10/1/2010

CHBI 502
REACTION ENGINEERING

CHBI 502

HWs will be distributed after the chapters are covered, deadlines will be
posted
NO late submission

MT dates will be determined (mid of the semester)

Final exam date will be determined by the registrars office

You can contact me anytime through e-mail (okeskin@..)

You are wellcome during office hours, you need to ask me if I will be at the
office other than these hours.

No cheating (HWs, projects, exams)

10/1/2010

POLICY ON COLLABORATION AND ORIGINALITY

Academic dishonesty in the form of cheating, plagiarism, or collusion are serious offenses and
are not tolerated at Ko University. University Academic Regulations and the Regulations for
Student Disciplinary Matters clearly define the policy and the disciplinary action to be taken in
case of academic dishonesty.
Failure in academic integrity may lead to suspension and expulsion from the University.
Cheating includes, but is not limited to, copying from a classmate or providing answers or
information, either written or oral, to others. Plagiarism is borrowing or using someone elses
writing or ideas without giving written acknowledgment to the author. This includes copying
from a fellow students paper or from a text (whether printed or electronic) without properly
citing the source. Collusion is getting unauthorized help from another person or having
someone else write a paper or assignment. You can discuss the lecture and reading material,
and the general nature
nat re of the homework
home ork problems,
problems with
ith anyone.
an one Also,
Also you
o ma
may per
peruse
se all
previous ChBI 502 material available anywhere, such as on the web, and in the library
accumulated over the years. However, your final solutions should be your own original work.
Jointly prepared solutions, and solutions closely resembling those available, are unacceptable.

Textbook

Elements of Chemical Reaction Engineering

(4th ed.), H.S. Fogler Prentice Hall,
Upper Saddle River, NJ (2005).

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Course Outline, Tentative schedule

Review:
Chemical Kinetics and Ch1-6, Two-three weeks
Chapter 1:
Mole Balances
Chapter 2:
Conversion and Reactor Sizing
Chapter 3:
Rate Law and Stoichiometry
Chapter 4:
Isothermal Reactor Design
Chapter 5:
Collection and Analysis of Rate Data
Chapter 6:
Multiple Reactions
Chapter 7:
Reaction Mechanisms, Pathways, Bioreactions and Bioreactors , Two weeks
Chapter 8:
Steady-State Nonisothermal Reactor Design, Two weeks
Chapter 9:
Unsteady-state Nonisothermal Reactor Design, One week
Chapter 10:
Catalysis and Catalytic Reactors, Two weeks
Chapter 11:
External Diffusion Effects on Heterogeneous Reactions
Reactions, One Week
Chapter 12:
Diffusion and Reaction in Porous Catalysts, Two Weeks
Student presentations on projects, One week

Elements of Chemical Rxn Enginnering

Chemical kinetics is the study of chemical rxn rates and reaction
mechanisms.
Chemical reaction engineering (CRE) combines the study of chemical
kinetics with the reactors in which the reactions occur.
Objective of the course: Learn how to design equipment for
carrying out desirable chemical reactions
(what size and what type of equipment)
Chemical Kinetics & Reactor Design
The reaction system thet operates in the safest and most efficient manner
ca
t e key
ey to tthe
e success of
o the
t e plant.
pa t
can be the
Modelling of;
Chemical plant
Pharmacokinetics
Microelectronics
Digestive system of an animal

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Chapter1 MOLE BALANCES

1.

Chemical Identity
A chemical species is said to have reacted when it has lost its
chemical
h i l id
identity.
tit Th
The id
identity
tit off a chemical
h i l species
i iis d
determinde
t
i d
by the kind, number, and configuration of that species atoms.

Three ways a chemical species can lose its chemical identity:

1. Decomposition CH3CH3 H2 + H2C = CH2

2.

2 C
2.
Combination
bi ti

N2 + O2 2NO

3. Isomerization

C2H5CH = CH2 CH2 = C(CH3)2

Reaction Rate:
The reaction rate is the rate at which a species looses its chemical
identity per unit volume
volume. The rate of a reaction can be expressed as
the rate of disappearance of a reactant or as the rate of appearance
of a product. Consider species A:

AB
p
Ap
per unit volume
rA = the rate of formation of species
-rA = the rate of disappearance of species A per unit volume
rB = the rate of formation of species B per unit volume

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Example:

AB

If B is being created 0.2 moles per decimeter cubed per second, ie,
rB = 0.2 mole/dm3 s
Then A is disappearing at the same rate:
-rA = 0.2 mole/dm3 s
For catalytic reaction, we refer to rA, which is the rate of disappearance of
species A on a per mass of catalyst basis.

NOTE: dCA/dt is not the rate of reaction

(This is only true for a batch system, we will see)

If continuous dCA/dt = 0
The rate law does not depend on reactor type!
-rA is the # of moles of A reacting (disappearing) per unit time per unit volume
(mol/dm3 s)

In a reactor, two extreme conditions are considered:

1. No mixing of streams
2. Complete mixing (desirable)
Classification of reactions
Ideal mixing (no axial mixing, complete radial mixing)
Steady-state : conditions donot change with time at any point (PFR)

Complete mixing
non-steady-state: Uniform composition and temperture at any given instant,
change with time (t)

FA0
Stirrer, rpm and design are important

FA

Batch

CSTR)

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Thus,
Batch or continuous
Tank or tubular
Homogeneous or heterogeneous

Consider species j:
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.
We use an algebraic equation to relate the rate of reaction, -rA, to the
concentration of reacting species and to the temperature at which the reaction
occurs [e.g. rA = k(T) CA2]
For example, the algebraic form of the rate law for rA for A (products) may be;
a linear function of concentrations:

rA = k C A

or, it may be some other algebraic function of concn as:

rA = k C A2

or can be determined by experiments:

rA =

k1 C A
1 + k2 C A

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3. General Mole Balance Equation:

IN OUT + GENERATION = ACCUMULATION
V

FA0 FA + rA dV =
0

dN A
d
dt

[moles / time]

NA: # of moles
of species A in
the system at
time t.

GA = rA V (if all system variables (T, CA, etc.) are spatially uniform
throughout system volume)

G A = rA V
moles
moles

time = time volume [volume ]

If the rate of formation of A varies with position:

V1
V2

r1A
r2A

G A1 = r1 A V1 etc. for all subvolumes

GA =

i 1
=

GiA =

i 1
=

riA Vi

for M subvolumes

G A = rA dV

FA0 FA + rA dV =

dN A
dt

Basic equation for any species A

entering, leaving, reacting ...

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Mole Balance on Different Reactor Types

Batch Reactor is used for small-scale operations, for testing new
processes, for the manufacture of expensive products, and for the
processes that are not easy to convert to continuous.
high conversion rates (time spend is longer)
high labor cost and & variability of products from batch-to-batch

FA0 = 0

FA = 0

dN A
= rA V
dt
dN j
= rj dV
dt

If perfect mixing
(no volume change throughout
volume)

The # of moles changing (in A B) is as follows:

NA

NB

NA0
NB1
NA1

t1

t1

What time is the necessary to produce NA1

starting from NA0?
dN A
= rA V
dt
dN A
dt =
rA V
t1

N A1

dN A
r
V
N A0 A

dt =
0

t1 =

N A1

dN A
r
V
N A0 A

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Continuous Flow Reactors (CFR) operate at steady state.

Continuous Stirred Tank Reactor (CSTR)
Plug Flow Reactor (PFR)
Packed Bed Reactor (PBR)
usually used for liquid-phase rxns

CSTR

usually operated at steady state

FA0

usually assumed to be perfectly mixed

T f(t,V)
FA

General Mole Balance on System Volume V

IN OUT + GENERATION = ACCUMULATION
V

FA0 FA + rA dV =
0

dN A
dt

Assumptions

FA0

Steady State
V

FA

Well mixed

dN
dt

= 0

dV

= rA V

F A 0 F A + rA V = 0
Design eqn for CSTR

FA0 = CA0 v
Molar flow rate

V =

FA0 FA
rA

V =

A0

v0 C
rA

concentration

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Tubular Reactors consists of a cylindirical pipe and is operated at

steady state. Mostly used for gas phase rxns.
PFR Derivation: uniform velocity in turbulent flow (no radial variation in
velocity, concentration, temperature, reaction rate)
IN OUT + GENERATION = ACCUMULATION
V

FA0 FA + rA dV =
0

Reactants

dN A
dt

Products

10

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FA0

FA

Fj

GA

V + V

G A =

dV = rA V

FA V FA V + V + rA V = 0
Divide by V and rearrange:

Taking the limit as V0:

FA V + V FA V
= rA

dF A
= rA
dV
V =

FA

FA0

dF A
rA

Packed Bed Reactors (PBR) are not homogenous, the fluid-solid

heterogenous rxn take place on the surface of the catalyst. Rate (r) is
dependent on the mass of catalyst (W).
-rA = mol A reacted / (s) (g catalyst)
General Balance on W
IN OUT + GENERATION = ACCUMULATION
V

FA0 FA + rA 'dW =
0

dN A
dt

W
W

W+W

FA(W) FA(W+W)

11

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Steady State

dN A
=0
dt
V

FA0 FA + rA 'dV =
0

dN A
dt

Differentiate with respect to W and rearrange

dFA
= rA '
dW
When pressure drop through the reactor and catalyst decay are
neglected, the integral egn can be used to find W:
FA

dFA
W=
=
r
'
A
FA 0

FA 0

FA

dFA
rA '

Batch Reactor Times

AB
Calculate the time to reduce the number of moles by a factor of 10 (NA =
NA0/10) in a batch reactor for the above reaction with
-rrAA = k CA when k = 0.046 min-1

Mol balance :
In Out + Generation = Accumulation
0 0 + rA V =

dN A
dt

Rate law :
N
rA = k C A rA = k C A = k A
V
dN A
= k N A
rA V = k N A
dt

12

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Solve :
NA

A
dN A
dN A
t=
=
r V
rA V
N A0 A
N A0

rA V = k C A V = k
t=

N A0

NA

NA =

NA
V = k N A
V

N
1
dN A
= ln A0
k NA k
NA
N A0
10

t=

1
ln(10)
0.046 min

Therefore, t = 50 minutes

Summary of Chapter 1
Define the rate of chemical reaction.
Apply the mole balance equations to a batch reactor, CSTR, PFR,
and PBR.

Batch reactor:

no in-out streams, no spatial variations in

concn

CSTR: no spatial variations in the tank, steady state

PFR: spatial variations along the reactor
reactor, steady state
PBR: spatial variations along the reactor, steady state
V

FA0 FA + rA dV =
0

dN A
dt

Basic equation for any species A

entering, leaving, reacting ...

13

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Reactor

Differential

Algebraic

Integral

Batch

CSTR

PFR

PBR

general reaction, A->B

14

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15

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Compartments for perfusion

Alcohol

Stomach
VG = 2.4 l

Gastrointestinal
VG = 2.4 l
tG = 2.67 min
Liver
VL = 2.4 l
tL = 2.4 min

Perfusion interactions between

compartments are shown by arrows.
VG, VL, VC, and VM are -tissue water
volumes for the gastrointestinal,
liver, central and muscle
compartments, respectively.

Central
VC = 15.3 l
tC = 0.9 min

Muscle & Fat

VM = 22.0 l
tM = 27 min

VS is the stomach contents volume.

16

10/1/2010

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)
Dow, DuPont, Amoco, Chevron
Pharmaceutical Antivenom, Drug Delivery
Medicine Pharmacokinetics, Drinking and
Driving
Microelectronics CVD

17

CONVERSION AND REACTOR SIZING

Objectives:
Define conversion and space time.
Write the mole balances in terms of conversion for a
batch reactor, CSTR, PFR, and PBR.
Size reactors either alone or in series once given the
molar flow rate of A, and the rate of reaction, -rA, as
a function of conversion, X.

Conversion: Choose one of the reactants as the basis

of calculation and relate the other species involved in
the rxn to this basis.
Space time: the time necessary to process one
reactor volume of fluid based on entrance conditions
(holding time or mean residence time)

CONVERSION AND REACTOR SIZING

1. Conversion
Consider the general equation

aA
A + bB cC
C + dD
We will choose A as our basis of calculation.

b
c
d
A+ B C + D
a
a
a
The basis of calculation is most always the limiting reactant. The
conversion of species A in a reaction is equal to the number of moles of A
reacted per mole of A fed.

Batch

X=

Flow

( N A0 N A )
N A0

X=

(FA0 FA )
FA0

X = Moles of A reacted
Moles of A fed

For irreversible reactions, the maximum value of conversion, X, is

that for complete conversion, i.e. X = 1.0.
For reversible reactions, the maximum value of conversion, X, is the
equilibrium conversion, i.e. X = Xe.

2. Design Equations
Batch Reactor Design Equations:

Moles of A

reacted = Moles of A Moles of A reacted

fed
(consumed )
Moles of A fed

= [N A 0 ]

[X ]

[1]

Now the # of moles of A that remain in the reactor after a time t, NA can be
expressed in terms of NA0 and X;

[N A ] = [N A 0 ] [N A 0 X ]

[2]

N A = N A 0 (1 X )

dN A
= rA V
dt

( prefect mixing )

[3]

dN A
= rA V
dt

For batch reactors, we are interested in determining how long to leave the
reactants in the reactor to achieve a certain conversion X.

dN A
dX (Since N is constant)
A0
= 0 N A0
dt
dt
dX
N A0
= rA V
dt
Batch reactor design eqn
dX
N A0
= rA V
(in differential form)
dt

[4]

[5]

For a constant volume batch reactor: (V = V0)

1 dN A d ( N A / V0 ) dC A

=
=
V0 dt
dt
dt

From [3]

dC A
= rA
dt

Constant volume batch

reactor

dt = N A 0

dX
rA V

From [5]

Batch time, t, required

to achieve a
conversion X.

t = N A0
0

dX
rA V

As t

Flow Reactor Design Equations:

For continuous-flow systems, time usually increases with increasing reactor
volume.

