SOLVED OBJECTIVE EXAMPLES

Example 1:
The solubility product of BaSO4 is 1.5  10−9 at 18oC. Its solubility in water at 18oC is
(a) 1.5  10−9 M (b) 1.5  10−5 M
(c) 3.87  10−9 M (d) 3.87  10−5 M
Solution:
Let the solubility of BaSO 4 be x M.

 [Ba2+] = x M; [SO24− ] = x M

x 2 = 1.5  10 −9 ; x = 1.5  10 − 9 = 3.87  10 − 5 M

 (d)

Example 2:
Which of the following solution will have pH value close to 1.0?
(a) 100 ml of M/10 HCl + 100 ml of M/10 NaOH
(b) 55 ml of M/10 HCl + 45 ml of M/10 NaOH
(c) 10 ml of M/10 HCl + 90 ml of M/10 NaOH
(d) 75 ml of M/5 HCl + 25 ml of M/5 NaOH
Solution:
The answer has to be either (b) or (d) since only in these two choices, HCl is greater than
NaOH (only when HCl is in greater amount, pH can be acidic).
10  M10
In (b), 10 ml of M/10 HCl will be left out after neutralization. [H+] = = 0.01 M.
100
 pH = 2
 (d)

Example 3:
At −50C, the self−ionization constant (ion product) of NH3 is K NH3 = [NH +4 ] [NH2− ] = 10 −30 M2.
How many amide ions are present per mm3 of pure liquid ammonia?
(a) 600 ions/mm3 (b) 6  106 ions/mm3
(c) 6  104 ions/mm3 (d) 60 ions/mm3
Solution.
2NH3(l) + NH +4 + NH 2−

1− x x x
−30
K NH3 = x2 = 10

Thus, x = 10−15 M = [NH 2− ]

10 −15
[NH 2− ] = 10−15 moles/lit = moles / mm 3
10 6

[NH 2− ] = 10−21  6  1023 ions/mm3 = 600 ions/mm3

 (a)

Example 4:
In which of the following solvents, will AgBr have highest solubility?
(a) 10−3 M NaBr (b) 10−3 M NH4OH
(c) pure water (d) 10−3 M HBr
Solution:
With ammonia, Ag+ forms a complex of the type, [Ag(NH3)2]+. This increases its solubility compared
to pure water. In NaBr and HBr, AgBr will encounter a common ion effect, which would reduce its
solubility compared to pure water.
 (b)

Example 5:
One litre of a saturated solution of CaCO3 is evaporated to dryness due to which 7.0 mg of
residue is left. The solubility product for CaCO3 is
(a) 4.9  10−8 (b) 4.9  10−5
(c) 4.9  10−9 (d) 4.9  10−7
Solution:
7  10 −3
Moles of CaCO3 in the residue = = 7  10 −5
100
Moles of CaCO3 in 1 litre solution = 7  10−5

CaCO3(s) Ca2+ + CO 32−

7  10−5 7  10−5

Ksp = [Ca2+]  [ CO 32 − ] = 7  10−5  7  10−5 = 4.9  10−9

 (c)
Example 6:
M (OH)x has KSP = 4  10−12 and solubility = 10−4 M. Then the value of x is
(a) 1 (b) 2
(c) 3 (d) −4

Solution:
M(OH)x will ionise as
M(OH)x M+x + x OH−
10−4 x 10−4
 Ksp = [M+x] [OH−] x
 (10−4) (x  10−4)x = 4  10−12
By inspection, we can find that the relation will hold good when x = 2.
 (b)

Example 7:
Consider the reaction, A− + H3O+ HA + H2O. The Ka value for acid HA is
1.0  10−6. What is the value of K for this reaction?
(a) 1.0  106 (b) 1.0  10−8
(c) 1.0  108 (d) 1.0  10−6

Solution:
The reaction is the reverse of the ionization reaction of HA, hence the equilibrium constant is the
reciprocal of Ka.
[HA ] 1 1
K= = = = 1.0  10 6
− + K a 1.0  10 −6
[ A ] [H ]

 (a)

Example 8:
The precipitate of Ag2CrO4 (Ksp = 1.9  10−12) is obtained when equal volumes of the following
are mixed.

