Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
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.
13 March 2019 1
Content
13 March 2019 2
Structure of solid surfaces
Assumption for general equations of adsorption,
Active centre:
Emphasized by H. S. Taylor.
13 March 2019 3
Structure of solid surfaces
Active centres
Evidences:
o Heating of surface
o Decomposition of ammonia on molybdenum surface.
13 March 2019 4
Structure of solid surfaces
Adsorption also depends on interatomic distance
on surface (Balandin).
Multiple adsorption
13 March 2019 5
Structure of solid surfaces
Example :
Adsorption of hydrogen on carbon surface.
H
C
w
Adsorption of hydrogen on carbon surface
13 March 2019 6
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.
13 March 2019 7
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.
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.
13 March 2019 9
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.
13 March 2019 10
Detailed structure of solid surfaces
This adsorption occurs two process
13 March 2019 12
Mechanism of surface reaction
(continue)
13 March 2019 13
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.
13 March 2019 14
Mechanism of surface reaction
13 March 2019 15
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.
13 March 2019 16
Mechanism of surface reaction
13 March 2019 17
Mechanism of surface reaction
13 March 2019 18
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.
13 March 2019 19
13 March 2019 20
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.
13 March 2019 21
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
13 March 2019 22
Constable Argument
13 March 2019 23
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.
13 March 2019 25
Kinetic Effect of Interaction
13 March 2019 26
Kinetic effect of interactions
13 March 2019 27
Kinetic effect of interactions
13 March 2019 28
Thanks to all
13 March 2019 29