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Reactor Design 1
Klaus Möller
Department of Chemical Engineering
University of Cape Town
March 8, 2012
Contents
1 Mole (or mass) balances 5
1.1 Chemical Reaction Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.1.1 Generic ﬂow diagram of a chemical process . . . . . . . . . . . . . . . 6
1.1.2 What do we need to know . . . . . . . . . . . . . . . . . . . . . . . . 8
1.1.3 Industrial processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.1.4 The Chemical Feed stocks . . . . . . . . . . . . . . . . . . . . . . . . 10
1.2 Rate of a reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.2.1 Deﬁning when a chemical reaction takes place . . . . . . . . . . . . . 12
1.2.2 Deﬁning the rate of reaction . . . . . . . . . . . . . . . . . . . . . . . 13
1.2.3 The volume in the reaction rate and its relationship to the mass of the
reacting system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.2.4 The rate equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.3 The general mole balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.4 Mole balance for batch reactors . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.5 Mole balance for continuous stirred tank reactor (CSTR) . . . . . . . . . . . . 18
1.6 Mole balance for a homogeneous plug ﬂow reactor (PFR) . . . . . . . . . . . 19
1.7 Mole balance for a heterogeneous ﬁxed bed reactor (FBR) . . . . . . . . . . . 22
1.8 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2 Reactor sizing for single reactions using conversion 24
3 Properties and deﬁnitions of the reaction rate equation (reaction rate law) (Fogler
chapter 3) 47
4 Reaction stoichiometry and the reaction rate law (Fogler chapter 3) 60
5 Isothermal reactor design for single reactions (Fogler chapter 4) 78
6 Isothermal reactor design for multiple reactions (Fogler chapter 6) 79
7 Collection and data analysis (Fogler chapter 5) 80
7.1 Algorithm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
7.1.1 Limitations on data collected . . . . . . . . . . . . . . . . . . . . . . . 81
7.1.2 Postulate a rate law . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
7.1.2.1 Homogeneous reactions : . . . . . . . . . . . . . . . . . . . 82
1
CONTENTS CONTENTS
7.1.2.2 Heterogeneous reactions (those with a catalyst): . . . . . . . 82
7.1.3 Choose the same reactor type that matches the data collected . . . . 82
7.1.4 Write the rate equation in terms of the data that has been collected . 83
7.1.5 Make simpliﬁcations based on good chemical reaction engineering principles 83
7.1.6 Diﬀerential analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
7.1.7 Integral analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
7.1.8 Goodness of ﬁt and variance in model parameters . . . . . . . . . . . . 85
7.2 batch reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
7.2.1 Method of excess . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
7.2.2 Example : Diﬀerential method . . . . . . . . . . . . . . . . . . . . . . 86
7.2.3 Example : Integral method . . . . . . . . . . . . . . . . . . . . . . . . 91
7.2.3.1 The standard (linearised) analyses . . . . . . . . . . . . . . . 91
7.2.3.2 Example 5.2 (Fogler) . . . . . . . . . . . . . . . . . . . . . 93
7.2.4 Example : Nonlinear regression . . . . . . . . . . . . . . . . . . . . . 94
7.3 Method of initial rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
7.3.1 Example (Fogler 54) . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
7.4 Method of half lives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
7.5 Diﬀerential reactors (including CSTR and recycle reactors) . . . . . . . . . . . 99
7.5.1 Mole balances : CSTR (and recycle reactor with rapid recycle) . . . . 100
7.5.2 Mole balances : Tubular and packed bed systems . . . . . . . . . . . . 101
7.5.3 Example : Fogler 55 . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
8 Developing rate laws from reaction mechanisms and reaction pathways 107
9 Bioreactor engineering mechanisms 108
10 Bioreactor design 109
11 Analysis of reactor ﬂow patterns on reactor performance (Fogler chapter 13) 110
2
List of Figures
1.1 Generic ﬂow diagram of a process. (adapted from Schmidt, 2005) . . . . . . 6
1.2 Phthalic anhydride process. (Fogler, 2006) . . . . . . . . . . . . . . . . . . . 6
1.3 The face of chemical reaction engineering. (Fogler, 2006) . . . . . . . . . . . 7
1.4 The multidisciplinary nature of chemical reaction engineering. (Schmidt, 2005) 8
1.5 The reaction rate in a reactor. . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.6 General mole balance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.7 Batch reactor. (Fogler, 2006) . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.8 Change of moles with time in a batch reactor. . . . . . . . . . . . . . . . . . 17
1.9 Continuous stirred tank reactor, abbreviated as CSTR. . . . . . . . . . . . . . 18
1.10 Diagrams of typical plug ﬂow reactors commonly known as PFR’s. . . . . . . 19
1.11 The PFR mole balance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.12 Arbitrary shaped PFR. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.13 Molar ﬂow rate proﬁles across the PFR. . . . . . . . . . . . . . . . . . . . . 21
1.14 Tubular ﬁxed bed reactor. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
7.1 Cubic and polynomial ﬁt to the data. . . . . . . . . . . . . . . . . . . . . . . 89
7.2 Comparing the linear data ﬁt with the nonlinear data ﬁt. The green line repre
sents the nonlinear ﬁt. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
7.3 Batch reactor integral analysis linear plots for zero, ﬁrst and second order kinetics
using concentrations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
7.4 Standard regression plot for the second order reaction. . . . . . . . . . . . . 94
7.5 Predicted and experimental data when using the nonlinear leasts squares method
applied to concentration data. . . . . . . . . . . . . . . . . . . . . . . . . . . 96
7.6 Data for example (Fogler54). . . . . . . . . . . . . . . . . . . . . . . . . . . 97
7.7 Linearised initial rate plot for the dissolution process. . . . . . . . . . . . . . 98
7.8 Halflife analysis plot. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
7.9 Diﬀerential reactor operation : concepts. . . . . . . . . . . . . . . . . . . . . 100
7.10 Regression plot for the −r
CO
dependence on P
CO
. . . . . . . . . . . . . . . . 104
7.11 Plotting the −r
CO
dependence on P
H
2
. . . . . . . . . . . . . . . . . . . . . . . 104
7.12 The prediction of the reaction rate when regressing for all the rate law constants.106
7.13 The prediction of the reaction rate when regressing for k, K
H
2
in the rate law. . 106
3
List of Tables
1.1 Summary of reactor mole balances. . . . . . . . . . . . . . . . . . . . . . . . 23
7.1 Reaction rate as a function of concentration using cubic spline and polynomial
ﬁtting. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
7.2 Experimental reaction data for the conversion of CO to CH
4
. . . . . . . . . . 102
7.3 Processed reaction data. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
4
Chapter 1
Mole (or mass) balances
5
1.1. CHEMICAL REACTION ENGINEERINGCHAPTER 1. MOLE (OR MASS) BALANCES
1.1 Chemical Reaction Engineering
1.1.1 Generic ﬂow diagram of a chemical process
Figure 1.1: Generic ﬂow diagram of a process. (adapted from Schmidt, 2005)
Figure 1.2: Phthalic anhydride process. (Fogler, 2006)
• Reactors are the key unit operation on plant. A plant is typically designed around a reactor.
The operation of the reactor determines the operability and performance of the plant. See
Fig’s 1.1 and 1.2.
• Almost all the worlds commodities and essential items are made using a reactive process.
• The reactors can be as simple as a long hollow tube or a complex reaction vessel many
10’s of meters tall with many reactions occurring in multiple phases and with the aid of a
catalyst.
• It is their knowledge of chemical reaction engineering that makes chemical engineers unique
Reactors come in all shapes and sizes and arise in many interesting places, see Fig 1.3
6
1.1. CHEMICAL REACTION ENGINEERINGCHAPTER 1. MOLE (OR MASS) BALANCES
Figure 1.3: The face of chemical reaction engineering. (Fogler, 2006)
7
1.1. CHEMICAL REACTION ENGINEERINGCHAPTER 1. MOLE (OR MASS) BALANCES
1.1.2 What do we need to know
Some facts about practicing chemical engineers
• Single reactions never happen. Reactors are complex unit operations with many simultane
ous chemical reactions occuring in multiple phases. The engineer needs to know enough
about the reactions, the ﬂow patterns in the vessel, the interaction of heat and mass
transfer in order to assemble the basic understanding of the reactor operation.
• The kinetic rate equation almost never exists. Rate equations must be estimated, approx
imated from reaction engineering fundamental knowledge and from experimental or plant
data. The rate equation indicates how fast a reaction proceeds and thus determines both
the size, productivity and selectivity of the reacctor.
• Industrial processes are often severely limited by heat and mass transfer. The engineer
must know how to integrate these into the reactor design to yield its actual performance.
Reactor design typically proceeds according to a well deﬁned path
Bench Scale reactor (batch, continuous) → pilot plant → operating plant
Very few engineers will have the honour of following this process. Practicing engineers will most
likely encounter and old reactor that has been modiﬁed many times which the engineer must
now operate in such a way to double the throughput, improve selectivity and reduce the waste.
Alternatively, reactor has failed and the engineer must understand the reasons of failure and
recommission the reactor to operate better without failing.
The typical tasks are
• Maintain and operate a process,
• Fix a problem,
• Increase the capacity or selectivity at minimum cost.
The task must be solved as quickly as possible,for there are many more tasks that need doing.
Often, gaining a deeper understanding is often not possible due to the presssure of other more
pressing tasks. Besides being competent at “back of the envelope” calculations and having a
good intuitive feel for reaction engineering, the engineer also needs to be able to build quick
practical models of the reaction process by integrating all the other engineering disciplines, see
Fig 1.4.
Figure 1.4: The multidisciplinary nature of chemical reaction engineering. (Schmidt, 2005)
8
1.1. CHEMICAL REACTION ENGINEERINGCHAPTER 1. MOLE (OR MASS) BALANCES
This course is the ﬁrst course of two in reaction engineering and will aim to develop good
reactor engineering skills for optimal homogeneous, isothermal reactor design by combining the
knowledge of
• kinetic models and their structure,
• elementary reactor design equations,
• various type of reactors and conﬁguration of multiple reactor sequences,
• multiple reactions and nature of the reactions,
• experimental data to determine the rate equation.
There will essentially be two types of problems
1. The ones that can be solved in 3 lines often without a calculator. These will build good
reaction engineering intuition;
2. The ones that require more rigorous calculation and in many cases a computer. These
are the design type problems that will exercise the procedural skills and study the “what
if” scenario’s.
1.1.3 Industrial processes
The following table shows the interesting contrasts between the large volume producers and
high value chemicals produced by the pharmaceutical companies.
(Schmidt, 2005)
9
1.1. CHEMICAL REACTION ENGINEERINGCHAPTER 1. MOLE (OR MASS) BALANCES
1.1.4 The Chemical Feed stocks
The following tables shows the usage of chemicals in the USA in 1994. This ranking of these
chemicals isn constantly changing. It provides an interesting incetive for the development of
alternative processes.
(Schmidt, 2005)
This is in contrast to the prices of chemicals shown in the following table. Note the low value
of the crude oil in contrast to solvents and more so pharmaceuticals (see insulin).
10
1.1. CHEMICAL REACTION ENGINEERINGCHAPTER 1. MOLE (OR MASS) BALANCES
11
1.2. RATE OF A REACTION CHAPTER 1. MOLE (OR MASS) BALANCES
(Schmidt, 2005)
1.2 Rate of a reaction
1.2.1 Deﬁning when a chemical reaction takes place
Chemical species are deﬁned by the type, the number and arrangement of the atoms. For
example isomers diﬀer only by the arrangement of the chemical species
These, isomers, although they have the same type and number of atoms, the diﬀerent arrange
ment of the atoms results in these molecules having diﬀerent physical properties and are thus
chemically distinct from each other.
A chemical reaction has taken place when one of more of the chemical species in the system
of study are transformed by an inﬁnitesimal amount into (an)other chemical species.
This transformation can be one of the following
• Change the arrangement of the atoms :
double bond isomerisation :
skeletal isomerisation :
• Decomposition :
12
1.2. RATE OF A REACTION CHAPTER 1. MOLE (OR MASS) BALANCES
• disproportionation :
• Addition :
• and many more other types of reactions (see organic chemistry hand book!)
Often it is simpler to work with letters such as A, B, C, D for chemical species. Thus the
reaction of methanol to dimethylether and water written as
2CH
3
OH →CH
3
OCH
3
+ H
2
O
can be written as
2A →D + W
or
A →
1
2
D +
1
2
W (1.1)
1.2.2 Deﬁning the rate of reaction
Consider that A is reacting in the vessel in Fig 1.5. −r
A
represents the consumption of A at
some position in the reactor vessel and it is deﬁned as follows.
Figure 1.5: The reaction rate in a reactor.
Deﬁnition of reaction rate : The number of moles of A that are being reacted (consumed or
produced) per unit volume per unit time [mol .m
−3
.s
−1
].
13
1.2. RATE OF A REACTION CHAPTER 1. MOLE (OR MASS) BALANCES
Deﬁnition of r
A
: r
A
represents the rate of formation of species A. Thus −r
A
represents the
rate of consumption of A. Thus r
A
is positive for a product and negative for a reactant.
Reaction stoichiometry : In reaction 1.1, the consumption of one mole of A will yield 0.5 moles
of D and 0.5 moles of W. For example if the rate of consumption of A is 5 mol .m
−3
.s
−1
then r
A
= −5 or −r
A
= 5 and r
D
= 2.5 and r
W
= 2.5. Similarly the rate equations for A,
D and W are related by the reaction stoichiometry: −r
A
= 2r
D
= 2r
W
=
r
D
1
/2
=
r
W
1
/2
.
It is good practice to decide on a convention and stick to it. This course will work with the
deﬁnition of r
A
as given above.
1.2.3 The volume in the reaction rate and its relationship to the mass of
the reacting system.
Homogeneous reactors well mixed : When the vessel is well mixed such that the concentra
tion of A is equal trhough the reacting vessel, the volume represented by the m
3
term
refers to the vessel volume. In gas phase systems the actual volume of the vessel is used.
In liquid phase systems, if the vessel is not completely ﬁlled, the liquid volume is used.
Homogeneous reactors with concentration gradient : When the species concentrations vary
throughout the reactor volume, the volume refered to in the rate equation is that of a
diﬀerential element in which it can be assumed that the concentration is uniform for all
species (i.e. well mixed).
Heterogeneous reactors : In these reactors the reaction takes place on a catalyst surface (or
a solid surface or within the catalyst pores). The volume refered to in the rate equation is
then the volume of the catalyst. Since the density of a catalyst is constant, it is easy to
convert the rate equation into a mass basis using the catalyst density and then the rate
equation is deﬁned as moles of A reacting per mass of catalyst per time [mol .kg
−1
.s
−1
] and
is denoted as r
A
. (Note that the activity per unit surface area can similarly be converted
into a mass basis by using the catalyst properties which deﬁne the surface area to mass
ratio.
Multiphase reactions : If the reaction contains a vapour and a liquid phase, then there will be
a rate equation for each phase, r
vap
A
and r
l i q
A
and the volume refered to will be the vapour
phase volume and the liquid phase volume respectively. Similarly, for more phase including
solids and catalysts.
1.2.4 The rate equation
The rate equation
r
A
= f uncti on(C
i
, T, P, C
catal yst
)
is a function of the concentration (activities) of all or some of the chemical species in the reacting
system, or the temperature and pressure of the system and the properties of the catalyst. The
rate equation is an algebraic expression deﬁning how the reaction rate varies with the chemical
and physical properties of the reacting system.
NOTE : The rate equation is independent of the reactor in which the reaction is being
carried out in.
14
1.3. THE GENERAL MOLE BALANCE CHAPTER 1. MOLE (OR MASS) BALANCES
Examples of possible rate equations for the reaction
A →Pr oducts
• Linear variation of reaction rate with concentration : r
A
= −kC
A
• Quadratic variation of the reaction rate with concentration : r
A
= −kC
2
A
• Saturation of the reaction rate : r
A
=
−k
1
C
A
(1 + k
2
C
A
)
2
NOTE : Although r
A
=
dC
A
dt
is true from the deﬁnition of the units of the reaction rate, this
equation is actually the design equation for a constant volume batch reactor, which will be
developed later in this course. It is not the deﬁnition of the rate equation.
1.3 The general mole balance
Consider a mole balance of species j in a arbritary shaped reaction vessel (or control volume) in
Fig 1.6. , For example in the reaction
A →pr oducts
A would represent j . It is not necessary the know what the other products are at this stage.
Also species j can be a reactant of a product (i.e. sometimes products are fed to the reactor
as a result of recycle)
Figure 1.6: General mole balance.
The mole balance then can be written as
IN −OUT + Gener ati on = Accumul ati on
_
¸
¸
_
rate of ﬂow
of j INTO
the system
[mol .s
−1
]
_
¸
¸
_
−
_
¸
¸
_
rate of ﬂow
of j OUT of
the system
[mol .s
−1
]
_
¸
¸
_
+
_
¸
¸
_
rate of generation
of j by chemical
reaction in the system
[mol .s
−1
]
_
¸
¸
_
=
_
¸
¸
_
rate of accumulation
of j within
the system
[mol .s
−1
]
_
¸
¸
_
15
1.4. MOLE BALANCE FOR BATCH REACTORS CHAPTER 1. MOLE (OR MASS) BALANCES
and in symbols this is
F
j,0
−F
j
+ G
j
=
dN
j
dt
(1.2)
where N
j
is the total number of moles of j in the system. G
j
represents the total transformation
of j that has occurred when passing through this reaction vessel. G
j
can be related to the
reaction rate for two special cases
1. When the concentration of all species is constant throughout the entire system volume
: Then the reaction rate r
j
is the same throught the whole reaction vessel and G
j
= r
j
V
where V is the volume of the vessel. The general mole balance, equa 1.2 then becomes
F
j,0
−F
j
+ r
j
V =
dN
j
dt
(1.3)
2. When the concentration of all species varies throughout the reaction volume : Then the
reaction rate will be diﬀerent at all locations. Dividing the system volume into diﬀerential
elements (see Fig 1.6), ∆V
i
and assuming that the concentration of all species is constant
in each diﬀerential element, means that the reaction rate is constant on each diﬀerential
element. Thus the rate of generation of species j in each element is given by r
j,i
∆V
i
. The
rate of generation of species j in the system is thus the sum of all the diﬀerential elements
: G
j
= r
j,1
∆V
1
+r
j,2
∆V
2
+r
j,3
∆V
3
· · · =
M
i =1
r
j,i
∆V
j
. In the diﬀerential limit, as ∆V →0 and
M →∞ then G
j
=
_
V
r
j
dV . The general mole balance in this case becomes
F
j,0
−F
j
+
V
_
r
j
dV =
dN
j
dt
(1.4)
Equation 1.4 is the GENERAL DESIGN EQUATION for chemical reaction engineering. When
used on its own, it is applicable to all ISOTHERMAL reaction systems. For NONISOTHERMAL
reaction systems an ENERGY BALANCE will also be needed in order to solve equation 1.4.
1.4 Mole balance for batch reactors
Figure 1.7: Batch reactor. (Fogler, 2006)
16
1.4. MOLE BALANCE FOR BATCH REACTORS CHAPTER 1. MOLE (OR MASS) BALANCES
Fig 1.7(A) shows a schematic diagram of a industrial batch reactor. Its a vessel with a lid so
that it can be opened for cleaning. It has ports for adding and removing chemicals. It almost
always has a stirrer (agitator) and they are almost always used for liquid phase operations. There
are coils or a jacket around the outside of the vessel for heating and cooling. Some vessels have
coils internally, others use evaporation cooling or direct steam heating. The vessel is always
raised oﬀ the ground.
Fig 1.7(B) shows the text book schematic of a batch reactor as a vessel ﬁlled with liquid and a
stirrer to provide perfect mixing, such that the concentration oﬀ all species in the reactor are
the same everywhere in the vessel. The reactor volume is that of the reactive mixture, in this
case the liquid volume and NOT the volume of the vessel.
A batch reactor is operated by ﬁlling the vessel with the required reactants. The reactor is
then heated to the desired reaction temperature and the reaction is allowed to proceed for a
predetermined amount of time, called the reaction time. During this time there is no ﬂow into
or out of the reactor. An the end of the the reaction time the mixture is removed (pumped...)
out of the vessel. The reactor is then cleaned and the cycle starts again with fresh reactants.
Since there is no ﬂow into or out of the vessel, the general mole balance on species j becomes
V
_
r
j
dV =
dN
j
dt
Assuming that the system is well mixed, the reaction rate equation will be the same through
the whole vessel, thus the design equation is
dN
j
dt
= r
j
V (1.5)
Notice that the general equation, equa 1.5 is based on the number of moles in the vessel and
not the concentration. More on this later.
For a reaction A →B the number of moles of A decrease with time while the number of moles
of B increase with time, as shown in Fig 1.8.
