Ionic Equlibrium Final

CHEMISTRY IONIC EQUILIBRIUM
IONIC EQUILIBRIUM
INTRODUCTION
Ionic equilibrium is the study of the reversible reaction involving formation of ions in water or we
can say that the equilibrium existing in solution involving ions. Whereas in the chemical equilibrium we
study involvent of molecules only.
Arrhenius Concept
a) Acid: A substance which furnishes H+ ions in aqueous solution i.e. when dissolved in water. e.g.
HCl, CH3COOH.
HCl (aq) 
→ H+(aq) + Cl-(aq)
KHSO4 (aq)  → K+(aq) + H+(aq) + SO 24 − (aq)
Base: A substance which furnishes OH- ions in aqueous solution i.e. when dissolved in water.
e.g. NH4OH, KOH etc.
KOH (aq)  → K+(aq) + OH − (aq)
ˆˆ† NH4+ (aq) + OH − (aq)
NH4OH (aq) ‡ˆˆ
b) Strength of acids and bases according to Arrhenius concepts: Acids and bases which are almost
completely ionized in aqueous solution are termed as strong acids & strong bases respectively
where as acids and bases which are weakly ionized in aqueous solution are called weak acids &
weak bases respectively.
Strong Acid HCl(aq)  → H+(aq) + Cl − (aq)
ˆˆ† H+(aq) + CH3COO-(aq)
Weak Acid CH3COOH(aq) ‡ˆˆ
→ Na+(aq) + OH − (aq)
Strong Base NaOH(aq) 
ˆˆ† NH +4 (aq) + OH-(aq) .
Weak Base NH4OH (aq) ‡ˆˆ
c) According to Arrhenius concept, neutralization of acids and bases is basically a reaction between
H+ and OH- ions in solutions :
H+ (aq) + OH-(aq)  → H2O (l)
In the above reaction, complete neutralization has taken place, therefore sign of single arrow
( → ) has been used.
Bronsted - Lowry Concept

It may be summarized as below:
a) Acid: An acid is a substance (a molecule or a cation or an anion) that can furnish proton i.e. H+
ion i.e. proton donor
Acid 
→ H+ + [Base]
→ H+ + Cl −
Molecular species : HCl 
Cationic species : [Al(H2O)6]3+ 
→ H+ + [(Al(H2O)5OH]2+
Anionic species : HCO3−  → H+ + CO 32 −
Base: A base is a substance ( a molecule or a cation or an anion) that can accept proton i.e. H+
ion i.e. proton acceptor. e.g.
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IONIC EQUILIBRIUM CHEMISTRY
Base + H+ 
→ [Acid]
Molecular species: H2O + H+ 
→ H3O+
Anionic species: CO3−2 + H+ 
→ HCO3−
Anionic species: CN- + H+ 
→ HCN.
b) Lowry-Bronsted concept does not vary appreciably from Arrhenius concept for acids, but in
case of bases, it varies and need not contain OH - ions only. Therefore, ions like Cl -,
CH3COO-, Br − are bases, although OH- ions are absent in them e.g.
→ H + + Br −
HBr 
Acid Base
c) Conjugate Acid-Base Pairs

Conjugate acid: Chemical species, that is formed from the base by the gain of proton or H+ ion
e.g.
Base + H + 
→ [conjugate acid]
e.g. H 2 O + H + 
→ H 3O +
Conjugate Base: Chemical speices, that is formed from the acid by the loss of proton or H+ ion
e.g.
Acid  → H+ + [conjugate base]
e.g. HCl → H+ + Cl − .
d) Formation of conjugate acids and bases are simultaneous process.
Conjugage Acid-Base pair
Acid 1 + Base2 ˆˆ† Acid2 + Base1

‡ˆˆ
(HCl) (H 2 O) (H 3 O+ ) (Cl − )
Conjugage Acid-Base pair
e) Relative strength of conjugate acid-base pair: In the above reaction, two acids (HCl & H3O+
ion) are competing to donate protons, since the acid HCl wins, it is stronger acid. Similary H2O
accepts proton more readily than Cl-, therefore H2O is stronger base than Cl-. Hence, we conclude
that :
a) Stronger acid  → weak conjugate base & vice-versa
b) Stronger base 
→ weak conjugate acid & vice-versa
Conjugate Acid-Base pair
Stronger acid + Stronger Base Weaker acid + Weaker Base
Conjugate Acid-Base pair

Lewis Concept
a) Lewis acid: species which can accept electron pair(s).
b) Lewis base: species which can donate electron pair(s)
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→ H3N+ →B−F3
: NH3 + BF3 
Lewis base Lewis acid
c) All Bronsted bases are Lewis bases but all Bronsted acids are not Lewis acids because Bronsted acid
can give a proton, but may not be capable of accepting a pair of electron e.g HCl, H2SO4.
Conditions for Lewis Acid
1. Molecules whose central atom have an incomplete octet e.g. BF3, AlCl3.
H H H H
BMe3 + N N N N BMe3
H H H H
2. Simple cations: e.g. H+, Ag+.

..
2 N H3 + Ag+ 
→ [H3N → Ag ← NH3]+
3. Compounds in which the central atom has empty d-orbital and/or other orbitals (s and p) of
suitable energy and may acquire more than an octet of valence electrons e.g. PF3 . SiF4.
SiF4 + 2 F − 
→ [SiF6 ]2−
4. Molecules containing multiple bonds. e.g. between atoms of dissimilar electronegativity e.g.
CO2, SO2.
OH
δ+ δ–
O = C = O + OH 
→
Lewis a cid Lewis base
O O
5. A closed shell molecule may be able to use one of the unoccupied antibonding molecular orbitals
to accommodate an incoming electron pair.
e.g. - Tetracyano ethane.
Conditions for Lewis Bases
1. Molecule(s) whose central atom has unshared pair(s) of electrons e.g. -

H 2 O , NH 3 , ROH, ROR
2. Multiple bonded compounds which form coordination compounds with transition metals e.g. CO,
NO, ethylene.
3. Simple negative Cl− , F− anions : etc.
4. Solvent system concept

Acid: A species that increases the concentration of the characteristic cation of the solvent e.g.
ˆˆ† SO2+ + 2Cl-
SOCl2 ‡ˆˆ

Base: A species that increases the concentration of the characteristic anion of the solvent. e.g.
sulfite salts.
ˆˆ† SO2+ + SO 32 −
2SO2 ‡ˆˆ
Strength of Acids And Bases

Protonic acid may be classified as
1. Hydroacid: Acid in which acidic hydrogen atom is directly linked to the second element is called
Hydro acid e.g. -
Binary hydrides: HF, HCl, H2S etc.
2. Oxy acid: Acid in which acidic hydrogen is linked to central atom via an oxygen atom e.g.
O
H2SO4, HNO3,
O S
HO OH
What is meant by strength of acids and bases:

According to Lowry-Bronsted concept, a stronger acid has a greater tendency to donate a
proton and a strong base has a greater tendency to accept a proton.
Quantitatively, the magnitude of strength of Bronsted acid & Bronsted base in aqueous solution
is expressed by acidity constant (Ka) and basicity constant (Kb) respectively.
ˆˆ† H3O+ (aq) + F-(aq)

a) For acid: HF(aq) + H2O( l ) ‡ˆˆ
[H 3 O+ ] [F− ]
Ka = and thus, pKa = - log Ka
[HF]
If K a → ∞ , given substance is a strong acid.
If K a << 1 or pKa > 0, given substance is a weak acid.
ˆˆ† NH +4 (aq) + OH-(aq)

b) For Base: NH3(aq) + H2O ( l ) ‡ˆˆ
[NH +4 ] [OH − ]
Kb = and thus pKb = -log Kb.
[NH 3 ]
If K b → ∞ , given substance is a strong base.
If K b < < 1 or pKb > 0, given substance is a weak base.
c) Polyprotic Acids: substance that can donate more than one proton. e.g. H2S.
For polyprotic acids.
K a1 > K a 2
pK a1 < pK a 2
For cis-Butanedioic (maleic) acid, pK a1 = 1.92, pK a 2 = 6.23
For trans-Butanedioic (fumaric) acid, pK a1 = 3.02, pK a 2 = 4.38

Thus, it is also seen that cis-butanedioic (maleic) acid is much stronger acid than trans-butanedioic
(fumaric) acid due to intramolecular H-bonding.
Relative Strength of Inorganic Acids
1. Hydro acids of the elements of the same period: We know that, if the charge is spread over
larger volume then,
· Smaller is the charge density.
· Smaller is the basic character of the ion to attract a proton.
· Larger is the acidity of the conjugate acid. Now, consider the hydroacids of 2nd period
CH4, NH3, H2O, HF. We find that, from left to right
· Size of central atom over which the negative charge is present is decreasing
· The volume of central atom overlapped by hydrogen is 3/4th, 2/3rd, ½ and 1 respectively.
C– N– O– F–
H H H H H
CH3– NH –2 OH – F–
Increasing volume available to electron
Increasing electron delocalisation
Decreasing electron density
Decreasing bascity
· Volume available for negative charge is increasing in the conjugate bases

(CH 3− < NH 3− < OH − < F− )
· Charge density of the conjugate bases is decreasing
· Basicity of the conjugate bases is decreasing
· Acidity of the acids is increasing
· Stability of conjugate bases is increasing (CH 3− < NH 3− < OH − < F− )
· Acidity constant is increasing CH4 (10-58) < NH3 (10-35) < H2O (10-14)< HF (10-4)
· Basicity constant is decreasing
Therefore, the acidic character is increasing (CH 4 < NH 3 < H 2 O < HF) .
2. Hydro acids of the elements of the same group:

In each Group : from top to bottom
Atomic size of the central atom is increasing.
Volume available for the negative charge is increasing
Charge density is decreasing
Basicity of the ions is decreasing

Acidity of conjugate acids is increasing

Acidity constant is increasing
Basicity constant is decreasing
Therefore; order of acidic character can be also explained as following along with the above
reasons
a) VII A group (Halogens) - HF < HCl < HBr < HI
(Due to decreasing bond energy of H - X bond).
b) VI A group - H2O < H2S < H2Se < H2Te
(Due to decreasing trend in electron donar ability of OH-, HS-, HSe-, HTe- ions).
c) V A group - NH3 < PH3 < AsH3 < BiH3
(Due to decreasing order of electron density).
d) IV A group - CH4 < SiH4 < GeH4 < SnH4 < PbH4
(Due to decreasing order of electronegativity.)
e) III A group - BH3 < AlH3 < GaH3 < InH3 < TlH3
(Due to decreasing order of electronegativity.)
3. Among hydrides of elements with same electronegativity, acidic strength increases with size of
the central atom e.g.
CH 4 < H 2S < HI .
4. The ability of Borontrihalides to act as Lewis acid increases in the order of BF3 < BCl3 < BBr3
< BI3 due to decreasing order of strength of p bond.
X X
B X B X
X X
5. Acids that require only one electron pair to complete an outer shell are stronger than those
requiring two. Thus GaCl3 > ZnCl2.
Illustration 1: The order of increasing acidic strength of CH 4 , NH 3 , H 2 O and HF is:

(A) CH 4 < NH 3 < H 2 O < HF (B) HF < NH 3 < H 2 O < CH 4
(C) HF < CH 4 < H 2 O < NH 3 (D) H 2O < NH3 < CH 4 < HF
Solution: (A) To predict their relative acidities we shall evaluate the relative basicities of their
conjugate bases, viz.
CH 3– , NH –2 , OH – , F –
Although size of the central atom decreases from C to F, volume available to electron on
the central atom decreases in the order : C, N, O and F. Consider the case of CH 3–
(methide ion),
Three-fourth of the volume of the carbon atom is overlapped by 2 hydrogen atoms and
thus the negative charge on C is concentrated over 1/4th of the volume of the carbon
atom.
Thus the increasing basic character of these conjugate bases is
F – < OH – < NH 2– < CH 3–

