CHEMICAL EQUILIBRIUM

for GENERAL CHEMISTRY 2/Grade 12

Quarter 4 / Week 2
APRIL 7-12, 2024
 OBJECTIVES

At the end of the lesson, you should be able to:

K : explain chemical equilibrium in terms of the reaction rates
and the Le Chatelier’s principle
S : write the mass action expression for a given balanced
chemical equation for homogeneous and heterogeneous
equilibria.
A : recognize the application of chemical equilibrium in real-life
situations.

LEARNING COMPETENCIES

- Explain chemical equilibrium in terms of the reaction rates of the

forward and the reverse reaction (STEM_GC11CEIVb-e-145)
- Calculate equilibrium constant and the pressure or concentration
of reactants or products in an equilibrium mixture
(STEM_GC11CEIVb-e-148)
- 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 (STEM_GC11CEIVb-e-
149)
DISCUSSION:

Chemical Equilibrium

Assuming the rate (say number of cars per hour) at which cars
enter the city is the same as the rate at which the cars leave the
city, then the two opposing processes are in balance. This also
means that there is a constant number of cars inside the city.

A state of balance is also referred to as a state of equilibrium.

In a reversible reaction, when the reactants start to form the
products, the products would then start to reform the reactants. The
two opposing processes happen at different rates but a certain
point in the reaction will be reached where the rates of the forward
and backward reactions are the same (marked by the broken line
in Figure 1). This is the state of chemical equilibrium.
 Figure 1. Changes in the rate of the forward and
backward reactions in a reversible reaction
Source: www.dynamicscience.om

The state of chemical equilibrium is a highly dynamic state.

This means that though there are no change in the composition of
the reaction mixture and no visible changes taking place, the
particles are continuously reacting. Also, a system at chemical
equilibrium can be easily disturbed by changes in the reaction
conditions.
EQUILIBRIUM CONSTANT

The relationship between the concentrations of the reactants

and products may be expressed using the law of mass action
expression/equilibrium constant expression. For the general
equilibrium reaction:

the law of mass action expression is written as

where the [] is the concentration expressed in molarity and Keq is

the equilibrium constant. If molar concentrations are used, Keq may
also be referred to as Kc. The law of mass action is basically the ratio
of the concentrations of the products raised to their respective
stoichiometric coefficients to that of the reactants.

Example:

For the reaction , the law of mass

action expression is written as:

[𝑁𝑂]2
𝐾𝑐 =
[𝑁2𝑂4]

Other examples:

Equilibrium Constant
Balanced Chemical Equation
Expression
[𝑂2]3
2O3(g) → 3O2(g)
𝐾𝑐 =
[𝑂 ]2
3
[𝑁𝑂𝐶𝑙]2
2NO(g) + Cl2(g) → 2NOCl(g) 𝐾𝑐 =
[𝑁𝑂]2[𝐶𝑙2 ]

[𝐹−]2 [𝐻2𝐶2𝑂4]
2HF(aq) + C2O42-(aq) → 2F -(aq) + H2C2O4(aq) 𝐾𝑐 =
[𝐻𝐹]2[𝐶4 𝑂 42−]

Equilibrium constants for homogeneous gaseous equilibria

may also be expressed in terms of partial pressures. The expression
is written in much the same way as described, only that the partial
pressure is raised to the coefficient instead of the molar
concentration.

