BKF2453

Chemical Reaction Engineering

Chapter 1

MOLE BALANCES AND

REACTION KINETICS
PREPARATORY TESTS
 The reaction: Hexanol + Oxygen -> Hydrogen + Carbon
Monoxide. If 2 moles of hexanol and 3 moles of oxygen
were used, how many moles of hydrogen will be
produced after the reaction is complete
 The reaction: Pentane + Oxygen -> Hydrogen + Carbon
Monoxide. If 2 g of pentane and 0.3 g of oxygen were
used, how many grams of hydrogen will be produced
after the reaction is complete
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
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  Chlorobenz ene  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)
 Expressed in (can be calculated from) the rate
equation/model/law.

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

batch/continuous)
 But often 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:

AB
If 3 moles A are 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
Not because of mass transfer but of
WHEN YOU PLOT A GRAPH how we analyze

3.5

3
Concentration (mol/L)

2.5
1 Transient
2 What is rate
2?
1.5
Rate
1 1 2
Rate
0.5 A
2
Rate 3 B
0
0 1 2 3 4 5 6 7 8 9 10 11 12
t (min)
 WHEN YOU PLOT A GRAPH ln(-rA) VS lnCA

0.5 Ln(-rA) = 0.9898LnCA+Ln

0.428
f(x) = 0.99 x − 0.85 0  -rA = 0.428CA1
-2 -1.5 -1 -0.5 0 0.5 1 1.5
R² = 1 This equation is the rate law
-0.5
determined via graphical
Ln (-rA)

method, 0.428 is rate

-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, you’d learn how to
Ln CA formulate the rate law
using several methods
including this one
 You’d find out this
later, so please don’t
drop this subject
FINDING FROM THE CASE STUDY

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.
 −𝑟
  𝐴 = [ 𝑘 𝐴 ( 𝑇 ) ] [ 𝑓𝑛 ( 𝐶 𝐴 ,𝐶 𝐵 ,… ) ] E

Energy
A+B

 C
HR

Reaction Coordinate
  At T0:
Arrhenius Eqn.
𝐸
  − 𝐸 1 1
𝑘 𝐴 ( 𝑇 ) =𝐴 𝑒 𝑅𝑇   𝑅 (𝑇 )
−
𝑇
𝑘 𝐴 ( 𝑇 ) =𝑘 𝐴 ( 𝑇 0 ) 𝑒 0

  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  kC A C B
where k = specific reaction rate
 = order with respect to A
 = order with respect to B
+ = overall order

 What happen if
1.  = a and  = b

2.  ≠ a and  ≠ b
 REACTION ORDER

Non-elementary Rate Law

Elementary Rate Law
 CO+CI2→COCI2
 if the Stoichiometry
coefficients are the same as
the individual reaction order   r  kC st C 3/ 2
ThisCOrxn is 1CO order
CI 2 with
of each species. respect to CO, 3/2 order
 H2 +I2  2HI with respect to CI2 and
5/2 order overall.
(rHI) = k CH2 CI2
 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
Zero mol/dm
mol/dm3.s
3
.s ?
?

One
One s -1
s-1 ?
?

Two (dm)33/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+ ½ BC if the reaction is elementary? What is rB? What is rC ?

 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
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 k1

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)
COMMON ERRORS IN DETERMINING
RATE LAW PARAMETERS
1. No steps, just a graph hoping examiners to understand
themselves
2. Graphical: Histogram: CA vs t instead of -CA/ t vs t
3. Wrong drawing of imaginary line: area of triangle not
equal for a box
4. Wrong identification of –dCA/dt from histogram
5. Remove negative sign for logarithmic plot of rate vs CA
6. Imbalance points around linear trend line
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
 TI

BATCH REACTOR [2] Temperature

[1] Flange
Lid
Stirrer
shaft
probe
[5] [2] pH electrode
Magnetic bar Electroni
c Stirrer
[3] Oil
Hot-plate Sampling Heater
magnetic stirrer 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      accumulation 
 
into the system  out of the system   by chemical reaction   
     within the system   within the system 
   
dNj
Fjo  Fj  G j 
dt

M M
Knowing that G j  rj ΔV, G ji  r ΔW and G j   ΔG ji   rji ΔVi   rjdV
'
j
i1 i1

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)  0C jo  C j
 (rj ) V
(rj )
MODELS DEVELOPMENT:
PFR SYSTEM
V ∆V V + ∆V

Fjo Fj
∆Gj

Fjo - Fj + Gj = dNj/dt

FjV - FjV+∆V + rj V =

(FjV+∆V - FjV ) /∆V = rj

Taking the limit as ∆V→0,

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

FjW - FjW+∆W+ rj’ W = 0

Taking the limit as ∆W→0,

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

CSTR Conc. inside reactor is

Fjo  Fj uniform. (rj) is constant.
V
 (rj ) Exit conc = conc inside
reactor.

Fj
PFR dFj Concentration and hence
dFj
 rj V  (r ) reaction rates vary
dV FjO j spatially.
PBR Fj Concentration and hence
dFj dFj
dW
 r j' W  (r )
FjO
'
reaction rates vary
spatially.
j
 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

4. Simplification: no side reactions,

constant temperature and ??
 CASE STUDY: CONTINUES
5. Calculate rate

5.1 Polynomial (using Polymath)

• using Polymath, MS Excel, Spreadsheet, MATLAB
CA = ao + a1t + a2t2 + a3t3 +a4t4
                                  

5.2 Numerical method (pg 258-259)

 dC   3C A0  4C A1  C A 2
Initial Point 1. A  
 dt  2t
Equal interval Interior point
 dC 
2. A  
dt 2
1
 t
 
C A( i 1)  C A(i 1)
 
 dC  1
e.g.,  A    C A4  C A2 
 dt t 3 2 t

 dC  1
Last point 3.e.g .,  A    C A3  4C A4  3C A5 
 dt t 5 2t
CASE STUDY: CONTINUES
5.3. Graphical
                                                                               

This method accentuates measurement error!

CASE STUDY: CONTINUES
5.4. If you prefer the integral method: trial and error to fit with an order, graph
just only one but fitness may vary and resulting in numerous trials.
Zero order First order Second order
 dC A   dC A   dC A 
  rA  k   rA  kC A
2
   
 A r   kC A
 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
6. 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
5.5 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 σ2 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 AB 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
1  1 1 
t   1   1 
k (  1)  C A C A0 

1  C  1 
t   1  A0   1
kC A0 (  1)  C A  


When CA=½CA0 and t=t½, thus

2 1  1  1 
t1    1 
2 k (  1)  C A0 
 Taking the natural log of both sides,

2 1  1
ln t1/ 2  ln   1    ln C A0
   1 k

Slope = 1-
ln t1/2

ln CA0
THANK YOU