Allen SRG Chemistry Examplar Class 11th

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EXAMPLAR
1. MOLE CONCEPT (1-10) 5. REDOX (34-43)

l Fill in the Blanks l Fill in the Blanks
l Assertion–Reason l Assertion–Reason
l Single Choice Correct l Single Choice Correct

l Comprehension
l Multiple Choice Correct
l Subjective Questions
l Comprehension
6. ATOMIC STRUCTURE (44-57)
l True and False
2. PERIODIC TABLE (11-18)
l Fill in the Blanks
l True and False
l Assertion–Reason
l Fill in the Blanks l Single Choice Correct
l Assertion–Reason l Multiple Choice Correct
l Single Choice Correct l Match the Column
l Multi Choice Correct l Comprehension
l Comprehension l Subjective Questions
7. GASEOUS STATE (58-68)
3. CHEMICAL BONDING (19-26) l True and False
l True and False l Fill in the Blanks
l Fill in the Blanks l Assertion–Reason

l Single Choice Correct
l Match the Column
l Comprehension
l Match the Column
l Comprehension
8. CHEMICAL EQUILIBRIUM (69-86)
l True and False
4. MOLE CONCEPT (27-33) l Fill in the Blanks
l Fill in the Blanks l Assertion–Reason
l Assertion–Reason l Single Choice Correct
l Single Choice Correct l Multiple Choice Correct
l Multiple Choice Correct l Match the Column
l Comprehension l Comprehension
l Subjective Questions l Subjective Questions
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9. IONIC EQUILIBRIUM (87-102) 11. THERMOCHEMISTRY (114-130)
l Assertion–Reason l True and False
l Single Choice Correct l Fill in the Blanks
l Multiple Choice Correct l Assertion–Reason
l Match the Column l Single Choice Correct
l Comprehension l Multiple Choice Correct
l Subjective Questions l Match the Column
l Comprehension
10. THERMODYNAMICS (103-113) l Subjective Questions
l True and False
l Fill in the Blanks 12. CHEMICAL BONDING (131-140)
l Assertion–Reason l Assertion–Reason
l Single Choice Correct l Single Choice Correct
l Multiple Choice Correct l Multiple Choice Correct
l Match the Column l Match the Column
l Comprehension l Comprehension
l Subjective Questions l Subjective Questions

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Mole Concept
MOLE CONCEPT
Fill in the blanks
1. Ratio of number of protons to neutrons in 3.011 × 1022 molecules of D3O+ is “_____”
2. Nitrogen has an atomic number of 7 and oxygen has an atomic number of 8. The total number of electrons in
the nitrate ion (NO–3) is ......................... .
3. The maximum number of electrons that can be accommodated in all the orbitals for which l = 3
is ......................... .
True/False
4. The electron density in xy plane of 3d 2 - 2 orbital is zero..
x y
5. 3d6 configuration is more stable than 3d5.
Assertion-Reason
These questions contains, Statement I (assertion) and Statement II (reason).
(A) Statement-I is true, Statement-II is true ; Statement-II is correct explanation for Statement-I.
(B) Statement-I is true, Statement-II is true ; Statement-II is NOT a correct explanation for statement-I
(C) Statement-I is true, Statement-II is false
(D) Statement-I is false, Statement-II is true
NA N
6. Statement-I : 16 g each O2 and O3 contains and A atoms respectively..
2 3
Because
Statement-II : 16 g O2 and O3 contains same no. of atoms.
7. Statement-I : The average mass of one Mg atom is 24.305 amu, which is not the actual mass of one Mg atom.
Because
Statement-II : Three isotopes, 24Mg, 25Mg and 26Mg, of Mg are found in nature.
8. Statement-I : A molecule of butane, C4H10 has a mass of 58.12 amu.

Because
Statement-II : One mole of butane contains 6.022 × 10 23 molecules and has a mass of 58.12 g.
9. Statement-I : Both 12 g. of carbon and 27 g. of aluminium will have 6.02 × 1023 atoms.
Because
Statement-II : Gram atomic mass of an element contains Avogadro's number of atoms.
10. Statement-I : The ground state configuration of Cr is 3d5 4s1.

Because
Statement-II : A set of exactly half filled orbitals containing parallel spin arrangement provide extra
stability.
11. Statement-I : The electronic configuration of nitrogen atom is represented as :
not as
Because
Statement-II : The configuration of ground state of an atom is the one which has the greatest multiplicity.
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12. Statement-I : The configuration of B atom cannot be 1s 2 2s3.
Because
Statement-II : Hund's rule demands that the configuration should display maximum multiplicity.
13. Statement-1 : The groundstate configuration of Cr is [Ar] 3d 54s1

Statement-2 : The energy of atom is lesser in 3d5 4s1 configuration compared to 3d4 4s2 configuration.
14. Statement-1 :Minimum principal quantum number of an orbital belonging to 'g' sub-shell is 5.
Statement-2 : For a given value of principal quantum number (n), l may have values 0 to (n–1) only.
Single Choice Correct
15. 112.0 ml of NO2 at 1atm & 273 K was liquefied, the density of the liquid being 1.15 gm/ml. Calculate the
volume of and the number of molecules in the liquid NO2.
(A) 0.10 ml and 3.01 × 1022 (B) 0.20 ml and 3.01 × 1021
(C) 0.20 ml and 6.02 × 1023 (D) 0.40 ml and 6.02 × 1021
16. The shape of Tobacco Mosaic Virus (TMC) is cylindrical, having length and diameter 3000 Å and 170 Å,
respectively. The density of the virus is 0.08 gm/ml. The molecular weight of TMC is
(A) 3.28 (B) 5.44 × 10–24 (C) 5.44 × 10–18 (D) 3.28 × 106
17. What time, it would take to spend Avogadro’s number of rupees at the rate of 10 lac rupees per second?
(A) 6.023 × 1017 sec (B) 1.909 × 1010 year (C) 1.673 × 1014 hour (D) all of these
18. The sodium salt of methyl orange has 7% sodium. What is the minimum molecular weight of the compound?
(A) 420 (B) 375 (C) 329 (D) 295
19. In the preceding problem, if the compound contains 12.8% nitrogen 9.8% sulphur how many nitrogen and
sulphur atoms are present per atom of sodium :
(A) 2 and 1 (B) 1 and 3 (C) 1 and 2 (D) 3 and 1
20. Na2SO4. xH2O has 50% H2O. Hence, x is :

(A) 4 (B) 5 (C) 6 (D) 8
21. In the following final result is ....0.1 mol CH4 + 3.01 × 1023 molecules CH4 – 9.6 g CH4 = x mol H atoms :
(A) 0 mol H atom (B) 0.2 mol H atom (C) 0.3 mol H atom (D) 0.4 mol H atom
22. In a gaseous mixture an alkane (CxH2x+2) and an alkene (CyH2y) are taken in 2 : 1 mole ratios, the average
molecular weight of mixture is observed to be 20. If the same alkane and alkene are taken in 1 : 2 mole ratios,
the average molecular weight of mixture is observed to be 24. Then the value of ‘x’ and ‘y’ respectively are :
(A) 2, 1 (B) 1, 2 (C) 2, 3 (D) 3, 2
23. 3.06 L of H2O(vap) is taken at a pressure of 1 atm and 373 K. It is now condensed to H 2O (l) at 373K. Calculate
the volume occupied by H2O(l) (Density of liquid water = 1 g/ml)
(A) 3.06 L (B) 1.8 ml (C) 1.8 L (D) 3.06 ml
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Mole Concept
24. Nylon is prepared using a compound having formula HOOC(CH2)4COOH. What is the total number of atoms
present in 0.73 mg of the above compound :
(A) 6.023 × 1019 (B) 6.023 × 1022 (C) 60.23 × 1023 (D) 20
25. A substance has 16% by mass of Sulphur and 4% by mass of Oxygen. Calculate minimum molar mass of the
substance.
(A) 200 (B) 400 (C) 600 (D) 100
26. In an experiment, it is found that 2.0769 gm of pure X produces 3.6769 gm of pure X2O5. Then number of
moles of X is :
(A) 0.04 (B) 0.06 (C) 0.4 (D) 0.02
27. Two isotopes of an element ( atomic mass = x + 2.35) have mass (x + 2) and (x + 7) respectively. Calculate
natural abundance of heavier isotope in percentage.
(A) 3 (B) 5 (C) 7 (D) 9
28. Two elements A and B form two different sets of compounds A 2B3 and A3B4. 2.02 kg of A2B3 has 1.806 × 1025
atoms of B and 1.44 kg of A3B4 has 9.03 × 1024 atoms of A. What will be gram molecular mass (GMM) of
another compound AB formed from combination of A and B.
(A) 75 (B) 86 (C) 94 (D) 97
29. An element exist in three isotopic form 40X, 41X and 42X .
40
Percentage abundance of X = 30% by mole.
If average atomic mass of ‘X’ is 41.25. Find out percentage abundance of 41X.
[Divide your answer by 3 and fill OMR sheet]
(A) 2 (B) 3 (C) 5 (D) 7
30. A solution of palmitic acid (M =256) in benzene contains 5 gm acid per litre. When this solution is dropped on
surface, C6H6 gets evaporated and acid forms a unimolecular layer on the surface. If we wish to cover an area
6000 cm2 with unimolecular film. What volume of solution in ml should be used? Area covered by one molecule
of acid is 0.32 nm2. (Given : NA = 6 × 1023)
Write your answer multiplying with 1000.
(A) 120 ml (B) 140 ml (C) 160 ml (D) 180 ml
31. An element exist in two isotopic forms X120 and X122, in equal abundance. The average atomic mass of element
is 121.44. If each atom of X120 are 10.04 times heavier than one C12 atom, then how many times each atom
of X122 is heavier than one C12 atom ?
(A) 10.04 (B) 10.4 (C) 10.2 (D) 10.167
32. How many moles of e– weight one Kg : [JEE 2002]
1 6.023 1
(A) 6.023 × 1023 (B) ´ 1031 (C) ´ 1054 (D) ´ 108
9.108 9.108 9.108 ´ 6.023
33. Which has maximum number of atoms : [JEE 2003]

(A) 24 g C(12) (B) 56 g Fe(56) (C) 27 g Al (27) (D) 108 g Ag(108)
34. An alloy of gold and silver contains 38.5% silver by mass and has a density of 14.6 g.mL –1. What is the molar
concentration of silver in this alloy :
(A) 52.1 mol.L–1 (B) 45.6 mol.L–1 (C) 3.57 mol.L–1 (D) 2.64 mol.L–1
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35. "Suvarnabhasm", an ayurvedic drug, is found to contain 400 ppm of colloidal gold. Mass % of gold (atomic
mass of Au = 197) will be :
(A) 0.040 % (B) 7.88 % (C) 0.0788 % (D) 4 × 10–4 %
36. Which orbit would be the first to have 'g' subshell :-

(A) 3rd (B) 4th (C) 5th (D) 6th
37. The decreasing order of energy of the 3d, 4s, 3p, 3s orbitals is :-
(A) 3d > 3s > 4s > 3p (B) 3s > 4s > 3p > 3d (C) 3d > 4s > 3p > 3s (D) 4s > 3d > 3s > 3p
38. If n and l are respectively the principle and azimuthal quantum numbers, then the expression for calculating the
total number of electrons in any orbit is :-
l =n l =n -1 l =n +1 l =n -1
(A) å 2(2l + 1) (B) å 2(2l + 1) (C) å 2(2l + 1) (D) å 2(2l + 1)
l =1 l =1 l =0 l =0
39. The quantum numbers +1/2 and –1/2 for the electron spin represent :-
(A) Rotation of the electron in clockwise and anticlockwise direction respectively.
(B) Rotation of the electron in anticlockwise and clockwise direction respectively.
(C) Magnetic moment of the electron pointing up and down respectively.
(D) Two quantum mechanical spin states which have no classifical analogue.
40. What are the values of the orbital angular momentum of an electron in the orbitals 1s, 3s, 3d and 2p :-
(A) 0, 0, 6h, 2h (B) 1, 1, 4h, 2h (C) 0, 1, 6h, 3h (D) 0, 0, 20h, 6
41. If m = magnetic quantum number and l = azimuthal quantum number then :-
m -1
(A) m = l + 2 (B) m = 2l2 + 1 (C) l = (D) l = 2m + 1
2
4+
42. The number of unpaired electrons in Mn (Z = 25) is :-
(A) Four (B) Two (C) Five (D) Three
43. Which of the following has maximum number of unpaired electron (atomic number of Fe 26)
(A) Fe (B) Fe (II) (C) Fe (III) (D) Fe (IV)
44. Suppose a particle has four quantum numbers such that the permitted values are:
n = 1, 2, 3........
l = (n – 1), (n – 3), (n – 5) ...........but no negative value
æ 1ö æ 1ö
j = çè l + ÷ø or çè l - ÷ø , the later is not negative
2 2
m = –j in integer step to +j what are the other permitted values for n = 2?
3 3 1 1
(A) l = 1, j = ,m = - (B) l = 0, j = ;m = -
2 2 2 2
1 3
(C) l = 1, j = ;m = - (D) All of these
2 2
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Mole Concept
45. Which of the following is / are false.
(A) Multiplicity in Fe3+ is greater than Co3+.
(B) Ti3+, Cr+, Sc2+ ions are diamagnetic.
(C) Value of (n + l + m) for last electron in Na is 3.
(D) Number of neutron in 1.07 gm Fe(OH) 3 is 3.25 × 1023
46. The orbital diagram in which Hund’s rule is violated is
(I) (II)
(III) (IV)
(A) I & II (B) II & III (C) III & IV (D) II & IV
47. Match the column:

(‘l’ and ‘m’ are respectively the azimuthal and magnetic quantum numbers)
Column I Column II
(I) Total number of values of (l) for a shell (P) 0, 1, 2, .................(n–1)
(II) Values of (l) for a shell (Q) +l, .....+2, +1, 0, –1, –2, .......–l
(III) Total number of values of (m) for a subshell (R) (2l + 1)
(IV) Values of (m) for a subshell (S) n
(A) (I) S (II) P (III) R (IV) Q (B) (I) S (II) R (III) P (IV) Q
(C) (I) P (II) S (III) R (IV) Q (D) (I) P (II) R (III) Q (IV) S
48. Which of the following statements regarding subshell filling order for a neutral atom is/are correct ?
(I) Electrons are assigned to the 4s subshell before they are assigned to the 3d subshell
(II) Electrons are assigned to the 4f subshell before they are assigned to the 6s subshell
(III) Electrons are assigned to the 4d subshell before they are assigned to the 5p subshell
(A) I only (B) II only (C) I and III (D) I, II and III
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49. If the nitrogen atom had electronic configuration 1 s , it would have energy lower that of normal ground state
configuration 1s2 2s2 2p3, because the electrons would be closer to the nucleus. Yet 1 s 7 is not observed because
it violates :-
(A) Heisenberg uncertainty principle (B) Hunds rule
(C) Pauli's exclusion principle (D) Bohr postulate of stationary orbits
50. The explanation for the presence of three unpaired electrons in the nitrogen atom can be given by
(A) Pauli’s exclusion principle (B) Hund’s rule
(C) Aufbau’s principle (D) Uncertainity principle
51. Which of the following has the maximum number of unpaired electrons ? [JEE 1996]
(A) Mg2+ (B) Ti3+ (C) V3+ (D) Fe2+
52. After np orbitals are filled, the next orbital filled will be :-
(A) (n + 1) s (B) (n + 2) p (C) (n + 1) d (D) (n + 2) s
53. The value of the magnetic moment of a particular ion is 2.83 Bohr magneton. The ion is :-
(A) Fe2+ (B) Ni2+ (C) Mn2+ (D) Co3+
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54. The electrons, identified by n & l ; [JEE 1999]
(i) n = 4 , l = 1 (ii) n = 4 , l = 0 (iii) n = 3 , l = 2
(iv) n = 3 , l = 1 can be placed in order of increasing energy, from the lowest to highest as :
(A) (iv) < (ii) < (iii) < (i) (B) (iii) < (ii) < (iv) < (i)
(C) (i) < (iii) < (ii) < (iv) (D) (iii) < (i) < (iv) < (ii)
55. The magnetic moment of cobalt of the compund Hg[Co(SCN)4] is [Given : Co+2] [JEE 2004]
(A) 3 (B) 8 (C) 15 (D) 24
(A) 3 (B) 8 (C) 15 (D) 24
Multiple Choice Correct
57*. X gm A atoms on combining with Y atoms of B form 5 molecules of a compound containing A & B. Find the
molecular weight of compound formed. (Atomic weight of B = M)
(XN A + MY) X+M X + MY æ X + MYN A ö

(A) (B) (C) (D) ç ÷
5 5 5 è 5 ø
58. Calculate mass % & mole % of H2 in a mixture of H2 and O2 if average molecular mass of the mixture is 14.
(A) 50 % by mole (B) 60 % by mole (C) 8.57% by mass (D) 10% by mass
59*. Which of the following options is/are incorrect.

(A) 10 gm of Boron is having 5 mole of nucleons.
(B) One atom of an element weight 1.8 × 10–22 gm, then its atomic mass is 108.36
(C) 10 gm of CaCO3 contains 1 gm atom of C.
(D) Number of atoms in 2 moles of S8 is greater than 5.5 moles of SO2
60. A polymeric organic compound contains 0.07% iron and 0.035% nitrogen by mass. Which of the following
statement(s) is/are correct for the compound ? (Fe = 56, N = 14)
(A) The molecular mass of compound may be 40000.
(B) The molecular mass of compound may be 160000.
(C) In each molecule of this compound, there are 2 nitrogen atoms per iron atom.
(D) In each molecule of this compound, there are 2 iron atoms per nitrogen atom.
61. Which of the following have equal no. of atoms ?

(A) 12 g MgSO4 (B) 0.2 mole CO2 (C) 5.6 L SO2 at STP (D) 24 g Ca
200
62. A mixture of two gases H2 and O2 has an average molecular mass 12 and is kept at a temperature of K
3
and pressure 0.821 atm. Select the correct options :
100
(A) Mixture contains % by mass of H2 gas. (B) Density of mixture is 1.8 gm/ml.
9
100 1
(C) Mixture contains % by mol of O2 gas (D) Mole ratio of O2 and H2 gas in the mixture is
3 3
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Mole Concept
63. Which of the statements is / are true for a chemical reaction occurring in a closed container?
(A) Total mass of all reactants and products always remain constant.
(B) Average molecular mass of the mixture may change during chemical reaction.
(C) Total number of atoms of each element will remain constant in a chemical reaction.
(D) Total volume of all reactants and products always remain constant.
64. The magnitude of the spin angular momentum of an electron is given by -
h h 3 h 1 h
(A) S = s(s + 1) (B) S = s (C) S = ´ (D) S = ± ´
2p 2p 2 2p 2 2p
65. Gaseous state electronic configuration of nitrogen atom can be represented as : [JEE 1999]
(A) ¯ ¯ (B) ¯ ¯ ¯ (C) ¯ ¯ ¯ ¯ (D) ¯ ¯ ¯ ¯ ¯
66. The electronic configuration of an element is 1s2 2s2 2p6 3s2 3p6 3d5 4s1. This represents its : [JEE 2000]
(A) excited state (B) ground state (C) cationic form (D) none
Comprehension
Comprehension-1
Azurite is a copper containing mineral that is a mixture of Copper (II) carbonate and copper (II) hydroxide,
[CuCO3]X. [Cu(OH)2]y. If the mineral is 55.31% Cu, 0.58% H and 6.97% C, with the remainder oxygen, what are
x and y in the general formula ? [Cu = 63.5]
67. What is the value of ‘x’ in general empirical formula ?

(A) 7 (B) 2 (C) 3 (D) 4
68. What is the value of ‘y’ in the general empirical formula b?

(A) 1 (B) 2 (C) 3 (D) 4
69. If the value of x and y be 1 and 2 respectively. Calculate the % composition of Cu ?

(A) 50 % (B) 59.8% (C) 51.2% (D) 60%
Comprehension-2
Calcium lactate is used in the food and beverage industries. It has also been used medicinally for treatment of
various allergies, for treatment of muscular leg cramps, and as an antidote for a variety of poisons, including
lead, arsenicals and carbon tetrachloride. A 0.8274 g sample of anhydrous calcium lactate is found by analysis
to contain 0.2732 g of C, 0.0382 g H, 0.1520 g Ca and 0.3640 g O. Each mole of calcium lactate is found to
contain one mole of calcium ions. Calcium lactate can be crystallised from water as pentahydrate salt.
70. Simplest formula of the calcium lactate is :

(A) CaO6C6H10 (B) CaO3C3H5 (C) CaO2C3H3 (D) CaO2C3H5
71. Formula weight of calcium lactate is :

(A) 129 g mol–1 (B) 111 g mol–1 (C) 218 g mol–1 (D) 113 g mol–1
72. How many grams of calcium lactate pentahydrate would be recovered from 1 g of anhydrous salt :
(A) 1.41 g (B) 1.00 g (C) 1.27 g (D) 1.51 g
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Comprehension-3
Read the following rules and answer the questions at the end of it.
Electrons in various suborbits of an orbit are filled in increasing order to their energies.
Pairing of electrons in various orbitals of a suborbit takes place only after each orbital is half-filled.
No two electrons in an atom can have the same set of quantum number.
73. Cr (Z = 24), Mn+ (Z = 25), Fe2+ (Z = 26) and Co3+ (Z = 27) are isoelectronic each having 24 electrons.
Thus,
(A) all have configurations as [Ar] 4s1 3d5
(B) Cr and Mn+ have configurations as [Ar] 4s1 3d5 while Fe2+ and Co3+ have configurations as [Ar]3d6.
(C) all have configurations as [Ar] 3d6
(D) all have configurations as [Ar] 4s2 3d6
74. A compound of vanadium has a magnetic moment of 1.73 BM. Electronic configuration of the vanadium ion
in the compound is :
(A) [Ar] 4s0 3d1 (B) [Ar] 4s2 3d3 (C) [Ar] 4s1 3d0 (D) [Ar] 4s0 3d5
75. Which of these ions are expected to be paramagnetic and coloured in aqueous solution ?
(A) Fe3+, Ti3+, Co3+ (B) Cu+, Ti4+, Sc3+ (C) Fe3+, Ni2+, V5+ (D) Cu+, Cu2+, Fe2+
76. While writing the following electronic configuration of Fe some rules have been violated :
I : Aufbau rule, II : Hund's rule III : Pauli's exclusion principle
Ar ¯
3d 4s
(A) I, II (B) II, III (C) I, III (D) III
77. How many elements would be in the second period of the periodic table if the spin quantum number (ms) could
1 1
have the value of - ,0, + ?
2 2
(A) 8 (B) 10 (C) 12 (D) 18
78. The sub-shell that arises after f sub-shell is called g sub-shell.

(A) it contains 18 electrons and 9 orbitals
(B) it corresponds to l = 4 and first occurs in 5th energy level
(C) a g-orbital can have maximum of two electrons
(D) all the above statements are true.
Subjetive Questions
79. A crystalline hydrated salt on being rendered anhydrous, loses 45.6% of its weight. The percentage composition
of anhydrous salt is : Al = 10.5%, K = 15.1%, S = 24.8% and O = 49.6%. Find the empirical formula of the
anhydrous and crystalline salt :
80. Two elements C and D combine to form two compounds CxDy & CyDx. 0.5 mole of CyDx weigh 40 gm & 1
molecule of CxDy weigh 1.66 × 10–25 kg. The atomic weight of C and D are 20 & 40 respectively. 'x' & 'y' are
respectively.
81. On a reference scale of C, at. weight of Al is 26.98 of Titanium is 47.48. What would be at. weight of Al on a
new reference scale where Titanium has a value of 48.
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Mole Concept
82. Three isotopes of an element have mass numbers M, (M+1) and (M+2). If the mean mass number is (M + 0.5),
then the ratio of number may be accepted for M, (M+1) and (M+2) in the order
83. 0.36 gm of a triatomic gas, X3, occupies 168 ml at 1 atm & 273 K. The atomic weight of X is
84. A mother cell disintegrate into sixty identical cells and each daughter cell further disintegrate into 24 smaller
cells. The smallest cells are uniform cylindrical in shape with diameter of 120 Å and each cell is 6000 Å long.
Determine molar mass of the mother cell if density of the smallest cell is 1.12 g/cm3 :
85. Instead of principal quantum number (n), azimuthal quantum number (l) & magnetic quantum number m, a set
of new quantum numbers s, t and u was introduced with similar logic but different values as defined below.
s = 1, 2, 3, ........¥ all positive integral values.
t = (s2 – 12), (s2 – 22), (s2 – 32) ........ No negative value
(t + 1) (t + 1)
u=- to + (including zero, if any) in integral steps.
2 2
Each orbital can have maximum four electrons.
(s + t) rule is defined, similar to (n + l) rule.
(i) Number of electrons that can be accommodated in s = 2 and s = 3 shell.
(ii) Number of electrons for which s = 2, t = 3 for an element with atomic number 24.
(iii) The number of subshells in which the third shell is subdivided equal to
86. If for any electron in an orbital another parameter ‘B’ is defined as

B = n + l + m, where n, l, m are the quantum numbers of that orbital then what will be the maximum value
of B for the last electron of 35Br.
87. In case of nitrogen, if M1 represents spin multiplicity if Hund’s rule is followed and M 2 represents spin multiplicity
M1
if only Hund’s Rule is violated then the value of M will be:
2
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ANSWERS
1. (1) 2. 32 3. 14
l True and False

4. False 5. False
6. (D) 7. (A) 8. (A) 9. (A) 10. (A)

11. (A) 12. (B) 13. (A) 14. (A)
15. (B) 16. (D) 17. (D) 18. (C) 19. (D)
20. (A) 21. (A) 22. (B) 23. (B) 24. (A)
25. (B) 26. (A) 27. (C) 28. (B) 29. (C)
30. (C) 31. (C) 32. (D) 33. (A) 34. (A)
35. (A) 36. (C) 37. (C) 38. (D) 39. (D)
40. (A) 41. (C) 42. (D) 43. (C) 44. (A)
45. (B) 46. (C) 47. (A) 48. (C) 49. (C)
50. (B) 51. (D) 52. (C) 53. (D) 54. (A)
55. (C) 56. (C)
57. (A) 58. (BC) 59. (ACD) 60. (BC) 61. (ABD)
62. (AC) 63. (ABC) 64. (AC) 65. (AD) 66. (BC)
l Comprehension
Comprehension 1 : 67. (B) 68. (A) 69. (B)

Comprehension 2 : 70. (A) 71. (C) 72. (A)
Comprehension 3 : 73. (B) 74. (A) 75. (A)
76. (D) 77. (C) 78. (D)
79. KAlS2O8 , KAlS2O8.12 H2O 80. x=1 y=2 81. 27.04
82. 4:1:1 83. 16 84. 6.6 × 1010 g
85. (i) 28, 76 ; (ii) (0) ; (iii) (3) 86. (6) 87. (2)
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Rankers Academy JEE
Periodic Table
PERIODIC TABLE
True/False
1. Al2O3 is an amphoteric oxide.
2. Third group of periodic table accommodates maximum number of elements.
3. First ionisation potential of Mg is higher than that of Al.
4. The electronic configuration of an element is 1s2 2s2 2p6 3s2 3p6 3d5 4s1. This represents its ground state
configuration.
5. Successive ionisation potentials are lower.
6. The alkali metals show increasing electronegativities from Li to Cs.
7. In group I of alkali metals, the ionization potential decreases down the group. Therefore lithium is a poor
reducing agent in gaseous state.
8. The decreasing order of electron affinity of F, Cl, Br is F > Cl > Br
Fill in the blanks

9. Most electropositive elements belong to ............................... group.
10. Most electronegative elements belong to ............................... group.
11. Transition elements are characterised by ............................... valency.
12. The second ionisation energy of calcium is ............................... than the ............................... ionisation
energy of calcium.
13. The electronegativity of the elements C, N. Si and P increases in the order of ...............................
14. Total number of inner transition elements are .............................. .
15. Two elements of equal electronegative values they form ............................... bond.
16. Among Na, Mg, Al & Si elements ............................... element has zero electron affinity.
17. Elements of group ............................... have greater tendency to form positive ions than elements of group
IIA.
18. In aqueous solution ............................ is the best reducing agent among the alkali metals.
19. Ca2+ has a smaller ionic radius than K+ because it has ...............................
20. Compounds that formally contain Pb4+ are easily reduced to Pb2+. The stability of the lower oxidation state is
due to ...............................
Assertion-Reason
(D) Statement-I is false, Statement-II is false.
21. Statement -1 : Two successive ionisation energies of Argon are 56.8 eV and 36.8 eV respectively.
because
Statement -2 : Zeff of Ar (3s23p6) is greater than Ar+ (3s23p5).
22. Statement -1 : Electron affinity of fluorine is greater than chlorine.

because
Statement -2 : Ionisation potential of fluorine is less than chlorine.
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JEE-Chemistr y
23. Statement -1 : Size of anion is larger than their parent atom.
because
Statement -2 : Zeff of anion is greater than that of their parent atom.
24. Statement -1 : Atomic radius of inert gases is largest in the period

because
Statement -2 : Effective nuclear charge of inert gases is minimum
25. Statement -1 : 2nd IP of alkali metals is maximum in the period.

because
Statement -2 : Alkali metals has smallest atomic size in the period.
26. Statement -1 : First ionization energy of nitrogen is lower than oxygen.

because
Statement -2 : Across the period effective nuclear charge decreases.
27. Statement -1 : The third period contains only 8 elements and not 18 like 4th period.
because
Statement -2 : In III period filling starts from 3s1 and complete at 3p6 whereas in IV period it starts from
4s1 and complete after 3d10 and 4s2.
28. An element with atomic number 106 has been discovered recently. Which of the following electronic configuration
will it posses :-
(A) [Rn] 5f14 6d5 7s1 (B) [Rn] 5f14 6d5 7s2 (C) [Rn] 5f14 6d6 7s0 (D) [Rn] 5f14 6d1 7s2 7p3
29*. Correct order of ionic radii is :-

(A) Ti4+ < Mn7+ (B) 37Cl– < 35Cl– (C) K+ > Cl– (D) P3+ > P5+
30. The correct order of stability of Al+, Al+2, Al+3 is :-

(A) Al+3 > Al+2 > Al+ (B) Al+2 > Al+3 > Al+
(C) Al+2 < Al+ > Al+3 (D) Al+3 > Al+ > Al+2
31. Which of the following general electronic configuration for transition elements is not correct :-
(A) (n + 1) s1–2 nd1–10 (B) ns1–2 (n – 1)d1 – 10(Where n = 2, 3, 4 .......)
(C) ns0,1,2
(n –1)s p d
2 6 1–10
(D) (n – 1)d1–10 ns0–2
32. Which of the following decreases in going down the halogen group :-
(A) Ionic radius (B) Atomic radius (C) Ionisation potential (D) Boiling point
33. Which of the following has 2nd IP < Ist IP

(A) Mg (B) Ne (C) C (D) None
34. The correct order of decreasing first ionization energy is :-

(A) Si > Al > Mg > Na (B) Si > Mg > Al > Na
(C) Al > Si > Mg > Na (D) Mg > Li > Al > Si
35. The electron affinity

(A) Of carbon is greater than oxygen (B) Of fluorine is less than iodine
(C) Of Cl– is less than Cl (D) Of S is less than oxygen
36. Which will have the maximum value of electron affinity Ox, Oy and Oz [x, y and z respectively are
0, – 1 and – 2] :–
(A) Ox (B) Oy (C) Oz (D) All have equal
37. If the atomic number of an element is 58, it will be placed in the periodic table in the -
(A) III B gp and 6th period (B) IV B gp and 6th period
th
(C) VB gp and 7 period (D) None of the above
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Rankers Academy JEE
Periodic Table
38. Which of the following ion has largest size :-
(A) F– (B) Al+3 (C) Cs+ (D) O–2
39. 1 2 3 4
H3C – CH = C = CH2
In the given compound which carbon atom will show maximum electronegativity -
(A) Fourth (B) First
(C) Third (D) EN of all the carbon atoms is same
40. (a) M–(g) ® M(g) (b) M(g) ® M+(g) (c) M+(g) ® M+2(g) (d) M+2(g) ® M+3(g)
Minimum and maximum I.P. would be of :-
(A) a, d (B) b, c (C) c, d (D) d, a
41*. Which is correct order of size of O, O2–, F– and F :-

(A) O2– > O > F– > F (B) O > O2– > F > F–
2– –
(C) O > F > F > O (D) O2– > F– > O > F
42. The right order of ionization potential of Li, Be, B & C is :

(A) C > Be > B > Li (B) C > B > Be > Li (C) C > B > Li > Be (D) B > C > Be > Li
43*. The correct order of second ionization potential of C, N, O and F is

(A) C > N > O > F (B) O > N > F > C (C) O > F > N > C (D) F > O > N > C
44. The correct sequence of the electron affinity of C, N, O and F is :

(A) C > N < O < F (B) O > N > C > F (C) C < N > O < F (D) C > N > O > F
45. The decreasing order of the ionization potential of the following elements is :
(A) Ne > Cl > P > S > Al > Mg (B) Ne > Cl > P > S > Mg > Al
(C) Ne > Cl > S > P > Mg > Al (D) Ne > Cl > S > P > Al > Mg
46. One element has atomic weight 39. Its electronic configuration is 1s2, 2s2 2p6, 3s2 3p6 4s1. The true statement
for that element is :
(A) More (IE) (B) Transition element (C) Isotone with 18Ar36. (D) Stable oxide M2O
47*. Is a data sufficiency problem in which it is to be decided on the basis of given statements whether the given
question can be answered or not. (No matter whether the answer is yes or no)
If DHsolution < 0 then compound acts as ionic in aqueous solution. Is AlCl3(s) ionic in aqueous solution.
Statement 1 : L.E. of AlCl3 is 5137 kJ/mol
Statement 2 : DHHE of Al+3 ion is – 4665 kJ/mol–1 & DHHE of Cl– is –381 kJ/mol–1
(A) Statments (A) alone is sufficient but statement (B) is not sufficient
(B) Statments (B) alone is sufficient but statement (A) is not sufficient
(C) Both statement together are sufficient but neither statement alone is sufficient
(D) Statement (A) & (B) together are not sufficient
48. Match List I with List II and select the correct answer using the codes given below :
List I List II
2 2 6 2 6
A. 1s , 2s 2p , 3s 3p , 4s 2 1. In
B. 1s2, 2s2 2p6, 3s2 3p6 3p6 3d10, 4s1 2. Pd
C. 1s2, 2s2 2p6, 3s2 3p6 3d10, 4s2 4p6 4d10 3. Ca
D. 1s2, 2s2 2p6, 3d10, 4s2 4p6 4d10, 5s2 5p1 4. Cu
Code : A B C D
(A) 1 2 3 4
(B) 1 3 2 4
(C) 3 4 2 1
(D) 1 4 3 2
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Rankers Academy JEE
JEE-Chemistr y
49. Match List I (Atomic Number of Element) with List II (Block to which the Element Belongs) and select the correct
answer using the codes given below :
List I List II
(Atomic Number of Element) (Block to which the element belongs)
A. 24 1. p
B. 38 2. f
C. 49 3. s
D. 59 4. d
Code : A B C D
(A) 2 1 3 4
(B) 4 3 1 2
(C) 2 3 1 4
(D) 4 1 3 2
50. The first ionization potentials (eV) of Be and B respectively are :
(A) 8.29eV, 9.32 eV (B) 9.32 eV, 9.32 eV (C) 8.29 eV, 8.29 eV (D) 9.32 eV, 8.29 eV
51*. If there were 10 periods in the periodic table then how many elements would this period can maximum comprise
of.
(A) 50 (B) 72 (C) 32 (D) 98
52. If each orbital can hold a maximum of three electrons, the number of elements in 9th period of periodic table
(long form) are :
(A) 48 (B) 162 (C) 50 (D) 75
53*. The electronic configuration of an element is 1s2 2s2 2p6 3s2 3p4. The atomic number and the group number of
the element ‘X’ which is just below the above element in the periodic table are respectively.
(A) 24 & 6 (B) 24 & 15 (C) 34 & 16 (D) 34 & 8
54. Alkaline earth metals always form dipositive ions due to

(A) IE2 – IE1 > 10 eV (B) IE2 – IE1 = 17 eV
(C) IE2 – IE1 < 10 eV (D) None of these
55. The correct order of second I.P.

(A) Na < Mg > Al < Si (B) Na > Mg < Al > Si
(C) Na > Mg > Al < Si (D) Na > Mg > Al > Si
56*. Two elements A & B are such that B.E. of A–A, B–B & A–B are respecitvely 81 Kcal/mole, 64Kcal/mole, 76
kcal/mole & electronegativity of B is 2.4 then the electronic configuration of A is, (if XB > XA )
(A) 1s2 2s2 2p1 (B) [Ne] 3s2 3p1 (C) [He] 2s2 2p4 (D) [Ne] 3s2 3p5
57. Moving from right to left in a periodic table, the atomic size is: [JEE 1995]
(A) increased (B) decreased (C) remains constant (D) none of these
58. The increasing order of electronegativity in the following elements: [JEE 1995]
(A) C, N, Si, P (B) N, Si, C, P (C) Si, P, C, N (D) P, Si, N, C
59. One element has atomic weight 39. Its electronic configuration is 1s2, 2s2 2p6, 3s2 3p6 4s1. The true statement for
that element is: [JEE 1995]
(A) High value of IE (B) Transition element
(C) Isotone with 18Ar38 (D) None
60. The number of paired electrons in oxygen atom is: [JEE 1995]
(A) 6 (B) 16 (C) 8 (D) 32
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Rankers Academy JEE
Periodic Table
61. The decreasing size of K+, Ca2+, Cl– & S2– follows the order: [JEE 1995]
(A) K+ > Ca +2 > S–2 > Cl– (B) K+ > Ca +2 > Cl– > S–2
(C) Ca >K > Cl > S
+2 + – –2
(D) S–2 > Cl– > K+ > Ca+2
62. Which of the following has the maximum number of unpaired electrons [JEE 1996]
(A) Mg2+ (B) Ti3+ (C) V3+ (D) Fe2+
63. The incorrect statement among the following is: [JEE 1997]
(A) the first ionisation potential of Al is less then the first ionisation potential of Mg
(B) the second ionisation potential of Mg is greater then the second ionisation potential of Na
(C) the first ionisation potential of Na is less then the first ionisation potential of Mg
(D) the third ionisation potential of Mg is greater then the third ionisation potential of Al

(i) n = 4 , l = 1
(ii) n = 4 , l = 0
(iii) n = 3 , l = 2
(A) (iv) < (ii) < (iii) < (i) (B) (iii) < (ii) < (iv) < (i)
(C) (i) < (iii) < (ii) < (iv) (D) (iii) < (i) < (iv) < (ii)

65. Ionization energy of an element is :
(A) Equal in magnitude but opposite in sign to the electron gain enthalpy of the cation of the element
(B) Same as electron affinity of the element
(C) Energy required to remove one valence electron from an isolated gaseous atom in its ground state
(D) Equal in magnitude but opposite in sign to the electron gain enthalpy of the anion of the element
66. Which one of the following statement (s) is (are) correct? [JEE 1998]
(A) The electronic configuration of Cr is [Ar] 3d 5 4s1.(Atomic No. of Cr = 24)
(B) The magnetic quantum number may have a negative value
(C) In silver atom, 23 electrons have a spin of one type and 24 of the opposite type. ( Atomic No. of Ag = 47)
(D) The oxidation state of nitrogen in HN 3 is –3.
67*. If Aufbau’s principle and Hund’s rule were not followed.

(A) K would have been d–block element & paramagnetic.
(B) Cu would have been s–block element.
(C) Cr would have been diamagnetic
(D) Fe+3 ion would have 5 unpaired electrons.
68*. Which of the following pair have nearly the same atomic radii
(A) Al and Ga (B) Fe and Ni (C) Zr and Hf (D) Pt & Pd
69*. Which of the following is false -

(A) Cr2+ (g) ion has greater magnetic moment compared to Co 3+ (g)
(B) The magnitude of ionization potential of iron anion (monoanion) would be equal to electron gain enthalpy
of iron.
(C) Lanthanide contraction is cause of lower I.P. of Pb than Sn
(D) If successive ionization energy are 332, 738, 849, 4080, 4958 (in kJ/mol). Then this element can be of 15th group
Comprehension Type
Pauling gave method to calculate univalent ion radii by assuming that
(i) In ionic crystal (let M+X¯ ) cations and anions are is contact of each other and sum of their radii is equal
to interionic distance, i.e.
d( M+ —X ¯) = r + + r -
M X
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Rankers Academy JEE
JEE-Chemistr y
(ii) The radius of an ion having noble gas configuration is inversely proportional to the effective nuclear
C C
charge felt at the periphery of the ion, i.e. r( M + ) = and ( X ¯) = Z
r
Z eff .( M + ) eff . ( X ¯)
Here C is constant of proportionality whose value depends on electronic configuration of ion.

Thus,
C C
d (M + - X ¯) = + pm
Z eff .( M + ) Zeff . ( X ¯)
Zeff. is the effective nuclear charge whose value can be calculated by the formula : Zeff.= Z – s. Here s is
shielding constant and for neon, the value of s when calculated by Slater’s rule, is found to be 4.5.
70*. The value of constant C for NaF crystals is [given that interionic distance of NaF = 231 pm] :
(A) 231 (B) 115.5 (C) 614.5 (D) 307.25
71*. The value of univalent radii for F¯ as calculated by Pauling method is (given that interionic distance of NaF =
231 pm) :
(A) 94.5 pm (B) 136.5 pm (C) 111.68 pm (D) 115.5 pm
72*. The value of ‘C’ for Na+, Mg2+ and Al3+ will be in the order :
(A) Al3+ > Mg2+ > Na+ (B) Al3+ < Mg2+ < Na+
(C) Al3+ = Mg2+ = Na+ (D) Can’t be compared.
Subjetive Questions
73*. Li+, Mg2+, K+,Al3+ (Arrange in increasing order of radii) [JEE 1997]
74. The ionic radii of S2– and Te2– are 1.84 and 2.2 Å respectively. What would you predict for the ionic radius of
Se2–.
75. How many chlorine atoms will be ionised (Cl ® Cl + + e – ) by the energy released from the process Cl
+ e– ® Cl– for 6.023 × 1023 atom (IP for Cl = 1250 kj mole–1 and EA = 350 KJ mole–1)
76. Na and Mg+ have same number of electrons. But removal of electron from Mg+ requires more energy. Explain.
77. Based on location in P.T., which of the following would you expect to be acidic & which basic.
(A) CsOH (B) IOH (C) Sr(OH2) (D) Se(OH)2
(E) FrOH (F) BrOH
78. From among the elements, choose the following : Cl, Br, F, Al, C, Li, Cs & Xe.
(i) The element with highest electron affinity.
(ii) The element with lowest ionisation potential.
(iii) The element whose oxide is amphoteric.
(iv) The element which has smallest radii.
(v) The element whose atom has 8 electrons in the outermost shell.
79*. For the gaseous reaction,

K + F ¾¾® K+ F–, DH was calculated to be 19 kcal per mole under conditions where the cations and anions
were prevented by electrostatic separation from combining with each other. The ionisation potential of K is 4.3
eV atom. What is the electron affinity of F ?
80*. Total number of enthalpy(s) (out of given nine) of A(g) which is/are not associated with conversion of
A(g)– ¾® A (g)+4 :
IE1, IE2, IE3, IE4, IE5, IE6, EGE1, EGE2
(IE = ionization energy, EGE = electron gain enthalpy)
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Rankers Academy JEE
Periodic Table
nd
81*. Write the number of pairs in which size of first element or ion is higher as compare to II out of following
nine pairs.
(O,S) , (He, Ne) , (Kr, Ne), (Na, Na+), (Cl, Cl–), (I– , Cl–), (LiAq.+ , NaAq.+ ), (Li, Na), (Li+ , Na+)
82*. Calculate E.N. of chlorine atom on Pauling scale if I.E. of Cl– is 4eV & of E.A. of Cl+ is + 13.0 eV.
83*. Calculate the E.N. of Cl from the bond energy of ClF (61 KCal/mol). Given that bond energies of F2 and Cl2 are
38 and 58 KCal/mol respectively.Given : Electronegativity of F = 4.
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Rankers Academy JEE
JEE-Chemistr y
ANSWERS
l True and False
1. True 2. True 3. True 4. True 5. False
6. False 7. True 8. False

9. IA group /1 10. VIIA/17 11. Variable
12. higher, first 13. Si, P, C, N 14. 28
15. (non polar) covalent 16. Mg 17. IA
18. Lithium 19. IA 20. IA
21. (D) 22. (D) 23. (C) 24. (C) 25. (C)
26. (D) 27. (A)
28. (A) 29. (D) 30. (A) 31. (D) 32. (C)
33. (D) 34. (B) 35. (C) 36. (A) 37. (A)
38. (C) 39. (C) 40. (A) 41. (D) 42. (A)
43. (C) 44. (A) 45. (B) 46. (D) 47. (C)
48. (C) 49. (B) 50. (D) 51. (B) 52. (D)
53. (C) 54. (C) 55. (B) 56. (A) 57. (A)
58. (C) 59. (C) 60. (A) 61. (D) 62. (D)
63. (B) 64. (A)
65. (AC) 66. (ABC) 67. (ABC) 68. (ABCD) 69. (ACD)
l Comprehension
70. (C) 71. (B) 72. (D)
73. Al3+ < Mg2+ < Li+ < K+
74. Ionic radius of Se2– is expected to be in between the ionic radii of S2– and Te2–. Thus
1.84 + 2.21
Ionic radius of Se2– = = 2.025 Å
2
75. Since 1250 kJ mole–1 energy is required to ionise 6.023 × 10 23 atoms. But 350 kJ mol–1 energy is released
6.023 ´ 10 23 ´ 350 kJ mole-1
hence the no. of ionised atoms – = = 1.686 × 1023
1250 kJ mole-1
76. Mg+ has more Zeff.

