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IONIC EQUILIBRIA
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A CIDS AND BASES

1. The Arrhenius Concept :

Arrhenius classified a substance into an acid or a base in terms of the characteristics ions of water
which it produces in aqueous solution. Thus a n a cid is a substance which ionizes in wa ter
to produce H + (a q) or the hydronium ion; a ba se is a substance which produces OH –(a q)

HCl(aq)  H+(aq) + Clă(aq)

NaOH(aq)  Na+(aq) + OHă(aq)

Ć The strength of an acid is defined in terms of concentration of H+(aq) that is present in the
aqueous solution of a given concentration of the acid. Likewise, the strength of a base
depends upon the relative concentration of OHă(aq) in an aqueous solution of the base.
Ć A neutralisation reaction involves the combination of H+ and OHă ions to form water.

H+(aq) + OHă(aq)  H2O

Ć By Arthenius concept NH3 should not be a base. It was proposed that in aqueous solution NH3

forms the compound NH4OH, which then dissociate as a weak base into NH4 and OHă ions

H+(aq) + OHă(aq)  H2O

 ă


NH4 OH(aq)  NH4 (aq)  OH( aq)

2. Bronsted–Lowry concept of Acids and Bases

According to this concept, any hydrogen containing species ( a molecule, a cation or an anion),
which is capable of donating one or more protons to any other substance, is called an acid.
Any species (molecule, cations or anions) which is capable of accepting one or more protons from
an acid, is called a base.
Thus, according to the Bronsted-Lowry concept, an acid is proton-donor, and a base is proton-
acceptor.
The reaction of an acid with a base involves transfer of a proton from the acid to the base. So,
an acid and a base should be present simultaneously in any system. The extent of an acid-base
reaction is governed not only by the proton-donating ability of the acid, but also by the proton-
accepting tendency of the base. Acids and bases classified on the basis of this concept are termed
as Bronsted acids and bases.


  
HCl( aq)  H2 O(l )  H3O( aq)  Cl( aq)

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In this reaction, HCl donates its one proton to become Clă, and H2O accepts one proton to become
H3O+. Thus, HCl is Bronsted acid and H2O is a Bronsted base. For the reverse reaction., H3O+
is able to transfer its proton to Clă. So, H3O+ is a Bronsted acid and Clă is a Bronsted base.
Every acid must form a base on donating its proton, and every base must form an acid on
accepting a proton. The base that is produced when an acid donates its proton is called the
conjugate base of the acid. The acid that is produced when a base accepts a proton is called
the conjugate acid of the base. The above reaction can be written as

HCl + H2O 


 H3O  Cl ă
acid1 base 2 acid2 base1

In this Clă is the conjugate base of the acid HCl and H2O is the conjugate base of the acid H3O+.
The conjugate acid differs from conjugate base by one proton. A pair of an acid and a base which
differ from one another by a proton constitute a conjugate acid base pair. Thus,


Conjugate acid-base pair 

HCl + H2O 

 H3O  Cl ă
acid1 base 2 acid2 base1


Conjugate acid-base pair

Bronsted acid  Conjugate base of the acid + H+

Bronsted base + H+  Conjugate acid

Although the Bronsted-Lowry concept of acids and bases is better than the Arrhenius concept, it
cannot account for the acidic and basic character of compound not containing hydrogen. For
example, acidic nature of oxides such as CO2, SO2 etc., and the basic nature of the compounds
of the type CaO, Na2O etc.

R elative Strengths of Conjugate Acid–Base Pairs

A stronger Bronsted acid will have a higher tendency for donating proton to the base, hence
would tend to exist as its conjugate base. The conjugate base so formed will have very little
tendency to pick up a proton, hence would act as a weak base. Thus, there exists an interdependent
relationship between the strengths of an acid and its conjugate base.
The stronger an acid, weaker is its conjugatte base, and stronger a base, weaker is its conjugate
acid.
In water, HCl acts as a strong acid. As the reverse reaction occurs to a very small extent Clă ion
acts as a weak base. So, the anion of a strong acid is a weak base. Similarly, the cation of a weak
+
base acts as a strong acid. e.g., NH4 ion in water is a strong acid.

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R elative strengths of common conjugate acid-base pairs

Bronsted acid  Conjugate base of the acid + H+

HClO4 
ClO4

H2SO4 
HSO4

HI Iă

HBr Bră

HCl Clă

HNO3 
NO3

CH3COOH CH3COOă

H2CO3 
HCO3

H2 S HS ă

+
NH4 NH3

HCN CNă

H 2O OH ă

NH3 
NH 2

Amphoteric substances

Substances which can act as an acid as well as a base are called amphoteric substances. For
example, Al(OH)3, Zn(OH)2 behave both as acids and as bases in their reactions. The substance,
which can donate or accept a proton to act as an acid or a base is termed amphiprotic. For
example, the species such as HSO4 and HCO3 are amphiprotic, because of the following reactions.

HSO4ă + H2 O  H3 O + SO24  (HSO4 acting as an acid)

ă ă
HSO4ă + H2 O  OH + H2 SO4 (HSO4 acting as base)

HCO3ă + H2O  H3 O+ + CO32  (HCO3 acting as an acid)

HCO3ă + H2 O  OH  H2 CO3 (HCO3 acting as an acid)

ă

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Water is the most common solvent showing a unique behaviour. It can act as an acid as well as
a base. In reactions like,


 + 
H2 O + NH3  NH4  OH
acid base

it acts as an acid, while it behaves like a base in a reaction of the type,


H2O + NH3 

 NH4  OH

The dual role of water molecule may thus be represented by the equation,

H 2O + H 2O 

 H3O  OH 
acid1 base 2 acid2 base1

Water is thus known as an amphiprotic solvent. Solvents which neither donate nor accept protons
are called aprotic solvents.

R elative Strength of Bronsted Acids and Bases

According to Bronsted-Lowry theory, an acid is a proton donor and base is a proton acceptor.
Therefore the strength of an acid or a base is determined by its tendency to lose or gain protons.
A strong acid is a substance which loses a proton easily to a base.

Relative strength of acids

The relative tendency of acids to transfer a proton to a common base, generally water is expressed
as the relative strength of bronsted acids. For example, HCl has a higher tendency to transfer a
proton to H2O than CH3COOH. This means HCl is a stronger acid than acetic acid. Thus,


 + 
HCl + H2O  H3O  Cl
(higher tendency for forward reaction)


 ă 
CH3COOH + H2O  CH3COO + H3O
(small tendency for forward reaction)

Similarly, a base having a higher tendency to accept a proton is stronger. For example, ammonia
accepts a proton more readily from water molecule than a water molecule from another water
molecule, and hence ammonia is more basic than water.


 + 
H2O + H2O  H3O  OH
(very little tendency for the forward reaction)

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
  
H2O + NH3  NH4  OH

(little tendency for the forward reaction)

The ability of an acid to lose a proton (acid strength) is described by its acid ionization constant.
The larger the value of the acid ionization constant Ka, higher is the concentration of H3O+ in
the solution, stronger is the acid. Knowing the ionization constants of acids one can get the
relative strengths of different acids at a particular temperature.


  
CH3COOH + H2O  CH3COO  H3O

Acetic acid, (CH3 COOH) K a  1.85  105

H O  CH COO 
 3   3 
Ka 
CH3 COOH


  
HF + H2O  F  H3O

H O  F  
3
Hydrofluoric acid, (HF) Ka  6.7  10 4
Ka    
[HF]

Since the ionization constant of HF is larger than the ionization constant of CH3COOH, hydrofluoric
acid (HF) is a stronger acid than acetic acid, (CH3COOH).

Relative strength of bases

The ability of a base to accept a proton (basic strength) is described by its base ionization constant
(Kb). The larger the value of Kb, higher is the concentration of OHă, stronger is the base.
For example,


  
H2O + NH3  NH4  OH

 NH   OH 
Kb  
4    1.8  10 5
[NH3 ]


  
H2O + C6 H5 NH2  C6 H5 NH3  OH ,

Since the value of Kb for aniline is much less than that of ammonia, hence aniline (C6H5NH2)
is a weaker base than ammonia (NH3).

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Example 1

Give the conjugate acids of the following :

(a) OHă, HCO3ă, HPO4-ă2, CH3NH2, CO3ă2, NH3, CH3COOH
(b) Give the conjugate bases of the following : HSă, H3O+, H2PO4ă, HSO4ă,HF, CH3COOH,
[Al(H2O)6]3+.
Solution :
(a) OH ă : H 2O
 : H2CO3
HCO3

2 
HPO4 : H2PO4

CH3NH2 : CH3 NH3

 
CO23 : HCO3


NH3 : NH4


CH3COOH : CH3COOH2

(b) HS ă : S2ă
H 3O + : H 2O

ă 2ă
H2 PO4 : HPO4

HF : Fă
CH3COOH : CH3COOă
[Al (H2O)6]3+ : [Al(H2O)5OH]2+

3. LEWIS CONCEPT OF ACIDS AND BASES

In 1938 G.N. Lewis put forward a more generalized acid-base concept.
According to this concept, an acid is a species (charged or uncharged) which, can accept a pair
of electrons and a base is a species (charged and uncharged), which can donate a pair of electrons
towards the formation of a covalent bond. Thus, a Lewis acid is an electrophilic, and a Lewis base
is a nucleophile. For example, in the reaction: NH3 is a donor of electron pair and BF3 accepts
a pair of electrons. So, according to he Lewis concept, : NH3 is a Lewis base, and BF3 is a Lewis
acid.

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Lewis acids

The following types of compounds or species are Lewis acids :

Ć All molecules possessing an atom with incomplete octet of electrons or Lewis acids.
Examples : BF3, AlCl3

Ć All cations are Lewis acids,

Examples : Ag+, Cu2+, Fe2+, Fe3+ etc. are Lewis acids.

Ć All molecules in which the central atom can acquire more than eight valence electrons.
Examples : SiCl4, SiF4, etc. are Lewis acids.
Ć Molecules with multiple bonds between atoms of different electronegativities e.g. CO2, SO2
etc. are Lewis acids.

Lewis bases

The following types of compounds or species are Lewis bases.

Ć All anions are Lewis bases e.g. OHă, CNă,CH3COOă etc.
Ć All molecules having ionăpair of electrons viz : HN3, H2O, CO; and amines etc. are Lewis
bases. It may be noted that all Bronsted bases are also Lewis bases, but all Bronsted acids
are not Lewis acids.

Lewis Acid–Base Reaction

Whenever a Lewis acid reacts with a Lewis base, a covalent bond is formed.
For example, CO2 (Lewis acid) reacts with OHă(Lewis base) to give HCO3ă (bicarbonate ion), BF3
(boron trifluoride) behaves as a Lewis acid and NH3 (ammonia) as a Lewis base.
Calcium oxide (CaO) behaves as a Lewis base, and sulphur trioxide (SO3) as a Lewis acid in the
reaction between the two.
The Lewis concept of acids and bases suffers from the following limitations.
Ć It fails to account for the relative strength of acids and bases, as it is not based on ionization.
Ć An acid-base reaction being an electron-transfer reaction, should be quite fast. However,
many Lewis acid-base reactions are slow.

