7 Equilibria (As)

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Equilibria
Learning outcome
Calculate the values of equilibrium constants in terms of concentrations or

partial pressures from appropriate data
Calculate the quantities present at equilibrium, given appropriate data

(such calculations will not require the solving of quadratic equations)
Describe and explain the conditions used in the Haber process and the
Contact process, as examples of the importance of an understanding of
chemical equilibrium in the chemical industry
Show understanding of, and use the Bronsted-Lowry theory of acids and
bases
Explain qualitatively the differences in behaviour between strong and

weak acids and bases and the pH values of their aqueous solutions in
terms of the extent of dissociation
Learning outcome
Explain, in terms of rates of the forward and reverse reactions, what is

meant by a reversible reaction and dynamic equilibrium
State Le Chateliers Principle and apply it to deduce qualitatively (from

appropriate information) the effects of changes in temperature,
concentration or pressure, on a system at equilibrium
Deduce whether changes in concentration, pressure or temperature or the

presence of a catalyst affect the value of the equilibrium constant for a
reaction
Deduce expressions for equilibrium constants in terms of concentrations,

Kc, and partial pressures, Kp
Reversible Reaction
A+BC+D
The reaction is complete and will stop when
one of the reactants is used up.
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Reversible Reaction
Reversible Reaction
A+BC+D
The reaction is incomplete.
The products can react to form reactants.
A mixture of products and reactants is produced.
This is known as reversible reactions;
represented by
Reversible Reactions
Example:
http://www.youtube.com/watch?v=br8lKynV1Hc
Dynamic Equilibrium
Characteristics of an equilibrium (under constant
conditions):
N2(g) + 3H2(g) 2NH3(g)

H2(g) + I2(g) 2HI(g)
CH3COOH(l) + C2H5OH(l) CH3COOC2H5(l) + H2O(l)
An equilibrium is reached when both reactants &
products are present.
1. Dynamic (not static)

2. Rate of forward reaction = rate of backward
reaction
3. [Reactant] & [Products] remains constant at
equilibrium.
4. Closed system
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Dynamic Equilibrium
Dynamic Equilibrium
[A] & [C] plotted against time at constant T:
t1
Dynamic Equilibrium
Equilibrium Constant
H2(g) + I2(g) HI(g)

In four separate experiments at 720 K, chemical equilibrium
was allowed to establish.
In each of the four experiments, the equilibrium
concentration of H2(g), I2(g) and HI(g) were measured.
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Equilibrium concentrations (mol dm-3)

[H2(g)]eqm
[I2(g)]eqm
[HI(g)]eqm
Equilibrium concentrations (mol dm-3)
1.14 x 10-2
0.12 x 10-2
2.52 x 10-2
[H2(g)]eqm
[I2(g)]eqm
[HI(g)]eqm
0.92 x 10-2
0.20 x 10-2
2.96 x 10-2
1.14 x 10-2
0.12 x 10-2
2.52 x 10-2
46.4
10-2
10-2
10-2
10-2
10-2
10-2
47.6
0.34 x
0.86 x 10-2
0.34 x
0.86 x 10-2
2.35 x
5.86 x 10-2
0.92 x
0.20 x
2.96 x
0.34 x 10-2
0.34 x 10-2
2.35 x 10-2
47.8
10-2
10-2
10-2
46.4
0.86 x
0.86 x
5.86 x
Average
47.1
A constant value, within experimental error, is

obtained. (47.1 at 720K)
Kc equilibrium values are expressed as

concentrations (mol dm-3)
The value of this ratio of equilibrium concentrations

(in mol dm-3) is known as the equilibrium constant,
represented by the symbol Kc.
Kp equilibrium values are expressed as partial

pressures (only for gas)
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Equilibrium Constant, Kc
For a system in equilibrium:
aA(g) + bB(g) cC(g) + dD(g)
Equilibrium Constant, Kp
Kp is the equilbirum constant in terms of partial
pressures.
Only applies on to gas reactions.
aA(g) + bB(g) cC(g) + dD(g)
The equilibrium expression is