(a) 10−4 M Ag+ + 10−4 M CrO 24− (b) 10−2 M Ag+ + 10−3 M CrO 24−

(c) 10−5 M Ag+ + 10−3 M CrO 24− (d) 10−4 M Ag+ + 10−5 M CrO 24−

Solution:
Precipitation occurs when the ionic product exceeds Ksp value. When equal volumes of two solutions
are mixed, the concentration of each is reduced to half. Therefore,
 In first case,
2
1  1  1
Ionic product, I.P. =   10 − 4    10 − 4  =  10 −12 = 1.25  10 −13
2  2  8
As, I.P. < Ksp
 No precipitation occurs.
In second case,
2
1  1  1
I.P. =   10 − 2    10 − 3  =  10 − 7 = 1.25  10 − 8
2  2  8
As, I.P. > Ksp
 Precipitation occurs.
In third case,
2
1  1  1
I.P. =   10 − 5    10 − 3  =  10 −13 = 1.25  10 −14
 2   2  8
As, I.P. < Ksp
 No precipitation occurs.
In fourth case,
2
1  1  1
I.P. =   10 − 4    10 − 5  =  10 −13 = 1.25  10 −14
2  2  8
As, I.P. < Ksp
 No precipitation occurs.
 (b)

Example 9.
A weak base (BOH) with Kb = 10−5 is titrated with a strong acid, HCl. At 3/4th of the equivalence
point, pH of the solution is
(a) 5 + log 3 (b) 5 − log 3
(c) 14 − 5 + log 3 (d) 8.523
Solution:
Let the initial equivalent of BOH be x.
BOH + HCl ⎯→ BCl + H2 O
Initial equivalent x 3/4x 0 0
3x x 3 3
At ¾ th eqv. pt. x − = 0 x x
4 4 4 4
[Salt ] 3x  4
pOH = pKb + log = 5 + log
[Base] 4 x

pH = 14 − 5 −log 3 = 8.523
 (d)

Example 10:
When equal volumes of the following solutions are mixed, precipitation of AgCl
(Ksp = 1.8  10−10) will occur only with
 (a) 10−4 M [Ag+] and 10−4 M [Cl−] (b) 10−5 M [Ag+] and 10−5 M [Cl−]
(c) 10−6 M [Ag+] and 10−6 M [Cl−] (d) 10−10 M [Ag+] and 10−10 M [Cl−]
Solution:
We look for the case where the ionic product exceeds the Ksp.
2
1 
(a) [ Ag + ] [Cl − ] =   10 − 4  = 2.5  10 −9 [As the dilution factor for Ag+ and Cl− is 2]
2 
 (a)

Example 11:
Calculate the pH of a solution prepared by mixing 2.0 ml of a strong acid (HCl) solution of pH
3.0 and 3.0 ml of a strong base (NaOH) of pH 10.0.
(a) 2.5 (b) 3.5
(c) 4.5 (d) 6.5

Solution:
Number of milliequivalents of HCl = 2  10−3.
We know that pH + pOH = 14
 10 + pOH = 14. ; pOH = 4
Number of milliequivalents of NaOH = 3  10−4.
The resulting solution is acidic.
(2  10 −3 − 3  10 −4 )m. eq.
[H+] = = 3.4  10−4 M.
(2 + 3)ml
or pH = −log[H+] = −log(3.4  10−4) = 3.5.
 (b)

Example 12:
Calculate the pH at the equivalence point in the titration of 25 ml of 0.1 M formic acid with a 0.1
M NaOH solution (given that pKa of formic acid = 3.74).
(a) 4.74 (b) 8.22
(c) 8.37 (d) 6.06

Solution:
At the equivalence point, 0.05 M of HCOONa (sodium formate) is formed. This problem is solved by
the considering the concept of hydrolysis equilibria.
1 1 1 1  1  1
pH = pK w + pK a + log c =   14  +   3.74  + log 0.05 = 8.22.
2 2 2  2   2  2
 (b)
Example 13:
A weak acid HX has Ka = 1.0  10−5 and it forms a salt NaX when treated with caustic soda.
The percentage of hydrolysis of a 0.1 M NaX solution is
(a) 0.1% (b) 0.01%
(c) 0.001% (d) 1%
Solution:
Kw 10 −14
h= = = 10−4 ; Percentage h = 10−4  100 = 0.01%
Ka  c 10 − 5  0.1

 (b)