Hence the increasing acidic character of the corresponding conjugate acids is

CH 4 < NH3 < H 2 O < HF
Oxyacids
1. Oxyacids with same central atom at different oxidation state: Among oxyacids of the same
central atom having general formula. (HO)m ZOn
Where Z = central atom
m = no of oxygen atoms attached to z and attached to H.
n = No of oxygen atoms attached to z but not attached to H.
Acidic strength increases with increasing oxidation no e.g.-
+1 +3 +5 +7
a) HOCl < HOClO < HOClO 2 < HOClO3

very weak weak strong very strong
They give OCl, OClO, OClO2 ,OClO 3 anions after removal of a proton. The species which
have more than one oxygen atom show resonance.
We see that from left to right, acidic strength increases
Due to :
· More the no. of oxygen atoms, more the resonance.
· Volume available for the negative charge is increasing
· Charge density is decreasing
· Basicity of the anion is decreasing
· Acidity of the conjugate acid is increasing.
+4 +6
b) H 2 SO3 < H 2 SO 4
+3 +5
c) H NO 2 < H NO3
2. Oxyacids with different central atom of same oxidation state and same configuration.
a) HOI < HOBr < HOCl
b) HIO4 < HBrO4 < HClO4
c) HPO3 < HNO3
d) H3AsO4 < H3PO4.
Among above; acidity increases from left to right due to moving towards top in the group.
Due to:
· Decreasing size of the central atom
· Increasing order of the electro negativity
· Increasing order of pull of electron of O-X bond towards X.
· Resulting into increasing positive character on O.
· Ultimately, increasing order of release of H+.
3. The strength of oxyacids increases from left to right across a period e.g. -
H2SiO4 < H3PO4 < H2SO4 < HClO4,
Which is attributable to increase in electronegativity of the central atom,
4. Hydrated metal ions: Under favourable conditions, one or more protons may dissociate to
form the coordinated aqua groups.
[M(H 2 O)6 ]n + + H 2 O
(Hydrated metal ion ) 
→ [M(H2O)5OH]n-1 + H3O+

For hydrated metal ion or aqua acids, acidity increases with the increase of positive charge of the
central metal ion and with decreasing ionic radius.
[Fe(H 2O)6]3+ > [Fe(H2O)6]2+.
Exceptions are some times seen due to the effect of covalent bonding.
[Fe(OH 2 ) 6 ]2 + < [Fe(OH 2 ) 6 ]3+ < [Al(OH 2 ) 6 ]3+ ≈ [Hg(OH 2 ) 6 ]2+
Relative Strength of Inorganic Bases
1. In Period: The basicity of the compound decreases from left to right along a period e.g.:
NH3 > H 2 O > HF
Due to:
a) Increase in the electronegativity of the atom holding the electron pair(s)
b) Decrease in the availability of electron pair(s) for sharing with the proton.
2. In group: The basicity of a compound decreases from top to bottom in a group e.g. :
a) F − > Cl − > Br − > I −
b) O2 − > S2 −
c) NH3 > PH3 > AsH3 > SbH3 > BiH3.
Due to:
a) Increase in the size of atom holding the unshared electron pair(s).
b) Decrease in the availability of electrons.
3. Presence of negative charge on the atom holding the electron pair(s) increases the basicity while
presence of positive charge decreases basicity e.g.
H O > H — OH > H3 O+
4. Alkali and Alkaline Hydroxides: Basic nature increases on going down the group e.g.
a) LiOH < NaOH < KOH < RbOH < CsOH
b) Be(OH)2 < Mg(OH)2 < Ca(OH)2 < Sr(OH)2 < Ba(OH)2.
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."

ˆˆ† ionized molecules

For: unionized molecules ‡ˆˆ
∝<< 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 applied law of mass action upon ionic euqilibrium to verify whether eqiulibirum really
exits or not. The constancy of equilibrium constant (K) of the dissociation equilibrium of a weak electrolytes
conformed that equilibrium really exits. In the case of strong electrolyte the equilibrium constant do not
come to be constant indicating thereby that a strong electrolyte remains completly ionised and hence
there is no question of equilibrium.
Consider a weak binary electrolyte having concentration C and degree of dissociation α
AB ˆˆ†
‡ˆˆ A + + B−
At. time = 0 C 0 0
at time = t C(1 - α ) Cα 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
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 completely
ionized at all dilution and hence does not give accurate results.
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
ˆˆ† H O+ + OH-
2H2O( l ) ‡ˆˆ 3
Cα Cα
[H3O + ][OH − ]
K eq =
[H 2 O]2

K eq [H 2O(l)] = [H3 O+ ][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 mol2/lt2.
Kw depends upon temperature dissociation of water gives equal no. of H3O+ and OH- ions.
So 1× 10−14 = [H 3 O+ ]2 = [OH − ]2 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.
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 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 2: The Kw for 2H2O H3O+ + OH- changes from 10-14 at 25°C to 9.62 × 10-14 at
60°C. The pH and nature of water at 60°C will be
(A) 6.51, neutral (B) 6.51, acidic
(C) 6.51, alkaline (D) 7.51 alkaline
Solution: (A) Kw for H2O at 25°C = 10-14

[H+] [HO-] = 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 extends from 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.
e.g. let us take CH3COOH (C mole/litre and having degree of dissociation α ).
ˆˆ†
CH3COOH ‡ˆˆ CH3COO- + H+
C(1- α ) Cα Cα
[CH 3COO − ][H + ]
K a(CH3COOH) =
[CH 3COOH]
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]
Cα 2
Note: For calculating the pH of a weak acid first of all we calculate from the equation K a = ,
1− α
if α comes out to be α ≤ 0.1 then 1 - α will be taken as one and we use formula otherwise we would
use the formula K a = Cα 2
Cα 2
Ka = for all calculations.
1− α
Illustration 3. The degree of dissociation of 0.05 M NH3 at 25°C in a solution of pH = 11 will

be
(A) 0.02 (B) 0.04
(C) 0.01 (D) 0.8
Solution. (A) NH4OH ˆˆ† NH + + OH −

‡ˆˆ 4

C 0 0
C(1 - α ) αC αC
Given, pH = 11
 H +  = 10−11
 OH −  = 10−3 = Cα
Since, C = 0.05
10−3 10−3
α= = = 2 ×10−2 = or 2%
C 0.05
Illustration 4. A solution of HCl has a pH = 5. If one ml of it is diluted to 1 litre, pH of resulting

solution will be
(A) 6.9586 (B) 4.9586
(C) 5.9586 (D) 2.9586
Solution: (A) HCl1 = 10-5 M since pH = 5

Meq. Of HClI in 1 mL = 10 × 1-5
Meq. Of HClII in 1000 mL = N × 1000

Since II is prepared by diluting I and Meq. Does not change on dilution.
i.e., Meq. of HCl (concentrated) = Meq. of HCl (dilute)
10-5 × 1 = N × 1000
−8
∴ N HCl = 10
II
HCl  → H
+
+ Cl-
Conc. before ionisation 10-8N 0 0
Conc. after ionisation 0 10-8 10-8
[H ] = 10 M but pH = 8 is not possible because it is acid. Now [H+] = 10-7M are
+ -8
already present in solution and since 10-8 < 10-7 and thus, it should not be neglected.
[H+] = 10-8 + 10-7 = 10-7 (1.1)M = 1.1 × 10-7 M
∴ pH = 6.9586.
Illustration 5. The pH of a solution which contains 100 mL of 0.1 M-HCl and 9.9 mL of 1.0 M
NaOH will be
(A) 2.0409 (B) 3.0409
(C) 1.0409 (D) 4.0409
Solution (B) HCl + NaOH → NaCl + H2O

Meq. before reaction 100 × 0.1 9.9 × 1
= 10 = 9.9 0
Meq. after ionisation 0.1 0 9.9 9.9
 0.1 
[H+] left from HCl =   = 9.099 × 10−4
 100 + 9.9 
pH = - log H = - log 9.099 × 10-4
+
pH = 3.0409.

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
ˆˆ† H+ + A-. The degree of dissociation
HA ‡ˆˆ
Ka
α=
C
BA (another electrolyte) added whose molarity is M, due to this the new degree of dissociation becomes
BA ˆˆ† B+
‡ˆˆ + A-
0 M M
HA ˆˆ† H +
‡ˆˆ + A-
C(1 - α′ ) C α′ C α′
[H + ][A − ] [Cα′][Cα′ + M]
K a ( HA) = =
[HA] [C(1 − α′)]
K a(HA) = Cα′2 + Mα′ 1 − α′ ≅ 1
Cα′2 Neglecting Mα ' because α′ < < 1
Ka
α′ =
M
As a result of common ion effect, the conc. of the ion, which is not common changes to make the Ka
constant, because Ka only depends upon temperature not on concentration.
Note: The use of this phenomenon is made in qualitative analysis to adjust the conc. of S2 − 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
HCl  → H+ + Cl-
10-8 M HCl furnishes 10-8M H+
H2O 
→ H+ + OH- , Kw = 10-14
x x
Hence, (10-8 + x)x = 10-14
x2 + 10-8 x - 10-14 = 0

Solving, we get x = 9.6 × 10-8

Total [H+] = 10-8 + 9.6 × 10-8 = 10.6 × 10-8.
pH of solution = log(10.6 × 10-8) = 8 - log 10.6
= 8 - 1.0253 = 6.9747
Same rule applies for pH of 10 −8 M NaOH.
Illustration 6: What is molar concentration of Ca(OH)2 if its solution has pH of 12 ?

(A) 10-3 M (B) 10-2 M
(C) 0.5 × 10 M
-2
(D) 0.5 × 10-3
Solution: (C) 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 molecule of 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 is α1
ˆˆ† H + + A1–
HA1 ‡ˆˆ
[H + ] = C1α1
For HA 2 if concentration is C2 and degree of dissociation is α 2
ˆˆ† H + + A 2–
HA 2 ‡ˆˆ
[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 C 2   K a1 C1 
R.S. = ×   =  
C2 K
 2 
a C 1 K
 2 
a C 2
If C1 and C2 are same, then
 Ka 
R.S. =  1 
 Ka
 2 

pH OF MIXTURES :
(A) 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 concentration is C2 and degree of dissociation of α
HA = H+ + A −
C2(1- α ) C2 α C2 α
Total (H+) conc. = C1 + C2 α
pH = - log [C1 + C2 α ]
Illustration 7: 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 ] .
(A) 1.35 × 10 −5 M (B) 1.35 × 10 −4 M
(C) 1.35 × 10 −6 M (D) 1.35 × 10 −3 M
Solution: (B) Given,

[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.
ˆˆ† HCOO – + H +
HCOOH ‡ˆˆ
[H + ][HCOO – ]
Ka =
[HCOOH]
[0.02][HCOO – ]
1.8 ×10 = –4
[0.015]
[HCOO – ] = 1.35 ×10 –4 M
(B) pH calculation of solution of a mixture of two weak Monobasic Acids in water

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

[H3 O+ ][B− ] [C1α1 + C 2 α 2 ][C2 α 2 ]

K a[HB] = =
[HB] [C2 (1 − α 2 )]
pH = – log[H + ] = – log[C1α1 + C 2 α 2 ] = -log K a C1 + K a C2

1 2
where K a1 = Ka(HA) and K a2 = Ka(HA)
Illustration 8: The [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 ] respectively will be
(A) 7.13 × 10 −2 M (B) 7.13 × 10 −3
(C) 7.13 × 10 −5 (D) 7.13 × 10 −6
Solution: (B) In this problem both the acids contribute for [H + ] due to appreciable dissociation.
Thus,
ˆˆ† H + + HCOO –
HCOOH ‡ˆˆ
0.1 - x x+y x 0.1 - x ≅ 0.1
ˆˆ† H + + OCN –
HOCN ‡ˆˆ
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 … (A)
[HCOOH]
[H + ][OCN – ]
K HOCN = = 3.3 ×10–4 … (B)
[HOCN]
(x + y)x
or K HCOOH = = 1.8 × 10 –4 … (C)
0.1
(x + y)y
K HOCN = = 3.3 × 10 –4 … (D)
0.1
Thus, by eqs. (C) and (D)
x 1.8
= or y = 1.83 x … (5)
y 3.3
From Eq. (C) (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

