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Chem340
Physical Chemistry for Biochemists
Dr. Yoshitaka Ishii
Homework 7
Due Date Mar. 9, 2011

Ch 6 P6.2-6.8, P6.10, P6.13, P6.14, P6.16-6.20. P6.24, P6.28, P6.30, P6.38
P6.2) Calculate AA for the isothermal compression of 2.00 mol of an ideal gas at 298
K from an initial volume of 35.0 L to a final volume of 12.0 L. Does it matter whether
the path is reversible or irreversible?
At constant T, we consider the reversible process. Because is a state function, any path
whether reversible or irreversible, between the same initial and final states will give the same r
dA SdT PdV
A
=
1 1 3
esult.
12.0 L
ln 2.00 mol 8.314 J mol K 298 K ln 5.30 10 J
35.0 L
f
i
V
f
i V
V
A PdV nRT
V

A = = = =
}

P6.3) Calculate AG for the isothermal expansion of 2.50 mol of an ideal gas at 350 K
from an initial pressure of 10.5 bar to a final pressure of 0.500 bar.
At constant T, we consider the reversible process. Because G is a state function, any path
between the same initial and final states will give the same result.
ln 2.50 mol
f
i
P
f
i P
dG SdT VdP
P
G VdP nRT
P
= +
A = = =
}
1 1 3
0.500 bar
8.314 J mol K 350 K ln 22.1 10 J
10.5 bar

=

2

P6.4) A sample containing 2.50 mol of an ideal gas at 298 K is expanded from an
initial volume of 10.0 L to a final volume of 50.0 L. Calculate AG and AA for this
process for (a) an isothermal reversible path and (b) an isothermal expansion against a
constant external pressure of 0.750 bar. Explain why AG and AA do or do not differ
from one another.
a) for the isothermal reversible path
1 1 3
ln ln
10.0 L
2.50 mol 8.314 J mol K 298 K ln 9.97 10 J
50.0 L
f
i
P
f
i
i f P
P
V
G VdP nRT nRT
P V

A = = =
= =
}

1 1 3
ln
50.0 L
2.50 mol 8.314 J mol K 298 K ln 9.97 10 J
10.0 L
f
i
V
f
i V
V
A PdV nRT
V

A = =
= =
}

b) Because A and G are state functions, the answers are the same as to part a) because
the systems go between the same initial and final states, T,V
i
T,V
f
.

AG AA = AH AU = APV) = AnRT). Therefore, AG = AA for an ideal gas if T is
constant.
P6.5) The pressure dependence of G is quite different for gases and condensed
phases. Calculate G
m
(C, solid, graphite, 100 bar, 298.15 K) and G
m
(He, g, 100 bar,
298.15 K) relative to their standard state values. By what factor is the change in G
m

greater for He than for graphite?
3
( )
( ) ( )
3
5
3
For a solid or liquid,
( , ,100 bar) ( , ,1 bar) ( , ,1 bar)
12.011 10 kg
0 99.0 10 Pa = 52.8 J
2250 kg m
f
i
P
f i
P
m m m f i m f i
G VdP V P P
M
G C s G C s V P P G C s P P

A = =
= + = +

= +
}

( ) ( )
1 1 3
Treating He as an ideal gas,
, ,100 bar , ,1 bar
100 bar
0 ln 1 mole 8.314 J mol K 298.15 K ln =11.4 10 J
1 bar
f
i
P
m m
P
f
i
G He g G He g VdP
P
RT
P

= +
= + =
}

This result is a factor of 216 greater than that for graphite.

P6.6) Assuming that

AH
f

## is constant in the interval from 275 to 600 K, calculate

AG for the process (H
2
O, g, 298 K) (H
2
O, g, 525 K).
f
G A

( H
2
O, g, 525 K).

( )
( )
( )
( )
1
2 2 1
1 2 1
3 1
3 1
3 1
1 1
228.6 10 J mol 1 1
525 K 241.8 10 J mol
298.15 K 525 K 298.15 K
525 K 218.5 10 J mol
f
f f
f
G T
G T T H T
T T T
G

( A | |
A = + A
(
|
\ .

( | |
=
| (
\ .

