CPP 20220411175754709142

C HE M IS T R Y
RANK BOOSTING COURSE-2022

CPP
CLASSROOM PRACTICE PROBLEMS
ST
MOLE CONCEPT NO. 01
Type : 1 (Average Atomic Mass And Molar Mass)

1. The average molar mass of chlorine is 35.5 g mol–1. The ratio of 35
Cl to 37
Cl in naturally
occurring chlorine is close to [JEE(Main)-2020]
(1) 4 : 1 (2) 3 : 1 (3) 2 : 1 (4)1 : 1
Type : 2 (Empirical Formula And Molecular Formula)
2. The formula of a gaseous hydrocarbon which requires 6 times of its own volume of O2 for
complete oxidation and produces 4 times its own volume of CO2 is CxHy. The value of y is
_______. [JEE Main 2021]
3. At 300 K and 1 atmospheric pressure, 10 mL of a hydrocarbon required 55 mL of O2 for

complete combustion and 40 mL of CO2 is formed. The formula of the hydrocarbon is.
(1) C4H7Cl (2) C4H6 (3) C4H10 (4) C4H6
4. 25 g of an unknown hydrocarbon upon burning produces 88 g of CO2 and 9 g of H2O. This

unknown hydrocarbon contains
(1) 20 g of carbon and 5g of hydrogen (2) 22 g of carbon and 3g of hydrogen
(3) 24 g of carbon and 1g of hydrogen (4) 18 g of carbon and 7g of hydrogen
Type : 3 (Stoichiometry)
5. 1.86 g of aniline completely reacts to form acetanilide. 10% of the product is lost during
purification. Amount of acetanilide obtained after purification (in g) is _______ × 10–2.
[JEE Main 2021]
6. When 35 mL of 0.15 M lead nitrate solution is mixed with 20 mL of 0.12 M chromic sulphate
solution, _______ × 10–5 moles of lead sulphate precipitate out. (Round off to the Nearest
Integer).
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7. Complete combustion of 3 g of ethane gives x × 1022 molecules of water. The value of x is
_____. (Round off to the Nearest Integer).
[Use : NA = 6.023 × 1023; Atomic masses in u : C : 12.0 ; O : 16.0 ; H : 1.0]
8. The volume (in mL) of 0.1 N NaOH required to neutralize 10 mL of 0.1 N phosphonic acid is
………... .
9. The minimum number of moles of O2 required for complete combustion of 1 mole of propane
and 2 moles of butane is
10. The ammonia (NH3) released on quantitative reaction of 0.6 g urea (NH2CONH2) with sodium
hydroxide (NaOH) can be neutralized by
(1) 100m L of 0.2 N HCl (2) 200 mL of 0.4 N HCl
(3) 200 mL of 0.2 N HCl (4) 100 mL of 0.1 N HCl
11. The volume (in mL) of 0.125 M AgNO3 required to quantitatively precipitate chloride ions in 0.3
g of [CO(NH3)6] Cl3 is
M[CO(NH3 )6 ]Cl3 = 267.46 g/mol
M AgNO3 = 169.87 g/mol
12. Ferrous sulphate heptahydrate is used to fortify foods with iron. The amount (in gm) of the salt
required to achieve 10 ppm of iron in 100 kg of wheat is …..
Atomic weight = Fe = 55.85; S = 32.00; O = 16.00
13. NaClO3 is used, even in spacecrafts to produce O2. The daily consumption of pure O2 by a
person is 492 L at 1 atm 300 K. How much amount of NaClO3 in gm is required to produce O2
for the daily consumption of a person at 1 atm, 300 K…….?
NaClO3 (s) + Fe(s)  O2 (g) + NaCl (s) + FeO(s)
R = 0.082 L atm mol–1 K–1
Type : 4 (Percentage Composition)
14. Complete combustion of 1.80 g of an oxygen containing compound (CxHyOz) gave 2.64 g of
CO2 and 1.08 g of H2O. The percentage of oxygen in the organic compound is:
(1) 51.63 (2) 63.53 (3) 53.33 (4) 50.33
[JEE Main 2021]

15. Complete combustion of 750 g of an organic compound provides 420 g of CO2 and 210 g of
H2O. The percentage composition of carbon and hydrogen in organic compound is 15.3 and
_________ respectively. (Round off to the Nearest Integer)
16. A 10 mg effervescent tablet containing sodium bicarbonate and oxalic acid releases 0.25 mL
of CO2 at T= 298.15 K and p =1 bar. If molar volume of CO2 is 25.0 L under such condition,
What is the percentage of sodium bicarbonate in each tablet ?
[Molar mass of NaHCO3 = 84 g mol-1]
(1) 8.4 (2) 0.84 (3)16.8 (4) 33.6
Type : 5 (Concentration Terms)
17. 4.5 g of compound A (MW = 90) was used to make 250 mL of its aqueous solution.
Themolarity of the solution in M is x × 10–1. The value of x is ________.
(Rounded off to the nearest integer) [JEE Main 2021]
18. The NaNO3 weighed out to make 50 mL of an aqueous solution containing 70.0 mg Na+ per
mL is ______g. (Rounded off to the nearest integer)
[Given : Atomic weight in g mol–1 – Na : 23 ; N : 14 ; O : 16]
19. A 6.50 molal solution of KOH (aq.) has a density of 1.89 g cm–3. The molarity of the solution is
___________ mol dm–3. (Round off to the Nearest Integer).
[Atomic masses : K : 39.0 u; O : 16.0 u; H : 1.0 u]
20. The mole fraction of a solute in a 100 molal aqueous solution _____ × 10–2.
(Round off to the Nearest Integer).
[Given : Atomic masses : H : 1.0 u, O : 16.0 u]
21. 6.023 × 1022 molecules are present in 10 g of a substance ‘x’. The molarity of a solution
containing 5g of substance ‘x’ in 2L solutions is …… × 10–3.
22. A 100 mL solution was made by adding 1.43 g of Na2CO3.xH2O. The normally of the solution
is 0.1 N. The value of x is :
23. The molarity of HNO3 in a sample which has density 1.4 g/mL and mass percentage of 63% is
…… (Molecular weight of HNO3 = 63)

Type : 6 (Miscellaneous)
24. The strengths of 5.6 volume hydrogen peroxide (of density 1 g/mL) in terms of mass
percentage and molarity (M), respectively, are (Take molar mass of hydrogen peroxide as 34
g/mol) [JEE(Main)-2020]
(1) 0.85 and 0.25 (2) 0.85 and 0.5 (3) 1.7 and 0.5 (4) 1.7 and 0.5
25. 0.27 g of a long chain fatty acid was dissolved in 100 cm3 of hexane. 10 ml of this solution
was added dropwise to the surface of water in a round watch glass. Hexane evaporates and a
monolayer is formed, The distance from edge to center of the watch glass is 10 cm. What is
the height of the monolayer?
[Density of fatty acid = 0.9 g cm-3; π=3]
(1) 10-6 m (2) 10-4 (3) 10-5 (4) 10-2
26. The minimum amount of O2 (g) consumed per gram of reactant is for the reaction (Given
atomic mass ; Fe= 56, O= 16, Mg= 24, P= 31, C= 12, H= 1)
(1) C3H8(g) + 5O2(g)  3 CO2 (g) + 4H2O(I)
(2) P2(s) + 5O2 (g)→ P4O10 (s)
(3) 4Fe(s) + 3O2(g) →2Fe2O3(s)
(4) 2Mg(s) + O2 (g) → 2MgO(s)

ANSWER KEY
1. (2) 2. (8) 3. (2) 4. (3) 5. (243)
6. (525) 7. (18) 8. 10 9. 18 10. (1)
11. 26.92 12. 4.97 13. 2130 14. (3) 15. 3
16. (1) 17. (2) 18. (13) 19. (9) 20. (64)
21. 25 22. 10 23. 14.00 24. (3) 25. (1)
26. (2)
SOLUTIONS
1. Given,
Average molar mass of chlorine is 35.5 g mol–1.
Naturally occurring chorine are
35 37
Cl Cl
Mass ratio x 1–x
Total molar ratio = x + 1 – x = 1
Mass average = 35 × x + 37 × (1 – x)
35.5 = 35x + 37 – 37x
1.5 3
2x = 37 – 35.5; x = = 0.75 =
2 4
35 3
For Cl , x =
4
37 3
For Cl , 1 –
4
35 37
Cl ; Cl
3  3 3 1
;  1–   :
4  4 4 4
On simplify this ratio, we get 3 : 1
2. Combustion reaction :
 y y
CxHy(g) +  x   O2(g)  xCO2(g) + H2O()
 4 2
V 6V –
– – Vx = 4V
 x  4
Sinc : (I) Vo2  6  VCxH y
 y
 V  x    6V
 4
 y y
 x    6  4 4  6
 4
 y8

3. In eudiometry,
 y 300K y
C2H2   x   O2 
1atm
 xCO2  H2O
 4 2
 y
1 mol  x   mol x mol
 4
 y
1 mL  x  4  mL x mL
 
 y
10 mL  x   ×10 mL 10x mL
 4
Given, (i) VCO2 = 10x = 40 mL ⇒ x = 4
 y
(ii) VO2 = 10  x   mL = 55 mL
 4 
 y
⇒ 10  x   = 55 [∵ x = 4]
 4
×
⇒ 40 + = 55
⇒ y× = 15 ⇒ y = 15 × =6
So, the hydrocarbon (CxHy) is C4H6
4. Hydrocarbon containing C and H upon turning produces CO2 and water vapour respectively,
The equation is represented as
C2H2 + (x + y/4)O2 → xCO2 + (y/2)H2O
Mass of carbon = × mass of CO2
= × 88g = 24 g
Mass of hydrogen = × mass of H2O

= × 9 = 1g
So, the unknown hydrocarbon contains 24 g of carbon and 1g of hydrogen.
M = 98 M = 135
O
90% efficiency
5. C6H5NH2 C6H5–NH2–C–CH3
(Aniline) (Acetanilide)
Given 1.86 g
O
 1 mol C6H5NH2 give 1 mol C6H5NHCCH3
O
 moles of C6H5 NH2 = moles of C6H5NHCCH3
1.86 Wacetanilide
 
93 135

1.86  135
 W acelanilide = g  2.70 g
93
But efficiency of reaction is 90% only
90
 Mass of acetanilide produced = 2.70  g
100
= 2.43 g
= 243 × 10–2 g  x = 243
6. 3Pb (NO3)2 + Cr2(SO4)3  3PbSO4 + 2Cr(NO3)3

35 mL 20 ml
0.15 M 0.12 M
= 5.25 m.mol = 2.4 m.mol 5.25 m.mol = 5.25 × 10–3 mol
Therefore moles of PbSO4 formed = 5.25 × 10–3 = 525 × 10–5
7. C2H6  3H2O
0.1 0.3 = 0.3 × 6 × 1023 = 18 × 1022
mol mol
No. of molecules = 0.3 × 6.023 × 1023
= 18.069 × 1022
8. Base + Acid  Salt + H2O

NaOH HPO3  NaH2PO3  H2O

Base Phosphonic acid Salt Water
0.1 N 0.1 N
Given 
 V = ? 10mL
On dilution (N1V1)NaOH =  N2 V2 H PO
2 3
0.1×10mL
0.1V1 = 0.1 × 10 mL  V1 =
0.1
V1 = 10 mL
Volume of NaOH = 10 mL
9. Combustion of propane
C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)
For 1 mole propane combustion 5 mole O2 is required.
Combustion of butane
13
C4H10  g+ O2 (g)  4 CO2 (g) + 5H2O (l)
Butane 2
2mol
For 2 moles of butane 13 moles of O2 is required.

Hence. Minimum number of moles of O2 required to oxidize 1 mole of propane and 2 moles of
13
butane = 5 + 2 × = 18
2

10. NH 2CONH2 + 2 NaOH  2 NH3 + Na2CO3
(M=60)
No. of moles of urea = Given mass / molar mass

0.6
= = 0.1 mol NH2CONH2
60
 It gives 0.02 mol NH3 as per the equation.
To neutralize it, 0.02 equivalents of HCl needed.
As we know, no. of equivalents of HCl = Normally × Volume
11. Given, Mass of [Co(NH3)6]Cl3 = 0.3 g

Molar mass = 267.46 g mol–1
0.3
 n= mol
267.46
From the formula 1 mol complex will give 3 mol Cl–
0.3 0.9
 nCl– = ×3 =
267.46 267.46
The predicated reaction is takes place as follows :
[Co  NH3  6 ]Cl3 + 3AgNO 3 
 2AgCl
(0.3 g) (VmL0.125g)
0.3×3
 = 0.125 × V × 10–3
267.46
 Volume of AgNO3 (in mL)
0.9×1000
= = 26.92 mL
0.125×267.46
This value may vary from 26.60 to 27.00
12. Ferrous sulphate heptahydrate FeSO4 .7H2O

If the amount of the salt is ‘x’ gm
Mass of iron contained in it
x × atomic mass of Fe  = 55.85  55.85x
= =
Molar mass of FeSO 4 .7H2O  = 277.85  277.85
10 ppm of iron in 100 kg of wheat, can be achieved as
mass of iron  10 6
= = 10
mass of wheat  = 100kg =10 5 g 
55.85x ×106 277.85
= = 10  x= = 4.97 g
277.85×105 55.85
This value may vary from 4.95 to 4.99

13. Volume of O2 = 492 L
PV 1atm× 492L 492
 n= = –1 –1
= mol
Rt 0.082L atmK mol ×300K 8.2×3
Form the reaction,
NaClO3 (s) + Fe (s)  O2 (g) + NaCl (s) + FeO (s)
492
nNaClO3 = no2 = = 20 mol
82×3
nNaClO3 = n × molar mass of NaClO3 (= 106.5)
= 20 × 106.5 = 2130 g
The value in different situations may range from 2120 to 2140.
2.64
14. nc  nco2   0.06
44
1.08
nH  2  nH2O   2  0.12
18
2.64 1.08
m0  1.80  12   2
44 18
= 1.80 – 0.72 – 0.12 = 0.96 gm
0.96
%0   100  53.33%
1.80
Hence answer is (3)
15. 44 gm CO2 have 12 gm carbon

12
So, 420 gm CO2  × 420
44
1260
 gm carbon
11
 114.545 gram carbon
114.545
0So, % of carbon =  100
750
15.3%
18 gm H2O  2 gm H2
2
210 gm  × 210
18
= 23.33 gm H2
23.33
So, % H2  × 100 = 3.11%  3%
750
16. 2NaHCO3 + H2C2O4 → 2CO2 + Na2C4O4 + H2O

2 mol 1 mol 2 mol
⟹ In the reaction, number of mole of CO2 produced.
× . ×
n= = = 1.02 × 10-5mol
. × .

Number of mole of NaHCO3
=
∴ W NaHCO3 = 1.02 × 10-5 × 84 × 103 mg

= 0.856 mg
.
⟹ NaHCO3 % = × 100
= 8.56 %
4.5 / 90
17. M  0.2 = 2 × 10–1
250 / 1000
70mg
18. Na+ present in 50 ml =  50ml = 3500 mg = 3.5 gm
1 ml
3.5
Moles of Na+ = = moles of NaNO3
23
3.5
Weight of NaNO3 =  85 = 12.993 gm
23
19. 6.5 molal KOH = 1000 gm solvent has 6.5 moles KOH
So wt of solute = 6.5 × 56
= 364 gm
Wt of solution = 1000 + 364 = 1364
1364
Volume of solution = m
1.89
mole of solute
Molarity =
Vsolution in Litre
6.5  1.89  1000

=
1364
= 9.00
20. 100 molal aqueous solution means there is 100 mole solute in 1 kg = 1000 gm water.
Now,
nsolute
Mole-fraction of solute =
nsolute  nsolvent
100 1800
=   0.6428
1000 2800
100 
18
= 64.28 × 10–2

21. Given 6.023 × 1023 molecules are present in 10 g substance.
Number of molecules Mass(given)
Number of moles = 
6×1023 Molar mass
10× 6.023 ×1023
Molar mass = = 100 g/mol
6.023×1022
We know that
Moles of solute
Morality =
Volume of solution(l)
Given, morality of solution containing = 5
Of substance, Volume = 2L
=
 5/100  = 5
= 0.025 = 25 × 10–3
2 100 + 2
22. Molar of mass Na2CO3.xH2O

(Atomic mass of Na = 23, C = 12, O = 16)
= 23 × 2 + 12 + 48 + 18x
= 46 + 12 + 48 + 18x = (106 + 18x)
Equivalent weight of Na2CO3.xH2O
Molar mass M
=  = (53 + 9x) [Here m = molar mass and n factor = 2]
n factor 2
Weight
Gran equivalent = [Given weight of Na2CO3.xH2O = 1.43 g]
Equivalent weight
Hence gram equivalent of
1.43
Na2CO3.xH2O =
53 + 9x
Gmeq. 1.43
Normally = ; 0.1 =
Vlitre 53 + 9x
0.1
{As volume = 100 mL = 0.1 L
1.43
So, 10–2 =  53 + 9x = 143
53 + 9x
9x = 90  x = 10.00
23. For 100 g sample of the solution,

63
Mass of HNO3 = 63 g  = 1 mol nHNO3 =
63
Mass 100g 100 1
Volume of solution = = = mL = L
Density 1.4g/mL 1.4 14
n 1
Morality = = = 14 M
V L  1/14

24. Volume of hydrogen = 5.6
Volume strength = 11.2 × morality
Volume strength 5.6
 Morality = = = 0.5
11.2 11.2
Suppose that the solution taken is = 1L
Mass of solution = 1000 mL × 1 g/mL = 1000 g
Mass of solute = Moles × Molar mass = 0.5 × 34 = 17 g [ molar mass of H2O2 = 34]
17
 Mass % = × 100 = 1.7%
1000
25. 100 mL (cm3) of hexane contains 0.27 g of fatty acid

In 10 mL solution, mass of the fatty acid
0.27
m= × 10 = 0.027
100
Density of fatty acid of = 0.9 g cm-3
Volume of the fatty acid over the watch glass
m 0.027
V= = = 0.03 cm
d 0.9
Let height of the cylindrical monolayer = h cm
Volume of the cylinder = Volume of fatty acid
h cm
10 cm
⇒ V = πr × h
.
⇒ h= =
×( )
= t×10 cm = t×10-6 m
-4

26.
(a) C3H8(g) + 5O2 (g) →3 CO2 (g)+ 4H2O(I)
44 g 160g
⟹ 1g of reactant = g of O2 consumed
= 3.64 g
(b) P2(s) + 5O2 (g)→ P4O10 (s)
124g 150g
⟹ 1g of reactant g of O2 consumed = 129 g
(c) 4Fe(s) + 3O2(g) →2Fe2O3(s)

244g 96g
⟹ 1g of reactant g of O2 consumed
= 0.43 g
(d) 2Mg(s) + O2 (g) → 2MgO(s)
48g 32g
⟹ 1g of reactant g of O2 consumed
= 0.67 g
So, minimum amount of O2 is consumed per gram of reactant (Fe) in reactant (C).

Type : 1 (Earlier Model, Electromagnetic Waves)
1. Electromagnetic radiation of wavelength 663 nm is just sufficient to ionise the atom of metal A.
The ionization energy of metal A in kJ mol–1 is _______. (Rounded-off to the nearest integer)
[h = 6.63 × 10–34 Js, c = 3.00 × 108 ms–1, NA = 6.02 × 1023 mol–1] [JEE Main 2021]
Type : 2 (Bohr Model)

2. According to Bohr's atomic theory :-
(A) Kinetic energy of electron is μ
(B) The product of velocity (v) of electron and principal quantum number (n), 'vn' ∝ Z2.
(C) Frequency of revolution of electron in an orbit is .
(D) Coulombic force of attraction on the electron is .
Choose the most appropriate answer from the options given below :
(1) (C) Only (2) (A) Only
(3) (A), (C) and (D) only (4) (A) and (D) only [JEE Main 2021]
3. Given below are two statements :

Statement I : Bohr’s theory accounts for the stability and line spectrum of Li+ ion.
Statement II : Bohr’s theory was unable to explain the splitting of spectral lines in the
presence of a magnetic field.
In the light of the above statements, choose the most appropriate answer from the options
given below :
(1) Both statement I and statement II are true.
(2) Statement I is false but statement II is true.
(3) Both statement I and statement II are false.
(4) Statement I is true but statement II is false.
4. The difference between the radii of 3rd and 4th orbits of Li2+ is ∆R1. The difference between the
radii of 3rd and 4th orbits of He+ is ∆R2. Ratio ∆R1 : ∆R2 is
(1) 3 : 2 (2) 8 : 3 (3) 2 : 3 (4) 3 : 8
5. The radius of the second Bohr orbit in terms of the Bohr radius, a0, in Li2+ is
(1) (2) (3) (4)

6. Which one of the following about an electron occupying the 1s-orbital in a hydrogen atom is
incorrect? (The Bohr radius is represented by a0)
(1) The electron can be found at a distance 2a0 from the nucleus.
(2) The magnitude of the potential energy is double that of its kinetic energy on an average.
(3) The probability density of finding the electron is maximum at the nucleus.
(4) The total energy of the electron is maximum when it is at a distance a0 from the nucleus.
7. The ground state energy of hydrogen atom is –13.6 eV. The energy of second excited state of
He+ ion in eV is
(1) –54.4 (2) –3.4 (3) –6.04 (4) –27.2
8. If the de-Broglie wavelength of the electron in nth Bohr orbit in a hydrogenic atom is equal to
1.5 πa0 (a0 is Bohr radius), then the value of n/Z is
(1) 1.0 (2) 0.75 (3) 0.40 (4) 1.50
Type : 3 (Hydrogen Spectrum)
9. The figure that is not a direct manifestation of the quantum nature of atoms is [JEE Main 2020]
Increasing wavelength
Rb K Na
Kinetic energy of
(1) (2) photoelectrons
Absorption spectrum
Frequency of incident
radiation
T2 > T1
Internal Internal
(3) energy of (4) of black body
Ar radiation T1
300 400 500 600
Temperature (K) Wavelength
10. The region in the electromagnetic spectrum where the Balmer series lines appear is
(1) infrared (2) ultraviolet (3) microwave (4) visible
11. The shortest wavelength of H atom in the Lyman series is λ1. The longest wavelength in the
Balmer series of He+ is
36λ1 5λ1 9λ1 27λ1
(1) (2) (3) (4)
5 9 5 5
1 1
12. For the Balmer series in the spectrum of H atom, = v RH  2 − 2  , the correct statements
 n1 n2 
among (I) to (IV) are :
(I) As wavelength decreases, the lines in the series converge
(II) The integer n1 is equal to 2
(III) The lines of longest wavelength corresponds to n2 = 3
(IV) The ionisation energy of hydrogen can be calculated from wave number of these lines
(1) I, II, IV (2) II, III, IV (3) I, III, IV (4) I, II, III

13. For any given series of spectral lines of atomic hydrogen, let =
∆ν v max − v min be the difference
in maximum and minimum frequencies in cm–1. The ratio ∆νLyman / ∆νBalmer is

(1) 27 : 5 (2) 5 : 4 (3) 9 : 4 (4) 4 : 1
14. The ratio of the shortest wavelength of two spectral series of hydrogen spectrum is found to
be about 9. The spectral series are
(1) Lyman and Paschen (2) Brackett and Pfund
(3) Paschen and Pfund (4) Balmer and Brackett
15. For emission line of atomic hydrogen from ni = 8 to nf = n, the plot of wave number (ν) against
 1
 2  will be (The Rydberg constant, RH is in wave number unit)
n 
(1) non linear (2) linear with slope –RH
(3) linear with slope RH (4) linear with intercept –RH
16. Heat treatment of muscular pain involves radiation of wavelength of about 900 nm. Which
spectral line of H-atom is suitable for this purpose ?
[RH = 1 × 105 cm–1, h = 6.6 × 10–34 Js, c = 3 × 108 ms–1]
(1) Paschen, 5 → 3 (2) Paschen, ∞ → 3 (3) Lyman, ∞ → 1 (4) Balmer, ∞ → 2
Type : 4 (Photoelectric Effect)
17. The work function of sodium metal is 4.41 × 10–19 J. If photons of wavelength 300 nm are
incident on the metal, the kinetic energy of the ejected electrons will be (h = 6.63 × 10–34J s;
c = 3 × 108 m/s) ………… × 10–21 J. [JEE Main 2020]
18. Which of the graphs shown below does not represent the relationship between incident light
and the electron ejected from metal surface ?
K.E of K.E of
e e
es es
(1) (2)
0 0
Energy of Intensity of
light light
Number K.Eof
of ees e
es
(3) (4)
0 0
Frequency of Frequency of
light light

19. What is the work function of the metal, if the light of wavelength 4000 Å generates
photoelectron of velocity 6 × 105 ms–1 from it ? (Mass of electron = 9 × 10–31 kg, velocity of
light = 3 × 108 ms–1, Planck's constant = 6.626 × 10–34 JeV–1)
(1) 4.0 eV (2) 2.1 eV (3) 0.9 eV (4) 3.1 Ev
Type : 5 (De Broglie Wavelength)

20. A proton and a Li3+ nucleus are accelerated by the same potential. If λLi and λP denote the de
λLi
Broglie wavelengths of Li3+ and proton respectively, then the value of is x × 10–1. The
λP
value of x is_______.
(Rounded off to the nearest integer)
(Mass of Li3+ = 8.3 mass of proton) [JEE Main 2021]
21. When light of wavelength 248 nm falls on a metal of threshold energy 3.0 eV, the de-broglie
wavelength of emitted electron is ________ Å. (Round off to the Nearest Integer).
[Use : 3 = 1.73, h = 6.63 × 10–34 Js

Me = 9.1 × 10–31 kg ; c = 3.0 × 108 ms–1 ; 1eV = 1.6 × 10–19]
22. The de Broglie wavelength of an electron in the 4th Bohr orbit is

(1) 6πa0 (2) 2πa0 (3) 8πa0 (4) 4πa0
23. If p is the momentum of the fastest electron ejected from a metal surface after the irradiation
of light having wavelength λ, then for 1.5 p momentum of the photoelectron, the wavelength of
the light should be : (Assume kinetic energy of ejected photoelectron to be very high in
comparison to work function)
4 3 2 1
(1) λ (2) λ (3) λ (4) λ
9 4 3 2
24. The de-Broglie wavelength (λ) associated with a photoelectron varies with the frequency (ν) of
the incident radiation as, [ν0 is threshold frequency]
1 1 1 1
(1) λ ∝ (2) λ ∝ (3) λ ∝ (4) λ ∝
( ν − ν0 )
1/4
( ν − ν0 )
3/ 2
( ν − ν0 ) ( ν − ν0 )
1/ 2
Type : 6 (Heisenberg Uncertainty Principle)

25. A ball weighing 10 g is moving with a velocity of 90 ms–1. If the uncertainty in its velocity is 5%,
then the uncertainty in its position is_______× 10–33 m. (Rounded off to the nearest integer)
[Given: h = 6.63 × 10–34 Js] [JEE Main 2021]

Type : 7 (Schrodinger Wave Equation)
26. The plots of radial distribution functions for various orbitals of hydrogen atom against 'r' are
given below: [JEE Main 2021]
4πr R n,/(r) 8 3
4πr R n,/(r)
2
2
2
(A) (B)
2
2
4
1
0 5 10 0 5 10
r(Å) → r(Å) →
2.0
3
4πr R n,/(r)
4πr R n,/(r)
1.5
2
2
2 1.0
(C) (D)
2
2
1 0.5
0 5 10 0 5 10
r(Å) → r(Å) →
The correct plot for 3s orbital is:
(1) (B) (2) (A) (3) (D) (4) (C)
27. The correct statement about probability density (except infinite distance from nucleus) is
(1) it can be zero for 1s orbital (2) it can be negative for 2p orbital
(3) it can be zero for 3p orbital (4) it can never be zero for 2s orbital
28. The graph between |ψ|2 and r (radial distance) is shown below. This represents
2
|ψ|
r
(1) 1s-orbital (2) 2p-orbital (3) 3s-orbital (4) 2s-orbital
29. The electrons are more likely to be found
a Ψ(x)
b x
–x
(1) in the region a and c (2) in the region a and b

(3) only in the region a (4) only in the region c

Type : 8 (Quantum Numbers)
30. The orbital having two radial as well as two angular nodes is - [JEE Main 2021]
(1) 3p (2) 4f (3) 4d (4) 5d
31. The number of orbitals with n = 5, m1 = + 2 is ______. (Round off to the Nearest Integer).
32. A certain orbital has n = 4 and mL = –3. The number of radial nodes in this orbital is _______ .
33. A certain orbital has no angular nodes and two radial nodes. The orbital is :
(1) 2s (2) 3s (3) 3p (4) 2p
34. The number of subshells associated with n = 4 and m = –2 quantum numbers is

(1) 8 (2) 2 (3) 16 (4) 4
35. Consider the hypothetical situation where the azimuthal quantum number, l takes values 0, 1,
2,...n + 1, where n is the principle quantum number. Then, the element with atomic number
(1) 8 is the first noble gas (2) 13 has a half-filled valence subshell
(3) 9 is the first alkali metal (4) 6 has a 2p-valance subshell
1
36. The number of orbitals associated with quantum numbers n = 5, ms = + is
2
(1) 25 (2) 50 (3) 15 (4) 11
37. Hydrogen has three isotopes (A), (B) and (C). If the number of neutron(s) in (A), (B) and (C)
respectively, are (x), (y) and (z), the sum of (x), (y) and (z) is
(1) 4 (2) 3 (3) 2 (4) 1
38. The quantum number of four electrons are given below :

1 1
I. n = 4, λ = 2, mλ = –2, ms = − II. n = 3, λ = 2, mλ = 1, ms = +
2 2
1 1
III. n = 4, λ = 1, mλ = 0, ms = + IV. n = 3, λ = 1, mλ = 1, ms = −
2 2
The correct order of their increasing energies will be :
(1) IV < III < II < I (2) I < II < III < IV (3) IV < II < III < I (4) I < III < II < IV
39. Which of the following combination of statements is true regarding the interpretation of the
atomic orbitals ?
I. An electron in an orbital of high angular momentum stays away from the nucleus than an
electron in the orbital of lower angular momentum.
II. For a given value of the principal quantum number, the size of the orbit is inversely
proportional to the azimuthal quantum number.
h
III. According to wave mechanics, the ground state angular momentum is equal to .
2π
IV. The plot of ψ vs r for various azimuthal quantum quantum numbers, shows peak shifting
towards higher r value.
(1) I, III (2) II, III (3) I, II (4) I, IV
40. The 71st electron of an element X with an atomic number of 71 enters into the orbital
(1) 4f (2) 6p (3) 5d (4) 6s

ANSWER KEY
1. 180 2. (3) 3. (2) 4. (3) 5. (2)
6. (4) 7. (3) 8. (2) 9. (3) 10. (4)
11. (3) 12. (4) 13. (3) 14. (1) 15. (3)
16. (2) 17. 222 18. (4) 19. (2) 20. 2
21. 9 22. (3) 23. (1) 24. (4) 25. 1
26. (3) 27. (3) 28. (4) 29. (1) 30. (4)
31. 3 32. 0 33. (2) 34. (2) 35. (2)
36. (1) 37. (2) 38. (3) 39. (4) 40. (3)
SOLUTIONS
hc NA
1. =
E ×
λ 1000
6.63 × 10 −34 × 3 × 108 × 6.02 × 1023
=
663 × 10 −9 × 1000
= 3 × 6.02 × 10 kJ
= 180.6 kJ
2. According to Bohr’s theory :

z 2 eV z2
(A) KE = 13.6 ⇒ KE α
n2 atom n2
z
(B) speed of e– α
n
∴ v ×nα z
v
(C) Frequency of revolution of e − =
2πr
z2
∴ frequency α 3
n
kq1q2 kze2  n2
=
(D) F = rα
r2 r2  z
z
⇒ Fα 2
 n2 
 
 z 
z3
⇒ Fα
n4

3. Statement-I is false since Bohr’s theory accounts for the stability and spectrum of single
electronic species (eg : He+, Li2+ etc)
Statement II is true.
n2
4. We know that, r = 0.529 Å
Z
For Li2+ − (rLi2 + )n
(rLi2 + )n 4=
= 3
0.529
⇒ (16–9) = ∆R2 …(i)
3
For He+ = (r
He+ n 4=
)
He+ n 3
− (r )
0.529
⇒ (16–9) = ∆R2 …(ii)
3
∆R1 3 2
= =
∆R2 0.529
(16 − 9) 3
2
Hence, the ratio of ∆R1 : ∆R2 is 2 : 3
5. According to Bohr model, radius of orbit

a 0 × n2
rn = , where a0 = Bohr radius
Z
(Radius of 1st orbit of H-atom)
For, Li2+, Z = 3 and n = 2
22 × a0 4a0
∴ =r =
3 3
6. Statement (D) is incorrect. For 1s-orbital radial probability density (R2) against r is given as :
2
R
1s
r
For 1s-orbital, probability density decreases sharply as we move away from the nucleus. The
radial distribution curves obtained by plotting radial probability functions vs r for 1s-orbital is
2
4πrR

The graph initially increases and then decreases. It reaches a maximum at a distance very
close to the nucleus and then decreases. The maximum in the curve corresponds to the
distance at which the probability of finding the electron in maximum.
7. The ground state energy of H-atom is +13.6 eV.