FA0 X =

moles of A fed moles of A reacted

time
moles of A fed

FA0 FA0 X = FA
inlet molar
flow rate

Outlet flow rate

Molar flow rate at which A is

consumed within the system

F A = F A 0 (1 X )
FA0 = C

A0

v0

moles /volume

volume / time (volumetric flow rate, dm3/s)

For liquid systems, CA0 is usually given in terms of molarity (mol/dm3)

For gas systems, CA0 can be calculated using gas laws.
Partial pressure

C A0 =

PA 0
y P
= A0 0
R T0
R T0

Entering molar flow rate is

y P
FA0 = v0 CA0 = v0 A0 0
R T0

yA0

= entering mole fraction of A

P0

= entering
t i total
t t l pressure (kP
(kPa))

CA0

= entering concn (mol/dm3)

= 8.314 kPa dm3 / mol K

= T(K)

CSTR (Design Equation)

For a rxn:

A+

b
c
d
B C+ D
a
a
a

V =
Substitute for FA

FA0 FA
rA

FA = FA 0 FA 0 X
V =

FA 0 ( FA 0 FA 0 X )
rA

V =

FA 0 X
( rA ) exit

PFR (Design Equation)

dFA
= rA
dV
FA = FA0 FA0 X

dFA = FA0 dX
Substitute back:

dFA
dX
= FA 0
= rA
dV
dV

Seperate the variables V = 0 when X = 0

X

V = FA0
0

dX
rA

Applications of Design Equations for

Continuous Flow Reactors
3. Reactor Sizing
Given rA as a function of conversion, -rA = f(X), one can size any type of
reactor. We do this by constructing a Levenspiel Plot. Here we plot either
FA0 / -rA or 1 / -rA as a function of X. For FA0 / -rA vs. X, the volume of a
CSTR and the volume of a PFR can be represented as the shaded areas
in the Levelspiel Plots shown below:

Levenspiel Plots

A particularly simple functional dependence is the first order dependence:

rA = k C A = k C A0 (1 X )
Specific rxn rate
((function of T))

initial concn

For this first order rxn, a plot of 1/-rA as a function of X yields :

1
1
1
=

rA k C A0 1 X

-1/rA

Example: Lets consider the isothermal gas-phase isomerization:

AB
X

-rA(mol/m3s)

0 45
0.45

0.1

0.37

0.2

0.30

0.4

0.195

0.6
0.7

0.113
0.079

08
0.8

0 05
0.05

[T = 500 K]
[P = 830 kPa = 8.2 atm]
initial charge was pure A

Example: Lets consider the isothermal gas-phase isomerization:

AB
X

-rA(mol/m3s)

1 / -rA

0 45
0.45

2 22
2.22

0.1

0.37

2.70

0.2

0.30

3.33

0.4

0.195

5.13

0.6
0.7

0.113
0.079

8.85
12.7

08
0.8

0 05
0.05

20 0
20.0

[T = 500 K]
[P = 830 kPa = 8.2 atm]
initial charge was pure A

Draw -1/rA vs X:
We can use this figure to size flow reactors for
different entering molar flow rates.

-1/rA

Keep in mind :

1. if a rxn is carried out isothermally,

y, the rate is
usually greatest at the start of the rxn, when
the concn of reactant is greatest. (when x
0 -1/rA is small)
2. As x 1, rA 0 thus 1/-rA & V

An infinite reactor volume is needed to reach complete conversion.

For reversible reactions (A B), the max X is the equilibrium conversion
Xe. At equilibrium, rA 0.
As X Xe, rA 0 thus 1/-rA & V
An infinite reactor volume is needed to obtain Xe.

if FA0 = 0.4 mol/s, we can calculate [FA/-rA](m3)

Plot FA0/-rA vs X obtain Levenspiel Plot!
Example: Calculate volume to achieve 80 % conversion in CSTR.

find rA at X = 0.8
1
m3
= 20
mol s
rA 0.8
F X
V = A0
(rA ) exit
= 0.4
For instance:
3.6 m3

mol
m3
20
0.8 = 6.4m 3
s
mol s
CSTRs are usually used for liquid-phase rxns.

1.5 m3

4. Numerical Evaluation of Intergrals

The integral to calculate the PFR volume can be evaluated using a
method such as Simpsons One-Third Rule.

NOTE: The intervals (X) shown in the

sketch are not drawn to scale. They
should be equal.

Simpsons One-Third Rule is one of the most common numerical methods. It

uses three data points. One numerical methods for evaluating integrals are:
1. Trapezoidal Rule (uses two data points)
2. Simpsons Three-Eighths Rule (uses four data points)
3. Five-Point Quadrature Formula

Trapezoidal Rule

x1

f ( x) dx = h [ f ( x ) + f ( x )]
0

f(x)

x0

A1 = f ( x0 ) h

f(x1)

[ f ( x1 ) f ( x0 )] h
2
A = A1 + A2

A2 =

A2
f(x0)

A1
x0

x1

f ( x1 ) f ( x0 )

= h f ( x0 ) +

2
2

h
= [ f ( x0 ) + f ( x1 )]
2

Five Point Quadrature formula:

x4

f ( x) dx = 3 ( f

+ 4 f1 + 2 f 2 + 4 f 3 + f 4 ) where

h=

x0

xN

f ( x) dx =

x0

x 4 x0
4

3h
( f 0 + 3 f1 + 3 f 2 + 2 f 3 + 3 f 4 + 3 f 5 + 2 f 6 .....)
8

For N+1 points, where

N is an integer.

Example: Consider the liquid phase reaction;

A Products
which is to take place in a PFR. The following data was obtained in a
batch reactor.

0.4

0.8

-rA(mol/dm3s)

0.01

0.008

0.002

If the molar feed of A to the PFR is 2 mol/s, what PFR volume is

necessary to achieve 80 % conversion under identical conditions as
those under which the batch data was obtained?

10

Hint :
FA0 = 2 mol/s, fed to a plug flow reactor
X

PFR V = FA0
0

1
dX
rA

Thus one needs (1/-rA) as a function of X.

For Simpsons three point formula we have:

dX
X
= FA0
3

r
A
0

PFR : V = FA0

0.8

PFR : V = FA0
0

1
4
1
+
+

rA ( X = 0) rA ( X 1 ) rA ( X 2 )

dX
mol 0.4
dm 3 s
3
=2
[100 + 4 (125) + 500]
= 293dm
s 3
mol
rA

To reach 80 % conversion
conversion, your PFR must be 293
293.3
3 dm3.

11

Sizing in PFR
Example: Determine the volume in PFR to achieve a 80 % conversion.

For PFR : FA0

dX
= rA
dV
0 .8

0.8

dX
F
Re arranging : V = FA0
= A0 dX
rA 0 rA
0
Lets numerically evaluate the integral with trapezoidal rule
0.8

FA0

r
0

dX

f (X ) =

f (X ) =

V=

FA 0
rA

X =0

FA 0
rA

X = 0 .8

= 0.89
= 8 .0

0 .8
(0.89 + 8.0) = 8.89 0.4 = 3.556m 3
2
With five point quadrature V = 2.165 m3

Comparing CSTR & PFR Sizing

VCSTR > VPFR for the same conversion and rxn conditions.
The reason is that CSTR always
y operates
p
at lowest rxn rate. PFR starts at a high
g
rate, then gradually decreases to the exit rate.

12

Reactors in Series: The exit of one reactor is fed to the next one.
Given rA as a function of conversion, one can design any sequence of
reactors.

Xi =

moles of A reacted up to po int i

moles of A fed to first reactor

Only valid if there are no side streams.

FAi = FA0 FA0 X i

Example: Using Levenspiel plots to calculate conversion from known

reactor volumes.
Pure A is fed at a volumetric flow rate 1000 dm3/h and at a concentration of 0.005
mol/dm3 to an existing CSTR, which is connected in series to an existing tubular
reactor If the volume of the CSTR is 1200 dm3 and the tubular reactor volume is
reactor.
600 dm3, what are the intermediate and final conversions that can be achieved
with the existing system? The reciprocal rate is plotted in the figure below as a
function of conversion for the conditions at which the reaction is to be carried out.

13

Solution:
By trial and error, we find that a conversion of 0.6 gives the appropriate
CSTR volume of 1200 dm3.

Therefore, the intermediate conversion is X = 0.6

Similarly for the PFR, through trial and error, we find that a conversion
of 0.8 gives the appropriate PFR volume of 600 dm3.

Therefore, the final conversion is X = 0.8

14

CSTRs in Series
Two CSTRs in series

Reactor 1:
Mole Balance: FA0 FA1 + rA1 V1 = 0
FA1 = FA0 FA0 X1

FA0

[1]
[2]

Combining [1] & [2]:

FA1
X1 = 0.4

V1 = FA0 (1 / -rA1) X1

[3]

Mole Balance: FA1 FA2 + rA2 V2 = 0

[4]

-rA1

Reactor 2:
-rA2

FA2
X1 = 0.8

FA2 = FA0 FA0 X2

[5]

Combining [4] & [5]:

V2 =

FA1 FA 2 ( FA0 FA0 X 1 ) ( FA0 FA0 X 2 ) FA0

=
=
( X 2 X1)
rA 2
rA 2
rA 2

if we have the data:

X = 0.4

FA0

= 2.05m 3
rA1 X =0.4

X = 0.8

FA0

= 8 .0 m 3

A 2 X = 0 .8

F
V1 = A0 X 1 = 0.82m 3
rA1 0.4
F
V2 = A0 ( X 2 X 1 ) = 3.2m 3
rA 2

-FA0/rA

VCSTR,2 > VCSTR,1

X
0.4

0.8

Total V = V1 + V2 = 4.02 m3 < 6.4 m3

volume necessary to get 80 %

conversion with one CSTR

15

One can approximate a PFR by a large # of CSTRs in series:

-FA0/rA

4
X
n

V PFR = VCSTR ,i
i =1

PFRs in Series
FA0
-rA1

FA1
X1 =0.4
-rA2

X2

FA0
0

VTOTAL = VPFR,1 + VPFR,2

FA2
X1 = 0.8
X

1
2
dX
dX
dX
= FA0
+ FA0
rA 0
rA X 1
rA

The overall conversion of

two PFRs in series is the
same as one PFR with the
same total volume

Reactors in Series: CSTR PFR CSTR

Using the data in the table, calculate the reactor volumes V1, V2 and V3
for the CSTR/PFR/CSTR reactors in series sequence along with the
corresponding conversion.

16

F
Use the plot of A0 vs. X
rA

(a) The CSTR design equation for Reactor 1 is:

F X
V1 = A 0

rA1
at X = X1 = 0.4 the (FA0 / -rA1) = 300 dm3
V1 = (300 dm3) (0.4) = 120 dm3
The volume of the first CSTR is 120 dm3

(b) Reactor 2: PFR The differential form of the PFR design is

dX
rA
=
dV
FA0
Rearranging and intergrating with limits
when V = 0

X = X1 = 0.4

when V = V2

X = X2 = 0.7
0.7
FA0
F
dX = A0 dX
V =
rA
rA
X1
0.4
X2

17

Choose three point quadrature formula with

X =

V2 =

X 2 X 1 0.7 0.4
=
= 0.15
2
2

FA0
4 FA0
FA0
+
+

rA (0.4) rA (0.55) rA (0.7)

X
3

Interpreting for (FA0/-rA) at X = 0.55 we obtain

FA0

= 370dm 3

r
A X =0.55
V2 =

0.15
300dm 3 + 4 (370dm 3 ) + 600dm 3 = 119dm 3
3

The volume of the PFR is V2 = 119 dm3

(c) Reactor 3: CSTR

Balance

in out + generation
FA 2 FA3 + rA3 V3 = 0
V3 =

FA 2 FA3
rA3

FA 2 = FA0 (1 X 2 )
FA3 = FA0 (1 X 3 )
V3 =

FA0
(X3 X2)
rA3

V3 = 600dm 3 (0.7 0.4) = 180dm 3

The volume of last CSTR is 180 dm3

18

Summary:
CSTR X1 = 0.4

V1 = 120 dm3

PFR

X2 = 0.7
07

V2 = 119 dm3

CSTR X3 = 0.8

V3 = 180 dm3

Total volume = 120 + 119 + 180 = 419 dm3

Reactor Sequencing
Is there any differences between having a CSTR PFR system & PFR
CSTR system? Which arrangement is best?

or

The volumes are different!

V1 + V2 =? V3 + V4
V1

V2

V3

V4

For isothermal rxns

FA0

The choice of reactors depend on ;

the Levenspiel plots
relative reactor sizes.
X
Adiabatic rxns

19

Space Time
The space time, tau, is obtained by dividing the reactor volume by
the volumetric flow rate entering the reactor:

V
v0

Space time is the time necessary to process one volume of reactor

fluid at the entrance conditions. This is the time it takes for the amount
of fluid that takes up the entire volume of the reactor to either
completely enter or completely exit the reactor. It is also called holding
time or mean residence time.

Example: v0 = 0.01 m3/s and V = 0.2 m3 = 0.2 m3 / 0.01 m3/s = 20 s

It would take 20 s for the fluid at the entrance to move to the exit.

Typical space time for different reactors:

Batch : 15 min 20 h (few kg/day 100,000 tons/year 280 tons/day)
CSTR : 10 min 4 h

(10 to 3 x 106 tons/yr)

Tubular: 0.5s
0 5s 1h

(50 to 5 x 106 tons/yr)

20

Space Velocity (SV) is defined as:

SV =

v0 1
=
V

instead of using volumetric flow rate at the entrance, you use liquid
hourly & gas hourly space velocities (LHSV, GHSV).
v0 (for LHSV) is that of a liquid feed rate at 60F or 75F.
v0 (for GHSV) is that of the one that measured at STP.

LHSV =

v0 liq
V

GHSV =

v0 STP
V

21

 HW (due date: Feb 25):

Solve
S l th
the prpblem
bl
iin your own way.
http://www.engin.umich.edu/~cre/web_mod/hippo/index.htm

Suggested problems from the web:

http://www.engin.umich.edu/~cre/
htt //
i
i h d /
/
Additional Homework Problems at each
chapter

Example: Consider cell as a reactor. The nutrient corn steep liquor enters the cell of the
microorganism Penicillium chrysogenum and is decomposed to form such products as
amino acids, RNA and DNA. Write an unsteady mass balance on (a) the corn steep liquor,
(b) RNA, and (c) pencillin. Assume the cell is well mixed and that RNA remains inside the
cell.

In

Out

Corn Steep Liquor

Penicillin
Penicillium chrysogenum

Assumption:
Penicillin is produced in the stationary state.
no cell growth & nutrients are used in making the product.

