IONIC EQUILIBRIUM

1. SYLLABUS
Acids and Bases, pH, Common ion effect, Buffer solutions, Hydrolysis of salts and Solubility Product.

2. IONIZATION OF WATER
Water is a weak electrolyte. It does not dissociate completely, the undissociated water and the
dissociated H+, OH– remain in the equilibrium. Let us take pure water whose density is 1 gram/c.c.
and hence its concentration would be (1000/18 = 55.55 M). Let the degree of dissociation of water
be .

2H2O( ℓ ) □ □ □ H3 O+ + OH–
C C
[H3O ][OH ]

Keq  

[H2O]2

K eq [H 2O(ℓ)]  [H 3O ][OH ]

Since conc. of pure water remain constant

K eq k  [H 3O ][OH ]

Kw  [H3O ][OH ]

Kw  dissociation constant of water at 25°C, K w comes out to be 1  10–14 mol2/lit2.

Kw depends upon temperature dissociation of water gives equal no. of H 3O+ and OH– ions.

11014  [H3O ]2  [OH ]2

So [H3O ]  [OH ]  107 mole/litre

pH = –log [H 3O+]
= – log [10–7] = 7.
pOH = – log [OH–] = – log 10–7 = 7.
 Chemistry : Ionic Equilibrium

Note: In case of water

[H3O+]w [OH–]w = 10–14.
But in case of acidic or basic solution.
[H O+] [OH–] = 10–14, where [H O+] and [OH–] are the conc. of [H O+] and [OH–] totally
3 T T 3 T T 3
present in the solution.
pH Scale
The pH of a solution is the negative logarithm (to the base 10) of the concentration (in moles per
litre) of hydrogen ions which it contains.
pH = –log10 [H O+]
3
pOH = –log [OH–]
10

pkw = –log10 [Kw]

Kw = [H+] [OH–]
taking –ve log10 both side
–log Kw = –log [H 3O+] + [– log (OH–)]
pKw = pH + pOH
14
at 25°C, Kw = 110 , pKw = 14
pH + pOH = 14
Kw = is also called as auto protolysis constant, it increases with temperature.
The value of Kw decides the range of pH scale. Since value of equilibrium constant depends on
temperature only so Kw is only a function of temperature only. Since value of Kw decides the length
of pH scale so change in temperature should be compensated by the callibration of pH scale in order
to obtain the correct result. Illustration (1) will help in understanding the above said concept.
Ionic product of water (Kw) increases with temperature
Kw2
log H  T2  T1 
=   and ionization of water is endothermic
Kw1 2.303R  T1T2 

i.e. H > 0
so, Kw2 > Kw1

Illustration 1 : The pH of a solution at 60°C is 7. The nature of solution will be

(a) acidic (b) Basic (c) Neutral (d) None of these
Solution : If the temeprature of pure water sample is increased the value of Kw will increase and
pKw
pKw will decrease, as a result of which the neural point i.e. will be less than 7. So
2
solution of pH = 7 will be basic.
Illustration-2 The K for 2H O H O+ + OH– changes from 10–14 at 25°C to 9.62  10–14
w 2 3
at 60°C. What is pH of water at 60°C ? What happens to its neutrality ?
Solution: Kw for H2O at 25°C = 10–14
 [H+] [HO–] = 10–14 ( K w = [H+] [OH–])
 [H+] = 10–7 M  pH = 7
NowK w for H 2O at 60°C = 9.62  10–14
 [H+] = [OH–] = 9.62  10–14
For pure water [H+] = [OH–]

 [H+]2 = 9.62  10–14  [H+] = (9.62 1014 ) = 3.10  10–7 M

 pH = – log H+ = – log 3.10  10–7,
pH = 6.51
Thus, pH of water becomes 6.51 at 60°C but the nature is neutral since calculation for
pure water has been made, i.e., pH scale at 60°C becomes in between 0 to 13.02.

3. CALCULATION OF pH OF SOLUTIONS
3.1 CALCULATION OF pH OF STRONG ELECTROLYTES (STRONG ACIDS OR
STRONG BASES)
Step :
(i) Write the balanced chemical equation of the dissociation of strong acid and strong base
(ii) Calculate the molarity of H+ or OH–
(iii) Take –ve logarithm of [H+] or [OH–] in order to find the pH or pOH

Illustration-3 Calculate the pH of 10–3 M HCl solution.

Solution : Step I : Dissociation of HCl
HCl  H+ + Cl–
1 mole of HCl produces 1 mole of H+ upon dissociation
Step II : So molarity w.r.t. to HCl = molarity w.r.t. H+
[H+] = 10–3
Step III : pH = – log [H+] = – log 10–3 = 3

Illustration-4 Calculate pH of 10–4 M NaOH soluton.

Solution :
Step 1 : Dissociation of NaOH
NaOH  Na+ + OH–
1 mole of NaOH upon dissociation produces 1 mole of OH–
So molarity w.r.t. NaOH = molarity w.r.t. OH–
Step II : [OH–] = 10–4
Step III: pOH = – log [OH–] = – log 10–4 = 4
pH = 14 – pOH = 10
 Chemistry : Ionic Equilibrium

Illustration-5 Calculate pH when 9.8 g H2SO4 is dissolved in 2 litre of solution

Solution : Molarity w.r.t. H SO = Number of moles of H2SO4

2 4
Volume of solution in litres

9.8 / 98 1
= = M
2 20
Step I : 1 mole of H2SO 4 upon dissociation produces 2 moles of H+
Step II : So molarity w.r.t. to H+ = 2 × Molarity w.r.t. H 2SO 4
1 1
= 2 = = 0.1
20 10
Step III : pH = – log [H+] = – log 0.1 = 1

3.2 CALCULATION OF pH OF MIXTURES OF STRONG ACID AND STRONG

BASE
Step I : If strong acid and strong base is present in the mixture they will react i.e. the constituents
are reactive.
Step II : Write a balanced chemical equation of the neutralization reaction.
Step III : If the amounts present are in accordance with the stoichiometry then the pH of solution
will be equal to 7 i.e. solution will be neutral.
Step IV : If the amount present are not in accordance with the stoichiometry then make the problem
of pH of strong acid or strong base as discussed earlier.
i.e. If strong acid is in excess the problem will be dealt as the problem of strong acids and
if strong base is in excess the problem will be dealt as the problem of strong base.

Illustration-6 Calculate the pH of a solution obtained by mixing 50ml of 0.2 NHCl and 50ml of
0.1N NaOH.
Solution : Method of millimoles Number of millimoles = Vml × M
NaOH + HCl  NaCl + H2O
Initial millimoles 5 10 0
Milliomoles after reaction 0 5 5
total milliomoles
Molarity of HCl after the reaction = = 5/100 = 5 × 10–2M
total volume in ml
HCl  H+ + Cl–
1 millimole of HCl produces 1 millimole of H+
So molarity of H+ = molarity of HCl = 5 × 10–2
pH = – log [H+] = – log [5 × 10–2]
= 2 – log 5 = 2 – 0.6990
= 1.3010
 3.3 pH OF WEAK ELECTROLYTES (pH OF SOLUTION OF WEAK ACID OR
WEAK BASES)
Weak acids do not dissociate completely in the water their % degree of dissociation is very less.
e.g. let us takes CH 3COOH (C mole/litre and having degree dissociation ).

CH3COOH □ □□ CH3COO– + H+
C(1–) C C
[CH 3COO ][H ] C.C
Ka(CH 3COOH)  
[CH3COOH] C(1 )
C2
Ka 
1 
if  <  0.1 , then we can neglect
1   1
K a  C2
Ka
 
C

Ka
[H ]  C = C = Ka C
C
pH = –log [H+] = – log [ Ka C]
10
C2
Note : For calculating the pH of a weak acid first of all we calculate  from the equation Ka  ,
1 
if  comes out to be  < 0.1 then 1 –  will be taken as one and we use formula K a  C2
otherwise we would be use the formula
C2
Ka  for all calculation.
1 
Similarly if only weak base is present we can always calculate pH
For weak base
OH– = Kb  C
Where Kb is base dissociation constant, C is the molarity of base and degree of dissociation of weak
base  = Kb / C

3.4 OSTWALD’S DILUTION LAW

Ostwald’s pointed out that like chemical equilibrium in ionic equilibrium we can apply law of mass
action. An equilibrium between ionized and unionized molecules.
Consider a binary electrolyte having conc C and degree of dissociation is .
AB □ □ □ A  B
At. time = 0 C 0 0
at time = t C(1 – ) C  C
 Chemistry : Ionic Equilibrium


[A ][B ] C  C C2
Keq    , for a weak electrolyte
[AB] C(1  ) 1  

1   1


 Keq
Keq  C2 ,  
C
If 1 mole of AB is present in ‘V’ litre of solution.
1
C
V
  Keq  V
Thus law thus explains that  is directly proportional to volume or with dilution degree of
dissociation of weak electrolytes increases.
Keq
Conc. of [A+] = Conc. [B–]  C  C  KeqC
 C
Limitation
(i) This is only for weak electrolytes not for strong electrolytes.
(ii) This law is not applicable for strong electrolyte because strong electrolytes are almost
completely ionized at all dilution
Illustration 7 : What is the pH of a 1 M solution of acetic acid? To what volume must one litre of
this solution be diluted so that the pH of the resulting solution will be twice the
original value? Given : Ka = 1.8 × 10–5.

Solution : CH3COOH □ □□ CH3COO– + H+

1–x x x

x2
Ka =  x2 = 1.8 × 10–5; x = 4.2 × 10–3 = [H+]
1 x
 pH = – log [H+] = – log (4.2 × 10–3) = 2.37.
Now, let 1 litre of 1 M CH3COOH be diluted by V lires so that the pH of the solution
doubles. Let the concentration of the diluted solution be c moles/lire. Thus,
c
CH3COOH □ □□ CH3COO– + H+
(c – x) x x
x  x
Ka = = 1.8 × 10–5 ...(1)
(c  x)
Further, pH = – log x = 2 × 2.37 = 4.72 (pH doubles on dilution)
or log x = – 4.74 = 5.26
x = 1.8 × 10–5.
 Substituting x in (1), we get, c = 3.6 × 10–5M
As the number of moles of CH3COOH before and after dilution will be the same
 moles of CH3COOH = molarity × volume in litres
 3.6 × 10–5 × V = 1 × 1 (Initial molarity = 1, Initial volume = 1)
V = 2.78 × 104 litres.
Illustration-8 Calculate the pH of 0.1 M CH 3 COOH which is 10% ionized and have
Ka = 1 × 10–5
Solution : CH COOH □ □ □ CH COO– + H+
3 3

Concentration of H+ ions = Ka  C for monoprotic acid.

