CHAPTER

Ionic Equilibrium
7B
Chapter Outline
■ Types of Substances ■ Arrhenius Theory ■ Ostwald Dilution Law ■ Ionic Product of Water ■ Buffer Solution
■ Solubility and Solubility Product ■ Salt Hydrolysis ■ Acid and Base

Types of Substances • Electrolytes on dissolving in a solvent, ionize into ions.

Solvent

AB  A+ + B–
Substances can be classified into following two types, viz.,
H2O Ions
non-eletrolytes and electrolytes.
[Ionization]
Non-electrolytes
• The process of ionization is reversible and the ionization
Non-electrolytes do not conduct electricity in aqueous solu-
constant (K) is given as
tion or molten state, for example, solution of urea, glucose, [A+] [B+]
sugar, glycerine. K =
[AB]
Electrolytes • The ions are always discharged in equivalent amount, no
Electrolytes conduct electricity in aqueous solution or mol- matter what their relative speeds are during electrolysis.
ten state, for example, NaCl. These can be further divided • Ions act like molecules towards elevating the boiling
into following types: point, depressing the freezing point, lowering vapour
Strong electrolytes These get strongly ionized in pressure and osmotic pressure.
water, hence they exhibit high conduction, for example,
Evidence in Support of lonic Theory
strong acids like HCl, H2SO4, HNO3, strong bases like
KOH, NaOH and salt of strong acid or strong base like • Presence of ions in solid electrolytes can be noticed by
NaCl, CH3COONa, NH4X. X-ray diffraction method.
• Ions obey Ohm’s law (I = E/R)
Weak electrolytes These are ionized in water less strong-
• Ionic reactions, for example,
ly, hence they show less conduction, for example, weak
acids like CH3COOH, HCN, H3PO4, H2CO3, weak bases AgNO3 + NaCl Ag+ Cl− ↓ + Na+NO −3
like NH4OH and their salts like NH2CN, CH3COONH4. • Colour of some solutions is due to the presence of ions,
Arrhenius Theory for example, CuSO4 solution is blue due to Cu2+.

Arrhenius theory is also known as introduction of ionic Degree of lonization

theory or dissociation of electrolytes theory. The main pos- Degree of ionization is the extent to which an electrolyte
tulates of this theory are: gets ionized in a solvent. It is denoted by α.
7.34 ■ Chapter 7

Number of molecules dissociated Hence, at constant temperature, degree of dissociation

α= is inversely proportional to the square root of its
Total number of molecules
concentration.
Degree of ionization or α depends on:
• Nature of solute and solvent. For strong electrolytes α is • α=
more than that for weak electrolytes.
• α ∝ Dielectric constant of solvent  Here λv or Λv is equivalent conductivity at V dilution.
Greater the dielectric constant of a solvent, more will be λ∞ or Λ∞ is equivalent conductivity at infinite dilution.
ionization of electrolyte in it.
• The degree of dissociation of weak electrolyte is directly • λv = Kv × V
proportional to dilution, that is, α is maximum at infinite Here Kv = Specific conductivity
dilution.        V = Dilution
1
• α∝
Concentration • λ∞ = λc + λα
• α ∝ Temperature  Here λc and λα are the ionic mobilities of cation and
anion respectively.
Ostwald Dilution Law
• Ostwald dilution law is the law of mass action for weak Common Ion Effect
electrolytes and dilute solutions and gives the relation- The value of degree of dissociation for a weak electrolyte
ship between the dissociation of a weak electrolyte. is decreased by the addition of a strong electrolyte having
• It is not applicable for strong electrolytes or highly con- a common ion.
centrated solutions. • A
 s a result of this effect, the concentration of the uncom-
Consider a weak electrolyte AB in V litres of a solution. mon ion of the weak electrolyte decreases.
AB  A+ + B− Examples:
Initial moles 1 0 0 (1) NH4OH 