For second excited state, n = 2 + 1 = 3
Z2
∴ E3(He+) = −13.6 × +
eV [Θ for He , Z = 2]
n2
22
= −13.6 × eV = –60.4 eV
32
Circumference
8. Number of waves =
Wavelength
2πr
n=
λ
∴ 2πr = nλ … (i)
Also we know that radius (r) of an atom is given by
a 0 n2
r=
Z
Thus, Eq. (i) becomes
n2
2πa0 = nλ … (ii)
Z
n2
∴ 2πa0 = n (1.5πa0) [Given, λ = 1.5 πa0]
Z
n 1.5πa0 1.5
= = = 0.75
Z 2πa0 2
9. Quantum nature of atoms are associated with following phenomena or process :

(i) Absorption spectrum
(ii) Emission spectrum
(iii) Black body radiation
(iv) Photo-electricity
Internal energy (U) of particles like atoms depends upon the thermodynamics variables (p, V,
T) of the system. Thus, U = f(p, T)
or U = f1(TV)
or U = f2(p, V)
So, quantum nature of atom is not associated with its internal energy.
Graph (c) is not a direct manifestation of the quantum nature of atoms.
10. Balmer series lies in the visible region of the electromagnetic spectrum. Photons that
correspond to these energies will not strongly absorb highly excited hydrogen gas. So, there
is the possibility for detecting adsorption at Balmer line wave length.
Paschen, bracket and Pfund series lies in the infrared region where as, only Layman series
lies in the ultraviolet region of the electromagnetic spectrum.

hc
11. As we know that, ∆E =
λ
hc
Hence λ will be, λ=
∆E
For, λ = minimum, i.e. shortest, ∆E = maximum
For Lyman series, n = 1 and for ∆Emax transition must be form n = ∞ to n = 1.
1  1 1
= RH Z 2  2 − 2 
So, (Θ n1 = 1 = 1 and n2 = ∞)
λ  n1 n2 
1 1 1 
= RH  2 − 2  × (1)2
λ 1 ∞ 
1 1 1
= RH (1 − 0) ⇒ = R × (1)2 ⇒ λ1=
λ λ R
For longest wavelength, ∆E = minimum for Balmer series, n = 3 to n = 2 will have ∆E
minimum.
For He+, Z = 2
1  1 1
So, =×
RH 2 2  2 − 2 
λ  n1 n2 
1 5 9
= RH × ⇒ λ 2 = λ1 =
λ2 9 5
12. Statements I, II and III are correct. The explanation of these statements are as follows :
(I) In each series of hydrogen spectrum, lines coverage at the higher frequency or lower
wavelength limit.
Frequency
Wavelength
∴ This is correct.
(II) For Balmer series, n1 = 2
∴ This is correct.
(III) Longest wavelength represents the smallest wave number
1 1
= v RH  2 − 2  . (n2 > n1)
 n1 n2 
When n1 = 2 smallest value of v is for n2 = 3
∴ This is a correct statement.
(IV) This statement is not correct. It's corrected from is as follows : Ionisation energy of
hydrogen can be calculated from Lyman series lines (n = 1) only by using the following
formula.
 1 1 
=v RH  2 − 2 
 (1) ∞ 

13. For any given series of spectral lines of atomic hydrogen.
–1
Let =
∆ν v max − v min be the difference in maximum and minimum frequencies in cm .
For Lyman series, =
∆ν v max − v min
General formula :
1 1
=ν 109677  2 − 2 
 ni nf 
For Lyman n1 = 1, n2 = 2, 3,….
1 1  1 
=
v max 109,677  =
−  109,677  − 0  = 109,677
1 ∞  1 
1 1 
=
νmin 109,677  − 2 
 1 (2) 
∆νLyman = νmax − νmin
109,677 × 3  109,677
=
109,677 −  =
 4  4
For Balmer series,
 1 1  109,677
=νmax 109,677  2 −  ⇒
 (2) ∞  4
 1 1  109677 × 5
=νmin 109,677  2 − ⇒
 (2) (3)2  36
∆ν = νmax − νmin
109,677 109,677   1
=
∆νBalmer − × 5  = 109,677  
4  36  9
∆νLyman 109,677 / 4
=
∆νBalmer 109,677 / 9
∆νLyman 9
=
∆νBalmer 4
∆νLyman
∴ The ratio of is 9 : 4.
∆νBalmer
14. According to Rydberg's equation,

1 RH  1 1  1  1 1 
=  2 − 2  or ∝  2 − 2 
λ hC  n1 n2  λ  n1 n2 
For shortest wavelength, i.e. highest energy spectral line, n2 will be (∞).
For the given spectral series, ratio of the shortest wavelength of two spectral series can be
calculated as follows :
1 1 1 1 1
− −0 −
λL 3 2 ∞ 2 9 1 λBk 52 ∞ 2 = 1 × 16 = 16
(A) = = = (B) =
λP 1 1 1− 0 9 λPf 1 1 25 1 25
− − 2
12 ∞ 2 42 ∞
1 1 1 1
− 2 − 2
λP 5 2
∞ 1 9 9 λB 4 2
∞ = 1 ×4 = 1
(C) = = × = (D) =
λPf 1 1 25 1 25 λBk 1 1 16 1 4
− − 2
32 ∞ 2 22 ∞
Note :Lyman = L(n1 = 1), Balmer = B(n1 = 2), Paschen = P(n1 = 3), Brackett = Bk(n1 = 4),
Pfund = Pf(n1 = 5)

15. According to Rydberg's formula,
 1 1 
wave number ( ν ) = RH Z2  2
− 2
 ni nf 
Given, ni = 8, nf = 8 [Θ it is the case of emission]
1 1
ν= RH × (1)2  2 − 2 
n 8 
1 1  RH RH
=
ν RH  2 − = =
n 64  n2 64
On comparing with equation of straight line, y = mx + c, we get
−RH
Slope = RH, intercept =
64
1
Thus, plot of wave number ( ν ) against will be linear with slope (+RH).
n2
1   1 1  
16. ∆E = hc × = hc × RH  2 − 2  × Z2 
λ   n1 n2  
1 1 hc
⇒ − 2 = [for H, atom Z = 1]
2
n1 n2 RH × λ × Z 2 × hc
1 1 1
= = ×
RH × λ (1× 107 m−1 ) (900 × 10 −9 m)
1 1 1
⇒ − =
n12 n22 9
1 1 1 1
So, in option (D) − 2 = −0 = [∴ n1 = 3, n2 = ∞]
3 2
∞ 9 9
17. For photoelectrons, its kinetic energy will be

hc
KE = E – Ea = – E0
λ
6.63 × 10 −34 × 3 × 108
= −9
− 4.41× 10 −19 J = 222 × 10–21 J
300 × 10
λ = Wavelength of photon
= 300 nm = 300 × 10–9 m
λ = Threshold energy
= Work function of sodium metal = 4.41 × 10–9 J
18. For photoelectric effect,

(i) KE = E –E0
where,
KE = Kinetic energy of ejected electrons,
E = Energy of incident light = hν
E0 = Threshold energy = hν0
ν = Frequency of incident light

ν0 = Threshold frequency
KE
0
E0 E
Slope = ± 1, intercept = – E0
So, option (A) is correct.
(ii) KE of ejected electrons does not depend on the intensity of incident light.
KE
0
Intensity of light
So, option (B) is correct.
(iii) When, number of ejected electrons is plotted with frequency of light, we get
Number
of e –'s
0
Frequency of light(v)
So, option (C) is also correct.
(iv) KE = hν – hν0
KE
0
v0 v
Slope = +h, intercept = – hν0

So, option (D) is not correct.
19. Work function of metal (φ) = hν0

where, ν0 = threshold frequency
1
Also, m e v 2 = hν − hν 0
2
1
or m e v 2 = hν − φ … (i)
2
1 hc
me v=
2
−φ … (ii)
2 λ
Given : λ = 4000 Å = 4000 × 10–10 m, v = 6 × 105 ms–1, me = 9 × 10–31 kg, c = 3 × 108 ms–1
h = 6.626 ×10–34 Js

Thus, on substituting all the given values in Eq. (i), we get
1
× 9 × 10–31 kg × (6 × 105 ms–1)2
2
6.626 × 10 −34 Js × 3 × 108 ms−1
= −φ
4000 × 10 –10 m
∴ φ = 1.62 × 10–24 kgm2s–2 – 4.96 × 10–19 J = 3.36 × 10–19 J [1 kgm2s–2 = 1J]
= 2.1 eV
h
20. λ=
2mqV
λLi mp (e)V
= mLi = 8.3 mp
λP mLi (3e)(V)
λLi 1 1
= = = 0.2= 2 × 10 −1
λP 8.3 × 3 5
hc
21. Energy incident =
λ
6.63 × 10−34 × 3.0 × 108
= eV
248 × 10−9 × 1.6 × 10−19
6.63 × 3 × 100
=
248 × 1.6
= 0.05 eV × 100 = 5 eV
Now using
E = φ + K.E.
5 = 3 + K.E.
K.E. = 2eV = 3.2 × 10–19 J
h
For debroglie wavelength λ =
mv
1
K.E. = mv 2
2
2KE
So v =
m
h
hence v =
2KE × m
6.63 × 10−34
=
2 × 3.2 × 10−19 × 9.1× 10−31
6.63 10 –34 66.3 × 10−10 m
= × =
7.6 10−25 7.6
= 8.72 × 10–10 m
≈ 9 × 10–10 m
= 9Å

h h
22. The de*Broglie wavelength of an electron, λ = , or
p mv
But, from the Bohr's postulate of quantization of angular momentum of electrons,
nh
I = mvr = ,
2π
nh
∴ mv =
2πr
h
Upon substitution, λ = ,
 nh  2πr
 2πr  = n
 
n2 a 0
where, r is the radius of orbits in Bohr model =
Z
2π × n2 × a0 2πna0 Z = 1 for hydrogen 
∴ λ= = = 8πa0  
n× Z Z n = 4 (given) 
23. The expression of kinetic energy of photo electrons,

1
KE= mv 2= E − E0
2
When, KE >> E0, the equation becomes,
1
=
KE = mv 2 E
2
1 hc p2 hc
⇒ mv 2 = ⇒ =
2 λ 2m2 λ
1 1
⇒ λ = hc × 2m2 × 2
⇒λ ∝ 2
p p
hc
E= = energy of incident light, E0 = threshold energy or work functions,
λ
1 1 (mv)2 1 p2
mv 2 = × = ×
2 2 m2 2 m2
Θ p = momentum = mv
As per the given condition,
2
λ 2  p1 
= 
λ1  p2 
2
λ2  p 
2
2 4
⇒ =  =  = 
λ  1.5 × p   
3 9
4
⇒ λ2 = λ [Θλ1 = λ, p1 = p]
9

24. de-Broglie wavelength (λ) for electron is given by
h
λ= … (i)
2mK.E
Also, according to photoelectric effect
KE = hν – hν0
On substituting the value of KE in Eq. (i), we get
h
λ=
2m × (hν − hν 0 )
1
∴ λ∝
( ν − ν0 )
1/ 2
5
25. ∆v = 90 ×
100
= 4.5 m/s
h
∆v.∆x =
4πm
h
∆x =
4πm.∆v
6.63 × 10 −34
=
4 × 3.14 × 0.01× 4.5
= 1.17 × 10–33
26. Number of radial nodes = n – l– 1

=3–0–1=2
Therefore corresponding graph is (D)
Hence answer is (3)
[R(r)]2
27. 3p
r
φ2 (Probability density) can be zero for 3p orbital other than infinite distance.
Since, n = 3, I = 1 for 3p orbital, the number of radial nodes = 3 – 1 – 1 = 1

28. The graph between |ψ|2 and r are density plots having (n – λ –1) number of radial nodes. For
1s, 2s, 3s and 2p-orbitals these are respectively.
2 For 1s-orbital
|Ψ| number of radial node = 1–0–1=0
For 2s-orbital
number of radial node = –2–0–1=1
|Ψ|2
For 3s-orbital
2
number of radial node = 3–0–1=2
|Ψ|
2
For 2p-orbital
|Ψ| number of radial node = 2–1–1 = 0
Thus, the given graph between |ψ|2 and r represents 2s-orbital.
29. The electrons are more likely to be found in the region a and c. At b, wave function becomes
zero and is called radial nodal surface or simply node.
a Ψ(x)
b +x
–x
The graph between wavelength (ψ) and distance (r) from the nucleus helps in determining the
shape of orbital.

30. n–l–1=2
l=2
n–2–1=2
n=5
31. For, n = 5
λ = (0, 1, 2, 3, 4)
If λ = 0, m = 0
λ = 1, m = {–1, 0, +1}
λ = 2, m = {–2, –1, 0, +1, +2}
λ = 3, m = {–3, –2, –1, 0, +1, +2, +3}
λ = 4, m = {–4, –3, –2, –1, 0, +1, +2, +3, +4}
5d, 5f and 5 g subshell contain one-one orbital having mλ = +2
32. n = 4 and mλ = –3
Hence. λ value must be 3.
Now, number of radial nodes = n – λ – 1
=4–3–1=0
33. 1 = 0 ⇒ 's' orbital

n–l–1=2
n–1=2
n=3
34. Principal quantum number (n) signifies the shell or orbit number.
From the number of values of azimuthal quantum number (I), we can calculate number of
subshells present in a shell as,
I = 0 … (n-1)
So, when n = 4
The permissible values of I and subshells are
I = 0 → s-subshell
= 1 → p-subshell
= 2 → d-subshell
= 3 → f-subshell
But, here values of I are restricted by the value of magnetic quantum number, m = –2, where,
m depends on / as
m = – I …. 0 … + I
So, m = – 2 values of / are restricted by the value of magnetic quantum number, m = – 2,
where, m depends on / as
m=–I…0…+I
So, m = – 2 value is possible for two subshells, viz,
I = 3 (f-subshell) and I = 2 (d-subshell) only.
I = 3 ⇒ m = – 3, – 2 – 1, 0, + 1, + 2, +3
I = 2 ⇒ m = – 2, – 1, 0, + 1, + 2

35. Hypothetical situation :
Azimuthal quantum number (I) = 0 – (n – 1)
n = Principal; quantum number
For, n = 1 I= 0, 1, 2
↓ ↓ ↓
1s 1p 1d
2 6
1s 1p 1d10
Number of electrons is s-orbital = 2
Number of electrons in p-orbital = 6
Number of electrons in d-orbital = 10
Z = 13 (Half-filled valence sub-shell)
For n = 1, 1s21p61d5 (Z = 13)
Number of electrons in 1d-orbital are 5. (It is half-filled).
Element with atomic number 9 is not first alkali metal but a halogen 1s22s22p5.
First noble gas has atomic number 2 not 8.
36. According to quantum mechanical atom model, for each value of n (principal quantum
number), there are 'n' different values of I (azimuthal quantum number), i.e. I = 0, 1, 2, …. (n –
1). And for each value of I, there are 2I + 1, different values of mI (magnetic quantum number),
i.e. mI = 0, ±1, ±2 … ±I.
∴ Total number of possible combinations of n, I and mI, for a given value of n is n2, and each
such combination is associated with an orbital. Each orbital can occupy a maximum of two
1 1
electrons, having a different value of spin quantum number (ms), which are +
or – .
2 2
∴ Number of orbitals associated with n = 5 is n = 25. Each of those orbitals can be
2
1 1
associated with ms = + as well as ms = – .
2 2
∴ Answer = 25
37. Number of neutrons in protium (11H) is zero (x).

Number of neutrons in deuterium (12 H or 12D) is 1 (y)
Number of neutrons in tritium (13 H or 13 T) is (z)
So, the sum of x, y and z is x + y + z = 3
38. Smaller the value of (n + λ), smaller the energy. If two or more sub-orbits have same values of
(n + λ), sub-orbits with lower values of n has lower energy. The (n + λ) values of the given
options are as follows :
I. n = 4, λ = 2, n + λ = 6
II. n = 3, λ = 2, n + λ = 5
III. n = 4, λ = 1, n + λ = 5

IV. n = 3, λ = 1, n + λ = 4
Among, II and III, n = 3 has lower value of energy. Thus, the correct order of their increasing
energies will be IV < II < III < I
nh
39. (I) Angular momentum, mvr =
2π
⇒ mvr∝n ∝ distance from the nucleus
(II) This statement is incorrect as size of an orbit ∝ Azimuthal quantum number (λ)
[Θ n = constant]
(III) This statement is incorrect as at ground state, n = 1, λ = 0
⇒ Orbital angular momentum (wave mechanics)
h
= 
(+ 1) =0 [Θλ = 0]
2π
(IV) The given plot is
l=0(n=1)
l=0(n= 2)
l=2(n = 3)
Ψ
l=3(n=4)
40. In the lanthanoid series, atomic number of fourteen 4f-block elements ranges from 58 (Ce) to
71(Lu).
Ytterbium, Yb(Z = 70) has electronic configuration : [Xe]4f14 6s2. So, the 71nth electron of
lutetium,
Lu(Z = 71) should enter into 5d orbital and its (here, Lu is 'X') electronic configuration will be :
[Xe]4f14 5d1 6s2. It happens so, because f-block elements have general electronic
configuration,
(n –2)f1-14 (n–1)d1-10 ns2. Therefore, option (C) is correct.

Type : 1 (Ideal Gas Equation)
1. The volume occupied by 4.75 g of acetylene gas at 50°C and 740 mmHg pressure is _____ L.
[Given R = 0.0826 L atm K–1 mol–1] [JEE Main 2021]
2. A car tyre is filled with nitrogen gas at 35 psi at 27°C. It will burst if pressure exceeds 40 psi.
The temperature in °C at which the car tyre will burst is _______. (Rounded-off to the nearest
integer)
3. The pressure exerted by a non-reactive gaseous mixture of 6.4 g of methane and 8.8 g of
carbon dioxide in a 10 L vessel a 27º C is ________ kPa. (Round off to the nearest Integer).
[Assume gases are ideal, R = 8.314 J mol–1 K–1 Atomic masses: C : 12.0 u, H : 1.0 u, O : 16.0 u]
4. Which one of the following graphs is not correct for ideal gas ?
d = density, p = pressure, T = Temperature

(1) III (2) I (3) IV (4) II
5. A spherical balloon of radius 3 cm containing helium gas has a pressure of 48 × 10–3 bar. At
the same temperature, the pressure, of a spherical balloon of radius 12 cm containing the
same amount of gas will be .......... × 10–6 bar.
: 353, Rajeev Gandhi Nagar, Instrumentation Limited Colony, Kota, Rajasthan 324005
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6. Among the following statements, that which was not proposed by Dalton was
(1) chemical reactions involve reorganisation of atoms. These are either created nor
destroyed in a chemical reaction.
(2) when gases combine or reproduced in a chemical reaction they do so in a simple ration by
volume provided all gases are at the same T and P.
(3) all the atoms of a given element have identical properties including identical mass. Atoms
of different elements differ in mass.
(4) matter consists of indivisible atoms.
7. An open vessel at 27° C is heated until two fifth of the air (assumed as an ideal gas) in it has
escaped from the vessel. Assuming that the volume of the vessel remains constant, the
temperature at which the vessel has been heated is
(1) 750 K (2) 500 K (3) 750°C (4) 500°C
Type : 2 (Dalton’s law of partial pressure)
8. A mixture of one mole each of H2, He and O2 each are enclosed in a cylinder of volume, V at
temperature T. If the partial pressure of H2 is 2 atm, the total pressure of the gases in the
cylinder is [JEE Main 2020]
(1) 14 atm (2) 38 atm (3) 22 atm (4) 6 atm
Type : 3 (Maxwell Boltzmann distribution equation of speed)

9. Identify the correct labels of A, B and C in the following graph from the option given below :
A B
C
No. of
molecules
Speed
Root mean square speed (Vrms); most probable speed (Vmp); Average speed (Vav)
[JEE Main 2020]
(1) A – Vrms; B – Vmp; C – Vav
(2) A – Vmp; B – Vrms; C – Vav
(3) A – Vmp; B – Vav; C – Vrms
(4) A – Vav; B – Vrms; C – Vmp
10. Points I, II and III in the following plot respectively correspond to (vmp : most probable velocity)
Distribution function f(v) →
I II III
Speed , v →
(1) vmp of H2(300K); vmp of N2(300K); vmp of O2(400K)
(2) vmp of O2(400K); vmp of N2(300K); vmp of H2(300K)
(3) vmp of N2(300K); vmp of O2(400K); vmp of H2(300K)
(4) vmp of N2(300K) vmp of H2(300K); vmp of O2 (400K)
Type : 4 (Real Gas)

 ∂Z  xb
11. A certain gas obeys P(Vm – b) = RT. The value of   is RT . The value of x is_____.
 ∂P T
(Integer answer) (Z : compressibility factor) [JEE Main 2021]
12. Consider the van der Waals’ constants, a and b, for the following gases.
Gas Ar Ne Kr Xe
a/(atm dm6mol–2) 1.3 0.2 5.1 4.1
b/(10–2dm3mol–1) 3.2 1.7 1.0 5.0
Which gas is expected to have the highest critical temperature?
(1) Kr (2) Xe (3) Ar (4) Ne
13. At a given temperature T, gases Ne, Ar, Xe and Kr are found to deviate from ideal gas
RT
behavior. Their equation of state is given as, p= at T, Here, b is the van der Waals'
V −b
constant. Which gas will exhibit steepest increase in the plot of Z (compression factor) vs p?
(1) Xe (2) Ar (3) Kr (4) Ne
14. Consider the following table.
Gas a/(k Pa dm6mol–1) b/(dm3mol–1)
A 642.32 0.05196
B 155.21 0.04136
C 431.91 0.05196
D 155.21 0.4382
a and b are van der Waals' constants. The correct statement about the gases is
(1) Gas C will occupy lesser volume than gas A; gas B will be lesser compressible than gas D
(2) Gas C will occupy more volume than gas A; gas B will be more compressible than gas D
(3) Gas C will occupy more volume than gas A; gas B will be lesser compressible than gas D
(4) Gas C will occupy more volume than gas A; gas B will be lesser compressible than gas D
15. The vaolume of gas A is twice than that of gas B. The compressibility factor of gas A is trice
than that of gas B at same temperature. The pressures of the gases for equal number of
moles are:
(1) pA = 2pB (2) 2pA = 3pB (3) pA = 3pB (4) 3pA = 2pB
ANSWER KEY
1. (5) 2. (70) 3. (150) 4. (4) 5. (750)
6. (2) 7. (2) 8. (4) 9. (3) 10. (3)
11. (1) 12. (1) 13. (1) 14. (2) 15. (2)
SOLUTIONS
1. Given Mass = 4.75 g ⇒ C2H2(g)
4.75
⇒ Moles = mol
26
Temp = 50 + 273 = 323 K
740
P= atm
760
atm
R = 0.0826
mol K
nRT 4.75 0.0826 × 323
⇒ =V = ×
P 26  740 
 760 
 
96314.078
=
⇒ V = 5.00595
19240
2. P∝T
P2 T2 40 T
= ⇒ = 2
P1 T1 35 300
T2 = 342.854 K
= 69.70°C 70°C
Hence answer is (70)
6.4 8.8
3. Total moles of gases, n = nCH + nCO = + = 0.6
4 2
16 44
nRT 0.6 × 8.314 × 300

Now, P = =
V 10 × 10−3
= 1.49652 × 105 Pa = 149.652 kPa ≈ 150 kPa
4. Graph (II) is not correct for ideal gas.
For n mole of an ideal gas,
W
pV = nRT = RT
M
W RT RT  W 
⇒ p= × =×
d  M =d
V M M  
p·M
⇒ d=
RT
Where, p = pressure, V = volume,
T = temperature in K, R = molar gas constant,
w = mass of the gas in g,
M = gram molar mass of the gas and
W
d= = density of the gas.
V
1
(i) When, p = constant ⇒ d ∝
T
So, nature of the plot, d vs T is rectangular hyperbolic (I) but not linear (II). Again,
1
nature of the plot, d vs will be linear in (III).
T
(ii) When, T = constant ⇒ d ∝ p
Here, nature of the plot, d vs p will be linear as (IV).
5. Initial pressure (p1) = 48 × 10–3 bar

Final pressure (p2) = ........ × 10–6 bar
4
Initial volume (V1) = π(3)3
3
4
Final volume (V2) = π(12)3
3
According to Boyle’s law p1V1 = p2V2
4
48 × 10−3 × π(3)3 −3
3 = 48 × 10 × (3)
3
p1V1
=
p2 = 3
V2 4 (12)
π(12)3
3
48 × 10−3 × 27
= = 0.0277 × 27 × 10–3 = 750 × 10–6 bar
1728
Hence, the correct answer is 750.
6. The postulates given in options (a), (c) and (d) are proposed by Dalton.
Option (b) is defining the Gay-Lussac’s law of combining volumes of gases.
7. Given, temperature (T1) = 27°C = 273 + 27 = 300 K
Volume of vessel = constant
Pressure in vessel = constant
2 3
Volume of air reduced by so the remaining volume of air is
5 5
3
Let at T1 the volume of air inside the vessel is n so at T2 the volume of air will be n.
5
Now, as p and V are constant, so
3
n·T1 = nT2 ….(i)
5
Putting the value of T1 in euation (i) we get,
3 5
n × 300 = n × T2 or T2 = 300 × = 500K
5 3
8. Volume of cylinder = V, Temperature = T,

Partial pressure of H2 = 2 atm
According to law of partial pressure
pi = χi × pT
pi = partial pressure of the ith component,
χi = mole fraction, pr = total pressure
 nH2 
⇒ 2atm 
=  × pr
 nH2 + nHe + nO2 
3
Then, pr = 2 × = 6 atm
1
9. The increasing order of molecular velocities of gas molecules is as follows:

Most probable velocity (Vmp) < average velocity (Vav) < rms velocity (Vrms).
Because,
2RT 8RT
=Vmp = , Vav
M πM
3RT
and Vrms =
M
10.
Key Idea From kinetic gas equation, most
probable velocity (vmp) =
Where, R = gas constant, Where, R = gas

constant, T = temperature,
2RT
vmp =
M
T
i.e. vmp ∝
M
Gas M T (k) T/M
H2 2 300 300 / 2 = 150... III (Highest)
N2 28 300 300 / 28 = 10.71... I (Lowest)
O2 32 400 400 / 32 = 12.5...II

So,
I corresponds to vmp of N2 (300 K)
II corresponds to vmp of O2 (400 K)
III corresponds to vmp of H2 (300 K)
Pb
11. Z=1+
RT
 ∂Z  b
 dP  =0+ ×1
 T RT
12. Critical temperature is the temperature of a gas above which it cannot be liquefied whatever
high the pressure may be. The kinetic energy of gas molecules above this temperature is
sufficient enough to overcome the attractive forces. It is represented as Tc.
8a
Tc = 27Rb
8x1.3
= 0.0144
For Ar, Tc = 27x8.314x3.2
8x0.2
= 0.0041
For Ne, Tc = 27x8x.314x17
8x5.1
8x5.1
= 0.18
For Kr, Tc = 278.314x1.0
8x4.1
8x4.1
= 0.02
For Xe, Tc = 27x8.314x5.0
The value of Tc is highest for Kr (krypton).
13. Noble gases such as Ne, Ar, Xe and Kr found to deviate from ideal gas behavior. Xe gas will
exhibit steepest increase in plot of Z vs P. Equation of state is given as:
RT
p=
(V − b)
p(V – b) = RT
pV – pb = RT
⇒ pV = RT+ pb
pv pb
= 1+
RT RT
pv
As, Z=
RT
pb
So, Z=1+ ⇒ y = c + mx
RT
The plot of z vs p is found to be
b
Slope =
RT
p
The gas with high value of b will be steepest as slope is directly proportional to b. b is the
vander Waals' constant andis equal to four times the ac actual volume of the gas molecules.
Xe gas possess the largest atom volume among the given noble gases (Ne,Kr Ar,).Hence, it
gives the steepest increase in the plot of Z (compression factor )vsp.
14. For 1 mole of a real gas, the van der Waals' equation is
 a 
 p + 2  (v − b) =
RT
 v 
The constant 'a' measures the intermolecular force of attraction of gas molecules and the
constant 'b' measures the volume correction by gas molecules after a perfectly inelastic binary
collision of gas molecules.
For gas A and gas C given value of 'b' is 0.05196 dm3 mol–1. Here,
a ∝ intermolecular force of attraction
∝ compressibility ∝ real nature
1
∝
volume occupied
Value of a/(kPa dm6 mol–1) for gas A (642.32) > gas C (431.91.) So, gas will occupy more
volume than gas A. Similarly, for a given value of a say 155.21 kPa dm6 mol–1 for gas B and
1
gas D ∝ intermolecular force of attraction
b
∝ compressibility ∝ real nature
1
∝
volume accupied
b/(dm3 mol–1) for gas B (0.04136) < Gas D (0.4382)
So, gas B will be more compressible than gas D.
15. Given ZA = 3ZB

pV
Compressibility factor (Z) = [for real gases]
nRT
On substituting in equation (i), we get
p A VA 3p V
= B B ….(ii)
nARTA nBRTB
Also, it is given that
VA = 2VB, nA = nB and TA = TB
∴ Eq. (ii) becomes
p A × 2VB 3pB VB
= ⇒ 2pA = 3pB
nBRTB nBRTB
Type : 1 (Introduction, Kp & Kc)
1. At 1990 K and 1 atm pressure, there are equal number of Cl2 molecules and Cl atoms in the
reaction mixture. The value KP for the reaction Cl2(g) 2Cl(g) under the above conditions is
–1
x × 10 . The value of x is ______. (Rounded of to the nearest integer) [JEE Main 2021]
2. A homogeneous ideal gaseous reaction AB2(g) A(g) + 2B(g) is carried out in a 25 litre flask
at 27°C. The initial amount of AB2 was 1 mole and the equilibrium pressure was 1.9 atm. The
value of KP is x × 10–2. The value of x is______.(Integer answer)
3. Consider the reaction N2O4(g) (g) 2NO2(g). The temperature at which KC = 20.4 and
KP = 600.1, is ______ K. (Round off to the Nearest Integer).
[Assume all gases are ideal and R = 0.0831 L bar K–1 mol–1]
4. For the equilibrium A B, the variation of the rate of the forward (a) and reverse (b)
reaction with time is given by
(1) (2)
(3) (4)
5. If the equilibrium constant for A B + C is and that of B + C P is , the
equilibrium constant for A P is

(1) (2) (3) (4)
6. For a reaction, X + Y = 2Z
1.0 mol of X, 1.5 mol of Y, and 0.5 mol of Z, were taken in a 1 L vessel and allowed to react.
At equilibrium, the concentration of Z was 1.0 mol L–1, The equilibrium constant of the reaction
x
is ………. . The value of x is …………
15
3
7. For the reaction, Fe2N(s) + H2(g) 2Fe(s) + NH3(g)
2
(1) KC = Kp(RT) (2) KC = Kp(RT)–1/2 (3) KC = Kp(RT) (4) KC = Kp(RT)3/2
8. The value of KC is 64 at 800 K for the reaction,

N2(g) + 3H2(g) 2NH3(g)
The value of KC for the following reaction is
1 3
NH3 (g) N2 (g) + H2 (g)
2 2
(1) 1/64 (2) 8 (3) 1/4 (4) 1/8
K
9. In a chemical reaction, A + 2B 2C + D, the initial concentration of B was 1.5 times of
the concentration of A, but the equilibrium concentration of A and B were found to be equal.
The equilibrium constant (K) for the aforesaid chemical reaction is.
1
(1) (2) 16 (3) 1 (4) 4
4
Type : 2 (le chatelier’s principle)
10. Consider the following reaction :
N2O4(g) 2NO2(g) ; ∆Hº = + 58 kJ
For each of the following cases (A, B), the direction in which the equilibrium shifts is
(A) temperature is decreased.
(B) pressure is increased by adding N2 at constant T. [JEE Main 2020]
(1) (A) towards product, (B) towards reactant
(2) (A) towards reactant, (B) no change
(3) (A) towards reactant, (B) towards product
(4) (A) towards product, (B) no change
Type : 3 (Thermodynamics of equilibrium)

11. For the reaction A(g) 
→ (B)(g), the value of the equilibrium constant at 300 K and 1 atm is
equal to 100.0. The value of ∆rG for the reaction at 300 K and 1 atm in J mol–1 is –xR, where
x is ______ (Rounded of to the nearest integer)
(R = 8.31 J mol–1 K–1 and ln 10 = 2.3) [JEE Main 2021]
12. Assuming ideal behaviour, the magnitude of log K for the following reaction at 25°C is x × 10–1.
The value of x is _______. (Integer answer)
3HC ≡ CH(g) C6H6(l)
[Given : ∆fG°(HC ≡ CH) = –2.04 × 105 J mol–1; ∆fG°(C6H6) = –1.24 × 105 J mol–1;
R = 8.314 J K–1 mol–1]
13. The gas phase reaction

2A(g) A2(g)
At 400 K has ∆Gº = + 25.2 kJ mol–1.
The equilibrium constant KC for this reaction is ______ × 10–2. (Round off to the Nearest
integer.
[Use : R = 8.3 J mol–1 K–1, ln 10 = 2.3 log10 2 = 0.30, 1 atm = 1 bar]
[Antilog (–0.3) = .0501]
14. For the equilibrium, 2H2O H3O+ + OH–, the value of ∆G° at 298 K is approximately
(1) – 80 kJ mol–1 (2) 100 kJ mol–1 (3) 80 kJ mol–1 (4) – 100 kJ mol–1
15. The stepwise formation of [Cu(NH3)4]2+ is given below
K1
Cu2+ + NH3 [Cu(NH3)]2+
K2
[Cu(NH3)]2+ + NH3 [Cu(NH3)2]2+
K3
[Cu(NH3)2]2+ + NH3 [Cu(NH3)3]2+
K4
[Cu(NH3)3]2+ + NH3 [Cu(NH3)4]2+
The value of stability constants K1, K2, K3 and K4 are 104, 1.58 × 103, 5 × 102 and 102
respectively. The overall equilibrium constants for dissociation of [Cu(NH3)4]2+ is x × 10–12.
The value of x is :
[JEE Main 2021]
16. For the reaction A(g) B(g) at 495 K, DrGº = –9.478 kJ mol–1.
If we start the reaction in a closed container at 495 K with 22 millimoles of A, the amount of B
is the equilibrium mixture is _______ millimoles.
[R = 8.314 J mol–1 K–1; ln 10 = 2.303]
17. For the following Assertion and Reason, the correct options is
Assertion (A) When Cu (II) and sulphide ions are mixed, they react together extremely quickly
to give a solid
Reason (R) The equilibrium constant of Cu2+(aq) + S2– (aq) CuS(s) is high because the
solubility product is low.
(1) Both (A) and (R) are false
(2) Both (A) and (R) are true and (R) is the explanation for (A)
(3) Both (A) and (R) are rue but (R) is not the explanation for (A)
(4) (A) is false and (R) is true
18. The variation of equilibrium constant with temperature is given below :

Temperature Equilibrium constant
T1 = 25ºC K1 = 10
T2 = 100ºC K2 = 100
The values of ∆Hº, ∆Gº at T1 and ∆Gº at T2 (in kJ mol–1) respectively , are close to
[use R = 8.314 JK–1 mol–1]
(1) 28.4, – 7.14 and –5.71 (2) 0.64, – 7.14 and –5.71
(3) 28.4, – 5.71 and 14.29 (4) 0.64, – 5.71 and –14.29
19. Two solids dissociate as follows:

A(s) B(g) + C(g); K p1 = x atm2
D(s) C(g) + E(g); K p2 = y atm2
The total pressure when both are solids dissociate simultaneously is
(1) x + y atm (2) x2 + y2 atm (3) (x + y) atm (4) 2 ( )

x + y atm
20. For the following Assertion and Reason, the correct options is
Assertion (A) When Cu (II) and sulphide ions are mixed, they react together extremely quickly
to give a solid
Reason (R) The equilibrium constant of Cu2+(aq) + S2– (aq) CuS(s) is high because the
solubility product is low.
(1) Both (A) and (R) are false
(2) Both (A) and (R) are true and (R) is the explanation for (A)
(3) Both (A) and (R) are rue but (R) is not the explanation for (A)
(4) (A) is false and (R) is true
ANSWER KEY
1. (5) 2. (74) 3. (354) 4. (1) 5. (3)
6. (16) 7. (3) 8. (4) 9. (4) 10. (2)
11. (1380) 12. (855) 13. (166) 14. (3) 15. (1)
16. (20) 17. (3) 18. (3) 19. (4) 20. (3)
SOLUTION
1. Cl2(g) 2Cl(g)
Let mol of both of Cl2 and Cl is x
x 1
PCl= × 1=
2x 2
x 1
PCl2 = × 1=
2x 2
2
 1
2
K p=   = = 0.5 ⇒ 5 × 10–1
1
1 2
2
2. AB2 = A + 2B
1 – –
1–α α 2α
= 0.535 0.465 0.93
1.9 × 25 = nT × 0.08206 × 300
nT = 1.93 = 1 + 2α
α = 0.465
 0.465   0.93 
 1.93 × 19   1.93 × 1.9 
Kp =    = 73 × 10–2 atm2
 0.535 
 1.93 × 1.9 
 
3. N2O(g) 2NO2(g); ∆n = 2 – 1 = 1
Now, KP = KC. (RT) ∆ngg
or, 600.1 = 20.4 × (0.0831 × T)1
∴ T = 353.99 K = 354 K
4. Fro the equilibrium, A B
At equilibrium, ra rb
Equilibrium is the condition when a forward chemical reaction and its reverse reaction proceed
at equal rates. It can be illustrated by following graph.
Rate of reaction
a
Equilibrium
b
Time
[B][C]
5. A eq =
B + C; K (1)
[A]
[P]
B+C eq =
P; K (2)
[B][C]
Equilibrium equation (i) and (ii)
[P]
(eq) × K (eq) =
K (1) =K eq
(2)
[A]
6. x+y 2z
t = teq. 1–a 15–a 0.5 + 2α(a = 1 mol)
x + y → 2z (z = 0.25)
0.75 mol 1.25 mol 1 mol
[z]2 1 x
=
K eq =
[x][y] 0.75 × 1.25 15
15
⇒ x= 16
0.75 × 1.25
∆ng
7. K p = K C (RT)
∆ng = number of gaseous product molecules – number of gaseous reactant molecules

3 1
=−
1 =−
2 2
Now, K p = K C (RT)−1/2
Kp
∴ KC = −1/2
⇒ Kp(RT)1/2
(RT)
Hence, the correct option (3).
8. Equilibrium constant for equation,
N2(g) + 3H(g) 2NH3(g)
[NH3 ]2
KC = = 64
[N2 ][H2 ]3
and for
1
2NH3 (g) N2 (g) + 3H2 (g),K 'C =
KC
and for equation,
1 3
NH3 (g) N2 (g) + H2 (g)
2 2
1 1 1 1
=
K 'C =1/2
=1/2
= 1/2
KC KC (64) 8
9. For the given chemical reaction.

