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INFINITE DILUTION ACTIVITY COEFFICIENT
MEASUREMENTS
OF ORGANIC SOLUTES IN
FLUORINATED IONIC LIQUIDS BY
GAS-LIQUID
CHROMATOGRAPHY AND THE INERT GAS
STRIPPING METHOD
Submitted in fulfillment of the academic requirements for the
degree of Master of Science,
Faculty of Engineering, School of Chemical
Engineering,
University of KwaZulu-Natal
by
Kaniki Armel Tumba
[BSc. Eng (Chem)]
Supervisor: Prof. Deresh Ramjugernath
Co-Supervisor: Dr. Paramespri Naidoo
i Declaration
DECLARATION
I, Kaniki Armel Tumba, declare that:
(i) The research reported in this thesis, except where otherwise
indicated, is my
original work.
(ii) This thesis has not been submitted for any degree or
examination at any other university.
(iii) This thesis does not contain other persons` data,
pictures, graphs or other information, unless specifically acknowledged as
being sourced from other persons.
(iv) This thesis does not contain other persons` writing,
unless specifically acknowledged as being sourced from other researchers. Where
other written sources have been quoted, then:
a) their words have been re-written but the general information
attributed to them has been referenced;
b) where their exact words have been used, their writing has
been placed inside quotation marks, and referenced.
(v) Where I have reproduced a publication of which I am an
author, co-author or editor, I have indicated in detail which part of the
publication was actually written by myself alone and have fully referenced such
publications.
(vi) This thesis does not contain text, graphics or tables
copied and pasted from the internet, unless specifically acknowledged, and the
source being detailed in the thesis and in the References sections.
Kaniki A. Tumba (Candidate) Date
As the candidate`s Supervisor I agree/do not agree to the
submission of this thesis.
Prof. Deresh Ramjugernath Date
ABSTRACT
Environmental and safety concerns have prompted an active quest
for green? alternatives to
molecular solvents currently used in industrial
chemical processes. In recent years, ionic liquids
have been reported as
potentially good replacements for conventional solvents. Activity
coefficients at infinite dilution, of various organic solutes
have been measured in the
temperature range from 313.15 to 373.15 K by gas-liquid
chromatography and the inert gas
stripping techniques in seven fluorinated
ionic liquids (FILs). Partial molar excess enthalpies at
infinite dilution
of the solutes in the ionic liquids have been derived from the temperature-
dependence of experimental values. Selectivities and capacities
have been calculated for
various separation problems and compared to literature values for
other ionic liquids, as well as conventional solvents. The effect of structure
on the selectivity has been investigated.
The present work, initiated in the context of South Africa`s
Fluorochemical Expansion Initiative is a contribution to the understanding of
how structure influences FILs selectivity and capacity in different separation
problems. FILs are interesting for South Africa as its geology contains large
amounts of fluorine ores.
For the n-hexane/benzene, and n-hexane/hex-1-ene systems which
represent the aliphatics/aromatics and paraffins/olefins separation problems,
higher selectivities at infinite dilution were obtained with FILs consisting of
short-chained cations and small anions. The opposite trend was observed for the
methanol/acetone and the ethanol/butan-2-one systems as representatives of the
alcohols/ketones separation problem as well as the methanol/benzene system
which refers to the alcohols/aliphatics mixtures. FILs with long cation alkyl
chains and large anions tend to be the most selective for the benzene/
butan-2-one system, indicative of the aliphatics/ketones separation problem.
The natural logarithm of has been found to vary linearly with
the carbon number of the alkyl
chain attached to the methylpyrrolidinium or
methylimidazolium group. On this ground, a
simple equation correlating as
well as selectivity with the cation alkyl chain length has been
proposed. It has been successfully tested using experimental data
related to pyrrolidinium and imidazolium-based ionic liquids.
ACKNOWLEDGEMENTS
Glory and Praise to Jehovah, the all mighty God who allowed me to
achieve this research work.
I express my utmost gratitude to Prof. Deresh Ramjugernath for
his dedicated supervision and his priceless assistance throughout this study.
Dr Paramespri Naidoo, the co-supervisor is sincerely acknowledged for her
pertinent suggestions and skillful guidance.
This work is based upon research supported by the South
African Research Chairs Initiative of the Department of Science and Technology
and National Research Foundation (NRF) which is acknowledged for its financial
support.
I would be remiss if I do not extend my appreciations to the
following individuals as well:
· My wife Fanny Tshabu Kaniki who deserves a medal for her
patience and support;
· My parents, brothers and sisters for their
encouragements;
· Messers Lindinkosi Mkinze and Ayanda Khanyile, The
Thermodynamics Research Unit laboratory technicians;
· Messers Ken Jack and Kelly Robertson, Mechanical workshop
staff in the School of Chemical Engineering;
· Glass blower Peter Siegling and UKZN Chemical Engineering
ICT manager P. Nayager;
· Prof. Urszula Domañska and Dr. Andrzej Marciniak
(Warsaw University of Technology, Poland) for insightful discussions on the
behavior of ionic liquids;
· Dr. Fabrice Mutelet (Laboratoire de Thermodynamique
des Milieux Polyphasés, Nancy, France) for his availability to answer
some tricky questions on the GLC experimental procedure;
· Dr. Christophe Coquelet (Laboratoire des Equilibres
Thermodynamiques, ENSM, Fontainebleau, France) who helped in advising on the
construction of the inert gas stripping apparatus;
· All Thermodynamics Research Unit postgraduate students
and friends: J. Chiyen, M. Tshibangu, J. Kapuku, T. P. Benecke, M. Tadie, S.
Iwarere, B. Moller, F. Kabulu, P.N. Thokozani, ...
· E. Olivier and N. Gwala who authorized the use of
their experimental data in this study;
· All UKZN Chemical Engineering lecturers who expressed
interest in this project: Prof. J.D. Raal, Prof. D. Arnold, Mr Baah,...
TABLE OF CONTENTS
DECLARATION i
ABSTRACT ii
ACKNOWLEDGEMENTS iii
TABLE OF CONTENTS iv
LIST OF FIGURES ix
LIST OF PHOTOGRAPHS xxi
LIST OF TABLES xxiiNOMENCLATURE
.......................................................................
