Ionic Equilibrium - Final

CHEMISTRY
MICRO-XI
IONIC EQUILIBRIUM
" A SPECIALLY DESIGNED KIT FOR LEARNING."

THE KEY  Basic principles of subjects. An outline of the topics to be
discussed in class lectures.
GLOSSARY  A list of important terms in brief
THE ATLAS  Basic layout of subject. A route map correlating different
subtopics in coherent manner.
EXERCISE I  Introductory problems based on JEE to get first hand
experience of problem solving.
EXERCISE II  A collection of good problems.
QUESTION BANK  Test your objective skill.
EXERCISE III  A collection of previous twenty years JEE problems.
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JEE Syllabus :
Solubility product, Common ion effect, pH and buffer solutions; Acids and bases (Bronsted and Lewis
concepts); Hydrolysis of salts.
THE KEY
Concepts of Acids & Bases
Arrhenius Theory
When dissolved in water, the substances which release
(i) H+ ions are called acids e.g. HNO3, HClO4,CH3COOH,
(ii) OH ions are called bases, e.g. NaOH, KOH, NH4OH
Bronsted & Lowry Concept

Acids are proton donors, bases are proton acceptors
Note that as per this definition, water is not necessarily the solvent.
When a substance is dissolved in water, it is said to react with water e.g.
HCl + H2O  H3O+ + Cl ; HCl donates H+ to water, hence acid.
NH3 + H2O  NH4 + + OH ; NH3 takes H+ from water, hence base.
For the backward reaction, NH4+ donates H+, hence it is an acid; OH accepts H+, hence it is base. NH3
(base) & NH4+ (acid) from conjugate acid base pair.
Conjugate acid and bases

To get conjugate acid of a given species add H+ to it. e.g. conjugate acid of N2H4 is N2H5+.
To get conjugate base of any species subtract H+ from it. e.g. Conjugate base of NH3 is NH2.
Note: Although Cl is conjugate base of HCl, it is not a base as an independent species. In fact, anions of all strong
acid like Cl, NO3, ClO4 etc. are neutral anions. Same is true for cations of strong bases like K, Na+, Ba++
etc. When they are dissolved in water, they do not react with water (i.e. they do not undergo hydrolysis) and
these ions do not cause any change in pH of water (others like CN do).
Some examples of :
Basic Anions : CH3COO, OH, CN (Conjugate bases of weak acids)
Acid Anions: HSO3, HS etc. Note that these ions are amphoteric, i.e. they can
behave both as an acid and as a base. e.g. for H2PO4 :
HS + H2O S + H3O+ (functioning as an acid)
HS + H2O H2S + OH (functioning as a base)
Acid Cations : + +
NH4 , H3O etc.(Conjugate acids of weak bases)
Lewis Concept : Acids are substances which accept a pair of electrons to form a coordinate
bond and bases are the substances which donate a pair of electrons to
form a coordinate bond.
IONIC EQUILIBRIUM_MICRO-XI
H F H F
| | | |
e.g. H  N: + B  F  H  N B  F
| | | |
H F H F
(Lewis base) (Lewis acid)
Important : Ca + S  Ca2+ + S2 is not a Lewis acidbase reaction since dative bond is not formed.
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Lewis Acids : As per Lewis concept, following species can acts as Lewis Acids :
(i) Molecules in which central atom has incomplete octet. (e.g. BF3, AlCl3 etc.)
(ii) Molecules which have a central atom with empty d orbitals (e.g. SiX4, GeX4,
PX3, TiCl4 etc.)
(iii) Simple Cations: Though all cations can be expected to be Lewis acids, Na+, K+ etc. show no
tendency to accept electrons. However H+, Ag+ etc. act as Lewis acids.
(iv) Molecules having multiple bond between atoms of dissimilar electronegativity.
—
e.g. CO2, SO2, SO3  (O  C  O  OH —  O  C  O or HCO 3— )
|
Lewis acid Lewis base
OH
Lewis bases are typically :
(i) Neutral species having at least one lone pair of electrons.

e.g. NH2 – NH2, R – O – H
(ii) Negatively charged species (anions). e.g. CN, OH, Cl etc.
CLASSIFICATION OF ELECTROLYTES
On the basis of their dissociation nature in water
(i) Strong electrolytes : Substances which are largely dissociatedand are strong electrolytes. e.g. HCl, HBr,
HI, HNO3, NaOH, KOH etc.
(ii) Weak electrolytes : Substances which dissociate only to a small extent in aqueous solution. e.g.
HCOOH, H3BO3, C6H5COOH etc.
(iii) Non electrolytes : Which do not dissociate. e.g. C6H12O6
Note: The above classification of substances in weak electrolyte and strong electrolyte is based on their dissociation
nature in aqueous medium. However, an electrolyte strong in water, might behave as a weak one when
dissolved in some other solvent or vice-versa. For example, sodium chloride acts as strong electrolyte in
water but it acts as weak electrolyte in methanol.
ARRHENIUS THEORY OF ELECTROLYTE IONISATION (DISSOCIATION):
A chemical equilibrium exists between the undissociated electrolyte molecules and the ions that result from
dissociation. consider ionisation of a weak electrolyte say a monoprotic a id, acid HA
Concentration before dissociation C 0 0

Concentration after dissociation C(1–) C C
where,  is degree of ionisation of weak acid HA. ‘C’ is intial concentration of acid HA in mole litre–1
According to equilibrium constant expression
Ka =
H  A   C.C 
 
=
C 2
where, Ka is Ionisation constant of an acid.
 HA  C1   1  
DEGREE OF IONISATION (DISSOCIATION):

 is fractional conversion of reactant or
Moles of reactant dissociate d

= Initial moles of reactant
The value of  depends
(1) Nature of solute (electrolyte): Strong electrolyte dissociate completely where as weak electrolytes dissociate
paritally.
(2) Nature of solvent : A solvent having high value of dielectric constant and high solvation (in case of water
hydration) will favour dissociation.
(3) Temperature : On increasing temperature degree of dissociation increases.
(4) Concentration : For weak electrolytes degree of dissociation increases by increasing dilution or decreasing
concentration (Ostwald’s dilution law)
Ostwald dilution law: Applicable for weak electrolytes (weak acids/bases)
If  is negligiable with respect to 1 (< .05)
than for mono basic acid and mono acidic base
 KC 
 KC = c2 or =   = KCV where, V is the volume of solution.
 C 
1
So   or   V.
C
at infinite dilution  reaches its maximum value value, unity.
(5) Presence of other solute (Common ion effect) :
When other substance is also present in water it may effect the  of the weak electrolyte. Degree of ionisation
of a weak electrolyte is suppressed by the addition of a substance having an ion common to weak electrolyte
is known as common ion effect.
IONIC PRODUCT OF WATER
Pure water is weak electrolyte and dissociated as:
H2O H+ + OH–
Before dissociation C 0 0
After dissociation C(1 – ) C C
Ki =
H OH 
 
 H2O
where, Keq is dissociation constant or equilibrium constant of water. Since, dissociation of water is too less
and thus, [H2O], i.e., undissociated H2O can be taken as constant, therefore
Ki [H2O] [H +] [OH –]
Kw = [H+] [OH–]
The new constant Kw is known as ionic product of water. The numerical value of Kw increases considerably
with temperature. It is 1.0 × 10–14 at 25°C. The variation of ionic product of water with temperature is given by
K w2 rH T2  T1
2.303 log K  R T T
w1 1 2
Autoprotolysis of water (or any solvent)

Autoprotolysis (or selfionization) constant (Kw) = [H3O+] [OH]
Hence, pH + pOH = pKw at all temperatures
Condition of neutrality [H3O+] = [OH] (for water as solvent)
At 25°C, KW = 1014. KW increases with increase in temperature. Accordingly, the neutral point of water
(pH = 7 at 25°C) also shifts to a value lower than 7 with increase in temperature.
Important: KW = 1014 is a value at (i) 25°C (ii) for water only. If the temperature changes or if some other
solvent is used, autoprotolysis constant will not be same.

pH CONCEPT
S.Sorenson used a new term pH to express the hydrogen ion concentration.
pH = – log [H+] or pH = log [H3O+] or [H+] = 10–pH
For simplicity hydrogen ions are simply written as H+, with the understanding that H+, ions in solution are
always solvated.
Similarly pOH = log [OH]
Note : As per thermodynamics pH has no unit, pH is difined as
pH = – log aH
Where, aH is the hydrogen ion activity. The H+ activity is obtained by multiplying [H+] by a suitable activity
coefficient () based on thermodynamic measurements. They approach 1.0 for very dilute solutions but get
smaller as concentration increases.
* for concentrate solution pH values greater than 14 are possible for concentrated strong base and negative
pH values are possible for concentrated strong acids.
* pH of very dilute (~ 108M or Lower) acids (or bases) is nearly 7 (not simplylog[acid] etc. due to ionization
of water.
* At 25°C, if pH = 7, then solution is neutral, pH > 7 then solution is basic.
Ionisation Constants
For dissociation of weak acids (eg. HCN), HCN + H2O H3O+ + CN the equilibrium
[H3 O  ][CN – ]
constant expression is written as Ka =
[HCN]
For the Polyprotic acids (e.g. H3PO4), sucessive ionisation constants are denoted by K a1 , K a2 , K a3 etc. For
H3PO4,
[H3 O  ][H 2 PO –4 ] [H3 O  ][HPO 24– ] [H3O  ][PO 34– ]

K a1 = ; K a2 = ; K a3 =
[H3PO 4 ]
–
[H2PO 4 ] [HPO 24– ]
Similarly, Kb denotes basic dissociation constant for a base.

