1

CHE 4473
Kinetics
Instructor:
Daniel E. Resasco

PhD ( Yale University, 1984 )

Research Interests:
Heterogeneous Catalysis
Materials Science
Reaction Engineering
 2

Introduction

• What is Chemical Reaction

Engineering (CRE)

• Fogler Textbook

• Syllabus

• Course organization

• Timeline. Exams, HW, Quizzes

 3

Chemical Reaction Engineering

• Chemical processes turn
inexpensive chemicals into valuable
ones,

• The chemical reactor is the heart

of any chemical process.

• Chemical engineers are the only

people technically trained to
understand and handle them.
 4

Reactor Analysis is Multidisciplinary

Different disciplines incorporated in the study of

chemical reactors and chemical processes

Numerical
Fluids Methods

Thermodynamics
Design Economics

Chemical
kinetics
Reactors Process Safety
$

Control
Heat-Mass
transfer Materials
 5

Minimizing Separation Costs

Raw By-products
Products
materials

$ $$$
Separation
Separation process
process

Chemical By-products
Reactor

Selection of reaction system that operates in the safest and

most efficient manner is KEY to the economic success of a
chemical plant
 6

Reactor in Refineries and Chemical Plants

Everything depends
on what happens
HERE
 7

Reactor in Refineries and Chemical Plants

Fractionation Can you

columns identify the
different units ?

reactor

Storage
Heat tanks
exchangers
 8

Industrial reactors: What do we need to know?

• Stoichiometric
equation: AèB
• Rate Law (Mechanism)
• Mole balances
• Extent of reaction
• Reaction rate
• Reactor type
• What reactor size
• Pressure drop?
• Volume changes during
reaction?
• Lab data needed to size
reactor

• Heat effects? Temperature increases/decreases through reactor

• Catalyst needed? How much? Does catalyst deactivate?
• Mass transfer limitations? External – Internal ?
 9

The world of CRE ( beyond chemical plants)

enzymes
grinding enzymes
wind ht pH, stirring
lig ♒
♒ ♒
SMOG <♒

NOx VOC PM SOx O2 etc.

City Smog Digestive System

Enhanced
Oil
Recovery
 10

TEXTBOOK
Essentials of Chemical Reaction Engineering
H. Scott Fogler
A. & C. Vennema Professor
and A. F. Thurnau Professor
The University of Michigan

FOGLER WEB SITE:

(www.umich.edu/~essen)
 11

Aspects of ChE 4473

Prerequisites
Mole balances
ChE 2033. ChE Fundamentals Energy balances
Gas behavior
Heat transfer
ChE 3113 and 3123. Mo, Heat,
Mass transfer (diffusion in pores)
Mass Transfer
Unsteady state problems
Reaction equilibrium
ChE 3473. ChE Thermodynamics Liquid Vapor equilibrium
Open Vs. closed systems

First and second order differential

MATH 3113. Differential equations
equations

Use of software
Systems of algebraic equations
ChE 3723. Numerical methods
Numerical differentiation
Numerical integration
 12

Aspects of ChE 4473

Course Activities

Lectures Tue, Thur

In-class problem solving

Tue, Thur
(bring your laptop)

Quizzes on chapter readings

Home and in-class
Homework problems
Submitted to Canvas
In EXCEL and
(handwritten + pdf) files
ON-LINE (Canvas)
e.g. Thursdays 11:59 PM
Fixed Deadline
NO LATE WORK ACCEPTED

Thursday (3:00-6:00 PM)

Office Hours
Sarkeys (T 327)
 13

Aspects of ChE 4473

In Canvas, you can find

1. Syllabus 2. Lecture Notes

3. Homework 4. Homework
Assignments Solutions
6. Quiz
5. Quizzes
Solutions

7. Screencast videos 8. Study guides

 14

Some rules of courtesy and respect

While, class attendance is not mandatory, we definitely
encourage class attendance every period.

But it is implicit that if you attend you

should pay attention and participate in
class activities

We encourage use of smart phones, tablets, and

laptops in class for course-related
activities.

