Contents IIT-JEE Syllabus: Solulbility Product,

1. Ostwald’s Dilution Law .................. 01 Commom Ion Effect, pH and Buffer

2. Relative Strength of Acids and Solutions, Acids and Bases (Bronsted and
Bases ............................................ 02 Lewis Concepts), Hydrolysis of Salts.
3. Common ion effect ......................... 03
4. Ionization of Water ......................... 05
5. pH Calcuation ............................... 05 Ionic equilibrium is the study
6. pH determination for Weak Acids.... 06
7. Determination of pH of of the reversible reaction
acids or bases ................................ 07
8. pH for the mixture of weak acid involving formation of ions
and strong acid .............................. 08
9. pH calculation of solution of a mixture in water or we can say that
of two weak acids in water ............. 09
10. pH of a dibasic Acids and the equilibrium existing in
Polyprotic acid............................... 10
11. pH of the Mixtures ......................... 11 solution involving ions.
12. Buffer Solution ............................... 12
13. Acid Buffer.................................... 12
Whereas in the chemical
14. Calculation of pH of Acidic Buffer equilibrium we study the
Solution......................................... 13
15. Basic Buffer ................................... 14 molecules equilibrium
16. Calculation of pH of Basic Buffer
Solution......................................... 13 means involence of
17. Salt Buffer ..................................... 16
18. Buffer capacity of Buffer index ........ 16 molecules only.
19. Buffer Range ................................. 17
20. Hydrolysis of Salts ......................... 17 In this chapter we would
21. Case IV: Salt of strong Acid +
Strong Base ................................... 22 study electrolytes, Acid-Base
22. Solubility and solubility product ....... 22
23. Common-ion Effect on Solubility ..... 23 concepts, pH calculation
24. Ionic Product
25. Preferential Precipitation of salts ...... 24 Buffer solution, Indicators,
26. Solubility of a salt of weak acid and
weak base in acidic buffer ............... 25 Hydrolysis of salt and
27. Solubility of a salt of weak acid and
weak base in basic buffer ................ 25 solubility product.
28. Solubility of AgCl in an aqueous
solution containing NH3 ................................. 26
29. Acid-base indicators ...................... 26
30. Indication (basic) action of MeOH .. 27
31. Ostwald’s theory............................ 29
DPP (1 to14) ................................. 31
32. Solved Problem (Subjetive) ............ 47
33. Solved Problem (Objetive) ............. 51
34. Assignments (Objetive)
Level (I to IV) ............................... 57
35. Assignments (Subjetive)
Level (I to IV) ............................... 64
36. Answers ........................................ 76
[CHEMISTRY] [IONIC EQUILIBRIUM]

JEE EXPERT
IONIC EQUILIBRIUM
Electrolytes: Whose aqueous solution conduct electricity.
Electrolytes are classified into two groups.
1. Strong Electroytes: Are those whose ionization is almost 100%, in aqueous solution generally
all ionic compounds are strong electrolytes e.g. NaCl, NaNO3, HCl, KCl.
2. Weak Electrolytes: Whose degree of dissociation is < 10-15%. Generally covalent compounds
are weak electrolytes. e.g. NH 4 OH, CH3 COOH .
Strong and Weak electrolytes is a value term it only depends upon degree of ionization. Some
times covalent compounds acts as a strong electrolytes in highly diluted solution.
2 Ka ionized molecules
Ka = C  
 Ka V      =

C Total molecules
“The fraction of total no. of molecules of electrolytes dissolved, that ionizes at equilibrium is
called degree of ionization or degree of dissociation.”
For: unionized molecules ionized molecules  << 1
Generally strong and weak electrolyte property depends upon nature of solvent NaCl in H2O
acts strong electrolyte whereas CH3COOH is weak electrolyte in water. But in liquid NH3, the
dissociation of NaCl and CH3COOH both are same.

1. Ostwald’s Dilution Law :

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

K eq
K eq  C 2 ,  
C
If 1 mole of AB is present in ‘V’ litre of solution.
1
C    K eq  V
V
K eq
Conc. of [A+] = Conc. [B–]  C  C  K eq C
C

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Limitation
(i) This is only for weak electrolytes not for strong electrolytes.
(ii) This law is not applicable for strong electrolytes because strong electrolytes are almost completely
C
ionized at all dilution and hence  does not give accurate results.


2. 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 dissociations 1
HA1 H+ + A1–  [H  ]  C11
For HA 2 if concentration is C 2 and degree of dissociation is 2
HA2 H+ + A2–  [H  ]  C2  2

[H  ] furnished by I acid C11

Then, Relative strength  
[H  ] furnished by II acid C2  2

C1  K a1 C 2   K a1 C1 
R.S.       
C2 K
 2 
a C 1 K
 2 
a C 2

If C1 and C 2 are same, then

 Ka 
R.S.   1 
 Ka
 2 
Illustration 1:
Calculate the degree of ionization of 0.01 M solution of HCN, Ka of HCN is 4.8  10 –10 .
Also calculate hydronium ion concentration.
Solution:
The ionization of HCN may be represented as,
 CN – (aq)  H 3O  (aq)
HCN(aq)  H 2O() 
If degree of ionization of HCN is  then equilibrium concentration of various species are
[HCN]  C(1 – ) , [CN – ]  C , [H3 O  ]  C
where C = concentration of HCN.
Applying law of chemical equilibrium
[CN – ][H 3O  ] (C )(C ) C 2
Ka   
[HCN] C(1 –  ) (1 – )
Since  is very small as compared with unity therefore , 1 –  in the denominator may be taken
as 1.
Ka 4.8 10 –10
K a  C 2     2.2  10 –4 .
C 0.01
[H3 O  ]  C  0.01 2.2 10 –4  2.2 10 –6 mol L–1 .
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Illustration 2:
Calculat e t he co ncent r at io n of fluor oacet ic acid which is requir ed t o get
[ H  ]  1.50  10 –3 M . [ Ka . of acid  2.6  10 –3 ].
Solution:
FCH2COOH FCH2COO– + H+
[FCH2COO–] = [H+] = 1.5 × 10–3
(1.5 10 3 ) 2
 2.6 × 10–3 =  C – l.5 × 10–3 = 8.65 ×10–4  C = 2.365 × 10–3
C  1.5 10 3

3. Common Ion Effect :

The degree of dissociation of a weak electrolyte is suppressed by the addition of another

electrolyte containing the common ion.
Quantitative Aspect
 H+ + A– its degree of dissociation be .
HA 

Ka

C
BA (another electrolyte) added whose molarity is M, due to this the new degree of dissociation
becomes  .
BA  B+
 + A–
0 M M
HA  H+
 + A–
C(1 –  ) C  C 
[H  ][A  ] [C][C  M]
K a (HA)  
[HA] [C(1  )]
K a (HA)  C2  M 1    1
C2 Neglecting because    1
Ka
 
M
As a result of common ion effect, the conc. of the ion, which is not common changes to make
the Ka constant, because K only depends upon temperature not on concentration.
Note: The use of this phenomenon is made in quantities analysis to adjust the conc. of S– – ions in
second group (reagent H2S and HCl) and OH– ion conc. in third group (NH4Cl + NH4OH).

Illustration 3:
Calculate the degree of ionization of 0.02 M acetic acid if its Ka  1.8  10 –5 . What
would be the degree of ionization if the solution also contains 0.01 M sodium acetate ?
Solution:
CH 3COOH(aq)  CH 3COO – (aq)  H  (aq)
The degree of ionization of this weak acid can be calculated by the approximate relation :

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[CHEMISTRY] [IONIC EQUILIBRIUM]

Ka 1.8  10 –5
   0.03  3  10 –2 .
C 0.02

Now let us calculate the degree of ionization when the solution also contains 0.01 M sodium
acetate. Sodium acetate being a strong electrolyte would be completely ionized in solution. Let
x mol L–1 of acetic acid be ionized.
 CH 3COO – (aq)  H  (aq)
CH 3COOH(aq) 
(0.02– x )M xM xM

 CH 3COO – (aq)  Na  (aq)

CH 3COONa(aq) 
0.01 M 0.01 M

[H  ]  x mol L–1
[CH 3COO – ]  (x  0.01) mol L–1  0.01 mol L–1
[ x is very small as compared to 0.01]
[CH 3COOH]  (0.02 – x) mol L–1  0.02 mol L–1

[H  ][CH 3COO – ] (x)(0.01)

Ka   1.8 10 –5 
[CH3 COOH] (0.02)

1.8 10 –5  0.02

x  3.6 10 –5 M
0.01
x 3.6 10 –5
Degree of ionization,     1.8  10 –3
0.02 0.02
Thus, it may noted that the degree of ionization of acetic acid has decreased from 3  10 –2 to
1.8  10 –3 due to the presence of sodium acetate.

Illustration 4:
Calculate the degree of ionization of pyridine (C 5 H 5 N) in its 0.1 M solution K b for
pyridine is 1.5  10 –9 . What would be the degree of ionization of pyridine if the solution
also conta in
0.1 M in NaOH?
Solution:

C6H5N + H2O C6H5 N H + OH

Kb 1.5 10 9
= = = 1.23 × 10–4
C 0. 1
In presence of 0.1 M NaOH solution, common ion effect operates hence OH– ions are poduced
only by NaOH
(0.1)(0.1)
 1.5 × 10–9 =
(0.1)
 = 1.5 × 10–8

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4. 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 .
 H O+ + OH–
2H2O(  )  3

C C
[H 3O  ][OH  ]
K eq 
H2 O

K eq [H 2O()]  [H3O  ][OH  ]

Since conc. of pure water remain constant
K eq k  [H 3O  ][OH  ]
k w  [H 3O  ][OH  ]
K w  dissociation constant of water at 25°C, Kw comes out to be 1  10–14.
Kw depends upon temperature dissociation of water gives equal no. of H3O+ and OH– ions.
1 1014  [H 3O  ]2  [OH  ]2
So [H3 O ]  [OH  ]  10 7 mole/litre
pH = –log [H3O+] = – log [10–7] = 7.
pOH = – log [OH–] = – log 10–7 = 7.
Note: In case of water
[H3O+]w [OH–]w = 10–14.
But in case of acidic or basic solution.
[H3O+]T [OH–]T = 10–14, where [H3O+]T and [OH–]T are the conc. of [H3O+] and [OH–] totally
present in the solution.

5. pH Calculation :

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 [H3O+]
pOH = –log10 [OH–]
pkw = –log10 [Kw]
kw = [H+] [OH–]
taking –ve log10 both side
–log Kw = –log [H3O+] + [– log (OH–)]
pKw = pH + pOH
at 25°C, Kw = 1  1014 , pKw = 14
pH + pOH = 14
Kw = is also called as auto protolysis constant, it increases with temperature.
Since with increase in temperature dissociation of water increases, therefore the value of Kw increases
as the temperature is increased, however at all temperature [H3O  ] remain equal to [OH – ] in pure
water.
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Illustration 5:
The Kw for 2H 2 O H 3O + + OH – changes from 10 –14 at 25°C to 9.62  10 –14 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+] [OH–] = 10–14 ( Kw = [H+] [OH–])
 [H+] = 10–7 M  pH = 7
Now Kw for H2O 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.

Illustration 6:
Calculate pH for (a) 0.0008M Mg(OH) 2 , (b) 0.01 N Ca(OH) 2
Solution:
(a) 0.0008M Mg(OH)2
Mg(OH)2  Mg+2 + 2OH–
 [OH–] = = 2 × 8 × 10–4 = 1.6 × 10–3  pOH = 2.8  pH = 11.2
(b) 0.01N Ca(OH)2
Ca(OH)2  Ca+2 + 2OH–
[OH–] = 0.01 N ( equivalents are always same)
 [OH–]= 0.01 M  pOH = 2  pH = 12

6. pH Determination for Weak Acids :

Weak acids do not dissociate completely in the water their % degree of dissociation is very less.
e.g. lets takes CH3COOH (C mole/litre and having degree dissociation ).

CH3COOH  CH3COO– + H+
C(1–) C C
 
[CH 3COO ][H ] C.C
K a (CH3COOH )  
[CH3 COOH] C(1  )
C 2
Ka 
1 
if   0.1 , then we can neglect 1    1
Ka
K a  C 2  
C
Ka
[H  ]  C = C = KaC
C
pH = –log [H+] = – log10 [ K a C]

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C 2
Note: For calculating the pH of a weak acid first of all we calculate  from the equation K a  ,
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 

Illustration 7:
(a) pH of a solution is 10 in NaOH solution. What is concentration of NaOH ?
(b) What is molar concentration of Ca(OH)2 if its solution has pH of 12 ?
Solution:
(a) [H+] = 10–pH
[OH–] = 10–pOH
NaOH is strong base, hence [OH–] = [NaOH]
In pH = 10, pOH = 4
 [OH–] = 10–4 = [NaOH]
(b) pH of Ca(OH)2 = 12  pOH = 2  [OH–] = 10–2 M
102
 [Ca(OH)2] = M = 0.5  10–2 M
2
[Every Ca(OH)2 gives two OH– ions]

Illustration 8:
A solution of HCl has a pH = 5. If one mL of its is diluted to 1 litre, what will be pH of
resulting solution ?
Solution:
pH = 5  [H+] = 10–5  [HCl] = 10–5 M
now using dilution formla, M1V1 = M2V2
10–5 ×1 = M2 × 1000  M2 = 10–8 M
At this low concentration, H+ ions are also produced from water
 [H+] = 1.05 × 10–7  pH = 6.978

7. Determination of pH of Acids or Bases:

For strong acid

HCl   H+ + Cl–
pH = –log [H+]
If conc. of HCl is less than 10–6M than we take conc. of H+ from water into accounts i.e. 10–7.
Otherwise we would neglect the conc. of H+ from water.
e.g. find the pH of 10–8 M HCl
According to rule
pH = –log [H+] = –log [10–8] = 8
But pH of an acid can’t be 8 so we have to take contribution of H+ from water
Total H+ ion in solution = H+ (from HCl) + H+ (from H2O) = 10–8 + 10–7 = 1.1 107 mole/litre
and hence
pH = –log [H+] = – log [ 1.1 107 ] = 7 – log 1.1 = 7 – 0.0414
pH = 6.9586 (Acidic).
8. pH for the Mixture of Weak Acid and Strong Acid :
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8. pH for the Mixture of Weak Acid and Strong Acid :

Let strong acid be HB whose conc. is C1

+ –
HB   H +B
0 C1 C1
and weak acid whose conc. is C2 and degree of dissociation is 
HA   H+ + A–
C2(1 –) C2 C2
+
Total (H ) conc. = C1 + C2
pH = – log [C1 + C2]
[H  ][A  ] [C1  C 2 ][C2 ]
K a (HA )  
[HA] [C 2 (1  )]

Illustration 9:
What concentration of HCOO– is present in a solution of 0.015 M HCOOH and 0.02
M HCl ?
Ka for HCOOH = 1.8  10 –4 .
Solution:
Given, [HCOOH]  0.015M  [HCl] = 0.02 M  [H  ] in solution = 0.02 M
The dissociation of HCOOH is suppressed due to common ion effect in presence of HCl. The [H  ]
is provided by HCl in solution.
 HCOO –  H 
HCOOH 
[H  ][HCOO – ]
Ka 
[HCOOH]
[0.02][HCOO – ]
1.8 10 –4   [HCOO – ]  1.35  10 –4 M
[0.015]

Illustration 10:
Calculate [H +] in a 0.20 M solution of dichloroacetic acid ( Ka  5  10 –2 ) that also
contains 0.1 M sodium dichloroacetate. Neglect hydrolysis of sodium salt.
Solution:
CHCl2COOH CHCl2COO– + H+
CHCl2COONa  CHCl2COO– + Na+

[CHCl2COO ][H ] (0.1 0.2)(0.2) 1 (1  2 ) 
 Ka =  5 × 10–2 =  =
[CHCl2 COOH] 0.2(1) 2 1 
 1 –  = 2 + 42
 3  9  16 3 5 2
 42 + 3 –1 = 0   = = = = 0.25
8 8 8
 +
[H ] = 0.2  = 0.2 × 0.25 = 0.5

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9. pH Calculation of Solution of a Mixture of a Mixture of two Weak
Acids in Water :

Let two weak acids be HA and HB and their conc. are C1 and C2, 1 is the degree of dissociation of
HA in presence of HB (due to common ion effect) and 2 be degree of dissociation of HB in presence
of HA. In aqueous solution of HA and HB following equilibrium exists.

HA + H2O(l)  H3O+ + A–
conc. at equi. C1(1 – 1) C11 + C22 C 1 1
HB + H2O(l)  H O+
 + B–
3

C2(1 – 2) (C1 1 + C2 2) C 2 2

[H 3O  ][A  ] [C11  C1 2 ][C1 2 ]
K a[HA]  
[HA] C1 (1  1 )

[H3 O ][B ] [C11  C 2  2 ][C2  2 ]

K a[HB]  
[HB] [C 2 (1   2 )]
pH  – log[H  ]  – log[C11  C2  2 ]

Illustration 11:
Calculate [H + ] in a solution containing 0.1 M HCOOH and 0.1 M HOCN. Ka for
HCOOH and HOCN are 1.8  10 –4 and 3.3  10 –4 .
Solution:
In this problem both the acids contribute for [H  ] due to appreciable dissociation. Thus,
 H   HCOO –
HCOOH 
0.1 – x x+y x 0.1 – x  0.1
HOCN  H   OCN –
0.1 – y x+y y 0.1 – y  0.1

Because [H ] will remain common in solution. Thus,

[H  ][HCOO – ]
K HCOOH   1.8 10 –4 … (1)
[HCOOH]

[H  ][OCN – ]
K HOCN   3.3  10 –4 … (2)
[HOCN]
(x  y)x
or K HCOOH   1.8  10–4 … (3)
0.1
(x  y)y
K HOCN   3.3  10 –4 … (4)
0.1
Thus, by eqs. (3) and (4)
x 1.8
 or y = 1.83 x … (5)
y 3.3
From Eq. (3) (x  1.83x).x  1.8  10 –5

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 x  2.52 10 –3
Therefore, y  4.61 10 –3
Thus, [H  ]  x  y  2.52  10 –3  4.61 10 –3  7.13 10 –3 M

10. 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
H2A is C and 1 and 2 be degree of dissociation for first and second dissocation.
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 
[H 2 A]
[C1 (1   2 )][C1 C1 2 ]
Ka1 
C(1  1 )

[H  ][A   ] [C1  C1 2 ][C1 2 ]

Ka 2  
[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]

Illustration 12:
Find the concentrations of H  , HCO3– and CO3–2 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
[H  ][HCO3– ]
 H  HCO
H 2CO3   –
 K1 
3 [H 2 CO3 ]

[6.6110 –5 ][HCO3– ]
or 4.45  10 –7  or [HCO3– ]  6.73  10 –5 mol litre –1
[0.01]
Again for dissociation of HCO3– , we have
 H   CO3–2
HCO3– 

[H  ][CO3–2 ] –11 [6.6110 –5 ][CO3–2 ]

K2  or 4.69  10 
[HCO3– ] [6.73  10 –5 ]

 [CO3–2 ]  4.78  10 –11 mol litre –1

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11. pH of a Mixture :

Let one litre of an acidic solution of pH 2 be mixed with two litre of other acidic solution of pH 3. The
resultant pH of the mixture can be evaluated in the following way.
Sample 1 Sample 2
pH = 2 pH = 3
[H+] = 10–2 M [H+] = 10–3 M
V = 1 litre V = 2 litre
M1V1 + M2V2 = MR(V1 + V2)
10–2  1 + 10–3  2 = MR(1 + 2)
12 103
 MR
3
4  103  M R (Here, MR = Resultant molarity)
pH R  – log[4 10 –3 ]  2.3980
Illustration 13:
Calculate the pH of the resultant mixture
(a) 10 mL of 0.2 M Ca(OH)2 + 25 mL of 0.1 M HCl
(b) 10 mL of 0.01 M H2SO4 + 10 mL of 0.01 M Ca(OH)2
(c) 10 mL of 0.01 M H2SO4 + 10 mL of 0.1 M KOH.
Solution:
(a) Ca(OH)2 + 2HCl  CaCl2 + 2H2O
2 2.5
0.75 –
0.75 0.75 1.5
 [Ca(OH)2] =  [OH–] = 2 × =
35 35 35
 pOH = 1.37  pH = 12.63

(b) H2SO4 + Ca(OH)2  CaSO4 + 2H2O

millimoles at t = 0 0.1 0 .1
hence both will neutalise each other so solution will be neutrall, So pH = 7
(c) H2SO4 + 2KOH  K2SO4 + 2H2O
millimoles at t = 0 0.1 1
– 0.8
0. 8
 [KOH] = = 0.04  [OH–] = 0.04  pOH = 1.4
20
 pH = 12.6
pKa and pKb for a conjugate acid-base pair
For an acid HX
 H   X –
HX 

[H  ][X – ]
 Ka  … (A)
[HX]
For conjugate base X – of acid HX
 HX  OH –
X –  H 2O 
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[HX][OH – ]
Kb  … (B)
[X – ]
By eqs. (A) and (B),
K a  K b  [H  ][OH – ]  K w
or pK a  pK b  pK w  14
Note : 1. Stronger is acid, weaker is its conjugate base.
2. Higher is the value of pK a of an acid, lower is acid strength and higher is basic
strength of its conjugate base.

12. Buffer Solution :

A Buffer solution is that which resist the pH change by addition of small quantity of acid or alkali.
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. CH3COONH4 exists almost entirely in
form of it’s ion CH3COO– or NH 4 if an acid is added to that solution, the H+ ion furnished by the
acid combine with CH3COO– ions to form feebly dissociated molecule of CH3COOH.
CH3COO– + H+   CH COOH
3
Since most of the H ions added are taken up by CH3COO– to form CH3COOH which itself slightly
+

dissociated, the pH of CH3COONH4 changes only slightly.

Now, suppose a base is added to CH3COONH4 solution the OH– furnished by the base will be
taken up by NH 4 ion to form feebly dissociated NH4OH.
 NH 4OH
NH 4  OH  
Since most of the OH– ions are taken up by NH 4 ions to form feebly dissociated NH4OH. Due 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.

13. Acid Buffer :

A very common acidic buffer is prepared by mixing equimolar solutions of acetic acid and sodium
acetate. Acetic acid is very slightly dissociated while sodium acetate, being a salt, is almost completely
dissociated. The mixture thus contains CH 3COOH molecules as well as CH 3COO – and Na  ions.
Let us consider the buffer action of this mixture.
Suppose a strong acid is added to the above mixture. The H  ions added will be taken up immediately
by CH 3COO – ions to form very slightly dissociated CH 3COOH :
H   CH 3COO – 
 CH3COOH
Feebly dissociated

Thus, the H  ions added are neutralized by the acetate ions present in the mixture. There is very little
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change in the pH of the mixture.
If, on the other hand, a strong base is added, the OH – ions added are neutralized by the acetic acid
present in the mixture :
OH –  CH 3COOH   CH 3COO –  H 2O
Thus, again, there is very little change in the pH of the mixture.

