1
Manuscript No. S04 Q38- Revised
Eletronic Supplementary Material - EPOC
Note on composition scales
There is extensive literature on the correlation between compositions of binary mixture composition and their properties,
including macroscopic, spectroscopic, etc. The following are representative references, showing that the mole fraction scale is
most extensively employed, relative to other possible scales.
Mole Fraction Scale
Thermodynamic Properties of water- HBD solvents binary mixtures
1- See ref.16b, c and 25c of manuscript.
2- B. Andersson and G. Olofsson, J. Solution Chem., 1988, 17, 1169.
3- R. F. Lama and B. C.-Y. Lu, J. Chem. Eng. Data, 1965, 10, 216.
4- M. Rosés, F. Rived and E. Bosch, J. Chem. Soc. Faraday Trans., 1993, 89, 1723.
5- W. Siu and Y. Koga, Can. J. Chem., 1989, 67, 671.
6- H. Tanaka and K. E. Gubbins, J. Chem. Phys., 1992, 97, 2626.
Spectrophotometric Studies of water- HBD solvents binary mixtures
1- See ref.12, 25a and 27 of manuscript.
2
2- E. Bosch and M. Rosés, J. Chem. Soc. Faraday, 1992, 88, 3541.
3- E. Bosch, M. Rosés, K. Herodes, I. Koppel, I. Leito, I. Koppel and V. Taal, J. Phys. Org. Chem., 1996, 9, 403.
4- M. Brai and U. Kaatze, J. Phys. Chem., 1992, 96, 8946.
5- R. L. Brinkley and R. B. Gupta, Ind. Eng. Chem. Res., 1998, 37, 4823.
6- U. Buhvestov, F. Rived, C. Ràfols, E. Bosch and M. Rosés, J. Phys. Org. Chem., 1998, 11, 185.
7- C. Czeslik and J. Jonas, Chem. Phys. Lett., 1999, 302, 633.
8- M. D’Angelo, G. Onori and A. Santucci, J. Chem. Phys., 1994, 100, 3107.
9- J. M. Harvey, S. E. Jackson and M. C. R. Symons, Chem. Phys. Lett., 1977, 47, 440.
10- U. Kaatze, M. Schäfer and R. Pottel, Z. Phys. Chem. Neue Folge, 1989, 165, 103.
11- U. Kaatze, A. Schumacher and R. Pottel, Ber. Bunsenges. Phys. Chem., 1991, 5, 585.
12- C. Lerf and P Suppan, J. Chem. Soc. Faraday Trans., 1992, 88, 963.
13- N. Micali, S. Trusso, C. Vasi, D. Blaudez and F. Mallamce, Phys. Rev. E, 1996, 54, 1720.
14- J. Ortega, M. Rosés and E. Bosch, J. Solution Chem., 1994, 23, 735.
15- J. Ortega, C. Ràfols, E. Bosch and M. Rosés, J. Chem. Soc. Perkin Trans 2, 1996, 1497.
16- M. Rosés, J. Ortega and E. Bosch. J. Solution Chem., 1995, 24, 51.
17- M. Rosés, C. Ràfols, J. Ortega and E. Bosch, J. Chem. Soc. Perkin Trans 2, 1995, 1607.
18- M. Rosés, U. Buhvestov, C. Ràfols, F. Rived and E. Bosch, J. Chem. Soc. Perkin Trans 2, 1997, 1341.
19- A. Sacco, F. M. De Cillis and M. Holz, J. Chem. Soc. Faraday Trans., 1998, 94, 2089.
20- M. A. R. Silva, D. C. Da Silva, V. G. Machado, E. Longhinotti and V. L. A. Frescura, J. Phys. Chem A, 2002,
106, 8820.
21- R. D. Skierczynski and K. A. Connors, J. Chem. Soc. Perkin Trans. 2, 1994, 467.
3
22- J. A. Soroka and K. B. Soroka, J. Phys. Org. Chem., 1997, 10, 647.
Volumetric and Viscosity Data of water- HBD solvents binary mixtures
1- G. Douhéret and A. Pal, J. Chem. Eng. Data, 1988, 33, 40.
2- G. Douhéret, M. I. Davis and H. Hoiland, J. Mol. Liq., 1999, 80, 1.
