Infinite dilution activity coefficient measurements of organic solutes in fluorinated ionic liquids by gas-liquid chromatography and the inert gas stripping method

APPENDIX B: STRUCTURE OF IONIC LIQUIDS

[3C6C14P]⁺ [Tf2N] - [PF6]

[BF4]^- [OMIM] + [SbF6]

[BMIM]⁺ [EMIM] + [TfO] - [C83C1N] +

Figure B-1: Ions present in the structure of ionic liquids used in this work.

Appendix C: Origin and purity of chemicals

APPENDIX C: ORIGIN AND PURITY OF CHEMICALS

Table C-1: Origin and Stated purity of solutes and solvents.

Compound	Origin	Stated purity (Mass %)
[3C6C14P] [Tf2N]	Cytec	= 0.98
[3C6C14P] [BF4]	Cytec	= 0.98
[3C6C14P] [PF6]	Cytec	= 0.98
[3C8C1N] [Tf2N]	Solvent innovation	0.98
[BMIM] [SbF6]	Capital Lab	= 0.98
[EMIM] TfO]	Capital Lab	= 0.98
[MOIM] [PF6]	Capital Lab	= 0.95
NMP	Merck	= 0.98
n-hexadecane	Acros	0.99
n-alkanes (C5 to C12)	Capital Lab	= 0.98
Alk-1-enes (C5 to C12)	Capital Lab	= 0.98
Alk-1-ynes (C5 to C12)	Capital Lab	= 0.98
Cycloalkanes (C5 to C10)	Capital Lab	= 0.98
n-alkanols (C1 to C4)	Capital Lab	= 0.98
Alkylbenzenes (C6 to C9)	Capital Lab	= 0.98
Ket-2-ones (C3 to C4)	Capital Lab	= 0.98

Table C-2: Densities of solvents after purification at different temperatures-Accuracy: #177; 0.4
%.;*Interpolated value;^# Extrapolated data ^aFrom Rodriguez and Brennecke (2006); ^b From
Pereiro et al. (2007); ^c From Kneisl and Zondlo, (1987); ^d From Khasanshin et al (2009).

Solvents	293.15 K	303.15 K	313.15 K	323.15 K	333.15 K	Literature Data at 293.15 K
[3C6C14P] [Tf2N]	1.068870	1.062387	1.056497	1.051422	1.047132
[3C6C14P] [BF4]	-	-	-	0.925100	-
[3C6C14P] [PF6]	-	-	-	0.987150	-
[3C8C1N] [Tf2N]	1.112700	-	-	-	-
[BMIM] [SbF6]	1.694300	-	-	-	-
[EMIM] TfO]	1.387070	1.375511	1.369032	1.363705	1.359564	1.387392^a*
[MOIM] [PF6]	1.238510	-	-	-	-	1.23957^b
NMP	-	1.025173	1.017633	1.010888	1.004919	1.032313^c#
n-hexadecane	0.770522	-	-	-	-	0.77418^d#

Table C-3: Refractive indices of solvents after purification at 293.15 K. ^#Extrapolated data;
^aMehra, (2003); ^bFrom www.haochem.com?; ^cFrom Pereiro et al. (2007).

Solvents	Refractive index	Literature Data
[3C6C14P] [Tf2N]	1.45069
[3C8C1N] [Tf2N]	-
[BMIM] [SbF6]	1.41568
[EMIM] TfO]	1.43434
[MOIM] [PF6]	1.42430	1.42440^c
NMP	1.47047	1.465-1.470^b
n-Hexadecane	1.43463	1.4356^a#

Appendix D: Fugacities, critical data and ionization energies

APPENDIX D: FUGACITIES, CRITICAL DATA AND
IONIZATION ENERGIES

Table D-1: Saturation fugacity coefficients of selected solutes at different temperatures
determined from second virial coefficients (Smith et al (2005).