 NH+4 + OH−
Moles at equilibrium 1−α α α Weak
Concentration (1−α)/V (α/V) (α/V) NH4Cl  
 NH+4 + Cl−
at equilibrium Common ion
[B− ][A + ] Here the value of α for NH4OH will be decreased by
K = NH4Cl.
[AB]
(2) CH3COOH   
 CH3COO− + H+
K= CH3COONa     CH3COO− + Na+
Common ion
So, K = Here the value of α for CH3COOH will be decreased
by CH3COONa.
As 1 > > > α so (1−α) = 1
• S
 olubility of a partially soluble salt decreases due to
K= or α = KV
2
or α = .9 common ion effect, for example, presence of AgNO3 or
KCl, decreases the solubility of AgCl in water.
α∝ 9
• Salting out of soap by addition of NaCl.
Hence, at constant temperature, degree of dissociation is
• Purification of NaCl by passing HCl gas.
directly proportional to the square root of its dilution.
• If C is the concentration then Isohydirc Solution
AB 
 
 A+ + B− These are solutions having same concentration of common
C (1−α) Cα Cα ions.

K=

K = C α2 or α2 = K/C Ionic Product Of Water

α = (K/C) Ionic product of water is the product of the molar concen-
that is, α ∝ (1/C) trations of H+ or H3O+ and OH− ions. It is denoted by Kw.
 Ionic Equilibrium ■ 7.35

H2O + H2O  

 H+3 O + OH− pOH
Kw = [H3O ] . [OH−]
+
[OH−] = 10−pOH
or [H+]. [OH−] pOH = −log10 [OH−] or
Here Kw = Ionic product of water
• pH + pOH = 14
• Kw = Ka. Kb
• pH + pOH = pKw
• pKw = −log10 Kw
• pKa = −log10 Ka
• Kw = Ka × Kb
• pKw = pKa + pKb • pKa ∝
• At 25°C Kw = 1 × 10−14
• pK b = −log10 K b
pKw = 14
• The value of Kw increases with increase in temperature, • pKb ∝
for example, at 98°C Kw is 1 × 10−12.
• pK = −ve log of dissociation constant
pH Scale • A weak acid has high value of pKa
• p H scale was introduced by Sorenson, to measure acidity • A weak base has high value of pKb
or basicity of a solution.
• pH stands for potentiel de-H+ or concentration of H+. Facts to Remember
It is given as: • p H of strong acid or base does not depend upon
[H+] = 10−pH temperature.
pH = –log10 [H+] • pH of weak acid decreases with increase in
pH of aqueous solution is equal to negative logarithm of temperature, due to increase in ionization.
H+ (H+3 O) concentration in mole/litre. • pH of weak base increases with increase in
pH = log10 temperature, due to increase in ionization or [OH− ]
ion concentration.
pH of weak acid
CH3COOH  
 CH3COO− + H+
1 0 0 pH Value and Nature of a Solution
C(1−x) Cx Cx • If [H+] > 10−7, pH is less than 7 and the solution is acidic.
K = Cx2 • If [H+] = 10−7, pH is 7 and the solution is neutral.
x = (Ka/C)
• If [H+] < 10−7, pH is more than 7 and the solution is basic.
[H+] = Cx = C (Ka/C) ≈ (Ka/C)
pH = −log10 Cx
Table 7.1 pH Range of Some Substances
pH = −log10 (Ka/C)
Here C = Molar concentration of acid Substance pH range
x = Degree of dissociation Gastric juice 1−3.0
Ka = Dissociation constant of acid Soft drink 2−4.0
Lemon 2.2−3.4
pH of weak base
Vinegar 2.2−2.4
NH4OH 
 
 NH+4 + OH− Urine 4.8−8.4
1 0 0
Milk 6.3−6.6
(1−x) Cx Cx
Saliva 6.5−7.5
[OH−] = Cx= (Kb.C)
Blood 7.3−7.5
pOH = −log10 Cx
Sea water 8.5
pOH = −log10 (Kb.C)
Here Kb = Dissociation constant of the base Tears 7.4
7.36 ■ Chapter 7

