Tutorial 1:

Adsorption
Jimmy Faria
Catalytic Processes and Materials
MESA+ Institute of Nanotechnology

12/09/2018 MasterMeeting
Course 1
 Learning targets
§ Critically analyze catalyst performance data
§ Derive and apply LH and BET adsorption isotherms
§ Determine, analyze, and discuss the implications of
chemisorption data

2
 On-line Questioner
Can you define the following terms

TON The number of molecules converted per active

site

TOF The number of molecules converted per active

site per unit of time

Rate of Moles or mass of reactants converted per

reaction active site or unit of catalyst (mass, volume,
surface area) per unit of time

3
 Which catalyst is the most active?

100
Catalyst X
Catalyst Y
Conversion (%)

50 We do
not
know!!!

0 50 100
Time on stream (days)

4
 Which catalyst is the most stable?

100

Catalyst X
Conversion (%)

Catalyst Y

50
We do
not
know!!!

0 50 100
Time on stream (days)

5
 Which catalyst is the most selective?

Concentration
1) A ------> B
2) B ------> C We do
not
know!!!
W/F
100
Selectivity to B (%)

Catalyst X
Catalyst Y

50

0
Catalyst X Catalyst Y
6
 Kinetics vs. Thermodynamics
1) A ------> B Exothermic
T1 < T2 < T3 Reaction
T1
T2
Thermodynamic T3
Equilibrium at T1
Conversion

Thermodynamic
Equilibrium at T2

Thermodynamic
Equilibrium at T3

W/F (Catalyst to feed ratio)

7
 Pop Quiz!
1) Why is the chemisorption and exothermic process?

2) What are the key assumptions in the Langmuir Isotherm?

3) How does the Potential Energy Changes as the molecule

approaches the catalyst surface in physisorption and
chemisorption?

8
 Pop Quiz!
1) Why is the chemisorption and exothermic process?

∆" = ∆$ − &∆'

- Change in Gibbs Free Energy should be negative for

adsorption to take place

- Change in Entropy must be negative (lower degrees

of freedom)

9
 Pop Quiz!
2) What are the key assumptions in the Langmuir Isotherm?
a. Homogeneous surface
(all sites identical)

b. Localized adsorption sites

(one adsorbate per site)

c. No adsorbate-adsorbate =
interaction
(constant DHads)

d. Equilibrium between surface

species and gas phase
10
 Potential Energy
3) How does the Potential Energy Changes as the molecule
approaches the catalyst surface in physisorption and
chemisorption?

11
NIOK Book Potential Energy Diagram
Heterogeneous Catalysis

metal + 2 Agas

ΔH A-A
f
Potential energy

E dis
act 0 = metal + A2, gas

ΔH mol
ads
ΔH phys
ads

atom physisorption
2ΔHads of the molecule A2
molecular
chemisorption
of the molecule A2

dissociative
chemisorption
of 2 A-atoms

distance from the surface

12
 Deriving Langmuir isotherms
1) Non-dissociative adsorption

2) Dissociative adsorption

3) Competitive adsorption

13
 Adsorption Isotherms
a)
$" ∗ &"
A + * A-* !" =
1 + $" ∗ &"

b) )
$" ∗ &" *
A2 + 2* 2A - * !" = )
1 + $" ∗ &" *

c)
$" ∗ &"
A + * A-* !" =
1 + $" ∗ &" + $+ ∗ &+
$+ ∗ &+
B + * B-* !+ =
1 + $" ∗ &" + $+ ∗ &+

14
Tutorial Exercises

15
 Non-ideal Isotherms
Adsorption on Pt(111) 35 kcal/mol

QUESTION 1:
Can we say that the sites on
this surface are NO
CO
homogeneous?
20
QUESTION 2: Lateral
Why does the heat of repulsion
H2
adsorption decrease so much (CO dipole
for the CO but not for and H2 is 10
neutral)
hydrogen?

