Stopped-Flow Studies of the Oxidation of Organic Substrates by Cerium(IV), Thallium(III) and Vanadiu (V)

Amjad, Zahid (1975) Stopped-Flow Studies of the Oxidation of Organic Substrates by Cerium(IV), Thallium(III) and Vanadiu (V). PhD thesis, University of Glasgow.

Abstract

The Cerium(lV) ion has been shown to exist in perchloric acid solution as a mixture of Ce4+ and CeOH3+ The hydrolysis constant has been determined spectrophotometrically and compared with the existing data on tetravalent ions. From a spectrophotometric study, values of the molar extinction coefficients of each ion have been determined over a wavelength range of 300-400 nm. Two different types of apparatus utilizing the stopped-flow technique have been used to study the following reactions: a) the cerium(lV) oxidation of alpha-hydroxy acids, malonic acid, L-cysteine and DL-penicillamine b) the reaction of thiomalic acid with thalliuim(III) and c) the vanadium(v) oxidation of thiourea. Ceriuro(lV) has been shown to oxidise alpha-hydroxy acids (HI) in perchlorate media via well defined intermediate complexes. The ultraviolet spectra and the equilibrium constants of these complexes have been determined and a comparison made with the kinetically derived values and compared with other oxygen containing substrates. The rates of decomposition of the intermediate complex, CeL3+, have been evaluated over a range of acidities (0.25-1.50M) and temperatures (6.8-30

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: Physical chemistry, Organic chemistry
• Date of Award: 1975
• Depositing User: Enlighten Team
• Unique ID: glathesis:1975-78706
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 30 Jan 2020 15:00
• Last Modified: 30 Jan 2020 15:00
• URI: http://theses.gla.ac.uk/id/eprint/78706