REACTOR ENGINEERING I- CHP 481

Course Outline

(1) Chemical Kinetics: (a) Elementary reactions (b) Orders of reactions (c) Rate laws (d)
Reaction constants (e) Reactions mechanisms (f) Pseudo-steady state approximations or
assumptions (PSSA) (g) Complex and reversible reactions
(2) Chemical Reactors: (a) Classification of chemical reactors (b) Modes of operation (c)
Mathematical models and design equations for chemical reactors (d) Ideal reactors (e)
Ideal reactor performance (f) Non-ideal reactors (g) Multiple and cascade reactors (h)
Isothermal operations (i) Yield and selectivity in reactors

Bibliography: (1) Principles of chemical kinetics by Gordon G. Hammes (2) Elements of

chemical reaction engineering by Scott Fogler (3) Chemical reaction engineering by Octave
Levenspiel

Introduction

Chemical kinetics and reactor design are at the heart of the production of almost all industrial
chemicals. It is knowledge of chemical kinetics and reactor design that distinguishes the
chemical engineer from all other engineers. Chemical kinetics is concerned with the
dynamics of chemical reactions. It deals with the rate of chemical reactions and how these
rates can be explained in terms of a reaction mechanism or a reaction pathway.

Industrial chemical reactors are mainly classified according to their modes of operation. The
common chemical reactors are: Batch reactors, semi-batch reactors, Continuous stirred tank
reactors (CSTR) and Plug flow reactors (PFR).

CHEMICAL REACTION KINETICS

Reaction Rates and Rate Laws

In a closed-volume system, the rate of a reaction can be expressed either from a

thermodynamic point of view or from a chemical kinetics point of view. From a chemical
kinetics point of view, the rate of a chemical reaction can be defined as the rate of change
with time of the concentration of any of the reactants or products. The concentration can be
expressed in any convenient units of quantity per unit volume e.g. moles per liter. For the
−dNA −dCA
reaction: A + B C + D ( Stoichiometric equation), -rA = = or
Vdt dt
−dNB −dCB dNC dCC dND dCD
–rB = = or rC = = or rD = = .
Vdt dt Vdt dt Vdt dt

From the thermodynamic point of view, -r = kCAαCBβ.. or generally r = f(CA, CB, CC, CD …).
This equation is called the rate law or rate equation or rate expression for a given reaction.

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 The form of the rate law is determined by experiment and cannot, in general, be predicted
from the stoichiometric expression for the overall reaction. One of the objectives of
experimental kinetics is to propose a reasonable mechanism which will conform to the
experimentally observed rate law. In many cases, the rate law takes the particularly simple
form as expressed above i.e. the rate equals a constant multiplied by the product of powers of
concentrations, so that r = f(CA, CB, CC, CD …) = kCAαCBβ... In such cases, the overall
reaction order is defined as the sum of the exponents and the reaction order with respect to
any one chemical species is simply the exponent associated with the particular component in
question. The constant ‘k’ appearing in the rate equation is called the rate constant and is
temperature-dependent and according to Arrhenius, k = Ae-E/RT where A = frequency factor, E
= activation energy, R = universal gas constant and T = temperature. The activation energy is
determined experimentally by carrying out the reaction at several temperatures. After taking
E 1
the natural logarithm of the Arrhenius equation, ln k = ln A – ( ), it can be seen that a
R T
1
plot of ln k versus should be a straight line whose slope or gradient is proportional to the
T
activation energy.

Types of reactions

A homogeneous reaction is one that involves only one phase while a heterogeneous reaction
involves more than one phase. A phase is a distinct part of a reaction system. An irreversible
reaction is one that proceeds in only one direction and continues in that direction until the
reactants are exhausted. A reversible reaction can proceed in either direction depending on the
concentrations of reactants and products relative to the corresponding equilibrium
concentrations. An irreversible reaction behaves as if no equilibrium condition exists. Strictly
speaking, no chemical reaction is completely irreversible, but in very many reactions, the
equilibrium point lies so far to the right so much so that they are treated as irreversible reactions.

