[Type text]

Electrolytes: Whose aqueous solution conduct electricity.

Electrolytes are classified into two groups.

1. Strong Electrolytes: 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

compound are weak electrolytes. e.g. NH 4 OH, CH 3COOH .

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.

Ka = C ∝2
Ka
∝= = Ka V
C
ionized molecules
∝=
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.

Ostwald’s Dilution Law

Ostwald’s pointed out that like chemical equilibrium in ionic equilibrium we can apply law of
mass action. An equilibrium between ionized and unionized molecules.

Consider a binary electrolyte having conc C and degree of dissociation is α.

AB A + + B−
At. time = 0 C 0 0
at time = t C(1 – α) C α Cα
+ −
[A ][B ] Cα × Cα Cα 2
K eq = = = , for a weak electrolyte
[AB] C(1 − α) 1− α
1− α ≅ 1
K eq
K eq = Cα 2 , α =
C

[Type text]
[Type text]

If 1 mole of AB is present in `V’ litre of solution.

1
C=
V
α = K eq × V
K eq
Conc. of [A+] = Conc. [B–] = Cα = C = K eq C
C

Limitation

i) This is only for weak electrolytes not for strong electrolytes.

ii) This law is not applicable for strong electrolyte because strong electrolytes are almost
λC
completely ionized at all dilution and hence ∞ does not give accurate results.
λ

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 α.

2H2O( l ) H3O+ + OH–

Cα Cα
[H O ][OH − ]
+
K eq = 3
[H 2 O]2
K eq [H 2 O(l)] = [H3O+ ][OH − ]
Since conc. of pure water remain constant
K eq k = [H3O+ ][OH − ]
K w = [H 3O + ][OH − ]
K w = dissociation constant of water at 25°C, Kw comes out to be 1 × 10–14 m2/lt2.
Kw depends upon temperature dissociation of water gives equal no. of H3O+ and OH– ions.
1× 10−14 = [H 3O + ]2 = [OH − ]2
So [H 3O + ] = [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.

[Type text]
[Type text]

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
presence in the solution.

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 [H 3O + ] remain equal to
[OH – ] in pure water.

Illustration 1: The Kw for 2H2O H3O+ + 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+] [HO–] = 10–14 (Q 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.

pH determination for Weak Acids

Weak acids do not dissociate completely in the water their % degree of dissociation is very less.

[Type text]
[Type text]

e.g. lets takes CH3COOH (C mole/litre and having degree dissociation α).

CH3COOH CH3COO– + H+
C(1–α) Cα Cα
− +
[CH 3COO ][H ] Cα.Cα
K a (CH3COOH) = =
[CH 3COOH] C(1 − α )
Cα 2
Ka =
1− α
if α < ≤ 0.1 , then we can neglect
1 − α ≅1
K a = Cα 2
Ka
α=
C
Ka
[H + ] = Cα = C = KaC
C
pH = –log [H+] = – log10 [ K a C]

Note: For calculating the pH of a weak acid first of all we calculate α from the equation
Cα 2
Ka = , if α comes out to be α ≤ 0.1 then 1 – α will be taken as one and we use
1− α
formula K a = Cα 2 otherwise we would be use the formula
Cα 2
Ka = for all calculation.
1− α

Illustration 2: What is pH of 1M CH3COOH solution? To what volume must one litre of this
solution be diluted so that the pH of resulting solution will be twice the original
value. Given : Ka = 1.8 × 10–5
Solution: H3CCOOH + H2O H3CCOO– + H3O+
t=0 1M 0 0
-xM xM xM
–———————————–––————————
t = teq (1-x)M x x
x2 x2
Ka = ≈
1− x 1
∴ x = K a = 4.2 × 10–3 = [H3O+]
pH = – log [H3O+] = – log {4.2 × 10–3} = 3 – log 4.2 = 2.37
Now, let 1L of 1M ACOH solution be diluted to VL to double the pH and the
conc. of diluted solution be C.
H3COOH + H2O H3COO– + H3O+
t=0 C 0 0
– 1.8 × 10 –5
1.8 × 10 –5
1.8 × 10–5

[Type text]
[Type text]

–————————————————————
t = teq C– 1.8 × 10–5 1.8 × 10–5 1.8 × 10–5
New pH = 2 × old pH = 2 × 2.37 = 4.74
pH = – log [H3O+] = 4.74
∴ [H3O+] = 1.8 × 10–5
[CH 3COO − ] × [H 3O + ]
Ka =
[CH 3COOH]
1.8 × 10−5 × 1.8 ×10 −5
1.8 × 10–5 =
C − 1.8 × 10−5
∴ C = 3.6 × 10 L
–5

on dilution
M1V1 = M2V2
1M × 1L = 3.6 × 10–5 L × V2
∴ V2 = 2.78 × 104 L

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
HA H+ + A– its degree of dissociation be α.

Ka
α=
C

BA (another electrolyte) added whose molarity is M, due to this the new degree of dissociation
becomes α′ .

BA B+ + A–
0 M M
HA H+ + A–
C(1 – α′ ) C α′ C α′
[H ][A ] [Cα′][Cα′ + M]
+ −
K a (HA ) = =
[HA] [C(1 − α′)]
K a (HA ) = Cα′ + Mα′
2
1 − α′ ≅ 1
Cα′2 Neglecting because α′ < < 1
K
α′ = a
M

As a result of common ion effect, the conc. of the ion, which is not common changes to make the
Ka constant, become K only depends upon temperature not on concentration.

[Type text]
[Type text]

Note: The use of this phenomenon is made in qualitative analysis to adjust the conc. of S– – ions in
second group (reagent H2S and HCl) and OH– ion conc, in third group (NH4Cl + NH4OH).

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 then 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).
Same rule applies for pH of 10 –8 M NaOH.

Illustration 3: 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

[Type text]
[Type text]

10−2
∴ [Ca(OH)2] = M = 0.5 × 10–2 M
2
[Every Ca(OH)2 gives two OH– ions]

Relative strength of Acids and Bases

For weak acids

Strength of I acid
Relative strength =
Strength of II acid

For Acids HA1 if concentration is C1 and degree of dissociation α1

HA1 H + + A1–
[H + ] = C1α1

For HA 2 if concentration is C2 and degree of dissociation is α 2

HA 2 H + + A 2–
[H + ] = C 2 α 2

Then, Relative strength

[H + ] furnished by I acid C1α1

= + =
[H ] furnished by II acid C2 α 2

C1  K a1 C2   K a C1 
R.S. = ×   =  1 
C2  K a 2 C1   K a 2 C2 
If C1 and C2 are same, then
 Ka 
R.S. =  1 
 Ka
 2 

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 α
HA  → H+ + A–
C2(1 –α) C 2α C 2α

[Type text]
[Type text]

Total (H+) conc. = C1 + C2α

pH = – log [C1 + C2α]
[H + ][A − ] [C1 + C 2 α][C2 α ]
K a (HA) = =
[HA] [C 2 (1 − α )]
Illustration 4: 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.
HCOOH HCOO – + H +
[H + ][HCOO – ]
Ka =
[HCOOH]
[0.02][HCOO – ]
1.8 × 10 –4 =
[0.015]
∴ [HCOO ] = 1.35 × 10 –4 M
–

pH calculation of solution of a mixture of two weak Acids in water

Let two weak acids be HA and HB and their conc. are C1 and C2, α1 is the degree of dissociation
of HA in presence of HB (due to common ion effect) and α2 be degree of dissociation of HB in
presence of HA. In aqueous solution of HA and HB following equilibrium exists.
HA + H2O(l) H3 O+ + A–
conc. at equi. C1(1 – α1) C1α1 + C2α2 C1α1
HB + H2O(l) H3 O+ + B–
C2(1 – α2) (C1 α1 + C2 α2) C2α2
+ −
[H O ][A ] [C1α1 + C 2 α 2 ][C1α1 ]
K a[HA] = 3 =
[HA] C1 (1 − α1 )
[H 3O + ][B− ] [C1α1 + C2 α 2 ][C 2 α 2 ]
K a[HB] = =
[HB] [C2 (1 − α 2 )]
pH = – log[H + ] = – log[C1α1 + C 2 α 2 ]

Illustration 5: 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 .