A + 2B 2C + D
At, t = 0 a0 1.5a0 0 0
t = teq a0 – x 1.5a0 – 2x 2x x
[x = degree of dissociation]
Given, at equilibrium
[A] + [B]
a0 – x = 1.5a0 – 2x
x = 0.5a0
∴ [A] = a0 – x = a0 – 0.5a0 = 0.5a0
[B] = 1.5a0 – 2x = 1.5a0 – 2 × 0.5a0 = 0.5a0
[C] = 2x = 2 × 0.5a0 = a0
[D] = x = 0.5a0
[C]2 [D]
Now, K =
[A][B]2
Now, substituting the values in above equation, we get
(a0 )2 × (0.5 a0 )
K=
(0.5 a0 ) × (0.5 a0 )
10. N2O4(s) 2NO2(s) ; DHº = + 58 kJ

Because in case of an endothermic reaction (∆H = + ve), the equilibrium constant increases
with rise in temperature and hence, the reaction moves in forward direction. On adding N2,
pressure is increases at constant T, and volume would also be constant, so no change is
observed.
11. ∆G° = –RT ln Kp
= –R(300) (2) ln (10)
= –R(300 × 2 × 2.3)
∆G° = –1380 R
12. 3HC ≡ CH(g) → C6H6(l) : ∆G0 = –RT ln k

J
∆G0f − 2.04 × 105 –1.24 × 105 J/mol
mol
⇒ ∆G0 = ∑ ( ∆G ) − ∑ ( ∆G )
0
f P
0
f R
⇒ –RT nk = 1 × (–124 × 105) – (–3 × 2.04 × 105)

⇒ –2.303 × R × T log k = 4.88 × 105
4.88 × 105 488000

=
⇒ log k = = –85.52
2.303 × R × T 5705.848
⇒ 855 × 10–1
⇒ x = 855
13. Using formula

∆rGº = – RTlnKp
25200 = –2.3 × 8.3 × 400 log (Kp)
Kp = 10–3.3 = 10–3 × 0.501
= 5.01 × 10–4 Bar–1
= 5.01 × 10–9 Pa–1
KC
=
8.3 × 400
KC = 1.66 × 10–5 m3/mole
= 1.66 × 10–2 L/mol
Ans = 2
14. We know that, ∆G° = –2.303 RTlogK

Also, given equilibrium is
2H2O H3O+ + OH
[H+][OH–] = 10–14 or K = 10–14
∴ ∆G° = –2.303 × 8.314 JK–1 mol–1 × 298K × log 10–14
–79881.8 J mol–1
= 79.8 kJ ≈ 80 kJ mol–1
K1
15. Cu2+ + NH3 [Cu(NH3)]2+
K2
[Cu(NH3)]2+ + NH3 [Cu(NH3)2]2+
K3
[Cu(NH3)2]2+ + NH3 [Cu(NH3)3]2+
K4
[Cu(NH3)3]2+ + NH3 [Cu(NH3)4]2+
K4
[Cu2+ + 4NH3 [Cu(NH3)4]2+
So
K = K1 × K2 × K3 × K4
= 104 × 1.58 × 103 × 5 × 102 × 102
K = 7.9 × 1011
Where K → Equilibrium constant for formation of [Cu(NH3)4]2+
1
So equilibrium constant (K’) for dissociation of [Cu(NH3)4]2+ is
K
1
K' =
K
1
K' = = 1.26 × 10–12 = (x × 10–12)
7.9 × 1011
So the value of x = 1.26

OMR Ans = 1 (After rounded off to the nearest integer)
16. ∆Gº = –RT ln Keq

Given ∆Gº = –9.478 KJ/mole
T = 495K R = 8.314 J mol–1
So –9.478 × 103 = –495 × 8.314 ×ln Keq
ln Keq = 2.303
= ln 10
So Keq = 10
Now A(g) B(g)
t=0 22 0
t=t 22 – x x
[B] x
K= = = 10
[C] 22 − x
eq
or x = 20
So millmoles of B = 20
17. Both (A) and (R) are correct, but (R) is not the correct explanation of (A).
[A] Cu2 (aq) and S2–(aq) ions undergo ionic reaction whose are of reaction is very fast.
Cu2+(aq) + S2–(aq) → CuS(s) ↓
[R] For the reaction :
Cu2+(aq) + S2–(aq) CuS(s)
The expression of equilibrium constant is,
[CuS]
K eq =
[Cu2+ ][S2− ]
But, the expression of solubility product (Ksp) of CuS(s) will be

CuS(s) Cu2+(aq) + S2–(aq)
Ksp = [Cu2+] [S2–]
[CuS] 1
So, =K eq is,K eq ∝
K sp K sp
Because of high stability CuS, the value of Keq is high, i.e. the value of Ksp of CuS will be low.
18. T1 = 298 K, T2 = 373 K, K1 = 10, K2 = 100
K  ∆Hº  1 1 
=
log  2   − 
 K1  2.303R  T1 T2 
 100  ∆Hº  1 1 
=
∴ log    − 
 10  2.303 × 8.314  298 373 
∴ ∆Hº = 28.4 kJ/mol
We know that, ∆Gº = – RT ln K
∴ ∆Gº at T1 = – 8.314 × 298 × 2.303 × log(10)
⇒ –5.71 kJ/mol
∆Gº at T2 = – 8.314 × 373 × 2.303 × log(100)
⇒ –14.29 kJ/mol
Hence, the correct option is (3).
19. The equilibrium reactions for the dissociation of two solids is given as:
A(s) B(g)+ C(g)
p1 p1 +p2
at equilibrium
K p1 = x = pB ⋅ pC = p1(p1 + p2) ....(i)
Similarly, D(s) C(g) + E(g)

At equilibrium p1 + p2 ⋅ p2
K p2 = y = pC ⋅ pE = (p1 + p2)p2 ....(i)
On adding Eq. (i) and (ii), we get.

K p1 + K p2 = x + y = p1(p1 + p2) + p2(p1 + p2)
= (p1 + p2)2
or x + y = p1 + p2 ...(iii)
Now, total pressure is given as

p1 = pB + pC + pB
= p1 + (p1 + p2) + p2
2(p1 + p2) ...(iv)
On substituting the value of p1 + p2 from Eq. (iii) to Eq. (iv), we get
pr = 2 x + y
20. Both (A) and (R) are correct, but (R) is not the correct explanation of (A).
[A] Cu2 (aq) and S2–(aq) ions undergo ionic reaction whose are of reaction is very fast.
Cu2+(aq) + S2–(aq) → CuS(s) ↓
[R] For the reaction :
Cu2+(aq) + S2–(aq) CuS(s)
The expression of equilibrium constant is,
[CuS]
K eq =
[Cu2+ ][S2− ]
But, the expression of solubility product (Ksp) of CuS(s) will be

CuS(s) Cu2+(aq) + S2–(aq)
Ksp = [Cu2+] [S2–]
[CuS] 1
So, =K eq is,K eq ∝
K sp K sp
Because of high stability CuS, the value of Keq is high, i.e. the value of Ksp of CuS will be low.
C H E M I S TR Y

CPP
ST
IONIC EQUILIBRIUM NO. 05
Type : 1 (Introduction calculation of ph of acid and base and their mixture)

1. Sulphurous acid (H2SO3) has Ka1 = 1.7 × 10–2 and Ka2 = 6.4 × 10–8. The pH of 0.588 M H2SO3
is______ . (Round off to the Nearest Integer) [JEE Main 2021]
2. 0.01 moles of a weak acid HA(Ka = 2.0 × 10–6) is dissolved in 1.0 L of 0.1 M HCl solution. The
degree of dissociation of HA is ______ × 10–5 (Round off to the Nearest Integer).
Neglect volume change on adding HA. Assume degree of dissociation <<1]
3. 3 g of acetic acid is added to 250 mL of 0.1 M HCl and the solution made up to 500 mL. To 2o
1
mL of this solution mL of 5 M NaOH is added. The pH of the solution is ………. .
2
[Given : pKa of acetic acid = 4.75, molar mass of acetic acid = 60g/mol, log 3 = 0.4771]
Neglect any changes in volume.
4. Two solution, A and B, each of 100 L was made by dissolving 4 g of NaOH and 9.8 g of
H2SO4 in water, respectively. The pH of the resultant solution obtained from mixing 40 L of
solution A and 10 L of solution B is ………….
5. For the following Assertion and Reason, the correct option is

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

(a) pOH of 0.01 M HCl (b) pOH of 0.01 M NaOH
 
(c) pOH of 0.01 M CH3CO ONa (d) pOH os 0.01 M NaCl
(1) (a) > (c) > (d) > (b) (2) (a) > (d) > (c) > (b)
(3) (b) > (c) > (d) > (a) (4) (b) > (d) > (c) > (a)

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

8. The pH of ammonium phosphate solution, if pKa of phosphoric acid and pKb of ammonium
hydroxide are 5.23 and 4.75 respectively, is ______.
[JEE Main 2021]
9. The pH of a 0.02 M NH4Cl solution will be [Given Kb(NH4OH) = 10–5 and log2 = 0.301]
(1) 4.65 (2) 2.65 (3) 5.35 (4) 4.35
Type : 3 (Buffer Solution)

10. In order to prepare a buffer solution of pH 5.74, sodium acetate is added to acetic acid. If the
concentration of acetic acid in the buffer is 1.0 M, the concentration of sodium acetate in the
buffer is ______ M. (Round off to the Nearest Integer).
[Given : pKa (acetic acid = 4.74] [JEE Main 2021]
11. An acidic buffer is obtained on mixing

(1) 100 mL of 0.1 CH3COOH and 100 mL of 0.1 M NaOH
(2) 100 mL of 0.1 HCl and 200 mL of 0.1 M NaCl
(3) 100 mL of 0.1 CH3COOH and 200 mL of 0.1 M NaOH
(4) 100 mL of 0.1 HCl and 200 mL of 0.1 M CH3COONa
Type : 4 (Solubility Product (KSP))

12. The solubility product of PbI2 is 8.0 × 10–9. The solubility of lead iodide in 0.1 molar solution
of lead nitrate is x × 10–6 mol/L. The value of x is __________.
(Rounded off to the nearest integer) [Given : 2  1.41 ] [JEE Main 2021]
13. The solubility of AgCN in a buffer solution of pH = 3 is x. The value of x is:

[Assume : No cyano complex is formed; Ksp(AgCN) = 2.2 × 10–16 and Ka(HCN) = 6.2 × 10–10]
(1) 0.625 × 10–6 (2) 1.9 × 10–5 (3) 2.2 × 10–16 (4) 1.6 × 10–6
14. The solubility of Ca(OH)2 in water is :

[Given: The solubility product of Ca(OH)2 in water = 5.5 × 10–6]
(1) 1.77 × 10–6 (2) 1.11 × 10–6 (3) 1.11 × 10–2 (4) 1.77 × 10–2
15. Two salts A2X and MX have the same value of solubility product of 4.0 × 10–12. The ratio of
S(A 2 X)
their molar solubilities i.e. = ________ .
S(MX)
(Round off to the Nearest Integer)
16. The solubility of CdSO4 in water is 8.0 × 10–4 mol L–1. Its solubility in 0.01 M H2SO4 solution is
______ × 10–6 mol L–1. (Round off to the Nearest integer)
(Assume that solubility is much less than 0.01 M)

17. The stoichiometry and solubility product of a salt with the solubility curve given below is,
respectively :
[]y/mM
2
1
1 2 3
[X]/mM
(1) X2Y, 2 × 10–9 M3 (2) XY, 2 × 10–6 M3 (3) XY2, 1 × 10–9 M3 (4) XY2, 4 × 10–6 M3
18. The solubility product of Cr(OH)3 at 298 K is 6.0 × 10–31. The concentration of hydroxide ions
in a saturated solution of Cr(OH)3 will be
(1) (2.22 × 10–31)1/4 (2) (18 × 10–31)1/4 (3) (4.86 × 10–29)1/4 (4) (18 × 10–31)1/2
19. If solubility product of Zr3(PO4)4 is denoted by Ksp and its molar solubility is denoted by S, then
which of the following relation between S and Ksp is correct?
1/6 1/7 1/9 1/7
K   K  K  K 
(1) S =  sp  (2) S =  sp  (3) S =  sp  (4) S =  sp 
 144   6912   929   216 
20. What is the molar solubility of Al(OH3) in 0.2 M NaOH solution? Given that, solubility product
of Al(OH)3 = 2.4 × 10–24
(1) 3 × 10–19 (2) 12 × 10–21 (3) 3 × 10–22 (4) 12 × 10–23
21. If Ksp of Ag2CO3 is 8 × 10–12, the molar solubility of Ag2CO3 in 0.1 M AgNO3 is
(1) 8 × 10–12 M (2) 8 × 10–13 M (3) 8 × 10–10 M (4) 8 × 10–11 M
22. If the solubility product of AB2 is 3.20 × 10–11 M3, then the solubility of AB2 in pure water is
…… × 104 mol L–1
[Assuming that neither kind of ion reacts with water]
23. If Ksp of Ag2CO3 is 8 × 10–12, the molar solubility of Ag2CO3 in 0.1 M AgNO3 is
(1) 8 × 10–12 M (2) 8 × 10–13 M (3) 8 × 10–10 M (4) 8 × 10–11 M
Type : 5 (Indicators and Titration)

24. The strength of an aqueous NaOH solution is most accurately determined by titrating :
(Note : consider that an appropriate indicator is used)
(1) Aq. NaOH in a volumetric flask and concentrated H2SO4 in a conical flask
(2) Aq. NaOH in a pipette and aqueous oxalic acid in a burette
(3) Aq. NaOH in a burette and aqueous oxalic acid in a conical flask
(4) Aq. NaOH in a burette and concentrated H2SO4 in a conical flask
[JEE Main 2020]

25. 100 mL of 0.1 M HCl is taken is a beaker and to it 100 mL of 0.1 M NaOh is added in steps of
2 mL and the pH continuously measured. Which of the following graphs correctly depicts the
change in pH ?
(1) pH 7 (2) pH 7
vol. of NaOH vol. of NaOH
(3) pH 7 (4) pH 7
vol. of NaOH vol. of NaOH
26. The Ksp for the following dissociation is 1.6 × 10–5
PbCl2(s) Pb2+(aq) + 2Cl–(aq)
Which of the following choices is correct for a mixture of 300 ml of 0.134 M Pb(NO3)2 and 100
mL 0.4 M NaCl ?
(1) Q < Ksp (2) Q > Ksp
(3) Q = Ksp (4) No enough data provided
[JEE Main 2020]
27. Consider the following statements.

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

ANSWER KEY
1. (1) 2. (2) 3. (5.23) 4. (10.60) 5. (3)
6. (2) 7. (2) 8. (7) 9. (3) 10. (10)
11. (4) 12. (141) 13. (2) 14. (3) 15. (50)
16. (64) 17. (4) 18. (4) 19. (2) 20. (3)
21. (3) 22. 2 23. (3) 24. (3) 25. (1)
26. (2) 27. (4)
SOLUTIONS
1. H2SO3 [Dibasic acid]
C = 0.588 M
 pH of solution  due to First dissociation only since Ka, >> Ka2
 First dissociation of H2SO3
H2SO3(aq) H(aq) + HSO3–(aq) : ka1 = 1.7 × 10–2
t=0 C
t C–x x x
1.7 [H ][HSO3 ]
 Ka1 = 
100 [H2SO3 ]
 1.7 × 0.588 – 1.7x = 100 x2

 100x2 + 1.7x – = 0
1.7 (1.7)2  4  100  1

 [H] = x =  0.09186
2  100
Therefore pH of sol. Is : pH = log [H]

 pH = –log (0.09186) = 1.036  1
2. HA H+ + A–
Initial conc. 0.01M 0.1.M 0
Equ. conc. (0.01 – x) (0.1 + x) xM
Q 0.01m  0.1 M
[x  ][A – ] 2  10 –7
Now, Ka =   2  105
[HA] 0.01
3 1
3. 3g CH3COOH (M = 60) =  mol
60 20
250
250 mL of 0.1 M HCl = M × V =  0.1
1000
= 25 × 10–3 mol

After mixing these two, solution is diluted to 500 mL.
Then from that solution, 20 mL is taken.
20 1
Number of moles of both CH3COOH and HCl will be now only  of original solution.
500 25
1 1 1
nCH3COOH    = 2 × 10–3 mol
20 25 500
1
nHCl = 25 × 10–3 × = 10–3 mol
25
1
nNaOH added = M × V = × 5 × 10–3 = 2.5 × 10–3
2
After mixing, all HCl and NaOH will be neutralized. Remaining number of moles.
nNaCl = 10–3
nCH3COONa  1.5  103
nCH3COOH (unreacted) = 0.5 × 10–3
 Now the solution is a buffer solution.

[salt]
pH = pKa = log
[acid]
(nCH3COONa )
= pKa + log
(nCH3COOH )
= 4.75 + log 3 = 4.75 + 0.4771 = 52271 = 5.23

4. (A) 4 g NaOH in 100 L
4 / 40
 M  103 mol L–1.
100
(B) 9.8 g H2SO4 in 100 L
9.8 / 98
 M  10 3 mol L–1
100
40 L of solution A contains
= 40 × 10–3 mol NaOH ( n = M × V)
= 40 × 10–3 mol OH–

10 L of solution B contains
= 10 × 10–3 mol H2SO4
= 20 × 10–3 mol H+
When they are mixed, total volume = 50 L and all H+ is neutralized by OH–.
Number of moles (nOH ) of excess OH–.
= (40 – 20) × 10–3 = 20 × 10–3

nOH
[OH ]  (in liter)
Vsolution
nOH
or [OH ] 
Total volume
20  103
=  4  104 M
50
As we know,
pOH = log[OH–]
 pOH = –log 4 × 10–4 = 4 – log 4
or pH = 14 – pOH
= 14 – (4 – log 4) = 10 + log 4 = 10.602
5. The dissociation of water into H+ and OH– is an endothermic reaction.

 As temperature increase, its equilibrium constant also increases :
 [H+] and [OH–] in water at equilibrium increases with increases in temperature.
 pH = – log[H+] decreases, as temperature increases.
So, both Assertion and Reason are false.
6. (a) pOh of 0.01 M HCl :

 H  OH
HCl 
(0.01M) (0.01M) (0.01M)
[OH+] = (0.01 M); pH = – log [H+]

 –log(10–2)  2
pOH = 14 – pH  14 – 2 = 12
(b) pOH of 0.01 M NaOH :
 Na  OH
NaOH 
(0.01M) (0.01M)0. (0.01M)
[OH–] = 10–2
 pOH = – log[OH–]
 –log(10–2) = 2
 
(c) pOH of 0.01 M CH3CO ONa : (salt of weak acid + strong base)
1
pH = 7 + [pKa + log(10–2)]
2
 pH > 7, thus pOH < 7
(d) pOH os 0.01 M NaCl :
(It is a salt of strong acid + strong base)

7. Among the given options, distilled water has the lowest ionic conductance at 298 K.
Water from well or sea contains mineral ions,
 they have ionic conductance.
Saline water is an electrolyte and contain ions
 It also has ionic conductance.
8. Since (NH4)3PO4 is salt of weak acid (H3PO4) & weak base (NH4OH).
1
pH = 7 + (pKa – pKb)
2
1
= 7 (5.23 – 4.75)
2
= 7.24  7
9. Key Idea NH4Cl is a salt of weak base (NH4OH) and strong acid (HCl). On hydrolysis, NH4Cl
will produce an acidic solution (pH > 7) and the expression of pH of the solution is
1
pH = 7 – (pKb + logC)
2
Given, kb(NH4OH) = 10–5
 pKb = –logKb = – log(10–5) = 5
C = concentration of salt solution = 0.05 M = 2 × 10–2 M
1
Now, pH = 7 – (pKb + logC)
2
On substituting the given values in above equation, we get
1
=7– [5 + log(2 × 10–2)]
2
1
=7– [5 + log2 – 2]
2
1
=7– [5 + 0.301 – 2]
2
= 7 – 1.65 = 5.35
[CB]
10. pH = pKa + log
[WA]
[CB]
5.74 = 4.74 + log
1
 [CB] = 10 M

11. An acidic buffer is a mixture of weak and its salt with strong base. Now, let us study the
composition of each mixture obtained by mixing of two solutions.

(a) CH3COOH + NaOH  CH3COONa + H2O
t  0 100  0.1 100  0.1 0 0

milimol
ta 0 0 10 10
So, it is not a buffer.
NaCl, a salt of strong acid (HCl) and strong base (NaOH) is not hydrolysable by HCl also. So,
it is not a buffer.

CH3COOH + NaOH  CH3COONa + H2O
t  0 100  0.1 200  0.1 0 0

(Limiting)
milimol
ta 0 20  10  10 10 10
After mixing, the solution contains equimolar amounts by NaOH(a strong base) and

CH3COONa (salt). So, it is also not a buffer.

CH3COONa + HCl  + CH3COOH + NaO
t0 200  0.1 100  0.1 0 0

(Limiting)
milimol
t  a 20  10  10 0 10 10
Now, the resultant solution contains equimolar amount of CH3COOH (an week acid) and
CH3COONa (a salt of CH3COOH with strong base, NaOH).
So, it is an acid buffer.
9
12. Given : [K sp ]PbI2  8  10
To calculate : solubility of PbI2 in 0.1 M sol of Pb(NO3)2

2 
(I) Pb(NO3)2  Pb(aq)  2NO3 (aq)
0.1 M – –
– 0.1 M 0.2 M
(II) PbI2(s) Pb+2(aq) + 2I–(aq)
s 2s
= s + 0.1
 0.1

Now : Ksp = 8 × 10–9 = [Pb+2] [I–]2
 8 × 10–9 = 0.1 × (2s)2
 8 × 10–8 = 4s2  s = 2  10 4
 S  141 106 M
 x = 141
K sps2 K sp 
13.   ; s (H )
Ka (H ) Ka
2.2  10 16
s 10
 103
6.2  10
s = 1.9 × 10–5
Hence answer is (2)
14. Ca(OH)2 Ca2+(aq) + 2OH–(aq)

s 2s
2 –6 3
ksp = s(2s)  5.5 × 10 = 4S
1
 5.5  3
 s   102 = 1.11 × 10–2
 4 
15. (For A2X)

A2X  2A+ + X2–
2S1 S1
Ksp = 4S13 = 4 × 10–12
S1 = 10–4
For MX
MX  M+ + X–
S2 S2
Ksp = S22 = 4 × 10–12
S2 = 2 × 10–6
SA2 X 104
so   50
SMX 2  10 6
16. In pure water,

Ksp = S2 = (8 × 10–4)2

= 64 × 10–8
In 0.01 M H2SO4
H2SO4(aq)  2H+ (aq) + SO42–(aq).
0.02 0.01
BaSO4(s) Ba2+(aq.) + SO42–(aq)
X x (x + 0.01)
–8
Ksp = x (x + 0.01) = 634 × 10
x + 0.01  0.01 M
So, x (0.01) = 64 × 10–8
x = 64 × 10–6 M
17. Units given for all option is M3, or (mol L–1)3, which implies that, the equilibrium has three ions.
Therefore,
XY2 X2+ (aq) + 2Y–(aq), Ksp = [X2+] [Y–]2
or X2Y 2X+(aq) + Y2–(aq), Ksp = [X+]2 [Y2–]
(i) Ksp in case of XY2,
Ksp = (1 × 10–3) (2 × 10–3)2 = 4 × 10–9 M3
(ii) Ksp in case of X2Y,
Ksp = (1 × 10–3)2 (2 × 10–3) = 2 × 10–9M
The only matching value of Ksp from options that satisfies the concentration values from graph
is [X2+] = 1 mM = 1 × 10+ M and [Y–] = 2 × 10–3 M
thus, salt is XY2 and Ksp = (10–3) (2 × 10–3)2 = 4 × 10–9 M3
18. Ksp of Cr(OH)3 at 298 K is 6.0 × 10–31.

[OH–] in saturated solution of Cr(OH)3 = ?
Cr(OH)3 Cr3+ + 3OH–
S S
In a saturated solution, Ksp = [Cr3+] [OH–]3
= S(3S)3 = 27S4 = 6.0 × 10–31
1
6.0  1031  6.0  10 31  4
 S4  S 
27  27 
1
 6.0  1031  4
[OH–] = 3S = 3  
 27 

1
1
 6.0  34 31 
4
31 4
= 3
 10  (18  10 )
 3 
19. Key Idea The concentration of a substance in a saturated solution is defined as its
solubility(S).
For AxBy xAy+ + yBx– ; Ksp = [Ay+]x[Bx–]y
For, Zr3(PO4)4,
Zr3(PO4)4(s) 3Zr 4  (aq) + 4PO 34 (aq)
3SM 4 SM
Ksp = [Zr4+]3 [PO 34  ] 4

1
3 4  K sp  7
7
Ksp = (3S) (4S) = 6912 S or S =  
 6912 
1
 K sp  7
Thus, the relation between molar solubility(S) and solubility product (Ksp) will be S =  
 6912 
20. Key Idea Concentration of substance in a saturated solution is defined as its solubility (S). Its
value depends upon the nature of solvent and temperature. For reaction,
AB A+ + B–
Ksp = [A+] [B–]
Al(OH)3 Al3+ + 3OH–
Initially 1 0 0
At equilibrium 1 – S S 3S + 0.2
+ –
NaOH  Na + OH
0.2 0.2
Ksp of Al(OH)3 = 2.4 × 10–24 (Given)
Ksp = [Al]3+ [OH–]3
2.4 × 10–24 = [S] [3S + 0.2]3 [ 0.2 >> S]
2.4 × 10–24 = [S] [0.008]

[S] = 3 × 10–22
21. Let solubility of Ag2CO3 is S. Now,

0.1 M of AgNO3 is added to this solution after which let the solution of Ag2CO3 becomes S'
 [Ag+] = S + 0.1 and CO23   = S'
Ksp = (S + 0.1)2 (S') ...(i)

Given, Ksp = 8 × 10–12
 Ksp is very small, we neglect S' against S in Eq.(i)

 Ksp = (0.1)2S'
or 8 × 10–12 = 0.01 S'
or S' = 8 × 10–12 × 102 = 8 × 10–10 M
Thus, molar solubility of Ag2CO3 in 0.1 M AgNO3 is 8 × 10–10 M.
22. AB2(s) A2+(aq) + 2B–(aq)
If the molar solubility of the solid substance is S mol L–1 then
Ksp = [A2+]1 [B–]2 ; Ksp = S1 × (2S)2 = 4S3
Solubility product of AB2 = 3.20 × 10–11 M3
–11 3 3.20  10 11

3
3.20 × 10 =4×S S =
4
1/3
 320  1011 
S=    S = 2 × 10–4 mol L–1
 4 
23. Let solubility of Ag2CO3 is S. Now,

0.1 M of AgNO3 is added to this solution after which let the solution of Ag2CO3 becomes S'
 [Ag+] = S + 0.1 and CO23   = S'
Ksp = (S + 0.1)2 (S') ...(i)

–12
Given, Ksp = 8 × 10
 Ksp is very small, we neglect S' against S in Eq.(i)
 Ksp = (0.1)2S'
or 8 × 10–12 = 0.01 S'
or S' = 8 × 10–12 × 102 = 8 × 10–10 M
Thus, molar solubility of Ag2CO3 in 0.1 M AgNO3 is 8 × 10–10 M.
24. The strength of aqueous NaOH solution is most accurately determined by titrating aqueous
NaOH in burette and aqueous oxalic acid in conical flask with phenolphthalein as an indicator.
(For weak acid-strong base titration, methyl orange cannot be used).
Thus, solution turns colourless to pink at the end point. (Phenolphthalein has pink colour when
pH > 10 and it is colourless when pH < 8 (approximately) which is easily to perceive.
If NaOH is taken in conical flask and oxalic acid is added from burette, the end point will be
the decolourisation of pink colour which is more difficult to perceive by human eye quickly.
25. Given 100 mL of 0.1 M HCl is taken in beaker and to it 100 mL of 0.1 M NaOH is added. This
is acid (HCl) and base (NaOH) titration. Here, phenolphthalein act as an indicator and colour

change is pink. The correct graph that depicts the change in pH is as follows. At first HCl
(acid) is take in beaker and base (NaOH) is taken in burette.
When base is added drop wise then acid-base reaction is occurs and following changes are
observed.
pH  0 to 7 is acidic. pH  7 is neutral
pH  7 to 14 is basic.
Initially, the graph increases steeply but when concerntration of acid becomes equal to base
then no change is seen in graph.
This point is called neutral point or equivalence point. Equivalence point, where pH = 7.
After the equivalence point (pH = 7, base (NaOH) is continuously mixed drop by drop then pH
increases by 7 and graph also increases slowly. At the point B solution become basic, again
base (NaOH) is mixed drop by drop and the solution becomes basic at point B. Following
inference can be seen in the graphs.
(1) According to this graph, pH = 7 is equivalence point and use of naOh (base) drop by drop
leads to basic solution as a result, value of pH increases slowly. This is correct option.
(2) According to graph, it shows straight line that mean graph increases instantly but this
titration show pH increases slowly because base (NaOH) is mix drop by drop.
(3) After equivalence point (pH = 7) graph is constant. It is wrong because graph increases
and the solution becomes pure basic then graph show constant value.
(4) According to graph, equivalence point (pH = 7) graph should increases but it decreases.
26. PbCl2(s) Pb2+(aq) + 2Cl–(aq); Ksp = 1.6 × 10–5

For mixture, 300 mL 0.134 M Pb(NO3)2 and 100 mL 0.4 M NaCl
After mixing, total volume = 400 m
[Pb2+] after mixing (before any precipitate forms)
300  0.134 3  0.134 1
  
400 4 10
[Cl–] after mixing (before any precipitate forms)
100  0.4
  0.1
400
As we know,
3  0.134
Q = [Pb2+] [Cl–]2 = × 10–2 = 10–3
4
27. The explanation of given statements are as follows:

In statement (I), millimoles of H+ = 400 × 0.1 × 2 = 80
Millimoles of OH– = 400 × 0.1 = 40 (Limiting reagent)

 Millimoles of H+ left = 80 – 40 = 40
40 40 1
[H+] =  M M
400  400 800 20
 1
 pH = –log[H+] = –log   
 20 
  = –log1 + log2 + log10
= –0 + 0.301 + 1  1.30
Hence, the option (1) is correct.
In statement (II), ionic product of H2O is temperature dependent.
Kw = [H+] [OH–]  10–14(mol/L)2 at 25°C
With increases in temperature, dissociation of H2O units into H+ and OH– ions will also
increase. As a result, the value of ionic product, [H+] × [OH–] will be increased. e.g.
Temperature Kw (mol/L2)
5°C 0.186 × 10–14
25°C 1.008 × 10–14
45°C 4.074 × 10–14
In statement (III), for a weak monobasic acid HA
HA H + A
(1 – ) CM CM
 pH of the solution is 5, i.e.
[H+] = 10–5 M = C
C  C 10 5  
 Ka = 
(1   )C 1 
10 5  
 10–5 =   = 0.5  a% = 50
1 
In statement (IV), Le-Chatelier's principle is applicable to common ion effect. Because, in
presence of common ion (given) by strong electrolyte (say, Na+ + A ), the product of the
concentration terms in RHS increases. For the weaker electrolyte, HA H + A.
As a result dissociation of HA gets suppressed.
Hence, the option (4) is incorrect.

CHEMISTRY

CPP
ST
REDOX REACTION NO. 06
Type : 1 (Oxidation state and oxidation number)

1. The oxidation states of iron atoms in compounds (A), (B) and (C), respectively, are x, y and z.
The sum of x, y and z is
Na4[Fe(CN)5(NOS)], Na4[FeO4], [Fe2(CO)9] [JEE Main 2020]
2. The oxidation states of transition metal atoms in K2Cr2O7, KMnO4 and K2FeO4, respectively,
are x,y and z. The sum of x, y and z is …………..
3. Oxidation number of potassium in K2O, K2O2 and KO2, respectively, is

(1) +1, +4 and +2 (2) +1, +2 and +4
1
(3) +1, +1 and +1 (4) +2, +1 and
2
4. The redox reaction among the following is

(1) reaction of H2SO4 with NaOH reaction of [Co(H2O)6]Cl3 with NaOH
(2) reaction of [Co(H2O)6]Cl3 with AgNO3
(3) combination of dinitrogen with dioxygen at 2000 K
(4) formation of ozone from atmospheric oxygen in the presence of sunlight
5. The compounds that cannot act both as oxidizing and reducting agent is
(1) H2SO3 (2) H3PO4 (3) HNO2 (4) H2O2
6. An example of a disproportionation reaction is
(1) 2MnO4 + 10 I– + 16H+2Mn2+ + 5I2 + 8H2O
(2) 2NaBr + Cl2  2NaCl + Br2

(3) 2KMnO4 K2MnO4 + MnO2 + O2
(4) 2CuBr CuBr2 + Cu
Type : 2 (Balancing redox reactions)
7. The reaction of sulphur in alkaline medium is the below:
 2 2
S8(s)  aOH(aq)  bS(aq)
  c S2O3(aq)  dH2O(  )
The values of ‘a’ is_______. (Integer answer) [JEE Main 2021]
–
8. 2MnO4 + b C2O42– + c H+  x Mn2+ + y CO2 + z H2O
If the above equation is balanced with integer coefficients, the value of c is _______ .
(Round off to the Nearest Integer)
9. Consider the following equations :
2Fe2+ + H2O2  xA + yB
(in basic medium)
2MnO4 + 6H+ + 5H2O2  x’C+y’ D + z’ E
(in acidic medium)
The sum of the stoichiometric coefficients x, y, x’, y’ and z’ for products A, B, C, D and E,
respectively, is ………
Type : 3 (Equivalent Concept)
10. In basic medium CrO42– oxidises S2O32– to form SO42– and itself changes into Cr(OH)4–. The
volume of 0.154 M CrO42– required to react with 40 mL of 0.25 M S2O32– is _______ mL.
(Rounded-off to the nearest integer)
[JEE Main 2021]
11. The exact volumes of 1 M NaOH solution required to neutralise 50 mL of 1 M H3PO3 solution
and 100 mL of 2 M H3PO2 solution, respectively, are :
(1) 100 mL and 100 mL
(2) 100 mL and 50 mL
(3) 100 mL and 200 mL
(4) 50 mL and 50 mL
12. 15 mL of aqueous solution of Fe2+ in acidic medium completely reacted with 20 mL of 0.03 M
aqueous Cr2O72–. The molarity of the Fe2+ solution is ____ × 10–2 M
13. In order to oxidise a mixture of one mole of each of FeC2O4, Fe2(C2O4)3, FeSO4 and Fe2(SO4)3
in acidic medium, the number of moles of KMnO4 required is.
(1) 2 (2) 1 (3) 3 (4) 1.5
14. 100 ml of a water sample contains 0.81 g of calcium bicarbonate and 0.73 g of magnesium
bicarbonate. The hardness of this water sample expressed in terms of equivalents
of CaCO3 is
(molar mass of calcium bicarbonate is 162 g mol-1 and magnesium bicarbonate is 146 g mol-1)
(1) 5,000 ppm (2) 1,000 ppm (3) 100 ppm (4) 10,000 ppm
Type : 4 (Titration)
N
15. 0.4 g mixture of NaOH, Na2CO3 and some inert impurities was first titrated with HCl using
10
phenolphthalein as an indicator, 17.5 mL of HCl was required at the end point. After this
methyl orange was added and titrated. 1.5 mL of same HCl was required for the next end
point. The weight percentage of Na2CO3 in the mixture is _______.
[JEE Main 2021]
16. Consider titration of NaOH solution versus 1.25M oxalic acid solution. At the end point
following burette readings were obtained.
(i) 4.5 mL (ii) 4.5 mL (iii) 4.4 mL (iv) 4.4 mL (v) 4.4 mL
If the volume of oxalic acid taken was 10.0 mL then the molarity of the NaOH solution is
_______M. (Rounded-off to the nearest integer)
17. 10.0 ml of Na2CO3 solution is titrated against 0.2 M HCl solution. The following titre values
were obtained in 5 readings.
4.8 ml, 4.9 ml, 5.0 ml and 5.0 ml
Based on these readings, and convention of titrimetric estimation of concentration of Na2CO3
solution is _______ mM.
(Round off to the Nearest integer)
18.  H3O+ + Cl– + O2

(A) HOCl + H2O2 
(B) I2 + H2O2 + 2OH– 

 2I– + 2H2O + O2
Choose the correct option.
(1) H2O2 acts as reducing and oxidising agent respectively in equation (A) and (B)
(2) H2O2 acts as oxidising agent in equation (A) and (B)
(3) H2O2 acts as reducing agent in equation (A) and (B)
(4) H2O2 act as oxidizing and reducing agent respectively in equation (A) and (B)
[JEE Main 2021]
19. Which of the following equation depicts the oxidizing nature of H2O2?
(1) KIO4 + H2O2  KIO3 + H2O + O2
(2) 2I– + H2O2 + 2H+  I2 + 2H2O + O2
(3) I2 + H2O2 + 2OH–  2I– + 2H2O + O2
(4) Cl2 + H2O2  2HCI + O2
ANSWER KEY
1. (6) 2. (19) 3. (3) 4. (3) 5. (2)
6. (4) 7. 12 8. (16) 9. (19) 10. (173)
11. (3) 12. (24) 13. (1) 14. (4) 15. (4)
16. (6) 17. (50) 18. (3) 19. (2)
SOLUTION
1. Na[Fe(CN)5NOS]  4 × (+1) + x + 5
×(–1) + (+1)+ (–2) = 0
x=+2
CN– S2–
NO+
y
Na4 [F eO4 ]  4(+1) + y + 4 × (–2) = 0
y=+4
[Fe2(CO)9]  2 × z + 9 × 0 = 0  z = 0
So, x + y + z = (+2) + (+4) + (0) = 6
x
2. K 2 Cr2O7  2(+1) + 2x + 7 × (–2) = 0  x = + 6
x
KMnO4  1 (+ 1) + x + 4 × (–2) = 0  y = + 7
x
K2FeO4  2 × (+ 1) + z + 4 × (–2) = 0
 z=+6
So, (x + y + z) = 6 + 7 + 6 = 19
3. Elements of group 1 (alkali metals) shown only one non-zero oxidation number, which is equal
to +1. K2O consists of K+ and O2– ions
K2O2 (potassium peroxide) consists of K+ and O22  ions. KO2 (potassium superoxide) consists
of K+ and O2 ions.

Thus, in all the given compounds potassium exhibits +1 oxidation state.
4. (1) The given reaction are as follows :

H2SO 4  2NaOH  Na2SO4  2H2O
( 6) ( 1) ( 1)( 6)
(No change in oxidation state, so not a redox reaction) .

(2) [Co(H2O)6 ]Cl3  3 AgNO3 [Co(H2O)](NO3 )3  3AgCl 
( 3) ( 1) ( 3) ( 1)
(No change in oxidation state, so not a redox reduction).

200 K
(3) N2  O2   2N O
(0) (0) ( 2) ( 2)
(N2 oxidised from 0 to +2 oxidation state and O2 reduced from 0 to –2 oxidation state).

