Equilibrium

Topic 7
Topics:
● Dynamic Equilibrium
● Le Chatelier’s Principle
● Measuring an Equilibrium Constant
● Equilibrium and Industry
● Gibbs Free Energy and Equilibrium – HL

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Dynamic Equilibrium

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We Are Here

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 Dynamic Equilibrium

● Objectives:

● Outline the characteristics of a system under dynamic

equilibrium

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 Writing equilibrium equations
● Reversible reactions are written using a double arrow
● Each of the arrows only has a single-sided head

REACTANTS PRODUCTS

● The unit will make a lot of reference to the rate of the:

● ‘forward reaction’ (reactants becoming products)
● ‘back reaction’ (products becoming reactants)

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 At dynamic equilibrium….
● 1. The concentration of
reactants and products is
constant
● They are NOT equal to each
other
● They are just not changing

● 2. The rate of the forward

reaction is equal to the rate
of the back reaction
● At equilibrium these are not
zero…even though it looks
like it on the graph
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 Equilibrium Position
● Even though the concentrations of reactant and product are
constant at equilibrium this does not mean they are equal

● aA + bB ⇌ cC + dD

● If there are more products than reactants at equilibrium

then equilibrium “lies to the right”

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 Why ‘dynamic’ equilibrium?
● The reaction hasn’t stopped, it is
still going, but the rate of the
forward and back reactions are
equal, so there is no overall
change.

● This is different to a static

equilibrium (for example a
see-saw) where there is no
change at all.

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Main
 Characteristics of Equilibria
● 3. At equilibrium there is no
change in macroscopic properties

● Explanation: Observable
properties, like color do not
change

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 Characteristics of Equilibria

● 4. Equilibrium can be reached from either direction

● Explanation: The same equilibrium mixture will result under

the same conditions

● No matter whether the reaction started with all reactants, all

products, or a mixture of both

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Liquid-vapor equilibrium

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 Dynamic Equilibrium
● Consider what happens
when bromine is placed in
a sealed container at room
temperature

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 Dynamic Equilibrium
● Br2(l) ⇌ Br2(g)
If we start with Br2(l) and we leave
the bottle for a while, some of the
liquid will evaporate to form Br2(g).

This occurs at rtp, what does this

tell us about the types of bonds/
IMFs in Br2(g)?

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 Dynamic Equilibrium
● At some point in time there
will be no net change in the
amount of liquid and gas
present

● Then the system will be at

equilibrium

● Rate of evaporation= Rate

of condensation

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● As water evaporates from your skin
● The water molecules with the highest energy
evaporate first
● Average kinetic energy of the molecules that are left
is less
● You feel cooler!
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Main
 Enthalpy of vaporization
● The energy required to convert one mole of substance
from its liquid state into one mole of gas at 298 K

● Vaporization is always endothermic

● Why?
● Condensation is always exothermic
● Why?

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 Increasing temperature?
● Increases evaporation

● Liquid ⇌ Vapor
● More liquid turns into vapor so equilibrium shifts to the
right

● The pressure from the vapor increases

● More moles of particles will be in the gas phase

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 VAPOR Pressure

● Why does food take a longer time to cook at a higher

altitude?

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● Substances with
high vapor
pressure have
low boiling points

● Volatile

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 Equilibrium Constant, Kc
● aA + bB ⇌ cC + dD

● Kc= [C]c[D]d
[A]a[B]b
Every reaction has its own Kc and it is a fixed value at a specific
temperature
● Different reactions have different Kc values.
● What does Kc tell us?

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 The equilibrium constant, Kc
● The equilibrium constant describes where the position
of equilibrium lies:
● Minimum: 0, maximum: ∞, half-way: 1
● Greater than 1: products favoured
● Less than 1: reactants favoured

● For the reaction:

wA + xB ⇌ yC + zD

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 Key Points:
● At dynamic equilibrium:
● Concentrations of reactants and products are constant
● The rate of the forward and backward reactions are equal

● The position of an equilibrium is given by Kc

● Kc > 1 means products are favoured

● Kc < 1 means reactants are favoured

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Le Chatelier’s Principle

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We Are Here

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 Le Chatelier’s Principle

● Objectives:

● Understand the impact of Le Chatelier’s Principle

● Use Le Chatelier’s Principle to explain the effect of

changes on a system at equilibrium

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 Le Chatelier’s Principle
● This describes how a dynamic chemical equilibrium responds to
disturbances
● https://phet.colorado.edu/en/simulation/reversible-reactions

‘A system at equilibrium responds to disturbances in such a way as to

minimise that disturbance’

● This applies to changes in:

● Concentration
● Pressure
● Temperature

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 Disrupted Equilibrium
Whenever a system is at equilibrium, and we change
something, the system tries to negate what we did.

