The Terrible Beauty of Thermodynamics

Bonus: You can ignore everything in boxes if you like!

The whole point of thermodynamics is not that it provides any theoretical insight into
the behaviour of matter but rather that it describes accurately the state or condition of
substances and how they behave in chemical or physical changes. This means that,
rather than actually having to carry out experiments, which may well be tedious, time-
consuming or difficult, or some combination of these, we can discover the results with
a few ‘simple’ calculations.

Thermodynamics also deals with the movement of energy from one system to another,
from one form to another, from one chemical species to another. As we are quite
besotted by doing exactly this in our modern world, thermodynamics is increasingly
important.

The trouble is that thermodynamics is expressed in the language of calculus and

worse, the calculus of functions of many variables, so that if you are not sufficiently
familiar with this language you see only the terror and none of the beauty of
thermodynamics.

A Couple of Calculus Rules:

 ∂F   ∂F 
• If F is a state function, then dF =   dx +   dy
 ∂x  y  ∂y  x
where x and y are variables of state of the system.

• The Euler reciprocity relation (for F a state function):

 ∂M   ∂N 
If dF = Mdx + Ndy , then   =  
 ∂y  x  ∂x  y

If this were the only problem, we could just take a deep breath and get on with it, but
to make things properly unpleasant, most of the important quantities are difficult or
impossible to measure directly. The fundamental relations are a bit like eigenfunctions
in quantum mechanics, once you know them you can calculate any thermodynamic
property but finding out what they are, by measurement or calculation, is a serious
problem.

Additionally, more than any other topic, thermodynamics is littered with fossils from
its past and, worse, seems to take a perverse pride in this amazing palaeodiversity. It
is this feature more than any other that makes thermodynamics confusing, at least
initially. (Or, in many people’s cases, terminally!)

The origin of the confusion lies in the fact that the variables we use to describe the
state of a system are not independent. Thus, instead of having just one thermodynamic
potential F(S, T, V, P, n), there are many equivalent potentials that depend on which
of the parameters of state you choose to express in terms of the others. The situation is
analogous to using different languages to express exactly the same ideas.

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Unfortunately, people who do thermodynamics are not inclined to stick to just one
language (forget about them ever agreeing on just one standard version!) but jump
annoyingly from one language to another.

Even if we get rid of n by performing all our calculations on one mole (so all our
quantities are ‘per mole’) there are still four equivalent, commonly used languages:

U ( S ,V ) , H ( S , P) , G (T , P) and A(T ,V )

Three of these fundamental relations we have already encountered, the fourth, A, is

called the Helmholtz free energy.

In U-language, for example, U is expressed as a function of S and V (remember that

we are doing everything ‘per mole’) and the other parameters are given by derivatives
of U (partial derivatives because U is a function of more than one variable):
∂U ∂U
T= and P = −
∂S ∂V
The other languages have a similar structure.

The Babel fish: Legendre Transformation

While we might blame mathematicians for the horrors of the calculus of functions of
many variables, we nevertheless have cause to thank them for providing us with a
device that will translate automatically from one thermodynamic language into
another. This device is called Legendre Transformation.

In a form in which we can use it easily, Legendre transformation goes like this:

Suppose that we have a function of two variables, f ( x, y ) ,

the differential of which is: df = wdx + zdy .
Then the transformation g ≡ f − wx will change the differentials from [dx and dy] to
[dw and dy]. That is, dg = − xdw + zdy .

Proof:
Let g ≡ f − wx , then
dg = df − d ( wx)
= df − wdx − xdw
= wdx + zdw − wdx − xdw
= − xdw + zdy

To put this result into a more user-friendly form, if you have a differential
df = wdx + zdy and you want to ‘swap’ w and x, then:
• in the differential, swap the variables and change the sign, and
• the new function is the old function minus the product of the variables.
You can swap x and w, or z and y, or both
Be careful with signs!

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So, how does this work?

The differential dU = TdS − PdV is a convenient combination of the First and Second
laws.
U = q−w (First Law)
∴ dU = dq − dw
 dq 
= TdS − PdV  dS = 
 T 

Well, this is just the differential for U-language, so let’s translate into the others.