(4) 3O2  2O3
h
(0) (0)
(No change in oxidation state, so not a redox reaction).
5. In H3PO4. P is in its highest oxidation state(+5), I can only act as oxidising agent but not as
reducing agents, because it can be reduced but not oxidized.
H2SO3 : S = +4 can ge oxidized or reduced.
HNO2 : N = + 3 can ge oxidized or reduced.
H2O2 : O = – 1 can get oxidized or reduced
6. In disproportionation reactions, same element undergoes oxidation as well as reduction.

e.g.
Reduction
+1 +2 0
2CuBr CuBr2 + Cu
Oxidation
Here, CuBr get oxidised to CuBr2 and also it get reduced to Cu. other given reactions and
their types are given below.
Reduction
+7
2 MnO4 + 10I– + 16H+ 2Mn+2 + 5I2 + 8H2O
Oxidation
In the given reaction, MnO4 get oxidised to Mn2+ and I– get reduced to I2. It is an example of
redox reaction. The reaction takes place in acidic medium.
2KMnO4 K2MnO4 + MnO2 + O2
The given reaction is an example of decomposition reaction, Here, one compound split into
two or more simpler compounds, atleast one of which must be in elemental form.
2NaBr + Cl2  2NaCl + Br2
The given reaction is an example of displacement reaction. In this reaction, an atom (or ion)
replaces the ion (or atom) of another element from a compound.
7.  8S2–
16e + S8 
 4S2O32– + 24H+ + 16e

12H2O + S8 
_____________________________________
 8S2– + 4S2O32– + 24H+
2S8 + 12H2O 
for balancing in basic medium add equal number of OH! that of H+
 8S2– + 4S2O82– + 24H2O
2S8 + 12H2O + 24OH 
 8S2– + 4S2O82– + 12H2O
2S8 + 24OH 
 4S2– + 2S2O82– + 6H2O
S8 + 12OH 
a = 12
8. Writing the half reaction oxidation half reaction

MnO4–  Mn2+
balancing oxygen
MnO4–  Mn2+ + 4H2O
balancing Hydrogen
8H+ + MnO4–  Mn2+ + 4H2O
balancing charge
5e– + 8H+ + MnO4–  Mn2+ + 4H2O
Reducing half
C2O42–  CO2
Balancing charge
C2O42–  2CO2 + 2e–
Net equation
16H+ + 2MnO4– + 5C2O42–  10CO2 + 2Mn2+ + 8H2O
So c = 16
9. In basic medium
[Fe2+  Fe3+ + e–] × 2
H2O2 + 2e–  2HO–
2Fe2+ + H2O2  2Fe3  2HO
( A) (B)
Hence, x = 2 and y = 2
In acidic medium
[8H+ + MnO4 + 5e–  Mn2+ + 4H2O] × 2
[H2O2  O2(g) + 2H+ + 2e–] × 5
16H+ + 2MnO4 + 5H2O2  2Mn2 + 8H2O 5O2 (g)
(C) (D) (E)
So, x’ = 2, y’ = 8, z’ = 5
So, x + y + x’ + y’ + z’
 2 + 2 + 2 + 8 + 5  19
6 2 6 3
10. CrO24  S2O32 
 SO42  Cr(OH)4
gm equi. of CrO42– = S2O32–
0.154 × 3 × v = 0.25 × 40 × 8
v = 173.16 = 173 ml
11. H3PO3 + 2NaOH  Na2HPO3 + 2H2O

50 ml 1M
1M V=?
nNaOH 2
 
nH3PO3 1
1 V 2
   VNaOH  100ml
50  1 1
H3PO2 + 2NaOH  NaH2PO3 + H2O

100 ml 1M
2M V=?
nNaOH 1 1 V 1
     VNaOH  200ml
nH3PO3 1 2  100 2
12. neq Fe2+ = neq Cr2O72+

 15  MFe2    20  0.03 
or,   1  6
 1000   1000 
 MFe = 0.24 M = 24 × 10–2 M

2
13. The oxidation of a mixture of one mole of each of

FeC2O4, Fe2(C2O4)3FeSO4 and
Fe2(SO4)3 in acidic medium with KMnO4 is as follows
FeC2O4 + KMnO4 → Fe3++CO2 + Mn2+ …… (i)
Fe2(C2O4)3 + KMnO4 → Fe3++CO2 + Mn2+ …… (ii)
3+ 2- 2+
FeSO4+ KMnO4 → Fe + SO 4+ Mn …… (iii)
Change in oxidation number of Mn is 5. Change in oxidation number of Fe in (i), (ii) and (iii)
are +3,+6,+1, respectively
neqKMnO4 = neq[FeC2O4 + Fe2(C2O4)3 + FeSO4]
n×5 = 1×3+1×6+1×1
n=2
14. Given, WCa(HCO3 )2  0.81g
WMg(HCO3 )2  0.73g
MCa(HCO3 )2  162 gmol–1
MMg(HCO3 )2  146 gmol–1
MH2O= 100 ml
Now, neq(CaCO3) = neq[Ca(HCO3)2] + neq[Mg(HCO3)2]
W 0.81 0.73
2 2 2
100 162 146
W
   0.005  0.005 
100
   W = 0.01 × 100 = 1
1
Thus, hardness of water sample =  106
100
= 10,000 ppm
15. Upto first end point
gm equi. of (NaOH + Na2CO3) = HCl
1
x+y×1=  17.5
10
x + y = 1.75 …(1)
Upto second end point
NaOH + Na2CO3  HCl
1
x+y×2=  19
10
x + 2y = 1.9 …(2)
y = 0.15
0.15  10 3
%Na2CO3   100
0.4
= 3.975%
= 4%
Hence answer is (4)
16. VNaOH = 4.4 ml

eq. of NaOH = eq. of H2C2O4
or, M × 4.4 × 1 = 1.25 × 10 × 2
or, M = 5.68 M
 Nearest integer answer is 6
17. Most precise volume of HCl = 5 ml at equivalence point

Meq. Of N2CO3 = meq. Of HCl.
Let molarity of Na2CO3
Solution = M, then
M × 10 × 2 = 0.2 × 5 × 1
M = 0.05 mol / L
= 0.05 × 1000 = 50 Mm
18.  H3O+ + Cl– + O2

(A) HOCl + H2O2 
In this equation, H2O2 is reducing chlorine from +1 to –1.
(B) I2 + H2O2 + 2OH– 
 2I– + 2H2O + O2
In this equation, H2O2 is reducing iodine from 0 to –1.
In (A) reduction of HOCl occurs so it will be a oxidising agent hence H2O2 will be a reducing
agent.
In(B) reduction of I2 occurs so it will be a oxidising agent and H2O2 will be a reducing agent.
19. I– is oxidised to I2 by H2O2. Hence answer is (2)
CHEMISTRY

CPP
ST
THERMODYNAMICS NO. 07
Type : 1 (F.L.O.T. (First law Thermodynamics)

1. Five moles of an ideal gas at 293 K is expanded isothermally from an initial pressure of 2.1
MPa to 1.3 MPa against a constant external pressure 4.3 MPa. The heat transferred in this
process is _______ kJ mol–1. (Rounded-off to the nearest integer) [Use R = 8.314 J mol–1 K–1]
[JEE Main 2021]
2. At 25ºC, 50 g of iron reacts with HCl to form FeCl2. The evolved hydrogen gas expands
against a constant pressure of 1 bar. The work done by the gas during this expansion is
_______ J. (Round off to the Nearest Integer)
[Given : R = 8.314 J mol–1 K–1. Assume, hydrogen is an ideal gas]
[Atomic mass off Fe is 55.85 u]
3. Five moles of an ideal gas at 1 bar and 298 K is expanded into vacuum to double the volume.
The work done is
(1) –RT 1n V2 / V1 (2) –RT(V2–V1) (3) Cv(T2 – T1) (4) zero
4. The magnitude of work done by a gas that undergoes a reversible expansion along the path
ABC shown in the figure is ……. .
Pressure
(Pa) 10
8 B
6
4
C
(2,2) 4 6 8 10 12 Volume
(m3)
5. At constant volume, 4 mol of an ideal gas when heated from 300 K to 500 K changes its
internal energy by 500 J. The molar heat capacity at constant volume is ………..

6. Which one of the following equations does not correctly represent the first law of
thermodynamics for the given processes involving an ideal gas ? (Assuming non-expansion
work is zero)
(1) Cyclic process : q = – W (2) Adiabatic process : U = – W
(3) Isochoric process : U = q (4) Isothermal process : q = – W
7. 5 moles of an ideal gas at 100 K are allowed to undergo reversible compression till its
temperature becomes 200 K. If CV = 28 JK–1 mol–1, calculate U and pV for this process
(R = 8.0 JK–1 mol–1)
(1) U = 2.8 kJ ; (pV) = 0.8 kJ (2) U = 14 J ; (pV) = 0.8 J
(3) U = 14 kJ ; (pV) = 4 kJ (4) U = 14 kJ ; (pV) = 18 kJ
8. Among the following the set of parameters that represents path functions, is
(A) q + W (B) q (C) W (D) H – TS
(1) (A) and (D) (2) (A), (B) and (C)
(3) (B), (C) and (D) (4) (B) and (C)
9. An ideal gas is allowed to expand from 1 L to 10 L against a constant external pressure of

1 bar. The work done in kJ is
(1) –90 (2) +10.0 (3) –0.9 (4) –2.0
10. Consider the reversible isothermal expansion of an ideal gas in a closed system at two
different temperatures T1 and T2 (T1 < T2). The correct graphical depiction of the dependence
of work done (W) on the final volume (V) is
|W| T2 |W| T2 |W| T2 |W| T2
T1 T1
T1 T1
(1) (2) (3) (4)
O ln V O ln V O ln V O ln V
11. An ideal gas undergoes isothermal compression from 5 m3 to 1 m3 against a constant external
pressure of 4 Nm–2. Heat released in this process is used to increase the temperature of 1 mol
of Al. If molar heat capacity of Al is 24 J mol–1 K–1, the temperature of Al increases by
3 2
(1) K (2) 1K (3) 2K (4) K
2 3

12. The combination of plots which does not represent isothermal expansion of an ideal gas is
pVm
p p U
(1) (2) (3) (4)
O 1/Vm O Vm O p O Vm
(A) (A) (C) (D)
Type : 2 (Second law of Thermodynamics)

13. During which of the following processes, does entropy decrease ?
(A) Freezing of water to ice at 0ºC (B) Freezing of water to ice at –10ºC
(C) N2(g) + 3H2(g)  2NH3(g) (D) Adsorption of CO(g) and lead surface
(E) Dissolution of NaCl in water
(1) (A), (B), (C) and (D) only (2) (B) and (C) only
(3) (A) and (E) only (4) (A), (C) and (E) only [JEE Main 2021]
14. The true statement amongst the following is

(1) S is not a function of temperature but S is a function of temperature.
(2) Both S and S are functions of temperature.
(3) Both S and S are not functions of temperature.
(4) S is a function of temperature but S is not a function of temperature.
15. The entropy change associated with the conversion of 1 kg of ice at 273 K to water vapours at
383 K is (Specific heat of water liquid and water vapour are 4.2 kJK–1 kg–1 and 2.0 kJK–1 kg–1;
heat of liquid fusion and vapourisation of water are 334 kJ kg–1 and 2491 kJkg–1 respectively).
16. The process with negative entropy change is

(1) synthesis of ammonia from N2 and H2
(2) dissociation of CaSO4(s) to CaO(s) and SO3(g)
(3) dissolution of iodine in water
(4) sublimation of dry ice
17. Two blocks of the same metal having same mass and at temperature T1 and T2 respectively,
are brought in contact with each other and allowed to attain thermal equilibrium at constant
pressure. The change in entropy, S, for this process is
1
 
 (T1  T2 ) 2
  (T1  T2 )   (T1  T2 ) 2   T1  T2 
(1) Cp ln  (2) Cp ln   (3) Cp ln   (4) Cp ln  
T1T2   4T1T2   4T1T2   2T1T2 
 

Type : 3 (Gibbs Free Energy)
18. For a chemical reaction A + B C + D (rH0 = 80kJ mol–1) the entropy change rS0
depends on the temperature T (in K) as (rS0 = 2T (J K–1 mol–1).
Minimum temperature at which it will become spontaneous is ______K.(Integer)
[JEE Main 2021]
19. For a dimersiation reaction

2A(g)  A2(g),
At 298 K, UΘ = – 20 kJ mol–1,
SΘ = – 30JK–1 mol–1, then the GΘ will be………….. J.
20. For a reaction,

4 M(s) + nO2(g)  2M2On(s)
The free energy change is plotted as a function of temperature. The temperature below which
the oxide is stable could be inferred from the plot as the point at which
Less –ve
fGº
More –ve
T
(1) the slope changes from negative to positive

(2) the free energy change shows a change from negative to positive value
(3) the slope changes from positive to negative
(4) the slope changes from positive to zero
21. For the reaction ; A(l)  2B(g)

U = 2.1 kcal, S = 20 cal K–1 at 300 K.
Hence, G in kcal is …………
22. A process will be spontaneous at all temperature if

(1) H > 0 and S < 0 (2) H < 0 and S > 0
(3) H < 0 and S < 0 (4) H > 0 and S > 0

23. The incorrect match in the following is
(1) Gº < 0, K > 1 (2) Gº = 0, K = 1 (3) Gº > 0, K < 1 (4) Gº < 0, K < 1
24. A process has H = 200 J mol–1 and S = 40 JK–1 mol–1. Out of the values given below,
choose the minimum temperature above which the process will be spontaneous
(1) 20 K (2) 4 K (3) 5 K (4) 12 K
25. For the chemical reaction, X Y, the standard reaction Gibbs energy depends on
3
temperature T (in K) as, rGº (ln kJ mol–1) = 120 – T
8
The major component of the reaction mixture at T is
(1) Y if T = 280 K (2) X if T = 350 K (3) X if T = 315 K (4) Y if T = 300 K
26. The reaction MgO(s) + C(s)  Mg(s) + CO(g), for which rHº = + 491.1 kJ mol–1 and
rSº = 198.0 JK–1 mol–1, is not feasible at 298 K. Temperature above which reaction will be
feasible is
(1) 2040.5 K (2) 1890.0 K (3) 2380.5 K (4) 2480.3 K
27. The standard reaction Gibbs energy for a chemical reaction at an absolute temperature T is
given by, rGº = A – BT
Where A and B are non-zero constants.
Which of the following is true about this reactions ?
(1) Endothermic if, A < 0 and B > 0 (2) Exothermic if, B < 0
(3) Exothermic if, A > 0 and B < 0 (4) Endothermic if, A > 0
28. For one mole of an ideal gas, which of these statements must be true ?
(A) U and H each depends only on temperature.
(B) Compressibility factor Z is not equal to 1.
(C) Cp,m – Cv,m = R
(D) dU = CvdT for any process [JEE Main 2020]
(1) (B), (C) and (D) (2) (A) and (D) (3) (A), (C) and (D) (4) (C) and (D)
29. For silver, Cp(J K–1 mol–1) = 23 + 0.01 T. If the temperature (T) of 3 moles of silver is raised
from 300 K to 1000 K at 1 atm pressure, the value of H will be close to
(1) 62 kJ (2) 16 kJ (3) 21 kJ (4) 13 Kj

ANSWER KEY
1. (15) 2. 2218 3. (4) 4. 48 5. 6.25
6. (2) 7. (3) 8. (4) 9. (3) 10. (3)
11. (4) 12. (3) 13. (1) 14. (2) 15. (1)
16. (1) 17. (3) 18. (200) 19. (–13537.57) 20. (2)
21. –2.70 22. (2) 23. (4) 24. (3) 25. (3)
26. (4) 27. (4) 28. (3) 29. (1)
SOLUTIONS
1. n = 5, T = 293 K = const, U = 0,
P1 = 2.1 MPa, P2 = 1.3 MPa
Pext = 4.3 MPa = const.
 nRT nRT 
W = –Pext (V2 – V1) = –Pext   
 2P P1 
 1 1
or, W = –Pext nRT   
 P2 P1 
 1 1 
= –4.3 × 5 × 8.314 × 293   
 1.3 2.1 
 2.1  1.3 
= –4.3 × 5 × 8.314 × 293  
 1.3  2.1 
= –15347.7J
or, W = –15.35 kJ
U0 = q + W
 q = –W
or, q = 15.35 kJ (for 5 moles)
15.35
 q/mole = = 3kJmol–1
5
J
2. T = 298 K, R = 8.314
molK
 Chemical reaction is
Fe + 2HCl  FeCl2 + H2(g)
50 g P = 1 bar

50
 mol
55.85
50
 mol
55.85
 Work done for 1 mol gas
= –Pext × V
= ng RT
= –1 × 8.314 × 298 J
50
 Work done for J mol of gas
55.85
50
= –1.8314 × 298 × J
55.85
= –2218.059 J
= –2218 J
3. Expansion of a gas in vacuum (pext = 0) is called free expansion, No work is done during free
expansion, since as the expansion is done in vacuum that is in absence of external pressure,
hence w will be
W = – pext V  w = 0
(Here, pext = 0), because expansion takes place in vacuum
4. Work done is equal to the area under pV-curve.
1
 work done (|W|) = (6 + 10) × 6
2
= 48.00 Pa. m3 = 48.00 J.
5. n = 4 mol
T = 500 J – 300 K = 200 K
U = 5000 J
U = nCvT
U 5000 50
Cv =    6.25
nT 4  200 8
6. From the 2st law of thermodynamics,

U = q + W
Where, U = change in internal energy
q = heat, W = work done
The above equation can be represented for the given processes involving ideal gas as follows :

(1) Cyclic process For cyclic process, U = 0
 q=–W
Thus, option (a) is correct.
(2) Adiabatic process For adiabatic process,
q = 0  U = W
Thus, option (b) is incorrect.
(3) Isochoric process For isochoric process,
V = 0. Thus, W = 0 (W = pV).
 V = q
Thus, option (c) is correct.
(4) Isothermal process For isothermal process,
U = 0
 q=–W
Thus, option (d) is correct.
7. Given, n = 5 mol, T2 = 200 K, T1 = 100 K

CV = 28 JK+ mol–1
U = nCVT = nCV(T2 – T1)
= 5 mol × 28 JK–1 mol–1 × (200 – 100) K
= 14000 J = 14 kJ
pV = nRT = nR(T2 – T1)
= 5 mol × 8 JK–1 mol–1 × (200 – 100) K
= 4000 J = 4 kJ
8. q (heat) and W (work) represents path functions. These variables are path dependent and
their values depends upon the path followed by the system in attaining that state. They are
inexact differentials whose integration gives a total quantity depending upon the path.
Option (1), i.e. q + W and option (4), i.e. H-TS are state functions. The value of state function
is independent to the way in which the state is attained. All the state functions are exact
differentials and cyclic integration involving a state function is zero.
9. Work done during isothermal expansion of an ideal gas is given by the equation.
W = –pext(V2 – V1)

According to the given conditions, the expansion is against constant external pressure. So,
the work done is given by following formula.
W = –Pext(V2 – V1)
= –1 bar (10L – 1L) = –9 L bar ( 1L bar = 100 J)
= – 9 × 100 J = –0.9 kJ
10. For isothermal reversible expansion.

Vf V
| W | nRT ln  nRT ln
Vi Vi
Where, V = final volume, Vi = initial final.

Or |W| = nRt ln V – nRT ln Vi
On comparing with equation of straight line,
Y = mx + c, we get
slope = m = + nRT
intercept = – nRT ln Vi
Thus, plot of |W| with ln V will give straight line in which slope of 2(T2) is greater than slope of
1(T1) which is given in all options.
Now, it Vi < 1 then y intercept (–nRT Vi) becomes positive and if it is positive for one case then
it is positive for other case also. Thus, it is not possible that one y-intercept goes above and
other y-intercept goes below. Thus, option (b) and 9d) are incorrect.
If we extent plot given in option (a) it seems to be merging which is not possible because if
they are merging they give same +ve y-intercept. But they cannot give same y-intercept
because value of T is different.
Now, if we extent the line of T1 and T2 given in option (c) it seems to be touching the origin. If
they touch the origin then y-intercept becomes zero which is not possible. Thus, it is not the
exactly correct answer but among the given options it is the most appropriate one.
11. It is an irreversible isothermal compression of an ideal gas.

(i) dE = dq + p(Vf – Vi)
Where, dE = Internal energy change
Dq = amount of heat released
0 = dq + p(Vf – Vi)
[ dE = 0 for an isothermal process]
 dq = – 4(1 – 5) = 16 J
(ii) dq = n × C × T (for Al)

 16 J = 1 mol × 24 J mol–1 K–1 × T
16 2
 T  K K
24 3
12. In isothermal expansion, pVm = K (constant)
This relation is plotted in graph 'C'
K
Likewise, p 
Vm
This relation is plotted in graph "A" Thus, graph B and D are incorrect.
For them the correct graphs are :
p and U
Vm Vm
for graph B for graph D
0ºC
13. (A) Water   ice ; S = –ve
(B) N2(g) + 3H2(g)  2NH3(g) ; S = –ve

(D) Adsorption ; S = –ve
(E) NaCl(s)  Na+(aq) + Cl–(aq) ; S = +ve
14. Statement (b) is a true statement whereas all other statements are incorrect.
By definition.
dQ  dQ
dS  and S 
T T
 S is a function of temperature :
S is also a function of temperature.
15. The conversion of 1 kg of ice at 273 K into water vapours at 383 K takes place as follows :
S1 S2
H2O(s) H2O(l) H2O(l)
273K 273K 373K
S3
H2O(g) S4
H2O(g)
383K 373K
HFusion 334kJkg1
S1    1.22kg1K 1
TFusion 273K
T2  373K 
S2  Cln 4.2kJK 1kg1 ln  
T1  273K 

= 4.2 × 2.303 (log 373 – log 273) kJ
K kg–1 = 4.2 × 2.303 (2.572 – 2.436)
–1
= 1.31 kJ K–1kg–1
Hvap. 2491 kJkg1
S3    6.67kJkg1K 1
Tvap. 373K
T2  383K 
S4  C ln  2kJK 1kg1 ln  
T1  373K 
= 2 × 2.303 (log 383 – log 373) kJ K–1 kg–1

= 2 × 2.303 (2.583 – 2.572) kJ K–1 kg–1
= 0.05 kJ K–1 kg–1
STotal = S1 + S2 + S3 + S4
= 1.22 + 1.31 + 6.67 + 0.05
= 9.26 kJ kg–1 K–1
16. The explanation of all the options are as follows :
(1) N2(g) + 3H2(g)  2NH3(g),
ng = 2 – (1 + 3) = – 2
So, S is also negative (entropy decreases)

(2) CaSO4(s)   CaO(s) + SO3(g),
ng = (1 + 0) – 0 = + 1
So, S = + ve
(3) In dissolution, S = +ve because molecules/ions of the solid solute (here, iodine)
become free to move insolvated/dissolved state of the solution,
CO2 (s)  CO2 (g)
Dry ice
So, S will be positive.
17. At the thermal equilibrium,

T1  T2
Final temperature Tf 
2
Tf
 for the 1st block, SI = CPln
T1
Tf
 for the 2nd block, SII = CP ln
T2
When brought in contact with each other,

Tf T
S = SI + SII = CP ln  CP ln f
T1 T2

 Tf Tf   T2 
= CP ln     CP ln  f 
 T1 T2   T1T2 
  T1  T2  2 
 
2    (T  T2 )2 
= CP ln    CP ln  1 
 T1T2   4T1T2 
 
 
18. G0 = H0 – T × S0

G0 = H0 – T × (2T)
T = 200K
19. H = U + ngRT
H = – 20 × 1000 – 1 × 8.314 J/mol. K × 298 K
= – 22477.572 J
G = H – TS
G = – 22477.572 + 298 × 30
G = – 13537.57 Joule
20. Ellingham diagram usually consists of plots of fGΘ vs T for the formation of oxide of various
elements.
For the reaction,
4M(s) + nO2(g)  2M2On(s)
Free energy change plot as a function of temperature is as follows :
Less –ve
fGº
More –ve
T
In this reaction, O2 (a gas) is used up and M2On(s), a solid is formed, Since, gases have
higher entropy than solids, S becomes negative. Thus, on increasing the temperature,
TrSΘ becomes more negatie, hence fGΘ becomes less negative which is shown infigure.
The slope of the curves for the formation of metal oxides is positive as fGΘ becomes less
negative. Any metal oxide having lower value of fGΘ is more stable as compared to metal
oxide with higher value of fGΘ.

From the graph it is evident, that the temperature below which the oxide is stable, is the point
at which free energy change shows a change from negative to positive
21. Given U = 2.1 kcal
20
S = 20 cal K–1 = kcal K–1
1000
A(l) 2B(g)
 ng = 2 mol
R = 2 cal K–1 mol–1
2
= kcal–1 mol–1
1000
As we know,
G = H – TS and H = U + ngRT
 G = U + ngRT – TS
2  2  300 300  20
 G = 2.1 + 
1000 1000
= 2.1 + 1.2 – 6 = – 2.70
22. A process will be spontaneous when its free energy (Gibb’s energy) change will be negative,
i.e. G < 0. Spontaneity of a process is decided by the value of G, which can be predicted
from the Gibb’s equation, G = H – TS for positive/negative signs of H and S at
any/higher/lower temperature as :
H S Comment on temperature (T) G Comment on the process

  at any temp.  Spontaneous
  At any temp.  Non-spontaneous
  At lower temp.  Spontaneous
  at higher temp.  spontaneous
23. The incorrect match is Gº < 0, K < 1.

For an ideal gas Gº = – RTlnK.
Gº
 ln K = – and K = e–DGº/RT
RT
The above equation is helpful in predicting the spontaneity of the reaction e.g.
(i) If Gº < 0, –Gº/RT = + ve
and e–Gº/RT > 1 and hence, K > 1

It means that the reaction occur spontaneously in the forward director or products
predominate over reactants.
(ii) If Gº > 0; – Gº/RT = – ve and e–Gº/RT < 1 and hence, K < 1. It means that the
reaction is non-spontaneous in forward direction (i.e. product side) but spontaneous in reverse
direction (i.e. reactatns predominate over products or the reaction occurs rarely).
(iii) When K = 1, then Gº = 0. This situation generally occur at equilibrium.
24. G = H – TS
The process will be spontaneous, when
G = – ve. i.e. |TS| > |H|
Given : H = 200 J mol–1
and S = 40 JK–1 mol–1
| H | 200
 T   5K
| S | 40
So, the minimum temperature for spontaneity of the process is 5 K.

25. For a given value of T.
(i) If rGº becomes < 0, the forward direction will be spontaneous and then the major and
minor components will be Y and X respectively.
(ii) If rGº becomes > 0, the forward direction will be non-spontaneous and then the major
and minor components will be X and Y respectively.
3
(1) rGº = 120 –
8
i.e. rGº > O 0, major component = X;

3
(2) rGº = 120 – × 350 = – 11.25
8
i.e. rGº < 0, major component = Y

3
(3) rGº = 120 – × 315 = 1.875
8
i.e. rGº > 0, major component = X

3
(4) rGº = 120 – × 300 = 7.5
8
i.e. rGº > 0 major component = X
26. According to Gibbs-Helmholtz equation,

rGº = rHº – TrSº
For a reaction to be feasible (spontaneous)

rGº < 0
rHº – TrSº < 0
Given rHº = + 491.1 kJ mol–1,
rSº = 198 JK+ mol–1
 491.1 × 103 – T × 198 < 0
491.  103
T  2480.3K
198
 Above 2480.3 K reaction will become spontaneous
27. According to Gibb’s Helmohtz, equation,

rGº = rHº – TrSº
Given rGº = A – BT
On comparing above two equations, we get,
A = Hº and Sº = B
We know that, if Hº is negative, reaction is exothermic and when it is positive, reaction is
endothermic.
 If A > 0, i.e. positive, reaction is endothermic.
28. Statement (A), (C) and (D) are true whereas (B) is false.
(A) For 1 mole, U = internal energy and H = enthalpy. Heat capacity at constant volume.
dU
nC v 
dt
dU  nCv dT (n = 1 mol)
dU = 1 × Cv × dt ( Cv = constant)
U = f(T) (Function of temperature)

U depends on temperature.
Heat capacity at constant volume.
dH
nCp = dT
dH = nCpdT (n = 1 mol)
dH = 1 × Cp × dT
In mathematically term,
H = f(T) [ Cp = constant]
Hence, H depends on function of temperature

(b) Compressibility factor (Z) describe the deviation of real gas from ideal gas behaviour.

pV
Z
RT ...(i)
For ideal gas, pV = nRT [n = 1 mol]
pV = RT ...(ii)
Put in the value of pV from eq. (ii) to Eq. (i)
RT
Z 1
RT
Compressibility factor is 1 for ideal gas then option (b) is incorrect.
(c) For ideal gas.
Cp – Cv = nR [n = 1 mol]
Cp – Cv = R
It is correct statement.
dU
(d) U = CvdT  nCv = dT
dU = nCvdT (n = 1 mol)
dU = CvdT
It is also correct.
29. According to Kirchoff’s relation,
T2
H  n  Cp dT …(i)
T1
Where H = Change in enthalpy

Cp = Heat capacity at constant pressure.
Give, n = 3 moles, T1 = 300 K, T2 = 1000 K,
Cp = 23 + 0.01 T
On substituting the given values in Eq. (i), we get
1000 1000
H  3  (23  0.01T)dT  3  23dT  0.01T dT

300 300
1000
 0.01T 2 
 3 23T 
 2 300
 0.01 
 3  23(1000  300)  (1000 2  300 2 ) 
 2 
= 3[16100 + 4550] = 61950 J  62 kJ

CHEMISTRY

CPP
ST
THERMOCHEMISTRY NO. 08
Type : 1 (Bomb Calorimeter)

1. The reaction of cyanamide, NH2CN(s) with oxygen was run in a bomb calorimeter and U was
found to be –742.24 kJ mol–1. The magnitude of H298 for the reaction,
3
NH2CN(s) + O2(g) 
 N2(g) + O2(g) + H2O(l) is _______ kJ. (Rounded off to the nearest
2
integer) [Assume ideal gases and R = 8.314 J mol–1 K–1]
[JEE Main 2021]
Type : 2 (Various Heat of Reactions)
2. The standard enthalpies of formation of Al2O3 and CaO are –1675 kJ mol–1 and –635 kJ mol–1
For the reaction
3 CaO + 2Al  3Ca + Al2O3 the standard reaction enthalpy rH0 = _______ kJ.
[JEE Main 2021]
3. For the reaction

C2H6  C2H4 + H2
The reaction enthalpy rH = _____ kJ mol–1.
[Given : Bond enthalpies in kJ mol–1 : C–C : 347, C=C : 611 ; C–H : 414, H–H : 436]
4. The standard heat of formation (fH0298 ) of ethane (in kJ/mol), if the heat of combustion of
ethane, hydrogen and graphite are –1560, –393.5 and –286 kJ / mol, respectively is .......
5. The heat of combustion of ethanol into carbon dioxides and water is –327 kcal at constant
pressure. The heat evolved (in cal) at constant volume and 27ºC (if all gases behave ideally)
is (R = 2 cal mol–1 K–1)…………

6. The internal energy change (in J) when 90 g of water undergoes complete evaporation at
100ºC is ...... (Given : Hvap for water at 373 K = 41kJ / mol, R = 8.314 JK–1 mol–1)
7. The difference between H and U (H – U), when the combustion of one mole of heptanes
(l) is carried ou at a temperature T, is equal to
(1) –4 RT (2) 3 RT (3) 4 RT (4) –3 RT
8. Given :
(i) C(graphite) + O2(g)  CO2(g); rHΘ = x kJ mol–1
1
(ii) C(graphite) + O2(g)  CO(g) ; rHΘ = y kJ mol–1
2
1
(iii) CO(g) + O2(g)  CO2(g); rHΘ = z kJ mol–1
2
Bases on the above thermochemical equations, find out which one of the following algebraic
relationships is correct ?
(1) y = 2z – z (2) x = y – Z (3) z = x + y (4) x = y + z
Type : 3 (Various kind of bond Enthalpy)
9. The average S–F bond energy in kJ mol–1 of SF6 is ______. (Rounded off to the nearest
integer) [Given: The values of standard enthalpy of formation of SF6(g), S(g) and F(g) are
–1100, 275 and 80 kJ mol–1 respectively.] [JEE Main 2021]
10. Enthalpy of sublimation of iodine is 24 cl g–1 at 200ºC. If specific heat of I2(s) and I2(vap.) are
0.055 and 0.031 cal g–1 K–1 respectively, then enthalpy of sublimation of iodine at 250ºC in cal
g–1 is
(1) 2.85 (2) 5.7 (3) 22.8 (4) 11.4
Type : 4 (Hess Law)

11. The ionization enthalpy of Na+ formation from Na(g) is 495.8 kJ mol–1, while the electron gain
enthalpy of Br is –325.0 kJ mol–1. Given the lattice enthalpy of NaBr is –728.4 kJ mol–1. The
energy for the formation of NaBr ionic solid is (–) _______ × 10–1 kJ mol–1.
[JEE Main 2021]

ANSWER KEY
1. (741) 2. (230) 3. (128) 4. (–192.50)
5. (–326400) 6. (189494) 7. (1) 8. (4) 9. (309)
10. (3) 11. (5576)
SOLUTIONS
1. H = U + ngRT
1 8.314
= –742.24 +   298
2 1000
= –741 kJ/mol
2. Given reaction :
3CaO + Al  Al2O3 + 3Ca
Now, rHº =  fHºproducts – fHºReactions
= [1 × (–1675) + 3 × 0] – [3 × (–635) + 2 × 0]
= + 230 kJ mol–1
3. rH = [CC 2 ]  [CC  HH ]

C H
= [347 + 2 × 414] – [611 + 436] = 128
4. fHº of ethane is Hº of the reaction :

2C(graphite) + 3 H2(g)  C2H6(g)
From CHº (heat of combustion) values,
fHº = (2 × CHº graphite + (3 × CHº of H2) – C Hº of C2H6)
= (–2 × 286) + (–393.5 × 3) – (–1560) kJ mol–1
= –192.50 kJ mol–1
5. The combustion equation of ethanol (C2H5OH or C2H6O is C2H6O) is

6 1 6
C2H6O(l) +  2    O2(g) 
300K
 2CO2(g) + H2O(l)
 6 2 2
Or C2H6O(l) + 3O2(g)  2CO2(g) + 3H2O(l)

ng = (2 + 0) – (0 + 3) = – 1
 dqp = duv + ngRT
 duv = dqp + ngRT
= –327 – (–1) × (2 × 10–3) × 300
= –326.400 kcal = –326400 cal
 dqp = Heat at constant pressure of enthalpy of change duv = Heat at constant volume or
internal energy change
6. Give, dH = 41 kJ/mol = 41 × 1000 × 5J [For 90 g or 5 mol H2O(l)]

H2O(I)  H2O(g)
90
t=0 mol –
18
t= 0 5 mol
 ng = 5  T = 373 K
We know that ,
dH = dU + ng RT
dU = Internal energy change
= dH – ng RT
= 41 × 1000 × 5 – 5 × 8.314 × 373
= 189494.39 J  189494.00 J
7. Key Idea he relation between H and U is

H = U + ngRT
Where, ng = np – nR
= number of moles of gaseous products – number of moles of gaseous reactants.
The general combustion reaction of a hydrocarbon is as follows :
 y y
C xHy   x   O2  xCO2  H2O
 4 2
For heptanes, x = 7, y = 16
 C7H16(l) + 11O2(g)  7CO2(g) + 8H2O(l)
 ng = 7 – 11 = – 4
Now, from the principle of thermochemistry,
H = U + ngRT
 H – U = ngRT = –4RT

8. Second equation given in this question is wrong. Hence, No answer in correct. If corrected
second equation is given, i.e.
1
C(graphite) + O2(g)  CO(g)
2
And if we take the above reaction in consideration then x = y + z will be the answer as :
1
(ii) C(graphite) + O2(g)  CO(g), rHº = y kJ/mol
2
1
(iii) CO(g) + O2(g)  CO2(g), rHº = z kJ/mol
2
Summing up both the equation you will get equation (i) C(graphite) + O2(g)  CO2(g), rHº = x
kJ/mol
Hence, x, y and z are related as :
x=y+z
9. SF6(g)  S(g) + 6F(g)

If  - bond enthalpy
rH = 6 S F
= fH(S,g) + 6 × fH(F,g) – fH(SF6,g)

= 275 + 6 × 80 – (–1100)
= 1855 kJ
1855
S–F = = 309.16 kJ/mol.
6
10. Key Idea When q is the amount of heat involved in a system then at constant pressure
q = qp and CpT = H
Given reaction :
I2(s)  I2(g)
Specific heat of I2(s) = 0.055 cal g–1 K–1.
Specific heat of I2(vap) = 0.031 cal g–1 K–1.
Enthalpy (H1) of sublimation of iodine = 24 cal g–1
If q is the amount of heat involved in a system then at constant pressure q = qp and
H = CpT
H2 – H1 = Cp(T2–T1)
H2 = H1 + Cp(T2 – T1)
H2 = 24 + (0.031 – 0.055) (250 – 200)
H2 = 24 + (–0.024) (50) = 24 – 12 = 22.8 cal/g
Thus, the enthalpy of sublimation of iodine at 250 is 22.8 cat/g.