A B. This is the stoichiometry for an irreversible reaction.

A B. This is the stoichiometry for a reversible reaction.

In parallel reactions, the reactant is consumed by two different reactions to form different
products e.g.
B

A
C

An elementary reaction is one in which the reaction order of each chemical species is identical
with the stoichiometric coefficient for the reaction as given e.g.

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A+B Products, -rA = kCACB.

In the study of reaction orders and kinetic mechanisms, reference is sometimes made to the
molecularity of a reaction. The molecularity of a reaction is the number of atoms, ions or
molecules involved or colliding in the reaction. Complex reactions are reactions that have
complex rate expressions e.g. H2 + Br2 2HBr. This reaction proceeds by a free
radical mechanism and its rate law is:

k1CH2CBr21/2
rHBr =
k2 +CHBr/CBr2

Reaction Mechanisms and Pseudo-steady state approximations/ assumptions (PSSA)

The mechanism of a reaction is the molecular path of the reaction. A more restrictive definition
of an elementary reaction is sometimes encountered and it involves the mechanism of the
reaction. Previously, homogeneous reactions whose rate laws involved concentrations raised to
some power n which is an integer were mentioned i.e.

–rA = kCAn. If n=1, the reaction was first-order. If n=2, the reaction was second-order etc.
However, a large number of homogeneous reactions involve the formation and subsequent
reaction of an intermediate species or activated complex. When this is the case, it is not
uncommon to find a reaction order that is not an integer. An example of this type of kinetic
expression is observed for the formation of hydrogen bromide as indicated above i.e.

rHBr = k1CH2CBr21/2

k2 +CHBr/CBr2

For such rate expressions, reaction orders cannot be defined i.e. for rate laws where the
denominator is a polynomial function of the species concentrations, reaction orders are described
only for limiting values of the reactant and/or product concentrations. Reactions of this type are
non-elementary and complex in that there is no direct correspondence between reaction order
and stoichiometry.

Non-elementary and complex rate laws similar to the above, come about as a result of the overall
reaction taking place by a mechanism consisting of a series of reaction steps. We assume each
reaction step in the reaction mechanism to be elementary. To illustrate how rate laws of this type
are formed, we shall consider the gas-phase decomposition of azo-methane (AZO) to give ethane
and nitrogen as products. Experimental observations show that the rate law for the formation of
nitrogen is first-order w.r.t. AZO at pressures greater than 1 atm. i.e. at high concentrations of

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AZO ( rN2 α CAZO) and second-order at pressures below 50mmHg i.e. low concentrations of AZO
(rN2 α CAZO2). This apparent change in reaction order can be explained by the theory explained by
Lindemann. He explained that an activated molecule, (CH3)2N2* results from collision or
interaction between molecules i.e.

(CH3)2N2 + (CH3)2N2 k1 (CH3)2N2 + [(CH3)2N2 ]*. This activation can occur when
translational kinetic energy is transferred into energy stored in internal degrees of freedom,
particularly vibrational degrees of freedom. An unstable molecule or active intermediate is
formed solely as a consequence of the molecule moving at a high velocity (high translational
kinetic energy). The energy must be absorbed into the chemical bonds where high-amplitude
oscillations lead to bond ruptures, molecular rearrangement and then decomposition. In the
absence of photochemical effects or similar phenomena, the transfer of translational energy to
vibrational energy to produce an active intermediate can occur as a consequence of molecular
collision or interaction. Other types of active intermediates that can be formed are free radicals
(one or more unpaired electrons e.g. H*), ionic intermediates (e.g. carbonium ion C+) and
enzyme-substrate complexes. In Lindemann’s theory of active intermediates, decomposition of
the intermediate does not occur instantaneously after internal activation of the molecule. Rather,
there is a time lag (infinitesimally small) during which the species remains activated. Because
the reaction is elementary, the rate of formation of the AZO active intermediate from the
reaction,

(CH3)2N2 + (CH3)2N2 k1 (CH3)2N2 + [(CH3)2N2 ]* is rAZO* = k1CAZO2. There are two

reaction paths that the active intermediate or activated complex may follow after being formed.
In one path, the activated molecule may become deactivated through collision with another
molecule as follows:

(CH3)2N2* + (CH3)2N2 k2 (CH3)2N2 + (CH3)2N2 with the rate equation

-rAZO* = k2CAZO*CAZO. This reaction is of course just the reverse reaction of the reaction:

(CH3)2N2 + (CH3)2N2 k1 (CH3)2N2 + [(CH3)2N2 ]*.

