Ionic Equilibrium

Electrolytes &
LECTURE 2 Degree of Dissociation
Anupam Gupta
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Ionic Equilibrium
Electrolytes &
LECTURE 2 Degree of Dissociation
 What happens after electrolytes start dissolving?

Question Do all electrolytes completely break down or ionize in aqueous solutions?

Answer No

Question How much do they break?

Answer Some break more - strong electrolytes

Some break less - weak electrolytes

Strong vs weak electrolytes
 Electrolytic equilibrium

All electrolytes attain equilibrium on dissociation

HCl H+ + Cl- CH3COOH H+ + CH3COO-

 Quantification of dissociation

Question What determines the extent of equilibrium?

Answer Equilibrium constant at that temperature

Question Are we going to use Kc and KP terms which we studied in chemical equilibrium
chapter?
No. We are going to use equilibrium constants based on concentration but are
Answer
going to use different terms.
 Various terms for equilibrium constants

Question What are the terms of equilibrium constants are we going to use here?

Answer Ionisation constant for acids Ka

Ionisation constant for bases Kb

Ionisation constant for salts (solubility product) Ksp

Ionisation constant for water (ionic product) Kw

Formation constant of complexes Kf

 Various terms for equilibrium constants

Ka

Kb

Kw
 Practise for writing Ka

HCl

CH3COOH
 Practise for writing Ka

H2S
 *****Simultaneous Equilibriums*****

Ka and Kw are constants for “simultaneous equilibriums”

 Various terms for equilibrium constants

Question What other terms are we going to use?

Answer “c” - initial concentration of the electrolyte

“α” - degree of dissociation
 Degree of dissociation

The degree of dissociation of a substance is defined as the fraction of its molecules

dissociating at a given time.

When a weak electrolyte A+ B- is dissolved is water and if α is the degree of dissociation then

AB ⇌ A+ + B-

Initial conc C 0 0

Change -Cα +Cα +C α

Conc-at eq. C(1 - α) Cα Cα Concentration of B- ion

Concentration of
Concentration of A+ ion
undissociated electrolyte
Degree of dissociation
 Degree of dissociation of acid

HA ⇌ H+ + A -

Initial conc C 0 0

Change -Cα +Cα +C α

Conc-at eq. C(1 - α) Cα Cα
Degree of dissociation of Acids
 Concept of equilibrium and dissociation constant

AB ⇌ A+ + B-

Initial conc C 0 0

Change -Cα +Cα +C α

Conc-at eq. C(1 - α) Cα Cα

Keq = ionization/ dissociation constant of the

weak electrolyte
Factors affecting degree of dissociation

Nature of electrolyte

Nature of solvent

Dilution

Temperature

Common ion effect

 Nature of electrolytes

Nature of electrolyte: Strong electrolytes dissociates more as compared to weak electrolytes.

Nature of electrolytes
 Nature of solvent

Dielectric constant
Nature of solvent: A solvent
having high value of dielectric
constant and high solvation
will favour dissociation.
 Dilution: Ostwald’s Law (for weak electrolytes)

Dilution: Increasing dilution i.e. decreasing concentration of substance increases degree of

dissociation.
 Dilution: Ostwald’s Law (for weak electrolytes)

At infinite dilution α reaches its maximum value, unity i.e. 1.

Here, weak electrolyte also starts behaving like strong electrolyte
 Temperature

Temperature: Electrolytes dissociates more at higher temperature (endothermic

dissociations)

T(0C) Kw(mol2/litre2)

0 0.114 x 10-14

10 0.293 x 10-14

20 0.681 x 10-14

25 1.008 x 10-14

30 1.471 x 10-14

40 2.916 x 10-14

50 5.476 x 10-14
 Common ion effect

Common ion effect: Dissociation of weak electrolytes is suppressed in presence

of strong electrolytes releasing a common ion

Recall Le Chatelier's principle from chemical equilibrium

Summary of background information for calculations

Concepts of Acid and Base

Concepts of Electrolytic equilibrium

Equilibrium constants and its values

Degree of dissociation and its values

Cases for pH calculation

Simple Stoichiometric Calculation

Strong Acid

Strong Base

Mixture of Strong Acids

Mixture of Strong Bases

Mixture of Strong Acid and Strong Base

Cases for pH calculation

Formula Derivation through equilibrium equation

Weak (monoprotic) Acid

Weak (polyprotic) Acid

Mixture of Weak (monoprotic) Acids

Mixture of weak (monoprotic) and a strong acid

Mixture of a weak acid/ weak base with strong

base/acid respectively
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