JEE

ADVANCED

CHEMISTRY
PHYSICAL CHEMISTRY

Atomic Structure
Mole Concept
Gaseous State

Chemical Equilibrium
Ionic Equilibrium
Thermodynamics
 CONTENT
CONTENT
CONTENT

TOPIC PAGE No.

1 ATOMIC STRUCTURE

1.1 Exercise 1-15

1.2 Answer Key 16-16

2 MOLE CONCEPT

2.1 Exercise 17-28

2.2 Answer Key 29-29

3 IDEAL GASES

3.1 Exercise 30-42

3.2 Answer Key 43-43

4 REAL GASES

4.1 Exercise 44-50

4.2 Answer Key 50-50

5 CHEMICAL EQUILIBRIUM

5.2 Exercise 51-66

5.3 Answer Key 67-67

6 IONIC ELEMENTRY

6.1 Exercise 68-72

6.2 Answer Key 72-72

7 IONIC ADVANCED

7.1 Exercise 73-80

7.2 Answer Key 81-81

8 THERMODYNAMICS

8.1 Exercise 82-96

8.2 Answer Key 97-97

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 Atomic Structure

EXERCISE-4
PART - 1 : SINGLE OPTION CORRECT TYPE
1. Which is not true with respect to cathode rays ?
(A) A stream of electrons (B) Charged particles
(C) Move with same speed as that of light (D) Can be deflected by electric field
2. The mass to charge ratio (m/e) for a cation is 1.5 × 10–8 kg/C. What is the mass of this atom ?
(A) 2.4 × 10–19 g (B) 2.4 × 10–27 g (C) 2.4 × 10–24 g (D) None of these
3. An oil drop has 6.39 × 10–19 C charge. Find out the number of electrons in this oil drop.
(A) 2 (B) 4 (C) 6 (D) 8
4. Which of the following statement is true in the context of photoelectic effect ?
(A) The kinetic energy of ejected electron is independent of the intensity of a radiation.
(B) The number of photoelectrons ejected depends upon the intensity of the incident radiation.
(C) The kinetic energy of the emitted electrons depends on the frequency of the incident radiation.
(D) All of these
5. A light source of wavelength  illuminates a metal and ejects photo-electrons with (K.E.)max = 1 eV.

Another light source of wavelength , ejects photo-electrons from same metal with (K.E.)max = 4eV..
3
Find the value of work function ?
(A) 1 eV (B) 2 eV (C) 0.5 eV (D) None of these
6. In Bohr's model of the hydrogen atom the ratio between the period of revolution of an electron in the orbit
of n = 1 to the period of the revolution of the electron in the orbit n = 2 is -
(A) 1 : 2 (B) 2 : 1 (C) 1 : 4 (D) 1 : 8
7. In an atom, two electrons move round the nucleus in circular orbits of radii R and 4R. The ratio of the time
taken by them to complete one revolution is : (Consider Bohr model to be valid)
(A) 1 : 4 (B) 4 : 1 (C) 1 : 8 (D) 8 : 1
8. The angular momentum of an electron in a given orbit is J, Its kinetic energy will be :
1 J2 Jv J2 J2
(A) (B) (C) (D)
2 mr 2 r 2m 2
9. The potential energy of the electron present in the ground state of Be3+ ion is represented by:
e2 e e2 e2
(A)  (B)    r (C)  (D) 
 0 r 0  0 r 2  0 r

10. The kinetic energy of the electron present in the ground state of Li2+ ion is represented by :

3e 2 3e 2 3e 2 3e 2
(A) (B)  (C) (D) 
8 0 r 8 0 r 4 0 r 4  0 r
11. Which transition in Li2+ would have the same wavelength as the 2  4 transition in He+ ion ?
(A) 4  2 (B) 2  4 (C) 3  6 (D) 6  2
12. Let 1 be the frequency of the series limit of the Lyman series, 2 be the frequency of the first line of the
Lyman series, and 3 be the frequency of the series limit of the Balmer series :
(A) 1 – 2 = 3 (B) 2 – 1 = 3 (C) 3 = 1/2 (1 – 3) (D) 1 + 2 = 3
13. No. of visible lines when an electron returns from 5th orbit upto ground state in H spectrum :
(A) 5 (B) 4 (C) 3 (D) 10
14. If the shortest wave length of Lyman series of H atom is x, then the wave length of the first line of Balmer
series of H atom will be -
(A) 9x/5 (B) 36x/5 (C) 5x/9 (D) 5x/36

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 Atomic Structure
15. In a sample of H-atoms, electrons de-excite from a level ‘n’ to 1. The total number of lines belonging to
Balmer series are two. If the electrons are ionised from level ‘n’ by photons of energy 13 eV. Then the
kinetic energy of the ejected photoelectrons will be :
(A) 12.15 eV (B) 11.49 eV (C) 12.46 eV (D) 12.63 eV
16. A particle X moving with a certain velocity has a debroglie wave length of 1Å, If particle Y has a mass of
25% that of X and velocity 75% that of X, debroglies wave length of Y will be :
(A) 3 Å (B) 5.33 Å (C) 6.88 Å (D) 48 Å
17. The ratio of the de-broglie wavelength of a proton and -particles will be 1 : 2 if their :
(A) velocity are in the ratio 1 : 8. (B) velocity are in the ratio 8 : 1.
(C) kinetic energy are in the ratio 1 : 64. (D) kinetic energy are in the ratio 1 : 256.
18. De Broglie wavelength of an electron after being accelerated by a potential difference of V volt from rest
is
12.3 12 . 3 12. 3 12. 3
(A)  = Å (B)  = Å (C)  = Å (D)  = Å
h V E m
19. If wavelength is equal to the distance travelled by the electron in one second, then -
h h h h
(A)  = (B)  = (C)  = (D)  =
p m p m
20. Uncertainty in position is twice the uncertainty in momentum. Uncertainty in velocity is :
h 1 h 1 h
(A) (B) (C)  (D)
 2m  2m 4
21. Consider an electron in the nth orbit of a hydrogen atom in the Bohr model. The circumference of the orbit
can be expressed in terms of the de Broglie wavelength  of the electron as :
(A) (0.529) n (B) n (C) (13.6)  (D) n

22. Which orbital is non-directional.

(A) s (B) p (C) d (D) All

23. In case of d x 2  y 2 orbital

(A) Probability of finding the electron along x-axis is zero.
(B) Probability of finding the electron along y-axis is zero.
(C) Probability of finding the electron is maximum along x and y-axis.
(D) Probability of finding the electron is zero in x-y plane
24. In an atomic orbital, the sign of lobes indicates the :
(A) sign of the probability distribution (B) sign of charge
(C) sign of the wave function (D) presence or absence of electron
25. The correct set of four quantum numbers for the valence electron of Rubidium (Z = 37) is :
1 1
(A) n = 5,  = 0, m = 0, s = + 2 (B) n = 5,  = 1, m = 0, s = + 2

1 1
(C) n = 5,  = 1, m = 1, s = + 2 (D) n = 6,  = 0, m = 0, s = + 2
26. The value of the spin magnetic moment of a particular ion is 2.83 Bohr magneton. The ion is :
(A) Fe2+ (B) Ni2+ (C) Mn2+ (D) Co3+
27. What are the values of the orbital angular momentum of an electron in the orbitals 1s, 3s, 3d and 2p -
(A) 0, 0, 6  , 2 (B) 1, 1, 4  , 2 (C) 0, 1 6  , 3  (D) 0, 0 20  , 6

28. After np orbitals are filled, the next orbital filled will be :
(A) (n + 1) s (B) (n + 2) p (C) (n + 1) d (D) (n + 2) s

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 Atomic Structure
29. If n and  are respectively the principal and azimuthal quantum numbers, then the expression for calculating
the total number of electrons in any orbit is :
 n   n 1   n1   n 1

(A)  2 (2  1) (B)  2 (2  1) (C)  2 (2  1)

0
(D)  2 (2  1)
0
 1  1

30. The quantum numbers + 1/2 and – 1/2 for the electron spin represent :
(A) Rotation of the electron in clockwise and anticlockwise direction respectively.
(B) Rotation of the electron in anticlockwise and clockwise direction respectively.
(C) Magnetic moment of the electron pointing up and down respectively,
(D) Two quantum mechanical spin states which have no classical analogue.
206
31. The number of  and  particles lost when 238 changes to 82 Pb :
92 U
(A) 8, 6 (B) 6, 6 (C) 6, 8 (D) 4, 4

PART- 2: ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

76
1. Isotone of 32 Ge is/are :
(A) 77
(B) 77 As (C) 77
(D) 78
32 Ge 33 34 Se 34 Se

2. Which of the following is iso-electronic with neon?

(A) O2– (B) F– (C) Mg (D) Na
3. When alpha particles are sent towards a thin metal foil, most of them go straight through the foil because
(A) alpha particles are much heavier than electrons
(B) alpha particles are positively charged
(C) most part of the atom is empty space
(D) alpha particles move with high speed
4. From the -particle scattering experiment, Rutherford concluded that
(A) -particle can come within a distance of the order of 10–14 m from the nucleus
(B) the radius of the nucleus is less than 10–14 m
(C) scattering followed Coulomb’s law
(D) the positively charged parts of the atom move with extremely high velocities
5. A sodium street light gives off yellow light that has a wavelength of 600 nm. Then
12400 eV Å
(For energy of a photon take E =  (Å)
)
14 –1
(A) frequency of this light is 7× 10 s (B) frequency of this light is 5× 1014 s–1
(C) wavenumber of the light is 3 × 106 m–1 (D) energy of the photon is approximately 2.07 eV
6. The spectrum of He+ is expected to be similar to that of :
(A) Li2+ (B) He (C) H (D) Na
7. Choose the correct relations on the basis of Bohr’s theory.
1 1
(A) Velocity of electron  (B) Frequency of revolution 
n n3
1
(C) Radius of orbit  n2 Z (D) Electrostatic force on electron 
n4
8. 1st excitation potential for the H-like (hypothetical) sample is 24 V. Then :
(A) Ionisation energy of the sample is 36 eV (B) Ionisation energy of the sample is 32 eV
(C) Binding energy of 3rd excited state is 2 eV (D) 2nd excitation potential of the sample is 32 x 8 V
9
9. In which transition, one quantum of energy is emitted ?
(A) n = 4  n = 2 (B) n = 3  n = 1 (C) n = 4  n = 1 (D) n = 2  n = 1

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 Atomic Structure
10. In a H-like sample, electrons make transition from 4 excited state upto 2nd state. Then :
th

(A) 10 different spectral lines are observed

(B) 6 different spectral lines are observed
(C) number of lines belonging to the balmer series is 3
(D) Number of lines belonging to paschen series is 2.
11. The change in angular momentum corresponding to an electron in Balmer transition inside a hydrogen atom
can be :
h h h h
(A) (B) (C) (D)
4  28
12. The qualitative order of Debroglie wavelength for electron, proton and  particle is e > P >  if
(A) If kinetic energy is same for all particles
(B) If the accelerating potential difference 'V' is same for all the particles (from rest)
(C) If velocities are same for all particles
(D) None of the above
13. Which of the following statements is/are correct for an electron of quantum numbers n = 4 and m = 2 ?
(A) The value of  may be 2. (B) The value of  may be 3.
(C) The value of s may be +1/2. (D) The value of  may be 0, 1, 2, 3.
14. If element 25X+Y has spin magnetic moment 1.732 B.M then
(A) number of unpaired electron = 1 (B) number of unpaired electron = 2
(C) Y = 4 (D) Y = 6
15. The magnitude of the spin angular momentum of an electron is given by
h h 3 h 1 h
(A) S = s(s  1) (B) S = s (C) S =  (D) S = ± 
2 2 2 2 2 2
16. Which of the following statement(s) is (are) correct?
(A) The electronic configuration of Cr is [Ar] (3d)5 (4s)1. (Atomic number of Cr = 24)
(B) The magnetic quantum number may have negative values.
(C) In silver atom, 23 electrons have a spin of one type and 24 of the opposite type. (Atomic number of Ag =
47)
(D) None of these
17. The configuration [Ar] 3d10 4s2 4p4 is similar to that of
(A) boron (B) oxygen (C) sulphur (D) aluminium
18. Which consists of charged particles of matter?
(A) -particle (B) -particle (C) -rays (D) Anode rays
19. Which of the following does not occur ?
40 1 40
(A) 20 Ca  0 n  19 K  11H (B) 24 4
12 Mg  2 He  27 1
14 Si  0 n

113 1 112 0 43 4 46
(C) 48 Cd  0 n  48 Cd  1e (D) 20 Ca  2 He  21Sc  11H

20. Pickout the correct statements :

(A) Negative -decay decreases the proportion of neutrons and increases the proportion of proton.
(B) Positive -decay increases the proportion of neutrons and decreases the proportion of proton.
(C) K-electron capture increases the proportion of neutrons and increases the proporiton of proton.
(D) Positrons and electrons quickly unite to produce photons.
PART- 3: SUBJECTIVE QUESITONS
1. The ratio of specific charge (e/m) of a proton and that of an -particle is :
2. Compare the energies of two radiation one with a wavelength of 300 nm and other with 600 nm.
3. The latent heat of fusion of ice is 330 J/g. Calculate the number of photons of radiation of frequency
5 × 1013 s–1 to cause the melting of 1 mole of ice. Take h = 6.6 × 10–34 J.S. Express your answer as X ×
1022, what is the value of 'X'.

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 Atomic Structure
4. The work function for a metal is 40 eV. To emit photo electrons of zero velocity from the surface of the
metal the wavelength of incident light should be x nm.
5. Electrons in a sample of H-atoms make transition from state n = x to some lower excited state. The
emission spectrum from the sample is found to contain only the lines belonging to a particular series. If one
of the maximum energy photons has an energy of 0.6375 eV, find the value of x.
3
[Take 0.6375 eV = 4 × 0.85 eV]

6. If first ionization potential of a hypothetical atom is 16 V, then the first excitation potential will be :
7. In hydrogen atom an orbit has a diameter of about 16.92Å. What is the maximum number of electrons that
can be accommodated.
8. Electrons in the H-atoms jump from some higher level upto 3rd energy level. If six spectral lines are
possible for the transition, find the initial position of electron.
9. Photon having energy equivalent to the binding energy of 4th state of He+ atom is used to eject an electron
from the metal surface of work function 1.4 eV. If electrons are further accelerated through the potential
difference of 4V then the minimum value of De–broglie wavelength associated with the electron is :
10. An electron in Li2+ ion makes a transition from higher state n2 to lower state n1 = 6. The emitted photons is
used to ionize an electron in H–atom from 2nd excited state. The electron on leaving the H–atom has a
de–Broglie wavelength  = 12.016 Å. Find the value of n2.
150  144 150
Note : Use (12.016)2 = 13.6 11 Å = KEeV
.

11. The radial distribution curve of 2s sublevel consists of x nodes, Find out value of x.
12. The wave function of atomic orbital of H like atoms is given as under
1
2s = z3/2 [2 – Zr]eZr/2
4 2
Given that the radius is in Å , then which of the following is radius for nodal surface for He+ Ion ?
13. How many of these orbitals have maximum orbital angular probability distribution is maximum at an angle
of 45° to the axial direction.
dxy, d x 2  y 2 , dyz, dxz, d z2 , Px, Py, Pz, s

14. Total number of electrons having n +  = 3 in Cr (24) atom in its ground state is :
15. An ion Mna+ has the spin magnetic moment equal to 4.9 BM. The value of a is : (atomic no. of Mn = 25)
139 94
16. The number of neutrons accompanying the formation of 54 Xe and 38 Sr from the absorption of a slow
neutron by 235
92 U followed by nuclear fision is :

PART- 4: COMPREHENSION
Read the following passage carefully and answer the questions.
Comprehension # 1
In the photoelectric effect the electrons are emitted instantaneously from a given metal plate, when it is
irradiated with radiation of frequency equal to or greater than some minimum frequency, called the threshold
frequency. According to planck's idea, light may be considered to be made up of discrete particles called
photons . Each photon carries energy equal to h. When this photon collides with the electron of the metal,
the electron acquires energy equal to the energy of the photon. Thus the energy of the emitted electron is
given by :
1
h = K.Emaximum + P. E. = mu2 + PE
2
If the incident radiation is of threshold frequency the electron will be
emitted without any kinetic energy i.e. h0 = PE

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 Atomic Structure

1
 mu2 = h – h0
2
A plot of kinetic energy of the emitted electron versus frequency of the
incident radiation yields a straight line given as

1. A beam of white light is dispersed into its wavelength components by a Quartz prism and falls on a thin
sheet of potassium metal. What is the correct decreasing order of maximum kinetic energy of the electron
emitted by the different light component.
(A) blue > green > orange > yellow (B) violet > blue > orange > red
(C) yellow > green > blue > violet (D) orange > yellow > blue > violet
2. A laser producing monochromatic light is used to eject electron from the sheet of gold having threshold
frequency 6.15 x 1014 s–1 which of the following incident radiation will be suitable for the ejection of
electron:
(A) 1.5 moles of photons having frequency 3.05 × 1014 s–1
(B) 0.5 moles of photon of frequency 12.3 × 1012 s–1
(C) One photon with frequency 5.16 × 1015 s–1
(D) All of the above
3. The number of photoelectrons emitted depends upon :
(A) The intensity of the incident radiation
(B) The frequency of the incident radiation
(C) The product of intensity and frequency of incident radiation
(D) None of these
.Comprehension # 2

The only electron in the hydrogen atom resides under ordinary conditions
on the first orbit. When energy is supplied, the electron moves to
higher energy orbit depending on the amount of energy absorbed.
When this electron returns to any of the lower orbits, it emits energy.
Lyman series is formed when the electron returns to the lowest orbit
while Balmer series is formed when the electron returns to second
orbit. Similarly, Paschen, Brackett and Pfund series are formed when
electron returns to the third, fourth and fifth orbits from higher energy
orbits respectively (as shown in figure)
Maximum number of lines produced when electrons jump from nth
n(n  1)
level to ground level is equal to .
2
For example, in the case of n = 4, number of lines produced is 6. (4  3, 4  2, 4  1, 3  2, 3  1, 2 
1). When an electron returns from n2 to n1 state, the number of lines in the spectrum will be equal to
(n2  n1 )(n 2  n1  1)
2
If the electron comes back from energy level having energy E2 to energy level having energy E1, then the
difference may be expressed in terms of energy of photon as :
hc
E2 – E1 = E ,   , E = h ( - frequency)
E
Since h and c are constants, E corresponds to definite energy; thus each transition from one energy level
to another will produce a light of definite wavelength. This is actually observed as a line in the spectrum of
hydrogen atom.

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 Atomic Structure
 1 1
Wave number of line is given by the formula   RZ 2  2  2  .
 n1 n2 
where R is a Rydberg constant (R = 1.1 × 107 m–1)
(i) First line of a series : It is called ‘line of longest wavelength’ or ‘line of shortest energy’.
(ii) Series limit or last line of a series : It is the line of shortest wavelength or line of highest energy.

4. Last line of Brackett series for H–atom has wavelength 1 Å and 2nd line of lyman series has wavelength
 2 Å, then :

128 9 16 9 4 1 128 8
(A)  =  (B)  =  (C)  =  (D)  = 
1 2 1 2 1 2 1 2

5. Consider the following statements

1. Spectral lines of He+ ion belonging to Balmer series are not in visible range.
2. In the balmer series of H-atom maximum lines are in ultra violet region.
3. 2nd line of lyman series of He+ ion has energy 48.4 eV
The above statements 1, 2, 3 respectively are (T = True, F = False)
(A) T F F (B) F T T (C) T F T (D) T T T
6. Wave number of the first line of Paschen series in Be3+ ion is
7R 7R 7R R
(A) (B) (C) (D)
16 144 9 144
Comprehension # 3
h
de Broglie proposed dual nature for electron by putting his famous equation  = mv . Later on Heisenberg

h
proposed uncertainty principle as p. x  4 . On the contrary, particle nature of electron was established
on the basis of photoelectric effect. When a photon strikes the metal surface, it gives up its energy to the
electron. Part of this energy (say W) is used by the electrons to escape from the metal and the remaining
energy imparts kinetic energy (1/2 mv2) to the ejected photoelectron. The potential applied on the surface
to reduce the velocity of photoelectron to zero is known as stopping potential.
7. Uncertainity in the position of an electron (mass 9.1  10–31 kg) moving with a velocity 300 ms–1, accurate

upto 0.001% will be : ( 2m = 5.8  10–5)
e

(A) 19.2  10–2 m (B) 5.76  10–2 m (C) 3.84  10–2 m (D) 1.92  10–2 m
8. When a beam of photons of a particular energy was incident on a surface of a particular pure metal having
work function = (40 eV), some emitted photoelectrons had stopping potential equal to 22 V, some had 12 V
and rest had lower values. Calculate the wavelength of incident photons assuming that at least one
photoelectron is ejected with maximum possible kinetic energy. .
(A) 310 Å (B) 298 Å (C) 238 Å (D) 200 Å
9. The circumference of third orbit of a single electron species is 3 nm. What may be the approximate
wavelength of the photon required to just ionize electron from this orbit.
(A) 91.1 nm (B) 364.7 nm (C) 821 nm (D) 205 nm
Comprehension # 4
After the failure of Bohr atomic theory but its ability
to explain the atomic spectra a need was felt for
the new model that could incorporate, the concept
of stationary orbit, de Broglie concept,

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 Atomic Structure
Heisenberg uncertainty principle. The concept that in corporate above facts is called quantum mechanics
of the atomic model wave mechanical model. It includes set of quantum numbers and |2|a mathematical
expression of the probability of finding an electron at all points in space.
This probability function is the best indication available of how the electron behaves, for as a consequence
of the Uncertainty Principle, the amount we can know about the electron is limited. While quantum mechanics
can tell us the exact probability of finding an electron at any two particular points, it does not tell us how the
electron moves from one of these points to the other. Thus the idea of an electron orbit is lost; it is replaced
with a description of where the electron is most likely to be found. This total picture of the probability of
finding an electron at various points in space is called an orbital.
There are various types of orbitals possible, each corresponding to one of the possible combinations of
quantum numbers. These orbitals are classified according to the value of n and l associated with them. In
order to avoid confusion over the use of two numbers, the numerical values of l are replaced by letters;
electrons in orbitals with l = 0 are called s-electrons those occupying orbitals for which l = 1 are p-
electrons and those for which l = 2 are called d-electrons. The numerical and alphabetical correspondences
are summarized in table. Using the alphabetical notation for l, we would say that in the ground state of
hydrogen atom (n = 1, l = 0) we have a 1s-electron, or that the electron moves in a 1s-orbital. The relation
of the spherical polar co-ordinates r, and to Cartesian coordinates x, y and z. To make the concept of an
orbital more meaningful, it is helpful to examine the actual solution of the wave function for the one-
electron atom. Because of the spherical symmetry of the atom, the wave functions are most simply expressed
in terms of a spherical polar-coordinate system, shown in fig., which has its orbit at the nucleus. It is found
that the wave functions can be expressed as the product of two functions, one of which (the “angular part”
X) depends only the angle  and , the other of which (the “radial part” R) depends only on the distance
from the nucleus. Thus we have (r, , ) = R(r) X (, )
Angular and radial parts of hydrogen atom wave functions
Angular part X() Radial part Rn, (r)
1/ 2 3/ 2
 1   z 
X(s) =   R(1s) = 2   e  / 2
 4   a0 

1/ 2 3/ 2
 3   z 
1
X(px) =   sin cos R(2s) =   (2 – ) e   / 2
 4  2 2  a 0 

1/ 2 3/ 2
 3   z 
1
X(py) =   sin sin R(2p) =    e / 2
 4  2 6  a 0 

1/ 2
 3 
X(pz) =   cos
 4 
1/ 2
 5 
X(dz ) = 
2
 (3 cos2 – 1)
 16 

1/ 2 3/ 2
 15  1  z 
X(dxz) =   sin coscos R(3s) =   (6  6   2 )e  / 2
 4  9 3  a 0 

1/ 2 3/ 2
 15  1  z 
X(dyz) =   sin cossin R(3p) =   (4  )e  / 2
 4  9 6  a 0 

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 Atomic Structure

1/ 2 3/ 2
 15  1  z 
 
X(dx2 – y2) =    2 e  / 2
2
sin  cos2 R(3d) =
 4  9 30  a0 
1/ 2
 15 
X(dxy) =   sin2 sin 2
 4 


2Zr h2
a 
na 0  0 42 me 2
This factorization helps us to visualize the wave function, since it allows us to consider the angular and
radial dependences separately. It contains the expression for the angular and radial parts of the one electron
atom wave function. Note that the angular part of the wave function for an s-orbital it always the same, (1/
4)1/2, regardless of principal quantum number. It is also true that the angular dependence of the p-orbitals
and of the d-orbitals is independent of principle quantum number. Thus all orbitals of a given types (s, p, or
d) have the same angular behaviour The table shows, however, that the radial part of the wave function
depends both on the principal quantum number n and on the angular momentum quantum number l.
To find the wave function for a particular state, we simply multiply the appropriate angular and radial parts
together called normalized wave function.
The probability of finding an electron at a point within an atom is proportional to the square of orbital wave
function, i.e., 2 at that point. Thus, 2 is known as probability density and alwyas a positive quantity.
2 dV (or 2.4r2dr). represents the probability for finding electron in a small volume dV surrounding the
nucleus.
10. The electron probability density for 1s-orbital is best represented by the relation
3/2 r 3 2 zr
 
1  Z  a0 1 Z 
(A)   e (B)    e a0
  
2   a0    a0 

3/2 r 3 2 zr
   a0
1 Z  a0 2 Z
(C)  
 e (D)   e

  a0    a0 

11. The angular wave function of which orbital will not disturb by the variation with azimuthal angle only
(A) 1s and 2s (B) 2pz and 2dz2 (C) 2px and 3dz2 (D) 2px and 2s
Comprehension # 5
Quantum numbers are assigned to get complete information of electrons regarding their energy, angular
momentum, spectral lines etc. Four quantum numbers are known i.e. principal quantum numbers which tell
the distance of electron from nucleus, energy of electron in a particular shell and its angular momentum.
Azimuthal quantum number tells about the subshells in a given shell and of course shape of orbital. Magnetic
quantum number deals with study of orientations or degeneracy of a subshell.
1 1
Spin quantum number which defines the spin of electron designated as + or – represented by and
2 2
respectively. Electron are filled in orbitals following Aufbau rule. Pauli's exclusion principal and Hund's rule
of maximum multiplicity. On the basis of this answer the following questions.
12. Two unpaired electrons present in carbon atom are different with respect to their
(A) Principle quantum number (B) Azimuthul quantum number
(C) Magnetic quantum number (D) Spin quantum number
1
13. Number of electron having the quantum numbers n = 4,  = 0, s =  in Zn+2 ion is/are :
2
(A) 1 (B) 0 (C) 2 (D) 5

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 Atomic Structure
14. Spin angular momentum for unpaired electron in sodium (Atomic No. = 11) is
3 3 h
(A) (B) 0.866 h/2 (C) – (D) None of these
2 2 2

PART- 5: COLUMN MATCHING

1. List-I List-II
(i) Cathode rays (a) Helium nuclei
(ii) Dumb-bell (b) Uncertainty principle
(iii) Alpha particles (c) Electromagnetic radiation
(iv) Moseley (d) p-orbital
(v) Heisenberg (e) Atomic number
(vi) X-rays (f) Electrons
2. Frequency = f, Time period = T, Energy of nth orbit = En, radius of nth orbit = rn, Atomic number = Z,
Orbit number = n
List-I List-II
(i) f (p) n3
(ii) T (q) Z2
1
(iii) En (r)
n2
1
(iv) r (s) Z
n

3. List-I List-II
(i) Aufbau principle (p) Line spectrum in visible region
(ii) de broglie (q) Maximum multiplicity of electron
(iii) Angular momentum (r) Photon
(iv) Hund’s rule (s)  = h/(mv)
(v) Balmer series (t) Electronic configuration
(vi) Planck’s law (u) mvr
4. Match List-I with List-II and select the correct answer using the codes given below in the lists (n, and m
are respectively the principal, azimuthal and magnetic quantum no.)
List-I List-II
(A) Number of value of  for an energy level(n) (p) 0, 1, 2, ............. (n - 1)
(B) Values of  for a particular type of orbit (q) + to – through zero
(C) Number of value of m for  = 2 (r) 5
(D) Values of 'm' for a particular type of orbital (s) n

EXERCISE-5

1. The orbit having Bohr radius equal to 1st Bohr orbit of H–atom is : [JEE 2004]
(A) n = 2 of He+ (B) n = 2 of B+4 (C) n = 3 of Li+2 (D) n = 2 of Be +3

2. (a) The wave function of an electron in 2s orbital in hydrogen atom is given below :
3/2
1  z   r 
2s =   2  
4( 2) 1/ 2 a
 0



 a 0  exp (– r/2a0) [JEE 2004]

where a0 is the Bohr radius. This wave function has a radial node at r = r0. Express r0 in terms of a0.
(b) Calculate the wavelength of a ball of mass 100 g moving with a velocity of 100 ms–1.
–8 
(c) 92
X238   Y. Find out atomic number, mass number of Y and identify it.
– 6

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 Atomic Structure
3. (a) Using Bohr’s model for hydrogen atom, find the speed of electron in the first orbit if the Bohr’s
radius is a0 = 0.529 × 10–10 m. Find deBroglie wavelength of the electron also.
h
(b) Find the orbital angular momentum of electron if it is in 2p orbital of H in terms of .
2
[JEE 2005]
4. According to Bohr’s theory,
En = Total energy, Kn = Kinetic energy, Vn = Potential energy, rn = Radius of nth orbit
Match the following: [JEE 2006]
Column I Column II
(A) Vn / Kn = ? (p) 0
th x
(B) If radius of n orbit  En , x = ? (q) – 1
(C) Angular momentum in lowest orbital (r) – 2
1
(D)  Zy , y  ? (s) 1
rn
Paragraph for Question Nos. 5 to 7
The hydrogen-like species Li2+ is in a spherically symmetric state S1 with one radial node. Upon absorbing
light the ion undergoes transition to a state S2. The state S2 has one radial node and its energy is equal to the
ground state energy of the hydrogen atom.
5. The state S1 is : [JEE 2010]
(A) 1s (B) 2s (C) 2p (D) 3s
6. Energy of the state S1 in units of the hydrogen atom ground state energy is : [JEE 2010]
(A) 0.75 (B) 1.50 (C) 2.25 (D) 4.50
7. The orbital angular momentum quantum number of the state S2 is : [JEE 2010]
(A) 0 (B) 1 (C) 2 (D) 3
8. The work function () of some metals is listed below. The number of metals which will show photoelectric
effect when light of 300 nm wavelength falls on the metal is [JEE 2011]
Metal Li Na K Mg Cu Ag Fe Pt W
 (eV) 2.4 2.3 2.2 3.7 4.8 4.3 4.7 6.3 4.75

9. The maximum number of electrons that can have principal quantum number, n = 3, and spin quantum
number, ms = –1/2, is [JEE 2011]
10. Bombardment of aluminum by -particle leads to its artificial disintegration in two ways, (I) and (ii) as
shown. Products X, Y and Z respectively are,

[JEE 2011]

(A) proton, neutron, positron (B) neutron, positron, proton

(C) proton, positron, neutron (D) positron, proton, neutron
11. The kinetic energy of an electron in the second Bohr orbit of a hydrogen atom is [a0 is Bohr radius] :
h2 h2 h2 h2
(A) 42ma 2 (B) 162ma2 (C) 322ma2 (D) 642ma2 [JEE 2012]
0 0 0 0

12. The periodic table consists of 18 groups. An isotope of copper, on bombardment with protons, undergoes a
nuclear reaction yielding element X as shown below. To which group, element X belongs in the periodic
table?
63 1
29 Cu 1 H  610 n  24   211H  X [JEE 2012]

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 Atomic Structure
13.* In the nuclear transmutation
9 8
4 Be  X  4 Be Y
(X, Y) is (are) : [JEE(Advanced) 2013]
(A) (  , n) (B) (p, D) (C) (n, D) (D) (  , p)
14. In an atom, the total number of electrons having quantum numbers n = 4, |m| = 1 and ms = –1/2 is
[JEE(Advanced) 2014]
15. Not considering the electronic spin, the degeneracy of the second excited state (n = 3) of H atom is 9, while
the degeneracy of the second excited state of H– is [JEE(Advanced) 2015]
16. P is the probability of finding the 1s electron of hydrogen atom in a spherical shell of infinitesimal thickness,
dr, at a distance r from the nucleus. The volume of this shell is 42 dr . The qualitative sketch of the
dependence of P on r is: [JEE(Advanced) 2016]

(A) (B) (C) (D)

Answer Q.17, Q.18 and Q.18 by appropriately matching the information given in the three
columns of the following table.

