BKF2453

Chemical Reaction Engineering

Chapter 1

MOLE BALANCES AND

REACTION KINETICS
QUIZ
Benzene (C6H6) is partially oxidized to produce
maleic anhydride (CH(CO)O), carbon dioxide and
water in an irreversible reaction. Initial feed ratio
of benzene to oxygen is 1:5.
1. What is the limiting reactant? (3 marks)
2. If the rate of benzene is -1 mol/gcat/s, what are
the rates of other components (4 marks)
OBJECTIVES
Upon the completion of this chapter, students are able to:

Describe concepts of rate of reactions and explain the

chemical kinetics, emphasizing definitions, which illustrates how
the reaction rate depends on the concentrations of the reacting
chemicals
To model a reaction kinetics using the batch
reactor data and the analysis methods include graphical,
numerical, polynomial, initial rates, half-lives and least-
square analysis
Develop a general mole balance that can be
applied to any species entering, leaving and/or remaining in
the reaction system volume
Apply general mole balance equation to
develop a preliminary form of design equations for batch and
continuous reactors
Decide suitable mode of reactor for a
chemical/biochemical process
 MIND MAPPING
Reaction rate
Power
-rA or rA
Chapter 1 Rate laws

Analyze data
Batch
Reactor
Equation

Continuous/ Flow Elementary/ Non-E

Stirred tank

Tubular

Hollow Packed/fixed bed

REACTION KINETICS
INTRODUCTION

Kind
Chemical
Number
Identification

Alkene Configuration
e.g. Cis-2-butene
H H
Trans-2-butene C=C

H CH3 CH3 CH3

C=C

CH3 H
INTRODUCTION
Reaction ?
Occurs when a detectable number
of molecules of one or more
species lost their identification
and new compound forms

decomposition

3 way combination

isomerization
REACTION KINETICS:
RATE OF REACTION
Considering the reaction below
Chloral Chlorobenzene DDT Water
CCl3CHO 2C 6H5Cl (C6H4Cl)2 CHCCl3 H2O
A 2B C D
Rate of reaction
rA the no. of moles reacting (A) per unit time per
unit volume (mol/dm3 . s)
rA the no. of moles A per unit time per unit
catalyst mass (mol/ s . g catalyst)
rA is an intensive quantity, algebraic equation
+ formation - transformation
RATE OF REACTION (CONTINUED)
Expressedin (can be calculated from) the rate
equation/model/law.

Independent of the type of reactor (e.g.,

batch/continuous)
Butoften limited by mass transfer (poor mixing
associated with reactor design and unsuitable
catalyst particle), thus falsification of rate law
CASE STUDY
1 mol B
3 mol A
? mol A

Consider an irreversible reaction for species A:

AB
If 3 mole A is put into a1-dm3 beaker and it reacts at a certain
condition. After 1 min, 1 mole B is being formed. The
temperature is controlled to be constant.

Thus,
the apparent rate of formation of B is rB = 1 mole/dm3/min

And the apparent rate of transformation (consumption) of A,

-rA = 1 mol/dm3/min
HOWEVER THE RATE IS NOT
DIRECTLY PROPORTIONAL TO TIME

1 mol B 2 mol B
3 mol A 2 mol A 1 mol A

1 mol A consumed at the first 1 min

But for the next 1 mole of A consumption,

the time is not simply the same (1 min).
The rate of A consumption usually varies
with time.
 Actually the rate is 0.85
mol/dm3/min and NOT 1
mol/dm3/min
WHEN YOU PLOT A GRAPH Not because of mass transfer but
of how we analyze

3.5

2.5
Transient
1 What is
2
rate 2?
Concentration (mol/L) 1.5
Rate
1 2 1

Rate 0.5
2 A
Rate0
B
3 0 1 2 3 4 5 6 7 8 9 101112

t (min)
 WHEN YOU PLOT A GRAPH ln(-rA) VS
lnCA

Ln(-rA) = 0.9898LnCA+Ln
0.5 0.428
0 -rA = 0.428CA1
-2 f(x) = 0.99x
-1.5 -1 -0.5 - 0.850 0.5 1 1.5
This equation is the rate law
R = 1 -0.5 determined via graphical
method, 0.428 is rate
Ln (-rA) -1 constant and 1 is the
order of the rate law
-1.5
In Math, we can also
determine the constant
-2
and power in rA = kCA
-2.5 using numerical method
In CRE1, youd learn how to
Ln CA formulate the rate law
using several methods
including this one
 Youd find out this
later, so please
dont drop this
FINDING FROM THE CASE STUDY subject

