Reaction Engineering

CHE 3164
SEMESTER 2, 2017

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ACADEMIC STAFF
Lecturer and Unit Coordinator (Clayton):

Prof. Sankar Bhattacharya (Department of Chemical Engineering)

Email: sankar.bhattacharya@monash.edu

Lecturer and Unit Coordinator (Malaysia):

A/P Dr. Chai Siang Piao (School of Engineering)

Email: chai.siang.piao@monash.edu
Room: 5-4-27

Tutors: Mr. Ng Boon Junn (ng.boon.junn@monash.edu)

Lab demonstrator: Ms. Lutfi Kurnianditia Putri (lutfi.putri@monash.edu)

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 SCHEDULE OF LECTURES, LABORATORY SESSIONS AND PROBLEMS CLASSES
3

Tutorial will start in week 2.

Laboratory will start in week 4/5

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UNIT OUTLINE
PRESCRIBED TEXTBOOK: H. Scott Fogler, Elements
of Chemical Reaction Engineering, 5th edition, Prentice
Hall, USA, 2016.

OTHER REFERENCE: Octave Levenspiel, Chemical

Reaction Engineering, 3rd edition, Wiley, New York,
USA, 1999.

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UNIT OUTLINE
Chapter Topic Sections in text*
1 Mole balances 1.1-1.5
Conversion and Reactor sizing 2.1-2.6
Rate laws and stoichiometry 3.1-3.4, 4.1-4.3
2 Isothermal reactor design 5.1-5.6, 6.1-6.6
3 Collection and analysis of rate data 7.1-7.7
4 Multiple reactions 8.1-8.8
Reaction mechanisms, Bioreactions and 9.1-9.4,
Bioreactors
5 Non-isothermal reactors and Energy Balance 11.1-11.7
6 Catalysis and catalytic reactors 5.5, 10.1-10.7
7 Heterogeneous reactions 14.1-14.5
8 Diffusion and reactions 15.1-15.11

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 UNIT SCHEDULE
Week Lecture (chapters in Fogler)/Test Tutorial classes Laboratory
1 Introduction - -

2 Mole balances: 1.1-1.5 Homework from -

Conversion and reactor sizing: 2.1-2.6 week 1 & 2
3 Rate laws and stoichiometry: 3.1-3.4, 4.1-4.3 Homework from -
week 2 & 3
4 Isothermal reactor: 5.1-5.6, 6.1-6.6 Homework from Yes
Collection/analysis of raw data: 7.1-7.7 week 3 & 4

5 Collection/analysis of raw data: 7.1-7.7 continued Homework from Yes

Multiple Reactions: 8.1-8.8 week 4 & 5
Test 1
6 Multiple Reactions: 8.1-8.8 - continued Homework from Yes
Bio reactions and bio reactors: 9.2-9.4 week 5 & 6

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UNIT SCHEDULE
7 Reaction mechanisms: 9.1 Homework from Yes
Non-isothermal reactor: 11.1-11.7 week 6 & 7
8 Non-isothermal reactor: 11.1-11.7 - continued Homework from Yes
week 7 & 8
9 Non-isothermal reactor: 11.1-11.7 - continued Homework from Yes
Catalysis and catalytic reactor: 10.1-10.7 week 8 & 9
10 Catalysis and catalytic reactor: 10.1-10.7 - continued Homework from Yes
Test 2 week 9 & 10

11 Catalytic reactors with pressure drop: 5.5 Homework from Yes

Catalysis and catalytic reactor - Heterogeneous reactions week 10 & 11
and diffusion effects: 14.1-14.5 , 15.1-15.11
12 Catalysis and catalytic reactor - Heterogeneous reactions Homework from -
and diffusion effects: 14.1-14.5 , 15.1-15.11 week 11 & 12
Reactor safety
Revision, Q & A

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ASSESSMENT
Week Activity Value
5 Test 1 on materials taught up to week 4 8%
Closed book
10 Test 2 on materials taught up to week 9 12%
Closed book
Continuous class participation (throughout the semester) 10%

One Laboratory report covering both experiments (due one week 10%
after the second experiment)
Total continuous assessment 40%
Final Examination (2 hours closed book) 60%
Total assessment 100%

To pass this unit, you must achieve at least a minimum of 45% on the class-work (total
continuous assessment), and a minimum of 45% on the final exam. Otherwise you will
receive a maximum mark of 45 as the final grade. The overall pass mark is still 50%.

