Statistical and Quantum Physics Examples 1

P. Alexander and M.S. Longair

1 The variance of a distribution

Starting from the expressions for the mean and variance of a discrete distribution
X
µ = pi xi
i
X
2
σ = pi (xi − µ)2
i

Show that the variance can be written as

σ 2 = x2 − µ2

Show that the same relationship holds for a continuous distribution f (x) dx.

2 An exercise on distribution functions

The normal distribution function, f (x), is given by

x2
 
1
f (x) = √ exp − 2 .
2πσ 2 2σ

(a) Sketch on squared paper the function f (x) for −3σ < x < 3σ, noting the values at
x = σ, 2σ, and 3σ.

(b) Explain how f (x) is related to the probability of finding x in a given range, x to
x + dx. Estimate roughly from your sketch the probabilities that x lies in the range
−0.05σ < x < 0.05σ, and −σ R u < x < σ. Find the exact probabilities by looking up a
set of statistical tables for 0 f (x) dx. By integrating the normal distribution, check
that the total probability of finding x in the range ∞ < x < +∞ is exactly unity.

(c) Check that the variance 2

p of the normal distribution is σ and show that the mean
value of |x|, h|x|i, is (2/π) σ.

You will need to use the following standard integrals:

√ √
Z ∞ Z ∞ Z ∞
−x2 −x2 2
e dx = π, xe 1
dx = 2 , x2 e−x dx = 1
2 π.
−∞ 0 −∞

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3 Radioactive decay and distribution functions

At a time t = 0 there are N0 atoms of the unstable carbon isotope 14 C. The probability
of a given 14 C nucleus decaying in a time interval dt is dt/τ .

(a) Write down an expression for the number of 14 C nuclei decaying at the time interval
t to t + dt. Hence derive a differential equation for the number of 14 C nuclei as a
function of time, and integrate it to find N (t).

(b) Calculate the fraction of the original 14 C nuclei which decay in the time interval t
to t + dt.

(c) What is the probability that a 14 C nucleus will have decayed after a time t?

(d) What is the half-life of the species, namely the time it takes for half of the 14 C atoms
to have decayed?

4 The classical Boltzmann distribution

A system is in thermal equilibrium at temperature T . If the number of states of the system

with energy E is proportional to E explain why the probability of finding the system in
the energy range E to E + dE is given by

p(E) dE = AE exp(−E/kT ) dE

(a) Find the constant A.

(b) Sketch this distribution function.

(c) What is the most likely energy for the system?

(d) What is the mean energy of the system?

5 A descriptive question about the ideal gas equation of state (write your answer in the
form of a short essay).

What is an ideal gas? To what extent is the ideal gas equation of state pV = nRT an
expression of experimental results, and to what extent a definition? What is meant by
Boltzmann’s constant k.
Describe the assumptions underlying the kinetic theory of gases. What rôle do collisions
play in establishing thermodynamic equilibrium?

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6 The distribution of speeds in a gas

(a) The distribution of molecular speeds, v, in an ideal gas in thermal equilibrium has
the form
2
f (v) dv = Av 2 e−mv /2kT dv
where A is a constant, m is the mass of a molecule, k is Boltzmann’s constant, and
T is the temperature. Explain what is meant by f (v), and how the factors v 2 and
exp(−mv 2 /2kT ) arise. Explain how the constant A is determined and find its value.

(b) Show that the average kinetic energy averaged over all molecules in the body of the
gas is 23 kT , exactly as predicted by the equipartition theorem.

(c) Show that the mean speed is given by

r
8kT
v= .
πm

(d) Consider now the kinetic energy averaged over all the molecules hitting the sides of
the container. Would you expect this to be less than, equal to, or greater than 23 kT ?
Argue your case clearly in a few lines.

(e) (More demanding) Calculate the average kinetic energy of the molecules hitting the
sides of the container.

7 The mean speed in a gas

(a) Derive an expression for the escape velocity from the surface of a planet of radius R
and acceleration due to gravity at the surface g.

(b) Estimate the escape velocity for (i) the Earth for which R = 6.37 × 10 6 m,
g = 9.8 m s−2 and (ii) Mars for which R = 3.88 × 106 m, MMars /MEarth = 0.108.
1/2
(c) The surface temperature of Mars is typically 270 K. Calculate the rms speeds (v 2 )
for H2 , O2 and CO2 . Do you think these molecules are likely to be found in the
atmosphere of Mars?

(d) Estimate the escape velocity at the surface of the Moon where g is about one-sixth
its value on earth and R = 1.74 × 106 m. Use this result to discuss why the Moon
does not have an atmosphere.

