BITS, PILANI – K. K.

BIRLA GOA CAMPUS

KINETICS & REACTOR DESIGN

PROF. SRINIVAS KRISHNASWAMY

PROFESSOR
DEPARTMENT OF CHEMICAL ENGINEERING
BITS PILANI, K. K. BIRLA GOA CAMPUS
What next???
If the going is real easy, beware, you may be
headed down hill and don’t know it.

Source: Unknown

When the going gets tough, the tough get going

After this chapter you will be able to write the

rate of reaction as a function of conversion for
both gas phase and liquid phase contacting
systems
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Rationale for moving ahead
Earlier 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. Rate Law – Find the rate as a function of concentration,

–rA = k fn (CA, CB …)

2. Stoichiometry – Find the concentration as a function of

conversion
CA = g(X)
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Basic definitions
➢Homogeneous reaction: One phase
➢ Heterogeneous reaction: 2 phase, interface
➢ Irreversible reaction
➢ Reversible reaction

➢ Molecularity: Number of atoms, molecules or ions

involved in a reaction step

• Unimolecular
• Bimolecular
• Tetramolecular

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Relative rates of reactions

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?

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 Reaction Order and Rate Laws
Consider the general equation

We will choose A as our basis of calculation

The basis of calculation is most always the limiting reactant.

–rA = kA (T) fn (CA, CB …) RATE LAW

k is the specific rate of reaction or rate constant

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Power law models

–rA = kA (T) fn (CA, CB …)

Experiments Theory

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Order of a reaction

The order of a reaction refers to the powers to which the

concentrations are raised in the kinetic rate law.

The unit of – rA is always in terms of concentration per unit

time while the units of rate constant will vary with the order of
the reaction. For A → Products with reaction order n,

k = (Concentration)1 – n / time

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Order of a reaction
Strictly speaking the reaction rate is in terms of the activities,

ai = iCi

For many reacting systems the activity co-efficient does not

change appreciably during the course of the reaction and they
are absorbed into the specific reaction rate

DIY

1. What are zero, first, second and third order

reaction?
2. What are the units of k for the above?

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Elementary reactions
A reaction follows an elementary rate law if and only if
the stoichiometric coefficients are the same as the
individual reaction order of each species. For the
reaction in the previous example
the rate law would be:

If 2NO + O2 → 2NO2, then -rNO = kNO (CNO)2 CO2,

Is this reaction elementary!

H2 + I2 → 2HI –rH2 = kH2 CH2 CI2

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Non-elementary reactions

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.

The overall order of the reaction does not have to be an integer nor
does the order have to be an integer with respect to any individual
component. For e.g. CO + Cl2 → COCl2 (phosgene synthesis)

–rCO = kCCOCCl23/2

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Elementary reactions
Rate laws are determined experimentally. They are a
function of the reaction chemistry and not on the type of
reactor in which the reaction occurs.

CHECK LITERATURE BEFORE YOU RUN TO THE LAB

What is the reaction rate law for the reaction below 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/dm3, CB = 9 mol/dm3 and
kA = 2 (dm3/mol)(1/2)(1/s).

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Non-elementary reactions
Sometimes reaction have complex rate expressions that
cannot be separated into solely temperature dependent and
concentration dependent portions

DECOMPOSITION OF NITROUS OXIDE

2N2O → 2N2 + O2
Rate
can be
in terms –rN2O = kN2OCN2O / 1 + k’CO2
of
partial
The concept of apparent reaction order
pressur
es (1 >> k’CO2) or (1 << k’CO2)

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Things getting tougher by the day…
When things go wrong, you'll find
they usually go on getting worse
for some time; but when things
once start going right they often
go on getting better and better.

But then, left to themselves,

things always go from bad to
worse

Be what nature intended you for,

and you will succeed; be anything
For you and me else and you will be ten thousand
(making ppt’s) times worse than nothing

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The reaction rate constant
❑ Not truly a constant
❑ Independent of the concentration of the species involved in the
reaction
❑ Almost always strongly dependent on temperature
❑ Depends on whether a catalyst is present or not
❑ In gas-phase reactions, maybe a function of total pressure
❑ In liquid systems, it can be a function of other parameters
such as ionic strength and choice of solvent
❑ Other parameters are less important and may assume
importance for supercritical solvents

FOR THE TIME BEING k = f(T) ENOUGH

This dependence is given by Arrhenius’ equation

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 The reaction rate constant

E = activation energy (cal/mol) or J/mol

R = gas constant (cal/mol.K) or J/mol.K
T = Absolute temperature in K
A = frequency factor or pre-exponential factor

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A little about Arrehenius

Svante August Arrhenius was born in Vik, Sweden in 1859. At age

25, he turned in his PhD thesis at the University of Uppsala,
Sweden. His PhD examining committee did not think very highly of
his thesis and rated it 4th class. His oral thesis defense did not fair
much better as they rated it as only 3rd class. Arrhenius left
Sweden for five years to work with Oswald, Boltzmann and Van't
Hoff. In 1889 his interpretation of temperature-dependent
equation by Van't Hoff led to the universal accepted Arrhenius
equation for kinetic rate laws in chemistry.

He received the Nobel Prize in 1903. From 1905 until his death in
1927 he was director of Physical Chemistry at the Nobel Institute.

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Activitation Energy
The activation energy is a measure of how temperature sensitive
the reactor is. Reactions with large activation energies are very
temperature sensitive.

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Activitation Energy

❑ Barrier to a reaction
❑ For any reaction to occur, the reactants must overcome an
energy barrier or activation energy EA

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Activitation Energy
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

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Activitation Energy

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Problem Time

Data on the tenebrionid beetle whose body mass

is 3.3 g, show that it can push a 35 g ball of dung
at 6.5 cm/s at 27 oC, 13 cm/s at 37 oC and 18
cm/s at 40 oC. How fast can it push dung at
41.5 oC?

