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388

Statistical Mechanics

change in temperature scale; it is sho:vn as the dotted curve of Figure 27-3b. And finally the metastable mixture of i orthodeuterium plus 1 paradeuterium, obtained by cooling deuterium gas without the presenc! of a catalyst, is given by the formula

1

a2

a 2

] (27-23)

Cvt = NkT

[

3aT 2 (T ln z;ot) + 3aT 2 (T ln z~at)

2

(metastable mixture)

and is shown, for Orat = 43°K, as the solid line of Figure 27-3b. All of these curves are verified by experimental data, taken under the different conditions, appropriate for the three cases. Thus the effects of quantum statistics turn up in odd corners of the field, at low temperatures and for substances a part of which can gaslike to low enough temperatures for the effects of degeneracy to become evident. For the great majority of substances and over the majority of the range of temperature and density, classical statistical mechanics is valid, and the calculations using the canonical ensemble of Chapters 19 through 22 quite accurately portray the observed results. The situations where quantum statistics must be used to achieve concordance \Vith experiment are in the minority (luckily; otherwise our computational difficulties would be much greater). But, when they are all considered, these exceptional situations add up to exhibit an impressive demonstra- tion of the fundamental correctness of quantum statistics. They are some of the aspects of reality, mentioned at the beginning of Chapter 16, the explanation of which is the sole justification for the theoretical super- structure of statistical mechanics discussed in these last twelve chapters.

PROBLEMS

Chapter 2

2-l. The amount of heat !::.Q added to a unit mass of some homogeneous material raises its temperature by an amount !::.T, where !::.Q = cmi::.T, Cm being the heat capacity of the material per unit mass. A temperature gradient in the material will produce a heat flow J heat units per second per unit area perpendicu- lar to the flow. The relationship is J = - Kr grad T, where Kr is the thermal conductivity of the material. Use the equation of continuity for fluid flow to

relate the divergence of J to the time rate of change of Q and therefore of T. From this obtain the differential equation for the temperature distribution in the material, as a function of x, y, z, and t, in terms of em, K1·, and p, the density of the material. 2-2. Suppose that all the atoms in a gas are moving with the same speed v, but that their directions of motion are at random.

(a) Average over directions of incidence to compute the mean number

of atoms striking an element of wall area dA per second (in terms of N, V, v, and dA) and the mean momentum per second imparted to dA.

(b) Suppose, instead, that the number of atoms having speeds between

v and v + dv is 2N[1 - (vfvm)](dvfvm) for v < Vm (the directions still at random). Calculate for this case the mean number per second striking dA and the mean momentum imparted per second, in terms of N, V, vm, and dA. Show that Eq. (2-4) holds for both of these cases. 2-3(a) For a perfect gas of point particles the mean kinetic energy per particle (K.E.)tran is a function f(T) of the temperature T. Thus any change in temperature will produce a change in the internal energy U of the gas. But an addition of heat !::.Q produces an increase !::.T in temperature; by definition the relationship is !::.Q = C !::.T, where Cis the heat capacity of the gas. Therefore, for the gas of Eq. (2-1), an addition of heat is equivalent to an increase in internal

energy of the gas. If !::.Q is expressed in the same energy units (joules) as U, what is the equation relating em, the heat capacity per unit mass of the gas, to N m, the number of molecules per unit mass and f', the slope of f( T)?

(b) When there is a temperature gradient in a substance there cannot

be thermodynamic equilibrium because heat is flowing (see Problem 2-1). There can be mechanical equilibrium, however, if the pressure is uniform throughout the material. Suppose the material is a perfect gas of point particles, and sup- pose the temperature gradient is small enough so that Eq. (2-4) holds at each point in the gas, with (K.E.)tran = f(T). What must be the value of the gradient of the density p of the gas, in terms of the gradient of T, of p, em and U, for there to be mechanical equilibrium?

389

390

Chapter 3

3-l.

Thermodynamics

The coefficient of thermal expansion {3 and the compressibility K

of a substance are defined in terms of partial derivatives

f3 =

(1/V)(av;aT)p

(a) Show that

(a{3jaP)r =

and that

-(aKjaT)p

K =

-(1/V)(av;aP)r

({3/K) =

(aP;aT)v

for any substance.

(b)

What are the values of {3 and K and (aPjaT)v for a perfect gas?

For a substance with the virial equation of state given by Eq. (3-5)?

{3

=

3-2.

It is found experimentally that, for a given gas,

RVZ(V- nb)

R=T=v::-;:a-_---'="2-an-(:-:oV=--'---n--=b:-:-:)2

VZ(V- nb)2

K = ----~~----~-----

nRTV3 -

2an 2 (V -

nb) 2

where a and b are constants, and also that the gas behaves like a perfect gas for

large values of T and V.

Partial derivatives analogous to the coefficient of thermal expan-

sion and the compressibility can be defined for the magnetic equation of state,

Find the equation of state of the gas.

3-3.

am= -(1/9R)(aiJ)(jaT)~

Find the expressions for these quantities for substances obeying Curie's law,

Eq. (3-8).

Also find (aS)jaT) 911.

3-4.

A gas obeys equation of state (3-4).

Show that for just one

critical state, specified by the values T, and V" both (aPjaV)r and (a 2 PjaV 2 )r

are zero.

Plot three curves for P jP, as a function of V V,, one forT = ~T,, one for T = T" and one for T = 2T,. What happens physically when the equation indicates

three allowed values of V for a single P and T?

From Figure 3-3 estimate the volume of a mole of COz at 300°K

and 20 atmospheres. A mole of steam at 600°K occupies 1.4 cubic meters; what

Write the equation of state giving P jP, in terms of T T, and V V,.

3-5.

is its pressure in atmospheres?

parallel-plate condenser,

calculate the work done by a homogeneous, isotropic dielectric in terms of the volume v of the dielectric and the uniform electric field ~ applied, when the

electric polarization of the dielectric changes by dll3.

3-6(a)

By

considering

the

charging

of

a

(b) It is found experimentally that

(a~jall3)r = [T/(AT +B)]

and

(a~jaT)m =

[Bil3/(AT + B)2]

Compute ('all3jaT) 1\: and, by integration, obtain the equation of state, ll3 as a

function of ~ and

T.

3-7.

Express the van der Waals equation of state (3-4) in the form of

the virial equation (3-5).

Find B(T) and C(T) in terms of a, b, and T.

Problems

391

Chapter 4

energy

4-I.

A gas with van der Waals equation of state (3-4) has an internal

U = jnRT- (an 2 /V) + U 0

Compute Cv and CP as functions of V and T and computeT as a function of V for an adiabatic expansion. 4-2. An ideal gas for which Cv = tnR and (aU jaV)r = 0 is taken from point a to point bin Figure P-1, along three paths, acb, adb, and ab, where

P2 =

2PJ,

V2

=

2VJ.

(a) Compute the heat supplied to the gas, in terms of n, R, and T 1 , in

each of the three processes.

(b) What is the heat capacity of the gas, in terms of R, for the process

ab?

FIGURE

P-1

. 4-3. A par~magnetic solid, obeying Eqs. (3-6), (3-8), and (4-8) and

havmg a heat capacity C.911 = nAT 3 , is magnetized isothermally (at constant

volume) at temperature To from 9)( = 0 to a maximum magnetic field of ·~m· How much heat must be lost? It is then demagnetized adiabatically (at con-

~tant volume) to IJJC = 0 again. Compute the final temperature T 1 of the solid,

m terms of S)m, To, A, and D. How do you explain away the fact that, if S)m is large enough or To small enough, the formula you have obtained predicts that T1 should be negative? 4-4. Derive equations for (aU;aT)P and (aU ;aP)r analogous to E~s. (4-4) and (4-6). Obtain an expression for (aHjaP)r. For a perfect gas, wrth. CP = tnR and (CP- Cv)j(aVjaT)p = P, integrate the partials of H to obtam the enthalpy.

