Chapter 7

Legendre transforms and other potentials

7.1

New thermodynamic potentials from baths

We began our discussion of equilibrium by considering how the entropy emerges for
isolated systems, finding that it is maximized under constant
conditions. In
practical settings, however, systems are rarely isolated, and it is often difficult to control
the energy and volume of a system when outside forces are acting on it. Instead, it is easier
to control so-called field parameters like temperature and pressure.
In this chapter, we will discuss the proper procedure for switching the independent
variables of the fundamental equation for other thermodynamic quantities. In doing so, we
will consider systems that are not isolated, but rather held at constant temperature,
pressure, and/or chemical potential through coupling to various kinds of baths. In such
cases, we find that entropy maximization requires us to consider the entropy of both the
system and its surroundings. Moreover, new thermodynamic quantities will naturally
emerge in this analysis: additional so-called thermodynamic potentials.

Figure 8.1. A system can be coupled to different kinds of baths. Because the bath is so large, its
equilibrium state remains constant even though different quantities (energy, volume, particles) can
be exchanged with the system.

To achieve constant temperature, pressure, or chemical potential conditions, one

couples a system to a bath. As discussed before, a bath is a large reservoir of energy,
1

volume, or particles that can exchange with the system of interest. While exchanging
volume/energy/particles alter the system state, such changes are so miniscule for the bath
that it is essentially always at the same equilibrium condition. Fig. 7.1 gives a schematic of
ways in which a system can be coupled to different kinds of baths.
Recall our earlier result in Chapter 4: systems that freely exchange / / reach
thermal/mechanical/chemical equilibrium by finding the same / / . Here, the main
difference with these previous results is that the bath is so large that it stays at the same
/ / , and hence it sets the final equilibrium values of these parameters for the system.
We consider the bath to be ideal in that it is infinitely large.

7.2

Constant temperature coupling to an energy bath

Let us consider the specific case in which a system is held at constant temperature by
coming to thermal equilibrium with an ideal energy bath. In reaching equilibrium, the
entropy of the world is maximized subject to energy conservation,
(
(

)
)

(7.1)

Here, the unsubscripted variables are those pertaining to the system. Since the state of the
bath does not change for any measurable energy transfer with the system, we write the
integrated form of its fundamental equation with the implicit approximation that all of its
intensive state parameters are constant,

(7.2)
(

where
is fixed due to the constancy of state but
depends on the exchange with
the system. We also know that the energy of the bath can be found from the total energy
and that of the system; therefore,
(

Since the energy of the world does not change, we can absorb
(

Finally, we insert this expression into the entropy of the world,

(7.3)

)
into the constants,

(7.4)

(7.5)

To find the point of equilibrium between the two systems, we maximize

with respect
to the energies of the system and bath. Note here that
is constant and does not affect
the maximization procedure. Because
is the final equilibrium temperature of our
system, we will simply write it as . Moreover, the constants group is unaffected by the
energies, and hence we can neglect it during minimization. On the other hand,
is
dependent on since changes to the system energy are generally large enough to affect the
value of its entropy. As a result, we might write the equilibrium expression as,
[

[ (

(7.6)

That is, equilibrium occurs at the energy of the system that maximizes (7.6) where is
treated as a constant. By convention, we define a quantity that entails this particular
combination of variables, albeit in a slightly rearranged manner. The Helmholtz free energy
is given by,
(7.7)
Sometimes the Helmholtz free energy is written as
in the physics literature, a mere
matter of convention. Now the equilibrium condition becomes,
[
Because

(7.8)

is constant, the extremum is equivalent to,

[ ]

(7.9)

That is, the Helmholtz free energy attains a minimum at equilibrium. is a new function to
us that, importantly, is specific to the system. It does not rely on the detailed properties of
the bath, and it is a distinct thermodynamic potential of the system. We showed that
maximizing the entropy of the world, which includes both the system and the bath, is
equivalent to minimizing the Helmholtz free energy of the system alone.
Crucially, the equilibrium, minimized value of
is not a function of
, the
variables of the entropy, but instead a function of
. That is, we lose
as an
independent variable but gain as one. Physically, this should make sense. For one, we
know that is determined by the bath. It is something that we specify independently since
we choose the particular kind of bath that we bring in contact with the system. Moreover,
the value of the system is determined by the entropy maximization / Helmholtz free
energy minimization procedure. We cannot set
independently because its value is
controlled by coupling to the bath; it becomes an internal degree of freedom.