The wave function,  n , l, m1 is a mathematical function whose value depends upon spherical polar
coordinates (r, , ) of the electron and characterized by the quantum numbers n, l and ml. Here r is
distance from nucleus,  is colatitude and  is azim uth. In the mathematical functions given in the Table,
Z is atomic number and ao is Bohr radius.

17. For He+ ion, the only INCORRECT combination is [JEE(Advanced) 2017]
(A) (I) (i) (S) (B) (II) (ii) (Q) (C) (I) (iii) (R) (D) (I) (i) (R)

18. For the given orbital in Column 1, the only CORRECT combination for any hydrogen-like species is
[JEE(Advanced) 2017]
(A) (II) (ii) (P) (B) (I) (ii) (S) (C) (IV) (iv) (R) (D) (III) (iii) (P)

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 Atomic Structure
19. For hydrogen atom, the only CORRECT combination is [JEE(Advanced) 2017]
(A) (I) (i) (P) (B) (I) (iv) (R) (C) (II) (i) (Q) (D) (I) (i) (S)

PART - 2 : PRACTICE PROBLEMS (JEE ADVANCED)

SECTION-1 : (Only One option correct Type)

This section contains 7 multiple choice questions. Each questions has four choices (A), (B), (C)
and (D) out of which Only ONE option is correct.

1. Find the quantum number of the excited state of electrons in He+ ion which on transition to first excited
state emit photons of wavelengths 108.5 nm. (RH = 1.09678 × 107 m–1)
(A) 6 (B) 5 (C) 4 (D) 2
1/ 2
1  1
2. For a 3s orbital  (3s) =   (6 – 6+ 2)   / 2
9 3  aº 
2Zr
Where  = . What is the maximum radial distance of node from nucleus ?
3aº

2 (3  3 )a 0 3 (3  3 )a 0 3 (3 – 3 3)a0 3 (3 – 3 )a0
(A) (B) (C) (D)
3 Z 2 Z 2 Z 2 Z
3. A glow–worm of mass 5.0 g emits red light (650 nm) with a power of 0.10 w. entirely in the backward
direction. To what speed will it have accelerated after 10 y if released into free space and assumed to live?
(A) 21 ms–1 (B) 29 ms–1 (C) 31.8 ms–1 (D) 0.08 ms–1
4. Calculate the energy required to excited one litre of hydrogen gas at 1 atm and 298 K to the first excited
state of atomic hydrogen. The energy for the disociation of H–H bond is 436 kJ mol–1. Also calculate the
minimum frequency of photon to break this bond.
(A) 98.19 Hz (B) 10.93 × 1014 Hz (C) 1015 Hz (D) 6.22 × 1014 Hz
5. O2 undergoes photochemical dissociation into 1 normal oxygen atom (O) and more energetic oxygen atom
O*. If (O) has 1.967 eV more energy than (O) and normal dissociation energy of O2 is 498 kJmol–1, what
is the maximum wavelength effective for the photo chemical dissociation of O2?
(A) 1.01 nm (B) 1.64 nm (C) 1.74 nm (D) 2.74 nm
6. If the subsidiary quantum number of a subenergy level is 4, the maximum and minimum values of the spin
multiplicities are :
(A) 9, 1 (B) 10, 1 (C) 10, 2 (D) 4, –4
7. 1 mol of He+ ion is excited. Spectral analysis showed existence of 50% ions in 3rd level, 25% in 2nd level
and remaining 25% in ground state. Ionization energy of He+ is 54.4 eV; calculate total energy evolved
when all hte ions return ground state.
(A) 331.13 × 104 J (B) 400.14 × 104 J (C) 104 J (D) 6.66 × 104 J

Section-2 : (One or More than one options correct Type)

This section contains 5 multipole choice questions. Each questions has four choices (A), (B),
(C) and (D) out of which ONE or MORE THAN ONE are correct.

8. Consider the following six electronic configurations (remaining inner orbitals are completely filled) and
mark the correct option.

(I) (II) (III)

(IV) (V) (VI)

(A) Stability order : II > I > IV > III

(B) Order of spin multiplicity : IV > III = I > II

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 Atomic Structure
(C) V does not violate all the three rules of electronic configuration
(D) If VI represents A and A+ when kept near a magnet, acts as diamagnetic substance.
9. Choose the correct statement(s) :
(A) The shape of an atomic orbital depends upon azimuthal quantum number
(B) The orientation of an atomic orbital depends upon the magnetic quantum number
(C) The energy of an electron in an atomic orbital of multi-electron atom depends upon principal quantum
number only
(D) The number of degenerate atomic orbitals of one type depends upon the value of azimuthal quantum
number
10. The radial distribution functions [P(r)] is used to determine the most probable radius, which is used to find
dP(r ) dP
the electron in a given orbital for 1s-orbital of hydrogen like atom having atomic number Z, is =
dr dr
4Z 3  2Zr 2  2Zr / a0
2r  e :
a 30  a0 
dP(r )
(A) At the point of maximum value of radial distribution function = 0; one antinode is present
dr
a0 a0
(B) Most probable radius of Li2+ is pm (C) Most probable radius of He+ is pm
3 2
(D) Most probable radius of hydrogen atom is a0 pm
11. For radial probability curves, which of the following is/are correct ?
(A) The number of maxima in 2s orbital are two
(B) The number of spherical or radial nodes is equal to n –  – 1
(C) The number of angular nodes are ‘’
(D) 3dz2 has 3 angular nodes
12. dxy orbital has four lobes between x- and y-axes. The wave functions of two lobes are positive and those of
other two are negative. The positive wave function signifies that :
(A) both x and y are positive (B) both x and y are negative
(C) either x or y is negative (D) none of these

Section-3 : (One Integer Value Correct Type.)

This section contains 6 questions. Each question, when worked out will result in one integer
from 0 to 9 (both inclusive)

13. The dissociation energy of H2 is 430.53 kJ mol–1. If H2 is exposed to radiant energy of wavelength 253.7
nm. What % of radiant energy will be converted into kinetic energy? (Report your answer as nearest
integer).
14. The IE1 of H is 13.6 eV. It is exposed to electromagnetic waves of 1028Å and gives out induced radiation.
Find out orbit of these induced radiation.
15. A hydrogen like atom (atomic number Z) is in a higher excited state of quantum number n. This excited
atom can make a transition to the first excited state by successively emitting two photons of energies 10.20
eV and 17.00 eV respectively. Alternatively, the atom from the same excited state can make a transition to
the second excited state by successively emitting two photons of energy 4.25 eV and 5.95 eV respectively.
Determine the values of n and Z (ionisation energy of hydrogen atom = 13.6 eV). Give answer = n + Z.
16. A moving particle is associated with wavelength 5 × 10–8m . If its momentum is reduced to half of its value,
compute the new wavelength. If answer is 10–x then find ‘x’.
17. According to Bohr theory, the electronic energy of a hydrogen atom in the nth Bohr atom is given by
21.76  1019
En= – J. Calculate the longest wavelength of light that will be needed to remove an electron from
n2
the third Bohr orbit of the He+ ion (If the wavelength is x × 10–7 (in meter) and x is an integer. Report ‘x’).

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 Atomic Structure
7
18. 4 Be captures a K-electron into its nucleus. What will be the sum of mass number and atomic number of
the nuclide formed?

SECTION-4 : Comprehension Type (Only One options correct)

This section contains 1 paragraphs, each describing theory, experiments, data etc. 3 questions
relate to the paragraph. Each question has only one correct answer among the four given options
(A), (B), (C) and (D)

Paragraph For Questions 19 to 21

Werner Heisenberg considered the limits of how precisely we can measure the properties of an electron or
other microscopic particle. He determined that there is a fundamental limit to how closely we can measure
both position and momentum. The more accurately we measure the momentum of a particle, the less
accurately we can determine its position. The converse is also true. This is summed up in what we now call
the Heisenberg uncertainty principle.
h
The equation is x.(mv) 
4
The uncertainty in the position or in the momentum of a macroscopic object like a baseball is too small to
observe. However, the mass of microscopic object such as an electron is small enough for the uncertainty
to be relatively large and significant.
19. If the uncertainties in position and momentum are equal, the uncertainty in the velocity is :
h h 1 h
(A) (B) (C) (D) none of these
 2 2m 
20. If the uncertainty in velocity and position is same, then the uncertainty in momentum will be :
hm h h 1 h
(A) (B) m (C) (D)
4 4 4 m m 4
21. What would be the minimum uncertainty in de-Broglie wavelength of a moving electron accelerated by
7
potential difference of 6 volt and whose uncertainty in position is nm ?
22
(A) 6.25 Å (B) 6 Å (C) 0.625 Å (D) 0.1325 Å

SECTION-5 : Matching List Type (Only One options correct)

This section contains 1 questions, each having two matching lists. Choices for the correct
combination of elements from List-I and List-II are given as options (A), (B), (C) and (D) out of
which one is correct

22. Match each List-I with an appropriate pair of characteristics from List-II and select the correct answer
using the code given below the lists.
List-I List-II
P. Lyman series 1. maximum number of spectral line observed = 6
Q. Balmer series 2. maximum number of spectral line observed = 2
8R
R. In a sample of H-atom for 5 upto 2 transition 3. 2nd line has wave number 9
3R
S. In a single isolated H-atom for 3 upto1 transition. 4. 2nd line has wave number 16
Code :
P Q R S P Q R S
(A) 3 4 1 2 (B) 1 2 4 3
(C) 3 1 2 4 (D) 2 3 1 4

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 Atomic Structure

ANSWER KEY
PART- 1
1. (C) 2. (C) 3. (B) 4. (D) 5. (C)
6. (D) 7. (C) 8. (A) 9. (D) 10. (A)
11. (C) 12. (A) 13. (C) 14. (B) 15. (A)
16. (B) 17. (B) 18. (B) 19. (D) 20. (C)
21. (D) 22. (A) 23. (C) 24. (C) 25. (A)
26. (B) 27. (A) 28. (A) 29. (D) 30. (D)
31. (A)

PART- 2
1. (B,D) 2. (A,B) 3. (A,C) 4. (A,B,C) 5. (B,D)
6. (A,C) 7. (A,B,D) 8. (B,C,D) 9. (A,B,C,D) 10. (B,C,D)
11. (B,C) 12. (A,B,C) 13. (A,B,C) 14. (A,D) 15. (A,C)
16. (A,B,C) 17. (B,C) 18. (A,B,D) 19. (C) 20. (A,B,D)

PART- 3
1. 2 2. 2 3. 18 4. 31 nm 5. 8
6. 12 7. 32 8. 6 9. 5Å 10. 12
11. 1 12. 1Å 13. 3 14. 8 15. +3
16. 3

PART- 4
1. (B) 2. (C) 3. (A) 4. (A) 5. (D)
6. (C) 7. (D) 8. (D) 9. (C) 10. (B)
11. (A) 12. (C) 13. (B) 14. (B)

PART- 5
1. (i – f) ; (ii – d) ; (iii – a) ; (iv – e) ; (v – b) ; (vi – c) 2. (i – q) , (ii – p), (iii – q, r) , (iv – r, s).
3. (i – t) ; (ii – s) ; (iii – u) ; (iv – q) ; (v – p) ; (vi – r) 4. (A – s) ; (B – p) ; (C – r) ; (D – q)

EXERCISE-5
PART- 1
1. (D)
2. (a) r = 2a0 , (b)  = 6.626 × 10–25 Å , (c) 82Y206 ; (Atomic no. 82, Mass no. 206)
 h 
3. (a) 2.18  106 m/s, 3.32 × 10–10 m (b) 2 .  2 

4. [A - r] ; [B - q] ; [C - p] ; [D - s]. 5. (B) 6. (C) 7. (B)

8. 4 9. 9 10. (A) 11. (C) 12. 8
13. (A,B) 14. 6 15. 3 16. (D) 17. (C)
18. (A) 19. (D)

PART- 2
1. (B) 2. (B) 3. (A) 4. (B) 5. (C)
6. (C) 7. (A) 8. (A,B,C) 9. (A,B,D) 10. (A,B,C,D)
11. (A,B,C) 12. (A,B) 13. 9 (8.68%) 14. 3 15. 9
16. 7 17. 2 18. 10 19. (C) 20. (A)
21. (C) 22. (A)

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 Mole Concept

EXERCISE-4
PART - 1 : SINGLE OPTION CORRECT TYPE
1. A sample of Calcium phosphate Ca3(PO4)2 contains 8 mol of O atoms. The number of mol of Ca atoms in
the sample is :
(A) 4 (B) 1.5 (C) 3 (D) 8
2. 64 g of an organic compound has 24 g carbon and 8 g hydrogen and the rest is oxygen. The empirical
formula of the compound is :
(A) CH4 O (B) CH2 O (C) C2H4 O (D) None
3. Formation of polyethene from calcium carbide takes place as follows :
CaC2 + H2O  Ca(OH)2 + C2H2  ; C2H2 + H2  C2H4
n(C2H4)  (CH2CH2)n .
The amount of polyethylene possibly obtainable from 64.0 kg CaC2 can be
(A) 28Kg (B) 14kg (C) 21kg (D) 42 kg
4. The hourly energy requirement of an astronaut can be satisfied by the energy released when 34 g of
sucrose (C12H22O11) are burnt in his body. How many g of oxygen would be needed to be carried in space
capsule to meet his requirement for one day :
(A) 916.2 g (B) 91.62 g (C) 8.162 g (D) 9.162 g.
5. If 10 g of Ag reacts with 1 g of sulphur , the amount of Ag2S formed will be :
(A) 7.75 g (B) 0.775 g (C) 11 g (D) 10 g
6. If a piece of iron gains 10% of its weight due to partial rusting into Fe2O3 the percentage of total iron that
has rusted is :
(A) 23 (B) 13 (C) 23.3 (D) 25.67
7. When a mixture of 10 mole of SO2 , 15 mole of O2 was passed over catalyst , 8 mole of SO3 was formed.
How many mole of SO2and O2 did not enter into combination ?
(A) 2 moles of SO2, 11 moles of O2 (B) 3 moles of SO2, 11.5 moles of O2
(C) 2 moles of SO2, 4 moles of O2 (D) 8 moles of SO2, 4 moles of O2
8. When x grams of carbon are heated with y grams of oxygen in a closed vessel, no solid residue is left
behind. Which of the following statements is correct ?
(A) y/x must lie between 1.33 and 2.67 (B) y/x must be greater than or equal 2.67.
(C) y/x must be less than or equal 1.33 (D) y/x must be greater than or equal 1.33.
9. When a 12 g mixture of carbon and sulphur is burnt in air, then a mixture of CO2 and SO2 is produced, in
which the number of moles of SO2 is half that of CO2. The mass of the carbon in the mixture is :
(A) 4.08 g (B) 5.14 g (C) 8.74 g (D) 1.54 g
10. 1 mol of iron (Fe) reacts completely with 0.65 mol O2 to give a mixture of only FeO and Fe2O3. Mole ratio
of ferrous oxide to ferric oxide is :
(A) 3 : 2 (B) 4 : 3 (C) 20 : 13 (D) none of these
11. When ZnS is boiled with strong nitric acid, the products are zinc nitrate, sulphuric acid and nitrogen dioxide.
What are the changes in the oxidation numbers of Zn, S and N :
(A) + 2, + 4, – 1 (B) + 2, + 6, – 2 (C) 0, + 4, – 2 (D) 0, + 8, – 1
12. The following equations are balanced atomwise and chargewise.
(i) Cr2O72– + 8H+ + 3H2O2  2Cr3+ + 7H2O + 3O2
(ii) Cr2O72– + 8H+ + 5H2O2  2Cr3+ + 9H2O + 4O2
(iii) Cr2O72– + 8H+ + 7H2O2  2Cr3+ + 11H2O + 5O2
The precise equation/equations representing the oxidation of H2O2 is/are :
(A) (i) only (B) (ii) only (C) (iii) only (D) all the three

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 Mole Concept
13. When arsenic sulphide is boiled with NaOH, sodium arsenite and sodium thioarsenite are formed according
y
to reaction x As2S3+ y NaOH  x Na3AsO3 + x Na3AsS3 + H O. What are the values of x and y?
2 2
(A) 1, 6 (B) 2, 8 (C) 2, 6 (D) 1, 4
14. xNO3– + yI– + zH+  2NO + 3I2 + 4H2O x , y, z respectively in the above equation are :
(A) 2, 6, 8 (B) 1, 6 , 4 (C) 0, 6 , 8 (D) 2 , 3 , 4
15.  Balance the following equation and choose the quantity which is the sum of the coefficients of reactants
and products :
....... KMnO4 +....... H2O2 +....... H2SO4  ....... MnSO4 +....... O2 +....... H2O +....... K2SO4

(A) 26 (B) 23 (C) 28 (D) 22

16. A solution of glucose received from some research laboratory has been marked mole fraction x and
molality (m) at 10ºC. When you will calculate its molality and mole fraction in your laboratory at 24ºC you
will find
(A) mole fraction (x) and molality (m) (B) mole fraction (2x) and molality (2m)
(C) mole fraction (x/2) and molality (m/2) (D) mole fraction (x) and (m ± dm) molality
17. 36.5 % HCl has density equal to 1.20 g mL–1. The molarity (M) and molality (m), respectively, are
(A) 15.7, 15.7 (B) 12, 12 (C) 15.7, 12 (D) 12, 15.7
18. An aqueous solution of ethanol has density 1.025 g/mL and it is 2M. What is the molality of this solution ?
(A) 1.79 (B) 2.143 (C) 1.951 (D) None of these.
19. Mole fraction of ethyl alcohol in aqueous ethyl alcohol (C2H5OH) solution is 0.25. Hence percentage of
ethyl alcohol by weight is :
(A) 54% (B) 25% (C) 75% (D) 46%
20. Calculate the mass percent (w/w) of sulphuric acid in a solution prepared by dissolving 4 g of sulphur
trioxide in a 100 ml sulphuric acid solution containing 80 mass percent (w/w) of H2SO4 and having a density
of 1.96 g/ml. (molecular weight of H2SO4 = 98). Take reaction SO3 + H2O  H2SO4
(A) 80.8% (B) 84% (C) 41.65% (D) None of these
21. On mixing 15.0 ml of ethyl alcohol of density 0.792 g ml1 with 15 ml of pure water at 40C, the resulting
solution is found to have a density of 0.924 g ml 1. The percentage contraction in volume is :
(A) 8 % (B) 2 % (C) 3 % (D) 4 %

PART- 2: ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

1. Which is/are correct statements about 1.7 g of NH3 :
(A) It contain 0.3 mol H-atom (B) it contain 2.408  1023 atoms
(C) Mass % of hydrogen is 17.65% (D) It contains 0.3 mol N-atom
2. If 27 g of Carbon is mixed with 88 g of Oxygen and is allowed to burn to produce CO2 , then :
(A) Oxygen is the limiting reagent. (B) Volume of CO2 gas produced at NTP is 50.4 L.
(C) C and O combine in mass ratio 3 : 8. (D) Volume of unreacted O2 at STP is 11.2 L.
3. The density of air is 0.001293 g/cm3 at STP. Identify which of the following statement is correct
(A) Vapour density is 14.48 (B) Molecular weight is 28.96
(C) Vapour density is 0.001293 g/cm3
(D) Vapour density and molecular weight cannot be determined.

4. + AgNO3 (Excess)  Silver salt  Ag (metal)

If 0.5 mole of silver salt is taken and weight of residue obtained is 216 g. (Ag = 108 g/mol).

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 Mole Concept
Then which the following is correct :
(A) n = 4 (B) n = 2
(C) M.wt. of silver salt is 718 g/mol (D) M.wt. of silver salt is 388 g/mol
5. (i) K4Fe(CN)6 + 3H2SO4  2K2SO4 + FeSO4 + 6HCN
(ii) 6HCN + 12H2O  6HCOOH + 6NH3
H2SO 4
(iii) (a) 6NH3 + 3H2SO4  3(NH4)2SO4 (b) 6HCOOH   6CO + 6H2O
Above steps of reactions occur in a container starting with one mole of K4[Fe(CN)6], 5 mole of H2SO4 and
enough water. Find out the limiting reagent in step (i) and calculate maximum moles of CO gas and (NH4)2
SO4 that can be produced.
(A) LR = H2SO4 (B) LR = K4Fe(CN)6,
(C) 6 moles of CO, 2 moles of (NH4)2SO4 (D) 5 moles of CO, 2.5 moles of (NH4)2SO4
6. A sample of a mixture of CaCl2 and NaCl weighing 4.44 g was treated to precipitate all the Ca as CaCO3,
which was then heated and quantitatively converted to 1.12 g of CaO. (At . wt. Ca = 40, Na = 23, Cl =
35.5)
(A) Mixture contains 50% NaCl (B) Mixture contains 60% CaCl2
(C) Mass of CaCl2 is 2.22 g (D) Mass of CaCl2 1.11 g
7. For the following reaction : Na2CO3 + 2HCl  2NaCl + CO2 + H2O
106.0 g of Na2CO3 reacts with 109.5 g of HCl.
Which of the following is/are correct.
(A) The HCl is in excess. (B) 117.0 g of NaCl is formed.
(C) The volume of CO2 produced at NTP is 22.4 L (D) None of these
8. A + B  A3B2 (unbalanced) ; A3B2 + C  A3B2C2 (unbalanced)
Above two reactions are carried out by taking 3 moles each of A and B and one mole of C. Then which
option is/are correct ?
(A) 1 mole of A3B2C2 is formed (B) 1/2 mole of A3B2C2 is formed
(C) 1/2 mole of A3B2 is formed (D) 1/2 mole of A3B2 is left finally
9. Which of the following statements is/are correct ? 1.0 g mixture of CaCO3(s) and glass beads liberate
0.22 g of CO2 upon treatment with excess of HCl. Glass does not react with HCl.
CaCO3 + 2HCl  CO2 + H2O + CaCl2 [Mw of CaCO3 = 100, Mw of CO2 = 44, Atomic weight of Ca
= 40]
(A) The weight of CaCO3 in the original mixture is 0.5 g
(B) The weight of calcium in the original mixture is 0.2 g
(C) The weight percent of calcium in the original mixture is 40% Ca.
(D) The weight percent of Ca in the original mixture is 20% Ca.
10. 100 g sample of clay (containing 19% H2O, 40% silica, and inert impurities as rest) is partially dried so as
to contain 10% H2O.
Which of the following is/are correct statements (s) ?
(A) The percentage of silica in paritially dried clay is 44.4%
(B) The mass of paritially dried clay is 90.0 g.
(C) The percentage of inert impurity in paritially dried clay is 45.6%
(D) The mass of water evaporated is 10.0 g
11. 21.2 g sample of impure Na2CO3 is dissolved and reacted with a solution of CaCl2, the weight of precipitate
of CaCO3 is 10.0 g. Which of the following statements is/are correct ?
(A) The % purity of Na2CO3 is 50%
(B) The percentage purity of Na2CO3 is 60%
(C) The number of moles of Na2CO3 = CaCO3 = 0.1 mol.
(D) The number of moles of NaCl formed is 0.1 mol.
12. Which of the following are examples of disproportionation reaction :
(A) HgO  Hg + O2 (B) KClO3  KCl + O2
(C) KClO3  KClO4 + KCl (D) Cl2 + OH–  ClO– + Cl– + H2O

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 Mole Concept
– – 2– –
13. In the following reaction : Cr(OH)3 + OH + IO3  CrO4 + H2O + I
(A) IO3– is oxidising agent (B) Cr(OH)3 is oxidised
–
(C) 6e are being taken per iodine atom (D) None of these
14. Consider the redox reaction 2S2O32– + 2  S4O62– + 2 – :
(A) S2O32– gets reduced to S4O62– (B) S2O32– gets oxidised to S4O62–
–
(C) 2 gets reduced to  (D) 2 gets oxidised to –
15. Which of the following reactions is not a redox reaction ?
(A) H2O2 + KOH  KHO2 + H2O (B) Cr2O72– + 2OH–  2CrO42– + H2O
 1
(C) Ca(HCO3)2  CaCO3 + CO2 + H2O (D) H2O2  H2O + O
2 2
16. Which of the following statements is/are correct ?
In the reaction xCu3P + yCr2O72– + zH+  Cu2+ + H3PO4 + Cr3+
(A) Cu in Cu3P is oxidised to Cu2+ whereas P in Cu3P is also oxidised to PO43–
(B) Cu in Cu3P is oxidised to Cu2+ whereas P in Cu3P is reduced to H3PO4
(C) In the conversion of Cu3P to Cu2+ and H3PO4, 11 electrons are involved
(D) The value of x is 6.
17. Solutions containing 23 g HCOOH is/are :
w
(A) 46 g of 70%  v  HCOOH (dsolution = 1.40 g/mL)
 
(B) 50 g of 10 M HCOOH (dsolution = 1 g/mL)
w
(C) 50 g of 25%  w  HCOOH
 
(D) 46 g of 5 M HCOOH (dsolution = 1 g/mL)
18. Select dimensionless quantity(ies) :
(A) vapour density (B) molality (C) specific gravity (D) mass fraction
19. Which of the following solutions contains same molar concentration ?
(A) 166 g. KI/L solution (B) 33.0 g (NH4)2 SO4 in 200 mL solution
(C) 25.0 g CuSO4.5H2O in 100mL solution (D) 27.0 mg Al3+ per mL solution
20. If 100 ml of 1M H2SO4 solution is mixed with 100 ml of 9.8%(w/w) H2SO4 solution (d = 1 g/ml) then :
(A) concentration of solution remains same (B) volume of solution become 200 ml
(C) mass of H2SO4 in the solution is 98 g (D) mass of H2SO4 in the solution is 19.6 g
21. Equal volume of 0.1M NaCl and 0.1M FeCl2 are mixed with no change in volume due to mixing. Which of
the following will be true for the final solution. (No precipitation occurs). Assume complete dissociation of
salts and neglect any hydrolysis.
(A) [Na+] = 0.05 M (B) [Fe2+] = 0.05M (C) [Cl] = 0.3M (D) [Cl] = 0.15M

PART- 3: NUMERIC VALUE TYPE

1. How many gram ions of SO4–2 are present in 1.25 mole of K2SO4.Al2(SO4)3.24H2O :
2. A certain organic substance used as a solvent in many reactions contains carbon, hydrogen, oxygen and
sulphur. Weight % of hydrogen in the compound is 7.7. The weight ratio C : O : S = 3 : 2 : 4. What is the
least possible molar mass (in g) of the compound ?

3. Consider the following reaction involved in the preparation of teflon polymer .

XeF6 +  + HF + XeF4.
Determine the moles of XeF6 required for preparation of 100 g Teflon.

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 Mole Concept
1 1
4. When 1 mole of A reacts with mole of B2 (A + B2  AB), 100 Kcal heat is liberated and when 1 mole
2 2
of A reacted with 2 mole of B2 (A + 2B2  AB4 ), 200 Kcal heat is liberated. When 1 mole of A is
completely reacted with excess, of B2 to form AB as well as AB4, 140 Kcal heat is liberated calculate the
mole of B2 used. [Write your answer as number of mole of B2 used × 10]
5. The reaction Cl2 (g) + S2O32–  SO42– + Cl– is to be carried out in basic medium. Starting with 1.5
mole of Cl2, 0.1 mole S2O32– and 3 mole of OH–. How many moles of OH– will be left in solution after the
reaction is complete. Assume no other reaction occurs.
6. In the reaction : 2Al + Cr2O3  Al2O3 + 2Cr, 49.8 g of Al reacted with 200.0 g Cr2O3. How much
grams of reactant remains at the completion of the reaction ?
7. A fluorine disposal plant was constructed to carryout the reactions :
1
F2 + 2NaOH  2 O2 + 2NaF + H2O

2NaF + CaO + H2O  CaF2 + 2NaOH

As the plant operated, excess lime was added to bring about complete precipitation of the fluoride as CaF2.
Over a period of operation, 1900 kg of fluorine was fed into a plant and 10,000 kg of lime was required.
What was the percentage utilisation of lime ? [Lime : CaO]
8. A 3 : 2 molar ratio mixture of FeO and Fe2O3 react with oxygen to produce a 2 : 3 molar ratio mixture of
FeO and Fe2O3. Find the mass (in g) of O2 gas required per mole of the initial mixture.
60%
9. Cl2 + KOH  KCl + KClO + H2O
50 %
KClO  KCl + KClO3
80 %
KClO3  KClO4 + KCl
112 L Cl2 gas at STP is passed in 10 L KOH solution, containing 1 mole of potassium hydroxide per liter.
Calculate the total moles of KCl produced, rounding it off to nearest whole number. (Yield of chemical
reactions are written above the arrow () of respective reaction)
10. If 240 g of carbon is taken in a container to convert it completely to CO2 but in industry it has been found
that 280 g of CO was also formed along with CO2. Find the mole percentage yield of CO2. The reactions
1
occurring are : C + O2  CO2 ; C + 2 O2  CO

11. 92 g mixture of CaCO3 and MgCO3 heated strongly in an open vessel. After complete decomposition of
the carbonates it was found that the weight of residue left behind is 48 g. Find the mass of MgCO3 in
grams in the mixture.
12. Among the following compounds given below, what is the sum of the oxidation states of all underlined
elements ?
CO2 , K2MnO4
13. Find the sum of average oxidation number of S in H2SO5 (peroxy monosulphuric acid) and Na2S2O3
(sodium thiosulphate).
14. In the following reaction; xZn + yHNO3(dil)  aZn(NO3)2 + bH2O + cNH4NO3
What is the sum of the coefficients (a + b + c) ?
15. What is the quantity of water (in g) that should be added to 16 g. methanol to make the mole fraction of
methanol as 0.25 :
16. H3PO4 (98 g mol–1) is 98% by mass of solution. If the density is 1.8 g/ml, calculate the molarity.
17. What volume (in mL) of 90% alcohol by weight (d = 0.8 g mL–1) must be used to prepare 80 mL of 10%
alcohol by weight (d = 0.9 g mL–1) ?

