The third law of thermodynamics states that:

“The entropy of all the perfect crystalline solids is zeros at absolute

zero temperature”. The third law of thermodynamics is also
referred to as Nernst law. It provides the basis for the calculation
of absolute entropies of the substances.

Mathematically,
LimT –>0 S = 0

If the entropy is zero at temperature T = o, then this law states

that the absolute entropy Sab of a substance at temperature T
and pressure P is expressed by the following expression:
SabT∫0 (δQ) rev / T

Importance of third law of thermodynamics is given below:

1) It helps in calculating the thermodynamicproperties.

2) It is helpful in measuring chemical affinity. Because of this it is

known as Nernst theorem.

3) It explains the behavior of solids at very low temperature.

4) It helps in analyzing chemical and phase equilibrium.

Third law of thermodynamics

The third law of thermodynamics is sometimes stated as follows:

The entropy of a perfect crystal at absolute zero is exactly equal to zero.

At zero kelvin the system must be in a state with the minimum

possible energy, and this statement of the third law holds true if the perfect
crystal has only one minimum energy state. Entropy is related to the number
of possible microstates, and with only one microstate available at zero kelvin,
the entropy is exactly zero.[1]

A more general form of the third law applies to systems such as glasses that
may have
We know that entropy is the rate of change of disorder occurring in a system. Walther
Nernst introduced the concept of entropy in the third law of thermodynamics which states that:

For a perfect crystal at the absolute zero temperature, the entropy would be exactly equal to
zero.When only one minimum energy state is possessed by a perfect crystal the law would hold
true.
If we consider systems such as glasses which are not perfect crystal then a generalized form of
3rd law would be:
When the temperature approaches zero, the randomness or entropy of a system would approach
a constant value.

The Constant value of entropy is called Residual Entropy and it should be noted that it is not
necessarily zero.

Third Law of Thermodynamics Equation

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The third law can be expressed as:

limT→0 S = 0 ...............................(a)Here
-1 -1
S = entropy which is expressed as J s K .

T = absolute temperature which is expressed in K.

It can also be written as:

T → 0 ⇒ S → Smin .....................................(b)Hence we can say if the temperature approaches

zero then the entropy approaches to its minimum value.
Another application of third law of thermodynamics:

S = 2.303 Cp log T ..........................................(c)Using this we can find the absolute entropy of any
substance at a given temperature T.
Here Cp is the heat capacity of the substance at a constant pressure.

Limitations of the law:

Even at 0 K Glassy solids have entropy which is greater than zero.

Solids that have mixtures of isotopes do not possess zero entropy at 0 K.

For example: Solid chlorine does not have zero entropy at 0 K.

Crystals of CO, N2O, NO, H2O, etc., do not possess perfect order even at 0 K, thus their entropy is
not equal to zero.

Third Law of Thermodynamics Examples

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We can consider H2O if we want to understand the concept of the third law of thermodynamics.

Water exists in three different states:

Gaseous state

Liquid state

Solid state

In Gaseous state
The entropy or randomness is very high. Here we are talking about the randomness in motion of
the molecules of which the water is made up of. They move with very high entropy.
In Liquid state
Now the randomness is reduced. It is not as free as the gaseous state and hence we can say that
entropy of the molecules is reduced. This is because the movement between the molecules is
reduced.

In Solid state
In this state the moment between molecules is almost zero. The entropy approaches almost zero
value. This is because the molecules are packed very tightly in the solid state and hence the
randomness is very low. This is when it is cooled at very low temperature or at an absolute zero
temperature.

Now if it cooled further then all the motion between the molecules would stop. This is because
these are no free spaces for the motion of the particles. And hence the entropy becomes almost

zero.more than one minimum energy state:

The entropy of a system approaches a constant value as the temperature

approaches zero.

