FAD 1007

CHEMISTRY 3

PREPARED BY : DR. LIEW SOOK YEE

Chemical Equilibrium
 CONTENT:
• Reversible reactions
-Dynamic equilibrium
• The equilibrium law
-Equilibrium constant
-Kc (in terms of concentration)
-Kp (in terms of partial pressure of gases)
• Equilibrium constant in homogeneous and heterogeneous
reaction
-Expression for equilibrium constant
 CONTENT (continue…)

• Position of equilibrium

• Calculations involving Kc
-Calculate Kc
-Calculation involving concentration, mass, no. of mole…
• Degree of dissociation, α
• Calculations involving Kp
-Mole fraction
• Relationship between Kc and Kp

• Reaction quotient (Q)

-Prediction for the direction of a reaction
 CONTENT (continue…)

• Le Chatelier’s Principle
-Factors affecting chemical equilibrium
-Concentration
-Pressure
-Temperature
-not affecting chemical equilibrium
-Catalyst
 Reversible reactions

-Chemical reaction from the LEFT to RIGHT: Forward reaction

-Chemical reaction from the RIGHT to LEFT: Reverse reaction

-Chemical reactions take place in both direction:

Reversible reactions
 Reversible reaction (continue…)

Examples of reversible reaction:

• Dissociation of dinitrogen tetroxide

• Contact process

• Haber process
 Reversible reaction (continue…)

When:
• Rate of reaction: Forward = Reverse
• Concentration of reactants & products remain
constant
-> The system is said to be in equilibrium state
which is called:
Chemical Equilibrium
 Dynamic equilibrium

Reaction rate

Forward reaction rate A & B decrease

Time

As reactants A & B start to react, products will start

to form. Concentration of A & B start to decrease.
Hence rate of reaction of A & B decreases with
time.
 Dynamic equilibrium(continue…)

Reaction rate
Reverse reaction rate C & D increase

Time

As reactants A & B react, more products (C & D) will

be formed. Products C & D will collide and react.
Hence rate of reaction of C & D increases with time.
 Dynamic equilibrium(continue…)

rate A & B = C & D

Reaction rate Dynamic equilibrium

t
Time

At certain point/time (t), rate of reactions of A & B and C & D are

equal. Reactants converting into products are at the same rate as
the products converting back into reactants. Forward and
reverse reactions continue indefinitely (reaction NOT stop)
although chemical equilibrium is achieved. At this point, the
chemical equilibrium is a dynamic process called dynamic
equilibrium (in a state of dynamic equilibrium after time t).
 Dynamic equilibrium
equilibrium established

Reaction rate
at time t

Dynamic equilibrium

t
Time

equilibrium established equilibrium established

Concentration
Concentration

at time t at time t
Dynamic equilibrium Dynamic equilibrium

t t
Time Time
 Dynamic equilibrium(continue…)

Example:
2SO2(g)+O2(g) ⇌ 2SO3(g)

https://socratic.org/questions/5933f79ab72cff624f77d212
 Dynamic equilibrium(continue…)

Concepts/Characteristics of dynamic equilibrium/chemical equilibrium:

- Equilibrium can be achieved in a closed system only.
- The concentrations/pressure/colour of reactants and products remain
constant
- The reaction rates for both forward and reverse reactions are the same.
- The final equilibrium position is the same regardless of whether the
equilibrium is approached from the forward and reverse direction.

*Although the concentrations are NOT necessarily equal, the concentrations

must eventually remain constant since the forward and reverse reactions are
occurring simultaneously and at the same rate.
equilibrium established
Concentration

at time t
Dynamic equilibrium
Concentrations
remain constant

t
Time
 Equilibrium law
The equilibrium law (law of mass action) states
that for any equilibrium at a constant
temperature, the product of the concentrations
of the products divided by the product of the
concentrations of the reactants, each raised to a
power equal to its coefficient in the balanced
chemical equation, is a constant, and is known
as equilibrium constant.
 Equilibrium constant, Kc
For a reaction, k1
aA (g) + bB (g) cC (g) + dD (g)
k−1 / k1 '