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This type of 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

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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 as electrolytes while those substances which are non-conducting are called as
non-electrolytes.

I onization in electrolytes

Strong electrolytes are almost completely dissociated/ionized into the constituent ions in aqueous
solution. Even at higher concentrations, very small amount of any strong electrolyte is present in
the unionized form. Weak electrolytes are however, partially ionized and a dynamic equilibrium
exist between the inonized and unionized forms.
In 1887, s. Arrhenius postulated the first theory of electrolytic ionization. The basic postulates of
his theory are.
Ć When an electrolyte is dissolved in water, it ionizes to produce ions in the solution. These
ions are free to move throughout the bulk of the solution.

Ć The total number of positive charges is equal to the total number of negative charges in any
solution of any electrolyte. The ions tend to recombine to form the unionized electrolyte.
Hence, a dynamic equilibrium exists between the ionized and unionized form of the electrolyte.
For example, an electrolyte AB ionizes in the solution to form A+ and Bă. The equilibrium
established in the solution is :

AB 

 A+ + B

The ionization constant (K) is then given by,

 A   B  
K    
[AB]

Ć The properties of an electrolyte in the solution are due to the ions it gives in the solution.
For example, a solution of copper sulphate is blue due to the presence of Cu2+(aq) ions in
it.

Ć The fraction of the total number of molecule present as free ions in the solution is known
as the degree of ionization (). This is defined as,

Number of molecules split into ions

 
Total number of molecules dissolved

The degree of ionization at any concentration (C) of AB in moles per litre is denoted as (C).

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OSTWALD’S DILUTION LAW

This law deals with the law of mass action to the equilibrium between the ions and unionized
molecules in aqueous solutions of weak binary electrolytes such as acetic acid, propionic acid,
HCN, NH4OH etc.
Consider a dilute solution of weak binary electrolyte AB containing C moles in 1 litre. At any
given temperature, there will be equilibrium between the unionized molecules of AB and the ions
A+ and Bă. Let () be the degree of dissociation of AB at equilibrium.

Initial Conc. AB 


 A+ + Bă
C O O
Conc. at equilibrium C (1 ă ) C C

Then according to law of mass action,

 A    B 
(C) (C) C 2
K      
[AB] C(1 ă ) (1  )

As ÂÊ is generally small, the term 1    1 .

Hence, K = C2

or  K /C = K.V

where ÂVÊ is the volume of the solution in litres containing one mole of the solute. From the above
equation it follows that if the concentration decreases, the degree of ionization () must increase.
Thus, at constant temperature, an electrolyte in solution gets ionized to a larger extent with
increasing dilution. This is called Ostwald dilution law. This law is not applicable to solutions of
strong electrolytes as they are completely dissociated and there is no equilibrium between the
dissociated and undissociated molecules.

Ionization of an acid (weak)

An acid of the type HA can undergo ionization when dissolved in water as.


  
HA + H2O  H 3O  A

If ÂnÊ moles of the acid are dissolved in ÂVÊ units of volume (litres L) and () is the degree of
ionization, then the equilibrium amounts of various species and the concentration in moles per
litre in the solution are,
Number of moles of [HA] = n (1 ă ) = C (1 ă ) mol Lă1
Number of moles of [H3O+] = n = C mol Lă1

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ă
Number of moles of [A ] = n = C mol Lă1
Where ÂCÊ is the molar concentration of the acid. The ionization constant for the above reaction
is given by,

H O+   A ă  2
Ka = 
3     (C) (C)  C
[HA] C(1  ) (1  )

If ÂÊ is amall then 1    1

Hence, Ka = C2

or   Ka / C  KaV

where ÂVÊ is the volume of the solution in litres containing one mole of the acid HA. As the degree
of ionization increases with-dilution the, the hydronium ion or hydrogen ion concentration is
given by.

Ka
[H3O ]  C  C  K aC
C

Ionization of a base (weak)

The ionization of a weak base is characterized by the equilibrium,


  
MOH  H2O (excess)  M ( aq)  OH ( aq)

If ÂnÊ moles of the base are dissolved in ÂVÊ units of volume (litres L) and  is the degree of
ionization, then the equilibrium amounts of various species and the concentration in moles per
litre in the solution are,
Number of moles of [MOH] = n (1 ă ) = C (1 ă ) mol Lă1
Number of moles of [OHă] = n = C mol Lă1
Number of moles of [M+] = n = C mol Lă1
where ÂCÊ is the molar concentration of the base. The ionization constant for the above reaction
is given by,

 M   OH ă  2
Kb      (C) (C)  C
[MOH] C(1  ) (1 ă )

If ÂÊ is small then 1    1

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Hence, Kb = C2

Or   Kb / C  Kb V

where ÂVÊ is the volume of the solution in litres containing one mole of the base MOH. As the
degree of ionization increase with dilution then, the hydroxide concentration is given by.

Kb
[OH ]  C  C  Kb C
C

Protic acids

Acids which contain ionizable hydrogen are called protic acids. These are classified as.

Types of protic acids

Monoprotic acids

These acids contains only one ionizable hydrogen in its molecule. It is denoted by HA.

Example : HCl, CH3COOH, HNO3 etc.

Diprotic acids

The diprotic acids contain two ionizable hydrogen in its molecule. They are denoted by H2A.
Example : H2SO4, (COOH)2, H2CO3 etc.

Triprotic acids

These acids contain three ionizable hydrogen in its molecule. It is denoted by H3A.
Example : H3PO4 etc.

In all these acids, the primary ionization constant (K1) is stronger than the secondary (K2), which
is much stronger than the tertiary (K3) ionization constant. This is because a proton (H3O+) would
be released more readily from an uncharged molecule than from a mono-negative ion, and more
readily from a mono-negative ion than from a bi-negative ion. Also the hydronium concentration
from the first ionization will suppress the subsequent ionizations due to common ion effect (this
will be discussed a little later in the chapter)
Some general observations on the behaviour of protic acids in aqueous solution are :
Ć The protic acids which have very high value of the acid dissociation or ionization constant,
ionize/dissociate almost completely in aqueous solution at ordinary dilutions. They are called
strong acids.
Example : HCl, H2SO4, and HNO3.

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Ć Acids, which dissociate in aqueous solution to a smaller extent at ordinary dilution, to give
low concentration of H+ ions in solution, are called weak acids.
Example : CH3COOH, (COOH)2, H3PO4, HCN, HF, etc. The Ka or K1 values of such acids
are much smaller than one.
Ć On dilution, the ionization of an acids increase. So, concentration of H+ ions also increase
on dilution. Therefore, strength of the acid increases with dilution. It is for this reason that
the acid strengths are compared at equal concentrations.
Ć For di-and tri- protic acids, first dissociation is stronger than the second, which in turn is
much stronger than the third dissociation i.e., K1  K2  K3. This is because the removal
of a proton from a negatively charged species is more difficult than from a neutral molecule.

Example 2

Which of the following acids is the strongest and which one is the weakest. Explain.
Solution :
Nitrous acid (HNO2) Ka = 5.1 ï 10ă4
Sulphurous acid (H2SO3) Ka = 1.7 ï 10ă2
Phosphoric acid (H3PO4) Ka = 7.1 ï 10ă3

 A   H  
For, HA  A  H K a    

  + 
[HA]

Thus, larger the Ka value stronger is the acid. Therefore,

H2SO3  H3PO4  HNO2

strongest weakest

Example 3

Calculate the degree of ionization and [H3O+] of a 0.1 mol/L solution of acetic acid. Given
Ka (CH3COOH)=1.8 ï 10ă5 mol/L.
Solution :
Let ÂÊ be the degree of ionization. The concentration of various species involved in the equilibrium
are as follows.


  
CH3COOH + H2O  CH3COO  H3O

At equilibrium : C (1 ă ) C C

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The equilibrium constant for the ionization of CH3COOH can be written as follows :

CH COOă  H O+  2
Ka = 
3   3   (C) (C)  C
[CH3COOH] C (1 ă ) (1 ă )

CH3COOH is very feebly ionized. So, ÂaÊ may be ignored in comparison to 1. Then,

Ka 1.8  10 5 mol/L
   1.34  10 3
C 0.1mol/L

Then, [H3O+] = C = (0.1 mol/L) ï (1.34 ï 10ă2)

= 1.34 ï 10ă3 mol/L

Example 4

At 298 K a 0.1 M solution of acetic acid is 1.34% ionized. What is the ionization constant
(Ka ) for the acid ?
Solution :
Acetic acid ionized as follows :



CH3 COOH  H2 O  CH3 COO   H3 O 

Initial conc/mol Lă1 0.1 0 0

Equilibrium conc/mol Lă1 0.1 (1 ă ) (0.1) (0.1)

 CH COO    H O 
 3  3  0.1   0.1 
Ka  
[CH3COOCH] 0.1 (1 ă )

1.34
   0.0134
100

0.1  2 0.1  (0.0134)2

So, Ka    1.82  105
(1  ) (1  0.0134)

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I onic Product of Water

The dissociation constant K of H2O, dissociating very slightly into H+ and OHă (H2O  H+ +
OHă) is given by

[H+ ] [OH ă ]
K
[H2O]

The concentration of an undissociated molecule of H2O (i.e., [H2O]) is practically equal to the
initial molar concentration of water as water dissociated feebly. [H2O] may thus be taken as
constant, the value of which is equal to 100/18, i.e., 55.54 moles per litre supposing the density
of water as 1 g per mL.
K ï [H2O] = [H+] [OHă]
or Kw = [H+] [OHă]
Kw is known as ionic product of water which increases with the increase in temperature.
At 25ĈC, Kw = 1 ï 10ă14 (mole/L)2.

At the body temperature (37ĈC), Kw = 2.5 ï 10ă14 (mole/L)2

For pure water (neutral) [H+] = [OHă]

 [OH+] = [OHă] = K w  10 14  107 mole/L

For any acidic solution, [H3O+] > [OHă]

Or [H3O+] > 10ă7 M
For any alkaline solution,
[H3O+] < [OHă]
Or [OHă] > 10ă7 M

Note : Kw is a constant irrespective of the presence of other ions in the solution.

Effect of temperature on K

The value of Kw varies with the change in temperature. The values of [H3O+] and [OH] are
always equal to each other at all temperatures but the values of Kw are different at different
temperatures. The value of Kw increases with the rise in temperature. This is because increase
in temperature will shift the equilibrium in the forward direction producing large concentrations
of [H3O+] and [OH] ions (Le ChatellerÊs principle).
Hence, Kw increases with rise in temperature.

