chemical calculations confirmed
partial deformation of five-member boron cycles, which is caused by inhomogene-
ity of distances between the atoms. Distances between B(12)-0 (13) and B (12).0
(16) 1, 38 A, also 0 (13) C (14), and 0 (16) C (15), correspondingly are 1.49 A and
1.46 A. Analysis of electronic charges shows that biggest deficiency of electrons are
characterized carbon atoms C(3) and C(6), which is explained by their connection
with the strong electronegative atoms. Calculated E = 7.94.107 kJ/mole and D(dip.
moment)
= 7.48 Debai.
The study of thermal properties of obtained compounds by thermogravimet-
ric (TGA) and differential-thermal analysis (DTA) method shows that they, except
compound I (Table 16.1), do not have distinctly expressed melting points and before
melt were decomposed, which is easy to detect visually too. The character of thermal
processes current in temperature intervals 20–600°C are almost identical and con-
sists of three stages: soften (not melt), partial reduce to coal, and final destruction.
By gas–liquid chromatography analysis, isolation of CO2 and H2O (350°C) were
established. Comparatively high temperature of beginning of intensive destruction
(450–570°C), how it seems, is conditioned by content of cyclic structure of borates
in the molecule structure. In the 550–650°C temperature range with the maximum
600°C (exothermic effect) must be caused by oxidation process of residual carbon
(with organic component). By this time, the mass decreases are 55%. The remain-
ing black welded residue, as expected, is a mixture of boron and arsenic oxides,
43.8%. A similar picture, except in the case of borates of aromatic dioles, with the
difference that the endothermic peak respective to their melting points, also the peak
respective to initial and intensive destruction is shifted toward higher temperatures
(580–670°C).
Some Coordination Compounds of Arsenic and Stibium 267

16.8.1  VIRTUAL (THEORETICAL) BIOSCREENING OF ARSENIC-

CONTAINING BORATES
We have carried out the preliminary virtual (theoretical) bioscreening of synthesized
compounds by using Internet-system program PASS C&T.50
The estimation of probable bioactivity of chosen compounds was carried out
via parameters Pa (active) and Pi (inactive); when Pa > 0.7, the compound also could
be shown bioactivity experimentally.124–130 Following from above-mentioned virtual
bioscreening, based on analysis of obtained results, the synthesized compounds (I–
IV) with experimentally high probability (Table 20) (Pa = 0.70–0.98) possibly will
show the following bioactivity: antibacterial (antispirochetal, antitreponemal, sub-
tilisin inhibitor, Salmonella), antiparasitic (antiprotozoal—amoeba, Histomonas,
Trypanosoma, Trichomonas), growth stimulant etc.
The synthesized compounds were tested as inhibitors of growth of some phyto-
pathogenic bacteria. As test objects, the following microorganisms were used: Agro-
bacterium tumefaciens (causing a grapevine disease), Xanthomonas campestric and
Pectobacterium aroideae (striking some melons and gourds), and Streptomyces spp.
(destroys some water dissolved polymers).
Biocide properties of compounds were determined by an alveolar standard
method. Test results are presented in the Tables 16.18–16.19. Results of experi-
ences showed that the synthesized compounds of I and II in various degree oppress
growth of studied test organisms and can be used against these phytopathogenic
microorganisms.

TABLE 16.18  Relative Bioactivity of Synthesized Compounds (I–III).

Antibacterial Antiparasitic
Subtilisininhibitor

Growth stimulant
Antitreponemal

Non mutagenic,
Antispirochetal

(Trypanosoma)

(Trichomonas)
Antiprotozoal

Antiprotozoal

Antiprotozoal

Antiprotozoal

Antiprotozoal
(Histomonas)
Salmonella

(amoeba)

Compounds

Pa / Pi
I 0.840 0.900 0.837 0.880 0.984 0.983 0.907 0.985 0.769 0.853
0.000 0.000 0.004 0.010 0.001 0.001 0.000 0.001 0.001 0.001
II 0.818 0.880 0.809 0.739 0.978 0.975 0.878 0.977 0.702 0.802
0.001 0.000 0.004 0.025 0.001 0.001 0.000 0.001 0.001 0.002
III 0.837 0.899 0.825 0.717 0.982 0.981 0.904 0.984 0.769 0.835
0.000 0.000 0.004 0.029 0.001 0.001 0.000 0.001 0.001 0.001
268 Process Advancement in Chemistry and Chemical Engineering Research

TABLE 16.19  Influence of the Synthesized Compounds on the Growth of Various

Microorganisms.

Compounds
I II
No Concentration of compound, g/l
Microorganisms 0.1 0.01 0.001 0.1 0.01 0.001
Zone of suppression of test microorganisms, mm
1 Xanthomonas campestric 6.0 5.0 3.0 7.0 6.0 3.0
2 Pectobacterium aroideae 5.0 4.5 3.0 8.0 6.5 4.0
3 Agrobacterium tumefaciens 7.0 6.0 4.0 8.0 7.0 4.0
4 Streptomyces spp. 4.0 4.0 3.0 6.0 4.0 2.0

KEYWORDS

•• arsenic
•• stibium
•• chemical compounds
•• coordination
•• inorganic–organic complexes
•• mechanism of reactions
•• biomedical nano

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CHAPTER 17

SURFACE-MODIFIED MAGNETIC
NANOPARTICLES FOR CELL LABELING
B. A. ZASONSKA1, V. PATSULA1, R. STOIKA2, and D. HORÁK1
1
Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic,
Heyrovskeho Sq. 2, 162 06 Prague 6, Czech Republic
2
Institute of Cell Biology, National Academy of Science of Ukraine, Drahomanov St.
14/16, 79005 Lviv, Ukraine

CONTENTS
17.1 Introduction.................................................................................................276
17.2  Preparation of Magnetic Nanoparticles......................................................277
17.4  Properties of the Surface-Modified Iron Oxide Nanoparticles ..................280
17.5  Engulfment of the Nanoparticles by Stem Cells and Macrophages...........283
17.6 Conclusion..................................................................................................285
Acknowledgment...................................................................................................286
Keywords...............................................................................................................286
References..............................................................................................................287
276 Process Advancement in Chemistry and Chemical Engineering Research

17.1 INTRODUCTION
A great effort has been recently devoted to the design and synthesis of new mag-
netic nanoparticles driven by the rapid development of the nanomedicine and
nanobiotechnology.1Among them, iron oxide nanoparticles, in particular magnetite
(Fe3O4) and maghemite(γ-Fe2O3), play a prominent role since iron is indispens-
able component of living organisms and has reduced toxicity.2Surface-modified
iron oxide nanoparticles have been found very attractive for cell separation3 and
labeling,4cancer therapy,5drug delivery,6 and as contrast agents for magnetic reso-
nance imaging (MRI).4
There are many methods to obtain various types of iron oxide nanoparticles
differing in shape, morphology, size, and availability of the reactive groups on the
surface.3The oldest preparation involves the size reduction,7that is, grinding of bulk
magnetite in the presence of large amounts of surfactant in a ball mill for 500–1000 h.
Other synthetic approaches for development of magnetic nanomaterialsinclude hy-
drothermal process,8 sol–gel method,9or spray pyrolysis.10However, the most popu-
lar techniquesfor preparation of such particles include coprecipitation of Fe(III) and
Fe(II) salts in the presence of an aqueous base (e.g., NH4OH or NaOH)or thermal
decomposition of organometalliccomplexesin high-boiling solvents.11For the latter,
precursors, such as Fe(III) acetylacetonate,12FeN-nitrosophenylhydroxylamine13 or
Fe(CO)5 were suggested.14
Iron oxide nanoparticles possess a lot of unique properties, such as small size
(˂100nm) allowing them to function at the cellular level, superparamagnetism, high
magnetization, and large specific surface area. However, neat(uncoated) particles
show high nonspecific adsorption of biomolecules,undesirablein vitroandin vivoin-
teractions, relative toxicity, and tendency to aggregate.15 This can be avoided by their
surface modification with biocompatible polymers, which also determines ability
of the nanoparticles to interact with living cells in a well-defined and controlled
manner, as well as ensures immunotolerance and biocompatibility.Typical polymer
shells are made from organic materials, like polyethylene glycol (PEG),16poly(vinyl
alcohol),17poly(N,N-dimethylacrylamide) (PDMAAm),18 or inorganic materials, for
example,silica.19This additional layer can render the particles with colloidal stabil-
ity, avoids interactions with thesurrounding environment, and introducesspecific
functional groups on the surface.
In this chapter, synthesis, properties, and some applications of new
poly(N,N-dimethylacrylamide)-coated maghemite (γ-Fe2O3@PDMAAm), sili-
ca-coated maghemite(γ-Fe2O3@SiO2),andmethoxy polyethylene glycol-coated
magnetite(Fe3O4@mPEG)nanoparticles aredescribed.Both PDMAAmand silica
are hydrophilic,chemically inert,andbiocompatible materials, hence,they are at-
tractivefor drug delivery systems and applications in medical diagnostics. More-
over, the polymerscan behave like transfection agents enabling efficient engulfment
of the particles by the cells, for example, stem or neural cells and macrophages.
Macrophages,that are formed in response to an infection and accumulate damaged
Surface-Modified Magnetic Nanoparticles for Cell Labeling 277

or dead cells, are important in the immune system.20These large, specialized cells
can recognize, engulf, and destroy foreignobjects.Through their ability to clear
pathogens and instruct other immune cells, theyplay a pivotal role in protecting the
host. They also contribute to the pathogenesis of inflammatory and degenerative
diseases.21Labeling of macrophages with magnetic particles enables, thus their trac-
ing in the organism using magnetic resonance imaging (MRI).

17.2  PREPARATION OF MAGNETIC NANOPARTICLES

Chemical and physical properties of magnetic nanoparticles, such as size and size
distribution, morphology and surface chemistry, strongly depend on selection of the
synthetic method, starting components, and their concentration.11,22 Nanoparticles
ranging in size from 1 to 100nm exhibit superparamagneticbehavior.22 In this report,
two methods of iron oxide synthesis are presented.
Coprecipitation method. Typical synthesis of magnetic nanoparticles is ex-
emplified by formation of maghemite (γ-Fe2O3) duringcoprecipitation of Fe(II) and
Fe(III) salts followed by oxidation of Fe3O4 with sodium hypochlorite.23 Briefly,0.2
Maqueousiron(III) chloride (100ml) and 0.5 M iron(II) chloride (50 ml) were soni-
cated for a few minutes and mixed with 0.5 Maqueous ammonium hydroxide (100
ml). The mixture was then continuously stirred (200 rpm) at room temperature
for 1h. Formed Fe3O4 nanoparticles were magnetically separated and seven times
washed with distilled water.Subsequently, the colloid was sonicated with 5 wt.%
sodium hypochlorite solution (16 ml) and again five times washed with water to
obtain the final γ-Fe2O3 nanoparticles.
Thermal decomposition.Another possibility to produce superparamagnet-
ic nanoparticles consists in thermal decomposition of iron organic compounds,
for example, iron(III) oleate.24The method allows preparation of monodisperse
Fe3O4 nanoparticles with controlled size. As an example, we describe preparation
of iron(III) oleateby reaction of FeCl3·6H2O (10.8 g) and sodium oleate (36.5 g)
in a water/ethanol/hexane mixture(60/80/140 ml) at 70°C for 4 hunder vigorous
stirring. The upper organic layer was then separated, three times washed with wa-
ter (30 ml each), and the volume reducedon a rotary evaporator. Obtained brown
waxy product was vacuum-dried under phosphorus pentoxide for 6 h. The result-
ing Fe(III) oleate (7.2 g) and oleic acid (4.5 g) were then dissolved in octadec-
1-ene (50 ml) andheated at 320°C for 30 min under stirring (200 rpm). The reac-
tion mixture wascooled to room temperature, the particles precipitated by addition
of ethanol (100 ml) and collected by a magnet. Obtained nanoparticles were then
five times washed with ethanol (50 ml) and redispersed in toluene and stored.

<H1>17.3MODIFICATION OFTHE NANOPARTICLE SURFACE

Disadvantage of neat iron oxide colloidsis that they induceundesirable interactions,
for example, adhesiontothe cells. To prevent this,it is recommended to coat theiron
278 Process Advancement in Chemistry and Chemical Engineering Research

oxide surface with a biocompatible polymer shell. Surface of theγ-Fe2O3nanoparticles

was, therefore, firstly modified with an initiator and N,N-dimethylacrylamide was
then polymerized from the surface. 2,2’-Azobis(2-methylpropionamidine) dihydro-
chloride (AMPA)servedasuitablepolymerization initiator.In contrast, if the particles
were hydrophobic, that is, obtainedfrom the thermal decomposition, they weredis-
persible only in organic solvents. To make them waterdispersible and suitable for
biomedical applications, their surface was modified with mPEGderivatives via a
ligand exchange.

17.3.1  COATING WITH POLY(N,N-DIMETHYLACRYLAMIDE)

(PDMAAM)
Coating of the γ-Fe2O3 nanoparticles with PDMAAm via grafting from approach is
schematically shown in Figure17.1. In the following section, example of this syn-
thetic approach is described in more detail. The polymerizationwas run in a 30-ml
glass reactor equipped with an anchor-type stirrer.First, the AMPAinitiator (4.8 mg)
was added to 10 ml of the colloid (47 mg γ-Fe2O3/ml) during 5 min, DMAAm (0.3
g) was dissolved and the mixture purged with nitrogen for 10 min. The polym-
erization was started by heating at 70°C for 16 h under stirring(400 rpm). After
completion of the polymerization, the resulting γ-Fe2O3@PDMAAm particles were
magnetically separated and washed 10 times with distillated water until all reaction
byproducts were removed.Advantage of the γ-Fe2O3@PDMAAm particles consists
in possibility to introduce additional functional comonomer into the shell to attach a
highly specific bioligand, such as antibody, peptide, or drug.

FIGURE 17.1  Scheme of preparation γ-Fe2O3@PDMAAm nanoparticles via grafting-from

approach using 2,2’-Azobis(2-methylpropionamidine) dihydrochloride (AMPA) initiator.

17.3.2  COATING WITH TETRAMETHOXYORTOSILICATE

(TMOS) AND (3-AMINOPROPYL)TRIETHOXYSILANE(APTES)
Another frequently used coating of iron oxide particles is based on silica. Silic-
ais generally synthesized by hydrolysis and condensation of tetraethylorthosili-
cate (TEOS) or tetramethylorthosilicate (TMOS) (Fig.17.2). Neat silica particles
are obtained by Stöber method in ethanol underthe presence of ammonia catalys-
Surface-Modified Magnetic Nanoparticles for Cell Labeling 279

t25or in surfactant-stabilizedreverse microemulsion containing two phases.26Theγ-

Fe2O3nanoparticles were coated by a silicashell using TMOS according to earlier
publishedmethod.27Shortly, solution containing 2-propanol (24 ml), water (6 ml),and
25 wt.%aqueous ammonia (1.5 ml) was mixed with γ-Fe2O3 colloid (1 ml; 50 mg
γ-Fe2O3) for 5 min. TMOS (0.2 ml) was added and the mixture stirred (400 rpm)
at 50°C for 16 h. Resulting γ-Fe2O3@SiO2colloid(Fig.17.3c,g) was then five times
washed with ethanol using magnetic separation. In the next step, amino groups were
introduced on the particle surface using (3-aminopropyl)triethoxysilane(APTES).
In a typical experiment,γ-Fe2O3@SiO2 nanoparticles were dispersed in ethanol (50
ml) under sonication for 15 min and APTES (0.15 ml), ethanol (20 ml), and water (1
ml) were added. After completion of the reaction, the resulting γ-Fe2O3@SiO2–NH2
particles (Fig.17.3d,h) were washed with water.

FIGURE 17.2  Scheme of silanization of γ-Fe2O3 with tetramethylorthosilicate (TMOS) and

modification of γ-Fe2O3@SiO2 nanoparticles with(3-aminopropyl)triethoxysilane(APTES).

FIGURE 17.3(A–D)  TEM and (e–h) SEM micrographsof (a, e) neatsuperparamagnetic

γ-Fe2O3 nanoparticles synthesized by coprecipitation method, (b, f) γ-Fe2O3@PDMAAm (via
grafting-from approach), (c, g) γ-Fe2O3@SiO2, and (d, h) γ-Fe2O3@SiO2–NH2 nanoparticles.
280 Process Advancement in Chemistry and Chemical Engineering Research

17.3.3  COATING WITH METHOXY POLYETHYLENE

GLYCOL(MPEG)
In order to make the hydrophobic iron oxide particles dispersible in water, their sur-
face was modified by a ligand exchange method.28 As a hydrophilic ligand, mPEG
was selected due to its nontoxicity, hydrophilicity, and low opsonization in biologi-
cal media. mPEG was terminated with groups, such as phosphonic (PO(OH)2)29 and
hydroxamic (NHOH) acid,30 exhibiting strong interactions with the iron ions.Fe3O4
particles prepared by thermal decomposition were coated bymPEG,terminated with
phosphonic(PA-mPEG) or hydroxamicacid (HA-mPEG).In the following section,
the surface modification is described in more detail.HA- or PA-mPEG (70 mg) and
hydrophobic Fe3O4 nanoparticles (10 mg) were added to 4 ml of tetrachloromethane/
toluene mixture (1:1 v/v) and sonicated for 5 min. The mixture was then heated at
70°C for 48 h under vigorous stirring. The Fe3O4@PEGnanoparticles were purified
by repeated precipitation with petroleum ether (3 × 30 ml ) at 0°C and diethyl ether
(3 × 30 ml) and redispersed in water.

17.4  PROPERTIES OF THE SURFACE-MODIFIED IRON OXIDE

NANOPARTICLES
The synthesized surface-modified iron oxide particles were thoroughly character-
ized by a range of methods including transmission (TEM) and scanning electron
microscopy (SEM), atomic absorption spectroscopy (AAS), attenuated total reflec-
tance–Fourier transform infrared spectroscopy (ATR–FTIR),dynamic light scatter-
ing (DLS), and magnetic measurements.Shape of the iron oxideparticles, prepared
by the coprecipitationand thermal decomposition methods,was sphericaland cubic,
respectively. The number-average diameter (Dn)of the γ-Fe2O3particles prepared by
precipitationwas 10 nm (TEM) andpolydispersity index PDI (Dw/Dn) = 1.24 (Dw is
the weight-average diameter) suggesting a moderately broad particle size distribu-
tion (Fig. 17.3a).Since it was rather difficult to control size and particle size distribu-
tion by the precipitation method, thermal decomposition approach was investigated.
Size of the Fe3O4 particles was controlled in the 8–25 nmrange andmonodispersity
was achieved (Fig.17.4).For example, if the reaction temperature increased from
320 to 340°C, the Dnis increased from 8 (Fig.17.4a) to 17 nm (Fig.17.4b) due to
anincrease in the growth rate of the nanoparticles. If the concentration of oleic acid
stabilizer increased from 0.008 to 0.08 mmol/ml, the particle size decreased from 12
to 8 nm (Fig.17.5) because more stabilizersstabilizes more particles. However, the
particles prepared by this method were hydrophobic; the organic shell formed ~80
wt.% of the total mass according toAAS. Such particles formed very stable colloids
in organic solvents,such as toluene or hexane, but not in water.Magnetic properties
of the nanoparticles were described earlier.28
Surface-Modified Magnetic Nanoparticles for Cell Labeling 281

FIGURE 17.4  TEM micrographs of (a) 8 and (b)17 nm superparamagnetic Fe3O4

nanoparticles prepared by thermal decomposition method at (a) 320 and (b) 340°C.

FIGURE 17.5  Dependence of number-average diameter Dn of Fe3O4 nanoparticles on oleic

acid concentration. Particles were prepared in octadec-1-ene at 320°C for 30 min.

