Chemistry 360

Dr. Jean M. Standard

Problem Set 7 Solutions

1.

Calculate the entropy change when neon at 25C and 1 atm is allowed to expand from 0.780 L to 1.250 L.
The system is simultaneously heated to 85C. Assume ideal behavior.
For an ideal gas, we derived in class that

dSideal =

Cv
P
dT +
dV .
T
T

P
nR
=
For an ideal gas, we can use the relation that
. Substituting,
T
V

dSideal =

Cv
nR
dT +
dV .
T
V

Integrating,

V2 nR
Cv
dT +
dV
V1 V
1 T
$T '
$V '
= C v ln& 2 ) + nR ln& 2 ) .
% T1 (
% V1 (

Sideal =

T2

Neon is a monatomic ideal gas and so its constant volume heat capacity is C v = 23 nR . The expression for the
entropy change therefore becomes

#T &
#V &
Sideal = C v ln% 2 ( + nRln% 2 (
$ T1 '
$ V1 '
#T &
#V &
= 23 nR ln% 2 ( + nR ln% 2 ( .
$ T1 '
$ V1 '
The number of moles of neon must be determined in order to complete the calculation. Assuming ideal gas
behavior, the number of moles may be calculated from the initial conditions,

n =
=

PV
RT

(1 atm)( 0.780 L)
( 0.08206 Latm/molK)( 298.15 K)

n = 0.03188 mol.
Substituting,

Sideal =
=

3
2

# 358.15 K &
# 1.250 L &
1 1
( + ( 0.03188 mol) 8.314 J mol K ln%
(
$ 298.15 K '
$ 0.780 L '

( 0.03188 mol)(8.314 J mol1K1) ln%

Sideal = 0.20 J/K .

&
#V &
+ nR ln% 2 (
$ V1 '

3 nR ln T 2
% (
2
$ T1 '

2
2.

Determine A for a process in which 0.160 mol of an ideal gas expands reversibly and isothermally from
1.0 L to 3.5 L at 37C.
A good place to start is the fundamental equation for A,

dA = S dT P dV .
Since the temperature is constant, dT = 0 , so the equation becomes

Integrating yields

dA = P dV .

1 dA

1 P dV .

Since the system is an ideal gas, we can substitute the ideal gas relation for P,

A =

nRT
dV .
V

The process is isothermal, so the factor nRT can be pulled out and the integration performed,

nRT
dV
V
V2 1
= nRT
dV
V1 V
%V (
A = nRT n' 2 * .
& V1 )
A =

Substituting,

$V '
A = nRT n& 2 )
% V1 (

$ 3.5 L '
= ( 0.160 mol) 8.314 Jmol1K1 ( 310.15 K) n&
)
% 1.0 L (
A = 517 J .

3
3.

A sample of 0.988 moles of argon gas expands from 25.0 L to 35.0 L at a constant temperature of 350 K.
Determine the change in Gibbs free energy G for this process.
Starting from the fundamental equation for G, we have

dG = S dT + V dP .
Since the temperature is constant, dT = 0 , and the equation becomes

Integrating yields

dG = V dP .

1 dG

1 V dP .

Since the system is an ideal gas, we can substitute the ideal gas relation for V,

G =

nRT
dP .
P

The process is isothermal, so the factor nRT can be pulled out and the integration performed,

P2

nRT
dP
P
1
P2 1
= nRT
dP
P1 P
$P '
G = nRT n& 2 ) .
% P1 (
G =

Note that we do not know the change in pressure, but we do know the change in volume. At constant
P2
V
= 1 , and the Gibbs free energy change becomes
temperature, P1V1 = P2V2 . Therefore,

P1
V2

#V &
G = nRT n% 1 ( .
$ V2 '

Substituting,

#V &
G = nRT n % 1 (
$ V2 '

# 25.0 L &
= ( 0.988 mol) 8.314 Jmol1K1 ( 350 K) n %
(
$ 35.0 L '
G = 967 J .

4
4.