[Type text]
[Type text]

Solution: In this problem both the acids contribute for [H + ] due to appreciable dissociation.
Thus,
HCOOH H + + HCOO –
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
∴ 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

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 α1 and α2 be degree of dissociation for first and second dissocation.
H2 A HA– + H+
C(1 –α1) Cα1 (1 – α2) Cα1 + Cα1 α2
HA– H+ + A– –
Cα1 (1 – α2) Cα1 + Cα1 α2 Cα1 α2.
[HA − ][H + ]
Ka1 =
[H 2 A]
[Cα1 (1 − α 2 )][Cα1 +Cα1α 2 ]
Ka1 =
C(1 − α1 )
[H + ][A − − ] [Cα1 + Cα1α 2 ][Cα1α 2 ]
Ka 2 = =
[HA − ] [Cα1 (1 − α 2 )]
After solving for α1 and α2. We can calculate the H+ conc.
[H+] = Cα1 + Cα1 α2

[Type text]
[Type text]

pH = – log [Cα1 + Cα1 α2]

Illustration 6: 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. K 1 = 4.45 × 10 –7 , K 2 = 4.69 × 10 –11 .

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

∴ [H + ] = 6.61×10 –5 mol litre –1
H 2 CO3 H + + HCO3–
[H + ][HCO3– ]
K1 =
[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
HCO3– H + + CO3–2
[H + ][CO3–2 ] [6.61× 10 –5 ][CO3–2 ]
K2 = or 4.69 × 10 –11
=
[HCO3– ] [6.73 × 10 –5 ]
∴ [CO3–2 ] = 4.78 ×10 –11 mol litre –1

pH of 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
+ –2
[H ] = 10 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

pKa and pKb for a conjugate acid-base pair

For an acid HX
HX H+ + X –
[H + ][X – ]
∴ Ka = … (A)
[HX]
For conjugate base X – of acid HX

[Type text]
[Type text]

X – + H 2O HX + OH –
[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.

Problem 7: 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
∴ KW = 10–12
Now using
K w2 ∆H  T2 − T1 
2.303 log10 =  
K w1 R  T1 × T2 
10−12 ∆H  308 − 298 
2.303 log10 =
10−14 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 8: Calculate the pH of solution obtained by mixing 10 mL of 0.1 M HCl and 40 ml

of 0.2 M H2SO4.

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+] = = 3.4 × 10−1 Q [H ] = 
50  Vin mL 
∴ pH = – log [H+] = – log 0.34
pH = 0.4685

Buffer Solution
A Buffer solution is that which resist the pH change by addition of small quantity of acid or
alkali.

[Type text]
[Type text]

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+ CH3COOH
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 +4 + OH − 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.

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 – 
→ CH 3COOH
Feebly dissociated
+
Thus, the H ions added are neutralized by the acetate ions present in the mixture. There is very
little change in the pH of the mixture.

[Type text]
[Type text]

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 2 O

Thus, again, there is very little change in the pH of the mixture.

Calculation of pH of Acidic Buffer Solution

e.g. Mixture of (CH3COOH + CH3COONa)
CH3COOH CH3COO– + H+
[CH 3COO − ][H + ]
Ka =
[CH 3COOH]

Since most of CH3COO– comes from salt (CH3COONa) and hence conc. of CH3COO– will be
conc. of CH3COONa.

[Salt][H + ]
Ka =
[Acid]
K [Acid]
[H + ] = a
[Salt]
Taking (–ve) log on both sides
[Acid]
–log [H+] = – log Ka – log
[Salt]
[Salt]
Henderson’s equation pH = pK a + log
[Acid]

Illustration 9: 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.α = C   = (K a .C) = (K a ) Q C=1
 C 
1
∴ pH1 = – log Ka
2
Case II : pH when 1 mole CH3COONa and 1 mole of CH3COOH; a acidic buffer
solution forms
Q [Salt] = 1 M, [Acid] = 1 M

[Type text]
[Type text]

[Salt]
∴ pH2 = – log Ka + log
[Acid]
pH1 1
pH2 = –log Ka ∴ =
pH 2 2

Illustration 10. Twenty mL of 0.2 M NaOH is added to 50 mL of 0.2 M acetic acid to give 70
mL of the solution. What is the pH of the solution ? Calculate the additional
volume of 0.2 M NaOH required to make pH of the solution 4.74. The
ionization constant of acetic acid is 1.8 × 10-5.

Solution : The addition of NaOH converts equivalent amount of acetic acid into sodium
acetate. Hence,
concentration of acetic acid after the addition of sodium hydroxide
30
= × 0.2 M
70
Concentration of sodium acetate after the addition of sodium hydroxide
20
= × 0.2 M
70
Hence, using the expression = pH = pKa + log
[ Salt ] , we get . . . . . (1)
[ acid ]
 20 
pH = -log(1.8 × 10-5) + log   = 4.745 – 0.177 = 4.568
 30 
Let V be the additional volume of 0.2 M NaOH that need to be added to make
pH of the solution equal to 4.74.
Substituting this value is eq. (1) we would be
 20 mL + V 
4.74 = 4.745 + log  
 30 mL − V 
20mL + V 20mL + V
or log = −0.005 or = 0.9866
30mL − V 30mL − V
30 mL × 0.9866 − 20mL
or V = = 4.83 mL
1.9866

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+

[Type text]
[Type text]

If a strong base is added, the OH – ions added are neutralized by NH +4 ions forming very slightly
dissociated NH 4 OH .

OH– + NH +4 
→ NH 4 OH

Calculation of pH of Basic Buffer Solution

e.g. Mixture of (NH4OH + NH4Cl)
NH4OH NH +4 + OH–
[NH +4 ][OH − ]
Ka =
[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 × [Base]
[OH − ] = b
[Salt]
Taking (–log10) both side
[Base]
–log [OH–] = – log Kb – log
[Salt]
[Salt]
pOH = pK b + log
[Base]

Hence pH = 14 – pOH at 25°C, K w = 1× 10 –14 mol2/litre2

Salt Buffer
A salt buffer is a solution of a salt which itself can act as a buffer. Such salt is the salt of a weak
acid and weak base.

For example, CH3COONH 4 CH 3COO – + NH 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 .

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.

[Type text]
[Type text]

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]

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.

Hydrolysis of Salt
Salts are strong electrolytes when dissolved in water, they dissociated almost completely into
cation or anions. If anion reacts with water it is called as anionic hydrolysis.

[Type text]
[Type text]

A– + H2O 
→ HA + OH– Akaline 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 Cl + H 2 O NH 4 OH + HCl
NH +4 + Cl− + H 2 O NH 4 OH + H + + Cl−
NH +4 + H 2 O NH 4 OH + H +
(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]
H2O H + + OH −
K w = [H + ][OH − ] … (2)
Dividing (2) ÷ (1)
Kw [H + ][OH − ]
= × [NH 4 OH]
K b [NH 4+ ][OH − ]
Kw
= Kh
Kb

Degree of hydrolysis

NH +4 + H 2 O NH 4+ + OH −
C(1− h ) Ch Ch

Ch . Ch
Kh = = Ch 2 (1 – h ≅ 1)
C(1 − h)

[Type text]
[Type text]

Kh
h=
C
Kw
h=
K bC
Kw
[H + ] = Ch = C
K bC
Kw × C
[H + ] =
Kb
Taking –log10 both side
1
pH = [pK w − pK b − log C]
2
1 1
pH = 7 − pK b − log C
2 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).
CH3COONa + H 2 O(l) CH 3COOH + NaOH
CH3COO − + Na + + H 2 O(l) CH 3COOH + Na + + OH −
[CH3COOH][OH − ]
Kh =
[CH3COO− ]

Relation B/w, K h , Kw and Ka

CH3COOH CH 3COO− + H +
[CH 3COO − ][H + ]
Ka = … (1)
[CH3COOH]
H 2O H + OH −
K w = [H + ][OH − ] … (2)
Dividing equation (2) ÷ (1)
K w [H + ][OH − ] × [CH 3COOH] [OH − ][CH 3COOH]
= = = Kh
Ka [CH3COO − ][H + ] [CH 3COO − ]

Degree of Hydrolysis

CH3COO − + H 2 O(l) CH 3COOH + OH −

at time = 0 C 0 0

[Type text]
[Type text]

at time = t C(1 – h) Ch Ch
Ch . Ch
Kh = = Ch 2 (1 – h ≅ 1) h should be smaller than 0.1 then 1 – h = 1.
C(1 − h)
Kh
h=
C
Kw
h=
KaC
OH − = Ch
Kw KwC
OH − = C =
KaC Ka
Kw Ka Ka × K w
H 3O + = −
= Kw =
[OH ] KwC C
Taking (–ve) log both side
1 1 1
− log[H + ] = log K w − log K a + log C
2 2 2
1
= [pK w + pK a + log C]
2
1 1
pH = 7 + pK a + log C
2 2

pH will be more than 7, hence resultant solution will be basic in nature.

