Ionic Equilibrium Explained

ACC- CH-IONIC EQUILIBRIUM 1
IONIC EQUILIBRIUM
INTRODUCTION
Chemical reactions mostly take place in solutions. Solution chemistry plays a very significant role in
chemistry. All chemical substances are made up of either polar units (called ions) or non-polar units. The
behaviour of these substances depends upon their nature and conditions of the medium in which they are
added. It is therefore necessary to understand the principles that govern their behaviour in solution.
Ionic equilibrium is observed in substances that undergo ionization easily, or in polar substances in which
ionization can be induced. Ionic and polar substances are more easily soluble in polar solvents because
of the ease of ionization taking place in the solvent medium. With the dissolution of ionic and polar
substances in the solvent, these solutions become rich in mobile charge carriers (ions) and thus can
conduct electricity. Substances, which are capable of conducting electricity are called electrolytes
while those substances which are non-conducting are called non-electrolytes.
The concepts and principles underlying chemical equilibrium are also applicable for ionic
equilibrium. The fundamental concepts of chemical equilibrium, which are useful in ionic
equilibrium are :
 The equilibrium are dynamic in nature.
 The equilibrium constant is independent of the initial concentration of reactants.
 The equilibrium constant depends on temperature and nature of reactants and products.
 The equilibrium can be attained from either side.
 The concentration of pure solids, pure liquids and solvents do not appear in the equilibrium constant
expression.
 The equilibrium in solutions will only have equilibrium constant.
 The degree of dissociation of a weak electrolyte is the fraction of a mole of electrolyte that underwent
dissociation.
 The equilibrium constant for the overall reaction is given by the product of the equilibrium constant of the
individual reactions
 In order to predict the direction of equilibrium movement, reaction quotient (Q) should be compared
with equilibrium constant, K. If Q = K. reaction is at equilibrium, if Q < K, reaction will move from right
to left to attain equilibrium.
 According to Le Chatelier principle if an external stress is applied to a system at equilibrium, the system
will adjust to partially offset the stress.
IMPORTANT TERMS
Electric conductivity
Substance which allow the electric current to pass through them are called electric conductors and
this property is called electric conductivity.
On the basis of Electric conductivity, substances are of two types :
1 Non conductors :
Substance which do not allow the electric current to pass through are called nonconductors. eg. All
covalent compounds & nonmetals.
2 Conductors :
Substance which allow the electric current to pass through are called conductors. eg. all metals,
alloys, all acid and bases, salt and graphite etc.
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2 ACC- CH-IONIC EQUILIBRIUM
On the basis of conducting units conductors are of two types :
Metallic or Electric Conductors :
Electricity conduct due to the presence of free and mobile electron which act as electricity conducting
unit called metallic or electric conductors. eg. Metals, Alloys, Graphite, Gas, Carbon etc.
Ionic Conductors or Electrolytes :
Conductors in which the current is passes through due to the presence of free ions are called Ionic
Conductors or Electrolyte or Electrolytic conductors.
Ionisation :
The process in which molecules of acids bases and salts when melted or dissolve in water dissociate
into ions is called ionization.
ARRHENIUS THEORY OF ELECTROLYTIC DISSOCIATION
The compounds which give ions either in molten state or in solution are called electrolytes. In the
solid state they are bad conductors, but become good conductors either in the molten state in
solution.
(i) When an electrolyte is dissolved in a solvent (usually water) or is melted by heating, it spontaneously
dissociates into oppositely charged particles called ions, to a considerable extent.
H2SO4 2H+ + SO42–
NaCl Na+ + Cl¯
The positively charged ions are called cations and the negatively charged ions are called anions.
(ii) Since the solution of an electrolyte, as a whole, is electrically neutral, i.e; the total charge on the cations
is equal to the total charge on the anions.
(iii) Electrolytic dissociation or ionization produces equilibrium between unionized molecules and the ions in
solution. The degree of dissociation of an electrolyte () is the fraction of one mole of an electrolyte that
has dissociated under the given conditions.
The value of  depends on
(a) the nature of the electrolyte (b) the nature of the solvent
(c) the dilution and (d) the temperature
(a) Nature of electrolyte : Some electrolyte , e.g., mineral acid such as H2SO4, HCl and HNO3, alkalis

such as NaOH and KOH and all salts have a very high degree of ionization (1) at all reasonable
concentration. They are known as strong electrolytes. The number of ions of strong electrolytes is large
and thus such solutions have high conductance.
Some electrolytes, e.g., organic acids such as acetic acid and bases like ammonium hydroxide have a
low degree of ionization in solution. They are called weak electrolytes. The number of ions in solutions of
weak electrolytes is quite small and thus such solutions have low conductance.
(b) Nature of the solvent : A solvent which has a high dielectric constant weakens the attractive force

between the cations and anions. Hence a solvent of high dielectric constant favours the dissociation of
the electrolyte.
Likewise a solvent which can solvate the ions readily, and can release energy by solvation, favours the
dissociation of the electrolyte . Thus the dissociation of acids in water is favoured by the hydration of the
hydrogen ions to form hydronium ions. The enthalpy of hydration of the proton has a very high value.
(c) Dilution : For some electrolytes, degree of dissociation increases with dilution as explained by Ostwald’s

dilution law (explained later)
(d) Temperature : Increase of temperature generally increases ionization.
TYPES OF ELECTROLYTES
There are two types of electrolytes:
(1) Strong electrolytes : These electrolytes are almost completely ionized when dissolved in a polar medium
like water. In solution they are excellent conductors, e.g., HNO3, HCl, KOH, NaOH, etc. Their degree
of ionization is high and approaches unity.
(2) Weak electrolytes : These are not completely ionized when dissolved in a polar solvent and they

behave as poor conductors of electricity, e.g., CH3COOH, H3PO4, H3BO3, NH4OH, etc., Equilibrium
between ions and unionized molecules is established in solution, e.g.,
1 0 0 Initially
CH3COOH CH3COO¯ + H+ At equilibrium
1–   
The above equilibrium is termed as ionic equilibrium. Degree of ionization of weak electrolytes is much
less than unity. ( < < 1)
Degree of ionization, may be defined as a fraction of total number of molecules of an electrolyte which
dissociate into ions.
% ionization
 =
100
Number of mole dissociated
Degree of Ionization () = Total number of moles taken
The following classification of electrolytes is based on their behaviour in a particular solvent, i.e., water.
Solution (aqeuous)
Conducting electrolytes N o n-c on d uc t in g e le ct r o ly t es

(solutions of electrolytes (Solution of non-electrolytes such as
i.e. acids, bases and salts) urea, glucose, sugar, glycerine, etc.)
Strongly conducting (solutions of Strong Weakly conducting (solutions of

electrolytes which ionize almost completely weak electrolytes which slightly ionize
in water such as HCl, H2SO4, HNO3, in water such as CH3COOH, NH4OH,
NH4Cl, NaCl, NaOH, KOH, etc.) H3PO4, HCN, etc.)
Note : - Electrolyte may behave as a strong one in aqueous solution, but it may behave as a weak
one in another solvent. For example, sodium chloride behaves as a strong electrolyte and acetic
acid as a weak electrolyte when dissolved in water but their conducting abilities are comparable
in liquid ammonia solvent.
Illustration
1. Identify the non-electrolyte, strong electrolyte and weak electrolytes in aq. medium of the following
substance.
NaOH, HCl, NaCl, NH2CONH2(Urea), H2SO4, H3PO4, HCN, NH4OH, KOH, C2H5COOH, NH4Cl,
HNO3, C12H12O11(Sugar), C6H12O6(glucose)
Sol. Non-electrolyte : NH2CONH2, C12H12O11, C6H12O6
Weak-Electrolyte : H3PO4, HCN, NH4OH, C2H5COOH
Strong-Electrolyte : NaOH, HCl, NaCl, H2SO4, KOH, NH4Cl, HNO3
OSTWALD’S DILUTION LAW
The application of law of mass action to weak electrolytes is known as ostwald dilution law. There exists
dynamic equilibrium between ions and undissociated molecules of the electrolytes in solution and law of
mass action can be applied to this. Consider a binary electrolyte AB
AB A+ + B-
Initially C 0 0
At equilibrium C(1-  ) C  C  (  = degree of dissociation)
A B  CxC C 2
K  
AB b gb g
C 1  1 
K is termed as ionization constant. For a weak electrolyte value of  is very-very small compared to 1
and (1-  )  1
K 1
 K  C 2    
C C
1
If V be the volume of the solution containing 1 mole of the solute C = .
V
 Hence   KV or   V as ionic equilibrium is set up in case of weak electrolytes.
 Ostwald’s dilution is applicable only in case of weak electrolytes.
 The approximation (1-  )  1 can be applied only if   5% . If on solving a problem by applying the
approximate formula  comes out to be>5% the problems may be solved by applying exact formula
and  may be calculated applying solution of quadratic equation
 b  b 2  4ac
 ( for , a 2 + b + c = 0)
2a
Illustration
1. What concentration of acetic acid is needed to give a hydrogen ion concentration of
3.5  10–4 M? (Ka = 1.8  10–5)
(A) 3.5  10–4 M (B) 6.80  10–3 M (C) 4.2  10–4 M (D) 7.2  10–4 M
Ans. (B)
Sol. Let the concentration of acetic acid be ‘C’.
CH3COOH CH3COO– + H+
C–C C C
C.C
Ka = 1.8  10–5 =   C 2
C 1 
2 Ka Ka
Now   or  = or C = K a .C
C C
5
C = [H+] = 3.5  10–4 M  3.5  10–4 = 1.8 10 C
3.5 104  3.5  104 2 12.25 108

Or C = or C = = = 6.80  10–3 mol L–1
1.8 105 1.8 10 5 1.8 105
Exercise
1. Calculate the concentration of C2H5COOH that is needed to give a hydrogen ion concentration of
10–4 M? (Ka = 2  10–6)
Ans. 5 × 10–3 M
Limitations of Ostwald's dilution law : It holds good only for weak electrolytes and fails completely

in the case of strong electrolytes
CONCEPT OF ACIDS AND BASES
(A) The Arrhenius concept
Arrhenius acid :
An acid is a substance which gives hydrogen ions in aqueous solution as the only cations. e.g.,
HCl H+ + Cl¯
CH3COOH H+ + CH3COO¯
Ex. HNO3, HClO4, HCl, HI, HBr, H2SO4, H3PO4 etc.
Types of Acids
Mono basic acid Di basic acid Tri basic acid
Gives single H+ Gives two H+ Gives three H+

per molecule per molecule per molecule
e.g. HA (HNO3, e.g. H2A (H2SO4, e.g. H3A (H3PO4)
HCIO4, HCl) H3 PO3)
Note :
 H3BO3 is not an Arrhenius acid.
 H+ ion in water is extremely hydrated (in form of H3O+, H5O2+, H7O3+)
 The structure of solid HClO4 is studied by X-ray, It is found to be consisting of H3O+ and ClO4¯
HCIO4 + H2O H3O+ + CIO4¯ (Better representation)
Arrhenius base :
A base is a substance which gives hydroxyl (OH¯) ions in a aqueous solution as the only anions.
NaOH Na+ + OH¯
NH4OH NH4+ + OH¯
Types of Base
Mono acidic base Di acidic based Tri acidic basic
Gives single OH¯ Gives two OH¯ Gives three OH¯

per molecule per molecule per molecule
e.g. CsOH, RbOH, e.g. Ba (OH)2, e.g. Fe(OH)3
NH4OH Ca(OH)2
Note :
 OH¯ ion is present also in hydrated form of H3O2¯, H7O4¯, H5O3¯
 First group elements (except Li) form strong bases
 Neutralization is the combination of H+ ions of the acid and OH¯ ions of the base to form unionized
water.
Na+ + OH¯ + H+ + Cl¯ Na+ + Cl¯ + H2O(l)
i.e. H+ + OH¯ H2O(l)
Strength of acid or base :

(i) Strength of acid or base depends on the extent of its ionisation. Hence equilibrium constant Ka or Kb.
respectively of the following equilibria gives a quantitative measurement of the strength of the acid or
base.
(ii) HA + H2O H3O+ + A¯;
K =
H O  A¯ 
3

a
HA 
(iii) Similarly
B + H2O BH+ + OH¯
K =
BH  OH¯ 

b B
Here H2O is solvent.
(B) The Bronsted-Lowry theory (Protonic concept)
According to this concept, an acid is a substance which has tendency to lose a proton (H+), i.e. an
acid is a proton donor and a base is a substance, which has a tendency to accept a proton, i.e.,
it is a proton acceptor. When an acid loses a proton, the residue will have a tendency to regain a
proton and hence it is referred as conjugate base
Acid Proton + Conjugate base
HCl H+ + Cl¯
+ +
NH4 H + NH3
HSO4¯ H+ + SO42–
The acid and the conjugate base, which differ by a proton, forms a conjugate pair. For example, HCl
and Cl¯ ions form a conjugate pair, Cl¯ is the conjugate base of HCl and HCl is the conjugate acid of
Cl¯. From the examples given above, it is clear that acids and bases may be molecules or ions, but at
least one of the members of a conjugate pair should be an ion.
Conjugate acid–base pairs

In a typical acid base reaction
HX + B HB+ + X¯
+
HX + B HB + X¯
acid base Conjugate Conjugate
acid base
Conjugate
pair
* Forward reaction – Here HX being a proton donor is an acid
B being a proton acceptor is a base
Backward reaction – Here HB+ being a proton donor is an acid
X¯ being a proton acceptor is a base
Acid Base Conjugate Conjugate

acid base
HCl + H2 O H3O+ + Cl¯

HSO4¯ + NH3 NH4+ + SO4–3
[Fe(H2O)6]3+ + H2 O H3O+ + [Fe(H2O)5 (OH)]2+
Note :
 Conjugate acid - base pair differ by only one proton.
 Strong acid will have weak conjugate base and vice versa.
 Reaction will always proceed from strong acid to weak acid or from strong base to weak base.
. Acid Conjugate Base Conjugate acid

base
Ex. HCl Cl¯ NH3 NH4+
H2SO4 HSO4¯ H2 O H3O+
HSO4¯ SO42– RNH2 RNH3+
H2 O OH¯
Amphoteric (amphiprotic) : Substance which can act as acid as well as base are known as amphoteric
HCl + H2O H3O+ + Cl¯
Base
NH3 + H2O NH4+ + OH¯
Acid
Behaviour of acids and bases in aqueous solution
(i) Acids in water : Water functions as a weak base and accepts a proton from the acid, thus

HA + H2O H3O+ + A¯
A¯ can be considered as the conjugate base of anion of salt of the acid HA. So an aqueous solution of
an acid contains hydronium (H3O+) ions (and not H+ ions)
(ii) Strong and Weak acids : (Relationship between a conjugate pair). An acid is considered to be a
strong acid, it can give up its proton readily. In an aqueous solution of HCl, there is equilibrium
HCl + H2O H3O+ + Cl¯
Since HCl can give up its proton readily, this equilibrium will lie far to the right. Consequently the base
Cl¯ cannot take up the proton from H3O+ readily, i.e., Cl¯ is a weak base. In general, the conjugate
base of a strong acid will be a week base.
In the case of a weak acid like phenol,
C6H5OH + H2O H3O+ + C6H5O¯
The equilibrium will lie far to the left. So the conjugate base (C6H5O¯) of a weak acid (C6H5OH) will be
moderately strong. Again there is little ionization in the aqueous solution of a weak acid so the acid is a
weak electrolyte and the solution has a low conductance.
Based on studies of acids it is established that,
HClO4 > HCl > HNO3
(iii) Relationship between the ionization constants of acids and their conjugate bases
Let us derive a relationship between the ionization constants of acid, CH3COOH and its conjugate
CH3COO¯. The equilibrium reaction of CH3COOH in water is written as
CH3COOH(aq) + H2O(l) CH3COO¯ (aq) + H3O+ (aq)
CH3COO¯ H2O 
Keq [H2O] = CH COOH = Ka ......(i)
3
The conjugate base of acetic ion (CH3CO2¯) acts as base in its reaction with water as
CH3COO¯ + H2O(l) CH3COOH(aq) + OH¯ (aq)
CH3COOH OH  
K’eq [H O] =  Kb
2 CH3COO¯ 
Kw
[OH¯] =
H 
 ......(ii)
CH3COOH K W
 K =
b
CH3COO¯  H  
KW
Kb = K
a
Thus, stronger the acid (the larger Ka), weaker will be its conjugate base (the smaller Kb) and vice versa.
Therefore, for an acid-conjugate base pair.
KW = Ka × Kb
Illustration
1. Which is the strongest Bronsted base in the following anion-
(A) ClO¯ (B) ClO2¯ (C) ClO3¯ (D) ClO4¯
Ans. (A)
Sol. HClO is weakest acid among HClO, HClO2, HClO3 and HClO4
2. Give appropriate equation and label acid and base-
Sol. NH2CONH2 + NH3  NH4+ + NH2CONH¯
Acid Base Acid Base
In liquid NH3 solution urea can show weak acidic nature, while in water urea does not dissociate
Exercise
1. Ammonium ion is-
(A) A Lewis acid (B) Lewis base (C) Bronsted acid (D) Bronsted base
Ans. (C)
2. (a) Write conjugate acids of SO42–, NH2¯, F¯
(b) Write conjugate base of HNO2, H2CO3, HClO4
(c) Write conjugate acids and conjugate base of amphoteric species
HS¯, NH3, H2O, HSO4¯
Ans. (a) HSO4¯, NH3, HF
(b) NO2¯, HCO3¯, ClO4¯
(c) (H2S, S2–) (NH4+, NH2¯) (H2SO4, SO42–)
3. Which of the following is the strongest base-
(A) NH2¯ (B) CH3COO¯ (C) C2H5O¯ (D) OH¯
Ans. (A)
(C) Lewis Electronic theory
According to this theory an acid is a molecule or ion, which can accept an electron pair with the formation
of a coordinate bond. For example, in BF3 the boron atom can accept a pair of electron; so BF3 is a
Lewis acid. A base must therefore be any molecule or ions, which has a lone pair of electron, which it
can donate . For example, ammonia molecule has a lone pair of electron; so it is a Lewis base.
H F H F

| | | |
H – N : + B – F H – N B – F
| | | |
H F H F
Other examples of Lewis acid-base neutralization
Base Acid Products
H2O + HCl H2O  HCl or H3O+ + Cl¯
CaO + CO2 CaO  CO2 or Ca2+ + CO32–
H2O + H2O H2O  HOH or H3O+ + OH¯
Classification of Solvents :
There are two types of solvents : (i) Protonic (protic) and (ii) Aprotic
(i) Protonic or protic solvent

(a) They are characterized by the presence of a transferable hydrogen and the formation of “Onium” ions
Autoionisation takes place as :
Ex. (a) H2O + H2O H3O+ + OH¯ (b) NH3 + NH3 NH4+ + NH2¯
(c) 3HX H2X + HX2¯ (d) 2H2SO4 H3SO4+ + HSO4¯
(b) Protonic solvents may be
(a) Acidic (Anhydrous sulphuric acid, liquid HF, Glacial acetic acid etc.)
(b) Basic (liquid NH3)
(c) Amphiprotic (H2O, proton containing anions)
(c) Aprotic solvents :
Such solvents do not have replaceable hydrogen ion in them. These can be classified into three categories.
(a) Non polar or very weakly polar, nondissociated liquids, which do not solvate strongly.
Ex. CCl4, hydrocarbons, C6H6, C6H12 etc.
(b) Non-ionised but strongly solvating, generally polar solvents.
Ex. Acetonitrile CH3CN, DMSO (dimethyl sulfoxide), THF (Tetra hydro furan) and SO2.
(c) Highly polar, autoionising solvents.
Ex. Inter halogen compounds (BrF, IF5 and trichloro phosphine)
(a) 2BRF3 BrF2+ + BrF4¯
(b) 2 IF5 IF4+ + IF6¯
(c) 2Cl3PO Cl2PO+ + Cl4PO¯
LEVELLING SOLVENTS
(i) The Bronsted - Lowery theory can be extended to acid-base reactions in non-aqueous solvents. It can
be used in differentiating the acid strength of a particular acid and in titration of weak bases.
(ii) In water solvent, mineral acids appear to be equally strong because of their complete ionisation, so
water is called levelling solvent because it levels all the acids to the same strength.
(iii) If instead of water solvent, we take mineral acids in pure acetic acid solvent (which is poor proton
acceptor as compared to water) it is found acids become weak and can be differentiated.
Ex. HCl + CH3COOH Cl¯ + CH3COOH2+
Acid Base Base Acid
In above example acetic acid and Cl¯ ions both complete for protons and the former being a poor
proton acceptor does it much less effectively than water. Thus HCl in acetic acid solvent appears to be
a much weaker acid than that in water.
(iv) Mineral acids in acetic acid solvent follow the following order of their strengths.
HNO3 < HCl < H2SO4 < HBr < HClO4
COMMON ION EFFECT
The degree of dissociation of a weak electrolyte is suppressed by the addition of another electrolyte
(strong) containing common ion. This is referred to as common ion effect e.g. Acetic acid is a weak
electrolyte and its ionization is suppressed in presence of strong acid (H+ ion as common ion).
Let AB be the weak electrolyte, considering its dissociation
AB A+ +B-
A  B
K
AB
The equilibrium constant K has a definite value at a given temperature. If another electrolyte containing
A + or B- ions added to the above solution will increase the concentration of A+ or B- ions, in order, that
K remain constant, the concentration of AB must increase, equilibrium will shift to the left side.
Illustration
1. Determine the degree of dissociation of 0.05 M NH3 at 250C in a solution of PH =11
Sol. NH4OH NH4 + + OH-
C 0 0
Given pH = 11  [H+] = 10–11
[H+][OH-]= 1 × 10-14
1×1014
 OH   11
 103  C
10
OH  10 3
    2 ×10 2 or 0.2%
C 0.05
2. What will be the resultant pH when 200 ml of an aqueous solution of HCl (pH=2.0) is mixed with 300
ml of an aqueous solution of NaOH (pH=12.0)
Sol. pH of HCl = 2,  HCl  102 M
pH of NaOH = 12, pOH= 2  NaOH  10 2 M
HCl + NaOH  NaCl + H2 O
Meq.initial 200x10-2 300x10-2 0 0
=2 =3
Meq. final 0 1 2 2
1
 OH  from NaOH=  2x103 M
500
pOH = - log[OH-]=-log(2 ×10-3)
 pOH  2.6989  pH=14-pOH = 14-2.6980 = 11.3010.
3. Ka for acid HA is 4.9 x 10-8. After making the necessary approximation, calculate for its decimolar
solution at 250C.
(i) % dissociation (ii) pH (iii) OH- concentration
Sol. HA H+ + A-
C 0 0
H A C. C C 2
Ka   Ka    C 2
HA C(1   ) (1   )
4.9 x108
i)   
Ka
C

