Ionic Equilibrium

IIT CHEMISTRY
HYDROCARBON
Physical & Inorganic Organic Chemistry

NV Sir VKP Sir
B.Tech. IIT Delhi M.Sc. IT-BHU
NUCLEON IIT-JEE
Be in Equilibrium with JEE
A-475 Indra vihar, kota Ph. - 8209916365 (NV Sir) 9057586906(VKP Sir)
NUCLEON IIT-JEE
CLASSES FOR IIT-JEE
HYDROCARBON
Contents
Topic Page No.
Theory 01 - 48
Board Level Exercise 49 - 50
Exercise - 1 51 - 63
ANSWER KEY 76 - 86
Syllabus
IIT-JEE 2019
Name : ____________________________ Contact No. __________________
A - 475 Indra Vihar , Kota

IONIC EQUILIBRIUM
Strong electrolytes :
(i) Those substance which are almost completely ionize into ions in their aqueous solution are
called strong electrolytes.
(ii) Degree of ionization for this type of electrolyte is one i.e.  1. eg. HCl, H2SO4, NaCl.HNO3,
KOH, NaOH, HNO3, AgNO 3, CuSO 4, etc. Means all strong acids and bases and all types of
salts.
Weak electrolytes :
(i) Those substance which are ionize to a small extent in their aqueous solution are known weak
electrolytes.eg. H2O, CH3COOH, NH4OH, HCN, HCOOH, Liq. SO2 etc. Means all weak acids
and bases.
(ii) Degree of ionization for this types of electrolytes in  <<< 1.
DEGREE OF DISSOCIATION
 When an electrolyte is dissolved in a solvent (H2O), it spontaneously dissociates into ions.
 It may dissociate partially ( << < 1 ) or sometimes completely (  1 )
Eg. NaCl + aq Na+ (aq) + Cl – (aq)
CH3COOH + aq CH3COO– (aq) + H+ (aq)
 The degree of dissociation of an electrolyte () is the fraction of one mole of the electrolyte
that has dissociated under the given conditions.
No. of moles dissociate d
=
No. of moles taken initially
For a weak electrolyte A+B– dissolved is water, if  is the degree of dissociation then
AB (aq) A+ (aq) + B– (aq)
initial conc C 0 0
conc-at eq. C(1 – ) C C
Then according to law of mass action,
[ A  ][B – ] C . C C 2
Keq =   = dissociation constant of the weak electrolyte
[ AB ] C(1   ) (1   )
1
[C = , then V = 1/C(volume of solution in which 1 mole is present) is called dilution,
V
2
so Keq =
(1   ) V
Physical & Inorganic By Organic Chemistry By

NV Sir A-475 Indra vihar, kota
VKP Sir Ionic Equilibrium # 1
B.Tech. IIT Delhi
Ph. - 8209916365 (NV Sir) 9057586906(VKP Sir)
M.Sc. IT-BHU
K eq
If  is negligible in comparison to unity then, 1 –  ~
– 1. So Keq = 2 C  = = K eq . V
c
1
  { Thumb rule }
concentrat ion
ACIDS BASES AND SALTS :

 Arrhenius concept :
Arrhenius Acid : Substance which gives H+ ion on dissolving in water (H+ donor)
eg. HNO3, HClO4, HCl, HI, HBr, H2SO 4, H3PO 4 etc.
Types of acids
 H3BO 3 is not Arrhenius acid.

 H+ ion in water is extremely hydrated (in form of H3O+, H5O2+, H7O3+) and high charge density.
 The structure of solid HClO4 is studied by X-ray, It is found to be consisting of H3O+ and ClO4¯.
HClO4 + H2O H3O + + ClO 4¯ (better representation)
Arrhenius base : Any substance which releases OH¯ (hydroxyl) ion in water (OH¯ ion donor)
Types of base
 OH¯ ion also in hydrated form of H3O2¯, H7O 4¯, H5O3¯
 First group elements (except Li.) form strong bases.
Bronsted - Lowery concept : (Conjugate acid - base concept) (Protonic concept)

Acid : Substances which donate H+ are Bronsted Lowery acids (H+ donor)
Base : Substances which accept H+ are Bronsted Lowery bases (H+ acceptor)
Conjugate acid - base pairs

In a typical acid base reaction
HX + B X– + HB+

B.Tech. IIT Delhi
Ph. - 8209916365 (NV Sir) 9057586906(VKP Sir)
M.Sc. IT-BHU
 Forward reaction – Here HX, being a proton donor, is an acid
B, being a proton acceptor, is a base.
 Backward reaction – Here HB+, being a proton donor, is an acid

X–, being a proton acceptor, is a base.
Acid Base Conjugate Conjugate

Acid Base
 HCl + H2O H3O + + Cl¯
 HSO4– + NH3 NH4+ + SO42–
 [Fe(H2O)6]3+ +H2O H3O + + [Fe(H2O)5 (OH)]2+
 Conjugate acid - base pair differ by only one proton

 Strong acid will have weak conjugate base and vise versa
 Reaction will always proceed from strong acid to weak acid or from strong base to weak base.
eg. Acid Conjugate base Base Conjugate acid
HCl Cl¯ NH3 NH4+
H2SO4 HSO4¯ H2O H3O+
HSO4¯ SO 42– RNH2 RNH3+
H2O OH¯
Amphoteric (amphiprotic) : substances which can act as acid as well as base are known as amphoteric
HCl + H2O H3O + + Cl¯
base
NH3 + H2O NH4+ + OH¯
acid
LEWIS CONCEPT (ELECTRONIC CONCEPT) :

 An acid is a molecule/ion which can accept an electron pair with the formation of a coordinate
bond.
Acid  e– pair acceptor
e.g. Electron deficient molecules : BF3, AlCl 3
Cations : H+, Fe2+, Na+
Molecules with vacant orbitals : SF4, PF 3
 A base is any molecule/ion which has a lone pair of electrons which can be donated.
Base  (electron pair donor)
e.g. Molecules with lone pairs (ligands) : NH3, PH3, H2O, CH3OH
PROPERTIES OF WATER :
 Amphoteric (amphiprotic) Acid/base nature:
Water acts as an acid as well as base according to Arhenius and Bronsted-Lowry theory but
according to Lewis concept it can be generally taken as base.
In pure water [H+] = [OH–] so it is Neutral.
 Molar concentration / Molarity of water :
1000 gm / litre
Molarity   No. of moles/litre = 18gm / mole = 55.55 mole /litre = 55.55 M (density
= 1 gm/cc)
 Ionic product of water : According to Arrhenius concept
H2O H+ + OH– so, ionic product of water, Kw = [H+][OH–] = 10–14 at 25° (exp.)

B.Tech. IIT Delhi
Ph. - 8209916365 (NV Sir) 9057586906(VKP Sir)
M.Sc. IT-BHU
 dissociation of water, is endothermic, so on increasing temperature Keq. increases
Kw increases with increase in temperature.
Now pH = –log[H+] = 7 and pOH  log[OH–] = 7 for water at 25° (experimental)

pH = 7 = pOH  neutral
pH < 7 or pOH > 7  acidic at 25°C
pH > 7 or pOH < 7  Basic
 Ionic product of water is always a constant whatever has been dissolved in water
since its an equilibrium constant so will be dependent only on temperature.
 Degree of dissociation of water :
no. of moles dissociated 10 7
H2O H+ + OH–    =  18 x10 10 or 1.8 x 10 7%
total no. of moles initially taken 55.55
 Absolute dissociation constant of water :

[H ][OH ] 10 7  10 7
H2O H+ +OH– Ka = Kb = =  1.8  10 16
[H2O] 55.55
So, pKa of H2O = pKb of H2O = – log (1.8 × 10-16) = 16 – log 1.8 = 15.74
pH CALCULATIONS OF DIFFERENT TYPES OF SOLUTIONS :

Strong acid Solution :
(i) If concentration is greater than 10–6 M
In this case H+ ions coming from water can be neglected,
so [H+] = normality of strong acid solution.
(ii) If concentration is less than 10–6 M
In this case H+ ions coming from water cannot be neglected,
So [H+] = normality of strong acid + H+ ions coming from water in presence of this strong acid
Strong base Solution :

Calculate the [OH–] which will be equal to normality of the strong base solution and then use
KW = [H+] × [OH–] = 10–14 , to calculate [H+].
pH of mixture of two strong acids :

If V1 volume of a strong acid solution of normality N1 is mixed with V2 volume of another strong
acid solution of normality N2 , then
m. equi. of H+ ions from -solution = N1V1
m. equi. of H+ ions from -solution = N2 V2
If final normality is N and final volume is V, then
NV = N1 V1 + N2 V2
[dissociation equilibrium of none of these acids will be disturbed as both are strong acid]
N1V1  N2 V2
[H+] = N =
V1  V2
pH of mixture of two strong bases :
similar to above calculation
N1V1  N2 V2 1014
[OH–] = N = & [H+] =
V1  V2 [OH]
pH of mixture of a strong acid and a strong base :

 Acid Base neutralisation reaction will take place.
 The solution will be acidic or basic depending on which component has been taken in excess.

B.Tech. IIT Delhi
Ph. - 8209916365 (NV Sir) 9057586906(VKP Sir)
M.Sc. IT-BHU
 If V1 volume of a strong acid solution of normality N1 is mixed with V2 volume of a strong
base solution of normality N2 , then
Number of m. eq. H+ ions from -solution = N1V1
Number of m. eq. OH– ions from -solution = N2 V2
pH of a weak acid(monoprotic) Solution :

 Weak acid does not dissociated 100% therefore we have to calculate the percentage
dissociation using Ka dissociation constant of the acid.
 We have to use Ostwald’s Dilution law (as we have been derived earlier)
HA H+ + OH–
t = 0 C 0 0
[H ] [OH ] C 2
t = teq C(1–) C C Ka = =
[HA ] 1 
Ka
If  <<1  1 –   1    Ka  C2  = ( is valid if  < 0.1 or 10%)
C
Ka 1
[H+] = C = C = Ka  C  So pH = pK a  log C
C 2
on increasing dilution  C           and [H+]   pH 
pH of a mixture of weak acid(monoprotic) and a strong acid Solution :

 Weak acid and Strong acid both will contribute H+ ion.
 For the first approximation we can neglect the H+ ions coming from the weak acid solution
and calculate the pH of the solution from the concentration of the strong acid only.
 To calculate exact pH, we have to take the effect of presence of strong acid on the dissociation
equilibrium of the weak acid.
If [SA] = C1 and [WA] =C2 , then [H+] from SA = C1
the weak acid will dissociate as follows.
HA H+ + A –
C2 0 0
(C 2   C1 ) C2 
C2(1– C2  C1 C2  Ka = C 2 (1   )
 (    )
(The weak acids dissociation will be further suppressed because of presence of strong acid,
common ion effect)
Ka = (C2  C1)
Total H+ ion concentration = C1 + C2
 If the total [H+] from the acid is greater than 10–6 M, then contribution from the water can be
neglected at 25ºC temp., if not then we have to take [H+] from the water also.

B.Tech. IIT Delhi
Ph. - 8209916365 (NV Sir) 9057586906(VKP Sir)
M.Sc. IT-BHU
pH of a mixture of two weak acid (both monoprotic) solutions :
 Both acids will dissociate partially.
 Let the acid are HA1 & HA2 and their concentrations in the mixture are C1 & C2 respectively,
then
HA1 H+ + A1 – HA2 H + + A 2–
t= 0 C1 0 0 C2 0 0
At eq. C1(1– 1) C11+C22 C11 C2(1– 2) C22+C11 C22
C1(C11  C2  2 ) (C 2  2  C11 )C 2  2
Ka1 = Ka2 =
C 2 (1   2 )
C1(1  1 )
(Since 1, 2 both are small in comparision to unity)
K a1 1
Ka1 = (C1  C22)               Ka2 = (c1  c2 2)  K a2
=
2
C1K a1 C 2K a2
[H+] = C11 + C2 = +  [H+]= C1K a1  C 2K a2
C1K a1  C2K a2 C1K a1  C2K a2
 If the dissociation constant of one of the acid is very much greater than that of the second
acid then contribution from the second acid can be neglected.
So, [H+] = C11 + C2  C11
pH of a Solution of a polyprotic weak acid :

 Diprotic acid is the one, which is capable of giving 2 protons per molecule in water.
Let us take a weak diprotic acid (H2A) in water whose concentration is C molar.
In an aqueous solution, following equilbria exist.
1 = degree of ionization of H2A in presence of HA¯ Ka1 = first ionisation constant of H2A.
2 = degree of ionisation of HA¯ in presence of H2A. Ka2 = second ionisation constant of
H2A.
I step II step
H2A HA¯ + H+ HA¯ A 2– + H+

c(1 – 1) c(1 – 2) (c1 + c1  ) c(1 – 2) c2 (c1 + c1  )
[H ] [HA  ] [H ] [ A 2 ]

Ka1 = Ka2 =
[H2 A ] [HA  ]
(c1  c1 2 )[c1(1   2 )] (c1  c1 2 )(c1c 2 )

 Ka1 = c(1  1 )
Ka2 = c1 (1   2 )
[c1(1   2 )][1(1   2 )] [c1(1   2 )]  2

= ........(i) = ..........(ii)
1  1 1 2
Knowing the values of Ka1 , Ka2 and c, the values of 1 and 2 can be calculated using equations
(i) and (ii).
After getting the values of 1 and  [H3O+] can be calculated as.
[H3O +]T = c1 + c12
Finally, for calculating pH

 If the total [H3O+] < 10–6 M, the contribution of H3O + from water should be added
 If the total [H3O+] > 10–6 M, then [H3O+] contribution from water can be ignored.
Using this [H3O+], pH of the solution can be calculated.

