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Calorimetry

physical science Maturity 11-13 Next article →

Calorimetry is the scientific study of measuring heat transfer. It focuses on measuring changes in state variables of a body. Scientists use these measurements to find the heat associated with specific changes. These changes might include chemical reactions or physical changes like phase transitions. A phase transition is when a substance changes from one state to another, such as ice melting into water.

Ice-calorimeter
Ice-calorimeter

To perform these measurements, scientists use a specialized tool called a calorimeter.

There are several ways to measure heat depending on the subject. Indirect calorimetry is used to study the heat produced by living organisms. This method does not put the organism inside the device. Instead, it measures the consumption of oxygen or the production of waste products. These wastes might include carbon dioxide or nitrogen, such as ammonia in aquatic life or urea in land animals.

Indirect calorimetry laboratory with canopy hood
Indirect calorimetry laboratory with canopy hood

Direct calorimetry is different because the entire organism is placed inside the calorimeter. Modern technology also includes the differential scanning calorimeter. This device measures small amounts of material by heating them at a controlled rate. It records the heat flow into or from the specimen.

Scientists use different mathematical rules to calculate heat. In classical calorimetry, researchers use a reference material with known thermal properties. A key rule from Clausius and Kelvin states that pressure is determined by temperature and volume. This applies to changes that do not involve a phase change. For these processes, scientists measure heat capacity at a constant volume. This is called isochoric calorimetry. The heat capacity at constant volume is the heat needed to raise temperature while volume stays the same.

Snellen human calorimeter, uOttawa
Snellen human calorimeter, uOttawa

Another method involves constant-pressure calorimetry. In this version, the volume is allowed to change freely while pressure stays steady.

When a substance undergoes a phase change, the math changes. During these transitions, scientists must account for latent heat. Latent heat is the heat involved in a change of state at a constant temperature. For example, Joseph Black recognized that adding heat to ice at its melting point does not change its temperature. This is because the energy is used for the phase change rather than raising the temperature. There is latent heat with respect to volume and latent heat with respect to pressure. These two values are always of opposite signs.

The history of heat is thousands of years old. In the Graeco-Roman era, Plato and Aristotle viewed heat as a part of fire. Later, Isaac Newton thought heat moved through the vibrations of a substance called aether. René Descartes suggested heat was the accelerated motion of air particles caused by light. For many centuries, scientists believed in "caloric." This was a theory that heat was a weightless, self-repelling fluid.

Ice-calorimeter
Ice-calorimeter

This idea was eventually proven wrong as the science of thermodynamics grew.

Many important discoveries shaped modern calorimetry. In 1750, Georg Wilhelm Richmann created the first general calorimetric equation. In 1761, Joseph Black discovered latent and specific heat. This allowed scientists to distinguish between heat and temperature. In 1789, Antoine Lavoisier and Pierre-Simon Laplace built the first calorimeter.

Ice-calorimeter
Ice-calorimeter

Later, Sir Benjamin Thompson concluded that heat is a form of energy rather than a material substance. In the 1840s, James Prescott Joule proved this by linking mechanical work to thermal energy. He found that 4.184 joules of work produce one calorie of heat.

Other major milestones include the work of Germain Henri Hess and Pierre Eugène Berthelot. In 1840, Hess formulated Hess's law. This law states that the total enthalpy change of a chemical reaction is independent of the reaction path. This remains a fundamental principle in thermochemistry today. In the 1870s, Berthelot developed the first modern bomb calorimeter. He also introduced the terms endothermic and exothermic. These terms describe whether a reaction absorbs or releases heat. This history shows how calorimetry moved from simple observations to precise mathematical science.

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File:Ice-calorimeter.jpg
Ice-calorimeter.jpg
File:Snellen human calorimeter, uOttawa.jpg
Snellen human calorimeter, uOttawa.jpg
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Indirect calorimetry laboratory with...
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