A =

P6.7) Calculate

AG
reaction

2
(g) CO
2
(g) at 298.15
K. Calculate

AG
reaction

## at 650 K assuming that AH

reaction

is constant in the
temperature interval of interest.
( ) ( ) ( ) ( )
2 2
3 1 3 1
3 1
1
298.15 K CO , CO, O ,
2
394.4 10 J mol + 137.2 10 J mol 0
257.2 10 J mol
reaction f f f
G G g G g G g

A = A A A
=
=

4
( ) ( ) ( ) ( )
2 2
3 1 3 1
3 1
1
298.15 CO , CO, O ,
2
393.5 10 J mol + 110.5 10 J mol 0
283.0 10 J mol
reaction f f f
H K H g H g H g

A = A A A
=
=

( )
( )
( )
1
2 2 1
1 2 1
1 1
reaction
reaction reaction
G T
G T T H T
T T T
( A | |
A = + A
( |
\ .

( )
3 1
3 1
3 1
257.2 10 J mol 1 1
650 K 650 K 283.0 10 J mol
298.15 K 650 K 298.15 K
226.8 10 J mol
reaction
G

( | |
A =
| (
\ .

=

P6.8) Calculate

AA
reaction

and AG
reaction

## for the reaction CH

4
(g) + 2O
2
(g)
CO
2
(g) + 2H
2
O(l) at 298 K from the combustion enthalpy of methane and the
entropies of the reactants and products.
All reactants and products are treated as ideal gases
( ) ( ) ( ) ( )
2 2 4 2
1 1 1 1 1 1 1 1
1 1
3
CO , 2 H O, CH , 2 O ,
213.8 J mol K + 2 70.0 J mol K 186.3 J mol K 2 205.2 J mol K
242.9 J mol K
890.3 10 J m
combustion combustion combustion
combustion
combustion
G H T S
S S g S l S g S g
G

A = A A
A = +
=
=
A =

( )
1 1 1 3 1
ol 298.15 K 242.7 J mol K 817.9 10 J mol

=
( )
( )

combustion combustion combustion
combustion combustion
combustion
combustion combustion combustion
combustion
A U T S
H PV T S
G T S PV T S
G nRT
A = A A
= A A A
= A + A A A
= A A

( )
3 1 1 1
3 1
where is the change in the number of moles of gas phase species in the reaction
817.9 10 J mol 2 8.314J mol K 298.15 K
812.9 10 J mol
combustion
n
A

A
=
A =

P6.10) The standard Gibbs energy of formation AG
f

## for carbon dioxide gas is

394.4 kJ mol
1
. Calculate the Gibbs energy of formation of carbon dioxide at its
normal sea level partial pressure of 0.00031 atm.
5
The Gibbs energy of formation is given by:
( ) ( )
( ) ( ) ( ) ( )
( )
( )
0 0
f f 0
-1 -1 -1
-1
p
G p G p n R Tln
p
0.00031 atm
394.4 kJ mol 1 mol 8.314472 J K mol 298 K ln
0.99969 atm
414.4 kJ mol
| |
= +
|
\ .
| |
= +
|
\ .
=

P6.13) Nitrogen is a vital element for all living systems; except for a few types of
bacteria, blue-green algae, and some soil fungi, organisms cannot utilize N
2
from the
atmosphere. The formation of fixed nitrogen is therefore necessary to sustain life
and the simplest form of fixed nitrogen is ammonia NH
3
. Living systems cannot fix
nitrogen using the gas-phase components listed in Problem P6.12. A hypothetical
ammonia synthesis by a living system might be:

1
2
N
2
g ( )+
3
2
H
2
O l ( )NH
3
aq ( )+
3
2
O
2
g ( )
where (aq) means the ammonia is dissolved in water. Calculate the standard free
energy change for the biological synthesis of ammonia and calculate the equilibrium
constant as well. Based on your answer, would the biological synthesis of ammonia
occur spontaneously? Note that AG
f

NH
3
, aq ( )= 80.3 kJ mol
1
.
( )
( )
( )
( )
( )
( ) ( ) ( )
1 - 1 - 1 -
0
H
0
NH
0
i
0
i
0
reaction
mol kJ 75.35 2 mol kJ 1 . 237
2
3
mol kJ 3 . 80 1
G
2
3
G 1 G G
2 3
= |
.
|