Nernst-Simon statement follows:

The entropy change associated with any condensed system undergoing a

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

Another simple formulation of the third law can be:

It is impossible for any process, no matter how idealized, to reduce the

entropy of a system to its zero point value in a finite number of operations.
The constant value (not necessarily zero) is called the residual entropy of the
system.[2]

Physically, the law implies that it is impossible for any procedure to bring a
system to the absolute zero of temperature in a finite number of steps.[3]

History [edit]

The third law was developed by the chemist Walther Nernst during the years
1906-1912, and is therefore often referred to as Nernst's theorem or Nernst's
postulate. The third law of thermodynamics states that theentropy of a
system at absolute zero is a well-defined constant. This is because a system at
zero temperature exists in its ground state, so that its entropy is determined
only by the degeneracy of the ground state.

In 1912 Nernst stated the law thus: "It is impossible for any procedure to lead
to the isotherm T = 0 in a finite number of steps."[4]

An alternative version of the third law of thermodynamics as stated

by Gilbert N. Lewis and Merle Randall in 1923:

If the entropy of each element in some (perfect) crystalline state be taken as

zero at the absolute zero of temperature, every substance has a finite positive
entropy; but at the absolute zero of temperature the entropy may become
zero, and does so become in the case of perfect crystalline substances.
This version states not only ΔS
Δ will reach zero at 0 K, but S itself will also
reach zero
ro as long as the crystal has a ground state with only one
configuration. 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.
overcome [5]

With the development of statistical mechanics,

mechanics the third law of
thermodynamics (like the other laws) changed from a fundamental law
(justified by experiments) to a derived law (derived from even more basic
laws). The basic law from which it is primarily derived is the statistical
statistical-
mechanics definition of entropy for a large system:

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

of microstates consistent with the macroscopic configuration. The counting
of states is from the reference state of absolute zero, which corresponds to
the entropy of S0

Explanation [edit]

In simple terms, the third law states that the entropy of a perfect crystal
approaches zero as the absolute temperature approaches zero. This law
provides an absolute reference point for the determination of entropy. The
entropy determined relative to this point is the absolute entropy.
Mathematically, the absolute entropy of any system at zero temperature is
the natural log of the number of ground states times Boltzmann's constant
k B.

The entropy of a perfect crystal lattice as defined by Nernst's theorem is zero

provided that its ground state is unique, because ln(1) = 0.

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 ln(2)kB (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 0K, 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; indeed, from
an entropic perspective, this can be considered to be part of the definition of
"perfect crystal". Only ferromagnetic, antiferromagnetic,
and diamagnetic materials can satisfy this condition. Materials that remain
paramagnetic at 0K, by contrast, may have many nearly-degenerate ground
states (for example, in a spin glass),
glass or may retain dynamic disorder
(a quantum spin liquid).[citation
citation needed]
neede

Mathematical
ematical formulation
formulatio [edit]

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 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 δ
δQ is
then given by the second part of the Second law of thermodynamics
thermodynamicswhich
states that the entropy change of a system undergoing a reversible process is
given by

(1)

The temperature rise δT due to the heat δQ

δ is determined by the heat
capacity C(T,X)) according to

(2)

The parameter X is a symbolic notation for all parameters (such as pressure,

magnetic field, 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 the fraction of one of the two components.
Combining relations (1) and (2) gives

(3)

Integration of Eq.(3) from a reference temperature T0 to an arbitrary

temperature T gives the entropy at temperature T

(4)

We now come to the mathematical formulation of the third law. There are
three steps:

1: in the limit T0→0 the integral in Eq.(4) is inite. So that we may take T0=0
and write

(5)

2. the value of S(0,X)) is independent of X. In mathematical form

(6)
So Eq.(5) can be further simplified to

(7)

Equation (6) can also be formulated as

(8)

In words: at absolute zero all isothermal processes are isentropic. Eq.(8) is

the mathematical formulation of the third law.

