Module 08
Module 08
Module 8
Chapter 14
1
Irreversible and
reversible reactions
Irreversible reaction: Only reactants react to
form the products
KCℓO3 → KCℓ + O2
2
Equilibrium
Equilibrium is a state in which there are no observable
changes in concentration as time goes by.
Chemical equilibrium
N2 O4 𝑔 ⇄ 2NO2 𝑔
3
Law of Mass Action
C 𝑐 D𝑑
𝐾= 𝑎 B 𝑏
A
4
Equilibrium of N2 O4
N2 O4 𝑔 ⇄ 2NO2 𝑔
constant
5
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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6
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
− +
CH3 COO H3 O
𝐾𝑐′ = H2 O = constant
CH3 COOH H2 O
CH3 COO− H3 O+
𝐾𝑐 = = 𝐾𝑐′ H2 O
CH3 COOH
8
Heterogeneous Equilibrium
CaO CO2
𝐾c′ = CaCO3 =constant
CaCO3
CaO =constant
𝐾𝑐 = CO2 𝐾𝑝 = 𝑃co2
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
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 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)
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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
20
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)
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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)
𝑎A + 𝑏B ⇄ 𝑐C + 𝑑D
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Le Châtelier’s Principle (2)
A 𝑔 +B 𝑔 ⇄C 𝑔
25
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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Change Equilibrium
Change Shift Equilibrium Constant
Concentration yes no
Pressure yes* no
Volume yes* no
Temperature yes yes
Catalyst no no
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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:
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