Calculate the molar quantities U m , H m , Sm , G m , and Am for the isothermal expansion of argon
gas at 500 K from 1.0 L to 3.0 L. Assume that argon behaves ideally.
Starting with U m , we know that for an ideal gas

dU = C v dT .

Since the process is isothermal, dT = 0 , and therefore dU = 0 , or U m = 0 .

Similarly for H m , we know that for an ideal gas

dH = C p dT .

Therefore, for an isothermal process, dH = 0 , and H m = 0 .

The entropy is defined as

dqrev
.
T

dS =

For an isothermal process, since dU = 0 , we have dq = dw . The work is dw = PdV for a reversible
process, and for an ideal gas it may be expressed as

dw =

nRT
dV
.
V

Thus, from the First Law, the heat is

dq = dw =

nRT
dV .
V

Substituting for the entropy, we have

dS =

dqrev
nR
=
dV .
T
V

Integrating,

V2

nR
dV
1 V
$V '
S = nR n& 2 ) .
% V1 (
S =

The molar entropy change is therefore

#V &
Sm = R n % 2 ( .
$ V1 '

5
4.

Continued
Substituting, the molar entropy change becomes

#V &
Sm = R n% 2 (
$ V1 '
# 3.0 L &
= 8.314 J mol1K1 n %
(
$ 1.0 L '

Sm = 9.13J mol1K1 .
For the Gibbs free energy, we have at constant temperature that G m = H m TSm . Since H m = 0 ,
the molar Gibbs free energy change is

G m = TSm

= ( 500 K) 9.13J mol1K1

G m = 4570 J/mol.
For the Helmholtz energy, we have at constant temperature that Am = U m TSm . Since U m = 0 , the
Helmholtz energy is

Am = TSm

= ( 500 K) 9.13J mol1K1

Am = 4570 J/mol.

6
5.

Starting from G = H TS , derive the fundamental equation for G.

To begin, we take the differential of G,

dG = dH d (TS )
= dH TdS SdT .

Next, we can substitute the fundamental equation for H, dH = TdS + VdP ,

dG = dH TdS SdT
= TdS
+ VdP TdS SdT
dG = VdP SdT .

Thus, we see that the natural variables of G are P and T.

6.

Toluene is vaporized at its boiling point of 111C. The enthalpy of vaporization is 361.9 J/g. Determine
H m , Sm , and G m for the phase transition.

The molar enthalpy of vaporization can be determined using the molecular weight of toluene, which is 92.14
g/mol,

# 92.14 g &
H m = ( 361.9 J/g)%
(
$ mol '
H m = 33350 J/mol (or 33.35 kJ/mol) .

H m
. Therefore, the molar entropy of vaporization is
T

For a phase transition, Sm =

Svap,m =

H vap,m

T
33350 J/mol
=
384.15 K

Svap,m = 86.8 J mol1K1 .

The molar Gibbs free energy at constant temperature is G m = H m TSm . Substituting the expression for

the entropy yields

G m = H m TSm

$ H m '
= H m T &
)
% T (
= H m H m
G m = 0 .

7
7.

Liquid water is compressed isothermally from 1 bar to 1000 bar. Calculate the change in the molar
Gibbs free energy. Assume that the molar volume is independent of pressure.
The best place to start is from the fundamental equation for the Gibbs free energy,

dG = S dT + V dP .
At constant temperature, dT = 0 , so

dG = V dP .

In terms of molar quantities,

dG m = Vm dP .

Integrating,

G m =

P2

Vm dP .

P1

If the molar volume is constant (independent of pressure), then it can be pulled out of the integral to yield

G m =

P2
P1

= Vm

Vm dP

P2
P1

dP

G m = Vm ( P2 P1) .
In order to evaluate the change in molar Gibbs free energy, we need the molar volume of liquid water. This can
be calculated from the inverse of the density (1 g/mL) and the molar mass,

" 1mL %" 18.0 g %" 1L %

Vm = $
'$
'$
'
# 1.0 g &# mol &# 1000 mL &
Vm = 0.0180 L/mol.
Substituting,

G m = Vm ( P2 P1)
= ( 0.0180 L/mol)(1000 bar 1 bar )

G m

$ 100 J '
= 18.0 L bar mol1&
)
% 1 L bar (
= 1800 J/mol.

