Differential thermal analysis peak-area measurement

In the classical differential thermal analysis (DTA) system both sample and reference are heated by a single heat source. The two temperatures are measured by sensors embedded in the sample and reference. In the so-called Boersma system, the temperature sensors are attached to the sample pans. The data are recorded as the temperature difference between sample and reference as a function of time (or temperature). The object of these measurements is generally the determination of enthalpies of changes, and these in principle can be obtained from the area under a peak together with a knowledge of the heat capacity of the material, the total thermal resistance to heat flow of the sample and a number of other experimental factors. Many of these parameters are often difficult to determine hence, DTA methods have some inherent limitations regarding the determination of precise calorimetric values. 

Another technique related to DSC is DTA, differential thermal analysis. In this method sample and reference are heated by a single source and temperatures are measured by thermocouples embedded in the sample and reference or attached to their pans. Because heat is now supplied to the two holders at the same rate, a difference in temperature between the sample and the reference develops, which is recorded by the instrument. The difference in temperature depends, among other things, on the value of K, which needs to be low to obtain large enough differences in temperature to measure accurately. The area under a transition peak now depends on k and it is difficult to determine this accurately or to maintain it at a constant... 

Heats of solid-solid transitions must be determined direcdy, either by calorimetry or by measurement of the area under the endothermic peak on a differential-thermal analysis trace. The heats of transition from one polymorphic crystal form to another are listed in order of decreasing temperature, each value having the designation of the form which is stable below the transition temperature. 

Information on the free energy, heat, and entropy of water adsorption on clays during the subsequent stages of the adsorption and desorption process can be calculated from water-vapor sorption isotherms obtained at different temperatures. Alternatively, these quantities can be determined by combining the data of a single isotherm with data for the heats of adsorption obtained directly. In appropriate calorimeters, one can measure the heat of adsorption of increments of vapor admitted to the sample, or one can measure the heats of immersion of samples that are previously equilibrated with water vapor at various relative vapor pressures. The heat of desorption can also be obtained from the peak areas of differential thermal analysis curves of partially and completely hydrated samples (Barshad [1952]). 

The adsorption up to 50 bars was carried out by means of a Tian-Calvet type isothermal microcalorimeter built in the former CNRS Centre for Thermodynamics and Microcalorimetry. For these experiments, around 2 g of sample was used which were outgassed by Controlled Rate Thermal Analysis (CRTA) [7]. The experiments were carried out at 30°C (303 K). Approximately 6 hours is required after introduction of the sample cell into the thermopile for the system to be within 1/100 of a degree Celsius. At this point the baseline recording is taken for 20 minutes. After this thermal equilibrium was attained, a point by point adsorptive dosing procedure was used. Equilibrium was considered attained when the thermal flow measured on adsorption by the calorimeter returned to the base line. For each point the thermal flow and the equilibrium pressure (by means of a 0-70 bar MKS pressure transdueer providing a sensitivity of 0.5% of the measured value) were recorded. The area under the peak in the thermal flow, Q eas, is measured to determine the pseudo-differential... 

DSC plots are obtainetl as the differential rate of heating (in units of watts per second, calories per second, or Joules per second) against temperature, and thus they represent direct measures of the heat capacity of the sample. The area under a DSC peak is directly proportional to the heat absorbed or evolved by the thermal event, and integration of these peak areas yields the heat of reaction (in units of calories per second per gram or Joules per second per gram). Owing to the ability to facilitate quantitative data interpretation, the use of DSC analysis has virtually supplanted the use of DTA analysis. 

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