Lecture1 & 2

Chemical equilibrium
Chemical reactions often seem to stop before they are completed. Such
reactions are reversible. That is the original reactants form products, but
then the products react with themselves to give back the original
reactants. Actually 2 reactions of reactants are occurring, and the eventual
result is a mixture of products.
For eg.:
CO(g) +3 H2(g)

CH4(g) + H2O(g)

This reaction is a reversible reaction, and depending on the reaction

conditions, the final reaction mixture will have varying amounts of the
products methane and steam,
as well as the starting substance CO and
H2. It is possible to start with methane and
steam under the right conditions, forming a mixture that is predominantly
CO and H2
CH4(g) + H2O(g)

CO(g) +3 H2(g)

We will see how to determine the composition of a reaction mixture at

equilibrium and how to alter this composition by changing the conditions
for the reaction.
Many chemical reactions are like the catalytic method reaction. Such
reaction can be made to go predominantly in one direction or the other
depending on the conditions.
Chemical equilibrium a dynamic equilibrium:
When substances react, they form a mixture of reactants and products in
dynamic equilibrium.
This dynamic equilibrium consists of reaction, in which substances react to
give product, and a reverse reactions (occur at the same rate) to give the
original reactants
Forward and rate = revisable rate
CO(g) + 3 H2 (g)

CH4(g) + H2O(g)

At 1st their concs.

are large
but as they react, concs

are zero

decrease

increase

The forward rate decreases and the reverse rate increases until the rates
become equal.
The conclusion of reactants and products no longer change, reaction
reached equilibrium.

Example 1: for the reaction: CO(g)+3H2(g)

CH4(g) + H2O(g)

When 1.00molCO and 3.00 mol H2 are placed in a 10.00L vessel at 927c
(1200K) and allowed to come to equilibrium o.387 mol H2O. what is the
molar composition of the equilibrium mixture (that is how many moles of
each substance are present)
Answer:
CO(g) + 3 H2 (g)
At start
Change

CH4(g) + H2O(g)

1.00 mol 3.00 mol

-3x

+x

+x

3.00-3x

+x

+x

-x

At equilibrium 1.00-x

Equilibrium amount of CO = 1.00 x mol

= 1.00-0.387 = 0.613 mol
Equilibrium amount of H2 = 3.00 3 X 0.378 = 1.839 mol
Equilibrium amount of CH4 = 0.387 mol

Example2: CO(g) + H2O

CO2(g) + H2(g)

(g)

Suppose you start with a gaseous mixture containing 1.00 mol CO and
1.00 mol H2O. When equilibrium is reached at 1000C, the mixture
contains 0.43 mol H2. what is the molar composition of the equilibrium
mixture?
CO(g) + H2O
Starting
Change

1.00 mol
-x

CO2(g) + H2(g)

(g)

1.00 mol
-x

+x

+x

At equilibrium

1.00-x

1.00-x

x =0.43

CO : 1.00 -0.43 = 0.57 mol H2O: 1- 0.43 = 0.57 mol

CO2 : 0.43 mol

H2 : 0.43 mol

The equilibrium constant: Kc

aA + bB

cC + dD

A,B,C,D denote reactants and products, and a,b,c,d are coefficients in the
balanced chemical equation.
Equilibrium constant is an expression obtained by multiplying the conc. of
the products dividing concs. of the reactants and raising each conc. Term
to a power equal to the coefficient in the chemical equation
Kc =
Where [A], [B ], [c}, [D] are molar conc.
This relation was determined after doing different experiments, and seeing
what is the best method for giving constant values.
1- Write the equilibrium const. expression Kc for catalytic methanation.
CO(g) + 3H2 (g)

CH4(g) +H2O(g)

2- Write Kc for the reverse of the previous reaction

3- Write Kc expression for the synthesis of ammonia.
N2(g) + 3H2(g)

2NH3(g)

4- Write Kc for:
2NH3(g)

N2(g) +H2(g)

Obtaining equilibrium constants for reactions:

Exp.1:
Calculate the Kc for the following equation:

CO (g) + 3H2 (g)

CH4(g)

+H2O(g)
The eq. composition is 0.613 mol CO, 1.830 mol H 2, 0.387 mol CH4 and
0.387 mol H2O.
The volume of the reaction vessel is 10.00 L so the equilibrium conc. Of
CO is:
[CO] = 0.613/10 = 0.0613 M , [H2] = 1.839/10,
[H2O] = 0.387/10

[CH4] = 0.387/10,

Kc = [

= 3.93

Examples:
1) Find the equilibrium constant of the following reaction :
CO(g) + 2 H2(g)

CH3OH(g)

This reaction takes place at 780C , initially contains [CO]= 0.50 M

and[H2] =1.0 M. At equilibrium the CO concentration is found to
be 0.15 M.
CO(g) + 2 H2(g)
initial
change
equilibrium

CH3OH(g)

0.5

1.0

-x

-2x

+x

0.5- x

1-2x

[CO] = 0.15 M at equilibrium = 0.5- x

X = 0.5- 0.15 = 0.35
[H2] =1- 0.70 =0.3M
Kc = [CH3OH]/ [CO][H2]2
= 0.35/0.15x(0.3)2
= 26 M-2

2) Find the equilibrium constant for the following reaction

2 CH4 g)
C2H2(g) + 3 H2(g) at 1700 C initially contains [CH4] =
0.115 M. At equilibrium the mixture contains [C 2H2] =0.035 M.
2 CH4 g)

C2H2(g) + 3 H2(g)

Initial

0.115

Change

-2x

+3x

At equilibrium

0.115-2x

3x

X = 0.035 x2 = 0.07 M
At equilibrium
[CH4] = 0.115 0.070 = 0.045 M ,[C2H2] = 0.035 M, [H2] = 3x
0.035= 0.105 M
Kc = [H2]3[C2H2]/ [CH4]
= 0.035(0.105)3/ (0.045)2

= 0.02