The thermodynamic acidity (pKa) of iodoform in methanol was determined at 25°C and 35°C; the values are 18.74 and 18.05, respectively . These acidity constants were determined by a modification of the equilibrium quenching technique which involves the conversion of the conjugate base of iodoform, present at equilibrium, to the radioactively labelled acid.
The rate constants for the methoxide-catalyzed hydrogentritium exchange of chloroform, iodoform, 9-phenylfluorene and indene were determined in methanol at various temperatures. The second-order rate constants obtained from these studies were shown to be the rate constants for removal of a triton. The activation parameters (ΔH‡ and ΔS‡) for the exchange reactions were also determined for these hydrocarbons from the results of the exchange studies at various temperatures.
The hydrogen-deuterium isotope effects for the reaction of chloroform, iodoform or 9-phenylfluorene with methoxide were determined in methanol at various temperatures. These isotope effects were found to be small for chloroform and iodoform (1.25 and 1.02 at 0°C, respectively), and large for 9-phenylfluorene (5 .3 at 10°C). The low isotope effects for the haloforms are suggested as evidence of a highly asymmetric transition state for the proton transfer. A method was developed to determine the hydrogen-tritium isotope effects for the reaction of methanol with the conjugate bases of chloroform, iodoform and 9-phenylfluorene in methanol at bases of chloroform, iodoform and 9-phenylfluorene in methanol at various temperatures. The values for these isotope effects at 0°C are 1.50 and 1.27 for the chloroform and iodoform conjugate bases, respectively and 12.9 for the conjugate base of 9-phenylfluorene at 10°C.
From the results of the kinetic exchange studies on iodoform and chloroform, along with the thermodynamic pKa's determined for iodoform, and assuming a Bronsted exponent of unity, the pKa of chloroform in methanol at 25°C was calculated to be 21.1\"--Abstract, pages iii-iv.
","abstract_html":"<p>The thermodynamic acidity (pK<sub>a</sub>) of iodoform in methanol was determined at 25°C and 35°C; the values are 18.74 and 18.05, respectively . These acidity constants were determined by a modification of the equilibrium quenching technique which involves the conversion of the conjugate base of iodoform, present at equilibrium, to the radioactively labelled acid.</p> <p>The rate constants for the methoxide-catalyzed hydrogentritium exchange of chloroform, iodoform, 9-phenylfluorene and indene were determined in methanol at various temperatures. The second-order rate constants obtained from these studies were shown to be the rate constants for removal of a triton. The activation parameters (ΔH<sup>‡</sup> and ΔS<sup>‡</sup>) for the exchange reactions were also determined for these hydrocarbons from the results of the exchange studies at various temperatures.</p> <p>The hydrogen-deuterium isotope effects for the reaction of chloroform, iodoform or 9-phenylfluorene with methoxide were determined in methanol at various temperatures. These isotope effects were found to be small for chloroform and iodoform (1.25 and 1.02 at 0°C, respectively), and large for 9-phenylfluorene (5 .3 at 10°C). The low isotope effects for the haloforms are suggested as evidence of a highly asymmetric transition state for the proton transfer. A method was developed to determine the hydrogen-tritium isotope effects for the reaction of methanol with the conjugate bases of chloroform, iodoform and 9-phenylfluorene in methanol at bases of chloroform, iodoform and 9-phenylfluorene in methanol at various temperatures. The values for these isotope effects at 0°C are 1.50 and 1.27 for the chloroform and iodoform conjugate bases, respectively and 12.9 for the conjugate base of 9-phenylfluorene at 10°C.</p> <p>From the results of the kinetic exchange studies on iodoform and chloroform, along with the thermodynamic pK<sub>a</sub>'s determined for iodoform, and assuming a Bronsted exponent of unity, the pK<sub>a</sub> of chloroform in methanol at 25°C was calculated to be 21.1"--Abstract, pages iii-iv.</p>","abstract_has_math":false,"creators":["Filger, Dennis L."],"institution":"University of Missouri--Rolla","degree_name":"Ph. D. in Chemistry","degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2016,"date_issued":"2016-02-10T08:00:00Z","date_published":"2016-02-10T08:00:00Z","updated_at":"2026-07-24T03:18:57Z","subjects":["Chemistry"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://scholarsmine.mst.edu/doctoral_dissertations/297","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Filger, Dennis L."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.available","label":"Dc Date Available","values":["2016-02-10T08:00:00Z"]},{"key":"dc:type","label":"Dc Type","values":["Dissertation - Open Access"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph. D. in Chemistry"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Missouri--Rolla"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://scholarsmine.mst.edu/doctoral_dissertations/297"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The thermodynamic acidity (pKa) of iodoform in methanol was determined at 25°C and 35°C; the values are 18.74 and 18.05, respectively . These acidity constants were determined by a modification of the equilibrium quenching technique which involves the conversion of the conjugate base of iodoform, present at equilibrium, to the radioactively labelled acid.
