Synthesis, Acid Hydrolysis and Formation of the Molybdatopentaamminechromium(III) Ion in Aqueous Solution
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Alvin A. Holder
Abstract
The title complex has been synthesised for the first time and characterised by elemental analysis and spectroscopic analyses. The kinetics of the acid hydrolysis and formation of the title complex have been studied using the stopped-flow technique. The acid hydrolysis experiments were carried out over the ranges, 0.01 < [H'] < 0.14 mol dm 3, 22.4° C < θ < 30.1 C and at ionic strength 1.0 mol dm 3 (NaNO3), whereas the formation kinetics were studied over the ranges 7.22 < pH < 8.18 and 25.0 C < θ < 33.9 C, with ionic strength 1.0 mol dm 3 (NaClO4). The rate of acid hydrolysis is inversely dependent on [Η ' ] which has been ascribed to the expansion of the coordination number of the molybdenum(VI) from four to six on protonation, along with resonance stabilisation. The rate constant, k f o r the hydrolysis is 22.6 ± 0.3 s1 at 25.1 C for which ΔΗ' = 89±5 kJ mol 1 and ΔS'= 81 ± 2 1 J mol1 Κ 1 The rate constants for the reactions of (NH3)5CrOH3 and (NH3)5CrOH2 to form the title complex are (1.18 ±0.07) x 107 mol1 dm3 s1 and (1.13 ± 0.05) x 105 mol1 dm3 s1 respectively at 25.0 C. The results indicate that both processes are occurring via a mechanism involving MoVI -O bond breakage.
© 2014 by Walter de Gruyter Berlin/Boston
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- Notes for Contributors Inorganic Reaction Mechanisms
- Journal Order Form
Artikel in diesem Heft
- Synthesis, Acid Hydrolysis and Formation of the Molybdatopentaamminechromium(III) Ion in Aqueous Solution
- Kinetic and Mechanistic Studies on the Interaction of Adenosine with Diaquaethylenediamineplatinum(II) Ion
- On the Mechanism of Oxidation of Formate by Ni(III) (meso-5,7,7,12,14,14-hexamethy 1-1,4,8,11 - tetraazacyclotetradecane) in Aqueous Solutions
- Substitution Reactions on Pd(II) L-Histidine-diaqua Complexes: Comparative View from Chloride to Nucleobases and Dinucleotides
- Thermo-kinetic and Spectral Studies of Lanthanide(III) Complexes with 2-Hydroxy-l -benzylidene-2-furoyl Hydrazine
- Free Radical Induced Oxidation of L-Cystine by Alkaline Permanganate - A Kinetic Study
- Reaction between [Ru(H2O)6]2+ and DMF: A Complete Volume Profile of a Monocomplex Formation Reaction on a d6 Low Spin Aquaion
- Notes for Contributors Inorganic Reaction Mechanisms
- Journal Order Form
