PHYSICAL CHEMISTRY

(JEE-ADVANCED)

IONIC EQUILIBRIUM DPP

1. Arrange the following solutions in the decreasing order of pOH.
(A) pOH of 0.01 M HCl (B) pOH of 0.01 M NaOH
− +
(C) pOH of 0.01 M CH3COONa (4) pOH os 0.01 M NaCl
(1) (A) > (C) > (D) > (B) (2) (A) > (D) > (C) > (B)
(3) (B) > (C) > (D) > (A) (4) (B) > (D) > (C) > (A)

2. If the solubility product of AB2 is 3.20 × 10–11 M3, then the solubility of AB2 in pure water is
…… × 104 mol L–1
[Assuming that neither kind of ion reacts with water]

3. Two solution, A and B, each of 100 L was made by dissolving 4 g of NaOH and 9.8 g of
H2SO4 in water, respectively. The pH of the resultant solution obtained from mixing 40 L of
solution A and 10 L of solution B is ………….

4. The stoichiometry and solubility product of a salt with the solubility curve given below is,
respectively :

3
[]y/mM

2
1

1 2 3
[X]/mM
(1) X2Y, 2 × 10–9 M3 (2) XY, 2 × 10–6 M3
(3) XY2, 1 × 10–9 M3 (4) XY2, 4 × 10–6 M3

5. The strength of an aqueous NaOH solution is most accurately determined by titrating :

(Note : consider that an appropriate indicator is used)
(1) Aq. NaOH in a volumetric flask and concentrated H2SO4 in a conical flask
(2) Aq. NaOH in a pipette and aqueous oxalic acid in a burette
(3) Aq. NaOH in a burette and aqueous oxalic acid in a conical flask
(4) Aq. NaOH in a burette and concentrated H2SO4 in a conical flask

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6. For the following Assertion and Reason, the correct option is
Assertion The pH of water increases with increase in temperature.
Reason The dissociation of water into H+ and OH– is an exothermic reaction.
(1) Assertion is not true, but Reason is true.
(2) Both assertion and Reason are true and the Reason is the correct explanation for the
Assertion
(3) Both Assertion and Reason are false.
(4) Both Assertion and Reason are true, but the Reason is not the correct explanation for the
Assertion.

7. The Ksp for the following dissociation is 1.6 × 10–5

PbCl2(s) Pb2+(aq) + 2Cl–(aq)
Which of the following choices is correct for a mixture of 300 ml of 0.134 M Pb(NO3)2 and 100
mL 0.4 M NaCl ?
(1) Q < Ksp (2) Q > Ksp
(3) Q = Ksp (4) No enough data provided

8. Amongst the following, the form of water with the lowest ionic conductance at 298 K is
(1) saline water used for intravenous injection
(2) distilled water
(3) water from a well
(4) sea water

9. The solubility product of Cr(OH)3 at 298 K is 6.0 × 10–31. The concentration of hydroxide ions
in a saturated solution of Cr(OH)3 will be
(1) (2.22 × 10–31)1/4 (2) (18 × 10–31)1/4 (3) (4.86 × 10–29)1/4 (4) (18 × 10–31)1/2

10. If solubility product of Zr3(PO4)4 is denoted by Ksp and its molar solubility is denoted by S, then
which of the following relation between S and Ksp is correct?
1/6 1/7 1/9 1/7
K   K  K  K 
(A) S =  sp  (2) S =  sp  (3) S =  sp  (4) S =  sp 
 144   6912   929   216 

11. Consider the following statements.

I. The pH of a mixture containing 400 mL of 0.1 M H2SO4 and 400 mL of 0.1 M NaOH will be
approximately 1.3.
II. Ionic product of water is temperature dependent.
III. A monobasic acid with Ka = 10–5 has a pH = 5. The degree of dissociation of this acid is
50%.
IV. The Le-Chatelier's principle is not applicable to common-ion effect. The correct statements
are
(1) I, II and IV (2) II and III (3) I and II (4) I, II and III

12. The pH of a 0.02 M NH4Cl solution will be [Given Kb(NH4OH) = 10–5 and log2 = 0.301]
(1) 4.65 (2) 2.65 (3) 5.35 (4) 4.35
13. What is the molar solubility of Al(OH3) in 0.2 M NaOH solution? Given that, solubility product
of Al(OH)3 = 2.4 × 10–24
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 (1) 3 × 10–19 (2) 12 × 10–21 (3) 3 × 10–22 (4) 12 × 10–23

