A PRESENTATION ON

Surface properties

Presented By Presented to
Team -B Dr. Md. Shakhawat H. Firoz
Lokman Hosen Professor
Md. Abdullah-Al-Mamun Department of Chemistry
Rajan paul
Sharmin sultana
Sathi khatun

Department of Chemistry
Bangladesh University of Engineering & Technology, BUET
Dhaka-1000, Bangladesh.

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 Content

Structure of solid surfaces

 Detailed structure of solid surfaces
Mechanism of surface reaction
Kinetic effects of surface heterogeneity
 Kinetic effect of interactions

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 Structure of solid surfaces
Assumption for general equations of adsorption,

 surfaces are smooth

 all surface atoms behave in the same way.

Active centre:

 Concept of active centre was 1st pointed by Constable.

 Emphasized by H. S. Taylor.

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 Structure of solid surfaces

Active centres
Evidences:
o Heating of surface
o Decomposition of ammonia on molybdenum surface.
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 Structure of solid surfaces
 Adsorption also depends on interatomic distance
on surface (Balandin).

Multiple adsorption

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 Structure of solid surfaces
Example :
 Adsorption of hydrogen on carbon surface.

H
C
w
Adsorption of hydrogen on carbon surface

 An optimum interatomic distance is 360 pm

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 Detailed structure of solid surfaces
Field Ion Microscope (FIM)
The field ion microscope (FIM) can image the atomic structure of
sharp metal tips with nanometer-sized radii and produce atomically
resolved images of matter in real space.

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 Detailed structure of solid surfaces
Principle
A stream of helium gas enters an
evacuated chamber and impinges on
the surface of a crystal to which a
high electric field is applied. This
produces He ions which are repelled
from the surface, and analysis of the
image produced on a screen by these
ions permits an identification of the
position of the atoms on the surface.

Fig: Schematic diagram of SIM

analysis
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 Detailed structure of solid surfaces
Low Energy Electron Diffraction(LEED)
The surface crystallography structures can be determined by bombarding the
surface with low energy electrons (10-200eV) and diffracted electrons are
observed as spots on a phosphorescent screen.

PRINCIPLE
Which involves the backscattering of low-energy electrons from a surface.
In order for there to be effective diffraction, the de Broglie wavelength of the
radiation must be similar to the interatomic distances. The backscattering
electrons are caused to impinge on a fluorescent screen, and analysis of the
pattern provides detailed information about the atomic configuration of the
surface.

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 Detailed structure of solid surfaces
Different crystal faces show a different
distribution of the different types of
surface atom, such as follows:
1. The (111)face is relatively smooth.
2. The (557) surface is less smooth.
3. The (679) surface is more less smooth.

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 Detailed structure of solid surfaces
This adsorption occurs two process

1. Dissociative Chemisorption: e.g, where in etylene H atom

having split off. Admission of hydrogen , however, results in
the disappearance of bands due to carbon carbon double bond
and to the appearance of bands characteristics of adsorbed
ethyl groups.

2. Associative chemisorption: adsorbate does not break bonds

during chemisorption.
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 Detailed structure of solid surfaces
An experimental technique that has revealed valuable
information about the detailed nature of surface and of
adsorbed films is infrared spectroscopy.

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 Mechanism of surface reaction

 The mechanism involves 5 steps:

 Step-1: Diffusion of the reactant molecules to the surface.

 Step-2: Adsorption of the gas on the surface.
 Step-3: Reaction on the surface.
 Step-4: Desorption of the products from the surface.
 Step-5: Diffusion of the desorbed products in the gas.

(continue)

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 Mechanism of surface reaction
• Step-1: Diffusion of reactants to the surface of the catalyst.
• Step-2: Adsorption of reactants molecules on the surface of the catalyst.
• Step-3: Occurrence of chemical reaction on the catalyst’s surface
through formation of an intermediate.
• Step-4: Desorption of reaction products from the catalyst surface and
thereby making the surface available again for more reaction to occur.
• Step-5: Diffusion of reaction products away from the catalyst’s surface.
The surface of the catalyst unlike the inner part of the bulk has free
valencies which provide the seat for chemical force of attraction. When
a gas comes in contact with a such a surface, its molecules are held up
there due to loose chemical combination. If different molecules are
adsorbed side by side, the may react with each other resulting in the
formation of new molecules may evaporate leaving the surface for the
fresh reactant molecules.
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 Mechanism of surface reaction

