Republic of Iraq

Ministry of Higher Education

and Scientific Research
Al-Nahrain University
College of Science
Department of Chemistry

Investigation of Thermal Properties for

some Ionic Liquids containing Urea and
Acetamide
A Thesis
Submitted to the College of Science/Al-Nahrain University as a partial
fulfillment of the requirements for the Degree of Master of Science in
Chemistry

By:
Huda Salam Abid
B.Sc. Chemistry / College Sciences / Al-Nahrain University

Supervised by:
Dr. Hadi M. A. Abood
(Assist. Prof.)

May 2015 Rajab 1436

 Supervisor Certification
I certify that this thesis entitled ''Investigation of Thermal Properties for
some Ionic Liquids containing Urea and acetamide'' under my supervision at
the College of Science/Al-Nahrain University as partial fulfillment of the
requirements for the Degree of Master of Science in Chemistry.

Signature:
Name: Assist. Prof. Dr. Hadi M. A. Abood
Date: 16 \ 2 \ 2015

______________________________________________
In view of the available recommendation, I forward this thesis
for debate by the examining committee.

Signature:
Name: Nasreen Raheem Jber
Scientific Degree: Assist. Prof. Dr.
Head of Chemistry Department
College of Science
Al-Nahrain University
Date: 16 \ 2 \ 2015
 Committee Certification
We, the examining committee certify that we read this thesis
entitled ''Investigation of Thermal Properties for some Ionic Liquids
containing Urea and acetamide'' in its contents and that in our
opinion, it is accepted for the Degree of Master of Science in
Chemistry.

Signature:
Name: Mahasin F. Alias
Scientific Degree: Prof. Dr.
Date: \ \ 2015
(Chairman)

Signature: Signature:
Name: Rashed T. Rasheed Name: Ammar J. Alabdali
Scientific Degree: Assist. Prof. Dr. Scientific Degree: Lect. Dr.
Date: \ \ 2015 Date: \ \ 2015
(Member) (Member)

Signature:
Name: Hadi M. A. Abood
Scientific Degree: Assist. Prof. Dr.
Date: \ \ 2015
(Member/Supervised)
___________________________________________________________
I, hereby certify upon the decision of the examining committee.

Signature:
Name: Hadi M. A. Abood
Scientific Degree: Assist. Prof. Dr.
Dean of the College of Sciences
Date: \ \ 2015
 ‫الرِح ِ‬
‫يم‬ ‫بِ ْس ِم اهلل َّ‬
‫الر ْحم ِن َّ‬

‫اِ ََ ِِ اَأ ْْ ِ‬
‫ ِ‬ ‫ْخ ُذهُ ِسنةٌ َال ن ْوٌم لَّهُ َ ِِ َّ‬
‫السم َ ِ‬
‫﴿اهللُ ال إِله إِالَّ ُهو الْح ُّ الْقيُّ ُ‬
‫وم ال تأ ُ‬

‫َن ذا الَّ ِذي ُ ََْ ُع ِع ْندهُ إِالَّ بِِإ ْذنِِه ُ ْعْل ُم َ ب ْين أُْ ِدُ ُِ ْم ََ خْلَْ ُُ ْم َال ُُ ِحيُُوَ بَِ ْ ٍ نَ ْن‬

‫يم ﴾‪.‬‬ ‫ِ‬ ‫ِ‬ ‫ِ‬ ‫ِعْل ِْم ِه إِالَّ بِم ش ٍ َ ِسع ُكر ِسيُّهُ َّ ِ‬
‫السم َاِ َاَأ ْْ ِ َال ُ ُؤ ُدهُ ح َْظُ ُُم َ ُهو الْعْل ُّ الْعظ ُ‬ ‫ْ‬
‫يم‬ ‫ِ‬
‫صدق اهللُ الْعظ ْ‬
‫ﺁُة (‪ )522‬سوْة البقرة‬
 ‫األهداء‬
‫الى من أضاء بعلمه عقل غيره وهدى بالجواب الصحيح حيرة سائليه‪ ,‬فأظهر‬
‫بسماحته تواضع العلماء وبرحابته سماحة العارفين‪ ,‬الى أستاذي الفاضل‬
‫المشرف على رسالتي (أ‪.‬م‪.‬د‪ .‬هادي محمد علي عبود) المحترم أدامه هللا منهال‬
‫للعلم والمعرفة‪.‬‬

‫الى من علمني أن اصمد أمام الصعاب‪ ,‬إلى من علمني العطاء‪,‬‬

‫إلى من أحمل أسمه بكل افتخار … (والدي الحنون)‬

‫إلى معنى الحب والحنان والتفاني‪ ,‬إلى بسمة الحياة وسر الوجود‪,‬‬
‫إلى من كان دعائها سر نجاحي وحنانها بلسم جراحي‪ ,‬إلى أغلى الحبايب ‪...‬‬
‫(أمي الحبيبة)‬

‫الى من بهم أكبر وعليهم أعتمد وبهم استمد عزتي وإصراري‪ ,‬الى من‬
‫بوجودهم أكتسب قوة الحدود لها‪( ...‬إخوتي األحبة)‬

‫الى االخوات اللواتي لم تلدهن أمي‪ ,‬الى من كانوا معي على طريق النجاح‬
‫والخير‪ ,‬الى من اوجدهم هللا لي‪ ,‬وعلمني أن ال أضيعهم‬
‫‪( ...‬قريباتي وصديقاتي العزيزات)‬
 First of all, Thanks to ALLAH for his blesses. The honor is mine to
express my sincere thanks and gratitude to my supervisor Dr. Hadi M. A.
Abood for suggestion this project, advice, continuous encouragement, his
valuable guidance and sustained efforts throughout my study.

Sincere thanks are due to the Chemistry Department, Al-Nahrain

University and to Staff of the department, specially the head of the
department Dr. Nasreen Raheem Jber and M. Widad Mohammed Shaaban.

A great thanks are gone to the Physics Department, Al-Nahrain

University especially to Dr. Hassan N. Hashim.

My deepest thanks and appreciation to my lovely family, for their

patience with me, their financial and moral support.

Finally, sincere thanks and deep respect go to all my doctors in

chemistry department for their support. Thanks to all my friends for their help
and support.

Huda 2015
Summary
Characterization of some room temperature ionic liquids (RTILs) as
candidates for thermal storage media and heat transfer fluids in thermal
applications were investigated. Five ionic liquids prepared from ammonium
alum [NH4Al(SO4)2.12H2O] pronounced S, as inorganic salt with urea
[NH2CONH2] pronounced U, or acetamide [CH3CONH2] pronounced A, as
organic compounds, and aluminum nitrate [Al(NO3)3.9H2O] pronounced N
with urea or acetamide compounds in different mole ratios were investigated
alone and with addition of some improving materials to study their synergetic
effect using thermo-gravimetric analysis (TGA), Differential Scanning
Calorimetery (DSC), X-ray diffraction (XRD), Fourier Transform Infrared
(FTIR) spectroscopy and conductivity measurements. Thermo-physical
properties such as enthalpy ∆H, heat capacity Cp and thermal energy storage
capacity were determined. It was found that hydrated aluminum
nitrate:acetamide (1:22 mole ratio, AN2IL) alone and hydrated ammonium
aluminum sulfate:urea (1:5 mole ratio, USIL) alone or with addition of some
materials characterized with high density, chemical stability, heat capacity,
thermal energy storage capacity and wide temperature range. The results
indicated that ionic liquids alone or with addition of some materials could be
considered as a promising candidate for liquid thermal storage media and heat
transfer fluids.
Studying the synergetic effect by addition of some alkali metal hydroxide
(NaOH) with hydrated aluminum nitrate:urea (1:1.2 mole ratio, UNIL) and
KOH with hydrated ammonium aluminum sulfate:urea (1:5 mole ratio, USIL)
ionic liquids increased thermal energy storage capacity of these ionic liquids,
while the addition of NaOH to hydrated aluminum nitrate:acetamide (1:22
mole ratio, AN2IL) gave less thermal stability and storage capacity of ionic
liquid.
Also addition of alkaline earth metal oxide MgO, CaO to hydrated
ammonium aluminum sulfate:urea (1:5 mole ratio, USIL) and BaO to
hydrated aluminum nitrate:urea (1:1.2 mole ratio, UNIL) decreased thermal
stability, heat capacity and thermal energy storage capacity than ionic liquid
alone.
Moreover, addition of transition metal oxide (VOSO4.5H2O, CuO and ZnO)
to hydrated ammonium aluminum sulfate:urea (1:5 mole ratio, USIL)
increased thermal stability and storage capacity of hydrated ammonium
aluminum sulfate:urea (1:5 mole ratio, USIL), while the addition of NiO to
hydrated ammonium aluminum sulfate:urea (1:5 mole ratio, USIL) only
improve thermal stability of ionic liquid.
 Subject Page

Abstract. I
Contents. III
List of Figures. V
List of Tables. X
Abbreviations. XII
Notations. XIII

Chapter One
Introduction
1.1 Introduction. 1
1.2 Some thermal and physical properties of ionic liquids. 3
1.3 Important applications of ionic liquids. 9
1.4 Heat storage materials. 11
1.4.1 Rocks. 12
1.4.2 Water. 14
1.4.3 Organic materials. 15
1.4.4 Thermal oils. 16
1.4.5 Molten salts. 17
1.4.6 Ionic liquids. 18
1.5 Thermal analysis. 23
1.5.1 Simultaneous thermal analysis (STA). 24
1.5.2 Thermogravimetric analysis (TGA). 24
1.5.3 Differential Scanning Calorimetry (DSC). 27
1.5.4 Determination of thermo-physical properties. 28
1.6 Aim of the work. 32

Chapter Two
Experimental Part
2.1 Chemicals. 33
2.2 Experimental methods. 34
2.2.1 Preparation of Room Temperature Ionic Liquids (RTILs). 34
2.2.1.1 Ionic liquid preparation with acetamide. 34
2.2.1.2 Ionic liquid preparation with urea. 34
2.2.2 Added salts to ionic liquids. 35
2.3 Instruments and measurements. 36
2.3.1 Simultaneous thermal analysis (STA). 36
2.3.2 X-Ray Diffraction (XRD). 36
2.3.3 Fourier Transform Infrared Spectroscopy (FTIR). 36
2.3.4 Conductivity, Density and Freezing Point measurements. 37

Chapter Three
Results and Discussion
3.1 Thermal Analysis (TGA/DTG & DSC), ATR-FTIR 38
spectroscopy and X-ray diffraction (XRD) of Ionic Liquids.
3.1.1 ATR-FTIR spectroscopy, thermal decomposition behavior 39
X-ray diffraction (XRD) of hydrated ammonium aluminum
sulfate:acetamide (ASIL).
3.1.2 ATR-FTIR spectroscopy, thermal decomposition behavior 46
X-ray diffraction (XRD) of hydrated ammonium aluminum
sulfate:urea (USIL).
3.1.3 ATR-FTIR spectroscopy, Thermal decomposition behavior 52
and X-ray diffraction (XRD) of hydrated aluminum
nitrate:acetamide (ANIL, 1:2.4 mole ratio) and (AN2IL,
1:22 mole ratio).
3.1.4 ATR-FTIR spectroscopy, Thermal decomposition behavior 63
and X-ray diffraction (XRD) of hydrated aluminum nitrate:urea
(UNIL).
3.2 Thermo-physical properties of ionic liquids. 68
3.2.1 Thermal properties. 68
3.2.2 Conductivity (k). 71

3.2.3 Density (ρ). 73

3.2.4 Enthalpy (∆H). 74
3.2.4 Heat capacity (Cp) and thermal energy storage capacity (E). 75
3.3 Addition of some materials to ionic liquids (ILs). 80
3.3.1 Addition of alkali metal hydroxide to ILs. 80
3.3.2 Addition of alkaline earth metal oxide to ILs. 86
3.3.3 Addition of transition metal oxide to ILs. 92
Conclusion. 99
Future Work. 101
References. 102
 List of Figures

Figure Description Page

No. No.
1-1 A general STA chart. 24
1-2 A general TGA/DTG curve. 25
1-3 TGA/DTG for calcium oxalate. 27
1-4 A general DSC thermogram. 28
1-5 DSC measurement of specific heat capacity. (a) baseline 29
(empty), (b) sample and (c) reference.
3-1 FTIR of (hydrated ammonium aluminum sulfate: 40
acetamide, ASIL with 1:5 mole ratio) (black line),
hydrated ammonium aluminum sulfate (blue line) and
urea (red line).
3-2 Thermogravimetric Analysis TGA (1), Differential 43
Thermal Analysis DTG (2), Differential Scanning
Calorimeter DSC (3) of (hydrated ammonium aluminum
sulfate: acetamide, ASIL with 1:12 mole ratio) heated
from room temperature to 500 °C at 10 °C/min.
3-3 X-ray diffraction of (hydrated ammonium aluminum 44
sulfate:acetamide, ASIL with 1:12 mole ratio) after
heating it from room temperature up to 500 °C.
3-4 FTIR of (hydrated ammonium aluminum sulfate: 46
acetamide, ASIL with 1:12 mole ratio) (black line) and
(red line) after heating it to 500 °C.
3-5 FTIR of (hydrated ammonium aluminum sulfate:urea, 47
USIL with 1:5 mole ratio) (black line), hydrated
 ammonium aluminum sulfate (blue line) and urea (red
line).
3-6 Thermogravimetric Analysis TGA (1), Differential 50
Thermal Analysis DTG (2), Differential Scanning
Calorimeter DSC (3) of (hydrated ammonium
aluminum:urea, USIL with 1:5 mole ratio) heated from
room temperature to 517 °C at 10 °C/min.
3-7 X-Ray diffraction of (hydrated ammonium aluminum 50
sulfate:urea, USIL with 1:5 mole ratio) after heating to
500 °C.
3-8 FTIR of (hydrated ammonium aluminum sulfate:urea, 52
USIL with 1:5 mole ratio) (black line) and (red line) after
heating it to 500 °C.
3-9a FTIR of (hydrated aluminum nitrate:acetamide, ANIL 54
with 1:1.2 mole ratio) (black line), hydrated aluminum
nitrate (blue line) and acetamide (red line).
3-9b FTIR of (hydrated aluminum nitrate:acetamide, AN2IL 55
with 1:22 mole ratio) (black line), hydrated aluminum
nitrate (blue line) and acetamide (red line).
3-10 Thermogravimetric Analysis TGA (1), Differential 59
thermal Analysis DTG (2), Differential scanning
calorimeter DSC (3) of (hydrated aluminum nitrate:
acetamide, ANIL with 1:2.4 mole ratio) heated from room
temperature to 495 °C at 10 °C/min.
3-11 Thermogravimetric Analysis TGA (1), Differential 60
thermal Analysis DTG (2), Differential scanning
calorimeter DSC (3) of (hydrated aluminum nitrate:
 acetamide, AN2IL with 1:22 mole ratio) heated from
room temperature to 495 °C at 10 °C/min.
3-12 X-ray diffraction of (hydrated aluminum nitrate: 62
Acetamide, AN2IL with 1:22 mole ratio) after heating it
up to 500 °C.
3-13 FTIR of (hydrated aluminum nitrate: Acetamide, ANIL 62
with 1:2.4 mole ratio) (black line) and (red line) after
heating it up to 500 °C.
3-14 FTIR of (hydrated aluminum nitrate: Acetamide, AN2IL 63
with 1:22 mole ratio) (black line) and (red line) after
heating it up to 500 °C.
3-15 FTIR of (hydrated aluminum nitrate:urea, UNIL with 64
1:1.2 mole ratio) (black line), hydrated aluminum nitrate
(blue line) and urea (red line).
3-16 Thermogravimetric TGA (1), Differential thermal 66
Analysis DTG (2), Differential scanning calorimeter DSC
(3) of (hydrated aluminum nitrate: urea, UNIL with1:1.2
mole ratio) heated from room temperature to 471 °C at 10
°C/min.
3-17 X-Ray diffraction of (hydrated aluminum nitrate:urea, 67
UNIL with 1:1.2 mole ratio) after heating to 500 °C
3-18 FTIR of (hydrated aluminum nitrate:urea, UNIL with 68
1:1.2 mole ratio) (black line) and (red line) after heating to
500 °C.
3-19 Conductivity (mS/cm) of (a): hydrated aluminum 73
nitrate:urea, UNIL with 1:1.2 mole ratio, (b): hydrated
ammonium aluminum sulfate: urea, USIL with 1:5 mole
 ratio), (c): hydrated ammonium aluminum sulfate:
acetamide, ASIL with 1:12 mole ratio and (d): hydrated
aluminum nitrate:acetamide, ANIL with 1:2.4 mole ratio
versus temperature up to 70 °C.
3-20 DSC thermogram in µV for; (1): baseline, (2): reference 78
material (Al2O3), (3): hydrated ammonium aluminum
sulfate:acetamide, ASIL with 1:12 mole ratio, (4):
hydrated ammonium aluminum sulfate:urea, USIL with
1:5 mole ratio, (5): hydrated aluminum nitrate:acetamide,
ANIL with 1:2.4 mole ratio, (6): hydrated aluminum
nitrate:acetamide, AN2IL with 1:22 mole ratio, (7):
hydrated aluminum nitrate:urea, UNIL with 1:1.2 mole
ratio at 10 °C/min.
3-21 TGA/ DSC of (hydrated aluminum nitrate:urea, UNIL 81
with 1:1.2 mole ratio) (blue color) and with addition of
sodium hydroxide (red color) at 10 °C/min.
3-22 TG/DSC of (hydrated aluminum nitrate:acetamide, AN2IL 83
with 1:22 mole ratio) (blue color) and with addition of
sodium hydroxide in (red color) at 10 °C/min.
3-23 TG/DSC of (hydrated ammonium aluminum sulfate:urea, 85
USIL with 1:5 mole ratio) (blue color) and with addition
of potassium hydroxide (red color) at 10 °C/min.
3-24 TG/DSC of (hydrated ammonium aluminum sulfate:urea, 87
USIL with 1:5 mole ratio) (blue color) and with addition
of magnesium oxide(red color) at 10 °C/min.
3-25 TG/DSC of (hydrated ammonium aluminum sulfate:urea, 89
USIL with 1:5 mole ratio) (blue color) and with addition
 of calcium oxide (red color) at 10 °C/min.
3-26 TG/DSC of (hydrated aluminum nitrate:urea, UNIL with 91
1:1.2 mole ratio) (blue color) and with addition of barium
oxide(red color) at 10 °C/min.
3-27 TGA/DSC of (hydrated ammonium aluminum sulfate: 93
urea, USIL with 1:5 mole ratio) (blue color) and with
addition of nickel oxide in red color (red color) at 10
°C/min.
3-28 TGA/DSC of (hydrated ammonium aluminum sulfate: 95
urea, USIL with 1:5 mole ratio) (blue color) and with
addition of copper oxide in red color(red color) at 10
°C/min.
3-29 TGA/DSC of (hydrated ammonium aluminum sulfate: 96
urea, USIL with 1:5 mole ratio) (blue color) and with
addition of zinc oxide in red color(red color) at 10 °C/min.
3-30 TGA/DSC of (hydrated ammonium aluminum sulfate: 98
urea, USIL with 1:5 mole ratio) (blue color)and with
addition of vanadyl sulfate pentahydrate in red color(red
color) at 10 °C/min.

