General Chemistry

Prem Narayan Paudel

Chapter 3: Chemical Equilibrium

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Chemical equilibrium
Reversible reaction
A + B → C + D (forward reaction);
Some examples of Reversible reactions
A + B ← C + D (backward reaction)
PCl5(g) PCl3 (g) + Cl2(g)
A + B C + D

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

• A chemical reaction which can go in the
forward direction and backward direction
N2O4(g) 2 NO2(g)
simultaneously is called a reversible reaction

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

Irreversible reactions:
• That proceeds in one direction only. Like,
precipitation reaction , neutralization
reaction
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Nature of chemical equilibrium:

• Let a chemical reaction between

H2O(g) and CO(g) in a closed
vessel,represented as:
H2O(g) + CO(g) H2 (g) + CO2(g)

• At certain time, the system attains a

state of equilibrium in which two Fig: The changes in concentrations with time for the reaction
opposing reactions proceed equally
• Thus, chemical equilibrium may be
defined as the state of a reversible in
which the rates of the forward and
reverse reactions are equal and the Forward reaction rate equals the reverse
reaction rate
concentrations of the reactants and
products remain constant.
Fig: Reaction at equilibrium
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Characteristics of Chemical Equilibrium
• Cannot be attained in an Open Vessel
• Dynamic in nature (in constant motion)
• Reversible and attains equilibrium state spontaneously
• Can be approached from either side.
• Represents a compromise between opposing tendencies.
• A catalyst cannot change the equilibrium point
• Constancy of concentrations
The Equilibrium Constant:
Let a general reaction
aA + bB cC + dD
Where, molar concentration (active mass) of A, B, C and D at the equilibrium point
be represented as, [A], [B], [C] and [D]
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Contd...

• 'Active mass' means the molar concentration of any substances which

determines the rate of chemical reaction.
• Law of Mass action states that : the rate of a chemical reaction is proportional to
the active masses of the reactants.
• According to law of mass action,
rate of forward reaction = kf[A]a[B]b…………..(i)
rate of reverse reaction = kr[C]c[D]d…………..(ii)
• kf and kr are called rate constants
• Eventually the two processes are proceeding at the same rate, and the reaction is
at equilibrium:
• rate of forward reaction = rate of reverse reaction
i.e. kf[A]a[B]b= kr[C]c[D]d
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Contd...

Now, the above eqn. is written , kf/ kr = [C]c[D]d / [A]a[B]b………………..(iii)

• At specific temperature, kf and kr are constant and the ratio of kf/ kr is also
constant. Then, this ratio ,kf/ kris replaced by new constant term, Keqm.
which is known as equilibrium constant and the equation is called
equilibrium constant expression or equilibrium law.

• Keqm = [C]c[D]d / [A]a[B]b………………..(iv)

• Thus, equilibrium constant may be defined as the ratio of product of equilibrium
concentration of the products to the product of equilibrium concentration of the
reactants, with each concentration term raised to a power equal to the coefficient of the
species in the balanced chemical equation.
• Characteristics of equilibrium constant:
• The value of Keqm. of a reaction at constant temperature and pressure is same.
• The value of Keqm. of a reaction does not depend upon the initial concentration of
reacting species in the reaction.
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Contd...

• Characteristics of equilibrium constant:

• The value of Keqm does not depend upon the use of catalyst.
• The value of Keqm in fact depends on temperature and identity of the
reactants and products.
• The value of Keqm of a reversible reaction provides following ideas.
⇒ If the Kc value is large (Kc >> 1), the equilibrium lies to the right and
the reaction mixture contains mostly products.
⇒ If the Kc value is small (Kc <<1), the equilibrium lies to the left and
the reaction mixture contains mostly reactants.
⇒ If the Kc value is close to 1 (0.10 < Kc < 10), the mixture contains
appreciable amounts of both reactants and products.
Writing Equilibrium constant expressions:

• 1. N2O4(g) 2 NO2(g) Kc = [ NO2]2 / [N2O4] ; Kp= [ PNO2]2 / [PN2O4]

• 2. CaCO3(s) CaO (s) + CO2(g) K' = [ CO2][CaO] / [CaCO3]

• Since, concentrations of pure solids and liquids are fixed by their density
and molar mass (both constants) and do not vary with the amount, and
their concentration taken to be unity.
• Therefore, equilibrium constant exoression is given as.

• [ CO2]= [CaCO3]/ [CaO] .K' = Kp

• 3. Zn(s) + Cu2+(aq) Cu (s) + Zn2+(aq) ; Kc = [Zn2+] / [Cu2+]

• 4. 3Cu(s) + 2NO3-(aq) + 8H+(aq) 3Cu2+(aq) + 2NO(g) + 4H2O(l) ?????