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CHAPTER 1

INTRODUCTION

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What is Reaction?

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Differentiate chemical
engineers from other
engineers

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 Recycle

Physical Physical
treatment Reaction treatment
processes processes

To purify raw materials: To separate products from reactants:

Distillation, UF, RO, separator Distillation, separator

Typical chemical plant

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 Definition - chemical reaction

A chemical species is said to have reacted when it has

lost its chemical identity.
Three main ways a chemical species can lose its
chemical identity:
- decomposition CH 3CH 3 H 2 H 2C CH 2 (dehydrogenation)

- combination N 2 O2 2 NO

- isomerization C2 H 5CH CH 2 CH 2 C (CH 3 ) 2

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 Classification of reactions:

- According to the number of phases involved in the reaction

a) Homogeneous chemical reactions in which the reactants
(or catalyst and reactants) are in the same phase
b) Heterogeneous chemical reactions in which the reactants
(or catalyst and reactants) are in two or more phases
Catalytic reactions: Ammonia synthesis, hydrocracking of crude oil,
Gas-To-Liquid (GTL)
Non-catalytic reactions: Burning of coal, attack of solids by acids, etc.

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 Definition - Catalyst
- A substance that initiates and accelerates a chemical
reaction without itself being consumed.
- Homogeneous catalysts, heterogeneous catalysts and
biocatalyst

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- Equipment used to carry out reaction - Reactor
a) Batch reactor
b) Flow reactor CSTR, tubular reactor
c) Catalytic reactor Fixed bed, moving bed, fluidised bed

Batch CSTR
Tubular

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 Industrial reactors
Type of Reactor Characteristics

Simple Batch Reactor is charged via two holes in the top of the tank; while reaction is
carried out, nothing else is put in or taken out until the reaction is done;
tank easily heated or cooled by jacket

Kinds of Phases Usage Advantages Disadvantages

Present

1. Gas phase 1. Small scale 1. High conversion per unit 1. High operating cost
production volume for one pass
2. Liquid phase
2. Intermediate or one 2. Flexibility of operation-
3. Liquid Solid
shot production same reactor can produce
one product one time and a
3. Pharmaceutical
different product the next
4. Fermentation
3. Easy to clean

Assumptions
1) No inflow or out flow FA0 = FA = 0
2) Well mixed

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Type of Reactor Characteristics

Continuously Stirred Tank Run at steady state with continuous flow of reactants and products; the
Reactor (CSTR) feed assumes a uniform composition throughout the reactor, exit stream
has the same composition as in the tank

Kinds of Phases Usage Advantages Disadvantages

Present

1. Liquid phase 1. When agitation is 1. Continuous operation 1. Lowest

required conversion per
2. Gas-liquid rxns 2. Good temperature control
unit volume
2. Series configurations
3. Solid-liquid rxns 3. Easily adapts to two phase
for different 2. By-passing and
runs
concentration streams channeling
5. Simplicity of construction possible with poor
agitation
6 Low operating (labor) cost

7. Easy to clean

Assumptions
1) Steady state therefore
2) Well mixed therefore rA is the same throughout the reactor

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Type of Reactor Characteristics

Plug flow reactor (PFR) Arranged as one long reactor or many short reactors in a tube bank ; no
radial variation in reaction rate (concentration); concentration changes
with length down the reactor