C H = Ka  C = 105 101 = 10
–3

pH = 3
Illustration-9 The pH of 0.1 M hydrocyanic acid solution is 5.2. What is the value of Ka for
hydrocyanic acid?
Solution : pH = – log [H+]

Conc of H+ = Ka  C where Ka is ionization constant of acid and C is the molarity of

the acid
Since pH = 5.2
– log [H+] = 5.2

So [H+] = Anti log 6.8 = 6.3 × 10–6

But, [H+] = Ka  C

6.3 × 10–6 = Ka  C

(6.3 106 )2
or Ka = = 6.3 × 6.3 × 10–12 × 10 = 3.69 × 10–10
0.1

3.5 pKa AND pKb FOR A CONJUGATE ACID-BASE PAIR

For an acid HX

HX □ □ □ H  X–

[H ][X– ]
 Ka  … (A)
[HX]

For conjugate base X– of acid HX

X–  H2O □ □ □ HX  OH–

[HX][OH– ]
Kb  … (B)
[X– ]
 Chemistry : Ionic Equilibrium

By eqs. (A) and (B),

Ka  Kb  [H ][OH– ]  Kw

or pKa  pKb  pKw  14

Note : 1. Stronger is acid, weaker is its conjugate base.
2. Higher is the value of pKa of an acid, lower is acid strength and higher is basic strength of
its conjugate base.

3.6 RELATIVE STRENGTH OF ACIDS AND BASES

For weak acids
Strength of I acid
Relative strength = Strength of II acid

For Acids HA1 if concentration is C1 and degree of dissociation 1

HA1 □ □ □ H  A–1
[H ]  C11
For HA2 if concentration is C2 and degree of dissociation is 2
HA2 □ □ □ H  A–2
[H ]  C22
Then, Relative strength
[H ] furnished by I acid C11
 
[H ] furnished by II acid C22

C  Ka1 C2   K a1 C1 
R.S.  1  
C  K C   K C 
2  a2 1   a2 2 

If C1 and C2 are same, then

 K a 
R.S.  1

 K a 
 2 
The Ionization constants of some selected weak acids at (298 K)

Acid Ionization constant, Ka

Hydrofluoric acid (HF) 3.5 × 10–4
Nitrous acid (HNO2) 4.5 × 10–4
Formic acid (HCOOH) 1.8 × 10–4
Acetic acid (CH3COOH) 1.74 × 10–5
Benzoic acid (C6H5COOH) 6.5 × 10–5
Hydrocyanic acid (HCN) 4.9 × 10–10
Phenol (C6H5OH) 1.3 × 10–10
 The values of the ionization constant of some weak bases at 298 K
Base Kb
Dimethylamine, (CH3)2NH 5.4 × 10–4
Triethylamine, (C5H5)3N 6.45 × 10–5
Ammonia (NH3) or (NH4OH) 1.77 × 10–5
Pyridine (C5H5N) 1.77 × 10–9
Aniline (C6H5NH2) 4.27 × 10–10
Urea, CO(NH2)2 1.3 × 10–14

3.7 COMMON ION EFFECT

Suppression in the dissociation of a weak electrolyte by adding a strong electrolyte having one ion
common to it is known as common ion effect. As a result of common ion effect, the concentration of
the ion not in common in the two electrolytes is decreased, e.g. Acetic acid is a weak electrolyte and
its ionization is suppressed in the presence of a strong acid or a strong salt like sodium acetate.
The common ion effect is used to control the pH of weak acid or base e.g. If ammonium chloride is
added to a solution of ammonia, the NH4+ from the salt increases the total concentration of NH4+
and equilibrium will be displaced towards left resulting in the decrease in concentration of OH–

NH4OH □ □ □ NH4+ + OH– NH4Cl  NH4+ + Cl–

3.8 CALCULATION OF pH OF MIXTURE OF WEAK ACID AND STRONG ACID

Illustration-10 Calculate pH of mixture of 0.1 M HCl and 0.1M CH3COOH and degree of
dissociation of CH3COOH. Given KaCH 3COOH = 10–5.
Solution : Here the constituents are weak acid and strong acid
HCl  H+ + Cl–
Let  be the degree of dissociation of CH3COOH in the presence of 0.1 M HCl.
Since  < 10–2 (Because of common ion effect CCH 3COOH = 0.1
So C < 10–3 i.e. 0.001

CH3COOH □ □ □ CH3COO– + H+
Initial conc. C O 0.1
Conc. at eq. C – C C 0.1 + C
+
[H ] = 0.1 + C
i.e. 0.1 + something less than 10–3  0.1
pH = – log [H+] = – log 0.1 = 1
[CH3COO ] [H ] C 0.1
Now Ka = = C (1  ),  <<< 1
[CH3COOH]
C 0.1
so 1 –  ~ 1 Ka =
C
10–5 = 0.1   = 10–4
This means degree of dissociation of CH3COOH is 100 times suppressed in the presence
of a srong electrolyte having an ion common to it.
 Chemistry : Ionic Equilibrium

Illustration-11 What is the pH of a solution that is 0.10 M in NH3 and 0.10 M in NH4 NO3? Kb for
NH3 = 1.6 × 10–5.

Solution : NH3 + H O
2 □ □□
NH +4 + OH–
NH4NO 3  NH 4+ + NO 3–
[NH ] [OH ]
4
Kb =
[NH3 ]
Since NH3NO3 is a strong electrolye so it will dissociate completely hence the
concentration of [NH4 +] = 0.1 M.

NH3 + H 2O □ □ □ NH4+ + OH–

Initial conc. 0.10 0.10 0
Conc. at eq. 0.10 – x 0.10 +x x
 0.10

(0.10) (x)
Kb = = 1.6 × 10–5 [0.01 + x  0.1]
(0.10  x)

0.10x
Kb = = 1.65 × 10–5
0.10
x = 1.65 × 10–5
[OH–] = 1.65 × 10–5
pOH = – [log 1.65 + log 10–5] = 4.80
pH + pOH = 14
so pH = 14 – 4.80 = 9.20
Illustration-12 Calculate the pH of 10–8 M HCl
Solution : For pure water sample [H+] = 10–7
So in the presence of 10–8 M HCl (strong electrolyte)
Water will furnish [H+] < 10–7
Suppose [H+] concentration from water in the presence of 10–8 M HCl is x mole/litre
(x < 10–7 because of common ion effect)
HCl  H+ + Cl–

H2O □ □ □ H+ + OH–
x + 10–8 x
–8 –14
(x + 10 ) x = 10 [K wof water]
x2 + 10–8 x – 10–14 = 0

108  1016  4 1014 108  1016 (1  400)

x= =
2 2
 108 108 401 20 108 108 19 108
= = =
2 2 2
–8
x = 9.5 × 10
[H+] = 10–8 + x = 10–8 + 9.5 × 10–8
[H+] = 10.5 × 10–8
pH = 8 – log 10.5 = 6.96

3.9 pH OF A DIBASIC ACIDS AND POLYPROTIC ACID

Let’s take the eg. of a dibasic acid H2A. Assuming both dissociation is weak. Let the initial conc. of
H A is C and  and  be degree of dissociation for first and second dissocation.
2 1 2

H2A □ □□ HA– + H+

C(1 –1) C1 (1 – 2) C1 + C1 2

HA– □ □□ H+ + A– –

C1 (1 – 2) C1 + C1 2 C1 2.

 
[HA ][H ]

Ka1  

[H2A]

[C1 (1  2 )][C1 C12 ]

Ka1 
C(1  1)

[H ][A  ] [C1  C12 ][C12 ]

Ka2  [HA ]  [C (1   )]
1 2

After solving for  1 and  .2 We can calculate the H+ conc.

[H+] = C 1 + C 1 2
pH = – log [C1 + C1  2]
Note : For polyprotic acid Ka1  Ka2  Ka3 always hence 1  2  3 for stepwise ionisation.
The ionization constants of some common polyprotic acids (298 K)
Acid Ka1 Ka2 Ka3
Oxalic acid 5.9 × 10–2 6.4 × 10–5
Ascorbic acid 7.4 × 10–4 1.6 × 10–12
Sulphurous acid 1.7 × 10–2 6.4 × 10–8
Sulphuric acid Very large 1.2 × 10–2
Carbonic acid 4.3 × 10–7 5.4 × 10–11
Citric acid 7.4 × 10–4 1.7 × 10–5 4.0 × 10–7
Phosphoric acid 7.5 × 10–3 6.2 × 10–8 4.2 × 10–13
 Chemistry : Ionic Equilibrium

Illustration-13 Find the concentrations of H , HCO–3 and CO–2

3 in a 0.01 M solution of

carbonic acid if the pH of solution is 4.18. K1  4.45 10–7 , K2  4.69 10–11 .

Solution: Given, pH = 4.18 = –log [H ]

 [H ]  6.6110–5 mol litre–1

H2CO3 □ □ □ H  HCO–3

[H ][HCO– ]
3
K1 
[H2CO3 ]

[6.6110–5 ][HCO– ]
–7 3
or 4.45 10  or [HCO–3 ]  6.7310–5 mol litre–1
[0.01]

Again for dissociation of HCO–3 , we have

HCO– □ □ □ H  CO–2
3 3

[H ][CO–2 ] –11

[6.6110–5 ][CO–2 ]
3
K2  – or 4.69 10  3
[HCO 3 ] [6.73 10–5 ]

 [CO–2
3 ]  4.78 10
–11
mol litre–1

Illustration-14 Calculate the concentration of various species in a 0.1 M H2S saturated solution. K1
= 1 ×10–7 and K2 = 1.3 × 10–13.
Solution : Let 1 be the degree of dissociation of 1st step.

H2 S □ □□ H+ + HS– ...(i)
Initial conc. C 0 0
Conc. at
equilibrium C–C 1C C1 + (C12) C1 – (C12)
 C1  C1
C – C1  C since H2S is a very weak acid.
Let 2 be the degree of dissociation of 2nd step.

HS– □ □□ H+ + S2–.............................(ii)
C1 – C12  C1 (C1) + C12  C1 C12
Now make the concentration of all common species in both equilibrium as same indicated
by ( ).
Now C12 is the product of three small quantities so this will be negligible in comparison
to C1.
[H ][S2 ]
Ka2 =
[HS ]
 Since [H+] = [HS–1]
so [S2–] = K a 2 = 1.3 × 10–13.
[H2S] = C = 0.1
[H ] [HS ]
Ka =
1 [H2S]

C1  C1
=
C

Ka 1
1 = = 10–3
C
[H+] = [HS–] = C1 = 0.1 × 10–3 = 10–4.

EXERCISE – 1
1. What is percent dissociation of 0.01 M aq. NH3 in 0.01 M NH4Cl ? Also calculate pH.
[Kb (NH3) = 1.8 × 10–5].
2. Calculate the pH in a solution prepared by dissolving 0.01 mole of solid NH4Cl in 0.5 L of 0.40
M NH3. Assume that there is no volume change. [pKb (NH3) = 4.74]

3. For the equilibrium AB (s) □ □ □ A+(aq) + B– (aq); K = 1 × 10–6

What is [A+ (aq)] in 0.01 M [B– (aq)]?
4. Calculate the per cent dissociation of 0.1 M HN3 (hydrazoic acid, Ka = 1.9 × 10–5. Recalculate
the percent dissociation of 0.10 M HN3 in presence of 0.10 M HCl.

