Kinetics of Homogenous Reactions

ChE 145
Kinetics of Homogenous Reactions
Mathematical Representation of Reaction Rates
Concentration Dependent Term
Temperature Dependent Term
Kinetic Models
Mathematical Representation of Reaction
Rates
Although reaction rates can be represented by many
factors, a majority of reactions can be represented
mathematically as a function of :
Temperature
Composition

Temperature Concentration
dependent term dependent term
Mathematical Representation of Reaction
Rates
kA reaction rate constant
constant implies that it is independent of species
concentration
Strongly dependent on temperature
Normally subscripted to a particular species
 Rate Law
Reaction orders for simple reactions
Units of KA
Elementary vs Non-elementary reactions
Molecularity
Stoiciometric relationsip of reaction rates
Reaction orders for complex reactions
Kinetic view of equilibrium

Concentration dependent term

Concentration Dependent Term
The dependence of rA on the concentration of the species
present is almost always determined by experimental
observation
Although this functional dependence, i.e.
-rA = kA f(concentration of reacting species)
may be postulated from theory (example, Law of mass action),
experiments are still necessary to confirm the proposed
form.
The algebraic equation that relates rA to the species
concentration is called the kinetic expression or the Rate
Law.
Concentration Dependent Term
One of the most common general forms of this
concentration dependence on rA is the product of the
concentration of individual reaction species, each raised
to a power.

= reaction order with respect to A

= reaction order with respect to B
N = (+) = overall order of reaction
Concentration Dependent Term
In general, first and second order reactions are more
commonly observed than zero and third-order reactions.
The reaction order does not necessarily have to be an
integer value.
Concentration Dependent Term
Units KA
Varies with the order of the reaction

Consider the following reaction:

If rA = moles A consumed/dm3-s
Concentration Dependent Term
Overall Reaction Rate Law Unit of KA
Order

Zero

First

Second
Concentration Dependent Term
Elementary reaction
Rate law corresponds to the stoichiometric equation.
Rate law for an elementary reaction is called an elementary
rate law.
Non-elementary reaction
Rate law does not correspond to the stoichiometric equation.
Concentration Dependent Term
Consider the reaction:

If =a, =b, then the rate law corresponds to the

stoichometric equation.
Concentration Dependent Term
Molecularity
The number of atoms, ions or molecules involved in an
elementary chemical reaction
a) Unimolecular
b) Bimolecular
c) Trimolecular
Important points
Always refers to a chemical reaction
Always take an integer value
Concentration Dependent Term
When writing the equation for the rate of reaction for a
particular chemical species, the rate constant referred to
that particular chemical species is usually used

The rate constant given is referred to reactant A. Thus:

Concentration Dependent Term
For reactant B and C:

kA, kB, kC since stoichiometric coefficients to A, B, and C

are not equal.
If only kA is given, how do we obtain the rate equations in
terms of B and C?
Concentration Dependent Term
Use stoichiometric relationships
Consider:

Reaction rates are stoichiometrically related as shown:

Concentration Dependent Term
Substituting:
Concentration Dependent Term
Reaction Orders for More Complex Rate Laws

The rate law expression cannot be distinctly separated

into a temperature dependent term and a concentration
dependent term
How to determine the reaction order?
Concentration Dependent Term
Use limiting conditions
At very low concentrations of N2O, the second term in the
denominator becomes negligible.

Apparent order: 2
At very high concentration of N2O, kCN2O >>1

Apparent order: 1
Concentration Dependent Term
Kinetic view of Equilibrium (Elementary Reactions)
Consider:

By Law of Mass Action:

How to derive this from a kinetic point of view?

Concentration Dependent Term
k1

k-1
Stoichiometric coefficients are 1
K values can represent any species
rAf = rate of forward reaction = k1CACB
rAb = rate of backward reaction = - k1CRCS
rAnet = net rate of reaction for A = sum of all reactions = rAf +
rAb = rAnet = -k1CACB + k-1CRCS
Concentration Dependent Term
At equilibrium, rAnet = 0 and therefore:

then