Lecture

Chemical Equilibrium

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 Learning objectives

• Nature of Chemical Equilibrium

• Meaning of K
• Relationship between Equilibrium
Expressions

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 Equilibrium
We’ve already used the phrase “equilibrium”
when talking about reactions.

In principle, every chemical reaction is

reversible ... capable of moving in the
forward or backward direction.
2 H2 + O 2 2 H2O

Some reactions are easily reversible ...

Some not so easy ...
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The Concept of Equilibrium
• Consider colorless frozen N2O4. At room temperature, it
decomposes to brown NO2:
N2O4(s)  2NO2(g).
• At some time, the color stops changing and we have a mixture
of N2O4 and NO2.
• Chemical equilibrium is the point at which the rate of the
forward reaction is equal to the rate of the reverse reaction.
At that point, the concentrations of all species are constant.
• Using the collision model:
– as the amount of NO2 builds up, there is a chance that two
NO2 molecules will collide to form N2O4.
– At the beginning of the reaction, there is no NO2 so the
reverse reaction (2NO2(g)  N2O4(g)) does not occur. 4
The Concept of Equilibrium
• As the substance warms it begins to decompose:
N2O4(g)  2NO2(g)
• When enough NO2 is formed, it can react to form
N2O4:
2NO2(g)  N2O4(g).
• At equilibrium, as much N2O4 reacts to form NO2 as
NO2 reacts to re-form N2O4

• The double arrow implies the process is dynamic.

N2O4(g) 2NO2(g)

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 N2O4(g) 2NO2(g)

A reversible reaction can proceed in both the forward

and backward directions.

Equilibrium is when the rate of the forward

reaction equals the rate of the reverse reaction.
All reactant and product concentrations are 6
constant at equilibrium.
 Chemical Equilibrium
• At chemical equilibrium, no net change
occurs in the actual amounts of the
components of the system
• When the rates of the forward and reverse
reactions ae equal the reaction has
reached a state of balance called chemical
equilibrium

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The Equilibrium Constant
• No matter the starting composition of reactants and
products, the same ratio of concentrations is achieved
at equilibrium.
• For a general reaction
aA + bB(g) pP + qQ
the equilibrium constant expression is
p
P  Qq
Kc 
a
A Bb
where Kc is the equilibrium constant.

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The Equilibrium Constant
• Note that the equilibrium constant expression
has products over reactants.
• We generally omit the units of the equilibrium
constant.
• Kc is based on the molarities of reactants and
products at equilibrium.
• Kp is based on partial pressures of reactants and
products at equilibrium
p 
PP  PQ q
KP 
a
PA  PB b
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What does K mean?

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The Equilibrium Constant
The Magnitude of Equilibrium Constants
• The equilibrium constant, K, is the ratio of products
to reactants.
• Therefore, the larger K the more products are present
at equilibrium.
• Conversely, the smaller K the more reactants are
present at equilibrium.
• If K >> 1, then products dominate at equilibrium and
equilibrium lies to the right.
• If K << 1, then reactants dominate at equilibrium and
the equilibrium lies to the left.
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The Equilibrium Constant
The Magnitude of Equilibrium Constants
• An equilibrium can be approached from any
direction.
Example:
N2O4(g) 2NO2(g)

 NO 2 2
Kc  0.212
N 2 O 4 

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 Gibbs Free Energy (∆G)
∆G : free energy transfer of system as work
–∆G : work done by system (–w) favorably
+∆G : work done on system (+w) to cause rxn
(not react to
completion)
+DG
–DG

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 Relationship among
equilibrium expressions

The equilibrium constant for a net reaction made up of

two or more steps is the product of the equilibrium
constants for the individual steps.

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 Equilibrium constant, Kc
(Keq or K)
• Always products divided by reactants.
• All concentrations are equilibrium values.
• Each concentration is raised to its stoichiometric
coefficient.
• Kc depends on the rate constants which in turn
depend on the reaction (Ea) and temperature.
• No units on Kc.
• Pure solids and pure liquids are excluded from Kc.
• A catalyst does not change the equilibrium
concentrations, so it does not change Kc. 16
 Finding the Equilibrium constant
using
Write the equation for the
ICE table
REACTION, and use it as a guide
to prepare the Initial, Change and
Equilibrium (ICE) table. [H2] [I2] [HI]
initial ≈0
Complete the ICE table based on change
the given information. Keep in equilibrium
mind the reaction stoichiometry
for the change line.
because no products initially,
Qc = 0, and the reaction is
Substitute the expressions for
proceeding forward
equilibrium concentrations into the
K expression.

