Lecture 1

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.

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 Lecture 1
 Introduction

 Definitions

 General Mole Balance Equation

 Batch (BR)
 Continuously Stirred Tank Reactor (CSTR)
 Plug Flow Reactor (PFR)
 Packed Bed Reactor (PBR)

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 Chemical Reaction Engineering
 Chemical reaction engineering is at the heart of
virtually every chemical process. It separates the
chemical engineer from other engineers.

Industries that Draw Heavily on Chemical

Reaction Engineering (CRE) are:
CPI (Chemical Process Industries)
Examples like Dow, Amoco, Chevron, BSR, SK
Energy, etc.

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4
 Smog (Ch. 1)
Wetlands (Ch. 7 DVD-ROM)

Hippo Digestion (Ch. 2)

Oil Recovery Cobra Bites

(Ch. 7) (Ch. 8 DVD-ROM)

Lubricant Design Plant Safety

5
Chemical Plant for Ethylene Glycol (Ch. 5) (Ch. 9) (Ch. 11,12,13)
 Let’s Begin CRE
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.
 Chemical Identity

• A chemical species is said to have reacted

when it has lost its chemical identity.
 Chemical Identity
• A chemical species is said to have reacted
when it has lost its chemical identity.

• The identity of a chemical species is

determined by the kind, number, and
configuration of that species’ atoms.
 Chemical Identity
• A chemical species is said to have reacted
when it has lost its chemical identity.

1. Decomposition
 Chemical Identity
• A chemical species is said to have reacted
when it has lost its chemical identity.

1. Decomposition

2. Combination
 Chemical Identity
• A chemical species is said to have reacted
when it has lost its chemical identity.

1. Decomposition

2. Combination

3. Isomerization
 Chemical Identity
 A chemical species is said to have reacted when
it has lost its chemical identity.
 There are three ways for a species to loose its
identity:

1. Decomposition CH3CH3  H2 + H2C=CH2

2. Combination N2 + O2  2 NO
3. Isomerization C2H5CH=CH2  CH2=C(CH3)2

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 Reaction Rate
• The reaction rate is the rate at which a
species looses its chemical identity per unit
volume.
 Reaction Rate
• The reaction rate is the rate at which a
species looses its chemical identity per unit
volume.
• The rate of a reaction (mol/dm3/s) can be
expressed as either

the rate of Disappearance: -rA

or as
the rate of Formation (Generation): rA
 Reaction Rate

Consider the isomerization AB

rA = the rate of formation of species A per unit volume

-rA = the rate of a disappearance of species A per unit volume

rB = the rate of formation of species B per unit volume

 Reaction Rate
• EXAMPLE: AB
If Species B is being formed at a rate of
0.2 moles per decimeter cubed per second, ie,

rB = 0.2 mole/dm3/s
 Reaction Rate
• EXAMPLE: AB

rB = 0.2 mole/dm3/s

Then A is disappearing at the same rate:

-rA= 0.2 mole/dm3/s

 Reaction Rate
• EXAMPLE: AB
rB = 0.2 mole/dm3/s

Then A is disappearing at the same rate:

-rA= 0.2 mole/dm3/s

The rate of formation (generation of A) is

rA= -0.2 mole/dm3/s
 Reaction Rate
• For a catalytic reaction, we refer to -rA',
which is the rate of disappearance of
species A on a per mass of catalyst basis.
(mol/gcat/s)

NOTE: dCA/dt is not the rate of reaction

 Reaction Rate
Consider species j:
• rj is the rate of formation of species j per
unit volume [e.g. mol/dm3/s]
 Reaction Rate
• rj is the rate of formation of species j per
unit volume [e.g. mol/dm3*s]

• rj is a function of concentration,
temperature, pressure, and the type of
catalyst (if any)
 Reaction Rate
• rj is the rate of formation of species j per unit
volume [e.g. mol/dm3/s]
• rj is a function of concentration, temperature,
pressure, and the type of catalyst (if any)

• rj is independent of the type of reaction system

(batch reactor, plug flow reactor, etc.)
 Reaction Rate
• rj is the rate of formation of species j per
unit volume [e.g. mol/dm3/s]
• rj is a function of concentration,
temperature, pressure, and the type of
catalyst (if any)
• rj is independent of the type of reaction
system (batch, plug flow, etc.)

• rj is an algebraic equation, not a

differential equation
 Building Block 1:
General Mole Balances
System
Volume, V

Fj0 Gj Fj

 Molar Flow  Molar Flow   Molar Rate   Molar Rate 

 Rate of    Rate of   Generation    Accumulation
       
 Species j in   Species j out  of Species j  of Species j 
dN j
Fj 0  Fj  Gj 
dt
 mole   mole   mole   mole 
          
24  time   time   time   time 
 Building Block 1:
General Mole Balances
If spatially uniform:
G j  r jV

If NOT spatially uniform:

 V1
V2
rj1
rj 2
G j1  rj1V1
G j 2  rj 2 V2

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
 Building Block 1:
General Mole Balances
n
G j   rji Vi
i 1

Take limit
n
Gj   rjiVi   r dV
j
i1 lim V  0 n  

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 Building Block 1:
General Mole Balances
System
Volume, V

FA0 GA FA

General Mole Balance on System Volume V

In  Out  Generation  Accumulation

dN A
FA 0  FA   rA dV 
dt
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Batch Reactor Mole Balance
 Batch Reactor - Mole Balances

Batch

dN A
FA0  FA   rAdV 
dt
FA0  FA  0

Well-Mixed  r dV
A  rAV
dN A
 rAV
29 dt
 Batch Reactor - Mole Balances
dN A
Integrating dt 
rAV

t  0 N A  N A0
when
t  t NA  NA

NA
dN A
t  rAV
N A0

Time necessary to reduce the number of moles of A from NA0 to NA.