The rate constants for the methoxide-catalyzed hydrogentritium exchange of chloroform, iodoform, 9-phenylfluorene and indene were determined in methanol at various temperatures. The second-order rate constants obtained from these studies were shown to be the rate constants for removal of a triton. The activation parameters (ΔH‡ and ΔS‡) for the exchange reactions were also determined for these hydrocarbons from the results of the exchange studies at various temperatures.
The hydrogen-deuterium isotope effects for the reaction of chloroform, iodoform or 9-phenylfluorene with methoxide were determined in methanol at various temperatures. These isotope effects were found to be small for chloroform and iodoform (1.25 and 1.02 at 0°C, respectively), and large for 9-phenylfluorene (5 .3 at 10°C). The low isotope effects for the haloforms are suggested as evidence of a highly asymmetric transition state for the proton transfer. A method was developed to determine the hydrogen-tritium isotope effects for the reaction of methanol with the conjugate bases of chloroform, iodoform and 9-phenylfluorene in methanol at bases of chloroform, iodoform and 9-phenylfluorene in methanol at various temperatures. The values for these isotope effects at 0°C are 1.50 and 1.27 for the chloroform and iodoform conjugate bases, respectively and 12.9 for the conjugate base of 9-phenylfluorene at 10°C.
From the results of the kinetic exchange studies on iodoform and chloroform, along with the thermodynamic pKa's determined for iodoform, and assuming a Bronsted exponent of unity, the pKa of chloroform in methanol at 25°C was calculated to be 21.1\"--Abstract, pages iii-iv.
"]},{"key":"dc:title","label":"Title","values":["A study of the kinetic and thermodynamic properties of carbon acids in methanol"]}]}],"canonical_facts":{"dc:creator":["Filger, Dennis L."],"dc:date.available":["2016-02-10T08:00:00Z"],"dc:description.abstract":["The thermodynamic acidity (pKa) of iodoform in methanol was determined at 25°C and 35°C; the values are 18.74 and 18.05, respectively . These acidity constants were determined by a modification of the equilibrium quenching technique which involves the conversion of the conjugate base of iodoform, present at equilibrium, to the radioactively labelled acid.
The rate constants for the methoxide-catalyzed hydrogentritium exchange of chloroform, iodoform, 9-phenylfluorene and indene were determined in methanol at various temperatures. The second-order rate constants obtained from these studies were shown to be the rate constants for removal of a triton. The activation parameters (ΔH‡ and ΔS‡) for the exchange reactions were also determined for these hydrocarbons from the results of the exchange studies at various temperatures.
The hydrogen-deuterium isotope effects for the reaction of chloroform, iodoform or 9-phenylfluorene with methoxide were determined in methanol at various temperatures. These isotope effects were found to be small for chloroform and iodoform (1.25 and 1.02 at 0°C, respectively), and large for 9-phenylfluorene (5 .3 at 10°C). The low isotope effects for the haloforms are suggested as evidence of a highly asymmetric transition state for the proton transfer. A method was developed to determine the hydrogen-tritium isotope effects for the reaction of methanol with the conjugate bases of chloroform, iodoform and 9-phenylfluorene in methanol at bases of chloroform, iodoform and 9-phenylfluorene in methanol at various temperatures. The values for these isotope effects at 0°C are 1.50 and 1.27 for the chloroform and iodoform conjugate bases, respectively and 12.9 for the conjugate base of 9-phenylfluorene at 10°C.
From the results of the kinetic exchange studies on iodoform and chloroform, along with the thermodynamic pKa's determined for iodoform, and assuming a Bronsted exponent of unity, the pKa of chloroform in methanol at 25°C was calculated to be 21.1\"--Abstract, pages iii-iv.
"],"dc:identifier":["https://scholarsmine.mst.edu/doctoral_dissertations/297"],"dc:subject":["Chemistry"],"dc:title":["A study of the kinetic and thermodynamic properties of carbon acids in methanol"],"dc:type":["Dissertation - Open Access"],"thesis:degree_name":["Ph. D. in Chemistry"],"thesis:institution_name":["University of Missouri--Rolla"]},"updated_at":"2026-07-24T03:18:57Z"}