Limitations of pH scale 3. Ampholytes These are compounds that contain both

acidic and basic groups and therefore exist as zwitter-
• p H value of a solution does not instantaneously give us ions at a certain pH (isoelectric point). Hence, proteins
an idea of the relative strength of the solution. and amino acids also act like a buffer solution.
• pH is zero for 1N solution of strong acid.
• pH is negative for concentrations 2N, 3N, 10N of strong Note: Zwitterions are ions that contain both positive and
acids. negative charges and are thus amphotieric.
• At higher concentrations, in place of pH, Hammelt
acidity functions are used. 4. A mixture of acidic salt and normal salt of a polybasic
acid. For example,
Na2HPO4 + Na3PO4
Buffer Solution 5. Salt of weak acid and weak base (in water).
• B uffer solution is the solution whose pH, on addition of For example, CH3COONH4, NH4CN
a small amount of strong acid or a base, does not change
much or noticeably. Uses of Buffer solutions
• It is also called reserve acidity or basicity of the solu- • T
 o determine pH value of unknown solution with the
tion, as it resists change in pH value and this action to help of an indicator.
resists pH change is called buffer action.
• N
 H4Cl + NH4OH and (NH4)2CO3 buffer solutions are
used to precipitate carbonates of group V elements of
Features the periodic table group.
• I t has a definite pH, that is a definite reserve acidity or • C
 H3COOH and CH3COONa buffer is used to remove
basicity. PO4–3 in qualitative inorganic analysis after IInd group.
• Its pH does not change over a long period time. • C H3COOH and CH3COONa buffer is used to precipitate
• Its pH does not change on dilution. lead chromate quantitatively in gravimetric analysis.
• Its pH changes slightly (unnoticeable) on the addition of
• They are also used in paper, dye, printing ink, dairy
small quantity of a strong acid or base.
product.
Buffer Capacity Solubility And Solubility Product
Buffer capacity is the ratio of number of moles of the acid
or base added in one litre of the solution, so as to change its Solubility
pH by unity. It is denoted by φ. • S olubility is the weight of solute in grams, present in
100 mL of solvent.
1XPEHURIPROHVRIDFLGEDVHDGGHGWRO/RIVROXWLRQ
φ= • It is denoted by s and is expressed in mole per litre or
&KDQJH LQ S+ gram per litre.

Types of Buffer Solutions • Solubility (s) ∝
&RQFHQWUDWLRQ RI FRPPRQ LRQV
Acidic buffer It is a solution of a weak acid and its salt
1.  ar number of common ions
with a strong base. For example,
Solubility increases due to complex ion formation. For
• CH3COOH + CH3COONa example, the solubility of AgCl in water, in presence of
• Phthalic acid + potassium phthalate AgNO3.
• Boric acid + borax Here, AgCl has more solubility in ammonia, due to com-
• H2CO3 + NaHCO3 plex formation.
• Citric acid + sodium citrate AgCl + 2NH3 Ag(NH3) 2Cl
2.  asic buffer It is a solution of a weak base and it salt
B
HgCl2 has more solubility in KI due to complex forma-
with a strong acid. For example,
tion (Nesseler’s reagent).
• NH4OH + NH4Cl
HgI2 +2KI K2HgI4
• Glycerine + Glycerine hydrogen chloride
 Ionic Equilibrium ■ 7.37

In the analysis of IInd group elements, SnS, Sb2S3, As2S3 If α is given:

are soluble in (NH4)2S due to complex ion formation. Ksp = xx yy (α s)x+y
For example, Cu2Cl2   
+
 2Cu + 2Cl
−
SnS + S−2 SnS2−2
2s 2s
Sb2S3 + 3S−2 2SbS3−3 So Ksp = 22 22 (s)2+2 = 16 s4
As2S5 + 3S−2 2AsS4−3 Fe(OH)3  
+3
 Fe + 3OH
−

s 3s
Simultaneous solubility It is solubility of a solution of
two electrolytes having common ions. Ksp = 11 33 (s)1 + 3 = 27 s4
Examples: Al2(SO4)3  
+3
 2Al +3SO4
−2

1. AgBr + AgSCN 2s 3s
2 3 2+3 5
2. CaF2 + SrF2 Ksp = 2 3 (s) = 108 s
3. MgF2 + CaF2 Na3Li3(AlF6)2   
+ +3
 3Na + 3Li + 2AlF6
−3

Ksp = 33 33 22 (s)3 + 3 + 2 = 2916 s8

Solubility Product
Solubility product is the product of the molar concentra- Solubility Product and Precipitation
tions of ions of an electrolyte in saturated solution at a par- • I f Ksp ≈ ionic product, the solution is saturated, and for
ticular temperature. It is denoted by Ksp or S. precipitation, more solute should be added.
• If ionic product > Ksp, the solution is super saturated, and
For a binary electrolyte AB therefore gets easily precipitated.
AB  

 AB 

 A+ + B− • If ionic product < Ksp, the solution is unsaturated and
Solid Un-ionized therefore no precipitation takes place.

