CHAPTER

8 Ionic Equilibrium

Chapter Highlights
Arrhenius theory, Ostwald dilution law, Ionic product of water, pH value, Buffer, Solubility and Solubility product,
Salt hydrolysis, Concept of acid and base and various levels of multiple-choice questions.

IONIC EQUILIBRIUM

TYPES OF SUBSTANCES ARRHENIUS THEORY

Substances can be classified into following two types, viz., Arrhenius theory is also known as introduction of ionic
non-eletrolytes and electrolytes. theory or dissociation of electrolytes theory. The main pos-
tulates of this theory are:
Non-electrolytes • Electrolytes on dissolving in a solvent, ionize into
ions.
Non-electrolytes do not conduct electricity in aqueous Solvent
solution or molten state, for example, solution of urea, AB A+ + B-
H2O
glucose, sugar, glycerine. Ions
[Ionization]
Electrolytes • The process of ionization is reversible and the ioniza-
tion constant (K) is given as
Electrolytes conduct electricity in aqu ous solution or
 A +   B− 
K =   
molten state, for example, NaCl. These can be further
divided into following types: [ AB ]
Strong electrolytes
• The ions are always discharged in equivalent amount,
These get strongly ionized in water, hence they exhibit high
no matter what their relative speeds are during
conduction, for example, strong acids like HCl, H2SO4,
electrolysis.
HNO3, strong bases like KOH, NaOH and salt of strong
acid or strong base like NaCl, CH3COONa, NH4X. • Ions act like molecules towards elevating the boiling
point, depressing the freezing point, lowering vapour
Weak electrolytes pressure and osmotic pressure.
These are ionized in water less strongly, hence they show
less conduction, for example, weak acids like CH3COOH, Evidence in Support of lonic Theory
HCN, H3PO4, H2CO3, weak bases like NH4OH and their • Presence of ions in solid electrolytes can be noticed
salts like NH4CN, CH3COONH4. by X-ray diffraction method.
• Ions obey Ohm’s law (I = E/R)
8.2 Chapter 8

• Ionic reactions, for example, As 1 > > > α so (1−α) = 1

AgNO3 + NaCl Ag+ Cl− ↓ + Na+NO −3 α 2
K= or α2 = KV or α = .9
• Colour of some solutions is due to the presence of V
ions, for example, CuSO4 solution is blue due to α∝ 9
Cu2+. Hence, at constant temperature, degree of dissociation
is directly proportional to the square root of its dilution.
Degree of lonization
• If C is the concentration then
Degree of ionization is the extent to which an electrolyte
gets ionized in a solvent. It is denoted by α. AB 
↽⇀
 A+ + B−
C (1−α) Cα Cα
1XPEHU RI PROHFXOHV GLVVRFLDWHG
α= Cα 2
7RWDO QXPEHU RI PROHFXOHV K=
(1 − α )
Degree of ionization or α depends on:
K = C α2 or α2 = K/C
• Nature of solute and solvent. For strong electrolytes α = √(K/C)
α is more than that for weak electrolytes.
that is, α ∝ √(1/C)
• α ∝ Dielectric constant of solvent
Hence, at constant temperature, degree of dissociation
Greater the dielectric constant of a solvent, more will
is inversely proportional to the square root of its con-
be ionization of electrolyte in it.
centration.
• The degree of dissociation of weak electrolyte is
λv Λv
directly proportional to dilution, that is, α is maxi- • α= or
mum at infinite dilution. λ∞ Λ∞
 Here λv or Λv is equivalent conductivity at V dilution.
• α∝ λ∞ or Λ∞ is equivalent conductivity at infinite dilution.
&RQFHQWUDWLRQ
• α ∝ Temperature • λv = Kv × V
Here Kv = Specific conductivity
OSTWALD DILUTION LAW V = Dilution
• λ∞ = λc + λα
• Ostwald dilution law is the law of mass action for
Here λc and λα are the ionic mobilities of cation and
weak electrolytes and dilute solutions and gives
anion respectively.
the relationship between the dissociation of a weak
electrolyte.
• It is not applicable for strong electrolytes or highly
concentrated solutions.
Consider a weak electrolyte AB in V litres of a
solution.
AB ↽⇀
 A+ + B−
Initial moles 1 0 0
Moles at equilibrium 1−α α α 
↽⇀

