EP318 Surface Chemistry and Catalysis

Chapter 3: Part II

Adsorption & Desorption

Prepared by Dr. Tan, M.C.

 BET Adsorption Isotherm
• In Langmuir model, the maximal adsorption is that of monolayer.
• Langmuir adsorption isotherms all saturate at high vapor pressure.
• This is unrealistic for many cases.
• In order to consider the adsorption of multilayers, Brunauer,
Emmett, and Teller extended the Langmuir theory and derived the
so-called BET adsorption isotherm.
• The basic idea in the BET theory was to assume a Langmuir
adsorption for each of the layers.
• Adsorbed molecules are not allowed to move from one layer
directly to another.
• In equilibrium, the desorption rate for each layer must be equal to
the adsorption rate.
 BET Adsorption Isotherm
The assumptions made in the derivation of the BET model are:
• The adsorbed molecules are arranged in multiple layers on the
surface of the adsorbent.
• The adsorbed molecules do not move on the surface of the
adsorbent.
• A layer does not need to be completed before the next layer starts
to fill up.
• The enthalpy of adsorption is the same for all molecules in a given
layer.
• All molecules in layers other than the first have the same
adsorption energy.
 BET Adsorption Isotherm
• The BET equation is used to find the volume of gas needed to form
a monolayer on the surface of the sample.
• The BET equation can be mathematically represented by:
𝑽𝒎𝒐𝒏𝒐 𝑪𝒇
𝑽=
𝟏−𝒇 𝟏+ 𝑪−𝟏 𝒇

Where:
V = volume of gas adsorbed at pressure P
𝑉𝑚𝑜𝑛𝑜 = amount of gas corresponding to one monolayer
C = constant (function of energy of adsorption and temperature)
f = Equilibrium pressure / Saturation pressure
BET Adsorption Isotherm

𝑽𝒎𝒐𝒏𝒐 𝑪𝒇
𝑽=
𝟏−𝒇 𝟏+ 𝑪−𝟏 𝒇
 BET Adsorption Isotherm
The BET isotherm can be rearranged to give:
𝒇 𝟏 𝑪−𝟏
= + 𝒇
𝟏 − 𝒇 𝑽 𝑪𝑽𝒎𝒐𝒏𝒐 𝑪𝑽𝒎𝒐𝒏𝒐

Accordingly, a plot of 𝑓/[(1−𝑓)𝑉] vs. 𝑓 should produce a straight line

with:
𝑪−𝟏
Slope =
𝑪𝑽𝒎𝒐𝒏𝒐

1
Intercept =
𝑪𝑽𝒎𝒐𝒏𝒐
 BET Adsorption Isotherm

𝑪−𝟏
𝑪𝑽𝒎𝒐𝒏𝒐

𝒇 𝟏 𝑪−𝟏
= + 𝒇
𝟏 − 𝒇 𝑽 𝑪𝑽𝒎𝒐𝒏𝒐 𝑪𝑽𝒎𝒐𝒏𝒐
1
𝑪𝑽𝒎𝒐𝒏𝒐

𝒇
 BET Adsorption Isotherm
Limitations of BET Isotherm
• The BET isotherm is accurate when 𝑃/𝑃𝑜 is between 0.05 and 0.3,
pressure at which only a few complete layers have formed.
• At low pressure, the BET isotherm does not do a good job at
describing adsorption because in deriving the isotherm it was
assumed that all the sites on the adsorbent surface are equivalent.
This is not really the case when only a few molecules have
adsorbed.
• At high pressures, the cracks and roughness of the surface cause
the BET isotherm to fail. This is especially true for very porous
materials where the indents have a width of only a few monolayers.
This is because the cracks can only hold a few monolayers and as
the cracks fill up, the effective surface area of the solid where the
adsorbate adsorbs can change.
 BET Adsorption Isotherm : Problem 1
The data given below are for the adsorption of nitrogen on
alumina at 77.3 K. Show that they fit in a BET isotherm in the
range of adsorption and find 𝑉𝑚𝑜𝑛𝑜 and surface area of alumina
(𝑚 /𝑔). At 77.3 K, saturation pressure, 𝑃∗ = 733.59 torr. The
2 pressure exerted by gas at this T

volumes are corrected to STP and refer to 1g of alumina. Given

contact area of one nitrogen molecule = 16.2 𝑥 10−20 𝑚2 .

