Onsager reciprocal relations
Encyclopedia
In thermodynamics
, the Onsager reciprocal relations express the equality of certain ratios between flow
s and force
s in thermodynamic system
s out of equilibrium, but where a notion of local equilibrium exists.
"Reciprocal relations" occur between different pairs of forces and flows in a variety of physical systems. For example, consider fluid systems described in terms of
temperature, matter density, and pressure. In this class of systems, it is known that temperature
differences lead to heat
flows from the warmer to the colder parts of the system; similarly, pressure
differences will lead to matter
flow from high-pressure to low-pressure regions. What is remarkable is the observation that, when both pressure and temperature vary, temperature differences at constant pressure can cause matter flow (as in convection
) and pressure differences at constant temperature can cause heat flow. Perhaps surprisingly, the heat flow per unit of pressure difference and the density
(matter) flow per unit of temperature difference are equal. This equality was shown to be necessary by Lars Onsager
using statistical mechanics
as a consequence of the time reversibility
of microscopic dynamics (microscopic reversibility
). The theory developed by Onsager is much more general than this example and capable of treating more than two thermodynamic forces at once, with the limitation that "the principle of dynamical reversibility does not apply when (external) magnetic fields or Coriolis forces are present", in which case "the reciprocal relations break down".
Though the fluid system is perhaps described most intuitively, the high precision of electrical measurements makes experimental realisations of Onsager's reciprocity easier in systems involving electrical phenomena. In fact, Onsager's 1931 paper refers to thermoelectricity and transport phenomena in electrolytes
as well-known from the 19th century, including "quasi-thermodynamic" theories by Thomson and Helmholtz respectively. Onsager's reciprocity in the thermoelectric effect manifests itself in the equality of the Peltier (heat flow caused by a voltage difference) and Seebeck (electrical current caused by a temperature difference) coefficients of a thermoelectric material. Similarly, the so-called "direct piezoelectric" (electrical current produced by mechanical stress) and "reverse piezoelectric" (deformation produced by a voltage difference) coefficients are equal. For many kinetic systems, like the Boltzmann equation
or chemical kinetics
, the Onsager relations are closely connected to the principle of detailed balance and follow from them in the linear approximation near equilibrium.
For his discovery of these reciprocal relations, Lars Onsager
was awarded the 1968 Nobel Prize in Chemistry
. The presentation speech referred to the three laws of thermodynamics and then added "It can be said that Onsager's reciprocal relations represent a further law making possible a thermodynamic study of irreversible processes." Some authors have even described Onsager's relations as the "Fourth law of thermodynamics".
. In a fluid
system, changes in the energy density
depend on changes in matter density 
and entropy
density
in the following way:
where
is temperature and 
is a combination of pressure and chemical potential
. This formula is simply an expression of the first law of thermodynamics
, namely energy conservation, where the
term represents heat
exchange, and the
term represents (mechanical and chemical) work
done. For non-fluid or more complex systems there will be a different collection of variables describing the work term, but the principle is the same. We can write
The extensive quantities
and 
are conserved
and their flows satisfy continuity equation
s:
and
where
indicates the partial derivative
with respect to time
(that is, the local time-rate of change), and 
indicates the divergence
of the flux densities
.
The above expression of the first law in terms of entropy change defines the conjugate variables
of
and 
, which are 
and 
and are intensive quantities analogous to potential energies
; their gradients of are called thermodynamic forces as they cause flows of the corresponding extensive variables as expressed in the following equations.
In the absence of matter flows, we have a version of Fourier's law
and, in the absence of heat flows, we have a version of Fick's law
where
now indicates the gradient
.
):
and
The Onsager reciprocity relations state the equality of the cross-coefficients
and 
. Proportionality follows from simple dimensional analysis
(i.e., both coefficients are measured in the same units of temperature times mass density).
denote fluctuations from equilibrium values in several thermodynamic quantities, and let 
be the entropy. Then, assuming the fluctuations are small (gaussian
), the probability distribution function
can be expressed as
(where we are using Einstein summation convention and 
is some symmetric matrix)
Using the quasi-stationary equilibrium approximation, that is, assuming that the system is only slightly non-equilibrium, we have
Suppose we define thermodynamic conjugate quantities as
, which can also be expressed as linear functions (for small fluctuations): 
Thus, we can write
where 
are called kinetic coefficients
The principle of symmetry of kinetic coefficients or the Onsager's principle states that
is a symmetric matrix, that is 
and 
of fluctuating quantities 
and 
respectively such that they take given values 
at 
Note that 
Symmetry of fluctuations under time reversal implies that
or, with
, we have 
Differentiating with respect to
and substituting, we get 
Putting
in the above equation, 
It can be easily shown from the definition that
, and hence, we have the required result.
