1

B t h Batch
Plug flow
Steady-state flow
Mixed flow
Ideal Batch Reactor
It has neither inflow nor outflow of
reactants or products when the reaction is reactants or products when the reaction is
being carried out.
Uniform composition everywhere in the p y
reactor (perfectly mixed)
No variation in the rate of reaction
th h t th t l throughout the reactor volume
Batch Reactor
All reactants are supplied to the reactor at the outset. The
reactor is sealed and the reaction is performed. No addition
f l f d d i h i of reactants or removal of products during the reaction.
Vessel is kept perfectly mixed. This means that there will p p y
be uniform concentrations. Composition changes with time.
The temperature will also be uniform throughout the The temperature will also be uniform throughout the
reactor - however, it may change with time.
Generally used for small scale processes.
Low capital cost. But high labour costs. Low capital cost. But high labour costs.
Multipurpose, therefore allowing variable product
specification specification.
Typical Laboratory Typical Laboratory
Glass Batch Reactor
Typical Commercial Batch Reactor
Ideal Mixed Flow Reactor
Normally run at steady state.
Uniformly mixed, same composition Uniformly mixed, same composition
everywhere within the reactor and at the exit.
G ll d ll d h i ti l Generally modelled as having no spatial
variations in concentration, temperature, or
reaction rate throughout the vessel
CONTINUOUS STIRRED TANK REACTOR (CSTR)
BACKMIX REACTOR BACKMIX REACTOR
Backmixed, Well mixed or CSTR
U ll l d f
,
Usually employed for
liquid phase
F
A0
(C
A0
)
reactions.
F
A
(C )
Use for gas phase
usually in laboratory
(C
A
)
C
A
C
A
usually in laboratory
for kinetic studies.
C
A
Assumption: Perfect mixing occurs.
Characteristics
Perfect mixing: the properties of the reaction mixture are
uniform in all parts of the vessel and identical to the
properties of the reaction mixture in the exit stream (i.e.
C
A, outlet
= C
A, tank
)
The inlet stream instantaneously mixes with the bulk of
the reactor volume.
A CSTR t i d t h t d t t A CSTR reactor is assumed to reach steady state.
Therefore reaction rate is the same at every point, and
time independent time independent.
What reactor volume, V
r
, do we take?
V refers to the volume of reactor contents V
r
refers to the volume of reactor contents.
Gas phase: V
r
= reactor volume = volume contents
Liquid phase: V = volume contents Liquid phase: V
r
= volume contents
Cutaway view of a Cutaway view of a
CSTR/ Batch
Reactor Reactor
Ideal Plug Flow Reactor
N ll t d t t d t t Normally operated at steady state
Fluid passes through the reactor with no mixing p g g
of earlier and later entering fluid
No radial variation in concentration No radial variation in concentration
Referred to as a plug-flow reactor
The reactants are continuously consumed as
they flowdown the length of the reactor they flow down the length of the reactor.
PLUG FLOW REACTOR (PFR), TUBULAR REACTOR
All fluid element have same residence time.
Used for either gas phase or liquid phase reactions.
The plug flow assumptions tend to hold when there is
d di l i i ( hi d t hi h fl t R good radial mixing (achieved at high flow rates Re
>10
4
) and when axial mixing may be neglected (when
the length divided by the diameter of the reactor > 50 the length divided by the diameter of the reactor > 50
(approx.))
Selection of Reactors
Batch
Small scale
Production of expensive products (e g pharmacy) Production of expensive products (e.g. pharmacy)
High labor costs per batch
Difficult for large-scale production
CSTR : most homogeneous liquid-phase flow reactors
When intense agitation is required
Relatively easy to maintain good temperature control Relatively easy to maintain good temperature control
The conversion of reactant per volume of reactor is the smallest
of the flow reactors - very large reactors are necessary to obtain
high conversions g
PFR : most homogeneous gas-phase flow reactors
Usually produces the highest conversion per reactor volume of
any of the flow reactors any of the flow reactors
Difficult to control temperature within the reactor
Hot spots can occur
S i l h ti
The Rate Equation
Suppose a single-phase reaction
The most useful measure of reaction rate for reactant A is then:
In addition, the rates of reaction of all materials are related by: , y
Experience shows that the rate of reaction is influenced by the
composition and the energy of the material composition and the energy of the material.
By energy we mean the temperature (randomkinetic energy of
the molecules), the light intensity within the system (this may the molecules), the light intensity within the system (this may
affect the bond energy between atoms), the magnetic field
intensity, etc.
Ordinarily we only need to consider the temperature, so let us
focus on this factor. Thus, we can write
Rate constant, k
It isstronglydependent ontemperature It is stronglydependent on temperature.
In gas-phase reactions
It depends on catalysts and may be a function of total pressure.
I li id In liquid system
It can be a function of total pressure.
It d d i i t th d h i f l t It may depend on ionic strength and choice of solvent.
H id th t t l Here, we consider the temperature only.
Rate of reaction and temperature
Empirical Observations.
It wastheSwedishchemist SvanteArrheniuswhofirst suggestedthat
thetemperaturedependenceof thespecific reaction rateconstant, k,
couldbecorrelatedbyanequationof thetype:
RT
E
A k