3- Y. Koga, J. Phys. Chem., 1992, 96, 10466.
4- Y. Koga, Chem. Phys. Lett., 1995, 240, 340.
5- Y. Koga and P. Westh, Bull. Chem. Soc. Jpn., 1996, 69, 1505.
6- P. Petong, R. Pottel and U. Kaatze, J. Phys. Chem. A, 2000, 104, 7420.
7- V. K. Reddy, K. S. Reddy and A. Krishnaiah, J. Chem. Eng. Data, 1994, 39, 615
8- S. A. Wieczorek, J. Chem. Thermodynamics, 1991, 23, 717.
Volume Fraction Scale
1- R. P. W. Scott, Analyst, 2000, 125, 1543.
Molality Scale
1- A. Inglese and R. H. Wood, J. Chem. Thermodynamics, 1996, 28, 1059.
2- M. Sakurai, K. Nakamura and K. Nitta, Bull. Chem. Soc. Jpn., 1994, 67, 1580.
4
Manuscript No. S04 Q38- Revised
Eletronic Supplementary Material
Table ESI 1. Polynomial dependence of ET(33), kcal/mol, on the analytical mole fraction of water in ROH-W mixtures,
xwAnalytical , calculated according to the equation: E (33)
T
obs
= ET(33)ROH + B (W) + C (W)2 + D (W)3 + E (W)4 + F (W)5 + G (
(W)7.
ET(33)ROH; a
Binary Mixture
T,
B
C
D
E
F
G
H
C
EtOEtOH / W
10
59.388
5.510
-30.887
133.618
-207.434
110.846
[0.032]
25
58.790
4.581
-23.897
114.231
-183.754
100.539
[-0.010]
40
57.689
9.711
-49.798
177.763
-253.267
126.816
[0.071]
60
56.521
12.222
-56.423
189.945
-262.869
129.743
[0.069]
PrOEtOH / W
10
59.238
4.682
-30.050
312.248
-1347.933
2710.423
-2541.642
903.890
[0.002]
25
58.154
21.501
-286.424
187.935
-5881.280
9463.187
-7522.766
2344.954
[0.006]
40
56.806
35.396
-422.181
2464.588 -7165.583
10932.644
-8372.685
2540.685
[0.004]
60
55.738
44.318
-55.715
3265.520 -9514.151
14428.105
-10928.733
3270.052
[0.002]
BuOEtOH / W
10
59.169
28.385
-366.944
2437.079 -7815.094
12807.346
-10341.887
3262.841
[0.151]
25
57.324
30.006
-387.831
2639.196 -8572.329
14110.948
-11396.688
3589.000
[0.146]
40
56.033
35.954
-382.199
2376.714 -7458.520
12147.468
-9811.491
3104.910
[0.177]
a- Calculated by regression. The values in brackets are ET(33)ROH = Experimental ET(33)ROH - calculated ET(33)ROH
b- Abbreviations: r2 = correlation coefficient for the polynomial regression, SD = standard deviation.
6
W) + H
r2b
SDb
0.9993
0.112
0.9994
0.100
0.9993
0.111
0.9992
0.129
0.9985
0.155
0.9972
0.213
0.9992
0.116
0.9987
0.155
0.9908
0.374
0.9895
0.414
0.9878
0.455
5
Manuscript No. S04 Q38- Revised
Eletronic Supplementary Material
Table ESI 2. Polynomial dependence of ET(QB), kcal/mol, on the analytical mole fraction of water in ROH-W mixtures,
xwAnalytical ,
calculated according to the equation: ET(QB)obs = ET(QB)ROH + B (W) + C (W)2 + D (W)3 + E (W)4 +
F (W)5 + G (W)6 + H (W)7.
