UNIT-8

CHEMICAL EQUILIBRIUM

Substances were classified into electrolytes and non-electrolytes by Michael Faraday (1824).

Electrolytes
Compounds which dissociate into ions either in molten state or in solution are called electrolytes.
Electrolytes conduct electricity due to the presence of ions.
Eg: Acids, bases and salts

Electrolytes are classified into strong electrolytes and weak electrolytes

Strong Electrolytes:
The electrolytes which are almost completely ionized in solutions are called strong electrolytes
Eg: Aq: solutions of NaCl, KCl, NaOH, H2SO4, HCl etc.

Weak electrolytes:
The electrolytes which are weakly ionized in solution are called weak electrolytes.
Eg. CH3COOH, NH4OH etc

Non – electrolytes:
Compounds which do not ionize in their solution are called non-electrolytes. They do not conduct
electricity.
Eg: Sugars.

Ionisation of weak electrolytes (Ostwald’s dilution law)

Weak electrolytes are only partially ionized in solutions. As a result a dynamic equilibrium is
present between the ions and un-dissociated molecules

The fraction of the total number of molecules of an electrolyte which dissociate into ions at
equilibrium is called degree of ionisation or degree of dissociation.

Consider a weak electrolyte AB in water. Let ‘C’ be the initial concentrated and α be its degree of
ionistion

Initial concentration +
Equilibrium concentration

Applying law of chemical equilibrium

K= =

= =

For a weak electrolyte ‘α’ is very small. Hence 1- α can be taken as 1

K = Cα2

α2 = K
C
α = K/C

α ∞ 1/ C
So the degree of ionization is inversely proportional to concentration. Therefore as concentration
decreases, the degree of ionization increases. Аs C approaches zero (dilution approaches infinity), the
degree of dissociation approaches unity. This generalization is called Oswald’s dilution law.

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ACIDS AND BASES

There are 3 concepts regarding acids and bases

1. Arrhenius concept of acids and bases

According to Arrhenius concept

An acid is a substance which produce hydrogen ions in its aqueous solution.
A base is a substance which produce hydroxyl ions in its aqueous solution.
Eg:
Substances such as HCl, HNO3, CH3 COOH etc are acids because they give H+ ions in water.

HCl(aq) → H+ + Cl‾(aq)
HNO3(aq) → H+ + NO3‾(aq)

Substance such as NaOH, KOH, NH4OH etc are bases because they give OH‾ ions in water

NaOH (aq) → Na+(aq) + OH‾ (aq)

KOH (aq) → K+(aq) + OH‾ (aq)

Hydronium ions and hydroxyl ions

In aquous solution H+ ion is considered to be present in hydrated form in combination with water
molecules.
H+ + H2O → H3O+

H3O+ ion is called hydronium ion. In aquous solution the hydronium ion is further hydrated to give species
such as H5O2+, H7O3+ etc.

Similarly hydroxyl ion is hydrated to give several species like H 3O2‾, H5O3‾, H7O4‾ etc.

Limitations of Arrhenius theory.

1. The theory fails to explain the behaviour of acids and bases in non-aquous solvents.
2. It cannot explain the acidic character of certain salts like AlCl3, BF3 etc and basic character of
NH3, PH3 etc.

Lowry – Bronsted Concept of Acids and Bases

According to this concept.

An acid is a substance that can donate a proton
A base is a substance that can accept a proton
For example

HCl (aq) + H2O(l) H3O+(aq) + Cl‾ (aq)

Acid Base

HCl (g) + NH3(g) NH4+(g) + Cl‾ (g)

Acid Base
Thus this concept is applicable even in non aqueous medium

Conjugate acid and base pair:

When an acid loses a proton, the residual part has a tendency to gain the proton. Therefore, it
behaves as a base. These acid and base differ by a proton. Such a pair of an acid and a base which differ
by a proton is called a conjugate pair of acid and base.

For example

H2O(l) + NH3(ag) NH4+(aq) + OH‾ (aq)

Acid Base Conjugated Conjugated
acid base

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 In the forward reaction water donates a proton to ammonia (base) and acts as an acid. In the
reverse reactions NH4+ ions donate a proton to OH‾ ions (base) and acts as an acid. Thus H 2O/OH‾ and
NH4+/NH3 are conjugate acid base pairs.

Amphoteric substances

Certain substance like H2O, HCO3‾ etc are capable of donating as well as accepting the protons.
Such substances which can act both as an acid and as a base are called amphoteric or amphiprotic
substances.

