heat

Notation and units

As a form of energy, heat has the unit joule (J) in the International System of Units (SI). In addition, many applied branches of engineering use other, traditional units, such as the British thermal unit (BTU) and the calorie. The standard unit for the rate of heating is the watt (W), defined as one joule per second.

The symbol Q for heat was introduced by Rudolf Clausius and Macquorn Rankine in c. 1859.

Heat released by a system into its surroundings is by convention, as a contributor to internal energy, a negative quantity (Q < 0); when a system absorbs heat from its surroundings, it is positive (Q > 0). Heat transfer rate, or heat flow per unit time, is denoted by

Q

˙

{\displaystyle {\dot {Q}}}

, but it is not a time derivative of a function of state (which can also be written with the dot notation) since heat is not a function of state. Heat flux is defined as rate of heat transfer per unit cross-sectional area (watts per square metre).

History

In ordinary language, English 'heat' or 'warmth', just as French chaleur, German Hitze or Wärme, Latin calor, Greek θάλπος, etc. refers to either thermal energy or temperature, or the human perception of these. Later, chaleur (as used by Sadi Carnot), 'heat', and Wärme became equivalents also as specific scientific terms at an early stage of thermodynamics. Speculation on 'heat' as a separate form of matter has a long history, involving the phlogiston theory, the caloric theory, and fire. Many careful and accurate historical experiments practically exclude friction, mechanical and thermodynamic work and matter transfer, investigating transfer of energy only by thermal conduction and radiation. Such experiments give impressive rational support to the caloric theory of heat. To account also for changes of internal energy due to friction, and mechanical and thermodynamic work, the caloric theory was, around the end of the eighteenth century, replaced by the "mechanical" theory of heat, which is accepted today.

17th century–early 18th century

As scientists of the early modern age began to adopt the view that matter consists of particles, a close relationship between heat and the motion of those particles was widely surmised, or even the equivalency of the concepts, boldly expressed by the English philosopher Francis Bacon in 1620. "It must not be thought that heat generates motion, or motion heat (though in some respects this be true), but that the very essence of heat ... is motion and nothing else." "not a ... motion of the whole, but of the small particles of the body." In The Assayer (published 1623) Galileo Galilei, in turn, described heat as an artifact of our minds.

... about the proposition "motion is the cause of heat"... I suspect that people in general have a concept of this which is very remote from the truth. For they believe that heat is a real phenomenon, or property ... which actually resides in the material by which we feel ourselves warmed.

Galileo wrote that heat and pressure are apparent properties only, caused by the movement of particles, which is a real phenomenon. In 1665, and again in 1681, English polymath Robert Hooke reiterated that heat is nothing but the motion of the constituent particles of objects, and in 1675, his colleague, Anglo-Irish scientist Robert Boyle repeated that this motion is what heat consists of.

Heat has been discussed in ordinary language by philosophers. An example is this 1720 quote from the English philosopher John Locke:

Heat, is a very brisk agitation of the insensible parts of the object, which produces in us that sensation from whence we denominate the object hot; so what in our sensation is heat, in the object is nothing but motion. This appears by the way, whereby heat is produc'd: for we see that the rubbing of a brass nail upon a board, will make it very hot; and the axle-trees of carts and coaches are often hot, and sometimes to a degree, that it sets them on fire, by the rubbing of the nave of the wheel upon it.

When Bacon, Galileo, Hooke, Boyle and Locke wrote "heat", they might more have referred to what we would now call "temperature". No clear distinction was made between heat and temperature until the mid-18th century, nor between the internal energy of a body and the transfer of energy as heat until the mid-19th century.

18th century

Unstated distinctions between heat and "hotness" may be very old, heat seen as something dependent on the quantity of a hot substance, "heat", vaguely perhaps distinct from the quality of "hotness". In 1723, the English mathematician Brook Taylor measured the temperature—the expansion of the liquid in a thermometer—of mixtures of various amounts of hot water in cold water. As expected, the increase in temperature was in proportion to the proportion of hot water in the mixture. The distinction between heat and temperature is implicitly expressed in the last sentence of his report.