List of Tables

Table Description Page

No. No.
1-1 Heat capacity of some important heat storage materials 12
with their temperature range.
1-2 Some physical properties of imidazolium based ionic 19
liquids.
1-3 Thermo-physical characteristic of tetrabutylammonium 20
based ionic liquids.
1-4 Thermal characteristics of tetraethylammonium based ionic 20
liquids.
2-1 Specification of the chemicals. 33
3-1 FTIR vibration frequencies of hydrated ammonium 40
aluminum sulfate:acetamide, ASIL with 1:12 mole ratio.
3-2 X-ray data of the product of (hydrated ammonium 45
aluminum sulfate:acetamide, ASIL with 1:12 mole ratio)
heated up to 500°C compared with Al2(SO4)3 standard data.
3-3 FTIR vibration frequencies of hydrated ammonium 48
aluminum sulfate:urea, USIL with 1:5 mole ratio.
3-4 X-ray data of the product of (hydrated ammonium 51
aluminum sulfate:urea, USIL with 1:5 mole ratio) heated
up to 500°C compared with NH4Al(SO4)2 standard data.
3-5 FTIR vibration frequencies of hydrated aluminum nitrate: 55
acetamide, ANIL with 1:2.4 and AN2IL with 1:22 mole
ratios.
3-6 FTIR vibration frequencies of hydrated aluminum nitrate: 64
urea, UNIL with 1:1.2 mole ratio.
3-7 Thermo-physical properties of five room temperature ionic 70
liquids.
3-8 Conductivity (k) and PH of five room temperature ionic 72

liquids.
3-9 Enthalpy (∆H) and entropy (∆S) of five room temperature 75
ionic liquids.
3-10 A comparison of reported heat capacities (Cp), densities (ρ), 77
 temperature range (°C) and thermal energy storage
capacities (E) of some heat storage materials compared
with ionic liquids present work.
3-11 Thermal characteristics of ionic liquids with some alkali 81
metal hydroxide.
3-12 Thermal characteristics of ionic liquids with some alkaline 86
earth metal oxide.
3-13 Thermal characteristics of (hydrated ammonium aluminum 92
sulfate:urea, USIL with 1:5 mole ratio) with some
transition metal oxide.

Abbreviations

Abbreviation Name
ILs Ionic Liquids
RTILs Room Temperature Ionic Liquids
SAIL Hydrated ammonium aluminum
sulfate:acetamide in 1:12 mole ratio
USIL Hydrated ammonium aluminum sulfate:urea
in 1:5 mole ratio
ANIL Hydrated aluminum nitrate:acetamide in
1:2.4 mole ratio
AN2IL Hydrated aluminum nitrate:acetamide in
1:22 mole ratio
UNIL Hydrated aluminum nitrate:urea in 1:1.2
mole ratio
 [C2MIm]+ 1-ethyl-3-methylimidazolium
[BF4] tetraflouroborate
[PF6]- hexaflourophosphate
[Tf2N]- bis(trifluorosulfonyl)imide
CF3SO3- trifluoromehtylsulfonate
[C2EIm]+ 1-ethyl-3-ethyimidazolium
[C4EIm]+ 1-butyl-3-ethyimidazolium
[C2MIm]+ 1-ethyl-3-methyimidazolium
[C4MIm]+ 1-butyl-3-methyimidazolium
[C8MIm]+ 1-octyl-3-methyimidazolium
[CH3SO3]- Methane sulfonate
[CF3CO3]- Trifluoroacetate
[C3F7CO2]- Perfluorobutanoate
[(CF3SO2)2N]- 1,1,1-trifluoro-N-[(trifluoromethylsulfonyl]-
[C4MP]+ N-butyl-N-methyl-pyrrolidinium
[MMC3Im] 1-2-dimethyl-3-propylimidazolium
[RMIm] 1-Alkyl-3-methyimidazolium
[N(CN)2]− Dicyanamide anion
[1C6–2C3–3,5C2py] 1-hexyl-2- propyl-3,5-diethylpyridinium salt
TFA Trifluoroacetate
[C8MIm] 1-octyl-3-methyimidazolium
[C16CPTS] N-hexadecyl-ϵ-caprolactam Cation-Based
Toluene-p-sulfonate
[N+4444] tetrabutylammonium cation
 Notations

Symbols Name Units

E Thermal energy storage density kJ/m3
 density kg/m3
Cp specific heat capacity kJ/K.kg
Cp(s) specific heat of the sample kJ/K.kg
Cp(r) specific heat of the reference kJ/K.kg
∆T change in temperature K
Mwt Molecular weight g/mol
m Weight mg
M(s) mass of the sample mg
M(r) mass of the reference mg
H(s) differential potential (in µV) of the µV
signal between the base line and the
sample
H(r) differential potential (in µV) of the µV
signal between the baseline and
reference
∆H Latent heat, enthalpy kJ/kg
∆Hf heat of fusion kJ/kg
∆S Entropy kJ/kg.°C
∆G Gibbs free energy kJ/kg
D crystallite size nm
k conductivity mS.cm-1

k constant
λ wave length of X-ray A°
β full width of diffraction peak at half
maximum (FWHM) intensity
θ Bragg angle degree
Chapter One
Introduction
 Chapter One
Introduction
1.1 Introduction:-
The early history of ionic liquids began in 1888, when ethanolammonium
nitrate (mp 52-55 °C) was reported by Gabriel[1]. Later in 1914, one of the
earlier known room temperature ionic liquids was [C2H5NH3][NO3],
excogitated by Walden[2]. He viewed the physical properties of ethyl
ammonium nitrate, [C2H5NH3][NO3], which had a melting point of 12 oC
produced from the reaction of concentrated nitric acid with ethylamine.

In 1951 Hurly and Weir declared that a room temperature ionic liquid could
be prepared by mixing and warming 1-ethylpyridinium chloride with
aluminum chloride[3]. In 1970s and 1980s Osteryoung et al. and Hussy et al.
carried extensive studies on organic chloride- aluminum chloride ambient
temperature ionic liquid and the first major review of room temperature ionic
liquids was published[4]. The ionic liquids based on aluminum chloride
[AlCl3] can be considered as the first generation of room temperature ionic
liquids. The hygroscopic nature of AlCl3 based ionic liquids has delayed the
development in their use. In multiple science applications they have to be
prepared and handled under inert gas atmosphere. Thus, the synthesis of air
and water stable ionic liquids, which are considered as the second generation
of ionic liquids attracted further interest in the use of ionic liquids in various
fields[5].

In 1992, Wilkes and Zaworotko confessed the first air and moisture stable
ionic liquids based on 1-ethyl-3-methylimidazolium [C2MIm]+ cation with
either tetrafluoroborate [BF4]- or hexaflourophosphate [PF6]- as anions like
[C2MIm]+[BF4]-, was prepared via metathesis of [C2MIm]+I- with Ag[BF4] in
methanol. Unlike the chloroaluminate ionic liquids, these ionic liquids should
be prepared and safely stored out off an inert atmosphere. Generally, these
ionic liquids are water stable, however, the exposure for a moisture to long
time may cause some change in their physical and chemical properties [6].

In 2006 several scientists, e.g. Welton, Wasserscheid, MacFarlane, Endres,

and others, came in this field having a strong impact in offering the ionic
liquids in many applications. They focused on the syntheses and
characteristics of environmentally friendly ionic liquids as green solvents.
They measured and established physicochemical characteristics for many
ionic liquids with the aim of providing data to start evaluating the use of ionic
liquids in a variety of processes. Also, they work on the development of new
materials from cellulose employing ionic liquids [7].

Wasserscheid is an active member of the ionic liquids community

concentrated on the preparation and characterization of ionic liquids for use in
the biphasic catalysis. For example, he could show that the use of
hexaflorophosphate ionic liquids give selective, biphasic oligomerization of
ethylene to 1-olefins. Together with Welton; they edited important book
entitled "ionic liquids in synthesis", which proffers the synthesis and
physicochemical properties of ionic liquids as well as their use in catalysis,
polymerization, organic and inorganic synthesis[8]. MacFarlane has prepared a
new air and water stable ionic liquids to employing such ionic liquids as
indicators for sensing and displaying an environmental parameter like
humidity. This process was controlled by the color change of the ionic liquids
where they are synthesized with either a colored cation or anion, so that the
ionic liquids themselves are indicators. Also, he has published many papers
on the use of ionic liquids in electropolymerization and in the batteries [9,10].
1.2 Some Thermal and Physical properties of ionic
liquids:-

1.2.1 Melting point:

As a class, ionic liquids have been defined to have melting points less than
100 oC and most of them are liquids at room temperature. Both cations and
anions share to the low melting point of ionic liquid. The increase in anion
size result in a decrease in melting point[8]. Another example, the melting
point of [C2MIm]+ type ionic liquid with different anions such as [BF4]- and
[Tf2N]- are 15 oC and -3 oC[11], respectively. Cations size and the symmetry
make an important effect on the melting points of ionic liquids. Large cations
and increased asymmetric substitution leads to a melting point reduction [8].

1.2.2 Density:

In general ionic liquid are denser than water with values ranging from 1 to
1.6 g/ml and their densities decrease with increase in the length of the alkyl
chain in the cation. For example, the density in ionic liquids composed of
substituted imidazolium cation and CF3SO3- anions decrease from 1.39 g/ml
for [C2MIm]+ to 1.33 g/ml for [C2EIm]+, to 1.29 g/ml for [C4MIm]+ and to
1.27 g/ml for [C4EIm]+ [12], the densities of ionic liquid are also affected by the
identity of anions. Another example, the densities of 1-buty-3-methyl
imidazolium type ionic liquids with various anions, such as BF4-, PF6-, and
Tf2N- are 1.12 g/ml, 1.21 g/ml, and 1.43 g/ml, respectively. The order of
increasing density for ionic liquid consisted of a single anions is: [CH3SO3]- =
[BF4]-[CF3CO3]- < [C3F7CO2]- < [(CF3SO2)2N]- [13,14].
1.2.3 Conductivity:

Ionic liquids have relatively good ionic conductivities compared with those
of organic solvents/electrolyte systems (up to 10 mScm-1)[8,11]. At high
temperature of e.g. 200 oC a conductivity of 0.1 mScm-1 can be achieved for
some systems.
However, at room temperature their conductivities are usually lower than
those of concentrated aqueous electrolyte. Upon the fact that ionic liquids are
consisted only of ions, it could be exerted that ionic liquids have elevated
conductivities. This was not the case, yet the conductivity of any solution
relies not only on the number of charge carrier but also their mobility [15]. The
large constituent ions of ionic liquids decrease the ion mobility which cause in
lower conductivities. Moreover ion pair formation and/or ion aggregation
results in conductivity reduction[11].

The conductivity of ionic liquid is inversely related to their viscosity.

Hence ionic liquids of higher viscosity show lower conductivity. Increasing
the temperature increase conductivity and reduce viscosity[13].

1.2.4 Viscosity:

Generally, ionic liquids are more viscous than popular molecular solvents
and their viscosities are ranging from 10 mPas to about 500 mPas at room
temperature. The viscosities of some common air and water stable ionic liquid
at room temperature are: 312 mPas for [C4MIm]+ PF6-[16], 154 mPas for
[C4MIm]+ BF4-; 52 mPas for [C4MIm]+ Tf2N-,[11] 85 mPas for [C4MP]+ Tf2N-.
The viscosity of ionic liquid is demonstrated, by Vander Waals forces and
hydrogen bonding. Electrostatic forces may also play significant role. Alkyl
chain lengthening in the cation resulted in an increase in viscosity as a result
of stronger Van der Waals forces between cations resulting in increase the
energy needed for molecular motion. Also, the ability of anions to form
hydrogen bonding has an obvious effect on viscosity. The fluorinated anions
as BF4 - and PF6- form viscous ionic liquid due to the formation of hydrogen
bonding[16]. In general, all ionic liquids exhibit a significant decrease in
viscosity as the temperature increases[17].

1.2.5 Thermal stability:

Ionic liquid can be thermally stable up to temperature of 450 oC. The

thermal stability of ionic liquid is limited by the strength of their hetero atom-
carbon and their heteroatom–hydrogen bonds[18]. Wilkes et al. reported that
the ionic liquids 1-ethyl-3-methyl imidazolium tetraflouro borate
[C2MIm][BF4], 1-butyl-3-methy imidazolium tetrafluoro borate
[C4MIm][BF4], and1-2-dimethyl-3-propyl imidazolium bis(trifluorosulfonyl)
imide [MMC3Im] [Tf2N] are stable up to temperature of 445 oC, 423 oC, and
457 oC, respectively[19].

Thermogravimetric analysis indicates high thermal stability for many ILs,

generally up to 350 °C. Such high temperatures are only tolerated by most
liquids for a short time. For example, after 10 h, even at temperatures as low
as 200 °C, [RMIm][PF6] and 1-decyl-3-methylimidazolium triflate show an
appreciable mass loss. Long time exposure to such high temperature
inevitably leads to decomposition. The ILs with low thermal stability are
[C2MIm][X], where X = [Tf2N]− and Br−[20]. Phosphonium ILs with [Tf2N]−
or [N(CN)2]− anions decompose completely to volatile products in a single
step. The degradation products indicate that Hofmann elimination process
and/or dealkylation reactions occurred. Conversely, ILs based on nitrogen
cations do not decompose completely[21]. The start of thermal decomposition
is furthermore similar for the different cations but appears to decrease as the
anion hydrophilicity increases. It has been suggested that the stability
dependency on the anion is in the order [PF6]− > [Tf2N]− > [BF4]− > halides.

An increase in cation size, at least from 1-butyl to 1-octyl, does not offer
[22]
large effect . Commonly most of the ionic liquids have extremely low
vapor pressures. This allows removing water by simple heating under
vacuum. Water contents below 1 ppm are quite easy to achieve with most of
the liquid [23].

1.2.6 Volatility:

Ionic liquids (ILs) are actual nonvolatile in the sense at near ambient
temperatures, their vapor pressure is negligible[24]. For typical ILs, normal
boiling temperatures (Tb), which related to the vapor pressure of ILs at one
atmosphere, cannot be experimentally determined as ILs decomposes at a
lower temperature. It has nevertheless been reported that ILs can be distilled
at 200–300 °C but under significantly reduced pressure and at very low
distillation rate (<0.01 gh−1). Vapor pressure of ILs remains, however,
negligible at near ambient conditions; thus, for all practical purposes, they
[25]
may be considered as nonvolatile solvents . On the whole, the negligible
volatility of these ILs denotes that air pollution by gaseous release is not a
concern. ILs are considered as nonvolatile and, consequently, nonflammable
at ambient and higher temperatures. However, the potential release of IL
vapors (or decomposition products) must be considered when ILs are used at
high temperatures [2] .

1.2.7 Electrochemical window:

The electrochemical window is an important character and plays a key role

in using ionic liquids in electrodepositing of metals and semiconductors. By
definition, the electrochemical window is the electrochemical potential range
[26]
in which the electrolyte is neither reduced nor oxidized at an electrode .
This value indicates the electrochemical stability of solvents. As known, the
electrodepositing of elements and compounds in water is limited by it's low
electrochemical window of only about 1.2 V, versus, ionic liquids have
significantly larger electrochemical windows, e.g., 4.15 V for [C4MIm]+PF6-
at a platinum electrode, 4.10 V for [C4MIm]+BF4-[27] and 5.5 V for
[C4MP]+Tf2N- at a glassy carbon electrode. In general, the broad
electrochemical windows of ionic liquids have opened the door to
electrodeposited metals and semiconductors at room temperature which were
olden obtained only from high temperature molten salts. For example, Al,
Mg, Si, Ge, and rare earth elements can be obtained from room temperature
ionic liquids. The thermal stability of ionic liquids permits to electrodeposits
Ta, Nb, V, Se and presumably many other ones at elevated temperature[16].

1.2.8 Heat Capacity:

Heat capacity refers to the amount of energy per molecule that a compound
can store by increasing temperature. Generally this energy is stored in
translational, vibrational and rotational modes. Thus higher heat capacity
expected to found in materials with greater number of atoms in its
composition[28]. The values of heat capacities of 24 ILs, pyridinium-based,
imidazolium, and ammonium ILs were presented. The high value (766 J mol −1
K−1 at 298 K) was observed for 1-hexyl-2- propyl-3,5-diethylpyridinium salt,
[1C6–2C3–3,5C2py][Tf2N]. Also it was found that heat capacity increases
linearly with increasing molar mass for these compounds that are comprised
of a limited number of different atoms[30].

1.2.9 Heat of Fusion (ΔH):

 It is the amount of thermal energy that a material must absorb or release in
order to change its phase from solid to liquid and vice versa. These values can
be straight away calculated from the area included in the DSC melting
endotherm. High values of heat of fusion lead to more efficient thermal
energy storage devices TESDs[30]. Certain ionic liquids possessing liquid
crystalline behavior can have multiple values of heat of fusion ranged from
100 kJ.mol-1 to 200 kJ.mol-1. These values correspond to the morphological
change in the material occurring in the same phase. The changes usually
occur in a narrow temperature range. Thus it is possible to use ILs as thermal
energy storage TES devices. While using ILs as TESD, the summation of
small heat changes occurring in the neighborhood of the phase change
temperature can be considered as effective heat of fusion[31].

1.2.10 Hygroscopic:

The water content has an impact on the viscosity of the ionic liquid.
Viscosity measurement determines that ionic liquids become less viscous with
rise water content. Hydrolysis problems may also occur[3]. Moisture
sensitivity and the difficulty of separation of products owning heteroatom
from the ionic liquid infect. In order to progress chemistry of ionic liquids,
and increase the robustness of processes, water-stable ionic liquids have been
found to be hydrophobic but yet readily dissolve many organic molecules [32].

1.2.11 The color:

The high quality ionic liquid has been showed to be colorless, but they are
not 100 % pure. Generally, the color of less pure ionic liquids ranges from
yellowish to orange. The formation of the color was resulted from using raw
materials with color or excessive heating through the synthesis of
imidazolium salt. Several precautions for synthesis of colorless ionic liquid
has been described. A procedure to remove the color from impure ionic liquid
using acidic alumina (Al2O3) and activated charcoal has also been suggested
[8]
.

1.3 Important applications of Ionic Liquids:-

Ionic liquids (ILs), considered to be a relatively recent magical chemical
due to their unique properties, have a large diverse applications in all field of
the chemical industries. The most important applications are:

1.3.1 Homogeneous and heterogeneous catalyst:-

For some applications, ionic liquids exhibit the better benefit of both
homogeneous and heterogeneous catalysts. Because of chosen ionic liquids
could be immiscible with the reactants and products and the catalysts still
soluble.

This has the advantages of a solid for immobilizing the catalyst, with
the advantages of a liquid for permitting the catalyst to mobilize freely [33-35].

1.3.2 Biological reactions media:-

Enzymes are stable in ionic liquids, opening the probability of ionic liquids
to be applied in biological reactions. Synthesis of pharmaceuticals is an
example of such application[34,35].
Ionic liquid-water biphasic systems were widely studied and applied as new
energy-storage processes for condensation, separation, extraction and of
biopolymers[36]. Mainly stabilization and solubilization of proteins in isolated
hydrophobic ionic liquid phase more than aqueous phase could lead to the
interesting application of ionic liquids for product separation systems and/or
continuous enzymatic reaction.

1.3.3 Removing of metal ions:-

 In another application, Davis and Rogers were designed and synthesized a
number of novel ionic liquids to eliminate cadmium and mercury from
pollutant water. When these water immiscible ionic liquids become in contact
with pollutant water, they arrest the metal ions outside of water and insulate
them in the ionic liquid[37] .

1.3.4 Purification of gases:-

Ionic liquids can selectively dissolve and remove gases and might be
applied for air purification on spaceships and submarines, it was found that
aluminum chloride-urea ionic liquid effective in carbon dioxide capture[38].
RTILs had a special potential as designer solvents in the gas capturing and
can be used in CO2/CH4 and ethylene (C2H4)/ethane (C2H6) isolations. RTILs
can be used as a basis for development substituent strong absorption solvents.
Generally, pattern ionic liquids with fluorine-constituent anions, such as BF4,
PF6, Tf2N, TFA, gave the higher CO2 absorption capacity. The highest CO2
solubility was performed with the ionic liquid [C2MIm][NTf2], with a molar
fraction of 0.23 at 303 K. The large gas capacity of this ionic liquid might be
belonged to weaker anion-cation interaction, which permits a large interaction
with ions of the liquid and the gas solute[39].

1.3.5 Heat storage media:-

Ionic liquids had excellent technical features for the applications as liquid
heat transfer fluids and thermal storage media. The features include high heat
capacity, high chemical stability, wide liquid temperature range, high density,
non-volatility and high storage density. For example C8MImPF6 ionic liquid,
have storage density of 378 MJ/m3 and liquid temperature range from (–75 to
416) oC[40], also it is found that [C4MIm][Tf2N] ionic liquid have some
advantages over other ILs. The calculated sensible heat storage density for
[C4MIm][Tf2N] was more than 170 MJ/m3 when the inlet and outlet region
temperature were 210 °C and 310 oC. It is found that these ionic liquids were
suitable for application as heat-transfer fluids and they are over present
commercial heat transfer fluids due to low vapor pressure, wide liquid
temperature range and ability to store essential sensible heat [41].

1.4 Heat Storage materials:-

The demand and supply gap for energy sources increased day by day.
Moreover, the fact that ''energy can neither be created nor destroyed'' has lead
in focused of some scientific research in the direction of storing the different
forms of energy using various heat storage materials. Heat storage materials
are materials with the ability to store energy and then release it in a
continuous manner, which were chosen on the basis of several limited
physical, chemical and economic properties[41,42].
Recently, various conventional and unconventional compounds were
studied to demonstrate their capability to store thermal energy. Such materials
had their melting points within the usable temperature range and hence known
as phase changing materials (PCMs)[43].

Several thermophysical, chemical and economic assets were desired of an

ideal phase change material to be used as heat storage materials. It is expected
that PCMs would have high value of density, heat capacity, thermal
conductivity and heat of fusion[3,44]. There were a large range of various
materials which could be used for thermal storage. One of the most significant
physical parameters of a thermal storage was its storage capacity and
temperature range. These two parameters determine the volume and
suitability of the storage for an application, respectively[44,45]. Table (1-1) gave
a summary of the storage capacity and temperature range of some important
storage materials.
Table (1-1): Heat capacity of some important heat storage materials with their temperature
range[41].
Heat capacity Temperature
Heat storage (kJ/K.kg) range(°C)
materials
Water 1.6 at 100 °C 0 – 100
Rock as Granite 0.76 -
Ethylene glycol 2.1 at 100 °C -37 - 110
Thermal oil 1.90 -30 - 300
Molten salts as 50% 1.56 142 - 540
KNO3+ 7%NaNO3+
43% NaNO2
Ionic liquid 2.50 -75 - 416

1.4.1 Rocks:-
Energy can be stored at low and intermediate temperatures by heating
rocks held in isolated containers. This type of storage was used often for
temperatures up to 100 °C conected with solar air heaters since rocks could be
heated by just blowing air within the spaces between the rocks (if Iiquid is
used in the collectors, a more developed heat-exchange mechanism will
required). Rock storage could be simple and inexpensive, but designing an
optimum system might be difficult since the performance efficiency is
affected by the volume, shape, specific heat, density and other characteristic
for the used rocks[45].

Direct contact between the solid storage medium and heat transfer fluid is
required to minimize the expense of heat exchange of a solid storage medium.
Using rocks as thermal storage[46] provides several advantages:
1. Rocks are non-flammable and not toxic.
2. Rocks had low cost.
3. Rocks can behave as both heat transfer surface and heat storage medium.
4. Heat transfer between air and a rock surface was good, arise from very
large heat transfer area with effective thermal conductance of the rock hill
was low, due to the low area for a touching between the rocks. Then the heat
lost from the hill is small.
The main disadvantages of using rocks as heat storage are associated with
the larger air mass flow rates and surface area needed due to the lower
volumetric heat capacity and thermal conductivity of air as compared to those
of thermo-oils, molten salts or other heat transfer fluids proposed. These
drawbacks translate into higher pressure drops and concomitant energy
penalties. Energy densities for a concrete-based thermal storage system have
been estimated at 22 kWh/m3, resulting in 50,000 m3 sized storage for a 50
MW parabolic trough power plant with 1100 MWhth storage capacity[47] .
The difficulties and limitations relative to liquids can be avoided by using
solid materials for storing thermal energy as sensible heat. However, larger
amounts of solids are required compared with using water, a rise from the fact
that solids, in general, shown less storing capacity than water. The cost of the
storage media per unit energy stored is, anyway, still agreeable for rocks.
The use of rocks as heat storage is more limited due to their low heat
capacity (~0.9 kJ/kg/K), low thermal conductivity (~6.6 W/m/K), and
unknown response to long-term thermal cycling[48]. The presence of a
confined aquifer, an impermeable cap rock, compatible underground water
regime, high porosity, and high permeability of the rock formation [49].

1.4.2 Water:-

For most industrial applications, water is the most popular heat transfer
fluid and the use of water as the storage medium for liquid systems has been
the dominant approach and is likely to remain so for at least a decade [50,51]. It
has high specific heat capacity, high latent thermal energy (ΔH), high density,
high thermal conductivity, moderate viscosity and wide availability with low
environmental impact. In contrast, the use of rocks as sensible heat storage is
more limited due to their low heat capacity, low thermal conductivity, and
unknown response to long-term thermal cycling[49].

In most solar heating and hot water systems they use an insulated hot water
tank located in the building equipment room or buried in the ground. It may
also be possible to store very large amounts of low temperature thermal
energy by pumping hot water into contained underground aquifers. Water
storage tanks were made from a diverse of materials such as concrete, steel
and fiberglass. The tanks were suitably insulated by mineral wool, glass wool
or polyurethane resulting in high cost[43], but the biggest difficulties for use
water as a heat transfer fluid was the limited range of temperature above
which it could be used. Theoretical liquid range is between 0 oC and 100 oC,
but the practical temperature range of water applied as heat transfer fluid was
much less than 100 oC, because of the high vapor pressure at near boiling
point. The extension of the application temperature range to below freeze
point can be accomplished by using antifreeze (e.g., ethylene glycol water
mixture), but the extension over the boiling point of the aqueous system is
extremely difficult. High pressure is needed to keep water in the liquid state
when the temperature is over 100 oC, which could cause very high costs for
the related pressure vessels and pipes. High temperature water (over 100 oC)
was suggested for many industrial applications[52,53], but corrosiveness and
volume expansion at high temperature are its major downsides for thermal
applications so it is not suitable as a heat transfer fluid nor thermal media for
a solar energy power plant.
 Water storage is probably not an attractive option for storage above 150 to
200 °C since the pressure required would greatly increase the cost and danger
of operating such systems.

1.4.3 Organic Compounds:-

Organic compounds can also be used for storing energy as latent heat (ΔH).
These materials have the advantage of relatively high heats of fusion, and few
of the materials examined present problems of supercooling or high vapor
pressures. Unfortunately, some of the most attractive organic materials under
consideration e. g., paraffins[54] have a relatively large volume change upon
melting nearly 10 % in some cases, are flammable, and can cause stress
cracking if the containment vessel is not constructed from a material as strong
as steel. Experimental paraffin storage systems, however, have been operated
successfully. Other materials suitable for heating include artificial spermaceti
manufactured by Lipo Chemicals and paraffin wax possibly mixed with
carbon tetrachloride. These materials melt in the range of 58 to 60 °C, and
have heats of fusion on the order of 200 to 210 kJ kg-1[55].
Organic materials can be classified as phase change materials (PCM), and
it can be subdivided into paraffin and non-paraffin compounds. Paraffin
compounds are among the most reliable in latent heat storage (ΔH) systems
due to their availability, cost, and safeness. They also have a wide range of
melting points, are chemically inert (stable below 500 oC), and exhibit volume
change upon melting on the order of 10 %[48]. The latent heat of fusion (∆H)
of paraffins is about 200 kJ/kg. For a mass density ρ 850 kg/m3, the
approximate energy density (E) of paraffin is 170 MJ/m3. However, paraffin
compounds have low thermal conductivity and are chemically incompatible
with some plastic containers[49].
1.4.4 Thermal Oils:-
Heat transfer oils are used in sensible heat storage systems for intermediate
temperatures ranging from 100 to 300 °C as Dowtherm and Therminol. Some
of the sensible heat storage systems utilize a mixture of rocks and a heat-
transfer fluid such as Therminol[49].

All heat transfer oils share a common set of problems are low
decomposition temperature, low density, inflammability, high vapor pressure,
harmfulness, and low chemical stability;[56] and they all degrade with time[52].
Their degradation is increased rapidly if they are operated above their
recommended temperature limits for any length of time. This degradation
requires a filtering system and means that the relatively expensive oils must
be continually replaced. The oils also can present safety problems, since they
can be ignited by open flames at temperatures in the range of 165 °C (fire
point) and have a high enough vapor pressure to sustain combustion at
temperatures in the range of 550 °C to 600 °C ignition temperature, This
means that great care should be taken to ensure that the material is not
overheated, dikes will be needed to prevent the material from spreading if a
leak should occur. Some systems require an inert gas (such as nitrogen) over
the liquids in the tanks to inhibit reactions which might degrade the storage
material[57].

A further limitation to the use of heat transfer oils is their cost. For these
reasons, they could be seriously considered to use only for small storage
systems[58] .

1.4.5 Molten Salts:-

 A molten salt heat transfer medium was commercialized in 1937[59]. A
number of molten inorganic salts were considered for their high temperatures
300 °C and above. One is an eutectic mixtures composed of 7 % NaNO3, 40

% NaNO2 and 53 % KNO2 by weight which is available in trade name of

‘Hitec’. Hitec has a melting point of 145 °C and could be used up to a
temperature of 425 °C. Over this temperature; decomposition and oxidation
appear to take place[60]. A good candidate alternative molten salt formulation
also available at a reasonable cost is a commercial ternary molten salt
mixture known as Hitec-XL, an eutectic mixture of 48 % Ca(NO3)2, 7 %
NaNO3, 45 % KNO3 (by weight), has freezing point of about 120 ºC and
stable to temperatures around 500 ºC[61]. Another molten salt was taken in to
account for high temperature storage is NaOH, that had a melting point of
320 °C and can be used for temperatures up to 800 °C. Anyway, it is highly
corrosive and there was a difficulty in containing it at higher temperatures
storage in a parabolic trough plant[62].

Due to the avoidance of high pressure, the wall thickness of the piping and
the pump casings, heat exchangers, and other items of equipment were much
lower than those required for high pressure steam systems operating in this
temperature range. One problem is that the heat exchanger system has to be
preheated to ensure that liquid metal and molten salts remain liquid. When the
temperature is not high enough, molten salts freeze and cause operation
problems. Although there are some operation problems as described above,
the molten salts have been used in cracking units in the petroleum refining
industry. The reason is that there is no better heat transfer medium
available[61,62].
 Currently molten salt is used as liquid storage media. The main problems
for molten salt media is its high melting point (e.g. 220 oC). The high melting
point could lead to molten salt freezing in evening or cold weather, causing
high operating costs[40].

1.4.6 Ionic Liquids:-

Ionic liquids are liquid salts consist solely of ions (cations and anions) have
melting point of 100 °C or below and considered as green solvents[63]. Ionic
liquids have a couple of unique features that open the door for the
development of new highly specialized applications[64,65]. Based on the
experimental results, it's found that ionic liquids have excellent technical
properties for the applications as liquid heat transfer fluids and thermal
storage media in a solar thermal power plant[66]. These properties include high
heat capacity, wide liquid temperature range, and high density, on the other
hand the combination of very low vapor pressure, good heat capacity, wide
usable temperature range and great thermal stability of ionic liquids permit of
their using as heat transfer media under vacuum or very low pressures[67],
another properties contribute to the qualification of ionic liquids as heat
transfer fluids and liquid thermal storage media were high chemical stability,
non-volatility, high storage density, non-harmfulness, and non-flammable[68].

The use of ionic liquids as thermal fluids was first suggested by Rogers et
al. in 2001[40]. They studied a number of ionic liquids based on imidazolium
cations with a varity of inorganic anions such as [C4MIm][PF6],
[C4MIm][BF4], [C4MIm][Tf2N], [C4MIm][(CF3SO2)2N], [C8MIm][BF4],
[C8MIm][PF6], and found that they have advantages of high density, low
viscosity, non-volatility, wide liquid temperature range, high chemical
stability, high heat capacity, and high storage density ,Table(1-2) offer some
of these properties[40,41].
Table (1-2): Some physical properties of imidazolium based ionic liquids.
Ionic liquid Melting Decomposition Density at 25 Viscosity at
Point (°C ) point (°C ) °C ( kg/m3) 25°C(mPa s)
[C4mIm][PF6] 4 390 1370 312
[C4mIm][BF4] -75 407 1119 219
[C4mIm][Tf2N] -89 402 1429 54.2
[C8mIm][PF6] -75 416 1400 -

These properties make ionic liquids excellent candidates as heat transfer

fluids for solar thermal power plant system but economic application cost of
ionic liquids as heat transfer fluids and liquid thermal storage media needs to
further investigation[41].

In 2010, Bhatt et al.[28] study thermal energy storage capacity of some

phase changing materials and ionic liquids and after a rigorous study of their
properties, they unable to place ionic liquids in the final list as heat storage
material due to lack of information of properties of some ionic liquids. But,
in 2013 Bhatt and G. Kuldip found seven ionic liquids (ILs) based on
tetrabutylammonium cation [N+4444] and inorganic anions, have good
thermophysical characteristics to use as thermal energy stored materials for
their applications in a solar cooker, Table(1-3) show these properties more
clearly[69].
 Table (1-3): Thermo-physical characteristics of tetrabutylammonium based ionic liquids.
ILs Tm ρ ∆H Cp
(°C) (kg/m3) (kJ/kg) (kJ/kg.°C)
[N+4444][BF4-] 71 1291 253.75 1.00
[N+4444][P F6-] 71 1234 155.00 0.40
[N+4444][BrO3-] 86 1050 153.71 0.30
[N+4444][NO3-] 98 1195 144.00 1.50
[N+4444][SCN-] 110 1143 253.00 0.20
[N+4444][Br-] 102 1039 193.00 2.00
[N+4444][I-] 44 1279 113.00 2.70
Recently, Bhatt and G. Kuldip[43] made further investigation on eight
ionic liquid salts based on tetraethylammonium cation [N+2222] with inorganic
anions like BF4−, NO3− , NO2− , SCN−, BrO3− , IO3− , PF6− and HCO3−. They
found that these ionic liquids ILs deserve a consideration to replace the
traditional materials used as thermal energy storage TES, due to unique
properties of storing and releasing a significant amount of thermal energy in
both solid and molten phases, as illustrated in Table(1-4).
Table (1-4): Thermal characteristics of tetraethylammonium based ionic liquids[43].
Tm Tdec. ρ Cp ∆H
ILs (°C) (°C) (kg/m3) (kJ/kg°C) (kJ/kg)

[N+2222][HCO3] 74 170 1145 1.60 142.26

[N+2222][BF4−] 91 190 1132 1.00 102.08
[N+2222][PF6−] 82 170 1074 1.40 132.00
[N+2222][BrO3−] 46 180 1153 0.70 118.00
[N+2222][NO3−] 115 190 1029 0.90 137.44
[N+2222][NO2−] 58 180 1023 1.50 157.17
[N+2222][SCN−] 62 160 1057 1.10 127.67
[N+2222][IO3−] 53 180 1162 1.70 147.29
 Now days, they are being studied for their use in the fields of thermal
energy storage, solar power plant, solar cell[70] and heat transfer fluids[71].
Nucleating agents such as copper and graphite powder have been used for
releasing the stored energy from super cooled ionic liquids[72].

The efficacy of ionic liquids as thermal fluids determined by comparing the

properties of ionic liquids with an existing thermal fluid, and by comparing
properties with the specific needs of a device or technology[43]. The matrix of
properties determined so far indicate that ionic liquids are attractive
candidates for heat transfer and storage. Properties of material that may be
compared with the ionic liquids are: composition, freezing point, moisture
content, viscosity, density, heat of fusion, decomposition temperature, electric
conductivity, use range of temperature, cost and appearance. A set of thermal
fluid target specifications for thermal trough technology was promulgated by
the National Renewable Energy Laboratory. Ionic liquid properties that may
be compared now with those targets are: latent heat storage density, sensible
heat storage density, freezing point, thermal stability, vapor pressure,
viscosity, cost. But they lack in quantitative data on materials compatibilities.

The most commonly used ILs [C4MIm][PF6] and [C4MIm][BF4] were

known to decompose in the presence of water and as a result phosphoric and
hydrofluoric acids were produced. Therefore, both toxicity and ecotoxicity
provided data which give metabolism and degradability of ionic liquids were
also required to label them as green solvents or study their environmental
impact[74].

Ionic liquids contain PF6− and BF4– anions were reported to be

decomposed in the presence of water, giving of HF. Wasserscheid et al.
referred that ionic liquids containing halogen anions generally showed poor
stability in water and also form toxic and corrosive fumes such as HCl and
HF[75]. Therefore, they suggested the use halogen-free and relatively
hydrolysis stable anions for example octylsulfate compounds. The degree of
hydroscopic character and interaction between water and ionic liquids were
strongly dependent on anions. The quantity of water absorbed was higher in
the BF4− and lower in PF6−. However, [Tf2N] −
showed much more water
stability and having the advantage of an increased hydrophobic property.
Ionic liquids which are water immiscible tend to absorb moisture from the
atmosphere[76].

The FTIR studies explained that the water molecules absorbed from the
air were mostly found in the free state and bonded via H-bonding with the
PF6– and BF4− anions. The presence of water might have great effect on the
reactivity of ionic liquids[74,77].

The newly synthesized ionic liquids were much stable than the old
halogenoaluminated systems. The new ionic liquid alum such as (NH4Al
(SO4)2.XH2O, Al2(SO4)3.XH2O and AlK(SO4)2.XH2O) with urea considered
useful as a green solvent because these have low vapor pressure and stable to
air or moisture. New types of ionic liquids were prepared from alum sulfate
(AlNH4(SO4)2.12H2O) instead of aluminum chloride with urea salt[78]. These
ionic liquids much stable than chloroaluminate ionic liquids, offering
relatively cheaper, easily prepared ionic liquids with promising similar
properties. As this is green ionic liquid as it expected to be used in variable
process such as metal coating as it offer good media for some insoluble
compounds in aqueous media to be dissolve easily in this ionic liquid such as
silver sulfate [79].
 Another room temperature ionic liquids based on alum of the type
Al2(SO4)3.XH2O, AlNH4(SO4)2.XH2O and AlK(SO4)2.XH2O with urea or
Acetamide and hydrated aluminum nitrate Al(NO3)3.XH2O with urea[80] or
Acetamide for its ease of handling ,cheaper ,greener and incorporating of
these compounds in variable industrial applications such as water purification.
The ionic liquids chosen have the advantages of being stable towards air and
moisture.

1.5 Thermal Analysis:-

Thermal analysis is defined as an analytical experimental technique which
investigates the physical properties of a sample as a function of temperature
or time under controlled conditions. This definition is broad and the following
techniques are referred to conventionally as thermal analysis, i.e.
thermogravimetry (TG), differential thermal analysis (DTA), differential
scanning calorimetry (DSC)[81,82].

Most common is the simultaneous thermal analysis (STA) apparatus as

the combination of thermogravimetric analysis (TGA) and differential
scanning calorimetry (DSC)[83].

1.5.1 Simultaneous Thermal Analysis (STA):-

The STA combines two analytical techniques together. It combines TGA
and DSC. Simultaneously the STA collects the data of both heat flow from
DSC and weight loss from TGA. The STA Simultaneous Thermal Analyzer
applies leading border sensor technology to give high accuracy and quality
results [83].
 TG

DSC

Figure (1-1): A general STA chart.

1.5.2 Thermo-gravimetric Analysis (TGA):-

Thermo-gravimetry study changes in the mass of a sample under a

controlled temperature program. The temperature program is most often a
linear increase in temperature[84]. TGA is originally quantitative, and so an
extremely powerful thermal technique, but do not gives direct chemical
information and the ability for analyzing the volatile products through a
weight loss is of great value. Applications ability of TGA to create
fundamental quantitative information from almost any class of materials, had
lead to its widespread used in field of science and technology. Mainly the key
application areas were thermal stability; related materials could be compared
at elevated temperatures through the required atmosphere and can help to
elucidate decomposition mechanisms.
1.5.2.1 Data Analysis:-

Thermogram: is graph of mass versus temperature. Sometimes given as

percent of original mass (m %)[85].