77. (A) Basic, (B) Acidic, (C), Basic, (D) Acidic, (E) Basic, (F) Acidic.
78. (i) Cl, (ii) Cs, (iii) Al, (iv) F, (v) Xe. 79. 3.476 ev.
80. (3) ; I.E5 , I.E6 , EGE2 not involved.
81. (4) ; Size of first is greater as compared to second for following :

(Kr, Ne) , (Na, Na+), (I–, Cl–), (Li+(aq), Na+(aq))
82. 3.03 (Pauling) 83. 3.2
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Rankers Academy JEE
Chemical Bonding
CHEMICAL BONDING
True/False
1. The polarising power of a cation is directly proportional to its size.
2. The polarisability of an anion is directly proportional to its charge.
3. Ionic interactions are directional.
4. All molecules having polar bonds are polar.
5. The net dipole in the water molecules is the resultant of its bond dipoles.
6. SO2 is polar whereas CO2 is non-polar.
7. If all bonds in a molecule are polar, the molecule as a whole must be polar.
8. The bond angle around B in BCl3 and BF3 is same.
9*. Dipole moment of NF3 is less than that of NH3.
10. In ionic bond formation octet is completed.
11. Normally the covalent bond is non-directional.
12. O2, O2– and O2+ all are paramagnetic.
13. When bond order increases, bond length decreases.
14. SF6 molecule is octahedral.
15. Ethyne is a linear molecule.
16. CO2 is a polar molecule but not have polar bond.
17. C–C sigma bond in ethyne is sp2 –sp2.
18. XeF4 molecule is square planar in shape.
19. The bond angle in Cl2O is equal to that of OF2.
20. HCl is a gas while HF is high boiling point liquid because H–F bond is stronger.
21*. Liquid NH3 does not contain H–bond.
22. Odd electron molecule is paramagnetic.
23. During the formation of covalent bond both shared electron having opposite spin.
24*. The solubility of ionic solids decreases when hydration energy of ions increases.
25. Between layers of graphite, bond will be covalent.
26*. The polarising power of Zn2+ is greater than Ca2+ ions.
27. The colour of PbI2 is yellow. The reason for this is large size of Pb+2 ion.
28. The H – N – H bond angle in NH3 is greater than H – As – H bond angle in AsH3.
29. The dipole moment of CH3F is greater than that of CH3Cl.

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Rankers Academy JEE
JEE-Chemistry
Fill in the blanks
30. Hydrogen bond energy is around ...................... .
31. The valence atomic orbitals on carbon in silver acetylide are ...................... hybridised.
32. The hybridisation state of oxygen in water molecule is ...................... .
33. When N2 goes to N2+, then N–N bond distance ...................... and when O2 goes to O2+, then O–O bond
distance ...................... .
34. Among N2O, SO2, I3+ and I3– , the linear species are ...................... and ...................... .
Assertion-Reason
These questions contains, Statement-I (assertion) and Statement-II (reason).
(A) Statement-I is True, Statement-II is True ; Statement-II is a correct explanation for Statement-I
(B) Statement-I is True, Statement-II is True ; Statement-II is NOT a correct explanation for Statement-I
(C) Statement-I is True, Statement-II is False.
(D) Statement-I is False, Statement-II is True.
35*. Statement-I : SF6 exists but SH6 does not.

Because
Statement-II : dp-pp bonding cannot take place in SH6
36*. Statement-I : The first ionization energy of Be is greater than that of B.

Because
Statement-II : The 2p orbital is lower in energy than the 2s.
37*. Statement-I : CO2 is non polar while SO2 is polar molecule.

Because
Statement-II : S-O bonds are polar while C-O non polar.
39. Statement-I : N2O, CO2 & I3– are isostructral.

Because
Statement-II : All three have same hybridised central atom.
41*. Statement-I : Al(OH)3 is amphoteric in nature.

Because
Statement-II : Al–O and O–H bonds can be broken with equal ease in Al(OH)3.
42*. Statement-I : Boron does not show univalent nature but unipositive nature of thallium is quite stable.
Because
Statement-II : Inert pair effect predominates in thallium.
43*. Statement-I : H3BO3 is monobasic acid in water.

Because

Statement-II : In water ionise as H3BO3 H2BO3 + H .
– +
46. Statement-I : Bond order of O2 and BN is same.

Because
Statement-II : O2 and BN are isoelectronic
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Rankers Academy JEE
Chemical Bonding
47. Statement-I : In NF3 molecule lone pair resides in sp3 hybrid orbital.
Because
Statement-II : NF3 has pyramidal shape.
48. Statement-I : Super oxide ion is paramagnetic whereas peroxide ion is diamagnetic.
Because
Statement-II : Super oxide ion has one unpaired electron whereas per oxide ion has no unpaired electron.
49*. Statement-I : Although PF5, PCl5 and PBr5 are known, the penta halide of nitrogen have not been observed.
Because
Statement-II : Phosphorus has lower electronegativity than nitrogen.
50. Statement-I : HNO3 is a stronger acid than HNO2.

Because
Statement-II : In HNO3, there are two N–O linkage whereas in HNO2 there is only one.
51. Statement-I : H2SO4 in more viscous than water.

Because
Statement-II : In H2SO4, S has highest oxidation state.
52*. Statement-I : F3– ion is known, which has same geometry as X3– (X = Cl, Br, I)
Because
Statement-II : F is most electronegative element.
53. Which of the following Lewis dot diagrams is(are) incorrect ?
Cl
·· ··
·
(A) Na - O - C l · (B) Cl C Cl
·· ··
Cl
+
é H ù H H
ê | ú | |
(C) 2 ê H - N - H ú (D) H - N - N - H
ê | ú ·· ··
êë H úû
54. The valency of sulphur in sulphuric acid is :

(A) 2 (B) 8 (C) 4 (D) 6
55*. Which of the following has been arranged in increasing order of size of the hybrid orbitals ?
(A) sp < sp 2 < sp 3 (B) sp 3 < sp 2 < sp (C) sp 2 < sp 3 < sp (D) sp 2 < sp < sp 3
58*. For H 2O2 , H 2 S , H 2 O and HF , the correct order of decreasing strength of hydrogen bonding is :
(A) H 2O > HF > H 2 O2 > H 2 S (B) HF > H2O2 > H2O > H2S
(C) HF > H 2 O > H 2 O2 > H 2 S (D) H 2O2 > H 2 O > HF > H 2 S
59. Which one of the following does not have intermolecular H-bonding?
(A) H2O (B) o-nitro phenol (C) HF (D) CH3COOH
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Rankers Academy JEE
JEE-Chemistry
60. The order of strength of hydrogen bonds is:
(A) ClH ...Cl > NH ... N > OH ...O > FH ... F (B) ClH ...Cl < NH ... N < OH ...O < FH ...F
(C) ClH ...Cl < NH ...N > OH ...O > FH ...F (D) ClH ...Cl < NH ...N < OH ...O > FH ...F
61. The pairs of bases in DNA are held together by :

(A) Hydrogen bonds (B) Ionic bonds (C) Phosphate groups (D) Deoxyribose groups
62. The geometry & the type of hybrid orbitals present about the central atom in BF3 is : [JEE '98]
(A) linear, sp (B) trigonal planar, sp2 (C) tetrahedral sp3 (D) pyramidal, sp3
63. The correct order of increasing C - O bond length of, CO, CO32- , CO2 is [JEE '99]
(A) CO3 < CO2 < CO (B) CO2 < CO3 < CO (C) CO < CO3 < CO2 (D) CO < CO2 < CO32-
2- 2- 2-
64. The geometry of H2S and its dipole moment are [JEE '99]
(A) angular & non zero (B) angular & zero (C) linear & non zero (D) linear & zero
65. In compounds type E Cl3, where E = B, P, As or Bi, the angles Cl - E - Cl for different E are in the order
[JEE '99]
(A) B > P = As = Bi (B) B > P > As > Bi (C) B < P = As = Bi (D) B < P < As < Bi
66. The most likely representation of resonance structure of p–nitrophenoxide is: [JEE '99]
(A) (B) (C) (D)
68. The hybridization of atomic orbitals of nitrogen in NO +2 , NO 3- and NH +4 aree [JEE 2000]
(A) sp2, sp3 and sp2 respectively (B) sp, sp2 and sp3 respectively
(C) sp2, sp and sp3 respectively (D) sp2, sp3 and sp respectively
70. Specify hybridization of N and B atoms in a 1 : 1 complex of BF 3 and NH3 [JEE 2002]
(A) N : tetrahedral, sp3 ; B : tetrahedral, sp3 (B) N : pyramidal, sp3; B : pyramidal, sp3
(C) N : pyramidal, sp3 ; B : planar, sp2 (D) N : pyramidal, sp3; B : tetrahedral, sp3
71. The nodal plane in the p-bond of ethene is located in [JEE 2002]
(A) the molecular plane
(B) a plane parallel to the molecular plane
(C) a plane perpendicular to the molecular plane which bisects, the carbon-carbon s bond at right angle.
(D) a plane perpendicular to the molecular plane which contains, the carbon-carbon bond.
- 2- -
72. Which of the following are isoelectronic and isostructural ? NO 3 , CO 3 , ClO 3 , SO3 [JEE 2003]
- 2- - 2- 2-
(A) NO 3 , CO 3 (B) SO3, NO 3- (C) ClO 3 , CO 3 (D) CO3 , SO3
73. Which species has the maximum number of lone pair of electrons on the central atom? [JEE 2005]
(A) ClO3 – (B) XeF4 (C) SF4 (D) I3 –
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Rankers Academy JEE
Chemical Bonding
74. Atoms combine so that,

(A) They can always attain stable configuration to that of nearest nobel gas.
(B) They can attain stable configuration if possible, to that of nearest nobel gas.
(C) Their potential energy can increase and hence bond energy may increase.
(D) Their potential energy can decrease and hence bond energy may increase.
75. Most ionic compounds have :

(A) high melting points and low boiling points
(B) high melting points and nondirectional bonds
(C) high solubilities in polar solvents and low solubilities in nonpolar solvents
(D) three-dimensional arrangements of ions in solid state, and are good conductors of electricity in the molten
state
77. Which of the following statements is/are true?

(A) Covalent bonds are directional
(B) Ionic bonds are nondirectional
(C) A polar bond is formed between two atoms which have the same electronegativity value.
(D) The presence of polar bonds in a polyatomic molecule suggests that it has zero dipole moment
79. Which of the following species contain coordinate covalent bond :
(A) AlCl 3 (B) CO (C) [ Fe (CN ) 6 ]4 - (D) N 3-
80. Which of the following statement is/are correct

(A) Hybridisation is the mixing of pure atomic orbitals having less energy difference
(B) sp 3 d 2 - hybrid orbitals are at 90º to each other
(C) sp 3 d - hybrid orbitals are directed towards the corners of a regular tetrahedron
(D) sp 3 d 2 - hybrid orbitals are directed towards the corners of a regular octahedron
81. sp 3 hybridisation is in :
(A) AlH 4- (B) CH 3- (C) ClO2- (D) NH 2-
82. Shape of NH 3 is very similar to :
(A) SeO32 - (B) CH 3- (C) BH 3 (D) CH 3+
83. Which of the following species are linear ?

- - -
(A) ICl 2 (B) I 3 (C) N 3 (D) ClO2
84*. Which of the following statements are correct?

(A) The crystal lattice of ice is formed by covalent as well as hydrogen bonds
(B) The density of water increases when heated from 0º C to 4º C
(C) Above 4º C the thermal agitation of water molecules increases. Therefore, intermolecular distance increases
and water starts expanding
(D) The density of water decreases from 0º C to a maximum at 4º C
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Rankers Academy JEE
JEE-Chemistry
85. Molecule(s) having both polar and non polar bonds is / are
(A) O2F2 (B) S2Cl2 (C) N2H4 (D) S2F10
OH
CHO
86*.
(A) has intermolecular H - bonding (B) has intramolecular H- bonding

(C) has low boiling point (D) is steam-volatile
87. Intermolecular hydrogen bonding increases the enthalpy of vapourization of a liquid due to the:
(A) decrease in the attraction between molecules
(B) increase in the attraction between molecules
(C) decrease in the molar mass of unassociated liquid molecules
(D) increase in the effective molar mass of hydrogen - bonded molecules
Match the Column

88. Column–I Column–II
(A) XeF4 (P) sp3d hybridised with 2 lone pair on central atom
(B) BrF5 (Q) sp3d2 hybridised with 2 lone pair on central atom
(C) ClF3 (R) sp3 hybridised with 1 lone pair on central atom
(D) SO32– (S) sp3d2 hybridised with 1 lone pair on central atom
Comprehension
Hybridisation is a theoretical concept, as state of hybridisation cannot be detected even by spectroscopically;
unlike intermediates or transition state in various reactions. but it corrects the predictions which are based
simple on overlapping of pure atomic orbitals. VSEPR theory predicts precisely shape and bond angle in a
given molecule.
89. In which pair of molecules bond angles are not same:
+
(A) CCl4 & SiCl4 (B) NH4+ & N F4 (C) ClF6+ & SF6 (D) None
90. The molecules / ions which are planar as well as polar.

(A) BF3 , H2O, H F , NH2¯ (B) SnCl2 , I3+ , NH2¯, IF3
(C) CO32– , I3¯, SF2, XeF2 (D) NO2¯, XeF4, ICl4¯, NH2+
91. The correct order of energy levels of hybrid orbitals.

(A) sp > sp2 > sp3 (B) sp < sp2 < sp3 (C) sp2 > sp3 > sp (D) sp3 > sp > sp2
Subjetive Questions
92. Explain the structure of Boric acid in solid state.
93. Boiling point of o-Nitrophenol is less than meta and para nitrophenol. Why?
94. H – F is only liquid among halogen acid. Why?
95. Ammonia is more easily liquefied than HCl, explain.
96. Why ice floats on water?

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Rankers Academy JEE
Chemical Bonding
97. Water shows maximum density at 4°C. Why?
98. HI is the strongest halogen acid, whereas H–F is the weakest. Why?
99. Wood pieces are used to hold ice-cream. Why?
100. KHF2 is possible but not KHBr2 or KHI2. Why?
101. O – Nitrophenol is less soluble in H2O than p – Nitrophenol. Why?
102. o-Hydroxy benzaldehyde is a liquid at room temperature while p-hydroxy benzaldehyde is a high melting
solid.
103. Glycerol is more viscous than ethanol. Explain.
104. CH4 and H2O have nearly same molecular weight. Yet CH4 has a boiling point 112 K and water 373 K.
Explain.
105. The experimental molecular weight of acetic acid in just double than theoretical molecular weight of acetic
acid. Why?
106. Although chlorine has same electronegativity as nitrogen but the former does not form effective H-bonding.
Explain.
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Rankers Academy JEE
JEE-Chemistry
ANSWERS
l True and False
1. False 2. True 3. False 4. False 5. False

6. True 7. False 8. True 9. True 10. True
11. False 12. True 13. Ture 14. True 15. True
16. False 17. False 18. True 19. False 20. False
21. False 22. True 23. True 24. False 25. False
26. True 27. False 28. True 29. False
–1 3
30. 4.2 – 8.4 kJ mol 31. sp 32. sp
–
33. increases, decreases 34. N2O, I3
35. (B) 36. (C) 37. (C) 39. (C) 41. (C)
42. (A) 43. (C) 46. (C) 47. (A) 48. (A)
49. (B) 50. (C) 51. (B) 52. (D)
53. (A) 54. (D) 55. (A) 58. (C) 59. (B)
60. (B) 61. (A) 62. (B) 63. (D) 64. (A)
65. (B) 66. (A) 68. (B) 70. (A) 71. (A)
72. (A) 73. (D)
74. (BD) 75. (BCD) 77. (AB) 79. (BCD) 80. (ABD)
81. (ABCD) 82. (AB) 83. (ABC) 84. (ABC) 85. (ABCD)
86. (BCD) 87. (BD)
l Match the Column
88. A-Q, B-S, C-P,D-R
l Comprehension
89. (D) 90. (B) 91. (B)
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Rankers Academy JEE
Mole Concept
MOLE CONCEPT
Fill in the blanks
1. Ratio of number of protons to neutrons in 3.011 × 1022 molecules of D3O+ is “_____”
Assertion-Reason
NA N
2. Statement-I : 16 g each O2 and O3 contains and A atoms respectively..
2 3
Because
Statement-II : 16 g O2 and O3 contains same no. of atoms.
3. Statement-I : The average mass of one Mg atom is 24.305 amu, which is not the actual mass of one Mg
atom.
Because
Statement-II : Three isotopes, 24Mg, 25Mg and 26Mg, of Mg are found in nature.
4. Statement-I : A molecule of butane, C4H10 has a mass of 58.12 amu.

Because
Statement-II : One mole of butane contains 6.022 × 1023 molecules and has a mass of 58.12 g.
5. Statement-I : Both 12 g. of carbon and 27 g. of aluminium will have 6.02 × 1023 atoms.
Because
Statement-II : Gram atomic mass of an element contains Avogadro's number of atoms.
6. 112.0 ml of NO2 at 1atm & 273 K was liquefied, the density of the liquid being 1.15 gm/ml. Calculate the
volume of and the number of molecules in the liquid NO2.
(A) 0.10 ml and 3.01 × 1022 (B) 0.20 ml and 3.01 × 1021
23
(C) 0.20 ml and 6.02 × 10 (D) 0.40 ml and 6.02 × 1021
7. The shape of Tobacco Mosaic Virus (TMC) is cylindrical, having length and diameter 3000 Å and 170 Å,
respectively. The density of the virus is 0.08 gm/ml. The molecular weight of TMC is
(A) 3.28 (B) 5.44 × 10–24 (C) 5.44 × 10–18 (D) 3.28 × 106
8. What time, it would take to spend Avogadro’s number of rupees at the rate of 10 lac rupees per second?
(A) 6.023 × 1017 sec (B) 1.909 × 1010 year (C) 1.673 × 1014 hour (D) all of these
9. The sodium salt of methyl orange has 7% sodium. What is the minimum molecular weight of the compound?
(A) 420 (B) 375 (C) 329 (D) 295
10. In the preceding problem, if the compound contains 12.8% nitrogen 9.8% sulphur how many nitrogen and sulphur
atoms are present per atom of sodium :
(A) 2 and 1 (B) 1 and 3 (C) 1 and 2 (D) 3 and 1
11. Na2SO4. xH2O has 50% H2O. Hence, x is :

(A) 4 (B) 5 (C) 6 (D) 8
12. In the following final result is ....0.1 mol CH4 + 3.01 × 1023 molecules CH4 – 9.6 g CH4 = x mol H atoms :
(A) 0 mol H atom (B) 0.2 mol H atom (C) 0.3 mol H atom (D) 0.4 mol H atom
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Rankers Academy JEE
JEE-Chemistr y
13. In a gaseous mixture an alkane (CxH2x+2) and an alkene (CyH2y) are taken in 2 : 1 mole ratios, the average
molecular weight of mixture is observed to be 20. If the same alkane and alkene are taken in
1 : 2 mole ratios, the average molecular weight of mixture is observed to be 24. Then the value of ‘x’ and ‘y’
respectively are :
(A) 2, 1 (B) 1, 2 (C) 2, 3 (D) 3, 2
14. 3.06 L of H2O(vap) is taken at a pressure of 1 atm and 373 K. It is now condensed to H 2O (l) at 373K. Calculate
the volume occupied by H2O(l) (Density of liquid water = 1 g/ml)
(A) 3.06 L (B) 1.8 ml (C) 1.8 L (D) 3.06 ml
15. Nylon is prepared using a compound having formula HOOC(CH2)4COOH. What is the total number of atoms
present in 0.73 mg of the above compound :
(A) 6.023 × 1019 (B) 6.023 × 1022 (C) 60.23 × 1023 (D) 20
16. A substance has 16% by mass of Sulphur and 4% by mass of Oxygen. Calculate minimum molar mass of the
substance.
(A) 200 (B) 400 (C) 600 (D) 100
17. In an experiment, it is found that 2.0769 gm of pure X produces 3.6769 gm of pure X2O5. Then number of
moles of X is :
(A) 0.04 (B) 0.06 (C) 0.4 (D) 0.02
18. Two isotopes of an element ( atomic mass = x + 2.35) have mass (x + 2) and (x + 7) respectively. Calculate
natural abundance of heavier isotope in percentage.
(A) 3 (B) 5 (C) 7 (D) 9
19. Two elements A and B form two different sets of compounds A 2B3 and A3B4. 2.02 kg of A2B3 has 1.806 × 1025
atoms of B and 1.44 kg of A3B4 has 9.03 × 1024 atoms of A. What will be gram molecular mass (GMM) of
another compound AB formed from combination of A and B.
(A) 75 (B) 86 (C) 94 (D) 97
20. An element exist in three isotopic form 40X, 41X and 42X .
40
Percentage abundance of X = 30% by mole.
If average atomic mass of ‘X’ is 41.25. Find out percentage abundance of 41X.
[Divide your answer by 3 and fill OMR sheet]
(A) 2 (B) 3 (C) 5 (D) 7
21. A solution of palmitic acid (M =256) in benzene contains 5 gm acid per litre. When this solution is dropped on
surface, C6H6 gets evaporated and acid forms a unimolecular layer on the surface. If we wish to cover an area
6000 cm2 with unimolecular film. What volume of solution in ml should be used? Area covered by one molecule
of acid is 0.32 nm2. (Given : NA = 6 × 1023)
Write your answer multiplying with 1000.
(A) 120 ml (B) 140 ml (C) 160 ml (D) 180 ml
22. An element exist in two isotopic forms X120 and X122, in equal abundance. The average atomic mass of element
is 121.44. If each atom of X120 are 10.04 times heavier than one C12 atom, then how many times each atom
of X122 is heavier than one C12 atom ?
(A) 10.04 (B) 10.4 (C) 10.2 (D) 10.167
23. How many moles of e– weight one Kg : [JEE 2002]

1 6.023 1
(A) 6.023 × 1023 (B) ´ 1031 (C) ´ 1054 (D) ´ 108
9.108 9.108 9.108 ´ 6.023
24. Which has maximum number of atoms : [JEE 2003]

(A) 24 g C(12) (B) 56 g Fe(56) (C) 27 g Al (27) (D) 108 g Ag(108)
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Rankers Academy JEE
Mole Concept
–1
25. An alloy of gold and silver contains 38.5% silver by mass and has a density of 14.6 g.mL . What is the molar
concentration of silver in this alloy :
(A) 52.1 mol.L–1 (B) 45.6 mol.L–1 (C) 3.57 mol.L–1 (D) 2.64 mol.L–1
26. "Suvarnabhasm", an ayurvedic drug, is found to contain 400 ppm of colloidal gold. Mass % of gold (atomic
mass of Au = 197) will be :
(A) 0.040 % (B) 7.88 % (C) 0.0788 % (D) 4 × 10–4 %
27. 1 mol of iron (Fe) reacts completely with 0.65 mol O2 to give a mixture of only FeO and Fe2O3. Mole ratio of
ferrous oxide to ferric oxide is :-
(A) 3 : 2 (B) 4 : 3 (C) 20 : 13 (D) none of these
28. The molar ratio of Fe++ to Fe+++ in a mixture of FeSO4 and Fe2(SO4)3 having equal number of sulphate ion in
both ferrous and ferric sulphate is :-
(A) 1 : 2 (B) 3 : 2 (C) 2 : 3 (D) can't be determined
29. If a piece of iron gains 10% of its weight due to partial rusting into Fe 2O3. The percentage of total iron that has
rusted is :-
(A) 23 (B) 13 (C) 23.3 (D) 25.67
30. 29.5 mg of an organic compound containing nitrogen was digested according to Kjeldahl’s method and the
evolved ammonia was absorbed in 20 mL of 0.1 M HCl solution. The excess of the acid required 15 mL of 0.1
M NaOH solution for complete neutralization. The percentage of nitrogen in the compound is :[AIEEE 2010]
(A) 59.0 (B) 47.4 (C) 23.7 (D) 29.5
31*. For the estimation of nitrogen, 1.4 g of an organic compound was digested by Kjeldahi method and the evolved
M M
ammonia was absorbed in 60 mL of sulphuric acid. The unreacted acid required 20 mL of sodium
10 10
hydroxide for complete neutralization. The percentage of nitrogen in the compound is:
[JEE Mains-2014]
(A) 6% (B) 10% (C) 3% (D) 5%
32. The molecular formula of a commercial resin used for exchaging ions in water softening is C8H7SO3Na
(Mol. wt. 206). What would be the maximum uptake of Ca2+ ions by the resin when expressed in mole per gram
resin ? [JEE Mains-2015]
1 1 2 1
(A) (B) (C) (D)
103 206 309 412
33*. 3 g of activated charcoal was added to 50 mL of acetic acid solution (0.06 N) in a flask. After an hour it was
filtered and the strength of the filtrate was found to be 0.042 N. The amount of acetic acid adsorbed
(per gram of charcoal) is [JEE Mains-2015]
(A) 18 mg (B) 36 mg (C) 42 mg (D) 54 mg
34. In Carius method of estimation of halogens, 250 mg of an organic ompound gave 141 mg of AgBr. The
percentage of bromine in the compound is: (at mass Ag = 108; Br = 80) [JEE Mains-2015]
(A) 24 (B) 36 (C) 48 (D) 60
35. At 300 K and 1 atm, 15 mL of a gaseous hydrocarbon requires 375 mL air containing 20% O 2 by volume for
complete combustion. After combustion the gases occupy 330 mL. Assuming that the water formed is in liquid
form and the volumes were measured at the same temperature and pressure, the formula of the hydrocarbon is:
[JEE Mains-2016]
(A) C3H6 (B) C3H8 (C) C4H8 (D) C4H10
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Rankers Academy JEE
JEE-Chemistr y
36*. A 10 gram sample of natural gas containing CH4 and C2H4 was burnt in excess of oxygen to give 29.0 grams
of CO2 and some water. How many grams of water are formed :
(A) 9.42 g (B) 18.81 g (C) 11.42 g (D) 15.31 g
37*. 50 g of ZnS are strongly heated in air to effect partial oxidation and the resultant mass weighed 44 g. What
is the ratio of ZnO to ZnS in the resultant mixture :
(A) 13.5 : 30.5 (B) 27 : 12.58 (C) 27 : 15.31 (D) 30.52 :13.48
38. The % loss in weight after heating a pure sample of potassium chlorate (M. wt. 122.5) will be :
(A) 12.25 (B) 24.50 (C) 39.17 (D) 49.0
39*. Iodobenzene (C6H5I) is prepared from aniline (C6H5NH2) in a two step process as shown below
C6H5NH2 + HNO2 + HCl ® C6H5N2 +Cl– + 2H2O
C6H5N2 +Cl– + KI ® C6H5I + N2 + KCl
In an actual preparation 9.30 g of aniline was converted to 16.32 g of iodobenzene. The percentage yield of
iodobenzene is :
(A) 8 % (B) 50 % (C) 75 % (D) 80 %
40. An aqueous solution of concentrated hydrobromic acid contains 48% HBr by mass. If the density of the solution
is 1.50 g / mL, what is its concentration :
(A) 11.4 mol/L (B) 8.9 mol/L (C) 5.9 mol/L (D) 18.5 mol/L
41*. X gm A atoms on combining with Y atoms of B form 5 molecules of a compound containing A & B. Find
the molecular weight of compound formed. (Atomic weight of B = M)
(XN A + MY) X+M X + MY æ X + MYN A ö
(A) (B) (C) (D) ç ÷
5 5 5 è 5 ø
42. Calculate mass % & mole % of H2 in a mixture of H2 and O2 if average molecular mass of the mixture is 14.
(A) 50 % by mole (B) 60 % by mole (C) 8.57% by mass (D) 10% by mass
43*. Which of the following options is/are incorrect.

(A) 10 gm of Boron is having 5 mole of nucleons.
(B) One atom of an element weight 1.8 × 10–22 gm, then its atomic mass is 108.36
(C) 10 gm of CaCO3 contains 1 gm atom of C.
(D) Number of atoms in 2 moles of S8 is greater than 5.5 moles of SO2
44. A polymeric organic compound contains 0.07% iron and 0.035% nitrogen by mass. Which of the following
statement(s) is/are correct for the compound ? (Fe = 56, N = 14)
(A) The molecular mass of compound may be 40000.
(B) The molecular mass of compound may be 160000.
(C) In each molecule of this compound, there are 2 nitrogen atoms per iron atom.
(D) In each molecule of this compound, there are 2 iron atoms per nitrogen atom.
45. Which of the following have equal no. of atoms ?

(A) 12 g MgSO4 (B) 0.2 mole CO2 (C) 5.6 L SO2 at STP (D) 24 g Ca
200
46. A mixture of two gases H2 and O2 has an average molecular mass 12 and is kept at a temperature of K
3
and pressure 0.821 atm. Select the correct options :
100
(A) Mixture contains % by mass of H2 gas. (B) Density of mixture is 1.8 gm/ml.
9
100 1
(C) Mixture contains % by mol of O2 gas (D) Mole ratio of O2 and H2 gas in the mixture is
3 3
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Rankers Academy JEE
Mole Concept
47. Which of the statements is / are true for a chemical reaction occurring in a closed container?
(A) Total mass of all reactants and products always remain constant.
(B) Average molecular mass of the mixture may change during chemical reaction.
(C) Total number of atoms of each element will remain constant in a chemical reaction.
(D) Total volume of all reactants and products always remain constant.
Comprehension
Comprehension-1
Azurite is a copper containing mineral that is a mixture of Copper (II) carbonate and copper (II) hydroxide,
[CuCO3]X. [Cu(OH)2]y. If the mineral is 55.31% Cu, 0.58% H and 6.97% C, with the remainder oxygen, what
are x and y in the general formula ? [Cu = 63.5]
48. What is the value of ‘x’ in general empirical formula ?

(A) 7 (B) 2 (C) 3 (D) 4
49. What is the value of ‘y’ in the general empirical formula b?

(A) 1 (B) 2 (C) 3 (D) 4
50. If the value of x and y be 1 and 2 respectively. Calculate the % composition of Cu ?

(A) 50 % (B) 59.8% (C) 51.2% (D) 60%
Comprehension-2
Calcium lactate is used in the food and beverage industries. It has also been used medicinally for treatment
of various allergies, for treatment of muscular leg cramps, and as an antidote for a variety of poisons, including
lead, arsenicals and carbon tetrachloride. A 0.8274 g sample of anhydrous calcium lactate is found by analysis
to contain 0.2732 g of C, 0.0382 g H, 0.1520 g Ca and 0.3640 g O. Each mole of calcium lactate is found
to contain one mole of calcium ions. Calcium lactate can be crystallised from water as pentahydrate salt.
51. Simplest formula of the calcium lactate is :

(A) CaO6C6H10 (B) CaO3C3H5 (C) CaO2C3H3 (D) CaO2C3H5
52. Formula weight of calcium lactate is :

(A) 129 g mol–1 (B) 111 g mol–1 (C) 218 g mol–1 (D) 113 g mol–1
53. How many grams of calcium lactate pentahydrate would be recovered from 1 g of anhydrous salt :
(A) 1.41 g (B) 1.00 g (C) 1.27 g (D) 1.51 g
Subjetive Questions
54. A crystalline hydrated salt on being rendered anhydrous, loses 45.6% of its weight. The percentage composition
of anhydrous salt is : Al = 10.5%, K = 15.1%, S = 24.8% and O = 49.6%. Find the empirical formula of
the anhydrous and crystalline salt :
55. A compound containing Ca, C, N and S was subjected to quantitative analysis and formula mass
determination. A 0.25 g of this compound was mixed with Na2CO3 to convert all Ca into 0.16 g CaCO3. A
0.115 g sample of compound was carried through a series of reactions until all its S was changed into SO -42 and
precipitated as 0.344 g of BaSO4 . A 0.712 g sample was processed to liberate all of its N as NH 3 and 0.155
g NH3 was obtained. The formula mass was found to be 156. Determine the empirical and molecular formula
of the compound :
56. One mole of a mixture of N2, NO2 and N2O4 has a mean molar mass of 55.4. On heating to a temperature
at which N2O4 may be dissociated : N2O4 ¾® 2NO2, the mean molar mass tends to the lower value of 39.6.
What is the mole ratio of N2 : NO2 : N2O4 in the original mixture?
57. Two elements C and D combine to form two compounds CxDy & CyDx. 0.5 mole of CyDx weigh 40 gm & 1
molecule of CxDy weigh 1.66 × 10–25 kg. The atomic weight of C and D are 20 & 40 respectively. 'x' & 'y' are
respectively.
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Rankers Academy JEE
JEE-Chemistr y
58. On a reference scale of C, at. weight of Al is 26.98 of Titanium is 47.48. What would be at. weight of Al on
a new reference scale where Titanium has a value of 48.
59. Three isotopes of an element have mass numbers M, (M+1) and (M+2). If the mean mass number is (M + 0.5),
then the ratio of number may be accepted for M, (M+1) and (M+2) in the order
60. 0.36 gm of a triatomic gas, X3, occupies 168 ml at 1 atm & 273 K. The atomic weight of X is
61. A 1.85 g sample of mixture of CuCl2 and CuBr2 was dissolved in water and mixed thoroughly with
1.8 g portion of AgCl. After reaction, the solid which now contain AgCl and AgBr was filtered, dried and weighed
to be 2.052 g. What was the % by weight of CuBr2 in the mixture?
62. A mixture of CuSO4 . 5H2O and MgSO4 . 7H2O was heated until all the water was driven-off. If 5.0 g of mixture
gave 3 g of anhydrous salts, what was the percentage by mass of CuSO4 . 5H2O in the original mixture :
63*. A 0.2 g sample, which is mixture of NaCl, NaBr and NaI was dissolved in water and excess of AgNO3 was
added. The precipitate containing AgCl, AgBr and AgI was filtered, dried and weighed to be 0.412 g. The solid
was placed in water and treated with excess of NaBr, which converted all AgCl into AgBr. The precipitate was
then weighed to be 0.4881 g. It was then placed into water and treated with excess of NaI, which converted
all AgBr into AgI. The precipitate was then weighed to be 0.5868 g. What was the percentage of NaCl, NaBr
and NaI in the original mixture :
64. A mother cell disintegrate into sixty identical cells and each daughter cell further disintegrate into 24 smaller
cells. The smallest cells are uniform cylindrical in shape with diameter of 120 Å and each cell is 6000 Å long.
Determine molar mass of the mother cell if density of the smallest cell is 1.12 g/cm3 :
65. A2 + 2B2 ¾® A2B4

3
A + 2B2 ¾® A3B4
2 2
Two substance A2 & B2 react in the above manner when A 2 is limited it gives A2B4 in excess gives A3B4. A2B4
can be converted to A3B4 when reacted with A2. Using this information calculate the composition of the final
mixture when the mentioned amount of A & B are taken :c
(a) 4 moles A2 & 4 moles B2
1
(b) moles A2 & 2 moles B2
2
(c) 1.25 moles A2 & 2 moles B2
66. 20% surface sites have adsorbed N2. On heating N2 gas evolved from sites and were collected at 0.001 atm
and 298 K in a container of volume is 2.46 cm 3. Density of surface sites is 6.023 × 10 14/cm2 and surface area
is 1000 cm2, find out the no. of surface sites occupied per molecule of N2 : [JEE 2005]
67. N2H4, Hydrazine a rocket fuel can be produced according to the following reaction :
ClNH2 + 2NH3 ¾® N2H4 + NH4Cl
When 1000 g ClNH2 is reacted with excess of NH3, 473 g N2H4 is produced. What is the % yield of the reaction.
68*. Calculate the percent of BaO in 29.0 g of a mixture of BaO and CaO which just reacts with 100.8 mL of 6.00
M HCl.
BaO + 2HCl ® BaCl2 + H2O
CaO + 2HCl ® CaCl2 + H2O
69*. 10 ml of ammonia were enclosed in an eudiometer and subjected to electric sparks. The sparks were continued
till there was no further increase in volume. The volume after sparking measured 20 ml. Now 30 ml of O 2 were
added and sparking was continued again. The new volume then measured 27.5 ml. All volumes were measured
under identical conditions of temperature and pressure. V.D. of ammonia is 8.5. If the molecular formula of
ammonia is NxHy then calculate (x + y). Nitrogen and Hydrogen are diatomic.
32
Rankers Academy JEE
Mole Concept
ANSWERS
1. (1)
2. (D) 3. (A) 4. (A) 5. (A)
6. (B) 7. (D) 8. (D) 9. (C) 10. (D)

11. (A) 12. (A) 13. (B) 14. (B) 15. (A)
16. (B) 17. (A) 18. (C) 19. (B) 20. (C)
21. (C) 22. (C) 23. (D) 24. (A) 25. (A)
26. (A) 27. (B) 28. (B) 29. (C) 30. (C)
31. (B) 32. (D) 33. (A) 34. (A) 35. (BONUS)
36. (B) 37. (D) 38. (C) 39. (D) 40. (B)
41. (A) 42. (BC) 43. (ACD) 44. (BC) 45. (ABD)
46. (AC) 47. (ABC)
l Comprehension
Comprehension 1 : 48. (B) 49. (A) 50. (B)

Comprehension 2 : 51. (A) 52. (C) 53. (A)
54. KAlS2O8 , KAlS2O8.12 H2O 55. CaC2N2S2, CaC2N2S2 56. 0.5 : 0.1 : 0.4
57. x=1 y=2 58. 27.04 59. 4:1:1
60. 16 61. 34.18 62. 74.4
10
63*. 50, 20.23, 29.77 64. 6.6 × 10 g
1
65. (a) A3B4 = 2 & A2 = 1 ; (b) A2B4 = & B2 = 1 (c) A2B4 = 0.5 & A3B4 = 0.5
2
66. (2) 67. 76.12% 68. 65.65%
69*. (4)
33
Rankers Academy JEE
JEE-Chemistr y
REDOX
Fill in the blanks
1. The reactant which reacts completely in a reaction is called ................... .
2. In the reaction 2 H2O2 ¾® 2 H2O + O2, hydrogen peroxide is .................... .
3. In the reaction 2 KClO3 ¾® 2 KCl + 3 O2, the element which has been oxidised is .................... and the
element which has been reduced is .................... .
4. The compound YbBa2Cu3 O7 which shows superconductivity, has copper in oxidation state .................... Assume
that the rare earth element ytterbium is in the usual + 3 oxidation state.
5. In HCN oxidation number of carbon is .................... .
Assertion & Reason

6. Statement-I : The percentage weight of a compound A in a solution is given by
Mass A
% of A = Total mass of solution × 100
Because
Statement-II : The mole fraction of a component A is given by,
No. of moles of A
Mole fraction of A = Total no. of moles of all components
7. Statement-I : A one molal solution prepared at 20°C will retain the same molality at 100°C, provided there
is no loss of solute or solvent on heating.
Because
Statement-II : Molality is independent of temperature.
8. Statement-I : The oxidation state of superoxide ion in KO2, CsO2 and RbO2 is –1/2.
Because
Statement-II : Since the oxidation state of an alkali metal in any compound is always +1, the oxidation state
of oxygen is –1/2 in the O2– ion.
9. Statement-I : In the redox reaction

8 H+ (aq) + 4 NO3– + 6 Cl– + Sn (s) ® SnCl62– + 4 NO2 + 4 H2O
the reducing agent is Sn (s),
Because
Statement-II : In balancing half reaction, S2O32– ® S(s), the number of electrons added on the left is 4.
10. Statement-I : Among Br–, O22–, H– and NO3–, the ions that could not act as oxidising agents are Br– and H.
Because
Statement-II : Br Q and H– could not be reduced.
34
Rankers Academy JEE
Redox
11. 28 NO3– + 3As2S3 + 4H2O ® 6AsO43– + 28 NO + 9SO42– + H+

