Nernst Heat Theorem

In 1906, Walther Nernst, a German chemist (1864-1941) formulated an equation which relates
change in Gibbs free energy and enthalpy with temperature, commonly called Nernst heat theorem.
This theorem helped pave the way for the third law of thermodynamics, for which he won the 1920
Nobel Prize in Chemistry.
According to Gibbs-Helmholtz equation, we know that
𝛿𝐹
𝐹 = 𝐻+𝑇( )
𝛿𝑇 𝑃
For a finite change of a process, we can write above equation.
𝛿(𝛥𝐹)
𝛥𝐹 = 𝛥𝐻 + 𝑇 ( )
𝛿𝑇 𝑃

𝛿(𝛥𝐹)
𝛥𝐹 − 𝛥𝐻 = 𝑇 ( )
𝛿𝑇 𝑃

When K=0, above equation becomes;

𝛥𝐹 − 𝛥𝐻 = 0
or
𝛥𝐹 = 𝛥𝐻 Eq.1
Eq.1 explained when temperature approaches to zero (K=0), Gibb’s free energy becomes equal
to enthalpy change. Mathematically,
Lim
T→0 𝛥𝐹 = LimT→0 ΔH Eq.2
𝛿(𝛥𝐹)
As per Nernst heat theorem, the ( ) decreases with temperature asymptotically and finally
𝛿𝑇 𝑃
becomes equal to zero at absolute zero. Mathematically, we can write above statement as;

Lim 𝛿(𝛥𝐹) 𝛿(𝛥𝐻)

T→0 ( 𝛿𝑇
) = LimT→0 ( 𝛿𝑇
) =0 Eq.3
𝑃 𝑃

Case -1
Gibbs free energy is based on enthalpy and entropy (F=H-TS), so we can relate above equation
with entropy as;
∵ we know that dF=VdP-SdT
𝛿𝐹
At constant pressure, we have dF= -SdT ⇒ (𝛿𝑇 ) = -S Eq.4
𝑃
Eq. 4 can be written for a change in free energy and entropy for a process, hence
𝛿(𝛥𝐹)
( 𝛿𝑇
) = -ΔS
𝑃

At K=0, left hand side of equation becomes zero, therefore

-ΔS = 0

⇒ LimT→0 ΔS = 0

⇒ LimT→0 (S2-S1) = 0

⇒ when T=0, S2 = S1 Eq.5

Eq. 5 implies that at absolute zero, entropy at constant pressure during any transformation remain
unchanged.
Case -2
Nernst heat theorem can also be used to study the variation in molar specific heat at constant
pressure for the process occurring near absolute zero.
𝛿𝐻
∵ we know that CP = ( 𝛿𝑇 ) Or
𝑃
𝛿(𝛥𝐻)
ΔCP = ( 𝛿𝑇
) Or in the vicinity of absolute zero, we have
𝑃

Lim 𝛿(𝛥𝐻)
T→0 ΔCP = LimT→0 ( )
𝛿𝑇 𝑃
At T=0, right hand side of equation becomes zero, so we get;
Lim
T→0 ΔCP = 0

⇒ LimT→0 (CP2- CP1) =0

⇒ LimT→0 (CP2) = LimT→0 (CP1) Eq.6

Eq. 6 implies that at absolute zero, molar heat capacity at constant pressure during any
transformation remain unchanged.
The variation of 𝛥𝐻 and 𝛥𝐹 with temperature can be shown graphically in Figure 1. It can be
seen 𝛥𝐻 and 𝛥𝐹 meet each other’s at a short region above absolute zero and run coinciding upto

Figure 1: Graphical representation of Nernst Heat Theorem

absolute zero (solid lines in graph). While the dotted lines reveals that the two value 𝛥𝐻 and 𝛥𝐹
not only become equal to each other at absolute zero but they also approach to each other rapidly.

Significance of Nernst heat theorem: The Nernst heat theorem was later used by Max Planck to
give the third law of thermodynamics, which is that the entropy of all pure, perfectly crystalline
homogeneous materials in complete internal equilibrium is 0 at absolute zero.

