Chemical Equilibrium

LACKSON NGWIRA
DEPARTMENT OF BASIC SCIENCES
CHEMISTRY UNIT

1
 OBJECTIVES
You should be able to :
■ Define equilibrium and its conditions.
■ Discuss the equilibrium constants.
■ Describe equilibrium involving pressure.
■ Solve problems involving equilibrium.
■ Explain La Châtelier’s Principle.
■ Know the application of equilibrium constant.

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Chemical equilibrium is the state reached by a reaction
mixture when the rates of forward and reverse reactions have
become equal
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
H2O H2O (g)
(l)
Chemical equilibrium
N2O4 (g) 2NO2 (g)
 The Concept of Equilibrium
• The point at which the rate of decomposition:
N2O4(g) → 2NO2(g)
equals the rate of dimerization:
2NO2(g) → N2O4(g).
is dynamic equilibrium.
• The equilibrium is dynamic because the reaction
has not stopped: the opposing rates are equal.
• Consider frozen N2O4: only white solid is present.
On the microscopic level, only N2O4 molecules are
present.
 N2O4 (g) 2NO2 (g)

equilibrium
equilibrium
equilibrium

Start with NO2 Start with N2O4 Start with NO2 & N2O4
constant
Simulations

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 N2O4 (g) 2NO2 (g)

[NO2]
K 2 = 4.63 x 10-
= [N2O4 3

]
aA + bB cC + dD

[C]c[
K Law of Mass
D] d
[A]a[B
= Action
]b
Equilibrium Will
K >> Lie to the right Favor products
1
K << Lie to the left Favor reactants
1
Homogenous equilibrium applies to reactions in which all
reacting species are in the same phase.

N2O4 (g) 2NO2 (g)

[NO2] P
Kp = NO2
Kc =2 2
[N2O4 PN O
2 4
] In most
cases
Kc ≠ Kp
aA (g) + bB (g) cC (g) + dD (g)

Kp = Kc(RT)Δn
Δn = moles of gaseous products – moles of gaseous reactants
= (c + d) – (a + b)
 Homogeneous Equilibrium

CH3COOH (aq) + H2O (l) CH3COO- (aq) + H3O+ (aq)

[CH3COO-]
Kc‘ = [H2O] = constant
[CH
[H3O3COOH]
+
]
[H2O]
[CH3COO-]
Kc = = Kc‘ [H2O]
[H3[CH
O+] 3COOH]

General practice not to include units for the

equilibrium constant.
 The equilibrium concentrations for the reaction between
carbon monoxide and molecular chlorine to form COCl2 (g)
at 740C are [CO] = 0.012 M, [Cl2] = 0.054 M, and [COCl2] =
0.14 M. Calculate the equilibrium constants Kc and Kp.

CO (g) + Cl2 (g) COCl2 (g)

[COC 0.14
Kc = l ] = = 2.2 x 102
[CO][Cl
2 2] 0.012 x
0.054
Kp = Kc(RT)Δn

Δn = 1 – 2 = -1 R = 0.0821 T = 273 + 74 = 347

K
Kp = 220 x (0.0821 x 347)-1 = 7.7
The equilibrium constant Kp for the reaction
2NO2 (g) 2NO (g) + O2 (g)
is 158 at 1000K. What is the equilibrium pressure of O2 if
the PNO 2= 0.400 atm and PNO = 0.270 atm?

2
PNO PO 2
Kp = 2
PNO 2

2
PNO
P 2 = Kp 2
2
O
PNO

P 2 = 158 x = 347
O (0.400)2/(0.270)2 atm
Heterogenous equilibrium applies to reactions in which
reactants and products are in different phases.

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

[CaO] [CaCO3] =
Kc‘ = [CO 2] 3]
[CaCO constant
[CaO] = constant
[CaCO3]
Kc = [CO2] = Kc‘ x Kp = PCO 2
[CaO
]
The concentration of solids and pure liquids are not
included in the expression for the equilibrium constant.
 CaCO3 (s) CaO (s) + CO2 (g)

PCO 2 = Kp

PCO 2 does not depend on the amount of CaCO3 or

CaO
Consider the following equilibrium at 295 K:
NH4HS (s) NH3 (g) + H2S (g)
The partial pressure of each gas is 0.265 atm. Calculate
Kp and Kc for the reaction?

Kp = P P = 0.265 x 0.265 =
NH3 H2S
0.0702

Kp = Kc(RT)Δn

Kc = Kp(RT)-Δn
Δn = 2 – 0 = 2 T = 295 K

Kc = 0.0702 x (0.0821 x 295)-2 = 1.20 x 10-4

 [C] [E][F]
A+B C+ Kc‘ Kc‘ = [D] Kc‘‘ =
[A][B] [C]
D
C+D E+ Kc‘‘ [D]
F [E][F]
A+B E+ Kc Kc =
[A][B]
F

Kc = Kc‘ x Kc‘‘

If a reaction can be expressed as the 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.
N2O4 (g) 2NO2 (g) 2NO2 (g) N2O4 (g)

