Temperature

Temperature is a physical quantity that expresses quantitatively the perceptions of hotness and coldness. Temperature is measured with a thermometer.

Thermometers are calibrated in various temperature scales that historically have relied on various reference points and thermometric substances for definition. The most common scales are the Celsius scale with the unit symbol °C (formerly called centigrade), the Fahrenheit scale (°F), and the Kelvin scale (K), the latter being used predominantly for scientific purposes. The kelvin is one of the seven base units in the International System of Units (SI).

Absolute zero, i.e., zero kelvin or −273.15 °C, is the lowest point in the thermodynamic temperature scale. Experimentally, it can be approached very closely but not actually reached, as recognized in the third law of thermodynamics. It would be impossible to extract energy as heat from a body at that temperature.

Temperature is important in all fields of natural science, including physics, chemistry, Earth science, astronomy, medicine, biology, ecology, material science, metallurgy, mechanical engineering and geography as well as most aspects of daily life.

Effects

Many physical processes are related to temperature; some of them are given below:

the physical properties of materials including the phase (solid, liquid, gaseous or plasma), density, solubility, vapor pressure, electrical conductivity, hardness, wear resistance, thermal conductivity, corrosion resistance, strength
the rate and extent to which chemical reactions occur
the amount and properties of thermal radiation emitted from the surface of an object
air temperature affects all living organisms
the speed of sound, which in a gas is proportional to the square root of the absolute temperature

Scales

Main article: Scale of temperature Temperature scales need two values for definition: the point chosen as zero degrees and the magnitudes of the incremental unit of temperature. The Celsius scale (°C) is used for common temperature measurements in most of the world. It is an empirical scale that developed historically, which led to its zero point 0 °C being defined as the freezing point of water, and 100 °C as the boiling point of water, both at atmospheric pressure at sea level. It was called a centigrade scale because of the 100-degree interval. Since the standardization of the kelvin in the International System of Units, it has subsequently been redefined in terms of the equivalent fixing points on the Kelvin scale, so that a temperature increment of one degree Celsius is the same as an increment of one kelvin, though numerically the scales differ by an exact offset of 273.15.

The Fahrenheit scale is in common use in the United States. Water freezes at 32 °F and boils at 212 °F at sea-level atmospheric pressure.

Absolute zero

At the absolute zero of temperature, no energy can be removed from matter as heat, a fact expressed in the third law of thermodynamics. At this temperature, matter contains no macroscopic thermal energy, but still has quantum-mechanical zero-point energy as predicted by the uncertainty principle, although this does not enter into the definition of absolute temperature. Experimentally, absolute zero can be approached only very closely; it can never be reached (the lowest temperature attained by experiment is 38 pK). Theoretically, in a body at a temperature of absolute zero, all classical motion of its particles has ceased and they are at complete rest in this classical sense. The absolute zero, defined as 0 K, is exactly equal to −273.15 °C, or −459.67 °F.

Absolute scales

Referring to the Boltzmann constant, to the Maxwell–Boltzmann distribution, and to the Boltzmann statistical mechanical definition of entropy, as distinct from the Gibbs definition, for independently moving microscopic particles, disregarding interparticle potential energy, by international agreement, a temperature scale is defined and said to be absolute because it is independent of the characteristics of particular thermometric substances and thermometer mechanisms. Apart from the absolute zero, it does not have a reference temperature. It is known as the Kelvin scale, widely used in science and technology. The kelvin (the unit name is spelled with a lower-case 'k') is the unit of temperature in the International System of Units (SI). The temperature of a body in a state of thermodynamic equilibrium is always positive relative to the absolute zero.

Besides the internationally agreed Kelvin scale, there is also a thermodynamic temperature scale, invented by Lord Kelvin, also with its numerical zero at the absolute zero of temperature, but directly relating to purely macroscopic thermodynamic concepts, including the macroscopic entropy, though microscopically referable to the Gibbs statistical mechanical definition of entropy for the canonical ensemble, that takes interparticle potential energy into account, as well as independent particle motion so that it can account for measurements of temperatures near absolute zero. This scale has a reference temperature at the triple point of water, the numerical value of which is defined by measurements using the aforementioned internationally agreed Kelvin scale.