So, K = Salt Hydrolysis

or K.[AB] = [A+] [B−] • W hen a salt is added to water, ions of the salt interact
with water to cause acidity or basicity in aqueous solu-
Ksp = [A+][B−] (At constant temperature) tion. This ionic interaction is called salt hydrolysis.
• Interaction of cation is cationic hydrolysis and interac-
General representation tion of anion is anionic hydrolysis.

AxBy 
+y
 xA + yB
−x
• Hydrolysis is reverse of neutralization and is an endo-
Ksp = [A+y]x [B−x]y thermic process.
• If hydrolysis constant is Kh and neutralization constant is
Examples:
Kn, then Kn = 1/Kh.

1. CaF2 
+2
 Ca + 2F
−
• A solution of the salt of strong acid and weak base is
Ksp = [Ca+2] [F−]2 acidic and for it pH < 7 or [H+] > 10−7, for example,
 FeCl3 (salt of a weak base + strong acid). Here, the solu-

+ −2
2. Ag2CrO4   2Ag + CrO4
tion is acidic and involves cationic hydrolysis.
Ksp = [Ag+]2 [CrO4−2] • A solution of the salt of strong base and weak acid is
basic and for it, pH > 7 or [H+] < 10−7, for example, KCN
Relation Between Solubility (s) and (salt of a strong base + weak acid). Here, the solution is
Solubility Product (Ksp) basic and involves anionic hydrolysis.
 • A solution of the salt of a weak acid and a weak base is:

+y
AxBy   xA + yB−x
1. Acidic, if Ka > Kb
a 0 0
2. Basic, if Ka < Kb
a – s x s ys
3. Neutral, if Ka = Kb is neutral
Ksp = (x s)x (y s)y
• CH3COONH4 (salt of a weak acid + weak base) Here, the
or solution is neutral and involves both cationic and anionic
Ksp = xx yy (s)x+y hydrolysis.
7.38 ■ Chapter 7

• A solution of the salt of strong acid and strong base is Acid

neutral or pH = 7 or [H+] = 10−7 • H A + H2O A– + H3O+ 
• A salt of a strong acid and a strong base is never hydro- +
where H3O hydronium ion or hydrated proton.
lyzed. • Water can accept H+ to form hydronium ion (H3O+) due
However, ions are hydrated, for example K2SO4 (salt of a to hydrogen bonding. For example, [H5O+2, H7O+3 ]
strong base + strong acid) • H+ can hold water molecule by hydrogen bond, as it has
high heat of hydration. For example, HNO3, H2SO4, HX
Degree of Hydrolysis • H3O+ has sp3 hybridization and is trigonal pyramidal in
It is the amount or fraction of the salt which is shape.
hydrolyzed.
It is denoted by h.  umber of H+ donated = Basicity or protosity of the acid
• N
Examples:
Number of moles of salt hydrolyzed
h= 1. H3PO4 (tribasic)
Total moles of the salt taken
O
↑
Various Expressions for Kh­, h and pH for H–O–P–O–H
Different Type of Salts ½
1. For the salt of weak acid and strong base like KCN, O–H
.Z 2. H3PO3 (dibasic)
Kh= H
.D
½
h = (Kh/C) H–O–P–O–H
h = (Kw/Ka · C) ↓
_1 O
pH = 2 [pKw + pKa + log C]
_1 3. H3PO2
pOH = 2 [pKw – pka – logC]
O
2. For the salt of strong acid and weak base like FeCl3, ↑
. Z
H–P–H
Kh = ½
. E
O–H
h = (Kh/C)
Base
h = (Kw/Kb · C)
_1 • B
 .OH + H2O B+ + H3O2– [or H5O3– ]
pH = 2 [pKw – pKb – log C] For example, NaOH, KOH.
3. For the salt of weak acid and weak base like
Strength of Acid and Base
CH3 COONH4,
1. Acidic strength ∝ Ka
. Z Ka = Dissociation constant of the acid
Kh =
.. D E 2. Base strength ∝ Kb
h = (Kw/Ka Kb) Kb= Dissociation constant of the base
_1 3. Relative strength = (K1/K2)
pH = 2 [pKw + pKa–pKb]
K1
H3PO4   
–
 H2PO4 + H+ or H3O+
Acid and Base K2
H2PO4–    HPO–2 + H+
Arrhenius Concept of Acid and Base K3
4