At equilibrium for closed, single-component systems held at a constant

temperature and volume, the Helmholtz free energy
is at a
minimum. This equilibrium value of has independent variables
, so
that we have the thermodynamic potential (
).
EXAMPLE 7.1
Find the Helmholtz free energy of a monatomic ideal gas, whose entropy function can be written as
(
where

[( ) ( )]

is a constant.

Conceptually we will put the gas in equilibrium with a heat bath with which it can exchange energy.
The Helmholtz free energy is minimized, and its form is,
[( ) ( )]
We minimize with respect to

for fixed

,
(

Solving for ,

Back-substitution into the Helmholtz free energy expression finally gives,

) ( )]

[(
{
which is only a function of

7.3

[(

) ( )]}

, as we should have.

Complete thermodynamic information and natural variables

Having introduced the function (

), it is worthwhile discussing the completeness of
thermodynamic information contained in it. Recall that only three pieces of information
are required in order to completely specify the (extensive) thermodynamic state of a
single-component system, after which all other thermodynamic variables have a unique
value. The complete list of variables includes
. So, if we pick three of these
to specify the state, then we seek a thermodynamic function that can provide the values of
the other four. In the case of the entropy, the three variables to be specified are
; the
function (
) gives the entropy directly, and
extend from its partial derivatives.

In that sense,
information.

) is a function that gives a complete set of thermodynamic

When we changed to in what we held constant, we had to switch from to as

the relevant potential for our system. One might wonder why we were not able to use the
) Indeed, (
) is a perfectly valid function
function (
) instead of (
because we can always tabulate the entropy using the state parameters
, which come
from different conjugate pairs. However, even though such a function can be constructed
and is useful, it ultimately results in a loss of some information. That is, we cannot
manipulate (
) so as to extract the complete set of thermodynamic variables at a
given state point. For example, what if we wanted to compute from (
)? We
would take the following approach:
(

(7.10)

Integrating,
(

(7.11)

In finding , we end up with an unknown and -dependent constant due to the fact that
we needed to perform an integration. We can never find the value of that constant from the
function (
) alone. In contrast, if we knew (
), we
incur any
unknown constants in the determination of the other thermodynamic properties (
)
because all of these stem from derivatives of the function of interest. In this sense, we call
(
) fundamental, in that it contains all thermodynamic information, while (
)
is not. We also say that the natural variables of the thermodynamic potential are
.
These are general terms in thermodynamics that apply to all potentials.
thermodynamic potential

natural variables

fundamental form

entropy

internal energy

Helmholtz free energy

As alluded to above, the Helmholtz free energy (

) is also fundamental. That means

y f
(
) despite the fact that it represents a function
where
is now an independent variable rather than . All other thermodynamic
properties extend from derivatives of , easily shown from its differential form,
(

(7.12)

where we have substituted the differential form for the fundamental energy equation.
Simplifying,
(7.13)
This expression implies that the partial derivatives of the Helmholtz free energy are,
(

(7.14)

We see that a complete set of thermodynamic information can be derived from given that
the current state conditions are specified by
. Therefore, we conclude that (
)
is the fundamental thermodynamic potential at constant
conditions.

7.4

Legendre transforms: mathematical convention

Above we derived by considering the physical process in which a system is attached to a

heat bath. Mathematically speaking, however, there is a deep theoretical foundation for
transforming the function (
) into (
). Per the considerations above in (7.6),
we can find the value of at any state point using the following mathematical construction,
(

(7.15)

where
is the value of the internal energy that minimizes the expression on the right
hand side, for given values of
. Equivalently, we can switch to the energy version of
the fundamental equation to show that,
(

(7.16)

where now is the value of the entropy that minimizes . In either case, we find the value
of one free variable that minimizes the Helmholtz free energy.
These constructions are closely related to a mathematical operation called the
Legendre transform. Consider a generic function ( ) and let its derivative be
. A
Legendre transform produces from ( ) a new function ( ), where the independent
variable has changed to . This new function contains all of the same information as the
original function, so that it can easily be transformed back. The exact procedure is,
[ ( )]

( )
[

( )]
( )

( )

(7.17)

( ),
In other words, the Legendre transform produces a new function equivalent to
where is independently specified and
is the value of that maximizes this expression
6

for given . This is easy to see: simply take the -derivative of

zero to obtain the third line in (7.17).