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I n acidic solution

When an acidic solution of HCl is added to a pure neutral solution of water, the concentration
of [H3O+] becomes larger than 1.0 ï 10ă7 mol Lă1. The dissociation equilibrium of water shifts in
the reverse direction (Le ChatelierÊs principle). The excess [OH]ă ions combine with hydronium
ions to form undissociated water molecules so that he value of Kw remains constant in the
solution. The concentration of [OH] ions will then be equal to

Kw
[OH  ] 
H O 
 3 

The concentration of [H3O+] is more than the concentration of the [OHă] ions in acidic solution.
When a few drops of a base like NaOH is added to pure water, the concentration of [OHă]
incr eases and t hat of hydr ogen ions decr eases. The concent r at ion of [H 3O+] can be calculated
as :

Kw
[H3 O ] 
OH 
 

Thus in basic solution the concentration of [OH] will be greater than of [H3O+]
It can be concluded that the hydronium and hydroxyl ions are always present in solution whether
they are acidic or basic. However their concentrations differ.

In acidic solution : [H3O+] > [OHă]

In basic solution : [H3O+] < [OHă]
In neutral solution : [H3O+] = [OHă]

pH SCALE :
pH of solution is the negative logarithm to the base 10 of the concentration of H+ ions which it
contains (Basically P acts as a mathematical operator : p(A) = ă log10 [A])

 pH = ă log10[H+]

At 25ĈC, using this definition, a scale called pH scale is developed as follows :

For H2O, H+ = 10ă7 M

pH (H2O) = ă log (10ă7) = 7

 For a neutral solution; pH = 7

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+ ă7
(1) If [H ] > 10 in a solution i.e., solution is acidic then pH < 7
+ ă7
(2) If [H ] < 10 (or [OHă] > 10ă7) i.e. solution is basic then pH > 7.

Acidic H2O Basic

At 25ĈC 3 4 5 6 7 8 9 10 11
(298 K)

Acidity increases  pH  Basicity increases

(Neutral)

1. pH Calculation of strong acid

A strong acid completely ionises in water.

For example, HCl  H+ + Clă

Let C be the concentration of HCl.

The concentration of H+ obtained from HCl will also be C.

 pH = ă log C

This process cannot be used to calculate the pH of 10ă7 M HCl. Since, we know that any acidic
solution will have pH less than 7, we must adopt some other method.

M ethod I

We already know the concentration of H+ (or H3O+) ions from pure water is 10ă7 M. So all we
need to do is to add the H+ ion concentration from water and H+ (or H3O+) ion concentration from
HCl to get the [H+]Total.

 (H  ) T  (H  )HCl  (H  ) water  10 7 M  107 M  2  10 7 M

 pH = ă log (H+) = ă log 2 ï 10ă7 = 6.6989

Though the method looks correct but there is a mistake in it. In chemical equilibrium we have
learnt about Le-ChatelierÊs Principle, which states that when concentration of a reactant or
product is changed the reaction tends of go forward or reverse to finally reestablish equilibrium.
We can see that in the present case, by adding 10ă7 M HCl to water, we are increasing the [H+].
This should make the reaction go in the reverse direction. Therefore the [H+] from water would
become less than 10ă7 M. So the method will yield incorrect result.

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M ethod II

The statement given above that ÂÂthe addition of an ion to an equilibrium, having the same ion
makes the equilibrium move in a direction to consume that ion’’ is called the c ommon ion effect.
This implies that water would dissociate less in the presence of HCl. Let the amount of water
dissociated be x´ in the presence of 10ă7 M HCl.

 + 
2H2O  H3O  OH
(x´ + 10ă7) x´

At equilibrium

[H3O+] [OHă] = 10ă14

(x´ + 10ă7) (x´) = 10ă14

Calculating for x´, we get x´ = 0.618 ï 10ă7 M.

Here we can clearly see the common ion effect in operation. Water which was dissociating to give
10ă7 M H3O+ ions, has now experienced the common ion effect and has now yielded only
0.618 ï 10ă7 M H3O+ ions.

Therefore, [H3O+]T = (10ă7 + 0.618 ï 10ă7) M

 pH = ălog (1.618 ï 10ă7) = 6.7910

Now, let us answer the question as to why we take the [H+] from water into account for calculating
the pH of 10ă7 MHCl while for calculating the pH of 10ă6 M, 10ă5 M, 10ă4 M, 10ă3 M, 10ă2 M
and 10ă1 M HCl, we have not considered it. It can be seen that the H+ ions from water, decreases
due to the common ion from HCl. Greater the concentration of the common ion added, greater will
be the effect. Therefore, for concentrations higher than 10ă6 M (and inclusive of 10ă6 M), the H+
from water will be even less than 0.618 ï 10ă7 M and would be so small in comparison to the [H+]
from HCl, that we can ignore it.

Thus, it is concluded that [H3O+] from water needs to be considered only if the [H3O+]
from acid is < 10ă6 M and if [H3O+] from acid is > 10ă6 M, the [H3O+] from water can be
ignored.

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Example 6

While calculating the pH of 10ă7 M HCl, we have taken into account the common ion effect
of HCl on water. Why did we not take the common ion effect of water on HCl ?
Solution :
Let us assumed that the Kw of water be 10ă10 at 25ĈC. Then in pure water, x2 = 10ă10 ; x = 10ă5
Let us now calculate [H3O+] from the water in the presence of 10ă7 M HCl using the same value
of Kw.
(x ´ + 10ă7) x´ = 10ă10
 x´ = 0.995 ï 10ă5 M
5 5
The percentage decrease in the concentration of H3O+ of water is 10  0.995  10  100  0.5%
10 5
Thus, it can be concluded that larger the value of equilibrium constant of the weak electrolyte,
lesser is the common ion effect produced. So, the common ion effect is experienced more by the
weak electrolyte (having smaller equilibrium constant) than the strong electrolyte (having larger
equilibrium constant).

Example 7

Calculate the pH value of (i) 0.001 M HCl and (ii) 0.01 M NaOH
Solution :
(i) Since HCl is a strong acid, it completely ionizes and therefore, H3O+ ions concentration is equal
to that of the acid itself i.e.,
[H3O+] = [HCl] = 0.001 M = 1 ï 10ă3 M
now, pH = ă log [H3O+]
pH = ă log [1 ï 10ă3]
= ă (ă 3) log 10 = 3
(ii) Since NaOH is a strong base, it completely ionizes and therefore, OHă ions concentration is equal
to that of the base itself i.e.,
[OHă] = [NaOH] = 0.01 M = 1 ï 10ă2 M
Kw = [H3O+] [OHă]

Kw 1  1014
[H3O ]    1  1012
OH   1 10 2
 

pH = ă log [H3O+]
pH = ă log [1 ï 10ă12]
= ă (ă 12) log 10 = 12

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Example 8

Acid A, B, C and D have the following pKa values : A = 1.5, B = 3.5, C = 2.0, D = 5.0. Arrange
these acids in the increasing order of acid strength.
Solution :
We know that,
pKa = ă log Ka or Ka = 10ăpKa
Therefore, for the given acids,
Ka (A) = 10ă1.5 Ka (B) = 10ă3.5
Ka (C) = 10ă2.0 Ka (D) = 10ă5.0
Since, 10ă5.0 < 10ă3.5 < 10ă2.0 < 10ă1.5
Hence, the strength of acids follows the order, D < B < C < A
Weakest Strongest

Example 9

The value of Kw is 9.55 ï 10ă14 at a certain temperature. Calculate the pH of water at this
temperature.
Solution :
Kw = 9.55 ï 10ă14
For water [H 3O+] = [OHă]
If K w = [H3O+] [OHă] = 9.55 ï 10ă14 then,
[H3O+] [H 3O+] = 9.55 ï 10ă14
[H 3O+] 2 = 9.55 ï 10ă14

or [H3O ]  9.55  1014  3.09  10 7 mol L1

pH = ă log [H3O+]
pH = ă log [3.09 ï 10ă7]
= ă (log 3.09 + log 10ă7)
= ă (0.49 ă 7) = 6.51

2. pH Calculation of Weak Acid

Weak acid is that which dissociate partially in water and soon comes in equilibrium with its ions
as


  
CH3 COOH  H2 O  CH3 COO  H3 O

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The equilibrium constant is called Ka (dissociation or ionization constant).

[CH3COO ]  [H3O ]
Ka 
[CH3COOH]

Let the degree of dissociation of weak acid be .


  
CH3COOH  H2O  CH3COOH  H3O

Initial conc. c 0 0
Conc. at equilib. căc c c
If  < < 1 than 1 ă   1 (i.e. for  less than or equal to 0.1)

Ka
Ka  c2 or 
c

Ka
[H3O ]  c  c   Ka  c
c

Using the value of Ka and c, [H3O+] can be calculated and then pH of the solution can be
calculated.
Taking log of both the sides of above equation,
log [H3O+] = ólog Ka + ólog c
Multiplying both sides by ă 1,
ă log [H3O+] = ă ólog Ka ă ólog c

pH = ópKa ă ólog c = ó(pKa ă log c )

Example 10

The self ionisation constant for pure formic acid, K = [HCOOH2+] [HCOOă] has been estimated
as 10ă6 at room temperature. What percentage of formic acid molecules in pure formic acid
are converted to formate ion ? The density of formic acid is 1.22 g/cm3.
Solution:
Given density of formic acid = 1.22 g/cm3
 Weight of formic acid in 1 litre solution = 1.22 ï 103 g

1.22  103
Thus, [HCOOH]   26.5 M
46

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Since in case of auto ionisation [HCOOH2+] = [HCOOă]

and [HCOOă] [HCOOH2+] = 10ă6
[HCOOă] = 10ă3

[HCOO ă ] ï 100 103

Now % dissociation of HCOOH =   100
[HCOOH] 26.5

 C 
  C(1  )  = 0.004%
 

Example 11

Liquid ammonia ionises to a slight extent. At ă50ĈC, its self ionisation constant, KNH =
3
[NH4+] [NH2ă] = 10ă30. How many amide ions, are present per cm3 of pure liquid ammonia ?
Assume N = 6.0 ï 1023.
Solution :


  
2NH3  NH4  NH2 (self ionization)

K  [NH4 ] [NH2 ]
ă
and

[NH4 ]  [NH2 ]
ă


[NH4 ]  [NH2 ]
ă


K  1030  1015 M
 ă
[NH2 ] 

Number of amide ions in 103 cm3 = 10ă15 ï 6 ï 1023

3
10 15  6  1023
Number of amide ions in one cm =
103

= 6 ï 105 ions

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Example 12

Calculate the concentration of fluoroacetic acid which is required to get [H+] = 1.50 ï 10ă3 M.
Ka of acid = 2.6 ï 10ă3.

Solution : CH2 FCOOH 


 CH2 FCOO  H 

Mole before dissociation 1 0 0

Mole after dissociation (1 – )  
Given, [H+] = C = 1.5 ï 10ă3 mol litreă1

(C) (C) C 2
 Ka  
C(1  ) (1  )

1.5  103  
2.6  103 
(1 ă )

  = 0.634
Now, C = 1.50 ï 10ă3

1.50  103
 C  2.37  10 3 M
0.634

Note : Since Ka is of the order of 10ă3 M and thus it is not advisable to use Ka = C2. Because
(1 ă ) is not equal to 1 since a is not small.