(C) pH of a dibasic Acids and Polyprotic Acid

Let's take the e.g. of a dibasic acid H2A. Assuming both dissociation is weak. Let the initial conc. of H2A
is C and α 1 and α 2 be degree of dissociation for first and second dissociation.
H2 A ˆˆ† HA -
‡ˆˆ + H+
C(1 - α 1) C α 1 (1 - α 2) C α 1 + Cα 1 α 2
HA - ˆˆ† H+
‡ˆˆ + A2 −
Cα 1 (1 - α 2) C α 1 + C α 1 α 2 C α 1 α 2.
[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 1 and 2. We can calculate the H+ conc.
[H+] = C α 1 + C α 1 α 2
pH = - log [C α 1 + C α 1 α 2]
Illustration 9: The molar concentrations of H + , HCO 3– 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 , K 2 = 4.69 × 10 –11 ]

will be
(A) 6.61× 10−6 ,6.73 × 10−11 and4.78 × 10−6
(B) 6.61× 10−5 ,6.73 × 10−11 and4.78 × 10−6
(C) 6.61× 10−5 ,6.73 × 10−5 and4.78 × 10−11
(D) 6.61× 10−6 ,6.73 × 10−5 and4.78 × 10−11
Solution: Given, pH = 4.18 = -log [H + ]
[H + ] = 6.61×10 –5 mol litre –1

ˆˆ† H + + HCO3–
H 2 CO3 ‡ˆˆ
[H + ][HCO3– ]
K1 =
[H 2 CO3 ]
[6.61×10 –5 ][HCO3– ]
or 4.45 ×10 –7 = or [HCO 3– ] = 6.73 × 10 –5 mol litre –1
[0.01]
Again for dissociation of HCO3– , we have
ˆˆ† H + + CO3–2
HCO3– ‡ˆˆ

[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
(D) pH of mixture of acids

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
pKa and pKb for a conjugate acid-base pair

For an acid HX
ˆˆ† H + + X –
HX ‡ˆˆ
[H + ][X – ]
∴ Ka = … (A)
[HX]
For conjugate base X – of acid HX
ˆˆ† HX + OH –
X – + H 2O ‡ˆˆ
[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.

Illustration 10: The pH of pure water at 25°C and 35°C are 7 and 6 respectively. The heat of
formation of water from H+ and OH- will be
(A) +84.551 kcal / mole (B) −84.551 kcal / mole
(C) +8.4551 kcal / mole (D) −8.4551 kcal / mole
Solution: (B) At 25°C; [H+] = 10-7

KW = 10-14
At 35°C; [H+] = 10-6
KW = 10-12
Now using
Kw ∆H  T − T 
2.303 log10 K = R  T × T 
2 2 1
w1  1 2
10−12 ∆H  308 − 298 

=
2  298 × 308 
2.303 log10
10−14
∆ H = 84551.4 cal/mol = 84.551 kcal/mol
Thus H2O H+ + OH-; ∆ H = 84.551 kcal/mol
∆ H = - 84.551 kcal/mol
+ -
H + OH H2O;
Illustration 11: The pH of solution obtained by mixing 10 mL of 0.1 M HCl and 40 ml of 0.2 M
H2SO4 will be
(A) 1.4685 (B) 0.685
(C) 2.4685 (D) 1.9685
Solution: (B) 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
 Meq. 
Q [H ] =
17 +
= 3.4 × 10−1 
Vin mL 
+
[H ] =
50 
pH = - log [H+] = - log 0.34
pH = 0.4685
Hydrolysis of Salt
Salts are strong electrolytes when dissolved in water, they dissociated almost completely into cation or
anions. If anion interacts with water it is called as anionic hydrolysis.
A − + H2O  → HA + OH- Akaline solution (pH increases).
If cation intereacts 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 and 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.
ˆˆ† NH 4 OH + HCl
NH 4 Cl + H 2 O ‡ˆˆ
ˆˆ† NH 4 OH + H + + Cl−
NH +4 + Cl − + H 2 O ‡ˆˆ
ˆˆ† NH 4 OH + H +
NH +4 + H 2 O ‡ˆˆ
(acidic)
[NH 4 OH][H + ]
Kh =
[NH +4 ]
Relation between K h , K b and K w :
ˆˆ† NH 4+ + OH −
NH 4 OH‡ˆˆ
[NH +4 ][OH − ]
Kb = … (A)
[NH 4 OH]
ˆˆ† H + + OH −
H 2 O ‡ˆˆ
K w = [H + ][OH − ] … (B)
Dividing (B) by (A)
Kw [H + ][OH − ]
= × [NH 4 OH]
K b [NH 4+ ][OH − ]
Kw
= Kh
Kb
Degree of hydrolysis
ˆˆ† NH 4+ + OH −
NH +4 + H 2 O ‡ˆˆ
C(1− h ) Ch Ch
Ch . Ch
Kh = = Ch 2 (1 - h ≅ 1)
C(1 − h)
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
Illustration 12. The degree of hydrolysis and pH of 0.2 M solution of NH4Cl will be [Given Kb
for NH4OH is 1.8 × 10 −5 ]
(A) 5.27 × 10−5 , 5.9771 (B) 5.27 × 10−4 , 5.9771
(C) 5.27 × 10−5 , 4.9771 (D) 5.27 × 10−4 , 4.9771
Ans. (C)
Solution: NH4 Cl + H2O ˆˆˆ
†
‡ˆˆ
ˆ NH4OH + HCl
Before hydrolysis C 0 0
After hydrolysis C(1 - h) Ch Ch
Where h is degree of hydrolysis
 KH   Kw  10−14
h=   =   = = 5.27 × 10-5
 C   K b .C  1.8 × 10−5 × 0.2
From HCl, a strong acid
K   Kw 
∴  H +  = C.h = C  H  = ( K H .C ) =  .C 
 C   Kb 
 1o −14 × 0.2 
=  −5 
= 1.054 × 10−5
 1.8 × 10 
pH = - log [H ] = - log(1.054 × 10-5)
+
= 4.9771.
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).
ˆˆ† CH 3COOH + NaOH
CH 3COONa + H 2 O(l) ‡ˆˆ
[CH 3COOH][OH − ]
ˆˆ† CH 3COOH + Na + + OH −
CH 3COO + Na + H 2 O(l) ‡ˆˆ
− + Kh =
[CH 3COO − ]
Relation between, K h , Kw and Ka
ˆˆ† CH 3COO − + H +
CH 3COOH ‡ˆˆ

[CH3COO − ][H + ]
Ka = … (A)
[CH3COOH]
ˆˆ
H2O ‡ˆ†
+
ˆ H + OH
−
K w = [H + ][OH − ] … (B)
Dividing equation (B) ÷ (A)
K w [H + ][OH − ] × [CH3COOH] [OH − ][CH3COOH]
= = = Kh
Ka [CH 3COO − ][H + ] [CH3COO − ]
Degree of Hydrolysis
ˆˆ† CH 3COOH + OH −
CH 3COO − + H 2 O(l) ‡ˆˆ
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 then 1 - h = 1.
C(1 − h)
Kh
h=
C
Kw
h=
KaC
[ [OH − ] = Ch
Kw KwC Kw Ka Ka × Kw
[OH− ] = C = [H3O+ ] = = Kw =
Ka C Ka [OH− ] KwC C
Taking -log both sides
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 13. The percentage hydrolysis in 0.0003 M aqueous solution of NaOCN will be
[Ka for HOCN = 3.33 × 10 −4 ].
(A) 10-3 (B) 10-2
(C) 10-4 (D) 10-5

Solution. ˆˆ†
(B) NaOCN + H2O ‡ˆˆ NaOH + HCN
 KH   Kw  10−14
h=  =  =
 C   K a .C  3.33 × 10−4 × 0.003
h = 10-4
∴ % hydrolysis = 10-4 × 100 = 10-2.
Illustration 14. The pH of a 0.5 M aqueous NaCN solution will be [pKb of CN- = 4.70].
(A) 11.5 (B) 9.5
(C) 10.5 (D) 5.5
Solution: (A) pKa for HCN = 14 - 4.70 = 9.30

1
pOH = [ pK w − log C − pK a ] = [14 − log0.5 − 9.30]
1
2 2
1
= [14 + 0.3010 − 9.30] = 2.5
2
∴ pH = 14 - 2.5 = 11.5.
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).
ˆˆ† CH 3COOH + NH 4 OH
CH 3COONH 4 + H 2 O ‡ˆˆ
CH 3COO − + NH 4+ + H 2 O ‡ˆˆ
[CH 3COOH][NH 4 OH]

Kh =
[CH 3COO − ][NH 4+ ]
Relation B/w, K h , K w , K a & K b
ˆˆ† CH 3COO − + H +
CH 3COOH ‡ˆˆ
[CH3COO − ][H + ]
Ka = … (A)
[CH3COOH]
ˆˆ† NH +4 + OH −
NH 4 OH ‡ˆˆ
[NH +4 ][OH − ]
Kb = … (B)
[NH 4 OH]
ˆˆ† H + + OH −
H 2 O ‡ˆˆ
K w = [H + ][OH − ] … (C)
Kw [H + ][OH − ] × [CH 3COOH][NH 4 OH]

=
Ka × Kb [CH 3COO − ][H + ][NH+4 ][OH − ]

Kw
= Kh
Ka × Kb
Degree of Hydrolysis
CH 3COO − + NH 4+ + H 2 O ‡ˆˆ
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 KaKh
The acetic acid formed would partially decompose to give CH 3COO – and H + . But because of
common ion effect (that is, due to the unhydrolysed CH 3COO – ) it is possible to neglect the acetate ion
coming from CH 3COOH .
ˆˆ† CH3COO – + H +
Therefore CH 3COOH ‡ˆˆ
Cα C(1 – α )
C(1 – α)[H + ]
Ka =
Cα
[H + ]
Ka = (1- α ≅ 1)
α
Kw KwKa
[H + ] = K a α = K a =
KaKb Kb
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 < K b 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
hydrolysed, 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.
ˆˆ† HCN + OH −
CN − + H 2 O ‡ˆˆ

which can react with NH +4 ions as
ˆˆ† NH 4 OH
OH − + NH 4+ ‡ˆˆ
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 extent 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 15. The pH of mixture obtained by mixing 50 ml of 0.05 M NH4OH and 50 ml of 0.05
M CH3COOH will be [ K a = 1.8 × 10−5 and K b = 1.8 × 10 −5 ]
(A) 7 (B) 6
(C) 2 (D) 8
Solution: (A) NH4OH + CH3COOH  → CH3COONH4 + H2O

mM before 2.5 2.5 0 0
reaction
mM after 0 0 2.5 2.5
reaction
In this case pH is decided on the basis of hydrolysis of salt.
2.5
[CH3COONH4 ] = = 2.5 × 10−2 M
100
1 1
pH = + [log K b − logK w − logK a ] = [pK w + pKa − pKb ]
2 2
1
= + [log(1.8 × 10−5 ) − log 10−14 − log(1.8 × 10−5 )]
2
pH = 7
Case IV : Salts of strong Acid + Strong Base

e.g., NaCl, KNO3 , … etc.
This category of salts does not undergo salt hydrolysis
Buffer Solution
A Buffer solution is that which resist the pH change by addition of small quantity of acid or alkali
or on dilution or on langstanding. 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+ ˆˆˆ
†
‡ˆˆ
ˆ 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.
ˆˆ† NH 4 OH
NH +4 + OH − ‡ˆˆ
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 ionised into
Na+ and Cl-. If H+ ions are added to this solution the H+ combines with Cl- to form HCl which completely
ionised 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 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
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 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)

ˆˆ† CH COO − + H+
CH3COOH ‡ˆˆ 3
[CH3COO − ][H + ]
Ka =
[CH3COOH]
Since most of CH3COO- comes from salt (CH3COONa) and hence conc. of CH3COO − will be conc.
of CH3COONa.

