CHEMISTRY

Assignment

Statistical Thermodynamics

CSIR NET Previous Year

Tm
1. A certain system of noninteracting particles has the single-particle partition function f = A
V
where A is some constant. The average energy per particle will be [NET June 2011]
(a) mkT (b) AkT (c) kT/m (d) kT/A
2. For an assembly of molecules (molar mass = M) at temperature T, the standard deviation of
Maxweller’s speed is approximately [NET June 2011]

RT RT M M
(a) 0.7 (b) 1.4 (c) 0.7 (d) 1.4
M M RT RT
3. At room temperature, which molecule has the maximum rotational entropy? [NET June 2011]
(a) H2 (b) O2 (c) D2 (d) N2
4.

(a) 2/3
CHEM ACADEMY
If r denotes the characteristic temperature of rotation then the magnitude of [r(H2) r (D2)]/ [r
(HD)]2 (assume the bond lengths to be the same for all the molecules) is [NET Dec. 2011]
(b) 3/2 (c) 8/9 (d) 9/8
5. A system consisting of 4 identical and distinguishable particle, each possessing three available state
of 1,2 and 3 units, has 10 units of energy. The number of ways, W, in which these condition are
satisfied is [NET Dec. 2011]
(a) 2 (b) 4 (c) 6 (d) 10
6. The energy levels of the harmonic oscillator (neglecting zero point energy) are v = nhv for n = 0, 1,
2, ...... . Assuming hv = KBT, the partition function is: [NET June 2012]
1
1 1
(a) e (b) (c) 1  (d) 1  1
e e e
7. The correct entropy for 6 identical particles with their occupation number {0, 1, 2, 3} in four states
is [NET June 2012]
(a) k B n6 (b) k B n12 (c) k B n60 (d) k B n720
8. The rotational partition function of H2 is: [NET Dec. 2012]
 hcBJ J 1  hcBJ J 1
(a)   2J  1 e
J  0,1,2.....
(b)   2J  1 e
J 1,3,5,.....

hcBJ  J 1
(c)   2J  1 e
J  0,2,4,.....

1  hcBJ J 1 
(d) 4    2J  1 e  3   2J  1 e hcBJ J 1 
 J 0,2,4...... J 1,3,5...... 

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9. A system has 100 dengenerate energy levels and 100 bosons are kept in it. Find the entropy of the
system at equilibrium. [NET June 2013]
–2 2
(a) 10 kB (b) 10 kB (c) 460.6kB (d) 4.606 kB
10. Calculate the total number of microstates for 6 identical particles with their occupation number {1,
2, 3} in three states is: [NET Dec. 2013]
(a) 6 (b) 12 (c) 60 (d) 720
11. The number of ways in which four molecules can be distributed in two different energy levels is
[NET Dec. 2013]
(a) 6 (b) 3 (c) 16 (d) 8
12. The molecule with the smallest rotation partition function at any temperature among the following
is [NET Dec. 2013]
(a) CH3  C  C  H (b) H  C  C  H
(c) H  C  C  D (d) D  C  C  D
13. The translational, rotational and vibrational partition function for a molecule are
[NET June 2014]
ftranslation  1010m–1, frotation  10, fvibration  1, (kBT/h)  1013 at room temperature, NA = 6×1023 Using
the approximate data given above, the frequency factor (A) for a reaction of the type: atom +
diatomic molecule  non-linear transtion state  product, according to the conventional transi-
tion state theory is
(a) 2×103 (b) 6 × 107 (c) 2 × 1012 (d) 6 × 1013
14.
CHEM ACADEMY
The number of configurations in the most probable state, according to Boltzmann formula, is
[NET June 2014]
(a) eS/ k B (b) eS/ k B (c) e  E/ k BT (d) e G / k BT
15. Using Boltzmann distribution, the probability of an oscillator occupying the first three levels (n=0,
and 2) is found to be p0 = 0.633, p1 = 0.233, and p2 = 0.086. [NET June 2014]
The probability of finding an oscillator in energy levels in n > 3 is
(a) 0.032 (b) 0.048 (c) 0.952 (d) 1.000
16. If temparature is doubled and the mass of the gaseous molecule is halved, the rms speed of the
molecular will change by a factor of [NET June 2014]
1 1
(a) 1 (b) 2 (c) (d)
2 4
 hv 
17. The low and high temperature limits of vibrational partition function are    
 k 
[NET Dec. 2014]

