Homework # 2

ADSORPTION

1) Explain how you might experimentally determine if adsorption of N2 on iron is

chemical or physical.
- a) is a plateau found as pressure increases? If, so è chemisorption
- b) does the extent of adsorption decreases when temperature is low enough?
If, so è chemisorption
- c) one expects physisorption at low T and high P
- d) one expects mostly chemisorption at moderate T and low P

2) The pre-exponential factor for associative adsorption of A on Pt is 1017

molecules/(cm2·sec·atm) (where the adsorption rate in molecules/ cm2·sec is given by
rads = kads·PA·θv). The desorption pre-exponential factor is 1028 molecules/(cm2·sec),
where the rate of desorption is given by rdes = kdes·θA) The heat of adsorption for A on
Pt is -30 kcal/mol, and the desorption activation energy is 34 kcal/mol.

a. Using this information, develop a numerical expression for the dependence of θA as a

function of PA and T (i.e., the Langmuir adsorption isotherm).
b. At what temperature T will θA = 0.1 when PA = 1 atm?
c. At what pressure PA will θA = 0.5 at T = 800 K?
d. At what pressure PA will θA = 0.01 at T = 800 K?
e. The platinum surface is initially clean at 800 K. At t = 0, the surface is exposed to a partial
pressure of 1 atm of A. What is the eventual fractional coverage of the surface θA? What is the
initial rate of adsorption of A on the surface (molecules/ cm2·sec)? At this rate, how long would
it take to completely saturate the surface (assuming 1015 Pt atoms/cm2)?

3) The following data was collected for the chemisorption of H2 at 25°C on 1.0 g of a 0.5
wt% supported metal catalyst:

H2 partial pressure, torr Vads (cm3 at 25°C and 1 atm)

6.25 0.00712
12.5 0.00936
125 0.01704
250 0.02016

a. Determine the moles H2/g catalyst and the moles H2/g metal adsorbed at monolayer
coverage (saturation) of the active surface area, using both Langmuir associative and
Langmuir dissociative adsorption isotherms. Also, for each isotherm, determine the
adsorption equilibrium constant KH2.

b. From the data, which isotherm, associative or dissociative, best fits the data?

c. Using the best (associative or dissociative) isotherm, calculate the value of θH (i.e., the
fractional coverage of the surface by adsorbed hydrogen) at each of the partial pressures
given above.
HW #2, problem 3
Data:
P Vads 1/P 1/sqrt(P) 1/Vads
6.25 0.00712 0.16 0.4 140.4494 6.25 0.239182
12.5 0.00936 0.08 0.2828427 106.8376 12.5 0.31443
125 0.01704 0.008 0.0894427 58.68545 125 0.572425
250 0.02016 0.004 0.0632456 49.60317 250 0.677235

Associative Langmuir Dissociative Langmuir

160 160
y = 573.04x + 52.792 y = 264.75x + 33.593
140 R² = 0.9788 140
R² = 0.99887

120 120

100 100
1/Vads

1/Vads
80 80

60 60

40 40

20 20

0 0
0 0.05 0.1 0.15 0.2 0 0.1 0.2 0.3 0.4 0.5
1/P sqrt(1/P)

Associative
Vm = 1/intercept = 0.018942264 cm3 H2
n = PV/RT = 7.74612E-07 mole H2/g cat KH = 0.092126
1.55E-04 mole h2/g metal
Dissociative
Vm = 1/intercept = 0.029768106 cm3 H2
n = PV/RT = 1.21746E-06 mole H2/g cat KH = 0.0161
2.43E-04 mole h2/g metal