14. Calculation of pH of Acidic Buffer Solution :

e.g. Mixture of (CH3COOH + CH3COONa)

 CH COO– + H+
CH3COOH  3

[CH3 COO  ][H  ]

Ka 
[CH 3COOH]
Since most of CH3COO– comes from salt (CH3COONa) and hence conc. of CH3COO– will be
conc. of CH3COONa.
[Salt][H  ] K a [Acid]
Ka   [H  ] 
[Acid] [Salt]
Taking (–ve) log both side
[Acid]
–log [H+] = – log Ka – log
[Salt]
[Salt]
Handerson’s equation pH = pK a  log
[Acid]

Illustration 14:
Calculate the ratio of pH of a solution containing 1 mole of CH3COONa + 1 mole of
HCl per litre and of other solution containing 1 mole CH3COONa + 1 mole of acetic
acid per litre.
Solution:
Case I: pH when 1 mole CH3COONa and 1 mole HCl are present.
CH3COONa + HCl   CH3COOH + NaCl
Before reaction 1 1 0 0
After reaction 0 0 1 1
 [CH3COOH] = 1 M

 Ka 
 [H+] = C. = C  C   (K a .C)  (K a )  C=1
 
1
 pH1 = –
log Ka
2
Case II : pH when 1 mole CH3COONa and 1 mole of CH3COOH; a acidic buffer solution forms
 [Salt] = 1 M, [Acid] = 1 M
[Salt]
 pH2 = – log Ka + log
[Acid]
pH2 = –log Ka

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pH1 1
 
pH 2 2

Illustration 15:
Calculate pH change when 0.01 mol CH3COONa solution is added to one litre of 0.01
M CH 3COOH solution.
Ka (CH 3 COOH) = 1.8  10 –5 , pKa = 4.74.
Solution:
On addition of CH3COONa to CH3COOH solution resulting solution will be a buffer solution hence
on using Handerson eq. for acidic buffer.
[salt ]
pH = pKa + log
[acid ]
0.01
= 4.74 log = 4.74
0.01
 For initial pH, [H+] = K a  C = 1.8 10 5  0.01 = 4.24 × 10–4
 pH = 3.37
pH = 4.75 – 3.37 = 1.37

15. Basic Buffer :

A mixture containing equimolar solutions of ammonium hydroxide and its almost completely dissociated
salt, ammonium chloride, constitutes another good basic buffer. The mixture contains undissociated
NH 4 OH as well as NH 4 and Cl – ions. The buffer action of this mixture may now be considered.
If a strong acid is added, the H  ions added are neutralized by the base NH 4 OH :
H   NH 4 OH 
 H 2 O  NH 4
If a strong base is added, the OH – ions added are neutralized by NH 4 ions forming very slightly
dissociated NH 4 OH .

16. Calculation of pH of Basic Buffer Solution :

e.g. Mixture of (NH4OH + NH4Cl)

 NH 4 + OH–
NH4OH 

[NH 4 ][OH  ]
Kb 
[NH 4 OH]
Since most of NH 4 ions comes from salt (NH4Cl) so we take NH 4 conc. as conc. of salt (NH4Cl).

[Salt][OH  ]
Kb 
[Base]
K b  [Base]
[OH  ] 
[Salt]
Taking (–log10) both side

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[Base]
–log [OH–] = – log 10 Kb – log
[Salt]
[Salt]
pOH = pK b  log
[Base]
Hence pH = 14 – pOH at 14°C, K w  1 10 –14 mol/litre
Illustration 16:
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.
Solution:
(NH4)2SO4 2 NH 4 + SO 24
Thus, every one mole of (NH4)2SO4 gives two moles of NH 4 .
 millimoles of NH3, (NH4OH) = 100  0.1 = 10 millimol
millimoles of (NH4)2SO4 = 100  x = 100 x millimol
millimoles of NH 4 = 200  x = 200 x millimol
 pH = 9.26  pOH = 14 – 9.26 = 4.74
[NH 4 ]
pOH  pK b  log
[NH 4 OH]
200x
4.74 = 4.74 + log
10
1
log 20x = 0  20 x = 1  x= = 0.05.
20
Illustration 17:
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 NH 4 is 9.26, Calculate pH.
Solution:
Using Handerson equation for basic buffer
[salt]
pOH = pKb + log
[base]

 For NH4OH, pK a   NH 
4
+  pK b NH OH = 14
4

  pK b NH OH = 14– 9.26 = 4.74

4

NH4Cl + NaOH  NH4OH + NaCl

t=0 7.5 5
t=t 2.5 – 5 5
2. 5
 pOH = 4.74 + log = 4.44  pH = 14 – 4.44 = 9.56
5

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17. 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.
 CH 3COO –  NH 4
For example, CH 3COONH 4 
When an acid is added, it reacts with CH 3COO – to produce CH 3COOH and when a base is
added, it reacts with NH 4 to produce NH 4 OH .

18. Buffer Capacity or Buffer Index :

Buffer capacity of a solution is defined in terms of buffer index which is the change in the concentration
of Buffer acid (or base) required for change of it’s pH value by one, keeping (Csalt + Cacid) or (Cbase
+ Csalt) constant.
Let there be a buffer solution of volume 1 litre with ‘x’ mole of acid and ‘S’ moles of ‘salt’.
S
pH = pKa + log10
x S
1 S
pH  pK a  log e
2.303 x S
(pH) 1 1 1 
 
S 2.303  S x  S 


(pH) 1  x  S  S

S 2.303  S(x  S) 

S 1  S(x  S) 

(pH) 2.303  x 

Maximum value of Buffer Index

1 S(x  S)
B.I =
2.303 x
d 1 1 
(B.I) =  [x  2s]
dS 2.303  x 
for maximum value of Buffer index
d
(B.I) = 0
dS
After solving S = x/2
[Salt] S x/2
Thus   1
[Acid] x  S x  x / 2
[Salt]
Hence max. value of Buffer index occurs when  1,
[Acid]

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19. Buffer Range :

It is difficult to give an exact limit upto which a buffer can be used it in generally accepted that a
solution has useful buffer capacity provided that the value of [Salt]/[Acid] lie within the range of 10 to
0.1.Hence from Henderson equation
pK a  log 0.1  pH  pK a  log10 10
pK a  1  pH  pK a  1
Outside this range the Buffer capacity is too small to be of any practical application.

20. Hydrolysis of Salt :

Salts are strong electrolytes when dissolved in water, they dissociated almost completely into cations
or anions. If anion reacts with water it is called as anionic hydrolysis.
A– + H2O   HA + OH
–
Alkaline solution (pH increases).
If cation reacts with water it is called as cationic hydrolysis.
B+ + 2H2O   B(OH) + H3O
+
Acidic solution (pH lowers down).
“The phenomenon of the interaction of anions and cations of the salt with H+ and OH– ions furnished
by water yielding acidic or alkaline solution is known as salt hydrolysis.
For the study of hydrolysis salts are divided into 4 groups.
Hydrolysis of salt of strong Acid or weak base:
NH4Cl is a salt of weak base (NH4OH) and strong acid (HCl). After hydrolysis resultant solution will
be acidic due to presence of strong acid HCl.
 NH 4 OH  HCl
NH 4 Cl  H 2 O 

 NH 4 OH  H   Cl
NH 4  Cl   H 2 O 

 NH 4 OH  H 
NH 4  H 2 O 
(acidic)

[NH 4 OH][H  ]
Kh 
[NH 4 ]
Relation B/w K h , K b and K w :
 NH 4  OH 
NH 4 OH

[NH 4 ][OH  ]
Kb  … (1)
[NH 4 OH]
 H   OH 
H 2 O 

K w  [H  ][OH  ] … (2)
Dividing (2)  (1)
Kw [H  ][OH  ]
  [NH 4 OH]
K b [NH 4 ][OH  ]
Kw
= Kh
Kb

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Degree of hydrolysis
 NH 4  OH 
NH 4  H 2 O 
C(1 h ) Ch Ch

Ch . Ch
Kh   Ch 2 (1 – h  1)
C(1  h)

Kh Kw
h  h
C KbC

Kw Kw  C
[H  ]  Ch  C  [H  ] 
KbC Kb
Taking –log10 both side
1 1 1
pH  [pK w  pK b  log C]  pH = 7 - pK b - log C
2 2 2

Illustration 18:
Calculate degree of hydrolysis and pH of 0.2 M solution of NH 4 Cl . Given Kb for
NH 4 OH is 1.8  10 –5 .
Solution:
 NH 4 OH  HCl
NH 4Cl  H 2O 
Before hydrolysis 1 0 0
After hydrolysis 1 –h h h
Where h is degree of hydrolysis

K   Kw  10 –14
h  h      –5
 5.27 10–5
 C   K b .C  1.8  10  0.2
From HCl, strong acid

 Kh   Kw   10 –14  0.2 


[H ]  C.h  C    (K h .C)   .C    –5 
 1.054  10 –5
 C   Kb   1.8  10 

 pH  – log[H  ]  – log1.054  10 –5
= 4.9771

Illustration 19:
Find out the amount of NH4Cl dissolved in 500 mL to have pH = 4.5. Kb for NH4OH
is 1.8  10 –5 .
Solution:
Using salt hydrolysis formula
pK b log c 4.74 log c
pH = 7 – –  4.5 = 7 – –  log c = 0.26
2 2 2 2
 c =1.82 M

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1.82
 WNH = × 53.5 = 48.7 gm
4Cl 2

Hydrolysis of salt of weak acid and strong base:

CH3COONa is a salt of weak acid (CH3COOH) and strong base (NaOH). After hydrolysis resultant
solution will be basic due to presence of strong base (NaOH).
 CH 3COOH  NaOH
CH 3COONa  H 2 O() 

 CH3COOH  Na   OH 
CH 3COO   Na   H 2 O() 

[CH 3COOH][OH  ]
Kh 
[CH 3COO  ]
Relation between, K h , Kw and Ka
 CH 3COO   H 
CH 3COOH 

[CH3 COO  ][H  ]

Ka  … (1)
[CH 3COOH]
 H  OH 
H 2 O 

K w  [H  ][OH  ] … (2)
Dividing equation (2) ÷ (1)
K w [H  ][OH  ]  [CH 3COOH] [OH  ][CH 3COOH]
   Kh
Ka [CH 3COO ][H  ] [CH 3COO  ]

Degree of Hydrolysis
 CH 3COOH  OH 
CH 3COO   H 2 O() 
at time = 0 C 0 0
at time = t C(1 – h) Ch Ch
Ch . Ch
Kh   Ch 2 (1 – h  1) h should be smaller than 0.1 than 1 – h = 1.
C(1  h)

Kh Kw
h  h
C KaC

 Kw KwC
OH   Ch OH   C 
KaC Ka

Kw Ka K a  Kw
H3 O   Kw 
[OH  ] KwC C
Taking (–ve) log both side
1 1 1 1
 log[H  ]  log K w  log K a  log C  [pK w  pK a  log C]
2 2 2 2
1 1
pH = 7  pK a  log C
2 2
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pH will be more than 7, hence resultant solution will be basic in nature.

Illustration 20:
Calcium lactate is a salt of weak organic acid and strong base, represented as Ca(Lac)2.
A saturated solution of Ca(Lac)2 contains 0.13 mole of this salt in 0.50 L solution. The
pOH of this solution is 5.60. Assuming a complete dissociation of the salt, calculate Ka
of lactic acid.
Solution:
Formula of calcium lactate suggests that lactic acid is dibasic acid. Each mole of salt furnishes two
moles of lactate ion
Ca(Lac)2 Ca2+ + 2 Lac–
0.50 L solution contains = 0.13 mol of salt = 0.26 mol of lactate ion
 1 L of solution contains = 0.52 mol of lactate ion
[lactate] = 0.52 M.
given pOH = 5.6
 pH = 8.4
using equation of pH for salt of weak acid and strong base
pK a log C
pH = 7 + 
2 2
pK a log 0.52 pK a
8.4 = 7 +  =7+  0.14
2 2 2
pKa = 3.08
Ka = 10–3.08 = 8.3  10–4.

Illustration 21:
What is the pH of a 0.5 M aqueous NaCN solution? pKb of CN –  4.70 .
Solution:
1 1
PH = [14 + pKa + log c] = [14 + 9.3 + log 0.5] = 11.5
2 2
Hydrolysis of salt of Weak Acid and Weak Base:
Let’s take the salt CH3COONH4 made of salt of weak acid (CH3COOH) and Weak base (NH4OH).
 CH 3COOH  NH 4 OH
CH 3COONH 4  H 2 O 

 CH 3COOH  NH 4OH

CH 3COO   NH 4  H 2O 

[CH 3COOH][NH 4OH]

Kh 
[CH 3COO  ][NH 4 ]
Relation between, K h , K w , K a & K b
 CH 3COO   H 
CH 3COOH 

[CH3 COO  ][H  ]

Ka  … (1)
[CH 3COOH]
 NH 4  OH 
NH 4 OH 

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[NH 4 ][OH  ]
Kb  … (2)
[NH 4 OH]
 H   OH 
H 2 O 

K w  [H  ][OH  ] … (3)

Kw [H  ][OH  ]  [CH 3COOH][NH 4 OH]


K a  Kb [CH3 COO  ][H  ][NH 4 ][OH  ]
Kw
= Kh
Ka ×Kb

Degree of Hydrolysis
 CH 3COOH  NH 4OH
CH 3COO   NH 4  H 2 O 
at time = 0 C C 0 0
at time = t C(1 – h) C(1 – h) Ch Ch
Ch . Ch h2
Kh  
C(1  h)C(1  h) (1  h) 2
if h  0.1, 1  h  1

h Kw
=
1-h K aK h

The acetic acid formed would partially decompose to give CH 3COO – and H  . But because of
common ion effect (that is, due to the unhyrolysed CH 3COO – ) it is possible to neglect the acetate
ion coming from CH 3COOH .
 CH 3COO –  H 
Therefore CH 3COOH 
C C(1– )

C(1– )[H ]
Ka 
C
[H  ]
Ka  (1–   1)

Kw K w Ka 1
[H  ]  K a   K a  or pH = pK w + pK a - pK b
Ka Kb Kb 2
This expression is independent of conc. of the salt.
(i) if Ka = Kb, pH = 7 solution will be neutral
(ii) if Ka > Kb, pH < 7, acidic solution
(iii) if Ka < Kb then pH > 7, alkaline solution
In the hydrolysis of salt of weak acid and a weak base such as NH4CN, CH3COONH4. Both the
ions are hydrolysied, if we assume K a  K b , then the hydrolysis of the cation and anion of the salt
occur approximately to equal extent for a salt which has K a  K b , it would be expected at the first
glance that CN  ions hydrolysed to a much greater extent than NH 4 ions. However, the hydrolysis

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of CN– ions produced OH– ions according to the equation.
 HCN  OH 
CN   H 2 O 

which can react with NH 4 ions as

 NH 4 OH
OH   NH 4 
This latter reaction causes equilibrium in the from reaction to be displaced to the right. Because OH–
ions are removed from the solution. Also the production of OH– by the former reaction displaces the
latter reaction to the right. Therefore the hydrolysis of one ion drags the hydrolysis of the other ion
along so that both the hydrolysis are fairly extensive not too far in extant from each other so it is fairly
safe to assume that [HCN] = [NH4OH], even in the case of the salt where K a  K b .

Illustration 22:
The dissociat ion const ant s for aniline, acet ic acid and wat er at 25°C ar e
3.83  10 –10 , 1.75  10 –5 and 1.008  10 –14 respectively. Calculate degree of hydrolysis
of aniline acetate in a deci normal solution. Also report the pH.
Solution:
  Aniline + Acetic acid
Aniline+ + Acetate– +  H 2O 
Before hydrolysis 1 1 0 0
After hydrolysis 1– h 1–h h h
Let concentration of salt be C mol litre –1

[Aniline][Acetic Acid] C.h.C.h

 Kh   –

[Aniline] [Acetate] C.(1 – h).C.(1– h)

h2
 Kh 
(1 – h)2

h h  Kw   1.008 10 –14 

  (K h )       –5 –10 
1– h 1– h  K a .K b   1.75 10  3.83 10 
 h = 54.95%

Illustration 23:
Calculate the pH of an aqueous solution of 1.0 M ammonium formate assuming complete
dissociation. (pKa of formic acid = 3.8 and pKb of ammonia = 4.8)
Solution
1 1
pH = [pKw + pKa – pKb] = (14 + 3.8 – 4.8) = 6.5
2 2

21. Case IV : Salts of Strong Acid + Strong Base :

e.g., NaCl, KNO3 , … etc.

This category of salts does not undergo salt hydrolysis

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22. Solubility and Solubility Product :

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.
 xAy+ + yBx–
AxBy 

K sp  [A y ]x [B x  ]y
Let the solubility of AxBy is S then
K sp  [xS]x [yS]y
K sp  x x .y y [Sx  y ]
The principle of solubility product is applicable for sparingly soluble salt.

23. Common-ion Effect on Solubility :

The common ion present 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
 Ag   Cl –
AgCl(s)  aq. 

 K   Cl –
KCl  aq. 
For AgCl K SP  [Ag  ][Cl – ]
[Cl – ] Increases in solution due to presence of KCl and thus to have K SP 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 – ]
K SP  s(s  0.1)
s being small in comparison to 0.1 and thus may be neglected therefore,
K SP
K SP  s  0.1 or s AgCl 
0.1
where s is solubility of AgCl in presence of 0.1 M KClaq.

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24. Ion 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
dissolve in it.
If ionic product greater than solubility it means solution is holding more salt than can dissolve in it,
therefore ppt started till, until or unless ionic product becomes equal to Ksp.

25. 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 CrO4–2 both of these ions form ppt with Ag+ though
the Ksp (AgCl) > Ksp (Ag2CrO4). Yet it is AgCl (less soluble) which ppted first when Ag+ ions added
to the solution. In order to predict which ion (Cl– or CrO4 2 ) ppt first. We have to calculate the conc.
of Ag+ ion needed to start ppt through the Ksp and given conc. of Cl– and CrO4 2 if the conc. of Ag+
ions needed to start the ppt of CrO4 2 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4 2 . 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.
(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.
 CH COO–
CH3COONH4  + NH 4 … (1)
3

S–y S–y
CH3COO– + NH 4  CH COOH + NH OH
+ H2O  3 4

S–y S–y y y … (2)

K sp  (S  y)(S  y)  (S  y)2
Due to hydrolysis of salt from equation (2)

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[CH 3COOH][NH 4OH] y.y
Kh   

[CH3COO ][NH 4 ] (S  y)(S  y)
2
 y 
Kh   
 S y 
and we also know that
Kw
Kh 
Ka K b
26. 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 COO– + NH 4
CH3COONH4  3

S–y y
– +
CH3COO + H   CH3COOH … (2)
S–y (from Acidic Buffer) y
K sp  [CH3COO  ][NH 4 ] = [S – y] [y] = y [S – y]
for equation (2)
1 [CH3 COOH] y
 Ka  
K a (CH3COOH ) [CH 3COO ][H ] (S  y)(H  )
 

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

27. Solubility of a salt of weak acid and weak base in basic buffer :

 CH COO– + NH 4
Similarly CH3COONH4  3

y             S – y
NH 4  OH   NH OH
 4

S – y (from buffer) y
K sp (CH3COONH 4 )  [CH3COO  ][NH 4 ]  K sp  y(S – y)

1 [NH 4 OH] y
 K b  
Kb [NH 4 ][OH ] (S  y)(OH  )
 

The solubility of CH 3COONH 4 in basic buffer would be higher than pure water..

Illustration 24:
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:
CaSO4(s) Ca2+ (aq) + SO 24  (aq), Ksp = ?
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

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 [Ca2+] = [ SO 24  ]  0.01765 M .
 Ksp = [Ca2+] [SO 24  ] = (0.01765)2 = 3.115  10–4.

Illustration 25:
Zn salt is mixed with (NH4)2S of molarity 0.021 M. What amount of Zn2+ will remain
unprecipitated in 12 mL of the solution? KSP of ZnS = 4.51  10–24.
Solution:
(i) Ksp = [Zn+2] [S–2]
4.51 × 10–24 = [Zn+2] × 0.021  [Zn+2] = 2.15 × 10–22 M
12
 amount = 2.15 × 10–22 × 65.4 × = 1.68 ×10–22 g
1000

Illustration 26:
Calculate the solubility of AgCN in a buffer solution of pH = 3. Given KSP of AgCN =
1.2  10–16 and Ka for HCN = 4.8  10 –10.
Solution:
AgCN Ag+ + CN– Ksp = 1.2 × 10–16 ......(1)
x x–y
– –
Kw 1014
CN + H2O HCN + OH Kh = = 10 ......(2)
–11 Ka 4.8  10
x–y y 10
Fom (1), x(x – y) = 1.2 × 10–16
 11
1014 y  10
From (2) =
4.8 10 10 (x  y)
16 14
1.2  10 10
Multiplying both, xy × 10–11 = 10
4.8  10
 xy = 2.5 × 10–11
now x – xy = 1.2 × 10–16  x2 = 1.2 × 10–16 + 2.5 × 10–11
2

 x2 = 2.5 × 10–10
x = 1.58 × 10–5 M

28. 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+ +  Ag (NH 3 )2 (aq.)
2NH3 
b–y a –2y y
where y is the amount of Ag+ which reacted with NH3.
K sp  [Ag  ][Cl ]  (b  y)y

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[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.

29. Acid-base Indications :

An acid & base indicator are substance which changes it’s colour within limits with variation in pH of
the solution to which it is added. Indicators, in general are either organic weak acid or weak bases
with a characteristics of having different colours in the ionized and unionized form e.g. phenophthalein
is a weak acid (ionized form is pink and unionized form is colourless).
Acidic Indicator Action (e.g. HPh)
HPh (Phenolpthalein) is a colourless weak acid
 H   Ph 
HPh 
Colourless (Pink )

[H  ][Ph  ]
K IN 
[HPh]
If the solution is acidic, the H+ by the acid increases and since Kin is constant and it does not depend
upon the concentration so HPb also increases mean equilibrium will shift towards left means solution
remain colourless. By addition of alkali, OH– will be furnished and that OH– will combines with H+ of
HPh to form water and equilibrium will moves towards right and therefore solution becomes pink.
Thus HPh appears colourless in acidic and pink in alkaline solution pH range of HPh is (8.3 –10).
[In  ]
pH  pK In  log
[HIn]
The colour of the indicator changes from colour A to colour B at a particular point known as end
point of indicator. At this point [HIn]  [In – ] means pH  pK ln (at this point half of indicator is in the
acid form and half in the form of its conjugate form.

30. Indications (Basic) action of MeOH (Methyl) Orange :

When MeOH is dissolved in water and undergoes dissociation to a small extent. The undissociated
molecules are yellow while dissociated Me+ are red in colour.
 Me  OH 
MeOH 
yellow red colourless

If the solution is acidic, the H furnished by the acid combines with OH– ions furnished by the indicators
+

to form undissociated water. This shifts the equilibrium towards right giving red coloured solution.
Therefore in acid solution, this indicator gives red colour. In the presence of alkali, OH– increases and
due to common ion effect the dissociation of MeOH surpress means equilibrium will shifts towards
left. Hence the solution in alkaline medium remains yellow in colour.
Colour of solution depends upon relative amount of ionized form to unionized form (ratio of Me+/
MeOH).

In general pH range of indicator lies B/w pK ln  1 to pK ln  1

Case 1 : pH = pK ln  1

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In 
Means  0.1  10%
[HIn]
Percentage ionization of indicator would be
In  0.10 HIn

 100%   100%
[In ]  [HIn] 0.10 HIn  (HIn)
1
=  100  9.1%
11
In fact, pH = pKIn – 1 is the maximum pH upto which the solution has a distinct colour characteristic
of HIn. At pH smaller than this value, more of the indicator is present in the unionized form.
Thus at pH  pKin –1, the solution has a colour characteristic of HIn.
Case 2 : at pH = pK In  1

[In  ]
Mean  10
[HIn]
Percentage of ionization of indicator is
[In  ] 10 [HIn] 1000

 100%  100%   91%
[In ]  [HIn] 10 [HIn]  [HIn] 11
Thus most of the indicator is present in the ionized form In  and solution gets the colour characteristic.
Infact pH = pKIn + 1 is the minimum pH upto which the solution has a distinct characteristic of In  .
At pH greater than this value, still more of the indicator is present in the ionized form. Thus at
pH  pK In  1 , the solution has a colour characteristics of In  .

Illustration 27:
An indicator is a weak acid and pH range of its colour is 3.1 to 4.5. If the neutral point
of the indicator lies in the centre of the hydrogen ion concentrations corresponding to
the given pH range, calculate the ionization constant of the indicator.
Solution:
pH = – log [H3O+], or log [H3O+] = – pH
 [H3O+] = antilog of (–pH)
for pH = 3.1 [H3O+]1 = antilog of (–3.1) = antilog of (4.9)  7.94  104
for pH = 4.5 [H3O+]2 = antilog of (–4.5) = antilog of (5.5)  3.16  105
Since neutral point lies at the centre of the hydrogen ion concentration in the given pH range, hence
[H3O+] at the neutral point
[H O ]  [H 3O  ]2
[H3O+]  3 1
2
7.94  104  3.16  105
  4.13  104 M
2
Let indicator be HIn behaving as weak acid, then
HIn + H2O H3O+ + In–
[H 3O  ][In  ]
K In  [ionization constant of indicator is KIn]
[HIn]
= [H3O+] {since at neutral point [In–] = [HIn]} = 4.13  10–4.