What will be the equivalent mass of As2S3 in above reaction
M.wt. M.wt. M.wt. M.wt.
(A) (B) (C) (D)
2 4 24 28
12. When ZnS is boiled with strong nitric acid, the products are zinc nitrate, sulphuric acid and nitrogen dioxide.
What are the changes in the oxidation numbers of Zn, S and N.
(A) +2, +4, –1 (B) +2, +6, –2 (C) 0, +4, –2 (D) 0, +8, –1
13. When arsenic sulphide is boiled with NaOH, sodium arsenite and sodium thioarsenite are formed
y
x As2S3 + y NaOH ¾® Na3AsO3 + x Na3AsS3 + H O. What are the values of x and y ?
2 2
(A) 1, 6 (B) 2, 8 (C) 2, 6 (D) 1, 4
14. An element forms two different sulphates in which its weight % is 28 and 37. What is the ratio of oxidation
numbers of the element in these sulphates ?
(A) 1 : 2 (B) 1 : 3 (C) 2 : 1 (D) 3 : 2
15. CN– is oxidised by NO3– in presence of acid :

c
a CN– + b NO3– + c H+ ¾® (a + b) NO + a CO2 + HO
2 2
What are the values of a, b, c in that order :
(A) 3,7,7 (B) 3,10,7 (C) 3,10,10 (D) 3,7,10
16. Which of the following solutions will exactly oxidize 25 mL of an acid solution of 0.1 M Fe (II) oxalate :-
(A) 25 mL of 0.1 M KMnO4 (B) 25 mL of 0.2 M KMnO4
(C) 25 mL of 0.6 M KMnO4 (D) 15 mL of 0.1 M KMnO4
17*. 4.9 gm of K2Cr2O7 is taken to prepare 0.1 L of the solution. 10 mL of this solution is further taken to oxidise
Sn2+ ion into Sn4+ ion Sn4+ so produced is used in 2nd reaction to prepare Fe3+ ion then the millimoles of Fe3+
ion formed will be (assume all other components are in sufficient amount) [Molar mass of K2Cr2O7 = 294 g].
(A) 5 (B) 20 (C) 10 (D) none of these
18. 35 mL sample of hydrogen peroxide gives of 500 mL of O2 at 27°C and 1 atm pressure. Volume strength of
H2O2 sample will be :-
(A) 10 volume (B) 13 volumes (C) 11 volume (D) 12 volume
19. 20 mL of 0.1 M solution of compound Na 2CO3.NaHCO3.2H2O is titrated against 0.05 M HCl, x mL of HCl is
used when phenolphthalein is used as an indicator and y mL of HCl is used when methyl orange is the indicator
in two separate titrations. Hence (y – x) is :-
(A) 40 mL (B) 80 mL (C) 120 mL (D) none of these
20*. 0.10 g of a sample containing CuCO3 and some inert impurity was dissolved in dilute sulphuric acid and volume
made up to 50 mL. This solution was added into 50 mL of 0.04 M KI solution where copper precipitates as CuI
and I – is oxidized into I3– . A 10 mL portion of this solution is taken for analysis, filtered and made up free I 3– and
then treated with excess of acidic permanganate solution. Liberated iodine required 20 mL of 2.5 mM sodium
thiosulphate solution to reach the end point.
Determine weight percentage of CuCO3 in the original sample.
(A) 7.41 (B) 74.1 (C) 61.75 (D) none of these
21. A mixture of H2SO4 and H2C2O4 (oxalic acid) and some inert impurity weighing 3.185 g was dissolved in water
and the solution made up to 1 litre, 10 mL of this solution required 3 mL of 0.1 N NaOH for complete
neutralization. In another experiment 100 mL of the same solution in hot condition required
4 mL of 0.02M KMnO4 solution for complete reaction. The wt. % of H2SO4 in the mixture was :-
(A) 40 (B) 50 (C) 60 (D) 80
35
Rankers Academy JEE
JEE-Chemistr y
22*. 0.80 g of sample of impure potassium dichromate was dissolved in water and made upto 500 mL solution.
25 mL of this solution treated with excess of KI in acidic medium and I 2 liberated required 24 mL of a sodium
thiosulphate solution. 30 mL of this sodium thiosulphate solution required 15 mL of N/20 solution of pure
potassium dichromate. What was the percentage of K 2Cr2O7 in given sample?
(A) 73.5 % (B) 75.3 % (C) 36.75 % (D) none of these
23. The oxidation number of phosphorus in Ba(H2PO2)2 is : [JEE 1990]

(A) +3 (B) +2 (C) +1 (D) –1
24. The number of electrons to balance the following equation :- [JEE 1991]
NO3– + 4H+ + e– ® 2H2O + NO is
(A) 5 (B) 4 (C) 3 (D) 2
25. What is the volume strength of 1.5 N H2O2 : [JEE 1991]
(A) 4.8 (B) 8.4 (C) 3.0 (D) 8.0
26. The oxidation states of the most electronegative element in the products of the reaction of BaO2 with
dilute H2SO4. [JEE 1991]
(A) 0 and –1 (B) –1 and –2 (C) –2 and 0 (D) –2 and +2
27. For the redox reaction, [JEE 1992]

MnO4– + C2O42– + H+ ® Mn2+ + CO2 + H2O
the correct coefficients of the reactants for the balanced reaction are :
MnO4– C2O42– H+
(A) 2 5 16
(B) 16 5 2
(C) 5 16 2
(D) 2 16 5
28. The number of mole of KMnO4 that will need to react completely with one mole ferrous oxalate in acidic solution
is : [JEE 1997]
(A) 2/5 (B) 3/5 (C) 4/5 (D) 1
29. The number of mole of KMnO4 that will be needed to react with one mole of sulphite ion in acidic solution
is : [JEE 1997]
(A) 2/5 (B) 3/5 (C) 4/5 (D) 1
30. The equivalent mass of MnSO4 is half its molecular mass when it is converted to : [JEE 1998]
– 2–
(A) Mn2O3 (B) MnO2 (C) MnO4 (D) MnO4
31. The oxidation number of sulphur in S8, S2F2 and H2S respectively are : [JEE 1999]
(A) 0, +1 and –2 (B) +2, +1 and –2 (C) 0, +1 and +2 (D) –2, +1 and –2
32. The normality of 0.3 M phosphorus acid (H3PO3) is : [JEE 1999]

(A) 0.1 (B) 0.9 (C) 0.3 (D) 0.6
33. Among the following species in which oxidation state of the element is +6 : [JEE 2000]
(A) MnO4– (B) Cr(CN)63– (C) NiF62– (D) CrO2Cl2
34. Oxidation number of iron in Na2 [Fe(CN)5 NOÅ] is : [JEE 2001]

(A) +2 (B) +3 (C) +8/3 (D) none of these
35. An aqueous solution of 6.3 g of oxalic acid dihydrate is made upto 250 mL. The volume of 0.1 N NaOH required
to completely neutralise 10 mL of this solution is : [JEE 2001]
(A) 40 mL (B) 20 mL (C) 10 mL (D) 4 mL
36
Rankers Academy JEE
Redox
– – –
36. In basic medium I oxidises by MnO4 . In this process I replaces by : [JEE 2004]
(A) IO3– (B) I2 (C) IO4– (D) IO –
37. Amongst the following, the pair having both the metals in their highest oxidation state is : [JEE 2004]
(A) [Fe(CN)6]3– and [Co(CN)6]3– (B) [CrO2Cl2] and [MnO4– ]
(C) TiO2 and MnO2 (D) [MnCl4]2– and [NiF6] –2
38. O3 does not oxidise : [JEE 2005]

(A) KI (B) FeSO4 (C) KMnO4 (D) K2MnO4
39. An ore of iron, Wustite has the formula F 0.93O1.00. The mole fraction of total iron present in the form of Fe(II) is:-
(A) 0.82 (B) 0.85 (C) 0.15 (D) 0.37
40. HNO3 oxidises NH4+ ions to nitrogen and itself gets reduced to NO2. The moles of HNO3 required by 1 mol of
(NH4)2SO4 is :-
(A) 4 (B) 5 (C) 6 (D) 2
41*. 25 mL of a 0.1 M solution of a stable cation of transition metal Z reacts exactly with 25 ml of 0.04 mL acidified
KMnO4 solution. Which of the following is most likely to represent the change in oxidation state of Z correctly :-
(A) Z+ ® Z2+ (B) Z2+ ® Z3+ (C) Z3+ ® Z4+ (D) Z2+ ® Z4+
42. How many litres of Cl2 at S.T.P. will be liberated by oxidation of NaCl with 10 g KMnO 4 :-
(A) 3.54 litres (B) 7.08 litres (C) 1.77 litres (D) none of these
43. During the disproportionation of iodine to iodide and iodate ions, the ratio of iodate and iodide ions formed in
alkaline medium is :-
(A) 1 : 5 (B) 5 : 1 (C) 3 : 1 (D) 1 : 3
Match the Column
44*. Column-I Column-II

Molecular weight
(A) Eq. wt. of underlined = (p) When CrI3 oxidises into Cr2O72– and IO4–
33
Molecular weight
(B) Eq. wt. of underlined = (q) When Fe(SCN)2 oxidises into Fee3+, SO42–, CO32–
27
and NO3–
Molecular weight
(C) Eq. wt. of underlined = (r) When NH 4 SCN oxidizes into SO42–, CO32–
28
and NO3–
Molecular weight
(D) Eq. wt. of underlined = (s) When As 2S 3 oxidises into AsO3– and SO42–
24
Comprehension
Comprehension-1
Oleum is considered as a solution of SO3 in H2SO4, which is obtained by passing SO3 in solution of H2SO4.
When 100 g sample of oleum is diluted with desired weight of H2O then the total mass of H2SO4 obtained
after dilution is known as % labelling in oleum.
For example, a oleum bottle labelled as '109% H2SO4' means the 109 g total mass of pure H2SO4 will be
formed when 100 g of oleum is diluted by 9 g of H2O which combines with all the free SO3 present in oleum
to form H2SO4 as SO3 + H2O ¾® H2SO4
37
Rankers Academy JEE
JEE-Chemistr y
45. What is the % of free SO3 in an oleum that is labelled as '104.5 % H2SO4'?
(A) 10 (B) 20 (C) 40 (D) none of these
46. 9.0 g water is added into oleum sample labelled as '112% H2SO4' then the amount of free SO3 remaining
in the solution is :
(A) 14.93 L at STP (B) 7.46 L at STP (C) 3.73 L at STP (D) 11.2 L at STP
47. If excess water is added into a bottle sample labelled as '112 % H2SO4' and is reacted with 5.3 g Na2CO3,
then find the volume of CO2 evolved at 1 atm pressure and 300 K temperature after the completion of the
reaction:
(A) 2.46 L (B) 24.6 L (C) 1.23 L (D) 12.3 L
Comprehension-3
The strength of H2O2 is expressed in several ways like molarity, normality, % (w/V), volume strength, etc.
The strength of "10 V" means 1 volume of H2O2 on decomposition gives 10 volumes of oxygen at STP or
1 litre of H2O2 gives 10 litre of O2 at STP. The decomposition of H2O2 is shown as under :
1
H2O2 (aq) ¾® H2O (l) + O (g)
2 2
H2O2 can acts as oxidising as well as reducing agent, as oxidizing agent H2O2 converted into H2O and as
reducing agent H2O2 converted into O2, both cases it's n-factor is 2.
\ Normality of H2O2 solution = 2 × Molarity of H2O2 solution
48. What is the molarity of "11.2 V" of H2O2 ?

(A) 1 M (B) 2 M (C) 5.6 M (D) 11.2 M
49. What is the percentage strength (% w/V) of "11.2 V" H2O2 ?

(A) 1.7 (B) 3.4 (C) 34 (D) none of these
50. 20 mL of H2O2 solution is reacted with 80 mL of 0.05 M KMnO4 in acidic medium then what is the volume
strength of H2O2 ?
(A) 2.8 (B) 5.6 (C) 11.2 (D) none of these
51*. 40 g Ba(MnO4)2 (mol. wt. = 375) sample containing some inert impurities in acidic medium is completely
reacted with 125 mL of "33.6 V" of H2O2. What is the percentage purity of the sample ?
(A) 28.12 % (B) 70.31 % (C) 85 % (D) none of these
Subjetive Questions
52. A solution containing 4.2 g of KOH and Ca(OH2) is neutralized by an acid. It consums 0.1 equivalent of acid,
calculate the percentage composition of the sample.
53. 10 g CaCO3 were dissolved in 250 mL of M HCl and the solution was boiled. What volume of 2 M KOH would
be required to equivalence point after boiling? Assume no change in volume during boiling.
54. 1.64 g of mixture of CaCO3 and MgCO3 was dissolved in 50 mL of 0.8 M HCl. The excess of acid required
16 mL of 0.25 M NaOH for neutralization. Calculate the percentage of CaCO3 and MgCO3 in the sample.
55. A solution contains Na2CO3 and NaHCO3. 10 mL of this requires 2 mL of 0.1 M H2SO4 for neutralisation
using Ph indicator. MeOH is then added when a further 2.5 mL of 0.2 M H 2SO4 was needed. Calculate strength
of Na2CO3 and NaHCO3.
56*. A sample containing Na2CO3 & NaOH is dissolved in 100 mL solution. 10 mL of this solution requires 25 mL
of 0.1 N HCl when Ph is used as indicator. If MeOH is used as indicator 10 mL of same solution requires 30
mL of same HCl. Calculate % of Na2CO3 and NaOH in the sample.
38
Rankers Academy JEE
Redox
4+ 2+ 4+
57. It required 40.05 mL of 1 M Ce to titrate 20 mL of 1 M Sn to Sn . What is the oxidation state of the
cerium in the product.
58. A volume of 12.53 mL of 0.05093 M SeO2 reacted with exactly 25.52 mL of 0.1 M CrSO4. In the reaction,
Cr2+ was oxidized to Cr3+. To what oxidation state was selenium converted by the reaction.
59. Pottasium acid oxalate K2C2O4.3H2C2O4.4H2O can be oxidized by MnO4– in acid medium. Calculate the volume
of 0.1 M KMnO4 reacting in acid solution with one gram of the acid oxalate.
60. Metallic tin in the presence of HCl is oxidized by K2Cr2O7 to stannic chloride, SnCl4. What volume of
deci-normal dichromate solution would be reduce by 1 g of tin.
61. 5 g sample of brass was dissolved in one litre dil. H 2SO4. 20 mL of this solution were mixed with KI, liberating
I2 and Cu+ and the I2 required 20 mL of 0.0327 N hypo solution for complete titration. Calculate the percentage
of Cu in the alloy.
62. 0.84 g iron ore containing x percent of iron was taken in a solution containing all the iron in ferrous condition.
The solution required x mL of a dichromatic solution for oxidizing the iron content to ferric state. Calculate
the strength of dichromatic solution.
63*. The neutralization of a solution of 1.2 g of a substance containing a mixture of H2C2O4.2H2O, KHC2O4.H2O
and different impurities of a neutral salt consumed 18.9 mL of 0.5 N NaOH solution. On titration with KMnO4
solution, 0.4 g, of the same substance needed 21.55 mL of 0.25 N KMnO4. Calculate the % composition of
the substance.
64. 50 g of a sample of Ca(OH)2 is dissolved in 50 mL of 0.5 N HCl solution. The excess of HCl was titrated with
0.3 N – NaOH. The volume of NaOH used was 20cc. Calculate % purity of Ca(OH)2.
65*. One g of impure sodium carbonate is dissolved in water and the solution is made up to 250 mL. To 50 mL
of this made up solution, 50 mL of 0.1 N – HCl is added and the mix after shaking well required
10 mL of 0.16 N – NaOH solution for complete titration. Calculate the % purity of the sample.
66*. What amount of substance containing 60% NaCl, 37% KCl should be weighed out for analysis so that after
the action of 25 mL of 0.1 N AgNO3 solution, excess of Ag+ is back titrates with 5 mL of NH4SCN solution.
Given that 1 mL of NH4SCN = 1.1. mL of AgNO3.
67. 50 mL of an aqueous solution of H2O2 were treated with an excess of KI solution and dilute H2SO4, the lib-
erated iodine required 20 mL of 0.1 N Na 2S2O3 solution for complete interaction. Calculate the concentration
of H2O2 in g/l.
68. 10 g sample of bleaching powder was dissolved into water to make the solution one litre. To this solution 35
mL of 1.0 M Mohr salt solution was added containing enough H2SO4. After the reaction was complete, the
excess Mohr salt required 30 mL of 0.1 M KMnO4 for oxidation. Find out the % of available Cl 2
approximately is (mol wt. 71).
69*. Calculate the amount (in milligrams) of SeO3–2 in solution on the basis of following data 20 mL of M/60 solution
of KBrO3 was added to a definite volume of SeO3–2 solution. The bromine evolved was removed by boiling
and excess of KBrO3 was back titrated with 5 mL of M/25 solution of NaAsO 2. The reactions are given below.
(Atomic mass of K = 39, Br = 80, As = 75, Na = 23, O = 16, Se = 79)
(a) SeO3–2 + BrO3– + H+ ¾® SeO4–2 + Br2 + H2O
(b) BrO3– + AsO2– + H2O ¾® Br– + AsO4–3 + H+
70. A 1.0 g sample of Fe2O3 solid of 55.2% purity is dissolved in acid and reduced by heating the solution with
zinc dust. The resultant solution is cooled and made upto 100.0 mL. An aliquot of 25.0 mL of this solution
requires 17.0 mL of 0.0167 M solution of an oxidant for titration. Calculate the number of moles of electrons
taken up by the oxidant in the reaction of the above titration.
39
Rankers Academy JEE
JEE-Chemistr y
71. How much quantity of zinc will have to be reacted with excess of dilute HCl solution to produce sufficient hydrogen
gas for completely reacting with the oxygen obtained by decomposing 5.104 g of potassium chlorate?
72. 1.0 g of a sample containing NaCl, KCl and some inert impurity is dissolved in excess of water and treated
with excess of AgNO3 solution. A 2.0 g precipitate to AgCl separate out. also sample is 23% by mass in sodium.
Determine mass percentage of KCl in the sample :
73. 2.5 g of a sample containing Na 2CO3 ; NaHCO3 and some non-volatile impurity on gentle heating loses 12%
of its weight. Residue is dissolved in 100 mL water and its 10 mL portion required 15 mL 0.1 M aqueous solution
of BaCl2 for complete precipitation of carbonates. Determine mass percentage of Na2CO3 in the original sample?
74. Based on the following information, determine value x and y :

AgNO 3
(CH 3 )x AlCl y ¾¾® xCH 4 (g) + yCl - + Al 3 + ¾¾¾¾ ® AgCl(s)
0.643 g 0.222g 0.996 g
75*. A 5.0 g sample of felspar containing Na2O, K2O and some inert impurity is dissolved in dilute HCl solution and
NaCl and KCl formed are separated by fractional crystallization. During crystallization some less soluble im-
purities also comes out. Mass of NaCl, KCl and impurity accompanying these salts was found to be 6.47 g.
Solid crystal was then re-dissolved and required 300 mL of 0.3 M AgNO3 for complete precipitation of chlorides.
The precipitate this, obtained was found to contain 4.23 % insoluble impurity. Determine mass percentage of
Na2O and K2O in the original sample :
76. Pb(NO3)2 and KI reacts in aqueous solution to form an yellow precipitate of PbI2. In one series of experiments,
the masses of two reactants varied, but the total mass of the two was held constant at 5.0 g. What maximum
mass of PbI2 can be produced in the above experiment :
77. A sample is a mixture of Mohr's salts and (NH4)2SO4. A 0.5 g sample on treatment with excess of BaCl2 solution
gave 0.75 g BaSO4. Determine percentage composition of the salt mixture . What weight of Fe2O3 would be
obtained if 0.2 g of the sample were ignited in air ?
78. A chloride mixture is prepared by grinding together pure BaCl2.2H2O, KCl and NaCl. What is the smallest and
largest volume of 0.15 M AgNO3 solution that may be used for complete precipitation of chloride from a 0.3
g sample of the mixture which may contain any one or all of the constituents ?
79. One mole of a mixture of N2, NO2 and N2O4 has a mean molar mass of 55.4. On heating to a temperature
at which N2O4 may be dissociated : N2O4 ¾® 2NO2, the mean molar mass tends to the lower value of 39.6.
What is the mole ratio of N2 : NO2 : N2O4 in the original mixture?
80. A sea water sample has a density of 1.03 g/cm3 and 2.8% NaCl by mass. A saturated solution of NaCl in
water is 5.45 M NaCl. How much water would have to be evaporated from 1.00 × 106 L of the sea water
before NaCl would precipitate ?
81. One litre of milk weighs 1.035 kg. The butter fat is 4% (v/v) of milk has density of 875 kg/m 3. Find the density
of fat free skimed milk.
82*. A 1g sample of K2Cr2O7 containing some inert material was entirely reduced with conc. HCl. The chlorine
liberated was passed through hot solution of NaOH at 80 0C, and it completely diproportionates to form ClO3-
and Cl-. This NaClO3 was isolated and its reduction with KI (aq) liberated iodine, giving Cl-.The iodine thus
liberated required 100 mL of decinormal hypo solution for complete titration. What is the percentage purity of
the dichromate sample?
83. 2.5g of mixture of crystalline oxalic acid (H2C2O4. 2H2O) and sodium oxalate (Na2C2O4) was dissolved in 100
mL of water. 50 mL of this solution was titrated against N/10 NaOH solution when 119.05 mL of the base was
found necessary to reach the end point with phenolphthalein as the indicator. 1g of the mixture was dissolved in
water and the solution titrated against N/10 KMnO4 in the presence of dil. H2SO4. What is the volume of KMnO4
needed for getting the end point with 0.5g of the mixture?
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Rankers Academy JEE
Redox
84*. 0.6213 g of sample contains an unknown amount of As2O3. The sample was treated with HCl resulting in-
formation of AsCl3 (g) which was distilled into a beaker of water. The hydrolysis reaction is as follows :
AsCl3 + 2H2O ® HAsO2 + 3H+ + 3Cl–
The amount of HAsO2 was determined by titration with 0.04134 M I2, requiring 23.04 mL to reach the equivalence
point. The redox products in the titration were H3AsO4 and I–. Find the amount of KMnO4 needed to oxidize
As in As2O3 to its maximum possible oxidation state in acidic medium.
85*. In the presence of fluoride ion, Mn2+ can be titrated with MnO4–, both reactants being converted to a complex
of Mn(III). A 0.545 g sample containing Mn3O4 was dissolved and all manganese was converted to Mn2+. Titration
in the presence of fluoride ion consumed 31.1 mL of KMnO4 that was 0.177 N against oxalate.
(a) write a balanced chemical equation for the reaction, assuming that the complex is MnF4–.
(b) what was the % of Mn3O4 in the sample ?
86*. A steel sample is to be analysed for Cr and Mn simultaneously. By suitable treatment the Cr is oxidized to Cr2O72–
and the Mn to MnO4–. A 10.00 g sample of steel is used to produce 250.0 mL of a solution containing Cr 2O72–
and MnO4–. A 10.00 mL portion of this solution is added to a BaCl2 solution and by proper adjustment of the
acidity, the chromium is completely precipitated as BaCrO 4 ; 0.0549 g is obtained. A second 10.00 mL portion
of this solution requires exactly 15.95 mL of 0.0750 M standard Fe 2+ solution for its titration (in acid solution).
Calculate the % of Mn and % of Cr in the steel sample.
87*. 1.16 g CH3(CH2)nCOOH was burnt in excess air and the resultant gases (CO 2 and H2O) were passed through
excess NaOH solution. The resulting solution was divided in two equal parts. One part required 50 mL of 1
N HCl for neutralization using phenolphthalein as indicator. Another part required 80 mL of 1 N HCl for
neutralization using methyl orange as indicator. Find the value of n and the amount of excess NaOH solution
taken initially.
88*. A 1.5 g sample containing oxalic acid and some inert impurity was dissolved in enough water and volume made
up to 250 mL. A 20 mL portion of this solution was then mixed with 30 mL of an alkali solution. The resulting
solution was then treated with stoichiometric amount of CaCl2 just needed for precipitation of oxalate as CaC2O4.
Solution was filtered off and filtrate was finally titrated against 0.1 M HCl solution. 8.0 mL of acid was required
to reach the equivalence point. At last, the above neutral solution was treated with excess of AgNO3 solution
and AgCl obtained was washed, dried and weighed to be 0.4305 g. Determine mass percentage of oxalic acid
in the original sample :
89*. A 1 g sample containing NaOH as the only basic substance and some inert impurity was left exposed to atmosphere
for a very long time so that part of NaOH got converted into Na2CO3 by absorbing CO2 from atmosphere. The
resulting sample was dissolved in water and volume made upto 100 mL. A 20 mL portion of this solution required
16 mL 0.25 M HCl solution to reach the equivalence point when methyl orange was used as indicator. In a
separate analysis, 20 mL portion of the same solution was taken along with phenolphthalein indicator and mixed
with 50 mL of 0.1 M HCl solution. An additional 9.00 mL 0.1 M Ba(OH) 2 solution was required to just restore
the pink colour of solution. Determine mass percentage of NaOH in the original sample and mass percentage
of Na2CO3 in the sample after exposure to atmosphere.
90. A 5.0 cm3 solution of H2O2 liberates 0.508 g of iodine from an acidified KI solution. Calculate the strength
of H2O2 solution in terms of volume strength at STP. [JEE 1995]
91*. A 3.00 g sample containing Fe3O4, Fe2O3 and an inert impure substance, is treated with excess of KI solution
in presence of dilute H2SO4. The entire iron is converted into Fe2+ along with the liberation of iodine. The resulting
solution is diluted to 100 mL. A 20 mL of the diluted solution require 11 mL of 0.5 M Na2S2O3 solution to
reduce the iodine present. A 50 mL of diluted solution after complete extraction of the iodine requires 12.80
mL of 0.25 KMnO4 solution in dilute H2SO4 medium for the oxidation of Fe2+. Calculate the percentages of
Fe2O3 and Fe3O4 in the original sample. [JEE 2000]
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JEE-Chemistr y
92*. One litre of a mixture of O2 and O3 at NTP was allowed to react with an excess of acidified solution of KI.
The Iodine liberated required 40 mL of M/10 sodium thiosulphate solution for titration. What is the percent
of ozone in the mixture ? Ultraviolet radiation of wavelength 300 nm can decompose ozone. Assuming that
one photon can decompose one ozone molecule, how many photons would have been required for the complete
decomposition of ozone in the original mixture? [JEE 1997]
93*. A sample of hard water contains 96 ppm of SO2–4 and 183 ppm of HCO–3 , with Ca2+ as the only cation. How
many moles of CaO will be required to remove HCO–3 from 1000 kg of this water? If 1000 kg of this water
is treated with the amount of CaO calculate above, what will be the concentration (in ppm) of residual Ca 2+
ions (Assume CaCO3 to be completely insoluble in water)? If the Ca 2+ ions in one litre of the treated water
are completely exchanged with hydrogen ions, what will be its pH (one ppm means one part of the substance
in one million part of water, weight / weights)? [JEE 1997]
94. An aqueous solution containing 0.10 g KIO3 (formula wt. 214.0) was treated with an excess of KI solution.
The solution was acidified with HCl. The liberated I2 consumed 45.0 mL of thiosulphate solution to decolourise
the blue starch – iodine complex. Calculate the molarity of the sodium thiosulphate solution. [JEE 1998]
95. How many millilitre of 0.5 M H2SO4 are needed to dissolve 0.5 g of copper II carbonate ? [JEE 1999]
96. Hydrogen peroxide solution (20 mL) reacts quantitatively with a solution of KMnO4 (20 mL) acidified with dilute
H2SO4. The same volume of KMnO4 solution is just decolorized by 10 mL of MnSO4 in neutral medium
simultaneously forming a dark brown precipitate of hydrated MnO2. The brown precipitate is dissolved in 10
mL of 0.2 M sodium oxalate under boiling condition in the presence of dilute H 2SO4. Write the balanced equations
involved in the reactions and calculate the molarity of H2O2. [JEE 2001]
97. A sample of oleum is such that ratio of "free SO3" by "combined SO3" is equal to unity. Calculate its labelling
in terms of percentage oleum.
98. In a solution the concentration of CaCl2 is 5 M & that of MgCl2 is 5 m. The specific gravity of solution is 1.05,
calculate the concentration of Cl– in the solution in terms of Molarity.
99*. 1.2475 g of crystalline copper sulphate was dissolved in water and excess of KI was added. The liberated iodine
consumed 50 mL N/10 Na2S2O3 solution to reach the end point of the titration. Calculate the number of water
molecules of hydration in crystalline copper sulphate salt.
100. 25 mL of a solution containing HCl was treated with excess of M/5 KIO3 and KI solution of unknown concentration
where I2 liberated is titrated against a standard solution of 0.021 M Na2S2O3 solution whose 24 mL were used
up. Find the strength of HCl and volume of KIO3 solution consumed :
101*. A sample of steel weighing 0.6 g and containing S as an impurity was burnt in a stream of O2, when S was
converted to its oxide SO 2.SO 2 was then oxidized to SO 4– – by using H 2O 2 solution containing
30 mL of 0.04 M NaOH. 22.48 mL of 0.024 M HCl was required to neutralize the base remaining after oxidation.
Calculate the % of S in the sample :
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Rankers Academy JEE
Redox
ANSWERS
1. Limiting Reagent 2. Oxidised as well as reduced
3. Oxygen has been oxidised and chlorine has been reduced 4. +7/3
5. +2
6. (B) 7. (A) 8. (A) 9. (B) 10. (A)
11. (D) 12. (D) 13. (A) 14. (D) 15. (D)
16. (D) 17. (C) 18. (B) 19. (B) 20. (B)
21. (A) 22. (A) 23. (C) 24. (C) 25. (B)
26. (B) 27. (A) 28. (B) 29. (A) 30. (B)
31. (A) 32. (D) 33. (D) 34. (A) 35. (A)
36. (A) 37. (B) 38. (C) 39. (B) 40. (C)
41. (D) 42. (A) 43. (A)
l Match the Column
44. (A) ® q ; (B) ® p ; (C) ® s ; (D) ® r
l Comprehension
Comprehension 1 : 45. (B) 46. (C) 47. (C)
Comprehension 2 : 48. (A) 49. (B) 50. (B) 51. (B)
52. KOH = 35%, Ca(OH)2 = 65% 53. V = 25 mL

54. MgCO3 = 51.22%, CaCO3 = 48.78 % 55. 4.24 g/L ; 5.04 g/L
56. 39.85% ; 60.15% 57. +3
58. zero 59. V = 31.68 mL
60. 337 mL 61. 41.53 %
62. 0.15 N 63. H2C2O4.2H2O = 14.36%, KH2O4.H2O=81.71%
64. 1.406 % 65. 90.1%
66. 0.1281 g 67. 0.68 g/L
68. 7.1% 69. 84mg
70. (6.23) 71. 8.124 g Zn
72. 29.28 73. 53.3 % Na2CO3
74. 2, 1 75. 31.16, 37.34
76. 3.464 g 77. 18.77 mg
78. 16.38 ml, 34.18 ml 79. 0.5 : 0.1 : 0.4
80. 9.095 × 105 L 81. 1.041 g/mL
82. 58.8% 83. 77.45 mL
84. 0.06 g 85. 61.67%
86. Cr = 2.821% , Mn = 1.498% 87. n = 4, NaOH = 6.4 g
88. 82.5 89. 80, 36.05 %
90. 4.48 91. Fe2O3 = 48.1 %, Fe3O4 = 33.9%
92. 6.57% O3 (by weight), 1.2 × 1021 photons 93. 1.5, 40 ppm, pH = 2.6989
94. 0.0623 M 95. 8.097 ml
96. 0.1 M 97. 110.11 %
98. [Cl–] = 13.36 M 99*. (5)
100. VKIO3 = 0.42 mL , [HCl] = 0.02016 N 101*. 1.76 %
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JEE-Chemistr y
ATOMIC STRUCTURE
True/False
1. The electron density in xy plane of 3d 2 2 orbital is zero..
x -y
2. 3d6 configuration is more stable than 3d5.
3. The potential energy of an electron in an orbit is twice in magnitude as compared to its kinetic energy.
4. The increasing order for the values of e/m (charge/mass) for electron (e), proton (p), neutron (n) and alpha
particle (a) is n < a < p < e.
5. The orbital 3dxy has no probability of finding electron along x and y-axis.
Fill in the blanks

6. Nitrogen has an atomic number of 7 and oxygen has an atomic number of 8. The total number of electrons in
the nitrate ion (NO–3) is ......................... .
7. h/p is the angular momentum of the electron in the ......................... orbit of He+.
8. An emission spectrum has electromagnetic radiation of definite ......................... .
9. The maximum number of electrons that can be accommodated in all the orbitals for which l = 3
is ......................... .
10. The values of n1 and n2 in the Paschen spectral series of hydrogen atom are ......................... and .........................
respectively.
Assertion-Reason
11. Statement-I : Nodal plane of px atomic orbital is yz plane.

Because
Statement-II : In px atomic orbital electron density is zero in the yz plane.
12. Statement-I : No two electrons in an atom can have the same values of four quantum numbers.
Because
Statement-II : No two electrons in an atom can be simultaneously in the same shell, same subshell, same
orbitals and have same spin.
13. Statement-I : p-orbital has dumb-bell shape.

Because
Statement-II : Electrons present in p-orbital can have one of three values for 'm', i.e. 0, +1, –1.
14. Statement-I : The ground state configuration of Cr is 3d5 4s1.

Because
Statement-II : A set of exactly half filled orbitals containing parallel spin arrangement provide extra
stability.
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Rankers Academy JEE
Atomic Structure
15. Statement-I : Limiting line in the balmer series has a wavelength of 36.4 mm.
Because
Statement-II : Limiting lines is obtained for a jump of electron from n = ¥ to n = 2 for Balmer series.
16. Statement-I : The electronic configuration of nitrogen atom is represented as :
not as
Because
Statement-II : The configuration of ground state of an atom is the one which has the greatest multiplicity.
17. Statement-I : The configuration of B atom cannot be 1s 2 2s3.

Because
Statement-II : Hund's rule demands that the configuration should display maximum multiplicity.
18. Statement-1 : The groundstate configuration of Cr is [Ar] 3d 54s1

Statement-2 : The energy of atom is lesser in 3d5 4s1 configuration compared to 3d4 4s2 configuration.
19. Statement-1 :Minimum principal quantum number of an orbital belonging to 'g' sub-shell is 5.
Statement-2 : For a given value of principal quantum number (n), l may have values 0 to (n–1) only.

20. The binding energy of an electron in the ground state of the He atom is equal to 24.6 eV. The energy required to
remove both the electrons from the atom will be
(A) 59 eV (B) 81 eV (C) 79 eV (D) None of these
21. Given DH for the process Li (g) ¾® Li+3 (g) + 3e– is 19800 kJ/mole & IE1 for Li is 520 then IE2 & IE1 of Li+ are
respectively (approx value) :-
(A) 11775, 7505 (B) 19280, 520 (C) 11775, 19280 (D) Data insufficient
22*. From the following observations predict the type of orbital :

Observation 1 : x y plane acts as nodal plane
Observation 2 : The angular function of the orbital intersect the three axis at origin only.
Observation 3 : R2(r)v/s r curve is obtained for the orbital is
2
R (r)
(A) 5pz (B) 6dxy (C) 6dx2 – y2 (D) 6 dyz
23. For which orbital angular probability distribution is maximum at an angle of 45° to the axial direction :-
(A) dx2 – y2 (B) dz2 (C) dxy (D) Px
24. Which orbit would be the first to have 'g' subshell :-

rd th th th
(A) 3 (B) 4 (C) 5 (D) 6
25. The decreasing order of energy of the 3d, 4s, 3p, 3s orbitals is :-
(A) 3d > 3s > 4s > 3p (B) 3s > 4s > 3p > 3d (C) 3d > 4s > 3p > 3s (D) 4s > 3d > 3s > 3p
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26. If n and l are respectively the principle and azimuthal quantum numbers, then the expression for calculating the
total number of electrons in any orbit is :-
l =n l =n -1 l =n +1 l =n -1
(A) å 2(2l + 1) (B) å 2(2l + 1) (C) å 2(2l + 1) (D) å 2(2l + 1)
l =1 l =1 l =0 l =0
27. If wavelength is equal to the distance travelled by the electron in one second, then :-
h h h h
(A) l =
pv
(B) l = (C) l = (D) l =
m p m
28. According to Schrodinger model nature of electron in an atom is as :-

(A) Particles only (B) Wave only
(C) Both simultaneously (D) Sometimes waves and sometimes particle
29. Which describes orbital :-

(A) y (B) y2 (C) |y2|y (D) All
30. In order to have the same wavelength for the electron (mass me) and the neutron (mass mn) their velocities
should be in the ratio (electron velocity/neutron velocity) :-
(A) mn/me (B) mn × me (C) me/mn (D) one
31. The quantum numbers +1/2 and –1/2 for the electron spin represent :-
(A) Rotation of the electron in clockwise and anticlockwise direction respectively.
(B) Rotation of the electron in anticlockwise and clockwise direction respectively.
(C) Magnetic moment of the electron pointing up and down respectively.
(D) Two quantum mechanical spin states which have no classifical analogue.
32. Which is true about y :-

(A) y represents the probability of finding an electron around the nucleus
(B) y represent the amplitude of the electron wave
(C) Both A and B
(D) None of these
th
33. Consider an electron in the n orbit of a hydrogen atom in the Bohr model. The circumference of the orbit can
be expressed in terms of the de Broglie wavelength l of the electron as :-
(A) (0.529) nl (B) nl (C) (13.6) l (D) nl
34. A particle X moving with a certain velocity has a debroglie wave length of 1A°. If particle Y has a mass of 25%
that of X and velocity 75% that of X, debroglies wave length of Y will be :-
(A) 3 A° (B) 5.33 A° (C) 6.88 A° (D) 48 A°
35. What are the values of the orbital angular momentum of an electron in the orbitals 1s, 3s, 3d and 2p :-
(A) 0, 0, 6h, 2h (B) 1, 1, 4h, 2h (C) 0, 1, 6h, 3h (D) 0, 0, 20h, 6
36. If m = magnetic quantum number and l = azimuthal quantum number then :-
m -1
(A) m = l + 2 (C) l = (D) l = 2m + 1
2
(B) m = 2l + 1
2
37. The number of unpaired electrons in Mn4+ (Z = 25) is :-

(A) Four (B) Two (C) Five (D) Three
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Rankers Academy JEE
Atomic Structure
38. After np orbitals are filled, the next orbital filled will be :-
(A) (n + 1) s (B) (n + 2) p (C) (n + 1) d (D) (n + 2) s
39. The value of the magnetic moment of a particular ion is 2.83 Bohr magneton. The ion is :-
(A) Fe2+ (B) Ni2+ (C) Mn2+ (D) Co3+
40. In Bohr's model of the hydrogen atom the ratio between the period of revolution of an electron in the orbit of
n = 1 to the period of the revolution of the electron in the orbit n = 2 is :-
(A) 1 : 2 (B) 2 : 1 (C) 1 : 4 (D) 1 : 8
41. Let u1 be the frequency of the series limit of the Lyman series, u2 be the frequency of the first line of the lyman
series, and u3 be the frequency of the series limit of the Balmer series :-
(A) u1 – u2 = u3 (B) u2 – u1 = u3 (C) u3 = 1/2 (u1 – u3) (D) u1 + u2 = u3
42. The energies of energy levels A, B and C for a given atom are in the sequence E A < EB < EC. If the radiations
of wavelengths l1, l2 and l3 are emitted due to the atomic transitions C to B, B to A and C to A respectively then
which of the following relations is correct :-
l1l2
(A) l1 + l2 + l3 = 0 (B) l3 = l1 + l22 (C) l3 = l1 + l2 (D) l3=
l1 + l 2
43. The wavelengths of photons emitted by electron transition between two similar levels in H and He + are l1 and
l2 respectively. Then :-
(A) l2= l1 (B) l2= 2l1 (C) l2= l1/2 (D) l2 = l1/4
44. If first ionization potential of an atom is 16 V, then the first excitation potential will be :-
(A) 10.2 V (B) 12 V (C) 14 V (D) 16 V
45. In which transition minimum energy is emitted :-

(A) ¥ ® 1 (B) 2 ® 1 (C) 3 ® 2 (D) n ® (n – 1) (n ³ 4)
46. No. of visible lines when an electron returns from 5 th orbit to ground state in H spectrum :-
(A) 5 (B) 4 (C) 3 (D) 10
47. Which of the following has maximum number of unpaired electron (atomic number of Fe 26)
(A) Fe (B) Fe (II) (C) Fe (III) (D) Fe (IV)
48. Suppose a particle has four quantum numbers such that the permitted values are:
n = 1, 2, 3........
l = (n – 1), (n – 3), (n – 5) ...........but no negative value
æ 1ö æ 1ö
j = çl + ÷ø or çè l - ÷ø , the later is not negative
è 2 2
m = –j in integer step to +j what are the other permitted values for n = 2?
3 3 1 1
(A) l = 1, j = ,m = - (B) l = 0, j = ;m = -
2 2 2 2
1 3
(C) l = 1, j = ;m = - (D) All of these
2 2
49. Which of the following is / are false.