1.
-rA = and not simply (or )
2. Rate of reaction affected by the reactant
concentration under the power equation (so-
called the Power Law model)
proportionality can be seen in logarithmic plots
REACTION KINETICS STUDY
The reaction kinetics are formulated based on
experimentally proven mechanism, not an arbitrary
phenomenon
Rate law is the simplest model, for instance:

A Products
The rate of transformation of A can be:-
1. Linear function of concentration; or
-r = kC
A A

2. Quadratic function of concentration; or

-rA = kCA2
Other function of concentration, such as
-rA = k1CA/(1+k2CA) and etc., refer the textbooks.
RELATION OF RATE IN REACTIONS
For a reaction given below:
aA + bB cC + dD

rA rB rC rD

a b c d

Example:
2NO + O2 2NO2

rNO rO2 rNO2

2 1 2
REACTION
KINETICS
RATE LAW
ACTIVATION ENERGY
REACTION ORDER
 RATE LAW: DEFINITION & FACTORS
RATE LAW
-rA = [kA(T)][fn(CA,CB,)]
Reaction rate depends on temperature and chemical
concentration
Rate law gives the correlation of the reaction rate with
temperature and concentrations.
Temperature varies exponentially under the Arrhenius
equation to give the rate constant, k
Concentrations formulated based on the kinetic model
yielded from experimentations: Power Law, Langmuir-
Hinshelwood, Eley-Rideal etc.
 E
A+B

C
HR

Reaction Coordinate
At T0:
Arrhenius Eqn.

At T:

Linearization
lnk Non-linear curve
ln A
k
Slope = -E/R

1/T T
EXAMPLE
POLYMATH Results
07-20-2009

Linear Regression Report

T
Model: lnk = a0 + a1*K Rxn1: High E

Variable Value 95% confidence

lnk
a0 38.923319 0.9924566
a1 -1.461E+04 320.53961
Rxn 2: Low E
General
Regression including free parameter 1/T
Number of observations = 5
k with higher E is more sensitive to
Statistics temperature than those with low E
R^2 = 0.9998574
R^2adj = 0.9998099
Rmsd = 0.0051949
Variance = 2.249E-04
RATE LAW: CONCENTRATION FORMULATION
BASED ON POWER LAW MODEL
Consider the following reaction:
aA + bB cC + dD
The rate law may be written as :

rA kCA C B
where k = specific reaction rate
= order with respect to A
= order with respect to B
+ = overall order

What happen if
= a and = b
a and b
 REACTION ORDER
Non-elementary Rate
Elementary Rate Law Law
if the Stoichiometry CO+CI2COCI2
coefficients are the same
as the individual rCO kCCO CCI3 / 22
reaction order of each
This rxn is 1st order
species. with respect to CO, 3/2
order with respect to
H2 +I2 2HI
CI2and 5/2 order
(rHI) = k CH2 CI2 overall.
 REACTION ORDER
Overall reaction order can be determined by the unit of k

Reaction Rate Law k unit k' unit

Order (no catalyst) (with catalyst)
Zero mol/dm33.s ?

One s-1 ?

Two
Two (dm)
(dm)3/mol.s
3
/mol.s ?
?

