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Pitzer equations

Pitzer equations

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Published by Paul Muljadi
Pitzer equations
Pitzer equations

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Published by: Paul Muljadi on Jan 06, 2013
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Pitzer equations1
Pitzer equations
Pitzer equations
are important for the understanding of the behaviour of ions dissolved in natural waters such asrivers, lakes and sea-water.
They were first described by physical chemist Kenneth Pitzer.
The parametersof the Pitzer equations are linear combinations of parameters, of a virial expansion of the excess Gibbs free energy,which characterise interactions amongst ions and solvent. The derivation is thermodynamically rigorous at a givenlevel of expansion. The parameters may be determined by measuring osmotic coefficients. They can be used tocalculate single-ion activity coefficients in solutions for which the Debye
Hückel theory is inadequate. They aremore rigorous than the equations of specific ion interaction theory (SIT theory), but Pitzer parameters are moredifficult to determine experimentally than SIT parameters.
Historical development
A starting point for the development can be taken as the virial equation of state for a gas.
is the pressure,
is the volume,
is the temperature and
 B, C, D
... are known as virial coefficients. Thefirst term on the right-hand side is for an ideal gas. The remaining terms quantify the departure from the ideal gaslaw with changing pressure,
. It can be shown by statistical mechanics that the second virial coefficient arises fromthe intermolecular forces between
of molecules, the third virial coefficient involves interactions between threemolecules, etc. This theory was developed by McMillan and Mayer.
Solutions of uncharged molecules can be treated by a modification of the McMillan-Mayer theory. However when asolution contains electrolytes electrostatic interactions must also be taken into account. The Debye-Hückel theory
was based on the assumption that each ion was surrounded by a spherical "cloud" made up of ions of the oppositecharge. Expressions were derived for the variation of single-ion activity coefficients as a function of ionic strength.This theory was very successful for dilute solutions of 1:1 electrolytes and, as discussed below, the Debye-Hückelexpressions are still valid at sufficiently low concentrations. The values calculated with Debye-Hückel theorydiverge more and more from observed values as the concentrations and/or ionic charges increases. Moreover,Debye-Hückel theory takes no account of the specific properties of ions such as size or shape.Brønsted had independently proposed an empirical equation,
= (
in which the activity coefficient depended not only on ionic strength, but also on the concentration,
, of the specificion through the parameter
. This is the basis of SIT theory. It was further developed by Guggenheim.
extended the theory to allow the interaction coefficients to vary with ionic strength. Note that thesecond form of Brønsted's equation is an expression for the osmotic coefficient. Measurement of osmoticcoefficients provides one means for determining mean activity coefficients.
Pitzer equations2
The Pitzer parameters
The exposition begins with a virial expansion of the excess Gibbs free energy
is the mass of the water in kilograms,
 , m
... are the molalities of the ions and
is the ionic strength. The firstterm,
represents the Debye-Hückel limiting law. The quantities
represent the short-range interactions in thepresence of solvent between solute particles
. This binary interaction parameter or second virial coefficientdepends on ionic strength, on the particular species
and the temperature and pressure. The quantities
represent the interactions between three particles. Higher terms may also be included in the virial expansion.Next, the free energy is expressed as the sum of chemical potentials, or partial molal free energy,and an expression for the activity coefficient is obtained by differentiating the virial expansion with respect to amolality.For a simple electrolyte
, at a concentration
, made up of ions
+ and
, the parameters , andare defined asThe term
is essentially the Debye-Hückel term. Terms involving and are not included asinteractions between three ions of the same charge are unlikely to occur except in very concentrated solutions.The
parameter was found empirically to show an ionic strength dependence (in the absence of ion-pairing) whichcould be expressed asWith these definitions, the expression for the osmotic coefficient becomesA similar expression is obtained for the mean activity coefficient.These equations were applied to an extensive range of experimental data at 25 °C with excellent agreement to about6 mol kg
for various types of electrolyte.
The treatment can be extended to mixed electrolytes
and toinclude association equilibria.
Values for the parameters
for inorganic and organic acids, bases
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
= ln
+ 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
,pp. 75
[1][1]Pitzer (1991)[2]Stumm, W.; Morgan, J.J. (1996).
Water Chemistry
. New York: Wiley. ISBN 0-471-05196-9.[3]Snoeyink, V.L.; Jenkins, D. (1980).
 Aquatic Chemistry: Chemical Equilibria and Rates in Natural Waters
. New York: Wiley.ISBN 0-471-51185-4.[4]Millero, F.J. (2006).
Chemical Oceanography
(3rd ed.). London: Taylor and Francis. ISBN 0-8493-2280-4.[5]Connick, Robert E., "Kenneth Pitzer" (http:/ 
pdf), Proceedings of the AmericanPhilosophical Society, Vol. 144, No. 4, December 2000, pp. 479-483[6]McMillan, 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.[7]Debye, P.; Hückel, E. (1923). "Zur Theorie der Electrolyte".
 Phys. Z.
: 185.[8]Brønsted, J.N. (1922). "Studies on solubility IV. The principle of the specific interaction of ions".
 J. Am. Chem. Soc.
(5): 877

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