Chapter 4.

Thermodynamic Variables and Relations 12

Coefficient relations:

Chapter 4. Thermodynamic Variables and

Relations

4.1. Write out the combined statements of the first and second
laws for the energy functions, U= U(S,V), H = H(S,P), F =
F(T,V) and G = G(T,P). Assume * W' is zero.

a. Write out all eight coefficient relations,

b. Derive all four Maxwell relations

for these equations.

Answer to 4.1.

Combined statements:
Maxwell relations:
Chapter 4. Thermodynamic Variables and Relations 13
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4.2. Derive the ratio relation equation (4.30):

[Hint: Begin with the differential form of Z = Z(X,Y); solve Write the differential of dX directly from X = X(Y, Z)
for dX; write the differential form of X = X(Y,Z); compare
coefficients.]

Answer to 4.2.

Write out the function and its differential: Compare coefficients of dY in these two expressions for dX:

or

Solve this equation algebraically for dX:

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Chapter 4. Thermodynamic Variables and Relations 15
c. One mole of zirconia is heated at one atmosphere
from 300 to 1300K.
d. One mole of zirconia at 300K is isothermally
compressed from 1 atm to 100 kbars. (Use V = 22.0 (cc
/ mol) and " = 10 x 10 - 6 K - 1).
e. One mole of oxygen is heated at one atmosphere
from 300 to 1300K. (Assume oxygen is an ideal gas
with CP = 7/2 R.)
f. One mole of oxygen at 300K is isothermally
compressed from 1 atm to 100 kbars.

What general qualitative conclusions do you draw from these

calculations?

Answer to 4.4.

a. Need S = S(T, P) with P constant.

The volume at the end of the process is:
The heat capacity of nickel is given by

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4.4. Compare the entropy changes for the following

processes:

a. One gram atom of nickel is heated at one

atmosphere from 300 to 1300K.
b. One gram atom of nickel at 300K is isothermally
compressed from 1 atm to 100 kbars.
Chapter 4. Thermodynamic Variables and Relations 16

b. Need S = S(T,P)

Substitute and integrate:

The atomic volume of nickel is 6.60 cc/mol; the coefficient of

thermal expansion is 40 X 10-6 K-1. Assume these are
independent of pressure: d. This problem is analogous to part b:

The molar volume of zirconia is 22.0 cc/mol; the coefficient of

thermal expansion is 7 X 10-6 K-1:

c. Again need S = S(T, P)

e. This problem is analogous to parts a and c. The heat

capacity of O2 is

The heat capacity of zirconia is

Chapter 4. Thermodynamic Variables and Relations 17

The change in entropy is

General conclusion: For condensed phases the effect of

f. The differential form to be integrated is the same as in parts pressure on entropy is much smaller than the effect of
b and d: temperature; both effects are important for gases.
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4.5. Express the results obtained for parts c and d of problem

For an ideal gas, 4.4. in values per gram atom of ZrO2. [Each mole of zirconia
contains three gram atoms of its elements: one gram atom of
zirconium and two of oxygen.] How does this result influence
the conclusions you made in the comparisons in problem 4.4?

Answer to 4.5.
so that
The change in entropy associated with heating zirconia from
300 to 600 K at one atmosphere per gram atom is obtained by
dividing the result in 4.4c by the number of gram atoms in one
mole of ZrO2, i.e., be 3:

Integration gives:
Chapter 4. Thermodynamic Variables and Relations 26
programmed control of the pressure and volume of the gas that
it contains. The system is filled with one gram atom of helium
and brought to an initial condition of one atmosphere and 18
liters. It is then reversibly compressed to 12 liters along a
programmed path given by the relationship

b. Since the process is reversible, the heat absorbed along the

where P is in atmospheres and V is in liters. Compute: specified path is:

a. The initial and final temperature of the system.

b. The heat absorbed by the system.
c. The work done by the system.
d. The changes in U, H, F, G and S.

