Introduction to Chemical Reaction Engineering

Aims:
To introduce and develop an understanding of reaction rate kinetics and the
application of this understanding to the design of a chemical reactor.

Learning Outcomes
By the end of the module the student should be able to:
 Derive simple differentiated and integrated rate equations for series, parallel and
reversible chemical reactions.
 Explain the development of the theories resulting in the Arrhenius temperature
dependence of reactions rates.
 Apply quantitative methods to design and size reactors (batch, CSTR and PFR)
for simple chemical reactions schemes.

Learning Resources

• Fogler HS, Elements of Chemical Reaction Engineering, 4th Edition, Prentice-Hall,

2005 (This book is the key text. Only the first six chapters will be used but CRE in
the second year will follow on from this. The 3rd edition is also useful.)

http://www.engin.umich.edu/~cre/index.htm (This is the website associated with the

text book and contains a large amount of supplementary material from lecture notes
and derivations to example problems and further learning resources)

http://vig.prenhall.com/samplechapter/0135317088.pdf (This is a pdf file of Chapter 1

of the 3rd Edition of Fogler)

• Metcalfe IS, Chemical Reaction Engineering – A First Course, OUP 1997 (An
inexpensive, accessible book which goes deeper into the subject than this
introductory course)

• Levenspiel O, Chemical Reaction Engineering, 3rd Edition, Wiley 1998

• Pilling MJ and Seakins PW, Reaction Kinetics, 2nd Edition, OUP 2000 (excellent
from the chemistry aspects including reaction mechanisms and complex reactions)

• http://www.chm.davidson.edu/ChemistryApplets/kinetics/ReactionRates.html (good
to investigate basics of reaction kinetics with animated experiments)

1
Lecturer:

Dr Sam P. de Visser
Room 3.013 Manchester Institute of Biotechnology (MIB)

Email: sam.devisser@manchester.ac.uk

Outline Synopsis

1. Introduction to CRE
Importance of CRE
Example application areas
Basic definitions

2. General mole balance for ideal reactors

Ideal reactor types: batch, CSTR, PFR

3. Rate Laws and stoichiometry

Relative rates of reaction, Reaction order, Rate limiting, Half life, Stoichiometric
tables, Conversion

4. Theories of reaction rates

Temperature dependence of reaction rates
Arrhenius, collision theory, transition state theory

5. Collection and analysis of batch reactor rate data

Determining reaction order: Differential method of analysis, Integral method, Method
of initial rates, Method of half-lives
Zero order, 1st order irreversible, 2nd order

6. Complex reactions
Reversible, parallel, series

7. Reactor design and sizing

Sizing reactors
Choice of reactor
Reactors in series

2
 Nomenclature

A pre-exponential/frequency factor
Cj molar concentration of species j (mol m–3 or dm–3)
E activation energy (J mol–1)
k reaction rate constant (units depend on order)
nj molar flow rate of species j (mol s–1)
Nj number of moles of species j (mol)
rj rate (mol m–3 s–1)
t time (s)
t1/2 half-life (s)
 volumetric flow rate (m3 s–1)
V volume (m3)
X conversion (-)

Subscripts:
e exit
o input
T total

3
 Introduction to Chemical Reaction Engineering (CRE)

Ideal Reactors

Synopsis
General mole balance equation for ideal reactors
Assumptions used in ideal reactors
Design equations for ideal reactors

Learning outcomes:
 Describe the assumptions used in ideal reactors.
 Derive the general mole balance equation.
 Apply the general mole balance equation to the three most common types of reactors.

Definitions of reaction rate

Reaction rate, rj: moles of j appearing (or formed) because of the reaction per unit volume of
reacting mixture per unit time (molj/m3 s)

• If j is reacting (disappearing), rate is –ve (i.e. = –rj)

• If j is product (appearing), rate is +ve (i.e. = rj)

• Several sign conventions – take care!

Reaction Equation or Rate Law

An algebraic equation that is solely a function of the properties of the reacting materials and
reaction conditions (e.g. species concentration, temperature, pressure or type of catalyst) at
any point in the system.
The rate equation is independent of the type of reactor (e.g. batch or continuous flow) in
which the reaction is carried out.

A → products

It may be a linear function of concentration: –rA = kCA

or it may be some other algebraic function of concentration:

kC
–rA = kCA 2 or  rA  1 A
1  k 2C A

The concentration dependence must be determined from experimental observation

–rA = kCA An example of a first order reaction

–rA = kCA 2 An example of a second order reaction

k is called the rate constant. It varies with temperature.

4
Ideal Reactors
Model reactors, or ideal reactors, approximate the real thing. In this course we are to going
study three types of ideal reactor: the batch reactor, the continuously stirred tank reactor
(CSTR) and the plug flow reactor (PFR).