Kinds of Phases Usage Advantages Disadvantages

Present

1. Primarily Gas 1. Large Scale 1. High Conversion per 1. Undesired thermal

Phase Unit Volume gradients may exist
2. Fast Reactions
2. Low operating (labor) 2. Poor temperature
3. Homogeneous
cost) control
Reactions
3. Continuous 3. Shutdown and
4. Heterogeneous
Operation cleaning may be
Reactions
expensive
4. Good heat transfer
5. Continuous
Production

6. High Temperature

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Type of Reactor Characteristics

Tubular fixed bed reactor Tubular reactor that is packed with solid catalyst particles

Kinds of Phases Usage Advantages Disadvantages

Present

1. Gas phase/ solid 1. Used primarily in 1. High conversion 1. Undesired thermal

catalyzed heterogeneous has per unit mass of gradients may exist
phase reactions with catalyst
2. Gas-solid rxns 2. Poor temperature
a catalyst
2. Low operating control
cost
3. Channeling may
3. Continuous occur
operation
4. Unit may be
difficult to service
and clean

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 Type of Reactor Characteristics

Fluidized Bed Reactor Heterogeneous reactions; like a CSTR in that the reactants are well
mixed
Kinds of Phases Usage Advantages Disadvantages
Present

1. Gas-solid 1. Heterogeneous has 1. Good mixing 1. Bed-fluid mechanics

phase reactions with a not well known
2. Gas-solid catalyzed 2. Good uniformity of
catalyst
temperature 2. Severe agitation can
result in catalyst
3. Catalyst can be
destruction and dust
continuously
formation
regenerated with the
use of an auxiliary loop 3. Uncertain scale-up

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 Elementary & non-elementary reactions

i) Elementary reaction
A B R
rA kCAC B
The rate equation corresponds to a stoichiometric
equation
A 2B R
rA kCAC B2

ii) Non-elementary reaction

H 2 Br2 2 HBr
No direct correspondence between stoichiometry
k1 H 2 Br2 2
1

rHBr and rate

k 2 HBr /Br2

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1.1 Rate of Reaction
The rate of reaction can be expressed as the rate of
disappearance of a reactant or as the rate of appearance
(formation) of a product.
The rate of reaction is (the number of moles of reactant
disappearing) or (the number of moles of product formation)
per (unit time) per (unit volume).

A single-phase reaction aA + bB cC + dD
Rate of disappearance of A

1 dN A (amount of A disappearing) mol

rA , 3
V dt (volume)(time) m .s

The minus sign means disappearance

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A single-phase reaction aA + bB cC + dD

The minus sign means disappearance

1 dN B (amount of B disappearing) mol

rB , 3
V dt (volume)(time) m .s
1 dN C (amount of C forming) mol Relative rates
rC , 3
V dt (volume)(time) m .s
rA rB rC rD

1 dN C (amount of D forming) mol a b c d
rD , 3
V dt (volume)(time) m .s

Rate of formation of D

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AB

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

Example: A B
If B is being created at a rate of 0.2 moles/dm 3/s. What are the rate of
formation of B, rates of formation and disappearance of A ?
rA rB
Rate of formation of B: rB = 0.2 mole/dm3/s
a b
Rate of disappearance of A: -rA = 0.2 mole/dm3/s
Rate of formation of A: rA = -0.2 mole/dm3/s

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Example 1.1
A rocket engine burns a stoichiometric mixture of fuel (liquid hydrogen) in oxidant (liquid oxygen).
The combustion chamber is cylindrical, 75 cm long and 60 cm in diameter, and the combustion
process produces 108 kg/s of exhaust gases (H2O). If combustion is complete, find the rate of
reaction of hydrogen and oxygen. Complete combustion: H2 + O2 H2O

Solution
1 dN H 2 1 dN O2
Rate of reaction: rH 2 and rO
V dt 2
V dt

Reactor volume: V = /4 (0.6)2(0.75) = 0.2121 m3

H2O produced = 108 kg/s (1kmol/18 kg) = 6 kmol/s

According to the stoichiometry equation, to produce 6 kmol/s of H2O requires 6 kmol/s of H2 and