In the alternative reaction path, the active molecule decomposes spontaneously to form
ethane and nitrogen as follows:

(CH3)2N2* k3 C2H6 + N2 with a rate law, -rAZO* = k3CAZO*.

The overall reaction (CH3)2N2 + (CH3)2N2 C2H6 + N2 for which the rate law is
non-elementary, consists of a sequence of elementary reactions. Nitrogen and ethane are only
formed in the reaction (CH3)2N2* k3 C2H6 + N2 and consequently, the net rate of
formation of nitrogen is rN2 = k3CAZO*. The concentration of the active intermediate AZO* is
very difficult to measure because it is highly reactive and very short-lived (approximately 10 -
9
seconds). Consequently, the evaluation of the following reaction rate laws:

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(1) -rAZO* = k2CAZO*CAZO
(2) -rAZO* = k3CAZO*
(3) rN2 = k3CAZO*= -rAZO*

in their present forms, becomes quite difficult, if not impossible. To overcome this difficulty,
we need to express the concentration of azo-methane intermediate CAZO* in terms of the
concentration of azomethane CAZO. The total or net rate of formation of a particular chemical
species involved in many simultaneous reactions is sum of the rates of formation of each
n
individual reaction for that species i.e. rj = ∑ rji where j= chemical species occurring in n
i=1

different reactions.

Energy Ea

(CH3)2N2* + (CH3)2N2

k1 k2

k3

C2H6 + N2

(CH3)2N2 + (CH3)2N2

Molecular path

Because the active intermediate AZO* is present in all three reactions in the decomposition
mechanism, the net rate of formation of AZO* is the sum of the reaction steps above i.e.

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 rAZO* = k1CAZO2- k2CAZO*CAZO- k3CAZO*. To express CAZO* in terms of measurable
concentrations, we use the pseudo-steady state approximation ( assumption or hypothesis),
PSSA or PSSH.

Pseudo-steady State Approximation (PSSA) or Pseudo-steady State Hypothesis (PSSH)

The active intermediate molecule has a very short life span because of its high reactivity. We
shall also consider it to be present only in very low concentrations. These two assumptions
lead to the pseudo-steady state approximation in which the rate of formation of the active
intermediate is assumed to be equal to its rate of disappearance. As a result, the net rate of
formation of the active intermediate rAZO* is zero i.e. rAZO* = 0.

The rate of formation of the product nitrogen is rN2 = k3CAZO* and the rate of formation of
AZO* is rAZO* = k1CAZO2- k2CAZO*CAZO- k3CAZO*.

Using PSSA, the above two equations can be combined to obtain a rate law for the formation
of nitrogen solely in terms of the concentration of azo-methane.

rAZO* = 0 = k1CAZO2- k2CAZO*CAZO- k3CAZO*. Solving for CAZO* gives

CAZO* = k1CAZO2

k3 + k2CAZO

But rN2 = k3CAZO* = k3 k1CAZO2

k3 + k2CAZO

At low concentrations of azomethane i.e. k2CAZO « k3,

rN2 = k3k1CAZO2 = k1CAZO2 while at high concentrations rN2 = k3k1CAZO =kCAZO.

k3 + k2CAZO k2

In describing reaction orders for this rate equation, one would say the reaction is apparent
first-order at high azo-methane concentrations and apparent second-order at low azo-methane
concentrations.

