16

TOPIC 4 - THE COLLISION THEORY

Example of solved problems
1. For molecular oxygen at 25
o
C, (a) calculate the collision frequency z
11
and (b)
the collision density Z
11
at a pressure of 1 atm. Given: d
oxy.
= 0.361 nm.
Answer:
The collision diameter of O
2
is 0.361 nm or 0.36110
-9
m
(a) Collision frequency z
11
= (d
2
) rel C = (d
2
) <v
11
>
Collision cross-section= = d
2
= (0.36110
-9
m)
2
= 4.09410
-19
m
2

Relative mean speed, rel C = <v
11
> > < =
1
2 v
<v
1
>
2 / 1
1 3
1
10 32
298 314 . 8 8
|
|

\
|


=

mol kg
K s m kg

= 444 ms
-1

<v
11
>= 2 2
1
>= < v (444 ms
-1
) = 627.9 ms
-1
Molecule density = =
) 298 )( 08206 . 0 (
) 10 )( 10 022 . 6 )( 1 (
1 1
3 3 1 23
K mol K L atm
m L mol atm
RT
PN
V
N
A

= =
= 2.4610
25
m
-3
So z
11
= (d
2
) <v
11
> =(4.09410
-19
m
2
)( 627.9 ms
-1
)( 2.4610
25
m
-3
)
= 6.3310
9
s
-1

(b) Collision density Z
11
= =
2
1
2
1
11
z (d
2
) rel C = 7.7810
34
m
-3
s
-1
=
1 23
1 3 3 1 3
10 022 . 6
) 10 )( 1034 78 . 7 (

mol
L m s m
= 1.2910
8
mol L
-1
s
-1
2. Large vacuum chambers have been built for testing space vehicles at 10
-7
Pa. Calculate
the number of molecular impacts per square meter of wall per second for molecular
CO
2
(d = 0.40 nm) at 35
o
C?

Answer:
Use formula of collision with wall, J
N
=
4
> < v

Calculate one item after another:

i. Molecule density:
3 13
1 1 3
1 23 7
10 34 . 2
15 . 308 3145 . 8
10 02 . 6 10



=

= = = m
K mol K m Pa
mol Pa
RT
PN
V
N
A

17
ii. Mean speed :

1
2 / 1
1 3
1 1 1
2 / 1
07 . 385
10 44
308 314 . 8 8 8



=
(

=
(

= ms
mol kg
K mol K s m kg
M
RT
v


iii. Put together:
4
) 07 . 385 )( 10 34 . 2 (
4
1 3 13

=
> <
= =
ms m v
J Zw
N

= 2.2510
15
m
-2
s
-1
3. A 10 mL container with a hole1m in diameter is filled with hydrogen. This
container is placed in an evacuated chamber at 10
o
C. How long will it take for
80% of the hydrogen to effuse out?

Answer:

h hh h 13.15 13.15 13.15 13.15 min min min min 789 789 789 789 =
=

= =
> <
=
= =
> <
=
= > <
> <
=
=
> <
=
> <
= =

s t
t ms m
t
m
m
t
V
v A
N
N
N A dt
V
v A
N
dN
v dt
V
v A
N
dN
V
v
V
N v
dt
dN
A
J
t
o
t Nt
N
N
47355
88 . 1730 10 963 . 1 6094 . 1
10 2
283 3145 . 8 8
10 10 4
)
2
10 1
(
20
100
ln
4
ln
molecules of no. , area
4
speed mean
4
volume
4 4
1
1 8
2 / 1
3 3 6
2
6
0
0

4. An effusion cell has a circular hole of diameter 2.50 mm. If the molar mass of
the solid in the cell is 260 g mol
-1
and its vapor pressure is 0.835 Pa at 400 K,
by how much will the mass of the solid decrease in a period of 2 h?