AlsopKb = log10Kb, pKb = log10Kb
pH CALCULATION :-
Case (i)
A weak acid in water :
Ka
(a) if   is < 0.05, then [H+]  KaC .
C
(b) General Expression : [H  ]  0 .5( K a  K a2  4K a C )

Similarly for a weak base, substitute [OH] and Kb instead of [H+] and Ka respectively in these expressions.
Case (ii)
(a) A weak acid and a strong acid : [H+] is entirely due to dissociation of strong acid may be both depend on
conditions.
(b) A weak base and a strong base : [OH¯] is entirely due to dissociation of strong base may be both depend
on conditions.
Neglect the contribution of weak acid/base if  is negligiable.
Case (iii)
Two (or more) weak acids
If acids dissociate to a negligible extent, [H+] = K aC1  K a2 C 2
If we consider contribution of H+ from water then [H+] = K aC1  K a2 C2  K w
Case (iv)
When dissociation of water becomes significant :
Dissociation of water contributes significantly to [H+] or [OH] only when for
Strong acids (or bases) : 108M < C < 106M. Neglecting ionisation of water at
106M causes 1% error (approvable). Below 108M, contribution of acid (or base) can be neglected and pH
can be taken to be practically 7.
SALT HYDROLYSIS :-
Salts of strong acids and strong bases: do not undergo hydrolysis. solutions is always neutral.
Salts of a strong acids and weak bases give an acidic solution. e.g. NH4Cl when
dissolved, it dissociates to give NH4+ ions and NH4+ + H2O NH3 + H3O+.
Kh = [NH3][H3O+] / [NH4+] = Kw/Kb of conjugate base of NH4+
Important! In general : Ka(of an acid). Kb(of its conjugate base) = Kw
If the degree of hydrolysis(h or ) is small (<<1),  = K h C , [H+] = C
1
then pH = pk w  pk b  log C , C = concentration of cation
2
 K h  K h2  4K h C
Otherwise  = , [H+] = C
2C
Salts of strong base and weak acid: give a basic solution when dissolved in water, e.g. NaCN,
CN + H2O  HCN + OH  = K h C , [OH] = C,
1
If the degree of hydrolysis(h or ) is small ( < 0.05) then pH = pk w  pk a  log C
2
Salts of weak base and weak acid : Give a solution that may be acidic or basic or neutral when dissolved
in water, e.g. CH3COONH4
CH3COO– + NH4+ CH3COOH + NH3
Assuming degree of hydrolysis to be same for the both the ions,

Kh = Kw / (Ka.Kb), [H+] = [Ka Kw/Kb]1/2
1
pH = pk w  pk a  p k b 
2
Note : Exact treatment of this case is difficult to solve. So use this assumption in general cases.
Also, degree of anion or cation will be much higher in the case of a salt of weak acid and weak base. This is
because each of them gets hydrolysed, producing H+ and OH ions. These ions combine to form water and
the hydrolysis equilibrium is shifted in the forward direaction.
* Salts of polyvalent acid/base : Na2C2O4, Na2CO3, ZnCl2
Hydrolysis takes places in more than one step , in general effective hydrolysis of only first step takes place.
* Amphiprotic salts (acidic/basic) : NaHCO3, NaHC2O4, NaHS
1
pH =
2

pk a1  pk a2 
* Buffer Solutions are the solutions whose pH does not change significantly on adding a small quantity of
strong base or on little dilution. this does not mean that the pH will not change, and it means is that the pH
change would be less than the change that would have occurred had it not been a buffer.
In general buffer solutions are simple (salts of weak acid and weak base), or mixed buffer.
mixed buffer are of two types :
(A) Acidic buffer solutions : weak acid with its conjugate base :
made by mixing a weak acid (or base) with its conjugate base (or acid). e.g. CH3COOH with CH3COONa,
NaHCO3 & H2CO3, H3PO4 & NaH2PO4
(B) Basic buffer solutions : weak base with its conjugate acid :
NH3(aq) with NH4Cl (aq), RNH2 & RNH3Cl etc,
If Ka for acid (or Kb for base) is not too high, we may write :
Henderson's Equation :
pH = pKa + log {[salt] / [acid]} for weak acid with its conjugate base.
pOH = pKb + log {[salt] / [base]} for weak base with its conjugate acid.
Important : For good buffer capacity, [salt] : [acid] ratios should be as close to one as possible. In such a case,
pH = pKa. (This also is the case at midpoint of titration)
* Buffer capacity = (no. of moles of acid (or base) added per litre of buffer solution) / (change in pH)
Maximum buffer capacity :
It can be proved that maximum buffer is achieved when the salt and acid or base concentration is equal.
Indicators : Indicator is a substance which indicates the point of equivalence in a titration by undergoing a
change in its colour. They are weak acids or weak bases.
Theory of Indicators :The ionized and unionized forms of indicators have different colours. If 90 % or more
of a particular form (ionised or unionised) is present, then its colour can be distinclty seen.In general, for an
indicator which is weak acid, HIn H+ + In–, the ratio of ionized to unionized form can be determined from
[In  ]
pH = pKa + log
[HIn ]
So, for detectable colour change, pH = pKa ± 1
This roughly gives the range of indicators. Ranges for some popular indicators are
Table : Indicators
Indicators pH range Colour
acid medium basic medium
Methyl Orange 3.1-4.4 pink yellow
Methyl red 4.2-6.3 red yellow
Litmus 5.5-7.5 red blue
Phenol red 6.8-8.4 yellow red
Phenolphathlene 8.3-10 colourless pink
Thymol blue 1.2-2.8 red yello
Equivalence point: The point at which exactly equivalent amounts of acid and base have been mixed.
Acid Base Titration : For choosing a suitable indicator titration curves are of great help. In a titration curve,
change in pH is plotted against the volume of alkali to a given acid. Four cases arise.
(a) Strong acid vs strong base : The curve is almost vertical over the pH range 3.5-10. This abrupt change
corresponds to equivalence point. Any indicator suitable.
(b) Weak acid vs strong base : Final solution is basic 9 at equivalence point. Vertical region (not so sharp) lies
in pH range 6.5-10. So, phenolphathlene is suitable.
(c) Strong acid vs weak base : Final solution acidic. Vertical point in pH range 3.8-7.2. Methyl red or methyl
orange suitable.
(d) Weak acid vs weak base : No sharp change in pH. No suitable indicator.
Note : at midpoint of titration, pH = pKa, thus by pH measurements, Ka for weak acids (or Kb for weak bases)
can be determined.
Polyprotic acids and bases : Usually K2, K3 etc. can be safely neglected and only K1 plays a significant
role.
Solubility(S) & Solubility Product(Ksp) :

This is generally used for sparingly soluble salts,
Let the salt is Ax By, present in water. let the solubility of Ax By, is S
Ax By (S) xAy+ (aq) + yBx– (aq)
– xS yS  Ksp = (xS)x (yS)y = xxyy. (S)x + y
e.g. For sparingly soluble salts (e.g. Ag2C2O4) an equilibrium which exists as
Ag2C2O4 (S) 2Ag+ (aq.) + C2O42– (aq.)
Then Ksp= [Ag+]2[C2O42–]
Precipitation : Whenever the product of concentrations (raised to appropriate power) exceeds the solubility
product, precipitation occurs.
Common ion effects : Suppression of dissociation by adding an ion common with dissociation products.
e.g. Ag+ or C2O42– in the above example.
Simultaneous solubility : When two sparingly soluble salts present in water, solubility of both salts decreses
e.g. AgCl & AgBr, SrSO4 & BaSO4
Effect of complex formation & hydrolysis on solubility : Solubility increses due to complex formation &
hydrolysis of anion(cation/anion)
GLOSSARY
Amphoteric substance. A molecule which can act both as an acid and as a base.
Autoprotolysis constant. The equilibrium constant for the reaction in which one solvent molecule loses a
proton to another, as 2H2O H3O+ + OH–.
Amphiprotic solvent. A solvent which possesses both acidic and basic properties.
Aprotic solvent. A solvent which is neither appreciably acidic or basic.
Bronsted acid. A substance which furnishes a proton.
Bronsted base. A substance which accepts a proton.
Buffer capacity. A measure of the effectiveness of a buffer in resisting changes in pH; the capacity is
greater the concentrations of the conjugate acid-base pair.
Buffer solution. A solution which contains a conjugated acid-base pair. Such a solution resists large changes
in pH when H3O+ or OH– ions are added and when the solution is diluted.
Charge-balance equation. The equation expressing the electroneutrality principle; i.e., the total
concentration of positive charge must equal the total concentration of negative charge.
Common-ion effect. The effect produced by an ion, say from a salt, which is the same ion produced by the
dissociation of a weak electrolyte. The "common" ion shifts the dissociation equilibrium in accordance with
LeChatelier's principle.
Central metal atom. A cation which accepts electrons from a ligand to form a complex ion.
Conjugate acid-base pair. An acid-base pair which differ only by a proton, as HCl and Cl–.
Diprotic acid. An acid which furnishes two protons.
Electrolyte. A compound which produces positive and negative ions in solution. Strong electrolytes are
completely dissociated, whereas weak electrolytes are only partially dissociated.
Hydrolysis. An acid-base reaction of a cation or anion with water.
Isoelectric point. The pH at which there is an exact balance of positive and negative charge on an amino
acid.
Indicator. A visual acid-base indicator is a weak organic acid or base which shows different colors in the
molecular and ionic forms.
Ligand. An anion or neutral molecule which forms a complex ion with a cation by donating one or more pairs
of electrons.
Nonelectrolyte. A substance which does not dissociate into ions in solution.
pH. The negative logarithm of the hydrogen ion concentration.
pK. The negative logarithm of an equilibrium constant.
Polyprotic acid. An acid which furnishes two or more protons.
Range of an indicator. That portion of the pH scale over which an indicator changes color, roughly the pK
of the indicator ± 1 unit.
Salt. The product other than water which is formed when an acid reacts with a base; usually an ion solid.
Simultaneous equilibria. Equilibria established in the same solution in which one molecule or ions is a
participant in more than one of the equilibria.
Solubility product constant, Ksp. The constant for the equilibrium established between a slightly soluble
salt and its ions in solution.
Stability constant. The equilibrium constant for a reaction in which a complex is formed. Also called a
formation constant.
THE ATLAS
* Water as amphiprotic solvent. + – * Concepts of acids and bases