22

Mass balance for penicillin:

In Out + Generation = Accumulati on

dN p
Fin + Fout + G p =
dt
Fin = 0 ( no penicilin in _ flow )
V
V
dN p
G p = rp dV rp dV Fout =
dt

Assuming steady state for the rate of production of penicilin in the cells
stationary state,
dN p
=0
dt
F Fout
F
V = in
V = out
rp
rp
Similarity, for Corn Steep Liquor with FC = 0
V =

FC 0 FC
F
= C0
rC
rC

No RNA is generated or destroyed.

Summary
Batch

X=

Flow

( N A0 N A )
N A0

X=

(FA0 FA )
FA0

X = Moles of A reacted
Moles of A fed

For irreversible reactions, the maximum value of conversion, X, is

that for complete conversion, i.e. X = 1.0.
For reversible reactions, the maximum value of conversion, X, is the
equilibrium conversion, i.e. X = Xe.

23

dX
N A0
= rA V
dt

V=

FA0 X
(rA ) exit
X

V = FA0
0

dX
rA

Batch reactor design eqn

(in differential form)

CSTR

PFR

Reactors in series

Space time

V
v0

24

Ch 3. Rate Laws and Stoichiometry

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)

Part 1: Rate Laws

Basic Definitions:
A homogenous rxn is the one that involves only one phase.
A heterogeneous rxn involves more than one phase, rxn occurs at the interface
between the phases, i.e., solid gas phase.
An irreversible rxn proceeds in only one direction A B
A reversible rxn can proceed in both directions A B (equilibrium)
Molecularity of a rxn is the number of atoms, ions, or molecules involved in a rxn
step.
The terms unimolecular, bimolecular, and termomolecular refer to rxns involving,
respectively, one, two or three atoms interacting in any one rxn step.
Unimolecular: radioactive decay
Bimolecular: rxns with free radicals Br. + X XBr + Y.
Termolecular: rxn pathway following a series of bimolecular rxns.

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.
1. Relative Rates of Reaction
aA + bB cC + dD

Rate of formation of C = c/a (Rate of disappearance of A)

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/dm3s, what are the rates of B and C?
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

(2A + 3B 5C)

The rate of disappearance of B, -rb, is

Species C
The rate of formation of species C, rc, is

Rxn Order & Rate Law:

Algebraic equation that relates rA to the concentrations of the reactants
is called the kinetic expression or rate law.
Usually, rate can be written as the product of rxn rate constant and
concentrations. In these expressions, usually the limiting reactant is
chosen as basis for calculations.
-rA = kA(T) fn (CA, CB,..)
In reality activities should be used
rA = -kA aA aB
(ai = i Ci)
rA = (-kA A B) CA CB
kA

Power Law and Elementary Rate Laws

In general
-rA = kA CA CB
: order in A
: order in B
n = + = overall rxn order
The unit of rA is always = concentration / time
For a rxn with n order:
{k} = (concentration)1-n / time
Therefore for a zero-, first-, second-, and third-order rxn
zero order ( n = 0)
1st order (n = 1)
2 nd order (n = 2)

rA = k A ;

rA = k AC A ;

{k} =
{k} =

rA = k AC A ;

mol
dm3 s

1
s

{k} =

dm3
mol s
2

3 order (n = 3)
rd

rA = k AC A C B ;

dm3 1
s
{k} =

mol

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 (A + B C + D), the rate law
would be: -rA = k CA CB These rate laws can be derived from Collision
Theory.

if 2NO + O2 2NO2 then rNO = kNO (CNO)2 CO2 if elementary!!!

Question
What is the reaction rate law for the reaction A + B C 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/s)

Solution:

A+BC

Lets calculate the rate if,

Then,

For A + B C + D

C C
rA = k C A C B C D
KC

Elementary

Non Elementary Rate Laws:

A large number of homogeneous or heterogeneous rxns do not follow
simple rate laws.
If the rate law for the non-elementary reaction A + B 2C + D is found to
be rA = k CA CB2, then the rxn is said to be 2nd order in A and 1st order in
B, and 3rd order overall.
For the homogeneous rxn

CO + Cl 2 COCl 2
2 N 2 O 2 N 2 + O2

rCO = k C CO C Cl 2
rN 2O =

k C N 2O
1 + k 'C O2

3/ 2

k and k strongly
temperature
dependent

In this case we can not state overall rxn order.

Here, we can speak of reaction orders under certain limiting conditions

as at very low concn of O2 (1 >> k CO2)

rN 2O = k N 2O C N 2O
If 1 << k CO2 rN2O

rN 2O =

k N 2O C N 2O
k 'CO2

1st order (apparent rxn order)

0th order (apparently)

These types are very common for liquid & gas phase rxns on solid
catalysts

For the heterogeneous rxn

C6 H 5CH 3 + H 2 catalyst
C6 H 6 + CH 4
(toluene: T)

(benzene: B) (methane: M)

In these types of rxns, partial pressures are used instead of concns:

Specific rxn rate {k} = molT / kg cat s atm2

rT ' =

k PH 2 PT
1 + K B PB + K T PT

Per mass of catalyst

Adsorption constant
{KT} = 1 / atm

if ideal gas law is applied Pi = Ci R T

Example: Gas Phase Catalytic Reactions

When studying gas phase catalytic reactions the rate law is developed
in terms of partial pressure,

To rewrite the rate law, just use ideal gas law to relate to concentrations
CA and CB

and then write concentration in terms of conversion

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 0 and the rate law must reduce to an equation
that is thermodynamically consistent with the equilibrium constant for the
reaction.
Example: Consider the exothermic, heterogeneous reaction;
A+BC
At low temperature, the rate law for the disappearance of A is

Recall PA = CA R T

At high temperature, the exothermic reaction is significantly reversible:

What is the corresponding rate law?

If the rate of formation of A for the forward reaction (A + B C) is

then we need to assume a form of the rate law for the reverse reaction
that satisfies the equilibrium condition. If we assume the rate law for the
reverse reaction (C A + B) is

Then:

and:

Deriving rA:
The forward rate is:
And the reverse rate law is:

The net rate for species A is the sum of the forward and reverse rate laws:

Substituting for rfor and rrev:

Solving for Kp:

Does this rate law satisfy our requirement at equilibrium.
For a rxn at equilibrium

At equilibrium, rnet 0, so;

Solving for Kp:

The conditions are satisfied.

Rate Law for Reversible Reactions

Example: 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.
(1)
(2)

At equilibrium

The equilibrium constant decreases as T

increases (exothermic rxns)
Ke increases as T increases (endothermic rxns)

10

Reaction Rate Constant, k:

k is the specific rxn rate constant given by Arrhenius Equation:
k = A eE/RT
where,
E: activation energy (cal/mol)
R: gas constant (cal/mol K)
T: temperature (K)
A: frequency factor (unit depends on rxn order)
k

T kA
T0 k0
A 1013
T

EA (Activation Energy)
Molecules need some energy to distort/stretch their bonds so that they
break them to form new bonds.
The steric & repulsion forces must be overcome as the reacting
molecules come close together.

A
2a

C
b+c

B
a+b

C
a+c

11

A rxn coordinate is usually used:

A + BC A B C AB + C
High energy complex
EA-B-C

Energy Barrier

EA + EBC
EAB + EC

Rxn Coordinate
The rxn coordinate denotes the energy of the system as a function of
progress along the reaction path.

More on Activation Energy

The activation energy can be thought of as a barrier to the reaction. One
way to view the barrier to a reaction is through the reaction coordinates.
These coordinates denote the energy of the system as a function of
progress along the reaction path. For the reaction

the reaction coordinate is

for the reaction to occur, the reactants must overcome an energy barrier
or activation energy EA.

12

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
Energy Distribution of reacting molecules
In our development of collision theory we assumed all molecules had the
same average energy. However, all the molecules dont have the same
energy, rather there is distribution of energies where some molecules
have more energy than others. The distraction function f(E,T) describes
this distribution of the energies of the molecules. The distribution function
is read in conjunction with dE
f(E, T) dE = fraction of molecules with energies between E and E + dE

One such distribution of energies in the following figure

13

Increase Temperature

By increasing the temperature we increase the kinetic energy of the

reactant molecules which can in turn be transferred to internal energy to
increase the stretching and bending of the bonds causing them to be in
an activated state, vulnerable to bond breaking and reaction.
As the temperature is increased we have greater number of molecules
have energies EA and hence the reaction rate will be greater.

14

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

If you know two points EA is known!

ln k
1
( )
T
E
slope =
R

slope =

One can also write the specific reaction rate as:

15

Specific Reaction Rate Derivation

Taking the ratio:

This says if we know the specific rxn rate ko(To) at a temperature To, and
we know E, then we can find reaction rate k(T) at any other temperature
T for that rxn.

STOICHIOMETRY
We shall set up Stoichiometric Tables 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).

16

1. Batch System Stoichiometric Reactor

where;
and

Concentration -- Batch System:

Constant Volume Batch:
Note:
if the reaction occurs in the liquid phase
or
if a gas phase reaction occurs in a rigid (e.g., steel) batch reactor
Then

if

then

and we have -ra=f(x)

17

Example:
Write the rate law for the elementary liquid phase reaction
3A + 2B 4C
solely in terms of conversion. The feed to the batch reactor is equal molar
A and B with CA0 = 2 mol/dm3 and kA= .01 (dm3/mol)41/s.
1) Rate Law: -rA=kCA3CB2
2) Stoichiometry:
Species A
Liquid phase, v = vo (no volume change)

Species B

What is B?
Species A is the limiting reactant because the feed is equal molar in A
and B, and two moles of B consumes 3 moles of A.

We now have -rA=f(X) and can size reactors or determine batch reaction times.

18

2. Flow System Stoichiometric Table

Where:

and

Concentration -- Flow System:

Liquid Phase Flow System:

etc.

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

This gives us -rA = f(X). Consequently, we can use the methods discussed
in Chapter 2 to size a large number of reactors, either alone or in series.

19

For Gas Phase Flow Systems: (Variable Volumetric Flow Rate)

Combining the compressibility factor equation of state with Z = Z0
FT=CTV

with

FTo=CToVo

we obtain
The total molar flow rate
Substituting for FT gives:

yA0 =
holds for both
flow & batch
reactors

Example: Calculate
For the gas phase reaction
2A + B C
the feed is equal molar in A and B. Calculate .
Solution
A is the limiting reactant

20

Gas Phase Flow Systems

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

The molar flow rate of A:

FA = FA0 + A (FA0 X)
Stoichiometric coefficient

FA = FA0 ( + A X)

21

Calculating the equilibrium conversion for gas phase reaction

Consider the following elementary reaction with KC and = 20 dm3/mol
and CA0 = 0.2 mol/dm3. Pure A is fed. Calculate the equilibrium
conversion, Xe, for both a batch reactor and a flow reactor. Assume
constant volume.

Solution
At equilibrium

Stoichiometry

Constant Volume V = V0

22

Solving

23

Stoichiometric Table - Conversion

Lets 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
kT=250(dm6/mol2s). The entering pressure is 8.2 atm and the entering
temperature is 227C and the reaction takes place isothermally with no
pressure drop.

24

Basis of Calculation
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.
Entering Concentrations of ethylene and toluene
Let A = toluene, B = ethylene, C = ethyl benzene and D = propylene

Ethylene

Since toluene, i.e. A, is the limiting reactant and has a stoichiometric

coefficient of 1

Leaving FB

25

Complete the stoichiometric table including coolant flow rates

Write the volumetric flow rate in terms of conversion

P = P0 and T = T0

In terms of conversion
For a flow system at constant T and P

26

In terms of conversion

We now have rA solely as a function of X

27

Summary
We learned to write the rate expression for a given reaction
A B
or A B
Meaning of rate constant, activation energy
k= A e {-E/RT}

Summary
1. Batch System Stoichiometric Reactor (similarly for CSTR and PFR!!)

where;
and

28

ISOTHERMAL REACTOR DESIGN

In Chapter 1 & 2, we discussed balances on batch & flow reactors. In
Chapter 3, we discussed rxns. Here, we will combine rxns and
reactors.
Topics
Part 1: Mole Balances in Terms of Conversion
1. Algorithm for Isothermal Reactor Design
2. Applications/Examples of CRE Algorithm
3. Reversible Reactions
4. ODE Solutions to CRE Problems
5. General Guidelines for California Problems
6. PBR with Pressure Drop
7. Engineering Analysis
Part 2: Measures Other Than Conversion
1. Measures Other Than Conversion
2. Membrane Reactors
3. Semibatch Reactors

Part 1: Mole Balances in Terms of Conversion

1. Algorithm for Isothermal Reactor Design
The algorithm for the pathway of interest can be summarized as:
1. Mole Balance and Design Equation

(choose reactor type)

2. Rate Law

(choose rxn type; gas or liq. phase)

3. Stoichiometry
4. Combine
5. Evaluate
The Evaluate Step can be carried out
A. Graphically (Plots)
B. Numerically (Quadrature Formulas)
C. Analytically (Integral tables)
D. Using Software Packages

Elementary gas phase reaction in different reactor types

CSTR
The elementary gas phase reaction 2A + B C
takes place in a CSTR at constant temperature (500 K) and constant pressure
(16.4 atm). The feed is equal molar in A and B. x = 0.9, k= 10dm6/mol2s
VCSTR =?

Mole balance
Rate Law
Stoichiometry gas phase, isothermal (T = T0), no pressure drop (P = P0)

Derivation

Combine

Evaluate

PFR and Batch Reactors

Elementary Gas Phase Reaction: 2A + B C
PFR
Mole Balance
Rate Law
Stoichiometry

gas phase, isothermal (T = T0), no pressure

drop (P = P0), CAo=CBo (=1), v=vo(1+X)

Combine

Parameter Evaluation

CAo=0.2, v=vo=25 dm3/s, k=10 dm6/mol2 s, =-0.5,

X=0.9

V=227 dm3

Deriving CA and CB
Remember that the reaction is:
For a gas phase system:

If the conditions are isothermal (T = T0) and isobaric (P = P0):

We must divide by the stoichiometric coefficient of our basis of

calculation yielding:

And if the feed is equal molar, then:

This leaves us with CA as a function of conversion alone:

Similarly for CB:

Batch Reactor Constant Volume, V=Vo and the pressure changes.