xxvi
ABBREVIATIONS xxix
CHAPTER ONE: INTRODUCTION 1
CHAPTER TWO: LITERATURE REVIEW 4
2.1. Ionic liquids 4
2.1.1. Definition and structure 4
2.1.2. History 4
2.1.3. Properties of ionic liquids 6
2.1.4. Potential applications of ionic liquids in the chemical
industry 6
2.1.5. Commercial applications of ionic liquids 7
2.1.6. Use of ionic liquids as solvents in separation processes.
8
2.1.7. Barriers to the commercial use of ionic liquids 10
2.1.8. Fluorinated ionic liquids. (FILs) 11
2.2. Infinite dilution activity coefficients 12
2.2.1. Definition 12
2.2.2. Importance and use of infinite dilution activity
coefficient data 12
2.2.3. Temperature dependence of activity coefficient 15
2.2.4. Predictive activity coefficient models 16
2.2.5. Experimental techniques for IDACs measurements 19
2.3. Advances in the design of IGS equipment 21
2.3.1. Major developments in the use of the IGSM 21
2.3.2. The number of cells required for IDAC measurements 22
2.3.3. Cell design parameters. 22
2.3.4. Review of previous equilibrium cells 24
v
CHAPTER THREE: THEORETICAL CONSIDERATIONS 34
3.1. Gas liquid chromatography 34
3.2. Inert gas stripping method 37
3.2.1. Equations for IDACs computation 37
3.2.2. Mass Transfer considerations in the equilibrium cell.
50
CHAPTER FOUR: EXPERIMENTAL APPARATUS AND PROCEDURE
52
4.1. Limiting activity coefficient measurements by gas liquid
chromatography 52
4.1.1. Chemicals 52
4.1.2. Experimental set up 53
4.1.3. Experimental procedure 54
4.2. The inert gas stripping technique 56
4.2.1. Chemicals 56
4.2.2. Experimental Set-up 56
4.2.3. Experimental procedure 60
CHAPTER FIVE: RESULTS 62
5.1. Results from Gas-Liquid Chromatography 63
5.1.1. Hexadecane 63
5.1.2. Trihexyltetradecylphosphonium bis
(trifluoromethylsulfonyl) imide,
[3C6C14P] [Tf2N] 64
5.1.3. Trihexyltetradecylphosphonium tetrafluoroborate,
[3C6C14P] [BF4] 71
5.1.4. Trihexyltetradecylphosphonium hexafluorophosphate,
[3C6C14P] [PF6] 78
5.1.5. Methyltrioctylammonium bis (trifluoromethylsulfonyl)
imide, [C13C8N] [Tf2N] 85
5.1.6. 1-Butyl-3-methylimidazolium hexafluoroantimonate, [BMIM]
[SbF6]. 92
5.1.7.1-ethyl-3-methylimidazolium trifluoromethanesulfonate,
[EMIM] [TfO] 99
5.1.8. 1-methyl-3-octylimidazolium hexafluorophosphate,
[MOIM][PF6] 106
5.2. Results from the inert gas stripping technique 112
5.2.1. N-methyl-2-pyrrolidone, NMP 112
5.2.2. Trihexyltetradecylphosphonium bis
(trifluoromethylsulfonyl) imide 113
5.3.Separation potential of the investigated ionic liquids.
113
CHAPTER SIX: DISCUSSION 115
6.1. Fluorinated Ionic Liquids investigated in this work 115
6.1.1. Gas-Liquid Chromatography 115
6.1.2. The inert gas stripping technique 118
6.1.3. Error estimation 119
vi
6.2. Limiting activity coefficients of fluorinated ionic liquids
120
6.2.1. Hierarchy of IDACs values. 122
6.2.2. Effect of structure on IDACs of organic solutes in
Fluorinated Ionic Liquids, FILs 125
6.3. Limiting selectivity and capacity of fluorinated ionic
liquids 127
6.3.1. n-Hexane (1)/Benzene (2) separation problem 128
6.3.2. Methanol (1)/benzene (2) separation problem 130
6.3.3. Methanol (1)/acetone (2) separation problem 131
6.3.4. n-hexane (1)/ hex-1-ene (2) separation problem 132
6.3.5. Benzene (1)/ butan-2-one (2) separation problem 134
6.3.6. Ethanol (1)/ butan-2-one (2) separation problem 135
6.4. Correlation of limiting activity coefficient and selectivity
with the FIL alkyl chain 135
CHAPTER SEVEN: CONCLUSION AND RECOMMENDATIONS
137
REFERENCES 141
APPENDIX A: SOURCES OF IDACs LITERATURE DATA
160
APPENDIX B: STRUCTURE OF IONIC LIQUIDS 165
APPENDIX C: ORIGIN AND PURITY OF CHEMICALS
166
APPENDIX D: FUGACITIES, CRITICAL DATA AND IONIZATION
ENERGIES167
APPENDIX E: CALIBRATION DATA 168
APPENDIX F: SELECTIVITIES AND CAPACITIES 169
APPENDIX G: EFFECT OF STRUCTURE ON IDAC VALUES
170
1. Infinite dilution activity coefficients of alkanes in
fluorinated ionic liquids 170
1.1. Infinite dilution activity coefficients
of alkanes in imidazolium-based
fluorinated ionic liquids. 170
1.2. Infinite dilution activity coefficients of alkanes in
phosphonium-based FILs 172
1.3. Infinite dilution activity coefficients of alkanes in
ammonium-based FILs 173
1.4. Infinite dilution activity coefficients of alkanes in
pyridinium-based FILs 173
1.5. Infinite dilution activity coefficients of alkanes in
pyrrolidinium-based FILs 173
1.6. Infinite dilution activity coefficients of alkanes in
sulfonium-based FILs 174
2. Infinite dilution activity coefficients of alk-1-enes
in fluorinated ionic liquids. 174
2.1. Infinite dilution activity coefficients of alk-1-enes in
imidazolium-based FILs 174
2.2. Infinite dilution activity coefficients of alk-1-enes in
phosphonium-based FILs 177
2.3. Infinite dilution activity coefficients of alk-1-enes in
ammonium-based FILs 177
2.4. Infinite dilution activity coefficients of alk-1-enes in
pyridinium-based FILs 178
2.5. Infinite dilution activity coefficients of alk-1-enes in
pyrrolidinium-based FILs 178
3. Infinite dilution activity coefficients of alk-1-ynes
in fluorinated ionic liquids. 179
3.1. Infinite dilution activity coefficients of alk-1-ynes in
imidazolium-based FILs 179
3.2. Infinite dilution activity coefficients of alk-1-ynes in
phosphonium-based FILs 181
3.3. Infinite dilution activity coefficients of alk-1-ynes in
ammonium, pyrrolidinium and sulfonium-based FILs 182
4. Infinite dilution activity coefficients of
cycloalkanes in fluorinated ionic liquids. 182
4.1. Infinite dilution activity coefficients of cycloalkanes in
imidazolium-based FILs 182
4.2. Infinite dilution activity coefficients of cycloalkanes in
phosphonium-based FILs 185
4.3. Infinite dilution activity coefficients of cycloalkanes in
ammonium-based FILs 185
4.4. Infinite dilution activity coefficients of cycloalkanes in
pyridinium-based FILs 185
4.5. Infinite dilution activity coefficients of cycloalkanes in
pyrrolidinium-based FILs 186
4.6. Infinite dilution activity coefficients of cycloalkanes in
sulfonium-based FILs 186
5. Infinite dilution activity coefficients of
alkan-1-ols in fluorinated ionic liquids 186
5.1. Infinite dilution activity coefficients of alkan-1-ols in
imidazolium-based FILs 186
5.2. Infinite dilution activity coefficients of alkan-1-ols in
phosphonium-based FILs 189
5.3. Infinite dilution activity coefficients of alkan-1-ols in
ammonium-based FILs 189
5.4. Infinite dilution activity coefficients of alkan-1-ols in
pyridinium-based FILs 190
5.5. Infinite dilution activity coefficients of alkan-1-ols in
pyrrolidinium-based FILs 190
5.6. Infinite dilution activity coefficients of alkan-1-ols in
sulfonium-based FILs 190
6. Infinite dilution activity coefficients of
alkylbenzenes in fluorinated ionic liquids. 191
6.1. Infinite dilution activity coefficients of alkylbenzenes in