I successively fill'd the Vessels with one, two, three, &c. Parts of hot boiling Water, and the rest cold ... And having first observed where the Thermometer stood in cold Water, I found that its rising from that Mark ... was accurately proportional to the Quantity of hot Water in the Mixture, that is, to the Degree of Heat.

In 1748, an account was published in The Edinburgh Physical and Literary Essays of an experiment by the Scottish physician and chemist William Cullen. Cullen had used an air pump to lower the pressure in a container with diethyl ether. The ether boiled, while no heat was withdrawn from it, and its temperature decreased. And in 1758 on a warm day in Cambridge, England, Benjamin Franklin and fellow scientist John Hadley experimented by continually wetting the ball of a mercury thermometer with ether and using bellows to evaporate the ether. With each subsequent evaporation, the thermometer read a lower temperature, eventually reaching 7 °F (−14 °C).

In 1756 or soon thereafter, Joseph Black, Cullen's friend and former assistant, began an extensive study of heat. In 1760 Black realized that when two different substances of equal mass but different temperatures are mixed, the changes in number of degrees in the two substances differ, though the heat gained by the cooler substance and lost by the hotter is the same. Black related an experiment conducted by Daniel Gabriel Fahrenheit on behalf of Dutch physician Herman Boerhaave. For clarity, he then described a hypothetical but realistic variant of the experiment: If equal masses of 100 °F water and 150 °F mercury are mixed, the water temperature increases by 20 ° and the mercury temperature decreases by 30 ° (both arriving at 120 °F), even though the heat gained by the water and lost by the mercury is the same. This clarified the distinction between heat and temperature. It also introduced the concept of specific heat capacity, being different for different substances. Black wrote: "Quicksilver [mercury] ... has less capacity for the matter of heat than water."

Classical thermodynamics

The modern understanding of heat is often partly attributed to Thompson's 1798 mechanical theory of heat ("An Inquiry Concerning the Source of the Heat Which Is Excited by Friction"), postulating a mechanical equivalent of heat.

A collaboration between Nicolas Clément and Sadi Carnot (Reflections on the Motive Power of Fire) in the 1820s had some related thinking along similar lines. In 1842, Julius Robert Mayer frictionally generated heat in paper pulp and measured the temperature rise. In 1845, Joule published a paper entitled The Mechanical Equivalent of Heat, in which he specified a numerical value for the amount of mechanical work required to "produce a unit of heat", based on heat production by friction in the passage of electricity through a resistor and in the rotation of a paddle in a vat of water. The theory of classical thermodynamics matured in the 1850s to 1860s.

In 1850, Clausius, responding to Joule's experimental demonstrations of heat production by friction, rejected the caloric doctrine of conservation of heat, writing:

If we assume that heat, like matter, cannot be lessened in quantity, we must also assume that it cannot be increased; but it is almost impossible to explain the ascension of temperature brought about by friction otherwise than by assuming an actual increase of heat. The careful experiments of Joule, who developed heat in various ways by the application of mechanical force, establish almost to a certainty, not only the possibility of increasing the quantity of heat, but also the fact that the newly-produced heat is proportional to the work expended in its production. It may be remarked further, that many facts have lately transpired which tend to overthrow the hypothesis that heat is itself a body, and to prove that it consists in a motion of the ultimate particles of bodies.

The process function Q was introduced by Rudolf Clausius in 1850.

Clausius described it with the German compound Wärmemenge, translated as "amount of heat".

James Clerk Maxwell in his 1871 Theory of Heat outlines four stipulations for the definition of heat:

Heat transfer

Heat transfer between two bodies

Referring to conduction, Partington writes: "If a hot body is brought in conducting contact with a cold body, the temperature of the hot body falls and that of the cold body rises, and it is said that a quantity of heat has passed from the hot body to the cold body."

