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Materials Science and Engineering
Kłodzińska
Volume 2: Physiochemical Concepts, Properties, and Treatments
Materials Science andand
Engineering
Zaikov
Materials Science Engineering
Haghi
Kłodzińska
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Materials Science and Engineering:
___________________________________________________________________
___________________________________________________________________
Volume 1: Physical
Also available: Process, Methods, and Models
Also available:
EwaEwaKłodzińska,
Kłodzińska,
PhD PhD
Editor: Materials
Abbas Hamrang,
Science
Materials PhD
and Engineering:
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Reviewers &
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Volume Members:
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Methods,
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and
Methods, Models DSc, and A. K. Haghi, PhD
and Models
Hardbound ISBN:
Editor: 978-1-77188-000-8
Abbas Hamrang, PhD
Editor: Abbas Hamrang, PhD
Reviewers & Editorial
Reviewers BoardBoard
& Editorial Members:
Members:Gennady E. Zaikov,
Gennady DSc, and
E. Zaikov, DSc,A. K. Haghi,
and PhD PhD
A. K. Haghi,
Hardbound ISBN: ISBN:
Hardbound 978-1-77188-000-8
978-1-77188-000-8
ISBN: 978-1-77188-009-1
90000
Volume 2
MATERIALS SCIENCE
AND ENGINEERING
Physiochemical Concepts,
Properties, and Treatments
Volume 2
Edited by
Gennady E. Zaikov, DSc, A. K. Haghi, PhD,
and Ewa Kłodzińska, PhD
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ABOUT THE EDITORS
A. K. Haghi, PhD
A. K. Haghi, PhD, holds a BSc in urban and environmental engineering
from University of North Carolina (USA); a MSc in mechanical engineer-
ing from North Carolina A&T State University (USA); a DEA in applied
mechanics, acoustics and materials from Université de Technologie de
Compiègne (France); and a PhD in engineering sciences from Université
de Franche-Comté (France). He is the author and editor of 65 books as
well as 1000 published papers in various journals and conference proceed-
ings. Dr. Haghi has received several grants, consulted for a number of
major corporations, and is a frequent speaker to national and international
audiences. Since 1983, he served as a professor at several universities. He
is currently Editor-in-Chief of the International Journal of Chemoin-
formatics and Chemical Engineering and Polymers Research Journal and
on the editorial boards of many international journals. He is also a member
of the Canadian Research and Development Center of Sciences and Cul-
tures (CRDCSC), Montreal, Quebec, Canada.
vi About the Editors
List of Contributors..................................................................................... ix
List of Abbreviations................................................................................. xiii
List of Symbols............................................................................................xv
Preface...................................................................................................... xix
Index.......................................................................................................... 361
LIST OF CONTRIBUTORS
D. S. Andreev
Volgograd State Architect-build University, Sebrykov Department Michurin Street 21, Michailovka,
Volgograd region, Russia
Yu. S. Artemova
Volgograd State Architect-build University, Sebrykov Department Michurin Street 21, Michailovka,
Volgograd region, Russia
V. A. Babki
Volgograd State Architect-Build University Sebrykov Department, 403300 Michurin Street 21, Mi-
chailovka, Volgograd region, Russia, E-mail: [email protected]
Heinrich Badenhorst
SARChI Chair in Carbon Materials and Technology, Department of Chemical Engineering, University
of Pretoria, Lynwood Road, Pretoria, Gauteng, 0002, South Africa, P.O. Box 66464, Highveld Ext.
