Calorimeter microcalorimeter

Recent developments m calorimetry have focused primarily on the calorimetry of biochemical systems, with the study of complex systems such as micelles, protems and lipids using microcalorimeters. Over the last 20 years microcalorimeters of various types including flow, titration, dilution, perfiision calorimeters and calorimeters used for the study of the dissolution of gases, liquids and solids have been developed. A more recent development is pressure-controlled scamiing calorimetry [26] where the thennal effects resulting from varying the pressure on a system either step-wise or continuously is studied. 

A survey of the literature shows that although very different calorimeters or microcalorimeters have been used for measuring heats of adsorption, most of them were of the adiabatic type, only a few were isothermal, and until recently (14, 15), none were typical heat-flow calorimeters. This results probably from the fact that heat-flow calorimetry was developed more recently than isothermal or adiabatic calorimetry (16, 17). We believe, however, from our experience, that heat-flow calorimeters present, for the measurement of heats of adsorption, qualities and advantages which are not met by other calorimeters. Without entering, at this point, upon a discussion of the respective merits of different adsorption calorimeters, let us indicate briefly that heat-flow calorimeters are particularly adapted to the investigation (1) of slow adsorption or reaction processes, (2) at moderate or high temperatures, and (3) on solids which present a poor thermal diffusivity. Heat-flow calorimetry appears thus to allow the study of adsorption or reaction processes which cannot be studied conveniently with the usual adiabatic or pseudoadiabatic, adsorption calorimeters. In this respect, heat-flow calorimetry should be considered, actually, as a new tool in adsorption and heterogeneous catalysis research. 

Since heat exchange between the calorimeter vessel and the heat sink is not hindered in a heat-flow calorimeter, the temperature changes produced by the thermal phenomenon under investigation are usually very small (less than 10 4 degree in a Calvet microcalorimeter, for instance) (23). For most practical purposes, measurements in a heat-flow calorimeter may be considered as performed under isothermal conditions. 

The Calvet microcalorimeter (16) is an improved version of the first heat-flow calorimeter described by Tian in 1924 (25). In this micro-... 

Calvet and Persoz (29) have discussed at length the question of the sensitivity of the Calvet calorimeter in terms of the number of thermocouples used, the cross section and the length of the wires, and the thermoelectric power of the couples. On the basis of this analysis, the micro-calorimetric elements are designed to operate near maximum sensitivity. The present-day version of a Tian-Calvet microcalorimetric element, which has been presented in Fig. 2, contains approximately 500 chromel-to-constantan thermocouples. The microcalorimeter, now commercially available, in which two of these elements are placed (Fig. 3) may be used from room temperature up to 200°C. 

In this microcalorimeter, the heat sink is not a massive metal block but is divided into several parts which are mobile with respect to each other. Each thermoelectric element (E) and a cell guide (D) are affixed to a fluxmeter holder (C). The holder (C) is mobile with respect to a massive arm (B) which, in turn, rotates around a vertical axle (A). All parts of the heat sink are made of brass. Surfaces in contact are lubricated by silicone grease. Four thermoelectric elements (E) are mounted in this fashion. They enclose two parallelepipedic calorimetric cells, which can be made of glass (cells for the spectrography of liquids are particularly convenient) or of metal (in this case, the electrical insulation is provided by a very thin sheet of mica). The thermoelectric elements surrounding both cells are connected differentially, the Petit microcalorimeter being thus a twin differential calorimeter. 

It is clear that in this microcalorimeter, only a fraction of the outside wrall of the inner vessel is covered by thermoelectric elements. Consequently, only a part of the total heat flux emitted by the cell is detected. This may be the cause of a systematic error which, however, can be avoided if the heat transfer via the thermoelectric elements constitutes a constant fraction of the total, irrespective of the process taking place in the calorimeter cell. The present version of the Petit microcalorimeter can be used only at moderate temperatures (<100°C), mainly because some components of the thermoelectric elements wrould be damaged at higher temperatures. 