1 / 10
b
C  1 / 10M g
= 7 × 10-4= 0.07 %
1
ii) [H+]=C  =  7  10 4  7  10 5 mol L1
10
iii) [H+][OH-]=1 × 10-14
1014
 OH   5
 1.43×1010 mol / Lt.
7 ×10
4. A solution of HCl has a pH = 5. If one ml of it is diluted to 1 liter what will be pH of resulting solution ?
Sol. [HCl]=10-5 M (As pH =5]
Meq of HCl in 1 ml = 10-5 x 1 = 10-5
Let normality after diluting
One ml of HCl (pH=5) to one liter is (N)
Meq of HCl (conc)= Meq of HCl dilute.
10-5 × 1 = N × 100  NHCl (dil.)=10-8
HCl  H + + Cl-
10-8 0 0 Initial
0 10-8 10-8 Final
 [H+]=10-8 but pH = 8 is not possible because solution is acidic. As (H+)=10-7 M are already present
in solution from the dissociation of water and since 10-8 < 10-7 and thus it should not be neglected
 H   108  10 7  (11
. ) x107 M
 pH =6.9586.
The above solution for pH of the resultant solution has discrepancy, that dissociation of
weak electrolyte is also suppressed in presence of HCl due to common ion effect.
[H+]H2O  10-7 but lesser than this.
H2 O H+ + OH¯
-8
(10 +x) x
Kw=(10-8+ x)x  x = 0.95 × 10-7
 H   108  0.95×107  2105
. ×107
 pH = 6.9788
1
5. Prove that degree of dissociation of weak acid is given by   . Where Ka is its dissociation
1  10bpK  pH g
a
constant of weak acid?
Sol. For a weak mono protic acid
HA H+ + A-
C 0 0
C(1-  ) C C
+
[H ]=C 
C 2
b g (Ostwall dilution law)
Ka= 1 
K b1   g
a
C 
2
 H 
b g
Ka 1  
2
b g
K 1 
×  a
 
  log[ H  ]   log K a  log(1   )  log 
 pH   log K a  log

 pH  pKa  log
b g
1 
(1  ) 
 log
(1   )

b
 pK a  pH  g
(1   )

1
 10bpKa  pH g  1  10bpKa  pH g

1

1  10bpKa  pH g
PROPERTIES OF WATER
Amphoteric (amphiprotic) Acid /Base nature :

Water act as an acid as well as a base according to Bronsted - Lowry theory but according to Lewis
concept it can only be taken as base only.
In pure water [H+] = [OH¯] so it is neutral.
Molar concentration / Molarity of water :

1000g / litre
Molarity = No. of moles/litres = = 55.55 moles / litre = 55.55 M (density = 1 g/cc)
18g / moles
Ionic product of water :
According to arrhenius concept
H2O H+ + OH¯ so, ionic product of water, kw = [H+] [OH¯] = 10–14 at 25º (exp.)
Dissociation of water is endothermic, so on increasing temperature Keq increase.
Kw increases with increase in temperature.
Now pH = – log [H+] = 7 and pOH = – log[OH¯] = 7 for water at 25ºC (experimental)
pH  7  pOH  neutral

pH  7or pOH  7  acidic  at 25ºC
pH  7or pOH  7  basic 
Ionic product of water is always a constant whatever has been dissolved in water since its an equilibrium
constant so will be dependent only on temperature.
Degree of dissociation of water :

no. of moles dissociated
H2O H+ + OH¯   = Total no. of moles initially taken
10 7
= = 18 × 10–10 or 1.8 × 10–7 %
55.55
Absolute dissociation constant of water :
H  OH ¯ 

10 7  10 7
H2O H+ + OH¯ Ka = Kb = H 2O = = 1.8 × 10–16
55.55
So, pKa = pKb = – log (1.8 × 10–16) = 16 – log 1.8 = 15.74
Acidity and pH scale :

Acidic strength means the tendency of an acid to give H3O+ or H+ ions in water.
So greater the tendency to give H+, more will be the acidic strength of the substance.
Basic strength means to give OH¯ ions, more will be basic strength of the substance.
The concentration of H+ ions is written in a simplified form introduced by Sorenson known as pH scale.
pH is defined as negative logarithm of activity of H+ ions.
 pH = – log a (where a H  , is the activity of H+ ions)

H
Activity of H+ ions is the concentration of free H+ ions or H3O+ ions in a solution.
The pH scale was marked from 0 to 14 with central point at 7 at 25º C, taking water as solvent.
If the temperature and the solvent are changed, the pH range of the scale will also change. For example
0 – 14 at 25 ºC (Kw = 10–14) Neutral point, pH = 7
–13
0 – 14 at 80 ºC (Kw = 10 ) Neutral point, pH = 6.5
pH CALCULATION OF DIFFERENT TYPES OF SOLUTIONS
(a) Strong acid solution :

(i) If concentration is greater than 10–6 M.
In this case H+ ions coming from water can be neglected.
so [H+] = normality of strong acid solution.
(ii) If concentration is less than 10–6 M but greater than 10–8 M
In this case H+ ions coming from water cannot be neglect.
So [H+] = normality of strong acid + H+ ions coming from water in presence of this strong acid.
(iii) If concentration is less than 10–8 M, in this case H+ ions coming from water is considered only.
Illustration
1. Calculate pH of 10–8 M HCl solution.
Sol. H2 O H+ + OH¯
10–8+ x x
+
kw = [H ] [OH¯]
10–14 = x (x + 10–8)
 x2 + x × 10–8 – 10–14 = 0
1
x =  10 8
 10 16
 4  10 14
=
 10 8  10 7 4 
100 =
 
401  1 10 8
= 0.95 × 10–7
2 2 2
[H+] = 10.5 × 10–8 = 1.05 × 10–7
pH = – log [H+]
pH = 7 – log 1.05  7
Exercise
1. Calculate pH of 10–10 M HCl solution.
Ans. pH  7
(b) Strong base solution :

Calculate the [OH¯] which will be equal to normality of the strong base solution and then use
Kw = [H+] × [OH¯] = 10–14, to calculate [H+]
Illustration
1. Calculate pH of 10–7 M of NaOH solution
Sol. [OH¯] from NaOH = 107
[OH¯] from water = x < 10–7 M (due to common ion effect)
H2 O OH¯ + H+
(x + 10–7) x
Kw = [H+] [OH¯] = 10–14 = x (x + 10–7)
x2 + 10–7 x – 10–14 = 0
5 1
 x = × 10–7 = 0.618 × 10–7 ( 5 = 2.236)
2
[OH¯] = 10–7 + 0.618 × 10–7 = 1.618 × 10–7
pOH = 7 – log (1.618) = 6.79
pH = 14 – 6.79 = 7.21
Exercise
1. Calculate pH of a KOH solution having
(a) 5.6 g of KOH mixed in 50 mL water (b) if it is further diluted to make 100 mL
Ans. (a) 14.3 (b) 14
(c) pH of mixture of two strong acids : If V1 volume of a strong acid solution of normality N1 is mixed

with V2 volume of another strong acid solution of normality N2, then
Number of H+ ions from I-solution = N1V1
Number of H+ ions from II- solution = N2V2
If final normality is N and final volume of V, then
NV = N1V1 + N2V2
[Dissociation equilibrium of none of these acids will be disturbed as both are strong acid]
N1V1  N 2 V2
[H+] = N = V1  V2
(d) pH of mixture of two strong bases : Similar to above calculation
N1V1  N 2 V2
[OH¯] = N = V1  V2
+
1014
[H ] =
OH ¯ 
Illustration
1. 500 mL of 10–5 M NaOH is mixed with 500 mL of 2.5 × 10–5 M of Ba(OH)2. To the resulting solution
99 L water is added. Calculate pH.
500  10 5  500  2  2.5  10 5
Sol. [OH¯] = (Normality of Ba(OH)2 = 2 × 2.5 ×10–5)
1000
–5
= 3 × 10 M
M1 = 3 × 10–5 M
V1 = 1L
V2 = 100 L
no. of moles of [OH¯] initially = no. of moles of [OH¯], in final solution.
3 × 10–5 = M2 × 100
 M2 = 3 × 10–7 < 10–6
H2O H+ + OH¯
x (x + 3 × 10–7)
Kw = x (x + 3 × 10–7) = 10–14
 13  3 
 x =  2  × 10–7
 
x = 0.302 × 10–7
 13  3   3  13 
[OH¯]Net = 3  2  × 10–7 =  2  × 10–7 = 3.302 × 10–7
   
Exercise
1. Calculate the pH for-
(a) 50 mL of 0.1 M HCl, 25 mL of 0.1 M H2SO4, 25 mL of 0.2 M HNO2 + 100 mL of H2O
(b) 50 mL of 0.2 M NaOH + 100 mL of 0.1 M RbOH the resulting solution is diluted by 350 mL H2O.
Ans. (a) 1.123 (b) 12.6
(e) pH of mixture of a strong acid and a strong base :

Acid base neutralisation reaction will take place.
The solution will be acidic or basic depending on which component is taken in excess.
If V1 volume of a strong acid solution of normality N1 is mixed with V2 volume of a strong base solution
normality N2, then
Number of H+ ions from I-solution = N1V1
Number of OH¯ ions from II-solution = N2V2
If N 1V 1 > N2V 2 If N 2V 2 > N 1V 1

 
N1V1  N 2V2 N 2 V2  N1V1
[H+] = N = V1  V2 [OH¯] = N = V1  V2
Solution will Solution will

be acidic in nature be basic in nature
1014
[H+] =
OH ¯ 
Illustration
1 1
1. Calculate pH of mixture of (400 mL, M Ba(OH)2) + (400 mL, M HCl) + (200 mL of water)
200 50
1 1
400   400  2
50 200
Sol. [H+] = = 4 × 10–3, so pH = 3 – 2 log 2 = 2.4
1000
2. What will be resultant pH when 150 mL of an aqueous solution of HCl (pH = 2.0) is mixed with 350 mL
of an aqueous solution of NaOH (pH = 12.0) ?
Sol. pH of HCl = 2
 [HCl] = 10–2 M
pH of NaOH = 12, pOH = 2  [NaOH] = 10–2 M
HCl + NaOH  NaCl + H2 O
Meq. initial 150 × 10–2 350 × 10–2 0 0
= 1.5 = 3.5
Meq. final 0 2 1.5 1.5
2
 [OH¯] from NaOH = = 4 × 10–3 M
500
pOH = – log [OH¯] = – log (4 × 10–3)
 pOH = 2.3979
 pH = 14 – pOH = 14 – 2.3979 = 11.6021
Exercise
1. Calculate pH of mixture 200 mL of 0.2 M H2SO4 + 300 mL of 0.2 M NaOH + 200 mL of 0.1 M KOH.
Ans. 7
2. Calculate the pH when 200 mL of 0.25 M H2SO4 is mixed with 200 mL of 0.2 M Ba(OH)2
Ans. 1.30
(f) pH of a weak acid (monoprotic) solution :

Weak acid does not dissociated 100% therefore we have to calculate the percentage dissociation using
(Ka) dissociation constant of the acid.
We have to use Ostwald’s Dilution law (as have been derived earlier)
HA H+ + A¯
t = 0 C 0 0
H  A ¯ 

C 2
At eq c(1 – ) C C Ka = =
HA 1 
Ka
If  << 1  (1 – )  1  Ka = C2   = (is valid if  < 0.5)
C
Ka 1
[H+] = C = C = K a  C So pH = (pKa – logC)
C 2
On increasing the dilution  C = a and [H+]  pH
Illustration
1. Calculate pH of (a) 10–1 M CH3COOH (b) 10–3 M CH3COOH

Ka = 2 × 10–5
Sol. (a) CH3COOH CH3COO¯ + H+
C 0 0
C(1–) C C
C 2 Ka 2 105
Ka =   = = = 2  10 4 ( << 0.1)
1  C 101
1
So, [H+] = 10–1 × 2 × 10–2  pH = 3 – log 2 = 2.85
2
Ka Ka 2 105
(b)  =   = = = 2 10 2 ( > 0.1)
C C 103
Since  > 0.1, exact calculation is required.
C 2 10 3   2
Ka =  2 × 10–5 =   = 13.14%
1  1 
[H+] = 10–3 × 0.1314 = 1.314 × 10–4  pH = 4 – log (1.314)  3.8
Exercise
1. Calculate pH of (a) 10–4 M CH3COOH (b) 10–6 M CH3COOH

Take Ka = 2 × 10–5
Ans. (a) 4.04 (b) 6.022
Note : At very low concentration (at infinite dilution) weak electrolyte will be almost 100% dissociate,
so behaves as strong electrolyte
(pH) of 10–6 M HCl = pH of 10–6 M CH3COOH = 6)
(g) pH of a mixture of weak acid (monoprotic) and a strong acid solution :

Weak acid and strong acid both will contribute H+ ion.
For the first approximation we can neglect the H+ ions coming from the weak acid solution and calculate
the pH of the solution from the concentration of the strong acid only.
To calculate exact pH, we have to take the effect of presence of strong acid on the dissociation equilibrium
of the weak acid.
If [SA] = C1 and [WA] = C2, then [H+] from SA = C1 (SA = Strong acid)
the weak acid will dissociate as follows, (WA = Weak acid)
HA H+ + A¯
C2 0 0
C2  C1  C2
C2(1 –) C2 + C1 C2 Ka = C 2 1    ( < < < 1)
(The weak acids dissociation will be further suppressed because of presence of strong acid, common
ion effect)
Ka = (C2 + C1) 
To H+ ion concentration = C1 + C2
If the total [H+] from the acid is more than 10–6 M, then contribution from the water can be neglected, but
if comparable then we take [H+] from water also.
(h) pH of a mixture of two weak acid (both monoprotic) solution :
 Both acids will dissociate partially
 Let the acid are HA2 & HA2 and their final concentrations are C1 & C2 respectively, then
HA1 H+ + A
A1 HA2 H+ + AA2
t = 0 C1 0 0 C1 0 0
At eq. C1(1 – 1) C11 + C22 C11 C2(1 – 2) C22 + C11 C22
C11 (C11  C 2 2 ) (C 2 2  C11 )C2 2
K a1  K a 2 
C1 (1  1 ) C 2 (1  1 )
(Since 1, 2 both are small in comparision to unity)
K a1 1
K a1 = (C11 + C22) 1 : K a 2 = (C11 + C22)2  
Ka2 2
C1K a1 C2 K a 2
[H+] = C11 + C22 =   [H+] = C1K a1  C2K a 2
C1K a1  C2K a 2 C1K a1  C2K a 2
 If the dissociation constant of one of the acid is very much greater than that of the second acid then
contribution from the second acid can be neglected.
So. [H+] = C11 + C22 = C11
Illustration
1. Calculate pH of solution obtained by mixing equal vol. of 0.02 M HOCl & 0.2 M CH3COOH solution
given that K a1 [HOCl] = 2 × 10–4
K a 2 [CH3COOH] = 2 × 10–5
also calculate OH–, OCl–, CH3COO–
Sol. Final solution volume become double
C1 = 0.01 C2 = 0.1
[H+] = K a1 C1  K a 2 C2  2  104  0.01  2 105  0.1  2  106  2 106  2  103
pH = 3 – log2 = 3 – 0.3010 = 2.69
2 104 –1
2 105
1 = = 10 2 = = 10–2
2 103 2 103
HOCl H+ + OCl– CH3COOH H+ + CH3COO–
C1(1 – 1) C11 + C22 C11 C2(1 – 2) C11 + C22 C 2 2
–
[OCl ] = C11 –
[CH3COO ] = C22
= 0.01 × 10–1 = 0.01 × 10–2
= 1 × 10 –1 = 1 × 10–1
KW 10 14
[OH]¯ =  = 0.5 × 10–11
[H  ] 2 103
= 5 × 10–12 M
HOCl = 10–2 (1– 0.01) = 9 ×10–3 M
[CH3COOH] = 10–1(1-0.01)  10–1
Exercise
1. Calculate pH of solution obtained by mixing equal vol. of 2 M HOCl & 3 M HA solution given that
K a1 [HOCl] = 2 × 10–4, K a 2 [HA] = 2 × 10–5
Ans. 1.4
RELATIVE STRENGTH OF WEAK ACIDS AND BASES
The relative strength of weak acids and bases are generally determined by their dissociation constants
Ka and Kb respectively. For weak acid i.e. CH3COOH
CH3COOH CH3COO¯ + H+
C 0 0
C(1–) C C
C.C C.2 2
Ka = =
C1    1     Ka = C (if  < < 1)
Similarly, for weak base, i.e. NH4OH
NH4OH NH4+ + OH¯
C 0 0
C(1–) Ca Ca
Ka = C2
Ka and Kb are just the equilibrium constants and hence depends only on temperature. Greater the value
of dissociation constant of the acid (Ka), more is the strength of the acid and greater the value of
dissociation constant of the base, more is the strength of the base. For two acids of equimolar
concentration.
Strength of acid (I) Ka

1
Strength of acid (II) = Ka

2
Strength of base ( I) Kb
1
Similarly for bases, Strength of base ( II) = K
b 2
The modern method is to convert Ka as a power of 10 and express acid strength by power of 10 with
sign changed and call this new unit pKa. Thus, if Ka for acid is equal to 10–4, pKa = 4. So higher pKa
value means lower acid strength,
that is pKa = – log Ka Also, pKb = – log Kb
Illustration
1. Ka for acid HA is 2.5 × 10–8 calculate for its decimolar solution at 25ºC.
(i) % dissociation (ii) pH (iii) OH– ion concentration
Sol. HA H+ + A–
C 0 0
C (1 – ) C C
[H  ][A  ] C · C C
Ka =   = C2
[HA] C(1 – ) (1  )
Ka 2.5  10 8
(i)   =  (C = 1/10 M)
C 1 / 10
–4
= 5 × 10 = 0.05%
1
(ii) [H+] = C = × 5 × 10–4 mol/L  So pH = 5 – log 5 = 4.30
10
(iii) [H+] [OH–] = 1 × 10–14
–
1014
 [OH ] = = 2 × 10–10 mol/L
5 104
2. Determine the degree of dissociation of 0.05 M NH3 at 25ºC in a solution of pH = 10.
Sol. NH4 NH 4 + OH–
C 0 0
Given, pH = 10
[H+] = 10–10
[H+] [OH–] = 1 × 10–14
11014
 [OH] = = 10–4 = C
1010
[OH  ] 104
  =  = 2 × 10–3 or 0.2%
C 0.05
3. Two weak monobasic organic acids HA and HB have dissociation constants as 1.6 × 10–5 and
0.4 × 10–5 respectively at 25ºC. If 500 mL of 1 M solutions of each of these two acids are mixed to
produce 1 litre of solution, what is the pH of the resulting solution?
Sol. In such cases, we have to consider H+ from both HA and HB simultaneously. The concentration of HA
and HB in the mixture = 0.5 M [equal volumes are mixed] = say ‘c’
HA  H+ + A–
BH  H+ + A–
Let, x = [H ] from HA and y = [H+] from HB
+
 [H+]final = x + y
( x  y) x ( x  y) y
KHA = and KHB =
C C
[H  ]HA x k HA  C

 
[H ]HB y k HB  C
x 1.6 105
 2
y 0.4 105
x
x = 2y  y =
2
x x 2  xy
Substitute for y = in KHA =
2 c
2x 2  x 2
1.6 × 10–5 =
2  0.5
2 –5
3x = 1.6 × 10  x2 = 5.33 × 10–6
x = 2.30 × 10–3 M, y = 1.15 × 10–3 M
[H ]Final = x + y = 2.30 × 10 + 1.15 × 10–3 = 3.45 × 10–3 M
+ –3
pH = –log10 (3.45 × 10–3)
pH = 2.462
Exercise
1. Saccharin (Ka = 2 × 10–12) is a weak acid represented by formula HSaC. A 8 × 10–4 mole amount of
Saccharin is dissolved in 400 cm3 water of pH = 3. Assuming no change in volume, calculate the
concentration of SaC¯ ions in the resulting solution at equilibrium.
Ans. [SaC¯] = 4 × 10–12 M
2. A solution contains 0.08 M HCl, 0.08 M CHCl2 COOH and 0.1 CH3COOH. The pH of this solution
is 1. If Ka for acetic acid is 10–5, calculate Ka for CHCl2COOH.
Ans. Ka = 3.33 × 10–2
ISOHYDRIC SOLUTIONS
(i) Solution of electrolytes are said to be isohydric if the concentration of the common ion present in them is
the same and on mixing such solution, there occurs no change in the degree of dissociation of either of the
electrolyte.
(ii) Let the isohydric solution is made by HA1 and HA2 acids, then [H+] of both should be equal i.e.
C Ka
K a C1  K a C 2 or
1
 2
1 2 Ka C1
2
Illustration
1. The degree of dissociation of pure water at 25ºC is found to be 1.8 × 10–9. Find Kw and Kd at 25ºC.
(A) 3.24 × 10–18; 5.83 × 10–20 (B) 1 × 10–14; 1.8 × 10–15
–16 –14
(C) 1.8 × 10 ; 1 × 10 (D) 1 × 10–14; 1 × 10–14
Ans. (B)
Sol. Since  = 1.8 × 10–14
1000
and for water C = = 55.56
18
[H+] = [OH¯] = C = 55.56 × 1.8 × 10–9 = 1 × 10–7 M
KW = [H+] × [OH¯] = (1 × 10–7)2 = 10–14
H  OH ¯ 

