The Boltzmann constant ( or ) is the
proportionality factor that relates the average relative
kinetic energy
In physics, the kinetic energy of an object is the energy that it possesses due to its motion.
It is defined as the work needed to accelerate a body of a given mass from rest to its stated velocity. Having gained this energy during its acc ...
of
particle
In the physical sciences, a particle (or corpuscule in older texts) is a small localized object which can be described by several physical or chemical properties, such as volume, density, or mass.
They vary greatly in size or quantity, from ...
s in a
gas
Gas is one of the four fundamental states of matter (the others being solid, liquid, and plasma).
A pure gas may be made up of individual atoms (e.g. a noble gas like neon), elemental molecules made from one type of atom (e.g. oxygen), or ...
with the
thermodynamic temperature
Thermodynamic temperature is a quantity defined in thermodynamics as distinct from kinetic theory or statistical mechanics.
Historically, thermodynamic temperature was defined by Kelvin in terms of a macroscopic relation between thermodynamic ...
of the gas.
It occurs in the definitions of the
kelvin
The kelvin, symbol K, is the primary unit of temperature in the International System of Units (SI), used alongside its prefixed forms and the degree Celsius. It is named after the Belfast-born and University of Glasgow-based engineer and phy ...
and the
gas constant
The molar gas constant (also known as the gas constant, universal gas constant, or ideal gas constant) is denoted by the symbol or . It is the molar equivalent to the Boltzmann constant, expressed in units of energy per temperature increment per ...
, and in
Planck's law of
black-body radiation and
Boltzmann's entropy formula
In statistical mechanics, Boltzmann's equation (also known as the Boltzmann–Planck equation) is a probability equation relating the entropy S, also written as S_\mathrm, of an ideal gas to the multiplicity (commonly denoted as \Omega or W), the ...
, and is used in calculating
thermal noise
A thermal column (or thermal) is a rising mass of buoyant air, a convective current in the atmosphere, that transfers heat energy vertically. Thermals are created by the uneven heating of Earth's surface from solar radiation, and are an example ...
in
resistors. The Boltzmann constant has
dimensions
In physics and mathematics, the dimension of a mathematical space (or object) is informally defined as the minimum number of coordinates needed to specify any point within it. Thus, a line has a dimension of one (1D) because only one coordin ...
of energy divided by temperature, the same as
entropy. It is named after the Austrian scientist
Ludwig Boltzmann
Ludwig Eduard Boltzmann (; 20 February 1844 – 5 September 1906) was an Austrian physicist and philosopher. His greatest achievements were the development of statistical mechanics, and the statistical explanation of the second law of ther ...
.
As part of the
2019 redefinition of SI base units
In 2019, four of the seven SI base units specified in the International System of Quantities were redefined in terms of natural physical constants, rather than human artifacts such as the standard kilogram.
Effective 20 May 2019, the 144 ...
, the Boltzmann constant is one of the seven "
defining constants" that have been given exact definitions. They are used in various combinations to define the seven SI base units. The Boltzmann constant is defined to be exactly .
Roles of the Boltzmann constant
Macroscopically, the
ideal gas law states that, for an
ideal gas
An ideal gas is a theoretical gas composed of many randomly moving point particles that are not subject to interparticle interactions. The ideal gas concept is useful because it obeys the ideal gas law, a simplified equation of state, and is a ...
, the product of
pressure
Pressure (symbol: ''p'' or ''P'') is the force applied perpendicular to the surface of an object per unit area over which that force is distributed. Gauge pressure (also spelled ''gage'' pressure)The preferred spelling varies by country and e ...
and
volume
Volume is a measure of occupied three-dimensional space. It is often quantified numerically using SI derived units (such as the cubic metre and litre) or by various imperial or US customary units (such as the gallon, quart, cubic inch). Th ...
is proportional to the product of
amount of substance (in
moles Moles can refer to:
* Moles de Xert, a mountain range in the Baix Maestrat comarca, Valencian Community, Spain
* The Moles (Australian band)
*The Moles, alter ego of Scottish band Simon Dupree and the Big Sound
People
*Abraham Moles, French engin ...
) and
absolute temperature :
:
where is the
molar gas constant (). Introducing the Boltzmann constant as the gas constant per molecule transforms the ideal gas law into an alternative form:
:
where is the
number of molecules of gas.
Role in the equipartition of energy
Given a
thermodynamic system at an
absolute temperature , the average thermal energy carried by each microscopic degree of freedom in the system is (i.e., about , or , at room temperature). This is generally true only for classical systems with a
large number of particles, and in which quantum effects are negligible.
In
classical statistical mechanics, this average is predicted to hold exactly for homogeneous
ideal gas
An ideal gas is a theoretical gas composed of many randomly moving point particles that are not subject to interparticle interactions. The ideal gas concept is useful because it obeys the ideal gas law, a simplified equation of state, and is a ...
es. Monatomic ideal gases (the six noble gases) possess three
degrees of freedom per atom, corresponding to the three spatial directions. According to the equipartition of energy this means that there is a thermal energy of per atom. This corresponds very well with experimental data. The thermal energy can be used to calculate the
root-mean-square speed of the atoms, which turns out to be inversely proportional to the square root of the
atomic mass. The root mean square speeds found at room temperature accurately reflect this, ranging from for
helium
Helium (from el, ἥλιος, helios, lit=sun) is a chemical element with the symbol He and atomic number 2. It is a colorless, odorless, tasteless, non-toxic, inert, monatomic gas and the first in the noble gas group in the periodic table. ...