* Autoionization of water K = [H3 O ][OH].
w
(A) Arrhenius concept
* K aH O  = Kw/[H2O]
2
(B) Bronsted lowery concept
(C) Lewis concept
pH = – log[H+ ] Arrhenius theory of electrolytes.
* Change in pH of neutral HO with temperature. * Ostwald's dilution law for weak electrolytes.
* 2
Related to
*
include
Cojugate base
Weak acid 
EXERCISE I
IONIZATION CONSTANTS AND pH OF SOLUTION
1. The value of Kw at the physiological temperature (37°C) is 2.56 × 10–14. What is the pH at the neutral point of
water at this temperature, where there are equal number of H+ and OH?
2. Calculate change in concentration of H+ ion in one litre of water, when temperature changes from 298 K to
310 K. Given Kw(298) = 10–14 Kw (310) = 2.56 × 10–14.
3. Calculate the number of H+ present in one ml of solution whose pH is 13.
4. pH of a dilute solution of HCl is 6.95. Calculate molarity of HCl solution. (take 100.05 = 1.121 and 100.95 = 8.9)
5. Calculate pH of following solutions :
(a) 0.1 M HCl (b) 10–8 M HCl (c) 10–10 M NaOH
(d) Decimolar solution of Baryta (Ba(OH)2), diluted 100 times.
(e) 10–3 mole of KOH dissolved in 100 L of water.
6. Calculate (i) Ka for H2O (Kw = 10–14) (ii) Kb for B(OH)4– , Ka (B(OH)3) = 6 × 10–10
(iii) Ka for HCN , Kb (CN–) = 2.5 × 10–5
7. Calculate :
(a) Ka for a monobasic acid whose 0.10 M solution has pH of 4.50.
(b) Kb for a monoacidic base whose 0.10 M solution has a pH of 10.50.
1
8. Calculate the ratio of degree of dissociation (21) when 1 M acetic acid solution is diluted to times.
100
[Given Ka=1.8 × 10–5]
9. Calculate the ratio of degree of dissociation of acetic acid and hydrocyanic acid (HCN) in 1 M their respective
solution of acids.[Given K a(CH COOH)  1.8  10 5 ; K a(HCN)  6  10 10 ]
3

(a) 0.1 M CH3COOH (Ka= 1.8 × 10–5) (b) 0.1 M NH4OH (Kb= 1.8 × 10–5)
(c) 10–6 M CH3COOH (d) 10–8 M CH3COOH
11. The pH of aqueous solution of ammonia is 11.5. Find molarity of solution. Kb (NH4OH) = 2 × 10–5 ( << 1).
12. The solution of weak monoprotic acid which is 0.01 M has pH = 3. Calculate Ka of weak acid.
13. In a solution of 10–2 M BOH (Kb = 10–4). The concentration of B+ is repersent as 9.5 × 10–x .
Calculate the value of x.
MIXTURE OF ACIDS & BASES

(a) 0.1 M H2SO4 (50 ml) + 0.4 M HCl 50 (ml)
(b) 0.5 M HCl (25 ml) + 0.5 M NaOH (10 ml) + 40 ml H2O
(c) Equal volume of HCl solution (pH = 4) + 0.0019 M HCl solution
15. Calculate [H+] and [CHCl2COO] in a solution that is 0.01 M in HCl and 0.01 M in CHCl2COOH.
Take (Ka = 1.5 × 10–2).

16. Calculate [H+], [CH3COO–] and [ C7 H5O2–] in a solution that is 0.02 M in acetic acid and 0.01M in benzoic
acid. Ka(acetic) = 1.8 × 10–5 , Ka (benzoic) = 6.4 × 10–5.
17. Calculate pH of resultant solution of 0.1 M HA + 0.1 M HB
[Ka (HA) = 4 × 10–5 ; Ka (HB) = 5 × 10–5]
POLYPROTIC ACIDS & BASES
18. Determine the [S2] in a saturated (0.1M) H2S solution to which enough HCl has been added to produce a
[H+] of 2 × 104 . K1 = 107 , K2 = 1014.
19. Calculate [H+], [H2PO4 ], [HPO42] and [PO43] in a 0.01M solution of H3PO4.
Take K1 = 5 × 103, K2 = 6.8 × 108 , K3 = 4.5 × 1013.
20. H3A is a weak triprotic acid ( K a1 = 10–5 , K a2 = 10–8, K a3 = 10–111)

If concentration of A3– present in 0.1 M H3A (aq) solution is represented as 10–X , then find the value of X.
21. What are the concentrations of H+, HSO 4 , SO 24 and H2SO4 in a 0.20 M solution of sulphuric acid ?
(Take 521  22.8 )
Given : H2SO4  H+ + HSO 4 ; strong
HSO 4 H+ + SO 24 ; K2 = 10–2 M
22. What are the concentration of H+, H2C2O4, HC 2O 4 and C 2 O 24 in a 0.1 M solution of oxalic acid ?
[K1 = 5 ×10–2 M and K2 = 6.4 × 10–5 M]
23. Nicotine, C10H14N2, has two basic nitrogen atoms and both can react with water to give a basic solution
Nic (aq) + H2O (l) NicH+ (aq) + OH– (aq)
+
NicH (aq) + H2O (l) NicH22+ (aq) + OH– (aq)
Kb1 is 7 × 10–7 and Kb2 is 1.1 × 10–10. Calculate the approximate pH of a 0.020 M solution.
24. Ethylenediamine, H2N–C2H4–NH2, can interact with water in two steps, giving OH– in each step. Calculate
the concentration of OH– and [H3N–C2H4–NH3]2+ in a 0.25 M aqueous solution of the amine.
K1 = 4.9 × 10–5, K2 = 2.7 × 10–8 for the base.
HYDROLYSIS
25. What is the OH concentration of a 0.8 M solution of CH3COONa. [Ka(CH3COOH)=2 × 105]
26. Calculate the pH of a 2.0 M solution of NH4Cl. [Kb (NH3) = 1.8 × 105]
27. 0.25 M solution of pyridinium chloride C5H6N+Cl was found to have a pH of 2.7. What is Kb for pyridine,
C5H5N ? (100.8 = 6.3)
28. Calculate the extent of hydrolysis & the pH of 0.02 M CH3COONH4.
[Kb (NH3)= 1.8 × 105, Ka(CH3COOH)=1.8 × 105]
29. Calculate the percent hydrolysis in a 0.06 M solution of KCN. [Ka(HCN) = 6 × 1010]
30. Calculate the extent of hydrolysis of 0.004 M K2CrO4. [K2 = 4 × 107 for H2CrO4]
(It is essentially strong for first ionization).
31. Calculate the percent hydrolysis in a 0.1 M solution of KCN.(Ka= 6.4 ×10–10)
32. A 0.010 M solution of PuO2(NO3)2 was found to have a pH of 4.0. What is the hydrolysis constant, Kh, for
PuO 22  ,and what is Kb for PuO2OH+ ?
33. Calculate the pH of 1.0 ×10–3 M sodium phenolate, NaOC6H5. Ka for HOC6H5 is 10–10. ( 41  6.4 )
34. What is the pH of 0.1M NaHCO3? K1 = 4 × 107, K2 = 4 × 1011 for carbonic acids.
35. Calculate pH of 0.05M potassium hydrogen phthalate, KHC8H4O4.
H2C8H4O4 + H2O H3O+ + HC8H4O4 pK1 = 2.94
HC8H4O4 + H2O H3O+ + C 8H4O24 pK2 = 5.44
36. The acid ionization (hydrolysis) constant of Zn2+
is 1.0 × 10–9
(a) Calculate the pH of a 0.001 M solution of ZnCl2
(b) What is the basic dissociation constant of Zn(OH)+ ?
BUFFER SOLUTION
37. Determine [OH–] of a 0.050 M solution of ammonia to which has been added sufficient NH4Cl to make the
total [ NH 4 ] equal to 0.100.[ K b(NH ) = 1.8 × 10–5]
3
38. Calculate the pH of a solution prepared by mixing 50.0 mL of 0.200 M HC2H3O2 and 50.0 mL of 0.100 M
NaOH.[ K a(CH3COOH) = 1.8 × 10–5]
39. 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.
40. 50 mL of 0.1 M NaOH is added to 75 mL of 0.1 M NH4Cl to make a basic buffer. If pKa of NH 4 is 9.26,
calculate pH.
41. (a) Determine the pH of a 0.2 M solution of pyridine C5H5N . Kb = 1.5 × 109
(b) Predict the effect of addition of pyridinium ion C5H5NH+ on the position of the equilibrium. Will the pH be
raised or lowered ?
(c) Calculate the pH of 1.0 L of 0.10 M pyridine solution to which 0.3 mol of pyridinium chloride C5H5NH+Cl,
has been added, assuming no change in volume.
42. Calculate the pH of a solution which results from the mixing of 50.0 ml of 0.3 M HCl with 50.0 ml of
0.4 M NH3 . [Kb (NH3) = 1.8 × 105]
43. Calculate the pH of a solution made by mixing 50.0 ml of 0.2M NH4Cl & 75.0 ml of 0.1 M NaOH.
[Kb (NH3 ) = 1.8 × 10 5]
44. A buffer solution was prepared by dissolving 0.02 mol propionic acid & 0.015 mol sodium propionate in
 16 
enough water to make 1.00 L of solution .(Ka for propionic acid is 1.5 × 105)  log  0.07 
 19 
(a) What is the pH of the buffer?
(b) What would be the pH if 1.0 × 105 mol HCl were added per 10 ml of the buffer ?
(c) What would be the pH if 1.0 × 105 mol NaOH were added per 10 ml of the buffer.
45. A solution was made up to be 0.01 M in chloroacetic acid, ClCH2COOH and also 0.002 M in sodium
chloroacetate ClCH2COONa . What is [H+] in the solution ? Ka = 1.5 × 103.
INDICATORS
46. For the indicator thymol blue, pH is 2.0 when half the indicator is in unionised form. Find the % of indicator
in unionised form in the solution with [H+] = 4 × 103 M.
47. At what pH does an indicator change colour if the indicator is a weak acid with Kind = 4 × 104. For which
one(s) of the following neutralizations would the indicator be useful ? Explain.
(a) NaOH + CH3COOH (b) HCl + NH3 (c) HCl + NaOH
48. What indicator should be used for the titration of 0.10 M KH2BO3 with 0.10 M HCl ?
Ka (H3BO3) = 7 × 1010 .
49. Bromophenol blue is an indicator with a Ka value of 6 × 105 . What % of this indicator is in its basic form at
a pH of 5 ?
50. An acid base indicator has a Ka of 3 × 105. The acid form of the indicator is red & the basic form
is blue. By how much must the pH change in order to change the indicator form 75% red to 75 % blue ?
ACID BASE REACTIONS & TITRATIONS