Example 14:
What will be the Kb value of a weak base (BOH) of which a 0.1 M solution has a pH of 8, when
it is half neutralized with 0.1 M HNO3?
(a) 10−8 (b) 10−4
(c) 10−6 (d) 10−7

Solution:
BOH + HNO3 ⎯→ BNO3 + H2O
At the half neutralisation of weak base (BOH) with HNO3, the solution behaves as a basic buffer in
which [BOH] = [BNO3].
 pOH = pKb ; pOH = 14 − pH = 14 − 8 = 6 = pKb
 Kb = 10−6
 (c)

Example 15:
50 ml of a solution containing 10−3 mol of Ag+ is mixed with 50 ml of a 0.1 M HCl solution. How
much Ag+ remains in solution (Ksp of AgCl = 1.0  10−10)?
(a) 2.5  10−9 (b) 2.5  10−7
(c) 2.5  10−8 (d) 2.5  10−10

Solution:
Ag+ + Cl− ⎯→ AgCl(s)
1  10 mol
−3
5  10 mol
−3

Moles of Cl− before the reaction = 50  10−3  0.1 = 5  10−3

Moles of Cl− after the reaction = 4  10−3
4  10 −3
[Cl−] after the reaction = = 4  10−2 M
0 .1

1.0  10 −10
[Ag+] left in the solution = = 2.5  10−9 M
4.0  10 − 2
Moles of Ag+ left in 100 ml solution = 2.5  10−10.
 (d)

SOLVED SUBJECTIVE EXAMPLES

Example 1:
 An indicator is a weak acid and the pH range of its colour is 3.1 to 4.5. If the neutral point of
the indicator lies in the center of the hydrogen ion concentrations corresponding to the given
pH range, calculate the ionization constant of the indicator.
Solution:
The hydrogen ion concentrations of the given pH range are
For pH 3.1,
pH = −log [H+] = 3.1
[H+] = 7.94  10−4 M
For pH 4.5,
pH = 4.5 = − log [H+]
 [H+] = 3.16  10−5 M
The average of these two hydrogen ion concentrations is
(7.9  10 −4 ) + (3.16  10 −5 )
= 4.128  10−4 M
2
At this concentration of H+, we will get neutral point of the indicator, at which [ In−] = [HIn].
 pH = pK HIn

or [H+] = K HIn = 4.128  10−4

Example 2:

At 25°C, the degree of ionization of water was found to be 1.8  10−9. Calculate the ionization
constant and ionic product of water at this temperature.

Solution:
If x is the degree of ionization of water, then
H2O H+ + OH−

c(1 − ) c c
1000
c = [H2O] = = 55.56 M
18

[H + ] [OH + ] (c ) 2
Keq = =  c 2 (since  is very much less than 1)
[H 2 O] c(1 −  )

Keq = 55.56  (1.8  10−9)2 = 1.8  10−16 M

Kw = [H+] [OH−] = (c)2 = (55.56  1.8  10−9)2
Kw = 1.0  10−14 M2

Example 3:

At 25°C, will a precipitate of Mg(OH)2 form in a 1  10−4 M solution of Mg(NO3)2 if pH of the

solution is adjusted to 9.0. [ K SP (Mg(OH) 2 = 8.9  10 −12 M 3 ]. At which minimum pH will the
precipitation start?

Solution:
If pH = 9.0, [H+] = 1  10−9 M, then
 KW 1  10 −14
[OH−] = = = 1  10−5 M
[H + ] 1  10 −9

The ionic product of Mg(OH)2 in the solution would be

[Mg2+] [OH−]2 = (1  10−4) (1  10−5)2 = 1  10−14 M3

Since, the value of ionic product in smaller than KSP (8.9  10−12), so no precipitate of Mg(OH)2 will
be formed.

The minimum concentration of OH− needed to precipitate Mg2+ from the solution is

K SP 8.9  10−12
[OH−] = = = 2.98  10−4 M
[Mg2+ ] 1  10− 4

 Maximum pOH = 3.54

and minimum pH = 14 − 3.54 = 10.46

Example 4:
Calcium lactate is a salt of a weak organic acid and is represented as Ca(Lac) 2. A saturated
solution of Ca(Lac)2 contains 0.13 mol of this salt in 0.5 litre solution. The pOH of this solution
is 5.6. Assuming complete dissociation of the salt, calculate Ka for lactic acid.
Solution:
Ca(Lac)2(s) ⎯→ Ca(Lac)2(aq) ⎯→ Ca2+(aq) + 2Lac−(aq)

Lac−(aq) + H2O LaCH(aq) + OH −(aq)

Since it is salt of strong base and weak acid, its pH is calculated as

pH =
1
pK w + pK a + log c 
2
pH = 14 – pOH = 14 – 5.6 = 8.4

1
8.4 = [14 + pKa + log 0.52] (  c = 2  0.13/0.5)
2
pKa = (2  8.4) –14 – log 0.52 = 3.08

 Ka = 8.31  10−4
Example 5:
(a) Calculate the pH of a 0.01 M solution of benzoic acid, the Ka being
7.3  10−5.
(b) 0.2 M solution of Ba(OH)2 is found to be 90% ionised at 25oC. Find the pH of the solution at
that temperature.
Solution:

Ka 7.3  10 −5
(a) First calculate  using the expression,  = = = 0.085
c 0.01
pH = ½ (pKa – log c) = ½ (4.13 − 0.01) = 2.06
(b) [OH−] = 0.2  0.9  2 = 0.36
pOH = 0.44; pH = 13.56

Example 6:
The solubility of BaSO4 and BaCrO4 at 25oC are 1  10−10 and 2.4  10−10 respectively. Calculate
the simultaneous solubilities of BaSO4 and BaCrO4.
Solution:
Let the solubility of BaSO 4 be x and that of BaCrO4 be y mole litre−1 in the presence of each other.
BaSO4(s) Ba2+ + SO42− ; BaCrO4(s) Ba2+ + CrO42−
(x + y) x (x + y) y

[Ba2+] [ SO 24− ] = 1  10−10 = (x + y) x ……..(i)

[Ba2+] [ CrO 24− ] = 2.4  10−10 = (x + y)y ……..(i)

Dividing (ii) by (i) we get

y
= 2.4 ;  y = 2.4 x
x
Substituting the value of y in (i), we get
3.4 x  x = 1  10−10
x = 5.42  10−6 M
 y = 2.4  5.42  10−6 = 1.3  10−5 M

Example 7:
A certain acid−base indicator is red in acid and blue in basic solution.
At pH = 5, 75% of the indicator is present in the solution in its blue form. Calculate dissociation
constant (Ka) for the indicator and pH range over which the indicator changes from 90%
red−10% blue to 90% blue−10% red.
Solution:
Since Ka is asked, the indicator must be an acid. Let the acid be represented by HIn.
HIn H+ + In−
In acid solution, the indicator will be predominantly present in the form of HIn (due to common ion
effect). Since in acid solution the colour is red, this would be due to HIn. In basic solution, the indicator
will be predominantly in the form of In−. Since the indicator is blue in basic solution, so
In− must be blue in colour.
At pH = 5, the indicator is 75% blue. This also means it is 25% red.
10 −5  0.75
 Ka = = 3  10 −5
0.25
K a  [HIn] 3  10 −5  0.9
pH when it is 90% red & 10% blue: [ H + ] = = = 2.7  10 − 4
[In − ] 0 .1

 pH = 3.56
K a  [HIn] 3  10 −5  0.1
pH when it is 90% blue and 10% red: [ H + ] = = = 3.3  10 − 6
[ In −] 0 .9

pH = 5.48

Example 8:
What is the pH of a 1.0 M solution of acetic acid? To what volume must 1 litre of the
solution be diluted so that the pH of the resulting solution will be twice the original value?
Given: Ka = 1.8  10−5.
Solution:
Ka
Let us first calculate  using  =
c

1.8  10 −5
= = 4.24  10−3
1
Since,  is very much smaller than 0.1, so the assumption is valid.  [H+] =  = 2.19  10−5

 [H+] = Ka c = 1.8  10 −5  1 = 4.24  10−3

pH = −log(4.24  10−3) = 3 – log 4.24 = 3 – 0.6273 = 2.37

Now pH on dilution = 2  2.37 = 4.74
[H+] = 1.8  10−5 = c

c 2 c   1.8  10 −5  
Ka = = = = 1.8  10−5
1−  1−  1− 


= 1;   = 0.5
1− 

[H+] = c
[H + ] 1.8  10 −5
c= = = 3.6  10−5 M
 0 .5
 Let the volume to which 1 l of 1 M acetic acid is diluted be V, then
11 = 3.6  10−5  V
1 1 10 5
V = = = 0.277 x 105 = 2.77  104 litres.
3.6  10 −5 3 .6

You can notice that  increases on dilution and it become considerable and cannot be ignored with
respect to 1.

