Calorimeter

The world’s first ice-calorimeter, used in the winter of 1782-83, by Antoine Lavoisier and Pierre-Simon Laplace, to determine the heat evolved in various chemical changes; calculations which were based on Joseph Black’s prior discovery of latent heat. These experiments mark the foundation of thermochemistry.

A calorimeter is an object used for calorimetry, or the process of measuring the heat of chemical reactions or physical changes as well as heat capacity. 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 a metal container full of water suspended above a combustion chamber.

To find the enthalpy change per mole of a substance A in a reaction between two substances A and B, the substances are added to a calorimeter and the initial and final temperatures (before the reaction started and after it has finished) are noted. Multiplying the temperature change by the mass and specific heat capacities of the substances gives a value for the energy given off or absorbed during the reaction. Dividing the energy change by how many moles of A were present gives its enthalpy change of reaction. This method is used primarily in academic teaching as it describes the theory of calorimetry. It does not account for the heat loss through the container or the heat capacity of the thermometer and container itself.

History

The name calorimeter was made up by Antoine Lavoisier.^[1] In 1780, he used a guinea pig in his experiments with this device to measure heat production. The heat from the guinea pig's respiration melted snow surrounding the calorimeter, showing that respiratory gas exchange is a combustion, similar to a candle burning.^[2]

Adiabatic calorimeters

An adiabatic calorimeter is a calorimeter used to examine a runaway reaction. Since the calorimeter runs in an adiabatic environment, any heat generated by the material sample under test causes the sample to increase in temperature, thus fuelling the reaction.

No adiabatic calorimeter is fully adiabatic - some heat will be lost by the sample to the sample holder. A mathematical correction factor, known as the phi-factor, can be used to adjust the calorimetric result to account for these heat losses. The phi-factor is the ratio of the thermal mass of the sample and sample holder to the thermal mass of the sample alone.

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 four main methods for measuring the heat in reaction calorimeter:

Heat flow calorimeter

The cooling/heating jacket controls either the temperature of the process or the temperature of the jacket. Heat is measured by monitoring the temperature difference between heat transfer fluid and the process fluid. In addition, fill volumes (i.e. wetted area), specific heat, heat transfer coefficient have to be determined to arrive at a correct value. It is possible with this type of calorimeter to do reactions at reflux, although the accuracy is not as good.

Heat balance calorimeter

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.

Power compensation

Power compensation uses a heater placed within the vessel to maintain a constant temperature. The energy supplied to this heater can be varied as reactions require and the calorimetry signal is purely derived from this electrical power.

Constant flux

Constant flux calorimetry (or COFLUX as it is often termed) is derived from heat balance calorimetry and uses specialized control mechanisms to maintain a constant heat flow (or flux) across the vessel wall.

Bomb calorimeters

Bomb calorimeter

Bomb calorimeter

A bomb calorimeter is a type of constant-volume calorimeter used in measuring the heat of combustion of a particular reaction. Bomb calorimeters have to withstand the large pressure within the calorimeter as the reaction is being measured. Electrical energy is used to ignite the fuel; as the fuel is burning, it will heat up the surrounding air, which expands and escapes through a tube that leads the air out of the calorimeter. When the air is escaping through the copper tube it will also heat up the water outside the tube. The change in temperature of the water allows for calculating calorie content of the fuel.

In more recent calorimeter designs, the whole bomb, pressurized with excess pure oxygen (typically at 30atm) and containing a weighed mass of a sample (typically 1-1.5 g) and a small fixed amount of water (to saturate the internal atmosphere, thus ensuring that all water produced is liquid, and removing the need to include enthalpy of vaporization in calculations), is submerged under a known volume of water (ca. 2000 ml) before the charge is electrically ignited. The bomb, with the known mass of the sample and oxygen, form a closed system - no gases escape during the reaction. The weighed reactant put inside the steel container is then ignited. Energy is released by the combustion and heat flow from this crosses the stainless steel wall, thus raising the temperature of the steel bomb, its contents, and the surrounding water jacket. The temperature change in the water is then accurately measured with a thermometer. This reading, along with a bomb factor (which is dependent on the heat capacity of the metal bomb parts), is used to calculate the energy given out by the sample burn. A small correction is made to account for the electrical energy input, the burning fuse, and acid production (by titration of the residual liquid). After the temperature rise has been measured, the excess pressure in the bomb is released.

Basically, a bomb calorimeter consists of a small cup to contain the sample, oxygen, a stainless steel bomb, water, a stirrer, a thermometer, the dewar or insulating container (to prevent heat flow from the calorimeter to the surroundings) and ignition circuit connected to the bomb. By using stainless steel for the bomb, the reaction will occur with no volume change observed.

