UNIVERSITY OF LONDON MSci/BSc EXAMINATION 2008

For Internal Students of Royal Holloway

DO NOT TURN OVER UNTIL TOLD TO BEGIN

PH2610 : CLASSICAL AND STATISTICAL THERMODYNAMICS PH2610R : CLASSICAL AND STATISTICAL THERMODYNAMICS - PAPER
FOR RESIT CANDIDATES

Time Allowed: TWO hours

Answer QUESTION ONE and TWO other questions.

No credit will be given for attempting any further questions.

Approximate part-marks for questions are given in the right-hand margin

Calculators will be provided

Royal Holloway and Bedford New College 2008

2007 -08

GENERAL PHYSICAL CONSTANTS Permeability of vacuum Permittivity of vacuum

0 0
1/40 c e me mu mp mn e/me h = = h/2

= = = = = = = = = = = = = = = = = = =

4 10-7 8.85 10-12 9.0 109 3.00 108 1.60 10-19 9.11 10-31 1.66 10-27 1.67 10-27 1.67 10-27 1.76 1011 6.63 10-34 1.05 10-34 1.38 10-23 5.67 10-8 8.31 6.02 1023 6.67 10-11 9.81 2.24 10-2 1.01 105

H m-1 F m-1 m F-1 m s-1 C kg kg kg kg C kg-1 Js Js J K-1 W m-2 K-4 J mol-1 K-1 mol-1 N m2 kg-2 m s-2 m3 N m-2

Speed of light in vacuum Elementary charge Electron (rest) mass Unified atomic mass constant Proton rest mass Neutron rest mass Ratio of electronic charge to mass Planck constant

Boltzmann constant Stefan-Boltzmann constant Gas constant Avogadro constant Gravitational constant Acceleration due to gravity Volume of one mole of an ideal gas at STP One standard atmosphere

R NA G g

P0

MATHEMATICAL CONSTANTS e 2.718 3.142 loge10 2.303

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PH2610
PART MARKS

1.

(a)

Starting from the differential form for the Helmholtz function

dF = SdT PdV
show that

S P = . V T T V
(b) Show that the general expression

[4]

P V C P CV = T T V T P
gives the particular result
C P CV = R

for one mole of ideal gas. (c) Calculate the total entropy change when a copper block of mass 0.4 kg, heat capacity 386 J kg-1 K-1, at 100 C is placed in a lake at 10 C. Calculate the entropy change when the same block at 10 C is dropped 100 m into the lake. (d) The Maxwell-Boltzmann distribution of particle speeds for an ideal classical gas is given by

[4]

[4]

mv 2 m 2 2 n(v ) = 4 v exp , 2kT 2kT where v is the speed, T is the temperature, m is the molecular mass and k is the Boltzmann constant. Sketch this distribution, indicating the approximate positions of the mean speed, the root-mean-square speed, and the most probable speed. Calculate the most probable speed of oxygen at room temperature. [The molecular mass of oxygen is 32 atomic mass units.] (e) State the Boltzmann definition of entropy of an isolated system in terms of the number of accessible microstates. Use this equation to express the second and third laws from a microscopic perspective. Define the Fermi-Dirac distribution function n(i) writing down its form. Sketch n(i) at T=0.

[4]

[4]

(f)

[4]

TURN OVER

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PH2610
PART MARKS

2.

(a) (b)

State briefly the principal features of a Carnot engine. State Carnots theorem. Briefly outline how this enables us to set up an absolute scale of temperature?

[2]

[4]

(c) (d)

Draw a diagram showing the heat and work transfers of a refrigerator, and state the appropriate measure of performance R. Determine R as a function of the temperature of the surroundings T1 and the temperature of the cold body T2 for a Carnot engine operating in reverse. Can R be greater than one?

[4]

[5]

(e)

A refrigerator requires 66.6 kJ of work to freeze 1 kg of water at 273 K when the temperature of the surroundings is 300 K. What is the efficiency R of the refrigerator? Is the operation of the refrigerator reversible? [The specific latent heat of fusion of water is 333 kJ kg-1.]
[5]

TURN OVER

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PH2610
PART MARKS

3.

(a) (b)

State the third law of thermodynamics. What distinguishes a first order phase transition? What happens to the entropy during such a transition? Give an example of a first order phase transition.

[1]

[3]

(c)

The specific Gibbs free energies are equal when two phases are in equilibrium at a phase boundary in the P-T plane. By considering two neighbouring points on this phase boundary, derive the ClausiusClapeyron equation
dP L = , dT TV

where L is the molar latent heat and V is the difference in molar volume of the two phases. (d) (e) What is the gradient of the phase boundary in the limit of zero temperature? Helium remains liquid at ambient pressure and absolute zero temperature, and pressure has to be applied to form a solid. Sketch on separate P-T diagrams the fusion curves for 4He and 3He. Explain the temperature dependence of the gradients of the phase boundaries in each case in part (e).

[6] [2]

[4]

(f)

[4]

TURN OVER

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PH2610
PART MARKS

4.

(a)

The Boltzmann distribution for the system of N identical localised particles is written as
n( i ) = N i e . Z
[6]

Define the symbols used and explain the physical significance of n(i). (b) A crystal of paramagnetic salt contains a large number N of noninteracting spin particles. Determine the partition function for this paramagnetic solid. Show that the entropy of the body in a field B is given by

[3]

(c)

B B B S = Nk ln 2 + ln cosh tanh . kT kT kT
(d) Use your expression from part (c) to find the limiting values of the B . entropy for large and small kT Explain why these values are expected for a two-state system. (e) Explain, using the equation from part (c), the principles of cooling by adiabatic demagnetisation. Explain why reducing B to zero does not cause T to fall to zero.

[5]

[3]

[3]

TURN OVER

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PH2610
PART MARKS

5.

(a) (b) (c)

Define the Bose-Einstein distribution function, explaining the symbols used and their physical meaning. Explain why the gas of photons can be treated as a gas of bosons with chemical potential equal to zero. The number of photons with wave vector in the range k to k+dk is given by
g (k )dk = V

[4] [2]

k 2 dk .

Show that the energy spectrum is given by

V= 3 U ( ) = 2 3 = . c kT e 1
(d) Sketch the form of U() for black body radiation at two different temperatures. How do the peak frequency and area under the curve vary with temperature? (e) According to Hubbles law, the Universe has been expanding at a constant rate since the big bang about 1.31010 years ago. Interstellar space is now filled with cosmic background black body radiation at T = 2.735 K, and it can be shown that during this expansion volume and temperature are related by
VT 3 = const .

[5]

[4]

How does temperature vary with time? Estimate the temperature of the cosmic background radiation when the earth was formed 4.7109 years ago.
[5]

END