, down to for
xenon
Xenon is a chemical element with the symbol Xe and atomic number 54. It is a dense, colorless, odorless noble gas found in Earth's atmosphere in trace amounts. Although generally unreactive, it can undergo a few chemical reactions such as the ...
.
Kinetic theory gives the average pressure for an ideal gas as
:
Combination with the ideal gas law
:
shows that the average translational kinetic energy is
:
Considering that the translational motion velocity vector has three degrees of freedom (one for each dimension) gives the average energy per degree of freedom equal to one third of that, i.e. .
The ideal gas equation is also obeyed closely by molecular gases; but the form for the heat capacity is more complicated, because the molecules possess additional internal degrees of freedom, as well as the three degrees of freedom for movement of the molecule as a whole. Diatomic gases, for example, possess a total of six degrees of simple freedom per molecule that are related to atomic motion (three translational, two rotational, and one vibrational). At lower temperatures, not all these degrees of freedom may fully participate in the gas heat capacity, due to quantum mechanical limits on the availability of excited states at the relevant thermal energy per molecule.
Role in Boltzmann factors
More generally, systems in equilibrium at temperature have probability of occupying a state with energy weighted by the corresponding
Boltzmann factor
Factor, a Latin word meaning "who/which acts", may refer to:
Commerce
* Factor (agent), a person who acts for, notably a mercantile and colonial agent
* Factor (Scotland), a person or firm managing a Scottish estate
* Factors of production, suc ...
:
:
where is the
partition function. Again, it is the energy-like quantity that takes central importance.
Consequences of this include (in addition to the results for ideal gases above) the
Arrhenius equation in
chemical kinetics.
Role in the statistical definition of entropy
In statistical mechanics, the
entropy of an
isolated system at
thermodynamic equilibrium is defined as the
natural logarithm of , the number of distinct microscopic states available to the system given the macroscopic constraints (such as a fixed total energy ):
:
This equation, which relates the microscopic details, or microstates, of the system (via ) to its macroscopic state (via the entropy ), is the central idea of statistical mechanics. Such is its importance that it is inscribed on Boltzmann's tombstone.
The constant of proportionality serves to make the statistical mechanical entropy equal to the classical thermodynamic entropy of Clausius:
:
One could choose instead a rescaled
dimensionless
A dimensionless quantity (also known as a bare quantity, pure quantity, or scalar quantity as well as quantity of dimension one) is a quantity to which no physical dimension is assigned, with a corresponding SI unit of measurement of one (or 1) ...
entropy in microscopic terms such that
:
This is a more natural form and this rescaled entropy exactly corresponds to Shannon's subsequent
information entropy
In information theory, the entropy of a random variable is the average level of "information", "surprise", or "uncertainty" inherent to the variable's possible outcomes. Given a discrete random variable X, which takes values in the alphabet \ ...
.
The characteristic energy is thus the energy required to increase the rescaled entropy by one
nat.
The thermal voltage
In
semiconductors, the
Shockley diode equation
The ''Shockley diode equation'' or the ''diode law'', named after transistor co-inventor William Shockley of Bell Telephone Laboratories, gives the I–V (current-voltage) characteristic of an idealized diode in either forward or reverse bias (appl ...
—the relationship between the flow of
electric current and the
electrostatic potential across a
p–n junction—depends on a characteristic voltage called the ''thermal voltage'', denoted by . The thermal voltage depends on absolute temperature as
where is the magnitude of the
electrical charge on the electron with a value Equivalently,
At
room temperature , is approximately which can be derived by plugging in the values as follows:
At the
standard state temperature of , it is approximately . The thermal voltage is also important in plasmas and electrolyte solutions (e.g. the
Nernst equation
In electrochemistry, the Nernst equation is a chemical thermodynamical relationship that permits the calculation of the reduction potential of a reaction ( half-cell or full cell reaction) from the standard electrode potential, absolute tempe ...
); in both cases it provides a measure of how much the spatial distribution of electrons or ions is affected by a boundary held at a fixed voltage.
History
The Boltzmann constant is named after its 19th century Austrian discoverer,
Ludwig Boltzmann
Ludwig Eduard Boltzmann (; 20 February 1844 – 5 September 1906) was an Austrian physicist and philosopher. His greatest achievements were the development of statistical mechanics, and the statistical explanation of the second law of ther ...
. Although Boltzmann first linked entropy and probability in 1877, the relation was never expressed with a specific constant until
Max Planck
Max Karl Ernst Ludwig Planck (, ; 23 April 1858 – 4 October 1947) was a German theoretical physicist whose discovery of energy quanta won him the Nobel Prize in Physics in 1918.
