CHEMICAL REACTION ENGINEERING 1

LITERATURE REVIEW AND PROBLEM SOLVING DISCUSSION

Based on:

H. Scott Fogler. (2006) Element of Chemical Reaction Engineering, 4th Edition

GROUP 5

Alif Nadhif Rabbani (1506788824)

Farhandi Fadillah Fedrizal (1506788894)

Hannah Natasha Andjani (1506788925)

CHEMICAL ENGINEERING DEPARTMENT

FACULTY OF ENGINEERING

UNIVERSITY OF INDONESIA

DEPOK 2017
 TABLE OF CONTENTS

CHAPTER I LITERATURE REVIEW

I.1 Mole Balances

I.1.1 Rate of Reaction

I.1.2 General Mole Balance Equation

I.1.3 Batch Reactors

I.1.4 Flow Reactors

I. 1.4.1 Continuous-Stirred Tank Reactor

I. 1.4.2 Plug Flow Reactor

I. 1.4.3 Packed Bed Reactor

I.2 Conversion and Reactor Sizing

I.2.1 Conversion

I.2.2 Batch Reactor Design Equation

I.2.3 Flow Reactors Design Equation

I.2.3.1 Continuous-Stirred Tank Reactor

I.2.3.2 Plug Flow Reactor

I.2.3.3 Packed Bed Reactor

I.2.4 Reactor Sizing

I.2.5 Reactors in Series

I.2.5.1 Continuous-Stirred Tank Reactor

I.2.5.2 Plug Flow Reactor

I.2.5.3 Packed Bed Reactor

I.2.6 Additional Theory

I.3 Rate Laws and Stoichiometry

Part 1: Rate Laws

1.3.1 Basic Definition of Rate Law

I.3.2 The Reaction Order and Rate Law

 I.3.3 Reaction Rate Constant

Part 2: Stoichiometry

I.3.4 Batch System

I.3.5 Flow Systems

I.4 Isothermal Reactor Design

I.4.1 Isothermal Reactors Design Structure

I.4.1.1 Batch Reactor

I.4.1.2 Continuous-Stirred Tank Reactor

I.4.1.3 Tubular Reactor

I.4.1.4 Packed Bed Reactor

I.4.1.5 Microreactor

I.4.1.6 Membrane Reactor

CHAPTER II PROBLEM SOLVING

II.1 Chemical Kinetic and Reactor Design

II.2 Questions from Chapter 3 Fogler

II.3 Questions from Chapter 4 Fogler

 CHAPTER I

LITERATURE REVIEW

I.1 Mole Balances

I.1.1 Rate of Reaction

Rate of reaction describes the speed of a number of moles of a certain chemical species being
consumed in a reaction to form the product chemical species. Chemical reaction happened
whenever lost their identity and assumed new form of identity is several ways such as
decomposition, combination, and isomerization. The reaction rate is defined as the rate of
appearance of a product or rate of disappearance of a reactant.

Factors that has affects reaction rates:

Reactant concentrations
Reaction temperature
Catalyst presence
Surface area of reactants of catalysts

Rate of reaction (-rA), is the number of moles of A reacting or disappearing per unit time
volume (mol/dm3s)
dC A
rA = dt

I.1.2 General Mole Balance Equation (GMBE)

Mole balance on species j any period of time (t), can be defined as:

Mole balance of the system is:

N represents the number of moles of species j at any given t. GMBE for chemical species j
within any system of volume V:

I.1.3 Batch Reactors

Used for small scale operations and not suitable for slow reactions.
It has the advantage of high conversions that can be obtained by leaving the reactant
in the reactor for long periods of time.
It has the disadvantages of high labor costs per batch, the variability of products from
batch to batch, and the difficulty of large-scale production.

Batch Reactor Illustration

General mole balance equation of an ideal batch reactor, since batch reactor has no inflow nor
outflow of reactants or products therefore:

[rate or reactant loss due to chemical reaction] = [rate of accumulation of reactant in the reactor]
dN A
( rA )V = dt

Therefore after rearrangement the general mole balance of a species j is defined as

When the reaction mixture has been perfectly mixed the equation is

Integral form of the mole balance on a batch reactor with boundary t = 0, NA = NAO and t = t1,
NA = NA1

I.1.4 Flow Reactors

Continuous flow reactors are always operated at steady state.