8
8.

Using information from the appendix of the text, calculate G ! at 25C for the reaction

CO ( g) +

1O
2 2

( g)

CO 2 ( g) .

Is the reaction spontaneous?

The standard molar Gibbs free energies of formation at 25C as obtained from the appendix are:
G !f

Compound

(kJ/mol)
CO (g)
O2 (g)

137.2

CO2 (g)

0
394.4

The standard molar Gibbs free energy of reaction is given by

G r! = G !f (CO 2 ) G !f (CO)

1
2

G !f (O 2 )

= (394.4 kJ/mol) (137.2 kJ/mol)

1
2

( 0 kJ/mol)

G r! = 257.2 kJ/mol.
The reaction is spontaneous since the standard molar Gibbs free energy is negative.

9.

Determine G ! at 25C for the following hydrogenation reaction using information from the appendix of
the text,

C 6 H 6 ( ) + 3H 2 ( g) C 6 H12 ( ) .

Is the reaction spontaneous?

The standard molar Gibbs free energies of formation at 25C as obtained from the appendix are:
G !f

Compound

(kJ/mol)
C6H6 (l)
H2 (g)

124.3

C6H12 (l)

0
26.8

The standard molar Gibbs free energy of reaction is given by

G r! = G !f (C 6 H12 ) G !f (C 6 H 6 ) 3G !f ( H 2 )
= ( 26.8 kJ/mol) (124.3 kJ/mol) 3 ( 0 kJ/mol)
G r!

= 97.5 kJ/mol.

The reaction is spontaneous since the standard molar Gibbs free energy is negative.

# U &
( for a gas that obeys an equation of state given by
10. Determine the expression for %
$ V 'T

Z = 1+

B
.
Vm

Since a partial derivative of U is requested, it is helpful to start with the fundamental equation for U,

dU = T dS P dV .

Take the partial derivative with respect to V (at constant T) of both sides of the equation,

# U &
# S &
%
( = T%
( P.
$ V 'T
$ V 'T

The partial derivative on the right side of the equation cannot be determined from the equation of state.
However, one of the Maxwell relations can be used,

# S &
# P &
%
( = %
( .
$ V 'T
$ T 'V
Substituting yields

# U &
# P &
%
( = T%
( P.
$ V 'T
$ T 'V

Now, the partial derivative on the right side can be calculated from the equation of state. Since the equation of
B
state is Z = 1 + V , solving
for P gives
m

PVm
B
= 1+
,
RT
Vm
RT
BRT
or P =
+
.
Vm
Vm2

Now, converting to V instead of Vm leads to the expression

P =

nRT
n 2 BRT
+
.
V
V2

Taking the partial derivative,

# P &
nR
n 2 BR
+
.
%
( =
V
$ T 'V
V2

10
10. Continued
Substituting into the expression for the partial derivative of U gives the result,

# U &
# P &
%
( = T%
( P
$ V 'T
$ T 'V
# nR
n 2 BR &
(( P
= T %%
+
V2 '
$V
# nRT
n 2 BRT &
(( P
= %%
+
V2 '
$ V
= P P
# U &
%
( = 0.
$ V 'T

11
11. Starting from dH = T dS + V dP , show that

# H &
%
( = V (1 T ) ,
$ P 'T

where is the thermal expansion coefficient,

1 $ V '
& ) .
V % T (P

Starting from the fundamental equation for H, we need to take the partial derivative with respect to P (at

constant T) of both sides of the equation,

# H &
# S &
%
( = T% ( + V.
$ P 'T
$ P 'T
The partial derivative on the right side of the equation can be determined from one of the Maxwell relations,

