3.

RATE LAWS AND

STOICHIOMETRY

Objectives:
After completing Chapter 3, you will be able to:
 Write the relationship between the relative
rates of reaction.
 Write a rate law and define reaction order
and activation energy.
 Set up a stoichiometric table for both batch
and flow systems and express concentration
as a function or conversion.
 Write -rA solely as a function of conversion
given the rate law and then entering
concentration.
 Calculate the equilibrium conversion for
both gas and liquid phase reactions.
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

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1. Part 1 Rate Law – Find the rate as a function
of concentration,
−𝑟𝐴 = 𝑘𝑓(𝐶𝐴 , 𝐶𝐵 , … )
2. Part 2 Stoichiometry – Find the
concentration as a function of conversion
𝐶𝐴 = 𝑔(𝑋)
Combine Part 1 and Part 2 to get −𝑟𝐴 = 𝑓(𝑋)

Part 1: Rate Laws

Types of reactions:
A homogeneous reaction is one that involves
only one phase.
A heterogeneous reaction involves more than
one phase.

An irreversible reaction is one that proceeds in

only one direction and continues in that direction
until the reactants are exhausted.
A reversible reaction is the one that can
proceed in either direction, depending on the
concentrations of reactants and products relative
to the corresponding equilibrium concentrations.

The molecularity of a reaction is the number

of atoms, ions, or molecule involved (colliding)
in a reaction step. The terms unimolecular,

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bimolecular, and termolecular refer to reactions
involving, respectively, one, two, or three atoms
(or molecules) interacting or colliding in any one
reaction step.
A rate law describes the behavior of a reaction.
The rate of a reaction is a function of
temperature (through the rate constant) and
concentration (activities).
−𝑟𝐴 = 𝑘𝐴 (𝑇)𝑓 (𝐶𝐴 , 𝐶𝐵 , … )
𝑓(𝐶𝐴 , 𝐶𝐵 , … ) is almost without exception
determined by experimental observation.
Although the functional dependence on
concentration may be postuIated from theory,
experiments are necerrary to confirm the
proposed form. One of the most common
general forms of this dependence is the power
law model.
Power Law Model
𝛽
−𝑟𝐴 = 𝑘𝐶𝐴𝛼 𝐶𝐵
The reaction is 𝛼 order in A, 𝛽 order in B. The
overall order of the reaction, n, is 𝑛 = 𝛼 + 𝛽.

Elementary Rate Laws

An elementary reaction is one that evolves a
single step. The stoichiometric coefficients in
this reaction are identical to the powers in the
rate law.

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There are many reactions where the
stoichiometric coefficients in the reaction are
identical to the reaction orders but the reactions
are not elementary owing to such things as
pathways involving active intermediates and
series reactions. For these reactions that are not
elementary but whose stoichiometric
coefficients are identical to the reaction orders in
the rate law, we say the reaction follows an
elementary rate law.
A reaction follows an elementary rate law if and
only if the (iff) stoichiometric coefficients are
the same as the individual reaction order of each
species.

Problem 3.1.
What is the reaction rate law for the reaction
if the reaction is elementary?
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).

Non-Elementary Rate laws

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Example: If the rate law for the non-elementary
reaction is found to be

then the reaction is said to be 2nd order in A, 1st

order in B, and 3rd order overall.

Reversible Reactions
The net rate of formation of any species is equal
to its rate of formation in the forward reaction
plus its rate of formation in the reverse reaction:
ratenet = rateforward + ratereverse
At equilibrium, ratenet 0 and the rate law must
reduce to an equation that is thermodynamically
consistent with the equilibrium constant for the
reaction.
Example: Consider the exothermic,
heterogeneous reaction
At low temperature, the rate law for the
disappearance of A is

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At high temperature, the exothermic reaction is
significantly reversible:
What is the corresponding rate law? Let's see.
If the rate of formation of A for the forward

reaction (A + B C) is
then we need to assume a form of the rate law
for the reverse reaction that satisfies the
equilibrium condition. If we assume the rate law
for the reverse reaction (C A + B) is

then:

and:

Does this rate law satisfy our requirement that,

at equilibrium, it must reduce to an equation that
is thermodynamically consistent with KP? Let's
see.
From Appendix C we know that for a reaction at

equilibrium:
At equilibrium, rnet 0, so:

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Solving for KP gives:

The conditions are satisfied.

Problem 3.2.
Write the rate law for the elementary reaction

Here kfA and krA are the forward and reverse

specific reaction rates both defined with respect
to A.

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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:
𝑘 = 𝐴𝑒 −𝐸⁄𝑅𝑇
Where:
E = activation energy (cal/mol)
R = gas constant (cal/mol∙K)
T = temperature (K)

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A = frequency factor (units of A, and k, depend
on overall reaction order)
(Concentration)1−𝑛
[𝑘 ] =
Time
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)
(mol/L) (mol/L∙s) 1st -rA = kCA s-1
-rA =
(mol/L) (mol/L∙s) 2nd (L/mol∙s)
kCA2

𝐸 1
ln 𝑘 = ln 𝐴 − ( )
𝑅 𝑇

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The larger the activation energy, the more
temperature sensitive k and thus the reaction
rate.
𝐸 1 1
𝑘 𝑇2 = 𝑘 𝑇1 exp [ ( − )]
𝑅 𝑇1 𝑇2
The activation energy can be thought of as a
barrier to the reaction. One way to view the
barrier to a reaction is through the reaction
coordinates. These coordinates denote the
energy of the system as a function of progress
along the reaction path. For the reaction

the reaction coordinate is

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 Progress along reaction path
We see that for the reaction to occur, the
reactants must overcome an energy barrier or
activation energy EA.
Thus, the activation energy is a measure of the
minimum energy that the reacting molecules
must have in order for the reaction to occur.
Akhir Kuliah 5 2013
Why is there an Activation Energy?
(1) the molecules need energy to distort or
stretch their bonds in order to break them and to
thus form new bonds
(2) as the reacting molecules come close
together they must overcome both steric and
electron repulsion forces in order to react
All the molecules don’t have the same energy,
rather there is distribution of energies where
some molecules have more energy than others.

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𝑓(𝐸, 𝑇) describes this distribution of the
energies of the molecules.
𝑓(𝐸, 𝑇)𝑑𝐸 = fraction of molecules with
energies between E and E+dE
One such distribution of energies is in the
following figure.

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By increasing the temperature we increase the
kinetic energy of the reactant molecules which
can in turn be transferred to internal energy to
increase the stretching and bending of the bonds
causing them to be in an activated state,
vulnerable to bond breaking and reaction.
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.

Problem 3.3.
Consider the following elementary reactions:

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1) Which reaction has the higher activation
energy?
2) Which reactions have the same activation
energy?
3) Which reaction is virtually temperature
insensitive?
4) Which reaction will dominate (i.e. take place
the fastest) at high temperatures if all reactions
were to take place in the same reactor?

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5) Which reaction will dominate (take place the
fastest) at moderate temperatures?

6) Which reaction will take place the fastest at

low temperatures?

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7) Which reactions will have the same rate of
reaction at a given temperature?

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