PolyE-304

Polymer Reaction Engineering

Dr.M.Bilal Manzoor
Polymer and process Engineering
UET, Lahore

Testing Kinetic Models

Two problems make the search for the correct mechanism of reaction difficult.

First, the reaction may proceed by more than one mechanism, say free radical
and ionic, with relative rates that change with conditions.

Second, more than one mechanism can be consistent with kinetic data.
Resolving these problems is difficult and requires an extensive knowledge of
the chemistry of the substances involved.

Leaving these aside, let us see how to test the correspondence between
experiment and a proposed mechanism that involves a sequence of
elementary reactions.

In these elementary reactions we hypothesize the existence of either of two

types of intermediates.

Type 1. An unseen and unmeasured intermediate X usually present at such

small concentration that its rate of change in the mixture can be taken to be
zero. Thus, we assume

This is called the steady-state approximation. Mechanism types 1 and 2,

above, adopt this type of intermediate, and Example 2.1 shows how to use
it.

Type 2. Where a homogeneous catalyst of initial concentration Co is present

in two forms, either as free catalyst C or combined in an appreciable extent to
form intermediate X, an accounting for the catalyst gives

We then also assume that either

or that the intermediate is in equilibrium with its reactants; thus,

SEARCH FOR THE REACTION MECHANISM

Example 2.1

solution

SEARCH FOR A MECHANISM FOR THE

ENZYMESUBSTRATE
REACTION
Example 2.2
Here, a reactant, called the substrate, is converted to product by the
action of an enzyme, a high molecular weight (mw > 10 000) protein-like
substance. An enzyme is highly specific, catalyzing one particular
reaction, or one group of reactions. Thus,enzyme
A------ >R
Many of these reactions exhibit the following behavior:
1. A rate proportional to the concentration of enzyme introduced into the
mixture [E,].
2. At low reactant concentration the rate is proportional to the reactant
concentration, [A].
3. At high reactant concentration the rate levels off and becomes
independent of reactant concentration.
Propose a mechanism to account for this behavior

Thank you