CHEMICAL EQUILBRIM

Classification of Reactions
Chemical reactions are either
homogeneous or heterogeneous
Reversible or Irreversible
Homogenous reaction: only one phase is present,
For Example
In the gas phase:
H2(g) + I2 (g) → 2HI(g)
In the liquid phase:
CH3COCl +CH3OH → CH3COOCH3 +HCl
Heterogeneous reaction: the mixture is not uniform
throughout
Irreversible reaction (complete reaction) when a
chemical reaction proceeds in one direction. i.e.
from reactant to products the reaction.
A + B →AB
Reversible reaction reaction that proceed either
in the forward or in the backward ( reverse)
direction
A+B ⇌ AB
 The Law of mass Action

A hypothetical reversible reaction

A2(g) + B2(g) ⇌ 2 AB
The rate of the forward reaction is
Rate f = Kf [A2] [B2]
The rate of the reverse reaction is
Rate r = Kr [AB]2
At equilibrium rate f = rate r
Kf [A2] [B2] = Kr [AB]2
Kf / Kr = [AB]2 / [A2] [B2]
Kf / Kr = Kc Which is called the equilibrium constant

Kc = [AB]2 / [A2] [B2]

• brackets denote equilibrium molar concentration
( mol / liter ).
• reaction involving gases, the partial pressure of
the reactants and products are proportional to
their molar concentration. The equilibrium
constant expression for these reactions can
therefore be written using partial pressures
instead of concentration. For example
N2(g) +3 H2(g) ⇌ 2 NH3(g)
Kp = (PNH3)2 / PN2. (PH2)3
Example
CH4(g) +2H 2s ⇌ CS2(g) +4H2(g)
What is the value of Kp at 1000 K if the partial
pressures in an equilibrium mixture at 1000 K are
0.20 atm of CH4 , 0.25 atm of H 2S , 0.52 atm of CS2 ,
and 0.10 atm of H2 ?
Solution
Kp = (P CS2) (PH2)4 / (P CH4 )( PH2S )2
Kp =(0.52) (0.10)4 / (0.2)(0.25) = 4.2 x 10-3
 The Relationship between Kp and Kc

For the general equation

a A +b B ⇌ eE +f F
Kp = PEe Pff / PAa. PBb Kc = [E]e [F]f / [A]a [B]b
Concentration has the units mol/ L ( n/v )
Assuming ideal gas behavior, we can use the gas law,
PV=nRT
To obtain the concentration of a gas x
[x] = nx / V = Px / RT
Where Px is its partial pressure
Px = [x] RT
Kp = PEe Pff / PAa. PBb = [E]e (RT)e [F]f (RT)f / [A]a(RT)a [B]b (RT)b
Kp = [E]e [F]f / [A]a [B]b (RT)(e+f)-(a+b)
Kp = [E]e [F]f / [A]a [B]b (RT)∆ n(g)
Kp = Kc ( RT) ∆ n
∆ n(g) = ( number of moles of gaseous products) – ( number of moles of gaseous
reactants).
Example :-
H2O(g) + CH4 (g) ⇌ CO(g) +3H2(g)
a)If Kc = 3.8 x 10-3 at 1000 K, What is the value of Kp at the same
temperature?
b) If Kp = 6.1 x 104 at 1125 °C ,What is the value of Kc at 1125 °C?
Solution
For the reaction, ∆ n = (1+3) - (1+1) = 2
Kp = Kc ( RT) ∆ n =( 3.8 x 10-3) ( 0.082x 1000 )2 =26
Kp = Kc ( RT) ∆ n = Kc ( RT) 2

Kc = Kp / ( RT) 2 =( 6.1 x 104) / [(0.082)(1398)]2 = 4.6

• Heterogeneous Equilibria:
As a general rule, the concentration of pure solid
and pure liquids are not included when write an
equilibrium equation because their
concentrations are constant .We include only
the concentration of gases and the
concentration of solute in solutions because
only those concentrations can be varied.
Example :
Write the equilibrium equation for each of the
following reactions
a)CO2(g) + C(s) ⇌ 2CO(g)
b)Hg(l) + Hg+2(aq) ⇌ 2 Hg2+2(aq)
Solution:
Because CO2 and CO are gases , the equilibrium
equation can be written using partial pressures
a) Kp =(P CO)2 / (P CO2)
b) Kc = [Hg2+2 ]2 / [Hg+2 ]
 Using the Equilibrium constant