7, Centurion, Gauteng, 0169, South Africa, Tel.: +27 12 420 4173; Fax: +27 12 420 2516; E-mail:
[email protected]
L. I. Bazylyak
Physical Chemistry of Combustible Minerals DepartmentInstitute of Physical−Organic Chemistry &
Coal Chemistry named after L. M. LytvynenkoNational Academy of Sciences of Ukraine3а Naukova
Str., Lviv–53, 79053, UKRAINEe–mail: [email protected]
V. U. Dmitriev
Volgograd State Architect-Build University Sebrykov Departament, 403300 Michurin Street 21, Mi-
chailovka, Volgograd region, Russia, E-mail: [email protected]
I. V. Dolbin
Kabardino-Balkarian State University, Nal’chik – 360004, Chernyshevsky st., 173, Russian Federa-
tion, E-mail: [email protected]
K. Z. Gumargalieva
N.N.Semenov Institute of Chemical Physics, RAS, 4 Kosygin Street
H. Hlídková
Institute of Macromolecular Chemistry Academy of Sciences of the Czech Republic, v.v.i. Heyrovský
Sq. 2, 162 06 Prague 6, Czech Republic
D. Horák
Institute of Macromolecular Chemistry Academy of Sciences of the Czech Republic, v.v.i. Heyrovský
Sq. 2, 162 06 Prague 6, Czech Republic, E-mail: [email protected]
Yu. M. Hrynda
Physical Chemistry of Combustible Minerals Department, Institute of Physical Organic Chemistry
and Coal Chemistry, NAS of Ukraine, 3a Naukova Str.Lviv, 79053, E-mail: Ukraineandriy_kytsya@
yahoo.com
x List of Contributors
A. N. Inozemtsev
M. V. Lomonosov MSU, Biological Faculty, Leninskie Gory, 119991 Moscow, Russia, E-mail: olga-
[email protected]
Yu. Kalashnikova
Volgograd State Architect-build University, Sebrykov Department Michurin Street 21, Michailovka,
Volgograd region, Russia
O. V. Karpukhina
N. N. Semenov Institute of Chemical Physics, RAS, 4 Kosygin Street
S. V. Kolesov
The Institute of Organic Chemistry of the Ufa Scientific Centre the Russian Academy of Science,
October Prospect 71, 450054 Ufa, Russia
G. V. Kozlov
Kabardino-Balkarian State University, Nal’chik – 360004, Chernyshevsky st., 173, Russian Federa-
tion
E. I. Kulish
Bashkir State UniversityRussia, Republic of Bashkortostan, Ufa, 450074, ul. Zaki Validi, 32Tel.: +7
(347) 229 96 14, E-mail: [email protected]
A. R. Kytsya
Physical Chemistry of Combustible Minerals Department, Institute of Physical Organic Chemistry
and Coal Chemistry, NAS of Ukraine, 3a Naukova Str.Lviv, 79053, E-mail: Ukraineandriy_kytsya@
yahoo.com
Hieronim Maciejewski
Poznań Science and Technology Park of Adam Mickiewicz University Foundation, Rubież 46, 61-612
Poznań, Poland
Przemysław Pietras
Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, 61-614 Poznań, Poland Zenon
Foltynowicz
Faculty of Commodity Science, Poznan University of Economics, Al. Niepodległości 10, 61-875
Poznań, Poland
V. V. Podmasteryev
N. M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, 4 Kosigin str. Mos-
cow 119334, Russia
S. D. Razumovsky
N. M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, 4 Kosigin str. Mos-
cow 119334, Russia
O. V. Reshetnyak
Department of chemistry, Army Academy named after Hetman Petro Sahaydachnyi, 32 Hvardiys-
ka Str., Lviv, 79012, Ukraine, Physical Chemistry of Combustible Minerals Department, Institute
of Physical Organic Chemistry and Coal Chemistry, NAS of Ukraine, 3a Naukova Str.Lviv, 79053,
[email protected]
Jozef Richert
Institut Inzynierii Materialow Polimerowych I Barwnikow, 55 M. Sklodowskiej-Curie str., 87-100
Torun, Poland, E-mail: [email protected]
List of Contributors xi
G. A. Savin
Volgograd State Pedagogical University, 40013, Lenin Street, 27, Volgograd, Russia, E-mail: gas-
[email protected]
A. S. Shurshina
Bashkir State University, Russia, Republic of Bashkortostan, Ufa, 450074, ul. Zaki Validi, 32; Tel.: +7
(347) 229 96 14, E-mail: [email protected]
D. V. Sivovolov
Volgograd State Architect-build University, Sebrykov DepartamentVolgograd State Architect-build
University, Sebrykov Departament
O. V. Stoyanov
Kazan National Research Technological University, Kazan, Tatarstan, Russia, E-mail: OV_Stoyanov@
mail.ru
E. S. Titova
Volgograd State Technical University, 40013, Lenin Street, 28, Volgograd, Russia
R. R. Usmanova
Ufa State technical university of aviation, Ufa, Bashkortostan, Russia, E-mail: [email protected];
G. E. Zaikov
Institute of Biochemical Physics Russian Academy of Sciences; 117977 Kosigin Street 4, Moscow,
Russia, E-mail: [email protected]
LIST OF ABBREVIATIONS
