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Onsager reciprocal relations
In thermodynamics, the Onsager reciprocal relations express the equality of certain relations between flows and forces in thermodynamical systems out of equilibrium, but where a notion of local equilibrium exists.
As an example, it is observed that temperature differences in a system 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. It was observed experimentally that when both pressure and temperature vary, pressure differences can cause heat flow and temperature differences can cause matter flow. Even more surprisingly, the heat flow per unit of pressure difference and the density (matter) flow per unit of temperature difference are equal. This was shown to be necessary by Lars Onsager using statistical mechanics.
Similar "reciprocal relations" occur between different pairs of forces and flows in a variety of physical systems.
The theory developed by Onsager is much more general than this example and capable of treating more that two thermodynamic forces at once.
Example: Fluid system
Thermodynamic potentials, forces and flows
- du = T ds + m dr
where T is temperature and m is a combination of pressure and chemical potential. We can write
- ds = (1/T) du - (m/T) dr.
- ; and
The gradients of the conjugate variables of u and r, which are 1/T and -m/T, are thermodynamic forces and they cause flows of the corresponding extensive variables. In the absence of matter flows,
and, in the absence of heat flows,
where now indicates the gradient.
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 L):
- ; and
The Onsager reciprocity relations state the equality of the cross-coefficients Lur and Lru. Proportionality follows from simple dimensional analysis (i.e., both coefficients are measured in the same units of temperature times mass density).
Let Ei be the extensive variables on which entropy (S) depends. In the following analysis, these symbols will refer to densities of these thermodynamic quantities. Then,
- dS = Σi Ii dEi,
defines the intensive quantity Ii conjugate to the extensive quantity Ei.
The gradients of the intensive quantities are thermodynamic forces:
and they cause fluxes Ji of the extensive quantities satisfying continuity equations
The fluxes are proportional to the thermodynamic forces by a matrix of coefficients Lij:
- Ji = Σj LijFj
Introducing a susceptibility matrix
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