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 Mole Concept
18. 3.0 litre of water are added to 2.0 litre of 5 M HCl. What is the molarity of HCl (in M) the resultant solution
?
19. A solution containing 0.1 mol of a metal chloride MClx requires 500 ml of 0.8 M AgNO3 solution for
complete reaction MClx + xAgNO3  xAgCl + M(NO3)x. Then the value of x is :

PART- 4: COMPREHENSION
Read the following comprehension carefully and answer the questions.
Comprehension # 1
A chemist decided to determine the molecular formula of an unknown compound. He collects following
informations :
(I) Compounds contains 2 : 1 'H' to 'O' atoms(number of atoms).
(II) Compounds has 40% C by mass
(III) Approximate molecular mass of the compound is 178 g
(IV) Compound contains C, H and O only.
1. What is the % by mass of oxygen in the compound
(A) 53.33% (B) 88.88% (C) 33.33% (D) None of these
2. What is the empirical formula of the compound
(A) CH3 O (B) CH2 O (C) C2H2 O (D) CH3O2
3. Which of the following could be molecular formula of compound
(A) C 6 H6 O6 (B) C6H12 O6 (C) C 6 H14 O12 (D) C6H14 O6
Comprehension # 2
According to the Avogadro’s law, equal number of moles of gases occupy the same volume at identical
condition of temperature and pressure. Even if we have a mixture of non-reacting gases then Avogadro’s
law is still obeyed by assuming mixture as a new gas.
Now let us assume air to consist of 80% by volume of Nitrogen (N2) and 20% by volume of oxygen (O2).
If air is taken at STP then its 1 mol would occupy 22.4 L. 1 mol of air would contain 0.8 mol of N2 and 0.2
mol of O2 hence the mole fractions of N2 and O2 are given by XN2  0.8 , XO 2  0 .2
4. Volume occupied by air at NTP containing exactly 11.2 g of Nitrogen :
(A) 22.4 L (B) 8.96 L (C) 11.2 L (D) 2.24 L
5. If air is treated as a solution of O2 and N2 then % W/W of oxygen is :
10 200 700 350
(A) (B) (C) (D)
9 9 9 9
6. Density of air at NTP is :
9 2
(A) 1 g/L (B) g/L (C) g/L (D) can’t be determined
7 7
Comprehension # 3
The concentrations of solutions can be expressed in number of ways; viz : mass fraction of solute (or mass
percent), Molar concentration (Molarity) and Molal concentration (molality). These terms are known as
concentration terms and also they are related with each other i.e. knowing one concentration term for the
solution, we can find other concentration terms also. The definition of different concentration terms are
given below :
Molarity : It is number of moles of solute present in one litre of the solution.
Molality : It is the number of moles of solute present in one kg of the solvent
moles of solute
Mole Fraction = moles of solute  moles of solvent

If molality of the solution is given as 'a' then mole fraction of the solute can be calculated by

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 Mole Concept

a a  Msolvent
Mole Fraction = ; = (a  M
1000 solvent  1000)
a
Msolvent
where a = molality and Msolvent = Molar mass of solvent

We can change : Mole fraction  Molality  Molarity

7. 60 g of solution containing 40% by mass of NaCl are mixed with 100 g of a solution containing 15% by mass
NaCl. Determine the mass percent of sodium chloride in the final solution.
(A) 24.4% (B) 78% (C) 48.8% (D) 19.68%
8. What is the molality of the above solution.
(A) 4.4 m (B) 5.5 m (C) 24.4 m (D) none
9. What is the molarity of solution if density of solution is 1.6 g/ml
(A) 5.5 M (B) 6.67 M (C) 2.59 M (D) none
Comprehension # 4
In chemistry, oxidation and reduction are taken as two mutually exclusive events. For example, if life is
oxidation then death is taken as reduction, taking off a flight is oxidation then standing would be reduction
and so many other. In brief it is used as redox in chemical science.
There are so many conceptual facts regarding redox such as adding oxygen or oxygenation, removing
hydrogen or dehydrogenation, removing electron or dielectronation are fixed for oxidation and their
corresponding antonyms would be reduction processes. Simple way of judging whether a monatomic species
has under gone oxidation or reduction is to note if the charge number of species has changed. It is possible
to assign to an atom in polyatomic species an operative charge number called their oxidation number or
state. (O. N. or O. S.). There is no standard symbol for this quantity so we say it is . An O. N. is assigned
to an element in a compound by assuming that it is present as ion with a characteristic charge for instance
oxygen is present as O(-II) and fluorine as F(–I) and some time it may be hypothetical also. For example

For ZnO 

For NH3 

In continuation to our study, species promoting oxidation are named as oxidant and those promoting reduction
are termed as reductant. At the same time their equivalent weights is the ratio of their molecular weight
and change is O. N. () involving one molecule/formula unit of the reactant i.e., molecular weight divided
by number of electrons lost or gained by one molecule/formula during their respective action.
Based on the above discussion answer the following objective question having one best answer.
10. Which corresponds to oxidation action
(A) = 0 (B) = 0 (C) > 0 (D)  < 0
11. A compound contain P(II), Q(V) R(-II). The possible formula of the compound is
(A) PQR 2 (B) Q2(PR 3 )2 (C) P3 [QR4]2 (D) P 3(Q4R)2
12. A compound has  number of carbon,  number of hydrogen and  number of oxygen their equation of
finding oxidation number (x) of carbon will be
 2
(A) 3 + 4x2 + = 0 (B) x + – 2 = 0 (C) x + – = 0 (D) none of these
x 3

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 Mole Concept

PART- 5: COLUMN MATCHING

1. Column - I Column - II
(A) A gaseous organic compound containing (p) One mole of compound contains 4NA atoms of

C = 52.17%, H = 13.04% & O = 34.78% Hydrogen.

(by weight) having molar mass 46 g/mol.
(B) 0.3 g of an organic compound containing (q) The empirical formula of the compound is same as
C, H and O on combustion yields 0.44 g its molecule formula.
of CO2 and 0.18 g of H2O, with two O
atoms per molecule.
(C) A hydrocarbon containing C = 42.857% (r) Combustion products of one mole of compound
and H = 57.143% (by mole) containing 3C contains larger number of moles of CO2 than that of
atoms per molecule. H2O.
(D) A hydrocarbon containing 10.5 g carbon (s) CO2 gas produced by the combustion of 0.25 mole
per gram of hydrogen having vapour of compound occupies a volume of 11.2 L at NTP.
density 46.
2 Column I Column II
(A) Zn(s) + 2HCl(aq)  ZnCl2(s) + H2(g) (p) 50% of excess reagent left
above reaction is carried out by taking
2 moles each of Zn and HCl
(B) AgNO3(aq) + HCl(aq)  AgCl(s) + HNO3(g) (q) 22.4 L of gas at STP is liberated
above reaction is carried out by taking
170 g AgNO3 and 18.25 g HCl (Ag = 108)
(C) CaCO3(s)  CaO(s) + CO2(g) (r) 1 moles of solid (product) obtained.
100 g CaCO3 is decomposed
(D) 2KClO3(s)  2KCl(s) + 3O2(g) (s) HCl is the limiting reagent
2/3 moles of KClO3 decomposed
3.  Column-I Column-II
(A) 100 ml of 0.2 M AlCl3 solution + 400 ml of 0.1 (p) Total concentration of cation(s) = 0.12M
M HCl solution
(B) 50 ml of 0.4 M KCl + 50 ml H2O (q) [SO42–] = 0.06 M
(C) 30 ml of 0.2 M K2SO4 + 70 ml H2O (r) [SO42–] = 2.5 M

EXERCISE-5

1. Amongst the following, the pair having both the metals in their highest oxidation state is :
(A) [Fe(CN)6]3– and [Co(CN)6]3– (B) CrO2Cl2 and MnO4– [JEE 2004]
(C) TiO2 and MnO2 (D) [MnCl4]2– and [NiF6]2–
2. Paragraph for Question Nos. (i) to (iii)
Chemical reactions involve interaction of atoms and molecules. A large number of atoms/molecules
(approximately 6.023 × 1023) are present in a few grams of any chemical compound varying with their
atomic/molecular masses. To handle such large numbers conveniently, the mole concept was introduced.
This concept has implications in diverse areas such as analytical chemistry, biochemistry, electrochemistry
and radiochemistry. The following example illustrates a typical case, involving chemical / electrochemical
reaction, which requires a clear understanding of the mole concept.
A 4.0 molar aqueous solution of NaCl is prepared and 500 mL of this solution is electrolysed. This leads to
the evolution of chlorine gas at one of the electrodes (atomic mass : Na = 23, Hg = 200 ; 1 Faraday = 96500
coulombs).
**[At the anode : 2Cl–  Cl2 + 2e –
At the cathode : Na+ + e–  Na

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 Mole Concept
Na + Hg  NaHg (sodium amalgam)]
** (These reactions were not present in IIT-JEE paper)

(i) The total number of moles of chlorine gas evolved is : [JEE-2007]

(A) 0.5 (B) 1.0 (C) 2.0 (D) 3.0
(ii) If the cathode is a Hg electrode, the maximum weight (g) of amalgam formed from this solution is :
(A) 200 (B) 225 (C) 400 (D) 446 [JEE-2007]
(iii) The total charge (coulombs) required for complete electrolysis is : [JEE-2007]
(A) 24125 (B) 48250 (C) 96500 (D) 193000
3. A student performs a titration with different burettes and finds titre values of 25.2 mL, 25.25 mL, and 25.0
mL. The number of significant figures in the average titre value is : [JEE 2010]
4. Reaction of Br2 with Na2CO3 in aqueous solution gives sodium bromide and sodium bromate with evolution
of CO2 gas. The number of sodium bromide molecules involved in the balanced chemical equation is :
[JEE 2011]
5. Dissolving 120 g of urea (mol. wt. 60) in 1000 g of water gave a solution of density 1.15 g/mL. The molarity
of the solution is : [JEE 2011]
(A) 1.78 M (B) 2.00 M (C) 2.05 M (D) 2.22 M
6. 29.2% (w/w) HCl stock solution has a density of 1.25 g mL–1. The molecular weight of HCl is 36.5 g mol–
1
. The volume (mL) of stock solution required to prepare a 200 mL solution of 0.4 M HCl is : [JEE 2012]
7.* For the reaction : I¯ + ClO3– + H2SO4  Cl¯ + HSO –4 + I2
The correct statement(s) in the balanced equation is/are : [JEE(Advanced) 2014]
–
(A) Stoichiometric coefficient of HSO 4 is 6. (B) Iodide is oxidized.
(C) Sulphur is reduced. (D) H2O is one of the products.
8. A compound H2 X with molar weight of 80 g is dissolved in a solvent having density of 0.4 g ml–1 .
Assuming no change in volume upon dissolution, the molality of a 3.2 molar solution is :
[JEE(Advanced) 2014]
9. The mole fraction of a solute in a solution is 0.1. At 298 K, molarity of this solution is the same as its
molality. Density of this solution at 298 K is 2.0 g cm–3. The ratio of the molecular weights of the solute and

 MWsolute 
solvent,   , is [JEE(Advanced) 2016]
 MWsolvent 
10. The order of the oxidation state of the phosphorus atom in H3PO2, H3PO4, H3PO3, and H4P2O6 is
[JEE(Advanced) 2017]
(A) H3PO4 > H3PO2 > H3PO3 > H4P2O6 (B) H3PO4 > H4P2O6 > H3PO3 > H3PO2
(C) H3PO2 > H3PO3 > H4P2O6 > H3PO4 (D) H3PO3 > H3PO2 > H3PO4 > H4P2O6
PART - 2 : PRACTICE PROBLEMS (JEE ADVANCED)

SECTION-1 : (Only One option correct Type)

This section contains 7 multiple choice questions. Each questions has four choices (A), (B), (C)
and (D) out of which Only ONE option is correct.

1. Calculate the number of Cl¯ and Ca2+ ions in 222 g anhydrous CaCl2
(A) 2NA ions of Ca+2, 2NA ions of Cl– (B) 2NA ions of Ca+2, 4NA ions of Cl–
(C) 2NA ions of Ca+2, 8NA ions of Cl– (D) 4NA ions of Ca+2, 4NA ions of Cl–
2. Equal masses of oxygen, hydrogen and methane are taken in a container in identical condition. Find the
ratio of the volumes of the gases.
(A) O2 : H2 : CH4 1 : 16 : 2 (B) O2 : H2 : CH4 1 : 8 : 1
(C) O2 : H2 : CH4 16 : 1 : 8 (D) O2 : H2 : CH4 8 : 1 : 8

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 Mole Concept

3. The elements A and B form a compound that contains 60% A and 40% B by mass. The atomic mass of B
is twice that of A. Find the empirical formula of the compound.
(A) A3 B2 (B) A3 B (C) A2B3 (D) AB3
4. Equal weight of Zn metal and iodine are mixed together and the iodine is completely converted to ZnI2.
What fraction of weight of the original Zinc remains unreacted. (Atomic wt. Zn = 65)
(A) 0.500 (B) 0.744 (C) 0.488 (D) 0.256
5. One litre of a mixture of CO and CO2 is passed through red hot charcoal in tube. The new volume becomes
1.4 litre. Find out % composition of mixture by volume. All measurements are made at same P and T.
(A) CO2 40 %, CO 60% (B) CO2 60 %, CO 40%
(C) CO2 25 %, CO 75% (D) CO2 30 %, CO 70%
6. The molality of a sulphuric acid solution is 0.2. Calculate the total weight of the solution having
1000 g of solvent.
(A) 1000 g (B) 1098.6 g (C) 980.4 g (D) 1019.6g
7. Generally commercial hydrochloric acid is prepared by heating NaCl with concentrated H2SO4. How
much H2SO4 solution containing 93.0% H2SO4 by mass is required for the production of 1000 kg of
concentrated hydrochloric acid containing 43% HCl by weight .
(A) 590.0 kg solution of H2SO4. (B) 310.3 kg solution of H2SO4.
(C) 620.7 kg solution of H2SO4. (D) 708.2 kg solution of H2SO4 .

Section-2 : (One or More than one options correct Type)

This section contains 5 multipole choice questions. Each questions has four choices (A), (B),
(C) and (D) out of which ONE or MORE THAN ONE are correct.

8. If H2SO4 is formed from it’s elements by taking 6.023 × 1023 atom of ‘O’ 5.6 litre of H2 gas at STP and 8
g S then
(A) 0.125 moles of H2SO4 are formed (B) 0.25 moles of H2SO4 are formed
(C) no moles of ‘S’ are left (D) 1/4 mole of O2 is left
9. 1120 mL of ozonised oxygen at S.T.P. weigh 1.76 g. Calculate the volume of oxygen in the ozonised
oxygen.
(A) It contain 400 mL O2 (B) It contain 224 mL O3
(C) It contain 400 mL O3 (D) It contain 896 mL O2
10. A 5L vessel contains 2.8 g of N2 . When heated to 1800 K , 30% molecules are dissociated into atoms.
(A) Total no. of moles in the container will be 0.13
(B) Total no. of molecules in the container will be close to 0.421 × 1023.
(C) Total no. of moles in the container will be 0.098.
(D) All of these are correct.
11. Equal masses of SO2 and O2 are placed in a flask at STP choose the correct statement.
(A) The number of molecules of O2 are more than SO2
(B) Volume occupied at STP is more for O2 than SO2
(C) The ratio of number of atoms of SO2 and O2 is 3 : 4.
(D) Moles of SO2 is greater than the moles of O2 .
12. For the reaction 2P + Q  R, 12 mol of P and 8 mol of Q are taken then
(A) 3 mol of R is produced (B) 6 mol of R is produced
(C) 25% of Q is left behind (D) 25% of Q has reacted

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 Mole Concept

Section-3 : (One Integer Value Correct Type.)

This section contains 6 questions. Each question, when worked out will result in one integer
from 0 to 9 (both inclusive)

13. XeF6 fluorinates 2 to F7 and liberates Xenon(g). 3.5 mmol of XeF6 can yield a maximum of_____ mmol of
IF 7 .
14. Balance the following equation and choose the quantity which is the sum of the coefficients of all species:
................. CS2 + ................. Cl2  CCl4 + ................. S2Cl2
15. Average atomic mass of magnesium is 24.31 a.m.u. This magnesium is composed of 79 mole % of 24Mg
and remaining 21 mole % of 25Mg and 26Mg. Calculate mole % of 26Mg. Report your answer after
multiplying by 0.1.

16. 200 g impure CaCO3 on heating gives 5.6 lt. CO2 gas at STP. Find the percentage of calcium in the lime
stone sample.
17. Molarity of H2SO4 is 18 M. Its density is 1.8 g/cm3, hence molality is (If your answer is ‘x’ then, Report
your answer x/500).
18. 1g of a mixture of equal number of moles of Li2 CO3 and M2 CO3 required 44.44 ml of 0.5 M HCl for
completion of the reactions.
Li2 CO3 + 2HCl  2LiCl + H2O + CO2
M2 CO3 + 2HCl  2 MCl + H2O + CO2
If the atomic mass of Li is 7 , then find the Atomic mass of M.
Report M – 16.

SECTION-4 : Comprehension Type (Only One options correct)

This section contains 1 paragraphs, each describing theory, experiments, data etc. 3 questions
relate to the paragraph. Each question has only one correct answer among the four given options
(A), (B), (C) and (D)

Comprehension #
Cis-platin is used as an anticancer agent for the treatment of solid tumors, and its prepared as follows :
K2[PtCl4] + 2NH3  [Pt(NH3)2Cl2] + 2KCl
Potassium tetra Cis-platin
chloro platinate (II)
Given 83.0 g of K2[PtCl4] is reacted with 83.0 g of NH3.
[Atomic weights : K = 39, Pt = 195, Cl = 35.5, N = 14]
19. Which reactant is the limiting reagent and which is in excess ?
Limiting Excess
(A) K2[PtCl4 ] NH 3
(B) NH3 K2 [PtCl4 ]
(C) None None
(D) Both Both
20. The number of mol of K2[PtCl4] and NH3 used, respectively, are
(A) 0.1, 0.2 (B) 0.2, 0.4 (C) 0.3, 0.6 (D) 0.03, 0.06
21. The number of mol of excess reactant is
(A) 4.68 (B) 4.78 (C) 4.58 (D) 4.48

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 Mole Concept

SECTION-5 : Matching List Type (Only One options correct)

This section contains 1 questions, each having two matching lists. Choices for the correct
combination of elements from List-I and List-II are given as options (A), (B), (C) and (D) out of
which one is correct

22. Match the reactions given in List-I with the number of electrons lost or gained in List-II
List-I List-II
Reaction Number of electrons lost or gained
(P) Mn (OH)2 + H2 O2  MnO2 + 2H2 O (1) 8
(Q) AlCl3 + 3K  Al + 3KCl (2) 2
(R) 3Fe + 4H2 O  Fe3 O4 + 4H2 (3) 3
(S) 3H2 S + 2HNO3  3S + 2NO + 4H2 O (4) 6
Code :
P Q R S P Q R S
(A) 2 3 1 4 (B) 3 2 1 4
(C) 2 1 3 4 (D) 1 4 3 2

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 Mole Concept

ANSWER KEY
EXERCISE-4
PART- 1
1. (C) 2. (A) 3. (A) 4. (A) 5. (A)
6. (C) 7. (A) 8. (D) 9. (B) 10. (B)
11. (D) 12. (A) 13. (A) 14. (A) 15. (A)
16. (A) 17. (D) 18. (B) 19. (D) 20. (A)
21. (C)

PART- 2
1. (A,B,C) 2. (B,C,D) 3. (A,B) 4. (A,C) 5. (B,C)
6. (A,C) 7. (A,B,C) 8. (B,D) 9. (A,B,D) 10. (A,B,C,D)
11. (A,C) 12. (C,D) 13. (A,B,C) 14. (B,C) 15. (A,B,C)
16. (A,C,D) 17. (A,B) 18. (A,C,D) 19. (A,C,D) 20. (A,B,D)
21. (A,B,D)

PART- 3
1. 5 2. 78 3. 4 4. 11 5. 2
6. 60 7. 28 8. 2 9. 4 10. 50
11. 42 12. 10 13. 8 14. 8 15. 27
16. 18 17. 10 18. 2 19. 4

PART- 4
1. (A) 2. (B) 3. (B) 4. (C) 5. (B)
6. (B) 7. (A) 8. (B) 9. (B) 10. (C)
11. (C) 12. (B)

PART- 5
1. (A - q,s); (B - p, s); (C - p, q, r); (D - q, r) 2. (A - p,q,r,s; (B - p,s; (C - q,r) ; (D - q)
3. (A - p,s); (B - s); (C - p,q); (D - r)

EXERCISE-5
PART- 1
1. (B) 2. (i) (B) (ii) (D) (iii) (D) 3. 3
4. 5 5. (C) 6. 8 mL. 7.* (A,B,D) 8. 8
9. (9) 10. (B)

PART- 2
1. (B) 2. (A) 3. (B) 4. (B) 5. (A)
6. (D) 7. (C) 8. (BC) 9. (BD) 10. (AB)
11. (ABC) 12. (BC) 13. 3 14. 6 15. 1
16. 5 17. 1 18. 7 19. (A) 20. (B)
21. (D) 22. (A)

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 Ideal Gases

EXERCISE-4
PART - 1 : SINGLE OPTION CORRECT TYPE
1. I, II, III are three isotherms respectively at T1, T2 and T3 as shown in graph. Temperature will be in order :

(A) T1 = T2 = T3 (B) T1 < T2 < T3 (C) T1 > T2 > T3 (D) T1 > T2 = T3

2. A 40 ml of a mixture of H2 and O2 at 18 ºC and 1 atm pressure was sparked so that the formation of water
was complete. The remaining pure gas had a volume of 10 ml at 18ºC and 1 atm pressure. If the
remaining gas was H2, the mole fraction of H2 in the 40 ml mixture is :
(A) 0.75 (B) 0.5 (C) 0.65 (D) 0.85
3. On the surface of the earth at 1 atm pressure, a balloon filled with H2 gas occupies 500 mL. This volume
is 5/6 of its maximum capacity. The balloon is left in air. It starts rising. The height above which the balloon
will burst if temperature of the atmosphere remains constant and the pressure decreases 1 mm for every
100 cm rise of height is
(A) 120 m (B) 136.67 m (C) 126.67 m (D) 100 m
4. A vessel of volume 5 litre contains 1.4 g of nitrogen at a temperature 1800 K. The pressure of the gas if
30% of its molecules are dissociated into atoms at this temperature is :
(A) 4.05 atm (B) 2.025 atm (C) 3.84 atm (D) 1.92 atm
5. Two closed vessel A and B of equal volume containing air at pressure P1 and temperature T1 are connected
to each other through a narrow open tube. If the temperature of one is now maintained at T1 and other at
T2 (where T1 > T2) then that what will be the final pressure ?
Ti 2P1T2 2P1T1 2P1
(A) 2P T (B) T  T (C) T  T (D) T  T
1 2 1 2 1 2 1 2

6. Two flasks of equal volume are connected by a narrow tube (of negligible volume) all at 27ºC and contain
0.70 mole of H2 at 0.5 atm. One of the flask is then immersed into a bath kept at 127ºC, while the other
remains at 27ºC. The final pressure in each flask is :
(A) Final pressure = 0.5714 atm (B) Final pressure = 1.5714 atm
(C) Final pressure = 0.5824 atm (D) None of these
7. Two flasks of equal volume are connected by a narrow tube (of negligible volume) all at 27ºC and contain
0.70 moles of H2 at 0.5 atm. One of the flask is then immersed into a bath kept at 127ºC, while the other
remains at 27ºC. The number of moles of H2 in flask 1 and flask 2 are :
(A) Moles in flask 1 = 0.4, Moles in flask 2 = 0.3 (B) Moles in flask 1 = 0.2, Moles in flask 2 = 0.3
(C) Moles in flask 1 = 0.3, Moles in flask 2 = 0.2 (D) Moles in flask 1 = 0.4, Moles in flask 2 = 0.2
8. One litre of a gaseous mixture of two gases effuses in 311 seconds while 2 litres of oxygen takes 20
minutes. The vapour density of gaseous mixture containing CH4 and H2 is :
(A) 4 (B) 4.3 (C) 3.4 (D) 5
9. Pure O2 diffuses through an aperture in 224 second, whereas mixture of O2 and another gas containing
80% O2 diffuses from the same in 234 second. The molecular mass of gas will be
(A) 51.5 (B) 48.6 (C) 55 (D) 46.6
10. A straight glass tube as shown , has 2 inlets X & Y at the two ends of 200 cm long tube. HCl gas through
inlet X and NH3 gas through inlet Y are allowed to enter in the tube at the same time and under the identical
conditions. At a point P inside the tube both the gases meet first. The distance of point P from X is :
(A) 118.9 cm (B) 81.1 cm (C) 91.1 cm (D) 108.9 cm

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 Ideal Gases
11. A teacher enters a classroom from front door while a student from back door. There are 13 equidistant
rows of benches in the classroom. The teacher releases N2O, the laughing gas, from the first bench while
the student releases the weeping gas (C6H11OBr) from the last bench. At which row will the students
starts laughing and weeping simultaneously.
(A) 7 (B) 10 (C) 9 (D) 8
12. A certain volume of argon gas (Mol. Wt. = 40) requires 45 s to effuse through a hole at a certain pressure
and temperature. The same volume of another gas of unknown molecular weight requires 60 s to pass
through the same hole under the same conditions of temperature and pressure. The molecular weight of
the gas is :
(A) 53 (B) 35 (C) 71 (D) 120
13. A sample of an ideal gas was heated from 30ºC to 60ºC at constant pressure. Which of the following
statement(s) is/are true.
(A) Kinetic energy of the gas is doubled (B) Boyle’s law will apply
(C) Volume of the gas will be doubled (D) None of the above
14. 10 ml of a gaseous hydrocarbon was exploded with excess of O2. On cooling the reaction mixture volume
was reduced by 10 ml while on adding KOH volume was reduced by 20 ml. Molecular formula of
hydrocarbon is :
(A) CH4 (B) C4H6 (C) C2H4 (D) C2H2
15. A mixture of methane, propane and carbon monoxide contain 36.5% propane by volume. If its 200 ml are
burnt in excess of O2, the volume of CO2 formed is :
(A) 173 ml (B) 346 ml (C) 200 ml (D) 519 ml

PART- 2: ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

1. A gas cylinder containing cooking gas can withstand a pressure of 14.9 atmosphere. The pressure guaze of
cylinder indicates 12 atmosphere at 27 ºC. Due to sudden fire in the building temperature starts rising. The
temperature at which cylinder will explode is :
(A) 372.5 K (B) 99.5 ºC (C) 199 ºC (D) 472.5 k
2. What conculsion would you draw from the following graphs for an ideal gas ?

(A) As the temperature is reduced, the volume as well as the pressure increase
(B) As the temperature is reduced, the volume becomes zero and the pressure reaches infinity
(C) As the temperature is reduced, the pressure derease
(D) A point is reached where, theoretically, the volume become zero
3. A open ended mercury manometer is used to measure the pressure
exerted by a trapped gas as shown in the figure. Initially
manometer shows no difference in mercury level in both columns
as shown in diagram.
After sparking 'A' dissociates according to following reaction
A(g)  B(g) + 3C(g)
If pressure of Gas “A” decrease to 0.9 atm. Then :
(Assume temperature to be constant and is 300 K)
(A) total pressure increased to 1.3 atm
(B) total pressure increased by 0.3 atm
(C) total pressure increased by 22.3 cm fo Hg
(D) difference in mercury level is 228 mm.
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 Ideal Gases
4. Which of the following is/are correct ?
(A) At constant volume, for a definite quantity of an ideal gas graph of PT v/s T2 will be parabolic
(B) At constant pressure, for a definite quantity of an ideal gas graph of VT v/s T will be parabolic
(C) In going from A to B for definite quantity of an ideal gas pressure increase

V B
A

T
p
(D) At constant volume, for a definite quantity of an ideal gas graph of v/s T2 will be straight line.
T
5. For gaseous state at constant temperature which of the following plot is correct ?

(A) (B) (C) (D)

6. In a closed rigid container, 3 mol of gas A and 1 mol of gas B are mixed at constant temperature. If 1mol
of another gas C at same temperature is introduced and all gases are considered to be non reacting, then
(A) Partial pressure of gases A and B remain unaffected due to introduction of gas C.
3
(B) Ratio of total pressure before and after mixing of gas 'C' is 5 .
(C) If the total pressure of gas mixture before introducing gas 'C' is 20atm, then the total gas pressure after
mixing 'C' will be 25 atm.
(D) If data of option'C' are used, then partial pressure of gas 'C' will be 5 atm.
7. Carbon mono oxide (CO) and oxygen O2 react according to :
2CO(g) + O2(g)  2CO2(g)
Assuming that the reaction takes place and goes to completion, after the valve is
opened in the apparatus represented in the accompanying figure. Also assume
that the temperature is fixed at 300 K. (Take R = 0.08 atm L/mole K)
(A) Partial Pressure of O2 = 6 atm. (B) Number of moles of CO2 formed = 2
(C) Number of moles of O2 left = 1 (D) Partial Pressure of O2 = 3 atm.
8. Which of the following statements are correct ?
(A) Helium diffuses at a rate 8.65 times as much as CO does.
(B) Helium escapes at a rate 2.65 times as fast as CO does.
(C) Helium escapes at a rate 4 times as fast as CO2 does.
(D) Helium escapes at a rate 4 times as fast as SO2 does.
9. The rate of diffusion of 2 gases ‘A’ and ‘B’ are in the ratio 16: 3. If the ratio of their masses present in the
mixture is 2 : 3. Then
(A) The ratio of their molar masses is 16 : 1
(B) The ratio of their molar masses is 1 : 4
(C) The ratio of their moles present inside the container is 1 : 24
(D) The ratio of their moles present inside the container is 8 : 3
10. If a gas is allowed to expand at constant tempeature then which of the following does not hold true :
(A) the kinetic energy of the gas molecules decreases
(B) the kinetic energy of the gas molecules increases
(C) the kinetic energy of the gas molecules remains the same
(D) Can not be predicted

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 Ideal Gases
11. Precisely 1 mol of helium and 1 mol of neon are placed in a container. Indicate the correct statements about
the system.
(A) Molecules of the two gases strike the wall of the container with same frequency.
(B) Molecules of helium strike the wall more frequently.
(C) Molecules of helium have greater average molecular speed.
(D) Helium exerts larger pressure.
12. Indicate the correct statement for equal volumes of N2(g) and CO2(g) at 25ºC and 1 atm.
(A) The average translational KE per molecule is the same for N2 and CO2
(B) The rms speed remains same for both N2 and CO2
(C) The density of N2 is less than that of CO2
(D) The total translational KE of both N2 and CO2 is the same
13. A hypothetical gaseous element having molecular formula Mx may be changed to another gaseous allotrope
having molecular formula My at 310 K. In this act volume of the gas is contracted by 12 ml to a volume of
8 ml. The simplest possible molecular formulae of the two allotropes are
(A) M2 (B) M3 (C) M4 (D) M5
14. A 100 ml mixture of CO and CO2 is passed through a tube containing red hot charcoal. The volume now
becomes 160 ml. The volumes are measured under the same conditions of temperature and pressure.
Amongst the following, select the correct statement(s) :
(A) Mole percent of CO2 in the mixture is 60. (B) Mole fraction of CO in the mixture is 0.40
(C) The mixture contains 40 ml of CO2 (D) The mixture contains 40 ml of CO

PART- 3: NUMERIC VALUE TYPE

d
1. From the graph of vs p at a constant tempreture of 300K calculate molar mass of gas.
p

2. 10 moles of an ideal gas is subjected to an isochoric process (volume const.) and a graph of log (p) v/s log (T)
is plotted where p is in (atm) & T is in kelvin. if volume of the container is 82.1 ml then calculate the sume
of a, b & c where a = slope of graph, b = x intercept of graph, c = y intercept of graph.
3. A tube of length 50 cm is containing a gas in two sections separated by a mercurycolumn of length 5 cm
as shown in figure. The open end of tube is just inside the Hg surface in container find pressure differance
of gases in two sections. [Assume atmospheric pressure = 75 cm of Hg column]

4. The closed cylinder shown in figure has a freely moving piston separating chambers
1 and 2. Chamber 1 contains 280 mg of N2 gas, and chamber 2 contains 200 mg
of helium gas. When equilibrium is established, what will be the ratio L2/L1 ?
(Molecular weights of N2 and He are 28 and 4).
5. A spherical balloon of 21 cm diameter is to be filled up with hydrogen at NTP, from a cylinder containing
the gas at 20 atm at 27°C. If the cylinder can hold 2.82 litre of water, calculate the number of balloons that
can be filled up.
6. A closed container of volume 0.02 m3 contains a mixture of neon and argon gases, at a temperature of 27°C and
pressure of 1 × 105 Nm–2. The total mass of the mixture is 28 g. If the gram molecular weights of neon and
argon are 20 and 40 respectively. Find the masses of the individual gases x and y in the container, assuming them
to be ideal. (Universal gas constant R = 8.314 J/mole K) Give your answer as x + y.

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 Ideal Gases
7. A column of Hg of 100 mm in length is contained in the middle of a narrow tube 1 m long which is closed
at both ends. Both the halves of the tube contained air at a pressure of 760 mm of Hg. By what distance
(in mm) will the column of Hg lie displaced if the tube is held vertical. Assume decrease in length of
mercury column to be negligible , also take the process at constant temperature. (Isothermal process).
8. Consider the arrangment of bulbs shown below.

1.0 L 1.0 L 0.5 L

N2 N2 H2
300 mm 240 mm 440 mm

If the pressure of the system when all the stopcocks are opened is x (in atm) then find 100 x ?
(760 mm = 1 atm)
9. Two vessels whose volumes are in the ratio 2 : 1 contain nitrogen and oxygen at 2500 mm and 1000 mm
pressures respectively when they are connected together what will be the pressure of the resulting mixture
(in meters) ?
10. At 20ºC, two balloons of equal volume and porosity are filled to a pressure of 2 atm, one with 14 kg N2 and
other with 1 kg of H2. The N2 balloon leaks to a pressure of 1/2 atm in 1 hr. How long will it take for H2
balloon to reach a pressure of 1/2 atm ?
11. Two flask A & B have capacity of 1 litre and 2 litre respectively. Each of them contain 1 mole of a gas. The
temperature of the flask are so adjusted that average speed of molecules in “A” is twice that in “B” &
pressure in flask “A” is x times of that in “B”. Then value of x is -
12. 50 ml of gaseous mixture of acetylene and ethylene is taken in a ratio of a : b requires 700 ml of air
containing 20% by volume O2 for complete combusion. Calculate the volume of air required for complete
combution of a mixture (50 ml) having ratio b : a. (Report your answer divide by 25).
13. 10 ml of a mixture of CH4, C2H4 and CO2 was exploded with excess of air. After explosion there was a
contraction of 17 ml and after treatment with KOH, there was further reduction of 14ml. What was the
composition of the mixture? Report your answer as VCH4 + VC2H4 + VCO2 .