Rate (forward) = k1[A]a[B]b Rate (reverse) = k-1[C]c[D]d

At equilibrium, rate (forward) = rate(reverse) k1 [C] c [D] d
= a b
k1[A]a[B]b = k-1[C]c[D]d or k-1 [A] [B]
So the equilibrium constant, Kc is given by the equilibrium law;

where
“c” in Kc refer to concentration
[ ] is equilibrium concentration in mol dm-3 / mol L-1 and others
 Equilibrium constant, Kc (continue…)

aA (g) + bB (g) cC (g) + dD (g)

Unit of Kc :
mol c+d-(a+b) dm-3[c+d-(a+b)]
Or

mol c+d-(a+b) L-[c+d-(a+b)]

Hence, in some equilibrium reactions, it is possible the
equilibrium constants has no units.
 Equilibrium constant, Kc (continue…)

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

Forward: [ HI ]2
H2 (g) + I2 (g) 2HI (g) Kc =
[ H 2 ][ I 2 ]
Reverse: Reversing the reaction results in a reciprocal equilibrium reaction

2HI (g) H2 (g) + I2 (g) [ H 2 ][ I 2 ]

Kc ' = 2
= 1/ Kc
[ HI ]

½ H2 (g) + ½ I2 (g) HI (g) 𝐻𝐼 [𝐻𝐼]2 1 1

𝐾𝑐 ′′ = 1 1 =( )2 = (𝐾𝑐 ) =
2 𝐾𝑐
𝐻2 𝐼2
[𝐻2 ]2 [𝐼2 ]2
 Equilibrium constant, Kc (continue…)
Write equilibrium constant expression and its unit for the following
reaction if the concentration is in mol dm-3:
2SO3(g) ⇌ 2SO2(g) + O2(g)

2SO2(g) + O2(g) ⇌ 2SO3(g)

SO2(g) + ½ O2(g) ⇌ SO3(g)

 Equilibrium Constant, Kp
aA(g) + bB(g) cC(g) + dD(g)

• KP is the equilibrium constant for reactions

involving gases, we can write:

KP =
( PC ) (PD )
c d

(PA ) (PB )
a b

where
P is partial pressure of the gas (atm, bar, Pa, kPa and others)
KP is partial pressure equilibrium constant
Summary for equilibrium constant:
aA (g) + bB (g) cC (g) + dD (g)

[C]c [D]d
For solutions/gases: Kc = [ ] = mol/L, mol/dm3......
[A]a [B]b

For gases:
KP =
(PC ) (PD )
c d
P in atm, bar, kPa, Pa….
(PA )a (PB )b

www1.udel.edu/chem/sametz/102Fall11/chapter15_lecture_finalJRB.ppt
 Equilibrium constant in homogeneous
and heterogeneous reactions

Homogeneous equilibrium
- All the reactants and products in same / one phase

Heterogeneous equilibrium
- one or more reactants or products are in a different
phase
 Equilibrium constant in homogeneous and heterogeneous reactions (continue…)

Example of homogeneous equilibrium:

KP =
( PC ) (PD )
c d

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

(PA )a (PB )b

Expression in Kc: Expression in KP:

KC = KP =

If [ ] in mol dm-3,
Unit KC :

If P in atm,
Unit KP :
 Equilibrium constant in homogeneous and heterogeneous reactions (continue…)

Example of heterogeneous equilibrium:

H2O (g) + C (s) H2 (g) + CO (g) KP =

( PC ) (PD )
c d

(PA )a (PB )b
Expression in Kc: Expression in KP:

[H2 ][CO] (PH2 )(PCO )

KC = KP =
[H2O] (PH2O )
If [ ] in mol dm-3, If P in atm,
unit = mol dm-3 unit = atm

Why carbon is not included in the Kc expression???