( ) and set it equal to

To show that the Legendre transform maintains all of the information in the original
function, we merely need to show that ( ) can be converted back to ( ). The inverse of a
Legendre transform turns out to be itself. We compute the derivative of ( ) to
demonstrate this,
( )

( )

( )]
( )

Then, computing ( )

( )

( )
( )

( )
(7.18)

[ ( )],

[ ( )]

( )

( )

( )

Substituting for ( ) from before, and using the fact that

[ ( )]

[
( )
( )

( )]
( )]

(7.19)
,
(7.20)

And so we see that the original function is recovered when we apply the Legendre
transform twice, [ [ ]]
.
EXAMPLE 7.2
Compute the single- and double-Legendre transforms of ( )
Starting with the definition of [ ( )],
( )
The equation for

( )

is,
( )

Back-substituting for

, we find,
( )

Now we compute the Legendre transform of ( ),

( )

[ ( )]
( )

The condition for

gives:

( )
So that,
( )
We see that we recover the same function, ( )

7.5

, as our original one, ( )

Legendre transforms: thermodynamic convention

Legendre transforms can convert one thermodynamic potential to another, but there is a
subtlety in that thermodynamics makes use of negative Legendre transforms, i.e., with a
sign change in their construction. Moreover, thermodynamics entails multivariate
functions, and one must specify which variable is the subject of the transform.
Consequently, in a thermodynamic context we define,
[ (

)]

)
[ (

]
(

(7.21)

Here, the subscript on the Legendre operator indicates that we are performing the
transform with respect to the independent variable , and not or . There is no need to
be concerned about the difference with the mathematical definition; this again is simply a
sign change. From now on, we will use the symbol to denote the Legendre transform in
the thermodynamic convention. In shortcut form, we write it as,
[ ]

(7.22)

Consider as an example the expression for the Helmholtz free energy in (7.16),
(
where

(7.23)

is the value of that minimizes this expression,

[ (

(7.24)

or equivalently,
(

(7.25)

This set of equations is exactly a Legendre transform. By comparing (7.21) and (7.23) with
(7.24), we see that
,
, and
. In fact, we can write the expression for the
Helmholtz free energy explicitly as the entropy Legendre transform of the internal energy,
(

[ (

)]

(7.26)

Here, the subscript indicates a transform with respect to the independent variable .
In performing a Legendre transform of the internal energy, we swapped for as
an independent variable to produce the Helmholtz free energy . However, this is not the
only Legendre transform that we can perform since there are three independent variables.
One can consider transformations between any two conjugate variables. This means that
we can also swap for and for , since Legendre transforms trade an independent
variable for the derivative of the thermodynamic potential with respect to it. One cannot,
however, swap non-conjugate pairs, like for . In general, Legendre transforms are the
mathematical equivalent of connecting our system to various kinds of baths.
Legendre transforms enable one to switch an independent variable of a
thermodynamic potential to its conjugate.
The function produced
corresponds to the relevant thermodynamic potential at constant conditions
of the new independent variables.

7.6

The Gibbs free energy

L
p
p
of equilibrium at both constant and . In other
words, consider a system exchanging both energy and volume with a bath. We proceed
using the second law as before,
(

)
(

(7.27)

The very large bath admits the behavior,

(

(7.28)

Expressing the bath quantities in terms of the difference between the world and system
gives,
(

The maximum entropy equilibrium condition therefore becomes,

9

(7.29)

(7.30)

where we replaced
with and
with since it is through the bath that the system
temperature and pressure are ultimately maintained. In multiplying the right hand side by
the constant , we find the equivalent equilibrium condition,
[ (

(7.31)

The quantity in brackets is called the Gibbs free energy,

. Here,
equilibrium is obtained by minimizing (7.31) with respect to the values of and , for
given independent parameters and . If we go ahead with the -minimization, we see
from our earlier results that this is equivalent to,
[ (

(7.32)