QUESTION 3: Lateral
Which Langmuir assumptions interaction 0 0.2 0.4 0.6 0.8 1.0
are not valid in these are negligible COVERAGE, molec/cm2x 10-15
examples?
16
 Adsorption on surfaces
Example 1.1:
P (Torr) V / V m
The following data of adsorbed volume vs. 0.10 0.30
pressure have been obtained during the 0.14 0.36
adsorption of a gas A on a solid at room 0.20 0.43
temperature. See whether the data are best
0.29 0.49
approximated by a Temkin, Freundlich, or
Langmuir isotherm. From this analysis 0.41 0.54
discuss what would be the nature of the solid 0.58 0.59
or the adsorbate-adsorbate interactions, if 0.82 0.64
they are present in this case. 1.16 0.67
1.65 0.71
2.35 0.74
3.33 0.78
4.73 0.81
6.72 0.84
9.54 0.87

17
 Results - Temkin
Temkin Temkin
Ln P V/Vm
1
-2.303 0.300
0.9
-1.966 0.360
0.8
-1.609 0.430 0.7
-1.238 0.490 0.6

V/Vm
-0.892 0.540 0.5 y = 0.1224x + 0.6293
-0.545 0.590 0.4
-0.198 0.640 R² = 0.9804
0.3
0.148 0.670 0.2
0.501 0.710 0.1
0.854 0.740 0
1.203 0.780 0 0.5 1 1.5 2 2.5
1.554 0.810 Ln P
1.905 0.840
2.255 0.870

18
 Results - Freundlich
Freundlich
0.000
Ln P Ln (V/Vm) -3.000 -2.000 -1.000 0.000 1.000 2.000 3.000
-2.303 -1.204 -0.200
-1.966 -1.022
-0.400
-1.609 -0.844 y = 0.215x - 0.5085
R² = 0.9216
-1.238 -0.713

Ln (V/Vm)
-0.600
-0.892 -0.616
-0.545 -0.528 -0.800
-0.198 -0.446 -1.000
0.148 -0.400
0.501 -0.342 -1.200
0.854 -0.301
-1.400
1.203 -0.248 Ln P
1.554 -0.211
1.905 -0.174
2.255 -0.139

19
 Results - Langmuir
P (Pa) P(Torr) V/Vm 4.00 y = 0.2145x + 1.2488
0.1 0.1 0.3 R² = 0.9903
3.50
0.14 0.14 0.36
0.2 0.2 0.43 3.00
0.29 0.29 0.49 2.50

1/(V/Vm)
0.41 0.41 0.54
2.00
0.58 0.58 0.59
0.82 0.82 0.64 1.50
1.16 1.16 0.67 1.00
1.65 1.65 0.71
0.50
2.35 2.35 0.74
3.33 3.33 0.78 0.00
4.73 4.73 0.81 0.00 2.00 4.00 6.00 8.00 10.00 12.00
6.72 6.72 0.84 1/P (Pa-1)
9.54 9.54 0.87

Conclusion:
Lagmuir is adequate

20
 Isosteric Heat of Adsorption
From the following adsorption data obtained at various temperatures determine the
isosteric heat of adsorption at several different coverages and see whether it
remains constant, as predict by the Langmuir model, or changes, as predicted by
the Temkin or Freundlich models. Draw a potential energy diagram that explains
these trends.
1.00

0.80

0.60 300
Coverage (q)

280
0.40 330

0.20

0.00
0 0.5 1 1.5 2
Pressure (Torr)

21
 Isosteric Heat of Adsorption
Temperature (K) 280 Temperature (K) 300 Temperature (K) 330

Partial Pressure (Torr) Coverage 1 Partial Pressure (Torr) Coverage 2 Partial Pressure (Torr) Coverage 2

