Comment on "Simulations of ionization equilibria in weak polyelectrolyte solutions and gels" by J. Landsgesell, L. Nová, O. Rud, F. Uhlík, D. Sean, P. Hebbeker, C. Holm and P. Košovan, , 2019, , 1155-1185.

Soft Matter

Instituto de Física, Universidade Federal do Rio Grande do Sul, Caixa Postal 15051, CEP 91501-970, Porto Alegre, RS, Brazil.

Published: May 2023

In a recent review Landsgesell , 2019, , 1155 stated that pH - p is a "universal parameter" for titrating systems. We show that this is not the case. This broken symmetry has important implications for constant pH (cpH) simulations. In particular, we show that for concentrated suspensions the error resulting from the use of cpH algorithm described by Landsgesell is very significant, even for suspension containing 1 : 1 electrolyte. We show how to modify the cpH algorithm to account for the grand-canonical nature of the cpH simulations and for the charge neutrality requirement.

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Source
http://dx.doi.org/10.1039/d2sm01393bDOI Listing

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