TOPIC : IONIC EQUILIBRIUM

LECTURE # 1
Introduction

When an electrolyte is dissolved in a solvent(water), it spontaneously dissociates into oppositly charged

ions, partially or sometimes fully
NaCl (aq) Na+ (aq) + Cl– (aq)
CH3COOH (aq) CH3COO– (aq) + H+ (aq)
The degree of dissociation of an electrolyte () is the fraction of one mole of the electrolyte that has dissociated
under the given conditions. The value of  depends on
(A) nature of the electrolyte (B) nature of the solvent
(C) the dilution (D) temperature
(a) Nature of electrolyte :
Electrolytes 100% dissociated at all reasonable concentrations under normal temperatures - strong
electrolytes.
Strong acids(generally HClO4, HI, HBr, HCl, H2SO4, HNO3), strong bases (generally (NaOH, KOH, RbOH,
CsOH and Ba(OH)2) and all type of salts (SASB, SAWB, WASB, or WAWB)are all examples of strong
electrolytes.
electrolytes not 100% dissociated - weak electrolytes. weak acids (CH3COOH, HCN), weak bases(NH3,
Zn(OH)2) are examples.

Electrolytic substances :
1. For strong electrolyte  is considered to be unity because of 100% ionisation.
2. For weak electrolyte In most practical cases  <<< 10% or  < 0.1 (generally valid if Keq < 10–3)

(b) Nature of solvent :

A solvent having high value of dielectric constant and high solvation(in water hydration) will favour
dissociation.
(c) Temperature :
On increasing temperature generally degree of dissociation increases.
(d) Ditultion :
For some electrolytes degree of dissociation increases by dilution (Ostwald’s dilution law)

ACIDS BASES AND SALTS :

1. Arrhenius concept :
Arrhenius Acid : Substance which generate H+ ion on dissolving in water (H+ generator)
eg. HNO3, HClO4, HCl, HI, HBr, H2SO4, H3PO4 etc.

If acid release only one H+ ion is known as mono basic/monoprotic symbol - H.A.
If two H+ ion releases then known as dibasic/diprotic symbol  H2A
If triprotic / tribasic eg. H3PO4 (symbol H3A)
* H3BO3 is not Arhenius acid.
* Due to high charge density, H+ ion in water is extremely hydrated (in form of H3O+, H5O2+, H7O3+)
* The structure of solid HClO4 is studied by X-ray, It is found to be consisting of H3O+ and ClO4¯.
HClO4 + H2O H3O+ + ClO4¯ (better representation)
 Arrhenius base :
Any substance which releases OH¯ ion in water (OH¯ ion generator)
 mono acidic base : CsOH, RbOH, NH4OH symbol BOH
 diacidic base : Ba(OH)2, Ca(OH)2 symbol B(OH)2
 Tri-basic base : Fe(OH)3
* OH¯ ion also in hydrated form of H3O2¯, H7O4¯, H5O3¯
2. Bronsted - Lowery concept : (Conjugate acid - base concept) (Protonic concept)
Acid : H+ doner
Base : H+ acceptor
HA + H2O  H3O+(aq) + A¯ (aq)
Hydronium ion

NH3 + H2O NH4+ + OH¯

Base-1 Acid -2 Acid-1 Base-2

HCl + H2 O H3O+ + Cl¯

Acid-1 Base-2 Acid-2 Base-1

** Congugate acid - base pair

Acid - base which differ only in one proton.

Acid Congugate base

(i) HCl Cl¯
(ii) H2SO4 HSO4¯
(iii) HSO4¯ SO42–
(iv) H2O OH¯

Base Congugate acid

(1) NH3 NH4+
(2) H2O H3O+
(3) RNH2 RNH3+

(i) Strong acid will have weak conjuagate base.

(ii) Reaction will always proceeds from strong acid to weak acid or from strong base to weak base.
H2 O H+ + OH¯

H2SO4 + HCO3– H2CO3 + HSO4–

S.A S.C.B. W.A W.C.B

Amphoteric (amphiprotic) : Can act as acid as well as base.

HCl + H2O H3O+ + Cl¯
Base

NH3 + H2O NH4+ + OH¯

Acid

Q. If equal concentrations are mixed (of products & reactants) then which of the reaction will proceed to the right
and which will proceed to the left.
(A) H2SO4 (aq) + NH3 (aq)  NH4+ (aq) + HSO4– (aq)
(B) HCO3– (aq) + SO42– (aq)  HSO4– (aq) + CO32– (aq)
Q. (a) Write conjugate acids of
SO42– , RNH2 , NH2– , C2H5O C2 H5 , F–
(b) Write conjugate basis of
HNO2 , OH–, H2CO3, HClO4.
(c) Write conjugate acids and conjugate basis of amphoteric species.
HS– , NH3, C2H4OH, H2O
3. Lewis concept (electronic concept) :
An acid is any molecule/ion which can accept an electron pair with the formation of a coordinate bond.
A base is any molecule/ion which has a lone pair of electrons which can be donated.
 Acid  e– pair acceptor
** BF3, AlCl3
** H+, Fe2+, Na+
** SF4, PF3

 Base  (One electron pair donate)

** NH3, PH3, H2O, CH3OH

Ex. In the reaction

(A) C2H5NH2 + H  (C2H5NH3)+ –. which reactant would be considered as Bronsted acid, is it also an
Arrhenous acid is it also a lewis acid.
Ans. [H, yes, no]

(B) What about the other species (C2H5NH2) in the above reaction is it Arrhenius base is it Bronsted base, is it
lewis base.
Ans. [No, yes, yes]

Ostwald’s Dilution Law (for weak electrolyte’s)

When a weak electrolyte A+B– is dissolved is water and if  is the degree of dissociation then
AB A+ + B–
initial conc C 0 0
conc-at eq. C(1 – ) C C
Then according to law of mass action,
[ A  ][B – ] C . C C 2
Keq =   = dissociation constant of the weak electrolyte
[ AB ] C(1   ) (1   )

1 2
[C = , then V = 1/C(volume of solution is which 1 mole is present) is called dilution, so keq = ]
V (1   )V

k eq
If  is negligible in comparision to unity 1 –  ~
– 1. so keq = 2 C =  k eq . V
c

1


0.1

as concentration increases   decreases  dilution decreases and at infinite dilution reaches

its maximum value, unity. C  ,   but (C) 
 LECTURE # 2

Acidity and pH scale :

Acidic stength means the tendency of an acid to give H3O+ or H+ ions in water and basic strength means the
tendency of a base to give OH– ions in water. So more the tendency of the substance to give H+ or OH– ions,
more will be the acidic or basic strength of the substance.
The concentration of H+ ions is written in a simplyfied scale introduced by Sorenson known as pH scale. pH
is negative logarithm of activity of H+ ions.
 pH = – log aH (where aH is the activity of H+ ions)
Activity of H+ ions is the concentration of free H+ ions or H3O+ ions in a solution.
For dilute solutions [H+]  1M concentration can be taken as activity of H+ ions while for higher concentrations
the activity would be much less than the concentration itself, so is calculated experimentally.
The pH scale was marked from 0 to 14 with central point at 7 at 25°C taking water as solvent. If the
temperature and the solvent are changed, the pH range of the scale will also change. For example
0 – 14 at 25°C
0 –13 at 80°C (Kw = 10–13)
[Note : pH can also be negative or > 14]

pH = – log [H+] ; [H+] = 10–pH

pOH = – log [OH–] ; [OH–] = 10–pOH
pKa = – log Ka ; Ka = 10–pKa
pKb = – log Kb ; Kb = 10–pKb

PROPERTIES OF WATER :
1. Acid/base nature:
Water - an acid as well as base according to Arhenius and Bronsted-Lowry theory but according to Lewis
concept it can only be taken as base only.
In pure water [H+] = [OH–] so it is Neutral.
2. Moler concentration / Molarity of water :
mass of 1  litre water in garms
No. of moles/liter of water =
molecular mass of water
1000gm
Molarity No. of moles/litre = 18gm = 55.55 mole /litre = 55.55 M (density = 1 gm/cc)
3. Ionic product of water :
According to Arrhenius concept
H2 O H+ + OH– so, ionic product of water, kw = [H+][OH–] = 10–14 at 25° (exp.)
increasing temp  kw increases (dissociation of water, is endothermic, so on increasing temperature
Keq. increases)
Now pH = –log[H+] = 7 and pOH  log[OH–] = 7 for water at 25° (exp.)
pH = 7 = pOH  neutral
pH < 7 or pOH > 7  acidic
pH > 7 or pOH < 7  Basic

Note. Ionic product of water is always a constant whatever has been dissolved in water since its an
equilibrium constant so will be dependent only on temperature.
4. Degree of dissociation of water :
no. of moles dissociated 10 7
H2 O H+ + OH–   =  18 x10 10 or 1.8 x 10 7%
Total No. of moles initially taken 55.55
5. Absolute dissociation constant of water :
[H ][OH ] 10 7  10 7
H2 O H+ +OH– Ka = Kb = =  1.8  10 16
[H2O] 55.55
So, pKa = pKb = – log (1.8 × 10-16) = 16 – log 1.8 = 15.74

Note: For a conujugate acid base pair prove that

pKa + pKb = pKw (pKw = – log Kw) =14 or Ka × Kb =Kw
Note: pKa of H3O+ ions = –1.74
Note: pKb of OH– ions = –1.74

Q.  For a conujugate acid base pair prove that

pKa + pKb = pKw (pKw = – log Kw) =14 or Ka × Kb =Kw
Sol. let B is Bronsted-lowry Base

[BH  ][OH ]
B + H2O BH + OH 
+ – Kb  ...(1)
[B]

[H ]  [B]
BH+ H+ + B  Ka = ...(2)
[BH ]
Ka × Kb = [H+] [OH–] = Kw
 – log Ka – log Kb = – log Kw  pKa + pKb = pKw = 14 at 25ºC

2. At a temperature under high pressure Kw(H2O) = 10–10, A solution of pH 5.4 under these conditions is said to
be:
(A) acidic (B) basic (C) neutral (D) amphitoric

Q.  Which is stronger acid H3O+ or acetic acid (Ka = 1.8 × 10–5)

 pKa(H3O+) < pKa (acetic acid)
so, H3O+ is stronger acid than acetic acid
pH Calculations of Different Types of Solutions :
(a) Strong acid solution :
(i) If concentration is greater than 10–6 M
In this case H+ ions coming from water can be neglected,
so [H+] = normality of strong acid solution
(ii) If concentration is less than 10–6 M
In this case H+ ions coming from water cannot be neglected and since water is a weak
electrolyte so its dissociation equilibrium will be disturbed much more than dissociation
equilibrium of strong acid.
So [H+] = normality of strong acid + H+ ions coming from water in presence of this strong acid
(b) Strong base solution :
Using similar method as in part (a) calculate first [OH–] and then use [H+] × [OH–] = 10–14

Q.  Caculate pH of a soultion obtanied by dissolving 490 mg of H2SO4 in water, so total volume of solution
becomes 100 ml.