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Illustration 28:
Calculate the pH at w hich an acid indicator w ith K a = 1  10–5 changes colour when
the indicator concentration is 1  10–3 M. Also report the pH at which coloured ion is
80% present.
Solution:

[In ]
pH = pKIn + log
[HIn]

[In ]
For colour change, =1
[HIn]
 pH = pKIn = – log (1 ×10–5) = 5
now [In–] = 80, [HIn] = 20
80
 pH = 5 + log = 5.6
20

31. Ostwald’s Theory :

According to this theory:

(a) The colour change is due to ionization of the acid-base indicator. The unionized form has different
colour than the ionized form.
(b) The ionization of the indicator is largely affected in acids and bases as it is either a weak acid or a
weak base. In case, the indicator is a weak acid, its ionization is very much low in acids due to
common H+ ions while it is fairly ionized in alkalies. Similarly if the indicator is a weak base, its
ionization is large in acids and low in alkalies due to common OH– ions.
Considering two important indicators phenophthalein (a weak acid) and methyl orange (a weak
base), Ostwald theory can be illustrated as follows:
Phenolphthalein: It can be represented as HPh. It ionizes in solution to a small extent as:
 H   Ph 
HPh 
Colourless Pink

Applying law of mass action,

[H  ][Ph  ]
K
[HPh]
The undissociated molecules of phenolphthalein are colourless while Ph– ions are pink in colour. In
presence of an acid, the ionization of HPh is practically negligible as the equilibrium shifts to left hand
side due to high concentration of H+ ions. Thus, the solution would remain colourless. On addition of
alkali, hydrogen ions are removed by OH– ions in the form of water molecules and the equilibrium
shifts to right hand side. Thus, the concentration of Ph– ions increases in solution and they impart pink
colour to the solution.
 H 3 O 
HIn  H 2 O  In 
`Acid form ' `Base form '

Conjuage acid-base pair

[In  ][H 3 O]  [HIn]

K In  ; K In  Ionization constant of indicator,, [H3 O]  K In 
[HIn] [In  ]

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[HIn]
pH = – log10 [H3 O] = – log10 [KIn] – log10
[In  ]

[In  ]
pH = pKIn + log10 (Handerson equation for indicator)
[HIn]
At equivalence point;
[In  ]  [HIn] and pH = pKIn

Methyl orange: It is a weak base and can be represented as MeOH. It is ionized in solution to
give Me+ and OH– ions.
 Me   OH 
MeOH 
Yellow Red

Applying law of mass action

[Me  ][OH  ]
K
[MeOH]
In presence of an acid, OH– ions are removed in the form of water molecules and the above equilibrium
shifts to right hand side. Thus, sufficient Me+ ions are produced which impart red colour to the
solution. On addition of alkali, the concentration of OH– ions increases in the solution and the equilibrium
shifts to left hand side (due to common ion effect), i.e., the ionization of MeOH is practically negligible.
Thus, the solution acquires the colour of unionized methyl orange molecules, i.e., yellow.
This theory also explains the reason why phenolphthalein is not a suitable indicator for titrating a weak
base against strong acid. The OH– ions furnished by a weak base are not sufficient to shift the
equilibrium towards right hand side considerably, i.e., pH is not reached to 8.3. Thus, the solution
does not attain pink colour. Similarly, it can be explained why methyl orange is not a suitable indicator
for the titration of weak acid with strong base.
Quinonoid Theory: According to this theory:
(a) The acid-base indicators exist in two tautomeric forms having different structures. Two forms are in
equilibrium. One form is termed benzenoid form and the other quinonoid form.

HO OH O O

(b) The two forms have different colours. The colour change is due to the interconversion of one tautomeric
form into other.
(c) One form mainly exists in acidic medium and the other in alkaline medium.
Thus, during titration the medium changes from acidic to alkaline or vice-versa. The change in pH
converts one tautomeric form into other and thus, the colour change occurs.
Phenolphthalein has benzenoid form in acidic medium and thus, it is colourless while it has quinonoid
form in alkaline medium which has pink colour.

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OH O

C 
OH
 
 C
H

O
OH OH
C COO

Methyl orange has quinonoid form in acidic solution and benzenoid form in alkaline solution. The
colour of benzenoid form is yellow while that of quinonoid form is red.
CH3

O3S NH N N
CH3
Quinonoid form — Acidic solution (red)
-

OH

H
CH3

O3S N N N
CH3

1. Daily Practice Problem Sheet

Dissociation of acids and base
I. For a weak acid HA
HA H+ + A– Ka = 10
When the concentration of acid is 10 M, then
Q. 1 The degree of dissociation of acid is -
(A) 1 (B) 0.618 (C) 0.309 (D) 0.418
Q. 2 With respect to Q. 1 what will be the concentration of H+ ion -
(A) 6.18 M (B) 10 M (C) 3.09 M (D) 4.18 M
Q. 3 When the concentration of acid is reduced to 1 M, then degree of dissociation will be
(A) 0.6 (B) 3.16 (C) 0.916 (D) 0.8
Q. 4 With Respect to Q. 3 the concentration of H+ ion will be -
(A) 0.916 (B) 3.16 (C) 0.6 (D) 0.8
Q. 5 Now the concentration of acid is further reduced to 0.1 M, then its degree of dissociation now be -
(A) 0.916 (B) 10 (C) 0.6 (D) 0.99
Q. 6 With respect to Q. 5 now the concentration of H+ ion is -
(A) 0.0916 (B) 0.1 (C) 0.06 (D) 0.099

II. Degree of dissociation of a weak acid having concentration 10–3 M is 0.1, then
Q. 7 Ka of the acid is -
(A) 1.1 × 10–5 (B) 10–5 (C) 1.1 × 10–4 (D) 10–4
Q. 8 Concentration of H+ ion is -
(A) 10–2 M (B) 10–5 M (C) 10–4 M (D) 10–3 M

III. A weak acid having Ka = 2.5 × 10–5 gives [H+] = 1.3 × 10–4 M.
Q. 9 On the basis of above information, degree of dissociation of acid is
(A) 0.25 (B) 0.161 (C) 0.05 (D) 0.025
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Q. 10 Concentration of acid would be

(A) 8.06 × 10–2 M (B) 4.03 × 10–4 M (C) 8.06 × 10–4 M (D) 4.03 × 10–2 M

IV. In a 10–2 M solution of acid HA having Ka = 10–4,

Q.11 What will be the [H+] -
(A) 9.5 × 10–4 M (B) 1× 10–3 M (C) 9.5 × 10–2 M (D) 1.1 × 10–4 M

V. For an acid HA having Ka = 2.1 × 10–4 & molecular weight = 90.

Q. 12 The amount of acid which should be dissolved in 10  of solution having = 8% is
(A) 34.67 gm (B) 29.53 gm (C) 13.63 gm (D) 27.17 gm

VI In a 10% dissociated solution of a weak acid HA, concentration of H+ ion is 3.5 × 10–3 M, then
Q. 13 Ka for the acid is
(A) 7.0 × 10–6 (B) 3.5 × 10–5 (C) 3.9 × 10–4 (D) 4.9 × 10–6

2. Daily Practice Problem Sheet

Q-1 to Q-9)
Generally all organic acids are weak acids. Acetic acid (CH3COOH) & formic acid (HCOOH) both
are organic acids, hence both are weak acids & most commonly used in ionic equilibrium CH3COOH
is weaker than HCOOH due to +I effect of –CH3 group. Stronger acid has higher value of Ka &
weaker acid has smaller value of Ka. Thus for
CH3COOH CH3COO– + H+ Ka = 1.8 × 10–5
HCOOH HCOO– + H+ Ka = 1.8 × 10–4
What will be the degree of dissociation and H+ ion concentration :
Q. 1 When concentration of acetic acid is 1 M -
(A) 4.24 × 10–4, 4.24 × 10–4 (B) 1.34 × 10–3, 1.34 × 10–3
(C) 4.24 × 10–3, 4.24 × 10–3 (D) 1.34 × 10–3, 1.34 × 10–4
Q. 2 If 1M formic acid is taken -
(A) 4.24 × 10–4, 1.34 × 10–2 (B) 1.34 × 10–2, 1.34 × 10–2
(C) 4.24 × 10–4, 4.24 × 10–4 (D) 3.4 × 10–5, 1.34 × 10–5
Q. 3 When concentration of acetic acid is reduced to 0.1 M
(A) 4.24 × 10–4, 1.34 × 10–2 (B) 1.34 × 10–2, 1.34 × 10–3
(C) 4.24 × 10–2, 1.34 × 10–3 (D) 1.34 × 10–2, 1.34 × 10–2
Q. 4 When 0.1 M HCOOH is considered -
(A) 4.24 × 10–2, 4.24 × 10–3 (B) 1.34 × 10–2, 1.34 × 10–3
(C) 4.24 × 10–3, 4.24 × 10–2 (D) 3.4 × 10–5, 3.4 × 10–6
Q. 5 When the concentration of acetic acid is further reduced to 10–2 M
(A) 3.4 × 10–5, 3.4 × 10–6 (B) 2.36 × 10–3, 2.36 × 10–4
(C) 1.34 × 10–2, 1.34 × 10–4 (D) 4.24 × 10–2, 4.24 × 10–4
Q. 6 Now 10–2 M HCOOH is taken, then
(A) 1.34, 1.34 × 10–3 (B) 0.125, 1.25 × 10–3
(C) 1.25, 1.25 × 10–3 (D) 0.25, 2.5 × 10–3

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Q. 7 When concentration of acetic acid is 10–4 M
(A) 0.34, 3.4 × 10–5 (B) 1.34, 1.34 × 10–5
(C) 0.71, 7.1 × 10–6 (D) 0.25, 2.5 × 10–3
Q. 8 Similarly, now 10–4 M HCOOH is considered
(A) 0.715, 7.15 × 10–5 (B) 1.34, 1.34 × 10–5
–6
(C) 0.61, 6.1 × 10 (D) 0.34, 3.4 × 10–5
Q. 9 Finally concentration of acetic acid is reduced to 10–5 M
(A) 0.34, 3.4 × 10–6 (B) 0.236, 2.36 × 10–5
–6
(C) 0.71, 7.1 × 10 (D) 0.25, 2.5 × 10–5
Q. 10 In a 5  solution of acetic acid, having= 1% and Ka = 1.8 × 10–5. The amount of acetic acid
present in the solution is -
(A) 54 gm (B) 27 gm (C) 60 gm (D) 30 gm
Q.11 of 0.1 M acetic acid is -
(A) 1.34 × 10–3 (B) 4.24 ×10–2 (C) 1.34 ×10–2 (D) 4.24 ×10–3
Q. 12 How much water must be added in 900 ml of 0.1 M CH3COOH solution to triple its degree of
dissociation (Assume < 5% is negligible) -
(A) 7.2  (B) 3.6  (C) 5.8  (D) 2.4 
Q. 13 When 35 gm of NH4OH is dissolved in 10 of water, then its degree of dissociation will be -
(A) 1.34 × 10–3 (B) 1.34 × 10–2 (C) 4.24 × 10–2 (D) 4.24 × 10–3
Q. 14 In the above question concentration of OH– ion is -
(A) 0.134 × 10–3 (B) 1.34 × 10–3 (C) 4.24 × 10–3 (D) 0.424 × 10–3
Q. 15 The amount of CH3NH2 dissolve in 2 of water so that it produces concentration OH– is equal to
5 ×10–4 M, is - [Given Kb of CH3NH2 = 2 × 10–6]
(A) 5.6 gm (B) 3.88 gm (C) 7.75 gm (D) 8.3 gm

3. Daily Practice Problem Sheet

Common ion effect
Whenever any electrolyte (strong/acid) producing common ion is dissolved in the solution of weak
acid & weak base, concentration of common ion increases but degree of dissociation of weak acid
or weak base decreases hence concentration of other ion also decreases. In terms of concentration,
more is the concentration of common ion, more will be the increase in the degree of dissociation.
In terms of nature of electrolyte, more strong electrolyte changes degree of dissociation more.
Case I : Mixture of strong electrolyte + weak electrolyte
Q. 1 In presence of 2M HCl solution degree of dissociation of 0.1 M CH3COOH is -
(A) 9 × 10–6 (B) 3 × 10–6 (C) 9.5 × 10–5 (D) 3.5 × 10–5
Q. 2 In the above question concentration of H+ ion will be -
(A) 1 M (B) 0.1 M (C) 2 M (D) 0.2 M
Q. 3 The pH of the solution containing 0.1 M HNO3 & 0.1 M HCOOH - [Ka of HCOOH is 1.8 ×10–4]
(A) 0.1 (B) 1 (C) 2 (D) 0.2
Q. 4 Degree of dissociation of 1 M CH3COOH in presence of 1 M (CH3COO)2Pb having degree of
dissociation 80% and 3 M (CH3COO)2 Ca, is -
(A) 2.36×10–6 (B) 1.36×10–6 (C) 1.34×10–3 (D) 4.24×10–3

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Q. 5 In the above question [H+] & [CH3COO–] is -
(A) [CH3COO–] = [H+] = 7.6 (B) [CH3COO–] = [H+] = 2.36 ×10–6
– + –6
(C) [CH3COO ] = 7.6 ; [H ] = 2.36 ×10 (D) [CH3COO–] = 1.34 ×10–2 ; [H+] = 7.6
Q. 6 Degree of dissociation of 1 M CH3COOH in presence of 2 M HClO4 + 0.1 M HCl having = 95%,
is -
(A) 2.36 ×10–6 (B) 8.6 ×10–6 (C) 3.34 ×10–5 (D) 1.86 ×10–5
Q. 7 In the above Q. [H+] & [CH3COO–] is -
(A) [CH3COO–] = [H+] = 8.6 ×10–6 (B) [CH3COO–] = [H+] = 2.095
(C) [CH3COO–] = 7.6 ; [H+] = 2.36 ×10–6 (D) [CH3COO–] = 8.6 ×10–6 ; [H+] = 2.095
(Q.8 to Q. 11) Degree of dissociation and [OH– ] in 0.1 M NH4OH
Q. 8 In presence of 1.2 M (NH4)3PO4 having  = 50% -
(A) 10–6, 10–5 (B) 10–5, 10–6
–2 –3
(C) 1.34 × 10 , 1.34 × 10 (D) 2.36 × 10–5, 2.36× 10–6
Q. 9 In presence of 2 M Ca(OH)2 having  = 90% -
(A) 5 × 10–5, 5 × 10–6 (B) 2.36 × 10–5, 2.36× 10–6
(C) 1.34 × 10–2, 3.6 (D) 5 × 10–6, 3.6
Q. 10 In presence of 0.1 M (NH4)2SO4 -
(A) 1.34 × 10–2, 3.6 (B) 10–5, 10–6
(C) 9 × 10–5, 9 × 10–6 (D) 5 × 10–6, 3.6
Q.11 In presence of 1.8 M Al(OH)3 having  = 10% -
(A) 3.34 × 10–5, 0.54 (B) 5 × 10–5, 0.54
–5 –6
(C) 9 × 10 , 9 × 10 (D) 5 × 10–6, 0.65
Q. 12 The amount of (NH4)2SO4 having degree of dissociation 75% which should be dissolved in 1500 ml
of 1 M NH4OH to decrease its degree of dissociation by 200 times, is -
(A) 112. 1 gm (B) 224.2 gm (C) 56.0 gm (D) 65.4 gm
Q. 13 500 ml of 0.2 M H2SO4 is mixed with 1500 ml of 0.1 M HCOOH solution. If Ka for formic acid is
1.8 × 10–4, then pH of the final solution is -
(A) 1 (B) 0.1 (C) 0.02 (D) 2
Q. 14 0.1 M CH3COONa is mixed with 0.05 M HCl, then the final pH of the solution is -
(A) 4.74 (B) 3.74 (C) 7.34 (D) 3.6

4. Daily Practice Problem Sheet

Common ion effect
Case-II : Mixture of two weak electrolytes
Q. 1 A solution contains 0.09 M HCl, 0.09 M CCl2HCOOH, and 0.1 M CH3COOH. If total [H+] = 0.1
and Ka for CH3COOH = 10–5, Ka for CCl2HCOOH is
(A) 1.35 × 10–4 (B) 0.18 × 10–2 (C) 0.18 × 10–5 (D) 1.25 × 10–2
Q. 2 If 0.1 M CH3COOH is mixed with 0.1 M CH2ClCOOH,
[Given : Ka CH3COOH = 1.8 × 10–5, Ka CH2ClCOOH = 1.8 × 10–4]
Find out total [H+] -
(A) 0.404 × 10–2 (B) 1.44 × 10–3 (C) 4.44 × 10–3 (D) 8.44 × 10–4

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Q. 3 In a solution containing 0.1 M HCOOH and 0.1 M HOCN, [H+] will be -
Given : Ka for HCOOH and HOCN are 1.8 × 10–4 and 3.3 × 10–4
(A) 7.13 × 10–3 M (B) 3.56 × 10–3 M (C) 1.35 × 10–4 M (D) 7.97 × 10–4 M
Q. 4 On addition of ammonium chloride to a solution of NH4OH
(A) dissociation of NH4OH increases (B) concentration of OH– decreases
(C) concentration of OH– increases (D) concentration of NH4+ and OH– decreases
(Q.5-Q.6)
Considering a 0.1 M H3PO4 solution, answer the questions given below :
[Given : K1 = 7.5 × 10–3, K2 = 6.2 × 10–8, K3 = 3.6 × 10–13]
Q. 5 In the given solution [H+ ] & [H2PO4– ] is
(A) [H+] = [H2PO4–] = 0.024 M (B) [H+] = 0.024 M ; [H2PO4–] = 0.012 M
+ –
(C) [H ] = 0.076 M ; [H2PO4 ] = 0.024 M (D) [H+] = [H2PO4–] = 0.076 M
Q. 6 concentration of [H3PO4] at equilibrium is
(A) 0.076 M (B) 0.024 M (C) 0.012 M (D) 0.76 M
Q. 7 The degree of dissociation of a weak electrolyte increases -
(A) on increasing pressure (B) on decreasing dilution
(C) on increasing dilution (D) on increasing concentration
Q. 8 The amount of H2SO4 solution, which should be mixed with 500 ml of 0.1 M H2S solution to obtain
concentration of sulphide ion equal to 10–20 moles/litre, is -
[Given : Ka for H2S is 1.3 × 10–21 ]
(A) 5.38 gm (B) 12.79 gm (C) 1.27gm (D) 2.79 gm
(Q.9–Q.11)
A solution is prepared by mixing one mole of HA with one mole of HB, diluting to a
total volume of 1 dm3 with water. Both HA and HB are weak acids which dissociate
according to the following reversible reactions.
HA + H2O H3O+ + A– ; K1 = 1.0 ×10 –6 M
HA + H2O H 3O + + B – ; K2 = 1.0 ×10 –6 M
Q. 9 Equilibrium concentrations of H3O+ is
(A) 2 × 10–6 M (B) 1.414 ×10–3 M (C) 0.707 ×10–3 M (D) 1×10–3 M
Q. 10 Equilibrium concentrations of A– and B– are
(A) [A—] = [B—] = 0.707 × 10–3 M
(B) [A—] = 1.414 ×10–3 M ; [B—] = 0.707 × 10–3 M
(C) [A—] = 2 × 10–3 M [B—] = 0.707 × 10–3 M
(D) [A—] = 0.707 × 10–3 M [B—] = 1 ×10–3 M
Q.11 How does the presence of HB affect the dissociation of HA ?
(A) no effect on concentration of H3O+ (B) no effect on dissociation of HA
+
(C) increases the concentration of H3O (D) suppresses the dissociation of HA
(Q.12–Q.13)
The dissociation constant of HF and HNO 2 are 6.71 × 10 –4 M and 4.5 × 10 –4 M,
respectively.

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Concentration is 0.5 M in HF and 0.5 M in HNO2, then -

Q. 12 pH of the solution is
(A) 0.65 (B) 2.36 (C) 1.63 (D) 1.49
Q. 13 The ratio of [F–] to [NO2–] in a solution is -
(A) 1.49 (B) 9.52 (C) 1.63 (D) 7.24

5. Daily Practice Problem Sheet

Dissociation of water
Q. 1 The ionization constant and degree of dissociation of water at 25°C, is -
(A) 1.8 × 10–9, 1.8 × 10–16 (B) 1.8 × 10–16, 1.8 × 10–9
–12 –14
(C) 1.8 × 10 , 1.8 × 10 (D) 1.8 × 10–14, 1.8 × 10–12
(Q.2–Q.3)
The degree of ionization of water was found to be 1.28 × 10–8.
Q.2 The ionization constant of water at 90°C is -
(A) 1.28 × 10–14 M (B) 12.81 × 10–15 M (C) 9.07 × 10–15 M (A) 7.52 × 10–12 M
Q.3 The ionic product of water at this temperature is -
(A) 5.04 × 10–13 M2 (B) 4.02 × 10–11 M2 (C) 6.34 × 10–14 M2 (D) 5.98 × 10–14 M2
Q. 4 The ionic product of water is 1 × 10–14 (mol/l)2. The number of H+ ions that present in one millionth
part of 1 ml of pure water is -
(A) 66.9 million (B) 52.2 million (C) 48.3 million (D) 60.3 million
Q. 5 The pH of pure water at 25º and 35ºC are 7 and 6 respectively. The heat of formation of water from
H+ and OH– will be-
(A) –77.11 kcal/mole (B) –84.55 kcal/mole (C) –92.36 kcal/mole (D) –66.25 kcal/mole
Q. 6 Kw for 2H2O H3O+ + OH– changes from 10–14 at 25ºC to 9.62 × 10–14 at 60ºC. The pH of
water at this temperature is -
(A) 6.51 (B) 7.02 (C) 8.17 (D) 6.99
Q. 7 If Kw of water at 50ºC is 5 × 10–14, then the nature of solutions having pH = 7, pH = 6 & pH = 8.2
is respectively -
(A) neutral, basic, acidic (B) neutral, acidic, basic
(C) basic, acidic, basic (D) basic, acidic , neutral
Q. 8 The value of ionic product of water at various temperature are given below
c /°C 0 25 40
–14 2
Kw × 10 /M 0.114 1.008 2.919
The pH value of the pure water at 0ºC, 25ºC & 40ºC is respectively -
(A) 7.47, 7.26, 6.76 (B) 7.26, 7.00, 6.76 (C) 7.47, 7.00, 6.76 (D) 7.26, 6.76, 6.63
Q. 9 The ionic product of water at 100°C is 55 times than that at 25°C. The value of pH of water at 100°C
is -
(A) 6.13 (B) 7.02 (C) 6.63 (D) 7.12
Q. 10 The pH of a solution at 25°C which is twice as alkaline as pure water will be -
(A) 7.0 (B) 7.3 (C) 6.8 (D) 8.1

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6. Daily Practice Problem Sheet