KT bulk modulus
L filler particle size
l length of a crack
l0 main chain skeletal length
lk specific spatial scale of structural changes
lst statistical segment length
M repeated link molar mass,
m∞ relative amount of water
m0 initial mass of ChT in a film
Mcl molecular weight of the chain part between cluster
Me molecular weight of chain
n the number of cracks
NA Avogadro number
p solid-state component
pc percolation threshold
pKa universal index of acidity
q parameter
q ρmax the greatest and the smallest density values
r the radius of a particle
R universal gas constant
Rcl distance between nanoclusters
S macromolecule cross
Sg cross-section of the contact channel
Sг cross-section of the contact channel
T testing temperature
Tg testing, glass transition
Tm melting temperatures
Wc optimum speed of gases
Wmax rate of the nucleus growth
Wr relative speed of gases in the channel
α the solubility coefficient
αm parameter
βp critical exponents
∆m weight the absorbed film of water
ε1 real part of the value of dielectric transmissivity
ε2 imaginary part of the value of dielectric transmissivity
List of Symbols xvii
εf strain at fracture
εm dielectric constant of the surrounding medium
εM dielectric transmissivity of the solvent
εY yield strain
η exponent
qIP angle between the normal to IP
λ length of a wave of the electromagnetic irradiation
λb the smallest length of acoustic irradiation sequence
λk length of irradiation sequence
ν Poisson’s ratio
νp correlation length
ρ polymer density
ρ polymer density
ρcl nanocluster density
ρd density if linear
τ0Y theoretical value of the shear stress at yielding
τin initial internal stress
ϕf polymer matrix
ϕif interfacial regions relative fraction
φn nanofiller volume contents
χ relative fraction of elastically
Wn nanofiller mass contents
PREFACE
THEORETICAL AND AN
EXPERIMENTAL RESEARCH OF
EFFICIENCY OF GAS PURIFICATION
IN ROTOKLON WITH INTERNAL
CIRCULATION OF A LIQUID
R. R. USMANOVA and G. E. ZAIKOV
CONTENTS
1.1 Introduction....................................................................................... 2
1.2 Survey of Known Constructions of Scrubbers with
Inner Circulation of the Fluid........................................................... 2
1.3 Architecture of Hydrodynamic Interacting of Phases....................... 6
1.4 Purpose and Research Problems......................................................11
1.5 Experimental Researches................................................................ 12
1.6 Conclusions..................................................................................... 22
Keywords................................................................................................. 23
References................................................................................................ 23
2 Materials Science and Engineering Vol 2
1.1 INTRODUCTION
For the machining of great volumes of an irrigating liquid and slurry sal-
vaging the facility of bulky, capital-intensive, and difficult systems of wa-
ter recycling are introduced. This process of clearing of gas considerably
do a rise to its commensurable with clearing cost at application of the most
difficult and cost intensive systems of dry clearing of gases (electrostatic
precipitators and bag hoses) is required.
In this connection necessity for creation of such wet-type collectors
which would work with the low charge of an irrigating liquid now has
matured and combined the basic virtues of modern means of clearing of
gases: simplicity and compactness, a high performance, a capability of
control of processes of a dust separation and optimization of regimes.
To the greatest degree modern demands to the device and activity of
apparatuses of clearing of industrial gases there match wet-type collectors
with inner circulation the fluids gaining now more and more a wide circu-
lation in systems of gas cleaning in Russia and abroad.
FIGURE 1.1 Constructions of scrubbers with inner circulation of a fluid: (a) rotoklon
N (USA); (b) PVM CNII (Russia); (c) a scrubber a VNIIMT (Russia); (d) a dust trap to
me (Czechoslovakia); (e) dust trap WNA (Germany); (f) dust trap “Аsco” (Germany); (g)
dust trap LGP (Russia); (i) dust trap “Кlayrator” (USA); (k) dust trap VDN (Austria); (l)
rotoklon RPA a NIIOGAS (Russia).