[Salt][H + ]
Ka =
[Acid]
K a [Acid]
[H + ] =
[Salt]
Taking -log on both sides
[Acid]
-log [H +] = - log Ka - log
[Salt]
[Salt]
Henderson's equation pH = pK a + log
[Acid]
Illustration 16. 20 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 ? (The ionization constant of acetic
acid is 1.8 × 10-5).
(A) 1.568 (B) 2.568
(C) 4.568 (D) 3.568
Solution: (C) 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
[ Salt ]
Hence, using the expression = pH = pKa + log
[ acid ] , we get . . . . . (A)
 20 
pH = -log(1.8 × 10-5) + log   = 4.745 - 0.177 = 4.568
 30 
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 .
OH- + NH +4 
→ NH 4 OH
Calculation of pH of Basic Buffer Solution

e.g. Mixture of (NH4OH + NH4Cl)

ˆˆ† NH +4
NH4OH ‡ˆˆ + OH- Since most of NH +4 ions come from salt
(NH4Cl) so we take NH +4 conc. as conc. of salt (NH4Cl).

[Salt][OH − ] [NH +4 ][OH − ]
Kb = Kb =
[Base] [NH 4 OH]
K b × [Base]
[OH − ] =
[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.
ˆˆ† CH 3COO – + NH +4
For example, CH3COONH 4 ‡ˆˆ
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.
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  S(x − S) 
= 2.303 × 
∂(pH)  x 

Maximum value of Buffer Index

S(x − S)
B.I = 2.303 ×
x
d 1 
(B.I) = 2.303×  (x − 2S)
dS 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
(pKa −1) < pH < (pKa +1)
Outside this range the Buffer capacity is too small to be of any practical application.
Illustration 17: The pH of buffer changes from 4.745 to 4.832 when 0.01 mole of KOH is added
to 0.5 litre of buffer. The buffer capacity of buffer will be
(A) 0.23 (B) 0.33
(C) 0.43 (D) 0.13
Solution. (A) Buffer capacity = No. of mole of Acid/Base add to one litre of buffer
Change in pH value
0.01× 2
= = 0.23
4.832 − 4.745
Illustration 18:The pH of a buffer solution prepared by 30 g of Na2CO3 in 1000 mL and 150 mL

of M HCl. [Ka for HCO3− = 5.63 × 10−11 ] will be
(A) 10.197 (B) 9.197
(C) 8.197 (D) 11.197
Solution (A) Na2CO3 + HCl 

→ NaCl + NaHCO3
30
Meq. before reaction × 1000 150 × 1
106
= 283 = 150 0 0
Meq. after reaction 133 0 150 150
The solution contains Na2CO3 and HCO3− and thus, acts as buffer..

 CO 2 − 
pH = - log Ka + log  3 
 HCO3− 
133
pH = - log Ka + log
150
133
= - log 5.63 × 10-11 + log = 10.249 - 0.052
150
pH = 10.197.
Illustration 19: 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 will be
(A) 7.248 g (B) 6.248 g
(C) 5.248 g (D) 52.48 g
[salt ]
Solution (C) pOH = - log Kb + log
[ Base]
 NH +4 
Or pOH = - log Kb + log
[ NH4OH]
Q  NH +4  is obtained form 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  = ; [NH4OH] =
500 500
a / 500
4.65 = - log (1.78 × 10-5) + log
100 / 500
a
4.65 = 4.7496 + log
100
∴ a = 79.51
a 79.51
Millimole of (NH4)2SO4 added = = = 39.755
2 2
w
∴ × 1000 = 39.755
132
∴ W( NH4 )
2
SO 4 = 5.248 g.
Illustration 20: The 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 ?
(A) 39.62 ml (B) 30.962 ml
(C) 396.2 ml (D) 49.962 ml

Solution. (A) Let V mL of 0.1 M HCOONa be mixed to 50 mL of 0.05 M HCOOH.

Total millimole
Q [Molarity] =
Total volume
0.1× V
∴ In mixture [HCOONa] = ( V + 50 )
50 × 0.05
[HCOOH] =
V + 50
[Salt ]
Q pH = - log Ka + log [ Acid]
( 0.1× V ) / ( V + 50 )
∴ 4.0 = 3.80 + log 2.5 / ( V + 50 )
V = 39.62 mL.
Illustration 21: A certain buffer solution contains equal concentration of X- and HX - Kb for X- is
10-10. The pH of buffer will be
(A) 10 (B) 4
(C) 6 (D) 8
Solution. (B)
−10
Q K b( x −1 ) = 10
Also for conjugate acid - base pair
K a ( HX ) × K b x −1 = 10−14
( )
∴ K a ( Hx ) = 10−4
[HX] =  X 
−
Now,
(acid) (salt)
[Salt ]
pH = - log Ka + log
[ Acid] = - log 10-4
pH = 4.
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.

ˆˆ† xAy+ + yBx −

AxBy ‡ˆˆ
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.
Calculation of Solubilities of Salts

We shall now discuss the solubilities types of salts under various conditins.
i) Solubilities of AgCl(salt of a strong acid and strong base) in Water :
AgCl would disolve in water as,
AgCI (S)  → Ag (aq) +Cl (aq)’
+ -
At saturation point,
AgCI(s) Ag+ (aq) +Cl- (aq)
If the solubility of the salt is x moles/ lit.
∴ [ Ag+] = xM, [Cl − ] = xM
⇒ x2 = KSP
x= K SP
ii) Solubility of AgCl in a solution that is having 0.1M in AgNO3:
AgCI would dissolve and finally reach saturation.
AgCl(s) Ag+(aq) + Cl-(aq)
The KSP of AgCl is approximately 10-10 . If AgCl were to be dissolved in water (pure), its solubil-
ity would have been 10-5M (previous section).In the presence of 0.1 M AgNO3 its solubility will
decrease due to common ion effect. This means that [Ag+] from AgCl would be less than 10-
5
M . Hence, we can ignore the contribution of Ag+ from AgCl.
If the solubility of AgCl is x’ moles / l in the presence of 0.1 M AgNO3, then
[Ag+] = 0.1 M, [Cl-] = x’ M
K SP
∴ x’ = = 10-9 moles / l
0.1
iii) Solubility of CH3COOAg(salt of weak acid and strong base) in water:
CH3COOAg dissolves and reaches saturation.Since it is a salt of weak acid and strong
base, it would hydrolyse. If the solubility of the salt is x moles /then
CH COOAg(s)3
CH COO − (aq) +
3
Ag+ (aq)
At eqb : x-y x
CH3COO − (aq) + H2O CH3COOH (aq) + H+ (aq)
x-y y
-
where y is the amount of CH3COO ion that is hydrolysed.
∴ (x - y) x = KSP

y2 K
= w
(x − y) K a
Knowing the values of KSP and Ka, solubility of the salt can be calculated.
iv) Solubility of CH3COOAg (salt of a weak acid and strong base) in an acid buffer of pH =
4 (assuming that the buffer does not have any common ion by CH3COOAg):
CH3COOAg would dissolve and reach equilibrium. It would then be hydrolysed.If the
solubility of the salt is x’ M in this solution ,then
At eq.; CH3COOAg(s) CH3COO- (aq) + Ag+ (aq)

x’ - y’ x’
CH3COO-(aq) + H2O CH3COOH (aq) + OH-
x’- y’ y’ 10-10
Since the solution is a buffer, the pH will be maintained.
∴ (x ’ - y’) x’ = KSP
y2 K
= w
(x − y) K a
knowing KSP and K a, the solubility can be calculated.
v) Solubilty of CH3COOAg in an buffer solution of pH =9:

Following the same logic as give in the earlier section,
CH3COOAg(s) CH3COO- (aq) + Ag+ (aq)
At eqb : x’’- y’’ x’’
CH3COO-(aq) + H2O CH3COOH + OH-
At eqb : x’’- y’’ y’’ 10-4
where x’’ M is the solubility of the salt and y’’ the extent to which it is hydrolysed.
∴ ( x’’ - y’’) x’’ = Ksp
y ''× 10 −5 K w
=
(x''− y '') K a
Knowing Ksp and K a, the solubility can be calculated.
vi) Solubility of AgCl in an aqueous solution containing NH3.
Let the amount of NH3 initially be ‘a’ M. If the solubility of the salt is x moles /L, then
AgCI (s) Ag+ (aq) + Cl- (aq)
x-y x
Ag+ (aq) + 2NH3 (aq) [Ag(NH3)2]+(aq)
x-y a - 2y y
Where y is the amount of Ag+ which has reacted with NH3.
∴ (x -y ) x = Ksp

y
= K f ( formation constant of [Ag(NH3)2]+
(x − y)(a − 2y)2
Knowing K sp and K f , the solubility can be calculated.
The common ion presence in the solution decrease the solubility of a given compound e.g. The
solubility of BaSO4 in Na2 SO4 solution is smaller than that in an aqueous solution .
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
ˆˆ† Ag + + Cl –
AgCl(s) + aq. ‡ˆˆ
→ K + + Cl –
KCl (s) + 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 = where s is solubility of AgCl in presence of 0.1 M KClaq.
0.1
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 and more salt can
be dissolve in it.
If ionic product is greater than solubility it means solution is holding more salt than it can dissolve
in therefore precipitation starts and continues till, ionic product becomes equal to Ksp.
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 stoichiometry 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 −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 . 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.
ˆˆ† CH3COO-
CH3COONH4 ‡ˆˆ + NH +4 … (A)
S-y S-y
CH3COO- + NH +4 ˆˆ† CH COOH + NH OH
+ H2O ‡ˆˆ 3 4
S-y S-y y y … (B)

K sp = (S − y)(S − y) = (S − y) 2
Due to hydrolysis of salt from equation (B)
[CH 3COOH][NH 4 OH] y.y
Kh = − +
=
[CH 3COO ][NH 4 ] (S − y)(S − y)
2
 y 
Kh =  
S− y 
and we also know that
Kw
Kh =
Ka Kb
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.
ˆˆ† CH COO- + NH +4
CH3COONH4 ‡ˆˆ 3
S-y y
CH3COO -
+ H 
+
→ CH3COOH … (B)
S-y (from Acidic Buffer) y

K sp = [CH3COO− ][NH 4+ ] = [S - y] [y] = y [S - y]
for equation (B)

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

ˆˆ† CH COO- + NH +4
Similarly CH3COONH4 ‡ˆˆ 3
y S-y
ˆˆ†
NH +4 + OH − ‡ˆˆ NH 4 OH
S-y (from buffer) y
K sp (CH3COONH4 ) = [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 22:A 100.0 mL sample is removed from an aqueous 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. The Ksp for CaSO4 at 25°C will be
(A) 3.115 × 10−4 (B) 3.115 × 10−5
(C) 3.115 × 10 −6 (D) 3.115 × 10 −3
Solution: (A) 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
[Ca2+] = [ SO 24 − ] = 0.01765 M .
Ksp = [Ca2+] [SO 24 − ] = (0.01765)2 = 3.115 × 10-4.

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) ˆˆ†
‡ˆˆ Ag+ + Cl-
At time = 0 b 0 0
at time = t b-y y
Ag+ + 2NH 3 ˆˆ† [Ag (NH3)2 ]+ (aq.)
‡ˆˆ
b-y a -2y y
+
where y is the amount of Ag which reacted with NH3.
K sp = [Ag + ][Cl− ] = (b − y)y
After knowing the value of Ksp and Kf the value of solubility can be calculated.