Thermodynamics
Thermodynamics is a physical science that studies the effects on material bodies, and on radiation in regions of space, of transfer of heat and of work done on or by the bodies or radiation...
, the Onsager reciprocal relations express the equality of certain ratios between flow
Flux
In the various subfields of physics, there exist two common usages of the term flux, both with rigorous mathematical frameworks.* In the study of transport phenomena , flux is defined as flow per unit area, where flow is the movement of some quantity per time...
s and force
Force
In physics, a force is any influence that causes an object to undergo a change in speed, a change in direction, or a change in shape. In other words, a force is that which can cause an object with mass to change its velocity , i.e., to accelerate, or which can cause a flexible object to deform...
s in thermodynamic system
Thermodynamic system
A thermodynamic system is a precisely defined macroscopic region of the universe, often called a physical system, that is studied using the principles of thermodynamics....
s out of equilibrium, but where a notion of local equilibrium exists.
"Reciprocal relations" occur between different pairs of forces and flows in a variety of physical systems. For example, consider fluid systems described in terms of
temperature, matter density, and pressure. In this class of systems, it is known that temperature
Temperature
Temperature is a physical property of matter that quantitatively expresses the common notions of hot and cold. Objects of low temperature are cold, while various degrees of higher temperatures are referred to as warm or hot...
differences lead to heat
Heat
In physics and thermodynamics, heat is energy transferred from one body, region, or thermodynamic system to another due to thermal contact or thermal radiation when the systems are at different temperatures. It is often described as one of the fundamental processes of energy transfer between...
flows from the warmer to the colder parts of the system; similarly, pressure
Pressure
Pressure is the force per unit area applied in a direction perpendicular to the surface of an object. Gauge pressure is the pressure relative to the local atmospheric or ambient pressure.- Definition :...
differences will lead to matter
Matter
Matter is a general term for the substance of which all physical objects consist. Typically, matter includes atoms and other particles which have mass. A common way of defining matter is as anything that has mass and occupies volume...
flow from high-pressure to low-pressure regions. What is remarkable is the observation that, when both pressure and temperature vary, temperature differences at constant pressure can cause matter flow (as in convection
Convection
Convection is the movement of molecules within fluids and rheids. It cannot take place in solids, since neither bulk current flows nor significant diffusion can take place in solids....
) and pressure differences at constant temperature can cause heat flow. Perhaps surprisingly, the heat flow per unit of pressure difference and the density
Density
The mass density or density of a material is defined as its mass per unit volume. The symbol most often used for density is ρ . In some cases , density is also defined as its weight per unit volume; although, this quantity is more properly called specific weight...
(matter) flow per unit of temperature difference are equal. This equality was shown to be necessary by Lars Onsager
Lars Onsager
Lars Onsager was a Norwegian-born American physical chemist and theoretical physicist, winner of the 1968 Nobel Prize in Chemistry.He held the Gibbs Professorship of Theoretical Chemistry at Yale University....
using statistical mechanics
Statistical mechanics
Statistical mechanics or statistical thermodynamicsThe terms statistical mechanics and statistical thermodynamics are used interchangeably...
as a consequence of the time reversibility
Time reversibility
Time reversibility is an attribute of some stochastic processes and some deterministic processes.If a stochastic process is time reversible, then it is not possible to determine, given the states at a number of points in time after running the stochastic process, which state came first and which...
of microscopic dynamics (microscopic reversibility
Microscopic reversibility
The principle of Microscopic reversibility in physics and chemistry is twofold:* First, it states that the microscopic detailed dynamics of particles and fields is time-reversible because the microscopic equations of motion are symmetric with respect to inversion in time ;* Second, it relates to...