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calculated value of K
A closed system initially containing 1.000 x 10-3 M H2 and
2.000 x 10-3 M I2 at 448˚C is allowed to reach equilibrium.
Analysis of the equilibrium mixture shows that the
concentration of HI is 1.87 x 10-3 M. Calculate Kc at 448 ˚C for
the reaction taking place, which is

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Ammonia made as given in equation Assume initial concertation of and
are 0.100 moles/L at 500 ˚C. Calculate equilibrium concentration of the
three components of this reaction if Kc =0.040 at 500 ˚C.
𝑁 2 ( 𝑔 ) +3 𝐻 2 ( 𝑔 ) ↔ 2 𝑁𝐻 3 (𝑔)
represent the change in the
concentrations in terms of x ,M ,M ,M
substitute x into the equilibrium initial 0.100 0.100 0
concentration definitions and solve
for Kc change -x -3x +2x

𝐾 𝑐 =¿ ¿ ¿
equilibrium 0.100-x 0.100-3x 2x
2
2𝑥
𝐾 𝑐=
because Kc is very small, ( 0.100 − 𝑥 ) ¿ ¿
approximate the [H2]eq = [H2]init
and solve for x

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 Solving for x gives 𝑁 2 ( 𝑔 ) +3 𝐻 2 ( 𝑔 ) ↔ 2 𝑁𝐻 3 (𝑔)

x
,M ,M ,M

Check our assumptions: 5% initial 0.100 0.100 0

rule change -x -3x +2x
.001 ×100 % /0.100=1 %
equilibrium 0.100-x 0.100-3x 2x
3 (0.001)× 100 % /0.100=3 %
So our assumption is valid Equilibrium concentrations are:
]=2x = 0.0020 M
If not Quadratic equation is
[] = 0.100 –x = 0.099 M
used.
[] = 0.100 –3x = 0.097 M

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 Relating Kp with Kc

• From ideal gas equation

• For the gas phase reaction

Where
• Relation between Kp and Kc
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The equilibrium constant for the reaction of nitrogen and hydrogen to give ammonia is 0.118 at 745 K. The balanced
equilibrium equation is:

What is Kp for this reaction at the same temperature?

Given: Kc= 0.118 at 745 K

Find: Kp
Conceptual
Plan: Dn Kp

Relationships:
Solution:
𝐾 𝑝 =𝐾 𝑐 ¿ Δn = (2 − 4)
= −2

Check: Kc relationship to Kp
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 For the synthesis of ammonia at 500˚C, the
equilibrium constant is 6.0 x 10 -2. Predict the
direction in which the system will shift to
reach the equilibrium .
Given • [NH3]0 = 1.0 x 10-3 M
• [N2]0 = 1.0 x 10-5 M
• [H2]0 = 2.0 x 10 -3 M

Q= 1.2 x 104 >> K= 6.0 x 10 -2

For the system to attain equilibrium, the concentration of the
products must be
decreased and the concentration of the reactants increased.
The system will shift to the left 28
 Principle of Le Châtelier
• A change in one of the variables that describe
a system at equilibrium produces a shift in the
position of the equilibrium that counteracts the
effects of this change.
 Principle of Le Châtelier
• A system in equilibrium that is
subjected to stress will react in a way
that tends to minimize the effect of the
stress.
• If the system at equilibrium is
subjected to a change of concentration
or temperature or pressure, the
system adjusts itself in such a way as to
annual the effect of that change i.e., the
effect of these changes can be
neglected or minimized. 30
Adding reagents

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Removing reagents

Remove
Product

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Reaction at equilibrium

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Adding reactants/products

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Removing reactants/products

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 Change in Volume

Changing the volume of a gas mixture at

equilibrium will change the concentrations of
gases in the mixture, upsetting the
equilibrium.

• Decreasing the mixture volume will increase the

concentration of gases.
• Increasing the mixture volume will decrease the
concentration of gases.

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Effect of Volume Change
Decreasing the volume of the Boyle's law is a gas law,
gas mixture shifts the stating that
the pressure and volume of
equilibrium towards the a gas have an
fewer number of moles. inverse relationship.
If volume increases,
Increasing the volume of the then pressure decreases and
vice versa, when temperature
gas mixture shifts the is held constant.
equilibrium toward the larger
number of moles.
 Pressure – the
number of gas
particles
colliding with
the walls of
the container

• CHANGING THE VOLUME A decrease in the volume of a

gaseous system causes an increase in the total pressure. Le
Châtelier's principle predicts that the system would respond, if
possible, in such a way as to reduce the total pressure.
• A decrease in volume shifts the reaction to the right (toward
product)
• An increase in Volume shifts the reaction to the left (toward
reactant) 38
Exothermic reaction

heat is a produc

heat is a reactan
Endothermic Reaction

heat is a reactan
\\\\\\

heat is a product
 Temperature and reactions
• Every chemical reaction is either exothermic or
endothermic

• Le Châtelier’s Principle states that if heat is

added to an equilibrium system, the
equilibrium shifts in the direction in which
heat is used up
• If heat is taken away from a system,
equilibrium shifts in the direction in which
heat is produced
 ΔH is the predictive tool

If heat is added, which direction will the

reaction go?
 Temperature Change and
Exothermic Reactions
For an exothermic reaction at equilibrium,
• an increase in temperature adds heat and
the equilibrium shifts toward the reactants.
• a decrease in temperature (T) removes
heat and the equilibrium shifts toward the
products.
 Temperature Change and
Endothermic Reactions
For an endothermic reaction at equilibrium,
heat is a
reactant.
• A decrease in temperature (T) removes heat,
shifting the equilibrium toward the reactants.
• An increase in temperature adds heat,
shifting the equilibrium toward the products.
 Problem
Indicate if each change on a reaction at equilibrium shifts

towards the products or reactants or does not change the equilibrium

1. adding NO(g)
The equilibrium shifts toward reactants.
2. raising the temperature
The equilibrium shifts toward products.
3. increasing the volume
The equilibrium shifts toward products.
The End

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