Thermochemistry is the study of the heat energy which is associated with

chemical reaction A chemical reaction is a process that leads to the chemical transformation of one set of chemical substances to another. Classically, chemical reactions encompass changes that only involve the positions of electrons in the forming and breaking ...

s and/or phase changes such as

melting Melting, or fusion, is a physical process that results in the phase transition of a substance from a solid to a liquid. This occurs when the internal energy of the solid increases, typically by the application of heat or pressure, which in ...

and

boiling Boiling is the rapid vaporization of a liquid, which occurs when a liquid is heated to its boiling point, the temperature at which the vapour pressure of the liquid is equal to the pressure exerted on the liquid by the surrounding atmosphere. Th ...

. A reaction may release or absorb energy, and a phase change may do the same. Thermochemistry focuses on the energy exchange between a system and its surroundings in the form of heat. Thermochemistry is useful in predicting reactant and product quantities throughout the course of a given reaction. In combination with

entropy Entropy is a scientific concept, as well as a measurable physical property, that is most commonly associated with a state of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodyna ...

determinations, it is also used to predict whether a reaction is spontaneous or non-spontaneous, favorable or unfavorable. Endothermic reactions absorb heat, while exothermic reactions release heat. Thermochemistry coalesces the concepts of thermodynamics with the concept of energy in the form of chemical bonds. The subject commonly includes calculations of such quantities as

heat capacity Heat capacity or thermal capacity is a physical property of matter, defined as the amount of heat to be supplied to an object to produce a unit change in its temperature. The SI unit of heat capacity is joule per kelvin (J/K). Heat cap ...

heat of combustion The heating value (or energy value or calorific value) of a substance, usually a fuel or food (see food energy), is the amount of heat released during the combustion of a specified amount of it. The ''calorific value'' is the total energy rele ...

heat of formation In chemistry and thermodynamics, the standard enthalpy of formation or standard heat of formation of a compound is the change of enthalpy during the formation of 1 mole of the substance from its constituent elements in their reference state, w ...

enthalpy Enthalpy , a property of a thermodynamic system, is the sum of the system's internal energy and the product of its pressure and volume. It is a state function used in many measurements in chemical, biological, and physical systems at a constant ...

, and free energy. Thermochemistry is one part of the broader field of chemical thermodynamics, which deals with the exchange of all forms of energy between system and surroundings, including not only heat but also various forms of

work Work may refer to: * Work (human activity), intentional activity people perform to support themselves, others, or the community ** Manual labour, physical work done by humans ** House work, housework, or homemaking ** Working animal, an animal t ...

, as well the exchange of matter. When all forms of energy are considered, the concepts of exothermic and endothermic reactions are generalized to

exergonic reaction In chemical thermodynamics, an exergonic reaction is a chemical reaction where the change in the free energy is negative (there is a net release of free energy). This indicates a spontaneous reaction if the system is closed and initial and fina ...

s and

endergonic reaction In chemical thermodynamics, an endergonic reaction (; also called a heat absorbing nonspontaneous reaction or an unfavorable reaction) is a chemical reaction in which the standard change in free energy is positive, and an additional driving fo ...

History

Thermochemistry rests on two generalizations. Stated in modern terms, they are as follows: #

Lavoisier Antoine-Laurent de Lavoisier ( , ; ; 26 August 17438 May 1794),
CNRS ( Laplace's law (1780): The energy change accompanying any transformation is equal and opposite to energy change accompanying the reverse process. # Hess' law of constant heat summation (1840): The energy change accompanying any transformation is the same whether the process occurs in one step or many. These statements preceded the

first law of thermodynamics The first law of thermodynamics is a formulation of the law of conservation of energy, adapted for thermodynamic processes. It distinguishes in principle two forms of energy transfer, heat and thermodynamic work for a system of a constant am ...

