Chemical equilibrium

Dr Shereen Samir
Associated Prof. in Chemical Engineering
 CHEMICAL EQUILIBRUIM
• Static and Dynamic Equilibrium:
• The state equilibrium can be observed in physical and chemical
systems.

• Also, equilibrium can be static or dynamic in nature.

• A book lying on the table is an example of static equilibrium.

• On the other hand, when an escalator is coming down and a

passenger is going up at the same speed it is a case of dynamic
equilibrium

• Equilibrium is a state in which there are no observable changes as

time goes by.
1. Physical Equilibrium

H 2O(l )  H 2O( g )

2. Chemical Equilibrium
N 2O4 ( g )  2 NO2 ( g )

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 Few reaction are proceed in one direction.
A B C  D
 Most reactions are reversible?

A B  C  D
 Chemical equilibrium: is achieved when
the rates of the forward and reverse reactions
are equal
and the concentrations of the reactants and
products remain constant
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 N2O4 (g) 2NO2 (g)

equilibrium
equilibrium
equilibrium

Start with NO2 Start with N2O4 Start with NO2 & N2O4
constant
 The Equilibrium Constant
aA  bB  cC  dD
 A, b, c, & d: are the stoichiometric
coefficients for A, B, C , & D ‫ثابت االتزان = كسر‬
 K is the equilibrium constant. ‫ هو ناتج ضرب‬:‫البسط‬
Concentration ‫تركيز النواتج كل مرفوع‬
[C ]c [ D]d of products
‫الى اس يساوي عدد‬
K ‫موالته في معادلة التفاعل‬
Equilibrium
constant [ A]a [ B]b Concentration
of reactants
‫الموزونه‬
 The equilibrium constant: for a reversible
reaction at equilibrium and at constant ‫ هو ناتج ضرب‬:‫والمقام‬
temperature, a certain ratio of reactant and ‫تركيز المتفاعالت كل‬
product concentrations has a constant value, ‫مرفوع الى اس يساوي‬
K, called the equilibrium constant. ‫عدد موالته في معادلة‬
‫التفاعل الموزونه‬
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The Equilibrium Constant
c d
[C ] [ D]
K a b
[ A] [ B]

The concentration of solids and pure

liquids and solvents are not included in
the expression for the equilibrium constant.
 K has no unit

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14.2 Writing Equilibrium Constant
Expressions
 Homogeneous Equilibrium: all species are in the
same phase
 Example: homogenous gas-phase equilibrium of the
dissociation of N2O4,

N 2O4 ( g )  2 NO2 ( g )
K is given by:
2
[ NO2 ] 2 P
Kp 
NO2
Kc 
[ N 2O4 ] PN 2O4
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Concentration Units Pressure Units
14.2 Writing Equilibrium Constant
Expressions
 Relationship between Kc & Kp:
 Kc ≠ Kp
n
K p  K c (0.0821T )
 ∆n = moles of gaseous products – moles of
gaseous reactants aA  bB  cC  dD
n  (c  d ) products (g)  (a  b) reactants (g)
 Kc = Kp, when ∆n = 0 10
The equilibrium concentrations for the reaction between carbon
monoxide and molecular chlorine to form COCl2 (g) at 740C are
[CO] = 0.012 M, [Cl2] = 0.054 M, and [COCl2] = 0.14 M. Calculate
the equilibrium constants Kc and Kp.

CO (g) + Cl2 (g) COCl2 (g)

[COCl2] 0.14
Kc = = = 220
[CO][Cl2] 0.012 x 0.054

Kp = Kc(RT)n

n = 1 – 2 = -1 R = 0.0821 T = 273 + 74 = 347 K

Kp = 220 x (0.0821 x 347)-1 = 7.7

The equilibrium constant Kp for the reaction
2NO2 (g) 2NO (g) + O2 (g)
is 158 at 1000K. What is the equilibrium pressure of O2 if the PNO
= 0.400 atm and PNO2 = 0.270 atm?

2
PNO PO2
Kp = 2
PNO2

2
PNO2
PO2 = Kp
2
PNO

PO2 = 158 x (0.400)2/(0.270)2 = 347 atm

 Heterogenous equilibrium applies to reactions in which
reactants and products are in different phases.

CaCO3 (s) CaO (s) + CO2 (g)

[CaO][CO2] [CaCO3] = constant

Kc‘ = [CaO] = constant
[CaCO3]

[CaCO3]
Kc = [CO2] = Kc‘ x Kp = PCO2
[CaO]

The concentration of solids and pure liquids are not

included in the expression for the equilibrium constant.

