FAST TRACK : QUICK REVISION

 Equilibrium : It is a state in a process when two opposing processes

(forward and reverse) occur simultaneously at the same rate. The free
energy change at equilibrium state is zero i.e., ∆G = 0.

 Equilibrium constant : For a general reaction :

aA + bB 

 cC + dD

Kc = and Kp =

 Relationship between Kp and Kc :

Kp = Kc (RT)∆ng
∆ng = np(g) – nr (g)

 Magnitude of equilibrium constant depends upon the way in which a

reaction is written :

Chemical equation Equilibrium constant

aA + bB 

 cC + dD K

cC + dD 

 aA + bB K =
1

naA + nbB 

 ncC + ndD K = Kn
2

1 1 1 1
aA + bB 
 cC + dD
n n n n K3 = K1/n

Equilibrium 135
  Predicting the direction of reaction :
If Qc = Kc ⇒ The reaction is in a state of equilibrium.
Qc > Kc ⇒ The reaction proceeds in reverse direction.
Qc < Kc ⇒ The reaction proceeds in forward direction.

 Ostwald’s dilution law : Degree of dissociation of weak electrolyte,

α=

 Ionic Product of water (Kw) = [H3O+] [OH–] = 10–14 at 298K

 Le-Chatelier’s Principle : When a system of equilibrium is subjected to

a change in temperature, pressure or concentration, the equilibrium shifts
itself in such a way so as to undo or nullify the effect of change.

 Outcomes of Le-Chatelier’s Principle

Change at equilibrium Shift in equilibrium

Increase in temperature Endothermic direction

Decrease in temperature Exothermic direction
Increase in pressure Towards lesser gaseous moles
Decrease in pressure Towards greater gaseous moles
Increase in Conc. of reactants Forward direction
Increase in Conc. of products Reverse direction

 Conjugate Acid or Base : Acid-base pair which differ by H+ ion.

Species – H+ = Conjugate base
Species + H+ = Conjugate acid
 pH of solution :
pH = –log [H3O+] or [H+] = 10–pH , pOH = –log [OH–]
pH + pOH = pKw = 14 at 298K
 Common ion effect : The depression of ionisation of weak electrolyte by
the presence of common ion from a strong electrolyte is called common
ion effect. For example degree of dissociation of NH4OH decreases in the
presence of strong electrolyte NH4Cl.

136 Chemistry Class XI

  Hydrolysis of salts and pH of their solutions : Hydrolysis of salt is
defined as the reaction of cation or anion with water as a result of which
the pH of water changes.
1. Salts of strong and strong bases (e.g., NaCl) do not hydrolyse. The
solution pH will be 7.
2. Salts of weak acids and strong bases (e.g., CH3COONa) hydrolyse,
pH >7 (The anion acts as a base).
X– + H2O 

 HX + OH–
(Weak acid) (Weak base)
pH = 7 + (pKa + log C)

3. Salt of strong acids and weak bases (e.g., NH4Cl) hydrolyse, pH < 7.
(The cation acts as an acid).
M+ + H2O 

 MOH + H+

pH = (pKb + logC)

4. Salt of weak acids and weak base (e.g., CH3COONH4) hydrolyse. The
cation acts as an acid and anion as a base but whether the solution
is acidic or basic depends upon the relative values of Ka and Kb for
these ions.
M+ + X– + H2O 

 MOH + HX

pH = (pKa – pKb)

 Buffer solutions : The solutions, which resist the change in pH on dilution

or addition of small amounts of acid or base, are called buffer solutions.

 Basic buffer : Solution of weak base and its salt with strong acid, For e.g.,
NH4OH + NH4Cl
 Acidic buffer : Solution of weak acid and its salt with strong base, For
e.g., CH3COOH + CH3COONa.

Equilibrium 137
  Henderson Hasselbalch Equation for the pH of Buffer solution—

pH = pKa + log (for acidic buffer)

= pKa + log
pOH (for basic buffer)

 Solubility Product (Ksp) : The equilibrium constant that represent the

equilibrium between undissolved salt (solute) and its ions in a saturated
solution is called solubility product constant (Ksp).
For
AxBy xAy+ + yBx–

Ksp = [Ay+]x [Bx–]y = (xs)x (ys)y = xx. yx. s(x+y)

where s = Molar solubility

If ionic product < Ksp ; salt remain dissolve.
If ionic product > Ksp ; salt will be precipitated.

 Relationship between solubility (s) and solubility product (Ksp).