Mole Balance

Rate Law
Stoichiometry

Combine

Parameter Evaluation

CAo=0.2, k=10 dm6/mol2 s,

Scale Up of Liquid Phase Batch Reactor Data to Design of a CSTR:

Scale Up a lab experiment to pilot plant operation of full scale
production. Find k from experimental data and use it to design a full scale
flow reactor.
Batch Operation:
Liquid phase: (density change is small V = V0)
Gas phase with constant volume V = V0.
1 dN A

= rA
V dt
1 dN A 1 dN A dN A / V0 dC A

=
=
= rA
=
V dt V0 dt
dt
dt
Since concn is a measured quantity in liquid phase rxns:

dC A
= rA
dt

Lets calculate the time necessary to achieve a given conversion X for

the irreversible second order rxn:
AB

dX
N A0
= rA V0
dt
2
rA = k C A
C A = C A0 (1 X )

[1]
[2]
[3]

Combine [1], [2] and [3];

dX
= k C A0 (1 X ) 2
dt
Rearrange:

dX
= k C A0 dt
(1 X ) 2

@ t = 0; X = 0; T = T0 (isothermal) k constant
t

t =
0

1
k C A0

dX

(1 X )
0

t=

1
X

k C A0 1 X

It is important to know the reaction time, tR, to achieve a certain

conversion.
Flow reactors use characteristic rxn times, tR.
The time for a total cycle is much longer than tR, as one must account for
the time to fill (tF), heat (th) and clean (tC).
t = tf + th + tC + tR
Design of Continuous Stirred Tank Reactors
CSTRs are usually used for liquid phase rxns:

V=

FA0 X v0 C A0 X
=
( rA ) exit
rA

Divide by v0:

[1]

V C A0 X
=
v0
rA

(Design Eqn for CSTR)

[2]

Volumetric flow rate

A single CSTR:
First order irreversible rxn:

rA = k C A
C A = C A0 (1 X )
1 X

k 1 X
k
X=
1+ k

Combine [4] and [6]

CA =

[3]
[4]

Combine [2], [3] and [4]

[5]
[6]

C A0
1+ k
rxn Damkhler #,
Da: a dimensionless # that for a first order rxn

says the degree of conversion that can be achieved in cont. flow reactor.

Da =

rate of rxn of A
rA0 V
:
FA0
rate of convective transport of A t =0

For a second order rxn:

rA0 V k C A0 V
=
= k C A0
FA0
v0 C A0
2

Da =

Da 0.1
Da 10

X < 0.10
X > 0.90

X=

Da
1 + Da

First order liq-phase rxn (Eqn [6])

CSTRs in Series
CA1, X1
CA0

For first order rxn (v = v0)

CA2, X2
-rA1

-rA2

V1

V2

The effluent concn of reactant

A from the first CSTR is

C A1 =

C A0
1 + 1 k1

where 1 =

V1
v0

From the mole balance on reactor 2:

V2 =
Solving for CA2:

C A2 =

FA1 FA2 v0 (C A1 C A2 )
=
rA2
k2 C A2

C A1
C A0
=
1 + 2 k 2 (1 + 2 k 2 )(1 + 1 k1 )

( 1 = 2 = )

If both reactors are of equal size,

and operate at the same T (k1 = k2 = k)

C A2 =

C A0
(1 + k ) 2

for n equal sized CSTR system

C An =

C A0
C A0
=
n
(1 + k )
(1 + Da) n

Substituting for CAn in terms of conversion

C A0 (1 X ) =
X = 1

C A0
(1 + Da) n

1
1
= 1
n
(1 + Da)
(1 + k ) n

CSTRs in Parallel:
Equal sized reactors are placed in parallel rather than in series:
FA01

X1

FA02

FA03

X2

X3

FA0n

Xn

Individual volume is given by

X
V = FA0i i
rAi
Since Vi = Vj, then Xi = X;

[1]

-rA1 = -rA2 = ...... = -rA

V
Vi =
n
FA0
FA0i =
n

[2]
[3]

Substitute [2] & [3] into [1]

V FA0 X i
X
= FA0
.
=
n
n rAi
rA

[4]

10

Example: 2nd order rxn, v = v0, CA = CA0 (1-X); FA0 X = v0 CA0 X

Combine rA = k CA2 and V = FA0 X / -rA

V=

FA0 X
v0 C A0 X
=
2
2
k CA
k C A0 (1 X ) 2

Divide by v0:

V
X
=
v0 k C A0 (1 X ) 2

(1 + 2 k C A0 ) (1 + 2 k C A0 ) 2 (2 k C A0 ) 2
X=
2 k C A0
X=

(1 + 2 Da) 1 + 4 Da
2 Da

Since k C A0 = Da
for a second order rxn.

Since X can not be greater than 1.0, ( - ) sign is chosen.

Example: The elementary liquid phase reaction

is carried out isothermally in a CSTR. Pure A enters at a volumetric flow

rate of 25 dm3/s and at a concentration of 0.2 mol/dm3.
What CSTR volume is necessary to achieve a 90% conversion when k = 10
dm3/(mol*s)?
Mole Balance
Rate Law
Stoichiometry

liquid phase (v = vo)

11

Combine

Evaluate

at X = 0.9,

V = 1125 dm3
Space Time

2. Applications/Examples of the CRE Algorithm

12

Applying the algorithm to the above reaction occuring in Batch, CSTR, PFR

13

3. Reversible Reaction
To determine the conversion or reactor volume for reversible
reactions, one must first calculate the maximum conversion that can
be achieved at the isothermal reaction temperature, which is the
equilibrium conversion. (See Example 3-8 in the text for additional
coverage of equilibrium conversion in isothermal reactor design.)
Equilibrium Conversion, Xe

Calculate Equilibrium Conversion (Xe) for a Constant Volume System

Example: Determine Xe for a PFR with no pressure drop, P = P0
Given that the system is gas phase and isothermal, determine the reactor
volume when X = 0.8 Xe

First calculate Xe:

Equilibrium constant Kc is;

C Be
2
C Ae
= C A0 (1 X e )

KC =
C Ae

1
C Be = C A0 X e
2

Xe = 0.89
X = 0.8Xe = 0.711

14

Deriving The Equilibrium Constant (KC) and Equilibrium

Conversion (Xe) for a Non-Constant Volume System:
The reversible reaction:

which takes place in gas phase PFR. Since gas phase reactions almost
always involve volume changes, we will have to account for volume
changes in our calculations. The equilibrium constant, KC, for this
reaction is:

A is the limiting reactant A B/2

where CAe and CBe are:

Substituting for CAe and CBe gives us:

Substituting known values (CA0 = 0.2 mol/dm3 and KC = 100 dm3/mol),

and realizing that:

Solving for the equilibrium conversion, Xe, yields:

Xe = 0.89

15

Batch Reactor With a Reversible Reaction

The following reaction follows an elementary rate law

Initially 77% N2, 15% O2, 8% inerts are fed to a batch reactor where 80%
of the equilibrium conversion (Xe = 0.02) is reached in 151 s. What is
the specific reaction rate constant k1?

Additional Information

16

For 80% of equilibrium conversion X = 0.8 Xe = 0.016

Use Simpson's three point formula to integrate

with X = 0.016/2 = 0.008

17

Tubular Reactors:
Gas-phase rxns are usually carried out in tubular reactors where the gas
is generally turbulent.

Reactants

Products
No radial variation in velocity, concn, T or rA.

Design Eqn:

FA0

dX
= rA
dV

In the absence of pressure drop or heat exchange, integral form of the

design equation is used:
X

V = FA0
0

dX
rA

Pressure Drop in Reactors

In liquid-phase rxns, the concn of reactants is not effected by the
changes in pressure.
However, in gas phase rxns, concn is propotional to total pressure.
Pressure Drop & Rate Law
Example: Analyze the following second order gas phase reaction
that occurs isothermally in a PBR:

Mole Balance
Must use the differential form of the mole balance to separate variables:

Rate Law
Second order in A and irreversible:

18

Stoichiometry
Isothermal, T = T0

Combine

Need to find (P/P0) as a function of W (or V if you have a PFR).

Pressure Drop in Packed Bed Reactors

Ergun Equation

P = pressure (kPa)
Dp = diameter of particle (m)
= porosity = volume of void / total bed volume
1 = volume of solid / total V
gC = 1 (metric)
= viscosity of gas (kg / m s)
z = length down the packed bed (m)
u = superficial velocity = v0 (volumetric flow) / A2 (cross-area)
= gas density (kg/m3)
G = u = superficial mass velocity (kg/m2 s)

m = m (st st )
0

0 v0 = v

Ergun, S., 1952. Fluid flow through packed columns. Chemical Engineering Progress 48, pp. 8994.

19

Variable Density

Catalyst Weight

Then

We will use this form for multiple reactions:

Since

FT = FT 0 + FA0X = FT 0 1 + A0 X
FT 0

F
FT
= y A0 = A0
= 1+ X
FT 0
FT 0

20

when <0;

P will be less than = 0.

when >0;

P will be greater than = 0.

Isothermal Operation

Recall that

Notice that

The two expressions are coupled ordinary differential equations. We can solve
them simultaneously using an ODE solver such as Polymath. For the special
case of isothermal operation and epsilon = 0, we can obtain an analytical
solution.

Analytical Solution

2y

, [e], PFR with

dy
=
dW

y = 1 ( P = P0 ) @ W = 0
y 2 = 1 W

CAUTION: Never use this form if

21

Combine

Solve

Could now solve for X given W, or for W given X.

For gas phase reactions, as the pressure drop increases, the concentration
decreases, resulting in a decreased rate of reaction, hence a lower
conversion when compared to a reactor without a pressure drop.

Effect of presure drop on P,rate, conn, and x.

22

Pressure Drop in Pipes:

Pressure drop for gases flowing through pipes without packing can be
neglected. For flow in pipes, P is given by:

dP
du 2 f G 2
= G

dL
dL
gD
Where
G = u (g/cm3s) = mass velocity is constant along L.
u = average velocity of gas, cm/s.
f = fanning friction factor
f = fnc (Re, pipe roughness

P
4 f G 2 V
1/ 2
= 1
= (1 pV )
P0 0 P0 AC D

Example p 187

23

Optimum Particle Diameter

Laminar Flow, Fix P0, 0,

0 = P0(MW)/RT0
0P0 P02

Cross-sectional area
Superficial mass velocity = u

24

Increasing the particle diameter descreases the pressure drop and increases
the rate and conversion.

However, there is a competing effect. The specific reaction rate decreases as the
particle size increases, therefore so deos the conversion.
k 1/Dp

DP1 > DP2

k1 > k2
Higher k, higher conversion

25

The larger the particle, the more time it takes the reactant to get in and out
of the catalyst particle. For a given catalyst weight, there is a greater
external surgace area for smaller particles than larger particles. Therefore,
there are more entry ways into the catalyst particle.

7. Engineering Analysis - Critical Thinking and Creative Thinking

We want to learn how the various parameters (particle diameter,
porosity, etc.) affect the pressure drop and hence conversion. We need
to know how to respond to "What if" questions, such as:
"If we double the particle size, decrease the porosity by a factor of 3, and
double the pipe size, what will happen to D P and X?"
To answer these questions we need to see how a varies with these
parameters

Turbulent Flow

26

Compare Case 1 and Case 2:

For example, Case 1 might be our current situation and Case 2 might be
the parameters we want to change to.

For constant mass flow through the system

= constant

Laminar Flow

Part 2: Mole Balances in terms of Concn & Molar Flow Rates

In some cases, it is more convenient to deal with number of moles or
molar flow rates rather than conversion.
Membrane reactors and multiple rxns taking place in gas phase are
examples.
The main difference in molar flow rates, you have to write the mole
balance on each and every species.
Membrane reactors can be used to increase conversion when the rxn is
thermodynamically limited as well as to increase the selectivity when
multiple rxns are occuring.
A. Membrane reactors
B. Multiple reaction
Liquids: Use concentrations, i.e., CA

27

1. For the elementary liquid phase reaction

carried out in a
CSTR, where V, vo, CAo, k, and Kc are given and the feed is pure A, the
combined mole balance, rate laws, and stoichiometry are:

There are two equations, two unknowns, CA and CB

Gases: Use Molar Flow Rates, I.E. FI

2. If the above reaction,

,carried out in the gas phase in a
PFR, where V, vo,CAo,k, and Kc are given and the feed is pure A, the
combined mole balance, rate laws, and stoichiometry yield, for isothermal
operation (T=To) and no pressure drop (P=0) are:

28

 Microreactors

Are characterized by their high surface area to volume ratios (due to many
micro-tubes and channels). Dchannel = 100m, Lch= 2 cm
Control of heat and mass transfer resistance!!
They are used for highly exothermis rxns, for rxns with toxic or explosive
intermediates. ALso,i for the productions of speciality chemicalsi
combinatorial chemical screening, chemical sensors.

In modeling, we assume they are PFR. dFa/dV = rA

29

Membrane Reactors
Membrane reactors can be used to achieve conversions greater than the original
equilibrium value. These higher conversions are the result of Le Chatelier's
Principle; you can remove one of the reaction products and drive the reaction to
the right. To accomplish this, a membrane that is permeable to that reaction
product, but is impermeable to all other species, is placed around the reacting
mixture.

Example: The following reaction is to be carried out isothermally in a membrane

reactor with no pressure drop. The membrane is permeable to Product C, but it is
impermeable to all other species.

For membrane reactors, we cannot use conversion. We have to work in

terms of the molar flow rates FA, FB, FC.
Mole Balances

Rate Laws

30

Stoichiometry
Isothermal, no pressure drop

Combine

Polymath will combine for you

Parameters

Solve

Polymath

3. Semibatch Reactors
Semibatch reactors can be very effective in maximizing selectivity in liquid
phase reactions.
kD
A + B
D ( product )
kU
A + B
U

(undesired )

rD = k D C A C B
2

rU = kU C A C B

Selectivity ( D / U ) =

kD C A
kU C B

The reactant that starts in the reactor is always the limiting reactant

31

Three Forms of the Mole Balance Applied to Semibatch Reactors

If you have multiple reactions, use concentrations to make mole balances!!