51. Calculate the hydronium ion concentration and pH at the equivalence point in the reaction of 22.0 mL of
0.10M acetic acid, CH3COOH(pKa = 4.74) with 22.0 mL of 0.10 M NaOH.
52. Calculate the hydronium ion concentration and the pH at the equivalence point in a titration of 50.0 mL of
0.40 M NH3 (pKb=4.74) with 0.40M HCl.
53. Calculate OH– concentration at the equivalent point when a solution of 0.1 M acetic acid is titrated with a
solution of 0.1 M NaOH. Ka for the acid = 2 × 10–5.
54. In the titration of a solution of a weak acid HX with NaOH, the pH is 5.8 after 10.0 mL of NaOH solution has
been added and 6.4 after 20.0 mL of NaOH has been added. What is the value of pKa(HX)?
55. The equivalent point in a titration of 40.0 mL of a solution of a weak monoprotic acid occurs when
35.0 mL of a 0.10M NaOH solution has been added. The pH of the solution is 5.82 after the addition of
20.0 mL of NaOH solution. What is the dissociation constant of the acid?
56. A weak base (50.0mL) was titrated with 0.1 M HCl. The pH of the solution after the addition of
10.0 mL and 25.0 mL were found to be 9.84 and 9.24, respectively. Calculate Kb of the base and pH at the
equivalence point.
57. A weak acid (50.0mL) was titrated with 0.1 M NaOH. The pH values when 10.0 mL and 25.0 mL of base have been
added are found to be 4.16 and 4.76, respectively. Calculate Ka of the acid and pH at the equivalence point.
58. CH3COOH (50 ml, 0.1 M) is titrated against 0.1 M NaOH solution. Calculate the pH at the addition of 0 ml,
10 ml 20 ml, 25 ml, 40 ml, 50 ml of NaOH. Ka of CH3COOH is 2 × 10–5.
SOLUBILITY & SOLUBILITY PRODUCTS
59. The values of Ksp for the slightly soluble salts MX and QX2 are each equal to 4.0 × 10–18. Which salt is more
soluble? Explain your answer fully.
60. The solubility of PbSO4 water is 0.0303 g/L. Calculate the solubility product constant of PbSO4.
61. Calculate the solubility of Mg(OH)2 in water. Ksp= 3.2 × 10–11.
62. How many mol CuI (Ksp = 5 × 10–12) will dissolve in 1.0 L of 0.10 M NaI solution ?
63. A solution of saturated CaF2 is found to contain 4 × 10–4 M fluoride ion. Calculate the Ksp of CaF2. Neglect
hydrolysis.
64. The solubility of ML2 (formula weight, 60 g/mol) in water is 2.4 × 10–5 g/100 mL solution. Calculate the
solubility product constant for ML2.
65. What is the solubility (in mol/L) of Fe(OH)3 in a solution of pH = 8.0 ? [Ksp for Fe(OH)3 = 1.0 × 10–36]
66. Calculate the solubility of A2X3 in pure water, assuming that neither kind of ion reacts with water. For A2X3,
[Ksp = 1.08 × 10–23]
67. Determine the solubility of AgCl in 0.1 M BaCl2. [Ksp for AgCl = 1 × 10–10]
68. A solution has a Mg2+ concentration of 0.0010 mol/L. Will Mg(OH)2 precipitate if the OH– concentration of the
solution is [Ksp= 1.2 × 10–11]
(a) 10–5 mol/L (b) 10–3 mol/L ?
69. Calculate solubility of PbI2 (Ksp = 2.916 × 10–9) in water at 25°, which is 90% dissociated.
70. Calculate solubility of AgCN (Ksp= 4×10–16) in a buffer solution of PH =3. [Ka(HCN) = 4×10–10 and 10 =3.16]
SIMULTANEOUS SOLUBILITY
71. Calculate the Simultaneous solubility of AgSCN and AgBr.
Ksp (AgSCN) = 1.17 × 10–12, Ksp(AgBr) = 5.2 × 10–13.
72. Calculate F– in a solution saturated with respect of both MgF2 and SrF2. [(3.375)1/3 =1.5]
Ksp(MgF2)= 9.5 × 10 –9, Ksp(SrF2) = 4 × 10–9.
COMPLEXATION EQUILIBRIA
73. Assuming no change in volume, calculate the minimum mass of NaCl necessary to dissolve 0.010 mol AgCl
in 100 L solution. [Kf(AgCl2–) = 3 ×105, Ksp = (AgCl) = 1 ×10–10]
74. A recent investigation of the complexation of SCN– with Fe3+ represented by constant K1, K2 and K3 as 130,
16, and 1.0 respectively. What is the overall formation constant of Fe(SCN)3 from its component ions, and
what is the dissociation constant of Fe(SCN)3 into its simplest ions on the basis of these data?
75. How much AgBr could dissolve in 1.0 L of 0.40 M NH3 ? Assume that Ag(NH3)2+ is the only complex formed.
[Kf ( Ag(NH3 )2 ) = 1 ×108 ; Ksp (AgBr) = 10–14]
EXERCISE II
–
1. Degree of ionization of 0.001 M HA (aq) is 0.20. Calculate the value of pK b ( A ) at 50ºC ?
(Given : Kw at 50ºC = 5 × 10–14)
2. A solution contains HCl, Cl2HCCOOH & CH3 COOH at concentrations 0.09 M in HCl, 0.09 M in
Cl2HCCOOH & 0.1 M in CH3COOH. pH for the solution is 1. Ionization constant of CH3COOH = 105.
What is the magnitude of Ka for dichloroacetic acid ?
3. A solution of chloroacetic acid, ClCH2COOH containing 9.45 grams in 500 ml of the solution has a pH of 2.0.
What is the degree of ionization of the acid?
4. The Kw of water at two different temperatures is :
T 25°C 50°C
Kw 1.08 × 10 14 5.4 × 1014
Assuming that H of any reaction is independent of temperature, calculate the enthalpy of neutralization of
25
a strong acid and strong base. (ln 5 = 1.8 and R = J/mol K)
3
5. What is the pH of a 1.0 M solution of acetic acid ? To what volume must 1 litre of the solution be diluted so
that the pH of the resulting solution will be twice the original value. Given Ka = 2 × 10–5.
6. An aqueous solution contains 0.01 M RNH2 (Kb = 10–6) and 10–3 M KOH. If concentration of RNH3+ is
represented as 10–z then what is the value of z?
7. It is desired to prepare 100 ml of a buffer of pH 5.00.Acetic, benzoic and formic acids and their salts are
available for use. Which acid should be used for maximum effectiveness against increase in pH? What acid-
salt ratio should be used? pKa values of these acids are : acetic 4.74; benzoic 4.18 and formic 3.68.
8. When a 40 mL of a 0.1 M weak base is titrated with 0.16M HCl, the pH of the solution at the end point is 5.23.
What will be the pH if 15 mL of 0.1 M NaOH is added to the resulting solution. (log 16.25 = 1.21)
9. A buffer solution was prepared by dissolving 0.05 mol formic acid & 0.06 mol sodium formate in enough water
to make 1.0 L of solution. Ka for formic acid is 1.80 × 104.
(a) Calculate the pH of the solution .
(b) If this solution were diluted to 10 times its volume, what would be the pH ?
10. How many moles of sodium hydroxide can be added to 1.00 L of a solution 0.1 M in NH3 & 0.1 M in NH4Cl without
changing the pOH by more than 1.00 unit ? Assume no change in volume. Kb(NH3) = 1.8 × 105.
11. Calculate the OH– concentration and the H3A concentration of a solution prepared by dissolving 0.1 mol of
Na3A in sufficient water to make 1L of solution. K1 = 104 , K2 = 107 , K3= 1011.
12. Equilibrium constant for the acid ionization of Fe3+ to Fe(OH)+2 and H+ is 6.5 ×10–3. What is the max.pH,
which could be used so that at least 95% of the total Fe3+ in a dilute solution. exists as Fe3+. (log1235=3.1)
13. The indicator phenol red is half in the ionic form when pH is 7.2. If the ratio of the undissociated form to the
ionic form is 1 : 5, find the pH of the solution. With the same pH for solution, if indicator is altered such that
the ratio of undissociated form to dissociated form becomes 1 : 4, find the pH when 50 % of the new indicator
is in ionic form.
14. A solution of weak acid HA was titrated with base NaOH. The equivalence / nutralisation point was reached
when 36.12 ml of 0.1 M NaOH has been added. Now 18.06 ml of 0.1 M HCl were added to titrated solution,
the pH was found to be 4.92. What will be the pH of the solution obtained by mixing 10 ml of 0.2 M NaOH and
10 ml of 0.2 M HA.
15. A weak base BOH was titrated against a strong acid . The pH at 1/4th nutralisation point was 9.24.
Enough strong base was now added (6m.mol) to completely convert the salt. The total volume was 50ml.
Find the pH at this point.
16. Calculate the pH of the following mixtures of soutions at 25ºC.
(Given : Ka1 (H3A) = 10–4, Ka2(H3A) = 10–7, Ka3(H3A) = 10–11)
(a) 50 ml of 0.12 M H3A + 20 ml of 0.15 M NaOH;
(b) 50 ml of 0.12 M H3A + 40 ml of 0.15 M NaOH;
(c) 40 ml of 0.12 M H3A + 40 ml of 0.18 M NaOH;
(d) 40 ml of 0.10 M H3A + 40 ml of 0.25 M NaOH.
17. Calculate the pH of the following mixtures of solution at 25ºC. (Use data of Q.10)
(a) 40 ml of 0.050 M Na2B + 50 ml of 0.040 M HCl;
(b) 40 ml of 0.020 M Na3A + 40 ml of 0.040 M HCl;
(c) 50 ml of 0.10 M Na3A + 50 ml of 0.10 M NaH2A;
(d) 40 ml of 0.10 M H3A + 40 ml of 0.10 M Na3A.
18. Calculate the pH of 0.1 M solution of (i) NaHB, (ii) Na2HA and (iii) NaH2A. Given that:
H2B H+ + HB– ; K1 = 10–6 M
HB– H+ + B2– ; K2 = 10–10 M
H3A H+ + H2A– ; K1 = 10–4 M
H2A– H+ + HA2– ; K2 = 10–7 M
HA2– H+ + A3– ; K3 = 10–11 M
19. At 25°C, will a precipitate of Mg(OH)2 form in a 10–4 M solution of Mg(NO3)2 if pH of the solution is adjusted
to 9.0. Ksp [Mg(OH)2] = 10–11 M3. At what min value of pH will precipitation start.
20. What is the solubility of AgCl in 0.20 M NH3?

