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Chemical Engineering Reactions

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Chemical
Reaction
Engineering
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CHEMICAL REACTION ENGINEERING
Chapter No. Topic
Overview/Introduction
1

Basics and Mole balances
Types of Chemical reactions
Reaction rate
General mole balance equation
Batch reactors
Continuous- flow reactors
2 Conversion and design equations
Definition of Conversion
Design Equations
Applications to Continuous flow reactors
Series reactors
Stoichiometric Table
Applications of stoichiometry to different reactions
3 Interpretation of Rate Data
Differential method
Integral method
Method of half lives
Least square analysis
4 Multiple reactions
Parallel reactions
Series reactions
Autocatalytic reactions
5 Non Isothermal reactor
Energy Balance
Non-isothermal continuous flow reactors
Equilibrium conversion
Non-isothermal non-adiabatic reactor design
6 Catalysis and catalytic reactor
Catalysts
Steps in catalytic reaction
Synthesize rate law, mechanism
Design of reactors for Gas-Solid reactions
7 Diffusion and reaction in Porous catalysts
Internal effectiveness factor
Falsified Kinetics
8 Basics of Non ideal reactor
Exit Age distribution, RTD measurement & characteristics
RTD in ideal reactors
9 Non Ideal Reactor model
Zero and One-parameter model
Conversion in Non Ideal Flow reactors


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OVERVIEW
Material and energy balances are the heart of chemical engineering. Combine them with
chemical kinetics and they are the heart of chemical reaction engineering. Add transport
phenomena and you have intellectual basis for chemical reactor design.
The chemical reactor is the heart of any chemical process. Chemical processes turn inexpensive
chemicals into valuable ones, and chemical engineers are the only people technically trained to
understand and handle them. While separation units are usually the largest components of a
chemical process, their purpose is to purify raw materials before they enter the chemical reactor
and to purify products after they leave the reactor.
Here is a very generic flow diagram of a chemical process.


Raw materials from another chemical process or purchased externally must usually be purified to
a suitable composition for the reactor to handle. After leaving the reactor, the unconverted
reactants, any solvents, and all byproducts must be separated from the desired product before it is
sold or used as a reactant in another chemical process.
The key component in any process is the chemical reactor; if it can handle impure raw materials
or not produce impurities in the product, the savings in a process can be far greater than if we
simply build better separation units. In typical chemical processes the capital and operating costs
of the reactor may be only 10 to 25% of the total, with separation units dominating the size and
cost of the process. Yet the performance of the chemical reactor totally controls the costs and
modes of operation of these expensive separation units, and thus the chemical reactor largely
controls the overall economics of most processes. Improvements in the reactor usually have
enormous impact on upstream and downstream separation processes.
Thus chemical reaction engineering becomes very important topic of chemical engineering. The
pillars holding up the application of chemical reaction engineering



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Analysis of chemical reactors incorporates essentially all the material in the chemical
engineering curriculum. In this course we will need to use material from thermodynamics, heat
transfer, mass transfer, fluid mechanics, and especially chemical kinetics.

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CHAPTER 1. BASICS AND MOLE BALANCES
CONCEPT 1. TYPES OF CHEMICAL REACTIONS
CHEMICAL REACTION
A process by which a chemical loses its chemical identity.
There are Three (3) ways a chemical can lose its identity:

- Dehydrogenation of ethane gas produces a useful petrochemical reagent, ethene. It also
produces hydrogen gas, which can be used for multiple synthesis reactions.
- The oxidation of nitrogen to form NO
x
is a very important reaction occurring at high
temperatures, nitrogen combustion occurs in many furnaces and internal combustion engines,
wherever nitrogen is present at temperatures > 800
o
C. NO
x
s are a major environmental
concern, as they play significant roles in smog formation and acid rain.
- Isomerization reactions are important in the petroleum industry, for raising the octane
number of alkenes for gasoline production.
From the perspective of species A, these are the three ways in which species A can change/lose
its chemical identity. Any reaction for any arbitrary species A can be classified in these terms.
There are some other useful classifications and definitions for describing chemical reactions:
- Homogeneous Reaction: Reactions in which all participating species (reactants, products,
catalysts) are in the same phase, i.e. gas, liquid or solid.
- Heterogeneous Reaction: Reactions in which participating species (reactants, products,
catalysts) are spread across multiple phases (e.g., gas-liquid reaction; gas-solid catalytic
reaction). A significant portion of industrial chemical reactors are heterogeneous systems.
A B + C
H
3
C-CH
3
H
2
C=CH
2
+ H
2