Figure (1-2): A general TGA/DTG curve.

In a TGA curve of one decomposition stage, there were two

characteristic temperatures; the initial Ti and the final temperature Tf (see Fig.
1-2). Ti is known as the lowest temperature at which the onset of a mass
change can be detected by thermo-balance working under particular
conditions and Tf as the final temperature in which the specific decomposition
appear to be complete. The difference Tf – Ti is termed as reaction time[86].

TGA curves of a pure compound are a property of that compound. Using

TGA curve we could relate the mass changes to the stoichiometry included.
This could often directly lead to the quantitative analysis of the samples that
their quantitative composition was known[87].
 For further illustration, weight loss detected by TG can be calculated
depending on two important factors weight lost percent and temperature at
that point; weight lost percent can calculated using molecular weight of each
fraction divided to the original molecular weight of the sample, for example if
there are three stages at which sample undergo three decomposes steps then
there are must be three fractions from the original sample are lost so each
weight will become[87,88]:

𝑀𝑤𝑡 𝑜𝑓 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛
First weight loss %(𝑚1 ) = ∗ 100 …(1.1)
𝑀𝑤𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒
𝑀𝑤𝑡 𝑜𝑓 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛
Second weight loss %(𝑚2 ) = ∗ 100 …(1.2)
𝑀𝑤𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒
𝑀𝑤𝑡 𝑜𝑓 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛
Third weight loss %(𝑚3 ) = ∗ 100 …(1.3)
𝑀𝑤𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒

The resulted calculation then compared with measured values found by TG

analysis. Both boiling points of vapors and weight loss percents enable us to
estimate fractions (gases) librated throw decomposition process.
Now see example how TG curve could be used for thermal stability
comparison between materials (qualitative interpretation). Predict product
efficiency and enhance product quality. The thermal decomposition of
calcium oxalate monohydrated (CaC2O4.H2O(s)), involve three decomposition
stages[86,89,90]:-

Calculated weight loss percent will be:

𝑀𝑤𝑡 𝑜𝑓 𝐻2 𝑂 18 𝑔. 𝑚𝑜𝑙 −1
𝑚1 = ∗ 100 = ∗ 100 = 12.3 %
𝑀𝑤𝑡 𝑜𝑓 𝐶𝑎𝐶2 𝑂4 . 𝐻2 𝑂 146 𝑔. 𝑚𝑜𝑙 −1
𝑀𝑤𝑡 𝑜𝑓 𝐶𝑂 28 𝑔. 𝑚𝑜𝑙 −1
𝑚2 = ∗ 100 = ∗ 100 = 19.2 %
𝑀𝑤𝑡 𝑜𝑓 𝐶𝑎𝐶2 𝑂4 . 𝐻2 𝑂 146 𝑔. 𝑚𝑜𝑙 −1
 𝑀𝑤𝑡 𝑜𝑓𝐶𝑂2 44 𝑔. 𝑚𝑜𝑙 −1
𝑚3 = ∗ 100 = ∗ 100 = 30.1 %
𝑀𝑤𝑡 𝑜𝑓 𝐶𝑎𝐶2 𝑂4 . 𝐻2 𝑂 146 𝑔. 𝑚𝑜𝑙 −1

Figure (1-3): Reference TG/DTG of calcium oxalate.

Interpretation data analysis will be

1. Stage: Dehydration: CaC2O4.H2O(s)  CaC2O4 (s) + H2O (g)
Mass change found (calculated): -11.89% (-12.3 % )
2. Stage: Building carbonate: CaC2O4(s)  CaCO3 (s)+ CO (g)
Mass change found (calculated): -19.42% (-19.2%)
3. Stage: Decarbonation: CaCO3 (s)  CaO (s) + CO2 (g)
Mass change found (calculated): -30.44% (-30.1%)

1.5.3 Differential Scanning Calorimetry (DSC):-

Differential Scanning Calorimetry (DSC) is most popular thermal analysis
technique, DSC measures endothermic and exothermic transitions as a
function of temperature[87,90], in endothermic transition heat flows into a
sample as a result of either heat capacity (heating) or some endothermic
process (glass transition, melting, evaporation, etc.). While in exothermic
transitions heat flows out of the sample as a result of either heat capacity
(cooling) or some exothermic process (crystallization, cure, oxidation, etc.)[91]
as showed in Figure (1-4). DSC used to characterize polymers,
pharmaceuticals, foods/biologicals, organic chemicals and inorganics[92-95].
DSC is able to provide all the thermodynamic parameters of a conformational
transition.

Figure (1-4): A general DSC thermogram.

1.5.4 Determination of thermo-physical properties:-

1. Heat Capacity, Enthalpy and Entropy:-
Specific heat capacity (Cp) is a material property describing the energy
required to induce a certain change in the temperature of a unit mass of the
material[96]. Measurement of this quantity, a differential scanning calorimeter
(DSC) may be used. The DSC measures specific heat capacity by heating a
sample and measuring the temperature difference between the sample and a
reference[97]. Three measurements are necessary for calculating specific heat.
First a “Baseline” is recorded. This is the response with both crucibles empty,
yielding a signal bias inherent in the system. Next is a reference test, in which
a sample with a well defined specific heat is tested for comparison to an
experimental sample. Finally, an experimental sample is tested. The
“Baseline” allows removal of system bias from the data, while the reference
test allows calculation of the specific heat of the experimental sample as a
ratio of the reference material specific heat[98,99].
The specific heat capacity of the sample was calculated by equation (1.4)
from the DSC data obtained (a, b and c in Figure 1-5).

Figure (1-5) DSC measurement of specific heat capacity, (a) base line (empty), (b) sample
and (c) reference.
 𝐻(𝑠)∗𝑀(𝑟)
𝐶𝑝(s) = ∗ 𝐶𝑝 (𝑟) …(1.4)
𝐻(𝑟)∗𝑀(𝑠)

Where:
Cp(s): specific heat of the sample.
Cp(r): specific heat of the reference.
M(s): mass of the sample.
M(r): mass of the reference.
H(s): differential potential (in µV) of the signal between the base line and the
sample.
H(r): differential potential (in µV) of the signal between the base line and
reference.

Heat capacity is the fundamental property from which all thermodynamic

quantities may be derived, and this is central to DSC measurements and to the
fundamental underlying thermodynamics[99].

Enthalpy (∆Htrs) is a measure of the net flow of energy, as heat, during a

chemical reaction. Reactions in which heat is produced have a negative ∆H
and are called exothermic. Endothermic reactions absorb heat from their
surroundings and have a positive (∆Htrs). The enthalpy value (∆Htrs),
calculated from the area under the transition peak. The ∆H value is actually a
net value from a combination of endothermic contributions [91,100].

∆H = KA/m ….(1.5)

Where K is calorimetric constant and A is area under the transition peak

and m is the mass of the sample. Another thermodynamic property is Entropy
(∆S; a measure of the disorder) calculated from change in enthalpy at its
transition temperature:
 ∆S = ∆H/T ….(1.6)

If the phase transition is exothermic (∆Htrs< 0, as in freezing or

condensing), then the entropy change is negative. This decrease in entropy is
consistent with localization of matter and energy that accompanies the
formation of a solid from a liquid or a liquid from a gas. If the transition is
endothermic (∆Htrs> 0, as in melting and vaporization), then the entropy
change is positive, which consistent with dispersal of energy and matter in the
system[84,100].
1.6 Aim of the work

Renewable energy sources are an alternative energy sources in natural oil

sources providing energy for valuable applications. Therefore storing heat
from the sun to be converted into electricity or used as such as challenged
method. One promising media is ionic liquids which are liquid below 100 °C.
The valuable properties of these ionic liquids (RTIL) open the door for this
applications. Thus some room temperature ionic liquids of ASIL, USIL,
ANIL, AN2IL and UNIL were investigated for their suitability of their
thermophysical properties studied aims TGA/DTG and DSC from room
temperature to 500 °C.

1. Preparation of new low temperature ionic liquids for sensible heat

storage media.
2. Improvement thermophysical properties of some existent ionic liquids
as a heat storage (heat capacity, Cp and thermal energy storage
capacity, E).
3. Improvement of the thermophysical properties intended by adding
some oxy anion compounds of alkali metal, alkaline earth metal and
some transition metal compounds to some ILs.
Chapter Two
Experimental
 Chapter Two
Experimental
2.1 Chemicals:-

All chemicals were used in current work with highest purity available and
without further purification, as in Table (2-1) shows the reagents, their
purities and suppliers:
Table (2-1): Specification of the chemicals.

Chemical Formula Purity Company

compounds %
Acetamide CH3CONH2 98 Fluka
Aluminum Nitrate Al(NO3)3.9H2O 99.3 MERCK
nanohydrate
Ammonium NH4Al(SO4)2.12H2O 99.5 BDH
aluminum sulfate
dodecahydrate
Barium Oxide BaO 99 BDH
Calcium Oxide CaO 99 BDH
Cupric Oxide CuO 99 MERCK
Magnesium Oxide MgO 99 BDH
Nickel Oxide NiO 99 MERCK
Potassium hydroxide KOH 99 BDH
Sodium hydroxide NaOH 99 BDH
Vanadyl sulfate VO(SO4).5H2O 99 MERCK
pentahydrate
Urea NH2CONH2 99.5 THOMAS BAKER
Zinc Oxide ZnO 99 MERCK
2.2 Experimental Methods:-
2.2.1 Preparation of Room Temperature Ionic Liquids (RTILs):-
Ionic liquid was prepared by mixing a proper amount of aluminum nitrate
nanohydrate [Al(NO3)3.9H2O] or hydrated ammonium alum
[NH4Al(SO4)2.12H2O] either with urea [NH2CONH2] or acetamide
[CH3CONH2] were milled, mixed together and heated with gentle stirring
until clear colorless liquids were obtained that left to cool and kept sealed in
container for further use as follow:

2.2.1.1 Ionic liquid preparation with acetamide:

- Aluminum nitrate and acetamide were prepared in different mole ratios and
among them two mole ratios of 1:2.4 and 1:22 were selected for the study due
to their proper stability. The mixtures were heated at a temperature of 50 °C
for 30 min and 80 °C for 1 hour respectively.
Aluminum nitrate:acetamide of 2:1 mole ratio showed melting point of 26 °C,
while 1:1 mole ratio gave higher melting point of 50 °C. However, when the
mole ratio of aluminum nitrate was less than acetamide gave much lower
melting point of (-20 °C) for 1:1.5-1:2.65 mole ratios and (-25 °C) for 1:4 up
to the liquid 1:22 mole ratios.
- Ammonium alum and acetamide in the mole ratio of 1:12 (ASIL) heat
gradually from 25 °C to 80 °C for 10 hours produced colorless liquid[78].

2.2.1.2 Ionic liquid preparation with urea:

- Hydrated aluminum nitrate and urea salts in the mole ratio of (1:1.2) (UNIL)
were heated gradually from room temperature to 80 °C for 3 hours, to obtain
colorless liquid [80].
- Ammonium alum and urea in the mole ratio of (1:5) (USIL) were also
heated gradually from room temperature to 80 °C for 3 hours producing
colorless liquid [78].

2.2.2 Added salts to ionic liquids:-

- 0.1 M blue solution of vanadyl sulfate pentahydrate prepared in ammonium
alum:urea (USIL) that heated to 80 °C for 2hrs.
- 0.1 M green solution of Nickel Oxide prepared in ammonium alum:urea
(USIL) that heated to 80 °C for 2hrs.
- 10 ml of 0.1 M blue solution of Cupric Oxide prepared in ammonium
alum:urea (USIL) that heated to 80 °C for 2hrs.
- 10 ml of 0.1 M colorless solution of Zinc Oxide prepared in ammonium
alum:urea (USIL) that heated to t 80 °C for 2hrs.
- 10 ml of 0.1 M colorless solution of Potassium hydroxide prepared in
ammonium alum:urea (USIL) that heated to 80 °C for 2hrs.
- 10 ml of 0.1 M colorless solution of Magnesium Oxide prepared in
ammonium alum:urea (USIL) that heated to 80 °C for 2hrs.
- 10 ml of 0.01 M colorless solution of Calcium Oxide prepared in
ammonium alum:urea (USIL) that heated to 80 °C for 2hrs.
- 10 ml of 0.1 M colorless solution of Sodium hydroxide prepared in
aluminum nitrate:acetamide (AN2IL) that heated to 80 °C for 2hrs.
- 10 ml of 0.1 M colorless solution of Sodium hydroxide prepared in
aluminum nitrate:urea (UNIL) that heated to 80 °C for 2hrs.
- 10 ml of 0.1 M colorless solution of Barium Oxide prepared in aluminum
nitrate:urea (UNIL) that heated to 80 °C for 2hrs.
2.3 Instruments and measurements:-
2.3.1 Simultaneous Thermal Analysis (STA):-
Thermal behavior of ionic liquids was investigated using LINSEIS
Simultaneous thermal analyzer (STA PT1000), with platinum Evaluation
V1.0.89 software. Ionic liquid samples were heated using alumina crucibles
under air atmosphere with heating rate of 10 °C/min and sample weight of
(23-25 mg) at room temperature up to 500 °C. The instrument was calibrated
using melting points of Aluminum, Indium and Lead, that was performed in
chemistry department of Al-Nahrain University.

2.3.2 X-Ray Diffraction (XRD):-

The crystalline and phase identification of samples were determined using
X-ray Diffractometer (PAN analytical Philips, X Pert PRO MPD PW 3040)
employing monochromatized radiation source of Cu-Kα of 1.5408 °A. The
voltage and current intensities were 8.5 kV*A. All samples were scanned in
the range of 20° to 80° 2θ with a step size of 0.01 and step time of 0.2 Sec. at
room temperature 20 °C that was performed in physics department of Al-
Nahrain University.

2.3.3 Fourier Transform Infra-Red Spectrophotometer (FTIR):-

The infrared spectra were measured using F.T.IR spectroscopy BRUKER,
with ALPHA module, using attenuated total reflector (ATR) equipped with
diamond composite crystal accessory. Each sample was scanned 25 times in
the range of wave number (4000-400) cm-1 at a resolution of 4 cm-1, that was
performed in chemistry department of Al-Nahrain University.
2.3.4 Conductivity, Density and Freezing Point measurements:-
The specific conductance was measured using HANNA instrument H1
9811 in (mS/cm), that was performed in chemistry department of Al-Nahrain
University. Density was measured using gravimetric density bottle, (5 ml) in
size at room temperature. Freezing temperatures obtained from a thermometer
immersed inside the tube containing 1 ml of ionic liquid stored in deep
freezing refrigerator and the temperature was recorded when the sample
changed its state.
Chapter Three
Results &
Discussion
 Chapter Three
Results and Discussion
Five room temperature ionic liquids; namely hydrated aluminum nitrate:
acetamide in two mole ratios [(1:2.4, ANIL) and (1:22, AN2IL)],
alum:acetamide, ASIL (1:12 mole ratio), alum:urea, USIL (1:5 mole ratio)
and hydrated aluminum nitrate:urea, UNIL (1:1.2 mole ratio) were prepared
for this study. They have the advantages of being stable towards air and
moisture at room temperature. Thermal properties of these ionic liquids alone
and with the additives have not yet been investigated; therefore thermal
measurements and thermal properties have been covered by this work to
establish their usefulness as thermal storage liquids.
Some thermo-physical properties such as melting point, decomposition
temperature, density, conductivity, heat of fusion, entropy, heat capacity and
thermal energy storage capacity were determined with and without the
addition of some enhanced materials, such as alkali metal hydroxides NaOH
and KOH, alkaline earth metal oxides MgO, CaO and BaO and transition
metal oxides VOSO4.5H2O, NiO, CuO and ZnO.
3.1 Thermal Analysis(TGA/DTG& DSC), ATR-FTIR spectroscopy
a and X-ray diffraction (XRD)of Ionic Liquids:-
These five RTILs: (ASIL, USIL, ANIL, AN2IL and UNIL) were heated to
500 °C. Thermal events are normally due to phase transition and
decomposition is of two types either exothermal or endothermal according to
the nature of the process and the material relied can be identified by
appearance of exothermic and endothermic peaks that help to identify thermal
changes occurred in ionic liquid. Thermogravimetric analysis and its
derivative (TGA/DTG) and Differential Scanning Calorimetry (DSC); both
combined within single measurement through Simultaneous Thermal
Analysis (STA).
3.1.1 ATR-FTIR spectroscopy, thermal decomposition behavior X-ray
diffraction (XRD) of hydrated ammonium aluminum sulfate:acetamide
(ASIL):-
The infrared spectrum of the ASIL Fig.(3-1), showed the appearance of
characteristic absorption bands resembled its components acetamide and
[101-103]
ammonium aluminum sulfate dodecahydrate . Two strong stretching
vibration bands at symmetric 3148 and asymmetric 3298 cm-1 of υ(N-H)
which attributed to –NH2 vibration in acetamide were shifted to higher wave
number (3191 and 3345) cm-1 respectively in AS ionic liquid. The stretching
vibration band of υ(C-H) appeared at (2817) cm-1 also shifted to higher
frequency (2824) cm-1. While stretching vibration bands of υ(C=O) at (1671)
cm-1, υ(C-N) at (1010 and 1144) cm-1 were shifted to lower wave numbers
(1650) cm-1 and (1127) cm-1 respectively in ASIL. The bands related to
hydrated ammonium aluminum sulfate showed the appearance of significant
stretching vibration bands (3188 and 3321) cm-1 were shifted to higher
frequencies (3121 and 3344) cm-1 in ASIL. The broad stretching vibration
band of υ(O-H), attributed to the H2O molecules at (2884) cm-1 reduced in AS
ionic liquid. The stretching vibration bands of υ(S-O) attributed to –SO4 at
(1074) cm-1 shifted to higher frequency (1127) cm-1, and the stretching
vibration bands of υ (Al-O) at (914 and 581) cm-1[104-107] shifted to lower
frequencies and (869 and 462) cm-1 respectively; as illustrated in Table (3-1).
 100
80
Transmittance [%]

60
40
20
0

3344.84
3321.06
3298.04
3191.36
3188.44
3147.67

2883.85
2823.84
2816.60

1650.35
1616.32

1432.18
1394.55
1386.47

1207.53
1143.93
1126.58
1074.40
1010.27
913.71
869.30
868.28

687.83
682.88
581.11
557.90
462.93
453.73
3500 3000 2500 2000 1500 1000 500
Wavenumber cm-1

Fig.(3-1): FTIR of (hydrated

C:\OPUS_7.0.129\Data\Dr.hadi\hadiA.0 Sampleammonium
description aluminum
Instrument sulfate: acetamide, ASIL with
type and / or accessory 1:12
09/04/2014

mole ratio) (black line), hydrated

C:\OPUS_7.0.129\Data\Dr.hadi\sulfate.0 ammonium
Sample description Instrumentaluminum sulfate (blue line) and acetamide
type and / or accessory 21/12/2014
C:\OPUS_7.0.129\Data\Dr.hadi\hadiAS1.0 Sample description Instrument type and / or accessory 06/04/2014
(red line).
Page 1/1

Table (3-1): FTIR vibration frequencies of hydrated ammonium aluminum

sulfate:acetamide, ASIL with 1:12 mole ratio.
Compounds H2NCOCH3 NH4Al(SO4)2.12H2O ASIL
group
υ(N-H) 3148 & 3298 3188 & 3321 3191 & 3345
υ(O-H) - 2884 3000 - 3200
υ(C-H) 2817 - 2824
υ(S-O) - 1074 1127
υ(C=O) 1671 - 1650
υ(C-N) 1144 & 1010 - 1127
δ(N-H) 1386 1432 1395
υ (Al-O) - 914 - 581 869 - 462