Differential Function
swap the variables and change the sign new f’n = old f’n – product of the variables

dU = TdS − PdV = TdS + (− P )dV U

swap V and (–P) swap V and (–P)

dH = TdS + VdP H = U + PV

swap T and S swap T and S

dG = − SdT + VdP G = H - TS

swap P and V swap P and V

dA = − SdT − PdV A = G – PV = H – TS – PV = U – TS

swap T and (–S) swap T and (–S)

dU = TdS − PdV U = A + TS

Easy once you get the hang of it, isn’t it.

In the brief glimpse of thermodynamics that follows we will derive some of the
equations and relationships that we have encountered in earlier chapters.

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Talking the Talk: G-language
Because we have done lots on Gibbs free energy in the earlier chapters, let’s ask
ourselves how G changes with P and T.

If you don’t use Legendre Transformations, which let you go from dU (with
differentials dS and dV) to dG (with differentials dT and dP) in one step, you have to
do this:

G = H –TS = U + PV – TS (def’n of G; def’n of H)

∴ dG = dU + PdV + VdP – TdS – SdT (product rule)

but dU = dq – dw = TdS – PdV (def’n of U, def’n of S)

∴ dG = TdS – PdV + PdV + VdP – TdS – SdT

∴ dG = VdP – SdT

Which, after all, is just the same result as from the Legendre Transformations.

dG = VdP – SdT

Let’s now use this equation to derive some familiar results.

Consider two phases in equilibrium i.e. at the same temperature and pressure.
The change in G here is that of a phase change, the changes in P and T are
infinitesimal ones along the coexistence line, that is keeping G1 = G2 but changing
both slightly by dG1 and dG2.

G1 = G2

∴ ∆G = 0 and G1 + dG1 = G2 + dG2

∴ V1 dP − S1 dT = V2 dP − S 2 dT

∴ (V2 − V1 )dP = (S 2 − S1 )dT

dP ∆S ∆H
∴ = = (at equilibrium, ∆H = T∆S)
dT ∆V T∆V

This is the Clapeyron Equation we encountered in calculating Phase Diagrams.

What is more, if the process of interest is sublimation or vaporisation so that:

∆V = Vgas – Vcondensed phase ≈ Vgas

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Then, for Vgas equal to the molar volume, the Clapeyron equation becomes:

dP ∆H ∆H
= = P (assuming ideal behaviour)
dT TVgas RT 2

⌠ dP = ∆H ⌠ dT
P2 T2
∴   (assuming ∆H constant)
⌡P1 P R ⌡T1 T 2

P  − ∆H  1 1 
∴ ln 2  =  − 
 P1  R  T2 T1 

This is the Clausius-Clapeyron Equation, which underpinned the whole of the first
chapter.

Consider an isothermal change (for which T is constant, so dT = 0).

dG = VdP – SdT = VdP

 ∂G 
∴   =V
 ∂P  T
RT
In the simple case of one mole of an ideal gas (for which V = )
P
 ∂G 
  =V
 ∂P  T

P2
dP
dG = RT ⌠
G2
∴ ∫G1

⌡P1 P

P 
∴ ∆G = RT ln 2 
 P1 
You may recall from the previous chapter that the work done by an ideal gas
P 
undergoing a reversible isothermal expansion is (per mole) RT ln 1  and that this is
 P2 
the maximum possible work.

P 
∴ − ∆G = RT ln 1  = wmax
 P2 

which agrees with what we said when we introduced Gibbs free energy. It is also
obvious that if P1 > P2 , ∆G is negative and the expansion is spontaneous.

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Consider an isobaric process (for which P is constant, so dP = 0).

dG = VdP – SdT

 ∂G  G−H
∴   = −S = (G = H – TS)
 ∂T  P T

 ∂  G  1  ∂G  G
Now,     =   − 2 (product rule)
 ∂T  T   P T  ∂T  P T

−G 1 G − H 
= +  
T2 T  T 

−H
=
T2

∂  ∆G  − ∆H
Thus,   =
∂T  T  P T2

but ∆G 0 = − RT ln K

∴
d
(ln K ) = ∆H2
dT RT
K2
⌠ ∆H ⌠ T2 dT
∴  d (ln K ) = 
⌡ K1 R ⌡T1 T 2

K  − ∆H  1 1 
∴ ln 2  =  − 
 K1  R  T2 T1 

and this is the Van’t Hoff Equation that we derived by other means in the interlude
between Chapters 1 and 2.