B.Tech. IIT Delhi
Ph. - 8209916365 (NV Sir) 9057586906(VKP Sir)
M.Sc. IT-BHU
Approximation
For diprotic acids, Ka < < Ka and 2 would be even smaller than 1 .
2 1
 1 – 2  1 and 1 + 2  1
C1  1
Thus, equation (i) can be reduced to Ka1 = 1  1
This is an expression similar to the expression for a weak monoprotic acid.
 Hence, for a diprotic acid (or a polyprotic acid) the [H3O +] can be calculated from its first
equilibrium constant expression alone provided Ka << Ka .
2 1
Neutralisation :
A reaction between acid and base to form salt and water molecule is known as neutralisation. In this
type of reaction acid gives H+ ion and base gives OH– ion.
Hydrolysis
It is defined as a process involving the reaction of water on a salt to form mixture of acid and base.
(a) It is the just reverse process of neutralization
Salt + water Acid + Base
(b) In this reaction the solution is always neutral when both acid and base are strong.
(c) If acid is stronger than base, the solution is acidic and if base is stronger than acid, the
solution is basic.
(d) Depending upon the nature of an acid or a base, there can be four types of salt -
(i) Salt of strong acid and strong base.
(ii) Salt of strong acid and weak base.
(iii) Salt of weak acid and weak base.
(iv) Salt of weak acid and strong base.
Strong Weak Strong Weak

acids acids bases bases
HCl CH3COOH NaOH NH4OH
H2SO4 HCN KOH LiOH
HNO3 H2CO3 RbOH Ca(OH)2
HClO4 H3PO4 CsOH Be(OH)2
HI H3PO3 Ba(OH)2 Zn(OH)2
H2SO3 HOCl Al(OH)3
COOH Fe(OH)3
| RNH2
COOH NH3
ANIONIC HYDROLYSIS
Anions can function as a base on reaction with water and hydrolyse as follows :
A–(aq) + H2O (l) HA (aq) + OH– (aq)
The extent of hydrolysis of a given anion depends on its basic strength
CATIONIC HYDROLYSIS
Cations can function as acid on reaction with water and hydrolyze as follows.
B+(aq) + 2H2O(l) BOH(aq) H3O+(aq)
The extent of hydrolysis of a given cation depends on its acidic strength.
(i) Hydrolysis of Salt of Strong acid and Strong base :
Salt of strong acid and strong base does not hydrolysed.

B.Tech. IIT Delhi
Ph. - 8209916365 (NV Sir) 9057586906(VKP Sir)
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(ii) Salt of strong acid and weak base
B+ + H2O BOH + H+
[ BOH ] [ H ]
Kh =
[B ]
KW
Kh 
Kb
Kh
h =
C
1 1
pH = 7 – pKb – log C
2 2
Here, on the study of above equation, we can say that the pH of the strong acid weak base is less than
7.
(iii) Salt of weak acid and strong base

A– + H2O OH– + HA
[ HA ] [OH ]
Kh =
[A ]
KW
Kh 
Ka
Kh
h =
C
1 1
pH = 7 + pKa + log C
2 2
(iv) Salt of weak acid and weak base

B+ + A– + H2O HA + BOH
[HA ] [BOH]
Kh =
[B ] [ A ]
KW
Kh =
Ka K b
KW
h =
Ka K b
1 1
pH = 7 + pKa – pKb
2 2

B.Tech. IIT Delhi
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Hydrolysis of Amphiprotic Anion.
(Cation is not Hydrolysed)
NaHCO3, NaHS, etc., can undergo ionisation to from H+ ion and can undergo hydrolysis to form OH¯
(Na+ ion is not hydrolysed)
(a) (i) HCO3¯ + H2O CO23  +
(ii) HCO3¯ + H2O H2CO 3 +
 pK a1  pK a2 
pH(HCO3–) =  
 2 
(b) Similarly for H2PO4¯ and HPO42– amphiprotic anions.

 pK a1  pK a2   pK a2  pK a3 
pH(H2PO 4–) =   and pH(HPO42–) =  
 2   2 
Buffer Solution
(if the acids and bases are mixed in different amounts (equivalents))
(i) In certain applications of chemistry and biochemistry we require solutions of constant pH.
Such solution are called buffer solution.
(ii) A solution whose pH is not altered to any great extent by the addition of small quantities of
either an acid (H+ ions) or a base (OH– ions) is called buffer solution.
(iii) Buffer solutions are also called solutions of reverse acidity or alkalinity.
(iv) Following are the characteristics of buffer solutions
(a) It must have constant pH.
(b) Its pH should not be changed on long standing
(c) Its pH should not be changed on dilution.
(d) It pH should not be changed to any great extent on addition of small quantity of acid
or base.
(v) Buffer solutions can be classified as follows.
(A) Simple buffer (B) Mixed buffer
Acidic buffer
These are the mixture of a weak acid and its salt with strong base.
e.g.
(a) CH3COOH + CH3COONa
(b) Boric acid (H3BO 3) + Borax (Na2 B4O7)
[Salt]
pH = pKa + log
[Acid]
Basic Buffer
These are the mixture of a weak base and its salt with strong acid.
e.g.
(a) NH4OH + NH4Cl
+
(b) Glycine (NH2CH2COOH) + Glycine hydrochloride (Cl NH3CH2COOH)
[Salt]
or pOH = pKb + log
[Base]

B.Tech. IIT Delhi
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Buffer Capacity
(i) The property of a buffer solution to resist alteration in its pH value is known as buffer capacity.
(ii) Buffer capacity is number moles of acid or base added in one litre of solution as to change
the pH by unity, i.e.
Number of moles acid or base added to 1l sol.
Buffer capacity () =
Change inpH
b
or =
 ( pH )
where b is number of moles of acid or base added and ( pH) is change in pH.
INDICATOR :
[Ionised form]
pH = pKn + log
[Unionised form]
SOLUBILITY(S) AND SOLUBILITY PRODUCT (KSP)

At a constant temperature, the mass of a solute or electrolyte dissolved in the 100 gm of solvent in
its saturated solution is called as solubility. Or number of gm mole of a solute dissolved in one litre
of water at constant temperature is called as solubility of that solute.
Solubility of a solute in moles / litre
Solubility of solute in gm / litre

=
molecular weight of the solute
Relationship between Solubility and Solubility Product :
The equilibrium for a saturated solution of a salt Ax By may be expressed as,
Ax By xAy+ + yBx–
Thus, solubility product KSP = [Ay+] x [Bx–] y
Let the solubility of the salt Ax By in water at a particular temperature be ‘s’ moles per litre then
Ax By xAy+ + yBx–
xs ys
So, KSP = [xs]x [ys] y
KSP = xx . yy(s)x + y
(a) 1 : 1 types salts or AB type of salts :

eg. AgCl, AgI, BaSO4, PbSO 4, etc.
AB A+ + B –
let the solubility of AB is s moles per litre.
So, KSP = [A+] [B–] = s × s = s2
s = KSP
(b) 1 : 2 or 2 : 1 type of salts or AB2 or A2B type of salts :
eg. Ag2CrO4, PbI2, Ag2CO 3, CaF2, CaCl 2 etc.
(i) AB2 A2+ + 2B–
s 2s
let the solubility of AB2 is ‘s’ moles per litre
So, KSP = [A2+][B–] 2 = s × (2s)2 = 4s3
K SP
s = 3
4
B.Tech. IIT Delhi
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(ii) A2B 2A+ + B2–
let s the solubility of A2B
So, A2B 2A+ + B2–
2s s
KSP = [A+]2 [B–2] = (2s)2 (s) = 4s3
K SP
s = 3
4
(c) 1 : 3 type of salts or salts of AB3 or A3B type of salt -
AB3 = Valency of A = 3 × Valency of B
eg. FeCl3, AlCl 3, PCl 3, Al(OH)3, Fe(OH)3 etc.
A3B = 3 × Valency of A = Valency of B
eg. Na3BO 3, Na3PO 4, H3PO4 etc.
(i) AB3 A3+ + 3B–
let the solubility of A3B is ‘s’ mole / litre.
AB3 A3+ + 3B–
s 3s
KSP = [A ] [B ] = s × (3s)3 = 27s4
3+ – 3
K SP
s = 4
27
(ii) A3B 3A+ + B–3
let the solubility of A3B is ‘s’ moles/litre.
A3B 3A+ + B–3
3s s
KSP = [A+]3 [B ] = (3s)3 × s = 27s4
–3
K SP
s = 4
27
(d) 2 : 3 or A2B3 type of salts :
eg. Al2(SO4)3
A2B2 2A+ 3 + 3B– 2
let the solubility of salt A2B3 is ‘s’ -

So, A2B3 2A+3 + 3B–2
2s 3s
KSP = [A+3]2 [B–2] 3
= (2s)2 × (3s)3
= 4s2 × 27 s3
KSP = 108 s5
K SP
s = 5
108

B.Tech. IIT Delhi
Ph. - 8209916365 (NV Sir) 9057586906(VKP Sir)
M.Sc. IT-BHU
PART - I : SUBJECTIVE QUESTIONS
Section (A) : Acid and Base Concept
A-1. Identify acid and base in the following reaction according to Bronsted - Lowry concept.
(a) [Cu(H2O)3(OH)]+ (aq.) + [Al(H2O)6]3+ (aq.)  [Cu(H2O)4]2+ (aq.) + [Al(H2O)5OH]2+ (aq.)
(b) [Fe(H2O)5(OH)]2+ (aq.) + [Al(H2O)6]3+ (aq.)  [Fe(H2O)6]3+ (aq.) + [Al(H2O)5(OH)]2+ (aq.)
(c) O2– (aq.) + H2O (aq.)  2OH¯ (aq.)
(d) CH3OH (aq.) + H¯ (aq.)  CH3O¯ (aq.) + H2 (g)
A-2. Classify the following into acid, base and amphiprotic in terms of protonic concept.
(i) H2PO2¯ (ii) H2PO3¯ (iii) H2PO4¯ (iv) HPO32–
(v) HPO4 2–
(vi) NH4+
(vii) CH3COOH2+
A-3. If equal concentrations are mixed (of products & reactants) then which of the reaction will proceed to the right
and which will proceed to the left.
(A) H2SO4 (aq) + NH3 (aq)  NH4+ (aq) + HSO4– (aq)
(B) HCO3– (aq) + SO42– (aq)  HSO4– (aq) + CO32– (aq)
A-4. (a) Write conjugate acids of SO42– , RNH2 , NH2– , C2H5O C2 H5 , F–

(b) Write conjugate base of HNO2 , OH–, H2CO3, HClO4.
(c) Write conjugate acids and conjugate base of amphoteric species.
HS– , NH3, C2H5OH, H2O
A-5. Which of the following ions or compounds in a solution tends to produce an acidic, a basic or a neutral
solution
–
(a) C2H5O (b) Cu+2 (c) SO32-
– +
(d) F (e) NH4 (f) CH3COONa
(g) KNO3 (h) NaOCl (i) Na2CO3
(j) ZnCl2
A-6. Arrange the following bases in order of decreasing basicity
– – –
CN , NH3, CH3COO , F
Section (B) : Properties of water & pH Scale, Autoprotolysis

B-1. Percentage ionisation of water at certain temperature is 3.6 × 10–7 %, Calculate Kw and pH of water.
B-2. What is pOH of solution with [H+] = 10-2M and Kw = 2 x 10-12
B-3. A 50 ml solution of strong acid of pH = 1 is mixed with a 50 ml solution of strong acid of pH = 2. The pH of the
mixture will be nearly (log 5.5 = 0.74)
B-4. Liquid NH3 has ionic product at –500C is 10-30 . How many amide ions are present per mm3 in pure liquid NH3
Section (C) : Relation between Ka and Kb for conjugate acid - base pair
C-1. What is ionisation constant of HOCl if Kb of OCl – = 4 x 10-10
C-2. Ka1 , Ka2 and Ka3 values for H3PO4 are 10–3 , 10–8 and 10–12 respectively. If Kw (H2O) = 10–14 then -
(i) What is dissociation constant of HPO42–.
(ii) What is Kb of HPO42–
(iii) What is Kb of H2PO4–
(iv) What is order of Kb of PO43– ( K b 3 ), HPO42–( K b 2 ) and H2PO4–( K b 1 )

B.Tech. IIT Delhi
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M.Sc. IT-BHU
Section (D) : Strong acid, Strong base and their mixtures
D-1. Calculate pH for :
(i) 0.001 M NaOH, (ii) 0.005 M Ca(OH)2 , (iii) 0.01 M Ca(OH)2
(iv) 10–8 M NaOH, (v) 0.0008 M Mg(OH)2 .
D-2. Calculate the pH of the following solutions :
(i) 2.21 g of TlOH dissolved in water to give 2 litre of solution. (Assume TlOH to be strong base)
(ii) 0.37 g of Ca(OH)2 dissolved in water to give 500 mL of solution.
(iii) 0.32 g of NaOH dissolved in water to give 200 mL of solution.
(iv) 1 mL of 12 M HCl is diluted with water to give 1 litre of solution.
D-3. Calculate the pH of the resulting solution formed by mixing the following solutions :
(a) 20 mL of 0.2 M Ca(OH)2 + 25 mL of 0.1 M HCl
(b) 10 mL of 0.01 M H2SO4 + 10 mL of 0.01 M Ca(OH)2
(c) 10 mL of 0.1 M H2SO4 + 10 mL of 0.1 M KOH.
D-4. A 1 litre solution of pH = 4 (solution of a strong acid) is added to the 7/3 litre of water. What is the pH of
resulting solution. (log 3 = 0.48)
Section (E) : Ostwald dilution concept, Degree of dissociation of single weak acid or
base
E-1. 0.1 mole of which of the reagents listed below [(i) to (vi)] could be added to one litre of water to make 0.10 M
solutions of each of the following ions separatly ?
(a) NH4+ ; (b) CH3COO¯ ; (c) Cl¯
(i) NH3 ; (ii) NH4Cl ; (iii) CH3COOH ; (iv) CH3COONa ; (v) HCl ; (vi) NaCl
E-2. Decinormal solution of acetic acid gets 1.3% ionised. What will be the ionisation constant of acetic acid ?
E-3. For a weak acid HX, Ka = 10 –4. The degree of dissociation of 10–4 M HX is :
E-4. Calculate the pH of 500 ml of 1M hydrazoic acid (HN3). (Ka = 2.5 × 10–5, log 5 = 0.7)
E-5. Calculate (a) Ka for a monobasic acid whose 0.10 M solution has pH of 4.52 (log 3 = 0.48)
(b) Kb for a monoacidic base whose 0.10 M solution has a pH of 10.48.
Section (F) : pH of polyprotic acids and bases