Concentration (1−α)/V (α/V) (α/V)
at equilibrium 
↽⇀

 B−   A + 

K=
[ AB ]
(α / V ) × (α / V )
K= 
(α − V ) / V ↽ ⇀


↽⇀
α2 / V2 α2
So, K = =
(1− α ) / V (1− α ) / V
 Ionic Equilibrium 8.3

K = Cx2
x = √(Ka / C)
[H+] = Cx = C√ (Ka/C) ≈ √(KaC)
pH = −log10 Cx
pH = −log10 √(KaC)
Here C = Molar concentration of acid
x = Degree of dissociation
Ka = Dissociation constant of acid

pH of weak base
NH4OH 
↽ ⇀
 NH+4 + OH−
1 0 0
(1−x) Cx Cx
IONIC PRODUCT OF WATER [OH−] = Cx= √(Kb.C)
Ionic product of water is the product of the molar concen- pOH = −log10 Cx
trations of H+ or H3O+ and OH− ions. It is denoted by Kw. pOH = −log10 √KbC
H2O + H2O ↽
 H+3 O + OH−
⇀ Here Kb = Dissociation constant of the base
Kw = [H3O+] . [OH−] pOH
or [H+]. [OH−] [OH−] = 10−pOH
Here Kw = Ionic product of water 
• Kw = Ka. Kb pOH = −log10 [OH−] or ORJ >2+ @ 


• pKw = −log10 Kw
• pH + pOH = 14
• Kw = Ka × Kb
• pH + pOH = pKw
• pKw = pKa + pKb
• pKa = −log10 Ka
• At 25°C Kw = 1 × 10−14
pKw = 14 1 1
• pK a ∝ ∝
• The value of Kw increases with increase in tempera- K a Acidic strength
ture, for example, at 98°C Kw is 1 × 10−12. • pK b = −log10 K b

pH Scale 1 1
• pK a ∝ ∝
• pH scale was introduced by Sorenson, to measure K a Basic strength
acidity or basicity of a solution. • pK = −ve log of dissociation constant
• pH stands for potential de-H+ or concentration of H+. • A weak acid has high value of pKa
It is given as • A weak base has high value of pKb
[H+] = 10−pH
pH = –log10 [H+]
pH of aqueous solution is equal to negative logarithm FA C T S TO R E M E M B E R
of H+ (H+3 O) concentration in mole/litre.
 pH of strong acid or base does not depend upon
1 temperature.
pH = log10
 H +   pH of weak acid decreases with increase in temperature,
due to increase in ionization.
pH of weak acid  pH of weak base increases with increase in tem-
perature, due to increase in ionization or [OH− ]
CH3COOH ↽ 
⇀
 CH3COO− + H+ ion concentration.
1 0 0
C(1−x) Cx Cx
8.4 Chapter 8

• Its pH changes slightly (unnoticeable) on the addi-

pH Value and Nature of a Solution
tion of small quantity of a strong acid or base.
l If [H+] > 10−7, pH is less than 7 and the solution is
acidic. Buffer Capacity
l If [H+] = 10−7, pH is 7 and the solution is neutral.
Buffer capacity is the ratio of number of moles of the acid
l If [H+] < 10−7, pH is more than 7 and the solution
or base added in one litre of the solution, so as to change
is basic.
its pH by unity. It is denoted by ϕ

Table 8.1 pH Range of Some Substances ϕ = 1XPEHU RI PROHV RI DFLG EDVHDGGHGWRO/RIVROXWLRQ

Substance pH range &KDQJH LQ S+
Gastric juice 1−3.0
Types of Buffer Solutions
Soft drink 2−4.0
Lemon 2.2−2.4 1. Acidic buffer It is a solution of a weak acid and its salt
Vinegar 2.4−3.4 with a strong base. For example,
Urine 4.8−8.4 • CH3COOH + CH3COONa
Milk 6.3−6.6
• Phthalic acid + potassium phthalate
Saliva 6.5−7.5
• Boric acid + borax
Blood 7.3−7.5
• H2CO3 + NaHCO3
Sea water 8.5
• Citric acid + sodium citrate
Tears 7.4 2. Basic buffer It is a solution of a weak base and it salt
with a strong acid. For example,
Limitations of pH Scale • NH4OH + NH4Cl
• Glycine + Glycine hydrogen chloride
• pH value of a solution does not instantaneously give
• Glycerol + Glycerine hydrogen chloride
us an idea of the relative strength of the solution.
3. Ampholytes These are compounds that contain both
• pH is zero for 1N solution of strong acid.
acidic and basic groups and therefore exist as zwitter-
• pH is negative for concentrations 2N, 3N, 10N of ions at a certain pH (isoelectric point). Hence, proteins
strong acids. and amino acids also act like a buffer solution.
• At higher concentrations, in place of pH, Hammelt
acidity functions are used. NOTE
 Zwitterions are ions that contain both positive and nega-
BUFFER SOLUTION tive charges and are thus amphotieric.
• Buffer solution is the solution whose pH, on addition
of a small amount of strong acid or a base, does not 4. A mixture of acidic salt and normal salt of a polybasic
change much. acid. For example,
• It is also called reserve acidity or basicity of the Na2HPO4 + Na3PO4
solution, as it resists change in pH value and this 5. Salt of weak acid and weak base (in water)
action to resists pH change is called buffer action. For example, CH3COONH4, NH4CN

