ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The Co(NH3)5OH23+ ion reacts with malonate to form Co(NH3)5O2CCH2CO2H2+ or Co(NH3)5O2CCH2CO2+, depending on the pH of the reaction solution. The kinetics of this anation reaction have been studied as a function of [H+] for the acidity range 1.5 ≤ pH ≤ 6.0 in the temperature range of 60 to 80°C, the [total malonate] ≤ 0.5 M, and the ionic strength 1.0M. The anation by malonic acid follows second-order kinetics, the rate constant being 8.0 × 10-5 M-1·sec-1 at 70°C, and the anations by bimalonate (Q1, k1) and malonate ion (Q2, k2) are consistent with an Id mechanism. Typical values at 70°C for the ion pair formation constants are Q1 = 1.3, Q2 = 5.4M-1; and for the interchange rate constants k1 = 5.3 × 10-4; k2 = 7.3 × 10-4 sec-1. The activation parameters for the various rate constants are reported and the results discussed with reference to previously reported data for similar systems.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550080308