Figure 1.8: Change of moles with time in a batch reactor.
17
1.5. MOLE BALANCE FOR CONTINUOUS STIRRED TANK REACTOR (CSTR) CHAPTER 1. MOLE (OR MASS) BALANCES
The time t
1
that is required to consume (N
A0
−N
A
) moles can be obtained by integrating equa
1.5:
t
1
=
_
N
A1
N
A0
dN
A
r
A
V
(1.6)
where N
A0
are the number of moles at the start of the reaction, t = 0 and N
A1
are the number
fo moles of A that are remaining after a reaction time of t
1
.
1.5 Mole balance for continuous stirred tank reactor (CSTR)
(A) (B)
Figure 1.9: Continuous stirred tank reactor, abbreviated as CSTR.
Fig 1.9(A) shows a schematic diagram of a continuous stirred tank reactor (CSTR). These
reactors always have a stirrer or some form of vigorous agitation to ensure that the composition
of all species is uniform throughout the reaction system. They also have a heating/cooling jacket
of coils to control the temperature in the vessel. They can be closed vessels or open vessels.
They can be ﬁlled to capacity or have partially ﬁlled with or without two phase operation.
These reactors are most often used for liquid applications involving poorly miscible streams
and/or solids. They are also used for systems which require the additiion of another phase e.g.
like bubbling a reactive gas through a liquid reactant.
Fig 1.9(B) shows the diagramatic way in which a CSTR is represented for calculation purposes.
The mole balance for species j across this vessel is
F
j,0
−F
j
+
V
_
r
j
dV =
dN
j
dt
If the reactor is operated at steady state, the there is no variation with time of all species on
the reactor, thus,
dN
j
dt
= 0 and the mole balance becomes;
F
j,0
−F
j
+
V
_
r
j
dV = 0
18
1.6. MOLE BALANCE FOR A HOMOGENEOUS PLUG FLOW REACTOR (PFR) CHAPTER 1. MOLE (OR MASS) BALANCES
In addition, since there are no spatial variations in the concentrations as the contents of the
vessel is well mixed, the reaction rate, r
j
is constant throughout the whole vessel, which means
that
_
V
r
j
dV = r
j
V and the mole balance then becomes;
F
j,0
−F
j
+ r
j
V = 0 (1.7)
V =
F
j 0
−F
j
r
j
This is the ﬁnal design equation for the CSTR. It is important to note that the concentration
of the species in the reactor have the same concentration as the species leaving the reactor
in the exit ﬂow.
1.6 Mole balance for a homogeneous plug ﬂow reactor (PFR)
Figure 1.10: Diagrams of typical plug ﬂow reactors commonly known as PFR’s.
A plug ﬂow reactor, Fig 1.10 is basically an empty tube through which a reactive ﬂuid ﬂows. The
reactive streams are mixed at the reactor inlet. The reactor can be heated or cooled depending
on the reaction requirements by using a jacket, by making steam on the outside of the tubes
or coils in the vessel. The important aspect of these reactors is that they are extremely long
in relation to their diameter, as it is best to have turbulent ﬂow. This is to promote plug ﬂow.
Plug ﬂow is deﬁned as ﬂow in which there is no axial mixing (no mixing along the length) by
good radial mixing (mixing perpendicular to the ﬂow). This means that all the species that enter
the reactor spend exactly the same amount of time in the vessel. Species interact only radially
and not axially. Plug ﬂow reactor can be mounted inside furnaces for very high temperature
operation.
19
1.6. MOLE BALANCE FOR A HOMOGENEOUS PLUG FLOW REACTOR (PFR) CHAPTER 1. MOLE (OR MASS) BALANCES
Figure 1.11: The PFR mole balance.
In developing the general mole balance for a PFR, consider the schematic in Fig 1.11. The
general mole balance can be applied to the whole reaction vessel, thus for species j it is
F
j,0
−F
j
+
V
_
r
j
dV =
dN
j
dt
Since the species concentrations (or molar ﬂow rates) are not constant, it is not possible to
simplify the integral expression. Furthermore, when more than one reaction is taking place,
the reaction rate term, r
j
does not only depend on species j but can also depend on the other
species in the reaction vessel, preventing the integration from being carried out. Thus in this
case the general mole balance in this form is not particularly useful. Assuming steady state
makes
dN
j
dt
= 0. Then diﬀerentiating with respect to the reactor volume yields
dF
j,0
dV
−
dF
j
dV
+ r
j
= 0
and since the feed does not depend on the reactor volume, thus
dF
j,0
dV
= 0 and thus
dF
j
dV
= r
j
(1.8)
which is the general mole balance for a PFR. Note that this is a diﬀerential equation.
The reactor mole balance can be obtained in a more intuitive way by considering a diﬀerential
element, in which it can be assumed that the species concentrations are constant and thus the
reaction rate is also constant. The diﬀerential mole balance over the diﬀerential element is then
IN −OUT + Gener ati on = Accumul ati on
_
¸
¸
_
molar ﬂow rate
of species j
IN at V
[mol .s
−1
]
_
¸
¸
_
−
_
¸
¸
_
molar ﬂow rate
of species j
OUT at V + ∆V
[mol .s
−1
]
_
¸
¸
_
+
_
¸
¸
_
Molar rate of
generation of
species j in ∆V
[mol .s
−1
]
_
¸
¸
_
=
_
¸
¸
_
rate of accumulation
of species j
within ∆V
[mol .s
−1
]
_
¸
¸
_
which in symbols, for a reactor at steady state becomes
F
j

V
−F
j

V +∆V
+ r
j
∆V = 0
Dividing through by ∆V and rearranging yields
F
j

V +∆V
−F
j

V
∆V
= r
j
20
1.6. MOLE BALANCE FOR A HOMOGENEOUS PLUG FLOW REACTOR (PFR) CHAPTER 1. MOLE (OR MASS) BALANCES
Since the ﬂow rate us a function of V in the sense that F = f (V ) the term
F
j

V +∆V
−F
j

V
∆V
represents an approximation to the dereivative of F with respect to V . In the limit as ∆V →∞
the PFR mole balance becomes
dF
j
dV
= r
j
as before.
IMPORTANT NOTE : for plug ﬂow conditions, the shape of the reactor does not matter
and is arbitrary (in the derivation volume was used with no mention of the shape of the
vessel). Thus Fig 1.12 could also have been used for the derivation of the mole balance. This
is no longer true once other factors are accounted for, on in particular is pressure drop, which
depends on the velocity, which would vary with crosssetional area.
Figure 1.12: Arbitrary shaped PFR.
Consider again the reaction A →B but this time in a PFR. The molar ﬂow rate proﬁles across
the reactor as shown in Fig 1.13. These are similar to the batch reactor, except that volume
has replaced time.
Figure 1.13: Molar ﬂow rate proﬁles across the PFR.
The design equation for this reaction is
dF
A
dV
= r
A
(1.9)
21
1.7. MOLE BALANCE FOR A HETEROGENEOUS FIXED BED REACTOR (FBR) CHAPTER 1. MOLE (OR MASS) BALANCES
To determine the volume of reactor required to achieve the exit ﬂow rates F
A1
and F
B1
in Fig
1.13 can be obtained by integrating equation 1.9 from the beginning of the reactor where V = 0
and F
A
−F
A0
until V
1
where F
A
= F
A1
;
_
V
1
0
dV = V
1
=
_
F
A1
F
A0
dF
A
r
A
1.7 Mole balance for a heterogeneous ﬁxed bed reactor (FBR)
(a) (b)
Figure 1.14: Tubular ﬁxed bed reactor.
Fig 1.14(a) shows a ﬁxed bed reactor with the catalyst packed in the tubes and coolant ﬂowing
around it (sometimes steam is made in this way). This conﬁguration is used if the reaction is very
exothermic (produces a lot of heat) and/or the reactants or products are heat sensitive and/or
the catalyst deactivates at higher temperatures and/or the catalyst selectivity deteriorates and
it is crucial to keep the reactor as close to isothermal operation as possible. For other reactions
where the exothermicity can be tolerated or the reaction is near thermoneutral, the vessel can
simply be packed with catalyst particles as a uniform bed.
The particle size and the bed diameter are key design parameters. The isothermal vessels are
typically long and thin with a relatively small vessel : particle diameter ratios (2040). Adiabatic
vessels are typically short and squat with large vessel : particle diameter ratios (>>100). Mass
and heat transfer in the catalyst particle to/from the active site becomes more diﬃcult as the
particle size increases. In contrast, the pressure drop across the bed increases as the particle
size decreases. These opposing eﬀects need to be optimised during the reactor design phase.
The interplay of heat and mass transfer in catalytic reactions is a leads to exciting reaction
systems. More of this will be the topic of reactor design 2.
In this ﬁrst level mole balance, it will be assumed that heat and mass can be neglected and that
pressure drop can be ignored and that the ﬂow in the vessel is perfect plug ﬂow. The reaction
rate is thus based on the catalyst mass (or catalyst volume), since it is the catalyst that is
responsible for the reaction that is taking place. (Vessel volume and catalyst volume can easily
be used or converted to, through the density of the catalyst particles). Thus the reaction rate
22
1.8. SUMMARY CHAPTER 1. MOLE (OR MASS) BALANCES
is deﬁned as
r
A
= [(mol Ar eacted).s
−1
.g
−1
catal yst
]
Fig 1.14(b) shows the diﬀerential element used in the mole balance;
IN −OUT + Gener ati on = Accumul ati on
F
j

W
−F
j

W+∆W
+ r
j
∆W = 0
Dividing through by ∆V and rearranging yields
F
j

W+∆W
−F
j

W
∆W
= r
j
Since the ﬂow rate us a function of W in the sense that F = f (W) the term
F
j

W+∆W
−F
j

W
∆W
represents an approximation to the dereivative of F with respect to W. In the limit as ∆W →∞
the PFR mole balance becomes
dF
j
dW
= r
j
(1.10)
and the catalyst weight required to achieve a exit ﬂoe rate of F
A
is given by
W =
_
F
A
F
A0
dF
A
r
A
1.8 Summary
Table shows summary of all the mole balances carried out in this chapter.
Table 1.1: Summary of reactor mole balances.
reactor Comment Mole balance
diﬀerential algebraic integral
Batch no spatial variation
dN
A
dt
= r
A
V t =
_
N
A
N
A0
dN
A
r
A
V
CSTR no spatial variation, steady state  V =
F
A0
−F
A
−r
A
PFR steady state
dF
A
dV
= r
A
V =
_
F
A
F
A0
dF
A
r
A
FBR steady state
dF
A
dW
= r
A
W =
_
F
A
F
A0
dF
A
r
A
(Fogler, 2006)
These represent the deﬁnite equations of the reactor design 1 course and for that matter all
reaction engineering design problems can be solved using these equations. The rest of this
course is on the application of these equations to speciﬁc problems.
23
Chapter 2
Reactor sizing for single reactions using
conversion
24
Chapter 3
Properties and deﬁnitions of the reaction
rate equation (reaction rate law) (Fogler
chapter 3)
47
Chapter 4
Reaction stoichiometry and the reaction
rate law (Fogler chapter 3)
60
Chapter 5
Isothermal reactor design for single
reactions (Fogler chapter 4)
78
Chapter 6
Isothermal reactor design for multiple
reactions (Fogler chapter 6)
79
Chapter 7
Collection and data analysis (Fogler
chapter 5)
80
7.1. ALGORITHM CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
This chapter develops some of the techniques that are used to obtain rate laws for chemical re
actions, which are then ultimately used in the design of a pilot plant and ultimately a commercial
unit. THE KNOWLEDGE AND TOOLS GAINED HERE ARE EXTREMELY IMPORTANT.
The purpose of this chapter is to develop the following knowledge
1. To be able to estimate the reaction rate constant, the reaction order and other constants
in the rate law from appropriately collected experimental data.
2. To be able to study experimental data and decide how it should be analysed
3. To be able to develop the appropriate reactor design equation and rate law that will
describe the experimental data
4. To be able to formulate the design equation in the appropriate form such that it is suitable
for regression with experimental data to determine the rate law parameters
5. To be able to formulate the objective function and use appropriate computer code to carry
out the nonlinear regression
6. To be able to select the best model based on good statistical methods.
7.1 Algorithm
The following steps are general and apply to all the examples and reactor types that follow.
7.1.1 Limitations on data collected
The following are guidelines when collecting data or looking at data to be analysed
1. Make every eﬀort to ensure that the data is collected under isothermal and isobaric con
ditions
2. Make sure that the data are collected at steady state and that the MASS BALANCE IS
OBEYED.
3. Make every eﬀort to ensure that the data collected is free of transport limitations such as
ﬁlm resistance, pore diﬀusion. (see later chapters)
4. Make every eﬀort to ensure that the idealisations of the assumed reactor type are obeyed.
For example, if a plug ﬂow reactor is assumed, the reactor conﬁguration choosen must
behave like a plug ﬂow reactor or else the estimated rate constant will depend on the
shape of the reactor and CANNOT BE USED FOR SCALEUP. For example in a two
phase batch reactor (gas bubbles in the liquid), it is necessary that the stirring is fast
enough such that the bubbles are small enough to ensure that there are no mass transfer
limitations.
5. Make every eﬀort to ensure that there are no unexpected concentration and temperature
gradients. For example, in a ﬂow reaction bomb (CSTR) in which a combustion reaction
is taking place, gfeat care needs to be taken to ensure that the mixing (stirring) is fas
enough to ensure that there are NO temoperature and concentration gradients in the
vessel. The same applies to fast liquid phase reactions in a batch reactor, the stirring
must be fast enough to ensure complete mixing at all times during the reaction.
81
7.1. ALGORITHM CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
6. There are ways to analyse nonisothermal and nonisobaric data, but it is considerably
more diﬃcult to get estimates of the kinetic constants that are reliable. It is also beyond
thre scope of this course. Similarly, nonideal reactor behaviour can be accounted for, but
this also leads to less accurate estimations of the rate constants.
7.1.2 Postulate a rate law
The design and development of rate laws is the topic of the next section (Fogler!!!!). In many
cases the rate law needs to be developed in conjunction with the data analysis and experimental
observations.
Good places to start
7.1.2.1 Homogeneous reactions :
monomolecular : −r
A
= kC
n
A
= k
P
α
A
(7.1)
bimolecular : −r
A
= kC
α
A
C
β
B
= k
P
α
A
P
β
B
(7.2)
reversible : −r
A
= k
_
C
A
C
B
−
C
C
C
D
K
e
_
(7.3)
In particular for reversible reactions it is important that the rate law is able to describe the
chemical equilibrium of the reaction(s) i.e. for reaction 7.3 the equilibrium limit is
K
e
=
C
Ce
C
De
C
Ae
C
Be
where the C
i e
are the equilibrium concentrations when r
A
= 0, and obtained from thermody
namics.
7.1.2.2 Heterogeneous reactions (those with a catalyst):
LangmiurHinshilwood (LH) : −r
A
=
kP
A
1 + K
A
P
A
(7.4)
LHreversible : −r
A
=
k
_
P
A
−
P
B
K
e
_
1 + K
A
P
A
+ K
B
P
B
(7.5)
Also here the rate law must obey the thermodynamic limitations of the reaction thermodynamics.
7.1.3 Choose the same reactor type that matches the data collected
Batch reactor :
−r
A
=
1
V
d(N
A
)
dt
=
dC
A
dt
=
dC
A
dt
=
1
RT
dP
A
dt
(7.6)
PFR :
−r
A
=
dF
A
dV
= −F
A0
dX
A
dV
(7.7)
CSTR :
−r
A
=
F
A0
−F
A
V
=
F
A0
V
X
A
(7.8)
82
7.1. ALGORITHM CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
7.1.4 Write the rate equation in terms of the data that has been collected
e.g. P
A
vs t, N
A
vs t, X
A
vs W etc.
7.1.5 Make simpliﬁcations based on good chemical reaction engineering
principles
Some typical examples are;
1. Reactants in excess : This means that for example that when the concentration of B
exceeds the concentration of A by more that a factor of 100, then the second order
reaction −r
A
= kC
α
A
C
β
B
can be approximated by −r
A
= k
C
α
A
where k
= kC
β
B
. NOTE that
in this csae the rate constant k
is a function of the concentration of B (C
B
). NOTE also
that this rate law cannot be used for conditions in which the concentration of B is of the
same order of magnitude as A. For situations like this new experimental data will have to
be collected.
2. Reactants are dilute in a reaction mixture : If for example the mole fractions of A, B in a
reacting mixture are less than 1%, then any volume expansion, pressure change, ﬂow rate
change, due to the change the number of moles, can be neglected (i.e. ε = 0). Similarly
for liquid phase reactions.
3. Fast reactions can be assumed to be at chemical equilibrium, which simpliﬁes the rate
equations.
7.1.6 Diﬀerential analysis
This method of analysis takes the approach that the data will be in the form
REACTION RATE vs RATE LAW
−r
A
=
_
−
dC
A
dt
,
dF
A
dV
, −
dP
A
dt
,
F
A0
V
X
A
, etc
_
vs kC
α
A
C
β
B
(7.9)
In a CSTR, the data automatically comes in this form i.e. −r
A
=
F
A0
V
X
A
. However, for
all other reactors this provides an approximation to the data collected. All other reactors will
collect primarily C vs t or F vs V data which has to be converted into rate data by numerical
diﬀerentiation. Numerical diﬀerentiation increases the scatter (error) in the data and leads
to poor data analysis and this method is not recommended, although its use will be quickly
demonsrated as is done in Fogler.
Often, data is collected in what is known as a diﬀerential reactor, in which the feed entering is
already partially converted (i.e. X
i n
> 0) and products leaving only increase the conversion by
a few percent (i.e. X
out
= X
i n
+ ≤ 0.05), then the reactor can be treated similarly to a CSTR,
viz. −r
A
= −F
A0
X
i n
−X
out
∆V
.
In all cases the data analysis normally follows the following approach:
−r
A
= kC
α
A
C
β
B
(7.10)
83
7.1. ALGORITHM CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
taking logs on both sides:
l n(−r
A
) = l n
_
−
dC
A
dt
_
= l n(k) + αl n(C
A
) + βl n(C
B
) (7.11)
which is a linear equation in (l n(k), α, β) which can then be found by linear regression. This is
a good approach when the reaction order are unknown and are needed to be estimated, since
the equation is linear in the reaction orders. NOTE : this methods uses log weighting of the
data, and this will have slightly diﬀerent answers than the direct nonlinear regression, which
can be formulated as :
mi n [f (k, α, β)] =
n
i =1
_
−r
A,i
−kC
α
A,i
C
β
B,i
¸
2
≈ 0
where −r
A,i
represents the measured data data at each experimental value i of the concentrations
C
A,i
, C
B,i
in the reaction system when a total number of n experiments have been carried out.
The objective function f (k, α, β) must be minimised by adjusting k, α, β until the least squared
error is as close to zero as possible (using excel’s solver or scilab’s lsqrsolve).
7.1.7 Integral analysis
This analysis is more applicable to standard reactors which generate data in the form:
C
A
, F
A
, P
A
, X
A
vs t, V, W, τ,
W
F
A0
(7.12)
In all these cases the design equation must be integrated. Note that integration is a smoothing
process and reduces the errors in the estimated rate constants as opposed to the diﬀerential
method. For the simple α
th
order reaction −r
A
= kC
α
A
in a liquid phase batch reactor this yields:
C
A
= C
A0
exp(−kt) α = 1 (7.13)
C
(1−α)
A
= −k(1 −α)t + C
(1−α)
A0
(7.14)
For the ﬁrst equation (α = 1) the linear plot l n(C
A
) vs t will yield rate constant from the slope.
However, for the second equation, the linear plot of C
(1−α)
A
vs t will require an estimate of α.
Thus the linear regression requires repeated guesses of α, which is silly. Thus this type of data
can only be analysed using nonlinear analysis except in some special cases. (typically when the
reaction order is given, linearisation is often possible).