1.4.1 Continuous-Stirred Tank Reactor

CSTR is used primarily for liquid phase reaction and operated at steady state. In
CSTR process it is assumed that the mixture of chemical species are perfectly mixed -
where each variable is the same at any point in the mixture.

The general mole balance equation for CSTR is

Where in a condition where it is operated at steady state and perfectly mixed

The design equation for a CSTR process is

Since there are no spatial variation

1.4.2 Plug Flow Reactor

PFR is normally operated at steady state. In PFR there is no radial variation on

concentration. It is used for gas-phase reactions. In PFR it is assumed that
concentration varies continuously in the axial direction through the reactor. The
reaction rate is defined as zero order reaction.

PFR illustration

General mole balance equation for PFR

Design equation for PFR

FA0dXA = (-rA)dV

V X Af
dX A
dV
F A0 = rA
0 0

1.4.3 Packed Bed Reactor

PBR is used for heterogenous reaction. The reaction takes place on the surface of the
catalyst. The reaction rate of PBR is based on mass solid catalyst (W). The mass of
solid is used because the amount of catalyst is what is important to the rate of product
formation.

PBR illustration

PBR is assumed to have no radial gradients in concentration, temperature, or reaction.

General mole balance equation for PBR:

Which would resulted in

The integral form of the PBR design equation to calculate catalyst weight is as follows

Summary of mole balance for each type of reactor

I.2 Conversion and Reactor Sizing

I.2.1 Conversion

Conversion is a measure of reactions progress toward completion. When defining

conversion, one reactant is chosen as the basis.

The general reaction equation:

With A as basis, the reaction equation is rearranged:

Conversion (X) of chemical species A can be defined as:

I.2.2 Batch Reactor Design Equation

The derived mole balance equation with conversion

NA = NA0 - NA0X

Differentiate with time

dN A
dt = rA V (1)
Equation (1); mole balance for batch reactor, substituted into the time-differentiated equation
resulting in:

The equation above is the design equation for batch reactor in terms of conversion
I.2.3 Flow Reactors Design Equation

In a continuous flow reactors system, the conversion is a function of reactor volume (V). The
general mole balance equation can be defined as:

Where the rearranged equation is also equivalent with the equation below:

FA0 = CA0 V0

2.3.1 Continuous-Stirred Tank Reactor

Design equation for CSTR from chapter 1

F A0 F A
V = rA (1)

Substituted with the flow reactor design equation in terms of conversion, resulted in
the design equation in terms of conversion for CSTR
F A0 X
V = rA
2.3.2 Plug Flow Reactor

Mole balance equation for PFR based on chapter 1 is defined as

dF A
dV = rA (1)
The mole balance for flow reactors in terms of conversion

FA = FA0 - FA0X (2)

Equation 2 to be differentiated in terms of X

dFA = - FA0dX (3)

Equation 3 substituted into equation 1, resulted in the design equation for PFR in
terms of conversion
dX
F A0 dV = rA
Equation above integrated with limit V=0 when X=0
X
V = F A0 dX
rA
0

2.3.3 Packed Bed Reactor

Design equation for PBR

dX
F A0 dW = rA
Equation for catalyst weight (W)
 X
W = F A0 dX
rA
0

I.2.4 Reactor Sizing

With any given rate of function in terms of conversion, with levenspiel plot any type of
reactor can be sized and the volume of reactors can be found. Volume of the reactors is
represented by the shaded area in the levenspiel plot.

In irreversible reaction, the rate usually the biggest at the initial of the reaction, that is when
the concentration is at its peak. For reversible reaction, the maximum conversion is the
equilibrium conversion. At equilibrium the reaction rate is zero.

