Refrigeration and Cryogenics

Aleksandra Bie
Seminar
Thermodynamic relations. Maxwell equations

James Clark Maxwell

Scottish physicist and matematician
Born: 13 June 1831, Edinburgh, Scotland
Died: 5 November 1879 Cambridge, England

Author of the second great unification in physics*

(after the first one released by Isaac Newton)

*Nahin, P.J., Spectrum, IEEE, Volume 29, Issue 3, March 1992 Page(s):45

James Clark Maxwell - Contributions

Electromagnetism:

the concept of the electromagnetic field in comparison to force lines that Faraday
discovered. His famous equations, in their modern form of four partial differential
equations, first appeared in fully developed form in his textbook A Treatise on
Electricity and Magnetism in 1873.

Colour analysis

contributed to the field of optics and the study of colour vision, creating the
foundation for practical colour photography;
Maxwell's discs were used to compare a variable mixture of three primary colours
with a sample colour by observing the spinning "colour top.

Control theory

Maxwell published a famous paper "On governors". This paper is quite frequently
considered a classical paper of the early days of control theory. Here governors refer to
the governor or the centrifugal governor used in steam engines.

James Clark Maxwell - Contributions

Kinetic theory and thermodynamics

investigated the kinetic theory of gases;

MaxwellBoltzmann kinetic theory of gases;

the Gedankenexperiment
as Maxwell's demon;

in 1871, he
relations.

established

(thought

experiment),

Maxwell's

known

thermodynamic

Maxwell's thermodynamic relations

Established in 1871. Statements of equality among the second derivatives of
the thermodynamic potentials with respect to different thermodynamic variables.
Maxwell's relations (general)

differentiation of an analytic function of two variables is irrelevant;

the partial derivatives are taken with all other natural variables held constant;
for every thermodynamic potential there are n(n 1)/2 possible Maxwell relations
where n is the number of natural variables for that potential.

Fundamental thermodynamic relations

Function of state

Natural
variables

Formula

Internal energy

S,V

Enthalpy

S,p

H=E+pV

Entropy

U,V

S=Q/T

Free energy

T,V

F=E-TS

Free enthalpy

T,p

G=H-TS

A thermodynamic potential is a scalar function used to represent

the thermodynamic state of a system.

Thermodynamic potential Internal energy

total energy contained by a thermodynamic system;

energy needed to create the system;
excludes the energy to displace the system's surroundings, any energy associated with a
move as a whole, or due to external force fields;
two major components, kinetic energy and potential energy;
can be changed by heating the system or by doing work on it;
increase in internal energy is equal to the total heat added and work done;
If the system is isolated, its internal energy cannot change.

E = (TdS pdV ) dE = TdS pdV

the total derivative of with respect to the natural variables:

E
E
dE ( S , V ) = dS +
dV
S V
V T

E = (TdS pdV ) dE = TdS pdV

E
E
dE ( S ,V ) = dS +
dV
S V
V S
This indicates that:

E
T =
S V

E
p=

Differentiation of the left equation by V and the right equation by S:

E
T

V s V S V S

E
p
=

S V
S V S V

In second derivation the order of differentiation does not matter, thus:

T
p

=
V s
S V

Thermodynamic potential Free energy

known as a Helmholtz potential;

measures the useful work obtainable from a closed thermodynamic system at a

constant temperature and volume;

change of free energy is equal to maximum work done by the system in constant
temperature;

Very often used, because of its natural variables (T,V), which are easy to measure.

F (T ,V ) = E TS

dF (T , V ) = dE TdS SdT = TdS pdV TdS SdT = SdT pdV

dF (T , V ) = SdT pdV

dF (T , V ) = SdT pdV
F
F
dF (T , V ) =
dT +
dV
T V
V T
This indicates that:

F
S =

F
p=

Differentiation of the left equation by V and the right equation by T:

F
S

V T V T V T

F
p

=

T V T V T V

In second derivation the order of differentiation does not matter, thus:

S p

=
V T T V

Thermodynamic potential Enthalpy

measure of the total energy of a thermodynamic system;

includes the internal energy and the amount of energy required to make room for it;
state function and an extensive quantity;
simplifies descriptions of energy transfer;
The total enthalpy, H, of a system cannot be measured directly;
H, is a more useful quantity than its absolute value.

