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Chapter 2
Adsorption
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2.1 Physisorption
In order to react, molecules must come into contact with each other. In
heterogeneous catalysis, the molecules must first adsorb on the catalyst
surface. Molecules will adsorb only when they are attracted to the surface,
i.e. when the enthalpy of adsorption is negative; otherwise the loss of
entropy, when molecules adsorb and lose mobility, will prevent adsorption.
Adsorption is an essential step in a catalysed reaction, because the adsorbed
molecules form intermediate surface complexes that are more likely to react.
In adsorbed molecules, the bonds are weaker and thus, reactions can occur.
Two interactions determine adsorption: physisorption and chemisorption.
Even though the interaction energy is weak (<40 kJ/mol), physisorption
plays an important role in nature. For instance, the van der Waals attraction
between surfaces and the hairs on the feet of geckos enables them to climb
vertical surfaces.
When molecules approach a surface, they undergo physisorption already
at long distance. At short distance they interact much more strongly by
chemical forces (chemisorption). However, the molecules must lose energy
in order to be trapped at the surface in the physisorption or in the
chemisorption well (Fig. 2.1). If the molecules do not lose energy during
collision with the surface they cannot be adsorbed and will reflect.
Physisorption is caused by interactions among permanent, induced and
transient electric dipoles as shown in Table 2.1. In Table 2.1, qi is the charge
on ion i, µi the dipole moment on dipole i, αi the polarisability of molecule i,
Ii the ionisation potential of molecule i and r the distance between the two
species.
25
26 Introduction to Heterogeneous Catalysis

Fig. 2.1 One dimensional representation of non-activated adsorption. (a) elastic

scattering, (b) inelastic scattering, (c) chemisorption, (d) physisorption.
Table 2.1 Types of interactions and their order of magnitude.
Magnitude
Interactions Energy (kJ/mol) Examples
Ion–ion q1 q2 /r 400 Ionic bonding

Ion–dipole −q1 µ2 cos θ/r2 40 Solvation energy
Dipole–dipole −µ1 µ2 (1 − 3 cos2 θ)/r3 4–20 Polar molecules
Ion-induced dipole −q21 α2 /2r4 4 Solvation energy
Dipole-induced dipole −µ21 α2 /r6 0.05 Solutions
Induced dipole- −3/2[I1 I2 /(I1 + I2 )]α1 α2 /r6 4–40 Non-polar
induced dipole molecules
The energy of most of these interactions can be calculated according to

Coulomb’s law. The interactions between an ion and an induced dipole
and between a dipole and an induced dipole moment were derived by
Debye (Nobel Prize in Physics, 1936). The interaction energy between
a dipole and an ion or other dipole depends on the orientation of the
dipole. In Table 2.1, θ is the angle between the dipole moment and the line
connecting the ion and centre of the dipole, or between the two dipoles.
Assuming that molecules rotate fast, that the statistical chance of an
orientation depends on the Boltzmann factor exp(−E/kT) and that the
energy is small compared to kT (then exp(−E/kT) ≈ 1−E/kT), the average
Adsorption 27
dipole–dipole interaction (Keesom) energy is E = −2/3.µ21 µ22 kT/r6 . Many

organic molecules have no dipole moment and are not ions and for these
molecules the interaction between their induced dipoles must be calculated
with the aid of quantum mechanics. The formula for this energy was first
derived by London [2.1] and the corresponding force between molecules is,
therefore, referred to as London or dispersion force.

All above interactions are referred to as van der Waals interactions (van
der Waals, Nobel Prize in Physics, 1910). Van der Waals interactions are
always attractive: molecules move as close as possible to each other. At

short distance, however, repulsive (quantum mechanical) forces play a role
and depend strongly on distance (∝1/r12). Together with the sixth power
dependence of the van der Waals interaction, this gives the Lennard–Jones
energy:
A B
E= − 6. (2.1)
r12 r
The Lennard–Jones energy has a minimum (Fig. 2.1), called the ‘physisorp-
tion well’.
Van der Waals interactions determine the boiling points of molecules.
Table 2.2 shows that noble gas atoms and small symmetric molecules
(which have no dipole moment) interact weakly and thus, have low
boiling points. This explains why it is difficult to make liquid H2 and
He (Kamerlingh Onnes liquefied helium in 1908 and discovered supercon-
ductivity in 1911; Nobel Prize in Physics 1913). Liquid helium is very
important in superconducting magnets, a component of modern Nuclear
Magnetic Resonance (NMR) spectrometers (see Section 3.6). Van der
Waals forces are more or less additive, meaning that contributions by
Table 2.2 Lattice energy of molecules in the solid state in kJ/mol.
Molecule Keesom Debye London Total
He 0.2 0.2
H2 1.5 1.5
N2 7.4 7.4
CO 0.0004 0.008 8.8 8.8
CH4 14.6 14.6
HCl 3.3 1.0 16.8 21.1
NH3 13.3 1.6 14.7 29.6
H2 O 36.4 1.9 9.0 47.3
Cl2 59.0 59.0
the atoms in molecules can be added together. As a consequence, larger

molecules interact more strongly and have higher boiling points. Thus,
in a series of hydrocarbons Cn H2n+2 , the boiling point increases almost
linearly with carbon number and branched hydrocarbons have lower boiling
points than linear hydrocarbons (pentane 36.1 ◦ C, methylbutane 27.8 ◦ C
and dimethylpropane 9.5 ◦ C). Branched hydrocarbons are shorter and their
atoms cannot get as close together as in unbranched hydrocarbons and the
interactions are weaker.
J. D. van der Waals H. Kamerlingh Onnes P. J. W. Debye
Van der Waals interactions between molecules are weak compared to

the binding energy between atoms in molecules. For instance, the binding
energy of the H atoms in H2 is 436 kJ/mol; that of the Cl atoms in
Cl2 is 243 kJ/mol; and that of the C–H bond in CH4 is 418 kJ/mol.
Physisorption of molecules on surfaces is, thus, also weak. Physisorption
is not specific, it occurs between all adsorbents and adsorbates. Therefore,
although physisorption leads to molecules coming to the surface, it does not
explain catalysis — the breaking and building of specific chemical bonds.
2.1.1 Adsorption on Surfaces