Illustration 11: 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

[Type text]
[Type text]

pKa = 3.08
Ka = 10–3.08 = 8.3 × 10–4.

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).

CH3COONH 4 + H 2 O CH3COOH + NH 4 OH
CH3COO − + NH +4 + H 2 O CH 3COOH + NH 4 OH
[CH3COOH][NH 4 OH]
Kh =
[CH 3COO − ][NH 4+ ]

Relation B/w, K h , K w , K a & K b

CH3COOH CH 3COO− + H +
[CH 3COO − ][H + ]
Ka = … (1)
[CH3COOH]
NH 4 OH NH 4+ + OH −
[NH +4 ][OH − ]
Kb = … (2)
[NH 4 OH]
H2O H + + OH −
K w = [H + ][OH − ] … (3)
Kw [H + ][OH − ] × [CH3COOH][NH 4 OH]
=
Ka × Kb [CH 3COO − ][H + ][NH +4 ][OH − ]
Kw
= Kh
Ka × Kb

Degree of Hydrolysis
CH3COO − + NH 4+ + H 2 O CH 3COOH + NH 4 OH
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 Ka Kh

[Type text]
[Type text]

The acetic acid formed would partially decompose to give CH3COO – and H + . But because of
common ion effect (that is, due to the unhyrolysed CH3COO – ) it is possible to neglect the
acetate ion coming from CH3COOH .

Therefore CH3COOH CH 3COO – + H +

Cα C(1 – α )
C(1 – α )[H + ]
Ka =
Cα
+
[H ]
Ka = (1– α ≅ 1)
α
Kw Kw Ka
[H + ] = K a α = K a =
Ka Kb Kb
1
or pH = pK w + pK a − pK b
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 of CN– ions produced OH– ions according to the equation.

CN − + H 2 O HCN + OH −

which can react with NH +4 ions as

OH − + NH +4 NH 4 OH

This latter reaction causes equilibrium in the form 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 .

Case IV : Salts of strong Acid + Strong Base

e.g., NaCl, KNO3 , … etc.

[Type text]
[Type text]

This category of salts does not undergo salt hydrolysis

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 b/w
the excess of the solute and ions furnished by that parts of the solute which has gone in solution.
The solubility product of a sparingly soluble salt is given as product of the conc. of the ions
raised to the power equal to the no. of times the ion occur in the equation after the dissociation of
the electrolyte.
AxBy xAy+ + yBx–
K sp = [A y + ]x [Bx − ]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.

Common-ion Effect on Solubility

The common ion presence in the solution decrease the solubility of a given compound e.g. The
solubility of BaSO4 in Na2SO4 solution is smaller than that in an aqueous solution.

Consider saturated solution of AgCl. If a salt having either of the ion common to AgCl say KCl
is added to it, then

AgCl(g) + aq. Ag + + Cl –
→ 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)

[Type text]
[Type text]

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

K
K SP = s × 0.1 or s AgCl = SP
0.1
where s is solubility of AgCl in presence of 0.1 M KClaq.

Ionic Product
For a solution of a salt at a specified concentration, the product of the concentration of the ions,
each raised to the proper power, is called as the ionic product for a saturated solution in
equilibrium with excess of solid, the ionic product is equal to solubility product.

At equilibrium, ionic product = solubility product

If ionic product is less than solubility product it means solution is unsaturated means more salt
can be 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.

[Type text]
[Type text]

Preferential Precipitation of Salts

Frequently, a solution contains more than one ion capable of forming a ppt. with another ion
which is added to the solution. e.g., in a solution containing Cl–, Br– and I–, if Ag+ ions are added
then out of the three, the least soluble silver salt is ppt first. If the addition of Ag+ ions is
continued, eventually a stage is reached when the next lesser soluble salt starts ppt along with the
least soluble salt and so on if the stocihiometry of the ppted salts is the same, then the salt with
the minimum Ksp or minimum solubility will ppted first followed by higher Ksp.

If the stoichiometry of the ppted salts is not the same, then with Ksp alone, we can’t predict which
ion will ppted first. e.g. a solution containing Cl– and CrO 4–2 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 −42 ) 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 −42 , if the conc. of Ag+ ions needed to start the ppt of CrO −42 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 −42 . 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.
CH3COONH4 CH3COO– + NH +4 … (1)
S–y S–y
CH3COO –
+ NH +4 + H2O CH3COOH + NH4OH
S–y S–y y y … (2)
K sp = (S − y)(S − y) = (S − y) 2
Due to hydrolysis of salt from equation (2)
[CH3COOH][NH 4 OH] y.y
Kh = − +
=
[CH3COO ][NH 4 ] (S − y)(S − y)
2
 y 
Kh =  
S− y 
and we also know that
Kw
Kh =
Ka Kb

[Type text]
[Type text]

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.

CH3COONH4 CH3COO– + NH +4
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 [CH 3COOH] y
= K′a = =
K a (CH3COOH) [CH3COO ][H ] (S − y)(H + )
− +

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

Solubility of a salt of weak acid and weak base in basic buffer

Similarly CH3COONH4 CH3COO– + NH +4

y S–y
+ −
NH + OH
4 NH4OH
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 CH3COONH +4 in basic buffer would be higher than pure water.

Illustration 12: 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) + SO24 − (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
∴ [Ca2+] = [ SO24 − ] = 0.01765 M .

∴ Ksp = [Ca2+] [SO 24− ] = (0.01765)2 = 3.115 × 10–4.

[Type text]
[Type text]

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+ + 2NH3 Ag (NH3 ) 2 (aq.)
b–y a –2y y
where y is the amount of Ag+ which reacted with NH3.
K sp = [Ag + ][Cl− ] = (b − y)y
[Ag(NH3 ]+2 ] y
Kf = +
=
[Ag ][NH 3 ] 2
(b − y)(a − 2y)

After knowing the value of Ksp and Kf the value of solubility can be calculated.

Acid-base Indicators
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. phenolphthalein 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
HPh H + + Ph −
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 Hph also increases means 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).

[I−n ]
pH = pK IN + log
[HI n ]

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 [HI n ] = [I n– ] means pH = pK IN (at this point half of indicator is in
the acid form and half in the form of its conjugate form.

[Type text]
[Type text]

Indication (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.

MeOH Me + + OH −
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 in − 1 to pK in + 1

Case 1 : pH = pK in − 1
I−n
Means = 0.1 = 10%
[HIn]
Percentage ionization of indicator would be
I −n 0.10 HI n 1
−
× 100% = × 100% = × 100 = 9.1%
[I n ] + [HI n ] 0.10 HI n + (HI n ) 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.

ii) at pH = pK in + 1
[I −n ]
Mean = 10
[HIn]
Percentage of ionization of indicator is
[I −n ] 10 [HIn] 1000
−
× 100% = × 100% = = 91%
[I n ] + [HIn] 10 [HIn] + [HIn] 11

Thus most of the indicator is present in the ionized form I −n and solution gets the colour
characteristic. In fact pH = pKin + 1 is the minimum pH upto which the solution has a distinct

[Type text]
[Type text]

characteristic of I −n . 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 I −n .

Illustration 13: 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 3O + ]1 + [H3O + ]2
[H3O+] =
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 O + ][In − ]
K In = 3 [ionization constant of indicator is KIn]
[HIn]
= [H3O+] {since at neutral point [In–] = [HIn]} = 4.13 × 10–4.

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 phenolphthalein (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:

HPh H + + Ph −
Colourless Pink

[Type text]
[Type text]

[H + ][Ph − ]
Applying law of mass action, 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.

HIn + H 2 O H 3+ O + In −
`Acid form ' `Base form '

Conjuage acid-base pair

[In − ][H 3+ O] [HIn]
K In = ; K In = Ionization constant of indicator, [H 3+ O] = K In ×
[HIn] [In − ]
[HIn]
pH = – log10 [H 3+ 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.
MeOH Me+ + OH −
Yellow Re d

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.

[Type text]
[Type text]

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.

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.
OH O

−
OH
C 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.
CH 3
−
O3S NH N N
CH 3
Quinonoid form — Acidic solution (red)
OH -
H+
CH3
−
O3S N N N
CH3

[Type text]
[Type text]

Solved Problems
Objective

Problem 1: 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.

[salt]
Solution: pH = pKa + log
[acid]
10
= 5 + log if [salt]/[acid] = 10:1, then pH = 6
1
∴ (b)
Problem 2: 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 (d) 2.8 × 10–5.