Kelvin scale

Many scientific measurements use the Kelvin temperature scale (unit symbol: K), named in honor of the physicist who first defined it. It is an absolute scale. Its numerical zero point, 0 K, is at the absolute zero of temperature. Since May, 2019, the kelvin has been defined through particle kinetic theory, and statistical mechanics. In the International System of Units (SI), the magnitude of the kelvin is defined in terms of the Boltzmann constant, the value of which is defined as fixed by international convention.

Statistical mechanical versus thermodynamic temperature scales[edit]

Since May 2019, the magnitude of the kelvin is defined in relation to microscopic phenomena, characterized in terms of statistical mechanics. Previously, but since 1954, the International System of Units defined a scale and unit for the kelvin as a thermodynamic temperature, by using the reliably reproducible temperature of the triple point of water as a second reference point, the first reference point being 0 K at absolute zero.^{[citation needed]}

Historically, the temperature of the triple point of water was defined as exactly 273.16 K. Today it is an empirically measured quantity. The freezing point of water at sea-level atmospheric pressure occurs at very close to 273.15 K (0 °C).

Classification of scales[edit]

There are various kinds of temperature scale. It may be convenient to classify them as empirically and theoretically based. Empirical temperature scales are historically older, while theoretically based scales arose in the middle of the nineteenth century.

Empirical scales[edit]

Empirically based temperature scales rely directly on measurements of simple macroscopic physical properties of materials. For example, the length of a column of mercury, confined in a glass-walled capillary tube, is dependent largely on temperature and is the basis of the very useful mercury-in-glass thermometer. Such scales are valid only within convenient ranges of temperature. For example, above the boiling point of mercury, a mercury-in-glass thermometer is impracticable. Most materials expand with temperature increase, but some materials, such as water, contract with temperature increase over some specific range, and then they are hardly useful as thermometric materials. A material is of no use as a thermometer near one of its phase-change temperatures, for example, its boiling-point.

In spite of these limitations, most generally used practical thermometers are of the empirically based kind. Especially, it was used for calorimetry, which contributed greatly to the discovery of thermodynamics. Nevertheless, empirical thermometry has serious drawbacks when judged as a basis for theoretical physics. Empirically based thermometers, beyond their base as simple direct measurements of ordinary physical properties of thermometric materials, can be re-calibrated, by use of theoretical physical reasoning, and this can extend their range of adequacy.

Theoretical scales[edit]

Theoretically based temperature scales are based directly on theoretical arguments, especially those of kinetic theory and thermodynamics. They are more or less ideally realized in practically feasible physical devices and materials. Theoretically based temperature scales are used to provide calibrating standards for practical empirically based thermometers.

Microscopic statistical mechanical scale[edit]

In physics, the internationally agreed conventional temperature scale is called the Kelvin scale. It is calibrated through the internationally agreed and prescribed value of the Boltzmann constant, referring to motions of microscopic particles, such as atoms, molecules, and electrons, constituent in the body whose temperature is to be measured. In contrast with the thermodynamic temperature scale invented by Kelvin, the presently conventional Kelvin temperature is not defined through comparison with the temperature of a reference state of a standard body, nor in terms of macroscopic thermodynamics.

Apart from the absolute zero of temperature, the Kelvin temperature of a body in a state of internal thermodynamic equilibrium is defined by measurements of suitably chosen of its physical properties, such as have precisely known theoretical explanations in terms of the Boltzmann constant.^{[citation needed]} That constant refers to chosen kinds of motion of microscopic particles in the constitution of the body. In those kinds of motion, the particles move individually, without mutual interaction. Such motions are typically interrupted by inter-particle collisions, but for temperature measurement, the motions are chosen so that, between collisions, the non-interactive segments of their trajectories are known to be accessible to accurate measurement. For this purpose, interparticle potential energy is disregarded.

In an ideal gas, and in other theoretically understood bodies, the Kelvin temperature is defined to be proportional to the average kinetic energy of non-interactively moving microscopic particles, which can be measured by suitable techniques. The proportionality constant is a simple multiple of the Boltzmann constant. If molecules, atoms, or electrons, are emitted from material and their velocities are measured, the spectrum of their velocities often nearly obeys a theoretical law called the Maxwell–Boltzmann distribution, which gives a well-founded measurement of temperatures for which the law holds. There have not yet been successful experiments of this same kind that directly use the Fermi–Dirac distribution for thermometry, but perhaps that will be achieved in the future.