FIGURE 1.2 Apparatuses with controlled variables. (a) under the patent №1546651
(Germany), (b) the ACE №556824 (USSR), (c) the ACE № 598625 (USSR), (d) the ACE
№573175 (USSR), (e) under the patent № 1903985 (Germany), (f) the ACE № 13686450
(France), (g) the ACE № 332845 (USSR), (i) the ACE № 318402 (USSR), (k) the ACE №
385598 (USSR), (l) type RPA a NIIOGAS (USSR).
vr Vr vr
= − (1)
sr bhk − bhg b( hk − hg )
(2)
8 Materials Science and Engineering Vol 2
0,2
585 ⋅ 103 s m Ll
l
Do = + 49,7 (3)
Wr ρl s Vr
l
where, Wr is the relative speed of gases in the channel, m/s; σl is the factor
of a surface tension of a fluid, N/m; ρ l is the fluid density, kg/m3; µl is the
viscosity of a fluid, the Pas/with; Ll is the volume-flow of a fluid, m3; Vr is
the volume-flow of gas, m3.
In Fig. 1.3, computational curves of average diameter of drops of water
in contact channels depending on speed of a gas flow are resulted. Calcula-
tion is conducted by Eq. (3) at following values of parameters: σ = 720 ×
103 N/m; ρ l = 1000 kg/m3; µ = 1.01 × 10–2 P/s.
FIGURE 1.3 Relation of an average size of drops of water in blade impellers from speed
of gas.
Theoretical and an Experimental Research of Efficiency 9
speed of a gas flow the increase in a size of drops will be observed. Tur-
bulence in an extending part of a flow more than in the channel with fixed
cross-section, and it grows with increase in an angle of jet divergence,
and it means that speed of turbulent concretion will grow in an extending
part of a flow also with increase in an angle of jet divergence. The more
full there will be a concretion of corpuscles of a fluid, the drop on an exit
from the contact device will be larger and the more effectively they will be
trapped in the drip pan.
Practice shows that the size a coagulation of drops on an exit makes of
the contact device, as a rule, more than 150 microns. Corpuscles of such
size are easily trapped in the elementary devices (the inertia, gravitational,
centrifugal, etc.).
The inertia and centrifugal drip pans are applied to branch of drops of a
fluid from gas in shock-inertial apparatuses in the core. In the inertia drip
pans the branch implements at the expense of veering of a water gas flow.
Liquid drops, moving in a gas flow, possess definitely a kinetic energy
thanks to which at veering of a gas stream they by inertia move rectilin-
early and are inferred from a flow. If to accept that the drop is in the form
of a sphere and speed of its driving is equal in a gas flow to speed of this
flow the kinetic energy of a drop, moving in a flow, can be determined by:
p D03 W 2r
Eκ = ρl
6 2 (4)
With the above formula, decrease of diameter of a drop and speed of a gas
flow the drop kinetic energy is sharply diminished. At gas-flow deflection
the inertial force forces to move a drop in a former direction. The more the
drop kinetic energy, the is more and an inertial force.
p D03 dWr
Eκ = ρl (5)
6 dτ
Theoretical and an Experimental Research of Efficiency 11
Thus, with flow velocity decrease in the inertia drip pan and diam-
eter of a drop the drop kinetic energy is diminished, and efficiency drop
spreads is reduced. However the increase in speed of a gas flow cannot be
boundless as in a certain velocity band of gases there is a sharp lowering
of efficiency drop spreads owing to origination of secondary ablation the
fluids trapped drops. For calculation of a breakdown speed of gases in the
inertia drip pans it is possible to use the formula, m/s:
ρl - ρκ
Wc = K (6)
ρr
The following was the primal problems, which were put by working out
of a new construction of the wet-type collector with inner circulation of a
fluid:
• creation of a dust trap with a broad band of change of operating
conditions and a wide area of application, including for clearing of
gases of the basic industrial assemblies of a mesh dispersivity dust;
• creation of the apparatus with the operated hydrodynamics, allowing
to optimize process of clearing of gases taking into account perfor-
mances of trapped ingredients;
• to make the analysis of hydraulic losses in blade impellers and to
state a comparative estimation of various constructions of contact
channels of an impeller by efficiency of security by them of hydro-
dynamic interacting of phases;
• to determine relation of efficiency of trapping of corpuscles of a dust
in a rotoklon from performance of a trapped dust and operating con-
ditions major of which is speed of a gas flow in blade impellers.
