A calorimetric approach is described for analysing the kinetics of periodat
e oxidation on a series of monosaccharidic substrates. Rate constants at se
veral temperatures were calculated from the calorimetric decay curves that
are proportional to the rate of conversion. Arrhenius plots provided the ac
tivation parameters for the various carbohydrates and a linear correlation
was found between the values of enthalpy and entropy of activation. The dep
endence of the values of kinetic rates on stereochemistry is interpreted in
terms of conformational probability of the reactive state. The suitability
of the calorimetric method to track the kinetic process of slow reactions
is emphasised, in particular its ability to monitor, directly and continuou
sly, the course of the reaction. (C) 2000 Elsevier Science Ltd. All rights
reserved.