Isothermal differential calorimetry techniques

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). 

Several authors have addressed crystallization measurements and kinetics of SPS [23-26,78-82]. The experiments were carried out in both isothermal and non-isothermal mode by means of differential calorimetry techniques (DSC) [24-26,78-82]. 

If the van t Hoff and isosteric methods are simple ways for estimating the adsorption enthalpy of single component from isothermal adsorption data, they have the disadvantage to not take into account the temperature dependence on the enthalpy and entropy and to be not enough accurate. Moreover they are not adapted to the adsorption of gas mixtures. The best mean to determine the adsorption and coadsorption enthalpy is to measure them by using a differential calorimetry technique coupled with others techniques allowing the measure of adsorbed amount and composition as for example the manometry and the chromatography. 

The total acidity deterioration and the acidity strength distribution of a catalyst prepared from a H-ZSM-5 zeolite has been studied in the MTG process carried out in catalytic chamber and in an isothermal fixed bed integral reactor. The acidity deterioration has been related to coke deposition. The evolution of the acidic structure and of coke deposition has been analysed in situ, by diffuse reflectance FTIR in a catalytic chamber. The effect of operating conditions (time on stream and temperature) on acidity deterioration, coke deposition and coke nature has been studied from experiments in a fixed integral reactor. The technique for studying acidity yields a reproducible measurement of total acidity and acidity strength distribution of the catalyst deactivated by coke. The NH3 adsorption-desorption is measured by combination of scanning differential calorimetry and the FTIR analysis of the products desorbed. 

Differential scanning calorimetry (DSC) is a sensitive method which has enabled changes in biological systems to be examined providing medical researchers with distinct opportunities. Other thermoanalytical techniques such as thermogravimetry (TG) and isothermal titration calorimetry (ITC) are useful in the evaluation of thermal stability and to measure the heat generated in physical and chemical reactions. 

J.W. Beckmann, J.S. Wilkes, R.R. McGuire, "2,4,6—Trinitrotoluene Thermal Decomposition Kinetic Parameters Determined by the Isothermal Differential Scanning Calorimetry Technique", Thermochim. Acta. 19. 111—118 (1977). 

Differential Scanning Calorimetry (DSC) and Isothermal Titration Calorimetry (ITC) have become standard techniques in the field of thermodynamic investigation of natural membranes and model membrane systems. Due to the new developments of more sensitive DSC instruments, studies of lipid-protein systems liave become feasible, which could previously not be perfonued because of the limitations on amount of material. It is to be expected that DSC methods will again make a large progress because of these improvements in sensitivity. 

The techniques referred to above (Sects. 1—3) may be operated for a sample heated in a constant temperature environment or under conditions of programmed temperature change. Very similar equipment can often be used differences normally reside in the temperature control of the reactant cell. Non-isothermal measurements of mass loss are termed thermogravimetry (TG), absorption or evolution of heat is differential scanning calorimetry (DSC), and measurement of the temperature difference between the sample and an inert reference substance is termed differential thermal analysis (DTA). These techniques can be used singly [33,76,174] or in combination and may include provision for EGA. Applications of non-isothermal measurements have ranged from the rapid qualitative estimation of reaction temperature to the quantitative determination of kinetic parameters [175—177]. The evaluation of kinetic parameters from non-isothermal data is dealt with in detail in Chap. 3.6. 

Thermoanalytical techniques such as differential scanning calorimetry (DSC) and thermogravi-metric analysis (TGA) have also been widely used to study rubber oxidation [24—27]. The oxidative stability of mbbers and the effectiveness of various antioxidants can be evaluated with DSC based on the heat change (oxidation exotherm) during oxidation, the activation energy of oxidation, the isothermal induction time, the onset temperamre of oxidation, and the oxidation peak temperature. 

FIGURE 13.5 Calorimetric and volumetric data obtained from adsorption calorimetry measurements Raw pressure and heat flow data obtained for each dose of probe molecule and Thermokinetic parameter (a), Volumetric isotherms (b), Calorimetric isotherms (c), Integral heats (d), Differential heats (e), Site Energy Distribution Spectrum (f). (From Damjanovic, Lj. and Auroux, A., Handbook of Thermal Analysis and Calorimetry, Further Advances, Techniques and Applications, Elsevier, Amsterdam, 387-438, 2007. With permission.)... 

The temperature of maximum transformation rate is easily determined using either of two similar techniques called differential scanning calorimetry (DSC) or differential thermal analysis (DTA). These techniques are extremely useful in the kinetic study of both isothermal and nonisothermal phase transformations. 

Differential Scanning Calorimetry (DSC) This is by far the widest utilized technique to obtain the degree and reaction rate of cure as well as the specific heat of thermosetting resins. It is based on the measurement of the differential voltage (converted into heat flow) necessary to obtain the thermal equilibrium between a sample (resin) and an inert reference, both placed into a calorimeter [143,144], As a result, a thermogram, as shown in Figure 2.7, is obtained [145]. In this curve, the area under the whole curve represents the total heat of reaction, AHR, and the shadowed area represents the enthalpy at a specific time. From Equations 2.5 and 2.6, the degree and rate of cure can be calculated. The DSC can operate under isothermal or non-isothermal conditions [146]. In the former mode, two different methods can be used [1] ... 

Temperature-rising elution fractionation (tref) is a technique for obtaining fractions based on short-chain branch content versus molecular weight (96). On account of the more than four days of sample preparation required, stepwise isothermal segregation (97) and solvated thermal analysis fractionation (98) techniques using variations of differential scanning calorimetry (dsc) techniques have been developed. 

Thermal techniques such as isothermal calorimetry (ITC) and differential scanning calorimetry (DSC) have been used in formulation screens to predict the formulation with the greatest stability based on the assumption that excipients that increase the of the protein will stabilize the molecule at the recommended storage temperature. For example, a screen of preservatives performed during formulation development for interleukin-1 receptor found that the for the formulation... 

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