Enzymatic reactions

The PSSH is applicable to enzymatic reactions. An enzyme (E) is a protein or protein-like

substance with catalytic properties. A substrate (S) is a substance that is transformed at an
accelerated rate as a result of the action of the enzyme. There are three major types of enzyme-
catalyzed reactions:
1. Soluble enzyme-insoluble substrate

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 2. Insoluble enzyme-soluble substrate
3. Soluble enzyme-soluble substrate.
Consider the reaction between a substrate urea (S) and enzyme urease (E) forming urea-substrate
complex E.S in the presence of water (W).

E+S k1 E.S

E.S k2 E+S

E.S + W k3 E+P where, S=NH2CONH2, P =2NH3 + CO2

The rate -rs is given by −r S =k 1 ( E)( S )−k 2 ( E . S )

The net rate of formation of enzyme-substrate complex is:

r E .S =k 1 ( E )(S)−k 2 ( E . S)−k 3 (W )( E . S)

Enzyme is not consumed and therefore the total conc. of the enzyme (Et) remains constant.

Et = (E) +(E.S) and hence (E) =Et -(E.S) where (E) and (S) are used instead of CE and CS,
respectively.

r E .S =0=k 1 [( Et )−( E .S)](S)−k 2 (E . S)−k 3 (W )( E. S)

k 1 (E t )( S )
Solving for E.S, E . S=
k 1 (S )+k 2 +k 3 (W )

−r S =k 1 [( Et )−( E .S)](S)−k 2 (E . S)
SUBTRACTING r E .S =k 1 ( E )(S)−k 2 ( E . S)−k 3 (W )( E . S) FROM −r S =k 1 ( E)( S )−k 2 ( E . S )
GIVES THE RATE OF PRODUCT FORMATION rp which is approximately equal to –rs since rE.S =0 from
PSSH.
k 1 k 3 ( W )( Et )( S )
Hence −r S =k 3 (W )(E . S) Substituting for E.S gives: −r S =
k 1 ( S )+ k 2 + k 3 (W )
Reaction of urea and urease is carried out in excess water and therefore the concentration of water
remains the same.

k '3 +k 2
k '3=k 3 ( W ) and K m=
k1

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Michaelis-Menten Equation

k 1 k 3 ( W )( Et )( S )
Dividing the numerator and denominator of −r S =
k 1 ( S )+ k 2 + k 3 (W )
by k1, Michaelis-Menten equation is obtained as
k '3 ( E t )(S )
−r S = where Km is referred to as Michaelis constant .
( S )+K m
Let Vmax represent the maximum rate of reaction for a given total enzyme reaction i.e.
V max ( S )
V max =k '3 ( Et ) Hence −r s=
( S )+ K m

V max ( S )
For low substrate concentration −r s≃
Km

For high substrate concentration −r s≃V max

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 -rS

0.5Vmax

Vmax
0
Km
Cs

Graph giving the physical interpretation of Michaelis-Menten parameters Vmax and Km

CHEMICAL REACTORS
Classification of chemical reactors

The principles of chemical reaction engineering are applied in areas ranging from production of
chemicals to the manufacture of computer chips.

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The application of enzyme kinetics to improve an artificial kidney is also part of chemical
reaction engineering.

The sizing of chemical reactors to achieve production objectives is an important segment in the
design of chemical reactors.

The most common industrial reactors are: batch, continuous stirred tank (CSTR) and tubular
reactor or Plug flow reactor (PFR). CSTR and PFR are both called continuous reactors because
of their mode of operation. As the reagents are being charged into the reactor, the products are
simultaneously being withdrawn. For batch reactors, the reagents are charged into the reactor and
allowed to react to completion before the product is discharged.

In chemical reaction engineering, it is first necessary to account for the various chemical species
entering and leaving a reaction system before embarking on the design aspects and the conditions
that affect chemical reaction rates.

This accounting process is achieved through overall mole balances on individual chemical
species in the reaction system.

Chemical species refers to any chemical compound or element with a given identity.

The identity of a chemical species is determined by the kind, number and configuration of that
species’ atoms e.g. cis 2-butene and trans 2-butene.

H H

C === C cis-butene

CH3 CH3

CH3 H

C === C trans-butene

H CH3

These two chemicals have exactly the same kind and same number of atoms but display
different chemical and physical properties because they have different configurations.