At equilibrium:
Kc =
[C]c[D]d
[A]a[B]b
Equilibrium Constants
The actual value and units of Kc or Kp will depend on the
balanced equation.
Kc or Kp is a constant and is not affected by changes in
concentration, pressure, surface area or the presence of
catalyst.
Kc or Kp is affected by temperature and its value changes with
temperature.
Kp =
(PC)c(PD)d
(PA)a(PB)b
Equilibria
Two different types of equilibria:
A homogeneous equilibrium has everything present in the
same phase. The usual examples include reactions where
everything is a gas, or everything is present in the same
solution.
A heterogeneous equilibrium has things present in more than
one phase. The usual examples include reactions involving
solids and gases, or solids and liquids.
The equilibrium law is only true if the concentration are

measured at equilibrium.
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Homogenous Equilibrium
Heterogenous Equilibrium
Example Write the Kc expression for the following:
Example:
1. 2SO2(g) + O2(g) 2SO3(g)
1. Steam in contact with hot carbon:

C(s) + H2O(g) H2(g) + CO(g)
2. CH3COOH(l) + C2H5OH(l) CH3COOC2H5(l) + H2O(l)
3. 2CrO42-(aq) + 2H+(aq) Cr2O72-(aq) + H2O(l)
Kc =
2. Copper shake with silver nitrate solution:
Cu(s) + 2Ag+(aq) Cu2+(aq) + 2Ag(s)
Kc =
Example 1
1 mol of ethanoic acid is mixed with 1 mol of ethanol in a

closed flask and allowed to achieve equilibrium at room
temperature. The equilibrium mixture was found to contain
0.67 mol of ethyl ethanoate.
Calculate the Kc for the equilibrium at room temperature.
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Example 2
CH3COCH3 + HCN CH3C(OH)(CN)CH3
A mixture of 0.0500 mol dm-3 propanone and 0.0500 mol dm-3

hydrogen cyanide is left to reach equilibirium at room
temperature. At equilibrium the concentration of product is
0.0233 mol dm-3. Calculate the Kc for this reaction.
Example 3
Ethyl ethanoate is hydrolysed by water:
CH3COOC2H5(l) + H2O(l) CH3COOH(l) + C2H5OH(l)
0.1000 mol of ethyl ethanoate are added to 0.1000 mol of
water. A little acid catalyst is added and the mixture made up
to 1 dm3 with an inert solvent.
At equilibrium, 0.0654 mol of water are present. Calculate Kc
for this reaction.
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Example 4
When 1.0 mol of HI is heated to 460C in a 1.0 dm3 container,
0.78 mol of HI remained at equilibrium. Calculate the Kc for the
following equilibrium:
2HI(g) H2(g) + I2(g)
Example 5
At a total pressure of 1.0 atm, N2O4 is 50% dissociated at a
temperature of 60C :
N2O4(g) 2NO2(g)
Determine the value of the equilibrium constant, Kp for this
reaction at 60C.
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Example 6
N2(g) + 3H2(g) 2NH3(g)
The pressure exerted by these gases at constant T is 2.000 x 107
Pa. Under these conditions, partial pressure of N2 & H2 is 1.490 x
107 Pa and 0.400 x 107 Pa respectively.
Calculate the value of Kp for this reaction.
Example 7
2SO2(g) + O2(g) 2SO3(g)
2SO2(g) and O2(g) at partial pressures of 1.00 atm and 0.50 atm
respectively, are allowed to reach equilibrium at 675 K. When
equilibrium is attained, the total pressure in the container is
found to be 1.01 atm.
Calculate the Kp for this reaction.
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Le Chteliers Principle
When a system in dynamic
equilibrium is subjected to a
disturbance that upsets the
equilibrium, the system changes
in a way to reduce the
disturbance.
Le Chteliers Principle
This principle is the basis of explaining the
changes of equilibrium positions.
The equilibrium positions are affected by:
concentration (of reactants and products)
pressure
temperature
Effect of Concentration
A and 2B are reacted and the system reaches

equilibrium.
Both T and V are held constant while [A] is increased.
The equilibrium is disturbed.
When a system in dynamic equilibrium is

subjected to a disturbance that upsets the
equilibrium, the system changes in a way to
reduce the disturbance.
disturbance = K or L of concentraMon of species

change = shifting of equilibrium position
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Effect of Concentration
B
The equilibrium is disturbed because [A] is increased.