Ksp = xx.yy. sx + y
For binary salts (e.g., AgCl, AgBr, AgI) Ksp = s2
For Ternary salts (e.g., PbI2) Ksp = 4s3

138 Chemistry Class XI

 MIND MAP : EQUILIBRIUM
Effect of Pressure
Equilibrium Constant EQUILIBRIUM ng = 0 No effect
aA + bB  cC + dD ng > 0 On increasing pressure
c d
[C] [D] Non Ionic Ionic Entities backward reaction favoured
Kc = a b Entities and vice-versa
[A] [B] Ionic Equilibrium
c d
ng < 0 On increasing pressure
[PC] [PD] backward reaction favoured
Kc = a b
Chemical
[PA] [PB] Equilibrium and vice-versa

K p = Kc(R5) and
ng = (c + d) + (a + b)
Effect of Concentration
Gaseous component A, B, C & D
Le-Chatlier If reactant concentration increases or
Principle product decreases then forward reaction
forward and vice-versa
Reaction Quotent
c d
[C] [D]
Qc = a b Effect of Volume (Opposite ‘P’ Effect)
[A] [B]
n = 0 No effect
Q c = Kc Reaction is at equilbrium n > 0 On increasing pressure
Q c < Kc Forward reaction favoured backward reaction favoured
Q c > Kc Backward reaction fovoured till and vice-versa
new equilibrium is re-establish n < 0 On increasing pressure
backward reaction favoured
and vice-versa

Equilibrium
Effect of Temperature Effect of Inert Gas (N2, Xe, Kr, etc.)
K2 H 1 1 If inter gas is added at constant condition then
log = = R ( – ) no effect is observed
K1 2.303 T1 T1
If inter gas is added at constant pressure then
For endothermic reaction H is + at ng = 0 No effect
If T increases, forward reaction favoure
ng > 0 Forward reaction fovoured
and otherwise backward reaction

139
If T decreases, For Exothermic opposite effect ng < 0 Forward reaction fovoured
 1 2 3

140
ACID / BASE WEAK ACID / BASE pH, pOH
Arrhenius Concept 2 +
+ K K pH = –log [H3O ]total
H Donar – Acid (Hcl) K= =
– C C + –pH
OH Donar – Base (NaOH) (dilute sol.) [H3O ] = 10
Bronsted Lowry Concept + –
+ [H ] = [c] = Ka.c pOH = –log [OH ]total
H Donar (Acid)
+ –
H Acceptor (Base) [OH ] = [c] pH + pOH = 14 (298K)
Lewis Concept 1
pH = [pKa – logC]
Lone Pair Donar – Base (NH3) 2
Lone Pair Acceptor – Acid (AlCl3)

Chemistry Class XI
IONIC
EQUILIBRIUM

4 5 6
SOLUBILITY PRODUCT BUFFER SOLUTIONS SALT HYDROLYSIS
AxBy Salt solution has solubility ‘S’ M Acid Buffer (CH3COOH + CH3COONa) Kw 1
4– x– Acid Salt (NH4Cl) : KH = pH = 7 – [pka + logC]
AxBr  xA (aq.) + B (aq.) +
Ka.[Acid] Kb 2
[H ] =
x y x+y
[Salt] h= Kw / Kb.c
Ksp = x .y [S]
Salt Kw 1
1 2 1+2 3 pH = pka + log Basic Salt (CH3COONa) : KH =
AxBy = Ksp= 1 .2 .S = 4S Acid Ka
pH = 7 + 2 [pka + logC]
2 3 2+3 3
A2b3 = Ksp= 2 .3 .S = 108.S Basic Buffer (NH4OH + NH4Cl) h= Kw / Kb.c
Kb.[Acid] Kw h
–
[OH ] = Mixed Salt (CH3COONH4) : KH = , = KH
[Salt] Ka.Kb 1– h
[Salt] Kw
pOH = pkb + log KH = Hydrolysis constant h= = KH
[Acid] KaKb
1
h = Degree of Hydrolysis pH = 7 + 2 [pka – pkb]
 CASE BASED STUDY QUESTIONS

PASSAGE -1

According to Arrehenius theory, acids are substances that dissociates in water to

give hydrogen ions and bases are substances that produce hydroxyl ions.

Bronsted-Lowry gave a more general definition of acids and bases. According to

Bronsted-Lowry theory , acid is a substance that is capable of donating a hydrogen
ion and bases are substance which are capable of accepting of a hydrogen ion.

According to Lewis Acids and Bases , an acid is a species which accepts electron
pair and base which donates an electron pair

The following questions are multiple choice questions. Choose the most
appropriate answer:

I. Which among of the following can act as Lewis as well as Bronsted-Lowry

base

(A)
H2O (B) HF

(C) NH4+ (D) CH4

II. Among following the one pair that does not act as conjugate acid-base
pair is

H2O, H3O+
(A) (B) HCO3-, H2CO3

HSO4-, H2SO4
(C) (D) NH4+, NH2-

III. Which among the following is weakest base

ClO4-
(A) (B) ClO3-

ClO2-
(C) (D) ClO-

IV. Which among the following is not Lewis acid

(A)
AlCl3 (B) Co3+

Mg2+
(C) (D) NH3

ANS: I. A, II. D, III. A , IV.D

Equilibrium 141
PASSAGE -2
Common Ion effect is the phenomenon in which weak acid or weak base
dissociation is suppressed due to the presence of the common ion provided by the
strong electrolyte . For example the dissociation of CH3COOH is suppressed by the
addition of the CH3COONa. Similarly the dissociation of NH4OH is suppressed
due to presence of NH4Cl.This occurs due to the Le-Chatlier’s principle .
In these questions (Q. No V-VIII , a statement of assertion followed by a
statement of reason is given. Choose the correct answer out of the following
choices.