We say that a chemical reaction has taken place when a detectable number of molecules of one
or more species have lost their identity.

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In the classical approach to chemical change, it is assumed that the total mass is neither created
nor destroyed i.e. the law of mass action applies.

There are 3 basic ways a species may lose its identity:

(1) Decomposition- A molecule breaks down into smaller, atoms or atom fragments

(2) Combination-Molecules’ combination with other molecules or atoms

(3) Isomerization- Change of configuration.

For an elementary reaction of the form: A→B with a rate constant ‘k’, the rate of reaction is
defined as the number of molecules that lose their chemical identity per unit time per unit
volume of reaction mixture as indicated above i.e. –rA =-(1/V)dNA/dt

Or

It is the number of moles of product species generated per unit time per unit volume of reaction
mixture i.e. rB = (1/V) dNB/dt

For a constant volume reaction system (liquids), the chemical reaction rate is an intensive
quantity and depends only on temperature and concentration.

Mole Balance Equation

To perform a mole balance on any system, the system boundaries must first be specified. The
volume enclosed by these boundaries will be referred to as the system volume.

A mole balance on species A at any instant in time t yields the following equation:

FAO + GA – FA = dNA/dt.

If all the system variables (temperature, concentration and catalytic activity) are spatially
uniform throughout the system volume, the rate of generation GA = rAV.

Suppose now that the rate of formation of species A for the reaction varies with the position in
the system volume.

V2, r2

V1,r1

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The rate at location 1 is r1 which is surrounded by a small volume ΔV1 within which the rate is
uniform. Similarly, the reaction rate has a value r2 at location 2 and an associated volume ΔV2
and so on.

The generation ΔG1 = r1ΔV1. Similar expressions can be written for ΔG2 and other sub-volumes
ΔVi.

The total rate of generation within the system volume is the sum of all the rates of generation in
each of the sub-volumes.

If the total system is divided into ‘m’ sub-volumes, the total rate of generation is: G =ΣΔGi =
ΣriΔVi. By taking the appropriate limits (m→∞ and ΔV→0) and making the use of the definition
of an integral, we can write G =ʃrdV

For the above equation, we see that r will be an indirect function of position since the properties
of the reacting materials (concentration and temperature) can have different values at different
locations in the reactor.

Since FAO + GA – FA = dNA/dt, the above equation becomes: FAO + ʃrAdV – FA = dNA/dt.

The above form is the final form of the general mole balance equation for any chemical species
A that is entering, leaving, reacting and /or accumulating within any system volume V. From this
general mole balance equation, we can develop the design equation for the various types of
industrial reactors: batch and continuous flow reactors (CSTR and PFR).

Batch Reactors

There is no flow in batch reactors (FA0=FA=0),

Therefore the equation above becomes dNA v

=∫ rAdV
dt
CSTRs

A common type of reactor used in processing industry is the continuous stirred tank reactor
(CSTR). In CSTR, the concentration of species in the reactor does not change with time,

dNA/dt = 0.
F A 0 −FA
By substituting , a design equation for CSTR is obtained: V =
−r A
Tubular Reactors

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 Tubular reactors consist of cylindrical pipes normally operated at steady state. There is no radial
variation of the concentration of the species and such flows are described as plug flow.

At Steady state dNA/dt=0.

Mixing is assumed to be homogeneous in a small volume, DV for which the mole balance
expression can be written as:
FA( y )−FA( y + Δy)+rA ΔV =0
where ΔV = AΔy
After substituting and rearrangement, we have:

− [ FA( y +Δy )−FA ( y )

Δy ]
=−r A A

After taking limits and dividing or multiplying by -1 and taking limits as Dy®0, the above
equation becomes
dF A
=r A A
dy

We take the cross-sectional area of the reactor to be constant and hence the equation reduces to
the following form:

dFA
=rA
dV

Conversion and reactor sizing

Definition of conversion:

Choose one of the reactants as the basis.

The limiting reactant is the best choice.

