6.

0 CHEMICAL EQUILIBRIUM

Homogenous &
define
heterogeneous equilibria
Expressions for Kc & Kp write
derive
6.2 use
Kc & Kp or quantities of species
Equilibrium present at equilibrium
Calculate
Constants define
determine

Reaction quotient, Q deduce

predict direction
of nett reaction
 HOMOGENEOUS
EQUILIBRIUM
Products and reactants are in the
same phase

EXAMPLE:

N2O4(g) 2NO2(g)

2SO2(g) + O2(g) 2SO3(g)

CH3COOH(aq) CH3COO(aq) + H+(aq)

 HETEROGENEOUS
EQUILIBRIUM
Reactants and products are in
different phase

EXAMPLE:

CaCO3(s) CaO(s) + CO2(g)

 WRITING KC EXPRESSIONS

aA(g) + bB(g) cC(g) + dD(g)

[C]c [D]d
KC =
[A]a [B]b

[ ] = equilibrium concentration

Unit of concentration = M or mol L-1

 WRITING KP EXPRESSIONS

aA(g) + bB(g) cC(g) + dD(g)

(PC )c (PD )d
KP =
(PA )a (PB )b

P = equilibrium partial
pressure of the gas

Unit of pressure = atm

 The concentration of pure liquids and pure solids
does not change (constant). Therefore it do not
appear in the equilibrium constant expression

EXAMPLE:

CaCO3(s) CaO(s) + CO2(g)

[CaO][CO2] [CaCO3] = constant

KC = [CaO] = constant
[CaCO3]

KC = [CO2] KP = (PCO2 )
 EXAMPLE 1
Write expressions for KC, and KP if applicable,
for the following reversible reactions at
equilibrium:
Note: balance the equations first.

(a) HF(aq) H+(aq) + F(aq)

(b) NO(g) + O2(g) NO2(g)

(c) H2SO4(l) + SO3(g) H2S2O7(l)

 DERIVATION OF
KP = KC(RT)n
Derive following equation:

KP = KC(RT)Dn

Hints:
aA(g) + bB(g) cC(g) + dD(g)

[C]c [D]d (PC )c (PD )d

KC = KP =
[A]a [B]b (PA )a (PB )b

PV = nRT
 aA(g) + bB(g) cC(g) + dD(g)

(PC )c (PD )d [C]c [D]d

KP = KC =
(PA )a (PB )b [A]a [B]b

PV = nRT P = n RT Or P = n
V RT v

At constant temperature, pressure is directly proportional to

molar concentration, n/v with unit of mol/L or [ ]

nA PC nC
PA = RT = RT
V V
= [A]RT = [C]RT

nB PD nD
PB = RT = RT
V V
= [B]RT = [D]RT
 aA(g) + bB(g) cC(g) + dD(g)

(PC )c (PD )d
KP =
(PA )a (PB )b

According to the Law of Mass Action, substitute the partial pressure,

Px = [X]RT
c d
= ([C]RT) x ([D]RT)
([A]RT)a x ([B]RT)b
[C]c [D]d
= x (RT)(c+d )(a+b)
[A]a [B]b

= KC(RT)Dn
n = no. of moles of gaseous products no. of moles of gaseous reactants
= (c+d) (a+b)
 EXAMPLE 2

The equilibrium concentrations for the reaction

between carbon monoxide, CO and molecular
chlorine, Cl2 to form COCl2 (g) at 74oC are
[CO] = 0.012 M, [Cl2] = 0.054 M and
[COCl2] = 0.14 M.

Calculate the equilibrium constants KC and KP.

 EQUILIBRIUM PROBLEMS

Equilibrium
Problems
Equilibrium quantities given Initial quantities given
(concentration, partial (initial concentrations, initial partial
pressures) pressures and Kc or Kp )
Solve for Solve for equilibrium quantities
Kc or Kp (concentrations, partial pressures)

Use Reaction Table

Solving equilibrium problems by using
REACTION TABLE

Reaction Table contains:

Initial quantities
Change in quantities

Equilibrium quantities

Quantities = concentration,
pressure
 EXAMPLE 3
Consider the gas phase reaction

H2(g) + I2(g) 2HI(g)