Here P and V have been chosen as independent variables

because the path is specified in terms of P and V. The values
of M and N for S = S(P, V) have been obtained in example 4.3:
Answer to 4.12.

a. The final pressure in the system is determined from the

equation for the path and the final volume:

For a monatomic ideal gas, " = 1/T, $ = 1/P and CP = 3/2R:

Initial and final temperatures may be obtained from the

equation of state:

The heat absorbed depends upon the path. Thus to compute Q

it is necessary to express V in terms of P (or P in terms of V)
Chapter 4. Thermodynamic Variables and Relations 27
using the path relationship. Since case, use the path equation to write dV in terms of dP:

Integration gives the work done for the process:

Insert these values into the expression for * Q:

Integration from Pi to Pf gives the heat absorbed along the

specified path: d. Changes in the state functions U, H, F, G and S.

1). The change internal energy may be obtained by

integration the expression for dU for an ideal gas
obtained in problem 4.9

along any path. The simplest path is a two step

reversible process, first at constant V, then at constant
P.
c. The work done is an integral of - PdV along the path. In this
Chapter 4. Thermodynamic Variables and Relations 28

For the second step, which is valid for any process for an ideal gas. As a
third check on this result apply the first law:

2). ) H may be computed in a variety of ways. Most

The total change in internal energy is the sum: direct is the general formula for dH for an ideal gas:

Or, apply the definitional relation:

Note that, since PV = RT, this result may also be

written
3). Since P, V and T values are computed for the initial
and final states, the change in entropy may be
Chapter 4. Thermodynamic Variables and Relations 29
computed for a two step path in (P,T) coordinates, or in
(P,V) coordinates, or in (T,V) space. From S = S(T,P):

4). To compute the change in Helmholtz free energy

between the initial and final states the simplest relation
to use is F(T,V):

The appropriate reversible two step process is a

constant volume change in temperature followed by the
Apply S = S(T,V): volume change at Tf. In order to integrate -SdT it is
first necessary to derive a function for the temperature
dependence of the entropy for a constant volume
change. The absolute value of the entropy function
requires as input the absolute entropy of helium at 298
K:

Consider a constant volume temperature change

followed by a constant temperature volume change:
Chapter 4. Thermodynamic Variables and Relations
where 126.04 (J/mol K) is the absolute entropy of
helium at 298 K. Substitute this result into the free
energy expression for the first step:
Step II is an isothermal (at Tf) volume change:
The total change in free energy is the sum:
5). A similar strategy may be used to compute ) G for
the process. An alternate approach applies the
definitional relations:
Thus,
30
This problem provides a numerical example that demonstrates
that, no matter what variables are used to describe the path and
the initial and final states, the changes in the state functions
computed will be the same.
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4.13. Estimate the pressure increase required to impart one
Joule of mechanical work in reversibly compressing one mole
of silver at room temperature. What pressure rise would be
required to impart one Joule of work to one mole of alumina at
room temperature? For alumina take the molar volume to be
25.715 (cc-mol-1) and $ = 7.0 x 10-7 (atm)-1
Answer to 4.13.
The independent variables are (P, T). The function to be
computed is the process variable, W. Assuming the process is
carried out reversibly,
Since the process is isothermal, dT = 0:
Chapter 4. Thermodynamic Variables and Relations
For a finite process,
To find the final value of the pressure for a given input of
work, solve for Pf:
For silver, the molar volume is 10.27 (cc/mol) and $ may be
estimated as 10-7 (atm-1). Insert the value of the initial pressure
and calculate:
For alumina the molar volume is 25.7 (cc/mol) and $ is 8.0 X
10-7 (atm-1). One joule of work is imparted to one mole of
Al2O3 if the pressure is raised to:
31
It may seem surprising that a lower pressure is required to
impart one Joule of work to alumina, a stiff ceramic, as
compared to titanium metal. This observation is attributed to
the fact that one mole of alumina has five times as many atoms
as one mole (gram atom) of titanium and as a consequence has
a larger molar volume. The pressure determines the fractional
change in volume. For the same fractional change (strain) ) V
is thus larger for alumina, and more work is done.
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4.14. Compute and plot the surface representing the Gibbs free
energy of hydrogen gas as a function of temperature and
pressure in the range from (298K, 10-10 atm) to (1000K, 100
atm). Use (298K, 1 atm) as the zero point for the calculation.
The absolute entropy of H2 at 298K and 1 atm is 130.57
(J/mol-K); assume that CP = 7/2 R (J/mol-K) is independent of
P and T.
Answer to 4.14.
The independent variables are T and P: dependent variable is
G. The function required is G = G(T,P):