EQUILIBRIUM CONSTANT IN GASEOUS SYSTEMS

If an equilibrium involves gaseous species, then the concentration terms may be

replaced by partial pressure because the partial pressure of gaseous component is
proportional to its concentration.
For a general reaction,
aA+bB↔ cC+dD
PA, PB, PC,PD are the partial pressures of reactants and products.
Equilibrium constant in terms of partial pressure
Kp = (PC)c (PD)d/(PA)a (PB)b
RELATION BETWEEN Kc and Kp
For a general reaction,
aA+bB↔ cC+dD
From ideal gas equation PV=nRT
P = ( n/V ) RT n/V = C
P= CRT
PA =CART PB=CBRT PC=CCRT PD=CDRT
Kp = (PC) c (PDd / (PA)a (PB)b
Kp = (CCRT)c (CDRT)d / (CART) a (CBRT)b
Kp = (CC)c (CD)d (RT) c+d / (CA)a (CB)b (RT) a+b
Kp = (CC)c (CD)d/(CA)a (CB)b (RT) (c+d)-(a+b)
Kp= Kc RTn2-n1
Kp=Kc RT Δn
APPLICATION OF EQUILIBRIUM CONSTANT
1. Predict the extent of the reaction on the basis of magnitude.
2. Predict the direction of the reaction.
3. Calculate the equilibrium constant.

1. Predict the extent of the reaction on the basis of magnitude.

 The reaction of H2 with O2 at 500 K has a very large equilibrium constant,

 Kc = 2.4 × 1047.
 The decomposition of H2O into H2 and O2 at 500 K has a very small
equilibrium constant,
Kc = 4.1 × 10–48
 For reaction of H2 with I2 to give HI, Kc = 57.0 at 700K
2. Predicting the direction of the reaction.

3. Calculating equilibrium concentration.

3.00 mol of PCl5 kept in 1L closed reaction vessel was allowed to attain equilibrium
at 380K. Calculate composition of the mixture at equilibrium. Kc = 1.80
Step 1. PCl5 PCl3 + Cl2
Step 2
Initial concentration: 3.0 0 0
Change in concentration is x mol/L
At equilibrium 3-x x x
Step 3
Kc = [PCl3] [Cl2]/ [PCl5]
(𝑥)(𝑥)
1.8 =
3−𝑥
x2 + 1.8x – 5.4 = 0
Step 4
−𝑏±√𝑏2 −4𝑎𝑐
x= 2𝑎

x = [–1.8 ± √(1.8)2 – 4(–5.4)]/2

x = [–1.8 ± √3.24 + 21.6]/2
x = [–1.8 ± 4.98]/2
x = [–1.8 + 4.98]/2
= 1.59
[PCl5] = 3.0 – x = 3 –1.59 = 1.41 M
[PCl3] = [Cl2] = x = 1.59 M

RELATION BETWEEN EQUILIBRIUM CONSTANT (K) AND CHANGE IN

GIBBS FREE ENERGY.

Refer text book , Sec 7.7, refer notes from Thermodynamics.

FACTORS AFFECTING EQUILIBRIA

Le- Chateliers Principle : It states that change in any of the factors that determine the
equilibrium conditions of a system will cause the system to change in such a manner
so as to reduce or to counteract the effect of the change.

a. Effect of concentration:
Reactants Products
When the concentration of one of the substance increased in a system at equilibrium,
then the equilibrium will shift so as to use up the substance added. If the
concentration of one of the substance is reduced at equilibrium, then the equilibrium
will shift so as to produce the substance.

i. Con of reactant increased- Forward reaction

ii. Con of product increased- Backward reaction
iii. Con of reactant decreased- Backward reaction
iv. Con of product decreased- Forward reaction
Applications:
1. Clothes dry quicker when there is breeze: - Water vapours of near by air are
removed and the clothes lose water vapours to re-establish the equilibrium with
the surrounding air.
2. On a humid day we sweat more:- The sweating on a humid day is more because
surrounding air has large amount of water vapours and our body cannot lose
water as water vapour.
3. Transport of oxygen by haemoglobin in blood: - The equilibrium may be
represented as Hb (s) + O2 (g) HbO2 (s). When the concentration of
oxygen is less in the lungs, some of the oxyhaemoglobin decompose to form
oxygen.

b. Effect of change of pressure.

Conditions: i. The number of moles of reactant and product must be different
ii. More applicable for gaseous phase equilibrium.

i. Low pressure favours those reactions which are accompanied by increase in

total volume.
 ii. High pressure favours those reactions which are accompanied by decrease
in total volume.
iii. Pressure has no effect on an equilibrium reaction which proceeds with no
change in total number of moles.
Illustration : N2(g) + 3H2(g) 2NH3(g)
Total number of Total number of
moles of reactant 1+ 3=4 moles of product 2
(4 V) ( 2V)
(1) At low pressure, volume increasing process takes place (backward reaction).
(2) At high pressure, Volume decreasing process takes place (forward reaction).

c. Effect of temperature:

i. Exothermic reactions are favoured by low temperature.