(a) Assertion and reason both are correct statements and reason is correct
explanation for assertion.

(b) Assertion and reason both are correct statements but reason is not correct
explanation for assertion.

(c) Assertion is correct statement but reason is wrong statement.

(d) Assertion is wrong statement but reason is correct statement.

V. ASSERTION : The dissociation of HCN is decreased when HNO3 is

added to solution.

REASON : HNO3 is a strong acid which provides H+ .

VI. ASSERTION : When NaOH (solid) is added to NH4OH solution , then

pH increases

REASON : NH4OH dissociation decreases by addition of NaOH

VII. ASSERTION : A mixture of CH3COOH and CH3COONa act as buffer
solution.

REASON : A buffer solution resist change in pH by addition of large

amount of Base or Acid.
VIII. ASSERTION : NH4Cl is basic salt
REASON : NH4Cl is produced by adding weak base NH4OH and strong
acid HCl.

ANS: V. A, VI. B, VII. C, VIII. D

142 Chemistry Class XI

 MULTIPLE CHOICE QUESTION (MCQ)
1. For the hypothetical reactions, the equilibrium constant (k) values are
given

A B : k1 = 2

B C: K2 = 4

C D : K3 = 8

The equilibrium constant (K) for the reaction A D is

(a) 48 (b) 24 (c) 12 (d) 64
2. The equilibrium constant for the reaction
1
SO2(g) + O (g) SO3(g) is 5 × 10–2 atm–1/2
2 2
The equilibrium constant for the reaction

2SO3(g) 2SO2(g) + O2(g) would be

(a) 100 atm (b) 25×10–4 atm (c) 400 atm (d) 125 ×19-6 atm–3/2

3. A(g) + 3B(g) 4C(g) initial concentration of A is equal to that of B. The

equilibrium concentrations of A and C are equal. What is the equilibrium
constant for

4C(g) A(g) + 3B (g)

(a) 4 (b) 1/8 (c) B (d) 16
4. The equilibrium reaction that is not affected by volume change at constant
temperature is

H2(g) + Cl2(g)
(a) 2HCl(g) (b) N2(g) + 3H2(g) 2NH3(g)

(c)
PCl5(g) PCl3(g) + C12(g) (d) H2(l) + CO2(g) H2CO3(l)

5. For the reaction CO(g) + Cl2 (g) COCl2(g), the value of Kc/Kp is
equal to
(a) RT (b) (RT)2 (c) 1/RT (d) 1.0
6. At 90°C pure water has Kw = 10–12. The solution with pH value 6.5 is
(a) Acidic (b) Basic (c) Amphoteric (d) Data insufficient

Equilibrium 143
 7. 40 ml of 0.1 M NH4OH is mixed with 20 mL of 0.1 M HCl. What is the
pH of the mixture? (pKb of ammonia solution = 4.74)
(a) 4.74 (b) 2.26 (c) 9.26 (d) 5
8. Identify Bronsted Lowry Acids in the reaction
[Al(H2O)6]3+ + HCO3– [Al(H2O)5(OH)]2+ + H2CO3
(X) (Y) (P) (Q)

(a) X, Y (b) Y, P (c) P, Q (d) X, Q

9. The pKa of weak acid HA is 4.80 and pKb of a weak base BOH is 4.78.
The pH of an aqueous solutions of corresponding salt BA will be
(a) 7.01 (b) 4.79 (c) 9.22 (d) 10.0
10 If ‘p’ M is the solubility of KAl(SO4)2, then Ksp is equal to
(a) p3 (b) 4p4 (c) p4 (d) 4p3

TRUE AND FALSE TYPE QUESTIONS

1. Equilibrium state can be achieved if a reversible reaction is carried out in
closed or open container.

2. For a reaction 2A(g) B (g) Qc > K if ‘A’ is added maintaining

Qc > K, the reaction will move in backward direction.
3. For the reaction at equilibrium
CaCO3 CaO(s) + CO2(g)
What CaO(s) is removed reaction moves in forward direction.
4. For a reaction aA + bB cC + dD at equilibrium ∆G0 = 0 always.

