Abstract
In Section 1 of this thesis, a spectroscopic investigation of the dehydrated periodate monoanion, IO[4-], is described. The electronic absorption spectrum of IO[4-] was measured in the range 210-230 nm at 25°C in various solvents. The solvent shifts provide evidence for the assignment of the electronic transitions. The weak band near 280 is assigned as to a n → pi* transition and the intense band near 222 nm to a pi → pi* transition. The IR spectra of the same ion in some of the solvents used provide some supporting evidence for the assignments of bands. A computer method for the analysis of two overlapping bands is presented. Section 2 describes a kinetic study of the oxidation of malonic, tartronic, ketomalonic and glyoxylic acids by periodate under conditions of excess acid. Evidence is presented to show that the periodate and acid monoanions are the most reactive species for all the reactions. From the values of the activation parameters for all the reactive species it is deduced that formation of a cyclic intermediate is involved in these reactions. In Section 3, several aspects of the oxidation of glycerol-l-monoacetate by periodate are discussed. Glycerol-1-monoacetate is a vicinal diol containing an electron-withdrawing substituent. Its oxidation by periodate is compared with previous work on analogous reactions of vicinal diols having electron-donating substituents.