Strength of acids and bases:

According to Lowry–Bronsted concept, the strength of an acid is a measure of its tendency to lose
protons and that of a base is a measure of its tendency to gain protons. Α strong acid would have large
tendency to donate protons and a strong base have a strong tendency to gain protons.

The conjugate base of a strong acid would be a weak base. Similarly, conjugate base of a weak
acid would be a strong base.

Eg: HCl + H 2O H2O+ + Cl‾

Strong acid weak base

CH3–COOH + H2O H3O+ + CH3–COO –

weak acid strong base

Limitations of Lowery–Bronsted concept

(1) It cannot explain the reaction between acidic oxide like CO2, SO2, SO3 etc with basic oxides like
CaO, MgO etc.
Eg: CaO + SO3 → CaSO4

(2) This theory cannot explain the acidic properties of substances like BF 3, ΑlCl3 etc which do not
contain hydrogen.

Lewis concept of acids and bases [Electronic concept]

According to Lewis concept

Αn acid is a substance which can accept a pair of electrons.
Α base is a substance which can donate a pairs of electrons

For example reactions between BF3 and NH3 can be considered as an acid – base reaction

F3B + ‫׃‬NH3 → F3B ‫ ׃‬NH3

Lewis acid Lewis bases

Here BF3 is a Lewis acid because it accepts a pairs of electrons. NH 3 is a Lewis base because it
donates a pair of electrons.

Lewis acids

Any substance which has an empty orbital that can accommodate a pair of electrons can act as Lewis
acid.
The following species can act as Lewis acids.
(1) Molecules having an atom with incomplete octet.
Eg: BF3, BCl3, AlCl3, FeCl3 etc.
(2) Simple cations like Ag+, Cu2+, Fe3+ etc.
(3) Molecules having central atom with vacant d-orbitals like SnCl4, SiF4 etc.
(4) Molecules containing multiple bonds. Eg CO2, SO2 etc.

Lewis bases
Any substance which has an unshared pair of electrons can act as a Lewis base. The following
species can act as Lewis bases.

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 (1) Neutral molecules like NH3, PH3, RNH2, R–OH, etc containing at least one lone pair of electrons
on the central atom.
(2) All negative ions like F¯, Cl¯, Br¯, I¯, OH¯, CN¯ etc.

All Bronsted bases are also Lewis bases. But all Bronsted acids are not Lewis acids (eg HCl, H 2SO4 ) etc)

Advantages and Limitations of Lewis concept:

Lewis concept is more general than Arrhenius as well as Bronsted concepts. It includes all the
coordination compounds and co-ordination reactions. But it has the following draw backs.

(1) It does not help to assign the relative strengths of acids and bases
(2) It does not explain the behavior of protonic acids such as HCl, H 2SO4 etc.
IONISATION OF ACIDS AND BASES

A strong acid ionise almost completely in solutions. But weak acids are not completely ionised in
solutions. Thus an equilibrium is present between ionized and unionised molecules. The relative strengths
of weak acids can be compared in terms of their ionisation constants (equilibrium constant)

Consider the ionisation of a weak acid HA

HA (aq) + H2O(l) H3O+(aq) + Α‾ (aq)
Applying law of chemical equilibrium
K = [H3O+] [Α-]
[HΑ] [H2O]
But in dilute solution, the concentration of water remains constant.

Therefore K [H2O] = [H3O+] [Α‾]

HΑ

Ka = [H3O+] [Αˉ]
[HA]

Here Ka is called ionization constant of acid or dissociation constant . The value of ionisation
constant gives an idea about the relative strength of the acid. Larger the value of Ka stronger is the acid.

[Eg: K CH 3 −COOH = 1.8 x 10 – 5 at 298 k

K HF = 6.7 x 10 – 4 at 298 k.
Here K HF > K CH −COOH . Therefore HF is stronger acid than CH3–COOH]
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Calculation of [H3O+] and degree of dissociation

From the knowledge of Ka, it is possible to calculate the hydronium ion concentration and degree
of dissociation.

For example consider the ionisation of acetic acid is aqueous solution. Let ‘C’ be the initial concentration
and α be the degree of ionisation.

CH3–COOH + H2O CH3 – COO- + H3O+

Initial conc. C 0 0
Con. at equalibrium C (1 – α) Cα Cα

Ka = [CH3–COO¯] [H3O+]
[CH3–COOH]

(For dilute solution, the concentration of water remains constant)

Ka = Cα Cα
C (1–α)

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 Ka = Cα2
1–α

For a weak electrolyte, the value of α is very small and hence 1-α may be taken as one.