5. For a reaction at equilibrium H2(g) + Cl2(g) 2HCl(g)

K b [HCl]2
K = 4, the value of is 1.
K f [H 2 ][Cl2 ]
6. For the electrolyte A2B if Ksp is solubility product then its solubling ‘S’
M is [Ksp]1/3 ÷ 4.
7. HCO–3 is conjugate base of H2CO3.
8. H2O can act as acid as well as base.
9. The pH of buffer solution remain same when any amount of dilution is
done.

144 Chemistry Class XI

 10. For a salt AB2(s) solution if Ionic product (I.P) > Ksp, then precipitation
will take place.

Ans. 1. False 2. True 3. False 4. False 5. True

6. True 7. True 8. True 9. False 10. True

FILL IN THE BLANKS

1. At equilibrium rate of forward reaction is always equal to ..................

2. Kp & Kc are ....... for reaction at equilibrium of type H2(g) + Br2(g) 2HBr(g).
3. If Kc for reaction CH3COOH(l) + C2H5OH CH3COOC2H5(l) + H2O(l)
is 4. Then Qc and Kc are ................. at equilibrium.
4. If A+B –70J/mol D, reaction temperature is increased then reaction
moves in ............... direction.
5. Presence of catalyst will ...... the equilibrium constant.
6. The conjugate acid of H2O is ..............
7. On dilution, the degree of dissociation of acetic acid will ..............
8. The presence of NH4Cl in NH4OH solution will ............. the degree of
dissociation of NH4OH.
9. If Ionic product (IP) < Ksp for a salt solution of AB, then addition of AB
further ........... lead to precipitation initially.
10. Kp is always equal to Kc if ∆ ng is ............
Ans. 1. rate of backward reaction, 2. equal, 3. equal, 4. backward direction
forward, 5. not change, 6. H3O+, 7. increase, 8. decrease, 9. will not,
10. zero.
MATCH THE COLUMNS
I. Match the reaction in Column I with the parameters in Column II and unit
(M=Molarity) of K eq in Column III
S.N. Column I Column II Column III
1.  2NH (g), ΔH= -ve (a) T increase then K increase (p) M0
N2(g)+3H2(g)  3

2.  4NO(g), ΔH= +ve (b) T increase then K decrease (q) M2-
2N2(g)+2O2(g) 

3. 2X(g)  Y(g)

 , ΔH= +Ve (c) P has not effect (r) M-1

4. PCl5(g) 
 PCl (g)+Cl (g), ΔH= +ve (d) Equilibrium move forward (s) M
3 2
On addition of Xe Gas

Equilibrium 145
II. Match the parameter in Column I with the pH expression in Column II and
examples in Column III
S.N. Column I Column II-pH Column III
1. Salt of weak acid and weak base (a)7+ 0.5(pka +logC) (p) NH4Cl
2. Salt of weak acid and strong base (b) 7+ 0.5(pka -pkb) (q) NaCl
3 Salt of strong acid and strong base (c)7- 0.5(pkb +logC) (r) CH3COONa

4. Salt of strong acid and weak base (d) 0.5 (pkw) (s) CH3COONH4

ANS. :
MATCH-I : 1. b, q 2. c, p 3. a, r 4. d, s
MATCH-II : 1. b, s 2. a, r 3. d, q 4. c, p

ASSERTION - REASON TYPE QUESTION

Each question contains statement-1 (assertion) and Statement-2 (Reason)
Examine the statements carefully and mark the correct answer according
to the instruction given below :
A. If both the statements are true and statement -2 is the correct explanation
of statement-I
B. If both the statements are true but statement-2 is not the correct explanation
of statement-I
C. If statement-I is true and statement-2 is false
D. If statement-I is false and statement-2 is true.
1. Statement-1 : The endothermic reactions are favoured at lower temperature
and the exothermic reactions are favoured at higher temperature.
Statement-2 : when a system in equilibrium is disturbed by changing the
temperature, it will tend to adjust itself so as to overcome the effect of
change.
2. Statement-1 : The melting point of ice decreases with increase of pressure
Statement-2 : Ice contracts on melting.
3. Statement -1 : The gas phase reaction PCl3(g) + Cl2(g) PCl5(g) shifts
to the right on increasing pressure.
Statement-2 : When pressure increase, equilibrium shifts towards more
number of moles.