Concentration of H + and OH – in aq. solution of acid and base
Q. 1 [H+] and [OH–] in a solution obtained by dissolving 0.365 g of HCl in 5 of water is -
(A) [H+] = 2 × 10–3, [OH–] = 5 × 10–12 (B) [H+] = 3 × 10–4, [OH–] = 5 × 10–10
(C) [H+] = 2 × 10–5, [OH–] = 4 × 10–13 (D) [H+] = 3 × 10–4, [OH–] = 4 × 10–13
Q. 2 On dissolving w gm of H2SO4 in 10  of pure water, concentration of H+ ion changed by 10, 000
times as compared to H+ ion in pure water at 25ºC. The value of w is -
(A) 1.8 gm (B) 1.2 gm (C) 0.98 gm (D) 0.49 g
Q. 3 Concentration of H+ ion in 10–5 M H2SO4 & 3.1 × 10–3 M HClO4 is respectively -
(A) 10–5 M, 3.1 × 10–3 M (B) 2 × 10–5 M, 3.1 × 10–3 M
(C) 2 × 10–5 M, 6.2 × 10–3 M (D) 2 × 10–10 M, 3.1 × 10–6 M
(Q.4–Q.6)
When 36.5  gm of HCl is dissolved in 1 litre of water, the solution will be acidic in
nature due to increase in concentration of H+ ion, then find out-
Q. 4 Concentration of H+ ion in the above solution if we neglect H+ due to water is -
(A) 10–5 (B) 10–7 (C) 10–6 (D) 10–8
Q. 5 Concentration of H+ ion in the above solution if we consider H+ due to water is -
(A) 1.0099 × 10–6 (B) 10.099 × 10–6 (C) 1 × 10–5 (D) 1.02 × 10–7
Q. 6 % error in the above two questions will be -
(A) 0.99 % (B) 9.9% (C) 99% (D) no error
(Q.7–Q.9)
A small amount of acid brings large difference in H+ ion concentration. If 10–7 moles of HCl are
dissolved in 1 litre of water then find out -
Q. 7 Concentration of H+ ion in the above solution if we neglect H+ due to water is -
(A) 10–5 (B) 10–7 (C) 10–6 (D) 10–8
Q. 8 Concentration of H+ ion in the above solution if we consider H+ due to water is -
(A) 1.0099 × 10–6 (B) 1.099 × 10–7 (C) 1 × 10–5 (D) 1.615 × 10–7
Q. 9 % error in the above two questions will be -
(A) 99 % (B) 9.9% (C) 61.5 % (D) no error
Q. 10 [H+] & [OH–] ion in 10–6 M H2SO4 solution is -
(A) [H+] = 2 × 10–6 [OH–] = 5 × 10–9 (B) [H+] = 2 × 10–6 [OH–] = 2 × 10–6
+ –6 – –8
(C) [H ] = 1 × 10 [OH ] = 1 × 10 (D) [H+] = 1 × 10–6 [OH–] = 5 × 10–9
Q.11 Concentration of H+ ion and OH– ion in a solution obtained by mixing 600 ml of 10–2 M H2SO4, 800
ml of 10–3 M HNO3 and 1100 ml of 10–7 M HCl, is -
(A) 5.12 × 10–3, 5.19 × 10–11 (B) 5.12 × 10–3, 1.99 × 10–11
–5 –9
(C) 3.21 × 10 , 2.19 × 10 (D) 5.12 × 10–3, 0.19 × 10–11
Q. 12 Concentration of H+ ion in 0.1 M HA solution having Ka = 10–14, is
(A) 1.045 ×10–7 (B) 1 ×10–7 (C) 0.1 ×10–7 (A) 1.45 ×10–7
Q. 13 [H+] and [OH–] ion in a 8 litre solution containing 9.25 gm/l of Ca(OH)2 at 25ºC, is
(A) [OH–] = 0.25 ×10–7, [H+] = 4 ×10–7 (B) [OH–] = 0.25, [H+] = 4 ×10–14
– –7 + –7
(C) [OH ] = 1.25 ×10 , [H ] = 4 ×10 (D) [OH–] = 2.5, [H+] = 4 ×10–14

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Q. 14 Concentration of H+ and OH– ion in 10–8 M NaOH, is respectively
(A) 1 × 10–6, 1 × 10–8 (B) 0.95 × 10–6, 1.05 × 10–8
–7 –7
(C) 0.95 × 10 , 1.05 × 10 (D) 1.05 × 10–7, 0.95 × 10–7

7. Daily Practice Problem Sheet

Ph and POH

(Q.1–Q.5)
In the question given below, find out the pH of the following solutions
Q. 1 0.1 M CH3COOH
(A) 2.87 (B) 2.37 (C) 1.34 (D) 4.74
Q. 2 0.1 M NH4OH
(A) 2.87 (B) 11.13 (C) 8.17 (D) 12.31
Q. 3 0.1 M HCOOH
(A) 1.37 (B) 4.74 (C) 2.37 (D) 3.18
Q. 4 1M CH3COOH
(A) 1.34 (B) 3.18 (C) 4.74 (D) 2.37
Q. 5 0.1M HA (Ka = 10–2)
(A) 1.57 (B) 2.72 (C) 3.14 (D) 2.33
Q. 6 The pH of 10–6 M HCl, 10–7 M HCl & 10–8 M HCl respectively is -
(A) 6, 7, 8 (B) 6, 6.79, 6.98 (C) 6, 6,79, 7.02 (D) 6, 6,98, 8
Q. 7 Find out pH of 0.1 M CH3COOH in presence of 0.1 M CH3COONa -
(A) 4.74 (B) 1.37 (C) 2.33 (D) 1.57
Q. 8 The pH of a solution obtained by mixing 200 ml of HCl solution having pH = 1 with 300 ml of NaOH
having pH =13 will be -
(A) 10.33 (B) 13 (C) 11.13 (D) 12.3
Q. 9 If 1 ml of 10–6 M HCl is diluted to 100 ml, the change in pH will be -
(A) 1.98 (B) 1.54 (C) 0.98 (D) 0.49
Q. 10 When 200 ml of solution of pH = 2 is mixed with 300 ml of solution of pH=3, the final pH of the
solution will be -
(A) 2.33 (B) 2.13 (C) 1.57 (D) 5
Q.11 What volume of NaOH solution having pH = 11 should be added in 1 litre of 0.1 M HCl solution to
increase its pH by 2 units.
(A) 54 litres (B) 49.5 litre (C) 62.7 litres (D) 98 litres
Q. 12 The pH of a solution is 5.0. To this solution sufficient acid is added to decrease the pH to 2.0. The
increase in hydrogen ion concentration is -
(A) 100 times (B) 10 times (C) 1000 times (D) 2.5 times
Q. 13 The pH of a solution is 2. Its pH is to be changed to 4. Then the H+ ion concentration of original
solution has to be -
(A) halved (B) doubled
(C) increased 100 times (D) decreased 100 times
Q. 14 An acid solution of pH 6 is diluted hundred times. The pH of the solution becomes -
(A) 6 (B) 6.98 (C) 4 (D) 8
Q. 15 The pH value of 0.1 mol/litre HCl is approximately 1. The approximate pH value of
0.05 mol/litre H2SO4 is most likely to be -

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(A) 0.05 (B) 0.5 (C) 1 (D) 2
–3
Q. 16 How much water must be evaporated from 5 litre of 10 M HCl to change its pH by 2 units -
(A) 1.5 litre (B) 0.5 litre (C) 2.54 litre (D) 4.95 litre
Q. 17 How much water must be added in 1 litre of 10–2 M H2SO4 to change its pH by 3 units -
(A) 850 litre (B) 999 litre (C) 99.9 litre (D) 1000 litre
Q. 18 The pH of the solution obtained by mixing 300 ml of 0.1 M NH4OH with 700 ml of 0.1 M NaOH
solution will be -
(A) 12.85 (B) 12.7 (C) 11.13 (D) 13.78
Q. 19 How much Ca(OH)2 must be added in 5 litre of water to change its pH by 3 units -
(A) 1.37 gm (B) 0.0185 gm (C) 0.037 gm (D) 1.85 gm
Q. 20 Correct order of the following equimolar (0.1 M) solution in increasing order of pH is -
(A) CH3COOH < NH4OH < Ca(OH)2 < H2S < H2O
(B) CH3COOH < H2S < H2O < Ca(OH)2 <NH4OH
(C) CH3COOH < H2S < H2O < NH4OH < Ca(OH)2
(D) H2S < CH3COOH < H2O < NH4OH < Ca(OH)2
Q. 21 When 100 ml of 0.1 M NH4OH is mixed with 100 ml of 0.1 M NaOH, the final pH of the solution is-
(A) 11.2 (B) 12.7 (C) 13.8 (D) 12.3
Q. 22 In the above question if instead of NH4OH, CH3COOH of same volume & concentration is taken &
volume of NaOH is reduced to one half of the initial, then the final pH of the solution is-
(A) 4.74 (B) 4.34 (C) 3.74 (D) 2.86
Q. 23 Consider the following equimolar (0.1 M) solution
HCl, H2SO4 , NaOH, Mg(OH)2 HClO4,
 = 30%  = 40%  = 80%  = 90%  = 10%
Increasing order of pH is -
(A) H2SO4 < HCl < HClO4 < NaOH < Mg(OH)2
(B) H2SO4 < HCl < HClO4 < Mg(OH)2< NaOH
(C) HClO4 < HCl < H2SO4 < NaOH < Mg(OH)2
(D) HClO4 < H2SO4 < HCl < Mg(OH)2 < NaOH

8. Daily Practice Problem Sheet

Acidic Buffer
Note : Always write acid-Base reaction first and identify the solution. (Buffer, salt, Strong Acid or Strong
Base)
[Salt]
Handerson equation for acidic buffer pH = pKa + log .
[Acid]

Q. 1 Calculate pH of solution which contains 0.1 M CH3COOH and 0.1 M CH3COONa pKa of
CH3COOH = 4.74
*(A) 4.74 (B) 2.87 (C) 7 (D) 5.74
Q. 2 Calculate pH of solution which contains 0.1 M HCOOH and 0.2 M (HCOO)2Ca.
pKa of HCOOH = 3.74
(A) 3.74 (B) 4.74 (C) 4.34 (D) 6
Q. 3 100 ml of 0.1 M NaOH is mixed in a container containing 200 ml of 0.2 M HA (a weak acid). Find
pH of solution (Ka of HA is 10–6)
(A) 6.48 (B) 5.52 (C) 6 (D) 7
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Q. 4 When 100 ml of 0.2 M CH3COOH with 50 ml of 0.1M Mg(OH)2 , the pH of the final solution is-
(A) 1 (B) 4.25 (C) 5 (D) 4.74
Q. 5 The amount of calcium formate which should be added in 500 ml of 0.1 M HCOOH to obtained a
solution with pH = 4 is -
[Given : Ka of HCOOH = 1.8 × 10–4 ]
(A) 4.36 g (B) 5.85 g (C) 3.76 g (D) 5.12 g
(Q.6–Q.10)
50 ml of 0.1 M CH3COOH is titrated with 0.1 M NaOH solution. pH of the solution after the
addition of:
Q. 6 0 ml of NaOH solution given above -
(A) 2.87 (B) 2.37 (C) 4.74 (D) 4.04
Q. 7 10 ml of NaOH solution given above -
(A) 3.18 (B) 5.34 (C) 4.14 (D) 2.34
Q. 8 25 ml of NaOH solution given above -
(A) 5.34 (B) 4.74 (C) 3.87 (D) 2.78
Q. 9 40 ml of NaOH solution given above -
(A) 5.34 (B) 4.14 (C) 4.34 (D) 2.85
Q. 10 60 ml of NaOH solution given above -
(A) 5.43 (B) 11.96 (C) 2.04 (D) 8.57
(Q.11–Q.12)
A weak acid (HA) is titrated with a strong base (NaOH) pH of the solution at 1/4th
neutralisation of the acid is 4.52. Enough strong acid (HCl) 25 meq is now added in
the above solution to completely convert the salt and total volume of the solution is 1
.
Q.11 Ka of the acid is
(A) 10–6 (B) 10–4 (C) 10–3 (D) 10–5
Q. 12 Final pH of the solution will be -
(A) 3 (B) 4.74 (C) 3.74 (D) 4 .52
Q. 13 A buffer solution with pH = 4 is to be prepared from sodium acetate and acetic acid. If solution
contains 1 litre of N/10 acetic acid, how many mole of CH3COONa be added ? Ka = 1.85 × 10–5.
(A) 0.18 (B) 0.018 (C) 0.036 (D) 0.009
(Q.14–Q15)
In a one litre of an aqueous solution containing 0.020 mole of propionic acid having Ka =
1.34 × 10–5 at 25ºC
Q. 14 How many moles of sodium propionate should be added in the above solution to obtain a buffer
solution of pH = 4.75
(A) 0.25 mole (B) 0.15 mole (C) 0.025 mole (D) 0.015 mole
Q. 15 When 0.010 mole of HCl dissolved in above buffer solution, pH of the solution will be -
(A) 4.09 (B) 2 (C) 4.75 (D) 3.87

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9. Daily Practice Problem Sheet

Basic Buffer
[Salt]
Handerson equation for basic buffer pOH = pKb + log
[Base]
Q. 1 pH of a solution which contains equal concentration NH4Cl and NH4OH is:
(A) 9.26 *(B) 4.74 (C) 7 (D) 8
Q. 2 pH of the solution obtained by mixing 20 ml of 0.1 M HCl with 50 ml of 0.1 M NH4OH, is -
(A) 2.0 (B) 4.55 (C) 9.44 (D) 4.92
Q. 3 The volume of 0.5 M H2SO4 solution which should be added in 100 ml of 0.4 M NH4OH solution to
obtain a solution with pH = 9, is -
(A) 25.8 ml (B) 20.6 ml (C) 11.4 ml (D) 18.7 ml
(Q.4–Q.5)
20 ml of 0.2 M HNO3 is added to 50 ml of 0.2 M NH4OH to give 70 ml of solution.
Q. 4 The pH of the solution will be -
(A) 4 (B) 9.44 (C) 4.56 (D) 8.32
Q. 5 What additional volume of 0.2 M HNO3 required to make pOH of the solution 4.74 -
(A) 20 ml (B) 10 ml (C) 30 ml (D) 5 ml
(Q.6–Q.7)
200 ml of 0.2 M NH4OH is mixed with 100 ml of 0.1 M H2SO4 solution, then
Q. 6 final pH of the solution, is -
(A) 9.25 (B) 4.43 (C) 9.56 (D) 5.04
Q. 7 change in pH when 20 ml of 0.1 M NaOH is added in the above buffer solution
(A) 0.045 (B) 0.087 (B) 0.027 (D) no change
Q. 8 How many mole of NH4Cl must be added to one litre of 1.0 M NH4OH to have a buffer of pH = 9.
KNH OH = 1.8 × 10–5 ?
4
(A) 1.59 (B) 3.6 (C) 1.80 (D) 2.85
Q. 9 The amount of (NH4)2SO4 in g which must be added to 500 ml of 0.2 M NH3 to yield a solution of
pH = 9.35. Kb for NH3 = 1.78 × 10–5.
(A) 5.248 g (B) 4.625 gm (C) 5.821 gm (D) 3.756 gm
(Q.10–Q.14)
100 ml of 0.5 M NH4OH is titrated with 0.2 M HCl solution, then the pH of the solution after the
addition of:
Q. 10 0 ml of above HCl solution-
(A) 11.48 (B) 9.26 (C) 11.13 (D) 2.87
Q.11 50 ml of above HCl solution -
(A) 9.26 (B) 8.27 (C) 9.86 (D) 8.66
Q. 12 100 ml of above HCl solution -
(A) 11.13 (B) 9.44 (C) 3.74 (D) 1.89
Q. 13 200 ml of above HCl solution -
(A) 0.698 (B) 8.66 (C)1.26 (D) 9.26

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Q. 14 300 ml of above HCl solution -
(A) 1.6 (B) 8.56 (C) 11.48 (D) 0.698

10. Daily Practice Problem Sheet

Salt hydrolysis
Q. 1 Find pH of
(i) 0.01 M NH4Cl (ii) 10–3 M CH3COONa (iii) 2M CH3COONH4
(iv) 10–2 M HCOONa (v) 0.5 M HCOONH4 (vi) 2M MgCl2
Q. 2 Find amount of
(i) CH3COONa dissolved in 200 ml to have pH = 9
(ii) HCOONa dissolved in 2 l to have pH = 10
(iii) NH4Cl dissolved in 100 ml to have pH = 5
Q. 3 20 g of a salt NaA having molecular mass 100 g/mole whn dissolved in 200 ml of water results a
solution having pH = 11. Calculate Ka of acid HA
Q. 4 50 ml of 0.1 M CH3COOH is mixed with 50 ml of 0.1 M NaOH. Find pH of solution. [Ka of
CH3COOH = 10–5]
Q. 5 The final pH of the solution obtained by mixing 200 ml of 0.1 M NH4OH with 50 ml of
0.2 M H2SO4
(A) 5.18 (B) 5.67 (C) 11.13 (D) 11.07
Q. 6 When equal volume of equimolar (0.1 M) solution of NH4OH & NH4Cl is mixed then hydrolysis
constant & degree of hydrolysis is -
(A) Kh = 55.5 × 10–10 , h = 2.05 × 10–5 (B) Kh = 55.5 × 10–11 , h = 7.44 × 10–5
–11 –3
(C) Kh = 5.55 × 10 , h = 1.05 × 10 (D) Kh = 5.55 × 10–10 , h = 1.05 × 10–4
Q. 7 Calculate pH of the following solutions
(i) 100 ml of 0.1 M CH3COOH + 0 ml of 0.1 M NaOH.
(ii) 100 ml of 0.1 M NH4OH + 0 ml of 0.1 M HCl
(iii) 100 ml of 0.1 M CH3COOH + 20 ml of 0.2 M Ca(OH)2
(iv) 100 ml of 0.3 M NH4OH + 150 ml of 0.2 M HCl
(v) 200 ml of 0.1 M HCOOH + 300 ml of 0.1 M H2SO4
(vi) 100 ml of 0.5 M CH3COOH + 500 ml of 0.1 M NH4OH
(vii) 300 ml of 0.2 M CH3COOH + 500 ml of 0.12 M NaOH
Q. 8 If we prepared an aqueous solution by mixing 100 ml of 0.2 M HCOOH with 100 ml of 0.2 M
NaOH, then its degree of hydrolysis & hydrolysis constant will be [Given : Ka (HCOOH) =
1.8 × 10–4] -
(A) Kh = 5.55 × 10–10, h = 1.04 × 10–5 (B) Kh = 55.5 × 10–10, h = 1.98 × 10–5
(C) Kh = 5.55 × 10–11, h = 1.67 × 10–5 (D) Kh = 55.5 × 10–11, h = 7.44 × 10–5
Q. 9 An aqueous solution is prepared by mixing 100 ml of 0.1 M CH3COOH & 100 ml of 0.1 M NaOH.
Degree of hydrolysis will be [Ka (CH3COOH) = 1.8 × 10–5]-
(A) 7.45 × 10–5 (B) 1.05 × 10–4 (C) 1.67 × 10–5 (D) 7.14 × 10–4
Q. 10 100 ml of 0.1 M CH3COOH is mixed with 50 ml of 0.1 M NaOH solution and pH of the resulting
solution is 5. The change in pH if 100 ml of 0.05 M NaOH is added in the above solution is-
(A)1.30 (B) 4.74 (C) 5 (D) 3.8

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11. Daily Practice Problem Sheet

Salt hydrolysis
Q. 1 How much must a 0.2 M solution of sodium acetate be diluted at 25ºC in order to double the degree
of hydrolysis –
(A) five times (B) three times (C) two times (D) four times
Q. 2 when 100 ml of 0.1 M solution of CH3COOH is mixed with 100 ml of 0.1 M NaOH solution. The
resulting solution will have pH –
(A) zero (B) 7 (C) more than 7 (D) less than 7
Q. 3 The dissociation constant of acetic acid is 1.8 × 10–5 the hydrolysis constant for 0.1 M sodium acetate
is-
(A) 1.8 × 10–19 (B) 1.8 × 10–5 (C) 5.56 × 10–10 (D) 55.6 × 10–10
Q. 4 What is the percentage hydrolysis of NaCN in N/80 solution ? When the dissociation constant for
HCN is 1.3 × 10–9 and Kw = 1 ×10–14.
(A) 2.48 (B) 5.26 (C) 8.2 (D) 9.6
Q. 5 The dissociation constant for NH4OH is 1.8 × 10–5. The degree of hydrolysis of 0.2 M NH4Cl
solution is –
(A) 2.35 × 10–5 (B) 5.27 × 10–5 (C) 3.62 × 10–5 (D) 4.85 × 10–5
Q. 6 In the hydrolytic equation A– + H2O HA+ OH– Ka = 1 × 10–5. The degree of hydrolysis of 0.001 M
solution of the salt is –
(A) 10–3 (B) 10–4 (C) 10–5 (D) 10–6
Q. 7 If pKb for CN– at 25ºC is 4.7, the pH of 0.5 M aqueous NaCN solution is –
(A) 12 (B) 10 (C) 11.5 (D) 11
Q. 8 The degree of hydrolysis of a salt of weak acid and weak base in its 0.1 M solution is found to be
50%. If the molarity of the solution is 0.2 M, the percentage hydrolysis of the salt should be –
(A) 100% (B) 50% (C) 25% (D) none of these
Q. 9 100 mL of 1 N NH4OH (Kb = 5 × 10–5) is neutralised to equivalence point by 1 N HCl. The pH of
solution at equivalence point is –
(A) 2.0 (B) 2.5 (C) 3.0 (D) 5.0
Q.10 If equilibrium constant for the reaction between BOH and HCl is 1012, then pH of 10–2 M BCl solution
is-
(A) 2.2 (B) 11.8 (C) 12.3 (D) 2.8
Q.11 It is found that 0.1 M solution of three sodium salts NaX, NaY and NaZ gave pH 7.0, 9.0 and 11.0
respectively.
The correct order of increasing strength of acid HX, HY, HX is
(A) HX < HY < HZ (B) HY < HZ < HX (C) HZ < HY < HX (D) HZ > HY < HX
Q. 12 In the above question, where possible, the ionisation constants of the acids are –
(A) Ka(HY) = 10–5 M , Ka(HZ) = 10–9 M
(B) Ka(HX) = 10–4 M , Ka(HY) = 10–6 M , Ka(Hz) = 10–9 M
(C) Ka(HY) = 10–4 M , Ka(HZ) = 10–10 M
(D) Ka(HX) = 10–5 M , Ka(HY) = 10–6 M , Ka(Hz) = 10–11 M
Q. 13 In the following reaction,
CN– + HN3  HCN + N3–

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Ka(HCN) = 1.4 × 10–10 , Ka(HN3) = 1.5 × 10–5, the equilibrium constant for the reaction at 25ºC is–
(A) 1.8 × 104 (B) 1.5 × 104 (C) 2.4 × 105 (D) 1.07 × 105

12. Daily Practice Problem Sheet

Solubility product
Q. 1 Write the equation for dissociation of following salts and determine their solubility in terms of Ksp.
(i) PbBr2 (ii) Hg2CrO4 (iii) BaC2O4 (iv) Fe(OH)3
(v) Ag2CO3 (vi) Sb2S3 (vii) AgCNS (viii) Ag3PO4
(ix) Li3Na3(AlF6)2 (x) Hg2I2 (xi) Ba3(PO4)2 (xii) Ca5(PO4)3F
(xiii) A3B4 (xiv) CaF2 (xv) Ag2CrO4

Q. 2 (i) Ksp of AgCl is 1.8 × 10–10. The solubility of AgCl in pure water in moles/litre –
(A) 1.34 × 10–5 (B) 4.24 × 10–5 (C) 1.8 × 10–5 (D) 3.6 × 10–5
(ii) In the above question the solubility in gram per litre will be –
(A) 180.26 × 10–5 (B) 192.29 × 10–5 (C) 210 × 10–4 (D) 176.85 × 10–4
Q. 3 Calculate solubility of AB2 in pure water. Ksp of AB2 = 25.6 × 10–8,
Q. 4 Solubility of a A2B salt in pure water is 2 × 10–5 moles in 100 ml. Calculate Ksp of salt
Q. 5 Ksp of AgBr is 4 × 10–13 and [Al+] is a solution is 1 × 10–6 m/l what is [Br–] in that solution.
Q. 6 If Ksp of AgI is 8.5 × 10–17. The maximum amount of AgI which can be dissolved in 2500 ml of water
will be –
(A) 9.22 × 10–9 gm (B) 2.3 × 108 gm (C) 5.42 × 10–5 gm (D) 2.17 × 10–5 gm
Q. 7 The volume of water needed to dissolve 1 g of BaSO4(Ksp = 1.1 × 10–10) at 25ºC is –
(A) 820 litre (B) 410 litre (C) 205 litre (D) none of these
Q. 8 How many grams of CaC2O4 will dissolve in distilled water to make one litre of saturated solution of
it ? (Ksp of CaC2O4 = 2.5 × 10–9 mol2 lit–2)
(A) 0.0064 gm (B) 0.1028 gm (C) 0.1280gm (D) 0.2056 gm
Q. 9 At 20ºC, the Ag+ ion concentration in a saturated solution Ag2CrO4 is 1.5 × 10–4 mole/lit. Ag 20ºC,
the solubility product of Ag2CrO4 could be –
(A) 3.37 × 10–12 (B) 1.68 × 10–10 (C) 1.68 × 10–12 (D) 1.12 × 10–10
Q. 10 In the system CaF2(s) Ca2+(ag) + 2F–
increasing the concentration of Ca2+ ions 4 times will cause the eq. concentration of F– ions to change
to .............. times the initial value.
(A) 4 (B) 1/2 (C) 2 (D) 1/4
Q.11 Concentration of Ag+ ion in a saturated solution of Ag2CrO4 is 5.4 × 10–6 g/litre when the salt is 50%
dissociated. Then solubility product of Ag2CrO4 is –
(A) 7.03 × 10–17 (B) 6.25 × 10–23 (C) 1.72 × 10–23 (D) 2.15 × 10–24
Q. 12 For an experiment Pb(OH)2 is taken , if salt is 80% dissociated & Ksp of Pb(OH)2 is 8 × 10–6. Then
solubility of salt in moles/litre is –
(A) 1.57 × 10–2 (B) 2 × 10–2 (C) 1.26 × 10–5 (D) 2.3 × 10–2
(ii) Considering the above question, what will be the solubility in gms/litre –
(A) 3.32 (B) 3.65 (C) 3.05 (D) 3.79
Q. 13 pH of a saturated solution of A(OH)3 is 10. Calculate Ksp of A(OH)3 at 25.
Q. 14 Solubility of As2S3 is 7.38 mg in 10ml of water. Calculate Ksp of As2S3.
Q. 15 Ksp of A3B4 is 6.912 × 10–18. Calculate solubility of A3B4.
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13. Daily Practice Problem Sheet