P (torr) 37.67 74.20 114.54 142.0 185.34

V (𝑐𝑚3 /𝑔) 23.14 28.1 33.1 36.35 41.49

Where, V = volume of gas adsorbed at pressure P

 BET Adsorption Isotherm : Problem 1
Solution:
ƒ 1 (𝐶 − 1)ƒ
1. BET equation: = +
𝑣(1 − ƒ) 𝑉𝑚𝑜𝑛𝑜 𝐶 𝑉𝑚𝑜𝑛𝑜 𝐶

2. Surface area of adsorbent (𝑚2 /𝑔)

𝑉𝑚𝑜𝑛𝑜 𝑥 𝑁𝐴 𝑥 𝐶𝑜𝑛𝑡𝑎𝑐𝑡 𝑎𝑟𝑒𝑎 𝑜𝑓 𝑜𝑛𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒 (𝑚2 )
=
𝑚𝑜𝑙𝑎𝑟 𝑣𝑜𝑙𝑢𝑚𝑒

0℃ 1 atm
• At STP (standard temperature and pressure), molar volume = 22.4 dm3
25℃ 1 atm
• At RTP (room temperature and pressure), molar volume = 24 dm3
 BET Adsorption Isotherm : Problem 1

Solution:
ƒ 1 (𝐶 − 1)ƒ
From BET equation: = +
𝑣(1 − ƒ) 𝑉𝑚𝑜𝑛𝑜 𝐶 𝑉𝑚𝑜𝑛𝑜 𝐶

ƒ
Plot against ƒ , where ƒ = P/ P ∗
𝑣(1−ƒ)

P (torr) 37.67 74.20 114.54 142.0 185.34

V (𝑐𝑚2 /𝑔) 23.14 28.1 33.1 36.35 41.49

From the data given above, we have

ƒ 0.051 0.101 0.156 0.194 0.253
ƒ/[v(1-ƒ)] (x 103 ) 2.32 4.00 5.58 6.62 8.16
 BET Adsorption Isotherm : Problem 1
ƒ
Plot against ƒ, where
𝑣(1−ƒ)
1
Intercept = = 0.987 x 10−3 𝑐𝑚−3
𝑉𝑚𝑜𝑛𝑜 𝐶 ƒ
𝑣(1 − ƒ)
(𝐶−1)
Slope = = 2.88 x 10−2 𝑐𝑚−3
𝑉𝑚𝑜𝑛𝑜 𝐶
1
(𝐶 -1) x =2.88 x 10−2 𝑐𝑚−3 ƒ
𝑉𝑚𝑜𝑛𝑜 𝐶
(𝐶 -1) x 0.987 x 10−3 𝑐𝑚−3 = 2.88 x 10−2 𝑐𝑚−3
(𝐶 -1) = 29.18
𝐶 = 30.18
1
Further, = 0.987 x 10−3 𝑐𝑚−3
𝑉𝑚𝑜𝑛𝑜 𝐶
𝑉𝑚𝑜𝑛𝑜 = 1/ (𝐶 x 0.987 x 10−3 𝑐𝑚−3 )
= 1/(30.18 x 0.987 x 10−3 )
= 33.57 𝑐𝑚3
𝑉𝑚𝑜𝑛𝑜 = 0.03357 𝑑𝑚3
 BET Adsorption Isotherm : Problem 1
Surface area of adsorbent (𝑚2 /𝑔)
𝑉𝑚𝑜𝑛𝑜 𝑥 𝑁𝐴 𝑥 𝐶𝑜𝑛𝑡𝑎𝑐𝑡 𝑎𝑟𝑒𝑎 𝑜𝑓 𝑜𝑛𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒 (𝑚2 )
=
𝑚𝑜𝑙𝑎𝑟 𝑣𝑜𝑙𝑢𝑚𝑒

0.03357 𝑥 6.02 𝑥 1023 𝑥 (16.2 𝑥 10−20 )

The total area =
22.4
= 146.16 𝑚2 /g

(Given: contact area of one nitrogen molecule = 16.2 𝑥 10−20 𝑚2 )

You should know:
Molar volume = 24 𝑑𝑚3 at room temperature and pressure
Molar volume = 22.4 𝑑𝑚3 at standard temperature and pressure (STP)
 Freundlich Isotherm

The Freundlich equation can be mathematically

represented by:
𝒒 = 𝑲𝑭 𝑪𝟏/𝒏

Where:
𝐾𝐹 = constant (function of energy of adsorption
and temperature)
n = constant
Freundlich Isotherm