According to arrhenius concept, “Acids are H+ ion donor in 

HPO4– 
 PO4–3 + H+
water and bases are OH– ion donor in water.’’
 Ionic Equilibrium ■ 7.39

Lewis Concept of Acid and Base

Here K1 > K2 >> K3 so the correct acidic strength order Lewis acids are electron deficient species which can
is H3PO4 > H2PO4– > HPO4–2 accept an electron pair. Following are the species which act
+
4. As negative charge develops the removal of H becomes as Lewis acids:
more and more difficult so acidic nature decreases. 1. Cations
–C+–, NO+2 , X+ (Halonium ion)
|
Facts to Remember
2. Electron deficient central atoms
• This concept fails to explain acidic and basic nature BeX2, BX3, FeX3, AlX3, SnCl2, ZnCl2
of AlCl3, BX3, NH3. ↓ ↓ ↓ ↓ ↓ ↓
4 6 6 6 4 4
Bronsted Lowery Concept or Proton 3. Central atom with multiple bonds only
Concept O=C=O, O=S=O, S=C=S, SO3
Acid 4. If in a molecule, central atom has vacant d orbit-
Acids are proton or H+ donor. als, it can have more than eight electrons, that is, an
HA A– + H+ expansion of octet state occurs and it can behave as
Acid Conjugate base a Lewis acid.
For example, HX H+ + X– For example,
Conjugate base –
H2SO4 H+ + HSO4– (1) PX5 + X PX6–
Acid Conjugate base Lewis acid Lewis base
–
HNO3 H + NO–3
+
(2) SiX4 + 2X SiX6–2
Base Lewis acid Lewis base
Bases are proton or H+ acceptor
• Some other examples of Lewis acids are:
Base + H+ (Base H)+
SnX4, PX3, GeX4, SF4, SeF4, TeCl4
Proton Conjugate base
given by acid • Elements with an electron sextet (for example O, S)
For example, OH– + H+ H2O
Base Conjugate base Strength of Lewis Acid
Amphoteric or Ampholyte Substances 1. Lewis acid strength ∝ Electronegativity difference
Such a substance can behave both like an acid and a base Example:
that is, it can donate or accept H+ or proton. $O) $O&O $O%U $O,
   
Examples: $FLGLF QDWXUHLQFUHDVHV
+H+ –H+ 2. In case of boron halide (BX3)
1. NH+4 NH3 NH 2–
Conjugate Ampholyte Conjugate BI3 > BBr3 > BCl3 > BF3
acid base No back Less back Maximum back
bonding bonding bonding
+H+ –H+
2. H3O+ H2O OH–
3. In BF3 fluorine shifts its electron pairs back to boron
Conjugate Ampholyte   Conjugate
atom. In F-atom, due to its small size and more
acid base
electron density (2p5), there is more e––e– repulsion.
Some other examples are HSO4–, HCO3–, H2PO4–, HPO42–,
But in case of B, the atom size is large and 2p orbital is
H2PO3–, HS– and HC2O4–
almost vacant.
Facts to Remember 4. The decreasing order of strength of some Lewis acids is
given below:
• H2PO2–and HPO32– are only bronsted bases. As H3PO2
and H3PO3 are monobasic and dibasic acid respectively, BX3, AlX3, FeX3, GaX3, SbX5, InX3, SnX4, AsX5, ZnX2,
HgX2
they can release only one and two H+ ions respectively.
7.40 ■ Chapter 7

