Chapter 11 Reactions Involving Gases

11-1 Introduction............................................................2
11-2 Reaction Equilibrium in Gas Mixture and.............2
11-3 Effect of Temperature on K ................................5
P

11-4 Effect of Pressure on Equilibrium Constant .........6

11-5 Reaction Equilibrium in SO - SO - O
2( g)

3( g)

2( g)

System..............................................................................9
11-6 In a system to keep a constant p

O2

through gas

mixture of SO / SO , CO/ CO , H / H O ................12

2


11-1 Introduction
When gases exhibiting marked chemical affinity for one another are mixed Final
composition ?
e.g.

A ( g ) + B ( g ) = 2C ( g )
2H 2( g ) + O 2( g ) = 2 H 2 O ( g )

at T

initial state : 1 mole H 2( g ) + 1 mole O 2( g )

final state : ? H 2( g )

1.

+ ? O 2( g )

+ ? H 2 O ( g)

If the pressure is low enough

ideal gas can be assumed .

partial pressure of i , p i = x i P

2. Change of Gibbs Free Energy : G

G

(1) G R ( chemical reaction )

(2) G M ( mixing of remaining reactant gases and final product gases )

3. Final equilibrium state G min

4. Equilibrium constant for reaction : K

11-2 Reaction Equilibrium in Gas Mixture and

Equilibrium Constant
Consider

A ( g ) + B ( g ) = 2C ( g)

At constant T , P ( total) = 1 atm

Initial : ( 1 mole A ) + ( 1 mole B )
Final (any time ) : ( n A mole A ) + ( n B mole B ) + ( n C mole C )
At any instant during reaction :
G ' = n A G A + n B G B + n C GC

n A , n B , n C G ' = G 'min reaction stops .

final

n A = n B ( Reaction consumes equal amount of A , B )

n C = 2 n A n B = 2 ( 1n A )

G ' = n A G A + n B G B + n C GC
G ' = n A ( G A + G B 2 G C ) + 2 G C
Ideal gas mixture :

d G i = RT d(ln p i )

G i = G io + RT ln p i
G i = G io + RT ln X i + RT ln P
X A=

nA
2

XB=

nB
,
2

XC =

2(1 n A )
= (1 n A )
2

G ' = n A ( G oA + G oB 2 G oC ) + 2 G oC + 2 RT ln P

n
+ 2RT n A ln A + (1 n A ) ln( 1 n A )
2

G = ( 2 G oC G oA G oB ) : Standard Gibbs Free Energy Change

o

G ' 2 G oC = n A ( G o ) + 2RT ln P

n
+2RT n A ln A + (1 n A ) ln( 1 n A )
2

If total pressure P = 1 atm

n
G ' 2 G oC = n A ( G o ) +2RT n A ln A + (1 n A ) ln( 1 n A )
2

First term : G due to reaction

Second term : G due to mixing of gas
G ' = G ' ( G oA + G oB )

= [ 2 G oC ( G oA + G oB )

+ n A ( G o )

n
+2RT n A ln A + (1 n A ) ln( 1 n A )
2

n
G ' = ( 1n A ) G o +2RT n A ln A + (1 n A ) ln( 1 n A )
2

Figure 11-1
point L : initial state ( 1 mole A , 1 mole B )
point Q: 2 mole C (complete reaction ) none of A , B
NQ = G o
LM =2RT ln 2 ( mixing 1 mole A , 1 mole B )

= G oM

MRN : ( n A : A ) + ( n B : B ) + ( n C : C )
G =RT n i ln X i = (2) ( ideal gas mixing )
M

S : Equilibrium state ( minimum G ' )

G '
=

n A T, P

G '

n A

= 0
T ,P

G ' = n A G A + n A G B + 2( 1n A ) G C
G '

n A

= G A + G B 2 G C = 0

( G oA + RT ln p A ) + ( G oB + RT ln p B ) = 2 G oC + 2RT ln p C

p 2C
2 G G G =RT ln
pA pB
o
A

o
C

o
B

Define : Equilibrium constant for reaction A + B = 2C

KP

p 2C
pA pB

G =RT ln K P
o

i.e. If G oA , G oB , G oC known
G o can be calculated at T , P
K P can be obtained
p A , p B , p C and then n A can be obtained
that is final equilibrium composition

e.g.