𝒒 = 𝑲𝑭 𝑪𝟏/𝒏
 Freundlich Isotherm

The Freundlich isotherm can be rearranged to

give:
𝟏
𝐥𝐨𝐠 𝒒 = 𝐥𝐨𝐠 𝑲𝑭 + 𝐥𝐨𝐠 𝑪
𝒏

Accordingly, a plot of log q vs. log C should

produce a straight line with:
1
Slope =
𝑛
Intercept = log 𝐾𝐹
Freundlich Isotherm

𝟏
𝐥𝐨𝐠 𝒒 = 𝐥𝐨𝐠 𝑲𝑭 + 𝐥𝐨𝐠 𝑪
𝒏
 Adsorption Kinetics – The Rate of Adsorption
The rate of adsorption of a molecule onto a surface can be
expresses in the same manner as any kinetic expression:
Rads = k C x where: x - kinetic order
k - rate constant
C - gas phase concentration
or
Rads = k' P x where: x - kinetic order
k' - rate constant
P - partial pressure of molecule
The rate of adsorption is governed by:
The rate of arrival of molecules at the surface
The proportion of incident molecules which undergo
adsorption
 Adsorption Kinetics – The Rate of Adsorption
We can express the rate of adsorption (per unit area of surface)
as a product of the incident molecular flux, F and the sticking
probability, S.
𝑹𝒂𝒅𝒔 = 𝑺 ∙ 𝑭 [molecules 𝑚−2 𝑠 −1 ]
𝐹 = 𝑃 (2𝜋𝑚𝐾𝑇)1/2
𝐸𝑎
𝑆 = 𝑓(𝜃) ∙ exp(− )
𝑅𝑇
Where, P = gas pressure [𝑁𝑚−2 ]
m = mass of one molecule [kg]
T = temperature [K]
𝑓(𝜃) = function of the existing surface coverage of
adsorbed species
 Adsorption Kinetics – The Rate of Adsorption
Combining the equation for S and F yield the following
expression for the rate of adsorption:
𝑓 𝜃 .𝑃 𝐸𝑎
𝑅= exp(− )
2𝜋𝑚𝐾𝑇 𝑅𝑇
Note:
• It should be recognised that the activation energy for
adsorption may itself be dependent upon the surface
coverage , i.e. Ea = E(q).
• If it is further assumed that the sticking probability is directly
proportional to the concentration of vacant surface sites
(which would be a reasonable first assumption for non-
dissociative adsorption) then f(q) = (1-q) ; where, in this
instance, q is the fraction of sites which are occupied (i.e. the
Langmuir definition of surface coverage).
 Surface Coverage
Fractional surface coverage,
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑎𝑑𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛 𝑠𝑖𝑡𝑒𝑠 𝑜𝑐𝑐𝑢𝑝𝑖𝑒𝑑
𝜃=
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑎𝑑𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛 𝑠𝑖𝑡𝑒𝑠 𝑎𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒
 Potential Energy Curves and Energetics of Adsorption
• In this section we will consider both the energetics of adsorption and
factors which influence the kinetics of adsorption by looking at the
"potential energy diagram/curve" for the adsorption process.
• The potential energy curve for the adsorption process is a representation
of the variation of the energy (PE or E) of the system as a function of the
distance (d) of an adsorbate from a surface.
• Within this simple one-dimensional model, the only variable is the
distance (d) of the adsorbing molecule from the substrate surface. Thus,
the energy of the system is a function only of this variable i.e. E = E(d)
Potential Energy Curves and Energetics of Adsorption
• It should be remembered that this is a very simplistic model
which neglects many other parameters which influence the
energy of the system (a single molecule approaching a clean
surface), including for example
the angular orientation of the molecule
changes in the internal bond angles and bond lengths of
the molecule
the position of the molecule parallel to the surface plane
 Case I - Physisorption
• Only the weak van der Waals forces between the adsorbing
species and the surface.
a v. small drop
• These forces give rise to a shallow minimum in the PE curve at
a relatively large distance from the surface (d > 0.3 nm).
before the strong repulsive forces arising from electron density overlap cause a rapid increase in the total energy.
• No barrier to prevent the atom or molecule which is
approaching the surface.
• The process is not activated and the kinetics of physisorption
always
are invariably fast.
repulsive force

d>0.3nm P.Emin

attractive force
 Case II – Physisorption + Molecular Chemisorption
• At some distance from the surface much higher forces than those
due to the van der Waals interaction begin to dominate. These
forces arise from the formation of chemical bonds.
• The PE curve is dominated by a much deeper minimum at shorter
value of d (higher binding energy).
• No activation energy associated with chemisorption.
• The crossing point of the physisorption and chemisorption curves
fall below the 0 potential energy point of the system and so the
molecule can cross from the physisorbed to the chemisorbed state
without an additional energy.

d at which chemical bond takes place, force arises from it

starts to dominate the weak Van der Waals interaction
 Case III – Physisorption + Dissociative Chemisorption
• The kinetics of how the molecule interacts with the surface depend
very strongly on the crossing point of the two curves as in figure.
• If the crossing point is below the zero potential energy point (Fig. a),
the molecule can pass easily from the physisorbed to chemisorbed
state.
• If the crossing point is above the zero potential energy (Fig. b), then
there is an activation energy associated with adsorption.