14. The molar solubility of Cd (OH)2 is 1.84 × 10–5m in water. The expected solubility of Cd(OH)2
in a buffer solution of pH = 12 is
2.49
(1) 1.84 × 10–9 M (2) × 10–9 M (3) 6.23 × 10–11 M (4) 2.49 × 10–10 M
1.84

15. 20 mL of 0.1 M H2SO4 solution is added to 30 mL of 0.2 M NH4OH solution. The pH of the
resultant mixture is [pKb of NH4OH = 4.7]
(1) 9.3 (2) 5.0 (3) 9.0 (4) 5.2

16. A mixture of 100 mmol of Ca(OH)2 and 2 g of sodium sulphate was dissolved in water and the
volume was made upto 100 mL.
The mass of calcium sulphate formed and the concentration of OH– in resulting solution,
respectively, are : (Molar mass of Ca(OH)2, Na2SO4 are 74, 143 and 136 g mol–1, respectively;
Ksp of Ca(OH)2 is 5.5 × 10–6)
(1) 13.6 g, 0.28 mol L–1 (2) 1.9 g, 0.28 mol L–1
–1
(3) 13.6 g, 0.14 mol L (4) 1.9 g, 0.14 mol L–1

17. If Ksp of Ag2CO3 is 8 × 10–12, the molar solubility of Ag2CO3 in 0.1 M AgNO3 is
(1) 8 × 10–12 M (2) 8 × 10–13 M (3) 8 × 10–10 M (4) 8 × 10–11 M

18. 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+?
(1) 5 × 10–9 M (2) 2 × 10–9 M (3) 1.1 × 10–9 M (4) 1.0 × 10–10 M

19. Which of the following are Lewis acids ?

(1) PH3 and BCl3 (2) AlCl3 and SiCl4
(3) PH3 and SiCl4 (4) BCl3 and AlCl3

20. Which of the following salts is the most basic in aqueous solution?
(1) Al(CN)3 (2) CH3COOK (3) FeCl3 (4) Pb(CH3COO)2

21. An alkali is titrated against an acid with methyl orange as indicator, which of the following is a
correct combination?
Base Acid End point
(1) Weak Strong Colourless to pink
(2) Strong Strong Pinkish red to yellow
(3) Weak Strong Yellow to pinkish red
(4) Strong Strong Pink to colourless

22. pKa of 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
(1) 7.2 (2) 6.9 (3) 7.0 (4) 1.0

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23. How many liters of water must be added to 1 L of an aqueous solution of HCl with a pH of 1 to
create an aqueous solution with pH of 2?
(1) 0.1 L (2) 0.9 L (3) 20. L (4) 9.0 L

24. The pH of a 0.1 molar solution of the acid HQ is 3. The value of the ionisation constant, Ka of
the acid is
(1) 3 × 10–1 (2) 1 × 10–3 (3) 1 × 10–5 (4) 1 × 10–7

25. The Ksp for Cr(OH)3 is 1.6 × 10–30. The molar solubility of this compound is water is
(1) 2
1.6 × 10 −30 (2) 4
1.6 × 10 −30 (3) 4
1.6 × 10 −30 / 27 (4) 1.6 × 10–30 / 27

26.  H+ + A– The pH of 0.1 M solution is 5. Its dissociation

An acid HA ionises as HA 
constant would be
(1) 1 × 10–10 (2) 5 (3) 5 × 10–8 (4) 1 × 10–5

27. Three reactions involving H2PO4− are given below

I. H3PO4 + H2O → H2PO4−
II. H2PO4− + H2O → HPO24− + H3O+
III. H2PO4− + OH– → H3PO4 + O2–
In which of the above does H2PO4− act as an acid?
(1) II only (2) I and II (3) III only (4) I only

28. Solubility product of silver bromide is 5.0 × 10–13. The quantity of potassium bromide (molar
mass taken as 120g mol–1) to be added to 1 L of 0.05 M solution of silver nitrate to start the
precipitation of AgBr is
(1) 1.2 × 10–10 g (2) 1.2 × 10–9 g (3) 6.2 × 10–5 g (4) 5.0 × 10–8 g

29. At 25°C, the solubility product of Mg(OH)2 is 1.0 × 10–11. At which pH, will Mg2+ ions start
precipitating in the from of Mg(OH)2 from a solution of 0.001 M Mg2+ ions?
(1) 9 (2) 10 (3) 11 (4) 8

30. Solid Ba(NO3)2 is gradually dissolved in a 1.0 × 10–4 M Na2CO3 solution. At what concentration
of Ba2+, will a precipitate begin to form?
(Ksp for BaCO3 = 5.1 × 10–9)
(1) 4.1 × 10–5 M (2) 5.1 × 10–5 M (3) 8.1 × 10–8 M (4) 8.1 × 10–7 M

