cH 44r/s41

Physical Chernistry Winter Quarter, 2012 D.Partment of Chemistry, Portland State LJniversity

HOMEWORK ASSIGNMENT 2

Assigned: 0 I ll8l20l2 Due: 02|0IDAI2

Problems from the text Chapter 18, pages 757-763.

Problem
19.4 18.5 1 9.7 1g.g
1g

Text Page
757 757 757 757 757 757 759 759 759

.I2
.2I

18.13
18

18.24
18 .25

19.39

76r

18-4. Using the data in Table 8.6, calculate 300 K. 1000 K. and 2000 K.
l0n We catr use the second line o[ Eq uat l( cxcrited state, with g, , - 2,, 8 12 : ) I 8"3 .fz

the fraction of sodium atoms in the first excitecl state a'

,:t

l0 to calculate the fraction of sodium atoms in the fir' -,\ . And B14:2:
2e*

r',,
'lle r'\ I
I r..

, + Zt-f, T
)r, X xp

rl a the Using the data in TaLrle 8.6, ws [i nd thalt rh

+ '2te -fl(ear-l-Icti()n rf )f tir Lln rer:altot 0 rh s fra m( :t

e + 4e
,-

is

r _,

tL

6 )5r

6 95 lc 50 )m

'9

I.li: ic n
.l

8:3 lmI

1-

I
I

*l

)r I

and thc denom inatol' is

2+Zexp _lc
LIsing
the.sc'.

I_* 16 956.183 cm- ' .|+ +e xpl

L(o
I
^oL
J 25 139.86

t-

It6 913.319 crrt

( l. (' (0 6950

I -l

L
,

cm-r.K-

cm

' I

l-r
t0
I

valttcs.

\\'Ll

ous flnd t hat thc valLtes ot' ,f ? for the variio S1te mperaturc s aro

- 4. 8x .frtr - looo K) - 2. 5x
frtr :
3oo

K)

*:1/.
_l

10
1

ll
6

f "(T

2000 K)

- 5. 0x

t0
I

1B-5. UsingthcdatainTable 18.l.$alrratcthcli'actionof lithiumalomsinthefirstexcitedstateat

300

K.

1000

K. and 2000 K.

ll We can use the secrond linc of Equat io n r8. 10 to calculate the l'r'act loln of lithium atoms in the ftrst excitccl statc, w ith g,,, - 2, S,z : 2, 8. 3 -A , and g*t:2'. -.?
n(

f,:

2e'-fl',,
2

+-2t;4
iL,

t'Je

r2

*
14

4e*u,n

2e

fie"e4

lat [Jsing the data in Table 8.6, we find th thc

t-

ll

r umerator of thi S flf :ti 101n is

11t

2e XT rrL
and the denominator is

-i ffi903.66 cm* )T;l

0.
I'

I
I

2+2exp

14 9)0 3,66

cm-

'1
I

[-.
^e

6,) )l 0'\, m n

*1

' )'l K"- ,} rJ J

.l r
I

l_

+,4e xpl
L

l4 904.00 cm-' (0 6e 50 cm*'.K-r) T

*2e

[-

:(u. 6 )5(0Icn I J cnl

'9
I

m' z',1 2l0t )6.1 2tcry -l

I .K- )r I + K"ry
.

Using these values, we find t hai rlht

Afl

v?. 35i alu, e alue

ll' fo the ofJIrf rrt

r0()K 300 ()
= 9.

iorus ten'llpe ratures are

(T= f;(
fr( J (7
/-,1

;:
9x

li0-32
1

TCK l= =l 000 K)

-A
-'f.

0-'0
0*5

T_ OK f,\ T_ t000 K) I (7

:-] 2x

18-7. Using the values of O,,o and

Wb can use the definitions

Do in Table 18.2, calculate rhe vaues of

D, for CO, NO, and K,.

Dn:

D,: Do- ft$ : D,r=

* hvlZ and Ou* : hvlko to write ko o.,,, Rouiu

Do z
2

D.(co':il:
:l ::l-:
D'(No',:

.-

.
::"1-,

D'(Kz):

lli "::I :l :"1-,

18-8. Calculate
and i,o, :

x 10-' kJ.mol-r .K*')(133 K)

the characteristic vibrational temperature @u,n for Hr(g) and Dr(S) (n",

4401 cm-'

3112 cm-t).