ethane
ethene
hydrogen
A + B C
N
2
+ O
2
2 NO
nitrogen oxygen
NO
x

A B

Decomposition
Combination
Isomerization
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- Irreversible Reaction: Reaction takes place in only one direction as indicated by a one-
way arrow when written. Irreversible reactions will run to completion, given enough time.
- Reversible Reaction: Reaction which can take place in both directions, i.e. can run in
reverse. Indicated by a two-way arrow when written. Most real-world reactions are
reversible. Reversible reactions will reach Equilibrium, given enough time.
- Autocatalytic Reaction: A reaction which is catalyzed by its own product; these are
particularly fun reactions, as the reaction rate will increase as reactants are consumed, owing
to the autocatalytic phenomena. We will use this rate expression later for reactor design.
- Catalytic Reaction: A reaction which occurs over a catalyst to accelerate the reaction rate.
Reaction rates are related to collision rates with catalytic species.
- Catalyst: A species which enhances the rate of reaction without being created, modified or
consumed by the reaction. Examples include enzymes, noble metal powders or metal-ligand
complexes for organic synthesis.

Molecularity is the number of molecules taking part in the given reaction.
Elementary reaction : An elementary reaction is the one that evolves a single step. Thus for such
reactions stoichiometric coefficients are identical to the powers in the rate law.
It is important to remember that the rate laws are determined by experimental observation. They
are the function of reaction chemistry and not the type of the reactor in which the reactions
occur.
Catalyst Surface
(Heterogeneous
Catalytic)
Collision
(Homogenous
Non-Catalytic)
Illustration 1: Cartoon of Chemical Reactions
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Past GATE Questions on Concept 1
1. Molecularity of an elementary reaction P + Q R + S is
A) 1 B) 2 C) 3 D) 4
2. For the reaction A + B 2B + C
A) r
A
= r
B
B) r
A
= -r
B
C) r
A
= 2r
B
D) r
A
= r
B
/2
3. The experimentally determined overall order for the reaction A + B C + D is
two. Then the
A) reaction is elementary with a molecularity of 2.
B) molecularity of the reaction is 2, but the reaction may not be elementary,
C) reaction may be elementary with a molelcularity of 2,
D) reaction is elementary but the molecularity may not be 2,
4. The extent of a reaction is
A) different for reactants and products
B) dimensionless
C) dependent on the stoichiometric coefficients
D) all of the above
5. For the reaction 2R + S T, the rates of formation, r
R
, r
S
and r
T
of the substances R, S
and T respectively, are related by
A) 2 r
R
= r
S
= r
T
B) 2 r
R
= r
S
= r
T

C) r
R
= 2 r
S
= 2 r
T
D) r
R
= 2 r
S
= 2 r
T
6. Which is the correct statement from the following statements on the Arrhenius model of
the rate constant k = Ae
-E/RT
?
A) A is always dimensionless
B) For two reactions 1 and 2, if A
1
= A
2
and E
1
> E
2
, then k
1
(T) > k
2
(T)
C) For a given reaction, the % change of k with respect to temperature is higher at
lower temperatures.
D) The % change of k with respect to temperature is higher for higher A.
7. The rate expression for the reaction of A is given by
The units of k
1
and k
2
are, respectively,
A) (mol
-1
m
3
s
-1
), (mol
-1/2
m
3/2
) B) (mol
-1
m
3
s
-1
), (mol
-1/2
m
3/2
)
C) (mol m
3
s
-1
), (mol
-1/2
m
3/2
s
-1
) D) (mol
-1
m
3
s
-1
), (mol
-1/2
m
3/2
s
-1/2
)

