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Thermodynamics:
Deriving the
Maxwell Relations
Posted by Youssef Moawad (/) on:
02/06/2018, in Physics
(/blog/section/physics)

INTRO AND WELCOME BACK TO THE

PHYSICS BLOG!
It has been a good bit of time since I posted the prelude article to
this, so it's about time I write this! Welcome back!!
In this blog, I will be deriving Maxwell's relations of thermodynamic
potentials. These are a set of relations which are useful because
they allow us to change certain quantities, which are often hard to
measure in the real world, to others which can be easily measured.
I will assume that you have read the prelude article to this
(/blog/exactDiffAndPartialDiffRel) about exact differentials and
partial differential relations and are comfortable with these
concepts.
Throughout the article, I will also be assuming the reader is familiar
with the basics of thermodynamics, including the first and second
laws, entropy, etc. Indeed, this topic is mostly mathematical, and
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 once the fundamental equations are found, everything else follows
Youssef Moawad > Blog
as a direct mathematical manipulation. I will try, however, to give as
much context as we go as I can. The main equations I will assume
you are familiar with are:

Work done on a gas during a change of volume: δW = −P dV

First law of thermodynamics: dU = δQ + δW = δQ − P dV

Second law of thermodynamics in terms of entropy: δQ = T dS

where δW and δQ are inexact differentials. We showed this in the

prelude article.
Now that's out of the way, let's get started!

THERMODYNAMIC POTENTIALS
A thermodynamic potential is some quantity used to represent
some thermodynamic state in a system. We can define many
thermodynamic potentials on a system and they each give a
different measure of the "type" of energy the system has. In this
article, we will consider four such potentials.

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Youssef Moawad > Blog

INTERNAL ENERGY
The first thermodynamic potential we will consider is internal
energy, which will most likely be the one you're most familiar with
from past studies of thermodynamics. The internal energy of a
system is the energy contained in it. This is excluding any energy
from outside of the system (due to any external forces) or the
kinetic energy of a system as a whole. This is only the energy of the
system due to the motion and interactions of the particles that make
up the system.
Let's consider the first law of thermodynamics, which gives us a
differetial form for the internal energy:

dU = δQ + δW

We know that the work done on a system, δW , is given by:

δW = −P dV . Additionally, from the second law of

thermodynamics, in terms of entropy, we know that the heat

transferred is given by: δQ = T dS . Substituting this in the above
expression for dU , we get:

dU = T dS − P dV

This differential form is often known as the fundamental

thermodynamic relation.
From the above we know that the natural variables of a
thermodynamic potentials are the ones which, if kept constant,
mean that the potential is conserved through some process. In this
case this means that dU = 0. This is achieved when dS and dV
are both zero. So entropy, S, and volume, V, are the natural
variables of internal energy, U.
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 ENTHALPY
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Enthalpy (represented by the letter H ) is a thermodynamic potential
of a system, which is equal to the internal energy of the system plus
the product of its pressure and volume:

H = U + PV

This represents the total heat content of a system and is often the
preferred potential to use when studying many chemical reactions
which take place at constant pressure. This is because when
pressure is constant, the change of enthalpy is equal to the change
in internal energy of the system.
There's definitely much more to be said about the usefulness of
using enthalpy in certain processes, but I will leave it here and
move on to find its differential form. Really all you need to know
about enthalpy to continue is its mathematical definition given
above.
Let's try to find dH from the above expression:

dH = dU + d(P V ) = dU + P dV + V dP

What I've done here in the last step is use the product rule for the
differential to expand d(P V ) into P dV + V dP . We can now use
the differential form of the internal energy dU = T dS − P dV to
substitute for dU :

dH = T dS − P dV + P dV + V dP

⇒ dH = T dS + V dP

where in the last step, −P dV cancels P dV and we're left with that
result. This is the differential form of enthalpy. We can apply the
same idea we applied to internal energy here to find the natural

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 variables of enthalpy. We can see that dH = 0 when dS and dP
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are zero. So entropy, S, and pressure, P, are the natural
variables of enthalpy, H.

HELMHOLTZ FREE ENERGY

The Helmholtz free energy (represented by the letter F ) of a
system is defined as the internal energy of the system minus the
product of its entropy and temperature:

F = U − TS

This represents the amount of useful work that can be obtained

from a closed system at constant temperature and volume. Again, I
won't spend too long on the uses of this thermodynamic potential.
Let's now find the differential form of this, the same way we did with
enthalpy:

dF = dU − d(T S) = dU − T dS − SdT

Substituting in the differential form of internal energy (

dU = T dS − P dV ):

dF = T dS − P dV − T dS − SdT

⇒ dF = −P dV − SdT

This is the differential form of the Helmholtz free energy. We can

now immediately see that volume, V, and temperature, T, are the
natural variables of the Helmholtz free energy, F.