146 Chemistry Class XI

 4. Statement-1 : The chemical equilibrium is not static but dynamic in nature.
Statement-2: The chemical equilibrium is a state in which two opposing
process are proceeding at the same rate.
5. Statement-1 : The catalyst does not change the equilibrium constant.
Statement-2 : Because for the catalysed reaction and uncatalysed reaction
∆H remains same and equilibrium constant depends on ∆H.
6. Statement-1 : If water is heated to 59°C, the pH will increase.
Statement-2 : Kw increases with increase in temperature.
7. Statement-1: Addition of HCl(aq.) to CH3COOH (aq.) decrease the
ionisation of CH3COOH (aq.).
Statement-2 : Due to common ion effect H+, ionisation of CH3COOH
decreases.
8. Statement-1: Sparingly soluble salts AB and XY2 with the same solubility
product, will have different solubility.
Statement 2: Solubility of sparingly soluble salts depends upon solubility
product.
9. Statement-1 : The ionisation constants of weak diprotic acid are in the
order of Ka1 > Ka2.
Statement-2 : Removal of H+ from anion is difficult as compared to neutral
atom.
10. Statement-1 : In a titration of weak acid with strong base, the pH at the
half equivalence point is pKa.
Statement-2 : At half equivalence point, it will form acidic buffer at its
maximum capacity where [Acid] = [Salt].
Ans.: 1. D, 2. A, 3. C, 4. A, 5. A, 6. D, 7. A, 8. B, 9. A, 10. A

ONE WORD ANSWER TYPE QUESTIONS

1. What is sum of pH + pOH at 25ºC? [Ans. 14]
2. Write the Henderson Hasselbalch equation for acidic buffer
[SALT]
Ans. pH = pka + l0g
[ACID]
3. How is degree of dissociation related with concentration terms and Ka,

for weak electrolyte. Ans. α = Ka / c
4. How NH3 is defined as Lewis base?
[Ans. It contain Lone paid of electrons]
5. How are Kp and Kc related? [Ans. Kp = Kc (RT)∆n]
6. How does K affected for endothermic reaction if temperature is increased?
[Ans. K get decreased]

Equilibrium 147
 7. What is the effect of catalyst on K? [Ans. K remains unaffected]
8. How is pH scale affected by increasing temperature?
[Ans. pH scale gets contracted]
9. What is the conjugate base of HCO3– ? [Ans. CO32–]
10. What is the nature of CH3COOH in conc. HCl solution?
[Ans. Bronsted Base]
1-MARK QUESTIONS
1. Define physical equilibrium. Give an example also.
2. Fizz is observed when soda water bottle is opened. Why ?
3. Justify the statement : ‘Both physical and chemical equilibrium are dynamic
in nature’
4. State Law of Chemical equilibrium.
5. In a reversible reaction, the two substances are in equilibrium. If the
concentration of each one is reduced to half, then what is the effect on the
equilibrium constant ?
6. K1 and K2 are equilibrium constant for reactions (1) and (2)
(i) N2(g) + O2(g) 2 NO(g)
(ii) NO(g) 1/2 N2(g) + 1/2 O2(g)
Calculate the relation between K1 and K2.
7. Write the equilibrium constant expression for the following reaction :
3 Fe(s) + 4 H2O(g) Fe3O4(s) + 4 H2(g)
8. Classify the equilibrium as homogeneous or heterogeneous :
CH3COOC2H5(aq.) + H2O(1) CH3COOH(aq.) + C2H5OH (aq.)
(PNH3 )
9. Kp = 3 1
(PH2 ) 2 (PN2 ) 2

Write the balanced chemical equation corresponding to the above

expression.
10. Give the direction in which the reaction would proceed if Qc > Kc.
11. Hb(s) + O2(g) HbO2(s)
Predict the direction in which equilibrium gets shifted if partial pressure
of O2(g) is lowered.

148 Chemistry Class XI

 12. Discuss the position of equilibrium if the following reaction is carried out
in the presence of catalyst.
2SO2(g) + O2(g) 2SO3(g)

13. Which of the following are Lewis acids ?

H2O, BF3, H+, NH4+
14. Write the conjugate acids for the following Bronsted bases.
C6H5OH, H2O
15. Write the conjugate bases for the following Bronsted acids.
H2O, CH3COOH.
16. Which of the following are Lewis acids ?
(a) H2O (b) AlCl3 (c) NH4+
17. Define Ostwald’s dilution law.
18. SO32– is Bronsted base or acid and why ?
19. Why pH of our blood remains almost constant at 7.4 though we quite often
eat spicy food ?
20. pH of black coffee is 5.0 at 25ºC. Is black coffee acidic or basic ?
[Ans. Acidic]
21. What will be the value of (pKa + pKb) at 25ºC.
22. What will be the pH of 1 M KNO3 solutions at 25ºC?
23. CaCl2(s) + H2O(l) CaCl2(aq.) + Heat
Discuss the solubility of CaCl2 if temperature is increased.
24. Why does the solubility of CO2 decrease with rise in temperature ?
25. The solubility of A2 X3 is y mol dm–3. Calculate its solubility product.
26. Write the Ksp expression for Al (OH)3.
27. What is the condition for precipitation of a salt ?
28. Pridict whether the solution is acidic, basic or natural when NH4NO3
undergo hydrolysis.
29. Explain why pure NaCl precipitates out when HCl gas is passed through
the solution of NaCl ?
30. Give the Henderson’s Hasselbalch equation for an acidic buffer solution.