Solubility in presence of common ion
P–I Solubility product of AgCl is 1.8 × 10–10, then find out solubility of AgCl in
Q. 1 0.1M NaCl
(A) 3.6 × 10–10 (B) 1.8 × 10–10 (C) 3.6 × 10–9 (D) 1.8 × 10–9
Q. 2 0.2M AgNO3
(A) 3 × 10–10 (B) 0.36 × 10–10 (C) 9 × 10–10 (D) 2.6 × 10–10
Q. 3 2M CaCl2
(A) 9 × 10–10 (B) 4.5 × 10–11 (C) 1.5 × 10–11 (D) 6 × 10–11
Q. 4 (iv) pure water.
(A) 1.34 × 10–5 (B) 4.34 × 10–5 (C) 2.87 × 10–5 (D) 1.89 × 10–5
P–II Ksp of PbCl2 is 4 ×10–15 calculate its solubility in–
Q. 5 pure water
Q. 6 0.2 M AlCl3 solution
Q. 7 5 × 10–3 M Pb3(PO4)2 solution
Q. 8 0.02 M NaCl solution
Q. 9 0.4 M Pb(NO3)2 solution
Q. 10 The solubility of AgCl will be minimum in –
(A) 0.01 M AgNO3 (B) pure water (C) 0.01 M CaCl2 (D) 0.1 M NaCl
Q.11 The solubility product of AgCl is 4 × 10–10 at 298 K. The solubility of AgCl in 0.04 M CaCl2 will be–
(A) 2 × 10–5 M (B) 1 × 10–4 M (C) 5 × 10–9 M (D) 2.2 × 10–4 M
Q. 12 The molar solubility of PbI2 in 0.2 M Pb(NO3)2 solution in terms of solubility product, Ksp of PbI2 is–
1/ 2 1/ 2 1/ 3 1/ 2
 K sp   K sp   K sp   K sp 
(A)   (B)   (C)   (D)  
 0. 2   0.8   0. 8   0. 4 
Q. 13 Ksp of Zn(OH)2 is 4.5 × 10–17 then its solubility in a solution having pH = 10 will be –
(A) 4.5 × 10–10 (B) 1.4 × 10–10 (C) 6.7 × 10–10 (D) 7.6 × 10–10
Q. 14 Solubility of Mg(OH)2 having Ksp equal to 8.9 × 10–13, in a solution containing 500 ml of 0.2 M
NH4OH and 500 ml of 0.4 M Ca(OH)2 is –
(A) 3.4 × 10–19 (B) 55.63 × 10–13 (C) 2.34 × 10–9 (D) 8.34 × 10–13
Q. 15 Molar solubility of As2S3 in 0.3 M Al2S3 solution in terms of solubility product Ksp or As2S3 is–
K sp K sp K sp K sp
(A) (B) 3 (C) (D) 3
2.918 2.916 1. 2 1.2

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14. Daily Practice Problem Sheet

Precipitate formation
Q. 1 A solution 10–5 M Ag+ ions and 10–5 M Cl– ion. If Ksp of AlCl is 1.8 × 10–10 then ppt of AgCl will form
or not?
Q. 2 Ksp of PbI2 is 8 × 10–12. A solution contains 2 × 10–3 M Pb+2 ions and 2 × 10–4 M I– ions. Predict ppt
of PbI2 will form or not
Q. 3 Ksp of AgBr is 5 × 10–13. If equal volumes of 8 ×10–8 M AgNO3 solution is mixed with 2 × 10–5 M
NaBr solution then ppt of AgBr will form or not.
Q. 4 Ksp of A2B3 is 3.5 × 10–20 if 200 ml of 10–3 M A+3 ion is mixed with 200 ml of 10–4 M B–2 ion then ppt
of A2B3 will form or not.
Q. 5 The ppt of PbCl2 (Ksp) = 1.6 × 10–5) is obtained when equal volumes of the following are mixed–
(A) 10–2 M Pb+2 + 10–2 M Cl– (B) 10–2 M Pb+2 + 10–1 M Cl–
(C) 10–3 M Pb+2 + 10–2 M Cl– (D) 2 ×10–1 MPb+2 + 10–2M Cl–
Q. 6 The precipitate of CaF2 (Ksp = 1.7 × 10–10) is obtained when equal volumes of the following are
mixed–
(A) 10–4 Ca2+ + 10–4 M F– (B) 10–2 M Ca2+ + 10–3 M F–
–5 2+ –3 –
(C) 10 M Ca + 10 M F (D) 10–3 M Ca2+ and 10–3 M F–
Q. 7 Ksp of Mn(OH)2 is 2 × 10–13. A solution is prepared by mixing 10–5 M Mn+2 salt and 10–4 M NaOH
solution. Will precipitate of Mn(OH)2 form or not ?
Q. 8 Ksp of PbI2 is 2 × 10–10. 50 ml of 10–2 M Pb(NO3)2 is mixed with 150 ml of 3 × 10–4 M CaI2 solution.
Predict whether ppt of PbI2 will form or not.
Q. 9 Equal volumes of 0.02 M CaCl2 and 0.04 M Na2SO4 are mixed, will a precipitate form ?
Q. 10 To Ag2CrO4 solution over its own precipitate, CrO4–2 ions are added. This result in
(A) increase in Ag+ concentration
(B) decrease in Ag+ concentration
(C) increase in solubility product

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(D) None of these
Q.11 What is the minimum concentration of SO42– required to precipitate BaSO4 in a solution containing
1 × 10–4 mole of Ba2+ ? Ksp for BaSO4 = 4 × 10–10
(A) 4 × 10–10 M *(B) 4 × 10–6 M (C) 2 × 10–7 M (D) 2 × 10–3 M
Q. 12 At 18ºC, the solubility product of AgCl is 1.8 × 10–10. In a solution, the value of [Ag+] is 4 × 10–3 mol/
lit. Calculate value of [Cl–] to precipitate AgCl from this solution
Q. 13 What would be the pH at which Fe(OH)2 begins to precipitate from a solution containing 0.009 M
Fe+2 ions. Ksp of Fe(OH)2 is 1.8 × 10–15.
(A) 8.37 (B) 6.35 (C) 7.65 (D) 9.28
Q. 14 How many grams of CaBr2 (MM = 200) can be added to 250 ml of 0.01 M solution of silver nitrate
to just start the precipitation of silver bromide. Ksp of AgBr is 5.0 × 10–13.
Q. 15 Ksp of PbI2 is 4 × 10–9 calculate concentration of I– erquired to precipitate PbI2 from a solution
containing 0.02 M Pb(NO3)2.
Q. 16 Will a precipitate of Mg(OH)2 be formed in a 10–3 M solution of Mg(NO3)2. If the pH of solution is
adjusted to 9. Ksp of Mg(OH)2 = 8.9 × 10–12.
Q. 17 A solution contains 0.1 M Zn–2 ions and is saturated with H2S. Calculatee amount of HCl which
should be added in 500 ml of solution to prercipitate ZnS. Ksp of ZnS = 13.5 × 10–23. K1 of H2S =
10–7 and K2 of H2S = 1.5 × 10–14. concentration of H2S in saturated solutin is 0.1N.
Q. 18 A solution has 0.02 M A+2 and 0.1M NH4OH calculate the concentration of NH4Cl required to
prevent the formation of A(OH)2 in solution. Ksp of A(OH)2 is 2 × 10–12 and Kb of NMH4OH is 10–5.
Q. 19 A solution contains a mixture of Ag+ (0.1M) and Hg2+2 (0.1M) which are to be separate by selective
percipitation.
(i) Cal[I–] req. to ppt AgI
(b) Cal [I–] req. to ppt Hg2I2
(c) which one will ppt first AgI or Hg2I2
Ksp of AgI = 8.5 10–17 and Ksp of Hg2I2 = 2.5× 10–26.
Q. 20 Calculate simultaneous solubility of AgCNS and AgBr in a solution of water Ksp of AgB = 5 × 10–13
and Ksp of AgCNS = 10–12

SOLVED PROBLEMS

SUBJECTIVE

Problem 1:
The self ionization constant for pure formic acid, K = [HCOO H 2 ][HCOO– ] has been
estimated as 10–6 at room temperature. What percentage of formic acid molecules in
pure formic acid are converted to formate ion? The density of formic acid is 1.22 g/
cm 3 .
Solution:
Given density of formic acid = 1.22 g/cm3
 Weight of formic acid in 1 litre solution = 1.22  103

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1.22  103
Thus, [HCOOH] =  26.5 M
46
Since in case of auto ionization [HCOO H 2 ] [HCOO–] = 10–6
 [HCOO–] = [HCOO H 2 ] = 10–3.

[HCOO ]  100 103

Now % dissociation of HCOOH =   100 = 0.004%
[HCOOH] 26.5

Problem 2:
Calculate the concentration of all species of significant concentrations present in 0.1
M H3PO 4 solution. K1 = 7.5  10–3 , K2 = 6.2  10 –8 , K3 = 3.6  10 –3 .
I step H3PO 4 H+ + H 2P O 4 ; K1 = 7.5  10–3
II step H2P O 4 H+ + HP O 24  ; K2 = 6.2  10 –8
III step HP O24  H+ + P O34 ; K3 = 3.6  10 –13
Solution:
for I step : H3PO4 H+ + H2P O 4
0.1 0 0
0.1 – C C C
[H  ][H 2 PO 4 ] C.C
K1  
[H 3 PO 4 ] (0.1  C)

C2
7.5  10–3 =
(0.1  C)
 C = 0.024  [H+] = 0.024 M
[H2 PO 4 ] = 0.024 M
[H3PO4] = 0.1 – 0.024 = 0.076 M
The value of K1 is much large 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 H2P O 4 H+ + HP O 24  ;
0.024 0.024 0
(0.024 – y) (0.024 + y) y
The dissociation of H2P O 4 occurs in presence of [H+] furnished in step I.

[H  ][HPO 24  ]
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.
0.024y
 6.2  10–8 =  y = 6.2  10–8
0.024
or [HP O 24  ] = K2 = 6.2 10–8.
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For III step : HP O 24  H+ + P O34
(6.2  10–8 –x) (0.024 + x) x
[H  ][PO34 ] (0.024  x).x
 K3  
[HPO24  ] (6.2 108  x)
Again neglecting x2 and assuming, 6.2  10–8 –x = 6.2  10–8
0.024x
 3.6  10–13 =
6.2  108
3.6 1013  6.2  108
 x  9.3  1019 .
0.024

Problem 3:
If CH3COOH (Ka = 10–5) reacts with NaOH at 298 K, then find out the value of the
maximum rate constant of the reverse reaction at 298 K at the end point of the
reaction. Given that the rate constant of the forward reaction is 10–11 mol–1 L sec–1 at
298 K. Also calculate Arrhenius parameter for backward reaction if H 298 = 44 kcal
and Ea(f) = 94 kcal.
Solution:
CH3COOH + NaOH CH3COONa + H2O;
Kf = 10–11 mol–1 L sec–1
The backward reaction is of hydrolysis of sodium acetate
1
K K  K
 K C  for  (K h )1   W   a
K bac  Ka  KW

K for 10 11  1014

 K bac   KW  5
 1020
Ka 10
Given, H298 = 44 kcal and E af = 94 kcal
H = E a f  E a b
44 = 94 – E a b
 Ea b  A b  e Eabac / RT

 50 103 
–20
10 = Ab  e  2  298   Ab = 2.71  10+16.
 

Problem 4:
The pH of pure water at 25°C and 35°C are 7 and 6 respectively. Calculate the heat of
formation of water from H+ and OH– .
Solution:
At 25°C; [H+] = 10–7
 KW = 10–14
At 35°C; [H+] = 10–6
–12
 KW = 10
Now using

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Kw2
H  T2  T1 
2.303 log10 K  R  T  T 
w1  1 2

1012 H  308  298 

2.303 log10 14 
10 2  298  308 
 H = 84551.4 cal/mol
= 84.551 kcal/mol
Thus H2O H+ + OH–; H = 84.551 kcal/mol
+ –
 H + OH H2O; H = – 84.551 kcal/mol

Problem 5:
Calculate the pH of solution obtained by mixing 10 mL of 0.1 M HCl and 40 ml of 0.2
M H 2 SO 4 .
Solution:
Milli-equivalent of H+ from HCl = 10  0.1 = 1
Milli-equvalent of H+ from H2SO4 = 40  0.2  2 = 16
 Total meq. of H+ in solution = 1 + 16 = 17
17  Meq. 
 [H ] 

 [H+] =  3.4  101 
50  Vin mL 
 pH = – log [H+] = – log 0.34
pH = 0.4685

Problem 6:
Calculate the pH of a solution which contains 100 mL of 0.1 M HCl and 9.9 mL of 1.0
M NaOH.
Solution:
HCl + NaOH   NaCl + H 2O
t = 0 100  0.1 9.9  1
t = t 10–9.9 9.9–9.9 = 0 9.9 9.9
0.1
 [H+] left from HCl =  9.099  104 M
109.9
 pH = – log H = – log 9.099  10–4
+

pH = 3.0409
Problem 7:
Calculate [H + ] in a solution containing 0.1 M HCOOH and 0.1 M HOCN. Ka for
HCOOH and HOCN are 1.8  10 –4 and 3.3  10 –4 .
Solution:
In this problem both the acids contribute for [H+] due to appreciable dissociation. Thus,
HCOON H+ + HCOO–
0.1 –x x+y x
+
HOCN H + OCN–
0.1–y x+y y
Because [H+] will remain common in solution. Thus,
[H  ][HCOO  ]
KHCOOH =  1.8 10 4 … (1)
[HCOOH]

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[H  ][OCN  ]
KHOCN =  3.3  104 … (2)
[HOCN]
(x  y)x
or KHCOOH =  1.8  10 4 … (3)
0.1
(x  y)y
KHOCN =  3.3 10 4 … (4)
0.1
Thus, by (3) and (4)
x 1.8

y 3.3
or y = 1.83 x … (5)
From (3) (x + 1.83x) . x = 1.8  10–5  x = 2.52 10–3
Therefore y = 4.61  10–3
Thus, [H+] = x + y = 2.52  10–3 + 4.61  10–3 = 7.13  10–3 M

Problem 8:
A 0.1 M solution of weak acid HA is 1% dissociated at 25°C. What is its Ka ? If this
solution is with respect to NaA 0.2 M, what will be the new degree of dissociation of
HA and pH ?
Solution:
1
For weak acid HA :  HA  = 0.01, [HA] = 0.1 M
100
 K a  C 2  0.1 (0.01) 2  10 5
Now 0.2 M NaA, a salt of HA,is added to it resulting a buffer solution of [HA] = 0.1 M and [NaA]
= 0. 2 M.
0.2
 pH = – log 10–5 + log
0.1
pH = 5.3010
Also HA H+ + A–
1 0 0
(1 – ) 
 [A–] is provided by NaA since dissociation of HA in presence of NaA is suppressed due to
a common ion effect.
[H  ][A  ] (C)  0.2
 Ka    105
[HA] C(1  )
   5  10 5

Problem 9:
Calculate the amount of (NH4) 2SO 4 in g which must be added to 500 mL of 0.2 M
NH3 to yield a solution of pH = 9.35. Kb for NH3 = 1.78  10–5.
Solution:
[Salt]
pOH = – log Kb + log
[Base]

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[NH 4 ]
or pOH = – log Kb + log
[NH 4 OH]

 [NH 4 ] is obtained from salt (NH4)2SO4.

 pH = 9.35
 pOH = 14 – 9.35 = 4.65
 Millimole of NH4OH in solution = 0.2  500 = 100
Let millimole of NH 4 added in solution = a
a 100
 [NH 4 ]  ; [NH 4 OH] 
500 500
a / 500
4.65 = log 1.78  10–5 + log
100 / 500
a
4.65 = 4.7496 + log  a = 79.51
100
a 79.51
 Millimole of (NH4)2SO4 added =   39.755
2 2
w
 1000  39.755
132
 w ( NH4 ) 2 SO4  5.248 g
OBJECTIVE
Problem 1:
A solution of HCl is diluted so that its pH changes by 0.3. How does concentration of
H+ ion change?
(a) 0.5 times of initial value (b) 0.3 times of initial value
(b) 10 –3 times increases (d) None
Solution: (a)
+
Let H ion concentration changes by x factor.
 pH = – log [H3O+]
 pH + pH = – log {x(H3O+]} = –log x – log [H3O+]
or pH = – log x = 0.3
 x = 0.5
Problem 2:
The pH of 0.1M CH3COOH is 2.873. What is pH of 0.1M NH4 OH. Ka(CH3 COOH)
= 1.8  10 –5 and Kb(NH 4OH) = 1.8  10–5
(a) 11.127 (b) 2.873 (b) 7 (d) 9.53.
Solution: (a)
Since Ka(CH3COOH) = Kb(NH4OH) and concentration are equal so pH (CH3COOH) = pOH
(NH4OH)
pH = 2.873
 pH = 14 – pOH = 14 – 2.873 = 11.127

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Problem 3:
Liquid ammonia ionises to a slight extent. At - 50°C, its ion product is K NH =
3
 NH +   NH –  = 10 –30. How many amide ions,
 4   2  NH 2– are present per mm3 of pure
liquid ammonia.
(a) 6.023  10 23 (b) 6.023  10 15 (b) 6.023  10 14 (d) 6.023  10 –15 .
Solution: (b)
[NH 2– ]  K NH3  10 –30  10 –15

mol 1L
n NH  MV  1015  6 = 10–9 mol
2
L 10 mm3
Number of NH2 ions = 6.023  1023 10–9 ions = 6.023  1014 ion

Problem 4:
To a 50 ml of 0.1 M HCl solution, 10 ml of 0.1 M NaOH is added and the resulting
solution is diluted to 100 ml. What is change in pH of the HCl solution?
(a) 4.398 (b) .398 (b) 0.1M (d) None.
Solution: (b)
Before adding HCl solution
pH = 1 [ [HCl] = [H3O]+ = 10–1 M]
nHCl (initially) = MV = 0.1 M  0.05 L = 5  10–3 mol
nNaOH added = MV = 0.1 M  0.01 L = 1  10–3 mol
HCl + NaOH  NaCl + H2O
t=0 5  10–3 mol 1  10–3 mol 0
–3
4  10 mol 0
Vfinal  = 100 ml = 0.1 L
n 4 10 –3 mol
[HCl] =  = 4  10–2 M
V 0.1L
pH = – log [H3O+] = 2 – log4 = 2 – 2 log2 = 2 – 2  0.301= 2 – 0.602 = 1.398
Increase in pH = (1.398 – 1) = 0.398

Problem 5:
What amount of solid sodium acetate be added into 1 litre of the 0.1 M CH3COOH
solution so that the resulting solution has pH almost equal to pKa (CH3COOH) = 4.74
(a) 12gm (b) 5 gm (b) 10 gm (d) 14.924 gm.
Solution: (d)
Since the resulting solution be acidic buffer, one may use Henderson equation.
[CH3 COO – ]
pH = pK a  log
[CH3COOH]
Let n mol of CH3COONa be added to do so
n mol
or, pH = 4.74 + log vL
0.1 mol
vL

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n
or, 5 = 4.74 + log
0.1
n
or, log = 0.26
0.1
n
or, = antilog 0.26 = 1.8197
0.1
 n = 0.18197 mol  0.182 mol
Amount of sodium acetate = 0.182  82 gm = 14.924 gm

Problem 6:
To a 100 ml solution of 0.1 M CH3COONa and 0.1 M CH3COOH, 0.4 gm of solid
NaOH was added. Assuming volume remains constant, calculate the change in pH
value? Given that pKa (CH 3 COOH) = 4.74.
(a) .125 (b) .225 (b) .01 (d) .872.
Solution: (d)
Before NaOH addition,
pH = pKa = 4.74 [Since [CH3COO–] = [CH3COOH]]
The following reaction occurs due to NaOH addition.
H3CCOOH + NaOH  H3CCOONa + H2O
t = 0 0.01 mol 0.001 mol 0
– 0.001 mol – 0.001 mol 0.001 mol
––––––––––––––––––––––––––––––––––––
(0.01 – 0.001) mol 0.001 mol
nH = 0.01 mole
3CCOONa

After reaction, n CH = 0.009 mol

3COOH

n CH CCOO  = (0.01 + 0.001) mol = 0.011 mol

3

[CH3COO  ]
pH = pKa + log [CH COOH]
3

0.011/ V 11
= 4.74 + log = 4.74 + log = 4.74 + 0.0872
0.009 / V 9
11
change in pH = log = 0.872
9

Problem 7:
A weak base (BOH) with Kb = 10–5 is titrated with a strong acid, HCl. At 3/4th of the
equivalent point, pH of the solution is:
(a) 5 + log3 (b) 5 – log3 (c) 14 – 5 + log3 (d) 8.523.
Solution: (d)
Let the initial equivalent of BOH be x
BOH + HCl ? BCl + H2O
Initial equivalent x 3/4x 0 0
3x x 3 3
At 3/4th eqv. pt. x  0 x x
4 4 4 4

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[salt] 3x  4
pOH = pK b  log [Base]  5  log 4  x
pH = 14 – 5 – log 3 = 8.523
Problem 8:
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[HCl] (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 –10M [Cl– ].
Solution: (a)
We look for that case where the ionic product exceeds the Ksp
2
1 
[Ag  ][Cl ]    104   2.5  105
 2 
Problem 9:
The solubility products of Al(OH) 3 and Zn(OH) 2 are 8.5 × 10 –23 and 1.8 × 10 –14
respectively. If NH 4 OH is added to a solution containing Al3+ and Zn2+ ions, then
substance precipitated first is:
(a) Al(OH) 3 (b) Zn(OH) 2 (c) Both together (d) None at all.
Solution: (a)
Solubility of Al(OH)3 is lesser than Zn(OH)2.