4. BUFFER SOLUTION
A buffer solution is a solution that can resist the change in pH on the addition of a small amount of
acid or alkali or when it is diluted. The action of a buffer solution is dependent upon the common ion
effect. It is the mixture of a weak acid and its conjugate base or a weak base and its conjugate acid
or it is the salt of a weak acid and weak base.
There are three types of buffer
(i) Acidic Buffer ii) Basic Buffer
(iii) Salt Buffer
Mechanism of Buffer Action: Let us see why CH3COONH4 is a Buffer while NaCl is not.
CH COONH exists almost entirely in form of it’s ion CH COO– and NH if an acid is added to
3 4 3 4
that solution, the H+ ion furnished by the acid combine with CH 3COO– ions to form feebly dissociated
molecule of CH3COOH.
CH COO– + H+ □ □ □ CH COOH
3 □ □□ 3
Since most of the H+ ions added are taken up by CH COO– to form CH COOH which itself slightly
3 3
dissociated, the pH of CH3COONH4 changes only slightly.
 Chemistry : Ionic Equilibrium

Now, suppose a base is added to CH 3COONH 4 solution the OH– furnished by the base will be
taken up by NH ion to form feebly dissociated NH OH.
4 4

 
NH  OH □ □ □ NH OH
4 4
–
Since most of the OH ions are taken up by NH ions to form feebly dissociated NH OH. Due
4 4
to this very little change in the pH of CH3COONH4 solution occurs.
Now let us see why a solution of NaCl is not a Buffer. In aqueous solution it is almost entirely
dissociated into Na+ and Cl–. If H+ ions are added to this solution the H+ combines with Cl– to form
HCl which completely dissociated due to strong electrolyte hence pH falls.
If OH– ions are added to the solution, it will combine with Na+ to form NaOH which will almost
completely dissociated. Hence pH will rise.

4.1 BUFFER SOLUTION OF TYPE – 1 (ACIDIC BUFFER)

It is the mixture of a weak acid and its salt with strong base i.e. mixture of weak acid and its
conjugate base.
e.g. CH3COOH and CH3COONa constitute an acidic bufer.
CH3 COONa is a strong electrolyte. So it will be in fully dissociated form
CH3COONa  CH3COO– + H2O and CH3COOH is a weak electrolyte so it will be in equilibrium
with its ions.

CH3COOH □ □ □ CH3COO– + H+
but this equilibrium will lie largely towards, left hand side because of common ion effect of CH3COO–
from CH3COONa on CH3COOH.i.e. CH3COOH will practically remain undissociated and only
CH3COONa will contribute to CH3COO–.
[CH3COO ] [H ]
Ka =
[CH3COOH]

Ka [CH3COOH]
or [H+] =
[CH3COO ]

[CH3COOH]
log [H+] = log Ka  log
[CH 3 COO ]

[CH3COO ] from salt

– log [H+] = – log Ka  log
[CH3COOH] [It remains paractically undissociated]

[salt]
pH = pKa  log
[acid]

[conjugate base]
or pH = pKa  log [Acid]
Illustration 15 : What is the pH change when 0.01 mol of HCl is added to a solution containing 0.05
mole of acetate ion and 0.05 mol of acetic acid in 1.0 L of solution? Given Ka of
acetic acid is 10–5.
Solution : CH3COO– and CH 3COOH will constitute an acidic buffer so initial pH will be
[Salt]
pH = pK a log
[Acid]
[Salt] = 0.05/1
[Acid] = 0.05/1
0.05
pH = 5  log =5
0.05
upon addition of HCl the following reaction will take place.
CH3COO– + H+  CH3COOH
initial moles 0.05 0.01 0.05
moles after the
reaction 0.04 0 0.06
[Salt] = 0.04/1
[Acid] = 0.06/1

0.04
Now pH = pKa  log = 4.8239
0.06
Change in pH = 5 – 4.8239 = 0.176

4.2 BUFER SOLUTION OF TYPE – 2 (BASIC BUFFER)

It is the mixture of weak base and its salt with strong acid
e.g. mixture of NH4OH and NH4Cl
NH4Cl is a strong electrolyte so it remains in fully dissociated form .
NH4Cl  NH4+ + Cl–
and since NH4OH is a weak base it is in equilibrium with its ions.

NH4OH □ □ □ NH4+ + OH–

but this equilibrium largely lies towards left hand side because of the common ion effect of NH4+ ion
from NH4Cl on NH4OH.
So the weak base NH4OH remains practically undissociated and all NH4+ are contributed by NH4Cl
[NH ] [OH ]
4
Kb =
[NH4OH]

Kb[NH4OH]
or [OH–] =
[NH4 ]
 Chemistry : Ionic Equilibrium

[NH4OH]
log [OH–] = log Kb  log
[NH
4 ]

[NH ] from salt

4
– log [OH–] = – log Kb  log
[NH4OH] It remains paractically undissociated

[salt]
pOH = pKb  log
[base]
[conjugate acid]
or pOH = pKb  log
[base]
Then pH of basic buffer = 14 – pOH
Illustration 16 : What is pH of a buffer solution prepared from 1.00 mol of NH3 and 0.40 mol of
NH4Cl in 1.0 L of solution ? Given Kb of NH3 = 10 –5.

Solution : It is mixture of weak base NH3 and its salt with strong acid (NH4Cl) so it will constitute
a basic buffer and pOH of basic buffer is given by

[salt]
pOH = pKb  log
[base]
[salt] = 0.4/1
[base] = 1/1
pOH = 5 + log 0.4 = 5 – 0.3980
pOH = 4.6020
pH = 14 – 4.6020 = 9.3980

4.3 BUFFER SOLUTION OF TYPE – 3 (SALT BUFFER)

A salt buffer is a solution of a salt which itself can act as a buffer. Such salt is the salt of a weak acid
and weak base.
For example, CH3COONH4 □ □ □ CH3COO–  NH4
When an acid is added, it reacts with CH3COO– to produce CH3COOH and when a base is
added, it reacts with NH4 to produce NH4OH .

4.4 BUFFERING ACTION OF SALT BUFFER

Upon the addition of small quantity of strong acid to a salt buffer the following reaction takes place.
CH3COO– + H+  CH3COOH
CH3COOH is practically undissociated because of common ion effect from the salt.
So H+ are digested and converted into a compound that does not produces H+, so pH will remain
constant.
Upon the addition of small quantity of strong base to a salt buffer the following reaction takes
places.
NH4+ + OH–  NH4OH
All the OH– are digested to form NH4OH, which does not produces OH–, so pH of solution will
remains constant.
4.5 pH OF A SALT BUFFER
pH of a salt buffer will be calculated in hydrolysis (refer salt hydrolysis)

4.6 BUFFER CAPACITY

Number of moles of acid or base required to be added to one litre of the buffer solution so as to
change its pH by one unit.
No. of moles of acid/alkali added per litre of buffer solution
Buffer Capacity = change in pH

Buffer capacity is maximum when the [salt] = [acid] for acidic buffer i.e. pH = pKa or
[salt]  [base] for basic buffer pOH  pKb
Illustration 17 : What is the pH of the solution when 0.2 mole of HCl is added to one litre of a
solution containing :
(i) 1 M each of CH3COOH and acetate ion
(ii) 0.1 M each of CH3COOH and acetate ion
Assume that the total volume is 1 litre.
Ka of CH 3COOH = 1.8 × 10–5.
Solution : (i) Addition of 0.2 mole of HCl increases the concentration of CH3COOH by 0.2 and
reduces the concentration of CH 3COO– by 0.2 mole/L.
 [CH3COOH] = 1 + 0.2 = 1.2 M
[CH3COO–] = 1 – 0.2 = 0.8 M = [CH 3COONa]
[salt] 0.8
–5
Using pH = pKa + log [acid] = – log (1.8 × 10 ) + log = 4.57.
1.2
(ii) In this case 0.1 M of CH 3COO– will combine with 0.1 M of HCl forming 0.1 M
CH3COOH.
Total [CH3COOH] = 0.1 + 0.1 = 0.2 M.
But in the presence of the remaining 0.1 M HCl, the dissociation of 0.2 M CH3COOH
will be further suppressed by the common-ion effect.
Hence neglecting [H+] produced by CH3 COOH, the pH may be calculated for just
0.1 M HCl.
pH = – log [H+] = – log (0.1) = 1.0.
Note : From the above illustration you can very well see that why Buffer capacity is
maximum when [salt] = [acid].
Illustration 18 : What is the pH of a buffer solution obtained by adding 25.00 mL of a 0.10 M
sodium hydroxide solution to 75.00 mL of a 0.10 M solution of acetic acid? Given
Ka acetic acid = 10–5?
Solution : The constituents are reactive so first of all we will take the reaction into consideration.
CH3COOH + NaOH  CH3COONa + H2O
initial millimoles 7.5 2.5 0 0
milimoles after the reaction 5.0 0 2.5
Since in final mixture only CH3COOH (weak acid) and CH3COONa (salt of CH3COOH
with strong base) is present so it will constitute an acidic buffer and pH of acidic buffer is
given by
 Chemistry : Ionic Equilibrium

[salt]
pH = pKa  log
[acid]
Total volume of the mixure = 75 + 25 = 100 ml
[CH3COONa] = 2.5/100
[CH3COOH] = 5/100
2.5 1
pH = 5  log = 5  log = 5 – 0.3010 = 4.6990
5 2

EXERCISE – 2
1. A buffer solution is 0.20 M in CH3COOH and in CH3COONa. Calculate change in pH upon
adding 1.0 mL of 0.10 M HCl to 10 mL of this buffer.
2. A buffer of pH 9.26 is made by dissolving x moles of ammonium sulphate and 0.1 mole of
ammonia into 100 mL solution. If pKb of ammonia is 4.74, calculate value of x.
3. 50 mL of 0.1 M NaOH is added to 75 mL of 0.1 M NH4Cl to make a basic buffer. If pKa of
NH4+ is 9.26, calculate pH.

5. HYDROLYSIS OF SALTS
Salts are the product of an acid and a base, other than water. Depending on the nature of an acid or
a base there can be four types of salts :
(i) Salt of a strong acid and a strong base
(ii) Salt of a weak acid and a strong base,
(iii) Salt of a strong acid and a weak base and
(iv) Salt of a weak acid and a weak base.

5.1 HYDROLYSIS OF A SALT OF STRONG ACID AND BASE

Examples of this type are :
NaCl, Na2SO4, K2SO4 etc
NaCl + H2O  NaOH + HCl
Na+ + Cl– + H2O  Na+ + OH– + H+ + Cl–
H2O □ □ □ H+ + OH–
So, salts of strong acid and strong bases do not undergo hydrolysis. i.e. pH of the salt solution of
strong acid and strong base is always 7 i.e. the solution is neutral.

