CY 6015 : Surface, Interfaces, dispersed systems and Macromolecules

Semester : 01 Aug to 11 Nov 2016

Teacher : Prof. G. Ranga Rao

Adsorption isotherms & Heat of adsorption measurements

08 Oct 2016 Prof. GRR : CY 6015

 Kinetic Aspects on surfaces

McQuarrie & Simon, p.1206

Interaction potential for chemisorption and physisorption of a molecule

that impinges the surface perpendicular, i. e. in the z-direction

08 Oct 2016 Prof. GRR : CY 6015

 Chemisorption of Unsaturated Hydrocarbons

Unsaturated hydrocarbons (alkenes, alkynes, aromatic) interact strongly with metal

atom surfaces. At low temperatures (and on less reactive metal) the adsorption may
be molecular with some distortion of bond angles around the carbon atom.

Ethene may bond to give both a -complex (A) or a di- adsorption

complex (B):

Side-on orientation
(A) (B)
Chemisorbed
ethene
As the temperature is raised, or even at low temperatures on more reactive surfaces,
a stepwise dehydrogenation may occur. One particularly stable surface intermediate
found in the dehydrogenation of ethene is the ethylidyne complex, whose formation
also involves H-atom transfer between the carbon atoms.

Ethylidyne :
this adsorbate preferentially occupies a 3-fold hollow site
to give pseudo-tetrahedral co-ordination for the carbon
atom.
Side-on orientation

08 Oct 2016 Prof. GRR : CY 6015

 The Desorption Process

An adsorbed species present on a surface at low temperatures may remain almost

indefinitely in that state. However, as the temperature of the substrate is increased
there will come a point at which the thermal energy of the adsorbed species is such
that one of the following things may occur :

 A molecular species may decompose to yield either gas phase products or other
surface species.

 An atomic adsorbate may react with the substrate to yield a specific surface
compound, or diffuse into the bulk of the underlying solid.

 The species may desorb from the surface and return into the gas phase.

Desorption Kinetics

The rate of desorption, Rdes, of an adsorbate from a surface can be expressed in

the general form :

where x - kinetic order of desorption

Rdes = k N x
k - rate constant for the desorption process
N - surface concentration of adsorbed species

08 Oct 2016 Prof. GRR : CY 6015

I. Atomic or Simple Molecular Desorption

A(ads)  A(g)
M(ads)  M(g)

This process is first order.

e.g. desorption of Cu atoms from a W surface (Cu (ads) / W  W(s)+ Cu(g))

desorption of CO molecule from Cu surface (CO (ads)/Cu Cu (s) + CO (g))

II. Recombinative Molecular Desorption

2 A (ads) A2 (g)

This process is usually a second order process.

e.g. Desorption of O2 from a Pt surface (O(ads)/Pt  Pt (s) + O2 (g))

Desorption of H2 from a Ni surface (H (ads)/Ni  Ni (s) + H2 (g))

The rate constant for desorption process may be expressed in Arrhenius form as

kdes =  exp ( -Eades / RT )

08 Oct 2016 Prof. GRR : CY 6015

 So the general expression for the rate of desorption can be given by

Surface Residence Times

This is the average time that a molecule will spend on the surface under a given set
of conditions before it desorbs into the gas phase.

For a first order process such as the desorption of a molecularly adsorbed species :
M(ads)  M(g)

the average time () prior to the process occurring is given by :  = 1/k1

where k1 is the first order rate constant

We know that k1 =  exp ( -Eades/RT )

If we assume, Eades ~ - Hads, then we have the following expression for surface
resident time
 = o exp ( Hads/RT)
o ( = 1/  ) corresponds to the period of vibration of the bond between the adsorbed
molecule and substrate and is frequently taken to be about 10-13s

08 Oct 2016 Prof. GRR : CY 6015

 The Langmuir Isotherm (Ideal adsorption isotherm)

Adsorption of reactants on the surface is the first step in every reaction of heterogeneous
catalysis

An equation that relates the amount of a substance attached to a surface to its

concentration in the gas phase or in solution, at a fixed T, is known as adsorption isotherm.