Compared with the neat nanoparticles, Dn of the dried γ-Fe2O3@PDMAAm

nanoparticles was larger(12 nm) due to presence of the shell, but thepolydispersity
substantially did not change(PDI 1.18; Fig. 17.3b).The hydrodynamic diameterD-
h
of γ-Fe2O3@PDMAAm, PA- and HA-mPEG-coated Fe3O4was substantially larger,
that is,206, 35,and 68 nm,respectively, than Dn. The reason consists in that the DLS
provided information about Dh of the particle dimers and clusters in water, where
hydrophilic PDMAAm chains swell. Zeta potential (ZP) of theγ-Fe2O3@PDMAAm,
PA- and HA-mPEG-Fe3O4was −53, 26.3, and 12.4 mV, respectively. Since ZP of
theγ-Fe2O3@PDMAAm was highly negative, the nanoparticle dispersions were
very stable (up to a few months) due to the electrostatic repulsion. Regardless of the
282 Process Advancement in Chemistry and Chemical Engineering Research

low positive ZP of theFe3O4@mPEGparticles, their colloidsolutions were also very

stable due to steric repulsion provided by mPEG. PA-mPEG-Fe3O4 colloid (Dh~40
nm) was stable also at various NaCl concentrations ranging from 1 to1000 mmol/l.
In contrast, HA-mPEG-coated Fe3O4(Dh~65 nm) demonstrated stability only at 1
and 10 mmol of NaCl/l.ATR–FTIR and Fe analysisconfirmed successful coating of
the iron oxide nanoparticleswith both PDMAAm by the grafting-from methodand
mPEGby ligand exchange method.23,28
Optionally, the γ-Fe2O3nanoparticles were covered with a silica shell at vari-
ous γ-Fe2O3/TMOS ratios (0.1–0.8 w/w) to control the morphology and size of
the nanoparticlesobserved by TEM (Fig.17.3c) and SEM (Fig. 17.3g). Size of the
γ-Fe2O3@SiO2 particles ranged from 12 to 192 nm depending on the γ-Fe2O3/SiO2
ratio (Fig.17.6). With increasing amounts of silica relative to the iron oxide and with
introduction of amino groups by reaction with APTES,Dnof theγ-Fe2O3@SiO2 and
γ-Fe2O3@SiO2–NH2nanoparticles increased (Fig.17.3d)due to their aggregation.
This was accompanied with broadening of the particle size distribution. Accord-
ing to AAS, content of iron decreased from 66.1 in γ-Fe2O3to 27.7 and 19.8 wt.%
in γ-Fe2O3@SiO2 and γ-Fe2O3@SiO2–NH2 nanoparticles, respectively. This was
inagreement with increasing thickness of the silica shell surrounding the γ-Fe2O3
particles. Nevertheless, this amount of iron was sufficient to confer the particles
with good magnetic properties. Coating of the γ-Fe2O3 particles with a thin silica
shell-hindered particles from aggregation and made them hydrophilic; as a result,
the particles were well dispersible in water. Secondary coating obtained by reac-
tion of γ-Fe2O3@SiO2 particles with APTES made possible prospective attachment
of a target biomolecule,for example, protein, antibody, enzyme, or drug. However,
γ-Fe2O3@SiO2–NH2 nanoparticles often formed aggregates at neutral pH suggest-
ing that the initial γ-Fe2O3@SiO2 particles agglomerated during the reaction with
APTES.

FIGURE 17.6  Dependence of number-average diameter Dn of γ-Fe2O3@SiO2 particles on

γ-Fe2O3/SiO2 ratio.
Surface-Modified Magnetic Nanoparticles for Cell Labeling 283

17.5  ENGULFMENT OF THE NANOPARTICLES BY STEM CELLS

AND MACROPHAGES
Labeling of the cells with surface-functionalized iron oxide nanoparticles is in-
creasingly important for diagnostic andseparation of DNA,31 viruses,32 proteins,33
and other biomolecules.34A great deal of attention is recentlydevoted tostem
cells and their ability to differentiate in any specialized cell type. Earlier, we
have developedpoly(L-lysine)-coated γ-Fe2O3 nanoparticles(γ-Fe2O3@PLL) and
γ-Fe2O3@PDMAAm particles obtained by the solution radical polymerization in
the presence of γ-Fe2O3.18,35Such particleswere found to be highly efficient forin
vitrolabeling of human (hMSCs) and rat bone marrow mesenchymal stem cells (rM-
SCs).In this report, bothγ-Fe2O3@PDMAAm obtained by grafting-from approach
and γ-Fe2O3@SiO2nanoparticleswere investigated in termsof their engulfment by
macrophages (Fig. 17.7).This is an important task from the point of view of control-
ling introduction, movement and overall fate of the labeled cells after their implan-
tation in the organism.

FIGURE 17.7  Fluorescence micrographs of murine J 774.2 macrophages treated with (a)
γ-Fe2O3,(b) γ-Fe2O3@PDMAAm (via grafting-from approach), (c) γ-Fe2O3@SiO2, and (d)
γ-Fe2O3@SiO2–NH2 nanoparticles.

In a typical stem cell labeling experiment, the hMSCs or rMSCswere cultured in

Dulbecco’s Modified Eagle’s Medium (DMEM) in a humidified 5% CO2 incubator;
the medium was replaced every 3 days until the cells grew to convergence. Uncoated,
284 Process Advancement in Chemistry and Chemical Engineering Research

γ-Fe2O3@PLL, γ-Fe2O3@PDMAAm particles (via the solution polymerization),and

the commercial contrast agent Endorem (dextran-coated iron oxide) were then used
for labeling of the stem cells. After 72 h of labeling, the contrast agent was stained
to produce Fe(III) ferrocyanide (Prussian blue). The quantification of labeled and
unlabeled cells wasperformed using TEM and inverted light microscope. Compared
with Endorem and unmodified nanoparticles, thePDMAAm- and PLL-modified
particles demonstrated high efficiency of intracellular uptake into the human cells.
Optionally, the labeled rMSCs cells were intracerebrallyinjected into the rat brain
and magnetic resonance(MR) images were obtained.MR images of theγ-Fe2O3@
PDMAAm (via the solution polymerization)- and γ-Fe2O3@PLL-labeled rMSCs
implanted in a rat brain confirmed their better resolution compared with Endorem-
labeled cells.18,35
In our experiments, both γ-Fe2O3@PDMAAm(via grafting from approach),γ-
Fe2O3@SiO2and γ-Fe2O3@SiO2–NH2nanoparticles(4.4 mg/ml) were opsonized with
FBS proteins at 37°C for 24 h. They were thenincubated with murine J774.2 macro-
phages and stainedwith acridine orange and Hoechst 33342. Uptakeof the particles
by the cells and their morphological changeswere analyzed using fluorescence mi-
croscopy. Cytotoxicity of the γ-Fe2O3@PDMAAm and neat γ-Fe2O3 nanoparticles
was estimated using a hemocytometer chamber for counting number of the cells
treated in the presence of nanoparticles (0.025, 0.5, and 1 wt.%) in the culture me-
dium for 24 h.
The efficiency of the engulfment of the γ-Fe2O3@ PDMAAmand neat γ-Fe2O3
nanoparticles by the murine J 774.2 macrophages was determined after 30 min, 1,
2, 3, and 24 h cell cultivation in the presence of the particles. Figure 17.7shows ac-
ridineorange and Hoechst 33342-stainedmacrophages treated with the nanoparticles
for 3 h. After 30-min treatment of J774.2 macrophages with γ-Fe2O3@PDMAAm
nanoparticles, their majority remained unengulfedin the culture medium. Visible
engulfment of the nanoparticles appeared after 1-h treatment. After 2-h treatment,
granulation of the cytoplasm was observed due to accumulation ofthe γ-Fe2O3@
PDMAAm nanoparticles in the peripheral region of the cytoplasm. After 3-h treat-
ment, majority of the γ-Fe2O3@PDMAAm nanoparticles were engulfed by the mac-
rophages and some cells demonstrated signs of lysosomal activation characterized
by red acridin orange fluorescence. Only a minimal amount of the γ-Fe2O3@PD-
MAAm nanoparticles remained unengulfed indicating that theengulfment was very
efficient.PDMAAm showed the affinity to cell membrane components facilitating,
thus the endocytosis.
As a control experiment, the engulfment of the neat γ-Fe2O3 nanoparticles in
the macrophages was investigated. Within 1–3-h treatment, the number of vacu-
oles, their size, as well as the number of lysosomal clusters associated with large
vacuoles, increased with time. Numerous unengulfed γ-Fe2O3 nanoparticles were
accumulated on the surface of treated macrophages, while free γ-Fe2O3nanoparticles
were almost absent. The size of the cells treated with γ-Fe2O3nanoparticles was also
increased.
Surface-Modified Magnetic Nanoparticles for Cell Labeling 285

All described superparamagneticnanoparticles were relatively nontoxic for

the cultured cells. Apparently, for the efficient particle engulfment by the macro-
phages, the presence of positively charged amidinegroups in γ-Fe2O3@PDMAAm
nanoparticles is beneficial. The efficiency of engulfment of the γ-Fe2O3@PD-
MAAm nanoparticles was quite high since after 2-h treatment most cells engulfed
the nanoparticles and only few nanoparticlesremained in the culture medium. Fluo-
rescence microscopy confirmed only weak activation of lysosomes, which mani-
fested itself by a change in the color of acridine orange from green to red. Acridine
orange,a weakly basic amino dye, is known to be a lysosomotropic agent. In its
stacked form, that is, in lysosomes, it emits red fluorescence, while in the cell nuclei
at neutral pH, it emits yellow-green fluorescence. Activation of macrophages during
the engulfment of foreign extracellular materials was accompanied by an increase
in the activity of digestive vacuoles, and thus it caused a red fluorescence shift due
to accumulation of the dye in lysosomes. Activation of lysosomal compartments
accompanied intracellular processing of the engulfed particles (microorganisms,
viruses, damaged cells, and foreign macromolecules).23 Chemical structure of un-
coated γ-Fe2O3 nanoparticles, thus provided potential toxicity for the treated cells,
which manifested itself by time-dependent evolution of vacuolesin the cell cytosol.

17.6 CONCLUSION
In summary, two different types of iron oxide nanoparticles were
synthesized,maghemite(γ-Fe2O3)and magnetite (Fe3O4). The first oneswere pre-
pared by coprecipitation of Fe(II) and Fe(III) salts with aqueous ammonia. Obtained
magnetite was then oxidized with sodium hypochlorite to chemically stable ma-
ghemite. However, the particle size distribution of these particles was rather broad
as determined by a range of physicochemical characterization methods including
SEM, TEM, and DLS measurements. In contrast, monodispersesuperparamagnetic-
Fe3O4nanoparticles with size controlledfrom 8 to 25 nm were produced by the ther-
mal decomposition of Fe(III) oleate at different temperatures and oleic acid concen-
trations. The particles were successfully transferred in water bythe ligand exchange
method. As a hydrophilic ligand, derivatives of mPEGwith specific functional
groupswere used that strongly chemically bonded with iron. Optionally, γ-Fe2O3
particles were surface-modified with PLL, PDMAAm(both by thesolution radical
polymerization and grafting-from method), or SiO2. The successful coating of the
iron oxide nanoparticle surface was confirmed by both ATR–FTIR spectroscopy and
Fe analysis. The colloidal particles were stable in aqueous media for several months.
The biotargetingcharacteristics of the nanoparticles are mainly defined by the
biomolecules conjugated to the particle surface.It is desirable that the particle shell
contains either membranotropic molecules like phospholipids, polyethylene glycol,
or macromolecules (proteins) present in biological fluids. In this work, surface of
the formed nanoparticles was opsonized with proteins available in the fetal bovine
286 Process Advancement in Chemistry and Chemical Engineering Research

blood serum. The γ-Fe2O3@PDMAAm and γ-Fe2O3@SiO2nanoparticles, in contrast

to the neat nanoparticles were shown to be noncytotoxic and intensively phago-
cytosed by the mammalian macrophages. Additionally, there was no cell irritation
during the phagocytosis of the γ-Fe2O3@PDMAAm nanoparticles. In contrast, time-
dependent vacuolization of neat γ-Fe2O3 nanoparticles in cytoplasm of the macro-
phages was observed suggesting cytotoxicity of the material.
Silica used as an inorganic inert coating of the γ-Fe2O3nanoparticles also proved
to be suitable modification agentpreventing aggregation of the particles and en-
hancing their chemical stability. This inorganic material is also easily susceptible
to chemical modifications, which make synthesis of particles for combined diagno-
sis and therapy possible. Biological experiments demonstrated that both γ-Fe2O3@
PDMAAm and γ-Fe2O3@SiO2 and γ-Fe2O3@SiO2–NH2core-shell nanoparticles were
recognized and engulfed by the macrophages. The uptake of the surface-coated iron
oxide nanoparticles by phagocytic monocytes and macrophages could provide a
valuable in vivotool by which magnetic resonance imaging can monitor introduc-
tion, trace movement, and observe short- and long-term fate of the cells in the or-
ganism.
In conclusion, high potential of the polymer-coated magneticnanoparticles can
be envisioned for many biological applications. The particles can be easily magneti-
cally separated and redispersed in water solutions upon removing of the external
magnetic field. Magnetically labeled cells can be steered and concentrated inside
the body by a magnet. The iron oxide particles, modified with organic, as well as
inorganic polymercoatings, seem to be very promising not only for cell imaging
and tracking, but also for drug and gene delivery systems and capture of various
cells and biomolecules required for diagnostics of cancer, infectious diseases, and
neurodegenerative disorders.

ACKNOWLEDGMENT
The financial support of the Ministry of Education, Youth, and Sports (project
LH14318) is gratefully acknowledged.

KEYWORDS

•• magnetic nanoparticles
•• polymerization
•• macrophages
•• silica
•• magnetite
•• maghemite
Surface-Modified Magnetic Nanoparticles for Cell Labeling 287

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CHAPTER 18

THE REINFORCEMENT OF
PARTICULATE-FILLED POLYMER
NANOCOMPOSITES BY
NANOPARTICLES AGGREGATES
G. E. ZAIKOV1, G. V. KOZLOV2, and A. K. MIKITAEV2
1
N. M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, 4,
Kosygin St., Moscow 119334, Russian Federation
Kh.M. Berbekov Kabardino-Balkarian State University, Chernyshevsky st., 173,
2

Nal’chik 360004, Russian Federation

CONTENTS
Abstract..................................................................................................................290
18.1 Introduction..................................................................................................290
18.2 Experimental................................................................................................291
18.3 Results and Discussion................................................................................292
18.4 Conclusion...................................................................................................301
Keywords...............................................................................................................302
References..............................................................................................................302
290 Process Advancement in Chemistry and Chemical Engineering Research

ABSTRACT
The applicability of irreversible aggregation model for theoretical description of
nanofiller particles aggregation process in polymer nanocomposites has been shown.
The main factors influencing on nanoparticles aggregation process were revealed. It
has been shown that strongly expressed particulate nanofiller particles aggregation
results in sharp (in about four times) formed fractal aggregates real elasticity modu-
lus reduction. Nanofiller particles aggregation is realized by cluster–cluster mecha-
nism and results in the formed fractal aggregates density essential reduction, which
is the cause of their elasticity modulus decreasing. Distinct from microcomposites,
nanocomposites require consideration of interfacial effects for elasticity modulus
correct description in virtue of a well-known large fraction of phases division sur-
faces for them.

18.1 INTRODUCTION
In the course of technological process of preparing particulate-filled polymer com-
posites in general1 and nanocomposites2–4 in particular, the initial filler powder
particles aggregation in more or less large particles aggregates always occurs. The
aggregation process exercises essential influence on composites (nanocomposites)
macroscopic properties.1–5 For nanocomposites, the aggregation process gains spe-
cial significance, since its intensity can be such that nanofiller particles aggregates
size exceeds 100 nm—the value that is assumed (although conditionally enough6) as
upper dimensional limit for a nanoparticle. In other words, the aggregation process
can be resulted in the situation when initially supposed nanocomposite ceases to
be as such. Therefore, at present, a number of methods exists, allowing to suppress
nanoparticles aggregation process.4,7
Analytically, this process is treated as follows. The authors5 obtain the equation:

k ( r ) = 7.5 × 10-3 Su , (18.1)

where k(r) is aggregation parameter, Su is specific surface of nanofiller initial par-

ticles, which is given in m2/g.
In turn, the value Su is determined as follows8:
6
Su =
ρ n Dp (18.2)

where ρn is nanofiller density, Dp is diameter of its initial particles.

From the eqs 18.1 and 18.2, it follows that Dp reduction results in Su growth that,
in turn, reflects in the aggregation intensification, characterized by the parameter
k(r) increasing. Therefore, in polymer nanocomposites, strengthening (reinforcing)
element are not nanofiller initial particles themselves, but their aggregates.9 This re-
Surface-Modified Magnetic Nanoparticles for Cell Labeling 291

sults in essential changes of nanofiller elasticity modulus, the value of which is deter-
mined with the aid of the equation9:
3 + dl
 a 
Eagr = Enan   , (18.3)
R
 agr 
where Eagr is nanofiller particles aggregate elasticity modulus, Enan is elasticity modu-
lus of material, from which the nanofiller was obtained, a is initial nanoparticles size,
Ragr is a nanoparticles aggregate radius, dl is chemical dimension of the indicated ag-
gregate, which is equal to ~1.1.9
As it follows from the eq 18.3, the initial nanoparticles aggregation degree en-
hancement, expressed by Ragr growth, results in Eagr decrease (rest of the parameters
in the eq 18.3 are constant) and, as consequence, in nanocomposite elasticity modu-
lus reduction.
Very often, the elasticity modulus (or reinforcement degree) of polymer com-
posites (nanocomposites) is described within the frameworks of numerous micro-
mechanical models, which proceed from elasticity modulus of matrix polymer and
filler (nanofiller) and the latter volume contents.10 Additionally, it is supposed that
the above-mentioned characteristics of a filler are approximately equal to the corre-
sponding parameters of compact material, from which a filler is prepared. This prac-
tice is absolutely inapplicable in case of polymer nanocomposites with fine-grained
nanofiller, since in this case, a polymer is reinforced by nanofiller fractal aggregates,
whose elasticity modulus and density differ essentially from compact material char-
acteristics (see the eq 18.3).5,9 Therefore, the microcomposite models application,
as a rule, gives a large error at polymer composites elasticity modulus evaluation
that, in turn, results in the appearance of an indicated models modifications large
number.10
Proceeding from the above-mentioned information, the present work purpose is
the theoretical treatment of particulate nanofiller aggregation process and elastic-
ity modulus (reinforcement degree) particulate-filled polymer nanocomposites with
due regard for the indicated effect within the framework of irreversible aggregation
models and fractal analysis.

18.2 EXPERIMENTAL
Polypropylene (PP) “Kaplen” of mark 01030 with average weight molecular mass of
~(2–3) × 103 and polydispersity index 4.5 was used as matrix polymer. Nanodimen-
sional calcium carbonate (CaCO3) in compound form of mark Nano-Cal P-1014
(production of China) with particles size of 80 nm and mass contents of 1–7 mass
% and globular nanocarbon (GNC) (production of corporations group “United Sys-
tems,” Moscow, Russian Federation) with particles size of 5–6 nm, specific surface of
1400 m2/g and mass contents of 0.25–3.0 mass % were applied as nanofiller.
292 Process Advancement in Chemistry and Chemical Engineering Research

Nanocomposites PP/CaCO3 and PP/GNC were prepared by components mix-

ing in melt on a twin screw extruder Thermo Haake, model Reomex RTW 25/42,
production of German Federal Republic. Mixing was performed at temperature
463–503 K and screw speed of 50 rpm during 5 min. Testing samples were prepared
by casting under pressure method on a casting machine, Test Sample Molding Ap-
paratus RR/TS MP of firm Ray-Ran (Taiwan) at temperature 483 K and pressure
43 MPa.
The nanocomposites melt viscosity was characterized by a melt flow index
(MFI). MFI measurements were performed on an extrusion-type plastometer, Nose-
lab ATS A-MeP (production of Italy), with capillary diameter of 2.095 ± 0.005 mm at
temperature 513 K and load of 2.16 kg. The sample was maintained at the indicated
temperature during 4.5 ± 0.5 min.
Uniaxial tension mechanical tests have been performed on the samples in the
shape of a two-sided spade with sizes according to GOST 112 62-80. The tests have
been conducted on a universal testing apparatus, Gotech Testing Machine CT-TCS
2000, production of German Federal Republic, at temperature 293 K and strain rate
~2 × 10−3 s−1.

18.3  RESULTS AND DISCUSSION

The particulate nanofiller aggregation degree can be evaluated and aggregates diam-
eter Dagr quantitative estimation can be performed within the framework of strength
dispersive theory,11 where shear yield stress of nanocomposite τn is determined as
follows:

GnbB , (18.4)
τ n = τ m' +
λ
where τm is shear yield stress of polymer matrix, bB is Burgers vector, Gn is nanocom-
posite shear modulus, λ is distance between nanofiller particles.
In case of nanofiller particles aggregation, eq 18.4 has the look11:

GnbB
τ n = τ m' +
k ( r ) λ , (18.5)
where k(r) is aggregation parameter.
The parameters included in the eqs 18.4 and 18.5 are determined as follows. The
general relationship between normal stress σ and shear stress τ has the look12:

s
τ= (18.6)
3
The intercommunication of matrix polymer τm and nanocomposite polymer matrix
τ m' shear yield stresses is given as follows5:
Surface-Modified Magnetic Nanoparticles for Cell Labeling 293

τ m' = τ m (1 − φn2/3 )
, (18.7)

where ϕn is nanofiller volume content, which can be determined according to the

well-known formula5:

Wn
φn =

ρn , (18.8)

where Wn is nanofiller mass contents, ρn is its density, which for nanoparticles is

determined according to the equation5:

ρ n = 188 ( Dp )
1/3
, kg/m3, (18.9)

where Dp is given in nm.