We could have also tackled this problem using Legendre transforms. Since the
system is connected to a bath with which it can exchange energy and volume, this means
that we swap both
and
by performing two Legendre transforms. We can start
with the Helmholtz free energy that already entails a Legendre transform in the entropy.
Now we perform an additional Legendre transform in the volume. The resulting potential
is the Gibbs free energy,
(

[ (

)]
(

(7.33)

Notice that the Gibbs free energy is naturally a function of the variables
. Moreover,
like the Helmholtz free energy, it is a minimum at equilibrium, but for systems at constant
conditions. We examine the partial derivatives of in the following manner,
(

(7.34)

where we have substituted the differential expression for

. Simplifying,
(7.35)

This result shows that the partials are in fact,

(

(7.36)

We can also relate the Gibbs free energy directly to the internal energy, as,
(

[ (

10

)]]

(7.37)

The Legendre transforms provide the mathematical equivalent of connecting our system to
energy and volume baths. In summary,
At equilibrium for closed, single-component systems held at a constant
temperature and pressure, the Gibbs free energy
is at a
minimum. This equilibrium value of has independent variables
, so
that we have the thermodynamic potential (
).

7.7

Physical rationale for Legendre transforms

Why do Legendre transforms naturally emerge when we consider alternate constant

conditions? The reason stems from the fundamental form of the bath entropy. In general,
we can express
in terms of its extensive properties
, and the intensive

conjugates of those,
(
),
(
), and so on.
A
g E

(7.38)

For example, if
then
. For a bath we take the intensive
parameters to be constant since its state is insensitive to small variations in the extensive
quantities. Presume now that a bath is coupled to a system such that it can exchange
extensive quantity with
constant. The second law then requires,

(7.39)
(

)
(

We recognize that the intensive parameter

sets or determines the equivalent
parameter in the system, . Thus we may rewrite the expression above more formally as,
[

[ (

(7.40)

where maximization takes place with respect to the value

for specified, fixed . Note
that the expression on the right hand side is equivalent to a Legendre transform. At the
),
maximum with respect to (
(

So that in shortcut form, we might write,

11

(7.41)

(7.42)

In other words, connecting a system to a bathregardless of the particular kind and what
is exchangednaturally leads to a Legendre transform of the entropy. Importantly, all
variables on the right of (7.42) are strictly properties of the system; we have removed
those of the bath by ignoring the constant terms. That is in fact the main feature of this
approach. Rather than consider the second law directly for the combined system and bath,
we convert to an equivalent form involving a different extremized quantity that depends
only on system properties, independent of the bath.

7.8

Extremum principles with internal constraints

The entropy maximization approach described above is always with respect to a system
variable that is in exchange with the bath, such as . In Chapter 4, however, we also
discussed the idea of internal constraints. When an internal constraint or internal degree
of freedom is released, an isolated system will behave so as to maximize its entropy
according to the second law. For example, we could have viewed a system plus an energy
reservoir as a single isolated supersystem with internal degree of freedom . In general,
however, a system could contain any number of internal constraints or degrees of freedom.
Naturally one wonders how other such degrees of freedom play out when a system
is connected to a bath. The resolution is really quite simple because we only need to
consider the possibility that our system entropy can change due to internal constraints in
addition to the bath-exchange variable. The state of maximum world entropy can be
achieved by varying the internal degree of freedom ( ) to maximize the system entropy for
any value of the exchanged variable,
[

[ (

)]

(7.43)

]]

(7.44)

A reordering of the maximization conditions gives,

[

[ (

Consider as an example a system connected to a thermal bath,

[
Since

[ (

is constant, we can rewrite this as,

12

]]

(7.45)

[ (

)]]

(7.46)

)]

Thus, the Helmholtz free energy is minimized at constant

with respect to any
unfixed internal degrees of freedom or internal perturbations to the system. Similarly for
the Gibbs free energy,
[

[ (

[ (

]]
]]

(7.47)

)]

The general idea of these results is that,

The relevant potential at a set of constant conditions is extremized not only
with respect to the variables describing what is being exchanged with baths,
but also with respect to any internal perturbations or degrees of freedom
released from internal constraints.

