Exothermic/endothermic change, measuring

Q.9.16 The energy of a system is easily measured by thermal techniques. When the state of a system and a change in the state observables is temperature dependent, an exothermic or endothermic change can be measured. For the following list of events indicate whether a physical change is endothermic or exothermic. 

DSC is a precise method of measuring the endothermic and exothermic behaviors of sample materials. Unlike the earlier version of the thermal analyzer, the differential thermometric analyzer (DTA) measures the temperature difference between two cells heating in the same furnace. The power-compensated DSC uses two independent furnaces, one for the sample and one for the reference. When an exothermic or endothermic change occurs in the sample materials, energy is applied to or removed from one or both furnaces to compensate for energy changes in the sample. This means that the system directly measures energy flows to or from a sample at all times. 

In calorimetry techniques, enthalpy changes accompanying physical or chemical events, whether they are exothermic or endothermic, are measured and monitored either as a function of temperature or time. Thus, a calorimeter is able to collect a heat flux exchanged between the sample and the sensible part of the apparatus, generally made of thermocouples, and to register it. The result is a profile of the rate of enthalpy change, either as a function of temperature as the sample is heated at a known linear rate in differential scanning calorimetry (DSC), or as a function of time when the calorimeter is held at constant temperatnre in isothermal differential calorimetry (DC). 

The resultant thermogram is similar to a DTA trace but more accurate and reliable. Endothermic changes are recorded as heat input into the sample, and exothermic changes as heat input into the reference. The area of the peaks is an exact measure of heat input involved. Differences in heat capacity or thermal conductivity do not affect the results. From the data, accurate quantitative analytical results can be obtained. 

In DSC or DTA, the heat input (endotherm) or heat generated (exotherm) of a material can he continuously monitored while it is subjected to a controlled temperature increase. The heat changes measured correspond to phase changes that occur at the indicated temperature for example, they may consist of glass transitions, softening, melting, oxidation, sublimation, or decomposition all characteristics of a given material. Applications... 

By allowing compounds to react in a calorimeter, it is possible to measure the heat evolved in an exothermic reaction or the heat absorbed in an endothermic reaction. Thousands of reactions have been studied to produce a rich library of thermochemical data. These data take the form of heats of reaction and correspond to the value of the enthalpy change A/-/° for a particular reaction of a particular substance. 

The decompositions of these compounds are of interest since they are used as binders in electron-emissive coatings [1023]. The initial stage of the endothermic reaction in vacuum or nitrogen (520—820 K) yields residual carbonate and a small quantity of carbon. Changes in surface area during reactions have been measured. The main volatile product is HCHO, but secondary, exothermic reactions occur on the surface of the product carbonate so that the overall reaction is... 

Although there are other ways, one of the most convenient and rapid ways to measure AH is by differential scanning calorimetry. When the temperature is reached at which a phase transition occurs, heat is absorbed, so more heat must flow to the sample in order to keep the temperature equal to that of the reference. This produces a peak in the endothermic direction. If the transition is readily reversible, cooling the sample will result in heat being liberated as the sample is transformed into the original phase, and a peak in the exothermic direction will be observed. The area of the peak is proportional to the enthalpy change for transformation of the sample into the new phase. Before the sample is completely transformed into the new phase, the fraction transformed at a specific temperature can be determined by comparing the partial peak area up to that temperature to the total area. That fraction, a, determined as a function of temperature can be used as the variable for kinetic analysis of the transformation. 

Measurements of thermal analysis are conducted for the purpose of evaluating the physical and chemical changes that may take place in a heated sample. This requires that the operator interpret the observed events in a thermogram in terms of plausible reaction processes. The reactions normally monitored can be endothermic (melting, boiling, sublimation, vaporization, desolvation, solid-solid phase transitions, chemical degradation, etc.) or exothermic (crystallization, oxidative decomposition, etc.) in nature. 

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