Chemical Equilibrium

Module 8
Chapter 14

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 Irreversible and
reversible reactions
Irreversible reaction: Only reactants react to
form the products
KCℓO3 → KCℓ + O2

Reversible reaction: Products also react to

form the reactants
N2 O4 𝑔 ⇄ 2NO2 𝑔

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 Equilibrium
Equilibrium is a state in which there are no observable
changes in concentration as time goes by.

Chemical equilibrium is achieved when:

• the rates of the forward and reverse reactions are equal and
• the concentrations of the reactants and products remain
constant
Physical equilibrium
H2 O 𝑙 ⇄ H2 O 𝑔

Chemical equilibrium
N2 O4 𝑔 ⇄ 2NO2 𝑔
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 Law of Mass Action

Law of Mass Action:

For a reversible reaction at equilibrium and at constant
temperature, a certain ratio of reactants and products
concentrations has a constant value, K (the equilibrium
constant).
𝑎A + 𝑏B ⇄ 𝑐C + 𝑑D

C 𝑐 D𝑑
𝐾= 𝑎 B 𝑏
A

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 Equilibrium of N2 O4

N2 O4 𝑔 ⇄ 2NO2 𝑔
constant

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 Relationship of Equilibrium and K

C 𝑐 D𝑑
𝐾= 𝑎A + 𝑏B ⇄ 𝑐C + 𝑑D
A 𝑎 B 𝑏

Equilibrium Will
𝐾≫1 Lie to the right Favor products
𝐾≪1 Lie to the left Favor reactants

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 Homogeneous Equilibrium
Homogeneous equilibrium applies to reactions in which all
reacting species are in the same phase.

Phases N2 O4 𝑔 ⇄ 2NO2 𝑔
Solid 2
Liquid NO2 2 𝑃NO
𝐾𝑐 = 𝐾𝑝 = 2
Gases N2 O4 𝑃N2 O4
Aqueous

The concentration of solids and pure liquids are not

included in the expression for the equilibrium constant.
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 Homogeneous Equilibrium (1)

CH3 COOH a𝑞 + H2 O 𝑙 ⇄ CH3 COO− a𝑞 + H3 O+ a𝑞

− +
CH3 COO H3 O
𝐾𝑐′ = H2 O = constant
CH3 COOH H2 O

CH3 COO− H3 O+
𝐾𝑐 = = 𝐾𝑐′ H2 O
CH3 COOH

General practice not to include units for the equilibrium

constant.

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 Heterogeneous Equilibrium

Heterogenous equilibrium applies to reactions in which

reactants and products are in different phases.

CaCO3 𝑠 ⇄ CaO 𝑠 + CO2 𝑔

CaO CO2
𝐾c′ = CaCO3 =constant
CaCO3
CaO =constant

𝐾𝑐 = CO2 𝐾𝑝 = 𝑃co2

The concentration of solids and pure liquids are not

included in the expression for the equilibrium constant.
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 Relationship between Kc and Kp
N2 O4 𝑔 ⇄ 2NO2 𝑔
2
NO2 2 𝑃NO 2
𝐾𝑐 = 𝐾𝑝 =
N2 O4 𝑃N2 O4

In most cases
𝐾𝑐 ≠ 𝐾𝑝
𝑎A 𝑔 + 𝑏B 𝑔 ⇄ 𝑐C 𝑔 + 𝑑D 𝑔
∆𝑛
𝐾𝑝 = 𝐾𝑐 𝑅𝑇
• ∆𝑛 = moles of products − moles of reactants
• = 𝑐 + 𝑑 − 𝑎 + 𝑏 (Only gases and aqueous phases)
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 Writing Equilibrium Constant Expressions
1. The concentrations of the reacting species in the
condensed phase are expressed in M. In the gaseous
phase, the concentrations can be expressed in M or in atm.
2. The concentrations of pure solids, pure liquids and solvents
do not appear in the equilibrium constant expressions.
3. The equilibrium constant is a dimensionless quantity.
4. In quoting a value for the equilibrium constant, you must
specify the balanced equation and the temperature.
5. If a reaction can be expressed as a sum of two or more
reactions, the equilibrium constant for the overall reaction is
given by the product of the equilibrium constants of the
individual reactions.
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Example 14.1
Write expressions for 𝐾c , and 𝐾𝑝 if applicable, for the following reversible
reactions at equilibrium:
(a) HF 𝑎𝑞 + H2 O 𝑙 ⇌ H3 O+ 𝑎𝑞 + F − 𝑎𝑞

