Single Reaction: - When the single stoichiometric equation and single

rate are chosen to represent the progress of a reaction, such

reactions are known as single reaction.

Multiple reactions: - When more than one stoichiometric equation is
used to represent the observed changes, then more than one kinetic
expression is needed to follow the changing composition

Reaction Orders
The manner in which the reaction rate varies with the concentrations
of the reactants and products is indicated by stating the order of the
reaction. If equation 3.0.15 is written in more explicit form as

..3.0.17

The reaction is said to be of the
A
th order with respect to A,
B
th
order with respect to B, etc.

The overall order of the reaction (m) is simply

(3.0.18)


These exponents
i
may be small integers or fractions, and they may
take on both positive and negative values as well as the value zero. In
many cases these exponents are independent of temperature.

In other cases where the experimental data have been forced to fit
expressions of the form of equation 3.0.17, the exponents will vary
slightly with temperature. In these cases the observed correlation
should be applied only in a restricted temperature interval.

It must be emphasized that, in general, the individual orders of the
reaction (
i
) are not related to the corresponding stoichiometric
coefficients v
i
. The individual
i
s are quantities that must be
determined experimentally.

It is important to recognize that by no means can all reactions be
said to have an order. For example, the gas phase reaction of H
2
and
Br
2
to form HBr has a rate expression of the following form: -


(

) (

()
(

)
(3.0.19)


Where,
k and k' are constants at a given temperature and where the
molecular species contained in brackets refer to the concentrations of
these species.

When one reactant is present in very large excess, the amount of
this material that can be consumed by reaction is negligible compared
to the total amount present. Under these circumstances, its
concentration may be regarded as remaining essentially constant
throughout the course of the reaction, and the product of the reaction
rate constant and the concentration of this species raised to the
appropriate order will also be constant. This product is then an
apparent or empirical pseudo rate constant, and a corresponding
pseudo reaction order can be determined from the new form of the
rate expression.
3.0.2 The Reaction Rate Constant
The term reaction rate constant is actually a
misnomer, since k may vary with temperature,
the solvent for the reaction, and the concentrations
of any catalysts that may be present in the
reaction system. The term is in universal use,
however, because it implies that the parameter k
is independent of the concentrations of reactant
and product species.
The reaction rate is properly defined in terms
of the time derivative of the extent of reaction. It
is necessary to define k in a similar fashion in
order to ensure uniqueness. Definitions in terms
of the various rt would lead to rate constants that
would differ by ratios of their stoichiometric
coefficients.
The units of the rate constant will vary depending
on the overall order of the reaction.
These units are those of a rate divided by the mth
power of concentration, as is evident from
equations 3.0.17 and 3.0.18.
(k) =
(r) (moles/volume-time)
(CT ~ (moles/volume)m
or
(k) =.time ^moles/volume)"
(3.0.20)
(3.0.21)
For a first-order reaction, the units of k are
time"1; for the second-order case, typical units
are m3/mole-sec.