Solution: 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 ∴ [OH–] = 2S = 2.8 × 10–4
4
∴ (c)

Problem 3: 1 ml of 0.1M HCl is added into 99 ml of water. Assume volumes are additive,
what is pH of resulting solution.
(a) 3 (b) 1
(c) 2 (d) 4

Solution: nHCl = MV = .1M × 10–3 L = 10–4 mol

Vfinal = (1+99) ml = 100 ml = .1L
[HCl] = n/v = 10–3 M = [H3O+]
pH = –log [H3O+] = – log 10–3 = 3

[Type text]
[Type text]

∴ (a)

Problem 4: What is pH of 0.02 M solution of ammonium chloride at 25°C? Kb(NH3)

= 1.8 × 10–5.
(a) 5.477 (b) 8.523
(c) 7 (d) 4.8732

Solution: For a salt of weak base and strong acid, at 25°C

1 1
pH = 7 – pKb – log C
2 2
1 1
= 7 – (– log 1.8 × 10–5) – log 0.02 = 5.477
2 2
∴(a)

Problem 5: The pH of 0.1M CH3COOH is 2.873. What is pH of 0.1M NH4OH.

Ka(CH3COOH) = 1.8 × 10–5 and Kb(NH4OH) = 1.8 × 10–5
(a) 11.127 (b) 2.873
(c) 7 (d) 9.53

Solution: Since Ka(CH3COOH) = Kb(NH3 and concentration are equal and so pH

(CH3COOH) = pOH (NH4OH)
pH = 2.873
∴ pH = 14 – pOH = 14 – 2.873 = 11.127
∴ (a)

Problem 6: 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: Let H+ ion concentration changes by x factor.

Q pH = – log [H3O+]
∴ pH + ∆pH = – log {x(H3O+]} = –log x – log [H3O+]
or ∆pH = – log x = 0.3
∴ x = 0.5
∴ (a)
0
Problem 7: Liquid NH3 ionises to a slight extent. At –60 C its ionic product
K NH3 =  NH 4+   NH 2−  = 10 −30
The number of NH 2− ions present per ml. of pure liquid NH3 are
(a) 300 ions (b) 400 ions
(c) 600 ions (d) 500 ions.

Solution: (c) K = [NH4+][NH2-] = x2

x = 10-15 = [NH2-]

[Type text]
[Type text]

1
[NH2-] = 10-15 × × 6.023 × 10 23
106
≈ 600 ions /mol

Problem 8: 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: Before adding HCl solution

pH = 1 [Q [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
4 × 10–3 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

∴(b)

Problem 9: 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: Since the resulting solution be acidic buffer, one may use Henderson equation.
[CH 3COO – ]
pH = pK a + log
[CH 3COOH]
Let n mol of CH3COONa be added to do so
n mol
or, pH = 4.74 + log vL
0.1 mol
vL
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

[Type text]
[Type text]

Amount of sodium acetate = 0.182 × 82 gm = 14.924 gm

∴(d)

Problem 10: 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 (CH3COOH) = 4.74.
(a) 0.125 (b) 0.225
(b) 0.01 (d) 0.872.

Solution: 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
nH3 CCOONa = 0.01 mole
After reaction, nCH3 COOH = 0.009 mol
nH − = (0.01 + 0.001) mol = 0.011 mol
3 CCOO

[CH 3COO − ]
pH = pKa + log
[CH 3COOH]
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
∴(d)

Problem 11. The expression for the solubility product of Al2(SO4)3 is

(a) Ksp = [Al3+] [SO42-] (b) Ksp = [Al3+]2 [SO42-]3
(b) Ksp = [Al3+]3 [SO42-]2 (b) Ksp = [Al3+]2 [SO42-]2
[MP PET 1999]
Solution: (b) Solubility of Al2(SO4)3
Al2(SO4)3 2Al+++ + 3SO4− −
Ksp = [Al3+]2 [SO42-]3

Problem 12. ON addition of amount chloride to a solution of ammonium hydroxide

(a) Dissociation of NH4OH increases
(b) Concentration of OH− decrease
(c) concentration of OH− decreases
(d) Concentration of NH4+ and OH− increases
[CPMT 1999, MP PMT 1989]
Solution: (c) Due to common ion effect.

[Type text]
[Type text]

Problem 13. The solubility product of a salt having general formula MX2, in water is :
4 × 10-12. The concentration of M2+ ions in the aqueous solution of the salt is
(a) 2.0 × 10-6 M (b) 1.0 × 10-4 M
(c) 1.6 × 10-4 M (d) 4.0 × 10-10 M
[AIEEE 2005]
2+ −
Solution: (b) MX2 M + 2X
s 2s
Ksp = (2S)2 (S) = 4S3
K sp 4 × 10−12
⇒ S = 23 =3 = 1.0 ×10 −4 M
4 4

Problem 14. If the solubility product Ksp of a sparingly soluble salt MX2 at 250C is 1.0 × 10-11,
the solubility of the salt in mole litre-1 at this temperature will be
(a) 2.46 × 1014 (b) 1.36 × 10-4
(c) 2.60 × 10−7 (d) 1.20 × 10-10
[RPMT 2000]

Solution: (b) MX2 M+ + 2X−; Ksp = 4S3

(s) (2s)2
K sp 1× 10−11
S= 2 3 = 3 = 1.35 × 10−4
4 4

Problem 15. Which of the following will occur if a 0.1 M solution of a weak acid is diluted to
0.01 M at constant temperature
(a) [H+] will decrease to 0.01 M
(b) pH will decrease
(c) Percentage ionization will increase
(d) Ka will increase
[UPSEAT 2001, 02]
Solution : (b)

Problem 16. 0.1 mole of CH3NH2 (Kb = 5 × 10 ) is mixed with 0.08 mole of HCl and diluted
-4

to one litre. What will be the H+ concentration in the solution ?

(a) 8 × 10-2 M (b) 8 × 10-11M
(c) 1.6 × 10-11 M (d) 8 × 10-5 M
[IIT 2005]

Solution : (b) CH3NH2 + HCl  → CH3NH3+Cl−

0.1 0.08 0
0.02 0 0.08
(Basic buffer solution)
0.08
pOH = pKb + log = pKb + 0.602
0.02

[Type text]
[Type text]

= 3.30 + 0.602 = 3.902

∴ pH = 10.09
[H+] = 7.99 × 10-11 ≈ 8 × 10-11 M

Problem 17. When solid potassium cyanide is added in water then

(a) pH will increase (b) pH will decrease
(c) pH will remain the same (d) Electrical conductivity will not change
[CPMT 2002; BHU 2002]

Solution : (a) KCN + H2O KOH + HCN . KOH is a strong base and HCN is
weak acid.

Problem 18. At 25 C, the dissociation constant of a base BOH is 1.0 × 10 . The

0 -12

concentration of Hydroxyl ions in 0.01 M aqueous solution of the base would

be
(a) 2.0 × 10-6 mol L-1 (b) 1.0 × 10-5 mol L-1
(c) 1.0 × 10−6 mol L-1 (d) 1.0 × 10-7 mol L-1
[CBSE PMT 2005]

Solution : (d) BOH B+ + OH−

initial C 0 0
At. eq. C - Cα Cα Cα
C 2α 2
Kb = = Cα 2 assuming α << 1; 1 - α ≈ 1
C (1 − α )
10-12 = 10-2 × α2; α2 = 10-10 ; α = 10-5

Problem 19. Aqueous solution of HCl has the pH = 4. Its molarity would be
(a) 4 M (b) 0.4 M
(c) 0.0001 M (d) 10 M
[RPMT 1999]
Solution : (c) pH = 4 means ; [H+] = 10-4 mol

Problem 20: How many gram of CaC2O4 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.
[CET 1997]

Solution: (a) CaC2 O 4 Ca ++ + C2 O 4– –

S S

K sp = S × S = S 2

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

[Type text]
[Type text]

Problem 21. If S and Ksp be the solubility and solubility product respectively, then
K sp
(a)For AgCl: S = K sp and for Al(OH)3: S = 3
9
(b) For BaSO4: S = K sp and for KI3 : S = K sp
K sp
(c) For Mg3(PO4)2: S = 5 and for AgBr: S = K sp
108
K sp
(d) For Bi2S3 and for Ca3(PO4)2 both: S = 5
108

Solution:. (b), (c), (d)

Problem 22: Kw of H2O at 373 K is 1 × 10-12. Identify which of the following is/are correct at
373K
(a) pKw of H2O is 12 (b) pH of H2O is 6
(c) H2O is neutral (d) A buffer solution of pH 6.5 is basic

Solution:. (a), (b), (c), (d)

Problem 23: 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) 14 – 5 – log3
(c) 14 – 5 + log3 (d) 8.523.

