Reactivity 2.

3
How far? The extent of chemical change

Reactivity 2.3
2.3.1 dynamic equilibrium
2.3.2 equilibrium law
2.3.3 magnitude of equilibrium
2.3.4 Le Châtelier’s principle Standard Level
 UNDERSTANDING 2.3.1

A state of dynamic equilibrium is

reached in a closed system when
the rates of forward and backward
reactions are equal.
• The system is at equilibrium when the
rate of the forward reaction equals the
rate of the reverse reaction and the
concentration of products and
reactants remains unchanged.
• A reversible reaction is a chemical
reaction in which the products can
react to re-form the reactants.
Arrows going both directions (  ) indicates equilibrium in a chemical equation.

2HgO(s)  2Hg(l) + O2(g)

 APPLICATIONS

Be familiar with the characteristics

of chemical and physical systems
in a state of equilibrium.
 EQUILIBRIUM IN
PHYSICAL SYSTEMS
• A physical system is one in which a chemical
reaction is not occurring.
• Equilibrium will only occur in a “closed” system.
• A “closed” system is one in which no matter can
be exchanged with the surroundings.
• A typical example is the evaporation-
condensation cycle of a volatile liquid in a closed
container.
– When the rate of evaporation equals the rate of
condensation, the system is at equilibrium.
 EQUILIBRIUM IN
PHYSICAL SYSTEMS
• When a liquid has reached its boiling point a
significant number of particles will have enough
energy to escape from the liquid state and form
vapour by evaporating.
• At the same time, some of these vapour molecules
will collide with the surface of the liquid, lose energy
and become liquid by condensing.
• There will come a time when the rate of evaporation
is equal to the rate of condensation and at this point
there's no net change in the amounts of liquid and
gas present. The system has reached equilibrium.
 EQUILIBRIUM IN
CHEMICAL SYSTEMS
• A chemical system is one in which a
chemical reaction is occurring.
• For the system to reach equilibrium, the
forward reaction must equal that of the
reverse reaction.
 CHARACTERISTICS OF THE
EQUILIBRIUM STATE
• Equilibrium is dynamic – the reaction has not stopped but
both reactions or processes are still occurring on the
microscopic level even though it looks like the reaction or
process has stopped.

Bromine in a closed system will establish a dynamic equilibrium between

the liquid and gaseous phases. Eventually the colour stops changing as
the equilibrium concentration of vapour is reached
• Equilibrium is achieved in a closed system so that
no matter can escape to the surroundings.

• The concentrations of reactants and products

remain constant at equilibrium – they are being
produced or consumed at an equal rate.

• There is no macroscopic change in properties –

meaning the observable properties do not change
at equilibrium because they depend on the
concentration of the mixture components.
• Equilibrium can be reached from either direction
– meaning that at the same conditions equilibrium
will be reached whether the reaction started with
all reactants, all products or a mixture of both.

• It is important to note that even though the

concentrations of reactants and products are
constant at equilibrium, this does not imply they
are equal.
 Equilibrium Position
• The equilibrium position is the proportion of the
reactants and products in the equilibrium mixture.
• A reaction with an equilibrium mixture with mostly
products is said to “lie to the right”.
• A reaction with an equilibrium mixture with mostly
reactants is said to “lie to the left”.
• We can quantitatively compare equilibrium mixtures
with different conditions by using the equilibrium
constant Kc.
• There can be numerous equilibrium positions, but
only one equilibrium constant, Kc, at a specified
temperature.
 UNDERSTANDING 2.3.2

The equilibrium law describes how

the equilibrium constant (K) can be
determined from the stoichiometry
of a reaction.
 Equilibrium Constant K
For the reaction:

jA + kB  lC + mD
l m
[C ] [ D ]
K= j k
[ A] [ B ]
Where K is the equilibrium constant, and
is unitless. The only thing that can
change K for a reaction is a change in
temperature.
 APPLICATION

Be able to deduce the equilibrium

constant (K) from an equation for a
homogeneous reaction.
Writing an Equilibrium Expression
Write the equilibrium expression for the
reaction:
2NO2(g)  2NO(g) + O2(g)
Remember that concentrations are written with
square brackets [ ]. K is calculated using molar
concentrations. Solids and liquids are not
included in the K expression.
K = ???
2
[ NO ] [ O 2 ]
K= 2
[ NO 2 ]
 GUIDANCE
Be familiar with the relationship
between Kc values for reactions
that are multiples or inverses of
each other.
COMBINING EQUILIBRIUM
CONSTANT
 Conclusions about Equilibrium Expressions
If an equation is written in reverse, the K
expression is the reciprocal of the original K.