When a molecule hits a surface it can do so elastically (without exchange of
energy) or inelastically (Fig. 2.1). In the latter case, the molecule exchanges
energy with the surface. However, it can leave the surface again if it still
has sufficient kinetic energy perpendicular to the surface. If the adsorption
process is dynamic, we can use statistics to define the average sticking
time τ of a molecule at the surface and the average collision number
n of molecules that hit the surface per second and per surface area. The
surface coverage σ — the average number of molecules adsorbed per unit
Adsorption 29
surface area — is then:
σ = nτ s, (2.2)
where s is the sticking probability — the probability that molecules that

hit the surface will adhere to the surface. For an ideal gas with density D
and molar mass M one can derive [2.2]:

kT NA P
n=D = √ . (2.3)
2πm 2πMRT
This Hertz–Knudsen equation (2.3) shows that the number of collisions

per unit surface area and per unit time is proportional to the pressure
and inversely proportional to the square root of the temperature. From
the Hertz–Knudsen equation, it can be calculated that, at 20 ◦ C and 1 atm
(101.3 kPa), H2 molecules collide 11×1023 times per second with a surface of
1 cm2 and N2 molecules 3 × 1023 times. This demonstrates that the number
of gas molecules colliding with a surface is enormous and that the frequency,
with which these collisions occur, is never a limiting factor for the coverage
of a surface with molecules.
The average residence time τ of molecules at a surface depends on
the probability that the molecule desorbs from the surface. In turn, this
probability depends on the heat of adsorption Q that must accumulate
in order to weaken the interaction between the molecule and the surface.
The desorption frequency ν is described by an Arrhenius-type equation,
because the probability that a molecule collects energy Q is proportional to
exp(−Q/RT). This gives ν = ν0 exp(−Q/RT), where ν0 is a frequency factor
that is roughly equal to ν0 = kT/h = 0.6 × 1013 s−1 at room temperature.
With τ = 1/ν, the Frenkel equation for the residence time is:
Q
τ = τ0 exp . (2.4)
RT
Note the positive sign of Q in equation (2.4) (Q = −∆Hads ). Table 2.3
gives the residence time for several heats of adsorption at 27 ◦ C and 327 ◦ C,
assuming that τ0 = 10−13 s. For Q < 4 kJ/mol, τ is of the same order of
magnitude as τ0 at room temperature. For Q = 6 kJ/mol — which is about
the heat of physisorption of H2 on a surface — τ is about 10τ0 and a
measurable degree of adsorption occurs. For a heat of adsorption of about
16 kJ/mol, as for Ar, O2 , N2 and CO on several surfaces, τ ≈ 10−10 s and a
small portion of the surface will be covered at room temperature and 1 atm.
At higher heat of adsorption, τ increases strongly, as does σ.
Table 2.3 Residence time of a molecule on a

surface as a function of heat of adsorption.
Q (kJ/mol) τ(s), 27 ◦C τ(s), 327 ◦C
4 5 × 10−13 2 × 10−13
20 3 × 10−10 6 × 10−12
40 9 × 10−7 3 × 10−10
80 9 9 × 10−7
160 7 × 1014 9
The degree of coverage of a surface is defined as θ = σ/σ0 , where

σ is the number of molecules adsorbed on unit surface area and σ0 is the
number of molecules that can cover a unit of surface area in a monolayer.
The degree of coverage is the number of monolayers adsorbed on a surface.
For N2 molecules, σ0 is about 1015 molecules/cm2 . At room temperature
and 1 atm, θ = 300 for Q = 40 kJ/mol (as for hexane on Pt) and θ = 109
for Q = 80 kJ/mol (as for dissociative chemisorption of H2 on Pt). Values
above 1 are unrealistic, because they would require more than monolayer
coverage and the heat of adsorption of hexane on hexane and of H2 on H,
is much lower than of hexane on Pt and H on Pt, respectively. However,
these calculated high degrees of coverage demonstrate the clear tendency
to cover the surface. At the higher temperature of 327 ◦ C and a pressure
of 1.3 × 10−4 Pa (10−6 Torr), the situation is different. For Q = 40 kJ/mol,
θ = 8 × 10−11 and for Q = 80 kJ/mol, θ = 10−7 , conditions, under which
molecules can be removed from a surface.
2.1.2 Adsorption Isotherms

The previous section demonstrated that

NA P Q
σ = nτ s = √ τ0 exp s. (2.5)
2πMRT RT
Because M, τ0 and s are constants for the adsorption of a certain molecule
on a certain surface, σ is a function of p and T:
P Q
σ = k0 √ exp .
T RT
At a constant temperature this gives σ = k1 P.
This most simple form of adsorption isotherm (constant T) predicts
that surface coverage is proportional to pressure when the molecules behave
ideally in the gas phase as well as on the surface and when Q is constant
Adsorption 31
and does not depend on coverage. This is true only when the surface is
homogeneous and when the adsorbed molecules do not hinder each other.
This might only be true at low coverage.
Another problem is that, after initial coverage of the surface, gas
molecules may collide with adsorbed molecules. If the interaction energy Q
of a molecule with an adsorbed molecule is low, then collision will not lead
to adsorption. Langmuir therefore corrected the simple adsorption isotherm
σ = k1 P by assuming that only the collision of molecules with the bare
surface, but not with already adsorbed molecules, leads to adsorption [2.3].
If that is true, then the sticking probability must be corrected for the degree
of coverage that has already taken place; thus s = 1−σ/σ0 , σ = nτ (1−σ/σ0 )
and σ = σ0 nτ /(σ0 + nτ ). This gives:
nτ
σ σ0 kL P nτ NA τ
θ= = nτ or θ = with kL = =√ .
σ0 1+ 1 + kL P σ0 P 2πMRT σ0
σ0
(2.6)
The coverage first increases with pressure but is saturated at high pressure,
because Langmuir assumed that the maximum coverage of the surface is a
monolayer (Fig. 2.2).
Fig. 2.2 Surface coverage as a function of pressure in a Langmuir isotherm.

Langmuir derived the Langmuir equation (2.6) in 1916 while working

in the laboratory of General Electric, USA, studying gas adsorption on
tungsten wires in order to produce better light bulbs. He was awarded the
Nobel Prize in Chemistry in 1932 for his work on the adsorption of molecules
on surfaces.
I. Langmuir
At low pressure, the Langmuir equation is identical to the simple

adsorption isotherm equation θ = k1 P. At high pressure the Langmuir
equation leads to the limiting coverage of θ = 1, due to the assumption
that only collisions with the bare surface can lead to adsorption. The
International Union of Pure and Applied Chemistry (IUPAC) refers to this
adsorption isotherm as a Type I isotherm. Other types will be discussed in
the next section.
Measurement of gas adsorption on a surface is based on Boyle’s law,
N = PV/RT. By measuring the pressure P1 of a gas in a volume V1 at
temperature T, the number of gas molecules is known. When one opens
the valve to an evacuated volume V2 that contains the material whose
surface area one wants to determine, the pressure in the total volume V1 +
V2 will be P = P1 V1 /(V1 + V2 ) if no adsorption takes place, but will
be lower when adsorption takes place. From this pressure decrease, one
can calculate the number of gas molecules adsorbed on the surface of the
material. Multiplication of this number by RT/P gives V, the volume of gas
that represents the adsorbed gas. By dividing V by the gas volume Vm that
represents monolayer coverage, one obtains the surface coverage θ = V/Vm .
Inserting this into the Langmuir equation gives:

1 1 1
= 1+ . (2.7)
V Vm kL P
Adsorption 33
The addition of varying amounts of gas to the adsorbate followed by

measurement of the equilibrium pressures, gives a series of V, P values.
Plotting 1/V against 1/P gives a linear plot, which cuts the vertical axis at
1/Vm . From this and the slope 1/VmkL it is possible to calculate Vm , the
number of molecules adsorbed in a monolayer. Today, such measurements
are automated. The Langmuir equation is used not only for the adsorption
of gaseous molecules onto solid surfaces, but also for the adsorption of
molecules from liquids onto solid surfaces.
2.1.3 Multilayer Adsorption, BET

The Langmuir equation is widely applied to chemisorption when adhesion
(binding of molecules to a surface) is much stronger than cohesion (binding
between molecules). It also finds application to the adsorption of molecules
from solution by solid surfaces (e.g. treatment of waste water). However,
when adhesion and cohesion do not differ significantly, the Langmuir
equation is of limited value, because then the adsorption of molecules as
well as already adsorbed molecules must be taken into account.
S. Brunauer P. Emmett E. Teller
Photo of S. Brunauer copyright of American Chemical Society, Jan 1, 1987. Photo of

P. Emmet from the Paul Emmett Papers, 1918–2001, OSU Libraries Special Collections
& Archives Research Centre.
Brunauer, Emmett and Teller (BET) therefore extended the Langmuir

model from monolayer to multilayer adsorption [2.4]. Figure 2.3 (left)
indicates how molecules are adsorbed at different heights. A model that
can describe multilayer adsorption mathematically is shown in Fig. 2.3,
right.