Develop the stoichiometric relationship e.g. aA +bB→ cC+ dD

and then the design equation. We take a, b, c and d as the stoichiometric coefficients and A, B,

C and D as the chemical species.

Taking A as the basis, b c d

A+ B → C+ D
a a a

Moles of A reacted 13
X A=
Moles of A fed
 Conversion of A is then defined as,

Let XA be simply X.

Design equation for batch systems is as follows:

[
[ Moles of A consumed ] =[ Moles of A fed ]⋅ moles of A reacted
moles of A fed ]
Thus [ moles of A consumed ] =[ N A 0 X ]

[ Moles of A in ¿ ] ¿ ¿ ¿
¿

That is

[ N A ]=[ N A 0 ]− [ N A 0 X ]
Hence the number of moles of A in the reactor after a conversion X has been achieved is given
by:
N A =N A 0 −N A 0 X=N A 0 (1−X )

For a batch reactor, reaction time is an important parameter and therefore it is necessary to know
how NA varies with time (i.e, find dNA/dt).

dN A dX
=N A 0
dt dt

dX X ( t)
Batch reactor design equation is then given by: −r A V =N A 0
dt
or t=
∫ N A 0 −rdXV
0 A

Conversion in Continuous Flow Reactors

Conversion for flow reactors is given by: X=

[ F A 0−F A
F AO ]
F A 0 −F A 0 X =F A
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 Mole balance for flow reactors is given by

Volumetric flow (n, dm3/s) and initial concentration (CA0, mol/dm3) are related with initial
molar flow rate (FA0, mol/s) as follows: F =C ν
A0 A0 0
PA 0 y A 0 P0
where, CA0 for ideal gas systems is given by the ideal gas law C A 0= =
RT 0 RT 0

X
dX dX
F A 0 =−r A becomes V PFR=F A 0 ∫
dV 0 −r A

F A 0 −FA
For a CSTR V= and hence VCSTR = FAOX/-rA.
−r A

Applications of the design equations

The rate of disappearance of reagent A, -rA is almost always a function of the concentration
of the various chemical species present. For an elementary reaction A B, a simple
functional dependence is –rA = kCA = kCA0(1-X). For this dependence, a plot of the
reciprocal rate of reaction (1/-rA) as a function of conversion yields a curve of the form:

1
/-rA

X
1
/-rA ∞ as X 1 i.e. the rate is usually greatest when the concentration of reactant
1
is highest and hence /-rA is small.
1
When CA X -rA /-rA

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 *Shade the area in the graph above which when multiplied by FA0 would give the
volume of a CSTR necessary to achieve 80% conversion.
*Shade the area in the graph above which when multiplied by FA0 would give the
volume of a PFR necessary to achieve 80% conversion.

Numerical Evaluation of Integrals

The area under the curve can be approximated using Trapezoidal rule (two-point rule),
Simpson’s one-third rule or five-point quadrature formula rule given by the integrals:
X1
Trapezoidal rule (two-point rule):
∫ f ( X )dX = h2 [ f ( X 0 )+ f ( X 1 )] where h=X1-X0.
X0

X2
Simpson’s one-third rule: ∫ f ( X )dX = h3 [ f ( X 0 )+ 4 f ( X 1 )+ f ( X 2 ]
X0

where h=(X1-X0)/2, X1=X0+h

X4

Five point quadrature formula: ∫ f ( X )dX = h3 [ f 0 + 4 f 1 +2 f 2 +4 f 3 +f 4 ]

X0
where h=(X4-X0)/4

Reactors in series

Many times, reactors are connected in series so that the exit stream of one reactor is the feed
stream for another reactor. When this arrangement is used, it is often possible to speed up
calculations by defining conversion in terms of location at a point downstream rather than with
respect to any single reactor i.e. the conversion X is the total number of moles of reagent A that
have reacted up to that point per mole of A fed to the first reactor. However, this definition can
only be used provided that there are no side streams withdrawn and the feed stream enters only
the first reactor in the series.