Whenever a gas is in contact with a solid there will be an equilibrium established

between the molecules in the gas phase and the corresponding adsorbed species
(molecules or atoms) which are bound to the surface of the solid.

As with all chemical equilibria, the position of equilibrium will depend upon a
number of factors :
1. The relative stabilities of the adsorbed and gas phase species involved.
2. The temperature of the system (both the gas and surface).
3. The pressure of the gas above the surface.

In general, factors (2) and (3) exert opposite effects on the concentration of
adsorbed species
The Langmuir isotherm describes the dependence of the surface coverage of an
adsorbed gas on the pressure of the gas above the surface at a fixed temperature.

08 Oct 2016 Prof. GRR : CY 6015

Postulates of Langmuir isotherm (by Irving Langmuir in 1916)

• All adsorption sites are fixed and energetically equivalent.

• There is no lateral interaction between the adsorbed molecules.
• Adsorption restricted to monolayer.
• At equilibrium, the rate of adsorption is equal to the rate of desorption.

The Langmuir isotherm can be derived from equilibrium considerations.

For a non-dissociative (molecular) adsorption process, we consider the adsorption

to be represented by the following chemical equation :

S -* + M(g) = S - M Where S -* represents a vacant surface site.

The equilibrium constant for the above process can be given by

number of surface sites occupied by adsorbate

The fractional coverage,  =
total number of substrate adsorption sites

08 Oct 2016 Prof. GRR : CY 6015

 Note that :

1. [S - M ] is proportional to the surface coverage of adsorbed molecules,

i.e. proportional to .
2. [ S - * ] is proportional to the number of vacant sites, i.e. proportional to (1- ).
3. [ M ] is proportional to the pressure of gas , P.

Hence, it is also possible to define another equilibrium constant, b, as given below.

atm-1 b = ka/kd

Rearrangement of the above equation gives following expression for surface coverage
After equilibrium is eatablished :
 : fraction of surface covered by
adsorbed molecules
The above expression is the Langmuir isotherm for non-dissociatively (1- ) : fraction fo surface not covered
chemisorbed molecules.
rads  ka [ A](1   )
rdes  kd
At equilibrium , ka [ A](1   )  kd
ka  b[ A]
08 Oct 2016 Prof. GRR : CY 6015 b[ A]  [ A]   
kd 1 1  b[ A]
 Langmuir Isotherm - extension to dissociative adsorption

Dissociative adsorption of a homonuclear diatomic molecule, A2 , can be represented

by the following chemical equation

2 (S -) + A2 (g) = 2 (S - A) where S - represents a vacant surface site (1-).

[S-A]2 ka d
K=
2
[S -] [A2]
=  k P N (1   ) 2
kd dt
a

d
  kd N  2
Substituting the values as in the previous case, we have dt
At equilibrium , ka P N (1   )2  kd N  2
ka 2 bP
bP  P  
1    1  bP
2
kd

The above expression is valid for the dissociative chemisorption of diatomic

molecules.

08 Oct 2016 Prof. GRR : CY 6015

Variation of Surface Coverage with Temperature & Pressure

For a reversible molecular adsorption process,

The following figure shows the variation of coverage with pressure

At low pressure, bP <<1,  = bP

At high pressure, bP>>1,  = 1
Surface well
covered write suitable expressions and
Surface sparsely 1 1 1
covered analyse plots of vs or
 P P
At a given pressure the extent of adsorption is determined by the value of b
Which in turn is dependent upon both the temperature (T) and the enthalpy
(heat) of adsorption.

Can we estimate surface area of the adsorbent using Langmuir isotherm data?

08 Oct 2016 Prof. GRR : CY 6015

 McQuarrie & Simon, p.1210

1/ (a.u.)