PART- 4: COMPREHENSION
Read the following passage carefully and answer the questions.
Comprehension # 1
MEASUREMENT OF PRESSURE
Barometer : A barometer is an instrument that is used for the measurement of pressure. The construction
of the barometer is as follows
Perfect Vaccum P0A
Hg
Hg is filled upto brim
P0 P0= Patm at equilibrium
P0A = mg.
Thin
nairow = (Ah)g.
glass P0
tube P0
Mg

Cross sectional view of the capillary column

A thin narrow calibrated capillary tube is filled to the brim, with a liquid such as mercury, and is inverted into
a trough filled with the same fluid. Now depending on the external atmospheric pressure, the level of the
mercury inside the tube will adjust itself, the reading of which can be monitored. When the mercury column
inside the capillary comes to rest, then the net forces on the column should be balanced.
Applying force balance, we get,
Patm × A= m×g (‘A’ is the cross-sectional area of the capillary tube)
If ‘’ is the density of the fluid, then m=  × g × h (‘h’ is the height to which mercury has risen in the
capillary)

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 Ideal Gases
hence, Patm × A = ( × g × h) × A
or, Patm = gh
Faulty Barometer :
An ideal barometer will show a correct reading only if the space above the mercury column is vacuum, but
in case if some gas column is trapped in the space above the mercury column, then the barometer is
classified as a faulty barometer. The reading of such a barometer will be less than the true pressure.
For such a faulty barometer
Pgas × A

P0A = mg + Pgas A
P0 = gh + Pgas
or gh = P0 – Pgas
Patm × A
mg

1. A tube closed at one end is dipped in mercury as shown in figure-3 such that
the closed surface coincides with the mercury level in the container. By how
much length of the tube should be extended such that the level of Hg in the
tube is 5 cm below the mercury level inside the container. (assume temperature
remains constant)
(A) 18 cm (B) 19 cm
(C) 24 cm (D) 30 cm
24 cm
2.
If above tube is placed vertically with the open end upward Patm = 75 cm
then the length of the air column will be (assume 10cm 10cm,  = 20.4 gm/ml
temperature remains constant) of Hg

(A) 20 cm (B) 36 cm (C) 18 cm (D) 15 cm

3. A gas column is trapped between closed end of a tube and a mercury case  case 
column of length (h) when this tube is placed with its open end upwards P0
P2
2
the length of gas column is (1) the length of gas column becomes (2)
when open end of tube is held downwards (as shown in fig.-4). Find Hg h Hg h
atmospheric pressure in terms of height of Hg column.
1
(assume temperature remains constant)
P1 P0
h ( 1   2 ) h ( 2   1 ) ( 1   2 )
(A) (   ) (B) (   ) (C) h (   ) (D) (h11 + h22)
2 1 1 2 2 1

Comprehension # 2
Dalton's Law : Suppose a mixture of two ideal gases, A and B, is contained in a volume V at a temperature
T. Then, since each gas is ideal, we can write
RT RT
PA = nA , PB = nB
V V
That is, in the mixture each gas exerts a pressure that is the same as it would exert if it were present alone,
and this pressure is proportional to the number of moles of the gas present. The quantities PA and PB are
called the partial pressures of A and B respectively. According to Dalton's law of partial pressures, the
total pressure, Pt , exerted on the walls of the vessel is the sum of the partial pressures of the two gases :
 RT 
Pt = PA + PB = (nA + nB)  V  .
 
The expression can be generalised so as to apply to a mixture of any number of gases. The result is
RT
Pt = Pi
i =
V
n ,
i
i ...(1)

where ' i ' is an index that identifies each component in the mixture and the symbol i stands for the

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 Ideal Gases
operation of adding all the indexed quantities together. Another useful expression of the law of partial
pressures is obtained by writing

nA  nA 
PA  
PA = nA
RT
, Pt =
RT
n , i =
 ni , PA = Pt  ni 
. ....(2)
V V i Pt i   i 

nA
The quantity ni , is called the mole fraction of component A, and equation (2) says that the partial
 i

nA
pressure of any component, such as component A, is the total pressure of the mixture multiplied by ni ,
 i

the fraction of the total moles which are component A.

4. A closed container of volume 30 litre contains a mixture of nitrogen and oxygen gases, at a temperature of
27°C and pressure of 4 atm. The total mass of the mixture is 148 gm. The moles of individual gases in the
container are (Take R = 0.08 litre atm/moleK).
(A) nN2 = 2 moles, nO2 = 3 mole (B) nN2 = 3 mole, nO2 = 2 mole
(C) nN2 = 4 mole, nO2 = 1 mole (D) nN2 = 2.5 mole, nO2 = 2.5 mole

5. If the whole mixture (of above problem) is transferred to a 5 litre vessel at same temperature, then choose
the correct one :
(A) Total pressure in the container remains same.
1
(B) mole fraction of gases will change by 2 unit.
(C) Partial pressure of each gases will be 6 times.
(D) Total pressure in the container becomes half of the initial pressure.
6. If the original mixture (as in Q.No. 16) is allowed to react at this temperature to form NO gas, then the total
pressure in the container after the reaction is :
(A) 2 atm (B) 8 atm (C) 4 atm (D) None of these

PART- 5: COLUMN MATCHING

1. For a fixed amount of the gas match the two column :
Column-I Column-II

(A) (p) T1 > T2 > T3

(B) (q) P1 > P2 > P3

(C) (r) V1 > V2 > V3

(D) (s) d1 > d2 > d3

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 Ideal Gases

2. Single option match maxtix :

Column-I Column-II
(A) P1V1 = P2V2 = P3V3 = .............. (p) Kinetic equation of ideal gases.
V1 V2 V3
(B) T = T = T = .... at constant pressure. (q) Boyle’s law
1 2 3

1
(C) r  (r) Dalton’s law of partial pressures at constant
d
temperature
(D) P = P1 + P2 + P3 +............ (s) Graham’s law
1
(E) PV = mnc2 (t) Charles’ law
3

EXERCISE-5

1. The average velocity of gas molecules is 400 m/sec calculate its r.m.s. velocity at the same temperature.
[JEE-2003]
2. For one mole of gas the average kinetic energy is given as E. The Urms of gas is : [JEE-2004]
2E 3E 2E 3E
(A) (B) (C) (D)
M M 3M 2M
3. Ratio of rates of diffusion of He and CH4 (under identical conditions). [JEE-2005]
1 1
(A) 2 (B) 3 (C) 3 (D) 2
4. At 400 K, the root mean square (rms) speed of a gas X (molecular weight = 40) is equal to the most
probable speed of gas Y at 60 K. The molecular weight of the gas Y is. [JEE-2009]
5.* According to kinetic theory gases [JEE-2011]
(A) collisions are always elastic
(B) heavier molecules transfer more momentum to the waal of the container
(C) only a small number of molecules have very high velocity
(D) between collisions, the molecules move in straight lines with constant velocities.
6. To an evacuated vessel with movable piston under external pressure of 1 atm., 0.1 mol of He and 1.0 mol
of an unknown compound (vapour pressure 0.68 atm. at 0ºC) are introduced. Considering the ideal gas
behaviour, the total volume (in litre) of the gases at 0°C is close to [JEE-2011]
7. The atomic masses of He and Ne are 4 and 20 a.m.u., respectively. The value of the de Broglie wave-
length of He gas at –73C is "M" times that of the de Broglie wavelength of Ne at 727C. M is
[JEE(ADVANCED)-2013]

Paragraph for Questions 8 to 9

A fixed mass 'm' of a gas is subjected to transormation of

states from K to L to M to N and back to K as shown in

the figure.
8. The succeeding operations that enable this transformation of states are [JEE(Advanced)-2013]
(A) Heating, cooling, heating, cooling (B) Cooling, heating, cooling, heating
(C) Heating, cooling, cooling, heating (D) Cooling, heating, heating, cooling

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 Ideal Gases
9. The pair of isochoric processes among the transormation of states is [JEE(Advanced)-2013]
(A) K to L and L to M (B) L to M and N to K (C) L to M and M to N (D) M to N and N to K
Paragraph for questions 10 and 11
X and Y are two volatile liquids L = 24 cm
with molar weights of 10 g mol–
1
and 40 g mol–1 respectively.
Two cotton plugs, one soaked
in X and the other soaked in Y, Cotton wool Cotton wool
soaked in X d
are simultaneously placed at the soaked in Y
Initial formation of
ends of a tube of length L = 24 the product
cm, as shown in the figure.
The tube is filled with an inert gas at 1 atmosphere pressure and a temperature of 300 K. Vapours of X and
Y react to form a product which is first observed at a distance d cm from the plug soaked in X. Take X and
Y to have equal molecular diameters and assume ideal behaviour for the inert gas and the two vapours.
10. The value of d in cm (shown in the figure), as estimated from Graham’s law, is :
[JEE(Advanced)-2014]
(A) 8 (B) 12 (C) 16 (D) 20
11. The experimental value of d is found to be smaller than the estimate obtained using Graham’s law. This is
due to [JEE(Advanced)-2014]
(A) larger mean free path for X as compared to that of Y.
(B) larger mean free path for Y as compared to that of X.
(C) increased collision frequency of Y with the inert gas as compared to that of X with the inert gas.
(D) increased collision frequency of X with the inert gas as compared to that of Y with the inert gas.
238
11. A closed vessel with rigid walls contains 1 mol of 92 U and 1 mol of air at 298 K. Considering
238 206
complete decay of 92 U to 82 Pb , the ratio of the final pressure to the initial pressure of the system
at 298 K is [JEE(Advanced)-2015]
12. One mole of a monoatomic real gas satisfies the equation p(V – b) = RT where b is a constant.
The relationship of interatomic potential V(r) and interatomic distance r for the gas is given by
[JEE(Advanced)-2015]

V(r)

(A) (B) 0
r

V(r)
V(r)

(C) 0
(D) 0 r
r

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 Ideal Gases
PART - 2 : PRACTICE PROBLEMS (JEE ADVANCED)

SECTION-1 : (Only One option correct Type)

This section contains 8 multiple choice questions. Each questions has four choices (A), (B), (C)
and (D) out of which Only ONE option is correct.

1. 10 moles of an ideal gas present in 8.21 litre container at constant temperature. The intercept on y-axis and
slope of curve plotted between P/T vs T.
(A) 0.01, 0 (B) 0.1, 1 (C) 0.1, 0 (D) 10, 1
2 The density of gas A is twice that of B at the same temperature the molecular weight of gas B is twice that
of A.The ratio of pressure of gas A and B will be :
(A) 1 : 6 (B) 1 : 1 (C) 4 : 1 (D) 1 : 4
3. An open flask containing air is heated from 300 K to 500 K. What percentage of air will be escaped to the
atmosphere, if pressure is keeping constant?
(A) 80 (B) 40 (C) 60 (D) 20
4. A gaseous mixture of three gases A, B and C has a pressure of 10 atm. The total number of moles of all the
gases is 10. If the partial pressure of A and B are 3.0 and 1.0 atm respectively and if C has mol. wt. of 2.0,
what is the weight of C in g present in the mixture ?
(A) 6 (B) 8 (C) 12 (D) 3
5. Two vessels connected by a valve of negligible volume. One container (I) has 2.8 of N2 at temperature
T1(K). The other container (II) is completely evacuated. The container (I) is heated to T2 (K) while
container (II) is maintained at T2/3 (K). Volume of vessel (I) is half that of vessel (II). If the valve is
opened then what is the weight ratio of N2 in both vessel (WI/WII) ?
(A) 1 : 2 (B) 1 : 3 (C) 1 : 6 (D) 3 : 1
6. Correct expression for density of an ideal gas mixture of two gases 1 and 2, where m1 and m2 are masses
and n1 and n2 are moles and M1 and M2 are molar masses.
(m1  m 2 ) (m1  m 2 ) P
(A) d = (M  M ) (B) d = (n  n ) RT
1 2 1 2

(n1  n 2 ) P
(C) d = (m  m ) × (D) None of these
1 2 RT
7. A balloon filled with ethyne is pricked with a sharp point and quickly dropped in a tank of H2 gas under
identical conditions. After a while the balloon will :
(A) Shrink (B) Enlarge
(C) Completely collapse (D) Remain unchanged in size
8. 10 ml of gaseous hydrcarbon is exploded with 100 ml O2. The residual gas on cooling is found to measure
95 ml of which 20 ml is abosrbed by KOH and the reminder by alkaline pyrogallol. The formula of the
hydrocarbon is :
(A) CH4 (B) C2H6 (C) C2H4 (D) C2H2

Section-2 : (One or More than one options correct Type)

This section contains 5 multipole choice questions. Each questions has four choices (A), (B),
(C) and (D) out of which ONE or MORE THAN ONE are correct.

9. The Ne atom has 10 times the mass of H2. Which of the following statements are true?
(A) Ten moles of H2 would have the same volume as 1 mole of Ne.
(B) One mole of Ne exerts the same pressure as one mole of H2 at STP
(C) A H2 molecule travels 10 times faster than an Ne atom.
(D) At STP, one litre of Ne has 10 times the density of 1 litre of H2.

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 Ideal Gases
10. Following represent the Maxwell distribution curve for an ideal
Umps1
gas at two temperature T1 and T2. Which of the following option(s)
T1 I
are true ?
Umps2
(A) Total area under the two curves is independent of moles of gas. 1 dN
 T2 II
(B) Umps decreases as temperature decreases. N dU
(C) T1 > T2 and hence higher the temperature, sharper the curve.
(D) The fraction of molecules having speed = Umps decreases as u
temperature increases.
11. If for two gases of molecular weights MA and MB at temperature TA and TB, respectively, TAMB = TBMA,
then which property has the same magnitude for both the gases ?
(A) PV if mass of gases taken are same (B) Pressure
(C) KE per mole (D) Vrms
12. Two non reacting gas A & B having mole ratio of 3 : 5 in a container exerts a pressure of 8 atm. If B
is removed what would be pressure of ‘A’ only, If A is removed what would be pressure of ‘B’ only,
temperature remaining constant.
(A) 3 atm (B) 4 atm (C) 5 atm (D) None of these
13. Which of the following does not shows explicitly the relationship between Boyle's law and Charles' law ?
P1 T1 P2 V1 V2 P1 T2
(A) P = T (B) PV = K (C) P = V (D) V = P × T
2 2 1 2 1 2 1

Section-3 : (One Integer Value Correct Type.)

This section contains 4 questions. Each question, when worked out will result in one integer
from 0 to 9 (both inclusive)

14. A container is divided into 3 identical parts by fixed semipermeable membrane as shown below.

In compartment (i) 4 moles of O2 are taken SPM I SPM II

(i) (ii) (iii)

In compartment (ii) 9 moles of H2 are taken O2 H2 N2
4 mole 9 mole 2 mole
In compartment (iii) 2 moles of N2 are taken
Permeable Permeable
Calculate the ratio of total pressure in the three compartments to H2 & O2 to H2 & N 2
after a sufficient long time. Assume temperature constant
throughout. If ratio is a : b : c (simplest ratio) then express
your answer as a + b + c.
15. The density of a gas filled in an electric lamp is 0.75 kg/m3. When lamp is switched on, the pressure in it
increases from 4 Pa to 25 Pa, then what is increase in urms in m/sec.
16. Gaseous decomposition of A follows Ist order kinetics. Pure A(g) is taken in a sealed flask where
decomposition occurs as
A(g)  2B(g) + C (g)
After 10 sec., a leak was developed in the flask. On analysis of the effused gaseous mixture (Obeying
Graham's law) coming out initially, moles of B(g) were found to be double of A. What is rate constant in sec–
1
.
Given : Molecular weight of A = 16, Molecular weight of B = 4, Molecular weight of C = 8.
[ n 3 = 1.1; n 2 = 0.7]
Write your answer by multiplying it with 100.
17. 0.75 mole of solid X4 and 2 mole of O2 are heated to completely react in a closed rigid container to form
only one gaseous compound (no reactant left behind). Find the ratio of final pressure at 327ºC to the initial
pressure at 27ºC in the flask. Fill your answer as x, where ratio is x : 1.

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 Ideal Gases

SECTION-4 : Comprehension Type (Only One options correct)

This section contains 1 paragraphs, each describing theory, experiments, data etc. 3 questions
relate to the paragraph. Each question has only one correct answer among the four given options
(A), (B), (C) and (D)

Paragraph For Questions 18 to 20

When a sample of an ideal gas is changed from an initial state to a final state, various curves can be plotted
for the process like P–V curve, V–T curve, P–T curve etc.
For example, P–V curve for a fixed amount of an ideal gas at constant temperature is a rectangular
hyperbola, V–T curve for a fixed amount of an ideal gas at constant pressure is a straight line and P–T
curve for a fixed amount of an ideal gas at constant volume is again a straight line. However, the shapes
may vary if the constant parameters are also changed.
Now, answer the following questions :

18. Which of the following statements is correct regarding a fixed amount of ideal gas
undergoing the following process :

(A) Root mean square (RMS) speed of gas molecules increases during the process
A  B.

(B) Density of the gas increases during the process A  B.

(C) Such a graph is not possible.

(D) If PB = 4PA, then VA = 4VB (where PA,VA, PB & VB represent pressure and volume values at states A
and B).
19. Two moles of an ideal gas is changed from its initial state (16 atm, 6L) to final state (4 atm, 15L) in such a
way that this change can be represented by a straight line in P–V curve. The maximum temperature
1
attained by the gas during the above change is : (Take R = 12 L atm K–1 mol–1)
(A) 324 K (B) 648 K (C) 1296 K (D) 972 K
20. Which of the following graphs is not possible for a fixed amount of ideal gas upon moving from initial state
A to final state B :

(A) (B) (C) (D) None of these

SECTION-5 : Matching List Type (Only One options correct)

This section contains 1 questions, each having two matching lists. Choices for the correct
combination of elements from List-I and List-II are given as options (A), (B), (C) and (D) out of
which one is correct

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 Ideal Gases
21. Match each List-I with an appropriate pair from List-II and select the correct answer using the code
given below the lists.
List-I List-II

1
P. vs. P for ideal gas at constant T and n. 1.
V2

1
Q. V vs. for ideal gas at constant P and n 2.
T

R. PT vs. T2 for ideal gas at constant T and n. 3.

1
S. V vs. for ideal gas at constant T and n. 4.
P2

Code :
P Q R S P Q R S
(A) 3 4 1 2 (B) 1 2 4 3
(C) 3 1 2 4 (D) 2 3 1 4

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 Ideal Gases

ANSWER KEY
EXERCISE-4
PART- 1
1. (C) 2. (A) 3. (C) 4. (D) 5. (B)
6. (A) 7. (A) 8. (B) 9. (A) 10. (B)
11. (C) 12. (C) 13. (D) 14. (D) 15. (B)

PART- 2
1. (A,B) 2. (C,D) 3. (A,B,D) 4. (B,C,D) 5. (A,B,C)
6. (A,C,D) 7. (A,B,C) 8. (B,D) 9. (B,D) 10. (A,B,D)
11. (B,C) 12. (A,C,D) 13. (A,D) 14. (A,B,D)

PART- 3
1. 4 2. 1 3. 5 4. 5 5. 10
6. 28 (mAr = 24 + mNe = 4) 7. 30 mm 8. 40 atm 9. 2 mm
10. 16 Minutes 11. 8 12. 27 13. 10

PART- 4
1. (B) 2. (C) 3. (A) 4. (B) 5. (C)
6. (C)

PART- 5
1. (A - s) ; (B - q, s) ; (C - r) ; (D - p, r) 2. (A - q), (B - t), (C - s),(D - r), (E - p)

EXERCISE-5
PART- 1
1. 434 m/s 2. (A) 3. (D) 4. MY = 4. 5.* (A,B,C,D)
6. 7 7. 5 8. (C) 9. (B) 10. (C)
11. (D) 11. 9 12. (C)

PART- 2
1 (C) 2. (C) 3. (B) 4. (C) 5. (C)
6. (B) 7. (B) 8. (D) 9. (B,D) 10. (A,B,D)
11. (A,D) 12. (A,C) 13. (A,B,C) 14. 15 15. 6
16. 4 17. 1 18. (B) 19. (B) 20. (D)
21. (A)

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 Real Gases

EXERCISE-4
PART - 1 : SINGLE OPTION CORRECT TYPE
1. Which of following statement (s) is true.
 – Slope of isotherm at critical point is maximum.
 – Larger is the value of TC easier is the liquification of gas.
 – Vander waals equation of state is applicable below critical temperature at all pressure.
(A) only  (B) &  (C) &  (D) only 
2. Consider the following statements: If the van der Waal’s parameters of two gases are given as
a (atm lit2 mol–2) b (lit mol–1)
Gas X: 6.5 0.056
Gas Y: 8.0 0.011
then (i) : VC (X) < VC (Y) (ii) : PC (X) < PC (Y) (iii) : TC (X) < TC(Y)
Select correct alternate:
(A) (i) alone (B) (i) and (ii) (C) (i), (ii) and (iii) (D) (ii) and (iii)
3. For a real gas the P-V curve was experimentally plotted
and it had the following appearance. With respect to
liquifaction. Choose the correct statement.
(A) at T = 500 K, P = 40 atm, the state will be liquid.
(B) at T = 300 K, P = 50 atm, the state will be gas
(C) at T < 300 K, P > 20 atm, the state will be gas
(D) at 300 K < T < 500 K, P > 50 atm, the state will be liquid.
4. A real gas most closely approaches the behaviour of an ideal gas at :
(A) 15 atm and 200 K (B) 1 atm and 273 K (C) 0.5 atm and 500 K (D) 15 atm and 500 K
5. Calculate the compressibility factor for CO2, if one mole of it occupies 0.4 litre at 300 K and 40 atm.
Comment on the result.
(A) 0.40, CO2 is more compressible than ideal gas (B) 0.65, CO2 is more compressible than ideal gas
(C) 0.55, CO2 is more compressible than ideal gas (D) 0.62, CO2 is more compressible than ideal gas
6. Consider the following statements:
The coefficient B in the virial equation of state
(i) is independent of temperature
 B C 
(ii) is equal to zero at boyle temperature PVm = RT 1 V  2  ..........
 m Vm 
(iii) has the dimension of molar volume
Which of the above statements are correct.
(A) i and ii (B) i and iii (C) ii and iii (D) i, ii and iii
7. At Boyle's temperature, the value of compressibility factor Z = (PVm / RT = Vreal/Videal) has a value of 1,
over a wide range of pressure. This is due to the fact that in the van der Waal’s equation
(A) the constant 'a' is negligible and not 'b'.
(B) the constant 'b' is negligible and not 'a'.
(C) both the constant 'a' and 'b' are negligible.
(D) the effect produced due to the molecular attraction compensates the effect produced due to the
molecular volume.
8. The critical density of the gas CO2 is 0.44 g cm–3 at a certain temperature. If r is the radius of the molecule,
r3 in cm3 is approximately. (N is Avogadro number).
25 100 6 25
(A)  N (B)  N (C)  N (D) 4N

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 Real Gases

9. The curve of pressure volume (PV) against pressure (P) of the

gas at a particular temperature is as shown, according to the
graph which of the following is incorrect (in the low pressure
region):
(A) H2 and He shows +ve deviation from ideal gas equation.
(B) CO, CH4 and O2 show negative deviation from ideal gas equation.
(C) H2 and He show negative deviation while CO, CH4 and O2
show positive deviation.
(D) H2 and He are less compressible than that of an ideal gas
while CO, CH4 and O2 more compressible than that of ideal gas.

PART- 2: ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

1. Which of the following statements are correct ?
(A) It is not possible to compress a gas at a temperature below TC
(B) At a temperature below TC, the molecules are close enough for the attractive forces to act and
condensation occurs
(C) No condensation takes place above TC
(D) Due to higher kinetic energy of gas molecules above TC, it is considered as super critical fluid
2. Which of the following is correct for critical temperature ?
(A) It is the highest temperature at which liquid and vapour can coexist
(B) Beyond this temperature, the gas and the liquid phases have different critical densities
(C) At this temperature, the gas and the liquid phases have different critical densities
(D) All are correct
3. The vander waal gas constant ‘a’ is given by
2 2
1 1 RTC 27 R TC
(A) V (B) 3 PC VC2 (C) 8 P (D)
3 C C 64 PC
4. Which of the following are correct statements ?
(A) vander Waals constant ‘a’ is a measure of attractive force
(B) van der Waals constant ‘b’ is also called co-volume or excluded volume
(C) ‘b’ is expressed in L mol–1
(D) ‘a’ is expressed in atm L2 mol–2
5. Select the correct statement(s) :
(A) At Boyle’s temperature a real gas behaves like an ideal gas at low pressure
(B) Above critical conditions, a real gas behave like an ideal gas
(C) For hydrogen gas ‘b’ dominates over ‘a’ at all temperature
(D) At high pressure van der Waals’ constant ‘b’ dominates over ‘a’
6. Which is/are correct for real gases ?
(A) PLt
0
(PVm) = constant at constant high temperature

(B) VmLt0 (PVm) = constant at constant low temperature

PV
 m
(C) PLt   = 1 at high temperature
0  RT 

 PV 
(D) VLt  m =R
0  RT 

7. Which of the following statements are incorrect ?

(A) Molar volume of every gas at STP is 22.4 L (B) Under critical states compressibility factor is 1
(C) All gases will have equal value of average KE at a given temperature
(D) At absolute zero, KE is 3/2 R.

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 Real Gases

PART- 3: NUMERIC VALUE TYPE

1. The vander waals constant ‘b’ of a gas is 4 × 10–4 L/mol. The radius of gas atom can be expressed in
scientific notation as z × 10–9 cm. Calculate the value of z. (Given NA = 6 × 1023)
2. For a fixed amount of real gas when a graph of z v/s P was plotted then at very high pressure slope was
observed to be 0.01 atm–1. At the same temperature if a graph is plotted b/w pv v/s P then for 2 moles of
the gas ‘Y’ intercept is found to be 40 atm-liter. Calculate excluded volume in litres for 20 moles of the real
gas.
D VC
3. If C & D are the third & fourth virial coefficients. If  then find the value of x.
C x
4. Calculate molecular diameter for a gas if its molar excluded volume is 3.2  ml. (in nenometer). Give the
answer by multiplying with 10. (Take NA = 6.0 × 1023).
x  P 
5. If the ratio of PVm & RT for a real gas is at a temp where  V  = 0. The find value of 10x.

24  m 

6. 1 mole of CCl 4 vapours at 77°C occupies a volume of 35.0 L.If van der Waal’s constant are
a = 20.39 L2 atm mol–2 and b = 0.1383 L mol–1, calculate compressibility factor Z under,
(a) low pressure region (b) high pressure region
Report your answer as nearest whole number of (a + b) × 10.
7. To an evacuated 504.2 mL steel container is added 25 g CaCO3 and the temperature is raised to 1500 K
causing a complete decomposition of the salt. If the density of CaO formed is 3.3 g/cc, find the accurate
pressure developed in the container using the Van der waals equation of state. The van der waals constants
L2  atm L
for CO2(g) are a = 4 2 , b = 0.04 mol . (Ca - 40, C - 12, O - 16). Report your answer as nearest whole
mol
number.

PART- 4: COMPREHENSION
Read the following passage carefully and answer the questions.
Comprehension # 1
One of the important approach to the study of real gases involves the analysis of a parameter Z called the
PVm
compressibility factor Z = where P is pressure, Vm is molar volume, T is absolute temperature and R
RT

 Vm real 
is the universal gas constant. Such a relation can also be expressed as Z =   (where V
 m ideal
and Vm real
 Vm ideal 
are the molar volume for ideal and real gas respectively). Gas corresponding Z > 1 have repulsive tendencies
among constituent particles due to their size factor, whereas those corresponding to Z < 1 have attractive
forces among constituent particles. As the pressure is lowered or temperature is increased the value of Z
approaches 1. (reaching the ideal behaviour)
1. Choose the conclusions which are appropriate for the observation stated.
Observation Conclusion
I. Z=1 I. The gas need not be showing the ideal behaviour
II. Z>1 II. On applying pressure the gas will respond by increasing its volume
III. Z<1 III. The gas may be liquefied.
IV. Z  1 for low P IV. The gas is approaching the ideal behaviour.
(A) All conclusions are true (B) Conclusions I, II & IV are true
(C) Conclusions I,III & IV are true (D) Conclusions III & IV are true
2. For a real gas ‘G’ Z > 1 at STP Then for ‘G’ :
Which of the following is true :
(A) 1 mole of the gas occupies 22.4 L at NTP

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 Real Gases
(B) 1 mole of the gas occupies 22.4 L at pressure higher than that at STP (keeping temperature constant)
(C) 1 mole of the gas occupies 22.4 L at pressure lower than that at STP (keeping temperature constant)
(D) None of the above
3. Following graph represents a pressure (P) volume (V)
relationship at a fixed temperature (T) for n moles of a
real gas. The graph has two regions marked (I) and (II).
Which of the following options is true.
(A) Z < 1 in the region (II)
(B) Z = 1 in the region (II)
(C) Z = 1 for the curve
(D) Z approaches 1 as we move from region (II) to region (I)

Comprehension # 2
Critical constant of A gas
When pressure is incerases at constant temp volume of gas decreases
AB  gases, BC  vapour + liquid, CD  liquid
critical point : At this point all the physical
properties of liquid phase will be same
as the physical properties in vapour such
as, density of liquid = density of vapour
TC or critical temp : Temperature
above which a gas can not be liquified
PC or critical pressure : minimum
pressure which must be applied at critical
temp to convert the gas into liquid.
VC or critical volume : volume occupied by one mole of gas at TC & PC

CRITICAL CONSTANT USING VANDER WAAL EQUATIONS :

 
P  a 
 2
Vm 
(Vm – b) = RT
T  ( PVm2  a ) (Vm – b) = RT Vm2


a V ab RT 
PVm3 + aVm – PbVm2 – ab – RTVm2 = 0  Vm3 + Vm2  b  P  + – =0
  P m P
since equation is cubic in Vm hence there will be three roots of equation at any temperature and pressure.
At critical point all three roots will coincide and will give single value of Vm = Vc
at critical point, Vander Waal equation will be

RTC  a ab
Vm3 – Vm2  b  P  + P Vm – P = 0 ...(1)
 C  C C

But at critical point all three roots of the equation should be equal, hence equation should be :
Vm, = Vc
(Vm – Vc)3 = 0
Vm3 – 3Vm2 VC + 3Vm VC2 – VC3 = 0 ...(2)
comparing with equation (1)
RTC a ab
b + P = 3VC ....(i) PC
= 3 VC2 ...(ii) PC
= VC3 ...(iii)
C

From (ii) and (iii), VC = 3b

a a a
From (ii) PC = 3 V 2 substituting PC = 3 (3b)2 =
C 27b 2

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 Real Gases
RTC 8a
From (i) PC
= 3 VC – b = 9b – b = 8b  TC = 27 Rb

At critical point, the slope of PV curve (slope of isotherm) will be zero at all other point slope will be
negative
zero is the maximum value of slope.
 P    P 
   
 V 
 m TC
=0 ...(i) Vm
 V 
 m TC
=0 ....(ii)

{Mathematically such points an known as point of inflection (where first two derivatives becomes zero)}

using the two TC PC and VC can be calculate by

RT B C
4. A scientist proposed the following equation of state P = V – V 2 + V3 . If this equation leads to the
m m m

critical behaviour then critical temperature is :

8B B B2
(A) 27RC (B) 8RC (C) (D) None of these
3RC
5. If the critical constants for a hypothetical gas are VC = 150 cm3 mol–1. PC = 50 atm and TC = 300 K. Then
1
the radius of the molecule is : [Take R = 12 Ltr atm mol–1 K–1]

1/ 3 1/ 3 1/ 3 1/ 3
 75   75   3   3 
(A)   (B)   (C)   (D)  
 2N   8N   N   256N 
 A   A   A   A 
6. Identify the wrong statement related to the above graph :
(A) between 50 K and 150 K temperature and pressure ranging from 10
atm to 20 atm matter may have liquid state.
(B) zero is the maximum value of the slope of P-V Curve
(C) If vander waal equation of state is applicable above critical temperature
then cubic equation of Vm will have one real and two imaginary roots.
(D) At 100 K and pressure below 20 atm it has liquid state only

PART- 5: COLUMN MATCHING

1. Column – I Column – II
(A) H2 gas at NTP (p) Molar volume = 22.4 L
10
(B) O2 gas having density more than g/L at NTP (q) Molar volume > 22.4 L
7
20
(C) SO2 gas at NTP having density more than g/L (r) More compressible with respect to ideal gas
7
1
(D) He gas at NTP having density less than g/L (s) Less compressible with respect to ideal gas
5.6

2. Column – I Column – II
pb
(A) At low pressure (p) Z = 1 + RT

a
(B) At higher pressure (q) Z = 1 – V RT
m

(C) At low density of gas (r) gas is more compressible

(D) For H2 and He at 0°C (s) gas is less compressible

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 Real Gases

EXERCISE-5

1. Figure displays the plot of the compression factor Z verses p for a few gases [JEE-2006]

Which of the following statements is/are correct for a van-der waals gas :
(A) The plot I is applicable provided the vander waals constant a is negligible.
(B) The plot II is applicable provided the vander waals constant b is negligible.
(C) The plot III is applicable provided the vander waals constants a and b are negligible.
(D) The plot IV is applicable provided the temperature of the gas is much higher than its critical temperature.
2. Match gases under specified conditions listed in Column-I with their properties / laws in Column-II.
[JEE-2007]
Column-I Column-II
(A) Hydrogen gas (P = 200 atm, T = 273 K) (p) compressibility factor  1
(B) Hydrogen gas (P ~ 0, T = 273 K) (q) attractive forces are dominant
(C) CO2 (P = 1 atm, T = 273 K) (r) PV = nRT
(D) Real gas with very large molar volume (s) P(V – nb) = nRT
3. A gas described by van der Waals equation [JEE-2008]
(A) behaves similar to an ideal gas in the limit of large molar volumes
(B) behaves similar to an ideal gas is in limit of large pressures
(C) is characterised by van der Waals coefficients that are dependent on the identity of the gas but are
independent of the temperature.
(D) has the pressure that is lower than the pressure exerted by the same gas behaving ideally
4. The term that corrects for the attractive forces present in a real gas in the vander Waals equation is :
an2 an 2
(A) nb (B) (C) – (D) –nb [JEE-2009]
V2 V2
5. For one mole of a van der Waals gas when b = 0 and T = 300 K, the PV vs.1/V plot is shown below. The
value of the vanderWaals constant a (atm.liter2 mol–2) : [JEE-2012]

(A) 1.0 (B) 4.5 (C) 1.5 (D) 3.0

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 Real Gases
6. One mole of a monoatomic real gas satisfies the equation p(V – b) = RT where b is a constant.
The relationship of interatomic potential V(r) and interatomic distance r for the gas is given by
[JEE(Advanced)-2015]

(A) (B) (C) (D)

ANSWER KEY
EXERCISE-4
PART- 1
1. (B) 2. (D) 3. (D) 4. (C) 5. (B)
6. (C) 7. (D) 8. (D) 9. (C)

PART- 2
1. (B,C,D) 2. (A,B) 3. (B,D) 4. (A,B,C,D) 5. (A,B,D)
6. (A,C) 7. (A,B,D)

PART- 3
1. 5 2. 4 3. 3 4. 2 5. 90
6. 20 7. 62 atm.

