CHEM120

Principles of
Chemical
Equilibrium

Prof. MD Bala
2
 Equilibrium
Equilibrium – state where the forward & reverse
processes are occurring at same speed/rate

Dynamic – processes/reaction constantly occurring but

NO net observable change

Physical Equilibria – changes in phase

H2O(l) ⇌ H2O(g)

Chemical Equilibrium – reversible reaction

3
 Chemical Equilibrium
Generally chemical reactions do not occur in one
direction only, but are REVERSIBLE.

In the general reaction:

aA+bB  cC+dD

At time zero:
Only A & B present, .: the reaction occurring is:
aA+bB  cC+dD
T > 0:
As time goes on, and more of the products (C & D) forms,
so they start to react to reform the “reactants”.
cC+dD  aA+bB
4
 Chemical Equilibrium

REACTANTS PRODUCTS

After a certain time period:

Rate of the Forward Rxn = Rate of Reverse Rxn

At this stage, the system is said to be at equilibrium.

aA + bB ⇌ cC + dD

Where an equilibrium state is denoted by the symbol:

⇌ 5
Consider the following general equilibrium
reaction:
aA + bB cC + dD

[C]c [D]d
Kc = a b
Kc ≡ equilibrium constant [A] [B]
[ ] ≡ molarity at equilibrium
K does vary with temperature
K > 1 products favoured, forward reaction favoured with mostly products
K < 1 reactants favoured, reverse reaction favoured with mostly reactant
K = 1 the equilibrium mixture contains appreciable amounts of both
reactants and products
 Chemical Equilibrium
Forward Reaction: Synthesis of Methanol
CO(g) + 2 H2(g)  CH3OH(g)

Reverse Reaction: Methanol formed decomposes

CH3OH(g)  CO(g) + 2 H2(g)

Dynamic Equilibrium:
CO(g) + 2 H2(g) ⇌ CH3OH(g)

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 Equilibrium Constant Expression
The equilibrium constant, K, is a ratio of the
equilibrium concentration of the products to
the reactants,
- Temperature dependent
- Solids & pure liquids NOT included

Dynamic Equilibrium:
CO(g) + 2 H2(g) ⇌ CH3OH(g)

(CH3OH)
K=
(CO) x (H2)2
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Equilibrium Constant Expression
KC – the equilibrium concentrations expressed
in molarities (mol L-1)

[PRODUCTS]eq
KC =
[REACTANTS]eq

KP – the equilibrium concentrations expressed

in pressures (atm)

(PPRODUCTS)eq
KP =
(PREACTANTS)eq
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 Example
Write the equilibrium constant expression for:
a) KP for: N2(g) + 3 H2(g) ⇌ 2 NH3(g)
(PNH3)2
KP =
(PN2) x (PH2)3
b) KC for: 2 H2O2(g) ⇌ 2 H2O(g) + O2(g)

[H2O]2 [O2]
KC =
[H2O2]2
How would KC for (b) change if water was H2O(l) not
H2O(g)?
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 Exercise
Calculate [H2(g)]eq at 483 K in the ⇌ below, given that
[CO(g)]eq & [CH3OH(g)]eq are 1.03 M & 1.56 M. Given KC
= 14.5 at 483 K.

CO(g) + 2 H2(g) ⇌ CH3OH(g)

Solution:
Derive the equilibrium constant expression, KC:

[CH3OH]eq
KC =
[CO]eq x [H2]eq2
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 Exercise
Solution:

Rearrange and substitute in the values:

[CH3OH]eq
[H2]eq2 =
KC x [CO]eq

(1.56)
[H2]eq2 = = 0.104
14.5 x (1.03)

and
[H2]eq = √ 0.104 = 0.322 M
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 Magnitude of K

Large K: K >> 1
Mainly PRODUCTS
present

Small K: K << 1
Mainly REACTANTS
present

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 Manipulation of Equilibria 1
The value of K is particular to a specific
equilibrium and a specific temperature
Eqn 1.:
CO(g) + 2 H2(g) ⇌ CH3OH(g) K1 = 14.5

Eqn 2.:
CH3OH(g) ⇌ CO(g) + 2 H2(g) K2 = ?

Eqn 2. is the reverse of Eqn 1., .: K2 is the inverse of K1:

1 1
K2 = = = 0.0690
K1 14.5
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 Manipulation of Equilibria 2
The value of K is particular to a specific
equilibrium and a specific temperature

Eqn 1.:
CO(g) + 2 H2(g) ⇌ CH3OH(g) K1 = 14.5

Eqn 3.:
2 CO(g) + 4 H2(g) ⇌ 2 CH3OH(g) K3 = ?