Since there is no heat exchange between the calorimeter and surroundings → Q = 0 (adiabatic) ; no work performed → W = 0 Thus, the total internal energy change ΔU(total) = Q + W = 0

Also, total internal energy change ΔU(total) = ΔU(system) + ΔU(surroundings) = 0 → ΔU(system) = - ΔU(surroundings) = -C_v ΔT (constant volume → dV = 0)

where C_v = heat capacity of the bomb

Before the bomb can be used to determine heat of combustion of any compound, it must be calibrated. The value of C_v can be estimated by C_v (calorimeter) = m (water). C_v (water) + m (steel). C_v (steel)

m (water) and m (steel) can be measured;

C_v(water)= 1 cal/g.K

C_v(steel)= 0.1 cal/g.K

In laboratory, C_v is determined by running a compound with known heat of combustion value: C_v = H_c/ΔT

Common compounds are benzoic acid (H_c = 6318 cal/g) or p-methyl benzoic acid (H_c = 6957 cal/g).

Temperature (T) is recorded every minute and ΔT = T(final) - T(initial)

A small factor contributes to the correction of the total heat of combustion is the fuse wire. Nickel fuse wire is often used and has heat of combustion = 981.3 cal/g

In order to calibrate the bomb, a small amount (~ 1 g) of benzoic acid, or p-methyl benzoic acid is weighed. A length of Nickel fuse wire (~10 cm) is weighed both before and after the combustion process. Mass of fuse wire burned Δm = m(before) - m(after)

The combustion of sample (benzoic acid) inside the bomb ΔH_c = ΔH_c (benzoic acid) x m (benzoic acid) + ΔH_c (Ni fuse wire) x Δm (Ni fuse wire)

ΔH_c = C_v. ΔT → C_v = ΔH_c/ΔT

Once C_v value of the bomb is determined, the bomb is ready to use to calculate heat of combustion of any compounds by ΔH_c = C_v. ΔT

^{[3] [4]}

Combustion of non-flammables

The higher pressure and concentration of O₂ in the bomb system can make compounds that are not normally flammable combustible, which is needed for this procedure, although some substances don’t combust completely, making the calculations harder once it have to take in consideration the remaining mass, making the possible error considerably bigger and compromising the data.

When working with compounds that are not as flammable (that might nor combust all the way) one solution would be to mix the compound with some flammable compounds with a known heat of combustion and make a pallet with the mixture. Once it’s known the Cv of the bomb, the heat of combustion of the flammable compound (C_FC), of the wire (C_W) and the masses (m_FC and m_W), and the temperature change (ΔT), the heat of combustion of the less flammable compound (C_LFC) can be calculated with:

C_LFC = C_v. ΔT - C_FC*m_FC - C_W*m_W ^[5]

Calvet-type calorimeters

The detection is based on a three-dimensional fluxmeter sensor. The fluxmeter element consists of a ring of several thermocouples in series. The corresponding thermopile of high thermal conductivity surrounds the experimental space within the calorimetric block. The radial arrangement of the thermopiles guarantees an almost complete integration of the heat. This is verified by the calculation of the efficiency ratio that indicates that an average value of 94% +/- 1% of heat is transmitted through the sensor on the full range of temperature of the Calvet-type calorimeter. In this setup, the sensitivity of the calorimeter is not affected by the crucible, the type of purgegas, or the flow rate. The main advantage of the setup is the increase of the experimental vessel's size and consequently the size of the sample, without affecting the accuracy of the calorimetric measurement.

The calibration of the calorimetric detectors is a key parameter and has to be performed very carefully. For Calvet-type calorimeters, a specific calibration, so called Joule effect or electrical calibration, has been developed to overcome all the problems encountered by a calibration done with standard materials. The main advantages of this type of calibration are as follows:

• It is an absolute calibration.
• The use of standard materials for calibration is not necessary. The calibration can be performed at a constant temperature, in the heating mode and in the cooling mode.
• It can be applied to any experimental vessel volume.
• It is a very accurate calibration.

An example of Calvet-type calorimeter is the C80 Calorimeter (reaction, isothermal and scanning calorimeter).^[6]

Constant-pressure calorimeter

A constant-pressure calorimeter measures the change in enthalpy of a reaction occurring in solution during which the atmospheric pressure remains constant.

