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.
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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 |
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