Solutes	303.15 K	313.15 K	323.15 K
n-hexane	0.982	0.977	0.970
Hex-1-ene	0.981	0.974	0.967
Cyclohexane	0.988	0.983	0.978
Methanol	0.997	0.995	0.993
Benzene	0.989	0.986	0.981
Acetone	0.988	0.984	0.980

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. (Reference: CRC
Handbook of Chemistry and Physics).

Solute	TC /K	VC/ cm^3.mol^-1	IC/ kJ.mol^-1
n-pentane	469.7	304	998.62
n-hexane	507.4	370	977.39
n-heptane	540.3	432	957.13
n-octane	568.8	492	947.48
n-nonane	594.7	555.2	937.83
Pent-1-ene	464.7	300	917.57
Hex-1-ene	504	350	910.82
Hept-1-ene	537.2	405	910.82
Oct-1-ene	566.6	464	909.85
Pent-1-yne	493.4	278	969.67
Hex-1-yne	539.29	331	960.02
Hept-1-yne	551.621	376.53	960.02
Oct-1-yne	598.46	441	960.02
Nony-1-ne	611	513.3	955.20
Cyclopentane	511.7	259	1014.05
Cyclohexane	553.8	308	951.34
Cycloheptane	604.2	353	961.95
Cyclooctane	647.2	410	941.69
Methanol	512.6	118	1046.86
Ethanol	516.2	167	1010.20
Propan-1-ol	536.7	218.5	986.07
Butan-1-ol	562.9	274	970.64
Benzene	562.1	259	892.10
Toluene	591.7	316	851.00
Acetone	508.1	209	935.90
Butan-2-one	535.6	267	918.54
Helium	5.2	57.5	2372.56

Appendix E: Calibration data

APPENDIX E: CALIBRATION DATA

y = 1.001x - 0.229
R² = 0.999

20 30 40 50 60 70

Display Temperature, (^oC)

70

Actual Temperature, (°C)

60

50

40

30

20

Figure E-1: Temperature calibration curve for the dilutor cell Pt 100.

y = 1.149x + 3.572
R² = 0.999

84 86 88 90 92 94

Display Pressure (kPa)

112

Actual Temperature (kPa)

110

108

106

104

102

100

Figure E-2: Pressure calibration curve for the dilutor cell pressure transducer.

Appendix F: Selectivities and capacities

APPENDIX F: SELECTIVITIES AND CAPACITIES

Table F-1: Infinite dilution selectivity and capacity data at 313.15 K for FIL`s and selected industrial solvents investigated in the literature (Subscripts are references given in Chapter 6) as well as in this work*; ^#Data obtained at 298.15 K.

Butan-2-one (2)

Benzene (2)

Hex-1-ene (2)

Acetone (2)

Hexane (1)

/benzene (2)

Cyclohexale

(1 )/benzene (2)

Methanol (1) /benzene (2)

Benzene (1)

/butan-2-one (2)

Hexane (1)

/he(-1-ene (2)

Methanol (1) /acetone (2)

Ethanol (1)

/butan-2-one (2)

