Macromolecular Rapid Communications, Vol.19, No.2, 89-96, 1998
Chain-length dependent termination in pulsed-laser polymerization, 3 -On the prospects of determining the bimolecular termination constant k(t) from rate data
The correct (event-weighted) average of k(t), [k(t)], has been calculated from simulation data for pseudostationary laser-induced polymerization for a kinetic scheme with chain-length dependent termination and compared to the average (k) over bar(t) which is obtained by employing the formal procedures, originally designed for the evaluation of individual rate constants from rate data in the case of chain-length independent termination. Satisfactory (and in fact excellent) results are obtained only if the complete equation for the conversion per laser pulse is solved for (k) over bar(t). This leads to an almost perfect recovery of the power-law governing the dependence of k(t) on chain-length, especially the exponent.