Three
Three (dm
(dm3/mol)
3
/mol)2.s
2
.s ?
?
SELF TEST : RATE LAW
1) What is the reaction rate law for the reaction
A+ BC if the reaction is elementary? What is r ? What is r
B C
?

rA k AC AC B1/ 2
rA rB

1 1/ 2
1 k
rB rA A C AC B1/ 2
2 2
rA r
C
1 1
rC rA k AC AC B1/ 2
Calculate the rates of A, B, and C in a reactor where the
concentrations are CA = 1.5 mol/dm3, CB = 9 mol/dm3 and kA = 2
(dm3/mol)(1/2)(1/s).

dm 3
1/ 2
1 mol mol
1/ 2

rA 2 1 . 5 9
mol s dm dm 3
3

mol
rA 9
dm 3s
mol
rB 4.5
dm 3s
mol
rC 9
dm 3s
RATE LAW FOR THE REVERSIBLE
REACTIONS
Rate law for reversible reaction must satisfy
thermodynamic relationships at equilibrium
General reaction

aA + bB k1 cC + dD
k-1

thermodynamic equilibrium relationship

c d
CCe CDe k1
KC a b
C AeCBe k1

Can be reduced to the irreversible rate law. How?

REVERSIBLE REACTION
Example (assumed elementary):
2C6H6 C12H10 + H2 ;

k-B
Rate of deformation of benzene 2B D + H2
-rB, forward = kBCB2
kB

Rate of formation of benzene

rB, reverse = k-BCDCH2
concentration
Thus, equilibrium
constant
rB,net = rB, forward + rB, reverse
Kc = kB/k-B
rB, net = -kBCB + k-BCDCH2
2

- rB, net = kB(CB2 (CDCH2)/KC)

RATE LAW FORMULATION: STEPS
OF DATA ANALYSIS Not simple
1. Postulate a rate law
2. Select reactor type and corresponding mole balance.
3. Process your data in terms of measured variables
4. Look for simplifications
5. Analyze the progress of reaction rate (-rA vs t for
irreversible one) by using any of the following:-
i. Graphical method
ii. Numerical method
iii. Polynomial Fit
iv. Non-linear regression
* Extrapolate rA0 using methods (i) and (iii) in the
method of initial rate for reversible reactions
RATE LAW FORMULATION: STEPS
OF DATA ANALYSIS (CONTINUES)

TIPS IN USING METHODS

1. Methods to derive linear equation from the combination of rate
law and mole balance
Integral
Differential

2. Tools
to determine slope (rate) of a curve
(time-based)
Graphical Methods
Numerical Methods (Finite Difference Method etc.)

Polynomial Fit (one example of non-linear regression)

Non-linear regression

3. Tools to determine equation of a curve

Linear regression (after linearization)
Non-linear regression (no linearization required)
 TYPES OF REACTORS
Continuous stirred tank reactor
(CSTR)
Batch

Reactor Continuous Plug Flow Reactor

(PFR)

Fixed Bed Reactor

Tubular reactors
(FBR)
Sizes or scales are based on production rate
1. Bench/Lab Packed Bed Reactor
2. Pilot (PBR)
3. Industrial
BATCH REACTOR [2] Temperature
[1] Flange
Lid
Stirrer
shaft
probe
[5] [2] pH electrode
Electroni
c Stirrer
[3] Oil
Sampling Heater
T pHI
Retort point
I
Stand [1] Baffle

[1] Six-bladed
Impeller

[1]
Reactor Silicone oil

[4] Oil Bath

Key Characteristics
unsteady-state operation (change with time)
no spatial variation of concentration or temperature (well-mixed)
mainly used for small scale operation
suitable for slow reactions
mainly (not exclusively) used for liquid-phase reaction
charge-in/clean-up times can be large
CONTINUOUS STIRRED TANK
REACTOR (CSTR)

CSTRs are also known as

back-mix reactor

Key Characteristics
steady state operation (do not change with time)
used in series
no spatial variation of concentration or temperature (well-mixed)
mainly used for liquid phase reaction
suitable for viscous liquid
TUBULAR REACTOR:
PLUG FLOW REACTOR

Key Characteristics
steady-state operation
spatial variation in axial direction but not in radial direction
suitable for fast reaction mainly used for gas phase reaction
temperature control may be difficult
there are no moving parts
MOLES BALANCES
 THE GENERAL MOLES BALANCE
EQUATION System
Volume
Gj and
Fjo dNj/dt Fj

Rate of generation Rate of

Rate of flow Rate of flow by chemical reaction

into the system out of the system accumulation
within the system within the system
dNj
Fjo Fj G j
dt