Example:
Equilibrium Constant
Balanced Chemical Equation
Expression
(𝑃𝑂2 )3
𝐾𝑝 = (𝑃 )2
𝑂
3

(𝑃𝑁𝑂𝐶𝑙 )2
𝐾𝑝 =
(𝑃 )2(𝑃 )
𝑁𝑂2 𝐶𝑙2

For equilibrium reactions where the reactants and products

are in different phases (heterogeneous equilibria), pure solids and
pure liquids are excluded in writing equilibrium constant
expressions. For example, consider the reaction:

The equilibrium constant expression for the reaction is:

𝐾𝑐 = [𝑃𝑏+2][𝐶𝑙−]2

THE EQUILIBRIUM CONSTANT, K

The equilibrium constant, K, is the numerical value that is

obtained when equilibrium concentrations are substituted to the
equilibrium constant expression. The value of K may vary from very
large to very small values. This value provides an idea of the relative
concentrations of the reactants and products in an equilibrium
mixture. Consider the reaction to produce phosgene (COCl2), a
toxic gas used in the manufacture of certain polymers and
insecticides, at 100°C:
[𝐶𝑂𝐶𝑙2]
𝐾𝑐 = = 4.56 𝑥109
[𝐶𝑂][𝐶𝑙2]

The large value of 4.56 × 109 suggests that the concentration

of COCl2 must be very large as compared to the individual
concentrations of CO and Cl2. The value suggests that at
equilibrium, the reactions mixture contains more of the product
COCl2 than the reactants CO and Cl2. This is experimentally verified.
In other words, the equilibrium lies to the right or towards the
product side based on the chemical equation given.
Example:
Gaseous hydrogen iodide is placed in a closed container at
425°C, where it partially decomposes to hydrogen and iodine as
shown in the chemical reaction below.

At equilibrium, it is found that [HI] = 3.53 × 10–3 M, [H2] = 4.79 ×

10–4 M and [I2] =4.79 × 10–4 M. What is the value of Kc at this
temperature?

[𝐻2][𝐼2] (4.79 𝑥 10−4)(4.79 𝑥 10−4)

𝐾𝑐 = = = 0.0184
[𝐻𝐼]2 (3.53 𝑥 10−3)2

In the second example, the value of Kc is small (< 1). For this to
happen, the value of the denominator must be larger compared
to the numerator. In the case of the given reaction, the equilibrium
concentration of HI is higher than the equilibrium concentrations of
the decomposition products. This means that the equilibrium lies on
the left or on the reactant side.

In general, if K >> 1 (large K value), the equilibrium lies to the

right and the products predominate in the equilibrium mixture. If K
<< 1 (small K value), the equilibrium lies to the left and the reactants
predominate in the equilibrium mixture.

Product Reactant

Reactants Product

a.) K >> 1 b.) K << 1

Figure 2. The relationship of K value and the composition of the equilibrium mixture.

If K > - Equilibrium favors the products; equilibrium lies to the right.

If K < - Equilibrium favors the reactants; equilibrium lies to the left.
If K = 1- Both the reactants and products are present at equilibrium.
EQUILIBRIUM CONSTANT WITH EQUILIBRIUM
CONCENTRATIONS/PARTIAL PRESSURES

Determining equilibrium constants when equilibrium

concentrations or partial pressures are known involves
straightforward substitution to the equilibrium constant expression.

Example:

1. A mixture of hydrogen and nitrogen in a reaction vessel is

allowed to attain equilibrium at 472 °C. The equilibrium mixture
of gases was analyzed and found to contain 7.38 atm H2, 2.46
atm N2 and 0.166 atm NH3. From these data, calculate the
equilibrium constant Kp for the reaction:

Given:
Equilibrium partial pressures: 7.38 atm H 2, 2.46 atm N2 and 0.166
atm NH3

Strategy: Using the balanced chemical equation, write the

equilibrium constant expression, Kp, then substitute the given
equilibrium partial pressures to it.

Solution:
(𝑃𝑁𝐻 )2 (0.166)2
𝐾𝑝 = 3 = = 2.79 𝑥 10−5
3
(𝑃𝑁2 )(𝑃𝐻2 ) (2.46)(7.38)3

2. An aqueous solution of acetic acid is found to have the following

concentrations at 25 °C: [CH3COOH] = 1.65 × 10–2 M; [H3O+] =
5.44 × 10–4 M; and [CH3COO–] = 5.44 × 10–4 M. Calculate the
equilibrium constant Kc for the ionization of acetic acid at 25 °C.
The reaction is:

Given:
Equilibrium concentrations: [CH3COOH] = 1.65 × 10–2 M; [H3O+] =
5.44 × 10–4 M; and [CH3COO–] = 5.44 × 10–4 M
Strategy: Using the balanced chemical equation, write the
 equilibrium constant expression, Kc, then substitute the given
equilibrium concentrations to it.

