title: A general theory of kinetics and thermodynamics of steady-state copolymerization.
abstract: Kinetics of steady-state copolymerization has been investigated since the 1940s. Irreversible terminal and penultimate models were successfully applied to a number of comonomer systems, but failed for systems where depropagation is significant. Although a general mathematical treatment of the terminal model with depropagation was established in the 1980s, a penultimate model and higher-order terminal models with depropagation have not been systematically studied, since depropagation leads to hierarchically-coupled and unclosed kinetic equations which are hard to solve analytically. In this work, we propose a truncation method to solve the steady-state kinetic equations of any-order terminal models with depropagation in a unified way, by reducing them into closed steady-state equations which give the exact solution of the original kinetic equations. Based on the steady-state equations, we also derive a general thermodynamic equality in which the Shannon entropy of the copolymer sequence is explicitly introduced as part of the free energy dissipation of the whole copolymerization system.
authors.affiliation: State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Chinese Academy of Sciences, Zhong Guan Cun East Street 55, PO Box 2735, Beijing 100190, People's Republic of China. School of Physics, University of Chinese Academy of Sciences, No 19A Yuquan Road, Beijing 100049, People's Republic of China.
authors.forename: Yao-Gen
authors.initials: YG
authors.lastname: Shu
authors.forename: Yong-Shun
authors.initials: YS
authors.lastname: Song
authors.forename: Zhong-Can
authors.initials: ZC
authors.lastname: Ou-Yang
authors.forename: Ming
authors.initials: M
authors.lastname: Li