F-1. 10–4 M HX acid solution (Ka = 5 × 10–5)
(a) Calculate degree of dissociation (b) Calculate PH
F-2. K1 and K2 for dissociation of H2A are 4 × 10–3 and 1 × 10–5, calculate concentration of A–2 Ion in 0.1 M H2A
solution. Also report [H+] and PH
F-3. What is the pH of 0.01 M H2S solution ? Ka1 = 9 × 108 , Ka2 = 1.2 × 1013 .
F-4. Which pH increases by higher value on dilution of
(a) CH3COOH solution (b) HCl solution from initial pH = 2.
F-5. Calculate the conc of H+ and A2– ion respectively in aquous solution of 0.1 M H2A (dibasic weak acid,)
Ka1 = 0.2 and ka2 = 2 × 10–6
Section (G) : Mixtures of acids or bases
G-1. What are [H+], [A¯] and [B¯] in a solution that contains 0.03 M HA and 0.1 M HB. Ka for HA and HB are
3.0 × 10–4 and 1.0 × 10–10 respectively.
G-2. Calculate [H+], [HCOO¯] and [OCN¯] in a solution that contains 0.1M HCOOH (Ka = 2.4 x 10-4) and 0.1 M
HOCN (Ka = 4 × 104).
G-3. What is concentration of S2– in solution of 0.01 M HCl and 0.1 M H2S. (Given K a1 = 10–7 and K a2 = 10–14)
Section (H) : Salt hydrolysis, amphiprotic species

H-1. A 0.25 M solution of pyridinium chloride C5H5NH+Cl was found to have a pH of 2.75. What is Kb for pyridine,
C5H5N? (log 2 = 0.3)

B.Tech. IIT Delhi
Ph. - 8209916365 (NV Sir) 9057586906(VKP Sir)
M.Sc. IT-BHU
H-2. Calculate the degree of hydrolysis of 0.005 M K2CrO4. K2 = 5.0 × 10–7 for H2CrO4. (It is essentially strong for
first ionization).
H-3. Calculate the percentage hydrolysis & the pH of 0.02 M CH3COONH4. Kb(NH3) = 1.6 × 10–5, Ka(CH3COOH) =
1.6 × 10–5.
H-4. What is the pH of 0.1M NaHCO3? K1 = 4.5 × 10-7, K2 = 4.5 × 10-11 for carbonic acids.
(Given : log 2 = 0.3, log 3 = 0.48)
PART - II : OBJECTIVE QUESTIONS

* Marked Questions may have more than one correct option.
Section (A) : Acid and Base Concept
A-1 The following equilibrium is established when hydrogen chloride is dissolved in acetic acid
HCl (aq) + CH3COOH (aq) Cl– (aq) + CH3 COOH2+(aq).
The set that characterises the conjugate acid-base pairs is
(A) (HCl, CH3COOH) and (CH3COOH2+, Cl–) (B) (HCl, CH3COOH2+) and (CH3COOH, Cl–)
(C) (CH2COOH2 , HCl) and (Cl , CH3COOH)
+ –
(D) (HCl, Cl–) and (CH3COOH2+, CH3COOH).
A-2 In the following reaction HC2O4– (aq) + PO43–(aq) HPO42–(aq) + C2O42–(aq), which are the two Bronsted
bases?
(A) HC2O4– and PO43– (B) HPO42– and C2O42– (C) HC2O4– and HPO42– (D) PO43– and C2O42–
A-3. The following equilibrium is established when HClO4 is dissolved in weak acid HF.
HF + HClO4 ClO4– + H2F+
Which of the following is correct set of conjugate acid base pair ?
(A) HF and HClO4 (B) HF and ClO4– (C) HF and H2F+ (D) HClO4 & H2F+
A-4. Boric acid H3BO3 is a :
(A) Arrhenius acid (B) Bronsted acid (C) Lewis acid (D) All of these
A-5. Identify the amphoteric species from the following :
(I) H2O (II) NH3 (III) H2PO4– (IV) HCO3–
(A) ,  (B) , IV (C) , ,  (D)V
Section (B) : Properties of water & pH Scale, Autoprotolysis

B-1. Which of the following expression is not true ?
(A) [H+] = [OH] = K W for a neutral solution at all temperatures.
(B) [H+] > K W & [OH] < K W for an acidic solution
(C) [H+] < K W & [OH] > K W for an alkaline solution
(D) [H+] = [OH] = 107 M for a neutral solution at all temperatures .
B-2. Which of the following relations is correct ?
(A) Gº = RT ln Keq (B) [H3O+] = 10pH
2 Hº
Kw 1 1  
(C) log Kw = 2.303 R  T  T  (D) [OH–] = 10–7, for pure water at all temperatures.
1  1 2
B-3. pOH of H2O is 7.0 at 298 K . If water is heated at 350 K, which of the following statement should be true?
(A) pOH will decrease.
(B) pOH will increase.
(C) pOH will remain 7.0.
(D) concentration of H+ ions will increase but that of OH will decrease.
B-4. Kw of H2O at 373 K is 1 × 10–12. Identify which of the following is incorrect.

(A) pKw of H2O is 12 (B) pH of H2O is 6 (C) H2O is neutral (D) H2O is acidic

B.Tech. IIT Delhi
Ph. - 8209916365 (NV Sir) 9057586906(VKP Sir)
M.Sc. IT-BHU
B-5. Which of the following is incorrect ?
(A) Ka (weak acid). Kb (conjugate weak base) = Kw
(B) Ka (strong acid). Kb (conjugate weak base) = Kw
(C) Ka (weak acid). Kb (weak base) = Kw
(D) Ka (weak acid). Kb (conjugate strong base) = Kw
B-6. Pure water ionise as
2H2O (l) H3O+(aq) + OH– (aq)
At 25°C the pH of pure water is approximately 7.0 At 37°C its pH is :
(A) More than 7.0 (B) Less than 7.0 (C) Equal to 7.0 (D) None of these
– -3 0
B-7. In pure liquid of HCOOH, concentration of HCOO = 10 M at 27 C. What is the self ionisation constant
(K = [HCOOH2+] [HCOO–])
(A) 10-3 (B) 103 (C) 106 (D) 10-6
Section (C) : Relation between Ka and Kb for conjugate acid - base pair.
C-1. Ka for the acid HA is 1 × 10–6. The value of K for the reaction A– + H3O+ HA + H2O is
(A) 1 × 10–6 (B) 1 × 1012 (C) 1 × 10–12 (D) 1 × 106
C-2. The pKa value of NH4 is 9. The pKb value of NH4OH would be :
(A) 9 (B) 5 (C) 7 (D) 8
C-3. K b1 of N2H4 is 4.0 × 10-6. Then what is the acid dissociation constant of N2H5+ and N2H6+2respectively..
(A) data insufficient, 4 × 10–6 (B) data insufficient, 2.5 × 10–8
(C) 2.5 × 10–9 ,data insufficient (D) 2.5 × 10–9 , 4 × 10–6
C-4. Given
Which relation is correct.

1 Ka
(A) Kb = Kw (B) Ka . Kb = Kw (C) K b  (D)  Kw
Kw Ka
Section (D) : Strong acid, Strong base and their mixtures
D-1. Which of the following solution will have a pH exactly equal to 8 ?
(A) 10–8 M HCl solution at 25ºC (B) 10–8 M H+ solution at 25ºC
(C) 2 × 10–6 M Ba(OH)2 solution at 25ºC (D) 10–5 M NaOH solution at 25ºC
D-2. The [OH–] in 100.0 ml of 0.016 M-HCl (aq) is :
(A) 5 × 1012 M (B) 3 × 10–10 M (C) 6.25 × 10–13 M (D) 2.0 × 10–9 M.
D-3. How many moles of NaOH must be removed from one litre of aqueous solution to change its pH from
12 to 11 ?
(A) 0.009 (B) 0.01 (C) 0.02 (D) 0.1
D-4. Which of the following solution will have pH close to 1.0 ?
(A) 100 ml of M/10 HCl + 100 ml of M/10 NaOH (B) 55 ml of M/10 HCl + 45 ml of M/10 NaOH
(C) 10 ml of M/10 HCl + 90 ml of M/10 NaOH (D) 75 ml of M/5 HCl + 25 ml of M/5 NaOH.
D-5. 0.1mol HCl is dissolved in distilled water of volume V then at lim V  (pH)solution is equal to
(A) zero (B) 1 (C) 7 (D) 14
D-6. The pH of a solution obtained by mixing 50 ml of 0.4 N HCl and 50 ml of 0.2 N NaOH is :
(A) 13 (B) 12 (C) 1.0 (D) 2.0
Section (E) : Ostwald dilution concept, Degree of dissociation of single weak acid or
base
E-1. Which of the following has the highest degree of ionisation ?
(A) 1 M NH3 (B) 0.001 M NH3 (C) 0.1 M NH3 (D) 0.0001 M NH3.

B.Tech. IIT Delhi
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M.Sc. IT-BHU
E-2. At infinite dilution the percentage dissociation of both weak acid and weak base is:
(A) 1% (B) 20% (C) 50% (D) 100%
E-3. Concentration of the anion will be 3c. for the following weak electrolytes.
(A) AB2 (B) AB (C) AB3 (D) A3B4
E-4. Ostwald's dilution law gives satisfactory results with the solution of which electrolyte ?
(A) HCl (B) HNO3 (C) CH3COOH (D) NaOH
E-5. Dissociation constant of mono basic acids A, B, C and D are 6 x 10-4, 5 x 10-5, 3.6 x 10-6 and 7 x 10-
10
respectively. The pH values of their 0.1M aqueous solution are in the order.
(A) D> C > B > A (B) A > B >C > D (C) D > C > A > B (D) None
E-6. Which statement/relationship is correct?
1
(A) pH of 0.1 M HNO3, 0.1M HCl, 0.1M H is not equal. (B) pH = – log
[H ]
(C) At 25°C the pH of pure water is 7. (D) The value of pKw at 25 °C is 7.
E-7. One litre of solution contains 10–5 moles of H+ ions at 25°C. Percentage ionisation of water in solution is :
(A) 1.8 × 10–7 % (B) 1.8 × 10–9 % (C) 3.6 × 10–9 % (D) 1.8 × 10–11 %.
Section (F) : pH of polyprotic acid or base
F-1. For ortho phosphoric acid,
H3PO4 (aq) + H2O (aq) H3O+ (aq) + H2 PO 4 (aq) ; Ka
H2PO4 (aq) + H2O (aq) H3O+ (aq) + HPO 24 (aq) ; Ka
2
HPO24 (aq) + H2O (aq) H3O+ (aq) + PO34 (aq) ; Ka

3
The correct order of Ka values is :
(A) K a1 > K a2 < K a3 (B) K a1 < K a2 < K a3 (C) K a1 > K a2 > K a3 (D) K a1 < K a2 > K a3
F-2. Approximate pH of 0.1 M aqueous H2S solution when K1 and K2 for H2S at 25oC are 1×10–7 and 1.3 × 10–13
respectively :
(A) 4 (B) 5 (C) 6 (D) 8
F-3. In a solution of 0.1 M H3PO4 acid, (given K a2  10 3 , K a2  10 7 , K a3  10 12 )
(i) Concentration of H3PO4 is :

(A) 0.01 (B) 0.09 (C) 0.05 (D) 0.1
(ii) Concentration of H2PO4– is :
(A) 0.01 (B) 0.09 (C) 0.02 (D) 0.04
(iii) Concentration of H2PO42– is :
(A) 10–7 (B) 10–8 (C) 10–3 (D) 10–4
(iv) Concentration of PO43– is :

(A) 10–20 (B) 10–17 (C) 10–15 (D) 10–12
(v) pH of solution is :
(A) 1 (B) 2 (C) 4 (D) 5
Section (G) : Mixtures of acids or bases

G-1. Consider an aqueous solution, 0.1 M each in HOCN, HCOOH, (COOH)2 and H3PO4, for HOCN, we can write
[H ][OCN ]
Ka(HOCN) = . [H+] in this expression refers to
[HOCN]
(A) H+ ions released by HOCN
(B) Sum of H+ ions released by all monoprotic acids
(C) Sum of H+ ions released only the first dissociation of all the acids.
(D) Overall H+ ion concentration in the solution.

B.Tech. IIT Delhi
Ph. - 8209916365 (NV Sir) 9057586906(VKP Sir)
M.Sc. IT-BHU
G-2. The dissociation constant of acetic acid at a given temperature is 1.69 × 10–5. The degree of dissociation of
0.01 M acetic acid in the presence of 0.01 M HCl is equal to
(A) 0.41 (B) 0.13 (C) 1.69 × 10–3 (D) 0.013.
Section (H) : Salt hydrolysis, amphiprotic species
H-1. A pair of salts are given in a solution each in 0.1M concentration. Which solution has a higher pH ?
(A) NaCN and NaOBr (B) NaF and NaOCl (C) NaF and NaOBr (D) NaCN and NaOCl
H-2. Which of the following salts undergoes anionic hydrolysis?
(A) CuSO4 (B) NH4Cl (C) AlCl3 (D) K2CO3.
H-3. The sodium salt of a certain weak monobasic organic acid is hydrolysed to an extent of 3% in its 0.1M
solution at 250C. Given that the ionic product of water is 1014 at this temperature, what is the dissociation
constant of the acid?
(A)  1 x 1010 (B)  1 x 109 (C) 3.33 x 109 (D) 3.33 x 1010
H-4. The pH of a solution obtained by mixing 100 ml of 0.2 M CH3COOH with 100 ml of 0.2 M NaOH would be :
(pKa for CH3COOH = 4.74)
(A) 4.74 (B) 8.87 (C) 9.10 (D) 8.57
H-5. pH of 0.1M Na2HPO4 and 0.2M NaH2PO4 are respectively : pKa for H3PO4 are 2.2, 7.2 and 12.0.
(A) 4.7, 9.6 (B) 9.6, 4.7 (C) 4.7, 5.6 (D) 5.6, 4.7
H-6. The pH of 0.1 M solution of the following salts increases in the order : [JEE-1999, 2/80]
(A) NaCl < NH4Cl < NaCN < HCl (B) HCl < NH4Cl < NaCl < NaCN
(C) NaCN < NH4Cl < NaCl < HCl (D) HCl < NaCl < NaCN < NH4Cl
PART - III : ASSERTION / REASONING

Each question has 5 choices (A), (B), (C), (D) and (E) out of which ONLY ONE is correct.
(A) STATEMENT-1 is true, STATEMENT-2 is true and STATEMENT-2 is correct explanation for STATEMENT-1.
(B) STATEMENT-1 is true, STATEMENT-2 is true and STATEMENT-2 is not correct explanation for STATEMENT-1.
(C) STATEMENT-1 is true, STATEMENT-2 is false
(D) STATEMENT-1 is false, STATEMENT-2 is true
(E) Both STATEMENTS are false
1. Statement-1 : The H3O+ has additional water molecules closely associated with it.
Statement-2 : In solid state the species H5O2+ and H9O4+ have been found to exist.
2. Statement-1 : The proton transfer reaction between NH3 and H2O proceeds only to a slight extent.
Statement-2 : Proton transfer reaction is virtually complete in the case of HCl in dilute solution.
3. Statement-1 : Aqueous solutions of all strong acids contain only the same acid, the hydronium ion.
Statement-2 : Hydronium ion is the strongest acid that can exist in any significant concentration in dilute
aqueous solution.
4. Statement-1 : Acids that have more than one proton that can be donated to base are called polyprotic acids.
Statement-2 : For all diprotic acids, the equilibrium constant Ka2, for the second stage of ionisation is
smaller than the equilibrium constant, Ka1 , for the first stage of ionisation.
5. Statement-1 : 0.20 M solution of NaCN is more basic than 0.20 M solution of NaF.
Statement-2 : Ka of HCN is very much less than that of HF.
6. Statement-1 : A substance that can either act as an acid as well as a base is called ampholyte.
Statement-2 : Bisulphide ion (HS–) and biscarbonate ion (HCO3–) are ampholytes.
7. Statement-1 : Addition of HCl(aq) to HCOOH(aq), decrease the ionization of HCOOH(aq)

Statement-2 : Due to common ion effect of H+, ionization of HCOOH decreased.
8. Statement-1 : pH of 10–7 M HCl is less than 7 at 25ºC.