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 Mechanism of surface reaction
 At one time it was believed that one of the diffusion processes, 1 or 5, was
the slowest process and therefore determined the overall rate. More
detailed investigations of surface reactions showed that this could not be
the case, except perhaps in certain technical process involving porous
catalysts. This is evident from the fact that heterogeneous processes
nearly always involve appreciable activations energies, whereas diffusion
in the gaseous state involves no activation energy; the diffusion process
therefore is much more rapid than the overall process and can not
constitute its slow step. The processes of adsorption or desorption are
much more likely to the slow steps in heterogeneous reactions, since both
may involve appreciable energies of activation. The activation energies for
desorption are generally high, and it appears that in most reactions the
desorption of the products is the rate determining step. In practice,
however, it is not always convenient to separate steps 3 and 4; because
one usually does not know the rate of desorption of the products. It is
usual, therefore, to regard the reaction on the surface, forming the
gaseous products, as a single step.
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 Mechanism of surface reaction

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 Mechanism of surface reaction

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 Surface heterogeneity
 There are two approaches in the description of surfaces heterogeneity. In one
approach, an energy distribution concept is utilized and the other assumes a
pore size distribution to describe the structural heterogeneity.
 First, method has been widely studied in the measurement of adsorption
equilibrium and in the steady-state surface diffusively calculations.
 Second, the pore size distribution concept is only studied for adsorption
equlibrium and steady-state surface diffusion.

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 Nonideal adsorption

 Deviations from the Langmuir equations are often observed. This will lead
to a deviations from the ideal adsorption equation
 causes are:
• The surface is not uniform.
• May be interactions between adsorbed molecules.
• Molecule to become attached to a neighbouring site.
• There may be adsorption in more than one layer, that is multilayer
adsorption.

• According to the Freundlich equation, the amount of a substances

adsorbed is related to the concentration,
 x=kcn
 where, x=adsorbed.
 c=concentration.

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 Kinetic Effects of Surface Heterogeneity
 When a reaction takes place on a surface on which there is a variation of
activity, the overall rate is the sum of the rates on the various types of site.
There are two types of site:
 1. A group of sites having a constant high activity.
 2. A second group of low activity.
 Suppose that ,
 c1and c2= are the concentrations of the two kinds of sites
 E1 and E2= are the activation energies.
 Then the rate of reaction is

 Where, k= is factor includes reactant concentrations.

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 Constable Argument

 There is very unusual distribution of surface sites, the

reaction occurs more dominately on the more active sites.
This argument was first given by Constable, who
considered probable distributions of the activities of
surface sites. That is likely to that on a nonuniform
surface the kinetices will correspond to a reaction on the
most active sites. For examples, Langmiur-Hinshelwood
mechanism on some of the surface sites.

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 Hasley’s Consideration
Hasley has been considered that the kinetic equations are affected by such
complexities
•Some types of site may be covered fully.
•While, others may be covered sparsely.
There is not necessarily a simple correlation the experimental adsorption
isotherms and the kinetic behavior that is observed.
the results of adsorption studies may indicate a wide range of surface activity, while
while the kinetic equations may be much simpler.

Figure.1. plot of fraction of surface covered versus concentration for a system

obeying the Langmuir equation.
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 Examples

 Kinetic behavior is affected by

interactions between adsorbed
molecules, that is ,by induced
heterogeneity. A reaction involving the
adsorption of hydrogen molecules on
neighboring pairs of surface sites:

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 Kinetic Effect of Interaction

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 Kinetic effect of interactions

 The effect of interaction is consider to what extent the

kinetic behavior is affected by interactions between
adsorbed molecules, that is, by induced heterogeneity.
But in theoretical treatment, the effect should not be
important.

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 Kinetic effect of interactions

 A reaction involving the adsorption of hydrogen

molecules on neighboring pairs of surface sites:
H H
 H2 + S S S S

The effect of repulsions is to spread the adsorbed

hydrogen atoms over the surface and thus to decrease
the concentration of duel sites on which additional
molecules may become adsorbed.

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 Thanks to all

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