KINETICS AND MECHANISMS OF THE OXIDATION - REDUCTION AND THE SUBSTITUTION REACTIONS OF SOME METAL ION COMPLEXES IN ACID SOLUTION.

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dc.contributor.authorIYUN, JOHNSON FEMI
dc.date.accessioned2014-02-10T10:31:00Z
dc.date.available2014-02-10T10:31:00Z
dc.date.issued1982-08
dc.descriptionA thesis submitted to the Postgraduate School, Ahmadu Bello University, in fulfilment of the requirements for the degree of Doctor of Philosophy in Chemistry.en_US
dc.description.abstractThe kinetics and mechanism of the oxidation of Ti(H20)g and Ti -edta by aqueous solutions of bromine and iodine has been investigated. At T = 25°C, I = 1.0M-(CFgS03-Li+ + CF3S03H)[H+] m 0.034 - 0.274M and X = 453nm, the rate equation 3 + for the oxidation of Ti(H20)6 by bromine was found to be: Z^ [ B r i = _JS| [Br9][Ti(lll)] + ——^ [Ti(lll)][Br:] d t 2 T [H +] + K [H ] + K 6 where k = 9.2 x 10- 3M- 1s- 1 and K = 4.5 x 10~3M. At [H ] = 1.0M, [Br-]. ='0.05 - 0.4M, the apparent second-order rate constant decreases as [Br-] increases. From the analysis of the data under these conditions, values of the second-order 2+ - rate constants for the oxidation of Ti(H20)fi by Br2 and Br„ were computed to be (3.88 ± °-4> x iP2*f" s" and (29.4 ± l.DM'V1 respectively. The rate equation for the oxidation of Ti(H20)6^+ by iodine was found to be, j r T -i — = kl Ka [Ti(lll)][I0] + k2 Ka [Ti(lll)][II]. j. & i> [H+] + Ka [H+] •+ Ka For the conditions [H+] = 0.0036 - 0.20M, 1= 1.OM (LiCl), T=25°C and X = 468m, k, = 5.3 x 102M-1s-1 kn = 6.9M-1s-1 and K • 3.2 x 10-3M.' The apparent second-order rate constant for the oxidation 111 of Ti -edta by bromine and iodine showed a biphasic dependence on pH in the range pH = 0.5 - 6.0 for bromine and pH = 0.15 - 7.45 for iodine. Below pH = 2.5, the second-order rate constant is independent of pH but for pH > 2.5 the rate constant increases with pH.en_US
dc.identifier.urihttp://hdl.handle.net/123456789/854
dc.language.isoenen_US
dc.subjectKINETICSen_US
dc.subjectMECHANISMSen_US
dc.subjectOXIDATIONen_US
dc.subjectREDUCTIONen_US
dc.subjectSUBSTITUTIONen_US
dc.subjectREACTIONSen_US
dc.subjectMETALen_US
dc.subjectCOMPLEXESen_US
dc.subjectACIDen_US
dc.subjectSOLUTIONen_US
dc.titleKINETICS AND MECHANISMS OF THE OXIDATION - REDUCTION AND THE SUBSTITUTION REACTIONS OF SOME METAL ION COMPLEXES IN ACID SOLUTION.en_US
dc.typeThesisen_US
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