GIBBS FREE ENERGY

The last thermodynamic potential we'll consider is the Gibbs free
energy (represented by the letter G). This potential is used to
calculate the amount of work a system can perform at constant
temperature and pressure. As such, it is very useful when studying /
 phase transitions, which happen at such conditions. This is defined
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as the enthalpy of a system minus the product of the temperature
and entropy of the system:

G = H − TS

Finding the differential form of this (as above):

dG = dH − d(T S) = dH − T dS − SdT

Substituting in the differential form of enthalpy (

dH = T dS + V dP ):

dG = T dS + V dP − T dS − SdT

⇒ dG = V dP − SdT

This is the differential form of the Gibbs free energy. We can see
that pressure, P, and temperature, T, are the natural variables of
the Gibbs free energy, G.

DERIVING MAXWELL'S RELATIONS

So far we have derived the differential forms of the four
thermodynamic potentials in which we're interested and have
identified their natural variables. This is summarised in the following
table:
Thermodynamic Potential Differential Form Natural Variables
Internal Energy, U dU = T dS − P dV S ,V
Enthalpy, H dH = T dS + V dP S ,P
Helmholtz Free Energy, F dF = −P dV − SdT V ,T
Gibbs Free Energy, G dG = V dP − SdT P ,T

We can now start using these in our derivation of the Maxwell

relations. But first, a recap!

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Youssef Moawad > Blog

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Youssef Moawad > Blog

INTERNAL ENERGY MAXWELL RELATION

Let's start by again considering the differential form of the internal
energy, given by dU = T dS − P dV . Consider now U as a
function of entropy, S, and volume, V, such that U = U (S, V ).
Notice that these are the natural variables of internal energy. We
can now write the total differential of U (S, V ) as:

∂U ∂U
dU = ( )V dS + ( )S dV
∂S ∂V

We can now equate the two expressions for dU (the above and the
differential form), to see that:

∂U ∂U
( )V dS + ( )S dV = T dS − P dV
∂S ∂V /
Youssef Moawad > Blog
From here, we can equate the coefficients of dS and dV :

∂U
( )V = T
∂S

∂U
( )S = −P
∂V

Let's only consider the first of these for now: ( ∂S )V . Consider

∂U
= T

here differentiating both sides with respect to V while keeping S

constant. This means we apply to both sides, such that:
∂
)S
∂V

∂ ∂U ∂T
)S ( )V = ( )S
∂V ∂S ∂V

Here the left hand side can be expressed as , such

∂ ∂
)S )V U
∂V ∂S

that we can indeed flip the order of differentiation freely. This is due
to the equality of the mixed second order partial derivatives. This is
important because now will consider the second equation,
.
∂U
( )S = −P
∂V

Consider differentiating both sides of ( ∂V with respect to

∂U
)S = −P

while keeping V constant. This means applying to both

∂
S )V
∂S

sides:

∂ ∂U ∂P
)V ( )S = −( )V
∂S ∂V ∂S

Again notice how we can express the left hand side as

∂
)V
∂
)S U , and that we can flip the order here as well. We have:
∂S ∂V

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Youssef Moawad > Blog
∂ ∂ ∂ ∂
)V )S U = )S )V U
∂S ∂V ∂V ∂S

And from the two results above, we can say that:

∂T ∂P
( )S = −( )V
∂V ∂S

And this is indeed our first Maxwell Relation. All the others follow
similar logic to the one applied here but using the other three
thermodynamic potentials.

ENTHALPY MAXWELL RELATION

Take the differential form of enthalpy (dH = T dS + V dP ) and
consider the enthalpy, H , as a function of its natural variables, S
and P , such that H = H (S, P ). We can find the total differential
of enthalpy from this:

∂H ∂H
dH = ( )P dS + ( )S dP
∂S ∂P

Now equate this to the differential form to get:

∂H ∂H
( )P dS + ( )S dP = T dS + V dP
∂S ∂P

Equating coefficients of dS and dP , we get:

∂H
( )P = T
∂S

∂H
( )S = V
∂P

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 Differentiating both sides of the first of these expresssions with
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respect to P while keeping S constant, we get:

∂ ∂H ∂T
)S ( )P = ( )S
∂P ∂S ∂P

And differentiating the second expression with respect to S while

keeping P constant, we have:

∂ ∂H ∂V
)P ( )S = ( )P
∂S ∂P ∂S

By the equality of the mixed second order partial derivatives, these

expressions are equivalent, so we have:

∂T ∂V
( )S = ( )P
∂P ∂S

This is our second Maxwell Relation.