Add something…the system will react to remove it

Decrease the no. of moles of a reactant and the system tries to

increase the no. of moles of that reactant.

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 Changes in Concentration
● aA + bB ⇌ cC + dD

● Applying Le Chatelier’s principle, what concentration

changes would cause the equilibrium to shift to the left?

Increase the concentration of a product

OR
Decrease the concentration of a reactant

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 Changes in Concentration
● Decrease in [Reactant] or increase in [Product]
● Equilibrium shifts to the left
● This has the effect of increasing [Reactant] and decreasing [Product]

● Increase in [Reactant] or decrease in [Product]

● Equilibrium shifts to the right
● This has the effect of decreasing [Reactant] and increasing [Product]

● Equilibrium constant is not affected

Ethanol + Ethanoic Acid ⇌ Ethyl ethanoate + water

CH3CH2OH(aq) + CH3CO2H(aq) ⇌ CH3CH2OOCCH3(aq) + H2O(l)

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FACTORS AFFECTING THE POSITION OF EQUILIBRIUM
SUMMARY

REACTANTS PRODUCTS

THE EFFECT OF CHANGING THE CONCENTRATION ON THE POSITION OF EQUILIBRIUM

INCREASE CONCENTRATION OF A REACTANT EQUILIBRIUM MOVES TO THE RIGHT

DECREASE CONCENTRATION OF A REACTANT EQUILIBRIUM MOVES TO THE LEFT

INCREASE CONCENTRATION OF A PRODUCT EQUILIBRIUM MOVES TO THE LEFT

DECREASE CONCENTRATION OF A PRODUCT EQUILIBRIUM MOVES TO THE RIGHT

 Changes in Pressure
● Increasing Pressure:
● Shifts equilibrium to the side with fewest gas molecules
● This has the effect of reducing the pressure increase

● Decreasing Pressure:
● Shifts equilibrium to the side with more gas molecules
● This has the effect of increasing the pressure

● Equilibrium constant is not affected

2N2(g) + 3H2(g) ⇌ 2NH3(g) ΔH = -91.8 kJ mol-1

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 PRESSURE
SUMMARY

THE EFFECT OF PRESSURE ON THE POSITION OF EQUILIBRIUM

INCREASE PRESSURE MOVES TO THE SIDE WITH FEWER GASEOUS MOLECULES

DECREASE PRESSURE MOVES TO THE SIDE WITH MORE GASEOUS MOLECULES

Kc does not change.

 Changes in Temperature
● 2NO2(g) ⇌ N2O4(g) ΔH=-24 kJ mol-1

● Exothermic or endothermic?

● If temperature decreases, what will happen?

● More product and higher yield

● What might be a disadvantage of the lower temperature?

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 Changes in Temperature
● N2(g) + O2(g) ⇌ 2NO(g) ΔH=+181kJmol

● How would decreased temperature effect Kc?

● At higher temperatures, the forward reaction is favored.

This reaction occurs in motor vehicles.

NO is toxic, it can be a chemical cause of acid rain and smog

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 TEMPERATURE
SUMMARY

• altering the temperature affects the rate of both backward and

forward reactions alters the rates to different extents

• the equilibrium moves producing a new equilibrium constant.

• the direction of movement depends on the sign of the enthalpy

change.

REACTION TYPE ΔΗ INCREASE TEMP DECREASE TEMP

EXOTHERMIC - TO THE LEFT TO THE RIGHT

ENDOTHERMIC + TO THE RIGHT TO THE LEFT

 Addition of a Catalyst
● The catalyst increases the rate of both the forward and the
backwards reactions

● So the catalyst does not effect the position of equilibrium,

or Kc

● Catalysts do not increase the yield of the products

● They just enable equilibrium to be reached more quickly

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Equilibrium and Industry

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 Recap
● A catalyst of iron is used in the Haber process. State and
explain how the catalyst affects Kc and the position of
equilibrium.

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We Are Here

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 Equilibrium and Industry

● Objectives:

● Summarise the impact of equilibrium effects on the Haber

Process and the Contact Process

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 Equilibrium and Industry
● Many industrial processes take advantage of equilibrium effects.

● Two of the most important are:

● Haber process for making ammonia
● Contact process for making sulphuric acid

Look up the Haber and Contact Process

● What are they used for?
● What are the reactions?
● What conditions would give the greatest yield of the product? What
are the conditions are used in industry and why?

