Objectives

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.

Rate Laws
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.

Relative Rates of Reaction

Example Relative Rates of Reaction

The Reaction:

is carried out in a reactor. If at a particular

point, the rate of disappearance of A is 10
mol/dm3/s, what are the rates of B and C?

Species A, basic of calculation

The rate of disappearance of A, -ra,
is
or the rate of formation of species A is

The relative rates are

Species B

The rate of formation of species B is

The rate of disappearance of B, -rb, is

Species C

The rate of formation of C, -rc, is

Power Law Model

Maxwell Boltzmann Distribution

Temperature Dependence of Rate Constant, k

Excel: Fitting logarithmic data

Excel Calculations

Units of Specific Reaction Rate

Elementary Rate Law Reactions

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. For the reaction in the previous example
(A+B C+D), the rate law would be:

If 2NO+O2 2NO2 Then

-rNO = kNO (CNO)2 CO2

Non-Elementary Rate Laws

If the rate law for the non-elementary reaction is
A+BC+D 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 and the rate law must reduce to an
equation that is thermodynamically consistent with the
equilibrium constant for the reaction.
Example

Rate Law for Reversible Reactions

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

Reversible Reaction
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.

At Equilibrium

Therefore

Stoichiometry
We shall set up Stoichiometric Tables for Batch
Reactors using A as our basis of calculation in the
following reaction.

We will use the stoichiometric tables to express

the concentration as a function of conversion. We
will combine Ci = f(X) with the appropriate rate law
to obtain -rA = f(X).
Example

For a reaction

Batch System Stoichiometric Table

Spe. Syb

Intial

Change

Remaing

NAo

-NAoX

NAo= NA(1-X)

NBo= NAo B

-(b/a)NBoX

NBo= NA(B-X)

NCo= NAo c

(c/a)NBoX

NCo= NA(C-X)

NDo= NAo D

(d/a)NBoX

NDo= NA(D-X)

Inert

NI= NAo I

------

NI= NAo I

NTo
Where:

NT= NTo+NAoX
and

Flow System Stoichiometric Table

Species

Symbol

Inert

Reactor Feed

Change

Reactor Effluent

------________

Where:
and

____________

Concentration -- Flow System:

Liquid Phase Flow System:

etc.

Gas

Phase Flow System:

etc.
Again, these equations give us information
about -rA = f(X), which we can use to size
reactors.
For example if the gas phase reaction has the
rate law
then

with

For Gas Phase Flow Systems:

Combining the compressibility factor equation of state with Z = Z 0
with

The total molar flowrate is:

Substituting for FT gives:

, FT=CTV, FTo=CToVo,

Example: Calculate
For the gas phase reaction

the feed is equal molar in A and B. Calculate .

Solution
A is the limiting reactant

Oxidation of Naphthalene to Phtahalic Anhydride

We are going to rework the class problem for the case of 3.5%
naphthalene and 96.7% air and for a pressure of 10 atm and a
temperature of 500K. A feed under these conditions phthalene
is the limiting reactant.

Stoichiomentric Table - Batch System

Species

Symbol

In

Change

Out

Naphthalene

NA0

-NA0X

NA = NA0(1-X)

Oxygen

NB0 =

-9/2NA0X

NB = NA0(

Phthalic Anhydride

NC = 0

+NA0X

NC = NA0X

Carbon Dioxide

ND = 0

+2NA0X

ND = 2NA0X

Water

NE = 0

+2NA0X

NE = 2NA0X

Nitrogen

NI =

---

NI =

Total

NT0

NA0

NA0

- 9/2X)

NA0

NT = NT0 +

NA0X

= [1 + 2 + 2 - 9/2 1] = -1/2

Stoichiometric Table - Flow System

Species

Symbol

In

Change

Out

Naphthalene

FA0

-FA0X

FA = FA0(1-X)

Oxygen

FB0 =

-9/2FA0X

FB = FA0(

Phthalic Anhydride

FC = 0

+FA0X

FC = FA0X

Carbon Dioxide

FD = 0

+2FA0X

FD = 2FA0X

Water

FE = 0

+2FA0X

FE = 2FA0X

Nitrogen

FI =

---

FI =

Total

FT0

FA0

FA0

- 9/2X)

FA0

FT = FT0 +

FA0X

Determine each of the following soley as a function

of the conversion of naphthalene, X for a constantpressureisothermal flow reactor.
1.Find the concentration of O2 Gas Phase Flow System:

2.Constant pressure and isothermal: P = Po; T = To

Find the volumentric flowrate

Constant pressure and isothermal: P = Po; T = To

Find the reaction rate

Rate Law:

-rA = kAC2ACB

For a constant volume isothermal batch reactor,

1.The concentration of O2
For Batch: V = V0, CB = NB/V = NB/V0

2.The total pressure, P.

The rate law

Rate Law: -rA = kAC2ACB