Brock University
A study of thermal decompositions of an allylic hydroperoxide /|nby Thomas A. McCarrick. -- 260 St. Catharines [Ont.] : Dept. of Chemistry, Brock University,
Abstract
dc:description.abstractThe thermal decomposition of 2,3-di~ethy l - J-hydr operox y- 1 - butene , p r epared f rol") singl e t oxygen, has been studied i n three solvents over the tempe r a ture r ange from 1500e to l o00e and t!1e i 111 t ial ~oncentrfttl nn r Ange from O. 01 M to 0.2 M. Analys i s of the kine tic data ind ica te s i nduced homolysis as the n ost probRble mode of d e composition, g iving rise to a 3/2 f S order dependence upon hy d.roperoxide concent :r8.tl on . Experimental activation e nergies for the decomposition were f ound to be between 29.5 kcsl./raole and 30.0 k cal./mole .• \,iith log A factors between 11 . 3 and 12.3. Product studies were conducted in R variety of solvents a s well as in the pr esence of a variety of free r adical initiators . Investigation of the kinetic ch a in length indicated a chain length of about fifty. A degenerat i ve chain branching mechanism 1s proposed which predicts the multi t ude of products which Rre observed e xperimentally as well as giving activation energies and log A factors si~il a r to those found experimentally .
Degree
thesis:*- Name thesis:degree_name
- M.Sc. Chemistry
- Level thesis:degree_level
- Masters
- Discipline thesis:degree_discipline
- Faculty of Mathematics and Science
- Department dc:contributor.department
- Department of Chemistry
- Grantor
- Brock University
- Year dc:date.issued
- 1974
Author and committee
dc:creator, dc:contributor.*- Author dc:creator
-
- McCarrick, Thomas A.
Subjects
dc:subject × 3Rights
- Language dc:language.iso
- eng
Identifiers
dc:identifier.*- Handle dc:identifier.uri
- http://hdl.handle.net/10464/1772
- OAI identifier oai:identifier
- oai:brocku.scholaris.ca:10464/1772