However, any other use (texting,

browsing, playing games, passing
solutions (cheating)) is strictly
forbidden.
Important: Homework & Exams Submission Format
15

HW: Handwritten papers è pdf files. ( be NEAT and CLEAR )

(1) Write down the RATE EQUATIONS including stoichiometry

A⇋B A→C 2B+C→3D Care

taki ful wh
ng en
(2) Identify RATE LAWS including kinetic parameters the h picture
an d s
writ of
pape ten
r1 = k1 CA - k-1 CB k1 = 93 h-1 rs
k-1 = 56 h-1
r2 = k2 CA k2 = 53 h-1
r3 = k3 CB CC k3 = 3564 h-1 L mol-1

(3) Determine whether the problem must be solved in terms of volumetric flow rates,
conversion, or molar flow rates; is it gas or liquid (partial pressures or
concentrations); does it have volume expansion or not … etc

(4) Include a schematic DIAGRAM of the reaction system, indicating known and
unknown terms
PT VR
Watch examples FA0 FA
in Screencasts !! yA0
(5) Write down Molar Balance ( one for each component ):

(A) dFA/dV = rA = - r1 – r2
(B) dFB/dV = rB = r1 – r3 Do n
(C) dFC/dV = rC = r2 – r3 ’t l
o se
(D) dFD/dV = rD = r3 po i
nts
Ci = yi C0 …
(6) Make all necessary conversions and = yi P0 /RT
Transformations:
Where yi = Fi /∑Fj

(7) Numerical Solution (spell out how you prepared your EXCEL spreadsheet):
e.g Euler Solution: è ΔFi = ri ΔV

Volume FA FB FC FD Ci r1 r2 r3 .
0 FA0 0 0 0 (Fi /FT) P/RT ki Cin … ...
Initial values

1 FA0 + ΔV rA … … … … …
Numerical integration equations
Important !
(8) Sketch out the graph you obtained in EXCEL

Molar Flow Rate label all axes and curves

FA

FCFC

FB FFD
D

Space Time (V/F)

 More about homework submission

• Be considerate with the person grading your work.

• The TA is grading ~ 100 assignments each week. If you send 10

separate pictures, the TA have to open 1000 files ! rather than
scrolling a single pdf.
è So, compile your work in a single pdf file.

• If your file is large ( 128 MB !) it takes time to open and downloading

è Reduce file size

• If you send your image upside down, it takes the TA much more
effort to edit your submission
è Make sure it reads well when opened

• If you send your work in Excel format only, without a written portion,
the TAs get confused. They can’t go over each of the cells in your
spreadsheet to see what you have done?
è Explain your procedure in the pdf file. Individual
No explanation, no credit work !
 About homework timing

No LATE SUBMISSIONS ACCEPTED

• On line submission (ONLY) Do not send HW to the instructor by email !!!

Typically, you will have 1 week between the day the HW is

assigned and the day it is due.

So, you should plan your timing as follows:

• Start to look at the assignment the same day it is posted

• Don’t wait until last minute ! Rather, complete all problems the day
before assignment is due.

• Make good use of office hours so you can clarify all your doubts
( highly recommended ! )
 Cheating is Academic Misconduct

• Working in groups to discuss HW assignment is OK,

cheating is NOT.
• HW and on-line-quizzes are intended as learning tools.
• Actual evaluation of student progress is done in the exams.
• Students are given these exercises to prepare more
effectively for exams.
• Getting 100 in a quiz or HW by copying without
understanding does not help anyone.
• If someone sends you a txt msg with 1(a), 2(c) … and that’s
how you answer the quiz you haven’t gained anything
 Grading

• Homework 5%
• On-line Quizzes 2%
• In-class problems and quizzes 3%
• Two 3-hour Tests 60 %
o Exam No. 1 FEB 20th DAH 218
( 7:00 – 10:00 PM )
o Exam No. 2 APR 23rd DAH 218
( 7:00 – 10:00 PM )
• Final Exam (comprehensive) 30 %

