Lecture 5

Chemical Reaction Engineering (CRE) is the

field that studies the rates and mechanisms of
chemical reactions and the design of the reactors in
which they take place.

Lecture 5

Block 1:
Block 2:
Block 3:
Block 4:

Mole Balances
Rate Laws
Stoichiometry
Combine

Review of Blocks 1, 2 and 3

Examples

Review Lecture 2

Building Block 1: Mole Balances

in terms of conversion, X
Reactor

Differential

Algebraic

Integral

X
Batch

N A0

dX
= r AV
dt

t
FA 0 X
V=
rA

CSTR

dX
V = FA0
rA
0

PFR

X
PBR
3

dX
FA 0
= rA
dW

Review Lecture 4

Building Block 2: Rate Laws

Power Law Model:

rA = kC A CB
2 A + B 3C

A reactor follows an elementary rate law if the reaction

orders just happens to agree with the stoichiometric
coefficients for the reaction as written.
e.g. If the above reaction follows an elementary rate law

Review Lecture 4

Building Block 3:
Stoichiometry

Part 1: Mole Balances in terms of

Conversion
Algorithm for Isothermal Reactor Design
1. Mole Balances and Design Equation
2. Rate Laws
3. Stoichiometry
4. Combine
5. Evaluate

Building Block:
Combine

Building Block 5:
Design Algorithm

Scale-up of Liquid-Phase Batch

Reactor Data to the Design of a CSTR
One of the jobs in which chemical engineers are involved is

the scale-up of laboratory experiments to pilot-plant

operation or to full-scale production.

To make this jump successfully requires a thourough

understanding of the chemical kinetics and transport

limitations.

Batch Operation
For most liquid-phase reactions, the density change with

reaction is usually small and can be neglected (i.e.,

)
In addition, for gas phases in which the batch reactor
volume remains constant, we also have V = Vo.

Lets calculate the time necessary to achieve a given

conversion X for the irreversible second-order reaction:

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Batch Operation

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Example 4-1
It is desired to design a CSTR to produce 200 million pounds of ethylene glycol per

year by hydrolyzing ethylene oxide. However, before the design can be carried out, it is
necessary to perform and analyze a batch reactor experiment to determine the specific
reaction rate constant.The reaction is first-order in ethylene oxide.

In the laboratory experiment, 500 mL of a 2 M

solution (2 kmol/m3) of ethylene oxide in
water was mixed with 500 mL of water
containing 0.9 wt % sulfuric acid, which is a
catalyst. The temperature was maintained at
55C. The concentration of ethylene glycol was
recorded as a function of time. From these data,
determine the specific reaction rate at 55C.
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Example 4-1: Solution

13

Design of Continuous Stirred Tank

Reactors (CSTRs)
General
Single CSTR
CSTRs in Series

14

Damkohler Number
For a first-order reaction the product k is often referred to as the

reaction Damkohler number. The Damkohler is a dimensionless

number that can give us a quick estimate of the degree of
conversion that can be achieved in continuous-flow reactors.
The Damkohler number is the ratio of the rate of reaction of A to
the rate of convective transport of A at the entrance to the
reactor.

For first- and second-order irreversible reactions the Damkijhler

numbers are

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Damkohler Number
It is important to know what values of the Damkohler

number, Da, give high and low conversion in continuousflow reactors. A value of Da = 0.1 or less will usually give
less than 10% conversion and a value of Da = 10.0 or
greater will usually give greater than 90% conversion.
The rule of thumb is:

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CSTRs in Series

17

CSTRs in Parallel

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A second-order reaction in a CSTR

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Example 4-2: Producing 200 Million

Pounds per Year in a CSTR
It is desired to produce 200 million pounds per year of
ethylene glycol.The reactor is to be operated isothermally. A 1
lb mol/ft3 solution of ethylene oxide in water is fed to the
reactor together with an equal volumetric solution of water
containing 0.9 wt % of the catalyst H2SO4. The specific
reaction rate constant is 0.311 min-1, as determined in
Example 4- 1.
a) If 80% conversion is to be achieved, determine the
necessary CSTR volume?

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Example 4-2: Solution

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Example 4-2: Solution

22

Tubular Reactors
Gas-phase reactions are carried out primarily in tubular reactors

where the flow is generally turbulent.