(A) Multiplicity in Fe3+ is greater than Co3+. (B) Ti3+, Cr+, Sc2+ ions are diamagnetic.
(C) Value of (n + l + m) for last electron in Na is 3. (D) Number of neutron in 1.07 gm Fe(OH)3 is 3.25 × 1023
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50. The orbital diagram in which Hund’s rule is violated is
(I) (II)
(III) (IV)
(A) I & II (B) II & III (C) III & IV (D) II & IV

(‘l’ and ‘m’ are respectively the azimuthal and magnetic quantum numbers)
Column I Column II
(I) Total number of values of (l) for a shell (P) 0, 1, 2, .................(n–1)
(II) Values of (l) for a shell (Q) +l, .....+2, +1, 0, –1, –2, .......–l
(III) Total number of values of (m) for a subshell (R) (2l + 1)
(IV) Values of (m) for a subshell (S) n
(A) (I) S (II) P (III) R (IV) Q (B) (I) S (II) R (III) P (IV) Q
(C) (I) P (II) S (III) R (IV) Q (D) (I) P (II) R (III) Q (IV) S
52. Which of the following statements regarding subshell filling order for a neutral atom is/are correct ?
(I) Electrons are assigned to the 4s subshell before they are assigned to the 3d subshell
(II) Electrons are assigned to the 4f subshell before they are assigned to the 6s subshell
(III) Electrons are assigned to the 4d subshell before they are assigned to the 5p subshell
(A) I only (B) II only (C) I and III (D) I, II and III
53. If the nitrogen atom had electronic configuration 1 s7, it would have energy lower that of normal ground state
configuration 1s2 2s2 2p3, because the electrons would be closer to the nucleus. Yet 1 s 7 is not observed because
it violates :-
(A) Heisenberg uncertainty principle (B) Hunds rule
(C) Pauli's exclusion principle (D) Bohr postulate of stationary orbits
54. The explanation for the presence of three unpaired electrons in the nitrogen atom can be given by
(A) Pauli’s exclusion principle (B) Hund’s rule
(C) Aufbau’s principle (D) Uncertainity principle
55. Which of the following has the maximum number of unpaired electrons ? [JEE 1996]
(A) Mg2+ (B) Ti3+ (C) V3+ (D) Fe2+

(i) n = 4 , l = 1 (ii) n = 4 , l = 0 (iii) n = 3 , l = 2
(A) (iv) < (ii) < (iii) < (i) (B) (iii) < (ii) < (iv) < (i) (C) (i) < (iii) < (ii) < (iv) (D) (iii) < (i) < (iv) < (ii)
57. Rutherfords experiment , which established the nuclear model of atom, used a beam of :– [JEE 2002]
(A) b - particles, which impinged on a metal foil and get absorbed.
(B) g - rays, which impinged on a metal foil and ejected electron.
(C) Helium atoms, which impinged on a metal foil and got scattered.
(D) Helium nuclie, which impinged on a metal foil and got scattered.
(A) 3 (B) 8 (C) 15 (D) 24
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Atomic Structure
59. The radius of which of the following orbit is same as that of the first Bohr’s orbit of hydrogen atom?
[JEE 2004]
(A) He+ (n = 2) (B) Li2+ (n = 2) (C) Li2+ (n = 3) (D) Be3+ (n = 2)
(A) 3 (B) 8 (C) 15 (D) 24
Multi Choice Correct

61. Which of the following statements is/are incorrect ?
(A) Lanthanum is the first element of lanthanides (B) Actinium violates the Aufbau's principle.
(C) Chromium violates the Pauli's exclusion principle. (D) Total 10 exchanges are possible for d electrons in Zn.
62. Bohr's theory is not applicable to -

(A) He (B) Li2+ (C) He2+ (D) the H-atom
63. In which transition, one quantum of energy is emitted -

(A) n = 4 ® n = 2 (B) n = 3 ® n = 1 (C) n = 4 ® n = 1 (D) n = 2 ® n = 1
64. Choose the correct relation on the basis of Bohr's theory -
1 Z2
(A) velocity of electron µ (B) frequency of revolution µ
n n3
Z3
(C) radius of orbit µ n2Z (D) force on electron µ
n4
65. The magnitude of the spin angular momentum of an electron is given by -
h h 3 h 1 h
(A) S = s(s + 1) (B) S = s (C) S = ´ (D) S = ± ´
2p 2p 2 2p 2 2p
66. A hydrogen - like atom has ground state binding energy 122.4 eV. Then :
(A) its atomic number is 3
(B) an photon of 90 eV can excite it to a higher state
(C) an 80 eV photon cannot excite it to a higher state
(D) an electron of 8.2 eV and a photon of 91.8 eV are emitted when a 100 eV electron interacts with it
67*. In a hydrogen like sample two different types of photons A and B are produced by electronic transition. Photon
B has it’s wavelength in infrared region if photon A has more energy then B, then the photon A may belong to
the region.
(A) ultraviolet (B) visible (C) infrared (D) None
68*. Hydrogen atoms in a particular excited state ‘n’, when all returned to ground state, 6 different photons are
emitted. Which of the following is/are incorrect.
(A) Out of 6 different photons only 2 photons have wavelength equal to that of visible light.
(B) If highest energy photon emitted from the above sample is incedent on the metal plate having work function
8 eV, AKE of liberated photo-electron may be equal to or less than 4.75 eV.
(C) Total number of radial nodes in all the orbitals of nth shell is 24.
(D) Total number of angular nodes in all the orbitals in (n-1)th shell is 23.
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JEE-Chemistr y
69*. In a H-like sample electrons make transition from 4th excited state to 2nd state then
(A)10 different spectral lines are observed
(B) 6 different spectral lines are observed
(C) number of lines belonging to the balmier series is 3
(D) Number of lines belonging to paschen series is 2.
70. Gaseous state electronic configuration of nitrogen atom can be represented as : [JEE 1999]
(A) ¯ ¯ (B) ¯ ¯ ¯ (C) ¯ ¯ ¯ ¯ (D) ¯ ¯ ¯ ¯ ¯
71. The electronic configuration of an element is 1s2 2s2 2p6 3s2 3p6 3d5 4s1. This represents its : [JEE 2000]
(A) excited state (B) ground state (C) cationic form (D) none
72. Which is true about an electron -

(A) rest mass of electron is 9.1 × 10–28 g
(B) mass of electron increases with the increase in velocity
(C) molar mass of electron is 5.48 × 10 –4 g/mole
(D) e/m of electron is 1.7 × 108 coulomb/g
73. In a hydrogen like sample electron is in 2nd excited state, the Binding energy of 4th state of this sample is 13.6 eV,
then
(A) A 25 eV photon can set free the electron from the second excited state of this sample.
(B) 3 different types of photon will be observed if electrons make transition up to ground state from the second
excited state
(C) If 23 eV photon is used then K. E. of the-ejected electron is 1 eV.
(D) 2nd line of Balmer series of this sample has same energy value as 1st excitation energy of H-atoms.
74*. A hydrogen like atom in ground state absorbs ‘n’ photons having the same energy and it emits exactly ‘n’
photons when electronic transition takes place. Then the energy of the absorbed photon may be
(A) 91.8 eV (B) 40.8 eV (C) 48.4 eV (D) 54.4 eV
Match the Column

75*. Frequency = f, Time period = T, Energy of nth orbit = En, radius of nth orbit = rn, Atomic number = Z, Orbit
number = n :
Column-I Column-II
(A) f (p) n3
2
(B) T (q) Z
1
(C) En (r)
n2
1
(D) r (s) Z
n
76. Match the following:

Column I Column II
(A) Orbital with equal number of radial and angular nodes (p) 3d x2 - y2
(B) Orbital with number of radial nodes less than the number of angular nodes (q) 2pz
(C) Orbital with zero radial nodes but two angular node. (r) 3px
(s) 5dxy
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Rankers Academy JEE
Atomic Structure
77. Column-I Column-II
(A) Aufbau principle (p) Line spectrum in visible region
(B) de broglie (q) Orientation of an electron in an orbital
(C) Angular momentum (r) Photon
(D) Hund's rule (s) l = h/mv
(E) Balmer series (t) Electronic configuration
(F) Planck's law (u) mvr
Comprehension
Read the following rules and answer the questions at the end of it.
Electrons in various suborbits of an orbit are filled in increasing order to their energies.
Pairing of electrons in various orbitals of a suborbit takes place only after each orbital is half-filled.
No two electrons in an atom can have the same set of quantum number.
78. Cr (Z = 24), Mn+ (Z = 25), Fe2+ (Z = 26) and Co3+ (Z = 27) are isoelectronic each having 24 electrons.
Thus,
(A) all have configurations as [Ar] 4s1 3d5
(B) Cr and Mn+ have configurations as [Ar] 4s1 3d5 while Fe2+ and Co3+ have configurations as [Ar]3d6.
(C) all have configurations as [Ar] 3d6
(D) all have configurations as [Ar] 4s2 3d6
79. A compound of vanadium has a magnetic moment of 1.73 BM. Electronic configuration of the vanadium ion
in the compound is :
(A) [Ar] 4s0 3d1 (B) [Ar] 4s2 3d3 (C) [Ar] 4s1 3d0 (D) [Ar] 4s0 3d5
80. Which of these ions are expected to be paramagnetic and coloured in aqueous solution ?
(A) Fe3+, Ti3+, Co3+ (B) Cu+, Ti4+, Sc3+ (C) Fe3+, Ni2+, V5+ (D) Cu+, Cu2+, Fe2+
81. While writing the following electronic configuration of Fe some rules have been violated :
I : Aufbau rule, II : Hund's rule III : Pauli's exclusion principle
Ar ¯
3d 4s
(A) I, II (B) II, III (C) I, III (D) III
82. How many elements would be in the second period of the periodic table if the spin quantum number (ms) could
1 1
have the value of - ,0, + ?
2 2
(A) 8 (B) 10 (C) 12 (D) 18
83. The sub-shell that arises after f sub-shell is called g sub-shell.

(A) it contains 18 electrons and 9 orbitals
(B) it corresponds to l = 4 and first occurs in 5th energy level
(C) a g-orbital can have maximum of two electrons
(D) all the above statements are true.
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Subjetive Questions
84*. An alpha particle after passing through a potential difference of 2 × 106 volt falls on a silver foil. The atomic
number of silver is 47. Calculate :
(i) the K.E. of the alpha–particle at the time of falling on the foil.
(ii) K.E. of the a–particle at a distance of 5 × 10–14 m from the nucleus,
(iii) the shortest distance from the nucleus of silver to which the a–particle reaches.
85*. A beam of some kind of particle of velocity 2 × 107 m/s is scattered by a gold (z = 79) foil. Find specific charge
of this particle (charge / mass) if the distance of closest approach is 7.9 × 10–14 m.
86*. A certain dye absorbs light of l = 4530 Å and then fluorescence light of 5080 Å. Assuming that under given
conditions 47% of the absorbed energy is re-emitted out as fluorescence, calculate the ratio of number of quanta
emitted out to the number of quanta absorbed. radiations. Find the wavelength of these induced radiations.
87. The IP1 of H is 13.6 V. It is exposed to electromagnetic waves of 1028 Å and gives out induced.
88. An electron in a hydrogen like species is in the excited state n2. The wavelength for the transition from
n2 to n1 = 2 is 48.24 nm. The corresponding wavelength for the transition n 2 to n1 = 3 is 142.46 nm. Find the
value of n2 and Z and report the H like atom.
89*. When electromagnetic radiation of wavelength 300 nm falls on the suface of sodium, electrons are emitted with
a kinetic energy of 1.68 × 105 J mol–1. What is the minimum energy needed to remove an electron from
sodium ? What is the maximum wavelength that will cause a photoelectron to be emitted?
90. How long would it take a radio wave of frequency 6 × 10 3 sec–1 to travel from mars to the earth, a distance of
8 × 107 km ?
91. The energy levels of hypothetical one electron atom are shown below.
0 eV —— n = ¥
–0.50 eV —— n = 5
–1.45 eV —— n = 4
–3.08 eV —— n = 3
–5.3 eV —— n = 2
–15.6 eV —— n = 1
(a) Find the ionisation potential of atom?
(b) Find the short wavelength limit of the series terminating at n = 2 ?
(c) Find the wave no. of photon emitted for the transition made by the electron from third orbit to first
orbit ?
(d) Find the minimum energy that an electron will have after interacting with this atom in the ground
state, if the initial kinetic energy of the electron is (i) 6eV (ii) 11 eV ?
92. Suppose 10–17 J of light energy is needed by the interior of the human eye to see an object. How many photons
of green light (l = 550 nm) are needed to generate this minimum amount of energy?
93. Find the number of photons of radiation of frequency 5 × 10 13 s–1 that must be absorbed in order to melt one
g ice when the latent heat of fusion of ice is 330 J/g.
94. The eyes of certain member of the reptile family pass a single visual signal to the brain when the visual receptors
are struck by photons of wavelength 850 nm. If a total energy of 3.15 × 10 –14 J is required to trip the signal,
what is the minimum number of photons that must strike the receptor?
95. To what series does the spectral lines of atomic hydrogen belong if its wave number is equal to the difference
between the wave number of the following two lines of the Balmer series 486.1 and 410.2 nm. What is the
wavelength of this ?
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Rankers Academy JEE
Atomic Structure
96. Calculate the threshold frequency of metal if the binding energy is 180.69 kJ mol–1 of electron.
97. Calculate the binding energy per mole when threshold wavelength of photon is 240 nm.
98. A metal was irradiated by light of frequency 3.2 × 1015 s–1. The photoelectron produced had its KE,
2 times the KE of the photoelectron which was produced when the same metal was irradiated with a light of
frequency 2.0 × 1015 s–1. What is work function ?
99. U.V. light of wavelength 800 A° & 700 A° falls on hydrogen atoms in their ground state & liberates electrons with
kinetic energy 1.8 eV and 4 eV respectively. Calculate planck's constant.
100. A potential difference of 20 kV is applied across an X-ray tube. Find the minimum wavelength of X-ray gener-
ated.
101. The K.E. of an electron emitted from tungsten surface is 3.06 eV. What voltage would be required to bring the
electron to rest.
æ 8kT ö
102. What is de-Broglie wavelength of a He-atom in a container at room temperature. ç Use Uavg. = ÷
è pm ø
103. Through what potential difference must an electron pass to have a wavelength of 500 A°.
104. A proton is accelerated to one tenth of the velocity of light. If its velocity can be measured with a precision
± 1%. What must be its uncertainty in position ?
105. To what effective potential a proton beam be subjected to give its protons a wavelength of 1 × 10 –10m.
106. Calculate the number of exchange pairs of electrons present in configuration of Cu according to Aufbau princi-
ple considering 3d orbitals.
107. He atom can be excited to 1s1 2p1 by l = 58.44 nm. If lowest excited state for He lies 4857 cm–1 below the
above. Calculate the energy for the lower excitation state.
108. A certain dye absorbs 4530 A° and fluoresence at 5080 A° these being wavelengths of maximum absorption that
under given conditions 47% of the absorbed energy is emitted. Calculate the ratio of the no. of quanta emitted
to the number absorbed.
109. The dissociation energy of H2 is 430.53 kJ/mol. If H2 is exposed to radiant energy of wavelength 253.7 nm, what
% of radiant energy will be converted into K.E ?
110. Iodine molecule dissociates into atoms after absorbing light of 4500 A 0 If one quantum of radiation is absorbed
by each molecule, calculate the K.E. of iodine atoms.
(Bond energy of I2 = 240 kJ/mol)
111. What is de-Broglie wavelength associated with an e – accelerated through potential difference of 100 kV ?
112. Calculate the de-broglie wavelength associated with motion of earth (mass 6 × 10 24 kg) orbiting around the sun
at a speed of 3 × 106 m/s.
113. A base ball of mass 200 g is moving with velocity 30 × 10 2 cm/s. If we can locate the base ball with error equal
in magnitude to the l of the light used (5000 Å), how will the uncertainty in momentum compared with the total
momentum of base ball ?
114. An electron has a speed of 40 m/s, accurate up 99.99 %. What is the uncertainty in locating position?
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Rankers Academy JEE
JEE-Chemistr y
115. Instead of principal quantum number (n), azimuthal quantum number (l) & magnetic quantum number m, a set
of new quantum numbers s, t and u was introduced with similar logic but different values as defined below.
s = 1, 2, 3, ........¥ all positive integral values.
t = (s2 – 12), (s2 – 22), (s2 – 32) ........ No negative value
(t + 1) (t + 1)
u=- to + (including zero, if any) in integral steps.
2 2
Each orbital can have maximum four electrons.
(s + t) rule is defined, similar to (n + l) rule.
(i) Number of electrons that can be accommodated in s = 2 and s = 3 shell.
(ii) Number of electrons for which s = 2, t = 3 for an element with atomic number 24.
(iii) The number of subshells in which the third shell is subdivided equal to
116. Calculate the Rydberg constant R if He+ ions are known to have the wavelength difference between the first (of
the longest wavelength) lines of Balmer and Lyman series equal to 133.7 nm.
117. Calculate the wavelength in angstrom of photon that is emitted when an e– in Bohr orbit n = 2 returns to the
orbit n = 1. The ionization potential of the ground state of hydrogen atom is 2.17 × 10 –11 erg/atom.
118. One mole He+ ions are excited. Spectral analysis showed existence of 50% ions in 3rd orbit, 25% in
2nd and rest in ground state. Calculate total energy evolved when all the ions return to the ground state.
119. Calculate the frequency of e– in the first Bohr orbit in a H-atom.
120. How many electrons are present in P–shell.
121. According to Aufbau’s Principle, the maximum of electron that can be accomodated in the outermost orbit (ab)
and the penultimate orbit (cd) is :
122. To what series does the spectral lines of atomic hydrogen belong if its wave number is equal number is equal to
the difference between the wave numbers of the following two lines of the Balmer series 486.1 and 410.2 nm?
What is the wavelength of this line ?
123. Hydrogen atom in its ground state is excited by means of monochromatic radiation of wavelength
975 A°. How many different lines are possible in the resulting spectrum? Calculate the longest wavelength
amongst them.
124. Identify number of correct statements.

(A) Weight of 0.002 gm–atom of fluorine is 38 mg.
(B) Average atomic weigth of an element is the weight of most of the atoms.
(C) The value of ‘l’ for 5th electron of any element (Z > 5) will be same.
(D) In case of CO weight of carbon atoms is equal to weight of oxygen atoms.
(E) The value of ‘m’ must be zero for last electron of Ne.
(F) To obtain 0.1 mole of K2SO4.Al2(SO4)3.24H2O weight of oxygen required is 64 g.
(G) N–3 and P–3 are isoelectronic.
(H) Hydrogen(H) and Deuterium (D) are isobars.
125. Find the number of electrons having the value of azimuthal quantum number ‘l’ = 1 for Cd2+.
126. (a) The Schrodinger wave equation for hydrogen atom is [IIT-2004]
3/2
1 æ 1 ö
æ r0 ö -r / a
y 2s = 1/ 2 ç ç 2 - ÷e
÷
4(2p) è a 0 ø
è a0 ø
Where a0 is Bohr's radius. Let the rdial node in 2s be at r 0. Then find r0 in terms of a0.
(b) A base ball having mass 100 g moves with velocity 100 m/s. Find out the value of wavelength of base ball.
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Rankers Academy JEE
Atomic Structure
127. (a) Calculate velocity of electron in first Bohr orbit of hydrogen atom (Given r = a 0) [IIT-2005]
(b) Find de-Broglie wavelength of the electron in first Bohr orbit.
(c) Find the orbital angular momentum of 2p-orbital in terms of h/2p units.
128. Find the quantum number 'n' corresponding to the excited state of He+ ion if on transition to the ground state
that ion emits two photons in succession with wavelengths 108.5 and 30.4 nm.
129*. A gas of identical H-like atom has some atoms in the lowest (ground) energy level A and some atoms in a
particular upper (excited) energy level B and there are no atoms in any other energy level. The atoms of the gas
make transition to a higher energy level by absorbing monochromatic light of photon energy 2.7 eV. Subse-
quently, the atoms emit radiation of only six different photons energies. Some of the emitted photons have
energy 2.7 eV. Some have more and some have less than 2.7 eV.
(a) Find the principal quantum number of initially excited level B.
(b) Find the ionisation energy for the gas atoms.
(c) Find the maximum and the minimum energies of the emitted photons.
130*. A hydrogen like atom (atomic number Z) is in a higher excited state of quantum number n. This excited
atom can make a transition to the first excited state by successively emitting two photons of energies
10.20 eV and 17.00 eV respectively. Alternatively, the atom from the same excited state can make a
transition to the second excited state by successively emitting two photons of energy 4.25 eV and 5.95 eV
respectively. Determine the values of n and z (ionisation energy of hydrogen atom = 13.6 eV).
131. An energy of 68 eV is required to excite a hydrogen like atom from its second Bohr orbit to the third. The nuclear
charge is Ze. Find the value of Z, the kinetic energy of the electron in the first Bohr orbit and the wavelength of
the radiation required to eject the electrons from the first Bohr orbit to infinity.
132. The ionisation energy of a H-like Bohr atom is 4 Rydbergs.

(i) What is the wavelength of radiation emitted when the e – jumps from the first excited state to the ground
state?
(ii)What is the radius of first Bohr orbit for this atom? [1 Rydberg = 2.18 × 10 –18 J]
133*. Photon having wavelength 12.4 nm was allowed to strike a metal plate having work function 25 eV. Calculate
the -
(a) Maximum kinetic energy of photoelectrons emitted in eV.
(b) Wavelength of electron with maximum kinetic energy in A°.
(c) Calculate the uncertainity in wavelength of emitted electron, if the uncertainity in the momentum is
6.62 × 10–28 kg m/sec.
134*. Electron present in single electron species jumps from energy level 3 to 1. Emitted photons when passed through
Z2
a sample containing excited He+ ion causes further excitation to some higher energy level (Given En = 13.6 )
n2
: Determine .
(i) Atomic number of single electron species.
(ii) Principal quantum number of initial excited level & higher energy of He +
135*. The angular momentum of an electron in a Bohr's orbit of H-atom is 3.1652 × 10 –34 kg-m2/sec. Calculate the
wave number in terms of Rydberg constant (R) of the spectral line emitted when an electron falls from this level
to the ground state. (Use h = 6.626 × 10–34 Js).
136. If for any electron in an orbital another parameter ‘B’ is defined as B = n + l + m, where n, l, m are the
quantum numbers of that orbital then what will be the maximum value of B for the last electron of 35Br.
137. In case of nitrogen, if M1 represents spin multiplicity if Hund’s rule is followed and M 2 represents spin multiplicity
M1
if only Hund’s Rule is violated then the value of M will be:
2
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Rankers Academy JEE
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ANSWERS
l True and False
1. False 2. False 3. True 4. True 5. True

6. 32 7. 2nd 8. frequency or wavelength 9. 14
10. 3, (4, 5, 6,....)
11. (A) 12. (A) 13. (B) 14. (A) 15. (A)
16. (A) 17. (B) 18. (A) 19. (A)

20. (C) 21. (A) 22. (D) 23. (C) 24. (C)
25. (C) 26. (D) 27. (D) 28. (B) 29. (B)
30. (A) 31. (D) 32. (B) 33. (D) 34. (B)
35. (A) 36. (C) 37. (D) 38. (A) 39. (B)
40. (D) 41. (A) 42. (D) 43. (D) 44. (B)
45. (D) 46. (C) 47. (C) 48. (A) 49. (B)
50. (C) 51. (A) 52. (C) 53. (C) 54. (B)
55. (D) 56. (A) 57. (D) 58. (C) 59. (D)
60. (C)
l Multi Choice Correct

61. (ACD) 62. (AC) 63. (ABCD) 64. (ABD) 65. (AC)
66. (ACD) 67*. (ABC) 68*. (CD) 69*. (BCD) 70. (AD)
71. (BC) 72. (ABCD) 73. (AB) 74. (AB)
l Match the Column

75*. (A) ® q ; (B) ® p ; (C) ® q,r ; (D) ® r,s
76. (A) - (rs), (B) - (qp), (C) - (p)
77. (A) ® t; (B) ® s ; (C) ® u ; (D) ® q ; (E) ® p; (F) ® r
l Comprehension
78. (B) 79. (A) 80. (A) 81. (D) 82. (C)
83. (D)
84. (i) 6.4 × 10–13 J (ii) 2.1 × 10–13 J, (iii) 3.4 × 10–14 m
85. 1.39 × 108 C/kg
86. 0.526
87. I induced = 1028 Å , II induced = 1216 Å, III induced = 6568 Å
88. n2 = 5, Z = 3, Li2+.
89. 517 nm.
90. 2.66 × 102sec
91. (a) 15.6 eV (b) 233.9 nm,
(c) 1.008 × 107 m–1 (d) (i) electron will not interact(ii) 0.7 eV
22
92. 28 photons 93. 10 94. 1.35 × 105
95. Brackett ; 2.63 × 10–4 m 96. 4.5 × 1014 s–1 97. 497 kJ/mol
–34
98. 319.2 kJ/mol 99. 6.57 × 10 Js 100. 0.62 A°
101. 3.06 V 102. 0.79 A° 103. 6.03×10–4volt
104. 1.05 × 10–13m 105. 0.0826 volts 106. (16)
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Rankers Academy JEE
Atomic Structure
–18
107. 3.3 × 10 J 108. 0.527 109. 8.68 %
110. 2.186 × 10–20 Joules 111. 3.88 pm 112. 3.68 × 10–65 m
113. 1.75 × 10–29 114. 0.0144 m 115. (i) 28, 76 ; (ii) (0) ; (iii) (3)
116. 1.096 × 107 m–1 117. 1220 A° 118. 331.13×104J
119. 6530 × 1012 Hz 120. (72) 121. (818)
–4
122. n1 = 4, n2 = 6, 2.63 × 10 cm 123. six, 18800 A°
124. (3) 125. (18) 126. (a) r0 = 2a0 ; (b) 6.626 × 10–35 m
127. (a) 2.197 × 106 m/s
(b) 3.31 Å
h
(c) 2.
2p
128. n = 5 129*. (a) n = 2, (b) 14.4 eV, (c) 13.5eV, 0.7eV
130*. n = 6, Z = 3 131. 6 ; 489.6 eV, 25.28 A°
132. 300.89 A°, 2.645 × 10–9 cm 133*. (a) 75 eV ; (b) 1.414 A° ; (c) 2 × 10–14 m
134*. (i) Z = 1 (ii) For He+ ion this energy corresponds to excitation from 2 to 6.
æ8ö
135*. R ç ÷ 136. (6) 137. (2)
è9ø
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Rankers Academy JEE
JEE-Chemistr y
GASEOUS STATE
True / False
1. The volume occupied by 32 g of oxygen is greater than that occupied by 16 g of methane, both being at the
same T and P.
2. A real gas can be liquefied if its temperature is greater than its critical temperature.
3. Kinetic energy of gaseous molecules is zero at 0°C.
4. The term Vm– b in vander waals equation represents the available volume where molecules of the gas can move.
5. The average speed of a gas varies linearly with increases of temperature.
6. A mixture of ideal gaseous is cooled upto liquid helium temperature (4.22 K) to form an ideal solution.
7. For a vander waals gas VC = 3b, PC = a/27 b2, TC = 8a/27b R. Numerically the compressibility factor of a
vander waals gas at the critical points is Z = 0.375.
Fill in the blanks

8. The value of PV for 5.6 L of an ideal gas is ......................... RT at STP.
9. The density of an ideal gas ......................... with increase in temperature of the gas, provided the pressure
remains constant.
10. The unit of vander waals constant 'a' in SI units is ......................... .
11. 0.5 L of a certain gas at STP weighs 0.58 g. Its molar mass is .........................g mol–1.
12. The root means square speed of methane gas will be ......................... that of helium gas both having the
same temperature and pressure.
13. (i) The rate of diffusion of a gas is ................ proportional to ..................... or square root of molecular mass.
(ii) The total energy of one mole of gas (ideal monoatomic) at 27°C is ......................... calorie.
(iii) Equal masses of SO2 and O2 are kept in a vessel at 27°C. The total pressure is 2 atm. The partial pressure
of SO2 is ......................... .
14. (i) There is no effect of ......................... on the motion of gas molecules.
(ii) If the density of a gas at 27°C and 1 atmospheric pressure is 1.8 g lit –1, its molecular mass is ..........................
(iii) If the speed of a molecule at 27°C is 0.25 metre sec–1, its speed at 927°C will be ......................... .
(iv) A steel vessel of capacity 22.4 litre contains 2 g of hydrogen, 8g of oxygen and 22 g of carbon dioxide
at a temperature of 0°C. The total pressure of the gas is ......................... .
15. A gas has a volume of 580 cm3 at a certain pressure. If its pressure is increased by 0.96 atm, its volume becomes
3
100 cm . The new pressure of the gas is ......................... .
Assertion & Reason

16. Statement-I : Plot of P Vs. 1/V (volume) is a straight line.

Because
Statement-II : Pressure is directly proportional to volume.
17. Statement-I : Absolute zero is a theoretically possible temperature at which the volume of the gas becomes zero.
Because
Statement-II : The total kinetic energy of the molecule is zero at this temperature.
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Rankers Academy JEE
Gaseous State
18. Statement-I : Critical temperature of the gas is the temperature at which it occupies 22.4 L of volume.
Because
Statement-II : Molar volume of every gas at NTP is 22.4 L.
19. Statement-I : Excluded volume or co-volume equals to (v–nb) for n moles.

Because
Statement-II : Co-volume depends on the effective size of gas molecules.
20. Statement-I : Most probable velocity is the velocity possessed by maximum fraction of molecules at the same
temperature.
Because
Statement-II : On collision, more and more molecules acquire higher speed at the same temperature.
21. Statement-I : The diffusion rate of oxygen is smaller than that of nitrogen.
Because
Statement-II : Molecular size of nitrogen is smaller than that of oxygen.

22*. A certain volume of argon gas (Mol Wt. 40) requires 45 s to effuse through a hole at a certain pressure and
temperature. The same volume of another gas of unknown molecular weight requires 60 s to pass through
the same hole under the same conditions of temperature and pressure. The molecular weight of the gas is
(A) 53 (B) 35 (C) 71 (D) 120
23*. Two closed vessel A and B of equal volume containing air at pressure P1 and temperature T1 are connected
to each other through a narrow open tube. If the temperature of one is now maintained at T1 and other at
T2 (where T1 > T2) then that what will be the final pressure ?
T1 2P1T2 2P1T2 2P1

(A) (B) T + T (C) T - T (D) T + T
2P1T2 1 2 1 2 1 2
24*. A balloon containing 1 mole air at 1 atm initially is filled further with air till pressure increases to 4 atm. The
initial diameter of the balloon is 1 m and the pressure at each stage is proportion to diameter of the balloon.
How many no. of moles of air added to change the pressure from 1 atm to 4 atm :
(A) 80 (B) 257 (C) 255 (D) 256
25*. What is the density of wet air with 75% relative humidity at 1 atm and 300 K? Given : vapour pressure of
H2O is 30 torr and average molar mass of air is 29 g mol–1 :
(A) 1.614 g/L (B) 0.96 g/L (C) 1.06 g/L (D) 1.164 g/L
26*. Consider the following statements :

The coefficient B in the virile equation on state
æ B C ö
PVm = RT çç 1 + V + 2 + .......... ÷÷
è m Vm ø
a : is independent of temperature
b : is equal to zero at boyle temperature
c : has the dimension of molar volume
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Rankers Academy JEE
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Which of the above statements are correct.
(A) a and b (B) a and c (C) b and c (D) a, b and c
27*. Consider the following statements : If the vander Waal's parameters of two gases are given as
a (atm lit2 mol–2) b (lit mol–1)
Gas X : 6.5 0.056
Gas Y : 8.0 0.011
then a : VC (X) < VC (Y)
b : PC (X) < PC (Y)
c : TC (X) < TC (Y)
Select correct alternate :
(A) a alone (B) a and b (C) a,b and c (D) b and c
28*. At low pressures, the vander Waal's equation is written as :
é a ù
êë p + V 2 úû V = RT
The compressibility factor is then equal to :
æ a ö æ RTV ö æ a ö æ RTV ö
(A) ç 1 - ÷ (B) ç 1 - (C) ç 1 + (D) ç 1 +
è RTV ø è a ÷ø è RTV ÷
ø è a ÷ø
29*. NH3 gas is liquefied more easily than N2. Hence :

(A) vander Waal's constants 'a' and 'b' of NH3 > that of N2
(B) vander Waal's constants 'a' and 'b' of NH3 < that of N2
(C) a (NH3) > a (N2) but b (NH3) < b (N2)
(D) a (NH3) < a (N2) but b (NH3) > b (N2)
30*. For the non-zero values of force of attraction between gas molecules, gas equation will be :
n 2a nRT
(A) PV = nRT – (B) PV = nRT + nbP (C) PV = nRT (D) P =
V V-b
31. Compressibility factor for H2 behaving as real gas is :
æ a ö æ Pb ö RTV
(A) 1 (B) ç 1 - ÷ (C) ç 1 + ÷ (D)
è RTV ø è RT ø (1 - a)
32. Equal masses of methane and oxygen are mixed in an empty container at 25°C. The fraction of the total
pressure exerted by oxygen is :
(A) 1/3 (B) 1/2 (C) 2/3 (D) (1/3) (273/298)
33. On the surface of the earth at 1 atm pressure, a balloon filled with H2 gas occupies 500 mL. This volume
5/6 of its maximum capacity. The balloon is left in air. It starts rising. The height above which the balloon
will burst if temperature of the atmosphere remains constant and the pressure decreases 1 mm for every 100
cm rise of height is :
(A) 120 m (B) 136.67 m (C) 126.67 m (D) 100 m
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Rankers Academy JEE
Gaseous State
34*. 11 moles N2 and 12 moles of H2 mixture reacted in 20 litre vessel at 800 K. After equilibrium was reached,
6 mole of H2 was present. 3.58 litre of liquid water is injected in equilibrium mixture and resultant gaseous
mixture suddenly cooled to 300 K. What is the final pressure of gaseous mixture ? Neglect vapour pressure
of liquid solution. Assume (i) all NH3 dissolved in water (ii) no change in volume of liquid (iii) no reaction
of N2 and H2 at 300 K :
N2 :11 moles T=800K N2,H2 T = 300 K ; P = ?

H2 :12 moles V=20L NH3(aq) solution
Initial condition
(A) 18.47 atm (B) 60 atm (C) 22.5 atm (D) 45 atm
35. The ratio between the r.m.s. velocity of H2 at 50 K and that of O2 at 800 K is. [JEE 1996]
(A) 4 (B) 2 (C) 1 (D) 1/4
36. X ml H2 gas effuses through a hole in a container in 5 sec. The time taken for the effusion of the same volume
of the gas specified below under identical conditions is [JEE 1996]
(A) 10 sec, He (B) 20 sec, O2 (C) 25 sec, CO (D) 55 sec, CO2
37. One mole of N2O4 (g) at 300 K is kept in a closed container under one atm. It is heated to 600 K when 20%
by mass of N2O4 (g) decomposes to NO2 (g). The resultant pressure is. [JEE 1996]
(A) 1.2 atm (B) 2.4 atm (C) 2.0 atm (D) 1.0 atm
rA
38. According to Graham's law, at a given temperature the ratio of the rates of diffusion of gases A and B
rB
is given by. [JEE 1997]
1/ 2 1/ 2 1/ 2 1/ 2
PA æ M A ö æ M A öæ PA ö PA æ M B ö M A æ PB ö
(A) ç ÷ (B) ç ÷ç ÷ (C) ç ÷ (D) ç ÷
PB è M B ø è M B øè PB ø PB è M A ø M B è PA ø
39. A gas will approach ideal behaviour at : [JEE 1999]

(A) low temperature and low pressure (B) low temperature and high pressure
(C) low pressure and high temperature (D) high temperature and high pressure
40. The compressibility of a gas is less than unity at STP. Therefore : [JEE 2000]
(A) Vm > 22.4 L (B) Vm < 22.4 L (C) Vm = 22.4 L (D) Vm = 44.8 L
41. The r.m.s. velocity of hydrogen is 7 times the r.m.s. velocity of nitrogen. If T is the temperature of the gas
[JEE 2000]
(A) T(H2) = T(N2) (B) T(H2) > T(N2) (C) T(H2) < T(N2) (D) T(H2) = 7 T(N2)
42. The root mean square velocity of an ideal gas at constant pressure varies with density as : [JEE 2001]
(A) d2
(B) d (C) d 1/2
(D) 1/d1/2
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Rankers Academy JEE
JEE-Chemistr y
43. Which one of the following V, T plots represents the behaviour of one mole of an ideal gas at one atm?
[JEE 2002]
38.8 L 28.8 L 30.6 L 14.2 L

V(L) 373 K V(L) 373 K V(L) 373 K V(L) 373 K
22.4 L 20.4 L 22.4 L 22.4 L
(A) 273 K (B) 273 K (C) 273 K (D) 273 K
T(K) T(K) T(K) T(K)
44. Positive deviation from ideal behaviour takes place because of. [JEE 2003]
PV
(A) molecular interaction between atoms and >1
nRT
PV
(B) molecular interation between atoms and <1
nRT
PV
(C) finite size of atoms and >1
nRT
PV
(D) finite size of atoms and <1
nRT
45. The ratio of the rate of diffusion of helium and methane under identical condition of pressure and temperature
will be : [JEE 2005]
(A) 4 (B) 2 (C) 1 (D) 0.5
46*. What conclusions would you draw from the following graphs for ideal gas :
P V
Mole & volume constant Moles & pressure constant
0 K(–273.15°C) T 0 K(–273.15°C) T
(A) As the temperature is reduced, the volume as well as pressure increase under given condition.
(B) As the temperature is reduced, the volume becomes zero and the pressure reaches infinity under given condition.
(C) As the temperature is reduced, the volume as well as the pressure decrease under given condition.
(D) A point is reached where theoretically, the volume as well as the pressure become zero under given condition.
47. For a fixed amount of an ideal gas P vs T plot is given as shown. Identify the incorrect option :
B
A
P(atm) straight line
graph
T(Kelvin)
(A) The change from A to B should be isochoric
(B) Volume first increases reaches maxima and then decreases
(C) PV = nRT is not applicable
(D) None of the statements are correct
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Rankers Academy JEE
Gaseous State
Match the Column
48*. Match the entries in column I with entries in Column II and then pick out correct options.
Column I Column II
1
(A) vs P for ideal gas at (p)
V2
constant T and n.
1
(B) V vs for ideal gas at (q)
T
constant P and n
(C) log P vs log V for ideal gas (r)
at constant T and n.
1
(D) V vs for ideal gas (s)
P2
at constant T and n.
Comprehension
The rate of change of pressure (p) of a gas at constant temperature and constant external pressure due to
effusion of gas from a vessel of constant volume is related to rate of change of number of molecules present
by
dp kT dN
=
dt V dt
where k = Boltzmann constant, T = temperature, V = volume of vessel & N = No. of molecules and
dN - pA 0 , where A0 = area of orifice and m = mass of molecule.

=
dt (2pmkT)1 / 2
49*. Time required for pressure inside vessel to reduce to 1/e of its initial value in (ln e = 1)
1/ 2 1/ 2 1/ 2
æ 2pm ö V æ kT ö V æ 2pmkT ö 2pm V
(A) ç ÷ (B) ç ÷ (C) ç ÷ (D) kT A 0
è kT ø A0 è 2pm ø A0 è A0 ø
50*. If the gas inside the vessel had molecular weight 9 times the gas in previous example and area of orifice
was doubled and temperature maintained at 4T, time required for pressure to fall to 1/e times of its initial
value would be (t = answer of previous option)
(A) 1.33 t (B) 4.24 t (C) 0.75 t (D) 1.125 t
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Rankers Academy JEE
JEE-Chemistr y
51*. The incorrect statement (s) is/are.
[I] Pressure will not fall to zero in infinite time.
[II] Time required for pressure to decrease to half its initial value is independent of initial pressure.
[III] The relations given above are true for real gases also.
(A) I (B) II (C) III (D) I and III
Subjetive Questions
52*. The liquids shown in the fig. in the two arms are mercury (specific gravity = 13.6) and water. If the
difference of heights of the mercury columns in 2 cm. Find the height h of the water column.
53*. A glass bulb of volume 400 cm 3 is connected to another bulb of volume 200 cm3 by means of a tube of
negligible volume. The bulbs contain dry air and are both at a common temperature and pressure of 20ºC
and 1.00 atm. The larger bulb is immersed in steam at 100ºC ; the smaller, in melting ice at 0ºC. Find the
final common pressure.
54*. 1500 mL flask contains 400 mg O2 and 60 mg H2 at 100°C.

(a) What is the total pressure in the flask ?
(b) If the mixture is permitted to react to form water vapour at 100°C, what will be their partial pressures?
55. Calculate the temperature values at which the molecules of the first two members of the homologous series
CnH2n+2 will have the same rms speed as CO2 gas at 770 K. The normal b.p. of n-butane is 273 K. Assuming
ideal gas behaviour of n-butane upto this temperature, calculate the mean velocity and the most probable
velocity of its molecules at this temperature.
56. Calculate the temperature at which the root mean square velocity, average velocity and most probable velocity
of oxygen gas are all equal to 1500 ms–1.
3
57. The density of mercury is 13.6 g/cm . Estimate the b value.
58*. The vander waals constants for gases A,B and C are as follows :
Gas a/dm6 kPa mol–2 b/dm3 mol–1
A 405.3 0.027
B 1215.9 0.030
C 607.95 0.032
Which gas has (i) the highest critical temperature , (ii) the largest molecular volume, and (iii) most ideal be-
haviour around STP?
2 –2 –1
59. The vander waals constant for O2 are a = 1.36 atm L mol and b = 0.0318 L mol . Calculate the tem-
perature at which O2 gas behaves, ideally for longer range of pressure.
60. Calculate from the vander waal's equation, the temperature at which 192 g of SO2 would occupy a vol. of
10 dm3 at 15 atm pressure. [a = 6.7 atm L2 mol2, b = 0.0564 L mol–1]
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Rankers Academy JEE
Gaseous State
61*. Calculate the pressure of 15 mol neon at 30°C in a 12 litre container using
(i) the ideal gas equation
(ii) the vander waals equation
[a = 0.2107 atm L2 mol2, b = 0.0171 L mol–1]
62. A mixture of ideal gases is cooled upto liquid He temperature (4.22 K) to form an ideal solution. Is this statement
true or false. Justify your answer in not more than two lines. [JEE 1996]
63. The absolute temperature of an ideal gas is ........ to/than the average kinetic energy of the gas molecules.
[JEE 1997]
é B ù
64. One way of writing the equation for state for real gases is, PV = RT ê1 + + .........ú where B is constant.
ë V û
Derive an approximate expression for 'B' in terms of Vander Waals constant 'a' & 'b'. [JEE 1997]
65. Calculate the total pressure in a 10 litre cylinder which contains 0.4 g He, 1.6 g oxygen and 1.4 g nitrogen at
27°C. Also calculate the partial pressure of He gas in the cylinder. Assume ideal behavious for gases.
[JEE 1997]
66. An evacuated glass vessel weighs 50.0 g when empty, 148.0 g when filled with a liquid of density 0.98 g /mL
and 50.5 g when filled with an ideal gas at 760 mm Hg at 300 K. Determine the molecular weight of the gas.
[JEE 1998]
67. Using Vander Waals equation, calculate the constant "a" when 2 moles of a gas confined in a 4 litre flask
exerts a pressure of 11.0 atm at a temperature of 300 K. The value of "b" is 0.05 litre mol–1. [JEE 1998]
68. The pressure exerted by 12 g of an ideal gas at temperature t°C in a vessel of volume V is one atm. When
the temperature is increased by 10 degrees at the same volume, the pressure increases by 10%. Calculate the
temperature 't' and volume 'V'. [molecular weight of gas = 120] [JEE 1999]
69. One mole of N2 gas at 0.8 atm takes 38 sec to diffuse through a pin hole, whereas one mole of an unknown
compound of Xenon with F at 1.6 atm takes 57 sec to diffuse through the same hole. Calculate the molecular
formula of the compound. [JEE 1999]
70. If the pressure of a fixed amount of an ideal gas is proportional to its temperature, then under these conditions
frequency of collision and their impact both increase in proportion to the square root of temperature. True/False.
[JEE 2000]
71. Calculate the pressure exerted by one mole of CO2 gas at 273 K, if the Vander Waals constant a = 3.592
dm6 atm mol–2. Assume that the volume occupied by CO2 molecules is negligible. [JEE 2000]
72. The compression factor (compressibility factor) for one mole of a vander Waals gas at 0°C and 100 atmos
phere pressure is found to be 0.5. Assuming that the volume of a gas molecule is negligible, calculate the vander
waals constant 'a'. [JEE 2001]
73. The density of the vapour of a substance at 1 atm pressure and 500 K is 0.36 Kg m –3. The vapour effuse through
a small hole at a rate of 1.33 times faster than oxygen under the same condition. [JEE 2002]
(a) Determine
(i) mol. wt. ; (ii) molar volume ; (iii) compressibility factor (z) of the vapour
(iv) which forces among the gas molecules are dominating the attractive or the repulsive.
(b) If the vapour behaves ideally at 1000 K, determine the average translational K.E. of a molecule.
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Rankers Academy JEE
JEE-Chemistr y
74. The average velocity of gas molecules is 400 m/sec. Calculate its (rms) velocity at the same temperature.
[JEE 2003]
75. Cv value of He is always 3R/2 but Cv value of H2 is 3R/2 at low temperature and 5R/2 at moderate temperature
and more than 5R/2 at higher temperature explain in two to three lines. [JEE 2003]
76. For a real gas obeying vander Waal's equation a graph is plotted between PVm (y-axis) and P(x-axis) where
Vm is molar volume. Find y-intercept of the graph. [JEE 2005]
77. The temperature and the relative humidity of air are 20°C and 80% on a certain day. Find the fraction of
the mass of water vapour that will condense if the temperature falls to 5°C. Saturation vapour pressures
at 20°C and 5°C are 17.5 mm and 6.5 mm of Hg respectively.
78*. 6.0 g of He having average velocity 4 × 102 ms–1 is mixed with 12.0 g of Ne20 having the same average velocity.
What is the average kinetic energy per mole in the mixture?
79. Molar volume of He at 10.1325 MPa and 273 K is 0.011075 times its molar volume at 101.325 kPa. Calculate
radius of He atom assuming negligible 'a'.
80*. Pressure of He gas confined in a steel chamber drops from 4.0 to 1.0 atmosphere in 4.0 hours due to diffusion
through a pin-hole in the steel chamber. If an equimolar mixture of He and methane gas at 20 atmosphere and
the same temperature are confined in the same chamber, what will be the parital pressure of He and methane
after 1.0 hour. Assume rate of diffusion to be linear function of gas pressure and inverse function of square root
of molar masses.
81*. A mixture of CH4 & O2 is used as an optimal fuel if O2 is present in thrice the amount required theoretically for
combustion of CH4. Calculate number of effusions steps required to convert a mixture containing 1 part of CH4
in 193 parts mixture (parts by volume). If calorific value (heat evolved when 1 mole is burnt) of CH 4 is
100 cal/mole & if after each effusion 90% of CH4 is collected. find out what initial mole of each gas in initial
mixture required for producing 1000 cal of energy after processing. [Given (0.9) 5 = 0.6]
82*. A water gas mixture has the composition by volume of 50% H 2, 45% CO and 5% CO2.
(i) Calculate the volume in litres at STP of the mixture which on treatment with excess steam will contain
5 litres of H2. The stoichiometry for the water gas shift reaction is
CO + H2O ® CO2 + H2
(ii) Find the density of the water gas mixture in kg/m 3.
(iii) Calculate the moles of the absorbants KOH, Ca(OH)2 and ethanolamine.
HO – CH2 – CH2 – NH2 required respectively to collect the CO2 gas obtained.
83*. Calculate the pressure exerted by 22 g of carbon dioxide in 0.5 dm3 at 298. 15 K using :
(a) the ideal gas law and (b) vander waals equation. Given :
6 –2
[a = 363.76 kPa dm mol and b = 42.67 cm3 mol–1]
84*. The compressibility factor for N2 at –50°C and 800 atm pressure is 1.95 and at 100°C and 200 atm, it is
1.10. A certain mass of nitrogen occupied one litre at –50°C and 800 atm. Calculate the volume occupied
by the same quantity of N2 at 100°C and 200 atm.
85. At 273.15 K and under a pressure of 10.1325 MPa, the compressibility factor of O2 is 0.927. Calculate the
mass of O2 necessary to fill a gas cylinder of 100 dm3 capacity under the given conditions.
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Rankers Academy JEE
Gaseous State
ANSWERS
l True and False
1. False 2. False 3. False 4. True 5. False
6. False 7. True

8. 0.25 9. decreases
6 –2
10. Pa m mol 11. 26
1
12. 13. (i) inversely, square root of density, (ii) 900, (iii) 2/3
2
14. (i) gravity (ii) 44.33 (iii) 0.5 m/s (iv) 1.75 atm
15. 1.16 atm
16. (C) 17. (B) 18. (D) 19. (D) 20. (C)
21. (C)

22. (C) 23. (B) 24. (C) 25. (D) 26*. (C)
27*. (D) 28*. (A) 29*. (C) 30*. (A) 31. (C)
32. (A) 33. (C) 34*. (C) 35. (C) 36. (B)
37. (B) 38. (C) 39. (C) 40. (B) 41. (C)
42. (D) 43. (C) 44. (C) 45. (B)

46. (CD) 47. (ABC)
l Match the Column
48*. (A) - (r), (B) - (s), (C) - (p), (D) - (q)
l Comprehension
49*. (A) 50*. (A) 51*. (C)
52. 27.2 cm 53. 1.13 atm
54. (a) 0.867 atm (b) 0.102 atm
55. 280 K, 525 K, 3.157 × 102 m/s, 2.798 × 102 m/s
56. RRMS 2886 K, Tav = 3399 K, Tmp = 4330 K
57. 58.997 cm3 58*. (i) B (ii) C (iii) A
59. 521 K 60. 350.5°C
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61*. (i) 31.1 atm (ii) 31.4 atm 62. Yes it is false statement
æ a ö
63. directly proportional 64. B =çb –
è RT ÷ø
65. 0.492 atm, 0.246 atm 66. 123

2 –2
67. 6.46 atm L mol 68. –173°C, 0.82 L
69. XeF6 70. True
71. 0.99 atm 72. 1.2544 atm L2 mol–2
73. (a) (i) 18.1 g/mol (ii) 50.25 L mol–1 (iii) 1.224 (iv) repulsive (b) 2.07 × 10–20 J
74. 434.17 m/sec
75. Since H2 is diatomic and He is monoatomic degree of freedom for mono is 3 and only translational but
for diatomic, vibrational and rotational are also to be considered.
76. RT
77. 0.51
78*. 807.84 J
79. 134 pm
80*. PHe = 7.07 atm, PCH4 = 8.4 atm
81*. 10 Steps, 27.78 mol CH4, 5333.3 mol O2

82*. (i) 5.263 L,
(ii) 0.7kg/m3,
(iii) KOH = 0.2348 moles, Ca(OH)2 = 0.1174 moles, ethanolamine = 0.2348 moles’
83*. (a) 2.479 × 103 kPa (b) 2225.55 kPa
84*. 3.77 L
85. 15.40 kg
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Rankers Academy JEE
Chemical Equilibrium
CHEMICAL EQUILIBRIUM
True / False
1. Van't Hoff's equation gives the quantitative relation between change in value of K with change in temperature.
2. The value of equilibrium constant changes with change in the initial concentration of the reactants.
3. KP is related to KC as KP = KC (RT)Dn.
4. Introduction of inert gas in a gaseous reaction (Dng ¹ 0) at equilibrium keeping pressure constant has no effect
on equilibrium state.
5.
For the reaction, N2O4 (g) 2NO2 (g), KP = KC (RT).
[NH 3 ]2
6.
For the reaction, N2 + 3H2 2NH3, the equilibrium expression may be written as K = [N ][H ]3 .
2 2
7. A catalyst increases the value of the equilibrium constant for a reaction.