Therefore Ka = Cα2
Or

Ka
 =
C

From the degree of ionisation, hydronium ion concentration can be calculated.

Ka
[H3O+] = Cα = C = KaC
C
Dissociation constants of bases

The relative strength of bases are also compared in terms of their dissociation or ionisation
constants. The ionisation constant Kb for a weak base B can be represented as.

B+(aq) + H2O(l) BH+(aq) + OH‾(aq)

Kb = [BH+][OH‾]
[B+]

Larger the value of ionisation constant Kb for a base, stronger is the base.

Kb
Similarly degree of dissociation α =
C
Also [OH‾] = Cα = K bC
Poly protic acids (Poly basic acids) and poly acidic bases

Acids having only one ionisable hydrogen are known as monoprotic acids. Eg: HCl, CH3–
COOH, HCl etc
HCl → H+ + Cl‾

But the acids which have more than one ionisable hydrogen atoms are known as polyprotic acids.
Eg: H3PO3, H2SO4, oxalic acids etc

H3PO4 ionises in 3 steps.

H3PO4 H+ + H2PO4‾ Ka1 = [H+] [H2PO4‾]

[H3PO4]

H2PO4‾ H+ + HPO42‾ Ka2 = [H+] [HPO42‾]

[H2PO4‾]

HPO42‾ H+ + PO43‾ Ka3 = [H+] [PO43‾]

[HPO42‾]

Here Ka1, Ka2 and Ka3 are called 1st , 2nd and 3rd ionisation constants.

Ka1 > Ka2 > Ka3

Similarly polyacidic bases also ionises in stages and the corresponding ionisation constant are Kb 1,
Kb2 , Kb3 etc.
Eg: Ethylene diamine.

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Common ion effect:

The degree of ionization of a weak electrolyte is suppressed by the addition a strong electrolyte
containing a common ion. This effect is called common ion effect.

For example consider the ionization of a weak acid CH3-COOH.

CH3–COOH CH3–COO– + H+
CH3–COONa CH3COO– + Na+
common ion
If sodium acetate is added to the solution, the concentration of acetate ion increases. This will shift
the equilibrium in backward direction according to Le-Chatlier’s principle. Thus the degree of ionization
decreases.

The degree of ionization is also suppressed by the addition of H + in the form of dil HCl.

Other examples:
(1) The dissociation of the weak electrolyte NH4OH is suppressed by the addition of NH4Cl which
contains the common ion NH4+.

NH4OH [NH4+] + OH-

NH4Cl [NH4+] + Cl-
common ion
Ionic product of water:

Water is a weak electrolyte. Therefore it undergoes ionization to a very small extent according to
the equation.

H2O(l) H+(aq) + OH–(aq)

The ionization constant of water may be given as

=
The concentration of hydrogen and hydroxyl ions at 298K are both equal to 10 -7M and the
molarity of pure water is 1000/18= 55.55M.

Therefore
Ka = = 1.8 10–16

Since water dissociates only slightly the concentration of undissociated molecules can be taken as constant.

Therefore Ka [H2O] = [H+] [OH–]

Kw = [H+] [OH–]

The constant Kw is called ionic product of water. Substituting the value of Ka and concentration of water
in the above equation

Kw = [H+] [OH–] = 10–14

[H+] ion concentration and pH

Sorensen in 1909 suggested a convenient method for expressing the H + ion concentration of a
solution called pH. The pH of a solution is defined as the negative logarithm of the H + ion concentration
expressed in mol L-1. [activity of hydrogen ion]

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 pH = –log [H+]

In neutral solution, [H+] [OH-] = 1 x 10–7 mol L–1 at 298K

Therefore pH of neutral solution = –log 1 x 10–7 = 7
In acidic solutions, pH is less than 7 and in basic solutions pH is greater than 7. The pH value generally
ranges from zero to 14.

pH decreases with increase of temperature.

pH scale being logarithmic, a change of one unit in the pH value corresponds to a ten fold change in
H+ ion concentration.

