"KINETIC STUDIES OF THE AQUATION OF SOME NITRO AMINE COBALT (III) COMPLEXES USING METAL IONS AS CATALYSTS"

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Date
1971-09
Authors
OLATUNJI, MOBOLANLE ADEGBOYEGA
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Abstract
The mercury (ii) and thallium (ill) catalysed aquation of transdinitrotetrammine Cobalt (ill) and trans-dinitrobisethylenediamine Cobalt (ill) nitrates have been studied over a wide temperature range of 30 "to 50 C at various constant hydrogen ion concentrations of between 0,1 to 1.8 M. The ionic strength of the different reactions were also kept constant between 0.2 to 2,0 M. In the cation concentration range used [0.01 to 0.30 M] the increase in rate in the different reactions with the exception of the one involving [Co(NH3 )4 (N02)2] N03 and Tl3+ were interpreted in terms of two complex species - a protonated species [co(AA)2(N02)(N02H]2+ and a cation associated species [CO(AA)2(N0 ) n+1 (N02M)J] . Reaction rate constants have been ubteined and thermodynamic parameters derived for all the reactions. For the reaction of the transdinitrotetrammine Cobalt (ill) complex using mercury (II) as catalyst, the activation energies and entropies of activation are as follows: Using thallium (ill) as catalyst for the same complex the calculated activation energy and entropy of activation for the thallium (ill) associated species at 25 are: Ea = 16.6 k cals/mole; A 6 = -6.80 e.u. Under the hydrogen ion concentration used, no reaction due to the protonated species was observed. However an initial fast reaction which was attributed to the hydroxide catalysed reaction was observed. In the case of trans-dinitrobisethylenediamine Cobalt (ill) complex, two intermediate complex species were involved in all the reactions involving the two metal ions. For the mercury (il) catalysed aquation,
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A Thesis Presented To AHMADU BELLO UNIVERSITY For The Degree Of MASTER OF SCIENCE
Keywords
KINETIC STUDIES,, AQUATION,, NITRO AMINE COBALT (III) COMPLEXES,, NITRO AMINE COBALT (III) COMPLEXES,, CATALYSTS,
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