Processes at solid surfaces (Chapter 25)

SURFACE CHEMISTRY

Surface mediated chemical processes

1.Diffusion of reactants to the active surface

2.Adsorption of one or more reactants onto the surface
3.Surface reaction
4.Desorption of products from the surface
5.Diffusion of products away from the surface
Adsorption

~Physical adsorption (physisorption, van der Waals adsorption)

*van der Waals force
*The heat evolved is less than 20 kJ mol-1
*no activation energy  rapid process
*multimolecular layer

~Chemical adsorption (chemisorption, activated adsorption)

*nature of bonds may lie between complete ionic or covalent character
*The heat evolved is 100 to 500 kJ mol-1
*appreciable activation energy  slow process
*unimolecular layer

Substrate Adsorbate
 Energetics of adsorption

~Figure prese nts the re l ationship b e tw ee n

physisorption and chemisorption with the potential-
energy diagram.
~It relates to the adsorption of hydrogen on a surface
such as that of a metal.
~Physisorption occurs first, the intact molecule being
held loosely to the surface by dispersion forces.
~The potential-energy curve for chemisorption, with
dissociation of the hydrogen molecule, has a much
deeper minimum, corresponding to stronger
bonding.
~The crossing of the two curves shows that there is a
small energy of activation for the chemisorption
process.
~This diagram shows that initial physisorption is an
important feature of the chemisorption process. If
there were no physisorption, there would be a much
higher activation energy for the chemisorption.
 Lennard-Jones Potential chemisorption

Activated chemisorption (with dissociation)

Un-ativated chemisorption (without dissociation)
Case 1: Simple Langmuir isotherm Case 2: Adsorption with dissociation
Single molecule adsorption - single molecule adsorbed dissociatively
Dynamic equilibrium on one site

A -B(g) + M(surface site) D A-M-B

A

A B

A B
case I

Cs K [ A]
  case II
C 1  K [ A]
Cs ( KPAB )1/2
k ads  
K  C 1  ( KPAB )1/2
k des
18.2 Adsorption Isotherms
An equation that relates the amount of a substance to a surface to its concentration in
the gas phase or in solution, at a fixed temperature, is known as an adsorption
isotherm.
The Langmuir Isotherm

~Suppose that, after equilibrium is established, a fraction  of the surface is covered by

adsorbed molecules; a fraction 1- will not be covered.
~The rate of adsorption will be proportional to the concentration [A] of the molecules in
the gas or liquid phase and also proportional to the fraction of the surface that is bare,

va  k a [A](1  θ)

~The rate of desorption vd is proportional only to the number of molecules attached to

the surface, which in turn is proportional to the fraction of surface covered:
vd  k d θ
~At equilibrium, the rates of adsorption and desorption are the same; thus
θ k
k a [A](1  θ)  k d θ  a [A]
1  θ kd

~The ratio ka/kd is an equilibrium constant and can be written as K; then

θ K [A]
 K [A] θ simple Langmuir isotherm
1 θ 1  K [A]

~a graph of  against [A].

~At sufficiently low concentrations we can
neglect K[A] in comparison with unity, and
then  is proportional to [A].
~At very high concentrations

K [A] 1 1
θ 1 θ  
K [A] 1 1 1  K [A] 1  K [A] K [A]
θ  1
1  K [A] θ K [A]
Adsorption with Dissociation

K [A] S represents a surface site and A

θ
1  K [A] the substance being adsorbed.