5.2 SALT OF A WEAK ACID AND STRONG BASE

Let us take a certain amount of weak acid (CH3COOH) and add to it the same amount (equivalents)
of a strong base (NaOH). They will react to produce CH3COONa.
CH3­COOH + NaOH  CH3COONa + H2O
CH3COONa being a strong electrolyte, completely dissociates into its constituent ions.
CH COONa  CH COO– + Na+
3 3
Now, the ions produced would react with H2O. This process is called hydrolysis.
 Na+ + CH3COO– + H 2O □ □ □ CH3 COOH + NaOH
We know that NaOH is a strong base and therefore it would be completely dissociated to give Na+
and OH– ions.

 Na+ + CH3COO– + H 2O □ □ □ CH3 COOH + OH– + Na+

Canceling Na+ on both the sides,

 CH 3COO– + H 2O □ □ □ CH3COOH + OH–

We can note here that ions coming from strong bases do not get hydrolysed. We should note here
that the solution will be basic. This is because the amount of CH3 COOH produced and OH-– produced
are equal. But CH 3COOH will not completely dissociate to give H+ ions. Therefore [OH–] ions will
be greater than [H+] ions.
Since the reaction is at equilibrium,
[CH3COOH][OH ]
KC = [CH3COO ]
This equilibrium constant Kc is given a new symbol, Kh.
[CH3COOH][OH ]
 Kh =
[CH3COO ]
If we multiply and divide the above equation by [H+] of the solution, then

[CH3COOH][OH ] [H ] [H ][OH ]

Kh = =
[CH3COO ] [H ] [CH3COO ][H  ]
[CH3COOH]

Kw [CH3COOH][OH ] Kw
 Kh = K  Kh = 
[CH3COO ] = Ka
a

CH 3COO–+H 2O □ □ □ CH3COOH + OH–

Initial: C 0 0
At eq: C(1–h) Ch Ch
Where h is the degree of hydrolysis of CH3COO– ion.
Ch  Ch K
 = w
C (1 h) K
a

If  is very much less than 1,

Kw Kw Kh
Ch2 = , h= =
Ka Ka C C

Kw Kw C
As [OH–] = Ch, [OH–] = C × = Ka
Ka C
 Chemistry : Ionic Equilibrium

Kw Kw Ka
[H+] = [OH ] =
C
  1 1 1
K w  Ka
or pH = – log [H ] = –log 
+  = pKw  pKa  log C
 C  2 2 2
Now, we will analyse the hydrolysis of this salt in detail. The reactions occurring were,
CH3COOH + NaOH  CH3COONa + H2O …(1)
CH3COONa  CH3COO– + Na+ …(2)
CH3COO– + H 2O □ □ □ CH3COOH + OH– …(3)
+ –
If we look at the first reaction, we can see that NaOH will be fully ionized as Na & OH ions and
CH3COONa as CH 3COO– & Na+ ions . Canceling Na+ from both the sides, the first reaction looks
like,
CH3COOH + OH–  CH3COO– + H 2O … (4)
You can see clearly that reaction (4) and (3) are the reverse of each other. Therefore, reaction (4)
is also in equilibrium.
 CH 3COOH + OH– □ □ □ CH3COO– + H 2O … (5)
This actually puts us in a dilemma. If we look at reaction (5) [which is basically the reverse of
reaction (1)], we see that when CH3COOH reacts with OH– the reaction reaches equilibrium. Now,
there are two possibilities: (i) either acetic acid reacts with OH– and the reaction reaches equilibrium
or (ii) acetic acid reacts with OH– and the reaction completely goes to produced CH3COO– which
then gets hydrolyses (by going in the reverse direction) and finally reaches equilibrium. On close
scrutiny we would realize that the first possibility is more realistic. It is not logical for a reaction to
completely go to the right and then go reverse to reach equilibrium. Now, if the first explanation is
correct then we find that actually no hydrolysis has taken place. What has happened is that the first
reaction has not gone to completion and has reached equilibrium.
Apart from this difference, both the explanation would give us the same result in terms of pH
calculation. For example, we can see that if a certain amount of CH3COOH reacts with the same
amount (equivalents) of OH– ions and the reaction reaches equilibrium, then equal amounts
(equivalents) of OH– ions and CH 3COOH would be left over. This is a similar situation which we
encountered earlier in hydrolysis. We can see that this solution would be basic.
To conclude we can say that hydrolysis of a salt occurs only when the salt is dissolved in water.
Illustration 19 : Calculate the degree of hydrolysis and pH of 0.1 M sodium acetate solution.
[Kb CH 3 COO– = 5.6 × 10–10]
Solution : CH3COO– + H2O □ □ □ CH3 COOH + OH– Kh = 5.6 × 10–10
Kh 1010
h= = 5.6  = 7.48 × 10–5
C 0.1
–
Since Kb of CH 3
COO = 5.6 × 10–10
1014
So Ka of CH3COOH = = 1.8 × 10–5
5.6 1010
1
pH = 7  pK  1 log C
a
2 2
1 1
= 7   4.74  log 0.1 = 8.87
2 2
Illustration 20 : What is the pH of 0.10 M KCN solution ?
Ka(HCN) = 6.2 × 10–10
Solution : KCN is salt of strong base KOH and weak acid HCN
pH expression for hydrolysis of salt of strong base and weak acid is given by
1
pH = 7  pK  1 log C
a
2 2
Ka = 6.2 × 10–10
pKa = 9.22
C = 0.1 M
1 1
pH = 7   9.22  log 0.1 = 11.11
2 2

5.3 SALT OF A STRONG ACID AND A WEAK BASE

Let the acid be HCl and the base be NH4OH.
Therefore the salt would be NH4Cl.
NH Cl completely dissociates into NH and Cl– ions.
4 4
 –
 NH4Cl  NH 4 + Cl
Cl– + NH +H O □ □ □ NH OH + HCl
4 2 4

HCl being a strong acid dissociates completely to give H+ ions and Cl– ions.

 Cl– + NH + H O □ □ □ NH OH + H+ + Cl–
4 2 4


or NH + H O □ □ □ NH OH + H+
4 2 4

We can see that the ion coming from the strong acid does not get hydrolysed. We had previously
seen that the ion coming from the strong base also does not get hydrolysed. Hence, one can conclude
that the salt of a strong acid and weak base does not get hydrolysed.
In this hydrolysis, NH4OH and H+ are being produced. This implies that the solution is acidic. To
calculate pH,
NH + H O □ □ □ NH OH + H+
4 2 4

Initial: C 0 0
At eqb: C(1–h) Ch Ch

Where h is the degree of hydrolysis of NH4 .

[NH4OH][H ]
Kh = [NH4 ]
Multiplying and dividing by OH– and rearranging,
[NH4OH][H ] [OH ] [H ][OH ]
Kh = 
[NH4 ] [OH ] [NH4 ][OH ]
[NH4OH]
 Chemistry : Ionic Equilibrium

Kw Kw
  Kh = K
Kb b

Now, substituting the concentrations,

[NH4OH][H ] Kw Ch  Ch Ch2
Kh = = K = =
[NH4 ] b C (1 h) 1 h

Kw
If h  0.1, then, Ch2 = K
b

Kw Kh
h= =
KbC C

Kw Kw C 1 1 1
Since [H+] = Ch, [H+] = C = Kb pH = 2 pK w  pK b  log C
or
KbC 2 2
–
Illustration 21 : Calculate the hydrolysis constant for NH Cl; pH value and [OH ] in 0.1 M NH Cl
4 4
solution.
[K b(NH OH) = 1.75 × 10-5 ]
4

Solution : Kb( NH4OH) Ka( NH ) = K

4 w

K Kw
(or K ) 1014
 = Kb =
a( NH4 ) h
1.75105
Kh [NH4 +] = 5.7 × 10–10
NH4Cl is a salt of weak base NH4OH and strong acid HCl pH expression for the hydrolysis
of salt of weak base and strong acid is given by
1
pH = 7  pK  1 log C
a
2 2
–5
Kb = 1.75 × 10
pKb = 4.74
1 1
pH = 7   4.74  log 0.1 = 5.13
2 2
pH = log [H+] = 5.13
[H+] = 7.55 × 10–6
Kw 1014
[OH–] =  =
[H ] 7.55106
[OH–] = 1.32 × 10–9

5.4 SALT OF WEAK ACID AND WEAK BASE

Let the weak acid be CH3COOH and the weak base be NH4OH. Therefore, the salt is CH3COONH4.
The salt completely dissociates.
CH COONH  CH COO– + NH
3 4 3 4
 The ions get hydrolysed according to the reaction.
CH COO– + NH + H O □ □□ NH OH + CH COOH
3 4 2 4 3

Initial : C C 0 0
At equilibrium: (1–h) C(1–h) Ch Ch

[NH4OH][CH3COOH]
Kh =
[NH4 ][CH 3COO ]
Multiplying and dividing by H+ & OH– and rearranging,
[NH4OH][CH3COOH][H ][OH ]
Kh = [NH4 ][CH 3 COO ] [H ][OH ]

[H ][OH ]  Kw
 
[CH3COO ][H  ] [NH4 ][H  ] Ka Kb
 
[CH3COOH] [NH4OH]

 Kw
 Kh =
Ka Kb
Substituting the concentration terms,
Kw
K = = Ch  Ch (Ch)2 h2
 
h
Ka Kb C (1  h) C (1  h) [C(1  h)] 2 (1  h) 2

h Kw
 =
1 h Ka Kb
There is an important issue that needs clarification before we move on further. In this case, we can
see that both the ions (i.e, cation and anion) get hydrolysed to produce a weak acid and a weak base
(hence, we can’t predict whether the solution is acidic, basic or neutral). We have considered the
degree of hydrolysis of both the ions to be the same. Now we present an explanation as to why this
is incorrect and then state reasons for the validity of this assumption.
Actually the hydrolysis reaction given earlier,

CH3COO– + NH 4+ + H 2O □ □ □ CH3COOH + NH 4OH

is made up of the following three reactions,

CH3COO– + H 2O □ □ □ CH COOH
3 + OH–

NH4+ + H 2O □ □ □ NH 4OH + H+

H+ + OH– □ □ □ H2O
If we add these three reactions, the net reaction is the one stated previously. This suggests that both
CH3 COO– and NH4 ions get hydrolysed independently and their hydrolysis depends on: (i) Their
 Chemistry : Ionic Equilibrium

Kw Kw
initial concentration and (ii) the value of Kh which is for CH COO– and for NH4+. Since
3
Ka Kb
both of the ions were produced from the same salt, their initial concentrations are same. Therefore
K Kw
unless and until the value of w and or Ka and Kb is same, the degree of hydrolysis of the ions
Ka Kb
cannot be same.
To explain why this assumption is valid, we need to now look at the third reaction, i.e., combination
of H+ and OH– ions. It is obvious that this reaction happens only because one reaction produced H+
ion and the other produced OH– ions. We can also note that this reaction causes both the hydrolysis
reaction to occur more since their product ions are being consumed. If you look at the solution of
Exercise 1, you will notice that the equilibrium which has smaller value of equilibrium constant is
affected more by the common ion effect. For the same reason if for any reason a reaction is made
to occur to a greater extent by the consumption of any one product ion, the reaction with the
smaller value of equilibrium constant tends to get affected more.
Therefore, we conclude that firstly the hydrolysis of both the ions occurs more in the presence of
each other (due to the consumption of the product ions) than in each other’s absence. Secondly the
hydrolysis of the ion which occurs to a lesser extent (due to smaller value of Kh) is affected more
than the one whose Kh is greater. Hence we can see that the degree of hydrolysis of both the ions
would be close to each other when they are getting hydrolysed in the presence of each other.
Now, to calculate the pH of this solution, we need to understand one more principle. Let us assume
that we have an aqueous solution of CH3COOH. Let us also assume that we do not know whether
CH3 COO– and H+ are in the solution or not (even though H+ would be there since the solution is
aqueous). We can see that the Qa for the reaction

CH3 COOH □ □ □ CH3 COO– + H+ is zero (if we assume no CH3COO– or H+) .