Suppose that a flask containing H2 and I2 has

been heated to 425oC and the initial concentrations
of H2 and I2 were each 0.0175 mol/L. At equilibrium
[HI] = 0.0276 mol/L. Use this experimental
information to calculate the equilibrium constant.
 EXAMPLE 4
The reaction
CO(g) + H2O(g) CO2(g) + H2(g)

has KC = 4.06 at 500oC. If 0.100 mol of CO and

0.100 mol of H2O(g) are placed in a 1.00 liter
reaction vessel at this temperature, what are the
concentration of the reactants and products
when the system reaches equilibrium?
 EXAMPLE 5
The equilibrium condition for SO2(g), O2(g),
and SO3(g) is important in sulfuric acid production.
When a 0.0200 mol sample of SO3 is introduced
into an evacuated 1.52 L vessel at 900 K, 0.0142 mol
SO3 is present at equilibrium.
What is the value of KP for dissociation of SO3(g) at
900 K?

2SO3(g) 2SO2(g) + O2(g)

 DEGREE OF DISSOCIATION (a)

Fraction of a molecule dissociate or

decompose into smaller molecules /
ions / atoms

Change in concentration of reactant

a =
Initial concentration of reactant
 EXAMPLE 6
A 0.0240 mol sample of N2O4(g) is allowed to
come to equilibrium with NO2(g) in a 0.372L
flask.
N2O4(g) 2NO2(g)
KC = 4.61 x 103 at 25oC
Calculate the degree of dissociation of N2O4(g).
 aA(g) + bB(g) cC(g) + dD(g)

Suppose you know the value of K at the temperature

of the reaction

How do you know if the reaction has reached

equilibrium?

If it hasnt, how do you know in which direction it

is progressing to reach equilibrium?

ANS: Compare the value of K and Q

 PREDICTING THE DIRECTION
OF A REACTION

The direction of a reaction can be predicted by

comparing the equilibrium constant, Kc or Kp with
the value of reaction quotient, Qc or Qp.

The expression for Q is the same as that for the

equilibrium constant, K.

The reaction quotient (Q) is defined as the

numerical value of the equilibrium expression

- Evaluated at any time not necessarily at

equilibrium.
aA(g) + bB(g) cC(g) + dD(g)

[C]c [D]d [A], [B], [C], [D] :

KC = equilibrium
[A]a [B]b
concentrations

[C]c [D]d [A], [B], [C], [D] :

QC = any (initial)
[A]a [B]b concentrations
To determine the direction in which the net reaction
will proceed to achieve equilibrium, the values of
Qc and Qp must be compared.

The system is not at equilibrium.

Initially, there are more

Q<K reactants in the reaction
mixture.

To reach equilibrium Q=K, the

reaction proceeds from left to right .
 The system is not at equilibrium.
Q>K Initially, there are more
product in the reaction
mixture

To reach equilibrium Q=K, the reaction

proceeds from right to left .

Q=K The system is at equilibrium. No nett

change.
 EXAMPLE 7
At a very high temperature, KC = 65.0 for
the following reaction.
2HI(g) H2(g) + I2(g)
The following concentrations were detected in
a mixture. Is the system at equilibrium?
If not, in which direction must the reaction
proceed for equilibrium to be established?
[HI] = 0.500 M, [H2] = 2.80 M, and [I2] = 3.40 M
 EXAMPLE 8

At 100oC, KP = 60.6 for the reaction

2NOBr(g) 2NO(g) + Br2(g)
In a given temperature, 1.00atm of each
component is placed in a container.
Is the reaction at equilibrium?
If not, in which direction will it proceed?
 EXAMPLE 9

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.

N2(g) + 3 H2(g) 2 NH3(g)

KC = 1.70 x 102

Is the reaction mixture at equilibrium?

If not, what is the direction of the net reaction?
 EXERCISE 01
An inorganic chemist studying the reactions of
phosphorus halides mixes 0.1050 mol of PCl5
with 0.0450 mol of Cl2 and 0.0450 mol of PCl3
in a 0.5000L flask at 250oC:
PCl5(g) PCl3(g) + Cl2(g) KC = 4.2 x 102
(a) In which direction will the reaction proceed?
(b) If [PCl5] = 0.2065 M at equilibrium, what are
the equilibrium concentrations of the
other components.