8. In case of endothermic reaction, the equilibrium shifts in backward direction on increasing the temperature.
9.
For the reaction, H2 + I2 2HI, the equilibrium constant, K is dimensionalless.
10.
The reaction 2SO2 (g) + O2 (g) 2SO3 (g), DH = –X kJ, is favoured by high pressure and high temperature.
11. The larger value of K indicates that the product is more stable relative to reactants.
12. Extent of a reaction can always be increased by increasing the temperature.
13. Solubilities of all solids in water increase with increase in temperature.
14. Dissolution of all gases in water is accompained by evolution of heat.
15.
For the reaction, CaCO3 (s) CaO (s) + CO2 (g), KP = pCO2.
16. If concentration quotient of reaction is less than K, the net reaction is proceeding in the backward direction.
17. The value of K increases with increase in pressure.
18. A very high value of K indicates that at equilibrium most of the reactants are converted into products.
19.
The value of K for the reaction, N2 + 3H2 2NH3, can be increased by applying high pressure or by
using a catalyst.
20. For a reaction the value of Q greater than K indicates that the net reaction is proceeding in backward direction.
Fill in the blanks
21.
K for the reaction 2 A + B 12
2C is 1.5 × 10 . This indicates that at equilibrium the concentration of
...................... would be maximum.

1 1
22. K for the reaction X2 + Y2 2XY is 100 K for this reaction XY X2 + Y2 would be ..................... .
2 2
23.
Compared to K for the dissociation, 2H2S + – + –
2H + 2HS , then K' for the H + HS H2S would
have ...................... .
24. For the reaction, N2O4 (g)

2NO2 (g), at equilibrium, increase in pressure shifts the equilibrium in
...................... direction.
25. When the reaction is at equilibrium, the value of DG is ..................... .
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26. The value of K for a reaction can be changed by changing ..................... .
27. The law of mass action was proposed by ..................... .
28.
The degree of dissociation of PCl5 [PCl5 (g) PCl3 (g) + Cl2 (g)], .................... with increase in pressure
at equilibrium.
29. If concentration quotient, Q is greater than KC, the net reaction in taking place in ...................... direction.
30.
The reaction, N2 + 3H2 2NH3 would be favoured by ...................... pressure.
31.
The reaction N2 + O2 2NO – Heat, would be favoured by ...................... temperature.
32. The equilibrium constant for a reaction decreases with increase in temperature, the reaction must be ................
33.
For the reaction, PCl5 (g) PCl3 (g) + Cl2 (g), KP and KC are related as ...................... .
34. DG° is related to K by the relation ..................... .
35. Vant Hoff's equation is ..................... .
36.
Dimensions of equilibrium constant, Kc for the reaction 2NH3 N2 + 3H2, are ..................... .
37. KP is related to KC as ..................... .
38. Solubility of a gas in water ...................... with increase in temperature.

39. Introduction of inert gas at constant volume to a gaseous reaction at equilibrium results in formation of
...................... product.
40. The product is more stable than reactants in reaction having ...................... K.
Assertion-Reason
41. Statement-I : The melting point of ice decreases with increase of pressure.
Because
Statement-II : Ice contracts on melting.

42*. Statement-I : The equilibrium of A(g) B(g) + C(g) is not affected by changing the volume.
Because
Statement-II : Kc for the reaction does not depend on volume of the container.
43. Statement-I : For the reaction A(g) B(g) + C(g), Kp = 1 atm. If we start with equal moles of all
gases at 9 atm of initial pressure, then at equilibrium partial pressure of A increases.
Because
Statement-II : Reaction quotient Qp > Kp hence equilibrium shifts in backward direction.
44*. Statement-I : For a reaction at equilibriu m, the Gibb's free energy of reaction is minimum at constant temp.
and pressure.
Because
Statement-II : The Gibb's free energy of both reactants and products increases and become equal at equilibrium.
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Rankers Academy JEE
45. Statement-I : Equilibrium constant for the reverse reaction is the inverse of the equilibrium constant for the
reaction in the forward direction.
Because
Statement-II : Equilibrium constant depends upon the way in which the reaction is written.
46. Statement-I : For the reaction H2(g) + I2(g)

2HI(g) if the volume of vessel is reduced to half of
its original volume, equilibrium concentration of all gases will be doubled.
Because
Statement-II : According to Le Chatelier's principle, reaction shifts in a direction that tends to minimized
the effect of the stress.
47. Statement-I : For the reaction at certain temperature

A(g) + B(g) C(g)
there will be no effect by addition of inert gas at constant volume.
Because
Statement-II : Molar concentration of all gases remains constant.
48. Statement-I : The catalyst does not alter the equilibrium constant.
Because
Statement-II : For the catalysed reaction and uncatalysed reaction DH remains same and equilibrium
constant depends on DH.

49*. For reaction : A(s)
B(g) + C(g) . What will be the value of natural logarithm of ratio of total pressure at 400
é P400 ù
K to that at 300 K ê = ln P ú if DH = 16.628 kJ. [Given : R = 8.314 J/K–mole]
ë 300 û
5 5 3 6
(A) (B) (C) (D)
3 6 5 5
D
50. In the above question, x varies with according to :
d
X X X X
(A) (B) (C) (D)
D D D D
d d d d
51*. In a 7.0 L evacuated chamber, 0.50 mol H2 and 0.50 mol I2 react at 427°C.

H2 (g) + I2 (g) 2HI (g). At the given temperature, KC = 49 for the reaction.
(i) What is the total pressure (atm) in the chamber ?

(A) 83.14 (B) 831.4 (C) 8.21 (D) None
(ii) What is the value of Kp ?

(A) 7 (B) 49 (C) 24.5 (D) None
(iii) How many moles of the iodine remain unreacted at equilibrium ?

(A) 0.388 (B) 0.112 (C) 0.25 (D) 0.125
(iv) What is the partial pressure (atm) of HI in the equilibrium mixture?

(A) 6.385 (B) 12.77 (C) 40.768 (D) 646.58
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52.
The reaction A + B C + D is studied in a one litre vessel at 250°C. The initial concentration of A was
3n and that of B was n. When equilibrium was attained, equilibrium concentration of C was found to the equal
to the equilibrium concentration of B. What is the concentration of D at equilibrium :
(A) n / 2 (B) (3n – 1/2) (C) (n – n/3) (D) n
53*. The value of Kp for the reaction

2H2O (g) + 2Cl2O (g) 4HCl (g) + O2 (g)
is 0.03 atm at 427°C, when the partial pressure are expressed in atmosphere then the value of K C for the same
reaction is :
(A) 5.23 × 10–4 (B) 7.34 × 10–4 (C) 3.2 × 10–3 (D) 5.43 × 10–5
54.
2 moles each of SO3, CO, SO2 and CO2 is taken in a one lit. vessel. If KC for SO3 + CO SO2 + CO2
is 1/9 then :
(A) total no. of moles at equilibrium are less than 8 (B) n (SO3) + n(CO2) = 4
(C) [n(SO2)/n (CO)] < 1 (D) both (B) and (C)
55*. Sulphide ion in alkaline solution reacts with solid sulphur to form polysulphide ions having formulae
S22–, S32–, S4--2– and so on. The equilibrium constant for the formation of S22– is 12 (K1) & for the formation
of S32– is 132 (K2), both from S and S2–. What is the equilibrium constant for the formation of S32– from S22–
and S ?
(A) 11 (B) 12 (C) 132 (D) None of these

56*. For the reaction CO (g) + H2O CO2 (g) + H2 (g) at a given temperature the equilibrium amount of
CO2 (g) can be increased by : [JEE 1998]
(A) adding a suitable catalyst (B) adding an inert gas
(C) decreasing the volume of the container (D) increasing the amount of CO (g)
57*. The equilibrium between, gaseous isomers A, B and C can be represented as
Reaction Equilibrium constant

A(g)
B(g) : K1 = ?

B(g)
C(g) : K2 = 0.4

C(g)
A(g) : K3 = 0.6
If one mole of A is taken in a closed vessel of volume 1 litre, then
(A) [A] + [B] + [C] = 1 M at any time of the reactions
(B) Concentration of C is 4.1 M at the attainment of equilibrium in all the reactions
1
(C) The value of K1 is
0.24
(D) Isomer [A] is least stable as per thermodynamics.
Comprehension
Read the following passage carefully and answer the questions.
Effect of temperature on the equilibrium process is analysed by using the thermodynamics
From the thermodynamics relation
DG0 = – 2.30 RT logk .......... (1)
0
DG : Standard free energy change
0 0 0
DG = DH – TDS .......... (2)
0
DH : Standard heat of the reaction.
From (1) & (2)
– 2.3 RT logk = DH0 – TDS0 DS0 : Standard entropy change
DH0 DS 0
Þ logk = - + .......... (3)
2.3RT 2.3 R
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Rankers Academy JEE
-DH°
Clearly if a plot of log k vs 1/T is made then it is a straight line having slope = 2.3 R
DS°
and Y intercept =
2.3 R
If at temp. T1 equilibrium constant be k1 and at temperature T2 equilibrium constant be k2 then :
The above equation reduces to:
DH0 DS0
Þ log k1 = - + .......... (4)
2.3 R T1 2.3 R
DH0 DS 0
Þ log k2 = - + .......... (5)
2.3 R T2 2.3 R
Substracting (4) from (5) we get
k2 DH0 æ 1 1 ö
Þ log = ç - ÷
ç
k1 2.30R è T1 T2 ÷ø
From the above relation we can conclude that the value of equilibrium constant increases with increase in
temperature for endothermic reaction but value of equilibrium constant decreases with the increase in
temperature for exothermic reaction.
1
58*. If standard heat of dissociation of PCl5 is 230 cal then slope of the graph of logk vs is :
T
(A) +50 (B) – 50 (C) 10 (D) None
1
59*. For exothermic reaction if DS0 < 0 then the sketch of logk vs may be :
T
(A) (B) (C) (D)

logk
1/T
60*. If for a particular reversible reaction at :
kC = 57 at 355 0C and kC = 69 at 450 0 then :
(A) DH < 0 (B) DH > 0
(C) DH = 0 (D) DH whose sign can’t be determined
Subjetive Questions
61.
Rate of disappearance of the reactant A at two different temperature is given by A B
-d[A]
= (2 × 10–2 S–1) [A] –4 × 10–3 S–1 [B] ; 300 K
dt
-d[A]
= (4 × 10–2 S–1) [A] –16 × 10–4 S–1 [B] ; 400 K
dt
Calculate heat of reaction in the given temperature range. When equilibrium is set up.
62. Among the solubility rules, the statement that all chlorides are soluble except Hg 2Cl2 , AgCl, PbCl2, and CuCl.
(a) Write the expression for the equilibrium constant for the reaction represented by the equation

AgCl (s) + –
Ag (aq) + Cl (aq)
Is K greater than 1, less than 1, or about equal to 1? Explain your answer.
(b) Write the expression for the equilibrium constant for the reaction represented by the equation

Pb2+ (aq) + 2Cl– (aq) PbCl2 (s)
Is K greater than 1, less than 1, or about equal to 1? Explain your answer.
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63*. At 1400 K, Kc = 2.5 × 10–3 for the reaction CH4 (g) + 2H2S CS2 (g) + 4H2 (g). A 10.0 L reaction
vessel at 1400 K contains 2.0 mol of CH4, 3.0 mol of CS2, 3.0 mol of H2 and 4.0 mol of H2S. Is this reaction
mixture at equilibrium ? If not, in which direction does the reaction proceed to reach equilibrium ?
64.
At a certain temperature, the reaction PCl5 (g) PCl3 (g) + Cl2 (g) has an equilibrium constant
–2
Kc = 5.8 × 10 . Calculate the equilibrium concentrations of PCl5, PCl3 and Cl2 if only PCl5 is present initially,
at a concentration of 0.160 M.
65*. The system N2O4 2 NO2 maintained in a closed vessel at 60°C & pressure of 5 atm has an average
(i.e. observed) molecular weight of 69, calculate Kp. At what pressure at the same temperature would the observed
molecular weight be (230/3) ?
66. The vapour density of N2O4 at a certain temperature is 30. Calculate the percentage dissociation of N2O4 at

this temperature. N2O4 (g) 2NO2 (g).
67*. In the esterification C2H5OH (l) + CH3COOH (l) CH3COOC2H5 (l) + H2O (l) an equimolar mixture
of alcohol and acid taken initially yields under equilibrium, the water with mole fraction = 0.333. Calculate
the equilibrium constant.
68. Solid Ammonium carbamate dissociates as : NH2COONH4 (s) 2NH3 (g) + CO2 (g). In a closed vessel
solid ammonium carbamate is in equilibrium with its dissociation products. At equilibrium, ammonia is added
such that the partial pressure of NH3 at new equilibrium now equals the original total pressure. Calculate the
ratio of total pressure at new equilibrium to that of original total pressure.
69*. A sample of CaCO3 (s) is introduced into a sealed container of volume 0.821 litre & heated to 1000 K until

equilibrium is reached. The equilibrium constant for the reaction CaCO3 (s) CaO (s) + CO2 (g) is
4 × 10–2 atm at this temperature. Calculate the mass of CaO present at equilibrium.
70*. (a) Water gas, a mixture of H2 and CO, is an important industrial fuel produced by the reaction of steam with
red-hot coke,essentially pure carbon. Write the expression for the equilibrium constant for the reversible
reaction.

C (s) + H2O (g) CO (g) + H2 (g) DH = 131.30 kJ
(b) Assume that equilibrium has been established and predict how the concentration of each reactant and product
will differ at a new equilibrium if (1) more C is added. (2) H 2O is removed. (3) CO is added (4) the pressure
on the system is increased. (5) the temperature of the system is increased.
71. The progress of the reaction 0.5

A nB with time, is presented in figure, Determine
(i) the value of n. 0.3
(ii) the equilibrium constant K.
(iii) the initial rate of conversion of A.
0.1
1 3 5 7
Time/Hour
72.
The KP for reaction A + B C + D is 1.34 at 60°C and 6.64 at 100°C. Determine the free energy change
of this reaction at each temperature and DH° for the reaction over this range of temperature?
73. At 100 K, then value of Kc for the reaction C(s) + H2O (g) –2
CO (g) + H2 (g) is 3.0 × 10 . Calculate
equilibrium concentrations of H2O, CO2 and H2 in the reaction mixture obtained by heating 6.0 mole of steam
and an excess of solid carbon in a 5.0 L container. What is the molar composition of the equilibrium mixture?
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Rankers Academy JEE
74*. When 1.0 mol of PCl5 is introduced into a 5.0 L container at 500 K, 78.5 % of the PCl5 dissociates to given
an equilibrium mixture of PCl5, PCl3 and Cl2.

PCl5 (g) PCl3 (g) + Cl2 (g)
(a) Calculate the values of Kc and Kp.
(b) If the initial concentrations in a particular mixture of reactants and products are [PCl5] = 0.5 M,
[PCl3] = 0.15 M, and [Cl2] = 0.6 M, in which direction does the reaction proceed to reach equilibrium?
What are the concentrations when the mixture reaches equilibrium?
75. The vapour pressure of water at 25°C is 0.0313 atm. Calculate the values of K p and Kc at 25°C for the equilibrium

H2O (l) H2O (g).
76. When 0.5 mol of N2O4 is placed in a 4.00 L reaction vessel and heated at 400 K, 79.3 % of the N2O4 de-

composes to NO2. Calculate Kc and Kp at 400 K for the reaction N2O4 (g) 2 NO2 (g).
77.
The equilibrium constant of the reaction 2 C 3H6 (g) C2H4 (g) + C4H8 (g) is found to fit the expression
1088
lnK = – 1.04 –
T
Calculate the standard reaction enthalpy and entropy at 400 K.
78*. The decomposition of solid ammonium carbamete, (NH4)(NH2CO2), to gaseous ammonia and carbon dioxide
is an endothermic reaction.

(NH4) (NH2CO2) (s)
2NH3(g) + CO2(g)
(a) When solid (NH4) (NH2CO2) is introduced into an evacuated flask at 25°C, the total pressure of gas at
equilibrium is 0.116 atm. What is the value of Kp at 25°C ?
(b) Given that the decomposition reaction is at equilibrium, how would the following changes affect the total
quantity of NH3 in the flask once equilibrium is re-established?
(i) Adding CO2
(ii) Adding (NH4) (NH2CO2)
(iii) Removing CO2
(iv) Increasing the total volume
(v) Adding neon
(vi) Increasing the temperature
79.
A container contains three gases. A, B and C in equilibrium A
2B + C
At equilibrium the concentration of A was 3 M, and of B was 4 M. On doubling the volume of container, the new
equilibrium concentration of B was 3M. Calculate K C and initial equilibrium concentration of C.
80. A mixture of hydrogen & iodine in the mole ratio 1.5 : 1 is maintained at 450°C. After the attainment of

equilibrium H2(g) + I2(g) 2HI(g), it is found on analysis that the mole ratio of I 2 to HI is 1 : 18. Calculate
the equilibrium constant & the number of moles of each species present under equilibrium, if initially, 127 g of
iodine were taken.
81. The equilibrium constant for the reaction CO(g) + H2O(g)
CO2(g) + H2(g) is 7.3 at 450°C & 1 atm
pressure. The initially concentration of water gas [CO & H2 in equimolar ratio] & steam are 2 moles &
5 moles respectively. Find the number of moles of CO, H 2, CO2 & H2O (vapour) at equilibrium.
82. At 1200°C, the following equilibrium is established between chlorine atoms & molecule.

Cl2(g)
2Cl(g)
The composition of equilibrium mixture may be determined by measuring the rate of effusion of the mixture
through a pin hold. It is found that at 1200°C and 1 atm pressure the mixture effuses 1.16 times as fast as
krypton effuses under the same condition. Calculate the equilibrium constant Kc.
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K1
83.
DG° (298 K) for the reaction 1/2N2 + 3H2 –1
NH3 is –16.5 kJ mol . Find the equilibrium constant (K1) at
25°C. What will be the equilibrium constants K 2 and K3 for the following reactions :
K

2
N2 + 3H2
2NH3
K

3
NH3
1/2 N2 + 3/2 H2
84. For the reaction, N2O5 (g) = 2 NO2 (g) + 0.5 O2 (g), calculate the mole fraction of N2O5 (g) decomposed at
a constant volume & temperature, if the initial pressure is 600 mm Hg & the pressure at anytime is 960 mm
Hg. Assume ideal gas behaviour. [JEE 1998]
85.
The degree of dissociation is 0.4 at 400 K & 1.0 atm for the gaseous reaction PCl 5 PCl3 + Cl2 (g). Assuming
ideal behaviour of all gases. Calculate the density of equilibrium mixture at 400 K & 1.0 atm pressure.
[JEE 1999]
86. When 3.06 g of solid NH4HS is introduced into a two litre evacuated flask at 27°C, 30% of the solid decomposes
into gaseous ammonia and hydrogen sulphide. [JEE 1999]
(i) Calculate KC & KP for the reaction at 27°C.
(ii) What would happen to the equilibrium when more solid NH4HS is introduced into the flask?
87. When 1-pentyne (A) is treated with 4N alcoholic KOH at 175°C, it is converted slowly into an equilibrium mixture
of 1.3% 1-pentyne (A), 95.2% 2-pentyne (B) & 3.5 % of 1,2-pentadiene (C). The equilibrium was maintained
at 175°C. Calculate DG° for the following equilibria.
B=A DG1° = ?
B=C DG2° = ?
From the calculated value of DG1° & DG2° indicate the order of stability of A, B & C. Write a reasonable reaction
mechanism sharing all intermediate leading to A, B & C. [JEE 2001]
88.
N2O4 (g) 2NO2 (g) [JEE 2004]
This reaction is carried out at 298 K and 20 bar. 5 mol each of N2O4 and NO2 are taken initially :
Given : DG°N O = 100 kJ mol–1 ; DG°NO = 50 kJ mol–1
2 4 2
(i) Find DG for reaction at 298 K under given condition.
(ii) Find the direction in which the reaction proceeds to achieve equilibrium.
89*. 0.15 mole of CO taken in a 2.5 litre flask is maintained at 750 K along with a catalyst so that the following
reaction can take place ;

CO(g) + 2H2(g)
CH3OH(g).
Hydrogen is introduced untill the total pressure of the system is 8.5 atm at equilibrium and 0.08 mole of
methanol is formed. Calculate :
(i) Kp & Kc ;
(ii) the final pressure if the same amount of CO and H2 as before are used, but with no catalyst so that the
reaction does not take place.
90. In a vessel, two equilibrium are simultaneously established at the same temperature as follows :

N2(g) + 3H2(g) 2NH3(g) .........(i)

N2(g) + 2H2(g)
N2H4(g) ........(ii)
Initially the vessel contains N2 and H2 in the molar ratio of 9 : 13. The equilibrium pressure is 7P0, in which
pressure due to ammonia is P0 and due to hydrogen is 2P0. Find the values of equilibrium constant (KP's) for
both the reactions.
91. At 90°C, the following equilibrium is established :

H2(g) + S(s) H2S(g) Kp = 6.8 × 10
–2
If 0.2 mol of hydrogen and 1.0 mol of sulphur are heated to 90°C in a 1.0 litre vessel, what will be the partial
pressure of H2S at equilibrium ?
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Rankers Academy JEE
92*. At 817°C, Kp for the reaction between pure CO2 and excess hot graphite to form 2CO(g) is 10 atm.
(a) What is the analysis of the gases at equilibrium at 817°C & a total pressure of 4.0 atm ? What is the partial
pressure of CO2 at equilibrium ?
(b) At what total pressure will the gas mixture analyze 6%, CO 2 by volume ?
93.
For the reaction N 2O4
2NO2, equilibrium mixture contains NO2 at P = 1.1 atm & N 2O4 at
P = 0.28 atm at 350 K. The volume of the container is doubled. Calculate the equilibrium pressures of the two
gases when the system reaches new equilibrium.
94. The degree of dissociation of HI at a particular temperature is 0.8. Find the volume of 1.5 M sodium thiosulphate
solution required to react completely with the iodine present at equilibrium in acidic conditions, when 0.135 mol
each of H2 and I2 are heated at 440 K in a closed vessel of capacity 2.0 L.
95*. SO3 decomposes at a temperature of 1000 K and at a total pressure of 1.642 atm. At equilibrium, the density

of mixture is found to be 1.28 g/L in a vessel of 90 litres. Find the degree of dissociation of SO 3 for SO3
SO2 + 1/2O2.
96. The density of an equilibrium mixture of N2O4 and NO2 at 101.32 KPa is 3.62 g dm–3 at 288 K and

1.84 g dm–3 at 348 K. What is the heat of the reaction for N2O4 2NO2(g).
97*. The equilibrium constant for the following reaction at 1395 K.

2H O 2H + O K = 2.1 × 10–13
2 2 2 1

2CO2 2CO + O2 K2 = 1.4 × 10–12

Calculate the value of K for the reaction : H2 + CO2 CO + H2O
98. A mixture of N2 & H2 are in equilibrium at 600 K at a total pressure of 80 atm. If the initial ratio of N 2 and H2
are 3 : 1 and at equilibrium NH3 is 10% by volume, calculate KP of reaction at given temperature.
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ANSWERS
l True and False
1. True 2. False 3. True 4. False 5. True
6. True 7. False 8. False 9. True 10. False
11. True 12. False 13. False 14. True 15. True
16. False 17. False 18. True 19. False 20. True

1 1
21. product C 22. 23.
10 K
24. backward 25. zero 26. Temperature
27. Guldberg and Waage 28. decreases 29. backward
30. high 31. high 32. exothermic
33. KP = KC(RT) 34. DGº = -RTlnK
K2 DHº é T2 - T1 ù
35. log = ê ú 36. mol2L–2 37. KP = KC(RT)Dn
K 1 2.303R ë T2 T1 û
38. decreases 39. same amount of 40. large value of
l Assertion - Reason
41. (A) 42*. (D) 43. (A) 44*. (C) 45. (A)
46. (B) 47. (A) 48. (A)

49. (B) 50. (B) 51. (i) (C) (ii) (B) (iii) (B) (iv) (A)
52. (A) 53*. (A) 54. (D) 55*. (A) 56*. (D)
57. (ACD)
l Comprehension
58*. (B) 59*. (B) 60*. (B)
61. Vant holf equation
K2 DH é 1 1ù
log = -
K 1 2.303R êë T1 T2 úû
–2 2 ´ 10 -2
log 2 × 10 At 300K K1 = =5
4 ´ 10-3
4 ´ 10 -2
At 400K K2 = = 25
16 ´ 10-4
25 DH é 1 1 ù
log = - DH = 16.06 × 103 J
5 2.303 ´ 8.314 êë 300 400 úû
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[Ag + ][Cl - ]
62. (a) k eq = = [Ag + ][Cl - ] (as conc. of solid is 1)
[AgCl]
keq < 1, AgCl is insoluble, so conc. of ions are match less than 1 M.
1
(b) k eq =
[Pb ][Cl - ]2
2+
keq > 1, as PbCl2 is insoluble of conc. of ions are much less than 1 M.
4
æ 3 öæ 3 ö
[CS 2 ][H 2 ] 4 çè ÷ø çè ÷ø
10 10
Q= = = 7.6 ´ 10-2
63*. [H 2 S]2 [CH 4 ] æ 4 ö 2 æ 2 ö
çè ÷ø çè ÷ø
10 10
64.
PCl5 (g) PCl3 (g) + Cl2 (g)
at t = 0 0.160
at eq. 0.160 – x x x
2
[PCl 3 ][Cl 2 ] x
KC = = = 5.8 ´ 10 -2
[PCl 5 ] (0.16 - x)
Þ x = 0.071
so, conc. of PCl3 = Cl2 = 0.071
conc. of PCl5 = 0.16 – 0.071 = 0.089
65*. N2O4 2NO2

at t = 0 PO O
at equation PO(1 – a) PO2a
total pressure at equation PO(1 – a) + 2POa = PO(1 + a) = 5 atm
PO (1 - a) ´ 92 + 2PO a ´ 46
average miolecular mass = = 69
PO (1 + a)
PO ´ 92(1 - a + a)
Þ = 69
PO (1 + a)
92
Þ (1 + a) =
69
92 23
Þ a= -1 =
69 69
and PO(1 + a) = 5
5 5
PO = = ´ 69
1 + a 92
(2PO a)2 4PO a 2

KP = =
PO (1 - a) (1 - a)
2
5 æ 23 ö
4´ ´ 69 ´ ç ÷
92 è 69 ø
= = 2.5 atm
æ 23 ö
çè 1 - ÷
69 ø
PO (1 - a) ´ 92 + 2PO a ´ 46 230
(ii) Average molecular mass = =
PO (1 + a) 3
92PO (1 - a + a) 230
Þ =
PO (1 + a) 3
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92 ´ 3 276 12
Þ 1+a = = =
230 230 10
12 2
a= -1 = = 0.2
10 10
(2aPO )2 4 a 2PO
Now KP = = = 2.5
P(1 - a) (1 - a)
4 ´ 0.2 ´ 0.2 ´ PO
Þ = 2.5
1 - 0.2
Þ PO = 12.5
Total pressure at equation = PO(1 + a) = 12.5(1 + 0.2) = 15 atm.
66. Vapour density = 30

So molecular mass = 30 × 2 = 60
N2O4
2NO2
at t = 0 100 0
at equation 100 – x 2x
total moleculer = 100 – x + 2x = 100 + x
(100 - x)92 + (2x + 46)
Average molecular mass = = 60
100 + x
9200
Þ = 60
100 + x
Þ x = 53.33%
67*. C2H5OH + CH3COOH CH3COOC2H5 + H2O

at t = 0 a a 0 0
at equation a–x a–x x x
total moleculer of equation = (a – x) + (a – x) + x + x = 2a
x
as given in equation mole fraction of H2O = = 0.333 x = 0.666a
2a
[CH 3COOC 2H 5 ][H 2O] 0.666a ´ 0.668a
x = K eq = = =4
[C 2H 5 OH][CH 3 OOH] (a - 0.666a) ´ (a - 0.666a)
68. NH2COONH4(s)

2NH3(g) + CO2(g)
at equation P.P. 2P P
so KP = [NH3]2 [CO2] = (2P)2(P) = 3P2
total pressure = 2P + P = 3P
IInd cose : Now P.P. of NH3 = Total pressure of cose I = 3P
NH2COONH4(s)

2NH3 + CO2
at new eq. past P is 3P P1
so KP = [3P]2[P1] = 4P3
4P
Þ P1 =
9
4P
so total pressure at new equation = 3 P.P. of NH3 + P.P.of CO 2
9
31P
=
9
31P / 9 31
Ratio of total pressure = =
3P 27
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Rankers Academy JEE
69*. CaCO3(g)
CaO(3) + CO2(g)
KP = [CO2]
= 4 × 10–2 atm
PV 4 ´ 10 -2 ´ 0.821
so moles of CO2 = = = 4 ´ 10-4
RT 0.0821 ´ 1000
Moles of CaO = moles of CO2 = 4 × 10–4
out of CaO = 4 × 10–4 × 56 = 224 × 10–4 of = 22.4 mg
70*. (a) K = [CO][H2] / [H2O] ;

(b) in each of the following cases the mass of carbon will change, but its concentration (activity) will not change.
1. [H2O] no change, [CO] no change, [H2] no change ; 2. [H2O] decrease, [CO] decrease, [H2] decrease ;
3. [H2O] increase, [CO] increase, [H2] decrease ; 4. [H2O] increase, [CO] decrease, [H2] decrease ;
5. [H2O] decrease, [CO] increase, [H2] increase ;
71. Each small cube represents 0.1 mol and 1 hour.

(i) In one hour 0.1 mole decreoses, but 0.2 mole increses of B so it
is A ® 2B, (value of n = 2)
(ii) At equation moles of A = 0.3, B = 0.6
so [B]2 (0.6)2
K eq = = = 1.2 mol / L
[A] (0.3)
0.1
(iii) In 1 hour conversion of A decreases from 0.6 to 0.5 so rate = moles hour–1
1
K2 DH æ 1 1ö
72. (i) log = ç - ÷
K 1 2.303R è T1 T2 ø
6.64 DH æ 1 1 ö
log = ´ç - ÷
1.34 2.303 ´ 8.314 è 333 373 ø
(ii) DG° = –RT ln K
= –8.314 × 333 × ln 1.34
= –810 J/mol
(iii) DG° = –RT ln K
= –8.314 × 373 × ln 6.64
= –5872 J/mol
6
73. initial conc. of H2O = = 1.2 M
5
CO + H2O(g)
CO2(g) + H2(g)
initially 1.2 0 0
1.2 – x x x
[CO 2 ][H 2 ] x2
KC = = = 3 ´ 10-2 x = 0.18
[H 2O] 1.2 - x
so [CO2] = [H2] = 0.18 and [H2O] = 0.02 M
1
74*. initial conc. of PCl5 = = 0.2M
5
78.5
78.5% of 0.2 = 0.2 ´ = 0.157
100
PCl5 PCl3 + Cl2
at t=0 0.2 0 0
0.2 – 0.157 0.157 0.157
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[PCl 3 ][Cl 2 ] 0.157 ´ 0.157

KC = = = 0.573
[PCl 5 ] 0.2 - 0.157
KP = KC (RT)1 (As Dng = 2 – 1 = 1)
= 0.573 × 500 × 0.0821 = 23.5
[PCl 3 ][Cl 2 ] 0.15 ´ 06
(b) Q= = = 0.18
[PCl5 ] 0.5
Q < KC so reaction will proceed in forward direction.
PCl5 PCl3 + Cl2
at t = 0 0.5 0.15 0.6
at equation 0.5 – x 0.15+x 0.6+x
(0.15 + x)(0.6 + x)
so = 0.573
(0.5 - x)
x = 0.135
so conc. of PCl5 = 0.5 – 0.135 = 0.365
Cl2 = 0.6 + 0.135 = 0.735
PCl3 = 0.15 × 0.135 = 0.285
75. K P = P(H2Og) = 0.0313 atm

Dny = 1 – 0 = 1
so KP = KC(RT)1
KP 0.0313
so KC = = = 1.28 ´ 10-3
RT 0.0821 ´ 298
76. N2O4

2 NO2
initial moles 0.5 0
moles at equation 0.5 – 0.3965 0.3965 × 2
(79.3%)
= 0.1035
0.1035 mole
so at equation conc. of N2O4 =
4 litre
0.3965 ´ 2 0.3965 [NO]2 (0.3965 / 2)2

NO 2 = = now K C = = = 1.51
4 2 [N 2O4 ] (0.1035 / 2)
KP = KC(RT)1 (as Dng = 2 – 1 = 1)
= 1.51 × 0.0821 × 400 = 49.6
1088
77. ln K = –1.04 –
T
RT ln K = –R × T × 1.04 – R × 1088
= –8.64T – 9045 ........(1)
we know that
DG° = –RT ln K = DH – TDS°
so RT ln k = –DH + TDS ........(2)
from equation (1) and (2)
DH = 9045 J/mol = 9.04 KJ/mole
–1 –1
DS = –8.64 J mol K
78*.

NH2COONH4 (s) 2NH3(g) + CO2(g)
at eq. 2P P
total pressure at eq. = 3P = 0.116
P = 0.03866
( ) ( P ) = (2P)2 (P) = 4P3 = 4(0.03866)3 = 2.31×10–4.

2
KP = PNH3 CO2
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79. Let equilibrium concentration of C be a M.
(4 2 )(a) 16a
KC = = ...(1)
3 3
on doubling volume all concentration are halved and equilibrium shifts forward
A
2B + C
3/2 – X 2+2X a/2 + X
Given : 2 + 2X = 3 Þ X = 1/2
æa 1ö
(3)2 ç + ÷
è 2 2ø
KC = ... (2)
æ3 1ö
ç – ÷
è 2 2ø
16a 9(a+1)
From (1) & (2), =
3 2
Þ 32a = 27a + 27
Þ 5a = 27
a = 5.4
9(3.2)
KC = = 28.8
(1)
80. H2(g) +

I2(g) 2HI(g)
1.5 a – x a–x 2x
a-x 1
= Þ 9a – 9x = x
2x 18
x = 9a/10
[2(9a/10)]2 81×4
KC = = = 54
æ 9a ö 6×1
ç 1.5a– ÷ (a–9a/10)
è 10 ø
81.
CO + H2O CO2 + H2
1–x 5–x x 1+x
x(1+x)
= 7.3 Solving x = 0.938
(1-x)(5-x)
rmix M Kr
82. rKr = M avg. = 1.16
83.8
Solving, M average =
1.16 2
71 4a2
= 1 + a. KP =
M avg. 1 - a2
KP
Þ KC = = 6.3 × 10–4
(0.0821)(1473)
83. –16.5 × 103 = –8.314 × 298 × 2.303 log K1
K2 = K12
1
K3 =
K1
let initial pressure of NO be p and of NO2 be 2p
84. Fraction decomposed = 0.4
85. 4.54 g dm–3

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86. (i) KC = 8.1 × 10–5 mol2 L2 ; KP = 4.84 × 10–2 atm2 ,
(ii) No effect ;
87. 15991 J mol–1, 12304 J mol–1 ; B > C > A
88. (i) 5.705 × 103 J mol–1

(ii) Since initial Gibbs free energy change of the reaction is positive, so the reverse reaction will take place.
89*. (i) CO + 2H2 CH3OH

t=0 0.15 a 0
t=¥ 0.15–x a – 2x x = 0.08
Total moles finally
= 0.15 + a – 2(0.08)
= a – 0.01
Þ 8.5 (2.5) = (a – 0.01) (0.0821) (750)
a = 0.355
Hence at equilibrium [CO] = 0.07M, [H2] = 0.195 M [CH3OH] = 0.08
0.08 / 2.5
\ KC = 2
æ 0.195 ö æ 0.07 ö
ç ÷ ç ÷
è 2.5 ø è 2.5 ø
(ii) Total moles = 0.15 + 0.355 = 0.505
P(2.5) = (0.505) (0.0821) 750
P = 12.43 atm
90. Let initial pressure of N2 be 9P and of H2 be 13P
N + 3H
2NH K
2 2 3 P1
9P–X–Y 13P–3X–2Y 2X
N2 + 2H

N2H4 KP2
2
9P–X–Y 13P – 3X – 2Y Y
9P–X–Y+13P–3X–2Y+2X+Y=7P0 ... (1)
2X = P0 ... (2)
13P – 3X – 2Y = 2P0 ... (3)
Solving x = P0/2 Y = 3P0/2 P = P0/2
(P0 )2
KP1 =
(4.5P0 - 0.5P0 - 1.5P0 )(6.5P0 - 1.5P0 - 3P0 )3
P0 2 1
= 3
= 2
(2.5P0 )(8P0 ) 20P0
3
and KP2 =
20P0 2
91.
H2(g) + S(s) H2S(g)
0.2 – x x
KP = KC = 6.8 × 10–2
x
= 6.8 × 10–2 Þ x = 0.012
0.2 - x
PH S = (x) RT = 0.012 (0.0821) (363)
2
92*. (a) CO2(g) +

C(g) 2CO(g) KP = 10atm
P0–x 2x
4x2
= 10 & P0 + x = 4
P0 – x
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Rankers Academy JEE
(b) Let total pressure be P atm
PCO = 0.06 P PCO = 0.94 P
2 2
(0.94P)2
KP = 10 = Þ P = 0.08 atm
0.06P
93. KP = 1.12/0.28 atm
On doubling volume
NO
2NO
2 4 2
0.14–x 0.55+2x
(0.55 + 2x)2 1.12
=
0.14 - x 0.28
94.
2HI H2 + I2
1–0.8 0.4 0.4
0.4×0.4
KC = =4
0.2 2
Let x mol of H2 & I2 react
(0.135 - x)2
4=
(2x)2
I2 + 2Na2S2O3 ® 2NaI + Na2S4O6
(0.135–x) 1.5 M
If V L of hypo are used
(0.135 – x) × 2 = 1.5 V
Let initially a mole I2 & (1.5 a) mol H2 be present
12.8 ´ 0.0821 ´ 1000

95*. M average = = 64
1.642
SO3
SO2 +1/2 O2
t=0 1
t=¥ 1–a a a/2
80
= 1 + a/2 Þ a = 0.5
64
3.62 ´ 0.0821 ´ 288

96. At 288 K, Mavg. =
1
92 4a 2
=1+a Þ KP1 =
M avg. 1 - a2
1.84 ´ 0.0821 ´ 348
Similarly at 348K, M'/avg.=
1
92 4 a '2
= 1 + a' Þ K P2 =
M ' avg 1 - a '2
KP DH° é 1 1 ù
êë 288 - 348 úû
2
log =
KP 2.303R
1
[H 2 ]2 [O 2 ] [CO]2 [O 2 ]
97*. K 1 = K2 =
[H 2 O]2 [CO 2 ]2
[CO][H 2 O] [CO][O 2 ]½ [H 2 O]
K= = ´
[H 2 ][CO 2 ] [CO 2 ] [H 2 ][O 2 ]½
K2 1.4 ´ 10 -12
= = = 2.58
K -1 2.1 ´ 10 -13
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98. N2 + 3H2

2NH3
t=0 60atm 20atm
t=¥ 60–x 20atm 2x
2x 1 80
= Þ 20x = 80 – 2x Þ x =
80 - 2x 10 22
2
é æ 80 öù
ê 2 çè 22 ÷øú
ë û
Þ KP = 3
é 80 ù é 240 ù
êë 60 - 20 -
22 úû êë 22 úû
86
Rankers Academy JEE
Ionic Equilibrium
IONIC EQUILIBRIUM
Assertion-Reason
1. Statement-1 : solubility of BaSO4 in 0.1 M Na2SO4 is 10-9 M hence its KSP is 10-18.
Statement-2 : because for BaSO4 KSP = (s)2 [symbols have their usual meanings].
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correctexplanation for Statement -1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement – 1 is False, Statement -2, is True.
2. Statement-1 : It is difficult to distinguish the strengths of the strong acids such as HCI, H2SO4, HNO3,HBr, HI
or HCIO4 in dilute aqueous solutions.
Statement-2 : In dilute aqueous solution all strong acids donate a proton to water and are essentially. 100%
ionised to produce a solution containing H3O+ ions plus the anions of strong acid .
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation forStatement-1.
(D) Statement-1 is False, Statement-2 is True.
3. Statement-1 : The titration curve for weak acid and weak base is as follows :
For this titration no suitable indicator is present.