Exams
Part A. Conceptual problems (analytical solutions) and questions
Closed book / closed notes – No calculator – no computer 1.5 h
Part B. Numerical problems (EXCEL)
Open book - open notes – Computers and Calculators allowed 1.5 h
No phones – no Internet 21
 22

Structure of the course

Non-isothermal reactors
Multiple reactions: series, parallel
Analysis of rate data, regression analysis
Special reactors: semibatch, membrane, recycle
Design of chemical reactors: PFR, CSTR, batch

Mole Balance Rate Laws Stoichiometry Energy Balance

 Part 1 (material covered in Exam 1)

Chapter Topics

1 Introduction to CRE – Definitions – Chemical Equilibrium Thermo

Vs. Kinetics – Mole Balances Batch Vs. Flow reactors (BR, CSTR, PFR).
Reactor sizing as f(rate).
---------------------------------------------------------------------------------------------------
2 Conversion and reactor sizing – reactor (BR, CSTR, PFR) sizing as f(x).
Levenspiel graphs
---------------------------------------------------------------------------------------------------
3 Rate Laws. Reaction order. Rate constant. Activation energy. Arrhenius
equation. Reaction mechanisms. Transition state theory. Reversible reactions.
---------------------------------------------------------------------------------------------------
4 Stoichiometry (Bookkeeping). Effect of change in No. moles on
concentration Vs x. Differences between liquid and gas phase cases
---------------------------------------------------------------------------------------------------
5 Isothermal reactor design è Conversion (Gas phase Vs. Liquid phase)
Pressure drop.
---------------------------------------------------------------------------------------------------
6 Isothermal reactor design è FA, FB, FT (Gas phase Vs. Liquid phase)
---------------------------------------------------------------------------------------------------
 Part 2 (material covered in Exam 2)

Chapter Topics

7 Collection and analysis of rate data. Different methods. Differential and

integral. Differential Vs. integral reactor. Fitting for obtaining kinetic parameters.
---------------------------------------------------------------------------------------------------
8 Multiple reactions. Parallel Vs. series reactions . Complex reactions in
PFR (integrate with Fi’s) – in CSTR (system of equations)
---------------------------------------------------------------------------------------------------
10 Catalysis and catalytic reactors. Adsorption, surface reactions (Langmuir)
Deriving rate expressions for catalytic reactions at surfaces.
Mass transfer and reaction – External and Internal mass transfer
Effectiveness Factor
---------------------------------------------------------------------------------------------------
11 Nonisothermal reactor design. Energy balance. Adiabatic reactors.
Reactor staging endo Vs, exothermic reactions
---------------------------------------------------------------------------------------------------
12 Nonisothermal reactor design. Energy balance. Heat-exchange reactors.
Multiple steady state. Non-isothermal multiple reactions.
PFR, CSTR, Safety, explosions
 25

Reaction Rate (r)

AàB (1)
r = rate of occurrence of reaction 1 (as written)
moles converted per unit V and unit t
(always a positive quantity)
rA = - r = rate of change of species A
(in a reactant, it is a negative quantity)
rB = + r = rate of change of species B
(in a product, it is a positive quantity)

• r is a function of concentration, temperature, pressure, and the type

of catalyst (if any)
• r is independent of the type of reaction system
(batch, plug flow, etc.)
• r is an algebraic equation, not a differential equation
(e.g. r = kCA or r = kCA2)
 26

STOICHIOMETRY
stoichiometric coefficients

½ A2 + ½ B 2 è C or A2 + B2 è 2 C or - A2 - B2 + 2C = 0

So, generalized single reaction S nj Aj = 0

where:
nj = stoichiometric coefficient > 0 for products e.g. 2 (for C)
< 0 for reactants e.g. -1 (for A2 and B2)

Many times, rate law is given as a generic equation r = k CA CB

With r = rate of occurrence of reaction as written)
Watch Screencast
“CONVERSION & Example:
EXTENT OF
A2 + B2 è 2 C
RXN”
rA2 = - r rB2 = - r rC = 2 r

