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Additional resources for Chemical Oceanography. Volume 8
As shown in Fig. 6, the values of AKtrans and Δ/Ctrans for cations do not correlate very well with Z2/r. Cations of different charge fall on two separate lines. Similar plots for monovalent monatomic anions show little or no dependence on 1/r. These findings are not surprising, since other factors, such as packing effects, are not the same in water and aqueous ionic media. The volume properties of ions can also be examined by using a simple hydration model (Millero et ai, 1974). The électrostriction molai volume is given by K(elect) = n(VE-VB), (58) where KE and VB are the molar volumes of water in the electrostricted (E) and bulk (B) solvent regions around an ion hydrated by n water molecules.
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.
IONIC STRENGTH PRINCIPLE The most direct method that can be used to estimate partial molai properties is based on the ionic strength principle. This method essentially states that the partial molai property of an electrolyte in an ionic medium is equal to the value in pure water at the ionic strength of the medium. This method is related 4 3 . 4' — — — — " Enns et al. (1965). h Tiepel and Gubbins (1972). c Kritchevsky and Ilinskaya (1945). Gardiner and Smith (1972). *" Weiss (1975). ■'"Bradshaw(1973).