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FA1 = FA0-FA0X1, FA2 = FA0-FA0X2, FA3 = FA0-FA0X3 etc.
¿
X2 = total moles of A reacted up ¿ point 2 Total moles of A fed ¿ first reactor ¿

Similar definitions exist for X1 and X3 etc.

A mole balance on species A for the CSTR in the middle gives:

IN – OUT + GENERATION = 0

FA1-FA2+rA2V2 = 0

FA 1−FA 2 FA 0(X 2− X 1)
V2 = but FA1 = FA0-FA0X1 and FA2 = FA0-FA0X2. Hence V2 =
−rA 2 −rA 2

Selectivity Parameter for one reactant

Of particular interest are reactants that are consumed in the formation of a desired product,
D, and the formation of an undesired product, U, in a parallel or side reaction.

A kD D

A kU U

We want to minimize the formation of U and maximize the formation of D. This is to save on
costs.

The undesired product, U, is minimized through selection of reactor type and conditions i.e.
we want the rate of formation of, D,rD, to be high w.r.t. the rate of formation of U, rU. Taking
the ratio of these rates, we obtain a rate selectivity parameter, S.

SDU = rD/rU= kD/kU(CAα1-α2)

Cases or scenarios :ED>EU, ED<EU, α1> α2, α1< α2

Reaction Yield

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The reaction yield YD, like the selectivity parameter, has two definitions: one based on the
ratio of reaction rates and the other based on the ratio of molar flow rates. The yield at a point
can be defined as the ratio of the reaction rate of a given product to the reaction rate of the
key or limiting reactant A.

YD =rD/-rA. For a batch system YD =ND/(NA0-NA) while for a flow system YD = FD/(FA0-FA).

Non-ideal reactors

Non-ideal reactors are chemical reactors whose performance deviates from the ideal. In ideal
reactors, all the atoms or molecules of material have been inside the reactor for exactly the
same amount of time. In real reactors, there is a distribution of residence times in the reactor.
Residence time is the time the atoms or molecules of material have spent inside the reactor.

Models of non-ideal reactors

FLOW PATTERN 1: Gas-liquid system

In a gas-liquid stirred tank reactor, the gaseous reactant is bubbled into the reactor while the
liquid reactant is fed through an inlet tube in the reactor’s side. The reaction takes place at the
gas-liquid interface of the bubbles. The reaction rate is proportional to the total bubble
surface area. The surface area of a particular bubble depends on the time it has spent in the
reactor. Some gas bubbles escape from the reactor almost immediately while others spend
enough time in the reactor for complete consumption. The time the bubble spends in the
reactor is termed the bubble residence time.

FLOW PATTERN 2: Liquid-solid system

When a reactor is packed with catalyst, the reacting fluid usually does not flow through the
reactor uniformly i.e. channeling occurs. The molecules following the channeling pathway do
not spend as much time in the reactor as those flowing through the regions of high resistance
to flow. We see there is a distribution of time that molecules spend in the reactor in contact
with the catalyst.

FLOW PATTERN 3: CSTR with channeling and dead zones

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In many CSTR reactors, the inlet and outlet pipes are close together and so short-circuiting
occurs. In addition to short-circuiting, stagnant regions or dead zones are often encountered.
In these regions, there is very little or no exchange of material with the well mixed regions.

FLOW PATTERN 4: Scaling in series reactors

In an industrial reactor system consisting of reactors in series, there is a serious problem of

scaling. The scale sometimes becomes as thick as to alter the volume of the reactors.

FLOW PATTERN 5: Viscosity increases with mixing

In a particular semi-batch reactor, polymerization would occur as one reactant is fed into a
mixture containing the other reactant. At the start, the material is not very viscous and the
feed is dispersed quite well throughout the tank. As the reaction proceeds however, the
mixing becomes less complete in the sense that this dispersion no longer takes place on a
molecular scale. Rather, the mixture separates into macroscopically small globules. Even
though the material could be regarded as perfectly mixed on a gross scale, yet on a molecular
level it could be imperfectly mixed. This quality of mixing has a significant effect on reactor
performance.

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