PART- 4
1. (D) 2. (B) 3. (D) 4. (C) 5. (D)
6.* (A,D)

PART- 5
1. (A) - q,s ; (B) - r ; (C) - r ; (D) - q,s 2. (A) - q,r (B) - p,s ; (C) - q,r ; (D) - p,s

EXERCISE-5
PART- 1
1.* (A,B,C) 2. A – p, s ; B – r ; C – p, q ; D – r 3.* (A,C,D) 4. (B)
5. (C) 6. (C)

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 Chemical Equilibrium

EXERCISE-4
PART - 1 : SINGLE OPTION CORRECT TYPE
1. The equilibrium constant (Kp) for the reaction PCl5(g) PCl3(g) + Cl2(g) is 16. If the volume of the
container is reduced to one half its original volume, the value of Kp for the reaction at the same temperature
will be :
(A) 32 (B) 64 (C) 16 (D) 4
2. If K1, K2, K3 are equilibrium constant for formation of AD, AD2, AD3 respectively as follows A + D
D ,
AD + D AD2, AD2 + D AD3 . Then equilibrium constant 'K' for A + 3D AD3 is related
as
(A) K1 + K2 + K3 = K (B) logK1 + logK2 + logK3 = log K
(C) K1 + K2 = K3 + K (D) log K1 + logK2 = logK3 + log K
3. In the reaction, N2 + O2 2NO, the moles/litre of N2, O2 and NO respectively 0.25, 0.05 and 1.0 at
equilibrium, the initial concentration of N2 and O2 will be respectively :
(A) 0.75 mol/litre, 0.55 mole/litre (B) 0.50 mole/litre, 0.75 mole/litre
(C) 0.25 mole/litre, 0.50 mole/ litre (D) 0.25 mole/litre, 1.0 mole/litre
4. The reaction, PCl5 PCl3 + Cl2 is started in a five litre container by taking one mole of PCl5. If 0.3 mole
of PCl5 is there at equilibrium, concentration of PCl3 and KC will respectively be :
49 23 23 49
(A) 0.14, (B) 0.12, (C) 0.07, (D) 20,
150 100 100 150
5. 'a' moles of PCl5, undergoes, thermal dissociation as : PCl5 PCl3 + Cl2, the mole fraction of PCl3 at
equilibrium is 0.25 and the total pressure is 2.0 atmosphere. The partial pressure of Cl2 at equilibrium is :
(A) 2.5 (B) 1.0 (C) 0.5 (D) None
6. A 10 litre box contains O3 and O2 at equilibrium at 2000 K. KP = 4 × 1014 atm for 2O3(g) 3O2(g).
Assume that PO2  PO3 and if total pressure is 8 atm, then partial pressure of O3 will be :
(A) 8 × 10–5 atm (B) 11.3 × 10–7 atm (C) 9.71 × 10–6 atm (D) 9.71 × 10–2 atm
7. Sulfide ion in alkaline solution reacts with solid sulfur to form polysulfide ions having formulae S22–, S32–,
S42– and so on. The equilibrium constant for the formation of S22– is K1 = 12 & for the formation of S32– is
K2 = 132, both from S and S2–. What is the equilibrium constant for the formation of S32– from S22– and S?
(A) 11 (B) 12 (C) 132 (D) None of these
8. Attainment of the equilibrium A(g) 2C(g) + B(g) gave the following graph. Find the correct option.
(% dissociation = fraction dissociated × 100)

(A) At t = 5 sec equilibrium has been reached and Kc = 128 (mol/litre)2

(B) At t = 5 sec equilibrium has been reached and % dissociation of A is 60%
(C) At t = 5 sec equilibrium has been reached and % dissociation of A is 40%
(D) None of these

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 Chemical Equilibrium
9. A 10 L container at 300 K contains CO2 gas at pressure of 0.2 atm and an excess solid CaO (neglect the
volume of solid CaO). The volume of container is now decreased by moving the movable piston fitted in the
container. What will be the maximum volume of container when pressure of CO2 attains its maximum
value given that CaCO3 (s) CaO(s) + CO2(g) Kp = 0.800 atm
(A) 5 L (B) 2.5 L (C) 1 L (D) The information is insufficient.
10. In the system, LaCl3(s) + H2O(g) + heat LaClO(s) + 2HCl(g), equilibrium is established. More
water vapour is added to restablish the equlibrium. The pressure of water vapour is doubled. The factor by
which pressure of HCl is changed is:
(A) 2 (B) 2 (C) 3 (D) 5

11. Some quantity of water is contained in a container as shown in figure. As neon is added
to this system at constant pressure, the amount of liquid water in the vessel
(A) increases (B) decreases
(C) remains same (D) changes unpredictably
12. The equilibrium constant for, 2H2S (g) 2H2(g) + S2(g) is 0.0118 at 1300 K while the heat of dissociation
is 597.4 kJ. The standard equilibrium constant of the reaction at 1200 K is :
(A) 1.180 × 10–4 (B) 11.80 (C) 118.0
(D) cannot be calculated from given data
13. For reaction, assuming large volume of water.
H2O() H2O(g) ; at temp. T K
Choose correct options :
(A) On introduction of an inert gas at constant temperature pressure in the container remains same at
equilibrium.
(B) For this system % relative humidity always remains 100% at constant temperature at equilibrium
(C) If steam at temperature ‘2T’ is passed into given system, after equilibrium is attained relative humidity
changes.
(D) This is a special case of equilibrium where pressure of H2O(g) remains same always due to unique
structural feature of H2O.

14.

Na2SO4.10H2O (s) Na2SO4.5H2O (s) + 5H2O (g) KP = 2.43 × 10–8 atm5

Incorrect statement is –
(A) If partial pressure of H2O in container is 3.5 × 10–2 atm amount of Na2SO4.5H2O decreases.
(B) If PH2O = 2.5 × 10–2 atm then amount of Na2SO4.5H2O should increases.
(C) If PH2O = 3 × 10–2 atm then both solid does not get altered.
(D) If Na2SO4.5H2O is completely removed then partial pressure of H2O increases at equilibrium.
15. For the equilibrium CuSO4.5H2O(s) CuSO4.3H2O(s) + 2H2O(g)
Kp = 2.25 × 10–4 atm2 and vapour pressure of water is 22.8 Torr at 298 K.
CuSO4.5H2O(s) is efflorescent (i.e., loses water) when relative humidity is :
(A) less than 33.3% (B) less than 50 % (C) less than 66.6% (D) above 66.6%
16. In the Haber process for the industrial manufacturing of ammonia involving the reaction,
N2(g) + 3H2(g) 2NH3(g) at 200 atm pressure in the presence of a catalyst, a temperature of about
500ºC is used. This is considered as optimum temperature for the process because
(A) yield is maximum at this temperature

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 Chemical Equilibrium
(B) catalyst is active only at this temperature
(C) energy needed for the reaction is easily obtained at this temperature
(D) rate of the catalytic reaction is fast enough while the yield is also appreciable for this exothermic
reaction at this temperature.
17. Addition of water to which of the following equilibria causes it to shift in the backward direction?
(A) CH3NH2 (aq) + H2O () CH3NH3 (aq) + OH– (aq)
+ –
(B) AgCl (s) Ag (aq) + Cl (aq)
(C) HCN (aq) + H2O () H3O+ (aq) + CN– (aq)
(D) [Cr(dien)2]3+ (aq) + 3H2O () + 3Cl– (aq) [Cr (H2O)3Cl3] (aq) + 2 dien (aq)
18. Consider the reactions
(i) PCl5(g) PCl3(g) + Cl2(g)
(ii) N2O4(g) 2NO2(g)
The addition of an inert gas at constant volume
(A) will increase the dissociation of PCl5 as well as N2O4
(B) will reduce the dissociation of PCl5 as well as N2O4
(C) will increase the dissociation of PCl5 and step up the formation of NO2
(D) will not disturb the equilibrium of the reactions
19. For a system at equilibrium some changes are made which is reported by a graph (shown below). Changes
has been made at constant temperature.

Choose the correct options :

(A) (B)

(C) (D)

20. An equilibrium mixture in a vessel of capacity 100 litre contain 1 mol N2, 2 mol O2 and 3 mol NO. Number
of moles of O2 to be added so that at new equilibrium the conc. of NO is found to be 0.04 mol/lit.:
(A) (101/18) (B) (101/9) (C) (202/9) (D) None of these
21. CaCl2.6H2O(s) CaCl2(s) + 6H2O(s)
–17
Kp = 6.4 × 10 atm 6

Excess solid CaCl2.6H2O & CaCl2 are taken in a container containing some water vapours at a pressure
of 1.14 torr at a particular temp.
(A) CaCl2(s) acts as drying agent under given condition.
(B) CaCl2(s) acts as hydrosceopic substance given condition.
(C) CaCl2.6H2O(s) acts as effluoroscent substance.
(D) Mass of CaCl2.6H2O(s) increases due to some reaction.

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 Chemical Equilibrium
22. A(s) B(g) + C(g) KP = 40 atm2
X(s) B(g) + E(g)
Above equilibrium is allowed to attain in a closed container and pressure of B was found to be 10 atm.
Calculate standard Gibb’s free energy change for X(s) B(g) + E(g)) at 300 K (take R = 2 cal/K/
mol)
(A) 3.5 Kcal/mol (B) 3 Kcal/mol (C) 2.5 Kcal/mol (D) 2 Kcal/mol

PART- 2: ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

1. Which of the following is correct about the chemical equilibrium ?
(A) (G)T,P = 0
(B) Equilibrium constant is independent of initial concentration of reactants
(C) Catalyst has no effect on equilibrium state
(D) Reaction stops at equilibrium
2. For a reaction N2 + 3H2 2NH3, the value of KC does not depends upon :
(A) Initial concentration of the reactants (B) Pressure
(C) Temperature (D) catalyst
3. Which of the following statement/s is/are correct :
(A) At equilibrium, vapour pressure of solution and refractive index of eq. mixture becomes constant.
(B) Equilibrium can be attained in both homogenous and heterogenous reaction.
(C) Approach to the equilibrium is fast in initial state but gradually it decreases.
(D) Equilibrium is dynamic in nature
4. Equilibrium constant for following reactions respectively K1, K2 and K3
N2 + 3H2 2NH3 K1
N2 + O2 2NO K2
1
H2 + O H2O K3
2 2

5
2NH3 + O 2NO + 3H2O K4
2 2
Which of the following relation is correct.

K 2  (K 3 )3 K 4  K1 K 2  (K 3 )3
3
(A) K1 = K4
(B) K4 = K1 × K2/(K3) (C) K2 = (K )3 (D) K4 = K1
3

kc 1
5. If log k  log RT = 0, then above is true for the following equilibrium reaction
p

1 3
(A) NH3(g) N2(g) + H2(g) (B) CaCO3(s) CaO(s) + CO2(g)
2 2
(C) 2NO2(g) N2O4 (g) (D) H2(g) + 2(g) 2H(g)
6. The reaction for which, KP = KC is satisfied
(A) A(g) + 2B(g) 3C(g) (B) A(s) B(g)
(C) 2A(g) B(g) + C(g) (D) A(s) + B(g)  C(s) + 2D(g)
7. At 300 K, the reactions satisfying the following graph is :

(A) A(s) 2B(g) (B) 2A(g) B(g) + 3C(g)

(C) A(s) B(g) + C(g) (D) 2A(g) B(g)

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 Chemical Equilibrium
8. N2O4(g) 2NO2(g), Kc = 4. This reversible reaction is studied graphically as shown in figure. Select
the correct statements.

(A) Reaction quotient has maximum value at point A

(B) Reaction proceeds left to right at a point when [N2O4] = [NO2] = 0.1 M
(C) Kc = Q when point D or F is reached
(D) None of these
Dd
9. The equation  = is not correctly matched for :
(n  1)d
(A) A(g) (n/2)B(g) + (n/3)C(g) (B) A(g) (n/3)B(g) + (2n/3)C(g)
(C) A(g) (n/2)B(g) + (n/4)C(g) (D) A(g) (n/2)B(g) + C(g)
10. If reaction A + B C + D, take place in 5 liter close vessel, the rate constant of forward reaction is nine
times of rate of backward reaction.
If initially one mole of each reactant present in the container, then find the correct option/s.
[C] 3
(A) = (B) log KP = log KC
[B] 1
(C) [D]eq = 15 × 10–2 mole L–1 (D) Keq = 9
11. Consider the following equilibrium
2AB(g) A2(g) + B2(g)
The vapour density of the equilibrium mixture does not depend upon
(A) Temperature (B) Initial concentration
(C) Volume of contain (D) Pressure of equilibrium mixture
12. Vapour density of equilibrium PCl5(g) PCl3(g) + Cl2(g) is decreased by
(A) increasing temperature (B) decreasing pressure
(C) increasing pressure (D) decreasing temperature
13. CuSO4.5H2O(s) CuSO4(s) + 5H2O(g) Kp = 10–10 (atm). 10–2 moles of CuSO4.5H2O(s) is taken in a
1
2.5L container at 27°C then at equilibrium [Take : R = litre atm mol–1 K–1]
12
(A) Moles of CuSO4.5H2O left in the container is 9 × 10–3
(B) Moles of CuSO4.5H2O left in the container is 9.8 × 10–3
(C) Moles of CuSO4 left in the container is 10–3
(D) Moles of CuSO4 left in the container is 2 × 10–4
14. CuSO4.5H2O(s) CuSO4.3H2O(s) + 2H2O (s) KP = 0.4 × 10–3 atm2
Which of following statement are correct :
(A) Gº = – RT ln PH2O where PH2O = Partial pressure of H2O at equilibrium.
(B) At vapour pressure of H2O = 15.2 torr relative humidity of CuSO4.5H2O is 100%.
(C) In presence of aqueous tension of 24 torr, CuSO4.5H2O can not loss moisture.
(D) In presence of dry atmosphere in open container CuSO4.5H2O will completely convert into CuSO4.3H2O
15. For a reversible reaction aA + bB cC + dD ; the variation of K with temperature is given by
K º  1 1
2  H
log K =    then,
1 2.303R  T2 T1 
(A) K2 > K1 if T2 > T1 for an endothermic change

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 Chemical Equilibrium
(B) K2 < K1 if T2 > T1 for an endothermic change
(C) K2 > K1 if T2 > T1 for an exothermic change
(D) K2 < K1 if T2 > T1 for an exothermic change
16. 1 mole each of H2(g) and 2(g) are introduced in a 1L evacuated vessel at 523K and equilibrium
H2(g) + 2(g) 2HI (g) is established. The concentration of HI(g) at equilibrium :
(A) Changes on changing pressure.
(B) Changes on changing temperature.
(C) Changes on changing volume of the vessel.
(D) Is same even if only 2 mol of HI (g) were introduced in the vessel in the begining.
(E) Is same even when a platinum gauze is introduced to catalyse the reaction.
17. For the reaction : PCl5 (g) PCl3 (g) + Cl2 (g)
The forward reaction at constant temperature is favoured by
(A) introducing chlorine gas at constant volume (B) introducing an inert gas at constant pressure
(C) increasing the volume of the container (D) introducing PCl5 at constant volume
18. Which of the following reaction will shift in forward direction. When the respective change is made at
equilibrium:
(A) N2(g) + 3H2(g) 2NH3(g) increase in pressure at eq.
(B) H2O(s) H2O() addition of inert gas at constant volume
(C) PCl5(g) PCl3(g) + Cl2(g) addition of inert gas at constant pressure
(D) H2 + I2 2HI increase in temperature
19. Which of the following does not affect the value of equilibrium constant of a reaction ?
(A) Change in temperature (B) Addtion of catalyst
(C) Change in concentration of the reactants (D) Change in pressure
20. If the volume of the reaction flask is reduced to half of its initial value and temperature is kept constant then
in which of the following cases the position of equilibrium will shift ?
(A) CO(g) + H2O(g) CO2(g) + H2(g) (B) I2(g) 2I(g)
(C) NH4HS(s) NH3(g) + H2S(g) (D) 2NOCl(g) 2NO(g) + Cl2(g)
21. 2CaSO4(s) 2CaO(s) + 2SO2(g) + O2(g), H > 0
Above equilibrium is established by taking some amount of CaSO4(s) in a closed container at 1600 K. Then
which of the following may be correct option.
(A) moles of CaO(s) will increase with the increase in temperature
(B) If the volume of the container is doubled at equilibrium then partial pressure of SO2(g) will change at
new equilibrium.
(C) If the volume of the container is halved partial pressure of O2(g) at new equilibrium will remain same
(D) If two moles of the He gas is added at constant pressure then the moles of CaO(s) will increase.
22. The dissociation of phosgene, which occurs according to the reaction
COCl2 (g) CO(g) + Cl2(g)
Is an endothermic process. Which of the following will increase the degree of dissociation of COCl2?
(A) Adding Cl2 to the system (B) Adding helium to the system at constant pressure
(C) Decreasing the temperature of the system (D) Reducing the total pressure
23. Consider the following two equilibria simultaneously established in a rigid vessel at a particular temperature:
NH2COONH4(s) 2NH3 (g) + CO2(g)
CaCO3(s) CaO(s) + CO2 (g)
Now, on adding some amount of NH3 to the reaction vessel, the orignal equilibrium is disturbed and a new
equilibrium state is obtained. On comparing the following at the initial & final equilibrium states, select the
INCORRECT statement (s) :
(A) Nothing can be said about the number of moles of CO2 gas in reaction vessel.
(B) Nothing can be said about the number of moles of NH3 gas in reaction vessel.

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 Chemical Equilibrium
(C) Number of moles of NH3 gas would have definitely increased.
(D) Number of moles of CaCO3 solid gas would have definitely decreased.

PART- 3: NUMERIC VALUE TYPE

1. How many of the following reactions are homogenous reversible reactions ?
(1) CH3COOH() + C2H5OH() CH3COOC2H5() + H2O()
(2) C(s) + CO2(g) CO(g) + H2O(g)
(3) H2(g) + CO2(g) CO(g) + H2O(g)
(4) CO(g) + Cl2(g) COCl2(g)
(5) NH4HS(s) NH3(g) + H2S(g)
(6) CaCO3(s) CaO(s) + CO2(s)
(7) N2(g) + O2(g) 2NO(g)
(8) CO2(g) + C(s) 2CO(g)
(9) SO2(g) + NO2(g) SO3(g) + NO(g)
1
(10) NO(g) + Br () 2NOBr(g)
2 2
1
2. The equilibrium SO2(g) + O (g) SO3 (g) is established in a container of 4L at a particular temperature.
2 2
If the number of moles of SO2, O2 and SO3 at equilibrium are 2, 1 and 4 respectively then find the value of
equilibrium constant.
3. A (g) + B (g) C (g) + D (g)
Above equilibrium is established by taking A & B in a closed container. Initial concentration of A is twice of
the initial concentration of B. At equilibrium concentrations of B and C are equal. Then find the equilibrium
constant for the reaction, C (g) + D (g) A (g) + B (g).
4. If the equilibrium constant of the reaction
2HI(g) H2(g) + I2(g) is 0.25, find the equilibrium constant of the reaction.
1 1
H2 + I2 HI(g)
2 2
5. In an experiment starting with 1 mole of ethyl alcohol, 1 mole of acetic acid and 1 mole of water at T0C, the
equilibrium mixture on analysis shows that 54.3% of the acid is esterfied. Calculate the equilibrium constant
of this reaction.
6. For the reaction, N2O5(g) 2NO2(g) + 1/2 O2(g), calculate the mole fraction of N2O5(g) decomposed
at a constant volume & temperature, if the initial pressure is 600 mm Hg & the pressure at any time is 960
mm Hg. Assume ideal gas behaviour. If answer is x then report 10x.
7. Consider the equilibrium, Ni(s) + 4CO(g) Ni(CO)4(g) ; Kp = 0.125 atm–3.
If equal number of moles of CO and Ni(CO)4 (ideal gases) are mixed in a small container fitted with a
piston, find the maximum total pressure (in atm) to which this mixture must be brought in order to just
precipitate out metallic Ni ?
8. In a container H2O(g), CO(g) and H2(g) are present in the molar ratio of 1 : 2 : 3 respectively at temperature
of 300 K. Find the pressure in the container at which solid carbon (graphite) will start forming in the
container given that :
C(s) + H2O(g) CO(g) + H2(g) Kp = 3 atm
9. Kp is 9 atm2 for the reaction : LiCl.3NH3 (s) LiCl.NH3(s) + 2NH3(g) at 40°C. How many moles of
ammonia must be added at this temperature to a 5 litre flask containing 0.1 mole of LiCl. NH3 in order to
completely convert the solid to LiCl.3NH3? Multiply the obtained answer by 100. Round off the answer to
the nearest integer.
10. The dissociation pressure of silver oxide at 4450C is 207 atm. Calculate G0 for the formation of 1 mole
Ag2O(s) from metal and oxygen at this temperature. (log 207 = 2.315). Report your answer in Kcal and
round of the value to nearest integer.

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 Chemical Equilibrium
11. Consider the reaction, 2Cl2(g) + 2H2O(g) 4HCl(g) + O2(g) ; Hº = + 113 kJ
The four gases, Cl2, H2O, HCl and O2, are mixed and the reaction is allowed to come to equilibrium.
Each operation is to be considered separately. Temperature and volume are constant unless stated
otherwise. Report the number of operations in the left column which lead to increase in the equilibrium
value of the quantity in the right column.
(a) Increasing the volume of the container Number of moles of H2O
(b) Adding O2 Number of moles of H2O
(c) Adding O2 Number of moles of HCl
(d) Decreasing the volume of the container Number of moles of Cl2
(e) Decreasing the volume of the container Partial pressure of Cl2
(f) Decreasing the volume of the container KC
(g) Raising the temperature KC
(h) Raising the temperature Concentration of HCl
(i) Adding He Number of moles of HCl
(j) Adding catalyst Number of moles of HCl
12. For given simultaneous reaction :
X(s) A(g) + B(s) + C(g) K P1 = 500 atm

Y(s) D(g) + A(g) + E(s) K P2 = 2000 atm

If total pressure = x, then write your answer after dividing by 25.
13. When C2H5OH and CH3COOH are mixed in equivalent proportion, equilibrium is reached when 2/3 of
acid and alcohol are used. How much ester will be present when 3 mole of acid were to react with 3 mole
of alcohol. Express your answer multiplying with 10.
14. For equilibrium, N2O4(g) 2NO2(g)
the observed vapour density of N2O4 is 40 at 350 K. Calculate percentage dissociation of N2O4(g) at
350K.
15. The vapour density of N2O4 at a certain temperature is 30.67. The % dissociation of N2O4 at this temperature
is :
16. Solid ammonium carbamate dissociates to give ammonia and carbon dioxide as follows:
NH2 COONH4 (s) 2NH3 (g) + CO2 (g)
At equilibrium, ammonia is added such that partial pressures of NH3 at new equilibrium equals the original
total pressure (at previous equilibrium). If the ratio of the total pressures now to the original total pressure
is a/b then report a + b.
17. If 50% of CO2 converts to CO at the equilibrium pressure of 12 atm. Calculate KP
C(s) + CO2(s) 2CO(s)

PART- 4: COMPREHENSION
Read the following passage carefully and answer the questions.
Comprehension # 1
Le chatelier's principle
If a system at equilibrium is subjected to a change of any one of the factors such as concentration, pressure
or temperature, the system adjusts itself in such a way as to nulify the effect of that change.
Change of pressure : If a system in equilibrium consists of gases, then the concentrations of all the
components can be altered by changing the pressure. To increase the pressure on the system, the volume
has to be decreased proportionately. The total number of moles per unit volume will now be more and the
equilibirum will shift in the direction in which there is decrease in number of moles i.e., towards the
direction in which there can be decrease in pressure.
Effect of pressure on melting point : There are two types of solids :

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 Chemical Equilibrium
(a) Solids whose volume decreases on melting, e.g., ice, diamond, carborundum, magnesium nitride
and quartz.
Solid (higher volume) Liquid (lower volume)
The process of melting is facilitated at high pressure, thus melting point is lowered.
(b) Solids whose volume increase on melting, e.g., Fe, Cu, Ag, Au, etc.
Solid (lower volume) Liquid (higher volume)
In this case the process of melting become difficult at high pressure; thus melting point becomes
high.
(c) Solubility of substances : When solid substance are dissolved in water, either heat is evolved
(exothermic) or heat is absorbed (endothermic).
KCl + aq KCl(aq) – heat
In such cases, solubility increase with increase in temperature. Consider the case of KOH; when
this is dissolved, heat is evolved.
KOH + aq KOH(aq) + heat
In such cases, solubility decrease with increase in temperature.
(d) Solubility of gases in liquids : When a gas dissolves in liquid, there is decrease in volume. Thus,
increase of pressure will favour the dissolution of gas in liquid.
1. A gas 'X' when dissolved in water heat is evolved. Then solublity of 'X' will increase :
(A) Low pressure, high temperature (B) Low pressure, low temperature
(C) high pressure, high temperature (D) high pressure, low temperature
2. Au(s) Au()
Above equilibrium is favoured at :
(A) High pressure low temperature (B) High pressure high temperature
(C) Low pressure, high temperature (D) Low pressure, low temperature

1 1
3. For the reaction, N (g) + O2(g) NO(g)
2 2 2
If pressure is increased by reducing the volume of the container then :
(A) Total pressure at equilibrium will change.
(B) Concentration of all the component at equilibrium will change.
(C) Concentration of all the component at equilibrium will remain same
(D) Equilibrium will shift in the forward direction
Comprehension # 2
Effect of temperature on the equilibrium process is analysed by using the thermodynamics
From the thermodynamics relation
Gº = – 2.30 RT logk .......... (1) Gº : Standard free energy change
Gº = Hº – TSº .......... (2) Hº : Standard heat of the reaction.
From (1) & (2)
– 2.3 RT logk = Hº – TSº Sº : Standard entropy change
Hº  Sº
 logK =  2.3RT  2.3 R .......... (3)

Hº
Clearly if a plot of log k vs 1/T is made then it is a straight line having slope = 2.3 R

S
and Y intercept = 2.3 R

If at temp. T1 equilibrium constant be k1 and at temperature T2 equilibrium constant be k2 then :

The above equation reduces to :

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 Chemical Equilibrium
Hº Sº
 log K1 =   .......... (4)
2.3 R T1 2.3 R

Hº Sº
 log K2 =   .......... (5)
2.3 R T2 2.3 R
Substracting (4) from (5) we get
K2  Hº  1 1 
 log    
K1 2.30 R  T1 T2 


From the above relation we can conclude that the value of equilibrium constant increases with increase in
temperature for endothermic reaction but value of equilibrium constant decreases with the increase in
temperature for exothermic reaction.
1
4. If standard heat of dissociation of PCl5 is 230 cal then slope of the graph of logk vs is :
T
(A) +50 (B) – 50 (C) 10 (D) None
1
5. For exothermic reaction if S0 < 0 then the sketch of logk vs may be :
T

(A) (B) (C) logk (D)

1/T
6. If for a particular reversible reaction KC = 57 at 355ºC and KC = 69 at 450ºC then :
(A) H < 0 (B) H > 0
(C) H = 0 (D) H whose sign can’t be determined

PART- 5: COLUMN MATCHING

1. Match the following : (Assume only reactants were present initially).

Column  Column 

(A) N2(g) + 3H2(g) 2NH3(g) (t = 300ºC) (p) ng > 0

(B) PCl5(g) PCl3(g) + Cl2(g) (t = 50ºC) (q) Kp < Kc

(C) C(s) + H2O(g) CO(g) + H2(g) (r) Kp not defined

(D) CH3COOH() + C2H3OH () CH3COOC2H5() + H2O() (s) Pinitial > Peq.
2. Match the following :
Column I (Assume only reactant were present initially) Column II

(A) For the equilibrium NH4(s) NH3(g) + H(g), (p) Forward shift
if pressure is increased at equilibrium

(B) For the equilibrium N2(g) + 3H2(g) 2NH3(g) (q) No shift in equilibrium
volume is increased at equilibrium

(C) For the equilibrium H2O(g) + CO(g) H2(g) + CO2 (g) (r) Backward shift
inert gas is added at constant pressure at equilibrium

(D) For the equilibrium PCl5 PCl3 + Cl2 (s) Final pressure is more than
Cl2 is removed at equilibrium. initial pressure

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 Chemical Equilibrium

[NH3 ] 2
3. For the reaction : N2 (g) + 3H2(g) 2NH3 (g) ; equilibrium constant Kc =
[N2 ] [H2 ] 3
Some reactions are written bellow in column I and their equilibrium constants in terms of Kc are written in
column II. Match the following reactions with the corresponding equilibrium constant

Column I (Reaction) Column II (Equilibrium constnat)

(A) 2N2 (g) + 6H2 (g) 4NH3 (g) (p) 2Kc

1
(B) 2NH3 (g) N2(g) + 3H2(g) (q) K 2
c

1 3 1
(C) N (g) + H2(g) NH3 (g) (r) K
2 2 2 c

(s) K 2c

EXERCISE-5

1. At constant temperature, the equilibrium constant (KP) for the decomposition reaction N2O4 2NO2 is
2
(4 x P)
expressed by KP = , where P = pressure, x = extent of decomposition. Which one of the following
(1  x 2 )
statements is true ? [JEE 2001]
(A) KP increases with increase of P (B) KP increases with increase of x
(C) KP increases with decrease of x (D) KP remains constant with change in P and x
2. Consider the following equilibrium in a closed container [JEE 2002]
N2 O4 (g) 2NO2 (g)
At a fixed temperature, the volume of the reaction container is halved. For this change, which of the
following statements holds true regarding the equilibrium constant (KP) and degree of dissociation ()?
(A) neither KP nor  changes (B) both KP and  change
(C) KP changes, but  does not change (D) KP does not change but  changes
6
3. N2 + 3H2 2 NH3 K = 4 × 10 at 298
K = 41 at 400 K
Which statements is correct ? [JEE 2006]
(A) If N2 is added at equlibrium condition, the equilibrium will shift to the forward direction because
according to IInd law of thermodynamics the entropy must increases in the direction of spontaneous reaction.
(B) The condition for equilibrium is 2GNH3 = 3GH2 + GN2 where G is Gibbs free energy per mole of the
gaseous species measured at that partial pressure.
(C) Addition of catalyst does not change Kp but changes H.
(D) At 400 K addition of catalyst will increase forward reaction by 2 times while reverse reaction rate will
be changed by 1.7 times.
4. The value of log10K for a reaction A B is :
(Given : rH298K = –54.07 kJ mol , –1
r S 298K = 10 JK–1 mol–1 and R = 8.314 JK–1 mol–1; 2.303 × 8.314 ×
298 = 5705) [JEE 2007]
(A) 5 (B) 10 (C) 95 (D) 100

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 Chemical Equilibrium
5. Statement-1 : For every chemical reaction at equilibrium, standard Gibbs energy of reaction is zero.
Statement-2 : At constant temperature and pressure, chemical reactions are spontaneous in the direction
of decreasing Gibbs energy. [JEE 2008]
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
6. The thermal dissociation equilibrium of CaCO3(s) is studied under different conditions.
CaCO3(s) CaO(s) + CO2(g)
For this equilibrium, the correct statement(s) is (are) : [JEE(Advanced) 2013]
(A) H is dependent on T
(B) K is independent of the initial amount of CaCO3
(C) K is dependent on the pressure of CO2 at a given T
(D) H is independent of the catalyst, if any

Paragraph 1
Thermal decomposition of gaseous X2 to gaseous X at 298 K takes place according to the following
equation : X 2 (g)  2X(g)

7. The standard reaction Gibbs energy,  r G o , of this reaction is positive. At the start of the reaction, there is
one mole of X2 and no X. As the reaction proceeds, the number of moles of X formed is given by  . Thus.
equilibrium is the number of moles of X formed at equilibrium. The reaction is carried out at a constant total
pressure of 2 bar. Consider the gases to behave ideally. (Given : R = 0.083 L bar K–1 mol–1) 8. The
equilibrium constant Kp for this reaction at 298 K, in terms of  equilibrium , is [JEE(Advanced) 2016]
2 2
8equilibrium 8equilibrium 42equilibrium 42equilibrium
(A) (B) (C) (D)
2  equilibrium 4  equilibrium 2  equilibrium 4  equilibrium

8. The INCORRECT statement among the following, for this reaction, is [JEE(Advanced) 2016]
(A) Decrease in the total pressure will result in formation of more moles of gaseous X
(B) At the start of the reaction, dissociation of gaseous X2 takes place spontaneously
(C)  equilibrium = 0.7
(D) KC < 1
PART - 2 : PRACTICE PROBLEMS (JEE ADVANCED)

SECTION-1 : (Only One option correct Type)

This section contains 7 multiple choice questions. Each questions has four choices (A), (B), (C)
and (D) out of which Only ONE option is correct.