Example 13

Determine degree of dissociation of 0.05 M NH3 at 25ĈC in a solution of pH = 11.


Solution : 

 NH4 OH  NH4  OH

1 0 0
(1 ă )  
Given, pH = 11
 [H + ] = 10ă11
 [OHă] = 10ă3 = C
Since, C = 0.05

10 3 10 3
  =   2  102 or 2%
C 0.05

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Example 14

K1 and K2 for dissociation of H2S are 4 ï 10ă3 and 1 ï 10ă5. Calculate sulphide ion
concentration in 0.1 M H2S solution. Also report [H+] and pH.

Solution : H2 S  H  HS 

[H+ ] [HS ă ]
K1   4  103
[H2S]

 [H+] = C; [Hă] = C; [H2S] = C (1 ă )

C . C C 2
or 4  103  
C(1  ) (1  )

0.1 C2
or 4  103   (1 ă  should not be neglected)
C(1  ) (1  )

  = 0.18
 [H+] = C = 0.1 ï 0.18 = 0.018 M  pH = 1.7447
[HSă] = C = 0.1 ï 0.18 = 0.018 M
[H2S] = C (1 ă ) = 0.1 (1 ă 0.18) = 0.082 M
Now HSă further dissociates to H+ and Să2; C1 = [HSă] = 0.018 M

HS  

 
 H  HS


1 0 0
(1 ă )  

[H  ] [S2 ]
 K a2  1  10 5 
[HS ]

 [H+] already in solution = 0.018 and thus, dissociation of HSă further supresses due to
common ion effect and 1 ă   1.

0.018  C11
 1  10 5   0.0018  1
C1 (1  1 )

1  105
 1  = 5.55 ï 10ă4
0.018

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 [S ] = C11 = 0.018 ï 5.55 ï 10ă4 = 10ă5
ă2

[HSă] = C1 (1 ă 1) = C1 = 0.018 M

Example 15

Calculate the pH of 10ă6 M CH3COOH. Ka (CH3COOH) = 1.8 ï 10ă5.

Solution :
We can solve this problem by two methods. The methods are as follows :

Method 1 :
[H3O+] due to a weak acid is given by

[H3O ]  K a  c  1.8 105  10 6  4.24  10 6

pH = 5.37
Though it seems that we have solved the problem correctly, there is an error in this method. This
error can be highlighted by comparing it with the pH of 10ă6 M HCl. We can see that the pH
of 10ă6 M HCl would be 6. As we know that lesser pH implies higher concentration of H3O+ ions.
So a weak acid having the same concentration as that of a strong acid cannot give higher
concentration of H3O+ ions. The error in pH calculation has occurred because we have assumed
that  is very much small compared to 1 without knowing the value of . In fact, if we make this
assumption, the  we get is,

Ka 1.8  105
   4.24
c 106

This value is no possible as  cannot be more than 1, ever. Therefore, the assumption made by
us is not valid and pH of 10ă6 M CH3CO2H is to be calculated without any assumption.

Method 2 :

c 2 106   2
Ka  , 1.8  10 5 
1 1

Solving for ,  = 0.95

Note that the value of a is quite high, so it cannot be ignored with respect to 1.
 [H3O+] = c = 0.95 ï 10ă6 = 9.5 ï 10ă7
The [H3O+] from acetic acid < 10ă6 M, so [H3O+] from water should also be considered.
 (x´ + 9.5 ï 10ă7) x´ = 10ă14 (where x´ is the [H3O+] coming from water in the presence of
10ă6 M CH3COOH).

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x´ = 1.04 ï 10ă8
[H3O+]T = (9.5 ï 10ă7 + 1.04 ï 10ă8) = 9.6 ï 10ă7
pH = 6.01.

The above illustration shows a need to know when the assumption (that  is very small compared
to 1) is valid and when not. Thus, to calculate the pH of a weak acid, we should proceed as

Ka
First calculate the value of  from the expression  = .
c

If this value of  comes out to be less than or equal to 0.1, then the assumption is valid and

[H3O+] is calculated using the expression, [H3O+] = K a  c but if the  value obtained from

the given expression > 1, then the assumption is not valid and one has to calculate  using the

c 2
expression, K a  and then calculate [H3O+] using the expression, [H3O+] = c.
1

It was suggested that for calculating the pH of weak acid, first calculate  from the expression,

= Ka and then compare its, value with 0.1. This statement looks a little odd. How can we
C

compare the value of  (which is obtained after making the assumption) with 0.1 and then claim
that it is correct if  < 0.1 ? Let us see how the given procedure works.

2
The actual expression for calculating the value of  is K a  c . If we make the assumption
1

that  is very small compared to one and ignore it with respect to 1 in the denominator, we get
Ka = c2. By ignoring the  in the denominator, we increase the value of the denominator. This
will consequently increase the value of the numerator (since the ratio is a constant). Thus, the
value of a calculated after the assumption will be greater than the actual value of . If this
approximated value of a is less than or equal to 0.1 then it means that the actual value of  will
be even less than 0.1. Therefore, the assumption is valid and if this approximated value of  is
greater than 0.1, then the actual value of  may be greater than, equally to or less than 0.1. So
in the later case, we are unable to predict and so we do not make any assumption and calculate
c 2
actual value of  using the expression, K a  .
1

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Some Important Points :
Ć Relative strength of two weak acids is a measure of [H3O+]

[H3 O ]1 K1C1

 K 2C2
[H3 O ]2

Ć pH of a weak monobasic acid

pH = ă log [H3O+] = ă log K aC

1
= [ pK a  log C]
2
Total [H3O+] in a mixture of two weak acids.

[H3O ]  K1C1  K 2C2

Ć For weak bases :


  
BOH  B  OH

[B ] [OH  ] Cx2

Kb    Cx2
[BOH] (1  x)

Kb
x
C

[OHă]weak base = Cx = Kb C

Ć Relative strength of two weak bases

[OH  ]1 K1C1

 K 2 C2
[OH ]2

Ć pOH of weak monoacid base

1
pOH   log (OH )  [ pK b  log C]
2
pH = 14 ă pOH

= 14  1 [ p K b  log C]
2
Total [OHă] in a mixture of two weak bases.

[OH ]  K1C1 + K 2C2

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HYDROLYSIS OF SALTS

Dissolution of different salts in water does not always result in neutral solutions. For example,
aqueous solution of copper sulphate is acidic whereas aqueous solution of sodium acetate is basic
and aqueous solution of sodium chloride forms neutral solution. This is due to the dissociation of
the salt in water to form ions. This process of the reaction of anion or cation of the salt with water
to produce an acidic or an alkaline solution is called hydrolysis. Thus, hydrolysis is reverse of
neutralization.
The equilibrium constant of such a reaction is called hydrolysis constant.
Hydrolysis of anion (Aă)

BA  H2O  HA  BOH

Salt Acid Base

or A   H2O  HA  OH

[HA] [OH ]
Kh 
[A ă ]

Hydrolysis of cation (B+)

[BOH] [H3O ]
Kh 
[B + ]

The fraction of the total salt that gets hydrolysed at equilibrium is called degree of hydrolysis. It
is written as ÂhÊ.

Relation of Hydrolysis Constant and Ka and Kb

(1) Salt of weak acid and strong base

Here, the anion (Aă) is a stronger base than OHă, hence it undergoes hydrolysis to give free OHă
ions. Therefore the resulting solution will be basic in character having pH greater than 7. For
example.


  
CH3COONa + H2O  CH3COOH  Na  OH
Weak acid

Other examples of this of salts are CH3COONa, Na2CO3, Na3PO4, etc.

The aqueous solution of a salt of weak acid and strong base it alkaline. For the general reaction :



BA  H2O  BOH  HA
Salt Strong Weak
base acid

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or B  A   H2O 

  
 B  OH  HA

or A   H2O 

 HA  OH
ă

This is called anion hydrolysis.

H ydrolysis constant

The hydrolysis constant may be written as :

[HA] [OH ]
Kh  ...(i)
[A  ]

For weak acid HA, HA  H+ + Aă

[H+ ] [A  ]
Ka  ...(ii)
[HA]

Also, Kw = [H+] [OHă] ... (iii)

Multiplying equation (i) and (ii) and dividing by equation (iii), we get

K h . K a [HA] [OH ] [H+ ] [A  ] 1

   1
Kw [A  ] [HA] [H  ] [OH  ]

Kw
Kh 
Ka

The hydrolysis constant ÂKhÊ, of the salt is inversely proportional to the dissociation constant, ÂKaÊ
of the weak acid. Therefore, the weaker the acid, the greater is the hydrolysis constant of the salt.

Degree of hydrolysis

If the original concentration of the salt in the solution is ÂcÊ mol/litre and ÂhÊ is the degree of
hydrolysis at that concentration, then

A  H2O 

 
 OH  HA

Initial concentration c o o

Concentration of equilibrium c(1 ă h) ch ch

IONIC EQUILIBRIA
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The hydrolysis constant, [HA] [OH ]

Kh 
[A  ]

ch . ch ch2
= 
c (1  h) (1  h)

If ÂhÊ is very small as compared to 1, we can assume 1 ă h  1.

Kh = ch2

Kh
or h
c

Kw
Substituting the value of Kh, h 
K a .c

pH of the hydrolysed salt solution [OHă] = CH

Kw Kw
[H ]  
[OH ] ch

Kw Ka .c
Substituting the value of h, [H ] 
c Kw

K w .Ka
or [H ] 
c

Now, pH = ă log [H+]

1
 K . Ka 2
  log  w 
 c 

1
pH  [log K w  log K a  log c]
2

Now, ă log Kw = pKw ă log Ka = pKa

1 1 1
pH  pK w  pK a  log c
2 2 2

IONIC EQUILIBRIA
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(2) Salt of a Strong Acid and Weak Base

Let us take a salt, NH4Cl. It is a salt made from the reaction of strong acid, HCl and weak base,
NH4OH.

NH4 Cl (s)  NH4Cl( aq)  NH4 (aq)  Cl ( aq)

Out of NH4 and Clă, only NH 4 ion hydrolyses and let its degree of hydrolysis be h and Kh be

its hydrolysis constant. Let ÂcÊ M be the concentration of the salt, so the concentration of NH 4
would also be ÂcÊ M.

NH4 

 2H2 O  NH4 OH + H3 O
+

Initial conc. c 0 0
Conc. at equilib c(1 ă h) ch ch

[NH4 OH] [H3O+ ]

K eq 
[H2O]2 [NH4 ]

[NH4 OH] [H3 O+ ]

K eq [H2 O]2   Kh ... (i)
[NH4 ]

Multiplying numerator and denominator of equation (i) by OHă gives

[NH4 OH] [H3O+ ][OH  ]

 Kh
[NH4 ] [OH ]

Kw [NH4 ] [OH  ]
 Kh  (since [H3O ] [OH  ]  K w and  Kb )
Kb [NH4 OH]

Kw ch  ch ch2
Kh   
Kb c (1  h) 1h

Assuming h to be smaller than 0.1, it can be ignored with respect to 1. So, 1 ă h  1.