31. Four species are listed below

I. HCO3− II. H3O+ III. HSO−4 IV. HSO3F
Which one of the following is the correct sequence of their acid strength?
(1) IV < II < III < I (2) II < III < I < IV (3) I < III < II < IV (4) III < I < IV < II

32. The pKa of a weak acid, HA is 4.80. The pHb of a weak base, B OH, is 4.78. The pH of an
aqueous solution of the corresponding salt, BA, will be
(1) 9.58 (2) 4.79 (3) 7.01 (4) 9.22

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33. The pKa of a weak acid (HA) is 4.5. The pOH of an aqueous buffered solution of HA in which
50% of the acid ionised is
(1) 4.5 (2) 2.5 (3) 9.5 (4) 7.0

34. Hydrogen ion concentration in mol/L in a solution of pH = 5.4 will be

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

−
35. The conjugate base of H2PO4 is
(1) PO34− (2) P2O5 (3) H3PO4 (4) HPO24−

36. The molar solubility (in mol L–1) of a sparingly soluble salt MX4 is S. The corresponding
solubility product is Ksp. S is given in terms of Ksp by the relation.
(1) S = (Ksp/128)1/4 (2) S = (Ksp/128)1/4 (3) S = (Ksp/256)1/5 (4) S = (Ksp/256)1/5

37. Which one of the following substance has the highest proton affinity?
(1) H2O (2) H2S (3) NH3 (4) PH3

38. The solubility in water of a sparingly soluble salt AB2 1.0 × 10–5 mol L–1. Its solubility product
will be
(1) 4 × 10–15 (2) 4 × 10–10 (3) 1 × 10–15 (4) 1 × 10–10

39. Which one of the following statements is not ture?

− 2−
(1) The conjugate base of H2PO4 is HPO4
(2) pH + pOH = 14 for all aqueous solutions
(3) The pH of 1 × 10–8 M HCl is 8
(4) 96,500 C of electricity when passed through a CuSO4 solution deposits 1g equivalent of
copper at the cathode

40. Which one of the following species acts as both Bronsted acid and base?
(1) H2PO2− (2) HPO32− (3) HPO24− (4) All of the above

41. Solibility of Ca(OH)2 is S mol L–1. The solubility product (Ksp) under the same condition is
(1) 4S3 (2) 3S4 (3) 4S2 (4) S3

42. An aqueous solution of 1M NaCl and 1M HCl is

(1) not a buffer but pH < 7 (2) not a buffer but pH > 7
(3) a buffer with pH < 7 (4) a buffer with pH > 7

43. pH of 0.005 M calcium acetate (pKa of CH3COOH = 4.74) is

(1) 7.04 (2) 9.37 (3) 9.26 (4) 8.37

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 ANSWER KEY
1. (2) 2. (1) 3. (10.60) 4. (4) 5. (3) 6. (3)
7. (2) 8. (2) 9. (4) 10. (2) 11. (4) 12. (3) 13. (3)
14. (4) 15. (1) 16. (2) 17. (3) 18. (3) 19. (4) 20. (2)
21. (3) 22. (2) 23. (4) 24. (3) 25. (3) 26. (1) 27. (1)
28. (2) 29. (2) 30. (2) 31. (3) 32. (3) 33. (3) 34. (1)
35. (4) 36. (3) 37. (3) 38. (1) 39. (3) 40. (3) 41. (1)
42. (1) 43. (1)
SOLUTION
1. (A) pOh of 0.01 M HCl :
→ H+ + OH−
HCl 
(0.01M) (0.01M) (0.01M)
[OH ] = (0.01 M); pH = – log [H+]
+

⇒ –log(10–2) ⇒ 2
pOH = 14 – pH ⇒ 14 – 2 = 12
(B) pOH of 0.01 M NaOH :
→ Na + + OH−
NaOH 
(0.01M) (0.01M)0. (0.01M)
– –2
[OH ] = 10
∴ pOH = – log[OH–]
⇒ –log(10–2) = 2
− +
(C) pOH of 0.01 M CH3COONa : (salt of weak acid + strong base)
1
pH = 7 + [pKa + log(10–2)]
2
∴ pH > 7, thus pOH < 7
(D) pOH os 0.01 M NaCl :
(It is a salt of strong acid + strong base)

