TY - JOUR
T1 - Thermodynamic modeling of aqueous polyelectrolyte solutions with mixed-valent counterions
AU - Li, Yuan
AU - Chen, Chau Chyun
N1 - Publisher Copyright:
© 2022 Elsevier Ltd
PY - 2022/6
Y1 - 2022/6
N2 - Thermodynamic modeling of aqueous polyelectrolyte solutions with salts is of significant interest for many industrial applications. This study applies the polyelectrolyte Nonrandom Two-liquid activity coefficient model to aqueous polyelectrolyte solutions with mixed-valent counterions. A modified Delocalized Binding Theory was proposed to determine the polyion condensation fractions of the mixed counterions. This modified theory accounts for the electrostatic binding of the counterions on the polyion, the dissociation entropy of the counterions, and the electrostatic interactions between the uncondensed ionic species. Given the polyion condensation fractions, the critical value of Manning's parameter ξ and the amounts of uncondensed polyions and counterions can be calculated along with the activity coefficients of mobile ions. The model successfully correlates experimental data for various aqueous polyelectrolyte systems with mixed-valent counterions.
AB - Thermodynamic modeling of aqueous polyelectrolyte solutions with salts is of significant interest for many industrial applications. This study applies the polyelectrolyte Nonrandom Two-liquid activity coefficient model to aqueous polyelectrolyte solutions with mixed-valent counterions. A modified Delocalized Binding Theory was proposed to determine the polyion condensation fractions of the mixed counterions. This modified theory accounts for the electrostatic binding of the counterions on the polyion, the dissociation entropy of the counterions, and the electrostatic interactions between the uncondensed ionic species. Given the polyion condensation fractions, the critical value of Manning's parameter ξ and the amounts of uncondensed polyions and counterions can be calculated along with the activity coefficients of mobile ions. The model successfully correlates experimental data for various aqueous polyelectrolyte systems with mixed-valent counterions.
KW - Aqueous polyelectrolyte solutions
KW - Counterion condensation
KW - Delocalized binding theory
KW - Mixed-valent counterions
KW - Polyelectrolyte NRTL model
UR - http://www.scopus.com/inward/record.url?scp=85125437379&partnerID=8YFLogxK
U2 - 10.1016/j.jct.2022.106761
DO - 10.1016/j.jct.2022.106761
M3 - Article
AN - SCOPUS:85125437379
SN - 0021-9614
VL - 169
JO - Journal of Chemical Thermodynamics
JF - Journal of Chemical Thermodynamics
M1 - 106761
ER -