By assuming that there is no dispersion and there are no radial
gradients in either temperature, velocity, or concentration, we can
model the flow in the reactor as plug-flow.
The differential form of the design equation

must be used when there is a pressure drop in the reactor or heat

exchange between the PFR and the surroundings.
In the absence of pressure drop or heat exchange the integral form
of the plug flow design equation is used
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Conversion as a function of distance

down the tubular reactor

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The effect of the change in the number

of moles in the gas phase reactions
For constant temperature and pressure:
When there is no change in the number of moles with reaction

(e.g., A B) = 0 and = 0, then the fluid moves through the

reactor at a constant volumetric flow rate ( = 0) as the
conversion increases.
When there is a decrease in the number of moles ( < 0, < 0) in
the gas phase (e.g., 2A B), the volumetric gas flow rate
decreases as the conversion increases; for example:
Consequently, the gas molecules will spend longer in the reactor
than they would if the flow rate were constant, = 0. As a result,
this longer residence time would result in a higher conversion than if
the flow were constant at 0.
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The effect of the change in the number

of moles in the gas phase reactions
On the other hand, if there is an increase in the total
number of moles ( > 0, > 0) in the gas phase (e.g., A
2B), then the volumetric flow rate will increase as the
conversion increases; for example:
and the molecules will spend less time in the reactor than
they would if the volumetric flow rate were constant. As a
result of this smaller residence time in the reactor, the
conversion will be less than what would result if the
volumetric flow rate were constant at 0.
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Example 4-3: Producing 300 Million Pounds per Year of

Ethylene in a Plug-Flow Reactor: Design of a Full-scale
Tubular Reactor
Determine the plug-flow reactor volume necessary to produce
300 million pounds of ethylene a year from cracking a feed
stream of pure ethane. The reaction is irreversible and follows
an elementary rate law. We want to achieve 80% conversion of
ethane, operating the reactor isothermally at 1100 K at a
pressure of 6 atm.

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Example 4-3: Solution

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Todays example
Example for Liquid Phase Undergraduate Laboratory

Experiment

Entering
Volumetric flow rate
Acetic Anhydride
Water
Elementary with k
Case I
Case II
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CSTR
PFR

v0 = 0.0033 dm3/s
7.8% (1M)
92.2% (51.2M)
1.95x10-4 dm3/(mol.s)

CSTR Laboratory Experiment

Example: (CH2CO)2O + H20 2CH3OOH

A + B 2C
1) Mole Balance:
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FA0 X
CSTR: V =
rA

CSTR Laboratory Experiment

rA = k AC AC B

2) Rate Law:
3) Stoichiometry:

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FA0B

-FA0X

FB=FA0(B-X)

CSTR Laboratory Experiment

CB =

FA0 ( B X )

= C A0 ( B X )

C B = C A0 (51.2 X ) C A0 (51.2 ) C B 0
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CSTR Laboratory Experiment

0 kC A0 X

kX
V
kX
V=

=
=
=
C A0 (1 X )
0 (1 X )
0 (1 X )
X

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k
=
1 + k

PFR Laboratory Experiment

A + B 2C
dm 3
0.00324
s

1) Mole Balance:
2) Rate Law:

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dX rA
=
dV FA0

rA = kC AC B

PFR Laboratory Experiment

4) Combine:

rA = k ' CB0CA0 (1 X ) = kCA0 (1 X )

1
ln
= k
1 X
X = 1 e k
0.311dm 3
= =
= 96 .0 sec
3
0 0.00324 dm sec
V

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k = 0.01 s 1

Todays example
Example for Gas Phase : PFR and Batch Calculation

Pure NOCl fed with CNOCl,0 = 0.2 mol/dm3 follows an

elementary rate law with k = 0.29 dm3/(mol.s)
Case I

Case II

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PFR with
v0 = 10 dm3/s
Find space time, with X = 0.9
Find reactor volume, V for X = 0.9
Batch constant volume

Gas Flow PFR Example

2 NOCl 2 NO + Cl2
2A 2B + C

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1) Mole Balance:

dX rA
=
dV FA0

2) Rate Law:

rA = kC A2

Gas Flow PFR Example

3) Stoichiometry:

= 0 (1 + X )

(Gas Flow)
A B + C
4) Combine:

38`1

kC (1 X )
rA =
(1 + X )2
2
A0

Gas Flow PFR Example

2
(
)
1
+

X
2
kC A0 = 2 (1 + ) ln (1 X ) + X +

1 X

kC A 0 = 17.02

17.02
=
= 294 sec
kC A0
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Constant Volume Batch Example

Gas Phase 2A 2B + C

2) Rate Law:
3) Stoichiometry:

t=?

rA = kC A2

V = V0

(Gas Flow)

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rA = kC

2
A0

(1 X )

Constant Volume Batch Example

4) Combine:

dX kC (1 X )
2
=
= kC A0 (1 X )
dt
C A0
2
A0

dX
= kC A0 dt
2
(1 X )

1
= kC A0t
1 X
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Heat Effects
Isothermal Design
Stoichiometry
Rate Laws
Mole Balance

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End of Lecture 5a

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