Eqn 3. is Eqn 1. multiplied by 2, .: K3 is K1 to the power 2:

K3 = (K1)2 = (14.5)2 = 210

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 Manipulation of Equilibria 3
Addition of equilibria – the values of K are multiplied
together

Eqn 1.: H2(g) + Br2(g) ⇌ 2 HBr (g) K1 = 7.9 x 1011

Eqn 2.: 2 H(g) ⇌ H2 (g) K2 = 2.1 x 1040

Eqn 3.: 2 Br(g) ⇌ Br2 (g) K3 = 4.5 x 1014

Calculate the value of K for:
2 H(g) + 2 Br(g) ⇌ 2 HBr(g) K4 = ?
Eqn 4. is the sum of eqn’s 1 + 2 + 3, .: K4 is the product:

K4 = K1 x K2 x K3
= 7.9 x 1011 x 2.1 x 1040 x 4.5 x 1014
= 7.47 x 1066 16
 Example
K for the conversion of O2 to O3 is 2.5 x 10-29

3/ O2(g) ⇌ O3(g)
2

a) Calculate K for: 3 O2(g) ⇌ 2 O3(g)

K2 = (K1)2 = (2.5 x 10-29)2 = 6.3 x 10-58

b) Calculate K for: 2 O3(g) ⇌ 3 O2(g)

1 1 57
K3 = = = 1.6 x 10
K2 6.3 x 10-58
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 Relationship between KP & KC
Ideal Gas Law:
n x RT
P= = Molarity x RT
V

.: can relate KP and KC:

KP = KC (RT)Δn

Where
Δn = mol gaseous products – mol gaseous reactants

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 Example
Determine Δn, and the KP to KC expression for:

a) N2(g) + 3 H2(g) ⇌ 2 NH3(g)

KC
Δn = 2 – (1 + 3) = -2 KP =
(RT)2

b) 2 H2O2(g) ⇌ 2 H2O(g) + O2(g)

Δn = 3 – 2 = +1 KP = KC (RT)1

c) CaCO3(s) ⇌ CaO(s) + CO2(g)

Δn = 1 – 0 = +1 KP = KC (RT)1
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 Example
Calculate KP or KC for the following equilibria at 25 oC:

a) N2(g) + 3 H2(g) ⇌ 2 NH3(g) KC = 2.5 x 108

KC 2.5 x 108
KP = = = 4.2 x 105
(RT)2 (0.08206 x 298)2

b) PCl5(g) ⇌ PCl3(g) + Cl2(g) KP = 29.2

Δn = 2 – 1 = +1
KP 29.2
KC = = = 1.20
(RT)1 (0.08206 x 298)1
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 Example
Calculate KP and KC for the reaction at 60 oC

H2S(g) + I2(s) ⇌ 2 HI(g) + S(s)

if PHI,e & PH2S,e are 3.65 x 10-3 & 9.96 x 10-1 atm,
respectively.
Solution:
Calculate KP from pressure data
(PHI)2 (3.65 x 10-3)2
KP = = = 1.34 x 10-5
PH2S (9.96 x 10-1)
Calculate KC from KP
KP 1.34 x 10-5
KC = = = 4.90 x 10-7
(RT)1 (0.08206 x 333)1 21
 Reaction Quotient, Q
System NOT at equilibrium – allows you to
predict the direction of net change in order to
reach equilibrium
Calculated exactly the same as K

[PRODUCTS]eq
QC =
[REACTANTS]eq

Where
Q < K – the forward rxn must proceed
Q = K – the system is at equilibrium,
Q > K – the reverse rxn must proceed
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 Q>K

Q<K Q=K
 Exercise
KC = 1.00 for the equilibrium at 1100 K:
CO(g) + H2O(g) ⇌ CO2(g) + H2(g)

1.00 M CO, 1.00 M H2O, 2.00 M CO2 and 2.00 M H2 are

mixed together and allowed to react at 1100 K. In
which direction will the reaction proceed in order to
reach equilibrium?
Solution:
[CO2][H2] (2.00)(2.00)
QC = = = 4.00
[CO] [H2O] (1.00)(1.00)

QC > KC .: Reverse reaction will proceed in order to

reach equilibrium
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 Le Chatelier’s Principle
“Every change of one of the factors of an equilibrium
brings about a rearrangement of the system in such
a direction as to minimize the original change”

When a system at ⇌ is subjected to a change (∆ ∆) in [ ]

of a reacting species, P, or T*, the system will respond
by attaining a new equilibrium in which the impact of
the change is partially offset

1) Changes in the amounts of the reactants and/or

products;
2) Changing the pressure or volume;
3) Changes of the temperature; and
4) The addition of a catalyst.
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LCP 1 Changing the Amounts of
Reactants and / or Products
KC for the equilibria is 2.8 x 102 at 1000 K:
2 SO2(g) + O2(g) ⇌ 2 SO3(g)

If more SO3 is added:

The reverse rxn occurs until Q again = K

i.e. a new equilibrium is established 26
LCP1 example
Predict the effect of adding more H2(g) to a system at
equilibrium governed by the equation

N2(g) + 3 H2(g) ⇌ 2 NH3(g)

Solution:
If the nH2 is increased, then
The ⇌ shifts to the Right, to reduce the extra H2

So
nH2(g) ↑, & nNH3(g) ↑, but nN2(g) ↓

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LCP 2 Changing the Pressure or Volume
1. Add or remove gaseous reactants or products
2. Add an inert gas to a constant volume rxn mixture
3. Change the pressure by changing the volume

When the pressure is increased or the volume decreased:

the equilibrium shifts to the side which has fewer moles
of gases (& vise versa) 28
 Example
What effect would an increase in the system volume
have on the original equilibrium?

N2(g) + 3 H2(g) ⇌ 2 NH3(g)

Solution:
Moles of gaseous products: 2
Moles of gaseous reactants: 4

An increase in the Volume  the equilibrium would

shift to side with more gaseous compounds
Therefore
⇌ shifts left
nH2(g) ↑, nN2(g) ↑, nNH3(g) ↓ 29
LCP 3 Changing the Temperature

Raising the temperature of a system at ⇌ results in a

shift in the direction of the endothermic reaction,
while lowering/decreasing the temperature causes a
shift in the direction of the exothermic reaction

For the equilibrium

CH4(g) + O2(g) ⇌ CO2(g) + H2O(g) + HEAT

Forward Rxn – Exothermic Reverse Rxn – Endothermic

T – Reverse Reaction (trying to lower the heat)

 T – Forward Reaction (trying to generate heat)

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 Example
What conditions of T and P would make the
equilibrium below most productive?

2 SO2(g) + O2(g) ⇌ 2 SO3(g) ∆Ho -197.8 kJ

We want the equilibrium to shift to the right!

Solution:
Moles of gaseous products: 2
Moles of gaseous reactants: 3
Therefore
High Pressure – fewer gases on product side;
Low Temperature – Forward rxn is exothermic
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LCP 4 The Addition of a Catalyst
Catalysts do not affect the position of an ⇌ (& ∴ the
magnitude of KC or KP), but they can decrease the time
required to get there, & thus make the overall process
more efficient

V2O5 – catalyst used in production of SO3

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 Exercise
Colourless N2O4(g) is partially dissociated into red-
brown NO2(g) at 25 oC, as shown below:
N2O4(g, colourless) ⇌ 2 NO2(g, brown)
Calculate the value of Kc for this reaction if the masses
of N2O4(g) & NO2(g) at ⇌ in a 3.00 L flask were found to
be 7.64 g and 1.56 g, respectively.

Solution:
1. Calculate the molarities of
each at equilibrium:
2. Calculate the KC:
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 Exercise
Solution:
Calculate the molarities of each at equilibrium:
m 7.64 g
MN2O4 = = = 0.0277 M
MM x V 92.01g mol-1 x 3.00 L
m 1.56 g
MNO2 = = = 0.0113 M
MM x V 46.01g mol-1 x 3.00 L

Calculate the KC:

[NO2]2 (0.0113)2
KC = = = 4.61 x 10-3
[N2O4] 0.0277
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 Exercise
When a 0.0200 mol sample of SO3 is introduced into an
evacuated 1.52 L flask and allowed to come to
equilibrium at 900 K, 0.0142 mol SO3 is still present.
Calculate KP for this reaction.

2 SO3(g) ⇌ 2 SO2(g) + O2(g)

Solution:
1. Calculate the molarities of SO3
2. Setup an ICE table
3. Calculate KC
4. Calculate KP
35
 Exercise
Solution:
Calculate the molarities of SO3:

n 0.0200 mol
MSO3, i = = = 0.0132 M
V 1.52 L
n 0.0142 mol
MSO3, eq = = = 0.00934 M
V 1.52 L

36
 Exercise
Solution:
Setup the ICE table:

2 SO3 ⇌ 2 SO2 + O2(g)

Initial [ ] 0.0132 0 0

Change - 2x + 2x +x

Equilib [ ] 0.0132- 2x + 2x +x

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 Exercise
Solution:
But at equilibrium

MSO3, eq = 0.00934 M

Therefore solve for x:

MSO3, eq = 0.0132 – 2 x = 0.00934 M

2x = 0.0132 – 0.00934 = 0.00386

x = ½ x 0.00386 = 0.00193 M

Substitute x into [SO2]eq and [O2]eq:

MSO2, eq = 2x = 0.00386 M MO2, eq = x = 0.00193 M

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 Exercise
Solution:

Calculate the KC:

[SO2]2 [O2] (0.00386)2(0.00193)

KC = = = 3.1 x 10-4
[SO3]2 (0.00934)2

Calculate the KP from KC:

Δn = 3 – 2 = 1

KP =KC(RT)Δn = (3.1 x 10-4)(0.08206 x 900)1 = 2.3 x 10-2

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 Exercise
NH4HS(s), used as a photographic developer, is unstable
and dissociates at 25 oC.