The speed of sound in a gas can be calculated theoretically from the molecular character of the gas, from its temperature and pressure, and from the value of the Boltzmann constant. For a gas of known molecular character and pressure, this provides a relation between temperature and the Boltzmann constant. Those quantities can be known or measured more precisely than can the thermodynamic variables that define the state of a sample of water at its triple point. Consequently, taking the value of the Boltzmann constant as a primarily defined reference of exactly defined value, a measurement of the speed of sound can provide a more precise measurement of the temperature of the gas.

Measurement of the spectrum of electromagnetic radiation from an ideal three-dimensional black body can provide an accurate temperature measurement because the frequency of maximum spectral radiance of black-body radiation is directly proportional to the temperature of the black body; this is known as Wien's displacement law and has a theoretical explanation in Planck's law and the Bose–Einstein law.

Measurement of the spectrum of noise-power produced by an electrical resistor can also provide accurate temperature measurement. The resistor has two terminals and is in effect a one-dimensional body. The Bose-Einstein law for this case indicates that the noise-power is directly proportional to the temperature of the resistor and to the value of its resistance and to the noise bandwidth. In a given frequency band, the noise-power has equal contributions from every frequency and is called Johnson noise. If the value of the resistance is known then the temperature can be found.

Macroscopic thermodynamic scale[edit]

Historically, till May 2019, the definition of the Kelvin scale was that invented by Kelvin, based on a ratio of quantities of energy in processes in an ideal Carnot engine, entirely in terms of macroscopic thermodynamics.^{[citation needed]} That Carnot engine was to work between two temperatures, that of the body whose temperature was to be measured, and a reference, that of a body at the temperature of the triple point of water. Then the reference temperature, that of the triple point, was defined to be exactly 273.16 K. Since May 2019, that value has not been fixed by definition but is to be measured through microscopic phenomena, involving the Boltzmann constant, as described above. The microscopic statistical mechanical definition does not have a reference temperature.

Ideal gas[edit]

A material on which a macroscopically defined temperature scale may be based is the ideal gas. The pressure exerted by a fixed volume and mass of an ideal gas is directly proportional to its temperature. Some natural gases show so nearly ideal properties over suitable temperature range that they can be used for thermometry; this was important during the development of thermodynamics and is still of practical importance today. The ideal gas thermometer is, however, not theoretically perfect for thermodynamics. This is because the entropy of an ideal gas at its absolute zero of temperature is not a positive semi-definite quantity, which puts the gas in violation of the third law of thermodynamics. In contrast to real materials, the ideal gas does not liquefy or solidify, no matter how cold it is. Alternatively thinking, the ideal gas law, refers to the limit of infinitely high temperature and zero pressure; these conditions guarantee non-interactive motions of the constituent molecules.

Kinetic theory approach

The magnitude of the kelvin is now defined in terms of kinetic theory, derived from the value of the Boltzmann constant.

Kinetic theory provides a microscopic account of temperature for some bodies of material, especially gases, based on macroscopic systems' being composed of many microscopic particles, such as molecules and ions of various species, the particles of a species being all alike. It explains macroscopic phenomena through the classical mechanics of the microscopic particles. The equipartition theorem of kinetic theory asserts that each classical degree of freedom of a freely moving particle has an average kinetic energy of k_BT/2 where k_B denotes the Boltzmann constant.^{[citation needed]} The translational motion of the particle has three degrees of freedom, so that, except at very low temperatures where quantum effects predominate, the average translational kinetic energy of a freely moving particle in a system with temperature T will be 3k_BT/2.

Molecules, such as oxygen (O₂), have more degrees of freedom than single spherical atoms: they undergo rotational and vibrational motions as well as translations. Heating results in an increase of temperature due to an increase in the average translational kinetic energy of the molecules. Heating will also cause, through equipartitioning, the energy associated with vibrational and rotational modes to increase. Thus a diatomic gas will require more energy input to increase its temperature by a certain amount, i.e. it will have a greater heat capacity than a monatomic gas.