A ( g ) + B ( g ) = 2C ( g)
G oA = G oB = 0 , G oC =2500 J , T = 500K , P = 1 atm

G =2 G oC G oA G oB =5000 J

K P = exp(

3.329 =

n A = 0.523 ( n A =11.4 nonphysical )

n B = 0.523 , n C = 2( 1n A ) = 0.954 mole

G o
) = 3.329
RT

p 2C
(X C P ) = (XC ) = (1 n A )
=
p A p B (X B P )(X A P) (X B )(X A ) n A 2

2
2

11-3 Effect of Temperature on K

In Figure 11-1 , LM = G M and NQ = G oR and are dependent on T

Minimum point of curve MSQ is influenced by T

i.e. K P is a function of T

(G o / T)
H o

= 2
T
T

ln K P
H o
=
T
RT 2
ln K P
H o
or
=
R
(1 / T )

and G o =RT ln K P

Vant Hoff Equation

If H o 0 , endothermic reaction
p 2C
T K P
Reaction shifts to right hand side
pA pB
i.e.

A + B

e.g.

Cl 2( g)

H o 0

2 Cl ( g)

KP=

p 2Cl
p Cl 2

T K P ( p Cl2 ) and

( p Cl 2 )

Le Chatelier s Principle :
Equilibrium is shifted toward in the direction to eliminate the
disturbance .

11-4 Effect of Pressure on Equilibrium Constant

G o = 2 G oC G oA G oB
G oi is defined as P = 1 atm , T

G o is independent of pressure
K P is independent of pressure ( But p i can change )
e.g.

Cl 2( g)

2 Cl ( g)

p 2Cl
(X Cl P ) 2
XCl 2
KP=
=
=
P = Kx P
p Cl 2
X Cl 2 P
X Cl 2

K x is defined in terms of mole fraction

In general , aA + bB = cC + dD

KP=

p cC p dD
= Kx P
p aA p bB

only if ( a+b ) = ( c+d ) ,

if ( a+b ) ( c+d ) ,
if ( a+b ) ( c+d ) ,
when K x changes p i

( c +d ) ( a +b )

K x is independent of P
P Kx
P Kx
( K P is constant )
changes

Reaction Equilibrium as a compromise between H and S

G = HTS
Constant T ,
G = HT S
G min H min and S max
e.g.

Cl 2( g) = 2 Cl ( g)

H 0 , S 0
o

i.e.

Cl ( g) has a higher H than Cl 2( g)

2 Cl ( g) has a higher S than Cl 2( g)

Cl ( g)

H G
S G

For

compromise is required

A ( g ) + B ( g ) = 2C ( g)

n
G ' 2 G oC = n A ( G o ) +2RT n A ln A + (1 n A ) ln( 1 n A )
2

n
= n A ( H o ) +T n A S o + 2R[n A ln A + (1 n A ) ln( 1 n A )]
2

'
'
= H T S

If T = 500K , G o =5000(J)
G oA G oB = 0

2 G o =5000(J)

Take H o =2500(J)

S o = 5 (J/K)

When T T S ' is more important

(n A ) eg , (n C ) eg
i.e. G 'min shifts to left
( Another viewpoint : H o 0

T K P equilibrium shifts to left)

Figure 11-2
Note:
G o = H o T S o = RT ln K P
T G o
for H o 0 ,
T K P

ln K P
H o
(
=
)
T
RT 2

G o 0

 11-5 Reaction Equilibrium in SO - SO - O

2( g)

System

SO 2( g)

Given

1
O 2( g) SO 3( g )
2

G =94600 + 89.37 T
o

1
mole
2
final composition ? and p i = ?

1. T = 1000 K , n o( SO2 ) = 1 mole , n o( O2 ) =

P = 1 atm
Sol :

SO 2( g)

1
O 2( g)
2

SO 3( g )

1
2

Initial

Final

1x

1
(1x)
2

T = 1000 K , G o = 5230 J
G o
ln K P =
=0.629 , K P =1.876
RT
KP=

p so3

K 2p =

p so2 p12/ 2

p so3 2
p so2 2 p O2

Total moles : n T = (1x) +

p i =X i P =

p SO3 =

K 2p =

1
1
(1x) + x =
(3x)
2
2

ni
P
nT

2xP
,
(3 x )

pSO2 =

2(1 x ) P
,
(3 x )

pO 2 =

(1 x )P
(3 x)

(3 x) x 2
(1 x ) 3 P

( 1P K 2p ) x 3 + ( 3 P K 2p 3) x 2 3 P K 2p x + P K 2p = 0 ..()
P = 1 atm , K P =1.876
Final composition :

x = 0.463

3( g)

2( g)

n SO2 = 0.537 mole

n O 2 = 0.269 mole
n SO3 = 0.463 mole
p SO2 = 0.423 atm
p O 2 =0.212 atm
p SO3 =0.365 atm
2. Effect of Temperature : T ( 1000K 900K )

G =94600 +89.37T

H o = (94600) 0

T equilibrium shifts to right p SO3 ,

S o = (89.37)0

From () , T= 900K K P =6.64 P = 1 atm

x = 0.704

n SO2 = 0.296 mole

n O 2 = 0.148 mo le
n SO3 = 0.704 mole

p SO2 = 0.258 atm

p O 2 =0.129 atm
p SO3 =0.613 atm

3.