1. Which of the following is correct for the equilibrium of the reaction C(s) + H2O(g) CO(g) + H2(g).
p H2 2O
(A) pH2  pH2O (B) pH2  pH2O (C) pH2  pH2 2O (D) pH2 
p CO
2. For the reaction PCl5 PCl3 + Cl2; Supposing at constant temperature, if the volume is increased 16
times the initial volume, the degree of dissociation for this reaction will becomes :
1 1
(A) 4 times (B) times (C) 2 times (D) times
4 2
3. A vessel of 10 L was filled with 6 mole of Sb2S3 and 6 mole of H2 to attain the equilibrium at 440oC as :

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 Chemical Equilibrium
Sb2S3(s) + 3H2(g) 2Sb(s) + 3H2S(g)
After equilibrium the H2S formed was analysed by dissolving it in water and treating with excess of Pb2+ to
give 708 g of PbS as precipitate. What is value of Kc of the reaction at 440ºC ? (At. weight of Pb = 206).
(A) 0.08 (B) 0.8 (C) 0.4 (D) 0.04
1
4. Variation of log10 K with is shown by the following graph in which straight line is at 45°, hence H° is :
T

(A) + 4.606 cal (B) – 4.606 cal (C) 2 cal (D) – 2 cal
5. aA + bB cC + dD
In above reaction low pressure and high temperature, conditions are shift equilibrium in back direction so
correct set :
(A) (a + b) > (c + d), H > 0 (B) (a + b) < (c + d), H > 0
(C) (a + b) < (c + d), H < 0 (D) (a + b) > (c + d), H < 0
6. The value of kp for the reaction at 270C
Br2() + Cl2(g) 2BrCl(g)
is ‘1 atm’. At equilibrium in a closed container partial pressure of BrCl gas is 0.1 atm and at this temperature
the vapour pressure of Br2() is also 0.1 atm. Then what will be minimum moles of Br2() to be added to 1
mole of Cl2 , initially, to get above equilibrium situation :
10 5 15
(A) moles (B) moles (C) moles (D) 2 moles
6 6 6
7. C(s) 2A(g) + B(s)
If the dissociation of C(s) is ‘’ and d is the density of the gaseous mixture in the container. Initially
container have only ‘C(s)’ and the reaction is carried at constant temperature and pressure.

(A) (B) (C) (D)

Section-2 : (One or More than one options correct Type)

This section contains 4 multipole choice questions. Each questions has four choices (A), (B),
(C) and (D) out of which ONE or MORE THAN ONE are correct.

Kp
8. For which reaction at 298 K, the value of K is maximum and minimum respectively :
c
(A) N2O4 2NO2 (B) 2SO2 + O2 2SO3
(C) X + Y 4Z (D) A + 3B 7C
9. For the equilibrium 2SO2(g) + O2(g) 2SO3(g), H = –198 kJ, the equilibrium concentration of SO3 will be
affected by
(A) doubling the volume of the reaction vessel (B) increasing the temperature at constant volume
(C) adding more oxygen to the reaction vessel (D) adding helium to the reaction vessel at constant
volume
10. AB(s) A (g) + B(g) Kp = 4, H = + ve
In a container, A (g) and B (g) are filled to partial pressure of 1 atm each. Now AB (s) is added (in excess
quantity). Which of the following is CORRECT ? (No other gas is present in container) :

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 Chemical Equilibrium
(A) At equilibrium, the total pressure in the container is 4 atm.
(B) Equilibrium pressure decreases uniformly on increasing the volume by container.
(C) At equilibrium, the total pressure in the container is more than 4 atm, if temperature is increased.
(D) None of these
11. Following two equilibria are established seperately in 2 different containers of unequal volume.
PCl5(g) PCl3(g) + Cl2(g)
COCl2(g) CO(g) + Cl2(g)
Now the containers are connected together by a thin tube of negligible volume.
Select incorrect statements. (Assume T constant)
(A) Degree of dissociation of both PCl5(g) & COCl2(g) will decrease
(B) Degree of dissociation of both PCl5(g) & COCl2(g) will increase
(C) Degree of dissociation of PCl5(g)may increase ; decrease or remain the same irrespective of effect on
degree of dissociation of COCl2(g).
(D) Degree of dissociation of PCl5(g) may increase, decrease or remain the same, but the effect would be
same as that on degree of dissociation of COCl2.

Section-3 : (One Integer Value Correct Type.)

This section contains 6 questions. Each question, when worked out will result in one integer
from 0 to 9 (both inclusive)

12. If 1 mole of CH3COOH and 1 mole of C2H5OH are taken in 1 litre flask, 50% of CH3COOH is converted
into ester as ;
CH3COOH() + C2H5OH() CH3COOC2H5() + H2O()
There is 33% conversion of CH3COOH into ester, if CH3COOH and C2H5OH have been taken initially in
molar ratio x : 1, find x.
13. Solid ammonium carbamate (NH2COONH4) was taken in excess in closed container of volume 5 Litre
according to the following reaction NH2COONH4(s) 2NH3(g) + CO2(g). If equilibrium partial pressure
of ammonia is 4 atm, it’s equilibrium constant Kp is x atm3. If the above equilibrium mixture is transferred
to another vessel of volume 10 Litre, total equilibrium pressure is y atm. Calculate the value of (x + y).
Assuming temperature is constant during the whole experiment.
14. Find the percentage dissociation of ammonia into N2 and H2 if the dissociation is carried out at constant
pressure and the volume at equilibrium is 20% greater than initial volume. (initially, equal moles of NH3 and
N2 are present with no hydrogen)
15. A2B(g) is introduced in a vessel at 1000 K. If partial pressure of A2B (g) is 1 atm initially and KP for
reaction A2B(g) 2A(g) + B(g) is 81 × 10–6 then calculate percentage of dissociation of A2B.

16. Consider the following two equilibrium established together in a closed container
A(s) 2B(g) + 3C(g) ; K P1

A(s) 3D(g) ; K P2
Starting with only A(s), molar ratio of B(g) & D(g) at equilibrium is found to be in a ratio 1 : 6 determine

KP2
8KP1 .

17. 0.1 mol each of ethyl alcohol and acetic acid are allowed to react and at equilibrium the acid was exactly
neutralised by 100 ml of 0.75 N NaOH. If no hydrolysis of ester is supposed to have undergo find KC in
–1
terms ( x) 10

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 Chemical Equilibrium

SECTION-4 : Comprehension Type (Only One options correct)

This section contains 1 paragraphs, each describing theory, experiments, data etc. 2 questions
relate to the paragraph. Each question has only one correct answer among the four given options
(A), (B), (C) and (D)

Paragraph for Question Nos. 18 to 19

There are different types of equilibria depending on the composition of equilibrium mixture. Homogenous
equilibrium contains all the species in same phase and heterogeneous equilibrium contains different phases.
If heterogeneous equilibrium involves pure solid or liquid, then their concentration or pressure term is not
included in KC or KP respectively.
18. 05 moles of NH4HS(s) are taken in a container having air at 1 atm. On warming the closed container to
50ºC the pressure attained a constant value of 1.5 atm, with some NH4HS (s) remaining unreacted. The
KP of reaction NH4HS(s) NH3(g) + H2S(g) at 50°C is :
(A) 0.25 (B) 0.625 (C) 0.025 (D) 0.0625

19. How many moles of water are in vapour phase present inside the vessel containing 1 L water after
25
sufficient time? (Vapour pressure of water at 27ºC = 3000 Pa, R = J/mol–K)
3
(A) 5 × 10–4 (B) 120 (C) 1.2 × 10–3 (D) None of these

SECTION-5 : Matching List Type (Only One options correct)

This section contains 1 questions, each having two matching lists. Choices for the correct
combination of elements from List-I and List-II are given as options (A), (B), (C) and (D) out of
which one is correct.

20. In given setup, container I has double the volume to that of container II. Container I & II are connected by
a narrow tube with two knobs.

Knob A : Closed – No gas is allowed to pass through

Open – All gases can pass
Knob B : Closed – A thin filter of Pd is introduced on complete cross section of tube
Open – All gases can pass.
Initially both knobs are closed. In container I, some amount of NH3 gas is introduced which sets up
equilibrium according to following reaction :
2NH3(g) N2(g) + H2(g)
Match the actions in column I to corresponding value in column II and select the correct answer using
the code given below the column. Assume each action from initial stage.

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 Chemical Equilibrium
Column I Column II

P. A & B are closed, pH2 / pN2 = ? 1. 1/3

Q. A is open & B is closed, nHI 2 / nNI 2 = ? 2. 3

R. A is open & B is open, nNI 2 / nHII2 = ? 3. 2

S. A & B are left open for long time ; 4. 2/3

now B is closed & volume of container II
is halved.

( nNI 2 + nNII2 )/( nHI 2 + nHII2 ) = ?

Code :
P Q R S P Q R S
(A) 4 2 3 1 (B) 2 3 4 1
(C) 2 1 3 4 (D) 1 2 3 4

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 Chemical Equilibrium

ANSWER KEY

EXERCISE-4
PART- 1
1. (C) 2. (B) 3. (A) 4. (A) 5. (C)
6. (B) 7. (A) 8. (C) 9. (B) 10. (B)
11. (B) 12. (A) 13. (B) 14. (D) 15. (B)
16. (D) 17. (D) 18. (D) 19. (B) 20. (A)
21. (C) 22. (C)

PART- 2
1. (A,B,C) 2. (A,B,D) 3. (A,B,C,D) 4. (A,C,D) 5. (A,B)
6. (A,C) 7. (A,B,C) 8. (B,C) 9. (A,C,D) 10. (A,B,C,D)
11. (A,B,C,D) 12. (A,B) 13. (B,D) 14. (B,C,D) 15. (A,D)
16. (A,B,C,D,E) 17. (B,C,D) 18. (A,B,C) 19. (B,C,D) 20. (B,C,D)
21. (A,C,D) 22. (B,D) 23. (A,B,C)

PART- 3
1. 05 2. 4 3. 3 4. 2 5. 4
6. 4 7. 4 8. 3 9. 78 mole 10. 4
11. 5 12. 4 13. 20 14. 15 15. 50
16. 58 17. 16

PART- 4
1. (D) 2. (C) 3.* (A,B) 4. (B) 5. (B)
6. (B)

PART- 5
1. (A - q, s) ; (B - p) ; (C - p) ; (D - r) 2. (A - r) ; (B - r) ; (C - q) ; (D - p)
3. (A - s) ; (B - r) ; (C - q)

EXERCISE-5
PART- 1
1. (D) 2. (D) 3. (B) 4. (B) 5. (D)
6. (A,B,D) 7. (B) 8. (C)

PART- 2
1. (B) 2. (A) 3. (A) 4. (B) 5. (D)
6. (C) 7. (D) 8. (B,D) 9. (A,B,C) 10. (A,C,D)
11. (A,B,D) 12. 2 13. 38 14. 40 15. 3
16. 8 17. 1 18. (D) 19. (A) 20. (B)

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 Ionic Equilibrium (Elementry)

EXERCISE-4
PART - 1 : SINGLE OPTION CORRECT TYPE
1. The self ionisation constant for pure formic acid, K = [HCOO H2 ][HCOO–] has been estimated as 10–6 at
room temperature. The density of formic acid is 1.15 g/cm3. What percentage of formic acid molecules in
pure fomic acid are converted to formate ion ?
(A) 0.002% (B) 0.004% (C) 0.006% (D) 0.008%

2. pKa for an acid HA is 6. The value of K for the reaction A– + H3O+ HA + H2O is :
(A) 1 × 10–6 (B) 1 × 108 (C) 1 × 10–8 (D) 1 × 106
3. 10–6 M HCI is diluted to 100 times. Its pH is :
(A) 6 (B) 8 (C) 6.98 (D) 7.02
4. Which of the following solutions has a pH exactly equal to 8 ?
(A) 10–8 M HCl solution (B) Solution containing 10–8 M H+
–6
(C) 2 × 10 M Ba(OH)2 solution (D) 10–8 M NaOH solution
5. 10 mL of a strong acid solution of pH = 2 are mixed with 990 mL of another strong acid solution of pH = 4.
The pH of the resulting solution will be :
(A) 3 (B) 3.3 (C) 3.7
(D) Molecular formula of both strong acids should be known to answer above question.
6. % dissociation of a 0.024 M solution of a weak acid HA (Ka = 2 × 10–3) is :
(A) 0.25% (B)  29% (C) 25% (D)  0.29%
7. For a weak base BOH, Kb = 10–4. Calculate pH of 10–4 M BOH solution. (Take log 6.2 = 0.79)
(A) 10 (B) 9.79 (C) 8 (D) None of these
M
8. In a solution obtained by mixing 100 mL of 0.25 M Triethylamine (Kb = 6.4 × 10–5) & 400 mL of NH4
18
OH (Kb = 1.8 × 10–5) :
(A) [NH4+] = 4 × 10–4 M (B) [C6NH16+] = 1.6 × 10–3 M
(C) Both (A) & (B) (D) None of these
9. Four separate solutions of sodium salts NaW, NaX, NaY and NaZ have pH 7, 9, 10 and 11 respectively,
when each solution has concentration 0.1 M. Then the strongest acid is :
(A) HW (B) HX (C) HY (D) HZ
10. To prepare a buffer of pH 8.26 amount of (NH4)2 SO4 to be added to 500 mL of 0.01 M NH4OH solution
is :
[pKa (NH4+) = 9.26]
(A) 0.05 mole (B) 0.025 mole (C) 0.10 mole (D) 0.005 mole
11. A weak acid (HA) after treatment with 12 mL of 0.1 M strong base (BOH) solution has a pH of 5. At the
end point, the volume of same base solution required is 27 mL. Ka of acid is :
(A) 1.8 × 10–5 (B) 8 × 10–6 (C) 1.8 × 10–6 (D) 8 × 10–5
12. Slaked lime, Ca(OH)2 is used extensively in sewage treatment. What can be the maximum pH of Ca(OH)2
(aq) ? (Take log11 = 1.04)
Ca(OH)2(s) Ca2+(aq) + 2OH–(aq) ; Ksp = 5.324 × 10–6
(A) 12.04 (B) 12.34 (C) 10.68 (D) 14
13. The solubility of Ag2CO3 in water is 1.26 × 104 mole/litre. What is its solubility in 0.02 M Na2CO3 solution
3
? Assume no hydrolysis of CO32 ion. (Take 2 = 1.26)
6 6
(A) 5 × 10 M (B) 50 × 10 M (C) 105 M (D) 2 × 105 M

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 Ionic Equilibrium (Elementry)

PART- 2: ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

1. Which statement(s) is/are correct ?
(A) All Bronsted bases are also Lewis bases.
(B) All Bronsted acids are not Lewis acids.
(C) Most cations are acids and most anions are bases.
(D) All Bronsted bases are also Arrhenius bases.
2. Select the incorrect statement(s) :
(A) NH4+ (aq) is a strong acid. (B) CH3COO– (aq) is a weak base.
(C) H– is a weak base. (D) HS– is a weak acid as well as a weak base.
3. For pure water :
(A) pKw increases with decrease in temperature.
(B) Absolute dissociation constant decreases with decrease in temperature.
(C) H2O increases with decrease in temperature.
(D) Both pH and pOH decrease with rise in temperature.
4. One litre of a strong acid solution contains 10–5 moles of H+ ions. Then :
(A) pOH = 9.
(B) Percentage ionisation of water in solution is 1.8 × 10–9 %.
(C) Number of OH– ions per mL of solution = 6.022 x 1015.
(D) [H+]from H2O = 10–9 M
5. Equal volumes of 0.2 M HCl and 0.2 M Sr(OH)2 are mixed. Which of the following statement is/are
correct ?
(A) [Sr2+] = 0.1 M (B) [Cl–] = 0.1 M
(C) pH of resulting solution = 13 (D) Solution is neutral.
6. If 0.1 M CH3COOH (Ka = 1.8 × 10–5) is diluted at 25°C, then which of the following will be correct ?
(A) [H+] will increase. (B) pH will increase.
(C) number of H+ ions will increase. (D) Ka will increase.
7. Degree of hydrolysis for a salt of strong acid and weak base :
(A) is independent of dilution (B) increases with dilution
(C) increases with decrease in Kb of the bases (D) decreases with decrease in temperature.
8. Equal volumes of following solutions are mixed, in which case the pH of resulting solution will be average
value of pH of two solutions.
(A) Aqueous HCl of pH = 2, aqueous NaOH of pH = 12
(B) Aqueous HCl of pH = 2, aqueous HCl of pH = 4
(C) Aqueous NaOH of pH = 12, aqueous NaOH of pH = 10
(D) Aqueous CH3COOH of pH = 5, aqueous NH3 of pH = 9. [Ka (CH3COOH) = Kb (NH3)]
9. A buffer solution can be prepared from a mixture of :
(A) Sodium acetate and acetic acid in water (B) Sodium acetate and hydrochloric acid in water
(C) Ammonia and ammonium chloride in water (D) Ammonia and sodium hydroxide in water
10. The solubility of a sparingly soluble salt AxBy in water is 1.4 × 10–4 M. The solubility product is
1.1 × 10–11. The possibilities are :
(A) x = 1, y = 2 (B) x = 2, y = 1 (C) x = 1, y = 3 (D) x = 3, y = 1

PART- 3: NUMERIC VALUE TYPE

1. If an acid-base reaction HA(aq) + B– (aq) HB(aq) + A– (aq) has Keq = 10–4, how many of the
following statements are true ?
(i) HB is stronger acid than HA (ii) HA is stronger acid than HB
(iii) HA and HB have the same acidic strength (iv) B– is stronger base than A–
(v) A– is stronger base than B– (vi) B– and HB are conjugate acid-base pair

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 Ionic Equilibrium (Elementry)
(vii) A– is the conjugate base of acid HA. (viii) HA can be HSO4– and HB can be HCOOH.
(ix) A– can be F– and B– can be CN–.
2. What is pOH of an aqueous solution with [H+] = 10–2 M and Kw = 2 × 10–12 ? Report your answer after
dividing by 2 and round it off to the nearest whole number.
3. Percentage ionisation of water as follows at certain temperature is 3.6 × 10–7 %. Calculate Kw and pH of
water at this temperature. 2H2O H3O + OH–

4. 0.1 mole HCl is dissolved in distilled water of volume V. Then, at lim , (pH)solution is equal to .....
V
5. Determine pKa (H2O) + pKa (H3O+).
6. What volume (in L) of water must be added to 1 L of 0.1 M solution of B (weak organic monoacidic base;
ionisation constant = 10–5) to triple the % ionisation of base ?
7. If pHx% is the pH of a 1 M weak monoprotic acid which is x % ionised, then find the value of
 pH50% 
  × 100.
 pH10% 

8. If the equilibrium constant for the reaction of weak acid HA with a strong base is 109, then determine pH
of 0.1 M NaA solution.

9. What is the concentration of CH3COOH(aq) in a solution prepared by dissolving 0.01 mole of NH4 CH3 COO –
in 1 L H2O ? Report your answer after multiplying by 9 × 105. [Ka(CH3COOH) = 1.8 × 10–5; Kb(NH3.H2O)
= 1.8 × 10–5]
10. How many of the following statement(s) is/are correct for making a buffer solution ?
(i) It can be formed by mixing equal concentrations of HCl and CH3COONa
(ii) It can be formed by mixing equal concentrations of HNO3 and NH3
(iii) It can be formed by mixing equal concentrations of HCOOH and Aniline.
(iv) It can be formed by mixing equal volumes of NH4OH and HClO4.
(v) It can be formed by mixing equal volumes of HCN and KOH.
(vi) There is no change in the pH of a buffer solution on adding small amount of a strong acid/base.
(vii) The concentrations of acid and base being mixed must be different to form a buffer.
(viii) The volumes of acid and base being mixed must be different to form a buffer.
(ix) The concentrations and volumes of acid and base being mixed must be different to form a buffer.
11. 1 M benzoic acid (pKa = 4.2) and 1M C6H5 COONa solutions are given separately. What is the volume of
benzoic acid required to prepare a 93 mL buffer solution of pH = 4.5 ?
12. How many of the following relations are correct for the solubility product (Ksp) & solubility (s g/litre) of
sparingly soluble salt A3B2 (producing A2+ & B3– ions ; mol. wt. M) in water ? (Assume no hydrolysis of
any ion).
3 2
 3s   2s 
1. Ksp = 108s5 2. Ksp =     3. Ksp = (3[A2+])3 (2[B3–])2
M M
1/ 2
2s [B 3 ] 1 M4 2  K sp 
4. [B3–] = 5. K  54 4 6. [ A ]   3  3 
M sp s  [B ] 

108s5 K sp
7. [A 2 ]3 M5  8.  36s 4 9. Ksp =[A2+]2 [B3–]3
[B3  ]2 [ A 2 ]

13. 8 × 10–6 M AgNO3 solution is gradually added in 1 L of 10–4 M KCl solution. Upto what volume of AgNO3
solution being added (in L), precipitation of AgCl will not take place? (Ksp of AgCl = 2 × 10–10)

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 Ionic Equilibrium (Elementry)

PART- 4: COMPREHENSION
Read the following passages carefully and answer the questions.
Comprehension # 1
pH calculation upon dilution of a strong acid solution is generally done by equating nH in original solution
& diluted solution. However, if strong acid solution is very dilute, then H+ from water are also to be
considered.
Take log 3.7 = 0.568 and answer the following questions.
1. A 1 litre solution of pH = 4 (solution of a strong acid) is added to the 7/3 litre of water. What is the pH of
resulting solution ?
(A) 4.52 (B) 4.365 (C) 4.4 (D) 4.432
2. A 1 litre solution of pH = 6 (solution of a strong acid) is added to the 7/3 litre of water. What is the pH of
resulting solution ? Neglect the common ion effect on H2O.
(A) 6.4 (B) 6.52 (C) 6.365 (D) 6.432
Comprehension # 2
Consider a solution of CH3COONH4 which is a salt of weak acid & weak base.
The equilibrium involved in the solutions are :
CH3COO– + H2O CH3COOH + OH– ..........(1)
–
NH4 + H2O NH3.H2O + H+ ..........(2)
+ –
H + OH H2O ..........(3)
If we add these three reactions, then the net reaction is :
CH3COO– + NH4+ + H2O CH3COOH + NH3.H2O ..........(4)
Both CH3COO– and NH4+ get hydrolysed independently and their hydrolysis depends on :
(i) their initial concentration
Kw Kw
(ii) the value of Kh which is K for CH3COO– and K for NH4+.
a b

Since both of the ions were produced from the same salt, their initial concentrations are same. Therefore
Kw Kw
unless & until the value of K and K or Ka and Kb is same, the degree of hydrolysis of ion can't be
a b

same.
To explain why we assume that degree of hydrolysis of cation and anion is same, we need to now look at
the third reaction i.e., combination of H+ and OH– ions. It is obvious that this reaction happens only because
one reaction produced H+ ion and the other produced OH– ions. We can also note that this reaction causes
both the hydrolysis reaction to occur more since their product ions are being consumed. Keep this thing in
mind that the equilibrium which has smaller value of equilibrium constant is affected more by the common
ion effect. For the same reason, if for any reason a reaction is made to occur to a greater extent by the
comsumption of any one of the product ion, the reaction with the smaller value of equilibrium constant
tends to get affected more.
Therefore we conclude that firstly the hydrolysis of both the ions ocurs more in the presence of each other
(due to consumption of the product ions) than in each other's absence. Secondly, the hydrolysis of the ion
which occurs to a lesser extent (due to smaller value of Kh) is affected more than the one whose Kh is
greater. Hence, we can see that the degree of hydrolysis of both the ions would be close to each other
when they are getting hydrolysed in the presence of each other.
Now answer the following questions :
3. In the hydrolysis of salt of weak acid & weak base :
(A) degree of hydrolysis of cation and anion is different
(B) degree of hydrolysis of cation and anion is same
(C) degree of hydrolysis of cation and anion is different and they can never be assumed same.
(D) degree of hydrolysis of cation and anion is different but they are very close to each other when they
are getting hydrolysed in the presence of each other.

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 Ionic Equilibrium (Elementry)
4. For 0.1 M CH3COONH4 salt solution given, Ka (CH3COOH) = Kb (NH3.H2O) = 2 × 10–5.
In this case, degree of hydrolysis of cation and anion are :
(A) exactly same (B) slightly different
(C) can't say (D) different but can be take approximatly same

PART- 5: COLUMN MATCHING

1. Match the Column.
Column-I Column-II
(A) HCl (P) Lewis acid
(B) KOH (Q) Arrhenius acid
(C) NH3 (R) Lewis base
(D) BF3 (S) Arrhenius base
2. At the equivalence point of titration of :
(A) a strong acid with a strong base (p) pH < 7
(B) a weak acid with a strong base (q) pH > 7
(C) a weak base with a strong acid (r) pH = 7
(D) a weak acid with a weak base (s) pH may be less than or greater than 7
3. Match the correct Ksp expression in terms of solubility (s) for given salts :
(Dont assume hydrolysis of any ion)
Column-I Column-II
(A) Ca 3(PO4) 2 (p) 4s 3
(B) Hg2I2 (q) 27s4
(C) Cr(OH)3 (r) 108s5
(D) CaF2 (s) 16s4

ANSWER KEY
EXERCISE-4
PART- 1
1. (B) 2. (D) 3. (C) 4. (B) 5. (C)
6. (C) 7. (B) 8. (C) 9. (A) 10. (B)
11. (B) 12. (B) 13. (C)

PART- 2
1. (A,B,C) 2. (A,C) 3. (A,B,D) 4. (A,B,D) 5. (A,B,C)
6. (B,C) 7. (B,C,D) 8. (A,D) 9. (A,B,C) 10. (A,B)

PART- 3
1. 4 (i, v, vi, vii) 2. 5 (Actual answer = 9.7) 3. Kw = 4 × 10–14, pH = 6.7
4. 7 5. 14 6. 8 7. 30 8. 9
9. 50 10. 5 [(i) to (v)] 11. 31 12. 4 (2, 4, 5 and 7). 13. 1

PART- 4
1. (A) 2. (D) 3. (D) 4. (A)

PART- 5
1. (A)  Q; (B)  S; (C)  R; (D)  P 2. (A)  R; (B)  Q; (C)  P; (D)  S
3. (A  r) ; (B  p) ; (C  q) ; (D  p)

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 Ionic Equilibrium (Advanced)

EXERCISE-4
PART - 1 : SINGLE OPTION CORRECT TYPE
1. Ratio of [HA2–] in 1 L of 0.1 M H3A solution ( K a1 = 10–5 ; K a2 = 10–8 & K a3 = 10–11) & upon addition of
0.1 mole HCl to it will be :
(A) 10 (B) 100 (C) 1000 (D) 10,000
2. Calculate the degree of hydrolysis and pH of 0.005 M K2CrO4. Ka2 = 5 × 10–7 for H2CrO4. (It is essentially
strong for first ionization)
(A) h = 2 × 10–3 (B) h = 0.01 (C) pH = 5 (D) pH = 9.7
3. A solution contains [NaCl] = [Na2CO3] = C M. Upon gradually adding AgNO3(s) : (Assume no hydrolysis
of any ion).
(A) Out of AgCl & Ag2CO3, one having lesser Ksp will start precipitating first.
(B) Out of AgCl & Ag2CO3, one having greater Ksp will start precipitating first.

K sp (Ag2CO3 ) K sp (AgCl)
(C) If  , then Ag2CO3 will start precipitating first.
C C

K sp (Ag2CO3 ) K sp (AgCl)
(D) If  , then AgCl will start precipitating first.
C C
4. For the reaction : [Ag(CN)2]–(aq) Ag+(aq) + 2CN–(aq), KC at 25ºC is 4 × 10–19. Calculate [Ag+] in
solution which was originally 0.1 M in KCN and 0.03 M in AgNO3.
(A) 1.5 × 10–17 M (B) 7.5 × 10–18 M
–19
(C) 4.6875 × 10 M (D) Value cannot be determined due to mathematical complications.
5. A solution of Na2CO3 is added drop by drop to one litre of a solution containing 10–4 mole of Ba2+ and 10–
5 mole of Ag+. If K for BaCO is 8.1 × 10–9 and K for Ag CO is 6.9 × 10–12, then which is not true ?
sp 3 sp 2 3
Assume no hydrolysis of CO32 ion.
(A) No precipitate of BaCO3 will appear until [ CO 23  ] reaches 8.1 × 10–5 mol per litre.

(B) A precipitate of Ag2CO3 will appear when [ CO 23  ] reaches 6.9 × 10–5 mol per litre.

(C) No precipitate of Ag2CO3 will appear until [ CO 23  ] reaches 6.9 × 10–2 mole per litre.
(D) BaCO3 will be precipitated first.

PART- 2: ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

1. If K a1 and K a2 of H2SO4 are 10–2 and 10–6 respectively at a certain temperature, then :

(A) K a1 > K a2 because it is easy to abstract H+ from H2SO4 and less easy to abstract H+ from HSO4–.
(B) K a1 and K a2 may be measured in acetic acid.
(C) K a1 and K a2 are measured in H2O.
(D) the H+ ion conc. of 0.01 M H2SO4 will be less than 0.02 M.
2. When 0.1 mole solid NaOH is added in 1 L of 0.1 M NH3(aq) (Kb = 2 × 10–5), then select the correct
statement(s) :
(A) degree of dissociation of NH3 approaches to zero.
(B) change in pH by adding NaOH would be 1.85.
(C) In solution, [Na+] = 0.1 M, [NH3] = 0.1 M, [OH–] = 0.2 M.
(D) on addition of OH–, Kb of NH3 does not changes.
3. Which of the following solutions when added to 1L of a 0.01 M CH3COOH solution will cause no change
in the degree of dissociation of CH3COOH and pH of the solution ? Ka = 1.6 × 10–5 for CH3COOH?