ODE Solutions to CRE Problems

dX rA
=
dV FA0
2

(1 X ) C A0 X
rA = k C A0

1 + X 2(1 + X ) K C

[V, X] = ode45(@vdp1, [0 500], [0])

Matlab solution

32

Example: Elementary Irreversible Reaction

Consider the following irreversible elementary reaction

-rA = kCACB
The combined mole balance, rate law, and stoichiometry may be written
in terms of number of moles, conversion, and/or concentrati

Polymath Equations

33

Equilibrium Conversion in Semibatch Reactors with Reversible

Reactions
Consider the following reversible reaction:

Everything is the same as for the irreversible case, except for the rate law

Where:

At equilibrium, -rA=0, then

34

function f=volume(V,x)
Ca0=0.2;
Kc=100;
Fa0=5;
k=2;
epsilon=-0.5;
ra=k*(((Ca0*(1-x(1))/(1+epsilon*x(1)))^2)(Ca0*x(1)/(2*Kc*(1+epsilon*x(1)))));
f(1)=ra/Fa0;

[V x]=ode45('volume',[0 500],[0]);
plot(V,x)
grid
xlabel('Volume')
ylabel('conversion')

0.9
0.8
0.7
0.6
conversion

>>
>>
>>
>>
>>

0.5
0.4
0.3
0.2
0.1
0

50

100

150

200

250
300
Volume

350

400

450

500

35

function f = packedbed(W,x)
alpha = 0.0002;
k = 10;
epsilon = -0.5;
FA0=2.5;
CA0 = 0.2;
f = zeros(2,1);
CA = (CA0*(1-x(1))*x(2))/(1 + epsilon*x(1));
ra = k*(CA.^2);
f(1) = ra / FA0;
f(2) = -alpha*(1 + epsilon*x(1))/(2*x(2));
>>
>>
>>
>>
>>
>>
>>

[W x]=ode45('packedbed', [0 1000], [0;1]);

plot(W,x(:,1))
xlabel('W, kg')
ylabel('X')
plot(W,x(:,2))
xlabel('W, kg')
ylabel('y')

1.001

0.999

0.998

0.997

0.996

0.995

10

20

30

40

50
W , kg

60

70

80

90

100

1
0.9
0.8
0.7
0.6
X

0.994

0.5
0.4
0.3
0.2
0.1
0

10

20

30

40

50
W , kg

60

70

80

90

100

36

Combining mole balances, rate laws and

stoichiometry

37

Pressure Drop in Packed Bed Reactors

Ergun Equation

P = pressure (kPa)
Dp = diameter of particle (m)
= porosity = volume of void / total bed volume
1 = volume of solid / total V
gC = 1 (metric)
= viscosity of gas (kg / m s)
z = length down the packed bed (m)
u = superficial velocity = v0 (volumetric flow) / A2 (cross-area)
= gas density (kg/m3)
G = u = superficial mass velocity (kg/m2 s)

m = m (st st )
0

0 v0 = v

Ergun, S., 1952. Fluid flow through packed columns. Chemical Engineering Progress 48, pp. 8994.

For gas phase reactions, as the pressure drop increases, the concentration
decreases, resulting in a decreased rate of reaction, hence a lower
conversion when compared to a reactor without a pressure drop.

Effect of presure drop on P,rate, conn, and x.

38

Part 2: Mole Balances in terms of Concn & Molar Flow Rates

In some cases, it is more convenient to deal with number of moles or molar flow rates
rather than conversion.
Membrane reactors and multiple rxns taking place in gas phase are examples.
Microreactors with multiple reactions

39

Chapter 5
Collection & Analysis of Rate Data
There are some basic steps in Analysis of Rate Data
1. Postulate a rate law:
a) Power law model for homogeneous rxns:

rA = k C A C B

b) Langmuir Hinshelwood for heterogeneous rxns:

k PA PB
(1 + K A PA + PB ) 2

rA ' =

2. Select reactor type; i.e.; Batch, CSTR, PFR, PBR......

3. Process your data in term of measured variables (NA, CA or PA)
4. Do simplifications (assumptions), if rA = k CACB and CA>>CB
-rA k CB

5. For batch reactors, find reaction order

i. Find (- dCA / dt) from CA vs t data.
Take ln.
Find the order of rxn by ln (- dCA / dt) = ln k + ln CA
Find the rate constant, k.
ii. Integral Form:
dC

A = k CA
dt
Integrate
1
1
t = C A0 ........
k

6. For PBR, find rA as a function of CA or PA.

SUMMARY
Differential Method:
dC A

= k A CA
dt
slope =

dC
ln A = ln k A + ln C A
dt

kA =

dC
ln A
dt

dC
ln A
dt P

ln C A

(dC A / dt )P
(C AP )

ln C AP

We should differentiate the concentration-time data either

graphically or numerically.
1. Graphical differentiation
2. Numerical differentiation formula
3. Differentiation of a polynomial fit to the data.

1. Graphical
Tabulate (CAi, ti) observations and for each interval calculate
Cn = Cn Cn-1 tn = tn tn-1
ti

Ci

t0

C0

t1

CA

CA/ t

t1 t0

C1 C0

(CA/ t)1

C1

(dCA / dt)1
t2 t1

t2

C2 C1

(CA/ t)2

C2

(dCA / dt)2
t3 t2

t3

(dCA / dt)

C3 C2

(CA/ t)3

C3

Plot these values as a histogram

Draw a smooth curve
Read estimates of (dCA/dt) at t1, t2, ......
x = xn xn-1
y = yn yn-1
Plot these
n

y n y1 =
i=2

y n y1 =

xn

y
xi
xi

dy

dx dx

x1

B
C

Try to find

Area(A) Area(B)
A+CB+D

Numerical Methods
If the data points are equally spaced, i.e., t1 t0 = t2 t1 = t
time (min)
Concn

(mol/dm3)
For initial point

interior point

End point

t0

t1

t2

...........

CA0

CA1

CA2

...........

3C A0 + 4C A1 C A2
dC A

=
2 t
dt t0

1
dC A
C A( i +1) C A( i 1)

=
dt
2
t

ti

1
dC A
C A( n 2 ) 4C A( n 1) + C A( n )

=
dt tn 2t

Polynomial fit:
Fit the concn time data to an nth order polynomial as:

C A = a o + a1t + a 2 t 2 + a 3 t 3 + a 4 t 4 ......a n t n
Find best values for {a o , a 1 , a 2 ,........, a n }
dC A
= a 1 + 2 a 2 t + 3a 3 t 2 + ......n a n t n -1
dt

Integral Method
We first guess the rxn order and integrate the differential equation used to
model the batch system. If the order is correct, the plot of concn time data
should be linear.
This method is used when rxn order is known but EA and kA are unknown.

Non Linear Regression

Non Linear LeastLeast-Square Analysis
We want to find the parameter values (alpha, k, E) for which the sum of
the squares of the differences, the measured rate (rm), and the calculated
rate (rc) is a minimum.
# of parameters to be determined

# of runs

That is we want
to be a minimum.
For concentration-time data, we can integrate the mole balance equation
for -rA = k CAalpha to obtain

We find the values of alpha and k which minimize S2

dC A

= k CA
dt
k dt = dC A C A
k t =

1
1
C A + Const
1
1

Const =

C A0
1
1

C A = 1 C A0

(1 )k t

Vary and k, obtain S2 (or use a search technique)

S(, k) is a minimum (optimization methods)

Concentration vs Time Equations for the proposed rate equations can be

done by differential or integration method.
Ex.: Liquid phase rxn btw trimethylamine(A) and n-propyl bromide (B)
was studied by Winkler & Hinshelwood. The results at 139.4oC are
shown below. Initial solns of A & B in benzene, 0.2 molal, were mixed
and placed in constant temperature bath. After certain times, they were
cooled to stop the rxn. Determine the first order and second order
specificrates, k1 and k2, asssuming the rxn is irreversible. Use integration
& differential methods.
Run

t, min

x (%)

13

11.2

34

25.7

59

36.7

120

55.2

Soln:

dC A
= k1 C A
dt
dC A
2 nd order - rA =
= k2 C A CB
dt

1st order - rA =

A + B C+ + DVolume is constant

Integration Method

1st order
- ln

CA
= k1 t
C A0

[1]

2 nd order
Stoichiome tric coefficien ts are equal and C A0 =C B0 = 0.1 molal
dC A
2
= k2 C A
dt
1
1

= k2 t
C A C A0

x=

C A0 C A
C A0

[2]

C A = C A 0 (1 x )

For the first run

C A =0.1 0.888

Substitute in [1]
1 C
1
0 .1
= 1 .54 10 4 sn 1
k 1 = ln A0 =
ln
t
C A 13 60 0 .0888
Substitute in [2]
k2 =

L
1 1
0 .112

1 =
= 1 .63 10 3
t C A0 1 - x
gmol s
(13 60 ) 0 .1 (1 0 .112 )

If you repeat for four of the runs:

Run

t, sec

k1 x 10-4 (s-1)

k2 x 10-3 (L/mol s)

CD

780

1.54

1.63

0.0112

2040

1.46

1.70

0.0257

3540

1.30

1.64

0.0367

7200

1.12

1.71

0.0552

-ln(CA /CA0)

0.5

800

1600

2400

3200
4000
time, sec

4800

5600

6400

7200

800

1600

2400

3200
4000
time, sec

4800

5600

6400

7200

1/CA -1/CA0

15

10

So, it is SECOND ORDER

Differential Method
CD = CA0 CA (moles of D produced = moles of A reacted)
CD = x CA0
A plot of CD vs t
0.06

[D] moles/L

0.05
0.04
0.03
0.02
0.01
0

r=

dC A dC D
=
dt
dt

1000

2000

3000

4000
time, sec

5000

6000

7000

8000

(the slope of the curve)

Slopes determined from the curve are given as follows

CD

CA

r = dCD/dt (105 gmol/L)

0.0

0.10

1.58

0.01

0.09

1.38

0.02

0.08

1.14

0.03

0.07

0.79

0.04

0.06

0.64

0.05

0.05

0.45

log rA = log k1 + log CA

(from rA = k1 CA)

log rA = log k2 + log CA2 = log k2 + 2 log CA

(from rA = k2 CA2)

1st: log r vs log CA should yield a straight line with a slope of 1.0.
2nd: log r vs log CA should yield a straight line with a slope of 2.0.

log r = -2.76 + 2.0 log CA

The data suggest a slope of 2!
log k2 = -2.76
k2 = 1.73 x 10-3 L / mol s

log r

slope = 2.0

log CA

Another Way (Batch Reactor Data)

B + A products
-rA = kA CACB if and are both unknown, the rxn could be run in an
excess of B so that CB remains essentially unchanged

- rA = k'C A where k' =k A C B k A C B0

In determining , the rxn is carried (excess of A)

- rA = k' 'C B where k' ' =k A C A k A C A0

Solving with search

S 2 = C Am,i C A0
i =1

i =1

(1 )k ti

1 / 1

CD

CA

780

0.0112

0.0888

2040

0.0257

0.0743

3540

0.0367

0.0633

7200

0.0552

0.0448

S = C Am,i abs C
2

1
A0

(1 )k ti

1 / 1

fminsearch

Method of Initial Rates

If there is a reverse rxn, it could render the differential method ineffective.
In these cases, initial rates could be used for k & .
Carry out a series of experiments with different CA0.
Determine rA0 for each run.
-rA0 = k CA0

ln(-rA0) vs ln(CA0)

Instead of doing at different time steps, repeat the rxn.

Method of Half Lives:

The half life of a rxn, t, is defined as the ime it takes for the concentration
of the reactant to fall to half of its initial value.
If you know t, find k & .
If there are more than 1 reactant, use method of excess.

rA = k C A

( A products )

dC A

= rA = k C A
dt

@t = 0
t=

C A = C A0

CA =

1
C A0
2

1
1
1
1

1
k ( 1) C A
C A 0

C
1
A0
t=
k ( 1) C A

t1 / 2

@ t = t1 / 2

2 1 1 1

=
k ( 1) C A 0

Similarly

t1 / n

n 1 1 1

=
k ( 1) C A 0

10

ln t1/ 2 = ln

2 1
+ (1 ) ln C A0
( 1)k

ln t1/ 2

slope = 1

ln C A 0

Differential Reactors

A differential reactor is used to determine the rate of a rxn as a function of

either concentration or partial pressure
L
FA0

FAe

FA0

FAe
W

Conversion is very small in bed

CA is constant CA0 (gradientless)
Rxn rate is uniform
(almost isothermal)

Design Equation is similar to a CSTR:

Rate of rxn
(mass of cat ) = 0
mass of cat
FA0 FAe + rA 'w = 0
FA0 FAe +

FA0 FAe
w
v C v C Ae
(in terms of conc' n)
rA ' = 0 A0
w
F x F
rA ' = A0 = P (in terms of flow rate)
w
w
v (C C Ae ) v0 (C P )
=
rA ' = 0 A0
w
w
rA ' =

11

Deviations from Ideal Reactors

When the mixing criteria of ideal reactors are not satisfied,
mathematical expressions for the conservation equations become more
difficult.

Deviations from ideal stirred tank reactors

a) Stagnant regions
b) by passing

Deviations from tubular-flow

a) Longtidunal mixing due to vortices and turbulence
b) Laminar flow (poor radial mixing)
c) By-passing in fixed-bed catalytic reactor.

12

Chapter 6 MULTIPLE REACTIONS

If there are multiple rxns, use concentrations not conversions.
intermediate

Consecutive rxns

1. Series Reactions
2. Parallel Reactions

3. Complex Reactions:
Series and Parallel

4. Independent

None of the products or reactants

are common.

These might occur in combination or by themselves.

Desired & Undesired Rxns

We want to get the desired product, D and avoid the formation of
undesired one, U.
kD
In the parallel rxn A
D
kU
A
U

In series

kU
kD
A
D
U

D
Cost

Reactor

Total Cost

Reactor Cost

Seperator
Seperator Cost

Low

Efficiency

High

Selectivity and Yield

Selectivity tells us how one product is favored over another when multiple
rxns take place

Exit flow rate

For batch

S DU =

ND
NU

tend

Reaction yield = ratio of the

rxn rate of a given product to
the rxn rate of key reactant A.

Determine the instantaneous selectivity, SD/U, for the liquid phase reactions:
A+B
D

rD = k 1 C A C B

A+B
U 1

rU 1 = k 2 C A C B

A+B
U 2

rU 2 = k 3 C A C B

Sketch the selectivity as a function of the concentration of A. Is there an

optimum and if so what is it?
2

SD/U1U 2 =

Find the optimum

concentration

rD
k1C A C B
k1C A
=
=
rU1 + rU 2 k 2 C A C B + k 3C A 3C B k 2 + k 3C A 2

dS
*2
*
*
= 0 = k1 k 2 + k 3C A k1C A 2k 3C A
dC A
CA =
*

k2
k3

Parallel Rxns:
For the following competing rxns
kD
A
D

(desired)

kU
A
U

(undesired )

rD = k D C A

rU = k U C A

Rate of disappeara nce of A

- rA = rD + rU = k D C A 1 + k U C A

where 1 and 2 are positive rxn orders.