11. Na(g) + Br(g) NaBr(s)
IE1 Heg1 L.E.
+ –
Na (g) + Br (g)
Hformation = IE1 + Heg1 + LE

= 495.8 + (–325) + (–728.4)
= –557.6
= –5576 × 10–1 KJ/mol.
Note: The above calculation is not for Hformation but for HReaction.
But on the basis of given data it is the best ans.

CHEMISTRY

CPP
ST
ELECTROCHEMISTRY NO. 09
Type : 1 (Electrode Potential)

Eext
1.

Zn rod Cu rod
–ve +ve
1M Salt 1M
ZnSO4 Bridge CuSO4
solution solution
EºCu2  |Cu  0.34V

E ºZn2 |Zn  0.76V
Identify the incorrect statement from the options below for the above cell.
(1) If Eext > 1.1 V, Zn dissolves at Zn electrode and Cu deposits at Cu electrode.
(2) If Eext = 1.1 V, no flow of electrons or currecnt occurs.
(3) If Eext = 1.1 V, electrons flows from Cu to Zn.
(4) If Eext < 1.1 V, Zn dissolved at anode and Cu deposits at cathode. [JEE Main 2020]
2. Given, that EO 2 /H2 O = + 1.23 V;

ES O2 /SO2  = 2.05 V
2 8 4

EBr s = +1.09 V
2 /Br
EAu3  /Au = 1.4 V

The strongest oxidising agent is
(1) Au3+ (2) O2 (3) S 2O82 (4) Br2
3. Given,
Co3+ + e– Co2+ ; E° = +1.81 V Pb4+ + 2e– Pb2+ ; E° = +1.67 V
Ce4+ + e– Ce3+ ; E° = +1.61 V Bi3+ + 3e– Bi ; E° = + 0.20 V
Oxidising power of the species will increase in the order
(1) Ce4+ < Pb4+ < Bi3+ < Co3+ (2) Bi3+ < Ce4+ < Pb4+ < Co3+
(3) Co3+ < Ce4+ < Bi3+ < Pb4+ (4) Co3+ < Pb4+ < Ce4+ < Bi3+

4. Consider the following reduction processes:
Zn2+ + 2e– Zn(s) ; E° = – 0.76 V
Ca2+ + 2e– Ca(s) ; E° = – 2.87 V
Mg2+ + 2e– Mg(s) ; E° = – 2.36 V
Ni2+ + 2e– Ni(s) ; E° = – 0.25 V
The reducing power of the metals increases in the order
(1) Zn < Mg < Ni < Ca (2) Ni < Zn < Mg < Ca
(3) Ca < Zn < Mg < Ni (4) Ca < Mg < Zn < Ni
Type : 2 (Nernst equation)

5. The magnitude of the change in oxidising power of the MnO 4 / Mn2  couple is x × 10–4 V, if
the H+ concentration is decreased from 1 M to 10–4 M at 25°C. (Assume concentration of
MnO 4 / Mn2  to be same on change in H+ concentration). The value of x is _______.
 2.303RT 
Given : F
 0.059  [JEE Main 2021]
 
6. Emf of the following cell at 298 K in V is x × 10–2. Zn|Zn2+ (0.1 M)||Ag+ (0.01 M)| Ag. The value
of x is ______. (Rounded off to the nearest integer)
2.303RT
[Given : E 0Zn2 /Zn  0.76V ; E0Ag / Ag  0.8V ;  0.059 ]
F
7. Given the equilibrium constant

(KC) of the reaction :
Cu(s) + 2Ag+(aq)  Cu2+ (aq) + 2Ag(s)
 RT 
is 10 × 1015, calculate the Ecell of this reaction at 298 K. 2.303 at 298K  0.059 V 
 F 
(1) 0.4736 V (2) 0.04736 mV (3) 0.4736 mV (4) 0.04736 V
8. For the disproportionation reaction 2Cu+ (aq) Cu(s) + Cu2+ (aq) at 298 K, In K (where K
is the equilibrium constant) is …….. × 10–1
RT
Given : ( EºCu
2
/Cu
º
 0.16V,ECu
/Cu
 0.52 V and  0.025 )
F
9. Given that the standard potentials (Eº) of Cu2+/Cu and Cu+/Cu are 0.34 V and 0.522 V
respectivey, the Eº of Cu+/Cu+ is
(1) –0.158 V (2) + 0.158 V (3) –0.182 V (4) 0.182 V
10. What would be the electrode potential for the given half-cell creation at pH = 5 ? ……….
2H2O  O2 + 4H + 4e– ; E0red = 1.23 V
(R = 8.314 J mol–1 K–1 ; Temp = 298 K; oxygen unde std. atm pressure of 1 bar)
11. Calculate the standard cell potential (in V) of the cell in which following reaction takes place

Fe2+(aq) + Ag+(aq) Fe3+ (aq) + Ag(s)
o
Given that, EoAg / Ag = x V, EFe 2
/Fe
=yV
o
EFe 3
/Fe
=zV
(1) x + 2y – 3z (2) x – y (3) x + y – z (4) x – z
12. In the cell

Pt(s) | H2 (g, 1bar)|HCl(aq)|AgCl(s)|Ag(s)|Pt(s) the cell potential is 0.92 V when a 10–6 molal
HCl solution is used. The standard electrode potential of (AgCl/Ag,Cl–) electrode is
 2.303RT 
Given,  0.06 V at 298K 
 F 
(1) 0.40 V (2) 0.20 V (3) 0.94 V (4) 0.76 V
13. For the cell, Zn(s) | Zn2+(aq) || Mx+(aq) | M(s), different half cells and their standard electrode
potential are given below.
Mx+(aq)/M(s) Au3+ (aq)/Au(s) Ag+ (aq)/Ag(s) Fe3+ (aq)/ Fe2+ (aq) Fe2+ (aq)/ Fe (s)

EM x
/M
/V 1.40 0.80 0.77 –0.44
If EZn2  /Zn =–0.76 V, which cathode will give a maximum value of Ecell per electron transferred?
Ag Fe2 Au3 Fe3 

(1) (2) (3) (4)
Ag Fe Au Fe2
Type : 3 (Thermodynamics of Cell Reaction)
14. The Gibbs energy change (inJ) for the given reaction at [Cu2+] = [Sn2+] = 1M and 298 K is
Cu(s) + Sn2+(aq)  Cu2+ (aq) + Sn(s);
–1
( EºSn2
/Sn
º
 0.160.16V,ECu2
/Cu
 0.34V, Take, F = 96500 C mol ) [JEE Main 2020]
15. An oxidation-reduction reaction in which 3 electrons are transferred has a Gº of 17.37 kJ
mol–1 at 25ºC. The value of Eºcell (in V) is …………. × 10–2. (1F = 96,500 C mol–1)
16. For the given cell ;

Cu(s)|Cu2+(C1M)||Cu2+(C2M)|Cu(s) change in Gibbs energy (G) is negative, if
C1
(1) C1 = C2 (2) C2  (3) C1 = 2C2 (4) C2  2C1
2
[Sn2  ]
17. For an electrochemical cell Sn(s) |Sn2+ (aq, 1 M ||Pb2+ (aq, 1 M) |Pb(s) the ratio when
[Pb2  ]
this cell attains equilibrium is ……………….
 º º 2.303 RT 
 Given: ESn2 |Sn  0.14V,EPb2 |Pb  0.13V, F
 0.06 
 
18. The standard Gibbs energy for the given cell reaction in kJ mol–1 at 298 K is

Zn(s) + Cu2+ (aq)  Zn2+ (aq) + Cu(s), E° = 2 V at 298 K
(Faraday’s constant, F = 96000 C mol–1)
(1) 384 (2) 192 (3) –384 (4) –192
19. If the standard electrode potential for a cell in 2V at 300K, the equilibrium constant (K) for the
reaction
Zn(s) + Cu2+ (aq) Zn2+ (aq) + Cu(s)
at 300 K is approximately
(R = 8 JK–1 mol–1, F = 96000 C mol–1)
(1) e–160 (2) e160 (3) e–80 (4) e320
 dE 
20. The standard electrode potential E and its temperature coefficient   for a cell are 2V
 dT 
and –5 × 10–4 VK–1 at 300 K respectively. The cell reaction is
Zn(s) + Cu2+ (aq)  Zn2+ (aq) + Cu(s)
The standard reaction enthalpy (1H) at 300 K in kJ mol–1 is, [Use, R = 8 JK–1 mol–1 and
F = 96000 C mol–1]
(1) – 412.8 (2) –384.0 (3) 206.4 (4) 192.0
Type : 4 (Faraday’s law of electrolysis)

21. Consider the following reaction
4 MnO4– + 8H+ + 5e–  Mn2+ + 4H2O, Eº = 1.51 V.
The quantity of electricity required in Faraday to reduce five moles of MnO4– is____.
[JEE Main 2021]
22. An acidic solution of dichromate is electrolysed for 8 minutes using 2A current. As per the
following equation
Cr2O72 + 14H+ + 6e–  2Cr3+ + 7H2O
The amount of Cr3+ obtained was 0.104 g. The efficiency of the process (in %) is
(Take : F = 96000 C, atomic mass of chromium = 52) ……….
23. 250 mL of a waste solution obtained from the workshop of a goldsmith contains 0.1 M AgNO3
and 0.1 M AuCl. The solution was electrolysed at 2V by passing a current of 1 A for 15
minutes. The metal/metals electrodeposited will be
( EºAg 
/ Ag
 0.80V,EºAu / Au  1.69 V )
(1) only silver

(2) silver and gold in equal mass proportion
(3) only gold
(4) silver and gold in proportion to their atomic weights

24. Potassium chlorate is prepared by the electrolysis of KCl in basic solution
– –  –
6OH + Cl  ClO + 3H2O+6e . If only 60% of the current is utilized in the reation, the time
3
(rounded to the nearest hour) required to produce 10g of KClO3 using a current of 2A is
……… . (Given : F = 96500 C mol–1 ; molar mass of KClO3 = 122 g mol–1
25. 108 g of silver (molar mass 108 g mol–1) is deposited at cathode from AgNO3(aq) solution by a
certain quantiy of electricity. The volume (in L) of oxygen gas produced a 273 K and 1 bar
pressure from water by the same quantity of electricity is …………
26. A solution of Ni(NO3)2 is electrolysed between platinum electrodes using 0.1 Faraday
electricity. How many mole of Ni will be deposited at the cathode?
(1) 0.20 (2) 0.10 (3) 0.15 (4) 0.05
27. The anodic half-cell of lead-acid battery is recharged using electricity of 0.05 Faraday. The
amount of PbSO4 electrolysed in g during the process is (Molar mass of PbSO4 = 303 g mol–1)
(1) 11.4 (2) 7.6 (3) 15.2 (4) 22.8
Type : 5 (Conductance and Conductivity)

28. A 5.0 m mol dm–3 aqueous solution of KCl has a conductance of 0.55 mS when measured in a
cell constant 1.3 cm–1. The molar conductivity of this solution is ________ mSm2 mol–1.
(Round off o the Nearest Integer) [JEE Main 2021]
29. A KCl solution of conductivity 0.14 S m–1 shows a resistance of 4.19  in a conductivity cell. If
the same cell is filled with an HCl solution, the resistance drops to 1.03 . The conductivity of
the HCl solution is ____ × 10–2 S m–1, (Round off to the nearest Integer).
30. The variation of molar conductivity with concentration of an electrolyte (X) in aqueous solution
is shown in the given figure.
Molar
Conductivity
The electrolyte X is
(1) HCl (2) NaCl (3) KNO3 (4) CH3COOH
31. Consider the statements S1 and S2 :

S1 : Conductivity always increases with decreases in the concentration of electrolyte.
S2 : Molar conductivity always increases with decrease in the concentration of electrolyte.
The correct option among the following is
(1) S1 is correct and S2 is wrong (2) S1 is wrong and S2 is correct
(3) Both S1 and S2 are wrong (4) Both S1 and S2 are correct

32. Which one of the following graphs between molar conductivity (  m ) versus C is correct?
NaC
KC
KC
Na
(1)  m (2)  m (3)  m KC (4)  m
KC Na
Na
C C C C
Type : 6 (Kohlrausch law)
33. The molar conductivities at infinite dilution of barium chloride, sulphuric arid and hydrochloric
acid are 280, 860 and 426 Scm2 mol–1 respectively. The molar conductivity at infinite dilution
of barium sulphate is _______ S cm2 mol–1 (Round off to the Nearest Integer).
[JEE Main 2021]
34. Ledt CNaCl and CBaSO be the conductances (in S) measured for saturated aqueous solution of
4
NaCl and BaSO4. Respectively, at a temperatures T. Which of the following is false ?

(1) Ionic mobiliies of ions from both salts increase with T.
(2) CBaSO (T2), > CBaSO (T1) for T2 > T1
4 4
(3) CNaCl(T2) > CNaCl(T1) for T2 > T1

(4) CNaCl ≫ CBaSO at a given T
4
35. The equation that is incorrect is

(1) (m0 )NaBr  (0m )NaCl  (m0 )KBr  ( 0m )KCl (2) (m0 )KCl  (0m )NaCl  (0m )KBr  (0m )NaBr
(3) (m0 )NaBr  (0m )Nal  ( 0m )KBr  (m0 )NaBr (4) ( m0 )H O  ( m0 )HCl  ( m0 )NaOH  ( m0 )NaCl
2
36. m for NaCl, HCl and NaA are 126.4, 425.9 and 100.5 S cm2 mol–1, respectively. If the
conductivity of 0.001 M HA is 5 × 10–5S cm–1, degree of dissociation of HA is
(1) 0.25 (2) 0.50 (3) 0.75 (4) 0.125
37. The photoelectric current from Na (work function, w0 = 2.3 eV) is stopped by the output
voltage of the cell Pt(s) |H2(g, 1 bar)| HCl(aq.,pH = 1) | AgCl(s)| Ag(s).
The pH of aqueous HCl required to stop the photoelectric current from K(w0 = 2.25 eV), all
other conditions remaining the same, is …………. × 10–2 (to the nearest integer).
RT
Given, 2.303 = 0.06 V; EºAgCl|Ag|cl  0.22 V [JEE Main 2020]
F

ANSWER KEY
1. (1) 2. (3) 3. (2) 4. (2) 5. (3776)
6. (147) 7. (1) 8. (144) 9. (2) 10. (–0.94)
11. (1) 12. (1) 13. (1) 14. (96500) 15. (–6)
16. (4) 17. (2.15) 18. (3) 19. (2) 20. (1)
21. (25) 22. (60) 23. (3) 24. (11.00) 25. (5.66)
26. (4) 27. (2) 28. 14.3 (14) 29. (57) 30. (4)
31. (2) 32. (3) 33. (288) 34. (3) 35. (3)
36. (4) 37. (58.3)
ANSWER KEY
1. Given, EºCu 2
/ Cu
 0.34 V
EºZn2  / Zn  0.76 V
EºCell  ECu
º
2
/Cu
º
 EZn2
/ Zn
= 0.34 – (–0.76) = 1.10 volt
Statement (1) is incorrect whereas all other statements are correct

If Eext > 1.1 V {act as electrolytic cell}
Cu  Anode
Zn  Cathode
If, Eext = 1.10 V
Zn  Anode
Cu  Cathode
So, Zn dissolves at copper electrode and Cu at Zn electrode.
2. Higher the standard reduction potantial
E o
Mn  /M  , better is oxidising agent. Among the given, E 
S2 O82  /SO24 
is highest, hence S 2O82 is the
strongest oxidising agent.

The decreasing order of oxidising agent among the given option is as follows:
S 2O82 > Au3+ > O2 > Br2
3. Negative E° means that redox couple in weaker oxidising agent that H+/H2 couple. Positive E°
means that redox couple is a stronger oxidising agent than H+/H2 couple
Given, Co3+ + e– Co2+ ; E° = +1.81 V
Pb4+ + 2e– Pb2+ ; E° = +1.67 V
Ce4+ + e– Ce3+ ; E° = +1.61 V
Bi3+ + 3e– Bi ; E° = + 0.20 V

Oxidising power of the species increases in the order of Bi3+ < Ce4+ < Pb4+ < Co3+.
Higher the emf value, stronger the oxidising power. The maximum value of emf is possessed
by Co3+. Hence, it has maximum oxidising power. whereas Bi3+ posses the lowest emf value.
Hence, it has minimum oxidising power.
4. Reducing power of an element

1
=
Standard reduction potential

Here, EM 2
/M
values of the given metals are as,
Metals Ni Zn Mg Ca
0.25 0.76  2.36  2.87
E(V)  
Re ducingpower
Thus, the correct order of increasing reducing power of the given metal is,
Ni < Zn < Mg < Ca.
5. Eqn is –
MnO4– + H+ 5e–  Mn+2 + 4H2O
Nernst equation:
8
0 0.059 [Mn2 ]  1 
Ecell  Ecell  log
5 [MnO4 ]  H 
(I) Given [H ] = 1M
0.059 [Mn2 ]
E1  E0  log
5 [MnO4 ]
(II) Now : [H ] = 10–4 M
0.059 [Mn2 ] 1
E2  E0  log 
5 [MnO 4 ] (104 )8

00.059 Mn2 0.059

=E  log 
 log10 32
5 [MnO4 ] 5
0.059
therefore : E1  E2   32
5
= 0.3776 V = 3776 × 10–4
x = 3776

2
6. Zn(s)  Zn(aq.) + 2e–
2Ag(aq.) + 2e–  2Ag(s)

_______________________________
 2
Zn(s) + 2Ag(aq.)  Zn(aq.) + 2Ag(s)
_______________________________
E0cell  E0Ag / Ag  E0Zn2 /Zn
= 0.80 – (–0.76)
= 1.56 V
0.059 [Zn2 ]
Ecell  1.56 log
2 [Ag ]2
0.059 0.1
 1.56  log
2 (0.01)2
0.059
 1.56  3
2
= 1.56 – 0.0885
= 1.4715
= 147.15 × 10–2
7. According to Nernst equation,

2.303 RT
Ecell = Ecell – logQ
nF
2.303 RT
Given, = 0.059 V
F
0.059
 Ecell = Ecell – logQ
n
At equilibrium, Ecell = 0
0.059
Ecell = logKC
n
For the given reaction, n = 2
Also, KC = 10 × 1015 [given]
0.059
 Ecell =  log (10 × 1015)
2
= 0.472 V  ~0.473 V

8. 2Cu+(aq) Cu(s) + Cu2+(aq)
For the cell reaction,
º º º
ECell  ECu
/Cu
 ECu 2
/Cu
= (0.52 – 0.16) V = 0.36 V
 Gº = – nF EºCell
 –RTlnK = – nF EºCell
E º
 lnK = n ×  ECell
RT
1
= 1  0.36
0.025
=14.4 = 144 × 10–1
9. The half cel reactions are :

(1) Cu2+ + 2e– Cu; Eº = 0.34 V
+ –
(2) Cu + e Cu; Eº = 0.522 V
(3) Cu2+ + e– Cu+ ; Eº = x
As we know, QGº = – nFE
 To obtaine the Eº of required equation, subtract Gº of equation (2) from Gº of (1) as
Gº of (3) = Gº of (1) – Gº (1) as
Or – 1× F × x = (–2 × F × 0.34) – (–1 × F × 0.522)
 x = 2 × 0.34 – 0.522 = 0.68 – 0.522 = 0.158 V
10. Give, E0red = 123 V

But as the given half cell reaction is an oxidation reaction, Therefore,
Eºoxi  Ered
º
= – 1.23 V  n = 4
T = 298 K  pH = 5  [H+] = 10–5

By Nerst equation, at 298 K :
0.0591
E  Eº  logQ [ Q = Po2 × [H+]4]
n
0.0591
= –1.23 – log1 × (10–5)4
4
1 
= –1.23 – 0.0591  log1020 
4 
= – 1.23 – 0.0591 × 5 log 10
= –1.23 – (0.0591 × – 5) = 1.23 × 0.295
= –0.935 V  –0.94 V

11. Fe2+ (aq) + Ag+ (aq)  Fe3+ (aq) + Ag(s)
 Eocell  EoAg / Ag  EFe
o
3
/Fe2 

o
  = xV – EFe3
/Fe2 
....(i)
Now, for two half-cells

o
(i) Fe2+ + 2e–  Fe; EFe 2
/Fe
= E1o = yV Go2 = 2FE1o
o
(ii) Fe2+ + 3e–  Fe; EFe 3
/Fe
= Eo2 = zV Go2 = 2FEo2
o
So, Fe3+ + e–  Fe2+ ; EFe3
/Fe2 
= Eo3 = ? ; Go3 = – 1 × FEo3
Again, Go3 = Go2 – G1o
 – FEo3 = – 3FEo2 – (– 2FE1o )
 – Eo3  2E1o  3Eo2
 Eo3  3Eo2  2E1o

o
 EFe3
/Fe2 
= (3z – 2y)V
So, from equation (i)

Eocell = xV – (3z – 2y) V = (x – 3z + 2y) V
12. It is electrochemical cell. The overall cell reaction can be written, as

H2(g) + 2AgCl(s)  2HCl(aq) + 2Ag(s)
(1 bar) (10–6 M)
(i) According to Nernst equation,
2.303  RT [HCl]2 [Ag]2

Ecell = Ecathode  Eanode   nF
log
pH [AgCl]2
2
Here, (i) Ec  EAgCl/ Ag, Cl = ECathode
(ii) ECathode = E2H /H = 0.00 V (Standard hydrogen electrode)

2
 0.92 = ( Ec – 0) – 0.06 × log

10  6
 12
1  12
= Ec = 0.92 – 0.72 = 0.20 V
Note 10–6 molal HCl is a very dilute solution.

So, 10–6 m = 10–6 M

13.
Cell
Ecell (SRP) = EC – EA Ecell free e transer
Anode(A) Cathode(C)
Zn Ag 1.56
1.  Zn  2Ag  Zn2  2Ag  0.80 – (– 0.76) = + 1.56 V for 2e–  = + 0.78 V
2
Zn Fe 0.32
2.  Zn  Fe2  Zn2  Fe  – 0.44 – (– 0.76) = + 0.32 V for 2e–  = + 0.16 V
2
Zn Au 2.16
3.  3Zn  2Au3   3Zn2  2Au  1.40 – (– 0.76) = + 2.4 V for 6e–  + 0.36 V
6
Zn Fe 1.53
4.  3Zn  2Fe3  Zn2  2Fe 2  0.77 – (– 0.76) = + 1.53 V for 2e–  = + 0.765 V
2
14. Cu(s) + Sn2+(aq)  Cu2+(aq) + Sn(s)

0.0591 [Cu2 ]
Ecell = ( EºSn2
º
 ECu2 )– log
/Sn /Cu
2 [Sn2  ]
0.0591 1
= (–0.16 – 0.34) – log = – 0.50 V
2 1
G = – nF Eºcell = – 2 × 96500 × (–0.50) J
= 96500.00 J
15.  Gº = –nF Eºcell
Here Gº = 14.37 kJ mol–1

n = number of electrons
F = Faracday constant = 96500 C/mol
= 17.37 × 1000 J mol–1
17.37 × 1000 = – 3 × 96500 × Eºcell
17.37  1000
Eºcell 
3  96500
Eºcell = –0.06 = – 6 × 10–2
16. Given, cell is Cu(s)|Cu2+(C1M)||Cu2+(C2M)|Cu(s)

Gibbs free energy, DG = – nFEcell
G is negative, if Ecell is positive, two half reaction are as follows for given cell reaction
At anode Cu(s)  Cu2+(C1) + 2e–
At cathode Cu2+(C2) + 2e–  Cu(s)

Total cell reaction
Cu2+(C2)  Cu2+(C1) ; Cºcell = 0
2.303RT C 
Ecell = 0 – log  1 
nF  C2 
C1
Ecell > 0 ; if < 1  C1 < C2
C2
C2 = 2 C1 is correct
17. (exact value –2.154

Cel notation
Sn(s) |Sn2+ (aq ; 1 M)| |Pb2+(aq; 1M)) |Pb(s)
Cell reaction :
Sn(s) + Pb2+(aq) Pb(s) + Sn2+(aq)
[Sn2  ]
Equilibrium constant (K) =  unknown
[Pb2  ]
EºCell  EºCathode  EºAnode
= (–0.13 V) – (–0.14 V) = 0.01 V

From Nernst equation,
2.303RT 0.06
Eº  logK  logK
nF n
nEº
 logK  ;(n  2)
0.06
2  0.01 1
=  0.33or
0.06 3
K = 100.33 or 101/3 = 3 10  2.154  2.15

The value may range from 2.13 to 2.17
18. Gibbs energy of the reaction is related to Eocell by the following formula
G° = nFEcell
G° = Gibbs energy of cell

nF = amount of charge passed
E = EMF of a cell
Give reaction is
Zn + Cu2+  Zn2+ + Cu
Ecell = 2.0 V

F = 96000 C
n=2
To find the value of G° (kJ mol), we use the formula
G° = nFEcell
G° = – 2 × 96000 × 2
= –384000 J/mol
384000
In terms of kJ/mol, G° = = –384 kJ/mol
1000
19. The relationship between standard electrode potential (E°) and equilibrium constant (K) of the
cell reaction,
Zn(s) + Cu2+ (aq) Zn2+ (aq) + Cu(s)
can be expressed as,
RT
E° = ln K  K nFE /RT 
nF
Given, n = 2, F = 96000 C mol–1
E° = 2 V, R = 8 JK–1 mol–1, T = 300 K
2960002
 K= e 8300 = e160

 dE 
20. Given, E° = 2V,   = –5 × 10–4 VK–1
 dT 
T = 300 K, R = 8 JK–1 mol–1,
F = 96000 C mol–1
According to Gibbs-Helmholtz equation,
G = H – TS ....(i)
Also, G = – nFEcell ....(ii)
On substituting the given values in equation (ii), we get

G = –2 × 96000 C mol–1 × V
[Q n = 2 for the given reaction]
–1
= – 4 × 96000 J mol
= –384000 J mol–1
 dE 
Now, S = nF  
 dT 
or S = 2 × 96000C mol–1 × (–5 × 10–4 VK–1)

= –96 JK–1 mol–1
Thus, on substituting the values of G and S in Eq. (i), we get – 384000 J mol–1
= H – 300 K × (–96 JK–1 mol–1)
H = –384000 – 28800 J mol–1
= – 412800 J mol–1 = –412.800 kJ mol–1
22. Given Cr2O72 + 14H+ + 6e–  2Cr3+ + 7H2O
 8  60  2 
Number of moles =   [ F = 96000 C]
 96000 
Using stoichiometry,
neused nCr3  Pr oduced

6 2
2 8  60  2 1
 nCr 3 produced =  
6 96000 30
Theoritically produced
 1 
Weight Cr 3     52  g [ Mass of Cr = 52]
 30 
Weight actual = 0.104 g
Weight (actual)
Efficiency =  100
Weight (theoritical)
0.104g
Efficiency of the process =  100  60%
 1 
 30  52 
 
it
23. Charge(q) = F
96500
1 15  60 900 9
=   F = 0.0093 F
96500 96500 965
Number of moles of Au+ = 0.01 and number of moles of Ag+ = 0.01
Species with higher value of standard reduction potential, ( EºAu 
/ Au
 1.69 V ) will get
Deposited first at cathode.

Au (aq)  e   Au(s)
0.01 0.0093 mol
So, only Au will get deposited.

24. For 1 mol of ClO3 , 6 F charge required but current efficiency is only 60%. So, to obtain 1 mol
10g
ClO3 , Now, moles of KClO3 =
122
10
 Charge =  10F
122
 Current using = 2 A
Applying, W=Z×l×t
10 2
  × 2 × 3600  t = 11 hrs
122 96500
Hence, the correct answer is (11).
25. Equal quantity of electricity produces same number of equivalent of productcs in electrolysis.
 No. of equivalent of O2 produced = No. of equivalents of Ag produced
No. of equivalent of Ag
Mass 108
=   1.
Equivalent mass 108
 No. of equivalents of O2 formed =1.

For production of O2 from water
2H2O  O2 + 4H+ + 4e–
n-factor = 4
1
 1 equivalent = moles
4
Volume of gas at 273 K and 1 bar pressure
1
= 22.7 × n = 22.7 × - 5.675 L
4
26. A solution of Ni(NO3)2 is electrolysed between platinum electrodes using 0.1 Faraday
electricity. It means that 0.1 equivalent of Ni2+ will be discharged.
Electrolysis of Ni(NO3)2 gives
Ni2+ + 2e–  Ni (atomic mass of Ni = 58.7)
Number of equivalents = Number of moles × number of electrons.
0.1 = Number of moles × 2
0.1
 Number of moles of Ni = = 0.05 
2


27. This question is based upon Faraday’s first law which states that “Mass of any substance
deposited of liberated at any electrode is directly proportional to the quantity of electricity
passed.”
During charging :
Pb + SO24 PbSO4 + 2e–
 1 F 1 g-equiv. of PbSO4
1 303
= mol of PbSO4  g PbSO4
2 2
303
 0.05 F  × 0.05 g PbSO4
2
= 7.575 g of PbSO4
m.mol
28. Given concn of KCl =
L
: Conductance (G) = 0.55 mS

: Cell constant   = 1.3 cm–1
A
To Calculate : Molar conductivity (m) of sol.

1 k
 Since m   .....(1)
1000 m
mol
 Molarity = 5 × 10–3
L
   1.3
 Conductivity = G     0.55 mS  m1 = 55 × 1.3 mSm–1
A 1
100
1 55  1.3 mSm2
eqn (1) m  
1000  5  mol
 1000 
 
mSm 2
 m = 14.3
mol
1
29.  ·G 
R
For same conductivity cell, G is constant and hence .R. = consant
 0.14 × 4.19 =  × 1.03
0.14  4.19
Or,  of HCl solution =
1.03
= 0.5695 Sm–1
= 56.95 × 10–2 Sm–1  57 × 10–2 Sm–1

30. Molar and activity, m is defined as the conducting power of all the ion produced by dissolving
one gram mole of on electrolyte in solution, it is a function of the ionic strength of a solution.
The molar conductivity of both weak and strong electrolytes increases with decrease in
concentration Molar conductivity is the conductivity affered by one mole of ions.
Increased dilution results in the dissociation of more electrolytes into ions and effectively
increasing the number of active ions in the solution. These active ions impart more
conductivity.
CH3COOH
/Scm–2mol–1 KCl
C1/2/mol1/2L1/2
31. The expiation of statements (S1 and S2) are as follows:

In conductivity cell, conductivity () is equal to the sum of ionic conductances (3), of an
electrolytic solution present is unit volume of the solution enclosed by two electrodes of unit
area (a  1) separated by a unit length (l = 1).
l
=c×  = c when l = 1, a = 1
a
So, with decreases in the concentration of electrolyte, number of ions in the given unit volume
also decreases, i.e. [conductivity] also decreases.
Thus, statement S1 is wrong. S2 : Molar conductivity (m) is defined as the conducting power
of all the ions present in a solution containing 1 mole of an electrolyte.
1000
m =  × VmL =  ×
M
where, VmL = Volume in mL containing 1 mole of electrolyte
m = molar concentration (mol/L)
1
m 
M
i.e. molar conductivity increases with decreases in the concentration (M) of electrolyte.
Thus, statements S2 is correct.
32. NaCl and KCl are strong electrolytes. So, the study of their molar conductances (m) can be
experimentally verified by Debye-Huckel
c
m  0m  B C

cm = molar conductance at concentration.
0m = molar conductance at infinite diution.
i.e. C  0
B = Debye-Hukel Onsgar constant.
For (both NaCl and KCl) a strong binary electrolyte like AB, the nature of the plot of  m vs
C will be
m
Na will remain in more hydrated state, i.e. larger sized in aqueous solution. As a result, ionic
mobility as well as ionic conductance of Na.
(or NaCl as Cl is common to NaCl and KCl) will be lower than K (or KCl). Thus, the plot of
 m vs C for NaCl and KCl is as follows :
KCl
NaCl
m
33. From Kohlrausch’s law

 m (BaSO 4 )   m (Ba 2 )   m (SO 42– )
 m (BaSO 4 )   m (BaCl2 )   m (H2SO 4 )  2  m (HCl)
= 280 + 860 – 2 (426)

= 288 Scm2 mol–1
34. NaCl is a strong electrolyte, whereas BaSO4 is a sparingly soluble (weaker) electrolyte. So,
even in saturated solution, NaCl will almost remain in dissociated form to give free Na+ and
Cl–. But availability of Ba2+ and SO24 in water will be very poor. But degree of dissociation of
BaSO4 will increase with a temperature to give more ions.
BaSO4(s) Ba2+(aq) + SO24 (aq)
Again, with increase in temperature ionic mobility alos increases. So options(1), (2) and (4)
are true but (3) is false.