Referring to radiation, Maxwell writes: "In Radiation, the hotter body loses heat, and the colder body receives heat by means of a process occurring in some intervening medium which does not itself thereby become hot."

Maxwell writes that convection as such "is not a purely thermal phenomenon". In thermodynamics, convection in general is regarded as transport of internal energy. If, however, the convection is enclosed and circulatory, then it may be regarded as an intermediary that transfers energy as heat between source and destination bodies, because it transfers only energy and not matter from the source to the destination body.

In accordance with the first law for closed systems, energy transferred solely as heat leaves one body and enters another, changing the internal energies of each. Transfer, between bodies, of energy as work is a complementary way of changing internal energies. Though it is not logically rigorous from the viewpoint of strict physical concepts, a common form of words that expresses this is to say that heat and work are interconvertible.

Cyclically operating engines that use only heat and work transfers have two thermal reservoirs, a hot and a cold one. They may be classified by the range of operating temperatures of the working body, relative to those reservoirs. In a heat engine, the working body is at all times colder than the hot reservoir and hotter than the cold reservoir. In a sense, it uses heat transfer to produce work. In a heat pump, the working body, at stages of the cycle, goes both hotter than the hot reservoir, and colder than the cold reservoir. In a sense, it uses work to produce heat transfer.

Heat engine

In classical thermodynamics, a commonly considered model is the heat engine. It consists of four bodies: the working body, the hot reservoir, the cold reservoir, and the work reservoir. A cyclic process leaves the working body in an unchanged state, and is envisaged as being repeated indefinitely often. Work transfers between the working body and the work reservoir are envisaged as reversible, and thus only one work reservoir is needed. But two thermal reservoirs are needed, because transfer of energy as heat is irreversible. A single cycle sees energy taken by the working body from the hot reservoir and sent to the two other reservoirs, the work reservoir and the cold reservoir. The hot reservoir always and only supplies energy, and the cold reservoir always and only receives energy. The second law of thermodynamics requires that no cycle can occur in which no energy is received by the cold reservoir. Heat engines achieve higher efficiency when the ratio of the initial and final temperature is greater.

Heat pump or refrigerator

Another commonly considered model is the heat pump or refrigerator. Again there are four bodies: the working body, the hot reservoir, the cold reservoir, and the work reservoir. A single cycle starts with the working body colder than the cold reservoir, and then energy is taken in as heat by the working body from the cold reservoir. Then the work reservoir does work on the working body, adding more to its internal energy, making it hotter than the hot reservoir. The hot working body passes heat to the hot reservoir, but still remains hotter than the cold reservoir. Then, by allowing it to expand without passing heat to another body, the working body is made colder than the cold reservoir. It can now accept heat transfer from the cold reservoir to start another cycle.

The device has transported energy from a colder to a hotter reservoir, but this is not regarded as by an inanimate agency; rather, it is regarded as by the harnessing of work . This is because work is supplied from the work reservoir, not just by a simple thermodynamic process, but by a cycle of thermodynamic operations and processes, which may be regarded as directed by an animate or harnessing agency. Accordingly, the cycle is still in accord with the second law of thermodynamics. The 'efficiency' of a heat pump (which exceeds unity) is best when the temperature difference between the hot and cold reservoirs is least.

Functionally, such engines are used in two ways, distinguishing a target reservoir and a resource or surrounding reservoir. A heat pump transfers heat to the hot reservoir as the target from the resource or surrounding reservoir. A refrigerator transfers heat, from the cold reservoir as the target, to the resource or surrounding reservoir. The target reservoir may be regarded as leaking: when the target leaks heat to the surroundings, heat pumping is used; when the target leaks coldness to the surroundings, refrigeration is used. The engines harness work to overcome the leaks.