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8 A question about the kinetic theory of gases

Molecules are sometimes bound to a flat solid surface at low density, but free to move
parallel to the surface. What is the analogue of the pressure for such a 2D gas? Develop
a 2D kinetic theory for such a gas, and in particular find or suggest 2D analogues of the
3D equations for J = 14 nv, p = 13 nmv 2 , 12 mv 2 = 32 kT , and pV = RT .

9 The flux density expression J = 14 nv

A vessel partly filled with mercury is closed except for a hole of area 0.1 mm 2 above the
liquid level and is kept at 0◦ C. The vessel is contained within a very much larger vessel in
which a very high vacuum is maintained. After 30 days, it is found that 24 mg of mercury
have been lost from the inner vessel. The relative atomic mass of mercury is 201.

(a) Draw a diagram, and explain why mercury is lost from the vessel.

(b) What is the average speed, v, of the mercury atoms in the vapour above the liquid?
You may wish to use the relationship
8 2
v2 = v .
3π

(c) What is the mean rate of flow of mercury atoms through the hole?

(d) Hence calculate the vapour pressure of mercury at 0 ◦ C.

10 A question about a one-dimensional random process

An individual, somewhat worse for wear, comes out of a pub in the middle of a very long
alley and takes steps of 1 m, one every second, randomly towards one end or the other. The
person does this every day for many months. On any particular day, we cannot predict
exactly where the person will be after taking a given number of steps since progress is
random at every step. However, by observing the outcome over many days we can write
down the probability of the person being a given distance from the pub after a given time.

(a) The individual’s first two steps can be taken in one of four combinations: LL, LR,
RL, and RR. Hence after having taken two steps, the person will be −2, 0, or +2
metres from the door of the pub, with the associated number of ways of getting there
being 1, 2, 1 respectively. Draw up a table showing the number of ways associated
with the possible distances from the pub after 2, 3, and 4 steps.

(b) Work out the expansion for (1 + x) 8 and note any similarities with the numerical
calculations for (a). Discuss the significance with your supervisor.

(c) Draw a histogram representing the √ possibilities after 8 steps, and show that the root
mean square distance travelled is 8 m. What is the most probable value? Note
that the histogram looks quite like a Gaussian distribution.

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 (d) As the number of steps increases, the Gaussian distribution becomes a better and
better approximation with an rms deviation equal to the square root of the number
of steps. Make a rough estimate of the time after which the person has a probability
of 1/3 of being at least 20 m from the pub. You may find it helpful to note that the
area under a normal distribution at values of |x| greater than 1σ is 0.317 (see your
answer to Question 2).
(e) Optional extra: If the alley is exactly 20 m long in each direction from the pub, the
individual no longer returns to the alley after randomly ‘diffusing’ 20 m. How does
this affect the answer you derived in (c)? Would the calculated time be greater than,
the same as, or less than the answer to (c)? Argue your case qualitatively in a few
lines.

11 An exercise on the random walks of molecules

(a) Explain what is meant by the mean free path l of a molecule in a gas. Why is it the
inverse of the scattering rate per unit path?
(b) Using the hard sphere model, show that l is given approximately by
1
l=
nπd2
for fast-moving molecules, where d is the hard-sphere diameter and n is the number
density. Why is this an overestimate for slower molecules? Use this formula to
find the mean free path of molecules in air at 20 ◦ C, if d is about 0.37 nm. (Take
atmospheric pressure to be 105 Pa.)
(c) A noxious gas is released from a small test-tube. On the unlikely assumption that
diffusion is the only process which matters, how long does it take typical molecules
of the noxious gas which has properties similar to those of the gas in (b) to travel a
distance of 1 m? Why is this answer unrealistic?

12 An example of detailed balance: a kinetic model for adsorption

Gas molecules incident on a surface may stick to the surface with a probability σ provided
they hit a part of the surface which is empty. The maximum number of molecules which
can be adsorbed per unit area of the surface is N and they then form a layer one molecule
deep. The probability of a molecule adsorbed on the surface leaving in unit time is r.

(a) Starting from the expression for the number of molecules striking unit area in unit
time (J = 14 nc), show that J can be written:
p
J=
(2πmkT )1/2

(b) If a fraction of the surface, θ, is covered with molecules explain why the number of
molecules from the gas adsorbing onto the surface per unit area per unit time, n a ,
is given by:
na = (1 − θ)σJ

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 (c) How many molecules leave the surface per unit area per unit time?

(d) Show that in equilibrium the fraction of the surface covered by molecules is given by

σJ
θ=
N r + σJ

(e) The rate of molecules leaving the surface is a thermally activated process
r = r0 e−E/kT . Sketch how the surface coverage, θ, depends on the temperature, T ,
for a gas at a fixed pressure p.