i
couldbecorrelatedbyanequationof thetype:
RT
Ae k = = constant rate reaction
Arrhenius Equation
Where:
A=preexponential factor or frequencyfactor (1/time) A preexponential factor or frequencyfactor (1/time)
E=Activationenergy, J /mol or cal/mol
R=Gasconstant, 8.314J /mol K (or 1.987cal/mol K)
T=Absolutetemperature, K
Arrhenius equation has been verified empirically to give the
temperature behaviour of most reaction rate constants (within p (
experimental accuracy) over fairylargeexperimental ranges.
Activation energy determined experimentally by carrying out the Activation energy determined experimentally by carrying out the
reactionat several temperatures. After takingthenatural logarithmof
theArrheniusequation:
| |
E 1
ln k
-E/R
|
.
|

\
|
=
T R
E
A k
1
ln ln
1/T
Example 3-1(Fogler) Calculate the activation energy for the first-
order decomposition reaction of benzene diazoniumchloride to p
give chlorobenzene and nitrogen:
ln k
A
1/T
Arrhenius Equation Arrhenius Equation
A
E 1
lnk lnA
R T
| |
=
|
\ .
E/RT
A
k (T) Ae

=
R T
|
\ .
A
( )
A
14017
lnk 37.12 =
A
lnk 37.12
T
| |
kJ kJ
E (14017K)R (14017K) 8.314 116.5
mol K mol
| |
= = =
|

\ .
16 1
A 1 32 10 s

= A 1.32 10 s =
14017K
(
Arrhenius Equation
16
A
14017K
k (T) 1.32 10 exp
T
(
=
(

Homogeneous Heterogeneous g g
Elementary Non-elementary
Single Multiple
Chemical Bio-chemical
Classification
of Reactions
Reversible Irreversible
of Reactions
Exothermic Endothermic
Constant density Variable density Constant density Variable density
Catalytic Non-catalytic Catalytic Non catalytic
When a single stoichiometric equation and single rate equation
are chosen to represent the progress of the reaction we have a are chosen to represent the progress of the reaction, we have a
single reaction.
When more than one stoichiometric equation is chosen to
represent the observed changes, then more than one kinetic
i i d d t f ll th h i iti f ll th expression is needed to followthe changing composition of all the
reaction components, and we have multiple reactions.
Multiple reactions may be classified as: Multiple reactions may be classified as:
series reactions:
parallel reactions, which are of two types:
and more complicated schemes, an example of which is
Here, reaction proceeds in parallel with respect to B, but in series p p p
with respect to A, R, and S.
Order of reaction
One of the most general forms:
a b d
A B D
r kC C ....C =
where k = velocity constant or specific rate constant.
If C C =1; then r = k If C
A
, C
B
, . = 1; then r = k
a , b = reaction order with respect to C
A
, C
B
.
a + b + ... +d = overall order (this treatment is only applicable
to simple reactions).
Reaction order
Power to which concentration is raised to make rate
proportional to it. p p
It can only be determined experimentally.
Elementaryreaction
Elementaryreactionisonethatevolvesasinglestep.
The stoichiometric coefficients in an elementary Thestoichiometriccoefficientsinanelementary
reactionareidenticaltothepowersintheratelaw:
- + - + - OH O CH OH CH O
3 3
OH CH O O O
C C k r
3
- - -
=
Anelementaryreactionhasanelementaryratelaw.
Some reaction follows an elementary rate law is not Somereactionfollowsanelementaryratelawisnot
anelementaryreaction.
C C k
2
2
O NO NO NO
C C k r =
2 2
2NO O 2NO +
HI I H 2
2 2
+
2 2 2 2
I H H H
C C k r =
Molecularity
This is the number of atoms, ions, or molecules involved
(colliding) in a reaction.
Examples:
(i)
2HI