I.2.5 Reactors in Series

The exit stream of one reactor is fed to the next one

T otal moles of A reacted up to point i
Xi = M oles of A f ed to the f irst reactor

F A0 F Ai
Xi = F A0 rearranged FAi = FA0
- FA0 . Xi

2.5.1 Continuous-Stirred Tank Reactor

Reactor 1:

Mole balance equation:

In - Out + Generation = 0

FA0 - FA1 + rA1V1 = 0 (1)

The molar flow rate of A at point 1:

FA1 = FA0 - FA0X1 (2)

Combining (1) and (2)

Reactor 2:

Mole balance equation:

In - Out + Generation = 0

FA1 - FA2 + rA2V2 = 0 (3)

The molar flow rate of A at point 2:

FA2 = FA1 - FA1X2 (4)

Combining (3) and (4) resulting in equation (5)

Substituting equation 2 and 4 into equation 5

F A0
V2 = rA2 (X 2 X 1)
2.5.2 Plug Flow Reactor

The overall conversion of two PFRs in series is the same as one PFR with the same
total volume.

X2 X1 X2
dX
F A0 r
A
= dX
F A0 r
A
+ dX
F A0 r
A
0 0 0

2.5.3 Combination of CSTR and PFR in Series

 Reactor 1: CSTR

Reactor 2: PFR
X2
F A0
V2 = rA2 dX
X1

Reactor 3: CSTR
F A0 (X 3 X 2 )
V3 = rA3 dX

I.2.6 Additional Theory

Space Velocity

Defined as:
V0 1
SV = V =

I.3 Chapter 3 Rate Laws and Stoichiometry

Part 1: Rate Laws

1.3.1 Basic Definition of Rate Law

Before going to the definition of rate law, some types of reactions need to be known. A
homogeneous reaction is one that involves only one phase. A heterogeneous reaction is one
that involves more than one phase, and the reaction usually occurs at the interface between
phases. An irreversible reaction is ones that proceeds in only one direction and continues in
that direction until the reactants become exhausted. A reversible reaction can proceed in
either direction, depending on the concentration of reactants and products relative to the
corresponding equilibrium concentrations. An irreversible reaction behaves as if there is no
equilibrium condition exists.

Relative Rates of Reaction

The relative rates of reaction of the various species involved in a reaction can be obtained
from the ratio of stoichiometric coefficient.

A + ab B ac C + ad D
For every mole of A that is consumed, c/a moles of C appear. In other words,

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

r c = ac ( r A ) = ac r A
The relationship can be expressed directly from the stoichiometry of the reaction .

aA+bB cC+dD

rA rB rc rD
For which,
a = b = c = d

I.3.2 The Reaction Order and Rate Law

Mathematically, rate of reaction is proportional to the concentration of reactants, raised into a

power. The rate law is the algebraic equation that relates the reaction rate and concentration.

-rA = [kA(T)][fn(CA,CB,Cn)]

kA = Specific rate of reaction / rate constant.

fn(CA,CB,Cn) = Dependency of reaction rate on the concentrations of the

reactants.
The overall reaction order for the reaction (n) is the sum of each species reaction order,
written as n=x+y.

The number of n, which is the reaction order, is any positive integer, that could be from zero,
one, two, three, etc. When n equals zero, it means the reaction ha a zero-order reaction. In
zero-order reaction, the concentration of reactants do not affect the reaction rate, in other
words, the rate is independent to the concentration. In this paper, only the zero, first, and
second order reaction will be explained. A first order reaction is when the concentration
doubles, then the rate will be also doubles, and for second order reaction, when the
concentration is doubled, the rate is 4 times larger. Further differences will be elaborated on

the table below.

An elementary reaction is a single step process of reaction. A reaction follows an elementary

rate law if and only if the stoichiometric coefficient are the same as the individual reaction
order for the species.

The following tables are the examples of reaction rate laws

Non elementary rate laws means that the process is a multi-steps. The rate of the reaction of
non-elementary reaction will be determined only by the reactants involved in the slowest step
(the rate-limiting steps).

I.3.3 Reaction Rate Constant

Quantity k is referred to as the specific reaction rate or the rate constant. It is almost always
dependent on temperature and depends on it is whether or not a catalyst is present and in gas
phase reaction it may be a function of total pressure.

Arrhenius Equation
Arrhenius suggested that the temperature dependence of the specific reaction
rate kA could be correlated by the equation

E a /RT
k = Ae

Where A represents the pre-exponential factor or frequency factor, EA is the activation energy
in J/mol, R is the gas constant (commonly use 8.314 J/mol.K) and T is the temperature (in
kelvin).