Frorn the detrnition of )u,0, we can write

@uiu(Hr) Ouiu(Dt)

@u,n

hcvlAu. Then

(6.626

(6.626

x 10-34 J.s) (2.9919 x l0r0 cm,r-')(4401 cm-r) - 6332K 1 .3 8 1 x 10*23 J.Kx 10-34 J .s) (2.9979 x 1010 crn.**') (31 l2 cm-r ) -4478K 1.381 x 10-23 J.K
I

18-12. Calculate

the value of the characteristic rotational temperature (O,o, for H2(g) and Dr(g). ('l$e bond lcngths of H, and Drare74.16 pm.) Thc atomic mass of deuterium is 2.014.

Thc rcduccd masscs of hydrogcn and dcutcrium, respectively, are

' \ z'
,,lLJ \

x 10-27 ks)2 2(r.614 x 10-16

(1.674

- s'370 x to-28 kg

and

\ \ ',, r'T\!' -

3.344 x

lA-27 kg)2

2(3.344 x10

tffi

Now use the formula @,o, = h' /Ztt R2k" (Equation 18.32) to find the value of O,o, for hydrogcn and deuterium:
( 1 .055

@ro,(Hz)

2(8.370

l0-28 kg)(7a.16

x l0-34 J.s)' x 10-rt *)'(1.38066 x 10-23 J.K*')

87,56 K
( 1 .055

o,".,(n.,) rot\'-?/

19

:t+

J.s)t
10-23

z(l .614 x

ra-21 kg)(7a.16

x 10-rt m)t(1.38066 x

J.K-')

-- 13.78 K

18-1

3.

of

The average molar rotational energy of a diatomic molecule is RZ. Show that typical value are given by J (J + l) : T /@-,. What are typical values of fbr Nr(g) at 300 K? "/

If' (E')

RT, then 6

--

kuT. From Equation l8 .30u,

r(J
For N, at 300 K,

2t kBT +r)- -i;-

J(J*l)ry104
and J

9 or 10.

18-21. Calculate the contribution of

HrO(g) at 600 K.

each trotrnal mode to lhe molar vibrational heat capacity

o1'

F'or

II,O, the values ol'@uo for

Ouit,7

the three normal modes are 2290 K,5160

K. and 5360 K. For

5360 K'

-?:
R
For O,iu.i

"--llu.',u#,, f=.*)' it-e'' --)- : \600/ .,

1.05

x ro-2

:5160 K,
9

#:\*/
eu,

r,,

/5

60\'z

n==.

e-5r60/600

Y:r36xro-l
-033'5

For

(4u,0,,

2290 K,

/2290\2

\.*/

"-tlttllrrt d-.',rof

18-24. The HCN(g) mnlecule is a linear molcculc,

and the following constants determined spectroscopically are I:18.816 x l0-47 kg'm2, it:2096.7 cm-r 1HC-Nsrrerch), iz:713.46cm I (H-C-N bend, two-fold degeneracy), and i., = 3311.47 cm-' 1H-C stretch). Calculate rhe values of @,o, and )u,n arrd Tu at 3000 K.

We can use thc delinitions of Orot and Ouib to wrile

@"' ,rr Uk.**2'1405K

lt?

o, -vrb
(Duit,,r

ftB

- 30 l7 K (IIC-N stretch) Ouit,,z : 1026 K (H-C-l\f hcnd) Ouih,3 * 4164K (H-C streLch)

For linear polyatomic molecules, Equation 18.59 holds, and so

(-5 -'l/

: R2

*TF -'vib,j ' L

i=l

.(#)'
4164

e-3417

/3000

I-

e-3ot1l3w)z

+2rg\' (1 \ /
3000

,-1026/300t)

- e

10z6l3rt{n12

\3ooo/ ( I - e-476+t3oaa)z 7.5 + 0.e2+ 1.9tt + 0.g t _ 6.21

*, (

\'

e-4764/3000

18-25. The acetylene molecule is linear, the C=C bond lcngth is 120.3 pm, and the C-II bond
length is 106.0 pm. What is the symmetry number of acetylene? Determine the momenr of inerria (Section 13-8) of acetylene and calculate the value of @,n,. The fundamental frequencies of the normal modes are ir:1975 cm-', i, :3310 cm-|, ;., :3277 cm-r, il, :729 cm-t, and is:600 cm-r. The normal modes io and i, ate doubly degenerate. All the other modes are
nondegenerate. Calculate Ouiu. i ond Eu at 300 K.

