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Third law of thermodynamics

1 History

The third law of thermodynamics is sometimes stated


as follows, regarding the properties of systems in equilibrium at absolute zero temperature:

The 3rd law was developed by the chemist Walther Nernst


during the years 190612, and is therefore often referred
to as Nernsts theorem or Nernsts postulate. The third
The entropy of a perfect crystal, at absolute
law of thermodynamics states that the entropy of a system
zero (zero kelvins), is exactly equal to zero.
at absolute zero is a well-dened constant. This is because
a system at zero temperature exists in its ground state, so
At zero kelvin the system must be in a state with the min- that its entropy is determined only by the degeneracy of
imum possible energy, and this statement of the third law the ground state.
holds true if the perfect crystal has only one minimum energy state. Entropy is related to the number of possible In 1912 Nernst stated the law thus: It is impossible for
microstates, and for a system containing a certain collec- any procedure to lead to the isotherm T = 0 in a nite
[4]
tion of particles, quantum mechanics indicates that there number of steps.
is only one unique state (called the ground state) with An alternative version of the third law of thermodynamics
minimum energy.[1] If the system does not have a well- as stated by Gilbert N. Lewis and Merle Randall in 1923:
dened order (if its order is glassy, for example), then in
practice there will remain some nite entropy as the system is brought to very low temperatures as the system beIf the entropy of each element in some (percomes locked into a conguration with non-minimal enfect) crystalline state be taken as zero at the
ergy. The constant value is called the residual entropy of
absolute zero of temperature, every substance
the system.[2]
has a nite positive entropy; but at the absolute
The NernstSimon statement of the third law of thermozero of temperature the entropy may become
dynamics is in regard to thermodynamic processes, and
zero, and does so become in the case of perwhether it is possible to achieve absolute zero in practice:
fect crystalline substances.

This version states not only S will reach zero at 0 K,


but S itself will also reach zero as long as the crystal has
a ground state with only one conguration. Some crystals form defects which causes a residual entropy. This
residual entropy disappears when the kinetic barriers to
transitioning to one ground state are overcome.[5]

The entropy change associated with any


condensed system undergoing a reversible
isothermal process approaches zero as temperature approaches 0 K, where condensed
system refers to liquids and solids.

With the development of statistical mechanics, the third


law of thermodynamics (like the other laws) changed
A simpler formulation of the NernstSimon statement from a fundamental law (justied by experiments) to a
might be:
derived law (derived from even more basic laws). The basic law from which it is primarily derived is the statisticalmechanics denition of entropy for a large system:
It is impossible for any process, no matter how idealized, to reduce the entropy of a
system to its absolute-zero value in a nite
number of operations.

S S0 = kB ln

where S is entropy, kB is the Boltzmann constant, and


is the number of microstates consistent with the macroPhysically, the NernstSimon statement implies that it is scopic conguration. The counting of states is from the
impossible for any procedure to bring a system to the ab- reference state of absolute zero, which corresponds to the
solute zero of temperature in a nite number of steps.[3] entropy of S0 .
1

MATHEMATICAL FORMULATION

Explanation

In simple terms, the third law states that the entropy of


a perfect crystal of a pure substance approaches zero as
the critical temperature approaches zero. The alignment
of a perfect crystal leaves no ambiguity as to the position
of the components of the system and the orientation of
each part of the crystal is identical. As the energy of the
crystal is reduced, the unique vibrations of each atom are
reduced to nothing. At that point no part of the crystal
is unique, hence it is in essence one thing. This law provides an absolute reference point for the determination of
entropy at any other temperature. Any increase in the entropy of a system, determined relative to this zero point,
is the absolute entropy of that system. Mathematically,
the absolute entropy of any system at zero temperature
is the natural log of the number of ground states times
Boltzmanns constant kB=1.38x1023, JK1 .
The entropy of a perfect crystal lattice as dened by
Nernsts theorem is zero provided that its ground state
is unique, because ln(1) = 0. If the system is composed
of one-billion atoms, all alike, and lie within the matrix
of a perfect crystal, the number of permutations of onebillion identical things taken one-billion at a time is =
1. Hence:

S S0 = kB ln = kB ln 1 = 0
The dierence is zero, hence the initial entropy S0 can
be any selected value so long as all other such calculations include that as the initial entropy. As a result the
initial entropy value of zero is selected S0 = 0 is used for
convenience.

