ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Equilibria and rates of interconversion between monomeric and dimeric glyoxal were measured in aqueous solution. The equilibrium constant [G2]/[G1]2 was 0.56 M-1 at 25°C, and was hardly affected by changes of ionic strength and pH but increased rapidly with increase of temperature. The rate of depolymerization was first-order in dimer, with the pseudo first-order rate coefficient in the pH range 1.3-7.8being of the form b1[H3O+] + b2 + b3[OH-]/(1 + b4[OH-]) + b5[OH-]. Coefficients b1 and b2 were more strongly affected by changes of temperature, though [OH-] was much the more effective catalyst. This rate form has not previously been observed for monomer-dimer inter-conversion of α-hydroxycarbonyls and α-dicarbonyls or for related reactions such as mutarotations and hydrations. Equivalent rate forms arisefrom reactions where an intermediate at steady state and low concentration is produced.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550180705
