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Calculation of Thermodynamic Properties of Polyelectrolytes

Marcus, R. A. (1955) Calculation of Thermodynamic Properties of Polyelectrolytes. Journal of Chemical Physics, 23 (6). pp. 1057-1068. ISSN 0021-9606. https://resolver.caltech.edu/CaltechAUTHORS:20140429-124648028

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Abstract

Expressions are derived which introduce an appreciable simplification into the calculation of the thermodynamic properties of solutions of polyelectrolytes in certain cases. For example, for a certain class of theoretical models of these systems it is found that the square of the mean ion activity coefficient of a uni-univalent salt in the presence of polymeric ions is V^2/∫e^(-eψ/kT)dV • ∫e^(eψ/kT)dV, the integration of the potential ψ being over a region whose volume is the volume of solution per macro-ion, V, and whose symmetry is that assumed for the polyelectrolyte. The osmotic pressure of a salt-polyelectrolyte system is, ignoring the contribution of the macro-ion, estimated to be Σ_ic_i^skT, where Σ_ic_i^s is the sum of the concentrations of all ions at the surface bounding the previously defined volume V. Other relations and various applications are given. The activity coefficient of salt in the presence of polyelectrolytes, calculated by extending the "parallel rod" picture of polymeric ions, is found to be in reasonable agreement with the experimental data. The use of the Poisson-Boltzmann equation to estimate ψ in these systems is shown not to render inconsistent several alternative expressions for the electrostatic contribution to the free energy.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.1742191DOIArticle
http://scitation.aip.org/content/aip/journal/jcp/23/6/10.1063/1.1742191PublisherArticle
Additional Information:© 1955 American Institute of Physics. Received October 7, 1954. The writer would like to express his appreciation to Dr. E. M. Loebl and Dr. H. Morawetz of this institute who read the manuscript critically and offered a number of helpful comments.
Issue or Number:6
Record Number:CaltechAUTHORS:20140429-124648028
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20140429-124648028
Official Citation:Marcus, R. A. (1955). Calculation of Thermodynamic Properties of Polyelectrolytes. The Journal of Chemical Physics, 23(6), 1057-1068. doi: doi:http://dx.doi.org/10.1063/1.1742191
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:45305
Collection:CaltechAUTHORS
Deposited By: Aucoeur Ngo
Deposited On:30 Apr 2014 14:52
Last Modified:03 Oct 2019 06:29

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