S S0 = S 0 = 0
S=0
In way of example, suppose a system consists of 1 cm3
of matter with a mass of 1 g and 20 g/gmole. The system
consists of 3x1022 identical atoms at 0 K. If one atom
should absorb a photon of wavelength of 1 cm that atom
is then unique and the permutations of one unique atom
among the 3x1022 is N=3x1022 . The entropy, energy,
and temperature of the system rises and can be calculated.
The entropy change is:

S = S S0 = kB ln

S = S S0 = kB ln() =

Q
T

Calculating entropy change:


S0 = kB ln N = 1.381023 ln 3 1022 = 701023 J/K
The energy change of the system as a result of absorbing
the single photon whose energy is :

Q = =

6.62 1034 J s 3 108 m/s


hc
=
= 21023 J

0.01m

The temperature of the system rises by:

T =

2 1023 J
1
=
=
K
S
70 1023 J/K
35

This can be interpreted as the average temperature of the


system over the range from 0 < S < 70x1023 J/K[6] A
single atom was assumed to absorb the photon but the
temperature and entropy change characterizes the entire
system.
An example of a system which does not have a unique
ground state is one whose net spin is a half-integer,
for which time-reversal symmetry gives two degenerate
ground states. For such systems, the entropy at zero
temperature is at least kB*ln(2) (which is negligible on
a macroscopic scale). Some crystalline systems exhibit
geometrical frustration, where the structure of the crystal
lattice prevents the emergence of a unique ground state.
Ground-state helium (unless under pressure) remains liquid.
In addition, glasses and solid solutions retain large entropy at 0 K, because they are large collections of nearly
degenerate states, in which they become trapped out of
equilibrium. Another example of a solid with many
nearly-degenerate ground states, trapped out of equilibrium, is ice Ih, which has proton disorder.
For the entropy at absolute zero to be zero, the magnetic
moments of a perfectly ordered crystal must themselves
be perfectly ordered; from an entropic perspective, this
can be considered to be part of the denition of a perfect crystal. Only ferromagnetic, antiferromagnetic, and
diamagnetic materials can satisfy this condition. Materials that remain paramagnetic at 0 K, by contrast, may
have many nearly-degenerate ground states (for example, in a spin glass), or may retain dynamic disorder (a
quantum spin liquid).

From the second law of thermodynamics:

3 Mathematical formulation
S = S S0 =
Hence:

Q
T

Consider a closed system in internal equilibrium. As the


system is in equilibrium there are no irreversible processes so the entropy production is zero. During the heat,

4.2

Specic heat

supply temperature gradients are generated in the material, but the associated entropy production can be kept
low enough if the heat is supplied slowly. The increase
in entropy due to the added heat Q is then given by the
second part of the Second law of thermodynamics which
states that the entropy change of a system is given by
The temperature rise dT due to the heat Q is determined
by the heat capacity C(T,X) according to
The parameter X is a symbolic notation for all parameters (such as pressure, magnetic eld, liquid/solid fraction, etc.) which are kept constant during the heat supply.
E.g. if the volume is constant we get the heat capacity
at constant volume CV. In the case of a phase transition
from liquid to solid, or from gas to liquid the parameter X
can be one of the two components. Combining relations
(1) and (2) gives
Integration of Eq.(3) from a reference temperature T 0 to
an arbitrary temperature T gives the entropy at temperature T
We now come to the mathematical formulation of the
third law. There are three steps:
1: in the limit T 0 0 the integral in Eq.(4) is nite. So
that we may take T 0 =0 and write
2. the value of S(0,X) is independent of X. In mathematical form

Fig.1 Left side: Absolute zero can be reached in a nite number


of steps if S(0,X1 )S(0, X2 ). Right: An innite number of steps
is needed since S(0,X1 )= S(0,X2 ).

The reason that T=0 cannot be reached according to the


third law is explained as follows: Suppose that the temperature of a substance can be reduced in an isentropic
process by changing the parameter X from X2 to X1 . One
can think of a multistage nuclear demagnetization setup
where a magnetic eld is switched on and o in a controlled way.[8] If there were an entropy dierence at absolute zero, T=0 could be reached in a nite number of
steps. However, at T=0 there is no entropy dierence so
an innite number of steps would be needed. The process
is illustrated in Fig.1.

So Eq.(5) can be further simplied to


Equation (6) can also be formulated as

4.2 Specic heat

In words: at absolute zero all isothermal processes are


isentropic. Eq.(8) is the mathematical formulation of the A non-quantitative description of his third law that Nernst
gave at the very beginning was simply that the specic
third law.
heat can always be made zero by cooling the mate3: as one is free to choose the zero of the entropy it is rial down far enough.[9] A modern, quantitative analyconvenient to take
sis follows. Suppose that the heat capacity of a sample
in the low temperature region can be approximated by
so that Eq.(7) reduces to the nal form
C(T,X)=C 0 T , then
The physical meaning of Eq.(9) is deeper than just a convenient selection of the zero of the entropy. It is due to The integral is nite for T 0 0 if >0. So the heat capacity of all substances must go to zero at absolute zero
the perfect order at zero kelvin as explained before.

4
4.1

Consequences of the third law


Can absolute zero be obtained?