Pure solids (s) and liquids (l) are not included in the equilibrium
constant expression. This is because they have constant concentration,
so they are disregarded and kept at 1.
*same thing is applied to Kp
 The Position of Equilibrium
• The equilibrium constant, K, is the ratio of products to
reactants.
• Therefore, the larger K the more products are present at
equilibrium.
• Conversely, the smaller K the more reactants are
present at equilibrium.
• If K > 1, then equilibrium favours the products and
equilibrium lies to the right.
• If K < 1, then equilibrium favours the reactants and the
equilibrium lies to the left.

KP =
( PC ) (PD )
c d

(PA )a (PB )b
 Calculations involving Kc
Qn. 1
Calculate Kc for the following equilibrium:

CO (g) + 3H2 (g) CH4 (g) + H2O (g)

Reactants Products
[CO]eq = 0.0613 mol dm-3 [CH4] eq = 0.0387 mol dm-3
[H2] eq = 0.1839 mol dm-3 [H2O] eq = 0.0387 mol dm-3
 Calculations involving Kc (continue…)

General method of calculating Kc :

1. Write the balanced equation and phase (if not given)

2. Write the Kc expression based on the equation
3. Determine the EQUILIBRUM concentrations (mol dm-3
/ mol L-1/ M)
-involving mole, mass, volume, relative molecular
mass…
4. Substitute all the necessary values and calculate the
Kc, check the unit of Kc.
Qn. 1
Calculate Kc for the following equilibrium:

CO (g) + 3H2 (g) CH4 (g) + H2O (g)

Reactants Products
[CO]eq = 0.0613 mol dm-3 [CH4] eq = 0.0387 mol dm-3
[H2] eq = 0.1839 mol dm-3 [H2O] eq = 0.0387 mol dm-3
 Calculations involving Kc (continue…)

CO (g) + 3H2 (g) CH4 (g) + H2O (g)

[CH 4][H 2O]

KC = 3
[CO][H 2]
(0.0387)(0 . 0387)
= 3
(0.0613)(0 .1839)
= 3.93 mol dm -2 6
Qn. 2 Calculations involving Kc (continue…)

Calculate the value of Kc for forward and reverse reaction for the
following system with the given equilibrium concentrations.
2HI (g) H2 (g) + I2 (g)
[HI] = 1.75 mol dm-3 [H2] = 1.125 mol dm-3 [I2] = 0.125 mol dm-3
 Calculations involving Kc (continue…)
Qn. 3
2A (aq) 2B (aq) + C (aq)
An amount of 0.5 mol of A was placed in a flask of volume 20.0 dm3 at T °C. When
the equilibrium was established, there was 0.35 mol of A in the flask. Calculate the
equilibrium constant Kc and predict the position of equilibrium for the above
reaction at T °C.
2A (aq) 2B (aq) + C (aq)
[B]2 [C]
Initial (mol): 0.5 0 0 KC =
[A] 2
Change (mol): -2x +2x +x (0.0075) 2(0.00375)
Equilibrium
=
0.5-2x 2x x (0.0175) 2
(mol):
0.5-2x = 0.35 A=0.35mol B = 2(0.075) C=0.075mol = 6.9 x 10−4 mol dm−3
x = 0.075 = 0.15mol
Equilibrium favours the
reactants so equilibrium
At equilibrium, [A] = 0.35/20 = 0.0175 mol dm-3 position lies to the left
[B] = 0.15/20 = 0.0075 mol dm-3 (Because Kc is less than 1)
[C] = 0.075/20 = 0.00375 mol dm-3
This method (ICE) can
use to find Kp if the Qn is
dealing with pressure
 Calculations involving Kc (continue…)
Qn. 4
Consider the reaction:
H2(g) + I2(g) 2 HI(g),
where Kc = 55.6 at 425oC.
If [H2]0 = [I2]0 = 0.10 M, and [HI]0 = 0.0 M, what are
their concentrations at equilibrium?

