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Competitive Cd2+/H+ complexation to polyacrylic acid described by the stepwise and intrinsic stability constants

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Issue date
2008
Author
Calin, David
Companys Ferran, Encarnació
Galceran i Nogués, Josep
Garcés, Josep Lluís
Mas i Pujadas, Francesc
Rey Castro, Carlos
Salvador, José
Puy Llorens, Jaume
Suggested citation
Calin, David; Companys Ferran, Encarnació; Galceran i Nogués, Josep; Garcés, Josep Lluís; Mas i Pujadas, Francesc; Rey Castro, Carlos; ... Puy Llorens, Jaume. (2008) . Competitive Cd2+/H+ complexation to polyacrylic acid described by the stepwise and intrinsic stability constants. Journal of Physical Chemistry B, 2008, vol. 112, núm. 33, p. 10092-10100. https://doi.org/10.1021/jp802571f.
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Abstract
Stepwise constants can be used to describe competitive proton and metal binding to macromolecules with a large number of sites. With the aim of accessing information on the microscopic binding model, we report an expression that connects the stepwise constants to the site-specific metal constants. This expression holds for a very general complexation model including heterogeneity, interactions, and chelate complexation. Assuming bidentate binding of the Cd ions to adjacent carboxylate groups in poly(acrylic acid), stepwise and intrinsic stability constants for proton and cadmium binding were estimated from the experimental data. Intrinsic values were split into specific and electrostatic contributions (by means of the Poisson - Boltzmann equation under cylindrical geometry). Free of the electrostatic contribution, the remaining Cd binding energy showed almost no dependence on the coverage and ionic strength, and the corresponding average values allowed for a reasonable reproduction of raw binding data. Small systematic discrepancies from the homogeneous behavior are critically discussed.
URI
http://hdl.handle.net/10459.1/57836
DOI
https://doi.org/10.1021/jp802571f
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Journal of Physical Chemistry B, 2008, vol. 112, núm. 33, p. 10092-10100
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