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 Batch Reactor - Mole Balances
NA
dN A
t 
rV
N A0 A

NA

31 t
Continuously Stirred Tank Reactor
Mole Balance
CSTR (Cont.)
CSTR (Cont.)
CSTR (Cont.)
CSTR (Cont.)
CSTR (Cont.)
Plug Flow Reactor
 PFR Mole Balances
PFR:
PFR Mole Balances (Cont.)
PFR Mole Balances (Cont.)
PFR Mole Balances (Cont.)
PFR Mole Balances (Cont.)
PFR Mole Balances (Cont.)
 Plug Flow Reactor - Mole Balances
PFR

dN A
FA0  FA   rA dV 
dt
dN A
Steady State 0
dt

FA0  FA   rA dV  0
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 Alternative Derivation
Plug Flow Reactor - Mole Balances
Differientiate with respect to V

0
dFA
 rA
dFA
 rA
dV dV
FA
dFA
The integral form is: V 
 FA 0
rA

This is the volume necessary to reduce the

entering molar flow rate (mol/s) from FA0 to the
exit molar flow rate of FA.
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 PFR Mole Balances (Cont.)
PFR:

FA dFA
The integral form is: V
FA 0 rA

This is the volume necessary to reduce the entering molar flow rate (mol/s) from FA0 to the
exit molar flow rate of FA.
Packed Bed Reactor Mole
Balance
PBR
 Packed Bed Reactor - Mole Balances
W
PBR
FA FA

W W  W
 
FA W   FA W  W   rA W 
dN A
dt
Steady State dN A
0
dt
FA W  W  FA W
lim  rA
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W 0 W
 Packed Bed Reactor - Mole Balances
Rearrange:
dFA
 rA
dW
The integral form to find the catalyst weight is:
FA
 dFA
W 
FA 0
rA

PBR catalyst weight necessary to reduce the

entering molar flow rate FA0 to molar flow rate FA.
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 Reactor Mole Balances Summary
The GMBE applied to the four major reactor types
(and the general reaction AB)
Reactor Differential Algebraic Integral
NA
NA
dN A
Batch dN A
 rAV t 
dt rV
N A0 A
t
CSTR FA 0  FA
V
rA FA
FA
PFR dFA V 
dFA
 rA
dV FA 0
drA
V

FA FA
dFA dFA
PBR
 dW
 rA W 
FA 0
rA
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W
 Reactors with Heat Effects

 EXAMPLE: Production of Propylene Glycol in

an Adiabatic CSTR

 Propylene glycol is produced by the hydrolysis of

propylene oxide:

H 2 SO4
CH2  CH  CH3  H2O CH2  CH  CH3
O OH OH

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 v0

Propylene Glycol

What are the exit conversion X and exit temperature T?

Solution
Let the reaction be represented by
A+BC
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 Evaluate energy balance terms

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 Analysis
We have applied our CRE algorithm to calculate the
Conversion (X=0.84) and Temperature (T=614 °R)
in a 300 gallon CSTR operated adiabatically.

T=535 °R

X=0.84
A+BC
T=614 °R
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 Keeping Up

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 Separations

Filtration Distillation Adsorption

These topics do not build upon one another.

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 Reaction Engineering

Mole Balance Rate Laws Stoichiometry

These topics build upon one another.

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 Heat Effects
Isothermal Design

Stoichiometry
Rate Laws
Mole Balance

CRE Algorithm

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 Mole Balance Rate Laws

Be careful not to cut corners on any of the

CRE building blocks while learning this material!

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 Heat Effects
Isothermal Design

Stoichiometry
Rate Laws

Mole Balance

Otherwise, your Algorithm becomes unstable.

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 End of Lecture 1

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 Supplemental Slides
Additional Applications of CRE

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 Supplemental Slides
Additional Applications of CRE

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 Supplemental Slides
Additional Applications of CRE

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 Supplemental Slides
Additional Applications of CRE

Hippo Digestion (Ch. 2)

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 Supplemental Slides
Additional Applications of CRE

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 Supplemental Slides
Additional Applications of CRE

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 Supplemental Slides
Additional Applications of CRE

Smog (Ch. 1)

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 Supplemental Slides
Additional Applications of CRE

Chemical Plant for Ethylene Glycol (Ch. 5)

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 Supplemental Slides
Additional Applications of CRE

Wetlands (Ch. 7 DVD-ROM) Oil Recovery (Ch. 7)

78
 Supplemental Slides
Additional Applications of CRE

Cobra Bites
(Ch. 8 DVD-ROM)

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 Supplemental Slides
Additional Applications of CRE

Lubricant Design (Ch. 9)

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 Supplemental Slides
Additional Applications of CRE

Plant Safety
(Ch. 11,12,13)

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Homework 1: A 200-dm3 constant-volume batch reactor is
pressurized to 20 atm with a mixture of 75% A and 25% inert. The
gas-phase reaction is carried out isothermally at 227 C.

V = 200-dm3
P = 20 atm
T = 227 C

a. Assuming that the ideal gas law is valid, how many moles of A are
in the reactor initially? What is the initial concentration of A?
b. If the reaction is first order:

Calculate the time necessary to consume 99% of A.

c. If the reaction is second order:

Calculate the time to consume 80% of A. Also calculate the pressure

in the reactor at this time if the temperature is 127 C.
Homework 2: