Physical Chemistry I

Instr: Dr. Jayadevan. K. P., B309

Chapter 6: Reaction Equilibrium in Ideal

Gas Mixtures 6.1-6.4

Review of concepts about

Eqb.
Material Eqb.: S Syst + SUniv is maximized at Eqb.
Phase Eqb.: i dni = 0

Reaction Eqb.: i i = 0
i

Consider (hypothetical) reaction of an ideal gas mixture:

aA + bB cC + dD
PC c
o

P
Eqb. Constant = a
PA

G o = RT ln K eq o

PD d
o

where P 0 = 1 bar.
PB b
o

BITS Pilani, K K Birla Goa Campus

Chemical Potential of an (pure)

Ideal Gas
Chemical potential
is an intensive property and
for ideal gases
depends on T and P

Variation of chemical potential

of a pure ideal gas with pressure
at constant temperature. o is the
standard chemical potential
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Chemical Potential of an (pure)

Ideal Gas
dG = SdT + V dP
d iv id in g b y n o . o f m o le s :
dG

= 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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Chemical Potentials in an Ideal

Gas Mixture
1. PV = ntot RT : all T , P, n
2. Pure gas i separated from
mixture through a
membrane permeable to gas i
Eqb. Partial Pressure:
Pi xi P = P* for pure substance
Phase Eqb. between mixture and pure i :

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
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Chemical Potentials in an Ideal

Gas Mixture
i = i

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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Ideal-Gas Reaction Eqb.

Consider a general ideal gas reaction:
aA + bB cC + dD
At Eqb.: i i = 0
i

in terms of :
a A + bB = cC + d D
or cC + d D a A bB = 0
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Ideal-Gas Reaction Eqb.

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

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Ideal-Gas Reaction Eqb.

c + d a b
o
C

o
D

o
A

o
B

=RT cln PC Po + d ln PD Po aln PA Po bln PB Po

-------------(A)
G = G
o
T

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

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Ideal-Gas Reaction Eqb.

From G o (T ) and R.H.S of Eqn. (A):

(
(

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

BITS Pilani, K K Birla Goa Campus

Ideal-Gas Reaction Eqb.

o
o

= 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

and since io (T ) = Gmo ,T ,i

G = i G
o
T

o
m ,T ,i

= i (T )
o
i

i
BITS Pilani, K K Birla Goa Campus

Ideal-Gas Reaction Eqb.

G o (T ) = RT i ln Pi , eq P o
i

= RT ln Pi , eq P
i

ln ai = ln a1 + ln a 2 + .... + ln a n = ln( a1a 2 ...a n )

i
n

= 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

Ideal gas reaction Eqb.

G o RT
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Summary: Ideal Gas Reaction

Eqb.
Ideal gas reaction:
0

Ai or 0

P
i = (T ) + RT ln o
P
G o = RT ln K Po
o
i

i are negative for reactants and positive products

K Po :(Std. Eqb.constant) products in the numerator &
reactants in the deno minator, dimensionless
K P : If only partial pressure is considered
K P will have a dimension (e.g. NH 3 formation, pressure 2 )
K P = ( Pi )

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Ideal Gas Reaction Eqb.: Kpo

and Go
A mixture of 11.02 mmol of H2S and 5.48 mmol of CH4
was placed in an empty container along with a Pt
catalyst and the eqb.
2 H2S (g) + CH4 (g) 4 H2 (g) + CS2 (g)
was established at 700oC and 762 torr. The reaction
mixture was removed from the catalyst and rapidly
cooled to room temperature, where the rates of
forward and reverse reactions are negligible.
Analysis of Eqb. Mixture found 0.711 mmol of CS2.
Find Kpo and Go