0 0.00 0 0.00 0.000 0.00

0.0028 0.03 0.012 0.08 0.010 0.05
0.0075 0.07 0.0075 0.05 0.025 0.12
0.024 0.18 0.012 0.08 0.025 0.12
0.045 0.30 0.034 0.20 0.045 0.20
0.06 0.36 0.044 0.25 0.077 0.30
0.075 0.40 0.058 0.30 0.100 0.36
0.11 0.50 0.09 0.40 0.120 0.40
0.18 0.60 0.135 0.50 0.170 0.50
0.26 0.70 0.21 0.60 0.265 0.60
0.35 0.75 0.32 0.69 0.350 0.65
0.42 0.78 0.47 0.76 0.470 0.71
0.6 0.83 0.6 0.80 0.650 0.76
0.7 0.85 0.7 0.82 0.700 0.78
0.8 0.86 0.8 0.84 0.800 0.80
1 0.88 1 0.86 1.100 0.84
1.2 0.90 1.2 0.88 1.200 0.84
1.5 0.91 1.5 0.89 1.500 0.87
1.9 0.92 1.9 0.91 1.900 0.88
22
 Calculating the Heat of Adsorption
1. Read the pressure for a give coverage and three temperatures to create a table.
1 280 300 330
ѳ P (Torr) P (Torr) P (Torr)
0.3 0.045 0.058 0.077
0.4 0.075 0.09 0.120
0.5 0.11 0.135 0.170
0.6 0.18 0.21 0.265

2. Plot the ln(p) vs 1/T Results:

-1

-1.5
y = -990.07x + 0.4414 ѳ=0.3 Coverage (ѳ) ∆H (KJ/mol)
y = -872.17x + 0.5155 ѳ=0.4 0.3 -8.23
-2
y = -802.52x + 0.6638
ѳ=0.5 0.4 -7.25
Ln(P)

-2.5
y = -717.11x + 0.8404
ѳ=0.6
0.5 -6.67
0.6 -5.96
-3
Conclusion:
-3.5 Lagmuir is not adequate as
0.0028 0.003 0.0032 0.0034 0.0036 0.0038 0.004 there are adsorbate-adsorbate
1/T (K-1)
interactions (forces) 23
 Energy Diagram
Repulsion by polar species causes increase in energy and consequently, a
decrease in heat of adsorption
repulsion
+ + + +
q = 1 - - - -
E(r) q = 0.5

q = 0

24
 BET Adsorption
Adsorption Desorption
Based on the following adsorption data Relative Pressure Quantity Adsorbed Relative Pressure Quantity Adsorbed

of N2 at 77.35 K respond the following (P/Po)

0.00011699
(cm³/g STP)
21.6003412
(P/Po)
0.99173996
(cm³/g STP)
453.823074

questions: 0.00026185
0.00065187
42.9538256
65.7249446
0.98358501
0.97687882
449.770465
444.809829
0.00180524 88.6515084 0.97087522 440.237838
1. What type of isotherm is this? 0.00509835
0.00961208
111.103318
125.402575
0.9511031
0.92247292
427.62362
420.035808

2. Is capillary condensation significant? 0.02393361

0.02969097
148.406879
154.602735
0.89175727
0.86207397
416.968389
415.276074
0.05768431 176.423602 0.83517032 414.118709
3. Using BET and Langmuir isotherms 0.08181807
0.09715818
190.268617
197.863586
0.82658944
0.8013199
413.752799
412.903107

determine the specific surface area 0.11613155

0.13578187
206.553568
215.036837
0.75403053
0.70333489
411.404565
409.864889
0.15532887 223.401091 0.65332376 408.324403
of the sample? 0.17437115
0.20177626
231.938777
246.480849
0.60314885
0.55313098
406.707169
404.957193

4. Based on the results which model 0.23870727

0.24604834
274.771082
282.165293
0.50336182
0.45490961
402.940068
396.248942
0.26991 309.267537 0.40295023 388.390806
fits the data more accurately? 0.28851216
0.29500091
332.009555
339.660245
0.3504709
0.30762944
378.271629
355.624447
0.32567062 367.228526 0.29872964 346.799437
0.34657753 376.314699 0.27413406 317.645989
0.40817975 387.676619 0.25357315 292.323454
0.45408837 392.152737 0.22468926 263.505384
0.51262819 396.284991 0.20406627 248.340791
0.54470842 398.345843 0.16171227 225.833713
Note: Raw data file is in 0.59627518
0.64683846
401.343323
403.798101
0.14809883
0.09793117
219.907116
197.779317