3 kmol/s of O2

Thus, H2 consumed= 6 kmol/s and O2 consumed = 3 kmol/s

Rate of equation: 1 (0 - 3) kmol mol

rO2 3
1.415 x 104 3
0.2121 m s m .s
rH 2 rO2
rH 2
1 (0 - 6) kmol mol
2.829 x 104 3
0.2121 m 3
s m .s 1 1/ 2

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1.2 Definition of Conversion
A single-phase reaction aA + bB cC + dD
(moles of A reacted) N A0 N A Amount of A at time t
XA
(moles of A fed) N A0 Initial amount of A
N A0 N A
XA
N A0
Moles of A that have
N A N A0 N A0 X been consumed
Flow systems
N A N A0 (1 X)
FA0 FA
X
FA0
FA FA0( 1 X) FA0 C A0v0
FA0 = entering molar flow rate (mol/s)
CA0 = molarity (initial concentration, mol/dm3) (for liquid)
V0 = entering volumetric flow rate (dm3/s)

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 For gas phase

PA0VA0 nRT0 Idea gas law

n P
C A0 A0
VA0 RT0
y A0 P0
C A0
RT0

CA0 = entering concentration (mol/dm 3)

yA0 = entering mole fraction of A
P0 = entering total pressure, kPa
T0 = entering temperature, K
PA0 = entering partial pressure, kPa
R = ideal gas constant

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Example 1.2
A gas mixture consists of 50% A and 50% inerts at 10 atm (1013 kPa) and enters
the reactor with a flow rate of 6 dm3/s at 422.2 K. Calculate the entering
concentration of A, CA0, and the entering molar flow rate, FA0. The ideal gas
constant is R = 0.082 dm3.atm/mol.K.

Solution

Given, To calculate CA0 and FA0

y A0 P0
P0 = 10 atm C A0
RT0
yA0 = 0.5
0.5(10 atm)
C A0 3
0.14442 mol/dm 3
PA0 = 0.5 x 10 = 5 atm 0.082 dm .atm/mol.K (422.2 K)
T0 = 422.2 K C A0 0.144 mol/L

V0 = 6 dm3/s
FA0 CA0 v 0 (0.14442 mol/dm 3 )(6.0 dm3 / s)
R = 0.082 dm3.atm/mol.K FA0 0.867 mol/s

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 1.3 Space Time
Definition: Space time (tau) is the time necessary to process one
volume of reactor fluid at the entrance condition.
V
(time)
v0

Where, V = reactor volume (dm3)

v0 = entering volumetric flow rate (dm3/min)

v0 1
Space velocity, SV (time-1)
V

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Example 1.3
The space time necessary to achieve 80% conversion in a CSTR is 5 h.
Determine the reactor volume required to process 2ft 3/min entering flow. What are
the reactor volume and space velocity for this system ?

V
V ( x v 0 )
Solution v0
t = 5 hrs Reactor volume, V = 5 hrs (2 ft 3/min)(60 min/1 hr)
X = 0.8 V = 600 ft 3
v0 = 2 ft3/min
v0 1
Space velocity, SV
V
1
SV 0.2 hr -1
5

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1.4 Basic Batch Reactor Design Equations
Mole Balance Equation

Fj,0 REACTOR Fj

[Rate of flow [Rate of generation [Rate of flow of j out [Rate of

of j into the + of j by chemical - the system] = accumulation of j
system] reaction within the
within the system]
system]
dN j
F jo G j F j
dt
G j r j V rj dV
V

dN j
F jo F j rj dV
V
dt
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 Batch Reactor

