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Equilibria

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Kimia 2

Chemical Equilibria

Reaction Coordinate

1 A 1 2 A 2 ...... 3 A 3 3 A 3 ......

CH 4 H 2 O CO 3 H 2

CH 4 1

H 2O 1

CO 1

H 2 3

dn1 dn 2 dn 3 dn 4

dn i

.....

d

1

2

3

4

i

dn CH 4

1

dn H 2O

1

dn CO dn H 2

dn i

.....

d

1

3

i

Reaction Coordinate

n i n i0 i

yi

n i n i0 i

n

n0

n n0

n

ni

n0

n i0

If, initially there are 2 mol CH4, 1 mol H2O, 1 mol CO, and 4 mol H2:

n CH 4 ,0 2

n H 2 O, 0 1

n CO,0 1

n H 2 ,0 4

n 0 n CH 4 ,0 n H 2O,0 n CO,0 n H 2 ,0 2 1 1 4 8

n CH 4 2

n H 2O 1

n CO 1

n H2 4 3

CH 4 H 2O CO H 2 1 1 1 3 2

n n CH 4 n H 2O n CO n H 2 8 2

y CH 4

2

8 2

y H 2O

1

8 2

y CO

1

8 2

y H2

4 3

8 2

Reaction Coordinate

Reactions

1 1 A1,1 2 1 A 2,1 ...... 3 1 A 3,1 3 1 A 3,1 ......

1 2 A1,2 2 2 A 2,2 ...... 3 2 A 3,2 3 2 A 3,2 ......

................................... ....................................

1 j A1, j 2 j A 2, j ...... 3 j A 3, j 3 j A 3, j ......

CH 4 H 2 O CO 3 H 2

CH 4 2 H 2 O CO 2 4 H 2

Reactions

dn1,1

1,1

dn1,2

1,2

dn1, j

1, j

dn CH 4 ,1

1

dn CH 4 ,2

1

dn 2,1

2,1

dn 2,2

2,2

dn 2, j

2, j

dn H 2O,1

1

dn H 2O,2

2

dn 3,1

3,1

dn 3,2

3,2

dn 3, j

3, j

dn CO,1

1

4,1

dn 4,2

4, 2

dn 4, j

dn CO 2 ,2

1

dn 4,1

4, j

.....

.....

.....

dn H 2 ,1

3

i,1

dn i,2

i, 2

dn i, j

i, j

.....

dn H 2 ,2

4

dn i,1

d1

d 2

d j

dn i,1

i,1

.....

d1

dn i,2

i, 2

d 2

Reaction Coordinate

n i n i0

i, j j

j

n i0

yi

ni

n

n0

i, j j

j

1, j j

j

n n0

n

1, j j

ni

n0

n i0

i, j

i

If, initially there are 2 mol CH4, 1 mol H2O, 1 mol CO, and 4 mol H2:

y CH 4

2 1 2

8 2 1 2 2

y H 2O

y CO 2

2

8 2 1 2 2

y H2

1 1 2 2

8 2 1 2 2

4 3 1 4 2

8 2 1 2 2

y CO

1 1

8 2 1 2 2

Reaction Coordinate

Equilibrium Condition

dG

t

T,P

Equilibrium Condition (Cont)

K

For gases:

(a i )

exp

i G i 0

R T

(f i )

CH 4 H 2 O CO 3 H 2

K fCH 4

fH 2O

K K y K P

For ideal gases:

K K y P

f CO fH 2

Method of

Equilibriu

m

Constant

Problems

Leads to The Same Results

Problems

Calculation of Equilibrium

Constant

G o298K

H o298K

C op

H

i

o

f , 298K

C

i

G

i

o

f , 298K

o

p

H T H o298

C op dT

298

d ln K H T

dT

R T2

ln K T

H T

d ln K R T 2 dT

ln K 298 K

G f ( 298K )

G f ( 298K )

G f

( 298K )

G f

( 298K )

H f

( 298K )

H f

( 298K )

H f

( 298K )

H f

( 298K )

Heat

Capacity

Data Solid

Problems

Problems

Problems

Problems

Problems

Problems

Problems

Problems

Problems

Multiple Reactions

A bed of coal (assume pure carbon) in a coal

gasifier is fed with steam and air and produce a

gas stream containing H2, CO, O2, H2O, CO2, and

N2. If the feed to the gasifier consists of 1 mol of

steam and 2.38 mol of air, calculate the

equilibrium composition of the gas stream at P

= 20 bar and T = 1500K

Multiple Reactions

Problems

Problems

Problems

Complex Reaction

First Step: Atomic Balances

n i a ik A k

#2 Step:

G ofi

ni

R T ln

i P

n

involved atom

k a ik 0

k

species involved

Use Computer to Solve All The Equation Simultaneously.

Problem

Calculate the equilibrium composition at 1000 K

and 1 bar of a gas-phase system containing the

species CH4, H2O, CO, CO2, and H2. In the initial

unreacted state ther are present 2 mol of CH4

and 3 mol of H2O. Assume ideal gases.

At 1000 K:

G of CH 19720 J mol -1

4

G of H

2O

192420 J mol -1

G of CO 200240 J mol -1

G of CO 395790 J mol -1

2

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