490  10 3 1
Sol. Molarity = × 1000 = = 0.05
98  100 20
Normality = 2 × molarity = 0.1
pH = – log 10–1 = 1

Q. Calculate pH of 10–7 M of NaOH solution

Sol. [OH–]from NaOH = 10–7
[OH–] from water = x < 10–7 M (due to common ion effect)
H2 O OH– + H+
– (x + 10–7) x
Kw = [H ] [OH–] = 10–14 = x (x + 10–7)
+

x2 + 10–7x – 10–14 = 0

5 1
 x= × 10–7 = 0.618 × 10–7 ( 5 = 2.236)
2
[OH–] = 10–7 + 0.618 × 10–7 = 1.618 × 10 –7
pOH = 7 – log (1.618) = 6.8
pH = 14 – 6.8 = 7.2

Ex.  Calculate the  of water and pH of 10 –7 M HCl solution.

Sol. [H+] HCl = 10–7 M
H 2O H++ OH¯
(10–7 + x) x
Kw = [H+] [OH¯]
10–14 = x (10–7 + x)
 x + 10–7x – 10–14 = 0
2

x = 0.618 x 10–7
Net [H+] = 10–7 + x
= 10–7 + 0.618 x 10–7
= 1.618 x 10–7
 pH = 7 – log 1.618

x
= 7 – 0.2 = 6.8 = x 100%
1000
18
= 0.618 x 1.8 x 10–9 /0.618 x 1.8 x 10–7%
% change in  of water
(1  0.618 ) x 1.8 x 10 9
= × 100% = 38.2%
1.8 x 10 9
Ex.  Calculate pH of 10 –8 M HCl solution.
Sol. H2O H+ + OH¯
10–8 + x x
Kw = [H+] [OH¯]
10–14 = x(x × 10–8)
 x 2 + x × 10–8 – 10–14 = 0

 10 8  10 16  4 x 10 14
x=
2

1
 10 8  10 7 4 
= 100
2

( 401  1)10 8
= = 0.95 x 10–7
2
[pH] = 10.5 x 10–8 = 1.05 x 10–7
[pH] = 7 – log 1.05  6.98
10–9 M HCl pH  7
10–16 M HCl pH  7

Ex.  Calculate amount of water added to the solution of pH = 2.1. So that pH may get increased to
4(log2 = 0.3)
Sol. [H+]f = 10–4 M
[H+]i = 8 x 10–3 M
Vi = 1Lt. = 1000 ml
no. of moles = (8 x 10–3) x (1)
of water initially
Finalley no. of moles = 10–4 x Vf
8 x 10–3 = 10–4 Vf
 80 = Vf
Volume of water added = 80 – 1 = 79 
 LECTURE # 3
(c) pH of mixture of two strong acids :
If V1 volume of a strong acid solution of normality N1 is mixed with V2 volume of another strong acid
solution of normality N2 , then
Number of H+ ions from -solution = N1V1
Number of H+ ions from -solution = N2 V2
If final normality is N and final volume is V, then
NV = N1 V1 + N2 V2
[dissociation equilibrium of none of these acids will be disturbed as both are strong acid]
N1V1  N2 V2
[H+] = N = V1  V2
(d) pH of mixture of two strong bases :
similar to above calculation
N1V1  N2 V2
[OH–] = N = V1  V2

1 1
Q. Calculate pH of mixture of (400ml , M H2SO4) + (400ml, M HCl) +( 200 ml of water)
200 100

1 400 4 4
Sol. N1V1 =   , N2 V2 = , H+ ions from water will be neglected
100 1000 1000 1000
N1V1+ N2V2 = 8 × 10–3

8  10 3
[H+] = = 8 × 10–3
1
pH = 3 – log 8 =2.1

Q. A 200 ml of 0.1 M HCl solution is added to a 500 ml solution of H2SO4 containing 4.9 gm/lt and water is added
to the resultant solution so that the final volume becomes one litre. Calculate the pH of resultant solution.
(log 7 = 0.84)
Sol. NHCl = 0.1 N, VHCl = 200 ml
 me. of HCl = 20
4 .9
me. of H2SO4 = × 500 = 50
49

20  50
 [H3O+] = = 0.07
1000
pH = – log (0.07) = 1.16

Ex.  500 ml of 10 –5 M NaOH is mixed with 500 ml of 2.5 x 10 –5 M of Ba(OH) 2. Inresulting solution
99 L water is added. Calculate pH.
.500  10 5  500  2  2.5  10 5
Sol. [OH–] = 
.1000
= 3 × 10–5 M
M1 = 3 × 10–5 M
V1 = 1 L
V2 = 100 L
no. of moles of [OH –] initially = no. of moles of [OH]– of
3 × 10–5 = M2 × 100
 M2 = .3 × 10–7 < 10–6
H2O H–1 + OH–
x (x + 3 × 10–7)
 Kw = x (x + 3 × 10–7) = 10–14

 13  3 
  –7
 x=  2  × 10
 

 13  3 
[OH–] Net = 3  
2  × 10
–7


 3  13 
=   × 10–7 = 2.36 × 10–7
 2 
(e) pH of mixture of a strong acid and a strong base :
There will be neutralisation of the acid and the base, and the solution will be acidic or basic depending
on which component has been taken in excess.
If V1 volume of a strong acid solution of normality N1 is mixed with V2 volume of a strong base
solution of normality N2 , then
Number of H+ ions from -solution = N1V1
Number of OH– ions from -solution = N2 V2
If N1V1 > N2V2, then solution will be acidic in nature and
N1V1  N2 V2
[H+] = N = V1  V2
If N2V2 > N1V1, then solution will be basic in nature and
N2 V2  N1V1
[OH–] = N = V1  V2

Q.  Calculate pH of mixture of (400ml,

1
200
M Ba(OH)2) + (400ml,
1
50
M HCl) + ( 200ml of Water)

1 1
400   400  2
Sol. [H+] = 50 200 = 4×10 –3 , so pH = 3 – 2 log 2 = 2.4
1000
Q. 560 ml of HCl gas (measured at STP) is added to a 500 ml solution of 0.01 M NaOH. Calculate pH of
resutting solution. (log 2 = 0.3)
560 1
Sol. moles of HCl =  ,
22400 40

1
m eq of HCl =  1000 = 25
40
meq. of NaOH = 500 × 0.01 = 5
 Resulting solution is acidic
25  5 20 1
[H+] =  
500 500 25
 pH = log (25) = 1.4

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

We have to use Ostwald’s Dilution law(as have been derived earlier)
HA H+ + OH–
t=o C 0 0

[H ] [OH ] C 2
teq. C(1–) C C Ka = =
[HA] 1 
 Ka
if <<1 1 –  1  Ka  C2  = ( is valid if  < 0.1 or 10%)
C

Ka 1
[H+] = C = C = Ka  C So pH = pK a  log C 
C 2
on increasing the dilution  C  and [H+]  pH 

Q. Calculate pH of (a) 10–1 M CH3COOH (b) 10–3 M CH3COOH (c) 10–6 M CH3COOH
Take Ka = 2 ×10–5.
Sol. (a) CH3COOH CH3COO– + H+
C 0 0
C(1–) C C

C 2 Ka 2  10 5
Ka =   = = = 2 104 (<< 0.1)
1  C 10 1

1
So, [H+] = 10 –1 × 2 ×10 –2  pH = 3 – log 2 = 2.85
2

Ka 2  10 5
(b) = = = 2 102 ( > 0.1)
C 10 3
So we have to do the exact calculations

C 2 10 3   2
Ka =  2×10–5 =   = 13.14%
1  1 
[H+] = 10–3 × 0.1314 =1.314 ×10–4 pH = 4 – log (1.314)  3.8

2  10 5
(c) If approximation is used then,  = = 20 > 1,
10 6

2
so we have to do the exact calculation, 2×10–5 = 10–6    0.95 or 95%
1 
[H+] = 0.95 ×10–6 = 9.5 × 10–7  pH = 7– log (9.5) = 6.022

** At very low concentricity (  dilution) weak electrolyte will be almost 100% dissociate, so
behave as strong electrolyte
[pH of 10–6 M HCl ~
 pH of 10–6 M CH3COOH ~
 6; pH of 10–8 M HCl = pH of 10–8 M CH3COOH]

(g) pH of a solution of a polyprotic weak acid :

Let us take a weak diprotic acid (H2A) in water whose concentration is c M. Diprotic acid is the one, which
is capable of giving 2 protons in water.
In an aqueous solution of a diprotic acid, following equilbria exist.
H2A + H2O HA¯ + H3O+
Conc. at equilbrium c(1 –1) c(1 –2) (c1 + c1 )
HA¯ + H2O A2– + H3O+
Conc. at equilibrium c(1 –2) c2 (c1 + c1 )
where 1 is the degree of ionization (dissociation) of H2A in presence of HA¯ and 2 is the degree of ionisation
of HA¯ in presence of H2A.
Knowing the values of K a1 , K a2 and c, the values of 1 and 2 can be calculated using equations (i) and (ii).
After getting the values of 1 and  [H3O+] can be calculated as.
[H3O+]T = c1 + c12
 Approximation
For diprotic acids, K a2 < < K a1 and 2 would be even smaller than 1 .
 1 – 2  1 and 1 + 2  1
C1  1
Thus, equation (i) can be reduced to K a1 =
1  1 So [H ] = C1
+

This is an expression similar to the expression for a weak monoprotic acid. Hence, even for a diprotic acid (or
a polyprotic acid) the [H3O+] can be calculated from its first equilibrium constant expression along provided
K a2  K a1 .
Finally, if the total [H3O+] from the acid is less than 10–6 M, the contribution of H3O+ from water should be
taken into account for calculating pH while if it is > 10–6 M, then [H3O+] contribution from water can be ignored.
Using this [H3O+], pH of the solution can be calculated.