BITS Pilani, K K Birla Goa Campus

Ideal Gas Reaction Eqb.: Kpo

and Go
Eqb. Composition calculation:
Products:
nCS2 = 0.711 mmol
=> 4 0.711 mmol = 2.84 mmol H 2 at Eqb.
Reactants:
nCH 4 = 0.711 mmol reacted
=> At Eqb.: nCH 4 = 5.48 0.711 = 4.77 mmol
nH 2 S = 2 0.711 = 1.42 mmol reacted
=> At Eqb.: nH 2 S = 11.02 mmol 1.42 = 9.6 mmol
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Ideal Gas Reaction Eqb.: Kpo

and Go
C a lc u la tio n o f p a r tia l p r e s s u r e s :
Pi = x i P w h e r e P = 7 6 2 t o r r .
M o le fr a c tio n s :
9 .6
x H 2S =
= 0 .5 3 6 , x C H 4 = 0 .2 6 6 ,
1 7 .9 2
x H 2 = 0 .1 5 8 , x C S 2 = 0 .0 3 9 7
P a rtia l p re s s u re s :
PH 2 S = 0 . 5 3 6 7 6 2 = 4 0 8 t o r r
PC H 4 = 2 0 3 t o r r , P H 2 = 1 2 0 t o r r
PC S 2 = 3 0 . 3 t o r r
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Ideal Gas Reaction Eqb.: Kpo

and Go

o
P

(
=
(P

)(
P ) (P

PH 2 P
H2S

)
P )

PCS2 P o

CH 4

120 750 ) ( 30.3 750 )

(
=
=
2
( 408 750 ) ( 203 750 )
4

0.000331

G o 973 = RT ln K Po at 700o C or 973 K

= 8.314 Jmol-1K -1 973 K ln 0.000331
= 64.8 kJ/mol
BITS Pilani, K K Birla Goa Campus

Concentration and MoleFraction Eqb. Constants

Expressing partial pressures in terms of concn.:
ni
ci =
V
ni RT
Pi =
= ci RT Ideal gas mixture.
V
aA + bB fF + dD
K

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

BITS Pilani, K K Birla Goa Campus

Concentration and MoleFraction Eqb. Constants

c o R T d im e n s io n a lly e q . to P o
n / m ol = f + d a b
N 2(g ) + 3 H 2(g ) 2 NH 3(g )
n / m ol = 2 1 3 = 2
S td .C o n c n .E q b .C o n s t:
K

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

BITS Pilani, K K Birla Goa Campus

Concentration and MoleFraction Eqb. Constants

KCo like K Po is dimensionless
o
P

K depends only on T ,
o

c and P are constants shows that

KCo = f (T ) only
Mole-fraction Eqb. Const.:

K x = xi ,eq
i

BITS Pilani, K K Birla Goa Campus

Concentration and MoleFraction Eqb. Constants

n/ mol

P
K = Kx o
P
Except for reactions with:
n = 0, Kx is a function of T and P.
o
P

Note: Any ideal gas Eqb.

can be solved using only KPo at Po = 1 bar
G = RT ln K
o

o
P

Only indirectly related to KCo and Kx .

BITS Pilani, K K Birla Goa Campus

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)

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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

(a)Ho298K = 57.2 kJ/mol, Go298K = 4730 J/mol

KPo,298K = 0.148
KPo
57200
1
1
ln

0.148 8.314 J/mol-K 298.15 K 600 K

=11.6
KPo,600 1.63104
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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
BITS Pilani, K K Birla Goa Campus

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
BITS Pilani, K K Birla Goa Campus

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

6. Eqb. mole numbers from eq and ni in step 3

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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Ideal-Gas Eqb. Calculations:

Example
6.12: For the reaction N2O4 (g) 2 NO2 (g),
measurements of compositions of the eqb. Mixtures
gave Kpo= 0.144 at 25oC and Kpo= 0.321 at 35oC. Find
Ho, Go , So at 25oC for this reaction.
6.25 Calculation of Eqb. amounts

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Example Problem List

Calculation of Go, KPo : 6.3, 6.4, 6.5, 6.9

Ideal Gas Reaction (True/False): 6.10, 6.11
Calculation of Go, Ho, So : 6.12, 6.13, 6.14
Temperature dependence of KPo : 6.15, 6.16, 6.17, 6.19, 6.33
Calculation of Eqb. Composition and KPo : 6.24, 6.25, 6.26, 6.33

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