As noted above, the speed of sound in a gas can be calculated from the molecular character of the gas, from its temperature and pressure, and from the value of the Boltzmann constant. Taking the value of the Boltzmann constant as a primarily defined reference of exactly defined value, a measurement of the speed of sound can provide a more precise measurement of the temperature of the gas.

It is possible to measure the average kinetic energy of constituent microscopic particles if they are allowed to escape from the bulk of the system, through a small hole in the containing wall. The spectrum of velocities has to be measured, and the average calculated from that. It is not necessarily the case that the particles that escape and are measured have the same velocity distribution as the particles that remain in the bulk of the system, but sometimes a good sample is possible.

Thermodynamic approach[edit]

Temperature is one of the principal quantities in the study of thermodynamics. Formerly, the magnitude of the kelvin was defined in thermodynamic terms, but nowadays, as mentioned above, it is defined in terms of kinetic theory.

The thermodynamic temperature is said to be absolute for two reasons. One is that its formal character is independent of the properties of particular materials. The other reason is that its zero is, in a sense, absolute, in that it indicates absence of microscopic classical motion of the constituent particles of matter, so that they have a limiting specific heat of zero for zero temperature, according to the third law of thermodynamics. Nevertheless, a thermodynamic temperature does in fact have a definite numerical value that has been arbitrarily chosen by tradition and is dependent on the property of particular materials; it is simply less arbitrary than relative "degrees" scales such as Celsius and Fahrenheit. Being an absolute scale with one fixed point (zero), there is only one degree of freedom left to arbitrary choice, rather than two as in relative scales. For the Kelvin scale since May 2019, by international convention, the choice has been made to use knowledge of modes of operation of various thermometric devices, relying on microscopic kinetic theories about molecular motion. The numerical scale is settled by a conventional definition of the value of the Boltzmann constant, which relates macroscopic temperature to average microscopic kinetic energy of particles such as molecules. Its numerical value is arbitrary, and an alternate, less widely used absolute temperature scale exists called the Rankine scale, made to be aligned with the Fahrenheit scale as Kelvin is with Celsius.

The thermodynamic definition of temperature is due to Kelvin. It is framed in terms of an idealized device called a Carnot engine, imagined to run in a fictive continuous cycle of successive processes that traverse a cycle of states of its working body. The engine takes in a quantity of heat Q₁ from a hot reservoir and passes out a lesser quantity of waste heat Q₂ < 0 to a cold reservoir. The net heat energy absorbed by the working body is passed, as thermodynamic work, to a work reservoir, and is considered to be the output of the engine. The cycle is imagined to run so slowly that at each point of the cycle the working body is in a state of thermodynamic equilibrium. The successive processes of the cycle are thus imagined to run reversibly with no entropy production. Then the quantity of entropy taken in from the hot reservoir when the working body is heated is equal to that passed to the cold reservoir when the working body is cooled. Then the absolute or thermodynamic temperatures, T₁ and T₂, of the reservoirs are defined such that

{\frac {T_{1}}{T_{2}}}=-{\frac {Q_{1}}{Q_{2}}}.

(1)

The zeroth law of thermodynamics allows this definition to be used to measure the absolute or thermodynamic temperature of an arbitrary body of interest, by making the other heat reservoir have the same temperature as the body of interest.

Kelvin's original work postulating absolute temperature was published in 1848. It was based on the work of Carnot, before the formulation of the first law of thermodynamics. Carnot had no sound understanding of heat and no specific concept of entropy. He wrote of 'caloric' and said that all the caloric that passed from the hot reservoir was passed into the cold reservoir. Kelvin wrote in his 1848 paper that his scale was absolute in the sense that it was defined "independently of the properties of any particular kind of matter". His definitive publication, which sets out the definition just stated, was printed in 1853, a paper read in 1851.^[1]^[2]^[3]^[4]

Numerical details were formerly settled by making one of the heat reservoirs a cell at the triple point of water, which was defined to have an absolute temperature of 273.16 K.^[5] Nowadays, the numerical value is instead obtained from measurement through the microscopic statistical mechanical international definition, as above.