Calculating equilibrium concentrations using initial

concentrations and value of Kc
 Calculations involving Kc (continue…)

*Using the ICE table to calculate equilibrium concentrations

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

• ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯

Initial (M)
Change (M)
Equilibrium (M)
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ ⎯⎯⎯⎯⎯⎯⎯

Kc = = = 55.6
 Calculations involving Kc (continue…)
4x 2
2 = 55.6
(0.10 − x)

4x 2 = 55.6 (0.10 − x)2

4x2 = 55.6 (0.01 − 0.2x + x2 )
4x2 = 0.556 − 11.12x + 55.6x2
51.6x − 11.12x + 0.556 = 0
2

x = 0.1367, x = 0.0789
(reject)

[H2] = 0.10 - 0.0789 [HI] = 2 x 0.0789

= 0.0211 M = 0.158 M

[I2] = 0.0211 M
 Calculations involving Kc (continue…)
Qn. 5
The decomposition of HI at low temperature was studied by injecting 2.50 mol
of HI into a 10.32 L vessel at 25 oC. What is [H2] at equilibrium for the
following reaction with Kc =1.26 x 10-3?
2 HI(g) H2(g) + I2(g)
 Qn. 6 Calculations involving Kc (continue…)
An equilibrium mixture contains 27.5 g of PCl3 (g), 8.52 g Cl2 (g) and 31.3 g PCl5
(g) in a 4000 cm3 container at 250 oC as shown in the equation below.
PCl5 (g) PCl3 (g) + Cl2 (g)
Calculate Kc. [Relative molecular mass of PCl5 = 208.5, Cl2 = 71, PCl3 =137.5]
Answer:
PCl5 (g) PCl3 (g) + Cl2 (g)
1

Need to find equilibrium concentration of PCl5, PCl3, Cl2

27.5 g
[PCl 3 ] = 2
137.5 g mol -1 x 4000 x 10−3 dm3
= 0.05 mol dm-3 [PCl 3][Cl 2]
Kc =
[PCl 5]
8.52 g
[Cl 2 ] = 0.050 mol dm−3x 0.030 mol dm−3
71 g mol -1 x 4000 x 10−3 dm3 =
0.0375 mol dm−3
= 0.03 mol dm -3

= 0.04 mol dm−3

31.3 g
[PCl 5 ] =
208.5 g mol -1 x 4000 x 10-3 dm−3
= 0.0375 mol dm−3
Qn. 7
A mixture of 2.0 mol of N2, 2.0 mol of H2 and 3.0 mol of ammonia was placed in a
2.0 L vessel at 472 oC as shown in the equation below. At equilibrium, 4.0 mol of
ammonia was obtained.

Calculate equilibrium constant Kc for the reaction.

Answer: 1 N2(g) + 3H2(g) 2NH3 (g) *Qn give initial
mol of the
Initial (mol): 2.0 2.0 3.0 product = 3.0, so
do not put initial
Change (mol) : -x -3x +2x no. of mol
equals to 0 for
Equilibrium (mol): 2.0-x 2.0-3x 3+2x product.

2 3+2x = 4.0 3
x = 0.5 [NH3]2
KC =
[N2][H2]3
So, at equilibrium:
4.0
No. of mol N2= 2.0 - 0.5 = 1.5 (2.0)2
=
1.5 0.5 3
No. of mol H2 = 2.0 - 3(0.5) = 0.5 ( )
2.0 2.0
= 𝟑𝟒𝟏. 𝟑 mol-2 L2
No. of mol NH3 = 4.0
 Degree of dissociation, α
Degree of dissociation is defined as the fraction of
a substance dissociated.
A B + C
Initial (M) a 0 0
Change (M) -x +x +x
Equilibrium (M) a-x x x

α = x/a

• When α = 1, there is complete dissociation (100%)

 Degree of dissociation, α (continue…)

Example

An amount of 0.8 mol L-1 HCOOH is dissociated and form

5.2 x 10-2 mol L-1 of H+ ion as shown in the equation below.
Calculate the degree of dissociation and percentage of
dissociation of HCOOH.
HCOOH (aq) H+ (aq) + HCOO- (aq)

Solution:
α= %α =
 Calculations involving Kp
Revision: Equilibrium Constant, Kp
aA + bB cC + dD
• KP is the equilibrium constant for reactions
involving gases, we can write:

KP =
( PC ) (PD )
c d

(PA ) (PB )
a b

where
P is partial pressure of the gas (atm, bar, Pa, kPa and
others)
KP is partial pressure equilibrium constant
 Calculations involving Kp (continue…)

All the partial pressures add up = total pressure

(Dalton’s law of partial pressure):

Ptotal = PA + PB +...