Equilibrium 149
 31. On which of the factors the equilibrium depend : Temperature, nature of
reactant and product, initial concentration and pressure of the reactants.
32. Arrange the following in increasing acidic strength HCl, HBr, HF, HI
[Ans. HF < HCl < HBr < HI]
33. Arrange the following in increasing Lewis base strength
NH3, BiH3, PH3, AsH3, SbH3
[Ans. BiH3< SbH3 < ASH3< PH3 < NH3]
34. Arrange following in increasing pH value
0.1M CH3COOH, 0.1 M NaCl, 0.1MHCl, 0.1MNaOH, 0.1MNH4OH
[Ans. 0.1MHCl < 0.1M CH3COOH < 0.1M NaCl <
0.1 NH4OH < 0.1M NaOH]
35. Arrange following in increasing order of degree of hydrolysis.
0.1M NH4OH, 0.01 M NH4OH, 10-5 M NH4OH, 10-3 M NH4OH, 10-6
M NH4OH
[Ans. 0.1M NH4OH < 10-2 M NH4OH, 10-3M NH4OH<
10-5MNH4OH < 10-6 M NH4OH]
36. Arrange following in increasing order of acidic strength
CH3COOH, HCOOH, CH3CH2COOH, C6H5COOH, CH2COOH
[Ans. CH3COOH < C6H5COOH < HCOOH < CH2FCOOH]
37. Arrange following in increasing order of basic strength in gas phase
NH3, (CH3)2NH, (CH3)3N, CH3NH2
[Ans. NH3 < NH3NH2 < (CH3)2NH < (CH3)3N]
38. Arrange the following pkb in increasing order

CH3

[Ans. pK2 < pK1 < pK4 < pK3]
39. Arrange the basic strength of following
F–, Br–, Cl–, I–
[Ans. I– < Br– < Cl– < F–]

150 Chemistry Class XI

 40. Arrange the following in increasing base strength
CH3–, NH2–, OH–, F–
[Ans. F– < OH– < NH2 < CH3–]

2-MARKS QUESTIONS

1. The standard Gibbs energy change at 300 k for the reaction 2A B+

C is 2494. 2 J. At a given temperature, and time. the composition of the
reaction mixture is [A] = ½, [B] = 2, [C] = ½. The reaction proceed in the
(R = 8.314J/K/mo1, = 2.718) [Ans. Reverse direction]

2. The equilibrium constant for

N2(g) + O2(g) 2NO(g) is K, then calculate equilibrium constant
for ½N2(g) + ½O2(g) NO(g). [Ans. √K]

3. For the reversible reaction N2(g) + 3H2(g) 2NH3(g) at 500°C, the

value of Kp is 1.44×10–5 atn–2. Find the Kc value.
[Ans. 1.44 × 10–5 / (0.082 × 773)–2]

4. The equilibrium constant at 298 K for the reaction A + B C + D is

100. If the initial concentration of all the four species were 1M each, then
equilibrium concentration of D will be [Ans. 1.818]

5. For the reaction

NH4COO NH2(s) 2NH3(g) + CO2(g)
If equilibrium pressure is 3 atm. Find the value of Kp [Ans. 4]

6. A buffer solution with pH 9 is to be prepared by mixing NH4Cl that should

be added to one litre of 1.0m NH4OH kb 1.8 × 10-5
[Ans. NH4Cl = 1.8 M]

7. Calculate the solubility of silver chloride in water at room temperature if

the Ksp of AgCl is 1.6×10-10. [Ans. 1.26 × 10-5M]

8. Calculate the molar solubility of Ni(OH)2 in 0.10m NaOH. The ionic

product of Ni(OH)2 is 2.0 × 10-15. [Ans. 2.0 × 10-13M]

Equilibrium 151
 9. Calculate the pH of 10-8 M HCl solution. [Ans. 6.96]

10. How many grams of NaOH must be dissolved in IL of the solution to give
it a pH value of 12? [Ans. 0.4g]

3-MARKS QUESTIONS

1. The equilibrium constant for the reaction H2(g) + Br2(g) 2HBr(g) at

1024 K is 1.6×105. Find the equilibrium pressure of all gases if 10.0 bar
of HBr is introduced into a sealed container at 1024K. [Ans. 10 bar]

2. For the reaction 2BrCl(g) Br2(g) + Cl2(g) Kc is 32 at 500 K. If initially

pure BrCl is present at a concentration of 3.30 ×10-3 M, what is its molar
concentration in the mixture at equilibrium? [Ans. 3.0 × 10-4 M]

3. What is the equilibrium constant Kp and Kc for the reaction PCl5(g)

PCl3(g) + Cl2(g) if the pressure is 1.0 atm in 8.0L container at equilibrium.