Solution:
[CH3COO−][H3O+] (5.44 𝑥 10−4 )(5.44 𝑥 10−4 )

𝐾𝑐 = =
[CH3 COOH] (1.65 𝑥 10−2 )

= 1.79 𝑥 10−5

3. Sulfur trioxide decomposes at high temperature in a sealed

container according to the reaction:
2SO3(g) → 2SO2(g) + O2(g)
Initially, the vessel is charged at 1000 K with SO3(g) at a partial
pressure of 0.500 atm. At equilibrium, the SO3 partial pressure is
0.200 atm. Calculate the value of Kp at 1000 K.

Given: Initial partial pressure for SO3(g) = 0.500 atm

Equilibrium partial pressure for SO3(g) = 0.200 atm

Strategy: Using the equilibrium table, tabulate the given initial

and equilibrium partial pressures. Denote the changes in partial
pressure using a variable as guided by stoichiometric coefficients
in the balanced chemical equation. Solve for the unknown to
calculate for the equilibrium partial pressures of SO2 and O2 and
then solve for Kp.

Solution: Let x = amount of SO3 that changes to attain

equilibrium
2SO3(g) → 2SO2(g) + O2(g)

Initial Pressure 0.500 0 0

Change in
-2x 2x x
Pressure
At Equilibrium 0.200 2x x

For the pressure of SO3(g) at equilibrium (based on the given):

0.500 – 2x = 0.200
 Rearrange to get x into:
0.500−0.200
x= = 0.150
2

For the pressure of SO2(g) at equilibrium:

2x = 0.200(0.150) = 0.300
For the pressure O2(g) at equilibrium:
x = 0.150
Substituting the values into the equilibrium constant expression
to get the Kp value:

[SO2]2[O2] [0.300]2[0.150]
𝐾𝑝 = = = 0.338
[SO3] [0.200]2

Le Chatelier’s Principle

Le Chatelier’s Principle states that if a stress (changes in

reaction conditions) is applied to a system in equilibrium, then the
systems adjust to reduce the effect of the stress applied. The stress
that may affect a system at chemical equilibrium include changes
in the concentration of either products or reactants, changes in
temperature and changes in pressure for gaseous equilibria.

Effects of Changing the Concentration

When the concentration of either a reactant or a product is

increased, the equilibrium shifts into the direction that would
consume that added component. If the concentration is
decreased, then the equilibrium shifts into the direction that
replenishes the lost component. Increasing the concentration of a
substance in an equilibrium mixture displaces the equilibrium in the
direction which consumes some of the added material. Conversely,
decreasing the concentration of a substance favors the reaction
which produces it.

Effect of Changing the Temperature

When the temperature is increased, the reaction which
consumes the applied heat is favored i.e. the reaction which is
endothermic. When the temperature is decreased, the reaction
which produces heat is favored i.e. the reaction which is
exothermic. Another way of interpreting the results is to treat heat
as either a reactant or product. When heat is added, equilibrium
shifts to the reaction that consumes it. The same generalization on
the effect of changes in concentration is applied.

Effect of Changes in Pressure (or Volume) for Gaseous Equilibria

For gaseous equilibria, changes in pressure due to changes in

the volume of the container affect chemical equilibrium. When the
pressure is increased (by decreasing the volume of the container),
the system adjusts by reducing the total pressure exerted by the gas
particles present. This can be done by shifting the equilibrium
towards the formation of a lesser number of gas particles which
may be predicted using a balanced chemical equation.