7.9

The enthalpy and other potentials

Now we will shift our perspective slightly and consider Legendre transforms of the energy
(
) rather than the entropy (
). What physical bath scenarios correspond to
cases in which remains constant? As we described in Chapter 4, conceptually we can hold
a system at constant by artificially and continuously adjusting its energy so that the
entropy stays at a fixed value, even if its volume or composition changes, say. If we
maintain constant
conditions in this way but allow our system to exchange other
quantities like volume or mass, then ,
(

(7.48)

L
y
g
specifically, in order to
maintain constant pressure conditions. Continuing as we have before by expanding the
bath entropy,

13

(7.49)

Since the temperature of the bath is constant, maximization of the entropy of the world can
finally be written as,
[

[ (

(7.50)

[ ]

In the last line we introduced the enthalpy. This important thermodynamic quantity is a
Legendre transform of the energy,
(

[ (

)]
(

(7.51)

The enthalpy is the thermodynamic potential for constant

conditions, and it is a
minimum at equilibrium. Like the internal energy, it relates to constant entropy
conditions, but at constant pressure rather than volume. The differential form of
is
found by differentiating (7.51). The final result is,
(7.52)
which summarizes the partial derivatives,
(

(7.53)

T
py
f
gy f
p
constant. The nomenclature f
f
f
and subtract the term
from the internal energy , which represents the part of the energy due to unorganized
molecular heat motion. In a loose sense, the remaining parts of represent energy potential
freely available to do useful work.
The enthalpy may seem like an unusual potential in that systems rarely achieve
constant
conditions. However, it naturally emerges as a useful quantity in many
scenarios as we have already seen in Chapters 5 and 6, such as isobaric heating, steadystate flow, and phase transitions. Even though the constant conditions in many of these
cases are not
, it can be shown that the enthalpy nonetheless contains relevant
information.

14

At equilibrium for closed, single-component systems held at a constant

entropy and volume, the enthalpy
is at a minimum. This
equilibrium value of has independent variables
, so that we have the
thermodynamic potential (
).
What about other thermodynamic potentials? We have only pursued Legendre transforms
in energy and volume, but we can transform the entropy and energy in the particle number
as well. If there are multiple components, we will be able to transform each separately,
so that the number of possible new thermodynamic potentials can be quite large. These
potentials are just as equally as valid as those we have discussed so far; it simply turns out
that the potentials
are most commonly useful.

7.10 Integrated and derivative relations

Recall that the internal energy is given in integrated form by
. We were
gE

rem for extensive quantities. This result simpllifies the

integrated relations for the other potentials,
(7.54)

W
p
y pp y g E

new thermodynamic potentials themselves, using the extensivity relations,

(

(7.55)

Here, only the extensive variables are scaled in each relation.

Notice in particular that the chemical potential in single component systems is
simply the per-particle Gibbs free energy,
. In general for multicomponent
systems, we have,

15

(7.56)


While these are integrated relations describing the four fundamental thermodynamic
potentials, there are also ways to relate them using derivatives. Consider, for example, the
relationship between and ,

(
where we rewrote

(7.57)

as a partial derivative of . Dividing by

(

(7.58)

( )
) from a derivative of (
).
Which shows that we can extract the function (
We could have also performed the transformation in the opposite direction, by expressing
as an -derivative of ,
(
which gives a route to
expressions
,
all we find that,

)
) from
, and

( )
(

).

(7.59)

Moreover, we can use all of the

to generate more such relations. In

( )

( )

( )

( )
(7.60)

( )

( )

( )

( )

And of course, there are such relations for the many other thermodynamic potentials that
can be constructed by Legendre-transforming the particle number variables in
multicomponent systems. In general, it is not advised to memorize these; rather, it is
important to understand the principles so such relations can be derived at any time.