Fig. 2.3 BET model of multilayer coverage of a surface.

Assuming that there are no lateral interactions between adsorbed

molecules, Brunauer, Emmett and Teller [2.4] derived the following BET
equation (2.8) (see [2.5] for derivation):
cP P
θ= with P = , (2.8)
(1 − P )(1 + (c − 1)P ) P0
where P0 is the saturation pressure of the adsorbate and c = τ0 /τ1 the

ratio of the residence times of a molecule adsorbed on the bare surface and
a molecule adsorbed on already adsorbed molecules. Figure 2.4 gives the
BET adsorption isotherms for three values of c.
Fig. 2.4 BET adsorption isotherms for c = 5, 20 and 100.

Adsorption 35
The BET equation is very important to determine the surface area of

powders, especially of catalyst supports. With automated equipment it is
possible to measure adsorption isotherms and determine the constant c,
the ratio of the residence times of a molecule adsorbed on the bare surface
and a molecule adsorbed on already adsorbed molecules. If the heat Qi of
adsorption on already adsorbed molecules is equal to the heat of evaporation

QL of liquid molecules and if the frequency factors of both types of
adsorbates are equal, then:

0 QA
τ0 · exp
τ0 RT Q − QL
c= = ≈ exp A . (2.9)
τ1 0 Q L RT
τ1 · exp
RT
When adsorption on the bare surface is stronger than on already adsorbed
molecules (QA > QL ), then c > 1, giving type II isotherms (Fig. 2.5).
Type II isotherms first increase strongly with pressure, but the increase
slows down at greater pressure, because multiadsorption is not favoured
to the same extent as monoadsorption. Type II isotherms are, thus,
convex at lower pressure. Multiadsorption becomes important above the
inflection point B (Fig. 2.5), when condensation begins and the coverage
increases sharply with pressure, leading to a concave isotherm. When
adhesion is weaker than cohesion, then QA < QL and c < 1. This
occurs when hydrophobic molecules (e.g. benzene) adsorb on glass, lead-
ing to type III concave adsorption isotherms over the whole pressure
range, because adsorption is initially weak but increases with pressure
(Fig. 2.5).
As expected, the Langmuir equation is included in the BET equation,
because for P 1 and c 1 the BET equation becomes θ = cP /(1 + cP )
and cP = cP/P0 = (τ0 /τ1 )(βτ1 /σ0 )P = (τ0 β/σ0 )P = kL P and thus, θ =
kL P/(1 + kL P).
Like the Langmuir model, the BET model is based on the assumption
that the surface is homogeneous and that no lateral interactions occur
between adsorbed molecules. This leads to the physically absurd notion
that molecules stack up in columns and do not form islands of molecules
[2.6], as shown in Fig. 2.3 (left). Furthermore, the heat of adsorption is
assumed to be constant from the second adsorption layer onwards. For these
reasons, the BET equation should not be applied to the region P/P0 > 0.3.
The region P/P0 < 0.05 should not be considered either, because the

Fig. 2.5 Types of adsorption isotherms according to IUPAC.
surface may contain defects that have a high heat of adsorption and strongly
adsorb the first molecules admitted to the surface. At intermediate pressure
(0.05 < P/P0 < 0.3) the heat of adsorption may vary only slightly and thus,
the BET isotherm gives acceptable results.
At higher relative pressure, deviations between the experiment and
the BET equation occur because, in the derivation of the BET equation
it is assumed that the adsorption becomes infinite when p reaches the
saturation pressure of the adsorbate. However, when the heat of adsorption
of the second and higher adsorption layers is different from the heat of
evaporation QL of the liquid molecules, then the residence time τ1 will
differ from the expected value and adsorption will increase more sharply or
less sharply. Furthermore, small pores can contain only a limited number of
layers, whereas an infinite number of layers is assumed in the derivation of
Adsorption 37
the BET equation. Despite its shortcomings, the BET method still enjoys
great popularity, because in the region 0.05 < P/P0 < 0.3 the advantages
outweigh the disadvantages.
Any gas that can be liquefied can be used for BET measurements; in
practice, however, N2 is used in most cases, or sometimes Ar, Kr or CO2 .
A standard measurement of the surface area of a porous material consists

of the automated determination of the adsorption isotherm of N2 at 77 K
(−196 ◦ C) between 0 and 1 atm. Just as for the Langmuir equation, it is
possible to linearise the BET equation:
P 1 (c − 1)
= + . (2.10)
V(P0 − P) Vm c P
(Vm c) ·
P0
Plotting P/V(P0 − P) against P/P0 gives a linear plot with slope (c −

1)/(Vm c), which cuts the vertical axis at 1/Vm c. This enables calculation
of Vm and c. The surface area is given by SA (m2 /g) = (Vm /22414) ×
6.023 × 1023 × 10−18 Sm (nm2 ). Sm is calculated from the density of the
liquid adsorbate at the boiling point at 1 atm, Sm = f(M/ρNA )2/3 , where
f is the stacking factor of the adsorbate molecules, M the molar weight,
ρ the density and NA the Avogadro number. This gives Sm = 0.162 nm2
and SA (m2 /g) = 4.36 Vm (cm3 gas) for N2 . The BET method enables
the calculation of surface areas up to 1000 m2 /g. For small surface areas, a
gas with a pressure lower than N2 at −196 ◦ C should be selected. With Ar
(b.p. −186 ◦ C) or Kr (b.p. −151 ◦ C, P0 = 2 Torr at −196 ◦ C) the change
in gas pressure due to adsorption can be measured much more accurately
at −196 ◦ C. Methane (b.p. −162 ◦ C) is used for surfaces up to 5 m2 /g.
After measuring a BET isotherm by increasing the pressure of N2 , it is
also possible to measure the desorption isotherm by decreasing the pressure
from high to low. Hysteresis of adsorption is often observed, with the
desorption isotherm above the adsorption isotherm (Fig. 2.6).
Hysteresis occurs when filling of the pores does not occur in the same
way as the emptying of the pores. Filling occurs when an increasing number
of layers is deposited on all the surfaces (walls of the pores). Emptying,
however, does not occur by removing one layer after another from all the
surfaces simultaneously, but starts at the widest pores (with the lowest
curvature) and ends with removal of the molecules from the narrowest
pores. Hysteresis can occur when adsorption on the bare surface is stronger
than on already adsorbed molecules (changing type-II behaviour to type-IV,