The value of Burgers vector bB for polymeric materials is determined as follows13:
1/2
 60.5 
bB =   , Å, (18.10)
 C∞ 
where C∞ is characteristic ratio, connected with nanocomposite structure dimension
df by the equation13:

2d f 4
C∞ = +
d ( d − 1)( d − d f ) 3 , (18.11)
where d is the dimension of Euclidean space, in which a fractal is considered (it is
obvious, that in our case d = 3).
The value df can be calculated according to the equation14:

d f = ( d − 1)(1 +ν ) , (18.12)
where ν is Poisson’s ratio, estimated according to the mechanical tests results with
the aid of the equation15:

En
Gn = , (18.13)
df
where σY and En are yield stress and elasticity modulus of nanocomposite, respec-
tively.
Nanocomposite moduli En and Gn are connected between themselves by the
equation14:
294 Process Advancement in Chemistry and Chemical Engineering Research

En
Gn = (18.14)
df
And at last, the distance λ between nanofiller non-aggregated particles is deter-
mined according to the equation11:

 4π  1/3  D p
λ =  - 2 . (18.15)
3f  2
 n  

From the eqs 18.5 and 18.15, k(r) growth from 5.65 up to 43.70 within the
range of Wn = 0.25–3.0 mass% for nanocomposites PP/GNC and from 1.0 up to
2.87 within the range of Wn = 1–7 mass% for nanocomposites PP/CaCO3 follows.
Let us note that the indicated variation k(r) for the considered nanocomposites cor-
responds completely to the eqs 18.1 and 18.2. Let us consider how such k(r) growth
is reflected on nanofiller particles aggregates diameter Dagr. The eqs 18.8, 18.9, and
18.15 combination gives the following equation:

(18.16)

allowing at Dp replacement on Dagr to determine real, that is, with accounting of

nanofiller particles aggregation, nanoparticles aggregates diameter of the used nano-
filler. Calculation according to the eq 18.16 shows Dagr increasing (corresponding
to k(r) growth) from 25 up to 125 nm within the range of Wn = 0.25–3.0 mass% for
GNC and from 80 up to 190 nm within the range of 1–7 mass% for CaCO3. Further
nanofiller particles aggregates density can be calculated according to the eq 18.9 at
the condition of Dp replacement by Dagr.
Within the framework of irreversible aggregation model, Dagr value is given by
the following relationship16:
1/ d agr
 4c kT  f 1/ dfagr , (18.17)
Dagr ~  0  t
 3η m0 
where c0 is nanoparticles initial concentration, k is Boltzmann constant, T is tem-
perature, η is medium viscosity, m0 is mass of initial nanoparticle, d fagr is fractal
dimension of particles aggregate, and t is aggregation process duration.
Let us consider estimation methods of the parameters included in the eq 18.17.
In the simplest case, it can be accepted that all particles of nanofiller initial powder
have the same size and mass. In this case, c0 ≈ ϕn, where ϕn value is determined ac-
cording to the eq 18.8 with using nanofiller particles aggregates diameter Dagr. η val-
ue is accepted equal to reciprocal of MFI value and m0 magnitude was calculated as
follows. In supposition of nanofiller initial particles spherical shape, the nanoparticle
Surface-Modified Magnetic Nanoparticles for Cell Labeling 295

volume was calculated according to the known values of their diameter Dp and then,
using ρn value, calculated according to the eq 18.8, their mass m0 can be estimated.
T value is accepted as constant and equal to nanocomposites processing duration,
that is, 300 s.
The fractal dimension of nanofiller particles aggregates structure d fagr was calcu-
lated with the aid of the equation17:
d agr − d
D  f
ρ n = ρdens  agr  , (18.18)
 2a 
where ρdens is density of compact material of nanofiller particles, a is self-similarity
(fractality) lower scale of nanofiller particles aggregates.
ρdens value for carbon is accepted equal to 2700 kg/m2, for CaCO3—2000 kg/m25 and
a value is accepted equal to the initial GNC particle radius, that is, 2.5 nm. d fagr val-
ues, calculated according to the eq 18.18, are equal to 2.09–2.67 and 2.47–2.75 for
GNC and CaCO3 nanoparticles aggregates, respectively.
In Figure 18.1, the dependences Dagr(Wn), plotted according to the eqs 18.16 and
18.17, comparison is adduced. As one can see, the good enough correspondence of
estimations according to both indicated methods was obtained (the average discrep-
ancy of Dagr values, calculated with the usage of these relationships, makes up ~16%).
This circumstance indicates that irreversible aggregation models can be used for the
theoretical description of particulate nanofiller particles aggregation processes. Be-
sides, eq 18.17 analysis demonstrates various factors influence on nanofiller particles
aggregates size (or their aggregation degree). So, c0, T, and t increasing results in
aggregation processes intensification and η, m0, and d fagr enhancement—to their
weakening.

FIGURE 18.1  The dependences of nanofiller particles aggregates diameter Dagr on nanofiller
mass contents Wn for nanocomposites PP/GNC (1, 3) and PP/CaCO3 (2, 4). 1, 2—calculation
according to the eq 18.16; 3, 4—calculation according to the eq 18.17.
296 Process Advancement in Chemistry and Chemical Engineering Research

Let us note in conclusion that proportionality coefficient in the eq 18.17 for

GNC and CaCO3 (cGNC and d fagr , respectively) can be approximated by the following
equation:
1/ dfav
cCaCO3  mCaCO3 
=  0GNC  , (18.19)
cGNC  m0 
where m0CaCO3 and d fav are masses of the initial particles of CaCO3 and GNC, respec-
tively, d fav is average fractal dimension of the indicated nanoparticles aggregates.
Further elasticity modulus Eagr of nanofiller particles aggregates according to the
eq 18.3 can be determined. Let us consider the concrete conditions of this equa-
tion usage in reference to nanocomposites PP/GNC. Two possible variants exist at
parameter a choice in the indicated equation. The first from them supposes that the
value a is equal to GNC initial particles diameter,9 that is, 5.5 nm. Such supposi-
tion means that GNC nanoparticles aggregates are formed by particle–cluster (P–
Cl) mechanism, that is, by separate particles GNC joining to a growing aggregate.18
However, such supposition gives unreal high Eagr values of order of 5 × 105 GPa. The
other variant assumes that nanofiller aggregation is realized by a cluster–cluster (Cl–
Cl) mechanism, that is, small clusters association in larger ones.18 In such model,
aggregate radius Ragr i −1
on the previous (i−1)th aggregation stage is accepted as a and
then the eq 18.3 can be rewritten as follows:

EnT . (18.20)
The elasticity modulus Eagr real values within the range of 21.3–5.0 GPa were ob-
tained at such calculation method. Further, the simplest microcomposite models can
be used for nanocomposite elasticity modulus En estimation. For the case of uniform
strain in nanocomposite phases, the theoretical value En ( EnT ) is given by a parallel
model10:

EnT , (18.21)

where Em is elasticity modulus of matrix polymer.

For the case of uniform stress in nanocomposite phases, the lower theoretical
boundary EnT is determined according to the serial model10:

Eagr Em (18.22)
EnT =
Eagr (1 − φn ) + Emφn
In Figure 18.2, the comparison of the experimentally received En and calculated
according to the eqs 18.21 and 18.22 EnT elasticity modulus values of the considered
nanocomposites PP/GNC is adduced. As one can see, the experimental data corre-
spond better to the determined, according to the eq 18.21 EnT upper boundary (in
Surface-Modified Magnetic Nanoparticles for Cell Labeling 297

this case, average discrepancy of En and EnT makes up ~8%). The indicated discrep-
ancy is due to objective causes. As it is known,10 at the eqs 18.21 and 18.22 deriva-
tion, the equality of Poisson’s ratio for nanocomposite both phases was supposed. In
practice, this condition nonfulfillment defines discrepancy between experimental
and theoretical data.

FIGURE 18.2  The dependences of elasticity modulus En on nanofiller mass contents Wn

for nanocomposites PP/GNC. 1—calculation according to the eq 18.22; 2—according to
the eq 18.21 at Eagr = variant; 3—according to the eq 18.21 at Eagr = const = 21.3 GPa; 4—
experimental data.
In Figure 18.2, the dependence EnT (Wn), calculated according to the eq 18.21 in
supposition Eagr = const = 21.3 GPa, is also adduced. As one can see, in this case,
the theoretical values of elasticity modulus EnT exceed the ones received essentially
experimentallyEn. Hence, the good correspondence of experiment and calculation
according to the eq 18.21 is due to real values Eagr usage only.
It is obvious that nanoparticles aggregates elasticity modulus reduction is due
to the indicated aggregates diameter growth and, as consequence, their density ρn
reduction, which can be calculated according to the eq 18.18. In Figure 18.3, the
dependence Eagr(ρn) is adduced, which, as was expected, proves to be linear, passing
through coordinates origin and is described analytically by the following empirical
equation:

En = Em (1 − φn ) + bEnanφn
, GPa, (18.23)

where ρn is given in kg/m3.

298 Process Advancement in Chemistry and Chemical Engineering Research

FIGURE 18.3  The dependence of GNC nanoparticles fractal aggregates elasticity modulus
Eagr on their density ρn for nanocomposites PP/GNC.

The limiting magnitude ρn = ρdens allows to obtain the greatest value Eagr ≈ 34 GPa
for GNC aggregates, which is the real value of this parameter.1
The authors19 proposed to use a modified mixtures rule for nanocomposites elas-
ticity modulus En determination, which in original variant gives upper limiting value
of composites elasticity modulus10:

En = Em (1 − φn ) + bEnanφn , (18.24)

where b < 1 is coefficient, reflected nanofiller properties realization degree in poly-

mer nanocomposite. In the present work context, the parameter bEnan as a matter of
fact presents nanofiller effective modulus or, more precisely, its aggregates modulus
Eagr (compared with the eq 18.21).
In Figure 18.4, the dependence of parameter b in the eq 18.24 on nanofiller par-
ticles aggregates diameter Dagr, calculated according to the eq 18.16, for the stud-
ied nanocomposites is adduced. As one can see, this dependence disintegrates on
two linear parts: at small Dagr, fast decay of b at Dagr growth is observed and at large
enough Dagr, the value b ≈ const ≈ 0.175. Let us note that dimensional interval of
the indicated transition showed in Figure 18.4 by a shaded area makes up Dagr ≈
70–100 nm, that is, it coincides approximately with upper dimensional boundary
of nanoparticles interval (although conditional enough6), which is equal to about
100 nm. As a matter of fact, the indicated dimensional interval defines the transi-
tion from nanocomposites to microcomposites, the dependence b(Dagr) for which
differs actually qualitatively. The adduced in Figure 18.4 dependence b(Dagr) can be
described analytically by the following integrated equation:
Surface-Modified Magnetic Nanoparticles for Cell Labeling 299

b = 0.67 − 6.7 ×10−3 Dagr , for Dagr ≤ 70 nm,

b = const = 0.175 , for Dagr > 70 nm. (18.25)

FIGURE 18.4  The dependence of parameter b on nanofiller particles aggregates diameter

Dagr for nanocomposites PP/GNC (1) and PP/CaCO3 (2). The shaded region indicates
transition of nanofiller particles aggregates from nano- to microbehavior.

In Figure 18.5, the comparison of experimentally obtained and calculated ac-

cording to the eq 18.25 dependences En(ϕn) is adduced for the studied nanocompos-
ites. In this case, the parameter b value was estimated according to the eq 18.25 and
values Enan were accepted equal to 30 GPa for GNC and 15 GPa for CaCO3. As one
can see, the good correspondence of theory and experiment is obtained (their mean
discrepancy makes up 3% that approximately equals to the experimental error of En
determination). Higher values En for nanocomposites PP/GNC in comparison with
PP/CaCO3, even at Dagr > 100 nm, are due to two factors: the initial nanoparticles a
smaller size, which gives higher values ϕn at the same Wn values (see the eq 18.8 and
18.9) and higher value Enan. It is important to note close values Eagr for nanocompos-
ites PP/GNC, determined according to the eq 18.20 and as bEnan.
300 Process Advancement in Chemistry and Chemical Engineering Research

FIGURE 18.5  The comparison of experimentally received (1, 2) and calculated according
to the eqs 18.24 and 18.25 (3, 4) dependences of elasticity modulus En on nanofiller volume
contents ϕn for nanocomposites PP/GNC (1, 3) and PP/CaCO3 (2, 4).

The authors8 proposed the following percolation relationship for polymer mi-
crocomposites reinforcement degree Ec/Em description:
Ec
= 1 + 11(φn ) , (18.26)
1.7

Em
where Ec is elasticity modulus of microcomposite.
Later, the eq 18.26 was modified in reference to the polymer nanocomposites
case20:
En
= 1 + 11(φn + φif ) , (18.27)
1.7

Em
where ϕif is relative fraction of interfacial regions.
It is easy to see that the modified eq 18.27 considers a factor of sharp increase of
division surfaces polymer matrix-nanofiller.21 In Figure 18.6, the comparison of ex-
perimentally obtained and calculated according to the eq 18.26 dependences En(ϕn),
for the considered nanocomposites, is adduced. As it follows from this figure data, eq
18.26 describes the experimental data for nanocomposites PP/CaCO3 well, but the
corresponding data for nanocomposites PP/GNC set essentially higher than theo-
retical curve. This discrepancy cause is obvious from the eqs 18.26 and 18.27 com-
parison—for nanocomposites PP/GNC, interfacial effects accounting is necessary,
that is, parameter ϕif accounting. Hence, in the considered case, only compositions
PP/GNC are true nanocomposites.
Surface-Modified Magnetic Nanoparticles for Cell Labeling 301

FIGURE 18.6  The comparison of experimentally received (1, 2) and calculated according
to the eq 18.26 (3) dependences of elasticity modulus En on nanofiller volume contents ϕn for
nanocomposites PP/GNC (1, 3) and PP/CaCO3 (2, 4).

18.4 CONCLUSION
The applicability of irreversible aggregation models for theoretical description of
particulate nanofiller particles aggregation processes in polymer nanocomposites
has been shown. Analysis within the framework of the indicated models allows to
reveal either factors influence on aggregation degree.
Strongly expressed aggregation of particulate nanofiller particles results in sharp
(in about four times) formed fractal aggregates real elasticity modulus reduction. In
turn, this process defines nanocomposites as the whole elasticity modulus reduction.
Nanofiller particles aggregation is realized by a cluster–cluster mechanism and re-
sults in the formed fractal aggregates density essential reduction, which is the cause
of their elasticity modulus decreasing.
A nanofiller elastic properties realization degree is defined by the aggregation
of its initial particles level. Unlike microcomposites, nanocomposites require inter-
facial effects accounting for elasticity modulus correct description in virtue of well-
known large fraction of phases division surfaces for them.
302 Process Advancement in Chemistry and Chemical Engineering Research

KEYWORDS

•• nanocomposite
•• globular nanocarbon
•• calcium carbonate
•• aggregation
•• interfacial effects
•• reinforcement

REFERENCES
1. Kozlov, G. V.; Yanovskii, Yu. G.; Zaikov, G. E. Structure and Properties of Particulate-Filled
Polymer Composites: The Farctal Analysis, Nova Science Publishers, Inc.: New York, 2010; p
282.
2. Kozlov, G. V.; Zaikov, G. E. Structure and Properties of Particulate-Filled Polymer Nano-
composites, Lambert Academic Publishing: Saarbrücken, DE, 2012; p 112.
3. Kozlov, G. V.; Yanovskii, Yu. G.; Zaikov, G. E. Particulate-Filled Polymer Nanocomposites.
Structure, Properties, Perspectives, Nova Science Publishers, Inc.: New York, 2014; p 273.
4. Edwards, D. C. J. Mater. Sci. 1990, 25 (12), 4175–4185.
5. Mikitaev, A. K.; Kozlov, G. V.; Zaikov, G. E. Polymer Nanocomposites: Variety of Structural
Forms and Applications, Nova Science Publishers, Inc.: New York, 2008; p 319.
6. Buchachenko, A. L. Adv.Chem. 2003, 72 (5), 419–437.
7. Kozlov, G. V.; Yanovsky, Yu. G.; Zaikov, G. E. Synergetics and Fractal Analysis of Polymer
Composites Filled with Short Fibers, Nova Science Publishers, Inc.: New York, 2011; p 223.
8. Bobryshev, A. N.; Kozomazov, V. N.; Babin, L. O.; Solomatov, V. I. Synergetics of Composite
Materials. Lipetsk NPO ORIUS 1994, 47, 154.
9. Witten, T. A.; Rubinstein, M.; Colby, R. H. J. Phys. II France 1993, 3 (3) 367–383.
10. Ahmed, S.; Jones, F. R. J. Mater. Sci. 1990, 25 (12) 4933–4942.
11. Sumita, M.; Tsukumo, Y.; Miyasaka, K.; Ishikawa, K. J. Mater. Sci. 1983, 18 (5) 1758–1764.
12. Honeycombe, R. W. K. The Plastic Deformation of Metals, Edwards Arnold Publishers: Cam-
bridge, UK, 1968; p 402.
13. Kozlov, G. V.; Zaikov, G. E. Structure of the Polymer Amorphous State, Brill Academic Pub-
lishers: Utrecht, Boston, 2004; p 465.
14. Balankin, A. S. Synergetics of Deformable Body, Publishers of Ministry Defence SSSR: Mos-
cow, RU, 1991; p 404.
15. Kozlov, G. V.; Sanditov, D. S. Anharmonic Effects and Physical-Mechanical Properties of
Polymers; Nauka: Novosibirs, RU, 1994; Vol. 29, p 261.
16. Weitz, D. A.; Huang, J. S.; Lin, M. Y.; Sung, J. Phys. Rev. Lett. 1984, 53 (17), 1657–1660.
17. Brady, L. M.; Ball, R. C. Nature, 1984, 309 (5965), 225–229.
18. Shogenov, V. N.; Kozlov, G. V. Fractal Clusters in Physics-Chemistry of Polymers. Nal’chik,
Polygraphservice T 2002, 18, 268.
19. Komarov, B. A.; Dzhavadyan, E. A.; Irzhak, V. I.; Ryabenko, A. G.; Lesnichaya, V. A.; Zve-
reva, G. I.; Krestinin, A. V. Polym. Sci., Ser. A 2001, 53 (6), 897–905.
20. Malamatov, A. Kh.; Kozlov, G. V.; Mikitaev, M. A. Reinforcement Mechanisms of Polymer
Nanocomposites. Publishers of D.I. Mendeleev RKhTU: Moscow, RU, 2006; p. 240.
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CHAPTER 19

A NEW CONCEPT OF
PHOTOSYNTHESIS
G.G. KOMISSAROV
N. N. Semenov Institute for Chemical Physics, Russian Academy of Sciences, Kosygin
St. 4, Moscow 119991, Russia. E-mail: [email protected]; [email protected]

CONTENTS
Abstract..................................................................................................................304
19.1 Functional Modeling of Photosynthesis......................................................305
19.2 The Becquerel Effect in Phtalocianine Films..............................................306
19.3 Hydrogen Peroxide—Source of Photosynthetic Oxygen (Hydrogen) ........310
19.4 Some Consequences Resulting from the New Concept of
Photosynthesis.............................................................................................315
19.5 Conclusion...................................................................................................322
Acknowledgment...................................................................................................324
Keywords...............................................................................................................325
References..............................................................................................................325
304 Process Advancement in Chemistry and Chemical Engineering Research