The intrinsic sensitivity of a heat-flow calorimeter is defined as the value of the steady emf that is produced by the thermoelectric elements when a unit of thermal power is dissipated continuously in the active cell of the calorimeter 38). In the case of microcalorimeters, it is conveniently expressed in microvolts per milliwatt (juV/mW). This ratio, which is characteristic of the calorimeter itself, is particularly useful for comparison purposes. Typical values for the intrinsic sensitivity of the microcalorimeters that have been described in this section are collected in Table I, together with the temperature ranges in which these instruments may be utilized. The intrinsic sensitivity has, however, very little practical importance, since it yields no indication of the maximum amplification that may be applied to the emf generated by the thermoelements without developing excessive noise in the indicating device. 

The value of the time constant depends upon the calorimeter itself p and upon the heat capacity of the calorimeter cell and of its contents p. Typical, but necessarily approximate, values of the time constant for some heat-flow microcalorimeters are given in Table II. 

It must be noted that the heat capacity of the calorimeter cell and of its contents p, which appears in the second term of Tian s equation [Eq. (12)], disappears from the final expression giving the total heat [Eq. (19)]. This simply means that all the heat produced in the calorimeter cell must eventually be evacuated to the heat sink, whatever the heat capacity of the inner cell may be. Changes of the heat capacity of the inner cell or of its contents influence the shape of the thermogram but not the area limited by the thermogram. It is for this reason that heat-flow microcalorimeters, with a high sensitivity, are particularly convenient for investigating adsorption processes at the surface of poor heat-conducting solids similar in this respect to most industrial catalysts. 

The basic principle of heat-flow calorimetry is certainly to be found in the linear equations of Onsager which relate the temperature or potential gradients across the thermoelements to the resulting flux of heat or electricity (16). Experimental verifications have been made (89-41) and they have shown that the Calvet microcalorimeter, for instance, behaves, within 0.2%, as a linear system at 25°C (41)-A. heat-flow calorimeter may be therefore considered as a transducer which produces the linear transformation of any function of time f(t), the input, i.e., the thermal phenomenon under investigation]] into another function of time ig(t), the response, i.e., the thermogram]. The problem is evidently to define the corresponding linear operator. 

The determination of these curves requires not only the measurement of small amounts of heat in a microcalorimeter, but also the simultaneous determination of the corresponding quantity of adsorbed gas. Volumetric measurements are to be preferred to gravimetric measurements for these determinations because it would be very difficult indeed to ensure a good, and reproducible, thermal contact between a sample of adsorbent, hanging from a balance beam, and the inner cell of a heat-flow calorimeter. 

Figure 15 gives a diagrammatic representation of a volumetric line which is used in connection with a high-temperature Calvet microcalorimeter 67). Other volumetric lines which have been described present the same general features (15, 68). In the case of corrosive gases or vapors, metallic systems may be used 69). In all cases, a sampling system (A in Fig. 15) permits the introduction of a small quantity of gas (or vapor) in a calibrated part of the volumetric line (between stopcocks Ri and Ro in Fig. 15) where its pressure Pi is measured (by means of the McLeod gage B in Fig. 15). The gas is then allowed to contact the adsorbent placed in the calorimeter cell C (by opening stopcock Ro in Fig. 15). The heat evolution is recorded and when it has come to completion, the final equi-...

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). 

Calvet microcalorimeters are particularly convenient for such studies. Figure 19 show s, for instance, the evolution of the differential heat of adsorption of oxygen, measured at 30°C with a Calvet calorimeter, as a function of the total amount of oxygen adsorbed on the surface of a sample (100 mg) of nickel oxide, NiO(200) (19, 73). The volume of the first... 

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)-... 

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... 

Other instruments include the Calvet microcalorimeters [113], some of which can also run in the scanning mode as a DSC. These are available commercially from SETARAM. The calorimeters exist in several configurations. Each consists of sample and reference vessels placed in an isothermally controlled and insulated block. The side walls are in intimate contact with heat-flow sensors. Typical volumes of sample/reference vessels are 0.1 to 100 cm3, The instruments can be operated from below ambient temperatures up to 300°C (some high temperature instruments can operate up to 1000°C). The sensitivity of these instruments is better than 1 pW, which translates to a detection limit of 1 x 10-3 W/kg with a sample mass of 1 g. 

Very high sensitivity and the concomitant use of minute samples justify the descriptor microcalorimeter for many heat flow instruments. In general, a calorimeter can be labeled a microcalorimeter when its sensitivity is better than 10 (xW. Note, however, that some authors adopt a tighter definition, indicating 1 (x W as the sensitivity upper limit [160], The cell volume is usually in the range of 0.5-25 cm3. 