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 Ionic Equilibrium (Advanced)
(A) 0.6 mM HCOOH (Ka = 8 × 10–4) (B) 0.1 M CH3COONa
(C) 0.4 mM HCl (D) 0.01 M CH3COOH
4. Aniline behaves as a weak base. When 0.1 M, 50 mL solution sample of aniline was mixed with 0.2 M, 12.5
mL solution of HCl, the pH of resulting solution was 8. Then :
(A) pH of 0.01 M solution of anilinium chloride is 5.
(B) pH of original solution of aniline is 3.5.
(C) Upon adding the same aniline sample to the above mixture, pH of resulting solution becomes 8.48.
(D) Upon adding the same HCl sample to the above mixture, pH of resulting solution becomes 4.59.
5. Which of the following mixtures will act as buffer ?
(A) H2CO3 + NaOH (1.5 : 1 molar ratio) (B) H2CO3 + NaOH (1.5 : 2 molar ratio)
(C) NH4OH + HCl (5 : 4 molar ratio) (D) NH4OH + HCl (4 : 5 molar ratio)
6. Titration curves for 0.1M solutions of three weak acids HA1, HA2 and HA3 with ionization constants K1,
K2 and K3 respectively with a strong base are plotted as shown in the figure. Which of the following
options is/are true ?

12

10

pH 8

6 K3
4 K2
K1
2

Volume of strong base added

(A) K2 = (K1 + K3)/2 (B) pK1 < pK3 (C) K1 > K2 (D) K2 > K3
PART- 3: NUMERIC VALUE TYPE
1. For a solution of weak triprotic acid H3A (Ka1 >> Ka2, Ka3 ; Ka2 = 10–8 ; Ka3 = 10–13), [A3–] = 10–17 M.
Determine pH of solution. Report your answer as ‘0’, if you find data insufficient.
2. Calculate [H+] in a 0.2 M solution of dichloroacetic acid (Ka = 5 × 10–2) that also contains 0.05 M H2SO4.
Report your answer after multiplying it by 400.
3. Calculate the ratio of concentrations of HCOO– & OCN– ions in a solution containing 0.1 M HCOOH
(Ka = 1.8 × 10–4) and 0.1 M HOCN (Ka = 4 × 10–4). If simplest ratio is a : b, report your answer as (a + b).
4. In a solution containing 0.01 M HCl and 0.1 M H2CO3, ratio of [H+] produced from strong acid & weak acid
respectively is x : 1. Report your answer as x/500. Given : K a1 & K a2 of H2CO3 are 4 × 10–7 & 4 × 10–11
respectively.
5. Calculate the change in pH of 0.1 M Na2HA solution after diluting it to ten times the original volume.
(Given that for H3A : K a1 = 10–4, K a2 = 10–7, K a3 = 10–11)

6. What is the pOH of a 0.5 M Na3PO4 solution ? Report your answer as 10 × pOH.
( K a1 = 7.5 × 10–3, K a2 = 6.2 × 10–8, K a3 = 4 × 10–13)
7. 15 mL sample of 0.15 M NH3(aq) is titrated against 0.1M HCl(aq). What is the pH at the end point ? Kb of
NH3(aq) = 1.8 x 105. Report the answer rounding it off to the nearest whole number.
8. A 0.252 g sample of unknown organic base is dissolved in water and titrated with a 0.14 M HCl solution.
After the addition of 20 mL of acid, a pH of 10.7 is recorded. The equivalence point is reached when a total
of 40 mL of HCl is added. If the base and acid combine in a 1 : 1 molar ratio, then 'a' g is the molar mass
 a 
of the organic base and 'b' is the ionisation constant of base. Report your answer as  1000 b  .
 
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 Ionic Equilibrium (Advanced)
9. When pure water is saturated with both CaCO3 and CaC2O4, the concentration of calcium ion in the solution under
equilibrium is 8 × 105 M. If the ratio of the solubility product of CaCO3 to that of CaC2O4 is 3, what is the
solubility product of CaCO3 in pure water ? Report your answer after multiplying by 109 and rounding it off
to nearest whole number.
10. On mixing equal volumes of 0.1 M AgNO3 & 0.8 M KCN solutions, what % of original Ag+ is in the form
of free Ag+ ions ? Given : Kd of [Ag(CN)2]– = 10–18. Report your answer after multiplying it by 4.5 × 1016.
(Assume no hydrolysis of any ion)

PART- 4: COMPREHENSION
Comprehension # 1
Read the following passage carefully and answer the questions.

[Base ]
The pH of basic buffer mixtures is given by : pH = pKa + log , whereas pH of acidic buffer mixtures
[Salt]

[Salt]
is given by : pH = pKa + log . Addition of little acid or base although shows no appreciable change in
[ Acid]

[Base ] [Salt]
pH for all practical purposes, but since the ratio for changes, a slight decrease or increase
[Salt] [ Acid]

in pH results.
1. A solution containing 0.2 mole of dichloroacetic acid (Ka = 5 × 10–2) and 0.1 mole sodium dichloroacetate
in one litre solution has [H+] :
(A) 0.05 M (B) 0.025 M (C) 0.10 M (D) 0.005 M

2. The volume of 0.2 M NaOH needed to prepare a buffer of pH 4.74 with 50 mL of 0.2 M acetic acid is :
(pKb of CH3COO– = 9.26)
(A) 50 mL (B) 25 mL (C) 20 mL (D) 10 mL

3. The ratio of pH of solution (I) containing 1 mole of CH3COONa and 1 mole of HCI and solution (II)
containing 1 mole of CH3COONa and 1 mole of acetic acid in one litre is :
(A) 1 : 2 (B) 2 : 1 (C) 1 : 3 (D) 3 : 1
Comprehension # 2
Read the following passage carefully and answer the questions.
Phosphoric acid ionizes according to the following equations :
H3PO4(aq) H+ (aq) + H2PO4– (aq) ; K1 = 7 × 10–3
H2PO4–(aq) H+ (aq) + HPO42– (aq) ; K2 = 6 × 10–8
HPO42–(aq) H+ (aq) + PO43– (aq) ; K3 = 4.5 × 10–13
4. If you are asked to prepare a buffer with a pH = 7.00, what may be the molar ratio of the species that
should be used in the solution ?
(A) 0.6 (B) 0.8 (C) 2 (D) 4
5. Assume 50 mL of the buffer prepared in the previous part is available in which more abundant species has
a concentration of 0.1 M. If to this solution, 20 mL 0.1 M NaOH is added further, what will be the new pH
?

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 Ionic Equilibrium (Advanced)
(A) 6.56 (B) 7.44
(C) 7.78 (D) Same as before as it's a buffer
Comprehension # 3
0.2 mole of MgCl2(s) are added in 1 litre volume of a solution (S), already containing 0.2 mole of NaOH(s).
Now answer the following questions :
6. Calculate pH of obtained solution. Ksp of Mg(OH)2 is 1.6 × 10–12.
(A) 8.6 (B) 8.5 (C) 8.65 (D) 8.56
7. What would be the new pH when 0.04 mole of NaOH(s) are added in the solution (S) ?
(A) 8.6 (B) 8.5 (C) 8.65 (D) 8.56
8. Find the pH of the solution obtained after adding 0.04 mole of HCl(g) to the solution .
(A) 8.6 (B) 8.5 (C) 8.65 (D) 8.56

EXERCISE-5

1. Will the pH of water be same at 4ºC and 25ºC ? Explain. [JEE-2003]

2. A weak acid HX at 25ºC has the dissociation constant 1 × 10–5. It forms a salt NaX on reaction with caustic
soda. The percentage hydrolysis of 0.1 M solution of NaX is : [JEE-2004]
(A) 0.0001% (B) 0.01 % (C) 0.1 % (D) 0.15 %
3. The dissociation constant of a substituted benzoic acid at 25ºC is 1.0 × 10–4 . The pH of 0.01 M solution of
its sodium salt is : [JEE-2009]
4. Amongst the following, the total number of compounds whose aqueous solution turns red litmus paper blue
is : [JEE-2010]
KCN K2SO4 (NH4)2C2O4 NaCl Zn(NO3)2
FeCl3 K2CO 3 NH 4NO 3 LiCN

5. 500 ml of 0.2 M aqueous solution of acetic acid is mixed with 500 mL of 0.2 M HCl at 25º C.
(a) Calculate the degree of dissociation of acetic acid in the resulting solution and pH of the solution.
(b) If 6 g of NaOH is added to the above solution, determine final pH. Assume there is no change in volume
on mixing. Ka of acetic acid is 1.75 × 10–5.

6. 0.1 M NaOH is titrated with 0.1 M HA till the end point. Ka for HA is 5.6 × 10–6 and degree of hydrolysis
is less compared to 1. Calculate pH of the resulting solution at the end point.

7. 0.1 mole of CH3NH2 (Kb = 5 × 10–4) is mixed with 0.08 mole of HCl and diluted to one litre. What will be
the H+ concentration in the solution ?
(A) 8 × 10–2 M (B) 8 × 10–11 M (C) 1.6 × 10–11 M (D) 8 × 10–5 M
2 2
8. 2.5 mL of 5 M weak monoacidic base (Kb = 1 x 10–12 at 25° C) is titrated with 15 M HCl in water at

25°C. The concentration of H+ at equivalence point is : (Kw = 1 x 10–14 at 25°C)

(A) 3.7 x 10–14 M (B) 3.2 x 10–7 M (C) 3.2 x 10–2 M (D) 2.7 x 10–2 M

9. Aqueous solutions of HNO3, KOH, CH3COOH and CH3COONa of identical concentrations are provided.
The pair (s) of solutions which form a buffer upon mixing is (are) :
(A) HNO3 and CH3COOH (B) KOH and CH3COONa
(C) HNO3 and CH3COONa (D) CH3COOH and CH3COONa
10. For a sparingly soluble salt ApBq, the relationship of its solubility product (Ls) with its solubility (S) is :
[JEE-2001]

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 Ionic Equilibrium (Advanced)
p+q p q p+q q p
(A) LS = S .p .q (B) LS = S .p .q (C) LS = Spq . pp . qq (D) LS = Spq . (pq)p+q

11. A solution which is 10–3 M each in Mn2+, Fe2+, Zn2+ and Hg2+ is treated with 10–16 M sulphide ion. If Ksp
values of MnS, FeS, ZnS and HgS are 10–15 , 10–23 , 10–20 and 10–54 respectively, which one will precipitate
first ? [JEE-2003]
(A) FeS (B) MgS (C) HgS (D) ZnS
12. Solubility product constant (Ksp) of salts of types MX, MX2 and M3X at temperature T are 4.0 × 10–8, 3.2 × 10–
14
and 2.7 × 10 –15, respectively. Solubilities (in mol dm–3 ) of the salts at temperature T are in the
order : [JEE-2008]
(A) MX > MX2 > M3X (B) M3X > MX2 > MX (C) MX2 > M3X > MX (D) MX > M3X > MX2
13. In 1 L saturated solution of AgCl [Ksp(AgCl) = 1.6 × 10–10], 0.1 mole of CuCl [Ksp(CuCl) = 1.0 × 10–6] is
added. The resultant concentation of Ag+ in the solution is 1.6 × 10–x. The value of "x" is : [JEE-2011]

PART - 2 : PRACTICE PROBLEMS (JEE ADVANCED)

SECTION-1 : (Only One option correct Type)

This section contains 7 multiple choice questions. Each questions has four choices (A), (B), (C)
and (D) out of which Only ONE option is correct.

1. Azhar prepared three different solutions of HCl, NaOH and brine (NaCl) but forgot to label them. In order
to identify he kept them on table and named them as solution I, solution II and solution III.
When he added a sample from solution II or solution III to a sample from solution I, the pH of the solution
I increased. However, when a sample from solution III was added to a sample from solution II, the pH of
the solution II decreased.
Identify the incorrect option :
(A) Solution I, II and III contain HCl, NaOH and NaCl respectively.
(B) Solutions I and solution III can be mixed to get the pH of solution II.
(C) pHI < pHII < pHIII
(D) Solutions II and III cannot be used as standard solutions in a titration.
2. An aqueous solution contains 0.01 M RNH2 (Kb = 2 × 10–6) & 10–4 M NaOH.
The concentration of OH– is nearly :
(A) 1.414 × 10–4 M (B) 10–4 M (C) 3 × 10–4 M (D) 2 × 10–4 M
3. A 0.01 M solution of PuO2(NO3)2 was found to have a pH of 4. Then select the INCORRECT option :
(A) % hydrolysis of PuO22 = 1 %. (B) Kb for PuO2(OH)+ = 10–8.
(C) Hydrolysis is expected to be endothermic. (D) None of these
4. 10 mL of 0.1 M HCl solution is added in 90 mL of a buffer solution having 0.1 M NH4OH and 0.1 M
NH4Cl. The percentage change in pH of solution is : (Ka of NH4+ = 5 × 10–10)
10 10 10 10
(A) % increase (B) % decrease (C) % increase (D) % decrease
4.7 4.7 9.3 9.3
5. Select INCORRECT statement :
(A) Phenolphthalein is not a suitable indicator for the titration of HCl(aq) with NH4OH(aq).
1000
(B) An acid-type indicator in a buffer solution of pH = pKln + 1 is ionized to the extent of %.
11
(C) In the titration of a monoacidic weak base with a strong acid, the pH at the equivalent point is always
1
calculated by pH = [pKw – pKb – log C].
2
(D) When Na3PO4(aq) is titrated with HCl(aq), the pH of solution at second equivalent point is calculated
1
by [ pK a1 + pKa ].
2 2

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 Ionic Equilibrium (Advanced)
6. The solubility of SrF2 (Ksp = 2.5 × 10–9) in 0.1 M SrCl2 solution is : (neglect hydrolysis of F–)
5 5 5
(A) × 10–4 mol/L (B) 5 × 10–3 mol/L (C) 5 × 10–5 mol/L (D) × 10–3 mol/L
2 2 2
7. pH of a saturated solution of silver salt of monobasic acid HA is found to be 9.
Find the Ksp of sparingly soluble salt AgA(s).
Given : Ka(HA) = 10–10
(A) 1.1 × 10–11 (B) 1.1 × 10–10 (C) 10–12 (D) Data insufficient

Section-2 : (One or More than one options correct Type)

This section contains 5 multipole choice questions. Each questions has four choices (A), (B),
(C) and (D) out of which ONE or MORE THAN ONE are correct.

8. Which of the following options is/are true for alkaline aqueous solution ?
pK w pK w
(A) pH > (B) pH > pOH (C) pOH < (D) pH < pOH
2 2
9. pH of aqueous solution of which of the following salt(s) is/are independent of its concentration ?
(A) CH3 COONa (B) C6 H5NH3Cl (C) KClO4 (D) CH3COONH4
10. A base type indicator is half in ionised form when pH is 7.2. If the ratio of unionised form to ionised form
is 1 : 5, let pH of the solution is pH1. With the same pH of solution, indicator is altered (not its type) such that
the ratio of unionised form to ionised form is 1 : 4. Let pH2 be the pH of solution when 50% of new indicator
is in ionised form. Then :
(A) pH1 = 7.9 (B) pH1 = 6.5 (C) pH2 = 7.3 (D) pH2 = 7.1
11. A 2.5 g impure sample containing weak monoacidic base (Mol. wt. = 45 u) is dissolved in 100 mL water
and titrated with 0.5 M HCl. When (1/5)th of the base was neutralised, the pH was found to be 9 and at
equivalence point, pH of solution is 4.5. Select correct statement(s) :
(A) Kb of base is less than 10–6.
(B) Concentration of salt (C) at equivalent point is 0.25 M.
(C) Volume of HCl is used at equivalent point is 100 mL.
(D) Weight percentage of a base in given sample is 80%.
12. The solubility of metal sulphides in saturated solution of H2S {[H2S] = 0.1 M} can be represented by :
[M2 ][H2 S]
MS + 2H+ M2+ + H2S ; Keq =
[H ]2
The value of Keq is given for few metal sulphides. If concentration of each metal ion in solution is 0.01 M,
which metal sulphide(s) is/are selectively precipated at total [H+] = 1 M in saturated H2S solution ?
Metal sulphide : MnS ZnS CoS PbS
K eq : 3 × 1010 3 × 10–2 3 3 × 10–7
(A) MnS (B) ZnS (C) CoS (D) PbS

Section-3 : (One Integer Value Correct Type.)

This section contains 6 questions. Each question, when worked out will result in one integer
from 0 to 9 (both inclusive)

13. Value of Keq at 25ºC for reaction : NH3 + H3O+ NH4+ + H2O is 2 × 109. Determine pKb of NH4OH,
rounding it off to nearest whole number. Report your answer as '0' if value cannot be determined.
14. In a 3.24 L closed cylindrical container, the following equilibrium is established at 0ºC :
2Ag(s) + 2I–(aq) + 2H2O() 2AgI(s) + H2(g) + 2OH–(aq)
th
–9
 1 
The equilibrium constant for the above reaction is 4 × 10 . At equilibrium, solution occupies   height
3.24 
of the container and contains 0.5 M I– and other species. If gaseous matter weighs 2 g, find pOH of
solution. Neglect aqueous tension.

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 Ionic Equilibrium (Advanced)
15. Calculate [A2–]/[H+] in an aqueous solution of 0.1 M H2A (dibasic weak acid).
Given : For H2A, Ka = 0.05, Ka = 2 × 10–6.
1 2
Report your answer after multiplying by 1,00,000.
16. To a 200 mL of 0.1 M weak base BOH solution, 46 mL of 0.2 M solution of HCl are added. Now, what
volume (in mL) of 0.1 M H2SO4 should be added into above solution, so that pH of resulting solution
becomes 9 ? [Kb(BOH) = 10–5]
17. 3.29 × 10–3 mg AgBr(s) (Ksp= 4.9 × 10–13) is added to 250 mL water. Determine the % saturation of
solution. Report your answer after dividing by 10. (Report your answer as '0', if the given amount of salt
cannot dissolve/just dissolves).
18. A buffer solution has 0.25 M CH3COOH, 0.15 M CH3COONa, [Mn2+] = 0.015 M and is saturated with
H2S (0.1 M). Given : Ka (CH3COOH) = 1.8 × 10–5, Ka(H2S) = 9 × 10–21, Ksp(MnS) = 2.4 × 10–13.
Concentration of a component of the buffer may have to be increased to start the precipitation of MnS.
What would be its new concentration (in mole per litre) ? Report your answer after multiplying by 10.
(Report your answer as '0', if the concentration of any component need not be increased to start the
precipitation).

SECTION-4 : Comprehension Type (Only One options correct)

This section contains 1 paragraph, describing theory, experiments, data etc. 3 questions relate
to the paragraph. Each question has only one correct answer among the four given options (A),
(B), (C) and (D)

Paragraph For Questions 19 to 21

Consider the following experiment set-up with stopcocks-S1,S2,S3,S4 and taps-T1,T2,T3,T4.

19. In which of the following cases will the solutions in tub have a pH different from others ?
(A) T1 and T4 are opened. (B) Only T2 is opened.
(C) T1, T2, T3 and T4 are all opened. (D) T1 is opened and the content of bucket is poured in the tub.
20. A pH meter is immersed in the bucket of the original set-up shown. It shows a reading of 7. Now, S1 is first
opened and all content is allowed to drain out into the bucket. pH of the solution in the bucket is measured
again. Similarly S2, S3 and S4 are sequentially opened and the the pH of the solution in the bucket is
measured each time after complete drainage. Opening which stop cock would cause maximum pH change
(increase/deacrease) compared to the previous pH in bucket ?
(A) S1 (B) S2 (C) S3 (D) S4

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 Ionic Equilibrium (Advanced)
21. The above apparatus was setup to study the functioning of the human stomach, where a low pH is
maintained at a nearly constant value even when reactions take place in it. Following the same procedure
as in the previous question, can a solution imitating stomach-like pH properties be generated in the bucket,
and if so, by opening which stopcock ? Would this solution have the lowest pH possible from this setup ?
If your answer is "No" for any of these questions, then after answering "No", choose the stopcock,
opening of which will lead to solution in bucket with minimum pH, following the same procedure as above.
(A) S4 ; Yes (B) No ; S4 (C) S3 ; No ; S1 (D) S3 ; No ; S4

SECTION-5 : Matching List Type (Only One options correct)

This section contains 1 question, having two matching lists. Choices for the correct combination
of elements from List-I and List-II are given as options (A), (B), (C) and (D) out of which one is
correct

22. 0.01 mole of AgNO3 are gradually added to 1 litre of a solution, which is 0.1 M in Na2CrO4 and 0.005 M in
NaIO3. (Ksp values of Ag2CrO4 and AgIO3 are 10–8 and 10–13 respectively )
Now match the values in list II with list I.
List-I List-II
(I) Mole of precipitate formed (P) 0.0975
(II) Equilibrium concentration of Ag+ (in mol/L) (Q) 0.00032
–
(III) Equilibrium concentration of IO3 (in mol/L) (R) 0.0075
(IV) Equilibrium concentration of CrO24– (in mol/L) (S) 3.125 × 10–10
Code :
(A) I–Q, II–R, III–S, IV–P (B) I–Q, II–P, III–S, IV–R
(C) I–R, II–S, III–Q, IV–P (D) I–R, II–Q, III–S, IV–P

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 Ionic Equilibrium (Advanced)

ANSWER KEY
EXERCISE-4
PART- 1
1. (D) 2. (A) 3. (C) 4. (B) 5. (B)

PART- 2
1. (A,B,D) 2. (A,B,D) 3. (A,C,D) 4. (A,C,D) 5. (A,B,C)
6. (B,C,D)

PART- 3
1. 4 2. 60 3. 29 (actual answer = 9 : 20) 4. 5
5. 0 6. 10 7. 5 (exact answer = 5.24)
8. 90 (a = 45 & b = 5 × 10–4) 9. 5 (actual answer = 4.8 × 10–9) 10. 50

PART- 4
1. (A) 2. (B) 3. (A) 4. (A) 5. (B)
6. (A) 7. (C) 8. (D)

EXERCISE-5
PART- 1
1. It will not be same at two different temperatures. 2. (B) 3. 8
4. 3 5. (a) 0.0175%, 1 (b) 4.757 6. 8.98  9 7. (B)
8. (D) 9.* (C,D) 10. (A) 11. (C) 12. (D)
13. 7

PART- 2
1. (A) 2. (D) 3. (D) 4. (D) 5. (C)
6. (C) 7. (A) 8. (A,B,C) 9. (C,D) 10. (B,D)
11. (B,C) 12. (D) 13. 5 (exact answer = 4.7) 14. 5
15. 4 16. 4 17. 1 18. 6 19. (C)
20. (B) 21. (D) 22. (D)

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 Thermodynamic Ist law

EXERCISE-4
PART - 1 : SINGLE OPTION CORRECT TYPE
1. In which one of the following sets, all the properties belong to same category (all extensive or all intensive)?
(A) Mass, volume, pressure (B) Temperature, pressure, volume
(C) Heat capacity, density, entropy (D) Enthalpy, internal energy, volume.

2.

The plots between P and V which represent isochoric and isobaric process respectively :
(A) I, II (B) IV, I (C) I, IV (D) II, III
3. Match the enteries of column I with appropriate entries of column II and choose the correct option out of
the four options (A), (B), (C) and (D).
Column I Column II
(X) Isothermal (p) T = 0
(Y) Isobaric (q) V = 0
(Z) Adiabatic (r) P = 0
(W) Isochoric (s) q = 0
(A) X–p, Y–q, Z-r, W-x (B) X–p, Y–r, Z-s, W-q
(C) X–s, Y–p, Z-r, W-q (D) X–s, Y–p, Z-q, W-r
4. Consider the cyclic process R  S  R as shown in the Fig. You are told that one of the path is
adiabatic and the other one isothermal. Which one of the following is(are) true?

(A) Process R  S is isothermal (B) Process S  R is adiabatic

(C) Process R  S is adiabatic (D) Such a graph is not possible
5. Work for the following process ABCD on a monoatomic gas is :

P
P0 A B

Isothermal

C
D

V0 2V0 4V0 V

(A) w = – 2 P0 V0 ln 2, (B) w = – 2 P0 V0 ln 2,
(C) w = – P0 V0 (1+ ln 2), (D) w = – P0 V0 ln 2,
6. 50 L of a certain liquid is confined in a piston system at the external pressure 100 atm. This pressure is
suddenly released and liquid is expanded against the constant atmospheric pressure, volume of the liquid
increases by 1 L and the final pressure on the liquid is 10 atm. Find the workdone.
(A) 1L.atm (B) 5 L.atm (C) 500 L.atm (D) 50 L.atm

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 Thermodynamic Ist law
7. Which one of the following equations does not correctly represent the first law of thermodynamics for the
given process in ideal gas ?
(A) Isothermal process : q = – w (B) Cyclic process : q = – w
(C) Adiabatic process : E = q (D) Expansion of a gas into vacuum : E = q
 5 
8. One mole of an ideal gas  Cv,m  2 R  at 300 K and 5 atm is expanded adiabatically to a final pressure of
 
2 atm against a constant pressure of 2 atm. Final temperature of the gas is :
(A) 270 K (B) 273 K (C) 248.5 K (D) 200 K
9. The magnitudes of enthalpy changes for irreversible adiabatic expansion of a gas from 1L to 2L is H1 and
for reversible adiabatic expansion for the same expansion is H2. Then
(A) H1 > H2
(B) H1 < H2
(C) H1 = H2, enthalpy being a state function ( H1 = H2½
(D) H1 = E1 & H2 = E2 where E1 & E2 are magnitudes of change in internal energy of gas in these
expansions respectively.
10. A certain mass of gas is expanded from (1L, 10 atm) to (4L, 5 atm) against a constant external pressure of
1 atm. If initial temperature of gas is 300 K and the heat capacity of process is
50 J/°C. Then the enthalpy change during the process is (1L atm ~ 100 J)
(A) H = 15 kJ (B) H = 15.7 kJ (C) H = 14.4 kJ (D) H = 14.7 kJ
11. Which of the following option the first compound has less entropy than second :
(A) (i) aqueous solution of 1 M of MgCl2 (ii) aqueous solution of 1 M of NaCl
(B) (i) Br2 liquid at 25ºC (ii) Br2 liquid at 20ºC
(C) (i) HgO solid (ii) HgS solid
(D) (i) Br2 liquid (ii) I2 solid
12. Select the correct statement(s) :
S1 : AlCl3 when dissolve in H2O its entropy decreases therefore it is a non-spontaneous process.
S2 : When H2 gas adsrobed at the surfce of Pd, some amount of heat is released.
S3 : Entropy of D2 gas is greater than H2 gas.
(A) S1, S2 & S3 (B) S1 & S3 (C) S2 & S3 (D) S1 & S2
13. Isoentropic process is
(A) adiabatic and irreversible process (B) isothermal and reversible process
(C) Adiabatic and reversible process (D) isothermal and reversible for which Q = 0
14. According to third law of thermodynamics
(A) The entropy of a substance at OK is zero.
(B) Entropy of hydrogen ion is zero at OK.
(C) Net change in entropy in coverssion H2(g) (130 K)  H2(g) (200K) is zero.
(D) Entropy generally decrease in combustion reactions.
15. One mole of an ideal diatomic gas (Cv = 5 cal) was transformed from initial 25°C and 1 L to the state when
temperature is 100°C and volume 10 L. The entropy change of the process can be expressed as
(R = 2 calories/mol/K)
298 373
(A) 3 ln 373 + 2 ln 10 (B) 5 ln 298 + 2 ln 10

373 1 373 1
(C) 7 ln 298 + 2 ln 10 (D) 5 ln 298 + 2 ln 10
16. Select correct statements :
S1 : For every chemical reaction at equilibrium, standerd gibbs energy of reaction is zero
S2 : At constant temperature and pressure, chemical reactions are spontaneous in the direction of decreas-
ing gibbs energy.
S3 : Spontancity is related to change in entropy of universe.

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 Thermodynamic Ist law
(A) S1 S2 S3 (B) only S1 (C) S2, S3 (D) S1, S3

17. Combustion of sucrose is used by aerobic organisms for providing energy for the life sustaining processes.
If all the capturing of energy from the reaction is done through electrical process (non P–V work) then
calculate maximum available energy which can be captured by combustion of 34.2 g of sucrose
Given : Hcombustion (sucrose) = – 6000 kJ mol–1
Scombustion = 180 J/K - mol and body temperature is 300 K
(A) 600 kJ (B) 594.6 kJ (C) 5.4 kJ (D) 605.4 kJ
18. Given the following data :
Substance  H° (kJ/mol) S°(J/mol K)  G° (kJ/mol)
FeO(s) – 266.3 57.49 – 245.12
C (Graphite) 0 5.74 0
Fe(s) 0 27.28 0
CO(g) – 110.5 197.6 – 137.15
Determine at what temperature the following reaction is spontaneous ?
FeO(s) + C (Graphite)  Fe(s) + CO(g)
(A) 298 K (B) 668 K (C) 964 K
(D) G° is +ve, hence the reaction will never be spontaneous

PART- 2: ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

1. Which of the following properties of a system are intensive?
(A) color (B) kinetic energy per mole
(C) X ( where X = U + H) (D) specific volume (volume per unit mass)
2. Choose the correct statement :
(A) system and surrounding are always separated by a real or imaginary boundary.
(B) perfectly isolated system can never be created.
(C) in reversible process, energy change in each step can be reversed.
(D) irreversible process is also called quasi-equilibrium state.
3. In an isothermal expansion of a gaseous sample, the correct relation is : (consider w (work) with sign
according to new IUPAC convention)
[The reversible and irreversible processes are carried out between same initial and final states.]
(A) wrev > wirrev (B) wirrev > wrev (C) qrev < qirrev (D) Erev = Eirrev
4. During the isothermal expansion of an ideal gas :
(A) The internal energy remains unaffected (B) The temperature remains constant
(C) The enthalpy remains unaffected (D) The enthalpy increases
5. P-V plot for two gases (assuming ideal) during adiabatic processes are given in the figure. Plot A and plot
B should correspond respectively to :

(A) He and H2 (B) H2 and He (C) SO3and CO2 (D) N2 and Ar

6. An ideal gas undergoes adiabatic expansion against constant external pressure. Which of the following
is incorrect :
(A) Temperature of the system decreases.
(B) The relation PV  = constant will be valid (where P and V are gas variables)
(C) E + PextV = 0
(D) Enthalpy of the gas remains unchanged.

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 Thermodynamic Ist law
7. For the sublimation of a solid at 1 atm, which of the following may be correct
(A) U > 0 at low temperature (B) q > 0
(C) U < 0 at high temperature (D) H > 0
8. In which of the following entropy increases :
(A) Rusting of iron (B) Melting of ice
(C) Crystallisation of sugar from solution (D) Vaporisation of camphor
9. When a liquid solidifies, generally, there is :
(A) Decrease in enthalpy (B) Decrease in entropy
(C) Increase in enthalpy (D) Increase in entropy
10. Which of the following is false about molar entropy ?
(A) It is same for all type of gases
(B) For the gas of comparable mass. It decreases with the increases in atomicity.
(C) Under identical condition, it is greater for heavier gas.
(D) For ideal gas of comparable molar mass it decreases with the increase in thermo molecular attractions.
11. Which of the following statements is/are correct
(A) Reversible adiabatic process is iso entropie process
(B) Ssystem for irreversible adiabatic compression is greater than zero
(C) Ssystem for free expension in zero
(D) Ssurrounding for irreversible isothermal compression is greater than zero
12. The normal boiling point of a liquid `X` is 400 K. Which of the following statement is true about the process
X(l)  X(g)?
(A) at 400 K and 1 atm pressure G = 0 (B) at 400 K and 2 atm pressure G = + ve
(C) at 400 K and 0.1 atm presure G = – ve (D) at 410 K and 1 atm pressure G = + ve
13. For isothermal expansion in case of an ideal gas :
(A) H = 0 (B) E = 0 (C) G = –T.S (D) Tfinal = Tinitial
PART- 3: NUMERIC VALUE TYPE
1. How many statements are false ?
(i) Thermodynamics is concerned with total energy of the system.
(ii) Ist law of thermodynamics can be applied on the individual particle enclosed in vessel.
(iii) Many thermodynamic properties can not be measured absolutely, so change in thermodynamic property
is required for calculation.
(iv) Feasibility of any chemical reaction can not be explained by thermodynamics.
(v) When surrounding is always in equilibrium with the system, the process called reversible.
(vi) Thermodynamics predict the time of attain the equilibrium.
2. How many of the following physical properties are extensive :
(i) Free energy (ii) vapour pressure (iii) mole (iv) Kinetic energy
(v) Entropy (vi) Internal energy (vii) Enthalpy (viii) specific heat capacity
(ix) Coefficient of viscosity (x) Total heat capacity
3. How many of the following are state function :
(i) Internal energy (ii) Heat (iii) Enthalpy (iv) Entropy
(v) Pressure (vi) Temp. (vii) volume (viii) Work
(ix) specific heat capacity (x) molar heat capacity
4. Two moler of He gas (=5/3) are initially at temp 27ºC and occupy a volume of 20 litres. The gas is first
expanded at constant pressure until its volume is doubled. then it undergoes and reversible adiabatic change,
2/3
4
unit the volume become 110 lit, then predict the value of T/100 (where T is the final temperature,  
 11 
= 21 )
5. A sample of an ideal gas is expanded from 1dm3 to 3 dm3 in a reversible process for which P = KV3 ,
with K = 1/5 (atm/dm3), what is work done by gas (L atm).