\
|
+ =
|
.
|

\
|
+ = =
O aq
i
v

The equilibrium constant is then:
( )
( ) ( )
49 -
1 - 1 -
-1 -1 0
reaction
p
10 .45 5
K 98 2 mol K J .314472 8
mol kJ mol kJ 75.35 2
Exp
T R
G
Exp K =
(

=
(

=

6
P6.14) Consider the equilibrium
NO
2
(g) NO(g) + O
2
One mole of NO
2
(g) is placed in a vessel and allowed to come to equilibrium at a total
pressure of 1 bar. An analysis of the contents of the vessel gives the following results:
T 700K 800K
P(NO)/P(NO
2
) 0.872 2.50
a. Calculate K
P
at 700 and 800 K.
952 . 3
] 1 [
] 5 . 2 ][ 5 . 2 [
] [
] ][ [
] [
] ][ [
) 800 (
934 . 0
] 1 [
] 872 . 0 ][ 872 . 0 [
] [
] ][ [
] [
] ][ [
) 700 (
2
1
2
1
2
2
1
2
2
1
2
1
2
2
1
2
2
2
2
2
= = = =
= = = =
NO
O NO
p
NO
O NO
p
P
P P
NO
O NO
K K
P
P P
NO
O NO
K K

b. Calculate
0
reaction
G A at 298.15K assuming that
0
reaction
H A is independent of
temperature.
= = A ) 700 ( ln
0
700
K K RT G
P
-0.397 kJ mol
-1

= = A ) 800 ( ln
0
700
K K RT G
P
-9.140 kJ mol
-1

P6.16) Consider the reaction FeO(s) + CO(g) Fe(s) + CO
2
(g) for which K
P
is
found to have the following values:
T 600
o
C 1000
o
C
K
P
0.9 0.396
a. Calculate
0
reaction
G A ,
0
reaction
S A , and
0
reaction
H A for this reaction at 600
o
C. Assume
7
that
0
reaction
H A is independent of temperature.
= = A ) 873 ( ln
0
873
K K RT G
P
-0.764 kJ mol
-1

= = A ) 1273 ( ln
0
1273
K K RT G
P
-9.804 kJ mol
-1

Using the Gibbs-Helmholtz equation:
mol kJ
G G
T T T
G
T
G
H
T T
H
T
G
T
G
T T
T T
/ 53 . 29
873
1
1273
1
873 1273
1 1
1 1
1
0
873
0
1273
1
1 2 2
0
1
0
1 2 2
0
1
0
2 1
2 1
= |
.
|

\
|

|
|
.
|

\
| A

A
=
|
|
.
|

\
|

|
|
.
|

\
| A

A
= A
|
|
.
|

\
|
A +
A
=
A

K J
G H
S
K J
G H
S
T
G H
S
S T H G
/ 6 . 22
873
/ 6 . 22
1273
873
873
1273
1273
=
A A
= A
=
A A
= A
A A
= A
A A = A

b. Calculate the mole fraction of CO
2
(g) present in the gas phase at 600
o
C.
900 . 0
] 0 . 1 [
] 9 . 0 [
] [
] [
] [
] [
) 873 (
2 2
= = = =
CO
CO
P
P
K K
CO
CO
p

47 . 0
] 0 . 1 9 . 0 [
] 9 . 0 [
2
2
=
+
= =
total
CO
n
n
X
CO

P6.17) If the reaction

Fe
2
N s ( )+ 3 2H
2
g ( )

2Fe s ( )+ NH
3
g ( ) comes to
equilibrium at a total pressure of 1 bar, analysis of the gas shows that at 700 and 800
K,

P
NH
3
P
H
2
= 2.165 and 1.083, respectively, if only H
2
(g) was initially present in
the gas phase and Fe
2
N(s) was in excess.
a. Calculate K
P
at 700 and 800 K.
8
b. Calculate

AS
reaction

## at 700 and 800 K and AH

reaction

assuming that it is
independent of temperature.
c. Calculate

AG
reaction

## for this reaction at 298.15 K.

a) FeN
2
(s) + 3/2 H
2
(g) 2Fe(s) + NH
3
(g)