2NO2(g)  2NO(g) + O2(g)

2
[ NO ] [ O 2 ]
K= 2
[ NO 2 ]
2NO(g) + O2(g)  2NO2(g)
2
1 [ NO 2 ]
K '= = 2
K [ NO ] [ O 2 ]
 Conclusions about Equilibrium Expressions
When the balanced equation for a reaction is
multiplied by a factor n, the equilibrium
expression for the new reaction is the
original expression, raised to the nth power.
2NO2(g)  2NO(g) + O2(g)
2
[ NO ] [ O 2 ]
K= 2
[ NO 2 ]
NO2(g)  NO(g) + ½O2(g)
1
1 2
[ NO ][O2 ]
K '= K =
2
[ NO2 ]
Try:
Try:
• If you add two reactions together, you will
multiply the two K expressions to obtain
the new K’.
 Practice:
The equilibrium constant for the reaction
between hydrogen and chlorine gas to produce
hydrogen chloride gas is 2.40 x 1033 at 298 K.
H2(g) + Cl2(g) 2HCl(g)
Calculate the equilibrium constant for the
reverse reaction, namely the decomposition of
HCl.
Practice:
The equilibrium constant for the equilibrium
between N2O4 and NO2 is 7.7 x 10-4 at 273 K:
N2O4(g) 2NO2(g)
Calculate the equilibrium constant for
½ N2O4 (g) NO2 (g) at 273 K.
TRY:
 UNDERSTANDING 2.3.3

The magnitude of the equilibrium

constant indicates the extent of a
reaction at equilibrium and is
temperature dependent.
Product Favored Equilibrium
Large values for K signify the reaction is
“product favored”

When equilibrium is achieved, most of

the reactants have been converted to
products.
Reactant Favored Equilibrium
Small values for K signify the reaction is
“reactant favored”

When equilibrium is achieved, very little

reactant has been converted to product.
 APPLICATION

Be able to determine the

relationship between different
equilibrium constants for the same
reaction at the same temperature.
• The equilibrium constant Kc has a fixed
value at the same temperature.
• You can derive Kc from different sets of
data for the same reaction at constant
temperature.
• All Kc values should be equal no matter
how you arrived at the value since only
temperature affects Kc.
 UNDERSTANDING 2.3.4
Le Châtelier’s principle enables the
prediction of the qualitative effects of
changes in concentration, temperature
and pressure to a system equilibrium.
 LeChâtelier’s Principle
When a system at equilibrium is placed under stress,
the system will undergo a change in such a way as
to relieve that stress.
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.
 LeChâtelier’s 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.
_______
 LeChâtelier’s 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.
 LeChâtelier’s Example #3
A closed container of water and its vapor is at
equilibrium. Vapor is removed from the system.

water + Energy  vapor

The system temporarily shifts to the

right to restore equilibrium.
_______
 LeChâtelier’s 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.
 Le Châtelier’s Principle

• Changes in Concentration

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
 Le Châtelier’s Principle

• 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
A catalyst has no effect on the
position of equilibrium or the
equilibrium constant.
 ADDITION OF A CATALYST
• When a catalyst is added, both the rate of
the forward and the rate of the reverse
reactions are increased by the same
amount so there is no effect on the
equilibrium position.
• It only speeds up how fast Kc is achieved.
 Le Châtelier’s Principle
• Adding a Catalyst
• does not change K
• does not shift the position of an equilibrium system
• system will reach equilibrium sooner

uncatalyzed catalyzed

Catalyst lowers Ea for both forward and reverse reactions.

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

• Changes in Temperature

Change Exothermic Rx Endothermic Rx

Increase temperature K decreases K increases
Decrease temperature K increases K decreases

colder hotter
Effect of Temperature Changes
•The equilibrium constant is temperature
dependent.

•For an endothermic reaction, H > 0 and heat

can be considered as a reactant.

•For an exothermic reaction, H < 0 and heat

can be considered as a product.
Case study: 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.
 HABER PROCESS: Production of NH3
• N2(g) + 3H2(g)  2NH3(g) ∆H = -93 kJ/mol
• First we need to get information from the
balanced equation.
– All products and reactants are in the gaseous
state with 4 moles on the left and 2 on the
right.
– The reaction is exothermic so we want to re-
write the equation as:
– N2(g) + 3H2(g)  2NH3(g) + heat
 N2(g) + 3H2(g)  2NH3(g) + heat
• To maximize the amount of NH3 obtained we can do several
things:
– Remove NH3 as it is produced so the reaction will
continue to the right producing more NH3 to achieve
equilibrium.
– Increasing the pressure pushes the equilibrium to the side
of the least gaseous molecules which is to the right;
therefore, producing more NH3.
– We want a lower temperature since the reaction is
exothermic, but not too low which would slow things down
too far.
– Adding a catalyst (iron) will speed up the reaction and
compensate for the lower temperature.
 Optimum Conditions
• Optimum temperature used: 450oC
• Optimum pressure used: 200 atm
• Why the optimum conditions are used in
industry ?
 Citations
Bylikin S., Horner G., Grant E.J.,, Tarcy., Chemistry Course Companion
edition 2023

Bylikin Sergey, Horner Gary, Murphy Brian, and Tarcy David. Chemistry
2014 edition

International Baccalaureate Organization. Chemistry Guide, First

assessment 2016. Updated 2015.

Brown, Catrin, and Mike Ford. Higher Level Chemistry. 2nd ed. N.p.:
Pearson Baccalaureate, 2014. Print.
ISBN 978 1 447 95975 5
eBook 978 1 447 95976 2