ABSTRACT
A history of the formation of a new concept of photosynthesis proposed by the
author is considered ranging from 1966 to 2013. Its essence is as follows: the pho-
tosynthetic oxygen (hydrogen) source is not water, but exogenous and endogenous
hydrogen peroxide; thermal energy is a necessary part of the photosynthetic process;
along with carbon dioxide, air (oxygen, inert gases) is included in the photosynthetic
equation. Here, the mechanism of the photovoltaic (Becquerel) effect in films of
chlorophyll and its synthetic analogue—phthalocyanine—is briefly touched. There
are presented works on artificial photosynthesis performed in the laboratory of Pho-
tobionics of the Semenov Institute of Chemical Physics RAS.
I know Gennady Efremovich Zaikov from the first day of my stay at the Institute
of Chemical Physics RAS (since 1967). I was always amazed and still am at his
lively mind, a fantastic performance, and a strong sense of humor. His gait is always
swift, handshake is vigorous, and at meetings I always see a smiling face.
Taking this opportunity, I wish dear Gennady Efremovich good health and new
successes, happiness.
Photosynthesis is the “global,” “fundamental,” and “unique” biological process.
Its mechanism study is one of the central tasks of the modern natural science. Inves-
tigations into photosynthesis started in 1771, when the outstanding English chemist,
Joseph Priestley, discovered the capacity of plants to “repair air, distorted by the
burning of candles”, that is, release oxygen. A significant contribution to the devel-
opment of the concept was introduced by Ingenhousz, who showed the necessity of
solar light for the occurrence of photosynthesis: the release of oxygen occurs only if
the plants are illuminated (in darkness, they lose this capacity). He also established
that photosynthesis is accompanied by the buildup of organic products. The experi-
ments carried out by J. Senebier and N.Th. Saussure revealed initial substances of
photosynthesis (carbon dioxide and water). The energy aspect of the problem was
discussed for the first time by J.R. Mayer. In 1941, A.P. Vinogradov and R.V. Teis
in USSR and S. Ruben with his colleagues in the USA established that oxygen is
released from water and not from carbon dioxide.1 During the last 70 years, the main
equation of photosynthesis does not change and is written as follows:
Light
CO2 + H2O → carbohydrates + O2 (19.1)
During breathing (reaction (1) taking place from the left to the right), the energy
stored in the final products by the plants is released. It should also be mentioned that
all living substances are constructed from molecules that initially formed in plants.
Examination of the unique biological process of storage of solar energy has been
continuing for more than two centuries, but the final mechanism has not as yet been
completely explained.
A New Concept of Photosynthesis 305

19.1  FUNCTIONAL MODELING OF PHOTOSYNTHESIS

Regardless of the complexity of photosynthesis, it is possible to define two main
stages in this process: the light stage, whose occurrence requires the direct effect of
light, and the dark stage, which follows the light stage. It is assumed that the first,
light stage, is characterized by the occurrence of photosplitting of water with the
generation of molecular oxygen, which is released into the atmosphere as a second-
ary product:
Light
Н2О → [H] + O2 (19.2)
Chlorophyll
The resultant hydrogen subsequently enters into the thermal cycle responsible
for the fixation of carbon dioxide, which is completed with the formation of carbo-
hydrates, conventionally denoted by {CH2O}:
Ferments

[H] + CO2 → {CH2O} (19.3)

This stage, including a large number of fermentation reactions, has been exam-
ined in detail in studies by the outstanding American chemist M. Calvin who was
awarded the Nobel Prize in 1961.
Thus, “photosynthesis” consists of two main stages: photolysis of water and
dark synthesis of carbohydrates. In the second stage, there are no specific photosyn-
thesis processes; the fixation of carbon dioxide in dark may be carried out by the
liver cells of a rat, if a suitable hydrogen donor is available.
In this chapter, we shall approach the problem of photosynthesis from the physi-
cal–chemical position. Can artificial physical–chemical systems reproduce the light
stage of photosynthesis?
The sequence of transformation of energy during photosynthesis, as described in
Refs 1–3, may be written in the following form:

EL → EE → EC (19.4)

where E is the energy with the appropriate indexes “light,” “electrical,” and “chemi-
cal.”. Equation 19.4 greatly simplified the problem of functional modeling of pho-
tosynthesis because it makes it possible to solve the problem in two independent
stages:

EL → EE (19.5)

EE → EC (19.6)
306 Process Advancement in Chemistry and Chemical Engineering Research

and transformation (eq 19.6). Electrolysis of water with the release of gaseous oxy-
gen has been solved a long time ago. On an industrial scale, the process is carried
out with high efficiency (current efficiency is 95–99%). Thus, the initial task is to
find a device capable of generating electrical energy under the influence of light.
In 1839, E. Becquerel4 first described the occasionally detected photoeffects.
The principle of the phenomenon, subsequently referred to as the Becquerel effect
or photovoltaic effect, is the formation of a difference of the potentials between two
metallic electrodes placed in an electrolyte; one of the electrodes is coated with a
layer of a light-sensitive substance.
In 1874, Becquerel observed that the illumination of a silver-coated platinum
electrode carrying a chlorophyll film, with red light, changes its potential.5 We be-
lieve that this date should be regarded as the basic date in the physical–chemical
modeling of photosynthesis, although Becquerel never mentioned this approach.
His work was directed to confirm the phenomenon of optical sensitization in pho-
tography, discovered by H.W. Vogel.6
Prior to starting modeling experiments, we thought that it was essential to evalu-
ate (at least approximately) the intensity of the photoflux in chloroplast. Using Fara-
day’s law, it can easily be shown that the total current in chloroplasts, containing 0.1
mg of chlorophyll, is equal to 10−5 A. However, in a single chloroplast, the current
is evidently many times smaller (10−13 A).
In 1966, as a functional model of chloroplast, we proposed a photovoltaic bat-
tery.1–3 Its first in the world variant was realized at the Institute of Chemical Physics
of the Academy of Sciences of the USSR in 1968.1,7,8 Then a similar battery was
built in the United States.9 The battery consisted of four electrodes coated with a
synthetic analogue of chlorophyll, that is, phthalocyanine. It was characterized by
the following parameters8: the light potential reached 2.4 V, which is fully sufficient
for electrolysis of water with the generation of molecular oxygen (the dissociation
potential of water 1.23 V); the current taken from the battery was 5.6 × 10−5 A so that
it was possible to record oxygen by the conventional methods. The quantum yield
of the photocurrent was not high, 0.01–0.1%. The proposed device is capable of
releasing oxygen from water under the effect of visible light, that is, reproduce one
of the main functions of the chloroplast, and the process, taking place in the battery,
is of photocatalytic nature.

19.2 THE BECQUEREL EFFECT IN PHTALOCIANINE FILMS

The maximum value of the quantum yield of the photocurrent is detected in the case
of monomolecular coating of the electrode with the pigment (Fig. 19.1).10 In the
chloroplast, the membranes are also covered on average by a monomolecular layer
of chlorophyll.
A New Concept of Photosynthesis 307

FIGURE 19.1  Dependence of the short circuit current (curve1) and the quantum yield
(curve 2) on the thickness of the pigment film.

To increase the quantum yield, it was necessary to carry out a systematic ex-
amination of the mechanism of the Becquerel effect. This was carried out in our
laboratory. As a result, the quantum yield was increased to units and, subsequently,
to tens of percent.1,10–14 In other words, it was possible to show that with regards
to efficiency, the modern photovoltaic systems are not inferior to photosynthetic
structures.
Examination of the dependence of the magnitude of current and potential of
pigmented electrodes on the pH value of the electrolyte gave an unexpected result.
Fixed value of pH in darkness was observed, these values are almost identical with
the values in platinum electrodes in the absence of the pigment in them. This indi-
cates that the pigment film was penetrated by a large number of pores (Fig. 19.2).1,13
The methods of the preparation of films, the values of current, potentials, and
the dynamics of these values unambiguously show that they used porous films, but
the interpretation of the observed relationships was based on the considerations re-
garding the monolithic pigmented layer of the electrode. This was followed by the
development of methods of production of pore-free films and at the present time, it
is possible to specify the main types of photovoltaic effects in the films of semicon-
ductor pigments contacting, on the one side, with the electrolyte and, on the other
side, with the metal (Fig. 19.3).1,12,13,15,16
308 Process Advancement in Chemistry and Chemical Engineering Research

FIGURE 19.2  Scheme of an electrode coated with a layer of pigment: 1—electrolyte, 2—

pigment layer, 3—platinum electrode, 4—insulating layer, 5—thickness of layer penetrated
by incident light, 6—main body of the pigment suspension.

FIGURE 19.3  Schematic of three types of pigment films (photovoltaic effects). Dark areas
show the pigment, dashes indicate electrolyte, the metal is shaded by solid inclined lines. (a)
A thick porous film (light does not reach the pigment–metal contact). Light-induced potential
arises due to a change in concentration of potential-governing ions at the electrode surface
(ϕ = A(B − ln C); ϕ is light-induced potential; A = RT/nF. R, T, n, and F have the commonly
accepted meaning). The time needed to reach the steady photo-induced potential is of photo-
induced potential in minutes, the dark current ≈ 10−6 A/cm3. (b) Intermediate type. (c) A
thin nonporous film (light penetration depth exceeds the film thickness). The response to
illumination is a result of semiconductor processes in the bulk of the film and its boundaries.
The time taken to reach the steady photo-induced potential is a fraction of second; the dark
current is 10−12 A/cm3.
A New Concept of Photosynthesis 309

The nature of the generation of photoresponse in the films differs principally.

The values of current and their kinetic parameters differ tens, hundred, or more
times. The previously described considerations enabled us to start investigations
in the area of structural–functional modeling, the development of artificial systems
reproducing the structure (composition) and function of natural photosynthetic for-
mations. The analysis of literature data on the generation of oxygen from water in
physical–chemical systems (electrolysis, photolysis, and radiolysis of water) and
also the data obtained in our laboratory on the generation of oxygen in natural and
modeling systems have made it possible to propose an original schema of photosyn-
thetic release of oxygen.1,12
According to the schema, the generation of a single molecule of oxygen requires
at least four light quanta, each of which generates an “electron–hole” couple, and
the electron is used in the reaction H+ + e →H, required for subsequent fixation
of CO2. The surface of lamellae (sheets from which chloroplasts is produced) is a
unique photoelectrode, consisting of alternating anodic and cathodic microregions
(Fig. 19.4).1,12,13 On the whole, the proposed schema of the dissociation of water has
made it possible to explain several relationships in the photosynthetic generation of
oxygen.

FIGURE 19.4  Structural scheme of the absorbed layer on the surface of the pigment (view
from above and from side).
310 Process Advancement in Chemistry and Chemical Engineering Research

The experimental confirmation required many years of work resulting in the

development of a new concept of photosynthesis.

19.3  HYDROGEN PEROXIDE—SOURCE OF PHOTOSYNTHETIC

OXYGEN (HYDROGEN)
19.3.1  THE EFFECT OF HYDROGEN PEROXIDE ON
THE KINETICS OF GENERATION OF OXYGEN DURING
PHOTOSYNTHESIS
The sequence of dissociation of water during photosynthesis, proposed by us in
1973, may be represented in the form: H2O → H2O2 → HO2 → O2, that is, water
is oxidized to hydrogen peroxide, which, in the final analysis, results in the gen-
eration of molecular oxygen (see the previous chapter). At present, there is a large
number of literature data indicating the participation of hydrogen peroxide as an
intermediate product in the course of formation of oxygen. We attempted to use the
kinetic methods for confirming the participation of hydrogen peroxide in the course
of photosynthetic generation of oxygen. For this purpose, we proposed a kinetic
model based on the representation of vector algebra and projection geometry.1,17 The
results of kinetic analyses and the experimentally obtained changes of the kinet-
ics of photosynthetic generation of oxygen in the presence of exogenous hydrogen
peroxide indicate that it is capable of penetrating in light into the oxygen-generating
complex of growth instead of water and act as an independent source of electrons
and an independent source of generation of oxygen situated outside the four-stage
oxygen cycle.

19.3.2  HYDROGEN PEROXIDE—A SINGLE SOURCE OF

PHOTOSYNTHETIC OXYGEN
As already reported, the main method of overcoming the problem of photosynthesis
is based on the light stage of photosynthesis (the stage of photodissociation of wa-
ter). The work of current investigators, concerned with the examination of the pho-
tosynthesis mechanism, has been and is still directed to finding approaches capable
of explaining the mechanism by which the chlorophyll (the photosynthetic oxygen-
generating reactions center) is capable of storing the energy of several light quanta
in order to use this energy for the formation of molecular oxygen. Many original
studies have been published in the course of these investigations.
Already in our first study, concerned with the justification of the photoelectro-
chemical hypothesis of photosynthesis,3 we paid attention to the need to take into
account the changes of the properties of water in the chloroplast where it is situated
between the lamellae with the distance between them not exceeding 100 Å. It is well
A New Concept of Photosynthesis 311

known that the properties of structured liquid (in particular, and/or situated at the
boundary with the solid phase) greatly differ from the properties in the volume. The
viscosity of water in capillaries is an order of magnitude higher than the viscosity of
water in the volume, and the heat conductivity of water in the layers increases tens
of times, dielectric permittivity decreases from 81 (water in the volume) to 3–4 (in
the interlayers with a thickness of 0.5–0.6 nm). Similar examples make it possible
to assume that the puzzle of biological oxidation of water with the generation of
oxygen is “hidden not only in the properties of the chloroplast but also of the water
itself.”3
The extensive and long-term examination of the physical–chemical properties of
water resulted in an unambiguous conclusion: in nature, there is no pure water, and
water always contains an impurity, that is, hydrogen peroxide. In a thridistillate, the
concentration of hydrogen peroxide is 10−9 M,18 in water of natural reservoirs (seas,
rivers, lakes), it reaches 10−6 M, in rainwater is 10−5 M.1,19 This makes it possible to
supplement the equation of biological oxidation of water (eq 19.2) by another term,
that is, hydrogen peroxide, which was discovered in 1818 by L.J. Thernard and re-
ferred to as “oxidized water”20:
Light
Н2О2, Н2О → [H] + O2 (19.7)
Chlorophyll
At first sight, it may appear that in this case, we are talking about some negligi-
bly small impurity, with no relationship to photosynthesis; however, this is not so.
By evaporating the aqueous solution of the peroxide, it is possible to increase its
concentration tens of times, because its volatility is considerably smaller than in the
case of water. The method of concentration of the aqueous solutions of hydrogen
peroxide by evaporation of water has been used in the chemical practice for a long
time now.20 Transpiration (evaporation of water by plants) evidently plays the same
function in addition to the protection of plants against overheating. For each kg of
water absorbed by the roots from soil, only 1 g (1/1000 part of) is used by the plant
for the construction of tissue. Thus, the green leaves may be regarded as a unique
concentrator of hydrogen peroxide. It should also be mentioned that the second
initial substance in photosynthesis is CO2 whose content in air is only 0.03% (less
than the content of inert gases). Its concentration is higher than the concentration of
hydrogen peroxide in the initial water. However, the solubility of hydrogen perox-
ide in water is seven times higher than that for CO2 (2 × 105 and 4.5 × 10−2 mole/L
atm, respectively). This results in a serious consequence. Regardless of the area of
formation of H2O2 (in air, in air bubbles in soil), its concentration in contacting water
will be higher than in CO2. Naturally, in this case, it is necessary to take into account
the initial concentration of these substances. In addition to exogenous hydrogen
peroxide, the photosynthesized cell also contains endogenous hydrogen peroxide.
Its source in the cytoplasm is the mitochondrin (in high-intensity photosynthesis,
it converges to chloroplasts), peroxisomes, and so forth. For example, up to 40%
312 Process Advancement in Chemistry and Chemical Engineering Research

of hydrogen peroxide, generated in peroxisomes, is transferred into the cytosol. In

other words, the hydrogen peroxide in vivo is completely sufficient for explaining
the observed intensity of the generation of molecular oxygen from this hydrogen
peroxide.1
The data, obtained in Ref 21, are most interesting from the viewpoint of examin-
ing the role of hydrogen peroxide in the generation of photosynthetic oxygen. The
authors carried out mass spectrometric examination of photosynthetic generation
of oxygen using hydrogen peroxide, marked with respect to oxygen (H2 18O2). The
results show that H2 18O2 is the source of the entire amount of generated oxygen. It
is well known18 that the hydrogen peroxide in chemical systems rapidly exchanges
hydrogen (deuterium) with water. This was already established in 1934. However,
when using the oxide marked with respect to oxygen, the situation is completely
different. As reported in the monograph,20 “the oxygen of water, used as a solvent,
does not take part in the dissociation or reaction of hydrogen peroxide; no exchange
was found between the water and the resultant molecular oxygen or oxidized prod-
ucts.” Consequently, if the photosynthesized systems contain water and hydrogen
peroxide, it is evident that the dissociation with the generation of oxygen explained
case of the latter compound.
In the photoelectrochemical mechanism of formation of oxygen in vivo from
two possible sources (hydrogen peroxide and water), the first mechanism is obvi-
ously preferred. In our laboratory, using the method of a spinning disk electrode
with a ring (the spinning speed up to 3000 rpm), we showed the catalase activity of
chlorophyll films that were in contact with the aqueous solution of hydrogen perox-
ide. Under the effect of light, the rate of dissociation of hydrogen peroxide increased
2–3 times in comparison with the darkness values.1
The results obtained in our laboratory and also the critical analysis of the lit-
erature data on the photosynthetic generation of oxygen have made it possible to
propose a completely new viewpoint. According to the viewpoint, the source of
photosynthetic oxygen (hydrogen) is not water but the exogenous and endogenous
hydrogen peroxide.1,22–26
Naturally, it is difficult for a conventional photosynthetist to understand our po-
sition, because in the current literature, water is regarded as a source of oxygen. It is
useful to mention that up to the studies carried out by A.P. Vinogradov27 and S. Ru-
ben,28 which appeared 70 years ago, the majority of investigators of photosynthesis
had assumed that CO2 is the source of oxygen in photosynthesis.
At the Fifth International Biochemical Congress (Moscow, 1961), A.P. Vinogra-
dov and V.M. Kutyurin29 attempted to evaluate the variants of the methods of dehy-
dration of water during photosynthesis. We believe that A.P. Vinogradov had experi-
mental justification for proposing the hydrogen peroxide as a source of oxygen in
photosynthesis. We shall discuss the results. The studies27,28 show convincingly that
CO2 cannot be the source of photosynthetic oxygen as assumed at that time by the
majority of researchers. This completed the revolutionary break in the examination
A New Concept of Photosynthesis 313

of the photosynthesis mechanism. Since it was not possible during the experiments
to achieve the equality of the isotope composition of the oxygen generated during
photosynthesis and the oxygen in water, it would be necessary to introduce an as-
sumption on the effect of breathing on the investigated process.29 The situation ex-
isting in 1961 and this problem was characterized by R. Wurmser 30 as “it is almost
evident (bold face by me, G.K.) that the generated oxygen comes from water.” In
1975, H.J. Metzner 31 published a large article: “The dissociation of water during
photosynthesis? Critical review.” Analyzing the literature data and his own results,
the author concluded that they reject the hypothesis on the oxidation of water in
photosynthesis. The study ended with the words: “If we take together the data of
published isotope experiments as a confirmation against the splitting of O–H bonds,
we should postulate the rapture of another oxygen-containing bond, that is, C–O
bond or O–O bond in the peroxide precursor of oxygen” (bold face by me, G.K.).
We have assumed (and we shall remain on these positions) that the pigment sys-
tem of the chloroplast is a highly autonomous structure, designed for the generation
of protons and molecular oxygen.