Nonlinear regression in this case yields:
mi n [f (k, α)] =
n
i =1
_
C
(1−α)
A,i
+ k(1 −α)t
i
−C
(1−α)
A0
_
2
≈ 0 (7.15)
or in terms of the measured variable, C
A
it is
mi n [f (k, α)] =
n
i =1
_
_
C
A,i
−
_
−k(1 −α)t
i
−C
(1−α)
A0
_
1
1 −α
_
_
2
≈ 0 (7.16)
There are many situations where integration is not possible. For example, consider the second
order nonequimolar reaction with the rate law : −r
A
= kC
α
A
C
β
B
. Writing in terms of conversions
84
7.1. ALGORITHM CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
for a constant ﬂow rate system yields, the PFR design equation is:
F
A0
dX
A
dV
= kC
α+β
A0
(1 −X
A
)
α
_
C
B0
C
A0
−X
A
_
β
(7.17)
V
F
A0
kC
α+β
A0
=
X
A
_
0
1
(1 −X
A
)
α
_
C
B0
C
A0
−X
A
_
β
dX
A
(7.18)
which can be formulated as an objective function
mi n [f (k, α, β)] =
n
i =1
_
¸
¸
¸
_
V
F
A0,i
kC
α+β
A0
−
X
A,i
_
0
1
(1 −X
A
)
α
_
C
B0
C
A0
−X
A
_
β
dX
A
_
¸
¸
¸
_
2
≈ 0 (7.19)
where the diﬀerent conversion are obtained by varying the ﬂow rate (this is the most common
way, changing V is the other way). In this formulation the integral must be evaluated each time
for each value of X
A,i
. All this is not a problem on a computer. (NOTE, that if C
A0
= C
B0
then it is no longer possible to distinguish α from β. The advantage of this approach is that
it is general, requires no guessing of α, β and has no limitations of these values either. The
disadvantage is that it needs some computer code to be written!
It is possible to have multiple reactions with multiple rate constants, where integration using an
ODE solver is needed each time is also easily done on a computer.
7.1.8 Goodness of ﬁt and variance in model parameters
The goodness of ﬁt can be obtained in two ways
(i) A correlation coeﬃcient can be obtained between the experimental and the predicted data
e.g plotting (−r
A
)
exp
versus (−r
A
)
model
and estimating the mean and variance.
(ii) looking at the least squares error :
¸
¸
¸
¸
_
n
i =1
_
(−r
A
)
exp
−(−r
A
)
model
¸
2
n −m
where n is he number
of data points and m is the number of estimated parameters (3 in the case shown here)
The variance in the model parameters can be obtained by studying the Jacobian matrix of the
objective function : J
i ,j
=
_
∂f (p)
j
∂p
i
_
where p is the vector p = [k, α, β] and f (p) is evaluated
at each data point j , and thus J is a m × n matrix. Then the variance in the parameters p is
given by
p
i
= p
i
±σ
i ,i
; σ
i ,i
=
¸
¸
¸
_
f (p) ×
_
_
J
T
J
_
−1
_
i ,i
n −m
(7.20)
where
_
_
J
T
J
_
−1
_
i ,i
refers to the diagonals of the matrix. When σ
i ,i
0.2p
i
then the parameter
is a poor estimated and the model is most likely over parameterised and that means that there
are most likely too many model parameters or there is not suﬃcient data.
85
7.2. BATCH REACTORS CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
7.2 batch reactors
7.2.1 Method of excess
The idea of this method is to reduce the dependence of the rate law on multiple concentrations
into one concentration. This method is particularlygood for getting ﬁrst estimates of the reaction
order with respect to the key component. For example, the reaction :
A + B →pr oducts
with the rate law
−r
A
= kC
α
A
C
β
B
(7.21)
is diﬃcult to analyse when both α, β are unknown. The idea then is to carry out the reation in
two ways (i) Using excess B such that C
B
= C
B0
and does not change signiﬁcantly during the
reaction. Then
−r
A
= kC
α
A
C
β
B
= kC
β
B0
C
α
A
= k
C
α
A
(7.22)
which can then be used to ﬁnd α.
(ii) Using excess A such that C
A
= C
A0
and remains eﬀectively constant during the reaction,
similarly
−r
A
= kC
α
A
C
β
B
= kC
α
A0
C
β
B
= k
C
β
B
(7.23)
which can be used to ﬁnd β.
(iii) Once α, β have been found, then normal concentration data can be analysed for k.
7.2.2 Example : Diﬀerential method
(Fogler, ex 5.1, p260)
The reaction of triphenyl methyl chloride (A) with methanol(B) viz
(C
6
H
5
)
3
CCl + CH
3
OH → (C
6
H
5
)
3
COCl + HCl
A + B → C + D
is carried out in a batch reactor in a solution of benzene and pyridine at 25°C. HCl reacts with
the pyridine, which then precipitates making the reaction irreversible. The concentration time
data is collected
time (min) 0 50 100 150 200 250 300
Concentration of A, C
A
[mmol.L
−1
] 50 38 30.6 25.6 22.2 19.5 17.4
The initial concentration of methanol was 500 mmol.L
−1
.
1. determine the reaction order with respect to triphenylmethylchloride
2. the reaction order of methanol was given as 1, determine the reaction rate constant
SOLUTION
PART 1
Looking at the data
the time vector is given by : [t] = [t
1
t
2
t
3
...t
n
]
the concentration vector is given by : [C
A
] = [C
A,1
C
A,2
C
A,3
...C
A,n
]
86
7.2. BATCH REACTORS CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
where n is the number of data points. This also means that you cannot estimate more than n
model parameters.
Proposed rate law : −r
A
= kC
α
A
C
β
B
now, C
B0
= 10C
A0
thus the it may be assumed that C
B
= C
B0
≈ constant over the range of
the data collected (well, not really that constant, by the change is less than 5%)
Then −r
A
= k
C
α
A
where k
= kC
β
B0
Mole balance :
dN
A
dt
= r
A
V
stoichiometry : N
A
= N
B
= −N
C
= −N
D
Since this is dilute liquid phase system, the density (volume) of the system is constant, thus the
design equation becomes;
−
dC
A
dt
= k
C
α
A
(7.24)
diﬀerential analysis then requires;
l n
_
−
dC
A
dt
_
i
= l n(k
) + αl n(C
A,i
) (7.25)
where the i values run over all data points. Thus it is necessary to ﬁnd the reaction rate as a
function of time.
The best way to do this is to ﬁt a cubicspline to the data
//fit a cubicspline to the data
d = splin(tt,Ca);
function Cat=spln(t)
Cat=interp(t,tt,Ca,d)
endfunction
Cas=interp(t,tt,Ca,d) //spline interpolated values
and then to diﬀerentiate the cubicspline
//get the gradient
ttt=tt;ttt(n)=ttt(n)0.1; //takingcare of the last point
dCa_dt_s=diag(numdiff(spln,ttt));
disp(’dCa/dt=’+string(dCa_dt_s))
. This yields the following data in table 7.1.
An alternative is to ﬁt a polynomial to the data. This is done as follows;
The error between each data point and the polynomial is given by
ε
i
= C
A,i
−(a
1
+ a
2
t + a
3
t
2
+ a
4
t
3
+ a
5
t
4
...) (7.26)
which can be vectorised as follows since it is a linear operation with basis sets
ε
i
= C
A,i
−[p]
i
[a]
T
(7.27)
[p]
i
= [1 t
i
t
2
i
t
3
i
t
4
i
...] [a] = [a
1
a
2
a
3
a
4
a
5
] (7.28)
Here the vectot [p] represents the basis sets. Note that these can be any set of independent
functions e.g. [p] = [1 t si n(t) exp(t) t
3
]. This can be expanded for every data point n :
_
¸
¸
¸
¸
¸
_
ε
1
ε
2
ε
3
.
.
.
ε
n
_
¸
¸
¸
¸
¸
_
=
_
¸
¸
¸
¸
¸
_
c
A,1
C
A,2
C
A,3
.
.
.
C
A,n
_
¸
¸
¸
¸
¸
_
−
_
¸
¸
¸
¸
¸
_
1 1 1 1 1
t
1
t
2
· · · · · · · · ·
t
2
1
t
2
2
.
.
.
.
.
.
t
3
1
.
.
.
.
.
.
t
n
1
· · · · · · · · · t
n
n
_
¸
¸
¸
¸
¸
_
_
¸
¸
¸
¸
¸
_
a
1
a
2
a
3
.
.
.
a
m
_
¸
¸
¸
¸
¸
_
= [ε] = [C
A
] −[p][a]
T
≈ 0 (7.29)
87
7.2. BATCH REACTORS CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
Note that m is the number of parameters [a] which in this case is 5. Note also that m ≤ n
for a meaningful solution. When m = n then the solution is unique, one parameter for every
equation. However, as with most data, n > m and the solution will never be exactly zero, rather
the objective function needs to be minimized, thus
mi n Ψ = [ε]
T
[ε] (7.30)
Matlab’s and Scilab’s backslash operator (\) does exactly that (i.e. the overdetermined system,
Ax = b yields the least squares solution x = A\b). Applying this concept here yields the
parameters of the polynomial that ﬁts the C
A
vs t data;
[a]
T
= [p]\[C
A
] = [50 −0.2978 1.34E −03 −3.485E −06 3.67E −09]
The code that does this is and the data is given in the table.
//polynomial fit to the data using a nonlinear leasts squares
solver (the long way)
function f=polfit(a,n)
tx=[ones(1:n); tt; tt^2; tt^3; tt^4]’; //define the
vector of polynomial basis sets
f=Ca’tx*a’ //calculate the error at each point
endfunction
a0=[1 1 1 1 1]; //initial guess
a=lsqrsolve(a0,polfit,n) //solve the nonlinear problem
disp(’a_cubic=[’+string(a)+’]’) //display
tx=[ones(1:nt); t; t^2; t^3; t^4]’;
Cap=tx*a’; //calculate the polynomial fitted values
function f=CaPol(t) //define a function in terms of t
tx=[ones(1:n)’ t t^2 t^3 t^4]; //changes since t is a
column vector
f=tx*a’ //the value of Ca
endfunction
//polynomial regression using linear leasts squares (the short
but abstract way)
txx=[ones(1:n); tt; tt^2; tt^3; tt^4];
aa=txx’\Ca’
disp(’a_poly=[’+string(a)+’]’)
Table 7.1: Reaction rate as a function of concentration using cubic spline and polynomial ﬁtting.
C
A
50 38 30.6 25.6 22.2 19.5 17.4
−
_
dC
A
dt
_
spl i ne
0.303 0.185 0.119 0.0814 0.0590 0.0485 0.0351
−
_
dC
A
dt
_
pol y
0.298 0.188 0.119 0.0801 0.0603 0.0485 .0334
The ﬁtted data is shown in Fig 7.1.
88
7.2. BATCH REACTORS CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
15
20
25
30
35
40
45
50
0 50 100 150 200 250 300
time; t [s]
c
o
n
c
e
n
t
r
a
t
i
o
n
;
C
A
[
m
m
o
l
:
L
¡
1
]
Figure 7.1: Cubic and polynomial ﬁt to the data.
The linear regression using equa 7.25 is
//linear regression for the rate constant and reaction order
//using cubic spline data
aa_s=regress(log(Ca’),log(dCa_dt_s)); //such that
log(dCa_dt)=aa(1)+aa(2)*log(Ca)
kr=exp(aa_s(1))
alpha=aa_s(2)
disp(’k=’+string(kr)+’ alpha=’+string(alpha));
//using polynomial data
aa_p=regress(log(Ca’),log(dCa_dt_p)); //such that
log(dCa_dt)=aa(1)+aa(2)*log(Ca)
kr=exp(aa_p(1))
alpha=aa_p(2)
disp(’k=’+string(kr)+’ alpha=’+string(alpha));
Linear regression of the spline ﬁt data this data yields :
l n(k) = −9.116; k
= 0.0001099 L.mmol
−1
.min
−1
and α = 2.035 and l sqr Er r r or = 0.0136
Linear regression of the poly ﬁt data this data yields :
l n(k) = −9.116; k
= 0.0001046 L.mmol
−1
.min
−1
and α = 2.048 and l sqr Er r r or = 0.0199
Direct nonlinear regression of the cubic spline data uses this equation
mi n f (k
, α) =
n
i =1
_
−
_
dC
A
dt
_
i
−k
C
α
A,i
_
and the following code
89
7.2. BATCH REACTORS CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
//direct nonlinear regression
function f=EE(b,n)
k=b(1);alpha=b(2)
f=dCa_dt_sk*(Ca^alpha)’
endfunction
b0=[1 1];
b=lsqrsolve(b0,EE,n)
disp(’k=’+string(b(1))+’ alpha=’+string(b(2)));
this data yields :
k
= 0.0001467 L.mmol
−1
.min
−1
and α = 1.954 and l sqr Er r r or = 0.00902
So why are these values diﬀerent :
Figure 7.2 shows the two diﬀerent plots which eﬀectively represent the two diﬀerent methods.
10
10
10
2
1
0
10 10
1 2
C
A
[mmol:L
¡1
]
¡
d
C
A
d
t
[
m
m
o
l
:
L
¡
1
:
m
i
n
¡
1
]
(a) linearﬁt
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
15 20 25 30 35 40 45 50
C
A
[mmol:L
¡1
]
¡
d
C
A
d
t
[
m
m
o
l
:
L
¡
1
:
m
i
n
¡
1
]
(b) nonlinearﬁt
Figure 7.2: Comparing the linear data ﬁt with the nonlinear data ﬁt. The green line represents
the nonlinear ﬁt.
The linear regression transforms the data into a loglog scale. This means that the error for
the small values of the concentrations and small rates are weighted much more heavily than the
values at the large concentrations. However, typically, small concentrations are more diﬃcult
to measure and thus also have the largest experimental error. This error is magniﬁed by the
loglog scaling. The nonlinear ﬁtting, on the other hand, leaves the data in its original for and
weights all errors on this basis.
Figure 7.2(a) shows the loglog plot is not able to distinguish between the diﬀerent regressions.
On the other hand Fig 7.2(b) shows that the nonlinear regression (green) shows a superior ﬁt to
the rate data at high concentrations. The nonlinear ﬁtting thus provides a more representative
set of rate constants. This deviation is more pronounced in the rate constant.
PART 2
Since β = 1 then the true rate constant k can eb calculated:
k =
k
C
B0
= 2.92E −7 [L.mol
−1
.min
−1
]
2
Thus the rate law is given by
−r
A
= 0.292C
2
A
C
B
[mol.L
−1
.s
−1
]
90
7.2. BATCH REACTORS CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
It is possible to ﬁt for all 3 parameters k αβ if the concentration of B can be found from the
concentration of A. (normally B should also be measured). This would give an idea of the errors
made in assuming that the concentration of B is constant. From the reaction stoichiometry
C
A
= C
A0
(1 −X); X = 1 −
C
A
C
A0
C
B
= C
B0
−C
A0
X = C
B0
−C
A0
+ C
A
Then the rate law becomes
−r
A
= kC
α
A
(C
B0
−C
A0
+ C
A
)
β
which can be used for dirrect nonlinear regression or linear regression using the loglog approach
nonlinear
mi n f (k, α, β) =
n
i =1
_
(−r
A,i
) −kC
α
A,i
(C
B0
−C
A0
+ C
A,i
)
β
_
2
which can be solved by a nonlinear leasts squares, Scilab’s “lsqrsolve”
[k, α, β] = [180, 2.13, −2.37] with l sqr Er r r or = 0.00712.
This has the smallest error of them all. Interesting, WHY
Linear loglog:
l n(−r
A
)
i
= l n(k) + αl n(C
A,i
) + βl n(C
B0
−C
A0
+ C
A,i
)
l n(−r
A
) = p ∗ a
p =
_
¸
¸
¸
¸
_
1 l n(C
A
) l n(C
B0
−C
A0
+ C
A,i
)
1
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
1
.
.
.
.
.
.
_
¸
¸
¸
¸
_
a =
l n(k)
α
β
which can be solved by the “backslash” (a = p\l n(−r
A
)).
[k, α, β] = [9.44E13, 2.47, −6.93] with l sqr Er r r or = 0.067.
This solution has failed. This is due to the linear dependence of the two concentration columns.
7.2.3 Example : Integral method
Contrary to what Fogler says, this is not a trial and error method. When the reaction orders are
known, then there are many standard rate laws for which the design equations can be integrated
and a appropriate regression can be carried out. If not, then they simply become partr of the
regression procedure.
7.2.3.1 The standard (linearised) analyses
For the reaction A → pr oducts it is always useful to test the data with the standard cases,
or make a standard plot. Assuming a constant volume batch reactor, the following analyses
can be used for zero, ﬁrst, second and nth order reactions. Fig 7.3 shows these plots on a
concentration basis for a batch reactor.
91
7.2. BATCH REACTORS CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
Zero order reaction
C
A
= C
A0
¡kt
slope = ¡k
WARNING
There is no natural limit
on the smallest value of C
A
it can go negative
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
time; t [s]
c
o
n
c
e
n
t
r
a
t
i
o
n
;
C
A
[
m
o
l
:
m
¡
3
]
¯rst order reaction
log
µ
C
A
C
A0
¶
= ¡kt
slope = ¡k
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
0.5
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
time; t [s]
l
o
g
µ
C
A
C
A
0
¶
o
r
l
o
g
(
1
¡
X
)
2nd order reaction; kC
2
A
1
C
A
= kt +
1
C
A0
slope = k
R
x
n
o
r
d
e
r
<
2
R
x
n
o
r
d
e
r
>
2
1.0
1.5
2.0
2.5
3.0
3.5
4.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
time; t [s]
1
C
A
2nd order reaction; kC
A
C
B
log
µ
C
A
C
B0
¡C
A0
+ C
A
¶
= ¡k(C
B0
¡C
A0
)t + log
µ
C
A0
C
B0
¶
slope = ¡k(C
A0
¡C
B0
)
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
time; t [s]
l
o
g
µ
C
A
C
B
0
¡
C
A
0
+
C
A
¶
Figure 7.3: Batch reactor integral analysis linear plots for zero, ﬁrst and second order kinetics
using concentrations.
Zero order reaction :
dC
A
dt
= −k; C
A
= C
A0
−kt; X =
k
C
A0
t (7.31)
So plotting C
A
vs t is a linear plot with an intercept C
A0
and slope −k, as shown in Fig
7.3. (or plotting X vs t has a slope of
k
C
A0
. Note that it is not necessary to know the
initial concentration C
A0
when making the C
A
vs t plot, since this given my the intercept.
First order reaction :
dC
A
dt
= −kC
A
;
C
A
C
A0
= exp(−kt); 1 −X = exp(−kt) (7.32)
linearisation yields
l n
_
C
A
C
A0
_
= −kt; l n(1 −X) = −kt (7.33)
So when plotting l n
_
C
A
C
A0
_
vs t the slope of the line is −k, as shown in Fig 7.3 (similarly
for plotting of l n(1 −X) vs t) Note that rearrangement to
l n(C
A
) = l n(C
A0
) −kt (7.34)
92
7.2. BATCH REACTORS CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
and plotting l n(C
A
) vs t also does not require knowledge of the intial concentration.
Furthermore, the reaction rate does not depend on the concentration, and thus it is not
important to keep the initial concentration constant during experimentation.
Second order reaction :
dC
A
dt
= −kC
2
A
;
dX
dt
= kC
A0
(1 −X)
2
Also for C
A0
= C
B0
(7.35)
dC
A
dt
= −kC
A
C
B
= −kC
A
(C
B0
−C
A0
+ C
A
);
dX
dt
= kC
A0
(1 −X)
_
C
B0
C
A0
−X
_
(7.36)
and their integrated forms rearranged into linear equations for C
A0
= C
B0
:
1
C
A
= kt +
1
C
A0
plot :
1
C
A
vs t slope : k intercept :
1
C
A0
(7.37)
X
1 −X
= kC
A0
t plot :
X
1 −X
vs t slope: kC
A0
(7.38)
And for C
A0
= C
B0
:
l n
_
C
A
C
B0
−C
A0
+ C
A
_
= −k(C
B0
−C
A0
)t + l n
_
C
A0
C
B0
_
(7.39)
plot : l n
_
C
A
C
B0
−C
A0
+ C
A
_
vs t slope : −k(C
B0
−C
A0
) intercept : ln
_
C
A0
C
B0
_
(7.40)
l n
_
_
_
_
C
A0
C
B0
X −1
X −1
_
_
_
_
= k(C
B0
−C
A0
)t (7.41)
plot : l n
_
_
_
_
C
A0
C
B0
X −1
X −1
_
_
_
_
vs t slope : k(C
B0
−C
A0
) (7.42)
Some of these standard plots are made in Fig 7.3. In all cases, except for
1
C
A
= kt +
1
C
A0
it is necessary to know the concentrations of A and B at the start of the reaction.
q
th
order reaction :
dC
A
dt
= −kC
q
A
;
dX
dt
= kC
q−1
A0
(1 −X)
q
(7.43)
1
C
q−1
A
= −k(1 −q)t +
1
C
q−1
A0
;
1 −(1 −X)
q−1
(1 −x)
q−1
= k(1 −q)t (7.44)
In these linearised equations it is necessary to know the reaction order q. (see Fig 7.3)
7.2.3.2 Example 5.2 (Fogler)
Continuation of example 5.1 : The purpose now is to regress the concentration data directly
without ﬁnding the reaction rate. Thus, assuming that teh reaction is second order;
−
dC
A
dt
= k
C
2
A
;
1
C
A
= k
t +
1
C
A0
(7.45)
93
7.2. BATCH REACTORS CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
Regression can be done by noting that the integrated equation is related to y = a + bx when
y =
1
C
A
and x = t. The the solution of this equation by for example Scilab’s “regress” routine,
yields b = k
and a =
1
C
A0
. The value obtained for a provides a check on the validity of the
model, since C
A0
is already known. So k
= 0.0001248 and ”C
A0
” = 49.7. So the model ﬁts
the data well as shown in Fig 7.4..