Macroscopic view

According to Planck, there are three main conceptual approaches to heat. One is the microscopic or kinetic theory approach. The other two are macroscopic approaches. One of the macroscopic approaches is through the law of conservation of energy taken as prior to thermodynamics, with a mechanical analysis of processes, for example in the work of Helmholtz. This mechanical view is taken in this article as currently customary for thermodynamic theory. The other macroscopic approach is the thermodynamic one, which admits heat as a primitive concept, which contributes, by scientific induction to knowledge of the law of conservation of energy. This view is widely taken as the practical one, quantity of heat being measured by calorimetry.

Bailyn also distinguishes the two macroscopic approaches as the mechanical and the thermodynamic. The thermodynamic view was taken by the founders of thermodynamics in the nineteenth century. It regards quantity of energy transferred as heat as a primitive concept coherent with a primitive concept of temperature, measured primarily by calorimetry. A calorimeter is a body in the surroundings of the system, with its own temperature and internal energy; when it is connected to the system by a path for heat transfer, changes in it measure heat transfer. The mechanical view was pioneered by Helmholtz and developed and used in the twentieth century, largely through the influence of Max Born. It regards quantity of heat transferred as heat as a derived concept, defined for closed systems as quantity of heat transferred by mechanisms other than work transfer, the latter being regarded as primitive for thermodynamics, defined by macroscopic mechanics. According to Born, the transfer of internal energy between open systems that accompanies transfer of matter "cannot be reduced to mechanics". It follows that there is no well-founded definition of quantities of energy transferred as heat or as work associated with transfer of matter.

Nevertheless, for the thermodynamical description of non-equilibrium processes, it is desired to consider the effect of a temperature gradient established by the surroundings across the system of interest when there is no physical barrier or wall between system and surroundings, that is to say, when they are open with respect to one another. The impossibility of a mechanical definition in terms of work for this circumstance does not alter the physical fact that a temperature gradient causes a diffusive flux of internal energy, a process that, in the thermodynamic view, might be proposed as a candidate concept for transfer of energy as heat.

Microscopic view

In the kinetic theory, heat is explained in terms of the microscopic motions and interactions of constituent particles, such as electrons, atoms, and molecules. The immediate meaning of the kinetic energy of the constituent particles is not as heat. It is as a component of internal energy.

In microscopic terms, heat is a transfer quantity, and is described by a transport theory, not as steadily localized kinetic energy of particles. Heat transfer arises from temperature gradients or differences, through the diffuse exchange of microscopic kinetic and potential particle energy, by particle collisions and other interactions. An early and vague expression of this was made by Francis Bacon. Precise and detailed versions of it were developed in the nineteenth century.

In statistical mechanics, for a closed system (no transfer of matter), heat is the energy transfer associated with a disordered, microscopic action on the system, associated with jumps in occupation numbers of the energy levels of the system, without change in the values of the energy levels themselves. It is possible for macroscopic thermodynamic work to alter the occupation numbers without change in the values of the system energy levels themselves, but what distinguishes transfer as heat is that the transfer is entirely due to disordered, microscopic action, including radiative transfer. A mathematical definition can be formulated for small increments of quasi-static adiabatic work in terms of the statistical distribution of an ensemble of microstates.

Calorimetry

Quantity of heat transferred can be measured by calorimetry, or determined through calculations based on other quantities.

Calorimetry is the empirical basis of the idea of quantity of heat transferred in a process. The transferred heat is measured by changes in a body of known properties, for example, temperature rise, change in volume or length, or phase change, such as melting of ice.

A calculation of quantity of heat transferred can rely on a hypothetical quantity of energy transferred as adiabatic work and on the first law of thermodynamics. Such calculation is the primary approach of many theoretical studies of quantity of heat transferred.

Engineering

The discipline of heat transfer, typically considered an aspect of mechanical engineering and chemical engineering, deals with specific applied methods by which thermal energy in a system is generated, or converted, or transferred to another system. Although the definition of heat implicitly means the transfer of energy, the term heat transfer encompasses this traditional usage in many engineering disciplines and laymen language.

Heat transfer is generally described as including the mechanisms of heat conduction, heat convection, thermal radiation, but may include mass transfer and heat in processes of phase changes.