Relation between pH, pOH and pKw

Just like pH value, the negative logarithm of the OH- ion concentration is called pOH.
–log[H+] = pH and -log[OH–] = pOH
Similarly –logKa = pKa and –logKb = pKb
Similarly –logKw = pKw
But, [H+] [OH–] = Kw = 1 x 10–14
On taking negative logarithm
–log[H+] + –log[OH–] = –logKw = –log 1 x 10–14
or
pH + pOH = pKw = 14

SALT HYDROLYSIS

Salt hydrolysis is the interaction of water with cations and anions of a salt to produce acidic or
alkaline solutions. Salt hydrolysis can be considered as reverse of neutralization.

If a salt B+A− reacts with water, the reaction is represented as

B+A− + H2O H+A− + B+OH−

Acid Base

The resulting solution will be acidic or alkaline depending upon the relative strength of HA and
BOH. If the acid is strong, then the solution will be acidic. If the base is strong, then the solution will be
basic.

The salt formed by a strong acid and strong base do not undergo hydrolysis and the resulting
solution is neutral.

Hydrolytic constant (Kh)

The general equation involving hydrolysis of a salt BA can be represented as

BA + H2O HA + BOH
HABOH
BAH 2O
Applying low of chemical equilibrium, K =

HABOH
BA
K[H O] =
2

Here K[H2O] = Kh which is known as hydrolytic constant.

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Degree of hydrolysis (h)

The fraction of the total salt that is hydrolysed at equilibrium is called degree of hydrolysis(h).
Number of moles of salt hydrolysed
h = ------------------------------------------
Total no of moles of the salt taken.

1. The hydrolysis of salt of a strong acid and weak base

The salts belonging to this type are NH4Cl, NH4NO3, CuSO4, AlCl3, FeCl3 etc. This type of
salts produce acidic solution on hydrolysis. This type of hydrolysis is also called cationic hydrolysis.

For example consider the hydrolysis of NH4Cl

NH4+ + Cl− + H2O NH4OH + H+ + Cl−

HCl being strong acid it is completely ionized. However NH 4OH is a weak base and ionizes
only slightly. Hence the resultant solution has large H+ ion concentration and it will be acidic in nature.

Hydrolysis constant:

Let BA is the salt of strong acid HA and weak base BOH. Its hydrolysis can be represented as
BA + H2O BOH + HA
B+ + A− + H2O BOH + H+ + A−
B+ + H2O BOH + H+

Applying law of mass action K = [H+] [BOH]

[B+] [H2O]

K[H2O] = [H+] [BOH] = Kh

[B+]
Where the constant Kh is called the hydrolysis constant of the salt.

For the dissociation of a weak base, we can write.

BOH B+ + OH−
Kb = [B+] [OH-]
[BOH].

Multiply with Kh,

Kb x Kh = [B+] [OH−] x [H+] [BOH]
[BOH] [B+]

= [H+] [OH−] = Kw.

Kh = Kw
Kb

Therefore weaker the base, greater is the hydrolysis constant of salt.

Degree of hydrolysis:

Let the initial concentration of salt is C and h is the degree of hydrolysis.

B+ + H2O BOH + H+
c(1-h) ch ch

Kh = ch ch = ch2
c(1-h) 1-h

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If the degree of hydrolysis is very small, (1-h) may be taken as equal to unity.

Kh
. . . Kh = ch2 or h =
C
Therefore the degree of hydrolysis is inversely proportional to square root of the concentration.

But Kh = Kw
Kb.
Therefore
Kw
h=
Kb  C

Calculation of pH

[H+] = Ch

Kh
= C = Kh.C
C

Kw.C
=
Kb
pH = - log [H+]

Kw.C
= -log
Kb
= ½ [-log Kw – log C + log Kb]

pH = ½ [pKw – log C – pKb]

pH = 7 – ½ [log C + pKb]

(2) Salt of weak acid and strong base

The salts belonging to this type are CH3–COONa, Na2CO3, KCN etc. This type of salts produce
alkaline solution on hydrolysis. This type of hydrolysis also called anionic hydrolysis.

For example consider the hydrolysis of CH3–COONa,

CH3 – COO– + Na+ + H2O ═ CH3 – COOH + Na+ + OH–

NaOH being strong base, it is completely ionised. However CH 3–COOH is weak acid and ionize
only slightly. Hence the resultant solution has large OH – concentration and it will be basic in nature.

