Equilibrium

TOPIC 7 and 17
 Equilibrium Systems

 Many chemical reactions are

reversible.
 Such reactions do not go to
completion.
 A state of balance exists between the
products and the reactants
 When the concentration of neither
the reactants nor the products is
changing, the system is in
equilibrium.
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 Chemical Equilibrium

Chemical equilibrium occurs in

chemical reactions that are reversible.
In a reaction such as:

CH4(g) + H2O(g)  CO(g) + 3H2 (g)

The reaction can proceed in both directions

CO(g) + 3H2 (g)  CH4(g) + H2O(g)

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 Equilibrium Conditions

 Atequilibrium the rate of reaction in

the forward direction and the rate in
the reverse direction are equal

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 An Equilibrium System
CH4(g) + H2O(g)  CO(g) + 3H2 (g)


 After some of the products are created, the

products begin to react to form the reactants.
 At equilibrium there is no net change in the
concentrations of the reactants and products.
 The concentrations do not change but they are
not necessarily equal.

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 Dynamic Equilibrium

 At equilibrium two opposing

processes are taking place at
equal rates.
 In other words the rate in the
forward direction = the rate in
the reverse direction
 Examples
H2O (l)  H2O (g)
H2O
NaCl (s)  NaCl (aq)


CO (g) + 2 H2 (g)  CH3OH (g)


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Equilibrium Conditions

H2O + CO  H2 + CO2


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Concentration vs time
Characteristics of Dynamic
Chemical Equilibrium
Characteristics of the equilibrium state
Feature Explanation

Dynamic The rxn has not stopped; the forward

and backward rxns are still occurring
(same rate).
Characteristics of the equilibrium state
Feature Explanation

Achieved in Prevents exchange of matter with

surroundings, so equilibrium is
a closed achieved where both reactants and
system products can react and recombine
with each other.
 Characteristics of the equilibrium state
Feature Explanation
Concentrations They are being produced and
destroyed at an equal rate.
of reactants
and products
remain
constant
Characteristics of the equilibrium state
Feature Explanation

No change This refers to observable properties

such as color and density; these do not
in change as they depend on the
macroscopic concentrations of the components in
the mixture.
properties
Characteristics of the equilibrium state
Feature Explanation

Can be The same equilibrium mixture will

result under the same conditions, no
reached matter whether the rxn is started with
from either all reactants, all products, or a
mixture of both.
direction
 Law of Mass Action

 Given the reaction

aA + bB  cC + dD
The rate in the forward direction is
rate forward = kf [A]a [B]b
The rate in the reverse direction is
rate reverse = kr [C]c [D]d

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 Law of Mass Action
 At equilibrium these rates are equal
rate forward = rate reverse
kf [A]a [B]b = kr [C]c [D]d

 The ratio of the rate constants is

Kc = [C]c [D]d
[A]a [B]b
kc is a measure of the extent to which a reaction occurs; it
varies with temperature (and only with temp) and is
UNITLESS.
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Writing Equilibrium Expressions

 N2 (g) + 3 H2 (g)  2NH3 (g)



 2 SO2 (g) + O2 (g)  2SO3 (g)



 H2 (g) + Br2 (g)  2 HBr(g)



 2N2O (g)  2 N2 (g) + O2 (g)


 Answers
Check your work against the following:

[NH3]2
1. Keq =
[N2] [H2]3

[SO3]2
2. Keq =
[SO2]2 [O2]

3. Keq = [HBr]2
[H2] [Br2]

[N2 ]2 [O2]
4. Keq =
[N2O]2
H2(g) + I2(g) ↔ 2HI(g)
If we carry a couple of different experiments we
obtain Initial concent Equilibrium
(mol/dm3) concent
(mol/dm3)
Experiment1 H2 0.1 0.022
I2 0.1 0.022
HI 0.1 0.156

Experiment2 H2 0.0 0.035

I2 0.01 0.045
HI 0.35 0.28

Experiment3 H2 0.015 0.015

I2 0.0 0.0135
HI 0.127 0.1
Experiment 1: Kc= (0.156)2/(0.022x0.022)=50.3

Experiment 2: Kc= (0.28)2/(0.035x0.045)=49.8

Experiment 3: Kc= (0.1)2/(0.015x0.0135)=49.4

 Different designations of
equilibrium constants

 Keq General designation for an equilibrium constant

 Kc Equilibrium constant based on concentration
 Kp Equilibrium constant based on pressure (gases)
 Ksp Solubility product
 Ka Acid equilibrium constant
 Kb Base equilibrium constant
 Kw Ion product of water
 The Meaning of the
Equilibrium Constant

 K>>1: The reaction is product-favored;

equilibrium concentrations of products
are greater than equilibrium
concentrations of reactants.
 K<<1: The reaction is reactant-favored;
equilibrium concentrations of reactants
are greater than equilibrium
concentrations of products.
 Calculating
Equilibrium Constants
Nitrogen dioxide decomposes at high temperatures
according to this equation:
2 NO2 (g)  2 NO (g) + O2 (g)
If the equilibrium concentrations are as follows:
[NO2]= 1.20 M, [NO] = 0.160 M, and [O2] = 0.080 M;
calculate the equilibrium constant.