M M
Knowing that G j rV,
j G ji r W and G j G ji r jiV i r dV
'
j j
i1 i1

Thus,
dNj
Fjo - Fj rjdV
dt
MODELS DEVELOPMENT:
BATCH SYSTEM

0 0
Fjo - Fj + Gj = dNj/dt

Knowing that : Gj = rjV

Thus, dN j
rj V (different ial form)
dt
Nj
dN j
t
N jo
rj V
(integral form)
MODELS DEVELOPMENT:
CSTR SYSTEM
Fjo

Fj

0
Fjo - Fj + Gj = dNj/dt
Thus,
Fjo Fj + rjV = 0 Fj = Cj.v

Fjo Fj
V (algebraic form) jC jo C j
(rj ) V
(rj )
MODELS DEVELOPMENT:
PFR SYSTEM
V V V + V

Fjo Fj
Gj

Fjo - Fj + Gj = dNj/dt

FjV - FjV+V + rj V =

(FjV+V - FjV ) /V = rj

Taking the limit as V0,

dFj
rj (different ial form)
dV
Fj
dFj
V (algebraic form)
(r )
Fjo j
Models Development:
PBR System
W W W + W
Fjo Fj
Gj

0
Fjo - Fj + Gj = dNj/dt

FjW - FjW+W + rj W = 0

Taking the limit as W0,

dFj
rj' (different ial form)
dW
Fj
dFj
W (r )
Fjo j
'
(algebraic form)
SUMMARY
Differential Algebraic Integral Remarks
Equation Equation Equation
Batch Nj
dN j Conc. changes with
dN j
(rj )V t (r )V time but is uniform
dt N jO j
within the reactor.
Reaction rate varies
Fjo Fj with time.
V
CSTR (rj ) Conc. inside reactor is
uniform. (rj) is
constant.
Fj
dFj dFj Exit conc = conc inside
rj V (r ) reactor.
dV FjO j

PFR Fj Concentration and

dFj dFj
rj '
W (r ) '
hence reaction rates
dW FjO j vary spatially.
PBR Concentration and
 CASE STUDY
Consider the following reaction

1. Rate Law: Power Law Model,

2. Reactor & mole balance: Batch reactor with constant volume

3. Process data with measured variable combination

CASE STUDY: CONTINUES
3.1. Graphical

This method accentuates measurement error!

CASE STUDY: CONTINUES
3.1 Polynomial (using Polymath)
using Polymath, MS Excel, Spreadsheet, MATLAB
CA = ao + a1t + a2t2 + a3t3 +a4t4

3.1 Numerical method (pg 258-259)

dC A 3C A0 4C A1 C A 2
Initial Point 1.
dt 2t
Equal interval
Interior point 2.
dC A
dt

2
1


t

C A( i 1) C A(i 1)

dC A 1
e.g., C A4 C A2
dt t3 2 t

dC A 1
Last point 3.e.g ., C A3 4C A4 3C A5
dt t5 2t
 CASE STUDY: CONTINUES
4. Simplification: no side reactions, constant temperature and ??
5. If you prefer the integral method: trial and error to fit with an order
Zero order First order Second order
dC A dC A dC A
rA k rA kCA
2
rA kCA
dt dt dt
CA t CA t CA t
dC A dC A
dC
C A0
A k dt
0
C C A k 0 dt CA
2
k dt
A0 C A0 0

C A C A0 kt ln C A CC A
kt 1
CA

C A C A0 kt
A0
kt
ln C A ln C A0 kt C
A C A0

ln C A0 ln C A kt 1 1
kt
C A0 C A C A0
ln kt
CA 1 1
kt
C A C A0
 CASE STUDY: CONTINUES
Finally we should also use the formula to plot reaction rate data in
terms of concentration vs. time for 0, 1st, and 2nd order reactions.
These types of plots are usually used to determine the values k for
runs at various temperatures and then used to determine the
activation energy.
Zero Order First Order Second Order

CASE STUDY: CONTINUES

If all the trials for 0, 1, 2 and 3 order failed to fit

(<95% of fit), then use the non-linear regression
CASE STUDY: CONTINUES
5. IF DIFFERENTIAL METHOD (P. 224-232)

Taking the natural log of

The reaction order can be found from a ln-ln plot
of:

 CASE STUDY: CONTINUES
Non-Linear Regression: Least-Squares Analysis (p. 252)
We want to find the parameter values (, k) for which the sum of
the squares of the differences, the measured variable and the
calculated variable is a minimum. The variable can be reaction
rate, concentration or time

for instance,

That is we want 2 to be a minimum.