( )
3
2
3/ 2
/
/
NH
P
H
P P
K
P P
=

P
total
= 1 atm =
3 2

NH H
P P +

At 700 K,
1 atm = 2.165
2 2
H H
P P + = 3.165
2
H
P

2
H
P = 0.316 atm,
3
NH
P = 0.684 atm

( )
3/ 2
0.684
(700 K) = =3.85
0.316
P
K

At 800 K
1 atm = 1.083
2 2
H H
P P + = 2.083
2
H
P

2
H
P = 0.480 atm,
3
NH
P = 0.520 atm
( )
( )
3/ 2
0.520
800 K 1.56
0.480
P
K = =

b) Assume that
reaction
H A

is independent of temperature

( )
( )
( )
( )
1
800 K 1 1
ln
700 K 800 K 700 K
800 K
ln
700 K
42.1 kJ mol
1 1
800 K 700 K
P reaction
P
P
P
reaction
K H
K R
K
R
K
H

A | |
=
|
\ .

A = =
| |

|
\ .

9

( ) ( )
( ) ( )
( )
( )
( )
1
1
1 1
1 1
700 K ln 700 K 7.81 kJ mol
800 K ln 800 K 2.91 kJ mol
700 K
700 K 48.9 J mol K
700 K
800 K 48.9 J mol K
reaction P
reaction P
reaction reaction
reaction
reaction
G RT K
G RT K
H G
S
S

A = =
A = =
A A
A = =
A =

The values of
reaction
S A

at 700 K and 800 K are nearly the same because
reaction reaction
G H A << A

( ) ( )
( ) ( )
3 1
1 1
P
1 1
c) ln 298.15 K ln 700 K
298.15 K 700 K
42.1 10 J mol 1 1
= ln 3.85 + 11.1
8.314 J mol K 298.15 K 700 K
298.15 K ln K 298.15 K
= 8
reaction
P P
reaction
H
K K
R
G RT

A | |
=
|
\ .
| |
=
|
\ .
A =

1 1 1
.314 J mol K 298.15 K 11.1= 27.5 kJ mol

P6.18) Many biological macromolecules undergo a transition called denaturation.
Denaturation is a process whereby a structured, biological active molecule, called the
native form, unfolds or becomes unstructured and biologically inactive. The
equilibrium is

native folded ( )

denatured unfolded ( )
For a protein at pH = 2, the enthalpy change associated with denaturation is AH =
418.0 kJ mol
1
and the entropy change is AS = 1.3 kJ K
1
mol
1
.
a. Calculate the Gibbs energy change for the denaturation of the protein at pH = 2
and T = 303 K. Assume the enthalpy and entropy are temperature independent
between 298.15 and 303 K.
b. Calculate the equilibrium constant for the denaturation of protein at pH = 2 and T
10
= 303 K.
c. Based on your answers for parts (a) and (b), is protein structurally stable at pH =
2 and T = 303 K?
a) We first need to calculate AG
den
at 298 K:
( ) ( ) ( ) ( ) ( )
1
-1 -1 -1
den den den
mol J 0600 3
K 298 K mol J 1300 mol J 418000 S T - K 298 H K 298 G

=
= A =

Then ( ) K 303 G
reaction
can be calculated using:
( )
( )
(

|
|
.
|

\
|
+ =
1 2
reaction
1
1 reaction
2 2 reaction
T
1
T
1
H
T
T G
T T G
( ) ( )
( )
( )
( )
( ) ( )
1 -
1 -
-1
reaction
mol J 24098.97
K 298
1
K 303
1
mol kJ 418.00
K 298
mol J 30600
K 303 K 303 G
=
(

|
|
.
|

\
|
+ =

b) The equilibrium constant at 303 K is:
( )
( )
( ) ( )
5 -
1 - 1 -
1 - 1 -
den
p
10 5.97
K 298 mol K J 8.314472
mol J mol J 24098.97
Exp
T R
G
Exp K 303 K
=
(

=
(

A
=

c) The large positive AG
den
and the small equilibrium constant indicate that the protein
is stable.
P6.19) The melting temperature of a protein is defined as the temperature at which
the equilibrium constant for denaturation has the value K = 1. Assuming that the
enthalpy of denaturation is temperature independent, use the information in Problem
P6.18 to calculate the melting temperature of the protein at pH = 2.
11
We first calculate the equilibrium constant at 298 K:
( )
( )
( )
( ) ( )
6 -
1 - 1 -
1 -
0
reaction
p
10 .329 4
K 98 2 mol K J .314472 8
mol J 0600 3
Exp
T R
K 298 G
Exp K 298 K
=
(