Intensive variability

In thermodynamic terms, temperature is an intensive variable because it is equal to a differential coefficient of one extensive variable with respect to another, for a given body. It thus has the dimensions of a ratio of two extensive variables. In thermodynamics, two bodies are often considered as connected by contact with a common wall, which has some specific permeability properties. Such specific permeability can be referred to a specific intensive variable. An example is a diathermic wall that is permeable only to heat; the intensive variable for this case is temperature. When the two bodies have been connected through the specifically permeable wall for a very long time, and have settled to a permanent steady state, the relevant intensive variables are equal in the two bodies; for a diathermal wall, this statement is sometimes called the zeroth law of thermodynamics.^[6]^[7]^[8]

In particular, when the body is described by stating its internal energy <span class="texhtml " {{#if: $U$ , an extensive variable, as a function of its entropy <span class="texhtml " {{#if: $S$ , also an extensive variable, and other state variables <span class="texhtml " {{#if: $V, N$ , with <span class="texhtml " {{#if: $U = U (S, V, N$ ), then the temperature is equal to the partial derivative of the internal energy with respect to the entropy:^[7]^[8]^[9]

T=\left({\frac {\partial U}{\partial S}}\right)_{V,N}.

(2)

Likewise, when the body is described by stating its entropy <span class="texhtml " {{#if: $S$ as a function of its internal energy <span class="texhtml " {{#if: $U$ , and other state variables <span class="texhtml " {{#if: $V, N$ , with <span class="texhtml " {{#if: $S = S (U, V, N)$ , then the reciprocal of the temperature is equal to the partial derivative of the entropy with respect to the internal energy:^[7]^[9]^[10]

{\frac {1}{T}}=\left({\frac {\partial S}{\partial U}}\right)_{V,N}.

(3)

The above definition, equation (1), of the absolute temperature, is due to Kelvin. It refers to systems closed to the transfer of matter and has a special emphasis on directly experimental procedures. A presentation of thermodynamics by Gibbs starts at a more abstract level and deals with systems open to the transfer of matter; in this development of thermodynamics, the equations (2) and (3) above are actually alternative definitions of temperature.^[11]

Local thermodynamic equilibrium

Real-world bodies are often not in thermodynamic equilibrium and not homogeneous. For the study by methods of classical irreversible thermodynamics, a body is usually spatially and temporally divided conceptually into 'cells' of small size. If classical thermodynamic equilibrium conditions for matter are fulfilled to good approximation in such a 'cell', then it is homogeneous and a temperature exists for it. If this is so for every 'cell' of the body, then local thermodynamic equilibrium is said to prevail throughout the body.^[12]^[13]^[14]^[15]^[16]

It makes good sense, for example, to say of the extensive variable <span class="texhtml " {{#if: $U$ , or of the extensive variable <span class="texhtml " {{#if: $S$ , that it has a density per unit volume or a quantity per unit mass of the system, but it makes no sense to speak of the density of temperature per unit volume or quantity of temperature per unit mass of the system. On the other hand, it makes no sense to speak of the internal energy at a point, while when local thermodynamic equilibrium prevails, it makes good sense to speak of the temperature at a point. Consequently, the temperature can vary from point to point in a medium that is not in global thermodynamic equilibrium, but in which there is local thermodynamic equilibrium.

Thus, when local thermodynamic equilibrium prevails in a body, the temperature can be regarded as a spatially varying local property in that body, and this is because the temperature is an intensive variable.