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Reaction quotient (Q) and Equilibrium constant (Keqm.):
• The reaction quotient, Q, is the resulting value when we substitute
reactant and product concentrations into the equilibrium expression at any
instance.
1. If Q > K, the reaction will go to the left.
• The ratio of products over reactants is too large & the reaction will
move toward equilibriumby forming more reactants.
2. If Q < K, the reaction will go to the right.
• The ratio of products over reactants is too small & the reaction will
move toward equilibrium by forming more products.
3. If Q = K, the reaction mixture is already at equilibrium, so no shift occurs.
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Example
1. For the reaction, N2(g) + 3H2(g) 2NH3(g)
K= 6.0×10-2 at 500 °C. Predict the direction in which the system will shift to
reach equilibrium. if [NH3] = 1.0×10-5 M , [N2] = 1.0×10-5 M and [H2] = 2.0
×10-3 M.

• Therefore, since Q>K the direction goes towards the reactants (Q = 1.3 x103)
2. For the reaction, B 2A,

Kc = 2. Suppose 3.0 moles of A and 3.0 moles of B are introduced into a

2.00 L flask. (a) In which direction will the reaction proceed to attain
equilibrium? (b) Will the concentration of B increase, decrease or remain
the same as the system moves towards equilibrium?
• Try yourself
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Modifying equilibrium constant expressions

1. Changing stoichiometric coefficients

 If a reaction is multiplied by a certain number, its equilibrium constant must

be raised to a power equal to that number in order to obtain the new
equilibrium constant, for the new reaction.

• Let reactions be; …………..(i)

• If this reaction is multiplied by ½ the new chemical reaction and new

equilibrium constant will be
…………..(ii)

• Now, by the comparison of these expressions (i) and (ii), we may write;
K2 = (K1)1/2 to justify the above statement.

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2. Reversing the reaction
 The equilibrium constant for a reaction and its reverse are reciprocals to
each other

 Let reactions be; …………..(i)

• Its reverse reaction is;

…………..(ii)

• Then, by comparison of above expressions ‘i’ and ‘ii’,

we may write K2 = (1/K1) to justify the above statement

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3. Adding the multiple equilibrium reactions to get final reaction
• When two or more elementary reactions are added, their equilibrium
constants must be multiplied to give the equilibrium constant of overall
reaction (a complex reaction proceeding with successive reversible
elementary reactions).
 Let reactions be; ………..(i)

………..(ii)
• Final reaction is;
……..(iii)

• Then, by comparison of above expressions (i), (ii) and (iii),

we may write K3 = K1×K2 to justify the above statement.
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Relation between equilibrium constants, Kp and Kc:
• Deduce the relation, Kp = Kc × [RT] ∆n where, symbols have their
ususal meanings. (Attempt yourself)
• Actually, ∆n is the difference between the total moles of the products and the
total moles of the reactants, R is universal gas constant and T is absolute
temperature
• If the unit of concentration is changed, the equilibrium constant for a chemical
reaction will changes if ∆n ≠ 0. The new equilibrium constant is obtained as:
• Knew = Kprevious [conversion factor]∆ n

• For the reaction, 2NH3 N2 + 3H2

• If equilibrium constant in atm unit is to be changed to equilibrium constant in
torr unit. Then, the unit relation is P(Torr) = 760 × P(Atm.), so the equilibrium
constant also holds following relation, KP(Torr) = KP(Atm.)× [760]2
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Predict the relation between Kp and Kc for the reactions:

1. H2 + I2 2 HI

Δn = 2-2 = 0 ; KP = Kc (RT)Δn or KP = Kc (RT)0 or KP = Kc.

2. PCl5(g) PCl3 (g) + Cl2(g) Try yourself for others!

Δn = 2-1 = 1 (+ve); KP = Kc (RT)Δn or KP = Kc (RT)1 or KP˃ Kc.

3. 2SO2 + O2 2SO3

Δn = 2-3 = -1 (-ve); KP = Kc (RT)Δn or KP = Kc (RT)-1 or KP˂ Kc .

