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CHEM 4641 Physical Chemistry I

Chapter 16 (long-book chapter 33) Recommended Problems


Chapter 16 (33) Problem 1 Maxwell speed distribution in two dimensions
The velocity distribution is simply the Maxwell-Boltzmann distribution, N e-E/(kT), where E =
(1/2)mv2. This must be normalized in two dimensions.
+

1=

N e

mv2
2kT

v x =

1
= 2
N

mv2x
2kT

dv x

v x =0

[(

1
2kT
= 2
N
4m

dv x dv y

1/ 2 2

The integral is in Appendix B.

( 2 mkT )

so N =

m
2 kT

To pass from the velocity distribution to the speed distribution change to polar coordinates (v,),
then integrate out the direction angle. Note that dvxdvy = v d.
2

P( v) =

=0

P(v x , v y )v d =

mv

m
ve
2 kT

mv2 2
2kT

d
0

m
P( v) =
v e 2kT
kT

Chapter 16 (33) Problem 5 Average speed and kinetic energy of O2 and CCl4 at 298K

8kT
1
m 3RT 3
Ek = m v 2 =
= RT
m
2
2 m
2
O2 and CCl4 have the same average kinetic energy.
Their average speeds differ.
v=

81.38061023 J / K298K

1/ 2

= 197168 = 444 m/s


321.66051027 kg
mO2 1/ 2
32
v CCl4 = v O2
=444 m/ s
= 203 m/s
mCCl4
153.8
v O2 =

( )

CHEM 4641 Physical Chemistry I


Chapter 16 (33) Recommended Problems, continued
Chapter 16 (33) Problem 7 Travel times of N2 and H2 at 298 K and 1 atm, moving 1 m in any direction
A simple approximate way to solve this problem is to change the question slightly. On may ask how
long a molecule, if traveling at its average speed, takes to move 1 m. Then t = R / <v>, where R is the
distance traveled. (R = 1 m)
a. hydrogen to travel 1 m, t = 1.0 m / <v> = 1.0 m X [ m / (8 k T)]1/2
m = 2.02 amu X 1.6605X10-27kg/amu = 3.347X10-27 kg
t = 0.000565 s
b. nitrogen
m = 28.02 amu X 1.6605X10-27kg/amu = 4.653X10-26 kg
t = 0.000565 X (28.02 / 2.02)1/2 = 0.0021 s
nitrogen requires an additional 0.0015 s for an average displacement of 1 m
c. The fraction of nitrogen molecules requiring more time will simply be the fraction of nitrogen
molecules traveling at speed less than the average speed. That is,
v

P(v < v

ave

)=

ave

P(v < v ave ) = 4


2

P (v ) d v

0
v
3/2 ave 2 m v 2 /(2 k T )

(2 mk T )

v e

dv

Let u m v /(2 k T ). u=v m/(2 k T )


The upper limit becomes v ave m/( 2k T ) = 8 k T /( m)

m/(2 kT )

= 2/ .

In the integrand, v 2 =(2 k T /m)u 2 and d v = 2 k T /m du


3/2 2 k T
m
P(v < v ave ) = 4
2k T
m

4
P(v < v ave ) =

2/

2 u2

u e

2/
2
2 k T 1/ 2
u 2 eu d u

m
0

( )

du

Numerical integration gives 0.533.


That is the fraction of molecules having speeds less than the average speed.

CHEM 4641 Physical Chemistry I


Chapter 16 (33) Recommended Problems, continued
Chapter 16 (33) Problem 7, continued
The question as asked, average time for a particular distance, requires the distribution of
molecular times. The relationship between t and v is simple: t = R/v, where R=1.0 m is the
distance traveled.
<t> = R <1/v> (which will not equal R/<v>)
One can calculate t from 1 /v

1
t =R P(v) d v
v
0
3/2 1 2 m v 2 /(2 kT )
m
dv
v v e
2 kT
0
3/2
m
m v 2 /(2 kT )
t =R 4
ve
dv

2 kT
0

t =R 4

(
(

)
)

Let u2 m v 2 /(2 k T ) Then v dv =(1/2) d( v 2 )=(2 kT /m)u du


3/2 2 k T u2
m
t =R 4
e du
2 kT
m 0

2
The integral eu du = is given in Appendix A.
4
0

m 1/2 1
= R 4 m 1/2 = 4 R

2kT
8k T
v ave
3 /2 4
Average time is longer than that calculated by the approximate method.
The fraction of longer-time molecules can be calculated using the same integral as in the
approximate solution, except that the upper limit is R/<t> instead of vave.
t = R 4

( )

( )

Chapter 16 (33) Problem 11 Probabilities of velocity ranges in one dimension


2
Given: P(|vx| vo) = erf( mvo /(2kT)) where erf ( z)
2

ex

dx.