imidazolium-based FILs 191
6.2. Infinite dilution activity coefficients of alkylbenzenes in
phosphonium-based FILs 193
6.3. Infinite dilution activity coefficients of alkylbenzenes in
ammonium-based FILs 193
6.4. Infinite dilution activity coefficients of alkylbenzenes in
pyridinium-based FILs 194
6.5. Infinite dilution activity coefficients of alkylbenzenes in
pyrrolidinium and sulfoniumbased FILs 194
7. Infinite dilution activity coefficients of ket-2-ones
in fluorinated ionic liquids. 195
7.1. Infinite dilution activity coefficients of ket-2-ones in
imidazolium-based FILs 195
7.2. Infinite dilution activity coefficients of ket-2-ones in
phosphonium-based FILs 196
7.3. Infinite dilution activity coefficients of ket-2-ones in
ammonium-based FILs 197
7.4. Infinite dilution activity coefficients of ket-2-ones in
pyridinium-based FILs 197
7.5. Infinite dilution activity coefficients of ket-2-ones in
pyrrolidinium-based FILs 197
APPENDIX H: EFFECT OF STRUCTURE ON LIMITING SELECTIVITY
AND CAPACITY 198
1. Benzene/n-hexane separation problem 198
1.1. Imidazolium-based fluorinated ionic liquids 198
1.2. Phosphonium-based fluorinated ionic liquids 199
1.3. Ammonium-based Fluorinated ionic liquids 199
2. Methanol/benzene separation problem 200
2.1. Imidazolium-based fluorinated ionic liquids 200
2.2. Phosphonium-based fluorinated ionic liquids 200
2.3. Ammonium-based fluorinated ionic liquids 201
3. Methanol/acetone separation problem 201
3.1. Imidazolium-based fluorinated ionic liquids 201
3.2. Phosphonium-based fluorinated ionic liquids 202
3.3. Ammonium-based fluorinated ionic liquids 203
4. n-Hexane/hex-1-ene separation problem 203
4.1. Imidazolium-based fluorinated ionic liquids 203
4.2. Phosphonium-based fluorinated ionic liquids 204
4.3. Ammonium-based fluorinated ionic liquids 204
4.4. Pyrrolidinium-based fluorinated ionic liquids 205
5.Benzene/butan-2-one separation problem 205
5.1 Imidazolium-based fluorinated ionic liquids 205
5.2 Phosphonium-based fluorinated ionic liquids 206
6. Ethanol/butan-2-one separation problem 206
6.1 Imidazolium-based fluorinated ionic liquids 206
6.2 Phosphonium-based fluorinated ionic liquids 206
APPENDIX I: CORRELATION OF INFINITE DILUTION ACTIVITY
COEFFICIENT, SELECTIVITY AND CAPACITY 207
1. Infinite dilution activity coefficient correlation
with the ionic liquid alkyl chain length 207
1.1. Imidazolium-based fluorinated ionic liquids 207
1.2. Pyrrolidinium-based fluorinated ionic liquids 208
2. Infinite dilution selectivity coefficient correlation
with the ionic liquid alkyl chain length 209
2.1. n-hexane/benzene system 209
2-2. n-hexane/hex-1-ene system 209
LIST OF FIGURES
Figure 2-1: Structure of ionic liquids.
Figure 2-2: Dilutor cell constructed by Leroi et
al. (1977).
Figure 2-3: Equilibrium cell constructed by
Richon et al. (1980).
Figure 2-4: Dilutor cell used by Richon and
Renon (1980).
Figure 2-5: Dilutor cell designed by Legret et
al. (1983).
Figure 2-6: Dilutor cell designed by Richon et
al. (1985) for viscous and foaming mixtures. Figure 2-7:
Equilibrium cell designed by Bao et al. (1994).
Figure 2-8: Equilibrium cell designed by Hovorka
et al. (1997).
Figure 2-9: Equilibrium cell designed by Miyano
et al. (2003) for the determination of Henry`s law constants using the dilutor
technique.
Figure 2-10: Dilutor cell designed by Dobryakov
et al. (2008).
Figure 2-11: The dilutor cell designed by
Kutsuna and Hori (2008).
Figure 4-1: Flow diagram of the experimental
set up for the inert gas stripping method.
Figure 4-2:
Cross Section of the cold trap to illustrate its inner working (George
2008).
Figure 4-3: Typical plots of solute GC peak area and
ln (solute peak area) versus time.
Figure 5-1: Plots of versus for alkanes in
[3C6C14P] [Tf2N] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-2: Plots of versus for alk-1-enes in
[3C6C14P] [Tf2N] together with a linear
correlation of the data
using the Gibbs-Helmholtz equation.
Figure 5-3: Plots of versus for cycloalkanes in
[3C6C14P] [Tf2N] together with a
linear correlation of the data
using the Gibbs-Helmholtz equation.
Figure 5-4: Plots of versus for alk-1-ynes in
[3C6C14P] [Tf2N] together with a linear
correlation of the data
using the Gibbs-Helmholtz equation.
Figure 5-5: Plots of versus for alkanols in
[3C6C14P] [Tf2N] together with a linear
correlation of the data
using the Gibbs-Helmholtz equation.
Figure 5-6: Plots of versus for alkylbenzenes in
[3C6C14P] [Tf2N] together with a
linear correlation of the data
using the Gibbs-Helmholtz equation.
Figure 5-7: Plots of versus for ketones in
[3C6C14P] [Tf2N] together with a linear
correlation of the data
using the Gibbs-Helmholtz equation.
Figure 5-8: Plots of versus the number of carbon
atoms for n-alkanes, alk-1-enes,
cycloalkanes, alk-1-ynes, ketones, alkanols
and alkylbenzenes in [3C6C14P] [Tf2N].
Figure 5-9: Plots of versus for n-alkanes in
[3C6C14P] [BF4] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-10: Plots of versus for alk-1-enes in
[3C6C14P] [BF4] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-11: Plots of versus for alk-1-ynes in
[3C6C14P] [BF4] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-12: Plots of versus for cycloalkanes in
[3C6C14P] [BF4] together with a
linear correlation of the data using the Gibbs-Helmholtz
equation.
Figure 5-13: Plots of versus for alkanols in
[3C6C14P] [BF4] together with a linear
correlation of the data
using the Gibbs-Helmholtz equation.
Figure 5-14: Plots of versus for alkylbenzenes
in [3C6C14P] [BF4] together with a
linear correlation of the data
using the Gibbs-Helmholtz equation.
Figure 5-15: Plots of versus for ketones in
[3C6C14P] [BF4] together with a linear
correlation of the data
using the Gibbs-Helmholtz equation.
Figure 5-16: Plots of versus the number of
carbon atoms for n-alkanes, alk-1-enes, alk-1-
ynes, cycloalkanes, alkanols,
alkylbenzenes and ketones in [3C6C14P] [BF4].
Figure 5-17: Plots of versus for alkanes in
[3C6C14P] [PF6] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-18: Plots of versus for alk-1-enes in
[3C6C14P] [PF6] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-19: Plots of versus for alk-1-ynes in
[3C6C14P] [PF6] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-20: Plots of versus for cycloalkanes in
[3C6C14P] [PF6] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-21: Plots of versus for alkanols in
[3C6C14P] [PF6] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-22: Plots of versus for alkylbenzenes
in [3C6C14P] [PF6] together with a
linear correlation of the data using the Gibbs-Helmholtz
equation.
Figure 5-23: Plots of versus for ketones in
[3C6C14P] [PF6] together with a linear
correlation of the data
using the Gibbs-Helmholtz equation.