 Qa < Ka. The reaction would therefore move forward to reach equilibrium. The same is true when
CH3COO– and H+ are present without CH 3COOH. Hence, we conclude that “Any equilibrium that
can exist (i.e., when all reactants and / or all products are present) will exist (except when pure
solids or liquids are not present, in which case this statement will not be true)”.
As can be seen in the hydrolysis reaction,

CH3COO– + NH 4+ + H 2O □ □ □ NH4OH + CH 3COOH,

CH COOH is present in the solution. This implies that the equilibrium between CH COOH, CH COO–
3 3 3
and H+ can exist and therefore would exist.

 CH3COOH □ □ □ CH3COO– + H+
In fact the equilibrium between NH 4OH, and OH– also exists.
Now, we calculate the pH of the solution as,
–
CH3COOH □ □ □ CH COO
3
+ H+
Ch C(1–h)

[CH3COO ] [H ] C (1  h) [H ]

Ka =
[CH3COOH] = Ch
  h 
+
 [H ] = Ka   
 1 h 

h Kw
Substituting as
1 h Ka Kb

 h  Kw Kw Ka
[H+] = K ×   = Ka × =
a
 1 h  Ka Kb Kb
1 1 1
or pH = 2 pK  pK a  pK b
w
2 2

In such case
(i) if Ka = Kb the solution will be neutral
(ii) if Ka > Kb the solution will be acidic
(iii) if Ka < Kb the solution will be alkaline

Illustration 22 : Calculate the pH of an aqueous solution of 1.0 M ammonium formate.

pKa HCOOH = 3.8
pKbNH4OH = 4.8
Solution : Since ammonium formate is salt of a weak acid and weak base.
1 1 1 1
So, pH = 7  pK  pK = 7   3.8   4.8 = 6.5
a b
2 2 2 2
Illustration 23 : The dissociation constant of aniline at 298 K is 5.93 × 10–10. Calculate the percentage
hydrolysis of aniline hydrochloride in 0.1 M solution at 298 K.
Solution : Aniline hydrochloride is a salt of a strong acid weak base

Kw
So, h =
Kb  C

1014
= = 1.3 × 10–2
5.931010  0.1
So, % hydrolysis = 1.3 × 10–2 × 100 = 1.3
Note : From above the illustration it is clear that outof 100 moles of aniline hydrochloride
only 1.3 moles are getting hydrolysed.
Illustration 24 : Calculate the pH of a solution which is obtained by mixing equal
volumes of 0.1M CH3COOH and 0.1M NaOH solution. Given Ka of CH3COOH =
10–5 .
Solution : Since the constituents are reactive, so first of all we will take the reaction into consideration.
Let V ml of each is mixed.
CH3COOH + NaOH  CH3COONa + H2O
initial millimoles 0.1V 0.1V 0
milimoles after the reaction 0 0 0.1V
After the reaction only salt is left so problem will be of salt hydrolysis [salt of weak acid
and strong base]
 Chemistry : Ionic Equilibrium

0.1V
[CH3COONa] = = 0.05
2V
pH expression for the hydrolysis of salt of weak acid and strong base is given by
1
pH = 7  pK  1 log C
a
2 2
where Ka is ionization constant of weak acid and C is concentration of salt
1 1
pH = 7   5  log 0.05 = 9.5 – 0.65 = 8.85
2 2

EXERCISE – 3
1. Equimolar quantities of each of the following substances are dissolved in enough water to
make 1.00 L of solution. Arrange the solution so prepared in order of increasing pH.
(a) KHSO4 (b) NaHCO3
(c) Na2O (d) HClO4
2. Calculate the pH of a 0.15 M aqueous solution of AlCl3. Given :

[Al(H2O)6]3+ + H2O (l) □ □ □ [Al(H2O)5OH]2+ (aq) + H3O+ (aq), Ka = 1.4 × 10–5

3. Find the pH of the solution obtained when 25 mL of 0.005 M benzylamine is titrated to the
equivalence point with 0.005 M HCl. pKb for benzylamine is 9.33.
4. 10 mL of 0.10 M CH3COOH (pKa = 4.74) is titrated with 0.10 M NaOH. What is the pH
when:
(a) 5 mL of NaOH has been added
(b) 10 mL of NaOH has been added
5. 50.0 mL of 0.1 M solution of protonated form of alanine (H2A+; pKa 1 = 2.34, pKa 2 = 9.70)
is treated with 50 mL of 0.01 M NaOH. Calculate pH.

6. SOLUBILITY AND SOLUBILITY PRODUCT

6.1 SOLUBILITY EQUILIBRIUM
A solution which remain in contact with excess of the solute is said to be saturated. The amount of
a solute, dissolved in a given volume of a solvent (in 1 litre) to form a saturated solution at a given
temperature, it termed as the solubility of the solute in the solvent at that temperature.
Molar Solubility: No. of moles of solute dissolved in per litre of solution
Solubility Product: In a saturated solution of a salt, there exists a dynamic equilibrium between
the excess of the solute and ions furnished by that parts of the solute which has gone in solution. The
solubility product of a sparingly soluble salt is given as product of the conc. of the ions raised to the
power equal to the no. of times the ion occur in the equation after the dissociation of the electrolyte.

AxBy □ □□ xAy+ + yBx–

Ksp  [Ay ]x[Bx ]y

 Let the solubility of AxBy is S then

K sp  [xS]x[yS]y

K sp  xx .yy[Sxy ]
The principle of solubility product is applicable for sparingly soluble salt.

6.2 IONIC PRODUCT

For a solution of a salt at a specified concentration, the product of the concentration of the ions, each
raised to the proper power, is called as the ionic product. For a saturated solution in equilibrium with
excess of solid, the ionic product is equal to solubility product.
At equilibrium, ionic product = solubility product
If ionic product is less than solubility product it means solution is unsaturated means more salt can be
dissolved in it.
If ionic product greater than solubility it means solution is holding more salt that can dissolve in it,
therefore precipitation start, until or unless ionic product becomes equal to Ksp.

6.3 COMMON-ION EFFECT ON SOLUBILITY

The common ion presence in the solution decrease the solubility of a given compound e.g. The
solubility of BaSO4 in Na2SO4 solution is smaller than that in an aqueous solution.
Consider saturated solution of AgCl. If a salt having either of the ion common to AgCl say KCl is
added to it, then

AgCl(g)  aq. □ □ □ Ag  Cl–

KCl  aq. K  Cl–

For AgCl K SP  [Ag ][Cl– ]

[Cl– ] Increases in solution due to presence of KCl and thus to have KSP constant, [Ag ] will
decrease or AgCl will precipitate out from solution, i.e., solubility of AgCl will decrease with increasing
concentration of KCl in solution.
Let 0.1 M KCl(aq.) solution with AgCl(aq.) . If solubility of AgCl is s mol litre–1 , then,

For AgCl K SP  [Ag ][Cl– ]

KSP  s(s  0.1)

s being small in comparison to 0.1 and thus may be neglected therefore,

KSP
KSP  s 0.1 or s AgCl 
0.1
where s is solubility of AgCl in presence of 0.1 M KClaq.
 Chemistry : Ionic Equilibrium

Illustration 25 : (i) Calculate the solubility of AgCl in water [K sp AgCl = 10–10]

(ii) Calculate the solubility of AgCl in 0.1 M KCl
Solution : (i) Let S mole/litre be the solubility of AgCl in water, this means that in 1 litre water. S
moles will go into solution and excess AgCl will settle down an equilibrium will exist
between undissolved solid and it’s ions in the solution.

AgCl(s) □ □ □ Ag (aq)  Cl (aq)

S S

Ksp = [Ag ][Cl ] = S2

S= Ksp = 10–5 moles/litres

Molecular wt. of AgCl = 143.5
S = 10–5 × 143.5 g/l
= 1.43 mg/l
this means that only 1.43 mg of AgCl will go in 1 litre of solution and will make it saturated
i.e. the concentration of solid will almost remain constant
(ii) Let S be the solubility of AgCl in 0.1 M KCl.
Definitely S < S (Because of common ion effect)

AgCl(s) □ □ □ Ag  Cl

S 0.1  S (S  105 )
 0.1
Ksp = [Ag+] [Cl–]
Ksp
+
[Ag ] = = 10–9 mole/litre
0.1
This means that presence of KCl has suppressed the solubility of AgCl by 104 times, this
is because of common ion effect.
Illustration-26 A 100.0 mL sample is removed from a water solution saturated with CaSO4 at
25°C. The water is completely evaporated from the sample and a deposit of 0.24 g
CaSO4 is obtained. What is Ksp for CaSO4 at 25°C ?
Solution: CaSO (s) Ca2+ (aq) + SO2 (aq), K = ?
4 4 sp

Data shows that the solubility of CaSO4 is 0.24 g per 100 mL.
0.24 1000
 [CaSO4] =  mol L1  0.01765 M
100 136
 [Ca2+] = [ SO2
4 ]  0.01765 M .
2+ 2 2 –4
 Ksp = [Ca ] [SO4 ] = (0.01765) = 3.115  10 .
6.2 PREFERENTIAL PRECIPITATION OF SALTS
Frequently, a solution contains more than one ion capable of forming a ppt. with another ion which is
added to the solution. e.g., in a solution containing Cl–, Br– and I–, if Ag+ ions are added then out of
the three, the least soluble silver salt is ppt first. If the addition of Ag+ ions is continued, eventually a
stage is reached when the next lesser soluble salt starts ppt along with the least soluble salt and so
on if the stocihiometry of the ppted salts is the same, then the salt with the minimum Ksp or minimum
solubility will ppted first followed by higher Ksp.
If the stoichiometry of the ppted salts is not the same, then with Ksp alone, we can’t predict which
ion will ppted first. e.g. a solution containing Cl– and CrO–24 both of these ions form ppt with Ag+
though the K (AgCl) > K (Ag CrO ). Yet it is AgCl (less soluble) which ppted first when Ag+ ions
sp sp 2 4

added to the solution. In order to predict which ion (Cl– or CrO2

4 ) ppt first. We have to calculate

the conc. of Ag+ ion needed to start precipitation through the K sp and given conc. of Cl– and CrO2
4 ,

if the conc. of Ag+ ions needed to start the precipitation of CrO2 –

4 is larger than that of Cl . Hence
as AgNO3 is added to the solution, the minimum of the two conc. of Ag+ to start the ppt will be
reached first and thus the corresponding ion (Cl– in this case) will be ppted in preference to the other.
During the course of ppt conc. of Cl– decreases and conc. of Ag+ increases when its’s conc. become
equals to the conc. required (of Ag+) for CrO2 –
4 . At this stages the whole of Cl ions have been
ppted the addition of more of AgNO3 causes the ppt of both the ions together.
(i) Solubility of a salt of weak acid and strong base in Basic Buffer suppresses than pure water
due to common ion effect. But in acidic buffer solution soubility increase than pure water.
Solubility of salt of weak acid and strong base follow the order – Acidic buffer > Pure water >
basic buffer. While solubility of salt of strong acid and weak base follow order – Basic buffer
> Pure water > Acid buffer.
(ii) Solubility of salt of weak acid and weak base in pure water: Let the solubility of salt be S,
and y mol/litre is the amount of salt getting hydrolysed.