Statement-2 : Indicator should change it colour sharply for indication of reaction to be complete so its pH-
range should lie perfectly with in sharp change to avoid experimental error.
4. Statement-1 : 0.20 M solution of NaCN is more basic than 0.20 M solution of NaF.
Statement-2 : 0.20 M solution of NaCN is more basic than 0.20 M solution of CH3COONa.
5. Statement-1 : A substance that can either act as an acid or a base is called ampholyte.
Statement-2 : Bisulphide ion (HS-) and biscarbonate ion (HCO3-) are ampholytes.
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6. Statement-1 : pH of amphiprotic anion is always independent upon concentration.
1
Statement-2 : pH of amphiprotic anion is given by [pK1 + pK2 ] where as pK1 and pK2 are the dissociation
2
congt. of the acid in which amphiprotic anion is formed –

7. 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. (Use antilog (0.5) = 3.16)
(A) 2.08 × 10–1 (B) 3.05 × 10–3 (C) 2.01 × 10–2 (D) None of these
8. What % of the carbon in the H2CO3 – HCO3– buffer should be in the form of HCO3– so as to have a neutral
solution? (Ka = 4 × 10–7)
(A) 20 % (B) 40 % (C) 60 % (D) 80%
9*. If K1 & K2 be first and second ionisation constant of H3PO4 and K1 >> K2 which is incorrect.
(A) [H+] = [ H2PO4- ] (B) [H+] = K 1 [H3PO4 ] (C) K2 = [HPO4-- ] (D) [H+] = 3[PO34- ]
10. 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
11. pKa of acetic acid is 4.74, which implies that:

(A) pH of 1 N acetic acid is 4.74
(B) at pH 4.74, the dissociation of acetic acid is maximum
(C) at pH 4.74 half of acetic acid molecules are dissociated in the solution
(D) at pH 4.74, the dissociation of acetic acid is minimum.
12. Pure water is added into the following solutions causing a 10% increase in volume of each :
(A) 0.1 M NaHCO3 (B) 0.2 M NaOH
(C) 0.3 M NH3 – 0.2 M NH 4
+
system (D) 0.4 M CH3COONH4
The greatest % change in pH would be observed in which case (A), (B), (C) or (D) ?
13. pH of an aqeous solution of NaCl at 85°C should be

(A) 7 (B) > 7 (C) < 7 (D) 0
14. 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
15. A certain acidic 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
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Rankers Academy JEE
Ionic Equilibrium
16. At what pH will a 1 × 10– 4 M solution of an indicator will Kb (indicator) = 1 × 10– 11 change colour?
(A) 7.0 (B) 3.0 (C) 5.5 (D) 11.0
17. One litre of saturated solution of CaCO3 is evaporated to dryness, 7.0 g of residue is left. The solubility product
for CaCO3 is:
(A) 4.9 × 10–3 (B) 4.9 × 10–5 (C) 4.9 × 10–9 (D) 4.9 × 10–7
18*. What will happen if the pH of the solution of 0.001 M Mg(NO 3)2 solution is adjusted to pH = 9 (Ksp of Mg(OH)2
= 8.9 × 10-12)
(A) ppt will take place (B) ppt will not take place
(C) Solution will be saturated (D) None of these
19. Equal volume of two solution having pH = 2 and pH = 10 are mixed together at 90°C. Then pH of resulting
solution is : (Take Kw at 90°C = 10-12)
(A) 2 + log 2 (B) 10 - log 2 (C) 7 (D) 6
20*. Which of the following is true

(A) pkb for OH¯ is – 1.74 at 25°C
(B) The equilibrium constant for the reaction between HA (pka = 4) and NaOH at 25°C will be equal to 1010.
(C) The pH of a solution containing 0.1 M HCOOH (ka = 1.8 × 10–4) and 0.1 M HOCN.
(ka = 3.2 × 10–4) will be nearly (3 - log 7).
(D) All the above are correct.
21. When 0.1 M NaOH is added in 0.1 M aq NH3 then which statement is going to wrong. (Kb = 2 × 10–5)
(A) degree of diosociation a approaches to zero (B) change in pH would be 1.85
(C) conc of [Na ] = 0.1, [NH3] = 0.1, [OH ] = 0.2
+ –
(D) on addition of OH– Kb of NH4OH does not changes.
22*. Which is/are correct statements :

(a) In any strong acid’s solution, the concentration of [OH–]
will be zero.
(b) If DGº of a reaction is positive, then the reaction will not
proceed at all, in the forward direction for any concentrations
of reactants and products.
(c) When titration curves are drawn for
(i) 1M HCl (50 mL) with 1 M NaOH and
(ii) 0.01 M HCl (50 mL) with 0.01 M NaOH on the same graph paper they look like:
(A) a & b (B) c only (C) b only (D) a & c
23. A solution prepared by dissolving 2.8 gm of lime, CaO in enough water to make 1.00 L of lime water (Ca(OH) 2(a)).
If solubility of Ca(OH)2 in water is 1.48 gm. The pH of the solution obtained will be:
[log 2 = 0.3, Atomic masses are Ca = 40 , O = 16, H = 1]
(A) 12.3 (B) 12.6 (C) 1.3 (D) 13
24. Pure AgCl(s) is added to (i) 0.01M AgNO3 solution (ii) 0.025 M KCl solution and both suspensions are shaken
well. What is the ratio of the [Cl-] in the first solution to the [Ag+] in the second solution? SAgCl = 1.7 × 10-10.
(A) nearly 2.5 (B) nearly 2.0 (C) nearly 3.0 (D) nearly 1.5
89
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25*. The curve represents a titration of weak monoprotic acid with NaOH. Calculate the initial concentration of the
acid using the data given in the curve. Assume that the final volume to be 100 mL :
(A) 1.8 × 10–5 (B) 2.6 × 10–2 (C) 3 × 10–4 (D) 2.6 × 10–6
26. A solution is 0.1 M each in HCl and CH3COOH. 20 ml of this solution is titrated against 0.1 M NaOH. By how
many units does the pH change from the beginning to the stage when the HCl is almost completely neutralized?
Ka for acetic acid is 1.8 × 10–5.
(A) 2.03 (B) 0.775 (C) 1.87 (D) 3.172
27. The pH of 0.1 M solution of the following salts increases in the order- [JEE 1999]
(A) NaCl < NH4Cl < NaCN < HCl (B) HCl < NH4Cl < NaCl < NaCN
(C) NaCN < NH4Cl < NaCl < HCl (D) HCl < NaCl < NaCN < NH4Cl
28. An aqueous solution of 6.3 g oxalic acid dihydrate is made up to 250 mL. The volume of 0.1 N NaOH required
to completely neutralise 10 mL of this solution is- [JEE 2001]
(A) 40 mL (B) 20 mL (C) 10 mL (D) 4 mL
29. For sparingly soluble salt ApBq, the relationship of its solubility product (Ls) with its solubility (S) is-
[JEE 2001]
(A) Ls = Sp+q, pp.qq (B) Ls = Sp+q, pp.qp (C) Ls = Spq pp.qq (D) Ls = Spq, (p.q)p+q
30. A solution which is 10–3 M each in Mn2+, Fe2+, Zn2+ and Hg2+ is treated with 10–16 M 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 ? [JEE 2003]
(A) FeS (B) MnS (C) HgS (D) ZnS
31. 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- [JEE 2004]
(A) 0.01 % (B) 0.0001 % (C) 0.1 % (D) 0.5 %
32*. 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- [JEE 2005]
(A) 1.6 × 10–11 (B) 8 × 10–11 (C) 5 × 10–5 (D) 2 × 10–2
33. 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]
90
Rankers Academy JEE
Ionic Equilibrium
34*. A weak acid (or base) is titrated against a strong base (or acid), volume v of strong base (or acid) is plotted
against pH of the solution in Fig. The weak protolyte (i.e. acid or base) could be
(A) Na2CO3 (B) Na2C2O4 (C) H2C2O4 (D) CH2(COOH)2
35. Which of the following are true for an acid-base titration ?

(A) Indicators catalyse the acid base reactions by releasing or accepting H+ ions.
(B) Indicators do not significantly affect the pH of the solution to which they are added.
(C) Acid-base reactions do not occur in absence of indicators.
(D) Indicators have different colours in dissociated and undissociated forms.
36. The charge balance condition for a solution is written as [Na +] + [H+] = [Cl¯] + [Br¯] + [I¯] + [OH¯]. The
solution could be :
(A) NaCl / NaBr / NaI simultaneously (B) NaCl / NaBr / HBr / HI simultaneously
(C) NaOH/ HCl/ HBr / HI simultaneously (D) NaI / HI / HBr / HCl simultaneously
37*. Successive acid dissociation constants for a tri basic acid, H3XO3, are K1 = 7.5 × 10–10, K2 = 2 × 10–13,
K3 = 1.6 × 10–14. Decimolar aqueous solutions of which of the following are expected to be basic ?
(A) H3XO3 (B) NaH2XO3 (C) Na2HXO3 (D) Na3XO3
38*. When 0.1 mol arsenic acid, H3AsO4 is dissolved in 1L buffer solution of pH = 4, which of the following hold
good ? K1 = 2.5 × 10–4, K2 = 5 × 10–8, K3 = 2 × 10–13 for arsenic acid [‘<<’ sign denotes that the higher
concentration is at least 100 times more than the lower one]
(A) [H3AsO4] << [H2AsO4–] (B) [H2AsO4] << [HAsO42–]
(C) [HAsO42–] << [H2AsO4–] (D) [AsO43–] << [HAsO42–]
39. Which of the following statement(s) is/are correct ? [JEE 1998]
(A) the pH of 1.0 × 10 M solution of HCl is 8
–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 against a strong base, at half - neutralization point pH
= (1/2) pKa.
40. A buffer solution can be prepared from a mixture of- [JEE 1999]
(A) sodium acetate and acetic acid in water
(B) sodium acetate and hydrochloric acid in water
(C) ammonia and ammonium chloride in water
(D) ammonia and sodium hydroxide in water.
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Match the Column
41*. Match the column.

Column I Column II
æ 10 litre of 0.03 NX(OH)2 (strong diacidic base) ö

ç ÷
ç+ ÷
(A) ç 5 litre of 0.08 M HNO 3 ÷ (p) pH ; 3.7
ç ÷
ç+ ÷
ç 485 litre of 0.01M NaNO ÷
è 3 ø
æ 10 ml of 0.5 M RNH 3 Cl (K h = 10 -9 ) ö
ç ÷
(B) ç+ ÷ (q) pH ; 11
çç 40 ml of 0.125 M KOH ÷÷
è ø
æ 100 ml of 0.8 M HCO-3 ö

ç ÷
ç+ ÷
(C) ç 2- ÷ (r) pH ; 7
ç 100 ml of 0.4 M CO3 ÷
çç (for H CO , use K = 4 ´ 10 -7 & K = 4 ´ 10 -11) ÷÷
è 2 3 a1 a2 ø
(D) Saturated aqueous of Co(OH)3 (KSP = 2.7 × 10–43) (s) pH ; 10
42*. Match the following :

If ka of HCN = 5 × 10-10 , ka of HOCN = 3.2 × 10-4 , kb of NH3 = 1.8 x 10-5, ka of CH3COOH = 1.8 × 105
Column-I Column-II
(A) 0.1 M NH4CN (p) pH > 7
(B) 100 ml of 10 M NaCI + 100 ml of
-1
(q) pH # 7
10 M HCI + 300 ml of 10 M NaOH
–1 -1
(C) 10–1 M HCI + 10-1 M HCN (r) pH < 7

(D) 10–1 M NH4OCN (s) pH = 7
43. (Use log 1.8 = 0.26, ka of formic acid = 1.8 × 10-4, ka of acetic acid = 1.8 × 10-5, kb of ammonia = 1.8 × 10-
5
, ka1 of H2S =10–7 and ka2 of H2S =10-14, for the following matchings)
Match the entries of column II for which the equality or inequality given in the column I are satisfied.
Column I Column II
(A) 10 M HCI solution > 0.1 M H2S solution
-5
(p) a water(degree of dissociation of water)
(B) CH3COOH solution at pH equal to 4.74 (q) [OH-]
= NH4OH solution at pH equal to 9.26
(C) 0.1 M CH3COOH solution = 1.0 M (r) a (degree of dissociation of weak electrolytes)
HCOOH solution
(D) 0.1 M of a weak acid HA/ (kb = 10-5) solution (s) pH
< 0.01 M of a weak acid HA2(ka = 10 ) solution-8
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Rankers Academy JEE
Ionic Equilibrium
Comprehension
Comprehension-1
Consider a solution of CH3COONH4 which is a salt of weak acid &weak base. The
equilibrium involved in the solutions are :
CH3C00– + H20 CH3COOH + OH– ...(1)
NH4– + H2 O NH4OH + H+ …(2)
H+ + OH– H2O ...(3)

If we add these three reactions, then the net reaction is
CH3C00- + NH4+ + H20 ——’ CH3COOH + NH4OH …(4)
Both CH3C00 and NH4' get hydrolysed independently and their hydrolysis depends on
-
(i) their initial concentration
Kw Kw
(ii) the value of Kh which is K for CH3COO- and K for NH +4 .
a b
Since both of the ions were produced from the same salt, their initial concentrations are same . Therefore
Kw
unless & untial the value of K and Kb is same, the degree of hydrolysis of ion can’t be same.
a
To explain why we assume that degree of hydrolysis of cation and anion is same, we need to now look at the
third reaction i.e., combination of H+ and OH– ions. It is obvious that this reaction happens only because one
reaction produced H+ ion and the other produced OH– ions. We can also note that this reaction causes both
the hydrolysis reaction to occur more since their product ions are being consumed. Keep this thing in mind that
the equilibrium which has smaller value of equilibrium conxtant is affected more by the common ion effect. For
the same reason if for any reason a reaction is made to occur to a greater extent by the consumption of any one
of the product ion, the reaction with the smaller value of equilibrium constant tends to get affected more.
Therefore we conclude that firstly the hydrolysis of both the ions ocurs more in the presence of each other (due
to consumption of the product ions) than in each other is absence. Secondly the hydrolysis of the ion which
occurs to a lesser extent (due to smaller value of Kh) is affected more than the one whose Kh is greater. Hence
we can see that the degree of hydrolysis of both the ions would be close to each other when they are getting
hydrolysed in the presence of each other.
44*. In the hydrolysis of salt of weak acid & weak base :

(A) degree of hydrolysis of cation and anion is different
(B) degree of hydrolysis of cation and anion is same
(C) degree of hydrolysis of cation and anion is different and they can never be assumed same.
(D) degree of hydrolysis of cation and anion is different but they are very close to each other when they are
getting hydrolysed in the presence of each other.
45*. For 0.1 M CH3COONH4 salt solution given, K aCH COOH = K bNH = 2 ´ 10 -5.
3 4OH
In this case : degree of hydrolysis of cation and anion is

(A) exactly same
(B) slightly different
(C) can’t say
(D) different but can be take approximatly same
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46*. In a solution of NaHCO3 , the amphiprotic anion can under ionization to form H+ ion and hydrolysis to from
OH– ion. ionization
HCO3– + H2O ¾¾® CO32–+ H2O
HCO3– + H2O ¾¾® HCO32– + OH–
To calculat PH, suitable approximation is :

(A) [CO32-] = [HCO3–] (B) degree of ionization = degree of Hydrolysis
(C) both (A) and (B) (D) neither ‘A’ nore ‘B’
Comprehension-2
The product of the concentrations of the ions of an electrolyte raised to power of their coefficients in the
balanced chemical equation in the solution at any concentration is called ionic product. Its value is not constant
and varies with change in concentration. Ionic product of the saturated solution is called solubility product Ksp.
(i) When Kip = Ksp , the solution is just saturated and no precipitation takes place.
(ii) When Kip < Ksp, the solution is unsaturated and precipitation will not take place.
(iii) When Kip > Ksp, the solution is supersaturated and precipitation takes place.
47. The solubility product Ksp, of sparingly soluble salt MX at 25°C is 2.5×10–9. The solubility of the salt in
mol L–1 at this temperature is
(A) 1×10–14 (B) 5×10–8 (C) 1.25×10–9 (D) 5×10–5
48. Which of the following is most soluble ?

(A) Bi2S3 (Ksp = 1 × 10–70) (B) MnS (Ksp = 7 × 10–16)
(C) CuS (Ksp = 8 × 10–37) (D) Ag2S (Ksp = 6 × 10–51)
49. The concentration of Ag+ ions in a given saturated solution of AgCl at 25° C is 1.06 × 10 –5 g ion per litre. The
solubility product of AgCl is :
(A) 0.353 × 10–10 (B) 0.530 × 10–10 (C) 1.12 × 10–10 (D) 2.12 × 10–10
Comprehension-3
Potash alum is K Al(SO4)2·12H2O. As a strong electrolyte, it is considered to be 100 % dissociated into K+, Al3+
and SO42–. The solution is acidic because of the hydrolysis of Al3+, but not so acidic as might be expected,
because the SO42– can sponge up some of the H3O+ by forming HSO4¯. Given a solution made by dissolving
11.85 gm of K Al(SO4)2·12H2O in enough water to make 100 cm3 of solution. What is [H3O+] of the solution if
50. None of the ion is hydrolysing.

(A) 10–7 M (B) less than 10–7 M (C) More than 10–7M (D) 0.0
51. Only Al3+ is hydrolysing and its first hydrolysis constant is 1.4 × 10–5 M
(A) 1.87 × 10–3 M (B) 6.24 × 10–4 M (C) 0.09 M (D) None of these
52. Only SO42– is hydrolysing and acid dissociation constant of HSO4¯ in water is 1.25× 10–2.
(A) 1.26 × 10–3 M (B) 6.32 × 10–7 M (C) 1.58 × 10–8 M (D) None of these
53. Both Al3+ and SO42– are hydrolysing.

(A) 2.93 × 10–4 M (B) 0.0114 M (C) 5.43 × 10–6 M (D) None of these
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Ionic Equilibrium
Subjetive Questions
54. 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?
55. All enviremental chemist needs a carbonate buffer of pH 10.00 to study the effects of the acidification of
limestone–rich soils. How many grams of Na2CO3 must be added to 1.5 L of freshly prepared 0.20 M NaHCO 3
to make the buffer? Ka of HCO3– = 4.7 × 10–11.(log 4.7 = 0.672)
56*. The dissociation constant for hydrogen sulphide (dissociated into 2H+ and S2–) is 1.1 × 10–22 at 18ºC. What is
the concentration of sulphide ion in a 0.1 N hydrochloric acid solution which is saturated with hydrogen sulphide
at 18ºC, assuming that the concentration of H2S is 0.1 M?
57. Calculate the extent of hydrolysis of 0.005 M K2CrO4. [K2 = 3.1 × 10-7 for H2CrO4]
(It is essentially strong for first ionization).
58. A solution of ammonia bought for cleaning the windows was found to be 10% ammonia by mass, having a
density of 0.935 g.mL–1. What is the pH of the solution. Take Kb for protonation of ammonia = 5.5 × 10–6.
59. A handbook states that the solubility of methylamine CH3NH2 (g) in water at 1 atm pressure at 25°C is 959
volumes of CH3NH2 (g) per volume of water (pkb = 3.39) :-
(a) Estimate the max. pH that can be attained by dissolving methylamine in water.
(b) What molarity NaOH (aq.) would be required to yield the same pH?
60*. Mixtured of solutions. Calculate the pH of the following solution.
Use data of above question & For H2CO3 ; K1 = 4.2 ´ 10-7 , K 2 = 4.8 ´ 10-11
(a) 40 mL of 0.050 M Na2CO3 + 50 mL of 0.040 M HCl ;
(b) 40 mL of 0.020 M Na3PO4 + 40 mL of 0.040 M HCl ;
(c) 50 mL of 0.10 M Na3PO4 + 50 mL of 0.10 M NaH2PO4 ;
(d) 40 mL of 0.10 M H3PO4 + 40 mL of 0.10 M Na3PO4.
61. 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 ?
(c) If the solution in (b) were diluted to 10 times its volume, what would be the pH?
62. Calculate the OH– concentration and the H3PO4 concentration of a solution prepared by dissolving 0.1 mol of
Na3PO4 in sufficient water to make 1 L of solution K1 = 7.1 × 10–3, K2 = 6.3 × 10–8, K3 = 4.5 × 10–13.
63*. A buffer solution was prepared by dissolving 0.02 mol propionic acid & 0.015 mol sodium
propionate in enough water to make 1.00 L of solution.(Ka for propionic acid is 1.34 x 10-5)
(a) What is the pH of the buffer .
(b) What would be the pH change if 1.0 × 10-5 mol HCl were added to 10 ml of the buffer.
(c) What would be the pH change if 1.0 × 10-5 mol NaOH were added to 10 ml of the buffer.
(d) Also report the percent change in pH of original buffer in cases (b) and (c).
64. Describe how would you prepare a phosphate buffer at a pH of about 7.40. Given for H 3PO4
K a1 = 7.5 × 10–3 , K a2 = 6.2 × 10–8, K a3 = 4.8 × 10–13.
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65. pK1 and pK2 for pyrophosphoric acid (H4P2O7, a tetraprotic acid) are 0.80 and 2.2 respectively.
Neglecting the third and fourth dissociations, find the concentration of the divalent anion in a 0.05 M acid
solution.
66. 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.
67. Bromophenol blue is an acid indicator with a K a value of 6 × 10-5 . What % of this indicator is in its basic form
at a pH of 5 ?
68*. An acid 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?
69. Calculate the pH during the titration of 40.00 ml of 0.1 M propanoic acid (HPr; Ka = 1 × 10–5) after adding the
following volumes of 0.1 M NaOH : (log 2 = 0.3, log 3 = 0.48)
(a) 0.00 ml (b) 30.00 ml (c) 40.00 ml (d) 50.00 ml.
70*. A small quantity of phenolphthalein is added to a decinormal solution of sodium butyrate at 25 0C. Calculate
the ratio of the coloured to the colourless form of the indicator. Ka for butyric acid = 1.5 x 10-5 at 250C. K for the
indicator = 3.16 x 10-10 and KW = 10-14 at 250C.
71. How many mol CuI (Ksp = 5 × 10–12) will dissolve in 1.0 L of 0.10 M NaI solution ?
72. What mass of Pb2+ ion is left in solution when 50.0 mL of 0.20M Pb(NO 3)2 is added to 50.0 mL of 1.5 M NaCl?
[Given Ksp for PbCl2 = 1.7 ×10–4]
73*. 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) = 5 × 10–13]
74. KSP of PbBr2 is 2.56 × 10–7. If the salt is 80% dissociated in solution, calculate the solubility of salt in g per litre.
75. KSP for PbCl2 is 10–13. What will be [Pb2+] in a solution prepared by mixing 100 mL of 0.1 M Pb(NO 3)2 and 1 mL
of 1 M HCl ?

76*. Given : Ag(NH3)2+ Ag + 2 NH3, Kc = 6.2 × 10 & Ksp of AgCl = 1.8 × 10 at 298 K. Calculate the
+ –8 –10
concentration of the complex in 1.0 M aqueous ammonia. [JEE 1998]
77. What will be the resultant pH when 200 mL of an aqueous solution of HCl (pH = 2.0) is mixed with 300 mL of
an aqueous solution of NaOH (pH = 12.0) ? [JEE 1998]
78. The solubility of Pb(OH)2 in water is 6.7 × 10–6 M. Calculate the solubility of Pb(OH)2 in a buffer solution of pH
= 8. [JEE 1999]
79*. The average concentration of SO2 in the atmosphere over a city on a certain day is 10 ppm, when the average
temperature is 298 K. Given that the solubility of SO2 in water at 298 K is 1.3653 moles litre–1 and the pKa of
H2SO3 is 1.92, estimate the pH of rain on that day. [JEE 2000]
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Rankers Academy JEE
Ionic Equilibrium
80. 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 6g 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]
81. Will the pH of water be same at 4 °C and 25 °C ? Explain. [JEE 2003]
82. 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 a << 1. [JEE 2004]
83. Salt mixture containing Cu3(AsO4)2 (Ksp = 8 × 10–36) and Pb3(AsO4)2 (Ksp = 4.096 × 10–36) is shaken with water.
Find the concentration of metal cations in the solution at equilibrium. Neglect any hydrolysis of the dissolved
ions.
84*. (a) At what minimum pH will 1.0 × 10–3 mol of Al(OH)3 go into 1 L solution as [Al(OH)4–].
(b) At what minimum pH will 1.0 × 10–3 mol of Al(OH)3 go into 1 L solution as Al3+ ?
Given : Ksp [Al(OH)3] = 5.0 × 10–33 and for [Al(OH)4–] Û Al3+ + 4OH– . K = 1.3 × 10–34.
85. 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 = 1.8 × 10–5 :-
86*. Mixture of solutions. Calculate the pH of the following solutions.
For H3PO4 ; K a1 = 7.5 ´ 10-3 , K a2 = 6.2 ´ 10-8 , Ka3 = 10-12
(a) 50 mL of 0.12 M H3PO4 + 20 mL of 0.15 M NaOH ;

(b) 50 mL of 0.12 M H3PO4 + 40 mL of 0.15 M NaOH ;
(c) 40 mL of 0.12 M H3PO4 + 40 mL of 0.18 M NaOH ;
(d) 40 mL of 0.10 M H3PO4 + 40 mL of 0.25 M NaOH.
87. When a 40 mL of a 0.1 M weak base is titrated with 0.16 M HCl, the pH of the solution at the end point is 5.23.
What will be the pH if 15 mL of 0.12 M NaOH is added to the resulting solution :-
88. 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.
89*. If 0.00050 mol NaHCO3 is added to 1 litre of a buffered solution at pH 8.00, how much material will exist in
each of the three forms H2CO3, HCO3– and CO32– ? For H2CO3, K1 = 5 × 10–7, K2 = 5 × 10–13.
90. How much Na2HPO4 must be added to one litre of 0.005 M solution of NaH2PO4 in order to make a 1 L of the
solution of pH = 6.7 ? K1 = 7.1 × 10–3, K2 = 6.3 × 10–8 , K3 = 4.5 × 10–13 for H3PO4.
91*. Liquid ammonia ionises to a slight extent. At – 50°C, its self ionisation constant K NH3 = [NH4+]
[NH2¯] = 10–30. How many amide ions are present per cm 3 of pure liquid ammonia.
92. Calculate the pH of a solution obtained by mixing 0.1 litre of a strong acid solution of pH = 4 and 0.2 lit,
solution of strong base of pH = 10.
93*. If both the functional groups of salicylic acid, HOC6H4COOH, ionise in water, with Ka = 1 × 10–3 for the
–COOH group and 4.2 × 10–13 for the –OH group, calculate pH of the saturated solution of the acid.
(Solubility of salicylic acid in water = 1.725 g/L, log 2 = 0.3).
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ANSWERS
1. (D) 2. (A) 3. (A) 4. (B) 5. (B)
6. (B)
7. (A) 8. (D) 9. (D) 10. (D) 11. (C)

12. (B) 13. (C) 14. (D) 15. (A) 16. (B)
17. (A) 18. (B) 19. (D) 20. (D) 21. (C)
22. (B) 23. (B) 24. (A) 25. (B) 26. (A)
27. (B) 28. (A) 29. (A) 30. (C) 31. (A)
32. (B) 33. (B)
34. (CD) 35. (BD) 36. (ABCD) 37. (BCD) 38. (CD)
39. (BC) 40. (AC)
l Match the Column

41*. (A – p), (B – q), (C – s), (D – r) 42. (A – p, q); (B – p, q) ; (C – q, r) ; (D – q, r)
43. (A – p, q, r, s) ; (B – p, r) ; (C – r) ; (D – p, q, s)
l Comprehension
Comprehension 1 : 44*. (D) 45*. (C) 46*. (C)

Comprehension 2 : 47. (D) 48. (B) 49. (C)
Comprehension 3 : 50. (A) 51. (A) 52. (C) 53. (A)
54. pKw = 14 - log 2.56 = 13.59 » 13.6

pK w
pH = =6.795
2
55. Ans. 15 g Na2CO3
For Na2CO3 + NaHCO3 buffer
[CO23- ]
pH = pKa of HCO -3 + log
[HCO -3 ]
56. Ans. 1.1 × 10–21 M

HCl saturated H2S solution , in presence of 0.1 N HCl
H 2S
2H + + S 2-

0.1 M 0.10 0
x ´ (0.1 + x)2
\ Ka =
0.1 - x 0.1 + x x 0.1 - x
Where x < < 0.1
57. Ans. 0.26%

For anionic hydrolysis of A 2-
Kh K
h= where K h = w
C K a2
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Rankers Academy JEE
Ionic Equilibrium
58. Ans. pH = 11.74
For ammonia solution i.e. NH4OH
1 1
pOH = pK b - log C
2 2
10 935
´
where C = 100 17 M
1
59. (a) 13.097 (b) 0.1252
Å
CH 3 NH 2 + H 2O
+ OH - Kb
CH 3 N H 3

t =0 CM 0 0
teq C - Cx Cx Cx
Cx 2
[OH–] = Cx and Kb =
1- x
60. (a) 8.347 (b) 4.66 (c) 9.6 (d) 7.2

(a) 2mg mol of H2CO3 will form after completion of reaction for weak acid of type H 2A, most of [H+] occurs
from 1st ionization only.
(b) Na 3 PO 4 + HCl ¾¾® NaCl + Na 2HPO4
Na 2 PO 4 + HCl ¾¾® NaH 2 PO 4 + NaCl
NaH 2 PO4 + HCl ¾¾® NaCl + H 3 PO4

pKa1 + pKa 2
Taken amount of reagents will results in formation of 0.8mg mol of NaH 2PO 4 \ pH =
2
(c) In this case mainly PO34 - hydrolysis occurs.
[H 3 PO 4 ] ´ K 1 ´ K 2 ´ K 3
(d) [H + ]3 =
[PO 34 - ]
61. (a) pH = 3.823 (b) pH = 3.846 (c) pH = 3.9899

For buffer of HCOOH & HCOONa.
[HCOO - ]
pH = pKa + log
[HCOOH]
With dilution degree of hydrolysis of HCOO– & degree of dissociation of HCOOH changes.
62. [OH –] = 3.73 × 10–2 M, [H3PO4] = 5.93 × 10–18 M

PO 34- + 3H 2O -
H 3PO 4 + 3OH Kh
[H3PO4] = Ch
[OH–] = 3Ch
Ch ´ (3Ch)3
Kh = = 27h4 C 3 (Assuming h << 1)
C - Ch
Kw
and K h =
K 1K 2K 3
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63. (a) pH = 4.75 (b) pH = 4.697 (c) pH = 4.798
(d) 1.116% on acid addition, 1.03% on base addition.
For acidic buffer of CH 3CH2COOH + CH3CH2COONa
[H + ][CH 3CH 2COO - ]

Ka =
[CH 3CH 2COOH]
[CH3CH 2COO- ]
\ pH = pKa + log
[CH 3CH 2COOH]
On adding of a HCl
CH 3 CH 2COONa + HCl ¾¾® CH 3CH 2COOH + NaCl

On adding of NaOH
CH 3CH 2COOH + NaOH ¾¾® CH 3 CH 2COONa + H 2O
[Na 2H PO 4 ]
64. [NaH2PO 4 ] = 1.55 M
Mixture of weak acid & its salt with strong base is acidic buffer.
65. [H2P 2O7–2 ] = 4.9 × 10–3 M

H4P2O7 –
H3 P2 O7 + H
+ K1
0.05 – x x–y x+y

H 3P2O7- 2-
H 2P2O7 + H
+
x–y y x+y K2
[H + ] = 2[H 2P2O72- ] + [H 3P2O7- ]
[H + ][H 2P2O72- ]
K2 =
[H 3P2O7- ]
[H + ][H 3P2O7- ]
K1 =
[H 4 P2O7 ]
0.05 = [H 4 P2O7 ] + [H 3P2O7- ] + [H 2P2O72- ]

Alternatively, if we assume that in weak diprotic acid most of [H +] comes from 1 st ionization only.
Then
x2
K1 = where [H+] = xM
0.05 - x
[H + ][H 2P2O72- ]
& K2 =
[H 3P2O7- ]
66. Ka = 1.73 × 10–5 pH = 8.73 67. 85.71%

68. D pH = 0.954 69. (a) pH = 3 (b) pH = 5.48, (c) pH = 8.85, (d) pH = 12.05
70. 0.257 71. [Cu+] = 5 × 10–11 M
72. 12 mg 73. 2.8 × 10–3 M
74. 1.84 g/lt 75. 9.4 × 10–2 mol litre–1
76. [Ag(NH3)2+] = 0.0539 77. pH = 11.3010
78. s = 1.203 × 10–3 M 79. 3.925
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Ionic Equilibrium
80. (a) 0.0175 %, pH = 1, (b) 4.75 81. NO
82. pH = 9
83. [Cu+2] = 8.825 × 10–8 , [Pb+2] = 7.119 × 10–8

Cu 3 (AsO4 )2 (s)
3Cu
2+
+ 2AsO 34-
3S1 2S1 + 2S 2
Pb3 (AsO 4 )2

3Pb
2+
+ 2AsO 42-
3S 2 2S 2 + 2S1
8 ´ 10-36 = (3S1 )3 ´ (2S1 + 2S 2 )2

4.096 ´ 10 -36 = (3S 2 )3 ´ (2S1 + 2S 2 )2
84*. (a) pH = 9.415 (b) pH = 4.23

-
Al(OH)3 + OH ¾¾® [Al(OH)4 ]-
Al(OH)3 + 3H + ¾¾® Al 3 + + 3H 2O
[OH–]required = [Al(OH)3] present
[H+]required = 3[Al(OH)3] present
85. V = 2.77 × 104 L

For weak acid of type HA, having a < < 1
1 1 1
pH = pKa - pKa - log C
2 2 2
86*. (a) 2.12 (b) 4.66 (c) 7.2 (d) 12
H 3 PO4 + NaOH ¾¾® NaH 2 PO4 + H 2O
NaH 2 PO4 + NaOH ¾¾® Na 2HPO4 + H 2 O
Na 2 HPO4 + NaOH ¾¾® Na 3 PO 4 + H 2 O
[H 2PO-4 ]
(a) pH = pKa1 + log
[H 3 PO4 ]
pKa1 + pKa 2
(b) pH =
2
[HPO42- ]
(c) pH = pKa 2 + log
[H 2 PO4- ]
[PO 34- ]
(d) pH = pKa 3 + log
[HPO 24- ]
87. Ans. 9.1628
BOH + HCl ¾¾® BCl + H 2O

weak base
\ Cationic hybrolysis occurs

1 1
pH = 7 - pK b - log C
2 2
Addition of NaOH is resulting solution will cause neutralization.
H + + OH - ¾¾® H 2O
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88. 0.0818 moles
On addition of NaOH in this buffer solution.
NH4Cl + NaOH ¾¾® NH4OH + NaCl–
t = 0 0.1 M xM 0.1M 0
t 0.1–x 0 0.1 + x x
[0.1]
[pOH]i = pK b + log
[0.1]
[0.1 - x]
[pOH]f = pK b + log
[0.1 + x]
DpOH = 1
[0.1 - x] [0.1 + x]
\ - log = 1 or = 10
[0.1 + x] [0.1 - x]
89*. [H2CO3] = 9.85 × 10–6 M, [HCO3–] = 4.9 × 10–4 M, [CO3–2] = 2.45 × 10–8 M

+ -
H + HCO 3 K1
H 2CO 3

HCO -3 + 2-
H + CO 3 K2
-8
10 ´ [HCO 3- ]
5 ´ 10 -7 =
[H 2CO 3 ]
[CO23- ]
5 ´ 10 -13 = 10-8 ´
[HCO -3 ]
[H + ] = [HCO -3 ] + 2[CO32- ]
90. Ans. 1.6 m mole

For solution contaning Na2HPO4 & NaH2PO4
[H + ][HPO -4 ]
Ka 2 =
[H 2PO 4- ]
91*. 6 × 105 ions

[NH -2 ] = K NH 3
92. Ans. 9.5228

H+ + OH– ¾¾® H2 O
10–2 mg mol 2 × 10–2 mg mol 0
-2
10
[OH– ]left = M
0.3
93*. Ans. 2.45
1.725 /(M.wt) salicylacacid
In saturated solution [Salicylic acid] =
1
salicylic acid will behave like weak diprotic acid in the solution
for weak diprotic acid of type H2A

H 2 A + -
H + HA Ka1

HA - + 2-
H + HA Ka 2
Q Ka1 > > Ka2 \ Most of [H+] will be from first ionization only..
[H + ] [HA - ] x2
\ 1 ´ 10 -3 = =
[H 2 A] 1.725
-x
(M.wt) Salicylicacid
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Thermo dynamics
THERMODYNAMICS
True/False
1. Pressure is an intensive property.
2. Like U and H, S is also a state function.
3. When a system undergoes a change at constant pressure, it is referred to an isothermal process.
4. The work done by a gas during free expansion is equal to zero.
5. First law of T.D. is applicable to all processes irrespective to whether they are reversible or irreversible.
6. All spontaneous process proceed in one direction only.
7. Positive value of DSsystem during the process can be taken as sole criterion of spontaneity.
8. The DH of a reaction is independent of temperature.
Fill in the blanks

9. According to IUPAC conventions work done on the surroundings is ................... .
10. A system is said to be ................... if it can neither exchange matter nor energy with surrounding.
11. The efficiency of a carnot engine can be increased by ................... sink temperature when the source tempera-
ture is held constant.
12. Entropy change of a system is determine by the ................... and ................... states only, irrespective of how
the system has changed its states.
13. Solidification of liquid shows ................... in entropy.
14. When Fe(s) is dissolved in a aqueous HCl in a closed rigid vessel, the work done is ................... .
15. For Non-spontaneous process at constant T & P DG is ................... .
Assertion-Reason
(B) Statement-I is true, Statement-II is true ; Statement-II is NOT a correct explanation for Statement-I
(C) Statement-I is true, Statement-II is false.
(D) Statement-I is false, Statement-II is true.
16. Statement-I : The heat absorbed during the isothermal expansion of an ideal gas against vaccum is zero.
Because
Statement-II : The volume occupied by the molecules of an ideal gas is zero.
17. Statement-I : The magnitude of the work involved in an isothermal expansion is greater than that involved in
an adiabatic expansion.
Because
Statement-II : P–V curve (P on y-axis and V on x-axis) decrease more rapidly for reversible adiabatic expan-
sion compared to reversible isothermal expansion starting from same initial state.
18. Statement-I : Entropy change in reversible adiabatic expansion of an ideal gas is zero.
Because
Statement-II : The increase in entropy due to volume increase just compensate the decrease in entropy due to
fall in temperature.
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19. Statement-I : The standard free energy changes of all spontaneously occuring reactions are negative.
Because
Statement-II : The standard free energies of the elements in their standard states at 1 bar and 298 K are taken
as zero.
20. Statement-I : Enthalpy and entropy of any elementary substance in the standard states are taken as zero.
Because
Statement-II : At absolute zero, particles of the perfectly crystalline substance become completely ordered.
21. Statement-I : A reaction which is spontaneous and accompained by decrease of randomness must be exothermic.
Because
Statement-II : All exothermic reactions are accompanied by decrease of randomness.
22. Statement-I : Decrease of free energy during the process under constant temperature and pressure provides a
measure of its spontaneity.
Because
Statement-II : A spontaneous change must have +ve sign of DSsystem.
23*. For a perfectly crystalline solid Cp.m. = aT3, where a is constant. If Cp.m. is 0.42 J/K–mol at 10 K, molar entropy
at 10 K is
(A) 0.42 J/K-mol (B) 0.14 J/K-mol (C) 4.2 J/K-mol (D) zero
24*. Given the following data :

Substance DH° (kJ/mol) S°(J/mol K) DG° (kJ/mol)
FeO(s) – 266.3 57.49 – 245.12
C (Graphite) 0 5.74 0
Fe(s) 0 27.28 0
CO(g) – 110.5 197.6 – 137.15
Determine at what temperature the following reaction is spontaneous ?
FeO(s) + C (Graphite) ¾¾® Fe(s) + CO(g)
(A) 298 K
(B) 668 K
(C) 966 K
(D) DG° is +ve, hence the reaction will never be spontaneous
25*. The piece of zinc at a temperature of 20.0°C weighing 65.38 g is dropped into 180 g of boiling water
(T = 100°C). The specific heat of zinc is 0.400 J g –1 °C–1 and that of water is 4.20 J g–1°C–1. What is the final
common temperature reached by both the zinc and water :-
(A) 97.3°C (B) 33.4°C (C) 80.1°C (D) 60.0°C
26*. A vessel contains 100 litres of a liquid x. Heat is supplied to the liquid in such a fashion that, heat given =
change in enthalpy. The volume of the liquid increases by 2 litres. If the external pressure is one atm, and 202.6
Joules of heat were supplied then, [U ® total internal energy] :-
(A) DU = 0, DH = 0 (B) DU = +202.6 J, DH = +202.6 J
(C) DU = –202.6 J, DH = –202.6 J (D) DU = 0, DH = +202.6 J
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27*. What is the net work done (in calories) by 1 mole of monoatomic ideal gas in a process described by 1, 2, 3,
4 in given V–T graph.
40 L 3
Use : R = 2cal / mole K
ln 2 = 0.7
V 2
(A) – 600 cal 20 L
(B) – 660 cal 10 L 4
1
(C) + 660 cal
T
(D) + 600 cal
300 K 600 K
28. How much energy must be supplied to change 36 g of ice at 0°C to water at room temperature 25°C
Data for water, H2O DH°fusion = 6.01 kJ mol–1 Cp.liquid = 4.18 J.K–1 g–1
(A) 12 kJ (B) 16 kJ (C) 19 kJ (D) 22 kJ
29*. One mole of an ideal diatomic gas (CV = 5 cal) was transformed from initial 25°C and 1 L to the state when
temperature is 100°C and volume 10L. The entropy change of the process can be expressed as (R = 2 calories/
mol/K) :-
298 373 373 1 373 1

(A) 3 ln + 2 ln 10 (B) 5 ln + 2 ln 10 (C) 7 ln + 2 ln (D) 5 ln + 2 ln
373 298 298 10 298 10
30. Calculate the total entropy change for the transition at 368 K of 1 mol of sulphur from the monoclinic to the
rhombic solid state, if DH = –401.7 J mol–1 for the transition. Assume the surrounding to be an ice-water both
at 0°C :-
(A) –1.09 JK–1 (B) 1.47 JK–1 (C) 0.38 JK–1 (D) None of these
31*. One mole of an ideal monoatomic gas expands isothermally against constant external pressure of 1 atm from
initial volume of 1L to a state where its final pressure becomes equal to external pressure. If initial temperature
of gas is 300 K, then entropy change of system in the above process is :-
(R = 0.082 L atm mol–1 K–1 = 8.3 J mol–1 K–1)
3
(A) 0 (B) Rln(24.6) (C) Rln (2490) (D) Rln(24.6)
2
32*. The enthalpy change for a given reaction at 298 K is –x J mol–1 (x being positive). If the reaction occurs
spontaneously at 298 K, the entropy change at that temperature :
x
(A) Can be negative but numerically larger than
298
x
(B) Can be negative but numerically smaller than
298
(C) Cannot be negative
(D) Cannot be positive
33*. One mole of a real gas is subjected to heating at constant volume from (P 1,V1,T1) state to (P2,V1,T2) state. Then
it is subjected to irrerversible adiabatic compression against constant external pressure P3 atm till system reaches
final state (P3,V2,T3). If the constant volume molar heat capacity of real gas is Cv. Find out correct expression for
DH from state 1 to state 3.
(A) Cv (T3 – T1) + (P3V1 – P1V1) (B) Cv (T2 – T1) + (P3V2 – P1V1)
(C) Cv (T2 – T1) + (P3V1 – P1V1) (D) Cp (T2 – T1) + (P3V1 – P1V1)
34*. When two equal sized pieces of the same metal at different temperatures T h(hot piece) and Tc (cold piece) are
brought into contact into thermal contact and isolated from it's surrounding. The total change in entropy of
system is given by ? [Cv (J/K) = heat capacity of metal]
Tc + Th T2 ( Tc + Th )2 ( Tc + Th )2
(A) Cv ln 2Tc (B) Cvln T (C) Cv ln (D) Cvln
1 2Th .Tc 4Th .Tc
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35*. The enthalpy of tetramerization of X in gas phase (4X(g) ® X4(g)) is – 100 kJ/mol at 300 K. The enthalpy of
vaporisation for liquid X and X4 are respectively 30 kJ/mol and 72 kJ/mol respectively.
DS for tetramerization of X in liquid phase is – 125 J / K mol at 300 K.
What is the DG at 300 K for tetramerization of X in liquid phase ?
(A) –52 kJ/mol (B) –89.5 kJ/mol (C) –14.5 kJ/mol (D) None of these
36. The change in entropy of 2 moles of an ideal gas upon isothermal expansion at 243.6 K from 20 litre until the
pressure becomes 1 atm, is :
(A) 1.385 cal / K (B) –1.2 cal / K (C) 1.2 cal / K (D) 2.77 cal / K
37. Molar heat capacity of water in equilibrium with ice at constant pressure is :- [IIT-JEE-1997]
(A) zero (B) ¥
–1 –1
(C) 40.45 kJ K mol (D) 75.48 JK–1 mol–1
38. Which of the following statement is false ? [IIT-JEE-2001]

(A) Work is a state function
(B) temperature is a state function
(C) Change of state is completely defined when initial and final states are specified
(D) Work appears at the boundary of the system
39*. One mole of non-ideal gas undergoes a change of state (2.0 atm, 3.0 L, 95 K) to (4.0 atm, 5.0 L, 245 K) with
a change in internal energy (DU) = 30.0 L-atm. The change in enthalpy (DH) of the process in L-atm :-
[IIT-JEE-2002]
(A) 40.0 (B) 42.3
(C) 44.0 (D) not defined, because pressure is not constant
40. Two mole of an ideal gas is expanded isothermally and reversibly from 1 litre to 10 litre at 300 K. The enthalpy
change (in kJ) for the process is :- [IIT-JEE-2004]
(A) 11.4 kJ (B) –11.4 kJ (C) 0 kJ (D) 4.8 kJ
41. The enthalpy of vapourization of a liquid is 30 kJ mol–1 and entropy of vapourization is 75 J mol–1 K. The boiling
point of the liquid at 1 atm is :- [IIT-JEE-2004]
(A) 250 K (B) 400 K (C) 450 K (D) 600 K
42*. One mole of monoatomic ideal gas expands adiabatically at initial temp. T against a constant external pressure
of 1 atm from one litre to two litre. Find out the final temp. (R = 0.0821 litre. atm K –1 mol–1)[IIT-JEE-2005]
T 2 2
(A) T (B) (C) T – (D) T +
5
3 ´ 0.0821 3 ´ 0.0821
( 2 ) 3 -1
43*. An ideal gas is taken from state A (Pressure P, Volume V) to the state B (Pressure P/2, Volume 2V) along a
straight line path in PV diagram as shown in the adjacent figure.
Select the correct statement(s) among the following.
A
Pressure
P
P/2 B
V 2V
Volume
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(A) The work done by gas in the process A to B exceeds the work that would be done by it if the system were
taken from A to B along the isotherm.
(B) In the T–V diagram, the path AB become part of parabola
(C) In the P–T diagram, the path AB becomes a part of hyperbola.
(D) In going from A to B, the temperature T of the gas first increases to a maximum value then decreases.
44*. Two moles of an ideal gas (Cv,m = 3/2R) is subjected to following change of state.
Single stage
adiabatic compression
A (500 K, 5.0 bar) ¾¾¾¾¾
Reversible
® B ¾¾¾¾® C (250 K, 1.0 bar) ¾¾¾¾¾¾¾¾
Isochoric
® D
isothermal (3 bar)
cooling
expansion
The correct statement is / are :

(A) The pressure at B is 2.0 bar (B) The temperature at D is 450 K
(C) DHCD = 1000 R (D) DUBC = 375 R
45*. If one mole monoatomic ideal gas was taken through process AB as shown in figure, then select correct option(s).
V
15 L B
10 L
A
300 600 T
(A) wAB = – 1496.52 J (B) qAB = 5237.82 J (C) DHAB = 3741.3 J (D) DSAB is +ve
46*. Which of the following statement(s) is/are correct :

(A) Reversible isothermal compression of an ideal gas represents the limiting minimum value of the workdone
(|w|) by the surrounding on the system.
(B) In an irreversible process, the cyclic integral of work is not zero.