# S &
# V &
% ( = % ( .
$ P 'T
$ T ' P

Substituting yields

# H &
# V &
%
( = T % ( + V .
$ P 'T
$ T ' P

# V &
The partial derivative % ( is related to the thermal expansion coefficient,
$ T 'P
# V &
% ( = V .
$ T 'P

Substituting,

#
# V &
H&
%
( = T %
( + V
$ P 'T
$ T 'P
= T V + V
# H &
%
( = V (1 T ) .
$ P 'T

12
12. Calculate the standard molar Gibbs free energy of reaction at 500 K for the reaction

N 2 ( g) + 3H 2 ( g) 2 NH 3 ( g) .
Use as a starting point values of the standard molar enthalpies and Gibbs free energies of formation at
25C, which are available in the appendix of your textbook.

The standard molar Gibbs free energy at another temperature may be estimated using the Gibbs-Helmholtz
equation,

$ ( G /T ) '
&&
)) = H .
% (1/T ) (P
If we approximate the partials by finite changes, the Gibbs-Helmholtz equation becomes

( G /T )
H ,
(1 /T )
$ G '
$1'
or &
) H & ) .
% T (
%T (
The changes are defined as the differences in the higher temperature (500 K in this case) and 298 K,

#1&
1
1
% ( =

$T '
Tf
Ti
# G &
G
and %
( =
$ T '
T

T=T f

G
T

.
T=Ti

Inserting these relations into the approximate Gibbs-Helmholtz equation,

# G &
#1&
%
( H % (
$ T '
$T '
G
T

T=T f

G
T

T=Ti

#1
1&
(.
H %%

T i ('
$T f

Substituting the temperatures,

G
G

T T=T f
T T=Ti
G 500
G 298

500 K
298 K

%1
1(
*
H ''

T i *)
&T f
% 1
1 (
H 298 '

*.
298 K )
& 500 K

13
12. Continued
Here, it has been assumed as indicated in the problem that the enthalpy of reaction is constant and the value at
298 K (available in tables) has been used. Isolating the unknown Gibbs free energy change at 500 K, we have

G 500
500 K

% 1
G 298
1 (
+ H 298 '

*,
298 K
298 K )
& 500 K

+ G
% 1
1 (.
298 + H
or G 500 ( 500 K)
*0 .
298 '
298 K )/
& 500 K
, 298 K
In order to complete the determination of the Gibbs free energy change at 500K, the values of the Gibbs free
energy and the enthalpy of reaction at 298 K are required. These can be obtained from the tables in the
appendix. Thestandard molar enthalpies and Gibbs free energies of formation at 25C of the reactants and
products are:
Compound
N2 (g)

H !f

G !f

(kJ/mol)

(kJ/mol)

H2 (g)
NH3 (g)

46.1

0
16.5

The standard molar enthalpy of reaction at 25C is

H r! = 2 H !f ( NH 3 ) H !f ( N 2 ) 3H !f ( H 2 )
= 2 (46.1kJ/mol) ( 0 kJ/mol) 3 ( 0 kJ/mol)
H r!

= 92.2 kJ/mol.

The standard molar Gibbs free energy of reaction at 25C is

G r! = 2 G !f ( NH 3 ) G !f ( N 2 ) 3G !f ( H 2 )
= 2 (16.5kJ/mol) ( 0 kJ/mol) 3 ( 0 kJ/mol)
G r! = 33.0 kJ/mol.

Now we can substitute these values into the expression above to get the Gibbs free energy of reaction at 500 K,

+ G
% 1
1 (.
298
G 500 ( 500 K) + H 298 '

*0
298 K )/
& 500 K
, 298 K
+ 33.0 kJ/mol
% 1
1 (.
( 500 K) + (92.2 kJ/mol) '

*0
298 K )/
& 500 K
, 298 K
G 500 7.1 kJ/mol.

This is a pretty big change from the value at 298 K and indicates a change in spontaneity at higher temperatures
(due to the change in sign of G from 298 to 500 K).