Answer:
( )
g gg g 0.0104 0.0104 0.0104 0.0104 = =

=
= |

\
|
|

\
|
=
> <
=

= =

kg
Pa
s m kg
mol kg s m kg
s m mol kg Pa
w
RTM
t PMA
RTM
t m A PN
w
RTM
PN
M
RT
RT
PN v
t m A
w
Zw J
o o A
A A
o
N
4
2 1
2 / 1 1 3 1 2
2 4 1 3
2 / 1 2 / 1
2 / 1
2 / 1
10 041 . 1
) 10 260 400 3145 . 8 2 (
60 60 2 ) 10 50 . 2
2
1
( 10 260 835 . 0
2 ) 2 (
) 2 (
8
4
1
4

18


Formula for collisions Same molecule Different molecules
1 . Collision frequency, or
collision per second, or
collision of a single
molecule.
z
11
= (d
2
) rel C

z
12
=
2
) 12 (
2
12
) ( rel C d

2. Collision density or
total number of coll. or
-coll. per volume per
second.

Z
11
=
11
2
1
z
=
2
1
d
2
rel C
2
Z
12
=
2 1
) 12 (
2
12
) ( rel C d

3. Collision flux or
collision with wall, or
with surface, or
coll. through a hole, or
coll. per area s
-1
or
rate of effusion.
Z
w
=J
N
=
4
> <
=
v
dt
dN
w

=
t MA
wN
o
A

Exersice 4a
1. What is the mean speed of nitrogen molecule relative to another nitrogen
molecule at 290 K?(662 m s
-1
)

2. What is the average relative speed of hydrogen molecules with respect to
oxygen molecules at 300 K? (1837 m s
-1
)

3. Calculate the average number of molecules per cubic centimeter for
nitrogen gas at 1 bar pressure and 25
o
C? (2.4310
19
)

4. The pressure in interplanetary space is estimated to be of the order of 10
-14

Pa. Calculate the collision frequency for an atom present in the space.
Assume that only hydrogen atoms (d = 0.2 nm) are present and that the
temperature is 1000 K and.(5.910
-10
s
-1
)

5. How many collisions does a single Ar atom (d

= 0.34 nm) make in 1.0 s
when the temperature is 25
o
C and the pressure is 1.0 atm? Given: Ar:
M
R
= 39.95 (4.9810
3
s
-1
)

6. How many collisions per second does an N
2
(d = 0.43 nm) molecule make
at an altitude of 15 km where the temperature is 217 K and the pressure
0.050 kPa. (4.110
6
s
-1
)

7. Calculate the collision frequency for hydrogen molecule in hydrogen gas
at 1.0 bar pressure and 20
o
C? Given: d
H2
= 2.47 . (1.210
7
s
-1
)

19

8.

Calculate the collision density for molecular chlorine at 35
o
C and 770
mmHg. The collision diameter is 5.44 10
-6
cm. (1.1410
35
s
-1
m
3
)

9. What is the average time between collisions of an oxygen molecule in
oxygen gas at 10
-12
bar and 50
o
C (d = 3.60 )?

10. Calculate the mean free path for chlorine gas (d= 0.544 nm) at 0.1 Pa and
25
o
C? (0.0312 m)

11. How many molecules of O
2
strike the wall per unit area per unit time at
600 mmHg at 25
o
C? (d
O2
=3.60 )( 2.110
27
m
-2
s
-1
)

12. Large vacuum chambers have been built for testing space vehicles at 10
-6
Pa.
Calculate the number of molecules of nitrogen (d = 0.375 nm) impact per
square meter of wall per second at 28
o
C. (2.610
21
m
-2
s
-1
)

13. A solid surface with dimensions 2.5 mm3.0 mm is exposed to He gas at 90 Pa
and 500 K. How many collision do the He atoms make with this surface in
15s?(He: M
R
= 4.00) (5.9 10
20
m
-2
s
-1
)



Exercise 4b

1. A box contains H
2
(molecule b) and He (molecule c) at a total pressure of 1.4
atm. If the mixture contains 18% H
2
by weight, calculate the ratio of
z
b
(b)/z
c
(c)? Given d
b
=0.247 nm and d
c
= 2.20 nm.(6.9710
-3
)

2. A gas mixture contains H
2
at 2/3 atm and O
2
at 1/3 atm at 27
o
C. Calculate the
number of collision per second of H
2
with other H
2
, O
2
with other O
2
, and H
2

with O
2
(d
H2
= 0.272 nm, d
O2
= 0.361 nm) (9.510
9
s
-1
, 2.110
9
s
-1
, 4.710
9
) .

