Chemistry-2X: Molecular Thermodynamics (Professor Alan Cooper)

Typical examination questions (with answer notes)

The following questions are adapted from previous class/degree examinations in this
topic, comprising a mixture of long (15 mark) and shorter (5 mark) examples.

Answer notes do not necessarily comprise the full solution, and are provided for your
guidance only.

You are strongly advised to attempt each of the questions before consulting the answer
notes.

Tables of physical constants are normally supplied with the examination papers.

Please be aware that slight variations in course content from year to year may be reflected
in these sample questions.

AC: November 2000

Qu. 1 (a) Write down the Boltzmann probability expression. Define each of the terms involved and explain
its relevance to a molecular understanding of thermodynamics. [4]

(b) Give the molecular statistical definition of entropy, and explain how this definition may be used to
explain the Second Law of Thermodynamics. [4]

(c) Show that when n moles of an ideal gas are allowed to expand at constant temperature, T , from
an initial volume V 1 to a final volume V 2 under ideal reversible conditions, the entropy
change is:

V 
∆S = nR. ln 2 
V 1 

What are ∆H and ∆G for this process ?

What is the maximum amount of work (W) that may be done in this expansion process ?

Where does the energy for this external work (W) come from, and is it consistent with the First
Law of Thermodynamics ?
[9]

Qu. 2 (a) Estimate the average thermal velocity of bromine (Br2) molecules in the vapour state at 250 °C,
given that the mean thermal kinetic energy per molecule is 3kT/2. [4]

(b) What fraction of these molecules might be vibrating at -273 oC ? [1]

[Atomic weight of Br = 79.9]

Qu. 3 (a) Give the molecular definitions of both entropy and Gibbs free energy. [2]

(b) The ionization energy of Na is 495.8 kJ mol-1. Estimate what proportion of sodium atoms might be
fully ionized in the atmosphere of a star at 6200°C. [3]

Qu. 4 (a) Explain why calculation of the exact motion of atoms or molecules in a typical sample is neither
feasible nor useful in understanding the thermodynamic properties of matter. [3]

(b) Write down the Boltzmann probability expression, defining each of the terms carefully. [3]

(c) The normal, non-degenerate vibrational stretching frequency for bromine (Br2 , mw 160) is 322
cm-1. Show that this corresponds to a difference in energy between the ground and first
vibrationally excited state of 6.4 x 10-21 J per molecule. Hence estimate the fraction of Br2
molecules in the first excited state at 200 °C . [5]

(d) Estimate the average thermal velocity of bromine molecules in the vapour state at 200 °C, given
that the mean thermal kinetic energy per molecule is 3kT/2. [4]
Qu. 5 (a) Give the molecular definitions of both entropy and Gibbs free energy. [2]

(b) The ionization energy of Li is 513.3 kJ mol-1. Estimate what proportion of lithium atoms might be
fully ionized in the atmosphere of a star at 6200°C. [3]

Qu. 6 (a) Give three examples of chemical, physical, or everyday phenomena that support the molecular-
statistical view of matter. Explain each case. [3]

(b) Starting from the Boltzmann distribution law, derive the barometric expression showing how
atmospheric pressure varies with height above sea level. [2]

Qu. 7 (a) Show how the Boltzmann probability expression can be used to derive the equilibrium constant
(K) for a simple chemical reaction A B. [3]

(b) Explain how the concepts of standard free energy change (∆G°) and entropy change (∆S°) follow
from this. [3]

(c) Define the terms “activity” and “activity coefficient” and explain why it is necessary to use them
in more exact thermodynamic expressions. [3]

(d) Nitric oxide (NO) in the air is formed by direct reaction of oxygen and nitrogen at high
temperatures, for example in the exhaust of jet engines. If the normal mode vibration of NO has a
frequency 1876 cm-1, estimate what fraction of NO molecules might be in the first vibrational state
at 600 °C . [6]

Qu. 8 (a) What is meant by Brownian motion and how does it support the molecular view of heat and
matter? [2]

(b) Estimate the average velocity of methane (CH4) molecules in the vapour state emitted from cows
at 300K, given that the mean thermal kinetic energy per molecule is 3kT/2. [3]