19.3.3  THE ROLE OF THERMAL ENERGY IN

PHOTOSYNTHESIS AND CORRECTION OF THE FUNDAMENTAL
PHOTOSYNTHESIS EQUATION
It is generally accepted (see any textbook on photosynthesis) that the thermal energy
is a waste production of the photosynthetic process. In the case of a high-intensity
process, only 0.5–5% of light energy is used up for photosynthesis, whereas ~95%
of energy “degrades into heat.” It is difficult to assume that in billions of years of
their existence on earth, the plants have not adapted themselves to a more efficient
utilization of light energy. In 1973, the author assumed that the thermal energy is not
only an important but also essential participant of the photosynthetic process.1,12,32
This viewpoint is presented in the most complete form in the study “Photosynthesis
as a thermal process.”33 According to this concept, in the regions with the size of
the order of the chlorophyll molecule, the local temperature may greatly exceed
(by several tens of degrees) the temperature of the surrounding medium. According
to our estimates, this temperature reaches 70°C as a result of the recombination of
charge carriers in the reaction center in which the adsorption of initial substances
has not been completed at the given moment. Increase of the temperature inside the
chloroplasts accelerates at the diffusion of both the products of photosynthesis and
initial substances. An increase of temperature also facilitates the transport of ions
through the membrane. According to calculations, the energy required for the trans-
port of anion from the electrolyte into a lipid membrane is 250 kJ/mole. However,
the energy of transport of the ion (e.g., sodium, potassium) through a membrane
channel is considerably lower (~20 kJ/mole).34
314 Process Advancement in Chemistry and Chemical Engineering Research

Already at the start of previous century, K.A. Timiryazev35 proposed a hypoth-

esis regarding the effect of thermal energy in photosynthesis. He assumed that the
heating of chloroplasts, caused by sunlight, may be sufficient for the occurrence, in
the chloroplasts, of a process thermodynamically reversed in relation to combustion,
and, consequently, this may be used to explain the principle of photosynthesis. This
viewpoint is at present of only historic interest because it was criticized. However,
in the light of our considerations regarding hydrogen peroxide as a source of mo-
lecular oxygen in photosynthesis and local heating of the chloroplasts, it is possible
that this hypothesis will be developed further.
It may be assumed that in photosynthesis, together with the photoelectrochemi-
cal mechanism, there is also the possibility of the thermal dissociation of hydrogen
peroxide as the release of molecular oxygen. The thermal stability of water is in-
comparably higher than that of hydrogen peroxide.1,20
An additional confirmation of the possibility of thermal dissociation of H2O2 in
photosynthesis may be the data of modeling systems—the films of phthalocyanine
(synthetic analogue of chlorophyll) on a Pt electrode, which is in contact with the
electrolyte, where the dependence of the photopotential of the films of phthalocya-
nine on heating of the electrolyte may be examined. At a temperature higher than
80°C, the photoresponse cannot be recorded. This can be naturally explained by the
thermal dissociation of hydrogen peroxide formed on the surface of the platinum
electrode.1,22
It should be mentioned that the assumptions regarding the local heating of chlo-
roplast, introduced by us in 1973, were initially met with excessive criticism, but
in recent years, these concepts in the sphere of biophysics do not lead to any dis-
pute.36 In addition, a number of studies have been published recently on polymers,
the theory of the photographic process, media for optical memory, glasses, where
the assumption on the local temperature is used successfully for explaining the ob-
served relationships. In the monograph by S.F. Timashev “Physics and chemistry of
membrane processes,”34 the role of the local heating is treated in a special section.
On the basis of all these considerations, it may be assumed that the local equa-
tion of photosynthesis should include not only light but also thermal energy.1,22–26,33
The point is that in the implicit form, the thermal energy, from our viewpoint, has
been included in the general equation of photosynthesis for a long time. We shall
pay attention to the thermodynamic potential of dissociation of water. The minimum
difference of the potentials, required for the electrolysis of water at 25°C, 1 atm,
and on the condition of the supply of thermal energy, is 1.23 V. The thermoneutral
potential of dissociation of water at 25°C is 1.47 V. In all investigations into pho-
tosynthesis, only the first magnitude (1.23 V) has been used, but the necessity for
supplying thermal energy in this case is simply not mentioned.
Thus, the previously presented data on the exogenous and endogenous hydrogen
peroxide as a source of oxygen (hydrogen) in photosynthesis and the role of thermal
A New Concept of Photosynthesis 315

energy make it possible to write the basic equation of photosynthesis in the follow-
ing form1,22–26:
Light energy
CO2 (air) + H2O2 (water)  carbohydrates + O2 (19.8)
Thermal energy (+/-)

The main difference between this equation and eq 19.1 is the replacement of
H2O by H2O2, and water plays the role of the reaction medium for CO2 and H2O2.
It should be mentioned that an identical situation was recorded previously with
CO2. Initially, it was assumed that “air” (my italics, the author) damaged by the
combustion of candles takes place in photosynthesis, and, subsequently, the modi-
fication- CO2 (G. Senebier, 1782) was introduced. The concentration of CO2 in air
is only 0.03%. It is also possible that in future, new components of both air and
natural water, taking part in photosynthesis, will be detected. For example, reports
have appeared according to which the inert gases affect the rate of splitting of cells.
Therefore, we regard it as useful to write in the main photosynthesis equation, air
in addition to CO2 and water together with H2O2 and, naturally, photosynthesis, like
any other life processes, is not possible without water.
The sign (+/−) in eq19.8 indicates that at high densities of the light the leaf
(chloroplast) transfers the energy to the surrounding medium, and at low densities,
it takes the energy from the surrounding medium. In the latter case, the coefficient of
transformation of solar energy may be higher than 100% because the contribution of
thermal energy is not taken into account. A similar situation was found in the early
stages of examination of the efficiency of operation of fuel elements.
Thus, we shall make a conclusion. A new concept, according to which the source
of oxygen (hydrogen) in photosynthesis is the exogenous and endogenous hydrogen
peroxide, and not water, has been proposed. The dissociation of hydrogen peroxide
with the generation of molecular oxygen is possible either by photoelectrochemical
and/or thermochemical mechanism.

19.4  SOME CONSEQUENCES RESULTING FROM THE NEW

CONCEPT OF PHOTOSYNTHESIS

19.4.1  THE EFFECT OF HYDROGEN PEROXIDE ON THE

GROWTH OF PLANTS
Within the framework of the proposed concept, it was reasonable to propose that
the variation of the concentration of peroxide in water has a significant effect on the
rate of growth of plants because photosynthesis, in particular, determines the rate of
the physiological processes. The authors of Ref 37 presented results of experimental
verification of this assumption. Naturally, the effect of different amounts of exog-
316 Process Advancement in Chemistry and Chemical Engineering Research

enous hydrogen peroxide may have an appropriate effect also on the rate of genera-
tion of endogenous peroxide. The mechanism of participation of hydrogen peroxide
in the physiological processes of growth is being studied intensively at the present
time. Peroxide determines the intensity of photophosphorylation, photobreathing,
fungitotoxicity of the surface of leaves, and so on.
In order to record the growth of plants in the presence of hydrogen peroxide,
in addition to the traditional biological approach, we have also used the recently
proposed method of laser interference auxanometry.1,24 It should be mentioned that
the problem of the growth of plants is one of the central problems in current phyto-
physiology.
Analysis of the literature shows that the stimulating effect of hydrogen peroxide
on the growth and development of plants has been known for a long period of time.
Already at the beginning of this century, it was known that the solutions of hydrogen
peroxide stimulate the growth of seeds. The introduction of hydrogen peroxide into
soil increases the yield of corn, soya beans, accelerates the growth of seeds, but the
reason for this effect, as reported in the above investigations, was not clear.20

USING PLANTS FOR THE GENERATION OF AIR IN A CLOSED

VOLUME
If we compare the traditional form of the main equation of photosynthesis (eq 19.1)
with eq 19.8 proposed by us, it may be seen that in addition to the differences men-
tioned previously, there is one important consequence in our view. The classic equa-
tion of photosynthesis assumes that there is complete agreement with respect to the
initial and final products between photosynthesis and breathing (eq 19.1, read from
right to left, is the equation of breathing). In the concepts proposed by us, the rela-
tionship between the fundamental biological process and breathing is complicated
because the final product in breathing is water which, in our view, does not split
during photosynthesis. This is illustrated by the diagram of formation of oxygen and
its usage during breathing (Fig. 19.5).
It is well known that in addition to photosynthesis, the leaf is characterized by
the occurrence of an opposite process stimulated by light, that is, the generation of
carbon dioxide and absorption of oxygen (photobreathing). In the dark conditions,
the intensity of the process, opposite photosynthesis (dark breathing), is 5–7% of
photosynthetic gas exchange (plants, like living creatures, require oxygen). How-
ever, the intensity of photobreathing is an order of magnitude higher in comparison
with dark breathing and equals ~50% of photosynthetic gas exchange.38,39 Since the
photobreathing greatly reduces the rate of real photosynthesis and, consequently, the
productivity of the plants, a larger number of attempts have been made to liquidate
this process (or, at least, reduce its intensity). These attempts have not been success-
ful. According to V.I. Chikov,38 “none of the directions in the search for the methods
of decreasing the intensity of photobreathing have resulted in a positive result for in-
A New Concept of Photosynthesis 317

creasing the productivity of the plants. In addition, it is believed that the conditions,
suppressing photobreathing, also decrease the productivity of the plants.”

FIGURE 19.5  The relationship between photosynthesis and (photo) breathing within the
framework of the conventional considerations regarding photosynthesis (A) and in accordance
with the concept proposed by the author of the article (B).

Previously, it was mentioned that breathing is accompanied by the formation of

endogenous hydrogen peroxide. In accordance with the proposed concept of pho-
tosynthesis, the endogenous hydrogen peroxide is a source of not only oxygen, re-
leased into the atmosphere, but also of hydrogen used in the synthetic processes of
growth. It should be mentioned that photobreathing is most active when the plant is
supplied with abundance of mineral nitrogen, that is, favorable conditions are cre-
ated for the growth of biomass. The stimulating effect of the exogenous hydrogen
peroxide (at the optimum concentration of the latter) was examined in the previous
section.
Thus, it may be assumed that the activity of synthetic processes in the plants
is determined in approximately equal parts by the intensity of photosynthesis and
photobreathing. Naturally, photobreathing uses the products stored as a result of
photosynthesis plus atmospheric oxygen. A further examination of this process by
physiologists of plants would enable, in our opinion, the development of the opti-
mum technology to cultivate agricultural plants.
The considerations described here cast doubts on the exclusive role of plants
in the formation of the current oxygen atmosphere of the earth, widely cited in the
biological literature. We believe that in the geochemical investigations, which, in
our view, are most important in the given problem, it is easy to find an opposite
viewpoint.
Explanation of the mechanism of generation of photosynthesizing oxygen is
very important in the current period because of the development of space technol-
ogy, the development of essential conditions for the life of man in a closed space. If
the plants ensure the supply of oxygen to our atmosphere, it is natural that it should
318 Process Advancement in Chemistry and Chemical Engineering Research

be attempted to use them for the generation of air in a closed system, for example,
in a space station. Our concept of photosynthesis is directly related to this problem.
In September 1991, eight volunteers started two-year tests in the Biosphere 2—
complex isolated from the outer world. The complex is a prototype of future cosmic
stations on the planets of the solar system.40 The Biosphere 2 is a large experimental
system generated for the examination of ecological processes taking place on the
earth, and also for the development of the conditions of life activity in future cosmic
stations, which will be constructed mainly on Mars. The experiment was planned for
two years. However, already in June 1992, the oxygen content inside the complex
was greatly reduced (from 20.94 to 16.4%). The subsequent decrease of the oxygen
concentration was 0.25–0.3% per month and it was, therefore, necessary to supply
oxygen into the complex.41 A special commission has been formed for investigating
the reasons resulting in a decrease of the oxygen concentration.
We believe that one of the reasons resulting in the unsatisfactory dynamics of
oxygen in the Biosphere 2 is associated with the fact that the developers of the ob-
ject used the conventional assumptions according to which the water is a source of
oxygen in photosynthesis. In accordance with our concept of photosynthesis (see eq
19.8 and Fig. 19.5), for the normal functioning of a hermetically sealed complex,
containing plants, it is necessary to ensure the occurrence in the complex of the pro-
cesses resulting in the generation of hydrogen peroxide. On the earth, the hydrogen
peroxide forms as a result of storm discharges, the radiolysis of underground water,
and so on.

19.4.2  ARTIFICIAL PHOTOSYNTHESIS AND A PROBLEM OF

THE LIFE ORIGIN
The attempts to model natural photosynthesis have been made since long ago. Back
in the early 20th century, there were studies aimed to reproduce the fundamental
biological process or its separate steps by means of simple photochemical systems.1
Currently, the number of publications dealing with this topic increases in an ava-
lanche-like fashion (Fig. 19.6). However, the attempts made did not result in the
design of artificial physicochemical systems able to form organic products from
carbon dioxide and water with simultaneous evolution of molecular oxygen under
the action of visible light. It was not until 1969 that only one of the key functions
of chloroplast was reproduced for this first time, in particular, photocatalytic evolu-
tion of molecular oxygen from water under the action of light absorbed by synthetic
analogs of chlorophyll.8,9
What is the main obstacle that precluded implementation of artificial photosyn-
thesis despite numerous attempts? Probably, the traditional equation of photosyn-
thesis bears some error, which prevents implementation of the process in vitro.
In 1993, a new photosynthesis equation was proposed at the Institute of Chemi-
cal Physics of the RAS and substantiated in detail in a monograph.1 According to
A New Concept of Photosynthesis 319

this equation, exogenic and endogenic hydrogen peroxide rather than water serves
as the source of oxygen (hydrogen) in the photosynthesis. In chloroplast, there is
one hydrogen peroxide molecule per chlorophyll molecule.1 As shown by quan-
tum chemical calculations, the bond energy of peroxide with chlorophyll dimers is
higher than that for water. Depending on the configuration of the dimeric complex,
the difference may reach 3.8 kcal/mol.

FIGURE 19.6  Annual number of publications mentioning artificial photosynthesis (1980–

2012).

In 1994, we proposed to organize the international project “Artificial photo-

synthesis.”42 It should be noted that the developed concept allows us to see a new
approach to the problem artificial photosynthesis. Thermodynamic estimates of the
enthalpy (∆H°) and the Gibbs energy (∆G°) for reactions of СО2 both with water
and with hydrogen peroxide to give formaldehyde, formic acid, glucose, and other
products were reported.43 The results demonstrated unambiguously that syntheses of
organic compounds from СО2 and Н2О2 require less energy than the corresponding
reactions using water. Indeed, replacement of Н2О by Н2О2 decreases the ∆G° of
product formation by 30% for formaldehyde, by 34% for methanol, and by 42% for
formic acid.
On the basis of the above, a successful attempt was made in 2004 to detect the
formation of organic compounds upon the action of light on an aqueous suspen-
sion of adsorbed phthalocyanines, which were used as synthetic analogs of chloro-
phyll.43,44 The suspension contained 0.2 mol/L of hydrogen peroxide and 0.4 mol/L
of NaHCO3. By means of chemical analysis and spectrophotometry, photocatalytic
formation of formaldehyde was detected (Fig. 19.7).
320 Process Advancement in Chemistry and Chemical Engineering Research

FIGURE 19.7  Kinetics of formaldehyde accumulation and hydrogen peroxide consumption

in the photocatalytic reduction bicarbonate anion ([NaHCO3]0 = 0.4 M, 20°C, photocatalyst is
aluminum phtalocyanine) (time, hours).

Analysis of the IR spectra of the irradiated reaction mixture attested to possible

formation of organic products of various nature in such systems.43–45
The work presented in Ref 46 deals with a GC/MS detection of photogenerated
organic products in an aqueous suspension of adsorbed aluminum phthalocyanine,
Н2О2, and HCO3 and in the system containing Н2О2 and СО2, which we considered
as a new step toward artificial photosynthesis.
The photophysical and photochemical properties of phthalocyanine are similar
to those of chlorophyll but the stability against destructive impacts is much higher.
This is why phthalocyanine was chosen for the experiment.1 We used spectral-grade
chlorinated aluminum phthalocyanine (Kodak). Since chlorophyll is linked in vivo
to a support (protein), we used phthalocyanine also in the adsorbed state. As a sup-
port with developed surface, we took silica gel L 40/100, which allowed easy sepa-
ration of the pigment from the reaction products by mere centrifugation. Aluminum
phthalocyanine was adsorbed from a solution in DMF. The adsorbed amount was
measured as the decrease in the pigment concentration in solution by spectropho-
tometry on a DR/4000V instrument (HACH-Lange, USA). As found from the ad-
sorption isotherm, a monomolecular layer of the phthalocyanine metal complex is
formed on the support surface when the phthalocyanine concentration in the initial
solution is in the range 10−4 mol/L.45 The preliminary experiments showed that the
highest photocatalytic activity of the adsorbed aluminum phthalocyanine in decom-
position of Н2О2 is observed in the region of pre-monomolecular coverage of the
support surface. Considering these data, the catalysts were prepared by adding 10
ml of a 5 × 10−4 M solution of aluminum phthalocyanine to 1 g of silica gel. The
adsorbates, thus obtained contained 5.4 × 10−7 mol of the pigment per g of silica gel.
Kinetic experiments were carried out in 10 ml of a reaction mixture containing
Н2О2 (0.2 mol/L), special purity grade NaHCO3 (0.4 mol/L) (Reakhim), and sup-
A New Concept of Photosynthesis 321

ported catalyst (200 mg) in distilled water. The suspension was distilled in a visible
light with intense stirring. A halogen lamp (150 W) fitted with lenses, a condenser,
and a KS-13 light filter cutting off the radiation below 630 nm was used as the
source of visible light. The light flux power was 10 mW/cm2. A quantitative deter-
mination of formaldehyde showed that its concentration reaches 10−5 mol/L after 24
h of irradiation. By this moment, more than 70% of the initial amount of Н2О2 has
been consumed, mainly via (photo) catalytic disproportionation. Under these condi-
tions, we did not observe destruction or poisoning of the catalyst. The conclusion
about the stability of the metal complex is also confirmed by the results of control
runs carried out without NaHCO3 in which no formaldehyde was detected. This
implies that only СО2 (HCO3−) can serve as the source of CH2O.
Other products were analyzed by the GC/MS method. The GC/MS facility used
to analyze the samples comprised a Thermo Focus GC gas chromatograph and a
Thermo DSQ II mass spectrometer with a 60 m × 0.25 mm capillary glass column
(0.25 m thick 100% dimethtylpolysiloxane as the stationary phase). The tempera-
ture program of the chromatograph included 10 min heating from 35 to 80°C (heat-
ing rate 1°C/min), then to 110°C (heating rate 5°C/min), and to 210°C (heating rate
10°C/min). The injector temperature was 200°C and the interface temperature was
250°C. Electron impact ionization was used, the electron energy being 70 eV and
the mass spectrum being scanned in the range of 20–270 amu. Helium served as the
carrier gas; the flow rate was 1 ml/min. Compounds were identified using the NIST
library of mass spectra. Under the conditions used, the GC/MS method revealed
organic compounds of alcohol and ketone classes in the reaction mixture (Fig. 19.8).
If one of the components (hydrogen peroxide, hydrocarbonate, or phthalocyanine) is
removed from the reaction mixture, organic products cannot be detected.

FIGURE 19.8  Composition of the organic products in the reaction mixture containing
Н2О2, NaHCO3, and adsorbed aluminum phthalocyanine after 24 h of irradiation according
to GC/MS data.
322 Process Advancement in Chemistry and Chemical Engineering Research

In the next experiment, NaHCO3 was replaced by gaseous СО2, which was
passed continuously through the suspension during the irradiation (24 h). All other
conditions were the same as in the previous experiment. The GC/MS analysis of the
reaction mixture after irradiation showed the presence of formic acid (Fig. 19.9).

FIGURE 19.9  Formation of formic acid in the reaction mixture containing Н2О2 and
adsorbed aluminum phthalocyanine after 24 h of irradiation with continuous purging with
CO2 according to GC/MS data.