 / T T  /T  / 2T T  / 2T
(a) e and e (b) e and e
 
 / 2T T  /T  / 2T 
(c) e ande (d) e and e / 2T
 T
18. The number of microstates the are possible, when two particles are distributed in four states such
that the resulting wave functions are antisymmetric with respect to exchange of the particle, is
[NET Dec. 2014]
(a) 16 (b) 12 (c) 8 (d) 6

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19. When T , value of the single-particle partition function will be (given: degeneracy of level j =
gj) [NET Dec. 2014]
1
(a) 1 (b) g0 (c) jgj (d)  g
j j

20. The probability of finding the harmonic oscillator in the enrgy level n = 1 is (neglect zero point
energy and assume hv = kBT) [NET Dec. 2014]
(a) e (b) e2 (c) 1–e–2 (d) e–2(e–1)

A
21.
B
F(V) C

Speed

Identify the speed distribution function of Ne, Ar, Kr with the curves in the figure above
(a) Ne-A, Ar-B, Kr-C (b) Ne-B, Ar-C, Kr-A [NET Dec. 2014]
(c) Ne-C, Ar-B, Kr-A (d) Ne-C, Ar-A, Kr-B
22. The single-particle partition function (f) for a certain system has the form f = AVeBT. The average
energy per particle will then be (k is the Boltzmann constant) [NET June 2015]

23.
(a) BkT
CHEM ACADEMY
(b) BkT 2
(c) kT/B (d) kT/B2
The indistinguishability correction in the Boltzmann formulation is incorporated i the following
way: (N = total number of particles, f= single-particle partition function) [NET June 2015]
(a) replace by f/N! (b) replace fN by fN/N!
(c) replace f by f/In (N!) (d) replace by fN by fN/In (N!)
24. Though a constant shift of energy levels of a system changes the partition function, the properties
that do not change are [NET Dec. 2015]
(a) average energy, entropy and heat capacity
(b) average energy and entropy
(c) average energy and heat capacity
(d) entropy and heat capacity.
25. The standard deviation of speed (c) for Maxwell’s distribution satisfies the relation
[NET Dec. 2015]
(a) c T (b) c  T (c) c  1/T (d) c  1/ T
26. The vibrational frequency of a homo-nuclear diatomic molecule is v. The temperature at which the
population of the first excited state will be half that of the ground state is given by
[NET Dec. 2015]
(a) hv·In 2/kB (b) hv/(In 2·kB) (c) In 2/(hv·kB) (d) hv·log2/kB
27. The single-particle translational partition function (f) for an ideal gas in a fixed volume V depends
on the thermal de-Broglie wavelength th as f ~(th)n where [NET June 2016]
(a) n = 3 (b) n = 1 (c) n = –1 (d) n = – 3

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28. 15 particles are distributed among 4 levels as shown in stateI. Heat is given to the system and no
work is done. The final state could be [NET June 2016]

I II III IV V
(a) II (b) III (c) IV (d) V
29. An ideal gas is composed of particles of mass M in thermal equilibrium at a temperature T in one
container. Another container ideal gas particles of mass 2M at a temperature 2T. The correct state-
ment about the two gases is [NET June 2016]
(a) average kinetic energy and average speed will be same in the two cases
(b) both the averages will be doubled in the second case
(c) only the average kinetic energy will be doubled in the second case
(d) only the average speed will be doubled in the second case
1
30. The weight of the configuration with two up and three down spins in a system with five spin
2
particles is [NET Dec. 2016]
(a) 120 (b) 60 (c) 20 (d) 10
31. CHEM ACADEMY
If the energies of a bare proton aligned along and against an external static magnetic field (Bz) are
Bz Bz
 and  , respectively, then the ratio of probabilities of finding the proton along and
2 2
against the magnetic field is [NET Dec. 2016]
(a) e  Bz / 4k B T (b) e  Bz / 2k B T (c) eBz /2k BT (d) e Bz / k BT
32. Partition function of a one-dimensional oscillator having equispaced energy levels with energy
spacing equal to kBT and zero ground state energy is [NET Dec. 2016]
1 e 1
(a) e (b)  e  1 (c) (d)  e  1
 e  1
33. Consider a system of three particles which can occupy energy levels with energy 0,  and 2, such
1
that the total energy E = 4. Cases A, B and C correspond to spin fermions, spin 0 bosons, and
2
classically distinguishable particles, respectively. The correct ordering of entropy is
[NET June 2017]
(a) SA > SB > SC (b) SB > SA > SC (c) SC > SB > SA (d) SC > SA > SB