CH3COONH4 □ □□ CH3COO– + NH4 … (1)

S–y S–y
CH3 COO– + NH4 + H2 O □ □□ CH3 COOH + NH4OH
S–y S–y y y … (2)
Ksp  (S y)(S y)  (S  y)2
Due to hydrolysis of salt from equation (2)
[CH3COOH][NH4OH] y.y
Kh  
[CH 3COO ][NH4 ] (S  y)(S  y)
2
 y 
Kh   
 S  y 
and we also know that
Kw
Kh 
Ka Kb
 Chemistry : Ionic Equilibrium

(iii) Solubility of a salt of weak acid and weak base in acidic buffer : Let the solubility of salt be
S and y be the amount of weak acid being formed.
CH COONH □ □□ CH COO– + NH
3 4 3 4

S–y y
– +
CH3 COO + H  CH 3COOH … (2)
S–y (from Acidic Buffer) y
K sp  [CH 3COO ][NH4 ] = [S – y] [y] = y [S – y]
for equation (2)
1
 K  [CH3COOH]  y
a
K [CH COO ][H ] (S  y)(H )


a(CH3COOH) 3

Solubility of CH3COONH4 in acidic buffer would be higher than in pure water

(iv) Solubility of a salt of weak acid and weak base in basic buffer
Similarly CH COONH □ □□ CH COO– + NH
3 4 3 4

y S – y
NH4  OH □ □□ NH4OH
S–y (from buffer) y
K sp (CH COONH )  [CH 3COO  ][NH 4]
3 4

Ksp  y(S – y)
1
 K  [NH4OH]  y
b
K [NH ][OH ] (S  y)(OH )


b 4

The solubility of CH 3COONH4 in basic buffer would be higher than pure water.
(v) Solubility of AgCl in an aqueous solution containing NH3
Let the amount of NH3 initially be ‘a’ M. if the solubility of salt be ‘b’ mole/ litre.

AgCl (s) □ □□ Ag+ + Cl–

At time = 0 b 0 0
at time = t b–y y
Ag+ + 2NH 3 □ □□ Ag (NH 3 )2 (aq.)
b–y a –2y y
+
where y is the amount of Ag which reacted with NH .3
K sp  [Ag ][Cl ]  (b  y)y

[Ag(NH 3]2 ]  y
Kf  2

[Ag ][NH 3 ] (b  y)(a  2y)
After knowing the value of Ksp and Kf the value of solubility can be calculated.
6.5 APPLICATIONS OF SOLUBILITY PRODUCT
(a) Calculation of Solubility : Suppose solubility of AgCl is S moles per litre.

AgCl □ □ □ Ag  Cl

Since AgCl is sparingly soluble. The saturated solution is highly dilute and the dissolved AgCl
may be supposed to be fully dissociated.
[Ag+] = S
[Cl–] = S
Ksp = [Ag+] [Cl–] = S2

S= Ksp
Let solubility of CaF2 be S mole /litre

CaF2(s) □ □ □ Ca   2F 
[Ca++] = S
[F–] = 2S, Ksp = [Ca++] [F–]2
4S3 = Ksp
1/ 3
K 
S =  sp 
 4 
(b) In qualitative Analysis. (Mixture Analysis).
Precipitation of Sulphides : The sulphides of second group cations have very low Ksp value.
While sulphides of IV group cations have relatively high Ksp values. If S– – concentration is high
than sulphides of IV group cations also precipitate in the II group. In order to check this, the
solution is acidified with HCl before passing H2S in the IInd group.

H2S □ □ □ 2H  S 

HCl □ □ □ H  Cl  
The presence of HCl supresses the dissociation of H2S due to the common ion effect of H+ and
keeps S– – concentration low. The ionic products of sulphides of second group cations exceed
their Ksp values but not those of IVth group. so sulphides of only II group cations precipitates.
(c) Precipitation of Hydroxides.
The hydroxides of III group cations Al3+, Cr3+ and Fe3+ have low Ksp values while hydroxide of
cations of subsequent groups have high Ksp values.
If OH– concentration is high then hydroxide of subsequent group cation also precipitate in the
III group. In order to check this NH4Cl is added before adding NH4OH in the third group.
NH4OH □ □ □ NH4+ + OH–
NH4Cl □ □ □ NH4+ + Cl–
The presence of NH4Cl supresses the dissociation of NH4OH due to the common ion effect of
NH4+ and keeps OH– concentration low.
The ionic products of hydroxide of III group cations exceed their Ksp values but not those of
subsequent groups.
So hydroxides of only III group precipitates.
 Chemistry : Ionic Equilibrium

Preparation of Pure NaCl from Common Salt

A saturated solution of common salt is prepared in water. The suspended impurities are removed
by filteration, HCl is gas is then passed.
NaCl(s)  NaCl (aq.) □ □ □ Na(aq.)  Cl(aq.)

HCl (aq.) □ □ □ H(aq.)  Cl(aq.)

[Na+] concentration is very low.
[Cl–] concentration rises. The product [Na+] [Cl–] exeeds Ksp of NaCl. So preceipitation of
NaCl takes place. The soluble impurities remain in the solution.
(d) Salting out of Soap
Soaps are Na+ or K salt of long chain fatty acid. They are obtained by the hydrolysis of oils or
fats with alkali solution.

CH2OCOR CH2OH
CHOCOR + 3NaOH  CHOH + 3RCOONa (Soap)
CH2OCOR (Oil or Fat) CH2OH
(Glycerol)

In order to precipitate soap from solution common salt is added.

RCOONa(s) □ □ □ RCOONa(aq.) □ □ □ RCOO(aq.)  Na(aq.)

Na+ concentration rises. The product [RCOO–] [Na+] exceeds Ksp of soaps. So precipitation
of soap takes place.

6.6 SOLUBILITY AND COMPLEX-IONS EQUILIBRIA

The stepwise formation of Complex ions
When a transition-metal ion binds Lewis base to form a coordination complex, or complex ion , it
picks up these ligands one at a time. The Ag+ ion, for example combines with NH3 in a two-step
reaction. It first picks up one NH3 molecule to form a one-cordinate complex :

Ag(aq.)  NH3(aq.) □ □ □ Ag(NH3 )(aq.)

This intermediate then picks up a second NH3 molecule in a separate step :

Ag(NH3 )(aq.)  NH3(aq.) □ □ □ Ag(NH 3 ) 2 (aq.)

It is possible to write equilibrium constant expressions for each step in these complex-ion formation
reactions. The equilibrium constant for these reactions are known as complex-formation equilibrium
constant, Kf .
The equilibrium constant expressions for the two steps in the formation of the Ag(NH3)2+ complex
ion are written as follows :

K  [Ag(NH3 ) ]
f1 [Ag  ] [NH 3 ]

K  [Ag(NH3 )2 ]
f2 [Ag(NH 3 ) ] [NH 3 ]
 The difference between Kf1 and Kf2 for the complexes between Ag+ and ammonia, for example, is
only a factor of 4 :

Ag(aq.)  NH3(aq.) □ □ □ Ag(NH3 )(aq.) Kf1 = 1.7 × 103

Ag(NH3 )(aq.)  NH3(aq.) □ □ □ Ag(NH 3 ) 2 (aq.) Kf2 = 6.5 × 103

This means that most of the Ag+ ions that pick up one NH3 molecule to form the Ag(NH3)+ complex
ion are likely to pick up another NH3 to form the two coordinate Ag(NH3)2+ complex ion.
Illustration-27 Calculate the complex formation equilibrium constant for the two-coordinate
Fe(SCN)2+ complex ion from the following data :
Fe3+ (aq). + SCN − (aq.) □ □ □ Fe(SCN )2+ (aq.) K f = 890
1

−
Fe(SCN ) 2+
(aq.) + SCN (aq.) □ □□ Fe(SCN )+2 (aq.) K f2 = 2.6
Solution : The difference between the stepwise formation equilibrium constant for this complex is
relatively small :
[Fe(SCN)2 ]
Kf 1   890
[Fe3 ] [SCN ]

[Fe(SCN)2 ]
Kf2   2.6
[Fe(SCN)2 ] [SCN]
Solutions of these complex ions are therefore best described in terms of an overall complex
formation equilibrium :

Fe3+ (aq.) + 2 SCN–(aq.) □ □ □ Fe(SCN) 2+ (aq.)

The equilibrium constant expression for the overall reactions is equal to the product of
the expressions for the individual steps in the reaction :

[Fe(SCN)2 ] [Fe(SCN)2 ] [Fe(SCN)2 ]

 
[Fe3 ] [SCN ]2 [Fe3 ] [SCN ] [Fe(SCN)2 ] [SCN ]
The overall equilibrium constant is therefore the product of Kf1 and Kf2 :
Kf = Kf1 × Kf2 = 2.3 × 103

6.7 COMPLEX DISSOCIATION EQUILIBRIUM CONSTANTS

Complex ions also can be described in terms of complex-dissociation equilibria. We can start by
assuming, for example, that most of the silver ions in an aqueous solution are present as the two-
coordinate Ag(NH3)2+ complex ion. We then assume that some of these ions dissociate to form
Ag(NH3)+ complex ions and then eventually Ag+ ions :
Ag(NH 3 ) 2 (aq.) □ □ □ Ag(NH3 )(aq.)  NH3(aq.)

Ag(NH3 )(aq.) □ □ □ Ag(aq.)  NH3(aq.)