Lewis bases These are species which donate lone pair of • Strength of oxyacids ∝ Oxidation number of
electrons. central atom
• Any anion or molecule with octate state and central +1 +3 +5 +7
atom with lone pair of electrons, is a Lewis base as it can 1. HOX < HXO2 < HXO3 < HXO4
donate its lone pair.
– – – Increasing order of acidic nature
For example, X , OH , CN
2. N–3 H3< H2 N2+1 O2 < HN+3 O2 < HN+5 O3
R R
:

:
:

N NH3 R – NH2 NH R N
Facts to Remember
R       R
p    s t • Order of acidic strength: H3PO2 > H3PO3 > H3PO4
:

:
PH3   H—O— H R—O—H R—O—R
Effects of a solvent on acidic strength A solvent
:

:
•  ome multiple bonded molecules which form com-
S also effects acidic strength and it is called levelling effect.
plexes with transition metals. For example, CO, NO, For example,
C2H4.
1. CH3COOH
•  H3COOH behaves like a weak acid in water, but in
C
Strength of Lewis Base
liquid ammonia, it is a strong acid as ammonia has
 a greater tendency to accept H+ than water.
Lewis base ∝
(OHFWURQHJDWLYLW\ GLIIHUHQFH For example,
NH3 > NI3 > NBr3 > NCl3 > NF3 
CH3COOH + H2O 
 CH3COO– + H3O+
Least electronegativity difference Acid Base   Conjugate Conjugate
base acid
Facts to Remember 
CH3COOH + NH3 
–
 CH3COO + NH4+
• CO, RCH=CH2, RC≡CH are border line Lewis bases. Acid Base    Conjugate Conjugate
+
• H O+, NH are neither Lewis acid nor Lewis bases. base acid
3 4
•  H3COOH in HF behaves like a base, as HF is stron-
C
Factors Affecting Acidic Strength ger acid than CH3COOH.
CH3COOH + HF CH3COO+H2 + F –
Effect of electronegativity difference
Base Acid    Conjugate Conjugate
• Acidic strength ∝ Electronegativity difference
   acid     base
1. HF > H2O > NH3 > CH4 2. HNO3
As electronegativity of F > O > N > C. HNO3 is a strong acid in water but a weak acid in
HNO3 > H2CO3 > H3BO3 CH3COOH and acts as a base in HF.
As electronegativity of N > C > B.
3. HClO4
2. HClO > HBrO > HIO
HClO4 (the strongest acid) behaves as a weak acid
HClO3 > HBrO3 > HIO3
in HF.
As electronegativity of Cl > Br > I.
• Acidic strength ∝ Size of central atom Strength of Lewis Base
or ease of removal of H+ HClO4, HClO3, Hl, H2SO4, HBr, HCl, H3O+, HNO3, HF,
HF < HCl < HBr < HI HSO4–, H3PO4, HCOOH, CH3COOH, H2CO3, H2S,
NH4+, HCN, C6H5OH, H2O, R–OH, HC≡CH, NH3,
H2O < H2S < H2Se
H2C=CH2, CH4, C2H6, C6H12 (cyclohexane)
NH3 < PH3 < AsH3 < SbH3
 Ionic Equilibrium ■ 7.41