Hydrolysis constant
Kh = Kw
Ka
Degree of hydrolysis

Kh
h =
C

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 Kw
h =
Ka x C
Calculation of pH
pH = ½ [ pKw + pKa + log C]

pH = 7 + ½ [pKa + log C]

(3) Hydrolysis of salt of weak acid and a weak base

The salts belonging to this type are CH3–COONH4, (NH4)2CO3, Ca3 (PO4)2 etc. Here both cation and
anion of the salt participate in hydrolysis. This type of hydrolysis produce acidic or basic or even neutral
solution depending upon the relative strength of acid and base that are formed on hydrolysis. Consider the
hydrolysis of CH3–COONH4.
CH3–COO– + NH4+ + H2O → CH3–COOH + NH4OH

Here both CH3–COOH and NH4OH are weak and are feebly ionised. Therefore the solution is almost
neutral. This type of hydrolysis is also called cationic as well as anionic hydrolysis.

Hydrolysis constant
Kh = Kw
Ka x Kb
Degree of hydrolysis

h = Kh
Kw
h =
Ka x Kb
Calculation of pH

pH = ½ [ pKw + pKa – pKb]

pH = 7 + ½ [pKa – pKb]

4. Salts of strong acid and strong base.

The salts belonging to the type are NaCl, KCl, NaNO3, BaCl2 etc. These type of salts do not
undergo hydrolysis. Hence their aqueous solutions are neutral.

NaCl + H2O → Na+ + Cl– + H+ + OH–

When dissolved in water the ion Na+ and Cl- have no tendency to react with water. As a result the
concentration of H+ and OH- remains unchanged and the solution is neutral.

Buffer solutions

A solution which can resist the change in pH on addition of small amount of acid or base is called
a buffer solution. The ability of buffer solution to resist change in pH on addition of acid or base is called
buffer action.

Buffer solutions are of different types.

1. Strong acid buffers

A solution of strong acid (nitric acid or HCl ) of reasonable concentration (~ 0.1M) can act as a
buffer with a low pH. The addition of a small amount of acid or base will have negligible effect on the pH
of the solution.

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2.Strong base buffers

A strong base such as NaOH, KOH etc at high concentration can act as a buffer with a high pH.
The addition of small amount of acid or base has negligible effect on pH of solution.

3.Buffer solution of weak acid and its salt

A solution of weak acid and its salt with strong base can act as a buffer solution. For example a
solution of acetic acid and sodium acetate can act as a buffer. This solution contains a large amount of
acetate ions and a large amount of un-dissociated acetic acid molecules.

CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)

CH3COONa(aq) → CH3COO-(aq) + Na+(aq)
When a small amount of HCl is added to this solution the H + ions will combine with CH3COO-
ions of buffer to form weakly ionized acetic acid molecules.

CH3COO-(aq) ) + H3O+(aq) CH3COOH(aq + H2O(l)

On the other hand if small amount of NaOH is added to the buffer solution, the OH - ions will
combine with H3O+ ions in the buffer solution to form unionized water molecules. The decrease in
concentration of H3O+ is restored by the greater ionization of acetic acid.

H3O+ + OH- → 2 H2O

CH3COOH(aq) + H2O(l) → CH3COO-(aq) + H3O+aq)

Therefore pH of the solution remains unchanged.

4.Buffer of weak base and its salt

A solution of weak base and its salt with strong acid can act as a buffer solution. For example a
solution of NH4OH and NH4Cl can act as a buffer. This solution contains a large amount of ammonium
ions and a large amount of un-dissociated ammonium hydroxide molecules.
NH4OH(aq) NH4+ + OH-
NH4Cl(aq) → NH4+(aq) + Cl- (aq)
When a few drops of HCl are added, the additional H3O+ ions are neutralized by OH- ions present
in the buffer.
OH- (aq) + H3O+(aq) → 2 H2O(l)

The decrease in concentration of OH- is restored by the greater ionization of NH4OH. On the other
hand when a few drops of NaOH solution are added, the OH - ions will combine with NH4+ ions to form
weakly dissociated NH4OH.

NH4+(aq) + OH- (aq) NH4OH(aq)

Therefore pH of the solution remains unchanged.

pH of buffer solutions [Henderson – Hasselbalch equation]

pH of buffer solutions is calculated by applying Henderson-Hasselbalch equation. Consider an

acidic buffer consisting of weak acid HA and its salt NaA

HA + H2O H3O+ + A-
NaA → Na+ + A-
Ka = [H3O+][A-]
[HA]

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 Since HA is weakly dissociated, the concentration of HA can be taken equal to the initial
concentration of the acid. Since NaA is completely ionized, concentration of A- can be taken equal to the
con. of NaA(salt).

