Agena Jayson A.

2011021286

Calorimeter . Device for measuring heat produced during a mechanical, electrical, or chemical reaction and for calculating the heat capacity of materials. A common design, known as a bomb calorimeter, consists of a reaction chamber surrounded by a liquid that absorbs the heat produced by the reaction. The amount of heat can be determined from the increase in temperature, taking into account the properties of the container and the liquid.

Types of Calorimeter
1. Adiabatic calorimeters Adiabatic calorimetry is used primarily for the study of thermal hazards and the consequences of a maloperation during a process, for instance a misfeed or loss of cooling. This is because on larger scales the effective natural cooling rates are negligible in comparison to heat generation, and many large process vessels can therefore be considered to be adiabatic. An adiabatic calorimeter is designed to simulate the thermal behaviour of larger scale chemical reactors, especially when studying uncontrolled and run-away reactions. 2. Reaction calorimeters A reaction calorimeter is an instrument that measures the amount of energy released or absorbed by a reaction. These measurements provide a more accurate picture of such reactions. Applications

Safety:- When considering scaling up a reaction to large scale from lab scale, it is important to understand how much heat is released. At a small scale heat released may not cause a concern, however when scaling up, that heat can build up and be extremely dangerous. Crystallization:- Crystallizing a reaction product from solution is a highly cost effective purification technique. It is therefore valuable to be able to

measure how effectively crystallization is taking place in order to be able to optimise it. The heat absorbed by the process can be a useful measure.

Kinetics:- The energy being released by any process in the form of heat is directly proportional to the rate of reaction and hence reaction calorimetry (as a time resolved measurement technique) can be used to study kinetics. Process Development:- The use of reaction calorimetry in process development has been historically limited due to the cost implications of these devices however calorimetry is a very fast and easy way to fully understand the reactions which are conducted as part of a chemical process.

3. Calvet-type Calorimeters A new method, ballistic Calvet calorimetry, is described for determining the enthalpy of vaporization of organic materials at high temperatures. A sample is dropped from room temperature into a Calvet-typecalorimeter set near the normal boiling temperature of the sample, producing an endothermic peak in the calorimetric signal. Because sample heat-up and evaporation are rapid, the peak height (as distinct from the more traditional peak area) is proportional to the total heat transferred. Results on pure organic compounds from 525 to 1025 K are compared with literature values derived from calorimetric, spectroscopic, and vapor-pressure measurements. These comparisons indicate that the total enthalpy change {Hmo(T,g) Hmo(298.15 K, cr or l)} is measured with an accuracy of 1.0 to 1.5 per cent when conditions are optimized. The method is rapid, convenient, and applicable to small samples (10 to 100 mg). Because of the short residence time of the organic sample at high temperatures, the danger of decomposition is reduced. A series of measurements on dibenzothiophene between 590 and 630 K is described, and the thermodynamic properties of this compound are reviewed. The method is also accurate for complex industrial mixtures. 4. Constant Pressure Calorimetry A simpler device than the constant-volume calorimeter, which is use to determine the heat changes for the non combustion reaction. A crude constant pressure calorimeter can be constructed from two Styrofoam coffee cups. This device measures the heat effects of a variety of reactions, such as acid base neutralization, as well as heat of solution and heat of dilution. Because the pressure is constant, the change of the process is equal to the enthalpy change. As in the case of constant volume calorimeter, we treat the calorimeter as an isolated system. Furthermore, we neglect the heat capacity of the coffe cups in our calculations.

5. Differential Scanning calorimeter An instrument for studying overall chemical reactions by measuring the associated exothermic and endothermic reactions that occur over a specified temperature cycle. Differential scanning calorimetry or DSC is a thermoanalytical technique in which the difference in the amount of heat required to increase the temperature of a sample and reference is measured as a function of temperature. Both the sample and reference are maintained at nearly the same temperature throughout the experiment. Generally, the temperature program for a DSC analysis is designed such that the sample holder temperature increases linearly as a function of time. The reference sample should have a well-defined heat capacity over the range of temperatures to be scanned. 6. Isothermal Titration Calorimetry Isothermal Titration Calorimetry (ITC) is the gold standard for measuring biomolecular interactions. ITC simultaneously determines all binding parameters (n, K, H and S) in a single experiment information that cannot be obtained from any other method. When substances bind, heat is either generated or absorbed. ITC is a thermodynamic technique that directly measures the heat released or absorbed during a biomolecular binding event. Measurement of this heat allows accurate determination of binding constants (KB), reaction stoichiometry (n), enthalpy (H) and entropy (S), thereby providing a complete thermodynamic profile of the molecular interaction in a single experiment. Because ITC goes beyond binding affinities and can elucidate the mechanism of the molecular interaction, it has become the method of choice for characterizing biomolecular interactions.

7. Bomb calorimeters A thick walled container in which organic material is burned completely in oxygen rich atmosphere to estimate the energy content of the material. Bomb calorimetry is used to measure the calorific value of food. Food of known mass is placed in the chamber and ignited with an electric spark. Combustion of the food liberates heat, which changes the temperature of water surrounding the chamber. The energy content of the food can be calculated from these temperature changes. A bomb calorimeter is used to measure the energy that is given out when one mole of a substance is completely burned in oxygen. A known amount of the substance is placed in the crucible, oxygen is added at 20 atmospheres

pressure, and then the substance is ignited using the heated wire. As the calorimeter heats, it heats the water. The rise in water temperature is measured and from this the heat generated by the burning substance is calculated.

The Mahler bomb calorimeter is a device used to determine the high calorific power of a solid or a liquid; for gaseous combustibles it's used the Junkers calorimeter. The heat generated from the combustion reaction of the analyzed combustible is absorbed from a water, or other liquid, mass of which is observed the temperature increase. It consists of a cylindrical container of about 500 cm^3, closed with a screw cap which has 2 holes. In one of them it's introduced an iron bar which sustaines a platinum crucible, in the other hole it's introduced another iron bar which sustaines a small iron curl connected to the first iron bar and put in the crucible. In the crucible it's introduced the sample of combustible (usually 40 cm^3) and then pressurized oxygen is introduced in the bomb [my note: I assume this is the reason it's called "bomb"]. The bomb is immersed in a calorimeter full of water which have a stirrer and a thermometer. The stirrer is started and when the thermometer reads a constant temperature, a voltage is created between the two iron bars which heats the little curl which burns by oxidation; the heat released burns the sample. The thermometer reads the temperature which arises suddenly to a certain value and then decreases slowly