4-5. Figure P-2 shows a thermally isolated cylinder, divided into two parts by a thermally insulating, frictionless piston. Each side contains n moles

of a perfect gas of point atoms. Initially both sides have the same temperature;

392

Po

Po

To

To

Vo

Vo

FIGURE

P-2

Thermodynamics

heat is then supplied slowly and reversibly to the left side until its pressure has

increased to (243P o/32).

Problems

3
3

0

393

(a)

How much work was done on the gas on the right?

FIGURE

P-3

(b)

What is the final temperature on the right?

(c)

What is the final temperature on the left?

(d)

How much heat was supplied to the gas on the left?

(a)

Express fiCa in terms of Th,

T.,

D,

C,

and

ffi12 and relate

ffi1 4

4-6. The ratio CP/Cv for air is equal to 1.4. Air is compressed from room temperature and pressure, in a diesel engine compression, to 1/15 of its

original volume. Assuming the compression is adiabatic, what is the final

temperature of the gas?

Find the relationship between T and V for the reversible, adiabatic

compression of a gas obeying van der Waals equations (3-4) and having a heat

Use the

capacity at constant volume C. which is independent of T and of V.

value of U given in Problem 4-1 to obtain Cp and thence 'Y =

0, satisfies the virial equation of

.

.

.

4-7.

(Cp/C.).

4-8.

A gas, for which (oU jaV)r =

state (3-5), with B and C independent of T.

.

.

.

(a) How much heat must be supplied to expand the gas, m a quas1statlc,

isothermal process, from volume V1 to volume Vz?

Cv) between the heat capamtles of

this gas in terms of T and V.

At low temperatures the heat capacity at constant volume of

NaCl is proportional to the third power ofT in degrees Kelvin; C. = 0.0874 n ra

joulesjkg-deg K.

Compare the

(b) Express the difference (CP -

4-9.

(a)

At

high

temperatures

C. = 3nR approximately.

high-temperature value with the value at T = 50°K.

(b) How much heat is required to raise the temperature of a mole of

NaCl from 25°K to 50°K?

Chapter 5

5-I.

Compute ~Q 12 and ~Q 4 a, for a Carnot's cycle using a perfect gas

of point particles in terms of nR and Th and T

temperature sho~ that ~W 23 = - ~W 41

Using the perfect-gas scale of

Show that the efficiency of the cycle

T.)./Th and thus prove that the perfect-gas temperature scale coincides

is (Th

-

with the thermodynamic scale of Eq. (5-5).

5-2.

A magnetic material satisfying Eqs. (4-8) and (3-8) has a. con~tant

heat capacity, Cv!ln = C. It is carried around a Carnot cycle shown m !1gur:e P-3 ffiC being reduced isothermally from ffi11 to ffiCz at Th, then reduced adiabatl- call~from 9)C 2 to fiCa, when it has temperature T., then remagnetized isothermally

at T. to ffi1 4 , and thence adiabatically back to Th and ffi11.

similarly with ffiC,.

(b) How much heat is absorbed in process 1-2? How much given off

in process 3-4?

(c)

How much magnetic energy aW is given up by the material in

each of the four processes? Show that aW 2a = - aW 41·

(d) Show that the efficiency of the cycle heat-magnetic-energy is

(Th- T.)/Th.

When a mole of liquid is evaporated at constant temperature T

and vapor pressure P .(T), the heat absorbed in the process is called the latent

heat Lv of vaporization. A Carnot cycle is run as shown in Figure P-4, going isothermally from 1 to 2, evaporating n moles of liquid and changing volume from VI to v2, then cooling adiabatically to T - dT, Pv - dPv by evaporating an additional small amount of liquid, then recondensing the n moles at T - dT,

from

5-3.

Va to V 4 , and thence adiabatically to Pv, T again.

(a) Show that V2 - V1 = V 0 - Vz where V 0 is the volume occupied

by n moles of the vapor, and Vz the volume of n moles of the liquid.

(b) Find the efficiency of the cycle, in terms of dPv, V 0 - Vz, and nLv.

(c) If this cycle is to have the same efficiency as any Carnot cycle, this

 

P.

T

V

 

vapor

 

- --

 

,

 

-

-

--- -

 

liquid::_::::

--

--

=---=- --

t

p

Pv

Pv- dPv

 

T

2

\

\

4

T

dT

3

VI

v2

P-4

FIGURE

.394

Thermodynamics

efficiency must be equal to (Th - Tc)/Th = dT jT.

sions for efficiency, obtain an equation for the rate of change dPv/dT of the

vapor pressure with temperature in terms of Va- V1, n,.Lv, ar:d T.

In the tropics the water near the surface IS considerably warmer

than the deep water. Would an engine operating between these two levels

violate the second law?

Electromagnetic radiation in an evacuated vessel of volume V,

at equilibrium with the walls at temperature T, behaves like a gas of photon~, having internal energy U and pressure P: U = aVT 4 , P = .fsaT4, where a IS

Equating the two expres-

5-4.

5-5.

Stefan's constant [see Eq. (7-8)].

(a) Find the relation between P and V for an adiabatic process and

the relationship between heat absorbed and change of volume in an isothermal

process, for this gas.

(b) Plot the closed curve, on the P

(c) Compute the heat absorbed and the work done in each part of the

V plane, for a Carnot cycle.

-

cycle and prove that the efficiency is [(Th- Tc)/Th].

Prove that it is impossible for two quasistatic adiabatics to inter-

sect.

Suppose we desire to use a temperature scale r

efficiency deficit function'¥ of Eq. (5-2) is a subtractive function of r, 'l'(rh - rc).

such that the

5-6.

(Hint: show that the second law is violated if they do.)

5-7.

(a) Show that the thermodynamic temperature T is an exponential

function of r.

(b) If we wish r to be zero at the melting-point of ice and to be 100 at

the boiling point of water, what is the exact functional relationship between T and

r?

What value of r corresponds to T = 0?

(c) What are the equation of state and the heat capacities Cv and CP

for a perfect gas of point atoms in terms of the r scale?

An ideal gas, satisfying Eqs. (4-7) and (4-12) is carried around the

cycle shown in Figure P-5; 1-2 is at constant volume, 2-3 is adiabatic, 3-1 is at

constant pressure, V 3 is 8V 1 , and n moles of the gas are used.

5-8.

is 8 V 1 , and n moles of the gas are used. 5-8. (a) What

(a)

What are the heat input, heat output, and efficiency of the cycle, vb n, and R?

cycle

Compare

in terms of PI,

(b)

this

efficiency with the efficiency of a

Carnot

operating between the same extremes of temperature.

Chapter 6

An amount of perfect gas of one kind is in the volume C1 V of

Figure P-6 at temperature T and pressure P, separated by an impervious dia-

6-l.

Problems

395

P,

T,

c1v

D

P,

T,

c2v

FIGURE

P-6

phragm D from a perfect gas of another kind, in volume C2V and at the same

pressure and temperature (C 1 + C 2 = 1). The volume Vis

What is the entropy of the combination? Diaphragm D is then ruptured and

the two gases mix spontaneously, ending at temperature T, partial pressure

of the first gas, C 2 P of the second gas, all in volume V. What is the entropy now?