Features Uses of Buffer solutions

• It has a definite pH, that is a definite reserve acidity
or basicity.
• Its pH does not change over a long period time.
• Its pH does not change on dilution.
• To determine pH value of unknown solution with the
help of an indicator.
• NH4Cl + NH4OH and (NH4)2CO3 buffer solutions are
used to precipitate carbonates of group V elements of
the periodic table group.
 Ionic Equilibrium 8.5

• CH3COOH and CH3COONa buffer is used to remove Solubility Product

PO4–3 in qualitative inorganic analysis after IInd
group. Solubility product is the product of the molar concentra-
tions of ions of an electrolyte in saturated solution at a
• CH3COOH and CH3COONa buffer is used to pre-
particular temperature. It is denoted by Ksp or S.
cipitate lead chromate quantitatively in gravimetric
analysis. For a binary electrolyte AB
• They are also used in paper, dye, printing ink, dairy  A + + B−
AB ↽ ⇀
 AB 
↽⇀

product. Solid Un-ionized
 A +   B− 
SOLUBILITY AND SOLUBILITY PRODUCT So, K =    
[ AB ]
Solubility or K.[AB] = [A+] [B−]
Ksp = [A+][B−] (At constant temperature)
• Solubility is the weight of solute in grams, present in
100 mL of solvent.
General representation
• It is denoted by s and is expressed in mole per litre or
gram per litre.
AxBy ↽⇀ xA+y + yB−x
Ksp = [A ] [B−x]y
+y x

• Solubility (s) ∝ Examples:
&RQFHQWUDWLRQ RI FRPPRQ LRQV
or number of common ions 1. CaF2 ↽  Ca+2 + 2F−
⇀
Solubility increases due to complex ion formation. For Ksp = [Ca+2] [F−]2
example, the solubility of AgCl in water, in presence of 2. Ag2CrO4 ↽  2Ag+ + CrO4−2
⇀
AgNO3.
Ksp = [Ag ] [CrO4−2]
+ 2

Here, AgCl has more solubility in ammonia, due to

complex formation.
Relation Between Solubility (s) and
AgCl + 2NH3 Ag(NH3) 2Cl Solubility Product (Ksp)
HgCl2 has more solubility in KI due to complex forma- AxBy ↽  xA+y + yB−x
⇀ 
tion (Nesseler’s reagent). a 0 0
HgI2 +2KI K2HgI4 as xs ys
Ksp = (x s)x . (y s)y
In the analysis of IInd group elements, SnS, Sb2S3 or
As2S3 are soluble in (NH4)2S due to complex ion for- Ksp = xx yy (s)x+y
mation.
If α is given
SnS + S−2 SnS2−2
−2 Ksp = xx yy (α s)x+y
Sb2S3 + 3S 2SbS3−3
As2S5 + 3S−2 2AsS4−3
For example, Cu2Cl2 ↽   2Cu+ + 2Cl−
⇀
2s 2s
2 2 2+2 4
Simultaneous solubility So Ksp = 2 . 2 . (s) = 16 s
It is solubility of a solution of two electrolytes having Fe(OH)3 ↽   Fe+3 + 3OH−
⇀
common ions. s 3s
Examples: Ksp = 11 .33 (s)1 + 3 = 27 s4
1. AgBr + AgSCN Al2(SO4)3 ↽  2Al+3 +3SO4−2
⇀
2. CaF2 + SrF2 2s 3s
3. MgF2 + CaF2 Ksp = 22 .33.(s)2+3 = 108 s5
8.6 Chapter 8

