Pitzer equations3and salts have been tabulated.
Temperature and pressure variation is also discussed.One area of application of Pitzer parameters is to describe the ionic strength variation of equilibrium constantsmeasured as concentration quotients. Both SIT and Pitzer parameters have been used in this context, For example,both sets of parameters were calculated for some uranium complexes and were found to account equally well for theionic strength dependence of the stability constants.
Pitzer parameters and SIT theory have been extensively compared. There are more parameters in the Pitzer equationsthan in the SIT equations. Because of this the Pitzer equations provide for more precise modelling of mean activitycoefficient data and equilibrium constants. However, the determination of the greater number of Pitzer parametersmeans that they are more difficult to determine.
Compilation of Pitzer parameters
Besides the set of parameters obtained by Pitzer et al. in 1970s mentioned in the previous section. Kim andFrederick
published the Pitzer parameters for 304 single salts in aqueous solutions at 298.15 K, extended themodel to the concentration range up to the saturation point. Those parameters are widely used, however, manycomplex electrolytes including ones with organic anions or cations, which are very significant in some related fields,were not summarized in their paper.For some complex electrolytes, Ge et al.
obtained the new set of Pitzer parameters using up-to-date measured orcritically reviewed osmotic coefficient or activity coefficient data.
A comparable TCPC model
Besides the well-known Pitzer-like equations, there is a simple and easy-to-use semi-empirical model, which iscalled the three-characteristic-parameter correlation(TCPC)model, which is first proposed by Lin et al.
It is acombination of the Pitzer long-range interaction and short-range solvation effect.ln
Ge et al.
modified this model, and obtained the TCPC parameters for a larger number of single salts aqueoussolutions. This model was also extended for a number of electrolytes dissolved in methanol,ethanol, 2-propanol, andso on.
Temperature dependent parameters for a number of common single salts were also compiled, availableat.
The performance of the TCPC model in correlation with the measured activity coefficient or osmotic coefficients isfound to be comparable with Pitzer-like models.
•Pitzer, K.S. (editor) (1991).
Activity coefficients in electrolyte solutions
(2nd ed.). C.R,C. Press.ISBN 0-8493-5415-3. Chapter 3. *Pitzer, K.S.
Ion interaction approach: theory and data correlation
Pitzer (1991)Stumm, W.; Morgan, J.J. (1996).
. New York: Wiley. ISBN 0-471-05196-9.Snoeyink, V.L.; Jenkins, D. (1980).
Aquatic Chemistry: Chemical Equilibria and Rates in Natural Waters
. New York: Wiley.ISBN 0-471-51185-4.Millero, F.J. (2006).
(3rd ed.). London: Taylor and Francis. ISBN 0-8493-2280-4.Connick, Robert E., "Kenneth Pitzer" (http:/
pdf), Proceedings of the AmericanPhilosophical Society, Vol. 144, No. 4, December 2000, pp. 479-483McMillan, W.G.; Mayer, J.E. (1945). "The statistical thermodynamics of multicomponent systems".
J. Chem. Phys.
(7): 276.Bibcode 1945JChPh..13..276M. doi:10.1063/1.1724036.Debye, P.; Hückel, E. (1923). "Zur Theorie der Electrolyte".
: 185.Brønsted, J.N. (1922). "Studies on solubility IV. The principle of the specific interaction of ions".
J. Am. Chem. Soc.