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 Thermodynamic Ist law
6. The valve on a cylinder containing initially 1 liters of an ideal gas at 7 atm and 25ºC is opened to the
atmosphere, Whose the pressure is 760 torr and the temperature is 25ºC. Assuming that the process is
isothermal, how much work (in L.atm) is done on the atmosphere by the action of expansion ?
7. A system is provided 50 joule of heat and the change in internal energy during the process is 60 J.
Magnitude of work done on the system is :
8. A system works in a cylic process. It absorbs 20 calories of heat and rejects 60 J of heat during the
process. The magnitude of work done (J) is [1 calorie = 4.2 J] :
9. The work done in adiabatic compression of 2 mole of an ideal monoatomic gas by constant external
pressure of 2 atm starting from intial pressure of 1 atm and initial temperature of 30 K (R = 2 cal/mol-
degree)
10. One mole of a non-ideal gas undergoes a change of state (2.0 atm, 3.0 L, 95 K)  (4.0 atm, 5.0 L, 245 K)
with a change in internal energy, U=30.0 L. atm. Calculate change in enthalpy of the process in L. atm.
11. The equilibrium constant for a reaction is 10. What will be the magnitude value of Gº ?
R = 8.31 JK–1 mol–1, T = 314 K. (Approximate integer value in KJ mol–1)
12. For the reaction at 298 K
A (g) + B (g) C (g) + D (g)
If Hº = – 29.8 Kcal and Sº = – 0.1 Kcal K–1 then calculate reaction constant (K) :
13. One mole of an ideal gas is expanded isothermally at 300 K until its volume is tripled. Find the values of
Stotal under the condition.
Expansion is carried out irreversibly where 900 J of heat is less absrobed than expansion is carried out
reversibly. (Approximate integer value, Used e1.09 = 3 & 8.314 × 1.09 = 9)
14. Calculate the magnitude of free energy in KJ mol–1 when 1 mole of a an ionic salt MX (s) is dissolved in
water at 27°C. Given Lattice energy of MX = 780 kJ mol–1, Hydration energy of MX = – 775.0 kJ mol–1,
Entropy change of dissolution at 27°C = 40 J mol–1 K–1
15. For the formation of C (g) at 300 K.
A (g) + 3 B (g)  2C (g)
Calculate the magnitude of Gº (Kcal) if given data :
A B C
-1
Hf º (Kcal mol ) 0 0 –10

S f º (Cal K –1 mol-1) 40 30 45

16. The entropies of H2 (g) and H (g) are 60 and 50 J mole–1 K–1 respectively at 300 K. Using the data given
below calculate the bond enthalpy of H2 (g) in Kcal mole–1.
H2 (g)  2H (g) ; Gº = 21.6 KJ mole–1
17. The standard free energy change for a reaction is – 213.3 kJ mol–1 at 25ºC. If the enthalpy change of the
reaction is – 217.77 kJ mole–1. Calculate the magnitude of entropy change for the reaction in Joule mole –1.
18. Calculate the magnitude of standard entropy change for reaction X Y if Hº = 25 KJ and Keq is 10–7 at 300
K.
19. Calculate the magnitude of standard free energy of formation of ammonium chloride at 250C (approximate
integer in Kcal mol–1), the equation showing the formation of NH4Cl from its elements is :
½N2(g) + 2H2(g) + ½Cl2(g)  NH4Cl(s)
For NH4Cl, H0f is – 313 kJ mol–1, Also given that
S N0 2  191.5 JK 1 mol 1 S0H2  130.6 JK 1 mol1

S 0Cl2  223.0J K 1 mol 1 S NH

0
4 Cl
 94.6 JK 1 mol 1

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 Thermodynamic Ist law
1 3
20. For the reaction N (g) + H (g)  NH3 (g) ; H = – 30 kJ to be at equilibrium at 477ºC. If
2 2 2 2
standard entropy of N2 (g) and NH3 (g) are 60 and 50 J mole–1 K–1 respectively then calculate the standard
entropy of H2(g) in Jmole–1K–1.

PART- 4: COMPREHENSION
Read the following passage carefully and answer the questions.
Comprehension #1
When a system is taken from state A to state B along path ACB as shown in figure below, 80 J of heat
flows into the system and the system does 30 J of work.

C B
P
A D
V
1. How much heat flows into the system along path ADB if the work done by the system is 10 J :
(A) 40 J (B) 60 J (C) 80 J (D) 100 J
2. When the system is returned from state B to A along the curved path, the work done on the system is 20 J.
Does the system absorb or liberate heat and by how much ?
(A) –70 J ; heat is liberated. (B) –60 J ; heat is liberated.
(C) +70 J ; heat is absorbed. (D) +60 J ; heat is absorbed.
3. If ED – EA = –40J, the heat absorbed in the processes AD and DB are respectively :
(A) qAD = 30 J and qDB = – 90 J (B) qAD = – 60 J and qDB = 30 J
(C) qAD = 30 J and qDB = 90 J (D) qAD = – 30 J and qDB = 90 J
Comperhension # 2
Entropy is a state function and its value depends on two or three variables temperature (T), Pressure (P)
and volume (V). Entropy change for an ideal gas having number of moles (n) can be determined by the
following equation.
 T2   V2 
S = 2.303 nCV log  T  + 2.303 nR log 
V 

 1  1
 T2   P1 
S = 2.303 nCp log  T  + 2.303 nR log  
P 
 1  2
Since free energy change for a process or a chemical equation is a deciding factor of spontaneity, which can be
obtained by using entropy change (S) according to the expression, G = H – TS at a temperature T.
4. What would be the entropy change involved in thermodynamic expansion of 2 moles of a gas from a
volume of 5 L to a volume of 50 L at 25°C [Given R = 8.3 J/mole – K]
(A) 38.23 J/K (B) 26.76 J/K (C) 20J/K (D) 28.23J/K
5. An isobaric process having one mole of ideal gas has entropy change 23.03 J/K for the temperature range
27°C to 327°C. What would be the molar specific heat capacity (CV) ?
10 10
(A) log 2 J/K mol (B) log 2 – 8.3 J/K mol (C) 10 x log2 J/K mol (D) 10 log2 + 8.3 J/K mol

1
6. For a reaction M2O(s)  2M(s) + O (g) ; H = 30 kJ/mol and S = 0.07 kJ/K-mol at 1 atm.
2 2
Calculate upto which temperature the reaction would not be spontaneous.
(A) T > 428.6 K (B) T > 300.8 K (C) T < 300.8 K (D) T < 428.6 K

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 Thermodynamic Ist law
Comprehension # 3
Dependence of Spontaneity on Temperature :
For a process to be spontaneous, at constant temperature and pressure, there must be decrease in free
energy of the system in the direction of the process, i.e. GP, T < 0. GP,T = 0 implies the equilibrium
condition and GP, T > 0 corresponds to non-spontaneity.
Gibbs-Helmholtz equation relates the free energy change to the enthalpy and entropy changes of the
process as : G P,T = H – T S ...(1)
The magnitude of H does not change much with the change in temperature but the entropy factor TS
changes appreciably. Thus, spontaneity of a process depends very much on temperature.
For endothermic process, both H and S are positive. The energy factor, the first factor of equation,
opposes the spontaneity whereas entropy factor favours it. At low temperature the favourable factor TS
will be small and may be less than H, G will have positive value indicating the nonspontaneity of the
process. On raising temperature, the factor TS increases appreciably and when it exceeds H, G would
become negative and the process would be spontaneous.
For an exothermic process, both  H and S would be negative. In this case the first factor of
eq. 1 favours the spontaneity whereas the second factor opposes it. At high temperature, when TS > H,
G will have positive value, showing thereby the non-spontaneity of the process. However, on decreasing
temperature, the factor TS decreases rapidly and when TS < H, G becomes negative and the process
occurs spontaneously. Thus, an exothermic process may be spontaneous at low temperature and non-
spontaneous at high temperature.
7. When CaCO3 is heated to a high temperature, it undergoes decomposition into CaO and CO2 whereas it is
quite stable at room temperature. The most likely explanation of it, is
(A) The enthalpy of reaction (H) overweighs the term TS at high temperature.
(B) The term TS overweighs the enthalpy of reaction at high temperature.
(C) At high temperature, both enthalpy of reaction and entropy change become negative.
(D) None of these.
8. For the reaction at 25°C, X2O4 ()  2XO2 (g)
H = 2.1 Kcal and S = 20 cal K–1. The reaction would be
(A) spontaneous (B) non-spontaneous (C) at equilibrium (D) unpredictable
9. For the reaction at 298 K, 2A + B  C
H = 100 kcal and S = 0.050 kcal K–1. If H and S are assumed to be constant over the temperature
range, above what temperature will the reaction become spontaneous ?
(A) 1000 K (B) 1500 K (C) 2000 K (D) 2500 K
10. A reaction has a value of H = – 40 kcal at 400K. Above 400 K, the reaction is spontaneous, below this
temperature, it is not. The values of G and S at 400 K are respectively.
(A) 0,– 0.1 cal K–1 (B) 0,100 cal K–1
(C) – 10 kcal, – 100 cal K–1 (D) 0, – 100 cal K–1
11. The enthalpy change for a certain reaction at 300 K is – 15.0 K cal mol–1. The entropy change under these
conditions is – 7.2 cal K–1 mol–1. The free energy change for the reaction and its spontaneous/non-spontaneous
character will be
(A) – 12.84 kcal mol–1, spontaneous (B) 12.84 kcal mol–1, non-spontaneous
(C) – 17.16 kcal rnol–1, spontaneous (D) None of these

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 Thermodynamic Ist law

PART- 5: COLUMN MATCHING

1. Columm-I Columm-II
V2  
(A) Reversible isothermal expansion of an ideal gas (p) w = –2.303 nRT log  V 
 1 
(B) Reversible adiabatic compression of an ideal gas (q) PV = constant


nR
(C) Irreversible adiabatic expansion of an ideal gas (r) w = (   1) (T2 – T1)
(D) Irreversible isothermal compression of an ideal gas (s) H = 0
2. Column I Column II
(A) A process carried out infinitesimally slowly (p) Adiabatic
(B) A process in which no heat enters or leaves the system (q) E = 0, H = 0
(C) A process carried out at constant temperature (r) Reversible
(D) Cyclic process (s) Isothermal
3. Columm-I Columm-II
(A) (Gsystem) T,P = 0 (p) Process is in equilibrium

(B) Ssystem + Ssurrounding > 0 (q) Process is nonspontaneous

(C) Ssystem + S surrounding

<0 (r) Process is spontaneous

(D) (Gsystem) T,P > 0 (s) System is unable to do useful work

4. Columm-I Columm-II
(A) Reversible adiabatic compression (p) Ssystem > 0

(B) Reversible vaporisation of liquid (q) Ssystem < 0

(C) 2N(g)  N2(g) (r) Ssurrounding < 0


(D) MgCO3(s)  MgO(s) + CO2(g) (s) Ssurrounding = 0

EXERCISE-5

1. The given reaction

2CO + O2  2CO2 H = – 560 kJ
2moles 1 mole
is carried out in one litre container, if the pressure in the container gets changes from 70 atm to 40 atm as
reaction gets completed. Calculate U of the reaction. [1L atm = 0.1 kJ] [JEE 2006]
2. Among the following, the state function(s) is(are) : [JEE 2009]
(A) Internal energy (B) Irreversible expansion work
(C) Reversible expansion work (D) Molar enthalpy
3.* Among the following, the intensive property is (properties are) : [JEE 2010]
(A) molar conductivity (B) electromotive force
(C) resistance (D) heat capacity
4. One mole of an ideal gas is taken from a and b along two paths denoted by the solid and the dashed lines
as shown in the graph below. If the work done along the solid line path is ws and that along the dotted line
path is wd, then the integer closest to the ratio wd / ws is : [JEE 2010]

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 Thermodynamic Ist law

5.* The reversible expansion of an ideal gas under adiabatic and isothermal conditions is shown in the figure.
Which of the following statement(s) is (are) correct ? [JEE 2012]

(A) T1 = T2 (B) T3 > T1 (C) wisothermal > wadiabatic (D) Uisothermal > Uadiabati]
6.* An ideal gas in a thermally insulated vessel at internal pressure = P 1 , volume = V1 and absolute
temperature = T 1 expands irreversibly against zero external pressure, as shown in the diagram. The
final internal pressure, volume and absolute temperature of the gas are P 2 , V2 and T 2 , respectively.
For this expansion, [JEE(Advanced) 2014]

(A) q = 0 (B) T 2 = T 1 (C) P 2 V2 = P1 V1 (D) P2 V2 = P1V1

7. The direct conversion of A to B is difficult, hence it is carried out by the following shown path:

S(A  C) = 50 ; S(C  D) = 30; S(B  D) = + 20

The entropy change for the process A  B is [JEE 2006]

(A) 100 (B) – 60 (C) – 100 (D) + 60
8. N2 + 3H2 2 NH3 K = 4 × 106 at 298
K = 41 at 400 K
Which statements is correct ? [JEE 2006]
(A) If N2 is added at equlibrium condition, the equilibrium will shift to the forward direction because
according to IInd law of thermodynamics the entropy must increases in the direction of spontaneous
reaction.
(B) The condition for equilibrium is 2GNH3 = 3GH2 + GN2 where G is Gibbs free energy per mole of the
gaseous species measured at that partial pressure.

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 Thermodynamic Ist law
(C) Addition of catalyst does not change Kp but changes H.
(D) At 400 K addition of catalyst will increase forward reaction by 2 times while reverse reaction rate will
be changed by 1.7 times.
9. The value of log10K for a reaction A B is : (Given : rHº298 K= –54.07 kJ mol–1, rSº298 K = 10 JK–1
mol–1 and R = 8.314 JK–1 mol–1 ; 2.303 × 8.314 × 298 = 5705) [JEE 2007]
(A) 5 (B) 10 (C) 95 (D) 100
10. For the process H2O() (1 bar, 373 K)  H2O(g) (1 bar, 373 K), the correct set of thermodynamic
parameters is : [JEE 2007,]
(A) G = 0, S = +ve (B) G = 0, S = –ve (C) G = +ve, S = 0 (D) G = –ve, S = +ve
11. Statement-1 : For every chemical reaction at equilibrium, standard Gibbs energy of reaction is zero.
Statement-2 : At constant temperature and pressure, chemical reactions are spontaneous in the direction
of decreasing Gibbs energy. [JEE 2008]
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True
12. Statement-1 : There is a natural asymmetry between converting work to heat and converting heat to
work.
Statement-2 : No process is possible in which the sole result is the absorption of heat form a reservoir and
its complete conversion into work. [JEE 2008]
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True
13. Match the transformation in column I with appropriate options in column II. [JEE 2011]
Column I Column II
(A) CO2(s)  CO2(g) (p) phase transition
(B) CaCO3(s)  CaO(s) + CO2(g) (q) allotropic change
(C) 2H   H2(g) (r) H is positive
(D) P(white, solid)  P(red, solid) (s) S is positive
(t) S is negative
14. For an ideal gas, consider only P-V work in going from an initial state X to the final state Z. The final state
Z can be reached by either of the two paths shown in the figure. Which of the following choice(s) is (are)
correct? [take S as change in entropy and w as work done]. [JEE 2012]

(A) Sxz =Sxy + Syz (B) wxz = wxy + wyz

(C) wxyz = wxy (D) Sxyz =Sxy
15. For the process, H2O()  H2O(g)
at T = 100 C and 1 atmosphere pressure, the correct choice is : [JEE(Advanced) 2014]
(A) Ssystem > 0 and Ssurroundings > 0 (B) Ssystem > 0 and Ssurroundings < 0
(C) Ssystem < 0 and Ssurroundings > 0 (D) Ssystem < 0 and Ssurroundings < 0

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 Thermodynamic Ist law
16. Match the thermodynamic processes given under Column I with the expressions given under Column II.
[JEE(Advanced) 2015]
Column I Column II
(A) Freezing of water at 273 K and 1 atm (P) q=0
(B) Expansion of 1 mol of an ideal gas into a (Q) w=0
vacuum under isolated conditions
(C) Mixing of equal volumes of two ideal gases at (R) Ssys < 0
constant temperature and pressure in an
isolated container
(D) Reversible heating of H2(g) at 1 atm from (S) U = 0
300 K to 600 K, followed by reversible cooling
to 300 K at 1 atm
(T) G = 0

PART - 2 : PRACTICE PROBLEMS (JEE ADVANCED)

SECTION-1 : (Only One option correct Type)

This section contains 8 multiple choice questions. Each questions has four choices (A), (B), (C)
and (D) out of which Only ONE option is correct.

1. One mole of ideal monoatomic gas is carried through the reversible cyclic process as shown in figure.
Calculate the max. temperature attained by the gas during the cycle.

25  Po V o  25  Po V o  35  Po V o  35  Po V o 
(A)   (B) –   (C)   (D) –  
8  R  8  R   R   R 
    8   8  

2. Determine Uº at 300 K for the following reaction using the listed enthalpies of reaction :
4CO(g) + 8H2(g) —— 3CH4 (g) + CO2(g) + 2H2O(  )
C(graphite) + 1/ 2O2(g) —— CO(g); H1º = – 110.5 kJ
CO(g) + 1/ 2O2(g) —— CO2(g); H2º = –282.9 kJ
H2(g) + 1/ 2O2(g) —— H2O(l); H3º = –285.8 kJ
C (graphite) + 2H2(g) —— CH4(g); H4º = –74.8 kJ
(A) –653.5 kJ (B) –686.2 kJ (C) –747.4 kJ (D) None of these
3. Determine enthalpy of formation for H2O2(), using the listed enthalpies of reactions :
N2H4() + 2H2O2()  N2(g) + 4H2O(); rHº1 = –818 kJ/mol
N2H4() + O2(g)  N2(g) + 2H2O(); rHº2 = –622 kJ/mol
1
H2(g) + O (g)  H2O(); rHº3 = –285 kJ/mol
2 2
(A) –383 kJ/mol (B) –187 kJ/mol (C) –498 kJ/mol (D) None of these
4. The enthalpy of neutralization of a weak monoprotic acid (HA) in 1M solution with a strong base is –55.95
kJ/mol. If acid HA requires 1.4 kJ/mol heat for it’s complete ionization and enthalpy of neutralization of the
strong monobasic acid with a strong monoacidic base is –57.3 kJ/mol. What is the % ionization of the weak
acid in molar solution ?
(A) 1% (B) 3.57% (C) 35.7% (D) 10%

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 Thermodynamic Ist law
5. Calculate fGº for (NH4CI, s) at 310 K.
Given : fHº (NH4CI, s)= –314.5 kJ/mol; rCp = 0
Sº N = 192 JK–1 mol–1; Sº H = 130.5 JK–1 mol–1;
2 ( g) 2 ( g)
SºCl2(g) = 233 JK–1 mol–1; Sº NH4 CI( s) = 99.5 JK–1 mol/–1
All given data are at 300 K.
(A) –198.56 kJ/mol (B) –426.7 kJ/mol (C) –202.3 kJ/mol (D) None of these
6. For a perfectly crystalline solid Cp.m. = aT3, where a is constant. If Cp.m. is 0.42 J/K–mol at 10 K, molar
entropy at 10 K is
(A) 0.42 J/K–mol (B) 0.14 J/K–mol (C) 4.2 J/K–mol (D) zero
7. The molar entropy content of 1 mole of oxygen (O2) gas at 300 K and 1 atm is 250 J mole–1 K–1. Calculate
G when 1 mole of oxgyen is expanded reversibily and isothermally from 300 K, 1 atm to double its volume
(Take R = 8.314 J mole–1 K–1, log e = 2.303)
(A) 1.728 KJ mole–1 K–1 (B) 0
–1 –1
(C) –1.728 KJ mole K (D) 0.75 KJ mole–1K–1
8. Fixed amount of an ideal mono atomic gas contained in a sealed rigid vessel (V = 24.6 litre) at 1.0 bar is
heated reversibly form 27oC to 127oC. Determine change in Gibb's energy (in Joule) if entropy of gas S =
10 + 10–2 T (J/K)
(A) 530 J (B) –530 J (C) 1778.5 J (D) 3778.5 J

Section-2 : (One or More than one options correct Type)

This section contains 6 multipole choice questions. Each questions has four choices (A), (B),
(C) and (D) out of which ONE or MORE THAN ONE are correct.

9. Which of the following statement(s) is/are ture?

(A) E = 0 for combustion of C2H6(g) in a sealed rigid adiabatic container
(B) fHº (S, monoclinic)  0
(C) If dissociation energy of CH4 (g) is 1656 kJ/mol and C2H6(g) is 2812 kJ/mol, then value of C—C bond
energy will be 328 kJ/mol
(D) If Hf(H2O,g) = – 242 kJ/mol; Hvap (H2O, l) = 44 kJ/mol then fHº (OH– ,aq.) will be – 142 kJ/mol
10. From the following data, mark the option(s) where H is correctly written for the given reaction.
Given : H+ (aq) + OH– (aq) — H2O(); H = – 57.3 kJ
Hsolution of HA(g) = –70.7 kJ/mol
Hsolution of BOH(g) = 20 kJ/mol
Hionization of HA = 15 kJ/mol and BOH is a strong base.
Reaction  Hr (kJ/mol)
(A) HA(aq) + BOH(aq) — BA(aq) + H2O –42.3
(B) HA(g) + BOH(g) — BA(aq) + H2O –93
(C) HA(g) — H+(aq) + A– (aq) –55.7
+ –
(D) B (aq) + OH (aq) — BOH(aq) –20
11. The value of Htransition of C (graphite) — C (diamond) is 1.9 kJ/mol at 25ºC entropy of graphite is higher
than entropy of diamond. This implies that :
(A) C (diamond) is more thermodynamically stable then C (graphite) at 25ºC
(B) C (graphite) is more thermodynamically stable than C (diamond) at 25ºC
(C) diamond will provide more heat on complete combustion at 25ºC
(D) Gtransition of C (diamond) — C (graphite) is –ve
12. Which of the following statement(s) is/are false ?
(A) All adiabatic processes are isoentropic (or isentropic) processes
(B) When (Gsystem) T,P < 0; the reaction must be exothermic
(C) dG = VdP – SdT is applicable for closed system, both PV and non–PV work
(D) the heat of vaporisation of water at 100ºC is 40.6 kJ/mol. When 9 g of water vapour condenses to liquid

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 Thermodynamic Ist law
at 100ºC of 1 atm, then Ssystem = 54.42 J/K
13. For the reaction 2Ag2O (s)  4Ag(s) + O2 (g), H is 61.17 kJ mol–1 and S is 132 J K–1 mol–1.
Compute the temperature above which the given reaction will be spontaneous.
(A) T > 463.4 K (B) T > 190.250 C (C) T < 190.250 C (D) T < 463.4 K
14. Select the correct enthalpy at corresponding temperature using following datas
(i) Heat capacity of solid from 0 K to normal melting point 200 K
CP,m(s) = 0.035 T JK–1 mol–1 .
(ii) Enthalpy of fusion = 7.5 KJ mol–1,
(iii) Enthalpy of vaporisation = 30 KJ mol–1.
(iv) Heat capacity of liquid form 200 K to normal boiling point 300 K
CP,m() = 60 + 0.016 T JK–1 mol–1 .
(v) Heat capacity of gas from 300 K to 600 K at 1 atm
CP,m (g) = 50.0 JK–1 mol–1 .
(A) S200 (s) = 7 (B) S300 () = 70.43 (C) S300 (g) = 170.43 (D) S600 (g) = 205.09

Section-3 : (One Integer Value Correct Type.)

This section contains 6 questions. Each question, when worked out will result in one integer
from 0 to 9 (both inclusive)

15. Two moles of a perfect gas undergo the following processes :

(a) a reversible isobaric expansion from (1.0 atm, 20.0 L) to (1.0 atm, 40.0 L)
(b) a reversible isochoric change of state from (1.0 atm, 40.0 L) to (0.5 atm, 40.0 L)
(c) a reversible isothermal compression from (0.5 atm, 40.0 L) to (1.0 atm, 20.0 L)
Calculate the magnitude of work (W) done in L.atm
16. The enthalpy of combustion of mol. wt. 180 glucose is – 2808 KJmol–1 at 25ºC. X and Y grams of glucose
do you need to consume respectively cases [Assume wt = 62.5 Kg].
(a) to climb a flight of stairs rising through 3M. (b) to climb a mountain of altitude 6000 M ?
Assume that 25% of enthalpy can be converted to useful work.
X and Y are related as Y = mX; then find m/1000.
17. A sample of certain mass of an ideal polyatomic gas is expanded against constant pressure of
1 atm adiabatically from volume 2 L, pressure 6 atm and temperature 300 K to state where its final volume
is 8L. Then calculate entropy change (in J / K ) in the process. (Neglect vibrational degrees of freedom)
[1L atm = 100 J, log 2 = 0.3, log 3 = 0.48, log e = 2.3] (aproximate integer)
18. The heat of combustion of acetylene is 312 kcal. If heat of formation of CO2 & H2O are –94 & –68 kcal
respectively. Given that heat of atomisation of C(s) & H2(g) are 150 & 100 kcal respectively and C–H
HC C
bond energy is 95 kcal. Calculate .
22
19. Boron exist in different allotropic forms. All allotropic form contains icosahedral units (icosahedral is a
regular shape with 12 corners & 20 faces) with boron atoms at all 12 corners and all bonds are equivalent.

B (g)  (g)

Calculate heat evolved at constant pressure (in kJ) per mole of boron atoms undergoing above change if
HBE(B–B) = 200 kJ/mol. Report you Answer after dividing by 100
20. 1 mole of an ideal gas is allowed to expand isothermally at 27ºC till its volume is tripled . If the expansion is
carried out reversibly then the Suniverse will be ?

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 Thermodynamic Ist law

SECTION-4 : Comprehension Type (Only One options correct)

This section contains 2 paragraphs, each describing theory, experiments, data etc. 3 questions
relate to the paragraph. Each question has only one correct answer among the four given options
(A), (B), (C) and (D).

Paragraph For Questions 21 to 23

Concerete is produced from a mixture of cement, water, sand and small stones. It consists primarily of
calcium silicates and calcium aluminates formed by heating and grinding of clay and limestone. In later
steps of cement production a small amount of gypsum, CaSO4.2H2O is added to improve subsequent
hardening of concrete. The use of elevated temperatures during the final production may lead to formation
of unwanted hemihydrate, CaSO4.1/2H2O. Consider the following reaction :
1 3
CaSO4.2H2O(s)  CaSO4. H2O(s) + H2O (g)
2 2
The following thermodynamic data apply at 27ºC, standard pressure : 1 bar
Compound Hºf(kJ / mol) Sº (JK 1mol1 )
CaSO 4 .2H2 O (s) 2021.0 194.0
1
CaSO4 . H2 O(s) 1575.0 119.5
2
H2O(g) 242.8 188
–1 –1
R = 8.314 JK mol
1
21. Hº for the formation of 1.45 kg of CaSO4. H O(s) from CaSO4.2H2O(s) is
2 2
(A) +446 kJ (B) –830 kJ (C) –446 kJ (D) +830 kJ
1
22. Equilibrium pressure (in bar) of water vapour in closed vessel containing CaSO4.2H2O(s), CaSO4. H O(s),
2 2
H2O(g) at 27ºC : (2.303R × 300 × 1.5 = 8645.83)
(A) 15 × 10–4 bar (B) 2 × 10–4 bar (C) 4 × 10–3 bar (D) 7.00 × 10–4 bar
23. Temperature at which the equilibrium water vapour pressure is 1.00 bar
(A) 127ºC (B) 400ºC (C) 200ºC (D) 240ºC
Paragraph For Questions 24 to 26
The accompanying diagram represents a reversible cannot cycle for an ideal gas :

24. How many heat is rejected at the lower temperature, 200 K, during the isothermal compression ?
(A) 150 kJ (B) 30 kJ (C) 120 kJ
(D) data are not sufficient to calculate exact value
25. What is the entropy increase during isothermal expansion at 1000 K ?
(A) 0.15 JK–1 (B) 150 kJ K–1 (C) 150 JK–1 (D) 750 JK–1
26. What is the Gibbs free energy change during the process A  B ?
(A) 150 kJ (B) –150kJ (C) 30kJ (D) Data are not sufficient

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 Thermodynamic Ist law

SECTION-5 : Matching List Type (Only One options correct)

This section contains 1 questions, each having two matching lists. Choices for the correct
combination of elements from List-I and List-II are given as options (A), (B), (C) and (D) out of
which one is correct

27. Match column-I to column-II standard entropy in kJ/K-molar at 25ºC

Column-I Column-II
1. HC–C (p) 733.48
2. HC–H (q) 97.81
3. HC=C (r) 434.3
4. HCC (s) 454.64
5. HC=O (t) 804.22
Using the data (all values are in kJ/mol at 25ºC) given below :
Hºcombustion (ethane) = –1559.8 ; Hºcombustion (ethene) = –1410.9
Hºcombustion (acetylene) = –1299.7 ; Hºcombustion (acetaldehyde) = –1192.3
Hºf CO2 (g) = –393.5 ; Hºf of H2O () = –285.8
Hº for C(s) (graphite)  C (g) = 716.68 ; Bond energy of H–H = 435.94
Bond energy of O=O = 498.94
1 2 3 4 5 1 2 3 4 5
(A) q s r p t (B) r p t q s
(C) q p s r t (D) p s q r t

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 Thermodynamic Ist law

ANSWER KEY

EXERCISE-4

PART- 1
1. (D) 2. (B) 3. (B) 4. (D) 5. (A)
6. (A) 7. (C) 8. (C) 9. (B) 10. (B)
11. (C) 12. (C) 13. (C) 14. (B) 15. (B)
16. (C) 17. (D) 18. (C)

PART- 2
1. (A,B,D) 2. (A,B,C) 3. (B,D) 4. (A,B,C) 5. (B,C,D)
6. (B,D) 7. (A,B,C,D) 8. (A,B,D) 9. (A,B) 10. (A,B,D)
11. (A,B,D) 12. (A,B,C) 13. (A,B,C,D)

PART- 3
1. 4 2. 7 3. 6 4. 3 5. 4
6. 6 7. 10 8.* 24 9. 72 10. 44
11. 6 12. 1 13. 3 J K–1 14. – 7 kJ mol–1. 15. 8
16. 8 17. – 15 18. 51 19. 48 20. 40

PART- 4
1. (B) 2. (A) 3. (D) 4. (A) 5. (B)
6. (D) 7. (B) 8. (A) 9. (C) 10. (D)
11. (A)

PART- 5
1. (A – p, s) ; (B – q, r) ; (C – r) ; (D – s) 2. (A – r) ; (B – p) ; (C – s) ; (D – q)
3. (A)  (p, s); (B)  (r) ; (C)  (q, s) ; (D)  (q, s).
4. (A)  (s); (B)  (p, r); (C)  (q); (D)  p, r)

EXERCISE-5

PART- 1
1. – 557 kJ. 2.* (A,D) 3.* (A,B) 4. 2 5.* (A,D)
6.* (A,B,C) 7. (D) 8. (B) 9. (B) 10. (A)
11. (D) 12. (A) 13. (A - p, r, s) ; (B - r, s) ; (C - t) ; (D - p, q, t)
14.* (A,C) 15. (B) 16. (A-R,T) (B-P,Q,S) (C-P,Q,S) (D-P,Q,S,T)

PART- 2
1. (A) 2. (D) 3. (B) 4. (B) 5. (A)
6. (B) 7. (C) 8. (B) 9. (A,B,C) 10. (A,B,C)
11. (B,C,D) 12. (A,B,C,D) 13. (A,B) 14. (A,B,C,D)
15. (a) – 20L atm (c) 6 L atm 16. 2 17. 3 18. 7
19. 5 20. 0 21. (D) 22. (C) 23. (A)
24. (B) 25. (C) 26. (B) 27. (A)

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