Figure 5-24: Plots of versus the number of
carbon atoms for n-alkanes, alk-1-enes, alk-1-
ynes, cycloalkanes, alkanols,
alkylbenzenes and ketones in [3C6C14P] [PF6].
Figure 5-25: Plots of versus for alkanes in
[C13C8N] [Tf2N] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-26: Plots of versus for alk-1-enes in
[C13C8N] [Tf2N] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-27: Plots of versus for alk-1-ynes in
[C13C8N] [Tf2N] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-28: Plots of versus for cycloalkanes in
[C13C8N] [Tf2N] together with a
linear correlation of the data using the Gibbs-Helmholtz
equation.
Figure 5-29: Plots of versus for alkanols in
[C13C8N] [Tf2N] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-30: Plots of versus for alkylbenzenes
in [C13C8N] [Tf2N] together with a
linear correlation of the data using the Gibbs-Helmholtz
equation.
Figure 5-31: Plots of versus for ketones in
[C13C8N] [Tf2N] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-32: Plots of versus the number of
carbon atoms for n-alkanes, alk-1-enes, and
alk-1-ynes, cycloalkanes, alkanols, alkylbenzenes and ketones in
[C13C8N] [Tf2N]. Figure 5-33: Plots of versus for alkanes in
[BMIM] [SbF6] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-34: Plots of versus for alk-1-enes in
[BMIM] [SbF6] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-35: Plots of versus for alk-1-ynes in
[BMIM] [SbF6] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-36: Plots of versus for cycloalkanes in
[BMIM] [SbF6] together with a
linear correlation of the data using the Gibbs-Helmholtz
equation.
Figure 5-37: Plots of versus for alkanols in
[BMIM] [SbF6] together with a linear
correlation of the data using the
Gibbs-Helmholtz equation.
Figure 5-38: Plots of versus for alkylbenzenes
in [BMIM] [SbF6] together with a
linear correlation of the data using the
Gibbs-Helmholtz equation.
Figure 5-39: Plots of versus for ketones in
[BMIM] [SbF6] together with a linear
correlation of the data using the
Gibbs-Helmholtz equation.
Figure 5-40: Plots of versus the number of
carbon atoms for alk-1-enes, alk-1-ynes,
cycloalkanes, alkanols,
alkylbenzenes and ketones in [BMIM] [SbF6].
List of figures
Figure 5-41: Plots of versus for alkanes in
[EMIM] [TfO] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-42: Plots of versus for alk-1-nes in
[EMIM] [TfO] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-43: Plots of versus for alk-1-ynes in
[EMIM] [TfO] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-44: Plots of versus for cycloalkanes in
[EMIM] [TfO] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-45: Plots of versus for alkanols in
[EMIM] [TfO] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-46: Plots of versus for alkylbenzenes
in [EMIM] [TfO] together with a
linear correlation of the data using the Gibbs-Helmholtz
equation.
Figure 5-47: Plots of versus the number of
carbon atoms for n-alkanes, alk-1-enes, alk-1-
ynes, cycloalkanes, alkanols and alkylbenzenes in [EMIM]
[TfO].
Figure 5-48: Plots of versus for n-alkanes in
[MOIM] [PF6] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-49: Plots of versus for alk-1-enes in
[MOIM] [PF6] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-50: Plots of versus for alk-1-ynes in
[MOIM] [PF6] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-51: Plots of versus for cycloalkanes in
[MOIM] [PF6] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-52: Plots of versus for alkanols in
[MOIM] [PF6] together with a linear
correlation of the data using the Gibbs-Helmholtz equation.
Figure 5-53: Plots of versus for alkylbenzenes
in [MOIM] [PF6] together with a
linear correlation of the data using the Gibbs-Helmholtz
equation.
Figure 5-54: Plots of versus the number of
carbon atoms for n-alkanes, alk-1-enes, alk-1-
ynes, cycloalkanes, alkanols and alkylbenzenes in [MOIM]
[PF6].
Figure 6-1: Experimental infinite dilution
activity coefficients of n-hexane and cyclohexane in
various fluorinated ionic liquids at 313.15 K.
Figure 6-2: Experimental infinite dilution
activity coefficients of hex-1-ene and hex-1-yne in
various fluorinated ionic liquids at 313.15 K.
Figure 6-3: Experimental infinite dilution
activity coefficients of ethanol, benzene and acetone in various fluorinated
ionic liquids at 313.15 K.
Figure B-1: Ions present in the structure of
ionic liquids used in this work. Figure E-1: Temperature
calibration curve for the dilutor cell Pt 100.
Figure E-2: Pressure calibration curve for the
dilutor cell pressure transducer.
Figure G-1: Plots of versus Nc for alkanes in
imidazolium-based FILs comprising
[BF4]- ion.
Figure G-2: Plots of versus Nc for alkanes in
imidazolium-based FILs comprising
[Tf2N] - ion.
Figure G-3: Plots of versus Nc for alkanes in
imidazolium-based FILs comprising [PF6]-
ion.
Figure G4: Plots of versus Nc for alkanes in
imidazolium-based FILs comprising [TfO]-,
[SbF6]- and [TFA]- ions.
Figure G-5: Plots of versus Nc for alkanes in
imidazolium-based FILs comprising
[EMIM]+ ion.
Figure G-6: Plots of versus Nc for alkanes in
imidazolium-based FILs comprising
[BMIM]+ ion.
Figure G-7: Plots of versus Nc for alkanes in
imidazolium-based FILs comprising
[HMIM]+ ion.
Figure G-8: Plots of versus Nc for alkanes in
imidazolium-based FILs comprising
[MOIM]+ ion.
Figure G-9: Plots of versus Nc for alkanes in
phosphonium-based FILs comprising
[3C6C14P]+ ion.
Figure G-10: Plots of versus Nc for alkanes in
ammonium-based FILs comprising
[Tf2N] - ion.
Figure G-11: Plots of versus Nc for alkanes in
pyridinium-based FILs
Figure G-12: Plots of versus Nc for alkanes in
pyrrolidinium-based FILs comprising
[Tf2N] - ion.
Figure G-13: Plots of versus Nc for alkanes in
pyrrolidinium-based FILs comprising
[BMPyrr]+ ion.
Figure G-14: Plots of versus Nc for alkanes in
the sulfonium-based FIL [Et3S] [Tf2N]
List of figures
xiv
Figure G-15: Plots of versus Nc for alk-1-enes
in imidazolium-based FILs comprising
[BF4]- ion.
Figure G-16: Plots of versus Nc for alk-1-enes
in imidazolium-based FILs comprising
[Tf2N] -ion.
Figure G-17: Plots of versus Nc for alk-1-enes
in imidazolium-based FILs comprising
[PF6]- ion.
Figure G-18: Plots of versus Nc for alk-1-enes
in imidazolium-based FILs comprising
[TfO]- ion.
Figure G-19: Plots of versus Nc for alk-1-enes
in imidazolium-based FILs comprising
[EMIM]+ ion.
Figure G-20: Plots of versus Nc for alk-1-enes
in imidazolium-based FILs comprising
[BMIM]+ion.
Figure G-21: Plots of versus Nc for alk-1-enes
in imidazolium-based FILs comprising
[HMIM] +ion.
Figure G-22: Plots of versus Nc for alk-1-enes
in imidazolium-based FILs comprising
[MOIM]+ion.
Figure G-23: Plots of versus Nc for alk-1-enes
in phosphonium-based FILs comprising
[3C6C14P]+ ion.