KW
10 14
and Kd = = = = 1.8 × 10–16
H 2O H 2O 55.56
2. When a 0.1 N solution of an acid at 25ºC has a degree of ionisation of 4%, the concentration of OH¯
present is-
(A) 2.5 × 10–3 (B) 2.5 × 10–11 (C) 2.5 × 10–12 (D) 2.5 × 10–13
Ans. (C)
10 14
Sol. [H+] = C = 0.1 × 4 × 10–2 = 4 × 10–3 M or [OH¯] = = 2.5 × 10–12 N
H 

Exercise
1. Calculate the molar concentration of a solution of acetic (HOAc) that has a pH of 4.00.
(Ka = 1.8 × 10–5)
(A) 1.0 × 10–3 (B) 1.0 × 10–6 (C) 0.057 × 10–2 (D) 0.010
Ans. (C)
2. Select the correct option from the following ?
(A) pKW increases with increase of temperature
(B) pKW decreases with increase of temperature
(C) PKW = 14 at all temperature
(D) pKW = pH at all temperature
Ans. (B)
SALTS
(i) Salts are the ionic compounds formed when its positive part (Cation) come from a base and its
negative part (Anion) come from an acid.
(ii) Salts may taste salty, bitter, astringer or sweet or tasteless
(iii) Solution of salts may be acidic , basic or neutral.
(iv) Fused salts and their aqueous solutions conduct electricity and undergo electrolysis
(v) The salts are generally crystalline solids
1. Classification of salts :
These salts may be classified into four categories.
1.1 Simples salts :

The salts formed by the neutralisation process between acid and base. These are of three types.
(i) Normal salt :
The salt formed by the loss of all possible protons (replaceable H+ ions)
Ex. NaCl, NaNO3, K2SO4, Ca3 (PO4)2, Na3BO3, Na2HPO, NaH2PO2 etc.
(ii) Acids salts :
Salts formed by incomplete neutralisation of polybasic acid. Such salts contain one or more replaceable
H atom.
Ex. NaHCO3, NaHSO4, NaH2PO4, Na2HPO4 etc.
Above salts when neutralized by base form normal salts.
(iii) Basic salts :
Salts formed by incomplete neutralisation of poly acidic bases are called basic salts. These salt contain
one or more hydroxyl groups.
Ex. Zn(OH)Cl, Mg(OH)Cl, Fe(OH)2, Cl, Bi(OH)2 etc.
Above salt when neutralised by acids form normal salts.
1.2 Double salts :

(i) The addition compounds formed by the combination of two simple salts are termed as double salts.
Ex. FeSO4 (NH4)2SO4 . 6H2O (Ferrous ammonium sulphate), K2SO4 Al2 (SO4)3. 24H2O (Alum) and
other alums.
(ii) Above salts are stable in solid state only.
(iii) When dissolved in water, it furnishes all the ions present in the simple salt form which it has been
constituted.
(iv) The solution of double salt shows the properties of the samples salts from which it has been constituted
1.3 Complex salts :

(i) The are formed by combination of simple salt or molecular compounds.
Ex. K4Fe(CN)6, Co(NH3)6 SO4 etc.
(ii) FeSO 4  6KCN  K 4 FeCH 6 + K2SO4
 complex salt
simple salts
(iii) CoSO4 + 6NH3  Co(NH3)6SO4

Simple Molecular Complex salt
salt compound
(iv) These are stable in solid states as well as solutions
(v) On dissolving in water, if furnishes a complex ion.
K4Fe(CN)6 H 2O 4K+ + [Fe(CN)6]2–
complex ion
(vi) The properties of the solution are different from the properties of the substance from which it has
been constituted.
1.4 Mixed salts :

(i) The salt which furnishes more than one cation or more than one anion when dissolved in water is
called mixed salt.
Ex. CaOCl2, NaKSO4, NaNH4HPO4 etc.
OCl Na Na
Ca SO4 NH4 PO4
, ,
Cl K H
HYDROLYSIS OF SALTS
Salts are the product of an acid and a base, other than water. Depending on the nature of an acid or a
base there can be four types of salts:
(i) Salt of a weak acid and a strong base.
(ii) Salt of a strong acid and a weak base.
(iii) Salt of a weak acid and a weak base and
(iv) Salt of a strong acid and a strong base.
We shall first look at what is hydrolysis and then find out how to calculate the pH due to it.
1. Salt of a Weak Acid and Strong Base

Let us take a certain amount of weak acid (CH3COOH) and add to it the same amount (equivalents) of
a strong base (NaOH). They will react to produce CH3COONa.
CH3COOH + NaOH  CH3COONa + H2O
CH3COONa being a strong electrolyte, completely dissociates into its constituent ions.
CH3COONa  CH3COO- + Na+
Now, the ions produced would react with H2O. This process is called hydrolysis.
Na+ + CH3COO- + H2O CH3COOH + NaOH
We know that NaOH is a strong base and therefore it would be completely dissociated to give Na+ and
OH- ions.
 Na   CH 3COO   H 2 O CH3COOH + OH- + Na+
Cancelling Na+ on both the sides,
 CH3COO- + H2O CH3COOH + OH-
We can note here that ions coming from strong bases do not get hydrolysed. We should note here
that the solution will be basic. This is because the amount of CH3COOH produced and OH¯
produced are equal. But CH3COOH will not completely dissociate to give H+ ions. Therefore
[OH-]ions will be greater than [H+] ions.
Since the reaction is at equilibrium,
CH 3COOH OH 
KC 
CH 3COO 
This equilibrium constant KC is given a new symbol, Kh.
CH 3COOH OH 
 Kh 
CH 3COO 
If we multiply and divide the above equation by [H+] of the solution, then
CH 3COOH OH  H  H  OH 
Kh  
CH 3COO  H  CH 3COO  H 
CH 3COOH
Kw CH 3COOH OH  K
Kh   Kh  
 w
Ka CH 3COO Ka
CH3COO- + H2O CH3COOH + OH-

Initial C 0 0
At eq: C(1-  ) C C
Where  is the degree of hydrolysis of CH3COO- ion?
C×C K w
 
C(1   ) K a
If  is very much less than 1,
Kw Kw
C 2  ,  
Ka Ka C
Kw KwC
As [OH-]=C  , [OH-]=C × K C  Ka
a
Kw Kw Ka FK . K I 1 pK 1 1
[H+]= OH   C or pH = - log[H+]=-log G
H C J
w a
K= 2 w 
2
pK a  log C
2
Illustration
1. Find out pH, h and [OH¯] of milli molar solution of KCN if the dissociation constant of HCN is 10–7.
Sol. (1) pH = 7 + 1/2 pKa + 1/2 log C = 7 + 1/2 × 7 + 1/2 log10–3
14  7  3 21 3
= 7 + 7/2 – 3/2 log 10 = = = 9
2 2
Kh 1014 103
(2) h =  7
 105
C 10
KW  C 1014 10 3
(3) [OH¯] =  7
 105
Ka 10
2. Calculate for 0.01 N solution of sodium acetate
(i) Hydrolysis constant (ii) Degree of hydrolysis (iii) pH
Given Ka of CH3COOH = 1.9 × 10–5
Sol. For CH3COONa + H2 O CH3COOH + NaOH
Initial C 0 0
After C(1–h) Ch Ch
Kw 1014
(i) Kh =  5
 5.26 10 10
Ka 1.9 10
Kh 5.26  10 10
(ii) h =   2.29  10 6 M
C 0.01
(iii) [OH¯] from NaOH, a strong base = Ch = 0.01 × 2.29 × 10–4 = 2.29 × 10–6 M
pOH = 5.64
 pH = 14 – 5.64 = 8.36
Exercise
1. Calculate the pH and degree of hydrolysis of 0.01 M solution of NaCN, Ka for HCN is 6.2 × 10–12.
Ans. pH = 11.6
Degree of hydrolysis = 4 × 10–11
2. Calculate the pH after the addition of 90 ml and 100 ml respectively of 0.1 N NaOH to 100 ml 0.1 N
CH3COOH (Given pKa for CH3COOH = 4.74)
Ans. pH = 8.71
2. Salt of a Weak Base and a Strong Acid

Let the acid be HCl and the base be NH4OH. Therefore the salt would be NH4Cl.
NH 4Cl  NH4++Cl-
Cl- + NH4 + + H2O NH4OH + HCl
HCl being a strong acid dissociates completely to give H+ ions and Cl- ions.
Cl- + NH4 + + H2O NH4OH + H+ +Cl¯
NH4+ + H2O NH4OH + H+
We can see that the ion coming from the strong acid does not get hydrolysed. We had previously seen
that the ion coming from the strong base also does not get hydrolyzed. Hence, one can conclude that the
salt of a strong acid and strong base does not get hydrolyzed. In this hydrolysis, NH4OH and H+ are
being produced. This implies that the solution is acidic. To calculate pH,
NH4 + + H2O NH4OH + H+

Initial C 0 0
Final C(1–h) Ch Ch
Where h is the degree of hydrolysis of NH4+.
NH 4 OH H 
Kh 
NH 4
Multiplying and dividing by OH- and rearranging.
NH 4 OH H  OH  H  OH  Kw K
Kh   
   K h  w
NH 4 OH NH 4 OH  Kb Kb
NH 4 OH
Now, substituting the concentrations,
NH4 OH H  K w ChxCh Ch 2
Kh   = =
NH4 Kb C(1- h) 1- h
Kw Kw
If h  0.1, then Ch 2   h 
Kb K bC
Kw KwC 1 1 1
Since [H+] = Ch, [H+] = C K C = K or pH = pK w  pK b  log C
b b 2 2 2
Illustration
1. Find out the Kh of centi normal [10–2 N] solution of NH4Cl (SA–WB) if dissociation constant of NH4OH
is 10–6 and Kw = 10–14. Find out degree of hydrolysis and also find [H+] and pH of solution?
Given : Kw = 10–14; Kb = 10–6
1014
Kw
Sol. (1) Kh =  6  108
K b 10
Kh 108
(2) h =  2
 10 6  10 3
C 10
(3) [H+] = Ch
= 10–2 × 10–3
= 10–5
(4) pH = – log [H+] = – log [10–5]
= + log [10–5] = + 5 × 1 = 5
2. How many grams of NH4Cl should be dissolved per litre of solution to have a pH of 5.13 ? Kb for NH3
is 1.8 × 10–5.
Sol. NH4Cl is a salt of strong acid and weak base for solutions of such salts.
1
pH = [pKw – log C– pKb]
2
 10.26 = 14 – log C – 4.74
 log C = 9.26 – 10.26 = – 1.0
 C = 10–1 M
[NH4Cl] = 10–1 M
WNH = 10–1 × 53.5 gL–1 = 5.35 gL–1
4Cl
Exercise
1. Find out the Kh at 363 K (90ºC) of a salt of [Strong acid - Weak base] if the value of Kb is 10–5 [At
90ºC Kw = 10–12]
Kw 10 12
Ans. Kh =  = 10–7
Kb 10 5
2. What is the pH of 0.4 M aqueous NaCN solution ? {Given pKb of CN¯ = 4.70)
Ans. pH = 11.45
3. Salt of a Weak Acid and Weak Base

Let the weak acid be CH3COOH and the weak base be NH4OH. Therefore, the salt is CH3COONH4
The salt completely dissociates.
CH3COONH4  CH3COO- +NH4+
The ions get hydrolyzed according to the reaction.
CH3COO- + NH4 + + H2O NH4OH + CH3COOH
Initial C C 0 0
At equilibrium C(1–h) C(1–h) Ch Ch
NH 4 OH CH 3COOH
Kh  
NH 4 CH 3COO 
Multiplying and dividing by H+ & OH- and rearranging.
NH 4 OH CH 3COOH H  OH  H  OH  Kw
Kh     
  

NH 4 CH 3COO H OH CH 3COO 
H 
NH 4 OH Ka K b
x
CH 3COOH NH 4 OH
Kw
 Kh 
Ka K b
Substituting the concentration terms,
K
Kh  w
Ch Ch bg  h

Ch
2 2
Ka Kb b gb g b g b1  hg
C 1- h C 1- h C 1 h
2 2
As can be seen in the hydrolysis reaction.
CH3COO- + NH4+ + H2O NH4OH + CH3COOH,
CH3COOH is present in the solution. This implies that the equilibrium between CH3COOH, CH3COO
and H+ can exist and therefore would exist.
CH3COOH CH3COO-+H+
In fact the equilibrium between NH4OH, NH4+ and OH- also exists.
Now, we calculate the pH of the solution as,
CH3COOH CH3COO- + H+
C C(1-  )
CH 3COO  H  b gc h
C 1  H
 H   K a×
FG  IJ
Ka 
CH 3COOH

C H1   K
 Kw
Substituting as K K
1  a b
F
G  I
H1  J
Kw K w Ka
[H+]= Ka × K K × a
Ka K b

Kb
1 1 1
or pH = pK w  pK a  pK b
2 2 2
Illustration
1. Calculate pH of the mixture (25 mL of 0.1 M NH4 OH + 25 mL of 0.1 M CH3 COOH)
Given that Ka : 1.8 × 10–5, and Kb = 1.8 × 10–5
Sol. NH4OH + CH3COOH  CH3COONH4 + H2O
Initially milli moles 25 × 0.1 25 × 0.1 0 0
= 2.5 = 2.5
Final milli moles 0 0 2.5 2.5
As salt is formed (salt of weak acid and weak base) and pH will be decided by salt hydrolysis
pK w  pK a  pK b 1
pH =  (–log 10–14 – log 1.8 × 10–5 + log 1.8 × 10–5) = 7
2 2
2. In the following which one has highest/maximum degree of hydrolysis.
(A) 0.01 M NH3Cl (B) 0.1 M NH4Cl
(C) 0.001 M NH4Cl (D) Same
Ans. C
 Kh 
h if C decreases, h increases 
Sol.  C 
 
Exercise
1. In the following which one has lowest value of degree of hydrolysis
(A) 0.01 M CH3COONH4 (B) 0.1 M CH3COONH4
(C) 0.001 M CH3COONH4 (D) Same
Ans. D
4. Salt of strong acid and strong base
Ex. NaCl, BaCl2, Na2SO4, KClO4 etc.
NaCl + H2O NaOH + HCl
+
Na + Cl¯ + H2O Na+ + OH¯ + H+ + Cl¯
H2O H+ + OH¯ (It is not salt hydrolysis)
(a) No hydrolysis
(b) Solution is always neutral
(c) pH = 7 at 25ºC
5. Salt of a weak polyprotic acid and strong base
(i) Salt containing multivalent cation or anion. Hydrolysis of multivalent cation or anion takes place in
stepwise manner and more than one hydrolytic products are formed. For example the hydrolysis of Fe2+
ions will occur in following steps
Fe 2  2H2O Fe(OH)   H3O
Fe (OH)   2H2O Fe(OH) 2  H3O
The hydrolysis constants K h1 and K h 2 are

[ Fe(OH)+ ][ H 3O ] K w
Kh  =
1
[Fe2+ ] Kb
2

[ Fe(OH)2 ][ H 3O ] K w
Kh  =
2 [Fe(OH)+ ] K b1
Where K b1 and K b2 are dissociation constants of Fe(OH)2 . Since K b1 >>>> K b2 thus K h >>> K h

1 2
hence the hydrolysis of Fe(OH)+ in comparision can be neglected and
H O  
3

K h1 C
1 1
or pH  7  pk b  log C
2 2 2
(ii) Salt containing weak conjugate cation and an amphiprotic cation : When a salt like NaHCO3 ,
NaHS , NaH2PO4 , Na2HPO4 etc is dissolved in water the amphiprotic anion can either accept a proton
from water (Hydrolysis) or can donate a proton to water. The pH of the solution can be calculated as
1
pH 
2

pK1  pK a
2

(iii) Salt containing strong conjugate cation and an amphiprotic cation :Examples of such salts are
NH4HCO3 , NH4HS etc. The [H3O+] of the solution can be calculated as
Ka K w
H O  
3
 1
Kb
 Ka Ka
1 2
(iv) Hydrolysis of amphiprotic anion

Let us consider hydrolysis of amphiprotic anion only, i.e., when counter cation is not hydrolysed, example
of some salts of this category are NaHCO3, NaHS, Na2HPO4, NaH2PO4.
Here, H2PO4¯ and HPO42- are amphiprotic anions. pH after their hydrolysis can be calculated as,

pH of H2PO4¯ in aqueous medium = pK a1  pK a 2 / 2 
pH of H2PO2-4 in aqueous medium = pK a2  pK a
3
/ 2
Here, H2PO2-4 is conjugate base of H2PO¯4 and H3PO4 is conjugate acid of H2PO¯4.
Similarly, PO3-4 is conjugate base of HPO-24 and HPO¯4 is conjugate acid of PO3-4 .
When these salts are dissolved in water, [H3O+] concentration can be determined as,
[H3O+] = K a1 K w / k b  K a 2 
pH = -log K a1 K w / k b  K a 2 
Hydrolysis at a Glance
Salt Nature Degree Hydrolysis pH
Constant
1. NaCl Neutral No Hydrolysis

(Strong acid +
Strong Base)
2. CH3COONa Base h = kw/Cka Kh = kw/ka pH=1/2[pkw + pka + logC]

(Weak acid +
Strong base)
3. NH4Cl Acidic h = kw/Ckb Kh = kw/Ckb pH=1/2[pkw- pkb - logC]

(Strong acid +
Weak base)
4. CH3COONH4 * h = kw/(ka + kb) Kh = kw/(ka + kb) pH=1/2[pkw + pka - pkb]

(Weak acid +
Weak base)
In the case of salt of weak acid and weak base, nature of medium after hydrolysis is decided in the
following manner:
(i) If Ka = Kb, the medium will be neutral.
(ii) If Ka > Kb, the medium will be acidic.
(iii) If Ka < Kb, the medium will be basic.
The degree of hydrolysis of salts of weak acids and weak bases is unaffected by dilution because there
is no concentration term in the expression of degree of hydrolysis.
Note : Degree of hydrolysis always increases with increase in temperature because at elevated
temperature increase in Kw is greater as compared to Ka and Kb.
BUFFER SOLUTIONS
 In certain applications of chemistry and biochemistry solutions of constant pH is required. Such solution
are called buffer solution.
 A solution whose pH is not altered to any great extent by the addition of small quantities of either an
acid (H+ ions) or a base (OH– ions) is called buffer solution.
 Buffer solutions are also called solutions of reverse acidity or alkalinity.
 Characteristics of buffer solutions
(a) It must have constant pH.
(b) Its pH should not be changed on long standing
(c) Its pH should not be changed on dilution.
(d) Its pH should not be changed to any great extent on addition of small quantity of acid or base.
 Buffer solutions can be classified as follows.
(A) Simple buffer (B) Mixed buffer
A. Simple buffer
(i) It is a solution of one compound (salts of WA + WB)
(ii) Buffer action of such solution can be explained as follows-
In the salt solution of CH3COONH4 equilibria will be,
(a) CH3COO+(aq.) + NH4+ (aq.)+ H2O l CH3COOH(aq.)+ NH4OH(aq.)
(Salt hydrolysis)
(b) NH4OH l NH4+ + OH– (weak base)

(c) CH3COOH l CH3COO–+H+(weak acid)
(d) H 2O+H 2 O l H3O+ + OH– (feebly ionised)
on addition of small amount of acid the [H+] in solution will increase and
CH3COO– + H+ l CH3COOH
(from acid) (very less ionised)
equilibria will shift in forward direction. Similarly on addition of small amount of base, the [OH–] in
solution will increase
NH4+ + OH– l NH4OH
(from base) (very less ionised)
equilibria will shift in forward direction. Hence one can conclude that there will be no change (almost)
in the pH of the solution.
(iii) Simple buffer solutions have very little significance since
1 1
pH = 7 + pKa – pKb
2 2
so solution of desired pH can not be prepared.
B. Mixed buffer
Mixed buffers are solutions of more than one compounds.They can be further classified as
(a) Acidic buffer (b) Basic buffer
1. Acidic buffer
(i) These are the mixture of a weak acid and its salt with strong base.
e.g.
(a) CH3COOH + CH3COONa
(b) Boric acid (H3BO3) + Borax (Na2 B4O7)
(ii) Buffer action of acidic buffer can be explained with following equilibria,
(a) CH3COOH  H+ + CH3COO–
(Feebly ionised.)
(b) CH3COONa  Na+ + CH3COO–
(completely ionised.)
(c) H2O  H + OH–
+
When a strong acid is added in the solution [H+] increases, which will combine with CH3COO– to
form feebly ionised CH3COOH, which is also suppressed by common ion effect,
CH3COO– + H+ (from acid) l CH3COOH (Weak Acid)
Again when strong base is added in the solution it will attack on unionised acid CH3COOH to form
feebly ionised H2O molecules
CH3COOH + OH– (from base) l CH3COO– + H2O
(iii) One can remember, buffer action of acidic buffer with the help of following figure -
(iv) pH calculation for acidic buffer
(a) CH3COOH l CH3COO– + H+ (Ka)
H O
(b) CH3COONa  2 CH3COO– (aq.) + Na+ (aq.)
CH3COOH is feebly ionised and its ionisation is also suppressed by presence of common ion
(CH3COO–).
So one can fairly assume [CH3COO–]=[salt] and [CH3COOH]=[Acid] taken initially in buffer
solution.
[H ][CH3 COO  ]
so Ka = [CH COOH]
3
Ka [CH3 COOH]
or [H+] = [CH COO  ]
3
log[H+]=logKa+log[CH3COOH]–log[CH3COO–]
–log[H+] = – logKa – log[CH3COOH] + log [CH3COO–]
[CH3 COO  ]
pH = pKa + log
[CH3 COOH]
[Conjugate base]
pH = pKa + log [ Acid]
[Salt]
or pH = pKa + log [ Acid]
Above equation is called Henderson's equation.
Note :
 If we increase the concentration of given salt in acidic buffer, pH will also increases.
 If we increase the concentration of acid in acidic buffer, pH will decreases.
 If conc. and volume are given for salt and acid then the pH is given by the following formula-
[N2 V2 ]
pH = pKa + log [N V ]
1 1
Where N2 V2 = conc. & volume of salt
N1V1 = conc. & volume of acid
 Mixture of weak acid and strong base solution can also act as an acidic buffer, if value of N1V1
of weak acid is greater than the value of N2 V2 of strong base.
2. Basic Buffer
(i) These are the mixture of a weak base and its salt with strong acid.
e.g.
(a) NH4OH + NH4Cl
+
(b) Glycine (NH2CH2COOH) + Glycine hydrochloride (Cl NH3CH2COOH)
(ii) Buffer action of basic buffer can be explained with the help of following equilibria
(a) NH4OH  NH4+ + OH– (Kb) (Feebly ionised)
(b) NH4Cl  NH4+ + Cl– (Completely ionised)
(c) H2O  H+ + OH– (Kw)
When a strong base is added in the solution [OH–] increases, which will combine with NH4+ to form
feebly ionised NH4OH, which is also suppressed by common ion effect.
NH4++OH–(From base) l NH4OH (Weak base)