A complex-dissociation equlibrium constant (Kd) expression, which is the inverse of Kf can be
written for each of these reactions. Our problem has two reactions and therefore two Kd’s :
[Ag(NH3) ] [NH3]

Kd1  

[Ag(NH3)2 ]
 Chemistry : Ionic Equilibrium


K  [Ag ] [NH3]
d2 [Ag(NH )]
3

Alternatively, the individual steps in this reaction can be collapsed into an overall equation, which can
be described by an overall equilibrium constant expression :
 
Ag(NH 3 ) 2 (aq.) □ □ □ Ag (aq.)  2NH 3(aq.)

 2
K  [Ag ] [NH3 ]
d [Ag(NH 3 ) 2 ]
Illustration-28 : Calculate the complex dissociation equilibrium constant for the Cu(NH3)42+ ion
from the value of Kf for this complex. [Cu(NH3)4]2+; Kf = 2.1 × 1013]
Solution : The equilibrium expression for the complex formation reaction is written as follows :
2
K f  [Cu(NH3 )4 ]
[Cu ] [NH 3 ] 4
2

The equilibrium constant expression for the complex dissociation reaction is nothing more
nor less than the inverse of the complex formation equilibrium expression :
2 4
K  [Cu ] [NH3 ]
d
[Cu(NH 3 ) 4 2 ]
The value of Kd is therefore equal to the inverse of Kf :
1 14
Kd   4.810
Kf

6.8 APPROXIMATE COMPLEX-ION CALCULATIONS

Illustration 29 : What fraction of the total iron (III) concentration is present as the Fe3+ ion in
a solution that was initially 0.10M Fe3+ and 1.0 M SCN – ? [Fe(SCN) 2 + :
Kf = 2.3 × 103]
Solution : Complex-formation equilibiria provide another example of the general rule that it is useful
to begin equilibrium calculations by comparing the reaction quotient (here disignated Qf)
for the initial conditions with the equilibrium constant for the reaction. The initial conditions
can be summarized as follows :

Fe3(aq.)  2SCN(aq.) □ □ □ Fe(SCN) 2(aq.) Kf  2.3 103

Initial : 0.10M 1.0M 0
The initial value of the reaction quotient is therefore equal to zero :

Qf  [Fe(SCN) 2 ]
 (0)  0  2.3 10 3
[Fe3 ] [SCN ]2 (0.10) (1.0)2
Because the reaction quotient is very much smaller than the equilibrium constnat for the
the reaction, it would be absurd to assume that the reaction is close to equilibrium. We
define a set of intermediate conditions in which we drive the reaction as far as possible
toward the right :
 Fe3(aq.)  2SCN(aq.) □ □ □ Fe(SCN) 2(aq.) Kf  2.3103
Initial : 0.10M 1.0M 0
Change: 0.10M 2(0.010)M 0.10M
Intermediate 0 0.8M 0.10M
We then assume that the reaction comes to
equilibrium from these intermediate conditions :

Fe 3(aq.)  2SCN (aq.) □ □ □ Fe(SCN)2(aq.) K f  2.3 103

Intermediate : 0 0.8M 0.10M
Equilibrium :  0.8  2 0.10  

Substituting this information into the equilibrium

expression for the reaction gives the following equation :
[0.10  ]
 2.3103
[] [0.8  2]2
We are now ready to assume that  is relatively small :
[0.10]
 2.3103
[] [0.8]2
Solving this approximate equation gives the following result :
  6.8 105
The assumption that  is relatively small is valid because the problem was defined so that
it would be valid. We can now use this value of  to answer the original question :
[Fe3 ]  6.8 105 M
Even though the complex formation equilibrium constant is not very large, essentially all
of the iron in this solution is present as the Fe(SCN)2+ complex ion. Only a negligible
fraction is present as the Fe3+ ion :
6.8 105
 100% 0.068%
0.10

Illustration-30 : Calculate the concentration of the Cu2+ ion in a solution that is initially 0.10 M Cu2+
and 1.0M NH3. [Cu(NH3)42+ : Kf = 2.1 × 1013]
Solution : We can set up this calculation as follows :

Cu2(aq.)  4 NH3(aq.) □ □ □ Cu(NH3 )42(aq.) Kf  2.11013

Initial : 0.10 M 1.0M 0
Because Kf for this complex is very large, essentially all of the Cu2+ ions should form
Cu(NH3)42+ ions at equilibrium. We therefore define a set of intermediate conditions in
which we shift the reaction to the right until all of the Cu2+ ion is converted into Cu(NH3)42+
complex ions :
 Chemistry : Ionic Equilibrium

Cu2(aq.)  4 NH3(aq.) □ □ □ Cu(NH3 )42(aq.) Kf  2.11013

Initial : 0.10M 1.0M 0
Change : 0.10 M 4(0.10 M) 0.10 M
Intermediate : 0 0.6 M 0.10 M

We then let the reaction come to equilibrium from these intermediate conditions:
2 2
Cu (aq.)  4 NH 3(aq.) □ □ □ Cu(NH 3 ) 4 (aq.) K f  2.11013
Intermediate : 0 0.6 M 0.10 M
Equilibrium :  0.6  4  0.10  

The next step in solving this problem involves writing the equilibrium constant expression
for the reaction :
2
K f  [Cu(NH3 )4 ]
[Cu 2 ] [NH 3 ] 4
We then substitute what we know about the equilibrium concentration of the three
components of this reaction into this equation :
[0.10  ]
 2.11013
[] [0.6  4]4
The value of Kf is so large that very little Cu(NH3)42+ complex ion dissociates as the
reaction comes to equilibrium. It is therefore reasonable to assume that  is relatively
small :
[0.10]
 2.11013
[] [0.6]4
Solving this approximate equation gives the following result :
  3.7 1014
The assumption that  is small is valid. We can therefore use the results of this calculation
to determine the concentration of the free (uncomplexed) Cu2+ ion in this solution :
[Cu2+] = 3.7 × 10–14 M
The result of the preceding excerise can be used to explain why Cu(OH)2 dissolves in
excess ammonia. Before we can do this, however, we need to understand why Cu(OH)2
precipitates in the first place. Ammonia acts as a base toward water :]

[NH4 ] [OH ]
Kb  1.8 105
[NH3 ]
Even fairly dilute solutions of the OH– ion have more than enough OH– ion to precipitate
Cu(OH)2 from an 0.10 M Cu2+ ion solution. As the amount of NH3 added to the solution
increases, the concentration of the OH– ion concentration in a 0.001 M NH3 solution is
1.3 × 10–4 M. By the time the NH3 concentration reaches 0.10 M, the OH– ion
concentration has increased by only a factor of 30, to 4.2 × 10–3 M.
As the amount of NH3 added to the solution increases, the concentration of Cu2+ ions
rapidly decreases because these ions are tied up as Cu(NH3)42+ complex ions. According
 to the preceding exercise, the Cu2+ ion concentration in 1.0 M NH3 is only 3.7 × 10–14 M.
Thus, the ion product for Cu(OH)2 under these conditions is about the same size as the
solubility product for this compound
Qsp = (Cu2+) (OH–)2 = (3.7 × 10–14) (4.2 × 10–3)2 = 6.5 × 10–19  Ksp
As soon as the NH3 concentration exceeds 1 M, the Cu2+ ion concentration becomes so
small that the ionic product for Cu(OH)2 is smaller than Ksp, and the Cu(OH)2 precipitate
dissolves.

6.9 USING COMPLEX-ION EQUILIBRIA TO DISSOLVE AN INSOLUBLE SALT

The key to using complex-ion equilibria to dissolve an insoluble salt is simple : Choose a complex for
which Kf is large enough that the concentration of the uncomplexed metal ion is too small for the ion
product to exceed the solubility product. To show how this is done, let’s return to a topic introduced
in previous section.
Illustration-31 Calculate the solubility of AgBr in 1 M S2O32–. (AgBr : Ksp = 5 × 10–13;
Ag(S2O3)23–: Kf = 2.9 × 1013)
Solution : Two equilibria must be considered in this problem, the solubility product for AgBr and the
complex formation equilirium for the Ag(S2O3)23– complex ion :
AgBr(s) □ □ □ Ag(aq.)  Br (aq.)
3
 2  □ □□ 
A g ( aq .)  2S 2 O 3 ( aq .) □ □□ A g (S 2 O )
3 2 ( aq .)

AgBr will dissolve if the Ag(S2O3)23– complex is strong enough to reduce the Ag+ ion
concentration to the point at which the product of the Ag+ and Br– ion concentrations at
equilibrium is small than the Ksp of AgBr.
One way to decide whether Kf for this complex ion is large enough to overcome the
solubility product equilibrium involves combining the equilibria in this solution to give the
following overall equation :

AgBr(s)  2S2O32(aq.) □ □ □ Ag(S2O3 )23(aq.)  Br(aq.)

The equilibrium constant for this reaction is the product of Kf times Ksp :
K = Kf × Ksp = (2.9 × 1013) (5 × 10–13) = 15
Because the equilibrium constant is larger than 1, a significant amount of AgBr should
dissolve in this solution :
[Ag(S2O3 )23 ] [Br ]
[S2O32 ]2
When AgBr dissolves in pure water, the concentration of the Ag+ and Br– ions must be
the same.
In pure water : [Ag+] = [Br–] = Cs
In 1 M S2O32– : [Ag(S2O3)23–)] = [Br–] = Cs
The concentration of the S2O32– ion at equilibrium will be equal to the initial concentration
of this ion minus the amount consumed when the Ag(S2O3)23–) complex is formed :
[S2O32–] = 1 – 2 Cs
Substituting this information into the equilibrium constant expression for the overall reaction
gives the following equation :
[Cs ] [Cs ]
 15
[1  2Cs ]2
 Chemistry : Ionic Equilibrium

Solving this equation with the quadratic formula gives the following result :
Cs = 0.44 M
The Ag(S2O3)23– complex ion is strong enough to dissolve up to 0.44 moles of AgBr per
liter of solution. It isn’t surprising that the thiosulfate ion is used as the filter in the processing
of virtually all commercial photographic films.