Qu. 9 (a) Write down the Boltzmann probability expression and explain what it means. [2]

(b) The bond dissociation enthalpy of O2N-NO2 is around 57 kJ mol-1. Estimate what proportion of
N2O4 molecules might be dissociated to NO2 in a motor vehicle exhaust at 250 °C . [3]

Qu. 10 (a) Give a statistical or molecular definition of the Second law of Thermodynamics. [3]

(b) Give THREE examples of chemical, physical, or everyday phenomena that depend on
thermodynamic fluctuations and which support the molecular-statistical view of matter. Explain
briefly. [4]

(c) Estimate the mean thermal velocity of iodine (I2) molecules in the vapour state at 70°C, given that
the average thermal kinetic energy per molecule is 3kT/2 and the relative atomic mass of iodine is
126.9 g mol-1. [4]
 (d) If the bond dissociation energy of I2 is 152 kJ mol-1, estimate what fraction of molecules might be
dissociated at 150°C. What is the actual number of molecules that might be dissociated in this
way in one mole of iodine under these conditions ?
[4]

Qu. 11 (a) Starting from the Boltzmann probability distribution law, derive the barometric expression
showing how atmospheric pressure varies with height above sea level. [2]

(b) List, with brief explanations, THREE practical consequences or applications of this effect. [3]

Qu. 12 (a) Give the molecular definitions of both entropy and Gibbs free energy. [2]

(b) The ionization energy of Li is 513.3 kJ mol-1. Estimate what proportion of lithium atoms might be
fully ionized in the interior of a star at 9500°C. [3]

[Answer notes start on next page]

 Answer Notes

[Do not consult these until you have attempted the questions.]

1. (a) Boltzmann: p(E) = w.exp(-E/kT) or equivalent, with appropriate explanations

(b) “The most probable things generally happen”

S = k.ln(w) ! ∆S ≥ 0 (2nd Law)

(c) w is proportional to the volume

This means that if we change the volume from V1 to V2:

w2/w1 = V2/V1 = P1/P2

And the entropy change is:

∆S(V1 → V2) = R.ln(V2/V1) = R.ln(P1/P2)

... for 1 mole of gas.

∆H = 0 (for perfect gas)

∆G = -T.∆S

W = -∆G

Energy comes from heat transfer from surroundings (to keep system isothermal)

2. (a) ½mv2 = 3kT/2 ≡ 3RT/2 ; m = 159.8/1000 kg (per mole) [2]

∴ v = (3 x 8.314 x 523/0.159)½ = 286 m s-1 [2]

(b) -273 oC = 0 K: fraction vibrating = zero [1]

3. (a) S = k.ln(w) G = -RT.ln(p) (or equivalent) [2]

(b) Boltzmann relative probability:

p(∆E) = exp(-∆E/RT) = exp(-495.8 x 1000/8.314 x 6473)

= exp(-9.21) = 1.0 x 10-4 [3]

[Note:- Units: kJ --> J ; O

C --> K ; Energy given per mole, ∴ use R not k ]

4. (a) Too many molecules ( ≈ 1023), and we only observe average collective effects...
(or anything sensible) [3]
 (b) p(E) = w.exp(-E/kT) or equivalent, with correct definitions [3]

(c) ∆E = hc/λ = 6.626x10-34 x 2.998x108 x 32200 = 6.4x10-21 J [1]

(units for 1/λ !!)

p(∆E) = 1.exp(-6.4x10-21/1.381x10-23 x 473) = e-0.98 = 0.375 [2]

Fraction = p/(1+p) = 0.375/1.375 = 0.27 (27%) [2]

(d) ½mv2 = 3kT/2 ≡ 3RT/2 ; m = 160/1000 kg (per mole) [2]

∴ v = (3 x 8.314 x 473/0.16)½ = 272 m s-1 [2]

5. (a) S = k.ln(w) G = -RT.ln(p) (or equivalent) [2]

(b) Boltzmann relative probability:

p(∆E) = exp(-∆E/RT) = exp(-513.3 x 1000/8.314 x 6473)

= exp(-9.54) = 7.2 x 10-5 [3]