Activation Energy

The activation energy is a energy level that reactant molecules must overcome before a
reaction can occur. Molecules need energy to distort or stretch their bonds so that they break
them and thus, form a new bonds. Steric and electron repulsion forces must be overcome as
the reacting molecules come close together.

The Reaction coordinates: denote the potential energy of the system as a function of the

progress along the reaction path as we go from reactants to an intermediate to products. As

along the reaction coordinate to the right, the reactants A and BC approach each other, the
BC bond begins to break, and the energy of the reaction pair increases until the top of the
barrier is reached. At the top, the transition state is reached where the intermolecular distance
between AB and BC are equal. As the reaction proceeds further, the distance between A and
B decreases, and the AB bond begins to form. The distance between AB and C increases and
the energy of the reacting pair decreases to that of the AB bond energy.

Implication of Arrhenius Equation

Ea
ln k = ln A RT

Activation energy can be determined by carrying out the reaction with different temperature.

Part 2: Stoichiometry

Before going further to the explanations for batch and flow systems stoichiometry, a basic
concept will be explained first. This concept will be useful for the next two points in this
section.

Stoichiometric Table presents the stoichiometric relationships between reacting molecules for
a single reaction. It tells us how many molecules of one species will be formed during a
chemical reaction when a given number of molecules of another species disappears.

I.3.4 Batch System

Batch reactors are primarily used or the production of specialty chemicals and to obtain rate
date in order to determine the reaction rate laws and the law parameters such as k, the specific
reaction rate.

NA=NA0-NA0X=NA0(1-X)

Stoichiometric table for batch system;

The stoichiometric table is for all species in the general equation.

 A + ab B ac C + ad D
The stoichiometric coefficients in (d/a + c/a b/a -1) represents the increase in the total
number of moles per mole A reacted. tells us the change in the total number of moles per
mole of A reacted.
d c b
= a + a a 1

The total number of moles can be calculated from equation

NT = NT 0 + dN A0 X

Batch Concentration

The concentration of species involved in the reaction can be calculated by

Nj
Cj = V
The calculation method for volume will depend on the reaction condition as well as on the
reactor type.

Reaction Condition: Gas-Phase reaction, Liquid-Phase reaction

Reaction Types: Constant volume reactors, Variables volume

reactors

Concentration of each component in terms of conversion of X

Constant Volume Batch Reaction Systems

In constant volume the equation change into:

I.3.5 Flow Systems

The form of stoichiometric table for continuous flow reactor is virtually identical to the batch

one, except that the difference in symbols, Nj0 is replaced by Fj0, Nj is replaced by Fj.
Fa M oles/time M oles
CA = v = Liters/time = liter

Liquid Phase Concentration

For liquids, volume change with reaction is negligible when no phase are taking place.

V=V0
Gas Phase Concentration

In a gas phase reaction, the volume is varied. The concentration of component can be
determined by expressing v as a function of conversion as:

P V = Z NT R
T

T = Temperature, K

P = Total Pressure, atm (kPa; 1 atm = 101.3 kPa)

Z = Compressibility Factor

R = Gas Constant

To find volume as a function of conversion x

At complete conversion

The temperatures and pressures will not change significantly during the course of the
reaction. Therefore we can assume Z Z0.

I.4 Isothermal Reactors Design

I.4.1 Isothermal Reactors Design Structure

The design structure for isothermal reactors in term of conversion combines the fourth
chapter with the knowledge from the previous three chapters explained above. For simpler
illustration, the diagram below outlines the overall steps for all reactors in the most
straightforward way.
Calculation for isothermal reactor design requires the use of algorithm, which is described
chronologically by five general steps:

1. Mole Balance:

Establish the appropriate mole balance equation, depending on the type of reactor

2. Rate Law:

Express the rate law in terms of limiting reactant

3. Stoichiometry:

Batch reactor - relate concentration VS volume and number of mole,

Flow reactor - relate concentration VS volumetric and molar flow rate,

Correlate volume/volumetric flow rate to conversion, pressure and temperature.

