COMMON ION EFFECT:

Let AB to the weak electrolyte. Considering its dissociation,

AB ↔ A+ + B-

and applying law of mass action we have

K = [A+][B-]/[AB]

The equilibrium constant, K, has a definite value at any given temperature. If

now another electrolyte furnishing the A+ and B- ions be added to the above
solution. It will increases the concentration of either A+ ions or B- ions
(whichever has been added) and in order that K may remain constant, the
concentration of AB must increases, i.e., the equilibrium will shift to the left
hand side.

In other words, the degree of dissociation of an electrolyte (weak) is

suppressed by the addition of another electrolyte (strong) containing a
common ion. This is termed as common ion effect. Acetic acid is a weak
electrolyte and its ionization is suppressed in presence of a strong acid (H+
ion as common ion) or a strong salt like sodium acetate (acetate ion as
common ion). Similarly, the addition of NH4Cl or NaOH to NH4OH solution will
suppress the dissociation of NH4OH due to common ion either NH-4 or OH-.

As a result of common ion effect, the concentration of the ion not in common
in two electrolytes, is decreased. The use of this phenomenon is made in
qualitative analysis to adjust concentration of S2- ions in second group and
OH- ion concentration in third group of analysis.

Ionic Product of Water:

Pure water is a very weak electrolyte and ionises according to the equation

H2O ↔ H+ + OH-

Applying law of mass action at equilibrium, the value of dissociation constant,

K comes to

K = [H+] [OH-]/[H2O]

or [H+][OH-] = K[H20]

Since dissociation takes place to a very small extent, the concentration of

undissociated water molecules, [H20], may be regarded as constant. Thus,
the product #[H20] gives another constant which is designated as Kw.

So, [H+][OH-] = Kw

The constant, Kw, is termed as ionic product of water.

The product of concentrations of H+ and OH- ions in water at a particular
temperature is known as ionic product of water. The value of Kw increases
with the increase of temperature, i.e., the concentration of H + and OH- ions
increases with increase in temperature.

Ionic Product of Water

The Ionic Product of Water, Kw, is the equilibrium constant for the reaction in which
water undergoes an acid-base reaction with itself. That is, water is behaving
simultaneously as both an acid and a base.

H2O(l) + H2O(l) = H3O+(aq) + OH-(aq)

Kw = [H3O+(aq)][OH-(aq)]

At 298 K, the value of Kw is 1 x 10-14 mol2 dm-6. This makes the concentration of H+ ions
equal to 1 x 10-7 mol dm-3, and therefore the pH is 7. This is defined as 'neutral'.

From the above equilibrium expression, taking -log10 throughout

pKw = pH + pOH = 14

Ionic Product does not apply only to water. It applies, for example, to the equilibrium in
liquid ammonia:

NH3 + NH3 = NH2- + NH4+

Salt Hydrolysis:

Pure water is a weak electrolyte and neutral in nature, i.e., H+ ion concentration is
exactly equal to OH" ion concentration

[H+] = [OH-]

When this condition is disturbed by decreasing the concentration of either of the two
ions, the neutral nature changes into acidic or basic. When [H+] > [OH-], the water
becomes acidic and when [H+] < [OH-], the water acquires basic nature. This is
exactly the change which occurs during the phenomenon known as salt hydrolysis.
It is defined as a reaction in which the cation or anion or both of a salt react
with water to produce acidity or alkalinity.

Salts are strong electrolytes. When dissolved in water, they dissociate almost
completely into ions. In some salts, cations are more reactive in comparison to
anions and these react with water to produce H+ ions. Thus, the solution acquires
acidic nature.

M+ + H2O ↔ MOH + H+

Weak base
In other salts, anions may be more reactive in comparison to cations and these react
with water to produce OH- ions. Thus, the solution becomes basic.

A- + H2O ↔ HA + OH-

Weak acid

The process of salt hydrolysis is actually the reverse of neutralization.

Salt + Water ↔ Acid + Base

If acid is stronger than base, the solution is acidic and in case base is stronger than
acid, the solution is alkaline. When both the acid and the base are either strong or
weak, the solution is generally neutral in nature.

As the nature of the cation or the anion of the salt determines whether its solution
will be acidic or basic, it is proper to divide the salts into four categories.