S D/U =

rD k D

=
CA 1 2
rU k U

Maximizing the Desired Product for one Reactant

Case1:

If 1 > 2 SD/U =

kD

CA 1 2
kU

SD/U

as C A

kD
1

k U C A 2 1

SD/U

as C A

Case2:

If 1 < 2 SD/U =

In Case 1: If gas rxn, we should run it without any inerts and at high
pressures to keep CA high.
If liquid phase rxn, the diluents should be minimum. CSTR should not be
used, batch or plug flow should be used.
In Case 2: Dilute the feed with inerts. CSTR should be used, because CA
decreases rapidly.

Effect of Temperature on Selectivity

It can be determined from

SD/U ~

k D A D -([E D -E U ]/RT)
=
e
kU AU

where A : freq factor,

E : activation energy
SD/U

Rxn should be operated at the highest

possible T to max. SD/U

ED > EU
T

SD/U

ED < EU
T

2. Series Reactions

This series reaction could also be written as

Reaction (1)
Reaction (2)

Species A:

Species B:

Using the integrating factor, i.f.:

at t = 0, CB = 0

When should you stop the reaction to obtain the maximum amount of B?
Let's see

Then

And

The Integrating Factor

(1)
If you only had an expression of the form

(2)

things would be much easier, then you could integrate with respect to z
and find y(z).
(3)
then you could manipulate equation (3):
(4)
where the term in brackets is the left hand side of equation (1). You need
du/dz = u f(z). Recall
(5)

If you define

and f(z) = dq/dz (i.e.

, then

(6)
This satisfies the condition that du/dz=u f(z). Therefore,
and substituting into equation (4),
(7)

where the term in brackets is the left hand side of equation (1).
CONCLUSION: If your problem is of the form

you can multiply both sides of the equation by the

(which you should be able to evaluate, since you know f(z)), to yield

or, substituting from equation (7)

Derivation

f(t)=k2, so

From equation (12), the solution is then

The constant can be obtained from the intitial condition that at t=0, CB=0;

3. Algorithm for Multiple

Reactions

Reactor Selection & Operating Conditions:

Consider two simultaneous rxns

k1
A + B
D

rD = k 1C A 1 C B

k2
A + B
U

rU = k 2 C A 2 C B

S D/U =

rD k 1
( )
( )
=
CA 1 2 CB 1 2
rU k 2

We usually want to max SD/U. So the reactors should be designed to max SD/U
B
B

H>>0

A
A

H>>0

A
D

Thermodinamically limited rxns A + B <-> C + D

Algorithm for Solution of Complex Reactions:

In combinations of parallel and series rxns, ODE solver packages
make life easier.

Write the rxns

Write the mole balances

Net rate laws

Stoichiometry

Combine & Solve

4. Applications of Algorithm
(1)
(2)

NOTE: The specific reaction rate k1A is

defined with respect to species A.
NOTE: The specific reaction rate k2C is
defined with respect to species C.

Case 1: PFR
Mole Balances
dF A
A:
dV
dF B
B:
dV
dF C
C:
dV
dF D
D:
dV

Rate Laws
= rA
= rB
= rC
= rD

rA = r1A + r2A

Species A

r1A = -k 1A C A C B

For reaction (1):

r1B = 2r1A
r1C = -r1A
r1A = -k 1A C A C B

- r2A
-r
= 2C
2
3
2
2
3
2
r2A = ( -r2C ) = k 2C C C C A
3
3
1
r2D = r2C
3
2
2
3
2
rA = k 1A C A C B k 2C C C C A
3

For reaction (2):

Species A
Species B

rB = r1B = 2 k 1A C A C B

Species C

rC = k 1A C A C B k 2C C C C A

Species D

rD = r2D =

2
3

r2C 1
3
2
= k 2C C C C A
3
3

Writing the net rates

Stoichiometry

liquid : v = v0
FA = CAv0

Combine
Species A

dC A rA
=
dV v 0
dC A
=
dV

Species B

2
2
3
2
k1A C A C B k 2C C C C A
3
v0

dC B rB
=
dV v 0

k1A = 0.5

dC B 2k1A C A C B
=
dV
v0
Species C

k2C = 2.0
v0 =5.0

dC C rC
=
dV v 0

@ t=0; V=0, CA0=4, CB0=4, CC0=0, CD0=0

dCC k1A C A C B k 2C C C C A
=
dV
v0
2

Species D

Evaluate solution using Polymath of

MatLab

Vf = 5 dm3

dC D rD
=
dV v 0
3

dC D 1 k 2C C C C A
=
v0
dV 3

10

Case 2: CSTR

(FA0 - FA )
v 0 (C A0 - C A )
=
2
2
3
2
- rA
k1A C A C B + k 2C C C C A
3
( F - F ) v (C - C )
V = B0 B = 0 B0 B2
- rB
2k1A C A C B
V=

Species A

Species B
Species C

V=

(FC0 - FC ) FC
v 0CC
=
=
- rC
rC k1A C A C B 2 k 2C C C 3C A 2

Species D

V=

(FD0 - FD ) FD
v 0C D
=
=
- rD
rD 1 k C 3C 2
2C C
A
3

We will specify V, CA0, CB0 along with the specific reaction rates kij.
This formulation leaves us with four equations and four unknowns (CA,
CB, CC and CD)

2
3
2
f(C A ) = - V k 1A C A C B + k 2C C C C A + v 0 (C A0 - C A )
3

f(C B ) = - V 2k 1A C A C B + v 0 (C B0 - C B )

f(C C ) = V k 1A C A C B k 2C C C C A v 0 C C
2

1
3
2
f(C D ) = V k 2C C C C A v 0 C D
3

11

Case 3: Semibatch Liquid Phase

Species A
Species B
Species C
Species D

dC A
dt
dC B
dt
dC C
dt
dC C
dt

= k 1A C A C B
2

2
vC
3
2
k 2C C C C A 0 A
3
V

v0 [C B0 C B ]
2
2 k 1A C A C B
V
vC
2
3
2
= k 1A C A C B k 2C C C C A 0 C
V
v0 C D
1
3
2
= k 2C C C C A
V
3

FB0

V = V0 +v 0 t
Parameters

dm 6
mol2 hr

k 2C = 2

dm 3
hr
Initial conditions

C B0 = 4

k1A = 0.5
v 0 = 1.2

dm 2
mol4 hr

mol
V0 = 2dm 3
dm 3
C Ai = 4 C Bi = 0 C Ci = 0 C Di = 0

t f = 8 hr

PolyMath Solutions

12

THE ALGORITHM
Mole balances

Rate Laws

Relative rates
Rxn (1) A + 2B ->C

Rxn (2) 2A + 3C ->D

Net rates
Species A
Species B
Species C
Species D

2
3
2
k 2C C C C A
3

Species A

rA = k 1A C A C B

Species B

rB = r1B = 2 k 1A C A C B

Species C

rC = k 1A C A C B k 2C C C C A

Species D

rD = r2D =

Stoichiometry

CA =

2
3

r2C
1
3
2
= k 2C C C C A
3
3

FT0 FA0 P T0
F
P T

= C T0 A0 0
v 0 FT0 P0 T
FT0 P0 T

13

Combine

P = 0, P = P0 , T =T0
Ci =C T0

Fi
FT

Species A

dFA
2
2
3
2
= k1A C A C B k 2C C C C A
dV
3

Species B

dFB
3 F F
= 2k1A C T0 A B
dV
FT0 FT0

Species C

dFC
1
3 F F
5 F
= k1A C T0 A B k 2C C T0 C
dV
F
F
3
FT0
T0 T0

Species D

dFD 1
5 F
= k 2C C T0 C
dV 3
FT0

FA

FT0

FA

FT0

FT = FD +FC + FB +FA
Parameters

k1A = 0.05, k 2C = 1.3

Initial Cond.

V = 0, FA = 10, FB = 20, FC = 0, FD = 0, Vf = 200

For a CSTR

C T0 = 0.8

Species A

V=

(FA0 - FA )
- rA

Species B

V=

(FB0 - FB )
- rB

Species C

V=

(FC0 - FC )
- rC

Species D

V=

(FD0 - FD )
- rD

Total :

FT = FD +FC + FB +FA

Five equations five unknowns

X=

FA0 - FA
FA0

14

ConcentrationConcentration-Time Trajectories
1. The following concentration-time trajectories were observed in a batch
reactor

Which of the following reaction pathways best describes the data

2. Sketch the concentration-time trajectory for the reaction

Solution: Part 1
Choice B is the answer. Choices A and C are incorrect because they
show species B eventually consumed, which is clearly not the case

15

Solution: Part 2

(1) B virtually consumed so no more D can be produced in reaction 2.

(2) Rates of Consumption of A and Ba are virtually the same.
(3) Rate of consumption of B greater than that of A owing to Reaction 2

16

Ch. 7 Reaction Mechanisms, Pathways, Bioreactions and Bioreactors

Active Intermediates and Non-elementary Rate Laws:
Usually we have seen that rate can be expressed as:
-rA = k CA where = 1, 2, 3, 0
However, a large # of rxns, the orders are non-integers
Rate laws may also involve a # of elementary rxns and at least one active
intermediate.
Active intermediate is a high energy molecule that reacts virtually as fast as it is
formed.

It is found in small amounts and shown as A*.

A + M A* + M
The high E is stored in the chemical bonds where high-amplitude oscillations
lead to bond ruptures, molecular rearrangement and decomposition
Collision
Free radicals, unpaired e Ionic intermediates
Enzyme-substrat complexes
In 1999, Ahmed Zewail got Nobel for fentosecond spectroscopy.

Pseudo-steady-state Hypothesis (PSSH)

The PSSH assumes that the net rate of species A* is zero.
rA* 0
The reaction
has an elementary rate law

However

Why does the rate law decrease with increasing temperature?

Mechanism:

(1)
(2)
(3)

Assume that reactions (1) and (2) are elementary reactions, such that

The net reaction rate for

is the sum of the individual reaction rates for

The PSSH assumes that the net rate of

if

k3
[NO] << k 2
2

if

k3
[NO] >> k 2
2

if k 2 >>
rNO2 =

[NO 3 *] =
[NO 3 *] =

is zero:

k1
[NO][O 2 ]
k2

2 k1
[O 2 ]
k3

k3
[NO] at low NO conc' n : since rNO 2 =k 3 C NO3 C NO
2

k1 k 3
A A
[NO] 2 [O 2 ] = 1 3 e
k2
A2

E 2 - (E 1 + E 3 )
RT

[NO] 2 [O 2 ]

if E2 > (E1 + E3) as T increases r decreases.

Apparent rxn order at low concns: 2nd order with NO
Apparent rxn order at high concns: 1st order with NO

you can say

Rxns consist of
a) Activation step
b) Deactivation step
c) Decomposition step

If you have

+
A

M
A*

k1
A + M
A * + M (for A P)
k2
A * + M
A+M
k3
A *
P

write the rate of formation of P : rp =k 3 C A *

rp = - rA =

k 3 k1 C A C M
k 2 CM + k 3

if C M is constant (inert) rp =k C A 1st order rxn

Searching for a Mechanism

In many cases the rate data are correlated before a mechanism is found.
If you have

rP =

k 1k 3 C A
k 2CA + k 3

rP =

k1C A
1 + k' C A

Steps in Mechanism Search

1. Species having concns appearing in the denominator of the rate law probably
collide with the active intermediate
A + A* Products
2. If a constant appears in the denominator, one of the rxn steps is probably the
spontaneous decomposition of the active intermediate
A* Decomposition products
3. Species having concns in the numerator probably produce the active
intermediate
Reactant A* + Other Products

1. Assume an active intermediate

2. Postulate a mechanism
3. Model each rxn as an elementary rxn
4. Write the rate laws for active intermediates
5. Use PSSH
6. Eliminate intermediate species
7. If the law obeys the experiment, OK.

Example 7-1 (pg 384)

Example: Chain rxns will have steps:

1. Initiation : Formation of active intermediate
2. Propagation : Interaction of A* with reactant
3. Termination : deactivation of A*
Active Intermediate C2H6 2CH3.
Reaction pathways help us to see the inter-connections for multiple rxns.
Metabolic pathways are examples.

Enzymatic Rxn Fundamentals

Enzymes (E) are proteins with catalytic properties. They act on substrates (S).
They increase the rate by 103 to 1017 times!
The rxn coordinate for enzyme catalysis:

E +S E S P + E

SP

E S

Active intermediate
(enzyme substrate
complex)

Enzymes are highly specific (1 enzyme 1rxn), remain unchanged and can be used over and over.
A typical enzyme will catalyze the rxn of about 1000 substrate molecules every second.
Although concn are low, how do they bind specifically, motions are enormously fast at molecular level. It
takes a small molecule 0.2 sec to diffuse a distance of 10 m. Active site will be bombarded by about
500,000 random collisions with the substrate molecule per second.
They are named by the type of rxn they catalyze (-ase).

E
S

E
+

If the enzyme is exposed to extreme T or pH it will denature.

(unfolding will make the active site disappear)

Two models for SE interactions.