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 ∂  ∂G  ∂  ∂G 
Consider the identity   =  
∂T  ∂P  T ∂P  ∂T  P

(which holds because the order of differentiation doesn’t matter)

 ∂G   ∂G 
From dG = VdP − SdT it is clear that   = V and   = −S
 ∂P  T  ∂T  P

so that, at constant temperature

 ∂V 
dS = −  dP
 ∂T  P

P2 P
⌠  ∂V  ⌠
2

Thus, ∆S = −   dP = − α V0 dP
⌡P1  ∂T  P ⌡P1

where α is the coefficient of thermal expansion

 ∂V  R
For one mole of an ideal gas,   =
 ∂T  P P

P  V 
So that ∆S = − R ln 2  = R ln 2 
 P1   V1 

which shows that an increase in volume leads to an increase in entropy, as you

would expect.

∆q rev
Also, as ∆S = , this is the same as a result we found in the previous
T
chapter for the heat change associated with a reversible isothermal change in
pressure or volume in an ideal gas.

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For a final example, let’s do something new with molar heat capacities.

dq V  ∂U  dq  ∂H 
By definition, C V = =  and C P = P =  
dT  ∂T  V dT  ∂T  P

 ∂H   ∂U 
∴ CP − CV =   − 
 ∂T  P  ∂T  V

 ∂U   ∂V   ∂U 
=  + P  −  (H = U + PV)
 ∂T  P  ∂T  P  ∂T  V

 ∂U   ∂U 
but, because U is a state function, dU =   dV +   dT
 ∂V  T  ∂T  V

and, differentiating with respect to T at constant pressure, we get

 ∂U   ∂U   ∂V   ∂U 
  =    + 
 ∂T  P  ∂V  T  ∂T  P  ∂T  V

 ∂V   ∂U   ∂V 
Thus C P − C V = P  +   
 ∂T  P  ∂V  T  ∂T  P

Now, the first term in the expression above can be interpreted as the contribution to
CP caused by the expansion of the system against the external pressure P.

The second term is the contribution to CP from the work done in expansion against the
internal forces – the forces between molecules.

 ∂U 
For solids and liquids,   , which is a sort of ‘internal pressure’, is large because
 ∂V  T
of strong cohesive forces between the molecules but for gases it is usually small
compared with P, the external pressure, and, of course, for the ideal gas it is zero.

In the case of one mole of the ideal gas we have:

 ∂V  R
C P − C V = P  = P = R as expected.
 ∂T  P P

[Another way of doing this would be:

∂H ∂U ∂V R
CP = = +P = CV + P = CV + R ]
∂T ∂T ∂T P

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It is possible to reduce all the basic thermodynamic relations to 7 fundamental equations relating state
functions and their differentials.

(1) dU = TdS – PdV

(2) H = U + PV
(3) G = H – TS
(4) A = U – TS

(5) dH = TdS + VdP

(6) dG = -SdT + VdP
(7) dA = -SdT – PdV

Also:
 ∂S   ∂V 
(8)   =  (derived from (6) by Euler relation)
 ∂P  T  ∂T  P
 ∂S   ∂P 
(9)   =  (derived from (7) similarly)
 ∂V  T  ∂T  V

Add to the list the definitions of molar heat capacities:

 dq   ∂S 
(10) CV =   = T 
 dT  V  ∂T  V
 dq   ∂S 
(11) CP =   = T 
 dT  P  ∂T  P
dT
(These expressions are equivalent to the expression for entropy as an integral of C encountered earlier.)
T
Then from these 11 equations, all other relations can be derived.

For example we can derive equations of state not just for gases but for any substance.
Starting from Equation (1) above:
dU = TdS – PdV

Partial differentiation with respect to V gives:

 ∂U   ∂S 
  = T  −P
 ∂V  T  ∂V  T

which, using equation (9) above gives

 ∂U   ∂P 
  + P = T 
 ∂V  T  ∂T  V

which is a relationship between energy and P, V and T, an equation of state.

Similarly, equation (5) leads to another equation of state, this time in terms of enthalpy rather than
internal energy.

 ∂H   ∂V 
  − V = −T  
 ∂P  T  ∂T  P

Reference: A.Tobolsky, J. Chem. Phys., 10 (1942), 644-645

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