Chemical reactions:

Chemical
reactions

Reversible (Rxns
Rxns that go to
that do not go to
completion
completion
 Reactions that go to completion:
 Chemical reactions that proceed until limiting reagent
is used up.
 For example, in the reaction between K2CO3 and
hydrochloric acid:

K 2CO 3 (s)  2HCl (aq) 


CO 2 (g)  2KCl (aq)  H 2O (l)
Chemical equilibrium: Reversible reactions
 Many chemical reactions do not proceed to
completion.
 For example: Molecular Representation of the
Reaction 2NO2(g) N2O4(g) over Time in a
Closed Vessel
The Reaction 2NO2(g) N2O4(g) Over Time
in a Closed Vessel

13-1
Chemical equilibrium: Reversible reactions

 Example 2: In the reaction between hydrogen gas and

iodine vapour to form hydrogen iodide.

H2(g) + I2(g) 2HI(g)

 Forward reaction ()
 Backward reaction or reverse reaction ()

Equilibrium is achieved at
Concentration the same time
(mol dm-3)
Forward [HI]
rxn

Reverse [I2]
rxn

Time
explain reversible rxn & dynamic equilibrium in terms
of forward and backward reactions
calculate the quantities present at equilibrium from
given data
 The concept of dynamic
equilibrium
 When chemical equilibrium is attained in a
reversible reaction,
1. Both forward and reverse reactions continue
indefinitely.
 Therefore, a chemical equilibrium is a dynamic
process.
2. The [reactants] and [products] remain constant
because both the forward and the reverse
reactions occur at the same rate.
Rate
Forward
rxn
Dynamic
equilibrium

Reverse
rxn
te Time
deduce expressions for equilibrium constants in term of
concentrations, Kc, & partial pressures, Kp
calculate values of Kc & Kp from given data
The Law of chemical Equilibrium/ Law of
mass action
 “For any equilibrium at a fixed temperature,
the product of the [products], each raised to a
power equal to its coefficient in the equation,
divided by the product of the [reactants], each
raised to a power equal to its coefficient in the
equation, is a constant.”
 The constant is given the symbol K, and is
known as the equilibrium constant.
Deduce expressions for equilibrium
constants, Kc
aA  bB 
cC  dD
k1

k 1

 
c  
d
C
  
D 
Kc 
a
 A  B  b
   

 Constant (At fixed temperature)

There is no standard unit for
equilibrium constants.
Example: (page 8,example7)
 Write expressions for the equilibrium
constants, Kc for each rxn; giving their units.
1. H2 (g) + F2 (g) 2HF (g)

2. ½H2 (g) + ½ F2 (g) HF (g)

3. 2H2 (g) + 2F2 (g) 4HF (g)

 Are the Kc for each equilibrium the same?
 The Kc are different for
each reaction.
Hmmm… meaning whenever
Kc is written, the
equilibrium must be shown
too.
 Equilibrium constants, K can be
expressed in term of concentrations
(Kc), & partial pressures (Kp).
Deduce expressions for equilibrium
constants, Kp (refer page 7)
aA(g)  bB(g) 
cC (g)  dD(g)
k1


k
1

Pc  Pd Pa, Pb, Pc & Pd =

Kp  Partial pressures of A,
Pa  Pb B, C & D at equilibrium

 Constant (At fixed temperature)

Example: (page 8,example 8)
 Write expressions for the equilibrium constants, Kp
for each reaction; giving their units
1. H2 (g) + F2 (g) 2HF (g)
2. ½H2 (g) + ½ F2 (g) HF (g)
3. 2H2 (g) + 2F2 (g) 4HF (g)
 Are the Kp for each equilibrium the same?
Equilibrium constants: Kc & Kp (Eg 6)
Δn
K p  K c  RT 
Where R  Gas constant
T  Temperatur e (K)
Δn  Σ number of moles of gaseous
products - Σ number of moles
of gaseous reactants
 When Δn = 0, Kp = Kc
Homogeneous equilibrium

 All reactants and products are in the

same phase/ physical state (solid/
vapour/ liquid/ solution) in a
homogeneous equilibrium.
Examples of Homogeneous equilibrium (Kc
or Kp)
1. CH3COOH (l) + C2H5OH (l)
CH3COOC2H5 (l) + H2O (l)

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

3. HF (aq) H+ (aq) + F– (aq)

Units of equilibrium constants
 The units of the equilibrium constant vary from one
equilibrium to another.