Mole fraction of A:
moleA
XA =
moletotal

Partial pressure of A (mole fraction of A x total pressure):

PA = XA Ptotal
 Calculations involving Kp (continue…)
Qn. 1
The gases SO2, O2 and SO3 are allowed to reach equilibrium at a constant
temperature as shown in the following equation.
2SO2(g) + O2(g) ⇌ 2SO3(g)
At equilibrium, the partial pressure of SO2 and SO3 are 0.050 atm and 1.00
atm respectively. The equilibrium constant Kp is 1.6 x 104 atm-1. Find the
partial pressure of O2 at equilibrium..

Answer: 2SO2(g) + O2(g) ⇌ 2SO3(g)

(PSO3 ) 2
Kp =
(PSO2 ) 2 (PO 2 )
2
(1.00)
1.6 x10 4 =
(0.050) 2(O 2 )
(1.00) 2
Partial pressure O 2 =
(0.050 ) 2 (1.6 x10 4)
= 0.025 atm
Qn. 2 Calculations involving Kp (continue…)
2.0 mol of hydrogen is reacts with 2.0 mol of iodine at 300 oC in a 3.0 dm3
container as shown in the equation below.
H2(g) + I2(g) 2HI (g)
At equilibrium, 1.6 mol of hydrogen iodide are obtained. If total pressure of
the system is 1.0 x 105 Pa, calculate the value of KP for equilibrium mixture.
Answer:
1 H2(g) + I2(g) 2HI (g) HI = 1.6 mol H2 = 2.0-x
2x = 1.6 = 2.0-0.8
Initial (mol): 2.0 2.0 0
x = 0.8 = 1.2 mol
Change (mol) :
-x -x +2x
I2 = 1.2 mol
Equilibrium (mol):
2.0-x 2.0-x 2x

2 PA = XA Ptotal 3
PHI 2
Total no. of mol = 1.2 + 1.2 + 1.6 = 4.0 mol KP =
PH2 PI2
1.6
PHI = x 1.0 x 105 = 4.0 x 104 Pa 4.0 x 104 2
4.0 =
3.0 x 104 3.0 x 104
1.2 = 1.78
PH2 = x 1.0 x 105 = 3.0 x 104 Pa
4.0
(No unit)
PI2 = 3.0 x 104 Pa
 Qn. 3 (calculation involving degree of dissociation, α) Calculations involving Kp (continue…)
At a pressure of 682 kPa and a temperature of 127 oC, 1 mol of dinitrogen
tetroxide is 80% dissociated as shown in the following equation.
N2O4 (g) 2NO2 (g)
Calculate the partial pressure equilibrium constant for this reaction.
Answer: 1 N2O4 (g) 2NO2 (g)
Initial (mol): 1.0 0
Change (mol) :
Equilibrium (mol):

2 % α = 80, α = 0.80 3 PA = XA Ptotal 4

80% of N2O4 is dissociated: PN2O4 =
KP =
0.8 = x/1
x = 0.8
So, at equilibrium:
No. of mol N2O4= PNO2 =

No. of mol NO2 =

Total no. of mol =

 Qn. 4 Calculations involving Kp (continue…)
Bromine gas Br2 reacts with chlorine gas Cl2 at 400 oC to form bromine
monochloride BrCl as shown in equation below.
Br2 (g) + Cl2 (g) 2BrCl (g)
The initial partial pressure of Br2 and Cl2 is 0.34 atm and 0.51 atm
Answer:
respectively. Calculate KP for the reaction at 400 oC if the partial pressure of
BrCl is 0.46 atm at equilibrium.
Answer:
 Relationship between Kc and Kp
Partial pressure of a gas is related to number of
moles of the gas by the ideal gas equation:
n/V = M
PV = nRT where M is the
concentration of the
P = (n/V) RT gas