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
0.055
0.060
0 50 100 150 200 250 300 350
time; t [min]
1
C
A
[
L
:
m
o
l
¡
1
]
Figure 7.4: Standard regression plot for the second order reaction.
7.2.4 Example : Nonlinear regression
Nonlinear regression requires the development of a objective function which is then used in a
nonlinear leasts squares solver (Scilab’s “lsqrsolve” is a particularly good one, EBEmatlab does
not have such routines and the nextbest bet is EXCEL!!!)
Continuation of Foglers example 51:
Noting that k
and α are to be found and that the data is given in the form C
exp
A,i
vs t
i
, it
therefore makes sense to integrate a general αorder rate equation and its integrated form.;
dC
A
dt
= −k
C
α
A
; C
model
A
=
_
C
1−α
A0
−(1 −α)kt
¸
1
1 −α
(7.46)
This is the batch reactor design equation and will from now on be called the model. Now the
purpose of this method is to minimise the error between the experimental concentrations and
the model predicted concentrations, thus this will form the objective function;
mi n f (k
, α) =
n
i =1
ε
i
ε
i
= εε
T
(7.47)
94
7.3. METHOD OF INITIAL RATES CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
where n is the number of experimental data points and ε
i
is the error between the experimental
and model concentrations;
ε
i
= C
exp
A,i
−C
model
A,i
(7.48)
ε
i
= C
exp
A,i
−
_
C
1−α
A0
−(1 −α)kt
i
¸
1
1 −α
(7.49)
where ε is a vector of values,one for each data point collected
ε =
_
ε
1
ε
2
. . . . . . ε
n
¸
(7.50)
The solution proceeds by developing a function that calculates the ε
i
values at each data point
and then call the scilab routine lsqrsolve to carry out the least squares minimisation. The scilab
function is
function f=model1(x,n)
kr=x(1);alpha=x(2); //x is a vector of two parameters
f=Ca(Ca(1)^(1alpha)(1alpha)*kr*tt)^(1/(1alpha))
endfunction
The calling of the least squares solver then has hte code
//call the least squares solver
x0=[0.0001 2]; //initial guess
x=lsqrsolve(x0,model1,n)
kr=x(1);alpha=x(2);
disp(’kr=’+string(kr)+’ alpha=’+string(alpha))
Cam=(Ca(1)^(1alpha)(1alpha)*kr*t)^(1/(1alpha)) //model predicted val
ues
The model parameters obtained are :
k
= 0.000111 α = 2.037
And the quality of the fata ﬁt can be seen in Fig 7.5.
It is possible to use the same code to regress with α = 2. When this is done then k
= 0.000126
similar to those obtained before. The values of k
are summarised here:
method k
α
diﬀerential : Linear regression of the spline ﬁt 0.1109 2.035
diﬀerential : Linear regression of the poly ﬁt 0.1046 2.048
diﬀerential : nonlinear regression 0.1467 1.95
Integral 0.1248 2.000
nonlinear regression C
A
0.111 2.037
nonlinear regression 0.126 2.000
7.3 Method of initial rates
The idea here is to study the reaction at very short reactions times, or more precisely, at small
conversions (say < 5% change in conversion over the reaction period). This avoids complications
from any possible reversible reaction steps, deactivation as a result of byproducts forming,
etc. These experiments are carried out a various inlet concentrations (C
A0
) and/or various
conversions at the inlet. Then the reaction rate at these conditions is estimated from data
collected over a very small conversion range. Possible sequences might be
95
7.3. METHOD OF INITIAL RATES CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
15
20
25
30
35
40
45
50
55
0 50 100 150 200 250 300
time; t [min]
C
A
[
m
o
l
:
L
¡
1
]
Figure 7.5: Predicted and experimental data when using the nonlinear leasts squares method
applied to concentration data.
C
A0
20 10 5 2 1
C
A
19 9.5 4.75 1.9 0.95
t 10 15 12 10 8
Which yields the reaction rate
∆C
A
∆t
=
C
A0
−C
A
t
at the concentration
C
A0
+ C
A
2
from which
the law parameters can be obtained. Or possibly
X
i n
0.1 0.2 0.3 0.4 0.5
X
out
0.11 0.21 0.31 0.41 0.51
F
A0
10 15 20 25 30
From which the reaction rate can be obtained from a diﬀerential reactor balance (see later)
Limitations of this method
1. Real reactions undergo deactivation. If deactivation is fast (FCC) then this method fails
since it becomes impossible to esrimate the initial reaction rate without the inﬂuence of
the deactivation.
2. Real reactors operate at very high conversions, contrary to the very low conversions used
here. High conversions almost always produce side products which can inﬂuence the
reaction kinetics, especially at high conversions, which are the conditions used under normal
operation. These methods fail to analyse such reaction systems
7.3.1 Example (Fogler 54)
The dissolution kinetics CalciumMagnesiumcarbonate within HCl has been measured and is
shown in the graphs below. The data in the tables have been extracted from the graphs. The
reaction is
4HCl + CaMg(CO
3
)
2
→Mg
2+
+ Ca
2+
4Cl
−
+ 2CO
2
+ 2H
2
O (7.51)
96
7.3. METHOD OF INITIAL RATES CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
Determine the reaction order with respect to HCl ?
DATA:
Run1, 4N HCl
C
HCl
4.0000 3.9993 3.9986 3.9980 3.9968
time [min] 0 2 4 6 8
Run2, 1N HCl
C
HCl
1 0.9996 0.9991 0.9986 0.9980
time [min] 0 2 4 6 8
Figure 7.6: Data for example (Fogler54).
SOLUTION
Assume a rate law with reaction order q :
−r
HCl
= kC
q
HCl
(7.52)
This is a batch reactor, so the design equation for a constant volume system is
−
dC
HCl
dt
= kC
q
HCl
(7.53)
Linearising:
l n
_
−
dC
HCl
dt
_
= l n(k) + ql n(C
HCl
) (7.54)
Thus need to estimate the reaction rate at t = 0 in each case. This can be done with a forward
diﬀerence formula since the data is equally spaced;
dC
CCl
dt
=
−3C
t=0
HCl
+ 4C
t=2
HCl
−C
t=4
HCl
2∆t
; ∆t = 2 (7.55)
which yields
C
HCl ,0
[mol.L
−1
] 1 4 2 0.1 0.5
−
dC
HCl
dt
[mol.L
−1
.min
−1
] 1.74E4 3.50E4 2.49E4 0.66E4 1.36E4
Regressing these to get the reaction order: q = 0.45 and Fig 7.7 shows that the model ﬁts the
data well.
97
7.4. METHOD OF HALF LIVES CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
10
10
10
5
4
3
10 10 10
1 0 1
µ
¡
d
C
A
d
t
¶
0
[
m
o
l
:
L
¡
1
:
m
i
n
¡
1
]
Figure 7.7: Linearised initial rate plot for the dissolution process.
7.4 Method of half lives
The half life of a reaction is the time it takes to reduce the conversion (concentration) by half
the initial value. Thus a irreversible reaction, A → pr oducts with a q
th
order rate law in a
batch reactor the design equation is;
−r
A
= −kC
q
A
−
dC
A
dt
= kC
q
A
(7.56)
Integration yields the reaction time to reach the concentration C
A
;
t =
1
k(q −1)
_
1
C
q−1
A
−
1
C
q−1
A0
_
=
1
kC
q−1
A0
(q −1)
_
_
C
A0
C
A
_
q−1
−1
_
(7.57)
Using the halflife concept : t = t
1/2
then C
A
=
1
2
C
A0
, thus
t
1/2
=
2
q−1
−1
k(q −1)
_
1
C
q−1
A0
_
(7.58)
or using a general concept, the n
th
life time, such that t = t
1/n
when C
A
=
1
n
C
A0
yields
t
1/n
=
n
q−1
−1
k(q −1)
_
1
C
q−1
A0
_
(7.59)
Linearising this equation
l n(t
1/2
) = l n
_
2
q−1
−1
k(q −1)
_
+ (1 −q)l n(C
A
)
The slope of the plot is (1 −q) from which the reaction order can be obtained as shown in Fig
7.8.
98
7.5. DIFFERENTIAL REACTORS (INCLUDING CSTR AND RECYCLE REACTORS) CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
Figure 7.8: Halflife analysis plot.
7.5 Diﬀerential reactors (including CSTR and recycle reac
tors)
The idea of these kinds of reactors is to directly calculate the reaction rate and not have to
diﬀerentiate the concentrationtime data. This reduces the error. These reactors also operate
with no pressure drop and isothermally as a result of the reaction zone and conversion being
small. There are essentially 2 types of diﬀerential reactors :
Fixed bed (plug ﬂow) : In these reactors the conversion in the reactive zone is small. The
feed enters the reactor at various degrees of conversion which is achieved by dilution with
product species. In this way the reaction rate can be estimated at diﬀerent conversions.
The ﬂow rate of reactants to the reactor remains largely unchanged.
CSTR’s and recycle reactors : The CSTR delivers the reaction rate at any concentration di
rectly from the measured variables. The conversion is changed by changing the feed rate
and not the feed conversion as is needed for the ﬁxed bed reactor. A recycle reactor (no
separation of the products must take place) can be assumed to have the same analysis as
a CSTR when the recycle ratio is greater than 20, which translates into a conversion per
pass of <5%.
These type of experiments are not generally carried out in Batch type reactors, since it is diﬃcult
to precisely deﬁne the conditions at t = 0. These ideas can be viewed in Fig 7.9.
99
7.5. DIFFERENTIAL REACTORS (INCLUDING CSTR AND RECYCLE REACTORS) CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
Figure 7.9: Diﬀerential reactor operation : concepts.
7.5.1 Mole balances : CSTR (and recycle reactor with rapid recycle)
−r
A
[mol.L
−1
.s
−1
] =
F
A0
−F
A
V
=
F
A0
V
X =
ν
0
C
A0
V
X =
C
A0
τ
X (7.60)
−r
A
[mol.kg
−1
.s
−1
] =
F
A0
−F
A
W
=
F
A0
W
X = (WHSV )C
A0
(7.61)
So CSTR’s yield the reaction rate directly at any concentration or conversion of the reactants
or products (even for multiple reactions). This is the ideal reactor conﬁguration to use for the
development of rate laws. However, it is very diﬃcult to achieve good CSTR operation, and
great care must be taken to ensure that the mixing is adequate such that the CSTR assumptions
are valid. The variation in reaction rate is obtained by changing the volume (V, W), the ﬂow
rate (F
A0
) or more precisely the τ, WHSV .
Fig 7.9 shows the concepts of how a recycle system relates to a real integral reactor. Essentially
the catalytic zone (reactive zone) represents a slice of the normal reactor. When this reactor
section of the reactor is placed within a recycle loop in which the recycle ﬂow rate exceeds 20
times the feed ﬂow rate, the reactor feed will no longer be pure feed, by will be mixed with
products of the reaction and will thus enter partially converted. The high ﬂow rates through the
reactor section ensure that (i) the conversion is low <5% (ii) the ﬁlm mass transfer limitations
are negligible. It thus provides a ideal reactor for studying the rate law of reactions.
100
7.5. DIFFERENTIAL REACTORS (INCLUDING CSTR AND RECYCLE REACTORS) CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
7.5.2 Mole balances : Tubular and packed bed systems
Fig 7.9 also shows that the diﬀerential reactor is also a slice of the full scale reactor. However,
in this reactor the feed must be premixed with products to yield feeds that reproduce the
conversion proﬁle of the fullscale reactor. For complex reactions this proves to be impossible.
In practice for complex reaction systems, the experimental system operates with two reactors
in series, the ﬁrst one large enough to generate the conversion desired to be used in the second
diﬀerential reactor. These systems are not popular for the study of complex chemical reaction
system kinetics.
The mole balances are best viewed through the ﬁrst order approximation to the PBR design
equation, thus;
F
A

Z
−F
A

Z+∆Z
−r
A
∆W = 0;
dF
A
dW
= ν
0
dC
A
dW
= −r
A
; F
A0
dX
dW
= r
A
(7.62)
Now making a ﬁrst order approximation of the diﬀerential to yield the average reaction rate
within the diﬀerential interval ∆W is
−r
A
=
F
A,out
−F
A,i n
∆W
= ν
0
C
A,out
−C
A,i n
∆W
= F
A0
X
out
−X
i n
∆W
(7.63)
Here the conditions F
A0
and C
A0
are reserved for the ﬂow rate and concentration of the un
converted feed and correspond to X = 0. The reaction rate so evaluated represents, to a
ﬁrst approximation the reaction rate at the middle of the ∆W interval, i.e. at
F
A,out
+ F
A,i n
2
;
C
A,out
+ C
A,i n
2
,
X
out
+ X
i n
2
. It is not the reaction rate at the inlet to the diﬀerential reactor as
proposed by Fogler, i.e. draw a parallel with the trapazoidal integration where the integration
uses the average value between the end points of the interval if the integration step.
7.5.3 Example : Fogler 55
The formation of methane from carbon monoxide(A) and hydrogen(B)
CO + 3H
2
→ CH
4
+ H
2
O
A + 3B → C + 2D
is being studied at 260°C in a diﬀerential reactor where the concentration of methane leaving
the reactor is measured.
(a) From the data supplied determine the conversion for each experiment and the partial pres
sures of CO and H
2
at the inlet and outlet of the reactor. Determine also the average
reaction rate of CO across the reactor.
(b) The reaction rate equation is proportional to the partial pressure of CO with the function
f (CO) and proportional to the partial pressure of H
2
with the function g(H
2
);
−r
CO
= f (CO) · g(H
2
)
Determine the reaction order with respect to P
CO
by assuming the rate equation;
−r
CO
= k
1
P
a
CO
101
7.5. DIFFERENTIAL REACTORS (INCLUDING CSTR AND RECYCLE REACTORS) CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
(c) Show that the data suggests a rate law for the hydrogen dependence of
−r
CO
=
k
2
P
b
1
H
2
1 + K
H
2
P
b
2
H
2
(d) By combining the two rate laws, yields the overall rate equation
−r
CO
=
kP
CO
P
b
1
H
2
1 + K
H
2
P
b
2
H
2
Regress this equation for the constants k, b
1
, b
2
, K
H
2
.
DATA:
Table 7.2: Experimental reaction data for the conversion of CO to CH
4
.
Run P
CO
[atm] P
H
2
[atm] C
CH
4
[mol.L
−1
]×10
4
1 1 1 1.73
2 1.18 1 4.40
3 4.08 1 10.0
4 1 0.1 1.65
5 1 0.5 2.47
6 1 4.0 1.75
The exit volumetric ﬂow rate was maintained at 300 [L.min
−1
]. The catalyst bed contained
10 g of catalyst. P
CO
and P
H
2
were measured at the reactor inlet and C
CH
4
was measured at the
reactor exit.
SOLUTION
(a)
Looking at the data
(i) There are 2 sets of data, runs 13 are at constant P
H
2
and runs 1,46 are at constant P
CO
.
Thus the CO and H
2
dependence can be analysed separately
(ii) The data required will require a stoichiometric table to relate all the quantities to each other.
Make the usual assumptions : ideal gases, isothermal reactor, ...
Design equation for the reaction rate of CO is
−r
CO
= F
A0
X
out
∆W
∝ f (P
CO
) · g(P
H
2
)
Thus it will be necessary to determine the conversion,X, the molar ﬂow rate of CO, F
A0
and
the average partial pressures of CO and H
2
across the reactor.
Stoichiometric table gives
A B C D
in F
A0
F
B0
0 0
out F
A0
(1 −X) F
A0
_
F
B0
F
A0
−3X
_
F
A0
X 2F
A0
X
total F
0
= F
A0
(1 + α) F
T
= F
A0
(1 + α −X) α =
F
B0
F
A0
=
P
B0
P
A0
102
7.5. DIFFERENTIAL REACTORS (INCLUDING CSTR AND RECYCLE REACTORS) CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
From the data, the methane concentration gives the reaction rate, and since the exit volume
ﬂow rate (ν) is given, the molar ﬂow rate of methane can be calculated from
F
C
= νC
CH
4
= F
A0
X
The conversion can be obtained by looking at the methane concentration
C
CH
4
=
F
C
F
T
P
RT
=
X
1 + α −X
C
T
Rearrangement gives the conversion
X =
C
CH
4
(1 + α)
C
CH
4
+ C
T
Note that the total presssure P and thus the total concentration, C
T
is not constant since,
P = P
A0
+P
B0
and varies from run to run. Thus F
A0
can be obtained from the above equation.
The partial pressures of CO and H
2
at the reactor exit are given by
P
A
=
1 −X
1 + α −X
(P
A0
+ P
B0
); P
B
=
α −3X
1 + α −X
(P
A0
−P
B0
)
and the reaction rate of CO can be obtained from the above equation. Making a new table 7.3.
Table 7.3: Processed reaction data.
Run P
A,i n
P
B,i n
α P C
T
X F
A0
P
A,out
P
B,out
−r
CO
P
A,ave
P
B,ave
1 1.00 1.00 1.000 2.00 0.0457 0.0075 6.88 0.996 0.981 0.0052 0.998 0.990
2 1.18 1.00 0.847 2.18 0.0498 0.0161 8.16 1.171 0.951 0.0132 1.175 0.975
3 4.08 1.00 0.245 5.08 0.116 0.0106 28.2 4.071 0.877 0.0300 4.075 0.938
4 1.00 0.10 0.100 1.10 0.0251 0.0071 6.90 0.999 0.079 0.0049 0.999 0.089
5 1.00 0.50 0.500 1.50 0.0342 0.0107 6.90 0.996 0.471 0.0074 0.998 0.485
6 1.00 4.00 4.000 5.00 0.114 0.0076 6.86 0.993 3.983 0.0052 0.996 3.99
P
A
is relatively constant, however the biggest variation (still not much) is in P
B
across the
reactor even when P
B0
is a constant, since 3 moles of B required for every mole of A that reacts
away.
(b)
Regression for k
1
, a :
l n (−r
CO
) = l n(k
1
) + a · l n(P
CO
)
thus k
1
= 0.00745 and a = 1.03. Fig 7.10 shows that the data scatter is large and too few
points!!
103
7.5. DIFFERENTIAL REACTORS (INCLUDING CSTR AND RECYCLE REACTORS) CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
10
10
10
3
2
1
10 10 10
1 0 1
P
CO
[atm]
l
n
(
¡
r
C
O
)
[
m
o
l
:
L
¡
1
:
m
i
n
¡
1
]
Figure 7.10: Regression plot for the −r
CO
dependence on P
CO
.
(c)
Looking at the second table and the rate law
−r
CO
=
k
2
P
b
1
H
2
1 + K
H
2
P
b
2
H
2
and making a plot of the data, Fig 7.11.
0.0045
0.0050
0.0055
0.0060
0.0065
0.0070
0.0075
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
P
H
2
[atm]
l
n
(
¡
r
C
O
)
[
m
o
l
:
L
¡
1
:
m
i
n
¡
1
]
Figure 7.11: Plotting the −r
CO
dependence on P
H
2
.
(i) plotting the data shows that at low P the rate is low,it then increase as P
H
2
increases, goes
through a maximum and then decreases again.
104
7.5. DIFFERENTIAL REACTORS (INCLUDING CSTR AND RECYCLE REACTORS) CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
(ii) At low P
H
2
: then 1 K
H
2
P
b
2
H
2
and the rate law reduces to : −r
CO
= k
2
P
b
1
H
2
. Thus as
P
H
2
increases, so does the reaction rate.
(ii) At high P
H
2
: then 1 K
H
2
P
b
2
H
2
and the rate law reduces to −r
CO
=
k
2
K
H
2
P
b
1
−b
2
H
2
. If b
1
−b
2
< 0
then increasing the pressure will decrease the reaction rate.
The data is rather few, but the trend of the rate law obeys the rate data at least conceptually.
