1

0.9

0.8

0.7

0.6

0.5
Oxygen

0.4

0.3

0.2

0.1

0
0 5 10 15 20 25 30
 13
13.13 Gi G i  RT ln J i xi
G i  RT ln J iy xiy where
Ni q
xi apparent mole fraction
¦ N jq
Ni
xiy actual mole fraction
¦ Nj
In the model, J iy 1 , since the ternary mixture is ideal.

xiy Ni N  NBq Ni N A  NBq

ŸJi u A u
xi N A  N B  N B2 Ni q Ni q N A  N B  N B2
N A  NBq NB N A  NBq
ŸJ A and J B
N A  N B  N B2 NBq N A  N B  N B2
Now consider the chemical equilibrium:

Initial Final Mole fraction

Number moles number moles xi
NA
A NA NA
N A  N Bq  N B2

B N Bq  2 N B2
N Bq N Bq  2 X
N A  N Bq  N B2
N B2
B2 — X
N A  N Bq  N B2
N A  N Bq  X
N A  N Bq  N B2

Ka
a B2 !
N B2 N A  N Bq  N B2 "
a B2 !N q
B  2 N B2 "
2

Solving this equation gives

N B2
!N q
B  NA k  " !N q
B  NA k "2
! "
 4 K A N Bq
2
k
2
where k 4 Ka  1 , and
2 kN B2
N A  N Bq
!
xa  kxB  kxB2  2kxa xB  xa2 "12

2 kxa  2 kxB  G 2k  G
and G !
2 k  1 xa  kxB  kxB2  2kxa xB  xa2
12
"
Also we obtain
 N B2
!N A  N Bq " 2k  G ; N B N Bq 
!N A  N Bq " 2k  G
2k k
N A  N B  N B2 ' N  N q(#$ 2Gk %&
A B and
N A  NBq
N A  N B  N B2
2k
G
Thus
N A  N Bq 2k
J A and
N A  N B  N B2 G

JB
!
N B N A  N Bq "
!
N Bq N A  N B  N B2 "
)+1  2k  G  ,. 2k 2
/! x 2
 2kx A xB  kxB2 " 12
 xA 0
* xk -G B xBG
A
 13
13.17 Suppose we start with 1 mole of hydrogen and z moles of nitrogen. The species balance table is:

Species Initial Final yi

1  3X
H2 1 1  3X
1 z  2 X
z X
N2 z z X
1 z  2 X
2X
NH 3 0 2X
1 z  2 X
¦ 1 z  2 X

and

%PNH 3 1 bar &

2 2
yNH ! 1 bar # 2
Ka
%P
N2 &%
1 bar PH 2 1 bar &3
3

yN 2 yH3 2 " P$
! P# 2
4 X 2 1  z  2 X 2
Ÿ Ka
" 1 bar $  z  X 1  3 X 3
(1)

Note: We are assuming P is low enough that no f P corrections are needed!

Now we want to know how X changes with z, so we will look at the derivative dX dz at constant T
and P. Starting from Eqn. (1) we obtain

8 X 1  z  2 X 2 dX 8 X 2 1  z  2 X  dX ! #
0 
z  X 1  3 X 3 dz z  X 1  3 X 3
1 2
dz " $
4 X 2 1  z  2 X 2 !
dX #
12 X 2 1  z  2 X 2 ! 3 dX #

z  X 2 1  3 X 3
1 
"
dz

$
z  X 1  3 X 4 " dz $
dX 1 z  X   2 1  z  2 X 
Ÿ
dz ' (
2 X  4 1  z  2 X   1  z  X   9 1  3 X 

where X must be equal to, or smaller than, the smallest of 1/3 and z.
z X
For yN 2 05
. Ÿ z 1 . Let z 1  G where G may be either + or –.
1 z  2 X

dX 1 1  G  X   2 2  2 X  G 
dz ' (
2 X  4 2  2 X  G   1 1  X   G   9 1  3 X 

Since X d 1 3 , the denominator is always positive, so we need only look at the numerator to
determine the sign of dX dz .
 1 1
Num 
1 G  X 1 X  G 2 ! "
G G
Now do Taylor series expansions in and .
1 X 21 X 
1 # G %
1 G #' G %(
Num
1 X $
1
1 X

&
1 X
1
21  X  $ 21  X 2 &
Thus, the sign of dX dz is the same as the sign of G  . If G ! 0 , i.e., more N 2 is added than is
required for yN 2 05. , dX dz  0 , so that NH 3 decomposes, and N 2 is produced.
If, however, G  0 , i.e., less N 2 is added than is needed for yN 2 . , the addition of N 2 causes
05
more NH 3 to be formed.
Note: If, instead of N 2 addition at constant pressure, the nitrogen was added at constant total
volume, so that partial pressure of either species were unaffected, and the partial pressure of N 2
increased, then, from

Ka
)P NH 3 1 bar *
2

)P H2 *)
1 bar PH 2 1 bar * 3

it is clear that the reaction would always go in the direction of increased ammonia production. This
is an important distinction between reactions at constant volume and at constant pressure in this case.
 13
13.20 Using the data in the problem statement, Tables 3.4 and Appendix A.IV, I find

aCaOSiO 2 aCO 2 yCO 2 P

Ka,1750 K 1481
. aCO 2 , (1)
aCaCO 3 aSiO 2 1 bar

since the activity of all the solids are unity.