The third law is equivalent to the statement that


It is impossible by any
procedure, no matter how
idealized, to reduce the
temperature of any system to zero temperature
in a nite number of nite
operations.[7]

The molar specic heat at constant volume of a


monatomic classical ideal gas, such as helium at room
temperature, is given by CV=(3/2)R with R the molar
ideal gas constant. Substitution in Eq.(4) gives
In the limit T 0 0 this expression diverges. Clearly a constant heat capacity does not satisfy Eq.(12). This means
that a gas with a constant heat capacity all the way to absolute zero violates the third law of thermodynamics.
The conict is solved as follows: At a certain temperature
the quantum nature of matter starts to dominate the behavior. Fermi particles follow FermiDirac statistics and
Bose particles follow BoseEinstein statistics. In both
cases the heat capacity at low temperatures is no longer
temperature independent, even for ideal gases. For Fermi
gases
with the Fermi temperature TF given by

7 FURTHER READING

Here NA is Avogadros number, V the molar volume,


and M the molar mass.

Timeline of thermodynamics, statistical mechanics,


and random processes

For Bose gases

Quantum refrigerators

with TB given by
The specic heats given by Eq.(14) and (16) both satisfy
Eq.(12).

4.3

Vapor pressure

The only liquids near absolute zero are He and He.


Their heat of evaporation has a limiting value given by
with L0 and C constant. If we consider a container, partly
lled with liquid and partly gas, the entropy of the liquid
gas mixture is
where S (T) is the entropy of the liquid and x is the gas
fraction. Clearly the entropy change during the liquidgas
transition (x from 0 to 1) diverges in the limit of T0.
This violates Eq.(8). Nature solves this paradox as follows: at temperatures below about 50 mK the vapor pressure is so low that the gas density is lower than the best
vacuum in the universe. In other words: below 50 mK
there is simply no gas above the liquid.

6 References
[1] J. Wilks The Third Law of Thermodynamics Oxford University Press (1961).
[2] Kittel and Kroemer, Thermal Physics (2nd ed.), page 49.
[3] Wilks, J. (1971). The Third Law of Thermodynamics,
Chapter 6 in Thermodynamics, volume 1, ed. W. Jost,
of H. Eyring, D. Henderson, W. Jost, Physical Chemistry.
An Advanced Treatise, Academic Press, New York, page
477.
[4] Bailyn, M. (1994). A Survey of Thermodynamics, American Institute of Physics, New York, ISBN 0883187973, page 342.
[5] Kozliak, Evguenii; Lambert, Frank L. (2008). Residual Entropy, the Third Law and Latent Heat. Entropy 10 (3): 27484. Bibcode:2008Entrp..10..274K.
doi:10.3390/e10030274.
[6] Reynolds and Perkins (1977). Engineering Thermodynamicsq. McGraw Hill. p. 438. ISBN 0-07-052046-1.

4.4

Latent heat of melting

The melting curves of He and He both extend down to


absolute zero at nite pressure. At the melting pressure
liquid and solid are in equilibrium. The third law demands that the entropies of the solid and liquid are equal
at T=0. As a result the latent heat of melting is zero and
the slope of the melting curve extrapolates to zero as a
result of the ClausiusClapeyron equation.

4.5

Thermal expansion coecient

The thermal expansion coecient is dened as


With the Maxwell relation
and Eq.(8) with X=p it is shown that
So the thermal expansion coecient of all materials must
go to zero at zero kelvin.

See also
Adiabatic process
Ground state
Laws of thermodynamics
Residual entropy
Thermodynamic entropy

[7] Guggenheim, E.A. (1967). Thermodynamics. An Advanced Treatment for Chemists and Physicists, fth revised edition, North-Holland Publishing Company, Amsterdam, page 157.
[8] F. Pobell, Matter and Methods at Low Temperatures,
(Springer-Verlag, Berlin, 2007)
[9] Einstein and the Quantum, A. Douglas Stone, Princeton
University Press, 2013.

7 Further reading
Goldstein, Martin & Inge F. (1993) The Refrigerator
and the Universe. Cambridge MA: Harvard University Press. ISBN 0-674-75324-0. Chpt. 14 is a nontechnical discussion of the Third Law, one including
the requisite elementary quantum mechanics.
Braun, S.; Ronzheimer, J. P.; Schreiber, M.; Hodgman, S. S.; Rom, T.; Bloch, I.; Schneider, U. (2013).
Negative Absolute Temperature for Motional Degrees of Freedom. Science 339 (6115): 52
5. arXiv:1211.0545. Bibcode:2013Sci...339...52B.
doi:10.1126/science.1227831. PMID 23288533.
Lay summary New Scientist (3 January 2013).
Levy, A.; Alicki, R.; Koslo, R. (2012). Quantum refrigerators and the third law of thermodynamics.
Phys.
Rev.
E 85: 061126.
doi:10.1103/PhysRevE.85.061126.

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