In out + generation = accumulation

dN A
FA0 FA G A
dt

FA0 and FA = 0; Assumption: the reactant is well-mixed

0 0
dN A
FA0 FA G A t N A0 1 dN A
dt
dt
GA rA dV r AV
0 NA V rA
Design equation
N A0 1 dN A
dN A 1 dN A t
rAV rA NA V rA
dt V dt

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Constant-volume reactor
1 dN A d ( N A / V )
rA
V dt dt
NA = CAV
dC A
rA Design equation
NA= mole of A (mol)
dt
CA = concentration of A (mol/m3)
V = volume of reactor (m3)

Constant-pressure reactor (volume varies)

1 dN A 1 d (C AV )
rA
V dt V dt
1 VdC A 1 C A dV
rA
V dt V dt
dC A C A d ln V
rA Design equation
dt dt

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Example 1.4
The gas phase reaction A B + C is carried out isothermally in a 20 dm 3
constant-volume batch reactor. Twenty moles of pure A is initially placed in the
reactor. The reactor is well mixed. Calculate the time necessary to reduce the
number of moles of A in the reactor to 0.2 mol.
-rA = kCA with k = 0.865 min-1

Solution
Design equation for constant-volume batch reactor rA
dC A
dC A dt
V = 20 dm3 rA
NA0 = 20 mol
dt
t CA 1 1 C A0 1 N A0 / V
NA = 0.2 mol 0
dt
CA 0 r
A
dC A t
k
ln
CA
ln
k N A /V
CA 1 1 20
t dC A t ln
CA 0 kC
A 0.865 0.2

t 5.32 min

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 Batch reactor

N A0 N A 1 dN A
XA rA Design equation for batch reactor
N A0 V dt
N A N A0 N A0 X
dX
N A N A0 (1 X) rA V N A0
dt

dN A dX
0 N A0 t X dX
dt
dN A dX
dt

0
dt N A0
0 - rA V
N A0
dt dt X dX
t N A0 Time required for the reaction to
0 - rA V achieve conversion X

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1.5 Basic Continuous Flow Reactor Design Equations

Continuous Stirred Tank Reactor (CSTR)

FA = CA x v

In out + generation = accumulation FA = molar flow rate (mol/s)

CA = concentration (mol/m3)
V dN A v = volumetric flow rate (m3/s)
FA0 FA rA dV
0 dt
dN A FA0 FA
At steady state, 0 XA
dt FA0
V
rA dV FA0 FA FA FA0 FA0 X
FA0 FA FA0 X
rAV FA0 FA
FA0 FA
V V
FA0 X Design equation
rA rA

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 Plug Flow Reactor (PFR)
V dN A
FA0 FA rA dV
0 dt
V
dN A
At steady state,
dt
0 ; Thus, A0
F FA rA dV 0

Differentiate with respect to V FA FA0 FA0 X

dFA FA0 dX
dFA dFA
0 rA rA FA0 dX
dV dV rA
dV
V FA1 dFA X F
dV
V

0 FA 0 rA 0 rA
A0
dX 0 dV
X dX Design equation as
V
FA1 dFA Design equation as V FA0 a function of X
FA 0 rA a function of FA 0 rA

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 For packed-bed reactor (PBR)
,
FA1 dFA
W W = mass of catalyst
FA 0 rA'
dFA
rA'
dW
FA FA0 FA0 X
dFA FA0 dX

FA0 dX
rA'
dW
X F W
0 rA' dX 0 dW
A0

X dX
W FA0 Design equation
0 rA'

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1.6 Reactors in Series and Parallel

FA0
VCSTR ( X1 ) VPFR FA0
X1 dX
rA 0 rA

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Example 1.5
The exothermic reaction (A + B C) was carried out adiabatically and the following data
recorded:
X 0 0.2 0.4 0.5 0.6 0.8 0.9
-rA (mol/dm3.min) 10 16.67 50 50 50 12.5 9.09