Again when strong acid is added in the solution it will attack on unionised base NH4OH to form feebly
ionised H2O molecules.
NH4OH + H+ (From acid) l NH4+ + H2O
(iii) One can remember the buffer action of basic buffer with the help of following figure -
(iv) pH of such basic buffer can be calculated from Henderson - equation as follows.
(a) NH4OH  NH4+ + OH– (Kb)
(b) NH4Cl H2 O
 NH4+ (aq.) + Cl– (aq.)
NH4OH is feebly ionised and its ionisation is also suppressed by presence of common ion (NH4+).
So one can fairly assume [NH4+] = [Salt] and [NH4OH] = [Base] taken initially in buffer
solution.
[OH ] [NH4 ]
so Kb = [NH4 OH]
K b [NH4 OH]
or [OH–] = [NH4 ]
K b Base
=
Salt 
Salt 
or pOH = pKb + log
Base
or pH = 14 – pOH
3. Buffer Capacity
(i) The property of a buffer solution to resist alteration in its pH value is known as buffer capacity.
(ii) Buffer capacity is number of moles of acid or base added in one litre of solution so as to change the
pH by unity, i.e.
Number of moles of acid or base added 1litre solution
Buffer capacity () = Change in pH
(iii) Higher the buffer capacity, better will be the buffer solution
(iv) For maximum buffer capacity of a given buffer concentration of salt should be equal to the concentration
acid/base
(v) A buffer solution work in a buffer range from pH = pKa ± 1
[Salt ]
(vi) A buffer solution work between O.1 < < 10
[Acid / Base]
Illustration
1. What will be the pH of the buffer solution containing 0.15 moles of NH4OH and 0.25 moles of NH4Cl.
Kb for NH4OH is 1.8 x 10–5.
(A) 9.08 (B) 10.03 (C) 9.05 (D) 9.03
Ans. D
Sol. Since it is a basic buffer so,
pOH = pKb+log[Salt]/[Base]
pOH = – log Kb+log[Salt/Base]
= –log(1.8x10–5)+log(0.25/ 0.15)
= 4.74 + 0.22 = 4.96
or pOH = 4.97
pH = 14–pOH
= 14 – 4.97 = 9.03
2. Calculate the pH of a buffer prepared by mixing 300 cc of 0.3 M NH3 and 500 cc of 0.5 M NH4Cl.
Kb for NH3 = 1.8 x 10–5–
(A) 8.11 (B) 9.81 (C) 8.82 (D) None of these
Ans. C
Sol. Total volume of the buffer solution
= 300 cc + 500 cc = 800 cc
Number of milli moles of NH3=300 × 0.3=90
Molarity of NH3 (Base) in the buffer = 90/800 M
Number of milli moles of NH4Cl = 500 × 0.5= 250.0
Molarity of [salt] in the buffer = 250/800 M
Henderson's equation for basic buffer is:
[Salt]
pOH = – log Kb + log
[Base]
250 / 800
= – log 1.8 × 10–5 + log
90 / 800
= 4.74 + log 250/90
= 4.74 + 0.44
= 5.18
pH = 14 – pOH = 14– 5.18 = 8.82
3. Calculate the pH of a buffer solution prepared by dissolving 10.6 g of Na2CO3 in 500 ml of an
aqueous solution containing 80 ml of 1M HCl. (Ka for HCO3– = 6 × 10–11)
(A) 8.6 (B) 9.6 (C) 11.6 (D) 12.6
Ans. B
Sol. Na2CO3 + HCl  NaCl + NaHCO3
10.6
Meq. before ×1000 80 × 1 0 0
106
Reaction = 100 80 0 0
Meq. After 20 0 80 80
Reaction
The solution Na2CO3 and HCO3– and thus acts as buffer
2
[CO 3 ] 20
pH = – log Ka + log [HCO  ] = – log 6 × 10–11 + log = 9.6
3 80
4. The concentration of H+ ion in a 0.2 M solution of HCOOH is 6.4 × 10–3 mole L–1 . To this solution
HCOONa is added so as to adjust the concentration of HCOONa to one mole per litre. What will
be the pH of this solution? Ka for HCOOH is 2.4 × 10–4 and the degree of dissociation of HCOONa
is 0.75
(A) 3.19 (B) 4.19 (C) 5.19 (D) 6.19
Ans. B
Sol. Assuming that the addition of HCOONa suppresses the ionization of HCOOH, we can use the
expression
[Salt]
pH = pKa + log
[ Acid]
to compute pH of the solution, since salt is 75% dissociated we will get,
0.75
pH = –log(2.4 × 10–4) + log
0.2
= 3.62 + 0.57 = 4.19
5. Calculate the ratio of pH of a solution containing 1 mole of CH3COONa + 1 mole of HCl per
litre and of other solution containing 1 mole CH3COONa + 1 mole of acetic acid per litre.
(A) 1 : 1 (B) 2 : 1 (C) 1 : 2 (D) 2 : 3
Ans. C
Sol. Case I - pH when 1 mole CH3COONa and 1 mole HCl are present
CH3COONa+HClCH3COOH+NaCl
Before 1 1 0 0
reaction
After 0 0 1 1
reaction
[CH3COOH] = 1M
Ka
 [H+] C = C. = C .K a = Ka
C
 C = 1
1
 pH1 = – log Ka
2
Case II - pH when 1 mole CH3COONa and 1 mole of CH3COOH, a buffer solution
[Salt]
 pH2 = – log Ka + log = – log Ka  [Salt] = [Acid] = 1M
[Acid]
pH1 1
pH2 = 2 or pH1 : pH2 = 1 : 2

6. In which case pH will not change on dilution
(A) 0.01 M CH3COONa + 0.01 M CH3COOH buffer
(B) 0.01 M CH3COONH4
(C) 0.01 M NaH2PO4
(D) in all cases
Ans. (D)
Sol. Mixture of Sodium acetate and acetic acid is a buffer of pH value equal to pKa so its buffer
capacity is maximum and hence its pH will not change significantly while CH3COONH4 is a salt
of weak acid CH3COOH and weak base NH4OH whose magnitude of Ka and Kb are equal.
So its pH does not depend upon concentration . Further more, NaH2PO4 is, in fact, a single
solute buffer.
Exercise
1. Calculate pH of the buffer solution containing 0.15 moles of NH4OH and 0.25 moles of NH4Cl. Kb
for NH4OH is 1.98 x 10–5.
(A) 7.034 (B) 9.04 (C) 8.043 (D) None of these
Ans. B
2. What volume of 0.1 M HCOONa solution should be added to 50 ml of 0.05 M formic acid to
produce a buffer solution of pH = 4.0, pKa of formic acid = 3.7
(A) 50 ml (B) 40 ml (C) 30 ml (D) 60 ml
Ans. A
3. What amount of HCl will be required to prepare one litre of a buffer solution (containing NaCN and
HCN) of pH 10.4 using 0.01 mole of NaCN. Given Kion (HCN) = 4.1 × 10–10 –
(A) 8.55 × 10–3 mole (B) 8.65 × 10–3 mole
(C) 8.75 × 10–3 mole (D) 9.9 × 10–4 mole
Ans. D
4. 20 ml of 0.2 M NaOH is added to 50 ml, of 0.2 M CH3COOH to give 70ml, of the solution.
What is the pH of the solution ? The ionization constant of acetic acid is 2 × 10–5 –
(A) 4.522 (B) 5.568 (C) 6.522 (D) 7.568
Ans. A
SOLUBILITY (S)
At a constant temperature, the mass of a solute or electrolyte dissolved in the 100 gm of solvent in its
saturated solution is called solubility.
Or
Number of gm mole of a solute dissolved in one litre of water at constant temperature is called
solubility of that solute.
Solubility of a solute in moles / litre
Solubility of solute in gm / litre
= molecular weight of the solute
1. Solubility product (KSP) :

It is the product of the ionic concentration of the ions of binary solid electrolyte in saturated state at
constant temperature.
(a) Let solubility of a compound Ax By be s moles L–1 it means that if more than s moles are dissolved in
solvent (one litre) only s moles will be soluble, rest will be insoluble, following equilibrium is established,
AB l AB  A A+ + B–
Insoluble Unionised Ions
Solute (Saturated solution)
Note : In the solubility s moles L–1, moles of only unionised are counted moles of ions and
insoluble solute do not have anything to do.
(b) According to law of mass action -
[ A  ] [ B ]
K1 =
[AB]
or K1 [AB] = [A+] [B–] = KSP
KSP is called solubility product.
(c) At a certain temperature solubility product of a compound is constant, it means that ions are formed in the
manner that product of their concentration is always a constant. However, it becomes clear that if one of
ions (A+ or B–) is added from outside, it would tend to increase KSP because [A+] or [B–] has increased,
so that extra ions will react with other ions to convert into insoluble part and it precipitates.
(d) KSP increases with increase in temperature.
(e) In a saturated solution.
KSP = [A+] [B–]
(f) In an unsaturated solution of AB
KSP > [A+] [B–]
i.e. more solute can be dissolved.
(g) In a supersaturated solution
KSP < [A+] [B–]
i.e. precipitation will start to occur.
2. Relationship between Solubility and Solubility Product :

The equilibrium for a saturated solution of a salt Ax By may be expressed as,
Ax By l xAy+ + yBx–
Thus, solubility product KSP = [Ay+]x [Bx–]y
Let the solubility of the salt Ax By in water at a particular temperature be ‘s’ moles per litre then
Ax By l xAy+ + yBx–
xs ys
So, KSP = [xs]x [ys]y
KSP = xx . yy(s)x + y
S & Ksp Relations

(a) 1 : 1 types salts or AB type of salts :
eg. AgCl, AgI, BaSO4, PbSO4, etc.
AB l A+ + B–
let the solubility of AB is s moles per litre.
So, KSP = [A+] [B–] = s × s = s2
s = KSP
(b) 1 : 2 or 2 : 1 type of salts or AB2 or A2B type of salts :
eg. Ag2CrO4, PbI2, Ag2CO3, CaF2, CaCl2 etc.
(i) AB2 l A2+ + 2B–
s 2s
let the solubility of AB2 is ‘s’ moles per litre
So, KSP = [A2+][B–]2 = s × (2s)2 = 4s3
1/ 3
 K sp 
s 
 4 
(ii) A2B l 2A+ + B2–
let s the solubility of A2B
So, A2B l 2A+ + B2–
2s s
KSP = [A+]2 [B–2] = (2s)2 (s) = 4s3
1/ 3
 K sp 
s 
 4 
(c) 1 : 3 type of salts or salts of AB3 or A3B type of salt -
AB3 = Valency of A = 3 × Valency of B
eg. FeCl3, AlCl3, PCl3, Al(OH)3, Fe(OH)3 etc.
A3B = 3 × Valency of A = Valency of B
eg. Na3BO3, Na3PO4, H3PO4 etc.
(i) AB3 l A3+ + 3B–
let the solubility of A3B is ‘s’ mole / litre.
AB3 l A3+ + 3B–
s 3s
KSP = [A3+] [B–]3 = s × (3s)3 = 27s4
1/ 4
 K sp 
s 
 27 
(ii) A3B l 3A+ + B–3
let the solubility of A3B is ‘s’ moles/litre.
A3B l 3A+ + B–3
3s s
KSP = [A+]3 [B–3]
= (3s)3 × s = 27s4
1/ 4
 K sp 
s   
 27 
(d) 2 : 3 or A2B3 type of salts :

eg. Al2(SO4)3
A2B2 l 2A+ 3 + 3B– 2
let the solubility of salt A2B3 is ‘s’ -
So, A2B3 l 2A+3 + 3B–2
2s 3s
+3 2
KSP = [A ] [B ] –2 3
= (2s)2 × (3s)3 = 4s2 × 27 s3
1/ 5
 K sp 
KSP = 108 s5 s 
 108 
Illustration
1. The solubility of CaF2 in water at 20ºC is 15.6 mg per dm3 solution. What will be the solubility
product of CaF2 –
(A) 4.0 × 10–4 (B) 8.0 × 10–8 (C) 32.0 × 10–12 (D) None
Ans. C
15.6  10 3
Sol. Solubility in moles per dm3 = 78 g / mole = 2.0 × 10–4
 CaF2 l Ca+2 + 2F–

 [Ca+2] = 2.0 × 10–4
and [F–] = 2 × 2.0 × 10–4
Hence, solubility product KSP
= [Ca+2] [F–]2 = [2.0 × 10–4] [4.0 × 10–4]2 = 32 × 10–12
2. Given the solubility product of F3B2 is 2 × 10–30. What will be the solubility in moles/litre.
1/ 5 1/ 5
 2  10 30   2  10 28 
(A) (1.85 × 10–32)1/5 (B)   (C)   (D) All
 108   5400 
Ans. B
Sol. KSP of A3B2 = 2 × 10–30.
A3B2 l 3A+2 + 2B–3
Assume s is the solubility of A3B2
then KSP = (3s)3 (2s)2 = 108 s5
K F2  10 I 30
1/ 5
s = 5 SP s = G 108 J

108 H K
Exercise
1. How many milligrams of AgBr will dissolve in water to give litres of aqueous solution. Given KSP for AgBr
(Mol. wt. 188) = 5.0 × 10–13 M2–
(A) 7.071 × 10–7 moles per litre (B) 70.71 × 10–7 moles per litre
–7
(C) 707.1 × 10 moles per litre (D) None of these
Ans. A
1. Effect of Common ion on Solubility :

As we saw that for a saturated solution product of concentration of ions should not exceed a constant
called solubility product. Now suppose, extra common ions are added to increase concentration of
ions it will tend to increase the value of Ksp , but it can not increase so ions will react to form molecule
and get precipitated e.g. let solubility of AB in water be s moles L–1. It is dissolved in solution CB
having a common ion B– let concentration of CB be C.
AB l A+ + B–
s s s
2 +
KSP = s = [A ] [B ]– -----(1)
2
(Product should not exceed s otherwise precipitation will start) Now. Let solubility of AB in CB be S1.
CB l C+ + B–
C C C
AB l A + B– +
s1 s1 s1
+
[A ] = s1
[B–] = s1 + C
KSP = (s1) (s1 + C)
If s1 <<< C
KSP = s1C = s2, from equation (1)
s2
or s1 =
C
So, solubility gets reduced.
Illustration
1. A salt M2 X3 dissolves in water such that its solubility is x g. mole/litre. Its KSP is –
(A) x5 (B) 6x2 (C) 108 x5 (D) 6x5
Ans. C
Sol. Solubility of M2X3 = x gm mole/litre
M2 X3 l 2M+3 + 3X–2
 [M+3] = 2x, [X–2] = 3x
Solubility product KSP = (2x)2.(3x)3=108 x5
2. Solubility product of AgCl is 2.8 × 10–10 at 25ºC. Calculate solubility of the salt in 0.1 M AgNO3 solution :
(A) 2.8 × 10–9 mole/litre (B) 2.8 × 10–10 mole/litre
(C) 3.2 × 10–9 mole/litre (D) 3.2 × 10–12 mole/litre
Ans. A
Sol. In 0.1 M AgNO3
AgNO3 l Ag + + NO3–, AgCl l Ag+ + Cl¯
KSP = [Ag+] [Cl¯]
Now [Ag+] can be taken as [AgNO3]
while [Cl¯] is the solubility of AgCl
KSP 2.8  1010
 Cl = =  Solubility of AgCl = 2.8×10–9 mole/litre
[Ag  ] 01.
3. 0.10 mol sample of AgNO3 is dissolved in one litre of 1.00 M NH3. If 0.010 mol of NaCl is added to
this solution will AgCl (s) Precipitate?
Sol. Ksp(AgCl) = 1.8 x 10-10, K f[Ag(NH3)2]+ =1.6x107
Ag+ + 2NH3 [Ag(NH3)2+]

0.10 M 1.00
x (1-0.20)M
= 0.80 M 0.10M
It is assumed than all Ag+ ion has been complexed and only its part x is left
Ag( NH 3 ) 2 010
.
. x107 
 16
Kf=
Ag 
NH 3
2
b g
x 0.80
2
 x = 9.8 x 10-9M = [Ag+] undissolved
[Cl-]=1.0 x 10-2 M
 [Ag+][Cl-]=9.8 x 10-9 x 1.0 x 10-2=9.8 x 10-11 < 1.8 x 10-10(Ksp(AgCl))
Hence AgCl(s) will not precipitate.
4. What is the minimum concentration of NH3 required to prevent AgCl(s) from precipitating from 1.00
litre of a solution containing 0.10 mol of AgNO3 and 0.010 mol NaCl ?
Ksp(AgCl) = 1.8 x 10-10
Kf [Ag(NH3)2] + = 1.6 x107
Sol. In order to prevent precipitation of AgCl
[Ag+][Cl¯]  K sp
b g
 [ Ag  ] 0.01  18
. x1010 , As [Cl¯] =0.01 M
 [Ag+]  1.8 x 10-8M
The maximum concentration of free uncomplexed Ag+ permitted in the solution is 1.8 x 10-8. That is
almost all Ag+ (0.10M) must be complexed
[Ag+]aq + 2NH3 [Ag(NH3)2+]
[NH3]= ?, [Ag+] = 1.8 × 10-8 M.
+
[Ag(NH3)2] = 0.10 M

Ag ( NH 3 ) 2 0.10
Kf =  1.6 × 107 =

[ Ag ] NH 3
2
 
1.8 10 8 NH3 
2
 [NH3]2 = 0.3472  [NH3]= 0.589 M
The concentration calculated above is that of free uncomplexed NH3 . [NH3] required by
0.1 M Ag+ in the formation of [Ag(NH3)]+ = 0.2 M
Hence [NH3]total = 0.2 + 0.589 = 0.789 M
Exercise
1. The solubility product of chalk is 9.3 × 10–8. Calculate its solubility in gram per litre –
(A) 0.3040 gram/litre (B) 0.0304 gram/litre (C) 2.0304 gram/litre (D) 4.0304 gram/litre
Ans. B
2. Given Ag+ (NH3)2 Ag++2NH3, Kc = 6.2 x 10-8 and Ksp (AgCl)= 1.8 x 10-10 at 298 K. Calculate the
concentration of complex in 1.0 M aqueous ammonia.
Ans. [Ag(NH3+)2]= 0.539.
3. Applications of KSP :
A. In purification of common salt : In a saturated solution of NaCl & impurities, by passing HCl gas
through it, increase the Cl– ion concentration which shifts the equilibrium NaCl Na+ + Cl– to left
& causes the precipitation of NaCl.
B. In preparation of NaHCO3 by solvay method : Precipitation of NaHCO3 from its saturated

solution is done by addition of NH4HCO3, HCO3– as common ion.
C. Predicting precipitation in Ionic reactions : Precipitation in an ionic reactions could be predicted

by comparing KSP to the ionic concentration product of ions.
D. Salting out action of Soap : When NaCl is added to saturated solution of soap (RCOONa)

concentration of Na+ increases & causes to precipitation of soap, it is due to [Na+] [RCOO–] > KSP.
E. In qualitative analysis : Selective precipitation of salt in salt analysis due to suppression of common

ion.
THEORY OF INDICATORS
An indicator is a substance which is used to determine the end point in a titration. In acid-base
titrations, organic substances (weak acids or weak bases) are generally used as indicators. They
change their colour within a certain pH range. The colour change and the pH range of some common
indicators are tabulated below:
Indicator pH range Colour change
Methyl orange 3.2-4.5 Pink to yellow

Methyl red 4.4-6.5 Red to yellow
Litmus 5.5-7.5 Red to blue
Phenol red 6.8-8.4 Yellow to red
Phenolphthalein 8.3-10.5 Colourless to pink
Theory of acid-base indicators: Two theories have been proposed to explain the change of
colour of acid-base indicators with change in pH.
1. Ostwald's Theory
(a) The colour change is due to ionisation of the acid-base indicator. The unionised form has different
colour than the ionised form.
(b) The ionisation of the indicator is largely affected in acids and bases as it is either a weak acid or
a weak base. In case, the indicator is a weak acid, its ionisation is very much low in acids due
to common H+ ions while it is fairly ionised in alkalies. Similarly if the indicator is a weak base,
its ionisation is large in acids and low in alkalies due to common OH¯ ions.
Let us derive Handerson equation for an indicator
HIn + H2 O  H+3O + In¯
'Acid form' 'Base form'
Conjugate acid-base pair

