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Ludwig Boltzmann
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Image:Boltzmann.jpg thumb|right|Ludwig Boltzmann
'''Ludwig Eduard Boltzmann''' (
February 20,
1844 –
September 5,
1906) was an
Austrian
physicist famous for the invention of
statistical mechanics. Born in
Vienna,
Austria-Hungary, he committed suicide in 1906 by hanging himself while on holiday in
Duino near
Trieste in
Italy. The motivation behind the suicide remains unclear, but it may have been related to his lingering resentment over the rejection by much of the
physics establishment of his thesis about the reality of
atoms and
molecules — a belief shared, however, by
James Clerk Maxwell Maxwell in
Scotland and
Josiah Willard Gibbs Gibbs in the
United States; and by
History of chemistry#The dispute about atomism most chemistry chemists since the discoveries of
John Dalton in 1808.
He was upset by his long-running dispute with the editor of the preeminent
Germany German physics journal of his day, who refused to let Boltzmann refer to atoms and molecules as anything other than convenient
Theory#Science theoretical constructs. Only a couple of years after Boltzmann's death,
Jean Baptiste Perrin Perrin's studies of
colloidal suspensions (1908-1909) confirmed the values of
Avogadro's number and
Boltzmann constant Boltzmann's constant, and convinced the world that the tiny particles
Atomic theory#History really exist.
To quote
Max Planck Planck, ''The
logarithmic connection between
entropy and
probability was first stated by L. Boltzmann in his
kinetic theory of gases.''{{Ref|1}} This famous formula for entropy
is{{Ref|2}} {{Ref|3}}
:
where
= 1.3806505(24) × 10
−23 Joule J Kelvin K−1 is
Boltzmann constant Boltzmann's constant, and the
logarithm is taken to the natural base
.
is the number of possible
microstate (statistical mechanics) microstates corresponding to the
macroscopic state of a system — the number of (unobservable) "ways" the (observable)
thermodynamics thermodynamic state of a system can be realized by assigning different
coordinate system positions and
momentum momenta to the various molecules. Boltzmann’s
Paradigm#Paradigm shifts paradigm was an
ideal gas of
''identical'' particles, of which
are in the
-th microscopic condition (range) of position and momentum.
can be counted using the formula for
Maxwell-Boltzmann statistics#Derivation of the Maxwell-Boltzmann distribution permutations
:
where ''i'' ranges over all possible molecular conditions. (
denotes
factorial.) The "correction" in the denominator is due to the fact that identical particles in the same condition are
Identical particles indistinguishable.
is called the "
thermodynamic probability" since it is an
integer greater than one, while
probability theory mathematical probabilities are always
numbers between zero and one.
The equation for
is engraved on Boltzmann's
headstone tombstone at the Vienna
Zentralfriedhof — his second grave.
The Boltzmann equation
Image:Ludwig Boltzmann at U Vienna.JPG thumb|left|250px|Boltzmann's bust in the courtyard arcade of the main building, [[University of Vienna.]]
{{main|Boltzmann equation}}
The Boltzmann equation was developed to describe the dynamics of an
ideal gas.
:
where
represents the distribution function of single-particle position and momentum at a given time (see the
Maxwell-Boltzmann distribution),
is a force,
is the mass of a particle,
is the time and
is an average velocity of particles.
This equation describes the
time temporal and
space spatial variation of the probability distribution for the position and momentum of a density distribution of a cloud of points in single-particle
phase space. (See
Hamiltonian mechanics.) The first term on the left-hand side represents the explicit time variation of the distribution function, while the second term gives the spatial variation, and the third term describes the effect of any force acting on the particles. The right-hand side of the equation represents the effect of collisions.
Image:Zentralfriedhof Vienna - Boltzmann.JPG thumb|right|200px|Boltzmann's grave in the [[Zentralfriedhof, Vienna, with bust and entropy formula.]]
In principle, the above equation completely describes the dynamics of an ensemble of gas particles, given appropriate
boundary conditions. This first-order
differential equation has a deceptively simple appearance, since
can represent an arbitrary single-particle distribution function. Also, the
force acting on the particles depends directly on the velocity distribution function ''f''. The Boltzmann equation is notoriously difficult to
integration integrate.
David Hilbert spent years trying to solve it without any real success.
The form of the collision term assumed by Boltzmann was approximate. However for an
ideal gas the standard
Chapman-Enskog solution of the Boltzmann equation is highly accurate. It is only expected to lead to incorrect results for an
ideal gas under shock-wave conditions.
Boltzmann tried for many years to "prove" the
second law of thermodynamics using his gas-dynamical equation — his famous
H-theorem.{{Ref.html">molecular chaos
"molecular chaos", an assumption which breaks
CPT symmetry time-reversal symmetry as is necessary for ''anything'' which could imply the second law. It was from the probabilistic assumption alone that Boltzmann's apparent success emanated, so his long dispute with
Johann Josef Loschmidt Loschmidt and others over
Loschmidt's paradox ultimately ended in his failure.