1/P (a.u.)

Langmuir plots for O2 and CO adsorbed on silica. The experimental

data fits the Langmuir adsorption isotherm,

1 1
 1
 bP

08 Oct 2016 Prof. GRR : CY 6015

Dependence of b on external parameters:
b is only a constant if the enthalpy of adsorption is independent of coverage.
As with all chemical equilibria, the position of equilibrium (determined by the value of b) will
depend upon a number of factors:
1. The relative stabilities of the adsorbed and gas phase species involved.
2. The temperature of the system (both the gas and surface, although these are normally the
same).
3. The pressure of the gas above the surface.

In general, factors (2) and (3) exert opposite effects on the concentration of adsorbed species
-that is to say that the surface coverage may be increased by raising the gas pressure
but will be reduced if the surface temperature is raised.

Graphical form of the Langmuir Isotherm

here b3 > b2 > b1

08 Oct 2016 Prof. GRR : CY 6015

 The value of b is increased by

1. A reduction in the system temperature

2. An increase in the strength of adsorption

Effect of the adsorption enthalpy

Effect of the temperature on coverage
on coverage at fixed temperature

Increasing H

A given equilibrium surface coverage may be attainable at various combinations of

pressure and temperature as highlighted above… note that as the temperature is
lowered the pressure required for a particular equilibrium surface coverage decreases.

08 Oct 2016 Prof. GRR : CY 6015

Determination of Enthalpies of Adsorption
The enthalpy of adsorption for a particular adsorbate/substrate system can be
evaluated by studying the P-T dependence of the surface coverage as follows.

Step 1 : Involves determination

of a number of adsorption isotherms
(where a single isotherm is a
coverage / pressure curve at a
fixed temperature).

Step 2 : It is then possible to read off

a number of pairs of values of pressure
and temperature which yield the same
surface coverage.

08 Oct 2016 Prof. GRR : CY 6015

 Step 3 : The Clausius-Clapeyron equation may then be applied to this set of (P-T)
data and a plot of ( ln P ) vs (1/T) should give a straight line, the slope of which
yields the adsorption enthalpy.
Clausius-Clapeyron eqn
d ln P H vap

dT RT 2
Isosteric (at constant ) heat of adsorption

Note - this method is applicable only when the adsorption process is

thermodynamically reversible.

08 Oct 2016 Prof. GRR : CY 6015

 Ref. Atkins book,
 9th ed., page 891
KP  bP 
1
ln K  ln P  constat
  ln K    ln P 
     T 
 T   
d ln K H ads
van ' t Hoff eqn : 
dT RT 2
  ln K    ln P  H ads
     
 T   T  RT 2

  ln P 

H ads d 1 
T  1
 
  (1 / T )  R dT T2

08 Oct 2016 Prof. GRR : CY 6015

 Empirical isotherms :
Temkin iostherm : θ = c1ln(c2 P)
1
Freundlich isotherm : θ = c1P c2
.. c1 and c2 are constants
This is for non - ideal adsorption systems, where surface heterogeneity
and repulsive forces between adsorbed molecules are considered.

Freundlich isotherm is also writen as, x = kcn

x is amount of sunstance adsorbed
c is concentration
k and n are empirical constants; x increasesas c increases.

Temkin isotherm takes into account the variations in adsorption enthalpy

linearly with pressure.

Freundlich isotherm incorporates the role of adsorbate-adsorbate interactions.