Kln = [ln][H+3O]/[HIn]; KIn = Ionization constant for indicator
[H+3O] = KIn * [HIn]/ln¯
pH = -log10 [H+3O] = -log10[KIn] - log10[HIn]/[In-]
pH = pKIn + log10[In-]/[HIn] (Handerson equation for indicator)
At equivalence point
[In¯] = [HIn] and pH = pKIn
Working principle of phenothalene & methyl orange indicators :

1. Phenolphthalein : It can be represented as HPh. It ionises in solution to a small extent as:
HPh  H+ + Ph¯
Colourless Pink
K = [H+] [Ph-] / [HpH]
The undissociated molecules of phenolphthalein are colourless while Ph¯ ions are pink in
colour. In presence of an acid the ionisation of HPh is practically negligible as the equilibrium
shifts to left hand side due to high concentration of H+ ions. Thus, the solution would remain
colourless. On addition of alkali, hydrogen ions are removed by OH¯ ions in the form of water
molecules and the equilibrium shifts to right hand side. Thus, the concentration of Ph¯ ions
increases in solution and they impart pink colour to the solution.
2. Methyl orange : It is a very weak base and can be represented as MeOH. It is ionized in solution

to give Me+ and OH¯ ions.
MeOH  Me+ + OH¯
Yellow Red
K = [Me+ ][OH¯]/[MeOH]
In presence of an acid, OH¯ ions are removed in the form of water molecules and the above
equilibrium shifts to right hand side. Thus, sufficient Me+ ions are produced which impart red
colour to the solution. On addition of alkali, the concentration of OH" ions increases in the
solution and the equilibrium shifts to left hand side, i.e., the ionisation of MeOH is practically
negligible. Thus, the solution acquires the colour of unionised methyl orange molecules, i.e.,
yellow.
This theory also explains the reason why phenolphthalein is not a suitable indicator for titrating a
weak base against strong acid. The OH¯ ions furnished by a weak base are not sufficient to shift
the equilibrium towards right hand side considerably, i.e., pH is not reached to 8.3. Thus, the solution
does not attain pink colour. Similarly, it can be explained why methyl orange is not a suitable indicator
for the titration of weak acid with strong base.
2. Quinonoid theory:
(a) The acid-base indicators exist in two tautomeric forms having different structures. Two forms are
in equilibrium.
Phenolphthalein has benzoid form in acidic medium and thus, it is colourless while it has quinonoid
form in alkaline medium which has pink colour.
Methyl orange has quinonoid form in acidic solution and benzenoid form in alkaline solution. The
color of benzenoid form is yellow while that of quinonoid form is red.
CH – CH CH = CH
– C C – = C C =
CH = CH CH = CH
(b) The two forms have different colors. The color change in due to the inter conversation of one
tautomeric form into other.
(c) One form mainly exists in acidic medium and the other in alkaline medium.
Thus, during titration the medium changes from acidic to alkaline or vice-versa. The change in pH
converts one tautomeric form into other and thus, the colour change occurs.
OH
OH¯
O H
+ C
O OH OH
C COO¯
O
Benzenoid form Quinonoid form
Phenolphthalein indicator
CH3
O3S NH N N
CH3
Quinonoid form – Acidic solution (red)
OH¯
H+
CH3
¯O3S N N N
CH3
Benzenoid form – Basic solution (Yellow)
Methyl orange indicator
Selection of suitable indicator

In order to choose a suitable indicator, it is necessary to understand the pH changes in different
types of titrations. The change in pH in the vicinity of the equivalence point is most important for
this purpose.
The curve obtained by plotting pH as ordinate against the volume of alkali added as abscissa is
known as neutralisation or titration curve.
Types of Neutralisation reaction

(i) Strong acid vs. strong base:
pH curve of strong acid (say HCI) and strong base (say NaOH) is vertical over almost the pH
range 4-10. So the indicators phenophthalein (pH range 8.3 to 10.5), methyl red (pH range
4.4-6.5) and methyl orange (pH range 3.2-4.5) are suitable for such a titration.
(ii) Weak acid vs. weak base:
pH curve of weak acid (say CH3COOH of oxalic acid) and strong base (say NaOH) is vertical
over the approximate pH range 7 to 11. So phenolphthalein is the suitable indicator for such a
titration.
(iii) Strong acid vs. weak base:

pH curve of strong acid (say HCl or H2SO4 or HNO3) with a weak base (say NH4OH) is vertical
over the pH range of 4 to 7. So the indicators methyl red and methyl orange are suitable for such
a titration.
(iv) Weak acid vs. Strong base :

pH curve of weak acid (say CH3COOH) with a strong base (say NaOH) is vertical over the pH
range 7 to 10. So phenopthalene is suitable indicator for such titration
Illustration
1. The pH at which an acid indicator with Ka = 1 × 10-5 changes colours when indicator concentration
is 1 × 10-5 M is
(A) 4 (B) 5 (C) 6 (D) 3
Ans. B
Sol. For acid indicator Hln
Hln H+ + ln-
Cololu(A) Colour (B)
[H ][ln ]
K ln  when [ln ] = [Hln ] indicator changes colour .
[Hln ]
 Kln  [H ]  1 x 10 5  pH = 5
Exercise
1. If an acidic indicator Hln lonises as Hln H+ + ln- .To which maximum pH value its solution
has distinct colour characteristic of Hln .
(A) pKln- 1 (B) pK ln  1 (C) pKln (D) 7
Ans. B
SOLVED EXAMPLES
Q.1 For an aqueous solution to be neutral it must have
(A) pH = 7 (B) [H+] = [OH-] (C) [H+] = K w (D) [H+] < [OH-]
Ans. B
Sol. For neutral solution [H+] always must be equal to [OH-]
Q.2 If an aqueous solution at 25oC has twice as many OH- as pure water its pOH will be
(A) 6.699 (B) 7.307 (C) 7 (D) 6.98
Ans. A
Sol. [OH ]  2 x10 7
pOH = 14 - pH or -log [OH-]
Q.3 The pH of a solution prepared by mixing 50.0 mL of 0.02 M NaOH and 50 mL of
0.04 M CH3COOH is (Ka = 1.8  10–5).
(A) 4.74 (B) 5.74 (C) 3.74 (D) 7.45
Ans. A
Sol. 50 mL of 0.02 M NaOH contains 1 milli moles of OH–
50 mL of 0.04 M CH3COOH contains 2 millimoles of H+
The combination of the two solutions will give 1 milli mole of salt, and 1 milli mole of acid will be left
behind. By using Henderson equation
Salt  0.1 milli mole per 100 mL of soln.
pH = pKa + log  or pH = pK + log
Acid  a 0.1 mill mole per 100 mL of soln.
Or pH = – log Ka = – log (1.8  10–5) = 4.74
Q.4 The pH of a solution containing 0.10 M H3BO3 and 0.18 M Na H2 BO3 is
(K1 H3BO3 = 7.3  10–10)
(A) 7.5 (B) 12.0 (C) 9.39 (D) 10.43
Ans. C
Sol. The dissociation of H3BO3 is
H3BO3 + H2O  H2BO3– + H3O+
 H 2 BO3   H 3O    0.18  .x
K1 =   7.3  1010
 H3BO3   0.10 
Or x = [H3O+] = 4.1  10–10 or pH = – log x = – log (4.1  10–10)
= 9.39
Q.5 What molar concentration of ammonia will provide a hydroxyl ion concentration of
1.5  10–3 ? (Kb = 1.8  10–5)
(A) 0.125 M (B) 0.12 M (C) 0.13 M (D) 0.14 M
Ans. C
Sol. The reaction is NH3 + H2O NH4+ + OH–
 NH 4    OH   1.5  103 1.5  103 

Kb = 1.8  10–5 =   1.8  105
 NH3   NH3 
Equilibrium conc. of ammonia [NH3] = 0.125 M
And, total [NH3] = 1.5  10–3 + 0.125 = 0.13 M
Q.6 A solution of a monoprotic weak acid has acidity constant equal to Ka. The value of minimum concentration
C in terms of Ka such that the concentration of undissociated acid can be equated to C within a limit of
error of 10% is
(A) C = 10 Ka (B) C =0.9 Ka (C) C = 0.1 Ka (D) C = 90 Ka
Ans. D
 H 3O   A  
Sol. The reaction is HA + H2O H3O+ + A
A– and Ka =
 HA 
Let C be the minimum initial concentration and x the degree of dissociation. Then
x2
Ka  .
Cx
Normally, we make the approximation that C – x ~ C within an error of 10%.
Therefore, C–x = 0.90 C or x = C–0.90 C = 0.10 C
2
x2  0.10C  0.01C2 C
Ka = =   or C = 90 Ka
Cx 0.90C 0.90C 90
Q.7 If the degree of ionization of water be 1.8 x 10-9 at 298 K. Its ionization constant will be
(A) 1.8 x 10-16 (B) 1 x 10-14 (C) 1 x 10-16 (D) 1.67 x 10-14
Ans. A
K 1014
Sol. Ka   . x 1016
 18
[H2 O] .
555
Q.8 The hydrolysis constant for ZnCl2 will be
2 2
K Kw Kw K b
(A) K h  Kb (B) K h  K (C) K h  2 (D) K h  K 2
b Kb w
Where kb is effective dissociation constant of base Zn++
Ans. B
Sol. Zn++ + 2H2O Zn(OH)2 + 2H+
[Zn(OH)2 ][H ]2
K h  .... (1)
[Zn ]
Zn(OH)2 Zn++ + 2OH-
[ Zn ][OH ]2 K 2w
K b  , K   [H ][OH ]   kh
[ Zn(OH)2 ] Kb
Q.9 The solubility product of Hg2 I2 is 1.2  10–28. The concentrations of cation and anion in a saturated
solution of Hg2 I2 in water is
(A) Hg22+ – 3.1  10–10 M and I– – 6.2  10–10 M
(B) Hg22+ – 6.2  10–10 M and I– – 12.4  10–10 M
(C) Hg22+ – 3.1  10–14 M and I– – 6.2  10–14 M
(D) Hg22+ – 3.6  10–12 M and I– – 1.8  10–12 M
Ans. A
Sol. Hg2 I2 Hg22+ + 2I– Ksp = [Hg22+].[I–]2 = 1.2  10–28
Let Hg22+ be x, then I– = 2x
1
1.2 1028  3
1.2  10–28 = x. [2x]2 = 4x3 or x =  
 4 
Or x = 3.1  10–10 M = [Hg22+]
2x = 6.2  10–10 M = [I–]
Q.10 Mg(OH)2 has a solubility product equal to 1.2  10–11. A solution contains 0.10 moles of magnesium
ions per litre. The maximum pH of the solution from which Mg(OH)2 will not precipitate is
(A) 4.96 (B) 9.04 (C) 12.13 (D) 6.94
Ans. B
Sol. Mg (OH)2 Mg2+ + 2OH– Ksp = 1.2  10–11
[OH–] higher than that contained in a saturated solution will cause precipitation. Therefore, the solution
must be at the point of attaining equilibrium and the concentration of ions in solution must be no greater
than those required to satisfy the solubility product constant. In this solution, [Mg2+] = 0.10 M and
[Mg2+] [OH–]2 = 1.2  10–11
1.2  1011
[OH–]2 =  1.2  1010 or [OH–] = 1.1  10–5 or pOH = 4.96
0.10
Or pH = 9.04
Q.11 Solubility of AgCl in water , 0.01 M CaCl2, 0.01 M NaCl and 0.05 M AgNO3 are S1 ,S2, S3 andS4
respectively then.
(A) S1 > S2 > S3 > S4 (B) S1 > S3 > S2 > S4 (C) S1 > S2 = S3 > S4 (D) S1 > S3 >S4 < S2
Ans. B
Sol. AgCl Ag + Cl -
In CaCl2
CaCl2 Ca+2 + 2Cl-

0.01 0.01 2 x 0.01
In NaCl
NaCl Na+ + Cl-

0.01 0.01 0.01
In A gNO3
AgNO3 Ag+ + NO3-
0.05 0.05 0.05
common ion effect is maximum in AgNO3
So, S1 > S3 > S2 > S4
Q.12 Calculate the pH of 0.01 N formic acid solution. The dissociation constant of the acid is 1.77  10–4.
Sol. HCOOH HCOO– + H+
C – C C C
and Ka = C2 or 1.77  10–4 = 0.01  2
1.77  104
or 2 =  1.77  102
0.01
Or  = 0.1245  10–2
Or [H+] = C. = 1.245  10–3 and pH = – log (1.245  10–3)
Or pH = –(0.015 – 3.00) = – (– 2.905)
= 2.9
Q.13 What will be the pH of a solution formed by mixing 40 mL of 0.10 M HCl with 10 mL of 0.45 M
NaOH?
0.1
Sol. 40 mL of 0.1 M HCl =  40  0.004 moles of HCl
1000
0.45
Similarly, 10 mL of 0.45 M NaOH =  10  0.0045 moles of NaOH
1000
Thus, NaOH left unneutralised = 0.0005 moles in a volume of 50 mL
1000  0.0005
Concentration of NaOH =  0.01 = 10–2 M
50
Therefore, [OH–] = 10–2 M or [H+] = 10–12 M or pH = 12.0
Q.14 A solution of HCl contains 0.1920 g of an acid in 0.5 litre of a solution. The degree of dissociation is
95%. The pH of the solution is ?
0.1920
Sol. Concentration C of HCl solution =  0.010 M
36.5  0.5
The degree of dissociation is 95% i.e., = 0.95
Therefore, [H+] = 0.010  0.95 = 0.0095
pH = –log[H+] = – log (0.0095) = –  3.9777     2.02   2.0
Q.15 A solution of acetic acid is 1.0% ionised. Determine the molar concentration of acid
(Ka = 1.8  10–5) and also the [H+].
Sol. CH3COOH CH3COO– + H+ where ‘C’ is the concn. of the acid and  is the

C–C C C degree of dissociation.
Ka = 1.8  10–5 = C2
 1.8  10–5 = C. (0.01)2 or C = 1.8  10–5  104 = 1.8  10–1 M
[H ] = C or [H+] = 1.8  10–1  0.01 = 0.18  0.01 = 0.0018 M or 1.8  10–3 M
+
Q.16 A reaction CaF2 Ca2+ + 2F– is at equilibrium. If the concentration of Ca2+ is increased four times,

what will be the change in F– concentration as compared to the initial concentration of F–?
Ca 2  F 2
Sol. The dissociation constant K of the reaction = . When the concentration of Ca2+ increases
 CaF2 
and becomes four times, the concentration of F– must decrease by the same value. This is necessary in
order to maintain K as constant. Since the F– concentration is raised to the power 2 in the expression,
the concentration of fluoride ion must decrease by 1/2.
Q.17 An acid solution of pH = 6 is diluted 1000 times, the pH of the final solution is
Sol. pH = 6 means [H+] = 10–6 M. After dilution, the hydrogen ion concentration becomes
10–9 M. Under such conditions, the hydrogen ions obtained from water cannot be neglected.
 Total [H+] = 10–9 + 10–7 (approx.)
= 10–7 (10–2 + 1)
= 10–7 (1.01)
[The contribution of H+ from water will not be exactly 10–7 but still we can make an approximation in an
objective problem and take it as 10–7]
pH = – log [H+] = – 1.01  10–7
= 7 – 0.0043 = 6.9957
Q.18 Calculate the pH of an aqueous solution of 1.0 M ammonium formate assuming complete dissociation

(pKa of formic acid = 3.8 and pKb of ammonia= 4.8)
Sol. HCOONH4 + H2O HCOOH + NH4OH
The pH of the salt of (weak acid and weak base) is given by
1 1
pH = [ pK   pK a  pK b ]  pH  14  38
.  4.8 = 6.5
2 2
Q.19 When 0.100 moles of NH3 are dissolved in sufficient water to make 1.00 L of solution, the solution is
found to have a hydroxide ion concentration of 1.33  10–3 M.
(a) What is the pH of this solution?
(b) What will be the pH of the solution when 0.100 mole of NaOH is added to it? Assume no change in
volume.
(c) Calculate Kb for ammonia.
(d) How does NaOH added to the solution affect the dissociation of ammonia?
1.00 1014
Sol. (a) [OH–] = 1.33  10–3 M  [H+] = 3
 7.52 1012 and pH = 11.12
1.33 10
(b)When 0.1 mole of NaOH is added, it will completely ionise to give 0.1 mole of
OH–. Hydroxyl ions obtained from NH3 are negligible in comparison to those obtained from NaOH.
Therefore [OH–] = 10–1 M or [H+] = 10–13 M or pH = 13
2
 NH 4 +   OH –  1.33 103 
(c) Kb =  NH4+ + OH– = 1.79  10–5
 NH3   0.100  0.00133 NH3 + H2O
(d) In the presence of NaOH, the ionisation of ammonia is suppressed.
Q.20 The pKb of NH4OH is 4.75. An aqueous solution of NH4OH is titrated with HCl. The pH of the solution
at a point when half of NH4OH is neutralised is
Sol. When half of NH4OH is neutralised
[NH4OH] = [NH4Cl]. By using the Henderson equation,
Salt 
pOH = pKb + log  or pOH = 4.75
Base 
pH = 14 – 4.75 = 9.25
Q.21 Calculate the pH at the equivalent point of the titration between 0.1 M CH3COOH (25 ml) with 0.05

M NaOH. Ka (CH3COOH)= 1.8 x 10-5.
Sol. We have already seen that even though when CH3COOH is titrated with NaOH the reaction does not
go to completion but instead reaches equilibrium. We can assume that the reaction is complete and then
salt gets hydrolysed because, this assumption will help us to do the problem easily and it does not effect
our answer.
K w Ka
 [H+]=
C
First of all we would calculate the concentration of the salt, CH3COONa. For reaching
equivalence point,
N1V1=N2V2
 0.1 x 25 = 0.05xV2
 V2 = 50 ml
Therefore [CH3COONa]= 0.1x25  0.1
75 3
1014 x18. x105 = 2.32 x 10-5  pH = -log 2.32 x 10-5 = 8.63

 [H+]=
01. /3
Q.22 Should Mg(OH)2 precipitate from a solution that is 0.01M MgCl2 if the solution is also made 0.10 M
in NH3. [K sp (Mg(OH)2) =1.8x10-11, Kb(NH4OH)= 1.8 x 10-5]
Sol. [OH-] in 0.10 M NH4 OH= K b C , (Ostwald’s dilution law)
= 18. x105 x0.010  134. x103 M  [ Mg 2  ]  0.01M
Ionic product = [Mg2+][OH-]2= (0.01)x (1.34x10-3)2 = 1.8 xx10-8 > Ksp
Ionic product is greater than Ksp of Mg(OH)2 hence precipitation should occur.
Q.23 The solubility of Pb (OH)2 in water is 6.7 x 10-6 M. Calculate the solubility of Pb(OH)2 in buffer solution
of pH = 8.
Sol. KspPb(OH)2 = 4S3 = 4 x (6.7x10-6)3
= 1.203 x 10-15
The p of buffer solution = 8, pOH = 6
 [OH-]=10-6
for left solubility of Pb (OH)2
[Pb2+][OH-]2= Ksp
 (s) (2s+10-6)2=1.203 x 10-15
. x1015
s
1203
10 12 c
2s  106  106 h
. x103 mol / lt
 s  1203
Q.24 Given the solubility product of Pb3 (PO4)2 is 1.5 x 10-32. Determine the solubility in gms/litre
Sol. Solubility product of pb3 (PO4)2= 1.5 x 10-32
Pb3(PO4)2 3Pb2+ + 2PO43-
If x is the solubility of Pb3 (PO4)2
Then Ksp = (3x)3(2x)2=108x5
F15. x10 IJ
1
32
K sp 5
G
108 H 108 K
x = 5
x = 1.692 x 10-7 moles/lit
Moleculer mass of Pb3 (PO4)2 = 811
x = 1.692 x 10-7 x 811 g/lit = 1.37 x 10-4 g/lit
Solubility product is
Ksp (SrC2O4)= [Sr2+][C2O42-]=(5.4x 10-4)2- = 2.92 x 10-7
Q.25 Calculate the pH at which an acid indicator with Ka = 1 x 10-5 changes colour when indicator concentra-
tion is 1 x 10-3 M. Also report the pH at which coloured ions is 80% present.
Sol. For indicator dissociation equilibrium
HIn H+ + In-
Colour A Colour B
H In
K ln 
HI n
The mid point of the colour change of an indicator HIn is the point at which [In-]= [HIn], KIn = [H+]
=1 x 10-5 1
 pH = 5
Thus at pH = 5 the indicator will change its colour
H In H  x80 / 100
K ln d  5
 1x10 
HI n 20 / 100
 [H+]= 0.25 x 10-5  H = 5.6020.
EXERCISE-1 (Exercise for JEE Mains)
[SINGLE CORRECT CHOICE TYPE]
Q.1 The conjugate acid of NH 2 is

(A*) NH3 (B) NH2OH (C) NH 4 (D) N2H4
[2020713307]
Sol. Conjugate of NH2– is NH3.
Q.2 Out of the following, amphiprotic species are
I HPO32– II OH– III H2PO4– IV HCO3–
(A) I, III, IV (B) I and III (C*) III and IV (D) All
[2020713058]
Sol. H2PO4– & HCO3– are amphoteric species.
Q.3 pH of an aqeous solution of NaCl at 85°C should be [2020713109]