Example 9:
20 ml of 0.2 M NaOH is added to 50 ml of 0.2 M acetic acid. What is the pH of the resulting
solution? Calculate the additional volume of 0.2 M NaOH required making the solution of pH
4.74. The ionization constant of acetic acid is 1.8  10−5.
Solution:
20 ml of 0.2 M NaOH would react with 20 ml of 0.2 M acetic acid.
30  0.2 6
[Acid] = 30 ml of 0.2 M present in 70 ml = = mole
70 70
20  0.2 4
[Salt] = 20 ml of 0.2 M present in 70 ml = = mole
70 70
pKa = −log 1.8  10−5 = 4.74
[Salt ] 4 70
pH = pKa + log = 4.74 + log 
[ Acid] 70 6

pH = 4.74 + log 0.66 = 4.74 − 0.18 = 4.56

To make a solution of pH = 4.74, [Acid] = [Salt]
So 25 ml of 0.2 M NaOH must be added to 50 ml of 0.2 M acetic acid.
Additional volume of NaOH to be added = 25 − 20 = 5 ml.

Example 10:
A weak base, BOH is titrated with a strong acid HA. When 10 ml of HA is added, the pH of the
solution is 10.2 and when 25 ml is added, the pH of the solution is 9.1. Calculate the volume of
acid that would be required to reach equivalence point.
Solution:
Let the molarity of HA be ‘M’ 2 and the molarity and volume of weak base (BOH) are ‘M’ 1 and ‘V’1
respectively.
In first case,
BOH + HA ⎯→ BA + H2O
mmole before reaction M1V1 10M2 0 0
mmole after reaction (M1V1 − 10M2) 0 10M2 10M2
Since the solution (after addition of 10 ml of HA) contains weak base (BOH) and salt of its conjugate
base (BA), the solution behaves like a basic buffer.
[Salt ]
 pOH = pKb + log
[Base]

10M2
14 − 10.2 = pKb + log
(M1V1 − 10M2 )

Dividing numerator and denominator of log tem by M2 gives

 10M 2
M2
 3.8 = pK b + log
 M1V1 10M 2 
 − 
 M2 M2 

10
3.8 = pK b + log …….(i)
V2 − 10

where V2 is the volume of acid required to get equivalence point (At equivalence point,
M1V1 = M2V2)
In second case,
BOH + HA ⎯→ BA + H2O
mmole before reaction M1V1 25M2 0 0
mmole after reaction (M1V1 − 25M2) 0 25M2 25M2
25M 2
14 − 9.1 = 4.9 = pKb + log
(M1V1 − 25M 2 )

Dividing numerator and denominator of log term by M2

25
4.9 = pK b + log …….(ii)
V2 − 25

Substracting equation (i) from (ii)

 25   10 
4.9 − 3.8 = 1.1 =  log  −  log 
 V2 − 25   V2 − 10 

5 V2 − 50
Taking antilog, 12.58 =
2V2 − 50

 V2 = 28.72 ml

Example 11:
The solubility product of calcium oxalate is 2  10−9 at 25°C. Calculate the solubility of calcium
oxalate at this temperature. What will be its solubility in a 0.1 M solution of ammonium oxalate?
Assume that ammonium oxalate is completely ionized in solution. Name the effect, which
operates on addition of ammonium oxalate to calcium oxalate
Solution:
The solubility product, KSP of calcium oxalate is given by
KSP = [Ca2+] [ C 2 O 24− ] = 2  10−9
Let ‘s’ be the solubility of calcium oxalate in mole litre−1.
s2 = 2  10−9

s= 2  10 −9 = 4.472  10−5 mole/ .

Let the solubility of CaC2O4 be s in the presence of 0.1 M ammonium oxalate solution.
CaC2O4 Ca2+ + C 2 O 24−

(NH4)2C2O4 ⎯→ 2 NH +4 + C 2 O 24−
0.1 M
Since CaC2O4 is sparingly soluble, the concentration of C 2 O 24− derived from CaC2O4 is negligible in
comparison to 0.1.
KSP = [Ca2+] [ C 2 O 24− ] = s  0.1 = 2  10−9

2  10 −9
s = = 2  10−8 mole/
0 .1
In the presence of ammonium oxalate, the solubility of CaC 2O4 drops from 4.472  10− 5 to
2  10−8 mole/ . This effect is called common−ion effect.