13 Adiabatic expansion

A balloon of volume V0 is tethered to the ground using a light, cable. It is filled with
helium gas of density ρHe . At ground level the pressure and density in the atmosphere
are p0 and ρ0 respectively. The atmosphere is isothermal with a temperature T 0 . The
balloon is allowed to rise through the atmosphere to a height h by very slowly letting out
the cable. At all heights the gas pressure niside the balloon equals the pressure outside.

(a) How do the pressure and density in the atmosphere vary with height h?

(b) The balloon is an excellent thermal insulator and the helium in the balloon expands
adiabatically. What is the pressure in the balloon at a height h and find its volume.

(c) What is the difference in tension in the cable when the balloon is tethered near to
the ground and at a height h.

14 Isothermal expansion

What is meant by the term a reversible process?

An ideal gas at pressure pi is expanded isothermally and reversibly from an initial volume
Vi to a final volume Vf .

(a) What is the change in internal energy of the gas?

(b) Calculate the work done on the gas during the expansion.

(c) Has heat entered or left the gas during the expansion and if it has how much?

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15 Application of the Classical Boltzmann distribution

A centrifuge spinning at 10 rev s−1 about a vertical axis has within it a horizontal tube
whose end is 100 mm from the spin axis. This tube contains a suspension of fine titanium
oxide particles in water. After equilibrium has been reached, it is observed that there is
an exponentially-decreasing distribution of particles in suspension with distance from the
end of the tube.

(a) Draw a diagram showing the forces acting on a particle in the frame of reference
of the tube. You may ignore gravity which acts at right angles to the tube axis.
Remember to include upthrust (Archimedes’ Principle) as well as the centrifugal
mass-acceleration, mω 2 r.

(b) Explain in a few lines why the particles are not all compressed into a solid lump at
the end of the tube, but instead arrange themselves in an exponential distribution
of concentration.

(c) The concentration of particles in suspension 1 mm from the end of the tube is found
to be 1500 times that at a distance of 2 mm from the end of the tube. If the average
mass of each particle is 10−19 kg, the density of titanium oxide is 4200 kg m −3 , and
the density of water is 1000 kg m−3 , what is the temperature in the tube? Note that
2 mm is a small fraction of 98.5 mm and so you can use an approximation.

16 Chemical Reactions and the Boltzmann Equation

A chemical reaction is observed to proceed at different rates depending on the temperature

as shown in the following table:

Chemical Reaction Rates as a function of temperature

T /◦ C Rate/(arbitrary units)
0 5.5
6 10.9
12 23.5
18 48.0
24 98.0
30 206.0

(a) Explain in a few lines why the rate of reaction depends upon the temperature.
Explain what is meant by the activation energy.

(b) Write down an expression showing the form of the dependence of the rate on tem-
perature. Hence, by re-expressing the figures in the table, fit a straight line to the
points. By drawing a graph, or by using your calculator, find the best-fitting slope.

(c) Hence find the characteristic energy for this reaction, that is, the activation energy
of the reaction.

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 Answers

(2) (b) The exact values are prob(−0.05σ < x < 0.05σ) = 0.040; prob(−σ < x < σ) =
0.683
1
(3) (a) N (t) = N0 exp(−t/τ ); (b) f (t)dt = τ exp(−t/τ )dt; (c) F (t) = 1 − exp(−t/τ );
(d) t1/2 = τ ln 2

(4) (a) 1/(kT )2 ; (c) kT ; (d) 2kT

(6) (a) A = 4π(m/2πkT )3/2 ; (e) 2kT

(7) (b) (i) 11 km s−1 (ii) 5 km s−1 ; (c) 1.9 km s−1 , 470 m s−1 , 270 m s−1 ;
(d) 2.4 km s−1

(8) (b) J = nv/π; p = 21 nmv 2 ; 12 mv 2 = kT ; pA = RT

(9) (b) 169 m s−1 (c) 2.76 × 1013 atoms s−1 (d) 2.5 × 10−2 N m−2

(10) (c) About 400 s; (d) a slightly shorter time.

(11) (b) 9.3 × 10−8 m; (c) about 6 hours

(12) (c) rθN

ρ p
(13) (a) ρ0 = p0 = exp(−mgh/kT ); (b) V = V0 exp(3mgh/5kT ); (c) ρ0 V0 g[1−exp(−2mgh/kT )];

(14) (a) no change; (b) −N kT ln(Vf /Vi ); (b) N kT ln(Vf /Vi )

(15) (c) 298 K

(16) (c) 0.88 eV