Solution: Let the initial equivalent of BOH be x

BOH + HCl → BCl + H2 O
Initial equivalent x 3/4x 0 0
3x x 3 3
At 3/4th eqv. pt. x− = 0 x x
4 4 4 4
[salt] 3x × 4
pOH = pK b + log = 5 + log
[Base] 4× x
pH = 14 – 5 – log 3 = 8.523
∴ (b),(d)
Problem 24: The pH at which Mg(OH)2 precipitate from a solution containing 0.10M Mg2+
ions [Kp of Mg(OH)2 = 1 × 10–11] is
(a) 5 (b) 9.5
(c) 4 (d) 10
Solution: When Mg(OH)2 starts precipitation, then
[Mg2+] [OH–]2 = Ksp of Mg(OH)2
[0.1] [OH–]2 = 1 × 10–11

[Type text]
[Type text]

∴ [OH–] = 10–5M
∴ pOH = 5
∴ pH = 14 – pOH
pH = 14 – 5 = 9: for more than 9 value of pH precipitation occurs
∴ (b), (d)

Problem 25: At what pH at 100°C, the solution will be basic

(Kw at 100°C is 5.6 × 10–13)
(a) 7 (b) 6.125
(c) 6.9 (d) 7.1

Solution: Kw = [H3O+] [–OH]

In water, [H3O+] = [–OH] ∴ Kw = [H3O+]2
log Kw = 2 log [H3O+]
1 1
pH = – log [H3O+] = – log Kw = – log {5.6 × 10–13}
2 2
= 6.1259 (for neutral solution)
∴(a), (c), (d)

26. Match the following

List – I List - II
(a) H2CO3 (pKa1 = 7.8) and (p) Dilution does not effect pH
NaHCO3 in 1:1 molar proportion
dissolved in water at 25°C
(b) BOH (pKb = 5.9) and B2SO4 in (q) Alkaline solution (pH = 7.8)
1:1 molar proportion dissolved in
water at 25°C
(c) pH of an aqueous solution of a (r) pH of solution increases with
salt of weak acid with a weak base concentration of salt
equal to 6.9 at which Kw = 10–13.8.
(d) Mixture at the exact end point (s) Acid buffer mixture
of titration of CH3COOH vs NaOH at
25°C.

Solution: (a - p, q, r, s) , (b – p, q), (c –p), (d – r)

Write-up – I

The degree of dissociation of weak electrolyte is inversely proportional to square root of

concentration. It is called Ostwald dilution law

[Type text]
[Type text]

Ka
α= As the temperature increases degree of dissociation will increase.
C
α1 K a1 α C2
= if conc. is same 1 = if acid is same.
α2 K a2 α2 C1

1. 0.01 M CH3COOH has 4.24% degree of dissociation. The degree of dissociation of 0.1
M CH3COOH will be
(a) 1.33% (b) 4.24%
(c) 5.24% (d) 0.33%

2. pH of 0.005 M HCOOH [Ka = 2 × 10-4] is equal to

(a) 3 (b) 2
(c) 4 (d) 5

3. Which of the following is strongest acidic solution

(a) pH = 1 (b) pH = 2
(c) pH = 3 (d) pH = 4

4. α1 and α2 are in ratio of 1 : 2 K a1 = 2 × 10 −4 . What will be K a2

(a) 8 × 10-4 (b) 2 × 10-4
(c) 4 × 10-4 (d) 1 × 10-4

Solution:
α1 c
1. (a) = 2
α2 c1

2. (a) [H+] = K a .c

3. (a) less in pH stronger in acid.

α1 Ka1
4. (a) =
α2 Ka2

Write-up – II

The solution which consumes [H+] or [OH-] or both simultaneously from externally added base
in order to give negligible change in pH, is known as buffer solution. In general, the solution
resists the change in pH. Buffer solution does not mean that there does not occur a pH change at
all. It implies the pH change occurs but in negligible amount. There are 2-types of buffer.
(i) Acidic buffer : it is a mixture of weak acid and its slat with strong base.
(ii) Basic buffer : it is a mixture of weak base and its salt with strong acid.

[Type text]
[Type text]

1. Which of the following mixture will be a buffer solution when dissolved in 500.00 mL of
water ?
(a) 0.200 mol of aniline and 0.200 mol of HCl
(b) 0.200 mol of aniline and 0.400 mol of NaOH
(c) 0.200 mol of NaCl and 0.100 mol of HCl
(d) 0.200 mol of aniline and 0.100 mol of HCl

2. pH of 0.01 M (NH4)2SO4 and 0.02 M NH4OH buffer (pKa of NH4+ = 9.26) is

(a) 4.74 + log2 (b) 4.74 – log 2
(c) 4.74 + log 1 (d) 9.26 + log 1

3. 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) 0.01 mol (d) 0.005 mol

Solution :

1. (d) For the formation of Buffer solution meq of weak base > meq of strong acid.

2. (d)
x
3. (c) 5.74 = 4.74 + log , calculating x = 0.02, hence (NH4)2SO4 required = 0.01
5 × 10 −3

Subjective

Problem 1: What amount of sodium propanoate should be added to one litre of an aqueous
solution containing 0.02 mol of propanoic acid to obtain a buffer solution of pH
4.75 ? What will be the pH if 0.01 mol of hydrogen chloride is dissolved in the
above buffer solution ? Compare the last pH value with the pH of 0.01 molar
HCl solution. Dissociation constant of propanoic acid at 250C is 1.34 × 10-5.

Solution : Using the expression

pH = pKa + log
[ salt ]
[ acid ]
We get 4.75 = -log(1.34 × 10-5) + log
[ salt ]
[ acid ]
which gives 4.75 = 4.87 + log
[ salt ]
0.02 M
or
[ Salt ] = 0.76 or [salt] = 1.52 × 10-2 M
0.02 M
Hence, Amount of sodium propanoate to be added = 1.52 × 10-2 mol
The addition of 0.01 mol of hydrogen chloride convert the equivalent amount of
sodium propanoate into propanoic acid .

[Type text]
[Type text]

Hence, we will have

(0.0152 - 0.01) mol L-1
pH = 4.87 + log = 4.87 + log(0.173)
(0.02+0.01)mol L-1
= 4.87 – 0.76 = 4.11
The pH of 0.01 molar HCl solution would be
pH = -log (0.01) = 2

Problem 2: The solubility of Mg(OH)2 in pure water is 9.57 × 10

-3
g L-1. Calculate its
solubility (g L-1) in 0.02 M Mg(NO3)2

Solution : We have
Molar mass of Mg(OH)2 = 58 g mol-1
9.57 × 10−3 gL−1
Concentration of Mg(OH)2 in pure water = −1
= 1.65 × 10−4 mol L−1
58 g mol
If follows that
Mg(OH)2 (s) Mg2+ (aq) + 2OH− (aq)
1.65 × 10-4 mol L-1 2 × 1.65 × 10-4 mol L-1
Hence, Ksp (Mg(OH)2) = [Mg2+] [OH−]2
= (1.65 × 10-4) (2 × 1.65 × 10-4)2 (mol L-1)3
= 1.80 × 10-11 (mol L-1)3
Now in 0.02 M Mg(NO3)2 solution. Concentration of Mg2+ ions = 0.02 M
The concentration of OH− that can exist in 0.02 M Mg(NO3)2 solution is
1/ 2
 K sp  1/ 2
 1.80 × 10 −11 (mol L−1 )3 
−
[OH ] =   =  = 3 × 10 −5 mol L−1
  Mg 2+    0.02 mol L−1 
 
1
Concentration of Mg(OH)2 in 0.02 M Mg(NO3)2 solution = × 3 × 10−5 mol L−1
2
Solubility of Mg(OH)2 in 0.02 M Mg(NO3)2 solution =
1 −5 −1  −1
 × 3 × 10 mol L  (58 g mol )
2 
= 8.7 × 10 g L .
-4 -1

Problem 3: 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.

10
Solution : Amount of SO2 in atmosphere = = 10 −5
10 6
molar conc. of SO2 in presence of water
= (Amount of SO2 × solubility of SO2 in water)
[SO2] = 10-5 × 1.3653 mol/L
= 1.3653 × 10-5 M

[Type text]
[Type text]

Now H2SO3 H+ + HSO3−

[1.3653 × 10-5] – x x x as eq.
2
x
ka = = 10 −1.92
(1.3653 × 10 −5 − x
solving x = 1.364 × 10-5
∴ pH = -log(1.364 × 10-5) = 4.865
2–
Problem 4: A solution contains 0.1 M H2S and 0.3 M HCl. Calculate the conc. of S and
–
HS ions in solution. Given K a1 and K a 2 for H2S are 10 –7
and 1.3 × 10–13
respectively.

