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 (T-symmetry);
- Second, it relates to the statistical description of the kinetics of macroscopic or mesoscopic systems as an ensemble of elementary processes: collisions, elementary transitions or reactions. For these processes, the consequence of the microscopic T-symmetry is:
Corresponding to every individual process there is a reverse process, and in a state of equilibrium the average rate of every process is equal to the average rate of its reverse process.[1]
History of microscopic reversibility
The idea of microscopic reversibility was born together with physical kinetics. In 1872, Ludwig Boltzmann represented kinetics of gases as statistical ensemble of elementary collisions.[2] Equations of mechanics are reversible in time, hence, the reverse collisions obey the same laws. This reversibility of collisions is the first example of microreversibility. According to Boltzmann, this microreversibility implies the principle of detailed balance for collisions: at the equilibrium ensemble each collision is equilibrated by its reverse collision.[2] These ideas of Boltzmann were analyzed in detail and generalized by Richard C. Tolman.[3]
In chemistry,
"Here, however, the chemists are accustomed to impose a very interesting additional restriction, namely: when the equilibrium is reached each individual reaction must balance itself. They require that the transition must take place just as frequently as the reverse transition etc."
The quantum theory of emission and absorption developed by Albert Einstein (1916, 1917)[7] gives an example of application of the microreversibility and detailed balance to development of a new branch of kinetic theory.
Sometimes, the principle of detailed balance is formulated in the narrow sense, for chemical reactions only[8] but in the history of physics it has the broader use: it was invented for collisions, used for emission and absorption of quanta, for transport processes[9] and for many other phenomena.
In its modern form, the principle of microreversibility was published by Lewis (1925).[1] In the classical textbooks[3][10] full theory and many examples of applications are presented.
Time-reversibility of dynamics
The Newton and the Schrödinger equations in the absence of the macroscopic magnetic fields and in the inertial frame of reference are T-invariant: if X(t) is a solution then X(-t) is also a solution (here X is the vector of all dynamic variables, including all the coordinates of particles for the Newton equations and the wave function in the configuration space for the Schrödinger equation).
There are two sources of the violation of this rule:
- First, if dynamics depend on a pseudovector like the magnetic field or the rotation angular speed in the rotating frame then the T-symmetry does not hold.
- Second, in microphysics of weak interaction the T-symmetry may be violated and only the combined CPT symmetry holds.
Macroscopic consequences of the time-reversibility of dynamics
In physics and chemistry, there are two main macroscopic consequences of the time-reversibility of microscopic dynamics: the principle of detailed balance and the Onsager reciprocal relations.
The statistical description of the macroscopic process as an ensemble of the elementary indivisible events (collisions) was invented by L. Boltzmann and formalised in the Boltzmann equation. He discovered that the time-reversibility of the Newtonian dynamics leads to the detailed balance for collision: in equilibrium collisions are equilibrated by their reverse collisions. This principle allowed Boltzmann to deduce simple and nice formula for entropy production and prove his famous H-theorem.[2] In this way, microscopic reversibility was used to prove macroscopic irreversibility and convergence of ensembles of molecules to their thermodynamic equilibria.
Another macroscopic consequence of microscopic reversibility is the symmetry of kinetic coefficients, the so-called reciprocal relations. The reciprocal relations were discovered in the 19th century by
References
- ^ PMID 16576866.
- ^ a b c Boltzmann, L. (1964), Lectures on gas theory, Berkeley, CA, USA: U. of California Press.
- ^ a b Tolman, R. C. (1938). The Principles of Statistical Mechanics. Oxford University Press, London, UK.
- ^ Van't Hoff, J.H. Etudes de dynamique chimique. Frederic Muller, Amsterdam, 1884.
- S2CID 197766994.
- ^ ISSN 0031-899X.
- ^ Einstein, A. (1917). Zur Quantentheorie der Strahlung [=On the quantum theory of radiation], Physikalische Zeitschrift 18 (1917), 121-128. English translation: D. ter Haar (1967): The Old Quantum Theory. Pergamon Press, pp. 167-183.
- ^ Principle of microscopic reversibility. Encyclopædia Britannica Online. Encyclopædia Britannica Inc., 2012.
- S2CID 18961678.
- ISBN 0-08-026480-8. Vol. 10 of the Course of Theoretical Physics(3rd Ed).