The entering molar flow rate of A was 300 mol/min. What are the CSTR and PFR volume
necessary to achieve 40% conversion ?
Solution
X1 dX
F X VPFR FA0
Design equation: VCSTR A0 1 0 rA
rA
(300 mol/min)(0 .4) VPFR = 300 x (area under the curve)
VCSTR
50 mol/dm 3 .min
Using Simpsons one-third rule to calculate the area
2.4 dm3
h 1 4 1
VPFR FA0 ( )
In this case, VCSTR < VPFR. Thus, 3 rA (0) rA (0.2) rA (0.4)
using CSTR is suitable 1 1 4 1
VPFR 300( )(0.2)
3 10 16.67 50
7.2 dm 3
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 Two CSTR in series

Mole balance on R1 Mole balance on R2

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 Two plug reactors in series

FA0 FA1 FA2

V1 V2
X1 X2

X1 dX X2 dX
V1 FA0 V2 FA0
0 rA X1 rA

X2 dX X 1 dX X 2 dX
VTotal FA0 FA0 FA0
0 rA 0 r
A
X1 r
A

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 PFR and CSTR in series

FA0 X 1 X2 FA0 FA0 ( X 3 X 2 )

V1 V2 dX V3
rA1 X1 rA2 rA3

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Example 1.6
The adiabatic exothermic irreversible gas phase reaction is to be carried out in a flow
reactor for a stoichiometric feed of A and B.

a) What PFR volume is necessary to achieve 50% conversion? (150 dm 3)

b) What CSTR volume is necessary to achieve 50% conversion? (250 dm 3)
c) What CSTR volume must be added to raise the conversion in Part (b) to 80%? (30 dm 3)
d) What PFR volume must be added to raise the conversion in Part (b) to 80%? (90 dm 3)

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1.7 Rate Laws
Rate laws: algebraic equation that relates rate of reaction (-rA) to the
species concentrations.
rA kCA CB
The rate of a reaction is a function of temperature (through the rate
constant) and concentration.
aA bB cC dD
For example, in the reaction
Relative rates of reaction 2 NO O2 2 NO2

rNO2 4mol / m 3 s
rA rB rC rD
rNO 4mol / m 3 s
a b c d
rO2 2mol / m3 s

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Example 1.7
The Reaction: 2A + 3B -> 5C is carried out in a reactor. If at a
particular point, the rate of disappearance of A is 10 mol/dm 3/s, what
are the rates of B and C ?
Solution

The rate of disappearance of A, -ra, is

The rate of formation of species A is

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

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 Power law
Power law model
rA kCA CB k = rate constant

The reaction is order with respect to reactant A, and

order with respect to reactant B. Overall reaction order = +

Example:
Gas phase synthesis of phosgene rCO kCCOCCl2
3/ 2

The reaction is first order with respect to carbon monoxide and

three-halves order with respect to chlorine.

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 n
r0 = k P CH 4
5
k 6 K 1 K 2 K 3 K 4 K 5 2 CT PCH 4
rC S
K 12 P 2 P 5 2 K K K K K 5 2 P K K K K 3 2 P 12 P K K K 3 2 P P K K P 3 2 P
5 H2 H2 1 2 3 4 5 CH 4 1 2 3 5 H 2 CH 4 1 2 5 H 2 CH 4 1 5 H 2 CH 4

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You can tell the overall reaction order by the units of k

Reaction
CA -rA Rate Law k
Order
(mol/dm3) (mol/dm3*s) zero -rA = k (mol/dm3*s)
(mol/dm3) (mol/dm3*s) 1st -rA = kCA s-1
(mol/dm3) (mol/dm3*s) 2nd -rA = kCA2 (dm3/mol*s)

For reactions in which the stiochiometric coefficient is 1 for all species, for
example,
NaOH HCl NaCl H 2 O
then, all ki are equal, or

k k NaOH k HCl k NaCl K H 2O

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k is the specific reaction rate (constant) and is given by the
Arrhenius Equation:

