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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

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par Kaniki TUMBA
University of Kwazalu-Natal - Master 2009
  

sommaire suivant

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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

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

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.

 

List of figures

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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