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Solutions to GATE Questions on Concept 1
Q. No. Ans.
1. C
2. B
3. A
4. D
5. D
6. C
7. A
CONCEPT 2. THE REACTION RATE
REACTION RATE
The rate at which a species loses its chemical identity, per unit volume, per unit time.
r
A
= rate of formation of species A per unit volume, [=] mol.s
-1
.dm
3

r
A
= rate of disappearance of species A per unit volume [=] mol. s
-1
.dm
3

r
B
= rate of formation of species B per unit volume [=] mol. s
-1
.dm
3

Why per-volume basis? Because from kinetic theory, reactions occur as a result of collisions;
collision rates are directly related to the concentration, or number of molecules in a given
volume.
WHAT IS REACTION RATE A DIRECT FUNCTION OF?

(1) Rate of reaction is a direct function of CONCENTRATION, i.e. -r
A
= f(C
A
)

volume
j species mol #
= =
V
n
C
j


if a liquid, then reaction rate has a weak
dependency upon pressure.

RT
p
RT
P
y
RT
P
n
n
C
i
i
T
j
= = =

if in gas phase, reaction rate can have a
strong dependence upon pressure.
(2) Rate of reaction is a direct function of TEMPERATURE, i.e. -r
A
= f(T)
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From kinetic theory, the rate of collisions between molecules is also a function of how much
energy those molecules. Likewise, the ability for a collision to result in chemical transformation
is related to the energy content of the species.
The most common temperature-functionality of the reaction rate is the Arrhenius Relationship,

RT E
o A
A
e k r
/


Where k
o
is the pre-exponential factor, sometimes referred to as a turnover frequency, E
A
is the
activation energy and R is the ideal gas constant.
- The rate constant k which is function of T can be obtained through different theories.
However: Arrhenius law given by
/
A
E RT
k Ae

is a good approximation.
- From Collision theory the temperature dependency is given by
/ 1/2
A
E RT
k T e


- From Transition theory the temperature dependency is given by
/
A
E RT
k Te


NOTE: Rate of reaction is an indirect function of TEMPERATURE when in Gas Phase:

RT
p
RT
P
y
RT
P
n
n
C
i
i
T
j
= = = for an ideal gas, thus r
A
= f(C
A
) and
T
C
1
.
We will also show that the rate of reaction can be indirectly affected by reaction stoichiometry
and the momentum balance in flowing systems, again through this direct concentration
dependence.
What is reaction rate NOT a function of? r
A
is NOT a function of reactor type, configuration,
flow behavior, transport patterns, etc
Another thing to keep in mind: r
A
is NOT a differential equation. It is an algebraic relationship
containing temperature and concentration dependences.
So, what does r
A
look like?
( ) ( ) T f C f r
A
= ,
where ( ) ( )
RT E
o
A
e k T k T f
/
= = (Arrhenius relationship, unless otherwise noted).
If isothermal reaction, then we can ignore temperature dependence of the reaction rate, and
simplify:
( ) k C f r
A
=
So, what is the concentration function, ( ) C f ?
If Elementary Reaction, then ( ) C f is defined as follows:
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aA + bB cC +dD,
( )
b
B
a
A
C C C f = , and under isothermal conditions, ( )
b
B
a
A A
C kC C r =
This is called a Power-Law dependence, because rates are related to concentrations to the n-
power (called an n-th order dependency), dictated by species stoichiometric coefficients.
For elementary reactions order of the reaction with respect to the reactant are obtained
from the stoiciometric coefficients.
For non-elementary reactions reaction orders have to be obtained experimentally.
Example 1: A B, elementary non-isothermal, gas-phase reaction.
( ) ( ) T f C f r
A
= , ( )
1
A
C C f = , ( ) ( )
RT E
o
A
e k T k T f
/
= = , therefore
RT E
o A A
A
e k C r
/ 1
= .