Devise a pair of processes, using semipermeable membranes (one of which will pass gas 1 but not 2, the other which will pass 2 but not 1), which will take the system from the initial to the final state reversibly and thus verify the change in entropy. What is the situation if gas 1 is the same as gas 2? 6-2. Two identical solids, each of heat capacity Cv (independent of T), one at temperature T + t, the other at temperature T- t, may be brought to common temperature T by two different processes:

(a) The two bodies are placed in thermal contact, insulated thermally

What is

the change of entropy of the bodies and of the universe caused by this process?

(b) First a reversible heat engine, with infinitesimal cycles, is operated

between the two bodies, extracting work and eventually bringing the two to

common temperature. Show that this common temperature is not T, but

and what is the entropy change in

this part of process b? Then heat is added reversibly to bring the temperature of the two bodies to T. What is the entropy change of the bodies during the whole of reversible process b? What is the change in entropy of the universe? 6-3. Show that T dS = Cv dT + T(aPjaT)v dV and that T dS = Cv(aTjaP)v dP + CP(aTjaV)P dV. 6-4. A paramagnetic solid, obeying Eqs. (3-6), (3-8), and (4-8), has a heat capacity Cpo(T) (at zero magnetic field) dependent solely on temperature. First, show that

from the rest of the universe and allowed to reach T spontaneously.

isolated thermally.

C 1 P

V(T 2 -

t 2 ).

What is the work produced

T dS

=

Cps;, dT-

T(aVjaT)p dP + T(aiJJtjaT)s;, d~

and, analogous to Eq. (8-13), that (aCps;,ja~)rp = show that

T(a 2 1JJtjaT 2 )s;,.

From this,

S

=

loT (Cpo/T) dT -

.JtnD(~jT)2- {3VoP

and thence obtain energy U as a function of T, P, and~. ObtainS as a function of T, V, and IJJt and thence obtain U as a function of T, V, and IJJt. 6-5. Express the entropy and the volume of a perfect gas of point atoms in terms of its pressure and temperature. Then integrate the Gibbs- Duhem Eq. (6-9) to obtain the chemical potentialp. of a mole of the gas. 6-6. At very low temperatures the entropy, magnetization, and internal energy of the atomic magnets in a paramagnetic crystal are fairly accurately

396

represented by the equations

396 represented by the equations where Thermodynamics and where Rm, {3, and Tm = 0.2°K are

where

396 represented by the equations where Thermodynamics and where Rm, {3, and Tm = 0.2°K are

Thermodynamics

396 represented by the equations where Thermodynamics and where Rm, {3, and Tm = 0.2°K are
396 represented by the equations where Thermodynamics and where Rm, {3, and Tm = 0.2°K are

and where Rm, {3, and Tm = 0.2°K are constants.

Compute (aff)jaT)IJJI and thence find (aUmja'illC)r as a function of

~and T. Plot it as a function ofT for 0 < T < 5T m for fO = 0 and for f3f0 = 2.

What does this predict regarding the relation between heat absorbed and rate of gain of um in an isothermal process?

of

{3~ = 2. Use these curves to recapitulate the arguments regarding the third law of thermodynamics. Roughly, what temperature can be reached by starting at T = 1°K, fO = 0, increasing to f3f0 = 2 isothermally and then reducing to fO = 0 isentropically? How much further could you go in two more such steps? How much in eight more steps?

0 < T < 5T m for fO = 0 and

(a)

(b) Plot

Sm

as

a function

T for

Chapter 7

7-l. A gas obeys the virial equation of state (3-5) with B and C independent of T and its heat capacity at constant volume C. = lnR. Compute the Joule-Thomson coefficient (aTjaP)H as a function ofT and V. Does this gas have an inversion point? 7-2. The Stirling cycle consists of two isothermal processes, at Th and

Tc and two processes at constant volume, as is shown in Figure P-7. The characteristics of the cycle depend on how the heat is transferred to and from the engine during the constant-volume parts of the cycle.

(a) Consider first the case where only two heat reservoirs are aYailable,

at temperatures Th and Tc. Find the entropy change of the universe for s"~ction 41 of the cycle.

(b) Show that this change is always positive.

t p
t
p

2

3

0

v-

FIGURE

P-7

Problems

397

(c) Jus~ify the use ~f the word ~fficiency for the fraction (net work)/ llQ

12

Fmd the efficiency, so defined, for this cycle, assuming

of Eq. (5-1) fo: this cycle.

that the workmg substance is a perfect gas of point atoms.

(d) Now suppose that a continuous set of heat reservoirs, for every

temperature between Tc and Th, is available, so that 23 and 41 can be traversed

reversibly.

(e) In view of your answers to (c) and (d), explain the detrimental

effect of the increase in entropy in the former case.

What now is the efficiency of the cycle?

7-3. A .ve:y ap~roxima~e set of formulas for the entropy and density of the normal flmd ~n helmm II IS sn = 1600 joules/kg deg (which thus equals the entropy per umt mass of the whole fluid sx at the transition point) and Pn = p(T/Tx) 4 , where P = Pn + Ps = 144 kg/m 3 is the density of the whole fluid and where Tx = 2.2°K is the temperature of the transition point.

(a) Enough heat is supplied to the coil H of Figure 7-2 to make the

temperature 1.2°K, whereas the temperature outside the vessel is 1.1 °K. What

is

atmospheres?

the velocity of second

outside of the vessel, in

the

pressure

(b)

difference

between

the inside and

Using

the formula

(p,pns~Tjp 2 c) 1 ' 2 , plot

sound versus T for the range iTx < T < Tx.

. 7-4.

Show: that, when temperature T and applied magnetic field ff) are

Um- ~WC, and thus that Hm is the magnetic heat content of the

the mdependent vanables, the heat capacity for constant fO is Cs;;, = (aHmjaT),

where Hm =

material at constant applied field.

Find Cs;;, for a material obeying Curie's law and having a heat

capacrty for constant magnetization CIJJI = [nRmT 2 /(02 + T2)]. What is the

entropy of this material? Can this formula be correct down to T = 0?

Plot it, as a function of

Show that for T much greater

than both T m and {3f{)T m this material obeys Curie's law and that its Cs;;, is inversely proportional to T2.

. (a)

(b) Find Cs;;, for the material of Problem 6-6.

< T

< 5T m, for f3ff) =

0 and for f3f0 =

2.

T

for 0

Chapter 8

. 8-l. The tension J in a plastic rod, stretched to a length L, at tempera- ture T, IS J =: A(T)(L - Lo), where Lois independent of T. Its heat capacity at constant£ IS CL = C(T)- M(T)N(L), where N = 0 when£= L 0 and where MN «Cover the range of interest of T and L.

(a) . Show .th~tM(T)N(L) = iTA"(T)(L -

L 0 ) 2 , where the primes on

What is the heat capacity of the

. .

A mdicate drfferent~atwn with respect to T. rod at constant tension?

 

(b)

Compute the entropy of the rod, as function of T and L, if S ~ 0

as

T

0.

What does this require of function A (T)?

 

.

. (c) Fi~d the rate of change (aT;aL), of the temperature of the rod for

adiabatic stretchmg. If the temperature rises when the rod is stretched adiabati- cally, does the.en.tropy increase or decrease as the rod is stretched isothermally? What does this mdicate about the change in the amount of disorder of the molecules of the rod on stretching?

(d) Compute the internal energy U of the rod and then compute

F

to T and Land show that they equal -Sand J, respectively.