2. AB2(s) A2+(aq) + 2B–(aq)

If the molar solubility of the solid substance is S mol L–1 then
Ksp = [A2+]1 [B–]2 ; Ksp = S1 × (2S)2 = 4S3
Solubility product of AB2 = 3.20 × 10–11 M3
3.20 × 10 −11
3.20 × 10–11 = 4 × S3 ⇒ S3 =
4
1/3
 320 × 10 −11 
S=   ⇒ S = 2 × 10–4 mol L–1
 4 

3. (A) 4 g NaOH in 100 L

4 / 40
=
⇒ M = 10−3 mol L–1.
100
(B) 9.8 g H2SO4 in 100 L
9.8 / 98
=
⇒ M = 10 −3 mol L–1
100
40 L of solution A contains
= 40 × 10–3 mol NaOH ( n = M × V)
= 40 × 10–3 mol OH–
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 10 L of solution B contains
= 10 × 10–3 mol H2SO4
= 20 × 10–3 mol H+
When they are mixed, total volume = 50 L and all H+ is neutralized by OH–.
Number of moles (nOH− ) of excess OH–.
= (40 – 20) × 10–3 = 20 × 10–3
nOH−
[OH− ] = (in liter)
Vsolution
nOH−
or [OH− ] =
Total volume
20 × 10 −3
= = 4 × 10 −4 M
50
As we know,
pOH = log[OH–]
∴ pOH = –log 4 × 10–4 = 4 – log 4
or pH = 14 – pOH
= 14 – (4 – log 4) = 10 + log 4 = 10.602

4. Units given for all option is M3, or (mol L–1)3, which implies that, the equilibrium has three ions.
Therefore,
XY2 X2+ (aq) + 2Y–(aq), Ksp = [X2+] [Y–]2
or X2Y 2X+(aq) + Y2–(aq), Ksp = [X+]2 [Y2–]
(i) Ksp in case of XY2,
Ksp = (1 × 10–3) (2 × 10–3)2 = 4 × 10–9 M3
(ii) Ksp in case of X2Y,
Ksp = (1 × 10–3)2 (2 × 10–3) = 2 × 10–9M
The only matching value of Ksp from options that satisfies the concentration values from graph
is [X2+] = 1 mM = 1 × 10+ M and [Y–] = 2 × 10–3 M
thus, salt is XY2 and Ksp = (10–3) (2 × 10–3)2 = 4 × 10–9 M3

5. The strength of aqueous NaOH solution is most accurately determined by titrating aqueous
NaOH in burette and aqueous oxalic acid in conical flask with phenolphthalein as an indicator.
(For weak acid-strong base titration, methyl orange cannot be used).
Thus, solution turns colourless to pink at the end point. (Phenolphthalein has pink colour when
pH > 10 and it is colourless when pH < 8 (approximately) which is easily to perceive.
If NaOH is taken in conical flask and oxalic acid is added from burette, the end point will be
the decolourisation of pink colour which is more difficult to perceive by human eye quickly.

6. The dissociation of water into H+ and OH– is an endothermic reaction.

∴ As temperature increase, its equilibrium constant also increases :
∴ [H+] and [OH–] in water at equilibrium increases with increases in temperature.
∴ pH = – log[H+] decreases, as temperature increases.
So, both Assertion and Reason are false.

7. PbCl2(s) Pb2+(aq) + 2Cl–(aq); Ksp = 1.6 × 10–5

For mixture, 300 mL 0.134 M Pb(NO3)2 and 100 mL 0.4 M NaCl
After mixing, total volume = 400 m
[Pb2+] after mixing (before any precipitate forms)
300 × 0.134 3 × 0.134 1
= = =
400 4 10
[Cl–] after mixing (before any precipitate forms)

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 100 × 0.4
= = 0.1
400
As we know,
3 × 0.134
Q = [Pb2+] [Cl–]2 = × 10–2 = 10–3
4

8. Among the given options, distilled water has the lowest ionic conductance at 298 K.
Water from well or sea contains mineral ions,
∴ they have ionic conductance.
Saline water is an electrolyte and contain ions
∴ It also has ionic conductance.

9. Ksp of Cr(OH)3 at 298 K is 6.0 × 10–31.

[OH–] in saturated solution of Cr(OH)3 = ?
Cr(OH)3 Cr3+ + 3OH–
S S
In a saturated solution, Ksp = [Cr3+] [OH–]3
= S(3S)3 = 27S4 = 6.0 × 10–31
1
6.0 × 10 −31  6.0 × 10 −31  4
∴ =S 4
= ⇒S  
27  27 
1
 6.0 × 10 −31  4
[OH–] = 3S = 3  
 27 
1
 6.0 × 3 4 −31 
4
−31 4
1
=  3
× 10  (18 × 10 )
 3 

