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NOVEMBER 31, 2014


Rate Laws are essential in Chemical Reaction Engineering. These will serve as the basic step in
solving problems in this course. But before proceeding to rate laws, it is vital that a student
understands what kind of reaction is happening so as to establish the proper equation. Rate Laws
are based on reactions. A chemical reaction involves transformation from one substance to
another and these different kinds of transformation also affect the equation to be used.

Types of Reaction
1) Homogenous Reaction a reaction involving only one phase
2) Heterogenous Reaction a reaction involving two or more phases
3) Irreversible Reaction a reaction that proceeds in only one direction
4) Reversible Reaction a reaction that can proceed in the forward direction and backward
direction. We can determine that a reaction is reversible if it has two arrows with each
heading in opposite directions.

Molecularity of Reaction
Definition: The molecularity of a reaction depends on the atoms involved in a certain chemical
1) Unimolecular only one atom is involved. (Ex. : Radioactive Decay)
2) Bimolecular two atoms are involved (Ex. : collision with free radicals)
3) Trimolecular three atoms are involved (Ex. : series of bimolecular reactions)
3.1 Relative Rates of Reaction
Stoichiometric coefficients of a reaction are related by:
A+ B C+ D
That for every mole of A consumed, moles of D are produced.
aA + bB cC+ dD
The species are related in that way for which

3.2 The Reaction Order and the Rate Law

Chemical Reaction Calculations need basis. Usually, species A which is considered as the
limiting reactant in a reaction is used for calculations. Since A is a reactant, the rate of
disappearance is calculated.
The rate of disappearance is described by the general equation:
-rA = {kA(T)}[fn(CA, CB,.)]
where kA is the reaction rate constant.
The rate of disappearance is the product of the reaction rate constant and the function of
concentrations. When the rate of disappearance, -rA, is related to the species concentrations in an
algebraic form, the equation becomes a kinetic expression also known as the Rate Law.

3.2.1 Power Law Models and Elementary Rate Laws

A power law model is one of the most common general forms used to confirm postulated forms.
The rate law is expressed as the product of concentrations of the individual reacting species with
each raised to a power.
-rA = kACACB
The sum of and is regarded as the reaction order. This is only valid for the reactions under
Elementary Rate Laws. Elementary Rate Laws apply for reactions that follow the molecularity of
the reaction.
The reaction order (n) is defined by the equation:
n = + .
There are four types of reaction order namely: Zero-Order, First-Order, Second-order and Thirdorder where n=0, 1, 2 and 3 respectively.

3.2.2 Non-elementary Rate Laws

Non-elementary rate laws are applicable for the reactions not following elementary rate laws.
Some of these include homogenous and heterogeneous reactions. Rate of disappearance of a
reactant per mass of catalyst in a heterogeneous reaction follow Langmuir-Hinshelwood kinetics.
These reactions cannot be deduced from the stoichiometry of the reaction involved. These
reactions are formed by a series of reactions wherein the reaction time is so fast that it could not
be considered as single reactions but as a whole overall reaction.

3.2.3 Reversible Reactions

Reversible reactions are the reactions that go forward and backward. The forward reaction is
where the reactants form products. The backward reaction, on the other hand, involves products
producing reactants. When equilibrium is reached, the rate of forward reaction becomes equal to
the rate of the backward reaction. An equilibrium constant, Kc, is considered wherein it is equal
to the concentration of the products at equilibrium all over the concentration of the reactants at
equilibrium with all concentrations raised to their own stoichiometric coefficient.

3.3 The Reaction Rate Constant

The reaction rate constant denoted as k is not truly a constant but rather a specific reaction rate
constant. This constant is independent of the concentrations but is strongly dependent on
temperature and also on pressure when gaseous reactions are involved.
Svante Arrhenius related the rate constant to temperature by the equation:
kA(T) = Ae-E/RT
where A = pre-exponential factor or frequency factor
E = activation energy, J/mol or cal/mol
R = gas constant= 8.314 J/mol K = 1.987 cal/mol K
T = absolute temperature, K
This relation is also known as the Arrhenius equation.
Arrehenius equation tells us that as the temperature increases, the rate constant also increases.
When connected to rate law, where the rate of formation is proportional to reaction rate constant
and the concentration of species present, the rate of formation/disappearance also increases.

The activation energy is a barrier to energy transfer between reacting molecules that in order for
a reaction to occur, this energy should be overcome. This energy is due to the requirements for
chemical bonding wherein energy must be provided to break and the eventually form new bonds
and to overcome the steric and electron repulsive forces.

Finally, the main purpose of knowing the way chemical reactions proceed is to create a design
for an equipment in which it will be contained. Volume and volumetric flowrate are just some of
the `important data that will be needed in designing effective equipment.