A+B Product + ΔH
ii. Endothermic reactions are favoured by high temperature
A+B Product
ΔH

iii. Equilibrium constant for an exothermic reaction decreases as the

temperature increases.
iv. Equilibrium constant for an endothermic reaction increases as the
temperature increases.

d. Effect of catalyst:
The presence of catalyst does not disturb the equilibrium because it increases the
rate of forward as well as backward reaction some extent catalyst does not disturb
the equilibrium composition of the reaction mixture.

e. Effect of inert gas addition:- Refer text book

Summary
 STRESS DIRECTION IN WHICH THE
EQUILIBRIUM SHIFTS
Increase in concentration of one or Forward direction
more reactants.
Increase in concentration of one or Backward direction
more products
Increase in temperature Endothermic reaction
Decreasse in temperature Exothermic reaction
Increase of pressure Towards lesser number of moles
Decrease of pressure Towards large number of moles
Addition of catalyst No effect
Addition of inert gas No effect.

IONIC EQUILIBRIUM

Equilibrium involving ions in aqueous solution is called ionic equilibrium.

Faraday’s classification of electrolysis:

1. Electrolytes: - Substance which conduct electricity in their aqueous

solutions or molten state are called Electrolytes.
2. Non –Electrolysis: - The substance which do not conduct electricity are
called non – electrolytes.
3. Electrolytes are classified into strong and weak electrolytes.
4. Strong electrolytes dissociates/ ionized completely in aqueous / molten
state.
5. Weak electrolytes partially ionized or dissociates into solution.
6. dissociation of strong electrolytes represented by a single arrow and or
weak electrolytes it is represented by double headed arrow.

THEORIES OF ACIDS AND BASES

1. Arrhenius concept of Acids and Bases.

 An acid is a substance which can furnish H+ ions in its aqueous solution.

 Base is a substance which can furnish OH— ions in aqueous solution.
  Strong acids ionize completely in aqueous solution and weak acid ionize
partially in aqueous solution.
 In aqueous solution, H+ ions combine with water to form H3O+ (Hydronium
 ion)

H+ + H2O H3O+
Shape of H3O+ is trigonal pyramidal structure.

Limitations:

 This concept is only applicable for aqueous solutions.

 It does not account for the acidic nature of substances like SO 2, SO3 etc which
do not contain any hydrogen ion.
 It does account for the basic nature of NH3, CaO etc which do not contain
hydroxyl group.

2. Bronsted – Lowry concept of acids and bases (Proton theory of acids and
bases)

 An acid is a substance that can donate H+ ion or proton.

 A base is a substance that can accept H+ ion or proton.


Water can act as acid and base, so it is amphoteric in nature.
Q. Write the conjugate base for the following Bronsted acids.
HCl, HNO3, HSO4—, H2SO4, H2S
Q. Write the conjugate acids for the following Bronsted bases.
NH2—, H2O, NH3, C2H5OH, HCOO—
3. Lewis theory of acids and bases.
 An acid is a substance which can accept a pair of electrons.
 A base is a substance which can donate a pair of electrons.
 IONIC PRODUCT OF WATER AND IONISATION CONSTANT

Ionic product is the product of concentration of ions of the electrolyte.

Consider a reaction

H2O (l)+ H2O (l) H3O+ + OH—

acid base CA CB

The dissociation constant/ Ionisation constant can be expressed as

K = [H3O+][ OH—] / [H2O][ H2O]

since the con of water can be considered as unity, the expression becomes

K= [H3O+][ OH—] is called ionic product of water.

(K or Kw)

 The con of H+ and OH— ions has been found experimentally 1 x 10 -7 M in 1 mole of
water.
 Kw = [H3O+][ OH—]
= [H+][ OH—]
= (1 x 10 -7) 2

pH Scale (Potenz hydrogen Scale )

 It is a logarithemic scale Invented by Sorensen.

 It is used to express the hydrogen ion concentration
 pH of a solution may be defined the negative log of activity of hydrogen ion. (a H+)

a H+ = [H+] in mol/L
 pH = ⸺ log [H+] / ⸺ log [H3O+]
 Acidic [H+] > [OH—]
Basic [OH—] > [H+]
Neutral [H+] = [OH—]
 FACTORS AFFECTING ACIDIC STRENGTH (H⸺X)

An acid having greater degree of ionisation is referred to as strong acid. The ionisation of acid
depends on the following factors.

1. Strength of H⸺X bond

2. Polarity of H⸺X bond

 Weaker the strength of bond, stronger the acid.

 Greater polarity of H⸺X bond, stronger the acid.
 As the size of the anion increases, bond length also increases, acidic strength
also increases.
HF< HCl< HBr< HI
 As the electronegativity of X increases, polarity also increases, the strength of
the acid increases.
CH4<NH3<H2O<HF

COMMON ION EFFECT

 The basic principle of common ion effect is Le- Chatelier principle.

 If a common ion is added to a weak acid or weak base equilibrium, then the
equilibrium shift towards the reactant side.
 The common ion supresses the ionisation of weak acid/base.
 The degree of ionisation of a weak electrolyte is supressed by the addition of a
strong electrolyte contain common ion is called common ion effect.
Consider the dissociation/ ionisation of NH4OH
NH4OH NH4+ + OH —
Addition of NH4Cl supress the dissociation by providing excess of NH4+ ions.
NH4OH NH4+ + OH —
NH4Cl NH4+ + Cl —
Due to increase in the concentration of product, the equilibrium will shift towards the reactant
side so as to consume the excess of NH4+ ions. Hence the ionisation of weak electrolyte
NH4OH can prevent.