Thermogravimetric measurements of ASIL (24.06 mg), Fig.(3-2) showed

two decomposition stages started from 203 °C reached to 500 °C with total
weight loss of (85.29 %, -20.52 mg) this weight loss was associated with
changes in heat through three endothermic peaks; the first was an
endothermic peak with an enthalpy of -250.51 kJ/kg refer to the sensible heat
stored in ASIL which in comparable with other thermal energy storage
materials. Other ionic liquids show relatively small values of heat of fusion
which are around 50 kJ/kg. On the other hand, the inorganic materials have a
very high heat of fusion of around 200 to 500 kJ/kg and the organic materials
including paraffins show these values around 100 to 200 kJ/kg. Thus ASIL
can be enclosed between organic and inorganic material. The
second/endothermic peak recorded an enthalpy of decomposition of -812.55
kJ/kg in a temperature range of 184 to 230 °C related to the decomposition of
ASIL in the first stage in which (58.40 %, -14.05 mg) weight percent is lost in
the temperature range of (203 to 235) °C that reached its maximum
decomposition at 211 °C with the possible candidate evolution products from
ASIL of [NH4Al(SO4)2.12H2O:12NH2COCH3], including water molecules
based on thermal decomposition of ammonium alum in which water
evaporated around 100 °C as shown in equation (3.1), in addition to the
partial decomposition of acetamide giving 6NH3 and 6CH3COOH based on
the decomposition of acetamide[108,109] at 425 °C (equation 3.2). These agreed
with calculated weight loss of (58.40%), thus the first decomposition stage of
ASIL was suggested as in equation (3.3):
NH4Al(SO4)2.12H2O(s)NH4Al(SO4)2(s)+12H2O(g) at 200 °C … (3.1)
2CH3CONH2(s)  CH3COOH(g) + NH3(g) + CH3CN(g) 425–545 °C…(3.2)
1. First decomposition stage was:
NH4Al(SO4)2.12H2O/12NH2COCH3 NH4Al(SO4)2+12H2O(g)+6CH3CN
+6NH3(g)+6CH3COOH(g) ...(3.3)
The initial decomposition temperature at 203 °C of the ionic liquid gave
evidence to the new nature of interaction in ionic liquid differs from these
experienced by it components ammonium alum and acetamide. As the above
temperature of water is much higher than the evaporation temperature of
water form Ammonium aluminum sulfate (around 100 °C) and in the same
sense much lower than the starting decomposition temperature of acetamide
alone (425 °C).
The second decomposition stage with weight loss percent of (26.89 %, -6.47
mg) in temperature range of (235 to 475) °C showed small exothermic
behavior between 240 °C to 250 °C could be referred to slow decomposition
of ammonium aluminum sulfate and complete decomposition of acetamide.
It's possible that the decomposition products of this stage were NH3, H2O,
SO3 and 6CH3CN that evolved from ammonium aluminum sulfate
decomposition[104] as shown in equation (3.4) and acetamide decomposition
(equation 3.2) that agreed with calculated weight loss percent 26.87 % as
shown in equation (3.5):
2NH4Al(SO4)2(s)Al2(SO4)3(s)+ 2NH3(g)+H2O(g)+SO3(g) 200 –500 °C
……………………………………………………………………..…(3.4)
2. Second decomposition stage was:
NH4Al(SO4)2(s)+6CH3CN(s)0.5Al2(SO4)3+NH3(g)+0.5H2O(g)+0.5SO3(g)
+ 6CH3CN(g) … (3.5)
 Figure (3-2): Thermogravimetric Analysis TGA (1), Differential Thermal Analysis DTG
(2), Differential Scanning Calorimeter DSC (3) of (hydrated ammonium aluminum sulfate:
acetamide, ASIL with 1:12 mole ratio) heated from room temperature to 500 °C at 10
°C/min.
The final decomposition products resulted from heating this ionic liquids to
500 °C was analyzed by X-ray diffraction Figure (3-3) and FTIR
spectroscopy Figure (3-4) to identify the remaining white powder. The X-ray
found the white powder to be pure crystalline rhombohedral aluminum sulfate
as shown in Table (3-2) with crystallite size of 48.151nm calculated from
Scherer equation [105]:
D=k*λ/β*cosθ …… (3.6)
Where k is a constant ~0.9, λ is the wave length of X-ray (1.5406 A°, β is the
full width of diffraction peak at half maximum (FWHM) intensity, 0.2952 and
θ is the Bragg angle, (25.437/2). The calculated crystallite size of aluminum
sulfate agreed with other report [105].
Fig.(3-3): X-ray diffraction of (hydrated ammonium aluminum sulfate: acetamide, ASIL
with 1:12 mole ratio) after heating it to 500 °C.
D = 0.9*1.5406*10 nm/0.2952*cos(25.437/2) = 48.151 nm –

The vibrational frequencies of the white powder after heating ASIL to

500°C, (Fig.3-4) indicated the disappearance of amide and hydroxyl group
bands with increased intensities of bands belong to sulfate (SO4-2) stretching
vibration at 1178.32cm-1[106] and aluminum-oxide Al-O stretching vibration at
497.58 to 678.78 cm-1[107]. This could be taken as further prove to
decomposition of ASIL producing aluminum sulfate Al2(SO4)3.
Table (3-2): X-ray data of the product of (hydrated ammonium aluminum
sulfate:acetamide, ASIL with 1:12 mole ratio) heated up to 500°C compared with
Al2(SO4)3 standard data[110].
2θ 2θ Intensity Intensity Miller indices
(measured) (reference) (measured) Al2(SO4)3 (reference) h k l[110]
20.969 20.934 17 20 104
24.181 24.780 34 20 006
25.437 25.427 100 100 113
30.603 30.644 26 17 024
33.535 33.497 18 18 116
33.675 - 16 -
34.233 34.222 11 10 211
34.373 35.036 11 2 122
37.910 37.933 6 5 214
40.889 40.777 7 7 303
44.333 44.118 6 6 119
45.403 45.545 4 6 217
52.291 52.222 5 5 226
55.363 55.549 6 4 211
56.247 56.139 5 6 137

The recorded weight of final product from TGA/DTG was (14.71 %, 3.54
mg) agreed with calculated weight percent of (14.73%) calculated on the
bases of sample weight of ionic liquid if completely decomposed to Al 2(SO4)3
also supported the predicted final formation of aluminum sulfate from X-ray
diffraction and FTIR spectroscopic measurements. The following equation
(3.7) summarized the overall decomposition of ASIL:
NH4Al(SO4)2.12H2O/12NH2COCH312.5H2O(g)+7NH3(g)+6CH3COOH(g)+
000000000000000000000000.5SO3(g)+6CH3CN(g) +0.5Al2(SO4)3(s) ... (3.7)
 80
Transmittance [%]

60
40
20
0

3852.59

3731.11

3344.84

3191.36

2823.84

2356.71
2301.11

2121.91
2029.49

1650.35

1394.55

1207.53
1178.32
1126.58

869.30

678.78

557.90
497.58
462.93
3500 3000 2500 2000 1500 1000 500
Wavenumber cm-1

Fig.(3-4): FTIR of (hydrated ammonium

C:\OPUS_7.0.129\Data\Dr.hadi\AS800C.0
Sample description
aluminum sulfate: acetamide, ASIL with
Instrument type and / or accessory 24/06/2014
1:12 mole ratio) (black line) and (red line) after heating it to 500 °C.
C:\OPUS_7.0.129\Data\Dr.hadi\hadiAS1.0 Sample description Instrument type and / or accessory 06/04/2014

Page 1/1

3.1.2 ATR-FTIR spectroscopy, Thermal decomposition behavior and X-ray

diffraction (XRD) of hydrated ammonium aluminum sulfate: urea (USIL):-
Initial identification of the US room temperature ionic liquid by FTIR
Fig.(3-5), showed the appearance of characteristic absorption bands resemble
to its components urea and ammonium aluminum sulfate dodecahydrate[101-
103]
. The two strong stretching vibration band of υ(N-H) which attributed to –
NH2 either in urea at (3326 and 3342) cm-1 or attributed to –NH4+ in
hydrated ammonium aluminum sulfate at (3188 and 3429) cm-1 were shifted
to lower wave number (3199 and 3340) cm-1 in ionic liquid. But the
stretching vibration band of υ(O-H) either in urea at (3200) cm-1 or the broad
stretching vibration band centered at (2884) cm-1 attributed to the H2O
molecules in hydrated ammonium aluminum sulfate that might made
hydrogen bonding with (C=O) might be responsible for the viscose nature of
US ionic liquid shifting to higher wave number (3400-2900) cm-1 in ionic
 liquid effecting the stretching vibration bands υ(C=O) at (1593) cm-1 to shift
to lower wave number (1591) cm-1. The bands related to hydrated ammonium
aluminum sulfate show the appearance of stretching vibration bands of υ(S-O)
attributed to –SO4 at (1074) cm-1, and the stretching vibration bands of υ (Al-
O) at (914 - 581)cm-1[104-107] which shifted in ionic liquid to lower frequencies
(1060) cm-1 and (771 - 537) cm-1 respectively; as illustrated in Table (3-3).
100
80
Transmittance [%]

60
40
20

3426.58
3340.83
3327.65
3321.06
3252.68
3199.92
3188.44

2883.85

1676.06
1616.32
1590.63
1456.28
1432.18

1146.75
1074.40
1060.30
1053.20
999.96
913.71
785.52
771.00
715.38
695.65
682.88
589.31
581.11
537.41
478.67
3500 3000 2500 2000 1500 1000 500
Wavenumber cm-1

Fig.(3-5): FTIR of (hydrated

C:\OPUS_7.0.129\Data\Dr.hadi\sulfate.0 Sampleammonium
description aluminum
Instrument type and / or sulfate:urea,
accessory USIL with 1:521/12/2014
mole
ratio) (black line), hydrated ammonium aluminum sulfate (blue line) and urea (red
C:\OPUS_7.0.129\Data\Dr.hadi\hadiU.0 Sample description Instrument type and / or accessory 09/04/2014
C:\OPUS_7.0.129\Data\Dr.hadi\hadiUS.0 Sample description Instrument type and / or accessory 06/04/2014
line).
Page 1/1
 Table (3-3): FTIR vibration frequencies of hydrated ammonium aluminum sulfate:urea,
USIL with 1:5 mole ratio.
Compounds H2NCONH2 NH4Al(SO4)2.12H2O USIL
group
υ(N-H) 3326 & 3328 3188 & 3321 3199 & 3340
υ(O-H) 3200 2884 3400-2900
υ(S-O) - 1074 1060
υ(C=O) 1593 - 1591
υ(C-N) 1142 - 1060
δ(N-H) 1442 1432 1456
υ(Al-O) - 914 - 581 771 - 537

Thermal analysis of USIL (20.06 mg) by TGA/DTG and DSC

measurements, Fig.(3-6) showed high thermal stability reached 280 °C with
large enthalpy value -2434.84 kJ/kg in which heat absorbed through two
stages as a resulted of two endothermic peaks (-2216.83 and -218.01) kJ/kg at
a temperature ranges of (109.6 – 163.5) °C and (200.2 – 238.8) °C
respectively. These two endothermic peaks might be referred to solid to liquid
transition due to non-eutectic mixture of USIL. Above 280 °C two
decomposition stages appeared giving total weight loss (68.54%, -16.49 mg)
up to 517 °C. The recorded weight lost in first decomposition stage was
(36.66 %, -8.82 mg) at a temperature range 280-336 °C associated with first
decomposition peak which include a complex decomposition process
exothermal and endothermal resulted in small value of ∆H in endothermic
value of -40.37 kJ/kg reached to maximum rate of decomposition at 296 °C
characteristic with rapid gaseous evaporation of water, ammonia and isocynic
acid. Equation (3.9) was suggested that based on the calculated 36.66 %
weight loss of decomposition of both ammonium alum as stated earlier
(equation 3.1) and urea which reported to evolve HNCO and NH3 above its
melting temperature to 360 °C[111,112]:
H2NCONH2NH3(g)+HCNO(s) … (3.8)
1. First decomposition step was:
NH4Al(SO4)2.12H2O/5CO(NH2)2NH4Al(SO4)2.4CO(NH2)2+12H2O(g)+
+++++++++++++++++ ++++++++++NH3(g)+HCNO(g) … (3.9)
The weight loss percent (31.88 %, -7.67 mg) of the second decomposition
stage of USIL in the temperature range between 336 °C to 517 °C, was
associated with libration of heat in an endothermic peak with enthalpy of -
51.19 kJ/kg with maximum rate of decomposition at 492 °C that attributed to
decomposition of remaining urea evolving ammonia and isocynic acid gases
that agree with the calculated weight loss percentage of 31.87 % as illustrated
in equation (3.10):
2. Second decomposition stage was:
NH4Al(SO4)2/4CO(NH2)2NH4Al2(SO4)2+4NH3(g) +4HCNO(g) … (3.10)
In similar examination procedure, the final white powder obtained from the
decomposition of USIL was also examined by X-ray diffraction (Fig.3-7 and
Table 3-4) and was found to has similar diffraction data to hexagonal
NH4Al(SO4)2 with crystalline size of 36.023 nm calculated from equation
(3.6) with the full width of diffraction peak at half maximum (FWHM)
intensity, β = 0.3936 and 2θ of 24.134/2.
 Figure (3-6): Thermogravimetric Analysis TGA (1), Differential Thermal Analysis DTG
(2), Differential Scanning Calorimeter DSC (3) of (hydrated ammonium aluminum sulfate
:urea, USIL with 1:5 mole ratio) heated from room temperature to 517 °C at 10 °C/min.

Figure (3-7): X-Ray diffraction of (hydrated ammonium aluminum sulfate:urea, USIL with
1:5 mole ratio) after heating up to 500°C.
 However, FTIR vibrational bands Fig. (3-8) indicated, an intense sulfate
vibrational frequency at maximum of 1171.17 cm-1 and Al-O stretching at
410.07-682.16 cm-1 amine vibrational bands at 1647.05 cm-1 with small
intensity, in contrast to the completely disappearance of latter frequency in the
white powder of final decomposition of ASIL at similar temperature of 500
°C.
Table (3-4): X-ray data of the product of (hydrated ammonium aluminum sulfate:urea,
USIL with 1:5 mole ratio) heated up to 500°C compared with NH4Al(SO4)2 standard
data[113].
2θ 2θ Intensity Intensity Miller indices
(measured) (reference) (measured) NH4Al(SO4)2 h k l[113]
(reference)
21.435 21.435 4 4 002
24.134 24.111 100 100 101
25.251 - 6 -
30.557 30.591 20 28 102
30.650 - 19 -
32.325 32.375 15 12 003
37.957 37.833 19 15 110
39.399 39.347 6 3 103
43.914 43.715 5 2 004
49.080 49.239 6 7 104
49.406 49.410 7 6 202
60.575 60.067 7 3 105
60.715 60.698 7 7 211
64.019 64.048 4 5 212
68.441 68.582 7 6 300
68.580 69.148 7 7 115
68.999 69.622 7 2 301
 The recorded weight percent obtained from TGA/DTG of USIL final
product was found to be (31.46%, 7.57 mg) which in agreement with
calculated weight percent of 31.47% based on the formation of NH4Al(SO4)2
as final product from USIL decomposition at 517 °C. Which support the
NH4Al(SO4)2 supported by X-ray diffraction and FTIR spectroscopic
measurements.

Fig.(3-8): FTIR of (hydrated ammonium aluminum sulfate:urea, USIL with 1:5 mole
ratio) (black line), and (red line) after heating to 500°C.

3.1.3 ATR-FTIR spectroscopy, Thermal decomposition behavior and X-ray

diffraction (XRD) of hydrated aluminum nitrate:acetamide (ANIL, 1:2.4
mole ratio) and (AN2IL, 1:22 mole ratio):-
The FTIR analysis of the ANIL Fig.(3-9a), showed the appearance of
both characteristic absorption bands of its components (i.e. acetamide and
aluminum nitrate nanohydrate)[101-103] with noticeable shifting. The two strong
stretching vibration band of υ(N-H) which attributed to –NH2 in acetamide at
3147 cm-1 and 3297 cm-1 shifted to higher frequency 3344 cm-1 in ionic liquid
while stretching vibration band of υ(C-H) at 2817 cm-1 that may be
overlapped with the broad band of υ(O-H) started from 2700 cm-1 to 3500 cm-
1
. Stretching vibration bands υ(C=O) at 1671 cm-1, υ(C-N) at 1146 - 456 cm-1
and bending vibration band υ(N-H) at 1392 cm-1 shifted to lower wave
numbers 1330 cm-1. The hydrated aluminum nitrate showed the appearance
of significant broad stretching vibration band of υ(O-H) centered at 2947 cm-1
attributed to the H2O molecules that related to hydrogen bond formation with
the oxygen of the carbonyl group of acetamide, shifting to higher frequency
3006 cm-1 in ionic liquid. Other frequencies of stretching vibration bands of
υ(N-O) resulted from –NO3 group at 1334 cm-1 shifted to higher frequency
1387 cm-1 and 1335 cm-1 in ionic liquid and the stretching vibration bands of
υ (Al-O) at 880 - 685 cm-1 were shifted to lower frequency 886-586 cm-1 in
ionic liquid as illustrated in Table (3-3) and Fig.(3-9a).
The shifting of FTIR either to lower or higher frequencies in ionic liquids
compared to the frequencies of the ionic liquid components alone, taken as an
indication to the chemical interaction between its components forming new
coordination ions in the liquid state [78].
The infrared spectrum of the AN2IL Fig.(3-9b), showed different
characteristic absorption bands compared with ANIL of same components[101-
103]
but with different mole ratios (1:2.4 compared to 1:22 respectively). The
two strong stretching vibration band of υ(N-H) which from –NH2 in
acetamide at (3147 and 3297) cm-1 were shifted to higher frequencies (3197
and 3342) cm-1 in ionic liquid with the disappearance of . υ(C-H) which
showed appeared at (2817) cm-1. The stretching vibration bands of υ(C=O) at
(1671) cm-1 and υ(C-N) at (1146-456) cm-1 were shifted to lower wave
numbers 1653, 1124 cm-1 respectively yet appeared at the same positions as
in ANIL with limited shifting. The bands related to υ(O-H) of hydrated
aluminum nitrate appeared at (2947) cm-1 with small intensity in AN2 ionic
liquid in contrast to that in AN ionic liquid which showed broad band. The
 stretching vibration bands of υ(N-O) of –NO3 at (1334) cm-1 shifted to higher
frequency (1387 and 1335) cm-1 respectively in ANIL and AN2IL and
stretching vibration bands of υ (Al-O) at (880 to 685) cm-1 shifted to lower
frequency of 870 to 559 cm-1 respectively as illustrated in Table (3-5).
100
80
Transmittance [%]

60
40
20

3343.69
3296.85

3147.11

3006.26

2816.98

2491.19

1671.30
1652.71
1627.85
1587.92

1392.20

1145.75

886.12
824.31

688.54
586.63
575.22
455.82
3500 3000 2500 2000 1500 1000 500
Wavenumber cm-1

Fig.(3-9a): FTIR of (hydrated

C:\OPUS_7.0.129\Data\Dr.hadi\hadiAN.0
C:\OPUS_7.0.129\Data\Dr.hadi\hadiA.1
aluminum
Sample description
Sample description
nitrate: acetamide, ANIL with 1:2.4)06/04/2014
Instrument type and / or accessory
Instrument type and / or accessory
mole
09/04/2014
ratio (black line), hydrated
C:\OPUS_7.0.129\Data\Dr.hadi\hadiN.0 Sample aluminum
description nitrate
Instrument type(blue line) and acetamide in (red09/04/2014
and / or accessory line).
Page 1/1
 100
80
Transmittance [%]

60
40
20

3850.32

3742.65

3529.85

3342.06
3296.77
3197.17
3147.14

2946.61

2816.99

2535.43

2361.09

2121.92

1652.61
1636.87
1626.79

1385.61
1334.72
1333.55
1219.36
1124.36
1044.40
1004.49
880.03
870.46
870.46
828.63
810.38
782.92
685.09
574.61
559.50
454.09
3500 3000 2500 2000 1500 1000 500
Wavenumber cm-1