=
(

=

We then solve for T
m
, with ( ) ( ) ( ) 0 1 ln T K ln
m p
= = :
( ) ( ) ( ) ( )
( )
|
|
.
|

\
|
=
K 298.15
1
T
1
R
H
298 K ln T K ln
m
0
reaction
p m p

( )
( ) ( ) ( ) ( ) { }
( )
( ) ( ) { }
( )
K 21.5 3
mol J 418000
10 .329 4 ln 0 mol K J 8.314472
K 298.15
1
1
H
298 K ln T K ln R
K 298.15
1
1
T
1 -
6 - 1 - 1 -
0
reaction
p m p
m
=
|
|
.
|

\
|

+
=
|
|
.
|

\
|

=

P6.20) Calculate the Gibbs energy change for the protein denaturation described in
Problem 5.45 at T = 310.K and T = 340.K.
From P5.45 we have:
( )
-1 -1
den
mol K J 4 . 1109 K 310 S =
( )
( )
1 - 1 -
den
-1 -1
den
mol K kJ 640.1 K 340 H
mol K kJ 43.9 3 K 310 H
=
=

( ) K 310 G
den
is then:
( ) ( ) ( )
( ) ( ) ( )
1 - 1 - 1 - 1 -
den den den
mol kJ 0 mol K J 4 . 1109 K 310 mol kJ 43.9 3
K 310 S T K 310 H K 310 G
= =
=

At 340 K we obtain:
12
mol kJ G
T T
H
T
G
T
G
T T
/ 945 . 61
310
1
340
1
) 1 . 640 )( 340 (
310
0
) 340 (
1 1
0
340
1 2 1
0
2
0
1 2
= |
.
|

\
|
+ |
.
|

\
|
= A
|
|
.
|

\
|
A +
A
=
A

P6.24) At T = 298 K and pH=3 chymotrypsinogen denatures with AG = 30.5 kJ
mol
1
, AH = 163 kJ mol
1
, and AC
P,m
= 8.36 kJ K
1
mol
1
. Determine AG for the
denaturation of chymotrypsinogen at T = 320. K and pH=3. Assume AC
P,m
is constant
between T = 298 K and T = 320. K.
First, we calculate AS
0
at T = 298 K:
( )
( ) ( )
( ) ( )
( )
1 - 1 -
1 - 1 -
mol K kJ .445 0
K 98 2
mol kJ 63 1 mol kJ 0.5 3
T
K 298 H K 298 G
K 298 S
=
|
|
.
|

\
|
=
|
.
|

\
|
=

To calculate AG at T = 320 K we need to calculate AH and AS at T = 320 K with a
constant AC
p,m
:
( ) ( )
( ) ( ) ( )
1 - 1 - 1 - 1 -
m p,
mol kJ 46.92 3 K 2 2 mol K kJ .36 8 mol kJ 63 1
T C K 298 H K 320 H
= + =
+ =

( ) ( )
( ) ( )
( )
( )
1 - 1 -
1 - 1 - 1 - 1 -
298
320
m p,
mol K J 040.46 1
K 298
K 320
ln mol K kJ .36 8 mol K J 45 4
T
T
ln C n K 298 S K 320 S
=
|
|
.
|

\
|
+ =
|
|
.
|

\
|
+ =

AG at T = 320 K is then:
( ) ( ) ( )
( ) ( ) ( )
1 - 1 - 1 - 1 -
mol kJ 3.97 1 mol K J 040.46 1 K 20 3 mol kJ 46.92 3
K 320 S T K 320 H K 320 G
= =
=

13
P6.28) Calculate

O
2
mixture
298.15 K, 1 bar ( ) for oxygen in air, assuming that the
mole fraction of O
2
in air is 0.200.
For pure O
2
:
( ) ( ) ( ) ( ) ( )
-1 -1 -1
2 m 2 m O
mol J 61180.38 K mol J 205.2 K 298.15 O S T O G pure
2
= = = =

