Chain statistics and heat of reaction in random copolymerization

Copolymer chain-statistics and other properties including the heat of copolymerization are derived using the joint concepts of the mean-length of the sequences of each species along the copolymer chain and the number of transitions from sequences of one species to the other. The approach originated in papers of Smoluchowski going back to 1915. By systematic use of the approach, classical relationships are derived for both the terminal and the penultimate models of copolymerization. Relationships are given for the heat of copolymerization and the spectroscopic determination of the monomer reactivity ratios. The simultaneous use of the terminal and penultimate models for specific comonomer species is discussed.