K h  ch2

Kh Kw
h 
c Kb  c

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 QUIZRR 33

Kw Kw  c
 [H3O ]  ch  c  
Kb  c Kb

Taking log of both the sides

log [H3O+] = ólog Kw + ólog c ă ólog Kb
Multiplying both sides by ă 1,
ă log [H3O+] = ă ólog Kw ă ólog c + ólog Kb
 pH = ópKw ă ópKb ă ólog c = ó(pKw ă pKb ă log c)
(since, ă log Kw = pKw and log Kb = ă pKb)

 pH = 7 ă ópKb ă ólog c.
Since, two terms are to be subtracted from 7, so, the pH of such salt solutions would be less than
7 and will behave acidic in nature. ÂcÊ in the above expression represents concentration of the ion
undergoing hydrolysis and not the concentration of the salt.

(3) Salt of Weak Acid and a Weak Base

In this case both the cation and anion undergo hydrolysis to the same or different extents. The
resulting solution may be neutral, acidic or basic depending upon the relative strengths of acids
and bases. The hydrolysis may be written as :



CH3COONH4  H2O  CH3COOH  NH4OH
weak acid weak base

Some common examples are CH3COONH4, (NH4)2 CO3, AlPO4, etc.

The aqueous solution of a salt of strong acid and weak base is acidic. For the general reaction :



BA  H2 O  BOH  HA
Salt Weak Weak
base acid

or

B  A   H2O 

 BOH + HA

This involves anionic and cationic hydrolysis.

Hydrolysis constant
The hydrolysis constant may be written as :

[BOH] [HA]
Kh  ... (vi)
[B  ] [A  ]

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34 QUIZRR
For weak acid,


  
HA  H A

[H+ ] [A ă ]
Ka 
[HA]

For weak base BOH


  
BOH  B  OH

[B+ ] [OHă ]
Kb 
[BOH]

Also, Kw = [H+] [OHă]

Multiplying equation (vi) by equation [H+] [OHă], we get

[BOH] [HA] [H  ]
Kh 
[B ] [A  ] [H  ] [OH  ]

[BOH] [HA] [H ] [OH ]

Kh 
[B  ] [A  ] [H  ] [OH  ]

[BOH] [HA]
 . . [H ] [OH ]
[B ] [OH ] [H ][A  ]

Kw
Kh 
K a  Kb

Degree of hydrolysis

If the original concentration of the salt in the solution is ÂcÊ mol/litre and ÂhÊ is the degree of
hydrolysis at that concentration, then

B  A   H2O 

 BOH + HA

Initial concentration c c o o

Concentration at equilibrium  c (1 ă h) c (1 ă h) ch ch

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 QUIZRR 35

ch. ch. h2
The hydrolysis constant, K h  
c(1  h)  c (1  h) (1  h)2

If ÂhÊ is very small as compared to 1, we can assume 1 ă h  1.

Kh = h2

or h  Kh

Kw
Substituting the value of h 
K a . Kb

Here the degree of hydrolysis is independent of the concentration of the solution. The weaker the
acid and the base, the greater is the degree of hydrolysis of the salt.
pH of the hydrolysed salt solution

[H  ] [A  ]
Ka 
[HA]

[HA]
[H ]  K a 
[A ă ]

K a . ch K .h
[H ]   a
c (1  h) (1  h)

[H ]  K a . h

 Ka Kh

Substituting the value of ÂhÊ, [H+] = Ka Kh

Kw
or [H ]  K a
K a . Kb

Kw K a

Kb

Now, pH = ă log [H+]

1
 K .K  2
  log  w a 
 Kb 
IONIC EQUILIBRIA
36 QUIZRR

1 1 1
pH   log K w  log K a  log K b
2 2 2

1 1 1
pH  pK w  pK a  p K b
2 2 2

Knowing the molar concentration ÂcÊ of the solution, Ka, Kb and Kw, the pH of the solution can
be calculated. It is clear from the above equation that pH of the solution will depend upon the
pK value of the acid and the base.

If pKa < pKb, pH of the solution will be less than ópKw and consequently the solution will be
acidic.

If pKa > pKb, then pH of the solution will be more than ópKw and hence the solution will be
alkaline.

If pKa = pKa, pH of the solution will be equal to ópKw and hence the solution will be neutral.

(4) Salt of A Strong Acid and a Strong Base

Let us consider a salt, NaCl made by the reaction of strong acid, HCl and strong base, NaOH.

NaCl (s)  NaCl (aq)  Na  (aq)  Cl (aq)

Neither of the two ions of the salt undergoes hydrolysis. So, the solution contain only the equilibrium
of ionization of water.


  
2H2O (l)  H3O ( aq)  OH ( aq)

Thus, the pH of such salts always remain constant and the solution behaves neutral at pH = 7
at 25ĈC.

Example 16

Calculate the hydrolysis constant of the salt containing NO ă2 ions. Given Ka for HNO2
= 4.5 ï 10ă10.
Solution :

Kw 1014
KH   = 2.2 ï 10ă5
Ka 4.5  10 10

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Example 17

What is the pH of a 0.5 M aqueous NaCN solution ? pKb of CNă = 4.70.

Solution :
pKa for HCN = 14 ă 4.70 = 9.30

NaCN + H 2O  NaOH + HCN

1 0 0
1 ă h h h

KH Kw . C
 [OH  ]  C.h.  C  KH . C 
C Ka

1
or pOH = [ p K w  log C  pK a ]
2

1
= [14  0.3010  9.30]
2

= 2.5
 pH = 14 ă 2.5 = 11.5

Example 18

Calculate the percentage hydrolysis in 0.003 M aqueous solution of NaOCN. Ka for HOCN
= 3.33 ï 10ă4.
Solution :



NaOCN  H2O  NaOH  HCN

 KH   Kw  1014
h  C    
   K aC  3.33  10 4  0.003

h = 10ă4

104
 % hydrolysis = = 10ă2
100

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Problem 19

Calculate degree of hydrolysis and pH of 0.2 M solution of NH4Cl. Given Kb for NH4OH is
1.8 ï 10ă5.
Solution :

NH4 Cl  H2 O 

 NH4 OH  HCl

Before hydrolysis 1 0 0
After hydrolysis 1 ă h h h
where h is degree of hydrolysis

 KH   Kw  10 14
h  C     K .C   = 5.27 ï 10ă5
   b  1.8  105  0.2

From HCl, a strong acid

K  K 
 [H ]  C.h  C  H   ( K H . C)   w .C 
 C   Kb 

 1014  0.2 
    1.054  105
 1.8  105 
 

 pH = ă log [H+] = ă log 1.054 ï 10ă5

= 4.9771

Example 20

Find out the amount of NH4Cl dissolved in 500 mL to have pH = 4.5. Kb for NH4OH is
1.8 ï 10ă5
Solution :
Let conc. of NH4Cl be C mol litreă1
NH4Cl + H2O  NH4OH + HCl

Before hydrolysis 1 0 0
After hydrolysis (1 ă h) h h

 Kw   1014  C 
 
[H ]  (K H .C) =  . C   
 Kb   1.8  105 
 

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 1014  C 
10ă4.5 =  
 1.8  105 
 

C = 1.8 mol litreă1

 Wt. of NH4Cl = 1.8 ï 53.5 g/litreă1

1
= 1.8 ï 53.5 ï g/500 mL
2

= 48.15 g

Example 21

Calculate the degree of hydrolysis of a mixture of aniline & acetic acid each of them being
0.01 M. Ka of acetic acid = 1.8 ï 10ă5 & Kb (aniline) = 4.6 ï 10ă10. Also calculate pH of the
mixture.
Solution :
Now when we mix equal concentrations of aniline and acetic acid, they will neutralise each other
to form acetanilide (salt). The alt is of weak base & weak acid, so hydrolysis takes place. The
degree of hydrolysis of the salt of weak acid and weak base is given by :

h Kh

Kw 1  1014
 Kh  
K a K b (1.8  105 ) (4.6  10 10 )

K h = 1.21           h  1.21  1.09

Which is impossible.
Hence, as done in earlier example 15, here also we cannot use the approximate formula. Therefore,

h2
Use : Kh 
(1  h) 2

h2
 1.21 
(1  h)2

h
  K h  1.09   h = 0.523
1h

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However the pH of solution can be calculated by using the standard result :

1
pH  7   pK a  p K b 
2

pH  7 
1 
2 
 
 log 1.8  105   log 4.6  1010 


pH = 4.703
Note : Solution in this case is acidic. In such salts, pH depends upon which of two i.e. weak acid
or weak base is stronger than the other, i.e. by comparing Ka & Kb ; one can theoretically get an
ideal about the pH of solution.

COMMON ION EFFECT

The addition of an ionic salt having a common ion (anion or cation) to weak acids or weak bases,
suppresses their degree of dissociation (following LechatlierÊs principle).
Weak Acids :
Let HA be a weak acid (like CH3COOH, HCN etc.) & B+ Aă be the ionic salt containing common
anion (Aă) that is added to the acid.


  
HA aq  H aq  A aq


  
BA aq  Baq  A aq

Now, the solution has excess of Aă ions. This means increasing concentration of products, in an
equilibrium state. (Following LechatlierÊs principle) the reaction (HA  H+ + Aă) must go in
backward direction, in order to mullity the effect of added Aă ions. As a consequence, amount of
H+ in new equilibrium state will be less than before, or one can see that the degree of dissociation
of acid (HA) is decreased.

Quantitative Aspect :

HA  H+ + Aă ; its degree of dissociation =  is given by :

Ka

c

Let M molar BA be added to it & ´ be its new degree of dissociation


BA  Baq + A aq

M M (Assuming BA to be 100% ionised)

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HA  H+ + Aă

c ă c´ c´ c´

Now in solution : [HA] = c ă c´ ; [H+] = c´

[Aă] = [Aă]HA + [Aă]BA = c´ + M

[H  ][A  ] (c´) ( c´  M) ´( c´  M)

Ka   
[HA] (c ă ca´) 1 ă ´

 Ka = c´2 + M´ (as 1 ă ´  1)

 Ka = M´
(neglecting C´2 in comparison to M´ as ´ << 1 & ´2 <<< 1]

Ka
 ´ 
E

Note :
One similar lines you can find Ê for a weak base, BOH and adding B+ ions to it.

BUFFERS

Certain solutions, such as that of ammonium acetate, have a tendency to resist any change in its
hydronium ion concentration or pH, whenever a small amount of a strong acid or a strong base
is added to it. This property of a solution is known as buffer action.

Buffer Solution

A solution which resists any change of pH when a small amount of a strong acid or a strong base
is added to it, is called a buffer solution or simply as a buffer.
Alternatively, a buffer solution may be defined as a solution whose pH value does not change
appreciatbly upon the addition of small amounts of a strong acid, base and/or water from outside.
Thus, buffers have reserve acidity and reserve alkalinity.
Buffer solutions usually consist of a mixture of a weak acid and its salt with a strong base e.g.,
CH3COOH and CH3COONa, or that of a weak base and its salt with a strong acid e.g., NH4OH
and NH4Cl. The solution of any salt of a weak acid and weak base e.g., ammonium acetate, also
shows buffering property.