Effect of Pressure :

P ( 1 atm 10 atm )

pSO2 ,

pO 2

T = 1000K , K P =1.876 ( independent of P ) , P = 10 atm

G = 5230 J
o

From() x = 0.686

n SO2 = 0.314 mole

n O 2 = 0.157 mole
n SO3 = 0.686 mole

p SO2 = 0.714 atm

p O 2 =1.357 atm
p SO3 =5.929 atm
i.e. K P is independent of P , but compositions change
Le Chatlier :
P equilibrium shifts to decrease of total moles
equilibrium shifts to right n SO3 ,
n O2
Effect of changes in both T , P
From equation ()
T KP
T , P changes P K P changes
solution of x changes

nSO2

 11-6 In a system to keep a constant p

O2

through

gas mixture of SO / SO , CO/ CO , H /

2

HO
2

1.

SO 2 / SO 3 mixture with

n SO 2
n SO 3

=a

at T=1000 K , P = 1 atm

(1) to keep p O 2 = 0.1 atm , a = ?

(2) ( p O 2 ) max = ?
sol (1) :

SO 2( g)

1
O 2( g)
2

SO 3( g )

Initial

Final

a+x

1
x
2

1x

and p O 2 = 0.1 atm

1
( 2a+2+x)
2
nO2
xP
p O2 = X O2 P =
P=
nT
2a + 2 + x

nT =

for P = 1 atm , p O 2 = 0.1 atm

2
p

K =

p so3 2
p so2 2 p O2

a = 4.5x1

X so3 2
Xso2 2 X O2

T = 1000 K , G o = 5230 J
96.45x 3 18.709x 2 6.481x = 0
x0
x = 0.374
then a = 0.683

1
(1 x) 2 ( 2a + 2 + x)
=
.()
P
(a + x) 2 x P
K P =1.876

Final p O 2 =0.1 atm

p SO2 =

p SO3 =

(a + x )
1
( 2a + 2 + x )
2
(1 x )
1
( 2a + 2 + x )
2

= 0.565 atm

= 0.335 atm

p O 2 / p SO3 = 1.7
c.p. ( p O 2 / p SO3 ) initial = a = 0.683
(2) O 2( g) is produced by decomposing SO 3( g ) into SO 2( g) + O 2( g)
maximum p O 2 can be obtained by setting a = 0
i.e. starting with 1 mole SO 3( g ) only , and from ()

Final

p O 2 =0.212 atm
p SO2 = 0.423 atm
p SO3 = 0.365 atm

P = 1 atm , T =1000K

2. To keep a very low p O 2 can be obtain by H 2 O/ H 2 or CO/ CO 2

mixture
e.g.

P = 1 atm , T =2000K p O 2 = 10 10 atm

in a H 2 O/ H 2 gas mixture , ( p H2 O / p H2 ) = ?
H2 +

1
O2 = H 2 O
2

G = 247500 + 55.85 T (J)

o

T =2000K , G o = 135800 J
G =RT ln K P
o

KP=

ln K P = 8.167 , K P = 3.521 10 3

p H 2O
1

pH pO2 2

p O 2 = 10 10 atm

( p H2 O / p H2 ) = 3.521 10 2

Operation : If p H2 = 1 atm , p H2 O = 0.03521 atm

Equilibrium vapor pressure of

H 2 O ( l)

log p H2 O (atm) =

2900
4.65 log T + 19.732
T

when T = 27

Bubbling H 2

p H2 O = 0.0352 atm

at 1 atm through water , T = 27 then feeding gas mixture into

( g)

2000 K chamber

3.

Keep

pO 2 =10 20 atm , T =1000K , P = 1 atm

using CO 2 /CO mixture , ( p CO 2 / p CO ) = ?

sol :

CO +

1
O2
2

CO 2

G = 282400 + 86.81 T (J)

o

T = 1000 K , G o = 195590 J = RT ln K P
ln K P = 23.52 , K P = 1.646 10 10
KP=

p CO2
1

p CO p O 2 2

p CO 2
p CO

= 1.646

p CO 2
p CO

1
1

(10 20 ) 2

P= 1 atm ( p CO 2 + p CO + p O 2 ) p CO 2 + p O 2 = 1 atm

p CO 2 = 0.622 atm

V CO 2 = 62.2

p O 2 = 0.378 atm

V CO = 37.8

V CO 2 / V CO = 1.646
Note : Mixture of A : a cm 3 , B : b cm 3 , P = 1 atm
Pa a
b
n A=
=
, nB =
Before mixing
RT RT
RT
After mixing
p A=
pB=

pA
pB

Ex 1 :

n A RT
a
=
V
a+b
n B RT
b
=
V
a+b
n
a
(a / a + b)
= A=
=
= V a / V b
nB
b
(b / a + b)