P = MRT
Partial pressure ∝ concentration

Gas constant, R = 0.08206 L atm K-1 mol-1

(0.0821)
 Relationship between Kc and Kp (continue…)

aA(g) + bB(g) cC(g) + dD(g)

PC c PD d
( )( )
K C = RT RT
P = MRT P P
( A )a ( B )b
For substance A: RT RT
PA = [A] RT 1
( )c +d (PC )c (PD )d
[A] = PA/RT 1 K C = RT
1
( )a+b (PA )a (PB )b
RT
[C] c[D] d
KC = a b 2 KC = (
1 c+d-(a+b)
) KP
[A] [B] RT
-Substitute 1 into 2 1 n
-do the same for B, C, D KC = ( ) KP
RT
𝐾𝐶 (RT)𝚫𝐧 = 𝐾𝑃

Δn = no. of moles of products – no. of moles of reactants.

 Relationship between Kc and Kp (continue…)

(a) 2 HI(g) H2(g) + I2(g), write the relation between Kc and

Kp.
𝐾𝐶 (RT)𝚫𝐧 = 𝐾𝑃
Δn = 2-2
=0 K C (RT) 0 = K P

So, Kc = Kp

(b) PCl5 (g) PCl3 (g) + Cl2 (g) , write the relation between Kc
and Kp.
𝐾𝐶 (RT)𝚫𝐧 = 𝐾𝑃
Δn = 2-1
=1 K C (RT) 1 = K P

So, Kc(RT)= Kp
 Relationship between Kc and Kp (continue…)
Example:
The equilibrium constant Kp for the following reaction is 7.73 x 10-4
atm-2 at 350 oC. What is the value of Kc for the reaction at the same
temperature? Given that R = 0.0821 L atm K-1 mol-1.
N2 (g) + 3H2 (g) 2NH3 (g)

𝐾𝐶 (RT)𝚫𝐧 = 𝐾𝑃

Δn = 2-(1+3)
= -2

Kc (RT)Δn= Kp
Kc [(0.0821 L atm K-1mol-1) (350+273K)]-2 = 7.73 x 10-4 atm-2
Kc = 7.73 x 10-4 atm-2
[(0.0821 L atm K-1mol-1) (350+273 K)]-2
= 2.02 mol-2 L2
 Relationship between Kc and Kp (continue…)
Question:
The equilibrium constant Kc for the following reaction is 5.2 x 10-3
mol L-1 at 250 oC. What is the value of Kp for the reaction at the same
temperature? Given that R = 0.0821 L atm K-1 mol-1.
PCl5 (g) PCl3 (g) + Cl2 (g
 Reaction Quotient, Q
• To predict the direction of any chemical reaction
• Obtain by substituting the initial concentrations/partial
pressures of reactants and products into equilibrium
constant expression which is almost the same as Kc /KP except
NOT at equilibrium. (P ) (P ) c d
K = C D

• Comparing with K value (P ) (P ) P

A
a
B
b

Relationship Direction of reaction

Q >K • Excess of products will react to form reactants to establish
equilibrium (more products in the reaction mixture initially).
• The reaction will go from the right to left (reverse reaction).

Q=K • The reaction is at equilibrium. The mixture contains equilibrium

concentrations of reactants and products.
Q<K • Excess of reactants will react to form products to establish
equilibrium (more reactants in the reaction mixture initially).
• The reaction will go from the left to right (forward reaction).
 Example: Reaction quotient, Q (continue…)
Consider the reaction between N2 (g) and H2 (g) to form NH3 (g).

A mixture of 1.0 mol of N2, 2.0 mol of H2 and 2.0 mol of ammonia is placed in a
1.0 dm3 vessel at 472 oC. The equilibrium constant for the reaction is 0.104 mol-2
dm6.
(a) What is the reaction quotient for the reversible reaction?
(b) Is the system at equilibrium?
(c) Predict the direction of reaction.