+I H
Bimolecular reaction, since two species
(i)
2HI
2 2
+I H
, p
are involved in the reaction step.
(ii)
Unimolecular
4
2
234
90
238
92
He Th U +
urianium-238 helium thorium
Representation of an Elementary Reaction
I i t i l t t In expressing a rate we may use any measure equivalent to
concentration (for example, partial pressure), in which case:
Whatever measure we use leaves the order unchanged; however Whatever measure we use leaves the order unchanged; however,
it will affect the rate constant k.
For brevity elementary reactions are often represented by an For brevity, elementary reactions are often represented by an
equation showing both the molecularity and the rate constant. For
example,
k
p ,
represents a biomolecular irreversible reaction with second-order
1
k
2A 2R
represents a biomolecular irreversible reaction with second order
rate constant k
1
, implying that the rate of reaction is
Representation of an Elementary Reaction
It would not be proper to write mentioned equation as: p p q
1
k
A R
for this would imply that the rate expression is:
Thus, we must be careful to distinguish between the one particular
equation that represents the elementary reaction and the many equation that represents the elementary reaction and the many
possible representations of the stoichiometry.
Representation of an Elementary Reaction
Representation of a Nonelementary Reaction
Anonelementary reaction is one whose stoichiometry does not A nonelementary reaction is one whose stoichiometry does not
match its kinetics.
Kinetic Models for Nonelementary Reactions
If the kinetics of the reaction:
Indicates that the reaction is nonelementary, we may postulate a
series of elementary steps to explain the kinetics, such as
Kinetic Models for Nonelementary Reactions
Free radicals
Types of intermediates
Ions and polar substances
Types of intermediates
Molecules
Transition complexes
Nonchain Reactions
Chain Reactions Chain Reactions
Examples of Examples of
mechanisms of mechanisms of
i ki d various kinds
Free radicals
chain reaction mechanism
1
k
2 2
H Br 2HBr +

2
2 2
k
H Br 2HBr +

2
2
2 1
1 Br H
C C k
2
2
2 Br HBr
f
C C k
r
+
=
This is not a bimolecular reaction. Thisisnot abimolecularreaction.
Because the reaction occurs as follows:
2Br Br
I iti ti
2Br
2
Br
Initiation
+ + H HBr H
2
Br
+ + r r H B HBr B
2
Propagation
+ + r H H B H Br
22
2
r Br 2 B
Termination
Each step has a molecularity, which must be an integer.
Th d d l l it t il Thus, order and molecularity are not necessarily
identical for a given reaction.
Molecular intermediates
nonchain mechanism
The general class of enzyme catalyzed fermentation reactions:
with experimental rate p
is viewed to proceed with intermediate (A. enzyme)* as follows:
Transition complex
nonchain mechanism
The spontaneous decomposition of azomethane p p
we hypothesize the existence of either of two types of
intermediates intermediates.
Type 1 Type 1.
An unseen and unmeasured intermediate X usually An unseen and unmeasured intermediate X usually
present at very small concentration
This is called the steady-state approximation.
Type 2.
a homogeneous catalyst of initial concentration Co
is present in two forms is present in two forms,
free catalyst C
combined in an appreciable extent to form combined in an appreciable extent to form
intermediate X
Example 2.1 SEARCH FOR THE REACTION MECHANISM
The irreversible reaction
A+B=AB A+B=AB
has been studied kinetically, and the rate of formation of product y, p
has been found to be well correlated by the following rate
equation:
2
AB A B
r kC independentof C =
What reaction mechanismis suggested by this rate expression if
the chemistry of the reaction suggests that the intermediate
consists of an association of reactant molecules and that a chain
reaction does not occur?
If this were an elementary reaction, the rate would be given by
AB A B
r kC C k[A][B] = =
Model 1
1
2
k
*
2
k
2A A

hi h ll i l f l t ti
3
4
k
*
2
k
A B A AB

+ +

which really involves four elementary reactions

1
k *
2
2A A
2
k *
2
A 2A
3
k *
2
A B A AB + +
4
k *
2
A AB A B + +
*
r k [A ][B] k [A][AB] =
AB 3 2 4
r k [A ][B] k [A][AB] =
2 * *
1
r k [A] k [A ] k [A ][B] k [A][AB] +
*
2
1 2 2 3 2 4
A
r k [A] k [A ] k [A ][B] k [A][AB]
2
= +
r 0
*
2
A
r 0 =
2
1
k [A] k [A][AB] +
2
1 4
*
2
2 3
k [A] k [A][AB]
2
[A ]
k k [B]
+
=
+
2 3
k k [B] +
2
1
k k [A] [B] k k [A][AB]
1 3 2 4
AB
2 3
k k [A] [B] k k [A][AB]
2
r
k k [B]

=
+
2 3
[ ]
2
1 3 2 4
1
k k [A] [B] k k [A][AB]
2

AB
2 3
2
r
k k [B]
=
+
if k
2
, is very small, this expression reduces to
2
1
k k [A] [B] k k [A][AB]
2
1 3 2 4
AB
1
k k [A] [B] k k [A][AB]
2
r
k k [B]