Calculate the partials ofF with respect

=

U -

TS as a function of T and L.

398

Thermodynamics

8-2. A gas obeys the van der Waals equation of state (3-4) and has

heat capacity at constant volume Cv = jnR. Write the equation of state in terms of the quantities t = T /T., p = P /P., and v = V jV., where T. = 8ajZ7 Rb,

V. = 3nb (see Problem 3-Z). Calculate T.S/PY. in terms of t

and v, likewise F /P. V. and G/P. V Fort = t plot pas a function of v from the equation of state. Then, for the same value of t, calculate and plot G/P. V. as a function of p, by graphically finding v for each value of p from the plot, and then

computing G/P. V. for this value of v (remember that for some values of p there are three allowed values of v). The curve for GjP. V. crosses itself. What is the physical significance of this?

8-3. The work done by a homogeneous, isotropic dielectric for a small change of electric polarization is - v~ dlj3, where ~ is the applied electric field strength and lj3 is the polarization, if the field is uniform.

P.

= ajZ7b 2 ,

(a) Find the Maxwell relations for this case. Assume constant V.

(b) Find the heat supplied to the dielectric when a parallel-plate

condenser is charged isothermally to a final field strength ~ 0 The dielectric obeys the law lj3 = [a + (b/T) ]~. Interpret your result in terms of entropy and disorder.

8-4.

The Gibbs function of a nonideal gas is

G = nRT ln P + P[nb- (najRT)] + j(T)

where a and bare constants and f is a function of T only. Find the equation of state and show that it agrees with the van der Waals equation of state if second-

order terms in a and b are neglected. pressure.

Compute the heat capacity at constant

8-5. Find the magnetic Gibbs function and the magnetic Helmholtz function for the material of Problem 6-6. Calculate expressions for the partials

(aTjaf)). and (aTjaf))u as functions ofT and f).

8-6.

The equation of state and the heat capacity of a gas are

= RT[(njV) + (njV) 2 B(T)]

= RT[(njV) + (njV) 2 B(T)]
= RT[(njV) + (njV) 2 B(T)]

P

Cv

=

jnR -

d

(n 2 R/V) dT (T 2 B')

where B'(T) = (dBjdT) and where the second term in the brackets is small compared to the first term for the useful range of T and V.

(a) Show that the second term in the expression for Cv must be

present if the equations are to be self-consistent. Compute Cw

(b)

ComputeS and U and show that (aU/aV)r is not zero.

(c)

Compute F, H, and Jl., all as functions of T and V.

8-7.

The Helmholtz function for a homogeneous, isotropic solid is

F =

(1/ZKoVo)(V- Vo)2 + 3nRT ln { 1- exp (- ~) [1 + a(Vo- V)]}

where R, Ko,

Vo, a, and Oo are independent of T and V.

(a) Compute the equation of state and thence find the compressibility

and the coefficient of thermal expansion

K= -(1/V)(av;aP)r

f3 = (1/V)(av;aT)p

Problems

399

(b) Compute the entropy S and the internal energy U of the solid.

Plot (Sj3nR) as a function of (T/Oo) from 0 to Z, for a(Vo- V) = 0 and = 0.5. Is this set of formulas consistent with the third law?

(c) Calculate the expressions for (aTjaV)u and (aTjaV)s.

(d)

Compute the heat capacities Cv and Cp.

0 0 and T >> () 0 ?

formulas for T «

What are their limiting

and

V,

8-8.

Express the entropy of the gas of Eq.

T,

and

V.

(8-ZZ) in terms of n, U,

Then show that the entropy parameters

rather than n,

Fo = (aSjaU)vn = (Jl./T).

=

(1/T),

Fv = (aSjaV)un =

(P/T),

and

Fn = (aSjan)uv

8-9. Use Eqs. (8-48) to show that, when electric current J. flows through a junction between a w!re of material A to one of material B, all kept at constant temperature T, heat Js evolved.

where G is the

Gibbs function.

osmotic process were reversible.

. (~) The gas diffusing through the porous partition is a perfect gas of

p~mt partwl.es. From Eqs. (8-4Z) devise an experiment to measure q indirectly

without havmg to measure Q or K or grad P. What is the formula for q in terms of the quantities measured?

8-lO(a)

Show that the enthalpy H = G- T(aGjaT)P

Thus show that q in Eq. (8-38) would be zero' if the thermo-

Chapter 9

9-l.

Assume that near the triple point the latent heats L

and L

are independent of P, that the vapor has the equation of state of a pe;fect gas:

that the volume of a mole of solid or liquid is negligible compared to its vapor ~olume, and that the difference Vz - V. is positive, independent of P or T, and IS small compared to nLm/T. Using these assumptions interrrate the three Clausius-Clapeyron equations for the vapor-pressure sublimati;n-pressure and melting-point curves. Sketch the form of these curv~son the P-T plane. '

. 9-2. The heat of fusion of ice at its normal melting point is 3.3 X 10 5

JOules/kg a~d t~e specific volume of ice is greater than the specific volume of water at this pomt by 9 X I0- 5 m 3 /kg. The value of (1/V)(aVjaT)P for ice is

16 X 10- 5

m 2 /newton.

per

degree

and

the

value

of

-(1/V) X (aVjaP)T is

lZ

x

10-11

iso-

thermally.

(b) Ice at -2'C and atmospheric pressure is kept in a container at

constant volume and the temperature is gradually increased. Find the tem- perature at which the ice begins to melt.

(c) Ice at -zoe and atmospheric pressure is compressed adiabatically.

(a)

~ce at

-zoe and

at

atmospheric

pressure

is

compressed

Fmd the pressure at which the ice starts to melt.

At what pressure will the ice melt?

9-3. Obtain an expression for the fraction (flU /nL) of the latent heat of evaporation, which goes into a chancre of internal eneray in the chano·e of

phase, in terms of Pv, T, and (dPv/dT). transition from water to ice at 0°C?

What is the value of this fraction fo~the

9-4.

?-5.

The sp~cific he~t of ice, near the melting point, is Z100 joules/kg

How much does the heat of fusion

deg and that of water IS 4ZOO JOUles/kg deg.

of ice change with

an increase of pressure of 10 atm?

!t mass m of water, originally at temperature Th, is placed inside

The refrigerator operates between the water and the

an electnc refngerator.

400

Thermodynamics

room at T which may be considered as a heat reservoir. The water is frozen and the icehis cooled further to a temperature To. The sp.ecific heats Cw and c; of water and ice may be considered as a con;;tant over this temperat_ure range. Find the minimum amount of elec.trical ener~:y that must b: s~pphed to the refrigerator for this process. What IS the numencal value of this mJmmal energy, in kilowatt-hours, if m = 1 kg, Th = 27aC, and To= -23°C? 9-6. The temperature of a long vertical column of a certam matenal is everywhere equal. When this tem~erature is To the. mat~ria~ b~lo': a certain point in the column is found to be ~ohd; that ~bo:ve ~h1~ pomt IS ~Iqmd. When the temperature is reduced by 0.2 C the sohd-hqmd m~erf~ce IS ob~erved to shift upward by 0.5 m. The heat of fusion of the ~aterialis.10,000 JOUle~/~g and the density of the liquid is 1000 kg/m 3 What IS the d.e~sity.of the solid. m the vicinity of the interface? (Hint: the pressure at the ongmal mterface pomt is not changed by the temperature change.) 9-7. Show that (oTc/oP)~, = (Tc/nLc)(Vn- V.) for a superconductor, where T is the transition temperature at pressure P, and where Vn and V, are the

volumesc of the normal and the superconducting phases.

