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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
BITS Pilani, K K Birla Goa Campus

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
BITS Pilani, K K Birla Goa Campus

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.
BITS Pilani, K K Birla Goa Campus

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
BITS Pilani, K K Birla Goa Campus

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

BITS Pilani, K K Birla Goa Campus

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 )

BITS Pilani, K K Birla Goa Campus

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
BITS Pilani, K K Birla Goa Campus

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
BITS Pilani, K K Birla Goa Campus

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)

BITS Pilani, K K Birla Goa Campus

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
BITS Pilani, K K Birla Goa Campus

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
BITS Pilani, K K Birla Goa Campus

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
BITS Pilani, K K Birla Goa Campus

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
BITS Pilani, K K Birla Goa Campus

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

BITS Pilani, K K Birla Goa Campus

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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