Fig. 2.6 Adsorption (open squares) and desorption (filled squares) isotherms of N2 at —
196 ◦ C in porous silica glass, consisting of spherical cavities with a diameter of 20 nm
connected by channels, 3 nm in diameter.
cf. Fig. 2.5) as well as when adsorption on the bare surface is weaker than
on already adsorbed molecules (changing type-III behaviour to type-V).
Hysteresis is explained quantitatively by the Kelvin equation. When
molecules adsorb on a curved surface with radii r1 and r2 , the gaseous
adsorbate is in equilibrium with the layer adsorbed on the curved surface
when the free enthalpy is constant or when dG is zero:
dS (µad − µG )
dG = µad dN − µG dN + γdS = 0, or − = .
dN γ
−dS/VdN = r11 + r12 , with µ the chemical potential and V the molar volume.
With µG = µ0G + RT ln PP0 and µad = µL = µ0G , the Kelvin equation is
obtained:

P 1 1
RT ln = −γV + . (2.11)
P0 r1 r2
For a cylinder (capillary) with radius r, the radii r1 and r2 are r1 = r and
r2 = ∞, thus:

P γV γV
ln =− or P = P0 exp − .
P0 RTr RTr
Molecules with pressure Pi in the gas phase are, thus, in equilibrium with
molecules on the surface when the radius of the adsorbed layer on the
Adsorption 39
capillary wall is ri . Whenever more molecules adsorb on the wall, the radius
r decreases. However, P decreases when r decreases and thus, the pressure
required to maintain equilibrium between the gas and the adsorbed phase
decreases as well. Hence, when the pressure of the gas is sufficient to start
adsorption on the wall of the cylindrical pore with radius r, the adsorption
will continue until the whole pore is filled. Concave surfaces will be filled
one by one. First the surfaces with the largest curvature (smallest r) will
become full at a certain pressure. At a slightly higher pressure surfaces with
a somewhat larger r will fill. This is what happens during an increase in
gas adsorption above about P/P0 = 0.3.

When all the pores are full, desorption starts at the end of the cylindrical
capillary (pore mouth) and the liquid surface takes the shape of a half sphere
with r1 = r2 = r. For desorption, we thus get ln (Pdes /P0 ) = −2γV/RTr.
Thus, Pdes /P0 = (Pads /P0 )2 and Pdes < Pads (because P/P0 < 1).
Desorption therefore starts at lower pressure than adsorption and the
desorption curve is above the adsorption curve. When measuring the
desorption isotherm of porous systems with many flat surfaces and a few
strongly curved surfaces — as in the so-called ink bottle pores, (see Fig. 2.6,
right) — lowering the pressure does not lead initially to strong desorption.
The liquid always contracts in the smallest of the ink bottle pores and
for this radius r desorption does not occur yet, according to the equation
ln(Pdes /P0 ) = −2γV/RTr. Finally, when the pressure is so low that
desorption of the narrow pores should occur, according to the desorption
equation, almost total desorption occurs and the desorption isotherm
drops sharply. Such a sharp drop is often observed for N2 adsorption at
P/P0 = 0.42. This is not due to ink bottle pores, but to an artifact of N2 .
2.2 Surface Diffusion

Until now the assumption has been that a molecule can adsorb (chemisorb)
only at the position (site) where it collides with the surface, but the
situation is more complex. It has been known for a long time that the
probability for desorption is not proportional to the surface coverage, but
increases much more slowly. As an explanation, Kisliuk proposed that
diffusion of molecules over the surface can increase the sticking coefficient
[2.7]. A molecule can hit the surface and be physisorbed at the site of
impact. To become physisorbed, it is unnecessary for the molecule to
transfer all the translational energy that it had in the gas phase to the
surface. It only needs to transfer its translational energy perpendicular

Fig. 2.7 Adsorption to a precursor state over empty (intrinsic) or filled (extrinsic) sites.
The intrinsic state can adsorb (pai ), desorb (pdi ) or diffuse. The extrinsic state can desorb
(pde ) or diffuse (pme ) to another site before adsorbing at an empty site. Reprinted with
permission from [2.8]. Copyright (2010) IOP Publishing.
to the surface and can maintain the translational energy parallel to this
and thus, can diffuse over the surface. After several diffusion steps, it may
lose more energy to the surface and become locally physisorbed (Fig. 2.7).
After more loss of energy, it becomes chemisorbed but is still in an excited
state. After losing more energy, it will finally reach the bottom of the
chemisorption well (see Fig. 2.1).
Because physisorption energy is low, the activation energy for diffusion
to a neighbouring position will also be low. A physisorbed molecule has,
therefore, three possibilities. It can desorb or adsorb, or it can migrate
(diffuse) to another position. The sum of the probabilities for adsorption
pa , desorption pd and migration pm at site 1 are pa1 + pd1 + pm1 = 1.
The sticking probability s is the sum of all probabilities that the molecule
adsorbs on sites 1, 2, 3 . . . , multiplied by the migration probabilities:
s = pa1 + pm1 pa2 + pm1 pm2 pa3 + · · · .
If pai and pmi are independent of i, then

1 pa
s = pA (1 + pm + p2m + · · · ) = pa = .
1 − pm pa + pd1
The probability of desorption depends on the desorption of molecules
from the bare surface and of molecules from adsorbed molecules. pd1 =
pd (1−θ)+pd θ, thus s = pa f(θ)+ppadf(θ)
(1−θ)+pd θ . For a clean surface, f(θ) = 1 and
s0 = pa /(pa + pd ). If each surface position can accommodate one molecule,
Adsorption 41
then f(θ) = 1 − α, as in the derivation of the Langmuir equation and:

pa (1 − θ)
s=
pa (1 − θ) + pd (1 − θ) + pd θ
pa (1 − θ) s0 (1 − θ)
= = ,
(pa + pd )(1 − θ) + pd θ pd θ

(1 − θ) +
pa + pd
s (1 − θ)
= ,
s0 (1 − θ) + K
where K = pd /(pa + pd ) is the precursor desorption coefficient.
Figure 2.8 shows that the sticking probability decreases linearly with
coverage (s/s0 = 1 − θ) for pure Langmuir adsorption without precursor
adsorption (K = 1, high coefficient for desorption). When K is small,
then the probability of desorption from the second layer is small and the
probability of diffusion becomes high. In that case, the precursor state
keeps the sticking probability close to 1, even at substantial coverage of
the surface by molecules. The smaller the coefficient for desorption of the
precursor, the greater the probability that the physisorbed molecule will
stick to the surface. Migration (diffusion) over the surface increases the
sticking coefficient considerably. When one molecule adsorbs at two surface
Fig. 2.8 The effect of the precursor parameter on the adsorption curve; K = 1
corresponds to the absence of a precursor effect and Langmuirian kinetics. Reprinted
with permission from [2.8]. Copyright (2010) IOP Publishing.