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 Fritz Haber
● Born in Poland then went to Germany

● Found a way to synthesize ammonia from elements

● Factory opened 1913, just before WW1

● Enabled production of explosives and chlorine gas which was also used in the war.
He was awarded the Nobel prize for chemistry, this was very controversial and
still is

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 Henri-Louis Le Chatelier
● “I let the discovery of the
ammonia synthesis slip
through my hands. It was
the greatest blunder of my
life.”

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 Haber Process
● N2(g) + 3H2(g) ⇌ 2NH3(g)
● ΔH = -93 kJ mol-1

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 Haber Process
● N2(g) + 3H2(g) ⇌ 2NH3(g) ΔH=-93 kJ mol-1

● How can concentration influence reaction?

● How can pressure influence reaction?
● How can temperature influence reaction?
● Catalyst?

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 Contact process
● Making sulfuric acid involves three reactions
● The combustion of sulfur
● S(s) + O2(g) ⇌ SO2(g)

● The oxidation of sulfur dioxide

● 2SO2(g) + O2(g) ⇌ 2SO3(g)
● And…The combination of sulfur trioxide with water
SO3(g) + H2SO4(l) →H2S2O7(l) + H2O(l) → 2H2SO4(l)
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 Contact process
SO3(g) + H2SO4(l) → H2S2O7(l)

H2S2O7(l) + H2O → 2H2SO4

Summarized as SO3(g) + H2O(l) → H2SO4(l)

Sulfur trioxide is absorbed into a flowing solution of concentrated sulfuric

acid

● Then the product of this reaction reacts with water

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 Contact Process
● The overall rate depends on step 2
● 2SO2(g) + O2(g) ⇌ 2SO3(g) ΔH = -196 kJ mol-1

● How can pressure, temperature and catalyst increase the yield

of this reaction?

● IB Textbook page 190 ex. 7.2 q 1-7, 8e–g, 9,10, 11c, d

● Page 195 ex 17.2 questions 1 - 4
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HL Only

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 Recap
Consider the following equilibrium reaction.

Cl2(g) + SO2(g) ⇌ SO2Cl2(g) ∆H = -84.5 kJ

In a 1.00 dm3 closed container, at 375 °C, 8.60x10–3 mol of

SO2 and 8.60x10–3 mol of Cl2 were introduced. At
equilibrium, 7.65x10–4 mol of SO2Cl2 was formed.

● Determine the value of the equilibrium constant, Kc.

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 ∆𝐺 and Equilibrium
Gibbs free energy change, ∆G, is a measure of the work
that is available from a system

● ∆G* = negative ⇒ reaction proceeds in the forward

direction

● ∆G* = positive ⇒ reaction proceeds in the

backward direction

● ∆G* = 0 ⇒ reaction is at equilibrium

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 ∆𝐺 and Equilibrium
● The position of equilibrium corresponds to a maximum
value of entropy and a minimum in the value of the
Gibbs free energy.

● The Gibbs free energy change of a reaction and the

equilibrium constant can both be used to measure the
position of an equilibrium reaction and are related by
the equation, ∆𝐺 = −𝑅T ln𝐾 .

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● The esterification reaction that produces ethyl ethanoate has a
free energy change ∆G* = –4.38 kJ mol–1.

CH3COOH(aq) + C2H5OH(aq) ⇌ CH3COOC2H5(aq) +H2O(aq)

● Calculate the value of the equilibrium constant of this reaction

at 298 K.

● ∆G* = –RT ln Kc

–4.38 × 1000 J mol–1 = –8.31 J K–1 mol–1 × 298 K × ln Kc

● –4380 J mol–1
ln Kc = 2478 J mol–1 = 1.77

● ∴ Kc = e1.77 = 5.9
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 Questions
1. The value of the equilibrium constant for the reaction

2HI(g) < -- > H2(g) + I2(g)

is 0.25 at 440°C. What would the value of the equilibrium constant be for
the following reaction at the same temperature?

H2(g) + I2(g) < -- > 2HI(g)

A. 0.25 B. 0.50

C. 2.0 D. 4.0

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2.

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4.

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5.

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 Do one of these
● Draw a mind-map, summarising the key detail

Draw a bull’s-eye Draw a connections

diagram Most
important
wheel Stoichiometry

Atomic Periodicit
Structur y
Important e

Kineti
Details
cs

Bondi
Equilibriu ng
m
Energet
ics

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