 Example 7 & 8 (Page 8)

 Test yourself 2
K1 and K–1
aA  bB 
cC  dD
k1


k
1

 
c  
d  
a  
b
C
  
D  
A
 
B 
K  & K 1

1
 
a  
b  
c  
d

A
 
B C
  
D 
1
 K 
1
K 1
Example 9 & 10 (Page 9 & 10)
Heterogeneous equilibrium

 Reactants and products in the rxn are in

more than one phase/ physical state
(solid/ vapour/ liquid/ solution).
Examples of Heterogeneous
equilibrium
1. NH3(g) + HCl (g) NH4Cl (s)
2. H2O(g) + C (s) CO (g) + H2 (g)
3. MgCO3(s) MgO (s) + CO2 (g)
 In systems where gas reagent(g) is/ are present, the
position of the equilibrium is influenced only by the
gas reagent(g).
Examples of Heterogeneous
equilibrium

 Example 11 (Page 11)

 Example 12  16 (Page 12  14)
 (Please go back and study……)
Dissociation reactions
 Many of the reversible reactions belong to the
type where a molecule is broken down into
smaller molecules, atoms or ions.
 These are called dissociation reactions.
 Examples of compounds which undergo
dissociation are:
1. PCl5 (g) PCl3 (g) + Cl2 (g)
2. N2O4 (g) 2NO2 (g)
Dissociation reactions
 How many percent of the molecules
dissociate?
 This called the degree of dissociation, α.
 E.g.:
1. When α = 1 or 100%, ALL molecules are
dissociated.
2. When α = 0.40 or 40%, only 40% of
molecules are dissociated.
 Tips: Use mole to represent the amount of
reagents.
Example 17 21 (Pg 14  18)
(Please look at Example 17)
 The applications of equilibrium
constants
a. Calculating the concentrations of reactants and
products when chemical equilibrium is established
b. Calculating the degree of dissociation
c. Determine the position of equilibrium
d. Judging the extent of reaction
e. Predicting the direction of reaction to achieve
equilibrium.
Q.1 The equilibrium constant, Kc for the
esterification of ethanoic acid by ethanol is 4.0
at room temperature.Calculate the composition
of the equilibrium mixture if 180g of ethanoic
acid, 230g of ethanol and 45g of water are
allowed to react and reach equilibrium.

No. of mol of ethanoic acid used=180/60 = 3.0

No. of mol of ethanol used=230/46 = 5.0
No. of mol of water present= 45/18 = 2.5
Let the no. of mol of ester produced= x
CH3COOH + C2H5OH CH3COOC2H5 + H2O
(b4) 3.0 5.0 0 2.5