Illustration 23. Ksp of AgCl is 1.5 × 10 −10 at 25°C. The solubility of AgCl in :
Pure water, 0.1 M AgNO3 and 0.01 M NaCl will be (respectively)
(A) 1.224 × 10−5 ,1.5 × 10−5 and 1.5 × 10−5
(B) 1.224 × 10−5 ,1.5 × 10−6 and 1.5 × 10−6
(C) 1.224 × 10−6 ,1.5 × 10−5 and 1.5 × 10−5
(D) 1.224 × 10−5 ,1.5 × 10−9 and 1.5 × 10−8
Solution. (D) In pure water :

Let solubility of AgCl be s mol litre-1
For AgCl (s) ˆˆ†
‡ˆˆ Ag+ (aq.) + Cl− ( aq.)
Ksp = [Ag+] [Cl-] = s × s
∴s= ( K ) = (1.5 ×10 )

sp
−10
= 1.224 × 10-5 mol litre-1

In 0.1 M AgNO3 :
+ −
AgCl (s) ˆˆ† Ag + Cls
‡ˆˆ s
AgNO3  Ag + + NO3−
→ 0.1 0.1
∴ Ksp = [Ag+] [Cl-] = (0.1 + s) (s)

( Q s < < < 0.1, presence of common ion decreases solubility)
∴ s(0.1) = 1.5 × 10-10
∴ s = 1.5 × 10-9 mol litre-1.
In 0.1 M NaCl :
+ −
AgCl (s) ˆˆ† Ag + Cls
‡ˆˆ s
+
NaCl → Na
 + Cl−
0.01 0.01
Ksp =  Ag +  Cl−  = [s ][ 0.01 + s] (s < < < 0.01)

  
∴ s = 1.5 × 10 mol litre-1.
-8
Illustration 24. The [Ag+] ion in a saturated solution of Ag2CrO4 at 25°C is 1.5 × 10 −4 M. Ksp of
Ag2CrO4 at 25°C will be
(A) 1.688 × 10 −10 (B) 1.688 × 10 −11
(C) 1.688 × 10 −9 (D) 1.688 × 10 −12
Solution. (D) For saturated solution of Ag2CrO4, if solubility is s mol litre-1. Then,
ˆˆ† 2Ag ( aq.) + CrO 24 − ( aq. )
+
Ag2CrO4 (s) ‡ˆˆ 2s s
Ksp = (2s)2 (s) = 4s3 [Q  Ag +  = 2s = 1.5 × 10−4 ⇒ s = 0.75 × 10-4 ]

= 4(0.75 × 10-4)3
Ksp = 1.688 × 10-12 mol3 litre-3.

Illustration 25. The solubility product of SrF2 in water is 8 × 10−10 , its solubility in 0.1 M NaF
aqueous solution will be
(A) 8 × 10−10 (B) 8 × 10 −6
(C) 8 × 10 −8 (D) 8 × 10 −7
2
Solution (C) Ksp = Sr 2+   F− 
8 × 10-10 = s[2s + 0.1]2
8 × 10−10
= 8 × 10-8 M.
s=
( 0.1)
2
Illustration 26. The pH at which Mg(OH)2 begins to precipitate from a solution containing 0.10
M Mg2+ ions will be [Ksp of Mg(OH)2 = 1× 10 −11 ]
(A) 5 (B) 9
(C) 6 (D) 8
Solution. (B) When Mg(OH)2 starts precipitation, then,

2
 Mg  OH  = K sp of Mg(OH)2
2+ −
2
[0.1] OH −  = 1 × 10-11
∴  OH  = 10 M
− −5
∴ pOH = 5
∴ pH = 14 - pOH
pH = 14 - 5 = 9.
Acid-base Indicators
An acid & base indicator is a 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 acids 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
ˆˆ† H + + Ph −
HPh ‡ˆˆ
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).
[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 In (at this point half of indicator is in the
acid form and half in the form of its conjugate form.
Indicator (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.
ˆˆ† Me + + OH −
MeOH ‡ˆˆ
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 supress 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 between pK in − 1 to pK in + 1
Case 1 : pH = pK in − 1
I−n
Means = 0.1 = 10% Percentage ionization of indicator would be
[HIn]
I−n 0.10 HI n 1
−
× 100% = × 100% = × 100 = 9.1%
[I n ] + [HIn ] 0.10 HIn + (HI n ) 11
In fact, pH = pK in - 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.
[I −n ]
ii) at pH = pK in + 1 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 characteristic colour..
In fact pH = pKin + 1 is the minimum pH upto which the solution has a distinct characteristic colour of I −n
. At pH greater than this value, 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 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, the ionization constant of the indicator will
be

(A) 4.13 × 10 −5 (B) 4.13 × 10 −3

(C) 4.13 × 10 −6 (D) 4.13 × 10 −4
Solution: (D) 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
[H3 O+ ]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-
[H3 O+ ][In − ]
K In = [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:
[H + ][Ph − ]
HPh ‡ˆˆ ˆˆ† H + + Ph − Applying law of mass action, K =
Colourless Pink [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.
ˆˆ† H +3O + In −
HIn + H2 O ‡ˆˆ
`Acid form' `Baseform'
Conjuage acid-base pair

[In − ][H3+ 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.
ˆˆ† Me+ + OH −
MeOH ‡ˆˆ
Yellow Re d
[Me+ ][OH − ]
Applying law of mass action 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.
ˆˆ†
‡ˆˆ
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
C ˆˆˆ†
‡ˆˆˆ ˆ
OH −
ˆ 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
−
O 3S NH N N
CH 3
Quinonoid form — Acidic solution (red)
ˆˆˆ†
-
‡ˆˆˆ
OH
+
H
CH 3
−
O 3S N N N
CH 3
KEY CONCEPTS
1. Solubility Product (Ksp)
AxBy(s) xAy+(aq) + yBx-(aq)
Ksp = [Ay+]x [Bx-] y
2. Realtion between Ksp and Solubility (s)

Salt Type Relation between Ksp and s
AB Ksp = s2
AB2orA2B Ksp= 4s3
AB3or A3B Ksp= 27s4
A3B2or A2B3 ksp= 108s5
3. Dissociation constants of Mono basic

Acid (HA)
H3O+   A − 
Ka=
[HA ]
[H3O+] = Ka × C
Ka
Degree of dissociation, α =
C
For a mixture of two weak monobasicacids:
[H3O+] = K a1C1 + K a2C2
Strengthof Acid1 K a1C1
=
Strengthof Acid2 K a2C2
Ka1
⇒ R.S = Ka2 when C1= C2
4. Ionic Product of Water (Kw)
Kw = [ H3O+] [OH-]
= 1 × 10-14 at 298 K
pKw = - log Kw= 14 at 298 K
Ka × Kb = Kw
where Ka and Kb are dissociation constant of an acid and its conjugate base respectively

5. pH Scale
pH=0 acidic 7 alkaline 14

at 25°C Neutral
pH = - log[H3O ], [H3O+] = 10-pH
+
pOH = - log [OH-], [OH-] = 10-pOH

pH + pOH = 14 at 298 K
6. Buffer solutions
7. Hydrolysis of Salts
For salts of Strong Acid and Weak Base
Kw
Hydrolysis constant, K h =
Kb
Kh Kw
Degree of hydrolysis, h = C = K × C
b
8. For salts of Weak Acid and Strong Base
Kw
Hydrolysis constant (Kh) = ,
Ka
Kh Kw
Degree of hydrolysis, h = =
C Ka × C
1
pH =
2
[pKw + pKa + logC]
9. For salts of Weak Acid and Weak Base
Kw
Hydrolysis constant (Kh)= K × K ,
a b
Degree of hydrolysis, h = K h = Kw when h << 1

Ka × Kb
1
pH =
2
[pK w + pKa − pKb ]

CONCEPTUAL QUESTIONS
1. Consider the complete ionization of H 2SO 4 (strong acid) and (COOH)2 , oxalic acid (weak
acid) in liquid NH 3 .
→ 2NH +4 + SO 2–
H 2SO 4 + 2NH 3  4
→ 2NH +4 + (COO – ) 2
(COOH) 2 + 2NH 3 
Liquid NH 3 is called :
(A) proton-acceptor (B) leveling solvent
(C) both (D) none of these.
2. The following acids have been arranged in order of decreasing acid strength. Identify the correct
order.
HClO (I) HBrO (II) HIO (III)
(A) I > II > III (B) II > I > III
(C) III > II > I (D) I > III > II
3. Which one of following is the strongest base

(A) ClO3- (B) ClO2-
(C) ClO4- (D) ClO-
4. The conjugate acid of NH3 is

(A) NH2- (B) NH2OH
(C) NH 4 + (D) N2H4
5. In the equilibrium CH3COOH + HF CH3 COOH2+ + F-, which of the following statement(s)
is/are correct:
(A) F- is the conjugate acid of CH3COOH
(B) F- is the conjugate base of HF
(C) CH3COOH is the conjugate acid of CH3COOCH2+
(D) CH3COOCH2+ is the conjugate acid of CH3COOH
6. 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 pair is/are not correct:
(A) (HCl, CH3COOH) and (CH3COOH2+ and Cl-)
(B) (HCl, CH3COOH2+) and (CH3COOH, Cl-)
(C) (CH3COOH2+, HCl) and (Cl-, CH3COOH)
(D) (HCl, Cl-) and (CH3COOH2+, CH3COOH)

7. 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
Comprehension I
The degree of dissociation of weak electrolyte is inversely proportional to square root of concentration.
It is called Ostwald dilution law
Ka
α= As the temperature increases degree of dissociation will increase.
C
α1 K a1 α1 C2
= if conc. is same =
α2 K a2 α2 C1 if acid is same.
8. 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%
9. pH of 0.005 M HCOOH [Ka = 2 × 10-4] is equal to

(A) 3 (B) 2
(C) 4 (D) 5
10. Which of the following is strongest acidic solution

(A) pH = 1 (B) pH = 2
(C) pH = 3 (D) pH = 4
−4
11. α1 and α 2 are in ratio of 1 : 2 K a1 = 2 ×10 . What will be the value of Ka2
(A) 8 × 10-4 (B) 2 × 10-4
(C) 4 × 10-4 (D) 1 × 10-4
Comprehension 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 two 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.
12. Which of the following mixture will be a buffer solution when dissolved in 500 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

13. 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
14. 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
STRAIGHT OBJECTIVE TYPE QUESTIONS

LEVEL - I
pH Calculation of acid base

1. The pH of 10-3 M H2SO4 will be
(A) 3.5 (B) 2.69 (C) 3.0 (D) 4.69
2. To what volume must one litre of 1 M CH3COOH solution be diluted so that the pH of resulting
solution becomes twice the original value. [Given : K a = 1.8 × 10-5]
(A) 2.78 × 105 (B) 2.78 × 10 4 (C) 2.78 × 103 (D) 2.78 × 102
3. The ionisation constant of NH +4 in water is 5.6×10–10 at 25°C. The rate constant for the reaction
of NH +4 and OH– to form NH3 and H2O at 25°C is 3.4×1010 L mol–1 s–1. The rate constant for
proton transfer from water to NH3 will be
(A) 3.07 × 104 (B) 6.07 × 105 (C) 6.07 × 103 (D) 6.07 × 106
4. The pOH of 10-8 M HCl is

(A) 8 (B) 6
(C) Between 6 and 7 (D) Between 7 and 8.
5. Given that the dissociation constant for H2O, Kw = 1 × 10-14 mol2 litre-2, the pH of a 0.001 M
KOH solution will be
(A) 10-11 (B) 10-3 (C) 3 (D) 11
6. 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
7. 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

8. H2O + H3PO4 H3O+ + H2PO4 − , pK1 = 2.15

H2O + H2PO4 − H3O+ + HPO42 − , pK2 = 7.20
Hence, pH of 0.01 M NaH2PO4 is :
(A) 9.35 (B) 4.675 (C) 2.675 (D) 7.350.
9. An acid solution of pH 6 is diluted thousand times. The pH of solution becomes approx.