[NO]2 [O2]
Keq =
[NO2] 2

(0.160)2 (0.080)
So Keq = = 0.0014
(1.20)2
 Calculating
Equilibrium Constants
The equilibrium equation for the oxidation of sulfur
dioxide is as follows:
2SO2 (g) + O2 (g)  2 SO3 (g)
If the equilibrium concentrations are as follows:
[SO2 ]= 0.44 M, [O2] = 0.22 M, and [SO3] = 0.78 M ,
Calculate the equilibrium constant

Keq= [SO3]2
[SO2]2 [O2]
(0.78)2
So Keq = = 14.3
(0.44)2 (0.22)
 Practice Problem 1
The equilibrium equation for the carbon monoxide with
steam to produce hydrogen gas is as follows:
CO2 (g) + H 2 (g)  CO (g) + H2O (g)
If the equilibrium concentrations are as follows: [CO] = 1.00
M, [H2O] = 0.025, [CO2] = 0.075 M and [H2] = 0.060 M,
calculate the equilibrium constant.
[CO] [H2O]
Keq =
[CO2] [H2]

(1.00) (0.025)
So Keq = = 5.56
(0.075) (0.060)
 Reaction Quotient
 The equilibrium constant is a constant
ratio only when the system is in
equilibrium.
 If the system is not at equilibrium the ratio
is known as a Reaction Quotient
 If the reaction quotient is equal to the
equilibrium constant then the system is at
equilibrium
 Combining equilibrium
constants
Change in Equilibrium Equilibrium
reaction constant constant
equation expression
reverse the reaction inverse the 1/Kc
expression
halve the coefficients square root of Sqrt(Kc)
expression
double the square the Kc2
coefficients expression
sum equation product of Kc= Kc1 x Kc2 x …
expressions
 Le Châtellier’s Principle
When a system in
chemical equilibrium is
disturbed by a change of
temperature, pressure, or
a concentration, the
system shifts in
equilibrium composition
in a way that tends to
counteract this change of
variable.
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 Translated:

 The system undergoes a temporary shift in order to

restore equilibrium.

 1. When you add a substance or heat, the system shifts

to the opposite side.

 2. When you take out a substance or heat, the system

shifts to the side of the take out.

3. When you increase pressure, the system shifts to the

side with the least number of gaseous molecules.
 LeChatelier Example #1
A closed container of ice and water is at
equilibrium. Then, the temperature is
raised.

 Ice + Energy  Water

 The system temporarily shifts to the
___right____ to restore equilibrium.
 LeChatelier Example #2
A closed container of N2O4 and NO2 is at
equilibrium. NO2 is added to the container.

 N2O4 (g) + Energy  2 NO2 (g)

 The system temporarily shifts to the
__left_____ to restore equilibrium.
 LeChatelier Example #3
A closed container of water and its vapor
is at equilibrium. Vapor is removed from
the system.
 water + Energy  vapor

 Thesystem temporarily shifts to the

___right____ to restore equilibrium.
 LeChatelier Example #4
A closed container of N2O4 and NO2 is at
equilibrium. The pressure is increased.

 N2O4 (g) + Energy  2 NO2 (g)

 The system temporarily shifts to the
__left_____ to restore equilibrium,
because there are fewer moles of gas on
that side of the equation.
 Industrial Applications
 ***Remember the only thing that can
change the value of Kc is a change in
temperature.
 In reactions involving the manufacture of a
chemical, the goal is to obtain the highest
yield possible.
 We use our knowledge of Le Chatelier’s
principle and kinetics to maximize the yield.
 Applications of
Le Chatelier’s Principle
N2 (g) +3 H2 (g)  2NH3 (g) ∆H = -92 kJ

Haber’s process for the production of ammonia is an

example of an industrial equilibrium system.