Note that in this run too, GC/MS analysis did not detect organic compounds
when either hydrogen peroxide or carbon dioxide was missing.
Positive results of experiments using hydrogen peroxide are of considerable in-
terest. They open up attractive prospects: selection of the most appropriate pigment
(variation of the ligands and the central atom), support, and reactant ratio, which
may provide significant results. At the current stage, we can say with confidence
that a new step was made toward artificial photosynthesis in a purely abiogenic
system. The value of these results is beyond the framework of photosynthesis. Par-
ticular paths to biofuel from carbon dioxide and hydrogen peroxide have been out-
lined, which is of paramount importance for modern ecology. According to various
estimates, the period when mankind will face the problem of exhaustion of the re-
sources of fossil combustibles is near at hand.
The obtained results can also be used in considering the problem of cosmic ori-
gin of life, as hydrogen peroxide was detected in space objects.47–50

19.5 CONCLUSION
In the justification of the new concept of photosynthesis resulting from all our previ-
ous investigations, carried out in the laboratory, we use the following results. Photo-
synthesis (or, more accurately, its light stage—the generation of oxygen) is basically
a relatively simple physical–chemical process taking place in a highly complicated
biological system. The pigments of the chloroplasts represented a highly autono-
mous system whose function is mainly the absorption of light (therefore, the in-
A New Concept of Photosynthesis 323

tensive color of the pigments) and transformation of the light to chemical energy.
The effect of light in the chloroplasts results in the formation of an excess number
of protons ensuring the possibility of occurrence of fermentation reactions leading
to the synthesis of hydrocarbons. The results of our literature analysis and the data
obtained in our laboratory convincingly indicate that the source of oxygen (hydro-
gen) in photosynthesis is the exogenous and endogenous hydrogen peroxide. Water
plays the role given to the solvent in conventional chemical reactions. Naturally,
the water protons may take part in the formation of endogenous hydrogen peroxide.
However, the problem of dissociation (oxidation) of water is not so important for
us at the moment because the amount of hydrogen peroxide (“oxidized water,” the
initial name of hydrogen peroxide) in the chloroplasts (cytoplasm) is such that it is
possible to explain the experimental detected intensity of generation of oxygen (for
each molecule of chlorophyll, including the molecule of the antennae, there is one
molecule of hydrogen peroxide). Evidently, if the system contains water and hy-
drogen peroxide, only hydrogen peroxide will undergo photodissociation under the
effect of visible light. Naturally, the development of detailed schema of the dissocia-
tion of hydrogen peroxide in photosynthesis requires a certain period of time. As an
example, in current catalysis, hydrogen peroxide is used widely in heavy and light
organic synthesis. This is one of the oldest variants of catalysis. However, according
to the descriptive expression by Academician I.I. Moiseev “Hydrogen peroxide is
widely used in organic synthesis industry, although the mechanism of its action is
not elucidated fully” (Report of the seminar on Catalysis in ICP RAS).
The participation of hydrogen peroxide in the photosynthetic generation oxygen
is far more likely than the participation of water, not only from the physical–chemi-
cal viewpoint (comparison of the dissociation potentials, thermal stability, etc.).
It makes it possible to explain the existence of a large number of physiological
processes accompanying photosynthesis. In the literature on physiology of plants,
transpiration is treated as an “unavoidable evil,” with attempts being made to elimi-
nate it, although these attempts have not been successful. Within the framework
of our considerations, transpiration is essential for the concentration of exogenous
hydrogen peroxide. The identical situation is also characteristic of the process of
photobreathing with which the physiologists “fight” without success and cannot get
rid of it. Our considerations, presented in this chapter, indicate that the plants ac-
cumulate not only light but also thermal energy (unique thermal pump). The signifi-
cance of the latter is especially large in the plant associations where the illumination
of leaves because of mutual shading is relatively low (in the individually standing
trees, the mutual screening of the leaves is also high). This makes it possible to use
a new approach to explain the fact that the intensity of photosynthesis in the case of
light illumination is almost an order of magnitude higher in comparison with high-
intensity illumination.
In conclusion, it should be mentioned that the long-term investigations into
modeling and examination of the photosynthesis mechanism, described in the chap-
324 Process Advancement in Chemistry and Chemical Engineering Research

ter, have been used by us in the formulation and computer analysis of the model in
which the process of search for the solution of a scientific problem by the investiga-
tor is examined in the generalized form.51,52

ACKNOWLEDGMENT
I am very grateful to the colleagues and graduates of the Laboratory of Photobion-
ics of the Institute of Chemical Physics. I am also grateful to a large number of
undergraduates and graduates (in most cases, of the Physical Department of the
Moscow State University and Moscow Physico-Technical Institute) for solving the
given problems.
I am especially grateful to Academician A.L. Buchachenko, the Head of the
Department of the Dynamics of Chemical and Biological Processes of the Institute
of Chemical Physics of the Russian Academy of Sciences, for supporting investi-
gations carried out in our laboratory. The experiments in recent years have been
supported by continuing financial support of the Russian Fund of Fundamental in-
vestigations to which we are grateful (Grants No. 94-02-04972a, No. 95-03-08982a,
No. 96-0334064a, No. 98-0332061a, No. 04-03-32890а and No. 00-15-97404a,
08-03-00875а; the Presidential program “Leading Scientific Schools (NSh–2003–
2013)”—Coordinator Academician A.L.Buchachenko.
2005–2007 Basic Research Program of the Presidium of RAS “Organic and hy-
brid nanostructured materials for photonics”—Program Coordinator Academician
M.V. Alfimov.
2005–2006 Program of Presidium of RAS No. 7P-05 “Hydrogen Energy”—Pro-
gram Coordinator Academician I.I. Moiseev.
2006–2014 Program of the Presidium of RAS No.18 “The problem of origin
of the Earth’s biosphere and its evolution”—Program Coordinator Academician
E.M.Galimov.
2009–2011 Program of the Presidium of RAS “Chemical aspects of energy”—
Program coordinator of Academician I.I. Moiseev.
2004–2007 ISTS project No. 2876 “Research and development of photoelectro-
chemical light energy converters based on organic semiconductors using the prin-
ciples of photobionics.”
2009–2013 ISTS project No. 3910 “Modeling of primary stages of photosynthe-
sis on the basis of nano-sized supramolecular systems.”
A New Concept of Photosynthesis 325

KEYWORDS
•• photosynthesis
•• artificial photosynthesis
•• photovoltaic effect (Becquerel effect)
•• photocells
•• quantum yield on a photocurrent
•• the types of structures of pigment films on electrodes (three kinds of
Becquerel effect)
•• new equation of photosynthesis
•• chlorophyll
•• phthalocyanine
•• chloroplast
•• transpiration
•• water
•• hydrogen peroxide
•• carbon dioxide
•• oxygen

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many, 1993, 420.
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21. Mano, J.; Takahashi, M. A.; Asada, K. Biochemistry 1987, 26, 2495–2497.
22. Komissarov, G. G. Chem. Phys. Rep. 1995, 14 (11), 1723–1732.
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24. Komissarov, G. G. J. Advanc. Chem. Phys. 2003, 2 (1), 28–61.
25. Komissarov, G. G. Optics Spectrosc. 1997, 83, 607–610.
26. Komissarov, G. G. A New Concept of Photosynthesis Mechanism in Book Problems of Eco-
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28. Ruben, S., et al. J. Amer. Chem. Soc. 1941, 63, 877–879.
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3–17.
51. Komissarov, G. G.; Avakyanz, G. S.; Mazo, M. A. Pros. Int. Conf. Nonlinear Word, Astrakhan
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Scien. Conf. Math. Methods in Technics and Technology Yaroslavl, 2007, Vol. 2, pp 253–256.
CHAPTER 20

APPLICATION OF ORGANIC
PARAMAGNETS IN BIOLOGICAL
SYSTEMS
M. D. GOLDFEIN and E. G. ROZANTSEV
Saratov State University, Saratov, Russia. E-mail: [email protected]

CONTENTS
Abstract..................................................................................................................330
20.1 Introduction..................................................................................................330
20.2 Application of Iminoxyl-Free Radicals Forstudying of Immune
Gamma Globulins........................................................................................331
20.3 Exploring Structural Transitions in Biological Membranes........................333
20.4 Exploring the Structure of Some Model Systems........................................335
20.5 Solving other Biological Problems with Stable Radicals............................339
Keywords...............................................................................................................342
References..............................................................................................................342
330 Process Advancement in Chemistry and Chemical Engineering Research

ABSTRACT
Research of the condensed phases containing stable radicals, by means of radio-
spectroscopy, represents a method of paramagnetic sounding. This method (using
iminoxyl radicals) allowed to set the mechanism of interaction of antigens with
antibodies in case of study of immune gamma globulins, particularly structural tran-
sitions in biological membranes, to study the structure of some model systems. It is
shown that certain derivatives of iminoxyl radicals have low toxicity and exhibit a
relatively high antileukemic activity, greatest quantities were observed for the inhi-
bition ratios hemocytoblasts in peripheral blood, bone marrow, and during chemo-
therapy of certain cancers.

20.1 INTRODUCTION
The presence of paramagnetic particles in liquid or solid objects opens new opportu-
nities to study it by the EPR technique. Ready free radicals and substances forming
paramagnetic solutions due to spontaneous homolization of their molecules in liquid
and solidmedia (such as triphenylmethyl dimer, Frémy’s salt or 4,8-diazaadaman-
tan-4,8-dioxide) can act as sources of paramagnetic particles.
The experimental technique of radio spectroscopic examination of condensed
phases with theaid of paramagnetic impurities is usually calledparamagnetic probe
method. Though iminoxyl radicals have found broadest applications for probing of
biomolecules, nevertheless, the first application of the paramagnetic probe tech-
nique to study a biological system is associated with a quite unstable aminazine
radical cation:
S

N Cl
(CH 2) 3N(CH ) 2
3

The progress in the theory and practice of EPR usage in biological research
isrestrained bythe narrow framework of chemical reactivity ofnonfunctionalized
stable radicals with alocalized paramagnetic center as follows:

N R N R

O O
Application of Organic Paramagnets in Biological Systems 331

The substances of this class only enter intocommon, well-known free radical
reactions, namely, recombination, disproportionation, addition to multiple bonds,
isomerization, and β-splitting.1 All these reactions proceed with the indispensable
participation of a radical center and steadily lead to full paramagneticloss,though
the synthesis ofnonfunctionalized stable radicalsplaysa very important role. No ex-
pressed delocalization of anuncoupled electronover amultiple-bond system has been
shown to beobligatory for a paramagnet to be stable.
Despite of the basic importance of thediscovery of stable radicals of anonar-
omatic type,2 this event has not changed contemporary ideas on the reactivity of
stable radicals.
In the early 1960s, one of the authors of this book laid the foundation of a new
lead in the chemistry of free radicals, namely, the synthesis and reactivity of func-
tionalized stable radicals with an expressed localized paramagnetic center.3
The opportunity toobtain and studya wide range of such compounds with vari-
ous functional substituents arose in connection with thediscovery of free radicalre-
actions with their paramagnetic center unaffected.
Functionalized free radicals have found broad applicationslikeparamagnetic
probes for exploring molecular motion in condensed phases of various natures. The
introduction of a spin-labeled technique (covalently bound paramagnetic probe) is
associated with itsusage;this idea isnot new and is based on the dependence of the
EPR spectrumshape of the free radical on the properties of its immediate atomic
environment and the way of interaction of the paramagnetic fragment with the me-
dium. The reactions of free radicals withtheir paramagnetic center unaffected (Neu-
mann–Rozantsev’s reactions)4have become the chemical basis forobtaining spin-
labeled compounds.
The concept of the usage of non-radical reactions tostudy macromolecules
was formulated at the Institute of Chemical Physics (USSR Academy of Scienc-
es) by G.I. Lichtenstein5in 1961, and the theoretical bases of this method, calcu-
lationof algorithmsfor thecorrelation times of rotary mobility of a paramagnetic
particle from their EPR spectrum shape were developed byMcConnell,6Freed and
Fraenkel,7Kivelson,8 and Stryukov9have investigated the behaviorofiminoxyl radi-
cals in various systems and obtained important and interesting results.10
Let us cite several important aspects of the application of organic paramagnets
to researching biological systems.

20.2  APPLICATION OF IMINOXYL-FREE RADICALS

FORSTUDYING OF IMMUNE GAMMA GLOBULINS
From the physicochemical viewpoint, the mechanism of various immunological
reactions is determined by changesinthe phase state of a system. Despite of the
wide use of these reactions in medical practice, the nature of interaction of antigens
with antibodies isnot quite clear. Tostudy this process,gamma globulins labeled with
332 Process Advancement in Chemistry and Chemical Engineering Research

iminoxyl radicals were used.11The molecule of gamma globulin is known to consist

four polypeptide chains bound with each other with disulfide bridges. When the in-
terchain disulfide bonds are split, the polypeptide chains continue to keep together.
A spin label (an iminoxyl derivative ofmaleimide)

O
H
N N O

H
O

was attached to the sulfhydryl groupsobtained by restoration of disulfide bonds

with β-mercaptoethanol. Experiments were made on the rabbit and human gam-
ma globulins. The EPR spectra in both cases corresponded to rather high mobil-
ity of free radicals (correlation times=1.1·10−9s for human gamma globulin and
7.43·10−9s for rabbit’sone). By comparing the correlation times in these proteins
with the values obtained in experiments with serum albumin labeled withsulfhydryl
groups, treatedwith urea (τ=1.09·10−9s) and dioxane (2.04·10−9s), it is possible to
conclude that the fragments of polypeptide chains bearing free radicalspossess no
ordered secondary structure. This is accordingto the data on very low contents of
α-helical structures in gamma globulins. Such a character of the EPR spectrum of
immune gamma globulinwith preservation of its specific activity opens the possi-
bility to explore conformational and phase transitions at specific antigen–antibody
reactions. Sharp distinctions in the mobility of spin labels were revealed at sedimen-
tation of the rabbit antibodies by salting-outwithammonium sulfate and precipita-
tion with a specific antigen (egg albumin). Precipitation of antibodies with a specific
antigen led only to a small reduction of the paramagnetic labelmobility,whereas
sedimentation withammonium sulfate caused strong retardation of the rotary mobil-
ity of free radicals (Fig. 20.1).
These results can be considered as direct confirmation of the alternative theory12
according to which theprecipitate formation is associated with the immunological
polyvalency of theantigen and antibody relative to each other. Really, exceptingth-
elocation of spinlabels inside the antibody’s active center, it is possible to conclude
that the rather mobile condition of spinlabels in theantigen–antibody precipitatemay
remain if only there is no strong dehydration of the antibodies due to intermolecular
interactions. Unlike gamma globulin precipitatedwithammonium sulfate, the spe-
cific precipitate, according to the lattice theory, has a microcellular structure. At
long storage of theantigen–antibody precipitate with no addition of stabilizers, the
mobility degree of iminoxyl radicals sharply decreased. This is apparently a result
Application of Organic Paramagnets in Biological Systems 333

of secondary dehydration of the antibodies owing to protein molecule interactions

in theprecipitate.

FIGURE 20.1  EPR spectra ofgamma globulin labeled with animinoxylradical with its free
valency unaffected: (a)in solution; (b)in theprecipitateobtained bysalting-out with ammonium
sulfate;(c)in thespecificprecipitate.

20.3  EXPLORING STRUCTURAL TRANSITIONS IN BIOLOGICAL

MEMBRANES
Biological membranes, in particular,mitochondrial membranesare known to play a
huge role in redox processes in the cell, being theonly place of respiratory chain en-
zyme localization. Baum and Riske13 have found essential distinctions in the prop-
erties of one of the mitochondrial membrane fragments (Complex III of Electron
Transport Chain) upon transition from the oxidized form to the reduced one: the
sulfhydryl groups, easily titrated in the oxidized form of this fragment, become in-
accessible in the reduced form. The nature of trypsin digestion of this complexalso
strongly changes.
Earlier, changes in the repeating structural units of mitochondria in conditions
leading to the formation of macroergic intermediate products or their provision,
for example, active ion transfer, wererevealed by electron microscopy.14All this has
allowed us to assume that anyredox reaction catalyzed by anenzymatic chain of
electron transfer is accompanied by some kind of “conformational wave”probably
covering not only the protein component of the membrane but also a higher level
of its organization, namely, fragments of the membrane of more or lesscomplex-
ity degree, including its lipidic part. To verify this assumption,a modification of
thespin-labeledmethod (a method of noncovalentlybound paramagnetic probe) was
used. The radical is kept by the matrix (membrane) involving only weak hydropho-
bic bonds. Such an approach allows studying of weak interactions in the system
334 Process Advancement in Chemistry and Chemical Engineering Research

without essential disturbance of the biochemical functions of the biomembrane and

its structure. The paramagnetic probe was 2,2,6,6-tetramethylpiperidine-1-oxyl ca-
prylic ester:

H-C H C
4 9
O N O

This compound was prepared from caprylic acid chloranhydride and 2,2,6,6-tet-
ramethyl-4-oxpiperidin-1-oxyl in a triethylamine mediumbya radical reaction with-
free valency unaffected. The paramagnetic probe was introduced into a suspension
of electrontransport particles (ETP) isolated from thebull heart mitochondriaby-
thetechnique described in Ref.at theLaboratory of Bioorganic Chemistry, Moscow
State University. These fragments of the mitochondrial membrane are characterized
by arather fullset of enzymes of the respiratory chain with the same molar ratio as in
the intact mitochondria.14The ability of oxidizing phosphorylation, however, is lost
under the used way of isolation.
The paramagnetic probe is insoluble in water but solubilized by ETPsuspended
in a buffer solution. Owing to this, the observed EPR spectrum is free fromany back-
grounddue to the radicalsnot attached with the object under study. The presence of a
voluminous hydrocarbonic chain provides “embedding” of a molecule of the probe
into the lipidic part of ETP. Therefore, the EPR spectrum reflects the condition of
exactly this fraction of the membrane. To detect conformational transitions, EPR
spectra were recorded before and after the introduction of oxidation substrata (suc-
cinate and NAD-N), and after oxidation of the earlier reduced respiratory chain with
potassium ferricyanide. Typical results are shown in Figure 20.2.14

FIGURE 20.2  Changes in theEPRspectrumanisotropyof thehydrophobiciminoxylradicalin

asuspension ofelectron transportparticlesfrom bovine heart mitochondriawith oxidation
substrates added.
Application of Organic Paramagnets in Biological Systems 335

The enhanced anisotropy of the EPR spectrumof iminoxyl after substratum in-
troduction is clearly seen. The spectrum in the ferricyanide-oxidized ETPalmost
doesnot differ from that in the intact ETP.
ETP inactivation by long storage at room temperature or cyanide inhibition elim-
inated this effect. Comparison of theshape of signals and correlation times shows
that the EPR spectrum ofiminoxyl in the intact ETP consists of two signals differing
by anisotropy. The radical localized in that part of the membrane where the effective
free volume available for radical motion is rather large gives aweakly anisotropic
signal. The strongly anisotropic (retarded) spectrum belongs to the radicals local-
ized in other sites of the system with a smaller effective free volume. Reduction of
the respiratory chain with substrata leads, owing to cooperative-type conformational
transitions, to a reducedfraction of sites with large free volume (i.e., to an increased
microviscosity of the immediate environment of the radical).The correlation time
of thewholespectrum changes from20.10−10s in the oxidized ETP to4.10−10s in the
reduced ETP.
Concurrently with enhancingthe anisotropy of the signal, its intensity de-
creases as well: iminoxyl reduces, apparently, to hydroxylamine derivatives. Po-
tassium ferricyanide inverts this process. It is necessary to consider that oxidation
substrata,themselves, donot interact considerably with iminoxyls. Obviously, the
conformational transition not only leads to achanged microviscosity but also elimi-
natesany steric obstacles complicating reduction of the radical. In principle, this
circumstance points to possiblya new, actually chemical, aspect of application of the
paramagnetic probe technique.

20.4  EXPLORING THE STRUCTURE OF SOME MODEL SYSTEMS

The application of the paramagnetic probe technique in systems like biological
membranes poses a number of questions concerning the behavior of hydrophobic
labels in media with an ordered arrangement of hydrophobic chains. As a first stage,
mixtures of a nonionic detergent(Tween80) and water were studied. Tween80 origi-
nates from polyethoxylated sorbitan and oleic acid (polyoxyethylene (20) sorbitan
monooleate) and classifies as anonionic detergent based on polyethylene oxide.14Our
choice of this object was determined by some methodical conveniences, and also
some literature data on the structure of aqueous solutions of Tween, obtained by
classical methods (viscometry, refractometry, etc.) The properties of this detergent
are also interesting in themselves since it finds quite broad applicationsfor biologi-
cal membrane fragmentation.
The esters of 2,2,6,6-tetramethyl-4-oxypiperidin-1-oxyl and saturated acids of
the normal structure with a hydrocarbonic chain length of 4,7,or 17 carbon atoms or
the corresponding amides were used as a paramagnetic probe. For comparison, the
behavior of hydrophobic labels IV and V in these systems was also studied
336 Process Advancement in Chemistry and Chemical Engineering Research

H-C H C
4 9
O N O

I
O

H-C H C
7 15
O N O

II
O

H-C H C
7 35
O N O

III

HO N O

IV
O

(CH ) N C
32
NH N O

V
Application of Organic Paramagnets in Biological Systems 337

The course of changesin thecorrelation time of radical rotation as a function of

the Tween concentration is shown in Figure 20.3.

FIGURE 20.3  Changes of the correlation timein the detergent–water system, for nitroxyl
radicals with astrongly localized paramagnetic center.

It is possible to resolve several areas, apparently, corresponding to various struc-

ture types. The initial fragment, only distinguishable for the easiest radicals, cor-
responds to an unsaturated Tween solution in water. This regionis better revealed
for thedetergents with ahigher critical micelle concentration (CMC), for example,
for sodium dodecyl sulfate (Fig. 20.4),15,16 after which micelle formation occurs.
Thecorrelation time of water-insoluble labels increases and comes to a plateau; at
further increasingdetergent concentration, it passes through a maximumand then
monotonously increases up to its value in pure Tween. It is useful to compare these
data with the results of viscosity measurements by usual macromethods. Figure 20.5
shows that viscosity has one extremum about 60% of Tween. Therefore, at a high
Tween concentration, the effective volume available for probe molecule rotation
and macroviscosity donot correlate.

