3.

RATE LAWS AND

STOICHIOMETRY

In Chapter 2 we saw that if we had –rA as a

function of X, [–rA= f(X)] we could size many
reactors and reactor sequences and systems.

How do we obtain –rA = f(X)?

We do this in two steps
1. Part 1 Rate Law – Find the rate as a function
of concentration,

2. Part 2 Stoichiometry – Find the

concentration as a function of conversion

Combine Part 1 and Part 2 to get

Part 1: Rate Laws

A rate law describes the behavior of a reaction.
The rate of a reaction is a function of

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temperature (through the rate constant) and
concentration (activities).

is almost without exception

determined by experimental observation. One of
the most common general forms of this
dependence is the power law model.
Power Law Model

The reaction is order in A, order in B. The

overall order of the reaction, n, is .

Problem 3.1.
What is the reaction rate law for the reaction
if the reaction follows an
elementary rate law? What is rB? What is rC?
Calculate the rates of A, B, and C in a CSTR
where the concentrations are CA = 1.5 mol/L, CB
= 9 mol/L and kA = 2 (L/mol)(1/2)(1/s).

Problem 3.2.
Write the rate law for the elementary reaction

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Here kfA and krA are the forward and reverse
specific reaction rates both defined with respect
to A.
In summary on reaction orders, they cannot be
deduced from reaction stoichiometry. They must
be determined from experiments.

Rate Constant, k
k is the specific reaction rate (constant) and is
given by the Arrhenius Equation:
⁄

Where:
E = activation energy (cal/mol)
R = gas constant (cal/mol∙K)
T = temperature (K)
A = frequency factor (units of A, and k, depend
on overall reaction order)

Thus, you can tell the overall reaction order by

the units of k
Rxn
CA -rA Rate Law K
Order
(mol/L) (mol/L∙s) Zero -rA = k (mol/L∙s)

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(mol/L) (mol/L∙s) 1st -rA = kCA s-1
-rA =
(mol/L) (mol/L∙s) 2nd 2 (L/mol∙s)
kCA

Activation energy is a measure of the minimum

energy that the reacting molecules must have in
order for the reaction to occur.
describes this distribution of the
energies of the molecules.
fraction of molecules with
energies between E and E+dE
One such distribution of energies is in the
following figure.

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We see that as the temperature is increased we
have greater number of molecules have energies
EA or greater and hence the reaction rate will be
greater.