1. Lock & Key Model
S

+
E S

2. Induced fit model

E
E
S

+
S

E
P

Mechanisms
As an example, we will look at urea decomposition by urease.
2O
S + E H

P+E

The corresponding mechanism:

k1
E + S
E S

(1)

E S E + S

(2)

k2

E S + W P + E (3)
k3

Corresponding rate laws are

r1S = - k1 (E) (S)
r2S = k 2 (E S)
r3P = k 3 (E S) (W)

Net rate of disappearance of S is: (-rS)

- rS = k1 (E) (S) - k 2 (E S)

(*) (from 1)

Net rate of formation of E-S complex

rES = k1 (E) (S) - k 2 (E S) - k 3 (W) (E S)

(combine 1 with 2 and 3)

Using PSSH, rES = 0

(E S) =

k1 (E) (S)
k 2 +k 3 (W)

(**)

Substitute into (*)

- rS = k1 (E) (S) - k 2

k1 (E) (S)
k 2 + k 3 (W)

Rearranging :
- rS =

k1 k 3 (E) (S) (W)

k 2 + k 3 (W)

But still there is (E) : unbound enzyme conc' n, but we can measure total enzyme conc' n :
(E t ) = (E) + (E S)
Solving for (E) using (**)
E=

(E t ) (k 2 + k 3 (W))
k 2 +k 3 (W) + k1 (S)

Substituting back in - rS =
- rS =

k1 k 3 ..........
k 2 + .........

k1 k 3 (E t ) (S) (W)
k1 (S) + k 2 + k 3 (W)

Michaelis Menten Eqn:

For a given enzyme concn, a sketch of rate of disappearance of the substrate is
shown as a function of substrate concn:
-rs
Vmax

Michaelis Menten Plot

Vmax/2

Km

where Vmax is the maximum rate of rxn S

for a given total enzyme concn.
Km is callad the Michaelis Menten constant, it is the measure of attraction of the enzyme for its
substrate (~affinity constant)
The Km is equal to substrate concn at which the rate of rxn is equal to one-half of its max rate.
- rs =

Vmax (S)
K m + (S)

At low substrate conc' n, K m >> (S)

- rs =

Vmax (S)
the rxn is 1st order
Km

At high conc' n, K m << (S)

- rs Vmax

t he rxn is zero order

Product Enzyme Complex:

In many rxns, the Enzyme and Product Complex (E-P) is formed directly from the
(E-S) complex as:
E +S E S E P E + P
Applying PSSH to (E S) and (E P), we obtain :
- rs =

Vmax (Cs - C p / K c )
Cs + K max +K p C p

{Briggs - Haldane Rate Law}

Batch Reactor Calculations for Enzyme Rxns:

Lets start writing the mole balance on urea in a batch reactor.

Urea + Urease 2NH 3 + CO 2 + Urease

- dN urea
= -rurea V
(1)
dt
In liq. phase {C V = N} and V is constant
- dC urea
= -rurea
dt

(2)

Rate Law :
- rurea =

Vmax C urea
K m + C urea

(3)

Substitute (3) into (2) :

C urea,0

t=

C urea

dC urea
=
- rurea

C urea,0

C urea

K m + C urea
dC urea
Vmax C urea

(4)

Integrate
t=

C
C
- C urea
Km
ln urea,0 + urea,0
Vmax
C urea
Vmax

(5)

Rewrite Eq' n (3) in terms of X : C urease = C urease,0 (1 - X)

t=

C
-X
1
Km
+ urea,0
ln
Vmax
Vmax 1 - X

(6)

Determine Km and Vmax from batch reactor data using integral method. Divide
both sides of (6) by (t Km / Vmax)

C
X
1
V
1
ln
= max urea,0
t 1- X Km
Km t

(7)

where a =

1
1
ln
t 1- X

Draw a vs (X / t): slope = - Curease,0 / Km

intercept = Vmax / Km

From a different approach, rewrite M-M Eqn in terms of S:

Multiply by S0 (LHS of (7))

S0 (1 - X) = S and C urease,0 = S0
S0 X = S 0 - S
1 S0 Vmax S0 - S
ln =
t S
Km Km t

1 S0
ln
t S

intercept = Vmax / Km

S0 : initial conc' n of substrate

slope = - 1 / Km

S0 S / t

Effect of temperature on Enzymatic Rxns

A very complex issue!
If the enzyme did not unfold, the rate would probably follow a Arrhenius
temperature dependence.
However, at a certain temperature the enzyme will denature and its activity will
be lost!
Therefore, we will first have an increase and then decrease:

temp. nactivation { thermal denaturation}

Vmax
T

Inhibition of Enzyme Reactions:

Temperature, pH and the presence of an inhibitor influences the rates. Even the
inhibition of a single (critical) enzyme may be fatal:
E.g.: Cyonide will cause the aerobic oxidation to stop when bound to cytochrome
oxidase death (the whole pathway will be affected)
Asprin inhibits the enzyme used in synthesis of pain-producing reactants
Types of Enzyme Inhibition
Competitive

E+I

I E (Inactive)

Uncompetitive

ES+I

I E S (Inactive)

Non-competitive

ES+I

I E S (Inactive)

IE+S

I E S (Inactive)

Lets look at them individually

10

Competitive Inhibition
Very important in drug design:
I competes with the substrate for the enzyme

E +S E S E P
E+I EI
k1
[1] E + S
E S
k2
[2] E S
E+S
k3
[3] E S
E+P
k4
[4] I + E
E I (inactive)
k5
[5] E I
E+I

rp = k 3 (E S)

(1)

Applying PSSH
rE,S = 0 = k 1 (E) (S) - k 2 (E S) + k 3 (E S)

(2)

Similarly :
rE I = 0 = k 4 (E) (I) - k 5 (E I)
The enzyme conc' n :
E t =E + (E S) + (E I)
Combining (1), (2), (3) and (4) :
rp = - rs =

Vmax S

I
S + K m 1 +
KI

Vmax = k 3 E t

Vma x and K m are unchanged!

and K m =

k2 + k3
k1

and K I =

k5
k4

I
K m ' > K m (apparent M - M constants)
Say K m ' = K m 1 +
KI
means a larger S is needed for the decomposition of S.
To reach it 1 Vmax
2

11

Rearrangin g :

1 +
{Lineweave r Burk}
K
I

As I increases the slope increases and - rS decreases.

1
1
1 Km
=
+
- rS Vmax S Vmax

1
- rS

I2 > I1

Comp. inhibition I1
No I

1
Vmax

1
S

Uncompetitive Inhibition
I has no affinity for the enzyme itself but for (E S) complex.
E +S E S E + P
+
I
k2
E S I

k1
E + S
E S
k2
E S
E+S
k3
E S
P+E
k4
I + E S
I E S (inactive)
k5
I E S
I + E S

12

we have :
1
1 Km
1
=
+
- rs
S Vmax Vmax
where K I =

I
1 +

K
I

k5
k4

1
- rS

Uncomp Inh. I2 > I1

Uncomp Inh. (I1)
No Inh.

1
S
Slope remains constant, I increases, Intercept increases, -rS decreases.

Non Competitive Inhibition (Mixed Inhibition)

I and S bind to different sites on E!

E +S E S E + P
+

KI

K I'

E I+S E SI

E +S

E S

E + I

I S (inactive)

I + E S I E S (inactive)
S+ IE

I E S (inactive)

E S P

13

We have:

1
1
=
rs Vmax

1
- rS

I 1 Km
1 +
+
K I S Vmax

I2 > I1

I
1 +

KI

I1
No Inh

1
S
Both the slope and intercept increase as I increases.

Summary to compare three types of inhibition

1
- rS

Non comp
Uncomp
Competitive
No Inh.

1
S
Substrate Inhibition
In some cases, S can act as a inhibitor. If we have uncompetitive substrat
inhibition:

S+ E S SE S
- rs =

Vmax S
K m + S + S 2 /K I

(1)

(replace I with S in normal uncomp inh.)

14

K m >> S + S2 / K I

- rs ~

Vmax S
Km

at high conc' n S2 / K I >> K m + S

- rs =

Vmax K I
S

at low conc' n

-rS
-rSmax

Smax = K m K I (from

- drs
= 0)
dS

Smax

Multiple E and S Systems:

We will look at multiple E and multiple S systems in which cyclic
regeneration of the activated E occurs.
Enzyme Regeneration:
Glucose (SR) is oxidized to -gluconolactone (P) by glucose oxidase (E0)

SR + E 0 SR E 0 P E R P + E R
E R cannot be used in further catalysis rxns, to regenerate :
E R + O 2 E 0 + H 2O 2
Overall
E

0
SR + O 2
H 2O 2 + P

Glucose (SR)
-gluconolactone (P)

E0

H2O2

ER

O2

Enzyme Cofactors
In enzymatic rxns, a second substrate is needed to activate the enzyme. Cofactor /
coenzyme bind to the enzyme
Unbound enzyme: apo-enzyme

Bound enzyme: holo-enzyme

15

Bioreactors
A bioreactor is a special reactor that sustains and supports life for cells and
tissue cultures. The use of living cells to produce marketable chemical products
made the biotechnology a growing industry. Chemicals, agricultural products,
food, etc.
Some organic chemicals are thought to be produced by living cells instead of
petroleum.
The advantages are mild rxn conditions, high yields and stereospecific
compounds.
Bacteria can be modified to be used as chemical factories.
In biosynthesis, the cells are called as biomass.

Nutrients

Cell

Products

The chemical rxns are simultaneous in the cell

We have
i)

Nutrient degradation (fueling) rxns, ATP molecules are used to provide

energy.

ii) Synthesis of small molecules (like aa, nucleotides)

iii) Synthesis of large molecules (like polymerization off aa to form proteins)

Cell Growth & Division

The four phases of cell division G1, S, G2 and M
The cell division eqn can be written as

More cells + Product

Substrate cells
Carbon, Nitrogen, Oxygen and Phosphate are some of the substrates.

16

Cell Growth
The number of living cells as a function of time can be shown in a batch reactor as:
Lag cell concn

In Phase I : lag phase, there is little

increase in cell concn. Cells are
adjusting to their new environment,
synthesizing enzymes, getting ready
to reproduce.

Phase II: exponential growth phase. Cell divide at maximum rate, all of the
enzymes pathways are in place.
Phase III: Stationary phase: Cells reach a minimum biological place where the one
or more of the nutrient are limiting.
Phase IV: Death phase: A decrease in live cell concn occurs.

Rate Laws
The most commonly used rate expression for
Cell + Substrate More cells + Product
is the Monod eq.n for exp growth.

rg = C c

Cell concn (g/dm3)

Cell Growth Rate

(g/dm3s)

Specific growth rate (s-1)

= max

Cs
K s +Cs

max : max spec. growth rate

rg = max

Cs C c
K s +Cs

Cs : Substrate (nutrient) concn (g/dm3)

Ks : Monod constant (g/dm3)

For most of the bacteria Ks is small (~10-5 mol/dm3) rg = max CC

17

Growth rate, rg, depends on the nutrient concn (Cs)

rg

Cs

In many systems, product inhibits the growth rate. Wine production is an

example, fermentation of glucose to produce ethanol is inhibited by the product
ethanol (ethanol kills the yeast)

rg = k obs

max Cc Cs
K s + Cs

where

k obs

Cp

= 1 C *
p

{Monod Eq.' n}

Cp * : product conc' n at which metabolism stops (g/dm 3 )

n : emprical constant

There are also Tessier & Moser eqns that fit experimental data better.
The cell death rate is given by

rd = (kd + kt Ct) Cc
Concn of the substance toxic to the cell

Effect of Temperature can be given as

rg

(T) = (Tm) I'

a T e -E1/RT
1 + b e -E 2 /RT
where

I' =
T

I' : fraction of max growth rate

Tm : temp. at which max growth occurs.

18

Stoichiometry for cell growth is complex, and chainges with microorganism/

nutrient system, and pH, T, etc.
Lets look at the case where one nutrient is limiting:
Cell + Subs More cells + Products

y C/S =

mass of new cells formed

1
C C
=
; y C/S =
mass of substrate consumed CS
yS/C

Product formation can take place during different phases of the cell growth
cycle if it occurs during the exp growth phase:

rp = y P/C rg = y P/C C c = y P/C

where y P/C =

max C c C s
K s + Cs

C p
mass of product formed
=
mass of new cells formed
C c

The stoichiometric yield coeff btw product & substrate is given by:

y P/S =

mass of product formed

mass of substrate consumed

Another term is the maintenance utilization term: (to maintain a cells daily
activities)

m=

mass of substrate consumed for maintenance

mass of cells Time

The rate of substrate consumption

rsm = m Cc
Neglecting the cell maintenance
Cc = yc/s [Cs0 Cs]

19

Substrate Utilization

Net rate of Rate

Rate

=
Substrate
consumed

+ consumed to
Consumptio n by cells form product

rS

y'S/C rg +

y'S/P rP

Rate

+ consumed for
maintenanc e

+

m Cc

Stoichiometric coeff

if there is production during growth, it is difficult to seperate amount of substrate

used in production and growth
-rs = ys/c + m Cc
The corresponding rate law is
rp = rg yp/c

growth associated product formation in the grwoth phase.

Apparently, no net growth during stationary phase

rp =

(k C
p

sn

Cc )

Non-growth-associated product formation in stationary phase

(K sn + Csn )
conc'n of a second nutrient which
is used for maintenance and
production (because the the
nutrient is used up for growth)

20

Mass Balances

There are two ways that we could account for the growth of microorganisms. Either # of
living cells or mass of the living cells.
For a CTSR: { called chemostats are the reactors that contain microorganisms}
Cso

Cell balance Accumulation = ln Out + Generation

Cc
Cs

dC c
= V0 C VC c + (rg rd )V
dt

Substrate Balance

dC S
= V0CSO VS C S + rSV
dt

(In most cases Cco = 0)

For a Batch System:

V = V0 = 0
Cell balance
(divide by V)

dCC
dC
= rgV rdV C = rg rd
dt
dt

Substrate

dCS
dCS
= rSV = yS / C ( rg )V mCCV
= yS / C ( rg ) mCC
dt
dt

dC s
= rsV = mC oV + y s / p ( rp )V
dt

(In growth phase)

for stationary phase (no growth)

21

Product Balance:

dC

dt

= r pV = y p / s ( rs )V

Design Equations
For a CSTR

V0 = V

C CO= 0
D=

V0
V

is called the dilution rate (a parameter used in bioreactors)

{D= 1/T }
CSTR Mass Balance:

Acc = ln Out + Gen' n

dCC
= 0 DCC + (rg rd )
dt

{ For Cell }

dC S
= DCSO DCS + rs
dt

{ For Substrate }

Using Monod Eq'n; the growth rate is determined as:

rg = CC =

( maxCS CC )
(K S + C S )

For stst operations

DCC = rg rd

D (C SO C S ) = rs
If we neglect death rate

F = C CV0 = rgV = muC CV D =

divide by Cc V
You can control specific growth rate by D!

22

We know

= max

Combining

Cs =

Cs
Ks + Cs

(Monod Eqn)

DKs

max D

If a single nutrient is limiting,

- cell growth is the only process to substrate consumption.
- cell maintanance is neglected.
Then;

ys
c
Cc = yc / s (Cso Cs )
rs = rg

DK s
Cc = yc / s Cso
max D

wash-out
Assume

rd = 0

dCc
= ( D)Cc
dt

if D>

rg = Cc

dCc
< 0 => Cc = 0
dt

(at some time)

the dilution rate at which wash-out will occur (Cc = 0)

is:
M C
Dmax = max so
K s + Cso

23

D for the max. cell production:

mass mass dm 3
=
time
dm 3 time

m c = Cc o

o Cc
V

= DCc

{Cell

production per unit volume is the

mass flow rate of cells out of the reactor}

Subs

Cc

DCc = Dyc / s (Cs / o

d ( DCc )
=0
dD

DK s
)
max D

Cs

DCc

For max D!