Statement-2 : At very low concentration of HCl, contribution of H+ from water is considerable.

B.Tech. IIT Delhi
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M.Sc. IT-BHU
1. If the acid-base reaction HA(aq) + B¯(aq) HB(aq) + A¯(aq) has a Keq. = 10–4, which of the following
statements are true ?
(i) HB is stronger acid than HA (ii) HA is stronger acid than HB
(iii) HA and HB have the same acidity (iv) B¯ is stronger base than A¯
(v) A¯ is stronger base than B¯ (vi) B¯ and HB are conjugate acid-base pair
(vii) the acid and base strengths connot be compared
2. A 1 litre solution of pH = 6 (solution of a strong acid) is added to the 7/3 litre of water. What is the pH of
resulting solution. (log 2 = 0.3) (Neglect the common ion effect on H2O).
3. Calculate the change in pH when 4 gm of solid NaOH & 10 mmol of H2SO4 are added to a solution of volume
5 litre, which was prepared by mixing 20 mmol of HCl, 40 mmol of H2SO4 and 2 gm of NaOH and sufficient
water. Ignore the volume change. (log 2 = 0.3, log 3 = 0.48)
4. If both the functional groups of salicylic acid, HOC6H4COOH, ionise in water, with Ka = 1 × 10–3 for the –COOH
group and 4.2 × 10 –13 for the –OH group, calculate pH of the saturated solution of the acid.
(Solubility of salicylic acid in water = 1.725 g/L, log 2 = 0.3).
5. A solution is prepared by mixing of acetic acid (Ka = 2 × 10–5) and HCl. In the mixture acetic acid is 0.2 M and
HCl is 0.1 M. Calculate
(i) pH of 0.2 M acetic acid and its degree of dissociation.
(ii) pH of final solution.
(iii) CH3COO– ion concentration in final solution.
(iv) % decrease of  of acetic acid due to common ion effect.
6. If the equilibrium constant for the reaction of weak acid HA with strong base is 109, then pH of 0.1 M Na A is
7. The ionization constant of nitrous acid is 4.5 × 10–4. Calculate the pH of 0.04 M sodiums nitrite solution and
also its degree of hydrolysis.
8. Ka for ascorbic acid (HAsc) is 5  10 5. Calculate the hydrogen ion concentration and percentage hydrolysis
in an aqueous solution in which concentration of Asc ions is 0.02 M .

Single choice type
1. At what molar concentration of HCl will its aqueous solution have an [H+] to which equal contributions come
from HCl and H2O.
(A) 60 × 10–7 M (B) 50 × 10–8 M (C) 40 × 10–9 M (D) 30 × 10–8
2. Consider following statements :

I : CH3COOH (a weak acid) behaves as a strong acid in NH3.
II : HNO3 (strong acid) behaves as a base in HF (anhydrous).
III : H2SO4 dissociates to a very small extent in glacial CH3COOH.
Select correct alternate for these statements.
(A) I, III (B) II, III (C) I, II (D) I, II, III
3. When 0.1 mole solid NaOH is added in 1lt of 0.1 M NH 3(aq) then which statement is wrong?
(Kb = 2 × 10–5, log 2 = 0.3)
(A) degree of dissociation of NH3 approaches to zero.
(B) change in pH by adding NaOH would be 1.85
(C) In solution, [Na+] = 0.1 M, [NH3] = 0.1 M, [OH–] = 0.2 M.
(D) on addition of OH–, Kb of NH3 does not changes.

B.Tech. IIT Delhi
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M.Sc. IT-BHU
4. A certain mixture of HCl and CH3COOH is 0.1 M in each of the acids. 20 ml of this solution is titrated against
0.1M NaOH. By how many units does the pH change from the start to the stage when the HCl is almost
completely neutralised and acidic acid remains unreacted ? Ka for acetic acid = 2 x 105.
(A) 1.5 (B) 3 (C) 2 (D) 3.25
5. The correct relationship between the pH of isomolar solutions of Na2O (pH1), Na2S (pH2) Na2Se(pH3) and
Na2Te(pH4) is:
(A) pH1 > pH2 > pH3 > pH4 (B) pH1 < pH2 < pH3 < pH4
(C) pH1 < pH2 < pH3 = pH4 (D) pH1 > pH2 = pH3 > pH4
6. The pH of which salt is independent of its concentration :
1. (CH3COO)C5H5NH 2. NaH2PO4 3. Na2HPO4 4.NH4CN
(A) 1, 2, 3, 4 (B) 1, 4 (C) 2, 3 (D) 1, 2, 3
More than one choice type

7.* Degree of hydrolysis for a salt of strong acid and weak base is
(A) independent of dilution (B) increases with dilution
(C) increases with decrease in Kb of the bases (D) decreases with decrease in temperature.
8. If Ka1 and Ka2 of H2SO4 are 10–2 and 10–6 respectively then
(A) Ka1 > Ka2 because it is easy to abstract H+ from H2SO4 and less easy to abstract H+ from HSO4–.
(B) Ka1and Ka2 may be measured in acetic acid.
(C) Ka1 and Ka2 are measured in H2O.
(D) the H+ ion conc. of 0.01 M H2SO4 will be less than 0.02 M.
9. Which of the following solutions when added to 1L of a 0.01 M CH3COOH solution will cause no change in the
degree of dissociation of CH3COOH and pH of the solution ? Ka = 1.6 × 10–5 for CH3COOH?
(A) 0.6 mM HCOOH (Ka = 8 × 10–4) (B) 0.1 M CH3COONa
(C) 0.4 mM HCl (D) 0.01 M CH3COOH
10. Equal volumes of following solutions are mixed, in which case the pH of resulting solution will be average
value of pH of two solutions.
(A) Aqeous HCl of pH = 2, aqueous NaOH of pH = 12
(B) Aqeous HCl of pH = 2, aqueous HCl of pH = 4
(C) Aqeous NaOH of pH = 12, aqueous NaOH of pH = 10
(D) Aqeous CH3COOH of pH = 5, aqueous NH3 of pH = 9. [Ka (CH3COOH) = Kb (NH3)]
11. Ka values for HA, HB and HD are 10-5, 10-7 and 10-9 respectively. Which of the following will be correct for
decimolar aqueous solutions of NaA, NaB and NaD at 250C?
(A) (pH)NaA < (pH)NaB (B) (pH)NaD < (pH)NaB (C) (pH)NaA < (pH)NaD (D) (pH)NaB = 7
12._ 0.1 M CH3COOH is diluted at 25°C (Ka = 1.8 × 10–5), then which of the following will be found correct
(A) [H+] will increase (B) pH will increase
(C) number of H+ will increase (D) all the above are correct
PART - III : MATCH THE COLUMN

1. (Use log 1.8 = 0.26, Ka of formic acid = 1.8 × 10–4, Ka of acetic acid = 1.8 × 10–5, Kb of ammonia=1.8×10–5,
Ka1 of H2S = 10–7 and Ka2 of H2S = 10–14, for the following matchings)
Match the entries of column II for which the equality or inequality given in the column I are satisfied.
Column I Column II
(A) 10–5 M HCl solution > 0.1 M H2S solution (p) water ( degree of dissociation of water)
(B) CH3COOH solution at pH equal to 4.74
= NH4OH solution at pH equal to 9.26 (q) [OH–]
(C) 0.1 M CH3COOH solution
= 1.0 M HCOOH solution (r) (degree of dissociation)
(D) 0.1 M of a weak acid HA1(Ka = 10–5) solution
< 0.01 M of a weak acid HA2(Ka = 10–6) solution (s) pH

B.Tech. IIT Delhi
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PART - IV : COMPREHENSION
Read the following passage carefully and answer the questions.
COMPREHENSION # 1
Consider a solution of CH3COONH4 which is a salt of weak acid & weak base.
The equilibrium involved in the solutions are :
CH3COO– + H2O CH3COOH + OH– ..........(1)
NH4 + H2O
–
NH4OH + H+ ..........(2)
H+ + OH– H2O ..........(3)
If we add these three reactions, then the net reaction is
CH3COO– + NH4+ + H2O CH3COOH + NH4OH ..........(4)
Both CH3COO– and NH4+ get hydrolysed independently and their hydrolysis depends on
(i) their initial concentration
Kw Kw
(ii) the value of Kh which is K for CH3COO– and K for NH4+.
a b
Since both of the ions were produced from the same salt, their initial concentrations are same. Therefore
Kw Kw
unless & untial the value of K and K or Ka and Kb is same, the degree of hydrolysis of ion can't be
a b
same.
To explain why we assume that degree of hydrolysis of cation and anion is same, we need to now
look at the third reaction i.e., combination of H+ and OH– ions. It is obvious that this reaction happens only
because one reaction produced H+ ion and the other produced OH– ions. We can also note that this reaction
causes both the hydrolysis reaction to occur more since their product ions are being consumed. Keep this
thing in mind that the equilibrium which has smaller value of equilibrium conxtant is affected more by the
common ion effect. For the same reason if for any reason a reaction is made to occur to a greater extent by
the comsumption of any one of the product ion, the reaction with the smaller value of equilibrium constant
tends to get affected more.
Therefore we conclude that firstly the hydrolysis of both the ions ocurs more in the presence of each
other (due to consumption of the product ions) than in each other is absence. Secondly the hydrolysis of the
ion which occurs to a lesser extent (due to smaller value of Kh) is affected more than the one whose Kh is
greater. Hence we can see that the degree of hydrolysis of both the ions would be close to each other when
they are getting hydrolysed in the presence of each other.
1. In the hydrolysis of salt of weak acid & weak base :
(A) degree of hydrolysis of cation and anion is different
(B) degree of hydrolysis of cation and anion is same
(C) degree of hydrolysis of cation and anion is different and they can never be assumed same.
(D) degree of hydrolysis of cation and anion is different but they are very close to each other when they are
getting hydrolysed in the presence of each other.
2. For 0.1 M CH3COONH4 salt solution given, Ka (CH3COOH) = Kb (NH4OH) = 2 × 10–5.

In this case : degree of hydrolysis of cation and anion are
(A) exactly same (B) slightly different
(C) can't say (D) different but can be take approximatly same

B.Tech. IIT Delhi
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PART - I : IIT-JEE PROBLEMS (LAST 10 YEARS)
1. 500 ml of 0.2 M aqueous solution of acetic acid is mixed with 500 mL of 0.2 M HCl at 25º C.
(a) Calculate the degree of dissociation of acetic acid in the resulting solution and pH of the solution.
(b) If 6 g of NaOH is added to the above solution, determine final pH. Assume there is no change in volume
on mixing. Ka of acetic acid is 1.75 × 10-5 M. [JEE-2002, 5/60]
2. Will the pH of water be same at 4ºC and 25º C? Explain. [JEE-2003, 2/60]
3. A weak acid HX has the dissociation constant 1 × 10–5 M. It forms a salt NaX on reaction with alkali. The
percentage hydrolysis of 0.1 M solution of NaX is : [JEE-2004, 3/84]
(A) 0.0001% (B) 0.01 % (C) 0.1 % (D) 0.15 %
4. The dissociation constant of a substituted benzoic acid at 25ºC is 1.0 × 10–4 . The pH of 0.01 M solution of
its sodium salt is [JEE-2009, 4/160]
5. Amongst the following, the total number of compounds whose aqueous solution turns red litmus paper blue
is : [JEE-2010, 3/163]
KCN K2SO4 (NH4)2C2O4 NaCl Zn(NO3)2
FeCl3 K2CO3 NH4NO3 LiCN
6. The initial rate of hydrolysis of methyl acetate (1M) by a weak acid (HA, 1M) is 1/100th of that of a strong acid
(HX, 1M), at 25C. The Ka of HA is : [JEE(Advanced) -2013, 4/120]
(A) 1  10–4 (B) 1  10–5 (C) 1  10–6 (D) 1  10–3
PART - II : AIEEE PROBLEMS (LAST 10 YEARS)

1. Species acting as both bronsted acid and base is [AIEEE-2002]
(1) HSO4– (2) Na2CO3 (3) NH3 (4) OH –
2. Which one of the following statements is not true? [AIEEE-2003]

(1) The conjugate base of H2PO4– is HPO42–.
(2) pH + pOH = 14 for all aqueous solutions at 25ºC.
(3) The pH of 1 × 10–8 M HCl is 8.
(4) 96, 500 coulombs of electricity when passed through a CuSO4 solution deposits 1 gram equivalent of
copper at the cathode.
3. When rain is accompanied by a thunderstorm, the collected rain water will have a pH value. [AIEEE-2003]
(1) slightly lower than that of rain water without thunderstorm
(2) slightly higher than that when the thunderstorm is not there
(3) uninfluenced by occurrence of thunderstorm
(4) which depends on the amount of dust in in air.
4. The conjugate base of H2PO4– is [AIEEE-2004]