[Ans. Kc = 0.04 Kp = 1.77]

4. The Kp for the reaction, N2O4(g) NO2(g) is 640 mm at 775 K. Calculate

the percentage dissociation of N2O4 at equilibrium pressure of 160mm.
At what pressure the dissociation will be 50%.

[Ans. 70.7%, P = 480 mm]

5. Show that degree of dissociation (α) for the dissociation

1/ 2 of PCl5 into PCl3
 Kp 
and Cl2 at pressure P is given by α = 
 P + kp 

6. How much of 0.3M NH4OH should be mixed with 30 mL of 0.2m solution

of NH4Cl to give a buffer solution of pH 10. pkb for NH4OH is 4.75.

[Ans. V = 112.5 mL]

7. Predict whether a precipitate will be formed or not on mixing 20 mL of

0.001 N NaCl solution with 80 mL of 0.01 M AgNO3 solution. Ksp for
AgCl is 1.5 × 10-10. [Ans. Yes, ppt will formed.]

152 Chemistry Class XI

 8. The values of Ksp of two sparingly soluble salts Ni(OH)2 and AgCN are
2.0 × 10-15 and 6.0 × 10-17 respectively. Which salt is more soluble. Explain

[Ans. SNi(OH) = 5.8 × 10-5M : S(Ag CN) = 7.8×10-9M . Ni(OH)2

2
is more soluble]

9. The ionization constant of propanoic acid is 1.32×10-15. Calculate the

degree of ionization if its solution is 0.05 M. What will be its degree of
ionization if the solution is 0.01 M in HCl solution.

[Ans. 1.62 × 10-2, 1.32 × 10-3]

10. Calculate the pH of a solution obtained by mixing 50ml of 0.2M HCl with
49.9 mL of 0.2m NaOH solution. [Ans. 3.699]

HOTS QUESTIONS

1. The molar solubility of Cd(OH)2 is 1.84 × 10-5M. Calculate the expected

solubility of Cd(OH)2 in a buffer solution of pH = 12.
2+ –
Ans. Cd(OH) 2  Cd (aq.) + 2OH (aq.)

S 10–2

2.49 × 10-14 = S(10-2)2 ∴ S = 2.49 × 10-10M

2. An aqueous solution contains an unknown concentration of Ba2+. When 50

ml of a 1M solution of Na2SO4 is added. BaSO4 just begins to precipitate.
The final volume is 500ml. The solubility product of BaSO4 is 1×10-10.
Find the original concentration.
50 ×1 
Ans. K=  2+   2–   Ba 2+   =
  500  10 × 500
–9
sp  Ba  SO 4= 

Ba2+ = 10–9 M

10–9 × 500 = 450 × M ∴ M = 1.11 × 10–9M

3. 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 4S– ions is 1.2×10–13, then find the concentration of S–2
ions in aqueous solution.

Equilibrium 153
 Ans. H2S(aq.) 2H+ + S2–

(0.1 – x) (2x + 0.29) x

Ka = Ka × Ka = 1.2 × 10–20
1 2

( 0.2 )2 S2– 
1.2 × 10–20 = , [S2–] = 3 × 10–20
0.1

4. 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?

Ans. 0.1 × 1 = (1 + v) (0.01) ⇒ v = 9L

5. A certain buffer solution contains equal concentration of X– and HX. The

Kb for X– is 10–10. Find the pH of the buffer .
10 –14
Ans. ka.kb = ∴= 10–14
ka = –10
10 –4
10
[x – ]
pH = pka + log
[Hx]

1
∴ pH = 4 + log = 4 ∴ pH = 4
1
6. The % yield of Ammonia as a function of time in the reaction N2(g) +
3H2(g) 2NH3(g), DH < O at (P, T) is given below:

If this reaction is conducted at T2 > T1, then plot the % yield of NH3 as a

function of time on same graph
T1
Ans. Initially on increasing temperature the T2
%
rate of reaction increases, however since the (yield)
reaction is exothermic therefore % yield of NH3
get decreased overall after a certain interval of
time. Time

154 Chemistry Class XI

 7. Consider the reaction NH4COONH2(s) 2NH3(g) + CO2(g) at a certain
temperature, the equilibrium pressure of the system is 0.318 atm. Find Kp
of the decomposition of ammonium carbonate.
Ans. Ptotal = 3P ∴ P = 0.318/3 = 0.106
Kp = 4P3 = 4.76 × 10–3

8. The equilibrium constant for the reaction CO(g) + H2O(g) CO2(g) +

H2(g) is 5. How many moles of CO2 must be added to 1 litre container
already containing 3 moles each of CO and H2O to make 2M equilibrium
concentration of CO?
Ans. CO + H2O CO2 + H2
t=0 3 2 x 0
At equilibrium 2 2 x+1 1
x +1
S
∴= x 19
⇒=
4

9. At constant temperature, the equilibrium constant Kp

N2O4 2NO2 is given by
4x 2 P
k p = where, P = Pressure and X = Extent of reaction
1– x
How does the value of Kp change on following changes
(a) ‘P’ increases
(b) X changes
(c)
‘P’ decreases
Ans. Kp is equilibrium constant which does not change on changing the
P, x.Kp depends on temperature.