Solubility of NaCl in water remains almost constant with increase in temperature. So, option ©
is false.
Solubility
NaCl
Temperature (ºC)
(Solubility curve)
35. According to Kohlrausch’s law,

Limiting molar conductivity of an electrolyte is the sum of the individual contributions of the
cation and the anion of the electrolyte. Therefore, for option(1).
mº (Na )  ºm (Br  )  mº (Na )  mº (Cl )
= mº (K )  mº (Br – )  mº (K )  mº (Cl )
Or mº (Br  )  mº (Cl )  mº (Br  )  mº (Cl )
 LHS = RHS
 The LHS of option (1) = mº (Br  )  mº (Cl ) and also RHS of that = mº (Br  )  mº (Cl )
LHS = RHS
For option(2),
mº (K )  mº (Cl )  mº (Na )  mº (Cl )
= mº (K  )  mº (Br  )  mº (Na )  mº (Br  )
Or mº (K  )  mº (Na )  mº (K  )  mº (Na )
 LHS = RHS
Similarly for option (3),
LHS = mº (Br  )  mº (I )
and RHS = mº (K )  mº (Na )
 LHS RHS
Thus, the correct answer is (3)
36. According to Kohlrausch’s law, the molar conductivity of HA at infinite dilution is given as,
m (HA) = [ m (H+) + m (Cl–)] + [ m (Na+) + m (A–)] – [ m (Na+) + m (Cl–)]
= 425.9 + 100.5 – 126.4
= 400 S cm2 mol–1

Also, molar conductivity at given concentration is given as,
100  
m =
M
Given,  = conductivity  5 × 10–5 S cm–1
M = Molarity  0.001 M
1000  5  10 5 S cm1
  m =
10 3 M
= 50S cm2 mol–1
Therefore, degree of dissociation (), of HA is,
m 50S cm2 mol1
=  = 0.125

m 400 S cm2 mol1
37. Pt(s) |H2(g), 1 bar| HCl(aq) (pH = 1) |(Ag(s)| Agcl) Reaction involved :
1
H2 + AgCl(s)  Ag(s) + H+ + Cl–
2
 0.06 
Ecell = EAg = 0.22  log[H ]Cl 
 1 
0.06
EK = 0.22 – log[H+] [Cl–]
1
hc
For Na,  2.3  ENa

hc
For K,  2.25  EK

Equation (i) and (ii)
2.3 ENa = 2.25 – EK
0.05 – 0.22 + 0.06log(10–1)(10–1) = –0.22 + 0.06log[H+] [Cl–]
5 + 6log(10–2) = 6log[H+]2
7
– = log[H+]
12
7
pH = + = 0.5833
12
pH = x × 10–2 = 58.3 × 10–2
So, value is 58.3

CHEMISTRY

CPP
ST
CHEMICAL KINETICS NO. 10
Type : 1 (Rate of Reaction, rate law and order of reaction)

1. The reaction 2A + B2  2AB is an elementary reaction.
For a certain quantity of reactants, if the volume of the reaction vessel is reduced by a factor
of 3, the rate of the reaction increases by a factor of ________.
(Round off to the Nearest Integer). [JEE Main 2021]
2. 2 NO(g) + C2(g) 2 NOCl(s)

This reaction was studied at –10ºC and the following data was obtained
Run [NO]0 [Cl2]0 r0
1 0.10 0.10 0.18
2 0.10 0.20 0.35
3 0.20 0.20 1.40
[NO]0 and [Cl2]0 are the initial concentrations and r0 is the initial reaction rate.
The overall order of the reaction is ______. (Round off to the nearest Integer).
3. The results given in the below table were obtained during kinetic studies of the following
reaction :
2A + B  C + D
Experiment [A]/mol L–1 [B]/mol L–1 Initial rate/mol L–1 min–1
I 0.1 0.1 6.00 × 10–3
II 0.1 0.2 2.40×10–2
–2
III 0.2 0.1 1.20 × 10
IV X 0.2 7.20 × 10–2
V 0.3 Y 2.88 × 10–1
X and Y in the given table are respectively

(1) 0.4, 0.4 (2) 0.4, 0.3 (3) 0.3, 0.4 (4) 0.3, 0.3
3
4. For the reaction 2A + 3B + C 3P, which statement is correct ?
2
dnA 2 dnB 3 dnC dnA 3 dnB 3 dnC
(1)   (2)  
dt 3 dt 4 dt dt 2 dt 4 dt
dn A dnB dnC dnA 2 dnB 4 dnC
(3)   (4)  
dt dt dt dt 3 dt 3 dt

5. Consider the following reactions
A  PI; B  P2; C  P3; D  P4,
The order of the above reactions are a, b, c and d, respectively. The following graph is
obtained when log[rate] vs log[concentration] are plotted:
[D]
[B]
[A]
log [rate]
[C]
log [conc.]
Among the following, the correct sequence for the order of the reactions is:
(1) D > A > B > C (2) A > B > C > D (3) C > A > B > D (4) D > B > A > C
6. For the reaction,

2H2(g) + 2NO(g)  N2(g) + 2H2O(g)
the observed rate expression is, rate = kf[NO]2[H2]. The rate expression for the reverse
reaction is
(1) kb[N2][H2O]2/[H2] (2) kb[N2][H2O] (3) kb[N2][H2O]2/[NO] (4) kb[N2][H2O]2
7. For the reaction. 2A + B  C, the values of initial rate at different reactant concentrations are
given in the table below. The rate law for the reaction is
[A](moll–1) [B] (molL–1) Initial rate (mol L–1s–1)
0.05 0.05 0.045
0.10 0.05 0.090
0.20 0.10 0.72
(1) rate = klA] [B]2 (2) rate = klA]2 [B]2 (3) rate = klA] [B] (4) rate = klA]2 [B]
8. In the following reaction; xAyB

 d[A]   d | B |
log10    log10    0.3010
 dt   dt 
A and B respectively can be
(1) n-butaneand iso-butane (2) C2H2andC6H6
(3) C2H4 and C4H8 (4) N2O4,andNO2
9. NO2required for a reaction is produced by the decomposition of N2O5 in CCl4 as per the
equation,
2N2O5 (g) 4NO2(g) + O2(g)
The initial concentration of N2O5 is 3.00 mol L–1 and it is 2.75 mol L–1 after 30 minutes. The
rate of formation of NO2 is
(1) 4.167 × 10–3mol L–1 min–1 (2) 1.667 × 10–2mol L–1 min–1
(3) 8.333 × 10–3mol L–1 min–1 (4) 2.083 × 10–3mol L–1 min–1

10. The following results were obtained during kinetic studies of the reaction;
Experiment [A] [B] Initial rate of reaction
(in mol L–1) (in mol L–1) (in mol L–1 min–1)
I. 0.10 0.20 6.93 × 10–3
II. 0.10 0.25 6.93 × 10–3
III. 0.20 0.30 1.386 × 10–2
The time (in minutes) required to consume half of A is
(1) 5 (2) 10 (3) 100 (4) 1
11. For the reaction, 2A + B  products when concentration of both (A and B) becomes double,
then rate of reaction increases from 0.3 mol L–1s–1 to 2.4mol L–1s–1.
When concentration of only A is doubled, the rate of reaction increases from 0.3mol L–1s–1 to
0.6mol L–1s–1. Which of the following is true?
(1)The whole reaction is of 4th order (2) The order or reaction w.r.t B is one
(3) The order of reaction w.r.t. B is 2 (4) The order of reaction w.r.t. A is 2
12. The reaction, 2 X  B is a zeroth order reaction. If the initial concentration of X is 0.2 M, the
half-life is 6h. When the initial concentration of x is 0.5 M, the time required to reach its final
concentration of 0.2 M will be
(1) 7.2 h (2) 18.0 h (3) 12.0 h (4) 9.0 h
Type : 2 (1st Order Reaction)

13. Gaseous cyclobutene isomerizes to butadiene in a first order process which has a 'k' value of
3.3 × 10–4 s–1 at 153°C. The time in minutes it takes for the isomerization to proceed 40 % to
completion at this temperature is _____.
14. Sucrose hydrolyses in acid solution into glucose and fructose following first order rate law with
 1
a half-life of 3.33 h at 25°C. After 9 h, the fraction of sucrose remaining is f. The value of  
f 
is _______ × 10–2. (Rounded off to the nearest integer) [Assume : ln 10 = 2.303, ln 2 = 0.693]
15. The decomposition of formic acid on gold surface follows first order kinetics. If the rate
constant at 300 K is 1.0 × 10–3 s–1 and the activation energy Ea =11.488 kJ mol–1, the rate
constant at 200 K is _______ × 10–5 s–1, (Round of to the Nearest Integer).
(Given : R = 8.314 J mol–1 K–1)
16. A and B decompose via first order kinetics with half-lives 54.0 min and 18.0 min respectively.
Starting from an equimolar non reactive mixture of A and B, the time taken for the
concentration of A to become 16 times that of B is _______ min. (Round off to the nearest
Integer)
17. For a certain first order reaction 32% of the reactant is left after 570 s. The rate constant of his
reaction is _______ × 10–3 s–1. (Round off to the Nearest Integer).
[Given : log102 = 0.301, 1n 10 = 2.303]

18. A first order reaction has a half life of 1 min. The time required for 99.9% completion of the
reaction is _____ min. (Round off to the Nearest integer) [Use : ln 2 = 0.69, ln 10 = 2.3]
19. If 75% of a first order reaction was completed in 90 minutes, 60% of the same reaction would
be completed in approximately (in minutes) …….… . (Take : log 2 = 0.30; log 2.5 = 0.40)
20. A flask contains a mixture of compounds A and B. Both compounds decompose by first order
kinetics. The Half-life for A and B are 300s and 180 s, respectively. If the concentrations of A
and B are equal initially, the time required for the concentration of A to be four times that of B
(in s) is (Use In 2 = 0.693)
(1) 120 (2) 180 (3) 300 (4) 900
90
21. During the nuclear explosion, one of the products is Sr with half-life of 6.93 years. If 1 g of
90
Sr was absorbed in the bones of a newly born baby in place of Ca, how much time, in years,
is required to reduce it by 90% if it is not lost metabolically……………
1
22. Consider the following plots of rate constant versus for four different reactions. Which of
T
the following orders is correct for the activation energies of these reactions?
a
log k
d c
1/T
(1) Eb > Ea > Ed > Ec (2) Ea > Ec > Ed > Eb (3) Eb > Ed > Ec > Ea (4) Ec > Ea > Ed > Eb
23. A sample of milk splits after 60 min. at 300 K and after 40 min. at 400 K when the population
of lactobacillus acidophilus in it doubles. The activation energy (in kJ/mol) for this process is
2
closest to (Given, R = 8.3 J mol–1 K–1 in    0.4, e–3 = 4.0)
3
24. A bacterial infection in an internal wound grows as N'(t) = N0exp (t), where the time t is in
hourse.A dose of antibiotic, taken orally needs 1 hour to reach the wound. Once it reaches
dN N
there, the bacterial population goes down as  5N2 . What wilbe the plot of 0 ust after 1
dt N
hours?
N0 N0 N0 N0
(1) N (2) N (3) N (4) N
t(h) t(h) t(h) t(h)

Type : 3 (Arrhenius Equation activation energy and Temperature coefficient)
1
25. For the reaction, aA + bB  cC + dD, the plot of log k vs is given below :
T
log k Slope = –10000 K
1/T
The temperature at which the rate constant of the reaction is 10–4 s–1 is _______ K.
[Given : The rate constant of the reaction is 10–5 s–1 at 500 K.] [JEE Main 2021]
26. The rate constant of a reaction increases by five times on increase in temperature from 27°C
to 52°C. The value of activation energy in kJ mol–1 is _______ (Rounded-off to the nearest
integer) [R = 8.314 J K–1 mol–1]
27. If the activation energy of a reaction is 80.9 kJ mol–1, the fraction of molecules at 700 K,
having enough energy to react to form products is e–x. The value of x is _______.
(Rounded off to the nearest integer) [Use R = 8.31 J K–1 mol–1]
28. The number of molecules with energy greater than the threshold energy for a reaction
increases five fold by a rise of temperature from 27°C to 42°C. Its energy of activation in J/mol
is…….. . (Take In 5 = 1.6094; R = 8.314 J mol–1 K–1)
29. The rate constant (k) of a reaction is measured at different temperature (T), and the data are
plotted in the given figure. The activation energy of the reaction in kJ mol–1 is (R is gas
constant)
10
In k 5
0
1 2 3 4 5
103/T
2 1
(1) (2) (3) r (4) 2R
R R
30. The rate of a reaction decreased by 3.555 times when the temperature was changed from
40°C to 30°C. The activation energy (in kJ mol–1) of the reaction is…………..
(Take; R = 8.314 J mol–1 K–1, In 3.555 = 1.268)

31. The rate of a certain biochemical reaction at physiological temperature (T) occurs 106 times
faster with enzyme than without. The change in the activation energy upon adding enzyme is:
(1) +6 RT (2) –6(2.303) RT (3) +6(2.303) RT (4) –6RT
32. For following reactions:

700K 500K
A   Product; A   Product
Catalyst
It was found that the Ea is decreased by 30 kJ/mol in the presence of catalyst. If the rate
remains unchanged, the activation energy for catalysed reaction is (Assume pre exponential
factor is same) :
(1) 198 kJ/mol (2) 105 kJ/mol (3) 75 kJ/mol (4) 135 kJ/mol
33. The given plots represent the variation of the concentration of a reaction R with time for two
different reactions (i) and (ii). The respective orders of the reactions are
(i) (ii)
In [R] [R]
time time
(1) 1.1 (2) 0,2 (3) 0, 1 (4) 1, 0
34. For the reaction or H2 with l2 the rale constant is 25 × 10–4 dm3mol–1s–1 at 327°C and 1.0
dm3mol–1 s–1 at 327°C and 1.0dm3mol–1 s–1 at 527°C. The activation energy for the reaction, in
kjmol–1 is (R=8.314 JK–1mol–1)
(1) 59 (2) 72 (3) 150 (4) 166
35. Consider the given plots for a reaction obeying Arrhenius equation (0°C < T < 300°C) : (k and
Ea are rate constant and activation energy, respectively)
K K
o
Ea T( C)
l lI
Choose the correct option.
(1)Both I and II are wrong (2) Both I and II are correct
(3) I is wrong but II is right (4) I is right but II is wrong
36. If a reaction follows the Arrhenius equation, the plot In kvs 1/(RT) given straight line with a
gradient (–y) unit. The energy required to activate the reactant is
y
(1) unit (2) –y unit (3) yR unit (4) y unit
R

37. For a reaction, consider the plot of Inkversus 1/T given in the figure. If the rate constant of this
reaction at 400 K is 10–5s–1, then the rate constant at 500 K is
(1) 4 ×10–4 s–1 (2) 10–6 s–1 (3) 10–4 s–1 (4) 2 × 10–4 s–1
k1 k2
38. For a reaction scheme. A  B  C, if the rate of formation of B is set to be zero then
the concentration of B is given by
k 
(1) k1k2[A] (2)  1  [A] (3) (k1–k2) [A] (4) (k1 + k2)[A]
 k2 
39. Consider the given plot of enthalpy of the following reaction between A and B.
A + BC+D
Identify the incorrect statement.
20
15
Enthalpy10
(KJ mol–1) D
5
A+B
C
Reaction
Coordinate
(1) D is kinetically stable product.
(2) Formation of A and B from C has highestenthalpy of activation.
(3) C is the thermodynamally stable product.
(4) Activation enthalpy to form C is 5 kjmol–1 less than that to formD.
d A 
40. 
For an elementary chemical reaction, A 2 1 k
2A , the expression for is
k 1 dt
(1) 2k1[A2] – k–1[A]2 (2) k1[A2] – k–1[A]2
(3) 2k1[A2] – 2k–1[A]2 (4) k1[A2] + k–1[A]2

ANSWER KEY
1. (27) 2. (3) 3. (3) 4. (4) 5. (4)
6. (1) 7. (1) 8. (3) 9. (2) 10. (2)
11. (3) 12. (2) 13. (26) 14. (81) 15. (10)
16. (108) 17. (2) 18. (10) 19. (60) 20. (4)
21. (23.03) 22. (4) 23. (3.98) 24. (1) 25. (526)
26. (52) 27. (14) 28. (84297.47) 29. (4) 30. (100.00)
31. (2) 32. (3) 33. (4) 34. (4) 35. (2)
36. (4) 37. (3) 38. (2) 39. (4) 40. (3)
SOLUTIONS
1. Reaction : 2A + B2  2AB
As the reaction is elementary, the rate of reaction is is
r = K. [A]2 [B2]
on reducing the volume by a factor of 3, the concentrations of A and B2 will become 3 times
and hence, the rate becomes 32 × 3 = 27 times of initial rate.
2. r = k[NO]m [Cl2]n
= k(0.1)m (0.1)n ...(1)
m n
= k(0.1) (0.2) ...(2)
m
= k(0.2) (0.2) ...(3)
n=1
m=2
m+n=3
3. Let the rate law is r  [A]a[B]b

 a and b are the order of reaction w.r.t A and B respectively
 Comparing first three (I, II, III) experiments :
a b
rII  0.1   0.2  2.4  10 2
      3
= 1 × 2b
rI  0.1   0.1  6  10
 2b = 4  b = 2
a 2
rIII  0.2   0.1  12  10 2
   = 2a × 1
rI  0.1   0.1  6  10 3
 2a × 2  a = 1
 rI × k × (0.1)1(0.1)2  6 × 10–3 = k × 10–3
 k = 6L2 mol–2 min–1
 Expt. IV : rII = 6 × (X)1 ×(0.2)2
 7.2 × 10–2 = 6 × (X) × (4 × 10–2)  X = 0.3 mol L–1
 Expt. V : rv = 6 × (0.3)1 ×(Y)2
 2.88 × 10–1 = 6 × 0.3 × (Y)2  0.4 mol L–1

4. For a reaction,
3
2A  3B  C  3P
2
For a reaction, aA + bB = cC
Rate of reaction,
1d [A] 1d [B] 1 d[C]
   
a dt b dt c dt
 For given reaction,s
1d [A] 1d [B] 2 d[C] 1 d[P]
   
2 dt 3 dt 3 dt 3 dt
d[A] 2 d[B] 4 d[C] 2 d[P]
    
dt 3 dt 3 dt 3 dt
5. We know that,
Rate = k (concentration)n
[n = order of reaction and k = rate constant]
Taking log both side, log (Rate) = log k + nlog [concentration]
Slope of graph is the order of reaction greater the slope, greater is the order of reaction.
 Concentration sequence for the order of reaction is D > B > A > C.
Hence, the correct option is (4).
6. 2H2(g) + 2NO(g) N2(g) + 2H2O(g)

Rate law for forward reaction is given as :
Rate = kf[NO]2 [H2]
Rate of forward reaction is equal to rate of reverse reaction at equilibrium and also, at
k1
equilibrium (K) =
kb
where, K(equilibrium constant)
[N2 ][H2O]2 k f [N2 ][H2O]2
=  
[H2 ]2 [NO]2 k b [H2 ]2 [NO]2
Rearranging :
kf[H2] [NO]2 = kb[N2] [H2O]2 / [H2]
 Rate of reverse reaction = kb[N2] [H2O]2 / [H2]
7. Let the rate equation be k [A]x [B]y

From Ist values,
0.045 = k[0.05]x [0.05]y …..(i)
Form 2nd values,
0.090 = k[0.10]x [0.05]y …..(ii)
Form 3rd values,
0.72 = k[0.20]x [0.10]y …..(iii)
On dividing equation (i) by (ii), we get

x
0.045  0.05 

0.09  0.10 
1 x
 0.05   0.05 
 0.10    0.10 
   
 x= 1
Similarly on dividing Eq. (ii) by (iii) we get
x y
0.09  01   0.05 
   
072  02   0.10 
y
0.01 01  0.05 

0.08 02  0.1 
y
 0.05 
025   
 0.10 
025 = [0.5]y[0.5]2 = [0.5]y
 y=2
Hence, the rate law for the reaction
Rate = k [A] [B]2
8. In the given reaction; x Ay B

 dA    d B  
log10    log10    0.3010
 dt   dt 
Value of log2 = 0.3010
Substituting 0.3010 by log2
 dA    d B  
log10     log10    log2
 dt   dt 
Using logarithm rules,
 dA   d B   1  d  A    d B  
   2      .....(i)
 dt   dt  2  dt   dt 
Using the rate equation (i) to determine the reaction involved is
2AB
Option that fits correct in the above reaction is (3).
9. Key Idea The rate of a chemical reaction means the speed with which the reaction takes
place.
For RP
Decrease in conc.of R  R 
Rate of disappearance of R = 
Time taken t
Increasein conc.of P  p 
Rate of appearance of P = 
Time taken t

Given [N2O5]nitial = 3.00 mol L–1
After 30 min, [N2O5] = 2 75 mol L–1
2N2O5(g)  4NO2(g) + O2(g)
t=0 3.0 M
t = 30 2.75 M
1  N2O5  1  NO2 
From the equation, It can be concluded that   
2 t 4 t
 N2O5  (2.75  3.00)molL–1 0.25  N2O5   N2O5 
   and  2
t 30 30 t t
 N2  0.25
  2 
t 30
= – 1.667 × 10 mol L–1 min–1
–2
10. Let the rate expression is r  [A]a [B]b

a b
r  0.1   0.25 
From experiment I, 2     
r1  0.1   0.20 
a b
r2  0.1   0.25 
     
r1  0.1   0.20 
b 0 b
5 5 5
  1           b  0
4 4 4
a b
r  0.2   0.30 
From experiment II, 3     
r1  0.1   0.20 
1.386  10 2 a 0
  2
  2   1.5 
0.693  10
  2 = 2a × 1  21 = 2a = 1
  So, r [A]1[B]0 r  [A]
Order of the reaction (n) = 1
 Now, let for the 1st experiment,
r1 = k  [A]
r1 6.93  10 3
    6.93  10 2 s1
[A] 0.1
0.693 0.693
  t 50    10s
k 6.93  10 2
11. For the reaction 2A + B  products.

Let, the rate expression is r a [A]a[B]b
a b
r2  2A   2B 
Expt 1    
r1  A   B 
2.4
  2 a  2b  2 3  2 a  b
0.3
  3 = a + b ….(i)

a b
r  2A   B 
Expt 2 2     
r1  A   B 
0.6 a
   2 × 1  21 = 2a a = 1 …(ii)
0.3
  From Eq. (i), 1 + b = 3  b = 2
   Order of the reaction (n) = a + b = 1 + 2 = 3
   Order of the reaction wrt. A = 1
   Order of the reaction wrt. B = 1
12. For zero order reaction, [A0] – [Ar] = kt ….(i)

Where, [A0] initial concentration
[Ar] = final concentration
k = rate constant
Also, for zero order reaction, t1/2 

A0 
2k
Givne, t1/2 = 6h
And [A0] = 0.2 M
0.2
 6 
2k
0.2 1
Or, k  
26 6
Now, from Eq. (i) [A0]–[At] = kt
Given [A0]= 0.5 M, [At] = 0.2M
1  1
 0.5 – 0.2 =
60
t  k  60 
 
1
0.3  t
60
t = 0.3 × 60 = 18h
13.  H2C = HC–CH = CH2
[A]0
Kt  n
[A]t
 100 
3.3 × 10–4 × t = n  
 60 
t = 1547.956 sec
t = 25.799 min
26 min

14. Given :
I order
C12H22O11 + H2O  10  C6H12O 6  C6H12O 6
t1/ 2  hr Glucose Fructose
3
t = 0 a = [A]0 – –
t = 9hr a – x = [A]t
kt A
from I order kinetic :  log 0
2.303 At
n 2  9  1
  log  
10 f
 2.303
3
0.693  9  3  1
  log  
23.03 f 
 1
 log   = 0.81246 = 81.24 × 10–2
f
 x = 81
15. K300 = 10–4 K200 = ?

Ea = 11.488 KJ/mole R = 8.314 J/mole-K
 K 300  Ea  1 1 
So n     
 K 200  R  200 300 
 K  11.488  1000  100
n  300  
 K 200  8.314  200  300
= 2.303
= n10
K 300
so  10
K 200
1
K200 =  K 300  10 4
10
= 10 × 10–5 sec–1
16. Given t2 = 54 min T1/2 = 18 min

A B
t = 0 'x' M t = 0 'x' M
 To calculate : [At] = 16 × [Bt] ...(1) time = ?
A0
 For I order kinetic : [A t ] 
(2)n
n  no of Half lives
 Now from the relation (1)
[At] = 16 × [Bt]

x x
 nt
 n2
 16  (2)n2 (2)nt  (2)4 
(2) (2)
t t
 n2 = n1 + 4  4
(t1/2 )2 (t1/2 )1
 1 1  4  18  54
 t     4 t 
 18 54  36
 t  108 min
17. For 1st order reaction,

2.303 [A ] 2.303  100 
K .log 0  .log  
t [A t ] 570 sec  32 
= 1.999 × 10–3 sec–1  2 × 10–3 sec–1
1 100
ln
t 99.9% K 0.1
18. 
t 50% 1
ln 2
K
ln1000
=  t 50%
ln2
3ln10
= 1
ln2
3  2.3
=  10
0.69
19. Given, first order reaction,

t75 = 90 minute  t60 = ?
Consider the following reaction,
A 
 B
(Reactant) (Product)
Time, t = 0 100
t15% = 90 min (100 – 75) = 25
t60% = ? (100 – 60) = 40
For first order reaction,
2.303 a   a0  Initial concentration 
t log  0   
k  a   a  Concentration 
For 75%
2.303  100   Initial concentration  100 
t 75%  log     ……(i)
k  25   Concentration  100  75  25 
For 60%
2.303  100   Initial concentration  100 
t 60%  log     ……(ii)
k  40   Concentration  100  60  40 

On equating Eqs. (i) and (ii),
2.303  100 
log  
t 60% k  40 

t75% 2.303  100 
log  
k  25 
 0.3979  0.3979
t 60%  t 75%     t 60%  90 
 0.602  0.602
t60% = 59.48 minute  60 min
20. We know that, N  N0e kt

ln 2
K can be calculated as : K  (Here, t1/2 = half-life)
t1/ 2
 The time required for the concentration of A to be four times that of B. Hence, A = 4B
ln2t In2t

300

180
ln2t ln2t
N0e  4.N0e    ln 4 
300 180
 1 1  2  180  300
 ln 2t     2ln 2 ; t  = 900s
 180 300  120
21. Radioactive decay follows first order kinetics.

 Time taken for decay from N0 to Nt is (N = number of nuclei)
1 N
t In 0
 Nt
1 N
t  × 2.303 log 0 …….(i)
 Nt
0.693
Also, we know  = (decay constant) =
t1/ 2
where, t1/2 = 6.93 yr (given)
Also, we know 90% nuclei are decayed
N0 100
   10
Nt 10
N0
Put the values of  and in Eq. (i), we get
Nt
6.93
 t × 2.303 × log 10 = 23.03 (yr)
0.693
22. According to Arrhenius equation

Eact
k  Ae Ea /RT  log k = log A –
2.303 RT
Eact = activation energy
1 Eact
Slope of the graph of ‘log k’ vs is 
T 2.303R

Greater the value of Eact, more will be the negative slope.
From the graph, most –ve slope = c, followed by a, d and b.
 Order of activation energies must be Ec > Ea > Ed > Eb
1
23. Time taken for milk to split 
k
where, k = rate constant of the process and, k at 2 different temperature and activation energy
are related.
k2 E 1 1 t
In   a     ln 1
k1 R  T1 T2  t2
 60  Ea  1 1 
 In     
 40  8.3  400 300 
Ea = 0.4 × 8.3 × 1200
= 3984 J mol–1 = 3.984 kJ mol–1
2 3
Given, In  0.4  In  0.4
3 2
2 3
(These are wrong values, because In is –ve and In is +ve, but assume them to be
3 2
correct.)
24. The expression for bacterial growth is

N = N0et
N0
 e– t
N
From 0 to 1 hour N’(t) = N0et
dN
From 1 hour onwards,  5N2
dt
On differentiating the above equation from N’ to N we get.
N t
N
–2
dN  5 dt [At 1 hour, N’ = eN0]
eN0 1
1 1 
    5(t  1)
 N eN0 
Multiply both sides by N0, we get
N0 1 N 1
  5N0 (t  1)or, 0  5N0 (t  1) 
N e N e
N0 1 
 5N0 t   5N0 
N e 

N0
N
t(h)
On comparing the above equation with equation of straight line, y = mx + c

1
We get m = 5N0, c =  5N0
e
N0
  Plot of vst is shown aside.
N
Ea
25. log K = log A –
2.303RT
Ea
|Slope| = = 10,000
2.303R
K  Ea  1 1 
log  2     
 K1  2.303R  T1 T2 
T2 = 526.31  526K
26. T1 = 300K, T2 = 325K, K2 = 5K,

K 2 Ea  1 1 
ln    
K1 R  T1 T2 
Ea  1 1 
or, ln 5  
8.314  300 325 

or, Ea = 0.7 × 2.303 × 8.314 × 12 × 325 = 52271 J = 52.271 kJ
Nearest integer answer will be 52 kJ
27. Fraction of molecules to have enough energy to react = e–Ea/RT

Ea
So, x=
RT
80.9  103
= = 13.9
8.31 700
28. Given, temperature rise 27°C to 42°C

Hence, T1 = 273 + 27 = 300 K
T2 = 273 + 42 = 315 K
{In 5 = 1.6094 R = 8.314 J mol–1K–1}
According to question k T2  5kT1 as molecules activated are increased five times so k will
increases 5 times. Now, k  Ae Ea /RT (Arrhenius equation).

On apply log both sides
 kT  E 1 1
ln  2  a  
 kT  R  T1 T2 
 1 
k T2
Here, 5
k T1
Ea  1 1 
In 5    
R  300 315 
Ea  315  300 
In 5   
8.314  300  315 
Ea 15
In 5  
8.314 300  315
Ea 15
1.6094  
8.314 300  315
1.6094  8.314  300  315
Ea 
15
Ea = 84297.47 50 Joules/mol
29.  k  Ae Ea /RT

Taking natural logarithm on both sides, the Arrhenius equation becomes.
E  1
 In k = In A –  a 
 R T
 E a  10 3
 In k = In A –  3 

 R  10  T
Ea 103
Slope of a graph =   
R  103 5
3 –1
Ea = 2R × 10 J mol  Ea = 2R kJ
30. The Arrhenius equation is

 KT  E  1 1 
In  2   a   
 KT1  R  T1 T2 
KT2
Given,  3.555
KT1
R = 8.314 JK–1 mol–1
T1 = 30 + 273 = 303 K; T2 = 40 + 273 = 313 K
Substituting the given values in the Arrhenius equation,
Ea  1 1 
In (3.555) =  (In 3.555 = 1.268)
8.314  303 313 

Ea  313  303 
1.268 =
8.314  303  313 
1.268  8.314  303  313
Ea 
10
= 99980.7 = 99.98 kJ/mol

31. Let the activation energy with and without enzyme be Ea* and Ea.
Rate constant of reaction without catalyst is given by Arrhenius equation.
k  Ae Ea /RT
Taking log on both sides, we get
Ea
logk  log A  ……..(i)
RT(2.303)
With catalyst, rate constant is 106 times more
Ea

 106k = Ae RT
E*a
log k + log 106 = log A –
RT(2.303)
E*a
 log k = log A – 6 ……..(ii)
RT(2.303)
Comparing Eqs. (i) and (ii)
Ea Ea*
 6
RT(2.303) RT(2.303)
 Ea* – Ea = –6(2.303)RT
32. For catalysed reaction, let Ea be x.

Then, for uncatalysed reaction, Ea = x + 30 (given in question).
Also, rate of reaction at 700 K (without catalyst) = rate of reaction at 500 K (with catalyst).
 k at 700 K without catalyst = k at 500 K with catalyst.
Using relation, k  Ae Ea /RT
Ea = Activation energy.
 Ae ( x  30 )/700R  Ae  x/500R
x  30 x
   7x = 5x + 150
700 500
2x = 150  x = 75 kJ
33. In first order reaction, the rate expression depends on the concentration of one species only
having power equal to unity.
 d r 
nrproducts  k r 
dt
On integration, in[r] = kt – In[r0]
Or In(r) = In(r0)–kt
Y = c + mx
M = slope = – k (negative)
C = intercept = In (r0)
The graph for first order reaction is
In (r)

In zero order reaction
[r] product
 d r  t
  = k or –d[r]t = kdt
dt
On integrating, –[r]t = kt + c
If t = 0, [r]t = [r]0
  –[r]t = –[r]0 –kt
Thus the graph plotted between [r]t and t gives a straight line with negative slope (–k) and
intercept equal to [r]0.
The graph for zero order reaction is
[r]
34. Key Idea The Arrhenius equation for rate constants at two different temperatures is
k2 Ea  T2  T1 
log    [where, T2> T1]
k1 2.30R  T1T2 
Where, k1 and k2 are rate constants at temperatures T1 and T2, respectively.
R = Gas constant, Ea = Activation energy
For the reaction, H2 + I2 2Hl
Given, k1 = 2.5 × 10–4 dm3mol–1s–1
T1 = (273 + 327)K = 600k
K2 = 1 dm3mol–1s–1 at T2 = (273 + 527)K = 800K
k2 Ea  T2  T1 
Now, log   
k1 2.30R  T1T2 
1 Ea
  log 4

2.5  10 2.303  8.314  10 3
 800  600 
 600  800 
 
(10  103 ) Ea 200
   
2.5 0.019 48  10 4
  log4 + 3log10  Ea × 0.022
2  10g2  3 3.6
 E a    163.6KJmol –1
0.022 0.022
Ea /RT
35. The Arrhenius equation is, k  A.e
Where, k = rate constant,
A = Arrhenius constant, Ea = activation energy, and T = temperature in K

From the equation, it is clear that k decrease exponentially with EaSo, the plot-I is correct.
In the plot-II k is plotted with temperature (in °C but not in K). So, at 0°C, k  0 and k will
increase exponentially with temperature upto 300°C, Therefore, the plot-II is also correct.
36. The temperature dependence of rate of a chemical reaction is expressed by Arrhenius

–E /RT
equation as, k = Ae
Where, A = Arrhenius factor of frequency factor or pre-exponential factor,
R = Gas constant, Ea = Activation energy
Ea
Taking log on both sides of the Eq. (i), the equation becomes In k  InA –
RT
In/k
1/R
1
On comparing with equation of straight line (y = mx + c), the nature of the plot of lnkvs will
RT
be.
(i) Intercept C = In A
(ii) Slope/gradient = m = –Ea = –y Ea = y
So, the energy required to activate the reactant, (activation energy of the reaction, Ea is = y)
37. The temperature dependence of a chemical reaction is expressed by Arrhenius equation,

k  AeEa /RT …(i)
Ea
Where,  is the slope of the plot and In A gives the intercept.
R
Eq.(i) at two different temperatures for a reaction becomes,
k 2 Ea  1 1 
In     …(ii)
k1 R  T1 T2 
 In the given problem,
T1 = 400 K, T2 = 500 K, k1 = 10–5 s–1, k= ?
Ea
  Slope   4606
R
On substituting all the given values in Eq. (ii), we get
k2  1 1 
In  4606   
10 5  400 500 
k2
 10  k 2  10 4 s 1
10 5
Therefore rate constant for the reaction at 500k is 10–4 s–1

K1 K2
38. A  B  C
Rate of formation of B is
dB 
 k1  A   K 2 B 
dt
 d B  
 0 = k1[A] – k2[B]   Give,  0
 dt 
 k2[B] – k1[A]
k1
 Concentration of B, [B] = A
K2
39. Only statement (4) is incorrect, Corrected statement is “Activation enthalpy to from C is 15 kg
mol–1 more than 5 kg mol–1 that is required to form D”. It can be easily explained by following
20
15
Activation
Enthalpy10
D enthalpy
(KJ mol–1)
5
A+B
Reaction C
Coordinate 
Activation enthalpy (or energy) is the extra energy required by the reactant molecules that
result into effective collision between them to form the products.
40. 
k1
The elementary reaction, A 2  2A follows opposing or reversible kinetics,
k 1
(i) Rate of the reaction

r = rforward –rbackward
= k1[A2] –k–1[A2] …(i)
d[A 2 ] 1d[t]
(ii) Again, rate of the reaction can be expressed as, r  
dt dt
So, the rate of appearance of A,
d[t]
i.e. = 2r = 2k1[A2] – 2k–1[A]2 [From Eq.(i)]
dt

CHEMISTRY

CPP
ST
LIQUID SOLUTION NO. 11
Type : 1 (Vapour pressure, ideal and non ideal solution)

1. At 35°C, the vapour pressure of CS2 is 512 mm Hg and that of acetone is 344 mm Hg. A
solution of CS2 in acetone has a total vapour pressure of 600 mm Hg. The false statement
amongst the following is
(1) Raoult’s law is not obeyed by this system
(2) CS2 and acetone are less attracted to each other than to themselves
(3) a mixture of 100 mL CS2 and 100 mL acetone has a volume < 200 mL
(4) heat must be absorbed in order to produce the solution at 35°C [JEE Main 2020]
2. A graph of vapour pressure and temperature for three different liquids X, Y and Z is shown
below :
X Y Z
800
Vapour pressure
(mm Hg)
500
400
200
0 293 313 333 353

Temperature 
The following inference are made :
(1) X has higher intermolecular interactions compared to Y.
(2) X has lower intermolecular interactions compared to Y.
(3) Z has lower intermolecular interactions compared to Y.
(1) (3) (2) (2) (3) (1) (4) (1) and (3)
3. At 363 K, the vapour pressure of A is 21 kPa and tat of B is 18 kPa, One mole of A and 2
moles of B are mixed, Assuming that this solution is ideal, the vapour pressure of the mixture
is _______ kPa. (Round of to the Nearest Integer).