(A) 7 (B) > 7 (C*) < 7 (D) 0
Sol. PH of NaCl at 85ºC should be < 7
Q.4 1 cc of 0.1 N HCl is added to 99 cc solution of NaCl. The pH of the resulting solution will be
(A) 7 (B*) 3 (C) 4 (D) 1
[2020712819]
0.1
Sol. [H+] = = 10–3
100
pH = 3
M M
Q.5 10 ml of H2SO4 is mixed with 40 ml of H SO . The pH of the resulting solution is
200 200 2 4
(A) 1 (B*) 2 (C) 2.3 (D) none of these
[2020712870]
Sol. +
Same concentration of [H ] for both solution, so pH will remain same and is equal to 2.
Q.6 If pKb for fluoride ion at 25° C is 10.83, the ionisation constant of hydrofluoric acid in water at this
temperature is :
(A) 1.74 × 105 (B) 3.52 × 103 (C*) 6.75 × 104 (D) 5.38 × 102
[2020712921]
Sol. kb = 10 –10.83
1014
ka = 10.83 = 10–3.17 = 6.75 × 10–4
10
Q.7 The pH of an aqueous solution of 1.0 M solution of a weak monoprotic acid which is 1% ionised is
(A) 1 (B*) 2 (C) 3 (D) 11 [2020712972]
1
Sol. [H+] = 1 × M , pH = 2
100
Q.8 If K1 & K2 be first and second ionisation constant of H3PO4 and K1 >> K2 which is incorrect.
(A) [H+] = [ H 2 PO4 ] (B) [H+] = K1[ H 3PO 4 ]
(C) K2 = [HPO4  ] (D*) [H+] = 3[PO34 ]
[2020713023]
Sol. H3PO4 H+ + H2PO4– k =

H PO H 
2 4
 
1 H 3PO 4 
C – x x + y x – y
–
H2PO4 H + + HPO42– k2 = [HPO42–]
y << x
[H+] = K1H 3PO 4 
[H+] = [H2PO4–]
Q.9 A solution with pH 2.0 is more acidic than the one with pH 6.0 by a factor of:
(A) 3 (B) 4 (C) 3000 (D*) 10000
[2020713074]
Sol. PH = 2 +
[H ]1 = 10 –2
PH = 6 [H+]2 = 10–6
H 

1 102
= = 10000
H 

2 10 6
Q.10 The first and second dissociation constants of an acid H2A are 1.0 × 10–5 and 5.0 × 10–10 respectively.
The overall dissociation constant of the acid will be :
(A) 5.0 ×10–5 (B) 5.0 ×1015 (C*) 5.0 ×10–15 (D) 0.2 ×105
[2020713125]
Sol. H2A +
H + HA – k1 = 1 × 10 –5
HA– H+ + A2– k2 = 5 × 10–10

H2A 2H+ + A
A2– k = k1 . k2
= 5 × 10–15
Q.11 An aqueous solution contains 0.01 M RNH2 (Kb = 2 ×10–6) & 10–4 M NaOH.
The concentration of OH¯ is nearly :
(A) 2.414 ×10–4 (B) 10–4 M (C) 1.414 × 10–4 (D*) 2 × 10–4
[2020712829]
Sol. RNH2 + H2O +
RNH3 + OH –
0.01 – x x (10–4 + x)


x 104  x  –6
0.01  x  = 2 × 10
x = 9.93 × 10–5
[OH ] = (10–4 + x) = 1.993 × 10–4
–
 2 × 10–4
Q.12 The degree of hydrolysis of a salt of weak acid and weak base in it’s 0.1 M solution is found to be 50%.
If the molarity of the solution is 0.2 M, the percentage hydrolysis of the salt should be
(A) 100% (B*) 50% (C) 25% (D) 10%
[2020712880]
Sol. % hydoysis for the given case comes out to be 50 % on solving the equation.
Q.13 What is the percentage hydrolysis of NaCN in N/80 solution when the dissociation constant for HCN is
1.3 × 10–9 and Kw = 1.0 × 10–14
(A*) 2.48 (B) 5.26 (C) 8.2 (D) 9.6
[2020712931]
Sol. CN – + H2O HCN + OH–
1 h h
(1 – h)
80 80 80
2
h 
 
 80  10 14
1 =
1  h  1.3 10 9
80
kh 10 5  80 8
= = × 10–4 < 10–3
C 1.3 1.3
so h << 1
h2 8 10  4
=
1 h 1.3
h = 2.48 %
Q.14 The compound whose 0.1 M solution is basic is
(A) Ammonium acetate (B) Ammonium chloride(C) Ammonium sulphate(D*) Sodium acetate
[2020712963]
Sol. Sodium Acetate hydrolysis will form basic solution.
Q.15 The  pH of the neutralisation point of 0.1 N ammonium hydroxide with 0.1 N HCl is
(A) 1 (B*) 6 (C) 7 (D) 9
[2020713014]
Sol. Due to hydrolysis, pH decreases and nearly equal to 6.
Q.16 The pKa of a weak acid, HA, is 4.80. The pKb of a weak base, BOH, is 4.78. The pH of an aqueous
solution of the corresponding salt, BA, will be :
(A) 8.58 (B) 4.79 (C*) 7.01 (D) 9.22
[2020713065]
1
Sol. pH = 7 + (Pka – Pkb)
2
1
= 7 + (Pka – Pkb)
2
= 7.01
Q.17 The range of most suitable indicator which should be used for titration of X– Na+ (0.1 M, 10 ml ) with
0.1 M HCl should be (Given: k b ( X  ) =10–6)
(A) 2–3 (B*) 3–5 (C) 6–8 (D) 8–10
[2020713116]
Sol. NaX + HCl  HX + NaCl
1014 1
[H+] = k a .C = 
106 20
pH = 4.651
so 3 – 5 range is most suitable
Q.18 If 40 ml of 0.2 M KOH is added to 160 ml of 0.1 M HCOOH [Ka = 2×10–4], the pOH of the resulting
solution is
(A) 3.4 (B) 3.7 (C) 7 (D*) 10.3
[2020712835]
Sol. 8 m moles of KOH + 16 m moles of H COOH
8 m mole of HCOO– + 8 m mole of HCOOH
salt
pH = pKa + log
aicd
4 = – log 2 = 3.7
pOH =10.3
Q.19 1 M NaCl and 1M HCl are present in an aqueous solution. The solution is
(A*) not a buffer solution and with pH < 7 (B) not a buffer solution with pH > 7
(C) a buffer solution with pH < 7 (D) a buffer solution with pH > 7
[2020712886]
Sol. Not a buffer solution and with pH < 7
Q.20 The pKa of a weak acid (HA) is 4.5. The pOH of an aqueous buffered solution of HA in which 50% of
the acid is ionized is :
(A) 4.5 (B) 2.5 (C*) 9.5 (D) 7.0
[2020712937]
salt 
Sol. pH = pKa + log
acid 
pH = 4.5 ( [salt] = [acid] )
pOH = 14 – 4.5 = 9.5
Q.21 The solubility of A2X3 is y mol dm–3. Its solubility product is
(A) 6 y2 (B) 64 y4 (C) 36 y5 (D*) 108 y5
[2020712988]
Sol. A2 X3 2A3– + 3X2–
KSP = (2S)2 (3S)3 = 108 y5
Q.22 If Ksp for HgSO4 is 6.4 ×10–5, then solubility of this substance in mole per m3 is
(A) 8 ×10–3 (B) 6.4 ×10–5 (C) 8 × 10–6 (D*) None of these
[2020713039]
Sol. HgSO4 2+
Hg + SO4 2–
KSP = [Hg2+] [SO42–]
= S2 = 6.4 × 10–5
S = 8 × 10–3 mole/lit. = 8 mole/m3
Q.23 The solubility of a sparingly soluble salt AB2 in water is 1.0 × 10–5 mol L–1. Its solubility product is:
(A) 10–15 (B) 10–10 (C*) 4 × 10–15 (D) 4 × 10–10
[2020713090]
Sol. AB2 A 2+
A + 2B –
Ksp = [A2+] [2B–]2 = 4S3 = 4 × (10–5)3 = 4 × 10–15
Q.24 Which of the following is most soluble in water?
(A) MnS (Ksp= 8×10–37) (B) ZnS (Ksp= 7×10–16)
(C) Bi2S3 (Ksp= 1×10–72) (D*) Ag3(PO4) (Ksp= 1.8×10–18)
[2020713141]
Sol. Solve for the solubility for each case with given KSP value.
Highest value cames for Ag3PO4.
Q.25 50 litre of a solution containing 10–5 mole of is mixed with 50 litre of a 2 × 10–7 M HBr solution. [Ag+]
in resultant solution is : [Given : Ksp (AgBr) = 5 × 10–13]
(A) 10–5 M (B) 10–6 M (C*) 10–7 M (D) None of these
[2020712851]
–5 –7
Sol. 50 lit10 mole AgCl + 50 lit of 2 × 10 M HBr
5
10
[Ag+] = = 10–7 M +10–7 M Br –
100
K =10–7 × 10–7 = 10–14 < KSP = 5 × 10–13
so no. precipitation
and [Ag+] = 10–7 M
Q.26 pH of a saturated solution of silver salt of monobasic acid HA is found to be 9.
Find the Ksp of sparingly soluble salt Ag A(s).
Given : Ka (HA) = 10–10
(A*) 1.1 × 10–11 (B) 1.1 × 10–10 (C) 10–12 (D) None of these
[2020712902]
Sol. A– + H2O HA + OH–
1014 10 5  HA  10 10

Kh = = 10–4 = = 
1010  
A A  
[A–] = 10–6
[Ag+] = [A–] + x
KSP = 10–6 × (10–6 × 10–5)
= 1.1 × 10–11
Q.27 Ksp of MX4 and solubility of MX4 is S mol/litre is related by :
(A*) S = [KSP /256]1/5 (B) S = [128 KSP ]1/4 (C) S = [256 KSP]1/5 (D) S = [KSP /128]1/4
[2020712953]
Sol. MX4 4+
M + 4X –
S 4S
KSP = [5] [45] = 256 S5
4
1/ 5
 K SP 
S =  
 256 
EXERCISE-2 (Exercise for JEE Advanced)
[PARAGRAPH TYPE]
Paragraph for question nos. 1 to 3
1.2 g of a monoprotic acid HA, is titrated with 0.222 M NaOH solution. The pH of the solution is
monitored with pH meter. A portion of the titration curve is shown in the diagram.
[2020712882]
Expanded titration
12.00 curve of
11.00 HA vs NaOH
10.00
pH 9.00
8.00
7.00
6.00
5.00
15 16 17 18 19 20
Volume of NaOH (mL)
Q.1 How many mL of NaOH is required to bring about the titration to its equivalence point ?
(A) 4.00 (B) 9.00 (C*) 19.00 (D) None of these
Sol. From the graph, i is obvious that volume of NaOH required for titration at equivalent point is 19 ml.
Q.2 What is the pH of solution at the equivalence point ?
(A) 3.50 (B) 7.00 (C*) 8.40 (D) 5.00
98
Sol. From graph at equivalent point, pH is around    8.5.
 2 
Q.3 What is the molar mass of HA ?
(A) 180 (B) 222 (C*) 282 (D) None of these
Sol. At equivalent point
moles of HA = moles of NaOH
1.2
-3
MHA = 0.222 × 19 × 10
MHA = 284.5
MHA  282
[REASONING TYPE]
These questions consists of two statements each, printed as Statement-I and Statement-II. While answering
these Questions you are required to choose any one of the following four responses.
(A) If both Statement-I & Statement-II are True & the Statement-II is a correct explanation of the Statement-
I.
(B) If both Statement-I & Statement-II are True but Statement-II i s not a correct expl anati on of the
Statement-I.
(C) If Statement-I is True but the Statement-II is False.
(D) If Statement-I is False but the Statement-II is True.
Q.4 Statement-I : pH of 10–7 M NaOH solution exists between 7 to 7.3 at 25°C.

Statement-II : Due to common ion effect ionization of water is reduced.
[Ans. A]
[2020712831]
Sol. Due to common ion effect from water dissociation
pH of 10–7 M NaOH solution lies between 7 & 7.3 at 25ºC.
Q.5 Statement-I: In general phenolphthalein is used as an indicator for the titration of weak acid (HA)
against strong base (NaOH).
Statement-II : At equivalent point solution is basic.
[Ans. B]
[2020712984]
Sol. Both statements are correct but the explanation is not correct.
Q.6 Statement-I : Moles of Sr2+ furnished by sparingly soluble substance Sr(OH)2 decreases due to
dilution in its saturated solution.
Statement-II : Solubility product constant of Sr(OH)2 is not affected by dilution.
[Ans. D]
[2020712933]
Sol. 2+
On dilution, Sr furnished by sparingly soluble salt remains constant becouse KSP is constant during
dilution.
[MULTIPLE CORRECT CHOICE TYPE]
Q.7 Which of the following statement(s) is/are correct ?
(A) the pH of 1.0 × 108 M solution of HCl is 8
(B*) the conjugate base of H2PO4 is HPO42
(C*) autoprotolysis constant of water increases with temperature
(D) when a solution of a weak monoprotic acid is titrated against a strong base, at halfneutralization
point pH = (1/2) pKa .
[2020713004]
Sol. (A) PH of 10–8 HCl < 10–8 due to [H+] due to [H+] contribution from water
(B) Conjugate base of H2PO4– is HPO42–.
(C) Autoprotolysis constant of water increases with temperature due to increase in dissoiation of water.
1
(D) pH  pKa at half neutralization point for weak monoprotic acid
2
Q.8 Select incorrect statement(s).
(A*) Phenolphthalein is suitable indicator for the titration of HCl (aq) with NH4OH (aq).
1000
(B) An acid-base indicator in a buffer solution of pH = pKIn + 1 is ionized to the extent of %.
11
(C*) In the titration of a monoacidic weak base with a strong acid, the pH at the equivalent point is
1
always calculated by pH = [pKw – pKb – log C]
2
(D) When Na3PO4 (aq) is titrated with HCl (aq), the pH of solution at second equivalent point is
1
calculated by [ pK a1  pK a 2 ]
2
[2020713055]
Sol. Statements A,C are true.
Q.9 Which of the following is true for alkaline aqueous solution?
pk w pk w
(A*) pH > (B*) pH > pOH (C*) pOH < (D) pH < pOH
2 2
[2020713106]
Sol. pH for alkalin solution > 7
[MATCH THE COLUMN]
Q.10 Match the column-
Column I Column II
(pH of resultant solution) (Exist between Colour transition
range of an indicator)
(A) 200 ml of H2SO4 solution (P) Phenol Red (6.8 to 8.4)
(specific gravity 1.225 containing
25% H2SO4 by weight) + 800 ml
of 0.525 M strong triacidic base (Q) Propyl red (4.6 to 6.4)
X (OH)3
(B) 50 ml of 0.1 M HCO3 + (R) Phenolphtalein (8.3 to 10.1)
50 ml of 0.8 M CO32
(H2CO3 : K a1 = 4 × 10–7 , K a 2 = 2 × 10–11 )
(C) 50 ml of 0.2 M HA (aq) (Ka = 10–5) (S) Malachite green (11.4 to 13)

+ 50 ml of 0.1 M HCl (aq)
+ 100 ml of 0.13 M NaOH (aq)
[2020713035]
[Ans. (A) S, (B) S, (C) Q ]
Sol.
 25 
 200 1.225  
 100 
(A) Moles of H+ = 2 ×  98 
 
 
= 1.250
moles of OH¯ = 0.8 ×0.525 × 3
= 1.260
remaining molarity of OH¯ = 0.01 M
pOH = 2
pH = 12
(B) [HCO3¯] = 0.050 M
[CO32–] = 0.40 M
Buffer solution :
pH = pK a (HCO3 ¯) + log 8
= 11 – log 2 + 3 log 2
= 11.6
(C) m moles of OH¯ = 13
m moles of H+ from HCl = 5
after reaction of NaOH & HCl, remaining OH¯ = 8 m moles
Calculate pH
EXERCISE-3 (Miscellaneous Exercise)
Q.1 Calculate the number of H+ present in one ml of solution whose pH is 13. [2020712127]

Ans. 6.022 ×107
Sol. [H+] = 10–13
1
n H  = 6.02 × 1023 × 10–13 × ml–1
1000
= 6.022 × 107 ml–1
Q.2 Calculate change in concentration of H+ ion in one litre of water, when temperature changes from 298 K
to 310 K. Given Kw(298) = 10–14 Kw (310) = 2.56 × 10–14. [2020712178]
Ans. 0.6 ×10 –7
Sol. [H+] = [H+]310 – [H+]298
= ( 2.56 – 1) × 10–7
= 0.6 × 10–7
Q.3 (i) Kw for H2O is 9.62 × 10–14 at 60°C. What is pH of water at 60°C.
(ii) What is the nature of solution at 60°C whose
(a) pH = 6.7 (b) pH = 6.35
[2020712229]
Ans. (i) 6.51 ; (ii) (a) Basic , (b) Acidic
Sol. (i) pH = – log [H+] = – log K w = 6.51
(ii) (a) Basic (b) Acidic
Q.4 The value of Kw at the physiological temperature (37°C) is 2.56 × 10–14. What is the pH at the neutral
point of water at this temperature? [2020712280]
Ans. 6.81
1
Sol. pH = (14 – log 2.56) = 6.796
2
Q.5 Calculate pH of following solutions : [2020712331]

(a) 0.1 M HCl
(b) 0.1 M CH3COOH (Ka= 1.8 × 10–5)
(c) 0.1 M NH4OH (Kb= 1.8 × 10–5)
(d) 10–8 M HCl
(e) 10–10 M NaOH
(f) 10–6 M CH3COOH (Ka= 1.8 × 10–5)
(g) 10–8 M CH3COOH (Ka= 1.8 × 10–5)
Ans. (a) +1, (b) 2.87, (c) 11.13 (d) 6.97, (e) 7, (f) 6.01, (g) 6.97
Sol. (a) [H+] = – log [H+] = 1
(b) C = 0.1 M , Ka = 1.8 × 10–5
[H+] from H2O can be neglected
Ka
 1.8  10  4  a < < c
C
[H+] = c = K a .C = 1.34 × 10–3
pH = 2.87
(c) NH4OH NH4+ + OH¯
0.1 0 0
0.1–x x x
x2
 K b = 1.8 × 10–5
0.1  x
x = 1.33 × 10–3
pOH = 2.873 pH = 11.13
(d) H2 O H+ + OH¯
(10–8 + x) x
–8
x (10 + x) = 10 –14
x = 9.51 × 10–8
pH = – log (10–8 + x) = 6.97
(e) H2O H+ + OH¯
x x + 10–10
x (10–10 + x) = 10–14
x » 10–7
pH = log x = 7.0
(f) Neglect [H+] from water
x2
= Ka = 1.8 × 10–5
cx
x = 9.45 × 10–7
pH = 6.01
(g) Very small value of CH3COOH, so it will completely dissociate into H+
H2O H+ + OH¯
10–8 + x x
–8
(10 + x)x = 10 –14
x = 9.5 × 10–8
pH = 6.97
Q.6 Calculate : [2020712382]

(a) Ka for a monobasic acid whose 0.10 M solution has pH of 4.50.
(b) Kb for a monoacidic base whose 0.10 M solution has a pH of 10.50.
Ans. (a) Ka = 10–8, (b) Kb = 10–6
Sol. (a) HA H+ + OH¯
0.1 0 0
0.1-x x x
= 3.16 × 10–5
Ka =
x2


3.16 105 2
 108
1 x 0.1
Ka = 10 –8
(b) [OH¯] = x = 3.16 × 10–14
Kb =
x2


3.16 10 4 2
 106
cx 0.1
Q.7 Calculate the ratio of degree of dissociation (21) when 1 M acetic acid solution is diluted to 100
times. [Given Ka=10–5 M] [2020712433]
Ans. 10
2 K a .C 2 C2
 
Sol.
1 K a .C1 C1 = 10
Q.8 Calculate the ratio of degree of dissociation of acetic acid and hydrocyanic acid (HCN) in 1 M their
respective solution of acids.[Given K a (CH COOH)  1.8 105 ; K a ( HCN)  6.2 1010 ]
3
[2020712490]
Ans. 170.4
1 K a1 .C1 K a1
 
Sol. 2 K a 2 .C 2 K a 2 (C1 = C2)
(1  CH3COOH, 2  HCN)
= 170.4
Q.9 pH of a dilute solution of HCl is 6.95. Calculate molarity of HCl solution. [2020712541]

Ans. 2.31×10–8 M
Sol. Let [H+]HCl = C
H  
H 2O x
H  
Total  c  x  1.12 10 7
H2O H+ + OH¯
c + x x
(c + x)x = 10–14
10 14
x = = 8.9 × 10-8
1.12 10 7
c = 1.12 × 10–7 – 8.9 × 10–8
= 2.31 × 10-8
Q.10 The solution of weak monoprotic acid which is 0.01 M has pH = 3. Calculate Ka of weak acid.
[2020712592]
Ans. 1.11 × 10 –4
Sol. NH4OH NH4+ + OH¯

0.01 – x x x
[H+] = 10–11, [OH¯] = 10-3
Ka =
x2 
10 3 
2
106 -4
.01  x  = .01  10 3  = 0.09 = 1.11 × 10
Q.11 Calculate pH of following solutions :
(a) 0.1 M H2SO4 (50 ml) + 0.4 M HCl 50 (ml)
(b) 0.1 M HA + 0.1 M HB [ Ka (HA) = 2 × 10–5 ; Ka (HB) = 4 × 10–5 ]
[2020712643]
Ans. (a) 0.522 , (b) 2.61
Sol. (a) 0.1 M H2SO4 (50 ml) + 0.4 M HCl (50 ml)
0.1 50  2   0.4  50 
[H+] =
100
= 0.3 M
pH = – log (0.3) = 0.522
(b) 0.1 M HA + 0.1 M HB
K a1 = 2 × 10-5 K a 2 = 4 × 10-5
K a1
 2 10 4 < 10-3
c1
Ka2
and  4 10 4 < 10-3
c2
so c1 >> x1 and c1 > > x2
[ H+ ] = K a1 c1  K a 2 c 2  2  10 6  4 10 6
pH = 2.61
Q.12 Calculate [H+] and [CHCl2COO] in a solution that is 0.01 M in HCl and 0.01 M in CHCl2COOH.
Take (Ka = 2.55 × 10–2).
[2020712694]
Ans. [H+] =1.612 × 102M, [CHCl2COO–] = 6.126 × 10–3M
Sol. HCl  H+ + Cl¯
(0.01 + x) 0.01
CHCl2 COOH CHCl2COO¯ + H+
0.01
(0.01 –x) x 0.01 + x
x 0.01  x 
Ka = 2.55 × 10-2 =
0.01  x 
on solving x = [CHCl2COO¯] = 6.126 ×10–3 M
and [H+] = (0.01 + x) = 1.612 × 10-2 M
Q.13 Calculate [H+], [CH3COO–] and [ C7 H5O2–] in a solution that is 0.02 M in acetic acid and 0.01M
in benzoic acid. Ka(acetic) = 1.8 × 10–5 , Ka (benzoic) = 6.4 × 10–5.
[2020712482]
Ans. [H+] = 103M, [CH3COO] = 3.6 × 104M, [C7H5O2] = 6.4 × 104M
Sol. CH3COOH CH3COO¯ + H+
0.02 – x x x + y
C 7H 6O 2 C 7 H5 O2 ¯ + H+
(0.01 - y) y y + x
x x  y 
 1.8  10 5 (Assuming x < < 0.02)
0.01
y x  y 
 6.4  10 5 (Assuming y < < 0.01)
0.02
[H+] = (x + y) = k a1 c1  k a 2 c 2 = 10-3
x 3.6

y 6.4
x = [CH3COO¯] = 3.6 × 10-4 M
y = [C7H5O2¯] = 6.4 × 10-4 M
Q.14 What are the concentration of H+, H2C2O4, HC2O 4 and C 2 O 24 in a 0.1 M solution of oxalic acid ?