Fig. 2.9 (Left) Coverage-dependent sticking probability for CO on Rh(100). Reprinted

with permission from [2.9]. Copyright (1999) the American Chemical Society. (Right)
Structure model for CO adsorbed on Rh(100) in the on-top position. Reprinted with
permission from [2.10]. Copyright (1994) AIP Publishing LLC.
positions, as in dissociative adsorption of H2 and O2 , then f(θ) = (1−θ)2 and

s/s0 = (1−θ)/[(1−s0θ)+Kθ/(1−θ)]. In that case too, the sticking coefficient
decreases only slowly with coverage, similar to the sticking coefficient in
Fig. 2.8.
When molecules repel each other at the surface, then the maximum
surface coverage may be lower than 1. Thus, for CO on Rh(100), the heat
of adsorption and sticking probability decrease at a surface coverage of
about 0.5, leading to a coverage with alternating filled and empty sites
(Fig. 2.9).
2.3 Chemisorption
2.3.1 Chemical Bonding
Chemisorption is the strong binding of molecules and atoms with surfaces.
Metallic bonds, as in pure metals, are responsible for the chemisorption of
alkali metals on metals (Cs on W) (see Chapter 6.4 for metal bonding).
Ionic bonds are responsible for the chemisorption of oxygen and halogens
at metal surfaces, when surface metal atoms are oxidised to metal cations
and the oxygen and halogen atoms become anions (O2 on Ni). Covalent
bonds describe the bonding of hydrogen on metals (H2 on Pt), CO on
metals (CO on Ni) and alkenes on metal oxides (propene on bismuth
molybdate). The strongest contributions to covalent bonding between two
molecules are made by the frontier orbitals, the highest occupied molecular
Adsorption 43
orbitals (HOMO) of one molecule and the lowest unoccupied molecular

orbitals (LUMO) of the other molecule (Fukui and Hoffmann, Nobel Prize
in Chemistry, 1981). This interaction can be seen as an acid–base interaction
between an orbital with fewer electrons (LUMO, the acceptor orbital) and
an orbital with more electrons (HOMO, the donor orbital).
R. Hoffmann
Photo by Armin Kübelbeck, work CC-BY-SA.
The bonding between atoms in a molecule as well as between molecules

is strongest when the interaction between orbitals A and B is strongest.
2
The interaction is proportional e to (H AB ) /∆EAB , where HAB is the
exchange interaction HAB = A r B dx and ∆EAB is the energy difference
e
between the orbitals. Because the exchange interaction A r B dx is roughly
proportional to the overlap A B dx between both orbitals, the interactions
between orbitals are strongest when the orbitals overlap substantially and
the energy difference ∆EAB between the orbitals is small.
When two orbitals interact, they form two new orbitals, which are a
mixture of the original orbitals and thus, surround both atoms [2.11]. They
are referred to as molecular orbitals (MOs). The energy E− = E0c − ∆E
of the new lower level (Fig. 2.10, right) decreases by ∆E and the energy
E+ = E0b + ∆E of the new higher level increases by ∆E .
If, before the interaction between the orbitals on atom A and on atom B
the level E0c contains two electrons while the level E0b is empty, then
following the interaction the new lower level with energy E− contains two
electrons and the new higher level with energy E+ is empty. In that case,
the interaction leads to an energy gain 2∆E = 2(E0c − E− ). Filling the lower
MO with electrons leads to a gain in energy and thus, to bonding of the

Fig. 2.10 Interaction between two orbitals b and c leads to two new MOs, a decrease
in energy of the lower orbital by ∆E and an increase in the energy of the higher orbital
by ∆E .
atoms (or molecule fragments) to which the orbitals A and B belong. This
MO is referred to as a bonding orbital.
If, on the other hand, each of the original levels E0c and E0b is filled
with two electrons, then each of the two new levels will also contain two
electrons. This would lead to an energy gain of 2∆E and an energy loss
of 2∆E , where ∆E is the upward shift of the higher original level. Since
quantum mechanics teaches us that the antibonding MO increases more
in energy than the bonding MO decreases (∆E > ∆E), the net result is
energy loss. Thus, the MO that has gone up in energy relative to the energy
E0b leads to a loss in energy when it is filled with electrons and to a repulsive
interaction between the atoms (or molecule fragments). This MO is referred
to as an antibonding orbital.
The interactions between orbitals can be summarised as follows. Interac-
tions of filled and empty orbitals (two-electron interactions) are attractive,
while interactions of filled orbitals (four-electron interactions) are repulsive.
Interactions of empty orbitals have no effect; as long as there are no
electrons there is no change in energy.
When several filled and empty orbitals (levels) exist on both interacting
atoms, or both molecules A and B (Fig. 2.10), all three types of interactions
(attractive, repulsive and no effect) will occur. Interactions between the
filled orbital a from A and the empty orbital d from B and between the filled
orbital c from B and the empty orbital b from A are attractive. The lower
orbital is filled with two electrons and gains energy, while the upper level
is empty and thus, cannot lose energy. Therefore, a–d and b–c two-electron
Adsorption 45
interactions lead to bonding. An interaction between orbitals b and d has

no energetic consequences, since the orbitals are empty. A four-electron
interaction between orbitals a and c is repulsive, because the total energy
is greater than that of the separate isolated levels [2.11].
Because the interaction between orbitals is proportional to (HAB )2 /
∆EAB , the dominating interactions are between orbitals that overlap

substantially and which are similar in energy. Orbitals overlap substantially
when they extend in space. This is the case for orbitals of the least bound
electrons (the upper levels) of an atom or molecule, the valence orbitals.
Orbitals of strongly bonded electrons, with low energy, are drawn close to
the nucleus and do not extend into space. The overlap of such contracted
orbitals is small. As a consequence, orbitals in the valence region determine
chemical reactivity: the highest filled and lowest empty orbitals.
The empty (acceptor) level b of atom (or molecule) A is closer in energy
to the filled (donor) level c of atom (or molecule) B than to the levels
h and i, which have a lower energy than level c. If the overlaps bhdr
and bidr are smaller than bcdr, then the numerator and denominator
of (HAB )2 /∆EAB set the b(A)–c(B) interaction apart as an important,
perhaps the most important interaction. The HOMO, or a small subset
of higher-lying levels and the LUMO, or a subset of unoccupied MOs,
often dominate the interaction between two molecules. These are referred
to as the frontier orbitals — the valence orbitals of the molecule and the
orbitals most easily perturbed in any molecular interaction. They control
the chemistry of the molecules [2.11].
This qualitative knowledge can explain the stability of molecules. Why
does H2 exist and why does He2 not exist? The energy difference ∆EAB is
smallest when A and B are the same atoms or molecules, then ∆EAB = 0.
This explains why the bonding between two H atoms is strong, as seen in
Fig. 2.11, which indicates what happens to the energy when a hydrogen
atom A approaches a hydrogen atom B. The 1s atomic orbitals (AOs) on
atoms A and B form two new MOs. One MO is lower in energy than
the original AOs and is referred to as the bonding orbital, because it
leads to a gain in energy when it is filled with electrons. The second
MO is higher in energy than the energy of the original 1s orbitals. This
MO is the antibonding orbital, leading to a loss of energy when filled
with electrons.
When two H atoms (each having one electron) are combined to a H2
molecule, the two electrons can be put in the lowest MO, because the Pauli
exclusion principle allows putting two electrons in one orbital when they

Fig. 2.11 MOs and MO energies of H2 and He2 .
have a different spin α and β. Pauli discovered the exclusion principle in

