TY - JOUR
T1 - Chemical association via exact thermodynamic formulations
AU - Fisher, Michael E.
AU - Zuckerman, Daniel M.
N1 - Funding Information:
The authors thank Professors Harold Friedman and George Stell for their interest in this work, and Dr. Stefan Bekiranov for ongoing discussions and comments on a draft manuscript. Professors Economou, Stell, and Widom kindly commented on the article. The support of the National Science Foundation (through Grant CHE 96-14495) has been appreciated.
PY - 1998/9/4
Y1 - 1998/9/4
N2 - It can be fruitful to view two-component physical systems of attractive monomers, A and B, "chemically" in terms of a reaction A+B⇌C, where C = AB is an associated pair or complex. We show how to construct free energies in the three-component or chemical picture which, under mass-action equilibration, exactly reproduce any given two-component or "physical" thermodynamics. Order-by-order matching conditions and closed-form chemical representations reveal the freedom available to modify the A-C, B-C, and C-C interactions and to adjust the association constant. The theory (in the simpler one-component, i.e., A ≡ B, case) is illustrated by treating a van der Waals fluid.
AB - It can be fruitful to view two-component physical systems of attractive monomers, A and B, "chemically" in terms of a reaction A+B⇌C, where C = AB is an associated pair or complex. We show how to construct free energies in the three-component or chemical picture which, under mass-action equilibration, exactly reproduce any given two-component or "physical" thermodynamics. Order-by-order matching conditions and closed-form chemical representations reveal the freedom available to modify the A-C, B-C, and C-C interactions and to adjust the association constant. The theory (in the simpler one-component, i.e., A ≡ B, case) is illustrated by treating a van der Waals fluid.
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U2 - 10.1016/S0009-2614(98)00786-6
DO - 10.1016/S0009-2614(98)00786-6
M3 - Article
AN - SCOPUS:0012522303
SN - 0009-2614
VL - 293
SP - 461
EP - 468
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 5-6
ER -