(b) 2NO 𝑔 + O2 𝑔 ⇌ 2NO2 𝑔

(c) CH3 COOH a𝑞 + C2 H5 OH a𝑞 ⇌ CH3 COOC2 H5 a𝑞 + H2 O 𝑙

Practice Exercise Write Kc and KP for the decomposition of dinitrogen pentoxide:

2N2O5(g) ⇌ 4NO2(g) + O2(g)
Example 14.2
The following equilibrium process has been studied at 230°C:
2NO 𝑔 + O2 𝑔 ⇌ 2NO2 𝑔
In one experiment, the concentrations of the reacting species at equilibrium are found
to be NO = 0.0542 M, O2 = 0.127 M, and NO2 = 15.5 M. Calculate the
equilibrium constant 𝐾c of the reaction at this temperature. (Answer = 6.44 x 105)

Practice Exercise Carbonyl chloride (COCl2), also called phosgene, was used in
World War I as a poisonous gas. The equilibrium concentrations for the reaction
between carbon monoxide and molecular chlorine to form carbonyl chloride
CO(g) + Cl2(g) ⇌ COCl2(g)
at 74°C are [CO] = 1.2 x 10-2 M, [Cl2] = 0.054 M, and [COCl2] = 0.14 M. Calculate
the equilibrium constant (Kc). (Answer = 220)
Example 14.3
The equilibrium constant 𝐾𝑃 for the decomposition of phosphorus pentachloride to
phosphorus trichloride and chlorine
PCl5 𝑔 ⇌ PCl3 𝑔 + Cl2 𝑔
is found to be 1.05 at 250° . If the equilibrium partial pressures of PCl5 and PCl3 are
0.875 atm and 0.463 atm, respectively, what is the equilibrium partial pressure of
Cl2 ? (answer = 1.98 atm)

Practice Exercise The equilibrium constant KP for the reaction is 158 at 1000 K.
2NO2(g) ⇌ 2NO(g) + O2(g)
Calculate Po2 if PNO2 = 0.400 atm and PNO = 0.270 atm. (Answer = 347 atm)
Example 14.4
Methanol CH3 OH is manufactured industrially by the reaction
CO 𝑔 + 2H2 𝑔 ⇌ CH3 OH 𝑔
The equilibrium constant 𝐾c for the reaction is 10.5 at 220° C. What is the value of
𝐾𝑃 at this temperature? (Answer = 6.41 x 10─3)

Practice Exercise For the reaction N2(g) + 3H2(g) ⇌ 2NH3(g)

KP is 4.3 x 10−4 at 375°C. Calculate KC for the reaction. (Answer = 1.2)
Example 14.5
Write the equilibrium constant expression 𝐾c , and 𝐾𝑃 if applicable, for each of the
following heterogeneous systems:
(a) NH4 2 Se 𝑠 ⇌ 2NH3 𝑔 + H2 Se 𝑔
(b) AgCl 𝑠 ⇌ Ag + 𝑎𝑞 + Cl− 𝑎𝑞
(c) P4 𝑠 + 6Cl2 𝑔 ⇌ 4PCl3 𝑙

