Physical Chemistry II Chem 402 Spring 2011

Chapter 16 (4, 15, 16, 22)

P16.4) Compute
ave
v for H
2
O, HOD, and D
2
O. Do you need to perform the same calculation each
time, or can you derive an expression that relates the ratio of average speeds for two gases to
their respective masses?


The average speed for H
2
O is calculated as follows:

( )( )
( )
1 1
1
ave
1
8 8.314 J mol K 298 K
8
592 m s
0.0180 kg mol
RT
M
v
t t
= = =

Since the average speed scales as M
-1/2
, the average speed for the other molecules can be easily
related to the average speed of H
2
O as follows:

( )
( )
( )
( )
( ) ( )
( )
( )
( )
( )
( ) ( )
2
2
2
1
ave
1
ave 2
1 1
ave
1
ave 2
1
ave 2
1 1
ave 2
0.018 kg mol
0.973
0.019 kg mol
0.973 592 m s 576 m s
0.018 kg mol
0.949
0.020 kg mol
0.949 592 m s 561 m s
H O
HOD
H O
D O
M HOD
H O M
HOD
M D O
H O M
D O
v
v
v
v
v
v
= = =
= =
= = =
= =

















P16.15) For N
2
at 298 K, what fraction of molecules has a speed between 200. and 300. m s
1
?
What is this fraction if the gas temperature is 500. K?

The fraction of N
2
particles can be found by integrating the speed distribution between
the speeds 200 and 300 m/s
1
:

( )( )
2
6 2
1
6 2 2
1 1
3/ 2
300.

2
2
200.
300.
8 2 5.65 10
200.
0.0280 kg mol
@ 298 K 5.65 10 m s
2 2 8.314 J mol K 298 K
4 e d
2
3.03 10 e d
M
RT
M
RT
M
f
RT
f
v
v
t v v
t
v v

= =
| |
=
|
\ .
=
}
}


Using numerical integration the above expression can be evaluated to yield f = 0.132.
With an increase in temperature to 500. K, the fraction becomes:

( )( )
2
6 2
1
6 2 2
1 1
3/ 2
300.

2
2
200.
300.
8 2 3.37 10
200.
0.0280 kg mol
@ 500 K 3.37 10 m s
2 2 8.314 J mol K 500 K
4 e d
2
1.39 10 e d

M
RT
M
RT
M
f
RT
f
v
v
t v v
t
v v

= =
| |
=
|
\ .
=
}
}
0.071 f =



















P16.16) A molecular beam apparatus employs supersonic jets that allow gas molecules to
expand from a gas reservoir held at a specific temperature and pressure into a vacuum through a
small orifice. Expansion of the gas allows for achieving internal temperatures of roughly 10 K.
The expansion can be treated as adiabatic, with the change in gas enthalpy accompanying
expansion being converted to kinetic energy associated with the flow of the gas:
2
1
2
P R
H C Mv T A = =

The temperature of the reservoir is generally greater than the final temperature of the gas,
allowing one to consider the entire enthalpy of the gas to be converted into translational motion.
a. For a monatomic gas C
P
= 5/2 R. Using this information demonstrate that the final flow
velocity of the molecular beam is related to the initial temperature of the reservoir (T
R
) by:
5
R
RT
M
v =

b. Using this expression, what is the flow velocity of the a molecular beam of Ar where T
R
=
298 K. Notice that this is remarkably similar to the average speed of the gas. Therefore, the
molecular beam resulting can be described as a gas that travels with velocity v, but with a
very low internal energy. In other words, the distribution of molecular speeds around the
flow velocity is significantly reduced in this process.

a)
2
1
2
5 2
R
Mv
v
H
RT H
M M
=
= A
A
=


b) Solving the above expression for Ar yields:

( )( )
( )
-1 -1
-1
-1
5 8.314 J mol K 298 K
5
557 m s
0.0400 kg mol
R
Ar
Ar
v
RT
M
= = =




P16.22) As discussed in Chapter 12, the nth moment of a distribution can be determined as
follows: ( ) ,
n n
x x f x dx =
}
where integration is over the entire domain of the distribution. Derive
expressions for the nth moment of the gas speed distribution.
( )
2
2
0
3/ 2

2
2
0
3/ 2
2
0
F d for 1, 2,...
4 e d
2
4 e d for =
2
n n
M
n
RT
n
n
M
RT
M
RT
v
|v
v v v v
v t v v
t
|
t v v |
t

+
= =
| |
=
|
\ .
| |
=
|
\ .
}
}
}


This integral has 2 possible forms, depending on the parity of the integrand. If n is even
(for n = 2, 4, 6) then 2m = n + 2 for m = 2, 3, 4and the integral becomes

( )
( )
( )
( )
( )
( )
2
3/ 2
2m
0
1/ 2
3/ 2
m
m
2
2
4 e d for m 2, 3, 4,...
2m 1 !
4
2 2
4 2m 1 !

2 2
2 1 !
for 2, 4, 6,....
2
n
n
n
n
n
|v
|
v t v v
t
| t
t
t |
|
|
|
|
v
|

+
| |
= =
|
\ .
| |
| |
=
| |
\ .
\ .

=
+
= =
}


If n is odd (n = 1,3,5,) then 2m + 1 = n + 2 for m = 1,2,3, . The integral becomes
2
3/ 2
2m 1
0
3/ 2
m+1
m
1
2
4 e d for m 1, 2, 3, 4,...
m!
4
2
m!
2
1
!
2
2
n
n
n
n
|v
|
v t v v
t
|
t
t |
|
t |
|
v
t
|

+
+
| |
= =
|
\ .
| |
=
|
\ .
=
+ | |
|
\ .
=
}
for 1, 3, 5,... n =