CH 11
CH 11
CH 11
11-1 Introduction............................................................2
11-2 Reaction Equilibrium in Gas Mixture and.............2
11-3 Effect of Temperature on K ................................5
P
3( g)
2( g)
System..............................................................................9
11-6 In a system to keep a constant p
O2
through gas
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
1.
+ ? O 2( g )
+ ? H 2 O ( g)
A ( g ) + B ( g ) = 2C ( g)
final
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 = n A ( G o ) + 2RT ln P
n
+2RT n A ln A + (1 n A ) ln( 1 n A )
2
n
G ' 2 G oC = n A ( G o ) +2RT n A ln A + (1 n A ) ln( 1 n A )
2
= [ 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
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
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 =
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
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
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 .
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
In general , aA + bB = cC + dD
KP=
p cC p dD
= Kx P
p aA p bB
( c +d ) ( a +b )
K x is independent of P
P Kx
P Kx
( K P is constant )
changes
Cl 2( g) = 2 Cl ( g)
H 0 , S 0
o
i.e.
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)
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
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 = ?
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
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)
G =94600 +89.37T
H o = (94600) 0
S o = (89.37)0
3.
Effect of Pressure :
P ( 1 atm 10 atm )
pSO2 ,
pO 2
From() x = 0.686
nSO2
O2
through
HO
2
1.
SO 2 / SO 3 mixture with
n SO 2
n SO 3
=a
at T=1000 K , P = 1 atm
SO 2( g)
1
O 2( g)
2
SO 3( g )
Initial
Final
a+x
1
x
2
1x
1
( 2a+2+x)
2
nO2
xP
p O2 = X O2 P =
P=
nT
2a + 2 + x
nT =
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
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
1
O2 = H 2 O
2
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
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
( g)
2000 K chamber
3.
Keep
CO +
1
O2
2
CO 2
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 )
(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)
sol :
,
,
(1)
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
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
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=
KP
1
2
5.196 x 2 P '
(1 4 x) 2
1
2
5.196x 2 (1 + 2x )
(1 2 x)(1 + 2x )
x = 0.4909
5.196x 2
(1 2 x)
p H2 = 1.4727 atm
p N2 = 0.4909 atm
p NH3 = 0.0182 atm
= 68.91
Ex 2-1
sol :
N 2( g)
+ 3 H 2( g)
= 2 NH 3( g )
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
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
G o4 =246400+54.8 T
CH 4( g) + CO 2( g) = 2 H 2( g) + 2CO ( g) (5)
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)
(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)
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
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
and
1
H 2( g) + O 2( g) = H 2 O ( g)
2
CO 2( g) +
1
O 2( g) =
2
CO ( g)
=2.6 10 23 atm
Note: This service is not intended for secure transactions such as banking, social media, email, or purchasing. Use at your own risk. We assume no liability whatsoever for broken pages.
Alternative Proxies: