UNIVERSITY OF LONDON

MSci/BSc EXAMINATION 2007

For Internal Students of Royal Holloway

DO NOT TURN OVER UNTIL TOLD TO BEGIN

PH2610B: Classical and Statistical Thermodynamics Time Allowed: TWO hours Answer QUESTION 1 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

Only CASIO fx85WA Calculators or CASIO fx85MS Calculators are permitted

PH2610A/63
Royal Holloway and Bedford New College 2007 2006-07

GENERAL PHYSICAL CONSTANTS Permeability of vacuum Permittivity of vacuum

0 0
1/40

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

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

c e me mu mp mn e/me h = = h/2

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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ANSWER ONLY FIVE sections of Question One. You are advised not to spend more than 40 minutes answering Question One. 1. (a) (b) Calculate the work done on one mole of an ideal gas when it is compressed isothermally, reducing its volume by a factor 20, at 20C. The Helmholtz free energy is defined as F = E TS . Find an expression for its differential, dF. Hence derive the Maxwell relation: [4]

S p = . V T T V
(c) (d) State the first, second and third laws of thermodynamics. The Maxwell-Boltzmann distribution of particle speeds of an ideal classical gas is given by
m f (v ) = 2 k BT
3/ 2

[4] [4]

mv 2 4 v 2 exp 2 k BT

Explain the physical meaning of f(v) and sketch the function at two different temperatures. Explain, without completing a full derivation, how one goes about calculating the mean particle speed. (e) The heat capacity of a sample at low temperatures is found to be well described by Cv(T) = AT, where A = 1.5 JK 2. Find the entropy at T = 4K. Briefly discuss the phenomenon of Bose-Einstein condensation.

[4]

[4] [4]

(f)

TURN OVER

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2.

(a)

The Boltzmann distribution for a system of identical localised particles is written as

n( ) = N e . Z

Define the symbols used and explain the physical significance of n( ) . (b) If each particle has three possible energy levels , 0, write down an expression for Z. If / k B = 2 K, determine the fraction of particles in the lowest energy level at T = 1 K and at T = 10 K. Make a sketch of the fraction of particles in the lowest energy level as a function of temperature. State the Boltzmann-Planck definition of entropy. Hence state the entropy of this system in the limits kBT >> and kBT << .
B

[4]

[3]

(c)

[4] [2] [2]

(d) (e) (f)

Show that the internal energy is given by the relation E= N Z . Z

Hence, for the present system of identical localised particles with the single particle energy levels given in (b), find an expression for E, and sketch the behaviour of E/N as a function of temperature.

[5]

TURN OVER

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PH2610B
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3.

(a)

A gas is expanded adiabatically, and reversibly. Explain the meaning of these two terms, and how these conditions are achieved. Explain why the entropy of the gas is constant in an adiabatic and reversible process. By considering the entropy as a function of T and V, show that the molar entropy difference of two states for an ideal gas is given by
S (T2 , V2 ) S (T1 , V1 ) = Cv ln T2 V + R ln 2 . T1 V1

[4] [3]

(b) (c)

where Cv is the molar heat capacity at constant volume.

S p [You may assume the Maxwell relation = ]. V T T V

(d) Hence show from the expression in (c), or otherwise, that in an adiabatic reversible expansion of an ideal gas TV 1 = const. , where = C p / Cv and Cp is the molar heat capacity at constant pressure. [ You may assume the result C p Cv = R .] (e) Estimate the initial pressure required to liquefy nitrogen gas from room temperature in an adiabatic expansion. State clearly any assumptions you make. [ Liquid nitrogen boils at 77 K].

[8]

[3]

[2]

TURN OVER

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PH2610B
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4.

(a)

Describe the Carnot cycle in detail. Obtain an expression for the efficiency of a Carnot engine. Describe how a Carnot cycle may be operated as a heat pump. An air-conditioning unit maintains the temperature of a laboratory at 21C, when the outside temperature is 27C. Running all the equipment in the laboratory generates 10 kW of heat. Estimate, clearly stating any assumptions you make, the minimum power consumption of the airconditioning unit.

[10] [2]

(b) (c)

[4]

(d)

An engine operates using the reversible cycle shown, where cd and ab are adiabats. It uses an ideal monatomic gas as the working substance. Let the temperature at each of the points a,b,c,d be Ta, Tb, Tc, Td respectively. By carefully considering the cycle show that
Q2 V1 = Q1 V2
1

, where = C p / Cv . [4]

Hence calculate the efficiency, if the compression ratio V2/V1= 10.

TURN OVER

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5.

(a) (b)

Discuss briefly the distinguishing features of a particle, which determine whether it is a boson or a fermion. Define the Fermi-Dirac distribution function n ( ) for an ideal gas of fermions, and write down its form, defining the symbols used. Discuss the energy dependence of the Fermi-Dirac distribution function n ( ) at T = 0 and how it changes with increasing temperature. Explain what is meant by the term energy density of states. Show that the heat capacity of an ideal free electron gas in a metal is proportional to temperature, at the lowest temperatures, and that it is much smaller than that of a classical gas of the same density. Using the information below show that the bulk modulus of a free 2N electron gas is given by B = EF . 3V Hence estimate the contribution of the electrons to the bulk modulus of potassium, and show that it is comparable to the measured value (2.8109 Nm-2). You may assume the following: (i) The energy density of states is given by g ( ) = where the Fermi energy EF =
=2 2 N 3 2m V
2/3

[4]

[3]

(c)

[3] [2]

(d) (e)

[4]

(f)

[4]

3 N 1/ 2 , 3/ 2 2 EF

(ii)

At T << EF , the internal energy E =

3 NEF . 5 dE , and dV

(iii)

Pressure exerted by the electron gas is given by p = the bulk modulus B = V

dp . dV

(iv)

N = 1.4.1028 m-3 and EF = 2.1 eV for potassium. V

END