1925, when he was 25 years old and received the Nobel Prize in Physics in
1945. The lowest MO of H2 is the bonding MO and thus, the combination
of two H atoms leads to a gain in energy (Fig. 2.11, left). Two H atoms
form a stable bond in the H2 molecule. If an attempt is made to combine
two He atoms to a He2 molecule, then four electrons must be transferred
to the MOs of the He2 molecule, because each He atom has two electrons.
As Fig. 2.11 (right) shows, two electrons must go into the bonding MO
and two into the antibonding MO. Because the antibonding MO increases
more in energy than the bonding MO decreases, the energy increases when
the two He atoms are combined to a molecule, meaning that two He atoms
repel each other.
W. E. Pauli
Photo copyright of Bettina Katzenstein/ETH Zürich.
Adsorption 47
Similarly, it is possible to construct the MOs and the energy levels

of other molecules, for instance of carbon monoxide. The CO molecule is
important in catalysis, not only in catalytic reactions (see the discussion
of methanation and Fischer–Tropsch reactions in Chapter 7), but also as a
probe molecule to characterise catalyst surfaces (Chapter 3). The bonding
of the C and O atoms in CO and the bonding of CO to a metal atom or

cation are, therefore, important issues. Figure 2.12 indicates how the 1s,
2s and 2p AOs of the C and O atoms combine to MOs. The 1s AOs are
not important in the chemical binding of the C and O atoms, because they
are small and do not overlap. Thus, the interaction energy is very low. The
valence-shell carbon and oxygen 2s and 2p AOs combine to MOs of two
types: σ orbitals, which are symmetric around the CO axis and π orbitals,
which have a plane through the CO axis as plane of antisymmetry (positive
orbital on one side and negative orbital on the other side of the plane). As
a consequence, the π orbitals have a zero electron density in the CO axis,
while the σ orbitals have a maximum electron density in the CO axis. With
six electrons from the C atom (1s2 , 2s2 , 2p2 ) and eight from the O atom
(1s2 , 2s2 , 2p4 ), the 1σ, 2σ, 3σ, 4σ, 1π and 5σ MO orbitals of CO will be
filled (Fig. 2.12). The bonding contributions of the 1σ, 2σ and 3σ orbitals
are small, but the contributions of the 4σ, 1π and 5σ orbitals are strong and
bonding. Therefore, bonding in the CO molecule is strong. The HOMO is
the 5σ MO, which is mainly a combination of the C 2pz and O 2pz orbitals
Fig. 2.12 MOs and MO energies of CO.


Fig. 2.13 5σ bonding HOMO (left) and 2π* antibonding LUMO (right) of CO.
(z axis is along the CO axis). Because the carbon levels are slightly higher
than the oxygen levels, the 5σ MO has a larger contribution from the C
atom than from the O atom. This is indicated by a larger cloud in Fig. 2.13.
The LUMO is the 2π* MO, which actually consists of two MOs with the
same energy (the label π indicates twofold degeneracy and the label * an
antibonding orbital). One MO is a combination of the C2px + O2px atomic
orbitals and the other is a combination of the C2py + O2py AOs (the x and
y axes are perpendicular to the CO axis). Both orbitals have exactly the
same shape, but are rotated 90 ◦ relative to each other. The 2π ∗ LUMO has
a larger contribution from the C atom than from the O atom (Fig. 2.13).
The HOMO and LUMO of CO have the ideal shape to interact strongly
with a metal atom. Figure 2.14 shows that the d(x 2 − z 2 ) AO can have a
large overlap with the 5σ CO MO (Fig. 2.13), while the d(xz ) AO can have
a large overlap with the 2π*(x) MO and the d(yz) orbital with the 2π*(y)
MO. The interaction of the empty d(x 2 − z 2 ) AO (LUMO on the metal
atom) with the filled 5σ CO MO (HOMO on CO) leads to a new M–C–O
orbital, a mixture of the 5σ CO MO and the d(x 2 − z 2 ) orbital. When two
dx2-z2 dxz
Fig. 2.14 Interactions between the metal d2x − z 2 AO and the CO 5σ MO and between
the metal dxz AO and the CO 2π* MO.
Adsorption 49
electrons fill this new σ MO, electron density moves from the CO to the
metal atom: electron donation or σ donation. The other interaction,
between the filled (HOMO) metal d(xz) orbital and the empty (LUMO)
CO 2π*(x) MO leads to an electron flow in the opposite direction, from the
metal atom to the CO ligand: π back donation or back bonding. Both
interactions, σ donation and π back donation, contribute to the bonding

between the metal atom and the C atom of the CO molecule. At the same
time the CO bond is weakened, because electron density is taken from the
5σ CO MO, which is bonding in CO and electrons are donated to the CO
2π*(x) MO, which is antibonding in CO. The weakened CO bond manifests

itself in a lowered frequency of the CO stretching infrared (IR) vibration.
At the same time new M-C IR vibrations occur at low frequency. The above
description of the bonding of CO to a metal is referred to as the Blyholder
model [2.12].
Similar σ donation and π back donation occur in the interaction between
the d orbitals of a transition-metal atom and the π electrons of the double
bond of an alkene molecule (Fig. 2.15). The two 2p AOs on the two carbon
atoms form a bonding π MO and an antibonding π ∗ MO. The bonding
alkene π MO interacts with a metal d orbital that is symmetric relative to
the M-alkene axis (Fig. 2.15, left), while the antibonding π ∗ MO interacts
with a metal d orbital that is antisymmetric relative to the M-alkene axis
(Fig. 2.15, right). The former interaction leads to σ donation and the latter
to π back donation. Both contribute to bonding of the alkene to the metal
atom and at the same time, to weakening of the double bond in the alkene
molecule. This model of σ donation and π back donation in metal-alkene
complexes is referred to as the Dewar–Chatt–Duncanson model.
Fig. 2.15 Dewar–Chatt–Duncanson model of σ-donation and π-back donation in a

metal–ethene complex.
The formation of new bonds and the weakening of old bonds due to
shifts in electron density form the basis of catalytic reactions. The new
bonds allow chemisorption of molecules on metal atoms at metal surfaces
or on metal ions in metal complexes and the weaker bonds in the molecules
prepare the molecules for reaction by lowering the activation energies.
2.3.2 Dissociative Chemisorption

Chemisorption can be associative when the molecule adsorbs and stays
intact, or dissociative when the molecule adsorbs and dissociates in atoms

or molecule fragments. The potential energy diagram of the dissociative
chemisorption of diatomic molecules such as H2 , N2 and O2 on a metal
surface consists of two parts. The first step in the dissociative adsorption
of H2 is physisorption of the H2 molecule on the metal surface. This leads
to a weak minimum at a relatively large distance, as in Fig. 2.16 (left). The
chemisorption of two H atoms at the metal surface starts at a large distance
and at high energy, because of the dissociation energy of H2 (436 kJ/mol).
The chemisorption curve has a minimum at a shorter distance than the
physisorption minimum. The depth of the minimum below the zero level
(H2 molecule far away from the surface) is the heat of adsorption Q of
H2 (Q = −∆H which is positive for exothermic adsorption). Q depends
Fig. 2.16 (Left) Potential energy (in kJ/mol) of dissociative adsorption of H2 on Cu.
(Right) Potential energy along the minimum-energy reaction path for H2 dissociation on
the (111) surfaces of Ni, Cu and Au.
Adsorption 51
on the M–H interaction and is about 120 kJ/mol for Ni, 90 kJ/mol for Pt,
30 kJ/mol for Cu and −50 kJ/mol for Au [2.13] as in Fig. 2.16 (right). When
the minimum of the chemisorption curve is deep, the crossing point between
the physisorption and chemisorption curves is below zero energy. As a
result, the dissociation of H2 on Ni occurs without an activation barrier.
For Cu, Fig. 2.16 (left), the crossing point is at E > 0 and H2 adsorption
on Cu is an activated process. When Q < 0 (endothermic adsorption, the
chemisorption minimum is above zero energy), the adsorption of H2 is both
activated and endothermic, as is the case for Au. Adsorption of H2 leads
to a very low coverage of Au.