Problem 10:
How many gram of CaC 2O 4 will dissolve in one litre of saturated solution? Ksp of
CaC2O4 is 2.5 × 10–9 mol–2 and its molecular weight is 128.
(a) 0.0064g (b) 0.0128g (c) 0.0032g (d) 0.0640g.
Solution: (a)
 Ca   C2O 4– –
CaC2 O 4 
S S

2
K sp  S  S  S
w
s  K sp = (2.5 × 10–9)1/2 = 5 × 10–5 mol litre–1   5  105
128
 w = 6.4 × 10–3g
Problem 11:
In the hydrolytic equilibrium
 HA+ OH -
A- + H 2 O 
Ka = 1.0 × 10–5. the degree of hydrolysis of 0.001M solution of the salt is
(a) 10 –3 (b) 10 –4 (c) 10 –5 (d) 10 –6 .
Solution: (a)

 K   1014 
K    10
3
h  h  w  =  5
10  0.001
 C   Ka  C   
Problem 12:
For preparing a buffer solution of pH 6 by mixing sodium acetate and acetic acid, the
ratio of concentration of salt and acid (Ka = 10–5) should be
(a) 1:10 (b) 10:1 (c) 100:1 (d) 1:100.
Solution: (b)

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[salt] 10
pH = pKa + log [acid] = 5  log if [salt]/[acid] = 10:1, then pH = 6
1
Problem 13:
Let the solubiliteis of AgCl in H2 O, 0.01 M CaCl2 ; 0.01 M NaCl and 0.05M AgNO3
be S1, S2, S3, S4 respectively. What is the correct relationship between these quantities.
(a) S1 > S2 > S3 > S4 (b) S1 > S2 = S3 > S4
(c) S1 > S3 > S2 > S4 (d) S4 > S2 > S3 > S1.
Solution: (c)
Solubility of AgCl in water = K sp = s1
In 0.01 M CaCl2 it is given by
K sp
Ksp = s × (0.01 × 2 +s)  s 2  In 0.01 M NaCl it is given by
0.02
K sp
K sp  s  (0.01  s)  s 3  In 0.05 M AgNO3 it is given by
0.01
K sp
K sp  s  (0.6  s)  s 4 
0.05
The solubilities are derived by neglecting s in comparison to 0.02, 0.01 and 0.05.
Problem 14:
The pH at which Mg(OH) 2 begins to precipitate from a solution containing 0.10M
Mg2+ ions [Kp of Mg(OH)2 = 1 × 10–11] is
(a) 5 (b) 9 (c) 4 (d) 10.
Solution: (b)
When Mg(OH)2 starts precipitation, then
[Mg2+] [OH–]2 = Ksp of Mg(OH)2
[0.1] [OH–]2 = 1 × 10–11  [OH–] = 10–5M
 pOH = 5  pH = 14 – pOH
pH = 14 – 5 = 9
Problem 15:
The concentration of hydroxyl ion in solution left after mixing 100 mL of 0.1 M MgCl2
and 100 mL of 0.2 M NaOH (Ksp of Mg(OH)2 = 1.2 × 10–11] is
(a) 2.8 × 10–3 (b) 2.8 × 10 –2 (c) 2.8 × 10–4
–5
(d) 2.8 × 10 .
Solution: (c)
MgCl2 + 2NaOH ? Mg(OH)2 + 2NaCl
mM before 10 20 0 0
mM after 0 0 10 20
reaction
thus, 10 m mole of Mg(OH)2 are formed. The product of [Mg2+] [OH–]2 is therefore
2
 10   20  4
 200    200   5  10 Which is more than
   
Ksp of Mg(OH)2. Now solubility (S) of Mg(OH)2 can be derived by
Ksp = 4S3
K sp
 S 3 1.4  10 –4
4
 [OH–] = 2S = 2.8 × 10–4

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JEE EXPERT
IONIC EQUILIBRIUM
OBJECTIVE QUESTION
LEVEL - I

Q. 1 100 mL of 1 M HCl is mixed with 50 mL of 2 M HCl. Hence, [H3O+] is –

(A) 1.00 M (B) 1.50 M (C) 1.33 M (D) 3.00 M
Q.2 At a temperature under high pressure
KW(H2O) = 1 × 10–10
A solution of pH 5.4 under these conditions is said to be :
(A) acidic (B) basic (C) neutral (D) amphoteric
Q.3 Which has maximum pH ?
(A) 0.01 M H2SO4 (B) 0.01 M HCl (C) 0.01 M Ca(OH)2 (D) 0.01 M NaOH
Q.4 We have acidic buffer of CH3COONa and CH3COOH. One or more of the following operations
will not change pH :
I : diluting the mixture ten times II : adding some HCl
III : adding some NaOH
IV : adding equal moles of CH3COONa and CH3COOH into the buffer
Select correct alternate :
(A) I, II, III, IV (B) II, III (C) I, IV (D) II, IV
Q.5 Degree of ionisation of 1 M HCOOH is decreased to a maximum extent in presence of :
(A) 1 M HCHO (B) 1 M NaOH (C) 1 M HCOONa (D) equally in all
Q.6 Buffer begins to lose its effectiveness when :
[Salt] [Salt]
(A) [weak electrolyte]  0.1 (B) [weak electrolyte]  10

(C) both (A) and (B) (D) none of these

Q.7 In what volume ratio should you mix 1.0 M solution of NH4Cl and NH3 to produce a buffer solution
of pH 9.80 ? [pKb (NH3)= 4.74]
(A) 1 : 3.5 (B) 3.5 : 1 (C) 2 : 1 (D) 1 : 2
Q.8 Number of (OH–) in 1 mL solution of pH = 13 is –
(A) 1 × 10–13 (B) 6.00 × 107 (C) 6.00 × 1013 (D) 6.02 × 1019
Q.9 pKa (CH3COOH) is 4.74. x mol of lead acetate and 0.1 mol of acetic acid in one L solution make a
solution of pH = 5.04. Hence, x is –
(A) 0.2 (B) 0.05 (C) 0.1 (D) 0.02
Q.10 Some chemist at ISRO wished to prepare a saturated solution of a silver compound and they wanted it
to have the highest concentration of silver ion possible. Which of the following compounds would they
use ?
Ksp(AgCl) = 1.8 × 10–10 ; Ksp(AgBr) = 5.0 × 10–13 , Ksp(Ag2CrO4) = 2.4 × 10–12
(A) AgCl (B) AgBr (C) Ag2CrO4 (D) any of them

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Q.11 Lemon juice normally has a pH of 2. If all the acid in the lemon juice is citric acid and there are no
citrate salts present, then what will be the citric acid concentration [HCit] in the lemon juice ?
(Assume that only the first hydrogen of citric acid is important)
HCit H+ + Cit–, Ka = 8.4 × 10–4 mol L–1
(A) 8.4 × 10–4 M (B) 4.2 × 10–4 M (C) 16.8 × 10–4 M (D) 12.0 × 10–2 M
Q. 12 10 mL of 10–6 M HCl solution is mixed with 90 mL H2O.pH will change approximately –
(A) by 1 unit (B) by 0.3 unit (C) 0.7 unit (D) by 0.1 unit
Q.13 The solubility product of BaSO4 is 1.5 × 10–9. The precipitation in a 0.01 M Ba2+ ions solution will
start on adding H2SO4 of concentration –
(A) 10–9 M (B) 10–8 M (C) 10–7 M (D) 10–6 M
Q.14 In a saturated solution of electrolytes, the ionic products of their concentration are constant at a
particular temperature. This constant for an electrolyte is known as –
(A) ionic product (B) ionisation constant
(C) dissociation constant (D) solubility product
Q.15 0.1 M acetic acid solution is titrated against 0.1 M NaOH solution. What would be the difference in
pH between 1/4 and 3/4 stages of neutralisation of acid ?
(A) 2 log 3/4 (B) 2 log 1/4 (C) log 1/3 (D) 2 log 3
Q.16 When 0.4 g of NaOH is dissolved in one litre of solution, the pH of the solution is –
(A) 12 (B) 2 (C) 6 (D) 10
Q.17 The hydrogen ion concentration and pH of the solution made by mixing 100 mL of 1.0 M HNO3 with
100 mL of 0.8 M KOH, are –
(A) [H+] = 0.1, pH = 1 (B) [H+] = 0.01, pH = 2
(C) [H+] = 1 × 10–12, pH = 12 (D) [H+] = 1 × 10–7, pH = 7
Q.18 If the solubility of lithium sodium hexafluoro aluminate, Li3Na3(AlF6)2 is ‘s’ mol L–1, its solubility
product is equal to
(A) s8 (B) 12s3 (C) 18s3 (D) 2916s8
Q.19 10 mL of 0.1 N HCl is added to 990 mL solution of NaCl. The pH of the resulting solution is –
(A) zero (B) 3 (C) 7 (D) 10

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LEVEL - II

Q.1 100 mL solution of pH = 6 is diluted to 1000 mL. Resulting solution has pH :

(A) 7.0 (B) 6.79 (C) 7.3 (D) 6.40
Q.2 The Ka value for the acid HA is 1.0 × 10–6. What is the value of K for the reaction ?
A– + H3O+ HA + H2O
–8
(A) 1.0 × 10 (B) 1.0 × 108 (C)1.0 × 10–3 (D) 1.0 × 106
Q.3 At 25°C, [H3O+] = 1 × 10–7 M in water, hence, Ka is –
(A) 1 × 10–14 (B) 5.55 × 10–15 (C) 1.8 × 10–16 (D) 55.5 × 10–10
Q.4 What is the value of Kw in 0.01 M NaOH ?
(A) 1 × 10–15 (B) 1 × 10–13 (C) 1 × 10–16 (D) 1 × 10–14
Q.5 [H3O+] in 0.1 M H2SO4 at two stages H2SO4 H+ + HSO4–
HSO4– H+ + SO42– are :
(A) 0.1 M, 0.1 M (B) 0.1 M, > 0.01 M (C) > 0.1 M, > 0.1 M (D) 0.1 M, < 0.1 M
Q.6 20 mL of 0.2 M NaOH is added to 50 mL of 0.2 M CH3COOH. Hence (pH – pKa) is –
3 2
(A) log (B) log (C) log 2 (D) 2 log 2
2 3
Q. 7 pH of a mixture which is 0.1 M in CH3COOH and 0.05 M in (CH3COOH)2Ba is
[pKa of CH3COOH = 4.74]
(A) 4.74 (B) 5.04 (C) 4.44 (D) 7.00
Q.8 In which case change in pH is maximum ?
(A) 1 mL of pH = 2 is diluted to 100 mL
(B) 0.01 mol of NaOH is added into 100 mL of 0.01 M NaOH solution
(C) 100 mL of H2O is added into 900 mL of 10–6 M HCl
(D) 100 mL of pH = 2 solution is mixed with 100 mL of pH = 12
Q.9 Which buffer solution has maximum pH ?
(A) mixture which is 0.1 M in CH3COOH and 0.1 M in CH3COONa [pKa (CH3COOH) = 4.74]
(B) mixture which is 0.2 M CH3COOH and 0.2 M in CH3COONa
(C) mixture which is 0.1 M in NH4Cl and 0.1 M in NH4OH [pKa (NH4+) = 9.26]
(D) all the solution have equal pH which is 4.74
Q.10 Ksp of CdS is 8.0 × 10–27 and that of H2S is 1 × 10–22, 1 × 10–14 M, CdCl2 solution is precipitated on
passing H2S when pH is about –
(A) 4 (B) 6 (C) 5 (D) 7
Q.11 100 mL of 0.02 M benzoic acid (pKa = 4.2) is titrated using 0.02 M NaOH. pH after 50 mL and 100 mL
of NaOH have been added are –
(A) 3.50, 7 (B) 4.2, 7 (C) 4.2, 8.1 (D) 4.2, 8.25
Q.12 The solubility products of Al(OH)3 and Zn(OH)2 are 8.5 × 10–23 and 1.8 × 10–14 at room temperature.
If the solution contains Al3+ and Zn2+ ions, the ion first precipitated by adding NH4OH is –
(A) Al3+ (B)Zn2+ (C) both (D) none
Q.13 To prepare a buffer of pH 8.26, amount of (NH4)2SO4 to be added into 500 mL of 0.01 M NH4OH
solution [pKa (NH4+) = 9.26] :
(A) 0.05 mol (B) 0.025 mol (C) 0.10 mol (D) 0.005 mol
Q.14 If the equilibrium constant of the reaction of weak acid HA with strong base is 109, then pH of 0.1 M
NaA is –
(A) 5 (B) 9 (C) 7 (D) 8

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Q. 15 pH of mixture of HA and A– buffer is 5. Kb of A– = 10–10. Hence [HA]/[A–] will be :
(A) 1 (B) 10 (C) 0.1 (D) 100
Q.16 pH of 0.01 M aqueous solution of NaX, NaY and NaZ are 8, 9 and 10 respectively. Strongest acid
among HX, HY and HZ is –
(A) HX (B) HY (C) HZ (D) can’t be predicted
Q.17 How many grams of CaC2O4 dissolve in distilled water to make one litre of saturated solution
(Ksp = 2.5 × 10–9 and its molecular mass is 128)
(A) 0.0064 g (B) 0.0128 g (C) 0.0032 g (D) 0.0640 g
Q.18 A certain buffer solution contains equal concentration of X– and HX. The Kb for X– is 10–10. The pH
of the buffer is –
(A) 4 (B) 7 (C) 10 (D) 14
Q.19 When the pH changes from 4 to 2, the hydrogen ion concentration will increase by a factor –
(A) 2 (B) 1/2 (C) 102 (D) 100.5
Q.20 pH of the buffer containing 0.6 g of acetic acid and 8.2 g of sodium acetate in 1 litre of water is (pKa
of acetic acid = 4.5)
(A) 7.5 (B) 4.5 (C) 5.5 (D) 6.5
Q.21 The correct order of increasing [H3O+] in the following aqueous solution is –
(A) 0.001 M H2S < 0.01 M H2SO4 < 0.01 M NaCl < 0.01 M NaNO2
(B) 0.01 M NaCl < 0.01 M NaNO2 < 0.01 M H2S < 0.01 M H2SO4
(C) 0.01 M NaNO2< 0.01 M NaCl < 0.01 M H2S < 0.01 M H2SO4
(D) 0.01 M H2S < 0.01 M NaCl < 0.01 M NaNO2 < 0.01 M H2SO4
Q.22 Which of the following statement/relationship is not correct ?
(A) Upon hydrolysis salt of strong base and weak acid gives solution with pH > 7
1
(B) pH = log
[ H ]
(C) only at 25°C, the pH of the pure water is 7
(D) the value of pKw at 25°C is seven
Q.23 For a concentrated solution of a weak electrolyte AxBy the degree of dissociation is given as –
(A)   K eq / c(x  y) (B)   K eq c /(x y)

(C) = (Keq/cx+y–1xxyy)1/(x+y) (D)   K eq / xyc

Q.24 The solubility of sparingly soluble electrolyte MmAa in water given by the expression –
m a 1/(m a) m a 1/(m  a)
 K sp   K sp   K sp   K sp 
(A) s   m a  (B) s   m a  (C) s   a m  (D) s   a m 
 m a   m a   m a   m a 
Q.25 If the salts M2X, QY2 and PZ3 have the same solubilities, their Ksp values are related as –
(A) Ksp (M2X) = Ksp(QY2) < Ksp (PZ3) (B) Ksp (M2X) > Ksp(QY2) = Ksp (PZ3)
(C) Ksp (M2X) = Ksp(QY2) = Ksp (PZ3) (D) Ksp (M2X) > Ksp(QY2) > Ksp (PZ3)

Q.26 Four solutions of NH4Cl are taken with concentrations 1 M, 0.1 M, 0.01 M and 0.001 M. Their
degree of hydrolysis are h1, h2, h3 and h4. What is the gradation of degree of hydrolysis ?
(A) h1 > h2 > h3 > h4 (B) h1 = h2 = h3 = h4 (C) h4 > h3 > h2 > h1 (D) none of these

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[CHEMISTRY] [IONIC EQUILIBRIUM]
LEVEL - III

Q.1 An acid-base indicator has a Ka of 3.0 × 10–5. The acid form of the indicator is red and the basic
form is blue. then:
(A) pH is 4.05 when indicator is 75% red (B) pH is 5.00 when indicator is 75% blue.
(C) pH is 5.00 when indicator is 75% red (D) pH is 4.05 when indicator is 75% blue.
Q.2 The equilibrium constant for the reaction
HONO(aq) + CN– (aq) HCN(aq) + ONO– (aq) is 1.1 × 10+6. From the magnitude of this
Keq one can conclude that
(A) CN– is stronger base than ONO– (B) HCN is a stronger acid than HONO
–
(C) The conjugate base of HONO is ONO (D) The conjugate acid of CN– is HCN
Q.3 The pH of a solution of 0.10 M CH3COOH increases when which of the following substances is
added?
(A) NaHSO4 (B) HClO4 (C) NH4NO3 (D) K2CO3
Q.4 All of the following are acid-base conjugate pairs:
(A) HONO, NO2– (B) H3O+, OH–
+
(C) CH3NH3 , CH3NH2 (D) HS–, S2–
Q.5 A 50.00 mL sample of 0.0100 M Ba(OH)2 is titrated with 0.0100 M HCl. The solution at the
equivalence point is:
(A) 3.33 × 10–3 M BaCl2 (C) 5.00 × 10–3 M BaCl2
(C) 2.50 × 10–3 M BaCl2 (D) 1.00 × 10–2 M BaCl2
Q.6 A flask contains 100.00 mL of 0.100 M HOAc. To prepare a buffer with pH = pKa which of the
followingsamples of barium acetate solution should be added to the flask?
(A) 50.00 mL of 0.400 M Ba (OAc)2 (B) 25.00 mL of 0.200 M Ba (OAc)2
(C) 50.00 mL of 0.200 M Ba (OAc)2 (D) 100.00 mL of 0.100 M Ba (OAc)2
Q.7 A 50.00 mL sample of acetic acid was titrated with 0.01200 M KOH and 38.62 mL of base were
required to reach the equivalence point. What was the pH of the titration mixture when 19.31 mL of
base had been added? [pKa (acetic acid) = 4.74]
(A) 2.94 (B)3.54 (C) 4.74 (D) 5.74
Q.8 In the following reaction:
[Cu(H2O)3 (OH)]+ + [Al(H2O)6]3+ [Cu(H2O)4]2+ + [Al(H2O)5(OH)]2+
A B C D
(A) A is an acid and B the base
(B) A is a base and B the acid
(C) C is the conjugate acid of A, and D is the conjugate base of B
(D) C is the conjugate base of A, and D is the conjugate acid of B
Q.9 Which does not react with NaOH or which is not acid salt?
(A) NaH2PO2 (B) Na2HPO3 (C) Na2HPO4 (D) NaHCO3
Q.10 pH of the following solution is not affected by dilution:
(A) 0.01 M CH3COONa
(B) 0.01 M NaHCO3
(C) buffer of 0.01 M CH3COONa and 0.01 M CH3COOH
(D) 0.01 M CH3COONH4

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Q . 11 Which of the following mixtures constitute a buffer?
(A) CH3COOH + CH3COONa (B) Na2CO 3 + NaHCO3
(C) NaCl + HCl (D) NH4Cl + (NH4)2SO 4
Q . 1 2 Which of the following mixtures constitute a buffer?
(A) Na2CO 3 + HCl (B) NaOH + CH3COOH
(C) NH3 + CH3COONH 4 (D) NaOH + BaCl2
Q.13 In which of the following pairs of solutions is there no effect on the pH upon dilution?
(A) 0.1 M NH3 and 0.1M(NH4)2SO 4
(B) 0.1 M NaH2PO4 and 0.1 M Na2HPO 4
(C) 0.1 M HCl and 0.01 M NaOH
(D) 0.1 M KCl and 0.1 M HCl
Q.14 Which of the following will suppress the ionization of phthalic acid in an aqueous
solution.
(A) KCl (B) H2SO (C) HNO3 (D) NaOH
Q.15 Which of the following will suppress the ionization of phthalic acid in an aqueous
solution?
(A) NaHCO3 + Na2CO 3 (B) CH3COOH + CH3COONa
(C) Na3PO 4 + NaH 2PO 4 (D) NH3 + (NH4)2SO 4
Q.16 Which of the following mixtures can act as a buffer?
(A) NaOH + CH3COONa (1 : 1 molar ratio)
(B) CH3COOH + NaOH (2 : 1 molar ratio)
(C) CH3COOH + NaOH (3 : 1 molar ratio)
(D) CH3COOH + NaOH (1 : 1 molar ratio)
Q.17 When HCl(g) is passed through a saturated solution of common salt, pure NaCl is
precipitated because
(A) HCl is highly soluble in water
(B) the ionic product [Na+] [Cl¯] exceeds its solubility product (Ksp)
(C) the ksp of NaCl is lowered by the presence of Cl¯ ions
(D) HCl causes precipitation

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LEVEL - IV
(Match the column)
Q. 1 Match the following
List I List II
(a) CH3COOH (P) weak base
(b) H2SO4 (Q) weak acid
(c) NaOH (R) strong acid
(d) NH3 (S) Stronge base
(A) a-R, b-Q, c-P, d-S (B) a-Q, b-R, c-S, d-P
(C) a-P, b-S, c-R, d-Q (D) a-S, b-P, c-Q, d-R
Q.2 Match the following
List I List II
Concentraiton of HCl pH
(a) 10–6 M (P) 7.0
(b) 10–7 M (Q) 6.98
(c) 10–8 M (R) 6.0
(d) 10–9 M (S) 6.79
(A) a-R, b-S, c-Q, d-P (B) a-S, b-R, c-Q, d-P
(C) a-Q, b-R, c-S, d-P (D) a-P, b-Q, c-R, d-S
Q.3 Match the following
List I List II
Components present in solution Method of determination of pH
(a) CH3COOH + HCl (P) Basic buffer
(b) NH4OH + NH4Cl (Q) Stronge base
(c) NH4Cl (R) Strong acid
(d) NH4OH + NaOH (S) Salt hydrolysis
(A) a-Q, b-R, c-S, d-P (B) a-R, b-S, c-P, d-Q
(C) a-Q, b-S, c-P, d-R (D) a-R, b-P, c-S, d-Q
Q.4 Match the following
List I List II
Salt pH
(a) HCOONa (P) 7
(b) NH4Cl (Q) <7
(c) MgSO4 (R) >7
(d) CH3 COONH4
(A) a–Q, b-P, c-R, d-P (B) a–P, b-Q, c-Q, d-R
(C) a–R, b-Q, c-P, d-P (D) a–R, b-R, c-Q, d-P

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Q. 5 A weak acid HA having Ka = 10–4 is given 100 ml of 0.1 M acid is taken in container. Now 0.1 M
NaOH is added in the container List I contains volume of NaOH added and List II contains pH.
Match them.
List I List II
1
(a) 10 ml NaOH solution (P) [pKw + pKa + log c]
2
(b) 25 ml NaOH solution (Q) pKa + log3
(c) 75 ml NaOH solution (R) pKa – log3
(d) 100 ml NaOH solution (S) pKa – 2log3.
(A) a-S, b-R, c-Q, d–P (B) a-P, b-Q, c-R, d–S
(C) a-Q, b-R, c-S, d–P (D) a-S, b-P, c-Q, d–R

SUBJECTIVE
LEVEL - I

Q. 1 The degree of dissociation of acetic acid in a 0.1 N solution is 1.32 × 10–2. At what concentration of
nitrous acid, its degree of dissociation will be same as that of acetic acid ? Ka (HNO2) = 4×10–4
Q.2 How many times is the H+ concentration in the blood (pH = 7.36) greater than in the spinal fluid
(pH = 7.53)?
Q.3 A 0.400 M formic acid solution freezes at –0.758°C. Calculate the Ka of the acid at that temperature.
(Assume molarity equal to molality). Kf (H2O) is 1.86° mol–1 kg.
Q.4 A sample of AgCl was treated with 5 mL of 1.5 M Na2CO3 solution to give Ag2CO3. the remaining
solution contained 0.00266625 g/litre Cl– ion. Calculate the solubility of AgCl in
(a) 0.1 M AgNO3 (b) 0.1 M BaCl2 (c) 0.2 M NaNO3..
Given that solubility of Ag2CO3 in 500 mL H2O = 13.8 mg.
Q.5 100 mL of solution S1 contains 0.17 mg of AgNO3. Another 200 mL solution S2 contains
0.117 mg of NaCl. On mixing these two solutions predict whether the precipitate of AgCl will appear
or not Ksp AgCl = 10–10 M2
Q.6 Calculate the value of Kh, h and pH of the following solution at 25°C.
(i) 0.1 M ammonium acetate Ka = Kb = 1.8 × 10–5 M
(ii) 0.1 M anilinium acetate Ka = 1.8 × 10–5 M; Kb = 4.6 × 10–10 M
(iii) 0.1 M ammonium carbonate Ka1 = 4.5 × 10–7 M, Ka2 = 4.7 × 10–11 M
Q.7 Calculate the pH of the following aqueous solutions :
(i) 5 × 10–8 M HCl (ii) 5 × 10–10 M HCl (iii) 10–8 M NaOH (iv)10–10 M NaOH
Q.8 A weak base BOH of concentration 0.02 mole/litre has a pH value of 10.45. If 100 ml of this base is
mixed with 10 ml of 0.1 M HCl, what will be the pH of the mixture ?
Q.9 A 0.02 M solution of CH3COONa in water at 25°C is found to have a H+ concentration of
3 × 10–9 g ionic weight per litre. What is the hydrolytic constant of the salt ?
Kw = 1.01 × 10–14, Ka(CH3COOH) = 1.75 × 10–5

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Q. 10 2.05 g of sodium acetate was added to 100 ml of 0.1 M HCl solution. Find the H+ ion concentration
of the resulting solution. If 6 ml of 1 M HCl is further added to it, what will be the new
H+ concentration ?
Q.11 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 centre of the hydrogen ion concentrations corresponding to given pH range,
calculate the ionization constant of the indicator.
Q. 12 Calculate the hydrolysis constant of NH4Cl ; determine the degree of hydrolysis of this salt in 0.01 M
solution and the pH of the solution. Kb (NH4OH) = 1.8 × 10–5
Q.13 Calculate the pH of 0.1 M acetic acid solution if its dissociation constant is 1.8 × 10–5. If 1 litre of this
solution is mixed with 0.05 mole of HCl, what will be the pH of the mixture ?
Q. 14 What is the solubility product of Ag2CrO4 if 0.0166 g of the salt dissolves in 500 ml of water at 18ºC?
Q. 15 When a 40 mL of a 0.1 M weak base is titrated with 0.16 M HCl, the pH of the solution at the end
point is 5.23. What will be the pH if 15 mL of 0.12 M NaOH is added to the resulting solution.
Q.16 Equal volumes of 0.02 N solution of CaCl2 and Na2SO4 are mixed, Will there be a formation of CaSO4
precipitate ? Ksp (CaSO4) = 1.4 × 10–4.
Q.17 Find the solubility of CaF2 in 0.05 M solution of CaCl2 and water. How many times is the solubility in
the second case greater than in the first ? Ksp (CaF2) = 4 × 10–11.
Q.18 How will the concentration of Ag+ in a saturated solution of AgCl diminish if such an amount of HCl is
added to it that the concentration of the Cl– in the solution becomes equal to 0.03 mole/litre.
[Ksp (AgCl) = 1.8 × 10–10]
Q.19 The solubility of lead sulphate in water is 1.03 × 10–4. Calculate its solubility in a centinormal solution
of H2SO4. Ksp (PbSO4) = 1.6 × 10–8.