To develop a method of calculation of a dust clearing efficiency in
scrubbers with inner circulation of a fluid.
12 Materials Science and Engineering Vol 2
The rotoklon represents the basin with water on which surface on a con-
necting pipe of feeding into of dusty gas the dust-laden gas mix arrives.
Over water surface gas deploys, and a dust contained in gas by inertia pen-
etrate into a fluid. Turn of blades of an impeller is made manually, rather
each other on a threaded connection by means of handwheels. The slope
of blades was installed in the interval 25°– 45° to an axis.
In a rotoklon three pairs lobes sinusoidal a profile, the regulations of
their rule executed with a capability are installed. Depending on cleanliness
level of an airborne dust flow the lower lobes by means of handwheels are
installed on an angle defined by operational mode of the device. The rot-
oklon is characterized by presence of three slotted channels, a formation
the overhead and lower lobes, and in everyone the subsequent on a course
of gas the channel the lower lobe is installed above the previous. Such ar-
rangement promotes a gradual entry of a water gas flow in slotted channels
and reduces thereby a device hydraulic resistance. The arrangement of an
input part of lobes on an axis with a capability of their turn allows creating
a diffusion reacting region. Sequentially had slotted channels create in a
diffusion zone organized by a turn angle of lobes, a hydrodynamic zone
of intensive wetting of corpuscles of a dust. In process of flow moving
through the fluid-flow curtain, the capability of multiple stay of corpuscles
of a dust in hydrodynamically reacting region is supplied that considerably
raises a dust clearing efficiency and ensures functioning of the device in
broad bands of cleanliness level of a gas flow.
The construction of a rotoklon with adjustable sinusoidal lobes is de-
veloped and protected by the patent of the Russian Federation, capable to
solve a problem of effective separation of a dust from a gas flow [6]. Thus
water admission to contact zones implements as a result of its circulation
in the apparatus.
The rotoklon with the adjustable sinusoidal lobes, introduced in Fig. 1.4
contains a body (3) with connecting pipes for an entry (7) and an exit (5) gases
Theoretical and an Experimental Research of Efficiency 13
in which steams of lobes sinusoidal a profile are installed. Moving of the over-
head lobes (2) implements by means of screw jacks (6), the lower lobes (1) are
fixed on an axis (8) with a capability of their turn. The turn angle of the lower
lobes is chosen from a condition of a persistence of speeds of an airborne dust
flow. For regulating of a turn angle output parts of the lower lobes (1) are en-
visioned handwheels. Quantity of pairs lobes is determined by productivity of
the device and cleanliness level of an airborne dust flow that is a regime of a
stable running of the device. In the lower part of a body there is a connecting
pipe for a drain of slime water (9). Before a connecting pipe for a gas make
(5) the labyrinth drip pan (4) is installed. The rotoklon works as follows. De-
pending on cleanliness level of an airborne dust flow the overhead lobes (5)
by means of screw jacks (6), and the lower lobes (1) by means of handwheels
are installed on an angle defined by operational mode of the device. Dusty
gas arrives in the upstream end (7) in a top of a body (3) apparatuses. Hitting
about a fluid surface, it changes the direction and passes in the slotted channel
organized overhead (2) and lower (1) lobes. Thanks to the driving high speed,
cleared gas captures a high layer of a fluid and atomizes it in the smallest
drops and foam with an advanced surface. After consecutive transiting of all
slotted channels gas passes through the labyrinth drip pan (4) and through the
discharge connection (5) is deleted in an aerosphere. The collected dust settles
out in the loading pocket of a rotoklon and through a connecting pipe for a
drain of slime water (9), together with a fluid, is periodically inferred from the
apparatus.
Lower (1) and the overhead (2) lobes; a body (3); the labyrinth drip pan
(4); connecting pipes for an entry (7) and an exit (5) gases; screw jacks (6);
an axis (8); a connecting pipe for a drain of slurry (9).
