Electrolyte Effects on the Kinetics of Comproportionation Electron-Transfer Reactions and on Intervalence Charge-Transfer Band Energies of Binuclear Ruthenium Ammine Complexes

<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_etx to uncatalyzed k_et 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^-.</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 (NH₃)₅Ru^II-(bis-bipyridylethylene)-Ru^III(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</p>

Name thesis:degree_name

Master of Science in Chemistry

Level thesis:degree_level

Thesis

Discipline thesis:degree_discipline

Chemistry

Year dc:date.available

2015

Author dc:creator

• Han, Zhiji

Contributors dc:contributor

• Jeff C. Curtis

• Electron-Transfer
• Ruthenium
• Stopped-Flow
• Inorganic Chemistry

Repository record dc:identifier

https://repository.usfca.edu/thes/122

OAI identifier oai:identifier

oai:repository.usfca.edu:thes-1139