(A) 6.99 (B) 6 (C) 4 (D) 9
Salt hydrolysis
10. A weak acid HX has the dissociation constant 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
11. The pH of 0.1M CH3COONH4 is ……. Ka(CH3COOH) = 1.8 × 10 and -5
Kb(NH4OH) = 1.8 × 10-5

(A) 11.127 (B) 2.873 (C) 7 (D) 9.53
Buffer solution
12. 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 will be
(A) 1 : 2 (B) 2 : 1 (C) 1 : 3 (D) 3 : 1
13. 20 mL of 0.2 M sodium hydroxide is added to 50 mL of 0.2 M acetic acid to give 70 mL of the
solution. The additional volume of 0.2 M NaOH required to make the pH of the solution 4.74 is
(A) 2.86 ml (B) 14.86 (C) 4.86 ml (D) 8.46 ml
–5
( The ionisation constant of acetic acid is 1.8×10 )
14. A 40 mL solution of a weak base, BOH, is titrated with 0.1 N HCl solution. The pH of the
solution is found to be 10.04 and 9.14 after the addition of 5 mL and 20 mL of the acid respectively.
The dissociation constant of the base will be
(A) 1.82×10–3 (B) 1.82×10–4 (C) 1.82×10–5 (D) 1.82×10–6
15. 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
16. 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.
17. 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.

18. 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.
Solubility Products.
19. 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.
20. The solubility of M(OH)3 is x mol L-1. Its Ksp would be

(A) 9 x3 (D) 3 x4 (C) 27 x4 (D) 9 x4
21. 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
22. 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
Indicator based problem
23. Phenolphthalein is not a good indicator for titrating :

(A) NaOH against oxalic acid (B) ferrous sulphate against KMnO4
(C) NaOH against HCl (D) NaOH against H2SO4
24. Phenolphthalein does not acts as an indicator for the titration between :
(A) KOH and H2SO4 (B) Ba(OH)2 and HCl
(C) NaOH and acetic acid (D) oxalic acid and KMnO4
25. The range of pH in which methyl orange works as indicator :

(A) 3 - 4 (B) 10 -12 (C) 8 - 10 (D) 6 - 8
LEVEL - II
pH calculation of acid base
26. A solution contains 0.1 M H2S and 0.3 M HCl. Calculate the conc. of S2- and HS- ions in solution.
Given K a1 and K a 2 for H2S are 10-7 and 1.3 × 10-13 respectively..
(A) 1.44 × 10−19 ,3.3 × 10 −7 (B) 1.44 × 10−20 ,3.3 × 10 −8
(C) 1.44 × 10−22 ,3.3 × 10 −3 (D) 1.44 × 10−18 ,3.3 × 10 −5

27. An aqueous solution of metal bromide MBr2 (0.05M) is saturated with H2S. The minimum pH at
which MS will ppt. will be
Ksp for (MS) = 6 × 10-21
Concentration of saturated H2S = 0.1
Ka1(H2S) = 1 × 10-7
Ka2(H2S) = 1.3 × 10-13
(A) 0.982 (B) 0.0983 (C) 1.96 (D) 2.96
28. The self ionization constant for pure formic acid, K = [HCOOH2+][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.
(A) 0.0037 (B) 0.037 (C) 0.37 (D) 1.037
29. 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, the pH of rain on that day is
(A) 4.865 (B) 3.865 (C) 5.865 (D) 6.865
30. 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) 0.2 times of initial value
31. The degree of dissociation of water at 250C is 1.9 x 10-7% and density is 1.0 g cm-3. The
ionic constant for water is
(A) 1.0 x 10-14 (B) 2.0 x 10-16 (C) 1.0 x 10-16 (D) 1.0 x 10-8
Salt hydrolysis
32. The pH of 0.2 M solution of NH 4 Cl will be. [Given K b for NH 4 OH is 1.8 × 10 –5 ].
(A) 3.977 (B) 4.977 (C) 2.977 (D) 5.977
33. The pH of 0.02 M solution of ammonium chloride at 25°C is [Kb(NH3) = 1.8 × 10-5.
(A) 5.477 (B) 8.523 (C) 7 (D) 4.8732
34. Which one is more acidic in aqueous solutions ?

(A) NiCl2 (B) FeCl3 (C) AlCl3 (D) BeCl2
35. A 0.004 M solution of Na2SO4 is isotonic with 0.010 M solution of glucose at same temperataure.
The percentage dissociation of Na2SO4 is
(A) 25% (B) 50% (C) 75% (D) 85%
Buffer solution
36. 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.
(A) 4.75 (B) 5.63 (C) 6.63 (D) 3.63

37. 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.
(A) 1.05 (B) 0.05 (C) 0.25 (D) 1.25
38. One litre of an buffer solution containing 0.02 mol of propanoic acid and some sodium
propanoate has pH = 4.75. What will be the pH if 0.01 mol of hydrogen chloride is dissolved
in the above buffer solution ? [Dissociation constant of propanoic acid at 250C is
1.34 × 10-5. ]
(A) 4.11 (B) 2.11 (C) 0.11 (D) 3.11
39. 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, the change in pH value will be [Given that pKa
(CH3COOH) = 4.74]
(A) 0.125 (B) 0.225 (B) 0.01 (D) 0.0872.
40. A weak base (BOH) with K b = 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) 9.523.
41. 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.
42. 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.
43. An acetic acid and sodium acetate buffer has pH = 5.36, the value of concentration of
[AcO]/[HOAc] is (pKa of acetic acid = 4.76)
(A) 6 : 1 (B) 4 : 3 (C) 1 : 1 (D) 4 : 1
Solubility Products
44. Given the solubility product of Pb3(PO4)2 is 1.5 x 10-32. Determine the solubility in g/litre.
(A) 1.57×10-3 g/L (B) 1.57×10-2 g/L (C) 1.57×10-4 g/L (D) 1.57×10-5 g/L
45. The solubility of Mg(OH)2 in pure water is 9.57 × 10-3 g L-1, its solubility (in g L-1) in 0.02 M
Mg(NO3)2 will be
(A) 8.7 × 10 −4 (B) 8.7 × 10 −3 (C) 8.7 × 10 −2 (D) 8.7 × 10 −5
46. How much Ag+ would remain in solution after mixing equal volumes of 0.080 M AgNO3 and
0.08N HOCN. [Given that : Ksp for AgOCN = 2.3 × 10-7; Ka(HOCN) = 3.3 × 10-4 ]
(A) 5 × 10−5 M (B) 5 × 10−4 M (C) 5 × 10−3 M (D) 5 × 10−2 M
47. 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 M (B) 2.8 × 10-2M (C) 2.8 × 10-4M (D) 2.8 × 10-5M
Indicator based problem

48. 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 pH of the solution to observe a complete colour
change? (Ka = 1.0 ×10–5).
(A) 3 (B) 2 (C) 1 (D) 4
49. An acid base indicator has Ka of 3 ×10–5. The acid form of the indicator is red and the basic form
is blue. By how much must the pH change in order to change the indicator from 75% red to 75%
blue?
(A) 1.95 (B) 2.95 (C) 0.95 (D) 3.95
50. Solid AgNO 3 is added to a solution which is 0.1 M in Cl– and 0.1 M in CrO24− . Ksp values for
AgCl and Ag2CrO4 are 1.7×10–10 and 1.9×10–12 respectively. The concentration of Cl– when
Ag2CrO4 starts precepitating will be
(A) 3.9×10–5 M (B) 2.9×10–5 M (C) 3.9×10–3 M (D) 1.9×10–2 M
LEVEL - III
51. The Ksp of Mg(OH)2 is 8.9 × 10 at 25°C. If the pH of solution is adjusted to 9.0. How much
-12
Mg2+ ion will be precipitated as Mg(OH)2 from a 0.1M MgCl2 solution at 25°C? Assume that
MgCl2 is completely dissociated.
(A) 0.011 (B) 0.089 (C) 0.11 (D) 0.89
52. A certain volume of a monobasic weak acid was titrated against 0.1M NaOH solution. The end
point reached upon addition of 30 ml of alkali. The pH of the solution upon the addition of 20 mL
of alkali was 6.3. Ka for the weak acid will be
(A) 10-5 (B) 10-6 (C) 10-7 (D) 10-4
53. An aqueous solution contains 10% ammonia by mass and has density of 0.99 gm cm-3. The pH
of this solution is [Ka for = 5 × 10-10 M].
(A) 11.033 (B) 12.033 (C) 9.033 (D) 7.2033
54. The solubility product of Ca(OH)2 at 2500C is 4.42 × 10-5. A 500 mL of saturated solution of
Ca(OH)2 is mixed with equal volume of 0.4M NaOH. How much Ca(OH)2 in milligrams is
precipitated ?
(A) 758.2 mg (B) 725.2 mg (C) 785.2 mg (D) 658.2 mg
55. A solution of 0.010 M CdCl2 contaning 0.010 M NH3. What conc. of NH+4 ion from NH4Cl is
necessary to prevent the precipitation of Cd(OH)2?
(Ksp= 2 × 10-14 and Kb for NH4OH =1.8 × 10-5)
(A) 0.13 M (B) 0.23 M (C) 0.33 M (D) 1.13 M

56. What is the pH of the solution when 0.2 mol of hydrochloric acid is added to one litre of a
solution containing (i) 1 M each of acetic acid and acetate ion and (ii) 0.1 M each of acetic
acid and acetate ion ? Assume that the total volume is one litre.
Ka for acetic acid = 1.8 × 10-5.
(A) 4.57, 2 (B) 4.57, 1 (C) 5.57, 1 (D) 5.57,2
57. A weak acid HA after treatment with 12 mL of 0.1 M strong base BOH has a pH of 5. At the
end point, the volume of same base required is 26.6 mL. The Ka of acid is
(A) 8.219 × 10 −5 (B) 8.219 × 10 −7 (C) 8.219 × 10 −6 (D) 8.219 × 10 −4
58. 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).
(A) 4.7033 (B) 5.7033 (C) 6.7033 (D) 8.7033
59. A certain buffer solution contains equal concentration of X- and HX. Kb for X- is 10-10. Calculate
pH of buffer.
(A) 3 (B) 4 (C) 5 (D) 10
60. Nicotinic acid (Ka = 1.4 × 10-5) is represented by the formula HNiC. Calculate its per cent
dissociation in a solution which contains 0.10 mole of nicotinic acid per 2.0 litre of solution.
(A) 2.67 (B) 1.87 (C) 1.67 (D) 1.37
MULTIPLE OBJECTIVE TYPE QUESTIONS

LEVEL - I
1. pH of the following solution is not affected markedly by dilution:

(A) 0.01M CH3COONa
(B) 0.01 M NaHCO3
(C) buffer of 0.01 M CH3COONa and 0.01 M CH3COOH
(D) 0.01 M CH3COONH4
2. If concentration of two weak acids are different and D.O.I ( α ) are very less then their
relative strength can be compared by:
[ H + ]1 α1
(A) (B) α
[ H + ]2 2
C1α1 K a1 C1
(C) C α (D) K C
2 2 a2 2
3. 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) is a base (B) (A) is a base and (B) is an 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)
4. 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
5. Which of the following solution will have pH = 13 assume complete dissociations

(A) 2 g of NaOH in 500 ml solution (B) 100 ml of solution of 0.05 M Ca(OH)2
(C) 100 ml of solution of 0.1N Ca(OH)2 (D) 4g of NaOH in 500 ml solution.
6. An acid is a substance which:

(A) accepts a lone pair of electron (Lewis concept)
(B) donates a proton (Lowry and Bronsted concept)
(C) acts as an acid only in presence of a base
(D) none of the above
7. Which of the following statements is/are correct in the context of buffer mixtures?
(A) It contains a weak acid and its conjugate base
(B) It contains a weak base and its conjugate acid
(C) The pH of the buffer solution does not change much on the addition of a small amount of
acid or base
(D) The pH of acidic buffer mixture is less than 7
8. A base is a substance which:

(A) donates a lone pair of electron (Lewis concept)
(B) accepts a proton
(C) acts as a base only in presence of a acid
9. A buffer solution can be prepared by mixing solutions of:

(A) sodium chloride and sodium hydroxide
(B) ammonium hydroxide and ammonium chloride
(C) formic acid and sodium formate
(D) boric acid and borax
10. Select the species which can act as an acid and as Base
(A) SO42 − (B) HS−
(C) HCO3− (D) HSO4−
11. Which is/are general property of acids?
(A) They turn litmus red
(B) They react with alkalies
(C) They burn the skin
(D) They contain H atom replaceable with metal
12. Which of the following is/are buffer solution(s)?
(A) 10 mL 0.1 M HC1 + 20 mL 0.2 M NaCN (B) NH4C1 + NH4OH
(C) NaOH + Na2SO4 (D) Borax + boric acid

13. 10 mL of N/20 NaOH solution is mixed with 20 ml N/20 HC1 solution. The resulting solution
will:
(A) turn phenolphthalein solution pink (B) turn blue litmus red
(C) turn methyl orange red (D) [H+]>[OH-]
14. Which of the following will change if a 0.1 M solution of a weak acid is diluted to 0.01 M at
constant temperature ?
(A) Ka (B) pH
+
(C) H ion concentration (D) lonization percentage
15. Which of the following is/are Lewis acid(s)?