). The theory developed by Onsager is much more general than this example and capable of treating more than two thermodynamic forces at once, with the limitation that "the principle of dynamical reversibility does not apply when (external) magnetic fields or Coriolis forces are present", in which case "the reciprocal relations break down".
Though the fluid system is perhaps described most intuitively, the high precision of electrical measurements makes experimental realisations of Onsager's reciprocity easier in systems involving electrical phenomena. In fact, Onsager's 1931 paper refers to thermoelectricity and transport phenomena in electrolytes
Electrolysis
In chemistry and manufacturing, electrolysis is a method of using a direct electric current to drive an otherwise non-spontaneous chemical reaction...
as well-known from the 19th century, including "quasi-thermodynamic" theories by Thomson and Helmholtz respectively. Onsager's reciprocity in the thermoelectric effect manifests itself in the equality of the Peltier (heat flow caused by a voltage difference) and Seebeck (electrical current caused by a temperature difference) coefficients of a thermoelectric material. Similarly, the so-called "direct piezoelectric" (electrical current produced by mechanical stress) and "reverse piezoelectric" (deformation produced by a voltage difference) coefficients are equal. For many kinetic systems, like the Boltzmann equation
Boltzmann equation
The Boltzmann equation, also often known as the Boltzmann transport equation, devised by Ludwig Boltzmann, describes the statistical distribution of one particle in rarefied gas...
or chemical kinetics
Chemical kinetics
Chemical kinetics, also known as reaction kinetics, is the study of rates of chemical processes. Chemical kinetics includes investigations of how different experimental conditions can influence the speed of a chemical reaction and yield information about the reaction's mechanism and transition...
, the Onsager relations are closely connected to the principle of detailed balance and follow from them in the linear approximation near equilibrium.
For his discovery of these reciprocal relations, Lars Onsager
Lars Onsager
Lars Onsager was a Norwegian-born American physical chemist and theoretical physicist, winner of the 1968 Nobel Prize in Chemistry.He held the Gibbs Professorship of Theoretical Chemistry at Yale University....
was awarded the 1968 Nobel Prize in Chemistry
Nobel Prize in Chemistry
The Nobel Prize in Chemistry is awarded annually by the Royal Swedish Academy of Sciences to scientists in the various fields of chemistry. It is one of the five Nobel Prizes established by the will of Alfred Nobel in 1895, awarded for outstanding contributions in chemistry, physics, literature,...
. The presentation speech referred to the three laws of thermodynamics and then added "It can be said that Onsager's reciprocal relations represent a further law making possible a thermodynamic study of irreversible processes." Some authors have even described Onsager's relations as the "Fourth law of thermodynamics".
Thermodynamic potentials, forces and flows
The basic thermodynamic potential is internal energyEnergy
In physics, energy is an indirectly observed quantity. It is often understood as the ability a physical system has to do work on other physical systems...
. In a fluid
Fluid
In physics, a fluid is a substance that continually deforms under an applied shear stress. Fluids are a subset of the phases of matter and include liquids, gases, plasmas and, to some extent, plastic solids....
system, changes in the energy density
depend on changes in matter density and entropyEntropy
Entropy is a thermodynamic property that can be used to determine the energy available for useful work in a thermodynamic process, such as in energy conversion devices, engines, or machines. Such devices can only be driven by convertible energy, and have a theoretical maximum efficiency when...
density
in the following way:
where
is temperature and is a combination of pressure and chemical potentialChemical potential
Chemical potential, symbolized by μ, is a measure first described by the American engineer, chemist and mathematical physicist Josiah Willard Gibbs. It is the potential that a substance has to produce in order to alter a system...
. This formula is simply an expression of the first law of thermodynamics
First law of thermodynamics
The first law of thermodynamics is an expression of the principle of conservation of work.The law states that energy can be transformed, i.e. changed from one form to another, but cannot be created nor destroyed...