4. Law Combination:

Substitute the rate law and stoichiometry into the mole balance equation

5. Evaluation:

Evaluate the combined steps analytically or graphically

For easier determination of mathematical forms used for each isothermal reactor
design, the following table briefly summarize the equations for the frequently used
reactors such as batch reactor, CSTR, PFR and PBR.
I.4.1.1 Batch Reactor

In batch operation system, the assumption is the absence of inlet and outlet flow. With
constant volume, the mole balance equation for batch reactor is written in terms of
concentration,

1 dN A dC A dC A
V ( dt ) = dt = rA or dt = rA

By applying the algorithmic steps, the mole balance equation can be evaluated in
order to achieve the equation of time needed for the operation within the reactor,

1. Mole Balance

2. Rate Law

3. Stoichiometry
 4. Law Combination

5. Evaluation

The integration yields the equation of operating time for batch reactor,

The complete algorithms that also cover the second-order reaction is provided in the
table below:
I.4.1.2 Continuous-Stirred Tank Reactor

The algorithmic steps for CSTR design is summarized below:

1. Mole Balance

v 0 C A0 X = rA V
2. Rate Law

rA = kC A
3. Stoichiometry

C A = C A0 (1 X )
4. Law Combination

= 1k ( 1X
X
)
5. Evaluation
C A0 k
CA = 1+ k and X = 1 + k
In prior to designing CSTR, the degree of conversion has to be identified by
calculating Damkohler Number (Da) i.e. a dimensionless value that serves quick
estimation for degree of conversion. Da 0.1 results < 10% conversion while Da 10
leads > 90% conversion. Thus, Da is directly proportional to the resulting conversion.

Formula of Da is further divided into first and second order of irreversible reaction:

First-Order Reaction

Second-Order Reaction

After knowing the Damkohler number as a parameter to determine the degree of

conversion, details about CSTR are then explained in series arrangement of
equally-sized CSTR. The purpose is to express the mole balance equations in term of
concentration for each CSTR.

First Order Reaction in CSTR

The series arrangement of two CSTRs below are said to be in the first order of
reaction with liquid-phase components (v = v0).

Mole balance on CSTR-1 (blue):

Mole balance on CSTR-2 (red):

The operating temperature for the example above is different for each CSTR.
Meanwhile in the next example illustrated below, equally-sized CSTRs are operated
at the same temperature i.e. k is the equal for all reactors.
In the case of n equal-sized CSTRs, the equation in the red box regarding the
concentration leaving the last reactor can also be expressed in terms of conversion.

Conversion plot as a function of number of reactor for a first order reaction is shown
As for the CSTR in parallel arrangement according to the picture below:
The formula for individual reactor volume,

The reactors have equal size and temperature, which leads to the same conversion and
reaction rate for each reactor. Then the molar flow rate and volume can be substituted.

Second Order Reaction in CSTR

For a second-order liquid-phase reaction that takes place in CSTR, the combination of
rate law and CSTR design equation yields,

Using stoichiometric table for constant density,

v = v 0 , C A = C A0 (1 X ) , and F A0 X = v 0 C A0 X

The obtained equation of V is then divided by v 0

The equation of conversion for second-order CSTR will be,

I.4.1.3 Tubular Reactor

The equations for tubular reactors are categorized in accordance to the phase of
substances inside the reaction, which is either liquid-phase or gas-phase.

Liquid-phase Tubular Reactor

Gas-phase Tubular Reactor

I.4.1.4 Packed Bed Reactor

General mole balance for packed bed reactors would be

Fluid flow through packed beds is accompanied by substantial pressure drop across
the bed. For liquid-phase reactions, slight changes in pressure do not affect
concentration and consequently does not affect the reaction rates. Meanwhile in the
case of gas-phase reactions, the concentration is a function of pressure. Reduction in
pressure implies reduction in concentration as well as the reaction rates.
The relationship between concentration and pressure in different phase reactions are
categorized into several cases:
Case I: Liquid-phase reactions
Concentration is independent of pressure, so pressure is unnecessary to be included
in the calculation of conversion.
v = v0 =constant
Case II: Gas-phase reactions
For isothermal reactor, (P/P0) may vary along the reactor length.