(d)
Regressing all the data,use a nonlinear regression for all the constants
mi n obj (k, b
1
, b
2
, K
H
2
) =
6
i =1
_
−r
CO,i
−
kP
CO,i
P
b
1
H
2
,i
1 + K
H
2
P
b
2
H
2
,i
_
In Scilab this looks like this
//least squares regression for all the parameters
function f=model(p,n)
k=p(1);b1=p(2);b2=p(3);Kh2=p(4);
//b1=0.5;b2=1;
f=ratek*Paa.*Pbb^b1./(1+Kh2*Pbb^b2)
endfunction
And calling the least squares solver with an initial guess
p0=[0.02 0.5 1 1];
[p v info]=lsqrsolve(p0,model,n)
disp(info,’info’);
disp(norm(v),’lsqrE’);
disp(p,’p’)
k=p(1);b1=p(2);b2=p(3);Kh2=p(4);
rate_m=k*Paa.*Pbb^b1./(1+Kh2*Pbb^b2) //predict the reaction rate from
parameters
The parameters are p = [k
2
, b
1
, b
2
, K
H
2
] = [0.01135, 0.33, 1.115, 0.510] with a LSQRerror of
0.0050 and a variance of σ = [0.79, 26, 46, 106] i.e p = p ± σ. The ﬁt of the model to the
reaction rate is shown inFig 7.12. It can be seen that the reaction rate at constant P
H
2
is not
was well predicted as the variation with P
H
2
. This is already noted in the scatter when ﬁtting
for the reaction order of CO. Furthermore the variance in the model parameters is very high,
in fact the model parameters are useless, since the variance exeeds the parameter value.
The rate law then is
−r
CO
=
0.01135P
CO
P
0.33
H
2
1 + 0.510P
1.115
H
2
Also the reaction orders are noninteger values, which from mechanistic considerations is not
realistic. Typically reaction orders are [0, 0.5, 1, 1.5, ...]
With this in mind and the fact that there are too many parameters for such few data, rounding
the orders of the reactions oﬀ to the nearest accepable value, yields
−r
CO
=
kP
CO
P
0.5
H
2
1 + K
H
2
P
H
2
Now regressing again yields k = 0.0287 and K
H
2
= 2.90 with a LSQRerror of 0.0050 and a
variance σ = [0.0484, 3.79] which is still very high, but at least better then before. Fig 7.13
shows the ﬁt of the reaction rate.
105
7.5. DIFFERENTIAL REACTORS (INCLUDING CSTR AND RECYCLE REACTORS) CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
P
H
2
[atm]
¡
r
C
O
[
m
o
l
:
L
¡
1
:
m
i
n
¡
1
]
Figure 7.12: The prediction of the reaction rate when regressing for all the rate law constants.
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
P
H
2
[atm]
¡
r
C
O
[
m
o
l
:
L
¡
1
:
m
i
n
¡
1
]
Figure 7.13: The prediction of the reaction rate when regressing for k, K
H
2
in the rate law.
This yields the ﬁnal rate law
−r
CO
=
0.0189P
CO
P
0.5
H
2
1 + 1.48P
H
2
The rate law is OK, just there are too few data points ot make these values reliable. Note, that
the LSQRerror does not change much between the last 2 rate laws. There are not enough data
points to accurately evaluate the reaction orders.
The Scilab code “FoglerEx55.sce” does all the calculations.
106
Chapter 8
Developing rate laws from reaction
mechanisms and reaction pathways
107
Chapter 9
Bioreactor engineering mechanisms
108
Chapter 10
Bioreactor design
109
Chapter 11
Analysis of reactor ﬂow patterns on
reactor performance (Fogler chapter 13)
110
Contents
1 Mole (or mass) balances 1.1 Chemical Reaction Engineering . . . . . . . . . . . . . . . . . 1.1.1 Generic ﬂow diagram of a chemical process . . . . . . 1.1.2 What do we need to know . . . . . . . . . . . . . . . 1.1.3 Industrial processes . . . . . . . . . . . . . . . . . . . 1.1.4 The Chemical Feed stocks . . . . . . . . . . . . . . . 1.2 Rate of a reaction . . . . . . . . . . . . . . . . . . . . . . . . 1.2.1 Deﬁning when a chemical reaction takes place . . . . 1.2.2 Deﬁning the rate of reaction . . . . . . . . . . . . . . 1.2.3 The volume in the reaction rate and its relationship to reacting system. . . . . . . . . . . . . . . . . . . . . 1.2.4 The rate equation . . . . . . . . . . . . . . . . . . . 1.3 The general mole balance . . . . . . . . . . . . . . . . . . . . 1.4 Mole balance for batch reactors . . . . . . . . . . . . . . . . 1.5 Mole balance for continuous stirred tank reactor (CSTR) . . . 1.6 Mole balance for a homogeneous plug ﬂow reactor (PFR) . . 1.7 Mole balance for a heterogeneous ﬁxed bed reactor (FBR) . . 1.8 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . Reactor sizing for single reactions using conversion 5 6 6 8 9 10 12 12 13 14 14 15 16 18 19 22 23 24
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. . . . . . . . . . . . . . . . . . . . . . . . mass . . . . . . . . . . . . . . . . . . . . . . . .
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2 3
Properties and deﬁnitions of the reaction rate equation (reaction rate law) (Fogler chapter 3) 47 Reaction stoichiometry and the reaction rate law (Fogler chapter 3) Isothermal reactor design for single reactions (Fogler chapter 4) Isothermal reactor design for multiple reactions (Fogler chapter 6) Collection and data analysis (Fogler chapter 5) 7.1 Algorithm . . . . . . . . . . . . . . . . . . . 7.1.1 Limitations on data collected . . . . . 7.1.2 Postulate a rate law . . . . . . . . . 7.1.2.1 Homogeneous reactions : . 1 60 78 79 80 81 81 82 82
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CONTENTS 7.1.2.2 7.1.3 7.1.4 7.1.5 7.1.6 7.1.7 7.1.8 7.2
CONTENTS Heterogeneous reactions (those with a catalyst): . . . . . . . . . . . 82 82 83
Choose the same reactor type that matches the data collected
Write the rate equation in terms of the data that has been collected .
Make simpliﬁcations based on good chemical reaction engineering principles 83 Diﬀerential analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83 Integral analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Goodness of ﬁt and variance in model parameters . . . . . . . . . . . . 84 85 86 86 86 91 91 93 94 95 96 98 99
batch reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.2.1 Method of excess . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.2.2 7.2.3 Example : Diﬀerential method . . . . . . . . . . . . . . . . . . . . . . Example : Integral method . . . . . . . . . . . . . . . . . . . . . . . . 7.2.3.1 7.2.3.2 7.2.4 The standard (linearised) analyses . . . . . . . . . . . . . . . Example 5.2 (Fogler) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Example : Nonlinear regression . . . . . . . . . . . . . . . . . . . . .
7.3 7.4 7.5
Method of initial rates
7.3.1 Example (Fogler 54) . . . . . . . . . . . . . . . . . . . . . . . . . . . Method of half lives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Diﬀerential reactors (including CSTR and recycle reactors) . . . . . . . . . . . 7.5.1 7.5.2 7.5.3
Mole balances : CSTR (and recycle reactor with rapid recycle) . . . . 100 Mole balances : Tubular and packed bed systems . . . . . . . . . . . . 101 Example : Fogler 55 . . . . . . . . . . . . . . . . . . . . . . . . . . . 101 107 108 109 110
8 9
Developing rate laws from reaction mechanisms and reaction pathways Bioreactor engineering mechanisms
10 Bioreactor design 11 Analysis of reactor ﬂow patterns on reactor performance (Fogler chapter 13)
2
. . . . . . . . Change of moles with time in a batch reactor. . . 7. . . . . . . .1 7. . . . . . .4 7. . . . . . . 7. . . Continuous stirred tank reactor. . 1. . . . . .13 The prediction of the reaction rate when regressing for k. . . . . . .10 Diagrams of typical plug ﬂow reactors commonly known as PFR’s. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Cubic and polynomial ﬁt to the data. KH2 in the rate law. . . . . . . . . . . . . . . . . . . . . . .6 1. . . 1. . . . . . . . . . . . . . . .11 The PFR mole balance. . . . . . . . . . . . . . . . . . . . . . .8 1. . . . . . . . . . . . .8 7. . . . . . . . . . . . 2005) Phthalic anhydride process. . . . 1. . . . . 2006) . General mole balance. . . . . . . 104 7. . . . . . . . . . . . . .4 1. . . . . . . . . . . . . . . The green line represents the nonlinear ﬁt. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106 3 . . . . . . . (Fogler. . . . . .1 1. . . . . 1. . . . Comparing the linear data ﬁt with the nonlinear data ﬁt. . . . . . . . . . . 2006) . . . . . .List of Figures 1. . . . . . The face of chemical reaction engineering.106 7. . . . . . . 104 7. . . . . . .9 . .10 Regression plot for the −rCO dependence on PCO . . . . . . . . .11 Plotting the −rCO dependence on PH2 . . . . . . . . . . . . . . . . . Data for example (Fogler54). . . . . (adapted from Schmidt. . . . . . . . . . . . . . . . . . . . ﬁrst and second order kinetics using concentrations. . . . . . . . . . . . . . . .7 7. . . . Diﬀerential reactor operation : concepts. . . . .12 The prediction of the reaction rate when regressing for all the rate law constants. . . . . . Standard regression plot for the second order reaction. . . . . . . .12 Arbitrary shaped PFR. The multidisciplinary nature of chemical reaction engineering. abbreviated as CSTR. . . .9 Generic ﬂow diagram of a process. . . . . . . . . . . . . Halflife analysis plot. . . . . . . .2 1.5 1.7 1. . . . . . .14 Tubular ﬁxed bed reactor. . . . . . .5 7. . 100 . . . . . . . . . . . . . . . . . . . 2005) The reaction rate in a reactor. . 6 6 7 8 13 15 16 17 18 19 20 21 21 22 89 90 92 94 96 97 98 99 . . (Fogler. . . . . . . . . . . . . . . . . . . . . . . Batch reactor integral analysis linear plots for zero.3 7. . . . . . . . . 2006) . .3 1.13 Molar ﬂow rate proﬁles across the PFR. . . Linearised initial rate plot for the dissolution process. . . . . . . . .6 7. . 1. . (Fogler. . . Predicted and experimental data when using the nonlinear leasts squares method applied to concentration data. . . . . . . . . . . . . . (Schmidt. . . . . . . . . .2 7. Batch reactor. . . . . . . . .
. . .3 Summary of reactor mole balances. . . . . . . . . . . . . . . . 23 Reaction rate as a function of concentration using cubic spline and polynomial ﬁtting. . . . . . . .1 7. . . 88 Experimental reaction data for the conversion of CO to CH4 . . . . . . . . . . .1 7. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2 7. . . . . . . . .List of Tables 1. . . . . . . . . . 102 Processed reaction data. . . . . . . . . . . . . 103 4 .
Chapter 1 Mole (or mass) balances 5 .
• The reactors can be as simple as a long hollow tube or a complex reaction vessel many 10’s of meters tall with many reactions occurring in multiple phases and with the aid of a catalyst.3 6 . MOLE (OR MASS) BALANCES 1. CHEMICAL REACTION ENGINEERING CHAPTER 1.1. 2005) Figure 1.1.2: Phthalic anhydride process. See Fig’s 1. • It is their knowledge of chemical reaction engineering that makes chemical engineers unique Reactors come in all shapes and sizes and arise in many interesting places. (Fogler.2. 2006) • Reactors are the key unit operation on plant.1. (adapted from Schmidt. • Almost all the worlds commodities and essential items are made using a reactive process. see Fig 1.1 Chemical Reaction Engineering Generic ﬂow diagram of a chemical process Figure 1.1 and 1. A plant is typically designed around a reactor.1 1. The operation of the reactor determines the operability and performance of the plant.1: Generic ﬂow diagram of a process.
(Fogler. CHEMICAL REACTION ENGINEERING CHAPTER 1.1.3: The face of chemical reaction engineering. 2006) 7 .1. MOLE (OR MASS) BALANCES Figure 1.
• Increase the capacity or selectivity at minimum cost.1.1. continuous) → pilot plant → operating plant Very few engineers will have the honour of following this process. see Fig 1. Figure 1. The engineer must know how to integrate these into the reactor design to yield its actual performance. Rate equations must be estimated. • Industrial processes are often severely limited by heat and mass transfer. improve selectivity and reduce the waste.4. gaining a deeper understanding is often not possible due to the presssure of other more pressing tasks. (Schmidt. • The kinetic rate equation almost never exists. CHEMICAL REACTION ENGINEERING CHAPTER 1. the ﬂow patterns in the vessel. Alternatively. Practicing engineers will most likely encounter and old reactor that has been modiﬁed many times which the engineer must now operate in such a way to double the throughput. The task must be solved as quickly as possible. The rate equation indicates how fast a reaction proceeds and thus determines both the size. The typical tasks are • Maintain and operate a process.4: The multidisciplinary nature of chemical reaction engineering. approximated from reaction engineering fundamental knowledge and from experimental or plant data. The engineer needs to know enough about the reactions.1.2 What do we need to know Some facts about practicing chemical engineers • Single reactions never happen. Reactors are complex unit operations with many simultaneous chemical reactions occuring in multiple phases. • Fix a problem. 2005) 8 . Besides being competent at “back of the envelope” calculations and having a good intuitive feel for reaction engineering. Often. reactor has failed and the engineer must understand the reasons of failure and recommission the reactor to operate better without failing. Reactor design typically proceeds according to a well deﬁned path Bench Scale reactor (batch. the interaction of heat and mass transfer in order to assemble the basic understanding of the reactor operation.for there are many more tasks that need doing. MOLE (OR MASS) BALANCES 1. productivity and selectivity of the reacctor. the engineer also needs to be able to build quick practical models of the reaction process by integrating all the other engineering disciplines.
isothermal reactor design by combining the knowledge of • kinetic models and their structure. The ones that can be solved in 3 lines often without a calculator. • multiple reactions and nature of the reactions.1. • various type of reactors and conﬁguration of multiple reactor sequences. 1. 2. 2005) 9 . These will build good reaction engineering intuition.1.1. These are the design type problems that will exercise the procedural skills and study the “what if” scenario’s. • elementary reactor design equations. MOLE (OR MASS) BALANCES This course is the ﬁrst course of two in reaction engineering and will aim to develop good reactor engineering skills for optimal homogeneous.3 Industrial processes The following table shows the interesting contrasts between the large volume producers and high value chemicals produced by the pharmaceutical companies. The ones that require more rigorous calculation and in many cases a computer. There will essentially be two types of problems 1. • experimental data to determine the rate equation. (Schmidt. CHEMICAL REACTION ENGINEERING CHAPTER 1.
10 .4 The Chemical Feed stocks The following tables shows the usage of chemicals in the USA in 1994. Note the low value of the crude oil in contrast to solvents and more so pharmaceuticals (see insulin).1. 2005) This is in contrast to the prices of chemicals shown in the following table. CHEMICAL REACTION ENGINEERING CHAPTER 1. This ranking of these chemicals isn constantly changing.1. MOLE (OR MASS) BALANCES 1. It provides an interesting incetive for the development of alternative processes. (Schmidt.1.
MOLE (OR MASS) BALANCES 11 . CHEMICAL REACTION ENGINEERING CHAPTER 1.1.1.
although they have the same type and number of atoms. RATE OF A REACTION (Schmidt. A chemical reaction has taken place when one of more of the chemical species in the system of study are transformed by an inﬁnitesimal amount into (an)other chemical species. the number and arrangement of the atoms.2 1.1 Rate of a reaction Deﬁning when a chemical reaction takes place Chemical species are deﬁned by the type.2. isomers. 2005) CHAPTER 1.2. the diﬀerent arrangement of the atoms results in these molecules having diﬀerent physical properties and are thus chemically distinct from each other. For example isomers diﬀer only by the arrangement of the chemical species These. MOLE (OR MASS) BALANCES 1.1. This transformation can be one of the following • Change the arrangement of the atoms : double bond isomerisation : skeletal isomerisation : • Decomposition : 12 .
Figure 1. MOLE (OR MASS) BALANCES • Addition : • and many more other types of reactions (see organic chemistry hand book!) Often it is simpler to work with letters such as A. B.m−3 .2. 13 . Thus the reaction of methanol to dimethylether and water written as 2CH3 OH → CH3 OCH3 + H2 O can be written as 2A → D + W or A → 1D + 1W 2 2 (1. C. D for chemical species. −rA represents the consumption of A at some position in the reactor vessel and it is deﬁned as follows. RATE OF A REACTION • disproportionation : CHAPTER 1. Deﬁnition of reaction rate : The number of moles of A that are being reacted (consumed or produced) per unit volume per unit time [mol.2.1) 1.1.2 Deﬁning the rate of reaction Consider that A is reacting in the vessel in Fig 1.5.s −1 ].5: The reaction rate in a reactor.
In gas phase systems the actual volume of the vessel is used.e.2. Homogeneous reactors well mixed : When the vessel is well mixed such that the concentration of A is equal trhough the reacting vessel. if the vessel is not completely ﬁlled. the consumption of one mole of A will yield 0.5. the liquid volume is used.2.5 moles of W.4 The rate equation rA = f uncti on(Ci . The volume refered to in the rate equation is then the volume of the catalyst. then there will be v liq a rate equation for each phase.2. Since the density of a catalyst is constant. or the temperature and pressure of the system and the properties of the catalyst.m−3 .5 and rW = 2.5 moles of D and 0. The rate equation is an algebraic expression deﬁning how the reaction rate varies with the chemical and physical properties of the reacting system. This course will work with the deﬁnition of rA as given above. Heterogeneous reactors : In these reactors the reaction takes place on a catalyst surface (or a solid surface or within the catalyst pores). NOTE : The rate equation is independent of the reactor in which the reaction is being carried out in. (Note that the activity per unit surface area can similarly be converted into a mass basis by using the catalyst properties which deﬁne the surface area to mass ratio.s −1 then rA = −5 or −rA = 5 and rD = 2. Multiphase reactions : If the reaction contains a vapour and a liquid phase. rA ap and rA and the volume refered to will be the vapour phase volume and the liquid phase volume respectively.1. P. MOLE (OR MASS) BALANCES Deﬁnition of rA : rA represents the rate of formation of species A. RATE OF A REACTION CHAPTER 1. Reaction stoichiometry : In reaction 1. Homogeneous reactors with concentration gradient : When the species concentrations vary throughout the reactor volume. it is easy to convert the rate equation into a mass basis using the catalyst density and then the rate equation is deﬁned as moles of A reacting per mass of catalyst per time [mol. Similarly the rate equations for A. the volume represented by the m3 term refers to the vessel volume. /2 /2 It is good practice to decide on a convention and stick to it.3 The volume in the reaction rate and its relationship to the mass of the reacting system. 1.1. rD rW D and W are related by the reaction stoichiometry: −rA = 2rD = 2rW = 1 = 1 . for more phase including solids and catalysts. the volume refered to in the rate equation is that of a diﬀerential element in which it can be assumed that the concentration is uniform for all species (i. Thus rA is positive for a product and negative for a reactant. T. For example if the rate of consumption of A is 5 mol.kg −1 . Ccataly st ) The rate equation is a function of the concentration (activities) of all or some of the chemical species in the reacting system. Thus −rA represents the rate of consumption of A. In liquid phase systems. 1. Similarly.s −1 ] and is denoted as rA . 14 . well mixed).
which will be developed later in this course. It is not the deﬁnition of the rate equation.s −1 ] [mol.s −1 ] .s −1 ] [mol.3 The general mole balance Consider a mole balance of species j in a arbritary shaped reaction vessel (or control volume) in Fig 1. For example in the reaction A → pr oducts A would represent j.s −1 ] 15 rate of ﬂow of jINTO the system − [mol. Also species j can be a reactant of a product (i. The mole balance then can be written as IN − OUT + Gener ati on = Accumulati on rate of ﬂow rate of generation rate of accumulation of jOUT of of jby chemical of jwithin = + the system reaction in the system the system [mol. 1.6.e. this dt equation is actually the design equation for a constant volume batch reactor. . sometimes products are fed to the reactor as a result of recycle) Figure 1. It is not necessary the know what the other products are at this stage.1. THE GENERAL MOLE BALANCE CHAPTER 1. MOLE (OR MASS) BALANCES Examples of possible rate equations for the reaction A → P r oducts • Linear variation of reaction rate with concentration : rA = −kCA 2 • Quadratic variation of the reaction rate with concentration : rA = −kCA • Saturation of the reaction rate : rA = −k1 CA (1 + k2 CA )2 dCA NOTE : Although rA = is true from the deﬁnition of the units of the reaction rate.6: General mole balance.3.
