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By Harold C. Helgeson

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ML n (omitting charges), coincides with the order of decreasing stabilities. It can be shown that for a divalent M in the presence of increasing concentration of monovalent L, changes in

The effect of the new yh data on calculated yAii values is slight ( < 20 per cent of the values calculated in this study) over most of the temperature interval for which calculations were made. These new data therefore have a negligible effect on the computed solubilities and degrees of formation of complexes below ~250°C. At higher temperatures the new yh values cause significant changes in the calculated yA values for monovalent species in the concentrated region. However, it will be seen in later pages that even large discrepancies in yA values have a minor effect (within the limits of uncertainty from other sources at those temperatures) on calculated solution equilibria results.

14. (14) Log K# s values were calculated for temperatures to 350°C using Eqn. 56kcal/mole), A ^r°,298,H2s = + 5 - 3 kcal/mole, and ACpr>H2S = -15cal/moledeg. 51 kcal/mole) and ACpr H s = —40 cal/mole deg. 62 was used in the two standard heat capacity calculations since it is consistent with both Wright and Maass,(202) and Ringbom's(161) empirical equation, l o g ^ s = - 7 . 0125(f - 25) where t = degrees centigrade. The heat capacity values are regarded only as approximations in view of the uncertainties in the thermodynamic data, the small temperature interval over which they were calculated, the assumption that ACp >H s is a constant and the necessary use of the same value for A / / ° 2 9 8 H s in all calculations.

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