Abstract
The kinetics of reduction of dodecatungstocobaltate(III) by oxalate follow the rate laws kobs.= 2k1[HC2O4–] and kobs.= 2k2[C2O42–] at high and low hydrogen ion concentrations respectively. Both these apparent second-order rate constants (k1 and k2) depend on the concentration and type of cation present; k1 and k2 decrease in the order K+ > Na+∼ Li+ and K+ > Na+ > Li+ respectively. The K+ and Na+ assisted paths have been studied in detail. The rate constants for these catalysed paths along with those for uncatalysed ones have been evaluated. Thermodynamic parameters (ΔH‡ and ΔS‡) associated with k1 and k2 have been determined. A cation-bridged outer sphere electron transfer mechanism is most likely to take place, with simultaneous generation of free radicals (C2O4˙–).
Sign-in/Register to access full text options 
Free) 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call