34. The first excited state  2

P1/ 2  of fluorine lies at an energy of 400 cm–1 above the ground state

 2
P3/2  . The fraction of Fluorine atoms in the first excited state at kBT = 420 cm–1 is close to
[NET June 2017]
1 1 1 1
(a) (b) (c) (d)
1 e 2e 1  4e 1  2e
Head Office: North Delhi: 72, Mall Road, G.T.B. Nagar, New Delhi - 110009
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35. The term symbol for the ground state of a metal ion is 3 P2 . The residual entropy of a crystal of a salt
of this metal ion at 0 K is [NET Dec. 2017]
(a) kB In 1 (b) kB In 3 (c) kB In 5 (d) kB In 7
36. Four distinguishable molecule are distributed in energy levels E1 and E2 with degeneracy of 2 and 3,
respectively. Number of microstates, with 3 molecules in energy level E1 and one in energy level E2,
is [NET Dec. 2017]
(a) 4 (b) 12 (c) 96 (d) 192
37. Translational partition function of a D2 molecule confined in a 100 cm3 vessel at 25º C is
(h = 6.626 × 10–34 J.s, k = 1.381 × 10–23 JK–1) [NET June 2018]
22 24 26
(a) 3.8 × 10 (b) 5.8 × 10 (c) 7.8 × 10 (d) 9.8 × 1028
38. PA and PB denote the populations of two energy states EA and EB, and EA > EB The correct statement
when the temperature T1 > T2 is [NET Dec. 2011]

(a) PA (T1) > PB (T1), PA (T2) < PB (T2) and  PA / PB  T1   PA / PB  T2

(b) PA (T1) < PB (T1), PA (T2) > PB (T2) and  PA / PB T1   PA / PB T2

(c) PA (T1) < PB (T1), PA (T2) < PB (T2) and  PA / PB  T1   PA / PB  T2

(d) PA (T1) < PB (T1), PA (T2) < PB (T2) and  PA / PB T1   PA / PB T2
39. According to transition state theory, the temperature-dependence of pre-exponential factor (A) for
CHEM ACADEMY
a reaction between a linear and a non-linear molecule, that forms products through a non-linear
transition state, is given by
2 2
[NET June 2015]
(a) T (b) T (c) T (d) T–1.5
40. According to the transition state theory, one of the vibrations in the activated complex is a loose
vibration. The partition function for this loose vibration is equal to (kB is the Boltzmann’s constant
and h is the Planck’s constant) [NET Dec. 2015]

k BT hv k BT
(a) (b) k T (c) kBT (d)
h B hv
41. For a gaseous reaction, 2NO(g) + Cl2(g)  Non-linear T.S.  2NOCl, the pre-exponential factor in
the rate constant is proportional to [NET Dec. 2014]
1/2 –1/2 –5/2
(a) T (b) T (c) T (d) T–7/2
42. A chemical reaction involving [NET June 2013]
nonlinear molecule + nonlinear molecule  nonlinear activated complex
The number of vibrational degrees of freedom in the activated complex, containing N atoms, is
(a) 3N–5 (b) 3N–6 (c) 3N–7 (d) 3N–8
43. The free energy [A–A(0)] of a system with 10 non-interacting spins (S=1) is [NET Dec. 2018]
(a) –KBT In (3) (b) –10kBT In (3) (c) –kBT In (0.3) (d) –10kBT In (0.3)
44. The translational partition function for Ar confined to a volume of 1 L at 300K, having thermal
wavelength of 1.60 × 10–11 m, is closest to [NET Dec. 2018]
29 29 29
(a) 24.4 × 10 (b) 2.44 × 10 (c) 0.244 × 10 (d) 244 × 1029