In certain cases there is evidence that the process of adsorption is accompanied by the
dissociation of the molecule when it becomes attached to the surface. For example, when
hydrogen gas is adsorbed on the surface of many metals, the molecules are dissociated into
atoms each of which occupies a surface site. This type of adsorption may be represented as

The process of adsorption

va  k a [A](1  θ)2

The desorption process

vd  k d θ 2
 ~At equilibrium the rates are equal, and therefore,
1/ 2
θ  ka 
  [A] 
  K 1 / 2 [A]1 / 2 K is equal to ka/kd.
1  θ  kd 

K 1 / 2 [A]1 / 2 1
θ 1 θ 
1  K 1 / 2 [A]1 / 2 1  K 1 / 2 [A]1 / 2

Figure 18.2

~Figure 18.2c shows a graph of  against

[A]1/2.
~When the concentration is very small,
K1/2[A]1/2 is much smaller than unity, and  is
then proportional to [A]1/2.
~At very high concentrations,
1 K1/2[A]1/2 is >>1,
1  θ  1/ 2 1/ 2
K [A]
K 1 / 2 [A]1 / 2 1 1
θ  1  1/ 2 1/ 2
1  K 1 / 2 [A]1 / 2 θ K [A]
Competitive Adsorption

~Suppose that the fraction of surface covered by molecules of type A is A and that the
fraction covered by B is B. The fraction bare is 1-A-B. If both substances are
adsorbed without dissociation, the rate of adsorption of A and B are
vaA  k aA [A](1  θ A  θ B ) vaB  kaB [B](1  θ A  θ B )
~The rates of desorption are

vdA  kdA θ A vdB  kdB θ B

θA k aA θB k aB
 [A]  K A [A]  [B]  K B [B]
1  θ A  θ B k dA 1  θ A  θ B k dB
K A [A] K B [B]
θA  θB 
1  K A [A]  K B [B] 1  K A [A]  K B [B]
~The fraction of the surface covered by one substance is reduced if the amount of the
other substance is increased. This is because the molecules of A and B are competing
with one another for a limited number of surface sites.
~There is evidence that sometimes two substances are adsorbed on two different sets of
surface sites, in which case there is no competition between them.
Case 3: Competitive Adsorption
- two molecules adsorbed on two sites

A(g) + B(g) + 2M(surface site) D A-M + B-M

A B

case III
 Adsorption On Solid Surface
• Langmuir adsorption isotherm
Cs
Cs BP
Strong adsorption kads>> kdes  1
case I   0 C
C 1  B0 P C
Weak adsorption kads<< kdes   s  B0 P
C
Cs ( B0 PAB )1/2
case II  
C 1  ( B0 PAB )1/2

Amount adsorbed
C B0 ,A PA
Case III  A  s ,A  mono-layer
C 1  B0 ,A PA  B0 ,B PB
large B0 (strong adsorp.)
C B0 ,B PB
 B  s ,B  moderate B0
C 1  B0 ,A PA  B0 ,B PB
small B0 (weak adsorp.)

Pressure

 Langmuir adsorption isotherm established a logic picture of adsorption process

 It fits many adsorption systems but not at all
 The assumptions made by Langmuir do not hold in all situation, that causing error
 Solid surface is heterogeneous thus the heat of adsorption is not a constant at different 
 Physisorption of gas molecules on a solid surface can be more than one layer
Isosteric enthalpy of adsorption can be
obtained from the slope of the plot (where
p is the pressure needed to achieve the
specified surface coverage
Other Isotherms

~Systems that obey the Langmuir type are often referred to as showing ideal adsorption.
~Systems frequently deviate significantly from the Langmuir equation. This may be because
the surface is not uniform, and also there may be interactions between adsorbed molecules;
a molecule attached to a surface may make it more difficult, or less difficult, for another
molecule to become attached to a neighboring site, and this will lead to a deviation from the
ideal adsorption equation.