1-Judging the Extent of reaction

-If Kc > 103, product predominate over reactant, If Kc is
very large value the reaction proceeds nearly to
completion.
-If Kc < 10-3
, reactant predominate over product, If Kc is very small
value
the reaction proceeds hardly at all.
-If Kc is in the range 10-3 to 103 ,appreciable concentration
of both reactants and products are present.
Example :
2SO2(g)+O2(g)⇋2SO3(g)
The reaction is at equilibrium at some temperature, and
the following equilibrium concentrations are measured:
[SO2 ] =0.9 M [O2 ] =0.35 [SO3 ] = 1.1
Solution:
Kc = [SO3 ]2 / [SO2 ]2 [O2 ] =(1.1 )2 / (0.9)2 ( 0.35) = 4.3
Note that since the calculated Kc, is between 0.001 and
1000, we would expect this reaction to have significant
concentrations of both reactants and products at
equilibrium.
2-Predicting the Direction of a reaction
For the reaction
H2(g) + I2(g) ⇌ 2 HI(g) Kc =57.0 at 700K
Suppose that we have a mixture of H2(g) , I2(g) and HI(g) at 700 K
with concentration [H2]t = 0.10 M , [I2]t = 0.20 M, and , [HI]t =
0.40 M.
The subscript on the concentration symbols means that the
concentration were measured at some arbitrary time t, not
necessary at equilibrium. If we substitute these concentration
into the equilibrium constant expression, we obtain a value
called reaction quotient Q.
Reaction quotient Q. = [HI]t2 / [H2]t [I2]t =( 0.40)2 / (0.10)(0.20)
=8.0
The reaction quotient Q is defined in the same
way as the equilibrium constant Kc except that the
concentration in Q are not necessary equilibrium
values.
For the case at hand, the numerical value of Q
(8.0) does not equal Kc (57.0), so the mixture of
H2(g) , I2 (g) , and HI(g) is not at equilibrium.
The reaction quotient Q is useful because it lets us
predict the direction of reaction by comparing the
values of Q and Kc .
• If Q < Kc , net reaction proceeds from left to
right.
• If Q > Kc , net reaction proceeds from right
to left.
• If Q = Kc, no net reaction occurs
Example :
A mixture of 1.57 mol of N2, 1.92 mol of H2 ,and
8.13 mol of NH3 is introduced into a 20.0 L
reaction vessel at 500 K. At this temperature,
the equilibrium constant Kc is 1.7 x102.
N2 + 3H2 ⇌ 2NH3
Is the reaction at equilibrium? If not, What is the
direction of the net reaction?
Solution:
Because we are given amounts in moles, we must first convert moles to
molar concentration before calculating Q
The initial concentration of N2 is (1.57 mol )/ (20.0 L) = 0.07785 M,
Similarly
[H2] = 0.0960 M and [NH3] = 0.406 M.
Q = [NH3]t2 /[N2]t [H2]t3 = (0.406)2 / (0.0785)(0.0960) = 2.37 x 103 .
Because Q does not equal Kc , the reaction mixture is not at equilibrium,
Because Q > Kc , net reaction will proceed from right to left, decreasing
the concentration of NH3 and increasing the concentration of N2 and H2
Until Q = Kc = 1.7 x102.
3-Calculating Equilibrium concentrations
If the equilibrium constant and all the equilibrium concentrations but one are
known, the unknown concentration can be calculated directly from the
equilibrium equation.

Example :
For the reaction
2NO(g) +O2(g) ⇌ 2NO2(g)
What is the concentration of NO in an equilibrium mixture of gases NO, O2
and NO2 at 500K that contains 1.0x 10-3 M of O2 and 5.0 x10-2 M of NO2 At
this temperature, the equilibrium constant Kc for the reaction is 6.9 x105 .
Solution:
Kc = [NO2 ]2/ [NO]2 [ O2]
6.9 105 = (5.0 10-2)2 / [NO]2 x 1.0x 10-3
[NO] = 1.9 x 10-3