Calorimetry

Calorimetry (OpenStax Chemistry 2e)

One technique we can use to measure the amount of heat involved in a chemical or physical process is known as calorimetry. Calorimetry is used to measure amounts of heat transferred to or from a substance. To do so, the heat is exchanged with a calibrated object (calorimeter). The temperature change measured by the calorimeter is used to derive the amount of heat transferred by the process under study. The measurement of heat transfer using this approach requires the definition of a system (the substance or substances undergoing the chemical or physical change) and its surroundings (all other matter, including components of the measurement apparatus, that serve to either provide heat to the system or absorb heat from the system).

A calorimeter is a device used to measure the amount of heat involved in a chemical or physical process. For example, when an exothermic reaction occurs in solution in a calorimeter, the heat produced by the reaction is absorbed by the solution, which increases its temperature. When an endothermic reaction occurs, the heat required is absorbed from the thermal energy of the solution, which decreases its temperature. The temperature change, along with the specific heat and mass of the solution, can then be used to calculate the amount of heat involved in either case.

Scientists use well-insulated calorimeters that all but prevent the transfer of heat between the calorimeter and its environment, which effectively limits the “surroundings” to the nonsystem components with the calorimeter (and the calorimeter itself). This enables the accurate determination of the heat involved in chemical processes, the energy content of foods, and so on. General chemistry students often use simple calorimeters constructed from polystyrene cups. These easy-to-use “coffee cup” calorimeters allow more heat exchange with the outside environment, and therefore produce less accurate energy values.

Commercial solution calorimeters are also available. Relatively inexpensive calorimeters often consist of two thin-walled cups that are nested in a way that minimizes thermal contact during use, along with an insulated cover, handheld stirrer, and simple thermometer. More expensive calorimeters used for industry and research typically have a well-insulated, fully enclosed reaction vessel, motorized stirring mechanism, and a more accurate temperature sensor.

Before discussing the calorimetry of chemical reactions, consider a simpler example that illustrates the core idea behind calorimetry. Suppose we initially have a high-temperature substance, such as a hot piece of metal (M), and a low-temperature substance, such as cool water (W). If we place the metal in the water, heat will flow from M to W. The temperature of M will decrease, and the temperature of W will increase, until the two substances have the same temperature—that is, when they reach thermal equilibrium. If this occurs in a calorimeter, ideally all of this heat transfer occurs between the two substances, with no heat gained or lost by either its external environment. Under these ideal circumstances, the net heat change is zero:

This relationship can be rearranged to show that the heat gained by substance M is equal to the heat lost by substance W:

The magnitude of the heat (change) is therefore the same for both substances, and the negative sign merely shows that q_{substance M} and q_{substance W} are opposite in direction of heat flow (gain or loss) but does not indicate the arithmetic sign of either q value (that is determined by whether the matter in question gains or loses heat, per definition). In the specific situation described, q_{substance M} is a negative value and q_{substance W} is positive, since heat is transferred from M to W.

When we use calorimetry to determine the heat involved in a chemical reaction, the same principles we have been discussing apply. The amount of heat absorbed by the calorimeter is often small enough that we can neglect it (though not for highly accurate measurements, as discussed later), and the calorimeter minimizes energy exchange with the outside environment. Because energy is neither created nor destroyed during a chemical reaction, the heat produced or consumed in the reaction (the “system”), q_reaction, plus the heat absorbed or lost by the solution (the “surroundings”), q_solution, must add up to zero:

This means that the amount of heat produced or consumed in the reaction equals the amount of heat absorbed or lost by the solution:

This concept lies at the heart of all calorimetry problems and calculations.

If the amount of heat absorbed by a calorimeter is too large to neglect or if we require more accurate results, then we must take into account the heat absorbed both by the solution and by the calorimeter.

The calorimeters described are designed to operate at constant (atmospheric) pressure and are convenient to measure heat flow accompanying processes that occur in solution. A different type of calorimeter that operates at constant volume, colloquially known as a bomb calorimeter, is used to measure the energy produced by reactions that yield large amounts of heat and gaseous products, such as combustion reactions. (The term “bomb” comes from the observation that these reactions can be vigorous enough to resemble explosions that would damage other calorimeters.) This type of calorimeter consists of a robust steel container (the “bomb”) that contains the reactants and is itself submerged in water. The sample is placed in the bomb, which is then filled with oxygen at high pressure. A small electrical spark is used to ignite the sample. The energy produced by the reaction is absorbed by the steel bomb and the surrounding water. The temperature increase is measured and, along with the known heat capacity of the calorimeter, is used to calculate the energy produced by the reaction. Bomb calorimeters require calibration to determine the heat capacity of the calorimeter and ensure accurate results. The calibration is accomplished using a reaction with a known q, such as a measured quantity of benzoic acid ignited by a spark from a nickel fuse wire that is weighed before and after the reaction. The temperature change produced by the known reaction is used to determine the heat capacity of the calorimeter. The calibration is generally performed each time before the calorimeter is used to gather research data.

Since the first one was constructed in 1899, 35 calorimeters have been built to measure the heat produced by a living person. These whole-body calorimeters of various designs are large enough to hold an individual human being. More recently, whole-room calorimeters allow for relatively normal activities to be performed, and these calorimeters generate data that more closely reflect the real world. These calorimeters are used to measure the metabolism of individuals under different environmental conditions, different dietary regimes, and with different health conditions, such as diabetes. In humans, metabolism is typically measured in Calories per day. A nutritional calorie (Calorie) is the energy unit used to quantify the amount of energy derived from the metabolism of foods; one Calorie is equal to 1000 calories (1 kcal), the amount of energy needed to heat 1 kg of water by 1 °C.

Related Research: Research Article: Bayesian analysis of isothermal titration calorimetry for binding thermodynamics

Source:

Flowers, P., Theopold, K., Langley, R., & Robinson, W. R. (2019, February 14). Chemistry 2e. Houston, Texas: OpenStax. Access for free at: https://openstax.org/books/chemistry-2e

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Related External Link:

Differential scanning calorimetry as a tool for protein folding and stability