[K1 = 10–2 M and K2 = 10–5 M ] [2020712533]
Ans. 0.027 M, 0.073 M, 0.027 M, 10–5 M
Sol. H 2C 2O 4 HC2O4¯ + H+
(0.1 – x) x – y x + y K1 = 10-2
K1
 10 1 > 10-3
c
HC2O4¯ C 2O 42- + H+
x-y y x + y K2 = 10-5
K1  K2 × 10-3 , So we can assume

x > > y
x2
K1 = 10-2 =
0.1  x
x = 0.027
[H+] = x + y = 0.027 M
y x  y 
K2 = = 10-5
xy
y = 10–5 = [C2O42]
[H2C2O4] = 0.1 – x = 0.073 M
[HC2O4¯] = 0.027 M
Q.15 What are the concentrations of H+, HSO 4 , SO 24 and H2SO4 in a 0.20 M solution of sulphuric acid ?
Given : H2SO4  H+ + HSO 4 ; strong

HSO 4 l H+ + SO 24  ; K2 = 10–2 M
[2020712584]
Ans. 0.2116 M, 0.1884 M, 0.0116 M, 0
Sol. H2SO4  H+ + HSO4¯
0.2 + x 0.2 – x
HSO4¯ H+ + SO42– K = 10–2
0.2 – x x + 0.2 x
x  0.2x
K =
0.2  x 
On solving
x = 1.16 × 10–2
[H+] = 0.2 + x = 0.2116 M
[HSO4¯] = 0.2 – x = 0.1885
[SO42–] = x = 0.0116
[H2SO4] = 0
Q.16 Calculate [H+], [H2PO4 ], [HPO42] and [PO43] in a 0.01M solution of H3PO4.
Take K1 = 103, K2 = 108 , K3 = 1013.
[2020712635]
+ 3 2 8 3
Ans. [H ] = [H2PO4 ] = 2.7 × 10 , [HPO4 ] = 10 , [PO4 ] = 3.7 × 10
      19
Sol. H3PO4 H+ + H2PO4

0.01–x (x + y + z) x-y K1 = 10-3
H2PO4 H+ + HPO42– K2 = 10–8
x-y x + y + z y-z
HPO4–2 H+ + PO43– K3 = 10–13

y – z x + y + z z
K1 > > K2 > > K3 , so x > > y > > z
x2
K1 = =10–3
0.01  x
x = 2.7 × 10-3
y = k2 = 10-8
xz
 k 3  10 13
y
z = 3.7 × 10-19
[H+] = [H2PO4¯] = x = 2.7 × 10–3
[HPO42–] = y = 10–8 M
[PO43–] = z = 3.7 × 10–19 M
Q.17 What is the OH concentration of a 0.08 M solution of CH3COONa. [Ka(CH3COOH)=1.8 × 105]
[2020712386]
Ans. [OH ] = 6.664 × 10
  6
Sol. CH3COO¯ + H2O CH3COOH + OH¯

0.08–x x x
Kw 10 14 x2
Kh =  =
K b 1.8 10 5 0.08  x
x = 6.6 × 10 -6
Q.18 Calculate the pH of a 2.0 M solution of NH4Cl. [Kb (NH3) = 1.8 × 105] [2020712737]

Ans. pH = 4.477
Kw 10 14
Sol. Kh = 
K b 1.8 10 5
Kh 109
  103
c 1.8  2
x2 10 9
Kh = 
2  x 1.8
x = 3.3 × 10-5
pH = – log x = 4.477
Q.19 0.25 M solution of pyridinium chloride C5H6N+Cl was found to have a pH of 2.699. What is Kb for
pyridine, C5H5N ? [2020712691]
Ans. Kb = 6.25 × 10  10
Sol. [H+] = x = 10-2.699
10 14 x2
Kh = =
Kb cx
taking x < < c and solving
Kb = 6.25 × 10–10
Q.20 Calculate the extent of hydrolysis & the pH of 0.02 M CH3COONH4.
[Kb (NH3)= 1.8 × 105, Ka(CH3COOH)=1.8 × 105] [2020712742]
Ans. 0.56%, pH = 7
Sol. CH3COO¯ + H2O CH3COOH + OH¯
0.02 (1 – h) 0.02h 0.02h
NH4+ + H2O NH4OH + H+
0.02 (1 – h) 0.02 h 0.02 h
2
 0.02h  Kw
Kh =   
 0.02 1  h   KaKb
h = 0.56 × 10-2
% hydrolysis = 0.56%
If Ka = Kb
pH = 7
Q.21 Calculate the percent hydrolysis in a 0.06 M solution of KCN. [Ka(HCN) = 6 × 1010]
[2020712793]
Ans. 1.667%
Sol. CN¯ + H2O HCN + OH¯
c(1–h) ch ch
c2h 2 kw
= k = 2.7 × 10-4 < 10–2
c1  h  a
assuming h < < 1
h = 2.77 104 = 0.0167

% hydrolysis = 1.667 %
Q.22 Calculate the percent hydrolysis in a 0.0100 M solution of KCN.(Ka= 6.2 ×10–10)
[2020712695]
Ans. 4.0%
10 14 1
Sol. Kh = 10 = × 10-4
6.2  10 6 .2
Kh
= 1.6 × 10-3
c
Assuming h < < 1
Kh
h2 =
c
h = 0.04
Percent hydrolysis = 4%
Q.23 Calculate the extent of hydrolysis of 0.005 M K2CrO4. [K2 = 3.1 × 107 for H2CrO4]
(It is essentially strong for first ionization). [2020712745]
Ans. 0.26%
Sol. H2Cr2O4  H+ + HCrO4¯ (Strong acid)
HCrO4¯ +
H + CrO4 2– Ka = 3.1 × 10-7
CrO42- + H2O HCrO4¯ + OH¯
10 14 10 7
Kh = =
3.1 107 3.1
K h 10 4
 < 10-3
c 15.5
h2 K
 h
1 h c
h = 2.6 × 10-3
Percent hydrolysis = 0.26 %
Q.24 Determine [OH–] of a 0.050 M solution of ammonia to which sufficient NH4Cl has been added to make
the total [ NH 4 ] equal to 0.100.[ K b ( NH3 ) =1.8 × 10–5] [2020712796]
Ans. [OH–] = 9.0 ×10–6
Sol. NH4OH NH4+ + OH¯ Kb = 1.8 × 10-5
0.05-x 0.1 x
0.1x
Kb = 1.8 × 10-5 =
0.05  x
x = [OH¯] = 9 × 10–6 M
Q.25 Calculate the pH of a solution prepared by mixing 50.0 mL of 0.200 M CH3COOH and 50.0 mL of
0.100 M NaOH.[ K a ( CH3COOH) =1.8 × 10–5] [2020712746]
Ans. 4.74
Salt 
pH = pKa + log
Sol.
Acid = 4.744
Q.26 A buffer of pH 9.26 is made by dissolving x moles of ammonium sulphate and 0.1 mole of ammonia into
100 mL solution. If pKb of ammonia is 4.74, calculate value of x. [2020712545]
Ans. 0.05 mol
Sol. x mole (NH4)2 SO4 + 0.1 mole of NH4OH
Salt 
pOH = pKb + log
Base
 2x 
14–pH = 4.74 + log  
 0.1 
x = 0.05 mole
Q.27 50 mL of 0.1 M NaOH is added to 75 mL of 0.1 M NH4Cl to make a basic buffer. If pKa of NH 4 is
9.26, calculate pH. [2020712746]
Ans. 9.56
Sol. 2.5 m mole of NH4+ + 5 m mole of NH4OH
Salt   2. 5 
pOH = pKb + log = 14–pKa + log  
Base  5 
pH = 14–pOH = 9.26 + 2.3 = 9.56
Q.28 For the acid indicator thymol blue, pH is 2.0 when half the indicator is in unionised form. Find the % of
indicator in unionised form in the solution with [H+] = 4 × 103 M. [2020712496]
Ans. [HIn] = 28.57%
Sol. HA H+ + A¯
pH = pKa = 2
H  A ¯ 

Ka = 10–2 =
HA
HA
% of unionised form =
HA  A × 100 = 28.57%
Q.29 Bromophenol blue is an acid indicator with a Ka value of 6 × 105 . What % of this indicator is in its basic
form at a pH of 5 ? [2020712491]
Ans. 85.71%
Sol. HA H+ + A¯
105  A ¯ 
Ka =
HA
6
 100  85.714%
7
Q.30 At what pH does an indicator change colour if the indicator is a weak acid with Kind = 4 × 104. For
which one(s) of the following neutralizations would the indicator be useful ? Explain.
(a) NaOH + CH3COOH (b) HCl + NH3 (c) HCl + NaOH
[2020712542]
Ans. (b), (c)
Sol. pKin = – log (4 × 10-4)
= 4 – 2 log 2
= 3.4
It would be useful for solution with pH 2.4 – 4.4.
So b and c are possible
Q.31 Calculate OH– concentration at the equivalent point when a solution of 0.1 M acetic acid is titrated with
a solution of 0.1 M NaOH. Ka for the acid = 1.9 × 10–5. [2020712468]
Ans. 5.12 ×10–6 M
Sol. CH3COOH (0.1 M) + NaOH (0.1M)
Salt hydrolysis
Kw
CH3COO¯ + H2O CH3COOH + OH ¯ Kh = K
a
c(1–h) ch ch

1014
Kh = < 10–3
1.9 105
[OH¯] = K h .C = 5.12 × 10–6
Q.32 Calculate the hydronium ion concentration and pH at the equivalence point in the reaction of 22.0 mL of

0.10M acetic acid, CH3COOH, with 22.0 mL of 0.10 M NaOH. [Ka = 1.8 × 10–5]
[2020712519]
Ans. 8.71
Sol. [CH3COO¯] = 0.05 M, Ka = 1.8 × 10–5
1014 1.8 10 5 10 14
[H+] = = 1.89 × 10-9
OH¯  = 0.05
pH = 8.7
Q.33 Calculate the hydronium ion concentration and the pH at the equivalence point in a titration of 50.0 mL
of 0.40 M NH3 with 0.40M HCl.[Kb = 1.8 × 10–5] [2020712672]
Ans. 4.98
Sol. NH4OH + HCl  NH4Cl
NH4+ + H2O  NH4OH + H+
Kw 10 14 10 9
Kh = K = =
b 1.8 105 1.8
[H+] = K h .c = 1.05 × 10–5
pH = 4.98
Q.34 A weak base (50.0mL) was titrated with 0.1 M HCl. The pH of the solution after the addition of
10.0 mL and 25.0 mL were found to be 9.84 and 9.24, respectively. Calculate Kb of the base and pH at
the equivalence point. [2020712723]
–5
Ans. Kb = 1.8 × 10 , 5.27
Salt 
Sol. pH = 14 – pOH = pK3 + log
Acid
 1 
14–9.84 = pKb + log   ...................(1)
 b 1 
 2.5 
14–9.24 = pKb + log   ...................(2)
 b  2.5 
from (1) & (2)
b = 5
Kb = 1.8 × 10 -5
Kw 10 14
Kh =
K b = 1.8 105
0.05  10 9
[H+] = K h .c = = 5.27 × 10-6
1.8
PH = 5.27
Q.35 A weak acid (50.0mL) was titrated with 0.1 M NaOH. The pH values when 10.0 mL and 25.0 mL of
base have been added are found to be 4.16 and 4.76, respectively. Calculate Ka of the acid and pH at
the equivalence point. [2020712774]
Ans. 8.73
Sol. 1 m mole of salt + (a – 1) m mole of acid pH = 4.16
2.5 m mole of salt + (a – 2.5) m mole of acid pH = 4.76
1
pH = pKa + log = 4.16 ................(1)
a 1
2.5
pH = pKa + log = 4.76 ................(2)
a  2 .5
a = 5
pKa = 4.76, Ka = 1.8 × 10-5
5m mole
at equivalent point, c = 100 ml
Kw
[OH¯] = c
Ka
pH = 8.73
Q.36 In the titration of a solution of a weak acid HX with NaOH, the pH is 5.8 after 10.0 mL of NaOH
solution has been added and 6.402 after 20.0 mL of NaOH has been added. What is the ionization
constant of HX?
[2020712474]
Ans. 6.1
x
Sol. pH = 5.8 = pKa + log .....................(1)
ax
 2x 
pH = 6.402 = pKa + log   ......................(2)
 a  2x 
a = 3x
pKa = 6.402 – log 2 = 6.1
Q.37 The solubility of PbSO4 in water is 0.038 g/L. Calculate the solubility product of PbSO4.
[2020712525]
Ans. 1.6 × 10–8
Sol. PbSO4 Pb2+ + SO42–
S S
2
 0.038 
Ksp = S2 =    1.6 × 10–8
 303 
Q.38 A solution of saturated CaF2 is found to contain 4.1 × 10–4 M fluoride ion. Calculate the Ksp of CaF2.
Neglect hydrolysis. [2020712576]
Ans. 3.4 × 10 –11
Sol. CaF2 2F¯ + Ca2+ 2S = 4.1 × 10–4 M

2S S
3
 4.1 10 4 
Ksp = (2S) (S) = 4 × 
2 
 2 
= 3.4 × 10 –11
Q.39 What is the solubility (in mol/L) of Fe(OH)3 in a solution of pH = 8.0 ? [Ksp for Fe(OH)3 = 1.0 × 10–36]
[2020712495]
Ans. 1.0 × 10–18 M
Sol. Fe (OH)3 Fe3+ + 3OH¯
S 3S
= 10-6 (pH = 8, [OH¯] = 10-6)
Ksp = S (10-6)3 = 1 × 10–36
S = 10–18 mol/lit
Q.40 Calculate the Simultaneous solubility of AgSCN and AgBr. Ksp (AgSCN) = 1.1 × 10–12,
Ksp(AgBr) = 5 × 10–13.
[2020712797]
Ans. 4 × 10–7mol/L AgBr, 9 × 10–7 mol/L AgSCN
Sol. AgSCN  Ag+ + SCN¯
x + y x
AgBr  Ag+ + Br¯
x + y y
x (x + y) = 1.1 × 10-12 .......................(1)
(x + y) y = 5 × 10-3 .......................(2)
x = 9 × 10-7 M
y = 4 × 10-7 M
Q.41 Calculate F– in a solution saturated with respect of both MgF2 and SrF2. Ksp(MgF2)= 9.5 × 10–9,
Ksp(SrF2) = 4 × 10–9. [2020712749]
– –3
Ans. [F ] = 3 × 10 M
Sol. Mg2+ + 2 F¯
x 2x + 2y
2+
Sr + 2F¯
y + 2x + 2y
x (2x + 2y)2 = 9.5 × 10–9 ...............(1)
y (2x + 2y)2 = 4 × 10–9 ................(2)
F¯ = 2x + 2y = 3 × 10–3
Q.42 Calculate the percent error in the [H3O+] concentration made by neglecting the ionization of water in a
10–6M NaOH solution. [2020712627]
Ans. error = 1%
Sol. Nelecting the ionization of water
1014
[H+] = –8
6 = 10 .
10
Now, Consider the ionization of water, for error calculation
 
H2O Hx + OH6
x 10
x (x + 10–6) = 10–14 = 0
on solving the quadratice equation
x = 0.99 × 10–8
10 8  0.01
% Error = 100 × = 1.01 %  1%
0.99 10 8
Q.43 A solution was made up to be 0.01 M in chloroacetic acid, ClCH2COOH and also 0.002 M in sodium
chloroacetate ClCH2COONa . What is [H+] in the solution ? Ka = 1.5 × 103. [2020712678]
Ans. [H+]=2.5×103
Ka 10 3  1.5
Sol. =  0.15 > 10–3
C 0.01
so, exact analysis is required
HA H+ + A A–
(0.01 – x) x (0.002 + x)
x 0.002  x 
–3
0.01  x  = 1.5 × 10
x2 + 0.0035 x – 1.5 × 10–5 = 0
x = 2.5 × 10–3 M
Q.44 Determine the [S2] in a saturated (0.1M) H2S solution to which enough HCl has been added to produce
a [H+] of 2 × 104 . K1 = 107 , K2 = 1014. [2020712729]
2
Ans. [S ] = 2.5 × 10
  15
Sol. H 2S H + HS

k1 = 10–7
0.1 x x  y 2104  x  y 

HS x  yH S2
 4 + y k2 =10–14
x  y   210 
2 × 10–4 >> x >> y, as k2 is very very small and HCl is also present in the solution.
 x + y + 2 × 10–4  2 × 10–4
y  2  10  4
k2 = = 10–14
x
x  2 10 4
K1 = 10-7 =
0.1
1 4
x = 10
2
y 1
= × 10–4
x 2
From (1) & (2) y = 2.5 × 10–15
Q.45 What is the pH of a 1.0 M solution of acetic acid ? To what volume must 1 litre of the solution be diluted
so that the pH of the resulting solution will be twice the original value. Given Ka = 1.8 × 10–5.
[2020712780]
4
Ans. V = 2.77 × 10 litre
Sol. [H+]1 = k a .C ( << 1)
= 1.8 10 5  1
pH1 = 2.372
pH2 = 2 pH1 = 4.744
[H+]2 = 1.8 × 10–5
[H+] contribution from water is neglected as [H+]2 > 10–6
CH 3COOH CH 3COO  + H
C x x x 1.8105
x2
= 1.8 × 10–5
Cx
C = 3.6 × 10–5
mole
=
Volume
1
V = = 2.77 × 104 lit
3.6 105
Q.46 It is desired to prepare 100 ml of a buffer of pH 5.00.Acetic, benzoic and formic acids and their salts are
available for use. Which acid should be used for maximum effectiveness against increase in pH? What
acid-salt ratio should be used ?pKa values of these acids are : acetic 4.74; benzoic 4.18 and
formic 3.68. [2020712486]
Ans. acetic acid, salt-acid molar ratio 1.8 :1
Sol. Pka should be closet to 5, so aceticacid should be used. (pka = 4.74)
Salt 
pH = pka + log
Acid
Salt 
5 = 4.74 +log
Acid
Salt  0.26
Acid = 10 = 1.8
Q.47 When a 40 mL of a 0.1 M weak base is titrated with 0.16M HCl, the pH of the solution at the end point
is 5.23. What will be the pH if 15 mL of 0.12 M NaOH is added to the resulting solution.
[2020712639]
Ans. 9.168
Sol. 40 ml of 0.1 M BOH
= 4 m mol of BOH
4 = 0.16 × V
V = 25 ml of HCl
Total volume = 40 + 25 = 65 ml
4
C = M
65
kw 10 14
kh = k =
b kb
B+ + H2O BOH + H+
k w .C 10 14  4
[H+] = =
kb 65k b
pH = – log [H+]
14
1 log 65 10   log k 
5.23 =  b
2   4 
 
pkb = 4.75
Now if 15 ml of 0.12 M NaOH is added
= 1.8 m mole of OH¯
nNaOH = 2.2 m moles
 2. 2 
pOH = pkb + log  
 1 .8 
= 4.75 + 0.087 = 4.83
pH = 9.16
Q.48 A buffer solution was prepared by dissolving 0.05 mol formic acid & 0.06 mol sodium formate in enough
water to make 1.0 L of solution. Ka for formic acid is 1.80 × 104.[pKa = 3.74]
(a) Calculate the pH of the solution .
(b) If this solution were diluted to 10 times its volume, what would be the pH ?
(c) If the solution in (b) were diluted to 10 times its volume,what would be the pH?
[2020712537]
Ans. (a) pH = 3.83 (b) pH = 3.85 , (c) pH = 3.99
Salt 
Sol. (a) pH = pKa + log
Acid
 0.06 
= 3.74 + log  
 0.05 
= 3.83
(b) HA = 5 × 10–3 M, [Salt] = 6 × 10–3 M
HA  A
Hx + 610
5103 x  3
x 

x 6 10 3  x  = 1.8 × 10 –4
5 10 3
 x
x = 1.4 × 10–4
pH = 3.85

(c) HA A + H 
C1  x C1  x x
C1 = 5 × 10–4 C2 = 6 × 10–4

x 6 10 4  x  = 1.8 × 10 –4
5 10 4
 x
x = 1.02 × 10–4
pH = 3.99
Q.49 How many moles of sodium hydroxide can be added to 1.00 L of a solution 0.1 M in NH3 & 0.1 M in
NH4Cl without changing the pOH by more than 1.00 unit ? Assume no change in volume. Kb(NH3) =
1.8 × 105. [2020712588]
Ans. 0.0818 moles