Example 12:
What is the solubility of PbS (a) ignoring the hydrolysis of ions and (b) including the hydrolysis
of ions (assume pH of the solution to be equal to 7)?
Given that Ksp (PbS) = 7.0  10−29 M2, K b (Pb (OH+) = 1.5  10−8 M, K a (H2S = 1.1  10−7 M
2 1

K a 2 (HS−) = 1.0  10−14 M.

Solution:
Solubility ignoring hydrolysis
Let x  be the solubility of PbS ignoring hydrolysis, then
Ksp (PbS) = [Pb2+] [S2−] = 7.0  10−29 M2
Hence, x  2 = 7.0  10−29 M2 or x  = 8.4  10−15 M
Solubility including hydrolysis
Let the solubility of PbS considering hydrolysis x moles/litre.
PbS(s) Pb2+ + S2−
(x − y) (x − z)
Pb2+ + 2H 2O [Pb (OH)]+ + H3O+
(x − y) y y
S2− + H2O HS− + OH−
(x − z) (z − a) (z + a)
HS− + H2O H2S + OH−
(z − a) a (z + a)
Ksp (PbS) = (x − y) (x − z) = 7  10−29 ……(i)
 y2 Kw 1  10 −14
Kh (Pb2+) = = = = 6.7  10 −7 M ……(ii)
( x − y ) K b [(Pb(OH + )] 1.5  10 −8
1

( z − a) ( z + a) K w 1 10 −14
K h (S 2 − ) = = = = 1M ……(iii)
( x − z) K a2 1 10 −14

a (a + z ) K w 1 10 −14
K h (HS − ) = = = = 9.1 10 −8 M ……(iv)
( z − a) K a1 1.1 10 −7

Solving for x, we get

x = 1.0146  10−10 M
Thus, the solubility of PbS including hydrolysis is 1.0146  10−10 M. Comparing this value with
that obtained after ignoring hydrolysis indicates that the solubility of PbS has been increased
1.1046  10 −10
by a factor = = 12078
8.4  10 −15

Example 13:
Determine the number of mole of AgI which may be dissolved in 1.0 litre of 1.0 M CN − solution.
Given: Ksp for AgI and Kc for Ag(CN) 2− are 1.2  10−17 M2 and 7.1  1019 M−2 respectively.

Solution:
Given, AgI(s) Ag+(aq) + I−(aq) ; Ksp = [Ag+] [I−] = 1.2  10−17 …(i)
[ Ag(CN) 2− ]
Ag+(aq) + 2CN−(aq) [Ag(CN2]−(aq) ; Kf = = 7.1  1019 …(ii)
[ Ag + ] [CN− ] 2
Let ‘x’ mole of AgI be dissolved in CN− solution, then
Now AgI(s) + 2CN− [ Ag(CN) 2− ] + I−
Mole before reaction 1 0 0
Mole at equilibrium ( 1 − 2x) x x
By equations (i) and (ii), Keq = Ksp  Kf
[ Ag(CN) 2− ] [I− ]
Keq = = 1.2  10−17  7.1  1019
[CN− ] 2
Keq = 8.52  102 …(iii)
2
x
 Keq = 8.52  102 =
(1 − 2 x ) 2
x
or = 29.2
1− 2 x
 x = 0.49 mole.
Example 14:
Calculate the concentrations of all the species present in 0.1 M H 3PO4 solution.
Given: K1 = 7.5  10−3, K2 = 6.2  10−8 and K3 = 3.6  10−13.
Solution:
I Step: H3PO4 H+ + H 2 PO −4 ; K1 = 7.5  10−3

II Step: H 2 PO −4 H+ + HPO −42 ; K2 = 6.2  10−8

III Step: HPO −42 H+ + PO −43 ; K3 = 3.6  10−13

For I Step: H3PO4 H+ + H 2 PO −4

0.1 M 0 0
(0.1 − c)M c c
[H + ] [H 2 PO −4 ] c2
K1 = =
[H 3 PO 4 ] ( 0 .1 − c )
c2
7.5  10−3 =
( 0 .1 − c )
Solving the quadratic equation,
c = 0.024
 [H+] = 0.024 M
 [H 2 PO −4 ] = 0.024 M
[H3PO4] = 0.1 − 0.024 = 0.076 M
The value of K1 is much larger than K2 and K3. Also dissociation of II and III steps occurs in presence
of H+ furnished in I step and thus, dissociation of II and III steps is further suppressed due to common
ion effect.

