
TY  - JOUR
A1  - O'Conner, CJ 
A1  - Odell, AL 
A1  - Bailey, AAT 
T1  - Mutarotation of D(+)-glucose. II. Volumes of activation for the uncatalysed and copper(II)-catalysed rates
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1983
VL  - 36
IS  - 2
SP  - 279
EP  - 287
KW  - 
UR  - https://doi.org/10.1071/CH9830279 
N2  - The effect of high pressure on the rate of mutarotation of &#945;-and &#946;-D(+)-glucose in aqueous sodium perchlorate solutions has been evaluated. The observed rate constant k&#936; = k&#945; + k&#946; increases with pressure while the equilibrium constant Keq = k&#945; /k&#946; is nearly unchanged from the 1.7 found at 1 bar. From the experimental results, the individual rate constants k&#945; and k&#946; and the corresponding activation volumes &#8710;V&#8225;&#945; and &#8710;V&#8225;&#946; can be evaluated. The values obtained, -10.7 ± 0.1 and -10.0 ± 0.1 cm3 mol-1, are discussed in relation to the reaction mechanism. In the presence of Cu(ClO4)2 the values of &#8710;V: form a continuous series, dependent upon the pH and the concentration of copper(II) catalyst, up to + 1.3 cm3 mol-1. The activation volumes for mutarotation by monomeric and dimeric copper(II) catalysts, &#8710;V&#8225;(Cu2+) and &#8710;V&#8225; {CU((OH)2Cu)2+}, are -1.2 ± 0.2 and + 3.6 ± 0.2 cm3 mol-1 respectively. Reaction mechanisms are discussed to account for these values of &#8710;V&#8225;. 
ER  -