Sol. OH¯ + NH 4 NH 4OH
0.1 x 0.1 x
Salt 
pH = pKb = log
Acid
1
(k = >>1, so we can assume that added OH– will completely react with salt to from NH4OH)
kb
 0 .1  x 
3.74 = 4.74 + log  
 0 .1  x 
0.9
x = = 0.0818
11
Q.50 20 ml of a solution of 0.1 M CH3COOH solution is being titrated against 0.1 M NaOH solution. The pH
values after the addition of 1 ml & 19 ml of NaOH are (pH)1 & (pH)2, what is pH ?
[2020712690]
Ans. 2.558
Sol. 2 m mole of CH3COOH + 1.9 m mole of NaOH
 1.9 m mole of CH3COO Na + 0.1 m mole of CH3COOH
Vol = 39 ml
Cs = 0.048, Ca = 2.564 × 10–3
Cs > Ca
y0.048  y 
ka =

2.56  10 3  y 
for pH, we solve H.E. for appronimate case
 0.1 
pH1 = pKa + log  
 1.9 
 0.1 
 1.9 
 1.9   1.9 
pH = pH2 – pH1 = log   –   log 
 0.1   1.0 
= 2 log 19
= 2.55
Q.51 Equilibrium constant for the acid ionization of Fe3+ to Fe(OH)+2 and H+ is 6.5 ×10–3. What is the
max.pH, which could be used so that at least 95% of the total Fe3+ in a dilute solution exists as Fe3+.
[2020712741]
Ans. 0.908
2
Sol. Fe3 + H2O FeOH  + H  k = 6.5 × 10–3
10.5 0.05 x
0.95
0.05x
k = 6.5 × 10–3 =
0.95
0.95
x = × 6.5 × 10–3
0.05
pH = 0.908
Q.52 A solution of weak acid HA was titrated with base NaOH. The equivalence point was reached when
36.12 ml of 0.1 M NaOH has been added. Now 18.06 ml of 0.1 M HCl were added to titrated
solution, the pH was found to be 4.92. What will be the pH of the solution obtained by mixing 10 ml of
0.2 M NaOH and 10 ml of 0.2 M HA. [2020712792]
Ans. 8.96
Sol. 3.612 m mole of HA + 3.612 m mole o NaOH
3.6 m mole of A– + 1.8 m mole of H C
A + H+  HA
3.6121.806 1.806
1.806
salt 
Buffer with
acid  = 1
salt 
pH = pKa + log
acid 
= 4.92 + 0
= 4.92
2 m moles of HA + 2 m mole of NaOH
= 2 m moles of A–
kw 2
[OH–] = k h .C = 
k a 20
pOH = 5.04
pH = 8.06
Q.53 A weak base BOH was titrated against a strong acid . The pH at 1/4th equivalence point was 9.24.
Enough strong base was now added (6m.eq.) to completely convert the salt. The total volume was
50ml. Find the pH at this point. [2020712492]
Ans. 11.22
Sol. BOH + H+ B + H2O

3 1
n n
4 4
1
pOH = pKb + log
3
4.76 = pKb – log3
pKb = 5.2
B + OH   BOH
n n n
4 4 4
= 6 meq.
or n = 24 m eq. in 50 ml sol.
24
C = M
50
pKb = 5.2
[OH–] = k b .C
kw
[H+] = k .C
b
1 1 
pH = pKw –  pK b  log C 
2 2 
= 11.22
Q.54 An organic monoprotic acid [0.1M] is titrated against 0.1M NaOH. By how much does the pH change
between one fourth and three fourth stages of neutralization? If at one third stage of neutralization, the pH
is 4.45 what is the dissociation constant of the acid? Between what stages of neutralisation may the pH
change by 2 units? [2020712543]
1 10
Ans. 0.9542, pKa = 4.751, th & th stages of neutralisation
11 11
Sol. HA + OH¯  A¯ + H2O
0.1M 0.1 M
V ml
1 3 V
th of N.P.. V× 0.1  0.1 pH1
4 4 4
3 V 3V
th of N.P..  0 .1  0 .1 pH2
4 4 4
1 2V V
rd of N.P.. × 0.1 × 0.1 pH3
3 3 3
(NP = Neutralisation point)
1
pH1 = pKa + log
3
1
3
pH = 2 log3 = 0.9542
1
2
pKa = 4.751
Q.55 At 25°C, will a precipitate of Mg(OH)2 form in a 10–4 M solution of Mg(NO3)2 if pH of the solution is
adjusted to 9.0. Ksp [Mg(OH)2] = 10–11 M3. At what min value of pH will precipitation start.
[2020712652]
Ans. No, 10.5
Sol. [Mg2+] = 10–4 M, [OH] = 10–5 M
k = 10–4 × 10–10 = 10–14 10–11
(No precipitation)
for min. [OH–] = x
10–11 = 10–4 × x2
x = 10–7/2
1014
max [H+] =
107 / 2
 
min pH = – log 10 14  7 / 2  = 10.5
EXERCISE-4
SECTION-A
(IIT JEE Previous Year's Questions)
Q.1 What will be the resultant pH when 200 ml of an aqueous solution of HCl (pH = 2.0) is mixed with
300 ml of an aqueous solution of NaOH (pH = 12.0) ? [JEE '1998]
[2020712808]
Ans. pH = 11.3010
Sol. [H+] = 10–2 M , 200 ml  2 m moles (Acid)
[OH–] = 10–2 M , 300 ml  3 m moles (Base)
1 m mole
Resullant [OH–] = –3
200  300ml = 2 × 10 M
pOH = 2.7
pH = 11.3
Q.2 The solubility of Pb(OH)2 in water is 6.7 × 106M. Calculate the solubility of Pb(OH)2 in a buffer
solution of pH = 8. [JEE '1999]
[2020712859]
Ans. s = 1.203 × 10-3M
Sol. KSP = (6.7 × 10–6)3 × 4
pH = 8,
pOH = 6
[OH–] = 10–6
K sp
S = [Pb2+] = –3 M
OH2 = 1.2 × 10
Q.3 A buffer solution can be prepared from a mixture of [JEE 1999]

(A*) sodium acetate and acetic acid in water
(B*) sodium acetate and hydrochloric acid in water
(C*) ammonia and ammonium chloride in water
(D) ammonia and sodium hydroxide in water.
[2020712910]
Sol. Buffer solution can be prepared by option A, B, C (WA – WB, SA - WB, W.A. – S.B.)
Q.4 The pH of 0.1 M solution of the following salts increases in the order [JEE 1999]

(A) NaCl < NH4Cl < NaCN < HCl (B*) HCl < NH4Cl < NaCl < NaCN
(C) NaCN < NH4Cl < NaCl < HCl (D) HCl < NaCl < NaCN < NH4Cl
[2020712961]
Sol. NaCN > NaCl > NH4Cl > HCl
Q.5 An aqueous solution of 6.3 g oxalic acid dihydrate is made up to 250 mL. The volume of 0.1 N NaOH
required to completely neutralise 10 mL of this solution is [JEE 2001]
(A*) 40 mL (B) 20 mL (C) 10 mL (D) 4 mL
[2020713012]
Sol. M H 2C2O4 .2H 2O = 126
 6.3  10 0.1 V
  × =
 126  250 2
V = 40 ml
Q.6 For sparingly soluble salt ApBq, the relationship of its solubility product (Ls) with its solubility (S) is
(A*) Ls = Sp+q, pp. qq (B) Ls = Sp+q, pp. qp (C) Ls = Spq, pp. qq (D) Ls = Spq, (p.q)p+q
[JEE 2001]
[2020713063]
Sol. ApBq pAq+ + qBp–
ps qs
solubility product = (ps)p (qs)q
= pp qq . sp+q
Q.7 500 ml of 0.2 M aqueous solution of acetic acid is mixed with 500 mL of 0.2 M HCl at 25°C.
(a) Calculate the degree of dissociation of acetic acid in the resulting solution and pH of the solution.
(b) If 6 g of NaOH is added to the above solution, determine final pH. Assume there is no change in
volume on mixing. Ka of acetic acid is 1.75 × 10–5 M. [JEE 2002]
[2020713114]
Ans. (a) 0.0175% , (b) 4.757
Sol. (a) CH3COOH CH3COO– + H+
0.1 (1 – x) 0.1 x 0.1(1 + x)
0.12 1  x x
k = 1.75 × 10–5 =  x % = 1.75 × 10–2
0.11  x 
= 0.0175 %
ka
(1 + x  1 – x  1 , Because = 1.75 × 10–3 << 1)
c
6 3
(b) = moles of NaOH = 0.15 moles
40 20
+ 0.1 moles of HCl
+ 0.1 moles of CH3COOH
Resultant 0.1 mole NaCl + 0.5 moles of CH3COONa + 0.5 moles o CH3COOH
Salt 
PH = Pka + log
Acid
= 5 – log 1.75
= 4.757
Q.8 A solution which is 10 –3 M each in Mn2+, Fe2+, Zn2+ and Hg2+ is treated with 10–16M sulphide ion. If Ksp,
MnS, FeS, ZnS and HgS are 10–15, 10–23, 10–20 and 10–54 respectively, which one will precipitate first ?
(A) FeS (B) MnS (C*) HgS (D) ZnS [JEE 2003]
[2020712821]
Sol. Check the concentration of each ion for given 10–16 M S2–.
HgS has lowest solubility product, so it will precipitete first.
Q.9 Will the pH of water be same at 4°C and 25°C ? Explain. [JEE 2003]

[2020712872]
Ans. No it will be > 7
Sol. With increase in temperature water disociation increases and pH decreases.
Q.10 HX is a weak acid (Ka = 10–5). It forms a salt NaX (0.1 M) on reacting with caustic soda. The degree
of hydrolysis of NaX is
(A*) 0.01% (B) 0.0001% (C) 0.1% (D) 0.5% [JEE 2004]
[2020712923]
kw
Sol. h = = 10–4
k a .c
Percent hydrolysis = 10–2 = 0.01 %
Q.11 0.1 M of HA is titrated with 0.1 M NaOH, calculate the pH at end point. Given Ka(HA) = 5 × 10–6
and  << 1. [JEE 2004]
[2020712974]
Ans. pH = 9
0. 1  V
Sol. = 0.05 M NaA
2V
NaA + H2O NaOH + HA (Hydrolysis)
kw
[OH–] =  C = 10–5
ka
pH = 9
Q.12 CH3NH2 (0.1 mole, Kb = 5 × 10–4) is added to 0.08 moles of HCl and the solution is diluted to one litre,
resulting hydrogen ion concentration is
(A) 1.6 × 10–11 (B*) 8 × 10–11 (C) 5 × 10–5 (D) 2 × 10–2 [JEE 2005]
[2020713025]
Sol. CH3NH2 + HCl CH3NH3+ + Cl–
0.02 0.08
CH NH 
3 3

0.08
pOH = pKb + log CH NH  = 4 – log 5 + log = 3.9,
3 2 0.02
[H+] = 8 × 10–11
Q.13 The species present in solution when CO2 is dissolved in water :
(A*) CO2, H2CO3, HCO3– , CO32– (B) H2CO3, CO32– [JEE 2006]
(C) CO32– , HCO3– (D) CO2 , H2CO3 [2020712905]
Sol. CO2 + H2O H2CO3
H2CO3 H+ + HCO3–
HCO3– H+ + CO32–
Q.14 Solubility product constants (KSP) of salts of types MX, MX2 and M3X at temperature 'T' are
4.0 ×10–8, 3.2 ×10–14 and 2.7 ×10–15 , respectively. Solubilities (mol dm–3) of the salts at temperature
'T' are in the order :
(A) MX > MX2 > M3X (B) M3X > MX2 > MX [JEE 2008]
(C) MX2 > M3X > MX (D*) MX > M3X > MX2
[2020712854]
2 –8
Sol. MX : S = 4 × 10 , S = 2 × 10 –4
MX2 : 4 S3 = 3.2 × 10–14 , S = 2 × 10–5
MX3 = 27 S4 = 2.7 × 10–15 , S = 10–4
MX2 < M3X < MX
2 2
Q.15 2.5 mL of M weak monoacidic base (Kb = 1 × 10–12 at 25°C) is titrated with M HCl in water at
5 15
25°C. The concentration of H+ at equivalence point is [JEE 2008]
–14
(Kw = 1 × 10 at 25°C)
(A) 3.7 × 10–13 M (B) 3.2 × 10–7 M (C) 3.2 × 10–2 M (D*) 2.7 × 10–2 M
[2020712803]
Sol. BOH + HCl  BCl + H2O
2 2
2.5 × × V = 1 m mole
5 15
V = 7.5 ml
B– + H2O BOH + H+
kw
C – x x x k = k = 10–2
b
k
0.1 – x = 0.1 > 10–3
C
10–2 = Kh =
H  BOH = x
 2
B  
0.1  x
x = 2.7 × 10–2
Q.16 The dissociation constant of a substituted benzoic acid at 25°C is 1.0 × 10–4. The pH of a 0.01 M
solution of its sodium salt is [JEE 2009]
[2020713076]
Ans. 8
Sol. C6H5COO Na + H2O C6H5COOH + OH¯
Ka = 10–14
10 14
kh = = 10–10
ka
C = 0.01 M
kh
= 10–8 < < 10–3
C
kw kw 1014
[H+] = = k .c = 6 = 10–8

OH   h 10
pH = 8
Q.17 Aqueous solutions of HNO3, KOH, CH3COOH, and CH3COONa of identical concentrations are
provided. The pair(s) of solutions which form a buffer upon mixing is(are) [JEE 2010]
(A) HNO3 and CH3COOH (B) KOH and CH3COONa
(C*) HNO3 and CH3COONa (D*) CH3COOH and CH3COONa
[2020713127]
Sol. C & D will for buffer solution
(w.A. + w.B., w.A. + s.B., s.A. + w.B.)
Q.18 In 1 L saturated solution of AgCl [Ksp (AgCl) = 1.6 × 10–10], 0.1 mol of CuCl
[Ksp (CuCl) = 1.0 × 10–6] is added. The resultant concentration of Ag+ in the solution is 1.6 × 10–x. The
value of “x” is [JEE 2011]
[2020712956]
[Ans. 7]
Sol. AgCl Ag+ + Cl–
C1 C1 + C2
CuCl Cu+ + Cl–
C2 C1 + C2
C1 (C1 + C2) = 1.6 × 10–10
C2 (C1 + C2) = 10–6
C1 + C2 ~ 10–3
C1 = 1.6 ×10–7
x = 7
Q.19 The initial rate of hydrolysis of methyl acetate (1M) by a weak acid (HA, 1M) is 1/100th of that of a
strong acid (HX, 1M), at 25°C. The Ka of HA is
(A*) 1 × 10–4 (B) 1 × 10–5 (C) 1 × 10–6 (D) 1 × 10–3
[JEE Advance-2013]
[2020614484]
Ans. [A]
Sol. Rate = K [Ester] [H+]
For strong acid [H+]= 1M
For weak acid [H+]= K a .C
Rate1 [H  ]1 1

1
  
Rate2 [H ]2 1 / 100 K a 1
Ka = 10–4 M
Q.20 The Ksp of Ag2CrO4 is 1.1 × 10–12 at 298 K. the solubility (in mol/L) of Ag2CrO4 in a 0.1 M AgNO3
solution is :
(A) 1.1 × 10–11 (B) 1.1 × 10–10 (C) 1.1 × 10–12 (D) 1.1 × 10–9
[JEE Advance-2013]
[2020614433]
Ans. [B]
Sol. (2S + 0.1)2 × S = 1.1 × 10–12
neglecting S as compared to 0.1
S = 1.1 × 10–10
SECTION-B
(JEE Main Previous Year's Questions)
Q.1 The pKa of a weak acid, HA, is 4.80. The pKb of a weak base, BOH, is 4.78. The pH of an aqueous
solution of the corresponding salt, BA, will be - [AIEEE-2008]
(A) 4.79 (B*) 7.01 (C) 9.22 (D) 9.58
[2020614382]
Sol. For salt of weak acid and weak base
1 1 1
PH = 7 – PK b  PK a  = 7 – (4.78 – 4.80) = 7 – (–0.02) = 7.01
2 2 2
Q.2 Solid Ba(NO3) is gradually dissolved in a 1.0 × 10–4 M Na2CO3 solution. At what concentration of
Ba2+ will a precipitate begin to form ? (Ksp for Ba CO3 = 5.1 × 10–9) [AIEEE-2009]
(A*) 5.1 × 10 M–5 –8
(B) 8.1 × 10 M –7
(C) 8.1 × 10 M –5
(D) 4.1 × 10 M
[2020614331]
Sol. Ksp [BaCO3] = [Ba+2] [CO3–2]
5.1109
[Ba+2] = = 5.1 × 10–5
10 4
Q.3 The pH of a 0.1 molar solution of the acid HQ is 3. The value of the ionization constant, Ka of this acid
is : [AIEEE-2012]
(A*) 1 × 10–5 (B) 1 × 10–7 (C) 3 × 10–1 (D) 1 × 10–3
[2020614280]
Sol. + +
[H ] = C  and PH = 3, [H ] = 10 –3
103
 = = 10–2
0.1
 For weak acid Ka = C2 = 0.1 × (10–2)2 = 1.0 × 10–5
Q.4 How many litres of water must be added to 1 litre of an aqueous solution of HCl with a pH of 1 to create
an aqueous solution with pH of 2?
(A) 0.9 L (B) 2.0 L (C*) 9.0 L (D) 0.1 L
[JEE Main-2013]
[2020614229]
Sol. 10–1 × 1 = 10–2 × Vf
 Vf = 10 L
 Volume of water (Vf – Vi) = 9 L

Ionic Equilibrium Explained

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ACC- CH-IONIC EQUILIBRIUM 1

ARRHENIUS THEORY OF ELECTROLYTIC DISSOCIATION

(a) Nature of electrolyte : Some electrolyte , e.g., mineral acid such as H2SO4, HCl and HNO3, alkalis

(b) Nature of the solvent : A solvent which has a high dielectric constant weakens the attractive force

(c) Dilution : For some electrolytes, degree of dissociation increases with dilution as explained by Ostwald’s

(d) Temperature : Increase of temperature generally increases ionization.

(2) Weak electrolytes : These are not completely ionized when dissolved in a polar solvent and they

Conducting electrolytes N o n-c on d uc t in g e le ct r o ly t es

Strongly conducting (solutions of Strong Weakly conducting (solutions of

OSTWALD’S DILUTION LAW

3.5 104  3.5  104 2 12.25 108

Limitations of Ostwald's dilution law : It holds good only for weak electrolytes and fails completely

CONCEPT OF ACIDS AND BASES

(A) The Arrhenius concept

Mono basic acid Di basic acid Tri basic acid

Gives single H+ Gives two H+ Gives three H+

Mono acidic base Di acidic based Tri acidic basic

Gives single OH¯ Gives two OH¯ Gives three OH¯

Strength of acid or base :

(B) The Bronsted-Lowry theory (Protonic concept)

Conjugate acid–base pairs

Acid Base Conjugate Conjugate

HCl + H2 O H3O+ + Cl¯

. Acid Conjugate Base Conjugate acid

Behaviour of acids and bases in aqueous solution

(i) Acids in water : Water functions as a weak base and accepts a proton from the acid, thus

(C) Lewis Electronic theory

H F H F

(i) Protonic or protic solvent

COMMON ION EFFECT

Amphoteric (amphiprotic) Acid /Base nature :

Molar concentration / Molarity of water :

H2O H+ + OH¯ so, ionic product of water, kw = [H+] [OH¯] = 10–14 at 25º (exp.)

Degree of dissociation of water :

Absolute dissociation constant of water :

Acidity and pH scale :

 pH = – log a (where a H  , is the activity of H+ ions)

pH CALCULATION OF DIFFERENT TYPES OF SOLUTIONS

(a) Strong acid solution :

(b) Strong base solution :

(c) pH of mixture of two strong acids : If V1 volume of a strong acid solution of normality N1 is mixed

(e) pH of mixture of a strong acid and a strong base :

If N 1V 1 > N2V 2 If N 2V 2 > N 1V 1

Solution will Solution will

(f) pH of a weak acid (monoprotic) solution :

1. Calculate pH of (a) 10–1 M CH3COOH (b) 10–3 M CH3COOH

1. Calculate pH of (a) 10–4 M CH3COOH (b) 10–6 M CH3COOH

(g) pH of a mixture of weak acid (monoprotic) and a strong acid solution :

(h) pH of a mixture of two weak acid (both monoprotic) solution :

RELATIVE STRENGTH OF WEAK ACIDS AND BASES

Strength of acid (I) Ka

Strength of acid (II) = Ka

1.1 Simples salts :

1.2 Double salts :

1.3 Complex salts :

(iii) CoSO4 + 6NH3  Co(NH3)6SO4

1.4 Mixed salts :

Ex. CaOCl2, NaKSO4, NaNH4HPO4 etc.

1. Salt of a Weak Acid and Strong Base

CH3COO- + H2O CH3COOH + OH-

2. Salt of a Weak Base and a Strong Acid

NH4 + + H2O NH4OH + H+

3. Salt of a Weak Acid and Weak Base