E k = rate constant
k Ae RT E = activation energy
R = gas constant
T = absolute temperature
E
ln k ln A A = frequency factor
RT
k E 1 1
ln 2
k1 R T1 T2

Activation energy:
The minimum energy that must be
possessed by reacting molecules
before the reaction will occur

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Example 1.8
Calculate the activation energy for the following reaction
AB+C

K (s-1) 0.00043 0.00180 R = universal gas constant = 8.314 J/mol K

T (K) 313.0 323.0

Solution

k2 E 1 1 1.432(8.314)
ln E
k1 R T1 T2 (0.00319 0.00310)

0.00180 E 1 1
ln E 120kJ / mol
0.00043 R 313 323

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Example 1.9 (Ex. 3.1 Fogler)

Calculate the activation energy for the decomposition of benzene

diazonium chloride to give chlorobenzene and nitrogen:

k(s-1) 0.00043 0.00103 0.00180 0.00355 0.00717

T (K) 313.0 319.0 323.0 328.0 333.0

Solution

E E
k Ae RT ln k ln A
RT
k 0.00043 0.00103 0.0018 0.00355 0.00717
T 313 319 323 328 333
ln k -7.75173 -6.8782 -6.31997 -5.64081 -4.93785
1/T 0.003195 0.003135 0.003096 0.003049 0.003003

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 1/T
-4
0.00295 0.003 0.00305 0.0031 0.00315 0.0032 0.00325
-4.5

-5
E
-5.5 ln k ln A
ln k
RT
-6
-E/R = -14,017K
-6.5
E = 14,017 x 8.314
-7 E = 116.5 kJ/mol
-7.5 y = -14017x + 37.12
R = 0.998 ln A = 37.12
-8
A = 1.32 x 1016 s-1
-8.5

-9

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1.8 Reversible Reaction
A+BC
The net rate of formation of any species is equal to its rate of formation on the
forward reaction plus its rate of formation in the reverse reaction
Rate = rate forward + rate reverse

At equilibrium, net rate = 0 and the rate law must reduce to an equation that is
thermodynamically consistent with the equilibrium constant for the reaction.

For the reaction: aA + bB cC + dD

Equilibrium constant,

Unit of KC= (mol/dm3)d+c-a-b

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How to write rate laws for reversible reaction?
2C6H6 C12H10 + H2
kA
2A
k
B+C
-A
kA
The rate of disappearance of A 2A B + C
-rA, forward = kACA2
k-A Equilibrium constant
The rate of formation of A B+CA

rA, reverse = k-ACBCC

rA, net = rA, forward + rA, reverse

= -kACA2 + k-ACBCC
- rA, net = kACA2 - k-ACBCC Thermodynamically consistent at
equilibrium

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Example 1.10
Suggest a rate law for the following reversible liquid-phase reaction and calculate
the equilibrium conversion and concentration
(A + B C) with CA0 = CB0 = 2 mol/dm3 and KC = 10 dm3/mol

Solution
rA, net = rA, forward + rA, reverse
= -kACACB + k-ACC
-rA, net = kA(CACB - CC/KC) where KC = kA/k-A

At equilibrium, rA = 0 CA0Xe = KCCA02(1-Xe)2 CA = 2(1-0.8) = 0.4 mol/dm3

Thus CC=KCCACB 2Xe = 10(4)(1-Xe)2 CB = 2(1-0.8) = 0.4 mol/dm3
CA = CA0(1-Xe) Solve for Xe CC = 2(0.8) = 1.6 mol/dm3
CB = CA0(1-Xe) Xe = 0.8
CC = CA0Xe
60
1.9 Stoichiometry
So far, we have shown how the rate law can be expressed as a function of
concentrations. Then, we need to express the concentration as a function of
conversion in order to size reactors.
Stoichiometry plays a major role if the rate law depends on more than one
species, we must relate the concentration of different species by
stoichiometric balance.
Consider the general reaction