So, r = rA2 = rB2 = rC = r = rj / nj

(-1) (-1) (2)
 27

Units of rate constant (k)

IMPORTANT: units of k are those needed to make units

of r meaningful.

rate [ moles / liter . min ]

if r = k Cn
[ moles / liter . min ] = [ ? ] [ moles/ liter ] n

k [ liter (n-1) mole (1-n) min -1 ]

Example: second order reaction è r = k CA2

r [ mol / liter min ] è then

k [ mol / liter min ] or [ 1 / min ] or [ liter ]
(mol/liter)2 (mol/liter) (mol min)
 28

Reversible Reactions

A + B ⇄ C + D

r = rforward - rreverse

r = kf CA CB - kr CC CD

at equilibrium r=0

then, kf / kr = (CC CD) / (CA CB)

Kc = (CC CD) / (CA CB)

 29

Kinetics Vs. Thermodynamics

• Thermodynamics: equilibrium systems, no net change

with time è It tells us: Can it happen ?

• Kinetics: Chemical changes, and energies and

masses associated with them. Reaction rate
expressions.
è It tells us: How fast does it happen ?

• Thermodynamic concepts needed in this course:

– Equilibrium constants, and equilibrium compositions
– Enthalpy changes accompanying reactions
– Energy balances
 30

CHAPTER 1

Objectives

• Analyze mole balance in reacting systems

• Introduce concept of ideal reactors:

(A) Discontinuous Batch

Reactors
(B) Continuous Reactors:
• tank
• tubular
• packed bed
 31

Material Balance for a Species i

Control volume
t i
t pu
Ou
Inp
ut
i
accumulation
dNi /dt

New term: GENERATION/

CONSUMPTION
by reaction
 32

Material Balance for a Species i

Input – output + generation = accumulation

t i
t pu
Ou
Inp
ut
i
enters
accumulaHon
built up within the system

through dNi /dt exits

system built up within the system through
boundaries system
boundaries

G = amount of i GENERATED
(or CONSUMED) by reaction
 33

Material Balance for a Species i

Expressed
in terms of
rates, i.e.
moles/time

[input] – [output] + [generation] = [accumulation]

Fio - Fi + V . ri = dNi/dt
[mol/min] [mol/min] [ L . mol/L min] [mol/min]

Ordinary Differential Equation (ODE)

 34

Material Balance for a Species A (reactant)

This reaction,
as written,
occurs at a rate r
Aè2B
r = rB/2 = - rA
[input] – [output] + [generation] = [accumulation]
FAo - FA + V . rA = dNA/dt
Since A is a reactant è rA = - r
So, in steady state:
FAo - FA = - V rA = V r

positive positive
 35

Material Balance for a Species B (product)

This reaction,
as written,
occurs at a rate r
Aè2B
r = rB/2 = - rA
[input] – [output] + [generation] = [accumulation]
FBo - FB + V . rB = dNB/dt

Since B is a product è rB = 2 r
So, in steady state:
FBo - FB = - V rB = - V 2 r

negative negative
 36

Attention: Source of confusion in problems

Aè2B
If this reaction, r = rB / 2 = - rA
as written,
occurs at a rate So, rA = - r r in each case will
r = k CAn be different, but in
rB = 2 r both cases
rB = - 2 rA

That’s why in most

½AèB problems we either
If this reaction, make nA= - 1
as written, r = rB = - rA / (½) or just report (-rA)
occurs at a rate
r = k CAn So, rA = - r / 2
rB = r
 37

What
Reactor
we have
Design
learned
Problems
so far ?

Most Chemical
Reactors

Solve Numerically

Multiple Reactions
Number of mole
balance equations =
Number of components

Complicated
Rate Laws
Additionally, we need
an energy balance

Non-Isothermal
Solving Differential Equations

Two methods:
A. Analytical Solution
(You may use Wolfram Alpha)
B. Numerical Method
(use EXCEL)

Example:
Solve the differential equation:
dy/dx = x / (1+x)
With y(0)=0
Make a plot of y vs. x for the range x = 0-1
A. Analytical (use Wolfram Alpha)

http://www.wolframalpha.com

To get the constant, we use the boundary condi:ons.