↑ Thomson, W. (Lord Kelvin) (1848).
↑ Thomson, W. (Lord Kelvin) (1851).
↑ Partington, J.R. (1949), pp. 175–177.
↑ Roberts, J.K., Miller, A.R. (1928/1960), pp. 321–322.
↑ Quinn, T.J. (1983). Temperature, Academic Press, London, ISBN 0-12-569680-9, pp. 160–162.
↑ Tisza, L. (1966). Generalized Thermodynamics, M.I.T. Press, Cambridge MA, pp. 47, 57.
↑ ^7.0 ^7.1 ^7.2 Münster, A. (1970), Classical Thermodynamics, translated by E.S. Halberstadt, Wiley–Interscience, London, ISBN 0-471-62430-6, pp. 49, 69.
↑ ^8.0 ^8.1 Bailyn, M. (1994). A Survey of Thermodynamics, American Institute of Physics Press, New York, ISBN 0-88318-797-3, pp. 14–15, 214.
↑ ^9.0 ^9.1 Callen, H.B. (1960/1985), Thermodynamics and an Introduction to Thermostatistics, (first edition 1960), second edition 1985, John Wiley & Sons, New York, ISBN 0-471-86256-8, pp. 146–148.
↑ Kondepudi, D., Prigogine, I. (1998). Modern Thermodynamics. From Heat Engines to Dissipative Structures, John Wiley, Chichester, ISBN 0-471-97394-7, pp. 115–116.
↑ Tisza, L. (1966). Generalized Thermodynamics, M.I.T. Press, Cambridge MA, p. 58.
↑ Milne, E.A. (1929). The effect of collisions on monochromatic radiative equilibrium, Monthly Notices of the Royal Astronomical Society, 88: 493–502.
↑ Gyarmati, I. (1970). Non-equilibrium Thermodynamics. Field Theory and Variational Principles, translated by E. Gyarmati and W.F. Heinz, Springer, Berlin, pp. 63–66.
↑ Glansdorff, P., Prigogine, I., (1971). Thermodynamic Theory of Structure, Stability and Fluctuations, Wiley, London, ISBN 0-471-30280-5, pp. 14–16.
↑ Bailyn, M. (1994). A Survey of Thermodynamics, American Institute of Physics Press, New York, ISBN 0-88318-797-3, pp. 133–135.
↑ Callen, H.B. (1960/1985), Thermodynamics and an Introduction to Thermostatistics, (first edition 1960), second edition 1985, John Wiley & Sons, New York, ISBN 0-471-86256-8, pp. 309–310.

[1] Thomson, W. (Lord Kelvin) (1848).

[2] Thomson, W. (Lord Kelvin) (1851).

[3] Partington, J.R. (1949), pp. 175–177.

[4] Roberts, J.K., Miller, A.R. (1928/1960), pp. 321–322.

[5] Quinn, T.J. (1983). Temperature, Academic Press, London, ISBN 0-12-569680-9, pp. 160–162.

[6] Tisza, L. (1966). Generalized Thermodynamics, M.I.T. Press, Cambridge MA, pp. 47, 57.

[Munster_49_69-7] 7.0 ^7.1 ^7.2 Münster, A. (1970), Classical Thermodynamics, translated by E.S. Halberstadt, Wiley–Interscience, London, ISBN 0-471-62430-6, pp. 49, 69.

[Bailyn_14_214-8] 8.0 ^8.1 Bailyn, M. (1994). A Survey of Thermodynamics, American Institute of Physics Press, New York, ISBN 0-88318-797-3, pp. 14–15, 214.

[Callen_146–148-9] 9.0 ^9.1 Callen, H.B. (1960/1985), Thermodynamics and an Introduction to Thermostatistics, (first edition 1960), second edition 1985, John Wiley & Sons, New York, ISBN 0-471-86256-8, pp. 146–148.

[10] Kondepudi, D., Prigogine, I. (1998). Modern Thermodynamics. From Heat Engines to Dissipative Structures, John Wiley, Chichester, ISBN 0-471-97394-7, pp. 115–116.

[11] Tisza, L. (1966). Generalized Thermodynamics, M.I.T. Press, Cambridge MA, p. 58.

[12] Milne, E.A. (1929). The effect of collisions on monochromatic radiative equilibrium, Monthly Notices of the Royal Astronomical Society, 88: 493–502.

[13] Gyarmati, I. (1970). Non-equilibrium Thermodynamics. Field Theory and Variational Principles, translated by E. Gyarmati and W.F. Heinz, Springer, Berlin, pp. 63–66.

[14] Glansdorff, P., Prigogine, I., (1971). Thermodynamic Theory of Structure, Stability and Fluctuations, Wiley, London, ISBN 0-471-30280-5, pp. 14–16.

[15] Bailyn, M. (1994). A Survey of Thermodynamics, American Institute of Physics Press, New York, ISBN 0-88318-797-3, pp. 133–135.

[16] Callen, H.B. (1960/1985), Thermodynamics and an Introduction to Thermostatistics, (first edition 1960), second edition 1985, John Wiley & Sons, New York, ISBN 0-471-86256-8, pp. 309–310.

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