• T he range of pH value between lower and upper limit

Corresponding Conjugate Bases in at which the colour of indicator changes, is called
Increasing Order of Acidic Strength pH range.
ClO4–, ClO3–, I –, H2O, NO3–, F –, SO42–, H2PO–4, HCOO–, • This pH range depends upon the nature and concentra-
CH3COO–, HCO3–, HS–, NH3, CN –, C6H5O–, OH –, OR–, tion of acid and base used in the titration. For example,
C – ≡ CH, NH2–, CH– = CH2, CH–3, C–2 H5, C–6 H11 phenolphthalein or methy1 red or methyl orange indica-
Strongest tor can be used in the range of titration of strong acid
conjugate base
versus strong base.
• Phenolphthalein can also be used in titration between
Nature of Oxides weak acid with a strong base, but it does not work in the
titration of a weak base with a strong acid titration.
Lux–flood concept • W hile titrating a base with a strong acid, both methy1
• A n acidic oxide takes up oxygen while a basic oxide orange and methy1 red can be used.
gives up oxygen. • In the titration of a weak acid with weak base, there is no
Example: suitable indicator, as pH change is not sharp at the end
CaO + CO2 CaCO3 point.
Basic Acidic • W hen several indicators are mixed in a definite propor-
6Na2O + P4O10 4Na3PO4 tion, a universal indicator is formed which exhibits char-
• An acidic oxide produces an acid with water while a acteristics colours at different pH values.
basic oxide produces a base with water. • An indicator exhibits dark colour in quinoid form, that is
Example: when benzoid form changes into quinoid form, a sharp
SO3 + H2O H2SO4 colour change occurs.
Acidic • At the end point in acid–base titration, acid is present in
Na2O + H2O 2NaOH slight excess.
Basic • The colour of an indicator is determined by the ratio of
[In–]/[HIn].
Some Acidic Oxides
Hard and Soft Acids and
Cl2O7, P4O10, SO2, CO2, SiO2, SO3, N2O3, B2O3, CrO3, WO3,
MoO3, Mn2O7.
Bases (HSAB Principle)
Some Basic Oxides Hardness is the property to retain valence electrons very
M2O (here M = IA metal), MO (Here M = IIA metal), strongly. On the basis of this concept, hard and soft acids or
Sc2O3, TiO2, ZrO2. bases are described as follows:
Some Amphoteric Oxides Hard acids Acceptor atom is small sized, has high
BeO, CrO, Al2O3, Sb2O3, SnO, PbO, ZnO, Cr2O3. charge and has no electron. For example, H+, Li+, Na+, Be2+,
Mg2+, Al3+, Cr3+, Fe3+, BF3, AlCl3.

Acid–Base Indicators Soft acids Acceptor atom is large sized, has a low charge
• A cid–base indicators are weak organic acids or bases and possesses electrons. For example, Pb2+, Cd2+, Hg2+,
which exhibit a sharp colour change at the end point of a Cu+, Ag+, Hg2+.
titration.
Hard bases These are Lewis bases that hold electrons
• Such indicators exhibit different colours in acidic and strongly. For example, H2O, NH3, R–OH, RNH2, OHˉ, Fˉ,
basic medium. For example, methy1 orange exhibits red
ROˉ.
colour in acidic medium while shows yellow colour in
basic medium. Soft bases These are Lewis bases from which, electron
• At the end point of an acid–base titration, a sharp change can be easily removed. For example, R2S, RSˉ, Iˉ, CNˉ,
of pH occurs, so colour of indicator changes. CO, Rˉ.
7.42 ■ Chapter 7

Table 7.2 Acid Base Titrations

7. T he buffer system present in blood is H2CO3 +
[Link]. Type of Example pH change at NaHCO3.
titration the end point 8. In case of strong acid with 10–8m concentration
1 Strong acid– 0.1 M HCl and 4–6.3 pH is 6.95 and in case of strong base with same
weak base 0.1 M NH4OH concn pH is 7.0414.
2 Strong base– 0.1 M NaOH 7.7–9.7
(H+) from acid = 1 × 10–8
weak acid and 0.1 M (H+) from H2O = 1 × 10–7
CH3COOH Net (H+) = 1.1 × 10–7
3 Weak acid– 0.1 M No sharp change pH = –log [1.1 × 10–7] = 6.95
– H] Net = 1.1 × 10–8
weak base CH3COOH and is observed Similarly, for base [O
0.1 M NH4OH pOH = 6.95
4 Strong acid– 0.1 M HCl and 5.5–8.5 pH = 14–6.95 = 7.05
strong base 0.1 M NaOH

Important formula
Table 7.3 S
 ome Indicators and Their Colour Changes Degree of lonization
with the Respective pH Range
1XPEHU RI PROHFXOHV GLVVRFLDWH
Indicator Colour Colour pH range α=
in acidic in basic
7RWDO QXPEHU RI PROHFXOHV
medium medium
Ostwald dilution law
Phenolphthalein Colourless Pink 8.2–10
For a binary weak electrolyte
Thymol blue Yellow Blue 8–9.6
Phenol red Yellow Red 6.8–8.4 K= or α2 = KV or α = (KV)
Methyl red Red Yellow 4.2–6.3
Methyl orange Red Yellow 3.1–4.4
• If ‘C’ is the concentration, then

