# Welcome back

## Find a book, put up your feet, stay awhile

Sign in with Facebook

Sorry, we are unable to log you in via Facebook at this time. Please try again later.

or

Welcome to Scribd. Sign in or start your free trial to enjoy unlimited e-books, audiobooks & documents.Find out more

Download

Standard view

Full view

of .

Look up keyword

Like this

Share on social networks

1Activity

×

0 of .

Results for: No results containing your search query

P. 1

Atkins, Solution, 7th EdRatings: (0)|Views: 164|Likes: 2

Published by api-3723327

Atkins, 7th edition solutions manual

Atkins, 7th edition solutions manual

See more

See less

https://www.scribd.com/doc/6667450/Atkins-Solution-7th-Ed

03/18/2014

text

original

19 Statisticalthermodynamics:

the concepts

Solutions to exercises

Discussion questions

E19.1(b)Consider the value of the partition function at the extremes of temperature. The limit ofq asT

approaches zero, is simplyg0, the degeneracy of the ground state. AsT approaches in\ufb01nity, each term in the sum is simply the degeneracy of the energy level. If the number of levels is in\ufb01nite, the partition function is in\ufb01nite as well. In some special cases where we can effectively limit the number of states, the upper limit of the partition function is just the number of states. In general, we see that the molecular partition function gives an indication of the average number of states thermally accessible to a molecule at the temperature of the system.

E19.2(b)The statistical entropy may be de\ufb01ned in terms of the Boltzmann formula,S= k lnW , whereW is the

statistical weight of the most probable con\ufb01guration of the system. The relation between the entropy and the partition function is developed in two stages. In the \ufb01rst stage, we justify Boltzmann\u2019s formula, in the second, we expressW in terms of the partition function. The justi\ufb01cation for Boltzmann\u2019s formula is presented inJusti\ufb01cation 19.6. Without repeating the details of this justi\ufb01cation, we can see that the entropy de\ufb01ned through the formula has the properties we expect of the entropy.W can be thought of as a measure of disorder, hence the greaterW , the greater the entropy; and the logarithmic form is consistent with the additive properties of the entropy. We expect the total disorder of a combined system to be the product of the individual disorders andS= k lnW= k lnW1W2=

kln W1+kln W2=S1+S2.

In the second stage the formula relating entropy and the partition function is derived. This derivation is presented inJusti\ufb01cation 19.7. The expression forW , eqn 19.1, is recast in terms of probabilities, which in turn are expressed in terms of the partition function through eqn 10. The \ufb01nal expression which is eqn 19.34 then follows immediately.

E19.3(b)Since\u03b2 and temperature are inversely related, strictly speaking one can never replace the other. The

concept of temperature is useful in indicating the direction of the spontaneous transfer of energy in the form of heat. It seems natural to us to think of the spontaneous direction for this transfer to be from a body at highT to one at lowT . In terms of\u03b2, the spontaneous direction would be from low to high and this has an unnatural feel.

On the other hand,\u03b2 has a direct connection to the energy level pattern of systems of atoms and molecules. It arises in a natural, purely mathematical, manner from our knowledge of how energy is distributed amongst the particles of our atomic/molecular system. We would not have to invoke the abstract laws of thermodynamics, namely the zeroth and second laws in order to de\ufb01ne our concept of temperature if we used\u03b2 as the property to indicate the natural direction of heat \ufb02ow. We can easily demonstrate that\u03b2 is directly related to the statistical weight W through the relation

\u03b2= (\u2202ln W/\u2202U)N.W, U , andN are all concrete properties of an atomic/molecular system.

E19.4(b)Identical particles can be regarded as distinguishable when they are localized as in a crystal lattice

where we can assign a set of coordinates to each particle. Strictly speaking it is the lattice site that carries the set of coordinates, but as long as the particle is \ufb01xed to the site, it too can be considered distinguishable.

302

INSTRUCTOR\u2019S MANUAL

Numerical exercises

E19.5(b)

ni=Ne\u2212\u03b2\u03b5i

q

whereq=

\ue000

j

e\u2212\u03b2\u03b5j

Thus

n2

n1

=e\u2212\u03b2\u03b52

e\u2212\u03b2\u03b51=e\u2212\u03b2(\u03b52\u2212\u03b51 ) =e\u2212\u03b2\ue000\u03b5 =e\u2212\ue000\u03b5/ kT

Givenn2

n1

=1

2, \ue000\u03b5=300 cm\u22121

k= (1.38066\u00d7 10\u221223 J K\u22121)\u00d7

\ue001

1 cm\u22121

1.9864\u00d7 10\u221223 J

\ue002

=0.69506 cm\u22121 K\u22121

n2

n1

=e\u2212\ue000\u03b5/ kT

ln

\ue003

n2

n1

\ue004

=\u2212\ue000\u03b5/ kT

T=

\u2212\ue000\u03b5

kln(n2/n1)=

\ue000\u03b5

kln(n1/n2)

=

300 cm\u22121

(0.69506 cm\u22121 K\u22121)ln(2)=622.7 K \u2248623 K

E19.6(b)(a)

\ue001= h

\ue003

\u03b2

2\u03c0m

\ue004

1/2

[19.22]=h

\ue003

1

2\u03c0 mkT

\ue004

1/2

=(6.626 \u00d710\u221234 J s)

\u00d7

\ue003

1

(2\u03c0 )\u00d7 (39.95)\u00d7 (1.6605\u00d7 10\u221227 kg)\u00d7 (1.381\u00d7 10\u221223 J K\u22121)\u00d7 T

\ue004

1/2

=276 pm

(T /K)1/2

(b)

q=V

\ue0013[22]=(1.00\u00d7 10\u22126m3)\u00d7 (T /K)3/2

(2.76\u00d7 10\u221210 m)3

=4.76 \u00d71022(T /K)3/2

(i) T=300 K, \ue001=1.59\u00d7 10\u221211m= 15.9 pm, q= 2.47\u00d7 1026

(ii) T=3000 K, \ue001=5.04 pm, q=7.82\u00d7 1027

Question. At what temperature does the thermal wavelength of an argon atom become comparable

to its diameter?