Q..  calculate pH of 0.1M H S solution 2

that Ka1 = 10–7

Ka

c
H2 S H+ + H S–
C O O
C( – C C (C = C1)

K a1 10 7
  = 10–3
c 10 1
 = 10 –3 ×10 –1 = 10–4  [H+] = 10–4 and pH =4
HS– H+ + S2–
C1 C1
C1(1–  C1+ C1 C1 
C1(1  1 )C11
Ka2 = C1(1  1 ) 1+   1

1–   1
14
10
 = = 10–10
10  4
net [H+] = C1+ C1

=10–4 + 10–4×10–14 =10–4+10–14

pH = 4
for H2S 2H+ + S2– K = Ka1 Ka2
C(1 –) 10–4 =10–21
[S 2  ]  10 8
K = 10–21 =
10 1
 LECTURE # 4
(h) pH of a mixture of two weak acid(both monoprotic) solutions :
let the acid are HA1 & HA2 and their final concentrations are C1 & C2 respectively, then
HA1 H+ + A1– HA2 H+ + A –2
t= 0 C1 0 0 C2 0 0
At eq. C1(1– 1) C11+C22 C11 C2(1– 2) C22+C11 C22
C11(C11  C 2  2 ) (C 2  2  C11 )C 2  2
K a1  ; Ka2 =
C1(1  1 ) C 2 (1   2 )
Ka1 = (C1C22)(1 <<< 1) ; 
Ka2 = (c1c2 2) (2 <<< 1)
K a1 1
 K a2 = 2

C1K a1 C 2K a2
[H+] = C11 + C2= C K  C K + C K C K  [H+] = C1K a1  C 2K a 2
1 a1 2 a2 1 a1 2 a2

If the dissociation constant of one of the acid is very much greater than that of the second acid then contribution
from the second acid can be neglected.
So, [H+] = C11 + C2  C11
** If water is again considered third weak acid in solution of two weak acid then
[H+] = K a1C1  K a2 C 2  K w

1000
Cw = = 55.5
18
Kaw = 1.8 × 10–16
CwKaw = 10–14 = Kw

[H+] = C1 K a1  C 2 K a 2  10 14

Ex. Calculate pH of solution obtained by mixing equal vol. of 0.02 M HOCl & 0.2 M CH3COOH solution
given that Ka1 (HOCl) = 2 × 10–4 (log2 = 0.3)
Ka2 (CH3COOH) = 2 × 10 –5

also calculate OH – , OCl–, CH3COO–

Sol. Final solution volume become double
C1 = 0.01, C2 = 0.1
[H+] = K a1C1  K a 2C 2

–3
= 2  10  4  0.01  2  10 5  0.1 = 2  10  6  2  10  6 = 2 × 10
pH = 3 – log2 = 3 – 0.3 = 2.7
4
2  10 2  10 5
1 = 3 = 10–1 ; 2 = = 10–2
2  10 2  10 3
HOCl H+ + OCl– CH3COOH H+ + CH 3COO¯
C1(1 – 1) C11+C22 C 11 C2(1 – 2) C11+C22 C 22
[OCl–] = C11 [CH3COO–] = C2 2
= 0.01 × 10–1 = 0.1 × 10–2
= 1 × 10–3 = 1 × 10–3

Kw 10 14
[OH–] =  = = 5 × 10–12 M
[H ] 2  10 3
[HOCl] = 10–2(1 –0.1) = 9 × 10–3 M
[CH3COOH] = 10–1 (1 – 0.01)  10–1
 (i) pH of a mixture of weak acid(monoprotic) and a strong acid solution :
For the first approximation we can neglect the H+ ions coming from the weak acid solution and
calculate the pH of the solution from the concentration of the strong acid only.
To be precise we have to take the effect of presence of strong acid on the dissociation equilibrium of
the weak acid.
If [SA] = C1 and [WA] =C2 , then [H+] from SA = C1 and [H+] from WA = C2
Let HA is a weak acid
HA H+ + A–
t=0 C2 0 0
(C 2   C1 ) C 2 
t = t(eq) C2(1– C2C1 C2  Ka = ()
C 2 (1   )
( The weak acids dissocia\tion will be further suppressed because of presence of strong acid)
Ka = (C2C1)
Finally, if the total [H+] from the acid is greater than 10–6 M, then contribution from the water can be neglected,
if not then we have to take [H+] from the water also.

** If a strong acid of low conc is added in water then [H+] of solution can be calculated as

C1  C12  4K w
[H+] =
2
KaC = Kw for water and this solution can be treated as SA + WA solution.

Ex.  Calculate pH 10 –1 M HCl if 10–3 M CH3OOH [Ka = 2 x 10–5]

Sol. CH3COOH CH3COO– + H+
(C1 – ) C 10–1 + C
C 10–1
+
H ion can be treated completely from HCl due to less dissociation of CH3COOH and its low conc.

C  10 1
2 × 10–5 =   = 2 × 10–4
C
[H+] CH COOH = C = 2 × 10–7
3

Ex.  In mixture [HCl] = 10 –4 M & [CH3COOH] = 10–2 M, Ka (CH3COOH) = 2 × 10–5

(i) Calculate pH, [OH–], [CH3COO–] (ii) %[H+] from CH3COOH (iii) % [H+] from H2O.
Sol. CH3COOH CH3COO– + H+
C C 10–4 + C
C–

C (C  10 4 )
Ka = 2 × 10–5 =
C
10–2 2 + 10–4  – 2 × 10–5 = 0
2 10–2  – 2 × 10–3 = 0

 10 2  10 4  8  10 3 9  10 2  10 2
 = = = 4 × 10–2 = 0.04 0.1
2 2
[H+] CH COOH = C = 10–2 × 4 × 10–2
3
[H+]net = 5 × 10–4  pH = 4 – log 5 = 3.3
[OH ] = 2 × 10 ; [CH3COO ] = 4 × 10–4
– –11 –

4  10 4
% [H+] from [CH3COOH] =  100 = 80%
5  10  4
2  10 11
% [H+] from H2O =  100 = 4 × 10–6 %
5  10  4
Ex.  Calculate pH [HS ], [S – 2– ], [Cl – ] in a solution which is 0.1 M HCl & 0.1 M H 2 S given that
Ka1(H2S) = 10–7 Ka2 (H2S) = 10–14. Also calculate 1 & 2
Sol. HCl + H2S
0.1 0.1
C1 = C2 = 0.1
 pH = 1 (most of [H+] comes from HCl)
H2S H+ + SH–
0.1(1 – 1) 10 –1 0.1 1

C1  10 1 10 7
Ka1 =  = 1  1 = 10–6
C(1  1 ) 10 1
HS¯ S2– + H+
C11(1 – 2) C12 0.1
10–14 = 0.1 × 2
 2 = 10–13
[S2–] = C1 2] = 10–6 × 10–1 × 10–13 = 10–20 M

Ex. Calculate pH, [H+], [OH–], [CH3COO–] [CH3COOH] [OH–], [H2S]

[S2–] in a solution obtained by mixing equal vol. of 0.2 M H 2S & 0.02 M acitic acid given that
Ka (CH3COOH) = 2 × 10–5
Ka (H2S) = 10–7
Ka (H2S) = 10–14
Sol. [H+] = 10 1  10 7  10  2  2  10  5 [H2S] = 0.1

= (0.1  2) x 10 7 [CH3COOH] = 0.01 in new solution

= 2.1 x 10 7 = 21 × 10
–4 * The only first [H+] of H2S is considered.

1
pH = 4 – log 21
2

2  10 5 2
() acitic acid = =  10 1 = 0.0436
4
21  10 21

10 7 10 7
(1) H2S =  = = 0.218 × 10–3
[H ] 21  10  4

[HS–] = C1 = 0.1 × 0.218 × 10–3 = 2.18 × 10–5 M

HS– H+ + S2–

21  10 4 [S 2  ]
10–14 = =
2.18  10 5 10 1

2.18  10 15
[S2–] =
4.56

2.18  10 15 10 10

2.18 × 10–5 × 2 = =
4.56 4.56
Ex. Calculate conc. of H 3PO4, H2PO4–, H2PO42–, PO 43–, [H+] ; pH, [OH–] of 0.1 M H3PO4 acid solution
given K a 2  10  3 , K a 2  10  7 , K a 3  10 12

Sol. H3PO4 H2PO4– + H+

0.1 – x x x

x2
Ka1 = = 10–3
0.1  x
x = 0.01 = [H+] = [H 2PO4–]
and [HPO 42–] = 10–7 M
3
[H ] [PO 4 ] 3
(0.01) [PO 4 ]
Ka3 = 2  10–12 =
[HPO 4 ] 10 7
[PO 43–] = 10–17 M
[OH–] = 10–12 M

LECTURE # 5
(k) pH of a mixture of a weak acid/ weak base with weak/strong base/acid respectively.
For this type of mixtures there can be two cases in general,
(i) if the acids and bases are mixed in equal amounts(equivalents)
(ii) if the acids and bases are mixed in different amounts(equivalents)
First case will lead to phenomenon of SALT HYDROLYSIS and second case will lead to formation of BUFFER
SOLUTIONS.

Salt Hydrolysis (Reverse of neutralisation) Salt +Water acid +base

When acids and bases are mixed in equal amounts(equivalents), then we will be having salt solutions only in
the water and we have to calculate pH of salt solutions.
When a salt is added to water, the solid salt first dissolves and breaks into ions completely(unless otherwise
specified). The ions of the salt may or may not react with water, the cations when react with water will always
produce H3O+ ions and the anions on reaction with water will produce OH– ions. Depending on the extent of
hydrolysis and on the amounts of H3O+ and OH– ions the solution can be acidic, basic or neutral. If salt is BA,
then
BA(s)  BA(aq)  B+(aq) + A–(aq)
A–(aq) + H2O(l) HA(aq) + OH–(aq) (anionic hydrolysis)
B+ (aq) + 2H2O(l) BOH (aq) + H3O+ (aq) (cationic hydrolysis)
ANIONIC HYDROLYSIS
Anions can function as a base on reaction with water and hydrolyze as follows :
A–(aq) + H2O (l) HA (aq) + OH (aq)
The extent of hydrolysis of a given anion depends on its basic strength
(a) Complete hydrolysis
The anions, which are stronger base than OH– and the conjugate acids of the anions are weaker acid
than H2O, they will show complete hydrolysis in aqueous medium. For example
H+ + H2O  H2 + OH–
(b) Hydrolysis to a limited extent
The anions, which are weaker base than OH– and the conjugate acids are stronger acid than H2O but
weaker acid than H3O+ will hydrolyse to a limited extent in aqueous medium
For Example
CN– + H2O HCN + OH–
Other examples are CH3COO–, NO–2 , S2– etc.
(c) No hydrolysis
The anions that are weaker base than OH– and the conjugate acids are stronger than both H2O and
H3O+ do not hydrolyse at all.
Cl– H2O HCl + OH–
Other examples include SO42– , NO3–, ClO4– etc.