16

EXAMPLE 7.3
An experimentalist determines the heat capacity of a substance to obey the empirical relation
(
)
, where is a constant. The experimentalist also finds the entropy and energy to be
zero at absolute zero, for all volumes. Compute the per-particle thermodynamic potentials
( ) ( ) (
), and (
).
To solve this problem, we start with the definition of heat capacity,
(

Using the fundamental equation at constant volume,

(

,
)

Now, we can perform integrals to compute the energy and entropy as a function of temperature,

( )

( )

( )

( )

But since we know the entropy and energy are both zero at
( )
To find (

, the constants are zero,

( )

) we need to solve for the temperature as a function of entropy,

(

( )(

To find the Helmholtz free energy, we use,

(

)
( )

[( )

( )
For the enthalpy, we need to find the pressure. One way is to use the energy derivative,

Another way is to take the Helmholtz free energy derivative,

(

17

( )

(
)
It is easy to verify that the two pressure expressions are equal, using
. Since the
enthalpy depends on the entropy, and not the temperature, we use the former. First we express
volume in terms of pressure, since pressure is the independent variable in the enthalpy:

Then, constructing the enthalpy and substituting for any

[(

terms,

[(

Finally, we can find the Gibbs free energy. First, we express the volume as a function of
temperature and pressure, based on the pressure expression derived from the Helmholtz energy,
( )
Constructing the Gibbs free energy from the Helmholtz free energy,

( )
(
We could have also formed

7.11

using

[( )

[( )

)
. The result would have been the same.

Multicomponent and intensive versions

The most general forms for each of the thermodynamic potentials involve multiple particle
number variables to indicate the amounts of different species. Let us denote the collection
}. Table 7.1 summarizes the general potentials and their
of these as { } {
interrelationships.

18

Table 7.1. Differential and integrated forms of extensive thermodynamic potentials.

potential
(

{ })

(
(

differential form

integrated form

{ })

{ })

{ })

{ })

An equivalent way of writing the sums involving chemical potentials is to use vectors,
(
). Then we can take advantage of vector dot products as,
(
) and

and
. This alternate notation is frequently encountered.
When the system contains only a single component, we can define per-particle or
molar versions of each of the thermodynamic potentials. The procedure is identical to
what we did earlier for the energy fundamental equation in Chapter 5, and can be applied
to both the differential and integrated forms of the potentials. As before, we will use lower
case letters to indicate quantities that are normalized by . Table 7.2 summarizes the
intensive potentials for a single-component system. Notice that the per-particle Gibbs free
energy is equal to the chemical potential. This is only the case for a single component.

19

Table 7.2. Differential and integrated forms of single-component intensive (per particle or per
mole) thermodynamic potentials.

per-particle or permole potential

7.12

differential form

integrated form and

relations

Summary and look-ahead

W
p
p
f g
z
f
. Systems
at conditions other than constant
require us to use a different thermodynamic
potential other than (
) or (
). That potential can be constructed by
connecting the system to a bath of some kind and maximizing the world entropy.
Equivalently, we obtain the appropriate potential by performing a Legendre
transformation, which constructs a new function as
( ). Legendretransformed potentials retain a complete set of thermodynamic information, and can be
interrelated in both integrated and derivative forms.
Before closing this topic, we highlight one point that we will revisit in Chapter 17.
Our current approach has been to couple a system to a bath and then maximize
.
Remember, however, that this maximization is really an approximation to find the most
probable macrostate with the largest number of microstates. This approximation works
well because the distribution of microstates is so sharply peaked around one value of what
is transferred between the system and its surroundings.
Despite the utility of the maximum term approximation, there are still fluctuations
around the maximum as slightly different amounts of, say, energy are exchanged between
the bath and the system. Indeed, these fluctuations are small and rare since they
correspond to states of the system with greatly diminished numbers of microstates, but
they nonetheless exist. That is, even though we cannot detect small variations in the
20

amount of energy exchanged between the system and the bath, these variations are real
such that the system energy is never rigorously constant when connected to a heat bath.
This leads to an important generality: only one of each conjugate pair of variables
can be truly constant at a time. If the temperature is held constant, by using an infinite heat
bath, then the energy of the system experiences slight fluctuations. If the volume is held
constant, then the pressure fluctuates. This point is not obvious at the macroscopic level
since the fluctuations are so small, but it is an essential feature at the microscopic scale.
Moreover, we will find in Chapter 17 that the magnitude of fluctuations is connected to
thermodynamic properties that we can actually measure.