(1845) and helped in its formulation. Thermochemistry also involves the measurement of the

latent heat Latent heat (also known as latent energy or heat of transformation) is energy released or absorbed, by a body or a thermodynamic system, during a constant-temperature process — usually a first-order phase transition. Latent heat can be underst ...

phase transition In chemistry, thermodynamics, and other related fields, a phase transition (or phase change) is the physical process of transition between one state of a medium and another. Commonly the term is used to refer to changes among the basic states ...

s. Joseph Black had already introduced the concept of latent heat in 1761, based on the observation that heating ice at its melting point did not raise the temperature but instead caused some ice to melt. Gustav Kirchhoff showed in 1858 that the variation of the heat of reaction is given by the difference in

between products and reactants: dΔH / dT = ΔC_p. Integration of this equation permits the evaluation of the heat of reaction at one temperature from measurements at another temperature. Atkins P. and de Paula J., "Atkins' Physical Chemistry" (8th edn, W.H. Freeman 2006), p.56

Calorimetry

The measurement of heat changes is performed using

calorimetry In chemistry and thermodynamics, calorimetry () is the science or act of measuring changes in ''state variables'' of a body for the purpose of deriving the heat transfer associated with changes of its state due, for example, to chemical re ...

, usually an enclosed chamber within which the change to be examined occurs. The temperature of the chamber is monitored either using a

thermometer A thermometer is a device that measures temperature or a temperature gradient (the degree of hotness or coldness of an object). A thermometer has two important elements: (1) a temperature sensor (e.g. the bulb of a mercury-in-glass thermometer ...

thermocouple A thermocouple, also known as a "thermoelectrical thermometer", is an electrical device consisting of two dissimilar electrical conductors forming an electrical junction. A thermocouple produces a temperature-dependent voltage as a result of th ...

, and the temperature plotted against time to give a graph from which fundamental quantities can be calculated. Modern calorimeters are frequently supplied with automatic devices to provide a quick read-out of information, one example being the differential scanning calorimeter.

Systems

Several thermodynamic definitions are very useful in thermochemistry. A system is the specific portion of the universe that is being studied. Everything outside the system is considered the surroundings or environment. A system may be: * a (completely)

isolated system In physical science, an isolated system is either of the following: # a physical system so far removed from other systems that it does not interact with them. # a thermodynamic system enclosed by rigid immovable walls through which neither ...

which can exchange neither energy nor matter with the surroundings, such as an insulated

bomb calorimeter A bomb is an explosive weapon that uses the exothermic reaction of an explosive material to provide an extremely sudden and violent release of energy. Detonations inflict damage principally through ground- and atmosphere-transmitted mechanica ...

* a thermally isolated system which can exchange mechanical work but not heat or matter, such as an insulated closed

piston A piston is a component of reciprocating engines, reciprocating pumps, gas compressors, hydraulic cylinders and pneumatic cylinders, among other similar mechanisms. It is the moving component that is contained by a cylinder and is made gas-t ...

balloon A balloon is a flexible bag that can be inflated with a gas, such as helium, hydrogen, nitrous oxide, oxygen, and air. For special tasks, balloons can be filled with smoke, liquid water, granular media (e.g. sand, flour or rice), or lig ...

* a mechanically isolated system which can exchange heat but not mechanical work or matter, such as an uninsulated

* a

closed system A closed system is a natural physical system that does not allow transfer of matter in or out of the system, although — in contexts such as physics, chemistry or engineering — the transfer of energy (''e.g.'' as work or heat) is allowed. In ...

which can exchange energy but not matter, such as an uninsulated closed piston or balloon * an open system which it can exchange both matter and energy with the surroundings, such as a pot of boiling water

Processes

A system undergoes a process when one or more of its properties changes. A process relates to the change of state. An

isothermal In thermodynamics, an isothermal process is a type of thermodynamic process in which the temperature ''T'' of a system remains constant: Δ''T'' = 0. This typically occurs when a system is in contact with an outside thermal reservoir, an ...

(same-temperature) process occurs when temperature of the system remains constant. An isobaric (same-pressure) process occurs when the pressure of the system remains constant. A process is adiabatic when no heat exchange occurs.

References

External links