(A) NH3 (B) Mg2+
(C) AlCl3 (D) Ag+
16. When NH4C1 is added to a solution of NH4OH, the:

(A) concentration of OH- decreases
(B) dissociation of NH4OH decreases
(C) concentration of NH4 increases
(D) concentration of OH- increases
(E) pH of the solution increases
17. Which of the following statements is/are correct?

(A) NH4OH is a weak base
(B) NH4C1 forms an acidic solution in water
(C) CH3COOH is a weak acid
(D) CH3COONa forms an acidic solution in water
18. When equal volumes of the following solution mixed, precipitation of AgCl(Ksp= 1.8 x 10-11)
occur only with:
(A) 10-4 M/(Ag +) and 10-4 M/(C1-) (B) 10-1 M/(Ag+) and 10-5 A/(C1-)
-6 + -6 -
(C) I0 M/(Ag ) and 10 M(Cl ) (D) 10-10 M(Ag +) and 10-10 M(C1-1)

(A) Arrhenius acids are also Bronsted acids but all Arrhenius bases are not Bronsted bases
(B) All Bronsted bases are also Lewis bases
(C) All Bronsted acids are also Lewis acids
(D) A strong acid has a weak conjugate base but a strong base has a strong conjugate acid
20. Strong electrolyte(s) is/are those which:

(A) do not dissolve readily in water
(B) conduct electricity in molten state
(C) dissociate completely into ions at all concentrations
(D) dissociate into ions at high dilution

LEVEL - II
21. Which of the following statements is/are correct regarding Lewis acids?
(A) Molecules having a central atom with an incomplete octet in it can act as Lewis acids b)
(B) Molecules in which atoms of dissimilar eiectronegativity are joined by multiple bonds can
act as Lewis acids
(C) SiF4, PF5 and FeCl3 are Lewis acids
(D) Neutral species having at least one lone pair of electrons can act as Lewis acids
22. Which of the following will qualify as Lewis base?

(A) BC13 (B) CH4
(C) PH3 (D) NH3
23. Which of the following salt’s solutions is/are acidic?

(A) NaOCl (B) NH4NO3
(C) NaHSO3 (D) FeCl3
24. Which of the following behave as Bronsted acids as well as Bronsted bases?
(A) H2O (B) HS-
(C) H2SO4 (D) HCO3−
25. The incorrect statement(s) is/are:

(A) CH3COOH is a weak acid
(B) NH4C1 gives an alkaline solution in water
(C) CH3COONa gives an acidic solution in water
(D) NH4OH is a strong base
26. The pH of solution(s) is/are defined as the:

(A) negative logarithm of the hydrogen ion concentration
(B) logarithm of reciprocal of hydrogen ion concentration
(C) negative power raised on 10 in order to express [H+ ] ion concentration
(D) none of these
27. Which of the following statements is/are true?

(A) The solubility product is the product of concentration of ions of an electrolyte each raised
to the power of its coefficient in the balanced chemical equation in a saturated solution
(B) The solubility product of an electrolyte is a function of temperature
(C) Cations of group III are precipitated as their hydroxides by NH4OH in the presence of
NH4C1 because the solubility products of these hydroxides are low
(D) The solubility product changes with the concentration of an electrolyte

LEVEL - III
28. The Ostwald’s dilution law:

(A) is valid for weak electrolyte dissociation
(B) is useful in calculating ionization constant of acids or bases
(C) fails completely when applied to strong electrolytes

(A) A buffer solution contains a weak acid and its conjugate base
(B) A buffer solution shows little change in pH on the addition of a small amount of acid or
base
(C) A buffer solution can be prepared by mixing a solution of ammonium acetate and acetic
acid
(D) The addition of solid potassium cyanid to water increases the pH of water
COMPREHENSIONS 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 :
ˆˆˆ
AgCl (aq) ‡ˆˆ †ˆ Ag+ (aq) + Cl (aq.)
The equilibrium constant
 Ag +  Cl − 
K eq = 
[ AgCl ]
Keq × [AgCl] = [Ag+] [Cl-]
⇒ Ksp(AgCl) = [Ag+] [Cl-] Q [AgCl] is constant
If there would not have been a saturated solution, then from equation (A), 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 < K sp, then the solution is unsaturated and there will be no precipitate formation.
When Q = K sp, then solution will be saturated, no ppt. will be formed
when Q > K sp, 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. For a sparingly soluble salt Ap Bq the relationship of its solubility product ( LS ) with its
solubility ( S ) is
(A) LS = S p + q . p p .q q (B) LS = S p + q . p q .q p
(D) LS = S pq . ( pq )
p+q
(C) LS = S pq . p p .q q
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.)
ˆˆˆ
†
Ca(OH)2(s) ‡ˆˆ
ˆ Ca (aq)
2+
+ 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-]
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, espectively. To confirm the above facts 0.5 M CH3COOH is taken for the experiments.
[Given : Ka of acetic acid = 1.8 ×10-5]
5. pH of the solution will be -

(A) 2.52 (B) 2.22
(C) 5 (D) 3.92
6. 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
(C) 4.6 × 10 −6 M (D) 1.25 × 10-3 M
7. 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

WRITE UP - III
In qualitative analysis, cations of group II as well as group IV 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: Ka 1 (H 2 S) = 10 -7 , Ka 2 (H 2 S) = 10 -14 , K sp (SnS) = 8 × 10 -29 K sp (CdS) = 10 -28 ,
Ksp(NiS) =3 × 10-21
8. If HCl solution is passed slowly then which sulphide will precipitate first -
(A) SnS (B) CdS
(C) NiS
(D) All of these will be precipitated simultaneously
9. At what pH precipitate of NiS will form -

(A) 12.76 (B) 7
(C) 1.24 (D) 4
10. Which of the following sulphide is more soluble in pure water-

(A) CdS (B) NiS
(C) SnS (D) all have equal solubility
MATRIX MATCH TYPE
1. Match the column

Column I (salt) Column II (pH)
1
(A) Salt of strong acid and strong base (p) [pK w + pKa − pK b ]
2
1
(B) Salts of weak acid and strong base (q) [pK w + pK a + logC]
2
1
(C) Salt of weak base and strong acid (r) [pK w − pK b − logC]
2
1
(D) Salt of weak acid and weak base (s) pK w
2

2. Match the column

Column I Column II
(A) NH4Cl (p) no hydrolysis
Kh
(B) NaCl (q) h =
C
Kw
(C) CH3COONa (r) h =
CK b
(D) CH3COONH4 (s) h = K h

(t) pH < 7 at 250C
3. Consider a buffer of CH3COOH and CH3 COONa of maximum buffer-capacity and match
the following :
Column I Column II
(A) For maximum buffer capacity (p) No change in pH
(B) Adding equal number of moles of
CH3COOH and CH3COONa (q) pH > pKa
(C) Diluting buffer 10 times (r) pH = pKa
(D) Adding some NaOH to buffer (s) pOH = pKb
4. Kw under conditions of high temperature and pressure is 1.0 x 10-10. Matching following
Column I Column II
(A) Solution of pH 5.5 (p) Neutral
(B) Solution of pH 5 (q) Acidic
(C) Solution of pH 4 (r) [OH-] = 10-3 M
(D) Solution of pH 7 (s) Basic

ASSERTION AND REASONING
Code:
(A) STATEMENT-1 is True, STATEMENT-2 is True, STATEMENT-2 is correct explanation of
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True, STATEMENT-2 is NOT correct explanation of
STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 & STATEMENT-2 both are False.
1. STATEMENT-1: At 250C, the pH of 10-8 M HCl is 8

STATEMENT-2: pH of acidic soltuion is always greater than 7 at 250C
2. STATEMENT-1: pH of a neutral solution is always 7

STATEMENT-2: pH of a solution does not depend upon temperature
3. STATEMENT-1: pH of buffer changes with temperature

STATEMENT-2: Ionic product of water (Kw) changes with temperature.
5. STATEMENT-1: The dissociation of water at 600C is 10-13.
STATEMENT-2: The pH of water is 6.5 and that it behaves as acid at 600C.
6. STATEMENT-1: Addition of NH4Cl suppresses the dissociation of NH4OH due to common

ion effect.
STATEMENT-2: The pH of NH4OH remains unchanged on addition of NH4Cl.

INTEGER TYPE QUESTIONS
1. What will be pH of the resulting solution obtained by mixing 20 mL of 0.1 N HCl and 20 mL of
0.1 N KOH solution?
2. What will be pH of the resulting solution obtained by mixing 10 mL of 0.1 N HCl and 990 mL
solution of NaCl?
3. CH 3 COONH 4 is dissolved in water at 25 0 C. What will be pH of the solution?
(Assume pKa = pKb)
4. What will be pH of one litre of a buffer solution containing 0.01 M NH4Cl and 0.01 M NH4OH
having pKb = 5?
5. What will be pH of the solution of the salt of weak acid and weak base?
(Kb = 1 × 10-6 and Ka = 1× 10-4)
6. Conjugate base of [Al(H2O)6]+3 is Al (H2O)x(OH)y, the value of x/y is,
7. The mixture of 10 ml 0.5 N CH3COOH and 10 ml of 0.25 M NaOH , having pH = 5, then find
the value of pKa?
8. Among these mixture
(i) 50 ml of N/10 HCl + 50 ml of N/10 NaOH
(ii) 55 ml of N/10 HCl + 45 ml of N/10 NaOH
(iii) 75 ml of N/10 HCl + 25 ml of N/10 NaOH
(iv) 30 ml of N/5 ml HCl + 70 ml of N/5 NaOH
How many mixutre is pH lies between (1 to 7)
9. Calculate the pH when one moles of NaCl is dissolves in 1Ltr. of water

SUBJECTIVE QUESTIONS
1. What [H3O+] must be maintained in a saturated H2S solution to precipitatePb2+, but not Zn2+
from a solution in which each ion is present at a concentration of 0.01 M?
[ K sp H2S = 1.1× 10 −22 ; K sp ZnS = 1.0 × 10 −21 ].
2. Calculate simultaneous solubility of AgCNS and AgBr in a solution of water. Ksp of
AgBr = 5 × 10-13 and Ksp of AgCNS = 1 × 10-12.
3. A sample of AgCl 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 littre. Calculate the solubility product of AgCl
(K sp Ag2 CO3 = 8.2 × 10 −12 )
4. A solution has 0.05 Mg2+ 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 ionization
constant of NH3 is 1.8 × 10 −5 .
5. 0.01 mol of AgNO3 is added to 1 litre of a solution which is 0.1 M in Na 2 CrO 4 and 0.005 M
in NaIO3 . Calculate the mol of precipitate formed at equilibrium and the concentrations of
Ag + , IO 3– and CrO 2–
4 . (
K sp values of Ag 2 CrO 4 and AgIO3 are 10 –8 and 10 –13 respec-
tively).
6. 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 precipitate almost completely. What % of that metal ion is precipitated.
KSP of AgI = 8.5 × 10-17 and KSP of Hg2I2 = 2.5 × 10-26
7. The KSP of Ag2C2O4 at 25°C is 1.29 × 10-111 mol3 L-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 ‡ˆˆ ˆˆˆ †ˆ 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.
8. 0.1 M NaOH is titrated wth 0.1 M HA till the end point. Ka of HA is 5.6 × 10 −6 and degree of
dissociation is less compared to 1. Calculate the pH of the resulting solution at the end point.
9. 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..
2 2
10. 2.5 mL of M weak monoacidic base ( K b = 1× 10 −12 at 25°C) is titrated with M HCl in
5 15
water at 25°C. Then calculate the concentration of H + at equivalence point
(K w = 1× 10−14 at 25o C) .