Figure (3-9b): FTIR of (hydrated

C:\OPUS_7.0.129\Data\Dr.hadi\hadiA.1
aluminum
Sample description
nitrate: acetamide, AN2IL with 1:22
Instrument type and / or accessory
mole
09/04/2014
C:\OPUS_7.0.129\Data\Dr.hadi\hadiN.0 Sample description Instrument type and / or accessory 09/04/2014
ratio) (black line),22.1hydrated
C:\OPUS_7.0.129\Data\Dr.hadi\AN aluminumInstrument
Sample description nitrate type (blue line) and acetamide in (red17/06/2014
and / or accessory line).
Page 1/1

Table (3-5): FTIR vibration frequencies of hydrated aluminum nitrate: acetamide, ANIL
with 1:2.4 and AN2IL with 1:22 mole ratios.
Compounds H2NCOCH3 Al(NO3)3.9H2O ANIL (1:2.4) AN2IL
group (1:22)
υ(N-H) 3147 & 3297 - 3344 3197 & 3342
υ(O-H) - 2947 3006 3000 - 3200
υ(C-H) 2817 - - -
υ(N-O) - 1334 1330 1386 & 1335
υ(C=O) 1671 - 1653 1653
υ(C-N) 1146 - 456 - 1140 1124
δ(N-H) 1392 - 1330 1386 & 1335
υ(Al-O) - 880 - 685 886 - 586 870 - 559

However, ANIL (24.02 mg) appeared to have similar thermal behavior as

AN2IL (24.22 mg), (Fig.3-10 and Fig.3-11) respectively in number of its
decomposition stages and endothermic /exothermic DSC peak with different
weight lost percents at each stage and area under their curves related to
different acetamide percent which increased from 2.4 to 22 causing such
different interactions influencing not only the decomposition temperature but
also further thermo-physical properties. Since ANIL and AN2IL were found
to be stable until 232 °C and 276 °C respectively with two endothermic peaks
in ANIL with negligible weight loss of an enthalpy value of -1536.4 kJ/kg,
(Fig.3-10) compared to an enthalpy of -3697.02 kJ/kg in AN2IL (Fig.3-11).
Both ANIL and AN2IL undergo three decomposition stages showing total
weight loss percents of (78.56 %, -18.87 mg) and (79.85 %, -19.34 mg)
respectively. ANIL decompose in temperature range of (232-254) °C as this
first decomposition stage gives (27.89 %, -6.70 mg) with a significant amount
of librated heat with small enthalpy -1.56 kJ/kg referred to gaseous
evaporation of water molecules through fast weight loss curve (i.e. fast
decomposition rate) that reached its maximum rate at 241 °C which agreed
with calculated weight loss percent of 27.87 % equation (3.13), followed by
second decomposition step, equation (3.14) involve weight a loss percent
(43.46 %, -10.44 mg) at temperature range of 254 to 351 °C reached its
maximum rate of decomposition at 273 °C with endothermic peak of recoded
enthalpy of -270.28 kJ/kg referred to the gaseous evaporation of water
molecule, nitric dioxide, oxygen and pyrolysis of organic portion; acetamide
giving ammonia, CH3COOH and CH3CN gases due to the calculated weight
loss percent of 43.48 %, resemble to the decomposition of acetamide
alone[108,109] and thermal decomposition of pure aluminum nitrate [104] as
expressed in equation (3.12) that assists the suggestion of thermal
decomposition of ANIL and AN2IL.
Al(NO3)3.9H2O  amorphous-Al2O3 at (200-700) °C …(3.12)
1. First decomposition stage of ANIL was:
Al(NO3)3.9H2O/2.4NH2COCH3(l)Al(NO3)3.H2O/2.4NH2COCH+8H2O(g)
……………………………………………………………………… …(3.13)
2. Second decomposition stage was:
Al(NO3)3.H2O/2.4NH2COCH3Mix.(Al(NO3)3+Al2O3)/NH2COCH3+H2O(g) +
O2(g)+2NO2(g)+0.7CH3COOH(g)+0.7CH3CN(g)+0.7NH3(g) … (3.14)
The first and second decomposition steps of ANIL appeared to merge in
one step in AN2IL at a temperature between (276-332) °C with weight loss
percent of (68.74 %, -16.65 mg) had an endothermic peak (Fig.3-11) with
enthalpy of -302.70 kJ/kg reaching a maximum decomposition rate at 291 °C
in which water molecules, NO, NO2 and O2 evaporated in addition to the
excess acetamide that decomposing produce NH3, CH3COOH and CH3CN
gave calculated weight loss of 68.74 % as illustrated in equation (3.15).
Decomposition of aluminum nitrate (equation 3.15) assisted with calculated
weight loss percent of 68.74 % and with equation (3.12) in which amorphous
alumina reported to be produced in temperature above 200 °C.
1. First decomposition stage of AN2IL:
Al(NO3)3.9H2O/22NH2COCH3(l)am-Al2O3/8NH2COCH3+NO(g)+
9H2O(g)+2NO2(g)+ 1.25O2(g)+7CH3COOH(g)+7NH3(g)+ 7CH3CN(g) … (3.15)
and the second decomposition stage was:
am-Al2O3/8NH2COCH3am-Al2O3/5NH2COCH3+1.5NH3+1.5CH3COOH
+++++++++++++++++++++++++++++1.5CH3CN … (3.16)
The second decomposition stage of AN2IL gave (11.11 %, -2.69 mg)
weight loss percent at a temperature range of (332-500) °C accompanied with
an exothermic crystallization peak and exothermic peak with an enthalpy
change of 101.07 kJ/kg referred to crystallization of the remaining product
followed by endothermic peak with enthalpy of -12.93 kJ/kg resulted from
decomposition giving calculated weight loss percent of 10.58 % as illustrated
in equation (3.16). The third decomposition stage of ANIL with weight loss
percent of (7.20 %, -1.73 mg) produced in the temperature range of (350 to
500) °C accompanied with exothermic peak of enthalpy change of 106.62
kJ/kg at temperature range of 358.6 to 371.3 °C related to solid to solid
crystallization transition reaching the maximum rate of weight loss at
temperature 356 °C related to libration of nitrogen oxide and oxygen based on
the calculated weight loss percent of 7.36 % as suggested in equation (3.17).
3. Third decomposition step of ANIL was:
Mix.(Al(NO3)3+Al2O3)/NH2COCH3(s)Al2O3/NH2COCH3(s)+NO(g)+0.25O2(g)
…(3.17)

Fig.(3-10): Thermogravimetric TGA (1), Differential thermal Analysis DTG (2),

Differential scanning calorimeter DSC (3) of (hydrated aluminum nitrate: acetamide,
ANIL with 1:2.4 mole ratio) heated from room temperature to 495 °C at 10 °C/min.

The X-Ray diffraction of final decomposition products of ANIL showed

an amorphous crystalline structure (Fig. 3-12) consisting only broad bands.
Not only high resolution of X-ray Diffractometer with a step size of 0.01 and
step time of 0.2 Sec. which give minimum details, and the possibility of
forming mixture of two compounds amorphous alumina and acetamide a final
decomposing product, in addition to the expected structure of the product due
to historical behavior of the starting material aluminum nitrate nanohydrate
that form an amorphous alumina after heated it above 200 °C as illustrated in
equation (3.12) leading to such bands (Fig. 3-12).

The FTIR spectra for final decomposition products of ANIL, Figure (3-
13) showed the disappearance of amide and hydroxyl groups with small
stretching vibration band at 1535.70 cm-1 that might be referred to the
presence of carbonyl group of acetamide with shifting to higher stretching
vibration band at 1653.80 cm-1 before heating ANIL to 500 °C. The stretching
vibration bands at 556.28 to 771.25 cm-1 was related to aluminum-oxide.
Fig.(3-11): Thermogravimetric Analysis TGA (1), Differential thermal Analysis DTG (2),
Differential scanning calorimeter DSC (3) of (hydrated aluminum nitrate: acetamide,
AN2IL with 1:22 mole ratio) heated from room temperature to 496 °C at 10 °C/min.

The FTIR of final product of heating AN2IL, Figure (3-14) gave different
bands than that of ANIL. In general, most bands before heating AN2IL
remained with lower intensities after heating. The stretching vibration did not
show the bands at 2800-3500 cm-1 in which amine group has 2-peaks (3000
and 3400) cm-1 but only very broad band appeared from 2500 cm-1 to 3700
cm-1. Vibration bands at 2361.09 cm-1 and 2121.92 cm-1 related to resonate
(C≡N) bond in acetamide and the bands at around 1600 cm-1 was attributed to
carbonyl of acetamide and the broad stretching vibration band in the range
870-454 cm-1 refer to (Al-O) while bands at 1385.61 and 1334.72 cm-1 related
to nitrate group disappeared. The vibrational frequencies of nitrate group at
1385.61 cm-1 and 1334.72 cm-1 of ANIL and AN2IL was also completely
disappeared after heating ionic liquids to 500 °C.
The obtained weight of final products of heating ANIL and AN2IL were
(21.44 %, 5.15 mg) and (20.15 %, 4.88 mg) respectively of the original
weight which were similar to those calculated for both liquids of 21.30% and
20.68% based on equation (3.17) and (3.16) respectively.
The presence of acetamide in the final product from heating ANIL and
AN2IL could be due to non complete decomposition process of acetamide at
500 °C with short of experiment as the complete decomposition could be
reached at 545 °C[108,109].

Fig.(3-12): X-ray diffraction of (hydrated aluminum nitrate: acetamide, ANIL with 1:2.4
mole ratio) after heating it to 500 °C.
 100
80
Transmittance [%]

60
40
20

3027.57

1653.80

1535.70

1308.62

1043.13

593.75
556.28
3500 3000 2500 2000 1500 1000 500
Wavenumber cm-1

Fig.(3-13): FTIR of (hydrated

C:\OPUS_7.0.129\Data\Dr.hadi\an2.4 aluminum
Sample description nitrate:
Instrument type and / oracetamide,
accessory ANIL with 1:2.4 mole
05/06/2014

ratio) (black Sample

C:\OPUS_7.0.129\Data\Dr.hadi\hadiAN.0 line)description
and (redInstrument
line) type
afterand /heating
or accessory it to 500 °C. 06/04/2014

Page 1/1
100
80
Transmittance [%]

60
40
20

3850.32

3742.65

2361.09

2121.92

1652.61

1385.61
1334.72

1124.36
1044.40

870.46
828.63
782.92

559.50
454.09

3500 3000 2500 2000 1500 1000 500

Wavenumber cm-1

Fig.(3-14): FTIR of (hydrated

C:\OPUS_7.0.129\Data\Dr.hadi\AN 22.1 aluminum
Sample description nitrate:
Instrument acetamide,
type and / or accessory AN2IL with 1:2217/06/2014
mole
ratio) (black
C:\OPUS_7.0.129\Data\Dr.hadi\an22.1 line) and
Sample description (red line) after heating
Instrument type and / or accessory it to 500 °C. 19/06/2014

Page 1/1
3.1.4 ATR-FTIR spectroscopy, Thermal decomposition behavior and X-ray
diffraction (XRD) of hydrated aluminum nitrate:urea (UNIL):-
The prepared UNIL[80] was Analyzed by FTIR Fig.(3-15), that showed
characteristic absorption bands of its components[101-103] with small shifting.
The two strong stretching vibration band of υ(N-H) of –NH2 in urea at (3328
and 3427) cm-1 were shifted to higher wave number (3352 and 3454) cm-1
respectively in UNIL. In addition the stretching vibration bands of υ(C=O) at
(1593) cm-1 was shifted to higher wave numbers (1693) cm-1 while bending
vibration band δ(N-H) at (1146)cm-1 was shifted to lower wave numbers
(1036)cm-1. Significant broad stretching vibration band centered at (2946) cm-
1
of υ(O-H), in H2O molecules of hydrated UNIL may involved in hydrogen
bonding with (C=O) and shifted to higher wave number of (2984) cm-1 in
ionic liquid which might be responsible for the viscose nature of ionic
liquid. Furthermore, the stretching vibration bands of υ (Al-O) at (880 to 685)
cm-1 shifted to lower frequency of (823 to 606) cm-1, stretching vibration
bands of υ(N-O) in –NO3 at (1334 and 1637) cm-1 shifted to lower frequency
(1309) cm-1 ; as shown in Table (3-6).
 100
80
Transmittance [%]

60
40
20

3861.77

3741.52

3529.85
3454.00
3429.40
3351.90
3326.00

2984.03
2946.61

2803.05

2535.43
2501.32

1673.31
1639.75
1636.87
1593.25
1510.32
1446.10
1333.55
1309.29

1160.68
1142.27
1036.21

880.03
823.01
810.38
785.77
727.38
712.22
685.09
606.31
539.53
3500 3000 2500 2000 1500 1000 500
Wavenumber cm-1

Fig.(3-15): FTIR of (hydrated

C:\OPUS_7.0.129\Data\Dr.hadi\hadiN.0 aluminum
Sample description nitrate:
Instrument urea,
type and / or UNIL with1:1.2 mole ratio)
accessory 09/04/2014

(black line), hydrated aluminum nitrate (blue line) and urea (red line). 06/04/2014
C:\OPUS_7.0.129\Data\Dr.hadi\hadiUN.0
Sample description Instrument type and / or accessory
C:\OPUS_7.0.129\Data\Dr.hadi\hadiU.0 Sample description Instrument type and / or accessory 09/04/2014

Page 1/1

Table (3-6): FTIR vibration frequencies of hydrated aluminum nitrate: urea, UNIL with
1:1.2 mole ratio.
Compounds H2NCONH2 Al(NO3)3.9H2O UNIL
group
υ(N-H) 3426 & 3429 3454 & 3352
υ(O-H). 3200 2946 2984
υ(N-O) - 1637 & 1334 1309
υ(C=O) 1593 1639
υ(C-N) 1142 1161
δ(N-H) 1146 1036
υ (Al-O) 880 - 685 823 - 606

The TGA/DTG and DSC measurements of UNIL (23.84 mg) showed

thermal stability up to 236 °C associated with an endothermic peaks refer to
enthalpy value of -3319.94 kJ/kg followed by three decomposition stages
until 500 °C with total weight loss percent of 56.59 % with changes in heat
through two decomposition peaks as shown in Figure (3-16). First
decomposition stage related to two endothermic peaks involve small weight
loss of (3.23 %, -0.77 mg) indicated by loss of non interacted water molecule
calculated to have 4.03 % weight loss percent and the recorded weight loss of
(24.16 %, -5.76 mg) at a temperature range (236-271) °C might be related to
rapid gaseous evaporation of water molecules which agree with calculated
weight loss percent of 24.16 % related to the first decomposition endothermic
peak with enthalpy value of -28.81 kJ/kg reached maximum rate of
decomposition at 248 °C as shown in equation (3.18).
1. First decomposition stage:
Al(NO)3.9H2O/1.2CO(NH2)2Al(NO3)3.3H2O/1.2CO(NH2)2+6H2O(g)
………………………………………………………………………… (3.18)
The second decomposition endothermic peak with weight loss percent of
(16.11 %, -3.84 mg) related to an enthalpy of -216.85 kJ/kg referred to urea
decomposition giving ammonia and isocyanic acid gases that agreed with
calculated weight loss percent of 16.11 % as illustrated in equation (3.19).
2. Second decomposition stage:
Al(NO)3.3H2O/1.2CO(NH2)2Al(NO3)3.3H2O+1.2NH3(g)+1.2HCNO(g)
………………………………………………………………… …(3.19)
The recorded weight loss percent in the slow third decomposition stage gave
(16.32 %, -3.89 mg) weight loss referred to gaseous evaporation of water
molecules and nitrogen dioxide due to the calculated weight loss percent of
16.30 % as explained in equation (3.20).
3. Third decomposition stage:
Al(NO3)3.3H2OMix.(Al(NO3)3+Al2O3)+3H2O(g)+0.41NO2(g) … (3.20)
Figure (3-16): Thermogravimetric TGA (1), Differential thermal Analysis DTG (2),
Differential scanning calorimeter DSC (3) of (hydrated aluminum nitrate: urea, UNIL
with1:1.2 mole ratio) heated from room temperature to 471 °C at 10 °C/min.

The X-Ray diffraction analysis of the final product of decomposition of

UNIL at 500 °C consisting broad bands Figure (3-17) indicating an
amorphous product.
The FTIR spectra for this remaining amorphous product of UNIL, Figure (3-
18) showed, only one broad band from 3748cm-1 and 2987 cm-1 to 821 cm-1
compared to multibands of original UNIL Fig.(3-17) which hardly to be
analyze.
Al(NO3)3.9H2O/1.2CO(NH2)2(l)Mix.(Al(NO3)3+Al2O3)(s)+9H2O(g)+++++++
++++++++++++++++++++++1.2NH3(g)+1.2HCNO(g)+ 0.41NO2(g) …(3.21)
However, recorded weight obtained from TGA/DTG (43.41 %, 10.35mg)
agreed with calculated weight percent of (43.42 %) based on equation (3.21).
 Fig.(3-17): X-Ray diffraction of (hydrated aluminum nitrate: urea, UNIL with1:1.2 mole
ratio) after heating to 500 °C.
100
80
Transmittance [%]

60
40
20

3819.41
3801.16
3748.84
3673.14
3648.57

2987.14
2987.14
2987.14

1637.59
1637.59
1637.59
1541.06

1309.70
1309.70
1309.70

1042.72
1042.72
1042.72

821.95
821.95
821.95

3500 3000 2500 2000 1500 1000 500

Wavenumber cm-1

Fig.(3-18): FTIR of (hydrated

C:\OPUS_7.0.129\Data\hadiUN.0
C:\OPUS_7.0.129\Data\hadiUN+unli.0
aluminum
Sample description
Sample description
nitrate: urea, UNIL with1:1.2 mole ratio)
Instrument type and / or accessory
Instrument type and / or accessory
06/04/2014
06/04/2014
(black line)
C:\OPUS_7.0.129\Data\hadiUN+unli.0
C:\OPUS_7.0.129\Data\hadiR UN dil.0
and in (red Instrument
Sample description
Sample description
line) after
Instrument type and / heating to 500 °C.
or accessory
type and / or accessory
06/04/2014
08/04/2014

Page 1/1

3.2 Thermo-physical properties of ionic liquids:-

 Thermal data of ionic liquids of present investigation were done by TGA
and DSC. The obtained data believed to be essential for both practical
research and industrial application.
3.2.1 Thermal properties:
Thermal measurements of ionic liquids of present investigation are shown
in Table (3-7) characterized by a wide range of freezing points (-25 to 50 °C)
for different composition of these ionic liquids.
The lowest freezing temperature for the prepared these ionic liquids were
-25 °C obtained for AN2IL in the mole ratios of (1:4 to 1:22) while the
highest freezing point was 50 °C recorded for aluminum nitrate:acetamide
ionic liquid of 1:1 mole ratio and 0 °C for ASIL with 1:12 mole ratio. The
highest decomposition temperature of 280 °C was found for USIL and lower
decomposition temperature of 203 °C was recorded for ASIL, but these
temperatures indicated no relation between the melting point and
decomposition temperature of these ionic liquids. However, it was expected
that water would be evolved from these ionic liquids if heated to around 100
°C, but the absence of such evaporation indicated a strong bond of water
molecules with species of ionic liquids as weight loss was only recorded
around 203 °C. Such coordination was concluded in other work suggested
from UV spectroscopic study of USIL[79]. The ionic liquids stability may be
arrenged in the following order USIL > AN2IL > UNIL >ANIL > ASIL
based on their decomposition temperatures.
Ionic liquid composed of sulfate and urea was found to be most stable
liquid compared with other ionic liquids. This could be arise from stronger
interaction of the constituent species of the cationic or anioinic species
formed from the original salts. Once the onset temperatures were reached for
each ionic liquid the rate of decomposition of these ionic liquid was found to
be very fast.
 The different stability of these ionic liquids might also be related to the
availability of amide groups coordinated with species in the liquid state. Other
factor might be related to the two amide groups present in urea than in
acetamide adding another coordination bond to the liquid containing urea than
acetamide. If this was true then expected that urea containing ionic liquids
have more thermal stability than acetamide containing ionic liquids. However,
the AN2IL which is the second most stable as indicated in the above series
could be related to the high mole ratio of acetamide percent in this liquid (i.e.
1:22) compared to other ionic liquids, Table (3-7), and acetamide known to
have higher stability than urea (compare 425 °C with 132 °C respectively).
Acidity value, Table (3-8), of ionic liquids could be put in the order UNIL >
ANIL > AN2IL > ASIL > USIL, which indicated the formation of acidic
species of lewis type formed with cationic charges (e.g. for UNIL [Al(NO3)2.n
Urea]+ [Al(NO3)4]- ) in analogous to those reported in aluminum chloride/urea
ionic liquid[114] which required additional identification to confirm its
formula.
Table (3-7): Thermo-physical properties of five room temperature ionic liquids.
IL Tm, °C Td, ρ, Cp, E, kJ/m3
°C kg/m3 kJ/kg.°C) *105
ASIL (1:12) 0.0 203 1116 2.1 4.758

USIL (1:5) -16 280 1460 2.2 9.508

ANIL (1:2.4) -20 232 1405 1.6 5.665

AN2IL (1:22) -25 276 1168 2.4 8.438

UNIL (1:1.2) -20 236 1522 1.9 7.403

Ionic liquids containing acetamide as organic compound in the formation

showed significant effect on liquid temperature range rather than inorganic
salts, thus it was found that the temperature at which ANIL in the (1:2.4) mole
ratio remaining liquid down to -20 °C resulted from structural lattice
deformation that was difficult to rearrange to its original structural solid
lattice due to new ion formation. This resulted in freezing point reduction and
a probable tendency for glass formation on cooling, rather than crystallization.
In the case ionic liquids containing urea showed that the effect of inorganic
salts (hydrated ammonium aluminum sulfate and hydrated aluminum nitrate)
more significant rather than urea liquid range reduction, since the presence of
several different anions in these ionic liquids have the effect of significantly
decreasing the freezing point and a pronounced possible tendency for glass
formation on cooling, rather than crystallization. This would be an indicative
of inefficient packing within the crystal structures.