(equi) 3.0-x 5.0-x x 2.5+x

Let the vol of the equilibrium mixture =v dm3

(x )(2.5+x)
Kc=4.0= v v
(3-x)(5-x)
v v
3x2 – 34.5x + 60 = 0
x=9.4 (unacceptable) or 2.13
Thus,no of mol of ester formed=2.13
no of mol of water formed=2.5+2.13=4.63
No of mol of ethanol remaining=5.0-2.13=2.87
No of mol of ethanoic acid remaining=3.0-
2.13=0.87
 aA + bB cC + dD
 If the [products] (C and D) < [reactants] (A and B),
 The position of equilibrium lies to the left, and
 The value of Kc or Kp is small.
 If the [products] (C and D) > [reactants] (A and B),
 The position of equilibrium lies to the right, and
 The value of Kc or Kp is great.
 The position of equilibrium changes
when the following external physical
properties of the equilibrium systems
are changed:
 Pressure (g)
 Concentration (aq)
 Temperature
 The equilibrium constants, Kc and Kp remain the same
at a constant temperature regardless of any changes
in the pressure of the system or changes in the
concentrations of reactants or products.
Judging the extent of reaction
 The magnitude of the equilibrium constant
for a reaction indicates how far the reaction
proceeds before chemical equilibrium is
reached.
Judging the extent of reaction
 If Kc very large (Kc>103) ~ the reaction proceeds almost
all the way to completion.
 If Kc very small (Kc<10-3) ~ the reaction hardly proceeds
& the equi. mixture will contain mainly reactants.
 If Kc in the range of 10-3 to 103 ~ appreciable [ ] of both
reactants & products are present.
The reaction quotient, Qc:
 For the rxn:
aA + bB cC + dD
c d
C   D 
   
Qc  a
   b
A B
   
 Q can be evaluated using any set of [A], [B], [C]
and [D].
Predicting the direction of rxn
N2(g) + 3H2(g) 2NH3(g)
 The mixture of 1.0 mol of N2, 2.0 mol of H2 & 2.0 mol
of NH3 is placed in a 1 dm3 vessel at 472oC.
 To find whether the system is at equilibrium, we need
to know the reaction quotient (Qc) & the equi.
constant for the reaction.
 [NH 3 ]2 2.0 2
 Qc when t = 0: Q c  [N ][H ]3  1.0  2.03
2 2
 0.50 mol  2 dm 6
2
0.00272
 At equilibrium, K c  0.040  0.1213
[N2] = 0.040 mol dm-3
[H2] = 0.121 mol dm-3  0.104 mol dm
2 6

[NH3] = 0.00272 mol dm-3

 Qc > Kc
 The system is not at equilibrium
 To achieve equilibrium, Qc will need to decrease to Kc.
 This changes can only happen if [NH3] decreases, [N2]
& [H2] increase.
 Thus, the reaction proceeds from right to left
(reverse reaction).
 To predict the direction of any chemical
reaction, compare the values of Qc & Kc.

Relationship Direction of reaction

The reaction goes from left to

Q c < Kc right (forward reaction)
The reaction mixture is already
Q c = Kc at equilibrium
The reaction goes from right to
Qc > Kc left (reverse reaction)
Learning Area
 Factors affecting chemical equilibria: Le Chatelier’s
principle. The following examples are useful.
 The synthesis of hydrogen iodide
 The dissociation of dinitrogen tetraoxide
 The hydrolysis of simple esters
 The Contact proses
 The synthesis of ammonia
LO
 state Le Chatelier’s principle and use it qualitatively
from given information
 discuss the effect of catalyst, or changes in
concentration, pressure, or temperature on a system
at equilibrium, using Le Chatelier’s principle
 state examples of equilibria which are referred to
studied in general
 explain the effect of temperature on equilibrium
constants from the equation ln K = -ΔH/ RT +C
 show awareness of the importance of an
understanding of chemical equilibrium in chemical
industry
 n
p  RT
V
Factors that affect the position
of equilibrium
 Temperature,
 Concentration and
 Pressure (in the case of reversible
reactions involving gases)
Catalyst speeds up the rxn rate.
It does not affect K and the
position of the equilibrium.
 The direction in which an equilibrium will
shift when one of these changes is made
can be predicted by applying Le
Chatelier’s principle.
Le Chatelier’s principle
When a system at equilibrium is subjected to a
change in temperature, pressure, or concentration
of a reactant or product, the system will shift its
equilibrium so as to partially counteract the effect
of the change.
In other words, if a stress is applied to a rxn mixture in
equilibrium, rxn occurs in the direction that relieves the
stress.
Some abb. :
 Rate of forward rxn = rf
 Rate of backward rxn = rb
(A)The effect of concentration on
equilibrium
 If the concentration of a reactant is increased, Le
Chatelier’s principle states that the equilibrium
position will shift in the direction that tends to reduce
the concentration of this reactant.
 Thus the position of equilibrium will shift to the right
(forward reaction).
 By doing so, some of the reactant will be used up.
 Conversely, if the concentration of the product is
increased, the equilibrium position will shift to the
left(reverse reaction).
 e.g.: The synthesis of hydrogen iodide
H2(g) + I2(g) 2HI(g)
 If H2 is added to the reaction mixture:
1. Initially, the rf will increase more than the
rb.
2. As the reaction progresses, [H2] & [I2]
decrease while [HI] increases, until a new
equilibrium position is established when
the rf = rb.
3. the addition of H2 increases the concentration of HI
and decreases the concentration of I2.