CATIONIC HYDROLYSIS
Cations can function as acid on reaction with water and hydrolyze as follows.
B+(aq) + 2H2O(l) BOH(aq) H3O+(aq)
The extent of hydrolysis of a given cation depends on its acidic strength.
(a) Complete hydrolysis
The cations, which are stronger acid than H3O+ and their conjugate bases are very much weaker
than H2O will show complete hydrolysis. Example is PH+4 ion.
PH+4 + H2O  H3O+ + PH3
(b) Hydrolysis to a limited extent
The cations, which weaker acid than H3O+ ion and their conjugate bases are stonger than H2O but
weaker than OH–, show hydrolysis to a limited extent. For example
NH+4 + 2H2O NH4OH + H3O+
Other ions showing hydrolysis to limited extent are C6H5NH3+, CH3NH3+ etc.
(c) No hydrolysis
The cations, which are weaker acid than H3O+ and their conjugate bases are stronger than both H2O
and OH– do not hydrolyze at all. Example is alkali and alkaline earth metal ions.
Na+ + 2H2O NaOH + H3O
There are four types of salt.
(i) Salt of strong acid and strong base
(ii) Salt of strong acid and weak base
(iii) Salt of weak acid and strong base
(iv) Salt of weak acid and weak base
Salts of first type does not undergo hydrolysis and rest three types undergo hydrolysis.
(i) Salt of strong acid and strong base
Neither of the ions will undergo hydrolysis so the solution contain only the equilibrium of ionization
of water.
2H2O(l) H3O+ + OH–
Thus, the pH of solution will be 7(neutral solution).
(ii) Salt of strong acid and weak base
The examples can be NH4Cl,(NH4)2 SO4, NH4Cl, C6H5NH4+Cl–, CuSO4, ZnCl3, FeCl3, AlCl3,
Only the cation will undergo hydrolysis and the solution will be acidic in nature. for example in the
solution of NH4Cl of concentration c, we will have
NH4+ + H2O NH4OH + H+
t= 0 c 0 0 0
at eq. c(1– h) ch ch (h - degree of hydrolysis)
[NH4 OH][H  ]
Kh=  = called hydrolysis constant of the salt
[NH 4 ]

[NH4 ][OH ]
NH4OH NH4+ + OH– , Kb=
[NH4 OH]
H2 O H+ + OH–, Kw =[H+] [OH–]
From above equations we can get
Kh × Kb = K w

ch .ch ch2 Kh
Kh = = (genarally 1-h 1) so we get, h =
c(1  h) (1  h) c
 Kw
 [H+] = ch = K h  c = c
Kb

1 1
 pH = – log [H+] = – [log Kw – log Kb + log c] = [pKw – pKb – log c]
2 2
(iii) Salt of weak acid and strong base
The examples can be CH3COONa, KCN, Na2C2O4, K3PO4
Similar to above analysis we will get

ch .ch ch2 Kh
Kh = = (genarally 1-h 1) so we get, h =
c(1  h) (1  h) c
Kh × K a = K w

Kw
[OH–] = ch = K h  c = c
Ka

1 1
pH = – log [H+] = – [ log K w  log K a  log C] = [pK w  pK a  log C]
2 2
(i v) Salt of weak acid and weak base
Examples can include CH3COONH4, NH4CN, Ca(CH3COO)2, MgC2O4
CH3COO– + NH4+ + H2O CH3COOH + NH4OH
t=0 c c 0 0
at eq. c – ch c – ch ch ch
[CH3COOH] [NH4 OH]
Kh =  .....(i)
[CH3 COO  ] [NH4 ]

[CH3COO  ][H ]
CH3COOH CH3COO + H , – +
Ka = .....(ii)
[CH3COOH]


[NH4 ][OH ]
NH4OH NH4+ + OH– , Kb = ......(iii)
[NH4 OH]
H2 O H+ + OH–, Kw =[H+] [OH–] ......(iv)
So, Kh× Ka × Kb = Kw ,
2
ch . ch  h   h 
 Kh =       Kh
c(1  h). c(1  h)  1  h   1 h 

from (ii) equation

[CH3 COOH] ch h Kw K w  Ka
[H+] = Ka = Ka = Ka × = Ka × K h = Ka × K  K = Kb
[CH 3 COO  ] c(1  h) 1 h a b

1
pH = – log [H+] = [pKw + pKa – pKb]
2

Ex.  Equal vol. of 0.2 M NH OH (or ammonia) of 0.1 M H SO

4 2 4 are mixed calculate pH of final solution.
Given : Kb of NH3 = 1.8 × 10–5
1 10.26
Sol. pH = [14 – 4.7 + 1] = = 5.13
2 2
Ex.  Calculate pH of 0.01 M ammonium chlorate solution given that K b (NH 3 = 1.8 × 10–5).
Sol. pH = 1/2 (14 – 4.74 + 2)
11.26
= 1/2 (16 – 4.74) = = 5.63
2
Q. Calculate pH of solution obtain by mixing 400 mL of 0.01 M C 6H5NH2 + 400 M of 0.01 M HCl + 1200 of
NaOH. Equilibrium constant of C6H5NH2 with any strong acid is 104.

Q.  Caluclate degree of hydrolysis(h) and pH of solution obtanied by dissolving 0.1 mole of CH COONa in water 3

to get 100ml of solution( take Ka of acetic acid = 2 ×10 ), (log2 = 0.3)

-5

0 .1
Sol. C=  1 10 3
100

Kw 10 14 Kh 5 10 10

Kh    5  10 10 ,  h  = = 5 ×10–3 = 0.5%
Ka 2  10  5
c 2 10 5

1 1 1
pH = [pKw + pKa + log C] = [14 + 5 – log 2 + log (10-3)] = (15.7) = 7.85
2 2 2

Q.  Calculate pH of 10-2 M Ba(Lac)2, given that Ka of lactic acid =10–4.

Sol. C = 2×10–2 M ( concentration of lacted ion, as it is the one which will be hydrolysed)
Lac– + H2O Lactic acid + OH–
2×10 -2

1 1
pH = [14 + 4 + log (2 ×10-2)] = [16 + log 2] = 8.15
2 2

Q.  Calcluate pH of 10-2 M NH4CN Solution given Ka of HCN = 5×10–10 and Kb of NH3(aq .) =2×10–5.

1 1 1
Sol. pH = [14+ pKa – pKb ]= [14 + 10 – log 5 – 5 + log 2 ] = [18.6] =9.3
2 2 2

h Kw 10 14 1
 Kh = = =1 2h = 1 h = = 0.5
1 h Ka  Kb 5  10 10  2  10 5

2

Q.  If the equilibrium constant for reaction of HCN with NaOH is 1010, then calculate pH of 10-3 M NaCN soulition.
Sol. HCN + NaOH H2O + NaCN k = 1010
 CN– + H2O HCN + OH- Kh = 10–10
t = 10-3 M
10–3 (1 – h) 10-3h 10-3h

103 h  103 h Kh 10 14

Kh = 10–10 =  h  = 10 7 ,  [H+] =
103 (1 h) c 10 3 10 7
1
pH = 7 + log10 = 7.5
2
Q. Calculate pH of soultion obtained by mixing equal volumes of 0.02M CH3 COOH and 0.02 M NaOH
0.02M CH3 COOH and 0.02 M NaOH
given that pKa of CH3COOH =4.74
1 1
Sol. pH = [14 + pKa + log c]= [14 + 4.74 + log (10–2) ] = 8.37
2 2
Q. 10 ml of 0.2 M H2SO4 is mixed with 20 ml of 0.2 M Ba(OH)2 solution , the solution obtained is filtered and the
obtanied solution after filtering is reacted with some of 20 ml of 0.2 M CH3COOH solution.Calculate pH of final
solution.(given that pKa of CH3COOH = 4.74)
Sol. H2SO4 + Ba(OH)2  BaSO4 + 2H2O
t =0 2 mmole 4 mmole 0 -
at eq. 0 2 mmole 2 mmole
Solution is containing 2 mmole of Ba(OH)2 in 30ml volume,
Ba(OH)2 + 2 CH3COOH (CH3COO)2 Ba + 2H2O
t =0 2 mmole 4mmole 0 -
at eq. 0 0 2 mmole
Finally it is a solution of a salt of type SBWA, having concentration of the anion being hydrolysed equal to

4 103
[CH3 COO-] = ×1000 = 8×10–2, so
50
1
pH = [14 + 4.74 – 2 + 3 log 2] = 8.82
2

LECTURE # 6
Hydrolysis of ployvalent anions or cations
The hydrolysis of these species will take place in steps( just like dissociation of weak acids). Out of different
steps generally first step hydrolysis dominants mainly because of two reasons
(a) The hydrolysis constant of second and further steps is generally negligible in comparison to first
step hydrolysis constant.
(b) The second and further step hydrolysis will be suppressed in presence of ions produced due to first
step hydrolysis.
For a polyprotic acid (H2S, H3PO4 ,H2CO3 ,H2 C2O4 ) we already know that the disscociation always takes
place in steps, so for example for H3PO4

[H ] [H2PO 4 ]
H3 PO4 H +
+ H2PO4 – K a1  ... (1)
[H3PO 4 ]

2
[H ][HPO 4 ]
H2PO4 –
H +
+ HPO4 2– K a2   ... (2)
[H2PO 4 ]

3
[H ][PO 4 ]
H2PO4 2–
H + +
PO4 3– K a3  2 ... (3)
[HPO 4 ]

For all acids we always have K a1  K a 2  K a3

pH of the solution can be caculated from Ist step only because [H+] from IInd & IIIrd step can be neglected as
(a) K a1  K a 2  K a3
(b) [H+] from Ist dissociation will suppress the dissociation of IInd & IIIrd step.
Now for the hydrolysis of polyvalent ions( of salts like K3PO4 , Na2CO4, ZnSO4, FeCl3, (NH4)2 C2O4 or ions like
PO43–, C2O42–, Zn2+, Fe3+ etc.)
Consider the hydrysis in stepe
PO43– + H2O HPO42– + OH–
c 0 0

[OH ][HPO 24 ]

c(1– h) ch ch K h1  ...(4)
[PO 34 ]
 [OH ][H2PO 4 ]
HPO4 2-
+ H2 O H2PO4 + OH
– – K h2  ...(5)
[HPO 24 ]

[OH ][H3PO 4 ]
H2PO4 + H2O –
H3PO4+ OH – K h3  ...(6)
[H2PO 4 ]

H2 O H+ + OH–, Kw =[H+] [OH–] ...(7)