(1) PO43– (2) P2O5 (3) H3PO4 (4) HPO 4
2–
5. What is the conjugate base of OH– ? [AIEEE-2005]

(1) O2 (2) H2O (3) O–
(4) O 2–
6. Hydrogen ion concentration in mol/L in a solution of pH = 5.4 will be [AIEEE-2005]

(1) 3.98 × 108 (2) 3.88 × 106 (3) 3.68 × 10–6 (4) 3.98 × 10 –6

B.Tech. IIT Delhi
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7. The first and second dissociation constants of an acid H2A are 1.0 × 10–5 and 5.0 × 10–10 respectively. The
overall dissociation constant of the acid will be [AIEEE-2007, 3/120]
(1) 5.0 × 10–15 (2) 0.2 × 105 (3) 5.0 × 10–5 (4) 5.0 × 1015
8. The pKa of a weak acid, HA, is 4.80. The pKb of a weak base, BOH, is 4.78. The pH of an aqueous solution
of the corresponding salt, BA, will be [AIEEE-2008, 3/105]
(1) 4.79 (2) 7.01 (3) 9.22 (4) 9.58
9. Three reactions involving H2PO4– are given below : [AIEEE-2010, 4/144]

(i) H3PO4 + H2O  H3O+ + H2PO4–
(ii) H2PO4– + H2O  HPO42– + H3O+
(iii) H2PO4– + OH–  H3PO4 + O2–
In which of the above does H2PO4– act as an acid ?
(1) (ii) only (2) (i) and (ii) (3) (iii) only (4) (i) only
10. In aqueous solution the ionization constants for carbonic acid are [AIEEE-2010, 4/144]
K1 = 4.2 × 10–7 and K2 = 4.8 × 10–11
Select the correct statement for a saturated 0.034 M solution of the carbonic acid.
(1) The concentration of CO32– is 0.034 M.
(2) The concentration of CO32– is greater than that of HCO3–.
(3) The concentration of H+ and HCO3– are approximately equal.
(4) The concentration of H+ is double that of CO32–.
11. How many litres of water must be added to 1 litre an aqueous solution of HCl with a pH of 1 to create an
aqueous solution with pH of 2 ? [JEE(Main) 2013, 4/120]
(1) 0.1 L (2) 0.9 L (3) 2.0 L (4) 9.0 L

B.Tech. IIT Delhi
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M.Sc. IT-BHU
EXERCISE - 1
PART - I
A-1. Acid Base
(a) [Al(H2O)6]3+ [Cu(H2O)3(OH)]+
(b) [Al(H2O)6]3+ [Fe(H2O)5(OH)]2+
(c) H2O O2–
(d) CH3OH H¯
A-2. Acidic – (vi), (vii) ; Basic – (i), (iv) ; Amphiprotic – (ii), (iii), (v)
A-3. (A) Right; (B) Left

A-4. (a) HSO4– , RNH3NH3 , (C2H5)2OH, HF
(b) NO2– , O2– , HCO3– , ClO4–
(c) Conjugate acids : H2S , NH4+ , C2H5OH2+ , H3O+
Conjugate base : S2– , NH2– , C2H5O– , OH–
A-5. (a) Basic (b) acidic (c) basic
(d) basic (e) acidic (f) basic
(g) neutral (h) basic (i) basic
(j) acidic
– – –
A-6. CN > NH3 > CH3COO > F
order of acidic strength (using bronsted table) HCN < NH4+ < CH3COOH < HF
B-1. Kw = 4 ×10–14, pH = 6.7 B-2. 9.7 B-3. 1.26 B-4. 600 ions / mm3
C-1. 2.5 x 10–5 C-2. (i) 10–12 (ii) 10–6 (iii) 10–11 (iv) K b 1 < K b 2 < K b 3
D-1. (i) 11, (ii) 12, (iii) 12.3, (iv) 7.02, (v) 11.2 D-2. (i) 11.7, (ii) 12.3, (iii) 12.6, (iv) 1.92
D-3. (a) 12.82 ; (b) 7 ; (c) 1.3. D-4. 4.52 E-1. (a) II (b) IV (c) II, V, VI
E-2. 1.69  10–5 E-3. 0.62 E-4. 2.3
E-5. (a) Ka = 9 × 10–9 ; (b) Kb = 9 × 10–7 F-1. (a)  = ½ ; (b) PH = 4.3
F-2.  = 0.18
= 5.55 × 10–4
[A–2] = 10–5 M
[H+] = 0.018 M
PH = 1.744
F-3. pH = 4.523 F-4. HCl F-5. [H+] = 7.3 × 10–2 ; [A2–] = 2 × 10–
6
G-1. [H+] = [A¯] = 3 × 10–3 M, [B¯] = 3.33 × 10–9 M
G-2. [H+] = 8 × 10-3 M, [HCOO¯] = 3 × 10–3 M, [OCN¯] = 5 × 10–3 M

G-3. 10–18 H-1. Kb = 8 × 10–10 H-2. 2 × 10–3
H-3. 0.625%, pH = 7 H-4. pH = 8.34
PART - II
A-1 (D) A-2 (D) A-3. (C) A-4. (C) A-5. (D)
B-1. (D) B-2. (C) B-3. (A) B-4. (D) B-5. (C)

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B-6. (B) B-7. (D) C-1. (D) C-2. (B) C-3. (C)
C-4. (B) D-1. (B) D-2. (C) D-3. (A) D-4. (D)
D-5. (C) D-6. (C) E-1. (D) E-2. (D) E-3. (C)
E-4. (C) E-5. (A) E-6. (C) E-7. (B) F-1. (C)
F-2. (A) F-3. (i) (B) (ii) (A) (iii) (A) (iv) (B) (v) (B)
G-1. (D) G-2. (C) H-1. (A) H-2. (D) H-3. (A)
H-4. (B) H-5. (B) H-6. (B)
PART - III
1. (B) 2. (B) 3. (A) 4. (B) 5. (A)
6. (B) 7. (A) 8. (A)
EXERCISE - 2
PART - I
1. I, V, VI 2. 6.4 3. 9.78 4. 2.52
5. (i) pH = 2.7,  = 10–2 (ii) pH = 1, (iii) [CH3COO–] = 4 × 10–5 (iv) new  = 2 × 10–4 , % decrease = 98%
6. 9 7. h = 2.36 × 10–5, pH = 7.975 8. [ H+ ] = 5 × 10–9 M, % hydrolysis =
0.01
PART - II
1. (B) 2. (D) 3. (C) 4. (C) 5. (A)
6. (A) 7 (B,C,D) 8. (A,B,D) 9. (A,C,D) 10. (A,D)
11. (A,C) 12._ (B,C)
PART - III
1. (A – p, q, r, s); (B – p, r) ; (C – r) ; (D – p, q, s)
PART - IV
1. (D) 2. (A)
EXERCISE - 3
PART - I
1. (a) 0.0175%, 1 (b) 4.757 2. It will not be same at two different temperatures.
3. (B) 4. 8 5. 3 6. (A)
PART - II
1. (1) 2. (3) 3. (1) 4. (4) 5. (4)
6. (4) 7. (1) 8. (2) 9. (1) 10. (3)
11. (4)

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Section (A) : Buffer Solution & Buffer Capacity
A-1. Calculate the pH of a solution of given mixtures ;
(a) (4 g CH3COOH + 4.1 g CH3COONa) in 100 mL of mixture ; Ka for CH3COOH = 1.8 × 10–5 .
(b) 5 mL of 0.1 M BOH + 25 mL of 0.1 M BCl ; Kb for BOH = 1.8 × 10–5 .
(c) (0.25 mole of CH3COOH + 0.4 mole of CH3COONa) in 500 mL mixture ; Ka for CH3COOH = 1.8 × 10–5.
A-2. 50 ml of 0.20 M solution of the acid HA (Ka = 1.0 x 105) & 50 ml of an NaA solution are given. What should
be the concentration of the NaA solution to make a buffer solution with pH = 4.00 ?
A-3. What amount of HCl will be required to prepare one litre of a buffer solution of NaCN and HCN of pH 8.5 using
0.01 mole of NaCN. pKb of CN¯ = 4.6 (log 2 =0.3)
A-4. Calculate the pH of a solution resulting from the addition of 12.5 ml of 0.1 M HCl to 50 ml of a solution
containing 0.15 M CH3COOH & 0.2 M CH3COONa. (pKa = 4.74)
A-5. Calculate the pH of 0.5 L of a 0.2 M NH4CI –0.2 M NH3 buffer before and after addition of (a) 0.05 mol of NaOH
and (b) 0.05 mol of HCl. Assume that the volume remains constant. (log2 = 0.3, log3 = 0.48) [pKb = 4.74]
A-6. Prove that Buffer capacity of 0.2 M CH3COOH and 0.2M CH3COONa is more than the 0.1 M CH3COOH and
0.1 M CH3COONa in 1 Lt solution.
A-7. What concentration of Ac – ions will reduce H3O + ion to 2 × 10–4 M in 0.40 M solution of HAc ?
Ka (HAc) = 1.8 × 10– 5 ?
Section (B) : Theory of indicators

B-1. At pH < 3.1, the indicator methyl red is coloured red, at pH > 6.3 it is yellow and at the intermediate values
of the pH it is orange. What will the colour of the indicator be in a 0.1 M solution of NH4Br. pKb (NH4OH) =
4.74.
B-2. A small quantity of phenolphthalein is added to a decinormal solution of sodium butyrate at 250C. Calculate
the ratio of the coloured to the colourless form of the indicator. Ka for butyric acid = 1.5 x 10-5 at 250C. K for
the indicator = 3.16 x 10-10 and KW = 10-14 at 250C.
Section (C) : Acid-base Titration

C-1. Calculate pH of the following mixtures. Given the Ka of CH3COOH = 2 × 10–5 and Kb of NH4OH = 2 × 10–5.
(a) 50 mL of 0.10 M NaOH + 50 mL of 0.05 M CH3COOH.
(b) 50 mL of 0.05 M NaOH + 50 mL of 0.10 M CH3COOH.
(c) 50 mL of 0.10 M NaOH + 50 mL of 0.10 M HCl.
(d) 50 mL of 0.10 M NH4OH + 50 mL of 0.05 M HCl.
(e) 50 mL of 0.10 M NH4OH + 50 mL of 0.10 M HCl.
(f) 50 mL of 0.05 M NH4OH + 50 mL of 0.05 M CH3COOH.
C-2. 15 mL sample of 0.15M NH3(aq) is titrated against 0.1M HCl(aq). What is the pH at the end point? Kb of
NH3(aq) = 1.8 x 105.
C-3. pH at the mid point of titration of 20mL of 1M formic acid with 1M NaOH is 3.7. Find the pH at the end point
of titration.
C-4. Calculate the pH during the titration of 40.00 mL of 0.1 M propanoic acid (HPr; Ka = 1 × 10–5) after adding the
following volumes of 0.1 M NaOH: (log 2 = 0.3, log 3 = 0.48)
(a) 0.00 mL (b) 30.00 mL (c) 40.00 mL (d) 50.00 mL.

B.Tech. IIT Delhi
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Section (A) : Buffer Solution & Buffer Capacity
A-1. A solution is 0.1 M CH3COOH and 0.1 M CH3COONa. Which of the following solution will change its pH
significantly?
(A) Addition of water
(B) Addition of small amount of CH3COONa with out change in volume
(C) Addition of small amount of CH3COOH with out change in volume
(D) None will change the pH significantly.
A-2. Ka for HCN is 5 × 10–10 at 25°C. For maintaining a constant pH of 9, the volume of 5 M KCN solution required
to be added to 10 ml of 2M HCN solution is (log 2 = 0.3)
(A) 4 ml (B) 8 ml (C) 2 ml (D) 10 ml
A-3. What % of the carbon in the H2CO3 – HCO3– buffer should be in the form of HCO3– so as to have a neutral
solution? (Ka = 4 × 10–7)
(A) 20 % (B) 40 % (C) 60 % (D) 80%
A-4. A buffer solution is prepared by mixing 'a' moles of CH3COONa and 'b' moles of CH3COOH such that
(a + b) = 1, into water to make 1L buffer solution. If the instantaneous (differantial) buffer capacity of this
buffer solution is plotted against moles of salt CH3COONa (a) then the plot obtained will be (to the scale)
approximately. (As shown in figure in options)
0.25
Buffer capacity
0.20
(A) 0.15
(B)
0.10
0.0 0.2 0.4 0.6 0.8 1.0
a
0.55
0.50
Buffer capacity
0.45
(C) 0.40 (D)

0.35
0.30
0.0 0.2 0.4 0.6 0.8 1.0
a
A-5. Buffer capacity of a buffer solution is x, the volume of 1 M NaOH added to 100 mL of this solution if change
the pH by 1 is
(A) 0.1 x mL (B) 10 x mL (C) 100 x mL (D) x mL
Section (B) : Theory of indicators

B-1. A certain indicator (an organic dye) has pKa = 5. For which of the following titrations may it be suitable.
(A) acetic acid against NaOH (B) aniline hydrochloride against NaOH
(C) sodium carbonate against HCl (D) barium hydroxide against oxalic acid
B-2. The best indicator for the detection of end point in titration of a weak acid and a strong base is :
(A) Methyl orange (3 to 4) (B) Methyl red (5 to 6)
(C) Bromothymol blue (6 to 7.5) (D) Phenolphthalein (8 to 9.6).