Ka = [H3O+][Salt]
[Acid]

[H3O+] = Ka [Acid]
[Salt]

-log[H3O+] = -logKa - log [Acid]

[Salt]

pH = pKa + log [Salt]

[Acid]

Similarly for basic buffers,

pOH = pKb + log [Salt]

[Base]

Buffer capacity

The capacity of a buffer to resist change in pH on addition of small amounts of acid or base is
called buffer capacity. It is measured in terms of the number of moles of monobasic acid or monoacidic
base required to change the pH of one litre of a buffer solution by 1 unit.

Importance of buffer solutions

Buffer solutions play an important role in many industrial processes such as electroplating,
manufacture of medicines etc. Many biological fluids such as blood have definite pH which is maintained
by buffer action of many substances. The pH of blood is maintained by buffer action of carbonic acid
(H2CO3), bicarbonate ions(HCO3-) and carbon dioxide.

Solubility product

The solids having solubility greater than 0.1M are classified as soluble solids, those having
solubility between 0.01M and 0.1 M are called slightly soluble and those having solubility less than 0.01 M
are called sparingly soluble solids. Salts like AgCl, PbCl2 , BaSO4 etc are sparingly soluble salts

In a saturated solution of a sparingly soluble salt, there is a dynamic equilibrium between the
unionised salt and the ions of the dissolved salt.

For example , in the case of AgCl the following equilinbrium exists.

AgCl Ag+ + Cl-

Applying the law of mass action to this equilibrium, we get

K = [Ag]+[Cl-] where K is the equilibrium constant.

[AgCl]

Since the solution is saturated, the concentration of un-ionised salt remains a constant. Hence the above
equation can be expressed as;

K[AgCl] = Ksp , a constant

Or Ksp = [Ag+][Cl-]

Where, the constant Ksp is known as the solubility product of the salt AgCl.

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 Solubility product of an electrolyte is defined as the product of the concentration of its ions in a
saturated solution. It is a constant at a given temperature but usually increases with increase in temperature.

In general , for a sparingly soluble salt of the type AxBy, the solubility product is given as

AxBy xA+ + yB- Ksp = [A+]x [B-]y

Similarly, the solubility product expression of some common sparingly soluble salts are.

PbCl2 Pb2+ + 2Cl- ; Ksp = [Pb2+] [Cl-]2

BaSO4 Ba2+ + SO42- ; Ksp = [ Ba2+][ SO42-]

Ca3(PO4)2 3Ca2+ + 2PO43- ; Ksp = [Ca2+]3[ PO43-]2

Relationship between solubility and Ksp

Consider a salt AxBy, which ionizes as

AxBy x A+ + y B-

Thus one mole of the salt gives ’x’ moles of A + and ‘y’ moles of B-. Let ‘S’ be the solubility of the
salt. Then S moles of the salt give Sx moles of A+ and Sy moles of B-

Ksp = (Sx)x (Sy)y = xx.yy.Sx+y ie Ksp = xx. yy. Sx+y

Thus if the solubility product of a salt is known , its solubility ‘S’ can be calculated.

Applications of solubility product

In a saturated solution, the ionic product is equal to the solubility product. If the ionic product is
less than the solubility product, the solution will be unsaturated and hence more of the salt will dissolve. On
the other hand, if the ionic product is greater than the solubility product, the solution will be super saturated
and hence crystallization of the salt will take place.

(i) In a saturated solution, Ionic product = Ksp

(ii) In an unsaturated solution, Ionic priduct < Ksp
(iii) In a super saturated solution, Ionic product > Ksp
This concept of solubility product finds a number of applications in analytical chemistry.

1. Predicting precipitation in ionic reactions

During ionic reactions, precipitation of the salt will take place when the product of the ionic
concentration exceeds its Ksp value.

2. Purification of common salt

On passing HCl gas through an impure saturated solution of NaCl leads to the precipitation of the
pure salt. Here the Cl- ion concentration increases and thus the ionic product value exceeds the solubility
product. The impurities will remain in solution.

3. Salting out of soap

Soap is sodium salts of higher fatty acids. From the soap solution, solid soap is precipitated out by
adding the salt NaCl. Here the Na+ ion concentration increases and hence the ionic product exceeds the
solubility product of soap. Therefore soap precipitates out from the solution.

4. In qualitative analysis
In qualitative analysis metal ion such as Pb2+ ,Cu2+ ,Zn2+ etc are precipitated and separated out. It
is based on the difference in the solubility products of their sulphides.

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