For O
2
in air:
( ) ( )
( ) ( ) ( ) ( )
1 - 1 - 1 - 1 -
O O O
mol kJ 2 . 65 200 . 0 ln K 98.15 2 mol K J .314472 8 mol J 61180.38
ln x T R pure mix
2 2 2
= + =
+ =

P6.30) You have containers of pure H
2
and He at 298 K and 1 atm pressure.
Calculate AG
mixing
relative to the unmixed gases of
a. a mixture of 10 mol of H
2
and 10 mol of He.
b. a mixture of 10 mol of H
2
and 20 mol of He.
c. Calculate AG
mixing
if 10 mol of pure He are added to the mixture of 10 mol of H
2

and 10 mol of He.
( )
1 1
1 1
1 1 1 1
a) 20 mol 8.314 J K mol 298 K ln ln 34.4 kJ
2 2 2 2
1 1 2 2
b) 30 mol 8.314 J K mol 298 K ln ln 47.3 kJ
3 3 3 3
c) pure gases

mixing
mixing
mixing mixing
mixi
G
G
G G
G

| |
A = + =
|
\ .
| |
A = + =
|
\ .
A = A
A ( ) 10 mol A + 10 mol B
= 47.3 34.4 12.9 kJ
ng
+ =

P6.38) Consider the equilibrium in the reaction 3O
2
g ( )

2O
3
g ( ), with

AH
reaction

= 285.4 10
3
J mol
1
at 298 K. Assume that AH
reaction

is independent of
temperature.
14
a. Without doing a calculation, predict whether the equilibrium position will shift
toward reactants or products as the pressure is increased.
b. Without doing a calculation, predict whether the equilibrium position will shift
toward reactants or products as the temperature is increased.
c. Calculate K
P
at 550 K.
d. Calculate K
x
at 550 K and 0.500 bar.
a) Since the number of moles on the product side (2) is smaller than on the reactant
side (3), increasing the pressure would shift the equilibrium towards the product side.
b) Since the reaction is endothermic (H > 0), increasing the temperature would shift
the equilibrium towards the products.
c) To obtain K
p
at 550 K, first K
p
at 298.15 has to be calculated. This requires the
calculation of

reaction
S , and subsequently

reaction
G at 298.15 K:
( ) ( ) ( )
-1 -1 -1 -1 -1 -1
i
i f, i reaction
mol K J 137.8 - mol K J 205.2 3 mol K J 238.9 2 S K 298.15 S = = =

( )
( )
( ) ( ) ( ) { }
( ) ( )
58 -
1 - 1 -
1 - 1 - 1 - 3
p
10 5.9865
K 550 K mol J 8.314472
mol K J 137.8 298.15K mol J 10 285.4
Exp
T R
K 298.15 G
Exp K 298.15 K
=
(

+
=
(

=

Then:
( ) ( )
( )
( ) ( ) ( )
35
10 4

=
(

|
|
.
|

\
|

= .98
K 298.15
1
K 550
1
K mol J 8.314472
mol J 10 285.4
K 298.15 ln Exp K 550 K
1 - 1 -
-1 3
p
d) K
x
at 550 K and 0.500 bar with Av = 1 is given by:
( )
35 35
p
1
p
-
p x
10 96 . 9 10 98 . 4 2 K 2
bar 1.0
bar 0.5
K
p
p
K K

= = = |
.
|

\
|
=
|
|
.
|

\
|
=
v

Q1. Prove that
( )
2
/
) (
/
T U
T
T A
V
A =
)
`

c
A c
and
( )
U
T
T A
V
A =
)
`

c
A c
) / 1 (
/
. They
are also known as Gibbs-Helmholtz equations. Write an expression analogous to Eq.
(6.37) to relate AA at two temperatures. (Modified from P6.27).
15
( )
( ) ( ) ( )
U
T
T A
T
T
T
T
T A
T
T A
T U
T
S T A
T
A
T
S
T
A
T
A
T T
T A
V
V
V
V
V
V
A = |
.
|

\
|
c
A c
=
|
|
.
|

\
|
c
c
|
.
|

\
|
c
A c
=
)
`

c
A c
A =
A + A
=
A

A
=
A
|
.
|

\
|
c
A c
=
)
`

c
A c
/
) / 1 (
/
) / 1 (
/
/
1
) (
/
2
2
2 2 2

( ) ( )
( )
2 2
1 1
2 1
1
2 1 2 1
At constant ,
1 1
T T
T T
V
A U
d d
T T
A T A T
U T
T T T T
A A
| | | |
=
| |
\ . \ .
A A | |
~ + A
|
\ .
} }

16
Q2. Figure 6.8 in p126 depicts the total Gibbs energy for a mixture of NO
2
(g) and
N
2
O
4
(g) at a different ratio in its equilibrium between (2 -2 ) mole of NO
2
and
mole of N
2
O
4
(g) at a constant pressure and temperature at 1 bar and 298 K. (a)
Reproduce the plots for G
pure
and G
mixture
assuming that G
m
0
(NO
2
, g) = -38.45 kJmol
-1
and G
m
0
(N
2
O
4
, g) = -79.60 kJmol
-1
. (b) Explain how you obtained the equations
to calculate G
pure
and G
mixture
. (c) How much is in the equilibrium state.
(Modified from P6.41)
(a)
0.0 0.2 0.4 0.6 0.8 1.0
-81
-80
-79
-78
-77
G
mixture
G
(
k
J

m
o
l
-
1
)

G
pure
=0.72,G=-81.0kJ mol
-1

(b)
(

+ =

+

+ =
+ + = + =
= +
= + =

2
ln
2
2 2
ln ) 2 - (2
mol kJ 298 10 8.314472 mol kJ 70 . 2 mol kJ -76.90
)
2
ln
2 2
2 2
ln
2
2 2
( ) - (2 G
) ln ln ( G G G G
mol kJ 70 . 2 mol kJ -76.90 ) mol kJ (-79.60
) mol kJ (-38.45 ) 2 - (2 ) , ( G ) , ( G ) 2 - (2 G
1 - 3 1 - 1 -
pure
pure mixing pure mixture
1 - 1 - 1 -
-1
4 2
o
m 2
o
m pure
4 2 4 2 2 2
RT
x x x x nRT
g O N g NO
O N O N NO NO

(c) At the equilibrium state, G
mixture
has a minimum is at = 0.72.

17
Q3. Plot G
mixture
() at 350K for the system described in Q2 (assume that the total
pressure is 1 bar). Does T affect in the equilibrium state? (Hint: first, obtain
G
m
0
(NO
2
, g) and G
m
0
(N
2
O
4
, g) at T = 400K.)

1 -
1 - 1 -
4 2
o
f 4 2
o
m 4 2
o
m
1 -
1 - 1 -
2
o
f 2
o
m 2
o
m
mol -95.43kJ
)
298K
1
-
350
1
( ) mol kJ 1 . 11 ( 350 ) mol kJ -50.95 (
298K
350K

)
298K
1
-
350
1
)( , ( H 350 ) 298 , , ( G
298K
350K
) 350 , , ( G
mol -50.95kJ
)
298K
1
-
350
1
( ) mol kJ 2 . 3 3 ( 350 ) mol kJ -38.45 (
298K
350K

)
298K
1
-
350
1
)( , ( H 350 ) 298 , , ( G
298K
350K
) 350 , , ( G
=
+ =
+ =
=
+ =
+ =
K
K
K
g O N K K g O N K g O N
K
K
K
g NO K K g NO K g NO
(

+ + =

+

+
+ =
+ + + =
+ + + =
+ + = + =

2
ln
2
2 2
ln ) 2 - (2
mol kJ 350 10 8.314472 mol kJ 3 . 15 mol kJ -125.94
)
2
ln
2 2
2 2
ln
2
2 2
( ) - (2
mol kJ 49 . 6 mol kJ -101.91
) ln ln ( ) mol kJ (-95.43 ) mol kJ (-50.95 ) 2 - (2
) ln ln ( ) 350 , , ( G ) 350 , , ( G ) 2 - (2
) ln ln ( G G G G
1 - 3 1 - 1 -
1 - 1 -
1 - 1 -
4 2
o
m 2
o
m
pure mixing pure mixture
4 2 4 2 2 2
4 2 4 2 2 2
4 2 4 2 2 2
RT
x x x x nRT
x x x x nRT K g O N K g NO
x x x x nRT
O N O N NO NO
O N O N NO NO
O N O N NO NO

T affects of this reaction,
eq
corresponds to ~0.16.