PREVIOUS YEARS IIT JEE QUESTIONS
SINGLE CORRECT ANSWER TYPE

1. Amongst the following hydroxides, the one which has the lowest value of K sp at ordinary
temperature (about 250C) is
(A) Mg(OH)2 (B) Ca(OH)2 (C) Ba(OH)2 (D) Be(OH)2
(IIT JEE 1990)
2. The following equilibrium is established when hydrogen chloride is dissolved in acetic acid.
HCl + CH3COOH ‡ˆˆ ˆˆ† 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 (CH3COOH2+,
CH3COOH)
(IIT JEE 1992)
3. 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 > III (C) III > II > I (D) I > III > II
(IIT JEE 1996)
0
4. If pKb for fluoride ion at 25 C is 10.83, the ionisation constant of hydrofluoric acid in water at
this temperataure is
(A) 1.74 × 10-5 (B) 3.52 × 10-3 (C) 6.75 × 10-4 (D) 5.38 × 10-2
(IIT JEE 1997)
5. The solubility of A2X3 is y mol dm-3. Its solubility product is
(A) 6y4 (B) 64y4 (C) 36y5 (D) 108y5
(IIT JEE 1997)
6. The pH of 0.1 M solution of the following salts increases in the order
(A) NaCl < NH4Cl < NaCN < HCl (B) HCl < NH4Cl < NaCl < NaCN
(C) NaCN < NH4Cl < NaCl < HCl (D) HCl < NaCl < NaCN < NH4Cl
(IIT JEE 1992)
7. The set with correct order of acidity is
(A) HClO < HClO2 < HClO3 < HClO4 (B) HClO4 < HClO3 < HClO2 < HClO
(C) HClO < HClO4 < HClO3 < HClO2 (D) HClO4 < HClO2 < HClO3 < HClO
(IIT JEE 2001)
8. For a sparignly soluble salt ApBq, the relationship of its solubility product (Ls) with its solubility
(S) is
(A) Ls = Sn + q. pp. qq (B) Ls = Sp + q.pq. qp (C) Ls = Spq.pp.qq (D) Ls = Spq.(pq)p +q
(IIT JEE 2001)
9. A weak acid HX has the dissociation constant 1 × 10 M. It forms a salt NaX on reaction
-5
with alkali. The percentage hydrolysis of 0.1 M solution of NaX?

(A) 0.0001% (B) 0.01% (C) 0.1 % (D) 0.15 %
(IIT JEE 2004)

10. 0.1 mole of CH3NH2 (Kb = 5 × 10-4) is mixed with 0.08 mole of HCl and diluted to one litre.
What will be the H+ concentration in the solution.
(A) 8 × 10-2 M (B) 8 × 10-11 M (C) 8 × 10-15 M (D) 8 × 10-5 M
(IIT JEE 2005)
11. Ag+ + NH3 ‡ˆˆˆˆ† [Ag(NH3)+]; k1 = 6.8 × 10-3
[Ag(NH3)]+ + NH3 ‡ˆˆˆˆ† [Ag(NH3)2]+ k2 = 1.6 × 10-3
then the formation constant of [Ag(NH3)2]+ is
(A) 1.08 × 10-7 (B) 1.08 × 10-5 (C) 1.08 × 10-9 (D) None of these
(IIT JEE 2006)
12. 2.5 mL of (2/5) M weak monoacidic base (Kb = 1 × 10-12 at 250C) is titrated with (2/15) M
HCl in water at 250C. The concentration of H+ at equivalence point is (Kw = 1 × 10-14 at
250C )
(A) 3.7 × 10-13 M (B) 3.2m × 10-7 M (C) 3.2 × 10-2 M (D) 2.7 × 10-2 M
(IIT JEE 2008)
13. Solubility product constants (Ksp) of salts of types MX, MX2 and M3X at temperature T are
4.0 × 10-8, 3.2 × 10-14 and 2.7 × 10-15 respectively. Solubility (mol dm-3) of the salts at
temperature ‘T’ are in the order.
(A) MX > MX2 > M3X B) M3X > MX2 > MX
(C) MX2 > M3X > MX (D) MX > M3X > MX2
MULTIPLE CORRECT ANSWER TYPE
14. Which of the following statement (s) is (are) correct ?

(A) The pH of 1.0 × 10-8 M solution of HCl is 8
(B) The conjugate base of H2PO4- is HPO42-
(C) Autoprotolysis constant of water increases with temperature
(D) When a solution of weak monoprotic acid is titrated against a strong base, at half-
neutralisation point pH = (1/2) pKa (IIT JEE 1998)
15. A buffer solution can be prepared from a mixture of (IIT JEE 1999)
(A) sodium acetate and acetic acid in water
(B) sodium acetate and hydrochloric acid in water
(C) ammonia and ammonium chloride in water
(D) ammonia and sodium hydroxide in water

SUBJECTIVE TYPE QUESTION

16. What is the pH of 1.0 M solution of acetic acid ? To what volume must one litre of this solution
be diluted so that the pH of the resulting solution will be twice the original value ?
Given : Ka = 1.8 × 10-5. (IIT JEE 1990)
17. The solubility product of Ag2C2O4 at 25°C is 1.29 × 10-111 mol3 L-3. A solution of K2C2O4
containing 0.1520 mole in 500 ml water is shaken at 25°C with excess of Ag2CO3 till the follow-
ing equilibrium is reached:
Ag2CO3 + K2C2O4 ‡ˆˆ ˆˆ† Ag2C2O4 + K2CO3
At equilibrium the solution contains 0.0358 mole of K2CO3. Assuming the degree of dissociation
of K2C2O4 and K2CO3 to be equal, calculate the solubility product of Ag2CO3.
18. A 40.0 ml solution of weak base, BOH is titrated with 0.1 N HC1 solution. The pH of the solution
is found to be 10.04 and 9.14 after adding 5.0 mL and 20.0 ml of the acid respectively. Find out
the dissociation constant of the base. (ITT JEE 1991)
19. The solubility product (Ksp) of Ca(OH)2 at 25°C is 4.4 × 10-5. A 500 ml of saturated solution of
Ca(OH)2 is mixed with equal volume of 0.4 M NaOH. How much Ca(OH)2 in milligrams is
precipitated ? (IIT JEE 1992)
20. An aqueous solution of a metal bromide MBr2 (0.05M) 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, Kl = 10-7 and K2 = 1.3 × 10-3, for H2S. (IIT JEE 1993)
21. Calculate the pH of an aqueous solution of 1.0 M ammonium formate assuming complete disso-
ciation. (pKa of formic acid = 3.8 and pKb of ammonia = 4.8.) (IIT JEE 1995)
22. What is the pH of a 0.50 M aqueous NaCN solution ? pKb of CN- is 4.70. (IIT JEE 1996)
23. A sample of AgCl 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). (IIT JEE 1997)
24. 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] in 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) ? (IIT JEE 1997)

25. Given : Ag(NH3)2+ ‡ˆˆˆˆ† Ag+ + 2NH3, Kc = 6.2 × 10-8 and Ksp of AgCl = 1.8 × 10-10 at 298
K. If ammonia is added to a water solution containing excess of AgCl(s) only, calculate the
concentration of the complex in 1.0 M aqueous ammonia. (IIT JEE 1998)
26. What will be the resultant pH when 200 ml of an aqueous solution of HC1 (pH = 2.0) is mixed
with 300 ml of an aqueous solution of NaOH (pH = 12.0) ? (IIT JEE 1998)
27. 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 (IJT JEE 1999)
28. 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 moles litre-1 and the pKa of H2SO3 is 1.92, estimate the pH of rain on that day.
(IIT JEE 2000)
29. 500 mL of 0.2 M aqueous solution of acetic add is mixed with 500 ml of 0.2 M HC1 at 250C.
(i) Calculate the degree of dissociation of acetic acid in die 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] (ITT JEE 2002)
30. 0.1 M NaOH is titrated with 0.1M HA till the end point; Ka for HA is 5.6 × 10-6 and degree of
hydrolysis is less compared to 1. Calculate pH of the resulting solution at the end point.
(IIT JEE 2004)

Ionic Equlibrium Final

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Ionic Equlibrium Final

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CHEMISTRY IONIC EQUILIBRIUM

Bronsted - Lowry Concept

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c) Conjugate Acid-Base Pairs

d) Formation of conjugate acids and bases are simultaneous process.

Conjugage Acid-Base pair

Acid 1 + Base2 ˆˆ† Acid2 + Base1

Conjugate Acid-Base pair

Stronger acid + Stronger Base Weaker acid + Weaker Base

Conjugate Acid-Base pair

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Conditions for Lewis Acid

2. Simple cations: e.g. H+, Ag+.

1. Molecule(s) whose central atom has unshared pair(s) of electrons e.g. -

4. Solvent system concept

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Strength of Acids And Bases

What is meant by strength of acids and bases:

ˆˆ† H3O+ (aq) + F-(aq)

ˆˆ† NH +4 (aq) + OH-(aq)

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Relative Strength of Inorganic Acids

· Volume available for negative charge is increasing in the conjugate bases

2. Hydro acids of the elements of the same group:

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Acidity of conjugate acids is increasing

Illustration 1: The order of increasing acidic strength of CH 4 , NH 3 , H 2 O and HF is:

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Hence the increasing acidic character of the corresponding conjugate acids is

a) HOCl < HOClO < HOClO 2 < HOClO3

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Relative Strength of Inorganic Bases

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ˆˆ† ionized molecules

Ostwald's Dilution Law

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K eq [H 2O(l)] = [H3 O+ ][OH − ]

Solution: (A) Kw for H2O at 25°C = 10-14

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[H+] = (9.62 × 10−14 ) = 3.10 × 10-7 M

pH determination for Weak Acids

Illustration 3. The degree of dissociation of 0.05 M NH3 at 25°C in a solution of pH = 11 will

Solution. (A) NH4OH ˆˆ† NH + + OH −

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Illustration 4. A solution of HCl has a pH = 5. If one ml of it is diluted to 1 litre, pH of resulting

Solution: (A) HCl1 = 10-5 M since pH = 5

Meq. Of HClII in 1000 mL = N × 1000

Solution (B) HCl + NaOH → NaCl + H2O

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Common ion effect

Determination of pH of acids or bases

e.g. find the pH of 10-8 M HCl

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Solving, we get x = 9.6 × 10-8

Illustration 6: What is molar concentration of Ca(OH)2 if its solution has pH of 12 ?

Solution: (C) pH of Ca(OH)2 = 12

Relative strength of Acids and Bases

If C1 and C2 are same, then

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Illustration 7: What concentration of HCOO- is present in a solution of 0.015 M HCOOH and

Solution: (B) Given,

(B) pH calculation of solution of a mixture of two weak Monobasic Acids in water

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[H3 O+ ][B− ] [C1α1 + C 2 α 2 ][C2 α 2 ]

pH = – log[H + ] = – log[C1α1 + C 2 α 2 ] = -log K a C1 + K a C2

where K a1 = Ka(HA) and K a2 = Ka(HA)