Figure G-24: Plots of versus Nc for alk-1-enes
in ammonium-based FILs comprising
[Tf2N] - ion.
Figure G-25: Plots of versus Nc for alk-1-enes
in the pyridinium-based FIL [Epy] [Tf2N]
Figure G-26: Plots of versus Nc for alk-1-enes
in pyrrolidinium-based FILs comprising
[Tf2N]- ion.
Figure G-27: Plots of versus Nc for alk-1-enes
in pyrrolidinium-based FILs comprising
[BMPyrr]+ ion.
Figure G-28: Plots of versus Nc for alk-1-enes
in the sulfonium-based FIL [Et3S] [Tf2N]
Figure G-29: Plots of versus Nc for alk-1-ynes
in imidazolium-based FILs comprising
[BF4]- ion.
Figure G-30: Plots of versus Nc for alk-1-ynes
in imidazolium-based FILs comprising
[PF6]- ion.
Figure G-31: Plots of versus Nc for alk-1-ynes
in imidazolium-based FILs comprising
Figure G-32: Plots of versus Nc for alk-1-ynes
in imidazolium-based FILs comprising
[TfO]- ion.
Figure G-33: Plots of versus Nc for alk-1-ynes
in imidazolium-based FILs comprising
[EMIM]+ ion.
Figure G-34: Plots of versus Nc for alk-1-ynes
in imidazolium-based FILs comprising
[BMIM]+ ion.
Figure G-35: Plots of versus Nc for alk-1-ynes
in imidazolium-based FILs comprising
[HMIM]+ ion.
Figure G-36: Plots of versus Nc for alk-1-ynes
in phosphonium-based FILs comprising
[3C6C14P]+ ion.
Figure G-37: Plots of versus Nc for alk-1-ynes
in an ammonium, a pyrrolidinium and a
sulfonium-based FILs.
Figure G-38: Plots of versus Nc for cycloalkanes
in imidazolium-based FILs comprising
[BF4]- .
Figure G-39: Plots of versus Nc for cycloalkanes
in imidazolium-based FILs comprising
[Tf2N] - ion.
Figure G-40: Plots of versus Nc for cycloalkanes
in imidazolium-based FILs comprising
[PF6]- ion.
Figure G-41: Plots of versus Nc for cycloalkanes
in imidazolium-based FILs comprising
[TfO]- ion.
Figure G-42: Plots of versus Nc for cycloalkanes
in imidazolium-based FILs comprising
[EMIM]+ ion.
Figure G-43: Plots of versus Nc for cycloalkanes
in imidazolium-based FILs comprising
[BMIM]+ ion.
Figure G-44: Plots of versus Nc for cycloalkanes
in imidazolium-based FILs comprising
[HMIM]+ ion.
Figure G-45: Plots of versus Nc for cycloalkanes
in imidazolium-based FILs comprising
[MOIM]+ ion.
Figure G-46: Plots of versus Nc for cycloalkanes
in phosphonium-based FILs
comprising [3C6C14P]+ ion.
Figure G-47: Plots of versus Nc for cycloalkanes
in ammonium-based FILs comprising
Figure G-48: Plots of versus Nc for cycloalkanes
in the pyridinium-based FILs [Epy]
[Tf2N] and [BMPy] [BF4].
Figure G-49: Plots of versus Nc for cycloalkanes
in pyrrolidinium-based FILs
comprising [BMPyrr]+ ion.
Figure G-50: Plots of versus Nc for cycloalkanes
in the sulfonium-based FIL [Et3S]
[Tf2N].
Figure G-51: Plots of versus Nc for alkan-1-ols
in imidazolium-based FILs comprising
[BF4]- ion.
Figure G-52: Plots of versus Nc for alkan-1-ols
in imidazolium-based FILs comprising
[Tf2N] -ion.
Figure G-53: Plots of versus Nc for alkan-1-ols
in imidazolium-based FILs comprising
[PF6]- ion.
Figure G-54: Plots of versus Nc for alkan-1-ols
in imidazolium-based FILs comprising
[TfO]- ion.
Figure G-55: Plots of versus Nc for alkan-1-ols
in imidazolium-based FILs comprising
[EMIM]+ ion.
Figure G-56: Plots of versus Nc for alkan-1-ols
in imidazolium-based FILs comprising
[BMIM]+ ion.
Figure G-57: Plots of versus Nc for alkan-1-ols
in imidazolium-based FILs comprising
[HMIM]+ ion.
Figure G-58: Plots of versus Nc for alkan-1-ols
in imidazolium-based FILs comprising
[EMIM]+ ion.
Figure G-59: Plots of versus Nc for alkan-1-ols
in phosphonium-based FILs comprising
[3C6C14P]+ ion.
Figure G-60: Plots of versus Nc for alkan-1-ols
in ammonium-based FILs comprising
[Tf2N]- ion.
Figure G-61: Plots of versus Nc for alkan-1-ols
in the pyridinium-based FILs [BMPy]
[BF4] and [Epy] [Tf2N].
Figure G-62: Plots of versus Nc for alkan-1-ols
in pyrrolidinium-based FILs comprising
[BMPyrr]+ ion.
Figure G-63: Plots of versus Nc for alkan-1-ols
in the sulfonium-based FIL [Et3S][Tf2N].
Figure G-64: Plots of versus Nc for
alkylbenzenes in imidazolium-based FILs
comprising [BF4]- ion.
Figure G-65: Plots of versus Nc for
alkylbenzenes in imidazolium-based FILs
comprising [Tf2N]- ion.
Figure G-66: Plots of versus Nc for
alkylbenzenes in imidazolium-based FILs
comprising [TfO]- ion.
Figure G-67: Plots of versus Nc for
alkylbenzenes in imidazolium-based FILs
comprising [EMIM]+ ion.
Figure G-68: Plots of versus Nc for
alkylbenzenes in imidazolium-based FILs
comprising [BMIM]+ ion.
Figure G-69: Plots of versus Nc for
alkylbenzenes in imidazolium-based FILs
comprising [HMIM]+ ion.
Figure G-70: Plots of versus Nc for
alkylbenzenes in imidazolium-based FILs
comprising [MOIM]+ ion.
Figure G-71: Plots of versus Nc for
alkylbenzenes in phosphonium-based FILs
comprising [3C6C14P]+ ion.
Figure G-72: Plots of versus Nc for
alkylbenzenes in ammonium-based FILs comprising
[Tf2N]- ion.
Figure G-73: Plots of versus Nc for
alkylbenzenes in the pyridinium-based FILs [BMPy]
[BF4] and [Epy] [Tf2N].
Figure G-74: Plots of versus Nc for
alkylbenzenes in [BMPyrr] [Tf2N] and [Et3S] [Tf2N].
Figure G-75: Plots of versus Nc for ket-2-ones
in imidazolium-based FILs comprising
[BF4]- ion.
Figure G-76: Plots of versus Nc for ket-2-ones
in imidazolium-based FILs comprising
[Tf2N] - ion.
Figure G-77: Plots of versus Nc for ket-2-ones
in imidazolium-based FILs comprising
[EMIM]+ ion.
Figure G-78: Plots of versus Nc for ket-2-ones
in imidazolium-based FILs comprising
[BMIM]+ ion.
Figure G-79: Plots of versus Nc for ket-2-ones
in imidazolium-based FILs comprising
[HMIM]+ ion.
Figure G-80: Plots of versus Nc for ket-2-ones
in phosphonium-based FILs comprising
[3C6C14P]+ ion.
