We present here a calorimetric method and the construction details of a differential calorimeter useful for studying the reactions in an electrolytic cell and more generally slow chemico-physical processes occurring in thermodynamically open systems. The method allows measurements of the heat balance of the cell, from which the enthalpy change of the process under investigation can be calculated. The theoretical description of the calorimetric cell and the results of several studies planned to describe the performances of the instrument up to the boiling point of the electrolytic solution are reported. The features of this calorimeter fulfil most of the requirements of ≪col fusion≫ experiments, where the heat production is the fundamental and controversial aspect. By controlling both the heat and the matter exchanged, the calorimeter can be utilised also to study bioenergetic processes,e.g. fermentation, microbial metabolism and biodegradation, and liquid phase chemical reactions, involving gases as reactants and/or products.

We report a new microcalorimetric technique which allows simultaneous measurements of the heat capacity and the rate of enthalpy release during the chemical reaction in a substance under quasi-isothermal conditions. The basic features of the instrument are presented together with brief experimental results on the polymerization of diglycidyl ether of bisphenol A mixed with ethylene diamine. The instrumentation is an advance for studies of both synthetic and biological formation of macromolecules, for now it becomes possible to measure the heat capacity of a time-variant system and to characterize its vitrification transition occurring at constant temperature, as the growth of the macromolecule by chemical reaction increases the sample’s viscosity. The abrupt decrease observed in the heat capacity curve corresponds to the vitrification transition, which cannot be observed in the corresponding enthalpy release curve. The present calorimeter has an important use in both technological assessment and in understanding the fundamental aspects of the vitrification phenomenon.

A microcalorimeter for liquid samples with high performance and low cost is described. It is essentially a differential apparatus in a ‘‘twin’’ configuration with two cylindrical cells. Two resistive sensors, put in a Wheatstone bridge, are wound on the cells to measure the temperature difference between them. Sensitivity, response time, and calibration procedure are reported. As illustrative example, the specific heat of some liquids at two temperatures has been measured.