‫المواد الصلبة ليس لها تركيز كالغازات حيث انها لم تنتشر في الوعاء بل هي كميات بسيطة في اسفل الوعاء‬
‫لذلك قانون االتزان يحوي فقط تراكيز الغازات‬
 CaCO3 (s) CaO (s) + CO2 (g)

PCO 2 = Kp

PCO 2 does not depend on the amount of CaCO3 or CaO

•Write the equilibrium constant Kc expression for the following
reactions
CH4 (g)+ 2 H2O (g) ⇋ CO2 (g)+4H2 (g)
CaCO3 (s) ⇋ CaO (s)+CO2(g)
H2 (g)+I2 (g) ⇋ 2HI (g)

3 Fe (s) + 4H2O (g) ⇋ Fe3O4 (s) + 4H2 (g)

Q: What is Kp in terms of Kc for the following
reaction ?

2 NO( g )  O2 ( g )  2 NO2 ( g )
A. Kp = KcRT
B. Kp = Kc/RT
Solution:
C. Kp = KcR/T
D. Kp = Kc K p  K c ( RT ) n
E. Kp = Kc/(RT)2 n  2  3  1
1 Kc
K p  K c ( RT ) 
RT

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N2O4 (g) 2NO2 (g) 2NO2 (g) N2O4 (g)

[NO2]2 [N2O4] 1
K= = 4.63 x 10-3 K‘ = = = 216
[N2O4] [NO2] 2 K

When the equation for a reversible reaction

is written in the opposite direction, the
equilibrium constant becomes the reciprocal
of the original equilibrium constant.
For the reaction A⇋B Rate constant =K1
So for the reaction n* (A⇋B ) rate constant K2= (K1) n
Example : Calculate the equilibrium constant for the reaction
A (g) + B (g) ⇋C (g) + D (g)

If at equilibrium 1 mol of A, 0.5 mole of B, 3.0 mole of C and 10 mol of D are

present in a one liter vessel.
Solution: From the law of equilibrium

KC = [C] [D]
[A] [B]
Kc = 3 * 10 /1 *0.5 = 60
Example :- In an experiment carried out at 298 K, 4.0 mol of
NOCl were placed in a 2 litre flask and after the equilibrium
was reached 1.32 mol of NO were formed. Calculate Kc at
298 K for the reaction
2NOCl (g) ⇋ 2 NO (g) + Cl2 (g)
 Le Châtelier’s Principle
If an external stress is applied to a system at equilibrium, the
system adjusts in such a way that the stress is partially offset
as the system reaches a new equilibrium position.

• Changes in Concentration

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

Equilibrium
Add
shifts left to
NH3
offset stress
‫ فان النظام سوف‬,‫عندما نؤثر بمؤثر خارجي على نظام في حالة اتزان‬
‫يعدل من نفسه لكي يعوض التاثير الحاصل وبتالي يصل الى حالة االتزان‬
‫مره اخرى‬
 Le Châtelier’s Principle

• Changes in Concentration continued

Add Add
Remove Remove

aA + bB cC + dD

Change Shifts the Equilibrium

Increase concentration of product(s) left
Decrease concentration of product(s) right
Increase concentration of reactant(s) right
Decrease concentration of reactant(s) left
 Le Châtelier’s Principle

• Changes in Volume and Pressure

A (g) + B (g) C (g)

Change Shifts the Equilibrium

Increase pressure Side with fewest moles of gas
Decrease pressure Side with most moles of gas
Increase volume Side with most moles of gas
Decrease volume Side with fewest moles of gas
 For each of the following equilibrium systems,
predict the direction of net reaction in each case as
a result of increasing the pressure (decreasing
the volume) on the system at constant temperature.

Solution:
↑ pressure ::::: shift to the side of fewest (less)
moles of gases moles
(a) 2PbS (s)  3O2 ( g )  2PbO(s)  2SO2 ( g )
Δn = 2 – 3 = -1 < 0 side of fewest gaseous moles is the product
THUS: the equilibrium will shift26 to the right
 (b) PCl5 ( g )  PCl3 ( g )  Cl2 ( g )
Δn = 2 – 1 = 1 > 0 side of fewest gaseous moles
is the reactant
THUS: the equilibrium will shift to the right
(c) H 2 ( g )  CO2 ( g )  H 2O( g )  CO( g )
Δn = 2 – 2 = 0
THUS: the change in pressure has NO
effect on the equilibrium

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Le Châtelier’s Principle
 Le Châtelier’s Principle
• Adding a Catalyst
• does not change K
• does not shift the position of an equilibrium system
• system will reach equilibrium sooner

uncatalyzed catalyzed

Catalyst lowers Ea for both forward and reverse reactions.

Catalyst does not change equilibrium constant or shift equilibrium.