Isoperibolic

A liquid serves as the calorimetric medium in which the reaction vessel is placed and facilitates the transfer of energy from the reaction. The liquid is part of the calorimeter (vessel) proper. The vessel may be isolated from the jacket (isoperibole or adiabatic), or may be in good themial contact (lieat-flow type) depending upon the principle of operation used in the calorimeter design. 

Figure Bl.27.4. Rotating bomb isoperibole calorimeter. A, stainless steel bomb, platinum lined B, heater C, thermostat can D, thennostat iimer wall E, themiostat water G, sleeve for temperature sensor H, motor for bomb rotation J, motor for calorimeter stirrer K, coimection to cooling or heating unit for thennostat L, circulation pump.

Albert H J and Archer D G 1994 Mass-flow isoperibole calorimeters Solution Calorimetry, Experimental Thermodynamics vol IV, ed K N Marsh and PAG O Hare (Oxford Blackwell)... 

Ways are discussed of measuring both compositions and heats of formation fi.e.. excess enthalpies) of two conjugate phases in model amphiphile/water systems by isoperibol titration calorimetry. Calorimetric and phase-volume data are presented for n-C H OH/water at 30... 

This paper considers systems of lesser dimensionality than the previous study, namely, systems of two compounds, which (ignoring the vapor) can form only one or two phases. Specifically, excess enthalpies and phase compositions have been measured (at ambient pressure) by isoperibol calorimetry for n-butanol/water at 30.0 and 55.0 °C and for n-butoxyethanol/water at 55.0 and 65.0 °C. (Butanol, or C4E0, is C HgOH butoxyethanol, or C4E1, is C HgCX OH.) The miscibility... 

In Figure 4 the results from the three different groups are in excellent agreement for butanol concentrations of 90 wt% and greater, although the data from the Russian group scatter somewhat more around our results than do the values interpolated from Westmeier s data.(14.16). At lower amphiphile concentrations the isoperibolic calorimeter measurements are in noticeably better agreement with the data of ref. 16 than with the Russian work (14-16). However, almost all results fall within the 95% confidence interval (dashed lines) for our results. 

Isoperibolic calorimetry measurements on the n-butanol/water and n-butoxyethanol/water systems have demonstrated the accuracy and convenience of this technique for measuring consolute phase compositions in amphiphile/water systems. Additional advantages of calorimetry over conventional phase diagram methods are that (1) calorimetry yields other useful thermodynamic parameters, such as excess enthalpies (2) calorimetry can be used for dark and opaque samples and (3) calorimetry does not depend on the bulk separation of conjugate fluids. Together, the present study and studies in the literature encompass all of the classes of compounds of the amphiphile/CO ydrocarbon/water systems that are encountered in... 

It appears therefore that during the operation of all usual calorimeters, temperature gradients are developed between the inner vessel and its surroundings. The resulting thermal head must be associated, in all cases, to heat flows. In isoperibol calorimeters, heat flows (called thermal leaks in this case) are minimized. Conversely, they must be facilitated in isothermal calorimeters. All heat-measuring devices could therefore be named heat-flow calorimeters. However, it must be noted that in isoperibol or isothermal calorimeters, the consequences of the heat flow are more easily determined than the heat flow itself. The temperature decrease... 

It is true, however, that many catalytic reactions cannot be studied conveniently, under given conditions, with usual adsorption calorimeters of the isoperibol type, either because the catalyst is a poor heat-conducting material or because the reaction rate is too low. The use of heat-flow calorimeters, as has been shown in the previous sections of this article, does not present such limitations, and for this reason, these calorimeters are particularly suitable not only for the study of adsorption processes but also for more complete investigations of reaction mechanisms at the surface of oxides or oxide-supported metals. The aim of this section is therefore to present a comprehensive picture of the possibilities and limitations of heat-flow calorimetry in heterogeneous catalysis. The use of Calvet microcalorimeters in the study of a particular system (the oxidation of carbon monoxide at the surface of divided nickel oxides) has moreover been reviewed in a recent article of this series (19). 

