The Proton's Absolute Aqueous Enthalpy and Gibbs Free Energy of Solvation from Cluster-Ion Solvation Data

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Ion-pair entries corresponding to strong electrolytes were determined from ΔHf°[AB(aq)] − ΔHf°[A+(g)] − ΔHf°[B-(aq)] where ΔHf°[A+(g)] is 1536.2(0.1), 685.7(1.0), 609.5(0.7), 514.0(0.8), and 490.1(0.8) kJ/mol for H+, Li+, Na+, K+, and Rb+, respectively, and ΔHf°[B-(g)] is −143.5, −255.0(0.3), −233.5(0.1), −218.9(0.2), and −194.6(0.1) for OH-, F-, Cl-, Br-, and I-, respectively. These values are in excellent agreement with the values in the 1982 NBS tables (ref 16):  ΔHf°[A+(g)] is 1536.2, 685.8, 601.4, 514.3, and 490.1 kJ/mol for H+, Li+, Na+, K+, and Rb+, respectively, and ΔHf°[B-(g)] is −143.5, −255.0, −233.5, −218.9, and −194.6 for OH-, F-, Cl-, Br-, and I-, respectively.

ΔGf°[A+(g)] is 1516.9, 648.6, 574.3, 481.1, and 457.7 kJ/mol for H+, Li+, Na+, K+, and Rb+, respectively, and ΔGf°[B-(g)] is −138.7, −262.3, −239.3, −238.9, and −223.9 kJ/mol for OH-, F-, Cl-, Br-, and I-, respectively. These values were determined from data in the 1982 NBS tables (ref 16) and calculations of the gas-phase entropies (ref 31).

Standard entropies of formation in J mol-1K-1for the gas-phase ions were determined using ΔSf°[X(g)] = 108.8555 + 12.4716 ln(M) −v*S(X*) ±S[e-(g)], whereMis the molar mass in grams,v* is1/2for H+and the anions and 1 for the alkali ions,S(X*) is the element's absolute entropy in the standard state, andS[e-(g)] is the absolute entropy of the gaseous electron. It is added for cations, subtracted for anions, and determined by using 108.8555 + 12.4716 ln(M) withM= 5.4858 × 10-4and addingR[ln(2)] for the spin degeneracy to obtain the value 20.980 J mol-1K-1.