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Entropy
Quanta
John D. Norton
Department of History and Philosophy of Science
University of Pittsburgh
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The Papers of
Einstein’s Year of
Miracles, 1905
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The Papers of 1905
"Light quantum/photoelectric effect paper" Einstein inferred from the thermal properties of high
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accord with E=mc2.
“Does the Inertia of a Body Depend upon its Energy
Content?”
Annalen der Physik, 18(1905), pp. 639-641. (September 1905; received 27
September, 1905)
Einstein to Conrad Habicht
18th or 25th May 1905
“…and is very revolutionary”
Einstein’s assessment of his light quantum paper.
…So, what are you up to, you frozen whale, you smoked, dried, canned piece of sole…?
…Why have you still not sent me your dissertation? …Don't you know that I am one of the
1.5 fellows who would read it with interest and pleasure, you wretched man? I promise you
four papers in return…
The [first] paper deals with radiation and the energy properties of light
and is very revolutionary, as you will see if you send me your work first.
The second paper is a determination of the true sizes of atoms from the diffusion and the
viscosity of dilute solutions of neutral substances.
The third proves that, on the assumption of the molecular kinetic theory of heat, bodies on
the order of magnitude 1/1000 mm, suspended in liquids, must already perform an
observable random motion that is produced by thermal motion;…
The fourth paper is only a rough draft at this point, and is an electrodynamics of moving
bodies which employs a modification of the theory of space and time; the purely
kinematical part of this paper will surely interest you.
Why is only the light quantum All the rest develop or
“very revolutionary”? complete 19th century physics.
Special relativity
4 “On the Electrodynamics of Moving Bodies,”
Annalen der Physik, 17 (1905), pp. 891-921. (June 1905; received 30 June, 1905)
Establishes the real significance
of the Lorentz covariance of
Maxwell’s electrodynamics.
E=mc2
5 “Does the Inertia of a Body Depend upon its Energy
Content?”
Annalen der Physik, 18(1905), pp. 639-641. (September 1905; received 27
Light energy has momentum;
extend to all forms of energy.
September, 1905)
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Why is only the light quantum All the rest develop or
“very revolutionary”? complete 19th century physics.
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If….
If we locate Einstein’s light quantum
paper against the background of his work
in statistical physics,
its methods are an inspired variation of
ones repeated used and proven effective
in other contexts on very similar
problems.
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Einstein’s Early Program
in Statistical Physics
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Einstein’s first two “worthless” papers Einstein to Stark, 7 Dec 1907, “…I am
sending you all my publications
excepting my two worthless beginner’s
works…”
“Conclusions drawn
from the
phenomenon of
Capillarity,”
Annalen der Physik,
4(1901), pp. 513-
523.
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Einstein’s first two “worthless” papers
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3 papers 1902-
Independent Discovery of the Gibbs Framework 1904
Einstein, Albert.
'Kinetische Theorie des
Waermegleichgewichtes und
des zweiten Hauptsatzes der
Thermodynamik'. Annalen
der Physik, 9 (1902)
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3 papers 1902-
Independent Discovery of the Gibbs Framework 1904
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3 papers 1902-
Independent Discovery of the Gibbs Framework 1904
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The Hidden Gem
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Einstein’s Fluctuation Formula
Any canonically distributed
Variance of energy from mean
system
E dE
p(E) exp (E E) kT
2 2
kT 2C
2
kT dT
Heat capacity is
macroscopically
measureable.
(1904)
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Applied to an Ideal Gas
Ideal monatomic gas, n molecules
3nkT 3nk
E C
2 2
dE
(E E) kT
2 2
kT 2C
2
dT
rms deviation of energy from mean
3n / 2kT
1 n=1024…. negligible
n=1
1
0.816
E (3n / 2)kT 3n / 2 3/ 2
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In 1904, no one had any solid
Applied to heat radiation idea of the constitution of
heat radiation!
Volume V of heat radiation (Stefan-Boltzmann law)
E VT 4 C 4VT 3
dE
2 (E E)2 kT 2 kT 2C
dT
rms deviation of energy from mean
2 kVT 5/2 k 1
2
E VT 4
V T 3/2
Hence estimate volume V in which
fluctuations are of the size of the
mean energy.
E2 2
(1904) 19
Einstein’s Doctoral
Dissertation
"A New Determination of
Molecular Dimensions”
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How big are molecules?
= How many fit into a gram mole? = Loschmidt’s number N
= (r/m) N (4p/3) P 3
r= sugar density in the solution
m = molecular weight of sugar
PV = nkT
Dilute sugar solution in a gravitational field.
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Recovering the equation for diffusion
The equilibrium sugar concentration
gradient arises from a balance of:
And
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“Brownian motion paper.”
“On the motion of small particles suspended
in liquids at rest required by the molecular-
kinetic theory of heat.”
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An easier way to estimate N?
Measure D and
Particles in suspension in a gravitational we can find N. 29
field
Brownian motion
“If it is really possible to observe the motion discussed here … then classical
thermodynamics can no longer be viewed as strictly valid even for
microscopically distinguishable spaces, and an exact determination of the
real size of atoms becomes possible.”
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Estimating the coefficient of diffusion for suspended particles
…and hence determine N.
To describe the thermal motions of small particles, Einstein laid the foundations of the
modern theory of stochastic processes and solved the “random walk problem.”
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Thermodynamics of
Systems of Independent
Components
(ideal gas law)
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The simplest case: an ideal gas
(e.g. most ordinary gases at ordinary temperatures and low pressures)
Pressure P x volume V =
number of molecules n
x Boltzmann’s constant k
x temperature T
PV = nkT
h
The ideal gas law
is the macroscopic
signature of…
Observed property
…And we can invert the inference.
Ideal gas law PV = nkT
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A much simpler derivation
Very many,
independent, small
particles at
equilibrium in a Pull of gravity
gravitational field. equilibrated by
pressure P.
Independence expressed:
energy E(h) of each particle
is a function of height h only.
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A much simpler derivation
Boltzmann Probability of one molecule at height h
distribution of P(h) = const. exp(-E(h)/kT)
energies
Density of gas at height h
r = r0 exp(-E(h)/kT)
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“Light
quantum/photoelectric
effect paper”
"On a heuristic viewpoint concerning the
production and transformation of light."
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Einstein’s astonishing idea
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Why the atomistic signature of radiation is hard to
see
Atomistic signature of systems with High frequency radiation is a system
• fixed, large number with
• spatially localized • variable, large number
• independent • spatially localized
components is the ideal gas law. • independent
components, so the ideal gas law is hard to see.
The signature of
independent atoms:
entropy depends on the
logarithm of volume
ratios. 42
…which he found in high frequency radiation
Spontaneous volume fluctuations in high frequency radiation are also possible.
Radiation of energy E may spontaneously halve in volume with very small probability.
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Conclusion
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Unity in Einstein’s statistical physics of
1905
Einstein investigated many different thermal systems in 1905.
What made these investigations tractable was a common feature:
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