Helmholtz function F(T,V)

Zhigang Suo @zhigangsuo

Part of a book on Thermodynamics
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Define the Helmholtz function by

F = U - TS

This function is also called Helmholtz free energy, or just free energy. Because U and S are
extensive quantities and T is an intensive quantity, the Helmholtz function is an extensive
quantity. Because U, T, and S are functions of state, F is also a function of state. The energy U
has an arbitrary additive constant, which also appears in F.

Helmholtz function F(T,V) is a characteristic function of a closed system 2

Maxwell relation 2
Increment of the function U(T,V) 3
Increment of the function S(T,V) 3
A closed system in a thermal environment 3
Massieu function 5
Helmholtz function 6

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Helmholtz function F(T,V) is a characteristic function
of a closed system
Note dF = dU - TdS - SdT. This equation, together with the equation dS = (1/T)dU + (P/T)dV,
gives that

dF = -SdT - PdV.

This equation suggests that the Helmholtz function should be a function of temperature and
volume, F(T,V).

Recall a fact of calculus. For any function F(T,V), when the independent variables change by dT
and dV, the function changes by

dF = (∂F(T,V)/∂T)dT + (∂F(T,V)/∂V)dV.

A comparison of the above two equations gives that

-S = ∂F(T,V)/∂T, -P = ∂F(T,V)/∂V.

These equations express two functions of state, S(T,V) and P(T,V), in terms of the Helmholtz
function F(T,V).

Recall the definition of the Helmholtz function, F = U - TS. This equation determines the function
U(T,V).

We have expressed functions S(T,V), P(T,V), and U(T,V) in terms of the Helmholtz function.
Thus, F(T,V) is a characteristic function of a closed system.

Recall the definition of the constant-volume thermal capacity:

CV = ∂U(T,V)/∂T.

The subscript V indicates that the volume is fixed. This definition interpretes one partial
derivative of the function U(T,V).

Maxwell relation
Recall a fact in calculus:

∂(∂F(T,V)/∂T)/∂V = ∂(∂F(T,V)/∂V)/∂T.

We obtain that

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∂S(T,V)/∂V = ∂P(T,V)/∂T.

This equation is called a Maxwell relation.

Increment of the function U(T,V)

Start with an identity in calculus:

dU = (∂U(T,V)/∂T)dT + (∂U(T,V)/∂V)dV.

Recall dU = TdS - PdV. Now we regard T and V as independent variable, so that

∂U(T,V)/∂V = T∂S(T,V)/∂V - P

Using a Maxwell relation, ∂S(T,V)/∂V = ∂P(T,V)/∂T, we change the above equation to

∂U(T,V)/∂V = T∂P(T,V)/∂T - P

Now we have both partial derivatives of the function U(T,V), so that

dU = CV(T,V)dT + (T∂P(T,V)/∂T - P)dV.

This equation relates dU to two functions CV(T,V) and P(T,V).

Increment of the function S(T,V)

Recall the equation dS = (1/T)dU + (P/T)dV, Inserting the above expression for dU, we obtain
that

dS = (CV(T,V)/T)dT + (∂P(T,V)/∂T)dV.

This relation indicates that we can determine the function S(T,V) by measuring the two functions
CV(T,V) and P(T,V).

A closed system in a thermal environment

Let us relate the Helmholtz function to an experiment. For a fluid in a cylinder sealed by a
piston, we fix the volume V of the fluid by jamming the piston. The weight placed above the
jammed piston does not affect the fluid, and will not be included in the analysis. If the fluid is a
steam-water mixture, the fraction of H2O molecules in the steam is an internal variable. The fluid
is thermal contact with a thermal environment of a fixed temperature.

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When the volume of a closed system is fixed, the closed system becomes a thermal system.
The analysis here is the same as that for a thermal system. We next analyze this experiment
using the BAT.

An isolated system with internal variables. A state of a closed system is specified by energy
U, volume V, and an internal variable x. A thermal environment is a thermal reservoir of a fixed
temperature Tenv. Associate the experiment with an isolated system of two parts: the closed
system and the thermal environment.

Energy is an extensive property. The energy of the isolated system, Uiso, is a sum:

Uiso = U + Uenv,

where Uiso is the energy of the isolated system, U the thermal energy of the closed system, and
Uenv the thermal energy of the thermal environment.