.

9-8.

The

magnetic

field

.Pc

for

superconductive

transition,

for

a

particular material, depends on T as follows:

.Pc =

3) 0 [1- (1- a)(T/To) 2 -

a(T/To)3]

Its heat capacity, in the superconductive phase, at very low temperatures, goes to zero quadratically with T,

Cc

=

{32V(T/To)2 + f3aV(T/To)3 +

Show that the heat capacity of the normal phase (for 5) > .Pc) at low tempera- tures must depend on T as follows:

.Pc) at low tempera- tures must depend on T as follows: Determine the values of 'Y

Determine the values of 'Y 1 and 'Y2 in terms of J.l.o, To, .Po, a, and f12·

Chapter 10

IO-l.

The observed equilibrium constant K(T) for a gaseous reaction

is usually expressed in the series form

ln K(T) =

(QjT)

+A In T + B + CT +

·

·

·

Show that Q is the heat evolved in the reaction at zero temperature.

10-2.

The coefficients in the expansion for ln K

(see Problem 10-1)

for the iodine dissociation reaction 2I ~ I2 are Q =

C, D, etc., are negligible, where Tis in °K and the d1menst~ns of K are (atm) . ·

What fraction of the iodine is dissociated at 1 atm and 500 K?

this fraction changing with T?

The equilibrium constant for the reactiOn 2 SO a~ 2 SOz + 02

has the value 0.29 atm at T = 1000°K. If one mole of S02 and 2 moles of 02 are introduced into a vessel and maintained at P = 4 atm and T = 1000, find

the number of moles of SOa present at equilibrium.

At what rate IS

1!400, :4- =

.

0.75, B

=

1, a~~

10-3.

Problems

Chapter II

mean value

following discrete probability distributions:

II-I.

Calculate the

(n) and

Geometric

Binomial

Poisson

11-2.

Pn

Pn =

Pn = (Nnjn!)e-N

=

(1

-

a)an

[N!jn!(N- n)!]pn(l- p)N-n

Calculate

the

mean

value

(x) and

variance

u~ of

n

for

401

the

variance u; of x for the

continuous distributions, having the following probability densities:

Exponential

f(x)

=

(1/f-)e-zii-

Erlang

f(x)

=

(4xjf-2)e-2z!A

ll-3.

The probability that a certain trial (throw of a die or drop of a

Show that the probability

bomb, for example)

that m successes are achieved in n trials is

is a success is p for every trial.

Pm(n) =

n!

·

m!(n- m)!

pm(l- p)n-m

(this is the binomial distribution)

Find the average number iii of successes inn trials, the mean-square (ili2) and the standard deviation !:J.m of successes in n trials.

The probability of finding n photons of a given frequency in an

a)an, where

a(O < a < 1) is a function of temperature, volume of the enclosure, and the frequency of the photons. What is the mean number n of photons of this fre- quency? What is the fractional deviation !:J.n/n of this number from the mean? Express this fractional deviation in terms of n, the mean number. For what limiting value of n does the fractional deviation tend to zero?

ll-4.

enclosure that is in thermal equilibrium with its walls is Pn =

(1

-

ll-5(a) Show that the number of different ways in which M dis-

objects can be placed in C numbered boxes, with no restriction on the

tinguishable

number of objects per box, is CM.

(b) Show that the number of different ways in which M distinguishable

objects can be placed inC numbered boxes, with no more than one object per box

is [C!j(C -

(c) Show that the number of ways in which iff indistinguishable

objects can be placed inC numbered boxes, with no more than one object per box

is (C!/M!(C -

'

M) !], where M

::::;

C.

::::;

M) !], where M

C.

(d) Show that the number of ways in which M indistinguishable objects

C numbered boxes, with no restriction on the number of objects

per box, is ((C + M - 1) !/M!(C- 1) !].

(e) Show that the number of ways in which M indistinguishable

C numbered boxes, with at least one object per box, is

[(M - 1) !j(C- 1) !(M - C)!], where (M ~ C).

more or less

randomly distributed in time. Suppose the probability density that the next arrival occurs at a timet after the previous arrival is a(t).

Show that the probability that no arrivals occur in a time t after

the last one is

can be placed in

objects can be placed in

ll-6.

(a)

Aircraft arrive at an airport at times that are

Au(t) = J"' a(x) dx

402

where A 0 (0) =

1, and that

T = Ia"' ta(t) dt = Ia"'

A 0(t) dt

Kinetic Theory

is the mean time between arrivals. Compute Ao(t) for an exponential distribu-

tion, a(t) = (1/T)e-tlr and for an Erlang distribution a = (4t/T 2 )e- 21 tr.

(b) Show that the probability that no arrivals occur in a timet chosen

at random is

U

0 (t)

=

(1/T) Jo"' dx J:'"' a(x + y) dy

=

(1/T) {"

Ao(Y) dy

Compute U 0 (t) for the exponential and the Erlang arrival distributions, and

compare them with the postarrival probabilities obtained in part (a).

Why does

U 0 =

A 0 in one case and

U o r" A o in the other?

Chapter 12

12-I. A molecule in a gas collides from time to time with another molecule. These collisions are at random in time, with an average interval r, the mean free time. Show that, starting at timet = 0 (not an instant of collision) the probability that the molecule has not yet had its next collision at time t is e-t!r. What is the expected time to this next collision? Show also that the probability that its previous collision (the last one it had before time t = 0) was earlier than time -Tis e-rlr. What is the mean time of this previous collision? Does this mean that the average time interval between collisions is 2r? Explain the paradox.

In interstellar space, the preponderant material is atomic

12-2.

hydrogen, the mean density being about 1 hydrogen atom per cc. What is the probability of finding no atom in a given cc? Of finding 3 atoms? How many H atoms cross into a given cc, through one of its l-cm 2 faces, per second, if the

temperature is 1°K?

(Figure P-8) in an evacuated chamber

If T is 1000°K?

furnace

F

12-3.

A

closed

contains sodium vapor heated to 1000°K. What is the mean speed vof the vapor atoms? At t = 0 an aperture is opened in the wall of the furnace, allowing a collimated stream of atoms to shoot out into the vacuum. The aperture is closed again at t = r. At a distance L from the aperture, a plate is moving with velocity u, perpendicular to the atom stream, so that the stream deposits its sodium atoms along a line on the plate; the position of the stream that strikes at timet hits the line at a point a distance X = ut from its beginning. Obtain a formula for the density of deposition of sodium as function of X along the line, assuming that

of sodium as function of X along the line, assuming that J~ L~l f FIGURE P-8

J~

L~l f

FIGURE

P-8

Problems

403

r « (L/v), and find the value of X for which this density is maximum. Sketch a curve of the density versus X.

The momentum distribution in a gas, which has particle density

12-4.

(N /V), is

f(p) =

(27rmkT)- 3 1 2 e-p'f 2 mkT(l + E cos a)

where E « 1 and where a is the angle between p and the x axis.

(a) Compute the mean drift velocity U of the gas.