10. When two reactants A and B are mixed to give product 'c' and 'p' the
reaction quotient 'Q' at the initial stages of the reaction will be?
Ans. In the beginning of the reaction Q = 0. As the reaction proceeds in
the forward direction Q starts increasing.
At chemical equilibrium Q = K

Equilibrium 155
 UNIT TEST-I
Time Allowed: 1 Hr. Maximum Marks : 20
General Instructions:
(i) All questions are compulsory.
(ii) Maximum marks carried by each question are indicated against it.

1. What is the pH 10–3 M HCl solution ? [1]

(a) 1 (b) 11 (c) 3 (d) 14
2. Which one can act as Arrhenius Acid ? [1]
(a) NH3 (b) H2O (c) HCl (d) C6H5OH
3. Write the conjugate base of CH3COOH, H2O. [1]
4. Write the relation between Kp and Kc. [1]
5. What is the nature of following reaction [1]
Exothermic or endothermic
A + B – 70J —→ C
6. The pka of CH3COOH and pkb of NH4OH are 4.76 and 4.75 respectively.
Calculate the pH of CH3COONH4. [2]
7. What is a buffer solution. Calculate the pH of the solution obtained by
adding 4mol of CH3COOH with 3 mol of NaOH in 1 litre container. [2]
pka, CH3COOH = 4.74 log2 = 0.3010 log3 = 0.4771
8. Calculate the molar solubility of Ni(OH)2 in 0.1M KOH solution. The Ksp
for Ni(OH)2 is 2.0×10–15. [3]
9. Kp = 0.04 atm at 899 K for the equilibrium shown below. What is the
equilibrium concentration of H2 when it is placed in a flask at 4.0 atm
pressure and allowed to come to equilibrium. [3]
C2H6(g) C2H4(g) + H2(g)
10. The first ionization constant of H2S is 9.1×10-4. Calculate the concentration
of HS-1 in its 0.1 M solution. How will this concentration be effected if
the solution is 0.1 M HCl also? If the second dissociation constant of H2S
is 1.2×10-12. Calculate the concentration of S2- in both conditions. [5]

156 Chemistry Class XI

 UNIT TEST-II
Time Allowed: 1 Hr. Maximum Marks : 20
General Instructions:
(i) All questions are compulsory.
(ii) Maximum marks carried by each question are indicated against it.

1. What is the pH 10–8 MHCl solution ? [1]

(a) pH>7 (b) pH<7

(c) pH=7 (d) Cannot be defined

2. What is the conjugate acid for the NH3? [1]

(a) NH2- (b) NH2-

(c) N3- (d) NH4+

3. Define Lewis acid and base with one example each. [1]

In following questions a statement of assertion followed by a statement of

reason is given. Choose the correct answer out of the following choices.

(a) Assertion and Reason both are correct statement and reason is correct
explanation for assertion.

(b) Assertion and Reason both are correct statements but reason is not correct
explanation for assertion.

(c) Assertion is correct statement but reason is wrong statement.

(d) Assertion is wrong statement but reason is correct statement.

4. Assertion : HI is stronger acid than HCl [1]

Reason : Size of I is more than Cl and hence H-I bond strength is less
than HCl.

5. Assertion : BF3 is Lewis acid and NH3 is Lewis base. [1]

Reason : NH3 is short of octet and BF3 molecule contain lone pair of
electron.

Equilibrium 157
 6. Arrange the following in increasing acidic strength. Give reason also

CH4, NH3, H2O, HF [2]

7. Kc for the reaction SO2 + 0.5O2 → SO3 at 600°C is 61.7. Calculate

Kp. [2]

8. 25.4 ml of hydrogen and 20.4 ml of iodine when heated in a closed

container, produced 30.8 mL of HI at equilibrium. Calculate the degree
of dissociation of HI at same temperature. [3]

9. Define common ion effect. The solubility of CaF2 in water at T K is

2x10-4 moles/L. Calculate (i) Ksp, and (ii) Solubility in 0.01 M NaF
solution. [3]

10. (i) What is a buffer solution? What are its types?

(ii) Derive the Henderson-Hasselbalch equation for an Acidic buffer with

the help of relevant example.

(ii) 8g of NaOH was dissolved in one litre of a solution containing one

mole of CH3COOH and one mole of CH3COONa. Find the pH of the
resulting solution. (The pKa of CH3COOH is 4.74). [5]

******

158 Chemistry Class XI