From above equations we get,
Ka1 × Kh3 = Kw
Ka1 × Kh2 = Kw
Ka3 × Kh1 = Kw
Generally pH is calculated only using the first step Hydrolysis
Ch.Ch Ch2
Kh1 = =
C(1  h) 1  h  Ch2

K h1 Kw K a3 K W  K a3
h= [OH–] = ch = K h1  c [H+] = = Kw K c =

c [OH ] w C

1
So pH = [pK w  pK a3  log C]
2
Hydrolysis of Amphiprotic Anion.
(Cation is not Hydrolysed)
NaHCO3, NaHS, etc., can undergo ionisation to from H+ ion and can undergo hydrolysis to form OH¯ (Na+ ion
is not hydrolysed)

(a) (i) HCO3¯ + H2O CO23 +

(ii) HCO3¯ + H2O H2CO3 +

 pK a1  pK a2 

pH HCO3 = 

 2



(b) Similarly for H2PO4¯ and HPO42– amphiprotic anions.

 pK a1  pK a2   pK a2  pK a3 
pH(H   
 and pH(HPO2 )   

2PO 4 ) 2  2 
  4
 

K a1 K a2 K a3
Now H3PO4  H2PO4¯  HPO42–  PO43– ionisation
 K  K  K
w
K h1  K h2  w
K h1  w
Hydrolysis (reverse of ionisation)
K a1 ka2 K a3

1
The pH of H3PO4 = (pKa1 – log C)  Ka1 >> Ka2 >> Ka3
2
1
pH of NaH2PO4 = (pKa1 + pKa2)
2
1
pH of Na2HPO4 = (pKa2 + pKa3)  sec ionisation can neglect
2
1
pH of Na3PO4 = (pKw + pKa3 + log C)  Sec hydrolysis can neglect
2
1 1
=7+ pKa3 + log C
2 2
Q. Calculate the pH of a 0.1 M K3PO4 solution. The third dissociation constant of orthophosphoric acid is
1.5 × 10–12 . (log3 = 0.48, log 2 = 0.3)
Sol. PO43– + H2O HPO42– + OH–

1 1  12  log 1.5  1
pH = 7 + pKa3 + log C = 7 +    (log 0.1)
2 2  2  2
= 7 + 5.91 – 0.5 = 12.41

LECTURE # 7

Buffer Solution :
(if the acids and bases are mixed in different amounts (equivalents))
Buffer solutions are those, which resist a change in pH upon addition of small amount of acid or base. this
does not mean that the pH will not change, and all it means is that the pH change would be less than the
change that would have occurred had it not been a buffer.

BUFFER CAN BE FORMED IN THREE WAYS.

Acidic buffer :
(i) Mixing of SAWB salt and weak acid. CH3COOH + CH3COONa
(ii) Mixing of WA and strong base [Condition [WA] > [SB]]
CH3COOH + NaOH  CH3COONa + H2O
1 0.5
0.5 0 0.5 0.5

buffer
(iii) Mixture of SBWA salt and strong [condition [Salt] > [SA]]
CH3COONa + HCl  CH3COOH + NaCl
1 0.5 0.5 0.5
0.5 0 0.5 0.5

buffer
To calculate the pH of a buffer solution made up of a weak acid and its salt with a strong base. We have

[CH3COO¯] [H ] [Salt ][H ] [ Acid]

CH3COOH CH3COO¯ + H +
Ka = =  [H+] = Ka ×
[CH3CO2H] [ Acid] [Salt]

[ Acid]
Taking log of both sides. log [H+] = log Ka + log
[Salt]

[Salt]
 pH = pKa + log
[ Acid]
This is known as the Henderson’s equation of a buffer.
For a buffer made up of weak base and its salt with a strong acid the Henderson’s equation looks like this :
[Salt]
pOH = pKb + log
[Base]
Use of various relations :
Let us consider three situations, (i) a solution of CH3COOH (ii) a solution of CH3COONa and (iii) a solution of
CH3COOH and CH3COONa (buffer). In all the three solutions, there will be some CH3COO and CH3COOH.
But the relations used for calculating the pH differs. For (i), the relation used is : pH = ½ (pK a – log c) ; for (ii)

1 [Salt]
the relation used is : (pKw + pKa + log c) and for (iii), the relation used is pH = pKa + log .
2 [ Acid]
To understand as to when a particular relation is to be used, the following chart should be kept in mind.
 [CH3COO–]
[CH3COOH]

< 0.1 < 0.1 to 10 > 10

1 [CH3COO  ] 1
pH = (pKa – log C) pH = pKa + log pH = (pKa + pKw + log C)
2 [CH3 COOH] 2

Although it is difficult to give an exact limit up to which a buffer can be used, it is generally accepted that a
buffer solution can be used for practical purposes when its [Salt]/[Acid] lies within the range of 0.1 to 10 (as
shown above).
Therefore, it can be concluded that a particular weak acid (or base) can be employed for making useful buffer
solution of pH (or pOH) lying within the range of (pKa ± 1) or (pKb ± 1). For example, acetic acid (pKa = 4.75
at 250C) and sodium acetate mixture can be used for preparing buffer solutions whose pH values are roughly
in the range of 3.75 to 5.75. Outside this range, the buffer capacity of acetic acid–sodium acetate solution is
too small to be used for any practical purpose.
Effect of dilution on the pH of buffer solution :
For acidic buffer of HA and A– .

[A  ]
pH = pKa + log
[HA ]
On increase in dilution [A–] and [HA] decreased upto equal extent, so there will be no effect on dilution
(generally).
Effect of addition of small amount of strong acid :
In acidic buffer of HA(n1 moles) and A– (n2 moles), x moles of strong acid (H+) is added.
A– + H+  HA
n2 x n1
n2 – x – n1 + x

[A  ]
pH = pKa + log
[HA ]

[n 2 ]
Before addition of strong acid, pH1 = pKa + log [n ]
1

[n2 – x]
After addition of strong acid, pH2 = pKa + log [n  x]
1

In basic buffer of B(n2 moles) and BH+(n1 moles), x moles of strong acid(H+) is added.
B + H+  BH+
n2 x n1
n2 – x – n1 + x

[BH  ]
pOH = pKb + log
[B]

[n1 ]
Before addition of strong acid, pOH1 = pKb + log [n ]
2
 [n1  x]
After addition of strong acid, pOH2 = pKb + log [n – x]
2

Effect of addition of small amount of strong base :

In acidic buffer of HA(n1 moles) and A– (n2 moles), x moles of strong base (OH–) is added.
HA + OH–  A–
n1 x n2
n1 – x – n2 + x

[A  ]
pH = pKa + log
[HA ]

[n 2 ]
Before addition of strong base, pH1 = pKa + log [n ]
1

[n2  x]
After addition of strong base, pH2 = pKa + log [n – x]
1

In basic buffer of B(n2 moles) and BH+(n1 moles), x moles of strong base(OH–) is added.
BH+ + OH–  B + H2O
n2 x n1
n2 – x – n1 + x –

[BH  ]
pOH = pKb + log
[B]

[n 2 ]
Before addition of strong base, pOH1 = pKb + log [n ]
1

[n2 – x]
After addition of strong base, pOH2 = pKb + log [n  x] .
1

Q. Calculate the amount of (NH4)2SO4 in grams which must be added to 500ml of 0.2 M NH3 to yeild a solution
of pH =9.3. Given pKb for NH3 = 4.7

[Cojugate acid]
Sol. pOH = pKb + log
[Base]

x
4.7 = 4.7 + log x = 0.2, so concentration of (NH4)2SO4 required = 0.1 M
0.2
 moles of SO4 needed = 0.05
 weight of (NH4)2SO4 needed = 132 × 0.05 = 6.6 gm

Q. The pH of a blood stream is maintained by a proper balance of H2CO3 and NaHCO3.What volume of 5 M
NaHCO3 solution should be mixed with 10 ml of a sample of solution which is 2.5 M in H 2CO3 (assume no
NaHCO3), in order to maitain a pH = 7.4.(pKa for H2CO3 = 6.7, log 2 = 0.3)

[HCO3 ]

[HCO3 ]
 
[HCO3 ] nHCO 
3
Sol. pH = pKa + log  7.4 = 6.7 + log  = 5  n = 5
[H2 CO3 ] [H2 CO3 ] [H2 CO3 ] H2CO 3

5 × 2.5 × 10 ×10–3 = 5 × V required volume = 25 ml

Q. 4 gm of NaOH were dissolved in 1 litre of a solution containing 1 mole of CH3COOH and 1 mole of CH3COONa.
Calculate [H+] in the resultant solution.(Given Ka(CH3COOH) =1.8×10–5).

Sol. NaOH + CH3COOH  CH3COONa + H2O

t=0 0.1 1.0 1.0
On completion 0 0.9 1.1

[CH3COO  ] 0 .9
[H+] = Ka × = 1.8 ×10–5 × = 1.47 × 10–5 M
[CH3 COOH] 1.1

LECTURE # 8
Q. The total phosphate conc. in a blood sample is determined to be 3 × 10–3 M. If the pH of the blood sample is
7.4. What are the conc. of H2PO4– & HPO42– in the blood ? (Ka2 of H3PO4 = 8 × 10–8 , log 2 = 0.1).
Sol. Let [H2PO4–] = y & [HPO42–] = x  x + y = 0.003

x
pH = pKa2 + log  y 
 

x x
 7.4 = 7.1 + log  y   y=  
  2
 x = 0.002 M = [HPO42–] & y = 0.001 M = [H2PO4–]

Q. A buffer solution of pH = 9.56 was obtained by mixing 2 mole of NH3(eq.) and 1 mole of NH4Cl to form 1 liter
solution. To 200ml of this solution, 10 ml of 10 M NaOH is added. Caculate pH of this resulting solution.