EXERCISE – 4
1. A saturated solution of Ag2CrO4 prepared by dissolving solid Ag2CrO4 in water has
[CrO42–] = 6.5 × 10–5 M. Calculate Ksp for Ag2CrO4.
2. Which has the greater molar solubility :
AgCl (K = 1.8 × 10–10) or Ag CrO (K = 1.1 × 10–12) ? Which has greater solubility in gram
sp 2 4 sp
per litre (= molar solubility × molecular weight) ?
Ag = 108, Cr = 52, Cl = 35.5, O = 16.
3. Solubility of AgCl(s) in aqueous saturated solution is 1.4 × 10–5 M at 30°C. What is molar
solubility in 0.1 M AgNO3?
4. Will a precipitate form on mixing equal volumes of the following solutions?
Ksp (BaCO3) = 2.6 × 10 –9

(a) 3 × 10–3 M BaCl and 2 × 10–3 M Na CO

2 2 3
(b) 1 × 10–5 M Ba(NO ) and 4 × 10–5 M Na CO
3 2 2 3

5. Predict whether the solubility of BaF2 will increase, decrease or remain the same on addition
of each of the following reagents :
(a) HCl (b) HF
(c) NaNO3 (d) Ba(NO3)2
6. What is the molar solubility of Mg(OH)2 in a solution that has a pH of :
(a) 12.0 (b) 9.00
Ksp [Mg(OH)2] = 5.6 × 10 –12

7. ACID BASE TITRATION USING INDICATORS

Acid and Bases are the substances that are so frequently used that it is necessary to determine their
concentrations. Acids and Bases react to form salt and water and the reaction is known as
neutralization. The concentration of acid or base is determined by titration. Titration is a technique to
determine quantitatively the concentration of one substance if that of the other is known.
Indicator : An indicator is a substance that is used to determine the end point in a titration. End point
is one when one equivalent of acid reacts with one equivalent of base. The change in colour of the
indicator is noted at the end point.
Equivalence point is the point where the two substances are present in equal milligram equivalent or
equal gram equivalents.
Acid/Base indicators are usually weak organic acids or weak organic bases which show the change
in colour with in a certain pH range.
 Colours of some common indicators in different pH range.
Indicators pH range
Methylorange Red < 3.1 > 4.5 Yellow
Phenolphthalein Colourless < 8.3 > 10 Pink
Methyl red Pink < 4.2 > 6.2 Yellow
Bromocresol Green Yellow < 3.8 > 4.6 Blue
Bromocresol Purple Yellow <5 > 6.8 Purple
Bromothymol Blue Orange <6 > 7.5 Blue
Thymolphthalein Colourless < 9.3 > 10.5 Blue

7.1 THEORY OF INDICATORS

Two theories have been put forward to explain he colour change of indicators at end point.
1. Ostwald theory : Since indicator is a weak organic acid or base hence unionized molecules
possess a colour different from ions.
2. Quinonoid theory : The acid base indicators are aromatic organic compounds, which can exist in
two tautomeric forms in equilibrium with one another.

CH CH CH CH
C C □ □□ C C
CH CH CH CH
Benzenoid form Quinonoid form

Quinonoid form has deeper colour than corresponding, benzenoid form.

Phenolphthalein [HPh]. it is a weak organic acid. The unionized molecules are colourless while
on ionization, it gives colourless H+ and pink coloured Ph– ions.

HPh □ □□ H  Ph
Colourless Pink
acid form conjugate base

Addition of H+ i.e. addition of acid suppresses the ionization of HPh due to the presence of
common ion, H+ ions, and solution remains colourless. When a base like NaOH or KOH is
added, OH– added form unionized water. The removal of H+ moves the equilibrium to right side
and the solution is of pink colour.
Methylorange [MeOH] : It is a weak base and ionizes as
MeOH □ □ □ Me+ + OH –
yellow red
When a strong base is added to the indicator, it suppresses the ionization and yellow colour is
observed. When a strong acid is added to methyl orange, it enhances the ionization and red
colour is observed.
Choice of indicator depends on
1. Abrupt change of pH during neutralization near the equivalence point.
2. A suitable indicator is one that have a colour change over a pH range that falls with in the steep
part of the titration curve close to the equivalence point.
3. The solution at the equivalence point is not necessary neutral. It is neutral if the acid and base
both are strong. But if either of the two is weak or both are weak then the salt formed will
undergo hydrolysis. So the pH will depend upon the hydrolysis constant of the salts.
 Chemistry : Ionic Equilibrium

7.2 ACID-BASE TITRATIONS AND USE OF INDICATORS

The process of acid-base titrations is accompanied by a change in pH. A plot between pH of the
solution during titration and the amount of acid (or alkali) added from a burette is called a titration
curve.
Indicators are frequently employed in detecting end points in acid-alkali titrations. Since, on account
of hydrolysis, the pH at the end point depends upon the relative strengths of the acid and the base
being titrated and since different indicators have different pH ranges within which they can be used,
the selection of a proper indicator for a given titration is very important. The pH changes occurring
in some acid-base titrations may be first considered.
Titration of a strong acid against a strong base : The titration of a strong acid with a strong base
may be illustrated by the reaction of hydrochloric acid and sodium hydroxide. Suppose, 25 ml of 0.1
M HCl is to be titrated against 0.1 M NaOH. The equivalence or end point will, evidently, occur on
the addition of 25 ml of the alkali solution. The pH values of the solution at different stages of
neutralization are plotted graphically in Fig. 1. against the increasing amounts of the alkali added. It
is seen that pH changes very slowly at first and rises from 1 to only about 4 when such a large
amount as about 24.99 ml of the alkali solution has been added, i.e., when about 99.9 per cent of the
acid has been neutralized. Further addition of such a small amount as 0.01 ml of the alkali raises the
pH by about 3 units to 7. The acid is now completely neutralized. Further addition of such a small
amount as 0.01 ml of the sodium hydroxide solution (0.1 M) will amount to adding free hydroxyl ions
and the pH will jump to a value above 9. Thus, near the end point, the titration curve is almost
vertical and there is a rapid change of pH from 4 to about 10.
Now an indicator is suitable only if it undergoes a change of colour at the pH prevailing near the end
point. A reference shows that there are a number of indicators including methyl orange, methyl red,
bromothymol blue and phenolphthalein which can undergo colour change within the pH range 4 to
10. Thus, while titrating a strong acid with a strong base, any of the above indicators may be used to
detect the end point. The pH range of these indicators are also shown in Fig. 1 for convenience of
reference.

11
10
9 Phenolphthalein
8
7 Bromothymol Blue
6
5
Methyl Orange
4
3
2
1

0 5 10 15 20 25 30 35
Value of Alkali Added

Fig. 1 The pH titration curves of different acids with sodium hydroxide.

The pH ranges of the indicators involved are also shown in the figure.
Titration of a weak acid with strong base : The titration of a weak acid like acetic acid, against
a strong base like sodium hydroxide, is included in Fig. 1. It will be seen that the vertical portion now
does not being until beyond pH 7 and the end point lies somewhere between pH 8 and 10. This is due
to hydrolysis of sodium acetate. This, being a salt of a weak acid and a strong base, gives excess of
free OH– ions in aqueous solution due to hydrolysis. Hence, phenolphthalein will be a satisfactory
indicator but not methyl orange, methyl red or even bromothymol blue. Thymol-phthalein, though not
so common, is another suitable indicator for such titrations.
Fig. 1 also includes a titration curve for boric acid against sodium hydroxide. This titration curve
does not show any sharp rise in pH. This is because boric acid is so weak (its dissociation constant
being 6.0  10–10) that its salt sodium borate formed during the reaction gets very largely hydrolysed
giving alkaline solution. The pH, therefore, goes on rising continuously and there is no sharp rise at
the equivalence point. Hence, there is no abrupt change in the colour of the indicator for the addition
of a small amount of sodium hydroxide at the equivalence point. Thus, the acids with dissociation
constants less than 10–7 cannot be successfully titrated.
Titrations of a weak base with a strong acid : The titration curve of a weak base like ammonium
hydroxide, against a strong acid like hydrochloric acid, is shown in Fig. 2 (dotted line). The pHof
NH4Cl (a salt of a weak base and a strong acid) lies in the acid range due to hydrolysis. The pH
change at the equivalence point, therefore lies in the range 6 to 4. Thus, methyl orange and methyl
red are useful indicators while phenolphthalein cannot be of any use.
Tirations of sodium carbonate with hydrochloric acid

12

10

6
pH
4

0 5 10 15 20 25 30 35
Value of HCl Added

Fig. 2 The pH titration curves of weak bases with a strong acid.

The titration curve obtained on reacting sodium carbonate with hydrochloric acid is also included in
Fig. 2. It shows two inflection points. One of these indicates the conversion of sodium carbonate into
bicarbonate:
Na2CO3 + HCl  NaHCO3 + NaCl
This is completed at about pH 8.5 and phenolphthalein can be used to detect the end point. The
second point of inflection indicates the neutralization of sodium bicarbonate:
NaHCO3 + HCl  NaCl + CO2 + H2O
This reaction gets completed at pH 4.3. Therefore, methyl orange is a highly suitable indicator in this
case while phenolphthalein is not of any use.
 Chemistry : Ionic Equilibrium

Illustration-32 If an acidic indicator ionizes as HIn □ □ □ H+ + In–, to which maximum pH value

its solution has distinct colourcharacteristics of HIn. [Assume for colour change the
ratio of [In-]/[HIn] is equal to 10 or 0.1].

Solution : HIn □ □□ H+ + In–

Colour A Colour B
[H ][In ]
KIn =
[HIn]

 [In ]
log KIn = log [H ]  log
[HIn]
[HIn]
log [H+] = log KIn  log
[In ]

[In ]
pH = pKIn  log
[HIn]
[In ] 10
If colour B is to be observed then =
[HIn] 1
pH = pKIn + 1
[In ] 10
If colour A is to be observed then =
[HIn] 1
pH = pKIn – 1
or pH = pKIn ± 1
Illustration-33 An acid type indicator HIn difers in colour from it’s conjugate base. (In–). The
human eye is sensitive to colour differences only when the ratio [In–]/[HIn] is greater
than 10 or smaller than 0.1 What minmum change in he pH of the solution to
observe a complete colour change (KIn = 1.0 × 10–5).

Solution : HIn □ □ □ H+ + In–

[H ][In ]
KIn = [HIn]
When [In–] / [HIn] = 10
1
[H+] = KIn   106
10
pH = 6
[In ] 1
When =
[HIn] 10
[H+] = 10–5 × 10 = 10–4
pH = 4
Minimum change = 6 – 4 = 2
Illustration-34 An acid indicator HPh has Ka = 10–5. The acid form of indicator is colourless and
basic form is pink. What change in [H+] is required to change indicator from 75%
colourless to 50% pink.

Solution : HPh □ □□ H+ + Ph–

Colourless Pink
Initial % 75% 25%
% after change in [H+] 50% 50%

[H ][Ph ]
KIn =
[HPh]

KIn [HPh]
[H+] =
[Ph ]

5 75
[H+]1 = 10   3105
25

5 50
[H+]2 = 10   105 Change in [H+] = 2 × 10–5.
50

EXERCISE – 5
1. The Ka of a certain indicator is 2.0 × 10–6. The colour of HIn is green and that of In– is red. A
few drops of the indicator are added to a HCl solution which is then titrated against a NaOH
solution. At what pH will the indicator change colour ?
2. The ionization constant K of an indicator HIn is 1.0 × 10–6. The colour of the non-ionised form
a
is red and that of the ionised form is yellow. What is the colour of this indicator in a solution
whose pH is 4.00?
3. The pKa of phenolphthalein is 9.10 over
(a) What pH range does this indicator change from 95 percent HIn to 95 percent In–?
(b) What is ratio of non-ionised form to the ionised form of the indicator at pH 8.00?