A Generalized Grand-Reaction Method for Modelling the Exchange of Weak (Polyprotic) Acids between a Solution and a Weak Polyelectrolyte Phase

TL;DR

This paper presents a Monte-Carlo simulation method for modeling weak polyelectrolyte systems coupled to reservoirs with complex chemical compositions, extending previous approaches to include more realistic reservoir conditions.

Contribution

The authors develop a generalized Grand-Reaction Monte-Carlo method and a chemical potential tuning algorithm for simulating polyelectrolyte systems with complex reservoir chemistries.

Findings

The method accurately models ionization and electrostatic interactions in polyelectrolyte systems.

Simulation reveals non-monotonous swelling behavior of weak polybase chains.

The approach is validated through extensive numerical tests.

Abstract

We introduce a Monte-Carlo method that allows for the simulation of a polymeric phase containing a weak polyelectrolyte, which is coupled to a reservoir at a fixed pH, salt concentration and total concentration of a weak polyprotic acid. The method generalizes the established Grand-Reaction Method by Landsgesell et al. [Macromolecules 53, 3007-3020 (2020)] and thus allows for the simulation of polyelectrolyte systems coupled to reservoirs with a more complex chemical composition. In order to set the required input parameters that correspond to a desired reservoir composition, we propose a generalization of the recently published chemical potential tuning algorithm of Miles et al. [Phys. Rev. E 105, 045311 (2022)]. To test the proposed tuning procedure, we perform extensive numerical tests for both ideal and interacting systems. Finally, as a showcase, we apply the method to a simple test system which consists of a weak polybase solution that is coupled to a reservoir containing a small diprotic acid. The complex interplay of the ionization various species, the electrostatic interactions and the partitioning of small ions leads to a non-monotonous, stepwise swelling behaviour of the weak polybase chains.