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By J. P. Riley

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11. 5% between 25 and 50 °C. These results demonstrate that the value of ypJy\ between 0 and 25 °C is strongly affected by temperature. It is hoped that future work will provide reliable molai volume and compressibility data over a wide temperature range and up to high concentrations. 0 for NaCl and MgCl 2 calculated from the molai volume data of Ellis (1966, 1967) (neglecting the compressibility term). 0 for NaCl and MgCb from 25 to 200 °C are shown in Fig. 12, which demonstrates that the effect of pressure on the activity coefficients of electrolytes at high temperatures is quite large.

ACID-BASE EQUILIBRIA The ionization of acids in sea-water can be represented by apparent, K'HX, or stoicheiometric, ΛΓ*χ, constants defined by K'm = ^ (73) A [HX]T K*HX = [H]T[X,„νΊ [HX]T » (74) where a'H is the apparent activity of the proton and [/]τ are the total or stoicheiometric concentrations of species /. The apparent activity of the proton is related to the real activity by a'H = kciH· The factor k is related to liquid junction potentials (at the salt bridge-solution interface in the reference electrode) and the salt potential (at the glass membrane-solution interface in the pH electrode).

Gardiner and Smith (1972). *" Weiss (1975). ■'"Bradshaw(1973). * Masterton (1954). A O'Sullivan and Smith (1970). ' Millero and Emmet (1976). (l to Harned's rule (Harned and Owen, 1958; Harned and Robinson, 1968) for the activity coefficient of an electrolyte (73) in a mixed electrolyte solution: log y3 = log 73 + a23 w2, (35) where 73 is the value of the activity coefficient in water at the ionic strength of the mixture with a molality of m2, and where 0(23 is an interaction coefficient. If 0C23 is assumed to be independent of pressure, the partial molai volume and compressibility of electrolyte 3 in the mixture will have the same values as they would have by itself at the same ionic strength (/) as the mixture.

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