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Thermodynamic and kinetic analysis of the dimerization of aqueous glyoxal

✍ Scribed by Alfred R. Fratzke; Peter J. Reilly

Publisher
John Wiley and Sons
Year
1986
Tongue
English
Weight
586 KB
Volume
18
Category
Article
ISSN
0538-8066

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✦ Synopsis

Equilibria and rates of interconversion between monomeric and dimeric glyoxal were measured in aqueous solution. The equilibrium constant [G2]/[GJ2 was 0.56 M-' 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 1.3-7.8 being of the form bl[H30*I + bp + b3[OH-]/(1 + b,[OH-I) + b,[OH-]. Coefficients 6, and bp 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 interconversion of Q -hydroxycarbonyls and a -dicarbonyls or for related reactions such as mutarotations and hydrations. Equivalent rate forms arise from reactions where an intermediate a t steady state and low concentration is produced.

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