Pressure Drop in Packed Bed Reactors

Ergun equation:

Where P = pressure drop (N/m2 or Pa)

Dp =
Particle diameter (m)

s = sphericity
= porosity
= density (kg/m 3 )
uo =
superficial velocity (m/s)

N RE = Dp uo /
Differential equation for pressure drop in spherical-packing bed reactor:

The packing characteristic such that the porosity and particle diameter are considered
invariant toward reactor length, so the parameters that will be evaluated as a function
of reactor length is the viscosity, density and operating parameter G.

Evaluating G (Superficial Mass Velocity)

G = 0 u0 = u
Where the unit of G is defined to be the mass flow rate per unit area (kg/ m2 -s).

Evaluating Viscosity
iscosity of gases are weak function of pressure. We can assume the gas mixture
V
viscosity to be independent of pressure. The viscosity of gases depends on the mixture
composition. In a reactor, mixture composition will change, the gas mixture viscosity
will also change.

Evaluating Density
Density of gases depend on pressure. There are two ways of handling the pressure
terms, in terms of inlet density, P/Po, T/To. In terms of local P, T and composition

Simplification in Calculating Pressure Drop in PBR

If numerical method is applied to solve for differential equation, a simpler and more
elegant approach is to calculate density at any given position (z) in the reactor using
ideal gas law and local conditions.

I.4.1.5 Microreactors

Microreactors are characterized by their high surface area-to-volume ratios in their

microstructured regions that contain tubes or channels.The resulting high surface
area-to-volume ratios reduce or eliminate heat/mass transfer resistances often found in
larger reactors. The advantages of of microreactors include their practical use in the
production of toxic or explosive intermediates, where a leak or microexplosion for a
single unit will do minimal damage because of the small quantities of material
involved. Also, the residence times are shorter.

The algorithmic steps are summarized below:

I.4.1.6 Membrane Reactors
The mentioned terminologies in the diagram of membrane reactors are defined:
Membrane - A material that allows selective permeation of certain molecules
Permeate - The part of the fluid stream that passes through the membrane.
Retentate - The part of the fluid stream that does not pass through the membrane.

Membrane reactor allows the separation and reaction processes to occur

simultaneously and in a single-vessel, and also to increase the yields of products from
reactions that are thermodynamically limited, i.e. from reversible reactions.

General mole balance equation of membrane reactor:

Because the permeability of membrane is only specified for C only, the general mole
balance equation on C includes the rate of permeation (Rc). This rate is usually
determined experimentally.
 CHAPTER II

PROBLEM SOLVING

II.1 Chemical Kinetic and Reactor Design

1. Example Problem 3: Page 7

Question

Table 3-11 gives the initial rate data [-d(B2H6)/dt] reported for the gas phase reaction of
diborane and aceone at 114oC: B2H6 + 4 Me2CO 2(Me2CHO)2BH. If a rate expression is of
the form

Rate = k P nB 2 H 6 P M
m
e2 CO6

Determine the constants n, m, and k.

Solution

Rate = k P nB H6
m
PM e CO
2 2 6

Linearizing the rate expression

ln (Rate) = ln k + n ln P nB 2 H 6 + m ln P M
m
e2 CO6

The linearized equation is already in the form of

Where the coefficients CO = k, C1 = n, and C2 = m. PROG3 program determine the coefficient

form multiple regression of the independent variables P nB H and P Mm
e CO and the dependent
2 6 2 6

variables rate. The results of the gives these values for the coefficients.

Therefore, Co = k = 4.68, C1 = n = 0.98, and C2 = m = 0.95. The rate of the equation is

0.98 0.95
expressed as Rate = 4.68P B 2 H 6 P M e2 CO6 or an approximation of,

The rate constant k can be determined with values of exponents, m = n = 1 as follows:

The average constant k = 3.85 and the final rate equation is Rate = 3.85 PB2H6PMe2CO. The
computed rate of constant from PROG3 is 4.68 and the calculated value from Table 3-12 is
3.85. The percentage deviation between these values is 17.8%. Figure 3-22 shows plots of
partial pressure of B2 H6 and Me2CO versus the initial rate.