Figure G-81: Plots of versus Nc for ket-2-ones
in ammonium-based FILs comprising
[Tf2N]- ion.
Figure G-82: Plots of versus Nc for ket-2-ones
in the imidazolium-based FILs [Epy]
[Tf2N] and [BMPy] [BF4].
Figure G-83: Plots of versus Nc for ket-2-ones
in the pyrrolidinium-based FIL [BMPyrr]
[Tf2N].
Figure H-1: Limiting selectivity at 313.15 K of
imidazolium-based fluorinated ionic liquids for the hexane (1)/benzene (2)
system, representing aliphatics/aromatics separation problems.
Figure H-2: Limiting capacity at 313.15 K of
imidazolium-based fluorinated ionic liquids for the hexane (1)/benzene (2)
system, representing aliphatics/aromatics separation problems.
Figure H-3: Limiting selectivity and capacity at
313.15 K of phosphonium-based fluorinated ionic liquids for the hexane
(1)/benzene (2) system, representing aliphatics/aromatics separation
problems.
Figure H-4: Limiting selectivity and capacity at
313.15 K of ammonium-based fluorinated
ionic liquids for the hexane (1)/benzene (2) system, representing
aliphatics/aromatics separation problems.
Figure H-5: Limiting selectivity at 313.15 K
of ammonium-based fluorinated ionic liquids for the methanol (1)/benzene (2)
system, representing alcohols/aromatics separation problems.
Figure H-6: Limiting selectivity and capacity at
313.15 K of phosphonium-based fluorinated ionic liquids for the methanol
(1)/benzene (2) system, representing alcohols/aromatics separation problems.
Figure H-7: Limiting selectivity and capacity at
313.15 K of ammonium-based fluorinated
ionic liquids for the methanol (1)/benzene (2) system,
representing alcohols/aromatics separation problems.
Figure H-8: Limiting selectivity at 313.15 K of
imidazolium-based fluorinated ionic liquids for the methanol (1)/acetone (2)
system, representing alcohols/ketones separation problems.
Figure H-9: Limiting capacity at 313.15 K of
imidazolium-based fluorinated ionic liquids for the methanol (1)/acetone (2)
system, representing alcohols/ketones separation problems.
Figure H-10: Limiting selectivity and capacity
at 313.15 K of phosphonium-based fluorinated
ionic liquids for the methanol
(1)/acetone (2) system, representing
alcohols/ketones separation problems.
Figure H-11: Limiting selectivity and capacity
at 313.15 K of ammonium-based fluorinated
ionic liquids for the methanol
(1)/acetone (2) system, representing
alcohols/ketones separation problems.
Figure H-12: Limiting selectivity at 313.15 K of
imidazolium-based fluorinated ionic liquids
for the n-hexane (1)/hex-1-ene (2) system, representing
paraffins/olefins
separation problems.
Figure H-13: Limiting capacity at 313.15 K of
imidazolium-based fluorinated ionic liquids for the n-hexane (1)/hex-1-ene (2)
system, representing paraffins/olefins separation problems.
Figure H-14: Limiting selectivity and capacity
at 313.15 K of phosphonium-based fluorinated ionic liquids for the n-hexane
(1)/hex-1-ene (2) system, representing paraffins/olefins separation
problems.
Figure H-15: Limiting selectivity and capacity
at 313.15 K of ammonium-based fluorinated
ionic liquids for the n-hexane (1)/hex-1-ene (2) system,
representing paraffins/olefins separation problems.
Figure H-16: Limiting selectivity and capacity
at 313.15 K of pyrrolidinium-based fluorinated ionic liquids for the n-hexane
(1)/hex-1-ene (2) system, representing paraffins/olefins separation
problems.
Figure H-17: Limiting selectivity at 313.15 K of
imidazolium-based fluorinated ionic liquids
for the benzene (1)/butan-2-one (2) system, representing
ketones/aromatics separation problems.
Figure H-18: Limiting capacity at 313.15 K of
imidazolium-based fluorinated ionic liquids for the benzene (1)/butan-2-one (2)
system, representing ketones/aromatics separation problems.
Figure H-19: Limiting selectivity and capacity
at 313.15 K of phosphonium-based fluorinated
ionic liquids for the benzene (1)/butan-2-one (2) system,
representing
ketones/aromatics separation problems.
Figure H-20: Limiting selectivity at 313.15 K of
imidazolium-based fluorinated ionic liquids
for the ethanol (1)/ butan-2-one (2) system, representing
alcohols/ketones separation problems.
Figure H-21: Limiting selectivity and capacity
at 313.15 K of phosphonium-based fluorinated ionic liquids for the ethanol (1)/
butan-2-one (2) system, representing alcohols/ketones separation problems.
Figure I-1: Variation of limiting activity
coefficients of various solutes depending on Nc, the carbon number of the alkyl
chain attached to the methylimidazolium group with [BF4]- anion.
Figure I-2: Variation of limiting activity
coefficients of various solutes depending on Nc, the carbon number of the alkyl
chain attached to the methylimidazolium group with [Tf2N] - anion.
Figure I-3: Variation of limiting activity
coefficients of various solutes depending on Nc, the carbon number of the alkyl
chain attached to the methylimidazolium group with [TfO]- anion.
Figure I-4: Variation of limiting activity
coefficients of n-hexane and hex-1-ene depending on Nc, the carbon number of
the alkyl chain attached to the methylpyrrolidinium group with
[Tf2N]- anion.
Figure I-5: Variation of limiting selectivities
of n-hexane to benzene depending on Nc, the carbon number of the alkyl chain
attached to the methylimidazolium group with common [BF4]-,
[Tf2N]- and [TfO]- anions.
Figure I-6: Variation of limiting selectivity of
n-hexane to hex-1-ene depending on Nc, the carbon number of the alkyl chain
attached to the methylpyrrolidinium or methylimidazolium group with common
[Tf2N]- anion.
LIST OF PHOTOGRAPHS
Photograph 2-1: The helical plate used in the
dilutor cell designed by Kutsuna and Hori (2008). Photograph 4-1:
Gas-Liquid Chromatography equipment.
Photograph 4-2: Set-up of the inert gas
stripping apparatus.
Photograph 4-3: The dilutor cell.
LIST OF TABLES
Table 2-1: Potential applications of ionic
liquids in the chemical industry (Plechkova and Seddon 2008).
Table 2-2: Ionic liquids versus molecular
solvents (Plechkova and Seddon, 2008).
Table 2-3: Literature selectivity and capacity
data at infinite dilution for selected ionic
liquids, NMP and sulfolane for different separation problems at
T = 313.15 K. Table 2-4: Advantages and disadvantages
of the Gas Liquid Chromatographic method. Table 2-5:
Advantages and disadvantages of the inert gas stripping method.
Table 4-1: GC specification and set-up.
Table 5-1: Infinite dilution activity
coefficients of selected organic solutes in n-hexadecane.
Table 5-2: Activity coefficients at infinite
dilution of organic solutes
intrihexyltetradecylphosphonium bis-(trifluoromethylsulfonyl)
imide with solvent column loading n3 = 1.577 mmol (29.5 %) at T
= (313.15, 333.15, 353.15 and 373.15) K.
Table 5-3: Activity coefficients at infinite
dilution of organic solutes in
trihexyltetradecylphosphonium bis (trifluoromethylsulfonyl) imide
with solvent column loading n3 =2.236 mmol (31.7 %) at T =
(313.15, 333.15, 353.15 and 373.15) K.
Table 5-4: Average activity coefficients at
infinite dilution of organic solutes in
trihexyltetradecylphosphonium bis-(trifluoromethylsulfonyl) imide
at T = (313.15, 333.15, 353.15 and 373.15) K.
Table 5-5: Partial molar excess enthalpies at
infinite dilution for organic solutes in the
ionic liquid trihexyltetradecylphosphonium
bis-(trifluoromethylsulfonyl) imide, calculated from the Gibbs Helmholtz
equation.
Table 5-6: Activity coefficients at infinite
dilution of organic solutes in
trihexyltetradecylphosphonium tetrafluoroborate with solvent
column loading
n3 = 2.395 mmol (25.09 %) at T = (313.15,
333.15, 353.15 and 373.15) K.
Table 5-7: Activity coefficients at infinite
dilution of organic solutes in
trihexyltetradecylphosphonium tetrafluoroborate with solvent
column loading
n3 = 2.236 mmol (30.97 %) at T = (313.15,
333.15, 353.15 and 373.15) K.
Table 5-8: Average activity coefficients at
infinite dilution of organic solutes in
trihexyltetradecylphosphonium tetrafluoroborate at T =
(313.15, 333.15, 353.15 and 373.15) K.
Table 5-9: Partial molar excess enthalpies at
infinite dilution for organic solutes in the
ionic liquid trihexyltetradecylphosphonium tetrafluoroborate,
calculated from the Gibbs-Helmholtz equation.
Table 5-10: Activity coefficients at infinite
dilution of organic solutes in
trihexyltetradecylphosphonium hexafluorophosphate with
n3 = 1.615 mmol (25.1 %) at T = (313.15, 333.15, 353.15 and
363.15) K.
Table 5-11: Activity coefficients at infinite
dilution of organic solutes in
trihexyltetradecylphosphonium hexafluorophosphate with
n3 = 2.659 mmol (29.4 %) at T = (313.15, 333.15, 353.15 and
363.15) K.
Table 5-12: Average activity coefficients at
infinite dilution of organic solutes in
trihexyltetradecylphosphonium hexafluorophosphate at T =
(313.15, 333.15, 353.15 and 363.15) K.
Table 5-13: Partial molar excess enthalpies at
infinite dilution for organic solutes in the
ionic liquid trihexyltetradecylphosphonium hexafluorophosphate
calculated from the Gibbs-equation.
Table 5-14: Activity coefficients at infinite
dilution of organic solutes in
methyltrioctylammonium bis-(trifluoromethylsulfonyl) imide with
n3 = 1.77 mmol (25.33 %) at T = (303.15, 313.15 and 323.15)
K.
Table 5-15: Activity coefficients at infinite
dilution of organic solutes in
methyltrioctylammonium bis-(trifluoromethylsulfonyl) imide with
n3 = 2.044 mmol (29.63 %) at T = (303.15, 313.15 and 323.15)
K.
Table 5-16: Average activity coefficients at
infinite dilution of organic solutes in
methyltrioctylammonium bis-(trifluoromethylsulfonyl) imide at
T = (303.15, 313.15 and 323.15) K.
Table 5-17: Excess molar enthalpies at infinite
dilution of organic solutes in the ionic
liquid methyltrioctylammonium bis-(trifluoromethylsulfonyl)
imide, calculated using the Gibbs-Helmholtz equation.
Table 5-18: Activity coefficients at infinite
dilution of organic solutes in 1-butyl-3-
methylimidazolium hexafluoroantimonate with n3 = 3.312
mmol (26.90 %) at T = (313.15, 323.15 and 333.15) K.
Table 5-19: Activity coefficients at infinite
dilution of organic solutes in 1-butyl-3-
methylimidazolium hexafluoroantimonate with n3 = 4.578
mmol (31.98 %) at T = (313.15, 323.15 and 333.15) K.
Table 5-20: Average activity coefficients at
infinite dilution of organic solutes in 1-butyl-3-
methylimidazolium hexafluoroantimonate at T = (313.15,
323.15 and 333.15) K. Table 5-21: Excess molar enthalpies at
infinite dilution of organic solutes in the ionic
liquid 1-butyl-3-methylimidazolium hexafluoroantimonate
calculated using the Gibbs-Helmholtz equation.
Table 5-22: Activity coefficients at infinite
dilution of organic solutes in 1-ethyl-3
methylimidazolium trifluoromethanesulfonate with n3 =
8.01 mmol (29.3 %) at T = (313.15, 323.15 and 333.15) K.
Table 5-23: Activity coefficients at infinite
dilution of organic solutes in 1-ethyl-3
methylimidazolium trifluoromethanesulfonate with n3 =
6.23 mmol (32.88 %) at T = (313.15, 323.15 and 333.15) K.
Table 5-24: Average activity coefficients at
infinite dilution of organic solutes in 1-ethyl-3
methylimidazolium trifluoromethanesulfonate at T =
(313.15, 323.15 and 333.15) K. Table 5-25: Excess molar
enthalpies at infinite dilution of organic solutes for the ionic
liquid 1-ethyl-3-methylimidazolium trifluoromethanesulfonate,
calculated using the Gibbs-Helmholtz equation.
Table 5-26: Activity coefficients at infinite
dilution of organic solutes in 1-methyl-3
octylimidazolium hexafluorophosphate with n3 = 6.69 mmol
(28.55 %) at T = 313.15, 323.15 and 333.15 K.
Table 5-27: Activity coefficients at infinite
dilution of organic solutes in 1-methyl-3-
octylimidazolium hexafluorophosphate with n3 = 5.135
mmol (33.26 %) at T = 313.15, 323.15 and 333.15 K.
Table 5-28: Average activity coefficients at
infinite dilution of organic solutes in 1-methyl-
3-octylimidazolium hexafluorophosphate at T = (313.15,
323.15 and 333.15) K. Table 5-29: Excess molar enthalpies at
infinite dilution of organic solutes for the ionic
liquid 1-methyl-3-octylimidazolium hexafluorophosphate,
calculated using the Gibbs-Helmholtz equation.
Table 5-30: Experimental infinite dilution
activity coefficients of n-hexane as well as Cyclohexane in NMP obtained by the
dilutor method and comparison with literature data taken from Gruber et al.
(1999).
Table 5-31: Experimental infinite dilution
activity coefficients obtained by the inert gas stripping method (IGST) for six
different organic solutes in the ionic liquid
Trihexyltetradecylphosphonium bis- (trifluoromethylsulfonyl)
imide, and comparison with similar data compiled with the help of the GC
method.
Table 5-32: Selectivity and Capacity at infinite
dilution at 313.15 K of the ionic liquids investigated in this work for
different separation problems and comparison with industrial separation agents
as well as other ionic liquids.
Table 6-1: Comparison of experimental IDACs in
the ionic liquid [3C6C14P] [Tf2N] at 313.15 K
from this work to available literature data.
Table 6-2: Comparison of experimental IDACs in
the ionic liquid [3C6C14P] [BF4] at 313.15 K
from this work to available literature data.
Table 6-3: Uncertainties on experimental
parameters for the GC method.
Table 6-4: Uncertainties on experimental
parameters for the dilutor method.
Table 6-5: Overall uncertainties on experimental
data and derived quantities.