4) Equation 1.2 then becomes dNj Fj. equa 1. Thus the rate of generation of species j in each element is given by rj.7: Batch reactor.4 is the GENERAL DESIGN EQUATION for chemical reaction engineering. MOLE BALANCE FOR BATCH REACTORS CHAPTER 1. ∆Vi and assuming that the concentration of all species is constant in each diﬀerential element.0 − Fj + Gj = 1. as ∆V → 0 and M → ∞ then Gj = V rj dV . (Fogler. MOLE (OR MASS) BALANCES and in symbols this is dNj (1. means that the reaction rate is constant on each diﬀerential element.4. Gj represents the total transformation of j that has occurred when passing through this reaction vessel.0 − Fj + rj dV = dNj dt (1. it is applicable to all ISOTHERMAL reaction systems.2) dt where Nj is the total number of moles of j in the system. Gj can be related to the reaction rate for two special cases Fj.2 ∆V2 + rj.1. Dividing the system volume into diﬀerential elements (see Fig 1.4 Mole balance for batch reactors Figure 1. When the concentration of all species is constant throughout the entire system volume : Then the reaction rate rj is the same throught the whole reaction vessel and Gj = rj V where V is the volume of the vessel.0 − Fj + rj V = (1. For NONISOTHERMAL reaction systems an ENERGY BALANCE will also be needed in order to solve equation 1. The rate of generation of species j in the system is thus the sum of all the diﬀerential elements M : Gj = rj. When the concentration of all species varies throughout the reaction volume : Then the reaction rate will be diﬀerent at all locations. The general mole balance in this case becomes V Fj.i ∆Vi .6).4.3 ∆V3 · · · = i=1 rj. In the diﬀerential limit.3) dt 2.1 ∆V1 + rj.i ∆Vj . When used on its own. 1. The general mole balance. 2006) 16 .
thus the design equation is dNj = rj V dt (1.7(B) shows the text book schematic of a batch reactor as a vessel ﬁlled with liquid and a stirrer to provide perfect mixing. It almost always has a stirrer (agitator) and they are almost always used for liquid phase operations. There are coils or a jacket around the outside of the vessel for heating and cooling. called the reaction time.4. as shown in Fig 1. The reactor volume is that of the reactive mixture. MOLE BALANCE FOR BATCH REACTORS CHAPTER 1. A batch reactor is operated by ﬁlling the vessel with the required reactants. the general mole balance on species j becomes V rj dV = dNj dt Assuming that the system is well mixed.. others use evaporation cooling or direct steam heating..8: Change of moles with time in a batch reactor.8.1. Since there is no ﬂow into or out of the vessel. The reactor is then cleaned and the cycle starts again with fresh reactants.5 is based on the number of moles in the vessel and not the concentration. 17 . equa 1. For a reaction A → B the number of moles of A decrease with time while the number of moles of B increase with time. Figure 1. More on this later. Its a vessel with a lid so that it can be opened for cleaning. the reaction rate equation will be the same through the whole vessel. Fig 1.5) Notice that the general equation. such that the concentration oﬀ all species in the reactor are the same everywhere in the vessel. in this case the liquid volume and NOT the volume of the vessel.) out of the vessel. The vessel is always raised oﬀ the ground. An the end of the the reaction time the mixture is removed (pumped.7(A) shows a schematic diagram of a industrial batch reactor. MOLE (OR MASS) BALANCES Fig 1. Some vessels have coils internally. It has ports for adding and removing chemicals. The reactor is then heated to the desired reaction temperature and the reaction is allowed to proceed for a predetermined amount of time. During this time there is no ﬂow into or out of the reactor.
They can be closed vessels or open vessels. abbreviated as CSTR.1. dt V Fj.6) NA0 rA V where NA0 are the number of moles at the start of the reaction. like bubbling a reactive gas through a liquid reactant.g. t = 0 and NA1 are the number fo moles of A that are remaining after a reaction time of t1 . The mole balance for species j across this vessel is V Fj. the there is no variation with time of all species on dNj the reactor.9(A) shows a schematic diagram of a continuous stirred tank reactor (CSTR). These reactors are most often used for liquid applications involving poorly miscible streams and/or solids. thus.9: Continuous stirred tank reactor. MOLE (OR MASS) BALANCES The time t1 that is required to consume (NA0 − NA ) moles can be obtained by integrating equa 1. = 0 and the mole balance becomes.5. They can be ﬁlled to capacity or have partially ﬁlled with or without two phase operation. They are also used for systems which require the additiion of another phase e. Fig 1. Fig 1. These reactors always have a stirrer or some form of vigorous agitation to ensure that the composition of all species is uniform throughout the reaction system.9(B) shows the diagramatic way in which a CSTR is represented for calculation purposes. 1. They also have a heating/cooling jacket of coils to control the temperature in the vessel. MOLE BALANCE FOR CONTINUOUS CHAPTER TANK REACTOR (CSTR) STIRRED 1.5: NA1 dNA t1 = (1.0 − Fj + rj dV = 0 18 .5 Mole balance for continuous stirred tank reactor (CSTR) (A) (B) Figure 1.0 − Fj + rj dV = dNj dt If the reactor is operated at steady state.
1.7) This is the ﬁnal design equation for the CSTR. This is to promote plug ﬂow. since there are no spatial variations in the concentrations as the contents of the vessel is well mixed. MOLE (OR MASS) BALANCES CHAPTER FLOW REACTOR (PFR) In addition. by making steam on the outside of the tubes or coils in the vessel. Fj. Plug ﬂow reactor can be mounted inside furnaces for very high temperature operation. The reactor can be heated or cooled depending on the reaction requirements by using a jacket. It is important to note that the concentration of the species in the reactor have the same concentration as the species leaving the reactor in the exit ﬂow. which means V that rj dV = rj V and the mole balance then becomes. This means that all the species that enter the reactor spend exactly the same amount of time in the vessel. as it is best to have turbulent ﬂow. Plug ﬂow is deﬁned as ﬂow in which there is no axial mixing (no mixing along the length) by good radial mixing (mixing perpendicular to the ﬂow). Species interact only radially and not axially. The important aspect of these reactors is that they are extremely long in relation to their diameter.0 − Fj + rj V = 0 Fj0 − Fj V = rj (1.10 is basically an empty tube through which a reactive ﬂuid ﬂows. the reaction rate. 1.10: Diagrams of typical plug ﬂow reactors commonly known as PFR’s. 19 . Fig 1.6. rj is constant throughout the whole vessel. A plug ﬂow reactor.6 Mole balance for a homogeneous plug ﬂow reactor (PFR) Figure 1. The reactive streams are mixed at the reactor inlet. MOLE BALANCE FOR A HOMOGENEOUS PLUG1.
MOLE (OR MASS) BALANCES CHAPTER FLOW REACTOR (PFR) Figure 1.s −1 ] [mol. The reactor mole balance can be obtained in a more intuitive way by considering a diﬀerential element. The general mole balance can be applied to the whole reaction vessel.0 − Fj + rj dV = dNj dt Since the species concentrations (or molar ﬂow rates) are not constant. Furthermore.s ] [mol.11.0 = 0 and thus dV (1.0 dFj − + rj = 0 dV dV and since the feed does not depend on the reactor volume. consider the schematic in Fig 1. for a reactor at steady state becomes Fj V − Fj V +∆V + rj ∆V = 0 Dividing through by ∆V and rearranging yields Fj V +∆V − Fj V = rj ∆V 20 .s ] molar ﬂow rate of species j − IN at V −1 [mol. it is not possible to simplify the integral expression. The diﬀerential mole balance over the diﬀerential element is then IN − OUT + Gener ati on = Accumulati on Molar rate of rate of accumulation molar ﬂow rate generation of of species j of species j + = within ∆V OUT at V + ∆V species jin ∆V −1 −1 [mol. the reaction rate term.1. Thus in this case the general mole balance in this form is not particularly useful. when more than one reaction is taking place. thus for species j it is V Fj. thus dFj = rj dV dFj. preventing the integration from being carried out.11: The PFR mole balance. rj does not only depend on species j but can also depend on the other species in the reaction vessel. in which it can be assumed that the species concentrations are constant and thus the reaction rate is also constant.s ] which in symbols. In developing the general mole balance for a PFR. Note that this is a diﬀerential equation. Then diﬀerentiating with respect to the reactor volume yields makes dt dFj.6. Assuming steady state dNj = 0.8) which is the general mole balance for a PFR. MOLE BALANCE FOR A HOMOGENEOUS PLUG1.
These are similar to the batch reactor.6. which would vary with crosssetional area.9) 21 . Consider again the reaction A → B but this time in a PFR. This is no longer true once other factors are accounted for. MOLE BALANCE FOR A HOMOGENEOUS PLUG1. on in particular is pressure drop.13. except that volume has replaced time. Figure 1. the shape of the reactor does not matter and is arbitrary (in the derivation volume was used with no mention of the shape of the vessel).12 could also have been used for the derivation of the mole balance. which depends on the velocity. In the limit as ∆V → ∞ the PFR mole balance becomes dFj = rj dV as before. The molar ﬂow rate proﬁles across the reactor as shown in Fig 1. The design equation for this reaction is dFA = rA dV (1.13: Molar ﬂow rate proﬁles across the PFR. MOLE (OR MASS) BALANCES CHAPTER FLOW REACTOR (PFR) Fj V +∆V − Fj V Since the ﬂow rate us a function of V in the sense that F = f (V ) the term ∆V represents an approximation to the dereivative of F with respect to V .1.12: Arbitrary shaped PFR. IMPORTANT NOTE : for plug ﬂow conditions. Thus Fig 1. Figure 1.
The particle size and the bed diameter are key design parameters.7. The isothermal vessels are typically long and thin with a relatively small vessel : particle diameter ratios (2040). Thus the reaction rate 22 . V1 FA1 dV = V1 = 0 FA0 dFA rA 1.9 from the beginning of the reactor where V = 0 and FA − FA0 until V1 where FA = FA1 .14: Tubular ﬁxed bed reactor. Mass and heat transfer in the catalyst particle to/from the active site becomes more diﬃcult as the particle size increases. The interplay of heat and mass transfer in catalytic reactions is a leads to exciting reaction systems. The reaction rate is thus based on the catalyst mass (or catalyst volume). In contrast. through the density of the catalyst particles). Adiabatic vessels are typically short and squat with large vessel : particle diameter ratios (>>100).7 Mole balance for a heterogeneous ﬁxed bed reactor (FBR) (a) (b) Figure 1. For other reactions where the exothermicity can be tolerated or the reaction is near thermoneutral. More of this will be the topic of reactor design 2. BED REACTOR (FBR) To determine the volume of reactor required to achieve the exit ﬂow rates FA1 and FB1 in Fig 1. This conﬁguration is used if the reaction is very exothermic (produces a lot of heat) and/or the reactants or products are heat sensitive and/or the catalyst deactivates at higher temperatures and/or the catalyst selectivity deteriorates and it is crucial to keep the reactor as close to isothermal operation as possible.1.14(a) shows a ﬁxed bed reactor with the catalyst packed in the tubes and coolant ﬂowing around it (sometimes steam is made in this way). These opposing eﬀects need to be optimised during the reactor design phase. Fig 1. (Vessel volume and catalyst volume can easily be used or converted to. MOLE BALANCE FOR A HETEROGENEOUS FIXED MOLE (OR MASS) BALANCES CHAPTER 1. it will be assumed that heat and mass can be neglected and that pressure drop can be ignored and that the ﬂow in the vessel is perfect plug ﬂow.13 can be obtained by integrating equation 1. the pressure drop across the bed increases as the particle size decreases. since it is the catalyst that is responsible for the reaction that is taking place. In this ﬁrst level mole balance. the vessel can simply be packed with catalyst particles as a uniform bed.
steady state V = −rA FA dFA dFA PFR steady state = rA V = dV FA0 rA FA dFA dFA FBR steady state = rA W = dW FA0 rA (Fogler.1. reactor Comment Mole balance diﬀerential algebraic integral NA dNA dNA = rA V t= Batch no spatial variation dt NA0 rA V FA0 − FA CSTR no spatial variation.1: Summary of reactor mole balances.14(b) shows the diﬀerential element used in the mole balance. MOLE (OR MASS) BALANCES −1 rA = [(mol A r eacted).10) dW and the catalyst weight required to achieve a exit ﬂoe rate of FA is given by FA W = FA0 dFA rA 1. Table 1. 23 . 2006) These represent the deﬁnite equations of the reactor design 1 course and for that matter all reaction engineering design problems can be solved using these equations.s −1 . IN − OUT + Gener ati on = Accumulati on Fj W − Fj W +∆W + rj ∆W = 0 Dividing through by ∆V and rearranging yields Fj W +∆W − Fj W = rj ∆W Fj W +∆W − Fj W Since the ﬂow rate us a function of W in the sense that F = f (W ) the term ∆W represents an approximation to the dereivative of F with respect to W .8. In the limit as ∆W → ∞ the PFR mole balance becomes dFj = rj (1.8 Summary Table shows summary of all the mole balances carried out in this chapter. SUMMARY is deﬁned as CHAPTER 1.gcataly st ] Fig 1. The rest of this course is on the application of these equations to speciﬁc problems.
Chapter 2 Reactor sizing for single reactions using conversion 24 .
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Chapter 3 Properties and deﬁnitions of the reaction rate equation (reaction rate law) (Fogler chapter 3) 47 .
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Chapter 4 Reaction stoichiometry and the reaction rate law (Fogler chapter 3) 60 .
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Chapter 5 Isothermal reactor design for single reactions (Fogler chapter 4) 78 .
Chapter 6 Isothermal reactor design for multiple reactions (Fogler chapter 6) 79 .
Chapter 7 Collection and data analysis (Fogler chapter 5) 80 .
To be able to select the best model based on good statistical methods. To be able to estimate the reaction rate constant.1. To be able to develop the appropriate reactor design equation and rate law that will describe the experimental data 4. Make every eﬀort to ensure that the data is collected under isothermal and isobaric conditions 2. ALGORITHM CHAPTER 7. Make every eﬀort to ensure that there are no unexpected concentration and temperature gradients. 5. the reactor conﬁguration choosen must behave like a plug ﬂow reactor or else the estimated rate constant will depend on the shape of the reactor and CANNOT BE USED FOR SCALEUP. 81 . For example in a two phase batch reactor (gas bubbles in the liquid). 3. which are then ultimately used in the design of a pilot plant and ultimately a commercial unit. the stirring must be fast enough to ensure complete mixing at all times during the reaction. it is necessary that the stirring is fast enough such that the bubbles are small enough to ensure that there are no mass transfer limitations. The same applies to fast liquid phase reactions in a batch reactor.1 Limitations on data collected The following are guidelines when collecting data or looking at data to be analysed 1. 7. THE KNOWLEDGE AND TOOLS GAINED HERE ARE EXTREMELY IMPORTANT. gfeat care needs to be taken to ensure that the mixing (stirring) is fas enough to ensure that there are NO temoperature and concentration gradients in the vessel. 7. For example. if a plug ﬂow reactor is assumed. pore diﬀusion. For example. The purpose of this chapter is to develop the following knowledge 1. To be able to study experimental data and decide how it should be analysed 3. 2. Make every eﬀort to ensure that the idealisations of the assumed reactor type are obeyed. To be able to formulate the design equation in the appropriate form such that it is suitable for regression with experimental data to determine the rate law parameters 5. Make sure that the data are collected at steady state and that the MASS BALANCE IS OBEYED. the reaction order and other constants in the rate law from appropriately collected experimental data. To be able to formulate the objective function and use appropriate computer code to carry out the nonlinear regression 6.1. in a ﬂow reaction bomb (CSTR) in which a combustion reaction is taking place. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) This chapter develops some of the techniques that are used to obtain rate laws for chemical reactions. Make every eﬀort to ensure that the data collected is free of transport limitations such as ﬁlm resistance.7. (see later chapters) 4.1 Algorithm The following steps are general and apply to all the examples and reactor types that follow.
3 Choose the same reactor type that matches the data collected −rA = 1 d(NA ) dCA dCA 1 dPA = = = V dt dt dt RT dt −rA = dFA dXA = −FA0 dV dV FA0 − FA FA0 = XA V V 82 (7.1 Homogeneous reactions : n α monomolecular : −rA = kCA = k PA (7.2) (7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) 6.3) reversible : −rA = k CA CB − CC CD Ke In particular for reversible reactions it is important that the rate law is able to describe the chemical equilibrium of the reaction(s) i.1) α β PA PB bimolecular : −rA = α β kCA CB =k (7.2. It is also beyond thre scope of this course.1.5) Also here the rate law must obey the thermodynamic limitations of the reaction thermodynamics.7) CSTR : −rA = (7. There are ways to analyse nonisothermal and nonisobaric data.4) PB Ke LHreversible : −rA = 1 + K A PA + K B PB (7.8) .2.1. 7.3 the equilibrium limit is Ke = CCe CDe CAe CBe where the Cie are the equilibrium concentrations when rA = 0. Good places to start 7. for reaction 7. but this also leads to less accurate estimations of the rate constants. 7.1.7. but it is considerably more diﬃcult to get estimates of the kinetic constants that are reliable. ALGORITHM CHAPTER 7.2 Postulate a rate law The design and development of rate laws is the topic of the next section (Fogler!!!!). Similarly.2 Heterogeneous reactions (those with a catalyst): LangmiurHinshilwood (LH) : −rA = kPA 1 + K A PA k PA − (7. 7.e.1.1. nonideal reactor behaviour can be accounted for. and obtained from thermodynamics.6) Batch reactor : PFR : (7. In many cases the rate law needs to be developed in conjunction with the data analysis and experimental observations.
although its use will be quickly demonsrated as is done in Fogler. Fast reactions can be assumed to be at chemical equilibrium. However. For situations like this new experimental data will have to be collected.e. which simpliﬁes the rate equations.05). 7. All other reactors will collect primarily C v s t or F v s V data which has to be converted into rate data by numerical diﬀerentiation.4 Write the rate equation in terms of the data that has been collected e. 2.5 Make simpliﬁcations based on good chemical reaction engineering principles Some typical examples are. due to the change the number of moles. can be neglected (i. Often. −rA = −FA0 . COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) 7. −rA = V all other reactors this provides an approximation to the data collected. XA . NOTE also that this rate law cannot be used for conditions in which the concentration of B is of the same order of magnitude as A.1. for In a CSTR. 3.− .1. Reactants in excess : This means that for example that when the concentration of B exceeds the concentration of A by more that a factor of 100. ∆V In all cases the data analysis normally follows the following approach: α β −rA = kCA CB (7. NOTE that in this csae the rate constant k is a function of the concentration of B (CB ). then any volume expansion. Xin − Xout viz. ALGORITHM CHAPTER 7.7. Xout = Xin + ≤ 0. Numerical diﬀerentiation increases the scatter (error) in the data and leads to poor data analysis and this method is not recommended.1.e. Xin > 0) and products leaving only increase the conversion by a few percent (i. etc v s kCA CB dt dV dt V (7. XA v s W etc. B in a reacting mixture are less than 1%.10) 83 . then the second order β α α β reaction −rA = kCA CB can be approximated by −rA = k CA where k = kCB . the data automatically comes in this form i. 1. in which the feed entering is already partially converted (i. ﬂow rate change. NA v s t. Reactants are dilute in a reaction mixture : If for example the mole fractions of A. PA v s t.g. 7.6 Diﬀerential analysis This method of analysis takes the approach that the data will be in the form REACTION RATE v s RATE LAW dCA dFA dPA FA0 α β −rA = − .e.1. data is collected in what is known as a diﬀerential reactor. . ε = 0).e. pressure change.9) FA0 XA . Similarly for liquid phase reactions. then the reactor can be treated similarly to a CSTR.
β until the least squared error is as close to zero as possible (using excel’s solver or scilab’s lsqrsolve).11) which is a linear equation in (ln(k).15) or in terms of the measured variable. W. (typically when the reaction order is given. τ. α.i . consider the second α β order nonequimolar reaction with the rate law : −rA = kCA CB .7 Integral analysis This analysis is more applicable to standard reactors which generate data in the form: CA .i 2 ≈0 where −rA. β) which can then be found by linear regression. CB. Nonlinear regression in this case yields: n mi n [f (k.i CB. α. V.16) There are many situations where integration is not possible.7.12) In all these cases the design equation must be integrated. ALGORITHM CHAPTER 7. For example. FA . The objective function f (k.i − kCA. PA . Thus this type of data can only be analysed using nonlinear analysis except in some special cases.i − −k(1 − α)ti − C (1−α) A0 mi n [f (k. CA it is n CA. This is a good approach when the reaction order are unknown and are needed to be estimated. Thus the linear regression requires repeated guesses of α. and this will have slightly diﬀerent answers than the direct nonlinear regression.i in the reaction system when a total number of n experiments have been carried out. since the equation is linear in the reaction orders.1.i + k(1 − α)ti − CA0 2 ≈0 (7. α. W FA0 (7. Note that integration is a smoothing process and reduces the errors in the estimated rate constants as opposed to the diﬀerential α method. β)] = i=1 β α −rA. the linear plot of CA vs t will require an estimate of α. 7.14) (1−α) (1−α) CA = −k(1 − α)t + CA0 For the ﬁrst equation (α = 1) the linear plot ln(CA ) vs t will yield rate constant from the slope.1. which is silly. NOTE : this methods uses log weighting of the data. XA vs t. For the simple αth order reaction −rA = kCA in a liquid phase batch reactor this yields: CA = CA0 exp(−kt) α=1 (7. (1−α) However. α. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) taking logs on both sides: ln(−rA ) = ln − dCA dt = ln(k) + αln(CA ) + βln(CB ) (7. α)] = i=1 (1−α) (1−α) CA.i represents the measured data data at each experimental value i of the concentrations CA. for the second equation. β) must be minimised by adjusting k. α)] = i=1 1 2 1 − α ≈ 0 (7. which can be formulated as : n mi n [f (k. linearisation is often possible).13) (7. Writing in terms of conversions 84 .