Practice Exercise Write equilibrium constant expressions for Kc and KP for the
formation of nickel tetracarbonyl, which is used to separate nickel from other
impurities: Ni(s) + 4CO(g) ⇌ Ni(CO)4(g)
Example 14.6
Consider the following heterogeneous equilibrium: 𝑪𝒂𝑪𝑶𝟑 𝒔 ⇌ 𝐂𝐚𝐎 𝒔 + 𝑪𝑶𝟐 𝒈
At 800° C, the pressure of CO2 is 0.236 atm. Calculate (a) 𝐾𝑝 and (b) 𝐾c for the
reaction at this temperature. (Answer Kp = 0.236 and Kc = 2.68 x10─3)

Practice Exercise Consider the following equilibrium at 395 K:

NH4HS(s) ⇌ NH3(g) + H2S(g)
The partial pressure of each gas is 0.265 atm. Calculate KP and KC for the reaction.
(Answer Kp = 0.0702 and Kc = 6.6 x10─5)
 Reaction Quotient
The reaction quotient 𝑸𝐜 is calculated by substituting the
initial concentrations of the reactants and products into the
equilibrium constant 𝐾𝑐 expression.
IF
• 𝑄𝑐 < 𝐾𝑐 system proceeds from left to right to reach equilibrium
• 𝑄𝑐 = 𝐾𝑐 the system is at equilibrium
• 𝑄𝑐 > 𝐾𝑐 system proceeds from right to left to reach equilibrium

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Example 14.8
At the start of a reaction, there are 0.249 mol N2 , 3.21 × 10−2 mol H2 , and 6.42 × 10−4
mol NH3 in a 3.50L reaction vessel at 375°C. If the equilibrium constant 𝐾c for the
reaction 𝑵𝟐 𝒈 + 𝟑𝑯𝟐 𝒈 ⇌ 𝟐𝑵𝑯𝟑 𝒈
is 1.2 at this temperature, decide whether the system is at equilibrium. If it is not,
predict which way the net reaction will proceed. (Answer = 0.611 Forward)

Practice Exercise The equilibrium constant (Kc) for the formation of nitrosyl
chloride, an orange-yellow compound, from nitric oxide and molecular chlorine
2NO(g) + Cl2(g) ⇌ 2NOCl(g)
is 6.5 x 10 4 at 35°C. In a certain experiment, 2.0 x 10−2 mole of NO, 8.3 x 10−3
mole of Cl2, and 6.8 moles of NOCl are mixed in a 2.0-L flask. In which direction will
the system proceed to reach equilibrium? (Answer = 27.8 x 106 Reverse)

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 Calculating Equilibrium Concentrations

1. Express the equilibrium concentrations of all species in

terms of the initial concentrations and a single unknown x,
which represents the change in concentration.
2. Write the equilibrium constant expression in terms of the
equilibrium concentrations. Knowing the value of the
equilibrium constant, solve for x.
3. Having solved for x, calculate the equilibrium
concentrations of all species.

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Example 14.9
A mixture of 0.500 mol H2 and 0.500 mol l2 was placed in a 1.00L stainless-steel
flask at 430° C. The equilibrium constant 𝐾c for the reaction
H2 𝑔 + l2 𝑔 ⇌ 2Hl 𝑔
is 54.3 at this temperature. Calculate the concentrations of H2 , l2 , and HI at
equilibrium. (Answer H2 and I2 = 0.107 and HI = 0.786)

Practice Exercise Consider the reaction in Example 14.9. Starting with a

concentration of 0.040 M for HI, calculate the concentrations of HI, H2 , and I2 at
equilibrium. (Answer H2 and I2 = 4.3 x10─3 and HI = 0.314)

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 Le Châtelier’s Principle
If an external stress is applied to a system at equilibrium, the
system adjusts in such a way that the stress is partially offset
as the system reaches a new equilibrium position.
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• Changes in Concentration

N2 𝑔 + 3H2 𝑔 ⇄ 2NH3 𝑔

Equilibrium
shifts left to Add
offset stress NH3

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 Le Châtelier’s Principle (1)