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Factors affecting the chemical equilibrium: Le Chatelier's Principle

• Le Chatelier's Principle
• If a system at equilibrium is subjected to a change of pressure,
temperature, or the number of moles of a substance, there will be a
tendency for a net reaction in the direction that tends to reduce the effect
of this change
• There are three factors:
• (1) Changing the concentration of a reactant or product.
• (2) Changing the pressure (or volume) of the system.
• (3) Changing the temperature.
• On applying to a chemical reaction in equilibrium, Le Chatelier’s principle can
be stated as: if a change in concentration, pressure or temperature is caused
to a chemical reaction in equilibrium, the equilibrium will shift to the right or
the left so as to minimise the change.
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Application of Le-chatelier principle to illustrate the effect of change of
concentration, pressure and temperature on equilibrium of chemical reactions

1. The effect of a change in Concentration:

• Let us illustrate this effect on a system at equilibrium with example:

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

i. On adding N2 (or H2) Equilibrium shift i. On removing NH3

ii. On removing N2 (or H2) ii. On adding NH3
Equilibrium shift

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contd...
2. The effect of a change in Pressure:
 There are three ways to affect a change in the pressure of gaseous reaction
mixture.
i. Addition or removal of gaseous reactants or products
• This process is similar to the change in concentration of reactant and
product. Remember, that the pressure of gases is related directly to the
concentration by P = n/V.

2SO2 + O2 2SO3 ∆H = - 42.0 Kcal

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contd...
ii. Change the volume of container.
• If the pressure of a gas is reduced, its volume will increase; the pressure and
volume are inversely proportional.
• If P increases (V decreases), the equilibrium of the system will shift in the
direction of less number of gas molecules (among reactant and product),
since this effectively reestablishes equilibrium by decreasing the pressure).
• If P decreases (V increases), the system shifts to the side with a greater
number of gas molecules.
• For example, N2(g) + 3H2(g) 2NH3(g); ∆H = - 22.4 Kcal
Q. Does the equilibrium shift left or right if the pressure is increased?

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contd...
• For example,
Q. Does the equilibrium shift left or right if we double the pressure, by
compressing the mixture to a smaller volume?
• For the chemical reactions with ∆n = 0, change of pressure has no any effect
on the equilibrium condition. Example H2 + I2 2 HI

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contd...
• iii. Addition of Inert gas.
• a. Addition of an inert gas into a system at eqm. under constant volume
causes, an increase in the pressure of the system and an increase in the total
no. of moles in the system. i.e. Pt V = nt RT or nt / Pt = V / RT Here, the ratio
of nt / Pt remains constant even on addition of any inert gas. In this case the
equilibrium constant is not affected by the inert gas.
• If the volume of the system is increased then partial pressure of each
component is decreased and shifts the eqm. towards the side with greater
no. of gaseous molecules.

• b. When inert gas is added without disturbing the total pressure (constant P),
in this case partial pressure of reactant and product decreases by certain factor
(increases the volume of the system). The equilibrium condition will be
disturbed if ∆n ≠ 0.

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contd...
Reaction having Direction of shift in eqm.
∆n value
∆n = + ve Right hand side (Product side)

∆n = -ve Left hand side ( Reactant side)

∆n = 0 Remains constant

• Here according to Le-chateliers principle equilibrium will shift towards

more number of mole side (among reactant and product), which minimizes
the stress to some extent. {Here the stress is the decrease in partial
pressure}.

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contd...
3. The effect of a change in Temperature:
• For a reversible reactions if the forward reaction proceeds by the evolution of
heat (exothermic), the reverse reaction occurs by the absorption of heat
(endothermic).

• The change of temperature affects the equilibrium state of both exothermic

and endothermic reaction.
• The magnitude of the equilibrium constant is also affected by the change of
temperature for such kind of reactions.
• When temperature of a reaction is increased, the equilibrium shifts in a
direction in which heat is absorbed

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contd...
• Consider following reactions, in which energy is released. (i.e. exothermic)in 1st
and energy is absorbed (i.e. endothermic) in 2nd.
• Since the new eqm. has less products
...............………..(1) ∆H = - 13.9 Kcal
than the old one, the new K constant <
old one. As T rises, K drops
...............………..(2) ∆H = + 43.5 Kcal • Since the new eqm. has more products
than the old one, the new K constant >old
one. As T rises, K also increases

Direction of equilibrium shift with increase in Temperature

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Effect of a Catalyst

 Catalysts lower Ea for the reaction, so a catalyst decreases the amount of

time taken to reach equilibrium for both the forward and reverse
reactions.
 The catalyst does not affect the equilibrium concentrations of reactants
and products in the equilibrium mixture; thus, the Kc value does not
change.