For concentration-time data, we can integrate the mole balance
equation for -rA=kCA to obtain

We find the values of and k which minimize S2

SELF TEST
The reaction AB is carried out in a constant volume batch
reactor. Determine the reaction order and specific reaction rate
from the following data.

t(min) 0 10 20 30
CA(mol/dm3) 1 0.6 0.4 0.3
METHOD OF HALF-LIVES
Half life, t1/2 time takes for the concentration of the reactant to
fall to half of its initial concentration.

1. Rate Law: Power Law Model,

2. Reactor & mole balance: Batch reactor with constant volume

3. Process data with measured variable combination

4. By integrating with the initial condition of CA=CA0 and t=t0,
thus t 1 1 1

k ( 1) C A 1 C A01
1
1 C A0
t 1 1
kCA0 ( 1) CA

When CA=CA0 and t=t, thus

2 1 1 1
t1 1
2 k ( 1) C A0
 Taking the natural log of both sides,

2 1
ln t 1 ln (1 ) ln C A0
2 ( 1)k

Slope = 1-
ln t1/2

ln CA0
DESIGN OF REACTOR IN A CHEMICAL
PROCESS
A chemical process has a specific production rate
Backward calculation to size reactor in which costs
also included.
Decisions are made hierarchically in a process
synthesis through the economic potential levels:-
1. Mode: batch, continuous or semi-batch
2. Input-output structure of flowsheet Reactor Design
3. Recycle stream
4. Separation system: a Vapour recovery, b liquid
recovery
5. Heat-exchanger network
REVISIT OF MATERIAL AND
ENERGY BALANCE SUBJECT
Based on the MEB subject, which of the following
methods are we using here?
1. Molecular species balance

2. Atomic species balance

3. Extent of reaction

Extent of reaction, in which limiting reactant

involves as the key chemical and conversion as the
key variable, for reactor design purpose in a
process
Would be taught later
FORMULA TO DETERMINE ECONOMIC
POTENTIAL
(EP 0 TO BE ACCEPTED AND TO PROCEED)

1. EP2 = Revenue Raw Material Cost (for X = 1 and

various yP) Utility Cost (e.g. Reactant Gas
Compressor, Reactant Pre-treatment or Impurities
Disposition)
2. EP3 = Revenue Raw Material Cost ( for 0 X 1
and various and yP) Utility Cost (EP2 utilities and
recycle utilities) Reactor Cost Catalyst Cost
3. EP4 = EP3 Separation Unit Cost (various
efficiency)
4. EP5 = EP4 heat exchanger network
INPUT INFORMATION
The reaction kinetics and conditions
The desired production rate
The desired product purity, or some information about
price versus purity
The raw material and/or some information about price
versus purity
Physical properties of all components
Information about the rate of catalyst deactivation
Any other processing constraints
Other plant and site data
Information concerning the safety, toxicity and
environmental impact of the materials involved in the
process
Cost data for by-products, equipment and utilities
DECISION AT LEVEL 1
Decision to process in which mode: batch, continuous or
semibatch
Guidelines:-
Production Rates: As a rule of thumb (based on experience),
<500tonnes per year Batch
>5000 tonnes per year Continuous.

Market Force: Seasonal demand is worth batch reactor, eg.

paint
Operational Problems: Problematic and slow reactions are
worth batch reactor, eg. Biological reaction, filtration or
crystallization unit in a continuous process and etc.
Selectivity limitation: multiple reactions are worth
semibatch reactor if desired product favoured at low
concentration of reactant
Other consideration from literature
THANK YOU