10. Key Idea The concentration of a substance in a saturated solution is defined as its
solubility(S).
For AxBy  xAy+ + yBx– ; Ksp = [Ay+]x[Bx–]y
For, Zr3(PO4)4,
Zr3(PO4)4(s)  3Zr 4 + (aq) + 4PO34− (aq)
3SM 4 SM
4+ 3
Ksp = [Zr ] [PO34− ]4
1
 K sp  7
Ksp = (3S)3 (4S)4 = 6912 S7 or S =  
 6912 
1
 K sp  7
Thus, the relation between molar solubility(S) and solubility product (Ksp) will be S =  
 6912 

11. The explanation of given statements are as follows:

In statement (I), millimoles of H+ = 400 × 0.1 × 2 = 80
Millimoles of OH– = 400 × 0.1 = 40 (Limiting reagent)
∴ Millimoles of H+ left = 80 – 40 = 40
40 40 1
[H+] = = = M M
400 + 400 800 20
 1 
⇒ pH = –log[H+] = –log  
 20 
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 = –log1 + log2 + log10
= –0 + 0.301 + 1 ⇒ 1.30
Hence, the option (a) is correct.
In statement (II), ionic product of H2O is temperature dependent.
Kw = [H+] [OH–] ≈ 10–14(mol/L)2 at 25°C
With increases in temperature, dissociation of H2O units into H+ and OH– ions will also
increase. As a result, the value of ionic product, [H+] × [OH–] will be increased. e.g.
Temperature Kw (mol/L2)
5°C 0.186 × 10–14
25°C 1.008 × 10–14
45°C 4.074 × 10–14
Hence, the option (b) is correct.
In statement (III), for a weak monobasic acid HA
HA   H⊕ + AΘ
(1 – α) αCM αCM
⇒ pH of the solution is 5, i.e.
[H+] = 10–5 M = αC
αC × αC 10 −5 × α
⇒ Ka = =
(1 − α )C 1− α
10−5 × α
⇒ 10–5 = ⇒ α = 0.5 ⇒ a% = 50
1− α
Hence, the option (c) is correct.
In statement (IV), Le-Chatelier's principle is applicable to common ion effect. Because, in
presence of common ion (given) by strong electrolyte (say, Na+ + A ), the product of the
 H⊕ + AΘ.
concentration terms in RHS increases. For the weaker electrolyte, HA 
As a result dissociation of HA gets suppressed.
Hence, the option (d) is incorrect.

12. Key Idea NH4Cl is a salt of weak base (NH4OH) and strong acid (HCl). On hydrolysis, NH4Cl
will produce an acidic solution (pH > 7) and the expression of pH of the solution is
1
pH = 7 – (pKb + logC)
2
Given, kb(NH4OH) = 10–5
∴ pKb = –logKb = – log(10–5) = 5
C = concentration of salt solution = 0.05 M = 2 × 10–2 M
1
Now, pH = 7 – (pKb + logC)
2
On substituting the given values in above equation, we get
1
= 7 – [5 + log(2 × 10–2)]
2
1
= 7 – [5 + log2 – 2]
2
1
= 7 – [5 + 0.301 – 2]
2
= 7 – 1.65 = 5.35

13. Key Idea Concentration of substance in a saturated solution is defined as its solubility (S). Its
value depends upon the nature of solvent and temperature. For reaction,
 A+ + B–
AB 
Ksp = [A+] [B–]
 Al3+ +
Al(OH)3  3OH–
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 Initially 1 0 0
At equilibrium 1 – S S 3S + 0.2
NaOH → Na+ + OH–
0.2 0.2
Ksp of Al(OH)3 = 2.4 × 10–24 (Given)
Ksp = [Al]3+ [OH–]3
2.4 × 10–24 = [S] [3S + 0.2]3 [ 0.2 >> S]
2.4 × 10–24 = [S] [0.008]
[S] = 3 × 10–22

14. Key Idea The concentration of substance in a saturated solution is defined as its solubility (S).
Its value depends upon the nature of solvent and temperature.
 xAy+ + yBx–
AxBy 
Ksp = [Ay+]x [Bx–]y
Solubility of Cd(OH)2 (S) = 1.84 × 10–5 M
Given, pH = 12 [for Cd(OH)2 in buffer solution]
So, pOH = 2 ( pH + pOH = pKw)
12 + pOH = 14
pOH = 14 – 12 = 2
∴ [OH–] = 10–2 in buffer solution.
For reaction Cd(OH)2 → Cd2+ + 2OH–
S S2
2+ – 2
Ksp = [Cd ] [OH ]
Ksp = (S) (2S2) = 4S3
= 4(1.84 × 10–5)3
Ksp = 24.9 × 10–15
K sp
[Cd2+] =
[OH− ]2
= 24.9 × 10–15 × 10+4
⇒ = 24.9 × 10–11 M
[Cd2+] ⇒ 2.49 × 10–10 M
The expected solubility of Cd(OH)2 in a buffer solution of pH = 12 is 2.49 × 10–10 M.