 This means that more HI will be formed and the

concentration of I2 decreases.
 Thus, the addition of H2
 will shift the equilibrium position to the right,
 will increase the rate at which equilibrium is attained,
and
 will not increase the value of the equilibrium constant.
 1st equi Equi re-established
Concentration

H2

I2

HI

0
Time
 H2(g) + I2(g) 2HI(g)

 ____ is added into the system

H2
at ____ s.
Concentration

I2
 According to le Chatelier
principle, the position of the
HI
equilibrium moves from ____
to ______ to minimise the
0 T1 T2 Time/s increase in [H2].
 H2(g) + I2(g) 2HI(g)
 H2 is added into the system
at T1 s.
H2
Concentration

I2
 According to le Chatelier
principle, the position of the
HI
equilibrium moves from left
to right to minimise the
0 T1 T2 Time/s increase in [H2].
 H2(g) + I2(g) 2HI(g)

 Hence, [I2] ____ and

H2
[HI] ____ .
 A new equilibrium is
Concentration

I2 attained at ___ s.
 During T2, the rate of
the forward reaction
HI
_____ the rate of the
backward reaction.
0 T1 T2 Time/s  Kc remains the ______
because there is no
change in T.
 H2(g) + I2(g) 2HI(g)

 Hence, [I2] decreases

H2
and [HI] increases .
 A new equilibrium is
Concentration

I2 attained at T2 s.
 During T2, the rate of
the forward reaction =
HI
the rate of the backward
reaction.
0 T1 T2 Time/s  Kc remains the same
because there is no
change in T.
Example:
N2(g) + 3H2(g) 2NH3(g)
 Consider the above system.
 Predict whether the forward or backward rxn
will occur when the equilibrium is disturbed
by:
1. Adding N2 4. Removing NH3
2. Removing N2 5. Adding H2
3. Adding NH3 6. Removing H2
 For the above cases, what is the effect on Kc?
(B) Effect of a pressure change on an
equilibrium
 For a reversible reaction, a change in pressure alters:
1. the rate of reactions (rf and rb)  [reagents] has
changed
2. the composition of the equilibrium mixture.
 The equilibrium constant stays constant.
 Example: The Haber process
N2(g) + 3H2(g) 2NH3(g)
 An increase in pressure will shift the position of the
equilibrium to decrease the total no. of moles of gas (pV =
nRT  p α n).
 Therefore, the position of equilibrium will move from left
to right.
 More ammonia will be obtained in the new equilibrium
system.
Summarising:
 An increase in pressure  The system will respond by
shifting its equilibrium position to decrease the no of
moles of gases.
 A decrease in pressure  The system will respond by
shifting its equilibrium position to increase the no of
moles of gases.
Example:
CaCO3(s) CaO(s) + CO2(g)
 Consider the above equilibrium system.
 Predict the effect of:
1. Decreasing the pressure of the system
2. Increasing the pressure of the system
3. Reducing the total volume of the system
4. Expanding the total volume of the system
Example:
CaCO3(s) CaO(s) + CO2(g)
1. Decreasing the pressure of the system
 Applying le Chatelier’s principle, the position
of the equilibrium will move in the direction to
Increase the pressure of the system.
__________
 i.e. one that causes an __________
Increase in the
number of moles of gas in the system.
 Therefore, the position of equilibrium will
Left to ______
move from ______ right

 More limestone dissociates.