ET(QB)ROH;a
r2b
Binary Mixture
T,
B
C
D
E
F
G
H
C
EtOEtOH / W
10
59.327
3.048
-18.275
71.223
-102.533
52.067
0.9990
[0.023]
25
58.910
2.714
-14.670
60.214
-87.813
45.150
0.9992
[0.028]
40
58.371
5.056
-28.276
94.765
-125.113
59.445
0.9990
[0.018]
60
57.647
7.402
-39.384
121.322
-153.003
69.893
0.9991
[0.053]
PrOEtOH / W
10
59.247
-1.903
46.640
-222.089
495.860
-510.167
197.210
0.9991
[-0.005]
25
58.706
0.018
40.766
-215.076
498.413
-521.516
203.289
0.9981
[-0.006]
40
58.107
0.041
39.061
-194.336
437.053
-450.301
174.694
0.9983
[-0.007]
60
57.515
1.317
41.421
-234.928
549.156
-569.575
-219.101
0.9988
[-0.001]
BuOEtOH / W
10
59.197
5.451
-72.737
543.074
-1782.758
2918.331
-2337.656
731.655
0.9986
[0.003]
25
58.886
-3.628
66.410
-214.266
194.346
231.857
-503.439
234.183
0.9985
[0.004]
40
58.058
15.144 -176.829
1026.415
2876.411
4193.312
-3070.142
894.514
0.9963
[0.002]
a- Calculated by regression. The values in brackets are ET(QB)ROH = Experimental ET(QB)ROH - calculated ET(QB)ROH
b- Abbreviations: r2 = correlation coefficient for the polynomial regression, SD = standard deviation.
SDb
0.064
0.057
0.068
0.066
0.060
0.088
0.089
0.078
0.075
0.079
0.138
6
Manuscript No. S04 Q38- Revised
Eletronic Supplementary Material
Table ESI 3. Polynomial dependence of ET(MC), kcal/mol, on the analytical mole fraction of water in ROH-W mixtures,
xwAnalytical ,
calculated according to the equation: ET(MC)obs = ET(MC)ROH + B (W) + C (W)2 + D (W)3 + E (W)4 +
F (W)5 + G (W)6 + H (W)7.
ET(MC)ROH; a
r2b
Binary Mixture
T,
B
C
D
E
F
G
H
C
EtOEtOH / W
10
54.859
11.921 -72.483
237.751 -311.753
144.523
0.9991
[0.072]
25
54.124
9.488
-49.218
173.506 -237.333
113.859
0.9991
[0.065]
40
53.460
10.078 -48.220
160.556 -213.651
101.855
0.9991
[0.101]
60
52.620
3.268
56.714
-345.267 889.659 -1075.379 579.856 -97.678 0.9996
[0.004]
PrOEtOH / W
10
54.269
-3.793 133.982 -655.641 1436.855 -1442.483 541.578
0.9989
[-0.009]
25
53.469
-0.172 110.686 -580.970 1307.422 -1323.521 494.444
0.9989
[-0.008]
40
52.739
1.205
93.408
-488.819 1096.282 -1108.788 418.039
0.9990
[-0.005]
60
51.940
-1.984 122.642 -573.134 1197.539 -1154.168 420.826
0.9988
[-0.003]
BuOEtOH / W
10
53.779
-4.454 107.142 -448.576 910.920
-884.174 329.590
0.9955
[-0.009]
25
53.017
0.356
49.534
-199.336 431.267
-459.225 188.476
0.9955
[-0.017]
40
52.203
3.434
36.870
-167.640 378.207
-407.622 168.358
0.9964
[-0.005]
a- Calculated by regression. The values in brackets are ET(MC)ROH = Experimental ET(MC)ROH - calculated ET(MC)ROH
b- Abbreviations: r2 = correlation coefficient for the polynomial regression, SD = standard deviation.
SDb
0.106
0.111
0.119
0.089
0.117
0.119
0.123
0.138
0.249
0.267
0.251
7
Manuscript No. S04 Q38- Revised
Eletronic Supplementary Material
1-PrOH / W
2-Me-2-PrOH / W
57
60
58
56
-1
ET(30), kcal mol
ET(30), kcal mol
-1
56
55
54
53
54
52
50
48
52
46
51
44
0
0.2
0.4
VF (W)
0.6
0.8
0
0.2
0.4
0.6
xw
0.8
1.0
0
0.2
0.4
0.6
FV (W)
0.8
0
0.2
0.4
0.6
0.8
1.0
xw
Figure 1. Dependence of ET(30) on volume fraction and mole fraction of water, VF(W) and
xw,
respectively, in
aqueous 1-PrOH and 2-Me-2-PrOH, at 25 C. The diagonal line represents the expected behavior if
solvatochromism were ideal, i.e. if there were no preferential salvation of the probe by one component of the binary
mixture.