The symmetry number of acetylene is 2 (Problem 18.24). Choose the coordinate axis to bisect the center of the triple bond, Then

.) ^(120.3 x |, _ 5a mizl 2( ::::- ? 10-12m\' rr.ee5 x 10'u ks) L )

i\L//

-1

o'(
2.368

20.3

0-r2 nr

lo6.o

x to-r' * ) /

\2

(1.67 x lt-t-27 kg;

0-46 kg.

*t

We can use the definitions ot' O,ot and Ooiu to write

rf O...-ror 2l kB
$t.,: vro
o,ib,2 *
ouib,z _ ouir.,,3 _
Ouiu,+ (Duiu5

hc:it
kB

2941 K 4g4g K
4J 15

: _

1049 K

963.3 K

'l'he vibrational molar heat capacities are given by (Equation 1S.26)

Rccause acctylene is a linear polyatomic molecule, we can use Equarion 1g.59 to find the molar heat capacity at 300 K:

(-5 --l/
_-t_

NL

I-t

-.t

l_t i:l

fr
7

vrD,

5
I

2
5 .-r -I
,/
I

(-r u'ib,t -Lfuvib.2 tT Luirr,3 + ZCviu.+ * * ',-.: 6.92 x 10-3 +2.50

2Cu,n,.,

*iz+

x IO-s + 3.69 x l0 t -f 2(0._1e4) + '2(0.s23)

molecules c0nstrained to move in a plane, that' 1B_38. Consider a system of independent clia|omic degrees of freotiom does a two-dimensional is, a two-dimensional ideai diaiomic gas' How many rotator afe that thc cnergy eigenvalues of a two-dimerisional rigid molecule have? Given diatomic

tt:-Ti(where

hz Jz

J=0, 1,2, "'

all Jexcept J :0' / isther'onrentof inertiaof themolecule)withadegeneracygr -2for

deriveanexpresslonfortherotationalpartitionfunction.Thevibrationalpartitionfunctionisthc
gas' Wtite out samc as for a three-dimensional diatomic
q

(T)

( Q,,o,,(T) Q,o,(T ) q",o 7')

ancl clcrivc an expression

diatomic gas' fbr the average energy of this two-dilnensional ideal

A two-dimcnsional diatomic molecule

two translational degrees of freedom' one vibrational of freedom We know that desree of freedom' and one rotational clegree
has

J: ,
So Qror:

h'

J'

-o.,tk'oJ'

-/:o'l'2''

: f,- dJS,r-''lk,r
roo

e,o,

:, *,

J,

rt J e-'l'c)r"t/7'

(ffi)'"

we arc told that

qu,o

is for a three-dimensional gas' is the same for a two-climensional gas as it

andweknowq,,on,tbranidealtwo-dimensionalgasfromPr.oblemlS'3.Wccannowobtainan
gas: expression for the average enelgy of this
q

(T)

:
=

q,,"n,(I){,o,( T){",0(T)

[---7--l \%/ \T:;67'l

ln(lnotcontaining '-et''n/zr1+torms
?"

(2u2nmkrT\ ( oT

\''t /

e-e'"*Pr

terms of ln q: We now wish to find the tenrperature-dependent

lnq

:1n, * |tn t -+(E)

Now. as in ExamPle 18'5, we can take

_Nk*r,(#)
,,

-: R,r.z(+

.#.W -rTG{'""JT)
g -(-.1
vrn'
I IT I '

, Ourn e-@v*l? \

--z

3RT

tR?''o+Rouit, ffi t 2