Chapter 1 describes an overview of electron-transfer reactions. The kinetic equations for ET reactions have also been described in detail.
Chapter 2 describes a series of novel kinetic accelerations which deviate strongly from the predictions of the classical Debye-Huckle theory with a range of different added “inert” electrolytes. The greater catalytic effects seen with the heavier halides and other catalytic electrolytes (especially certain dicarboxylates) indicate an important role for hole-transfer superexchange in the ET transition state. The hypothesis of a catalytic ternary association complex, [RuII--X--RuIII] has also been explored by kinetic modeling of the reaction. An increasing ratio of anion-catalyzed ketx to uncatalyzed ket is obtained when proceeding down the halide series. Activation parameters show a strong enthalpy-entropy compensation effect according to the identity of the added halide. Interestingly, the enthalpy activation decreases successively upon going to the heavier halides and in fact ∆H‡ becomes negative in the most extreme case of added I-.
Chapter 3 describes a detailed study of electrolyte effects on the position and band shape of the intervalence charge transfer (IVCT) band of dimeric systems in aqueous solution such as (NH3)5RuII-(bis-bipyridylethylene)-RuIII(NH3)5(5+). Unexpectedly, the energetics of optical electron transfer blue shift upon adding F- but red shift upon adding other halides. This interesting observation correlates with the known water structure “making” or “breaking” effects of the added halide anions
","abstract_html":"<p>Chapter 1 describes an overview of electron-transfer reactions. The kinetic equations for ET reactions have also been described in detail.</p> <p>Chapter 2 describes a series of novel kinetic accelerations which deviate strongly from the predictions of the classical Debye-Huckle theory with a range of different added “inert” electrolytes. The greater catalytic effects seen with the heavier halides and other catalytic electrolytes (especially certain dicarboxylates) indicate an important role for hole-transfer superexchange in the ET transition state. The hypothesis of a catalytic ternary association complex, [RuII--X--RuIII] has also been explored by kinetic modeling of the reaction. An increasing ratio of anion-catalyzed k<sub>etx</sub> to uncatalyzed k<sub>et</sub> is obtained when proceeding down the halide series. Activation parameters show a strong enthalpy-entropy compensation effect according to the identity of the added halide. Interestingly, the enthalpy activation decreases successively upon going to the heavier halides and in fact ∆H<sup>‡</sup> becomes negative in the most extreme case of added I<sup>-</sup>.</p> <p>Chapter 3 describes a detailed study of electrolyte effects on the position and band shape of the intervalence charge transfer (IVCT) band of dimeric systems in aqueous solution such as (NH<sub>3</sub>)<sub>5</sub>Ru<sup>II</sup>-(bis-bipyridylethylene)-Ru<sup>III</sup>(NH<sub>3</sub>)<sub>5</sub>(5+). Unexpectedly, the energetics of optical electron transfer blue shift upon adding F<sup>-</sup> but red shift upon adding other halides. This interesting observation correlates with the known water structure “making” or “breaking” effects of the added halide anions</p>","abstract_has_math":false,"creators":["Han, Zhiji"],"institution":null,"degree_name":"Master of Science in Chemistry","degree_level":"Thesis","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Jeff C. Curtis"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015-05-22T07:00:00Z","date_published":"2015-05-22T07:00:00Z","updated_at":"2026-07-24T05:42:56Z","subjects":["Electron-Transfer","Ruthenium","Stopped-Flow","Inorganic Chemistry"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://repository.usfca.edu/thes/122","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Jeff C. Curtis"]},{"key":"dc:creator","label":"Author","values":["Han, Zhiji"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.available","label":"Dc Date Available","values":["2015-03-03T08:00:00Z"]},{"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 Science in Chemistry"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Electron-Transfer","Ruthenium","Stopped-Flow","Inorganic Chemistry"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://repository.usfca.edu/thes/122"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Chapter 1 describes an overview of electron-transfer reactions. The kinetic equations for ET reactions have also been described in detail.
Chapter 2 describes a series of novel kinetic accelerations which deviate strongly from the predictions of the classical Debye-Huckle theory with a range of different added “inert” electrolytes. The greater catalytic effects seen with the heavier halides and other catalytic electrolytes (especially certain dicarboxylates) indicate an important role for hole-transfer superexchange in the ET transition state. The hypothesis of a catalytic ternary association complex, [RuII--X--RuIII] has also been explored by kinetic modeling of the reaction. An increasing ratio of anion-catalyzed ketx to uncatalyzed ket is obtained when proceeding down the halide series. Activation parameters show a strong enthalpy-entropy compensation effect according to the identity of the added halide. Interestingly, the enthalpy activation decreases successively upon going to the heavier halides and in fact ∆H‡ becomes negative in the most extreme case of added I-.
Chapter 3 describes a detailed study of electrolyte effects on the position and band shape of the intervalence charge transfer (IVCT) band of dimeric systems in aqueous solution such as (NH3)5RuII-(bis-bipyridylethylene)-RuIII(NH3)5(5+). Unexpectedly, the energetics of optical electron transfer blue shift upon adding F- but red shift upon adding other halides. This interesting observation correlates with the known water structure “making” or “breaking” effects of the added halide anions
"]},{"key":"dc:title","label":"Title","values":["Electrolyte Effects on the Kinetics of Comproportionation Electron-Transfer Reactions and on Intervalence Charge-Transfer Band Energies of Binuclear Ruthenium Ammine Complexes"]}]}],"canonical_facts":{"dc:contributor":["Jeff C. Curtis"],"dc:creator":["Han, Zhiji"],"dc:date.available":["2015-03-03T08:00:00Z"],"dc:description.abstract":["Chapter 1 describes an overview of electron-transfer reactions. The kinetic equations for ET reactions have also been described in detail.
Chapter 2 describes a series of novel kinetic accelerations which deviate strongly from the predictions of the classical Debye-Huckle theory with a range of different added “inert” electrolytes. The greater catalytic effects seen with the heavier halides and other catalytic electrolytes (especially certain dicarboxylates) indicate an important role for hole-transfer superexchange in the ET transition state. The hypothesis of a catalytic ternary association complex, [RuII--X--RuIII] has also been explored by kinetic modeling of the reaction. An increasing ratio of anion-catalyzed ketx to uncatalyzed ket is obtained when proceeding down the halide series. Activation parameters show a strong enthalpy-entropy compensation effect according to the identity of the added halide. Interestingly, the enthalpy activation decreases successively upon going to the heavier halides and in fact ∆H‡ becomes negative in the most extreme case of added I-.
Chapter 3 describes a detailed study of electrolyte effects on the position and band shape of the intervalence charge transfer (IVCT) band of dimeric systems in aqueous solution such as (NH3)5RuII-(bis-bipyridylethylene)-RuIII(NH3)5(5+). Unexpectedly, the energetics of optical electron transfer blue shift upon adding F- but red shift upon adding other halides. This interesting observation correlates with the known water structure “making” or “breaking” effects of the added halide anions
"],"dc:identifier":["https://repository.usfca.edu/thes/122"],"dc:subject":["Electron-Transfer","Ruthenium","Stopped-Flow","Inorganic Chemistry"],"dc:title":["Electrolyte Effects on the Kinetics of Comproportionation Electron-Transfer Reactions and on Intervalence Charge-Transfer Band Energies of Binuclear Ruthenium Ammine Complexes"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Thesis"],"thesis:degree_name":["Master of Science in Chemistry"]},"updated_at":"2026-07-24T05:42:56Z"}