(b) How many atoms per second are crossing, in the positive x direc-

tion, a unit area of the y-z plane? How many are crossing in the negative

direction? How are these quantities related to Ux?

t eWo '---_, t . -- : -- exterzor I •"'---metal surface interior
t
eWo
'---_,
t
.
--
: --
exterzor
I
•"'---metal surface
interior

FIGURE

P-9

12-5. Most conduction electrons in a metal are kept from leaving the

metal by a sudden rise in electric potential energy, at the surface of the metal, of

the inside

and the outside of the metal. Show that if the conduction electrons inside the metal are assumed to have a Maxwell distribution of velocity, there will be a

thermionic emission current of electrons from the surface of a metal at tem-

perature T

is the velocity distribution of these electrons just outside the surface? [The measured thermionic current is proportional to T 2 exp( -ecp/kT), where cp < Wo; see Problem 26-2.] 12-6. A gas of molecules with a Maxwell distribution of velocity at temperature Tis in a container having a piston of area A, which is moving outward with a velocity u (small compared to (v)), expanding the gas adiabatically (Figure P-10). Show that, because of the motion of the piston, each molecule that strikes

Figure P-9). What

an amount eW 0 , where W 0 is the electric potential difference between

that is proportional to yT exp( -e W 0 /kT) (see

u

t x_ /·~~v' ~ I 0 I 0' ,~ I FIGURE P-10
t
x_
/·~~v'
~
I
0
I
0'
,~
I
FIGURE
P-10

404

Kinetic Theory

the piston with velocity v at an angle of incidence 8 rebounds with a loss of kinetic energy of an amount 2mvu cos 8 (u « v). Show that consequently the gas loses energy, per second, by an amount -dU = PAu = P dV, where dV is the increase in volume of the container per second.

Helium atoms have a collision cross section approximately equftl

to 2 X lQ- 16 cm 2 In helium gas at standard conditions (1 atm pressure, 0°C),

assuming a Maxwell distribution, what is the mean speed of the atoms? What is their mean distance apart? What is the mean free path? The mean free time?

The Doppler formula for the observed frequency f from a source

12-7.

12-8.

moving with velocity v., along the line of sight to the observer is

f =

fo[1 + (v.,/c)]

where fo is the frequency radiated when the source is at rest and c is the velocity

of light. (a) What is the distribution in frequency of a particular spectrum line, radiated from a gas at temperature T?

(b) What is the variance (Cf- f 0 ) 2 ) of this radiated frequency? The

square root of the variance is called the breadth of the line.

(c) Atomic hydrogen and atomic oxygen are both present in a hot gas.

How much broader will the hydrogen lines be, compared to oxygen lines of

roughly the same frequency?

Chapter 13

13-l. A particle, moving vertically under the influence of gravity, periodically strikes and rebounds elastically from a horizontal plane. Sketch its phase-space trajectory between bounces. If particle 1 is released at t = 0 a distance h above the plane, with no initial velocity, and if particle 2 is released under similar conditions at time t:.t, how far apart in phase space are the two particles when particle 2 is released? How far apart are they when particle 1 just reaches the horizontal plane? Assume that t:.t is small compared to the time between bounces of each particle. If the two particles are released simul- taneously, one at height h the other at height h + t:.h, how far apart in phase space are they when the first particle hits the plane? 13-2. Use the Maxwell-Boltzmann distribution to show that, if the atmosphere is at uniform temperature, the density p and pressure P a distance z above the ground is exp( -mgz/kT) times p 0 and Po, respectively (where g is the acceleration of gravity). Express po and Po in terms of g, T, and M., the total mass of gas above a unit ground area. Obtain this same expression from the perfect gas law, P = pkT/m and the equation dP = - pg dz giving the fall-off of pressure with height (assuming T is constant). Find the corresponding expressions for p and Pin terms of z if the temperature varies with pressure in the way an adiabatic expansion does, i.e., P = (p/C)-r, T = (Dp)-r- 1 , where

(Cp/C.) [see Eqs. (4-12)]. 13-3. The collision cross section of an air molecule for an electron is about lQ- 19 m 2 . At what pressure will 90 percent of the electrons emitted from

a cathode reach an anode 20 em away? 13-4. A gas-filled tube is whirled about one end with an angular velocity w. Find the expression for the equilibrium density of the gas as a

function of the distance r from the end of the tube.

'Y =

Problems

f(r, p)

13-5(a)

The phase-space distribution for the N atoms in a gas is

=

(1 + "(X) (21T'mkT)-312e-p'l2mkT

405

where the origin of position coordinates is at the center of a rectangular box of volume V, occupied by the gas. What is the pressure in the gas? Is the gas in mechanical equilibrium if no forces are acting? What sort of force would have to be applied for the gas to be in mechanical equilibrium? Assume that 'YX is smaller than 1 everywhere inside the box.

(b) The phase-space distribution is changed to

f(r, p)

=

[21T'mkT(x)]-al2e-p 2 /2mkT(x)

T(x)

=

To(1

-

"(X)

What is the pressure now?

Is the gas in mechanical equilibrium?

(c) Finally, the distribution is changed to

f(r, p)

=

(1 + 'YX)[21T'mkT(x)]-a!2e-p'/2mkT(x)

- the gas m mechanical equilibrium?

~3-6. The atomic magnets in a paramagnetic crystal are not completely ~hgn themselves along the applied magnetic field; there is a small energy

free .to

of ~mdmg ('Y per magnet, where 'Y/k is a fraction of a degree K) to the crystal lattice. In the bound state the magnets cancel their polarization in pairs. In the unbo~nd state the magnets can align themselves parallel or antiparallel to the field (I:e., J = t. for each magnet). The behavior can be approximated by a model havmg five different quantum states for each pair of magnets:

To the first order in the small quantity 'Y is Is it in thermal equilibrium?

where T_ =

To(1

"fX) as before.

0-both magnets bound, energy e 0 = 0

- 2-unbound, magnet 1 parallel, magnet 2 antiparallel, e 2 =

1-unbound,

both magnets parallel to field, e 1 =

2"(

2 · tmn~

27

3-unbound,

magnet 1

antiparallel, magnet 2 parallel, e 3 =

2'Y

4-unbound,

both magnets antiparallel, e 4

=

2'Y + m 8

Show that the magnetization of the crystal is

X = 2e--rlkr cosh (mn~)

2kT

where mn is the Bohr magneton, N m is the total number of atomic mao-nets and

J.lo = (~/4)).

when kT « 'Y·

Sketch or describe the dependence of 9J( on 4) when kT »~and Over what range of T and 4) is Curie's law valid?

Chapter 14

14-l. A tube of length L = 2 m and of cross section A = lQ-4 m 2 cont~i~s C02 at. nor:nal conditions of pressure and temperature (under these conditiOns. the diffusiOn constant D for C0 2 is about w-s m2/sec). Half the C02 contams radioactive carbon, initially at full concentration at the left-hand ~nd,zero concentration at the right-hand end, the concentration varying linearly

m between.

What is the value of tc for

C0 2 under these conditions? Initially,

406

Kinetic Theory

how many radioactive molecules per second cross the mid-point cross section from left to right? [Use Eqs. (14-15).] How many cross from right to left? Compute the difference and show that it checks with the net flow, calculated from

the diffusion equation

(net flow) =

-D(dn/dx).

.

.

14-2.

A gas is confined between two parallel plates, one movmg w~th

respect to the other, so that there is a flo\~ shear ~n the gas,. the .mean ~as velocity a distance y from the stationary plate bemg (3y m the x ~1rectwn (Figure P-11). Show that the zero-order velocity distribution in the gas IS

(1/27rmkT) 3 1 2 exp{ -(l/2mkT)[(Pz -

m(3y) 2 + p; + p;Jl

=

fo(Pz -

m(3y, Pu, p,)

Show that the

mean rate of transport of x momentum across a unit area perpendicular to theY axis is

Use Eq. (14-7) to compute f to the first order of approximation.

(N /V) Ctcf3/m) III p~fodpz dpy dp, =

(N /V)tcf3kT,

which equals the viscous drag of the gas per unit area of the p~ate, which equals the gas viscosity 77 times (3, the velocity gradient. Express 77 m terms o~ T and f. (mean free path) and show that the diffusion constant D of Eq. (14-16) IS equal to (77/ p), where p is the density of the gas.

~v~IL

r-r- v~Py

~v=O

x-

FIGURE

P-11

14-3. A vessel containing air at standard conditions is radiate~ with x-rays so that about lQ-Io of its molecules are ionized. A uniform electnc. field of 104 ~olts/meteris applied. What is the initial net flux of electrons~ Of IOns? (See Problem 13-3 for the cross section for electrons; the cross. sectiOn .for the ions is four times this. Why?) What is the ratio between dnft velocity and mean thermal velocity for the electrons? For the ions? . 14-4. The free electrons in a partly ionized gas (plasma) have a density (N,/V) and an equilibrium distribution

fo(p) =

(1/V) (27rmkT)-312e-p'/2mkT.

An oscillating electric field (;t = {;t 0 eiwT is applied, where (;to is pointed in the x direction, and is uniform throughout V.

Problems

407

(a) Show that the Boltzmann equation for the resulting distribution is

f + tc(ajjat) = fo- eeotceiwr(afo/apz)

and thus show that f must have the form f 0 (p) + g(p)eiwT.

(b)

By equating coefficients of

independent terms, show that

the

time-dependent and

the

time-

g(p) = (e~;A)11+-(~~:)2(:;;) (1/v)fo(p)

where we have assumed that tc =

/.(1/v).

1 it is in

Show that when wtc » 1 it is out

of phase with (;t and corresponds to the separate motion of each electron in an oscillating field.

Explain its

dependence on frequency. 14-5. A paramagnetic gas is subjected to an oscillating magnetic field l8 = l8o cos wt (l8 = J.toS)). The atomic magnets have quantized directions eit~erbeing p~rallelto the field, with moment imB and energy imBlB, or bein~ ant1parallel, with moment -imB and energy +imBlB, where mB is the Bohr magneton.

Use the Boltzmann equation to find the first-order distribution

function f for orientation of the atomic magnets, corrected to allow for the time

variation of 18. Assume that imBlB « kT, expand the zero-order Maxwell- Boltzmann distributionfo in powers of (mBl8/2kT), and discard all powers higher than the first.

(c) Compute the drift velocity Vz.

phase with (;t and corresponds to Eq. (14-12).

(d)

Show that

when wtc «

Compute the joule heat production per unit volume.

(a)

J.toNM(moment) of the gas as a

function of time, to the first order in (mBlB/2kT).

Compute the energy gained by the gas JS) d?m (and therefore lost

by the oscillator) per second, to the first order. 14-6. A plasma is subjected to an electric field (;tz in the x direction and a magnetic field lB. in the z direction, both fields being independent of position and time.

(b) Calculate the magnetization ?In =

(c)

(a)

Show that the Boltzmann equation for the distribution in momen-

tum of the electrons in the plasma is

f =

fo

-

etc [{;tz(jf_) + ).8, Pv ( m

apx

aj) _ ).8, Pz (!L)J m

apx

ap.

+ tcf 1 + t2/2

and equating coefficients of powers of tc up to the second. Show that if fo is the Maxwell distribution, !1 = (e{;txPx/mkT) X fo and

(b) Compute f to the second order in tc by setting f = f 0

!2

=

[- (e 2 {;t;JmkT) + (e 2 {;t;p;/m 2 k 2 T 2 ) -

(e 2 {;txlBzPv/m 2kT)]f 0

Why does the magnetic field have no first-order effect on the distribution?

What is

the physical significance of the drift in the y direction?

. 14-7. It is suggested that the conduction electrons in a metal might be considered to be a gas in thermal equilibrium with the atomic ions which are held together in the crystal lattice. The electron collisions would be ~ainlywith

(c)

Compute the components Ux and Uv of the drift velocity.

408

Kinetic Theory

the ions and the t, in the Boltzmann equation would .then be .the time between collisions with the ions. In Chapter 26 we see that this model Is not a very good approximation, but it is useful to see what it ( ) Use the formulas of this chapter to compute the electric conduc-

kg/m 3 , density ?f

tivity (If~) of silver (mol. wt. = 108, density 10,500

ions = 6 x lQ2Bjm3) in terms of e, N,/V, t m, k, T, and (1/v). The electric

conductivity of silver at room temperatures is 7 X 1Q7 mhos/m. If we use the Maxwell distribution to compute (1/v), what does this predict f?r the me~n free th f of the electrons in silver? How does this compare with the distance

b:tween the ions?

at room temperatures

How does the formula predict the conductivity should vary

with T? The actual conductivity is proportional to T- and to T-4 at lower temperatures (see page 361).

,

1

(b) Write out the formula for the heat conductivity of the ~l~ctron.s,

assuming they have a Maxwell distribution, in terms of ~he same q~~ntities as I.n (a). Show that the ratio between thermal and electric conductiVIty, for this

model, divided by T,

measured value of this quantity, for silver, for 250 K < T < 500 K, IS 2.3 ~

What does the model predict? decreases rapidly.

10 . ·

Below 150°K the measured value of this ratio

is just (5k 2 /2e 2 ), indep~ndent of T,

t

6

or. (1/v).

T~se

.

(c) Use the formulas of this chapter to evaluate the thermoelectric

power, of Eqs. (8-47) et seq., for silver.

14-8.

. Suppose the mean free path 'A of the electrons IS not cons~a~t,

but is proportional to the electron's velocity v.

depend on T? Does this suggest an answer to some of the discrepancies of

How then would t~e conduc~Ivity

Problem 14-7?

Chapter 15

15-l. A solid cylinder of mass M is suspended from its center by a fine elastic fiber so that its axis is vertical. A rotatio~ of the cylinder through an angle (}from equilibrium requires a torque KO to tw1~t the fib~r When. sus- pended in a gas-filled container at temperature T, the cylmder exhi?It~ rotatwnal fluctuation due to Brownian motion. What is the st~n~ard deviati?n (C!.O) of the amplitude of rotation and what is the standard dev1atwn (ll.w) of Its angular velocity? What would these values be if the container we:e evacuated? . 15-2. An inductance L connected across the termmals of a capacitance C has electromagnetic energy of oscillation

U

=

(Q 2 j2C) + (LP/2)

I

=

(dQjdt)

Q being the charge on the capacitance plates. The circuit is in thermal equilib- rium with its surroundings at temperature T. There is a thermal noise current and a fluctuating charge in the capacitor.

(a) Calculate (Q 2 ) and (P).

what is the rms voltage across the .

. A piston slides without frictwn m a cyhnder of mternal cross

molecules. The force w~ich pushes the

piston downward has a magnitude F = P 0 A no matter what the displacement of the piston. Also assume that F is large enough so that we can neglect the effect

capacitor plates at T =

(b)

Assuming C =

10-12 farad,

300°K?

.

.

.

15-3.

section A, and encloses a perfect gas of N

of the mass of the piston.

Problems

4

(_a)

W:hat is the equilibrium distance Xo of the piston from the botto

of the cylmder, If the temperature of the gas is T?

(b) What additional force is required to displace the piston a distanc

x (small compared to Xo) from equilibrium? Express this force in terms of

same Xo, N, quantities. and T.

Calculate the potential energy of the displacement in terms of th

(c) The piston does not stay in its equilibrium position; it oscillate

up an~ down bec~use of the fluctuations of pressure of the gas of the cylinde

What IS the relative probability that the piston is displaced from equilibriur between x and x + dx?