But, if this is an ideal gas, then we want to account for concentration changing with volume and
temperature; therefore:

RT E
o A A
A
e k
RT
P
y r
/ 1
=
This rate expression has two temperature functionalities, and one pressure dependence.
Example 2: A + B C + D, elementary non-isothermal, gas-phase reaction.

RT E
o B A A
A
e k C C r
/ 1 1
= , and for gas-phase,
RT E
o B A A
A
e k
RT
P
y y r
/
2
1 1
|
.
|

\
|
=
This reaction can be manipulated to run much faster by pressurizing the reactor, as can be seen
from inspection of the second-order dependence of the rate.
What about Non-Elementary Kinetics? Many overall reactions do not follow elementary kinetics
(although, as well see later on in this course, these complex kinetics can be broken down into a
large array of elementary reactions), but can be described by a non-elementary rate law.
Example 3: A B, catalytic, isothermal, liquid-phase isomerization of A
A
A
A
C k
C k
r
2
1
1+
=
If k
2
C
A
>> 1, then
2
1
k
k
r
A
~ , appears zero-order.
If k
2
C
A
<< 1, then
A A
C k r
1
~ , appears first-order.
Depending upon operating conditions, the reaction may appear to have different orders!
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IRREVERSIBLE VS. REVERSIBLE REACTIONS
Irreversible Reaction: reaction takes place in only one direction as indicated by a one-way
arrow when written. Irreversible reactions will run to completion, given enough time.
Reversible Reaction: a reaction which can take place in both directions, i.e. can run in reverse.
Indicated by a two-way arrow when written. Most real-world reactions are reversible.
Reversible reactions will reach Equilibrium, given enough time.
Consider the exothermic, heterogeneous reaction: A + B C
At low temperatures, rate law for disappearance of A is irreversible (as drawn above):
A Ad
B A f
f A A
C K
C C k
r r
+
= =
1
,
, where k
f
is the forward rate coefficient. Just to complicate things, K
Ad

is the rate coefficient of adsorption of A on the catalyst. Dont worry about it for now
At high temperatures, the reverse reaction rate becomes appreciable, such that the overall
reaction is now reversible:
A + B C
A Ad
B A f
f A
C K
C C k
r
+
=
1
,
is still the expression for the forward rate of reaction. However, reaction
product C can decompose back into A and B (owing to the high energy of the environment,
perhaps).

A Ad
C r
r A
C K
C k
r
+
= +
1
,
; we can see from this that as C accumulates, the reverse reaction rate
increases; thus an equilibrium will eventually be reached where any excess C produced
immediately decomposes back into A and B (and vice versa).
The NET RATE of disappearance of A is the sum of all individual reactions producing and
consuming species A:
|
|
.
|

\
|

+
=
+

+
= =
f
C r
B A
A Ad
f
A Ad
C r
A Ad
B A f
r A f A A
k
C k
C C
C K
k
C K
C k
C K
C C k
r r r
1 1 1
, ,

The ratio of the forward rate coefficient to the reverse rate coefficient is the Equilibrium
coefficient,
( )
(


= = =

RT
E E
k
k
e
e
k
k
k
k
K
r A f A
r o
f o
RT E
RT E
r o
f o
r
f
eq
r A
f A
, ,
,
,
/
/
,
,
exp
,
,

So,
|
|
.
|

\
|

+
=
eq
C
B A
A Ad
f
A
K
C
C C
C K
k
r
1
.
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At equilibrium, the net rate of reaction is ZERO, and we can use the above equation to determine
the equilibrium coefficient from corresponding concentrations at equilibrium.
|
|
.
|

