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The Ehrenfest model (or dog–flea model) of
diffusion Diffusion is the net movement of anything (for example, atoms, ions, molecules, energy) generally from a region of higher concentration to a region of lower concentration. Diffusion is driven by a gradient in Gibbs free energy or chemical p ...
was proposed by
Tatiana Tatiana (or Tatianna, also romanized as Tatyana, Tatjana, Tatijana, etc.) is a female name of Sabine-Roman origin that became widespread in Eastern Europe. Variations * be, Тацця́на, Tatsiana * bg, Татяна, Tatyana * germ ...
and
Paul Ehrenfest Paul Ehrenfest (18 January 1880 – 25 September 1933) was an Austrian theoretical physicist, who made major contributions to the field of statistical mechanics and its relations with quantum mechanics, including the theory of phase transition an ...
to explain the
second law of thermodynamics The second law of thermodynamics is a physical law based on universal experience concerning heat and Energy transformation, energy interconversions. One simple statement of the law is that heat always moves from hotter objects to colder objects ( ...
. The model considers ''N'' particles in two containers. Particles independently change container at a rate ''λ''. If ''X''(''t'') = ''i'' is defined to be the number of particles in one container at time ''t'', then it is a
birth–death process The birth–death process (or birth-and-death process) is a special case of continuous-time Markov process where the state transitions are of only two types: "births", which increase the state variable by one and "deaths", which decrease the state ...
with transition rates * q_ = i\, \lambda for ''i'' = 1, 2, ..., ''N'' * q_ = (N-i\,) \lambda for ''i'' = 0, 1, ..., ''N'' – 1 and equilibrium distribution \pi_i = 2^ \tbinom Ni.
Mark Kac Mark Kac ( ; Polish: ''Marek Kac''; August 3, 1914 – October 26, 1984) was a Polish American mathematician. His main interest was probability theory. His question, " Can one hear the shape of a drum?" set off research into spectral theory, the i ...
proved in 1947 that if the initial system state is not equilibrium, then the
entropy Entropy is a scientific concept, as well as a measurable physical property, that is most commonly associated with a state of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynam ...
, given by :H(t) = -\sum_ P(X(t)=i) \log \left( \frac\right), is monotonically increasing (
H-theorem In classical statistical mechanics, the ''H''-theorem, introduced by Ludwig Boltzmann in 1872, describes the tendency to decrease in the quantity ''H'' (defined below) in a nearly-ideal gas of molecules. L. Boltzmann,Weitere Studien über das Wä ...
). This is a consequence of the convergence to the equilibrium distribution.


Interpretation of results

Consider that at the beginning all the particles are in one of the containers. It is expected that over time the number of particles in this container will approach N/2 and stabilize near that state (containers will have approximately the same number of particles). However from mathematical point of view, going back to the initial state is possible (even almost sure). From mean recurrence theorem follows that even the expected time to going back to the initial state is finite, and it is 2^N. Using
Stirling's approximation In mathematics, Stirling's approximation (or Stirling's formula) is an approximation for factorials. It is a good approximation, leading to accurate results even for small values of n. It is named after James Stirling, though a related but less p ...
one finds that if we start at equilibrium (equal number of particles in the containers), the expected time to return to equilibrium is asymptotically equal to \textstyle\sqrt. If we assume that particles change containers at rate one in a second, in the particular case of N=100 particles, starting at equilibrium the return to equilibrium is expected to occur in 13 seconds, while starting at configuration 100 in one of the containers, 0 at the other, the return to that state is expected to take 4\cdot 10^ years. This supposes that while theoretically sure, recurrence to the initial highly disproportionate state is unlikely to be observed.


Bibliography

* Paul and Tatjana Ehrenfest: Über zwei bekannte Einwände gegen das Boltzmannsche H-Theorem. ''
Physikalische Zeitschrift ''Physikalische Zeitschrift'' (English: ''Physical Journal'') was a German scientific journal of physics published from 1899 to 1945 by S. Hirzel Verlag. In 1924, it merged with ''Jahrbuch der Radioaktivität und Elektronik''. From 1944 onwards, ...
, vol. 8 (1907)'', pp. 311–314. * F.P. Kelly: ''The Ehrenfest model'', in ''Reversibility and Stochastic Networks''. Wiley, Chichester, 1979. pp. 17–20. * David O. Siegmund: ''Ehrenfest model of diffusion (mathematics)''.
Encyclopædia Britannica The (Latin for "British Encyclopædia") is a general knowledge English-language encyclopaedia. It is published by Encyclopædia Britannica, Inc.; the company has existed since the 18th century, although it has changed ownership various time ...
.


References

{{Reflist Queueing theory Diffusion Stochastic models