Chemical Oceanography. Volume 8 by J. P. Riley

By J. P. Riley

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To a pressure of 1000 bars, κ of electrolytes can be represented by 1 0 3 ^ = \03ic(P = 0) + AP. 23. For 1-1, 2-1 and 2-2 electrolytes, the values of\03A range from 1 to 3 cm3 mol~ l b a r - 2 at 25 °C in sea-water. The values in pure water are slightly higher (2-5 cm3 m o i - ] b a r - 2 at 25 °C). At lower temperatures, the effects of pressure on κ* in water and sea-water are greater. 4 in sea-water. Further measurements are needed to determine reliable values of A for other electrolytes in water and sea-water.

The differentiation of equations (75) and (76) with respect to pressure gives -AV'HX= -AV°ux + RT(d\nk/dP) -ΔΚ*χ = - Δ ^ Χ + (ΚΗΧ-^ Χ + (VHX-V^x)-(Vx-Vx), )-(ΚΗ-^)-(Κ Χ -Κ (77) Χ ), (78) where AV'HX = -RT(d In K'm/dP), (79) ΔΚ* χ = -RT(d In K*x/dP\ (80) V-V] (81) = RT(d\nyi/dP). If RT(d\nk/dP)~VH-VH, the values of AV and ΔΚ* are equal. This appears to be the case for the ionization of H 2 C0 3 , HC03~ and B(OH)3 in sea-water (Millero and Berner, 1972). Since the AV°UX= V°H+ Vx~ V°HX, equation (78) simplifies to AV*X= FH+KX+FHX, (82) where the values of K, are the partial molai volumes of species / in the media of interest.

A correlation of AVm and Aicm has also been demonstrated for these mixtures (see Fig. , 1980a). With the exception of HC0 3 ~, the values of ko appear to be linearly related to VQ. The values of k0 are the same sign as the appropriate values of v0. Thus, both ko and v0 correlate with the enthalpy interaction term RTho and have the opposite sign. , 1965) for common anion mixtures, the cations can be divided into two groups. The mixing of N a + with the so-called "structure-making" cations 4 3 . 31 "From Millero^fl/.

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