ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Rates of disproportionation of 0.015-0.4 mM aqueous glyoxal toglycolic acid were measured at 0.24-75 mM NaOH and constant ionic strength, leading to the empirical rate expression r = (a1[OH-] + a2[OH-]2) [GT]/(1 + a3[OH-]), where [GT] is the total glyoxal concentration. These results were confirmed in bicarbonate/carbonate buffer and at 2-20 mM [GT]. The rate form is in contradiction to earlier work on glyoxal, which suggested a second-order dependence on [OH-], but agrees with the rate equation for phenylglyoxal disproportionation. The kinetic data can be explained by a mechanism postulating the presence of monohydrated and dihydrated forms of glyoxal in equilibrium, with the rate-limiting steps being intramolecular hydride ion transfers to the unhydrated carbonyl carbon of the mono- and divalent anions of glyoxal monohydrate.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550180704