Batch Reactors

NA moles of A

Uses:
 Small-scale operation
 Testing new processes
 Manufacture of expensive products
 For processes difficult to convert to continuous

Advantages:
 High conversions by leaving reactants in reactor

Disadvantages:
 High labour costs
 Variability of products (batch to batch)
 Difficulty of large scale production

Assume:
 Well-mixed – Uniform composition at any time.
 Often assume constant V and constant P
 All reactants In at t = 0 and out at t = t

5
Continuously Stirred Tank Reactor (CSTR)

Inflow (reactants)

Outflow (products)

Assume
 Continuous supply of feed and product removal
 Well-mixed
 Steady-state – reaction rate the same everywhere and time independent.
Concentration the same everywhere so exit point the same
Products = reactor contents

Can use in series

Plug flow reactor (or tubular reactor)

reactants products

• Continuous supply of feed and product removal

• Complete radial mixing
– ‘flat’ velocity profile
• No axial mixing (‘plug’ flow)
• Steady state (?)
• Concentration varies along length
• No moving parts
• Mainly gas phase

6
General Mole Balance for Ideal Reactors

Now that we have been introduced to the three ideal reactors, batch, CSTR and PFR we can
apply a general mole balance to each of them. The mole balance can be written as:

In - Out + Generation = Accumulation

Rate of 
  Rate of 
Rate of  Rate of  generation   
flow of j in   flow of j out   of j by chemical   accumulati on 
      of j 
(moles/time)  (moles/time)  reaction  (moles/time) 
(moles/time)   

dN j
nj0 - nj + Gj =
dt

nj is the number of molar flow of species j.

If all the system variables (e.g. temperature, concentration) are spatially uniform throughout
the volume of the reactor then G is the product of reaction volume, V, and the rate of
formation of j, rj:

Gj = rj V

moles moles
 .volume
time time.volume

We can develop the design equations for ideal reactors in the following way:
Determine the time (for a batch reactor) or reactor volume (flow reactor) required to convert a
specified amount of reactants into products.

nj0 nj

Let’s consider the batch reactor first.

7
Mole Balance applied to Batch Reactors

NA moles of A

Apply Mole Balance

There is no inflow or outflow in a batch reactor, so

nj0 = nj = 0

Rearranging then gives us:

dN j
r jV  2.1
dt

For a constant volume V batch reactor we can take V to the right hand side and express the
rate in terms of the changing concentration, Cj:

1 dN j d ( N j / V ) dC j
rj   
V dt dt dt
Consider the reaction A → B

Mole-time trajectories
NA0
NB
NA
NA1 NB1

t1 t t1 t

Rearranging equation 2.1 for species A:

dN A
dt 
rAV
Integrating with limits at t = 0, NA = NA0 and t = t1, NA = NA1

8
 N A1
dN A
t1   rV
N A0 A

Substitute the rate law:

–rA = kCA (Rate equation for a 1st-order reaction)

–rAV = kCAV

= k(NA/V)V

= kNA

NA0
dN A
t1  
NA1
kN A
(Note the reversal of integral limits for the minus sign)

1 N A0
t1  ln
k N A1

Try substituting a second order rate equation –rA=kCA2

Mole balance applied to CSTR

nA0
CA0
T0 (m3/s)

CA nA
CA
T (m3/s)
Exit – representative of
contents

Assumptions
 Continuous supply of feed and product removal
 Well-mixed
 Steady-state – reaction rate the same everywhere and time independent.
Concentration the same everywhere so exit point the same

9
 CA

Design equation
Apply the mole balance with the assumption of steady state:

dN j
 0 (steady state)
dt
So
nj0 - nj + rj V = 0

Rearranging
n j0  n j
V 
 rj

This is the reactor volume required to reduce the entering flow rate, nj0 to nj when species j is
disappearing at a rate, –rj.

Molar flow rate

nj = Cj.  volumetric flow

moles moles volume


time volume time

Combining
 0 C j 0  C j
V
 rj
For a 1st-order reaction A → B (–rA=kCA and nA=CA

 C  C A
V  0 A0
kCA

10
 Mole Balance applied to Plug Flow Reactor (PFR)

Used mainly for gas phase reactions – may be packed with catalyst

reactants products

Assumptions
 Plug flow – no radial variations in velocity, concentration or temperature (‘flat’ velocity
profile)
 Steady state
 Continuous supply of feed and continuous product removal

Consider the mole balance on j in a differential segment of reactor volume V

nj0 nj|V+V nj
nj|V

V V+V

V
Applying the mole balance:

In - out + generation = accumulation

nj|V - nj|V+V + rjV = 0

Divide by V
n j|V  V  n j|V
 rj
V

In the limit V → 0

dn j
 rj
dV

11
Consider the reaction A → B again:

nA0

nA
nA1

V1 V

What is the reactor volume V1 necessary to reduce nA0 to nA?

dn
dV  A
rA
Integrating with limits at V = 0, then nA = nA0 and V = V1, nA = nA1
n A1 nA0
dn A dn A
V1    
nA0
rA n A1
 rA
For a 1st-order reaction (–rA=kCA and nA=CA
 nA0
dn A  A 0 dn A
n

 V   kCA k n n A

 n A1 A1


 n  C
V  ln A0  ln A0
k nA k CA

Compare this result with that of a batch reactor.