Table 6-6: List of fluorinated ionic liquids
investigated in the literature and assigned numbers.
Table A-1: Literature data for in
imidazolium-based fluorinated ionic liquids. Table A-2:
literature data for in phosphonium-based fluorinated ionic liquids.
Table A-3: Literature data for in pyridinium and
pyrrolidinium-based fluorinated ionic
liquids.
Table A-4: Literature data for in ammonium and
sulfonium-based fluorinated ionic liquids.
Table A-5: Literature data for in
non-fluorinated ionic liquids.
Table C-1: Origin and Stated purity of solutes
and solvents.
Table C-2: Densities of solvents after
purification at different temperatures-Accuracy: #177; 0.4 % Table C-3:
Refractive indices of purified solvents at 293.15 K.
Table D-1: Saturation fugacity coefficients of
selected solutes at different temperatures. Table D-2:
Critical volumes, critical temperatures, and ionization energies,
IC of the
solutes and the carrier gas used in the calculation of the virial
coefficients. Table F-1: Infinite dilution selectivity and
capacity data at 313.15 K for FILs and selected industrial solvents
investigated in the literature as well as in this work.
NOMENCLATURE
Symbols
-- Solute peak area detected by gas chromatography (mV.min) --
Slope (min-1)
B -- Second virial coefficient (cm3
mol-1)
-- Concentration (mol cm-3)
-- Pure carrier gas flow rate (cm3min-1)
-- Total gas flow at still exit
(cm3min-1)
-- Solvent gas flow in the stream entering the still
(cm3min-1) -- Diffusion constant of solute in
solvent(cm2 s-1)
-- Diameter of bubbles (cm)
-- Fugacity for pure species
-- Fugacity for species in solution
-- Gibbs energy
-- Gravitational acceleration (cm2s-1)
-- Henry`s law constant --Enthalpy (J)
-- Path length of bubbles in solution (cm)
-- Poynting correction
-- Partitioning coefficient -- Capacity
-- Correction factors
-- Mass transfer coefficient in the liquid
(mol.s-1.cm2)
-- Molar mass (g.mol-1) -- Mass (g)
-- Amount of solvent in the still
-- Amount of solute in the still
-- Pressure (kPa)
or - vapour pressure (kPa)
-- Partial pressure (kPa)
-- Gas constant (J.mol-1 K-1) -- Radius of
bubbles (cm)
-- Selectivity
-- Absolute temperature (K)
-- Boiling point temperature (K)
-- Volume (cm3)
-- Volume of the vapour space in the still (cm3)
-- Mole fraction in the liquid phase -- Mole fraction in the
vapour phase
-- Compressibility factor
Greek letters
-- Activity coefficient, species in solution
-- Fugacity coefficient -- Density (g.cm-3)
-- Separation factor
-- Calibration detector constant
-- Ratio of mass transfer in the cell to mass transfer to reach
equilibrium taking into account liquid phase resistance only
-- Same as taking into account gas phase diffusion only
-- Limiting speed of bubbles in solution (cm.s-1)
-- Corrected activity coefficient at infinite dilution
-- Kinematic viscosity (cSt) -- Dynamic viscosity (cP)
-- Acentric factor
Subscripts
1-- Solute
2-- Carrier gas
3-- Solvent.
CG-- Carrier gas
-- Properties related to pure component i -- Interaction
properties
-- Critical Properties -- Reduced Properties -- Liquid
phase
o -- Initial value
f -- Final value
--Flowmeter --Gas phase
V --Vapour phase
Superscripts
--Ideal solution --Liquid phase --Vapor phase -- Infinite
dilution
-- Initial value --At saturation
-- Excess properties
-- Property in vapour phase
-- Property in liquid phase
-- Experimentally determined
-- Literature value
ABBREVIATIONS
CG -- Carrier gas
IDAC -- Infinite dilution activity coefficient IGST -- Inert Gas
Stripping Technique GLC -- Gas-Liquid Chromatography
COSMO-RS -- Conductor-like Screening Model for Real Solvents
DCT -- Double Cell Technique
SCT -- Single Cell Technique
GC -- Gas Chromatography
VLE -- Vapour Liquid Equilibrium LLE --Liquid Liquid Equilibrium
RD-- Relative Deviation
GCMs -- Group Contribution Methods FILs - Fluorinated Ionic
Liquids
Cations
[EMIM]+-- 1-ethyl-3-methylimidazolium
[HMIM]+-- 1-hexyl-3-methylimidazolium [MOIM]+--
1-methyl-3-octylimidazolium [BMIM]+-- 1-butyl-3-methylimidazolium
[3C4C1P]+-- Tributylmethylphosphonium [3C6C14P]+--
Trihexyltetradecylphosphonium [Py]-- Pyridinium
[Epy]-- Ethylpyridinium
[BMPy]+-- n-butyl-4-methylpyridinium
[MOPyrr]+-- 1-octyl-1-methyl-pyrrolidinium [BMPyrr]+--
1-butyl-1-methyl-pyrrolidinium [HMPyrr]+--
1-hexyl-1-methyl-pyrrolidinium [Et3S]+-- Triethylsulfonium
[C13C8N]+-- Methyltrioctylammonium
[3C1C4N]+-- Trimethylbutylammonium [C16MIM]+--
1-hexadecyl-3-methylimidazolium [CpMIM]+--
1-butyronitrile-3-methylimidazolium [EDMIM]+--
1-ethyl-3-dimethylimidazolium
[CpMMIM]+-- 1-butyronitrile-2,
3-dimethylimidazolium
[PDMIM]+-- 1-propyl-3-dimethylimidazolium.
[MMIM]+--1-methyl-3-methylimidazolium.
[PBA-MIM]+-- 1-propyl boronic acid-3-methylimidazolium
[PBA-OMIM]+-- 1-propyl boronic acid-3-octylimidazolium
[PBA-C10MIM]+-- 1-propyl boronic acid-3-decylimidazolium
[PBA-C12MIM]+-- 1-propyl boronic
acid-3-dodecylimidazolium [PropOMIM]+--
1-propenyl-3-methyloctylimidazolium
[PropC10MIM]+--1-propenyl-3-decylimidazolium
[PropC12MIM]+-- 1-propenyl-3-dodecylimidazolium
[H-O-MIM]+--1-hexyloxymethyl-3-methylimidazolium
[DH-O-MIM]+--1, 3-dihexyloxymethylimidazolium
Anions
[SCN]--- Thiocyanide
[Tf2N] --- Bis (trifluoromethylsulfonyl) Imide
[BF4]--- Tetrafluoroborate [TOS]---
Tosylate
[MeSO4]--- Methyl sulfate
[(C2F5)3PF3]--- Tris (pentafluoroethyl)
trifluorophosphate
[TFA]--- Trifluoroacetate [TfO]---
Trifluoromethylsulfonate
[SbF6]--- Hexafluoroantimonate [PF6]---
Hexafluorophosphate
[MDEGSO4]--- Diethyleneglycolmonoethylethersulfate
[Me2PO4]--- Dimethylphosphate
[C1OC2SO4]--- Methoxyethylsulfate
[FeCl4]--- Tetrachloridoferrate (III)
[Et-SO4]--- Ethylsulfate [Oc-SO4]---
Octylsulfate [N (CN) 2]- -- Dicyanamide
[(C8 H17)2PO2]--- Dimethylpentylphosphinate
[n-C18H35OO]--- Stearate [n-C16H33OO]---
Palmitate
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