\
|

+
= =
eq
eq C
eq B eq A
eq A Ad
f
A
K
C
C C
C K
k
r
,
, ,
,
1
0 ,
so
|
|
.
|

\
|
=
eq
eq C
eq B eq A
K
C
C C
,
, ,
0 , or
eq
eq C
eq B eq A
K
C
C C
,
, ,
= , or
eq B eq A
eq C
eq
C C
C
K
, ,
,
=
This should look very familiar: it is the same definition for equilibrium given in your General
Chemistry, Organic Chemistry and Thermodynamics Courses.
What if we have multiple reactants?
reaction (I): aA + bB cC + dD
r
A
= rate of disappearance of species A per unit volume
r
B
= rate of disappearance of species B per unit volume
+r
C
= rate of appearance of species C per unit volume
+r
D
= rate of appearance of species D per unit volume
r = rate of reaction (I)
r =
d
r
c
r
b
r
a
r
D C B A
+
=
+
=


Past GATE Questions on Concept 2
1. The units of frequency factor in Arrhenius equation,
A) Are the same as those of the rate constant.
B) Depend on the order of the reaction.
C) Depend on temperature, pressure etc. of the reaction.
D) Are cycles per unit times.
2. The dimensions of rate constant for reaction 3AB are (1 /g mole)/min. Therefore the
reaction order is
A) 0 B) 1 C) 2 D) 3
3. From Collision Theory, the Reaction Rate Constant Is Proportional To



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4. For reaction P + 2Q 3R, molar rate of consumption of P is
A) double of that of Q B) same as that of Q,
C) half of that of Q D) 2/3 of that of Q
5. Overall order of reaction for which rate constant has units of (mol/L)
-(3/2)
sec
-1
is
A) 3/2 B) 1/2 C) 3/2 D) 5/2
6. The rate expression for the gaseous phase reaction is given by

Which of the following is NOT possible?
A) = 1, = 1, = 1 B) = 1, = 2, = 1
C) = 1/3, = 2/3, = 1/3 D) = 1/2, = 1, = 1/2
7. For a homogeneous reaction system, where
Cj is the concentration of j at time t
Nj is the number of moles of j at time t
V is the reaction volume at time t
t is the reaction time.
The rate of reaction for species j is defined as
A) B) C) D)
8. The rate constant of a chemical reaction increases by 100 times when the temperature is
increased from 400 K to 500 K. Assuming transition state theory is valid, the value of
E/R is
A) 8987 K B) 9210 K, C) 8784 K D) 8621 K,
9. At a given value of E/R (ratio of activation energy and gas constant), the ratio of the rate
constants at 500 K and 400 K is 2 if Arrhenius law is used. What will be this ratio if
transition-state theory is used with the same value of E/R?
A) 1.6 B) 2 C) 2.24 D) 2.5
10. The following rate-concentration data are calculated from experiment. Find the
activation energy temperature (E/R) of the first order reaction.
d
p
C
A
r
A
T

1 20 1 480
2 40 2 480
2 40 3 500
A) 2432.8 B) 4865.6 C) 9731.2 D) 13183.3
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Solutions to GATE Questions on Concept 2
Q. No. Ans.
1. A
2. C
3. D
4. A
5. D
6. A
7. C
8. C
9. D
10. B
CONCEPT 3: GENERAL MOLE BALANCES EQUATION
The mole balance is a mass balance applied to a specific molecular species, e.g. water, helium, p-
xylene, etc.
From first fundamentals, we draw a Control Volume, V:


