The reaction of dimethyldioxirane with a series of cis/trans-1,2-dialkylalkenes was carried out and produced the corresponding epoxides in high yield. As expected, the relative reactivity at 23 ºC of the cis-alkenes was at least 8-fold greater than that of the trans-counterparts with the magnitude of the relative reactivity increasing with increased steric bulk. Enhanced selectivity for cis- versus trans-alkene epoxidation was observed at lower temperatures. The reaction of dimethyldioxirane with selected alkenes was carried out in various solvent conditions (dried acetone:acetonitrile (1:9), dried acetone:methanol (1:9), dried acetone:carbon tetrachloride (1:9) and acetone:water (Xwater = 0.00, 0.01, 0.02, 0.03, 0.04, 0.05)) and produced the corresponding epoxides in high yield. The reactivity of dioxirane with simple di- and trialkylalkenes was enhanced as the polarity and hydrogen bonding capability of the solvent system were increased. Little to no change in reactivity was observed in the non-polar solvent system. Epoxidation of trisubstituted alkenes by dioxirane showed a greater rate enhancement in polar protic solvents compared to that for the epoxidation of the disubstituted alkenes. The epoxidation of an allylic alcohol by dimethyldioxirane showed a large increase in the non-polar solvent system compared to that in acetone. The reaction of dimethyldioxirane with the allylic alcohol also exhibited less of a rate increase in polar protic systems than its alkyl counterpart. Activation parameters for the epoxidation of cis/trans-1,2-dialkylalkenes by dioxirane in dried acetone and the previously mentioned solvent systems were determined using the Arrhenius method. In general, the ∆G‡ and ∆H‡ terms were greater for the reaction of dimethyldioxirane with trans-alkenes as compared to those for the corresponding cis-isomers regardless of solvent or alkyl steric bulk. The calculated ∆S‡ terms appeared essentially independent of steric bulk or solvent composition and were roughly identical, within experimental error, for all of the five cis/trans pairs. The ∆∆G‡ values, a comparison of the trans- to the cis-isomer data, yielded values of 1.2 to 1.8 kcal/mol in dried acetone for the five pairs of alkenes and appeared to be dependent on relative steric interactions. The ∆∆G‡ values for the epoxidation of cis/trans-alkenes carried out in solvents other than acetone showed no change from the value obtained in acetone. The experimental activation parameter data in dried acetone were consistent with predictions from ab initio calculations based on a spiro transition state model.

The kinetics of the oxidation of [Fe(CN)6]-4 by K[Co(HEDTA)NO2] was studied in order to get the mechanism and the activation parameters of the reaction. Using a freshly-made Na3PO4 solution as the reaction medium with a pH of 6.00 the ionic strength was maintained at 0.10 M and the buffer molarity was 0.001 M. The rate constant (kobs) of the reaction between [Fe(CN)6]-4 and K[Co(HEDTA)NO2] was determined at temperatures of 25.0°C, 27.5°C, 30.0°C, 35.0°, and 40.0°C. We explored this reaction by monitoring the evolution of ferricyanide, [Fe(CN)6]-3, spectroscopically for which ε420 = 1023 cm-1 M-1 by recording the absorbance as a function of time at 420 nm wavelength. The data were plotted and results analyzed to give activation parameters, energy of activation (Ea), entropy of activation (ΔS‡), and enthalpy of activation (ΔH‡) for the two reacting complexes under the specified reaction conditions. Based on previous results, an outer-sphere electron-transfer pathway and a first order rate of reaction for each of the reacting species 1 have been proposed.

The hydrolysis of acetic anhydride is a widely-studied liquid phase reaction studied since 1906. Different approaches have been used to study the kinetics of this reaction. Approaches used by researchers have involved the use of sophisticated experimental set-ups. In this work, the pH technique has been adopted which involves the use of a pH meter to monitor the hydrolysis reaction. Analysis of the hydrolysis reaction has been performed for water/acetone cosolvent systems over a range of temperatures and mole fractions. Eyring analysis was performed under isomole fraction conditions and activation enthalpy, entropy, and Gibbs free energy for hydrolysis of acetic anhydride have been determined. The isomole fraction Eyring plots are linear, because, activation enthalpy and entropy are independent of temperature under these conditions. Activation free Gibbs energy increases with increasing temperature at a constant water mole fraction, while it decreases with increasing water mole fraction at constant temperature.