Physiologically Based
Pharmacokinetic Models:(PBPK)
You can model runs in living systems. You can find concn-time
profiles for medications, toxins, alcohol and drugs in the body!
Compartments of body are either a PFR or CSTR.
Perfusion rate : Blood flow in/out of organs.
unst-st models are used as CSTR
liver : PFR(unst-st)
The interchange of material btw compartments is primarily through
blood flow.

24

For example, if organs are connected in series as shown

Blood 0

C A0

Organ 1

C A1

flow

V1

2
Organ 3

Organ 2

C A2

V2

C A3

C A0

Then the balance eqns on species A in the tissue water volumes of the organs

V1

V2

and

V3

are:

dC A1
= 1 (C A0 C A1 ) + rA1V1
dt
dC A 2
= 1 (C A1 C A 2 ) + 2 (C A3 C A 2 ) + rA 2V2
V2
dt
dC A3
V3
= 2 (C A0 C A3 ) + rA3V3
dt

V1

rAi

:matabolism rate of A in organs

25

Ch 8: Steady State Non-isothermal Reactor Design

Energy Balances, Rationale and Overview
Calculate the volume necessary to achieve a conversion, X, in a PFR for a firstorder, exothermic reaction carried out adiabatically.
For an adiabatic, exothermic reaction the temperature profile might look something
like this:

The combined mole balance, rate law, and stoichiometry yield:

To solve this equation we need to relate X and T. We will use the Energy
Balance to relate X and T. For example, for an adiabatic reaction,
energy balance can be written in the form

set X, then calculate T, -VA, and

, increment X, then plot

, the

vs. X

1. Adiabatic (Q = 0); CSTR, PFR, Batch and PBR:

2. CSTR with heat exchanger, UA(Ta-T) and large coolant flow rate.

3 . PFR/PBR with heat exchange

3A. In terms of conversion, X

3B. In terms of molar flow rates, Fi

4. For Multiple Reactions

5. Coolant Balance

These are eqns we will use to solve rxn engineering problems with heat changes.

3. Energy Balance

Typical units for each term are J/s; i.e. Watts

Energy Balance
1st Law of Thermodynamics:

dE = dQ dW

Energy of the
system

(for a closed system)

Heat flow to
the system

Work done by the

system on the
surroundings

dE
= Q W + Fin E in - Fout E out
123
dt

{for an open system}

rate of energy
added to the
system by mass
flow

Evaluation of the Work Term:

W = Wf + Ws
flow

shaft

= Fi P V i
i =1

dt

in

i =1

+ Ws
out

Hi = Ui + P Vi

Combining with

dE sys

+ Fi P V i

i =1

i =1

= Q+ W s Fi H i in + Fi H i out

(1)

1.
2.
3.
4.
5.
6.

Replace Ei by Ei=Hi-PVi
Express Hi in terms of enthalpies of formation and heat capacities
Express Fi in terms of either conversion or rates of reaction
Define HRX
Define CP
Manipulate so that the overall energy balance is either in terms of the
Equations above 1.A, 1.B, 2, 3A, 3B, or 4 depending on the application

Step 1:
Substitute
,

and

into equation (1) to obtain the General Energy Balance Equation.

General Energy Balance:

For steady state operation:

We need to put the above equation into a form that we can easily use to relate X
and T in order to size reactors. To achieve this goal, we write the molar flow rates
in terms of conversion and the enthalpies as a function of temperature. We now
will "dissect" both Fi and Hi.
Flow Rates, Fi
For the generalized reaction:

(2)
In general,

Fi = FA0 (i + i X)

A = -1 B = -

b
a

where i =

C =

c
a

D =

Fi0
FA0

(3)

d
a

Then
n

H
i =1

i0

H RX

i0

Fi0 - H i Fi = FA0 [(H A0 - H A ) + (H B0 - H B ) B ] + ...........

i =1

n
n
= FA0 [(H i0 - H i ) i ] - ( i H i ) FA0 X
14 2 43

i =1
i =1

H RX
d
c
b
= HD + HC - HB - HA
a
a
a
H i0 Fi H i = FA0 i (H i0 - H i ) - H RX (T) FA0 X

(4)
(5)

(6)

dE

for st - st
= 0; combining (1) and (6) :
dt

Q - W + FA0 i (H i0 - H i ) - H RX (T) FA0 X = 0

(7)

i =1

If a phase change takes place, it will be included in H RX .

Assuming no phase change:

H i = H i (TR ) + H Qi
o

Enthalpy of
formation at TR
(ref. temp.)

(8)

Change in enthalpy when T

is changed from TR to T.

If there is a phase change:

TM

TR

TR

H i = H i (TR ) + C ps,i dT + H mi (Tm ) + C pl,i dT

o

T2

H Qi = C pi dT

(if no phase change)

(9)

(10)

T1

H i = H i (TR ) + C pi dT
o

(11)

TR

Cp = i + i T + i T 2
T

H i H i0 =

pi

dT = C pi [T - Ti0 ]

(12)

Ti0

Substitute into (7) :

Q - W + FA0

i =1

C pi [T - Ti0 ] - H RX (T) FA0 X = 0

(13)

Combine eqn (11) & (5)

H RX = H RX + C p (T - TR )
o

(14)

d
c
b
o
o
o
o
H D (TR ) + H C (TR ) - H B (TR ) - H A (TR )
a
a
a

(15)

where
H RX =
o

C p =

d
c
b
C pD + C pC - C pB - C pA
a
a
a

(16)

Combine (13) and (14)

Q - W + FA0 i C pi [T - Ti0 ] - H RX + C p (T - TR ) FA0 X = 0

i =1

(17)

Adiabatic Operation:

Ws = 0

Q = 0

X=

C
i
o

pi

(T - Tio )

- HRX + Cp (T - TR )

for an exothermic, adiabatic rxn

for an exo. rxn why does X

increase?
This is from E balance, not
mole balance.

H RX > C p (T - TR )
o

so X vs T is linear!!!

Adiabatic Tubular Reactor

Rearrange (18):

T=

X - H RX + i C pi To + X C p TR
o

C
i

pi

+ X C p

(19)

Combine with differential mole balance:

FA0

dX
= - rA (X, T)
dV

(20)

To obtain T, X and concn profiles along the reactor!

Use (19) to construct a table of T vs X.
Obtain k(T) as a function of X -rA as a function of X.
Look at Table 8-2A.

Steady State Tubular Reactor with Heat Exchange:

Q = U A (Ta - T) = Ua (Ta - T) V
FA0

F H
i

To

Q+ Fi H i

Fi H i

F H

assume Ws = 0

FAe

Te

V+V

V + V

=0

(1)

The heat flow to the reactor Q

Overall heat transfer coefficient (U)
Heat exchange area (A)
Difference between ambient temperature (Ta) and reactor temperature (T)

Q = U A (Ta - T) = Ua V (Ta - T)
A 4
=
V D

(2)

Diameter of reactor

If V 0

d (Fi H i )

Ua (Ta - T) =

(3)

dV

mole balance :

dFi
= ri = i (-rA )
dV

(4)

diff. Eq' n (3)

Ua (Ta - T) =

dFi
dV

H i = C pi dT

H i - Fi

dH i
dV

(5)

dT
dH i
= C pi
dV
dV

(6)

Combine (5) & (4) & (6)

dT
Ua (Ta - T) = i H i (-rA ) - Fi C pi
1 4 2 43
dV

(7)

H RX

 Rearrange:

6Heat
4 generated
7 48 6 Heat
4 7removed
48
dT rA H RX Ua (T - Ta)
=
dV
Fi Cpi

(8)

Fi = FA0 ( + i X)
Substitute into (8)

dT
Ua (Ta - T) + rA H RX
=
dV FA0 ( i + i X + C p X )

Ua
for a PBR {dW = b dV}

dT
= b
dW

{for a PFR}

(Ta - T) + (rA ') H RX

F C
i

These eqns will be coupled with mole balance eqns

pi

dX - rA
=
dV FA0

Balance on the Coolant Heat Transfer Fluid:

Heat transfer fluid

Tao
R2

R1

FA0, To
V

V + V

Reactants

The fluid will keep the rxn temperature constant for endo/exo thermic rxns
You might have
A. Co current Flow
B. Counter current Flow

10

A. Co Current Flow
The Energy Balance

E in

Ta: coolant temperature

mc, Hc

+ Q conduction = 0

- E out

FA, T

V + V

+ Ua (T - Ta) V = 0

mc Hc - mc Hc

FA, T
V

V + V

mc, Hc

V + V

Divide by V and take limit as V 0

mc

dH c
+ Ua (T - Ta) = 0
dV

dH c
dT
= Cp a
dV
dV

dTa Ua (T - Ta)
=
dV
mc Cp

Tao

exothermic

Tao

endothermic

B. Counter Current Flow

Ta2

Ta

FAo, To

T
V

dTa Ua (Ta - T)
=
dV
m c C pc

V + V

V=0

V = Vf

At the entrance X = 0; V = 0; Ta = Ta2

At the exit

V = Vf; Ta = Tao

The soln to the counter-current flow problem to find {T X} is a trial & error
procedure.
Assume a coolant temp at the entrance (Ta2)
Solve ODEs to calculate X, T and Ta as a function of V:
Find Ta(V = Vo)

If Ta (V = Vo ) - Ta2 < Ta (V = Vo ) = Ta2

Else assume another Ta2

11

Equilibrium Conversion
As T

{For endothermic rxns}

As T

{For exothermic rxns}

Exothermic Rxns:

Xe =

Kc
1 + Kc

{1st order rxn}

From Le Chaltliers Law

(Kc

as T

Kc =

if H<0) exothermic

Kp
(RT )

To find the max X in an exothermic rxn carried adiabatically:

Energy balance
To1 >To
Xe
Xe1

To

Xe =

C pi (T - To )

H RXN (T )

if To is changed to To1

Xe
as T

To1

Adabatic temperature

dlnK
o
H
(T)
H

RXN (TR ) + C p (T - TR )
p
RXN

=
=

dT
R T2
R T2

~
if
C
0

=
p

K (T ) = K (T ) exp H RXN (TR ) 1 1

p
1

p 2
R
T1 T2

12

To increase the conversion in an exothermic rxn, use multiple reactors with

interstate cooling:

Xe
Xeb

For Endothermic Rxn (you need heating)

Xe

Optimum Feed Temperature

T = To -

Adiabatic Reactor of fixed size

Reversible & Exothermic Rxn

H rx
X
C pA

if H rx < 0 as X
X

350

As T

Xe

;T

500

600

T, K

but the (-rA) decreases!

(so the conversion is achieved at the end of the reactor)

So there must be an optimum temperature to achieve max X.
Curve A: Rxn rate slow, rxn dictated by rate of rxn and reactor volume
As T

,r

,X

Curve B: Rxn rate very rapid. Virtual equilibrium reached in X dictated by equilibrium
conversion

13

Adiabatic Rxn Algorithm

Suppose
1. Choose X
Calculate T

Calculate k
Calculate T/To
Calculate CA

Calculate CB

Calculate KC

Calculate -rA
2. Increment X and then repeat calculations.
3. When finished, plot

vs. X or use some numerical technique to find V.

Levenspiel Plot for an

exothermic, adiabatic reaction.

14

Consider:

PFR Shaded area is the volume.

For an exit conversion of 40%

CSTR

For an exit conversion of 70%

Shaded area is the reactor volume.

For an exit conversion of 40%

For an exit conversion of 70%

We see for 40% conversion very little volume is required.

CSTR+PFR

15

For an intermediate conversion of 40% and exit conversion of 70%

Looks like the best arrangement is a CSTR with a 40% conversion followed by
a PFR up to 70% conversion.

Evaluating the Heat Exchanger Term

Energy transferred between the reactor and the coolant:

Assuming the temperature inside the CSTR, T, is spatially uniform:

16

At high coolant flow rates the exponential term will be small, so we can expand
the exponential term as a Taylor Series, where the terms of second order or
greater are neglected, then:

Since the coolant flow rate is high, Ta1

Ta2

Ta:

Multiple Steady States (MSS)

where

Heat generated term

Heat removed term

17

R(T):
Varying Entering Temperature
R(T)
Slope = Cpo (1+)
Increase To
T
Vary non-adiabatic parameter :
if you increase FA0 (molar flow rate) or decrease heat exch area then will
decrease
R(T)

Ua

=
FA0 C p0

T + Ta
Tc = 0
1+

=
= 0
decrease
Ta

To

G(T)

G(T)

High E

G(T)

increasing T

Low E

For a first order rxn:

X=

k
1+ k

18

Ignition Extinction Curve:

The point of intersection of G(T) and R(T) give Tst-st.
By plotting Tst-st vs To, we obtain ignition extinction curve.

Upper st-st

As To

Tst-st

Lower st-st

Ignition temp
Extinction temp

Runaway Rxns in a CSTR:

R(T),
G(T)

Tc =

T0 + Ta
1+

Trc = T * - Tc =

Tc

T*

Tangency point

R T *2
E

Reactor T

if this diff. is exceeded, transition to the upper st st will occur.

At this high temp, it is undesirable or even dangerous.

19

PFR

dT Ua (Ta - T) + (-rA )(-H Rxn (T))

=
m
dV
Fi Cpi

(for a single rxn)

i =1

When q multiple rxns occur with m species:

dT
=
dV

Ua (Ta - T) + (-rij ) - H Rxn,ij (T)

i : rxn
j : species

i =1
m

F C
j=1

pj

Rxn 1 :

Ex:

k1
A
B
k2
B
C

dT Ua (Ta - T) + (-r1A )[- H Rxn,1A (T) ] + (-r2B )[- H Rxn,2B (T) ]

=
dV
FA C pA + FB C pB + FC C pC
CSTR

Q - W s + FA0

i =1

C pi [T - T0 ] - [ H RXN (T) ] [rA V ] = 0

(for a single rxn)

When q multiple rxns take place

Q - W s + FA0

i =1

UA(T a - T) + FA0

C pi [T - T0 ] - V rij H RXN, ij (T) = 0

i =1

i =1

i =1

i C pi [T - T0 ] - V rij H RXN, ij (T) = 0

20