2NO2(g) (brown) → N2O4(g)(colorless)

When the volume of the container is decreased, the total

pressure inside is increased and the equilibrium has to shift to the
direction that has a lesser number of gaseous particles in order to
relieve the pressure, i.e. towards the formation of N2O4. According
to the balanced equation, there are two moles of N2O on the
reactant side and 1 mole of N2O4 on the product side. When the
volume of the container is increased, then the total pressure is
decreased. When this happens, the equilibrium shifts to the
direction that would produce more gas particles, i.e. towards the
formation of N2O. The total pressure of the gaseous reaction may
also be increased by adding an inert gas which is not involved in
the equilibrium reaction. For example, addition of neon gas on an
equilibrium mixture of N2O and N2O4, will be able to change the
total pressure but not the partial pressures of the gases that are
involved in the equilibrium process. This will therefore not affect the
value of the equilibrium constant and will not cause a shift of the
equilibrium.
Summary of Le Chatelier’s Principle

Below is the summary of the effect on equilibrium to different

stress.
Table 1. Effects of Changes in Conditions on Equilibrium
Change Effect on Equilibrium
A. Concentration
- Adding reactant Equilibrium favors the products
- Removing reactant Equilibrium favors the reactants
- Adding product Equilibrium favors the reactants
- Removing product Equilibrium favors the products
B. Temperature
- Increasing - in an endothermic reaction, equilibrium favors the
temperature products
- in an exothermic reaction, equilibrium favors the
reactants
- Decreasing - in an endothermic reaction, equilibrium favors the
temperature reactants
- in an exothermic reaction, equilibrium favors the
products.
C. Pressure
- Increasing pressure Equilibrium favors the side that has fewer moles.
- Increasing pressure Equilibrium favors the side that has more moles.
Source: Janice Gorzynski Smith, General, Organic, & Biological Chemistry-183

PERFORMANCE TASK 2

A. Directions: Write the equilibrium constant expression, Kc, for the

following reactions on short bondpaper. Indicate also if the
equilibrium is homogeneous or heterogeneous.
1.) 3NO(g) N2O(g) + NO2(g)
2.) CH4(g) + 2H2S(g) CS2(g) + 4H2(g)
3.) Ni(CO)4(g) Ni(s) + 4CO(g)
4.) HF(aq) H+(aq) + F-(aq)
5.) 2Ag(s) + Zn2+(aq) 2Ag+(aq) + Zn(s)
B. Directions. Given the equilibrium reaction (column 1) and the
stress applied (column 2), choose the appropriate effect and shift
of equilibrium found in column 3 and 4, respectively. Write the letter
of the correct answer on short bondpaper.

Stress Effect Equilibrium

Equilibrium Reaction
Applied Shift
1.) A. increase A. Forward
B. decrease B. Backward
Decreasing
H2(g) + Cl2(g) → 2HCl (g) C. No effect C. No Shift
pressure
in the number of
moles of HCl(g)
2.) A. increase A. Forward
B. decrease B. Backward
Fe3O4 (s) + 4H 2(g) + heat → 3Fe(s) + 4H2O(g) Increasing C. No effect C. No Shift
Temperature in the volume of
water vapor
collected.
3.) A. increase A. Forward
B. decrease B. Backward
Addition of
2 NO(g) +O2 (g) → 2NO2(g) + heat C. No effect C. No Shift
helium
in the number of
moles of NO
4.) A. increase A. Forward
B. decrease B. Backward
Removal of
H2CO3(aq) → CO2(aq) + H2O(l) C. No effect C. No Shift
CO2
In the amount
of H2CO3
REFERENCES
Janice Gorzynski Smith, General, Organic, & Biological Chemistry.
New York: McGraw-Hill Companies, Inc., 2010. 174-178

Silberberg, Martin S. 2006. CHEMISTRY: The Molecular Nature of

Matter and Change. 4th ed. New York: McGraw-Hill
Companies, Inc
16