Peltier calorimeters

Fig. 8.1 Standard set-up of a reaction calorimeter [4]. Left side heat-flow, heat-balance and power-compensation calorimeters. Right side Peltier calorimeters.

Fig. 8.2 Main heat-flow rates that have to be considered in heat-flow, heat-balance and power-compensation reaction calorimeters running under strictly isothermal conditions [4]. The heat-flow rates inside a Peltier calorimeter are analogous (compare with Fig. 8.1). The direction of the heat-flow arrows corresponds to a positive heat-flow rate. For explanation of the different heat-flow rates, see the text.

When a Joule heating or a Peltier cooling are used to compensate part of the heat absorbed or liberated in the calorimeter cell, Eq. (17) gives... 

The efficiency of this method has been demonstrated for several types of heat-flow calorimeters. The rather long time constant of a Calvet-type calorimeter (200 sec), for instance, is decreased to 10 sec, when exact Peltier cooling is used (61). Similarly, the time constant of calorimeters... 

The first heat flow calorimeter based on Seebeck, Peltier, and Joule effects was built by Tian at Marseille, France, and reported in 1923 [156-158]. The set-up included two thermopiles, one to detect the temperature difference 7) — 7) and the other to compensate for that difference by using Peltier or Joule effects in the case of exothermic or endothermic phenomena, respectively. This compensation (aiming to keep 7) = T2 during an experiment) was required because, as the thermopiles had a low heat conductivity, a significant fraction of the heat transfer would otherwise not be made through the thermopile wires and hence would not be detected. 

Tian s instrument had several important advantages over other types of calorimeter available at the time, such as isoperibol or adiabatic instruments (1) It could monitor rather small temperature changes (less than 10-4 K) and therefore minute samples could be used (2) it could be applied to investigate the thermochemistry of very slow phenomena (up to about 24 h) and (3) the use of the compensating Peltier cooling or Joule heating allowed one to investigate the... 

Another problem related to the validity of equation 9.9 is that equation 9.6 applies only to heat conduction. If T — 12 is large, some significant fraction of heat will be transferred by convection and radiation and thus will not be monitored by the thermopile. Consequently, the use of partial compensating Peltier or Joule effects was essential in the experiments involving Calvet s calorimeter, whose thermopiles had a fairly low thermal conductivity. 

The calorimeter that has been used to obtain the results presented in this section basically combines the power-compensation and heat-balance principles (see Sections 8.2.2.2 and 8.2.2.3). The heat-balance principle is implemented by Peltier elements [18]. This new... 

Electrochemical calorimetry — is the application of calorimetry to thermally characterize electrochemical systems. It includes several methods to investigate, for instances, thermal effects in batteries and to determine the -> molar electrochemical Peltier heat. Instrumentation for electrochemical calorimetric studies includes a calorimeter to establish the relationship between the amount of heat released or absorbed with other electrochemical variables, while an electrochemical reaction is taking place. Electrochemical calorimeters are usually tailor-made for a specific electrochemical system and must be well suited for a wide range of operation temperatures and the evaluation of the heat generation rate of the process. Electrochemical calorimeter components include a power supply, a device to control charge and discharge processes, ammeter and voltmeter to measure the current and voltage, as well as a computerized data acquisition system [i]. In situ calorimetry also has been developed for voltammetry of immobilized particles [ii,iii]. 

Diathermal-compensation calorimeters here again, sample temperature follows surroundings temperature (usually constant in adsorption experiments), but now by means of a power compensation within the sample cell (i.e. Joule or Peltier effect). This reduces the response time. 

Development of simple, low-cost calorimeters for routine analysis, called thermal enzyme probes (TEP), has been attempted by several groups. These are fabricated by attaching the enzyme directly to a thermistor [4, 5]. However, in this configuration, most of the heat evolved in the enzymic reaction is lost to the surrounding, resulting in lower sensitivity. The concept of TEP was essentially designed for batch operation, in which the enzyme is attached to a thin aluminum foil placed on the surface of the Peltier element that acts as a temperature sensor [6]. 

On the other hand, for slow reactions, adiabatic and isothermal calorimeters are used and in the case of very small heat effects, heat-flow micro-calorimeters are suitable. Heat effects of thermodynamic processes lower than 1J are advantageously measured by the micro-calorimeter proposed by Tian (1923) or its modifications. For temperature measurement of the calorimetric vessel and the cover, thermoelectric batteries of thermocouples are used. At exothermic processes, the electromotive force of one battery is proportional to the heat flow between the vessel and the cover. The second battery enables us to compensate the heat evolved in the calorimetric vessel using the Peltier s effect. The endothermic heat effect is compensated using Joule heat. Calvet and Prat (1955, 1958) then improved the Tian s calorimeter, introducing the differential method of measurement using two calorimetric cells, which enabled direct determination of the reaction heat. 

Conduction calorimeters typically, the Tian-Calvet calorimeter. They comment that, in spite of its good external thermal insulation, this calorimeter is not adiabatic, because the calories produced are continuously eliminated from the calorimetric vessel. They also consider that, in spite of the very small temperature variations of the sample cell, this calorimeter is not strictly isothermal , which justifies a separate group, except when a Peltier compensation totally cancels the temperature variations in the sample. 

Figure 6 Schematic of an isothermal calorimeter unit showing the position of the reaction ampoule, Peltier units and heat sink. The instrument has different combination of application, including flow through or ampoule insertion (Courtesy Thermometric Ltd, Jafalla, Sweden)...

The overall calorimeter equation of the Calvet calorimeter is finally given by Eq. (4). The overall heat effect, AH, is equal to the time integral over the Peltier compensation, the major effect to be measured, corrected for two factors the time-integral over the just-discussed losses, 4>, and, if the temperature does not stay exactly constant during the experiment, a correction term which involves the heat capacity of the calorimeter and the sample, C. All three terms can be evaluated by the measurement of the Peltier current i, the measurement of the emf of the measuring thermocouples, and a measurement of the change of the emf with time. The last term is needed for the calculation of the heat capacity correction which is written in Eq. (4). The last two terms in Eq. (4) are relatively small as long as the operation is close to isothermal. 

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