A out A in A
A
G F F
dt
dN
+ =
, ,
, where ( )
}
=
V
A A
dV C T r G ,
V
F
AO

F
A

Rate of Accumulation = rate of flow in rate of
flow out + rate of generation by chemical reaction
! Neglecting diffusion
! Assuming one species flow in, one
flow out
! rates in units of moles/time
!
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Remember that r
A
= f
n
(T,C), in other words, is a function of both local temperature and
concentrations of multiple species. It may also be an indirect (via concentration dependence)
function of local pressure.
If T, C, P vary throughout the control volume, V, then we must integrate r
A
(T,C) across the
entire control volume, and
( )
}
=
V
A A
dV C T r G ,
If T, C, P are constant throughout control volume, V, then we can state that r
A
(T,C) is also
constant across the entire control volume, and
( ) ( ) V C T r dV C T r G
A
V
A A
= =
}
, ,
Obviously, the trick for setting up a manageable differential mole balance of species A is to
choose your control volume wisely.
PICKING A CONTROL VOLUME
How can T be uniform across the entire volume, V?
- Hard: If V is a differentially small volume, then one can apply a microscopic mole balance.
This analysis is covered in great detail elsewhere (Geankopolis, Bird, Stewart and Lightfoot).
Microscopic balances yield partial differential equations which can accurately account for
real spatial deviations, such as laminar pipe flow with diffusion and reaction. Well come
back to this more advanced class of modeling much later
- Easier: if V is well-mixed, then concentration, pressure and temperature are uniform, and we
can apply a simpler macroscopic mole balance.
So, let us pick some classic well-mixed volumes and practice mole balances with reaction.
Past GATE Questions on Concept 3
1. A second order liquid phase reaction A B is carried out in a mixed flow reactor
operated in semi-batch mode (no exit stream). The reactant A at concentration C
AF
is fed
to the reactor at a volumetric flow rate of F. The volume of the reacting mixture is V and
the density of the liquid mixture is constant. The mass balance for A is
A) B)
C) D)
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Solutions to GATE Questions on Concept

Q. No. Ans.
1. d

CONCEPT 4: THE BATCH REACTOR (OR THE CHEMISTS REACTOR)
- No flow in or out (closed system)
- Entire reaction volume is well-mixed (stirred tank or recirculated tank)
- Can be a 50 mL reaction flask or a 300 gallon tank with multiple mixing blades
- ENTIRE REACTOR VOLUME IS THE CONTROL VOLUME.

Species A molar balance:
A out A in A
A
G F F
dt
dN
+ =
, ,
, where ( )
}
=
V
A A
dV C T r G ,
Or
( )V C T r
dt
dN
A
A
, =
where T and C are the uniform temperature and concentration of the well-mixed fluid within the
flask / industrial reactor.
Case 1: if r
A
= kC
A
, solved for C
A
as f
n
(t) assuming temperature of reactor remains constant
throughout (therefore, k remains constant). Also, assume liquid-phase reaction.
( )V C T r
dt
dN
A
A
, =
( ) C T r
dt
dN
V
A
A
,
1
= , and if a liquid-phase system, then we can state that
A
A
C
V
N
= , so
Scale up
500 mL
500 L
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( ) C T r
dt
dC
A
A
, =
Now let us substitute in our rate expression, which is in terms of concentration.
A
A
kC
dt
dC
=
This is a first-order, ordinary differential equation. All terms in this equation are in terms of one
independent variable (t) and one dependent variable (C
A
). Let us solve by separation of variables.
dt k dC
C
A
A
=
1

Weve re-written the above term such that the left-hand side contains all terms of C
A
, along with
dC
A
. The right-hand side contains all terms of t, along with dt. We can now integrate both sides
from t = 0, corresponding to C
AO
, and t = t, corresponding to C
A
(t).
} }
=
t t C
C
A
A
dt k dC
C
A
AO
0
) (
1

kt
C
C
AO
A
=
|
|
.
|

\
|
ln , which can be re-written for C
A
as:
kt
AO A
e C C

= , which is the classic exponential decay equation.
Past GATE Questions on Concept 4
1. For the liquid phase reaction A P, in a series of experiments in a batch reactor, the
half-life t
1/2
was found to be inversely proportional to the square root of the initial
concentration of A. The order of the reaction is
A) 3/2

B) 1
C) + 1/2 D) 1/2
2. The reaction A B is conducted in an isothermal batch reactor. If the conversion of A
increases linearly with holding time, then the order of the reaction is
A) 0 B) 1 C) 1.5 D) 2
Solutions to GATE Questions on Concept

Q. No. Ans.
1. A
2. D

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