It has been speculated that this failure may have contributed to Boltzmann's suicide, despite his great successes in
kinetic theory, including the
Maxwell-Boltzmann distribution for molecular speeds in a gas. In addition,
Maxwell-Boltzmann statistics and the
Boltzmann distribution over energies remain the foundations of
classical mechanics classical statistical mechanics. They are applicable to the many
phenomenon phenomena that do not require
Maxwell-Boltzmann statistics#Limits of applicability quantum statistics and provide a remarkable insight into the meaning of
thermodynamic temperature temperature.
For higher density fluids, the Enskog equation was proposed. For moderately dense gases this equation, which reduces to the Boltzmann equation at low densities, is fairly accurate. However the Enskog equation is basically an
heuristic approximation without any rigorous mathematical basis for
extrapolation extrapolating from low to higher densities.
Finally, in the 1970s E.G.D. Cohen and J.R. Dorfman proved that a systematic (power series) extension of the Boltzmann equation to high densities is mathematically impossible. Consequently
non-equilibrium statistical mechanics nonequilibrium statistical mechanics for dense
gases and
liquids focuses on the
Green-Kubo relations, the
fluctuation theorem, and other approaches instead.
Energetics of evolution
In 1922,
Alfred J. Lotka [http://en.wikipedia.org/wiki/Maximum_power_principle#Proposals_for_maximum_power_principle_as_4th_thermodynamic_law] referred to Boltzmann as one of the first proponents of the proposition that available energy (also called
exergy) can be understood as the fundamental object under contention in the biological, or life-struggle and therefore also in the evolution of the organic world. Lotka interpreted Boltzmann's view to imply that available energy could be the central concept that unified physics and biology as a quantitative physical principle of evolution.
Howard T. Odum later developed this view as the
maximum power principle.
Significant contributions
1872 -
Boltzmann equation;
H-theorem
1877 -
Boltzmann distribution; relationship between thermodynamic entropy and probability.
1884 - Derivation of the
Stefan-Boltzmann law
Evaluations
Closely associated with a particular interpretation of the
second law of thermodynamics, he is also credited in some quarters with anticipating
quantum mechanics.
For detailed and technically informed account of Boltzmann's contributions to statistical mechanics consult the [http://xxx.lanl.gov/abs/cond-mat/9608054 article] by E.G.D. Cohen.
See also:
Philosophy of thermal and statistical physics.
Notes
* {{Note|1}} 1. Max Planck, p. 119.
* {{Note|2}} 2. The concept of
entropy was introduced by
Rudolf Clausius in 1865. He was the first to enunciate the
second law of thermodynamics by saying that ''entropy always increases''.
* {{Note|3}} 3. An alternative is the
Information entropy#Formal definitions information entropy definition introduced in 1948 by
Claude Elwood Shannon Claude Shannon.[http://cm.bell-labs.com/cm/ms/what/shannonday/paper.html] It was intended for use in communication theory, but is applicable in all areas. It reduces to Boltzmann's expression when all the probabilities are equal, but can, of course, be used when they are not. Its virtue is that it yields immediate results without resorting to
factorial factorials or
Stirling's approximation. Similar formulas are found, however, as far back as the work of Boltzmann, and explicitly in
H-theorem#Quantum mechanical H-theorem Gibbs (see reference).
* {{Note|4}} 4.
Wallace Carothers, who discovered
neoprene and
nylon and founded the science of long-
chain polymers, finally drank his cocktail of
cyanide-laced lemon juice in 1937, one year before nylon reached the
marketing market.
* {{Note|5}} 5. See Tolman, Chapter VI, for an extensive discussion.
See also
*
List of Austrian scientists
*
List of Austrians
External links
* {{MacTutor Biography|id=Boltzmann}}
-
Scienceworld biography
-
Biography from St Andrews University
-
Boltzmann's Work in Statistical Physics Article by Jos Uffink for the Stanford Encyclopedia of Philosophy
-
Claude E. Shannon, "The Mathematical Theory of Communication"
References
* {{cite book | author=Max Planck | title=The Theory of Heat Radiation | publisher=P. Blakiston Son & Co | year=1914}} English translation by Morton Masius of the 2nd ed. of ''Waermestrahlung''. Reprinted by Dover (1959) & (1991). ISBN 0486668118
* {{cite book | author=Richard C. Tolman | title=The Principles of Statistical Mechanics | publisher=Oxford University Press | year=1938}} Reprinted: Dover (1979). ISBN 0486638960
* {{cite book | author=
Josiah Willard Gibbs J. Willard Gibbs | title=Elementary Principles in Statistical Mechanics | publisher=Ox Bow Press (1981) | year=1901 |id=ISBN 0918024196}}
*
David Lindley (Physicist) ''Boltzmann's Atom: The Great Debate That Launched A Revolution In Physics.'' ISBN 0684851865
* A.J.Lotka (1922) 'Contribution to the energetics of evolution'. ''Proc Natl Acad Sci'', 8: pp. 147–51.
Category:1844 births Boltzmann, Ludwig
Category:1906 deaths Boltzmann, Ludwig
Category:Austrian physicists Boltzmann, Ludwig
Category:Scientists who committed suicide Boltzmann, Ludwig
Category:History of physics Boltzmann, Ludwig
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