Spectrophotometric techniques were used to elucidate the discrepancies surrounding the reduction of osmium tetroxide by several primary alcohols in a hydroxide matrix. In contrast to the documented literature, this reaction was observed to occur in two consecutive reaction steps. Geometrical and computational analysis of kinetic data revealed that the reaction proceeds by the following reaction model: Os(VIII) + RCH2OH Os(VI) + RCHO Os(VIII) + Os(VI) Os2(VII) k1 k+2 k-2 The conditional rate constants and molar extinction coefficients were calculated using custom written software. A hydride transfer mechanism, coupled with the synchronous removal of the hydroxyl proton of the alcohol, was postulated. The complexation between osmium(VIII) and osmium(VI) was investigated. Mole ratio titrations and mole fraction plots show that at pH 14.3 a 1:1 complexation occurs between osmium(VIII) and osmium(VI). The equilibrium constants and molar extinction coefficients calculated by these methods were found to be consistent with the parameters obtained from the reduction of osmium tetroxide by primary alcohols at pH 14.3. The formation of a mixed oxidation state dimeric osmium complex (denoted Os2(VII)) has been proposed. Key words: Spectrophotometric techniques, osmium tetroxide, osmium(VIII), primary alcohols, osmium(VI).
| Identifer | oai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:nmmu/vital:10395 |
| Date | January 2009 |
| Creators | Geswindt, Theodore Earl |
| Publisher | Nelson Mandela Metropolitan University, Faculty of Science |
| Source Sets | South African National ETD Portal |
| Language | English |
| Detected Language | English |
| Type | Thesis, Masters, MSc |
| Format | xiii, 139 leaves, pdf |
| Rights | Nelson Mandela Metropolitan University |
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