E19.7(b)The translational partition function is

qtr=V

h3(2kT \u03c0 m)3/2

soqXe

qHe=

\ue003

mXe

mHe

\ue004

3/2=

\ue003

131.3 u

4.003 u

\ue0043/2=187.9

STATISTICAL THERMODYNAMICS: THE CONCEPTS

303

E19.8(b)

q=

\ue000

levels

gje\u2212\u03b2\u03b5j= 2+ 3e\u2212\u03b2\u03b51+ 2e\u2212\u03b2\u03b52

\u03b2\u03b5=hc\u02dc

\u03bd

kT=1.4388(\u02dc

\u03bd/cm\u22121)

T/K

Thusq= 2+ 3e\u2212(1.4388\u00d71250/2000)+2e\u2212(1.4388\u00d71300/2000)

=2 +1.2207 +0.7850 =4.006

E19.9(b)

E= U\u2212 U (0)=\u2212Nq

dq

d\u03b2=\u2212Nq

d

d\u03b2(2+ 3e\u2212\u03b2\u03b51+ 2e\u2212\u03b2\u03b52 )

=\u2212Nq

\ue005

\u22123\u03b51e\u2212\u03b2\u03b51 \u22122\u03b52e\u2212\u03b2\u03b52

\ue006

=N hc

q

\ue005

3\u02dc

\u03bd1e\u2212\u03b2hc \u02dc

\u03bd1+2 \u02dc

\u03bd2e\u2212\u03b2hc\u03bd2

\ue006

=

\ue003

NAhc

4.006

\ue004

\u00d7

\ue0073(1250 cm\u22121)\u00d7

\ue005

e\u2212(1.4388\u00d71250/2000)

\ue006

+2(1300 cm\u22121)\u00d7

\ue005

e\u2212(1.4388\u00d71300/2000)

\ue006\ue008

=

\ue003

NAhc

4.006

\ue004

\u00d7(2546 cm\u22121)

=(6.022 \u00d71023mol\u22121)\u00d7 (6.626\u00d7 10\u221234 J s)\u00d7 (2.9979\u00d7 1010cm s\u22121)\u00d7 (2546 cm\u22121)

=7.605 kJ mol\u22121

E19.10(b)In fact there are two upper states, but one upper level. And of course the answer is different if the

question asks when 15 per cent of the molecules are in the upper level, or if it asks when 15 per cent

of the molecules are ineach upper state. The solution below assumes the former.

The relative population ofstates is given by the Boltzmann distribution

n2

n1

=exp\ue003

\u2212\ue000E

kT

\ue004

=exp

\ue003

\u2212hc \u02dc

\u03bd

kT

\ue004

so lnn2

n1

=\u2212hc \u02dc

\u03bd

kT

ThusT=

\u2212hc \u02dc

\u03bd

kln(n2/n1)

Having 15 per cent of the molecules in the upper level means

2n2

n1

=0.15

1\u2212 0.15son2

n1

=0.088

andT=\u2212(6.626 \u00d710\u221234 J s) \u00d7(2.998 \u00d71010 cm s\u22121) \u00d7(360 cm\u22121)

(1.381\u00d7 10\u221223 J K\u22121)\u00d7 (ln 0.088)

=213 K

E19.11(b)The energies of the states relative to the energy of the state withmI= 0 are\u2212\u03b3N\u00af

hB,0,+ \u03b3N\u00af

hB,

where\u03b3N\u00af

h=2.04\u00d7 10\u221227 J T\u22121. With respect to the lowest level they are 0, \u03b3N\u00af

h,2\u03b3N\u00af

h.

The partition function is

q=

\ue000

states

e\u2212Estate /kT

where the energies are measured with respect to the lowest energy. So in this case

q=1 +exp

\ue003

\u2212\u03b3N\u00af

hB

kT

\ue004

+exp

\ue003

\u22122\u03b3N\u00af

hB

kT

\ue004

AsB is increased at any givenT ,q decays fromq= 3 towardq= 1 as shown in Fig. 19.1(a).

- Read and print without ads
- Download to keep your version
- Edit, email or read offline

© Copyright 2015 Scribd Inc.

Language

Choose the language in which you want to experience Scribd:

Sign in with Facebook

Sorry, we are unable to log you in via Facebook at this time. Please try again later.

or

Password Reset Email Sent

Join with Facebook

Sorry, we are unable to log you in via Facebook at this time. Please try again later.

or

By joining, you agree to our

read free for two weeks

Unlimited access to more than

one million books

one million books

Personalized recommendations

based on books you love

based on books you love

Syncing across all your devices

Join with Facebook

or Join with emailSorry, we are unable to log you in via Facebook at this time. Please try again later.

Already a member? Sign in.

By joining, you agree to our

to download

Unlimited access to more than

one million books

one million books

Personalized recommendations

based on books you love

based on books you love

Syncing across all your devices

Continue with Facebook

Sign inJoin with emailSorry, we are unable to log you in via Facebook at this time. Please try again later.

By joining, you agree to our

Are you sure?

This action might not be possible to undo. Are you sure you want to continue?

CANCEL

OK

You've been reading!

NO, THANKS

OK

scribd