Potassium ferrate of known purity was used to oxidize three alcohols (propanol-2, 1,1,1-trifluoropropanol-2, and 1,1,1,3,3,3- hexafluoropropanol-2) in 8 ~ potassium hydroxide, and a series of substituted phenyltrifluoromethyl carbinols (m-nitrophenyl-, m-bromophenyl-, p-methylphenyl-, and unsubstituted) in 0.5 ~potassium hydroxide and 3.5 ~potassium fluoride. The reactions were found to obey pseudofirst order kinetics and shown to be first order in ferrate ion and first order in alkoxy i on (ionized carbinol or alcohol); acetone production I from the oxidation of propanol-2 al so followed first order kinetics; oxygen evolution was 3/2 order· in some reactive intermediate, other than iron-VI. Deuterium isotope effects show that the breaking of the C-1! bond on the alpha-carbon is the rate determining step for the oxidation. The isotope effects also indicate, by applying the Swain Criteria, that a hydride mechanism is likely. The salt effect, isokinetic relationship, and Hammett plot all give confirmation of the suggested hydride mechanism.
","abstract_html":"<p>Potassium ferrate of known purity was used to oxidize three alcohols (propanol-2, 1,1,1-trifluoropropanol-2, and 1,1,1,3,3,3- hexafluoropropanol-2) in 8 ~ potassium hydroxide, and a series of substituted phenyltrifluoromethyl carbinols (m-nitrophenyl-, m-bromophenyl-, p-methylphenyl-, and unsubstituted) in 0.5 ~potassium hydroxide and 3.5 ~potassium fluoride. The reactions were found to obey pseudofirst order kinetics and shown to be first order in ferrate ion and first order in alkoxy i on (ionized carbinol or alcohol); acetone production I from the oxidation of propanol-2 al so followed first order kinetics; oxygen evolution was 3/2 order· in some reactive intermediate, other than iron-VI. Deuterium isotope effects show that the breaking of the C-1! bond on the alpha-carbon is the rate determining step for the oxidation. The isotope effects also indicate, by applying the Swain Criteria, that a hydride mechanism is likely. The salt effect, isokinetic relationship, and Hammett plot all give confirmation of the suggested hydride mechanism.</p>","abstract_has_math":false,"creators":["Lewis, William C."],"institution":null,"degree_name":"Master of Arts (MA)","degree_level":"Thesis","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["C. M. Hull","B. E. Norcross"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":1965,"date_issued":"1965-03-09T08:00:00Z","date_published":"1965-03-09T08:00:00Z","updated_at":"2026-07-24T01:10:09Z","subjects":[],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://orb.binghamton.edu/dissertation_and_theses/113","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["C. M. Hull","B. E. Norcross"]},{"key":"dc:creator","label":"Author","values":["Lewis, William C."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Thesis"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Master of Arts (MA)"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://orb.binghamton.edu/dissertation_and_theses/113"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Potassium ferrate of known purity was used to oxidize three alcohols (propanol-2, 1,1,1-trifluoropropanol-2, and 1,1,1,3,3,3- hexafluoropropanol-2) in 8 ~ potassium hydroxide, and a series of substituted phenyltrifluoromethyl carbinols (m-nitrophenyl-, m-bromophenyl-, p-methylphenyl-, and unsubstituted) in 0.5 ~potassium hydroxide and 3.5 ~potassium fluoride. The reactions were found to obey pseudofirst order kinetics and shown to be first order in ferrate ion and first order in alkoxy i on (ionized carbinol or alcohol); acetone production I from the oxidation of propanol-2 al so followed first order kinetics; oxygen evolution was 3/2 order· in some reactive intermediate, other than iron-VI. Deuterium isotope effects show that the breaking of the C-1! bond on the alpha-carbon is the rate determining step for the oxidation. The isotope effects also indicate, by applying the Swain Criteria, that a hydride mechanism is likely. The salt effect, isokinetic relationship, and Hammett plot all give confirmation of the suggested hydride mechanism.
"]},{"key":"dc:title","label":"Title","values":["The oxidation of secondary alcohols by dipotassium tetraoxoferrate (VI) In concentrated and dilute potassium hydroxide solutions"]}]}],"canonical_facts":{"dc:contributor":["C. M. Hull","B. E. Norcross"],"dc:creator":["Lewis, William C."],"dc:description.abstract":["Potassium ferrate of known purity was used to oxidize three alcohols (propanol-2, 1,1,1-trifluoropropanol-2, and 1,1,1,3,3,3- hexafluoropropanol-2) in 8 ~ potassium hydroxide, and a series of substituted phenyltrifluoromethyl carbinols (m-nitrophenyl-, m-bromophenyl-, p-methylphenyl-, and unsubstituted) in 0.5 ~potassium hydroxide and 3.5 ~potassium fluoride. The reactions were found to obey pseudofirst order kinetics and shown to be first order in ferrate ion and first order in alkoxy i on (ionized carbinol or alcohol); acetone production I from the oxidation of propanol-2 al so followed first order kinetics; oxygen evolution was 3/2 order· in some reactive intermediate, other than iron-VI. Deuterium isotope effects show that the breaking of the C-1! bond on the alpha-carbon is the rate determining step for the oxidation. The isotope effects also indicate, by applying the Swain Criteria, that a hydride mechanism is likely. The salt effect, isokinetic relationship, and Hammett plot all give confirmation of the suggested hydride mechanism.
"],"dc:identifier":["https://orb.binghamton.edu/dissertation_and_theses/113"],"dc:title":["The oxidation of secondary alcohols by dipotassium tetraoxoferrate (VI) In concentrated and dilute potassium hydroxide solutions"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Thesis"],"thesis:degree_name":["Master of Arts (MA)"]},"updated_at":"2026-07-24T01:10:09Z"}