It is, of course, not necessary to use a heat-flow microcalorimeter in order to determine the heat released by rapid adsorption phenomena. Dell and Stone (74), for instance, using an isoperibol calorimeter of the Garner-Veal type, found an initial heat of 54 4 kcal mole-1 for the adsorption of oxygen on nickel oxide at 20°C. The agreement with the value (60 2 kcal mole-1) in Fig. 19 is remarkably good, particularly if it is considered that very different methods were used for the preparation of the nickel-oxide samples (19, 74)-... 

The measurement of an enthalpy change is based either on the law of conservation of energy or on the Newton and Stefan-Boltzmann laws for the rate of heat transfer. In the latter case, the heat flow between a sample and a heat sink maintained at isothermal conditions is measured. Most of these isoperibol heat flux calorimeters are of the twin type with two sample chambers, each surrounded by a thermopile linking it to a constant temperature metal block or another type of heat reservoir. A reaction is initiated in one sample chamber after obtaining a stable stationary state defining the baseline from the thermopiles. The other sample chamber acts as a reference. As the reaction proceeds, the thermopile measures the temperature difference between the sample chamber and the reference cell. The rate of heat flow between the calorimeter and its surroundings is proportional to the temperature difference between the sample and the heat sink and the total heat effect is proportional to the integrated area under the calorimetric peak. A calibration is thus... 

Adiabatic calorimetry uses the temperature change as the measurand at nearly adiabatic conditions. When a reaction occurs in the sample chamber, or energy is supplied electrically to the sample (i.e. in heat capacity calorimetry), the temperature rise of the sample chamber is balanced by an identical temperature rise of the adiabatic shield. The heat capacity or enthalpy of a reaction can be determined directly without calibration, but corrections for heat exchange between the calorimeter and the surroundings must be applied. For a large number of isoperibol... 

The solution experiments may be made in aqueous media at around ambient temperatures, or in metallic or inorganic melts at high temperatures. Two main types of ambient temperature solution calorimeter are used adiabatic and isoperibol. While the adiabatic ones tend to be more accurate, they are quite complex instruments. Thus most solution calorimeters are of the isoperibol type [33]. The choice of solvent is obviously crucial and aqueous hydrofluoric acid or mixtures of HF and HC1 are often-used solvents in materials applications. Very precise enthalpies of solution, with uncertainties approaching 0.1% are obtained. The effect of dilution and of changes in solvent composition must be considered. Whereas low temperature solution calorimetry is well suited for hydrous phases, its ability to handle refractory oxides like A1203 and MgO is limited. 

Some types of isoperibolic (quasi-isothermal) equipment using relatively large quantities of sample—see Section 2.3.I.2. 

Other types of equipment available to investigate the gas evolution are various autoclave tests (Section 2.3.3.2), isoperibolic autoclave tests (Section 2.3.1.2), and closed Dewar tests (Section 2.3.2.2). Mass flux data are also required in designing any vent facilities (Chapter 3). 

Constant jacket temperature measuring techniques, known as isoperibolic calorimetry, are designed to investigate the thermal behavior of substances and reaction mixtures under processing conditions [89,102-108]. 

Isoperibolic equipment consists of a sample container that is placed in a circulating air oven or heater. Typically, the sample container, of which there are several types, consists of a small tube or beaker that can contain a 5 to 30 g sample. The temperature range of commercial instruments is about 0 to 300°C. Some instruments include small autoclaves or small stirred vessels. Open vessels are made of glass while autoclaves are constructed of stainless... 

In an isoperibolic experiment, the jacket temperature of the sample container (or the surroundings of the container, i.e., the oven temperature) is held constant. On attaining a steady-state, a temperature difference between the sample and jacket may be obtained, which becomes (1) zero (within the detection limit of the equipment) if no energy is released from the sample, or (2) positive if energy is released due to chemical reaction or decomposition. If no temperature difference is recorded after a fixed time interval, the oven temperature is increased (typically 5°C) and held constant once again. This procedure is repeated until an exothermic event is observed. 

For the identification of the onset temperature of the exotherm, the steady-state temperature difference may be plotted against the sample temperature. After calibration, the evolved heat can be estimated. A typical plot of an isoperibolic measurement is illustrated in Figure 2.16. The sample is heated by step-wise adjustment of the jacket (or oven) temperature. The actual sample temperature results from the heat accumulation as net difference between the heat generated by the chemical reaction and the heat transferred to the jacket (or oven). The resulting mean temperature difference is relatively small and not easy to detect accurately. Thus, a range of step changes in temperature is used to define a curve, which enables a more accurate determination of the start of the exothermic event and of To to be made. 