Freundlich Isotherm (incorporate the BET Isotherm (Braunauer, Emmett, Teller)

role of substrate-substrate interactions
on the surface)
x  kcn
~x is the amount of a substance
adsorbed; c is the concentration of a
substance.
~k and n are empirical constants. The
value of n is usually less than unity.
PP0 1 P
 
V ( P0  P ) V0 K V0
~V is the volume of gas adsorbed at pressure
P ,
and V0 the volume that be adsorbed as a
monolayer; P 0 is the saturation vapor
pressure, and K is the equilibrium constant
for the adsorption.
~The BET isotherm is particularly useful for
determining surface area.
 BET Isotherm
• Use of BET isotherm to determine the surface area of a solid
– At low relative pressure P/P0 = 0.05~0.35 it is found that
P / P0 1 c 1
  ( P / P0 )  ( P / P0 )
V ( 1  P / P0 ) cVm cVm
P/P0 : Relative Pressure
Y = a +b X V : Weight of gas adsorbed at a P/P0
Vm : Weight of adsorbate constituting a monolayer of θ
θ : Surface coverage
C : BET C constant, related with heat of adsorption
(50 – 250 on most of solid surfaces)

Assumptions on the derivation of the BET model

-Adsorbates are arranged in multiple layers on the surface of the substrate
- adsorbates do not move on the surface of the substrate
-A layer does not need to be completed befored the next layer starts to fill up
- the enthalpy of adsorption is the same for all molecules in a given layer
 P / P0
V (1 P / P0 )

P/P0

The principle of surface area (and other parameters) determination by

BET method:
P / P0
A plot of V (1 P / P0 )
against P/P0 will yield a straight line with slope of equal to
(c-1)/(cVm) and intersect 1/(cVm).

For a given adsorption system, c and Vm are constant values, the surface area of a solid
material can be determined by measuring the amount of a particular gas adsorbed on
the surface with known molecular cross-section area Am,

Vm Vm - volume of monolayer adsorbed gas molecules calculated from the plot, L

As  Am N m  Am  6.022  1023 VT,P - molar volume of the adsorbed gas, L/mol
VT , P Am - cross-section area of a single gas molecule, m2

* In practice, measurement of BET surface area of a solid is carried out by N2

physisorption at liquid N2 temperature; for N2, Am = 16.2 x 10-20 m2
Problem
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/mm3 at 12.0 15.1 19.0 23.9 28.2 33.0
20 C and 1 atm
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 1015 molecules cover 1 cm2 of the surface. Make an estimate of the
effective area in Langmuir’s experiment.
Problem
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/cm3 (STP) 135 247
At 77 K the saturation vapor pressure P0 of nitrogen is 101.3 kPa. Estimate the surface
area of the gel, taking the molecular area of nitrogen to be 1.6210-19 m2.
Definition of Adsorption

The process through which a substance, originally present in one phase, is removed from that
phase by accumulation at the interface between that phase and separate phase.

In principle, adsorption can occur at any solid-fluid interface.

- gas-solid interface (as in the adsorption of a VOC on activated carbon)

- liquid-solid interface ( as in the adsorption of an organic pollutant on activated carbon)

Common adsorbents

- Activated carbon: A char-like material with high surface area

- silica gel: hard, granular, porous material made by precipitation from sodium silicate
solutions treated with an acid
- activated alumina: aluminum oxide activated at high temperature and used primarily for
moisture adsorption
- aluminosilicates (molecular sieves) – porous synthetic zeolites used primarily in separation
processes
Adsorption equilibrium

- Adsorption will continue until equilibrium will be established between the substance in
solution and the same substance in ther adsorbed state
- At equilibrium, a relationship exists between the concentration of the species in solution and
the ‘concentration‘ of the same species in the adsorbed state (i.e., the amount of species
adsorbed per unit mass of adsorbent)
 Adsorption On Solid Surface
• Five types of physisorption isotherms are found over all solids
I
– Type I is found for porous materials with small pores e.g. charcoal.
It is clearly Langmuir monolayer type, but the other 4 are not
II
– Type II for non-porous materials
amount adsorbed

III
– Type III porous materials with cohesive force between adsorbate
molecules greater than the adhesive force between adsorbate
molecules and adsorbent
IV – Type IV staged adsorption (first monolayer then build up of additional
layers)