4. At 300 K, the vapour pressure of a solution containing 1 mole of n-hexane and 3 moles of n-
heptane is 550 mm of Hg. At the same temperature, if one more mole of n-heptane is added
to this solution, the vapour presser of the solution increases by 10 mm of Hg. What is the
vapour pressure in mm Hg of n-heptane in is pure state ……….. ?
5. The vapour pressure of pure liquids A and B are 400 and 600 mmHg, respectively at 298 K.
On mixing the two liquids, the sum of their initial volumes is equal to the volume of the final
mixture. The mole fraction of liquids B is 0.5 in the mixture. The vapour pressure of the final
solution, the mole fraction of components A and B in vapour phase, respectively are
(1) 450 mmHg, 0.4, 0.6 (2) 500 mmHg, 0.5, 0.5
(3) 450 mmHg, 0.5, 0.5 (4) 500 mmHg, 0.4, 0.6
6. Liquid M and liquid N form an ideal solution. The vapour pressure of pure liquids M and N are
450 and 700 mmHg, respectively, at the same temperature. Then correct statement is
xM = mole fraction of M in solution;
xN = mole fraction of N in solution;
yM = mole fraction of M in vapour phase;
yN = mole fraction of N in vapour phase;
xM yM xM y M xM yM
(1) > (2) = (3) < (4) (xM – yM) < (xN – yN)
xN yN x N yN xN yN
7. Liquid A and B form an ideal solution in the entire composition range. At 350 K, the vapour
pressure of pure A and pure B are 7 × 103 Pa and 12 × 103 Pa, respectively. The composition
of the vapour in equilibrium with a solution containing 40 mole present of A at this temperature is
(1) xA = 0.76; xB = 0.24 (2) xA = 0.28; xB = 0.72
(3) xA = 0.4; xB = 0.6 (4) xA = 0.37; xB = 0.63
Type : 2 (Colligative properties)
8. C6H6 freezes at 5.5°C. The temperature at which a solution 10 g of C4H10 in 200 g of C6H6
freeze is _______ °C. (The molal freezing point depression constant of C6H6 is 5.12°C/m.)
[JEE Main 2021]
9. 1 molal aqueous solution of an electrolyte A2B3 is 60% ionised. The boiling point of the
solution at 1 atm is _______ K. (Rounded-off to the nearest integer)
[Given Kb for (H2O) = 0.52 K kg mol–1]
10. If a compound AB dissociates to the extent of 75% in an aqueous solution, the molality of the
solution which shows a 2.5 K rise in the boiling point of the solution is ______ molal.
(Rounded-off to the nearest integer) [Kb = 0.52K kg mol–1]

11. 224 mL of SO2(g) at 298 K and 1 atm is passed through 100 mL of 0.1 M NaOH solution. The
non-volatile solute produced is dissolved in 36 g of water. The lowering of vapour pressure of
solution (assuming the solution is dilute) ( P(H2O)  24 mm of Hg) is x × 10–2 mm of Hg, the
value of x is ______. (Integer answer)
12. When 12.2 g of benzoic acid is dissolved in 100 g of water, the freezing point of solution was
found to be –0.93°C (Kf (H2O) = 1.86K kg mol–1). The number (n) of benzoic acid molecules
associated (assuming 100% association) is ____.
13. AB2 is 10% dissociated in water to A2+ and B–. The boiling point of a 10.0 molal aqueous
solution of AB2 is ______ ºC. (Round off to the Nearest Integer)
[Given: Molal elevation constant of water Kb=0.5 K kg mol–1 boiling point of pure water=100ºC]
14. A 1 molal K4 Fe(CN)6 solution has a degree of dissociation of 0.4. Is boiling point is equal to
that of another solution which contains 18.1 weight percent of a non electrolytic solute A. The
molar mass of A is ______ u. (Round off to the Nearest Integer).
[Density of water = 1.0 g cm–3]
15. A solute a dimerizes in water. The boiling point of a 2 molar solution of A is 100.52ºC.
The percentage association of A is. ____ .
(Round off to the Nearest integer)
[Use : Kb for water = 0.52 K kg mol–1
Boiling point of water = 100ºC]
16. Molal depression constant for a solvent is 4.0 K kg mol–1. The depression in the freezing point
of the solvent for 0.03 mol kg–1 solution of K2SO4 is
(Assume complete dissociation of the electrolyte)
(1) 0.18 K (2) 0.36 K (3) 0.12 K (4) 0.24 K
17. The size of raw mango shrinks to a much smaller size when kept in a concentrated salt
solution. Which one of the following processes can explain this?
(1) Osmosis (2) Dialysis (3) Diffusion (4) Reverse osmosis
18. The osmotic pressure of a solution of NaCl is 0.10 atm and that of a glucose solution is 0.20
atm. The osmotic pressure of a solution formed by mixing 1 L of the sodium chloride solution
with 2 L of the glucose solution is x × 10–3 atm. X is ______ (nearest integer)

19. The elevation of boiling point of 0.10 m aqueous CrCl3.xNH3 solution is two times that of 0.05
m aqueous CaCl2 solution. The value of x is ………… .
[Assume 100 % ionization of the complex and CaCl2, coordination number of Cr as 6, and that
all NH3 molecules are present inside the coordination sphere]
20. A set of solution is prepared using 180 g of water as a solvent and 10 g of different non-
volatile solutes A, B and C. The relative lowering of vapour pressure in the presence of these
solutes are in the order
[Given, molar mass of A = 100 g mol–1; B = 200 g mol–1; C = 10,000 g mol–1]
(1) B > C > A (2) C > B > A (3) A > B > C (4) A > C > B
21. How much amount of NaCl should be added to 600 g of water ( = 1.00 g/mL) to decrease the
freezing point of water to –0.2°C ?.............
(The freezing point depression constant for water = 2 K kg mol–1)
22. The osmotic pressure of a dilute solution of an ionic compound XY in water is four times that
of a solution of 0.01 M BaCl2 in water. Assuming complete dissociation of the given ionic
compounds in water, the concentration of XY (on mol L–1) in solution is
(1) 4 × 10–2 (2) 16 × 10–4 (3) 4 × 10–4 (4) 6 × 10–2
23. Molal depression constant for a solvent is 4.0 K mol–1. The depression in the freezing point of
the solvent for 0.03 mol kg–1 solution of K2SO4 is
(Assume complete dissociation of the electrolyte)
(1) 0.18 K (2) 0.36 K (3) 0.12 K (4) 0.24 K
24. At room temperature, a dilute solution of urea is prepared by dissolving 0.60 g of urea in 360 g
of water. If the vapour pressure of pure water at this temperature is 35 mm Hg, lowering of
vapour pressure will be (Molar mass of urea = 60 g mol–1)
(1) 0.027 mmHg (2) 0.031 mmHg (3) 0.017 mmHg (4) 0.028 mmHg

25. 1 g of a non-volatile, non-electrolyte solute is dissolved in 100 g of two different solvents A
and B, whose ebullisocopic constant are in the ratio of 1 : 5. The ratio of the elevation in their
ΔTb (A)
boiling point, , is
ΔTb (B)
(1) 5 : 1 (2) 10 : 1 (3) 1 : 5 (4) 1 : 0.2

26. A solution is prepared by dissolving 0.6 g of urea (molar mass = 60g mol–1) and 1.8 g of
glucose (molar mass = 180 g mol–1) in 100 mL of water at 27°C. The osmotic pressure of the
solution is (R = 0.08206 L atm K–1 mol–1)
(1) 8.2 atm (2) 2.46 atm (3) 4.92 atm (4) 1.64 atm
27. A solution contain 62 g of ethylene glycol in 250 g of water is cooled upto –10°C. If Kƒ for
water is 1.86 K kg mol–1, then amount of water (in g) separated as ice is
(1) 32 (2) 48 (3) 64 (4) 16
28. Elevation in boiling point for 1 molal solution of glucose is 2K. The depression in the freezing
point for 2 molal solution of glucose in the same solvent is 2K. The relation between Kb and Kƒ
is
(1) Kb = 1.5 Kƒ (2) Kb = 0.5 Kƒ (3) Kb = Kƒ (4) Kb = 2 Kƒ
29. Two open beakers one containing a solvent and the other containing a mixture of that solvent
with a non-volatile solute are together sealed in a container. Over time
(1) the volume of the solution decreases and the volume of the solvent increases
(2) the volume of the solution does not change and the volume of the solvent decreases
(3) the volume of the solution increases and the volume of the solvent decreases
(4) the volume of the solution and the solvent does not change
30. K2HgI4 is 40% ionised in aqueous solution The value-of its van't Hoff factor (i) is
(1) 1.6 (2) 1.8 (3) 2.2 (4) 2.0
31. Freezing point of a 4% aqueous solution of X is equal to freezing point of 12% aqueous
solution of Y. If molecular weight of X is A, then molecular weight of Y is
(1) 4A (2) 2A (3) 3A (4) A
32. Molecules of benzoic acid (C6H5COOH) dimerise in benzene. 'w' g of the acid dissolved in 30
g of benzene shows a depression in freezing point equal to 2 K. If the percentage association
of the acid to form dimer in the solution is 80, then w is
(Given that Kƒ = 5 K kg mol–1, molar mass of benzene acid = 122 g mol–1)
(1) 1.8 g (2) 1.0 g (3) 2.4 g (4) 1.5 g
Type : 3 (Henry’s law)

33. The oxygen dissolved in water exerts a partial pressure of 20 kPa in the vapour above water.
He molar solubility of oxygen in water in water is _______ × 10–5 mol dm–3
(Round off to the Nearest Integer).[Given : Henry’s law constant = KH = 8.0 × 104 kPa for O2.
Density of water with dissolved oxygen = 1.0 kg dm–3] [JEE Main 2021]

34. Henry’s constant (in kbar) for four gases , ,  and  in water at 298 K is given below :
   
–5
KH 50 2 2 × 10 0.5
3 –3
(density of water = 10 kg m at 298 K) This table implies that
(1) a has the highest solubility in water at a given pressure
(2) solubility of  at 308 K is lower than at 298 K
(3) the pressure of a 55.5 molal solution of  is 1 bar
(4) the pressure of a 55.5 molal solution of  is 250 bar
35. For the solution of the gases w, x, y and z in water 298 K, the Henry's law constant (KH) are
0.5, 2, 35 and 40 K bar, respectively. The correct polt for the given data is
z
Partial pressure
Partial pressure
(1) z (2)
y
y
x
x
w w
(0, 0) Mole fraction of water (0, 0) Mole fraction of water
z z
y
Partial pressure
Partial pressure
(3) (4) x w
(0, 0) Mole fraction of water (0, 0) Mole fraction of water
36. Which one of the following statements regarding Henry's law not correct?
(1) Different gases have different KH (Henry's law constant) values at the same temperature
(2) Higher the value of KH at a given pressure, higher is the solubility of the gas in the liquids
(3) The value of KH increases with increase of temperature and KH is function of the nature of
the gas
(4) The partial pressure of the gas in vapour phase is proportional to the mole fraction of the
gas in the solution

Type : 4 (Miscellenous)
37. When 9.45 g of ClCH2COOH is added to 500 mL of water, its freezing point drops by 0.5°C.
The dissociation constant of ClCH2COOH is x × 10–3. The value of x is ________.
K f(H O)  1.86K kgmol1  [JEE Main 2021]

 2 
38. 2 molal solution of a weak acid HA has a freezing point of 3.885ºC. The degree of dissociation
of this acid is ______ × 10–3. (Round off to the Nearest Integer).
[Given:Molal depression constant of water=1.85K kg mol–1 Freezing point of pure water = 0ºC]
39. C cylinder containing an ideal gas (0.1 mol of 1.0 dm3) is in thermal equilibrium with a large
volume of 0.5 molal aqueous solution of ethylene glycol at its freezing point. If the stoppers S1
and S2 (as shown in the figure) are suddenly withdrawn, the volume of the gas in litres after
equilibrium is achieved will be ………..
(Given, Kf(water) = 2.0 K kg mol–1, R = 0.08 dm3 atm K–1 mol–1)
Frictionless
piston
S1 S2
Ideal gas
aq. Ethylene glycol
40. A soft drink was bottled with a partial pressure of CO2 of 3 bar over the liquid at room
temperature. The partial pressure of CO2 over the solution approaches a value of 30 bar when
44g of CO2 is dissolved in 1 kg of water at room temperature. The approximate pH of the soft
drink is ________×10–1.
(First dissociation constant of H2CO3 = 4.0 × 10–7) log 2 = 0.3;
density of the soft drink = 1 g mL–1)

ANSWER KEY
1. (3) 2. (2) 3. (19) 4. (600) 5. (4)
6. (1) 7. (2) 8. (1) 9. (375) 10. (3)
11. (12) 12. (2) 13. (106) 14. (85)15. (50) by Allen (100)
16. (2) 17. (1) 18. (167) 19. (5.00) 20. (3)
21. (1.76) 22. (4) 23. (2) 24. (3) 25. (3)
26. (3) 27. (3) 28. (4) 29. (3) 30. (2)
31. (3) 32. (3) 33. (25) 34. (4) 35. (1)
36. (2) 37. (35) 38. (50) 39. (2.18) 40. (37)
SOLUTION
1. The incorrect statement among the given statements in (3) and the explanation of all the
statements is as follows:
According to Raoult’s law, vapour pressure of the solution pid (ideal vapour pressure)
= pA° + (pB° – pA°)xB
(A = solvent: acetone, B = solute: CS2)
Given; pA° = 344 mm Hg.
pB° = 512 mm Hg
 pId = 344 + (512 – 344)xB
or pId = 344 + 168xB and so, 0 < xB < 1.
Also, total vapour pressure (p) = 600 mm Hg
 For any value of xB, p > pId
Since p  pId, so option (1) is correct.
Option (2) is also correct. Since p > pId, (i.e. positive deviation) therefore attractive force
between CS2 and acetone is weaker than CS2–CS2 or acetone-acetone attraction.
Option (3) is incorrect as for positive deviation, V > 0 because final volume of solution must
be greater than the sum of volumes of components taken.
Option (4) is correct. Since in such solution , mixH is positive because energy is required to
break A – A and B – B bonds.
2. From given graph it can be seen that, X has higher vapour pressure as compared to Y at
lower temperature (or to attain same vapour pressure, Y need higher temperature than X). It
means that intermolecular interactions must be weaker than Z compared to Y, which further
must be weaker than Z by the same reason also. Hence, option (2) is correct.

3. Given PA0 = 21kPa  PB0 = 18kPa
 An Ideal solution is prepared by mixing 1 mol A and 2 mol B.
1 2
 XA = and XB =
3 3
 Acc to Raoult’s low

PT = XAPA0 + XBPB0
1  2 
 PT    21    18 
3  3 
 PT = 7 + 12 = 19 KPa
4. Given
Vapour pressure of solution = 550 mmHg
Mole of hexane (nnex) = 1 mol
Mole of heptanes (nhep) = 3 mol
From Raoult’s law,
Vapour pressure in solution = vapour pressure of pure solvent × mole fraction
p = pº
Here, vapour pressure of solution = p,
Vapour pressure of pure solvent = pº and mole fraction = 
Total vapour pressure of solution,
ptotal = pºhex hex + pºhep hep
Case I : Mole fraction of hexane,
1
hex =  0.25
1 3
Mole fraction of heptanes,
3
hep =  0.75
1 3
p = pºhex 0.25 + pºhep × 0.75
550 = pºhex 0.25 + pºhep × 0.75 …(i)
Case II : According to question, when 1 mole of heptanes added and vapour pressure
increased by 10 mm of Hg.
Mole fraction of hexane,
1
hex =  0.20
1 4
Mole fraction of heptane,
4
hep =  0.80
1 4
p = pºhex hex + pºhep hep

vapour pressure increased by 10 mm of Hg then
p =560
 560 = pºhex 0.20 + pºhep 0.80 …(ii)
Eq. (i) multiplied by 0.20
 550 × 0.20 = (0.25 × 0.20)pºhex + (0.75 × 0.20)pºhep
 110 = 0.05pºhex + 0.15pºhep …(iii)
Eq. (ii) multiplied by 0.25,
 560 × 0.25 = (0.20 × 0.25)pºhex + (0.8 × 0.25)pºhep
140 = 0.05 pºhex + 0.20pºhep …(iv)
Now, Eq. (iii) and Eq. (iv)
 0.05pºhex + 0.15pºhep – 0.05pºhex – 0.20pºhep = 110 – 140
 0.15pºhep – 0.20pºhep = – 30  –0.05pºhep = – 30
30
 pºhep = = 600 mm of Hg
0.05
Thus, vapour pressure of pure n-heptane (pºhep) is 600 mm of Hg.
5. According to Dalton's law of partial pressure

ptotal = pA + pB
= p°A A + pB° B ...(i)
Given, p°A = 400 mm Hg, pB° = 600 mmHg
B = 0.5, A + B = 1
 A = 0.5
On substituting the given values in Eq. (i). We get, ptotal = 400 × 0.5 + 600 = 500 mmHg
Mole fraction of A in vapour phase,
pA p°  0.5 × 400
YA = = A A = = 0.4
ptotal ptotal 500
Mole of B in vapour phase,

YA + YB = 1
YB = 1 – 0.4 = 0.6  
6. Key Idea For a solution of volatile liquids the partial vapour pressure of each component of
the solution is directly proportional to its mole fraction present in solution. This is known as
Raoult's law.
Liquid M and N form an ideal solution. Vapour pressure of pure liquids M and N are 450 and
700 mm Hg respectively.

  p°N > p°M
So, by using Raoult's law
yN > x N ...(i)
and xM > y M ...(ii)
Multiplying (i) and (ii) we get
yN xM > y M xN
xM yM
  >
xN yN
Thus, correct relation is (1).
7. For ideal solution,

p = x'A p°A + x'B p°B
Q x'A = 0.4, x'B = 0.6
p°A = 7 × 103 Pa, p°B = 12 × 103 Pa
On substituting the given values in Eq. (i),
we get
p = 0.4 × 7 × 103 + 0.3 × 12 × 103
= 10 × 103 Pa = 1 × 104 Pa
In vapour phase,
p A x' A p°A 0.4 × 7 ×10 3
xA = = = = 0.28
p p 1×10 4
 xB = 1 – 0.28 = 0.72 [Q xA + xB = 1]
8. Pure Solvent : C6H6 (l)

Given : Tf = 5.5°C
Kf = 5.12° C/m
10g : Solute is non dissociative
200 g C6H6
Q Tf = kf × m
 10 
 58 
 Tf  Tf  5.12  
   mol
0 '
 200 
 1000  kg
 
' 5.12  5  10
 5.5  Tf 
58
'
 Tf  1.086 C 1 C

9. Tb = iKbm
= (1 + 4) × 0.52 × 1
= 3.4 × 0.52 × 1 = 1.768
Tb = 1.768 + 313.15 = 374.918 K = 375 K
10.  = 0.75, n = 2
i = 1 –  + n = 1 – 0.75 + 2 × 0.75 = 1.75
Tb = ikbm
or, 2.5 = 1.75 × 0.52 × m
2.5
or, m = = 2.74
1.75  0.52
 nearest integer answer will be 3
11.
Sol.(1) SO2 + 2NaOH Na2SO3 + H2O
224
10m mol 5m mol
0.0821 298 (L.R) (i  3)
= 9.2 m mol
2
Ps = P0. Xsolvent = 24  = 23.82
(2  15  10 3 )
P= 0.18 torr = 18 × 10–2 torr.
Sol.(2) SO2 + NaOH NaHSO3

9.2 10 –
– 0.8 9.2
0
P = P . Xsolute
(1.6  18.4)
= 24 × 24  = 0.2376 = 23.76 × 10–2
2020
12. Tf = i × kf × m
12.2
0 – (–0.93) = i × 1.86 ×  1000
122  100
0.93
i  0.5
1.86
1 
i  1    1  1
n 
n=2

13. AB2  A2+ + 2B–
t=0 a 0 0
t=0 a–a a 2a
nT = a –a + a + 2a
= a (1 + 2)
So i = 1 + 2
Now Tb = i × m × Kb
Tb = (1 + 2) × m × Kb
 = 0.1 m = 10 Kb = 0.5
Tb = 1.2 × 10 × 0.5
=6
So boiling point = 106
14. K4Fe(CN)6 4K+ + Fe(CN)64–

Initial conc. 1 m 0
= 0.6 m = 1.6 m
Effective molality = 0.6 + 1.6 + 0.4 = 2.6 m For same boiling point, the molality of another
solution should also e 2.6 m.
Now, 18.1 weigh percent solution means 18.1 gm solute is present in 100 gm solution and
hence, (100 – 18.1 =) 81.9 gm water.
18.1/ M
Now, 2.6 
81.9 / 1000
 Molar mass of solute, M = 85
15. Tb = Tb – Tb0

100.52 – 100
= 0.52ºC
 a
i  1  
 2
Tb = i Kb × m
 a
0.52 = i   1   × 0.52 × 2
 2 
a=1
So, percentage association = 100%.

16. Key Idea Depression in freezing point (Tƒ) is given by Tƒ = iKƒm
i = vant Hoff factor
Kƒ = molal depression constant, m = molality
Kƒ = 4.0 K kg mol–1 (Given)
m = 0.03 mol kg–1 (Given)
Tƒ = ?
For K2SO4, i = 3
It can be verified by the following equation :
K2SO4 2K+ + SO24

Using formula
Tƒ = iKƒ × m
Tƒ = 3 × 4 × 0.03 = 0.36 K
17. When a raw mango is kept in a concentrated salt solution, the mango will shrink because of
exo-osmosis. Mango cell membrane acts as semi-permeable membrane and its cell
cytoplasm is considered as a solution of concentration, C1M (say). Let the concentration of
salt solution is C2M, where C1 < C2 (mentioned).
So, osmotic pressure developed at salt solution, 2 will be greater than that at cell cytoplasm,
1 at a given temperature.
1 = C1RT and 2 = C2RT
So, solvent molecules (water) will flow out from mango cells to salt solution resulting shrinking
of mango. This state is also known as plasmolysis.
18. Osmotic pressure,  = i × C × RT

Here, i = van’t Hoff factor, T = temperature C = concentration and R = gas constant
For NaCl, i = 2
So, NaCl = i × CNaCl × RT
0.1 = 2 × CNaCl × RT
0.05
CNaCl 
RT
For glucose, i = 1 because it cannot ionise
So, glucose = i × Cglucose × RT
02 × 1 × Cglucose × RT
0.2
Cglucose =
RT
( nNaCl = numbers of moles NaCl)

NNaCl in 1L = CNaCl × Vlitre
0.05
= (nglucose = number of moles of glucose)
RT
0.05
So, final concentration NaCl =
3RT
0.4
Final concentration glucose =
3RT
total = NaCl + glucose
= [I × CNaCl + Cglucose]RT
 2  0.05 0.4  0.5
=    RT  atm
 3RT 3RT  3
= 0.1666 atm = 166.6 × 10–3 atm
= 167.00 × 10–3 atm
So, x = 167.00
19. Tb = i × m × Kb
For CaCl2, i = 3, m(CaCl2 ) = 0.05 m
 Tb = 3 × 0.05 × Kb = 0.15 Kb

 Molality of CrCl3.xNH3 = 0.1 m
 T’b = i × m × Kb = 0.1 iKb
Given that : 0.1 iKb = 2 × 0.15 × Kb
 i = 3 and coordinate number is 6.
Thus, complex will be [Cr(NH3)5Cl]Cl2
Hence, the correct answer is 5.
20. Relative lowering in vapour pressure

p  p s p
(RLVP) =  solube or RLVP =  solute
p p
w w
n  moles of solute = ; N  moles of solvent =
M M
Given, weight of solvent (water) = 180 g
Weight of different non-volatile solute wA, wB and wC = 10
Molar mass of MA = 100 g mol–1
MB = 200 g mol–1  MC = 10,000 g mol–1
RLVP for A,

10
 p  10 0.1
   10 180   0.091
 p  A 
1.1
100 18
RLVP for B,
10
 p  200 0.05
   10 180   0.0049
 p B 
10.05
200 18
RLVP for C,
10
 p  10,000 0.001 0.001
     = 0.000099
 p C 10 180 0.001  10 10.001

10,000 18
From the above value the relative lowering of vapour pressure in the presence of there solute
are in the following order :
 p   p   p 
     
 p  A  p B  p C
Hence, option (3) is correct.
i  K f  w NaCl  1000
21. Tf = i × m × Kf =
MNaCl  w H2O
( 58.5)
w B  1000
(m = molality) =
MB  w A
Tf = 0.2 because freezing point = –0.2°C

Kf of water 2 kg mol–1 (Given)
i = van’t Hoff factor, for NaCl = 2
Tf  MNaCl  w H2O
 w NaCl 
i  K f  1000
0.2  58.5  600

= =1.755 g 1.76 g
2  2  1000
22. Key Idea Osmotic pressure is proportional to the molarity (3) of the solution at a given
temperature,  = CRT
Concentration of BaCl2 = 0.01 M (Given)
XY = 4BaCl2 (Given)
i × CRT = 4 × i × CRT ...(i)

For the calculation of i,

XY  X+ + Y– (Here, i = 2)
BaCl2  Ba2+ + 2Cl– (Here, i = 3)
Putting the values of i in (i)
2 × [XY] = 4 × 3 × [BaCl2]
2 × [XY] = 12 × 0.01
12× 0.01
[XY] =
2
So, the concentration of XY = 0.06 mol L–1
= 6 × 10–2 mol L–1
23. Key Idea Depression in freezing point ( Tƒ) is given Tƒ = iKƒm
i = vant Hoff factor
Kƒ = molal depression constant
m = molality
Kƒ = 4.0 K kg mol–1 (Given)
–1
m = 0.03 mol kg (Given)
Tƒ = ?
for K2SO4, i = 3
It can be verified by the following equation :
K2SO4 2K+ + SO2–

4
Using formula
Tƒ = iKƒ × m
Tƒ = 3 × 4 × 0.03 = 0.36K
24. Key Idea For dilute solution, lowering of vapour pressure (p) = p0 and relative lowering of
Δp
vapour pressure = which is a colligative property of solutions.
p0
Δp
= B × i  p = B × i × p0
p0
where, p0 = vapour pressure of pure solvent

i = van't Hoff factor
B = mole fraction of solute
Given,
p0 = vapour pressure of pure water of 25°C
= 35 mmHg
B = mole fraction of solute (urea)

0.60
nB 60 0.01
= = =
n A + nB 360 + 0.60 20 + 0.01
18 60
0.01
= = 0.0005
20.01
i = van't Hoff factor = 1 (for urea)
Now, according to Raoult's law, p = B × i × p0
On substituting the above given values, we get
p = 0.0005 × 1 × 35 = 0.0175 mm Hg

25. The expression of elevation of boiling point,
w 2 ×1000
Tb = Kb × m × i = kb = × ×i
M2 × w 1
where, m = molality
i = van't Hoff factor = 1 (for non-electrolyte/non-associable)
w2 = mass of solute in g = 1g (present in both of the solutions)
M2 = molar mass solute in g mol–1 (same solute in both of the solutions)
w1 = mass of solvent in g = 100 g (for both the solvent A and B)
Kb = elullioscopic constant
So, the expression becomes,
ΔTb (A) K b (A) 1  K b (A) 1 
    Given = 
ΔTb (B) K b (B) 5  K b (B) 5 
26. Key Idea Osmotic pressure is proportional to the molarity (3) of the solution at a given
temperature (T).
Thus,   C,  = CRT (for dilute solution)
n
= RT
V
n
For the relation,  = CRT RT
V
Given, mass of urea = 0.6 g
Molar mass of urea = 60 g mol–1
Mass of glucose = 0.8 g
Molar mass of glucose = 180 g mol–1
=
n2 (urea) + n2 (glucose) RT
V

 0.6 1.8 
 + 
 60 180 
= × 1000 × 0.0821 × 300
100
= (0.01 + 0.01) × 10 × 0.0821 × 300
 = 4.92 atm
27. Considering the expression of the depression in freezing point of a solution,

DTƒ = Kƒ × m × i
w B ×1000
Tƒ – Tƒ = Kƒ × ×i ....(i)
MB × w A (ing)
Here, Tƒ = 0°C, Tƒ = – 10°C
wB = mass of ethylene glycol = 62 g

MB = molar mass of ethylene glycol
CH2 —CH2
OH OH
= 62 g mol–1
wA = mass of water in g as liquid solvent
i = van't-Hoff factor = 1
(for ethylene glycol in water)
Kƒ = 1.86 K kg mol–1
On substituting in Eq. (i), we get
62 ×1000
0 – (– 10) = 1.86 × ×1
62 × w A
1.86× 62×1000
 wA = = 186 g
10× 62
So, amount of water separated as ice (solid solvent)
= 250 – wA = (250 – 186)g = 64 g
28. Elevation in boiling point (Tb) = Kb × m × i

Depression is freezing point (Tƒ) = Kƒ × m × i
where, m = molality
For the glucose solution (van't Hoff factor, i = 1)
ΔTb1m = ΔTƒ2m = 2K
So, Kb × 1 × 1 = Kƒ × 2 × 1
 Kb = 2Kƒ

29.
Liquid Vapour
Only solvent-It has Solvent + non-

more vapour volatile solute-It
pressure has less vapour
pressure
If a non-volatile solute is added to a solvent to form a solution, the vapour pressure gets
decreased.
 According to Raoult’s law if vapour pressure of pure solvent is p°, vapour pressure of
solvent is p°, vapour pressure of solvent in solution (p) is = p°.xA.
 p < p°
Since, vapour pressure of solution is less, there will be net backward reaction [i.e., vapour 
liquid] in that beaker.
Thus, its volume increases.
In another beaker containing only net reaction is forward.
Thus, volume pressure.
30. The ionisation of K2HgI4 in aqueous solution is as follows :
K2[HgI4] 2K+ + [HgI4]2–

van't Hoff factor (i) for ionisation reaction is given as,
i = 1 +  (n – 1)
where n = number of ions
   = degree of ionisation or dissociation
From above equation, it is clear that n = 3
i = 1 + 0.4 (3 – 1) [Given, %  = 40% or  = 0.4] = 1.8
31. Given, Freezing point of 4% aqueous solution of X :

= Freezing point of 12% aqueous solution of Y
Or (Tƒ)X = (Tƒ)Y [ Tf = Tƒ° – Tƒ]
Kƒ × mx = KƒmY
where, mX and mY are molarity of X and Y,
respectively.

or mX = mY
Number of molesof solute(n)
Now, molality =
Mass of solvent (inkg)
Weight
n=
Molecular mass
wX wY
=
M X × (w solvent )1 MY × (w solvent )2
Given, wX = 4 and w(solvent)1 = 96

wY = 4 and w(solvent)2 = 88
MX = A
4 ×1000 12 ×1000
 =
M X × 96 MY × 88
12×1000×MX × 96
Thus, MY =
4×1000× 88
96×12
= × A = 3.27A  3A
4×88
32. Molecules of benzoic acid dimerise in benzene as:
2(C6H5COOH) (C6H5COOH)2
Now, we know that depression in freezing point (Tƒ) is given by following equation:
i×K ƒ × w solute ×1000
Tƒ = i × Kƒ × m = ...(i)
Mw solute w solvent
Given, wsolute (benzoic acid) = w g

wsolvent (benzoic acid) = 122 g mol–1, Tƒ = 2 K
Kƒ = 5 Kkg mol–1, % = 80 or  = 0.8
Initial 1 0
Final 1 –   / 2
= 1 – 0.8 = 0.2 0.8 / 2 = 0.4
Total number of moles at equilibrium
= 0.2 + 0.4 = 0.6
Number of moles at equilibrium
i=
Number of moles present initially
0.6
i= = 0.6
1
On substituting all the given values in Eq. (i), we get

0.6× 5× w ×1000
2= , w = 2.44 g
122× 30
Thus, weight of acid (w) is 2.4 g. molecules of benzoic acid dimerise in benzene as :
Now, we know that depression in freezing point (Tƒ) is given by following equation:
i×K ƒ × w solute ×1000
Tƒ = i × Kƒ × m = ...(i)
Mw solute × w solvent
Given, wsolute (benzoic acid) = w g

wsolute (benzoic acid) = 30 g
MwSolute (benzoic acid) = 122 g mol–1, Tƒ = 2 K
Kƒ = 5 Kkg mol–1, % = 80 or  = 0.8
Initial 1 0
Final 1 –   / 2
= 1 – 0.8 0.8 / 2 = 0.4
= 0.2
Total number of moles at equilibrium
= 0.2 + 0.4 = 0.6
Number of moles at equilibrium
i=
Number of moles present initially
0.6
i= = 0.6
1
On substituting all the given values in Eq. (i), we get
0.6× 5× w ×1000
2= , w = 2.44 g
122× 30
Thus, weight of acid (w) is 2.4 g.
33. P = KH · x
nO2
or, 20 × 103 = (8 × 104 × 103) ×
nO2  nwater
1 nO2 nO2
or,  
4000 nO2  nwater nwater
 1 
 4000 
Means 1 mole water (= 18 gm = 18 ml) dissolved =    1000  1 mol dm–3
18 72
= 1388.89 × 10–5 mol dm–3  1389 mol dm–3

34. Henry’s equation for solubility (S) of a gas () in a liquid is expressed in terms of mole-fraction
of the gas (B) at a given temperature.
p = KH × B = KH × S
1
So, solubility of gas, S  at T(K) and given pressure.
KH
Order of solubility of the gases (high the value of KH,) lower is the solubility :  >  >  > 
So, option (1) is not correct.
Again, KH  temperature, i.e. solubility of the gas will decreases with increases in temperature
alos. But this conclusion cannot be drawn from table,
We know, mole-fraction of a solute (2) in binary aqueous solution.
18m
B  [ m = molality]
1000  18m
For  at m = 55.5 molal
 18  55.5 
p  KH  m  (2  105 )   
 1000  18  55.5 
= 1.81 × 10–5 K bar = 1.8 × 10–2 bar
For  at m = 55.5 molal
 18  55.5 
p  K H  (0.5)   
 1000  18  55.5 
= 02498 k bar 250 bar
So, option (4) is correct.
35. According to Henry’s law (at constant temperature)

 pgas = KH × gas (solute) = KH × [1 –  H 2 O (solvent)]
 pgas = KH – KH  H 2 O
 pgas = partial pressure of the gas above its solution with a liquid (solvent) say water.
gas = mole fraction of the gas (solute) in the solution.
 H 2 O = mole fraction of water (solvent).

pgas pgas
KH KH
H 2O = 0 H 2O = 0
gas = 1 gas = 0
[i.e. pgas = KH] Higher the vlaue of KH, higher will be the partial pressure of the gas (pgas), at a
given temperature. The plot of pgas vs H2O gives a (–ve) slope.
pgas = KH – KH × H2O
Comparing the above equation with the equation of straight line y = mx + c

Slope = – KH, intercept = KH
So, (i) Higher the value of KH, more (–ve) will be the slope and it is for z (KH = 40 K bar)
(ii) Higher the value of KH, higher with the value of intercept, i.e. partial pressure and it is also
for z.
36. At constant temperature, solubility of a gas (S) varies inversely with Henry's law constant (KH)
Pressure P
KH = =
Solubility of a gasinaliquid S
Thus, higher the value of KH at a given pressure, the lower is the solubility of the gas in the
liquid.
37. ClCH2COOH ClCH2COO– + H+

i = 1 + (2 – 1) 
i=1+
Tf = ikfm
  9.45  
  94.5  
0.5 = (1 + a)(1.86)   
  500  
  1000  
 
5 1.28
 1    
3.72 3.72
32

93
ClCH2COOH ClCH2COO– + H+

C – C  C C
(C )2 C 2 0.1
Ka   C  0.2
C  C 1   500 / 1000
0.2(32 / 93)2 .2  (32)2
Ka   = 0.036
(1  32 / 93) 93  61
Ka = 36 × 10–3
38. Tf = (1 + ) Kfm

 = 0.05 = 50 × 10–3
39. Kf = 2.0 (Given) m = 0.5 m (Given)

Tf = Kf × m = 2 × 0.5 = 1
 Tf = Actual freezing point of water is –1.
= 273 – 1 = 272 K.
Pressure of gas after the stoppers are withdrawn = 1 atm (atmospheric pressure)
nRT 0.1 0.08  272
V=  = 2.176 L = 2.18 L
p 1 atm
40. At 30 bar pressure mass CO2 in 1 kg water = 44 g

At 3 bar pressure mass of CO2 in 1 kg
Water = 4.4 g
4.4
Moles of CO2 in 1 kg water =  0.1 mol
44
In solution, H2O + CO2 H2CO3 (0.1 mol)
or H2CO3 H+ + HCO3–
Initially 0.1 – –
At equil. 0.1(1 – ) 0.1  0.1 
Here,  = degree of dissociation
[H ][HCO3 ]
K a1 
[H2CO3 ]
[Here, K a1 = first dissociation of constant of H2CO3]
(0.1  )2  Ka 3 
4 × 10–7 =  0.12  C  10 ,1    1
0.1(1   )  
4.0 × 10–7 × 0.1 = 0.01 2;  = 2 × 10–3
[H+] = 0.1 = 0.1 × 2 × 10–3 = 2 × 10–4
pH = –log[H+] = – log[2 × 10–4]
= –[log2 + log[10–4]]
= –[0.3 – 4] = 3.7 = 3.7 × 10–1

CHEMISTRY

CPP
ST
SOLID STATE NO. 12
Type : 1 (Crystalline Solid)
1. A hard substance melts at high temperature and is an insulator in both solid and in molten
state. This solid is most likely to be a / an :
(1) Ionic acid (2) Molecular solid (3) Metallic solid (4) Covalent solid
[JEE Main 2021]
Type : 2 (Types of Unit Cell)
2. The coordination number of an atom in a body centered cubic structure is _______.