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Calculation with the equilibrium constant for gaseous reaction
( in terms of Total pressure (P) of reactants & products, and ‘f’ fractional amount dissociated of reactant)

• The equilibrium constant of a reaction between gases are often expressed in

terms of the partial pressure of reagent and generally units are atmosphere
• Thus for the reaction, N2O4(g) 2 NO2(g)
2
• We have, K  (NO2 )
P
P = 0.14 where the pressure are expressed in atm.
P(N O )
2 4

• Here, N2O4(g) 2 NO2(g)

At initial, 1 0
At eqm. 1-f 2f

• To express in terms of total pressure, PT and ‘f ‘of the original N2O4 dissociated,
• Total no. of moles of all particles present at eqm. is proportional to total fraction
of all i. e. (1-f+2f) or (1+f).
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contd...
• Then, mole fraction of N2O4 and NO2 are :
• XN2O4 = (1-f) / (1+f) , and XNO2 = (2f) / (1+f)
• Now, partial pressure of N2O4 and NO2 in terms of total pressure, PT.
• PNO2 = XNO2 . PT = [(2f) / (1+f)] . PT ; PN2O4 = XN2O4. PT = [(1-f) / (1+f)] . PT
2
P(NO
• Now, putting the values of PNO2 and PN2O4 in eqn. K P  2)

P(N O )
• We get 2 4

4f 2
• K P  PT  Here, PT = total pressure of reactants and products;
(1 - f 2 )
f = fraction of the original N2O4 that dissociated.
• Kp is constant that depends only on temperature. If total pressure, P is varied, the
fraction of N2O4 dissociated must change so as to keep the right-hand side of
constant.
• Q. Let, volume of the system is increased so that 'P' decreases. Does 'f ' increase or
K P  1 
decrease? PT    1
4 f2  27
 
Some Numerical Problems
• Q.N.1. A mixture of N2O4 and NO2has at eqm. a total pressure of 1.5 atm.
What fraction of N2O4has dissociated to NO2 at 250C? [Kp 0.14] [Ans. 0.15]

• Q.N. 2. If the volume of the system is increased so that pressure falls to 1 atm.
,what fraction of original N2O4 is dissociated? [Ans. 0.18]

• Q.N. 3. Suppose a reaction NH4HS(s) NH3(g) + H2S(g)

(i) Kp = PNH3PH2S = 0.11 Find the partial pressure of each NH3and H2S at
equilibrium. [Ans. PNH3= 0.33 atm. = PH2S]

(ii) If ammonium hydrosulfide is placed in a flask containing 0.50 atm of NH3.

What are pressures of NH3and H2S when equilibrium is reached. [PNH3 = 0.50 +
PH2S] [Ans. PH2S = 0.17 atm. ;PNH3 = 0.67 atm ]
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contd....
• Q.N. 4. Suppose a reaction, PCl5(g) PCl3 (g) + Cl2(g)

• Kp is 11.5 at 3000c. If P0 is(=1.5 atm) atm. then find equilibrium pressure of PCl5,
PCl3 and Cl2, and fraction (f) of PCl5 dissociated.
• The pure solid PCl5 is placed in a flask, on raising the temperature to 3000c, it
would vaporize to give a pressure of P0 atm, if no PCl5 dissocated. If some of PCl5
undergoes dissociation as shown above equation.
• Here, PPCl3 = PCl2, and P PCl5 = P0 - PCl2
• Then P(2Cl
2) = 11.5
𝐾𝑃 =
𝑃0 − P(Cl2 )

• PCl2 = 1.34 atm (= PPCl3 ) and P PCl5 = P0 - PCl2 = 1.5 – 1.34 = 0.16 atm
P(Cl
• Fraction (f) PCl5 dissociated, 𝑓= 2)
= 1.34/1.5 = 0.89
𝑃0
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contd....
• Q.N. 5. Suppose a reaction, PCl5(g) PCl3 (g) + Cl2(g)

• Kp is 11.5 at 3000c. If P0 is 3 atm. then find equilibrium pressure of PCl5, PCl3 and
Cl2, and fraction (f) of PCl5 dissociated.
[Ans. PPCl3 = PCl2, = 2.47 atm. and P PCl5 = 0.53 atm, f = 0.82]
• Increasing the total amount of material at fixed volume, or increasing the
total pressure, deceases the fraction of PCl5 that dissociates.
• Q.N. 6. What is the effect of adding Cl2 gas (1.5 atm) to reaction mixture of Q.N.
5?
• [Ans. PPCl3 = 2.26 atm, PCl2 = 3.76 atm. and P PCl5 = 0.74 atm, f = 0.75]
• Addition of chlorine gas will diminish the amount of PCl5 that dissociates.

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