aA bB cC dD
b c d
A B C D
a a a

The mole of B remaining in the system,

Mole of A reacted =
Mole of B reacted =
=

61
 Stoichiometric Table for Batch System

Species Symbol Initial Change Remaining

A A Ni 0 C y
i i0 i0
-NB0X N A0 C A0 y A0
B B

+NC0X
C C
d c b
+ND0X 1
D D a a a

Inert I
N T N T 0 N A0 X
Total

d c b
NT NT 0 ( 1) N A0 X
a a a

62
 Constant volume batch reactor

63
Example 1.11
Write the rate law for the liquid phase reaction (follow the elementary rate law)
solely in terms of conversion. The feed to the batch reactor is equal molar A and B
with CA0 = 2 mol/dm3 and kA= 0.01 (dm3/mol)4/s.

Solution

Rate Law: -rA=kC3AC2B

Species A is the limiting
Liquid phase, v = vo (no volume change) reactant because the feed
is equal molar in A and B,
and two moles of B
consumes 3 moles of A.

64
 Flow system

Fi 0 Ci 0v0 Ci 0 y
i i0
FA0 C A0v0 C A0 y A0

65
 Flow system

Liquid Phase Flow System:

Reactor
Species Symbol Reactor Feed Change
Effluent

A A

B B

C C
If the rate of reaction were -rA = kCACB
then we would have
D D

Inert I

66
 Volume change with reaction
N T 0 FT 0

For gas phase reaction, N T FT

F j F j P T0 N T 0
PV zNT RT (at time t), z compressibility factor C j
0 0 T
v v P T N
P0V0 z0 NT 0 RT0 (at t 0)
F j F F j P T0
P T Z N C j T 0
v v0 0 T 0 T 0 T
v v F P
P T0 Z 0 NT 0
F j P T0
C j CT 0
y A0 T 0 T
F P
N T NT 0 N A0 X
FA0 ( j v j X ) P T0
C j CT 0
NT N F T 0 F A0X P 0 T
1 A0 X 1 y A0 X
NT 0 NT 0 F j v j X P T0
C j CT 0 A0
F 1 ( F / F ) X P T
P T Z
T 0 A 0 T 0 0

v v0 0 (1 X ) C A0 y A0 CT 0
C A0 ( j v j X ) P T0
P T0 Z 0 Cj
1 X 0 T
P
P T
v v0 (1 X ) 0
P T0 y A0

67
 Incompressible liquid, gas phase at
Gas phase (volume change) constant volume in batch system

68
Example 1.12
For the gas phase reaction 2A + B C
The feed is equal molar in A and B. Calculate

Solution
A is the limiting reactant
A + B C
= - -1 = -1
= yA0 = (-1) = -0.5

69
Example (Book)

Gas phase reaction that does not have an

equal number of product and reactant moles

70
Example 1.13
A mixture of 28% SO2 and 72% air is charged to a flow reactor in which SO2 is oxidized.
2SO2 + O2 2SO3
The total pressure is 1485 kPa and temperature is constant at 227oC. Calculate the gas
concentrations (SO2, O2, SO3 and N2) at the reactor outlet if the conversion is 0.5.
Solution
Taking SO2 as basis of calculation: SO2 + 1/2O2 SO3
FSO2,0 = (0.28)(FT0)
FO2,0 = (0.72)(0.21)(FT0) P
CSO2,0 ySO2,0C T0 ySO2,0 0
FN2,0 = (0.72)(0.79)(FT0) RT0
O2 = FO2,0/FSO2,0 = 0.54 1485 kPa
0.28
N2 = FN2,0/FSO2,0 = 2.03 8.314 kPa. dm3. K(500K)
0.1mol/dm3
SO3 = 0

71
 At X = 0.5

O2

y A0

0.28(1 1 1 / 2) 0.14

72
 Summary variable volume gas flow system

CA

CB

CC

CD

CI

73
74