2. Example Problem 5: Page 12

Question
The reaction 2N OCl 2N O + Cl2 is studied at 200oC, The concentration of NOCl initially
consisting of NOCl changes as follows:

Determine the order of the reaction and the rate constant.

Solution

If the reaction is second order, the rate equation is:

Rearranging the 2nd order rate equation and integrating with the boundary condition at t = 0,
CA = CAO and at t = t, CA = CA, gives

Plot of 1/CA versus t gives a straight line with the slope = k = 0.06661/gmol.s. The program
PROG1 determines the rate constant for a second order rate of reaction. Equation 3-285 is of
the form 1/Y = A + BX where the slope B is the rate constant k. The results of the computer
program are shown in Table 3-14.

The constants used for the equation are:

Figure 3-24 shows the relationship between 1/CA as a function of time (t). The graph is a
straight linear line, therefore the assumed order of reaction is correct. The slope of the line
from regression analysis is the rate constant k.

3. Example Problem 3-9

Question

Huang and Dauerman (1969) have studied the acetylation of benzyl chloride in dilute
solution at 102oC. Using equimolal concentrations of sodium acetate and benzyl chloride
(0.757 kmol/m3), Table 3-16 lists reported data on the fraction of benzyl chloride remaining
unconverted versus time. Determine the order of the reaction and the reaction rate constant at
this temperature.
Solution

The reaction is assumed to be second order as represented by

+
N aAc + C 6 H 5 CH 2 Cl C 6 H 5 CH 2 Ac + Ca + Cl which can be expressed in terms of
components A and B as

The rate equation of component B is

The stoichiometry for components A and B is:

In terms of fractional conversion of B, XB

C BO C B
XB = CB

The equation above is further expressed as:

CB = CBO (1- XB)...(2)

Since the concentration of A and B is the same, then

CA = CB = CBO (1- XB)

And
dC a dX b
dt
= C BO dt
...(3)

Substituting equation (2) and (3) into the rate equation for component B gives
dX b
( ra ) = C BO dt
= k C 2BO (1 X a )2

Rearranging equation above and integrating between the limits t = 0, Xa = 0, and t = t, Xa =

Xa gives
XB t
1
(1X A )2
= k C BO dt
0 0

[ 1
1X B ]
1 = kC
BO
t

[ 1
C a /C BO ]
1 = k C BO t

The rate constant k can be calculated from the above equation as

k= 1
C BO t [ 1
C a /C BO
1 ]
Table 3-17 shows the calculated values of the rate constant k at various time (t).

Discounting the first and the last two values of rate constant k, the average value of the rate
constant is k = 0.0055 m3 /(mol.sec). This shows that rate of reaction is second order

II.2 Questions from Chapter 3

Question 3-7ab

a. The rule of thumb that the rate of reaction doubles for a 10C increase in temperature

occurs only at a specific temperature for a given activation energy. Develop a relationship
between the temperature and activation energy for which the rule of thumb holds. Neglect
any variation of concentration with temperature.

b. Determine the activation energy and frequency factor from the following data:

Answer:

a. We know that that the rate of reaction doubles for 10 C, and if a reaction rate doubles
for an increase in 10 C, when T = T1 then let k = k1 and when T = T2 = T1 + 10, let k
= k2 = 2k1. Then with k = Ae^-E/RT in general, k1 = Ae^-E/RTi and k2 =
Ae^-E/RT2.

Therefore:
The b part, We obtain k= Ae^(E/RT) From equation 3-18.
From the data, at T1 = 0 C, k= Ae^(E/RT) and T2 = 100 C, k2= Ae^(-E/RT2)
Dividing gives:

II.3 Questions from Chapter 4

Question 4-11B

The gaseous reaction A B has a unimolecular reaction rate constant of 0.0015 min-1 at
80F. This reaction is to be carried out in parallel tubes 10 ft long and 1 in. inside diameter
under a pressure of 132 psig at 260F. A production rate of 1000 lb/h of B is required.
Assuming an activation energy of 25,000 cal/mol, how many tubes are needed if the
conversion of A is to be 90%? Assume perfect gas laws, A and B each have molecular
weights of 58.

