The phthalimide N-oxyl (PINO) radical was generated by the oxidation of N-hydroxyphthalimide (NHPI) with Pb(OAc) 4 in acetic acid. The molar absorptivity of PINO • is 1.36 × 10 3 L mol - 1 cm - 1 at λ max 382 nm. The PINO radical decomposes slowly with a second-order rate constant of 0.6 ± 0.1 L mol - 1 s - 1 at 25 °C. The reactions of PINO • with substituted toluenes, benzaldehydes, and benzyl alcohols were investigated under an argon atmosphere. The second-order rate constants were correlated by means of a Hammett analysis. The reactions with toluenes and benzyl alcohols have better correlations with σ + (ρ = −1.3 and −0.41), and the reaction with benzaldehydes correlates better with σ (ρ = −0.91). The kinetic isotope effect was also studied and significantly large values of k H/ k D were obtained: 25.0 ( p-xylene), 27.1 (toluene), 27.5 (benzaldehyde), and 16.9 (benzyl alcohol) at 25 °C.

From the Arrhenius plot for the reactions with p-xylene and p-xylene- d 10, the difference of the activation energies, E a D − E a H, was 12.6 ± 0.8 kJ mol - 1 and the ratio of preexponential factors, A H/ A D, was 0.17 ± 0.05. These findings indicate that quantum mechanical tunneling plays an important role in these reactions.

General Overview Kinetics for Synthetic Chemists Bibliography: J. Espenson, “Chemical Kinetics and Reaction Mechanism”, 1st or 2nd Ed. Is there any free software that will allow me to model chemical reactions? For chemical kinetics studies. It's free and very similar to Chemkin. MATLAB software is hepful in modelling.

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