All modern heat flow calorimeters have twin cells thus, they operate in the differential mode. As mentioned earlier, this means that the thermopiles from the sample and the reference cell are connected in opposition, so that the measured output is the difference between the respective thermoelectric forces. Because the differential voltage is the only quantity to be measured, the auxiliary electronics of a heat flux instrument are fairly simple, as shown in the block diagram of figure 9.3. The main device is a nanovoltmeter interfaced to a computer for instrument control and data acquisition and handling. The remaining electronics of a microcalorimeter (not shown in figure 9.3) are related to the very accurate temperature control of the thermostat and, in some cases, with the... 

Calorimeters, see Microcalorimeters Calorimetry, surface acidity, 27 121 Calvet microcalorimeter, 22 197-201, 38 172-... 

Microcalorimetry has gained importance as one of the most reliable method for the study of gas-solid interactions due to the development of commercial instrumentation able to measure small heat quantities and also the adsorbed amounts. There are basically three types of calorimeters sensitive enough (i.e., microcalorimeters) to measure differential heats of adsorption of simple gas molecules on powdered solids isoperibol calorimeters [131,132], constant temperature calorimeters [133], and heat-flow calorimeters [134,135]. During the early days of adsorption calorimetry, the most widely used calorimeters were of the isoperibol type [136-138] and their use in heterogeneous catalysis has been discussed in [134]. Many of these calorimeters consist of an inner vessel that is imperfectly insulated from its surroundings, the latter usually maintained at a constant temperature. These calorimeters usually do not have high resolution or accuracy. 

An apparatus with high sensitivity is the heat-flow microcalorimeter originally developed by Calvet and Prat [139] based on the design of Tian [140]. Several Tian-Calvet type microcalorimeters have been designed [141-144]. In the Calvet microcalorimeter, heat flow is measured between the system and the heat block itself. The principles and theory of heat-flow microcalorimetry, the analysis of calorimetric data, as well as the merits and limitations of the various applications of adsorption calorimetry to the study of heterogeneous catalysis have been discussed in several reviews [61,118,134,135,141,145]. The Tian-Calvet type calorimeters are preferred because they have been shown to be reliable, can be used with a wide variety of solids, can follow both slow and fast processes, and can be operated over a reasonably broad temperature range [118,135]. The apparatus is composed by an experimental vessel, where the system is located, which is contained into a calorimetric block (Figure 13.3 [146]). 

The duration of each dosing experiment is about 15-50 minutes (depending on the sample and of the time constant of the calorimeter), which was long enough to yield well-resolved heat-flow peaks and a stable horizontal baseline of the microcalorimeter. For all catalysts presented here, adsorption always reached thermodynamic equilibrium. Prior to adsorption measurements, the samples were pretreated in the calorimetric cell by heating overnight under vacuum. 

For reliable measurements of heats of immersion with simple calorimeters, the surface area of the powder should be at least 5 sq. m./g. and might need to be larger depending on its density, bulk density, and polarity. With modern microcalorimeters, on the other hand, the surface area of the solid need be only a fraction of a square meter per gram. 

Twin differential microcalorimeters have been described by Berghausen el al. (S), by Hackerman (8), and by Whalen and Johnson (9). Hacker-man employs thermistors, whereas the other two are based on thermocouples and in addition are run adiabatically. These calorimeters appear to have about 10 times the sensitivity of simpler designs, but for many purposes the large additional diflSculties in design, construction, and operation do not seem to be warranted. Berghausen and coworkers, however, have shown that they can estimate slow heat evolutions, after the first few minutes, due to surface reactions. 

Standard heat capacities of transfer can be derived from the temperature dependence of standard enthalpies of solution (8). While this technique can give general trends in the transfer functions from water to mixed solvents (9), it is not always sufficiently precise to detect the differences between similar cosolvents, and the technique is rather laborious. Direct measurements of the difference between heat capacities per unit volume of a solution and of the solvent a — gq can be obtained with a flow microcalorimeter (10) to 7 X 10 5 JK 1 cm-3 on samples of the order of 10 cm3. A commercial version of this instrument (Picker dynamic flow calorimeter, Techneurop Inc.) has a sensitivity improved by a factor oi about two. 

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