Obtaining thermochemical data by the extended kinetic method

• DOI: 10.1002/jms.680
• Publication Date: 2004-09-14T08:01:33Z
• Authors: Guy Bouchoux; Michel Sablier; Florence Berruyer...
• Keywords: Base (topology)

Abstract A microcanonical analysis of the extended kinetic method is performed using statistical rate calculations based on orbiting transition state theory. The model systems simulate polydentate bases M which exhibit losses entropy upon protonation up to 35 kJ mol −1 K . It shown that correlations natural logarithm ratio constants vs proton affinity reference bases, at several effective temperatures, lead correct and base interest. systematic underestimate latter quantity (by 5–15%), mainly due use a linear rather than polynomial curve fitting procedure, noted, however. When considering experimental data, more severe underestimates are observed for entropies 50–90%). origins these considerable discrepancies beyond limits present modeling remain be determined. Copyright © 2004 John Wiley & Sons, Ltd.