2p i then the parameter refers to the diagonals of the matrix.i .20) 0. β and has no limitations of these values either. β] and f (p) is evaluated ∂pi at each data point j. ALGORITHM CHAPTER 7. Then the variance in the parameters p is given by f (p) × pi = p i ± σi.8 Goodness of ﬁt and variance in model parameters The goodness of ﬁt can be obtained in two ways (i) A correlation coeﬃcient can be obtained between the experimental and the predicted data e.i 2 1 CB0 − XA CA0 dXA ≈ 0 β (7. (NOTE.i A0 0 (1 − XA )α where the diﬀerent conversion are obtained by varying the ﬂow rate (this is the most common way. the PFR design equation is: FA0 dXA α+β = kCA0 (1 − XA )α dV XA CB0 − XA CA0 β β (7. requires no guessing of α. β)] = i=1 V kC α+β − FA0. The advantage of this approach is that it is general. 85 . where JT J −1 i.i JT J −1 i.1. where integration using an ODE solver is needed each time is also easily done on a computer.7.g plotting (−rA )exp versus (−rA )model and estimating the mean and variance.19) min [f (k. In this formulation the integral must be evaluated each time for each value of XA. n (−rA )exp − (−rA )model (ii) looking at the least squares error : i=1 2 where n is he number n−m of data points and m is the number of estimated parameters (3 in the case shown here) The variance in the model parameters can be obtained by studying the Jacobian matrix of the ∂f (p)j objective function : Ji. The disadvantage is that it needs some computer code to be written! It is possible to have multiple reactions with multiple rate constants.17) V α+β = kCA0 FA0 0 1 (1 − XA )α CB0 − XA CA0 dXA (7.i σi.18) which can be formulated as an objective function n XA.1. changing V is the other way). When σi. α.j = where p is the vector p = [k. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) for a constant ﬂow rate system yields. and thus J is a m × n matrix.i = n−m (7.i .i is a poor estimated and the model is most likely over parameterised and that means that there are most likely too many model parameters or there is not suﬃcient data. α. that if CA0 = CB0 then it is no longer possible to distinguish α from β. All this is not a problem on a computer. 7.
.2. HCl reacts with the pyridine.. The concentration time data is collected time (min) 0 50 100 150 200 250 300 −1 Concentration of A..2 7.6 22.2.CA.L−1 . determine the reaction order with respect to triphenylmethylchloride 2.tn ] the concentration vector is given by : [CA ] = [CA.2 CA.1 batch reactors Method of excess The idea of this method is to reduce the dependence of the rate law on multiple concentrations into one concentration. ex 5. The idea then is to carry out the reation in two ways (i) Using excess B such that CB = CB0 and does not change signiﬁcantly during the reaction. the reaction order of methanol was given as 1. the reaction : A + B → pr oducts with the rate law α β −rA = kCA CB (7. Then β α α α β (7.1. β have been found. determine the reaction rate constant SOLUTION PART 1 Looking at the data the time vector is given by : [t] = [t1 t2 t3 . 1.n ] 86 .22) −rA = kCA CB = kCB0 CA = k CA which can then be used to ﬁnd α.L ] 50 38 30. β are unknown. (ii) Using excess A such that CA = CA0 and remains eﬀectively constant during the reaction.3 .2 Example : Diﬀerential method (Fogler. which then precipitates making the reaction irreversible. CA [mmol.21) is diﬃcult to analyse when both α.5 17. For example.2 19.7.2.4 The initial concentration of methanol was 500 mmol. BATCH CHAPTER 7. 7. p260) The reaction of triphenyl methyl chloride (A) with methanol(B) viz (C6 H5 )3 CCl + CH3 OH → (C6 H5 )3 COCl + HCl A+B → C+D is carried out in a batch reactor in a solution of benzene and pyridine at 25°C. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) REACTORS 7. (iii) Once α. then normal concentration data can be analysed for k. This method is particularlygood for getting ﬁrst estimates of the reaction order with respect to the key component.1 CA.. similarly β β α β α −rA = kCA CB = kCA0 CB = k CB (7.6 25.23) which can be used to ﬁnd β.
7.2. BATCH CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) REACTORS where n is the number of data points. This also means that you cannot estimate more than n model parameters. α β Proposed rate law : −rA = kCA CB now, CB0 = 10CA0 thus the it may be assumed that CB = CB0 ≈ constant over the range of the data collected (well, not really that constant, by the change is less than 5%) β α Then −rA = k CA where k = kCB0 dNA = rA V Mole balance : dt stoichiometry : NA = NB = −NC = −ND Since this is dilute liquid phase system, the density (volume) of the system is constant, thus the design equation becomes; dCA α − = k CA (7.24) dt diﬀerential analysis then requires; ln − dCA dt = ln(k ) + αln(CA,i )
i
(7.25)
where the i values run over all data points. Thus it is necessary to ﬁnd the reaction rate as a function of time. The best way to do this is to ﬁt a cubicspline to the data //fit a cubicspline to the data d = splin(tt,Ca); function Cat=spln(t) Cat=interp(t,tt,Ca,d) endfunction Cas=interp(t,tt,Ca,d) //spline interpolated values and then to diﬀerentiate the cubicspline //get the gradient ttt=tt;ttt(n)=ttt(n)0.1; //takingcare of the last point dCa_dt_s=diag(numdiff(spln,ttt)); disp(’dCa/dt=’+string(dCa_dt_s)) . This yields the following data in table 7.1. An alternative is to ﬁt a polynomial to the data. This is done as follows; The error between each data point and the polynomial is given by εi = CA,i − (a1 + a2 t + a3 t 2 + a4 t 3 + a5 t 4 ...) which can be vectorised as follows since it is a linear operation with basis sets εi = CA,i − [p]i [a]T [p]i = [1 ti ti2 ti3 ti4 ...] [a] = [a1 a2 a3 a4 a5 ] (7.27) (7.28) (7.26)
Here the vectot [p] represents the basis sets. Note that these can be any set of independent functions e.g. [p] = [1 t si n(t) exp(t) t 3 ]. This can be expanded for every data point n : 1 1 1 1 1 ε1 cA,1 a1 ε2 CA,2 t1 t2 · · · · · · · · · a2 . a ... ε C 2 2 . 3 = [ε] = [CA ] − [p][a]T ≈ 0 (7.29) 3 = A,3 − t1 t2 . . . ... . . . . . . t3 . . . . 1 n n εn CA,n am t1 · · · · · · · · · tn 87
7.2. BATCH CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) REACTORS Note that m is the number of parameters [a] which in this case is 5. Note also that m ≤ n for a meaningful solution. When m = n then the solution is unique, one parameter for every equation. However, as with most data, n > m and the solution will never be exactly zero, rather the objective function needs to be minimized, thus min Ψ = [ε]T [ε] (7.30)
Matlab’s and Scilab’s backslash operator (\) does exactly that (i.e. the overdetermined system, Ax = b yields the least squares solution x = A\b). Applying this concept here yields the parameters of the polynomial that ﬁts the CA v s t data; [a]T = [p]\[CA ] = [50 − 0.2978 1.34E − 03 − 3.485E − 06 3.67E − 09] The code that does this is and the data is given in the table. //polynomial fit to the data using a nonlinear leasts squares solver (the long way) function f=polfit(a,n) tx=[ones(1:n); tt; tt^2; tt^3; tt^4]’; //define the vector of polynomial basis sets f=Ca’tx*a’ //calculate the error at each point endfunction a0=[1 1 1 1 1]; //initial guess a=lsqrsolve(a0,polfit,n) //solve the nonlinear problem disp(’a_cubic=[’+string(a)+’]’) //display tx=[ones(1:nt); t; t^2; t^3; t^4]’; Cap=tx*a’; //calculate the polynomial fitted values function f=CaPol(t) //define a function in terms of t tx=[ones(1:n)’ t t^2 t^3 t^4]; //changes since t is a column vector f=tx*a’ //the value of Ca endfunction //polynomial regression using linear leasts squares (the short but abstract way) txx=[ones(1:n); tt; tt^2; tt^3; tt^4]; aa=txx’\Ca’ disp(’a_poly=[’+string(a)+’]’)
Table 7.1: Reaction rate as a function of concentration using cubic spline and polynomial ﬁtting. CA dCA − dt dCA − dt 50 0.303
spline
38
30.6
25.6
22.2
19.5
17.4
0.185 0.119 0.0814 0.0590 0.0485 0.0351 0.188 0.119 0.0801 0.0603 0.0485 .0334
0.298
poly
The ﬁtted data is shown in Fig 7.1.
88
7.2. BATCH CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) REACTORS
50
concentration; CA [mmol:L¡1]
45 40 35 30 25 20 15
0
50
100
150
200
250
300
time; t [s]
Figure 7.1: Cubic and polynomial ﬁt to the data. The linear regression using equa 7.25 is //linear regression for the rate constant and reaction order //using cubic spline data aa_s=regress(log(Ca’),log(dCa_dt_s)); //such that log(dCa_dt)=aa(1)+aa(2)*log(Ca) kr=exp(aa_s(1)) alpha=aa_s(2) disp(’k=’+string(kr)+’ alpha=’+string(alpha)); //using polynomial data aa_p=regress(log(Ca’),log(dCa_dt_p)); //such that log(dCa_dt)=aa(1)+aa(2)*log(Ca) kr=exp(aa_p(1)) alpha=aa_p(2) disp(’k=’+string(kr)+’ alpha=’+string(alpha)); Linear regression of the spline ﬁt data this data yields : ln(k) = −9.116; k = 0.0001099 L.mmol−1 .min−1 and α = 2.035 and lsqr Er r r or = 0.0136 Linear regression of the poly ﬁt data this data yields : ln(k) = −9.116; k = 0.0001046 L.mmol−1 .min−1 and α = 2.048 and lsqr Er r r or = 0.0199 Direct nonlinear regression of the cubic spline data uses this equation
n
mi n f (k , α) =
i=1
−
dCA dt
α − k CA,i i
and the following code
89
alpha=b(2) f=dCa_dt_sk*(Ca^alpha)’ endfunction b0=[1 1]. typically.min−1 ]2 [mol.L−1 . COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) REACTORS //direct nonlinear regression function f=EE(b. this data yields : k = 0. This error is magniﬁed by the loglog scaling.2: Comparing the linear data ﬁt with the nonlinear data ﬁt.0001467 L. leaves the data in its original for and weights all errors on this basis.2.20 0. The nonlinear ﬁtting thus provides a more representative set of rate constants.00 15 10 1 ¡ 10 2 10 10 20 25 30 35 40 45 50 CA [mmol:L ] ¡1 CA [mmol:L¡1] (a) linearﬁt (b) nonlinearﬁt Figure 7.7.min−1 and α = 1.mmol−1 .15 0.mol−1 . The green line represents the nonlinear ﬁt.954 and lsqr Er r r or = 0.25 0. BATCH CHAPTER 7.2(b) shows that the nonlinear regression (green) shows a superior ﬁt to the rate data at high concentrations.92E − 7 CB0 [L.00902 So why are these values diﬀerent : Figure 7. 0 10 0.10 0. Figure 7. The linear regression transforms the data into a loglog scale. This means that the error for the small values of the concentrations and small rates are weighted much more heavily than the values at the large concentrations.292CA CB k = 2.EE.n) k=b(1).35 dCA [mmol:L¡1:min¡1] dt dCA [mmol:L¡1:min¡1] dt ¡ 1 2 0. This deviation is more pronounced in the rate constant. However. small concentrations are more diﬃcult to measure and thus also have the largest experimental error. On the other hand Fig 7.2(a) shows the loglog plot is not able to distinguish between the diﬀerent regressions. b=lsqrsolve(b0. on the other hand.05 0. The nonlinear ﬁtting.n) disp(’k=’+string(b(1))+’ alpha=’+string(b(2))).s−1 ] 90 .2 shows the two diﬀerent plots which eﬀectively represent the two diﬀerent methods. PART 2 Since β = 1 then the true rate constant k can eb calculated: k= Thus the rate law is given by 2 −rA = 0.30 0.
37] with lsqr Er r r or = 0. .7. 1 . the following analyses can be used for zero. This has the smallest error of them all. . ln(k) a= α β which can be solved by the “backslash” (a = p\ln(−rA )).3. . . . . 2. BATCH CHAPTER 7. second and nth order reactions. 1 .i )β 2 which can be solved by a nonlinear leasts squares. X =1− CA CA0 CB = CB0 − CA0 X = CB0 − CA0 + CA Then the rate law becomes α −rA = kCA (CB0 − CA0 + CA )β which can be used for dirrect nonlinear regression or linear regression using the loglog approach nonlinear n mi n f (k. 91 .44E13. β] = [9. then there are many standard rate laws for which the design equations can be integrated and a appropriate regression can be carried out. α. . If not. β) = i=1 α (−rA. . . From the reaction stoichiometry CA = CA0 (1 − X). . .i ) + βln(CB0 − CA0 + CA. This would give an idea of the errors made in assuming that the concentration of B is constant.3 shows these plots on a concentration basis for a batch reactor.93] with lsqr Er r r or = 0.i ) − kCA. When the reaction orders are known. . Scilab’s “lsqrsolve” [k. Assuming a constant volume batch reactor. This is due to the linear dependence of the two concentration columns.00712. (normally B should also be measured). [k. then they simply become partr of the regression procedure. −2. .2.i ) ln(−rA ) = p ∗ a p= 1 ln(CA ) ln(CB0 − CA0 + CA. β] = [180. .067. or make a standard plot. This solution has failed. α. .2. Interesting.1 The standard (linearised) analyses For the reaction A → pr oducts it is always useful to test the data with the standard cases. α.47. WHY Linear loglog: ln(−rA )i = ln(k) + αln(CA.2. 2. this is not a trial and error method.i (CB0 − CA0 + CA. −6. Fig 7. 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) REACTORS It is possible to ﬁt for all 3 parameters k α β if the concentration of B can be found from the concentration of A.3 Example : Integral method Contrary to what Fogler says.13. 7. ﬁrst. . .i ) . .
(or plotting X vs t has a slope of .2 0.34) 92 . CA [mol:m¡3] 0.0 2.0 1 CA 2.3 0. t [s] <2 2nd order reaction.2 0.0 0.5 1.2.8 0. X = t (7.7 0.3.0 time.6 0.7 0.7.5 3.0 3.5 0.6 0.2 0.32) CA vs t the slope of the line is −k.0 µ 1.0 0.3: Batch reactor integral analysis linear plots for zero.33) CA = exp(−kt).0 CA CB0 ¡ CA0 + CA 1 1 = kt + CA CA0 slope = k Rx ¶ Rx no r r de >2 r no de r 1.2 0. t [s] Figure 7. 3.7 0.0 0.5 slope = ¡ k(C ¡ C ) A0 B0 5.3 0.5 4.3 0.1 0.0 0.0 2.4 0. t [s] time.5 4.9 log WARNING There is no natural limit on the smallest value of CA it can go negative µ 0. CA = CA0 − kt.0 0.0 0.5 0.4 0.31) dt CA0 So plotting CA vs t is a linear plot with an intercept CA0 and slope −k.9 1.0 4.0 0. t [s] 4.6 0.9 1. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) REACTORS 1.0 0.5 2 kCA time.9 0.3 (similarly CA0 for plotting of ln(1 − X) vs t) Note that rearrangement to ln(CA ) = ln(CA0 ) − kt (7. Zero order reaction : dCA k = −k.5 concentration.0 0.0 0. ﬁrst and second order kinetics using concentrations.5 2nd order reaction.5 0.6 0.9 1. Note that it is not necessary to know the CA0 initial concentration CA0 when making the CA vs t plot. ln(1 − X) = −kt (7. First order reaction : dCA = −kCA .8 0.1 0. since this given my the intercept. as shown in Fig 7.3 0.8 0.0 1.5 2.7 0. kCACB log µ ¶ µ ¶ CA CA0 = ¡k(CB0 ¡ CA0)t + log CB0 ¡ CA0 + CA CB0 2.5 3.6 ¯rst order reaction log µ ¶ CA = ¡kt CA0 slope = ¡ k 0.5 0.0 1.4 0.1 0.1 0.0 time.0 3. CA0 1 − X = exp(−kt) (7.5 2.5 0.8 0. BATCH CHAPTER 7. dt linearisation yields ln So when plotting ln CA CA0 = −kt.0 1.8 0.3 0. as shown in Fig k 7.2 0.4 0.5 3.7 0.4 ¶ CA or log(1 ¡ X) CA0 Zero order reaction CA = CA0 ¡ kt slope = ¡ k 0.1 0.5 log 0.
In all cases. assuming that teh reaction is second order. except for qth order reaction : dX q−1 = kCA0 (1 − X)q dt 1 1 − (1 − X)q−1 = k(1 − q)t = −k(1 − q)t + q−1 .7. the reaction rate does not depend on the concentration.44) 1 q−1 CA In these linearised equations it is necessary to know the reaction order q. = kCA0 (1 − X)2 Also for CA0 = CB0 dt dt dCA dX = −kCA CB = −kCA (CB0 − CA0 + CA ).45) . Furthermore.35) CB0 (7. (1 − x)q−1 CA0 dCA q = −kCA .3.40) intercept : 1 CA0 (7. BATCH CHAPTER 7.2 (Fogler) Continuation of example 5. dt 93 1 1 =kt+ CA CA0 (7. Second order reaction : dX dCA 2 = −kCA .2. Thus. Some of these standard plots are made in Fig 7.42) 1 1 = kt + CA CA0 it is necessary to know the concentrations of A and B at the start of the reaction. and thus it is not important to keep the initial concentration constant during experimentation.39) CA0 CB0 (7. (see Fig 7. = kCA0 (1 − X) dt dt and their integrated forms rearranged into linear equations for CA0 = CB0 : 1 1 1 = kt + plot : vs t slope : k CA CA0 CA X X = kCA0 t plot : vs t 1−X 1−X And for CA0 = CB0 : ln plot : ln CA CB0 − CA0 + CA vs t = −k(CB0 − CA0 )t + ln slope : − k(CB0 − CA0 ) CA0 CB0 intercept : ln (7.3) 7.41) slope : k(CB0 − CA0 ) (7.3. dt (7.36) −X CA0 slope: kCA0 CA CB0 − CA0 + CA CA0 C X − 1 ln B0 X − 1 = k(CB0 − CA0 )t CA0 CB0 X − 1 plot : ln X − 1 vs t (7.38) (7.2 Example 5.1 : The purpose now is to regress the concentration data directly without ﬁnding the reaction rate. − dCA 2 = k CA . COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) REACTORS and plotting ln(CA ) vs t also does not require knowledge of the intial concentration.2.43) (7.37) (7.
7.030 0. n mi n f (k ..47) 94 . So k = 0.2.4: Standard regression plot for the second order reaction.040 0.i vs ti . t [min] Figure 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) REACTORS Regression can be done by noting that the integrated equation is related to y = a + bx when 1 y= and x = t. 7.060 0. 0.015 0. CA 1 yields b = k and a = . Now the purpose of this method is to minimise the error between the experimental concentrations and the model predicted concentrations. thus this will form the objective function.4.010 0 50 100 150 200 250 300 350 time. since CA0 is already known. it therefore makes sense to integrate a general αorder rate equation and its integrated form.7. α) = i=1 εi εi = εεT (7.035 0. dt model 1−α CA = CA0 − (1 − α)kt 1 1−α (7. So the model ﬁts the data well as shown in Fig 7.055 0..045 0. The the solution of this equation by for example Scilab’s “regress” routine.2.020 0.4 Example : Nonlinear regression Nonlinear regression requires the development of a objective function which is then used in a nonlinear leasts squares solver (Scilab’s “lsqrsolve” is a particularly good one. EBEmatlab does not have such routines and the nextbest bet is EXCEL!!!) Continuation of Foglers example 51: exp Noting that k and α are to be found and that the data is given in the form CA. BATCH CHAPTER 7.050 1 [L:mol¡1] CA 0.46) This is the batch reactor design equation and will from now on be called the model. dCA α = −k CA . The value obtained for a provides a check on the validity of the CA0 model.025 0.0001248 and ”CA0 ” = 49.