Types of Buffers

There are two types of buffers, acid buffer and basic buffer.

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Acid buffer

A buffer solution containing a large amounts of a weak acid, and its salt with a strong base, is
termed as an acid buffer. Such buffer solutions have pH on the acidic side i.e., pH is less than
7 at 298 K. The pH of an acid buffer is given by the equation.

[salt]
pH  pK a  log
[acid]

where Ka is the acid dissociation constant of the weak acid.

Basic buffer

A buffer solution containing relatively large amounts of a weak base and its salt with a strong
acid, it termed as a basic buffer. Such buffers have pH on the alkaline side i.e., pH is higher than
7 at 298 K.
The pH of a basic buffer is given by the equation :

[salt]
pOH  pK b  log
[base]

where Kb is the base dissociation constant of the weak base.

These equations are called Henderson equation.

Buffer-capacity and Buffer-range

The effectiveness of any buffer is described in terms of its buffer capacity. It is defined as, Âthe
number of equivalents of a strong acid (or a strong base) required to change the pH of one litre
of a buffer solution by one unit, keeping the total amount of the acid and the salt in the buffer
constantÊ.
The buffer capacity of a buffer in maximum when acid to salt or base to salt ratio is equal to 1
i.e. it contains equal number of moles of acid (or base) and the salt. All buffer solutions remain
effective over a small pH range : this pH-range is characteristic of the buffer and is termed as
the buffer-range.
For the two types of buffers, it is given by
Buffer range in pH units
Acid buffer : pKa ă 1 to pKa + 1
Basic buffer : (pKw ă pKb) ă 1 to (pKb) ă pKb) + 1
Consider acetic acid ă sodium acetate buffer, an acid buffer. the acid dissociation constant (Ka)
of acetic acid is 1.84 ï 10ă5.
Therefore, pKa for acetic acid is 4.74. Then, the buffer range of an acetic acid - sodium acetate

IONIC EQUILIBRIA
 QUIZRR 43

buffer is,
pH = (pKa) ă 1 to (pKa) + 1
= 4.74 ă 1 to 4.74 + 1
= 3.74 to 5.74
Thus, the acetic acid - sodium acetate buffer will act as an effective buffer over the pH range 3.74
to 5.74.
The pH of a buffer solution depends only on the ratio of the concentrations of the salt and the
acid, or salt and the base. It does not depend on the individual concentration. Since, the ratio
remains the same even when the solution is diluted. However, at high dilutions, buffers do not
remain effective as, they are not able to resist a change in the pH value due to the addition of
a strong acid or a strong base.

Example 22

Calculate the pH of a buffer solution containing 0.2 mole of NH4Cl and 0.1 mole of NH4OH
per litre. Kb for NH4OH = 1.85 ï 10ă5.
Solution :
According to HendersonÊs equation :

[salt]
pOH = pKb + log
[base]

pKb = ă log Kb = ă log 1.85 ï 1ă5 = 4.733

0.2
pOH = 4.733 + log
0.1

= 4.733 + 0.301 = 5.034

pH = 14 ă pOH = 14 ă 5.034 = 8.966

Example 23

A buffer solution contains 0.04 mole of Na2HPO4 and 0.02 mole of NaH2PO4 per litre. (a)
Calculate pH if pKa of NaH2PO4 is 6.84. (b) If 1 ml of 1 N HCl is added to a litre of the buffer,
calculate the change in pH.
Solution :
In this mixture NaH2PO4 is the acid and Na2HPO4 is the salt.

[Salt] 0.04
pH = pKa + log = 6.84 + log = 6.84 + log 2 = 6.84 + 0.30 = 7.14
[Acid] 0.02

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44 QUIZRR
(b) 1 ml of 1 N HCl contains 0.001 mole of H+. It will convert 0.001 mole of Na2HPO4 to 0.001
mole of NaH2PO4.

0.04  0.001 0.039

pH  pK a  log  6.84  log  7.109
0.02  0.001 0.021

The change in pH is 0.031.

Example 24

Calculate the pH of a solution made by adding 0.001 mole of NaOH to 100 ml of 0.5 M acetic
acid and 0.5 M sodium acetate solution.
Solution :

0.5
Moles of acetic acid in 100 ml of solution =  100  0.05
1000

0.5
Moles of sodium acetate in 100 ml of solution =  100  0.05
1000

When NaOH is added, acetic acid is converted into sodium acetate.

Moles of acetic acid after addition of 0.001 mole of NaOH = (0.05 ă 0.001) = 0.049
Moles of sodium acetate after addition of 0.001 mole of NaOH = (0.05 + 0.001)
= 0.051

[Salt] 0.051  10
pH  pK a  log   log (1.8  105 )  log
[Acid] 0.049  10

= 4.7447 + 0.0174 = 4.7621.

Example 25

20 ml of 0.2 M NaOH is added to 50 ml of 0.2 M acetic acid to give 70 ml of the solution. What
is the pH of the solution ? Calculate the additional volume of 0.2 M NaOH required to make
pH of the solution 4.74. The ionisation constant of acetic acid is 1.8 ï 10ă5.
Solution :
From the chemical reaction,

CH3COOH  NaOH  CH3COONa  H2O

20 ml 20 ml 20 ml

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It is evident that 70 ml of the product will contain

(i) 30 ml of 0.2 M unused CH3COOH
(ii) 20 ml of CH3COONa.

0.2
 No. of moles of CH3COOH in 70 ml of solution =  30  0.006 mole
1000

0.2
Similarly, No. of moles of CH3COONa in 70 ml of solution =  20  0.004 moles
1000

[Salt]
pH   log K a  log
[Acid]

Substituting the values of the various terms

0.004
pH   log 1.8  105  log
0.006

= 4.7447 ă 0.1761 = 4.5686

Calculation of the additional volume of 0.2 M NaOH required to make pH of solution 4.74.

[Salt]  Salt 
pH   log K a  log or 4.74   log 1.8  105  log  
[Acid]  Acid 

 Salt 
4.74  4.7447  log 
 Acid 
or

 Salt   Salt  1
 log   0.0047  Acid   1.011
 Acid 
or

Let x ml be the volume of additional 0.2 M NaOH added to make the pH of the solution 4.74. This
will further neutralise x ml of 0.2 M CH3COOH and produce x ml of 0.2 M sodium acetate. The
resulting solution (70 + x) will now contain
(i) (30 ă x) ml of 0.2 M acetic acid.
(ii) (20 + x) ml of 0.2 M sod. acetate.

Number of moles of acetic acid in (70 + x) ml solution  0.2  (30  x)  2  104 (30  x)
1000

0.2
Number of moles of CH3COONa in (70 + x) ml solution   (20  x)  2  10 4 (20  x)
1000

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[Salt] 2  104 (20  x) 20  x

Therefore,  
[Acid] 2  104 (30  x) 30  x

1 20  x

1.011 30  x

or 20.22 + 1.011 x = 30 ă x
2.011 x = 9.78 or x = 4.86
Therefore, the additional volume of 0.2 M NaOH required to make the pH of the solution 4.74
is 4.86 ml.

Example 26

500 mL of 0.2 M queous solution of acetic acid is mixed with 500 mL of 0.2 M HCl at 25ĈC.
(i) Calculate the degree of dissociation of acetic acid in the resulting solution and
pH of the solution.
(ii) If 6 g of NaOH is added to the above solution, determine the final pH. [Assume
there is no change in volume on mixing; Ka of acetic acid is 1.75 ï 10ă5 mol Lă1].
Solution :
Concentration of CH3COOH in 500 ml = 0.2 M
Concentration of HCl in 500 ml = 0.2 M
After mixing, [CH3COOH] = 0.1 M; [HCl] = 0.1 M
HCl being a strong electrolyte is completely ionised, hence concentration of H+ furnished by HCl
= 0.1 M
CH3COOH, being weak electrolyte, dissociates as below.

CH3COOH 

 CH3COOă + H+

At start c 0 0
At equilibrium c (1 ă ) c c + 0.1

[CH3COO ] [H  ] c ( c  0.1) c2  0.1 

 Ka   
[CH3COOH] c (1  ) (1  )

Since  is very very small, c2 can be neglected and 1 ă  can be taken as unity
 Ka = 0.1 

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Ka
or  =
0.1

1.75  105
=  1.75  104
0.1

Calculation of pH of the solution

[H+]total = 0.1 + c
since ca is very very small, it can be neglected
 [H+]total = 0.1
 pH = 1

6
(ii) No. of moles of NaOH added = = 0.15
40

No. of moles of NaOH left after reacting with 0.l mole of HCl = 0.15 ă 0.1 = 0.05 M
This 0.05 moles of NaOH will react with CH3COOH in the following way.

CH3COOH + NaOH  CH3COONa + H 2O

At start 0.1 mol 0.05 mol 0 0

At finish 0.05 mol 0 mol 0.05 mol 0.05 mol
Thus solution of CH3COOH and CH3COONa acts as an acid buffer. Hence in such cases

[Salt]
pH  pK a  log   log (1.75  105 )  log 1
[Acid]

= 4.75

Example 27

Two buffers, (X) and (Y) of pH 4.0 and 6.0 respectively are prepared from acid HA and the
salt NaH. Both the buffers are 0.50 M in HA. What would be the pH of the solution obtained
by m i x i n g equ al v ol u m es of t h e t w o bu f f er s ? (K HA = 1.0 ï 10ă5)
Solution :
Determination of concentration of salt, i.e. [Salt] in buffer X.

[Salt]
pH = pK  log
[Acid]

[Salt]
4.0 = 5.0  log
0.5

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[Salt]
log = ă 1
0.5

[Salt] 1
=
0.5 10

0.5
 [Salt = = 0.05 M
10

Determination of [Salt] in buffer Y

6.0 = 5.0 + log [Salt]

0.5

[Salt]
log = 1.0
0.5

[Salt] = 10 ï 0.5 = 5.0 M

0.05  5.0
 [Salt]mix =
2

= 2.525 M
Substituting the values in the relation

[Salt]
pH = pK + log
[Acid]

2.525
= 5.0 +
0.5

= 5.0 + log 5.05

= 5.0 + 0.70 = 5.7

Indicators

Indicators are substances, which indicate the completion (equivalence point or end point) of a
chemical reaction by change in colour. For example, in volumetric analysis, during the titration
of sodium hydroxide and hydrochloric acid (taken in the burette), phenolphthalein turns pink to
colourless when the whole of sodium hydroxide has been neutralized by hydrochloric acid. All
indicators show change in colour over some pH range, which varies considerably from one indicator
to another.