Given : Ksp(AgCl) = 3 × 10–10 M2, K1 = [Ag(NH3)+] / [Ag+][NH3] = 2 × 103 M–1 and
K2 = [ Ag(NH3 )2 ] / [Ag(NH3)+] [NH3] = 6 × 103 M–1.
21. A solution is 0.1 M in Cl– and 0.001 M in CrO2–

4 . If solid AgNO3 is gradually added to this solution, which will
precipitate first, AgCl or Ag2CrO4? Assume that the addition causes no change in volume.
Given: Ksp(AgCl) = 1.7 × 10–10 M2 and Ksp(Ag2CrO4) = 1.9 × 10–12 M3
22. H2S is bubbled into a 0.2 M NaCN solution which is 0.02 M in each AgCN
2
and Cd(CN) 24 – . Determine
which sulphide precipitates first.

Given : Ksp(Ag2S) = 1.0 × 10–50 M3 ; Ksp(CdS) = 7 × 10–28 M2
 
K inst Ag CN2 = 1.0 × 10–20 M2 ; K inst  CdCN24   = 8 × 10–18 M4
 
23. Silver ion forms a complex with thisulphate ion with their formula [Ag(S2O3)2]3–. Kf for this complex is
2 × 1013. How many grams of AgBr (Ksp = 5 × 10–13) will dissolve in 125 mL of a 1.20 M Na2S2O3 solution.
24. Equal volumes of 0.02M AgNO3 and 0.02M HCN were mixed. Calculate [Ag+] at equilibrium .
Given : Ka(HCN) = 9 × 10–10, Ksp (AgCN) = 4 × 10–16.
25. The salt Zn(OH)2 is involved in the following two equilibria,

Zn(OH)2 (s) Zn2+ (aq) + 2OH– (aq) ; Ksp = 1.2 × 10–17
Zn(OH)2 (s) + 2OH– (aq) [Zn(OH)4]2– (aq.) ; Kc = 0.13
Calculate the pH of solution at which solubility is minimum.
QUESTION BANK
1. According to Lewis concept, a reaction between an acid and a base is the transfer of
(A) A proton from acid to base (B) OH– ion from bases to acid
(C) Electron pair from acid to base (D) Electron pair from base to acid
2. The conjugate acid of NH2 is

(A) NH3 (B) NH2OH (C) NH 4 (D) N2H4
3. The strongest Bronsted base in the following anion is

(A) ClO– (B) ClO2 (C) ClO3 (D) ClO4
4. Out of the following, amphiprotic species are

(I) HPO32– (II) OH– (III) H2PO4– (IV) HCO3–
(A) I, III, IV (B) I and III (C) III and IV (D) All
5. Which one of the following statement is correct?
(A) pKw = 14 at all temperatures (B) pKw = 0 at 0ºC
(C) pKw decreases with increase temperature (D) pKw increases with increase in temperature
6. pH of an aqeous solution of NaCl at 85°C should be
(A) 7 (B) > 7 (C) < 7 (D) 0
7. 1 CC of 0.1 M HCl is added to 99 CC solution of NaCl. The pH of the resulting solution will be
(A) 7 (B) 3 (C) 4 (D) 1
8. The pH of the solution containing 10 ml of 0.1 M NaOH and 10 ml of 0.05 M H2SO4 would be
(A) 0 (B) 1 (C) > 7 (D) 7
M M
9. 10 ml of H SO is mixed with 40 ml of H SO . The pH of the resulting solution is
200 2 4 200 2 4
(A) 1 (B) 2 (C) 2.3 (D) none of these
10. If pKb for fluoride ion at 25° C is 10.83, the ionisation constant of hydrofluoric acid in water at this temperature
is :
(A) 1.74 × 105 (B) 3.52 × 103 (C) 6.75 × 104 (D) 5.38 × 102
11. The pH of an aqueous solution of 1.0 M solution of a weak monoprotic acid which is 1% ionised is
(A) 1 (B) 2 (C) 3 (D) 11
12. Pure water is kept in a vessel and it remains exposed to atmospheric CO2 which is absorbed, then its pH at 25ºC
will be
(A) Greater than 7 (B) Less than 7
(C) 7 (D) Depends on ionic product of water
13. Which of the following solution will have pH close to 1.0?

(A) 100 ml of M/100 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
14. If K1 & K2 be first and second ionisation constant of H3PO4 and K1 >> K2 which is incorrect.
(A) [H+] = [ H2PO 4 ] (B) [H+] = K1[H3PO 4 ] (C) K2 = [HPO 4  ] (D) [H+] = 3[PO 34 ]
15. The aqueous solution of FeCl3 is acidic due to

(A) Acidic impurities (B) Ionisation (C) Hydrolysis (D) Dissociation
16. The compound whose 0.1 M solution is basic is
(A) Ammonium acetate (B) Ammonium chloride
(C) Sodium chloride (D) Sodium acetate
17. An aqueous solution of CuSO4.5H2O turns blue litmus red. it is due to the
(A) Presence of Cu2+ ions (B) Presence of SO42– ions
(C) Hydrolysis of Cu2+ ions (D) Hydrolysis of SO42– ions
18. The degree of hydrolysis of a salt of weak acid and weak base in it’s 0.1 M solution is found to be 50%. If the
molarity of the solution is 0.2 M, the percentage hydrolysis of the salt should be
(A) 100% (B) 50% (C) 25% (D) none of these
19. What is the percentage hydrolysis of NaCN in N/80 solution when the dissociation constant for HCN is
1.3 × 10–9 and Kw = 1.0 × 10–14
(A) 2.48 (B) 5.26 (C) 8.2 (D) 9.6
20. The  pH of the neutralisation point of 0.1 N ammonium hydroxide with 0.1 N HCl is
(A) 1 (B) 6 (C) 7 (D) 9
21. What will be percentage degree of hydrolysis (% ) for the salt BA of 0.01 M concentration at 335 K?
[Given at 335 K; Ka (HA) = 10–7; Kb (BOH) = 10–7; Kw = 10–13]
1 3.16
(A) 3.16 (B) 31.6 (C)  100 (D)  100
4.16 4.16
22. If equilibrium constant of

CH3COOH + H2O CH3COO– + H3O+
Is 1.8 × 10–5, equilibrium constant for
CH3COOH + OH– CH3COO– + H2O is
(A) 1.8 ×10–9 (B) 1.8 × 109 (C) 5.55 × 10–9 (D) 5.55 × 1010
23. In a solution of acetic acid, sodium acetate is added, then its pH value
(A) Decreases (B) Increases
(C) Remains unchanged (D) (a) and (b) both are correct
24. A certain buffer solution contains equal concentration of X– and HX. The Kb for X– is 10–10. The pH of the buffer is
(A) 4 (B) 7 (C) 10 (D) 14
salt .
25. Henderson’s equation is pH = pKa + log
acid If the acid [pKa = 5] gets half neutralized the value of pH will be
(A) 5 (B) 5.3 (C) 4.7 (D) 7
26. A buffer solution with pH 9 is to be prepared by mixing NH4Cl and NH4OH. Calculate the number of moles of
NH4Cl that should be added to one litre of 1.0 M NH4OH. [Kb = 1.8 × 10–5]
(A) 3.4 (B) 2.6 (C) 1.5 (D) 1.8
27. 100 mL of 0.02 M benzoic acid (pka = 4.20) 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
28. What is the difference in pH for 1/3 and 2/3 stages of neutralisation of 0.1 M HCOOH with 0.1 M NaOH.
(A) – 2 log 3 (B) 2 log (1/4) (C) 2 log (2/3) (D) – 2 log 2
29. If 40 ml of 0.2 M KOH is added to 160 ml of 0.1 M HCOOH [Ka = 2×10–4], the pOH of the resulting solution is
(A) 3.4 (B) 3.7 (C) 7 (D) 10.3
30. What volume of 0.2 M NH4Cl solution should be added to 100 ml of 0.1 M NH4OH solution to produce a buffer
solution of pH = 8.7?
Given : pKb of NH4OH = 4.7 ; log 2 = 0.3
(A) 50 ml (B) 100 ml (C) 200 ml (D) none of these
31. An aqueous solution contains 0.01 M RNH2 (Kb = 2 × 10–6) & 10–4 M NaOH. The concentration of OH– is
nearly
(A) 2.414 × 10–4 (B) 10–4 M (C) 1.414 × 10–4 (D) 2 × 10–4
32. 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
(A) 8.58 (B) 4.79 (C) 7.01 (D) 9.22
33. How many gm of solid NaOH must be added to 100 ml of a buffer solution which is 0.1 M each w.r.t. Acid HA
and salt Na+ A– to make the pH of solution 5.5. Given pka (HA) = 5.
(A) 0.208 (B) 3.05 × 10–3 (C) 2.01 × 10–2 (D) None of these
34. What fraction of an indicator HIn is in the 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
35. An acid-base indicator which is a weak acid has a pKa value = 5.45. At what concentration 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]
(A) 4 : 1 (B) 6 : 1 (C) 5 : 1 (D) 3 : 1
36. The range of most suitable indicator which should be used for titration of X– Na+ (0.1 M, 10 ml ) with 0.1 M
HCl should be (Given: k b ( X  ) =10–6)
(A) 2 – 3 (B) 3 – 5 (C) 6 – 8 (D) 8 – 10
37. If Ksp for HgSO4 is 6.4 ×10–5, then solubility of this substance in mole per m3 is
(A) 8 ×10–3 (B) 6.4 ×10–5 (C) 8 × 10–6 (D) None of these
38. Ksp of AX4 and solubility of AX4 is S mol/litre is related by