(i) Salt of a strong acid and a weak base.

Examples: FeCl3, CuCl2, AlCl3, NH4Cl, CuSO4, etc.

(ii) Salt of a strong base and a weak acid.

Examples: CH3COONa, NaCN, NaHCO3, Na2CO3, etc.

(iii) Salt of a weak acid and a weak base.

Examples: CH3COONH4, (NH4)2CO3, NH4HCO3, etc.

(iv) Salt of a strong acid and a strong base.

Examples: NaCl, K2SO4, NaNO3, NaBr, etc.

ACID-BASE NEUTRALISATION-SALTS

When aqueous solutions of hydrochloric acid and sodium hydroxide are mixed in the
proper proportion, a reaction takes place to form sodium chloride and water.

HCl(aq) + NaOH(aqr) ↔ NaCl(aq) + H2O(l)

Sodium chloride

Such a reaction is termed neutralisation because both acidic (H+) and basic (OH-)
properties are eliminated during the reaction. The hydrogen ion, which is responsible
for the acidic properties, has reacted with the hydroxyl ion which is responsible for
the basic properties, producing neutral water. The Na+ and CI- ions have undergone
no chemical change and appear in the form of crystalline sodium chloride upon
evaporation of the solution. Sodium chloride is an example of the class of compounds
called salts.

H+(aq) + OH-(aq) ↔ H2O(l)

Thus, the neutralisation of a base with an acid involves the interaction between OH-
and H+ ions.

The reaction between an acid and a base to form salt and water is termed
neutralisation.

THEORY OF INDICATORS:

Selection of suitable indicator or choice of indicator

The neutralisation reactions are of the following four types:

(i) A strong acid versus a strong base. )

(ii) A weak acid versus a strong base. (Fig. 10.2)

(iii) A strong acid versus a weak base. (Fig. 10.3)

(iv) A weak acid versus a weak base. (Fig. 10.4)

In order to choose a suitable indicator, it is necessary to understand the pH

changes in the above four types of titrations. The change in pH in the vicinity of
theequivalence 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. The titration curves of the above four types of
neutralisation reactions are shown in Fig. 10.1, 10.2, 10.3 and 10.4.

In each case 25 mL of the acid (N/10) has been titrated against a standard solution
of a base (N/10). Each titration curve becomes almost vertical for somedistance
(except curve 10.4) and then bends away again. This region of abrupt change in pH
indicates the equivalence point. For a particular titration, the indicator should be
so selected that it changes its colour within vertical distance of the curve.

(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 phenolphthalein (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.

THEORY OF INDICATORS:

Selection of suitable indicator or choice of indicator

The neutralisation reactions are of the following four types:

(i) A strong acid versus a strong base. (Fig. 10.1)

(ii) A weak acid versus a strong base. (Fig. 10.2)

(iii) A strong acid versus a weak base. (Fig. 10.3)

(iv) A weak acid versus a weak base. (Fig. 10.4)

In order to choose a suitable indicator, it is necessary to understand the pH

changes in the above four types of titrations. The change in pH in the vicinity of
theequivalence 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. The titration curves of the above four types of
neutralisation reactions are shown in Fig. 10.1, 10.2, 10.3 and 10.4.

In each case 25 mL of the acid (N/10) has been titrated against a standard solution
of a base (N/10). Each titration curve becomes almost vertical for somedistance
(except curve 10.4) and then bends away again. This region of abrupt change in pH
indicates the equivalence point. For a particular titration, the indicator should be
so selected that it changes its colour within vertical distance of the curve.

(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 phenolphthalein (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. weak base:

pH curve of weak acid and weak base indicates that there is no vertical part and
hence, no suitable indicator can be used for such a titration.

Manufacture of sodium bicarbonate (baking soda):

In Solvay's soda process. CO2 gas is passed through ammonical brine to precipitate
out NaHCO3.

NH4OH + CO2 → NH4HCO3

 NH4HCO3 + NaCl → NaHCO3 + NH4Cl

NaHCO3 is precipitated first because of its lower solubility product as compared to

those of NH4Cl, NH3HCO3 and NaCl.

Thus, baking soda (NaHCO3) can be quantifiably estimated