• Changes in Concentration continued

𝑎A + 𝑏B ⇄ 𝑐C + 𝑑D

Change Shifts the Equilibrium

Increase concentration of product(s) left
Decrease concentration of product(s) right
Increase concentration of reactant(s) right
Decrease concentration of reactant(s) left
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 Le Châtelier’s Principle (3)
• Changes in Temperature
Change Exothermic Rx Endothermic Rx
Increase temperature K decreases K increases
Decrease temperature K increases K decreases
N2 O4 𝑔 ⇄ 2NO2 𝑔 ∆𝐻 ° = 58.0 kJΤmol

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 Le Châtelier’s Principle (2)

• Changes in Volume and Pressure

A 𝑔 +B 𝑔 ⇄C 𝑔

Change Shifts the Equilibrium

Increase pressure Side with fewest moles of gas
Decrease pressure Side with most moles of gas
Increase volume Side with most moles of gas
Decrease volume Side with fewest moles of gas

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 Le Châtelier’s Principle (4)
• Adding a Catalyst
• does not change K
• does not shift the position of an equilibrium system
• system will reach equilibrium sooner
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Catalyst lowers 𝐸a for both forward and reverse reactions.

Catalyst does not change equilibrium constant or shift 26
equilibrium.
 Le Châtelier’s Principle - Summary

Change Equilibrium
Change Shift Equilibrium Constant
Concentration yes no
Pressure yes* no
Volume yes* no
Temperature yes yes
Catalyst no no

*Dependent on relative moles of gaseous reactants and products

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Example 14.11
At 720° C, the equilibrium constant 𝐾c for the reaction 𝑵𝟐 𝒈 + 𝟑𝑯𝟐 𝒈 ⇌ 𝟐𝑵𝑯𝟑 𝒈
is 2.37 × 10−3 . In a certain experiment, the equilibrium concentrations are N2 =
0.683 𝑀, H2 = 8.80 𝑀, and NH3 = 1.05 𝑀. Suppose some NH3 is added to the
mixture so that its concentration is increased to 3.65 M. (a) Use Le Châtelier’s principle
to predict the shift in direction of the net reaction to reach a new equilibrium. (b)
Confirm your prediction by calculating the reaction quotient 𝑄c and comparing its value
with 𝐾c . (Answer 2.86 x 10─2 Reverse)

Practice Exercise At 430°C, the equilibrium constant (KP) for the reaction
2NO(g) + O2(g) ⇌ 2NO2(g)
is 1.5 x105. In one experiment, the initial pressures of NO, O2, and NO2 are 2.1 x10−3
atm, 1.1 x 10−2 atm, and 0.14 atm, respectively. Calculate Qp and predict the direction
that the net reaction will shift to reach equilibrium. (Answer 4 x 105 Reverse)

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Example 14.12
Consider the following equilibrium systems:

(a) 2PbS 𝑠 + 3O2 𝑔 ⇌ 2PbO 𝑠 + 2SO2 𝑔

(b) PCl5 𝑔 ⇌ PCl3 𝑔 + Cl2 𝑔
(c) H2 𝑔 + CO2 𝑔 ⇌ H2 O 𝑔 + CO 𝑔
Predict the direction of the net reaction in each case as a result
of increasing the pressure (decreasing the volume) on the
system at constant temperature.
Practice Exercise Consider the equilibrium reaction
involving nitrosyl chloride, nitric oxide, and molecular chlorine
2NOCl(g) ⇌ 2NO(g) + Cl2(g)
Predict the direction of the net reaction as a result of
decreasing the pressure (increasing the volume) on the
system at constant temperature.
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Example 14.13
Consider the following equilibrium process between dinitrogen
tetrafluoride N2 F4 and nitrogen difluoride NF2 :
N2 F4 𝑔 ⇌ 2NF2 𝑔 ∆𝐻 ° = 38.5 kJΤmol
Predict the changes in the equilibrium if
(a) the reacting mixture is heated at constant volume;
(b) some N2 F4 gas is removed from the reacting mixture at
constant temperature and volume;
(c) the pressure on the reacting mixture is decreased at
constant temperature; and
(d) a catalyst is added to the reacting mixture.

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