[NH 4 ]
Sol. pOH = pKb + log
[NH3 ]

1
pOH = 14 – 9.56 = 4.44 = pKb + log  pKb = 4.74
2
In 200 ml of this solution, no. of moles NH4Cl = 0.2 and no. of moles of NH3(eq )= 0.4
no. of moles of NaOH added = 0.1
NH4Cl + NaOH  NH4OH + NaCl
0.2 0.1 0.4

[NH 4 ] 0.1
0.1 0 0.5 pOH = pKb + log = 4.74 + log = 4.04
[NH3 ] 0.5
pH = 14 – 4.04 = 9.96

Q. You are given 0.1 M CH3COOH in a beaker and to that 0.1 M solution NaOH is gradually added from a
burrete. Calculate the pH of the solution in a beaker when acid is 25% neutralized. (Given pK a (acetic acid)
= 4.74)

Sol. CH3COOH + NaOH  CH3COONa + H2O

0.1 0.1 0
0.1–0.025 0.1 – 0.025 0.025
salt 0.025
pH = pKa + log = 4.74 + log = 4.263
acid 0.075
If HA is neutralized by SB then at any stage of neutralization

pH = pKa + log , where  is % neutralization
1 
 for any weak acid at his half equivalance point, pH = pka ,
Similarly for a weak base, at 50% neutralization, pOH = pkb.
Q. A 40ml solution of a weak base(BOH) is titrated with 0.1 M HCl the pH of the solution is found to be 10.04 and
9.14 after adding 5ml and 20 ml of the acid respectively. Calculate pKb of base. (log 2 = 0.3)
Sol. In first case pOH = 14 –10.04 = 3.96 and in second case pOH = 14 – 9.14 = 4.86
number of mmoles of salt = 5 mmole
number of mmoles of base = (40C – 0.5) mmole
0.5
(i) 3.96 = pKb + log
40C  0.5

2
(II) 4.86 = pKb + log
40C  2

0.5 2  2 40C  0.5 

3.96 – log = 4.86 – log log    = 0.9 = log 8
40C  0.5 40C  2  40C  2 0 .5 
40C – 0.5 = 2(40C – 2)  C = 0.0875
 3.96 = pKb + log (0.0875)  pKb = 5.02
Buffer Capacity :
It is defined as the amount of a strong acid or strong base required to change the pH of a buffer by one unit.
Let there be a buffer solution of volume 1 L with ‘b’ mole of salt and ‘a’ mol of salt. The pH of the buffer would
be given by
b
pH = pKa + log
a

bx
On adding x mole of a strong acid (monobasic), the pH changes to pH = pKa + log .
(a  x )

b bx
 pH = log log
a (a  x )
Differentiating with respect to x we get

dpH 1 1 b (a  b ) 1
= × ×
dx 2.303 b ax a (b  x ) 2
 
(a )  b  x 
1 ab
=
2.303 (a  x )(b  x )
Taking the inverse
dx (a  x )(b  x )
= 2.303 . This is defined as buffer capacity. It is the ratio of the small amount of
dpH ab
acid or base added to the change in pH caused in the buffer.

Maximum buffer capacity :

It can be proved that the maximum buffer is achieved when the salt and acid or base concentration is equal.
Differentiating buffer capacity with respect to ‘b’, the amount of salt present in the and equating it to zero,
gives
d  dx  [ 1 (b  x )]  [1 (a  b  x )]
  = 2.303 =0
db  dH  a
a – b + 2x = 0 ; since x is very small we ignore 2x and we get
a–b=0
 b=a  [Acid] = [Conjugate base]
The buffer shows maximum buffer capacity when the amount of acid or base and the salt are same.
Q. Calculate the batter capacity of 1lt of
(i) 0.1M CH3COOH and 0.1M CH3COONa
(ii) 0.2M CH3COOH and 0.2M CH3COONa
pKa CH3COOH = 4.74
which will you bay a better buffer
Solution
x (a  x )(b  x ) ab
 2.303 = 2.303 x << a,b
dph ab ab
0.1  0 .1 0.2  0.2
(i) Buffer capacity = = 0.05 x 2.303 (ii) Buffer capacity = = 0.1 x 2.303
0 .1  0. 1 0 .2  0 .2
Second buffer solution can be said better buffer

ACID-BASE TITRATION :
(A) Titration of SA us SB :
40 ml 0.1 M HCl, NaOH 0.1 M
Volume of NaOH added pH of solution 13
0 ml 1
10 ml 1.22 HPh
20 ml 1.48
30 ml 1.48 7
39 ml 1.84
39.9 ml 2.90 pH
MeOH
40.0 ml 3.90
40.1 ml 7 1
41 ml 10.1 40 ml
50 ml 11.1 Volume of NaOH
60 ml 12.05
60 ml 12.30

 Indication should change it colour sharply for indication of reaction to be complete so its pH - range should
lie perfectly with in sharp change to avoid experimental error. 13

 MeOH and HpH both can use for titration of SA and SB. HPh
Equivalence point

(B) Titration of SB is WA : 7
Volume of NaOH pH value
0 2.5 pH
MeOH
5 ml 4.23
10 ml 4.7 1
15 ml 4.7 log 3 = 5.17 20 ml
19 ml 4.7 + log 19/1 = 6 Volume of NaOH
20 ml 7 + 1/2 (4.7) + 1/2 log (1/4) = 9.05
21 ml 12.4
30 ml 13.23
* In sharp change of titration HPh is suitable indicator.
* Initially fast change in pH is due to free ions availabel fram weak acid.
* Slow down of pH change is due to Buffer formation, which is maximum at pH = pKa.
* Near equivalence point pH again increases fastly due to salt formation.
* After equiv. point pH changes very sharply due to presence of strong base.

(C) Titration of SA + wB

13

HPh

7 Equivalence point
pH
MeOH Sharp change between 4 to 7

1
20 ml
Volume of HCl
(D) Titration of W.A. S.B. salt + S.A.
50 mL of 0.1 M CH3COONa is titrated with 0.1 M HCl. Calculate pH when Vol. of HCl added is.
(a) 0 mL (c) 25 mL (e) 50 mL (g) 75 mL
(b) 10 mL (d) 40 mL (f) 60 mL
pKa of CH3COOHO = 4.74

(a) pH = 1/2 (pKw + pKa + log c)

= 1/2 (14 + 4.74 – 1) = 8.87

(b) CH3COONa + HCl  NaCl + CH3COOH

5 mm 1 mm 0 0
4 mm 0 1 mm –
pH = pka + log 4
= 4.74 + 0.6 = 5.34

(c) pH = pka = 4.74

(d) pH = pka + log 1/4 = 4.14
(e) equivalent point, WA’S solution
[CH3COOH] = 5/100 = 1/20

pH = 1/2 (pka – log C) = 1/2 (4.74 + 2 – 0.7)

6.04
= = 3.02
2

(f) [HCl] = 1/100 pH = 2.1

2.5
(g) [HCl] = pH = 1.7
125

(E) W.B.S.A salt + S.B.

(NH4Cl) + NaOH)
Q. 25 ml; 10–4 M NH4OH solution is titrated against 10–3 M solution of HCl. Calculate the pH of solution at
equivalent point. Also calculate the % of NH4OH present in the form of NH4+ ion at this point.
(Kb (NH4OH) = 1.8 × 10–5)
Sol. NH4OH + HCl  NH4Cl + H2O
For equivalent point
N1V1 = N2V2
V2 = 2.5 ml
 total vol. of solution at equivalent point
= 25 + 2.5 = 27.5 ml
 [NH4+] = 9.7 × 10–5 M

10 14
Kh = = ch2
1.8  10 5
h = 2.47 × 10–3
 [H+] = ch = 2.247 × 10–7 M
pH = 6.65 Ans.
% of NH4OH as NH4+ = 99.7753. Ans.

LECTURE # 9
(F) Titration of Poly protic acid v/s S.B. :
50 mL of 0.1 M H3PO4 agent 0.1 M NaOH. Calculate pH when vol. of NaOH added is
(a) 0 mL (b) 25 mL (c) 50 mL (d) 75 mL (e) 100 mL
(f) 125 mL (g) 150 mL (h) 200 mL (i) 90 mL

pka1 = 3 pka2 = 7 , pka3 = 11

(a) pH = 1/2 (pka1 – log C)
= 1/2 (3 + 1) = 2
(b)

H3PO4 + NaOH NaH2PO4 + H2O

t=0 5 M mol 2.5 M mol 0 –
2.5 M mol – 2.5 M mol
pH = pka1 + log 1/1 = pka1 = 3

(c) solution of H2PO4– amphoteric specis

pKa1  pKa 2 37
pH = = =5
2 2
(d) NaH2PO4 + NaOH  Na2HPO4 + H2O
t=0 5 M mol 2.5 M mol 0 –
2.5 M mol – 2.5 M mol –
pH = log 1/1 + pka2 = 7
 (e) HPO 42– solution (amphoteric speces)
pKa 2  pKa 3
pH = =9
2

(f) Na2HPO4 + NaOH  Na3PO4 + H 2O

5 2.5 0 –
2.5 – 2.5 –

pH = pka3 + 10 g 1/1 = 0

(g) 3rd eq. pt Na3PO4 solution

[Na3PO4] = 5/200 = 1/40
pH = 1/2{pk w + pk 3 + log C}
= 1/2 (14 + 11 – 2 + 0.4) = 11.7

(H) 200 mL
hydrolysis of Na3PO4 can be neglected in Presence of NaOH
[NaOH] = 5/250 = 1/50 pOH = 1.7
pH = 12.3
(i) 90 mL
NaH2PO4 + NaOH  Na2HPO4 + H 2O
5 4 0
1 0 4
pH = pka2 + log 4 = 7.6

Ex. Predict graph for (Na2CO 3 + HCl) . (W.A.S.B Vs S.B.)

Sol. Na2CO 3 + HCl  NaHCO 3 + NaCl
pKa1  pKa 2
pH = 9
2
Na2HCO 3 + NaCl  H2CO3 + NaCl
pH = 1/2 {log C + pka1}  3.5 – 4

Q. 1.06 gm of Na2CO3 is dissolved in 100 ml water. This solution is titrated against a 0.05 M HCl. Calcualte the
pH when.
(a) 200 ml of HCl is added K1 = 4.2 × 10–7
(b) 400 ml of HCl is added K2 = 4.8 × 10–11
1.06
Sol. m mole of Na2CO3 taken = × 1000 = 10
106
(a) m mole of HCl taken = 200 × 0.05 = 10
pKa1  pKa 2 6.38  10 .32
pH = = = 8.35 Ans.
2 2
 (b) m moles of HCl = 400 × 0.05 = 20
Na2CO3 + 2HCl  H2CO3 + 2NaCl
H2CO3 H+ + HCO3–
0.02 x x

x2
= 4.2 × 10–7
0.02  x
 x = 9.165 × 10–5 M = [H+]  pH = 4.04 Ans.