LEVEL - II

Q.1 A chemist needs a buffer with pH 4.35. How many milliliters of pure acetic acid (density = 1.049 g/mL) must be
added to 465 mL of 0.0941 M NaOH solution to obtain such buffer ? (Ka = 1.8 × 10–5)
Q.2 It is found that 0.1 M solution of three sodium salts NaX, NaY and NaZ have pHs 7.0, 9.0 and 11.0,
respectively. Arrange the acids HX, HY and HZ in order of increasing strength. Where possible,
calculate the ionisation constants of the acids.
Q.3 Given a solution that is 0.5 M CH3COOH. To what volume at 25°C must one dm3 of this solution be
diluted in order to (a) double the pH; (b) double the hydroxide-ion concentration.
Given that Ka = 1.8 × 10–5 M.
Q.4 The solubility of Mg(OH)2 is increased by addition of NH4+ ion. Calculate –
(a) KC for the reaction,
Mg(OH)2 + 2NH4+ 2NH3 + 2H2O + Mg2+
(b) Find solubility of Mg(OH)2 in a solution containing 0.5 M NH4Cl before addition of
Mg(OH)2 (Ksp of Mg(OH)2 = 1 × 10–11, Kb for NH4OH = 1.8 × 10–5)

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Q. 5 A buffer solution was prepared by dissolving 0.05 mol formic acid and 0.06 mol sodium formate in
enough water to make 1.0 L of solution. Ka for formic acid is 1.80 × 10-4.
(a) Calculate the pH of the solution.
(b) If this solution were diluted to 10 times its volume, what would be the pH?
(c) If the solution in (b) were diluted to 10 times its volume, what would be the pH?
Q.6 20 ml of a solution of 0.1 M CH3COOH solution is being titrated against 0.1 M NaOH solution. The
pH values after the addition of 1 ml and 19 ml of NaOH are (pH)1 and (pH)2, what is pH?
Q.7 (a) Determine the pH of a 0.2 M solution of pyridine C5H5N. Kb = 1.5 ×10-9
(b) Predict the effect of addition of pyridinium ion C5H5NH+ on the position of the equilibrium. Will
the pH be raised or lowered?
(c) Calculate the pH of 1.0 L of 0.10 M pyridine solution to which 0.3 mol of pyridinium chloride
C5H5NH+Cl–, has been added, assuming no change in volume.
Q.8 How many moles of sodium hydroxide can be added to 1.0 L of a solution 0.1 M in NH3 and 0.1 M
in NH4Cl without changing the pOH by more than 1.00 unit? Assume no change in volume.
Kb(NH3) = 1.8 × 10-5.
Q.9 To a solution of acetic acid, solid sodium acetate is gradually added. When x grams of the salt have
been added, the pH has a certain value. When y grams of the salt have been added, the pH has been
further raised by 0.6 units. What is the ratio of x : y? If now the second solution is diluted, what happens
to the pH?
Q.10 A weak base BOH was titrated against a strong acid. The pH at 1/4th equivalence point was 9.24.
Enough strong base was now added (6 meq.) to completely convert the salt. The total volume was
50 ml. Find the pH at this point.
Q.11 An unknown volume and unknown concentration of weak acid HX is titrated with NaOH of unknown
concentration. After addition of 10.0 cm3 of NaOH solution, pH of solution is 5.8 and after the
addition of 20.0 cm3 of NaOH solution, the pH is 6.4. Calculate the pH of aqueous solution of 0.1 M
NaX.
Q.12 A solution containing zinc and manganese ions each at a concentration of 0.01 mol dm–3 is saturated
with H2S. Calculate (i) pH at which the MnS will form a precipitate (ii) conc. of Zn+2 ions remaining.
Given : [H2S] = 0.1 mol/lit, Ksp(ZnS) = 1 × 10–22 mol2lit–2, Ksp(MnS) = 5.6 × 10–16 mol2 lit–2.
K1 and K2 for H2S are 1 × 10–7 and 1.1 × 10–14.
Q. 13 For the indicator thymol blue, the value of pH is 2.0, when half of the indicator is present in the
unionised form. Calculate the percentage of the indicator in the unionized form in a solution of 4.0 ×
10–3 mol/dm–3 hydrogen ion concentration.
Q.14 One of the substances sometimes responsible for the hardness of water is CaSO4. A particular water
sample has 131 ppm CaSO4 (131 g CaSO4 per 106 g of water). If this water boiled in a tea kettle,
approximately what fraction of water must be evaporated before CaSO4(s) begins to deposit ?
Assume that solubility of CaSO4 does not change with temperature in the range 0 to 100°C, Ksp
(CaSO4) = 9.1 × 10–6.
Q.15 The indicator phenol red is half in the ionic form when pH is 7.2. If the ratio of the undissociated form
to the ionic form is 1 : 5, find the pH of the solution. With the same pH for solution, if indicator is
altered such that the ratio of undissociated form to dissociated form becomes 1 : 4, find the pH when
50% of the new indicator is in ionic form.

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Q. 16 A solution of 0.1 mol dm in Cl , 0.1 mol dm in Br and 0.1 mol dm–3 in I–. Solid AgNO3 is
–3 – –3 –

gradually added to this solution. Assuming that the addition of AgNO3 does not change the volume.
Answer the following:
(a) What concentration of Ag+ ions will be required to start precipitation of each of the three ions ?
(b) Which ion will precipitate first ?
(c) What will be the concentration of this ion when the second ion starts precipitating ?
(d) What will be the concentration of both the ions when the third ion starts precipitating ?
Given : Ksp (AgCl) = 1.7 × 10–10 (mol dm–3)2
Ksp (AgBr) = 5.0 × 10–13 (mol dm–3)2
Ksp (AgI) = 8.5 × 10–17 (mol dm–3)2
Q.17 When 40 g of NaOH reacts with a mixture of 1 mole each of acids HX and HY, it is found that 75%
HX is neutralised. If the value of Ka of HX is 9 × 10–6 then calculate pH of 1 M solution of HY in
water and its degree of ionisation.
Q.18 A buffer solution is 0.25 M CH3COOH – 0.15 M CH3COONa, saturated in H2S (0.1 M) and has
[Mn2+] = 0.015 M. Ka = (CH3COOH) = 1.74 × 10–5, Ka (H2S) = 1.1 × 10–21 and Ksp (MnS) = 2.5
× 10–13
(a) will MnS precipitate ?
(b) Which buffer component should be increased in concentration and to which minimum value to just
start precipitation of MnS ?
Q.19 Given that 2 × 10–4 mole each of Mn2+ and Cu2+ was contained in one litre of a 0.003 M HClO4
solution, and this solution was saturated with H2S. Determine whether or not each of these ions, Mn2+
and Cu2+ will precipitate as sulphide. The solubility of H2S, 0.1 mole per litre is assumed to be
independent of the presence of other materials in the solution.
Ksp (MnS) = 3 × 10–14, Ksp (CuS) = 8 × 10–37
K1 and K2 for H2S are 1 × 10–7 and 1.1 ×10–14 respectively. Also calculate % of Cu remaining
unprecipitated. Will MnS precipitate if the above solution is made neutral by lowering the [H+] to
10–7 M ?
Q.20 A solution of weak acid HA was titrated with base NaOH. The equivalence point was reached when
36.12 ml of 0.1 M NaOH has been added. Now 18.06 ml of 0.1 M HCl were added to titrated
solution, the pH was found to be 4.92. What will be the pH of the solution obtained by mixing
10 ml of 0.2 M NaOH and 10 ml of 0.2 M HA.

LEVEL - III
[NCERT TEXT BOOK EXERCISE]
Q.1 What is meant by the conjugate acid-base pair? Find the conjugate acid/base for the following species:
HNO2, CN–, HClO4, F–, OH–, CO32–, and S2–
Q.2 Which of the followings are Lewis acids? H2O, BF3, H+, and NH4+
Q.3 What will be the conjugate bases for the bronsted acids: HF, H2SO4 and HCO3?
Q.4 Write the conjugate acids for the following bronsted bases: NH2–, NH3 and HCOO–
Q.5 The species: H2O, HCO3–, HSO4– and NH3 can act both as Bronsted acids and bases. For each
case give the corresponding conjugate acid and base.
Q.6 Classify the following species into Lewis acids and Lewis bases and show how these acts as Lewis
acid/base:
(a) OH– (b) F– (c) H+ (d) BCl3

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Q. 7 The concentration of hydrogen ion in a sample of soft drink is 3.8 × 10–3 M. What is its pH?
Q.8 The pH of a sample of vinegar is 3.76. Calculate the concentration of hydrogen ion in it.
Q.9 The ionization constant of HF, HCOOH and HCN at 298 K are 6.8 × 10–4, 1.8 × 10–4 and 4.8 ×
10–9 respectively. Calculate the ionization constants of the corresponding conjugate base.
Q.10 The ionization constant of phenol is 1.0 × 10–10. What is the concentration of phenolate ion in 0.05 M
solution of phenol? What will be its degree of ionization if the solution is also 0.01 M in sodium
phenolate?
Q.11 The first ionization constant of H2S is 9.1 × 10–8. Calculate the concentration of HS– ion in its 0.1 M
solution. How will this concentration be affected if the solution is 0.1 M in HCl also? If the second
dissociation constant of H2S is 1.2 × 10–13. Calculate the concentration of S2– under both conditions..
Q.12 The ionization constant of acetic acid is 1.74 × 10–5. Calculate the degree of dissociation of acetic
acid in its 0.05 M solution. Calculate the concentration of acetate ion in the solution and its pH.
Q.13 It has been found that the pH of a 0.01 M solution of an organic acid is 4.15. Calculate the concen-
tration of the anion, the ionization constant of the acid and its pKa.
Q.14 Assuming complete dissociation, calculate the pH of the following solutions:
(a) 0.003 M (b) 0.005 M NaOH (c) 0.002 M HBr (d) 0.002 M KOH
Q.15 Calculate the pH of the following solutions:
(a) 2 g of TlOH dissolved in water to give 500 ml of solution.
(b) 0.3 g of Ca(OH)2 dissolved in water to give 2 litre of solution
(c) 0.3 g of NaOH dissolved in water to give 200 mL of solution.
(d) 1 mL of 13.6 M HCl is diluted with water to give 1 litre of solution
Q.16 The degree of ionization of a 0.1 M bromoacetic acid solution is 0.l32. Calculate the pH of the
solution and the pKa of bromoacetic acid.
Q.17 The pH of 0.005 M codeine (C18H21NO3) solution is 9.95. Calculate its ionization constant and pKb.
Q.18 What is the pH of 0.001 M aniline solution? The ionization constant of aniline can be taken from
Table 7.7. Calculate the degree of ionization of aniline in the solution. Also calculate the ionization
constant of the conjugate acid of aniline
Q.19 Calculate the degree of ionization of 0.05 M acetic acid if its pKa value is 4.74. How is the degree of
dissociation affected when its solution also contains
(a) 0.01M (b) 0.1 M in HCl
Q.20 The ionization constant of dimethylamine is 5.4 ×10–4. Calculate its degree of ionization in its 0.02 M
solution. What percentage of dimethylamine is ionized if the solution is also 0.1M NaOH?
Q. 21 Calculate the hydrogen ion concentration in the following biological fluids whose pH are given below:
(A) Human muscle-fluid 6.83 (B) Human stomach fluid, 1.2
(C) Human blood, 7.38 (D) Human saliva, 6.4.
Q.22 The pH of milk, black coffee, tomato juice, lemon juice and egg white are 6.8, 5.0, 4.2, 2.2 and 7.8
respectively. Calculate corresponding hydrogen ion concentration in each.
Q.23 If 0.561 g of KOH is dissolved in water to give 200 mL of solution at 298 K. Calculate the concen-
trations of potassium, hydrogen and hydroxyl ions. What is its pH?
Q.24 The solubility of Sr(OH)2 at 298 K is 19.23 g/L of solution. Calculate the concentrations of strontium
and hydroxyl ions and the pH of the solution.
Q.25 The ionization constant of propanoic acid is 1.32 × 10–5. Calculate the degree of ionization of the acid
in its 0.05M solution and also its pH. What will be its degree of ionization if the solution is 0.01 M in
HCl also?

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Q. 26 The pH of 0.1 M solution of cyanic acid (HCNO) is 2.34. Calculate the ionization constant of the
acid and its degree of ionization in the solution
Q.27 The ionization constant of nitrous acid is 4.5 × 10–4. Calculate the pH of 0.04 M sodium nitrite
solution and also its degree of hydrolysis.
Q.28 A 0.02 M solution of pyridinium hydrochloride has pH = 3.44. Calculate the ionization constant of
pyridine.
Q.29 Predict if the solutions of the following salts are neutral, acidic or basic.
NaCl, KBr, NaCN, NH4NO3, NaNO2 and KF
Q.30 The ionization constant of chloroacetic acid is 1.35 × 10–3. What will be the pH of 0.1M acid and its
0.1M sodium salt solution?
Q.31 Ionic product of water at 310 K is 2.7 × 10–14. What is the pH of neutral water at this temperature?
Q.32 Calculate the pH of the resultant mixtures:
(A) 10 mL of 0.2M Ca(OH)2 + 25 mL of 0.1 M HCl
(B) 10 mL of 0.1 M H2SO4 + 10 mL of 0.01 M Ca(OH)2
(C) 10 mL of 0.1M H2SO4 + 10 mL of 0.1M KOH
Q.33 Determine the solubilities of silver chromate, barium chromate, ferric hydroxide, lead chloride and
mercurous iodide at 298 K from their solubility product constant given in Table 7.9. Determine also
the molarities of individual ions.
Q.34 The solubility product constant of Ag2CrO4 and AgBr are 1.1 ×10–12 and 5.0 × 10–13 respectively.
Calculate the ratio of the molarities of their saturated solutions.
Q.35 Equal volumes of 0.002 M solutions of sodium iodate and cupric chlorate are mixed together. Will it
lead to precipitation of copper iodate? (For cupric iodate Ksp = 7.4 × 10–8)
Q.36 The ionization constant of benzoic acid is 6.46 × 10–5 and Ksp for silver benzoate is 2.5 × 10–13. How
many times is silver benzoate more soluble in a buffer of pH 3.19 compared to its solubility in pure water.
Q.37 What is the maximum concentration of equimolar solutions of ferrous sulphate and sodium sulphide
so that when mixed in equal volumes, there is no precipitation of iron sulphide? (For iron sulphide,
Ksp = 6.3× 10–18).
Q.38 What is the minimum volume of water required to dissolve 1g of calcium sulphate at 298K? (For
calcium sulphate , Ksp is 9.1 × 10–6)
Q.39 The concentration of sulphide ion in 0.1M HCl solution saturated with hydrogen sulphide is 1.0 ×
10–19 M. If 10 mL of this is added to 5mL of 0.04 M solution of the following: FeSO4, MnCl2, ZnCl2
and CdCl2, in which of these solutions precipitation will take place?
LEVEL - IV

1986
Q.1 A sample of hard water contains 0.005 mole of CaCl2 per litre. What is the minimum concentration of
Na2SO4 which must be added for removing Ca+2 ions from this water sample ? Ksp for CaSO4 is
2.4 × 10–5 at 25°C.
Q.2 The solubility of Mg(OH)2 in pure water is 9.57 × 10–3 g litre–1. Calculate its solubility in g litre–1 in
0.02M Mg(NO3)2.
Q.3 The concentration of hydrogen ion in a 0.2 M solution of formic acid is 6.4 × 10–3 mole per litre. To
this solution sodium formate is added so as to adjust the concentration of sodium formate one mole
per litre. What will be the pH of this solution ? The dissociation constant of formic acid is 2.4 × 10–
4
and the degree of dissociation of sodium formate is 0.75.

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Q. 4 Calculate the approximate pH of 0.1 M aqueous H2S solution. K1 and K2 for H2S are 1.0 × 10–7 and
1.3 × 10–13 respectively at 25°C.
1987
Q.5 How many mole of Ca(OH)2 must be dissolved to produced 250 ml of an aqueous solution of pH
10.65, assuming complete dissociation ?
Q.6 What is the pH of the solution when 0.2 mole of HCl is added to one litre of a solution :
(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 CH3COOH = 1.8 × 10–5
1988
Q.7 A certain buffer solution contains equal concentration of X– and HX.Kb for X– is 10–10. Calculate pH
of buffer.
Q.8 How many gram mole of HCl will be required to prepare one litre of a buffer solution (containing
NaCN and HCN) of pH 8.5 using 0.01 gram formula weight of NaCN ? K(HCN) = 4.1 × 10–10.
Q.9 The pKa of acetyl salicylic acid (aspirin) is 3.5. The pH of gastric juice in human stomach is about 2-
3 and the pH in small intestine is about 8. Aspirin will be –
(A) unionised in the small intestine and in the stomach
(B) completely ionised in small intestine and in the stomach
(C) ionised in the stomach and almost unionised in the small intestine
(D) ionised in the small intestine and almost unionised in the stomach
Q.10 When equal volume 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–)
Q.11 The pH of 0.1 M hydrocyanic acid solution is 5.2. What is the value of Ka for hydrocyanic acid ?
1989
Q.12 Freshly precipitated Al and Mg hydroxides are stirred vigorously in a buffer solution containing 0.25
M of NH4Cl and 0.05 M of NH4OH. Calculate [Al+3] and [Mg+2] in solution.
Kb for NH4OH = 1.8 × 10–5. Ksp of Al(OH)3 = 6 × 10–32 and Ksp of Mg(OH)2 = 8.9 × 10–12.
Q.13 Ksp of BaSO4 is 1.5 × 10–9. Calculate its solubility in :
(i) pure water (ii) 0.10 M BaCl2
Q. 14 When 0.2 M acetic acid is neutralised with 0.2 M NaOH in 0.5 litre of water the resulting solution is
slightly alkaline. Calculate the pH of the resulting solution. Ka for CH3COOH = 1.8 × 10–5.
1990
Q.15 What is the pH of 1 M solution of acetic acid. To what volume one liter of this solution be diluted so
that pH of the resulting solution will be twice of the original value ? Ka = 1.8 × 10–5.
Q.16 What volume of 0.1 M sodium formate solution should be added to 50 mL of 0.05 M formic acid to
produce a buffer solution of pH = 4.0. pKa of formic acid = 3.80
Q.17 Calculate the pH at the equivalence point when a solution of 0.1 M acetic acid is titrated with a
solution of 0.1 M NaOH. Ka for acid = 1.9 × 10–5.
Q.18 Which hydroxide will have lowest value of solubility product at normal temperature (25°C) ?
(A) Mg(OH)2 (B) Ca(OH)2 (C) Ba(OH)2 (D) Be(OH)2

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Q. 19 The solubility product of a salt A2B is 4 × 10–9. Its solubility would be –
(A) 4 × 10–2 M (B) 2 × 10–4 M (C) 1 × 10–4 M (D) 1 × 10–3 M
Q.20 At 25°C, the dissociation constants of CH3COOH and NH4OH in aqueous solution are almost the
same. The pH of a solution of 0.01 N CH3COOH is 4.0 at 25°C. The pH of 0.01 N NH4OH
solution at the same temperature would be –
(A) 3.0 (B) 4.0 (C) 10.0 (D) 10.5
1991
Q.21 A 40 ml solution of weak base BOH is titrated with 0.1 N HCl solution. The pH of solution is found
to be 10.04 and 9.14 after the addition of 5.0 ml and 20.0 ml of acid respectively. Find out Kb for
weak base.
Q.22 A certain weak acid has Ka = 1.0 ×10–4. Calculate the equilibrium constant for its reaction with a
strong base.
Q.23 The Ksp of Ag2C2O4 at 25°C is 1.29 × 10–11 mol3L–3. A solution of K2C2O4 containing 0.152 mole in
500 ml water is shaken at 25°C with excess of Ag2CO3 till the equilibrium is reached.
Ag2CO3 + K2C2O4 Ag2C2O4 + K2CO3
At equilibrium the solution contains 0.0358 mole of K2CO3. Assuming degree of dissociation of
K2C2O4 and K2CO3 to be same, calculate Ksp of Ag2CO3.
Q.24 Calcium lactate is a salt of weak acid and represented as Ca(LaC)2. A saturated solution of Ca(LaC)2
contains 0.13 mole of salt in 0.50 litre solution. The pOH of this is 5.60. Assuming complete dissociation
of salt, calculate Ka of lactic acid.
Q.25 The concentration of HCN and NaCN in a solution is 0.01 M each. Calculate [H+] and [OH–], if Ka of HCN
is 7.2 × 10–10.
1992
Q.26 Calculate pH for (a) 0.001 N NaOH (b) 0.01 N Ca(OH)2
(c) 0.01 M Ca(OH)2 (d) 0.0008 M Mg(OH)2
Assume complete ionisation of each.
Q.27 A solution contains 0.1 M H2S and 0.3 M HCl. Calculate the con. of S–2 and HS– ions in solution.
Given Ka and Ka for H2S are 10–7 and 1.3 × 10–13 respectively.
1 2
Q.28 Calculate the change in pH of 1 litre buffer solution containing 0.1 mol each of NH3 and NH4Cl up on
addition of,
(i) 0.02 mole of dissolved gaseous HCl
(ii) 0.02 mole of dissolved NaOH.
Assume no change in volume. KNH = 1.8 ×10–5
3
Q. 29 The Ksp of Ca(OH)2 is 4.42 × 10–5 at 25°C. A 500 ml of saturated solution Ca(OH)2 is mixed with
equal volume of 0.4 M NaOH. How much Ca(OH)2 in mg is precipitated ?
Q.30 Calculate the pH at which Mg(OH)2 begins to precipitate from a solution containing 0.10 M Mg+2
ions. Ksp of Mg(OH)2 = 1 × 10–11.
Q.31 Which of the following solution will have pH 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

