Temperature-time curve calorimetry

Adiabatic calorimetry. Dewar tests are carried out at atmospheric and elevated pressure. Sealed ampoules, Dewars with mixing, isothermal calorimeters, etc. can be used. Temperature and pressure are measured as a function of time. From these data rates of temperature and pressure rises as well as the adiabatic temperature ri.se may be determined. If the log p versus UT graph is a straight line, this is likely to be the vapour pressure. If the graph is curved, decomposition reactions should be considered. Typical temperature-time curves obtained from Dewar flask experiments are shown in Fig. 5.4-60. The adiabatic induction time can be evaluated as a function of the initial temperature and as a function of the temperature at which the induction time, tmi, exceeds a specified value. 

Fluorine bomb calorimetry is in many aspects similar to oxygen bomb calorimetry. The experiments are carried out in isoperibol instruments, which, except for the bomb, are basically identical to those described in sections 7.1 and 7.2. The procedure used to calculate Acf/°(298.15 K) from the experimental results is also analogous to that discussed for oxygen bomb calorimetry in section 7.1. Thus, a temperature-time curve, such as the one in figure 7.2, is first acquired, and the corresponding adiabatic temperature rise, A Tad, is derived. 

The experiments are usually carried out at atmospheric pressure and the initial goal is the determination of the enthalpy change associated with the calorimetric process under isothermal conditions, AT/icp, usually at the reference temperature of 298.15 K. This involves (1) the determination of the corresponding adiabatic temperature change, ATad, from the temperature-time curve just mentioned, by using one of the methods discussed in section 7.1 (2) the determination of the energy equivalent of the calorimeter in a separate experiment. The obtained AT/icp value in conjunction with tabulated data or auxiliary calorimetric results is then used to calculate the enthalpy of an hypothetical reaction with all reactants and products in their standard states, Ar77°, at the chosen reference temperature. This is the equivalent of the Washburn corrections in combustion calorimetry... 

Figure 11.2 shows a typical temperature-time curve for a continuous isoperibol titration calorimetry experiment involving an exothermic process. In the initial and final periods (between points a and b, and c and d, respectively), the observed temperature change is determined by the heat of stirring, the heat dissipated by the temperature sensor, and the difference between the temperature of the calorimetric vessel and the temperature of the thermostatic bath. The titration... 

C. E. Vanderzee. Evaluation of Corrections from Temperature-Time Curves in Isoperibol Calorimetry under Normal and Adverse Operating Conditions. J. Chem. Thermodynamics 1981,13, 1139-1150. 

Enthalpies of reaction in solution are generally measured in an isothermal jacketed calorimeter. This consists of a calorimetric vessel that contains a certmn amount of one of the reactants that is either a liquid or, if a solid is involved, it has been dissolved in a suitable solvent. The other reactant is sealed in a glass ampoule that is placed in a holder. The vessel is enclosed in a container, which is placed in a thermostatted bath with the temperature controlled to 0.001 °C. When the system has reached thermal equilibrium, the ampoule is broken and the reaction is initiated. Throughout the experiments the temperature is measured as a function of the time and a temperature-time curve with approximately the same shape as the ones obtmned in combustion calorimetry, vdth fore-period, reaction-period and after-period is obtained. The observed temperature rise is due to several sources die heat transferred from the thermostatted bath, the energy of the reaction and the stirring energy. To correct... 

The temperature/time curves obtained from Dewar calorimetry can be analysed to yield thermodynamic and kinetic data. The procedure is much easier when the experimental data have been logged by computer. 

Adiabatic and Isoperibol Calorimeters.—Most calorimeters used in combustion and reaction calorimetry undergo a change of temperature when reaction takes place. If the calorimeter is surrounded by a jacket, the temperature of which is controlled to be the same as that of the calorimeter, no heat-exchange occurs between the siuroundings and the calorimeter, which is then described as adiabatic. However, if the temperature of the environment is maintained constant (in a type of calorimeter conveniently described as isoperibol and sometimes, incorrectly, as isothermal) some heat-exchange occurs between the calorimeter and its surroundings, but may be accurately determined by analysis of the temperature-time curves before and after reaction takes place, provided the reaction is of short duration (say not exceeding 15 min). With slower processes, isoperibol calorimeters are less useful, and the adiabatic principle is easier to effect and yields more accurate results. 

Isothermal differential scanning calorimetry (DSC) measurements were carried out to investigate the curing kinetics [85]. Conversion vs time curves of DGEBPA-PACP systems prepared with 1 wt % of catalyst and without catalyst at identical curing temperature are overlaid in Fig. 31. 

The cure enthalpy is obtained from the area under the curve expressing the variation of the heat flux as a function of either time with isothermal calorimetry or temperature in scanning calorimetry. The integration of the heat flux given in Equation 1.18 leads to ... 

Chater M., G. Chataing, and J.M. Vergnaud. 1985. Enhanced study of differential scanning calorimetry with determination of heat flux-time curves, profiles of temperature and state of cure. Thermochim. Acta. 90 135-47. 

Differential Scanning Calorimetry. A sample and an inert reference sample are heated separately so that they are thermally balanced, and the difference in energy input to the samples to keep them at the same temperature is recorded. Similarly to DTA analysis, DSC experiments can also be carried out isothermally. Data on heat generation rates within a short period of time are obtained. Experimental curves from DSC runs are similar in shape to DTA curves. The results are more accurate than those from DTA as far as the TMRbaiherm is concerned. 

Many different test methods can be used to study polymers and their physical changes with temperature. These studies are called thermal analysis. Two important types of thermal analysis are called differential scanning calorimetry (DSC) and differential thermal analysis (DTA). DSC is a technique in which heat flow away from a polymer is measured as a function of temperature or time. In DTA the temperature difference between a reference and a sample is measured as a function of temperature or time. A typical DTA curve easily shows both Tg and T . 

Nucleation from the melt has been studied for palm oil, composed of triglycerides of palmitic and oleic acids, and exhibiting at least three polymorphs (van Putte and Bakker 1987). Nucleation curves (induction time x vs temperature T) of palm oil and palm stearin show discontinuities at 297 and 306 °C respectively, indicating the onset of nucleation, and the demarcation of the occurrence of the polymorphs, as confirmed by isothermal Differential Scanning Calorimetry (DSC) studies (Ng I990a,b). 

The relationship between observed enthalpy-volume relaxations and thermal treatment of slightly oriented industrial PVC films was investigated. Differential scanning calorimetry at 20 -C per minute and specific volume analysis (density gradient column) were used to study the effects of annealing near and below Tg. Nonlinear effects in the volume relaxation at relatively long times and temperatures close to the glass transition produce deviations in the specific heat curves at temperatures far above Tg in addition to the normal overshoot effects. 

Isothermal exotherms were obtained in isothermal calorimetry at 160, 165, and 170°C, successively. The increase in heat follows the first-order law with respect to time because plots of log (heat rate) against log q -, ) are linear for the three temperatures, with a slope equal to 1 the temperature coefficients k were determined by measuring the ordinate intercept in these curves at the three temperatures. The energy of activation E was found from the slope of log k versus 1/T plots. The value... 

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