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B-3. What fraction of an indicator HIn is in basic form at a pH of 6 if the pKa of the indicator is 5 ?
1 1 10 1
(A) (B) (C) (D)
2 11 11 10
Section (C) : Acid-base Titration

C-1. Which is/are correct statements :
(i) In any strong acid’s solution, the concentration of [OH–] will be zero.
(ii) If Gº of a reaction is positive, then the reaction will not proceed at all,
in the forward direction for any concentrations of reactants and products.
(iii) Titration curves are drawn for (about the figure shown)
(a) 1M HCl (50 mL) with 1 M NaOH and
(b) 0.01 M HCl (50 mL) with 0.01 M NaOH on the same graph paper they look like:
(A) i & ii (B) iii only (C) ii only (D) i & iii
C-2. Which is/are correct statements :
(a) When 100 ml of 0.1 M NaCN solution is titrated with 0.1 M HCl solution
the variation of pH of solution with volume of HCl added will be (as
shown in figure):
(b) Variation of degree of dissociation  with concentration for a weak

electrolyte at a particular temperature is best represented by (as shown
in figure) :
(c) 0.1 M acetic acid solution is titrated against 0.1 M NaOH solution. The difference in pH between 1/4 and
3/4 stages of neutralization of acid will be 2 log 3.
(A) a & c (B) b & c (C) a, b & c (D) b only
C-3. To a 200 ml of 0.1 M weak acid HA solution 90 ml of 0.1 M solution of NaOH be added. Now, what volume of
0.1 M NaOH be added into above solution so that pH of resulting solution be 5. [(Ka(HA) = 10–5]
(A) 2 ml (B) 20 ml (C) 10 ml (D) 15 ml
C-4. 50 mL of 0.1 M NaOH is added to 60 mL of 0.15 M H3PO4 solution (K1, K2 and K3 for H3PO4 are 10–3, 10–8 and 10–
13
respectively). The pH of the mixture would be about (log 2 = 0.3)
(A) 3.1 (B) 5.5 (C) 4.1 (D) 6.5
C-5. 100 mL of 0.02 M benzoic acid (pKa = 4.2) is titrated using 0.02 M NaOH. pH after 50 mL and 100 mL of
NaOH have been added are
(A) 3.50, 7 (B) 4.2, 7 (C) 4.2, 8.1 (D) 4.2, 8.25
C-6. If 50 ml of 0.2 M KOH is added to 40 ml of 0.5 M HCOOH. the pH of the resulting solution is:
(Ka = 1.8 × 10–4, log 18 = 1.26)
(A) 3.74 (B) 5.64 (C) 7.57 (D) 3.42
C-7. When 100 ml of 0.4 M CH3COOH are mixed with 100 ml of 0.2 M NaOH, the [H3O+] in the solution is
approximately : [Ka(CH3COOH) = 1.8 × 10–5]
(A) 1.8 × 10–6 M (B) 1.8 × 10–5 M (C) 9 × 10–6 M (D) 9 × 10–5 M.
C-8. Which of the following solutions would have same pH?
(A) 100 ml of 0.2 M HCl + 100 ml of 0.4 M NH3 (B) 50 ml of 0.1 M HCl + 50 ml of 0.2 M NH3
(C) 100 ml of 0.3 M HCl + 100 ml of 0.6 M NH3 (D) All will have same pH.

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1. Statement-1 : In a titration of weak monoprotic acid with strong base, the pH at the half equivalent point is
pKa.
Statement-2 : At half equivalence point, it will form acidic buffer at it's maximum capacity where
[acid] = [salt].
(C) STATEMENT-1 is true, STATEMENT-2 is false.
(D) STATEMENT-1 is false, STATEMENT-2 is true.
(E) Both STATEMENTS are false.

1. A 0.252 g sample of unknown organic base is dissolved in water and titrated with a 0.14 M HCl solution. After
the addition of 20 mL of acid, a pH of 10.7 is recorded. The equivalence point is reached when a total of 40 mL
of HCl is added. The base and acid combine in a 1 : 1 ratio.
(a) What is the molar mass of the organic base ?
(b) What is the Kb value for the base ?
2. Phosphoric acid ionizes according to the equations
H3PO4(aq) H+ (aq) + H2PO4– (aq) ; K1 = 7 × 10–3
H2PO4 (aq)
–
H (aq) + HPO4 (aq) ;
+ 2–
K2 = 6 × 10–8
HPO4 (aq)
2–
H (aq) + PO4 (aq) ;
+ 3–
K3 = 4.5 × 10–13
(a) If you are asked to prepare a buffer with a pH = 7.00, identify the species that should be used in the
solution and calculate their molar ratio.
(b) Assume 50 mL of the buffer prepared in part (a) is available in which more abundant species has a
concentration of 0.10 M. If to this solution 20 mL 0.1 M NaOH is added further, what will be the new pH ?
(log2 = 0.3, log3 = 0.48)
3. 0.98 gm of H3PO4 is dissolved in 100 ml of buffer solution (pH = 5). Calculate the equilibrium concentrations
of H2PO4–, HPO42–, PO43– and H3PO4 in the solution. Ka1 = 10–3, Ka2 = 10–8, Ka3 = 0–12.
4. An NH4+ - NH3 buffer is supposed to keep the pH of the solution constant within 0.3 pH unit during the
reaction.
CH3COOCH3 (aq) + 2H2O (aq)   CH3COO–(aq) + H3O+ (aq) + CH3OH(aq)
If this solution had initial concentrations : [NH4+]0 = 0.1 M, [NH3]0 = 0.06 M, [CH3COOCH3]0 = 0.02 M.
What would be the initial and final pH of the solution ? Is this a satisfactory buffer ? [Kb(NH3) = 1.8 × 10–5,
log2 = 0.3, log3 = 0.48].
5. A certain solution has a hydrogen ion concentration 4 x 103 M. At pH = 2, half of the indicator, thymol blue
is in unionised form. Find the % of indicator in unionised form in the solution with [H+] = 4 × 103 M.

Single choice type
1. Aniline behaves as a weak base. When 0.1 M, 50 ml solution of aniline was mixed with 0.1 M, 25 ml solution
of HCl the pH of resulting solution was 8. Then the pH of 0.01 M solution of aniliniumchloride will be
(Kw = 10–14)
(A) 6 (B) 6.5 (C) 5 (D) 5.5
2. 1 M benzoic acid (pKa = 4.20) and 1M C6H5 COONa solutions are given separately. What is the volume of
benzoic acid required to prepare a 300 ml buffer solution of pH = 4.5 ? [log 2 = 0.3]
(A) 200 ml (B) 150 ml (C) 100 ml (D) 50 ml

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3. To prepare a buffer of pH 8.26 amount of (NH4)2 SO4 to be added to 500 mL of 0.01 M NH4OH solution
[pKa (NH4+) = 9.26] is
(A) 0.05 mole (B) 0.025 mole (C) 0.10 mole (D) 0.005 mole
4. Pure water is added into the following solutions causing a 10% increase in volume of each. The greatest %
change in pH would be observed in which case (A), (B), (C) or (D) ?
(A) 0.1 M NaHCO3 (B) 0.2 M NaOH
(C) 0.3 M NH3 – 0.2 M NH4 system
+
(D) 0.4 M CH3COONH4
5. An acid-base indicator which is a weak acid has a pKIn value = 5.45. At what cocentration ratio of sodium
acetate to acetic acid would the indicator show a colour half-way between those of its acid and conjugate
base forms? [pKa of acetic acid = 4.75, log 2 = 0.3]
(A) 4 : 1 (B) 6 : 1 (C) 5 : 1 (D) 3 : 1
6. What will be the pH at the equivalence point during the titration of a 100 mL 0.2 M solution of CH3COONa with
0.2 M solution of HCl ? Ka = 2 × 10–5.
(A) 3 – log 2 (B) 3 + log 2 (C) 3 – log 2 (D) 3 + log 2
7. 20 mL of a weak monobasic acid (HA) requires 20 mL 0.2 M NaOH for complete titration. If pH of solution
upon addition of 10 mL of this alkali to 25 mL of the above solution of HA is 5.8. The pKa of the weak acid is
(A) 6.1 (B) 5.8 (C) 5.98 (D) 5.58
8. What is the difference in pH for 1/3 and 2/3 stages of neutralisation of 0.1 M CH3COOH with 0.1 M NaOH.
(A) 2 log 3 (B) 2 log (1/4) (C) 2 log (2/3) (D) 2 log 2
9. 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 27 mL. Ka of acid is (log2 = 0.3)
(A) 1.8 × 10–5 (B) 8 × 10–6 (C) 1.8 × 10–6 (D) 8 × 10–5

10.* Which one is the correct graph (figure) for the corresponding acid base titration?
(A) (B)
(C) (D)
Volume of strong base Volume of strong acid

added to a weak dibasic acid added to a weak diacidic base

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11.* A weak acid (or base) is titrated against a strong base (or acid),
volume v of strong base (or acid) is plotted against pH of the solution
(as shown in figure). The weak electrolyte (i.e. acid or base) could
be
(A) Na2CO3 (B) Na2C2O4
(C) H2C2O4 (D) CH2(COOH)2
12.* Which of the following are true for an acidbase titration ?
(A) Indicators catalyse the acid base reactions by releasing or accepting H+ ions.
(B) Indicators do not significantly affect the pH of the solution to which they are added.
(C) Acidbase reactions do not occur in absence of indicators.
(D) Indicators have different colours in dissociated and undissociated forms.
13.* A buffer solution can be prepared from a mixture of [JEE-1999, 3/80]
(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 soldium hydroxide in water
14.* Which of the following is/are correct regarding buffer solution ?

(A) It contains weak acid and its conjugate base
(B) It contains weak base and its conjugate acid
(C) It shows large change in pH on adding small amount of acid or base.
(D) All of the above.
15. Choose the correct statement
(A) pH of acidic buffer solution decrease if more salt is added.
(B) pH of acidic buffer solution increases if more salt is added.
(C) pH of basic buffer decreases if more salt is added.
(D) pH of basic buffer increases if more salt is added.
16. Which of following can act as buffer ?
(A) NaCl + NaOH (B) NaHCO3 + H2CO3
(C) NaH2PO4 + Na2HPO4 (D) NH4Cl + NH4OH.
17. Which of the following will show common ion effect and form a buffer solution ?
(A) CH3COONH4 and CH3COOH (B) NH4Cl + NH4OH
(C) H2SO4 + NaHSO4 (D) NaCl + NaOH.
18. Titration curves for 0.1M solutions of three weak acids HA1, HA2
and HA3 with ionization constants K1, K2 and K3 respectively are
plotted as shown in the figure. Which of the following is/are true?
(A) K2 = (K1 + K3)/2

(B) K1 < K3
(C) K1 > K2
(D) K2 > K3
19. Let the colour of the indicator Hn (colourless) will be visible only when its ionised form (pink) is 25% or more
in a solution. Suppose Hn (pKa = 9.0) is added to a solution of pH = 9.6 predict what will happen.
(Take log 2 = 0.3)
(A) pink colour will be visible (B) pink colour will not be visible
(C) % of ionised form will be less than 25% (D) % of ionised form will be more than 25%
20. Which of the following mixtures will act as buffer ?

(A) H2CO3 + NaOH (1.5 : 1 molar ratio) (B) H2CO3 + NaOH (1.5 : 2 molar ratio)
(C) NH4OH + HCl (5 : 4 molar ratio) (D) NH4OH + HCl (4 : 5 molar ratio)

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21._ When weak base solution (50 ml of 0.1 N NH4OH) is titrated with
strong acid 0.1 N HCl, the pH of solution initially decreases fast
and then decreases slowly till near equivalence point (as shown)
in the figure. Which of the following is true.
(A) The slow decrease of pH is due to formation of an acidic buffer
solution after addition of some HCl
(B) The slope of shown pH graph magnitude only will be minimum
when 25 ml of 0.1 N HCl is added
(C) The slow decrease of pH is due to formation of a basic buffer
solution
(D) The initial fast decrement in pH is due to fast consumption of
free OH¯ ions by HCl.
22._ Which of the following is incorrect statement.
(A) If K1 and K2 for dissociation of H2A is 10–7 and 10–14 then A2– concentration in 0.1 M H2A solution is 10–7.
(B) A solution of pH = 1 has H+ ion concentration 3 times than that of a solution of pH = 3.
(C) If a salt solution of weak acid & weak base is diluted upto limited extent then its pH will decrease.
(D) pH of acidic buffer solution depends upon pKa and relative molar amount of weak acid and its conjugate
base.

1. Match the effect of addition of 1 M NaOH to 50 ml of 1 M H2C2O4 (diprotic acid) in column I with column II
(Given: Ka1 = 10–4, Ka2 = 10–9)
Column I Column II
(A) 25 mL of NaOH (p) Buffer solution
(B) 50 mL of NaOH (q) pH is independent of concentration of species
present in the solution.
(C) 75 mL of NaOH (r) anionic hydrolyisis
(D) 100 mL of NaOH (s) pH > 7
Comprehension #
[Base ]
The pH basic buffer mixtures is given by : pH = pKa + log , whereas pH of acidic buffer mixtures is
[Salt]
[Salt]
given by : pH = pKa + log . Addition of little acid or base although shows no appreciable change in pH
[ Acid]
[Base ] [Salt]
for all practical purposes, but since the ratio for changes, a slight decrease or increase in pH
[Salt] [ Acid]
results.
1. The amount of (NH4)2SO4 to be added to 500 mL of 0.01 M NH4OH solution (pKa for NH4 is 9.26) prepare a
buffer of pH 8.26 is:
(A) 0.05 mole (B) 0.025 mole (C) 0.10 mole (D) 0.005 mole
2. A solution containing 0.2 mole of dichloroacetic acid (Ka = 5 × 10–2) and 0.1 mole sodium dichloroacetate in
one litre solution has [H+]:
(A) 0.05 M (B) 0.025 M (C) 0.10 M (D) 0.005 M
3. The volume of 0.2 M NaOH needed to prepare a buffer of pH 4.74 with 50 mL of 0.2 M acetic acid (pKb of
CH3COO– = 9.26) is:
(A) 50 mL (B) 25 mL (C) 20 mL (D) 10 mL
4. The ratio of pH of solution(I) containing 1 mole of CH3COONa and 1 mole of HCI and solution(II) containing 1
mole of CH3COONa and 1 mole of acetic acid in one litre is:
(A) 1 : 2 (B) 2 : 1 (C) 1 : 3 (D) 3 : 1

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1. 0.1 M NaOH is titrated with 0.1 M 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. [JEE-2004, 2/60]
2. 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? What will be the H+ concentration in the solution? [JEE-2005, 3/84]
(A) 8 × 10 M –2
(B) 8 × 10–11
M
(C) 1.6 × 10 –11
M (D) 8 × 10 M –5
2 2
3. 2.5 mL of M weak monoacidic base (Kb = 1 x 10–12 at 25° C) is titrated with M HCl in water at 25°C.
5 15
The concentration of H+ at equivalence point is (Kw = 1 x 10–14 at 25°C) [JEE-2008, 3/163]