CANVAS – Tutorial-1 0.69622998

0.74676565
405.902714
407.683154
0.05648591
0.04947176
175.199142
170.451807
0.7958848 409.338622 0.03030938 154.712227
0.81821982 410.11697 0.01380025 133.455564
0.84771816 411.209939 0.01035714 126.533857
0.87266558 412.323241
0.89780175 413.648074
0.92173991 415.463984
0.94535042 418.456041
0.97079634 427.060386
0.97881699 433.472454
0.98675288 444.297778
0.99173996 453.823074
25
 Type of Isotherm
500 Adsorption Desorption

Quantity Adsorbed (cm3/g stp)

400

300
type IV This region corresponds to
monolayer formation (BET
Multilayer 200 and Langmuir)
coverage with
pore filling
100

0
0 0.2 0.4 0.6 0.8 1
Relative Pressure (P/Po)

26
BET Adsorption

27
BET Adsorption

28
 BET Surface Area
0.0012 BET Surface Area Plot
Linear (BET Surface Area Plot)

Quantity Adsorbed (cm3/g stp)

Surface Area: 903.9573 m2/g
0.001
Slope: 0.004734 g/cm³ STP
Y-Intercept: 0.000082 g/cm³ STP
C: 58.666251 0.0008
Qm: 207.6536 cm³/g STP
Correlation
0.9992 0.0006
Coefficient: y = 0.0047x + 8E-05
Molecular R² = 0.9992
Cross- 0.0004
0.1620 nm²
Sectional
Area:
0.0002

0
0 0.05 0.1 0.15 0.2 0.25
Relative pressure (P/Po)

29
 Langmuir Surface Area
0.1 Langmuir Surface Area Report
Linear (Langmuir Surface Area Report)

P/Q (kPa*g/cm3 STP)

Langmuir Surface
1269.2528 0.08
Area (m²/g)
0.003430 g/cm³
Slope:
STP
0.015098 0.06
Y-Intercept:
kPa·g/cm³ STP
b: 0.227165 1/kPa
Qm: 291.5678 cm³/g STP y = 0.0034x + 0.0151
0.04
R² = 0.9916
Correlation
0.995792
Coefficient:
Molecular Cross- 0.02
0.1620 nm²
Sectional Area:

0
0 5 10 15 20 25
Pressure (kPa)

30
CO-Chemisorption on Pt-Al2O3

Sample Mass: 0.5579 g

Pt = 0.5 wt. %
Density of Pt = 21.4 g/ml
Active Loop Volume at 25.0 °C: 0.10728 mL STP

31
 CO-Chemisorption on Pt-Al2O3
- Active Metal Dispersion
'()* ,-
%" = $% ∗ ∗ ∗ 100% ∗ 100% Eq. 1
'+ ,%
Sf: Stoichiometry CO to Pt
Vads: Vol. Adsorbed
Vg: Molar Volume of the gas at STP
MW: Molecular weight of the metal
%M: % Metal

- Active Metal Surface Area (per gram of sample)

'()* 56
,$0* = $% ∗ ∗ 12 ∗ 34 ∗ 78 6 Eq. 2
'+ 10 95
Sf: Stoichiometry CO to Pt
Vads: Vol. Adsorbed per mass of sample
Vg: Molar Volume of the gas at STP
NA: Avogadro’s Number
%M: cross-sectional area of active metal atom
32
 CO-Chemisorption on Pt-Al2O3
- Active Metal Surface Area (per gram of metal)

()*$ 100% 34
!"#$ = "& ∗ ∗ ∗ /0 ∗ 12 ∗ 56 4 Eq. 3
(+ %! 10 73

Sf: Stoichiometry CO to Pt
Vads: Vol. Adsorbed per mass of sample
Vg: Molar Volume of the gas at STP
NA: Avogadro’s Number
sm: cross-sectional area of active metal atom

- Average Crystallite Size

9+ 3; 10= 73
8= ∗ ∗ Eq. 4
: ∗ !"#2 10< 3; 13

33
 Results
CO Chemisorption TEM characterization

Do the results match?