Na3Li3(AlF6)2 ↽   3Na+ + 3Li+3 + 2AlF6−3

⇀
3 3 2 3+3+2
Ksp = 3 .3 .2 .(s) = 2916 s8

Solubility Product and Precipitation

1XPEHU RI PROHV RI VDOW K\GURO\]HG
• If Ksp ≈ ionic product, the solution is saturated, and 7RWDO PROHV RI WKH VDOW WDNHQ
for precipitation, more solute should be added.
• If ionic product > Ksp, the solution is super saturated,
and therefore gets easily precipitated. Various Expressions for Kh, h and pH for
• If ionic product < Ksp, the solution is unsaturated and Different Type of Salts
therefore no precipitation takes place.
1. For the salt of weak acid and strong base like KCN,
.Z
SALT HYDROLYSIS Kh=
.D
• When a salt is added to water, ions of the salt inter-
h = √(Kh / C)
act with water to cause acidity or basicity in aque-
ous solution. This ionic interaction is called salt h = √(Kw / Ka.C)
hydrolysis. pH = ½[pKw + pKa + log C]
• Interaction of cation is cationic hydrolysis and inter- pOH = ½ [pKw – pka – logC]
action of anion is anionic hydrolysis.
• Hydrolysis is reverse of neutralization and is an 2. For the salt of strong acid and weak base like FeCl3,
endothermic process. Kw
Kh =
• If hydrolysis constant is Kh and neutralization con- Kb
stant is Kn, then Kn = 1/Kh h = √(Kh/C)
• A solution of the salt of strong acid and weak h = √(Kw/Kb.C)
base is acidic and for it pH < 7 or [H+] > 10−7, for
pH = ½[pKw – pKb – log C]
example, FeCl3 (salt of a weak base + strong acid).
Here, the solution is acidic and involves cationic 3. For the salt of weak acid and weak base like
hydrolysis. CH3 COONH4,
• A solution of the salt of strong base and weak
Kw
acid is basic and for it, pH > 7 or [H+] < 10−7, for Kh =
example, KCN (salt of a strong base + weak acid). KaKb
Here, the solution is basic and involves anionic h = √(Kw/Ka.Kb)
hydrolysis. pH = ½ [pKw + pKa–pKb]
• A solution of the salt of a weak acid and a weak
base is: ACID AND BASES
1. Acidic, if Ka > Kb
2. Basic, if Ka < Kb Arrhenius Concept of Acid and Base
3. Neutral, if Ka = Kb is neutral According to Arrhenius concept, “Acids are H+ ion donor
• CH3COONH4 (salt of a weak acid + weak base) Here, in water and bases are OH– ion donor in water.’’
the solution is neutral and involves both cationic and
anionic hydrolysis. Acid
• A solution of the salt of strong acid and strong base • HA + H2O A– + H3O+
+
is neutral or pH = 7 or [H+] = 10−7. where H3O hydronium ion or hydrated proton.
• A salt of a strong acid a and strong base is never • Water can accept H+ to form hydronium ion (H3O+)
hydrolyzed. due to hydrogen bonding. For example, [H5O+2, H7O+3]
however, ions are hydrated, for example K2SO4 (salt • H+ can hold water molecule by hydrogen bond, as
of a strong base + strong acid) it has high heat of hydration. For example, HNO3,
H2SO4, HX.
 Ionic Equilibrium 8.7

• H3O+ has sp3 hybridization and is trigonal pyramidal

in shape. FA C T S TO R E M E M B E R
• Number of H+ donated = Basicity or protosity of the  This concept fails to explain acidic and basic nature of
acid. AlCl3, BX3, NH3.

Examples:

1. H3PO4 (tribasic)
Bronsted Lowery Concept or Proton
O
Concept
↑ Acid
H–O–P–O–H Acids are proton or H+ donor.
⎪ HA A– + H+
O–H Acid Conjugate base
2. H3PO3 (dibasic) For example, HX H+ + X–
H Conjugate base
⎪ H2SO4 H+ + HSO4–
H–O–P–O–H Acid Conjugate base
↓
HNO3 H+ + NO–3
O
3. H3PO2 Base
O Bases are proton or H+ acceptor
↑ Base + H+ (Base H)+
H–P–H Proton Conjugate base
⎪ given by acid
O–H For example, OH– + H+ H2O
Base Conjugate base
Base
• B.OH + H2O B+ + H3O2– [or H5O3– ] Amphoteric or Ampholyte Substances
For example, NaOH, KOH.
Such a substance can behave both like an acid and a base
that is, it can donate or accept H+ or proton.
Examples:
+H+ –H+
1. NH+4 NH3 NH–2
Conjugate Ampholyte Conjugate
acid base
+H+ –H+
2. H3O+ H2O OH–
Conjugate Ampholyte Conjugate
acid base

↽⇀
 Some other examples are HSO4–, HCO3–, H2PO4–, HPO42–,
H2PO3–, HS– and HC2O4–

↽⇀

FA C T S TO R E M E M B E R

↽⇀

 H2PO2– and HPO32– are only bronsted bases. As H3PO2
and H3PO3 are monobasic and dibasic acid respectively,
they can release only one and two H+ ions respectively.