Fig. (a) Fig. (b)

 Case III – Physisorption + Dissociative Chemisorption
• In Fig. (a) or (b), the molecule may enter precursor adsorption state,
where it is physisorbed on the surface.
• In Fig. (b), for the moleculeovercome
to enter the chemisorbed state, it must
acquire sufficient energy to surmount the activation or dissociation energy
barrier, 𝐸𝑑𝑖𝑠 .
• The magnitude of 𝐸𝑑𝑖𝑠 is given by the crossing point of the red and blue
curves.
• As the crossing point lies above the zero potential energy axis in Fig. (b),
then the adsorption is said to be activated. Fig. (a) is non-activated
chemisorption.
𝐸𝑎𝑑𝑠 = 𝐸𝑑𝑒𝑠 𝐸𝑎𝑑𝑠 < 𝐸𝑑𝑒𝑠

Fig. (a) Fig. (b)

Potential Energy Curves and Energetics of Adsorption
Potential Energy Curves and Energetics of Adsorption
 Desorption Kinetics
• The rate of desorption of an adsorbate from a surface can be expressed in
the general form:

Rdes = k N x where x - kinetic order of desorption

k - rate constant for the desorption process
N - surface concentration of adsorbed species
• The order of desorption can predicted
I. Atomic or Simple Molecular Desorption
A(ads) A(g)
- will usually be a first order process (x = 1). Example:
Cu / CO (ads) Cu (s) + CO (g) desorption of CO atoms from a Cu surface

II. Recombinative Molecular Desorption

2 A (ads) A2 (g)
- will usually be a second order process (x = 2). Example:
Ni / H (ads) Ni (s) + H2 (g) desorption of H atoms as H2 from a Ni surface
 Desorption Kinetics
1st and 2nd order desorption

1st order, desorption occurs from a

surface site

2nd order, desorption occurs

after surface reaction and
combination, e.g.;

Hads + Hads H2 desorbed

 Activation Energy

• Activation Energy (Ea) – is the energy level that the

reactant molecules must overcome before a reaction
can occur.

Exothermic Endothermic
 Activation Energy

• In order to calculate the activation energy, we

need an equation that relates the rate constant of
a reaction with the temperature (energy) of the
system. This equation is called the Arrhenius
Equation:
𝑘 = 𝑍𝑒 −𝐸𝑎 /𝑅𝑇
𝐸𝑎 1
ln 𝑘 = − + ln 𝑍
𝑅 𝑇
• K = rate constant
• 𝐸𝑎 = activation energy
• R = gas constant
• T = temperature in Kelvin
• Z = frequency factor constant or Arrhenius factor
 Activation Energy

• Calculate the Activation Energy by graphing ln k versus 1/T

𝐸𝑎 1
ln 𝑘 = − + ln 𝑍
𝑅 𝑇

• When the ln k (rate constant) is plotted versus the inverse of

the temperature (kelvin), the slope is a straight line.
• The value of the slope is equal to –Ea/R where R is a constant
equal to 8.314 J/mol.K.
 Exercise: Activation Energy

Variation of the rate constant with temperature for the first-

order reaction 2N2 O5 g 2N2 O4 g + O2 (g) is given in
the following table. Determine graphically the activation energy
for the reaction.

T (K) K (𝒔−𝟏 )
298 1.74 x 10−5
308 6.61 x 10−5
318 2.51 x 10−4
328 7.59 x 10−4
338 2.40 x 10−3
 Exercise: Activation Energy

Solution:

T (K) k (𝒔−𝟏 ) 1/T (𝑲−𝟏 ) ln k

298 1.74 x 10−5 0.003356 -10.96
308 6.61 x 10−5 0.003247 -9.62
318 2.51 x 10−4 0.003145 -8.29
328 7.59 x 10−4 0.003049 -7.18
338 2.40 x 10−3 0.002959 -6.03
 Exercise: Activation Energy
Plot ln k versus 1/T

0
0.0029 0.003 0.0031 0.0032 0.0033 0.0034
-2

-4
y = -12401x + 30.662
R² = 0.9998
ln k

-6

-8

-10

-12
1/T (1/K)
 Exercise: Activation Energy

𝐸𝑎
Slope = −
𝑅
𝐸𝑎 = − (slope) (R)

From equation, y = -12401x + 30.662

𝐸𝑎 = − (− 12401 K) (8.314 J/mol.K)
𝐸𝑎 = 103102 J/mol
𝐸𝑎 = 103 kJ/mol