3
aSiO a a
2 Fe 3O 4 CO
aCO yCO
Ka,2 750 K 3
0.0277 , (2)
aFeO ˜SiO 2 aCO 2 aCO 2 yCO 2

and

3
aFe 3O 4 aSiO 1 ! 1 bar $ 12

Ka,3750 K 3
aFeOSiO a1 2
2 O2
2
08973
. u 1014
aO1 22
#" y P &%
O2

yO 2 P
Ÿ .
1242 u 1028 (3)
1 bar

From eqn. (2) we have

yCO y
~ 0.0277 , while from spectroscopic observations CO # 104
yCO 2 yCO 2

Also, from eqn. (1), PCO 2 ~ 148 bar , while from the probe, the total atmospheric pressure is only
between 75 and 105 bar. Finally, from Eqn. (3), we conclude there is no O2 in the atmosphere,
compared to a trace from spectroscopic observations.
Conclusions? Somewhat ambiguous!
Calculations and data are not in quantitative agreement, but are certainly in qualitative agreement.
Consider the uncertainty in all the measurements, the atmospheric model is undoubtedly a
reasonable one, and can not be rejected.
 th
Solutions to Chemical and Engineering Thermodynamics, 4 ed Chapter 13

13.38 (also available as a Mathcad worksheet).

joule joule
R 8.31451  G rxn 2400  T 298.15  K V 4  liter
K  mole mole

a A xA J A x A J A aB 1

P
a C xA J C 1 x A J C a D( P )
5
10 Pa

G rxn
Ka exp Ka 2.633
R T

Part (a):

xA 0.5 (initial guess)

a D 0.5  10  Pa  a C x A  1
5

Given Ka xA Find x A
a B a A x A  1

xC 1 xA

xA 0.16 xC 0.84

Part (b):

Recognizing that the partial molar Gibb's excess is in the form of the one constant Margules
expression yields:

J A exp 0.3  x C J C exp 0.3  x A

2 2

a D 0.5  10  Pa  a C x A  exp 0.3  x A

5 2

Given Ka xA Find x A
a B a A x A  exp 0.3  1
2
xA
xC 1 xA

xA 0.132 xC 0.868
 th
Solutions to Chemical and Engineering Thermodynamics, 4 ed Chapter 13

Part (c):

Mass Balance Table:

Species In Out
A 1 1-X
B 2 2-X
C 0 X
D 0 X

Assuming that D is an ideal gas:

X R T
P=(n*R*T)/V P( X )
V

X 0.5 (initial guess)

X  R T  mole 
aD a C( X  1 )
V
Given Ka X Find ( X )
a B a A ( 1 X  1 )

X 0.425

NA 1 X NB 2 X NC X ND X
X  R T  mole
xA 1 X xC X PD
V

NA 0.575 NB 1.575 NC 0.425 ND 0.425

5
xA 0.575 xC 0.425 PD 2.633 10 Pa
 th
Solutions to Chemical and Engineering Thermodynamics, 4 ed Chapter 13

13.39 (also available as a Mathcad worksheet).

Without dissociation:

Assuming K1  a H2
the activity of molecular
Amount_Adsorbed_Without hydrogen gas is equal to the pressure of hydrogen g

Amount_Adsorbed_Without K1  P H2

With dissociation:
1
Amount_Adsorbed_With K1  a H2 K3  a H
2

Using the equilibrium constant for the reaction H2 = 2H, the activity of atomic hydrogen
solved for in terms of the activity of molecular hydrogen:

2
aH
Given K2 Find a H
a H2

Using the positive root for the activity of hydrogen yields:

1
Amount_Adsorbed_With K1  a H2 K3  K2  a H2
2

Assuming the activity of molecular hydrogen gas is equal to the pressure of hydrogen g

1
Amount_Adsorbed_With K1  P H2 K3  K2  P H2
2
If the amount adsorbed varies linearly with the partial pressure of molecular hydrogen then no
dissociation is occurring. If the amount adsorbed varies as the square root of the partial pressure,
then dissociation is occurring.

13.40 From the data in the problem statement we have that

kj
' rxn G o ' rxn H o  T ' rxn S o or ' rxn H o ' rxn G o  T ' rxn S o 148
mol
The equilibrium constant at 25oC is
§ ' Go · § 19600 ·
K exp ¨  rxn
¨ R ˜ 298.15 ¸¸
exp ¨ ¸ 2716
© ¹ © 8.314 ˜ 298.15 ¹
The equilibrium constant as a function of temperature is obtained from Eq.13.1-22b; the
results are shown below
 th
Solutions to Chemical and Engineering Thermodynamics, 4 ed Chapter 13

Equilibrium constant

5
1 10
4
1 10
3
K 1 10

100

10
260 280 300 320
T
This is for the reaction 2A U A2

The mass balance table for this reaction is

Species Initial Final

Monomer M M(1-2D)
Dimer 0 DM

The equilibrium relation is

aD DM D
Ka
aM2
1  2D  M 1  2D 2 M
2 2

which can be written as

§ 1 ·
4D 2  ¨ 4  ¸ 1 0
© M ˜K ¹
and has the solution
2
§ 1 · § 1 ·
¨4 ¸ ¨4 ¸  16
© M ˜K ¹ © M ˜K ¹
D
8

The solution for the fraction dimerized as a function of temperature is given below: