Calorimetric techniques

The partial molar entropy of a component may be measured from the temperature dependence of the activity at constant composition the partial molar enthalpy is then determined as a difference between the partial molar Gibbs free energy and the product of temperature and partial molar entropy. As a consequence, entropy and enthalpy data derived from equilibrium measurements generally have much larger errors than do the data for the free energy. Calorimetric techniques should be used whenever possible to measure the enthalpy of solution. Such techniques are relatively easy for liquid metallic solutions, but decidedly difficult for solid solutions. The most accurate data on solid metallic solutions have been obtained by the indirect method of measuring the heats of dissolution of both the alloy and the mechanical mixture of the components into a liquid metal solvent.05... 

Finally, a number of solution calorimetric techniques can be used to measure Af//°v For example, q for the solution of a metal in acid can be measured. Additional thermochemical results are then used to complete a cycle that yields AfH°m for the metallic salt. The process adds ArH° for the following reactions ... 

Drago and coworkers have also calculated the enthalpy values for the formation of many complexes or hydrogen bonds by NMR and calorimetric techniques. For example, in a series of phenols or t-BuOH, they observed the IR frequency shifts (Avqh) of the hydroxyl compounds and found that a linear relationship exists between bases and individual acids. In Table 7 shows some AH values calculated by equation 2, and Avqh values of t-BuOH" " while in Table 8 frequency data Avq of various substituted phenols and the AH values are given. 

Tuulmets [Kinetics and Catalysis, 5 (59), 1964] has studied the kinetics of the reaction of ethyl magnesium bromide with pinacolin. He used a calorimetric technique to monitor the progress of the reaction. The overall temperature increase of the reaction mixture was less than a degree. Mixture temperatures were determined with a sensitive potentiometer. The data below... 

In the various sections of this article, it has been attempted to show that heat-flow calorimetry does not present some of the theoretical or practical limitations which restrain the use of other calorimetric techniques in adsorption or heterogeneous catalysis studies. Provided that some relatively simple calibration tests and preliminary experiments, which have been described, are carefully made, the heat evolved during fast or slow adsorptions or surface interactions may be measured with precision in heat-flow calorimeters which are, moreover, particularly suitable for investigating surface phenomena on solids with a poor heat conductivity, as most industrial catalysts indeed are. The excellent stability of the zero reading, the high sensitivity level, and the remarkable fidelity which characterize many heat-flow microcalorimeters, and especially the Calvet microcalorimeters, permit, in most cases, the correct determination of the Q-0 curve—the energy spectrum of the adsorbent surface with respect to... 

An overview of typical calorimetric techniques indicating sensitivities, principal application areas, and the usual data acquired is shown on Table 2.1. A brief summary of advantages and disadvantages of the various tests is also given. The column "principal applications" indicates only the major applications of the respective techniques. In any of the tests listed, it is possible to obtain additional data or to use the test equipment for completely different hazard evaluations once the techniques are fully understood and the tests are run by fully qualified technical personnel. Testing techniques are discussed later in Section 2.3 on Practical Testing. 

Comparison of To and AHd for TBPB Using Different Calorimetric Techniques... 

As discussed in Section 2.3.1.2, SEDEX [103,104] and SIKAREX [106] types of apparatus are also used in adiabatic calorimetric techniques. Compensation for the heat capacity of the sample containment is also a feature. Typical sensitivity of this type of equipment is 0.5 W/kg, the sample size is 10 to 30g, and the temperature range is 0 to 300°C. 

The two sets of measurements of vE agree reasonably well with each other (cf. Fig. 3 of Ref. 25). The excess enthalpy has also been measured by Pool and Staveley26 by a calorimetric technique which seems somewhat less advanced than the one used by Lambert and Simon. Their results are in moderate agreement with (67). 

While awaiting the development of precise combustion calorimetric techniques on a micro scale, much of the thermochemical information obtained during the past... 

This is the third report on attempts to measure the propagation rate constant, kp+, for the cationic polymerisation of various monomers in nitrobenzene by reaction calorimetry. The first two were concerned with acenaphthylene (ACN) [1, 2] and styrene [2]. The present work is concerned with attempts to extend the method to more rapidly polymerising monomers. With these we were working at the limits of the calorimetric technique [3] and therefore consistent kinetic results could be obtained only for indene and for phenyl vinyl ether (PhViE), the slowest of the vinyl ethers 2-chloroethyl vinyl ether (CEViE) proved to be so reactive that only a rough estimate of kp+ could be obtained. Most of our results were obtained with 4-chlorobenzoyl hexafluoroantimonate (1), and some with tris-(4-chlorophenyl)methyl hexafluorophosphate (2). A general discussion of the significance of all the kp values obtained in this work is presented. 

The kinetics of the polymerising system styrene-perchloric acid-methylene dichloride have been studied in the temperature range +19 °C to -19 °C, by a calorimetric technique. The propagation is pseudocationic, its rate constant at 19 °C is kp = 10.6 1 mole 1 s 1, and Ep = 11.6 kcal mole1. The elementary reactions are interpreted in detail by a mechanism involving an ester as chain carrier. 

There are a number of different types of adiabatic calorimeters. Dewar calorimetry is one of the simplest calorimetric techniques. Although simple, it produces accurate data on the rate and quantity of heat evolved in an essentially adiabatic process. Dewar calorimeters use a vacuum-jacketed vessel. The apparatus is readily adaptable to simulate plant configurations. They are useful for investigating isothermal semi-batch and batch reactions, and they can be used to study ... 

Low cost is one of the main advantages of the vapor pressure methods, as compared with calorimetric techniques. An apparatus to measure the vapor pressures of low boiling temperature liquids can be built easily in an undergraduate chemistry laboratory. However, the same is not quite true if we want to measure the vapor pressures of low-volatility substances, such as most solids. In these cases, Knudsen cells are usually the method of choice, but they require more expensive high-vacuum equipment [36]. 

The classical calorimetric methods addressed in chapters 7-9, 11, and 12 were designed to study thermally activated processes involving long-lived species. As discussed in chapter 10, some of those calorimeters were modified to allow the thermochemical study of radiation-activated reactions. However, these photocalorimeters are not suitable when reactants or products are shortlived molecules, such as most free radicals. To study the thermochemistry of those species, the technique of photoacoustic calorimetry was developed (see chapter 13). It may be labeled as a nonclassical calorimetric technique because it relies on concepts that do not fit into the classification schemes just outlined. 

The greatest advantage of the drop calorimetric technique developed by the Manchester group is that it requires very little sample. Typically, less than 2 mg... 

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... 

The enthalpies of ionization corresponding to Eqs. (4), (3"), and (11) can be determined by means of the temperature effect on the respective standard free energy changes (70MI3) or by calorimetric techniques. 

Another calorimetric technique for measuring the heat of adsorption consists of comparing the heat of immersion (see Chapter 6, Section 6.6c) of bare solid with that of a solid preequilibrated with vapor to some level of coverage. Table 9.4 summarizes some results of this sort. The experiment consisted of measuring the heats of immersion of anatase (Ti02) in benzene with the indicated amount of water vapor preadsorbed on the solid. Small quantities of adsorbed water increase the heat of immersion more than threefold so that it approaches the value for water itself. Most laboratory samples will be contaminated with adsorbed water. 

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