15. The reaction takes place when H2SO4 is added to NH4OH is as follows :
H2SO4 + 2NH4OH → (NH4)2SO4 + 2H2O
Strong acid Weak base Salt of strong acid + weak base
Millimoles at t = 0.20 × 0.1 = 2 30 × 0.2 = 6 0
Millimoles at t = t 0 2 2
So, the resulting solution is a basic buffer
[NH4OH + (NH4)2SO4]
According to the Henderson's equation,
[(NH4 )2 SO4 ]
pOH = pKb + log
[NH4OH]
2
= 4.7 + log = 4.7
2
⇒ pH = 14 – pOH = 14 – 4.7 = 9.3
16. The reaction involved is as follows :
Ca(OH)2 + Na2SO4 → CaSO4 + 2OH– + 2Na+
2 × 1000
Millimoles at t = 0 100 = 14 0 0 0
142
Millimoles at t = t s 86 0 14 28
[Limiting reagent]

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 Weight
No. of moles =
Molecular mass
14
∴ Mass of CaSO4 = × 136 = 1.9 g
1000
No.of moles of solute
Also, Molarity =
Volume of solution(inL)
∴ Molarity of OH–
28 1000
[OH–] = × = 0.28 mol–1
1000 100
= 0.28 M

17. Let solubility of Ag2CO3 is S. Now,

0.1 M of AgNO3 is added to this solution after which let the solution of Ag2CO3 becomes S'
∴ [Ag+] = S + 0.1 and CO32−  = S'
Ksp = (S + 0.1)2 (S') ...(i)
Given, Ksp = 8 × 10–12
 Ksp is very small, we neglect S' against S in Eq.(i)
∴ Ksp = (0.1)2S'
or 8 × 10–12 = 0.01 S'
or S' = 8 × 10–12 × 102 = 8 × 10–10 M
Thus, molar solubility of Ag2CO3 in 0.1 M AgNO3 is 8 × 10–10 M.

18. Its given that the final volume is 500 mL and this final volume was arrived when 50 mL of 1 M
Na2SO4 was added to unknown Ba2+ solution. So, we can interpret the volume of unknown
Ba2+ solution as 450 mL i.e.
450mL + 50mL → 500mL
Ba2 + Na2SO4 BaSO4
solution solution solution

From this we can calculate the concentration of SO4−2 ion in the solution via
M1V1 = M2V2
1 × 50 = M2 × 500
(as 1 M Na2SO4 is taken into consideration)
1
M2 = = 0.1 M
10
Now for just precipitation,
lonic product = Solubility product (Ksp)
i.e. [Ba2+] [ SO24− ] = Ksp of BaSO4
Given Ksp of BaSO4 = 1 × 10–10
So, [Ba2+] [0.1] = 1 × 10–10
or [Ba2+] = 1 × 10–9 M
Remember This is the concentration of Ba2+ ions in final solution.
Hence, for calculating the [Ba2+] in original solution we have to use
M1V1 = M2V2
as M1 × 450 = 10–9 × 500
so, M1 = 1.1 × 10–9 M
19. Lewis acids are defined as,
"Electron deficient compounds which have the ability to accept atleast one lone pair."
The compound given are
PH3 Ocpet complete although P has vacant 3d-orbital but does not have the tendency to
accept lone pair in it. Hence, it cannot be considered as Lewis acid.
BCl3 Incomplete octet with following orbital picture.

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 2s 2p Vacant
1s
B- p-orbital

Used in bond formation

with Cl having one electron
each from B and Cl
Hence, vacant p-orbital of B can accept one lone pair thus it can be considered as Lewis acid.
AlCl3-Similar condition is visible in AlCl3 as well i.e. Al (Velence orbital only) =
Vacant p-orbital
3s 3p
3d vacant

Used in bond
formation with Cl
Hence this compound can also be considered as Lewis acid.
SiCl4 – Although this compound does not have incomplete octet but it shows the tendency to
accept lone pair of electrons in its vacant d-orbital. This tendency of SiCl4 is visible in following
reaction

Cl Cl
H
Si + H2O Si O
Cl Cl H
Cl Cl Cl
Cl
Lone pair acceptance
in d-orbital
Cl
Si – OH + HCl
Cl
Cl
Thus option (b) and (d) both appear as correct but most suitable answer is (d) as the condition
of a proper Lewis acid is more well defined in BCl3 and AlCl3.