=
+
2 3
k k [B] +
2
1
r k [A]
AB 1
r k [A]
2
=
if k
2
, is very small, this expression reduces to
2
1 3 2
AB
(k k 2k )[A] [B]
r
1 (k k )[B]
=
AB
3 2
1 (k k )[B] +
Model 2 Model 2
1
k *
2
B B B +
3
4
k
*
2
k
A B A AB

+ +

Example 2.2 SEARCH FOR A MECHANISM FOR THE

ENZYMESUBSTRATE REACTION
Here, a reactant, called the substrate, is converted to product by
the action of an enzyme, a high molecular weight (MW >10000)
protein-like substance. An enzyme is highly specific, catalyzing
one particular reaction, or one group of reactions. Thus,
Enzyme
A R
Many of these reactions exhibit the following behavior:
1. A rate proportional to the concentration of enzyme
introduced into the mixture [E ] introduced into the mixture [E
0
].
2. At lowreactant concentration the rate is proportional to the
t t t ti [A] reactant concentration, [A].
3. At high reactant concentration the rate levels off and
b i d d t f t t t ti becomes independent of reactant concentration.
Propose a mechanismto account for this behavior.
Michaelis and Menten (1913) were the first to solve this puzzle.
1
A E X

+

They guessed that the reaction proceeded as follows:
2
3
A E X
X R E

+

`
+
)
with the two assumptions
[E
0
]=[E]+[X] [E
0
] [E] [X]
d[X]
0 ~ 0
dt
~
d[R]
k [X]
3
[ ]
k [X]
dt
=
d[X]
k [A][E] k [X] k [X] 0
1 2 3
[ ]
k [A][E] k [X] k [X] 0
dt
= =
1 0
k [A][E ]
[X] =
3
d[R]
k [X]
dt
=
2 3 1
[X]
(k k ) k [A]
=
+ +
1 3 0 3 0
2 3 1 2 3 1
k k [A][E ] k [A][E ] d[R]
dt (k k ) k [A] (k k ) k [A]
= =
+ + + +
2 3 1 2 3 1
3 0
k [A][E ] d[R]
=
dt [M] [A]
=
+
0
[E ]
d[A] d[R]

d[A] d[R]
[A] when [A] [M]
dt dt
isindependentof [A]when[A] [M]

isindependentof [A]when[A] [M]

TEMPERATURE-DEPENDENT TERM OF A RATE
EQUATION EQUATION
Temperature Dependency from Arrhenius' Law
i 1 2
r f (temperature) f (composition) =
2
k f (composition) =
E RT
k k
E RT
0
k k e =
where k
0
is called the frequency or pre-exponential factor and E
k E 1 1
| |
0
q y p p
is called the activation energy of the reaction
2 2
1 1 1 2
r k E 1 1
ln ln
r k R T T
| |
= =
|
\ .
provided that E stays constant.
TEMPERATURE-DEPENDENT TERM OF A RATE
EQUATION EQUATION
Comparison of Theories with Arrhenius' Law
m E RT
0
k k T e 0 m 1

'
= s s
summarizes the predictions of the simpler versions of the collision
and transition state theories for the temperature dependency of
h the rate constant.
For more complicated versions mcan be as great as 3 or 4. Now,
because the exponential term is so much more temperature- because the exponential term is so much more temperature-
sensitive than the pre-exponential term, the variation of the latter
with temperature is effectively masked, thus p y ,
E RT
0
k k e

=
0
FromArrhenius' lawa plot of ln k vs 1/T gives a straight line, with
Reactions with high activation energies are very temperature-
Any given reaction is much more temperature-sensitive at a low
Fromthe Arrhenius law, the value of the frequency factor k, does
large slope for large E and small slope for small E.
sensitive; reactions with low activation energies are relatively
temperature-insensitive.
temperature than at a high temperature.
q y
not affect the temperature sensitivity.
Example 2.3 SEARCH FOR THE ACTIVATION ENERGY OF A
PASTEURIZATION PROCESS
Milk is pasteurized if it is heated to 63C for 30 min, but if it is
heated to 74C it only needs 15 s for the same result. Find the
activation energy of this sterilization process.
assuming anArrhenius temperature dependency
r t E 1 1
| |
2 1
1 2 1 2
r t E 1 1
ln ln
r t R T T
| |
= =
|
\ .
1
t 30 E 1 1
ln ln
| |
= =
|
\ .
E=422000 J/mol
2
0.25 t 8.314 336 347
|
\ .