FIGURE 20.4  Estimation of the critical micelleconcentrationof sodiumdodecylsulfatewith

the aid of 2,2,6,6-tertamethyl-4-hydroxypiperidyl-1-oxyl varerate.
338 Process Advancement in Chemistry and Chemical Engineering Research

FIGURE 20.5  Changes in themicroviscosityand macroviscosity of thewater–Tween 80

system.

These results suggest the following interpretation. In pure Tween,the lamellar

structure provides easy layer-by-layer sliding,hence, the macroviscosity of the sys-
tem is low. However,in the absence of water, the interaction of the polar groups is
strong, the hydrocarbonic chains are ordered, and the effective free volume in the
field of radical localization is small. Small water amounts lead to the formation
of defects in the layered structure. Sliding is hindered,and the viscosity increases.
However, moistening breaks the close interaction of the polar groups inTween. The-
segroups are deformed, at the same time,the hydrocarbonic chains are disordered.
Hence, the microviscosity of the hydrocarbonic layerdecreases. Upon termination
of hydration of the polar groups,water-filled cavities are formed. They are a struc-
tural element (micelle) from which the system is built, for example, a hexagonal
P-lattice is formed, byLuzzatti. Structure formation manifests itself as increasing
microbiscosity and macroviscosity. In the field of the maximum, phase inversion is
possible. Structural units of a new type (Tweenmicelles in water)are formed, passing
into colloidal solution upon further dilution. The course of microviscosity changes
at high Tweenconcentrations, amazingly resembles the change incorrelation time
when some lyophilized cellular organellesare moistened. This similarity confirms
that in the field of τmaximum, where restoration of the biochemical activity of chlo-
roplasts begins, a phase transition occurs of the same type as in theLC“detergent–
water” systems.
Some information on the behavior of radical particles in colloidal systems is
provided by the results of temperature measurements. Figure 20.6 illustrates the-
temperature dependence of the correlation time in Arrhenius’ coordinates for several
iminoxyl radicals of various hydrophobicity degrees.
Application of Organic Paramagnets in Biological Systems 339

FIGURE 20.6  Activatyion energy ofrotationaldiffusion offreeiminoxyl (nitroxyl) radicalsin

theTween–water (30% of Tween 80) system.

The strong dependence of the pre-exponential factoron chain length, apparently,

confirms that the observed correlation time really reflects rotation of theradical mol-
ecule as a whole. However, this result also allows another interpretation, namely,
depending on the hydrocarbonic chain length;the radical introducesitselfinto a de-
tergent micelle more or less deeply. This may lead to a changedrotation frequency
of iminoxyl groups round theordinarybonds in the molecule, depending on the en-
vironment of the polar end of the radical. If the polar group of the radical is on
themicelle–solvent interface, the measured frequency should depend on the surface
charge (potential) of the micelle. In our opinion, this circle of colloidchemical prob-
lems, closely connected with questions of transmembrane transfer in biological sys-
tems, will provide one more application field of the paramagnetic probe technique.

20.5  SOLVING OTHER BIOLOGICAL PROBLEMS WITH STABLE

RADICALS
Further progress in the field of the usage of stable paramagnets to solve various
biological problemsis reflected in numerous reviews and monographs.17–20
For dynamic biochemistry, of undoubted interest are local conformational
changes of protein molecules in solutions. The distances between certain loci of
biomacromolecules, in principle, can be estimated quantitatively by means of stable
paramagnets. Upon introduction of iminoxyl fragments into certain sites of native
protein (NRR-method),the distance between the neighboring paramagnetic centers
can be calculatedfrom the efficiency of their dipole–dipole interaction in vitrified
solutions of aspin-labeled preparation (the EPRmethod).
340 Process Advancement in Chemistry and Chemical Engineering Research

The first attempt to estimate the distances between paramagnetic centers in spin-
labeledmesozyme and hemoglobin was undertaken by Liechtenstein,21 who indi-
cated prospects of such an approach. In this regard, there appeared a need of identi-
fication of a simple empirical parameter in EPR spectra for quantitative assessment
of the dipole–dipole interaction of paramagnetic centers.
A convenient empirical parameter was found while studying vitrified solutions of
iminoxyl radicals. It was the ratio of the total intensity of the extreme components of
a spectrum to the intensity of the central one (Fig. 20.7). To establish a correlation of
the d1/dvalue with the average distance between the localized paramagnetic centers,
the corresponding calibration plots are drawn (Fig. 20.8). Calculations have shown
that the d1/dparameter depends on the value of dipole–dipole broadening,being in
fair agreement with independently obtained experimental results.

FIGURE 20.7  EPR spectrum of theiminoxyl-freebiradical (2,2,6,6-tetramethyl-4-

hydroxypiperidine-1-oxyl phthalate) vitrified in tolueneat 77K.

FIGURE 20.8  Dependence of thed1/dparemeterof an EPR spectrumon

themeandistancerbetweeninteractionparamagneticcenters ofiminoxylradicals (1)
andbiradicals (2) at 77 K.
Application of Organic Paramagnets in Biological Systems 341

Subsequently, the methods of quantitative assessment of the distances between

paramagnetic centers in biradicals and spin-labeled biomolecules became reliable
toolsfor structural research.
When determining relaxation rate constants of various paramagnetic centers in
solution,the values of these constants have appeared to be significantly dependent
on the chemical nature of the functional groups in iminoxyl radicals.
Sign inversion of the electrostatic charge of the substituent and itsdistance from
the paramagnetic iminoxyl group has the strongest impact on the values of the con-
stants. The electrostatic effect caused by the value and sign of the charge of para-
magnetic particles interacting in solution is a more essential factor. An increased
ionic strength leads to a change in thek value in qualitative agreement with Debye’s
theory. The substituent’smass is another factor considerably influencing the value of
the constant. If the substituent is a protein macromolecule, the value ofk decreases
twice. The possibilities of application of the paramagnetic probe technique for de-
tection of anion and cation groups and estimation of distances toexplore the micro-
structure of protein were analyzed. The dependences obtained in experiment show
that Debye’s equation with D = 80 can be successfully applied to experimental data
analysis, and, in particular, to estimatingthe distance from the iminoxyl group of
aspin label on protein to the nearest charged group, if this distance doesnot exceed
1.0–1.2 nm.
Considering the role of free radical processesin radiation cancer therapy, it was
offered to investigate the influence of iminoxyl radicals upon the organism of labo-
ratory animals. Pharmacokinetic studies22 have shown that the elementary function-
alized derivatives of 2,2,6,6-tetramethylpiperidin-1-oxyl possess rather low toxicity
and show an expressed antileukemic activity. The highest values of retardationcoef-
ficients were observed for hematopoietic stem cells in peripheral blood and bone
marrow. This circumstance stimulated further structural and synthetic research di-
rected toobtaining more effective and less toxic cancerolytics and sensibilizers for
radiation cancer therapy.
After the first publication, for a rather short time,many potential cancerolytics
were synthesizedin the Laboratory of Stable Radicals, Institute of Chemical Phys-
ics, USSR Academy of Sciences, among which of greatest interest from biologists
wereso-called paramagnetic analogs of some known antitumor preparations, for ex-
ample, a paramagnetic analog of Thiotepa22.
342 Process Advancement in Chemistry and Chemical Engineering Research

N P N

NH

O .

A briefreviewon theusage ofstableparamagnets of theiminoxylseriesintumor

chemotherapy is presented bySuskina.23

KEYWORDS

•• biology
•• organic paramagnetic method
•• study
•• radio spectroscopy
•• sensing
•• mechanism

REFERENCES
1. Rozantsev, E.G.Chem. Encyclopedic Dictionary. M. SE.1983,p489 [Russ].
2. Rozantsev, E.G.;Lebedev, O.L.;Kazarnovskii, S.N. Diploma for the opening number 248 of
05.10.1983. TS. 1982,6,p. 6. [Russ].
3. Rozantsev, E.G.Doctor Dissertation; Institute of Chemical Physics, USSR Academy of
Sciences:Moscow, RU,1965 [Russ].
4. Zhdanov, R.I. Nitroxyl Radicals and Non-Radical Reactions of Free Radicals Bioactive Spin
labels;Zhdanov R.I., Ed.; Springer: Berlin, Heidelberg, NY, 1991,pp 24.
5. Liechtenstein, G.I. Method of spin labels in molecular biology;Nauka: Moscow, RU,1974;pp
255. [Russ].
6. McConnell,N. J.Chem. Phys. 1956,25,709.
7. Freed, J.;Fraenkel, G.J. Chem. Phys. 1963,39,326.
Application of Organic Paramagnets in Biological Systems 343

8. Kivelson, D. J. Chem. Phys. 1960,33,4094.

9. Stryukov, V.B. Stable Radicals in Chemical Physics;Znanie: Moscow, RU, 1971 [Russ].
10. Goldfeld, M.G.;Grigoryan, G.L.;Rozantsev, E.G.Polymer (Gath. of preprints. M. ICP AS
SSSR.1979,p 269 [Russ].
11. Grigoryan, G.L.;Tatarinov, S.G.;Cullberg, L.Y.;Kalmanson, A.E.;Rozantsev, E.G.;Suskina,
V.I.Abst.of USSR Academy of Sciences. 1968;178,p 230.31,p 768 [Russ].
12. Pressman, D. Molecular Structure and Biological Specificity;Nova: Washington D. C. 1957.
13. Baum, H.; Riske, J.;Silman, H.; Lipton, S.Froc.Nature Acad. Sci. US.1967,57,798.
14. Rozantsev, E.G.Biochemistry of Meat and Meat Products (General Part). Manual for Students.
Depi.Print: Moscow, RU, 2006;p 240 [Russ].
15. Goldfeld, M.G.;Koltover, V.K.;Rozantsev, E.G.;Suskina, V.I.;Kolloid.ZS. Bioactive Spin La-
bels; Zhdanov, R. I., Ed.; SPRINGER,1970.
16. Schenfeld H. Nonionic Detergents. Marcel Dekker: New York,1963.
17. Smith, J.;ShrierMuchillo, Sh.;Murch, D. Method of Spin Labels.Free Radicals in Biology;
Mir: Moscow, RU, 1979;1,pp 179.
18. Method of Spin Labels and Probes, Problems and Prospects; Nauka:Moscow, RU, 1986
[Russ].
19. NitroxylRadicals. Synthesis, Chemistry, Applications; Nauka:Moscow, RU, 1987 [Russ].
20. Rozantsev, E.G.;Goldfein, M.D.;Pulin, V.F. Organic Paramagnetic. Saratov Gov.
Univ.:Saratov, RU, 2000;pp 340 [Russ].
21. Liechtenstein, G.I. J. Mol.Biol.1968,2,234.
22. Konovalova, N.P.;Bogdanov, G.N.; Miller, V.B.Abst.of USSR Academy of Sciences. T.
1964,157(3),pp 707. [Russ].
23. Suskina, V.I. Candidate Dissertation. Academy of Sciences: Moscow, RU, ICP USSR. 1970
[Russ].
CHAPTER 21

QUANTUM-CHEMICAL
CALCULATION OF THE MODELS
OF DEKACENE AND EICOSACENE
BY METHOD MNDO WITHIN THE
FRAMEWORK OF MOLECULAR
GRAPHENE MODEL
V. A. BABKIN1, V. V. TRIFONOV1, A. P. KNYAZEV1,
V. YU. DMITRIEV1, D. S. ANDREEV1, A. V. IGNATOV1,
E. S. TITOVA2, O. V. STOYANOV3, and G. E. ZAIKOV4
1
Sebrykov Department, Volgograd State Architect-build University, Akademicheskaya
ul., 1, Volgograd 400074, Volgograd Oblast, Russia
Volgograd State Technical University, Volgograd, Russia
2

Kazan State Technological University, Kazan, Tatarstan, Russia

3

4
N. M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, 4,
Kosygin St., Moscow 119334, Russian Federation

CONTENTS
21.1  Aims and Backgrounds...............................................................................346
21.2  Methodical Part...........................................................................................346
21.3  The Results of the Calculation and Discussion...........................................346
Keywords...............................................................................................................357
References..............................................................................................................358
346 Process Advancement in Chemistry and Chemical Engineering Research

Quantum-chemical calculation of molecules dekacene, eicosacene was done by

method MNDO. Optimized by all parameters geometric and electronic structures
of these compounds was received. Each of these molecular models has a univer-
sal factor of acidity equal to 33 (pKa = 33). They all pertain to class of very weak
Н-acids (рKа > 14).

21.1  AIMS AND BACKGROUNDS

The aim of this work is a study of electronic structure of molecules dekacene, eico-
sacene, and theoretical estimation of its acid power by quantum-chemical method
MNDO within the framework of molecular graphene model, which was discovered
by Novoselov and Game in 2004.1

21.2  METHODICAL PART

The calculation was done with optimization of all parameters by standard gradient
method built-in in PC GAMESS.2 The calculation was executed in approach the in-
sulated molecule in gas phase. Program MacMolPlt was used for visual presentation
of the model of the molecule.3

21.3  THE RESULTS OF THE CALCULATION AND DISCUSSION

Geometric and electronic structures, general and electronic energies of molecules
dekacene, eicosane were received by MNDO method and are shown in Figure 21.1,
Figure 21.2, and in Tables 21.1–21.3. The universal factor of acidity was calcu-
lated by formula: pKa = 49.4–134.61*qmaxH+ 4 (where, qmaxH+—a maximum posi-
tive charge on atom of the hydrogen (by Milliken1) R = 0.97, R−a coefficient of
correlations, qmaxH+ = + 0.06). pKa = 33. This formula was successfully used in the
following articles5,6,7:
Quantum-chemical calculation of molecules dekacene, eicosacene by MNDO
method was executed for the first time. Optimized geometric and electronic struc-
tures of these compounds were received. Acid power of molecules dekacene, eico-
sacene was theoretically evaluated (pKa = 33). These compounds pertain to class of
very weak Н-acids (рКа > 14).

FIGURE 21.1  Geometric and electronic molecular structure of dekacene (Е0 = −5, 50, 105
kDg/mol, Еel= −48, 50, 841 kDg/mol).
Quantum-Chemical Calculation of the Models of Dekacene 347

FIGURE 21.2  Geometric and electronic molecular structure of eicosacene (Е0 = −10, 69,
853 kDg/mol, Еel= −1, 17, 19, 827 kDg/mol).

TABLE 21.1  Optimized Bond Lengths, Valent Corners, and Atom Charges of Dekacene.

Bond lengths R,A Valent corners Grad Atom Charge

(by Mil-
liken)
C(1)–C(2) 1.46 C(3)–C(2)–C(1) 118 C(1) −0.04
C(2)–C(3) 1.45 C(12)–C(9)–C(1) 122 C(2) −0.04
C(3)–C(4) 1.38 C(4)–C(3)–C(2) 123 C(3) −0.02
C(4)–C(5) 1.47 C(9)–C(1)–C(2) 119 C(4) −0.06
C(5)–C(6) 1.38 C(5)–C(4)–C(3) 119 C(5) −0.06
C(6)–C(1) 1.45 C(10)–C(2)–C(3) 123 C(6) −0.02
H(7)–C(3) 1.09 C(6)–C(5)–C(4) 119 H(7) 0.06
H(8)–C(6) 1.09 C(54)–C(53)–C(4) 123 H(8) 0.06
C(9)–C(12) 1.44 C(1)–C(6)–C(5) 123 C(9) −0.02
C(9)–C(1) 1.39 C(53)–C(4)–C(5) 118 C(10) −0.02
C(10)–C(2) 1.39 C(2)–C(1)–C(6) 118 C(11) −0.04
C(11)–C(10) 1.44 C(9)–C(1)–C(6) 123 C(12) −0.04
C(12)–C(11) 1.46 C(4)–C(3)–H(7) 120 H(13) 0.06
H(13)–C(10) 1.38 C(1)–C(6)–H(8) 117 H(14) 0.06
H(14)–C(9) 1.45 C(11)–C(12)–C(9) 118 C(15) −0.02
C(15)–C(16) 1.42 C(15)–C(12)–C(9) 123 C(16) −0.04
348 Process Advancement in Chemistry and Chemical Engineering Research

C(15)–C(12) 1.41 C(1)–C(2)–C(10) 119 C(17) −0.04

C(16)–C(17) 1.45 C(18)–C(11)–C(10) 123 C(18) −0.02
С(17)–C(18) 1.42 C(2)–C(10)–С(11) 122 H(19) 0.06
С(18)–C(11) 1.41 C(15)–C(12)–С(11) 119 H(20) 0.06
H(19)–C(15) 1.09 C(10)–C(11)–С(12) 118 C(21) −0.02
H(20)–C(18) 1.09 C(16)–C(15)–С(12) 122 C(22) −0.04
C(21)–C(22) 1.41 C(2)–C(10)–H(13) 120 C(23) −0.04
C(21)–C(16) 1.42 C(12)–C(9)–H(14) 118 C(24) −0.02
C(22)–C(23) 1.46 C(17)–C(16)–C(15) 119 H(25) 0.06
С(23)–C(24) 1.40 C(21)–C(16)–C(15) 123 H(26) 0.06
С(24)–C(17) 1.42 C(18)–C(17)–C(16) 119 C(27) −0.02
H(25)–C(24) 1.09 C(22)–C(21)–C(16) 122 C(28) −0.02
H(26)–C(21) 1.09 C(11)–C(18)–С(17) 122 C(29) −0.04
C(27)–C(30) 1.39 C(21)–C(16)–С(17) 119 C(30) −0.04
C(27)–C(22) 1.44 C(12)–C(11)–С(18) 119 H(31) 0.06
C(28)–C(23) 1.44 C(24)–C(17)–С(18) 123 H(32) 0.06
С(29)–C(28) 1.39 C(16)–C(15)–H(19) 118 C(33) −0.02
С(30)–C(29) 1.46 C(11)–C(18)–H(20) 119 C(34) −0.04
H(31)–C(27) 1.09 C(23)–C(22)–C(21) 119 C(35) −0.02
H(32)–C(28) 1.09 C(27)–C(22)–C(21) 123 C(36) −0.04
C(33)–C(29) 1.45 C(24)–C(23)–C(22) 119 H(37) 0.06
C(34)–C(33) 1.38 C(30)–C(27)–C(22) 122 H(38) 0.06
С(35)–C(36) 1.38 C(17)–C(24)–C(23) 122 C(39) −0.02
С(35)–C(30) 1.45 C(27)–C(22)–C(23) 118 C(40) −0.04
С(36)–C(34) 1.47 C(16)–C(17)–C(24) 119 C(41) −0.04
H(37)–C(35) 1.09 C(28)–C(23)–C(24) 123 C(42) −0.02
H(38)–C(33) 1.09 C(17)–C(24)–H(25) 119 H(43) 0.06
C(39)–C(40) 1.38 C(22)–C(21)–H(26) 119 H(44) 0.06
C(39)–C(36) 1.46 C(29)–C(30)–C(27) 119 C(45) −0.04
C(40)–C(41) 1.48 C(35)–C(30)–C(27) 123 C(46) −0.06
С(41)–C(42) 1.38 C(22)–C(23)–C(28) 118 C(47) −0.06
Quantum-Chemical Calculation of the Models of Dekacene 349

С(42)–C(34) 1.46 C(33)–C(29)–C(28) 123 C(48) −0.04

H(43)–C(42) 1.09 C(23)–C(28)–C(29) 122 H(49) 0.06
H(44)–C(39) 1.09 C(35)–C(30)–C(29) 118 H(50) 0.06
C(45)–C(46) 1.36 C(28)–C(29)–C(30) 119 H(51) 0.06
C(45)–C(40) 1.47 C(36)–C(35)–C(30) 124 H(52) 0.06
C(46)–C(47) 1.45 C(30)–C(27)–H(31) 120 C(53) −0.02
C(47)–C(48) 1.36 C(23)–C(28)–H(32) 118 C(54) −0.04
C(48)–C(41) 1.47 C(30)–C(29)–C(33) 118 C(55) −0.04
H(49)–C(48) 1.09 C(42)–C(34)–C(33) 123 C(56) −0.02
H(50)–C(47) 1.09 C(29)–C(33)–C(34) 123 H(57) 0.06
H(51)–C(46) 1.09 C(39)–C(36)–C(34) 118 H(58) 0.06
H(52)–C(45) 1.09 C(34)–C(36)–С(35) 119 C(59) −0.04
C(53)–C(54) 1.38 C(39)–C(36)–С(35) 123 C(60) −0.06
C(53)–C(4) 1.46 C(33)–C(34)–С(36) 119 C(61) −0.06
C(54)–C(55) 1.48 C(40)–C(39)–С(36) 123 C(62) −0.04
C(55)–C(56) 1.38 C(36)–C(35)–H(37) 120 H(63) 0.06
C(56)–C(5) 1.46 C(29)–C(33)–H(38) 117 H(64) 0.06
H(57)–C(53) 1.09 C(41)–C(40)–C(39) 119 H(65) 0.06
H(58)–C(56) 1.09 C(45)–C(40)–C(39) 123 H(66) 0.06
С(59)–C(60) 1.36 C(42)–C(41)–C(40) 119
С(59)–C(54) 1.47 C(46)–C(45)–C(40) 122
С(60)–C(61) 1.45 C(34)–C(42)–C(41) 123
С(61)–C(62) 1.36 C(45)–C(40)–C(41) 118
С(62)–C(55) 1.47 C(36)–C(34)–C(42) 118
H(63)–C(59) 1.09 C(48)–C(41)–C(42) 123
H(64)–C(62) 1.09 C(34)–C(42)–H(43) 117
H(65)–C(61) 1.09 C(40)–C(39)–H(44) 120
H(66)–C(60) 1.09 C(47)–C(46)–C(45) 121
C(48)–C(47)–C(46) 121
C(41)–C(48)–C(47) 122
C(40)–C(41)–C(48) 118
350 Process Advancement in Chemistry and Chemical Engineering Research