Solution: [H2S] = 0.1 ; [HCl] = 0.3M

∴ [H+] = 0.3 M
H2S H+ + HS-
[H + ][HS- ] 10 −7 × 0.1
Ka = 10-7 = ⇒ [HS-] = = 3.3 × 10-8
[H 2 S] 0.3
− + 2−
HS H + S
−13
 H +   S 2 − 
K a2 = 1.3 × 10 =
 HS − 
1
1.3 × 10 −13 × × 10 −7
⇒  S 2 −  = 3 = 1.44 × 10-20
0.3

Problem 5: The dissociation constant of a weak acid HA is 4.9 × 10-8. After making the
necessary approximations, calculate (i) percentage ionization, (ii) pH and (iii)
OH− concentration in a decimolar solution of the acid. Water has a pH of 7.

Solution: (i) If α is the degree of dissociation of the weak of the weak acid HA, we will
have
HA H+ + A−
(0.1 M) (1 - α) (0.1 M)α (0.1 M) α
 H   A  (0.1M )α
+ - 2
Ka =     =
[ HA ] 1−α
Assuming α << 1, we will have
Ka = (0.1 M) α2
Ka 4.9 × 10−8 M
or α= = = 7 × 10−4
0.1M 0.1M
7 × 10−4
Hence, Percentage ionization = × 100 = 7 × 10−2
1
(ii) We have
[H+] = (0.1M) α = 7 × 10-5 M

[Type text]
[Type text]

pH = -log{[H+]/M} = -log(7 × 10-5) = 4.15

(iii) Since water has a pH = 7, we will have
[H+] = [OH−] = 10-7 M or [H+] [OH−] = 10-14 M2
Thus, [OH−] in 0.1 M solution of acid would be
10−4 M 2 10−14 M 2
[OH−] = = = 1.43 ×10−10 M
[H + ] 7 ×10−5 M

Problem 6: Calculate the pH at the equivalence point of the titration between 0.1M
CH3COOH ( 25 ml) with 0.05 M NaOH. Ka (CH3COOH) = 1.8 × 10–5.

Solution: We have already seen that even though when CH3COOH is titrated with NaOH
the reaction does not go to completion but instead reaches equilibrium. We can
assume that the reaction is complete and then salt gets hydrolysed because, this
assumption will help us to do the problem easily and it does not effect our answer.
Kw Ka
∴ [H+] =
C

First of all we would calculate the concentration of the salt, CH3COONa. For
reaching equivalence point,
N1V1 = N2V2
∴ 0.1 × 25 = 0.05 × V2 ⇒ V2 = 50 ml
0.1× 25 0.1
Therefore [CH3COONa] = =
75 3
10−14 × 1.8 × 10−5
∴[H+] = = 2.32 × 10–5
0.1 3
⇒ pH = – log 2.32 × 10–5 = 8.63
-32
Problem 7: Given the solubility product of Pb3 (PO4)2 is 1.5 x 10 . Determine the solubility
in gms/litre.

Solution: Solubility product of Pb3 (PO4)2 = 1.5 × 10–32

Pb3 (PO4)2 3Pb2+ + 2PO 34−
If x is the solubility of Pb3 (PO4)2
Then Ksp = (3x)3 (2x)2 = 108 x5
1
Ksp  1.5 ×10−32  5
x= 5 = 
108  108 
x = 1.692 × 10–7 moles/lit
Molecular mass of Pb3(PO4)2 = 811
x = 1.692 × 10–7 × 811 g/lit = 1.37 × 10–4 g/lit

[Type text]
[Type text]

Problem 8: 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 + SO24 −

Thus, every one mole of (NH4)2SO4 gives two moles of NH +4 .
∴ millimoles of NH3, (NH4OH) = 100 × 0.1 = 10 millimoles
millimoles of (NH4)2SO4 = 100 × x = 100 x millimoles
millimoles of NH +4 = 200 × x = 200 x millimoles
∴ 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
log 20x = 0
20 x = 1
1
x= = 0.05.
20

Problem 9: An aqueous solution of metal bromide MBr2 (0.05M) in saturated with H2S.
What is the minimum pH at which MS will ppt.?
Ksp =(MS) = 6 × 10–21
Concentration of standard H2S = .1
Ka1(H2S) = 1 × 10–7
Ka2(H2S) = 1.3 × 10–13

Solution: In saturated solution of MS

MS(s) M++ + S––
K SP 6 × 10 −21
∴ [S– –] = ++
= = 1.2 × 10–19
[M ] .05
The precipitate of MS will form only if [S––] exceeds the concentration of
1.2 × 10–19
H2S H+ + HS– Ka1
H2S– H+ + S-- Ka2
——————————————
H2S 2H+ + S–– K = 1.3 × 10–20
[H+ ]2 [S − − [
K=
[H2S]
[H+ ]2 × 1.2 × 10 −19
1.3 × 10–20 =
.1
∴[H+] = 0.109

[Type text]
[Type text]

pH = 0.96

Problem 10: How much Ag+ would remain in solution after mixing equal volumes of 0.080
M AgNO3 and 0.08N HOCN.
Given that : Ksp for AgCN = 2.3 × 10–7
Ka(HOCN) = 3.3 × 10–4

Solution: HOCN H+ + –OCN

Ag+ + –OCN AgOCN(s) Due to two fold dilution,
+
Let [Ag ] = x
Amount of [Ag+] pptted = (.04 –x)M
Amount of –CN ppted = (.04 – x)N
[HOCN] = x –[–OCN] = xM
[H+] = 0.4 - x
[OCN] Ka 3.3 × 10−4 2.3 × 10 −4 × n
Then, = = –
or, [ OCN} =
[HOCN [H + ] .04 − x .04 − x
3.3 × 10−4 x 2
And [Ag+][–OCN] = = Ksp = 2.3 × 10–7
.04 − x
or, x = [Ag+] = 5 × 10–3

Problem 11: 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/cm3.

Solution: Given density of formic acid = 1.22 g/cm3

∴ Weight of formic acid in 1 litre solution = 1.22 × 103
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 12: Calculate the concentration of all species of significant concentrations present
in 0.1 M H3PO4 solution. K1 = 7.5 × 10–3, K2 = 6.2 × 10–8, K3 = 3.6 × 10–3.
I step H3PO4 H+ + H2P O −4 ; K1 = 7.5 × 10–3
II step H2P O −4 H+ + HP O 24 − ; K2 = 6.2 × 10–8
III step HP O 24 − H+ + P O 34− ; K3 = 3.6 × 10–13
for I step : H3PO4 H+ + H2P O −4

[Type text]
[Type text]

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− ] (0.024 + y)y
Thus, K2 = −
or 6.2 × 10–8 =
[H 2 PO 4 ] (0.024 – y)
Q 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 4 ] = K2 = 6.2 ×10–8.
2−

For III step : HP O 24 − H+ + P O 34−

(6.2 × 10–8 –x) (0.024 + x) x
+ 3−
[H ][PO 4 ] (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 = ∴ x = = 9.3 × 10 −19 .
6.2 ×10−8 0.024

Problem 13: 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;

–11 –1 –1
Kf = 10 mol L sec
The backward reaction is of hydrolysis of sodium acetate

[Type text]
[Type text]

−1
K K  K
Q 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 ∴ E a b = A b × e− Eabac / RT
 −50 ×103 
10 –20
= Ab × e   ∴ Ab = 2.71 × 10+16.
 2 × 298 

Problem 14: Calculate degree of hydrolysis and pH of 0.2 M solution of NH 4 Cl . Given

K b for NH 4 OH is 1.8 × 10 –5 .

Solution: NH 4 Cl + H 2 O NH 4 OH + HCl
Before hydrolysis 1 0 0
After hydrolysis 1 –h h h
Where h is degree of hydrolysis
 Kh   Kw  10 –14
h=  =  = = 5.27 × 10 –5
 C   K b .C  1.8 × 10 × 0.2
–5

From HCl, strong acid

K  K   10 –14 × 0.2 
∴ [H + ] = C.h = C  h  = (K h .C) =  w .C  =  –5 
= 1.054 × 10 –5
 C   Kb   1.8 × 10 
∴ pH = – log[H + ] = – log1.054 ×10 –5
= 4.9771

Problem 15: 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?