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Q. 32 The following equilibrium is established when hydrogen chloride is dissolved in acetic acid :
HCl + CH3COOH Cl– + CH3COOH2+
The set that characterises the conjugate acid-base pairs is
(A) (HCl, CH3COOH) and (CH3COOH2+, Cl–) (B) (HCl, CH3COOH2+) and (CH3COOH,
Cl–)
(C) (CH3COOH2+,HCl ) and (Cl–, CH3COOH) (D) (HCl, Cl– ) and (CH 3COOH 2 + ,
CH3COOH)
1993
Q.33 Nicotic acid (Ka = 1.4 × 10–5) is represented by the formula HNiC. Calculate its percent dissociation
in a solution which contains 0.10 mole of nicotinic acid per 2.0 litre of solution.
Q.34 The pH of 0.05 M aqueous solution of diethyl amine is 12.0. Calculate Kb.
Q.35 The pH of blood stream is maintained by a proper balance of H2CO3 and NaHCO3 concentrations.
What volume of 5 M NaHCO3 solution, should be mixed with 10 ml sample of blood which is 2M in
H2CO3 in order to maintain a pH of 7.4. Ka for H2CO3 in blood is 7.8 × 10–7 ?
Q.36 An aqueous solution of a metal bromide MBr2 (0.05 M) is saturated with H2S. What is the minimum
pH at which MS will precipitate ? Ksp for MS = 6.0 ×10–21. Concentration of saturated H2S = 0.1 M;
K1 = 10–7 and K2 = 1.3 × 10–13 for H2S.
Q.37 A solution has 0.05 M Mg+2 and 0.05 M NH3. Calculate the concentration of NH4Cl required to
prevent the formation of Mg(OH)2 in solution. Ksp of Mg(OH)2 = 9.0 × 10–12 and ionisation constant of
NH3 is 1.8 ×10–5.
Q.38 What is the hydrogen ion concentration of 0.1 N CH3COOH solution ? The ionisation constant of
CH3COOH is 1.8 × 10–5. What is the pH of the solution.
Q.39 What is the decreasing order of strength of the bases OH–, NH2–, H – C  C– and CH3CH2– ?
(A) CH3CH2– > NH2– > H – C  C– > OH– (B) H – C  C– > CH3CH2– > NH2– > OH–
(C) OH– > NH2– > H – C  C– > CH3CH2– (D) NH2– > H – C  C– > OH– > CH3CH2–
Q.40 Fear and excitement generally cause one to breathe rapidly and it results in the decrease of CO2
concentration in blood. In what way will it change the pH of the blood ?
(A) pH will decrease (B) pH will increase (C) no change (D) pH will adjust to 7
1994
Q.41 Saccharin (Ka = 2 ×10–12) is a weak acid represented by formula HSaC. A 4×10–4 mole amount of
saccharin is dissolved in 200 cm3 water of pH 3. Assuming no change in volume, calculate the
concentration of SaC– ions in the resulting solution at equilibrium.
Q.42 Ka for butyric acid is 2.0 × 10–5. Calculate pH and hydroxyl ion concentration in 0.2 M aqueous
solution of sodium butyrate.
1995
Q. 43 An aqueous solution contains 10% ammonia by mass and has a density of 0.99 g cm–3. Calculate
hydroxyl and hydrogen ion concentration in this solution. Ka for NH4+ = 5.0 × 10–10 M
Q.44 0.15 mole of pyridinium chloride has been added into 500 cm3 of 0.2 M pyridine solution. Calculate
pH and hydroxyl ion concentration in the resulting solution assuming no change in volume.
(Kb for pyridine = 1.5 × 10–9 M)
Q.45 The solubility product of AgCl in water is 1.5 × 10–10. Calculate its solubility in 0.01 M NaCl.
Q.46 Calculate the pH of an aqueous solution of 1.0 M ammonium formate assuming complete dissociation.
(pKa of formic acid = 3.8 and pKb of ammonia = 4.8)

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1996
Q.47 An aqueous solution of aniline of concentration 0.24 M is prepared. What concentration of sodium hydroxide
is needed in this solution so that anilinium ion concentration remains at 1×10–8 M ? Ka for C6H5NH3+ is 2.4 ×
10–5 M.
Q.48 What is the pH of a 0.5 M aqueous NaCN solution ? pKb of CN– = 4.70.
Q.49 Calculate the percentage hydrolysis in 0.003 M aqueous solution of NaOCN. Ka for HOCN = 3.33 × 10–4.
Q.50 The ionisation constant of NH4+ in water is 5.6 × 10–10 at 25°C. The rate constant for the reaction of
NH4+ and OH– to form NH3 and H2O at 25°C is 3.4 × 1010 litre mol–1 sec–1. Calculate the rate
constant for proton transfer from water to NH3.
Q.51 The following acids have been arranged in the order of decreasing acid strength. Identify the correct
order :
ClOH (I) BrOH (II) IOH (III)
(A) I > II > III (B) II > I > II (C) III > II > I (D) I > III > II
1997
Q.52 Calculate the amount of NH3 and NH4Cl required to prepare a buffer solution of pH 9.0 when total
concentration of buffering reagents is 0.6 mol L–1. pKb for NH3 = 4.7, log 2 = 0.30
Q.53 The solubility product of SrF2 in water is 8 × 10–10. Calculate its solubility in 0.1 M NaF aqueous
solution.
Q.54 A sample ofAgCl was treated with 5.00 mL of 1.5 M Na2CO3 solution to give Ag2CO3. The remaining
solution contained 0.0026 g of Cl– per litre. Calculate the solubility product of AgCl
(Ksp Ag2CO3 = 8.2 × 10–12)
Q.55 An acid type indicator, HIn differs in colour from its 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
should be the minimum change in the pH of the solution to observe a complete colour change (Ka =
1.0 ×10–5) ?
Q.56 Ka for ascorbic acid (HAsc) is 5 × 10–5. Calculate the hydrogen ion concentration and percentage of
hydrolysis in an aqueous solution in which the concentration of Asc– ions is 0.02 M.
Q.57 If pKb for fluoride ion at 25°C is 10.83, the ionisation constant of hydrofluoric acid in water at this
temperature is –
(A) 1.74 × 10–5 (B) 3.52 × 10–3 (C) 6.75 × 10–4 (D) 5.38 × 10–2
Q.58 The solubility of A2X3 is y mol L–1. Its solubility product is –
(A)6y4 (B) 64y4 (C) 36y5 (D) 108y5
1998
Q. 59 What will be the resultant pH when 200 mL of an aqueous solution of HCl (pH = 2.0) is mixed with
300 ml of an aqueous solution of NaOH (pH = 12.0) ?
Q.60 Given Ag(NH3)2+ Ag+ + 2NH3, K c = 6.2 × 10–8 and Ksp of AgCl = 1.8 × 10–10 at 298 K.
Calculate the concentration of the complex in 1.0 M aqueous ammonia.
Q.61 Determine the number of mole of AgI which may be dissolved in 1.0 litre of 1.0 M CN– solution.
Ksp for AgI and KC for Ag(CN)2– are 1.2 × 10–17 M2 and 7.1 × 1019 M–2 respectively.
Q.62 0.16 g of N2H4 are dissolved in water and the total volume made up to 500 mL . Calculate the
percentage of N2H4 that has reacted with water at this dilution. The Kb for N2H4 is 4.0 × 10–6 M.

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Q. 63 If the Kb value in the hydrolysis reaction,
B+ + H2O BOH + H+
is 1.0 × 10–6, then the hydrolysis constant of the salt would be :
(a) 1.0×10–6 (B) 1.0 × 10–7 (C) 1 × 10–8 (D) 1.0 × 10–9
1999
Q.64 Two buffers, (X) and (Y) of pH 4.0 and 6.0 respectively are prepared from acid HA and the salt
NaA. Both the buffers are 0.50 M in HA. What would be the pH of the solution obtained by mixing
equal volumes of the two buffers? (KHA = 1.0 ×10–5)
Q.65 The solubility of Pb(OH)2 in water is 6.7 × 10–6 M. Calculate the solubility of Pb(OH)2 in a buffer
solution of pH = 8.
Q.66 Determine the concentration of NH3 solution whose one litre can dissolve 0.10 mole AgCl.
Ksp of AgCl and Kf of Ag(NH3)2+ are 1.0 × 10–10 M2 and 1.6 × 107 M–2 respectively.
Q.67 The pH of 0.1 M solution of the following salts increases in the order of :
(A) NaCl < NH4Cl < NaCN < HCl (B) HCl < NH4Cl < NaCl < NaCN
(C) NaCN < NH4Cl < NaCl < HCl (D) HCl < NaCl < NaCN < NH4Cl
2000
Q.68 What (H3O+) must be maintained in a saturated H2S solution to precipitate Pb2+, but not Zn2+ from a
solution in which each ion is present at a concentration of 0.01 M ?
(Ksp H2S = 1.1 ×10–22 ; Ksp ZnS = 1.0 × 10–21)
Q.69 The average concentration of SO2 in the atmosphere over a city on a certain day is 10 ppm, when the
average temperature is 298 K. Given that the solubility of SO2 in water at 298 K is
1.3653 mol litre–1 and the pKa of H2SO3 is 1.92, estimate the pH of rain on that day.
2001
Q.70
(a) A solution contains a mixture of Ag+ (0.10 M) and Hg22+ (0.10 M) which are to be separated by
selective precipitation. Calculate the maximum concentration of iodide ion at which one of them gets
precipitated almost completely. What % of that metal ion is precipitated ?
Ksp of AgI = 8.5 ×10–17 and Ksp of Hg2I2 = 2.5 × 10–26
(b) 0.01 Mol of AgNO3 is added to 1 litre of a solution which is 0.1 M in Na2CrO4 and 0.005 M in
NaIO3. Calculate the mol of precipitate formed at equilibrium and the concentrations of Ag+, IO3–
and CrO42–.
(Ksp values of Ag2CrO4 and AgIO3 are 10–8 and 10–13 respectively.)
2002
Q.71 500 mL of 0.2 M aqueous solution of acetic acid is mixed with 500 mL of 0.2 M HCl at 25°C.
(i) Calculate the degree of dissociation of acetic acid in the resulting solution and pH of the solution.
(ii) if 6 g of NaOH is added to the above solution, determine the final pH. [Assume there is no change
in volume on mixing; Ka of acetic acid is 1.75 × 10–5 mol L–1]
2003
Q.72 Will pH value of water be same at temperature 25°C and 4°C. Justify in not more than 2 or 3
sentences.
2004
Q.73 HX is weak acid (Ka = 10–5). It forms a salt NaX (0.1 M) on reacting with caustic soda. The degree
of hydrolysis of NaX is –
(A) 0.01% (B) 0.0001% (C) 0.1% (D) 0.5%
Q.74 0.1 M of HA is titrated with 0.1 M NaOH, Calculate the pH at end point. Given
Ka(HA) = 5 × 10–6 and  << 1

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2005
Q.75 CH3NH2 (0.1 mol, Kb = 5 × 10–4) is mixed with 0.08 mol of HCl and the solution is diluted to 1 litre.
The H+ ion concentration of the resulting solution will be
(A) 1.6 × 10–11 (B) 8 × 10–11 (C) 3 × 10–5 (D) 1.25 × 10–4
2006
Q.76 If CO2 be passed into water, what will remain present in solution
(A) CO2, H2CO3, CO 32 , HCO 3 (B) H2CO3, CO2
(C) HCO 3 , CO 32 (D) CO 2 , HCO 3
Q.77 Given:
Ag+ + NH3 Ag(NH3)+; K1 = 1.6  103
Ag(NH3)+ + NH3 [Ag(NH3)2]+; K2 = 6.8  103
The equilibrium constant for the reaction
Ag+ + 2NH3 [Ag(NH3)2]+ is
(A) 6.8  103 (B) 1.088  107
(C) 1.088  106 (D) 1.6  103

ANSWERS
1. Daily Practice Problem Sheet
1. B 2. A 3. C 4. A 5. D 6. D
7. A 8. C 9. B 10. C 11. A 12. D
13. C

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2. Daily Practice Problem Sheet
1. C 2. B 3. B 4. A 5. D 6. B
7. A 8. A 9. C 10. A 11. C 12. A
13. B 14. B 15. C

3. Daily Practice Problem Sheet

1. A 2. C 3. B 4. A 5. C 6. B
7. D 8. B 9. D 10. C 11. A 12. A
13. A 14. A

4. Daily Practice Problem Sheet

1. D 2. C 3. A 4. B 5. D 6. B
7. V 8. D 9. B 10. A 11. C, D 12. C
13. A

5. Daily Practice Problem Sheet

1. B 2. C 3. A 4. D 5. B 6. A
7. C 8. C 9. A 10. B

6. Daily Practice Problem Sheet

1. A 2. D 3. B 4. C 5. A 6. A
7. B 8. D 9. C 10. A 11. D 12. A
13. B 14. C

7. Daily Practice Problem Sheet

1. A 2. B 3. C 4. D 5. A 6. B
7. A 8. D 9. C 10. A 11. B 12. C
13. D 14. B 15. C 16. D 17. B 18. A
19. B 20. C 21. B 22. A 23. A

8. Daily Practice Problem Sheet

1. A 2. C 3. B 4. D 5. B 6. A
7. C 8. B 9. A 10. B 11. D 12. A
13. B 14. D 15. A

9. Daily Practice Problem Sheet

1. B 2. C 3. A 4. B 5. D 6. A
7. B 8. C 9. A 10. A 11. C 12. B

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13. B 14. A

10. Daily Practice Problem Sheet

1. (i) 5.5 (ii) 8 (iii) 7 (iv) 8 (v) 6.5 (vi) 7
2. (i) 1.64 gm (ii) 13.6 kg (iii) 0.535 gm
–8
3. 10
4. 8.85 5. B 6. D
7. (i) 2.87 (ii) 11.13 (iii) 5.34 (iv) 5.13 (v) 3.4 (vi) 7 (vii) 8.8
8. C 9. B 10. D

11. Daily Practice Problem Sheet

1. D 2. C 3. C 4. A 5. B 6. A
7. C 8. B 9. D 10. B 11. C 12. A
13. D

12. Daily Practice Problem Sheet

2. (i) A (ii) B 3. Ksp of AB2 = 25.6 × 10–8, A = 4 × 10–3 m/l
4. 3.2 ×10–11 5. Br–= 4 × 10–7 m/l 6. C 7. B
8. A 9. C 10. B 11. B
12 (i) A (ii) D 13 3.34 × 10–17 14. 26.24 × 10–12
15. 10–3 m/l

13. Daily Practice Problem Sheet

1. D 2. C 3. B 4. A
5. 10–5 M 6. 1.11 × 10–14 M 7. 2.58 ×10–7 M 8. 10–11 M
9. 5 × 10–8 M 10. C 11. C 12. B
13. A 14. B 15. A

14. Daily Practice Problem Sheet

1. No 2. Yes 3. No 4. 5. B
6 B 7. No 8. Yes 9. No 10. B
–8 –9
11. B 12. 4.5 × 10 13. C 14. 1.25 × 10 gm
15. 4.47 × 10–4 M 16. No 17. 6.01 gm
18. 0.1 M
19. (i) 8.5 × 10–16 M (ii) 5 × 10–13 M (iii) AgI
20. solubility of AgBr = 4 × 10–2 M, solubility of AgCNS = 8.16 × 10–7M

OBJECTIVE QUESTION ANSWERS

LEVEL–I

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1. C 2. B 3. C 4. C 5. C
6. C 7. A 8. D 9. C 10. C
11. D 12. C 13. D 14. D 15. D
16. A 17. A 18. D 19. B

LEVEL–II
1. B 2. D 3. C 4. D 5. D
6. B 7. A 8. D 9. C 10. C
11. C 12. A 13. B 14. B 15. C
16. A 17. A 18. A 19. C 20. B
21. C 22. D 23. C 24. B 25. A
26. C

LEVEL–III
1. A, B 2. A, C, D 3. D 4. A, C, D
5. A 6. B 7. C 8. B,C
9. A, B 10. B, C, D 11. A,B 12. A,B
13. A, B 14. B,C 15. A, B 16. B, C
17. B, D
LEVEL–IV

1. B 2. A 3. D 4. A 5. A

SUBJECTIVE QUESTION ANSWERS

LEVEL–I

1. 2.3 mol/lit 2. 1.5 times 3. 1.44 × 10–4

–4 –5
4. (a) 1.76 × 10 mg/L, (b) 8.8 × 10 mg/L, (c) 1.588 mg/L
5. No
6. (i) = 0.5553 × 10–2, Kh = 0.308 × 10–4, pH = 7 (ii) = 0.52, Kh = 1.208 , pH = 4.71
(iii) = 0.775, Kh = 11.82 , pH = 9.79
7. 6.89, 7, 7.02, 7 8. 8.59 9. 5.68 × 10–10
10. 1.2 × 10–5 M, 3.2 × 10–5 M 11. 4.11 × 10–4 M 12. 5.6 × 10–10, 2.4 × 10–4, 5.63
13. 2.87, 1.3 14. Ksp (Ag2CrO4) = 4 × 10–12 15. pH = 9.168
16. No 17. 1.4 × 10–5, 2.15×10–4 mole/litre; 15.4 time
1
18. of its initial value 19. 2.1 × 10–6
2230

LEVEL–II
1. 8.7 mL
2. HZ < HY < HX , Ka(HY) = 10–5 M, Ka(HZ) = 10–9 M
3. (a) 3.7 × 104 dm3 (b) 4 dm3 4. KC = 3.02 × 10–2, S = 0.123 M
5. (a) pH = 3.83 (b) pH = 3.85 (c) 3.99 6. pH = 2.558
7. (a) pH = 9.239 (b) lowered (c) pH = 4.699 8. 0.0818 moles
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9. x : y = 1 : 3.98, unaltered
10. pH = 11.22 11. 9.55 12. (i) pH = 4.35 (ii) 1.79 × 10–9 mol/lit
13. (i) 28.57% (ii) 4.11 × 10–4 mol dm–3 14. 67%
15. pH = 7.3
16. (a) for Cl – = 1.7 × 10–9 mol dm–3, For Br – = 5 × 10–3 mol dm–3, For I– 8.5 × 10–16 mol dm–3
(b) AgI (c) 1.7 × 10–5 mol dm–3 (d) 5.0 × 10–8 mol dm–3, 3.0 × 10–4 mol dm–3
17. pH = 3; 0.1 % 18. (a) No (b) [CH3COO–] = 1.7 M
19. CuS precipitate; 3.27 × 10–14%, MnS precipitates 20. pH = 8.96

LEVEL–III

1. NO2–, HCN, ClO4, HF, H2O, HCO3–, HS– 2. BF3, H+, NH4+
3. F–, HSO4–, CO32– 4. NH3, NH4+, HCOOH
7. 2.42 8. 1.7 × 10–4M
9. F– = 1.5 × 10–11, HCOO– = 5.6 × 10–11, CN– = 2.08 × 10–6
10. [Phenate ion] = 2.2 × 10–6, pH = 5.65, a = 4.47 × 10–5, pH of 0.01 M sodium phenate solution
= 9.30
11. [HS–] 9.54 × 10–5, in 0.1M HCl [HS–] = 9.1 × 10–8 M, [S2–] = 1.2 × 10–13 M, in 0.1 M HCl [S2–]
= 1.09 × 10–19 M
12. [Ac–] = 0.00093, pH = 3.03
13. [A–] = 7.08 × 10–5 M, Ka = 5.08 × 10–7, pKa = 6.29
14. (a) 2.52 (b) 11.70 (c) 2.7 (d) 11.30 15. (a) 11.65 (B) 12.21 (c) 12.57 (d) 1.87
16. pH = 1.88, pKa = 2.70 17. Kb = 1.6 × 10–6, pKb = 5.8
18.  = 6.53 × 10–4, Ka = 2.34 × 10–5 19. (a) 0.0018 (B)0.00018
20. a = 0.0054
21. (a) 1.48 × 10–7 M, (b) 0.063 (c) 4.17 × 10–8 M (d) 3.9u × 10–7
22. (a) 1.5 × 10–7 M, (b) 10–5 M (c) 6.31 × 10–5M (d) 6.31 × 10–3M
23. [K+] = [OH–] = 0.05 M, [H+] = 2.0 × 10–13 M
24. [Sr2+] = 0.158 M, [OH–] = 0.3162 M, pH = 13.50
25.  = 1.63 × 10–2 , pH = 3.09. In presence of 0.01 M HCl, a = 1.32 × 10–3
26. Ka = 2.09 × 10–4 and degree of ionization = 0.0457
27. pH = 7.97, degree of hydrolysis = 2.36 × 10–5 28. Kb = 1.5 × 10–3
29. NaCl, KBr solutions are neutral, NaCN, NaNO2 and KF solutions are basic and NH4NO3 solution
is acidic.
30. (a) pH of acid solution = 1.94 (b) its salt solution = 2.87
31. pH = 6.78 32. (a) 11.2 (b) 7.00 (c) 3.00
33. Silver chromate S = 0.65 × 10 M; Molarity of Ag = 1.30 × 10–4M
–4 +

Molarty of CrO42– = 0.65 × 10–4 M; Barium Chromate S = 1.1 × 10–5 M; Molarity of Ba2+ and
CrO42– each is 1.1 × 10–5M; Ferric Hydroxide S = 1.39 × 10–10M;
Molarity of Fe3+ = 1.39 × 10–10M; Molarity of [OH–] 4.17 × 10–10M
Lead chloride S = 1.59 ×10–2M ; Molarity of Pb2+ = 1.59 × 10–2M
Molarity of Cl– = 3.18 × 10–2M; Mercurous iodide S = 2.24 × 10–10M;
Molarity of Hg22+ = 2.24 × 10–10M and molarity of I– = 4.48 × 10–10 M
34. Silver chromate is more soluble and the ratio of their molarities = 91.9
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35. No precipitate 36. Silver benzoate is 3.317 times more soluble at lower pH
37. The highest molarity for the solution is 2.5 × 10–9M
38. 2.46 litre of water 39. Precipitation will take place in cadmium chloride solution

LEVEL–IV

1. 4.8 × 10–3mol/lit 2. 8.7 × 10–4 gm/lit 3. 4.19 4. pH = 4

5. 5.6 × 10–5 mole 6. (i) 4.57 (ii) 1 7. pH = 4 8. 8.85 × 10–3 mol
9. D 10. A 11. 3.98 × 10–1
12. [Al+3] = 1.28 × 10–15 M ; [Mg+2] = 0.686 M 13. (i) 3.87 × 10–5 (ii) 1.5 × 10–8 M
14. 9.02 15. 2.3724, 2.77 × 104 lit 16. 39.62 ml 17. 8.71
18. D 19. D 20. C 21. 1.81 × 10–5
22. 1010 23. 3.97 × 10–12 mol3lit–3 24. 8.25 × 10–4
25. [H+] = 7.2 × 10–10 M, [OH–] = 1.39 × 10–5 M 26. (a) 11 (b) 12 (c) 12.3010 (d) = 11.2041
–2 –20 – –8
27. [S ] = 1.44 × 10 M, [HS ] = 3.3 × 10 M
28. (i) change in pH = + 0.1761 unit; i.e. pH decreases (ii) change in pH = –0.1761; i.e. pH increases
29. 758.2 mg 30. 9 31. D 32. D
–3
33. 1.67% 34. 2.5 × 10 35. V = 78.36 ml
36. pH = 0.9826 37. 0.067 M 38. 1.34 × 10–3, 2.87
39. A 40. B 41. 4 × 10–12 M
42. [OH–] = 10–5 , pH =9
43. [OH–] = 1.07 × 10–2 M [H+] = 0.9268 × 10–12 M 44. [OH–] = 10–9, pH = 5
45. 1.5 × 10–8 mol/lit 46. 6.5 47. 0.01 M 48. 11.5
–2 5
49. 10 % 50. 6.07 × 10 51. A 52. 0.2 M, 0.4 M
–8 –10
53. 8 × 10 M 54. 1.71 × 10 55. pH = 2
56. [H]+ = 5 × 10–9; 0.01 %
57. C 58. D 59. pH = 11.3010 60. 0.0539
61. 0.49 mole 62. 2% 63. C 64. 5.7033
–3
65. 1.203 × 10 mol/lit 66. 2.79 M 67. B 68. 3.3 × 10–2 M
69. 0.49
70. (a) [I]– = 5 × 10–13 M, 99.83% (b) [CrO42–] = 0.0975; [Ag+] = 3.2 × 10–4 M ; [IO3–] = 3.1 × 10–10 M
71. = 0.000175, pH = 1 (ii) 4.757 72. No 73. A
74. 9 75. B 76. A 77. B

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