Noted structural features do not allow using correctly available solu-
tions on hydrodynamics of dust-laden gas flows for a designed construc-
tion. In this connection, for the well-founded exposition of the processes
occurring in the apparatus, there was a necessity of realization of experi-
mental researches.
Experiments were conducted on the laboratory-scale plant “rotoklon”
introduced in Fig. 1.5.
The examined rotoklon had three slotted channels speed of gas in which
made to 15 km/s. At this speed the rotoklon had a hydraulic resistance 800
passes. Working in such regime, it supplied efficiency of trapping of a dust
with input density 0.5 g/nm3 and density 1200 kg/m3 at level of 96.3% [7].
In the capacity of modeling system air and a dust of talc with a size of
corpuscles d = 2 ÷ 30 a micron, white black and a chalk have been used.
The apparatus body was filled with water on level hg = 0.175 m.
Cleanliness level of an airborne dust mix was determined by a direct
method [8]. On direct sections of the pipeline before and after the appara-
tus the mechanical sampling of an airborne dust mix was made. After de-
termination of matching operational mode of the apparatus, gas test were
taken by means of in-taking handsets. Mechanical sampling isokinetics on
Theoretical and an Experimental Research of Efficiency 15
umes of liquid and gas phases in contact channels and characterizing the
specific charge of a fluid on gas irrigating in channels. Obviously that
magnitude n will be determined, first of all, by speed of a gas flow on an
entry in the contact channel. The following important parameter is fluid
level on an entry in the contact channel, which can change cross-section of
the channel and influence speed of gas.
ϑg ϑg ϑg
= − (7)
Sg bhk − bhl b( hk − hl )
n = f ( ϑ g ⋅ hl ) (8)
0,68
467 ⋅ 103 s m Ll
d= + 17,869 ⋅ l (9)
ϑo ρl s Lr
where ϑî is the relative speed of gases in the channel, m/s; s is the factor
of a surface tension of a fluid, N/m; ρ l is the fluid density, kg/m3; m l is
the viscosity of a fluid,; Ll is the volume-flow of a fluid,; Lg is the volume-
flow of gas,.
The offered formula allows considering also together with physical
performances of phases and agency of operating conditions.
In Fig. 1.7, the design values of average diameter of the drops orga-
nized at transiting of blades of an impeller, from speed of gas in contact
channels and a gas specific irrigation are introduced. At calculation values
18 Materials Science and Engineering Vol 2
FIGURE 1.7 Computational relation of a size of drops to flow velocity and a specific
irrigation.
mp ϑ p
hè = f ⋅ (10)
ξ c d 0
2
mpϑ p 1 d r ϑ p ρ p Cc
= ⋅
ξc d0 18 m g d0 (11)
2
( )
Complex d p ϑ p ρ p Cc / 18m g d 0 is parameter (number) of the Stokes.
d 2p ϑ p ρ p Cc
hè = f ( Stk ) = f (12)
18m g d 0
The basis for calculation on this model is the Eq. (12). For calculation
realization it is necessary to know disperse composition of a dust, density
of corpuscles of a dust, viscosity of gas, speed of gas in the contact chan-
nel and the specific charge of a fluid on gas irrigating.
Calculation is conducted in the following sequence:
• by Eq. (9) determine an average size of drops D0 in the contact chan-
nel at various operating conditions;
• by Eq. (10) count the inertia parameter of the Stokes for each frac-
tion of a dust;
• by Eq. (11) fractional values of efficiency η for each fraction of a
dust;
• general efficiency of a dust separation determine by Eq. (12), %.
The observed inertia model full enough characterizes physics of the
process proceeding in contact channels of a rotoklon.
1.6 CONCLUSIONS
KEYWORDS
•• circulation of a liquid
•• experimental
•• gas purification
•• hydrodynamic interacting of phases
•• rotoklon
•• scrubbers with inner circulation
REFERENCES
1. Uzhov, N. V., Valdberg, J. A., Myagkov, I. B., Clearing of industrial gases of a dust,
Moscow: Chemistry, 1981.
2. Pirumov, I. A., Air Dust removal, Moscow: Engineering industry, 1974.
3. Shvydky, S. V., Ladygichev, G. M., Clearing of gases. The directory, Moscow: Heat
power engineering, 2002.