The equilibrium position must shift in a way to reduce
the [A].
A and B will react to form C and D.
[A] decreases because it is used to react with B
[B] decreases because it reacts with B
[C] and [D] increase because of reaction between A and B.
The equilibrium is disturbed because [A] is decreased.
concentration
equilibrium
achieved
disturbance
new equilibrium
position reached
A
[A]
[A] had reduced but still more

than initial concentration.
C
D
time
The equilibrium is disturbed because [C] is increased.
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Question
The equilibrium is disturbed because [C] is decreased.
Predict the shift in equilibrium position when:

more CH3COOC2H5(l) is added at equilibrium
some C2H5OH(l) is removed at equilibrium
Pressure only affects gaseous system.

Pressure is caused by gas molecules hitting the sides of
the container.
The more molecules in the container, the higher the
pressure will be.
A and B are placed in a vessel to react until

equilibrium is achieved.
At equilibrium, the pressure of the system is
increased.
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Effect of Pressure
Increase in pressure means more gaseous molecules per unit

volume.
Equilibrium position will shift towards the side with fewer

molecules.
Right-hand side of the equation has fewer molecules (2 vs. 3 on

the left).
A and B reacts to form more of C and D until equilibrium is

restored.
disturbance = K or L of pressure
Question
Question
2SO2(g) + O2(g) 2SO3(g)

Predict the effect of increasing pressure to the
system at equilibrium.
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Question
Question
2NO2(g) 2NO(g) + O2(g)

Predict the effect of decreasing the pressure on the
reaction.
Effect of Temperature
Temperature is the only factor that alters the value of
Kc or Kp.
The direction of the change depends on whether the
forward reaction is endothermic or exothermic.

disturbance = K or L of temperature
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Increase in temperature will cause the equilibrium position to

shift in such a way that the extra heat is absorbed.
Decrease in temperature will cause the equilibrium position to

shift in such a way that more heat is provided.
Since the forward reaction is exothermic (releasing heat), the

backward reaction is favoured.
Since the forward reaction is exothermic (releasing heat), A and B

will react to produce more of C and D until a new equilibrium is
established.
C and D will react to produce more of A and B until a new

equilibrium is established.
Increase in temperature will cause the equilibrium position to

shift in such a way that the extra heat is absorbed.
Decrease in temperature will cause the equilibrium position to

shift in such a way that more heat is provided.
Since the forward reaction is endothermic (absorbing heat), the

forward reaction is favoured.
Since the forward reaction is endothermic (absorbing heat), the

backward reaction is favoured.
A and B will react to produce more of C and D until a new

C and D will react to produce more of A and B until a new

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Increasing the temperature of a system in

dynamic equilibrium favours the endothermic
reaction. The system counteracts the change
by absorbing the extra heat.
Consider the following reversible reaction in

equilibrium
Decreasing the temperature of a system in

dynamic equilibrium favours the exothermic
reaction. The system counteracts the change
by producing more heat.
State whether the increase in temperature will

produce more ammonia or more N2 and H2.
N2(g) + 3H2(g) 2NH3(g)
H = -92.4 kJmol-1
Catalyst affects only the rate of reaction it

does not change the equilibrium position
because both forward and backward are
increased.
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Industrial Application
It is of great practical importance to be able to predict,
and to control, the equilibrium composition of a
chemical reaction.
In an industrial process it may be desirable to convert
as much as possible of reactants to products as well as
fast as possible.
Contact Process
3 steps process:
1. Production of SO2(g)
2. Production of SO3(g) reversible reaction
This can be manipulated by changing the reaction