Given data:

-rA = kCA

K = 0.0015 min-1 at 80F

E = 25,000 cal/g mol

X = 0.90

MB = 1000 lb/hr

MWA = MWB = 58 lb/lb mol

Dt = 1 inch (I.D)
L = 10 ft

P = 132 psig = 146.7 psia

T = 260F = 720R

number of tubes
Nt =

Flow Rate Calculation

= 17.21 lb mol/hr
FB =

FA0 = = = 19.1 lb mol/hr

PFR Design Equation

V = = FA0 where = 1-1 = 0 yA = 1.0 = yA = 0

-rA = kCA(1 X) CA = =

V = FA0 =
FA0 = ln 9() = ln 10

k2, V, and nt Calculation

At T2 = 260F = 720R, with k1 = 0.0015 min-1 at T1 = 80F = 540R,

K2 = k1 exp (()) = 0.0015 exp (( - )) = 53.6 min-1 = 3219 hr-1

V = ln 10 = = ln 10 = 0.72 ft3

nt = = 13.2 = 14 Therefore, 14 pipes are necessary

Question 4-15

It is desired to carry out the gaseous reaction A B in an existing tubular reactor consisting
of 50 parallel tubes 40 ft long with a 0.75-in. Inside diameter. Bench-scale experiments have
given the reaction rate constant for this first-order reaction as 0.00152 s-1 at 200F and 0.0740
s-1 at 300F. At what temperature should the reactor be operated to give a conversion of A of
80% with a feed rate of 500 lb/h of pure A and an operating pressure of l00 psig? A has a
molecular weight of 73. Departures from perfect gas behavior may be neglected, and the
reverse reaction is insignificant at these conditions. (Ans: T = 275F.)
 Given Data:

Tube dimensions: L = 40 ft, D = 0.75 in. nt = 50

V and FA0 Calculation

2
nt D2 (50)( 0.75
12 )
V = 4
L = 4
(40) = 6.14 ft3
m lb
500 hr
FA0 = M WA = 73 lb = 6.86 lb mol/hr
A lbmol

Tubular Reactor Design Equation

kC AO (1X) P
V = FA0 X rdX where -rA = 1+ X
= kCA0(1 X) and CA0 = RT
= yA0 RTP
A
0

X
F F A0 RT
FA0
dX 1 1
V = FA0 X rdX = kC AO (1X)
= kCAO ln ( 1X ) = ky A0 P
ln ( 1X )
A AO
0 0

F RT 1
k = V A0y ln ( 1X )
A0 P

Temperature Calculation with Rearrangement of k Equations

Assume Arrhenius equation applies to the rate constant

E
At T1 = 200F = 659.67R 660R, k1 =
0.00152 = A e
RT 1

E
At T2 = 300F = 759.67R 760R, k1 = 0.0740 = A e RT 2
k2
k1
= exp[ E 1
R (T
1
T 1 )]
2

k T T
ln k2 = E (1
R T
1
T1
) = E ( 2 1)
R T 1T 2
1 2

T 1T 2 k
ln k2 = (660)(760)
E
0.0740
R = T ln 0.00152 = 19500R
2 T 1 1 (100)

E
A = k1 exp[ RT 1
] so k = k1 exp [ E (1
R T
1
T1
)]
From the previous equation above,
F RT 1
k = V A0y ln ( 1X )
A0 P

F RT 1
Thus, k = V A0y ln ( 1X ) = k 1 exp [ E (1 1
)]
A0 P R T T1

Divide both sides of k equation by T

F A0 R k1 exp [ E 1 1
R ( T T )]
1
V y A0 P
ln ( 1X ) = T
1

psia f t3
(6.86 lbmol
hr )(10.73 lb molR )
exp[19500( T1 660R
1 )]

(0.00152 s1 )(3600 s )(6.14 f t3 )(114.7 psia)

ln 5 = T
hr

After further simplification,

exp[19500( T1 660R
1 )]
0.0308 R-1 = T
T = 738 R = 278 F

The operating temperature of reactor is 278 F to give 80% conversion of A

BIBLIOGRAPHY

H. Scott Fogler. (2006) Element of Chemical Reaction Engineering Fourth Edition