(A) 3.7 x 10 –14
M (B) 3.2 x 10 M –7
(C) 3.2 x 10–2 M (D) 2.7 x 10–2 M
4.* Aqueous solutions of HNO3, KOH, CH3COOH, and CH3COONa of identical concentrations are provided. The
pair (s) of solutions which form a buffer upon mixing is (are) : [JEE-2010, 3/163]
(A) HNO3 and CH3COOH (B) KOH and CH3COONa
(C) HNO3 and CH3COONa (D) CH3COOH and CH3COONa
1. 1 M NaCl and 1 M HCl are present in an aqueous solution. The solution is [AIEEE-2002]
(1) not a buffer solution with pH < 7 (2) not a buffer solution with pH > 7
(3) a buffer solution with pH < 7 (4) a buffer solution with pH > 7
2. The pKa of a weak acid (HA) is 4.5. The pOH of an aqueous buffered solution of HA, in which 50% of the acid
is ionized, is : [AIEEE-2007, 3/120]
(1) 9.5 (2) 7.0 (3) 4.5 (4) 2.5

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EXERCISE - 1
PART - I
A-1. (a) 4.62 (b) 8.57 (c) 4.94 A-2. 0.02 M A-3. 8.9 × 10–3 mol
A-4. pH = 4.74 A-5. pH = 9.26 ; (a) pH = 9.74 ; (b) 8.78
A-6. 0.23 for first and 0.115 for later. A-7. [Ac–] = 0.036 M B-1. Orange (pH = 5.13)
B-2. 0.257 C-1. (a) 12.4, (b) 4.7, (c) 7, (d) 9.3, (e) 1.6, (f) 7
C-2. 5.24 C-3. pH = 8.7
C-4. (a) pH = 3 (b) pH = 5.48, (c) pH = 8.85, (d) pH = 12.05
PART - II
A-1. (D) A-2. (C) A-3. (D) A-4. (B) A-5. (C)
B-1. (C) B-2. (D) B-3. (C) C-1. (B) C-2. (C)
C-3. (C) C-4. (A) C-5. (C) C-6. (A) C-7. (B)
C-8. (D)
PART - III
1. (A)
EXERCISE - 2
PART - I
1. (a) 45 , (b) 5 × 10–4 2. (a) 0.6, (b) 7.44
3. [H3PO4] = 10–3 M, [H2PO4–] = 0.1 M, [HPO42–] = 10–4 M , [PO43–] = 10–11 M
4. 9.04, 8.78, yes. 5. 28.57%
PART - II
1. (C) 2. (C) 3. (B) 4. (B) 5. (C)
6. (A) 7. (C) 8. (D) 9. (B) 10.* (A,B,C,D)
11.* (C,D) 12.* (B,D) 13.* (A,B,C) 14.* (A,B) 15. (B,C)
16. (B,C,D) 17. (A,B) 18. (C,D) 19. (A,D) 20. (A,B,C)
21. (B,C,D) 22. (A,B,C)
PART - III
1. (A – p, q); (B – q, r); (C – p, q, s) ; (D – r, s)
PART - IV
1. (B) 2. (A) 3. (B) 4. (A)
EXERCISE - 3
PART - I
1. 8.98  9 2. (B) 3. (D) 4.* (C,D)
PART - II
1. (1) 2. (1)

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Section (A) : Solubility product and simple solubility calculation, common ion effect
A-1. How many milligrams of gold(III) ion are there per litre of solution in a saturated aqueous solution of gold (III)
iodide ? AuI3(s) Au3+(aq) + 3 I (aq) . Ksp = 2.7 × 10–47 [Au = 197]
A-2. Calculate the solubility of silver phosphate (Ag3PO4) in mg/ml (a) in pure water and (b) in a solution that is
0.02 M in AgNO3 . [Ksp(Ag3PO4) = 2.7 × 10–23]
A-3. Although it is a violent poison if swallowed, mercury (II) cyanide, Hg(CN)2 has been used as a typical (skin)
antiseptic. (KSP = 1.35 × 10–23, Hg = 200)
(a) What is the molar solubility of this salt in pure water ?
(b) How many milligrams of Hg(CN)2 dissolve per litre of pure water ?
(c) How many milliliters of water are required to dissolve 1.134 g of the salt ?
A-4. Equal volumes of 0.002 M each of sodium iodate and cupric chlorate are mixed together. Will it lead to
precipitation of copper iodate? (For cupric iodate KSP = 7.4 × 10–8).
A-5. What is the maximum concentration of equimolar solution of ferrous sulphate and sodium sulphide so that
when mixed in equal volumes, there is no precipitation of iron sulphide ? (For iron sulphide KSp = 6.25 × 10–18)
A-6. A mixture of solid SrSO4 and solid BaSO4 is shaken up with water until equilibrium is established. Given that
Ksp (SrSO4) = 7.5 × 10–7, Ksp (BaSO4) = 6 × 10–8, calculate the concentrations of Sr2+, Ba2+, SO42– in the
solution at equilibrium.
Section (B) : Solubility in buffer, Complex formation, Selective precipitation

B-1. An aqueous solution of a metal bromide, MBr2 (0.05 M) is saturated with H2S. Calculate the minimum pH at
which the metal sulphide will be precipitated. Concentration of H2S in a saturated solution = 0.1M. [Ka1 of
(H2S) = 10–7, Ka2 of (H2S) = 1.2 × 10–13, Ksp for MS = 6 × 10–21]
B-2. A solution which is 0.1 M in NaI and also 0.1 M in Na2SO4 is treated with solid Pb(NO3)2. Which compound,
PbI2 or PbSO4, will precipitate first ? What is the concentration of anions of the least soluble compound when
the more soluble one starts precipitating ? Ksp(PbI2) = 9 × 10–9 , Ksp(PbSO4) = 1.8 × 10–8

Section (A) : Solubility product and simple solubility calculation, Common ion effect.
A-1. If the solubility of lithium sodium hexafluorido aluminate, Li3Na3 (AlF6)2 is ‘s’ mol lt–1, its solubility product is
equal to :
(A) 729 s8 (B) 12 s8 (C) 3900 s8 (D) 2916 s8
A-2. The solubility of CaF2 (Ksp = 3.4 × 10–11) in 0.1 M solution of NaF would be
(A) 3.4 × 10–12 M (B) 3.4 × 10–10 M (C) 3.4 × 10–9 M (D) 3.4 × 10–13 M.
A-3. In a saturated solution of Ag2CO3, silver ion concentration is 2 × 10–4 M. Its solubility product is
(A) 4 × 10–12 (B) 3.2 × 10–11 (C) 8 × 10–12 (D) 10–12
A-4. The solubility of Ag2CO3 in water at 250C is 1 × 104 mole/litre. What is its solubility in 0.01 M Na2CO3
solution? Assume no hydrolysis of CO32 ion.
(A) 6 × 106 mole/litre (B) 4 × 105 mole/litre (C) 105 mole /litre (D) 2 × 105 mole/litre

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A-5. Let the solubilities of AgCl in pure water, 0.01 M CaCl2, 0.01 M NaCl & 0.05 M AgNO3 be s1, s2, s3 & s4
respectively what is the correct order of these quantities . Neglect any complexation.
(A) s1 > s2 > s3 > s4 (B) s1 > s2 = s3 > s4
(C) s1 > s3 > s2 > s4 (D) s4 > s2 > s3 > s1
Section (B) : Solubility in buffer, Complex formation, Selective precipitation

B-1. The solubility product of AgCl is 1.8 × 10–10. Precipitation of AgCl will occur only when equal volumes of
solutions of
(A) 10–4M Ag+ and 10–4 M Cl– are mixed. (B) 10–7 M Ag+ and 10–7 M Cl– are mixed.
(C) 10 M Ag and 10 M Cl are mixed.
–5 + –5 –
(D) 2 × 10–5 M Ag+ and 2 × 10–5 M Cl– are mixed.
B-2. The solubility product of BaCrO4 is 2.4 × 10–10 M2. The maximum concentration of Ba(NO3)2 possible without
precipitation in a 6 × 10–4 M K2CrO4 solution is
(A) 4 × 10–7 M (B) 1.2 × 1010 M (C) 6 × 10–4 M (D) 3 × 10–4 M.
B-3. What is the solubility of Al(OH)3, (Ksp = 1 × 10–33) in a buffer solution pH = 4 ?

(A) 10–3 M (B) 10–6 M (C) 10–4 M (D) 10–10 M.
B-4. The solubility of Fe(OH)3 would be maximum in
(A) 0.1 M NaOH (B) 0.1 M HCl (C) 0.1 M KOH (D) 0.1 M H2SO4.
B-5. The best explanation for the solubility of MnS in dilute HCl is that :
(A) Solubility product of MnCl2 is less than that of MnS
(B) Concentration of Mn2+ is lowered by the formation of complex ions with chloride ions
(C) Concentration of sulphide ions is lowered by oxidation to free sulphur
(D) Concentration of sulphide ions is lowered by formation of weak acid H2S
B-6. Which of the following statements is correct for a solution saturated with AgCl and AgBr if their solubilities in
moles per litre in separate solutions are x and y respectively ?
(A) [Ag+] = x + y (B) [Ag+] = [Br–] + [Cl–]
(C) [Br–] = y (D) [Cl–] > x.
B-7. At 25ºC, the solubility product values of AgCl and AgCNS are 1.8 x 1010 and 1.6 x 1011 respectively. When
a solution is saturated with both solids, calculate the ratio [Cl]/[CNS] and also [Ag+] in the solution.
(A) 1.125, 4 × 106 M (B) 11.25, 1.4 × 105 M (C) 1.25, 4 ×105 M (D) 1.25, 4 × 106 M
B-8. Arrange in increasing order of solubility of AgBr in the given solutions.
(i) 0.1 M NH3 (ii) 0.1 M AgNO3 (iii) 0.2 M NaBr (iv) pure water
(A) (iii) < (ii) < (iv) < (i) (B) (iii) < (ii) < (i) < (iv)
(C) (iii) < (ii) = (i) < (iv) (D) (ii) < (iii) < (iv) < (i)
B-9.* A solution containing a mixture of 0.05 M NaCl and 0.05 M NaI is taken (Ksp of AgCl = 10–10 and Ksp of
AgI =4×10–16 ). When AgNO3 is added to such a solution.
(A) the concentration of Ag+ required to precipitate Cl– = 2 ×10–9 mol/L.
(B) the concentration of Ag+ required to precipitate I– = 8 × 10–15 mol/L.
(C) AgCl and AgI will be precipitated together.
(D) first AgI will be precipitated.

1. Statement-1 : Solubility of AgCl in NH3(aq) is greater than in pure water.
Statement-2 : When AgCl dissolve in NH3(aq), complex ion [Ag(NH3)2+] formation takes place and solubility
equilibrium of AgCl shifted in forward direction.
(C) STATEMENT-1 is true, STATEMENT-2 is false
(D) STATEMENT-1 is false, STATEMENT-2 is true
(E) Both STATEMENTS are false

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1. 0.2 moles of MgCl2(s) is mixed with 0.2 moles of NaOH(s) in a total volume of 1.0 litre.
(log2 = 0.3, log3 = 0.48)
(a) Calculate pH of this solution. Ksp of Mg(OH)2 is 1.6 × 10–12 .
(b) Also determine pH when 0.04 moles of NaOH(s) is added in the solution (a).
(c) Also determine pH of solution obtained after adding 0.04 mole of HCl(g) to solution (a).
2. The solubility product Mg(OH)2 in water at 25ºC is 2.56 × 1013(mol/lt)3 while that of Al(OH)3 is 4.32 × 1034
(mol/lt)4. If s1 and s2 are the solubilities of Mg(OH)2 and Al(OH)3 in water in mol/lt at 250C, what is the
approximate ratio, s1/s2 ?
3. Silver ion forms Ag(CN)2¯ in the presence of excess CN¯. How much solid KCN should be added to 1 litre of
a 0.0009 M Ag+ solution in order to reduce [Ag+] to 1 × 10–19. [Kdiss of Ag(CN)2¯= 1 × 10–21]
4. A buffer solution is 0.25 M CH3COOH and 0.15 M CH3COONa, saturated with H2S (0.1 M) and has
[Mn2+] = 0.015 M. Given : Ka (CH3COOH) = 1.8 × 10–5 , Ka(H2S) = 9 × 10–21 , Ksp(MnS) = 2.4 × 10–13.
(a) Will MnS precipitate
(b) Which buffer component should be increased in concentration and to which minimium value to just start
precipition of MnS ?
5. Calculate the solubility of CaC2O4 in a solution with a fixed H3O+ concentration of 10–4 M. The oxalate
containing species (C2O42– , HC2O4– , H2C2O4) exist in solution & the relevant equilibria are,
CaC2O4 (s) Ca2+ + C2O42– Ksp = 2.7 × 10–9
H2C2O4 + H2O H3O + + HC2O4– K1 = 5 × 10–2
HC2O4 + H2O
–
H3O + C2O4
+ 2–
K2 = 5 × 10–5
6. 0.01 mole of AgNO3 is added to 1 litre of a solution which is 0.1 M in Na2CrO4 and 0.005 M in NaIO3.
Calculate the mole of precipiate formed at equilibrium and the concentrations of Ag+, O3– and CrO42–.(KSP
values of Ag2CrO4 and AgIO3 are 10–8 and 10-13 respectively )

Single choice type
1. A well is dug in a bed of rock containing fluorspar (CaF2). If the well contains 20000 L of water, what is the
amount of F– in it ? Ksp = 4 × 10–11 (101/3 = 2.15)
(A) 4.3 mol (B) 6.8 mol (C) 8.6 mol (D) 13.6 mol
2. What is the minimum pH when Fe(OH)3 starts precipitating from a solution containing 0.1M FeCl3? Ksp of
Fe(OH)3 = 8 × 10–13 M3
(A) 3.7 (B) 5.7 (C) 10.3 (D) 8.3
3. The solubility product of AgCl is 10–10. The minimum volume (in L) of water required to dissolve 1.722 mg of
AgCl is (molecular weight of AgCl = 143.5).
(A) 10 lt. (B) 2.2 lt. (C) 1.2 lt. (D) 20 lt.
4. A solution prepared by dissolving 2.8 g of lime (CaO) in enough water to make 1.00 L of lime water
(Ca(OH)2(aq.)). If solubility of Ca(OH)2 in water is 1.48 gm/lt. The pH of the solution obtained will be:
[log 2 = 0.3, Ca = 40 , O = 16, H = 1]
(A) 12.3 (B) 12.6 (C) 1.3 (D) 13
5. 0.1 millimole of CdSO4 are present in 10 mL acid solution of 0.08 N HCl. Now H2S is passed to precipitate all
the Cd2+ ions. The pH of the solution after filtering off precipitate, boiling off H2S and making the solution 100
mL by adding H2O is
(A) 2 (B) 4 (C) 6 (D) 8

