SUPPORTING INFORMATION FOR
Composition Dependent Structural Organization in
Trihexyl(tetradecyl)phosphonium Chloride Ionic Liquid - Methanol Mixtures
Aditya Gupta, Shobha Sharma and Hemant K. Kashyap*
Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India
Email: hkashyap@chemistry.iitd.ac.in
Table S1: Composition dependence of bulk density of [P666, 14+][ Cl-] - Methanol mixture at 295
K.
Simulated Density (g/cm3)
0.784
0.814
0.832
0.850
0.856
0.866
0.870
0.875
0.875
0.875
0.875
Experimental Density(a)
(g/cm3)
0.00
0.7862
0.016
0.8091
0.035
0.8264
0.055
0.8392
0.080
0.8510
0.125
0.8638
0.154
0.8650
0.203
0.8750
0.349
0.8840
0.459
0.8877
0.704
0.8932
0.881
0.8928
1.00
0.8933
(a) Data taken from reference 67 in the main article.
xIL
0.00
0.02
0.04
0.08
0.10
0.20
0.30
0.50
0.70
0.90
1.00
xIL
1
Table S2: Composition dependence of excess molar enthalpy in [P666, 14+][ Cl-] -Methanol
mixture at 295 K.
xIL
0.02
0.04
0.08
0.10
0.20
0.30
0.50
0.70
0.90
Excess Molar Enthalpy
(kJ/mol)
-1.99
-3.84
-7.30
-9.04
-14.70
-14.93
-12.30
-6.32
-1.93
Table S3: Number of cations, anions and methanol molecules corresponding to each
composition used for the simulations.
xIL
No. of Cations (P666, 14+)
0.00
0.02
0.04
0.08
0.10
0.20
0.30
0.50
0.70
0.90
1.00
0
20
40
80
100
200
300
500
700
900
1000
No. of Anions
(Cl-)
0
20
40
80
100
200
300
500
700
900
1000
2
No. of Methanol Molecules
1000
980
960
920
900
800
700
500
300
100
0
Figure S1: Ionic liquid mole-fraction, xIL, dependence of characteristic distances obtained from
the low q peak positions from the simulated S(q) data for [P666, 14+][ Cl-] - Methanol mixture at
295K. The color coding is same as in Fig. 4 in the main text.
3
Figure S2: Partial structure function for Me OH- P666, 14+ at different IL mole-fractions.
Figure S3: Definition of CTS group in P666, 14+ cation.
4
(b)
(a)
Figure S4: Radial distribution function, g(r), for (a) methanol oxygen (OMeOH) and its hydroxyl
hydrogen (HOMeOH) and (b) its blown-up view near the close contact distances.
(b)
(a)
Figure S5: Blown-up view of (a) P - P and (b) Cl- - Cl- rdfs near close contact distances.
5
(a)
(b)
Figure S6: Blown-up view of (a) P - Cl- and (b) OMeOH - OMeOH rdfs near close contact
distances.
(a)
(b)
Figure S7: Blown-up view of (a) Cl- - OMeOH and (b) P - OMeOH rdfs near close contact
distances.
6