NH4HS(s) ⇌ NH3(g) + H2S(g) KP = 0.108

A sample of NH4HS (s) is placed in an evacuated flask

and allowed to equilibrate. Calculate Ptot, eq.

Solution:
1. Calculate the partial pressures of each at
equilibrium from the KP:

2. Using Dalton’s law of Partial Pressures, calculate

PTotal. 40
 Exercise
Solution:
1. Calculate the partial pressures of each at equilibrium
from the KP:
KP = (PNH3)(PH2S) = 0.108

From the stoichiometry:

1 mol NH4HS  1 mol NH3 & 1 mol H2S
.: PNH3 = PH2S = x

(PNH3)(PH2S) = (x)2 = 0.108

x = √0.108 = 0.329 atm

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 Exercise
Solution:
2. Using Dalton’s law of Partial Pressures, calculate
PTotal.
PTotal, eq = PNH3 + PH2S

PTotal, eq = 0.329 + 0.329

= 0.658 atm

42
 Exercise
A 0.0240 mol sample of N2O4(g) only is introduced into
an evacuated 0.372 L flask at 25 oC and allowed to come
to equilibrium. If KC for this system is 4.61 x 103, what
amount of N2O4(g) is present at equilibrium?

N2O4(g) ⇌ 2 NO2(g)
Solution:
1. Calculate [N2O4]initial:
2. Setup the ICE table

3. Use KC to solve for x, and the [ ]eq

43
 Exercise
Solution:
Calculate the molarities of each at equilibrium:

n 0.0240 mol
MN2O4, i = = = 0.0645 M
V 0.372 L

44
 Exercise
Solution:
Setup the ICE table:

N2O4 ⇌ 2 NO2

Initial [ ] 0.0645 0

Change -x + 2x

Equilib [ ] 0.0645 - x + 2x

45
 Exercise
3. Use KC to solve for x, and the [ ]eq
[NO2]2
KC = = 4.61 x 10-3
[N2O4]
Therefore
(2x)2
= 4.61 x 10-3
(0.0645 – x)
NOT
Multiply through, and rearrange getting a
x2 + 1.15 x 10-4x – 7.43 x 10-4 = 0 quadratic
in Exam!
Gives rise to a quadratic equation:
- b ± √ b2 – 4ac
x=
2a
x = 8.06 x 10-3 M, .: [N2O4]eq = 0.0565 M 46
 Aqueous Example
When Ag(s) is added to a solution of:
[Ag+(aq)]i = 0.200 M, [Fe2+(aq)]i = 0.100 M, &
[Fe3+(aq)]i = 0.300 M, a reversible reaction occurs:

Ag+(aq) + Fe2+(aq) ⇌ Ag(s) + Fe3+(aq) KC = 2.98

Calculate [ ]eq for all species present at equilibrium.

Solution:

1. Calculate QC to determine in which direction the

reaction will proceed
2. Setup the ICE table
3. Use KC to solve for x;
4. Substitute x and calculate the [ ]eq 47
 Aqueous Example
Solution:
1. Calculate QC to determine in which direction the
reaction will proceed

[Fe3+] (3.00)
QC = = = 15.0
[Ag+][Fe2+] (2.00)(1.00)

Since
QC > KC

.: The reverse reaction will dominate until

equilibrium is reached

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 Aqueous Example
Solution:
2. Setup the ICE table

Ag+ + Fe2+ ⇌ Fe3+

Initial [ ] 0.200 0.100 0.300

Change +x +x –x

Equilib [ ] 0.200 + x 0.100 + x 0.300 – x

49
3. Use KC to solve for x:

Ag(s) + Fe3+(aq) ⇌ Ag+(aq) + Fe2+(aq) KC = 2.98

[Ag+][Fe2+]
KC = = 2.98
[Fe3+]
(0.200 + x)(0.100 + x)
Therefore: = 2.98
(0.300 – x)
Multiply through, rearrange & solve for x: NOT
getting a
x = 0.16 quadratic
(Need to use the quadratic equation to solve) in Exam!
.: [Ag+]eq = 0.200 + x = 0.36 M
[Fe2+]eq = 0.100 + x = 0.26 M
[Fe3+]eq = 0.300 – x = 0.14 M 50