Convection may be described as the combined effects of conduction and fluid flow. From the thermodynamic point of view, heat flows into a fluid by diffusion to increase its energy, the fluid then transfers (advects) this increased internal energy (not heat) from one location to another, and this is then followed by a second thermal interaction which transfers heat to a second body or system, again by diffusion. This entire process is often regarded as an additional mechanism of heat transfer, although technically, "heat transfer" and thus heating and cooling occurs only on either end of such a conductive flow, but not as a result of flow. Thus, conduction can be said to "transfer" heat only as a net result of the process, but may not do so at every time within the complicated convective process.

Latent and sensible heat

In an 1847 lecture entitled On Matter, Living Force, and Heat, James Prescott Joule characterized the terms latent heat and sensible heat as components of heat each affecting distinct physical phenomena, namely the potential and kinetic energy of particles, respectively.

He described latent energy as the energy possessed via a distancing of particles where attraction was over a greater distance, i.e. a form of potential energy, and the sensible heat as an energy involving the motion of particles, i.e. kinetic energy.

Latent heat is the heat released or absorbed by a chemical substance or a thermodynamic system during a change of state that occurs without a change in temperature. Such a process may be a phase transition, such as the melting of ice or the boiling of water.

Heat capacity

Heat capacity is a measurable physical quantity equal to the ratio of the heat added to an object to the resulting temperature change. The molar heat capacity is the heat capacity per unit amount (SI unit: mole) of a pure substance, and the specific heat capacity, often called simply specific heat, is the heat capacity per unit mass of a material. Heat capacity is a physical property of a substance, which means that it depends on the state and properties of the substance under consideration.

The specific heats of monatomic gases, such as helium, are nearly constant with temperature. Diatomic gases such as hydrogen display some temperature dependence, and triatomic gases (e.g., carbon dioxide) still more.

Before the development of the laws of thermodynamics, heat was measured by changes in the states of the participating bodies.

Some general rules, with important exceptions, can be stated as follows.

In general, most bodies expand on heating. In this circumstance, heating a body at a constant volume increases the pressure it exerts on its constraining walls, while heating at a constant pressure increases its volume.

Beyond this, most substances have three ordinarily recognized states of matter, solid, liquid, and gas. Some can also exist in a plasma. Many have further, more finely differentiated, states of matter, such as glass and liquid crystal. In many cases, at fixed temperature and pressure, a substance can exist in several distinct states of matter in what might be viewed as the same 'body'. For example, ice may float in a glass of water. Then the ice and the water are said to constitute two phases within the 'body'. Definite rules are known, telling how distinct phases may coexist in a 'body'. Mostly, at a fixed pressure, there is a definite temperature at which heating causes a solid to melt or evaporate, and a definite temperature at which heating causes a liquid to evaporate. In such cases, cooling has the reverse effects.

All of these, the commonest cases, fit with a rule that heating can be measured by changes of state of a body. Such cases supply what are called thermometric bodies, that allow the definition of empirical temperatures. Before 1848, all temperatures were defined in this way. There was thus a tight link, apparently logically determined, between heat and temperature, though they were recognized as conceptually thoroughly distinct, especially by Joseph Black in the later eighteenth century.

"Hotness"

The property of hotness is a concern of thermodynamics that should be defined without reference to the concept of heat. Consideration of hotness leads to the concept of empirical temperature. All physical systems are capable of heating or cooling others. With reference to hotness, the comparative terms hotter and colder are defined by the rule that heat flows from the hotter body to the colder.

If a physical system is inhomogeneous or very rapidly or irregularly changing, for example by turbulence, it may be impossible to characterize it by a temperature, but still there can be transfer of energy as heat between it and another system. If a system has a physical state that is regular enough, and persists long enough to allow it to reach thermal equilibrium with a specified thermometer, then it has a temperature according to that thermometer. An empirical thermometer registers degree of hotness for such a system. Such a temperature is called empirical. For example, Truesdell writes about classical thermodynamics: "At each time, the body is assigned a real number called the temperature. This number is a measure of how hot the body is."