20. Among the given salts

FeCl3 is acidic in nature i.e., have acidic solution as it is the salt of weak base and strong acid.
Al(CN)3 and Pb(CH3COO)2 are the salts of weak acid and weak base.
CH3COOK is the salt of strong base and weak acid.
Hence, the solution of CH3COOK will be most basic because of the following reaction.
CH3COOK + H2O   CH3COOH+ KOH
(Weak acid) (Strongbase)

21. Methyl orange show pinkish colour towards more acidic medium and yellow orange colour
towards basic of less acidic media. Its working pH range is
←
Pinkish
 3.9 − 4.5 
Yellow
→
Re d Orange

Weak base have the pH range greater than 7, When methyl orange is added to this weak
base solution it show yellow orange colour.

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 Now when this solution is titrated against strong acid the pH move towards more acidic range
and reaches to end point near 3.9 where yellow orange colour of methyl orange changes to
pinkish red resulting to similar change in colour of solution as well.
22. For a salt of weak acid and weak base,
1 1
pH = 7 + pKa – pKb
2 2
Given, pKa(HA) = 3.2, pKa(BOH) = 3.4
1 1
∴ pH = 7 + (3.2) – (3.4)
2 2
= 7 + 1.6 – 1.7 = 6.9
23. pH = 1
∴ [H+] = 10–1 = 0.1 M
pH = 2
∴ [H+] = 10–2 = 0.01 M
For dilution of HCl,
M1V1 = M2V2
0.1 × 1 = 0.01 × V2
V2 = 10 L
Volume of water to be added = 10 – 1 = 9 L
24. HQ = H+ + Q–
[H+] = K a C by Ostwald's dilution law
[H+] = 10–pH = 10–3 M
C = 0.1 M
Thus, 10–3 = K a × 0.1
10–6 = Ka × 0.1
∴ Ka = 10–5
Alternate method
 H+ + Q–
HQ 
Initial concentration 0.1 M 0 0
Given, pH = 3, this suggest [H+] = 10–3 M at equilibrium
Thus, [Q–] at equilibrium = 10–3 M
Hence, [HQ] = 0.1 M – 10–3 M
≈ 0.1 M [ 10–3 M <<< 0.1 M]
Ka for the above reaction is given by
[H+ ][Q− ] [10 −3 ][10 −3 ]
Ka = =
[HQ] [0.1]
–5
Ka = 1 × 10

25. Let molar solubility of Cr(OH)3 = s mol L–1

 Cr 3 + (aq) + 3OH– (aq)
Cr(OH)3(s) 
s 3s
Ksp = 106 × 10–30
= [Cr3+] [OH–]3 = (s) (3s)3 = 27s4
1.6 × 10 −30
∴ s4 =
27
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 1.6 × 10 −30
∴ s= 4
27

26. pH of a solution = 5
∴ [H+] = 10–pH = 10–5
HA (a weak acid) ionises as
 H+ + A–
HA 
1.0 0 0
(1 – 10–5) 10–5 10–5
[H+ ][A − ] 10 −5 × 10 −5 10 −10
=Ka = =
[HA] (
1 − 10 −5 1 )
–5
[1>>> 10 ]
= 1 × 10–10 M

27. Only in reaction (II), H2PO4− , gives H+ to H2O. Thus, behaves as an acid.

28. [AgBr] = [Ag+] = 0.05 M

Ksp [AgBr] = [Ag+] [Br–]
K sp ( AgBr )
⇒ [Br–] =
 Ag+ 
 
5.0 × 10−13
= = 10–11 M [mol L–1]
0.05
Moles of KBr needed to precipitate AgBr
= [Br–] × V = 10–11 mol L–1 × 1L = 10–11 mol
Therefore, amount of KBr needed to precipitate AgBr
= 10–11 mol × 120g mol–1 = 1.2 × 10–9 g

29.  Mg2+ + 2OH–

Mg(OH)2 
Ksp = [Mg2+] [OH–]2
K sp 1× 10−11
[OH–] = =
[Mg2+ ] 0.001
–1 –4
pOH = –log [OH ] = –log [10 ]
pOH = 4 and pH = 10
∴ pH = 14 – pOH = 14 – 4 = 10

30.  2Na+ + CO32−

Na2CO3 
[Na2CO3] = [ CO32− ] = 1 × 10–4 M
BaCO3  Ba2+ + CO32−
K sp(BaCO3 ) = [Ba2+] [ CO32− ]
K sp (BaCO3 )
[Ba2+] =
[CO32− ]
5.1× 10−9
[Ba2+] =
1× 10−4
[Ba ] = 5.1 × 10–5 M
2+

Hence, at 5.1 × 10–5 M concentration of Ba2+, a precipitate will begin to form.