C(41)–C(48)–H(49) 118
C(48)–C(47)–H(50) 121
C(47)–C(46)–H(51) 118
C(46)–C(45)–H(52) 120
C(55)–C(54)–C(53) 119
C(3)–C(4)–C(53) 123
C(56)–C(55)–C(54) 119
C(60)–C(59)–C(54) 122
C(5)–C(56)–C(55) 123
C(59)–C(54)–C(55) 118
C(4)–C(5)–C(56) 118
C(6)–C(5)–C(56) 123
C(54)–C(53)–H(57) 120
C(5)–C(56)–H(58) 117
C(61)–C(60)–C(59) 121
C(53)–C(54)–C(59) 123
C(62)–C(61)–C(60) 121
C(55)–C(62)–C(61) 122
C(54)–C(55)–C(62) 118
C(56)–C(55)–C(62) 123
C(60)–C(59)–H(63) 120
C(55)–C(62)–H(64) 118
C(62)–C(61)–H(65) 121
C(61)–C(60)–H(66) 118

TABLE 21.2  Optimized Bond Lengths, Valent Corners, and Atom Charges of Eicosacene.
Bond lengths R,A Valence corners Grad Atom Charge (by
Milliken)
C(2)–C(1) 1.46 C(5)–C(6)–C(1) 122 C(1) −0.03
C(3)–C(2) 1.44 C(11)–C(10)–C(2) 122 C(2) −0.04
C(4)–C(3) 1.39 C(1)–C(2)–C(3) 118 C(3) −0.02
C(4)–C(5) 1.47 C(10)–C(2)–C(3) 123 C(4) −0.04
Quantum-Chemical Calculation of the Models of Dekacene 351

C(5)–C(54) 1.46 C(5)–C(4)–C(3) 119 C(5) −0.04

C(6)–C(5) 1.39 C(2)–C(3)–C(4) 122 C(6) −0.02
C(6)–C(1) 1.44 C(54)–C(5)–C(4) 118 H(7) +0.06
H(7)–C(3) 1.09 C(6)–C(5)–C(4) 119 H(8) +0.06
H(8)–C(6) 1.09 C(53)–C(54)–C(5) 123 C(9) −0.02
C(9)–C(1) 1.40 C(54)–C(5)–C(6) 123 C(10) −0.02
C(10)–C(2) 1.40 C(2)–C(1)–C(6) 118 C(11) −0.03
C(10)–C(11) 1.43 C(2)–C(3)–H(7) 118 C(12) −0.03
C(11)–C(18) 1.42 C(5)–C(6)–H(8) 120 H(13) +0.06
C(11)–C(12) 1.45 C(1)–C(6)–H(8) 118 H(14) +0.06
C(12)–C(9) 1.43 C(2)–C(1)–C(9) 119 C(15) −0.02
H(13)–C(10) 1.09 C(1)–C(2)–C(10) 119 C(16) −0.04
H(14)–C(9) 1.09 C(18)–C(11)–C(10) 123 C(17) −0.04
C(15)–C(12) 1.42 C(12)–C(11)–C(10) 119 C(18) −0.02
C(16)–C(15) 1.41 C(17)–C(18)–C(11) 122 H(19) +0.06
C(16)–C(17) 1.45 C(9)–C(12)–C(11) 119 H(20) +0.06
C(17)–C(24) 1.44 C(15)–C(12)–C(11) 119 C(21) −0.02
C(18)–C(17) 1.41 C(1)–C(9)–C(12) 122 C(22) −0.04
H(19)–C(15) 1.09 C(18)–C(11)–C(12) 119 C(23) −0.04
H(20)–C(18) 1.09 C(2)–C(10)–H(13) 119 C(24) −0.02
C(21)–C(16) 1.44 C(11)–C(10)–H(13) 118 H(25) +0.06
C(22)–C(21) 1.39 C(1)–C(9)–H(14) 119 H(26) +0.06
C(23)–C(22) 1.46 C(9)–C(12)–C(15) 123 C(27) −0.02
C(24)–C(23) 1.39 C(17)–C(16)–C(15) 119 C(28) −0.02
H(25)–C(24) 1.09 C(12)–C(15)–C(16) 122 C(29) −0.04
H(26)–C(21) 1.09 C(24)–C(17)–C(16) 118 C(30) −0.04
C(27)–C(22) 1.45 C(18)–C(17)–C(16) 119 H(31) +0.06
C(28)–C(23) 1.45 C(23)–C(24)–C(17) 122 H(32) +0.06
C(29)–C(28) 1.38 C(24)–C(17)–C(18) 123 C(33) −0.02
C(29)–C(30) 1.47 C(12)–C(15)–H(19) 119 C(34) −0.04
352 Process Advancement in Chemistry and Chemical Engineering Research

C(30)–C(27) 1.38 C(17)–C(18)–H(20) 119 C(35) −0.02

H(31)–C(27) 1.09 C(15)–C(16)–C(21) 123 C(36) −0.04
H(32)–C(28) 1.09 C(17)–C(16)–C(21) 118 H(37) +0.06
C(33)–C(29) 1.46 C(16)–C(21)–C(22) 122 H(38) +0.06
C(34)–C(33) 1.38 C(21)–C(22)–C(23) 119 C(39) −0.02
C(34)–C(36) 1.48 C(27)–C(22)–C(23) 118 C(40) −0.04
C(34)–C(42) 1.46 C(22)–C(23)–C(24) 119 C(41) −0.04
C(35)–C(30) 1.46 C(28)–C(23)–C(24) 123 C(42) −0.02
C(36)–C(35) 1.38 C(23)–C(24)–H(25) 120 H(43) +0.06
H(37)–C(35) 1.09 C(16)–C(21)–H(26) 118 H(44) +0.06
H(38)–C(33) 1.09 C(21)–C(22)–C(27) 123 C(45) −0.02
C(39)–C(36) 1.46 C(22)–C(23)–C(28) 118 C(46) −0.03
C(40)–C(39) 1.38 C(30)–C(29)–C(28) 119 C(47) −0.03
C(40)–C(41) 1.48 C(23)–C(28)–C(29) 123 C(48) −0.02
C(41)–C(48) 1.45 C(27)–C(30)–C(29) 119 H(49) +0.05
C(42)–C(41) 1.38 C(35)–C(30)–C(29) 118 H(50) +0.05
H(43)–C(42) 1.09 C(22)–C(27)–C(30) 123 C(51) −0.02
H(44)–C(39) 1.09 C(22)–C(27)–H(31) 117 C(52) −0.04
C(45)–C(40) 1.45 C(23)–C(28)–H(32) 117 C(53) −0.04
C(46)–C(45) 1.39 C(28)–C(29)–C(33) 123 C(54) −0.02
C(47)–C(46) 1.49 C(30)–C(29)–C(33) 118 H(55) +0.06
C(48)–C(47) 1.39 C(36)–C(34)–C(33) 120 H(56) +0.06
H(49)–C(48) 1.09 C(42)–C(34)–C(33) 123 C(57) −0.04
H(50)–C(45) 1.09 C(29)–C(33)–C(34) 123 C(58) −0.06
C(51)–C(4) 1.46 C(35)–C(36)–C(34) 120 C(59) −0.06
C(52)–C(51) 1.38 C(41)–C(42)–C(34) 123 C(60) −0.04
C(52)–C(53) 1.48 C(39)–C(36)–C(34) 118 H(61) +0.06
C(53)–C(60) 1.47 C(27)–C(30)–C(35) 123 H(62) +0.06
C(54)–C(53) 1.38 C(30)–C(35)–C(36) 123 H(63) +0.06
H(55)–C(51) 1.09 C(42)–C(34)–C(36) 118 H(64) +0.06
Quantum-Chemical Calculation of the Models of Dekacene 353

H(56)–C(54) 1.09 C(30)–C(35)–H(37) 117 C(65) −0.04

C(57)–C(52) 1.47 C(29)–C(33)–H(38) 117 C(66) −0.04
C(58)–C(57) 1.36 C(35)–C(36)–C(39) 123 C(67) −0.02
C(59)–C(58) 1.45 C(41)–C(40)–C(39) 119 C(68) −0.04
C(60)–C(59) 1.36 C(36)–C(39)–C(40) 123 C(69) −0.04
H(61)–C(57) 1.09 C(48)–C(41)–C(40) 118 C(70) −0.02
H(62)–C(60) 1.09 C(42)–C(41)–C(40) 119 H(71) +0.06
H(63)–C(59) 1.09 C(47)–C(48)–C(41) 124 H(72) +0.06
H(64)–C(58) 1.09 C(48)–C(41)–C(42) 123 C(73) −0.02
C(65)–C(70) 1.46 C(41)–C(42)–H(43) 120 C(74) −0.02
C(66)–C(65) 1.47 C(36)–C(39)–H(44) 117 C(75) −0.04
C(67)–C(66) 1.46 C(39)–C(40)–C(45) 123 C(76) −0.04
C(68)–C(67) 1.37 C(41)–C(40)–C(45) 118 H(77) +0.06
C(68)–C(69) 1.48 C(40)–C(45)–C(46) 124 H(78) +0.06
C(69)–C(120) 1.46 C(45)–C(46)–C(47) 119 C(79) −0.02
C(70)–C(69) 1.38 C(124)–C(46)–C(47) 118 C(80) −0.04
H(71)–C(67) 1.09 C(46)–C(47)–C(48) 119 C(81) −0.04
H(72)–C(70) 1.09 C(123)–C(47)–C(48) 123 C(82) −0.02
C(73)–C(65) 1.38 C(47)–C(48)–H(49) 119 H(83) +0.06
C(74)–C(66) 1.38 C(40)–C(45)–H(50) 117 H(84) +0.06
C(75)–C(74) 1.46 C(3)–C(4)–C(51) 123 C(85) −0.02
C(75)–C(76) 1.47 C(5)–C(4)–C(51) 118 C(86) −0.03
C(76)–C(73) 1.46 C(53)–C(52)–C(51) 119 C(87) −0.04
H(77)–C(74) 1.09 C(4)–C(51)–C(52) 123 C(88) −0.02
H(78)–C(73) 1.09 C(60)–C(53)–C(52) 118 H(89) +0.06
C(79)–C(76) 1.39 C(54)–C(53)–C(52) 119 H(90) +0.06
C(80)–C(79) 1.45 C(59)–C(60)–C(53) 122 C(91) −0.02
C(80)–C(81) 1.46 C(60)–C(53)–C(54) 123 C(92) −0.02
C(81)–C(82) 1.45 C(4)–C(51)–H(55) 117 C(93) −0.04
C(82)–C(75) 1.39 C(53)–C(54)–H(56) 120 C(94) −0.04
354 Process Advancement in Chemistry and Chemical Engineering Research

H(83)–C(79) 1.09 C(51)–C(52)–C(57) 123 H(95) +0.06

H(84)–C(82) 1.09 C(53)–C(52)–C(57) 118 H(96) +0.06
C(85)–C(80) 1.40 C(52)–C(57)–C(58) 122 C(97) −0.02
C(86)–C(85) 1.43 C(57)–C(58)–C(59) 121 C(98) −0.04
C(86)–C(87) 1.45 C(58)–C(59)–C(60) 121 C(99) −0.02
C(87)–C(88) 1.43 C(52)–C(57)–H(61) 118 C(100) −0.04
C(88)–C(81) 1.40 C(59)–C(60)–H(62) 120 H(101) +0.06
H(89)–C(88) 1.09 C(58)–C(59)–H(63) 118 H(102) +0.06
H(90)–C(85) 1.09 C(57)–C(58)–H(64) 121 C(103) −0.02
C(91)–C(86) 1.42 C(69)–C(70)–C(65) 123 C(104) −0.04
C(92)–C(87) 1.42 C(70)–C(65)–C(66) 118 C(105) −0.04
C(93)–C(92) 1.41 C(73)–C(65)–C(66) 119 C(106) −0.02
C(93)–C(94) 1.45 C(65)–C(66)–C(67) 118 H(107) +0.06
C(94)–C(91) 1.41 C(74)–C(66)–C(67) 123 H(108) +0.06
H(95)–C(91) 1.09 C(69)–C(68)–C(67) 120 C(109) −0.04
H(96)–C(92) 1.09 C(66)–C(67)–C(68) 123 C(110) −0.06
C(97)–C(93) 1.44 C(120)–C(69)–C(68) 118 C(111) −0.06
C(98)–C(97) 1.39 C(70)–C(69)–C(68) 120 C(112) −0.04
C(98)–C(100) 1.46 C(119)–C(120)–C(69) 123 H(113) +0.06
C(98)–C(106) 1.45 C(120)–C(69)–C(70) 123 H(114) +0.06
C(99)–C(94) 1.44 C(66)–C(67)–H(71) 117 H(115) +0.06
C(100)–C(99) 1.39 C(69)–C(70)–H(72) 120 H(116) +0.06
H(101)–C(99) 1.09 C(70)–C(65)–C(73) 123 C(117) −0.02
H(102)–C(97) 1.09 C(65)–C(66)–C(74) 119 C(118) −0.04
C(103)–C(100) 1.45 C(76)–C(75)–C(74) 118 C(119) −0.04
C(104)–C(103) 1.38 C(66)–C(74)–C(75) 123 C(120) −0.02
C(104)–C(105) 1.47 C(73)–C(76)–C(75) 118 H(121) +0.05
C(105)–C(112) 1.47 C(79)–C(76)–C(75) 119 H(122) +0.05
C(106)–C(105) 1.38 C(65)–C(73)–C(76) 123 C(123) −0.02
H(107)–C(106) 1.09 C(66)–C(74)–H(77) 120 C(124) −0.02
Quantum-Chemical Calculation of the Models of Dekacene 355

H(108)–C(103) 1.09 C(65)–C(73)–H(78) 120 H(125) +0.05

C(109)–C(104) 1.47 C(73)–C(76)–C(79) 123 H(126) +0.05
C(110)–C(109) 1.36 C(81)–C(80)–C(79) 118

C(111)–C(110) 1.45 C(76)–C(79)–C(80) 122

C(112)–C(111) 1.36 C(82)–C(81)–C(80) 118

H(113)–C(112) 1.09 C(88)–C(81)–C(80) 119

H(114)–C(111) 1.09 C(75)–C(82)–C(81) 122

H(115)–C(110) 1.09 C(74)–C(75)–C(82) 123

H(116)–C(109) 1.09 C(76)–C(75)–C(82) 119

C(117)–C(68) 1.46 C(76)–C(79)–H(83) 120

C(118)–C(117) 1.38 C(75)–C(82)–H(84) 120

C(118)–C(119) 1.49 C(79)–C(80)–C(85) 123

C(118)–C(123) 1.44 C(81)–C(80)–C(85) 119

C(119)–C(124) 1.44 C(87)–C(86)–C(85) 119

C(120)–C(119) 1.38 C(80)–C(85)–C(86) 122

H(121)–C(117) 1.09 C(88)–C(87)–C(86) 119

H(122)–C(120) 1.09 C(92)–C(87)–C(86) 119

C(123)–C(47) 1.42 C(81)–C(88)–C(87) 122

C(124)–C(46) 1.42 C(82)–C(81)–C(88) 123

H(125)–C(123) 1.09 C(81)–C(88)–H(89) 119

H(126)–C(124) 1.09 C(80)–C(85)–H(90) 119

C(85)–C(86)–C(91) 123

C(87)–C(86)–C(91) 119

C(88)–C(87)–C(92) 123

C(94)–C(93)–C(92) 119

C(87)–C(92)–C(93) 122

C(91)–C(94)–C(93) 119

C(99)–C(94)–C(93) 118

C(86)–C(91)–C(94) 122

C(86)–C(91)–H(95) 119

C(87)–C(92)–H(96) 119
356 Process Advancement in Chemistry and Chemical Engineering Research

C(92)–C(93)–C(97) 123

C(94)–C(93)–C(97) 118

C(100)–C(98)–C(97) 119

C(106)–C(98)–C(97) 123

C(93)–C(97)–C(98) 122

C(99)–C(100)–C(98) 119

C(105)–C(106)–C(98) 123

C(103)–C(100)–C(98) 118

C(91)–C(94)–C(99) 123

C(94)–C(99)–C(100) 122

C(106)–C(98)–C(100) 118

C(94)–C(99)–H(101) 118

C(93)–C(97)–H(102) 118

C(99)–C(100)–C(103) 123

C(105)–C(104)–C(103) 119

C(100)–C(103)–C(104) 123

C(112)–C(105)–C(104) 118

C(106)–C(105)–C(104) 119

C(111)–C(112)–C(105) 122

C(112)–C(105)–C(106) 123

C(105)–C(106)–H(107) 120

C(100)–C(103)–H(108) 117

C(103)–C(104)–C(109) 123

C(105)–C(104)–C(109) 118

C(104)–C(109)–C(110) 122

C(109)–C(110)–C(111) 121

C(110)–C(111)–C(112) 121

C(111)–C(112)–H(113) 120

C(110)–C(111)–H(114) 118

C(109)–C(110)–H(115) 121

C(104)–C(109)–H(116) 118
Quantum-Chemical Calculation of the Models of Dekacene 357

C(67)–C(68)–C(117) 123

C(69)–C(68)–C(117) 118

C(119)–C(118)–C(117) 119

C(123)–C(118)–C(117) 123

C(68)–C(117)–C(118) 123

C(124)–C(119)–C(118) 118

C(47)–C(123)–C(118) 124

C(120)–C(119)–C(118) 119

C(46)–C(124)–C(119) 124

C(123)–C(118)–C(119) 118

C(124)–C(119)–C(120) 123

C(68)–C(117)–H(121) 117

C(119)–C(120)–H(122) 120

C(46)–C(47)–C(123) 118

C(45)–C(46)–C(124) 123

C(47)–C(123)–H(125) 118

C(46) –C(124) –H(126) 118

TABLE 21.3  Total Energy (E0), Maximal Charge on the Hydrogen Atom (qmaxH+), and
Universal Factor of Acidity (pKa) of Molecules Dekacene and Eicosacene.
E0
Molecules qmaxH+ pKa
(kDg/mol)
Dekacene −5,50,105 +0.06 33
Eicosacene −10,69,853 +0.06 33

KEYWORDS

•• dekacene
•• eicosacene
•• molecular graphene model
•• H-acids
•• method MNDO
358 Process Advancement in Chemistry and Chemical Engineering Research

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 Process Advancement in
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ENGINEERING RESEARCH
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ENGINEERING RESEARCH
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CHEMISTRY and CHEMICAL ENGINEERING RESEARCH

surfaces, films nanoparticles (including inorganic, organic organometallic

CHEMISTRY and CHEMICAL ENGINEERING RESEARCH

solids, surfaces, films and nanoparticles (including inorganic, organic and organometallic

CHEMISTRY
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ABOUT application
THE EDITORS of the newest physical methods in chemical structure
ABOUT Gennady E. Zaikov, DSc, is Head of the Polymer Division at the N. M. Emanuel Institute of

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1976 (Ufa,
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Vladimir A. , DSc , DSc
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He is the author of more scientific (including 14 monographs).
RESEARCH Gennady E. Zaikov, DSc
Vladimir A. Babkin, DSc, DSc
Gennady E. Zaikov
Vladimir
Vladimir , DSc , DSc
A. Babkin
A. Babkin
ISBN: 978-1-77188-105-0
90000
ISBN: 978-1-77188-105-0
ISBN: 978-1-77188-105-0
ISBN: 978-1-77188-105-0
90000
90000 90000

9 781771 881050
9 781771 881050
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781771 881050

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