180
Chemical Oceanography, 4th Edition
where the term Σ ion- water is the weighted sum of the ion–water interactions of the major
ions of the solution, and Σ ion- ion is the weighted sum of the ion–ion interactions of the
major ions of the solution. The first term is completely additive and is related to ion–water
interactions in pure water. The second term is related to all the possible ion–ion interactions in the solutions. These interactions can be estimated using the Pitzer approach and
are related to
Σ ion- ion = DH + Σ Binary + Σ Ternary
(4.103)
where the binary interactions are related to β 0 , β 1 , and θ, and the ternary interactions are
related to Cϕ and Ψ. Thus, the use of Young’s rule is embodied in the formulation of the
Pitzer equations. The β 0 , β 1 , and C ϕ terms are for all the binary components (NaCl, Na 2 SO 4 ,
MgCl 2 , etc.), and the θ and Ψ terms are for all the ternary mixtures (NaCl + Na 2 SO 4 , NaCl
+ MgCl 2 , etc.). This general approach, although somewhat complicated, can account for all
the possible interactions in a stepwise manner.
References and Further Reading
Ball, P., H 2 O: A Bibliography of Water, Weidenfeld and Nicolson, London (1999).
Barber, R.T., and Ryther, J.H., Organic chelators: factors affecting primary production in the Cromwell
Current upwelling, J. Exp. Mar. Biol. Ecol., 3, 191 (1969).
Bernal, J.D., and Fowler, R.H., A theory of water and ionic solution, with particular reference to
hydrogen and hydroxyl ions, J. Chem. Phys., 1, 515 (1933).
Bjerrum, N., Ion association. I. Influence of ionic association on the activity of ion at moderate degree
of association, Kgl. Danske Videnskab Selskab. Mat. Fys. Medd., 7, 1 (1926).
Born, M., Volumes and heats of hydration of ions, Z. Physik., 1, 45 (1920).
Byrne, R.H., Kump, L.R., and Cantrell, K.J., The influence of temperature and pH on trace metal
speciation in seawater, Mar. Chem., 25, 163 (1988).
Danford, M.D., and Levy, H.A., The structure of water at room temperature, J. Am. Chem. Soc., 84,
3965 (1962).
Davis, C., and Litovitz, T., Two- state theory of the structure of water, J. Chem. Phys., 42, 2563 (1965).
Debye, P., and Hückel, E., Zür Theorie der Electrolyte. I. Gefrierpunkterniedindung und verwandte
Erscheinungen, Phys. Z., 24, 185 (1923).
Drude, P., and Nernst, W., Electrostriction of free ions., Z. Phys. Chem. (Frankfort), 15, 9 (1884).
Du, Q., Superfine, R., Freysz, E., and Shen, Y.R., Vibrational spectroscopy of water at the vapor/
water interface, Phys. Rev. Lett., 70, 2313 (1993).
Eigen, M., Proton transfer, acid- base catalysis and enzymatic hydrolysis, I. Elementary processes,
Angew. Chem. Int. Ed., 3, 1 (1964).
Eucken, A., Z. Elektrochem, 53, 102 (1949).
Eyring, H., Ree, T., and Hirai, N., Significant structures in the liquid state, Proc. Natl. Acad. Sci., 44,
683 (1958).
Falk, M., and Kell, G.S., Thermal properties of water: discontinuities questioned, Science, 155, 1013
(1966).
Frank, H.S., and Quist, A.S., Pauling’s model and the thermodynamic properties of water, J. Chem.
Phys., 34, 604 (1961).
Frank, H.S., and Wen, W.Y., Structural aspects of ion–solvent interactions in aqueous solutions,
Discussions Faraday Soc., 24, 133 (1957).
Chemical Oceanography, 4th Edition
where the term Σ ion- water is the weighted sum of the ion–water interactions of the major
ions of the solution, and Σ ion- ion is the weighted sum of the ion–ion interactions of the
major ions of the solution. The first term is completely additive and is related to ion–water
interactions in pure water. The second term is related to all the possible ion–ion interactions in the solutions. These interactions can be estimated using the Pitzer approach and
are related to
Σ ion- ion = DH + Σ Binary + Σ Ternary
(4.103)
where the binary interactions are related to β 0 , β 1 , and θ, and the ternary interactions are
related to Cϕ and Ψ. Thus, the use of Young’s rule is embodied in the formulation of the
Pitzer equations. The β 0 , β 1 , and C ϕ terms are for all the binary components (NaCl, Na 2 SO 4 ,
MgCl 2 , etc.), and the θ and Ψ terms are for all the ternary mixtures (NaCl + Na 2 SO 4 , NaCl
+ MgCl 2 , etc.). This general approach, although somewhat complicated, can account for all
the possible interactions in a stepwise manner.
References and Further Reading
Ball, P., H 2 O: A Bibliography of Water, Weidenfeld and Nicolson, London (1999).
Barber, R.T., and Ryther, J.H., Organic chelators: factors affecting primary production in the Cromwell
Current upwelling, J. Exp. Mar. Biol. Ecol., 3, 191 (1969).
Bernal, J.D., and Fowler, R.H., A theory of water and ionic solution, with particular reference to
hydrogen and hydroxyl ions, J. Chem. Phys., 1, 515 (1933).
Bjerrum, N., Ion association. I. Influence of ionic association on the activity of ion at moderate degree
of association, Kgl. Danske Videnskab Selskab. Mat. Fys. Medd., 7, 1 (1926).
Born, M., Volumes and heats of hydration of ions, Z. Physik., 1, 45 (1920).
Byrne, R.H., Kump, L.R., and Cantrell, K.J., The influence of temperature and pH on trace metal
speciation in seawater, Mar. Chem., 25, 163 (1988).
Danford, M.D., and Levy, H.A., The structure of water at room temperature, J. Am. Chem. Soc., 84,
3965 (1962).
Davis, C., and Litovitz, T., Two- state theory of the structure of water, J. Chem. Phys., 42, 2563 (1965).
Debye, P., and Hückel, E., Zür Theorie der Electrolyte. I. Gefrierpunkterniedindung und verwandte
Erscheinungen, Phys. Z., 24, 185 (1923).
Drude, P., and Nernst, W., Electrostriction of free ions., Z. Phys. Chem. (Frankfort), 15, 9 (1884).
Du, Q., Superfine, R., Freysz, E., and Shen, Y.R., Vibrational spectroscopy of water at the vapor/
water interface, Phys. Rev. Lett., 70, 2313 (1993).
Eigen, M., Proton transfer, acid- base catalysis and enzymatic hydrolysis, I. Elementary processes,
Angew. Chem. Int. Ed., 3, 1 (1964).
Eucken, A., Z. Elektrochem, 53, 102 (1949).
Eyring, H., Ree, T., and Hirai, N., Significant structures in the liquid state, Proc. Natl. Acad. Sci., 44,
683 (1958).
Falk, M., and Kell, G.S., Thermal properties of water: discontinuities questioned, Science, 155, 1013
(1966).
Frank, H.S., and Quist, A.S., Pauling’s model and the thermodynamic properties of water, J. Chem.
Phys., 34, 604 (1961).
Frank, H.S., and Wen, W.Y., Structural aspects of ion–solvent interactions in aqueous solutions,
Discussions Faraday Soc., 24, 133 (1957).