P 4( g) = 2 P 2( g) ( Endothermic Reaction )

G = 225400 +7.9 T ln T209.4 T

o

(1) P = 1 atm

X P4 = X P2 = 0.5

T=?

(2) T = 2000 K

X P4 = X P2 = 0.5

P=?

sol : (1) K P =

when P = 1 atm

p P2 2

p P4

X P2 2 P
X P4

X P4 = X P2 = 0.5

K P = 0.5 P = 0.5

G = RT ln K P
o

ln K P = ln (0.5) =

G o
27109
=
0.95 ln T + 25.18
RT
T

T = 1429 K
(2) when X P4 = X P2 = 0.5

K P = 0.5 P

 G = RT ln K P
o

T = 2000 K

G o
= 4.405
RT
K P = 81.83 = 0.5 P

ln K P =

P = 163.6 atm

Ex 2 :

2 NH 3( g ) = N 2( g)

+ 3 H 2( g)

G o = 87030 25.8 T ln T 31.7 T (J)

(1) T = 400
(2) T = 400

sol :

,
,

(1)

P = 1 atm Final composition : p i = ?

V = constant
pi = ?

2 NH 3( g ) = N 2( g)
initial

final
1-2x
n T =(1+2x) moles

3x

3x
P
1 + 2x

T = 400 = 673 K

p N2 =

x
P
1 + 2x

G o = 47370 J

KP=

KP

p H2 =

p NH3

+ 3 H 2( g)

1
2

p N 2 p H2 3
p NH3 2

G o
K P = exp(
) = 4748
RT

1 2x
=
P
1 + 2x

27 x 4 P 2
27 x 4 P 2
=
(1 + 2 x ) 2 (1 2x ) 2
[(1 4 x ) 2 ] 2

5.196 x 2 P
(1 4x ) 2

Substitute K P = 4748 , P = 1 atm

x = 0.4954

p H2 =

3x
P = 0.7465 atm
1 + 2x

p N2 =

x
P = 0.2488 atm
1 + 2x

p NH3 =

1 2x
P = 0.0047 atm
1 + 2x

(2) Initial 1 mole , Final ( 1+2x ) moles

nT ,
P = 1 atm = constant pressure
1
constant volume P =
P'
(1 + 2 x)
Assume final pressure = P ' at constant volume

p H2 =

3x
P'
1 + 2x

p N2 =

x
P'
1 + 2x

p NH3 =

1 2x '
P
1 + 2x

RT
(1 + 2 x) RT
=
P
P'

V=

P ' = ( 1+2x )P = ( 1+2x ) atm

KP

1
2

5.196 x 2 P '
(1 4 x) 2

Substitute K P = 4748 , P ' = ( 1+2x )

KP

1
2

5.196x 2 (1 + 2x )
(1 2 x)(1 + 2x )

x = 0.4909

5.196x 2
(1 2 x)

P ' = 1.9818 atm

p H2 = 1.4727 atm
p N2 = 0.4909 atm
p NH3 = 0.0182 atm

= 68.91

Ex 2-1

What is the equilibrium ratio of ( n H2 / n N2 ) = ? to maximize the yield of

NH 3 when mixing H 2 and N 2 ?

sol :

N 2( g)

+ 3 H 2( g)

= 2 NH 3( g )

Assume that at equilibrium , ( p H2 / p N2 ) = a

P = p H2 + p N2 + p NH3
p NH3 = P( a +1 ) p N2
p N2 =

P p NH3
a +1
p NH3 2

KP=

p H2 3 p N 2

p H2 =

a( P p NH3 )
a +1

p NH3 2 ( a + 1) 4
a 3 ( P p NH3 ) 4

When NH 3 is maximized , p NH3 is maximum

d ( p NH3 )

=0
da
ln K P + 3 ln a + 4 ln ( Pp) = 2 ln p + 4 ln (a+1)
3
4
2
4
da +
dp = dp +
da
a
P p
p
a+1
(

3
4
2
4

)da = ( +
) dp
a
a+1
p Pp

dp
3
4
= 0
(
) = 0
a=3
da
a
a +1
Ex 3 : ( 1 mole CH 4 + 1 mole CO 2 )