4. V. Straus. Industrial clearing of gases Moscow: Chemistry, 1981.
5. Kouzov, A. P., Malgin, D. A., Skryabin, M. G., Clearing of gases and air of a dust in
the chemical industry. St.-Petersburg: Chemistry, 1993.
6. Patent 2317845 RF, IPC, cl. B01 D47/06 Rotoklon a controlled sinusoidal blades, Us-
manova, R. R., Zhernakov, V. S., Panov, A. K.-Publ. 27.02.2008. Bull. № 6.
7. Usmanova, R. R., Zaikov, E. G., Stoyanov, V. O., E. Klodziuska, Research of the mech-
anism of shock-inertial deposition of dispersed particles from gas flow the bulletin of
the Kazan technological university №9, 203–207, 2013.
8. Kouzov, A. P., Bases of the analysis of disperse composition industrial a dust. Lenin-
grad: Chemistry, 1987, 183–195.
9. Vatin, I. N., Strelets, I. K., Air purification by means of apparatuses of type the cyclone
separator. St.-Petersburg, 2003.
CHAPTER 2
CONTENTS
2.1 Introduction..................................................................................... 26
2.2 Experimental................................................................................... 26
2.3 Results of Calculations................................................................... 27
Keywords................................................................................................. 37
References................................................................................................ 37
26 Materials Science and Engineering Vol 2
2.1 INTRODUCTION
2.2 EXPERIMENTAL
RO9C29 change from 1.8Å up to 1.4Å). Lengths of these bonds change from
1.88Å up to 4.14Å and from 1.64Å up to 1.93 Å accordingly (Table 2.2).
We define this stage, as a stage of break of bonds. Atom P10 of 5-acety-
loxymethyl-2-chlorine-5-ethyl-1,2,3-dioxaphosphorynan is attacked by
atom Cl32 of acetyl chloride at a stage III. Covalent bonds P10-Сl32 (2.00
Å) and O9-C29 (RO9C29 = 1.4Å) are formed. This stage is final. Formation
of 1-[2-(о-acetylmethyl)-3-о-acetyl-2-ethyl]-methyldichlorinephosphite
occurs.
Change of charges on atoms directly participating in reaction P10, C29
and Cl32, and also change E0 along coordinate of reaction RO9C29 is pre-
sented on Figs. 2.4–2.8 and in Table 2.1. Reaction has barrier character
(Fig. 2.4). The size of a barrier makes 176 kDg/mol. Charges on atoms
P10 and C29 change according to change Е0 (Figs. 2.5 and 2.7). Charges
reach the maximal values during the moment of break of bonds C29–Cl32
and P10–O9. The Negative charge on atom Cl32 is inversely to change Е0. It
reaches the maximal value (on the module) during the moment of break
of the same bonds. We analyze behavior of atoms directly participating
in reaction of synthesis of 1-[2-(о-acetylmethyl)-3-о-acetyl-2-ethyl]-
methyldichlorinephosphite P10, O9, C29 and Cl32, change of charges on these
atoms and power of reaction. We do a conclusion, that the mechanism
of studied synthesis represents the coordinated process with simultaneous
break of bonds P10-O9 and C29-Cl32 and formation of new bonds P10-Cl32 and
C29–O9. It is a process of nucleophylic substitution SN2. It is similar to the
mechanism of synthesis of the first stage of acidation of bicyclophosphites
by chlorine anhydrides of carboxylic acids, to the mechanism of synthesis
of 5-acetyloxymethyl-2-chlorine-5-ethyl-1,2,3-dioxaphosphorynan.
Thus, the mechanism of synthesis of the second stage of acidation
of bicyclophosphites for the first time is studied by quantum-chemical
semiempirical method MNDO. It is shown, that synthesis of this com-
pound—result of the coordinated interactions of acetyl chloride and
5-acetyloxymethyl-2-chlorine-5-ethyl-1,2,3-dioxaphosphorynan on the
mechanism of nucleophylic substitution SN2. It is positioned, that this
reaction is endothermic and has barrier character. It will qualitatively be
coordinated with experiment. The size of an energy barrier of studied reac-
tion is equal 176 kDg/mol.
Lecture Note on Quantum-Chemical Mechanism 29
FIGURE 2.2 The Model of a stage of break of bonds (a transition state). RO9C29 = 1.6Å.
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