Solid Catalyzed Reactions:

Rate Equations
by mujettegodmalin
With many reactions, the rates are
So what are
affected by materials which are
They are catalysts.
neither reactants nor products.
they?
 Catalysts
substance that affects the rate of reaction but
emerges from the process unchanged.

“a substance which alters the rate of a chemical reaction

but is chemically unchanged at the end of the reaction.”
"..... but is chemically unchanged
at the end of the reaction."

This means that there is just as much catalyst at the end

of a reaction as there was at the beginning. The catalyst
is used over and over again. Because catalysts work so
rapidly and are used again and again, it is only
necessary to have very small quantities of catalyst
present to make a chemical reaction go faster.
"A catalyst is a substance ....."

This means that it is some kind of chemical substance!

It could be a pure element; e.g. Platinum,
Nickel; or it could be a pure compound, e.g. Manganese
Dioxide, Silica, Vanadium V Oxide, Iron III Oxide; it
could be dissolved ions, e.g. Copper ions,
Cobalt II ions; or it could be a mixture, e.g. Iron-
Molybdenum, or it could be a much more complicated
compound such as protein
Normally
Catalystswhen we speed
can talk about a catalyst,
a reaction
we mean one that speeds up a reaction,
by a factor of a million or
although strictly speaking, a catalyst
much more,
can either or they
accelerate or may slow
slow the
aformation
reactionof(negative
a particularcatalyst).
product
species.
 2 broad classes:

Biochemical catalysts (enzymes)

Man-made catalysts
THINGS YOU OUGHT TO KNOW
Our bodies have hundreds of different enzymes and are other
catalysts that are busily at work all the time, keeping us alive.
Man-made catalysts play an important role in many industrial
processes. Over 50% of all the chemical products produced
today are made with the use of catalysts.
Catalysts select.

Although a catalyst can easily speed the rate of reactions a

thousandfold or millionfold, still, when a variety of reactions
encountered, the most important characteristic of a catalyst
is its selectivity.
 Selectivity
It only changes the rates of certain reactions,
often a single reaction, leaving the rest
unaffected.
How catalysts
work?
There are two ways in which catalysts work.

You already know that when two different molecules

bump into each other, they might react to make new
chemicals. We usually talk about "collisions" between
molecules, it would be much simpler to say that the
molecules bumped into each other. How fast a
chemical reaction is depends upon how frequently the
molecules collide. You have probably been told about
the "kinetic theory" which is all about heat and how
fast molecules move around. What catalysts are doing
when they make a chemical reaction go faster is to
increase the chance of molecules colliding.
The first method is by "adsorption", the second
method is by the formation of intermediate
compounds.
 Adsorption
This occurs when a molecule sticks onto the
surface of a catalyst.

“For a catalytic reaction to occur, at least one and frequently all

of the reactants must become attached to the surface.”
Intermediate Compounds
the chemicals involved in the reaction combine with
the catalyst making an intermediate compound, but
this new compound is very unstable. When the
intermediate compound breaks down, it releases the
new compounds and the original catalyst.
Representation of the action of a catalyst.
A catalyst changes a reaction rate by
promoting a different molecular path

(“mechanism”)
for the reaction.
Once a reactant has been adsorbed onto
the surface, it is capable of reacting in
There
a number of waysare 3 ways:
to form the reaction
product.
Single-site Mechanism
Only the site in which the reactant is adsorbed
is involved in the reaction.

A ·S B ·S
Dual-site Mechanism
Adsorbed reactant interact with another site to
form product.

A·S + S B·S + S
 Eley-Rideal
Mechanism
Between an adsorbed molecule and a molecule
in the gas-phase:

A · S + B (g) C · S + D (g)
 The RATE
EQUATION
 …reaction takes place on an active site
on the surface of the catalyst. Three
steps are viewed to occur successively at
the surface.
 Step 1:
A molecule is adsorbed onto the surface an is attached to an
active site. (adsorption)
Step 2:
It then reacts either with another molecule on an adjacent site (dual
site mechanism), with one coming from the main gas stream (single-
site mechanism), or it simply decomposes while on the site.
(surface reaction)

Step 3:
Products are desorbed from the surface, which then free the
site. (desorption)

STEPS IN A CATALYTIC REACTION

 All species of molecules, free reactants, and
free products as well as site-attached
reactants, intermediates, and products taking
part in these three processes are assumed to
be in equilibrium.
 Rate expressions derived from various postulated
mechanisms are all of the form

(kinetic term)(driving force or displacement from equilibrium)

Rate of reaction =
(resistance term)
For example, for the reaction

occurring in the presence of inert carrier

material U, the rate expression when adsorption of A controls is

When reaction between adjacent molecules

of A and B controls, the rate expression is

whereas for desorption of R, controlling it becomes

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