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Reaction Eqb.: i i = 0
i
P
Eqb. Constant = a
PA
G o = RT ln K eq o
PD d
o
where P 0 = 1 bar.
PB b
o
= d = S
= G
dT + V
dP
F o r c o n s ta n t T :
R T
d
P
=
m
P
c o n s t. T p u re id
d = V
dP
eal gas.
P2
( T , P 2 ) ( T , P1 ) = R T l n
P1
i f P1 = P
= 1 b a r = > ( T , P1 ) =
(T )
P
(T ) + R T ln
o
P
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i = i* Mixture at T , P, xi
Pi xi P = P* at Eqb.
i (T , P, x1 , x2 ,...) = i* (T , xi P) = i* (T , Pi )
: ideal gas mixture
BITS Pilani, K K Birla Goa Campus
Pi
+ R T ln
:
Po
F u n d a m e n ta l E q n . fo r
Id e a l g a s m ix tu re , P o = 1 b a r
o d e p e n d s o n ly o n te m p e ra tu re
Each of U, H, S, G and CP for an ideal gas mixture
is the sum of the corresponding
thermodynamic functions for the pure gases calculated
for each pure gas occupying a volume equal to
mixtures volume at a pressure equal to its
partial pressure in the mixture and at a temperature
equal to its temperature in the mixture.
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in terms of :
a A + bB = cC + d D
or cC + d D a A bB = 0
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Pi
i = + RT ln o
P
PC
PD
o
o
cC + cRT ln o + d D + dRT ln o
P
P
o
i
PA
PB
a aRT ln o bB bRT ln o = 0
P
P
o
A
o
D
o
A
o
B
o
i m,T ,i
= (T)
o
i i
= c + d a b L.H.S of (A)
o
C
o
D
o
A
o
B
(
(
o
P
P
C , eq
o
G = RT ln
o
P
P
A,eq
where K
o
P
P
(
=
(P
C ,eq
A , eq
) (P
) (P
c
D ,eq
B ,eq
) (P
P ) (P
D , eq
B ,eq
)
)
)
)
d
b
d
b
P o 1 bar
G o = RT ln K Po
= 0
+
RT
ln
P
P
i i i i
i , eqb
i
o
o
(
T
)
+
RT
ln
P
P
i i
i ( i ,eqb ) = 0
i
( ai + bi ) = ai + bi and
i
ca
= c ai
i
o
m ,T ,i
= i (T )
o
i
i
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G o (T ) = RT i ln Pi , eq P o
i
= RT ln Pi , eq P
i
= ln ai = a1a 2 ...a n
i =1
=> G = RT ln Pi , eq P o
i
o
T
K Pi , eq P
o
P
=> K
o
P
= e
G o RT
BITS Pilani, K K Birla Goa Campus
Ai or 0
P
i = (T ) + RT ln o
P
G o = RT ln K Po
o
i
o
P
(
=
(P
)(
P ) (P
PH 2 P
H2S
)
P )
PCS2 P o
CH 4
0.000331
o
P
c
(
=
(c
F , eq
(
=
(c
A , eq
o
D , eq
c F , eq c
A , eq
) (c
RT P ) ( c
) (c c )
) (c c )
RT P
B , eq
D , eq
B , eq
RT P
RT P
)
)
c RT
o
P
o
f + d a b
o
C
(c
i ,eq
w h e re c o = 1 m o l/L 1 m o ld m 3
K
o
P
= K
RTc
o
P
o
C
n / m ol
K depends only on T ,
o
K x = xi ,eq
i
P
K = Kx o
P
Except for reactions with:
n = 0, Kx is a function of T and P.
o
P
o
P
Qualitative discussion of
Chemical Eqb.
KPo =
1
Go RT
Go RT
G >> 0 => e
o
very large,
favors reactants
=> KPo is very small
and vice versa
Exponential reln. between
Go and KPo , unless Go range:
-12RT < Go < 12RT , KPo will be very large/small
if T is less, KPo varies rapidly with Go
At high T : Go T S o
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Qualitative discussion of
Chemical Eqb.: Kpo vs T
At low temperatures,
low value of Kpo implies
Large positive
Std. Gibbs energy.(Go)
Temperature dependence of
Eqb. constant
o
G
ln K Po =
RT
d ln K Po
1 d (G o )
G o
=
2
dT
RT
RT
dT
o
dG m , i
o
o
G = i G m ,i = i
dT
i
i
dG m = S m dT + V m dP =>
dG
o
m ,i
dT
= S mo , i
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Temperature dependence of
Eqb. constant
d G o
= i S mo , i = S o
dT
i
=>
d ln K Po
G o
S o
=
+
2
dT
RT
RT
d ln K Po
H o
=>
=
dT
RT 2
V an 't H o ff E q n .
H o
d ln K =
dT
2
RT
o
T2 H
K Po ( T 2 )
ln
=
dT
o
2
T
1
K P ( T1 )
RT
o
P
K Po ( T 2 )
H
ln
=
K Po ( T1 )
R
1
1
T1 T 2
N eg lectin g T d ep en d en ce
o
of H
o
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Temperature dependence of
Eqb. Constant: Example
Find Kpo at 600 K for the reaction
N2O4 (g) 2 NO2 (g) (a) using the approximation that
Ho is independent of T(b) using approximation that
CPo is independent of T
Temperature dependence of
Eqb. Constant: Example
(b) H o (T ) = H o (T1 ) + C Po (T1 )(T T1 )
Substituting this in Eqn for
temp. dependence of K Po and C Po , 298 K = 2 .88 J/mol-K
K Po (T2 ) H o (T1 ) 1
1
ln o
K P (T1 )
R
T1 T2
C Po (T1 ) T2 T1
+
1
ln +
R
T1 T2
K Po , 600 K = 1 .52 10 4
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Temperature dependence of
Eqb. Constant
d ln KPo
H o
=
Vant Hoff Eqn. in differentials
R
1
d
T
1
o
ln KP vs is linear and from the slope
T
H o can be calculated.
KPo = f (T ), Go , H o and S o can be calculated
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Ideal-Gas Eqb.
Calculations:Steps summary
1. GTo = i f GTo,i from a table of f GTo,i values.
i
2. GTo = RT ln K Po
3. Eqb. mole no.:
ni = ni ,o + i eq
4. Pi = xi P = ni
i ni P const.T&P
ni RT
At fixed T and V: Pi =
if V is known.
V
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Ideal-Gas Eqb.
Calculations:Steps summary
5. Pi as a fn. of x
K = Pi P
o
P
solve for eq
INITIAL
MOLES
CHANGE
EQB.
MOLES
N2
H2
NH3
1.0
2.0
0.5
-z
1.0-z
-3z
2.0-3z
2z
0.5 + 2z
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