Head Office: North Delhi: 72, Mall Road, G.T.B. Nagar, New Delhi - 110009
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45. Root mean square speed of the molecules of a perfect gas is proportional to [NET Dec. 2018]
(a) 1/T1/2 (b) T (c) T1/2 (d) 1/T
46. For a linear molecule the mean energies for translation, rotation (T >>R) and vibration (T >> V)
follow ratio: [NET June 2019]
3 3 1 1
(a) 1: :1 (b) :1:1 (c) 1: :1 (d) :1:1
2 2 2 2
47. The populations of proton spins in the highest energy level of a sample in magnetic fields of 1.5T
N
and 7.0 T are N’ and N, respectively. The value of In is (, h, k, T are gyromagnetic ratio of the
N
proton, Planck’s constant, Boltzmann constant and temperature of the sample, respectively; as-
sume that the partition functions for both systems can be approximated as 1)
[NET June 2019]
3 14
(a) 5.5 / kT (b)  / kT (c)  / kT (d) 8.5 / kT
14 3
48. The difference between standard molar entropies of two mono-atomic gases (A) and (B)
S 0
m,A  S0m,B  at a given temperature is (given that the molar mass of 9A) is twice the molar mass of
(B)) [NET June 2019]
3 5 7
(a) RIn 2 (b) R In 2 (c) RIn 2 (d) RIn 2
2 2 2
49. CHEM ACADEMY
The rotational partition function is expected to be the smallest for the molecule, among the follow-
ing [NET June 2019]
(a) H2 (b) Li2 (c) N2 (d) F2

GATE Previous Years’ Questions

1. The number of molecules of an ideal gas in a 8.2 1 container at 380 torr and 27ºC will be
[GATE 2000]
23 22 23
(a) 1.0 × 10 (b) 1.0 × 10 (c) 6.02 × 10 (d) 12.04 × 1023
2. The translational partition function of a hydrogen molecule confined in a 100 mL flask at 298 K
(Mol. wt. of hydrogen = 2.016) is: [GATE 2003]
(a) 2.8 × 1020 (b) 2.8 × 1025 (c) 2.8 × 1026 (d) 2.8 × 1027
3. The Vrms of a gas at 300 K is 30 R1/2. The molar mass of the gas, in kg mol–1, is
[GATE 2004]
(a) 1.0 (b) 1.0 × 10–1 (c) 1.0 × 10–2 (d) 1.0 × 10–3
4. The vibrational partition function for a molecule with fundamental frequency v is given by
1
       
(a) exp   k T  (b) 1  exp    [GATE 2005]
 B    k BT 
1 1
               
(c) exp    1  exp   (d) exp    1  exp  
 k BT    k BT   2k BT    k BT 

Head Office: North Delhi: 72, Mall Road, G.T.B. Nagar, New Delhi - 110009
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5. Given that the mean speed of H2 is 1.78 km s–1, the mean speed of D2 will be [GATE 2005]
–1 –1 –1 –1
(a) 1.26 km s (b) 2.52 km s (c) 5.04 km s (d) 3.17 km s .
6. As per the kinetic theory of ideal gases, which of the following statements is NOT correct?
[GATE 2006]
(a) gas particles have mass but no volume
(b) particles are in a Brownian motion between collisions.
(c) during the collision, the system does not lose energy
(d) particles exert same force per unit area on all sides of the container.
7. N non-interacting molecules are distributed among three non-degenerate energy levels
0 = 0, 1 = 1.38 × 10–21J and 2 = 2.76 × 10–21J, at 100K. If the average total energy of the system at
this temperature is 1.38 × 10–18J, the number of molecules in the system is:
[GATE 2007]
(a) 1000 (b) 1503 (c) 2354 (d) 2987
8. Assuming H2 and HD molecules having equal lengths, the ratio of the rotational partition function
of these molecules, at temperatures above 100K is [GATE 2007]
(a) 3/8 (b) 3/4 (c) 1/2 (d) 2/3
9. A certain molecule can be treated as having only a doubly degenerate state lying at 360 cm–1 above
the non-degenerate ground state. The approximate temperature (K) at which 15% of the molecule
will be in the upper state is [GATE 2008]
(a) 500 (b) 150 (c) 200 (d) 300
10.
(a) 20000
CHEM ACADEMY
(b) 8000
–1
At T = 300K, the thermal energy (kBT) in cm is approximately.
(c) 5000 (d) 200
[GATE 2008]

11. The molecular partition function of a system is given by [GATE 2012]

3 3
3
 k T   8 mk B T 
2 2
q(T) =  B    , where the symbols have their usual meanings.
 hc   h2 
The heat capacity at constant volume for this system is
(a) 3R (b) 6R (c) 9R/2 (d) 3R/2
12. The molecular partition function for a system in which the energy levels are equispaced by , is
[GATE 2014]
1 1 1 1
(a) (b) (c) (d)
1  e 1  e 1  e  1  e 
13. For an ideal gas with molar mass M, the molar translational enetropy at a given temperature is
proportional to [GATE 2015]
(a) M3/2 (b) M1/2 (c) eM (d) In (M)
14. The rotational partition function of a diatomic molecule with energy levels corresponding to J = 0,
1, is (where ,  is a constant) [GATE 2015]
–2 –2 –3
(a) 1 + 2e (b) 1 + 3e (c) 1+e (d) 1 + 3e–3
15. Consider N particles at temperature T, pressure P, volume V and chemical potential  having en-
ergy E. The parameters that are kept constant for a canonical ensemble are [GATE 2017]
(a) N, V, T (b) N, V, E (c) N, P, T (d) , V, T

Head Office: North Delhi: 72, Mall Road, G.T.B. Nagar, New Delhi - 110009
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16. For ortho-hydrogen, the nuclear wavefunction and the rotational quantum number, respectively, are
[GATE 2017]
(a) antisymmetric and even (b) symmetric and odd
(c) symmetric and even (d) antisymmetric and odd
17. The fundamental vibrational wavenumbers for H2 and I2 are 4403.2 cm–1 and 214.5 cm–1, respec-
tively. The relative population of the first excited vibrational states of these two molecule com-
pared to their respective ground states at 300K are respectively: [GATE 2009]
(a) 6.75 × 10–1 and 3.57 × 10–1 (b) 6.75 × 10–10 and 3.57 × 10–1
(c) 3.57 × 10–6 and 6.75 × 10–1 (d) 3.57 × 10–1 and 6.75 × 10–1
18. The temperature dependence of partition are as follows: [GATE 2013]
3/2 0
qtranslation T qvibration  T
qrotation  T (linear molecule) qrotation  T3/2 (non-linear molecule)
According to the Conventional Transition State Theory (CTST), the temperature denpendence of
the Arrhenius pre-exponential factor for a reaction of the type given below is
linear molecule + linear molecule  non-liner linear transition state  products.
(a) T–1 (b) T0 (c) T1 (d) T2
19. Consider a system of three identical and distinguishable non-interacting particles and three avail-
able non-degenerate single particle energy levels having energies 0,  and 2. The system is in
contact with a heat bath of temperature T (K). A total energy of 2 is shared by these three particles.
The number of ways the particles can be distributed is _________ [GATE 2019]
20.
CHEM ACADEMY
Consider a two-state system at thermal equilibrium having energies 0 and 2kBT for which the
degnerates are 1 and 2, respectively. The value of the partition function at the same absolute tem-
perature T is ___________ (Round off to two decimal places). [GATE 2019]
(kB is the Boltzmann constant)

ANSWER KEY
CSIR NET Previous Year
1. a 2. a 3. 4. c 5. d 6. d
7. c 8. d 9. b 10. c 11. c 12. b
13. b 14. a 15. b 16. b 17. b 18. d
19. c 20. d 21. c 22. a 23. b 24. d
25. b 26. b 27. d 28. a 29. c 30. d
31. d 32. c 33. c 34. d 35. c 36. c
37. c 38. c 39. d 40. d 41. d 42. c
43. b 44. b 45. c 46. b 47. a 48. a
49. a

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