If y (x=0) = 0 y (0) = 0 - ln (0+1) + c = 0 èc=0
So y (x) = x – ln (x+1)
A. Analytical (use Wolfram Alpha)

0.35

0.3
y 0.25
y (x) = x – ln (x+1)

0.2

0.15

0.1

0.05

0
0 0.2 0.4 0.6 0.8 1
x
B. Numerical Method (Euler with EXCEL)

dy/dx = Δy / Δx = f(x)

So, Δy = f(x) * Δx
B. Numerical Method (Euler with EXCEL)
0.26%
0.258%
0.256%
0.254%
0.252%
0.25%
0.248%
0.246%
0.244%

Blue Line: Blue Line:

0.242%
0.24%
Analytical Solution Analytical Solution0.8% 1%

Integration step size = 0.2 However, with

Too large Integration step size = 0.01
Poor approximation to real solution Approximation is excellent !
 43

(A) Discontinuous Batch

Reactors
(B) Continuous Reactors:
• tank
• tubular
• packed bed
 44

Reaction Systems: Batch System

DISCONTINUOUS

The stomach

A closed lake
 46

t=0
Batch NA = NA0
Reactor later,

NA = f(t)
 47

Reaction Systems: Flow System

CONTINUOUS

CSTR
Pool with flowing water
 48

FA0

CA inside is
constant
Continuous
Flow Stirred Mole Balance of
Tank Reactor species A:
(CSTR) FA0 – FA = (- rA) V
CA

FA

CA
 49

Reaction Systems: Flow System

CONTINUOUS

The intestines

A river
 50

Reaction Systems: Flow System

CA Plug-Flow Reactor
(PFR)
Tubular

FA

FA0
 51

Comparison of Flow Reaction Systems

In a well stirred tank, all the system
variables (e.g., temperature, catalytic activity, and
concentration of the chemical species) are
spatially uniform throughout the system volume.
By contrast, in a tubular reactor the system variables
change with position in the volume. That is, the rate has a
value at location 1 different from the value at location 2.

We can choose the volume . r (z)

j

small enough so the rate is

constant
è “control volume”
 52

Ideal reactors: Batch Vs. Flow

Plug-Flow
Reactor
Batch (PFR) Mixed-Flow
Reactor Reactor
(BR) (MFR) or (CSTR)
 54

QUIZ: Volumetric and Molar Flow Rates

A
B

A liquid stream of A and B is fed into a reactor at a volumetric flow of 2.5

L/min. The density of A, B and the liquid mixture is 1.5 kg/L, while the
molecular weights of A and B are 50 and 60 g/mol, respectively. Calculate
the molar flow rate of each reactant going into the reactor (FA0 and FB0).

Solution
CA0 = rA = 1500 g/L = 30 mol/L.
MWA 50 g/mol
CB0 = rB = 1500 g/L = 25 mol/L
MWB 60 g/mol
FA0 = v0 x CA0 = 2.5 L/min x 30 mol/L = 75 mol/min.
FB0 = v0 x CB0 = 2.5 L/min x 25 mol/L = 62.5 mol/min.
 55

QUIZ: Volumetric and Molar Flow Rates

Ideal gas
PV = N R T
A
P = N =C B
RT V

A gaseous stream of A and B is fed into a reactor at a constant pressure of

10 atm and temperature of 727 C. The reactants (A and B) are introduced
with equal initial concentrations and volumetric flow of 2.5 L/min.
Assuming they are ideal gases, calculate the molar flow rate of each
reactant going into the reactor (FA0 and FB0).

Solution

CA0 = pAo . = yAoP = 0.5 x 10 atm .

RT RT (0.082 atm L/mol K x 1000K)
CA0 = 0.061 mol/L = CB0

FA0 = FB0 = v0 x CA0 = 2.5 L/min x 0.061 mol/L = 0.17 mol/min