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The kinetics and solvent effects on the thermal decomposition of isopropyl peroxide and 1, 2-dioxane

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dc.contributor.author Rahimi, P. Mashhadi. en_US
dc.date.accessioned 2009-10-02T13:20:22Z
dc.date.available 2009-10-02T13:20:22Z
dc.date.issued 1975-10-02T13:20:22Z
dc.identifier.uri http://hdl.handle.net/10464/2768
dc.description.abstract Rates of H2 formation have been determined for the thermal decomposition of isopropyl peroxide at l30o-l50oC in toluene and methanol and at l400C in isopropyl alcohol and water. Product studies have been carried out at l400C in these solvents. The decomposition of isopropyl peroxide was shown to be unimolecular with energies of activation in toluene, and methanol of 39.1, 23.08 Kcal/mole respectively. It has been shown that the rates of H2 formation in decomposition of isopropyl peroxide are solvent dependent and that the ~ vs "'2';' values (parameters for solvent polarity) givesastraight line. Mechanisms for hydrogen production are discussed which satisfactorily explain the stabilization of the six-centered transition state by the solvent. One possibility is that of conformation stabilization by solvent and the other, a transition state with sufficient ionic character to be stabilized by a polar solvent. Rates of thermal decomposition of 1,2-dioxane in tert-butylbenzene at l40o-l70oC have been determined. The activation energy was found to be 33.4 Kcal/mole. This lower activation energy, compared to that for the decomposition of isopropyl peroxide in toluene (39.1 Kcal/mole) has been explained in terms of ring strain. Decomposition of 1,2 dioxane in MeOH does not follow a first order reaction. Several mechanisms have been suggested for the products observed for decomposition of 1;2-dioxane in toluene and methanol. en_US
dc.language.iso eng en_US
dc.publisher Brock University en_US
dc.subject Decomposition (Chemistry) en_US
dc.subject Peroxides. en_US
dc.title The kinetics and solvent effects on the thermal decomposition of isopropyl peroxide and 1, 2-dioxane en_US
dc.type Electronic Thesis or Dissertation en_US
dc.degree.name M.Sc. Chemistry en_US
dc.degree.level Masters en_US
dc.contributor.department Department of Chemistry en_US
dc.degree.discipline Faculty of Mathematics and Science en_US


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