The isolated system conserves energy. When the isolated system changes state, Uiso is
constant. We take U as an independent variable, and Uenv as a dependent variable.
Consequently, the isolated system has two internal variables: the thermal energy of the closed
system, U, and the internal variable of the closed system, x.

The subset entropy of the isolated system as a function of internal variables. The closed
system is characterized by the function S(U,V,x). The thermal environment has a constant
temperature Tenv, and is characterized by a linear function: Senv(Uenv) = Senv(Uiso) - U/Tenv.

Entropy is an extensive property. The subset entropy of the isolated system is a sum:

Siso(U, V, x) = S(U,V,x) + Senv(Uiso) - U/Tenv.

Maximize the subset entropy of the isolated system to reach equilibrium. We have
characterized a closed system with a function S(U,V,x), and a thermal environment with a
temperature T0. The volume V of the closed system and the temperature T0 of the environment
are fixed.

The closed system and the thermal environment constitute an isolated system. Because
Senv(Uiso) is constant, a change in the subset entropy of the isolated system is the same as a
change in the function

S(U,V,x) - U/Tenv.

Here S(U,V,x) is the entropy of the closed system, and - U/Tenv is the change in entropy of the
thermal environment. Here U and x are independent variables, but V is constant.

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For the isolated system to reach equilibrium, U and x reach the values that maximize the
function S(U,V,x) - U/Tenv.

For the isolated system to undergo a reversible process, U and x must change values in a way
that keeps the function S(U,V,x) - U/Tenv constant.

Increase the subset entropy of the isolated system for an irreversible process. For the
isolated system to undergo an irreversible process, U and x must change values to increase the
function S(U,V,x) - U/Tenv.

Because Tenv is a positive constant, increasing S(U,V,x) - U/Tenv is equivalent to decreasing U -

TenvS(U,V,x).

Massieu function
Partial equilibrium. Consider a special case in which U varies rapidly in time, but x varies
slowly in time, so that the isolated system reaches equilibrium with respect to U long before it
reaches equilibrium with respect to x. Such a partial equilibrium is called thermal equilibrium.

When the isolated system reaches thermal equilibrium at a fixed x, the energy U must reaches a
value that maximizes the quantity S(U,V,x) - U/Tenv. The condition for thermal equilibrium
recovers a familiar equation:

∂S(U,V, x)/∂U = 1/Tenv.

The left side is the inverse of the temperature of the closed system, 1/T. The right side is the
inverse of the temperature of the environment, 1/Tenv. In thermal equilibrium, the two systems
have the same temperature. We will drop the subscript in Tenv.

Free entropy. Given the function S(U,V, x), the above equation solves the function U(T,V,x). We
can also write the entropy of the closed system as a function S(T,V,x).

Thus, x is the only remaining internal variable of the isolated system. The basic algorithm
requires x to change to increase the function

J = S(T,V,x) - U(T,V,x)/T.

The term S is the entropy of the closed system, and the term - U/T is the reduction of the
entropy of the reservoir when the reserve transfers energy U to the closed system. The function
J(T,V,x) is called the Massieu function, or the Massieu entropy. In maximizing the function
J(T,V,x), T and V are fixed, and only x is variable.

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Algorithm of thermodynamics for a closed system in constant-volume,
constant-temperature process. We now paraphrase the basic algorithm of thermodynamics
for a closed system in a constant-volume and constant-temperature process.

1. Construct a closed system with a fixed volume V, fixed temperature T, and an internal
variable x.
2. Find the function J(T,V,x) = S(T,V,x) - U(T,V,x)/T.
3. For the isolated system to reach equilibrium, change the value of x to maximize the
function J(T,V,x). In this maximization, T and V are constant.
4. For the isolated system to undergo an irreversible process, change the value of x to
increase the function J(T,V,x).

Helmholtz function
Recall the definition of the Helmholtz function F = U - TS. Thus, F = - TJ. Because T is a positive
constant, maximizing J(T,V,x) is equivalent to minimizing F(T,V,x). The above algorithm can be
paraphrased in terms of minimizing the Helmholtz function F(T,V,x).