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Problem 1

A surface is half-covered by a gas when the pressure is 1 bar. If the simple Langmuir
isotherm applies:
a. What is K?
b. What pressures give 75%, 90%, 99%, 99.9% coverage?
c. What coverage is given by pressures of 0.1 bar, 0.5 bar, 1000 bar?
Solution
[A] 1
[A]

K
K
+
=
a.
bar 1 1
bar 1
5 . 0
+

=
K
K
1
bar 1

= K
b.
1
1
bar 1 1
bar 1

+

=
P
P
1

= P
bar 999 999 . 0
bar 99 99 . 0
bar 9 90 . 0
bar 3 75 . 0
P
P
P
P
= =
= =
= =
= =
1
1
bar 1 1
bar 1

+

=
P
P
c.
999 . 0 bar 1000
33 . 0 bar 5 . 0
091 . 0 bar 1 . 0
= =
= =
= =
P
P
P
Problem 2
The following results were reported by Langmuir for the adsorption of nitrogen on
mica at 20 C:
Pressure/atm 2.8 4.0 6.0 9.4 17.1 33.5
Amount of gas
adsorbed/mm
3
at
20 C and 1 atm

12.0

15.1

19.0

23.9

28.2

33.0
a. Make a linear plot of these values in order to test the Langmuir isotherm. If it
applies, evaluate the constant K.
b. Suppose that 10
15
molecules cover 1 cm
2
of the surface. Make an estimate of the
effective area in Langmuirs experiment.
Solution
The amount x adsorbed is proportional to u and therefore,
[A] 1
[A]

K
aK
a x
+
= =
To convert atmospheres to concentrations:
3
dm mol
15 . 293 08205 . 0
/atm

= =
P
RT
P
V
n
To convert amount of gas adsorbed to moles:
mol
15 . 293 08205 . 0 10
mm /
mol atmdm 15 . 293 08205 . 0
(atm) 1
6
3
1 3

=

= =

V

V
RT
PV
n
Concentration/mol dm
-3
0.116 0.166 0.249 0.391 0.711 1.39
Amount adsorbed/10
-7
mol 4.99 6.28 7.90 9.94 11.7 13.7
a. A linear plot may be obtained by plotting 1/x against 1/[A]:
[A] 1
[A]
K
aK
x
+
=
a aK x
1
[A]
1 1
+ =
[A]
-1
/mol dm
-3
8.62 6.02 4.02 2.56 1.41 0.719
x
-1
/10
6
mol 2.00 1.59 1.27 1.01 0.85 0.73
6
6
10 161 . 0
1
10 615 . 0
1
=
=
aK
a
0 2 4 6 8 10
1/[A]
0.0
0.5
1.0
1.5
2.0
2.5
1
/
x
Y = 0.161* X + 0.615
1 3
6
mol dm 82 . 3
mol 10 63 . 1

=
=
K
a
b.
Complete coverage corresponds to
1.6310
-6
mol=9.8210
17
molecules
The surface area was thus about
9.82 10
17
/10
15
=10
3
cm
2
=10
-1
m
2
Problem 3
The following data relate to the adsorption of nitrogen at 77 K on a 1.00-g sample of
silica gel:
P/kPa 15.2 54.8
V/cm
3
(STP) 135 247
At 77 K the saturation vapor pressure P
0
of nitrogen is 101.3 kPa. Estimate the surface
area of the gel, taking the molecular area of nitrogen to be 1.6210
-19
m
2
.
Solution
Insertion of the data into the BET equation gives the following two simultaneous equations:
0 0
2 . 15 1
132 . 0
V K V
+ =
0 0
8 . 54 1
483 . 0
V K V
+ =
) (kPa 17 . 3 ) (cm 113
1 3
0

= = K V
At STP, 22.4 L=22400 cm
3
is the volume occupied by 1 mol.
A volume of 113 cm
3
thus contains 113/22400=0.00504 mol; 0.005046.02210
23
=3.0410
21