3: as one is free to chose the zero of the entropy it is convenient to take

(9)

so that Eq.(7) reduces to the final form

(10)

The physical meaning of Eq.(9) is deeper than just a convenient selection of

the zero of the entropy. It is due to the perfect order at zero kelvin as
explained before.
Consequences of the third law
la [edit]

Fig.1 Left side: Absolute zero can be reached in a finite number of steps
ifS(0,X1)≠S(0, X2). Right: An infinite number of steps is needed
sinceS(0,X1)= S(0,X2).

Can absolute zero be obtained?

o [edit]

The third law is equivalent to the statement that

"It is impossible by any procedure,

procedure, no matter how idealized, to reduce the
temperature of any system to zero temperature in a finite number of finite
operations".[6]
The reason that T=0
=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 field is switched on and off in a controlled way. [7] If there would be
an entropy difference at absolute zero T=0
=0 could be reached in a finite
number of steps. However, at T=0
=0 there is no entropy difference so an infinite
number of steps would be
e needed. The process is illustrated in Fig.1.

Specific heat [edit]

Suppose that the heat capacity of a sample in the LT region can be

approximated by C(T,X)=C
C0Tα, then

(11)

The integral is finite for T0→0 if α>0.

0. So the heat capacity of all substances
must go to zero at absolute zero

(12)

The molar specific 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
 (13)

In the limit T0→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 conflict is solved as follows: At a certain

certain temperature the quantum
nature of matter starts to dominate the behavior. Fermi particles
follow Fermi-Dirac
Dirac statistics and Bose particles follow Bose-Einstein
Einstein
statistics.. In both cases the heat capacity at low temperatures is no longer
temperature independent, even for ideal gases. For Fermi gases

(14)

with the Fermi temperature TF given by

(15)

Here NA is Avogadro's number, Vm the molar volume, and M the molar mass.

For Bose gases

 (16)

with TB given by

(17)

The specific heats given by Eq.(14) and (16) both satisfy Eq.(12).

Vapor pressure [edit]

The only liquids near absolute zero are ³He and ⁴He. Their heat of
evaporation has a limiting value given by

(18)

with L0 and Cp constant. If we consider a container, partly filled with liquid

and partly gas, the entropy of the liquid-gas
liquid mixture is

(19)
where Sl(T) is the entropy of the liquid and x is the gas fraction. Clearly the
entropy change during the liquid-gas
liquid transition (x from 0 to 1) diverges in
the limit of T→0.
→0. 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.

Latent heat of melting

g [edit]

The melting curves of ³He and ⁴He both extend down to absolute zero at finite
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
atT=0.
As a result the latent heat
at of melting is zero and the slope of the melting
curve extrapolates to zero as a result of the Clausius-Clapeyron
Clapeyron equation
equation.

Thermal expansion coefficient

coeffi [edit]

The thermal expansion coefficient is defined as

(20)

With the Maxwell relation

 (21)

and Eq.(8) with X=p it is shown that

(22)

So the thermal expansion coefficient of all materials must go to zero at zero

kelvin.

References [edit]

^ J. Wilks The Third Law of Thermodynamics Oxford University Press

(1961).[page needed]

^ Kittel and Kroemer, Thermal Physics (2nd ed.), page 49.

^ 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,
Treatise, Academic Press, New York,
page 477.
^ Bailyn, M. (1994). A Survey of Thermodynamics, American Institute of
Physics, New York, ISBN 0–88318–797–3, page 342.

^ Kozliak, Evguenii; Lambert, Frank L. (2008). "Residual Entropy, the Third

Law and Latent Heat". Entropy 10 (3): 274–
84. Bibcode:2008Entrp..10..274K. doi:10.3390/e10030274.

^ Guggenheim, E.A. (1967). Thermodynamics. An Advanced Treatment for

Chemists and Physicists, fifth revised edition, North-Holland Publishing
Company, Amsterdam, page 157.

^ F. Pobell, Matter and Methods at Low Temperatures, (Springer-Verlag,

Berlin, 2007)[page needed]

Further reading [edit]

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.doi:10.1126/science.1227831. PMID 23288533. Lay summary – New
Scientist (January 3, 2013).