(A) S = [Ksp/256]1/5 (B) S = [128 Ksp]1/4 (C) S = [Ksp]1/5 (D) S = [Ksp/128]1/4
39. The solubility of A2X3 is y mol dm–3. Its solubility product is

(A) 6 y2 (B) 64 y4 (C) 36 y5 (D) 108 y5
40. If the solubility of lithium sodium hexafluoride aluminate, Li3Na3 (AlF6)2 is ‘S’ mol L–1. Its solubility product is
equal to
(A) 729 S8 (B) 12 S8 (C) 18 S8 (D) 2916 S8
41. Which of the following is most soluble in water?
(A) MnS (Ksp= 8×10–37) (B) ZnS (Ksp= 7×10–16)
(C) Bi2S3 (Ksp= 1×10–72) (D) Ag3(PO4) (Ksp= 1.8×10–18)
42. The precipitate of CaF2(Ksp = 1.7 × 10–10) is obtained when equal volumes of the following are mixed
(A) 10–4 M Ca3+ + 10–4 M F– (B) 10–2 M Ca2+ + 10–3 M F–
(C) 10–5 M Ca2+ + 10–3 M F– (D) 10–3 M Ca2+ + 10–5 M F–
43. Solid Ba(NO3)2 is gradually dissolved in a 1.0 × 10–4 M Na2 CO3 solution. At what concentration of Ba2+ will
a precipitate begin to form? (Ksp for BaCO3 = 5.1 × 10–9)
(A) 4.1 × 10–5 M (B) 5.1 × 10–5 M (C) 8.1 × 10–8 M (D) 8.1 × 10–7 M
44. Let the solubilities of AgCl in pure water, 0.01 M CaCl2, 0.01 M NaCl & 0.04 M AgNO3 be S1, S2 & S4
respectively what is the correct order :
(A) S1 > S2 > S3 > S4 (B) S1 > S2 = S3 > S4 (C) S1 > S3 > S2 > S4 (D) S4 < S2 > S3 > S1
45. The solubility of Fe(OH)3 would be minimum in
(A) 0.1 M NaOH (B) 0.1 M HCl (C) 0.05 M KOH (D) 0.1 M H2SO4.
46. Arrange in increasing order of solubility of AgBr in solutions given
(i) 0.1 M NH3 (ii) 0.1 M AgNO3 (iii) 0.2 M KBr (iv) Pure water
(A) (iii) < (ii) < (iv) < (i) (B) (iii) < (ii) < (i) < (iv)
(C) (iii) < (ii) = (i) < (iv) (D) (ii) < (iii) < (iv) < (i)
47. What is the minimum pH when Fe(OH)3 starts precipitating from a solution containing 0.1 M FeCl3?
Ksp of Fe(OH)3 = 8 × 10–13 M3
(A) 3.7 (B) 5.7 (C) 10.3 (D) 8.3
48. The solubility product of Mg(OH)2 is 1.2 × 10–11. The solubility of this compound in gram per 100 cm3 of
solution is
(A) 1.4 × 10–4 (B) 8.16 × 10–4 (C) 0.816 (D) 1.4
49. 50 litre of a solution containing 10–5 mole of Ag+ is mixed with 50 litre of a 2 × 10–7 M HBr solution. [Ag+] in
resultant solution is : [Given : Ksp (AgBr) = 5 × 10–13]
(A) 10–5 M (B) 10–6 M (C) 10–7 M (D) None of these
50. The solubilities of AgCl and AgBr in water are 10–5 and 10–6 mol/L. if an equimolar mixture of AgCl and AgBr,
are added into water then what is the ratio of [Br–]/[Cl–] in resultant solution.
(A) 100 : 1 (B) 1 : 100 (C) 1 : 99 (D) 99 : 1
51. When pure water is saturated with CaCO3 and CaC2O4, the concentration of calcium ion in the solution under
equilibrium is 8.43 × 10–5M. If the ratio of the solubility product of CaCO3 to that of CaC2O4 is 2, what is the
solubility product of CaCO3 in pure water?
(A) 4.80 × 10–8 (B) 9.60 × 10–9 (C) 9.60 × 10–8 (D) 4.73 × 10–9
52. pH of a saturated solution of silver salt of monobasic acid HA is found to be 9. Find the Ksp of sparingly
soluble salt Ag A(s). Given : Ka (HA) = 10–10
(A) 1.1 × 10–11 (B) 1.1 × 10–10 (C) 10–12 (D) None of these
Assertion & Reasoning Type Questions
53. Statement-1 pH of 10–7 M NaOH solution is exist between 7 to 7.3 at 25ºC.

Statement-2 Due to common ion effect ionization of water is reduced.
(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 NOTcorrect explanation for Statement-1
(C) Statement-1 is true, Statement-2 is false
(D) Statement-1 is false, Statement-2 is true
54. Statement-1 In general phenolphthalein is used as an indicator for the titration of weak acid (HA) against
strong base (NaOH).
Statement-2 At equivalent point solution is basic.

55. Statement-1 Moles of Sr2+ furnished by sparingly soluble substance Sr(OH)2 decreases due to dilution.
Statement-2 Solubility product constant of Sr(OH)2 is not affected by dilution.
(C) Statement-1 is true, Statement-2 is false (D) Statement-1 is false, Statement-2 is true
56. Statement-1 A substance that can either act as an acid or a base is called amphoteric.
Statement-2 HC2O4– and HCO3– are amphoteric.
(C) Statement-1 is true, Statement-2 is false (D) Statement-1 is false, Statement-2 is true
57. Statement-1 A mixture of the solutions of a weak acid and its conjugate base acts as a good buffer.
Statement-2 The pH of buffer solution does not change substantially when small amount of acid or alkaly
is added to the buffer.
More than one may be correct
58. Which of the following statement(s) are ture :

(A) ClO4 is weaker base than ClO3
(B) HPO 4 is a conjugate acid of H2PO 4

(C) The degree of dissociation of water is 1.8 × 10–9
(D) The equilibrium constant for dissociation of H2O is 1.8 × 10–16 at 25ºC
59. 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 a weak monoprotic acid is titrated again a strong base, at half-neutralization point
pH = (1/2) pKa
60. Which of the following is/are true for acidic aqueous solution?
pk w pk w
(A) pH  (B) pH > pOH (C) pOH  (D) pH < pOH
2 2
61. A 10 L buffer solution has 0.4 M CH3COOH and 0.4 M CH3COONa. Which of the following will not change the
pH significantly, of the solution ?
(A) Addition of large amount 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) Addition of small amount of HCl with out change in volume
62. Ka values HA, HB and HC are 10–5, 10–7 and 10–9 respectively. Which of the following will be correct for 0.1 M
aqueous solutions of NaA, NaB and NaC at 25°C?
(A) (pH)NaA < (pH)NaB (B) (pH)NaC < (pH)NaB (C) (pH)NaA < (pH)NaC (D) (pH)NaB = 7
63. Phenolphthalean can act as an indicator for the titration between
(A) NaOH and CH3COOH (B) H2C2O4 and KMnO4 (C) Ba(OH)2 and HCl (D) KOH and H2SO4
64. The pH of which salt is independent of its concentration :

(A) (CH3COO)C5H5N (B) NaH2PO4 (C) Na2HPO4 (D) Na2HPO3
65. Which of the following statement(s) is/are correct ?
(A) pH of an acidic buffer decreases if base is added
(B) pOH of a basic buffer decreases if salt is added
(C) At the saturation point the ionic product is equal to solubility product.
(D) The term solubility product is used for sparingly soluble salt.
66. A 2.5 gm impure sample containing weak monoacidic base (Mol. wt. = 45) is dissolved in 100 ml water and
th
 1
titrated with 0.5 M HCl when   of the base was neutralised the pH was found to be 9 and at equivalent
5
point pH of solution is 4.5. Given : All data at 25ºC & log 2 = 0.3.
Select correct statement(s)
(A) Kb of base is less than 10–6
(B) Concentration of salt (C) at equivalent point is 0.25 M
(C) Volume of HCl is used at equivalent point is 100 ml
(D) Weight percentage of base in given sample is 80%
67. Select incorrect statement(s)