Answer:
(a) [NH3 ]2
QC = (b) Qc not equals to Kc (Qc is larger than Kc).
[N2 ][H2 ]3
Hence, the system is not at equilibrium.
2.0
( )2
= 1.0
1.0 2.0 (c) The direction of reaction is from right to
( )( )3
1.0 1.0 left.
(2.0)2 (Because Qc > Kc)
=
(1.0)(2.0)3
= 0.50 dm
mol6-2mol
dm6−2
 Le Chatelier’s Principle
According to Le Chatelier’s principle:
If a chemical system at equilibrium experiences a change in
temperature, pressure or concentration of a reactant or
product, the position of the equilibrium shifts to partially
counteracts the effect of the change until a new
equilibrium is established.

Factors affecting position of equilibrium:

-concentrations of reactants and products
-temperature of the experiment
-pressure in reactions involving gases
 The Effect of Concentration
-When the concentration of the reactants/products at
equilibrium is increased, the equilibrium position will shift in the
direction that tends to reduce the concentration of the
reactants/products.

-Increasing the concentration of reactants to a system in

equilibrium will shift the equilibrium position to the right
(forward reaction).
-will reduces concentration of reactants added & increases
concentration of products
-new equilibrium achieved but relative amount of reactants &
products in equilibrium remains constant. So, concentrations
have no effect on the values of Kc & Kp.
 The Effect of Concentration (continue…)

Example: If more hydrogen gas/iodine gas is added to the

following equilibrium mixture, what will happen to the
equilibrium position and equilibrium constant?

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

Answer:
Equilibrium position will shift to right .
Kc unaffected.

(According to Le Chatelier’s principle, an increase of concentration

of hydrogen gas/iodine gas (reactants) to the equilibrium system,
the equilibrium position will shift to right (forward reaction) until
rate of forward reaction equals to reverse reaction (or the ratio of
the concentrations of products to reactants gives the original
value of Kc- Kc unaffected). New equilibrium is re-established.)
 The Effect of Temperature
- According to Le Chatelier’s principle, when the
temperature in an equilibrium system is increased, the
equilibrium position will shift in the direction of
endothermic (absorb heat).
- When the temperature in an equilibrium system is
decreased, the equilibrium position will shift in the
direction of exothermic (release heat).
- If the temperature of an equilibrium system is increased,
the rate of both forward and reverse reactions increase
but not increase by the same extent. Hence, a change in
temperature will cause a change in equilibrium position
and equilibrium constant, Kc & Kp.
 The Effect of Temperature (continue…)
Example:

Consider the following reaction:

ΔH = + 57.0 kJ/mol
N2O4 (g) 2NO2 (g)
(endothermic reaction)

According to Le Chatelier’s principle:

-Increasing temperature of the above reaction will shift the
equilibrium position to the right (endothermic reaction). Heat is
absorbed to lower the temperature. The concentration of NO2 will
increase but the concentration of N2O4 will decrease . Thus, the
value of Kc or Kp will increase with increase in temperature.

[NO2 ]2
KC =
[N2O4 ]
 The Effect of Temperature (continue…)
Example:

Consider the following reaction:

ΔH = + 57.0 kJ/mol
N2O4 (g) 2NO2 (g)
(endothermic reaction)

If decrease temperature?
According to Le Chatelier’s principle:
-Decreasing temperature of the above reaction will shift the
equilibrium position to the left ( exothermic reaction). Heat is
released to increase the temperature. The concentration of N2O4
will increase but the concentration of NO2 will decrease. Thus, the
value of Kc or Kp will decrease with decrease in temperature.
2
[NO2 ]
KC =
[N2O4 ]
 The Effect of Temperature (continue…)
Example:
Consider the following reaction:
PCl3(g)+Cl2(g)⇌PCl5(g) ΔH = -92.5 kJ

What will happen to the equilibrium system if temperature is

decreased?
According to Le Chatelier’s principle:
-Decreasing temperature of the above reaction will shift the
equilibrium position to the ( reaction). Heat is
released to increase the temperature. The concentration of PCl3
and Cl2 will but the concentration of PCl5 will .
Thus, the value of Kc or Kp will with decrease in
temperature.
[PCl5]
KC =
[PCl3][Cl2]
 The Effect of Pressure
• Only affects reversible reactions involving gaseous reactants &
products.