08 Oct 2016 Prof. GRR : CY 6015

A single-crystal adsorption calorimeter : W.A. Brown, R. Kose and D.A. King, Chem. Reviews 98 (1998) 797

A pulsed molecular beam is directed at a very thin single crystal (about 2000 Å
thick). A proportion of these molecules adsorb at the surface and cause the
liberation of adsorption heat within the surface region. The small heat capacity
of the crystal leads to a measurable rise in temperature (the adsorption of 1
percent of a monolayer typically leads to a temperature rise of 0.1 K). The heat is
conducted very efficiently to the back of the crystal and very in-efficiently to the
sides. This means that the cooling of the crystal occurs mostly by the emission of
thermal radiation. For this reason the back-side of the crystal is made black with
a carbon film such that it will emit most of the radiation which is then measured
with an infrared detector. The detector measures a short infrared pulse and the
crystal is cooled down again before the next pulse of molecules arrives. In this
way the heat of adsorption can be measured reliably and directly even for
systems where the adsorption is an irreversible process.
08 Oct 2016 Prof. GRR : CY 6015
 Heat is always liberated on adsorption and
enthalpy of adsorption is always – ve.
G  H  T S
Adsorption process involves decrease in entropy.
For adsorption S is  ve ,
 H must be  ve to have G negative for adsoption to occur.

08 Oct 2016 Prof. GRR : CY 6015

Statistical thermodynamics approach to adsorption (non-dissociative):
Derivation of Langmuir isotherm – expressing K in terms of partition functions

e   i ni
pi  = ; q   gi e   i
q N
q : molecular partition function
pi is the fraction of molecules in the state "i"

Suppose, volume of gas = v

Area of the surface = S
Number of gas molecules in the gas phase = Ng
Number of adsorbed molecules = Na
Number of bare sites at equilibrium =Ns

08 Oct 2016 Prof. GRR : CY 6015

 Langmuir isotherm in terms of partition functions:
(Non-dissociative adsorption on a surface)
Let us take:
Ng : total number of molecules in the gas
Nads : number of adsorbed molecules
Ns : number of bare sites at equilibrium
S : area of the surface
Concentration of these species are:
Ng
Conc. in the gas pahse : c g =
V
N ads
Conc. of adsorbed molecules : c ads = cads
S Kads =
Ns c g cs
Conc. of bare sites : c s =
S
08 Oct 2016 Prof. GRR : CY 6015
 Langmuir isotherm in terms of partition functions:

Equilibrium const. for the ads. process is Kads

N ads
c S N ads N ads
Kads = ads   
c g cs Ng Ns NgNs  Ng 
   Ns
V S V  V 

For a general chemical reaction, aA  bB yY  zZ

qYy qZz E / kB T
K y z e e   i ni
qY qZ pi  = ; q   gi e   i
q N
q : molecular partition function
pi is the fraction of molecules in the state "i"

08 Oct 2016 Prof. GRR : CY 6015

Equilibrium const. in terms of partition functions
qads E / RT
Kads = e
q g qs
qads and qs are for unit surface area; qg is for unit volume
cads cads qads E
Kads =   cg e / RT

c g cs cs q g qs
  fraction of surface covered
cads  qads E / RT
   cg e
cs 1   q g qs

08 Oct 2016 Prof. GRR : CY 6015

 Equilibrium const. in terms of partition functions

 qads E
  cg e / RT

1 q g qs

 2 mk BT 
3/ 2

qg  partition function per unit volume  3

q g , rot q g , vib
h
Adsorption sites have no freedom of motion,  qs  1
qads for adsorbed molecules involves only internal factors.
The adsorption isotherm becomes,
  h3 qads E

 cg  e / RT

1   2 mk T 3 / 2 q g , rot q g , vib 
 B 

08 Oct 2016 Prof. GRR : CY 6015

 The adsorption isotherm becomes,
 h3 qads
 cg e E / RT

1  2 mkBT 
3/ 2
q g ,rot q g ,vib

which is same as Langmuir isotherm,  bp
1
This is applicable to adsorbed molecules localised on the surface
(i.e. chemisorption). When the molecules move freely, they have
two translational degrees of freedom and another equation can
be derived.


dissociation
Using statistical approach, derive adsorption isotherm for A 2 +2S   2(S-A)

08 Oct 2016 Prof. GRR : CY 6015