1109 0. RATES where n is the number of experimental data points and εi is the error between the experimental and model concentrations. . Then the reaction rate at these conditions is estimated from data collected over a very small conversion range.000 2. at small conversions (say < 5% change in conversion over the reaction period).3 Method of initial rates The idea here is to study the reaction at very short reactions times. //x is a vector of two parameters f=Ca(Ca(1)^(1alpha)(1alpha)*kr*tt)^(1/(1alpha)) endfunction The calling of the least squares solver then has hte code //call the least squares solver x0=[0. . When this is done then k = 0.7. This avoids complications from any possible reversible reaction steps.i − CA0 − (1 − α)kti (7. .n) kr=x(1). or more precisely.alpha=x(2).48) 1 1−α (7. The values of k are summarised here: method diﬀerential : Linear regression of the spline ﬁt diﬀerential : Linear regression of the poly ﬁt diﬀerential : nonlinear regression Integral nonlinear regression CA nonlinear regression k 0.048 1.0001 2].035 2.i exp 1−α εi = CA. METHOD OF INITIAL COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) CHAPTER 7. These experiments are carried out a various inlet concentrations (CA0 ) and/or various conversions at the inlet.5.111 0.000 7. It is possible to use the same code to regress with α = 2.49) where ε is a vector of values.i − CA.000126 similar to those obtained before.3.model1.n) kr=x(1).126 α 2.037 2. //initial guess x=lsqrsolve(x0.037 And the quality of the fata ﬁt can be seen in Fig 7. deactivation as a result of byproducts forming.one for each data point collected ε= ε1 ε2 . . disp(’kr=’+string(kr)+’ alpha=’+string(alpha)) Cam=(Ca(1)^(1alpha)(1alpha)*kr*t)^(1/(1alpha)) //model predicted values The model parameters obtained are : k = 0. The scilab function is function f=model1(x.alpha=x(2).1467 0.95 2. .1248 0. ε n (7. exp model εi = CA. etc.50) The solution proceeds by developing a function that calculates the εi values at each data point and then call the scilab routine lsqrsolve to carry out the least squares minimisation.1046 0.000111 α = 2. Possible sequences might be 95 .
1 0.31 20 0.2 0. Real reactors operate at very high conversions. CA0 CA t 20 19 10 10 5 2 1 9.7. Real reactions undergo deactivation. 2. which are the conditions used under normal operation. Or possibly Xin Xout FA0 0.9 0. METHOD OF INITIAL COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) CHAPTER 7.41 25 0.51 30 From which the reaction rate can be obtained from a diﬀerential reactor balance (see later) Limitations of this method 1.5: Predicted and experimental data when using the nonlinear leasts squares method applied to concentration data. These methods fail to analyse such reaction systems 7.95 15 12 10 8 ∆CA CA0 − CA CA0 + CA Which yields the reaction rate = at the concentration from which ∆t t 2 the law parameters can be obtained.51) 96 .21 15 0.3. RATES 55 50 45 CA [mol:L¡1] 40 35 30 25 20 15 0 50 100 150 200 250 300 time. The data in the tables have been extracted from the graphs. t [min] Figure 7. contrary to the very low conversions used here.4 0.5 0. High conversions almost always produce side products which can inﬂuence the reaction kinetics. If deactivation is fast (FCC) then this method fails since it becomes impossible to esrimate the initial reaction rate without the inﬂuence of the deactivation.1 Example (Fogler 54) The dissolution kinetics CalciumMagnesiumcarbonate within HCl has been measured and is shown in the graphs below.75 1. especially at high conversions. The reaction is 4HCl + CaMg(CO3 )2 → Mg 2+ + Ca2+ 4Cl − + 2CO2 + 2H2 O (7.5 4.3.3 0.11 10 0.
dt 2∆t dCHCl q = kCHCl dt (7. 1N HCl CHCl 1 0. RATES Determine the reaction order with respect to HCl? DATA: Run1.55) which yields CHCl.66E4 0.36E4 1.9986 3. This can be done with a forward diﬀerence formula since the data is equally spaced.5 1. ln − t=0 t=2 t=4 dCCCl −3CHCl + 4CHCl − CHCl = .9980 time [min] 0 2 4 6 8 Figure 7.L−1 ] dCHCl − [mol.9968 time [min] 0 2 4 6 8 Run2.7 shows that the model ﬁts the data well.7.50E4 2.9986 0.0 [mol.54) dt Thus need to estimate the reaction rate at t = 0 in each case.1 0. 97 .45 and Fig 7.9991 0.6: Data for example (Fogler54).0000 3.52) This is a batch reactor.49E4 Regressing these to get the reaction order: q = 0. so the design equation for a constant volume system is − Linearising: dCHCl = ln(k) + qln(CHCl ) (7.9993 3. 4N HCl CHCl 4.9996 0.9980 3.74E4 3.min−1 ] dt 1 4 2 0.3.53) ∆t = 2 (7.L−1 . METHOD OF INITIAL COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) CHAPTER 7. SOLUTION Assume a rate law with reaction order q : q −rHCl = kCHCl (7.
q −rA = −kCA − dCA q = kCA dt (7. 7. thus 2 1 q−1 CA0 CA0 CA q−1 −1 (7.56) Integration yields the reaction time to reach the concentration CA .8. t= 1 k(q − 1) 1 q−1 CA − 1 q−1 CA0 = 1 q−1 kCA0 (q − 1) 1 CA0 . METHOD OF HALF LIVES CHAPTER 7.4.58) 1 CA0 yields n (7. 98 . the nth life time.57) Using the halflife concept : t = t1/2 then CA = t1/2 = 2q−1 − 1 k(q − 1) (7. Thus a irreversible reaction.7. such that t = t1/n when CA = t1/n = Linearising this equation ln(t1/2 ) = ln 2q−1 − 1 k(q − 1) + (1 − q)ln(CA ) nq−1 − 1 k(q − 1) 1 q−1 CA0 The slope of the plot is (1 − q) from which the reaction order can be obtained as shown in Fig 7.4 Method of half lives The half life of a reaction is the time it takes to reduce the conversion (concentration) by half the initial value. A → pr oducts with a q th order rate law in a batch reactor the design equation is.59) or using a general concept.7: Linearised initial rate plot for the dissolution process. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) 3 10 ¶ dCA ¡ [mol:L¡1:min¡1] dt 0 µ 10 4 10 5 10 1 10 0 10 1 Figure 7.
CSTR’s and recycle reactors : The CSTR delivers the reaction rate at any concentration directly from the measured variables. In this way the reaction rate can be estimated at diﬀerent conversions. There are essentially 2 types of diﬀerential reactors : Fixed bed (plug ﬂow) : In these reactors the conversion in the reactive zone is small. since it is diﬃcult to precisely deﬁne the conditions at t = 0. This reduces the error.9.5. The feed enters the reactor at various degrees of conversion which is achieved by dilution with product species. These ideas can be viewed in Fig 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) Figure 7.8: Halflife analysis plot.5 Diﬀerential reactors (including CSTR and recycle reactors) The idea of these kinds of reactors is to directly calculate the reaction rate and not have to diﬀerentiate the concentrationtime data.7. which translates into a conversion per pass of <5%. 7. These type of experiments are not generally carried out in Batch type reactors. These reactors also operate with no pressure drop and isothermally as a result of the reaction zone and conversion being small. DIFFERENTIAL REACTORS (INCLUDING CSTR AND RECYCLE REACTORS) CHAPTER 7. The ﬂow rate of reactants to the reactor remains largely unchanged. 99 . A recycle reactor (no separation of the products must take place) can be assumed to have the same analysis as a CSTR when the recycle ratio is greater than 20. The conversion is changed by changing the feed rate and not the feed conversion as is needed for the ﬁxed bed reactor.
7. W HSV .L−1 .9 shows the concepts of how a recycle system relates to a real integral reactor.7. It thus provides a ideal reactor for studying the rate law of reactions. However. The high ﬂow rates through the reactor section ensure that (i) the conversion is low <5% (ii) the ﬁlm mass transfer limitations are negligible. the ﬂow rate (FA0 ) or more precisely the τ.1 Mole balances : CSTR (and recycle reactor with rapid recycle) FA0 − FA FA0 ν0 CA0 CA0 = X= X= X V V V τ FA0 − FA FA0 −rA [mol.5. This is the ideal reactor conﬁguration to use for the development of rate laws. Essentially the catalytic zone (reactive zone) represents a slice of the normal reactor. When this reactor section of the reactor is placed within a recycle loop in which the recycle ﬂow rate exceeds 20 times the feed ﬂow rate. The variation in reaction rate is obtained by changing the volume (V.kg−1 . by will be mixed with products of the reaction and will thus enter partially converted. it is very diﬃcult to achieve good CSTR operation. the reactor feed will no longer be pure feed. and great care must be taken to ensure that the mixing is adequate such that the CSTR assumptions are valid.60) (7. 100 . COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) Figure 7. Fig 7. DIFFERENTIAL REACTORS (INCLUDING CSTR AND RECYCLE REACTORS) CHAPTER 7.s−1 ] = = X = (W HSV )CA0 W W −rA [mol. W ).61) So CSTR’s yield the reaction rate directly at any concentration or conversion of the reactants or products (even for multiple reactions).s−1 ] = (7.5.9: Diﬀerential reactor operation : concepts.
ﬁrst approximation the reaction rate at the middle of the ∆W interval. (a) From the data supplied determine the conversion for each experiment and the partial pressures of CO and H2 at the inlet and outlet of the reactor.3 Example : Fogler 55 The formation of methane from carbon monoxide(A) and hydrogen(B) CO + 3H2 → CH4 + H2 O A + 3B → C + 2D is being studied at 260°C in a diﬀerential reactor where the concentration of methane leaving the reactor is measured.e. a −rCO = k1 PCO 101 . FA Z − FA Z+∆Z − rA ∆W = 0.out − CA.in CA. −rCO = f (CO) · g(H2 ) Determine the reaction order with respect to PCO by assuming the rate equation. thus. (b) The reaction rate equation is proportional to the partial pressure of CO with the function f (CO) and proportional to the partial pressure of H2 with the function g(H2 ). dW dW FA0 dX = rA dW (7.in .5.out + CA. For complex reactions this proves to be impossible.2 Mole balances : Tubular and packed bed systems Fig 7. the ﬁrst one large enough to generate the conversion desired to be used in the second diﬀerential reactor. These systems are not popular for the study of complex chemical reaction system kinetics. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) 7.9 also shows that the diﬀerential reactor is also a slice of the full scale reactor. to a FA. i. at 2 CA. The mole balances are best viewed through the ﬁrst order approximation to the PBR design equation.in Xout + Xin . DIFFERENTIAL REACTORS (INCLUDING CSTR AND RECYCLE REACTORS) CHAPTER 7. In practice for complex reaction systems. However. dFA dCA = ν0 = −rA .e.in Xout − Xin = ν0 = FA0 ∆W ∆W ∆W (7. i. in this reactor the feed must be premixed with products to yield feeds that reproduce the conversion proﬁle of the fullscale reactor.62) Now making a ﬁrst order approximation of the diﬀerential to yield the average reaction rate within the diﬀerential interval ∆W is −rA = FA. It is not the reaction rate at the inlet to the diﬀerential reactor as 2 2 proposed by Fogler. the experimental system operates with two reactors in series. The reaction rate so evaluated represents. Determine also the average reaction rate of CO across the reactor.5.out + FA. 7. .7.out − FA.63) Here the conditions FA0 and CA0 are reserved for the ﬂow rate and concentration of the unconverted feed and correspond to X = 0.5. draw a parallel with the trapazoidal integration where the integration uses the average value between the end points of the interval if the integration step.
PCO and PH2 were measured at the reactor inlet and CCH4 was measured at the reactor exit. Run PCO [atm] PH2 [atm] CCH4 [mol.40 3 4.. Stoichiometric table gives A FA0 FA0 (1 − X) F0 = FA0 (1 + α) FA0 B FB0 FB0 − 3X FA0 α= C 0 FA0 X FB0 PB0 = FA0 PA0 D 0 2FA0 X in out total FT = FA0 (1 + α − X) 102 .73 2 1.. The catalyst bed contained 10 g of catalyst.1 1. isothermal reactor. .47 6 1 4. the molar ﬂow rate of CO.75 The exit volumetric ﬂow rate was maintained at 300 [L. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) (c) Show that the data suggests a rate law for the hydrogen dependence of −rCO = b k2 PH1 2 b 1 + KH2 PH2 2 (d) By combining the two rate laws.65 5 1 0.5. KH2 .5 2.X. SOLUTION (a) Looking at the data (i) There are 2 sets of data. yields the overall rate equation −rCO = b kPCO PH1 2 b 1 + KH2 PH2 2 Regress this equation for the constants k. Make the usual assumptions : ideal gases.0 4 1 0.min−1 ].L−1 ]×104 1 1 1 1. b1 . Thus the CO and H2 dependence can be analysed separately (ii) The data required will require a stoichiometric table to relate all the quantities to each other. runs 13 are at constant PH2 and runs 1.0 1. FA0 and the average partial pressures of CO and H2 across the reactor.08 1 10.18 1 4.2: Experimental reaction data for the conversion of CO to CH4 . b2 . DIFFERENTIAL REACTORS (INCLUDING CSTR AND RECYCLE REACTORS) CHAPTER 7.46 are at constant PCO . DATA: Table 7.7. Design equation for the reaction rate of CO is −rCO = FA0 Xout ∝ f (PCO ) · g(PH2 ) ∆W Thus it will be necessary to determine the conversion.
(b) Regression for k1 .000 PB. P = PA0 + PB0 and varies from run to run. a : ln (−rCO ) = ln(k1 ) + a · ln(PCO ) thus k1 = 0.in 1.03.2 4.99 PA is relatively constant.7.10 1.114 0.877 0. DIFFERENTIAL REACTORS (INCLUDING CSTR AND RECYCLE REACTORS) CHAPTER 7.996 0.485 3.10 0.18 5. since 3 moles of B required for every mole of A that reacts away.00745 and a = 1.3.975 0.0300 0.996 0.0052 PA.993 Run PA.500 4.00 0. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) From the data.av e 0.00 α 1.0251 0.90 0.0457 0.998 1.out 0.00 2 1.996 PB.88 0.0161 8. Fig 7. however the biggest variation (still not much) is in PB across the reactor even when PB0 is a constant.3: Processed reaction data.981 0.075 0.998 0.175 4.5. and since the exit volume ﬂow rate (ν) is given.100 0. the methane concentration gives the reaction rate.86 0.0074 0.171 0.out 0.00 PB.0071 6.079 0.00 6 1.00 1.983 −rCO 0.0132 0.938 0.0076 6.951 0.089 0.0107 6.990 0. Table P 2.0049 0. Thus FA0 can be obtained from the above equation.999 0. Making a new table 7.000 0. The partial pressures of CO and H2 at the reactor exit are given by PA = 1−X (PA0 + PB0 ).00 2.0106 28.245 0.18 3 4.00 7. CT X FA0 PA.999 0.08 1.071 0.0075 6. the molar ﬂow rate of methane can be calculated from FC = νCCH4 = FA0 X The conversion can be obtained by looking at the methane concentration CCH4 = Rearrangement gives the conversion X= CCH4 (1 + α) CCH4 + CT FC P X = CT FT RT 1+α−X Note that the total presssure P and thus the total concentration. CT is not constant since.0498 0.08 4 1. 1+α−X PB = α − 3X (PA0 − PB0 ) 1+α−X and the reaction rate of CO can be obtained from the above equation.av e 0.10 shows that the data scatter is large and too few points!! 103 .847 0.00 5 1.in 1 1.00 1.0342 0.50 4.50 5.0052 0.16 1.471 3.116 0.90 0.
Fig 7. 0.0045 0.11: Plotting the −rCO dependence on PH2 .5. (i) plotting the data shows that at low P the rate is low.0 1.5 2.0 3. DIFFERENTIAL REACTORS (INCLUDING CSTR AND RECYCLE REACTORS) CHAPTER 7.0070 0.0060 0.7.5 3.0 0.11. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) 1 10 ln(¡rCO) [mol:L¡1:min¡1] 10 2 10 3 10 1 10 0 10 1 PCO [atm] Figure 7.0 PH2 [atm] Figure 7.10: Regression plot for the −rCO dependence on PCO .0075 b k2 PH1 2 b 1 + KH2 PH2 2 ln(¡rCO) [mol:L¡1:min¡1] 0.5 4. goes through a maximum and then decreases again.it then increase as PH2 increases.5 1. 104 .0055 0.0 2. (c) Looking at the second table and the rate law −rCO = and making a plot of the data.0050 0.0065 0.
5.n) disp(info. rate_m=k*Paa.02 0.*Pbb^b1.115 1 + 0. 105 . 0. k2 b1 −b2 b (ii) At high PH2 : then 1 KH2 PH2 and the rate law reduces to −rCO = P .13 shows the ﬁt of the reaction rate.’info’). //b1=0. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) b b (ii) At low PH2 : then 1 KH2 PH2 and the rate law reduces to : −rCO = k2 PH1 .] With this in mind and the fact that there are too many parameters for such few data.Kh2=p(4).0484. 3.i − In Scilab this looks like this //least squares regression for all the parameters function f=model(p..12.5 1 1].i 2 mi n obj(k. The ﬁt of the model to the reaction rate is shown inFig 7. 46.i PH1 .b2=1. 1.b1=p(2).7. disp(p. which from mechanistic considerations is not realistic. b1 .n) k=p(1).*Pbb^b1.5.i 2 b 1 + KH2 PH2 . b2 .e p = p ± σ. KH2 ) = i=1 −rCO.01135.’lsqrE’). disp(norm(v). . This is already noted in the scatter when ﬁtting for the reaction order of CO.b2=p(3). 0.33. The rate law then is 0. DIFFERENTIAL REACTORS (INCLUDING CSTR AND RECYCLE REACTORS) CHAPTER 7.5.b1=p(2).115. 1. KH2 ] = [0.79.use a nonlinear regression for all the constants 6 b kPCO.0287 and KH2 = 2. [p v info]=lsqrsolve(p0.’p’) k=p(1). so does the reaction rate. rounding the orders of the reactions oﬀ to the nearest accepable value.0050 and a variance of σ = [0.01135PCO PH2 −rCO = 1. 0. It can be seen that the reaction rate at constant PH2 is not was well predicted as the variation with PH2 . Thus as 2 2 PH2 increases. If b1 −b2 < 0 2 KH2 H2 then increasing the pressure will decrease the reaction rate.510PH2 Also the reaction orders are noninteger values.510] with a LSQRerror of 0. but the trend of the rate law obeys the rate data at least conceptually. 1.33 0.model. yields −rCO 0. 106] i. (d) Regressing all the data. in fact the model parameters are useless. f=ratek*Paa.79] which is still very high. since the variance exeeds the parameter value. b1 . Typically reaction orders are [0.0050 and a variance σ = [0. Fig 7. but at least better then before..90 with a LSQRerror of 0. b2 .Kh2=p(4). The data is rather few./(1+Kh2*Pbb^b2) endfunction And calling the least squares solver with an initial guess p0=[0.b2=p(3)./(1+Kh2*Pbb^b2) //predict the reaction rate from parameters The parameters are p = [k2 . 26.5 kPCO PH2 = 1 + KH2 PH2 Now regressing again yields k = 0.5. Furthermore the variance in the model parameters is very high.
KH2 in the rate law.5 2.035 0.0 1.025 0.010 0. that the LSQRerror does not change much between the last 2 rate laws.020 0. Note.5 4. 106 .7.010 0.sce” does all the calculations. There are not enough data points to accurately evaluate the reaction orders.0 2.000 0.0 3.015 0. This yields the ﬁnal rate law −rCO 0.48PH2 The rate law is OK. 0.5 2. The Scilab code “FoglerEx55.030 ¡rCO [mol:L¡1:min¡1] 0. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5) 0.5.5 1.005 0.5 3.5 0.0 3.5 3.0 1.025 0.0 PH2 [atm] Figure 7.0189PCO PH2 = 1 + 1. just there are too few data points ot make these values reliable.13: The prediction of the reaction rate when regressing for k.5 4.0 PH2 [atm] Figure 7.0 0.0 0.005 0. DIFFERENTIAL REACTORS (INCLUDING CSTR AND RECYCLE REACTORS) CHAPTER 7.015 0.12: The prediction of the reaction rate when regressing for all the rate law constants.035 0.020 0.0 2.030 ¡rCO [mol:L¡1:min¡1] 0.5 1.000 0.
Chapter 8 Developing rate laws from reaction mechanisms and reaction pathways 107 .
Chapter 9 Bioreactor engineering mechanisms 108 .
Chapter 10 Bioreactor design 109 .
Chapter 11 Analysis of reactor ﬂow patterns on reactor performance (Fogler chapter 13) 110 .
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