æ C p,m ö
ç ÷
(C) For thermodynamic changes in adiabatic process T è R ø .P = constant
V2 - b é V1 ´ V2 ù
(D) Work done by 1 mole of a real (vander waals) gas W = – RT ln V - b - a ê V - V ú
1 ë 2 1û
Comprehension
Comprehension-1
An ideal gas, having ratio of specific heat g undergoes a process in which its internal energy relates to the volume
as U = a V , where a is a constant. If the gas is expanded from volume V 1 to V2.
47*. The work performed by gas is :
(A) 2a(g – 1) [ V2 - V1 ] (B) a(g – 1) [ V2 - V1 ] (C) 2a(g – 1) [V2 – V1] (D) a(g – 1) [V2 – V1]
48*. If the ideal gas is diatomic and its increase in internal energy is 100 J then the work performed by gas is: (Ignore
vibrational degree of freedom)
(A) 80 J (B) 180 J (C) 100 J (D) 20 J
49*. In the above question, the heat supplied to gas is :

(A) 80 J (B) 180 J (C) 100 J (D) 20 J
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Comprehension-2
Standard Gibb's energy of reaction (DrG°) at a certain temperature can be computed as DrG° = DrH° – T. DrS°
and the change in the value of DrH° and DrS° for a reaction with temperature can be computed as follows :
D r H °T - D r H °T1 = D r C °p (T2 - T1 )
2
æT ö
D r S°T - D r S°T1 = D r C°p ln ç 2 ÷
è T1 ø
2
DrG° = DrH° – T.DrS° and by DrG° = –RT ln Keq.

Consider the following reaction :

CO(g) + 2H2(g) CH3OH(g)
Given :
DfH° (CH3OH, g) = –201 kJ/mol ; DfH° (CO, g) = – 114 kJ/mol
S°(CH3OH, g) = 240 J/K-mol ; S°(H2, g) = 29 JK–1 mol–1
S°(CO, g) = 198 J/mol-K ; C°p, m(H2) = 28.8 J/mol-K
C°p, m(CO) = 29.4 J/mol-K ; C°p, m(CH3OH) = 44 J/mol-K
æ 320 ö
and ln ç ÷ = 0.06, all data at 300 K
è 300 ø
50. DrS° at 300 K for the reaction is :

(A) 152.6 J/K-mol (B) 181.6 J/K-mol (C) –16 J/K-mol (D) none of these
51. DrH° at 300 K for the reaction is :

(A) –87 kJ/mol (B) 87 kJ/mol (C) –315 kJ/mol (D) –288 kJ/mol
52*. DrS° at 320 K is :

(A) 155.18 J/mol-K (B) 150.02 J/mol-K (C) 172 J/mol-K (D) 18.58 J/mol-K
53*. DrH° at 320 K is :

(A) –288.86 kJ/mol (B) –289.1 kJ/mol (C) –87.86 kJ/mol (D) none of these
54*. DrG° at 320 K is :

(A) –48295.2 kJ/mol (B) –240.85 kJ/mol (C) 93.80 kJ/mol (D) –81.91 kJ/mol
Comprehension-3
9.0 g ice at 0°C is mixed with 36 g of water at 50°C in a thermally insulated container. Using the following data,
answer the question that follow ?
CP (H2O) = 4.18 Jg–1K–1 ; DHfusion (ice) = 335 J g–1
55. Final temperature of water is

(A) 304.43 K (B) 296.97 K (C) 303.93 K (D) 287 K
56*. DSice is
(A) 11.04 JK–1 (B) 3.16 JK–1 (C) 14.2 JK–1 (D) 7.84 JK–1
57*. DSwater is
(A) –12.64 JK–1 (B) –0.34 JK–1 (C) –5.42 JK–1 (D) 12.64 JK–1
58. What is the total entropy change in the process ?

(A) –1.56 JK–1 (B) –1.60 JK–1 (C) 1.56 JK–1 (D) 1.60 JK–1
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Subjetive Questions
59*. One mole of solid Zn is placed in excess of dilute H2SO4 at 27 °C, in a cylinder fitted with a piston. Find the
value of DE, q and w for the process if the area of piston is 500 cm2 and it moves out by 50 cm against a
pressure of 1 atm during the reaction. The heat given to surrounding is 36.5 kJ.
Zn(s) + 2H+ (aq) l Zn2+ (aq) + H2(g)
60*. Methane (Considered to be an ideal gas) initially at 25°C and 1 bar pressure is heated at constant pressure until
the volume has doubled. The variation of the molar heat capacity with absolute temperature is given by :
CP = 22.34 + 48.1 × 10–3 T. where CP is in JK–1 mol–1. Calculate molar (a) DH (b) DU.
61. One mole of NaCl(s) on melting absorved 30.5 kJ of heat and its entropy is increased by 28.8 JK –1. What is the
melting point of sodium chloride ?
62*. Oxygen is heated from 300 K to 600 K at a constant pressure of 1 bar. What is the increases in molar entropy?
The molar heat capacity in JK–1 mol–1 for the O2 is.
CP = 25.5 + 13.6 × 10–3 T – 42.5 × 10–7 T2
63. Calculate the free energy change at 298 K for the reaction :
Br2(l) + Cl2(g) ¾® 2BrCl(g). For the reaction DH° = 29.3 kJ & the entropies of Br2(l), Cl2(g) & BrCl(g) at the
298 K are 152.3, 223.0, 239.7 J mol–1 K–1 respectively.
64. Using the data given below, establish that the vaporization of CCl4(l) at 298K to produce CCl4(g) at 1 atm
pressure does not occur spontaneously.
Given : CCl4 (l, 1 atm) ¾® CCl4 (g, 1 atm) ; DS° = 94.98 JK–1 mol–1
DH°f (CCl4, g) = –106.7 kJ mol–1 & DH°f(CCl4, l) = –139.3 kJ mol–1
65*. From the given table answer the following questions :

Reaction : H2O (g) + CO(g) H2(g) + CO2(g)
(i) Calculate Dr H°298 (ii) Calculate Dr G°298
(iii) Calculate Dr S°298 (iv) Calculate Dr E°298
(v) Calculate S°298 [H2O(g)]
66*. Compute DrG for the reaction H2O (l, 1 atm, 323 K) ® H2O (g, 1 atm, 323 K)
Given that : DvapH at 373 K = 40.639 kJmol–1, CP(H2O, l) = 75.312 J K–1 mol–1,
CP(H2O, g) = 33.305 J K–1mol–1.
67*. (a) An ideal gas undergoes a single state expansion against a constant opposing pressure from (P1,V1, T) to
(P2,V2, T). What is the largest mass m which can be lifted through a height h in this expansion ?
(b) The system (a) restored to its initial state by a single state compression. What is the smallest mass m'
which must fall through the height h to restore system?
(c) What is the net mass lowered through height h in the cyclic transformation in (a) and (b) ?
68*. A sample of argon gas at 1 atm pressure and 27°C expands reversibly and adiabatically from 1.25 dm 3 to
2.50 dm3. Calculate the enthalpy change in this process. Cv.m. for argon is 12.48 JK–1 mol–1.[IIT-JEE-2000]
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1
69. Show that the reaction CO(g) + O (g) ¾® CO2(g) at 300 K is spontaneous and exothermic, when the
2 2
standard entropy is –0.094 kJ mol–1 K–1. The standard Gibbs free energies of formation for CO 2 and CO are –
394.4 and –137.2 kJ mol–1, respectively. [IIT-JEE-2001]
70*. Two moles of a perfect gas undergoes the following processes : [IIT-JEE-2002]
(a) a reversible isobaric expansion from (1.0 atm, 20.0 L) to (1.0 atm, 40.0 L) ;
(b) a reversible isochoric change of state from (1.0 atm, 40.0 L) to (0.5 atm, 40.0 L) ;
(c) a reversible isothermal compression from (0.5 atm, 40.0 L) to (1.0 atm, 20.0 L) ;
(i) Sketch with labels each of the processes on the same P–V diagram.
(ii) Calculate the total work (w) and the total heat change (q) involved in the above processes.
(iii) What will be the values of DU, DH and DS for the overall process ?
71*. One mole of a liquid (1 bar, 100 mL) is taken in an adiabatic container and the pressure increases steeply to 100
bar. Then at a constant pressure of 100 bar, volume decreases by 1 mL. Find DU and DH. [IIT-JEE-2004]
72. The increase in entropy of 1 kg of ice at 200 K which is heated to 400 K (super heated steam) at constant
atmospheric pressure, will be :
Given that Cp (ice) = 2.09 × 103 J/kg degree ; Cp(water) = 4.18 × 103 J/kg degree
3
Cp(steam) = 2.09 × 10 J/kg degree ; Lf (C, 273 K) = 3.34 × 105 J/kg ;
Lv (water, 273 K) = 22.6 × 105 J/kg
73*. Calculate workdone in adiabatic compression of one mole of an ideal gas (monoatomic) from an initial pressure
of 1 atm to final pressure of 2 atm. Initial temperature = 300 K
(a) If process is carried out reversibly.
(b) If process is carried out irreversible against 2 atm external pressure.
Compute the final volume reached by gas in two cases.
74*. 20.0 dm3 of an ideal gas (diatomic Cv,m = 5 R/2) at 673 K and 0.7 MPa expands until prressure of the gas is 0.2
MPa. Calculate q, w, DU and DH for the process if the expansion is :
(i) Isothermal and reversible
(ii) Adiabatic and reversible
(iii) Isothermal and adiabatic
(iv) Against 0.2 MPa and adiabatic
(v) Against 0.2 MPa and isothermal.
75*. One mole of an ideal gas is expanded isothermally at 298 K until its volume is tripled. Find the values of DSgas
and DStotal under the following conditions.
(i) Expansion is carried out reversibly.
(ii) Expansion is carried out irreversibly where 836.6 J of heat is less absorbed than in (i)
(iii) Expansion is free.
76*. 10 g of neon initially at a pressure of 506.625 kPa and temperature of 473 K expand adiabatically to a pressure
of 202.65 kPa. Calculate entropy change of the system and total entropy change for the following ways of
carrying out this expansion.
(i) Expansion is carried out reversibly.
(ii) Expansion occurs against a constant external pressure of 202.65 kPa.
(iii) Expansion is free expansion.
77. Pressure over 1000 mL of a liquid is gradually increases from 1 bar to 1001 bar under adiabatic conditions. If
the final volume of the liquid is 990 mL, calculate DU and DH of the process, assuming linear variation of
volume with pressure.
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78*. One mole of ideal monoatomic gas was taken through reversible isochoric heating from 100 K to 1000 K.
Calculate DSsystem, DSsurr, and DStotal in
(i) when the process carried out reversibly
(ii) when the process carried out irreversibly (one step)
79*. Fixed amount of an ideal gas contained in a sealed rigid vessel (V = 24.6 litre) at 1.0 bar is heated reversibly
from 27°C to 127°C. Determine change in Gibb's energy (in Joule) if entropy of gas S = 10 + 10 –2 T (J/K).
80*. A 32 g sample of CH4 gas initially at 101.325 kPa and 300 K is heated to 550 K. CP,m/JK–1 mol–1 = 12.552 +
8.368 × 10–2 T/K. Assuming CH4 behaves ideally, compute w, q, DU and DH for (a) an isobaric reversible
process and (b) an isochoric reversible process.
81*. At 298 K, DH°combustion (sucrose) = – 5737 kJ/mol & DG°combustion (sucrose) = –6333 kJ/mol. Estimate additional
non-PV work that is obtained by raising temperature to 310 K . Assume DrCP = 0 for this temperature change.
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ANSWERS
l True and False
1. True 2. True 3. False 4. True 5. True

6. True 7. False 8. False
l Fill in the blanks

9. Negative 10. Isolated 11. Decreasing 12. (i) initial (ii) final
13. decrease 14. zero 15. positive
16. (B) 17. (A) 18. (A) 19. (B) 20. (D)
21. (C) 22. (C)
23. (B) 24. (C) 25. (A) 26. (D) 27. (C)
28. (B) 29*. (B) 30. (C) 31*. (B) 32*. (D)
33*. (C) 34*. (D) 35*. (C) 36. (D) 37. (B)
38. (A) 39*. (C) 40. (C) 41. (B) 42*. (C)
43. (ABD) 44. (ABC) 45. (BD) 46. (AB)
l Comprehension
Comprehension 1 : 47*. (A) 48*. (A) 49*. (B)

Comprehension 2 : 50. (C) 51. (A) 52*. (A)
53*. (C) 54*. (D)
Comprehension 3 : 55. (B) 56*. (C) 57*. (A)
58. (C)
59. DE = – 39.03 kJ/mole; q = – 36.5 kJ;w = – 2.53 kJ
60*. (a) 13.064 kJ mol–1 (b) 10.587 kJ mol–1 61. T = 1059 k
62*. 21.18 Jk–1 mol–1 63. –1721.8 J
64. DG° = 4.3 kJ mol–1 > 0
65*. (i) –9,83 kcal mol–1 (ii) –6.81 kcal mol–1 (iii) –10.13 cal/K mol (iv) –9.83 kcal/mol
(v) +45.13 cal/K mole
66*. DrG = 5.59 kJ mol–1
nRT æ P2 ö nRT æ P1 ö nRT æ (P1 - P2 )2 ö

67*. (a) m = m = 1 - m ' = - 1 m' - m = ç ÷
gh çè P1 ÷ø , (b) gh çè P2 ÷ , (c)
ø gh è P1P2 ø
68*. DH = –114.52 J 69. DH° = –285.4 kJ/mol, DG° = –257.2 kJ/mol
70*. (ii) –w = q = 620.77 J, (iii) DH = 0, DU = 0, DS = 0

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71*. DU = 0.1 litre atm, DH = 9.9 litre atm
72. 9390 J kg–1
73*. (a) T2 = 395.8 ; V2 = 16.24 L ; wrev = 1194.72 J, (b) V12 =17.24 L ; T12 =420 K ; wirrev = 1496.52 J\
74*. (i) q = – w = 17.54 kJ, DU = 0 and DH = 0 ; (ii) q = 0, w = DU = – 10.536 kJ and DH = –14.75 kJ

(iii) q = 0, w = 0, DU = 0 and DH = 0 ; (iv) q = 0 ; DU = w = –7.14 kJ ; DH = –9.996 kJ
(v) q = – w = 9.94 kJ, DU = DH = 0
75*. (i) DSgas = – DSsurr and DStotal = 0, (ii) DStotal = 2.808 J K–1,
(iii) DStotal = DSsys = 9.134 J K–1
76*. (i) DSsys = 0 ; DSsurr = 0 and DStotal = 0, (ii) DSsurr = 0 ; DStotal = DSsys = 0.957 JK–1
(iii) DSsys = DStotal = 3.81 JK–1
77. DU = 501 J ; DH = 99.5 kJ
3 3
78*. (i) Rev. process DSsys = R ln 10 ; DSsurr =– R ln 10,
2 2
3 3 3
(ii) Irr. process DSsys = R ln 10 ; DSsurr =– (0.9) ; DStotal = R (1.403)
2 2 2
79*. –530 J
80*. (a) qp = DH = 24.058 kJ, w = – 4.157 kJ, DU = 19.90 kJ ;

(b) DU = 19.90 kJ, DH = 24.058 ; w = 0
81*. 24 kJ/mol
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THERMOCHEMISTRY
True/False
1. DH°f (C, diamond) ¹ 0
2. For a particular reaction DE = DH + P.DV
3. If BE (bond energy) of N º N bond is x1 that of H – H bond is x2 and N – H bond is x3 then enthalpy change of
the reaction is
N2 + 3H2 ¾® 2NH3 DHr = x1 + 3x2 – 2x3
4. Enthalpy change is dependent on temperature and on the path adopted.
5. Heat of hydrogenation of ethene is x1 and that of benzene is x2, hence resonance energy of benzene is
(x1 – x2).
6. The enthalpies of elements are always taken to be zero.
7. Heat of neutralisation of weak acid-strong base is not constant.
8. Resonance energy is always negative.
3 B x
9. For reaction 2A(g) + B(g) ¾® 3C (g) DH = -x kJ then for reaction C(g) ¾® A(g) + (g) DH = kJ.
2 2 2
Fill in the blanks

10. The combustion of a substance is always ................... .
11. If heat content of X is smaller than that of Y then the process X ® Y is ................... .
12. C (Diamond) ¾® C (Graphite) + x kJ. The heat change in this process is called ................... .
13. As per reaction, N2(g) + 2O2(g) ¾® 2NO2(g) –66 kJ the value of DHf of NO2 is ................... .
14. Heats of combustion of methane, carbon and hydrogen are –212, –94, –68 kcal mol–1. The heat of formation
of CH4 is ................... .
15. The heat of neutralisation of 1 mole of HClO4 with 1 gm-equivalent of NaOH in aqueous solutions is ...................
kJ mol–1.
16. The heat of combustion of graphite and carbon monoxide respectively are –393.5 kJ mol–1 and –283 kJ
mol–1. Thus heat of formation of carbon monoxide in kJ mol–1 is ................... .
17. For the reaction,

C3H8(g) + 5O2(g) ¾® 3CO2(g) + 4H2O(l) at constant temperature, DH – DU is ................... .
Assertion–Reason
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18. Statement-I : Enthalpy of neutralization of CH3COOH by NaOH is less than that of HCl by NaOH.
Because
Statement-II : Enthalpy of neutralization of CH3COOH is less because of the absorption of heat in the
ionization process.
19. Statement-I : Enthalpy changes are positive when Na2SO4.10H2O, CuSO4.5H2O and salts like NaCl, KCl, etc.,
which do not form hydrates are dissolved in water. But enthalpy changes are negative when anhydrous salts
capable of forming hydrates are dissolved in water.
Because
Statement-II : The difference in the behaviour is due to large differences in the molecular weight of hydrated
and anhydrous salts. The substances with larger molecular weights usually show positive enthalpy changes on
dissolution.
20. Statement-I : Heat of neutralisation of HF (aq.), a weak acid, with NaOH (aq.) is more than 13.7 kcal, in an
exothermic reaction.
Because
Statement-II : Some heat is lost in the ionisation of a weak acid.
21. Statement-I : Enthalpy of formation of HCl is equal to bond energy of HCl.

Because
Statement-II : Enthalpy of formation and bond energy both involve the formation of one mole of HCl from the
elements.
22. Statement-I : Enthalpy of atomization is the heat of reaction H2O(l) ¾® H2O(g).

Because
Statement-II : Gaseous molecules are far apart of each other due to less attraction.
23. Statement-I : The enthalpy of formation of H2O(l) is greater than that of H2O(g).
Because
Statement-II : Enthalpy change is negative for the condensation reaction, H2O(g) ¾® H2O(l).
24. Statement-I : As temperature increases, heat of reaction also increases for exothermic as well as for endothermic
reactions.
Because
Statement-II : DH varies with temperature as given by DH2 (at T2) = DH1 (at T1) + DCP(T2 – T1)
25. Statement-I : Heat of combustion is always negative.

Because
Statement-II : Heat of combustion is used to calculate of fuels.
26*. A gas mixture 3.67 L in volume contain C2H4 and CH4 is proportion of 2 : 1 by moles and is at 25°C and 1 atm.
If the DHC (C2H4) and DHC (CH4) are –1400 and –900 kJ/mol find heat evolved on burning this mixture:-
(A) 20.91 kJ (B) 50.88 kJ (C) 185 kJ (D) 160 kJ
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27. The fat, glyceryl trioleate, is metabolized via the following reaction. Given the enthalpies of formation, calculate
the energy (kJ) liberated when 1.00 g of this fat reacts.
(Atomic weights: C = 12.01, H = 1.008, O = 16.00).
C57H104O6(s) + 80 O2(g) ® 57 CO2(g) + 52 H2O(l)
DHo C57H107O6 = –70870 kJ/mole
DHo H2O(l) = –285.8 kJ/mole
DHo CO2(g) = –393.5 kJ/mole
(A) 40.4 (B) 33.4 (C) 37.8 (D) 42.6
28. A sheet of 15.0 g of gold at 25.0oC is placed on a 30.0 g sheet of copper at 45.0oC. What is the final
temperature of the two metals assuming that no heat is lost to the surroundings. The specific heats of
gold and copper are 0.129 J/goC and 0.385 J/goC respectively.
(A) 42.1 (B) 40.1 (C) 41.1 (D) 43.4
29. Calculate the heat of combustion (kJ) of propane, C3H8 using the listed standard enthapy of reaction data:
C3H8(g) + 5 O2(g) ® 3 CO2(g) + 4 H2O(g) 3 C(s) + 4 H2(g) ® C3H8(g) DHo/kJ = – 103.8
C(s) + O2(g) ® CO2(g) DHo/kJ = – 393.5
H2(g) + 1/2 O2(g) ® H2O(g) DHo/kJ = – 241.8
(A) – 2043.9 (B) – 1532.9 (C) – 1021.9 (D) –739.1
30. Use the given standard enthalpies of formation to determine the heat of reaction of the following reaction:
C2H5OH(l) + 3 O2(g) ® 2 CO2(g) + 3 H2O(g) DHof C2H5OH(l) = – 277.7 kJ/mole
DHof CO2(g) = – 393.5 kJ/mole
DHof H2O(g) = – 241.8 kJ/mole
(A) – 1456.3 (B) – 1234.7 (C) – 1034.0 (D) – 1119.4
31. Calculate DHo/kJ for the following reaction using the listed standard enthapy of reaction data:
2 N2(g) + 5 O2(g) ® 2 N2O5(s)
N2(g) + 3 O2(g) + H2(g) ® 2 HNO3(aq) DHo/kJ = –414.0
N2O5(s) + H2O(l) ® 2 HNO3(aq) DHo/kJ = –86.0
2 H2(g) + O2(g) ® 2 H2O(l) DHo/kJ = –571.6
(A) – 84.4 (B) – 243.6 (C) – 71.2 (D) – 121.8
32*. Use the given standard enthalpies of formation to determine the heat of reaction of the following reaction :
2 LiOH(s) + CO2(g) ® Li2CO3(s) + H2O(l)
DHof LiOH(s) = – 487.23 kJ/mole
DHof Li2CO3(s) = – 1215.6 kJ/mole
DHof H2O(l) = – 285.85 kJ/mole
DHof CO2(g) = – 393.5 kJ/mole
(A) +303.4 (B) – 133.5 (C) – 198.6 (D) +198.6
33*. NH3(g) + 3Cl2(g) NCl3(g) + 3HCl (g) ; –DH1

N2(g) + 3H2(g) 2NH3(g) ; DH2
H2(g) + Cl2 (g) 2HCl (g) ; DH3
The heat of formation of NCl3 (g) in the terms of DH1, DH2 and DH3 is ?
DH 2 3 DH 2 3
(A) DHf = –DH1 + – DH3 (B) DHf = DH1 + – DH3
2 2 2 2
DH 2 3
(C) DHf = DH1 – – DH3 (D) None of these
2 2
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o
34. Determine DH of the following reaction using the listed heats of formation :
4 HNO3(l) + P4O10(s) ® 2 N2O5(s) + 4 HPO3(s)
DHof HNO3(l) = –174.1 kJ/mole
DHof N2O5(s) = –43.1 kJ/mole
DHof P4O10(s) = –2984.0 kJ/mole
DHof HPO3(s) = –948.5 kJ/mole
(A) –176.3 (B) – 199.8 (C) +276.2 (D) – 242.4
35*. If x1, x2 and x3 are enthalpies of H–H, O=O and O–H bonds respectively, and x 4 is the enthalpy of vaporisation
of water, estimate the standard enthalpy of combustion of hydrogen.
x2 x2 x2 x2
(A) x1 + –2x3 + x4 (B) x1 + –2x3 – x4 (C) x1 + –x3 + x4 (D) 2x1 – x1 – – x4
2 2 2 2
36. Use the given bond enthalpy data to estimate the DHo (kJ) for the following reaction.
(C – H = 414 kJ, H – Cl = 431 kJ, Cl – Cl = 243 kJ, C – Cl = 331 kJ).
CH4(g) + 4 Cl2(g) ® CCl4(g) + 4 HCl(g)
(A) 620 (B) 330 (C) 420 (D) 105
37. DH0f of water is –285.8 kJ mol–1. If enthalpy of neutralisation of monoacid strong base is –57.3 kJ mol–1, DH0f
of OH– ion will be ?
(A) –228.5 kJ mol–1 (B) 228.5 kJ mol–1 (C) 114.25 kJ mol–1 (D) –114.25 kJ mol–1
38*. 4 grams of sodium hydroxide pellets were dissolved in 100 cm3 of water. The temperature before adding the
sodium hydroxide pellets was 25 degrees C, and after adding the pellets it was 35 degrees C. Calculate the
enthalpy change in kJ/mole of the reaction (Specific heat capacity of water = 4.2 J/K/g)
(A) 42 kJ/mole (B) 4.2 kJ/mole (C) 4200 kJ/mole (D) none
39. 50.0 mL of 0.10 M HCl is mixed with 50.0 mL of 0.10 M NaOH. The solution temperature rises by 3.0°C.
Calculate the enthalpy of neutralization per mol of HCl.
(A) –2.5 × 102 kJ (B) –1.3 × 102 kJ (C) –8.4 × 101 kJ (D) –6.3 × 101 kJ
40*. The standard enthalpies of formation of CO2(g), and HCOOH(l) are –393.7 kJ/mol and –409.2 kJ/mol respec-
tively:-
(A) –393.7 kJ/mol is the enthalpy change for the reaction C (s) + O2(g) ® CO2(g)
(B) the enthalpy change for the reaction CO2(g) + H2(g) ® HCOOH(l) would be +15.5 kJ/mol
(C) the enthalpy change for the reaction H2O + CO ® HCOOH is –409.2 kJ/mol
(D) the enthalpy change for the reaction H2(g) + CO2(g) ® H2O(l) + CO(g) is –409.2 kJ/mol
41*. Ethanol can undergoes decomposition to form two sets of products ?
C2H5OH (g) ¾®
if the molar ratio of C2H4 to CH3CHO is 8 : 1 in a set of product gases, then the energy involved in the
decomposition of 1 mole of ethanol is ?
(A) 65.98 kJ (B) 48.137 kJ (C) 48.46 kJ (D) 57.22 kJ
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42. Reactions involving gold have been of particular interest to a chemist. Consider the following reactions,
Au(OH)3 + 4 HCl ¾® HAuCl4 + 3 H2O, DH = –28 kcal
Au(OH)3 + 4 HBr ¾® HAuBr4 + 3 H2O, DH = –36.8 kcal
In an experiment there was an absorption of 0.44 kcal when one mole of HAuBr4 was mixed with 4 moles of
HCl. What is the percentage conversion of HAuBr4 into HAuCl4 ?
(A) 0.5 % (B) 0.6 % (C) 5 % (D) 50%
43. For which of the following change DH ¹ DE?

(A) H2 (g) + I2 (g)¾® 2HI (g) (B) HCl (aq)+ NaOH(aq) ¾® NaCl(aq) + H2O(l)
(C) C(s) + O2(g) ¾® CO2(g) (D) N2 (g)+ 3H2(g) ¾® 2NH3(g)
44*. The reaction CH4(g) + Cl2(g) ¾® CH3Cl(g) + HCl(g) has DH = –25 kCal.
Bond
Bond Energy
kCal
e C—Cl 84
e H—Cl 103
e C—H x
e Cl—Cl y
x:y= 9 :5
From the given data, what is the bond enthalpy of Cl—Cl bond
(A) 70 kCal (B) 80 kCal (C) 67.75 kCal (D) 57.75 kCal
45. For the allotropic change represented by the equation C (graphite) ¾® C (diamond), DH = 1.9 kJ. If 6 g of
diamond and 6 g of graphite are separately burnt to yield CO2, the enthalpy liberated in first case is
(A) less than in the second case by 1.9 kJ (B) more than in the second case by 11.4 kJ
(C) more than in the second case by 0.95 kJ (D) less than in the second case by 11.4 kJ
46*. Hydrazine, a component of rocket fuel, undergoes combustion to yield N2 and H2O.
N2H4 (l) + O2 (g) ¾® N2 (g) + 2H2O (l)
What is the enthalpy combustion of N2H4 (kJ/mole)
Given Reaction DH/kJ
2NH3 (g) + 3N2O (g) ¾® 4N2 (g) + 3H2O (l) – 1011 kJ
N2O (g) + 3H2 (g) ¾® N2H4 (l) + H2O (l) – 317 kJ
4NH3 (g) + O2 (g) ¾® 2N2H4 (l) + 2H2O (l) – 286 kJ
1
H2 (g) + O (g) ¾® H2O (l) – 285 kJ
2 2
(A) – 620.5 (B) – 622.75 (C) 1167.5 (D) + 622.75
47. Find DrU° for the reaction 4HCl (g) + O2 (g) l 2Cl2(g) + 2H2O (g) at 300 K. Assume all gases are ideal.
Given: H2(g) + Cl2(g) ¾® 2HCl (g) D r H o300 = – 184.5 kJ/mole
2H2(g) + O2(g) ¾® 2H2O (g) D r H o300 = – 483 kJ/mole (Use R = 8.3 J/mole)
(A) 111.5 kJ/mole (B) –109.01 kJ/mole (C) –111.5 kJ/mole (D) None
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48*. The enthalpy changes of the following reactions at 27°C are
1
Na(s) + Cl (g) ¾® NaCl (s) DrH = –411 kJ/mol
2 2
H2(g) + S (s) + 2O2 (g) ¾® H2SO4 (l) DrH = –811 kJ/mol
2Na(s) + S(s) + 2O2 (g) ¾® Na2SO4 (s) DrH = –1382 kJ/mol
1 1
H2(g) + Cl2(g) ¾® HCl (g) DrH = –92 kJ/mol; R = 8.3 J/K-mol
2 2
from these data, the heat change of reaction at constant volume ( in kJ/mol) at 27°C for the process
2NaCl (s) + H2SO4 (l) ¾® Na2SO4 (s) + 2HCl (g) is
(A) 67 (B) 62.02 (C) 71.98 (D) None
49. What is the ratio of the enthalpy yield on combustion of hydrogen atoms to steam to the yield on combustion of
an equal mass of hydrogen molecules to steam?
1
Given : H2(g) + O (g) ¾® H2O(g) ; DH = – 242 kJ
2 2
B.E. (H – H) = 436 kJ
(A) 0.80 : 1 (B) 1 : 0.80 (C) 1.80 : 1 (D) 2.80 : 1
50. The molar heat capacities at constant pressure (assume constant with respect to temperature) of A, B and C are
in ratio of 1.5 : 3.0 : 2.0. If enthalpy change for the exothermic reaction A + 2B ¾® 3C at 300 K is – 10
kJ/mol & Cp,m (B) is 300 J/mol then enthalpy change at 310 K is :
(A) – 8.5 kJ/mol (B) 8.5 kJ/mol (C) – 11.5 kJ/mol (D) none of these
51*. (i) Cis-2 - butene ® trans - 2 - butene, DH1

(ii) Cis - 2- butene ® 1 - butene, DH2
(iii) Trans - 2 - butene is more stable than cis - 2 - butene.
(iv) Enthalpy of combustion of 1-butene, DH = -649.8 kCal/mol
(v) 9DH1 + 5 D H2 = 0
(vi) Enthalpy of combustion of trans 2 - butene, DH = -647.0 kCal/mol.
The value of DH1 & DH2 in KCal/mole are
(A) -1.0 , 1.8 (B) 1.8, -1.0 (C) –5, 9 (D) –2, 3.6
52*. The lattice enthalpy of solid NaCl is 772 kJmol–1 and enthalpy of solution is 2 kJmol–1. If the hydration enthalpy
of Na+ & Cl– ions are in the ratio of 3:2.5, what is the enthalpy of hydration of chloride ion?
(A) –140 kJmol–1 (B) –350 kJmol–1 (C) –351.81 kJmol–1 (D) None
53. DH0f of water is – 285.8 kJ mol–1. If enthalpy of neutralisation of monoacid strong base is –57.3 kJ mol –1, DH0f
of OH– ion will be
(A) – 228.5 kJ mol–1 (B) 228.5 kJ mol–1 (C) 114.25 kJ mol–1 (D) –114.25 kJ mol–1
54. Which of the following reactions defines DH °f ?

(A) C(diamond) + C2(g) ¾® CO2(g) (B) 1/2 H2(g) + 1/2 F2(g) ¾® HF(g)
(C) N2(g) + 3H2(g) ¾® 2NH3 (D) CO(g) + 1/2O2(g) ¾® CO2(g)
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55*. Standard molar enthalpy of formation of CO2 is equal to :- [IIT-JEE-1997]
(A) Zero
(B) Standard molar enthalpy of combustion of carbon (graphite)
(C) Standard molar enthalpy of combustion of gaseous carbon
(D) Sum of molar enthalpies of formation of CO and O2
56. Which of the following is not an endothermic reaction :- [IIT-JEE-1999]

(A) Combustion of methane (B) Decomposition of water
(C) Dehydrogenation of ethene to ethylene (D) Conversion of graphite to diamond
57*. DH°f for CO2(g), CO(g) and H2O(g) are –393.5, –110.5 and –241.8 kJ mol–1 respectively. The standard enthalpy
change (in kJ) for the relation : [IIT-JEE-2000]
CO2(g) + H2(g) ¾¾® CO(g) + H2O(g) is :-
(A) 524.1 (B) 41.2 (C) –262.5 (D) –41.2
58. 100 ml 0.5 N H2SO4 (strong acid) is neutralised with 200 ml 0.2M NH 4OH in a constant pressure Calorimeter
which results in temperature rise of 1.4 °C. If heat capacity of Calorimeter content is 1.5 kJ/°C. Which statement
is/are correct
Given : HCl + NaOH ¾® NaCl + H2O + 57 kJ
CH3COOH + NH4OH ¾® CH3COONH4 + H2O + 48.1 kJ
(A) Enthalpy of neutralisation of HCl v/s NH4OH is – 52.5 kJ/mol
(B) Enthalpy of dissociation (ionization) of NH4OH is 4.5 kJ/mol
(C) Enthalpy of dissociation of CH3COOH is 4.6 kJ/mol
(D) DH for 2H2O(l) ¾® 2H+ (aq.) + 2OH¯(aq.) is 114 kJ
59*. From the following data at 25°C

Reaction D rH° kJ/mol
1 1
H (g) + O2(g) ¾® OH (g) 42
2 2 2
1
H2(g) + O (g) ¾® H2O(g) –242
2 2
H2(g) ¾® 2H(g) 436
O2(g) ¾® 2O(g) 495
Which of the following statement(s) is/are correct:
(A) DrH° for the reaction H2O (g) ¾® 2H(g) + O(g) is 925.5 kJ/mol
(B) DrH° for the reaction OH(g) ¾® H(g) + O(g) is 502 kJ/mol
(C) Enthalpy of formation of H(g) is –218 kJ/mol
(D) Enthalpy of formation of OH(g) is 42 kJ/mol
60*. Which of the following statement(s) is/are true?

(A) When (DGsystem)T,P < 0; the reaction must be exothermic
(B) Df H° (S, monoclinic) ¹ 0
(C) If dissociation enthalpy of CH4(g) is 1656 kJ/mole and C2H6 (g) is 2812 kJ/mole, then value of C–C bond
enthalpy will be 328 kJ/mole
(D) If H+(aq) + OH–(aq) ¾® H2O(l) DrH° = –56 kJ/mol
Df H°(H2O, g) = –242 kJ/mole; Enthalpy of vaporization of liquid water = 44 kJ/mol
–
then, Df H°(OH , aq) will be –142 kJ/mole
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61. Select the option in which heat evolved is maximum.
Given : DfH° (CO2,g) = – 75 kCal/mol ; DfH° (CO,g) = – 25 kCal/mol
The product will be CO if excess amount of carbon is present and CO 2 if excess O2 is present
(A) 10 moles of carbon and 4.5 moles of O2
(B) 24 gm of carbon and 64 gm of O2
(C) 4 moles of carbon and 3.5 moles of O2
(D) 30 gm of carbon and 80 gm of O2
62*. For the process: H2O (l, TK, P bar) ® H2O (g, TK, P bar)
(A) DG = 0, If P = vapour pressure of H2O(l) at TK
(B) DG = +ve, If P = vapour pressure of H2O(l) at a temperature above TK
(C) DG = +ve; If P > vapour pressure of H2O(l) at TK
(D) DG = –ve; If P < vapour pressure of H2O(l) at TK
Match the Column
63. List equation/law (in Column I) with statement (in Column II) :
Column-I Column-II
(A) Arrhenius equation (p) Variation of enthalpy of a reaction with temperature
(B) Kirchhoff equation (q) Variation of rate constant with temperature
(C) Second law of thermodynamics (r) Entropy of an isolated system tends to increase and reach
a maximum value
(D) Hess's law of constant heat summation (s) Enthalpy change in a reaction is always constant and
independent of the manner in which the reaction
occurs.
Comprehension
Comprehension-1
The industrial preparation of a polymer, PTFE, is based on the synthesis of the monomer CF 2 = CF2, which is
produced according to reaction (i) below :
2CHClF2(g) ¾® CF2= CF2(g) + 2HCl ...(i)
The monomer CF2= CF2 is also obtained by reaction (ii) below :
2CHF3(g) ¾® CF2= CF2(g) + 2HF(g) ; DH = 198.1kJ/mol ...(ii)
Consider the information below to answer the questions:
Compound DHf MoleculeX–X D(X–X)
HCl(g) –92.3 F–F 154.7
CHClF2(g) –485.2 Cl–Cl 246.7
CF2= CF2(g) –658.3
CF4 –679.6
CCl4 –106.6
64. The enthalpy change for reaction (i).