3. At 30 km above the Earths surface (roughly in the middle of the
stratosphere) , the temperature is roughly 1000 K and the gas density is
3.7410
23
molecules/m
3
. Assuming N
2
(d

= 0.38 nm) is representative of the
stratosphere, determine z
11;
undergoes in this region of the stratosphere in 1 s.
(2.0910
8
).

4. An equal number of moles of H
2
(d
1
=0.272 nm) and Cl
2
(d
2
=0.544 nm) are
mixed and held at 298 K and the total pressure of 1 kPa. (a) Calculate the
collision frequencies z
12
and z
21
, where hydrogen is component 1 and
chlorine is component 2. (b) Calculate the collision density, Z
12
. (1.1410
8
s
-1
,
1.1410
8
s
-1
, 2.3010
4
mol L
-1
s
-1
)

5. For O
2
(d

= 0.36110
-9
m) at 10
-3
bar at 25
o
C, (a) What is the collision
density Z
11
? (b) What is the average time between collisions of a single
molecule?(1.2610
2
mol L
-1
s
-1
,1.610
-7
s).



20
6. The average surface temperature of Mars is 220 K, and the surface pressure
is 4.7 torr. The Martian atmosphere is mainly CO
2
and N
2
with smaller
amounts of Ar, O
2
, CO, H
2
O, and Ne. Considering only the two main
components, we approximate the Martian atmospheric composition as
xCO
2
= 0.97 and xN
2
= 0.03. The collision diameters are dCO
2
=4.6 and
dN
2
= 3.7 . For gas at 220 K at the Martian surface, calculate (a) the
collision rate for one particular CO
2
molecule with other CO
2
molecules; (b)
the collision rate for one particular N
2
molecule with CO
2
molecules;(c) the
number of collisions per second made by one particular N
2
molecule;(d) the
number of CO
2
-N
2
collisions per second in 1.0 cm
3
.

7. A container of volume 110
-5
cm
3
holds three molecules of gas b, which we
label b
1
, b
2
, and b
3
. In 1 s, there are two b
1
-b
2
collisions, two b
1
-b
3
collisions,
and two b
2
-b
3
collsions. Find z
b
(b) and Z
bb
.

The vapor pressure of water at 25
o
C is 3160 Pa. If every water molecule that
strikes the surface of liquid water sticks, what is the rate of evaporation of
molecules from a square meter of surface? (1.210
26
m
-2
s
-1
)

8. A 5- mL container with a hole10m in diameter is filled with hydrogen. This
container is placed in an evacuated chamber at 0
o
C. How long will it take for
90% of the hydrogen to effuse out? (347 min)

9. Exactly 1 dm
3
of nitrogen, under a pressure of 1 bar, will it takes 5.80 minutes
to effuse through an orifice. How long will it take for Helium to effuse under
the same conditions? (2.19 min)

10. The best laboratory vacuum pump can generate a vacuum of about 1 nTorr. At
25
o
C and assuming that air consists of N
2
molecules with a collision diameter
of 395 pm, calculate the mean free path of the gas. (4.4610
4
m)

11. Dry air had a CO
2
mole fraction of 0.004. Calculate the total mass of CO
2
that
strikes 0.5 cm
2
of one side of a green leaf in 10 s in dry air at 39
o
C and 1
atm? (0.332 g )

12. A certain sample of a pure oxygen ( d = 3.61 ) has mean speed, <v> = 450 m
s
-1
and the average time between two successive collisions of a given
molecule with other molecules is 4.010
-10
s. Find the mean free path and
molecule density in this gas. (1.810
-7
m, 9.610
24
m
-3
)