3.2.2 Conductivity (k):

Conductivities of these ionic liquids have no relation with their pH values
as the smaller pH value is not necessarily gave higher conductivity, Table (3-
8). UNIL showed much higher conductivity than other ionic liquids while
acetamide ionic liquids show lower conductivity than urea ionic liquids. Yet
the presence of much higher mole ratio of acetamide of 22 in AN2IL did not
show appreciable increase in conductivity. This may be related to the
hindrance of ionic mobility in ionic liquids[7].
The highest conductivity found was (9.09mS.cm-1) for UNIL at 26 °C and
reached 13.61 mS.cm-1 at 70 °C as shown in Figure(3-19). Other ionic liquids
have lower conductivities of 4.56 mS.cm-1 at 26 °C for USIL down to 1.32
mS.cm-1 at 30 °C for ASIL. The lowest conductivity value from these ionic
liquids was much higher than reported ionic liquid of [C2MIm][amino acids] (
λ= 9.1 × 10-6 to 0.65 mS.cm-1)[115] and three times higher than [N2222][Pro]
(0.46 mS.cm-1) and eight times higher than [N2222][Ser] (0.16 mS.cm-1)[116].

The conductivity of these ionic liquids was found to be directly

proportional with temperature, Fig. (3-19). However, obtained conductivities
were found to be small if compared to aqueous electrolyte solution due to the
fact that conductivity depend on the mobility of ions and high concentration
of ions in ionic liquid block the movement of ions [8].

The temperature dependence of conductivity for ANIL, as in Figure (3-19)

involved a complex interplay of short- and long-range forces that is strongly
impacted by the type and character of the cation and anion[20]. At our current
level of understanding it is not possible to accurately predict how the
conductivity of a given ionic liquid will vary with temperature. Since this
conductivity reduction may be due to ion pairs or ion aggregation.
The proportion between conductivity and temperature is apply to some
extent ; it was observed at a certain temperature the conductivity of USIL and
UNIL ionic liquids become constant with temperature increase as in the figure
(3-19) at temperature 65 °C and 50 °C respectively, result in smaller than
expected conductivity of ionic liquids that can be attributed to the reduction of
available charge carriers due to ion pairing and/or ion aggregation, and to the
reduced ion mobility resulting from the large ion size found in many ionic
liquids [3].
Table (3-8): Conductivity (k) and pH of five room temperature ionic liquids at 22 °C.
IL ASIL (1:12) USIL (1:5) ANIL (1:2.4) AN2IL (1:22) UNIL(1:1.2)
pH 2.3 4.2 0.8 1.8 0.5
k (mS/cm) 1.32 4.56 4.10 3.72 9.09
 14
13 UNIL
12 USIL
ASIL
11
ANIL
Conductivity (mS/cm)

10
9
8
7
6
5
4
3
2
1
25 30 35 40 45 50 55 60 65 70 75
o
T ( C)

Figure (3-19): Conductivity (mS/cm) of (a): hydrated aluminum nitrate:urea, UNIL with
1:1.2 mole ratio, (b): hydrated ammonium aluminum sulfate:urea, USIL with 1:5 mole
ratio), (c): hydrated ammonium aluminum sulfate:acetamide, ASIL with 1:12 mole ratio
and (d): hydrated aluminum nitrate:acetamide, ANIL with 1:2.4 mole ratio versus
temperature up to 70 °C.
3.2.3 Density:
Five ionic liquids are reviewed here on the basis of their density at room
temperature 22 oC. Relatively small variation is observed in the density of the
studied ionic liquids as shown in Table (3-7). Here, the density range from
1405 to 1522 kg/m3 for ionic liquids shown here which were higher than
density value of water ( 998 kg/m3) as most ionic liquids, which are preferred
density values of the common organic liquids used for thermal energy storage
in the vicinity of 1100 kg/m3[28]. Thus, Materials with higher density as these
five ILs help to increases the energy storage capacity (E).
 The linearity of this relation holds only up to some extent. Solid materials
at room temperature with high density obviously possess higher energy
storage capacity but many of them show a significant decrease in density in
their molten state, the inorganic materials and their eutectic mixtures used for
the same purpose have very high density ranging from 1440 to 2260 kg/m3.
Interestingly, ionic liquids being composed of organic portions exhibit
density values 1320 kg/m3 for urea and 1159 kg/m3 for acetamide, and
inorganic portions exhibit density values 1640 kg/m3 for hydrated ammonium
aluminum sulfate and 1720 kg/m3 for hydrated aluminum nitrate had a density
values lower than inorganic salts and higher than the corresponding organic
compounds. Thus ionic liquids densities can be put between the densities of
its components.
3.2.4 Enthalpy (∆H):
Enthalpy is a state function that depending only on the initial and final
point and independent in the path between them, here the measured enthalpy
represent the energy stored in ionic liquid by heating it from room
temperature to its decomposition point using DSC thermogram. Enthalpy is
one of the most important properties for a potential thermal energy storage
device. These values were calculated from the area enclosed in phase change
endothermal DSC peaks.
It's found that the enthalpy of ASIL registered the lowest value (-250.51
kJ/kg) kJ/kg obviously appeared at the first endothermic DSC peak through
temperature range (91.8-171.75) °C and the highest values found in urea
based ionic liquids with an enthalpies of -2434.84 and -3319.94 kJ/kg
recorded for USIL and UNIL respectively as shown in Table (3-9). ANIL
exhibited an enthalpy value of -1536.4 kJ/kg and this value increased in
significant amount with increasing acetamide ratio to 22 in AN2IL reaching
to an enthalpy of -3697.02 kJ/kg.
 Since large values of enthalpy leads to more efficient thermal energy
storage in comparable with other thermal energy storage materials and other
ionic liquids that show relatively small values of heat of fusion which are
around 50 kJ/kg. On the other hand, the inorganic materials have a very high
heat of fusion of around 200 to 500 kJ/kg and the organic materials including
paraffins show these values around 100 to 200 kJ/kg. Thus ionic liquids of
ASIL, USIL, ANIL, AN2IL and UNIL found to higher than most heat storage
materials.
Table (3-9): Enthalpy (∆H) and entropy (∆S) of five room temperature ionic liquids.
IL ASIL (1:12) USIL (1:5) ANIL (1:2.4) AN2IL (1:22 UNIL(1:1.2)
∆S, kJ/kg.°C -1.976 -16.321 -8.963 -17.655 -18.799
∆H, kJ/kg -250.51 -2434.84 -1536.4 -3697.02 -3319.94
∆G, kJ/kg -201.11 -2026.82 -1312.33 -3255.65 -2849.97

3.2.5 Heat capacity (Cp) and thermal energy storage capacity (E):
The heat capacities (Cp), densities (ρ), and thermal energy storage
capacities (E) of some heat storage materials are listed in Table (3-10).
Heat capacities of these ILs were elucidated from DSC thermograms, Fig. (3-
20) using Al2O3 as reference material[92] with -7.6 µV heat flow and 0.80
kJ/kg.°C heat capacity, the average base line heat flow value was -4.08 µV
and the heat flow of ionic liquids in microvolt (µV) were obtained from DSC
thermogram as showed in Figure (3-20), that can be calculated using
equation(1.4) as illustrated previously in chapter one:

Cp(sample)=(H(sample)-H(baseline)) * M(ref.)* Cp(ref.)/(H(ref.)-H(baseline))*M(sample) … (1.4)

1.Cp(ASIL)=(-15.2+4.08)µV*19.9mg*0.8 kJ/kg.°C/(-7.6+4.08)µV*24.06mg
= 2.1 kJ/kg.°C heat capacity of ASIL.
2. Cp(USIL)=(-15.8+4.08)µV*19.9mg*0.8kJ/kg.°C/(-7.6+4.08) µV*24.06mg
 = 2.2 kJ/kg.°C heat capacity of USIL.
3.Cp(ANIL)=(-12.5+4.08)µV*19.9mg*0.8kJ/kg.°C/(-7.6+4.08) µV*24.02mg
= 1.6 kJ/kg.°C heat capacity of ANIL.
4.Cp(AN2IL)=(-16.9+4.08)µV*19.9mg*0.8kJ/kg.°C/(-7.6+4.08)µV*24.22mg
= 2.4 kJ/kg.°C heat capacity of AN2IL.
5.Cp(UNIL)=(-14.2+4.08)µV*19.90mg*0.8 kJ/kg.°C/(-7.6+4.08) µV*23.84mg
= 1.9 kJ/kg.°C heat capacity of UNIL.

The values of heat capacity were found in the range of 1.6–2.4 kJ/kg ◦C for
this work Table (3-10). These values were found to be higher in case of
AN2IL, USIL, UNIIL and ASIL. The ANIL showed the least value for heat
capacity. Also was found that the lowest value of heat capacity of ionic
liquids presented in this work still higher than those ionic liquids of
[N+4444][BF4-], [N+4444][PF6-] and [N+4444][NO3-], Table (3-10).
The value of heat capacity was not significant as the most important
property of thermal energy storage capacity depends on temperature range
and density. Thus, thermal energy storage capacities calculated in the usable
temperature range (Td − Tm) of ionic liquid using the following equation [43]:

E = ρ.Cp (Td − Tm) ……………………………………... (3.22)

1. E(ASIL)= 1116 kg/m3 * 2.1 kJ/kg.°C (203- 0) °C = 4.758*105 kJ/m3

2 .E(USIL)= 1460 kg/m3* 2.2 kJ/kg.°C (280+16) °C = 9.508*105 kJ/m3
3.E(ANIL)= 1405 kg/m3 * 1.6 kJ/kg.°C (232+20) °C = 5.665*105 kJ/m3
4.E(AN2IL)= 1168 kg/m3 * 2.4 kJ/kg.°C (276+25) °C = 8.438*105 kJ/m3
5.E(UNIL)= 1522 kg/m3 * 1.9 kJ/kg.°C (236+20) °C = 7.403*105 kJ/m3
 Table (3-10): A comparison of reported heat capacities (Cp), densities (ρ), temperature
range (°C) and thermal energy storage capacities (E) of some heat storage materials
compared with ionic liquids present work.
Heat storage Cp ρ Temp. E, Ref.
3
materials (kJ/kg.°C) (kg/m )3 range(°C) (kJ/m )
*105
Water 1.60 at 100 °C 1000 0 - 100 1.600* [40]
Therminol VP-1 1.78 at 130 °C 1060 - 1.887 [116]
Molten salt-Nitrate salts 1.45 at 300 °C 1992 120- 500 - [118]
[C2MIm][BF4]IL 1.28 at 130 °C 1253 - 1.609 [117]
[C4MIm][BF4]IL 1.66 at 130 °C 1175 - 1.949 [68]
[C16CPTS]IL 2.85 at 145 °C 922 - 2.628 [119]
[C8MIm][PF6]IL 2.50 1400 -75 - 416 - [40]
[N+2222][IO3−]IL 1.70 1162 53 - 180 2.293 [43]
[N+4444][BF4-]IL 1.00 1291 71 - - [69]
[N+4444][PF6-]IL 0.40 1234 71 - - [69]
[N+4444][NO3-]IL 1.50 1195 98 - - [69]
ANIL (1:2.4) 1.60 1405 -20 - 232 5.665 This work
AN2IL (1:22) 2.40 1168 -25 - 276 8.438 This work
ASIL (1:12) 2.10 1116 0 - 203 4.758 This work
USIL (1:5) 2.20 1460 -16 - 280 9.508 This work
UNIL (1:1.2) 1.90 1522 -20 - 236 7.403 This work
*calculated value from their reference information.

Most of ILs showed a significantly higher value of thermal energy storage

capacity in the diversity of (4.758 to 9.508)×105 kJ/m3. As the other thermo-
physical properties USIL, AN2IL, and UNIL exhibited the highest values of
thermal energy storage capacity across the series.
As shown in the Table (3-10) thermal energy storage capacity (E) of ionic
liquids presented in this work was much larger than many heat storage
material except molten nitrate salts and [C8MIm][PF6] ionic liquid. High
freezing points up to 120°C of nitrate salts restrict their usage as heat storage
 Figure (3-20): DSC thermogram in µV for; (1): baseline, (2): reference material (Al2O3),
(3): hydrated ammonium aluminum sulfate:acetamide, ASIL with 1:12 mole ratio, (4):
hydrated ammonium aluminum sulfate:urea, USIL with 1:5 mole ratio, (5): hydrated
aluminum nitrate:acetamide, ANIL with 1:2.4 mole ratio, (6): hydrated aluminum
nitrate:acetamide, AN2IL with 1:22 mole ratio, (7): hydrated aluminum nitrate:urea, UNIL
with 1:1.2 mole ratio at 10 °C/min.
and transfer fluid that add complexity of design, operation, and maintenance
of a trough plant[116] and ionic liquids containing PF6- ions are hydrolytically
unstable, have the propensity to decompose and release HPO2F2, H2PO3F,
H3PO4, and highly corrosive HF[75]. It is worth mentioning that several
‘uncatalyzed’ reactions reported in [cation][PF6] ionic liquids that were, in
fact, catalyzed by adventitious HF. Thus, a significant impact of IL anions is
the release of HF containing compounds for which considerable care should
be taken while using PF6 containing ionic liquids. Thus, ILs should be treated
with caution due to their unexplored toxicity and/or stability[20]. Rogers et al.
identified 1-butyl-3-methylimidazolium fluoride hydrate crystallographically
as a decomposition product that was obtained from hydrolytic degradation of
[C4MIm][PF6] during purification process. They observed the evolution of
acidic HF white fumes, which are colorless, highly toxic and corrosive[8].
Also it was found that the lowest value of heat capacity of ionic liquids
presented in this work was higher than some ionic liquids i.e. [N+4444][BF4-],
[N+4444][PF6-] and [N+4444][NO3-], Table(3-10).
Moreover, the studied ionic liquids have some interesting and favorable
properties, such as the higher enthalpies, higher specific heat capacities, and
higher thermal energy storage capacity. In addition, ammonium alum or
aluminum nitrate based RTILs could be considered safer than other ionic
liquids {[C4MIm][BF4] and [C8MIm][PF6] } which are liable to release high
toxic and corrosive product (HF)[8]. On basis of safety, moisture stability and
lower cost, these ionic liquids have the advantageous for usage in thermal
applications such as thermal storage media.

3.4 Addition of some materials to ionic liquids:

Some alkali metal hydroxides, alkaline earth meal oxides and transition
metal oxides were chosen according to their high temperature volatilization
and their relative stability mainly above 1200 K [120] were added to some ionic
liquids to investigate their ability to improve thermal characteristic of some
ionic liquid, these material and their effect are outlined.
3.4.1 Addition of alkali metal hydroxide to ILs:
Potassium hydroxide was added to USIL, and sodium hydroxide to AN2IL
and UNIL when their thermo-physical properties were investigated. It was
found that both hydroxides have different behavior in ionic liquids. Thus
addition of sodium hydroxide to UNIL increases storage capacity of UNIL,
 despite the negligible change in the pH from 0.5 to 0.3 that eliminate the
possibility of forming neutral mixture which would result from protonic acid-
base reaction. In addition to the negligible effect on the liquid temperature
range i.e. freezing point elevated from -20 to -17 °C and decomposition
temperature reduced from 236 to 188 °C with increasing the rate of
decomposition as shown in the (Fig.3-21). It had a significant effect on other
thermo-physical properties such as visual observed decrease in viscosity.
Despite the large decrease in enthalpy reached to 45 % from enthalpy of
UNIL alone which decreased to -1824.44 kJ/kg at a maximum decomposition
temperature of 188.3 °C with disappearance of second decomposition peak of
UNIL and decrease enthalpy of decomposition related to the third
decomposition step to -77.83 kJ/kg as shown in Figure (3-21). In addition to
the significant increase in heat capacity, thermal energy storage capacity
enhanced by 27 % and become 10.105*105 kJ/m3 as shown in Table (3-11).