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31. Conjugate bases of the given species are
species Conjugate base
−
HCO3 CO32−
H3O+ H2O
−
HSO4 SO24−
HSO3F HSO3−
Since, strong acid has a weak conjugate base.
Thus, the basic strength of the conjugate bases of the given acid is opposite to their acidic
strength. The basic strength of the conjugate bases of the given acids follows the order
HSO3− < H2O < SO24− < CO32− .
Hence, the acidic strength follows the order
HSO3F > H3O+ > HSO4− > HCO3−
32. For salt of weak acid and weak base
1
pH = [log Ka + log Kw – log Kb]
2
1 1 1
= pKa + pKw – pKb
2 2 2
1 1
= × 4.80 + 7 – × 4.78 = 7.01
2 2
33. When HA is 50% ionised. [HA] = [A–]
Buffer solution of weak acid HA → acidic buffer
[A − ]
pH = pKa + log
[HA]
or pH = pKa = 4.5
pOH = pKw – pH
pOH = 14 – 4.5 = 9.5
34. pH = 5.4
∴ [H+] = 10–5.4 = 10–6 . 100.6
Antilog of 0.6 is ≈ 3.98
∴ [H+] ≈ 3.98 × 10–6 M
35. H3PO4 is a tribasic acid, thus ionisec in three steps.
 H+ + H2PO4−
I. H3PO4 
II. H2PO4− 
 H+ + HPO24−
III. HPO24− 
 H+ + PO34−
2−
conjugate base is formed when an acid loses its proton. Thus, HPO4 is the conjugate base
−
of H2PO4 (Which is an acid in step II, but is the conjugate base of H3PO4 in step I).

36.  M4+ + 4X–

MX4 
Ksp = [M4+] [4X–]4
Ksp = (S) (4S)4
⇒ Ksp = 256 S5
1/5
K sp K 
5
S = ⇒ S =  sp 
256  256 
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37. The tendency to accept the proton by the donation of their lone pairs of electron is called
proton affinity. This proton affinity is also called basicity. Therefore, the molecule which
donates their lone pairs electron more readily, is said to be more basic. Since, N can easily
donate their lone pairs of electrons than O, S and P due to their smaller size and low
electronegativity.
Thus, NH3 possess the highest proton affinity. On the other hand, due to higher
electronegativity of O, it cannot donate their electron pair easily while P possess a larger size,
becomes less basic in nature.

38.  A2+ + 2B–

AB2 
S 2S
Ksp = [A ] [B ] = (S) (2S)2 = 4S3
2+ – 2

=4(1 × 10–5)3 = 4 × 10–15

39. In 1 × 10–8 M HCl solution, H2O is also present which also undergoes self ionisation.
 H+ + OH–
H2O 
10–7 M at 25°C
[Concentration of water (H2O)]
If it is taken simply even without common ion effect, higher concentration must be considered
which is 10–7 M but H+ from HCl decreases self ionisation of water and hence [H+] from H2O.
Hence, net concentration must be smaller than 10–7M.

40. According to Bronsted Lowry concept of acids and bases, an acid is a proton donor whereas a
base is a proton acceptor.
Thus, according to this concept, HPO24− can easily donate a proton and also accepts a proton
on reaction with water.
 PO34− + H3O+
HPO24− + H2O 
 H2PO24− + OH–
HPO24− + H2O 

41.  Ca2+ + 2OH–

Ca(OH)2 
Ksp = [Ca2+] [OH–]2
= (S) (2S)2 = 4S3

42. NaCl is salt of strong acid and strong base. Its not the case of buffer.
NaCl + H2O   NaOH + HCl
Aqueous NaCl, itself exact neutral solution.
HCl + H2O   H3O+ + Cl–
makes solution acidic.
43. Calcium acetate is a salt of weak acid and weak base.
0.005 M calcium acetate, (CH3COO)2Ca
(CH3COO)2Ca → Ca2+ + 2CH3COO–
0.005 M (2 × 0.005 = 0.01)
∴ [CH3COO ] = 0.01M
–

CH3COO– + H2O  CH3COOH + OH−

Alkaline

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 pK a logC
pH = 7 + +
2 2
log0.01
= 7 + 2.37 +
2
= 7 + 2.37 – 2.30 = 7.06

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