Calorimetric properties flow techniques

These preliminary results show that the promise of flow calorimetric techniques for investigating the thermodynamic properties of high temperature aqueous solutions has been realized. Although there are many experimental difficulties in adapting... 

Clearly, it would be desirable if the area under the peak was a measure of the enthalpy associated with the transition. However, in the case of DTA, the heat path to the sample thermocouple includes the sample itself. The thermal properties of each sample will be different and uncontrolled. In order for the DTA signal to be a measure of heat flow, the thermal resistances between the furnace and both thermocouples must be carefully controlled and predictable so that it can be calibrated and then can remain the same in subsequent experiments. This is impossible in the case of DTA, so it cannot be a quantitative calorimetric technique. Note that the return to baseline of the peak takes a certain amount of time, and during this time the temperature increases thus the peak appears to have a certain width. In reality this width is a function of the calorimeter and not of the sample (the melting of a pure material occurs at a single temperature, not over a temperature interval). This distortion of peak shape is usually not a problem when interpreting DTA and DSC curves but should be borne in mind when studying sharp transitions. 

When coupled to gas adsorption data, calorimetric data can be very useful for the textural characterization of carbons. The use of chemical probes with different molecular sizes allow determining the pore size distribution [288-295]. On the other hand, relevant information concerning chemical properties of the carbon surfaces and their influence on the sorption properties of carbons can be obtained when using the appropriate calorimetric technique. Immersion, flow adsorption and gas-adsorption calorimetry have been employed for the study of surface chemistry of carbons. For instance, immersion calorimetry provides a direct measurement of the energy involved in the interaction of vapor molecules of the immersion liquid with the surface of the solid. This energy depends on the chemical nature of the solid surfajoe and the probe molecules, i.e. the specific interaction between the solid and the liquid. Comparison between enthalpies of immersion into liquids with different polarities provides a picture of the surface chemistry of the solid. Although calorimetric techniques are not able to completely characterize the complex surface chemistry of carbons, they represent a valuable complement to other techniques. 

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