Limiting Selectivity Limiting Capacity

[EMIM][BF4]^[1][2]	38.65	20.06	0.17	1.54	2.02	0.39	0.47	0.41	0.02	0.91	0.62
[EMIM] [Tf2N] [3][4][5]	21.12	9.75	1.08	2.40	2.08	3.17	3.54	0.83	0.08	2.44	2.00
[MMIM] [Tf2N] [4]	27.26	15.48	-	-	2.24	-	-	0.74	0.06	-	-
[BMIM][BF4]^[2][6][7]	23.84	12.53	0.52	1.51	1.70	1.23	0.87	0.41	0.03	0.98	0.63
[BMIM] [Tf2N] [4][8]	15.13	9.16	1.23	-	1.89	2.97	-	1.12	0.14	2.70	-
[BMIM][TfO]^[9]	23.04	10.66	0.44	-	2.23	0.79	-	0.63	0.06	1.13	-
[DMPIM][BF4]^[10][11]	70.40	31.77	0.24	-	-	0.34	-	0.28	-	0.40	-
[EDMIM] [Tf2N] [3]	23.03	13.22	1.33	1.92	2.07	3.56	3.58	0.91	0.08	2.44	1.75
[HMIM][BF4]^[2][12]	19.53	5.61	0.41	1.49	2.00	0.82	1.42	0.61	0.11	1.22	0.91
[HMIM][PF6]^[13]	18.46	10.19	1.54	-	2.11	-	-	0.96	0.11	-	-
[HMIM] [Tf2N] [14][15][16]	11.22	6.70	1.65	1.64	1.69	3.54	3.50	1.46	0.22	3.13	2.38
[MOIM][BF4]^[17]	10.01	7.04	0.83	1.17	1.71	1.29	1.48	0.85	0.15	1.33	1.00
[MOIM] [Tf2N] [16]	7.89	5.52	1.75	-	1.57	-	-	1.54	0.31	-	-
[C16MIM][BF4]^[18]	3.10	2.13	1.52	0.76	1.35	1.29	1.47	1.27	0.55	1.08	0.96
[3C6C14P][BF4]^*	3.41	2.38	1.31	0.92	1.26	1.25	1.30	2.44	0.90	2.32	2.25
[3C6C14P] [Tf2N]^*	2.80	2.03	2.77	1.23	1.21	3.80	4.00	2.56	1.10	3.51	3.15
[3C6C14P][(C2F5)3PF3]^[20]	3.25	2.40	5.83	-	1.23	-	-	5.00	1.89	-	-
[3C1C4N] [Tf2N] [21]	13.94	0.58	1.07	-	1.89	3.38	-	0.75	0.10	2.38	-
[BMPy][BF4]^[22][23]	36.88	17.71	0.66	1.66	-	1.52	1.78	0.61	-	1.41	1.01
[BMPyrr] [Tf2N] [16]	15.47	-	-	1.62	1.92	-	3.26	1.16	0.14	-	1.89
[Et3S] [Tf2N] [24]	22.71	12.76	1.28	-	2.17	-	-	0.90	0.09	-	-
[Epy] [Tf2N] [25][26]	24.38	14.31	0.95	2.00	2.33	2.62	2.65	0.77	0.07	2.13	1.54
[3C6C14P][PF6]^*	2.96	2.15	3.12	0.97	1.20	3.17	3.21	1.47	0.59	1.49	1.42
[C13C8N] [Tf2N] [27]*	3.77	2.70	2.68	1.22	1.33	3.11	3.44	2.27	0.80	2.63	2.78
[EMIM][TfO]^[28]*	30.20	15.19	0.33	-	2.31	-	-	0.45	0.03	-	-
[MOIM][PF6^][29]*	11.27	7.03	1.88	-	1.72	-	-	1.04	0.16	-	-
[BMIM][SbF6]^[30]*	22.25	12.52	1.41	1.98	2.08	4.26	3.74	0.79	0.07	2.38	1.56
[BMIM][PF6]^[31]	-	-	-	-	3.06	3.06	-	-	-	1.41	1.01
[EMIM][TFA]^[32]	27.03	12.97	0.08	-	2.34	-	-	0.36	0.03	-	-
[HMIM][TfO]^[33]	14.37	7.37	-	-	-	-	-	0.68	-	-	-
[BMPyrr][TfO]^[34]	-	-	-	2.45	-	-	-	-	0.05	-	-
[HMPyrr] [Tf2N] [35]	-	-	-	1.70	-	-	-	-	0.22	-	-
[OMPyrr] [Tf2N] [35]	-	-	-	1.53	-	-	-	-	0.30	-	-
Sulfolane^[36]	18.17	9.81	0.91	1.20	-	1.38	1.52	0.43	-	0.64	0.51
NMP^[37]	11.24	7.05	-	-	0.53	-	-	0.95	0.16	-	-
Chlorobenzene^[38][39]	-	-	-	-	-	0.17*	8.29	-	-	-	0.47
Dimethylsulfoxide^[38][39]	-	-	-	-	-	0.35*	0.20*	-	-	0.38*	0.35*

Appendix G: Effect of structure on infinite dilution activity coefficient values