V
– Type V porous materials with cohesive force between adsorbate
molecules and adsorbent being greater than that between
1.0 adsorbate molecules
relative pres. P/P0
18.4 Chemical Reactions on Surfaces

~An important concept in connection with surface reactions is the molecularity, which is
the number of reactant molecules that come together during the course of reaction; we do
not count the surface site.
~The molecularity of a surface reaction is deduced from the kinetics on the basis of the
experimental results and of theoretical considerations.
~Reactions involving a single reacting substance are usually, but invariably, unimolecular.
*The mechanism of the surface-catalyzed ammonia decomposition is, for example, usually
unimolecular.
~Reaction involving two reacting substance are usually bimolecular.
*The kinetics of the decomposition of acetaldehyde on various surfaces can only be
interpreted on the hypothesis that two acetaldehyde molecules, adsorbed on neighboring
surface sites, undergo a bimolecular.
*When reactant molecules are dissociated on the surface, the reaction may involve
interaction between an atom or radical and a molecule; for example, the exchange
reaction between ammonia and deuterium on iron is a bimolecular interaction between a
deuterium atom and an ammonia molecule.
 adsorption
 Catalytic reaction involves 4 steps:

(1) adsorption of the reacting gases on the surface

of the catalyst

(2) activation of the adsorbed reactants

(3) reaction of the activated gases in the adsorbed

phase

(4) diffusion of the products of the reaction from the

surface into the gas phase
Unimolecular Reactions

Surface reactions involving one molecule may be treated in terms of the Langmuir adsorption
isotherm. In the simplest case the rate of reaction is proportional to  and is thus

kK[A] It has been derived on assumption of a rapid adsorption

v  kθ 
1  K [A] equilibrium followed by slow chemical reaction.

~The dependence of v on [A], shown in left Figure, is

Explore its form in the limits of
exactly the same as that given by the Langmuir
low/high pressure
isotherm
~At sufficiently high concentrations the rate is
independent of the concentration, which means that
the kinetics are zero order.
~At low concentrations, when K[A]<<1, the kinetics
are first order.
~A good example of this type of behavior is the
decomposition of ammonia into nitrogen and
hydrogen on a tungsten surface.
~Sometimes a substance other than the reactant is adsorbed on the surface, with the result
that the effective surface area, and therefore the rate, are reduced.
~Suppose that a substance A is undergoing a unimolecular reaction on a surface and that a
nonreacting substance I, known as an inhibitor or a poison, is also adsorbed.
~If the fraction of the surface covered by A is  and that covered by I is i, we have from the
Langmuir isotherm with competition adsorption that
K [A]
θ
1  K [A]  K i [I] K and Ki are the adsorption constants for A and I.
~The rate of reaction, equal to k, is thus
kK[A]
v
1  K [A]  K i [I]
~A case of special interest is when the surface is only sparsely covered by the reactant but is
fairly fully covered by the inhibitor. In other words
Ki[I]>>1+K[A]
and the rate is then A good example of this type reaction is provided by the decomposition of
ammonia on platinum, the rate law for which is
k[NH 3 ]
kK[A] v
v K i [H 2 ]
K i [I] Since hydrogen is a product of reaction, there is progressive inhibition as
reaction proceeds. There is no appreciable inhibition by the other reaction
product, nitrogen.
Bimolecular Reactions
Langmuir-Hinshelwood Mechanism

~In the first step the two molecules A and B become adsorbed on neighboring sites on the
surface. Reaction then takes place, by way of an activated complex, to give the reaction
products.
~When this mechanism applies, the rate is proportional to the probability that A and B
are adsorbed on neighboring sites, and this is proportional to the product of fractions of
the surface, A and B, covered by A and B. The rate of reaction is therefore
K A [A] K B [B] kKA K B [B][A]
θA  θB  v  k θ Aθ B 
1  K A [A]  K B [B] 1  K A [A]  K B [B] (1  K A [A]  K B [B]) 2
Figure 18.3
The rate first rises, pass through a maximum, and then
decreases toward zero.
~The physical explanation of the falling off of the rate at
high concentrations is that one reactant displaces the
other as its concentration is increased.
~The maximum rate corresponds to the presence of the
maximum number of neighboring A-B pairs on the surface.
~At sufficiently low concentrations of A and B, the second-order reaction kinetics is
predicted, and this has been observed in a number of systems.
kKA K B [A][B]
v  k θ Aθ B  v  kKA K B [A][B]
(1  K A [A]  K B [B]) 2