conditions to change the equilibrium position.
Le Chatelier's Principle helps us deal with this.
Contact Process
Step 2 Production of SO3
Sulfur dioxide gas is oxidized to sulfur trioxide gas by
oxygen.
2SO2(g) + O2(g) 2SO3(g)
H = -197kJmol-1
Conditions:
- Temperature 450C
- Atmospheric pressure
- Vanadium (V) oxide as catalyst; V2O5
3. Production of H2SO4(aq)
Contact Process
Using Le Chateliers Principles to predict for a high
yield of sulfur trioxide.
2SO2(g) + O2(g) 2SO3(g)
H = -197kJmol-1
The equilibrium yield of sulfur trioxide increases:

as temperature L (exothermic reacMon)
as pressure K (more molecules on the reactant side)
if excess reactant (O2 or SO2) is used or removal of products
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Contact Process
Contact Process
Low temperature increases yield BUT decreases rate of

reaction.
A compromised temperature of 450C is used.
High pressure increases yield and rate BUT requires high

cost for equipment, expertise and maintenance.
At 450C and P of 1 atm, almost 95% conversion is

achieved.
Excess reactant (O2 or SO2) increases yield BUT the cost

to obtain them must be considered.
High pressure is not used.
Removing product increases yield BUT the convenience &

complexity must be considered.
Haber Process
N2(g) + 3H2(g) 2NH3(g)
H = -46kJmol-1
Typical conditions:
temperature: 450C
pressure: 200 atm
catalyst: porous iron catalyst (Fe3O4)
ammonia is removed by condensing it into liquid.
Catalyst: Vanadium (V) oxide
Acid-base Equilibria
Arrhenius Theory
Acids are substances which produce hydrogen ions in
solution.
Bases are substances which produce hydroxide ions
in solution.
Neutralisation happens because hydrogen ions and
hydroxide ions react to produce water.
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Arrhenius Theory
Arrhenius Theory
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)
HCl(aq) + NH3(aq) NH4Cl(aq)
HCl + aq H+ (aq) + Cl-(aq)
NH3(aq) does not produce OH-
HCl is an acid produces H+ in solution
Maybe: NH3(aq) + H2O NH4+ + OH-
NaOH(s) + aq Na+(aq) + OH-(aq)

NaOH is a base produces OH- in solution
Brnsted-Lowry Theory
HCl(g) + NH3(g) NH4Cl(s)

In this case, there is no OH-.
An acid is a proton (hydrogen ion) donor.

A base is a proton (hydrogen ion) acceptor.
Species that
donates H+ is
an acid.
Species that
accepts H+ is
a base.
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Water is amphoteric can be acid or base.
Brnsted-Lowry acids and bases do not need
to involve solutions.
Species that
accepts H+ is
a base.
Species that
donates H+ is
an acid.
Conjugate Acids & Bases
HClO4 react with CH3COOH in inert solvent,

HClO4 donates H+ (acid) while CH3COOH
accepts H+(base)
An acid and a base which differ only by the

presence or absence of a proton are called a
conjugate acid-base pair.
HA + H2O H3O+ + A In this reversible reactions there 2 acids and 2
bases.
They are called conjugate pairs.
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Forward reaction:
NH3 is a base because it accepts a H+ to NH4+.
H2O is an acid because it donates a H+ to NH3.
NH3 and NH4+ are acid-base conjugate pair.
Backward reaction:
NH4+ donates H+ to form OH-, so it is conjugate
acid
OH- accepts H+ from NH4+, so it is conjugate base.
H2O and OH- are acid-base conjugate pair.
Strength of Acids & Bases
Strong Acids & Bases
Strong acids and strong bases are almost

completely ionized/dissociate in water. The
equilibrium lies heavily to the right; proton
transfer is almost complete.
The equilibrium position is so far to the right that we can

consider it as an irreversible reaction.
The vast majority of acids are weak and are

not fully ionised in water. The same is true for
most bases. The equilibrium lies more to the
left.
Strong base:
NaOH(s) + aq Na+(aq) + OH-(aq)
Strong acid:
HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq)
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Weak Acids & Bases
Weak Acids & Bases

