Publication Date

12-1985

Advisor(s) - Committee Chair

Robert Farina, Laurence Boucher, John Reasoner

Degree Program

Department of Chemistry

Degree Type

Master of Science

Abstract

Analyses of the kinetic data obtained on the redox reaction between cobalt(II)-4,4',4",4"-tetrasulfophthalocyanine [Co(II)TSPC4-] and iodine in the presence of air show three reactions in dimethylsulfoxide(DMS0), N,N-dimethylacetamide(DMA), and diethylene glycol(DEG) while there are two reactions in methanol(Me0H). Two of the three reactions in DMSO, DMA, and DEG are biphasic with one reaction in all of the solvents being too fast to be accurately measured on the Cary Model 14 spectrophotometer. When the reactant solutions are purged with argon for 40 minutes under identical conditions, the same biphasic reactions are observed in DMSO and DEG while only one of the three reactions is observed in DMA. In methanol, the same two reactions are present. In the absence of air, one of the biphasic reactions in DMSO and DEC,, and one of the two reactions in Me0H are still to fast to be measured accurately on the Cary Model 14 spectrophotometer. All reactions had a large excess of iodine over the Co(II)TSPC4- to ensure that they went to completion. The concentrations of Co(II)TSPC4- and iodine were varied in each solvent to determine their reaction order. The measurable iodine reaction in DMSO,Me0H, and DEC has a first order dependency on both the Co(II)TSPC4- and iodine concentration. In the DMA solvent, the iodine reaction has a one-half order dependency on the iodine concentration and a first order dependency on the Co(II)TSPC4- concentration. There seems to be no simple dependency on the concentrations of either iodine and oxygen in the oxygen related reactions in all solvents. The redox reaction in each solvent was examined over a range of temperatures in order to obtain the activation parameters, ΔH* and ΔS*. A brief kinetic study was made in DMSO with iodide introduced into the reaction system.

Disciplines

Chemistry | Physical Sciences and Mathematics

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