Example:
CaCO3(s) CaO(s) + CO2(g)
2. Increasing the pressure of the system
 Applying le Chatelier’s principle, the position
of the equilibrium will move in the direction to
decrease the pressure of the system.
__________
 i.e. one that causes an decrease
__________ in the
number of moles of gas in the system.
 Therefore, the position of equilibrium will
Right to ______
move from ______ left
Example:
CaCO3(s) CaO(s) + CO2(g)
3. Reducing the total volume of the system
 Results in a increase
_________ in the total pressure on
the system.
 The position of the equilibrium will move in the
decrease in the
direction that causes an __________
number of moles of gas in the system.
 Therefore, the position of equilibrium will move
Right to ______
from ______ left
Example:
CaCO3(s) CaO(s) + CO2(g)
4. Expanding the total volume of the system
 Results in a _________
decrease in the total pressure
on the system.
 The position of the equilibrium will move in
increase in
the direction that causes an __________
the number of moles of gas in the system.
 Therefore, the position of equilibrium will
Left to ______
move from ______ right
(C) The effect of adding noble gas at
constant volume
Does not alter the equilibrium.
(D) The effect of adding noble gas at
constant pressure
 Volume of the system is expanded.
 Partial pressure/ concentration of
reagents are decreased.
 Thus, according to Le Chatelier’s
principle, the presence of a noble gas
favours the direction that increases
the no of moles of gases.
Examples:
noble gas
a. PCl3(g) + Cl2 (g) PCl5(g)
The equilibrium favours the reactants (2
moles of gases).
noble gas
b. 2H2O(g) 2H2(g) + O2(g)
The equilibrium favours the products (3 moles
of gases).
Examples:
noble gas
c. H2(g) + I2(g) 2HI(g)
No effect on the equilibrium
(E) The effect of temperature on
equilibrium
 In a reversible reaction, the changes in
temperature will affect:
The rate of reaction
The rate constant
The position of equilibrium
The equilibrium constant
Figure 8.5: Exothermic forward rxn (-ΔH)
When T increases:
 Equilibrium shifts
E backward
n  [reactants] increases
e Reactants
r  Kc decreases
g
y
Products

Progress of reaction
Figure 8.6: Endothermic forward rxn (+ΔH)

When T increases:
 Equilibrium shifts
forward
E
n  [products] increases
e Products
r  Kc increases
g
y Reactants

Progress of reaction
T and K by van’t Hoff
equation:
 The effect of temperature on the equi. constant is
given by van’t Hoff equation:

ΔH
ln K    c
RT
 Or:

K2ΔH 1 1
ln    
K1 R T T 
 1 2 

This derived
equation is MORE
USEFUL!
The van’t Hoff equation shows that:
 For exothermic reactions, the equilibrium
constant decreases with temperature.

K ΔH
ln K    c
RT

T
 For endothermic reactions, the
equilibrium constant increases with
temperature.
K ΔH
ln K    c
RT

T
The effect of temperature on an equilibrium
can be explained by using Le Chatelier’s
principle
 E.g. : Dissociation of dinitrogen tetraoxide

