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8.333 Statistical Mechanics I: Statistical Mechanics of Particles

Fall 2007

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8.333: Statistical Mechanics I Fall 2007 Test 1

Review Problems

The first in-class test will take place on Wednesday 9/26/07 from
2:30 to 4:00 pm. There will be a recitation with test review on Friday 9/21/07.
The test is ‘closed book,’ but if you wish you may bring a one-sided sheet of formulas.
The test will be composed entirely from a subset of the following problems. Thus if you
are familiar and comfortable with these problems, there will be no surprises!
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You may find the following information helpful:

Physical Constants
Electron mass me ≈ 9.1 × 10−31 kg Proton mass mp ≈ 1.7 × 10−27 kg
Electron Charge e ≈ 1.6 × 10−19 C Planck’s const./2π h̄ ≈ 1.1 × 10−34 Js−1
Speed of light c ≈ 3.0 × 108 ms−1 Stefan’s const. σ ≈ 5.7 × 10−8 W m−2 K −4
Boltzmann’s const. kB ≈ 1.4 × 10−23 JK −1 Avogadro’s number N0 ≈ 6.0 × 1023 mol−1

Conversion Factors
1atm ≡ 1.0 × 105 N m−2 1˚
A ≡ 10−10 m 1eV ≡ 1.1 × 104 K

Thermodynamics
dE = T dS+dW
¯ For a gas: dW
¯ = −P dV For a wire: dW
¯ = Jdx

Mathematical Formulas
�∞ √
n! π
�1�
0
dx xn e−αx = αn+1 2
!= 2

�∞ �
x2
� √ � 2 2�
−∞
dx exp −ikx − 2σ 2 = 2πσ 2 exp − σ 2k limN→∞ ln N ! = N ln N − N

� −ikx � �∞ (−ik)n � �∞ (−ik)n

hxn i ln e−ikx = n=1 hxn ic
�
e = n=0 n! n!

x2 x4 x3 x5
cosh(x) = 1 + 2! + 4! +··· sinh(x) = x + 3! + 5! +···

2π d/2
Surface area of a unit sphere in d dimensions Sd = (d/2−1)!

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1. Surface tension: Thermodynamic properties of the interface between two phases are
described by a state function called the surface tension S. It is defined in terms of the
work required to increase the surface area by an amount dA through dW¯ = SdA.
(a) By considering the work done against surface tension in an infinitesimal change in
radius, show that the pressure inside a spherical drop of water of radius R is larger than
outside pressure by 2S/R. What is the air pressure inside a soap bubble of radius R?
(b) A water droplet condenses on a solid surface. There are three surface tensions involved
S aw , S sw , and S sa , where a, s, and w refer to air, solid and water respectively. Calculate
the angle of contact, and find the condition for the appearance of a water film (complete
wetting).
(c) In the realm of “large” bodies gravity is the dominant force, while at “small” distances
surface tension effects are all important. At room temperature, the surface tension of
water is S o ≈ 7 × 10−2 N m−1 . Estimate the typical length-scale that separates “large” and
“small” behaviors. Give a couple of examples for where this length-scale is important.
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2. Surfactants: Surfactant molecules such as those in soap or shampoo prefer to spread
on the air-water surface rather than dissolve in water. To see this, float a hair on the
surface of water and gently touch the water in its vicinity with a piece of soap. (This is
also why a piece of soap can power a toy paper boat.)
(a) The air-water surface tension S o (assumed to be temperature independent) is reduced
roughly by N kB T /A, where N is the number of surfactant particles, and A is the area.
Explain this result qualitatively.
(b) Place a drop of water on a clean surface. Observe what happens to the air-water­
surface contact angle as you gently touch the droplet surface with a small piece of soap,
and explain the observation.
(c) More careful observations show that at higher surfactant densities
� � �2 �
∂S �� N kB T 2a N ∂T �� A − Nb
= − , and =− ;
∂A �T (A − N b)2 A A ∂S A� N kB

where a and b are constants. Obtain the expression for S(A, T ) and explain qualitatively
the origin of the corrections described by a and b.
� �
(d) Find an expression for CS − CA in terms of ∂E � , S, ∂ S �� , and ∂T �� , for ∂E � =
� �
∂A T ∂A
T ∂S A ∂T A
∂E �
�
∂T S .

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3. Temperature scales: Prove the equivalence of the ideal gas temperature scale Θ, and
the thermodynamic scale T , by performing a Carnot cycle on an ideal gas. The ideal gas

satisfies P V = N kB Θ, and its internal energy E is a function of Θ only. However, you

may not assume that E ∝ Θ. You may wish to proceed as follows:
(a) Calculate the heat exchanges QH and QC as a function of ΘH , ΘC , and the volume

expansion factors.

(b) Calculate the volume expansion factor in an adiabatic process as a function of Θ.

(c) Show that QH /QC = ΘH /ΘC .

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4. Equations of State: The equation of state constrains the form of internal energy as

in the following examples.

(a) Starting from dE = T dS − P dV , show that the equation of state P V = N kB T , in fact

implies that E can only depend on T .

(b) What is the most general equation of state consistent with an internal energy that

depends only on temperature?