An example is a coffee-cup calorimeter, which is constructed from two nested Styrofoam cups and a lid with two holes, allowing insertion of a thermometer and a stirring rod. The inner cup holds a known amount of a solute, usually water, that absorbs the heat from the reaction. When the reaction occurs, the outer cup provides insulation. Then

$C_p = \frac {W\Delta H}{M\Delta T}$

where

$C_p$ = Specific heat at constant pressure

$\Delta H$ = Enthalpy of solution

$\Delta T$ = Change in temperature

$W$ = mass of solute

$M$ = molecular mass of solute

The measurement of heat using a simple calorimeter, like the coffee cup calorimeter, is an example of constant-pressure calorimetry, since the pressure (atmospheric pressure) remains constant during the process. Constant-pressure calorimetry is used in determining the changes in enthalpy occurring in solution. Under these conditions the change in enthalpy equals the heat.

Differential scanning calorimeter

In a differential scanning calorimeter (DSC), heat flow into a sample—usually contained in a small aluminium capsule or 'pan'—is measured differentially, i.e., by comparing it to the flow into an empty reference pan.

In a heat flux DSC, both pans sit on a small slab of material with a known (calibrated) heat resistance K. The temperature of the calorimeter is raised linearly with time (scanned), i.e., the heating rate dT/dt = β is kept constant. This time linearity requires good design and good (computerized) temperature control. Of course, controlled cooling and isothermal experiments are also possible.

Heat flows into the two pans by conduction. The flow of heat into the sample is larger because of its heat capacity C_p. The difference in flow dq/dt induces a small temperature difference ΔT across the slab. This temperature difference is measured using a thermocouple. The heat capacity can in principle be determined from this signal:

$\Delta T = K {dq\over dt} = K C_p\, \beta$

Note that this formula (equivalent to Newton's law of heat flow) is analogous to, and much older than, Ohm's law of electric flow: ΔV = R dQ/dt = R I.

When suddenly heat is absorbed by the sample (e.g., when the sample melts), the signal will respond and exhibit a peak.

${dq\over dt} = C_p \beta + f(t,T)$

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 respond to a changing heating rate (reversing) and that don't respond to the changing heating rate (non-reversing). It allows for the optimization of both sensitivity and resolution in a single test by allowing for a slow average heating rate (optimizing resolution) and a fast changing heating rate (optimizing sensitivity).^[7]

Safety Screening:- DSC may also be used as an initial safety screening tool. In this mode the sample will be housed in a non-reactive crucible (often Gold, or Gold plated steel), and which will be able to withstand pressure (typically up to 100 bar). The presence of an exothermic event can then be used to assess the stability of a substance to heat. However, due to a combination of relatively poor sensitivity, slower than normal scan rates (typically 2–3°/min - due to much heavier crucible) and unknown activation energy, it is necessary to deduct about 75–100 °C from the initial start of the observed exotherm to suggest a maximum temperature for the material. A much more accurate data set can be obtained from an adiabatic calorimeter, but such a test may take 2–3 days from ambient at a rate of 3 °C increment per half hour.

Isothermal titration calorimeter

In an isothermal titration calorimeter, the heat of reaction is used to follow a titration experiment. This permits determination of the midpoint (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.

See also

• Enthalpy
• Heat
• Calorie
• Heat of combustion
• Calorimeter constant
• Reaction calorimeter
• Calorimeter (particle physics)

References

1. Antoine Laurent Lavoisier, Elements of Chemistry: In a New Systematic Order; Containing All the Modern Discoveries, 1789: "I acknowledge the name of Calorimeter, which I have given it, as derived partly from Greek and partly from Latin, is in some degree open to criticism; but in matters of science, a slight deviation from strict etymology, for the sake of giving distinctness of idea, is excusable; and I could not derive the name entirely from Greek without approaching too near to the names of known instruments employed for other purposes."
2. Buchholz, Andrea C; Schoeller, Dale A. (2004). "Is a Calorie a Calorie?". American Journal of Clinical Nutrition 79 (5): 899S–906S. PMID 15113737. Retrieved 2007-03-12
3. Polik, W. (1997). Bomb Calorimetery. Retrieved from http://www.chem.hope.edu/~polik/Chem345-2000/bombcalorimetry.htm
4. Bozzelli, J. (2010). Heat of Combustion via Calorimetry: Detailed Procedures. Chem 339-Physical Chemistry Lab for Chemical Engineers –Lab Manual.
5. Bech, N., Jensen, P. A., & Dam-Johansen, K. (2009). Determining the elemental composition of fuels by bomb calorimetry and the inverse correlation of HHV with elemental composition. Biomass & Bioenergy, 33(3), 534-537. 10.1016/j.biombioe.2008.08.015
6. C80 Calorimeter from Setaram Instrumentation
7. http://csacs.mcgill.ca/francais/docs/CHEM634/DSC_Hunt.pdf

External Links

• Isothermal Battery Calorimeters - National Renewable Energy Laboratory
• Fact Sheet: Isothermal Battery Calorimeters, National Renewable Energy Laboratory, March 2015