CHEMICAL EQUILIBRIUM

INTRODUCTION:
• When water is allowed to stand in an
open jar, it will eventually evaporate
completely.
• However, when stored in a tightly
covered jar, vaporization of water is
balanced by condensation of its vapor,
and so the quantity of liquid water
remains constant indefinitely.
• The liquid water and its vapor are said to be in a state of
equilibrium, a balanced condition in which the rates of opposing
process are equal.
 LEARNING OUTCOMES:
This learning plan is designed for you to:
a. Explain chemical equilibrium in terms of the reaction rates
of the forward and the reverse reaction;
b. Calculate equilibrium constant and the pressure or
concentration of reactants or products in an equilibrium
mixture;
c. State the Le Chatelier’s principle and apply it qualitatively to
describe the effect of changes in pressure, concentration and
temperature on a system at equilibrium.
 LESSON 1: THE CONCEPT OF CHEMICAL EQUILIBRIUM
• In our discussion of chemical reactions, we
have always assumed that chemical reactions
go to completion, that means that all
reactants are transformed into products.
(forward reaction)
• However, only few chemical reactions
proceed to completion. There are
reversible reactions that can proceed in
two opposite direction.
CH4 (g) + Cl2 (g) ↔ CH3Cl (g) + HCl (g)
 LESSON 1: THE CONCEPT OF CHEMICAL EQUILIBRIUM
• Chemical Equilibrium refers to the state wherein opposing
reactions proceed at equal rates: The rate at which the products
form from the reactants equals the rate at which the reactants
form from the products.
 LESSON 1: THE CONCEPT OF CHEMICAL EQUILIBRIUM
Example:
A sample of frozen N2O4 inside a sealed
tube. The solid N2O4 becomes a gas as it
is warmed above its boiling point
(21.2°C), and the gas turns darker as the
colorless N2O4 gas dissociates into brown
NO2 gas. Eventually, even though there
is still N2O4 in the tube, the color stops
getting darker because the system reaches
equilibrium.
 LESSON 2: EQUILIBRIUM CONSTANT
• In 1864, two Norwegian scientist
named Cato Guldberg (1836-
1902) and Peter Waage (1833-
1900) proposed the law of mass
action which expresses the
relationship between the
concentration of the reactants and
products present at equilibrium.
 LESSON 2: EQUILIBRIUM CONSTANT
• Suppose we have the general equilibrium equation
aA + bB ⇋ dD + eE
• According to the law of mass action, the equilibrium
condition is described by the expression
["]! [$]"
Kc =
% # &$
• We call this relationship the equilibrium-constant expression.
• Note: Kc is highly dependent to Temperature.
 LESSON 2: EQUILIBRIUM CONSTANT
Example:
For the reaction below, write the equilibrium-constant
expression.
N2 (g) + 3 H2 (g) ⇋ 2 NH3 (g)
the equilibrium-constant expression is
["#!]!
Kc = "" [#"]"
 LESSON 2: EQUILIBRIUM CONSTANT
Activity 1:
Write the equilibrium expression, Kc, for the following
reactions:
["!]!
a. 2 O3 (g) ⇋ 3 O2(g) Kc = [""]"

[$"%&]"
b. 2 NO (g) + Cl2 (g) ⇋ 2 NOCl(g) Kc= [$"]"[%& ]
!

['( $)" !]
c. Ag (aq) + 2 NH3 (aq) ⇋ Ag(NH3)2(aq) Kc=
[$)"]" ['(]
 LESSON 2: EQUILIBRIUM CONSTANT
Writing Equilibrium-Constant expression for
Heterogeneous Reactions
• Heterogeneous reaction involving gases and a solid or a
liquid, the concentration of pure liquids and pure solids
are not included because they have constant
concentrations.
• They are already integrated in the equilibrium constant
itself.Their concentration does not change.
 LESSON 2: EQUILIBRIUM CONSTANT
Example:
Let us consider this reaction,
6Ca(s) + 2NH3(g) ⇋ 3CaH2(s) + Ca3N2(s)
the equilibrium expression is:
!
Kc =
[#$*]!
 LESSON 2: EQUILIBRIUM CONSTANT
Activity 2
Write the equilibrium expression, Kc, for the following
heterogenous reactions:
a. PCl5(s) ⇋ PCl3(l) + Cl2(g) Kc =[Cl2]

[%"]"
b. C(s) + CO2(g) ⇋ 2CO(g) Kc = [%"!]
 LESSON 2: EQUILIBRIUM CONSTANT
Sample Problem:
A mixture of H2, S and H2S is held in closed vessel at 90°C until
equilibrium is reached.
H2(g) + S(s) ⇋ H2S(g)
At equilibrium, the concentration of H2 is 0.40 M and H2S is 0.027M.
Calculate the equilibrium constant for the reaction.
Solution:
[)!+]
1. Write the equilibrium equation: Kc = [) ]
!
2. Calculate for its equilibrium constant.
[)!+] [,.,./0]
Kc = = = 0.068
[)!] [,.1, 0]
 LESSON 2: EQUILIBRIUM CONSTANT
Activity 3:
1.At a temperature of 927°C, the equilibrium concentrations for the reaction
CO(g) + 3H2(g) ⇋ CH4(g) + H2O(g)
are [CO]=0.3065M, [H2]= 1.46M, [CH4]= 0.1935M and [H2O]=0.1935M.
Calculate the value of the equilibrium constant for this reaction at this
temperature.

%)# [)!"]
Kc =
[)!]! [%"]
(,.34*50)(,.34*50)
Kc = 3.170 "(,.*,750)
Kc=0.03925 or 0.04
 LESSON 2: EQUILIBRIUM CONSTANT
1. Determine concentration of H2 at 298 K, from, the reaction H2(g) + I2(g) ⇋ HI(g),
given that Kc=794.The gas-phase equilibrium is composed of the following:
[HI]=2.05x10-3 M and [I2]=1.25x10-3 M
 LESSON 3: EQUILIBRIUM CONSTANT MAGNITUDE
• While equilibrium constant does not say anything
about time it takes to reached equilibrium, it does
provide information about the mixture of reactants and
products at equilibrium.
• The value of the equilibrium constant determines the
equilibrium position. The term equilibrium position is a
qualitative description of the extent of a chemical
reaction.
 LESSON 3: EQUILIBRIUM CONSTANT MAGNITUDE
• Consider the reaction of nitrogen and hydrogen to form
ammonia at 500°C.
N2(g) + 3H2(g) ⇋ 2NH3(g)
['(!]% -2
Kc = & = 6.02x10
['"][("]
• The value of the equilibrium constant is less than 1. This
indicates that the denominator is greater than numerator.
• Therefore, the position of the equilibrium is said to lie to the
left.
 LESSON 3: EQUILIBRIUM CONSTANT MAGNITUDE

• Conversely, when Kc is large, the reactant concentration

is smaller than the product, this indicate that the
forward formation of products is more favored and the
equilibrium position is said to lie to the right.