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.