3 ways to change the pressure of an equilibrium system at constant

temperature which will effect the equilibrium:
1. changing partial pressure by adding / removing a gaseous
reactant or product from equilibrium mixture - Px = [x]RT
( = effect of change in concentration)

2. changing external pressure will change the volume of the system

(external pressure , volume . external pressure , volume ) P α 1/V
3. Adding an inert gas (internal pressure) to equilibrium mixture at
- constant pressure
- constant volume
 The Effect of Pressure (continue…)

Changing external pressure will change the volume of the

system:
-When the external pressure in an equilibrium system is
increased, the equilibrium position will shift in the direction
that decrease the number of moles of gas (reduce its pressure
by reducing the number of gaseous molecules because the
pressure of the gas ∝ number of mole of gas).

-when the external pressure in an equilibrium system is

decreased, the equilibrium position will shift in the direction
that increase the number of moles of gas.

-a change in pressure will have no effect on the values of Kc &

Kp.
 The Effect of Pressure (continue…)

-Changes in pressure (external) will only affect the

equilibrium system if there is a change in coefficient in
the balanced chemical equation (Δn).
In other words:
Changes in pressure (external) will not affect the
equilibrium system when the total number of moles of
gaseous reactants is the SAME as the total number of
moles of gaseous products. For example:
H2 (g) + I2 (g) 2HI (g)

2 mol 2 mol

Δn = 2 - 2 = 0
 The Effect of Pressure (continue…)

Considering the following reaction:

N2O4 (g) 2NO2 (g) Δn = 1
1 mol 2 mol

OXFORD FAJAR 2016

 The Effect of Pressure (continue…)

1 mol 2 mol
-Increasing the external pressure (reducing the volume of the gas in the
container) of an equilibrium system causes the equilibrium position
shift to the left with lower number of moles of gaseous substances.
Hence, more reactants are formed until the ratio of the amount of
products with reactants give the value of Kp.
-Decreasing the external pressure (increasing the volume of the gas in
the container) of an equilibrium system causes the equilibrium position
shift to the right with higher number of moles of gaseous substances.
Hence, more products are formed until the ratio of the amount of
products with reactants give the value of Kp. OXFORD FAJAR 2016
 The Effect of Pressure (continue…)
Example:
What will happen to the equilibrium position and
equilibrium constant for following equilibrium if the
pressure is increased?

PCl3(g)+Cl2(g)⇌PCl5(g)

1 mol 1 mol 1 mol

Answer:
-No. of mol of gas (reactant-left) = 2, No. of mol of gas (product-right) = 1
-Equilibrium position shift to the right with lower number of moles
of gaseous substances.
-Equilibrium constant will not change / No effect on equilibrium
constant.
 The Effect of Pressure (continue…)

Effects of addition of inert gas:

At constant pressure,
-total pressures unchanged (PT before = PT after)
-so, partial pressure of reactants & products must
to keep the pressure constant.
-According to Le Chaterlier’s Principle, equilibrium
system will shift to direction that increases
number of moles of gas.
 The Effect of Pressure (continue…)

Effects of addition of inert gas:

At constant volume,
-total number of gaseous molecules
-so, total pressures
-partial pressure of reactants & products remain
unchanged.
-no shift/no effect on the position of equilibrium
system
 The Effects of Catalyst
Catalyst:
-increase reaction rates of both forward & reverse
reactions
-provide alternative reaction pathway with lower
activation energy, Ea
-not participate in the reaction
-no effect on equilibrium position & equilibrium
constant
-not increase the yield of products
-remain same properties and volume at the end of
reaction
 The Effects of Catalyst (continue…)

Energy profile:

OXFORD FAJAR 2003

Summary

Factor Equilibrium constant

Concentration No effect

Temperature Effected

Pressure No effect

Catalyst No effect
~Thank you~