B.Tech. IIT Delhi
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6._ In which of the following solutions, the solubility of AgCN will be greater than that in pure water :
Given Ksp(AgCN) = 4  10–16 , Ka (HCN) = 5  10–10
(A) 0.01 M Ag NO3 solution (B) A buffer solution of pH = 12
(C) 0.2 M NH3 solution (D) A buffer solution of pH = 5
7._ The solubility of a sparingly soluble salt Ax By in water at 25ºC = 1.4 × 10–4 M. The solubility product is
1.1 × 10–11. The possibilities are
(A) x = 1, y = 2 (B) x = 2, y = 1 (C) x = 1, y = 3 (D) x = 3, y = 1

1. Match the correct value of Ksp expression in term of solubility (s)
column-I Column-II
(A) Al 2O3 (p) 4s3
(B) CaO (q) 27s4
(C) Al(OH)3 (r) 108s5
(D) CaF2 (s) s2
Comprehension #
Strontium fluoride (SrF2) is a sparingly soluble salt. Let s1 be its solubility (in mol/lt.) in pure water at 25°C,
assuming no hydrolysis of F– ions. Also, let s2 be its solubility (in mol/lt.) in 0.1 M NaF solution at 25°C,
assuming no hydrolysis of F– ions and no complex formation.
However, it is known that s1 : s2 = 106 : 256. Now, answer the following questions.
1. The Ksp value of SrF2 at 25°C is :
(A) 2.048  10–9 (B) 1.372  10–9 (C) 1.864  10–9 (D) 2.916  10–9
2. The mass of NaF to be added to 100 ml solution of 0.0011 M Sr+2 ions to reduce its concentration to 2  10–
4
M is : [Assume no hydrolysis of F– ions]
(A) 0.42 g (B) 0.063 g (C) 0.021 g (D) 0.084 g
1
3. The solubility of SrF2(in mol/L) in a buffer solution of pH =5 at 25°C is : [Given : Ka for HF =  10–5]
7
(A) 1.6  10–3 (B) 3.2  10–3 (C) 4.8  10–3 (D) 6.4  10–3

1. For a sparingly soluble salt ApBq, the relationship of its solubility product (Ls) with its solubility (S) is :
[JEE-2001, 1/35]
(A) LS = Sp+q . pp . qq (B) LS = Sp+q . pq . qp
(C) LS = Spq . pp . qq (D) LS = Spq . (pq)p+q
2. A solution which is 10–3 M each in Mn2+, Fe2+, Zn2+ and Hg2+ is treated with 10–16 M sulphide ion. If Ksp values
of MnS, FeS, ZnS and HgS are 10–15, 10–23, 10–20 and 10–54 respectively, which one will precipitate first ?
[JEE-2003, 3/84]
(A) FeS (B) MgS (C) HgS (D) ZnS
3. Solubility product constant (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. Solubilities (mol dm–3) of the salts at temperature T are in the order:
[JEE-2008, 3/163]
(A) MX > MX2 > M3X (B) M3X > MX2 > MX (C) MX2 > M3X > MX (D) MX > M3X > MX2

B.Tech. IIT Delhi
Ph. - 8209916365 (NV Sir) 9057586906(VKP Sir)
M.Sc. IT-BHU
4. In 1 L saturated solution of AgCl [Ksp(AgCl) = 1.6 × 10–10], 0.1 mol of CuCl [Ksp(CuCl) = 1.0 × 10–6] is added.
The resultant concentation of Ag+ in the solution is 1.6 × 10–x. The value of "x" is : [JEE-2011, 4/180]
5. How many litres of water must be added to 1 litre of an aqueous solution of HCl with a pH of 1 to create an
aqueous solution with pH of 2 ? [JEE Main-2013]
(A) 0.1 L (B) 0.9 L (C) 2.0 L (D) 9.0 L
6. The Ksp of Ag2CrO4 is 1.1 × 10–12 at 298 K. The solubility (in mol/L) of Ag2CrO4 in a 0.1 M AgNO3 solution is:
[JEE-2013, Advanced]
(A) 1.1 × 10–11 (B) 1.1 × 10–10 (C) 1.1 × 10–12 (D) 1.1 × 10–9
Paragraph-1
When 100 mL of 1.0M HCl was mixed with 100 mL of 1.0 M NaOH in an insulated beaker at constant
pressure, a temperature increase of 5.7 °C was measured for the beaker and its contents (Expt.1). Because
the enthalpy of neutralization of a strong acid with a strong base is a constant (–57.0 kJ mol–1), this experiment
could be used to measure the calorimeter constant. In a second experiment (Expt. 2), 100 mL of 2.0 M actic
acid (Ka = 2.0 × 10–5) was mixed with 100 mL of 1.0 M NaOH (under identical conditions to Expt. 1) where a
temperature rise of 5.6 °C was measured. (Consider heat capacity of all solutions as 4.2 J g–1 K–1 and density
of all solution as 1.0 g mL–1) [JEE-2015, Advanced]
7. Enthalpy of dissociation (in kJ mol–1) of acetic acid obtained from the Expt. 2 is
(A) 1.0 (B) 10.0 (C) 24.5 (D) 51.4
8. The pH of the solution after Expt. 2 is

(A) 2.8 (B) 4.7 (C) 5.0 (D) 7.0

1. The solubility of Mg(OH)2 is s moles/litre. The solubility product under the same condition is[AIEEE-2002]
(1) 4S3 (2) 3S4 (3) 4S2 (4) S3.
2. The solubility in water of a sparingly soluble salt AB2 is 1.0 × 10–5 mol L–1. Its solubility product will be :
[AIEEE-2003]
(1) 4 × 10–15 (2) 4 × 10–10 (3) 1 × 10–15 (4) 1 × 10–10.
3. The molar solubility (in mol L–1) of a sparingly soluble salt MX4 is s. The corresponding solubility product is
Ksp.. s is given in terms of Ksp by the relation [AIEEE-2004]
(1) s = (Ksp/128)1/4 (2) s = (128Ksp)1/4 (3) s = (256Ksp)1/5 (4) s = (Ksp/256)1/5
4. The solubility product of a salt having general formula MX2, in water is : 4 × 10–12. The concentration of M2+
ions in the saturated aqueous solution of the salt is : [AIEEE-2005]
(1) 2.0 × 10–6 M (2) 1.0 × 10–4 M (3) 1.6 × 10–4 M (4) 4.0 × 10–10 M
5. In a saturated solution of the sparingly soluble strong electrolyte AgIO3 (Molecular mass = 283) the equilibrium
which sets in is
AgIO3(s) Ag+(aq) + O–3(aq)
If the solubility product constant Ksp of AgO3 at a given temperature is 1.0 × 10–8, what is the mass of AgO3
contained in 100 ml of its saturated solution? [AIEEE-2007, 3/120]
(1) 1.0 × 10–7 g (2) 1.0 × 10–4 g (3) 28.3 × 10 g
–2
(4) 2.83 × 10–3 g
6. Solid Ba(NO3)2 is gradually dissolved in 1.0 × 10–4 M Na2CO3 solution. At what concentration of Ba2+ will a
precipitate begin to form ? (Ksp for BaCO3 = 5.1 × 10–9) : [AIEEE-2009, 4/144]
(1) 5.1 × 10–5 M (2) 8.1 × 10–8 M (3) 8.1 × 10–7 M (4) 4.1 × 10–5 M
7. Solubility product of silver bromide is 5.0 × 10–13 . This quantity of potassium bromide (molar mass taken as
120 g mol–1) to be added to 1 litre of 0.05 M solution of silver nitrate to start the precipitation of AgBr is :
[AIEEE-2010, 4/144]
(1) 1.2 × 10 –10
g (2) 1.2 × 10 g
–9
(3) 6.2 × 10 g
–5
(4) 5.0 × 10–8 g
8. At 25°C, the solubility product of Mg(OH)2 is 1.0  10–11. At Which pH, will Mg2+ ions start precipitating in the
form of Mg(OH)2 from a solution of 0.001 M Mg2+ ions ? [AIEEE-2010, 4/144]
(1) 9 (2) 10 (3) 11 (4) 8

B.Tech. IIT Delhi
Ph. - 8209916365 (NV Sir) 9057586906(VKP Sir)
M.Sc. IT-BHU
EXERCISE - 1
PART-I
A-1. 1.97 × 10-7 mg/L A-2. (a) 4.19 × 10-4 mg/ml ; (b) 1.414 × 10-15 mg/ml
A-3. (a) 1.5 × 10–8 M ; (b) 3.78 × 10–3 mg ; (c) 3 × 108 ml A-4. No precipitate
A-5. 5 × 10–9 M A-6. 8.33 × 10–4 M, 6.67 × 10–5 M, 9 × 10–4 M
B-1. Minimum pH = 1 B-2. PbSO4, 0.02 M
PART-II
A-1. (D) A-2. (C) A-3. (A) A-4. (C) A-5. (C)
B-1. (A) B-2. (A) B-3. (A) B-4. (D) B-5. (D)
B-6. (B) B-7. (B) B-8. (A) B-9.* (A,B,D)
PART - III
1. (A)
EXERCISE - 2
PART - I
1. (a) 8.6, (b) 8.65, (c) 8.56 2. 9 × 107
3. 4.8 × 10–3 mol 4. (a) No , (b) [CH3COO–] = 0.6 M
5. 9 × 10–5 M 6. 0.0075, 3.2 × 10–4 M, 3.125× 10–10 M, 0.0975 M.
PART - II
1. (C) 2. (C) 3. (C) 4. (B) 5. (A)
6._ (C,D) 7._ (A,B)
PART - III
1. (A-r), (B-s), (C-q), (D-p)
PART - IV
1. (A) 2. (C) 3. (B)
EXERCISE - 3
PART - I
1. (A) 2. (C) 3. (D) 4. 7 5. (D)
6. (B) 7. (A) 8. (B)
PART - II
1. (1) 2. (1) 3. (4) 4. (2) 5. (4)
6. (1) 7. (2) 8. (2)

B.Tech. IIT Delhi
Ph. - 8209916365 (NV Sir) 9057586906(VKP Sir)
M.Sc. IT-BHU

Ionic Equilibrium

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IIT CHEMISTRY

Physical & Inorganic Organic Chemistry

Board Level Exercise 49 - 50

Name : ____________________________ Contact No. __________________

A - 475 Indra Vihar , Kota

Physical & Inorganic By Organic Chemistry By

ACIDS BASES AND SALTS :

 H3BO 3 is not Arrhenius acid.

 OH¯ ion also in hydrated form of H3O2¯, H7O 4¯, H5O3¯

 First group elements (except Li.) form strong bases.

Bronsted - Lowery concept : (Conjugate acid - base concept) (Protonic concept)

Conjugate acid - base pairs

Physical & Inorganic By Organic Chemistry By

 Backward reaction – Here HB+, being a proton donor, is an acid

Acid Base Conjugate Conjugate

 HCl + H2O H3O + + Cl¯

 HSO4– + NH3 NH4+ + SO42–

 [Fe(H2O)6]3+ +H2O H3O + + [Fe(H2O)5 (OH)]2+

 Conjugate acid - base pair differ by only one proton

LEWIS CONCEPT (ELECTRONIC CONCEPT) :

Physical & Inorganic By Organic Chemistry By

Now pH = –log[H+] = 7 and pOH  log[OH–] = 7 for water at 25° (experimental)

 Absolute dissociation constant of water :

pH CALCULATIONS OF DIFFERENT TYPES OF SOLUTIONS :

Strong base Solution :

pH of mixture of two strong acids :

pH of mixture of a strong acid and a strong base :

Physical & Inorganic By Organic Chemistry By

pH of a weak acid(monoprotic) Solution :

on increasing dilution  C           and [H+]   pH 

pH of a mixture of weak acid(monoprotic) and a strong acid Solution :

Physical & Inorganic By Organic Chemistry By

pH of a Solution of a polyprotic weak acid :

H2A HA¯ + H+ HA¯ A 2– + H+

[H ] [HA  ] [H ] [ A 2 ]

(c1  c1 2 )[c1(1   2 )] (c1  c1 2 )(c1c 2 )

[c1(1   2 )][1(1   2 )] [c1(1   2 )]  2

Finally, for calculating pH

Physical & Inorganic By Organic Chemistry By

Strong Weak Strong Weak

Physical & Inorganic By Organic Chemistry By

(iii) Salt of weak acid and strong base

(iv) Salt of weak acid and weak base

Physical & Inorganic By Organic Chemistry By

(a) (i) HCO3¯ + H2O CO23  +

(ii) HCO3¯ + H2O H2CO 3 +

(b) Similarly for H2PO4¯ and HPO42– amphiprotic anions.

Physical & Inorganic By Organic Chemistry By

SOLUBILITY(S) AND SOLUBILITY PRODUCT (KSP)

Solubility of solute in gm / litre

(a) 1 : 1 types salts or AB type of salts :

let the solubility of salt A2B3 is ‘s’ -

Physical & Inorganic By Organic Chemistry By

A-4. (a) Write conjugate acids of SO42– , RNH2 , NH2– , C2H5O C2 H5 , F–

Section (B) : Properties of water & pH Scale, Autoprotolysis

Physical & Inorganic By Organic Chemistry By

Section (F) : pH of polyprotic acids and bases

Section (H) : Salt hydrolysis, amphiprotic species

Physical & Inorganic By Organic Chemistry By

PART - II : OBJECTIVE QUESTIONS

Section (B) : Properties of water & pH Scale, Autoprotolysis

B-4. Kw of H2O at 373 K is 1 × 10–12. Identify which of the following is incorrect.

Name : __________ Contact No.