[NO2] [N2O4 1
K = 4.63 x 10 -3
K‘ = = =
2
[N2O4 ]
[NO2] K
= 216
] 2

When the equation for a reversible reaction

is written in the opposite direction, the
equilibrium constant becomes the reciprocal
of the original equilibrium constant.
 Writing Equilibrium Constant
Expressions
• 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.
• The concentrations of pure solids, pure liquids and solvents
do not appear in the equilibrium constant expressions.
• The equilibrium constant is a dimensionless quantity.
• In quoting a value for the equilibrium constant, you must
specify the balanced equation and the temperature.
• 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.
Chemical Kinetics and Chemical Equilibrium

kf ratef = kf [A][B]2
A + 2B
AB2 kr rater = kr [AB2]

Equilibrium
ratef = rater

kf [A][B]2 = kr [AB2]

kf [AB2]
= Kc =
kr [A]
[B]2
 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
 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.
The reaction
CO(g) + H2O(g) ⇌ CO2(g) + H2(g)
is used to increase the ratio of hydrogen in synthesis gas (mixtures of
CO and H2). Suppose you start with 1.00 mol each of carbon monoxide
and water in a 50.0-L vessel. How many moles of each substance are in
the equilibrium mixture at 1000oC? The equilibrium constant Kc at this
temperature is 0.58.

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The equilibrium constant Kc for the reaction H2(g) + I2(g) 2HI(g) is 54.3
at 430oC. Suppose that the initial concentrations of H2, I2, and HI are
0.00623 M, 0.00414 M, and 0.0224 M, respectively. Calculate the
concentrations of these species at equilibrium.

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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.

• Changes in
Concentration
N2 (g) + H2 (g) NH3 (g)

Equilibrium
Add
shifts left to
NH3
offset stress
 Le Châtelier’s
Principle
• Changes in Concentration
Remove Remove
continued Add Add

aA + bB cC + dD

Chang Shifts the

e 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
 Le Châtelier’s
Principle
• Changes in Volume and
Pressure
A (g) + B (g) C (g)

Chang Shifts the

e Equilibrium
Increase Side with fewest moles of gas
pressure
Decrease Side with most moles of gas
pressure
Increase volume Side with most moles of gas
Decrease volume Side with fewest moles of gas
 Le Châtelier’s
Principle
• Changes in
Temperature
Chang Exothermic Endothermic
e Rx Rx
Increase temperature K decreases K increases
Decrease temperature K increases K decreases

• Adding a Catalyst
• does not change K
• does not shift the position of an equilibrium system
• system will reach equilibrium sooner
 uncatalyze catalyzed
d

Catalyst lowers Ea for both forward and reverse reactions.

Catalyst does not change equilibrium constant or shift equilibrium.
 Le Châtelier’s
Principle
Change
Chang Shift Equilibrium
e Equilibrium Constant
Concentration yes no
Pressur yes no
e
Volume yes no
Temperature yes yes
Catalyst no no
 Solubility Product Equilibria
❑Insoluble salts are really very slightly soluble.
❑If we add Ag2SO4 to water, some of the slightly soluble
Ag2SO4 dissolves:
Ag SO (s) →
2 4 ← 2 Ag+(aq) + SO 2-(aq)4

❑We can write the solubility product equilibrium

constant, Ksp, for the reaction:
Ksp = [Ag+]2 [SO42-]
❑Recall, we don’t include pure solids or liquids in
equilibrium constant expressions.
 Experimental Determination of Ksp
❑We can calculate the numerical value of Ksp if we
know the concentrations of all the species in the
reaction.
Mg(OH)2(s) →← Mg2+(aq) + 2 OH-(aq)
❑If the concentrations at equilibrium are [Mg2+] =
0.00016 M, and [OH-] = 0.00033 M, what is Ksp?

Ksp = [Mg2+][OH-]2 = (0.00016)(0.00032)2

Ksp = 1.6 × 10-11

 Solubility Equilibria Shifts
❑Let’s look at the following solubility equilibrium:
AgCl(s) →
← Ag +
(aq) + Cl -
(aq)
Ksp = [Ag+][Cl-]
❑What happens if we add more AgCl?
🔾Nothing, since AgCl does not appear in Ksp.
❑What happens if we add some soluble NaCl?
🔾We increase [Cl-], and the equilibrium shifts to the
left producing more solid AgCl.
Application of chemical equilibria in human body
❑ In the human body, equilibrium plays a prominent role in
regulating the concentrations of various substances, notably
pH, in the bloodstream.
❑ Maintaining a level pH is vital for human survival because
enzymes and proteins both rely on pH to function properly.
❑ In addition, equilibrium exists between concentrations of
extracellular and intercellular fluids.
❑ The process of osmosis allows water to flow from one side to
the other.
❑ Maintaining an equilibrium of concentrations in both areas is
essential for the cell's health.
❑ Maintaining equilibrium of the human body is vital for survival.
❑ Through these three lessons, students will be able to apply
their knowledge of equilibrium to real life situations.
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 QUIZ 2
1. The rate constant for the reaction below is 0.54/M.s at 300°C
2NO2(g) ⟶ 2NO(g) + O2(g)
How long (in seconds) would it take for the concentration of NO2
to decrease from 0.62 M to 0.28 M?

2. If the activation energy for the reaction is 268 kJ mol-1 and the
rate constant at 660 K is 8x10-3 sec-1, what will be the
temperature at rate constant 6.67 x 10-2 sec-1?

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