(A) Phenolphthalein is suitable indicator for the titration of HCl (aq) with NH4OH (aq).
(B) An acid-base indicator in a buffer solution of pH = pKIn + 1 is ionized to the extent of 90.9%
(C) In the titration of a monoacidic weak base with a strong acid, the pH at the equivalent point is always
1
calculated by pH  [pKw – pKb – log C]
2
(D) When Na3PO4 (aq) is titrated with HCl (aq), the pH of solution at second equivalent point is calculated by
1
[pK a1  pK a2 ]
2
Match the Column
68. Column I Column II (At 25ºC)

10 litre of 0.015 M X(OH)2 (strong diacidic base ) 
 
  
(A)  5 litre of 0.08 M HNO  (P) pH ~ 3.7
 3 
  
 
 485 litre of 0. 01 M NaNO 3 
–9
(B) 10 ml of 0.5 M RNH3 Cl (K h  10 )  (Q) pH ~ 11
1
  
 
 40 ml of 0.125 M KOH 
 
–
(C) 100 ml of 0.8 M HCO 3 
 (R) pH ~ 7
  
 2– 
100 ml of 0.4 M CO 3 
 ( for H CO , use K  4  10 – 7 & K  4  10 –11 ) 
 2 3 a1 a2 
(D) Saturated aqueous solution of Co(OH)3 (Ksp = 2.7 × 10–43) (S) pH ~ 10
69. Match the effect of addition of 0.1 M NaOH to 50 ml of 0.1 M H2A (Ka1 = 10–5 , Ka2 = 10–9) in column I with
column II
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) Effective anionic hydrolysis
(D) 100 mL of NaOH (S) pH > 7
70. Column I Column II

(pH of resultant solution) (Exist between Colour transition
range of an indicator)
(A) 200 ml of H2SO4 solution (P) Phenol Red (6.8 to 8.4)
(Specific gravity 1.225 containing 25% H2SO4
by weight) + 800 ml of 0.525 M strong triacidic base X (OH)3
(B) 50 ml of 0.1 M HCO3– + 50 ml of 0.8 M CO32– (Q) Propyl red (4.6 to 6.4)
(H2CO3 : K a1  4  10 –7 , K a 2  2  10 –11 )
(C) 50 ml of 0.2 M HA (aq) (Ka = 10–5) (R) Phenolphthalein (8.3 to 10.1)

+ 50 ml of 0.1 M HCl (aq) + 100 ml of 0.13 M NaOH (aq)
(S) Malachite green (11.4 to 13)
EXERCISE-III
OBJECTIVE
1. A solution which is 10 –3 M each in Mn2+, Fe2+, Zn2+ and Hg2+ is treated with 10–16M sulphide ion. If Ksp, MnS,
FeS, ZnS and HgS are 10–15, 10–23, 10–20 and 10–54 respectively, which one will precipitate first ?
(A) FeS (B) MnS (C) HgS (D) ZnS
[JEE 2003]
2. HX is a weak acid (Ka = 10–5). It forms a salt NaX (0.1 M) on reacting with caustic soda. The degree of
hydrolysis of NaX is
(A) 0.01% (B) 0.0001% (C) 0.1% (D) 0.5% [JEE 2004]
3. CH3NH2 (0.1 mole, Kb = 5 × 10–4) is added to 0.08 moles of HCl and the solution is diluted to one litre,
resulting hydrogen ion concentration is
(A) 1.6 × 10–11 (B) 8 × 10–11 (C) 5 × 10–5 (D) 2 × 10–2 [JEE 2005]
2 2
4. 2.5 mL of M weak monoacidic base (Kb = 1 × 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 [JEE 2008]
(Kw = 1 × 10–14 at 25°C)
(A) 3.7 × 10–13 M (B) 3.2 × 10–7 M (C) 3.2 × 10–2 M (D) 2.7 × 10–2 M
5. 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]
(A) HNO3 and CH3COOH (B) KOH and CH3COONa
(C) HNO3 and CH3COONa (D) CH3COOH and CH3COONa
6. 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 Mains - 2013]
(A) 9.0 L (B) 0.1 L (C) 0.9 L (D) 2.0 L
7. pKa of a weak acid (HA) and pKb of a weak base (BOH) are 3.2 and 3.4, respectively. The pH of their salt
(AB) solution is [JEE Mains - 2017]
(A) 1.0 (B) 7.2 (C) 6.9 (D) 70
8. An aqueous solution contains an unknown concentration of Ba2+. When 50 mL of a 1 M solution of Na2SO4

is added, BaSO4 just begins to precipitate. The final volume is 500 mL. The solubility product of BaSO4 is
1 × 10–10. What is the original concentration of Ba2+ ? [JEE Mains- 2018]
(A) 1.0 × 10–10 M (B) 5 × 10–9 M (C) 2 × 10–9 M (D) 1.1 × 10–9 M
9. An aqueous solution contains 0.10 M H2S and 0.20 M HCl. If the equilibrium constants for the formation of
HS– from H2S is 1.0×10–7 and that of S2– from HS– ions is 1.2 × 10–13 then the concentration of S2– ions in
aqueous solution is [JEE Mains - 2018]
(A) 5 × 10–19 (B) 5 × 10–8 (C) 3 × 10–20 (D) 6 × 10–21
10. Dilution processes of different aqueous solutions, with water, are given in List-I. The effects of dilution of the
solutions on [H+] are given in List-II.
(Note : Degree of dissociation () of weak acid and weak base is << 1; degree of hydrolysis of slat << 1; [H+]
represents the concentration of H+ ions) [JEE Advance- 2018]
LIST-I LIST-II
(P) (10 mL of 0.1 M NaOH + 20 mL of (1) The value of [H+] does not change on dilution
0.1 M acetic acid) diluted to 60 mL
(Q) (20 mL of 0.1 M NaOH + 20 mL of (2) The value of [H+] changes to half of its initial
0.1 M acetic acid) diluted to 80 mL value on dilution.
(R) (20 mL of 0.1 M HCl + 20 mL of (3) The value of [H+] changes to two times of its
0.1 M ammonia solution) diluted initial value on dilution
to 80 mL
1
(S) 10 mL saturated solution of Ni(OH)2 in (4) The value of [H+] changes to times of its
2
equilibrium with excess solid Ni(OH)2 is initial value on dilution
diluted to 20 mL (solid Ni(OH)2 is still
present after dilution).
(5) The value of [H+] changes to 2 times of its
initial value on dilution.
Match each process given in List-I with one or more effect(s) in List-II. The correct option is
(A) P  4 ; Q  2 ; R  3 ; S  1 (B) P  4 ; Q  3 ; R  2 ; S  3
(C) P  1 ; Q  4 ; R  5 ; S  3 (D) P  1 ; Q  5 ; R  4 ; S  1
11. On decreasing the pH from 7 to 2, the solubility of a sparingly soluble salt (MX) of a weak acid (HX)
increased from 10–4 mol L–1 to 10–3 mol L–1. The pKa of HX is : [JEE Advanced- 2023]
(A) 3 (B) 4 (C) 5 (D) 2
SUBJECITVE
1. 500 ml of 0.2 M aqueous solution of acetic acid is mixed with 500 mL of 0.2 M HCl at 25°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]
2. Will the pH of water be same at 4°C and 25°C ? Explain. [JEE 2003]
3. 0.1 M of HA is titrated with 0.1 M NaOH, calculate the pH at end point. Given Ka(HA) = 5 × 10–6
and  << 1. [JEE 2004]
4. The dissociation constant of a substituted benzoic acid at 25ºC is 1.0 × 10–4. Calculate the pH of a
0.01 M solution of its sodium salt. [JEE 2009]
5. Amongst the following, the total number of compounds whose aqueous solution turns red litmus paper blue is
KCN K2SO4 (NH4)2C2O4 NaCl Zn(NO3)2 [JEE 2010]
FeCl3 K2CO3 NH4NO3 LiCN
6. 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 concentration of Ag+ in the solution is 1.6 × 10–x. The value of "x" is [JEE 2011]
7. The solubility of a salt of weak (AB) at pH 3 is Y × 10–3 mol L–1. The value of Y is ___________.
(Given that the value of solubility product of AB (Ksp) = 2 × 10–10 and the value of ionization constant of HB
(Ka) = 1 × 10–8) [JEE Advance- 2018]
8. An acidified solution of 0.05 M Zn2+ is saturated with 0.1 M H2S .What is the minimum molar concentration
(M) of H+ required to prevent the precipitation of ZnS ?
Use Ksp (ZnS) = 1.25 ×10–22 and overall dissociation of H2S, KNET = K1K2 1 ×10–21 [JEE Advance- 2020]
9. A solution of 0.1 M weak base (B) is titrated with 0.1 M of a strong acid (HA.)The variation of pH of the
solution with the volume of HA added is shown in figure below. What is the pKb of the base ?
The neutralization reaction is given by B + HA  BH+ + A– [JEE Advanced- 2020]
12
10
pH
0 2 4 6 8 10 12
Volume of HA (mL)
10. A solution is prepared by mixing 0.01 mol each of H2CO3, NaHCO3, Na2CO3, and NaOH in 100 mL of water.
pH of the resulting solution is _______. [JEE Advanced- 2022]
[Given : pKa1 and pKa2 of H2CO3 are 6.37 and 10.32, respectively; log 2 = 0.30]
11. Concentration of H2SO4 and Na2SO4 in a solution is 1 M and 1.8 × 10–2 M, respectively. Molar solubility of
PbSO4 in the same solution is X × 10–Y M (expressed in scientific notation). The value of Y is _________.
[Given : Solubility product of PbSO4 (Ksp) = 1.6 × 10–8. For H2SO4, Ka1 is very large and Ka2 = 1.2 × 10–2]
[JEE Advanced- 2022]
ANSWER KEY
EXERCISE I
Q.1 6.81 Q.2 0.6 ×10–7 Q.3 6.022 ×107
Q.4 2.31 × 10–8 M Q.5 (a) 1, (b) 6.97, (c) 7, (d) 11.30 (e) 9
Q.6 (i) 1.8 × 10–16, (ii) 1.66 × 10–5, (iii) 4 × 10–10 Q.7 (a) Ka = 10–8, (b) Kb = 10–6
Q.8 10 Q.9 173.2 Q.10 (a) 2.87, (b) 11.13, (c) 6.01, (d) 6.97
Q.11 0.5 M Q.12 1.11 × 10–4 Q.13 4
Q.14 (a) 0.522, (b) 1 , (c) 3 Q.15 [H+] = 1.5 × 102M, [CHCl2COO–] = 5 × 10–3M
Q.16 [H+] = 103M, [CH3COO] = 3.6 × 104M, [C7H5O2] = 6.4 × 104M Q.17 2.52
Q.18 [S2] = 2.5 × 1015
Q.19 [H+] = [H2PO4–] = 5 × 10–3, [HPO42–] = 6.8 × 10-8, [PO43–] = 6.12 × 10–18
Q.20 16.00 Q.21 0.209 M, 0.191 M, 0.009 M, 0
Q.22 0.05 M, 0.05 M, 0.05 M, 0.000064 M Q.23 10.07
Q.24 [OH–] = 3.5 × 10–3 M, [H2en]2+ = 2.7 × 10–8 M
Q.25 [OH] = 2 × 105 M Q.26 pH = 4.477 Q.27 Kb = 6.3 × 1010
Q.28 0.56%, pH = 7 Q.29 1.667% Q.30 0.25%
Q.31 1.25 % Q.32 10–6 ; 10–8 Q.33 pH = 10.43
Q.34 8.4 Q.35 4.19
Q.36 (a) 6, (b) 1 × 10–5 Q.37 [OH–] = 9.0 ×10–6 Q.38 4.74
Q.39 0.05 mol Q.40 9.56 Q.41 (a) pH = 9.239 (b) lowered (c) pH = 4.699
Q.42 8.7782 Q.43 9.7324
Q.44 (a) 4.7 (b) 4.64, (c) 4.75 Q.45 [H+]=2.5 × 103
Q.46 [HIn] = 28.57% Q.47 (b), (c)
Q.48 (methyl red), one with pH = 5.22 as midpoint of colour range
Q.49 85.71% Q.50 pH = 0.954 Q.51 8.71
Q.52 4.98 Q.53 5 ×10–6 M Q.54 6.1 Q.55 2 × 10–6
Q.56 Kb = 1.8 × 10–5, 5.27 Q.57 8.73