INDICATOR :
Indicators are the substance, which indicates the end-point of a titration by changing their colour. They are in
general, either weak organic acids or weak organic bases having characteristically different colours in the
ionised and unionised forms. For example, methyl organce is a weak base (having red colour in ionised form
and yellow colour in the unionised form) and phenolphthalein is a weak acid (having pink colour in the ionized
form while its unionised form is colourless)
Let us consider the equilibrium between the ionised and unionsed form of an acid indicator (Hn)

Hn H+ + n¯
[H  ][n ¯]
 KHn = [KHn = indicator constant or dissociation constant of indicator]
[Hn]

[Hn]
or [H+] = KHn ×
[n ¯]
Taking negative logarithm of both sides
[Hn]
– log [H+] = log KHn – log
[n ¯]

[n ¯] [Ionised form]

 pH = pKHn = log  pH = pKHn + log [Unionised form]
[Hn]
In general, the intensity of a coloured solution depends on the concentration of the colour imparting species.
If the solution contains two coloured species, then the colour of the solution depends on the relative
concentration of the colour imparting species. When the solution contains two coloured species as Hn and
n¯, then it is seen that the solution acquires a distinct colour of n¯ only when the concentration of n– is
approximately at least 10 times greater than the concentration of Hn and vice versa.
Let us consider two cases.
Case-I
[n ¯]
In order for the solution to show colour due to n¯ the minimum ratio of should be 10.
[Hn]
 pH = pKHn + log (10) = pKHn + 1
At this stage, the percentage of the indicator in n¯ form would be given by
[n¯] 10
× 100 = × 100  91.
[n¯]  [Hn] 10  1

Thus, nearly 91% of the indicator has been present in the ionised form (n¯). In fact pH = pKHIn + 1 is the
minimum pH up to which the solution has a distinct colour characteristic of n¯. At pH greater than this value,
some more indicator will be present in the ionised form. Thus at pH > pKHin + 1, the solution has a colour
characteristic of n¯.

Case - II
[n ¯] 1
In order for the solution to show colour due to Hn, the minimum ratio of should be .
[Hn] 10
 1
 pH = pKHn + log = pKHIn = – 1.
10
At this stage, the percentage of the indicator in n¯ form would be given by
[n ¯] 1
 100   100  9.1
[n¯]  [Hn] 10  1
Thus, nearly 9.1% of the indicator has been present in the ionised from (n¯) and  91 % of the indicator is
present in the uionzed from (Hn). In factr pH = pKHn – 1 is the maximum pH up to which the solution has a
distinct colour characteristic of Hn. At pH smaller than this value, some more indicator will be present in the
unionised form. Thus at pH < pKHn = 1, the solution has a colour characteristic of Hn.

Universal Indicator :
A mixture of the following indicator can be used to determine the approximate pH of the solution in the range
4 to 11. Methykl red, -naphtholphthalein, thymolphathalein, phenolphthalein and bromothymol blue.
This mixture gives different colour at different pH values of the solution. These are :
pH 4 5 6 7 8 9 10 11
colour Red Orange red Yellow Green yellow Green Blue green Blue violet Red violet

Q. A weak acid type indicator was found to be 60% dissociated at pH = 9. What will be the percent dissociation
at pH = 8.
Sol. HIn H+ + In–

[H  ] [In  ] 10 9  60
KIn = =
[HIn] 40

10 8  x 10 9  60 10 9  3
KIn = = =
1 x 40 2

300
 Percent dissociation = = 13.04.
23
Q. In indicator HIn has a standard ionisation constant of 10–10. The acid form of the indicator is yellow and the
alkaline form is red. The yellow colour is visible when the ratio of yellow form to red form is 30 to 1 and the red
colour is predominant when the ratio of red form to yellow form is 2 to 1. What is the pH range of indicator.
(log2 = 0.3, log3 = 0.48)
Sol. HIn H+ + In–

[H  ] [In  ]
KIn =
[HIn]
When yellow : red = 30 : 1
[HIn]
 [H+]1 = 10–10 × = 30 × 10–10  pH1 = 8.52
[In  ]
When red : yellow = 2 : 1

2
10–10 = [H+]2   .  pH2 = 10.3
 1
Q. pH of 0.1 M solution of NaA is 8.92. Caculate pk a of HA if a drop of HPh (pk a = 9.52 ) be added to the above
solution predict whether the pink colour will visible or not under the medical fact our eyes can see the pink
coler if the molar % ionised from of indicator is 25% or more .
1
Sol. pH = (pka + pkw + log c)
2

1 1
8.92 = 7 + pka + (–1)
2 2
 1
pk = 8.92 – 6.5 = 2.42
2 a
pka= 4.84
ionised
pH = pka (indicator) + log
unionised

ionised
8.92 = 9.52 + log
unionised

[IN¯] ionised 1
 =
[HIN] unionised 4
Since [IN¯] = 20% Colour wiil not be visible.

SIGNIFICANCE OF INDICATORS :
Indicators work in specific pH range i.e. they change their colour distinctly once a specific pH range is
crossed. e.g. phenolphthalein works in pH range 810 while methyl orange in the range 3 to 4.4

 Extent of reaction of different bases with acid (HCl) using these two indicators is summarised below

Phenolphthalein Methyl Orange

NaOH 100% reaction is indicated 100% reaction is indicated
NaOH + HCl  NaCl + H2O NaOH + HCl  NaCl + H2O
Na2CO3 50% reaction upto NaHCO3 100% reaction is indicated
stage is indicated
Na2CO3 + HCl  NaHCO3 + NaCl Na2CO3 + 2HCl  2NaCl + H2O + CO2
NaHCO3 No reaction is indicated 100% reaction is indicated
NaHCO3 + HCl  NaCl + H2O + CO2.
Isoelectric Point of amino acids :

Isoelectric point is the point when the net charge is equal to zero :
 At isoelectric point , [Anionic form] = [Cationic form]
[H+] = K a1 K a 2

pK a1  pK a 2
pH = .
2
Q. Calculate the pH of glycine at its is isoelectric point what % of 0.01 M neutral solution of glycine is present
in it s cationic form.

pK a1  pK a 2 2.35  9.78
Sol. At isoelectric point, pH = = = 6.065.
2 2
Now, +
H3N – CH2 – COO– + H2O +
H3N – CH2 – COOH + OH–
(G) (C)

Kw [C][OH – ]
Kh = K =
a1 [G]

[C] K w  100 K w [H ]  100 10 6.065  100

 × 100 = K [OH – ] = = = 0.0193%.
[G] a1 K a1  K w 10 – 2.35

LECTURE # 10

Solubility(s) and Solubility Product(k sp )

This is generally used for sparingly soluble salts, We will be dealing with the solubilities in the following tyupe
of solutions
1. Simple solution in H2O
2. Effect of common ions on solubility
3. Simultaneous solubility
4. Precipitate1 + electrolyte1  Precipitate2 + electrolyte2
5. Condition for precipitation
6. Solubility in a buffer solution
7. Solubilty due to complex formation

Solubility product(ksp) is a type of equilibrium constant, so will be dependent only on temperature

for a particular salt.
Following examples will illustrate the different type of solubilities and the effects of different factors or situations
on solubility of a salt.
1. Simple Solubility
Let the salt is AxBy, in solution in water, let the solubility in H2O = ‘s’ M, then
AxBy xAy+ + yB–x
– xs ys  KSP = (xs)x (ys)y = xx.yy.(s)x+y
Q. Calculate kSP of Li3Na3[AlF6]2
Sol. KSP = 33.33.22 (s)8 = 36.4.(s)8 = 2916 s8

Q. Solubility product of CaCO3 is 9 × 10–8 calcultate its solubility in gm/lt.

Sol. CaCO3 Ca2+ + CO32–
Ksp = s 2
= 9 × 10–8
s = 3 × 10–4 mol/lt. = 3 × 10–4 × 100 = 0.03 gm/lt.
Q. Calculate solubility of PbI2 in water at 25ºC which is 80% dissociated Ksp[PbI2] = 2.048 × 10–9
Sol. PbI2(s) Pb2+ + 2I–
0.8s 1.6s
Ksp = (0.8s) (1.6s) = 2.048 × 10
2 –9

s = 10–3 mol/lt.

2. Effect of common ions on solubility :

Because of the presence of common ion the solubility of the salt decreases.
Q. Calculate solubility of silver oxalate in 10–2 M potassium oxlalate solution. Given that KSP of silver oxalate = 10–10.
Sol. [C2O42–] = 10–2 + x, where x is the solubility of silver oxalate, this can be neglected in comparison to 10–2.. So,
10 8
Ksp = 10 = 10 × (2x)
–10 –2 2
 2  2 =x
2
 x = 5 ×10–5

Q. If Ksp of SrF2 = 8 ×10–10. Calculate its solubility in 0.1 M NaF solution.

Sol. If x be the solubility of SrF2 in presence of NaF, then

SrF2 Sr 2+ + 2F– NaF  Na+ + F–

x 2x 0.1 0 0
x (2x + 0.1) 0 0.1 (0.1 + 2x)
Ksp = x (2x + 0.1)2 = 8 ×10–10.
Neglecting 2x with respect to 0.1, as we have solubility of SrF 2 in pure water in the range of 10–3, in presence
of common ions from NaF the solubility will get further decreased so we can easily neglect F – ions from SrF2,
then we will have
K sp K SP
 = [Sr2+]  = x = solubility of SrF2 = 8 × 10–8
 2
[F ] 0.12
3. Calculation of simultaneous Solubility
Q. Calculate simultaneous solubility of silverthiocyanate and sliver bromide in water given that KSP of silver
thiocyanate = 10 – 12 and KSP of silver bromide = 5 ×10–13 respectively.
Sol. Let the solubility of AgSCN be x and that of AgBr is y, then
AgSCN Ag+ + SCN– AgBr Ag+ + Br–
x+y x x+y y
10–12 = x ( x + y) ----------------------(i)
5 × 10–13 = y (x + y) ----------------------(ii)
On solving we get, x = 2y
So, y = 4.08 ×10–7 and x = 8.16 ×10–7

Q. The ratio of solubility products of barium sulphate and barium chromate is 1 : 2.4. When pure water is
saturated with both the solids simultaneously the total [Ba2+] is found to be 1.85 ×10–5. Caculate Ksp of the
compounds.
Sol. Let the solubilities of the salts be x and y respectively, then
BaSO4 Ba2+ + SO42– BaCrO4 Ba2+ + CrO4–2
x+y x x+y y
x + y = 1.85 ×10–5
Ksp1 = x (x+y) Ksp2 = y (x+y)

1 x
 y = 2.4x
2.4 y

1 . 8  10 5
1.85 2
x=  Ksp1 = × 10–10 = 1 × 10–10 and Ksp2 = 2.4 × 10–10
3 .4 3.4
 LECTURE # 11
4. Condition of precipitation
For precipitation ionic product should be greater than KSP
Q. You are given 10–5 M NaCl solution and 10–8 M AgNO3 solution, they are mixed in 1 : 1 volume ratio, predict
whether AgCl will be precipitated or not, if solubility product of AgCl is = 10–10 mole per litre.