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Acid-Base Indicators

The amount of an acid (or a base), which is exactly equivalent chemically to the amount of some
standard base (or an acid), is determined by an acid-base titration. The point of equivalence is
called end point. The solution of a strong acid and strong base will be neutral at the end point
and have a pH of 7 as they are strong electrolytes. However, if either the acid or the base is a
weak electrolyte, the solution at the equivalence point will be either slightly alkaline (pH>7) or
slightly acidic (pH<7). Hence, for an acid-base titration, the correct end point will be characterized
by a definite value of H+ ion concentration (i.e. pH), which depends upon the nature of the acid
and the base and the concentration in the solution.
A large number of acid-base indicators are available which possess different colours according to
H+ ion concentration of the solution. These indicators do not change from predominantly ÂacidÊ
colour to predominantly ÂbaseÊ suddently and abruptly, but within a small interval of pH (generally
about 2 pH units). This is called colour-charge interval of the indicator. The position of the colour-
charge interval in the pH scale varies widely with different indicators. Therefore, for acid base
titrations, an indicator is chosen which shoes a distinct colour change at a pH close to that of
equivalent point.

Acid-base indicator behaviour

The mechanism of acid-base indicator was developed by Ostwald, which offered an explanation
for the colour change with change in pH. All acid-base indicators are weak organic acids or bases,
which posses different colours in unionized and ionized states. If the indicator acid is represented
as HIn and has its ionized form in, then equilibrium in aqueous solution may be represented as :


  ă
HIn  H  In
Unionized Ionized
colour colour

For a basic indicator,


  
InOH  OH  In
Unionised Ionised
colour colour

The unionized molecule has one colour while the ionized ions has another colour.
The equilibrium constant for a weak acid indicator may be written as :

[H  ] [In  ]
K Ind 
[HIn]

where, KInd is known as indicator constant.

[HIn]
or [H ]   K Ind
[In  ]

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Writing the above equation in logarithmic form

[HIn]
log [H  ]  log  KInd
[In  ]

[In + ]
or  log [H ]  ă log KInd + log (  pX = ă log X)
[HIn]

Thus the colour of the indicator, which is determined by the ratio

[In ă ]
is governed by the pH of the solution,
[HIn]

Similarly, for a weak organic base indicator, In OH,

[InOH]
[OH ]   KInd
[In  ]

Kw [In  ]
or [H ]  
K Ind [InOH]

Taking logarithms

Kw [In  ]
log [H  ]  log  log
K Ind [InOH]

[InOH]
or  log [H ]   log Kw  log K In  log
[In  ]

[InOH]
 pH  pKw  p K In  log
[In  ]

[InOH]
or pH  14  p K In  log at 25C
[In  ]

As the pH of the solution changes the colour of the indictor changes. This change is so minute
that it goes unnoticed by thehuman eye. therefore to see the colour change the concentration of
one of the forms should predominate. The solution will have the acid colour (i.e. of HIn form)
when the ratio [HIn] to [In] is approximately 10 and the alkaline colour (i.e. of Ină) when ratio
[Ină] to [HIn] is approximately 10.

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The acid colour will be visible when

[HIn]
 10
[In  ]

Only basic colour will be visible when

[In  ]
 10
[HIn]

Hence the colour interval or indicator pH range is

Indicator pH range = ă 1 + pKInd to 1 + pKInd

Indicator pH range = pKInd  1

This means that the colour change interval of an indictor lies over approximately 2 pH units.
Within this range, the change from one colour to the other another will be visible to human eye.

Acid Base Titration Curves

In acid base titrations, a base is added to an acid successively (or vice versa) and the pH of the
solution is noted after every addition. the plot of pH against the amount of base (or acid) added
is called a titration curve. The shape of the curve depends upon the ionization constants of the
acid and base used in the titration.

(1) Titration of strong acid and strong base

When we add a solution of NaOH to the solution of HCl, the pH progressively increases.

HCl( aq)  NaOH( aq)  NaCl (aq)  H2 O(l)

This is because OHă ions from the base will react with H+ ions of the acid to form water. This
decreases the concentration of H+ ions and therefore pH increases. The pH of the solution increases
only slightly in the beginning until just before the stoichiometric point, there is a sudden jump
in pH. The pH continues to increase after the stoichiometric point but then levels off because of
the presence of excess strong base in the solution. At the equivalence point the pH is 7, but has
increased sharply from 3.5 to 11 just before this point. Any indicator, which has effective range
between pH 3.5 to 11 may be used to detect the equivalence point. For example, phenolphthalein
and methyl orange are good indicators in this range.

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When we tirtate the base (NaOH) with the continuous addition of acid (HCl), the curve obtained
is exactly reversed. The pH decreases slowly in the beginning and near the equivalence point
there is sudden fall through pH = 7 as the concentration of H+ ions increases sharply.

14 14

12 12

10 10

8 8
Equivalence pH Equivalence
6 point 6 point
pH
4 4

2 2

0 10 20 25 30 40 50 0
Volume NaOH added Volume of HCl added (ml)
Tiration curve of strong acid Tiration curve of strong base
(HCl) with a strong base (NaOH) (NaOH) with strong acid (HCl)

(2) Titration of weak acid and a strong base

This type of titration is carried out between acetic acid and sodium hydroxide.

CH3 COOH( aq)  NaOH (aq)  CH3 COONa ( aq)  H2 O (l)

The free H+ ion from the weak acid is neutralized by OHă ions from the base and there is a small
increase in pH. Around the equivalence point large increase in pH is observed. However, the slope
of the curve is not as sleep as in the case of strong base and strong acid titration curve. Sodium
acetate formed after neutralization reacts with 14
OHă ions of water (hydrolysis) and so at the
12
equivalence point the pH is not 7. The H+ ion
concentration decreases and the pH is about 8.7 10
at the equivalence point. By the addition of small 8
amount of NaOH, pH change is observed from pH Equivalence
6 point
about 8.0 to 10.0 near the equivalence point. It is
therefore necessary to use an indicator with pH 4
range on alkaline side. Phenolphthalein is
2
commonly used. Methyl orange cannot be used
because it would give inaccurate indication of 0 5 15 25 35 45 55
Volume NaOH added (ml)
equivalence point.
The pH titration curve of weak acid (CH3COOH) and
strong base (NaOH)

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(3) Titration of weak base and a strong acid

This type of titration is carried out between a weak base such as ammonium hydroxide and strong
acid such as hydrochloric acid.

NH4 OH( aq)  HCl (aq)  NH4 Cl ( aq)  H2 O(l)

The equivalence point is below 7 because the salt (NH4Cl) formed at the neutralization reacts with
water to give H+ ions. The equivalence point lies at about pH 5.3. It is, therefore necessary to use
an indicator with pH range slightly on the acidic side. Methyl orange can be used. Phenolphthalein
is not suitable because its colour change occurs away from the equivalence point.

14

12

10

8
pH
6
Equivalence
4 point

0 5 15 25 35 45 55
Volume NaOH added (ml)

The pH titration curve of weak base (NH4OH) and

strong acid (HCl)

(4) Titration of weak acid and weak base

This type of titration is carried out between a weak acid such as acetic acid (CH3COOH) and weak
base such as ammonium hydroxide (NH4OH).

NH4 OH( aq)  CH3 COOH( aq)  CH3 COONH4( aq)  H2 O(l)

There is no sharp change in the pH during the titration. Hence, no sharp equivalence point can
be obtained with common indicators. However, a mixed indicator, which shows a sharp colour
change over limited pH range may be used.

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14

12

10

8
pH
6

0 5 15 25 35 45 55
Volume NH3 added (ml)

Titration curve of weak base (NH4OH) and

weak acid (CH3COOH)

SOLUBILITY, MOLAR SOLUBILITY AND SOLUBILITY PRODUCT

There are two ways to express a substanceÊs solubility (a) solubility and (b) molar solubility.
(a) The number of grams os solute in one litre of a saturated solution (g/litre) is termed as
solubility.
(b) The number of moles of solute in one litre of a saturated solution (moles / litre) is defined
as molar solubility.
Both these definitions refer to the concentration of saturated solutions at some given temperature
(usually 25Ĉ).
Let us consider solubility of any general salt, AxBy. Let the solubility of this salt be ÂsÊ mol per litre.


 y x
A x B y (s)  xA (aq)  yB ( aq)

xs ys
For saturated solution (at equilibrium),

[A y ] x  [B x ] y
K eq 
[A xB y ]

K eq [A xB y ]  [A y ]x [B x ] y

K sp  [A y ] x [B x ] y (since AxBy is a pure solid)

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where Ksp is called solubility product. The term on right hand side is called solubility product
if the solution is saturated and ionic product if the solution is not saturated (i.e., not at equilibrium).

K sp  ( xs) x  ( yx) y

K sp  x x  y y  s( x  y)

It should be noted that if the ionic product is more than KSP, the equilibrium will shift in
backward direction and some amount of salt is thrown out of solution (precipitation) and finally
an equilibrium is developed in such a way that the ionic product becomes equal to solubility
product. If ionic product is less than KSP, the solution is unsaturated and more of the salt can
be dissolved. If ionic product is equal to KSP, the solution is saturated and if ionic product is more
than KSP, the solution is called super saturated.
From the solubility product principle, we may infer that,

Ć When the ionic product of a salt in solution is equal to its solubility product, the solution is
saturated and the undissociated salt remains in equilibrium with its ions in the solution.

Ć The solubility of a salt in water depends upon other substances (ions) present is water (at
that time) and the solubility product is a constant value (at a given temperature) and is
independent of presence of any other ion present. Like other equilibrium constants such as :
Kp, Kc, Ka & Kb, it is also constant at a certain temperature & can change only when
temperature changes.

Ć The salts like AgCl are regarded as sparingly soluble salts. Some of them are : Ag2SO4,
Ag2CO3, PbCl2, PbCrO4, PbS, ZnS, Al(OH)3, Ca3(PO4)2, BaSO4, CaSO4, MnS etc.

Ksp for Ag2SO4 : Ag 2SO4  2Ag   SO24 

K sp  [2Ag  ] 2 [SO 42  ]

Ksp for Ca3(PO4)2 Ca3 (PO4 )2  3Ca 2   2PO43 

K sp  [Ca 2 ]3 [PO34 ]2

In solubilities of sparingly soluble salts, we will deal with mainly two types of problems : one to
find out soloubility in water if Ksp of a salt is given & vice-versa. Secondly, to find out solubility
of a salt in presence of other (common) ions in water.

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Comparison of solubility product and ionic product

Solubility product Ionic product

It is the product of the concentration of ions of It is the product of the concentration of ions of
the electrolyte each raised to the power of their the electrolyte each raised to the power of their
coefficients in the balanced chemical equation in coefficients in the balanced chemical equation in
a saturated solution a solution at any concentration.
It is applicable to only saturated solutions It is applicable to all types of solutions of any
concentration

It has a constant value for an electrolyte at a Its value is not constant and varies with change
constant temperature in concentration

Example 28

Ksp of calcium iodate Ca(IO3)3 = 6.3 ï 10ă7 at 18ĈC, find the solubility of salt (in gm/L) in
water at 18Ĉ C.
Solution :
Note : Ksp is expressed in concentration units.
In questions, solubility is generally asked (or given) to be expressed in gm/lt.
Now the following equilibrium is established.