For II Step: H 2 PO −4 H+ + HPO −42

0.024 0.024 0
(0.024 − y) (0.024 + y) y

The dissociation of H 2 PO −4 occurs in presence of [H+] furnished in step I.

[H + ] [HPO −42 ]
Thus, K2 =
[H 2 PO −4 ]

(0.024 + y )y
or 6.2  10−8 =
(0.024 − y )

y is small  0.024 − y  0.024 and neglecting y2.

0.024 y
 6.2  10−8 =
0.024

 y = 6.2  10−8

or [HPO −42 ] = K2 = 6.2  10−8 M

For III Step: HPO −42 H+ + PO −43

(6.2  10−8 − x) (0.024 + x) x
 [H + ] [PO −43 ] (0.024 + x )  x
K3 = =
[HPO ] −2
4 (6.2  10 −8 − x )

Again neglecting x2 and assuming, 6.2  10−8 − x = 6.2  10−8

0.024 x
 3.6  10−13 =
6.2  10 −8

3.6  10 −13  6.2  10 −8

 [PO 34− ] = x = = 9.3  10−19 M.
0.024

Example 15:
The pH of blood stream is maintained by a proper balance of H 2CO3 and NaHCO3
concentrations. What volume of 5 M NaHCO 3 solution, should be mixed with 10 ml sample
of blood, which is 2 M in H2CO3 in order to maintain a pH of 7.4. Ka for H2CO3 in blood is
7.8  10−7?
Solution:
Let the volume of 5 M NaHCO3 solution added be x ml.
Number of millimoles of NaHCO3 = 5x
Number of millimoles of H2CO3 = 10  2 = 20
[NaHCO 3 ]
For the acidic buffer, pH = pKa + log
[H 2 CO 3 ]
5x
7.4 = −log(7.8  10−7) + log
20
On solving, x = 78.37 ml
 Volume of NaHCO3 solution required = 78.37 ml.
 MIND MAP

1. The acidity of an aqueous solution is

expressed as its pH, which is defined as 3. The product of the ionization constant
2. At 25°C, an acidic solution has of an acid and the ionization constant
the negative logarithm of pH < 7, a basic solution has pH >
the hydrogen ion concentration of its conjugate base is equal to the
7 and a neutral solution has pH=7. ionic product (Kw) of water.
(in mol/litre). For dilute solutions,
pH = − log [H+] Kw = Ka  Kb.

4. For the pH calculation of a weak acid

10.The solubility product (Ksp) expresses first calculate  using the expression
the equilibrium between a solid and its Ka
ions in solution. The presence of a  = . If the  value from this
c
common ion decreases the solubility of a
expression is  0.1, then [H+] is
salt while complex ion formation
increases its solubility. calculated using [H+] = K a  c but if 
value is > 0.1 then calculate exact
value of  using the expression,
c 2
Ka = and then calculate [H+] as
1− 
IONIC [H+] = c.
EQUILIBRIUM
5. For the calculation of pH of a strong
9. Acid−base indicators are weak organic acid, the contribution of H+ from water
acids or bases that change colour at the would be taken into account if [H+]acid <
equivalence point in an acid−base 10−6 M and when the [H+]acid is  10−6
neutralization reaction. M, the H+ contribution from water can
be ignored. .

7. Most salts are strong electrolytes

8. A buffer solution maintains pH of the that dissociate completely into ions
solution almost constant. A mixed buffer 6. The common ion effect tends to
in solution. The reaction of these suppress the ionization of a weak acid
solution comprises of either a mixture of ions with water, called salt
weak acid and salt of its conjugate base or a weak base. This effect is seen
hydrolysis, can produce acidic or only on electrolyte with a smaller
or weak base and salt of its conjugate basic solutions. In salt hydrolysis,
acid. pH of an acidic buffer is given by pH equilibrium constant, by the electrolyte
the conjugate bases of weak acids having higher equilibrium constant.
[salt ] yield basic solutions and the
= pKa + log .
[acid] conjugate acids of weak bases yield
acidic solutions.