N2O4(g) 2NO2(g)
 The dissociation reaction is endothermic.
 LCP states that increasing the temperature shifts the
equilibrium to the endothermic direction so that heat is
absorbed and the temperature increase is minimised.
 That is, the concentration of NO2 increases while the
concentration of N2O4 decreases.
 Thus, the equilibrium constant increases.
 Hence, the concentration of NO2 in the equilibrium
mixture increases.
 An increase in temperature increases the rate of
reaction because at a higher temperature, the
proportion of molecules that have energies equal to or
higher than activation energy increases.
 The effect of temperature on the rate constant is given by
the Arrhenius equation

lnk = ln A – Ea
RT

 The value of k(the rate constant) increases if the

temperature is raised, regardless of whether the reaction
is exothermic or endothermic.
(F) The effect of a catalyst on the
equilibrium
 A catalyst changes the reaction rate and therefore the
rate constant.
 However, a catalyst does not change the position of the
equilibrium mixture.
 This is because a catalyst increases the reaction rates of
both the forward and the reverse reactions to the same
extent.
 As a result, the same equilibrium mixture is obtained at
a faster rate when a catalyst is present.
 Summary (Page 40 + 41)
Effect Rxn rate Rate Equilibriu Compositio
constant m constant n of mixture

Catalys Increase Increase No change No change

t rf↑, rb↑ k1↑, k-1↑
 Effect Reaction Rate Equilibrium Composition
rate constant constant of mixture
Increase in Increases Increases Increases Changes
temperature rf↑, rb↑ k1↑, k-1↑ ↑ [product]↑
∆H=+ve [reactant]↓
Increases Increases Decreases Changes
rf↑, rb↑ k1↑, k-1↑ ↓ [product]↓
∆H= -ve
[reactant]↑
Decrease in Decreases Decreases Decreases Changes
temperature rf↓, rb↓ k1↓, k-1↓ ↓ [product]↓
∆H=+ve [reactant]↑
Decrease Decrease Increases Changes
∆H= -ve ↑
rf↓, rb↓ k1↓, k-1↓ [product]↑
[reactant]↓
 Factor Reaction Rate Equilibrium Composition
rate constant constant of mixture

Increase in Increases No change No change Changes

pressure rf ↑, rb ↑ [product] ↑
nrea < nprod [reactant] ↑
Increases No change No change Changes
nrea>nprod
rf↑, rb ↑ [product] ↑
[reactant] ↑
Decrease in Decreases No change No change Changes
pressure rf ↓, rb ↓ [product] ↓
nrea <nprod [reactant] ↓
Decreases No change No change Changes
rf ↓, rb↓ [product] ↓
nrea >npro [reactant] ↓
 Factor Reaction Rate Equilibrium Composition of
rate constant constant mixture

Increasing increases No No change Changes

[ ] of rf↑, rb ↓ change [product]↑
reactant [reactant
added]↑
[other
reactant]↓

Decreasing Decreases No No change Changes

[ ] of rf ↑, rb↓ change [oroduct]↑
product [product
removed]↓
[reactant]↓
The importance of chemical
equilibrium in the chemical industry
1. The Haber process
 The Haber process is an industrial process for the
manufacture of ammonia.

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

ΔH= -92 kJ mol-1
 A higher pressure gives a high yield of
ammonia but the higher the pressure, the
higher the cost to maintain the pressure.
 Therefore, most ammonia plants operate
at a pressure of around 250 atm.
 A low temperature gives a high yield of
ammonia, but at low temperatures, the
reaction rate is excessively low.
 Hence, most plants operate at a
temperature around 500ºC to ensure that
the reaction proceeds at a reasonably rate,
and gives a reasonable yield of ammonia.
 A catalyst, finely divided iron, is used to
reduce the time to reach equilibrium.
 The efficiency of the iron catalyst used is
enhanced by the addition of small
amounts of potassium oxide and
aluminium oxide which act as promoters.
2. The Contact process
 The Contact process is the industrial
process for the manufacture of sulfuric
acid.
2SO2(g)+O2(g) 2SO3(g) ΔH= -197
kJ mol-1
 According to Le Chatelier’s principle,the
maximum yield of SO3 at equilibrium is
obtained at
a. Low temperature and
b. High pressure
Thus, the industrial conditions for the
synthesis of SO3 are
Temperature:450ºC
Pressure:1 atm
Catalyst:vanadium(v) oxide, V2O5
Percentage conversion of sulphur
dioxide to sulphur trioxide is 95%