Chemisorption of molecules is used to measure the surface area of small
metal particles. The molecules must have a much stronger interaction with
the metal surface (adhesion) than with other molecules (cohesion), so that
monolayer adsorption occurs on the metal surface (Langmuir adsorption).
At the same time, the van der Waals interaction of the molecule with the
support, on which the metal particles are located, will be weak. As a result,
the number of adsorbed molecules is directly proportional to the metal
surface area of the catalyst.
The surface area of metal particles is usually measured by hydrogen
chemisorption. Most metals have an H–M binding energy that is larger
than half the dissociation energy of H2 , so that H2 adsorbs dissociatively
in two H atoms (Fig. 2.16). By measuring the amount of H2 that a metal-
on-support catalyst adsorbs, it is possible to calculate the H/M ratio, i.e.
the number of adsorbed H atoms relative to the total number of metal
atoms in the sample. Assuming that each H atom binds to one metal atom,
the H/M ratio is equal to the Ms /M ratio, the number of metal atoms
on the surface divided by the total number of metal atoms. This ratio is
called the dispersion of the metal.
An example of a hydrogen chemisorption measurement is presented
in Fig. 2.17, for a catalyst consisting of rhodium particles supported
on alumina. By extrapolating the adsorption isotherm (curve a) to zero
pressure, an amount of 50 µmol H2 adsorbed per g catalyst is measured.
Some scientists use this extrapolated value based on one adsorption
isotherm for the H/M determination. Others measure two adsorption
isotherms, first an adsorption isotherm (Fig. 2.17, curve a), then evacuate
and measure a second adsorption isotherm (Fig. 2.17, curve b). In this
method it is assumed that hydrogen can also adsorb (weakly) on the support
and that this is the cause for the increase in H2 uptake with pressure.
Evacuation removes the weakly bonded molecules from the support, but not

Fig. 2.17 Hydrogen chemisorption isotherms of 0.6% Rh/Al2 O3 (a) and Al2 O3 (b) at
25 ◦ C. Reprinted with permission from [2.14]. Copyright (1986) Elsevier.
from the metal surface. The adsorption measured in the second isotherm
is then due to re-adsorption on the support surface. Subtraction of the
second isotherm from the first isotherm gives a new isotherm, which is
due to gas adsorption on the metal only. In the case of Rh/Al2 O3 , this
subtraction would give an isotherm with a constant amount of adsorbed
H2 of 50 µmol/g catalyst above 20 kPa [2.14]. The two-step chemisorption
method is not necessarily better, however. Because an adsorption isotherm
is based on thermal equilibrium, evacuation after measurement of the
first isotherm may desorb molecules not only from the support, but also
from the metal surface. In that case, the second isotherm is due to
adsorption on the support, as well as on the partially evacuated metal
surface.
Dissociative chemisorption of O2 and N2 is very important in catalysis
as well. Chemisorption of O2 is the basis of corrosion of metals, of catalytic
oxidation reactions of hydrocarbons to oxygen-containing molecules and
of harmful CO and hydrocarbons in exhaust gas to CO2 (Chapter 9).
Dissociation of N2 is the basis of the synthesis of ammonia, which finds its
main application in the production of fertiliser required to feed the world
population. The bond energy of N2 (945 kJ/mol) is much higher than that of
H2 (436 kJ/mol) and of O2 (497 kJ/mol). The adsorption and dissociation
Adsorption 53
of N2 , with physisorption of a molecular precursor and chemisorption of

adsorbed atoms, occurs similar to H2 (Section 7.5).
References
2.1. F. London, Zur Theorie und Systematik der Molekularkräfte, Z. Physik 63,
245–279, 1930.
2.2. The probability that an ideal gas molecule has a velocity vx is p(vx ) =
−v2 R∞
√ 1 exp 2α2x , where α2 = −∞ vx2 p(vx )dvx is the average of vx2 , because
R∞2πα2 √
−∞
x2 exp(−x2 )dx = 0.5 π. For a gas of density D, the number of
molecules with velocity vx in the x direction perpendicular to a surface
S that hit the surface S per second, is equal to DS vx p(vx ) =
1 −v2
DS vx √2πα exp 2α2x . The total number of molecules hitting the sur-
2
R∞
face with any velocity per second is, thus, n = 0 F dvx , with F =
2
−vx
1
DS vx √2πα exp Because Ekin = 0.5 mvx2 = 0.5 kT, α2 = vx2 = kT/m
2α2
.
2
q
kT
and D = N/V = NA P/RT (NA Avogadro constant), we get n = D 2πm =
NA P
√ .
2πMRT
2.3. I. Langmuir, The constitution and fundamental properties of solids and
liquids. Part 1. Solids, J. Am. Chem. Soc. 38, 2221–2295, 1916.
2.4. S. Brunauer, P. Emmett, E. Teller, Adsorption of gases in multimolecular
layers, J. Am. Chem. Soc. 60, 309–319, 1938.
2.5. In thermal equilibrium, the residence time τI of a molecule at layer i is equal
to the inverse of the rate of desorption νi−1 from layer i − 1: τi = 1/νi−1 .
With si = θi−1 this gives nθi−1 = νi−1 σ0 θi or θi = (nτi /σ0 )θi−1 . Thus,
θi = (nτi /σ0 )(nτi−1 /σ0 )(nτi−2 /σ0 ) . . . (nτ1 /σ0 )(nτ0 /σ0 )θ0 . If the residence
time of a molecule in all layers apart from layer 0 is equal, τi = τ1 for
i ≥ 1, then θi = (nτ1 /σ0 )i−1 (nτ0 /σ0P )θ0 = (nτ1 /σ0 )i (τ0 /τ P1∞)θ0 . The total
∞ i
coverage
P∞ i θ of the surface thus
P∞ is θ = 1 iθ i = (τ
P∞ i 0 /τ 1 )θ 0 1 i(nτ1 /σ0 ) =
cθP0 1 ix and θ0 = P∞ 1 − 1 θi = P 1 −i cθ0 1 x and thus θ0 = 1/(1 +
c ∞
P
i
1 x ) and θ = c ixi /(1 + c ∞
1 P 1 x ) = cx/(1 − x)(1 − x + cx) because
∞ i ∞ i
x = x/(1 − x) and 1 √ix = x/(1 − x)2 . In these formulae x = nτ1 /σ0
1 √
and c = τ0 /τ1 , n = NA P/ (2πMRT) = βP with β = NA / (2πMRT)
x = nτ1 /σ0 = βPτ1 /σ0 = P/q with q = σ0 /βτ1 . θ = V/Vm = cx/(1 −
x)(1 − x + cx) = cP/[(q − P)(1 + (c − 1))P/q]. This equation indicates that
V/Vm should become infinite when P approaches q. This happens when
condensation of the molecules at the surface occurs. The physical meaning
of q thus is q = P0 , the saturation pressure of the adsorbate. Therefore,
θ = cP /(1 − P )(1 + (c − 1)P ) with P = P/P0 .
2.6. S. Brunauer, About some critics of the BET theory, Langmuir 3, 3–4, 1987.
2.7. P. Kisliuk, The sticking probabilities of gases chemisorbed on the surfaces
of solids, J. Phys. Chem. Solids 3, 95–101, 1957.
2.8. M. Bowker, The role of precursor states in adsorption, surface reactions
and catalysis, J. Phys. Condens. Matter 22, 263002, 2010.
2.9. R. Kose, W. A. Brown, D. A. King, Role of lateral interactions in adsorption