Q.58 (i) 2.85, (ii) 4.0969, (iii) 4.5229, (iv) 4.699, (v) 5.301, (vi) 8.699
Q.59 QX2 is more soluble Q.60 10–8 Q.61 2 ×10–4
Q.62 [Cu+] = 5 × 10–11 M Q.63 3.2 × 10–11 Q.64 2.6 ×10–16
Q.65 1.0 × 10–18 M Q.66 1.0×10–5 mol/lit Q.67 5 × 10–10 M
Q.68 (a) no precipitation will occur, (b) a precipitate will form Q.69 10–3
Q.70 3.11 × 10–5 Q.71 4 × 10–7mol/L AgBr, 9 × 10–7 mol/L AgSCN
Q.72 [F–] = 3 × 10–3M Q.73 19.5 kg Q.74 Kd = 1/Kf = 4.8 × 10–4

Q.75 4 × 10–4 M
EXERCISE II
Q.1 9 Q.2 Ka = 1.25 × 102 Q.3  = 0.05
Q.4 Hneut = –57.75 kJ mol–1 Q.5 V = 2.5 × 104 litre Q.6 5.00
Q.7 acetic acid, salt-acid molar ratio 1.8 :1 ;
Q.8 9.03 Q.9 (a) pH = 3.83 (b) pH = 3.85
Q.10 0.0818 moles Q.11 10–2, 10–15 Q.12 0.9
Q.13 pH = 7.3 Q.14 8.96 Q.15 11.22
Q.16 (a) 4 (b) 5.5 (c) 7 (d) 11 Q.17 (a) 8 (b) 5.5 (c) 9 (d) 7
Q.18 (i) 8 (ii) 9 (iii) 5.5
Q.19 No, 10.5 Q.20 0.0107
Q.21 AgCl Q.22 CdS Q.23 12.22 g
Q.24 +
[Ag ] = 6.667 × 10 M –5
Q.25 9.99, s = 10–9 M
QUESTION BANK
Q.1 D Q.2 A Q.3 A Q.4 C Q.5 C Q.6 C Q.7 B
Q.8 D Q.9 B Q.10 C Q.11 B Q.12 B Q.13 D Q.14 D
Q.15 C Q.16 D Q.17 C Q.18 B Q.19 A Q.20 B Q.21 D
Q.22 B Q.23 B Q.24 A Q.25 A Q.26 D Q.27 C Q.28 D
Q.29 D Q.30 C Q.31 D Q.32 C Q.33 A Q.34 C Q.35 C
Q.36 B Q.37 D Q.38 A Q.39 D Q.40 D Q.41 D Q.42 B
Q.43 B Q.44 C Q.45 A Q.46 A Q.47 C Q.48 B Q.49 C
Q.50 B Q.51 D Q.52 A Q.53 B Q.54 B Q.55 D Q.56 B
Q.57 B
Q.58 A, C, D Q.59 B, C Q.60 C, D Q.61 B, C, D Q.62 A, C Q.63 A, C, D Q.64 A,B, C
Q.65 C, D Q.66 B, C Q.67 A, C Q.68 A  P; B  Q; C  S; D  R
Q.69 A  P, Q; B  Q, R; C  P, Q, S; D  R, S Q.70 A  S; B  S; C  Q
EXERCISE III
OBJECTIVE
Q.1 C Q.2 A Q.3 B Q.4 D Q.5 C, D Q.6 A Q.7. C
Q.8 D Q.9 C Q.10 D Q.11 B
SUBJECTIVE
Q.1 (a) 0.0175% , (b) 4.757 Q.2 No it will be > 7 Q.3 pH = 9 Q. 4 8

Q.5 3 Q.6 7 Q.7 4.47 Q.8 0.20 Q.9 3.00 10. 10.02
11. 6

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CHEMISTRY

" A SPECIALLY DESIGNED KIT FOR LEARNING."

VIBRANT ACADEMY (India) Private Limited

Bronsted & Lowry Concept

Conjugate acid and bases

(i) Neutral species having at least one lone pair of electrons.

Concentration before dissociation C 0 0

DEGREE OF IONISATION (DISSOCIATION):

Moles of reactant dissociate d

Autoprotolysis of water (or any solvent)

solvent is used, autoprotolysis constant will not be same.

Similarly pOH = log [OH]

[H3 O  ][H 2 PO –4 ] [H3 O  ][HPO 24– ] [H3O  ][PO 34– ]

Similarly, Kb denotes basic dissociation constant for a base.

(b) General Expression : [H  ]  0 .5( K a  K a2  4K a C )

If acids dissociate to a negligible extent, [H+] = K aC1  K a2 C 2

If we consider contribution of H+ from water then [H+] = K aC1  K a2 C2  K w

If the degree of hydrolysis(h or ) is small (<<1),  = K h C , [H+] = C

CN + H2O  HCN + OH  = K h C , [OH] = C,

Assuming degree of hydrolysis to be same for the both the ions,

Solubility(S) & Solubility Product(Ksp) :

* Water as amphiprotic solvent. + – * Concepts of acids and bases

10. Calculate pH of following solutions :

MIXTURE OF ACIDS & BASES

Take (Ka = 1.5 × 10–2).

20. H3A is a weak triprotic acid ( K a1 = 10–5 , K a2 = 10–8, K a3 = 10–111)

HSO 4 H+ + SO 24 ; K2 = 10–2 M

ACID BASE REACTIONS & TITRATIONS

20. What is the solubility of AgCl in 0.20 M NH3?

K2 = [ Ag(NH3 )2 ] / [Ag(NH3)+] [NH3] = 6 × 103 M–1.

21. A solution is 0.1 M in Cl– and 0.001 M in CrO2–

which sulphide precipitates first.

25. The salt Zn(OH)2 is involved in the following two equilibria,

Zn(OH)2 (s) + 2OH– (aq) [Zn(OH)4]2– (aq.) ; Kc = 0.13

Calculate the pH of solution at which solubility is minimum.

2. The conjugate acid of NH2 is

3. The strongest Bronsted base in the following anion is

4. Out of the following, amphiprotic species are

13. Which of the following solution will have pH close to 1.0?

15. The aqueous solution of FeCl3 is acidic due to

22. If equilibrium constant of

NaOH have been added are

HCl should be (Given: k b ( X  ) =10–6)

(A) 2 – 3 (B) 3 – 5 (C) 6 – 8 (D) 8 – 10

38. Ksp of AX4 and solubility of AX4 is S mol/litre is related by

39. The solubility of A2X3 is y mol dm–3. Its solubility product is

(C) Bi2S3 (Ksp= 1×10–72) (D) Ag3(PO4) (Ksp= 1.8×10–18)

Assertion & Reasoning Type Questions

53. Statement-1 pH of 10–7 M NaOH solution is exist between 7 to 7.3 at 25ºC.

Statement-2 At equivalent point solution is basic.

More than one may be correct

58. Which of the following statement(s) are ture :

(B) HPO 4 is a conjugate acid of H2PO 4

59. Which of the following statement(s) is/are correct?

(B) Addition of small amount of CH3COONa with out change in volume

64. The pH of which salt is independent of its concentration :

67. Select incorrect statement(s)

Match the Column

68. Column I Column II (At 25ºC)

(D) Saturated aqueous solution of Co(OH)3 (Ksp = 2.7 × 10–43) (S) pH ~ 10

70. Column I Column II

(C) 50 ml of 0.2 M HA (aq) (Ka = 10–5) (R) Phenolphthalein (8.3 to 10.1)

8. An aqueous solution contains an unknown concentration of Ba2+. When 50 mL of a 1 M solution of Na2SO4