Concentration
/ mol dm-3
1.0
pH
0.1
0.01
HCl
(strong)
CH3COOH
(weak)
NaOH
(strong)
2.4
2.9
3.4
14
13
12
11.6
11.1
10.6
The equilibrium position is well over to the left that.

Weak acids:
CH3COOH(l) + H2O(l) CH3COO-(aq) + H3O+(aq)
Weak bases:
NH3(g) + H2O(l) NH4+(aq) + OH-(aq)
NH3
(weak)
22

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24/10/2014

Calculate the values of equilibrium constants in terms of concentrations or

Calculate the quantities present at equilibrium, given appropriate data

Explain qualitatively the differences in behaviour between strong and

Explain, in terms of rates of the forward and reverse reactions, what is

State Le Chateliers Principle and apply it to deduce qualitatively (from

Deduce whether changes in concentration, pressure or temperature or the

Deduce expressions for equilibrium constants in terms of concentrations,

N2(g) + 3H2(g) 2NH3(g)

1. Dynamic (not static)

H2(g) + I2(g) HI(g)

Equilibrium concentrations (mol dm-3)

Equilibrium concentrations (mol dm-3)

A constant value, within experimental error, is

Kc equilibrium values are expressed as

The value of this ratio of equilibrium concentrations

Kp equilibrium values are expressed as partial

The equilibrium expression is

The equilibrium law is only true if the concentration are

Example Write the Kc expression for the following:

1. 2SO2(g) + O2(g) 2SO3(g)

1. Steam in contact with hot carbon:

2. CH3COOH(l) + C2H5OH(l) CH3COOC2H5(l) + H2O(l)

3. 2CrO42-(aq) + 2H+(aq) Cr2O72-(aq) + H2O(l)

1 mol of ethanoic acid is mixed with 1 mol of ethanol in a

A mixture of 0.0500 mol dm-3 propanone and 0.0500 mol dm-3

A and 2B are reacted and the system reaches

When a system in dynamic equilibrium is

disturbance = K or L of concentraMon of species

The equilibrium is disturbed because [A] is increased.

The equilibrium is disturbed because [A] is decreased.

[A] had reduced but still more

The equilibrium is disturbed because [C] is increased.

The equilibrium is disturbed because [C] is decreased.

Predict the shift in equilibrium position when:

some C2H5OH(l) is removed at equilibrium

Pressure only affects gaseous system.

A and B are placed in a vessel to react until

Increase in pressure means more gaseous molecules per unit

Equilibrium position will shift towards the side with fewer

Right-hand side of the equation has fewer molecules (2 vs. 3 on

A and B reacts to form more of C and D until equilibrium is

2SO2(g) + O2(g) 2SO3(g)

2NO2(g) 2NO(g) + O2(g)

When a system in dynamic equilibrium is

Increase in temperature will cause the equilibrium position to

Decrease in temperature will cause the equilibrium position to

Since the forward reaction is exothermic (releasing heat), the

Since the forward reaction is exothermic (releasing heat), A and B

C and D will react to produce more of A and B until a new

Increase in temperature will cause the equilibrium position to

Decrease in temperature will cause the equilibrium position to

Since the forward reaction is endothermic (absorbing heat), the

Since the forward reaction is endothermic (absorbing heat), the

A and B will react to produce more of C and D until a new

C and D will react to produce more of A and B until a new

Increasing the temperature of a system in

Consider the following reversible reaction in

Decreasing the temperature of a system in

State whether the increase in temperature will

N2(g) + 3H2(g) 2NH3(g)

Catalyst affects only the rate of reaction it

This can be manipulated by changing the reaction