T = 1000 K , P = 1 atm
Final equilibrium composition ? p i = ?
Given (1) CH 4( g) = C ( s) + 2H 2( g)

G o1 =6912022.25T ln T +65.35

(2) 2 C ( s) = O 2( g) + 2CO ( g)

G o2 =223400175.3 T

(3) C ( s) + O 2( g) = CO 2( g)

G o3 =3941000.8 T

1
(4) H 2( g) + O 2( g) = H 2 O ( g)
2

sol (I) : consider

G o4 =246400+54.8 T

CH 4( g) + CO 2( g) = 2 H 2( g) + 2CO ( g) (5)

(5) = (1)+ (2)(3)

G o5 = 23982022.25T ln T109.15 T
G o5 = 23027

T = 1000 K

G o5
) = 15.95
RT

CH 4( g) + CO 2( g) = 2 H 2( g) + 2CO ( g)
initial
final

1
1x
(1 x )P
p CH 4 = p CO 2 =
2(1 + x )

1
1x

p H2 = p CO =

K P5 = 15.95 =

K P5

K P 5 = exp(

1
2

0
2x

0
2x

n T =2(1+x)

xP
(1 + x )

p CO 2 p H 2 2
p CH4 p CO 2

( 2 x) 4 P 2
[2(1 + x )] 2 (1 x ) 2

(2 x ) 2 P
2x 2 P
= 3.99 =
=
2(1 + x )(1 x )
(1 x 2 )

P = 1 atm x = 0.8163

p CH 4 = p CO 2 = 0.4494 atm
p H2 = p CO = 0.0506 atm

(II)

Then consider furthermore :

H 2( g) + CO 2( g) = H 2 O ( g) + CO ( g) ..(6)

(6) = (4)(3)
T = 1000 K

(1)
2

G o6 = 3600032.05 T

G o6
, G = 3950 , K P6 = exp(
) = 0.62
RT
o
6

K P6 = 0.62 =

p CO p H 2O
p H2 p CO 2

H 2( g)
Initial
Final

2x
2xy

+ CO 2( g) = H 2 O ( g) + CO ( g)
2x
(1x)y

Final composition :

0
y

2x
2x+y

n CH = (1x)
4

n CO 2 = (1xy)
n H2

= (2xy)

n CO = (2xy)
n H2 O = y
p CH 4 =
p H2 =

(1 x )
P
2(1 + x )
(2 x y)
P
2(1 + x )

p H2 O =

y
P
2(1 + x )

K P5 = 15.95 =
K P6 = 0.62 =

p CO 2 =

(1 x y )
P
2(1 + x )

p CO =

( 2 x + y)
P
2(1 + x )

( 2x y) 2 (2 x + y ) 2 P 2
(1 x)(1 x y)( 2 + 2x ) 2
( 2x + y) y
(2 x y)(1 x y)

Computer solution with P = 1 atm

x = 0.785
y =0.0775

n T =2(1+x)

p CH 4 = 0.0602 atm
p CO 2 = 0.0385 atm
p H2 = 0.4181 atm
p CO = 0.4615 atm
p H2 O = 0.0217 atm

P total = 1 atm

(III) CO/ CO 2 and H 2 / H 2 O mixture will have their equilibrium p O 2

CO ( g ) +

(7) = (3)

1
O 2( g) =
2

(2)
2

CO 2( g) (7)

G o7 = 282400 + 86.85 T

G o7
T = 1000 K , G = 195550 , K P7 = exp(
) = 1.64 10 10
RT
o
7

K P7 =

p CO 2
p CO p O2

1
2

0.0385

0.4615 p O2

1
2

=1.64 10 10

p O 2 = 2.6 10 23 atm

Or ,

1
H 2( g) + O 2( g) = H 2 O ( g) ..(4)
2

T = 1000 K ,

K P4 =

G o4 =191600 , K P = 1.02 10 10
4

p HO2
p H p O2

1
2

0.0217
1

0.4181 p O2 2

p O 2 = 2.6 10 23 atm

Note : 1. part (III) is part(I):CH 4( g) + CO 2( g) = 2 H 2( g) + 2CO ( g)

and

1
H 2( g) + O 2( g) = H 2 O ( g)
2

CO 2( g) +

1
O 2( g) =
2

CO ( g)

i.e. further oxidation of H 2( g) and CO 2( g)

2. Final equilibrium composition
p CH 4 = 0.0602 atm
p CO 2 = 0.0385 atm
p H2 = 0.4181 atm
p CO = 0.4615 atm
p H2 O = 0.0217 atm
p O2

=2.6 10 23 atm