Table (3-11): Thermal characteristics of ionic liquids with some alkali metal hydroxide.
Tm, Td, pH k, ρ, ∆S, ∆H, ∆G, Cp, E
3 3
Mixture °C °C mS/c kg/m kJ/kg.° kJ/kg kJ/kg kJ kJ/m
5
m C /kg.°C *10
AN2IL -25 276 1.8 3.72 1168 -17.655 -3697.02 -3255.65 2.4 8.438
AN2IL+ -25 261 2.0 4.13 1140 -8.265 -2201.05 -1994.43 1.99 6.488
NaOH
UNIL -20 236 0.5 9.09 1522 -18.799 -3319.94 -2849.97 1.9 7.403
UNIL+ -17 188 0.3 8.69 1512 -7.290 -1824.44 -1642.19 3.26 10.105
NaOH
USIL -16 280 4.2 4.56 1460 -16.321 -2434.84 -2026.82 2.2 9.508
USIL+ -15 264 3.1 6.80 1420 -14.325 -2202.04 -1843.92 2.94 11.648
KOH
Figure (3-21): TGA/ DSC of (hydrated aluminum nitrate:urea, UNIL with 1:1.2 mole ratio)
(blue color) and with addition of sodium hydroxide (red color) at 10 °C/min.
In contrast, sodium hydroxide decrease thermal stability of AN2IL in
similar manner with UNIL (Fig. 3-22), eliminating the possibility of protonic
acid-base reaction resulted from negligible change in the pH from 1.8 to 2, in
addition to the small decrease in decomposition temperature which reduced
from 276 °C to 261 °C and reducing in liquid temperature range and
accelerate rate of the decomposition. The presence of NaOH decreased the
enthalpy by 40 % in which enthalpy of AN2IL alone -3697.02 kJ/kg became
-2201.05 kJ/kg with disappearance of second endothermic peak of the first
decomposition stage of AN2IL alone. The two exothermic/endothermic peaks
of the second decomposition stage of AN2IL alone were changed in which the
enthalpy of 103.98 kJ/kg at a maximum decomposition temperature of 358.1
°C increased to 109.28 kJ/kg with a maximum decomposition temperature of
314.9 °C in liquid mixture of NaOH and AN2IL and the enthalpy of -9.63
kJ/kg changed to an exothermic peak with an enthalpy of 23.06 kJ/kg at
maximum decomposition temperature of 348.8 °C might be associated with
solid crystallization of the decomposition product of the liquid mixture
producing during the decomposition process. A significant decrease in heat
storage capacity of AN2IL by decreasing heat capacity and thermal energy
storage capacity to lower value of 1.4 kJ/kg.°C and 6.565*105 kJ/m3 as shown
in Table (3-11) thus thermal energy storage capacity was reduced by 23 %.
From above results and behavior it could be concluded that the addition of
sodium hydroxide to AN2IL reduced thermal stability and storage capacity of
AN2IL alone and did not enhance heat storage capacity.
Figure (3-22): TGA/ DSC of hydrated aluminum nitrate:acetamide, AN2IL with 1:22 mole ratio) (blue color) and with addition of
sodium hydroxide (red color) at 10 °C/min.
 The addition of potassium hydroxide to USIL Fig. (3-23), it was found that
potassium hydroxide reduced thermal stability of USIL alone and increased
freezing point to higher temperature (from -20 to -15 °C) and decreased the
decomposition temperature down to 264 °C. Although enthalpy of USIL
alone was decreased by 10 % and second endothermic peak of USIL
increased with an enthalpy of -52.37 kJ/kg at maximum decomposition
temperature of 331.5 °C followed by exothermic enthalpy value of 193.07
kJ/kg as shown in the Figure (3-23) refers to solid crystallization of product
through decomposition process. On the other hand, thermal energy storage
capacity enhanced by 23 % due to significant increase in heat capacity and
thermal energy storage capacity to 11.648*105 kJ/m3, in Table (3-11).
In General, Table (3-11) shows that the addition of NaOH or KOH to
UNIL, AN2IL or USIL reduce decomposition temperature and density while
they have variable effect on other thermo-physical properties, as KOH and
NaOH increased thermal energy storage capacity of UNIL and USIL
respectively, while NaOH decrease it with AN2IL.
Figure (3-23): TGA/DSC of (hydrated ammonium aluminum sulfate:urea, USIL with 1:5 mole ratio) (blue color) and with
addition of potassium hydroxide (red color) at 10 °C/min.
 3.4.2 Addition of alkaline earth metal oxide to ILs:
Two alkaline earth metal oxides magnesium oxide and calcium oxide were
added to USIL individually while BaO was added to UNIL to establish their
behavior by TGA/DSC measurements. It was found that the addition of
magnesium oxide to USIL caused in dramatic change on overall thermo-
physical properties (Fig.3-24) resulted in reducing thermal energy storage
capacity by 30 %, through reducing freezing point, decomposition
temperature and heat capacity which became -14 °C, 230 °C and 1.93
kJ/kg.°C respectively, see Table (3-12). This resulted due to kind of
interaction of magnesium oxide with water molecules in ionic liquids resulted
in accelerating of decomposition process and evolving of water.
Table (3-12): Thermal characteristics of ionic liquids with some alkaline earth metal oxide.
Mixture Tm, Td, PH k, ρ, ∆S, ∆H, ΔG, Cp, E
°C °C mS/cm kg/m3 kJ/kg.°C kJ/kg kJ/kg kJ/kg.°C kJ/m3
5
*10
USIL -16 280 4.2 4.56 1460 16.321- -2434.84 -2026.82 2.2 9.508
USIL+ -14 230 3.2 6.75 1420 -7.456 -1144.06 -957.66 1.93 6.687
MgO
USIL+ -15 117 3.5 6.91 1490 -6.541 -826.18 -662.66 1.71 3.363
CaO
UNIL -20 236 0.5 9.09 1522 -18.799 -3319.94 -2849.97 1.9 7.403
UNIL+ -13 167 1.5 10.71 1472 -5.900 -988.89 -841.39 1.66 4.398
BaO

The enthalpy of USIL in presence of MgO decreased by 53% to a value of -

1144.06 kJ/kg (the summation of enthalpies of the first two endothermic
peaks) as shown in Figure (3-24), with small decrease in the third exothermic
peak with respect to the first decomposition stage of USIL alone to 19.94
kJ/kg, with the disappearance of the fourth endothermic peak of USIL.
Figure (3-24): TGA/DSC of (hydrated ammonium aluminum sulfate:urea, USIL with 1:5 mole ratio) (blue color) and with addition
of magnesium oxide ( red color) at 10 °C/min.
 The addition of calcium oxide showed the same reverse effect as shown in
Figure (3-25) in which most thermo-physical properties such as freezing point
elevation (-15 °C), decomposition temperature (117 °C), heat capacity and
thermal energy storage capacity reduction (1.4 kJ/kg.°C) and (2.754 kJ/m3)
respectively as indicated in Table (3-12). The overall reduction effect in
thermal energy storage capacity was 65 %. This unfavorable effect might be
related to an interactions between soluble calcium oxide with water of USIL
that weaken their attraction bond with ionic liquid ions leading to favorable
decomposition at earlier stage as noticed with an acceleration in the rate of
decomposition.
The effect of CaO present in USIL also appeared in reduction in the
enthalpy to – 826.18 kJ/kg and the successive endothermic peaks to -180.19
kJ/kg and -3.36 kJ/kg respectively. While crystallization peak was shifted to
higher temperature and lower enthalpy value of decomposition (362 °C, 19.52
kJ/kg) as shown in the Figure (3-25).
Figure (3-25): TGA/DSC of (hydrated ammonium aluminum sulfate:urea, USIL with 1:5 mole ratio) (blue color) and with addition of
calcium oxide ( red color) at 10 °C/min.
 The effect of addition of barium oxide to UNIL (Fig.3-26), and Table (3-
12) gave a small liquid temperature range due to the increase in the freezing
point and decrease decomposition temperature. Put it in a reduced heat
capacity and lowered thermal energy storage capacity by 41 %. This effect
was synchronized as with MgO and CaO addition to USIL due to weakening
the water molecules interaction with ionic liquid that leading to earlier release
of water from the mixture of BaO with UNIL.
It was concluded that the addition of either MgO or CaO and BaO to USIL
and UNIL respectively resulted in decreasing thermal stability of ionic liquids
alone. Yet the oxides had similar reduction effect of conductivity, freezing
point density, decomposition temperature, heat capacity and thermal energy
storage capacity, see Table (3-12).
Figure (3-26): TGA/DSC of (hydrated aluminum nitrate:urea, UNIL with 1:1.2 mole ratio) (blue color) and with addition of barium
oxide (red color) at 10 °C/min.
 3.4.3 Addition of transition metal oxide to USIL:
Oxy vanadyl sulfate pentahydrate VOSO4.5H2O and transition metal oxides
of NiO, CuO and ZnO were added to USIL to study some transition metal
compounds on the thermal behavior of USIL. The addition of nickel oxide to
USIL gives green liquid. Thermogravimetric analysis of NiO with USIL
liquid mixture, Figure (3-27) showed noticeable increase in thermal stability
by increasing decomposition temperature to 294 °C with low total weight loss
percent. This might be referring to an interaction of nickel oxide with the ions
of ionic liquid. On the other hand DSC analysis showed that the storage
capacity decreased due to significant decrease in the heat capacity of USIL as
shown in Table (3-13) by the effect of nickel oxide leading to reduction in
thermal energy storage capacity by 24 % and the enthalpy decreased by 49%
from -2434.84 kJ/kg to -1241.11 kJ/kg as shown in Table (3-13).
Table (3-13): Thermal characteristics of (hydrated ammonium aluminum sulfate:urea,
USIL with 1:5 mole ratio) with some transition metal oxide.
Tm, Td, pH k, ρ, ∆S, ∆H, ∆G, Cp, E
Mixture °C °C mS/c kg/m3 kJ/kg.° kJ/kg kJ/kg kJ kJ/m3
5
m C /kg.°C *10
USIL- -16 280 4.2 4.56 1460 -16.321 -2434.84 -2026.82 2.2 9.508
alone
USIL+ -15 332 2.8 8.33 1509 -16.023 -2423.26 -2022.69 3.03 15.86
VOSO4. 6
5H2O
USIL+ -10 294 3.1 4.42 1460 -8.331 -1241.11 -1032.84 1.63 7.235
NiO
USIL+ -14 320 3.4 5.72 1420 -8.132 -1216.76 -1013.46 2.40 11.38
CuO 3
USIL+ -15 303 3.6 4.7 1390 -10.902 -1687.23 -1414.68 2.36 10.43
ZnO 2
Figure (3-27): TGA/DSC of (hydrated ammonium aluminum sulfate:urea, USIL with 1:5 mole ratio) (blue color) and with addition of
nickel oxide (red color) at 10 °C/min.
 Thermal stability of USIL was increased by the addition of copper oxide to
USIL that gave blue liquid mixture with improving thermo-physical
properties of USIL despite a decrease in enthalpy of the mixture by 50 %
from -2434.84 kJ/kg to -1216.76 kJ/kg. However, thermal stability and
storage capacity were increased to significant values due to increase in
decomposition temperature, heat capacity and thermal energy storage capacity
by 20 % as shown in Table (3-13). This is might be refer to the interaction of
copper oxide with ionic liquid species resulted in stronger and more
complicated bonds make USIL liquid mixture more stable.
Like copper oxide, zinc oxide also had small enhancement of thermal
stability and storage capacity of USIL in which thermal energy storage
capacity only increased by 10 %. Beside that it showed slightly different
behavior to DSC of USIL alone through decrease in enthalpy of USIL by 31
% from -2434.84 kJ/kg to -1684.23 kJ/kg as shown in the Figure (3-29).
Generally, the addition of transition metal oxides of NiO, CuO and ZnO
to USIL changes in an enthalpy of first decomposition peaks from -40.37
kJ/kg at maximum decomposition temperature of 311.7 °C to -33.37 kJ/kg,
-48.03 kJ/kg and -41.40 kJ/kg at maximum decomposition temperatures of
331.6 °C, 337.0 °C and 328.8 °C respectively, these include a complex
decomposition process exothermal and endothermal resulted in small value of
∆H in endothermic value, while the second decomposition peaks of the liquid
mixtures with an exothermic enthalpy values of 55.26 kJ/kg, 157.36 kJ/kg and
509.38 kJ/kg at a maximum decomposition temperatures of 389.4 °C, 394.3
°C and 403.6 °C respectively as shown in (Fig.3-37), (Fig.3-28) and (Fig.3-
29) respectively could be related to a solid crystallization of the
decomposition product of the liquid mixtures producing during the
decomposition process.
Figure (3-28): TGA/DSC of (hydrated ammonium aluminum sulfate:urea, USIL with 1:5 mole ratio) (blue color)and with addition
of copper oxide (red color) at 10 °C/min.
Figure (3-29): TGA/DSC of (hydrated ammonium aluminum sulfate:urea, USIL with 1:5 mole ratio) (blue color)and with addition of
zinc oxide (red color) at 10 °C/min.
 The large effect was noted with the addition of vanadyl sulfate
pentahydrate to USIL, Figure (3-30), in which DSC of liquid mixture showed
three peaks in which the first two endothermic peaks at maximum
temperature of 143.6 °C and 219.7 °C related to an enthalpy of -2423.26
kJ/kg deceased by less than 0.5 % from enthalpy of USIL alone. Other
thermo-physical properties of decomposition temperature, density,
conductivity, heat capacity and thermal energy storage capacity were also
improved due to the possibility of strong interaction of hydrated vanadyl
sulfate with ionic species in USIL that responsible for this stability and hence
increasing thermal energy storage capacity by 67 %, Table (3-13).
Generally, the addition of transition metal oxides (VOSO2.5H2O, CuO and
ZnO) to USIL cause an improve in thermal stability temperature up to 300 °C
and increase storage capacity, Table (3-13). This might be related to
interaction of these metal ions with ionic liquid species. Since V+4 and Cu+2
had d1 and d9 electronic configuration respectively and these configurations
known to undergo octahedral distortion geometry due to Jahn-Teller effect
which might formed more stable complexes with ionic liquid compared with
Ni+2 of d8 electronic configuration with normal octahedral coordination
geometry this also proved in electronic spectroscopy in other work [81].
Then, the catalytically effect of these transition metal oxides on thermo-
physical properties of USIL can be arranged in the following order:
VOSO4.5H2O > CuO > ZnO > NiO.
Figure (3-30): TGA/DSC of (hydrated ammonium aluminum sulfate:urea, USIL with 1:5 mole ratio) (blue color) and with
addition of vanadyl sulfate pentahydrate (red color) at 10 °C/min.
Conclusions:
Ionic liquids deserve a consideration as valuable candidate with traditional
materials used as thermal energy storage. These RTILs have unique properties
of storing and releasing a significant amount of thermal energy with non
volatile properties. Ionic liquids under the present study, of hydrated
ammonium aluminum sulfate:urea, USIL in the mole ratio 1:5 and hydrated
aluminum nitrate:acetamide, AN2IL in the mole ratio (1:22) offered thermal
stability up to 280 °C and 276 °C respectively and working temperatures
down to -16 and -25 °C respectively in addition to the high storage capacity
by 9.508*105 kJ/m3 obtained for USIL.

The addition of KOH to USIL and NaOH to UNIL increase the storage
capacity of these ionic liquids by increasing their thermal energy storage
capacity up to 11.648*105 kJ/m3 and 10.105*105 kJ/m3 respectively. But the
effect of NaOH on AN2IL proceed in reverse behavior i.e. thermal energy
storage capacity was decreased to lower value 6.488 *105 kJ/m3.

It was found that MgO and CaO inhibit the activity of hydrated
ammonium aluminum sulfate:urea USIL as heat storage material through a
significant reduction in the thermal energy storage capacity down to
6.687*105 kJ/m3 and 3.363*105 kJ/m3 respectively.

It was also found that vanadyl sulfate pentahydrate, copper oxide and zinc
oxides enhanced thermal stability of hydrated ammonium aluminum
sulfate:urea USIL by increasing decomposition temperature from 280 °C to
332 °C, 320 °C and 303 °C respectively and increasing heat capacity from
2.20 kJ/kg.°C to 3.03 kJ/kg.°C, 2.40 kJ/kg.°C and 2.36 kJ/kg.°C respectively
and thermal energy storage capacity to 15.866*105 kJ/m3, 11.383*105 kJ/m3
and 10.432*105 kJ/m3 respectively. While NiO show reverse effect on heat
storage capacity through obvious decrease in heat capacity and thermal
energy storage capacity to 1.63 kJ/kg.°C and 7.235*105 kJ/m3 respectively.
Future work
The obtained result indicated a successful attempt to introduce these ionic
liquids as suggested thermal storage liquids either alone or with some added
materials. However, it was important to suggest further work:

1. Elaboration studying of the reaction mechanism of heating stage of ionic

liquids either alone or with added materials with the aid of mass spectroscopy,
NMR, CHN….etc.
2. Corrosion behavior of these liquids mixtures, to establish their effect on
metal parts if applied in piping or pumps.
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 ‫الملخص‪:‬‬
‫درست خواص بعض السوائل االيونية بدرجة حرارة الغرفة لترشيحها في التطبيقات الحرارية‬
‫كوسائط خازنة للحرارة وموائع ناقلة للحرارة لخمسة سوائل أيونية حضرت من شب االمونيوم كملح‬
‫العضوي مع اليوريا أو االستمايد كمركبات عضوية‪ ,‬و نترات االلمنيوم المائية مع مركبات اليوريا او‬
‫االستمايد بنسب مولية مختلفة‪ ,‬لوحدها او مع أضافة بعض المواد المحسنة لدراسة الثأثير التآزري‬
‫بأستخدام التحليل الحراري الوزني‪ ,‬المسعر الحراري التفاضلي‪ ,‬حيود االشعة السينية‪ ,‬وطيف االشعة‬
‫تحت الحمراء ومقياس التوصيلية الكهربائية‪ .‬كما تمت دراسة الخواص الفيزيائية الحرارية مثل‬
‫االنثالبي‪ ,‬الحرارة النوعية وسعة خزن الطاقة الحرارية‪ .‬وإمتازت السوائل االيونية لنترات االلمنيوم‪-‬‬
‫أستمايد بالنسبة المولية (‪ )::22‬وشب االمونيوم‪-‬يوريا بالنسبة المولية (‪ )122‬لوحدها أو بأضافة بعض‬
‫المواد بكثافة عالية وأستقرارية كيميائية عالية وحرارة نوعية عالية و مدى حراري واسع‪ .‬النتائج تشير‬
‫الى أن السوائل االيونية لوحدها او بأضافة بعض المواد من الممكن اعتبارها كمرشحات واعدة‬
‫ألستخدامها كوسائط خازنة للحرارة وموائع ناقلة للحرارة‪.‬‬

‫من جهة أخرى‪ ,‬هيدوكسيد الفلز القلوي (هيدوكسيد الصوديوم) مع نترات االلمنيوم المائية‪-‬يوريا‬
‫بالنسبة المولية (‪ )2.:22‬وهيدروكسيد الكالسيوم مع كبريتات االمونيوم االلمنيوم المائية‪-‬يوريا بالنسبة‬
‫المولية (‪ )122‬ساهمت في زيادة سعة خزن الطاقة الحرارية لهذه السوائل االيونية‪ .‬في حين أن أضافة‬
‫هيدوكسيد الصوديوم الى نترات االلمنيوم المائية‪-‬استمايد بالنسبة المولية (‪ )::22‬اعطت أستقرارية‬
‫الحرارية وسعة خزن للطاقة الحرارية أقل لهذا السائل االيوني‪.‬‬

‫لتحسين الخصائص تم إضافة بعض االكاسيد الفلزية من أجل بيان الثأثير التآزري لهذه المركبات‪,‬‬
‫حيث أن إضافة الفلزات القلوية الترابية (أوكسيد المغنيسيوم وأوكسيد الكالسيوم) الى كبريتات‬
‫االمونيوم االلمنيوم المائية‪-‬يوريا بالنسبة المولية (‪ )122‬وأوكسيد الباريوم الى نترات االمنيوم المائية‪-‬‬
‫يوريا بالنسبة المولية (‪ )2.:22‬قد قللت من االستقرارية الحرارية والحرارة النوعية وسعة خزن الطاقة‬
‫الحرارية بالمقارنة مع السائل االيوني لوحده‪.‬‬

‫عالوة الى ذلك‪ ,‬أضافة بعض أكاسيد العناصر االنتقالية (أوكسيد كبريتات الفناديوم المائية وأوكسيد‬
‫النحاس وأوكسيد الزنك) الى كبريتات االمونيوم االلمنيوم المائية‪-‬يوريا بالنسبة المولية (‪ )122‬زادت‬
‫من االستقرارية الحرارية و سعة خزن الطاقة الحرارية للسائل االيوني االصلي‪ ,‬بينما أضاف اوكسيد‬
‫النيكل الى السائل االيوني كبريتات االمونيوم االلمنيوم المائية‪-‬يوريا بالنسبة المولية (‪ )122‬حسنت من‬
‫االستقرارية الحرارية له فقط‪.‬‬
 ‫جمهورية العراق‬
‫وزارة التعليم العالي والبحث العلمي‬
‫جامعة النهرين‬
‫كلية العلوم‬
‫قسم الكيمياء‬

‫تحري الخواص الحرارية لبعض السوائل االيونية‬

‫الحاوية على اليوريا واالستمايد‬
‫رسالة‬
‫مقدمة إلى كلية العلوم‪ /‬جامعة النهرين‬
‫كجزء من متطلبات نيل درجة الماجستير في علوم الكيمياء‬

‫من قِبَ ِل‬

‫هدى سالم عبد‬
‫بكالوريوس‪2012‬‬

‫إشراف‬
‫االستاذ المساعد الدكتور‬
‫هادي محمد علي عبود‬

‫أيار‬ ‫رجب‬
‫‪ :121‬م‬ ‫‪ 2341‬ه‬