[Assume that the lattice is made up of atoms.]
[JEE Main 2021]
3. The unit cell of copper corresponds to a face centered cube of edge length 3.596 Å with one
copper atom at each lattice point. The calculated density of copper in kg/m3 is _______.
[Molar mass of Cu : 63.54 g ; Avogadro Number = 6.022 × 1023]
4. A certain element crystallises in a bcc lattice of unit cell edge length 27 Å. If the same element
under the same conditions crystallises in the fcc lattice, the edge length of the unit cell in Å will
be _______ . (Round off to the Nearest Integer).[Assume each lattice point has a single atom]
[Assume 3 = 1.73, 2 = 1.41]
5. In a binary compound, atoms of element A form a hcp structure and those of element M
occupy 2/3 of the tetrahedral voids of the hcp structure. The formula of the binary compound
is :
(1) M2A3 (2) M4A3 (3) M4A (4) MA3
6. An element with molar mass 2.7 × 10–2 kg mol–1 forms a cubic unit cell with edge length 405
pm. If its density is 2.7 × 103 kg m–3, the radius of the element is approximately….. × 10–12 m
(to the nearest integer)

7. A diatomic molecule X2 has a body-centred cubic (bcc) structure with a cell edge of 300 pm.
The density of the molecule is 6.17 g cm–3. The number of molecules present in 200 g of X2 is
(Avogadro constant (NA) = 6 × 1023 mol–1)
(1) 40NA (2) 2NA (3) 8NA (4) 4NA
8. An element crystallises in a face-centred cubic (fcc) unit cell with cell edge a. The distance
between the centres of two nearest octahedral voids in the crystal lattice is
a a
(1) (2) a (3) 2a (4)
2 2
9. Element ‘B’ forms ccp structure and ‘A’ occupies half of the octahedral voids, while oxygen
atoms occupy all the tetrahedral voids. The structure of bimetallic oxide is
(1) A2BO4 (2) AB2O4 (3) A2B2O (4) A4B2O
10. Consider the bcc unit cells of the solids 1and 2 with the position of atoms as shown below.
The radius of atom B is twice that of atom. A. The unit cell edge length is 50% more in solid
2 than in 1. What is the approximate packing efficiency in solid 2?
A A A A
A A A A
A B
A A
A A
A A A A
Solid 1 Solid 2
(1) 65% (2) 90% (3) 75% (4) 45%
11. The ratio of number of atoms present in a simple cubic, body centered cubic and face
Centered cubic structure are, respectively.
(1) 8 : 1 : 6 (2) 1 : 2 : 4 (3) 4 : 2 : 1 (4) 4 : 2 : 3
12. At 100C, copper (Cu) has FCC unit cell structure with cell edge length of xÅ. What is The
approximate density of Cu (in g cm–3 ) at [Atomic mass of Cu = 63.55 u]
211 205 105 422
(1) (2) (3) (4)
x3 x3 x3 x3
13. Which primitive unit cell has unequal edge lengths (a  b  c ) and all axial angles different
from 90?
(1) Hexagonal (2) Monoclinic (3) Tetragonal (4) Triclinic

14. A compound of formula A2B3 has the hcp lattice. Which atom forms the hcp lattice and what
fraction of tetrahedral voids is occupied by the other atoms?
2
(1) hcp lattice –A, tetrahedral voids – B
3
1
(2) hcp lattice –A, tetrahedral voids – B
3
1
(3) hcp lattice –B, tetrahedral voids – A
3
2
(4) hcp lattice –B, tetrahedral voids – A
3
15. A solid having density of 9 × 103 kgm–3 forms face centered cubic crystals of edge length
200 2 pm. What is the molar mass of the solid? [Avogadro constant = 6 × 1023 mol–1,  =3]
(1) 0.03050 kgmol–1 (2) 0.4320 kgmol–1 (3) 0.0432 kgmol–1 (4) 0.0216 kgmol–1
16. A metal crystallizes in a face centered cubic structure. If the edge length of its unit cell is 'a',
the closest approach between two atoms in metallic crystal will be
a
(1) 2a (2) 2 2 a (3) 2a (4)
2
17. Sodium metal crystalises in a body centred cubic lattice with a unit cell edge of 4.29 Å. The
radius of sodium atom is approximately
(1) 1.86 Å (2) 3.22 Å (3) 5.72 Å (4) 0.93 Å
Type : 3 (Voids and Radius ratio)
18. The number of octahedral voids per lattice site in a lattice is _____.
19. Ga (atomic mass 70 u) crystallizes in a hexagonal close packed structure. The total number of
voids in 0.581 g of Ga is ________ × 1021. (Round off to the Nearest Integer).
20. A crystal is made up of metal ions M1 and M2 and oxide ions. Oxide ions form a ccp lattice
structure. The cation M1 occupies 50% of octahedral voids and the cation M2 occupies 12.5%
of tetrahedral voids of oxide lattice. The oxidation numbers of M1 and M2 are, respectively
(1) +2, +4 (2) +1, +3 (3) +3, +1 (4) +4, +2

21. An element has a face-centred cubic (fcc) structure with a cell edge of a. The distance
between the centres of nearest tetrahedral voids in the lattice is
a 3
(1) 2a (2) a (3) (4) a
2 2
22. The radius of the largest sphere which fits properly at the centre of the edge of a body centred
cubic unit cell is (Edge length is represented by 'a')
(1) 0.134 a (2) 0.027 a (3) 0.047 a (4) 0.067 a
Type : 4 (Types of Crystal defects)
23. Which of the following compounds is likely to show both Frenkel and Schottky defects in its
crystalline form ? [JEE Main 2020]
(1) AgBr (2) CsCl (3) KBr (4) ZnS
24. Which tyyp of 'defect' has the presence of cations in the interstitial sites?
(1) Schottky defect (2) Vacancy defect
(3) Frenkel defect (4) Metal deficiency defect
Type : 5 (Doping and Vacancies)
25. KBr is doped with 10–5 mole percent of SrBr2. The number of cationic vacancies in 1 g of KBr
crystal is _______ 1014. (Round off to the Nearest Integer).
[Atomic Mass : K : 39.1 u, Br : 79.9 u, NA = 6.023 × 1023] [JEE Main 2021]

ANSWER KEY
1. (4) 2. 8 3. 9077 4. 33 5. (2)

6. 143.00 7. (4) 8. (1) 9. (2) 10. (2)
11. (2) 12. (4) 13. (4) 14. (3) 15. (1)
16. (4) 17. (1) 18. 1 19. 15 20. (1)
21. (3) 22. (4) 23. (1) 24. (3) 25. 5
SOLUTION
1. Covalent or network sold have very high melting point and they are insulators in their slid and
molten form.
Z M 4  63.54
3. FCC, d  3
 23 10 3
= 9076 kg/m3
NA  a 1000  6.022  10  (3.596  10 )
4. (For BCC 3 a =4r)
3
so r   27
4
for FCC a = 2 2 r
3 3
= 2 2   27 =  27 = 33
4 2
5. M 2 A6
12
3
M8A6
M4A3
6. For the cubic (Z = 4) unit cell,

Corner
r
2r
Face
r centre
a
r = Radium of the element

a = Edge length of the cubic unit cell (fcc) = 405 pm
2  405
4r  2a  r  pm
4
= 143.189 pm Q 143 pm = 143 × 10–12 m
Z M
7. We know that, d
a3  NA
Given, density d = 6.17 g,

edge length a = 300 pm = 3 × 10–8 cm,
NA = 6 × 1023 mol–1
2M
 6.17  (For bcc, Z = 2)
(3  10 )  6  1023
8 3
 M = 50 g/mol
Hence, number of molecules present in 200 g of X2 is
w 200
N  NA   NA  4NA 
M 50
8.
OV
OV
a/2
OV a/2
In fcc octahedral voids are present at the edge centrers at body center.
Minimum distance between centres of two octahedral at voids.
2 2
a  a a 2 a2 a
x        
 2  2 4 4 2
9. The number of element ‘B’ in the crystal

Structure = 4N
Number of tetrahedral voids = 2N
Number of octahedral voids = N
N 4
 Number of ‘A’ in the crystal =  2
2 2
Number of oxygen (O) atoms = 2N = 2 × 4 = 8
 The structure of bimetallic oxide = A2 B2 O8
= AB2 O4

Volume occupiedby sphere
10. Key Idea : packing efficiency  × 100
Volume of cube
Given, rB = 2rA
150
A2 = a 1 + a1  1.5 a 1
100
For bcc lattice
4ra= 3 a 1
3 a1
ra
4
4ra
a1
3
 4r  3  4r 
a2 =1.5  a    a 
 3  2 3 
a2= 2 3 rA
4 3 4
rA  z A  B3  ZB
Packing efficiency = 3 3
3
a2
1
[As the atoms A are present at the edges only Z A   8  1 , atom B is present only at the
8
body centre ZB = 1]
4 3  4 3 
 3 rA 1   3 rB 1
 PE2 =   
3

a2
4 3 4
A  (2rA )3
 3 3
(2 3 rA )3
4 3
A  9
3 
 
3
8  3 3 rA 2 3
= 90.72%  90%
11. The ratio of number of atoms present in simple cube, body structure are 1 : 2 : 4 respectively
12. For fcc. Rank of the unit cell (Z) = 4

Mass of one Cu-atom, M = 63.55 u
Avogadro’s number, NA = 6.023 × 1023 atom
Edge length, a = x Å = x × 10–8 cm

Z M
Density (4) =
NA  a 3
4  63.55
=
6.023x1023  (X  108 )3
422.048
= 3
g cm3
x
13. Triclinic primitive unit cell has dimensions as, a  b c and       90
Among the seven basic or primitive crystalline system the triclinic system is most
unsymmetrical. In other cases, edge length and axial angles are given as follows:
Hexagonal : a = b c and  =  = 90º,  = 120º
Monoclinic : a b c and = = 90º, 90º
Tetragonal : a b c and = = = 90º
14. Total effective number of atoms in hcp unit lattice =

Number of octahedral voids on hcp = 6
 Number of tetrahedral voids (TV) in hcp
= 2 × number of atoms in hcp lattice
= 2 × 6 = 12
As, formula of the lattice is A2B3.
Suppose, A B
1 
 3 TV  (hcp)
 
1
 × 12 6
3
2
 1
3
 2 3
1
So,A = tetrahedral voids, B = hcp lattice
3
15. Density of crystal

MZ d  NA  a 3
d=  M =
NA  a 3 Z
Given, d = 9 × 103 kgm–3

M = Molar mass of the solid
Z = 4 (for fcc crystal)

NA = Avogadro's constant = 6 × 1023 mol–1
a = Edge length of the unit cell
= 200 2 pm
= 200 2 × 10–12 m
On substituting all thegiven values, we get
(9  103 )kgm3  (6  1023 )mol1  (200 2  10 12 )3 m3
=
4
= 0.0305 kg mol–1
16. For cc arrangement, 4r = 2a
Where, r = radius and a = edge length

2a a
 Closest distance = 2r = 
2 2
17.
D
r
a
2r
C
r a
A B
a
For this figure,
(AC)2 = (AB)2 + (BC)2
(AC)2 = a2 + a2 = 2a2
Also, (AD)2 = (AC)2 + (DC)2
(4r)2 = 2a2 + a2
16r2 = 3a2
3
  r a
4
Now, when Na metal crystallizes in bcc unit cell with unit cell edge, a = 4.29Å
We have the forula for radius,
3
i.e. r × 4.29Å = 1.86 Å
4

18. If number of lattice points are N.
then effective octahedral voids = N
So, octahedral voids / lattice site = 1
19. HCP structure : Per atom, the there will be one octahedral void (OV) and two tetrahedral voids
(TV).
 therefore total no of atoms of Ga will be-
=
 Now, total Number of voids = 3 × total no. Of atoms
0.581
= 3  6.023  1023  14.99  1021
70
= 15 × 1021
20. Number of O2– ions in ccp = 4

Total charge on oxide = –8
Number of tetrahedral voids = 8
Number of voids = 4
Number of cation M1 occupies 50% of octahedral voids,
50
42
100
Number of cation M2 occupies 12.5% of tetrahedral voids of oxide lattice,
12.5
8  1
100
So, formula is (M1)2(M2)O4.
This must be neutral. Both metals must have +8 charge on total
Oxidaion number of M1  2
From given options: 
Oxidaion number of M2  4
 (2 × 2 + 2) + (1 × + 4) = + 8
Hence, correct option is (1).

21. In fcc unit cell. Two tetrahedral vords are formed on each of the four non–parallel body
diagonals of the cube at a distance of 3a / 4 from every corner along the body diagonal.
One of thebod
diagonal of cubic
A
¼ AB
3 A' Position of 2 TVs
a
4 ½ (AB) one one of the body
diagonal of the unit
cell
B' ¼ (AB)
B
3
a
4
The angle between body diagonal and an edge is cos–1 (1/ 3 ). So. The projection of the line
on an edge is a /4.
Similarly. Other tetrahedral void also will be a/4 away.
So, the distance between these two is
 a a a
a  4   4  2 .
 
22. For body centred cubic structure,
3
radius (R) = a …..(i)
4
Where, a = edge length
According to question, the structure of cubic unit cell can be shown as follows :
R 2r R
a
 a = 2(R + r) ……(iii)
On substituting the value of R from Eq. (i) to Eq. (ii),
we get
a 3
 ar
2 4

a 3 2a  3a
r=  a
2 4 4
a(2  3 )
r=
4
 r = 0.067a
r
23. AgBr shows both Schottky and Frenkel defects. Because the (radius of cation and radius of
r
anion) ration in AgBr is not verylarge or not very small. (Agcl shows only Schottky defect due
r r
to greater value of , whereas Agl shows only Frenkel defect due to smaller value of  ).
r r
24. It is the "Frenkel defect" in which cations leave their original site and occupy interstitial site as
shown below.
+ – + – + – +
– + – + – + – Original vacant
+ – + – + – + site of cation
– + – – + –
+ – + – + – + Cation in
– + – + – ++ – interstitial
+ – + – + – +
site
– + – + – + –
10 5
25. 1 Mole KBr (= 119 gm) have moles SrBr2 and hence, 10–7 moles cation vacancy
100
(as 1 Sr2+ will result 1 cation vacancy)
 Required number of cation vacancies

10 7  6.023  10 23
=  5.06  1014  1014
119

CHEMISTRY

CPP
ST
SURFACE CHEMISTRY NO. 13
Type : 1 (adsorption and absorption)

1. 3.12 g of oxygen is adsorbed on 1.2 g of platinum metal. The volume of oxygen adsorbed per
gram of the adsorbent at 1 atm and 300 K in L is______.
[R = 0.0821 L atm K–1 mol–1] [JEE Main 2021]
2. Amongst the following statements regarding adsorption, those that are valid are:
(A) DH becomes less negative as adsorption proceeds.
(B) On a given adsorbent, ammonia is adsorbed more than nitrogen
(C) On adsorption, the residual force acting along the surface of the adsorbent increases
(D) With increase in temperature, the equilibrium concentration of adsorbate increases.
(1) (D) and (A) (2) (B) and (C) (3) (A) and (B) (4) (C) and (D)
3. A mixture of gases O2, H2 and CO are taken in a closed vessel containing charcoal. The graph
that represents the correct behavior of pressure with time is
Pressure
Pressure
(1) (2)
Time Time
Pressure
Pressure
(3) (4)
Time Time
4. Given, Gas: H2,CH4,CO2,SO2

Critical temperature/K 33 190 304 630 On the basis of data given above, predict which of the
following gases shows least adsorption on a definite amount of charcoal?
(1) CH4 (2) SO2 (3) CO2 (4) H2

Type : 2 (Freundlich adsorption isotherm)
5. In Freundlich adsorption isotherm, slope of AB line is : [JEE Main 2021]
B
N
A
x
log
m
log P
(1) log n with (n > 1) (2) n with (n, 0.1 to 0.5)
1 1 1 
(3) log with (n < 1) (4) with   0 to 1
n n n 
x
6. In Freundlich adsorption isotherm at moderate pressure, the extent of adsorption   directly
m
proportional to Px. The value of x is
1
(1) zero (2) (3) 1 (4) 
n
7. The mass of gas adsorbed, x per unit mass of adsorbate, m was measured at various
x
pressure, p. A graph between log and log p gives a straight line with slope equal to 2 and
m
x
the intercept equal to 0.4771. The value of at a pressure of 4 atm is :
m
(Given, log 3 = 0.4771)
8. Adsorption of a gas follows Freundlich adsorption isotherm. If x is the mass of the gas
x
adsorption on mass m of the adsorbent, the correct plot of versus p is
m
200 K 270 K
x x 250 K
(1) 250 K (2)
m m
270 K 200 K
p p
200 K 270 K
250 K
x x
(3) (4) 250 K
m 700 K m
200 K
p p
x
9. For Freundlich adsorption isotherm, a plot of log   (y-axis) and log p(x-axis) gives a straight
m
line. The intercept and slope for the line is 0.4771 and 2, respectively. The mass of gas,
adsorbed per gram of adsorbent if the initial pressure is 0.04 atm, is………. × 10–4g.
(log 3 = 0.4771)

10. Adsorption of a gas follows Freundlich adsorption isotherm, x is the mass of the gas adsorbed
x x
on mass of the adsorbent. The plot of log versus log p is shown in the given graph. is
m m
proportional to
x
log 2
m
3
log p
(1) P2/3 (2) P3/2 (3) P3 (4) P2
11. A gas undergoes physical adsorption on a surface and follows the given Freundlich
x
adsorption isotherm equation Kp 6.5 . Adsorption of the gas increases with
m
(1)increase in p and increase in T (2) increase in p and decrease in T
(3) decrease in p and decrease in T (4) decrease in p and increase in T
12. Adsorption of a gas follows Freundlich adsorption isotherm. In the given plot, x is the mass of
the gas adsorbed on mass m of the adsorbent at pressure p (x/m) is proportional to
x 2 unit
log 4 unit
m
log p
(1) p2 (2) p1/4 (3) p1/2 (4) p
Type : 3 (Colloids and its properties)
13. The nature of charge on resulting colloidal particles when FeCl3 is added to excess of hot
water is :
(1) Positive (2) Sometimes positive and sometimes negative
(3) Neutral (4) Negative [JEE Main 2021]
14. The INCORRECT statement below regarding colloidal solution is :

(1) A colloidal solution shows colligative properties
(2) An ordinary filter paper can stop the flow of colloidal particles
(3) The flocculating power of Al3+ is more than that of Na+
(4) A colloidal solution shows Brownian motion of colloidal particles.

15. The charges on the colloidal CdS sol and TiO2 sol are, respectively :
(1) positive and positive (2) positive and negative
(3) negative and negative (4) negative and positive
16. Which of the following is used for the preparation of colloids ?

(1) Bredig’s Arc method (2) Ostwald process
(3) Mond process (4) van Arkel method
17. Identify the correct molecular picture showing what happens at the critical micelle
concentration (CMC) of an aqueous solution of a surfactant
(polar head; ~non-polar tail;  water).
(A) (B) (C) (D)
(1) (C) (2) (B) (3) (D) (4) (A)
18. Kraft temperature is the temperature

(1) below which the aqueous solution of detergents starts freezing
(2) below which the formation of micelles takes place
(3) above which the aqueous solution of detergents starts boiling
(4) above which the formation of micelles takes place.
19. The aerosol is a kind of colloid in which

(1) gas is Is dispersed in liquid (2) gas is dispersed in solid
(3) liquid is dispersed in water (4) solid is dispersed in gas
20. Match the catalysts Column I with products Column II.

Column I(Catalyst) Column II(Product)
(A)V2O5. (i)Poiyethlyene
(B)TiCl4/Al(Me)3 (ii)Elhanal
(C)PbCl3 (iii)H2SO4
(D)Iron oxide (IV)NH3
(1) (A)-(ii), (B)-(iii),(C)-(i), (D)-(iv) (2) (A)-(iv), (B)-(iii), (C)-(ii), (D)-(i)
(3) (A)-(iii), (B)-(i), (C)-(ii), (D)-(iv) (4) (A)-(iii), (B)-(iv), (C)-(i), (D)-(ii)
21. The correct option among the following is

(1) colloidal medicines nrc more effective, because they have small surface area.
(2) brownian motion in colloidal solution is faster if the viscosity of the solution is very high.
(3) addition of alum to water makes it unfit for drinking.
(4) colloidal particles in lyophobic sols can be precipitated by clcctrophoresis.

22. Peptisation is
(1) process of bringing colloidal molecule into solution
(2) process of converting precipitate into colloidal solution
(3) process of converting a colloidal solution into precipitate
(4) process of converting soluble particles to form colloidal solution
23. Among the following the incorrect statement about colloids is

(1) They can scatter light
(2) They are large than small molecules and have high molar mass
(3) The osmotic pressure of a colloidal solution at the same concentration
(4) The range of diameters of colloidal particles is between 1 and 1000 nm
24. Which of the following is not an example of heterogeneous catalytic reaction?

(1) Haber’s process (2) Combustion of coal
(3) Hydrogenation of vegetable oils (4) Ostwald’s process
25. Hemoglobin and gold sol are examples of

(1) negatively and positively charge sols, respectively
(2) negatively charged sols
(3) positively charged sols
(4) positively and negatively charged sols, respectively
26. An example of solid sol is

(1) gem stones (2) hair cream (3) butter (4) paint
27. Among the colloids cheese (3), milk (M) and smoke (S), the correct combination of the
dispersed phase and dispersion medium, respectively is
(1) C : liquid in solid; M : liquid in liquid; S: solid in gas
(2) C : solid in liquid ; M : liquid I liquid; S: gas in solid
(3) C : liquid in solid; M: liquid in solid; S: solid in gas
(4) C : solid in liquid; M: solid in liquid; S: solid in gas
28. Among the following the false statement is

(1) Tyndall effect can be used to distinguish between a colloidal solution and a true solution
(2) It is possible to cause artificial rain by throwing electrified sand carrying from an opposite
to the one on clouds from an aero-plane
(3) Lyophilic sol can be coagulated by adding an electrolyte
(4) Latex is a colloidal solution of rubber particles which are positively charged.

29. The Tyndall effect is observed only when following condition are satisfied
I. The diameter of the dispersed particles is much smaller than the wavelength of the light
used.
II. The diameter of the dispersed particle is not much smaller than the wavelength of the light
used.
III. The refractive indices of the dispersed phase and dispersion medium are almost similar in
magnitude.
IV. The refractive indices of the dispersed phase and dispersion medium differ greatly in
magnitude.
(1) I and IV (2) II and IV (3) I and III (4) II and III
Type : 4 (Hydrophilic and hydrophobic sol.)

30. Which one of the following statements is FALSE for hydrophilic sols ?
(1) Their viscosity is of the order of that of H2O.
(2) The sols cannot be easily coagulated.
(3) They do not require electrolytes for stability.
(4) These sols are reversible in nature. [JEE Main 2021]
Type : 5 (Hardy Schulze rule)

31. Most suitable salt which can be used for efficient clotting of blood will be :-
(1) NaHCO3 (2) FeSO4 (3) Mg(HCO3)2 (4) FeCl3
[JEE Main 2021]
32. For the coagulation of a negative sol, the species below, that has the highest flocculating
power is :
(1) SO2–
4 (2) Ba2+ (3) Na+ (4) PO34
33. The flocculation value of HCl for arsenic sulphide solution is 30 m mol L–1. If H2SO4 is used for
the flocculation of arsenic sulphide, the amount in grams of H2SO4 is 250 mL required for the
above purpose is………………..
(molecular mass of H2SO4 = 98 g/mol)
34. As per Hardy-Schulze formulation, the flocculation values of the following for ferric hydroxide
sol are in the order :
(1) K3[Fe(CN)6] < K2CrO4 < AlCl3 < KBr < KNO3
(2) AlCl3 > K3[Fe(CN)6] > K2CrO4 > KBr = KNO3
(3) K3[Fe(CN)6] < K2CrO4 < KBr = KNO3 = AlCl3
(4) K3[Fe(CN)6] > AlCl3 > K2CrO4 > KBr > KNO3
35. Which of the salt-solution is most effective for coagulation of aresinoussulphide?

(1) BaCl2 (2) AlCl3 (3) Na3PO4 (4) NaCl

ANSWER KEY
1. (2) 2. (3) 3. (3) 4. (4) 5. (4)

6. (2) 7. (6) 8. (1) 9. (48) 10. (1)
11. (2) 12. (3) 13. (1) 14. (2) 15. (4)
16. (1) 17. (4) 18. (4) 19. (4) 20. (3)
21. (4) 22. (2) 23. (3) 24. (2) 25. (4)
26. (1) 27. (1) 28. (4) 29. (2) 30. (1)
31. (4) 32. (2) 33. (0.37) 34. (3) 35. (2)
SOLUTION
3.12
 0.0821 300
1. V  32 = 2.40 l
1
Q 1.2 gm adsorbs 2.40 l
1 gm adsorbs 2 l
2. On adsorption (both physical and chemical), the residual force acting along the surface of
absorbent decreases. So, H of the adsorption becomes less negative as adsorption
proceeds. So, statement (1) is correct but statement (3) is incorrect. Ammonia molecules
(NH3) is larger in size and dipolar in nature. Nitrogen is smaller in size and it is a non-polar
molecule. So, degree of adsorption : NH3 > N2. So, Statement (2) is correct. With increase in
temperature, kinetic energy of adsorbate molecules will increase and hence, its equilibrium
concentration will decreases. So, statement (4) is not correct.
3. Option (3) is the graph that represents correct behavior of pressure with time. With passage of
time, the pressure of the gases decreases and finally reach a constant value.
It is due to adsorption of gases by charcoal. The decrease in pressure is faster in the
beginning, but as the adsorbent charcoal gets saturated, pressure attains constancy.
4. Same adsorbent (charcoal in this case) at same temperature will adsorb different gases to
different extent. The extent to which gases are adsorbed is proportional to the critical
temperature of gas.
8a
Tc 
27Rb
Where, a is the magnitude of intermolecular forces between gaseous molecules. Thus, higher
the critical temperature more is the gas adsorbed, Among the given gases, H2 has the
minimum critical temperature, i.e. 33k thus, it shows least adsorption on a definite amount of
charcoal.

x
5.  K(P)1/n
m
x 1
log    logK  logP
m n
y = c + mx
m = 1/n so slope will be equal to 1/n.
x/m
1<n< n=
n<1
P
N
1
Hence 0  1
n
1
x 1
6. As per Freundlich adsorption isotherm    KP n  x 
m n
Hence answer is (2)
7. From Freundlich adsorption isotherm equation,

x 1
log  logK  logp
m n
x 
log
m
log p
Where we plot log x/m vs log p, we get a straight line of

1 1
(i) Slope = 2  n
n 2
(ii) Intercept = log K = 0.4771  log K = log 3  K = 3
x
So,  Kp1/n = 3 × 42 = 48.00 ( p = 4 atm)
m

8. Freundlich adsorption gives the variation in the quantity of gas adsorbed by a unit mass of
solid adsorbent with the change in pressure of the system for a given temperature.
log x/m
Slop = 1/n
Intercept = log k
log p
The expression for the Freundlich isotherm can be represented by the following equation.
x
 kp1/n
m
where, n > 1
where, x is the mass of gas adsorbed, x is the mass of adsorbent. p is pressure and n is a
constant, which depends upon the nature of adsorbent and the gas at a given temperature.
Taking the logarithm on both side of the equation,
x 1
log  logk  logp
m n
x
p (At low pressure)
m
x
 p (At high pressure)
m
On increasing temperature physical adsorption decreases
(x/m)
Temperature
9. According to Freundlich adsorption isotherm

x
 Kp1/n ………(i)
m
Taking logarithm of Equation (i)

x 1
log = log K + log p ………(ii)
m n
1
Here, given slope =  2,
n
Pressure (p) = 0.04 atm and intercept = log K = 0.4771 ( K = 3)
Mass of gas adsorbed per gram of adsorbent
x
 K.p1/n
m
x x
= 3.p2  = 3 × (0.04)2 = 48 × 10–4.
m m
10. Key Idea According to Freundlich,

x
 Kp1/n [n  1]
m
x
Where, m = mass of adsorbent, x = mass of the gas adsorbed, = amount of gas adsorbed
m
per unit mass of solid adsorbent, p = pressure, k and n = constants.
x 1
The logarithm equation of Freundlich adsorption isotherm is log  logK  logp
m n
On comparing the above equation with straight line equation, (y = mx + c)
1
We get m = slope = Andc = log K
n
From the given plot.
Y2  Y1 1 2
m  
x 2  x1 n 3
x
   Kp2\3
m
11. For physisorption or physical adsorption. Adsorption isotherm (Temperature, T= constant) is

shown below:
x
m x
Moderate pressure zone,  p1/n
m
x
Where, x = amount of adsorb ate, m = amount of adsorbent, degree of adsorption
m

1 1
= order of the reaction, where 0 < < 1 and so, 1 < n <
n n
1
x
Here, =  Kp 2
m
1
x
i.e.  p2
m
Adsorption isobar (Pressure, p = constant)
x
m
So, the rate of physical adsorption of the gas, increases with p (when, T is constant) and
decreases with T (with p is constant).
1 1
x x
12. According to Freundlich adsorption isotherm,  pn   Kpn
m m
x 1
On taking log on both sides, we get log    logK  logp
m n
x
On comparing with equatin of straight line, y = mx + c, plot of log. vs log p gives.
m
(y 2  y1 ) 1 2 1
Slope   
(x 2  x1 ) n 4 2
x
 p1/ 2
m
13. If FeCl3 is added to hot water, a positively charged sol, hydrated ferric oxide is formed due to
adsorption of Fe3+ ions.
Fe2O3. xH2O/Fe3+ Positively charged.
14. Colloidel solution exhibits colligative properties

An ordinary filter can not stop the flow of colloidal particles.
Flocculating power increases with increase the opposite charge of electrolyte.
Colloidal particles show Brownian motion.
15. CdS sol  –ve sol

TiO2 sol  +ve sol

16. Using Bredig’s arc method, colloids (metal sols which are lyophobic) can be prepared.
In this method, two electrodes of metal (whose sol is to be prepared) are dipped in
concentration alkali. The electrodes act as arc for high voltage transmission of current. The
metal particles get dispersed in the medium to produce metal sols like Au-sol, Ag-sol, Pt-sol
etc.
Ostwald process is an industrial process for manufacturing HNO3. Reactions are as follows:
Pt gauge
(i) 4NH3 + 5O2 
500K,9atm
 3NO + 6H2O
(ii) 2NO + O2 
 2NO2
(iii) 3NO2 + H2O  2HNO3 + NO

Mond process is associated with refining of nickel.
80 C 200C
Ni + 4O   [Ni(CO)4] 
4CO
 Ni
Crude Pure
Van Arkel Method, ultra pure Zr, Hf, Ti metals get refined.
600C 1800 C
Zr + 4I2   Zrl4(g) 
2I
 Zr
Crude 2 Pure
17. CMC (critical micelle concentration) is the concentration of a surfactant in a bulk phase, above
which aggregates of surfactant molecules, so called micelles, start to form.
A micelle is an aggregate of monomer surfactant molecules dispersed in a liquid colloid.
Hydrophilic ‘Head’ regions in contact with surrounding solvent, sequestering the hydrophobic.
‘Tail’ ‘regions’ in the micelle centre.
18. Micelles formation take place only above a particular temperature called Kraft temperature
(TK). Hence, the correct option is (4).
19. The aerosol is a kind of coiioidInwhtch solid is dispersed in gas e g smoke, dust.
20. (A)(iii);(B)(i);(C)(ii);(D)(iv)
(i) TiCl4 + AlCl3 (Ziegler-Natta catalyst) is used to prepare polyethylene from ethane.
Zieglar Natta
n.CH2  CH2     CH2 – CH2 n
catalyst
Ethene Polyethylene
(ii) V2O5 (Vanadium pent oxide) is used as catalyst to prepare H2SO4 from contact process,
Reaction involved is
2SO2(g) + O2(g)   2SO3(g)
2 5 VO

It is the key step in the manufacture of H2SO4.
(iii) Fe (Iron) is used as catalyst in Haber’s process for the manufacture of ammonia.
N2(g) + 3H2(g)  Fe(s)
  2NH3(g)
(iv) Pd (Palladium) is used to prepare ethanol. Reaction involved is
PdCl2 /CuCl2
H2C = CH2 + O2 
H2O
 CH3CHO
This reaction is also known as Wacker’s process.
21. The explanation of the given statements are as follows:

(1) Colloidal medicines are more effective because they (dispersed phase) have larger
surface area.
Thus, option (1) is incorrect.
(2) Brownian motion of dispersed phase particles in colloidal solution is faster if the option (2)
is incorrect.
(3) Addition of alum (K2SO4Al2(SO2)324H2O) an electrolyte to water makes it fit for drinking
purpose because alum coagulates mud particles from water.
Thus, option (3) is incorrect.
(4) Precipitation of lyophobic solution particles by electrophoresis is called Cottrell
precipitation. Thus, option (4) is correct.
22. Peptisation is a process of converting precipitate into colloidal solution. This process involves
the shaking of precipitate with the dispersion medium in the presence of small amount of
electrolyte. The electrolyte added is called peptizing agent.
During peptisation, the precipitate adsorbs one of the lons of the electrolyte on its surface,
This causes the development of positive or negative charge on precipices, which ultimately
breakup into smaller particles of the size of a colloid.
23. Statement (3) is incorrect about colloids. Colligative properties such as relative lowering of
vapour pressure, such relative lowering of vapour pressure, elevation in boiling point,
depression in freezing point and osmotic pressure of a colloidal solution is of low order than
the true solution at the same concentration.
24. In heterogeneous catalytic reactions, physical state of reactants and that of catalyst(s) used
are different.
Haber’s process, hydrogenation of vegetable oils and Ostwald’s process all are
heterogeneous process. Combustion of coal is not a heterogeneous catalytic reaction.
  In Haber’s process

Fe(s),Mo(s)
N2(g) + 3H2(g)   2NH3(g)
  Hydrogenation of vegetable oils,
 3 3  (Ph P) Rh Cl
V egetable oil(I) 
or Ni(s)
 Vanaspati(s)
(Unsaturated)
  Ostwald’s process,

Pt(s)
4NH3(g) + 5O2(g) 
V2 O5 (s)
 4NO(g) + 6H2O(g)
 No catalyst is used in combustion of coal. The reaction is highly spontaneous in nature.
C  O2 
 O2
(Coal)
25. Hemoglobin and gold sol both are colloids and always carry an electric charge, Hemoglobin is
a positively charged sol, because in hemoglobin, Fe2+ ion is the central metal ion of the
octahedral complex.
All metal sols like, Au–sol, Ag–sol etc; are negatively charged sols.
26. Solid sol consists of solid as both dispersed phase and dispersion medium. In gemstones,
metal crystals (salt and oxides of metals) are dispersed in solid (stone) medium. Hair cream is
an emulsion (liquid in liquid). Butter is a colloidal solution of liquid in solid. Paint is also sol
(solid in liquid).
27.
Dispersed Dispersed Type of collold Examples
phase medium colloid
Liquid Solid Gel Cheese (3), butter, Jellies
Liquid Liquid Emulsion Milk (M), hair cream
Solid Gas Aerosol Smoke (S), dust
Thus, C : liquid in solid, M : liquid in liquid and S: solid in gas.
28. Statement given as statement (4) is incorrect. Latex is a stable dispersion, i.e. emulsion of
polymer micro particles in an aqueous medium.
These micro particles belong to rubber and are negatively charged in nature, Natural latex
contains some amount of sugar, resin, protein and ash as well.
These closest synthetic latex that can be associated with the properties of natural latex is
SBR, i.e. Styro Butane Rubber.
Rest of all the statements are correct.

29. Colloidal solution show Tyndall effect due to scattering of light by colloidal particles in all
directions in space, It is observed only under the following conditions.
(i) The diameter of the colloids should not be much smaller than the wavelength of light used.
(ii) The refractive indices of the dispersed phase and dispersion medium should differ greatly
in magnitude.
30.  Viscosity of hydrophilic sol > viscosity of H2O

 Hydrophilic sol is more stable so can't be easily coagulated.
 Hydrophilic sols are reversible sols.
 No electrolytes are required to stabilize hydrophilic sol.
31. Blood : negatively charged sol

According to Hardly-schulz rule, for the negatively charged sol, most (+) ve ion is needed for
its efficient coagulation.
32. To coagulate negative so, cation with higher charge has higher coagulation value.
33. (except value : 0.3675 g)

Flocculation value = number of m mol of electrolyte needed per litre.
Since, As2S3 is negatively charged colloid, H+ causes its flocculation.
Here, 30 m mol of HCl is needed per 1 L per 250 mL, HCl required would be
30  250
= = 7.5 m mol
1000
 nH required = 7.5 m mol
7.5m mol
So, mol of H2SO4 required = = 3.75 m mol
2
3.75  98
Mass of H2SO4 = = 0.3675 g.
1000
The value may range from 0.36 to 0.38.
34. Ferric hydroxide sol (and other metal oxide and hydroxide sols) is generally positively
charged. So, as per Hardy-Schulze rule, the flocculation power is greatest for electrolyte
having most highly negatively charged anion.
 Flocculation power follows the order
K 3 [Fe(CN)6 ]  K 2CrO 4  KBr = KNO3 = AlCl3
Anionic charge:(-3) (-2) (-1)

As flocculation power increases, flocculation value decreases. Therefore, order of flocculation
values is
K3[Fe(CN)6] < K2CrO4 < KBr = KNO3 = AlCl3
35. Arsenious supplied sol is a negative colloid, As2S3(S2–) so, it will be coagulated by the action
of an electrolyte.
According to the Hardy-Schulze rule, the higher the charge of the ion, the more effective it is
in bringing about coagulation. Here, the cations available are Al3 (from AlCl3) Ba2+ (from
BaCl2) and Na+ (from Na3PO4 and NaCl). So, their power to coagulate As2S3. (S2–) will follow
the order as Al3+> Ba2+> Na+

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C HE M IS T R Y

RANK BOOSTING COURSE-2022

MOLE CONCEPT NO. 01

Type : 1 (Average Atomic Mass And Molar Mass)

Type : 2 (Empirical Formula And Molecular Formula)

3. At 300 K and 1 atmospheric pressure, 10 mL of a hydrocarbon required 55 mL of O2 for

4. 25 g of an unknown hydrocarbon upon burning produces 88 g of CO2 and 9 g of H2O. This

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M AgNO3 = 169.87 g/mol

Type : 4 (Percentage Composition)

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Type : 5 (Concentration Terms)

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the height of the monolayer?

[Density of fatty acid = 0.9 g cm-3; π=3]

(1) 10-6 m (2) 10-4 (3) 10-5 (4) 10-2

atomic mass ; Fe= 56, O= 16, Mg= 24, P= 31, C= 12, H= 1)

(1) C3H8(g) + 5O2(g)  3 CO2 (g) + 4H2O(I)

(2) P2(s) + 5O2 (g)→ P4O10 (s)

(3) 4Fe(s) + 3O2(g) →2Fe2O3(s)

(4) 2Mg(s) + O2 (g) → 2MgO(s)

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Mass of hydrogen = × mass of H2O

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6. 3Pb (NO3)2 + Cr2(SO4)3  3PbSO4 + 2Cr(NO3)3

8. Base + Acid  Salt + H2O

For 2 moles of butane 13 moles of O2 is required.

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No. of moles of urea = Given mass / molar mass

11. Given, Mass of [Co(NH3)6]Cl3 = 0.3 g

12. Ferrous sulphate heptahydrate FeSO4 .7H2O

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15. 44 gm CO2 have 12 gm carbon

16. 2NaHCO3 + H2C2O4 → 2CO2 + Na2C4O4 + H2O

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∴ W NaHCO3 = 1.02 × 10-5 × 84 × 103 mg

6.5  1.89  1000

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22. Molar of mass Na2CO3.xH2O

23. For 100 g sample of the solution,

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25. 100 mL (cm3) of hexane contains 0.27 g of fatty acid

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(c) 4Fe(s) + 3O2(g) →2Fe2O3(s)

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Type : 2 (Bohr Model)

(A) Kinetic energy of electron is μ

(C) Frequency of revolution of electron in an orbit is .

(D) Coulombic force of attraction on the electron is .

3. Given below are two statements :

(1) (2) (3) (4)

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Temperature (K) Wavelength

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in maximum and minimum frequencies in cm–1. The ratio ∆νLyman / ∆νBalmer is

Type : 4 (Photoelectric Effect)

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Type : 5 (De Broglie Wavelength)

[Use : 3 = 1.73, h = 6.63 × 10–34 Js

22. The de Broglie wavelength of an electron in the 4th Bohr orbit is

Type : 6 (Heisenberg Uncertainty Principle)

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