2kT
(

m ) = erf (1) = 0.84


2k T
2k T
P (v
= 1 P (v
)
m
m ) = 1 erf (1) = 1 0.84 = 0.16

Let v 0 =
x

2k T
m

P v x
x

CHEM 4641 Physical Chemistry I


Chapter 16 (33) Recommended Problems, continued
Chapter 16 (33) Problem 12 speed of sound at T=1000K.
vsound = ( RT /M)1/2 where = CP/CV = CP/(CP-R)
For a monatomic ideal gas CP = (5/2) R = 20.79 J/(mol.K) so = 5 /3 = 1.667
a)
gas
M (kg/mol) vsound(m/s)
Ne
0.02018
829
Ar
0.03995
589
Kr
0.08380
407
b) vsound(Ar, 1000K) = vsound(Kr, T)
1000 / 39.95 = T / 83.80
T = 1000K X (83.80 / 39.95) = 2098 K
Chapter 16 Problem 19 Translational kinetic energy distribution for an ideal gas
3 /2 2 m v 2 /(2 k T )
m
P(v )=4
v e
2k T
dv
P( Etr ) = P(v)
d Etr

m 2
v
2
2 1/2
v=
E
m tr
dv
= (2m Etr )1 /2
d Etr
Etr =

P( Etr ) = 4
P( Etr ) =

3/2 2 E tr Etr /(kT )


m
e
(2 m Etr )1 /2
2 kT
m

2
( k T )3/2

Etr /(kT )

E 1/2
e
tr

Chapter 16 (33) Problem 23. Collision rate with walls of a cube


Wall area = 6 sides X area of one side = 6 cm2 = 6X10-4 m2.
P
Collisions per area per second = Z c =
(2 mkT )1/2
101325 Pa
Zc =
(2 39.95 amu1.66051027 kg /amu1.38061023 J / K298 K )1/2
Z c = 2.451027 m2 s1
Collisions/second = Zc X area = 1.5X1024/s

CHEM 4641 Physical Chemistry I


Chapter 16 (33) Recommended Problems, continued
Chapter 16 (33) Problem 26 rate of collisions of oxygen with a surface
P
kg
Zc =
. m=32.0g/mol1.661027
= 5.311026 kg
amu
2 mkT
(a)

Z =
c

101325 Pa

2 5.311026 kg1.3811023 J / K 298K


27 2 1

Z =2.7310
c

= 2.7310

23

23

3.7110

Js /m

2 1

cm

25

multiply by 60 to get collisions per minute: 1.6410 cm


101325
10
Torr = 1010
Pa = 1.33108 Pa
(b) P = 10
760

101325 J / m

min

8
At that pressure, Z = 2.731023 1.3310
= 3.61010 cm2 s1
c
101325

Chapter 16 (33) Problem 28 collision frequency and mean free path in nitrogen
N2 gas. m = 28.02 amu = 4.65310-26 kg.

P
(a) P = 1 atm. T = 298K. The single-particle collision frequency Z 11 = 2 v .
kT
8RT
v =
= 475 m/s
M
2
18 2
(Table 16.1 or 33.1)
=0.43 nm = 0.4310
m
P
101325 Pa
=
= 2.461025 m3
23
kT
1.38110 J / K298K

25

Z 11 =( 2.4610

)( 0.431018 m2) 2( 475 m/s) = 7.110 9 s1

The answer does not disagree with 1010 reported in the CRC Handbook.
(b) It is convenient to note that collision frequency is proportional to pressure and inversely
proportional to the square root of temperature.
P
298K
9 1
9 1
4
Z c =3.1610 s =7.1110 s
= 3.910 Pa = 0.38 atm
101325 220K

