Journal of the Chemical Society A Inorganic Physical Theoretical · 1969 · 15 citations · 0 references
Natural SciencesBiochemistryChemistryChemical KineticsInorganic ChemistryPhysical ChemistryCatalytic Reaction KineticsChemical Reaction KineticsCoordination ChemistryElectrochemical KineticsKinetic ModelingReaction OrderActivation EnergyApparent Activation EnergyIonic StrengthIonic Strength DependenceIonic Strength EffectsKinetic Studies Of Organometallic ReactionsKinetics Of Coordination CompoundsOxidation Kinetics
The kinetics of the reaction 2Mo(CN)83–+ 3I–→ 2Mo(CN)84–+ I3– have been studied as a function of temperature and ionic strength. The reaction is first-order with respect to both the octacyanomolybdate(V) and iodide concentrations and there is evidence of retardation by product octacyanomolybdate(IV). The second-order rate constant is kobs= 3·52 ± 0·13M–1 sec.–1 in the expression –d[Mo(CN)83–]/dt=kobs[Mo(CN)83–][I–] and the activation energy and entropy of activation have the values Ea= 5·68 ± 2·57 kcal./mole and ΔS*=–39 ± 8·5 e.u. at 25·7°C and I= 0·1M. The plot of log kobs against √I is linear with a slope of + 3·12, which suggests that ion-pairs may not play an important role in this reaction.