• Change in the concentration of one of the components

• Changes in pressure
• Changes in temperature
• Use of a catalyst

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 Haber process: production of ammonia
 The commercial synthesis of ammonia began with the necessities of
war. In the early years of the 20th century, Germany was bringing critical
war materials from abroad. The most important of these resources was
quano, manure from seagulls that roosted along the coast of Chile, rich
in nitrates and the basis of the German manufacture of explosives. It had
to be shipped by the tanker-load across the Atlantic and past patrolling
British warships.
 German chemists Fritz Haber and Walther Bosch found that it was
possible to produce ammonia from nitrogen and hydrogen
 The secret to the Haber-Bosch process proved to be a catalyst of
iron with a small amount of aluminium added
 Haber received the Nobel prize in 1918 for his ammonia process and
'contributions to agriculture', but because of his association with
chemical weapons, there were many objections to him receiving the
prize
 Applications of
Le Chatelier’s Principle

N2 (g) +3 H2 (g)  2NH3 (g) ∆H = - 92 kJ

The equilibrium constant for this reaction is
[NH3]2
Keq = [N2] [H2]3

Any change in the concentration (or partial pressure)

of any component will cause the equilibrium to shift in
such a way so as to return the equilibrium constant to
its original value.

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Kc will not change its value, although concentrations in new
equilibrium change.
Kc ONLY changes with temperature!!
 The Concentration Effect

N2 (g) +3 H2 (g)  2NH3 (g) ∆H = - 92 kJ

[NH3]2
Keq = [N2] [H2]3

An increase in the concentration of N2 results in

an increase in NH3 in such a way to keep the
equilibrium constant the same
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 The Temperature Effect

N2 (g) +3 H2 (g)  2NH3 (g) ∆H = - 92 kJ

 The reaction is exothermic in the forward

direction.
 An increase in the temperature would trigger a
response in the heat consuming (endothermic)
direction.
 An increase in temperature therefore causes the
reaction to shift in the reverse direction. Some
NH3 decomposes to N2 and H2.

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 The Pressure Effect

N2 (g) +3 H2 (g)  2NH3 (g) ∆H = - 92 kJ

 All molecules in the equilibrium are gases

 When the reaction proceeds in the forward
direction the number of moles are reduced from
4 to 2.
 Pressure is proportional to the number of moles
of gas
 An increase in pressure therefore causes the
reaction to move in the direction with the least
number of gaseous moles. Some N2 and H2
combine to form more NH3
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 The Effect of Catalysts

N2 (g) +3 H2 (g)  2NH3 (g) ∆H = - 92 kJ

 Catalysts lower the activation energy

 A catalyst affects the forward and the reverse
direction equally
 There is no change in the equilibrium position
from a catalyst
 A catalyst decreases the time required for the
system to achieve equilibrium

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 Contact Process
 Series of 3 simple reactions
 Combustion of sulfur to sulfur dioxide
 Oxidation of sulfur dioxide to sulfur trioxide

2SO2(g) + O2 (g) ⇔ 2 SO3(g) ∆H = -196kJ/mol

 Combination of sulfur trioxide with water to

produce sulfuric acid

 Catalyst used vanadium (V) oxide
 T= 450C
 P= 2 x 105 Pa
 Production of methanol
CO2(g) + 2H2 (g) ⇔ CH3OH(g) ∆H = -90kJ/mol

P= 5 to 10x106 Pa
T=250C
Catalyst= Cu – Zn – Al2O3
Calculating Equilibrium
Concentrations
Equilibrium Calculations –Using
I. C. E. Model
Equilibrium constants and
concentrations can often be deduced
by carefully examining data about the
initial and equilibrium concentrations

Initial Change Equilibrium

 Equilibrium Calculations
ICE Model problem 1

Hydrogen and iodine are in equilibrium with Hydrogen

iodide to this reaction:
H2 + I2  2HI
Suppose that 1.5 mole of H2 and 1.2 mole of I2 are
placed in a 1.0 dm3 container. At equilibrium it was
found that there were 0.4 mole of HI. Calculate the
equilibrium concentrations of [H2] and [I2] and the
equilibrium constant.