(c) Show that for a van der Waals gas CV is a function of temperature alone.
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5. Clausius–Clapeyron equation describes the variation of boiling point with pressure. It is
usually derived from the condition that the chemical potentials of the gas and liquid phases
are the same at coexistence. For an alternative derivation, consider a Carnot engine using
one mole of water. At the source (P, T ) the latent heat L is supplied converting water
to steam. There is a volume increase V associated with this process. The pressure is
adiabatically decreased to P − dP . At the sink (P − dP, T − dT ) steam is condensed back
to water.
(a) Show that the work output of the engine is W = V dP + O(dP 2 ). Hence obtain the
Clausius–Clapeyron equation �
dP �� L
= . (1)
dT boiling
� TV

(b) What is wrong with the following argument: “The heat QH supplied at the source to
convert one mole of water to steam is L(T ). At the sink L(T − dT ) is supplied to condense
one mole of steam to water. The difference dT dL/dT must equal the work W = V dP ,
equal to LdT /T from eq.(1). Hence dL/dT = L/T implying that L is proportional to T !”
(c) Assume that L is approximately temperature independent, and that the volume change
is dominated by the volume of steam treated as an ideal gas, i.e. V = N kB T /P . Integrate
equation (1) to obtain P (T ).
(d) A hurricane works somewhat like the engine described above. Water evaporates at the
warm surface of the ocean, steam rises up in the atmosphere, and condenses to water at

the higher and cooler altitudes. The Coriolis force converts the upwards suction of the
air to spiral motion. (Using ice and boiling water, you can create a little storm in a tea
cup.) Typical values of warm ocean surface and high altitude temperatures are 800 F and
−1200 F respectively. The warm water surface layer must be at least 200 feet thick to
provide sufficient water vapor, as the hurricane needs to condense about 90 million tons
of water vapor per hour to maintain itself. Estimate the maximum possible efficiency, and
power output, of such a hurricane. (The latent heat of vaporization of water is about
2.3 × 106 Jkg −1 .)
(e) Due to gravity, atmospheric pressure P (h) drops with the height h. By balancing
the forces acting on a slab of air (behaving like a perfect gas) of thickness dh, show that
P (h) = P0 exp(−mgh/kT ), where m is the average mass of a molecule in air.
(f) Use the above results to estimate the boiling temperature of water on top of Mount
Everest (h ≈ 9km). The latent heat of vaporization of water is about 2.3 × 106 Jkg −1 .
********

6. Glass: Liquid quartz, if cooled slowly, crystallizes at a temperature Tm , and releases

latent heat L. Under more rapid cooling conditions, the liquid is supercooled and becomes
glassy.
(a) As both phases of quartz are almost incompressible, there is no work input, and changes
in internal energy satisfy dE = T dS + µdN . Use the extensivity condition to obtain the
expression for µ in terms of E, T , S, and N .
(b) The heat capacity of crystalline quartz is approximately CX = αT 3 , while that of
glassy quartz is roughly CG = βT , where α and β are constants.
Assuming that the third law of thermodynamics applies to both crystalline and glass
phases, calculate the entropies of the two phases at temperatures T ≤ Tm .
(c) At zero temperature the local bonding structure is similar in glass and crystalline
quartz, so that they have approximately the same internal energy E0 . Calculate the
internal energies of both phases at temperatures T ≤ Tm .
(d) Use the condition of thermal equilibrium between two phases to compute the equilib­

rium melting temperature Tm in terms of α and β.

(e) Compute the latent heat L in terms of α and β.

(f) Is the result in the previous part correct? If not, which of the steps leading to it is
most likely to be incorrect?
********
7. Characteristic functions: Calculate the characteristic function, the mean, and the
variance of the following probability density functions:

1
(a) Uniform p(x) = 2a for −a < x < a , and p(x) = 0 otherwise;

4
 � �
(b) Laplace p(x) = 1
2a exp − |xa| ;
(c) Cauchy p(x) = π(x2a+a2 ) .
The following two probability density functions are defined for x ≥ 0. Compute only
the mean and variance for each.
2
x x
(d) Rayleigh p(x) = a2
exp(− 2a2) ,
�
2 x2 x 2
(e) Maxwell p(x) = π a3
exp(− 2a2) .
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8. Tchebycheff inequality: Consider any probability density p(x) for (−∞ < x < ∞),
with mean λ, and variance σ 2 . Show that the total probability of outcomes that are more
than nσ away from λ is less than 1/n2 , i.e.

1
�
dxp(x) ≤ .
|x−λ|≥nσ n2

Hint: Start with the integral defining σ 2 , and break it up into parts corresponding to
|x − λ| > nσ, and |x − λ| < nσ.
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9. Optimal selection: In many specialized populations, there is little variability among
the members. Is this a natural consequence of optimal selection?
(a) Let {rα } be n random numbers, each independently chosen from a probability density
p(r), with r ∈ [0, 1]. Calculate the probability density pn (x) for the largest value of this
set, i.e. for x = max{r1 , · · · , rn }.
(b) If each rα is uniformly distributed between 0 and 1, calculate the mean and variance
of x as a function of n, and comment on their behavior at large n.
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