(c) At T=220K, v = 475 m/ s


v
=
Z

11

408 m/s

220
= 408 m/s
298

9 1

3.1610 s

= 130 nm

CHEM 4641 Physical Chemistry I


Chapter 16 (33) Recommended Problems, continued
Chapter 16 (33) Problem 30 Collision frequency of carbon dioxide
a) P=1atm. T=298K. From Table 16.1 (or 33.1) in this chapter, =0.52 nm2 = 5.2X10-19 m2.
The total collision frequency Z11 = (1/2) (N/V)2 <vrel> = 2-1/2 (P/kT)2 [8RT/(M)]1/2
P/(kT) = 101325 Pa / ( 1.3806X10-23J/K X 298K) = 2.463X1025 m-3
[8RT/(M)]1/2 = [ 8X 8.3145 J/(mol K) X 298K / ( X 44.01X10-3kg/mol)]1/2
= [ 143360 (m/s)2 ]1/2 = 379 m/s
Z11 = 0.7071 X (2.463X1025 m-3)3 ( 5.2X10-19 m2 ) X 379 m/s
Z11 = 8.45X1034 m-3 s-1
b) At what T does Z11 = 0.10 X 8.45X1034 m-3 s-1 ? Suppose pressure is unchanged.
Z11 is proportional to T-3/2 at constant pressure.
8.45X1034 m-3 s-1 X (298)3/2 = 0.10 X 8.45X1034 m-3 s-1 X (T)3/2
10 X (298)3/2 = T3/2
T = 102/3 X 298K = 1380 K
Chapter 16 (33) Problem 32 mean free path of Argon at 298K and various pressures. =0.36 nm2.
kT
1 1.38061023 J /K 298 K
8.08 X 103 Pam
=
=
P 3.61019 m2 2
P
P 2
a) P = 0.5 atm.
= 8.08X10-3 Pa m /(0.5 X 101325 Pa) = 1.6X10-7 m = 160 nm
b) P = 0.005 atm.
= 8.08X10-3 Pa m /(0.005 X 101325 Pa) = 1.6X10-5 m = 16 m
-6
c) P = 5X10 atm. = 8.08X10-3 Pa m /(5X10-6 X 101325 Pa) = 0.016 m = 16 mm
=

Chapter 16 (33) Problem 33 mean free path of Ne, Kr and CH4 at 500K and 1 atm.
23

26 2

kT
1.380610
J / K500 K
4.82 X 10
m
=
=

P 2 101325 Jm3 2
a) Ne. =0.24 X 10-18 m2. = 2.01 X 10-7 m
b) Kr.
Kr = Ne ( Ne /Kr)
= 2.0X10-7m (0.24 / 0.52) = 9.3X10-8 m
=

c) CH4.

CH4 = Ne ( Ne /CH4) = 2.0X10-7m (0.24 / 0.48) = 1.1X10-7 m

CHEM 4641 Physical Chemistry I


Chapter 16 (33) Recommended Problems, continued
Chapter 16 (33) Problem 34. Pressure required to obtain a desired mean free path.
kT
The basic equation is =
.
P 2
kT
It is easily rearranged to give P as a function of T. P =
2
The collision cross section = 0.40 nm2 = 4.0X10-19 m2.
= 20.0 cm = 0.200 m. k = 1.3806X10-23 J/K. T = 500.0 K.
P = 0.061 Pa = 4.6X10-4 torr
Chapter 16 (33) Problem 35 Compare vmp, vave, and vrms for the 1-d Maxwell speed distribution
The one-dimensional speed distribution is P(v ) = 2

m 1 /2 m v 2 /(2 k T )
e
, where v is
2k T

the speed and runs from from 0 to .

P( v)d v = 1 .

Normalization is

Most probable speed vmp=0, because P(v) is greatest at v=0.

Average speed v ave = v P (v ) d v


0

1/ 2
m
m v 2 /(2k T )
v ave = = 2
v
e
dv

2k T
0

1/ 2 k T u
m
v ave = = 2
e du
2k T
m 0

v ave = =

Let u = mv2/(2kT).

The integral equals 1.

2k T
m

v 2rms = v 2 P( v )d v .

Root-mean-square speed

1/2 2 m v 2 /(2 k T )

v 2rms

( 2 mk T )
m
=2(
2k T )

v 2rms = 2

rms

1/2 2 k T

kT
m

dv

4m

2 kT
kT
=
m
m

Just as in three dimensions, vmp < vave < vrms.

The integral is in Appendix A.