Nonisothermal kinetic analysis of the chemiluminescence from tetramethyl‐1,2‐dioxetane

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A computerized method is given for the evaluation of Arrhenius parameters which describe the chemiluminescent decomposition of tetramethyl‐1,2‐dioxetane. The parameters were determined in several solvents by linear regression methods and the equation ln ln \documentclass{article}\pagestyle{empty}\begin{document}$ [(\sum\nolimits_0^\infty I - \sum\nolimits_0^t I)/(\sum\nolimits_0^\infty I - \sum\nolimits_0^t I - \sum\nolimits_0^{t + \Delta t} I)] = \ln\, (A_1 \Delta t) - E_1 /RT$\end{document}, where I refers to photons counted by increments of Δt, and E1 and A are the first‐order Arrhenius parameters. The average of E1 and log A1 (s−1) from this method from six runs in CCl4 with initial concentrations of 4.9 × 10−5‐8.45 × 10−4M were 27.21 ± 0.88 kcal/mol (113.7 ± 3.7 kJ/mol) and 13.88 ± 0.50, respectively. Simulated curves of chemiluminescence versus time were obtained with the use of a computer program and an auxiliary plotter. Copyright © 1981 John Wiley & Sons, Inc.

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International Journal of Chemical Kinetics