Third law of Thermodynamics

Definitions:

Physical activities of substances tend to vanish as the temperature approaches absolute zero (By
Nernst Walther)

OR

Every substance has a finite positive entropy, but at zero kelvin the entropy may become zero,
and does so in the case of a perfectly crystalline substance. (Extended form by Max Planks)

OR

The entropy of pure solid in crystalline form may be taken as zero at absolute zero.

The Third Law of Thermodynamics is unlike the first two laws in that it introduces no new state
function. The first law gives us the energy and the second law give us the entropy; the third law
provides a numerical scale for entropy.
Since we already know that entropy is created or generated whenever a spontaneous or irreversible
process occurs in an isolated system. Therefore, entropy of an isolated system that is not in
equilibrium will increase until the system reaches equilibrium, from which time the entropy will
remain constant. Mathematically we can write this as dS ≥ 0 for a process that occurs at constant
E and V.

At a temperature of zero Kelvin, the following phenomena can be observed in a closed system:

1. The system does not contain any heat.

2. All the atoms and molecules in the system are at their lowest energy points.

Therefore, a system at absolute zero has only one accessible microstate – it’s ground state. As
per the third law of thermodynamics, the entropy of such a system is exactly zero.

Mathematical Derivation of third law of thermodynamics:

According to Nernst heat theorem, we have

Lim
T→0 ΔS = 0 (for perfect crystalline solid)

Third law of thermodynamics can be derived using concept of molar heat capacity such as.

Applications: The Third Law of thermodynamics used to calculate equilibrium constants from
thermal data and absolute values of the entropy of substances.

𝛿Q
CP = ( 𝛿𝑇 ) Eq.1
𝑃
According to second law of thermodynamics, we have
𝛿𝑄
= dS ⇒ 𝛿𝑄 = 𝑇𝑑𝑆 Eq.2
𝑇
Putting value of 𝛿𝑄 in Eq.1, we get
TdS
CP = ( 𝛿𝑇 ) On rearranging we have
𝑃
CP 𝛿𝑇 = TdS or
𝛿Q
CP = dS On integrating from above equation in between entropy
𝑇
at 0 K (S0 ) and entropy at absolute temperature (ST )we have

ST T
dT
∫ dS = ∫ CP
T
S0 0

T dT
ST - S0 = ∫0 CP Eq.3
T
For a finite value of ST - S0 , CP must be zero at absolute zero. Hence 3rd law can be restated as ;
Lim
T→0 CP = 0
Determination of Absolute entropy of a substance
One of the applications of 3rd Law of thermodynamics is the determination of absolute entropy of
a substance.
T dT
∵ we know that ST - S0 = ∫0 CP
T
According to 3rd Law of thermodynamics, entropy at temperature of pure substance in its pure
crystalline form is zero at 0K, so above Eq will become

T dT T CP
ST = ∫0 CP or ST = ∫0 dT Eq. 1
T T
Mathematically we know that
d 1 dT
(lnT) = ⇒ d ln T=
dT T T
Putting value of dT/T in Eq. 1 we get
T T
ST = ∫0 CP (d lnT) ⇒ 2.303∫ CP (d logT)
0
Eq. 2
The value of above Eq.2 can be determined by measuring the area under a curve of 𝐶𝑃 versus
𝑙𝑜𝑔𝑇.
In addition, entropy of gaseous substance at a temperature T is given by the sum of all the
entropies involved;
Tm 𝛥Hf Tb T
ST = ∫
0
C P (s) d ln T +
Tf
+ ∫ C
Tm P (f)
d ln T + 𝛥H
T
V
+∫T CP (g) d ln T Eq. 3
b b

Where
Tm = Entropy of melting
Tf = Entropy of fusion
Tb = Entropy of boiling
Tf = Entropy of vaporization
Eq. 3 is very useful to measure the entropy for different phase changes from solid to liquid and
liquid to gases.