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33947611180
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Since the forward reaction of Eq. (3) is called "hydration", we avoid the phrase "hydration" to denote the effect of intermolecular interaction between the solute and the solvent water. Instead, we use the phrase "solvation" to refer to the intermolecular interaction effects.
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When some of the reactive species are at finite concentration and are not coincident with the solvent species, K given by Eq. (6) is a function also of the solute concentration. In this case, although Eq. (6) is a valid expression, K depends on the solute concentration and cannot serve as an "equilibrium constant." When one of the reactive species is the solvent itself and is present in excess, its concentration (density) does not change in the course of reaction and the concentration value in Eq. (6) is simply equal to the input density. Eq. (6) is thus assured to be valid as an expression for the equilibrium constant when one of the reactive species is the solvent and the others are at infinite dilution.
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Gaussian 03, Revision C.02, M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery, Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A. Pople, Gaussian, Inc., Wallingford CT, 2004.
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2 in the PCM calculation was 2 kcal/mol, and the arguments in Results and Discussion are not affected.
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