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Problem Time

3.5

2.5
2.949436
Ln (Velocity)

1.5
y = -7127.4x + 25.605
1

0.5 19.09518
0
0.00315 0.0032 0.00325 0.0033 0.00335
1 / T (K)

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Problem Time

Calculate the activation energy for the

decomposition of benzene diazonium chloride to
give chlorobenzene and nitrogen

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So where are we? A Recap!!
Earlier 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. Rate Law – Find the rate as a function of concentration,

–rA = k fn (CA, CB …)

2. Stoichiometry – Find the concentration as a function of

conversion
CA = g(X)
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Stoichiometry: Batch reactor systems
Initial Change (mol) Remaining mol
(mol)
A NAo -NAoX NA= NAo - NAoX

B NBo -(b/a) NAoX NB= NBo – (b/a)NAoX

C NCo (c/a) NAoX NC= NCo + (c/a)NAoX

D NDo (d/a) NAoX ND= NDo + (d/a)NAoX

Inerts (I) NIo ********* NI= NIo

Total NTo

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Stoichiometry: Batch reactor systems
NAo(1 – X) / V

CB = NB / V NBo – (b/a)NAoX / V

CC = NC / V NCo + (c/a)NAoX / V

CD = ND / V NDo + (d/a)NAoX / V

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Stoichiometry: Batch reactor systems

Write the rate law for the elementary liquid phase reaction solely
in terms of conversion (2A + B = C). The feed to the batch
reactor is equal molar A and B with CA0 = 2 mol/dm3 and kA= .01
(dm3/mol)41/s. What is the rate law? What is the concentration
of A and B?

Hint

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Stoichiometry: Flow systems
Initial Change (mol) Remaining mol
(mol)
A FAo -FAoX FA= FAo - FAoX

B FBo -(b/a) FAoX FB= FBo – (b/a)FAoX

C FCo (c/a) FAoX FC= FCo + (c/a)FAoX

D FDo (d/a) FAoX FD= FDo + (d/a)FAoX

Inerts (I) FIo ********* FI= FIo

Total FTo

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Stoichiometry: Flow systems
FAo(1 – X) / V

CB = FB / v FBo – (b/a)FAoX / V

CC = FC / v FCo + (c/a)FAoX / V

CD = FD / v FDo + (d/a)FAoX / V

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Stoichiometry: Flow systems
(Gas Phase): Variable flow rate
Combining the compressibility factor equation of state with Z = Z0

with , , FT=CTv, FTo=CTovo, Take ratio

DIY: What will C be as a f(X)?

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Try a Problem!! Smile..
1. For the gas phase reaction, 2A + B → C, what is
 and ? The feed is equimolar is A & B.

2. What is the volume of a gas for a variable

volume batch reaction?

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Problem!!
1. Let us consider the production of ethyl benzene

The gas feed consists of 25% toluene and 75% ethylene. Set up a
stoichiometric table to determine the concentrations of each of the
reacting species and then to write the rate of reaction solely as a
function of conversion. Assume the reaction is elementary with .
The entering pressure is 8.2 atm and the entering temperature is
227 oC and the reaction takes place isothermally with no pressure
drop.

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 Problem!!Hint
1. What is the basis of your calculation?
2. What are the entering concentrations of ethylene and toluene?

3. What are  and ?

4. Write the row in the stoichiometric table for ethylene & Toluene?
5. Form the entire table including total flowrates?
6. Write the volumetric flowrates in terms of conversion?
7. Write the concentration of ethylene and propylene in terms of
conversion?
8. Write the disappearance of A as a function of conversion
9. What is the relative rate of ethylene?

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Problem!!Solution
1. The stoichiometric ratio is one toluene to two ethylene (1/2).
However, the feed is one toluene to three ethylene (1/3) and
there is not sufficient toluene to consume all the ethylene.
Therefore toluene is the limiting reactant and thus the basis of
calculation

2. Let A = toluene, B = ethylene, C = ethyl benzene and D =

propylene

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Problem!!Solution (3,4)
3. Since toluene, i.e. A, is the limiting reactant and has a
stoichiometric coefficient of 1

Species Symbol Entering Change Leaving

Toluene A FA0 �FA0X FA=FA0(1�X)

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 Problem!!Solution (6)
Species Symbol Entering Change Leaving
Toluene A FA0 −FA0X FA=FA0(1−X)

Ethylene B
Ethyl C 0
benzene
Proplyene D 0
Total

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Problem!!Solution (7, 8)

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Problem!!Solution (9)

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Problem!!Solution (10)

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Reversible reactions
aA + bB  cC +dD

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.

Consider the exothermic, heterogeneous reaction

At low temperature, the rate law for the disappearance of A is

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Reversible reactions
At low temperature, the rate law for the disappearance of A is

At high temperature, the exothermic reaction is

significantly reversible:
What is the corresponding rate law?

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Reversible reactions

(C A + B) is

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Reversible reactions
Does this rate law satisfy our requirement that, at equilibrium,
it must reduce to an equation that is thermodynamically
consistent with KP?

for a reaction at equilibrium:

At equilibrium, rnet = 0,

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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.

What is the rate of reaction?

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Sample Problem (Constant
volume batch reactor)

(CA0 = 0.2 mol/dm3 and KC

= 100 dm3/mol)

Xe = 0.83

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Objective Assessment of Chapter
➢ 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

Beliefs are what divide people.

Doubt unites them.

Peter Ustinov

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