Physical systems that are too turbulent to have temperatures may still differ in hotness. A physical system that passes heat to another physical system is said to be the hotter of the two. More is required for the system to have a thermodynamic temperature. Its behavior must be so regular that its empirical temperature is the same for all suitably calibrated and scaled thermometers, and then its hotness is said to lie on the one-dimensional hotness manifold. This is part of the reason why heat is defined following Carathéodory and Born, solely as occurring other than by work or transfer of matter; temperature is advisedly and deliberately not mentioned in this now widely accepted definition.

This is also the reason that the zeroth law of thermodynamics is stated explicitly. If three physical systems, A, B, and C are each not in their own states of internal thermodynamic equilibrium, it is possible that, with suitable physical connections being made between them, A can heat B and B can heat C and C can heat A. In non-equilibrium situations, cycles of flow are possible. It is the special and uniquely distinguishing characteristic of internal thermodynamic equilibrium that this possibility is not open to thermodynamic systems (as distinguished amongst physical systems) which are in their own states of internal thermodynamic equilibrium; this is the reason why the zeroth law of thermodynamics needs explicit statement. That is to say, the relation 'is not colder than' between general non-equilibrium physical systems is not transitive, whereas, in contrast, the relation 'has no lower a temperature than' between thermodynamic systems in their own states of internal thermodynamic equilibrium is transitive. It follows from this that the relation 'is in thermal equilibrium with' is transitive, which is one way of stating the zeroth law.

Classical thermodynamics

Heat and enthalpy

For a closed system (a system from which no matter can enter or exit), one version of the first law of thermodynamics states that the change in internal energy ΔU of the system is equal to the amount of heat Q supplied to the system minus the amount of thermodynamic work W done by system on its surroundings. The foregoing sign convention for work is used in the present article, but an alternate sign convention, followed by IUPAC, for work, is to consider the work performed on the system by its surroundings as positive. This is the convention adopted by many modern textbooks of physical chemistry, such as those by Peter Atkins and Ira Levine, but many textbooks on physics define work as work done by the system.

Δ

U

=

Q

−

W

.

{\displaystyle \Delta U=Q-W\,.}

This formula can be re-written so as to express a definition of quantity of energy transferred as heat, based purely on the concept of adiabatic work, if it is supposed that ΔU is defined and measured solely by processes of adiabatic work:

Q

=

Δ

U

+

W

.

{\displaystyle Q=\Delta U+W.}

The thermodynamic work done by the system is through mechanisms defined by its thermodynamic state variables, for example, its volume V, not through variables that necessarily involve mechanisms in the surroundings. The latter are such as shaft work, and include isochoric work.

Heat and entropy

In 1856, Rudolf Clausius, referring to closed systems, in which transfers of matter do not occur, defined the second fundamental theorem (the second law of thermodynamics) in the mechanical theory of heat (thermodynamics): "if two transformations which, without necessitating any other permanent change, can mutually replace one another, be called equivalent, then the generations of the quantity of heat Q from work at the temperature T, has the equivalence-value:"

Q

T

.

{\displaystyle {\frac {Q}{T}}.}

In 1865, he came to define the entropy symbolized by S, such that, due to the supply of the amount of heat Q at temperature T the entropy of the system is increased by

In a transfer of energy as heat without work being done, there are changes of entropy in both the surroundings which lose heat and the system which gains it. The increase, ΔS, of entropy in the system may be considered to consist of two parts, an increment, ΔS′ that matches, or 'compensates', the change, −ΔS′, of entropy in the surroundings, and a further increment, ΔS′′ that may be considered to be 'generated' or 'produced' in the system, and is said therefore to be 'uncompensated'. Thus

Δ

S

=

Δ

S

′

+

Δ

S

″

.

{\displaystyle \Delta S=\Delta S'+\Delta S''.}

This may also be written