Ca(IO3 )2  Ca 2   2IO3

Let x mole/lt be solubility of Ca(IO3)2


 [Ca 2  ]  xM & [IO 3 ]  2 xM

K sp  [Ca 2  ] [IO3 ]2

 6.3 ï 10ă7 = (x) (2x)2

 4x3 = 6.3 ï 10ă7

 x = 5.4 ï 10ă3 M
Now answer is to be expressed in gm/lt.
 solubility = x ï M0
= (5.4 ï 10ă3) ï 390 = 2.106 g/lt

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Example 29
The solubility of BaSO4 in water is 2.3 ï 10ă4 gm/100 mL. Calculate the % age loss in weight
when 0.2 gm of BaSO4 is washed with (a) 1 lt of water (b) 1 lt of 0.01 N H2SO4.
Solution :
(a) Solubility is in general expressed in gm/lt,
so solubility of BaSO4 = 2.3 ï 10ă3 g/lt.
Loss in weight of BaSO4 = amount of BaSO4 soluble.

2.3  10 3
 % loss   100  1.15%
0.2

2
(b) Now 0.01 N H2SO4  0.01 N SO4 ions

2
 0.005 N SO4 ions

2
Now presence of SO4 prior to washing BaSO4 will suppress the solubility of BaSO4 (due to

common ion effect). The suppression will be governed by Ksp value of BaSO4. So first calculate
Ksp of BaSO4.
Solubility of BaSO4 in fresh water = 2 ï 10ă3 g/lt

2.3  103
  Mol/lt  9.85  106 M
233.4

Ksp  [Ba 2  ] [SO42  ]

= (9.85 ï 10ă6)2 = 9.71 ï 10ă11

Now let x be solubility in mol/lt
[Ba2+] in solution = x mol/lt

& [SO24  ] in solution = (x + 0.005) mol/lt

Ionic product = [Ba2+] [SO24  ] = (x) (x + 0.005)

Ksp = Ionic Product at equilibrium (saturation)

 9.11 ï 10ă11 = (x) (x + 0.005)

 x2 + 0.005 x ă 9.71 ï 10ă11 = 0

New neglecting x2 (as x << 1)

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9.71  1011
 x = 1.94 ï 10ă8 mol /lt
0.005

= 1.94 ï 10ă8 ï 233.4 g/lt

= 4.53 ï 10ă8 g/lt
 4.53 ï 10ă6 gm of BaSO4 are washed away.

4.53 ï 10 ă6
 % loss = = 2.26 ï 10ă3 %
0.2

Precipitation of Salts :

For a salt (sparingly soluble) when dissolved in water : AB  A   B

at equilibrium (saturation) K sp  [A  ]  [B ]

When we mix ions or if there be two or more ions in water, we define reaction coefficient (Q),
called as ionic-product (IP) in this case, giving the products of ions in water (ions of soluble salts
& other common ions).

IP is product of ionic concentration due to ions already present in water or from a salt. It may
be & may not be equal to Ksp.

1. If Ionic Product (IP) > Ksp; precipitation takes place till I.P. equals Ksp.

2. If Ionic Product < Ksp ; a precipitate will not be formed and the solution will be unsaturated.

3. If Ionic Product = Ksp ; a precipitate will not form and the solution is saturated in that salt.

(Or we can say that solution is at a critical stage, when precipitation just begins, but actually
has not occurred yet in real sense).

Example 30

A solution contains a mixture of Ag+(0.1M) and Hg 2+

2 (0.l0 M) which are separated by
selected precipitation. Calculate maximum concentration of Iodide ion at which one of
them gets precipitated almost completely. What % age of that metal ion is precipitated ?
Solution :
First determine, which ion starts precipitating.

K sp of AgI
[Iă] required to precipitate AgI =
[Ag  ]

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8.5  1017
  8.5  1016 M
0.1

K sp of Hg 2 I2
[I ] for Hg 2I 2 
[Hg 2+
2 ]

2.5  1026
  5  10 13
0.1

This means that AgI will be precipitated first as [Iă] required for AgI is less.
But when [Iă] reaches 5 ï 10ă13 M then precipitation of Hg2I2 also starts.
So [Ag+] left at that stage is given as :

K sp of AgI 8.5  1017

[Ag  ]    1.7  104 M
ă 13
[I ]Hg I 5.0  10
2 2

% of Ag+ left unprecipitated

1.7  104
  100  0.17%
0.1

 % age of Ag+ = 99.83 %

This means when Hg2I2 starts precipitating, Ag+ is almost precipitated.

Example 31

Freshly precipitated Al & Mg Hydroxides are stirred vigorously in a buffer solution

containing 0.25 mol/lt of NH4Cl & 0.05 mol/lt of NH4OH. Calculate [Al3+] & [Mg2+] in solution.
Kb (NH4OH) = 1.8 ï 10ă5; Ksp (Mg(OH)2) = 8.9 ï 10ă12; Ksp (Al(OH)3) = 6 ï 10ă32.
Solution :
Note that Al (OH)3 & Mg (OH)2 are mixed with buffer which is basic. i.e. [OHă] are already
present in the solution so it will decrease the solubility of Al (OH)3 & Mg(OH)2 in the solution.
At equilibrium, [OHă] will determine the concentration of metal ions in solution.
First calculate [OHă] in the solution using basic buffer equation.

[salt]
pOH = pK b  log
[base]

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 0.25 
  log (1.8 ï 10 ă5 )  log  
 0.05 

pOH = 5.4431 = ă log [OHă]

 [OHă] = 3.59 ï 10ă6 M
Now this controls the following equilibria.
1. Mg(OH)2; Ksp = [Mg2+] [OHă]

8.9  10 12
 [Mg 2  ]   0.69 M
 3.59  106 
2. Al(OH)3 ; Ksp = [Al3+] [OHă]3

6  1032
 [Al3  ]   1.29  1015 M
3.59  10  6

Example 32

The solubility product of CaF2 is 3.9 ï 10ă11 at 25ĈC. What is the solubility (in grams) of this
salt in a litre of 0.1 N NaF solution ?
Solution :
Let the solubility of CaF2 in the presence of 0.1 N NaF be x.


 2 
CaF2  Ca  2F

[Ca2+] = x
[Fă] = 2x + 0.1
Ksp = [Ca2+] [Fă]2 = x (2x + 0.1]2 = 4x3 + 0.4x2 + 0.01 x
Since x is small, x2 and x3 terms would be very-very small and can be neglected.
 0.01 x = 3.9 ï 10ă11

3.9  10 11
x  3.9  10 9
0.01

The smalleness of x justifies the earlier supposition that x3 and x2 is negligible.

Molecular weight of CaF2 = (40 + 38) = 78
Mass of CaF2 per litre = 3.9 ï 10ă9 ï 78 = 3.042 ï 10ă7 g litreă1.

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Example 33

The solubility product (Ksp) of Ca(OH)2 at 25ĈC is 4.42 ï 10ă5. A 500 ml of saturated solution
of Ca(OH)2 is mixed with equal volume of 0.4 M NaOH. How much Ca(OH). How much
Ca(OH)2 in miligrams is precipitated ? [IIT 1992]
Solution :
Let the solubility of Ca (OH)2 in pure water = S moles / litre

Ca(OH)2  Ca 2+  2OH ă
s 2s

Then Ksp = [Ca2+] [OHă]2

4.42 ï 10ă5 = S ï (2S)2
4.42 ï 10ă5 = 4S3
S = 2.224 ï 10ă2 = 0.0223 moles litreă1
 No. of moles of Ca2+ ions in 500 ml of solution = 0.01115
Now when 500 ml of saturated solution is mixed with 500 ml of 0.4 M NaOH, the resultant
volume is 1000 ml. The molarity of OHă ions in the resultant solution would therefore be 0.2 M.

K sp 4.42  105
 [Ca 2+ ]    0.001105 M
[OH ]2 (0.2)2

Thus, No. of moles of Ca2+ or Ca(OH)2 precipitated = 0.01115 ă 0.001105 = 0.010045

Mass of Ca(OH)2 precipitated = 0.010045 ï 74 = 0.7433 g = 743.3 mg

Example 34

Given : Ag(NH3 )+2  Ag+ + 2NH3, Kc = 6.2 ï 10ă8 and Ksp of AgCl = 1.8 ï 10ă10 at 298 K. Calculate

the concentration of the complex in 1.0 M aqueous ammonia.

Solution :

For AgCl 

  
AgCl  Ag  Cl

 Ksp = [Ag+] [Că] ... (i)

Again it is given that

[Ag(NH3 ) 2 ] 

 
 Ag  2NH3 ; K c  6.2  10
8

 1 108
or Ag + + 2NH3 

 [Ag(NH3 ) 2 ] ; K f  
6.2  108 6.2

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[Ag(NH3 )2 ]
 Kf 
[Ag + ][NH3 ]

[Ag(NH3 )2 ]
or [Ag + ] 
K f [NH3 ]2

Since the formation constant of the complex is very high, most of the [Ag+] which dissolves
must be converted into complex and each Ag+ dissolved also requires dissolution of Clă.
 [Clă] = [Ag(NH3)2]+ and let it be c M
Equation (i) becomes

[Ag(NH3 )2 ]
Ksp =
K f [NH3 ]2

c
Ksp = c
K f [1]2

c2 = Ksp ï Kf [1]2

08
= 1.8  1010   (1)2
6.2

1.8  102
c2 = = 0.2903 ï 10ă2
6.2

c = 0.538 ï 10ă1 = 0.0538 M

Example 35

Predict whether a precipitate will be formed or not when equal volumes of 2 ï 10ă6 M BaCl2
solution and 2 ï 10ă5 M Na2SO4 solution are mixed ? The solubility product of barium
sulphate is 1 ï 10ă10.
Solution :

2
Calculation of concentrations of Ba2+ and SO4 ions before mixing.


 2 
BaCl2  Ba  2Cl

 [Ba2+] = 2 ï 10ă6 M

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Similarly, Na2SO4  2Na+ + SO4 

2

  SO2    2  105 M
 4 

Concentration of individual ions in the total solution which is doubled after mixing.

2  106 SO2    2  10
5
[Ba 2  ]   106 M or  105 M
2  4  2

Alternatively,
Let the volume before mixing = x litre
 The volume after mixing equal volumes of the two salts = x + x = 2x litres
Further let the molarity of the resulting solution = M2
Now applying molarity formula to Ba2+ ions.

M1 V1  M2I2
(Before mixing) (After mixing)

2 ï 10ă6 ï x = M2 ï 2x

2  10 6  x 2  106
M2    106
2x 2

Similarly, for SO4  ions

2

M1 V1  M2I2
(Before mixing) (After mixing)

2 ï 10ă5 ï x = M2 ï 2x

2  10 5  x 2  105
M2    105
2x 2

Calculation of ionic product of Ba2+ and SO4  ions

2

 Ionic product of BaSO4 = 10ă6 ï 10ă5 = 10ă11

Since here Ionic product < Solubility product
10ă11 < 10ă10
No precipitate will be formed.

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