34
 Discussion questions
Adsorption and desorption isotherms of N2 at
liquid-N2 temperature on porous catalyst supports
exhibits hysteresis. Which statement is correct?
Shortly explain why the other statements are not
correct.
a. Adsorption proceeds at lower pressure than (the opposite due to the
desorption. liquid curvature)

a. The hysteresis loop depends on pore volume, (shape of the support does
particle size, pore shape and shape of the not affect)
support.

b. The hysteresis loop depends exclusively on (also on size of pore-mouth,

pore volume and pore size. surface tension)

c. It is absolutely necessary to wait for equilibrium (correct)

for every point of the adsorption isotherm.
35
 Discussion questions
Which statement is correct? Shortly explain
why the other statements are not correct.
(4p)
a. A TOF is just another way to express a
reaction rate constant.
a. Atoms at edges and corners usually
interact stronger with adsorbates than
atoms in densely packed surfaces.
b. The TOF is constant when an ensemble
of surface atoms is needed.
c. The TOF usually depends on the
support particle size.
(No. k is the kinetic constant
depending only on T, and TOF is the
intrinsic rate of reaction and depends
on concentrations)
(correct)
(No. In smaller particles fewer
ensembles at a constant total metal
surface)
(Not. TOF usually depends on metal
particle size)
36
 Discussion questions
Which statement in false? Explain your answer.
a. Reactions proceeding on step sites are
particular sensitive to catalyst poisoning.
b. The support of catalyst can influence the rate
even if the metal particles are not influenced at
all by the support.
c. Reaction rate of an exothermic reaction
measured in the lab using an undiluted catalyst (False)
bed is likely lower than the real intrinsic value.
d. Increasing the concentration of the reactant in a
catalyzed decomposition reaction can never
cause a decrease in reaction rate.

37
 Discussion questions
Which statement is correct? Shortly explain why
the other statements are not correct.
a. The result of a chemisorption experiment using (correct)
the dynamic method (also called pulse
method) is not influenced by physisorption on
the support.
(metal loading and/or stoichiometry
b. The dispersion of a supported metal catalyst
of the chemisorption (i.e. probe
can be calculated based on exclusively a
molecules per surface metal atoms)
chemisorption experiment.
(The cause of deactivation cannot be
c. With a chemisorption experiment one can
addressed by chemisorption only the
distinct between catalyst deactivation caused
number of exposed surface metal
by sintering or by covering the surface with a
atoms; as both deactivation
poison.
mechanism will result in a decrease
d. The shape of the peak when performing in the # exposed sites)
chemisorption experiments with the dynamic
method (also called pulse method), after (peak broadening due to the
saturation of the metal surface is achieved, is physisorption)
not influenced by physisorption on the support.
38
Additional Exercise

39
 Isosteric Heat of Adsorption_2
From the following adsorption data
obtained at various temperatures
determine the isosteric heat of
adsorption at several loadings
(mmol/g) and see whether it
remains constant, as predict by
the Langmuir model, or changes,
as predicted by the Temkin or
Freundlich models.

Equilibrium adsorption isotherms at different

temperature for Cd(II)–BFA system (pH0: 6.0;
m: 10 g/dm3).
40
 Isosteric Heat of Adsorption_2

Adsorption isosters for determining isosteric

heat of adsorption for Cd(II)–BFA system.

41
 Isosteric Heat of Adsorption_2
From the following adsorption data
obtained at various temperatures
determine the isosteric heat of
adsorption at several loadings
(mmol/g) and see whether it
remains constant, as predict by
the Langmuir model, or changes,
as predicted by the Temkin or
Freundlich models.

Equilibrium adsorption isotherms at different

temperature for Cd(II)–RHA system (pH0: 6.0;
m: 10 g/dm3).
42
 Isosteric Heat of Adsorption_2

Equilibrium adsorption isotherms at different

temperature for Cd(II)–RHA system (pH0: 6.0;
m: 10 g/dm3).
43