~A case of special interest is when one reactant (e.g., A) is weakly adsorbed and the
other strongly adsorbed. This means that KB[B]>>1+KA[A], and it follows that

kKA K B [A][B] kKA [A]

v  k θ Aθ B  v
(1  K A [A]  K B [B]) 2 K B [B]

The order is 1 for A and -1 for B. An example is the reaction between carbon
monoxide and oxygen on quartz, where the rate is proportional to the pressure
of oxygen and inversely proportional to the pressure of carbon monoxide.
Langmuir-Hinshelwood Mechanism

 the rate
 to the probability that A & B are adsorbed on
neighboring sites, which is

 to the product of the fractions of the surface A

and B covered by A & B

rate = kAB
 An alternative mechanism for a bimolecular surface process
is for the reaction to occur between a molecule that is not
absorbed (e.g, A) and an adsorbed molecule (B). The
adsorption of A may occur; it is simply postulated, in this
mechanism, that an adsorbed A does not react.

Langmuir-Rideal Mechanism

The rate for this mechanism is proportional to the concentration of A and to the fraction
of the surface that is covered by B:
kKB [A][B]
v  k[A] θ B 
1  K A [A]  K B [B]
Figure 18.3
~The variation v with [A] is shown in Figure 18.3c; the
same type of curve is found if v is plotted against [B].
~There is no maximum in the rate, and this provides a
possible way of distinguishing between this mechanism
an the Langmuir-Hinshelwood mechanism.
~Not many ordinary chemical reactions occur by a Langmuir-Rideal mechanism. There
is evidence, however, that radical combinations on surface sometimes occur in this way.
~The combination of hydrogen atoms, for example, is sometimes a first-order reaction,
and it appears to occur by the mechanism

The fraction of the surface covered by hydrogen atoms is

K [H]
θ
1  K [H]

and the rate of combination is thus

kK[H] 2
v  k[H] θ 
1  K [H]
~At lower temperatures the surface may be fully covered, so that K[H]>>1 and
v=k[H] and the kinetics are first order.
~At higher temperatures the coverage decreases and if 1>>K[H], the rate is
v=kK[H]2
~An increase in order from 1 to 2 has in fact been observed as the temperature is raised.
 ELEY-RIDEAL Mechanism
= a gas-phase molecule collides with another molecule
adsorbed on the surface
- the rate of formation of the product is expected
to be
 to the partial pressure (PB) of the non-
adsorbed gas
 to the extent of surface coverage (A) of the
adsorbed gas
A + B  P
rate = kPBA
 adsorption
 the rate constant (k) might be larger than the
uncatalyzed gas-phase reaction because:
(a) the reaction on the surface has a low activation
energy,
(b) the adsorption itself, is often not activated

- adsorption isotherm for A can be expressed in terms of its

partial pressure, PA
= if it follows the Langmuir isotherm then,
rate  kPB  KP A

1  KPA 
1/2
 adsorption
 if A = diatomic molecules
and, 1/2

θ  KP 1/2
1  KP 

then, the rate will be,

rate  kKP A PB

1  KPA
 adsorption
 if the partial pressure of A is high
then, KPA >> 1  almost complete coverage
and,
rate = kPB
 means: the rate determining step is the
collision of B with the adsorbed species
 if the partial pressure of A if low
then, KPA << 1
and,
rate = kKPAPB
 means: the extent of surface coverage is
important in the rate determination