K=

Points to Remember
1. According to Ingold concept, an electrophile is an K = C α2 or α2 = K/C
acid while a nucleophile is a base. For example, α2 = (K/C)
AlCl3 (electrophile) is an acid and NH3 (nucleo- λv Λ
• α= or Λv
phile) is a base. λ– –

2. In the reaction I2 + Iˉ I3ˉ , the Lewis base  ere λv or Λv is equivalent conductivity at V dilution.
• H
is Iˉ. λ∞ or Λ∞ is equivalent conductivity at infinite dilution.
3. [Fe(H2O)6]3+ + H2O [Fe(H2O)5 OH]2+ + H3O+
• λv = Kv × V
Acid Base Conjugate Conjugate
Here Kv = specific conductivity
base acid
V = dilution
4. [Zn(H2O)5 OH]2+ + H3O+ [Zn(H2O)6]3+ + H2O
Base Acid Conjugate Conjugate • λ∞ = λc + λα
    acid base Here λc and λα are ionic mobilities of cations and
5. T
 he reaction of a cation or anion with water anions.
accompanied by cleavage of O–H bond, is called salt
hydrolysis. Ionic product of water
6. A change of 0.2 unit in pH of blood may cause death • Kw = Ka × Kb
also. • pKw = pKa + pKb
 Ionic Equilibrium ■ 7.43

pH scale Various expressions for Kh, h and pH

fordifferent types of salts
• [H+] = 10–pH
For salt of weak acid and strong base (KCN)
• pH = –log10 [H+]
Kh =
• pH = log10

h = (Kh/C)
pOH
[OH–] = 10–OH h = (Kw/Ka · C)
 _1
pOH = –log[OH–] or pH = 2 [pKw + pKa + log C]
ORJ> 2+ ±@
_1
pOH = 2 [pKw – pKa – log C]
Solubility product
Ksp = [A+] [B–] (At constant temperature.) For salt of strong acid and weak base (FeCl3)

AxBy 
 xA+y +yB–x Kh =

Ksp = [A+y]x [B–x]y h = (Kh/C)

Relation between solubility (s) and h = (Kw/Kb · C)
solubility product (Ksp) _1
pH = 2 [pKw – pKb – log C]
Ksp = (x s)x. (y s)y For salt of weak acid and weak base
or
Ksp = xx yy (s)x+y Kh =

Degree of hydrolysis h = (Kw/[Link])

1XPEHU RI PROHV RI VDOW K\GURO\]HG _1
pH = 2 [pKw + pKa – pKb]
h=
7RWDO PROHV RI WKH VDOW WDNHQ

Solved numericals
Dissociation Constant, Solution
Degree of Dissociation K (formic acid) = 1.77 × 10–4
1. The dissociation constant of CH3COOH at 298 K K (acetic acid) = 1.75 × 10–5
is 1.75 × 10–5. What will be the hydrogen ion
concentration of 0.1 M solution of acetic acid? Strength of formic acid K(formic acid)
=
Solution Strength of acetic acid K(acetic acid)
CH COOH + H O  
 CH COO– + H O+
3 2 3 3 = (1.77 × 10–4/1.75 × 10–5)
C(1 – α) C.α C.α
= 3.18
α = (Kα/C) = (1.75 × 10–5/0.1)
= 0.01323 3. The ionization constant of NH4+ in water is 5.6 × 10–10
[H3O+] = [H+] = C. α at 25oC. The rate constant for the reaction of NH4+ and
OH– to form NH3 and H2O at 25oC is 3.4 × 10–10 litre
= 0.1 × 0.01323
mol–1 sec–1. Find the rate constant for proton transfer
= 1.323 × 10–3 mole/litre. from water to NH3.
2. The dissociation constants of formic acid and acetic Solution
acid are 1.77 × 10–4 and 1.75 × 10–5, respectively. 
Find out the relative strength of two acids. NH4+ + HOH 
 NH4OH + H+