1
Solution: For weak acid HA : α HA = = 0.01, [HA] = 0.1 M
100
∴ K a = Cα 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

[Type text]
[Type text]

(1 – α) α α
–
Q [A ] is provided by NaA since dissociation of HA in presence of NaA is
suppressed due to a common ion effect.
[H + ][A − ] (Cα) × 0.2
∴ Ka = = = 10−5
[HA] C(1 − α)
∴ α = 5 × 10−5

[Type text]
[Type text]

KVPY
1. The pH of a 0.1M solution of a weak monoprotic acid having a degree of dissociation of 0.1 in water, is
(2007)
(A) 4.4 (B) 4.0 (C) 2.4 (D) 2.0

2. The volume of 0.1M acetic acid (pKa = 4.76) that should be added to 10ml of 0.2M sodium acetate
solution to prepare a buffer solution of pH 4.91 is – (2007)
(A) 14.2 ml (B) 4.0 ml (C) 20.0 ml (D) 70.0 ml

3. An aqueous solution of HCl has a pH of 2.0 When water is added to increase the pH to 5.0 the
hydrogen ion
concentration (2010)
(A) Remains the same (B) Decreases three-fold
(C) Increases three-fold (D) Decreases thousand-fold

4. The solubility curve of KNO3 in water is shown below. (2011)

250
Solubility (gram)/100

200 •
•
gram of water

150
100 •
50 •
0
0 10 20 30 40 50
Temperature (°C)

the amount of KNO3 that dissolves in 50g of water at 40°C is closest to

(A) 100g (B) 150g (C) 200g (D) 50g

5. The pH of 0.1 M aqueous solutions of NaCl, CH3COONa and NH4Cl will follow the order
(2014)
(A) NaCl < CH3 COONa < NH4 Cl (B) NH4 Cl < NaCl < CH3 COONa
(C) NH4 Cl < CH3 COONa < NaCl (D) NaCl < NH4 Cl < CH3 COONa

Answer Keys:
1. D 2. A 3. D 4.A 5.B

[Type text]
[Type text]

Assignments

SECTION – I Single Choice Questions

LEVEL - I

1. An indicator is a weak acid and pH range of its colour is 3 to 5. If the neutral points of the
indicator lies in the centre of the hydrogen ion concentration corresponding to given pH
range then pH at the equivalence points is :
(a) 3.3 (b) 4.0
(c) 7.0 (d) 5.0.

2. A buffer solution contains 100 mL of 0.01 M CH3COOH and 200 mL of 0.02 M

CH3COONa. 700 mL of water is added. pH before and after dilution are : (pKa = 4.74)
(a) 5.04, 5.04 (b) 5.04, 0.504
(c) 5.04, 1.54 (d) 5.34, 5.34.
3. H2O + H3PO4 H3O+ + H2 PO −4 , pK1 = 2.15
− + 2−
H2O + H2 PO 4 H3O + H PO , 4 pK2 = 7.20
Hence, pH of 0.01 M NaH2PO4 is :
(a) 9.35 (b) 4.675
(c) 2.675 (d) 7.350.

4. pH of a mixture of 1 M benzoic acid (pKa = 4.20) and 1 M sodium benzoate is 4.5. In

300 mL buffer, benzoic acid is :
(a) 200 mL (b) 150 mL
(c) 100 mL (d) 50 mL.
5. 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.
6. 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.

7. pH of a saturated solution of Ba(OH)2 is 12. Hence, Ksp of Ba(OH)2 is :

(a) 5 × 10–7 M3 (b) 5 × 10–4 M2
(c) 1 × 10 M
–6 3
(d) 4 × 10–6 M3.
8. A weak acid HX has the dissociation const 1 × 10–5 it forms a salt NaX on reaction with
alkali. The percentage hydrolysis of 0.1 M solution of NaX is
(a) 0.0001 (b) 0.01
(c) 0.1 (d) 0.15

[Type text]
[Type text]

9. 0.1 mole of CH3NH2 (Kb = 5 × 10–4) is mixed with 0.08 mole of HCl and diluted to 1 lt.
What will be the H+ ion conc in the solution
(a) 8 × 10–2M (b) 8 × 10–11M
(c) 1.6 × 10–11M (d) 8 × 10–5M

10. An acetic acid and sodium acetate buffer has pH = 5.36 the ratio of concentration of
[OAc]/HOAc] is (pKa of acetic acid = 4.76)
(a) 6 : 1 (b) 4 : 3
(c) 1 : 1 (d) 4 : 1

11. The solubility products of Al(OH)3 and Zn(OH)2 are 8.5 × 10–23 and 1.8 × 10–14
respectively. If NH4OH 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.

12. In the hydrolytic equilibrium A − + H 2 O HA + OH −

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.
13. 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

14. Let the solubilities of AgCl in H2O, 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

15. 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
16. 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
–4
(c) 2.8 × 10 (d) 2.8 × 10–5.
17. The solubility of Fe(OH)3 would be maximum in
(a) 0.1 M NaOH (b) 0.1 M HCl
(c) 0.1 M KOH (d) 0.1 M H2SO4.

18. pKa values of three acids A, B and C are 4.5, 3.5 and 6.5 respectively. Which of the
following represents the correct order of acid strength ?
(a) A > B > C (b) C > A > B

[Type text]
[Type text]

(c) B>A>C (d) C > B > A.

19. The solubility of M(OH)3 is x mol L–1. Its Ksp would be

(a) 9x3 (d) 3x4
4
(c) 27x (d) 9x4

20. 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
–3
(b) 10 times increases (d) None

LEVEL - II

1. A solution is a mixture of 0.05 M NaCl and 0.05 M Nal. The concentration of iodide ion
in the solution when AgCl just starts precipitating is equal to :
(Ksp AgCl = 1 × 10–10 M2; Ksp AgI = 4 × 10–16 M2)
(a) 4 × 10–6 M (b) 2 × 10–8 M
(c) 2 × 10–7 M (d) 8 × 10–15 M

2. 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 the small intestine is about 8. Aspirin will be
(a) un ionized in the small intestine and in the stomach
(b) completely ionized in the small intestine and in the stomach
(c) ionized in the stomach and almost un ionised in the small intestine
(d) ionized in the small intestine and almost un ionised in the stomach

3. If pKb for fluoride ion at 25°C is 10.83, the ionization const. of HF in water at the
temperature is
(a) 1.74 × 10–5 (b) 3.52 × 10–3
(c) 6.75 × 10–4 (d) 5.38 × 10–2

4. The pH of 0.1M CH3COOH is 2.873. What is pH of 0.1M NH4OH. Ka(CH3COOH) = 1.8

× 10–5 and Kb(NH4OH) = 1.8 × 10–5
(a) 11.127 (b) 2.873
(b) 7 (d) 9.53

5. 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.

6. The pOH of 10–8 M HCl is

(a) 8 (b) 6
(b) Between 6 and 7 (d) Between 7 and 8.

[Type text]
[Type text]

7. Given that the dissociation constant for H2O, Kw = 1 × 10–14 mol2 litre–2, what is the pH of
a 0.001 M KOH solution ?
(a) 10–11 (b) 10–3
(c) 3 (d) 11.

8. An acid solution of pH 6 is diluted thousand times. The pH of solution becomes approx.

(a) 6.69 (b) 6
(c) 4 (d) 9

9. The pH of an aqueous solution of a 0.1 M solution of a weak monoprotic acid, which is

1%, ionized is
(a) 1 (b) 2
(c) 3 (d) 11

10. In a mixture of weak of acid and its salt with strong acid, the ratio of concentration of salt
to acid is increased ten times the pH of the solution
(a) Increases by 10 (b) Decreases by 10
(c) Decreases by 1 (d) Increases by 1.

LEVEL - II

1. Which of the following is the correct. Expression of degree of dissociation for weak acid.
(Assume α is negligible w.r.t to unity).
Ka Kw × c
(a) (b)
c Ka
Kw 1
(c) × (d) K b of conjugate base × c
K b of conjugatebase c

2. 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 10–4M[HCl] (b) 10–3 M[Ag+] and 10–3 M [Cl–]
(c) 10–6M [Ag+] and 10–6 M [Cl-–] (d) 10–2 M [Ag+] and 10–2M [Cl–].