HELMHOLTZ FREE ENERGY MAXWELL

RELATION
This follows the same procedure here as we did in the above two,
so I will simply include the mathematical steps without much
commentary. If any part of this is unclear, please feel free to let me
know (/contact)!

dF = −P dV − SdT

Consider F = F (V , T )

∂F ∂F
⇒ dF = ( )T dV + ( )V dT
∂V ∂T

∂F ∂F
⇒ ( )T dV + ( )V dT = −P dV − SdT
∂V ∂T /
 ∂F ∂F
Youssef Moawad > Blog ⇒ ( )T = −P , ( )V = −S
∂V ∂T

∂ ∂F ∂P
⇒ )V ( )T = −( )V ,
∂T ∂V ∂T

∂ ∂F ∂S
)T ( )V = −( )T
∂V ∂T ∂V

∂P ∂S
⇒ −( )V = −( )T
∂T ∂V

And finally:

∂P ∂S
⇒ ( )V = ( )T
∂T ∂V

This is the third Maxwell Relation.

GIBBS FREE ENERGY MAXWELL RELATION

Again, like the above, I will simply include the mathematical steps
here:

dG = V dP − SdT

Consider G = G(P , T )

∂G ∂G
⇒ dG = ( )T dP + ( )P dT
∂P ∂T

∂G ∂G
⇒ ( )T dP + ( )P dT = V dP − SdT
∂P ∂T

∂G ∂G
⇒ ( )T = V , ( )P = −S
∂P ∂T

∂ ∂G ∂V
⇒ )P ( )T = ( )P ,
∂T ∂P ∂T
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 ∂ ∂G ∂S
Youssef Moawad > Blog )T ( )P = −( )T
∂P ∂T ∂P

And finally:

∂V ∂S
⇒ ( )P = −( )T
∂T ∂P

And that's our fourth Maxwell Relation.

CONCLUSIONS
In this post we derived the four most common Maxwell Relations.
There are summarised here:

∂T ∂P
( )S = −( )V
∂V ∂S

∂T ∂V
( )S = ( )P
∂P ∂S

∂P ∂S
( )V = ( )T
∂T ∂V

∂V ∂S
( )P = −( )T
∂T ∂P

Keep in mind that these are not the only Maxwell Relations we can
find. Indeed, there are other thermodynamic potentials that we can
define over a system, each one bringing a Maxwell Relation. In
addition, there could be other physical quantities that potentials we
discussed here could depend on. For example, we might have a
system affected by some magnetic field, in which case, we would
have to take that into account for internal energy. And this would
change our Maxwell Relation.

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 Maxwell Relations are useful because often times there are
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quantities in which we are interested, perhaps like ( ∂P
∂S
)T , which

are not easily measurable. We can use a Maxwell Relation to

change these into ones we can more readily measure, −( ∂V
∂T
)P for
this example.

WHAT'S NEXT?
In a future post, we will use these Maxwell Relations to derive
relationships between the heat capacities of systems. So be on the
lookout for that sometime soon. There's also a mnemonic that helps
with remembering the Maxwell Relations about which I may write a
brief post.

I hope you found this post informative! Please do feel free to leave
a comment below or contact me directly (/contact) to give me some
feedback. Feedback is always appreciated and will help improve
the blog and future articles. Thanks!
Update (16/04/2018): A Mnemonic to Remember the Maxwell
Relations is now up, here (/blog/mRelationsMnemonic).

RELATED
You may also be interested in:
Prelude to Maxwell Relations: Exact Differentials and Partial
Differential Relations (/blog/exactDiffAndPartialDiffRel)
Particle Physics, Part 1: Why is the Standard Model so cool?
(/blog/thestandardmodel)
Symmetries: The Beauty in Physics (/blog/physSymmetries)

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© Youssef Moawad (/) 2019

I'm a Computing Science and Physics undergraduate at the University of Glasgow. I build and publish
mobile apps and work on websites. I'm also a particle physics enthusiast and I enjoy blogging about
physics and tech.
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