kinetics: CO/Rh{100}, J. Phys. Chem. B 103, 8722–8725, 1999.
2.10. A. M. de Jong, J. W. Niemantsverdriet, The adsorption of CO on Rh(100):
Reflection absorption infrared spectroscopy, low energy electron diffraction,
and thermal desorption spectroscopy, J. Chem. Phys. 101, 10126–10133,
1994.
2.11. R. Hoffmann, A chemical and theoretical way to look at bonding on

surfaces, Rev. Mod. Phys. 60, 601–628, 1988.
2.12. G. Blyholder, Molecular orbital view of chemisorbed carbon monoxide,
J. Phys. Chem. 68, 2772–2777, 1964.
2.13. B. Hammer, J. K. Nørskov, Why gold is the noblest of all the metals, Nature
376, 238–240, 1995.
2.14. H. F. J. van ‘t Blik, R. Prins, Characterization of supported cobalt and
cobalt-rhodium catalysts, J. Catal. 97, 188–199, 1986.
Questions
2.1 Why are the boiling points of branched alkanes lower than the boiling
points of linear alkanes?
2.2 Why is cleaning of a surface carried out at elevated temperature and
low pressure?
2.3 In Section 2.3.1, we learned that two-electron interactions are attrac-
tive, while four-electron interactions are repulsive. What about three-
electron interactions? What is the lightest three-electron two-atom
molecule?
2.4 Adsorption of H2 leads to a very small coverage of Au. Despite this, it
is still possible to deposit H atoms on the surface of Au. How?
2.5 The bond energy of N2 , O2 and H2 are 945, 497 and 436 kJ/mol,
respectively. Explain these differences in bond energy.
2.6 The σ donation and the π back donation between an alkene and a metal
atom lead to the bonding of the alkene to the metal atom and to the
weakening of the double bond in the alkene molecule. How can you
prove the existence of the new bond and the weakening of the C=C
bond?
2.7 One g Pt/Al2 O3 catalyst with 0.3 wt.% Pt loading adsorbs 6 µmol H2 .
Calculate the Pt dispersion.

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March 2, 2016 14:51 Introduction to Heterogeneous Catalysis - 9in x 6in b2258-ch02 page 25

26 Introduction to Heterogeneous Catalysis

Fig. 2.1 One dimensional representation of non-activated adsorption. (a) elastic

Table 2.1 Types of interactions and their order of magnitude.

Ion–ion q1 q2 /r 400 Ionic bonding

The energy of most of these interactions can be calculated according to

dipole–dipole interaction (Keesom) energy is E = −2/3.µ21 µ22 kT/r6 . Many

therefore, referred to as London or dispersion force.

always attractive: molecules move as close as possible to each other. At

Table 2.2 Lattice energy of molecules in the solid state in kJ/mol.

Molecule Keesom Debye London Total

28 Introduction to Heterogeneous Catalysis

the atoms in molecules can be added together. As a consequence, larger

J. D. van der Waals H. Kamerlingh Onnes P. J. W. Debye

Van der Waals interactions between molecules are weak compared to

2.1.1 Adsorption on Surfaces

surface area — is then:

where s is the sticking probability — the probability that molecules that

and molar mass M one can derive [2.2]:

This Hertz–Knudsen equation (2.3) shows that the number of collisions

30 Introduction to Heterogeneous Catalysis

Table 2.3 Residence time of a molecule on a

Q (kJ/mol) τ(s), 27 ◦C τ(s), 327 ◦C

The degree of coverage of a surface is deﬁned as θ = σ/σ0 , where

2.1.2 Adsorption Isotherms

Fig. 2.2 Surface coverage as a function of pressure in a Langmuir isotherm.

32 Introduction to Heterogeneous Catalysis

Langmuir derived the Langmuir equation (2.6) in 1916 while working

At low pressure, the Langmuir equation is identical to the simple

The addition of varying amounts of gas to the adsorbate followed by

2.1.3 Multilayer Adsorption, BET

S. Brunauer P. Emmett E. Teller

Photo of S. Brunauer copyright of American Chemical Society, Jan 1, 1987. Photo of

Brunauer, Emmett and Teller (BET) therefore extended the Langmuir

34 Introduction to Heterogeneous Catalysis

Fig. 2.3 BET model of multilayer coverage of a surface.

Assuming that there are no lateral interactions between adsorbed

where P0 is the saturation pressure of the adsorbate and c = τ0 /τ1 the

Fig. 2.4 BET adsorption isotherms for c = 5, 20 and 100.

The BET equation is very important to determine the surface area of

adsorption on already adsorbed molecules is equal to the heat of evaporation

36 Introduction to Heterogeneous Catalysis

Fig. 2.5 Types of adsorption isotherms according to IUPAC.

A standard measurement of the surface area of a porous material consists

Plotting P/V(P0 − P) against P/P0 gives a linear plot with slope (c −

38 Introduction to Heterogeneous Catalysis

gas adsorption above about P/P0 = 0.3.

2.2 Surface Diﬀusion

40 Introduction to Heterogeneous Catalysis

s = pa1 + pm1 pa2 + pm1 pm2 pa3 + · · · .

If pai and pmi are independent of i, then

then f(θ) = 1 − α, as in the derivation of the Langmuir equation and:

(pa + pd )(1 − θ) + pd θ pd θ

42 Introduction to Heterogeneous Catalysis

Fig. 2.9 (Left) Coverage-dependent sticking probability for CO on Rh(100). Reprinted

positions, as in dissociative adsorption of H2 and O2 , then f(θ) = (1−θ)2 and

orbitals (HOMO) of one molecule and the lowest unoccupied molecular

The bonding between atoms in a molecule as well as between molecules

44 Introduction to Heterogeneous Catalysis

interactions lead to bonding. An interaction between orbitals b and d has

∆EAB , the dominating interactions are between orbitals that overlap

46 Introduction to Heterogeneous Catalysis

Fig. 2.11 MOs and MO energies of H2 and He2 .