(A) 100.23 kJ/mol (B) 127.5 kJ/mol (C) –127.5 kJ/mol (D) –100.23 kJ/mol
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65. (i) Use the expressions
CX4(g) ¾® C(s) + 2X2(g)
DH= –DHf
C(s) ¾® C(g) ; DH=718 kJ/mol
and
2X2(g) ¾® 4X(g) ; DH = 2D(X – X)
where X = F,Cl, to the enthalpy change for the two processes
CX4(g) ¾® C(g) + 4X(g)
What is the average C–X bond energies for the species CX 4(g) (where X = F, Cl).
(A) 329.5 kJ/mol, 426.75 kJ/mol (B) 426.75 kJ/mol, 329.5 kJ/mol
(C) –329.5 kJ/mol, –426.75 kJ/mol (D) –426.75 kJ/mol, –329.5 kJ/mol
(ii) Given that the C–H bond energy is 416.1 kJ/mol, the order of relative chemical reactivities of C–H,
C–F, and C–Cl bonds.
(A) C – H > C – Cl > C – F (B) C – F > C – Cl > C – H
(C) C – Cl > C – H > C – F (D) C – Cl > C – F > C – H
Comprehension-2
The hydration enthalpy of anhydrous copper (II) sulphate is defined as the heat absorbed or evolved when one
mole of anhydrous solid is converted to one mole of crystalline hydrated solid.
CuSO4(s) + 5H2O(l) ¾® CuSO4.5H2O(s)
It cannot be measured directly.
In an experiment to determine the hydration enthalpy indirectly, 4 g of the anhydrous solid were added to 50 g
of water and the rise in temperature was 8 degrees. When 4 g of the hydrated solid was added to
50 g of water the fall in temperature was 1.3 degrees.
66*. What is the heat produced when 4 g of anhydrous solid is added to 50 g of water.
(A) 400 kJ (B) 1672 J (C) 200 kJ (D) 836 kJ
67*. What is the enthalpy of solution of anhydrous copper (II) sulphate in kJ/mol.
(A) 68.88 kJ/mol (B) 4054.375 kJ/mol (C) 139.8948 kJ/mol (D) 8108.750 kJ/mol
68*. Given that the enthalpy of solution of the hydrated copper (II) sulphate is +11.3 kJ/mol, what is the
enthalpy of hydration of the anhydrous solid.
(A) 97.321 kJ/mol (B) –97.321 kJ/mol (C) –77.971 kJ/mol (D) 77.971 kJ/mol
Comprehension-3
The Born Haber cycle below represents the energy changes occurring at 298K when KH is formed from its
elements
DH
2K(s) + H2(g) 2KH(s)
v x
2K(g) + 2H(g)
w y z
+ –
2K (g) + 2H (g)
DHatomisation K = 90 kJ/mol DHionisation K = 418 kJ/mol

DHdissociation H = 436 kJ/mol DHelectron affinity H = –78 kJ/mol
DHlattice KH = –710 kJ/mol
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69. In terms of the letters v to z write down expressions for
(i) DH for the reaction 2K(s) + H2(g) ¾® 2KH(s) (ii) DHi of K
(iii) DHelectron affinity of H (iv) DHlattice of KH(s)
70. Calculate the value of DH showing all your working.
71. Calculate the DHf of KH(s).
72. Write a balanced equation for the reaction of KH with water.
73. On complete reaction with water, 0.1 g of KH gave a solution requiring 25 cm 3 of 0.1M HCl for neutralisation.
Calculate the relative atomic mass of potassium from this information.
Subjetive Questions
74*. Two mole of ideal diatomic gas (CV,m = 5/2 R) at 300 K and 5 atm expanded irreversly & adiabatically to a final
pressure of 2 atm against a constant pressure of 1 atm. Calculate q, w, DH & DU.
75. A bomb containing 5.4g of Al and 15.97g of Fe2O3 is placed in an ice calorimeter containing initially 8 kg of ice
and 8 kg of water. The reaction 2Al(s) + Fe 2O3(s) ® Al2O3(s) + 2Fe(s) is set off by remote control and it is then
observed that the calorimeter contains 7.746 kg of ice and 8.254 kg of water. Find the DH for the above
reaction.
DHfusion (ice) = 1.436 kcal/mole
76*. A sample of the sugar D-ribose (C5H10O5) of mass 0.727g was placed in a calorimeter and then ignited in the
presence of excess oxygen. The temperature raise by 0.910 K. In a separate experiment in the same calorimeter,
the combustion of 0.825 g of benzoic acid, for which the internal energy of combustion is -3251kJ mol-1, gave
a temperature rise of 1.940K. Calculate the internal energy of combustion of D-ribose and its enthalpy of
formation.
77. The heat of combustion of formaldehyde(g) is -134 kcal mole-1 and the heat of combustion of paraformaldehyde(s)
is -122 kcal per (1/n) (CH2O)n. Calculate the heat of polymerization of formaldehyde to paraformaldehyde.
78*. The disaccharide a - maltose can be hydrolysed to glucose according to the equation
C12H22O11(aq) + H2O(l) ¾® 2C6H12O6(aq)
Using the following values, calculate the standard enthalpy change in this reaction:
DfH°(H2O, l) = -285.85 kJ·mol-1
DfH°(C6H12O6, aq) = -1263.1kJ·mol-1
DfH°(C12H22O11, aq) = -2238.3 kJ·mol-1
79*. Diborane is a potential rocket fuel which undergoes combustion according to the reaction, [IIT-JEE-2000]
B2H6(g) + 3O2(g) ¾® B2O3(s) + 3H2O(g)
From the following data, calculate the enthalpy change for the combustion of diborane :
3
2B(s) + O (g) ¾¾® B2O3(s) ; DH = –1273 kJ
2 2
1
H2(g) + O2(g) ¾¾® H2O(l) ; DH = –286 kJ
2
H2O(l) ¾¾® H2O(g) ; DH = 44 kJ
2B(s) + 3H2(g) ¾¾® B2H6(g) ; DH = 36 kJ
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80*. For the reaction cis-2-butene ® trans-2-butene and cis-2-butene ® 1-butene, DH = – 950 and + 1771 cal/mol
respectively. The heat of combustion of 1-butene is –649.8 kcal/mol. Determine the heat of combustion of trans-
2-butene. Also calculate the bond energy of C=C bond in trans-2-butene. Given B.E of C = O = 196,
O—H = 110, O = O = 118, C—C = 80 and C—H = 98 kcal/mol respectively. DHv(H2O) = 11 kcal/mol.
81. Using the data (all values are in kJ/mol at 25°C) given below :
(i) Enthalpy of polymerization of ethylene = – 72.
(ii) Enthalpy of formation of benzene (l) = 49
(iii) Enthalpy of vaporization of benzene (l) = 30
(iv) Resonance energy of benzene (l) = – 152
(v) Heat of formation of gaseous atoms from the elements in their standard states H = 218, C = 715.
Average bond energy of C—H = 415. Calculate the B.E. of C—C and C= C. [A : 331 and 590 kJ/mol]
82*. Determine resonance energy of benzene [C6H6 (l)] from the following information :
DH°f of C6H6 (l) = + 49 kJ ;
DH°f of C2H2 (g) = +75 kJ DH°v of C6H6 (l) = + 45 kJ
B.E. C º C = 930 kJ/mol ; C = C = 615 kJ/mol ; C — C = 348 kJ/mol
83. Consider the following thermodynamic data :

Enthalpy of formation of CaC2 (s) = – 60 kJ/mol ;
Enthalpy of sublimation of Ca (s) = 179 kJ/mol ;
Enthalpy of sublimation of C (s) = 718 kJ/mol ;
First ionization energy of Ca (g) = 590 kJ/mol ;
Second ionization energy of Ca (g) = 1143 kJ/mol ;
Bond energy of C2 (g) = 614 kJ/mol ;
First electron affinity of C2 (g) = –315 kJ/mol ;
Second electron affinity of C2 (g) = +410 kJ/mol ;
Draw a clear Born-Haber cycle and determine lattice energy of CaC 2 (s).
84*. A swimmer breaths 20 times in one minute when swimming and inhale 200 mL of air in one breath. Inhalded
air contain 20% O2 by volume and exhaled air contain 10% O2 by volume. If all oxygen are consumed in
combustion of glucose in the body and 25% of energy obtained from combustion is available for muscular work.
Determine the maximum distance this swimmer can swim in one hour if 100 kJ energy is required for 1.0 km
swimming. Standard molar enthalpy of combustion of glucose is –2880 kJ/mol and body temperature is 37°C.
85*. Given the following standard molar enthalpies :

DH°f of CH3CN (g) = 88 kJ/mol, DH°f of C2H6 = – 84 kJ/mol, DH°Sublimation of C(gr) = 717 kJ/mol, bond
dissociation energy of N2 (g) and H2 (g) are 946 and 436 kJ/mole respectively, B.E. (C—H) = 410 kJ/mol.
Determine C—C and C º N bond energies.
86. By using the following data draw an appropriate energy cycle & calculate the enthalpy change of hydration of (i)
the chloride ion ; (ii) the iodide ion.
Comment on the difference in their values.
Enthalpy change of solution of NaCl(s) = – 2 kJ/mol.
Enthalpy change of solution of NaI(s) = + 2 kJ/mol.
Enthalpy change of hydration of Na+ (g) = – 390 kJ/mol.
Lattice energy of NaCl = – 772 kJ/mol.
Lattice energy of NaI = – 699 kJ/mol.
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Ther mochemi str y
87*. Use the following enthalpies of combustion in the calculations that follow.
Element/Compound Enthalpy of Combustion
C(s) – 394
H2(g) – 286
CH3CO2H(l) – 876
C4H6(g) – 2542
C2H6(g) – 1561
C2H4(g) – 1393
(i) Calculate the enthalpy change for the reaction :
2C(s) + 2H2(g) + O2(g) ¾® CH3CO2H(l)
(ii) Calculate the enthalpy of formation of buta–1, 3– diene C 4H6.
(iii) Calculate the enthalpy of formation of ethene C2H4.
(iv) Calculate the enthalpy change for the conversion of ethene C2H4 to ethane C2H6.
88. Cesium chloride is formed according to the following equation :

Cs(s) + 0.5Cl2(g) ¾® CsCl(s).
The enthalpy of sublimation of Cs, enthalpy of dissociation of chlorine, ionization energy of Cs & electron
affinity of chlorine are 81.2, 243.0, 375.7 and –348.3 kJ mol–1. The energy change involved in the formation of
CsCl is –388.6 kJ mol–1. Calculate the lattice energy of CsCl.
89*. The enthalpy of formation of ethane, ethylene and benzene from the gaseous atom are –2839.2, –2275.2 and
–5506 kJ mol–1 respectively. Calculate the resonance energy of benzene. The bond enthalpy of C–H bond is
given as equal to +410.87 kJ/mol.
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ANSWERS
l True and False
1. True 2. False 3. False 4. False 5. False

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

10. Exothermic 11. Endothermic
12. heat of transition 13. +33 kJ mol–1
14. –18 kcal mol–1 15. –57.2
16. –110.5 17. –RT
18. (A) 19. (C) 20. (C) 21. (A) 22. (D)
23. (A) 24. (D) 25. (B)
26. (C) 27. (C) 28. (A) 29. (A) 30. (B)
31. (A) 32. (B) 33*. (A) 34. (B) 35*. (B)
36. (C) 37. (A) 38*. (A) 39. (A) 40*. (B)
41*. (B) 42. (C) 43. (D) 44*. (D) 45. (C)
46*. (A) 47. (C) 48*. (B) 49. (D) 50. (C)
51*. (A) 52*. (C) 53. (A) 54. (B) 55*. (B)
56. (A) 57*. (B)
58. (ABD) 59. (AD) 60. (BC) 61. (C) 62. (ABCD)
l Match the Column
63. (A) - (q), (B) - (p), (C) - (r), (D) - (s)
l Comprehension
Comprehension 1 : 64. (B) 65.(i) (B) (ii) (C)

Comprehension 2 : 66*. (B) 67*. (A) 68*. (C)
Comprehension 3 : 69. (i) DH = (v + w + x + y + z)
w y
(ii) (DHf)K+ = (iii) (DH)EA for H =
2 2
z
(iv) (DH)lattice for KH =
2
70. –124 kJ/mol 71. –62 kJ/mol

72. KH + H 2O ¾¾® KOH + H 2 73. 39
74*. q = 0 DU = w
æ nRTf nRTi ö 5 æ nRTf nRTi ö

n Cv DT =Pavg. ç - n ´ R DT = - Pavg ç -
Pi ÷ø 2 è Pf Pi ÷ø
è Pf
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Ther mochemi str y
æ Tf 300 ö
5/2 (T – 300) = – ç - ÷
è 2 5 ø
Tf
5/2 T – 750 – + 60
2
3T = 810 T = 270 K
5
DU = w = 2 × R(-300) = – 150R = –1247.1J
2
DH= –150 R + 2 R(–30)= –210R = – 1745.9J
75. 2Al(s) + Fe2O3(s) ¾® Al2O3(s) + 2Fe(s)
0.2mole 0.1mole 0.1mole 0.2mole
0.254 kg ice melted
-254 ´ 1.436
DH = = 20.26 kcal
18
Heat liberated for 0.1 mole = 20.26 kcal
Heat liberated for 1 mole = –202.6 kcal
76*. C 5 H10 O 5(s) + SO 2(g) ¾¾® 5CO 2(g) + 5H 2 O(g)
C5 H10 O5 = 150
C6H5COOH = –2.13 – 5 × 8.314
15
C7 H 6 O 2 + O 2(g) ¾¾® 7CO2 + 3H 2 O
2
0.825
mSDT = ´ 0.3251 = mS(1.940)
122
mS = 11.33
11.33 × 0.910 ® 0.727
x ® 150 y
DH = –2.13 MS
DH
CH2=O (CH2O)
77. –134 –122
nCO2+nH2O
applying Hess law
DH – 122 = – 134 DH = 12 Kcal
1
78*. H 2 + O 2 ¾¾® H 2O –285.85 ...(i)
2
6C + 6H 2 + 3O 2 ¾¾® C 6H12O6 –1263.1 ...(ii)
11
12C + 11H 2 + O 2 ¾¾® C12H 22O11 –2238.13 ...(iii)
2
–(iii) + 2(ii) – (i)
= 2238.3 + 285.85 + 2(–1263.1) = –2.05 kJmol–1
79*. –2035 kJ mol–1
80*. Given
CH3 CH3 CH3
HC = CH HC = CH
CH 3
cal kcal
DH1 = –950 = –0.95 ...(i)
mole mole
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CH3 CH3 ®CH = CH – CH – CH
HC = CH 2 2 3
cal kcal
DH2 = +1771 = 1.771 ...(ii)
mole mole
CH2 = CH – CH2 – CH3 + 6O2 ¾® 4CO2 + 4H2O
kcal
DH3 = –649.8 ...(iii)
mole
(ii) + (iii) – (i)
CH3
HC = CH + 6O2 ® 4CO2 + 4H2O(l)
CH3
kcal
DH = –647.079 ...(iv)
mole
H2O(l) ¾® H2O(g)
kcal
DH4 = 11 ...(v)
mole
(iv) + 4 × (v)
CH3
HC = CH
+6CO2® 4CO2 + 4H2O(g)
CH3
DH = –603.079
[2 BC – C + BC = C + 8 BC – H]
+ 6BO = O–8 BC = O–8BO – H = –603.079
BC = C = 192.921 kcal/mole
81. Given
n(CH2=CH2)®(–CH2–CH2–)n DH = –72
i.e., BC = C – 2 BC – C = –72 ...(i)
6C(s) + 3H2(g) ¾® C6H6(l) DH = 49 ...(ii)
C6H6(l) ¾® C6H6(g) DH = 30
R.E. of C6H6 = – 152
1
H ¾® H DH = 218
2 2
C(s) ¾® C(g) DH = 715
BC–H = 415 for equation (2)
(6×715+6× 218)–(3BC–C+3BC=C+6×415 – RE) = 79
BC–C + BC=C = 959 ...(iii)
from equation (i) and (iii)
BC–C = 343.66 BC = C = 615.33
82*. Given
6C(s) + 3H2(g) ¾® C6H6(l) DH = 49
C6H6(l) ¾® C6H6(g) DH = 45
so 6C(s) + 3H2(g) ¾® C6H6(g) DH = 94 ...(i)
2C(s) + H2(g) ¾® C2H2(g) DH = 75 ...(ii)
(i) – 3 × (ii) 3C2H2(g) ¾® C6H6(g) = 131
3[BC º C+2BC–H]–[3BC–C+3BC=C + 6BC – H – RE]=–131
3[BC º C – BC – C– BC = C] + RE = – 131
RE = – 131 + 99 = –32
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Ther mochemi str y
83 Ca(s)¾®Ca(g)¾®Ca (g)¾®Ca (g) ü
+1 +2
–
ý ® CaC2(s)
C(s)¾®C(g)¾®C2(g)¾®C2(g)¾®C –22(g) þ
–60=[179+590+1143+718×2–614–315+410+ L.E.]
L.E. = – 2889 kJ/mole
84*. O2 consumed by body in 1 hr. = 20 × 60 × 200 (0.2 – 0.1) = 24000 mL.
V 24000
so volume of O2 at 273K is let V then =
273 310
V = 21135.48 mL moles of O2 = 0.9435
C6H12O6 + 6O2 ¾® 6CO2 + 6H2O
DH = –2880 kJ/mol
0.9435
moles of glucose ¾®
6
2880 ´ 0.9435
Heat released = = 452.9 kJ
6
Heat used for muscular work
= 452.9 × 0.25 = 113.22 kJ
so distance = 1.132 km
85*. Given :
3 1
2C(s)+ H2(g)+ N2(g)¾®CH3CN(g) DH = 88 ...(i)
2 2
2C(s) +3H2(g) ¾® C2H6(g) DH = –84 ...(ii)
C(s) ¾® C(g) DH = 717
N2(g) ¾® 2N(g) DH = 946
H2(g) ¾® 2H(g) DH = 436
BC – H = 410
from equation (i)
(2×717+1.5×436+0.5× 946)–(3× 410+BC – C+BC º N) = 88
BC – C + BC º N = 1243 ...(iii)
from equation (ii)
(2 × 717 + 3 × 436) – (BC – C + 6 × 410) = –84
BC – C = 366 kJ/mole from equation (iii)
BC º N = 877 kJ/mole
86. Given :
NaCl(s)+aq ¾® Na+(aq) + Cl–(aq) DH = –2 kJ/mole
Na+(g)+Cl–(g) ¾® NaCl(s) DH = –772 kJ/moles
so Na+(g)+Cl–(g)+aq. ¾®Na+(g)+Cl–(aq.) DH = –774
& Na+(g) + aq. ¾® Na+(g) DH = –390
so enthalpy of hydration of Cl– = –384
similarly enthalpy of hydration of I – = –307
87*. C(s) + O 2 ¾¾® CO 2

1
H2 + O 2 ¾¾® H 2O
2
CH 3 COOH + 3O 2 ¾¾® 2CO 2 + 2H 2O
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11
C4H6 + O 2 ¾¾® 4CO 2 + 3H 2O
2
7
C 2H6 + O 2 ¾¾® 2CO 2 + 3H 2O
2
C 2H 4 + 3O2 ¾¾® 2CO2 + 2H 2O

(i) 2(i) + 2(ii) - (iii)
= 2(–394 – 286) + 876
= –1360 + 876 = –484 kJ/mol
(ii) 4C(s) + 3H 2(g) ¾¾® C 4 H6(g)

= 4C (–394) + 3(–286) + 2542
= –1576 – 858 + 2542
= 108
(iii) 2C + 2H 2 ¾¾® C 2H 4
= 2(–394) + 2(–286) + 1393
= –1360 + 1393 = 33
(iv) C 2H 4 + H 2 ¾¾® C 2H 6
(vi) – (v) + (ii)
= –1393 – 286 + 1561 = –118
–388.6
88. Cs(s) +21 Cl2(g) CsCl(s)
1
81.2 (243)
2
Cs (g) Cl x
375.7 –348.3
Å
Cs + Cl
1
(g)
81.2 + 375.7 + 121.5 – 348.3 + x = –388.5

578.4 – 348.3 + 388.5 = –x
– x = 966.9 – 348.3
x = – 618.6
-2839.2
89*. 2C(g) + 6H(g) ¾¾¾¾® C2H6
-2275.2
2C(g) + 4H(g) ¾¾¾¾® C2H4
-5506
6C(g) + 6H(g) ¾¾¾¾
® C6H6
(C – C) + 6(C – H) = –2839.2 Þ C – C = 373.98
(C = C) + 4(C – H) = –2275.2 Þ C = C = 637.72
–6(410.87)+3(373.98) + 3(631.72) + RE = –5506
–5482.3 + RE = 0.5506
RE = –23.68 kJ/mol
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Chemical Bonding
CHEMICAL BONDING
Assertion-Reason
These questions contains, Statement-I (assertion) and Statement-II (reason).
(A) Statement-I is True, Statement-II is True ; Statement-II is a correct explanation for Statement-I
(B) Statement-I is True, Statement-II is True ; Statement-II is NOT a correct explanation for Statement-I
(C) Statement-I is True, Statement-II is False.
(D) Statement-I is False, Statement-II is True.
1. Statement-I : CO2 and SiO2 has same physical state at room temp.
Because
Statement-II : Carbon has more electronegativity than silicon atom.
Cl
2. Statement-I : Dipole moment of is similar as bromo benzene.
Because
Statement-II : Dipole moment of Cl - C bond is greater than Br- C bond.
3. Statement-I : The stability of peroxides and superoxides increases in passing from Li to Cs.
Because
Statement-II : The electropositive character of the elements in the periodic table increases on moving down a
group.
4. Statement-I : Borazole is aromatic in nature.

Because
Statement-II : Nitrogen contributes p-electrons to the system.
5. Statement-1 : CH4 and CH2F2 are having regular tetrahedron geometry.

Statement-2 : Both are having same hybridization.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
6. Statement-1 : Dipole moment of H2O is more than that of OF2.

Statement-2 :In H2O, the resultant bond dipole of O – H bond and the resultant lone pair moment are in
opposite direction.
7. Statement-1 : Allene is a non polar molecule.

Statement-2 : Allene is non planar molecule.
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8. The bond angle and hybridization in ether (CH 3OCH 3 ) is :
(A) 106º51¢, sp 3 (B) 104º31¢, sp 3 (C) > 109° 28', sp3 (D) None of these
9. The types of bonds present in CuSO4·5H2O are

(A) electrovalent and covalent (B) electrovalent , coordinate covalent & H-bond
(C) covalent, coordinate covalent & H-bonds (D) electrovalent, covalent, coordinate covalent & H-bond
10. Amongst H2O, H2S , H2Se and H2Te, the one with the highest boiling point is [JEE 2000]
(A) H2O because of hydrogen bonding (B) H2Te because of higher molecular weight
(C) H2S because of hydrogen bonding (D) H2Se because of lower molecular weight
11. The correct order of hybridization of the central atom in the following species NH3, PtCl -4 2 , PCl5 and BCl3 is
[JEE 2001]
(A) dsp2, sp3d, sp2 and sp3 (B) sp3 , dsp2 , sp3d, sp2 (C) dsp2, sp2, sp3, sp3d (D) dsp2, sp3, sp2, sp3d
12. All possible bond angles in anionic part of PCl5 are.

(A) 109° 28¢ only (B) 90°, 180° (C) 90°, 120° , 180° (D) 72°, 90°, 180°
13. Which of following pair of species is having different hybridisation but same shape.
(A) BeCl2 and CO2 (B) CO2 and SO2 (C) SO2 and I3+ (D) ICl -2 and BeH2
14. Which of the following statements is correct in the context of the allene molecule, C3H4?
(A) The central carbon is sp hybridized
(B) The terminal carbon atoms are sp2 hybridized
(C) The planes containing the CH2 groups are mutually perpendicular to permit the formation of two separate
p-bonds.
(D) All correct
15. Structure of Na2[B4O5(OH)4] · 8H2O contains

(A) Two triangular and two tetrahedral units (B) Three triangular and one tetrahedral units.
(C) All tetrahedral units. (D) All triangular units.
16. A : tetracyanomethane B : carbondioxide C : benzene D : 1,3-buta-di-ene

Ratio of s and p bonds is in order :
(A) A = B < C < D (B) A = B < D < C (C) A = B = C = D (D) C < D < A < B
17. The geometry of ammonia molecule can be best described as

(A) nitrogen at one vertex of a regular tetrahedron, the other three vertices being occupied by the three hydrogens
(B) nitrogen at the centre of the tetrahedron, three of the vertices being occupied by three hydrogens
(C) nitrogen at the centre of an equilateral triangle, three corners being occupied by three hydrogens
(D) nitrogen at the junction of a T, three open ends being occupied by three hydrogens.
18. Find the molecule which is planar and polar.

(A) B3N3H6 (B) F2C = C = C = CF2 (C) BrF2Cl (D) F2C = C = CF2
19. Find out the incorrect order of the dipole moment among the following pair of compound
(A) NH3 > NF3 (B) p-dichloro benzene > o-dichloro benzene
(C) CH3Cl > CH2Cl2 (D) SiF4 < SF4
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Chemical Bonding
20. Select the correct order of B.P.
(A) BF3 > BMe3 (B) BF3 < BMe3 (C) BF3 = BMe3 (D) None of these
21. In a change from PCl3 ¾® PCl5, the hybrid state of P changes from
(A) sp2 to sp3 (B) sp3 to sp2 (C) sp3 to sp3d (D) sp3 to dsp2
22. Select correct statement about hydrolysis of BCl3 and NCl3

(A) NCl3 is hydrolysed and gives HOCl but BCl3 is not hydrolysed.
(B) Both NCl3 and BCl3 on hydrolysis gives HCl
(C) NCl3 on hydrolysis gives HOCl but BCl3 gives HCl
(D) Both NCl3 and BCl3 on hydrolysis gives HOCl
23. Number of corner/oxygen atoms shared per tetrahedron in pyroxene chain silicate and sheet silicate
are .....and.......respectively–
(A) 2.5, 3 (B) 2, 3 (C) 3, 2 (D) 2, 2
24. Which of the following order is correct of the given property.

(A) LiCl >NaCl > KCl > RbCl > CsCl : Thermal stability order
(B) BeF2 < MgF2 < CaF2 < SrF2 < BaF2 : solubility order
(C) NO2– > NO— > NO = NO2+ > NO+ : bond length order
(D) BaO > SrO > CaO > BeO > MgO : basic character order
25. In which of the following cases, the strength of back bonding is maximum :-
(A) PF3 (B) BF3 (C) (H3Si)3N (D) (SiH3)2O
26*. Which of the following have a three dimensional network structure ?
(A) SiO2 (B) Diamond (C) P4 ( white ) (D) CCl 4
27*. Which of the following oxyacids of sulphur contain S - S bonds ?
(A) H 2 S 2 O8 (B) H 2 S 2 O6 (C) H 2 S 2O4 (D) H 2 S 2 O5
28. London force works in

(A) Polar molecule (B) Non-polar molecule
(C) All polar and non-polar molecule (D) Only in polar molecule
29. London forces depends upon

(A) Molecular weight (B) Number of polarisable electron
(C) Molecular size (D) None of these
30. Select the correct order of following property.

(A) % s-character : sp3 > sp2 > sp
^ bond angle — Å
(B) ONO : NO3 > NO 2 > NO2
(C) Second ionisation energy : O > F > N > C

(D) C – H bond length : CH3F > CH2F2 > CF3H
31. In which of the molecule on hydrolysis proton donor oxyacid is not formed from their central atom-
(A) NCl3 (B) BCl3 (C) SF4 (D) P4O10
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32. A mineral contain following tetrameric anion in which = Si, = oxygen
Select correct option (s) about anion in mineral –
(A) Formula of anion is (SiO 3 ) n2n- (where n = 4) .

(B) The total 10 negative charges are present in this anion.
(C) It has three shared oxygen/corners and ten unshared oxygen/corners.
(D) It is non planar
33. Choose the correct statements.

(A) CH3NCS molecule is linear (B) SiH3NCS molecule is linear
(C) GeH3NCS molecule is bent (D) P(SiH3)3 molecule is pyramidal
34. The molecule is/are having N – N bond.

(A) N2O (B) N2O3 (unsymm.) (C) N2O5 (D) N2O4
35. Which of the following statement is/are correct for CCl3- and ··CCl 2
(A) Back bonding in both cases from Cl to C-atom
(B) Back bonding in both cases from C to Cl-atom
(C) Back bonding in CCl 3- from C to Cl but reverse in ··CCl
2
(D) Direction of back bonding is just opposite in two cases.
36. Which of the following molecule(s) is/are having pp–pp back bonding
(A) BF3 (B) BeF2 (C) B3N3H6 (D) BCl3
Match the Column

37*. Column-I Column-II
(A) B3N3H6 (p) planar geometry
(B) H2O2 (q) non planar geometry
(C) B2H6 (r) no lone pair
(D) I2Cl6 (s) non polar molecule

Column -I Column-II
(Type of orbital) ( Orbitals involved in hybridisation )
(A) d z2 -orbital (P) sp3 (Tetrahedral)

(B) dxy - orbital (Q) sp3d2 (Octahedral)
(C) py - orbital (R) sp3d (TBP)
(D) dx2-y2- orbital (S) sp3d3 (PBP)
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Chemical Bonding
Comprehension
Cation and anion attract each other by electrostatic force of attraction to give a molecule A+ B–. Since the
electrostatic field of a charged particle extends in all directions, a positive ion is surrounded by a number of
negatively charge ions while each negative ion similarly surrounded by a number of positive ions. These cations
and anions arrange systematically in an alternating cation-anion pattern. This is called a crystal lattice. This
process of clustering ions increases the force of attraction and thus potential energy decreases. The energy
released when the requisite number of positive and negative ions are condensed into crystal to form one mole of
the compound is called lattice energy. Higher the lattice energy, greater will be the ease of forming an ionic
compound.
1
L.E. µ
r+ + r-
µ |z +| |z –|
r+ – radius of cation, r– – radius of anion z+ and z– are the charge on cation and anion respectively.
Lattice energy can be indirectly calculated using Born Haber cycle.
Solubility of an ionic solid AB can be explained
AB(s) + aq A+ (aq) + B– (aq) DHr = DHsolution
–DHL.E.
A+(g) + B– (g) + aq DHhydration
Þ DHsolution = DHhyd. – DHL.E.
1 1 1
Lattice energy (L.E.) µ and hydration energy (H.E.) µ + practically it is found, if r+ ~ r- then
r+ +r- r+ r-
L.E. dominates over H.E. But if r+ << r– or r+ >> r– then H.E. dominate over L.E. more the lattice energy
compared to hydration energy less will be the solubility but if less is the lattice energy & more is the hydration
energy more will be the solubility.
39*. A hypothetical compound MX2 (s) has lattice energy 1200 kJ mol–1 and DHhydration for M 2+(g) is
1000 kJmol–1 and DHHydration for X–(g) is 150 kJ mol–1 then if one mole of MX2(s) is dissolved in sufficient
amount of water then calculate the value of DH for this process in kJ mol–1
(A) – 100 (B) + 100 (C) 200 (D) + 50
40*. When one mole of CsF(s) is dissolved in sufficient amount of water then it releases 40 kJ energy. If lattice energy
of CsF is 750 kJmol–1 then the summation of heat of hydration of Cs+ & F– ion is (magnitude wise)
(A) – 750 kJ mol–1 (B) – 790 kJ mol–1 (C) – 710 kJ mol–1 (D) – 830 kJ mol–1
41*. True order of solubility is :

(A) MgCO3 > CaCO3 > SrCO3 > BaCO3 (B) BaCO3 > SrCO3 > CaCO3 > MgCO3
(C) MgCO3 > CaCO3 > BaCO3 > SrCO3 (D) SrCO3 > BaCO3 > CaCO3 > MgCO3
42*. The correct order of Lattice energy will be :

(A) Na2S > MgCl2 (B) MgCl2 > Na2S (C) MgCl2 ~ Na2S (D) Can’t be predicted
135
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JEE-Chemistr y
Subjetive Questions
Draw structcures of following:
1. H2SO4 2. C3O2
3. (CN)2 4. Na2S4O6
5. Cl2O7 6. P4
7. P4O6 8. P4O10
8. O2F2 (dimer form of OF) 10. S3O9
11. N2O5 12. S2O72 –
13. N2F4 14. N2O3
15. SiO2 16. HClO4
17. CaCN2 18. CuSO4.5H2O
19. P4S10 20. RbIO2
21. CsH2PO2 22. NaIO3
23. NH4OCN 24. H2S2O4
25. NaHSO3 26. H2PO3—
27. H2P2O52— 28. Dithionate ion (S 2 O62- )
29. Trithionate ion (S3O62–) 30. Thionyl chloride (SOCl2)
31. Sulpury chloride (SO2Cl2) 32. Pyrophosphoric acid (H4P2O7)
33. Meta phosphoric acid (HPO3) 34. Peroxy phosphoric acid (H3PO5)
35. Ammonium phosphite 36. Sodium hydrogen phosphate
37. Sodium dihydrogen phosphate 38. Sodium dihydrogen pyrophosphate
39. Potassium bicarbonate (KHCO3 ) 40. Calcium carbide (CaC 2 )
41. Peroxy diphophoric acid (H4P2O8) 42. Hyponitrous acid (H2N2O2)
43. Oleum (H2S2O7) 44. Marshall’s acid (H 2 S 2 O8 )
45. Caro’s acid (H 2 SO 5 )
43. In what hybridization state is the beryllium atom in BeCl 2 molecule? How will the type of hybridization change
when BeCl2 transform to the solid state.
44*. (a) What type of bonding holds the layer in graphite ? Why will graphite conduct electricity well in a direction
parallel to the planes of hexagons, but not at all well in a direction perpendicular to the planes ?
(b) PCl5 exists as solid in the form of [PCl4]+ [PCl6]–, yet it is a non conductor of electricity. Why?
45. What is the increasing order of the bond angle for the following compounds ?
O O O
H x H , Cl y Cl and F z F
46*. How many S – S linkage present in H2SnO6.
47*. Draw the structure of following compound

(i) Na[B3O3(OH)4] (ii) Na2[B4O5(OH)4].8H2O
–2
(iii) Na6P6O18 (iv) S3O6
(v) S3O9 (vi) (CN)2
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Chemical Bonding
48. Draw the geometry of following three molecules and explain with proper reasoning :
(i) N(CH3)3 (ii) N(SiH3)3 (iii) P(SiH3)3
49*. Find out total number of pp–dp bonds present in any one of its structures in case of PO 43–
50*. Find out total number of pp–pp bonds present in ClO3¯.
51*. How many number of atomic orbitals are required, so that their mixing produces hybrid orbitals each having %
of s-character equal to 17%.
52. AgNO3 gives a white precipitate with NaCl but not with CCl 4 . Why ?
53. Give reasons for the following :

(a) KHF2 is known whereas KHCl2 is unknown.
(b) (CH3 )3 N is pyramidal but (SiH3 )3 N is trigonal planar.
(c) CO2 is a gas but SiO2 is a solid.
54*. (a) BF3 has less lewis acidic property than BBr 3 . Why ?
(b) (CH3)3 C–OH is less acid than (CH3 )3 Si–OH. Why ?
(c) Why in the presence of ethyne HF exhibit more acidic character.
(d) Why SF4 can be hydrolysed easily but SF6 can not ?
55*. Give a suitable reason for the high mobility of H + ions through the ice than through liquid water.
56. HBr has dipole moment 2.6 × 10–30 CM. If the ionic character of the bond is 11.5 %, calculate the interatomic
spacing.
57. Maleic acid is more acidic than fumaric acid. Why?
58. Molar entropy change of vapourization of acetic acid is less than that of water. Explain
59. Heat of vapourization of water is higher than HF, however strength of H-bond in HF is higher than water. Explain
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ANSWERS
1. (D) 2. (D) 3. (A) 4. (B) 5. (D)

6. (C) 7. (B)
8. (C) 9. (D) 10. (A) 11. (B) 12. (B)

13. (C) 14. (D) 15. (A) 16. (A) 17. (A)
18. (C) 19. (B) 20. (B) 21. (C) 22. (C)
23. (A) 24. (A) 25. (B)
26. (AB) 27. (BCD) 28. (C) 29. (ABC) 30. (CD)
31. (AB) 32. (BCD) 33. (BCD) 34. (ABD) 35. (B)
l Match the Column
37. A - (p, r, s), B - (q), C - (q, r, s), D - (p, s)

38. A - (q, r, s), B - (s), C - (p, q, r, s), D - (q, s)
l Comprehension
39. (A) 40. (B) 41. (A) 42. (B)
44. ¾¾
® Cl - Be - Cl ¾¾
® sp hybridization
in solid state BeCl2 gets polymerized.
Cl Cl Cl
Be Be Be
Cl Cl
Cl
45. (a) In graphite layers are held together through weak Vander Waal’s forces in graphite each C – atom has one
unpaired electron which can move through. The plane from one end to another but between planes due to
larger distance electron can’t move between planes.
(b) In solid state ions are not free to move, so inspite of being ionic it does not conduct electricity.
O O O
95. C C C
< <
F F Cl Cl H H
96. H2SnO6 (n – 1) ¾¾
® S – S bond.
138
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Chemical Bonding
OH
B
O O OH +
Na
97. (i) Na[B3O3(OH)4] HO B B
–1 OH
O
OH
–
O—B —O
(ii) Na2[B4O5(OH)4].8H2O= Na2 HO—B O B—OH · 8H2O
–
O—B —O
OH
O O
S
O O O O
S S
(v) S3O9
O O
O
cyclic timer of SO3
(vi) (CN)2 N º C-C º N
H 3Si
98. (i) N(CH3)3 ¾¾
® N (ii) N(SiH3)3 ¾¾
® N SiH 3
CH3 H 3Si
H3C
CH3
(iii) P(SiH3)3 ¾¾ P
® SiH3
H3Si
SiH3
P One pp –dp bond

99.
O O O–1
–1
100. ClO -31 Cl Two pp –dp bond

–
O O
101. sp3d2
no.of s - orbital
% s–character = total no.of orbital ´ 100
1
= ´ 100 = 17%
6
139
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102. NaCl is an ionic compound so gives Cl– due to which AgCl is formed while CCl4 is a covalent molecule. So it
does not give Cl– ion so AgCl is not formed.
103. (a) F– due to smaller size and greater EN can form inter molecular H–bond but Cl – can’t form due to its larger
size and lesser EN.
H3Si
(b) N SiH3
H3Si
due to back bonding between N and Si hybridisation state of N becomes sp 2 and shape becomes planar.
® no such back bonding takes place.

while (CH3)3 N ¾¾
3
so hybridisation state ¾¾
® sp
® pyramidal
shpae ¾¾
(c) In CO2 due to smaller size of C atom stable pp–pp bond is formed between C and O so in CO2 all four
valencies of C is completed.
While in SiO2 due to larger size of Si it can’t form stable pp–pp bond so SiO2 form 3D network structure due
to which SiO2 exist in solid state.
While in CO2 molecules are hold together through weak vander waal’s forces.
104. (a) BF3 due to back bonding between F and B electron deficiency of B is completed so it is a weaker Lewis
Acid.
s
(b) (CH 3 )3 Si - O - H Å
The anion of (CH3)3 Si–OH is stabilized due to back bonding.
–
(CH3)3Si O
(c) because the proton given by HF is accepted by CHºCH so equilibrium shifted towards right.
CH º CH5+ + H+/F–
5– – + CH = CHÅ
F 2
(d) In SF6 due to symmetrical shape it is inert while SF4 due to unsymmetrical. See–saw shape is easily
hydrolyzed.
105. In ice due to open cage like structure H2O molecules are held at fixed positions so H+ can move easily while in
H2O(l). H2O molecules are not fixed so H+ ions are hindered by H2O molecules in water.
m obs
106. % ionic character = m ´ 100
cal
2.6 ´ 10 -30 ´ 100

11.5 =
1.6 ´ 10 -19 ´ d
2.6 ´ 10 -30 ´ 100 260

d= - 19
= ´ 10 -11 = 14.1×10–11 M
1.6 ´ 10 ´ 11.5 1.6 ´ 11.5
140
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Important Notes

Rankers Academy JEE
Important Notes

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Rankers Academy JEE

1. MOLE CONCEPT (1-10) 5. REDOX (34-43)

l Single Choice Correct l Single Choice Correct

l Fill in the Blanks l Assertion–Reason

For More Material Join: @JEEAdvanced_2024

For More Material Join: @JEEAdvanced_2024

5. 3d6 configuration is more stable than 3d5.

8. Statement-I : A molecule of butane, C4H10 has a mass of 58.12 amu.

10. Statement-I : The ground state configuration of Cr is 3d5 4s1.

11. Statement-I : The electronic configuration of nitrogen atom is represented as :

13. Statement-1 : The groundstate configuration of Cr is [Ar] 3d 54s1

Single Choice Correct

20. Na2SO4. xH2O has 50% H2O. Hence, x is :

32. How many moles of e– weight one Kg : [JEE 2002]

33. Which has maximum number of atoms : [JEE 2003]

36. Which orbit would be the first to have 'g' subshell :-

(A) 0, 0, 6h, 2h (B) 1, 1, 4h, 2h (C) 0, 1, 6h, 3h (D) 0, 0, 20h, 6

41. If m = magnetic quantum number and l = azimuthal quantum number then :-

46. The orbital diagram in which Hund’s rule is violated is

47. Match the column:

(A) 3 (B) 8 (C) 15 (D) 24

Multiple Choice Correct

(XN A + MY) X+M X + MY æ X + MYN A ö

59*. Which of the following options is/are incorrect.

61. Which of the following have equal no. of atoms ?

64. The magnitude of the spin angular momentum of an electron is given by -

67. What is the value of ‘x’ in general empirical formula ?

68. What is the value of ‘y’ in the general empirical formula b?

69. If the value of x and y be 1 and 2 respectively. Calculate the % composition of Cu ?

70. Simplest formula of the calcium lactate is :

71. Formula weight of calcium lactate is :

78. The sub-shell that arises after f sub-shell is called g sub-shell.

86. If for any electron in an orbital another parameter ‘B’ is defined as

l True and False

6. (D) 7. (A) 8. (A) 9. (A) 10. (A)

l Single Choice Correct

l Multiple Choice Correct

Comprehension 1 : 67. (B) 68. (A) 69. (B)

2. Third group of periodic table accommodates maximum number of elements.

3. First ionisation potential of Mg is higher than that of Al.

5. Successive ionisation potentials are lower.

6. The alkali metals show increasing electronegativities from Li to Cs.

8. The decreasing order of electron affinity of F, Cl, Br is F > Cl > Br

Fill in the blanks

10. Most electronegative elements belong to ............................... group.

11. Transition elements are characterised by ............................... valency.

14. Total number of inner transition elements are .............................. .

22. Statement -1 : Electron affinity of fluorine is greater than chlorine.

24. Statement -1 : Atomic radius of inert gases is largest in the period

25. Statement -1 : 2nd IP of alkali metals is maximum in the period.

26. Statement -1 : First ionization energy of nitrogen is lower than oxygen.

Single Choice Correct

29*. Correct order of ionic radii is :-

30. The correct order of stability of Al+, Al+2, Al+3 is :-

33. Which of the following has 2nd IP < Ist IP

34. The correct order of decreasing first ionization energy is :-

35. The electron affinity

41*. Which is correct order of size of O, O2–, F– and F :-

42. The right order of ionization potential of Li, Be, B & C is :

43*. The correct order of second ionization potential of C, N, O and F is