[Note:- Units: kJ --> J ; OC --> K

Energy given per mole, ∴ use R not k ]

6. (a) Several examples discussed in lectures, e.g. [3]

Brownian motion (molecular collisions, energy/momentum fluctuations)

Colour of sky/sunsets (light scattering, Rayleigh, density fluctuations)
Chemical kinetics (energy fluctuations over activation barriers)
Critical opalescence (large density fluctuations at critical points)

(b) Boltzmann: p(E) = exp(-E/kT)

Gravitational E = mgh

∴ p(h)/p(0) = exp(-mgh/kT) [2]

7. (a) Standard course work. A B

K ≈ [B]/[A] ≡ p(B)/p(A) [1]

Boltzmann p(A) = wA.exp(-HA/RT) ...etc

∴ K = (wB/wA).exp(-∆H/RT) where ∆H = HB - HA [2]

 (b) Following from above:

-RT.ln(K) = ∆H - RT.ln(wB/wA) [1]

By analogy with ∆G° = ∆H - T.∆S°

∆G° = -RT.ln(K) and ∆S° = R.ln(wB/wA) [2]

(c) Activity ai = γ[I] [1]

γ = activity coefficient - a correction factor to take into account

the effects of intermolecular forces between molecules in
complex mixtures. [2]

(d) Use Boltzmann, p(E) = exp(-E/kT) (assume non-degenerate)

where E = hc/λ = 6.626 x 10-34 x 2.998 x 108 x 187600

= 3.73 x 10-20 J
[3]
(Remember 1/λ = 1876 cm -1
≡ 187600 m ; T = 873 K)
-1

p(E) = exp(-3.73 x 10-20/1.381 x 10-23 x 873) = exp(-3.09) = 0.045

i.e. about 4.5% excited [3]

8. (a) Random, chaotic motion observed in microscopic particles immersed in a fluid. A consequence of
random molecular collisions, pressure fluctuations, etc...
[2]

(b) ½mv2 = 3kT/2 ≡ 3RT/2 ; m = 16/1000 kg (per mole) [1]

∴ v = (3 x 8.314 x 300/0.016)½ = 684 m s-1 [2]

9. (a) p(H) = w.exp(-H/RT) or equivalent [2]

(b) Straightforward application of Boltzmann...

p = exp(-57000/8.314x523) = exp(-13) = 2 x 10-6 (2 ppm) [3]

(Assuming - unrealistically - that the degeneracy factor w is unity. Give extra credit if students comment
sensibly on this.)

10. (a) “The most probable things generally happen” (or equivalent).

(b) Any 3 of the following:

Brownian motion.
Atmospheric light scattering (blue skies, sunsets).
Chemical kinetics (fluctuations-->transition state, over activation barrier).
Critical point fluctuations (demonstrated in lecture).
Protein dynamics.
 (c) ½mv2 = 3kT/2 --> v = (3kT/m)1/2

m = 253.8/(1000 x 6 x 1023) = 4.23 x 10-25 kg for I2 molecule

T = 343 K ; k = 1.38 x 10-23 J K-1

Hence: v = 183 m s-1

(d) Boltzmann relative probability:

p(∆E) = exp(-∆E/RT) = exp(-152 x 1000/8.314 x 423)

= exp(-44.2) = 1.7 x 10-19

x 6 x 1023 --> Number dissociated = 1 million (1.02 x 106)

11. (a) Boltzmann: p(E) = exp(-E/kT)

Gravitational E = mgh

∴ p(h)/p(0) = exp(-mgh/kT) [2]

(b) Consequences/applications (anything sensible), e.g.

Reduced pressure at elevated heights (mountains, aircraft)

Lower boiling point of liquids at height
Reverse effects down mines, etc.
Measurement of height
[1 mark each, upto 3]

12. (a) S = k.ln(w) G = -RT.ln(p) (or equivalent) [2]

(b) Boltzmann relative probability:

p(∆E) = exp(-∆E/RT) = exp(-513.3 x 1000/8.314 x 9773)

= exp(-6.32) = 1.8 x 10-3 [3]

[Note:- Units: kJ --> J ; OC --> K

Energy given per mole, ∴ use R not k ]

END