10 5 10 8
Sol. Ionic product = × = 25 ×10–15 < Ksp
2 2
Hence no precipitation will take place.

5. Selective Precipitation
Q. 2 × 10–4 moles of Mn2+ and Cu2+ each is present in one litre solution of 10–3 M HClO4, which is
saturated with H2S. Whether or not each of the ions will be precipitaed? Given that concentration of H2S in its
saturated solution is = 0.1 M, net dissociation constant of H2S = 10–21,
Ksp for MnS = 2.5× 10–10 and Ksp for (CuS) = 8.5×10–36
Sol. H2 S 2H+ + S2–
10–1
10–3 x

K=

x  10 3 
2

= 10–21 [S2–] = 10–16 M

[H2S]
Ionic Product of CuS = [Cu2+][S2–] = 2×10–4 ×10–16 = 2 ×10–20 > KSP of CuS
Ionic Product of MnS = 2×10–20 < KSP of MnS
CuS will be precipitated
Ex. A solution containing
[Cl–] = [Br –] = [–] = 10–2 M (initally) to this solution [AgNO 3] is added gradually.
Calculate
(a) which can will get ppt. final
(b) concentration of Ag+ ion when 1st ion start ppting.
(c) conc. of [–] & [Cl–] ion when AgBr start ppting.
(d) conc. of [Br–] & [–] ion when AgCl start ppting.
KSP of [Ag] = 10–17 , KSP of [AgBr] = 10–13 , KSP of [AgCl] = 10–10
(a) For the precipitation of – ion +
Conc. of Ag
[Ag+] [–] = KSP [Ag]
-7
10 All three will ppt
10 17
[Ag+] = = 10–15
10  2 10
-8
AgCl saturated
For the precipitation of Br– ion
AgBr, Ag ppt
-10
10

10 13 10-11 AgBr Saturated, Ag ppt

[Ag+] = 2 = 10–111
10 10
-13
Ag ppt only
For the precipitation of Cl– ion
Ag saturated
-15
10
10 10
[Ag+] = = 10–8 10-18 no ppt
10 2
-20
 1st Ag will be precipitated 10 no ppt
(b) [Ag+] > 10–15 -27
10 no ppt
(c) [Ag+] = 10–11
[Cl–] = 10–2 (  ppt. is not formed) 0
[Ag+] = [–] = KSP (Ag)
 10–10 [–] = 10–17
[–] = 10–6 M
10  6
% remaining iodide =  100 = 10–2 % = 0.01 %
10 2
 % ppt. of [–] = 99.99%

(d) [Ag+] = 10–8 ; [Ag+] [–] = KSP of Ag

10 17 10 13
 [–] = = 10–5 M ; [Br–] = = 99.9%
10 8 10 8
6. Solubility in appropriate buffer solutions.
Appropriate buffer means that the components of buffer should not interfere with the salt or only H + or OH–
ions should be interacting with the ions of the salt.

Q.1 The Solubility of Pb(OH)2 in water is 6.7 × 10–6 M. Calculate its solubility in buffer solution of pH = 8
Sol. Pb (OH)2 solubility in water = 6.7×10–6, Ksp = 4s3 = 4 × 300 ×10–18 = 1.2 ×10–15
Pb(OH)2 Pb2+ + 2OH–
Let [Pb2+] = x, then Ksp = x [OH–]2
1.2 ×10 = x × 10
–15 –12
 x = 1.2 × 10–3 M
Q.2 Calculate solubility of AgCN in a buffer solution of pH = 3, given that Ksp(AgCN) = 1.2 ×10–15, Ka for
HCN = 4.8×10–10.
Sol. let the new solubility be = x
[Ag+] = x = [CN–], but some of CN– ions will react with H+ ions from the buffer so,
x = [CN–] + [HCN]
HCN H+ + CN –

[H ][CN ] 10 3 [CN ] [CN ]  10 7

Ka = 4.8 ×10–10 =  [HCN] = 10 =
[HCN] 4.8  10 4.8
[CN ]  10 7
x= + CN– (CN– concentration can be neglegted in comparison to first term.)
4.8
4. 8 x
Ksp = x . = 1.2 × 10–15  x = 5 × 10–5
10 7

Q.3 Caculate solubility of MnS in a buffer of pH = 6.Given that for H2S, Ka1 = 10–7 & Ka2 = 10–14 and solubility of
MnS in water is 10–8 M.
Sol. let the solubility be = x
[Mn2+] = x = S2– , but free [S2–] < x
x = [S2–] + [HS–] + [H2S]
[H ][HS  ]
H2 S H+ + HS– Ka1 =
[H2S]
[H2S] = [H+] [HS–] Ka–1
[H2S] = 10–6 × (10–7)–1 [HS–] = 10 [HS–]
HS– H+ + S2–
[H  ][ S 2  ]
Ka2 = , [HS–] = 10–6 × [S2–] × 10+14 = 108 [S2–]
[HS  ]
[H2S] = 10 [HS–] = 10+9 [S2–]
x = [S2–] (1+ 108 + 109)
1 can be neglected
x x
[S2–] = = × 10–8
11 10 8 11

x2
Ksp = 10–16 = × 10–8 x2 = 11 × 10–8 x = 3.32 × 10–4
11
Ex. What must be [H+] in a satarated H2S solution, so as to precipitred Pb2+ ions but not Zn2+ ions
from a solution in which each ions is present at a contration of 0.1 M. Given that Ka for H2S = 1.1 × 10 –21Ksp
for ZnS = 1.0×10–21
 LECTURE # 12

7. Precipitate -1 + Ion-2 Precipitate -2 + Ion-1

Q. 2M solution of Na2CO3 is boiled in a closed container with excess of CaF 2. Very little amount of CaCO 3
and NaF are formed. If the solubility product of CaCO 3 is x and molar solubility of CaF 2 is y. Find the
molar concentration of F – in resulting solution after equilibrium is attained.
Sol. Na2CO 3(aq) + CaF2(s) 2NaF(aq) + CaCO3(s)
t=0 2
teq 2–a – 2a
where a is very small
For CaCO3, KSP = x = [Ca2+] [CO 32–]
x
[Ca2+] =
2

x 8y 3
For CaF2 , KSP = 4y3 =   [F –]2  [F –] =
2 x

Q. The solubility product of Ag2C2O 4 at 25ºC is 1.3 × 10–12 . A solution of K2C2O 4 containing 0.15 moles in
500 ml water is shaken at 25ºC with excess Ag2CO 3 till the following equilibrium is reached.
Ag2CO 3(s) + K2C2O 4 Ag2C2O4 (s) + K2CO 3
At, equilibrium, the solution contains 0.02 mole of K2CO 3. Assuming the degree of dissociation of
K2CO3 and K2C2O4 .
Sol. Ag2CO3(s) + C2O 42– A2C2O4(s) + CO 32–
0.3 – –
0.3 – x x = 0.04
2
K SP ( Ag2CO 3 ) [CO3 ]
 K = K ( Ag C O )  2
SP 2 2 4 [C 2 O 4 ]

K SP 0.04
 11
  KSP = 2 × 10–12
1.3  10 0.26

8. Effect on solubility because of complex formation

Q. What must be the concentaration of aq. NH3(eq.) which must be added to a solution containing 4 × 10–3 M
Ag+ and 0.001 M NaCl, to prevent the precipitation of AgCl. Given that KSP(AgCl) = 1.8 ×10–10 and the
10 8
formation constant of [Ag(NH3)2]+ is Kformation = .
6
Sol. Caculate silver ion concentration which can be allowed to remain in the solution,
1.8 ×10–10 = [Ag+] [Cl–]
1.8  10 10
[Ag+] = = 1.8 ×10–7 M, This quantity is so small that almost all the Ag + ion will be
0.001
consumed.
10 8
Ag + + 2NH3 [Ag(NH3)2]+ K=
6
4 × 10–3 b 0
10 8 4  10 3
1.8 ×10 –7
(b– 8×10 ) –3
4×10 –3
K=   b = 0.0445
6 1.8  10 7  (b  8  10 3 )2
Q. How much solid Na2S2O3 should be added to 1 lt of water so that 5 × 10–4 mol Cd(OH)2 would just barely
dissolve. K1 & K2 for S2O32– complexation with Cd2+ are 8.3 × 103 and 2.5 × 102 respectively. KSP of
Cd(OH)2 = 4.5 × 10–15
Sol. Cd(OH)2 Cd2+ + 2OH–
5 × 10–4 1 × 10–3
Cd2+ + 2S2O32– Cd(S2Cr3)22–
5 × 10–4 – x n – 2x x
=0
5  10 4
K1K2 = (8.3 × 10 ) (2.5 × 10 ) =
3 2
[Cd2 ](n  2x )2
& KSP = 4.5 × 10–15 = [OH–]2 [Cd2+]
(10 3 )2  (5  10 4 )
 (8.3 × 10 × 2.5 × 10 ) × (4.5 × 10 ) =
3 2 –15
(n  2x )2
 n – 2x = 0.2314
n = 0.2314 + 2(5 × 10–4) = 0.2324

6. Amphoterism : The hydroxides of certain metals can function as both bases and acids.
eg. Zn(OH)2 , Al(OH)3 , Sn(OH)2 , Cr(OH)2
Zn(OH)2 (s) Zn2+ (aq.) + 2OH– (aq.)
Zn(OH)2 (s) + 2OH– (aq.) Zn(OH)42– (aq.)
If the [OH–] is very small, then Zn2+ is present in high concentration.
On the other hand at high hydroxide concentration Zn(OH)42– is present in high concentration.
In other words, solubility at Zn(OH)2 is greater in an acidic or basic solution than in neutral water.

Q. (a) At what minimum concentration OH– will 10–3 mole of Zn(OH)2 go into solution as Zn(OH)42– in 1 L solution.
(b) At what maximum concentration of OH– with 10–3 moles of Zn(OH)2 go into solution as Zn2+ in 1 L solution.
Given : Zn(OH)4–2 (aq.) Zn2+ (aq) + 4OH– (aq) K = 10–15
Zn(OH)2 (s) Zn (aq) + 2OH (aq)
2+ –
KSP = 10–17
Sol. (a) If 10–3 mole Zn(OH)2 go into Zn(OH)42–.
Zn(OH)2 (s) + 2OH– (aq) Zn(OH)42– (aq)

10 –3
10–2 =  [OH–] = 0.316 M
[OH ] 2
(b) If 10–3 mole Zn(OH)2 go into Zn2+.
Zn(OH)2 (s) Zn2+ (aq) + 2OH– (aq)
10–17 = 10–3 × [OH–]2  [OH–] = 10–7 M