What is the mean-square amplitude (x 2 ) of its displacement frorr

eqmhbrmm?

Sh~w that if the Hamiltonian energy of a molecule depends on generalized. c~ordma.te q or mome~tum p in such a way that H ---7 'XI as p q ---7 ± 'XI, It Is possible to generalize the theorem on equipartition of energy tc

. (d)

~5-4.

Express the result in terms of x 0 and N.

01

( qiJH)

oq

av

=

(p iJH)

op

av

=

kT

Verify that this reduces to ordinary equipartition when H has a quadratic dependence on q or p. If H has the relativistic dependence on the momentum

H

=

c y' (p;, +

show that

p~ +

p;)

+

m2c2

(c 2 p~/H)av = · · · = (c 2 p~/H)av = kT

Analyze the thermal oscillations of electromagnetic waves along

a conductmg Wire of length L.

In this case of one-dimensional standing waves

the nth wave '':ill have the form cos(1rnxjL)eiwt, where w = 21rj = 1rnc/L, c bein~ the wave velocity, and f the frequency of the nth standing wave. Show that the number of allowed frequencies between f and f + df is (2Ljc) df and thus if every st~ndingwave has a mean energy kT, the energy content of the waves with

fr~q~enc:esbet":een.J and f + df is (2LkT /c) df. If the wire is part of a trans-

m.ISSion lm.e, whiCh IS ~e~mmated by its

Will be dehve~edto thiS Impedance in a time (2L/c). Show, consequently, that

the power delivered to the terminal impedance, the thermal noise power in the

frequency band

if every degree of freedom carries a mean thermal energy kT. This formula

correspon~swith experiment at frequencies less than about 1010 cycles per second or so, but It cannot be correct for all frequencies, clear out to f ---7 'XI or else each

25-5 wire for would the contain answer.) an infinite amount of electromagnetic energy.

characteristic impedance, all the energy

df at frequency j, is kT df if every wave is a derrree of freed~mand

(See Problem

of the Brownian motion of a spherical particle of

radms 4.4 X 10- 7 m m water at 300°K, which has viscosity 1J = w-a newton-

sec/m2 were made every 4 sec.

x(t - 4) are tabulated for 25 readings, as follows:

15-6. Obse:vations

.

The displacements in the x direction 0 = x(t) '

-5.8

+3.1

-1.0

-2.0

-1.5

+3.4

-0.2

+2.6

-1.9

+1.8

-1.8

-3.5

+0.3

-2.2

-0.2

-0.5

+1.3

+0.4

-0.4

+2.5

+0.5

+0.3

+0.6

+1.5

+1.9

410

Statistical Mechanics

Compute the mean value of oand its variance. How close is this distribution to the normal distribution of Eq. (11-23)? Use Eq. (15-11) to compute Avogadro's number N 0 from the data, assuming that R = kN o is known.

Chapter 18

18-l. A gas of N point particles, with negligible (but not zero) collision interactions enclosed in a container of volume V, has a total energy U. Show that the sy~tempoint for the gas may be anywhere on a surface in phase space which encloses a volume [VaNi•(27rmU)aNI•j(3N /2) !]. For an ensemble of these systems to represent an equilibrium state, how must the system points of the ensemble be distributed over this surface? 18-2. A harmonic oscillator has a Hamiltonian energy H related to its momentum p and displacement q by the equation

p' + (Mwq)' =

2MH

When H = U a constant energy, sketch the path of the system point in two- dimensional phase space. What volume of phase space does it enclose? In the case of N similar harmonic oscillators, which have the total energy U given by

N

l

i=l

p;' +

N

l

i=l

(Mwq;)' =

2MU

with additional coupling terms, too small to be included, but large enough to ensure equipartition of energy, what is the nature of the path traversed by the system point? Show that the volume of phase space "enclosed" by this path is (1/N!) (27rU/w)N.

Use the final result of Problem 18-2 to show that the entropy of

N distinguishable harmonic oscillators, according to the microcanonical ensemble is

18-3.

S = Nk[l + ln(kT/liw)]

18-4. A linear array of N particles is spaced equally along a straight line. Suppose each particle has two possible states, which may be designated as states A and B and that we have adjusted the energy origin so the A state has energy - {3 and 'the B state has energy +{3. Suppose also that there is interaction between nearest neighbors in the linear array, so that every pair with like states (AA or BB) contributes 0 to the energy and every pair with unlike states (A!3 or

BA) contributes a

ferromagnetic or antiferromagnetiC material, where state A IS onentatwn p~rallel to the field and B is anti parallel orientation, with {3 = ml8; the energy a Is the difference between the coupling energy between neighboring antiparallel magnets and that between neighboring parallel magnets. It could also be a model for the mixing of two substances in a binary alloy; state A is the presence of one sort of atom state B the presence of the other sort.) '(a) Let m be the number of particles in state A (so that N - m particles are in state B). These A particles can be placed anywhere along the line· they may be all at the beginning of the line, and all the B states may be at the end' or there may be a group of A's at the beginning and at the end, with all the B's 'grouped in the middle, and so on. Suppose the A's are grouped in n groups

(This is a. one-dirr:ensional model ~f t~e ma_gnets m a

Problems

411

(n .:::; m), each group comprised of one or more A's, separated from the nextAgrou by a group of one or more B's. Show that the number of B groups is eith!

1 or n or n + 1 ~nd.that the number of unlike pairs (divisions between A

n -

groups and B groups) IS either 2n -

when N, n, and mare large enough, the energy of the linear array is U = +N~

- 2{3m + 2om, where m 2: n.

2 or 2n- 1 or 2n, respectively.

Show that

(b) Use the results of Problem 11-5e to show that the number of dif-

ferent wa:ys in which the m states A may be arranged among the n different A

groups, w1t~ at least on~ par~icle in each group, is [m!/n!(m - n) !] and the

number of d.1fferent ways m whiCh the (N - n B groups IS

m) B states are arranged within the

[(N -

m) !jn!(N -

m -

n) !].

. (c) Show t~at ~he entropy of a microcanonical ensemble having a

m) particles in state Band having

lmear array of m particles m state A and (N - the A states in n separated groups is

S = k[mlnm + (N- m) ln(N- m)- 2nlnn

- (m- n) ln(m- n) -

(N- m- n) ln(N- m- n)]

(d) Show that application of Eq. (18-1) leads to the pair of equations

e2/3/kT =

(N

-

m)(m- n)

(N- m- n)m

e2a/kT = (N- m- n)(m- n) n'

which must be solved simultaneously to find equilibrium values of nand m and thus of U and S, for a specified T.

0 (zero applied magnetic field, if the system is a linear array

of magnets) show that the equilibrium value of m is itN, and those of nand S are

(e) If f3 =

n

=

-----,-(N--'-/---'2)_

ea/kT + 1

S = Nk ln [2 cosh(~)]-

2kT

2T aN tanh(

!!

2kT

)

What .is the most. likely or~ering of the states along the line when kT »a? Wh.at IS t~1emost likely ordermg for kT «a, when a is positive (binding between unhke pairs stronger than binding between like pairs)? When a is negative?

Chapter 19

19-l.

A system consists of three distinguishable molecules at rest each

of which has a quantized magnetic moment, which can have its z comp~nent

7-M, 0, or -ft!·. Show that there are 27 different possible states of the system; hst them all, givmg the total z component M,; of the magnetic moment for each.

-k"'2J; X ln(f;) of the system for the following a