H ( S , p) = E + pV

dH ( S , p ) = dE + pdV + Vdp = TdS pdV + pdV + Vdp = TdS + Vdp

dH ( S , p ) = TdS + Vdp

dH ( S , p ) = TdS + Vdp
H
H
dp
dH ( S , p ) =
dS +
S p
p S
This indicates that:

H
T =

V =

Differentiation of the left equation by p and the right equation by S:

H
T

=

p S p S p S

H
V

p
S p

In second derivation the order of differentiation does not matter, thus:

T V
=

p S S p

Thermodynamic potential Free Enthalpy

also known as a Gibbs Function;

a maximum work attainable in a closed system which is not related to the change of volume.

G(T , p) = H TS

dG (T , p ) = dH TdS SdT = TdS + Vdp TdS SdT = SdT + Vdp

dG (T , p ) = SdT + Vdp

dG (T , p ) = SdT + Vdp
G
G
dp
dG (T , p) =
dT +
T p
p T
This indicates that:

G
S =

V =

Differentiation of the left equation by p and the right equation by T:

G
S
=

p T p T p T

G
V

p
T p

In second derivation the order of differentiation does not matter, thus:

S V
=

p T T p

Thermodynamic potentials

When the temperature (T ) and external parameters of a closed system are held constant, the
Helmholtz free energy (F ) decreases and reaches a minimum value at equilibrium.

When the pressure (p ) and external parameters of a closed system are held constant, the enthalpy
(H ) decreases and reaches a minimum value at equilibrium.

When the temperature (T ), pressure (p ) and external parameters of a closed system are held
constant, the Gibbs free enthalpy (G ) decreases and reaches a minimum value at equilibrium.

Thus:

When the entropy (S ) and "external parameters" (e.g. volume) of a closed system are held constant,
the internal energy (U ) decreases and reaches a minimum value at equilibrium. This follows from the
first and second laws of thermodynamics and is called the principle of minimum energy. The following
three statements are directly derivable from this principle.

It is much more convenient to operate on volume and entropy related to mass of the
substance. Obtained Maxwell relations formula are recalculated for m, so that the most
common version of these formulas is obtained.

T
p

=
V S
S V

T
p

=
v s
s v

S p

=
V T T V

s p
m

=
v T T v

S
V
=

T p
p T

s
v

T p
p T

T V
=

p S S p

T v
m
=

p s s p

The four basic Maxwell relations enable transformation of any thermodynamic relation
with the aid of thermodynamic susceptibilities such as , , cp.

Thermodynamic susceptibilities
Thermal capacity at v=const:

cv =

1 E

n T V

Thermal capacity at p=const:

cp =

1 H

n T p

Thermal expansion:

Compressibility at T=const:

T =

Compressibility at S=const:

1 V

V T p

1 V

V p

T
1 V

S =
V p S

= const
V

dE = TdS cv =

T S

n T V

p =const

dE = TdS c p =

T S

n T p

Example of application adiabatic compression

In this process we increase pressure at constant entropy and observe the temperature change.

T
dp
dT =
p

S
x y z
T p S
= 1 thus


= 1

y
z
x
p
S
T
p
z x y

S T
Thermodynamic susceptibilities:

cpn
S

=
T
T p
1

x y
=
y z x z
Maxwell relation:

S V
=

p
T

p S
=
S T p T
thus

1 V

V T p

The temparature change at adiabatic compression of gas:

dT =

1
p
=
V
S T

T v
dp
cp

Mnemonic way to calculate Maxwell relations

Guggenheims square

T
p

=
V s
S V

Mnemonic way to calculate Maxwell relations

A mnemonic used by physics students to remember
the Maxwell relations in thermodynamics which helps
them remember the order of the variables in the square,
in clockwise direction is:
"Good Physicists Have Studied Under Very Fine Teachers
Another mnemonic used here is (letters in the normal left
to right writing direction) :
"Valid Factsand Theoretical Understanding Generate
Solutions to Hard Problems

Conclusions
Why use Maxwell relations?
Certain variables in thermodynamics are hard to measure experimentally such as
entropy. Maxwell relations provide a way to exchange variables;
Relations enable derivations of formulas of thermodynamic functions such as , , cp;
Can be used to estimate the amount of energy obtained from the thermodynamic
system under specific conditions.

Thank you for Your attention !