molecules.
Since each molecule occupies 1.6210
-19
m
2
, the estimated surface area is
3.0410
21
1.6210
-19
=492 m
2
Problem 4
A first-order surface reaction is proceeding at a rate of 1.510
-4
mol dm
-3
s
-1
and has a rate
constant 2.010
-3
s
-1
. What will be the rate and the rate constant if
a. the surface area is increased by a factor of 10?
b. the amount of gas is increased tenfold at constant pressure and temperature?
If these values of v and k apply to a reaction occurring on the surface of a spherical vessel of
radius 10 cm:
c. What will be the rate and rate constant in a spherical vessel, of the same material, of radius
100 cm, at the same pressure and temperature?
d. Define a new rate constant k that is independent of the gas volume V and the area S of the
catalyst surface.
e. What would be its SI unit?
Solution
a. The rate and the rate constant are both increased by a factor of 10:
v=1.5 10
-3
mol dm
-3
s
-1
; k= 2.010
-2
s
-1
b. The rate of conversion (mol s
-1
) remains the same, but since the volume is increased by a
factor of 10 the rate is reduced by a factor of 10, as is the rate constant:
v=1.5 10
-5
mol dm
-3
s
-1
; k= 2.010
-4
s
-1
c. Increasing the radius by a factor of 10 increases the surface area by a factor of 100 and
the volume by a factor of 1000. The rate and the rate constant are thus reduced by a
factor of 10:
v=1.5 10
-5
mol dm
-3
s
-1
; k= 2.010
-4
s
-1
d. Since k is proportional to S and inversely proportional to V, the constant k=kV/S is
independent of V and S.
e. Its SI unit is m s
-1
.
Problem 5
Suggest explanations for the following observations, in each case writing an appropriate
rate equation based on a Langmuir isotherm:
a. The decomposition of phosphine (PH
3
) on tungsten is first order at low pressures and
zero order at higher pressures.
b. The decomposition of ammonia on molybdenum is retarded by the product nitrogen,
but the rate does not approach zero as the nitrogen pressure is increased.
Solution
] [PH 1
] [PH
3
3
K
kK
v
+
=
a.
low pressure ] [PH
3
kK v =
k v =
high pressure
] [N ] [NH 1
] [NH
2 3
3
i
K K
kK
v
+ +
=
b.
c. On certain surfaces (e.g., Au) the hydrogen-oxygen reaction is first order in hydrogen
and zero order in oxygen, with no decrease in rate as oxygen pressure is greatly
increased.
d.The conversion of para-hydrogen into ortho-hydrogen is zero order on several
transition metals.
] [O ] [H 1
] ][O [H
2 O 2 H
2 2 O
2 2
2
K K
kK
v
+ +
=
c.
small is ] [H
2 H
2
K
islarge ] [O
2 O
2
K
] [H
2
k v =
d.
2 / 1
2
2 / 1
] [H
1
1
K
=
2
2
) 1 ]( [H = k v
K
k
v =
Solution
Problem 6
The surface tension of water at 20 C is 7.2710
-2
N m
-1
and its density is 0.998 g cm
-3
.
Assuming a contact angle u of zero, calculate the rise of water at 20 C in a capillary
tube of radius (a) 1mm and (b) 10
-3
cm.
Solution
2

g rh
=
(a)
g r
h

2
=
m 10 49 . 1
) s (m 81 . 9 ) m (kg 998 (m) 10
) m (N 10 27 . 7 2
2
2 3 3
1 2

h



=

=
r=10
-3
m
(b)
m 49 . 1
) s (m 81 . 9 ) m (kg 998 (m) 10
) m (N 10 27 . 7 2
2 3 5
1 2

h =

=


r=10
-5
m
Problem 7
The two arms of a U-tube have radii of 0.05 cm and 0.10 cm. A liquid of density 0.80 g
cm
-3
is placed in the tube, and the height in the narrow arm is found to be 2.20 cm higher
than that in the wider arm. Calculate the surface tension of the liquid, assuming u=0.
Solution
g r
h

2
=
|
|
.
|

\
|
=
2 1
1 1

r r g
h
|
.
|

\
|

=

001 . 0
1
0005 . 0
1
) s (m 81 . 9 ) m (kg 10 8 . 0
2
m 022 . 0
2 3 3

1 2
m N 086 . 0 s kg 086 . 0

= =
Problem 8
The density of water at 20 C is 0.998 g cm
-3
and the surface tension is 7.2710
-2
N m
-1
.
Calculate the ratio the vapor pressure of a mist droplet having a mass of 10
-12
g and the
vapor pressure of water at a plane surface.
Solution
3 3 18 3 12
12

3
4
m 10 002 . 1 cm 10 002 . 1
998 . 0
10
droplet Volumeof r = = = =

m 10 21 . 6
7
= r
0017 . 0
(K) 15 . 298 ) K (Jmol 3145 . 8 (m) 10 21 . 6 ) m (kg 10 998 . 0
) mol (kg 10 02 . 18 ) m (N 10 27 . 7 2

2
ln
1 1 7 3 3
1 3 1 2
0
=


=
=

rRT
M
P
P
0017 . 1
0
=
P
P