, namely energy conservation, where the
term represents heatHeat
In physics and thermodynamics, heat is energy transferred from one body, region, or thermodynamic system to another due to thermal contact or thermal radiation when the systems are at different temperatures. It is often described as one of the fundamental processes of energy transfer between...
exchange, and the
term represents (mechanical and chemical) workWork (thermodynamics)
In thermodynamics, work performed by a system is the energy transferred to another system that is measured by the external generalized mechanical constraints on the system. As such, thermodynamic work is a generalization of the concept of mechanical work in mechanics. Thermodynamic work encompasses...
done. For non-fluid or more complex systems there will be a different collection of variables describing the work term, but the principle is the same. We can write
The extensive quantities
and are conservedConservation law
In physics, a conservation law states that a particular measurable property of an isolated physical system does not change as the system evolves....
and their flows satisfy continuity equation
Continuity equation
A continuity equation in physics is a differential equation that describes the transport of a conserved quantity. Since mass, energy, momentum, electric charge and other natural quantities are conserved under their respective appropriate conditions, a variety of physical phenomena may be described...
s:
and
-
,
where
indicates the partial derivativePartial derivative
In mathematics, a partial derivative of a function of several variables is its derivative with respect to one of those variables, with the others held constant...
with respect to time
Time
Time is a part of the measuring system used to sequence events, to compare the durations of events and the intervals between them, and to quantify rates of change such as the motions of objects....
(that is, the local time-rate of change), and indicates the divergenceDivergence
In vector calculus, divergence is a vector operator that measures the magnitude of a vector field's source or sink at a given point, in terms of a signed scalar. More technically, the divergence represents the volume density of the outward flux of a vector field from an infinitesimal volume around...
of the flux densities
Flux density
-Formal Statement:The flux density is simply defined as the amount of flux passing through a unit-area. -Mathematical Statement:The flux density would essentially be the number of field lines passing through a defined unit-area...
.The above expression of the first law in terms of entropy change defines the conjugate variables
Conjugate variables (thermodynamics)
In thermodynamics, the internal energy of a system is expressed in terms of pairs of conjugate variables such as temperature/entropy or pressure/volume. In fact all thermodynamic potentials are expressed in terms of conjugate pairs....
of
and , which are and and are intensive quantities analogous to potential energiesPotential energy
In physics, potential energy is the energy stored in a body or in a system due to its position in a force field or due to its configuration. The SI unit of measure for energy and work is the Joule...
; their gradients of are called thermodynamic forces as they cause flows of the corresponding extensive variables as expressed in the following equations.
In the absence of matter flows, we have a version of Fourier's law
-
;
and, in the absence of heat flows, we have a version of Fick's law
-
,
where
now indicates the gradientGradient
In vector calculus, the gradient of a scalar field is a vector field that points in the direction of the greatest rate of increase of the scalar field, and whose magnitude is the greatest rate of change....
.
The reciprocity relations
In this example, when there are both heat and matter flows, there are "cross-terms" in the relationship between flows and forces (the proportionality coefficients are customarily denoted by):
and
The Onsager reciprocity relations state the equality of the cross-coefficients
and . Proportionality follows from simple dimensional analysisDimensional analysis
In physics and all science, dimensional analysis is a tool to find or check relations among physical quantities by using their dimensions. The dimension of a physical quantity is the combination of the basic physical dimensions which describe it; for example, speed has the dimension length per...
(i.e., both coefficients are measured in the same units of temperature times mass density).
Abstract formulation
Let denote fluctuations from equilibrium values in several thermodynamic quantities, and let be the entropy. Then, assuming the fluctuations are small (gaussianGAUSSIAN
Gaussian is a computational chemistry software program initially released in 1970 by John Pople and his research group at Carnegie-Mellon University as Gaussian 70. It has been continuously updated since then...
), the probability distribution function
Distribution function
In molecular kinetic theory in physics, a particle's distribution function is a function of seven variables, f, which gives the number of particles per unit volume in phase space. It is the number of particles per unit volume having approximately the velocity near the place and time...
can be expressed as
(where we are using Einstein summation convention and is some symmetric matrix)Using the quasi-stationary equilibrium approximation, that is, assuming that the system is only slightly non-equilibrium, we have
Suppose we define thermodynamic conjugate quantities as
, which can also be expressed as linear functions (for small fluctuations): Thus, we can write
where are called kinetic coefficientsThe principle of symmetry of kinetic coefficients or the Onsager's principle states that
is a symmetric matrix, that is Proof
Define mean values and of fluctuating quantities and respectively such that they take given values at Note that Symmetry of fluctuations under time reversal implies that
or, with
, we have Differentiating with respect to
and substituting, we get Putting
in the above equation, It can be easily shown from the definition that
, and hence, we have the required result.