Everything about Calorimeter totally explained
A
calorimeter is a device used for
calorimetry, the
science of measuring the heat of
chemical reactions or
physical changes as well as
heat capacity. The word
calorimeter is derived from the
Latin word
calor, meaning
heat. Differential scanning calorimeters, isothermal microcalorimeters, titration calorimeters and accelerated rate calorimeters are among the most common types. A simple calorimeter just consists of a thermometer attached to an insulated container. To find the
enthalpy change per mole of a substance X in a reaction between two liquids X and Y, they're added to the calorimeter and the initial and final (after the reaction has finished)
temperatures are noted. Multiplying the temperature change by the mass and
specific heat capacities of the liquids gives a value for the
energy given off during the reaction (assuming the reaction was exothermic.). Dividing the energy change by how many moles of X were present gives its enthalpy change of reaction. This method is used primarily in academic teaching as it describes the theory of calorimetry. It doesn’t however account for the heat loss through the container or the heat capacity of the thermometer and container itself. In addition, the object placed inside the calorimeter show that the objects transferred their heat to the calorimeter and into the liquid, and the heat absorbed by the calorimeter and the liquid is equal to the heat given off by the metals.
Types
Reaction calorimeters
A
reaction calorimeter is a calorimeter in which a
chemical reaction is initiated within a closed insulated container. Reaction heats are measured and the total heat is obtained by integrating heatflow versus time. This is the standard used in industry to measure heats since industrial processes are engineered to run at constant temperatures. Reaction calorimetry can also be used to determine maximum heat release rate for chemical process engineering and for tracking the global kinetics of reactions. There are three common methods for measuring heat in reaction calorimeter:
Heat flow calorimetry
The cooling/heating jacket controls the temperature of the process. Heat is measured by monitoring the temperature difference between heat transfer fluid and the process fluid as follows:
where
» = process heating (or cooling) power (W)
= overall heat transfer coefficient (W/(m
2K))
» = heat transfer area (m
2)
= process temperature (K)
» = jacket temperature (K)
Heat flow calorimetry allows the user to measure heat whilst the process temperature remains under control. It is however a difficult technique to use and not particularly accurate. The value of U has to be predetermined by careful experimentation and any change in product composition, liquid level, process temperature, agitation rate or viscosity will upset the calibration.
A variation of the 'heat flow' technique is called 'power compensation' calorimetry. This method uses a cooling jacket operating at constant flow and temperature. The process temperature is regulated by adjusting the power of the electrical heater. When the experiment is started, the electrical heat and the cooling power (of the cooling jacket) are in balance. As the process heat load changes, the electrical power is varied in order to maintain the desired process temperature. The heat liberated or absorbed by the process is determined from the difference between the initial electrical power and the demand for electrical power at the time of measurement. The power compensation method is easier to set up than heat flow calorimetry but it suffers from the similar limitations since any change in product composition, liquid level, process temperature, agitation rate or viscosity will upset the calibration. The presence of an electrical heating element is also undesirable for process operations.
Heat balance calorimetry
The cooling/heating jacket controls the temperature of the process. Heat is measured by monitoring the heat gained or lost by the heat transfer fluid as follows:
From the
integral of this peak the enthalpy of melting can be determined, and from its onset the melting temperature.
Differential scanning calorimetry is a workhorse technique in many fields, particularly in
polymer characterization.
A
modulated temperature differential scanning calorimeter (MTDSC) is a type of DSC in which a small oscillation is imposed upon the otherwise linear heating rate.
This has a number of advantages. It facilitates the direct measurement of the heat capacity in one measurement, even in (quasi-)isothermal conditions. It permits the simultaneous measurement of heat effects that are reversible and not reversible at the timescale of the oscillation (reversing and non-reversing heat flow, respectively). It increases the sensitivity of the heat capacity measurement, allowing for scans at a slow underlying heating rate.
Isothermal titration calorimeter
In an
isothermal titration calorimeter, the heat of reaction is used to follow a titration experiment. This permits determination of the mid point (
stoichiometry) (N) of a reaction as well as its enthalpy (delta H), entropy (delta S) and of primary concern the binding affinity (Ka)
The technique is gaining in importance particularly in the field of
biochemistry, because it facilitates determination of substrate binding to
enzymes. The technique is commonly used in the pharmaceutical industry to characterize potential drug candidates.
X-ray microcalorimeter
In 1982, a new approach to non-dispersive
X-ray spectroscopy, based on the measurement of heat rather than charge, was proposed by Moseley et al. (1984). The detector, and X-ray microcalorimeter, works by sensing the heat pulses generated by X-ray
photons when they're absorbed and thermalized. The temperature increase is directly proportional to photon energy. This invention combines high detector efficiency with high energy resolution, mainly achievable because of the low temperature of operation. Microcalorimeters have a low-heat-capacity mass that absorbs incident X-ray (UV, visible, or near IR) photons, a weak link to a low-temperature
heat sink which provides the thermal isolation needed for a temperature rise to occur, and a thermometer to measure change in temperature. Following these ideas, a large development effort started. The first astronomical spacecraft that was designed, built and launched with embarqued cryogenic microcalorimeters was
Astro-E2.
NASA as well as
ESA have plans for future missions (
Constellation-X and
XEUS, respectively) that will use some sort of micro-calorimeters.
Heat-loss calorimeter
High-energy particle calorimeter
In
particle physics, a calorimeter is a component of a
detector that measures the
energy of entering
particles.
Further Information
Get more info on 'Calorimeter'.
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