21

Problems
Conceptual and thought problems
1. A single-component, constant-volume system is connected to a bath that regulates its
temperature. The system can also exchange molecules with the bath. What is the
fundamental function for this system, in both differential and integrated form? What are
its natural variables?
2. Let ( )
. Find the Legendre transform ( )
[ ( )], using the thermodynamic
[ [ ( )]] and
definition. Then find the double negative Legendre transform, ( )
show that ( ) and ( ) are the same functions.
[ ] and [ [ ]]. To
3. Find the following Legendre transforms of the entropy: [ ]
what thermodynamic potentials do these relate? Write both the integrated and differential
form of each potential.
4. What is the fundamental function
integrated form?

of natural variables (

), in both differential and

5. What is the integrated form of the fundamental function of natural variables (

),
for a single-component system? Why does the integrated form have this special behavior?
6. Consider a single-component, single-phase system. For each of the following, consider
the uniqueness of the intensive thermodynamic state of the system. Indicate whether the
set of variables (i) under-specifies the state (i.e., does not provide enough information), (ii)
over-specifies the state (i.e., one or more variables are redundant), or (iii) exactly specifies
the state. Explain.
a)
b) (

c)

7. Show that ( )

for all substances.

22

8. For a single-component system, classify the following as either fundamental, not

fundamental, or incomplete (meaning not enough information is provided to completely
specify the function):
a) (

b) (

c) (

9. For a binary system, classify the following as either fundamental, not fundamental, or
incomplete (meaning not enough information is provided to completely specify the
function):
a) (

) where

b) (

) where

c) (

) where

10. For a two-component system of A and B, classify the following as either fundamental,
not fundamental, or incomplete (meaning not enough information is provided to specify
the function).
a) (

b) (

c) (

) where

is the mole fraction of A.

11. A friend suggests that the fundamental equation for the intensive Gibbs free energy in a
binary mixture of A and B is given by,

where
(
). W
g
y
should the differential form for
really be? Derive this.

? W

Fundamentals problems
12. For a single-phase, single-component system, consider the following list of intensive

. Write down the complete list of pairs of these

variables:
variables that each uniquely specifies the state of the system.

23

13. A pot of liquid molecules completely vaporizes at its boiling temperature

and at
pressure . Assume the process is slow enough to be considered quasi-static. The latent
heat of vaporization is
,
, , and
for the process,
p . Write expressions for ,
where
indicates
L . Assume ideal behavior for the vapor state, and that the liquid
molar volume is much smaller than that of the gas.

14. Prove that

15. Let

) , starting from an intensive fundamental equation.

, and

. Show that,
(

( )
)

16. Find the differential form for the fundamental equation of the energetic quantity
. Indicate the independent variables of this quantity. Also indicate the relationship
of to , in an integrated form.
17. A system exhibits a heat capacity
that is approximately constant with temperature.
Show that, at fixed pressure, the Gibbs free energy follows a form like:
(

)(

( )

where
is a reference temperature at which the entropy ( ) and Gibbs free energy (
( ) .
are known. Keep in mind that the extensive heat capacity is defined by

Applied problems
18. A simple model of a monatomic crystal is the following. Atoms interact with a
repulsive pairwise potential energy of the form
( )
where
is the
atom-atom separation distance and is a constant, typically 9 or 12. For such crystals, the
)
[( ) ] where
Helmholtz free energy is found to be (
(
) and is a constant with units of [temperature][volume]m. Using this, find
expressions for:
a) the thermodynamic potentials (
b) the intensive heat capacities
where
.

) and (
) and

24

).
), and the equation of state,

19. In water, there is a driving force for the association of nonpolar solutes that arises
because the overall free energy of the system can be reduced by minimizing the solutewater interface. A simple way of viewing this hydrophobic interaction is through the
problem of the solvation or hydration of a nonpolar solute. We can think of this process as

p
a bath of liquid water, held at constant and
,
f
:
a) What thermodynamic quantity associated with this process will determine whether or
not hydration is favorable?
)L
y
y
p
. For large spherical solutes of
radii greater than or equal to
nm, it can be shown that the following approximation
holds,
, where is an effective surface tension. If two solvated spherical
droplets of a hydrophobic solute of radius associate into a single spherical droplet, show
that the change in
for this process is given by,
(

Is this process favorable or unfavorable?

c) An order-of-magnitude estimate of is
y
. Assume that the density of oil
droplets is 0.9 g
. What is
for two single-molecule o p

,
in kcal/mol of oil? Assume the molecular weight of oil is equivalent to that of decane. How
does the strength of this interaction compare to the van der Waals force?

25