3. Correct options for the following reaction is :-

NH3 + H2O N+H4 + OH
+ 
(a) K a  N H 4  + Kb (NH3) = 10-14 (b) K a (NH + ) × K b ( NH 3 ) = 1/ K w
  4

(c) K a (NH 4+ ) × K b ( NH3 ) = K w (d) pK a ( NH + ) + pK b ( NH3 ) = 14

4

[Type text]
[Type text]

4. pH of 0.03 M NaH2PO4
(a) Increases with dilution (b) decreases with dilutions
(c) does not depend upon concentration (d) changes with change in temperature

5. Which of the following statements is are right

(a) The pH of 1 × 10-8 M solution of HCl is 8
(b) The conjugate also of H2 PO −4 is HPO24 −
(c) auto protolysis constant of water increases with temperature
(d) when a solution of weak monoprtic acid is titrated against a strong base, at half
1
neutralization point pH = pK a
2

6. When a 2 M aqueous solution of CH3COOH is diluted with water. The change which may
occure is
(a) The concentration of H+ increases (b) the degree of dissociation of Acid increases
(c) the value of ka increases (d) the number of H+ ion increases

7. Which of the following statement are true for a solution saturated with AgCl and AgBr.
If their solubilities in mol lit-1 in separate solutions are x and y respectively.
(a) [Ag+] = [Br−] + [Cl−] (b) [Cl−] > [Br−]
−
(c) [Br ] > y (d) [Ag+] = x + y

8. Pure NH3 is placed in a vessel at a temperature where its dissociation constant (K) is
appreciable, At equilibrium
(a) K does not change with pressure
(b) K does not change with [NH3]
(c) concentration of NH3 does not change with pressure
(d) concentration of Hydrogen in less than that of nitrogen.

9. Which of the following solution will have no effect on pH with dilution

(a) 0.1 M NaHS (b) 5 M H2CO3 + 5M NaHCO3
(c) 1 M CH3COONH4 (d) 1 M NH4Cl

10. Which of the following solution will have pH =13 assume complete dissociations
(a) 2g of NaOH in 500 ml solution (b) 100 ml of solution of 0.05 M Ca(OH)2
(c) 100 ml of solution of 0.1 N Ca(OH)2 (d) 4g of NaOH in 500 ml solution.

SECTION – III Comprehension Type Questions

Write-up I
If a sparingly soluble salt is placed in water, after some time an equilibrium is established when
the rate of dissolution of ions from the solid equals the rate of precipitation of ions from the
saturated solution at a particular temperature. Thus, a dynamic equilibrium exists between the
undissociated solid species and the dissolved ionic species in a saturated solution at a particular
temperature. For example, in AgCl, we have the following equilibrium :

[Type text]
[Type text]

AgCl (s) Ag+ (aq) + Cl− (aq.)

The equilibrium constant
 Ag +  Cl − 
K eq = 
[ AgCl ]
Q [AgCl] is constant
∴ Keq × [AgCl] = [Ag+] [Cl-]
⇒ Ksp(AgCl) = [Ag+] [Cl-]

If there would not have been a saturated solution, then from equation (1), Keq. [AgCl] ≠
Ksp, but Keq. [AgCl] = QAgCl, where Q is ionic product. It implies that for a saturated
solution, Q = Ksp
Ksp is temperature dependent.
When Q < Ksp, then the solution is unsaturated and then will be no precipitate.

When Q = Ksp, then solution will be saturated, no ppt.

when Q = Ksp, the solution will be supersaturated and there will be formation of precipitate.

1. pH of a saturated solution of Ba(OH)2 is 12. Hence Ksp of Ba(OH)2 is:

(a) 5 × 10-7 M3 (b) 5 × 10-4 M2
(c) 1 × 10-6 M3 (d) 4 × 10-6 M3

2. A solution is a mixture of 0.05 M NaCl and 0.05 M NaI. The concentration of iodide ion
in the solution when AgCl just starts precipitating is equal to:
(Ksp AgCl = 1 × 10-10 M2; Ksp AgI = 4 × 10-16 M2)
(a) 4 × 10-6 M (b) 2 × 10-8 M
(c) 2 × 10-7 M (d) 8 × 10-15 M

3. Silver iodide is used in cloud seeding to produce rain

AgI Ag+(aq) + I− (aq); Ksp = 8.5 × 10-7. AgNO3 and KI are mixed to give
[Ag ] = 0.010 M; [I−] = 0.015 M. Will AgI precipitate ?
+

(a) yes (b) no

(d) this depends on  NO3−  and [K ]
+
(c) can’t say

4. Slaked lime, Ca(OH)2 is used extensively in sewage treatment. What is the

maximum pH that can be established in Ca(OH)2(aq.)
Ca(OH)2(s) Ca2+ (aq) + 2OH− (aq) ; Ksp = 5.5 × 10-6
(a) 1.66 (b) 12.34
(c) 7 (d) 14
Write-up II
Acidity or alkalinity of a solution depend upon the concentration of hydrogen ion relative
to that of hydroxyl ions. The product of hydrogen ion & hydroxyl ion concentration is
given by
Kw = [H+] [OH–]

[Type text]
[Type text]

the value of which depends only on the temperature & not on the individual ionic
concentration. If the concentration of hydrogen ions exceeds that of the hydroxyl ions, the
solution is said to be acidic; whereas, if concentration of hydroxyl ion exceeds that of the
hydrogen ions, the solution is said to be alkaline. The pH corresponding to the acidic and
alkaline solutions at 25ºC will be less than and greater than seven, respectively. To
confirm the above facts 0.5 M CH3COOH is taken for the experiments.
[Given : Ka of acetic acid = 1.8 ×10–5]

1. Degree of dissociation of acetic acid is -

(a) 66 × 10–2 (b) 6 × 10–3
(c) 3 × 10–3 (d) 5 × 10–3
2. pH of the solution will be -
(a) 2.52 (b) 2.22
(c) 5 (d) 3.92

3. If pH of the solution is doubled, what will be the concentration of acetic acid -

(a) 1.8 × 10–5 M (b) 1.0 M
–5
(c) 1.374 × 10 M (d) 1.25 × 10–3 M
4. To what volume at 25º C must 1 dm3 of this solution be diluted in order to double the pH-
(a) 3.37 × 104 dm3 (b) 2.34 × 102 dm3
(c) 1.68 × 104 dm3 (d) 3.18 × 103 dm3

5. Now to increase the hydrogen ion concentration 100 dm3 of 0.1M HCl solution is added
to100 dm3 of 0.5 M acetic acid solution, then what will be the pH of the final solution -
(a) 6 (b) 1.3
(c) 3 (d) 1

Write-up III
In qualitative analysis, cations of group II as well as group IV both precipitated in the
form of sulphides due to low value of Ksp of group II sulphides, group reagent is H2S in
presence of dil. HCl and due to high value of Ksp of group IV sulphides, group reagent is
H2S in presence of NH4OH and NH4Cl.
In a 0.1M H2S solution, Sn2+, Cd2+ and Ni2+ ions are present in equimolar concentration
(0.1 M).
Given:
K a1 Ka2(H2S) = 10-7, K a 2 (H2S) = 10–14, Ksp (SnS) = 8 × 10–29 Ksp (CdS) = 10–28,
Ksp (NiS) =3 × 10–21

6. If HCl solution is passed slowly then which sulphide will precipitate first -
(a) SnS (b) CdS
(c) NiS (d) none of these

7. At what pH precipitate of NiS will form -

[Type text]
[Type text]

(a) 12.76 (b) 7

(c) 1.24 (d) 4

8. Which of the following sulphide is more soluble in pure water-

(a) CdS (b) NiS
(c) SnS (d) all have equal solubility

9. If 0.1 M HCl is mixed in the solution containing only 0.1 M Cd2+ and saturated with H2S
then concentration of Cd2+ remains in the solution after CdS has precipitated -
(a) 8.2 × 10-8 (b) 8.2 × 10-9
(c) 5.6 ×10-7 (d) 5.6 ×10-8

Answers to Assignments

SECTION - I

LEVEL - I
1. (a) 2. (d) 3 (b) 4 (c) 5. (c)
6 (c) 7 (a) 8 (b) 9 (b) 10 (d)
11 (a) 12. (a) 13. (b) 14. (c) 15. (b)
16 (c) 17. (d) 18. (c) 19. (c) 20. (a)

LEVEL - II
1. (a) 2. (d) 3 (c) 4 (a) 5. (b)
6 (d) 7 (d) 8 (a) 9 (c) 10 (d)

SECTION - II
1. (a, c) 2. (a, b, d) 3 (c, d) 4 (c, d)
5. (b, c) 6 (b, d) 7 (a, d) 8 (a, b, c)
9 (a, b, c) 10 (a, b, c)

SECTION - III

1. (a) 2. (c) 3. (a) 4. (b) 5. (b)

6. (a) 7. (c) 8. (a) 9. (b) 10. (a)
11. (c) 12. (b) 13. (a)

[Type text]
[Type text]

[Type text]