Planck made many substantial contributions to theoretical p ...
first introduced , and gave a more precise value for it (, about 2.5% lower than today's figure), in his derivation of the
law of black-body radiation in 1900–1901.
[. English translation: ] Before 1900, equations involving Boltzmann factors were not written using the energies per molecule and the Boltzmann constant, but rather using a form of the
gas constant
The molar gas constant (also known as the gas constant, universal gas constant, or ideal gas constant) is denoted by the symbol or . It is the molar equivalent to the Boltzmann constant, expressed in units of energy per temperature increment per ...
, and macroscopic energies for macroscopic quantities of the substance. The iconic terse form of the equation on Boltzmann's tombstone is in fact due to Planck, not Boltzmann. Planck actually introduced it in the same work as his
eponymous .
In 1920, Planck wrote in his
Nobel Prize
The Nobel Prizes ( ; sv, Nobelpriset ; no, Nobelprisen ) are five separate prizes that, according to Alfred Nobel's will of 1895, are awarded to "those who, during the preceding year, have conferred the greatest benefit to humankind." Alfr ...
lecture:
This "peculiar state of affairs" is illustrated by reference to one of the great scientific debates of the time. There was considerable disagreement in the second half of the nineteenth century as to whether atoms and molecules were real or whether they were simply a
heuristic tool for solving problems. There was no agreement whether ''chemical'' molecules, as measured by
atomic weight
Relative atomic mass (symbol: ''A''; sometimes abbreviated RAM or r.a.m.), also known by the deprecated synonym atomic weight, is a dimensionless physical quantity defined as the ratio of the average mass of atoms of a chemical element in a giv ...
s, were the same as ''physical'' molecules, as measured by
kinetic theory. Planck's 1920 lecture continued:
In versions of
SI prior to the
2019 redefinition of the SI base units
In 2019, four of the seven SI base units specified in the International System of Quantities were redefined in terms of natural physical constants, rather than human artifacts such as the standard kilogram.
Effective 20 May 2019, the 144th ...
, the Boltzmann constant was a measured quantity rather than a fixed value. Its exact definition also varied over the years due to redefinitions of the kelvin (see ) and other SI base units (see ).
In 2017, the most accurate measures of the Boltzmann constant were obtained by acoustic gas thermometry, which determines the speed of sound of a monatomic gas in a triaxial ellipsoid chamber using microwave and acoustic resonances. This decade-long effort was undertaken with different techniques by several laboratories; it is one of the cornerstones of the 2019 redefinition of SI base units. Based on these measurements, the
CODATA recommended to be the final fixed value of the Boltzmann constant to be used for the
International System of Units.
Value in different units
Since is a
proportionality factor between temperature and energy, its numerical value depends on the choice of units for energy and temperature. The small numerical value of the Boltzmann constant in
SI units means a change in temperature by
1 K only changes a particle's energy by a small amount. A change of is defined to be the same as a change of . The characteristic energy is a term encountered in many physical relationships.
The Boltzmann constant sets up a relationship between wavelength and temperature (dividing ''hc''/''k'' by a wavelength gives a temperature) with one micrometer being related to , and also a relationship between voltage and temperature (multiplying the voltage by ''k'' in units of eV/K) with one volt being related to . The ratio of these two temperatures, / ≈ 1.239842, is the numerical value of ''hc'' in units of eV⋅μm.
Natural units
The Boltzmann constant provides a mapping from this characteristic microscopic energy to the macroscopic temperature scale . In fundamental physics this mapping is often simplified by using the
natural units
In physics, natural units are physical units of measurement in which only universal physical constants are used as defining constants, such that each of these constants acts as a coherent unit of a quantity. For example, the elementary charge ma ...
of setting to unity. This convention means that temperature and energy quantities have the same
dimensions
In physics and mathematics, the dimension of a mathematical space (or object) is informally defined as the minimum number of coordinates needed to specify any point within it. Thus, a line has a dimension of one (1D) because only one coordin ...
.
[ In particular the SI unit kelvin becomes superfluous, being defined in terms of joules as .] With this convention temperature is always given in units of energy and the Boltzmann constant is not explicitly needed in formulas.
This convention simplifies many physical relationships and formulas. For example, the equipartition formula for the energy associated with each classical degree of freedom ( above) becomes
:
As another example the definition of thermodynamic entropy coincides with the form of information entropy
In information theory, the entropy of a random variable is the average level of "information", "surprise", or "uncertainty" inherent to the variable's possible outcomes. Given a discrete random variable X, which takes values in the alphabet \ ...
:
:
where is the probability of each microstate.
See also
* CODATA 2018
* Thermodynamic beta
In statistical thermodynamics, thermodynamic beta, also known as coldness, is the reciprocal of the thermodynamic temperature of a system:\beta = \frac (where is the temperature and is Boltzmann constant).J. Meixner (1975) "Coldness and Tempe ...
Notes
References
External links
Draft Chapter 2 for SI Brochure, following redefinitions of the base units
(prepared by the Consultative Committee for Units)
{{DEFAULTSORT:Boltzmann Constant
Constant
Fundamental constants
Statistical mechanics
Thermodynamics