Because of the medium or relatively large sample quantities used and the instrumental sensitivity, isoperibolic calorimetry is a useful tool in determining the onset temperature of an exotherm. In fact, in its simplest construction, this is really the only measurement. Digital data acquisition does allow computer analysis of the peak or area under the curve, which indicates the order of magnitude of the exotherm. Generally, the detected onset temperatures are similar to those found in the ARC (see later in Section 2.3.23) and are significantly lower than in the DSC (Section 2.3.1.1) [79]. 

Isoperibolic instruments have been developed to estimate enthalpies of reaction and to obtain kinetic data for decomposition by using an isothermal, scanning, or quasi-adiabatic mode with compensation for thermal inertia of the sample vessel. The principles of these measuring techniques are discussed in other sections. 

The equipment is quite adequate for screening purposes. In its simplest form (i.e., a glass tube in an oven), it is a relatively low cost technique that can be assembled with standard laboratory equipment. However, the simple test set-up provides no quantitative thermal data for scale-up purposes, but only T0 values. The more advanced instruments like the SEDEX and SIKAREX, which are also isoperibolic calorimetry equipment, acquire specific thermal stability data that can be used for scale-up. Furthermore, the small autoclave tests provide gas evolution data. 

Because of the operating principles of the equipment, especially in the isoperibolic mode, complex calculation and calibration procedures are required for the determination of quantitative kinetic parameters and the energy release during decomposition. Also, for a reaction with a heterogeneous mixture such as a two-phase system, there may be mass transfer limitations which could lead to an incorrect T0 determination. 

The RC1 reactor system temperature control can be operated in three different modes isothermal (temperature of the reactor contents is constant), isoperibolic (temperature of the jacket is constant), or adiabatic (reactor contents temperature equals the jacket temperature). Critical operational parameters can then be evaluated under conditions comparable to those used in practice on a large scale, and relationships can be made relative to enthalpies of reaction, reaction rate constants, product purity, and physical properties. Such information is meaningful provided effective heat transfer exists. The heat generation rate, qr, resulting from the chemical reactions and/or physical characteristic changes of the reactor contents, is obtained from the transferred and accumulated heats as represented by Equation (3-17) ... 

Isoperibolic system a system in which the controlling external temperature is kept constant. 

Methods. The equipment used consists of a TRONAC Model 450 (TRONAC, Inc., Orem, Utah) isoperibol titration calorimeter which... 

The calorimetry lexicon also includes other frequently used designations of calorimeters. When the calorimeter proper contains a stirred liquid, the calorimeter is called stirred-liquid. When the calorimeter proper is a solid block (usually made of metal, such as copper), the calorimeter is said to be aneroid. For example, both instruments represented in figure 6.1 are stirred-liquid isoperibol calorimeters. The term scanning calorimeter is used to designate an instrument where the temperatures of the calorimeter proper and/or the jacket vary at a programmed rate. 

Figure 6.2 Schematic representation of (a) an adiabatic calorimeter, (b) an isoperibol calorimeter, and (c) a heat conduction (or heat flow) calorimeter. fc and 7] are the temperatures of the calorimeter proper and the external jacket, respectively, and is the heat flow rate between the calorimeter proper and the external jacket.

Most static-bomb calorimeters used are of the isoperibol type, such as the one in figure 7.1. Here, the bomb A is a pressure vessel of 300 cm3 internal volume. Combustion bombs are usually made of stainless steel and frequently have an internal platinum lining to prevent corrosion. In a typical high-precision experiment, the platinum ignition wire B connects the two electrodes C, which are affixed to the bomb head. A cotton thread fuse D (other materials such as polyethene are also used), of known energy of combustion, is weighed to a precision of 10-5 — 10-6 g and tied to the platinum wire. A pellet E of the compound... 

Figure 7.1 Scheme of a macro static-bomb isoperibol combustion calorimeter (see text). 

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