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 Equilibrium Calculations
ICE Model Problem 1 -- Solution
Hydrogen and iodine are in equilibrium with Hydrogen
iodide to this reaction:
H2 + I2  2HI
Suppose that 1.5 mole of H2 and 1.2 mole of I2 are placed
in a 1.0 dm3 container. At equilibrium it was found that
there were 0.4 mole of HI. Calculate the equilibrium
concentrations of [H2] and [I2] and the equilibrium
constant.
[H2] [I2 ] [HI]
Since 2x = 0.4, x = 0.2
Initial 1.5 1.2 0 H2 = 1.5 – 0.2 = 1.3
I2 = 1.2 – 0.2 = 1.0
Change -x -x + 2x

Equilibrium 1.5-x 1.2-x 0.4

Keq = [HI]2 = (0.4)2 = 0.123

[H2 ] [ I2 ] (1.3) (1.0)
 Equilibrium Calculations
ICE Model Problem 2
Sulfur dioxide reacts with oxygen to produce sulfur
trioxide according to this reaction:
2 SO2 + O2  2SO3
Suppose that 1.4 mole of SO2 and 0.8 mole of O2 are
placed in a 2.0 dm3 container. At equilibrium it was
found that there were 0.6 mole of SO3. Calculate the
equilibrium concentrations of [SO2] and [O2] and the
equilibrium constant.

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 Equilibrium Calculations
ICE Model Problem 2 - Solution
Sulfur dioxide reacts with oxygen to produce sulfur
trioxide according to this reaction:
2 SO2 + O2  2SO3
Suppose that 1.4 mole of SO2 and 0.8 mole of O2 are
placed in a 2.0 dm3 container. At equilibrium it was found
that there were 0.6 mole of SO3. Calculate the equilibrium
concentrations of [SO2] and [O2] and the equilibrium
constant. [SO2 ] [O2 ] [SO3]
Initial 1.4 0.8 0
Change - 2x -x + 2x Since 2x = 0.6, x = 0.3
[SO2 ] =1.4 – 2( 0.3) = 0.8
Equilibrium 1.4-2x 0.80-x 0.6 [O2 ] = 0.8 – 0.3 = 0.5

Keq = [SO3]2 = (0.6/2)2 =

[SO2 ]2 [O2 ] (0.8/2)2(0.5/2) 52
Calculating Equilibrium Concentrations
from Keq
What is the concentration for each substance at equilibrium
for the following gaseous reaction
C2H6  C2H4 + H2 KC = 1.01
if the initial concentration of ethene, C2H4 and that of
hydrogen are both 0.300 M? [0.300-x][0.300-x]
[C2H4] [H2] 1.01 =
Keq = [x]
[C2H6] 1.01x = 0.09 - 0.6x +x2
x2 - 1.61x +0.09 = 0
C 2H 4 H2 C 2H 6
x = 1.61+ (1.61)2-4(1)(0.09)
Initial 0.300 0.300 0 2(1)
x = 0.0580 and 1.552. The
Change -x -x +x second root is extraneous.
so [C2H6] = 0.0580
Equilibrium 0.300-x 0.300-x x and [H2 ] = [C2H4] = 0.242
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 Gibbs Free Energy

▶Gibbs free energy describes the spontaneity

and temperature dependence of a reaction

▶The free energy will change as reactants are converted

into products

▶The reaction will be spontaneous in the direction

that results in a decrease in free energy (or in the
direction in which the free energy value becomes
more negative)
 Gibbs Free Energy
Gibbs free energy is a measure of the work available from a system
ΔG = G products – G reactants
Equilibrium Constant Description Gibbs Free Energy Change

K=1 At equilibrium; neither reactants ΔGº =0

or products favored

K>1 Products favored ΔGº <0 (negative value)

K<1 Reactants favored ΔGº >0 (positive value)

▶ A negative ΔG indicates the reaction is spontaneous and the

equilibrium concentrations of the products are larger than the
equilibrium concentrations of the reactants.
Gibbs Free Energy

ΔGº =ΔH º -TΔS º

ΔG - ΔG º reactants =ΔGº
º products

ΔG º =-RT lnK
 Example
Consider H2+I2 ⇄ 2HI. Given that the value of ΔG º at 298K for this reaction
is
+1.3 kJ mol-1, calculate the value of the equilibrium constant.
ΔG º =-R T lnK *R has units of JK-1 the value of ΔG must be converted into J
ΔG º =1300 J mol-1 mol-1

1300 = -8.31 x 298 x lnK

Ln K = -1300 = -0.525
8.31 x 298
Inverse function for lnx is
ex e-0.525 The equilibrium constant is less than 1, which implies that the position of
K=
lies closer to reactants than products, which is also consistent with value of
equilibrium
K= 0.59
ΔG being positive
 ∆𝐺𝐺° = −𝑅𝑅T lnK

Example:
The esterification reaction that produces ethyl
ethanoate has a free energy change
∆𝐺𝐺° =-4.38kJ/mol
Calculate value of equilibrium constant at 298K

∆𝐺𝐺°= -4.38 x 1000 J/mol= -(8.31 J/K.mol) x (298K) x lnKc

lnKc = -4380/2478 = 1.77
Kc= e1.77 = 5.9