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Calorimetry measures the change in energy of an object or system by observing the heat transfer that occurs with its surroundings.
This heat exchange may occur due to physical changes, chemical reactions, or even sudden phase changes in the object or systems being observed. The energy change attribution can vary.
This type of measurement is able to determine if a chemical reaction resulted in the loss or absorbance of heat, referred to as exothermic reactions or endothermic reactions, respectively.
A calorimeter, which applies calorimetry to measure the amount of heat energy that is either lost or gained during some chemical or physical process, is a ubiquitous lab instrument found across several varying industries.
Calorimeters are used to find the amount of heat required to raise the temperature of a system or object by one degree. This is known as finding a system’s heat capacity, and is expressed as joules per kelvin (J/K). When heat capacity is expressed in calories per gram, this is referred to as specific heat.
Calorimeters can also be used to determine entropy and enthalpy. Entropy measures how much energy is spread out in a process over time or how spread out the initial energy of a system becomes at constant temperature. Enthalpy, on the other hand, relates to entropy in that entropy is roughly the heat supplied—or change in enthalpy—divided by temperature.
In its most basic form, a calorimeter is an enclosed, well-insulated chamber, filled with a known reference material that can measure the heat of reaction inside the chamber. Water is often used because most of the important properties of it are already known.
Performing thermal analysis on materials has uses in a wide variety of fields, including chemistry, material science, and thermodynamics. As a method for the measurement of heat, calorimetry can be applied to both solid and liquid fuel testing, as well as explosives testing, the study of heat energy (typically performed in academia), water treatment, and soil characterization, just to name a few.
There are also many types of calorimeters that differ based on what kind of reaction you are looking for or what specific experimental conditions you need.
This thermal analysis technique is used to look at heat exchange inside a system without having any heat transfer to its surroundings. This type of process is referred to as adiabatic. Ideally, when heat is generated in this type of setup, 100% of that heat will go toward increasing the system’s temperature, feeding the reaction.
The reaction will then generate more heat, accelerating the increase in temperature, and thus, the reaction. These devices are used to study so-called “runaway reactions” for this reason. It is important to note that no adiabatic calorimeter is completely adiabatic.
When looking at exothermic or endothermic properties of a chemical reaction, a reaction calorimeter is used. These devices are composed of an insulated jacket surrounding a reaction container.
The temperature measurement device should be submerged within the container. There are four main subcategories for reaction calorimeters:
Constant volume calorimeters, also known as bomb calorimeters, measure the heat energy of a reaction in an environment with a constant volume. Bomb calorimetry is used to look at temperature change within a combustion reaction.
Since the volume must remain the same, bomb calorimeters are built to withstand immense pressure that increases while the reactions occur within them. The basic components that make up this device include:
Additionally, there is a thermometer and a stirrer that monitor and move the water in the container.
As the name indicates, constant pressure calorimeters provide a constant pressure environment to measure the enthalpy change of a reaction, a material’s aversion to change. A simple example would be what is known as a coffee-cup calorimeter.
These calorimeters consist of two Styrofoam coffee cups nested in one another with a lid on top that has a hole for the thermometer and a stirring rod. A known solvent (such as water) is stored inside the innermost cup. With the outer cup acting as an insulator, the heat of combustion from the reaction is absorbed into the solvent and measured with the thermometer.
Constant pressure calorimeters are also called isobaric calorimeters.
These devices observe how changes in a material’s temperature alter its heat capacity. While using a known material and monitoring the change in heat capacity, phase and physical changes can be detected with accuracy.
The speed and ease with which this thermal analysis technique can cause materials to hit these transition points are the reason why it is such a commonly used method.
There are two approaches to DSC, heat flux DSC and heat flow DSC.
ITC is a technique used for quantitative studies of a wide variety of biomolecular reactions. It works by directly measuring the amount of heat that is either released or absorbed during a biomolecular binding event. Furthermore, ITC is the only technique capable of simultaneously measuring all binding parameters within a single experiment.
Being able to measure the heat transfer during binding enables accurate determination of binding constants (KD), reaction stoichiometry (n), enthalpy (∆H) and entropy (ΔS). This holistic view provides a complete thermodynamic profile of the molecular interaction. Isothermal titration calorimetry can also shed light on the mechanisms that underlie molecular interactions.
This deeper understanding of structure-function relationships offers scientists and researchers the confidence to make decisions in both hit selection and lead optimization.
At its heart, calorimeters and calorimetry use known physical or environmental properties to find unknown thermal properties of materials. Each method of calorimeter changes a different known variable and observes how that changes the sample’s amount of energy.
The many different types of methods, calibrations, and classifications of these types of equipment go to show how complex and specific thermal analysis can be.
Calorimetry can even be found in particle physics in the form of hadron and electromagnetic calorimeters. Both are used to better understand the smallest known units of matter in our universe by studying the heat energy of particles.
A hadronic calorimeter is currently being used at the European Organization for Nuclear Research (CERN) in the study of the Higgs-Boson particle, however, not every application is so complex. The labels of any drink or food product that show how many calories are in food are derived using calorimetry.
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