Abstract

The behaviour of the calorimetric response in continuous injection devices, which are well suited for measurement of excess partial molar enthalpies at different concentrations, is analysed by means of heat transport models. Signal analysis of the thermal response gives the enthalpy values at very low concentrations. We establish an operating routine for the identification of the time-varying device, and a generalized deconvolution procedure to obtain, with high accuracy, the power released in the calorimeter as a function of time. The main features considered are the changes in sensitivity and dynamic properties of the experimental system due to the injection of one component in the mixture. A formal decomposition of the heat transport equations shows that typically time-invariant methods are able to deal with deconvolution in non-invariant systems.

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