Summary
The key design equations have been derived for each type of ideal reactor using the
assumptions involved in the ideal reactor definitions. Additionally, the expressions have been
derived to determine the time or volume required to achieve a reactant concentration for 1st-
order reactions.

12
 Conversion in ideal reactors
Topics:
Definition of reaction conversion.
Conversion in batch reactors
Conversion in flow reactors

Learning outcomes:
 Define conversion
 Show how to obtain the rate of reaction as a function of conversion
 Write the mole balances in terms of conversion for a batch reactor, CSTR, PFR.

Definition of conversion

Consider the reaction:

aA + bB → cC + dD

Chemical species
Stoichiometric
coefficients

Take species A as the basis of calculation so divide through by the coefficient of A

A + b/aB → c/aC + d/aD

Every quantity is now ‘per mole of A’

We can now ask,

 How can we quantify how far the reaction proceeds to the right?
 How many moles of C (or D) are formed for every mole of A consumed?

To answer these questions it is convenient to use a parameter: conversion

Conversion is defined as:
moles of A reacted
XA 
moles of A fed

Usually drop subscript A so X ≡ XA

For irreversible reactions, at the start X = 0, at the end X = 1

For reversible reactions, the maximum conversion is the equilibrium conversion Xe.

Let’s now consider the application of conversion to our ideal reactors.

13
Conversion in batch reactors

moles of A reacted   moles of A reacted 

(consumed)   moles of A fed x  moles of A fed 
   
 N A0 X

The number of moles of A that remain in the reactor after time, t, NA is

moles of A 
moles ofA   moles of A 
in reactor   initially fed   consumed 
   to reactor at   
at t      by reactor 
t  0 

N A  N A0  N A0 X  N A0 (1  X )

This can be rearranged

N A0  N A dN A
X  so dX  
N A0 N A0
When V is constant

C A0  C A dC A
X  so dX  
C A0 C A0

Differentiate the boxed equation with respect to time:

0
dN A dN A0 dX dX
  N A0   N A0
dt dt dt dt

The design equation for a batch reactor is

dN A
 rAV
dt

Combining gives the design equation in differential form

dX
rAV   N A0
dt

To determine the time to achieve a specified conversion X we must separate the variables

dX
dt  N A0
 rAV

14
 X
dX
t  N A0 
0
 rAV

This is the integral form of the design equation.

Consider the case of a 1st-order rate law.

rA = –kCA

rA = –kNA/V

–rAV = kNA
So
X
dX
t  N A0 
0
kN A

By definition, NA = NA0(1–X)
X X
dX 1 dX
t  N A0   
0
kN A0 (1  X ) k 0 (1  X )

t
1
 ln(1  X )0X  1  ln(1  X )  ln 1
k k

1
t   ln(1  X )
k

Conversion in Flow Reactors

Batch – conversion increases with time spent in the reactor

CSTR – conversion increases with volume
PFR – conversion increases with length

Molar flow rate at which species A is reacting within the entire system is nA0X:

moles of A fed moles of A reacted

n A0 X  .
time moles of A fed

moles of A reacted

time

Molar feed rate of A to the system minus the rate of reaction in the system equals molar flow
rate leaving

15
 molar flow rate  molar flow rate molar flow rate
at which A is fed   at which A is   at which A 
     
 to the system  consumed  leaves 

nA0 - nA0X = nA

Rearranging

nA = nA0(1 – X)

nA0 = CA00 0 is the volumetric flow

For gases CA0 can be calculated from the entering temperature and pressure conditions using
the ideal gas law
P y P
C A0  A0  A0 0
RT0 RT0

PA0= partial pressure

P0 = total pressure
yA0 = mole fraction

CSTR design equations for conversion

Design equation

n A0  n A
V
 rA

Substitute nA =nA0 – nA0X

n A0  ( n A0  n A0 X )
V
 rA

n A0 X
V
 rA

Because the reactor is perfectly mixed, the exit composition is the same as in the reactor so
the rate of reaction is evaluated at the exit conditions.

For a 1st-order reaction A → B (–rA=kCA and nA=CA

n A0 X
V
kCA

16
Mean residence time (Holding time or space time)

V

0

V = reactor volume
0 = volumetric flow rate entering

It is the time necessary to process one volume of reactor fluid at the entrance conditions

For a CSTR, nA0 = CA00

Rearranging,

C A0 0 X
 rA 
V

C A0 X
 rA 


PFR design equations for conversion

Starting from the design equation

dn A
 rA
dV

Substitute nA =nA0 – nA0X for a flow system

Differentiating, dnA = –nA0dX and substituting

dX
n A0  rA
dV

The integral form is obtained by separating the variables

X
dX
V  n A0 
0
 rA

The mean residence time for a 1st –order reaction

–rA = kCA

17
But CA = CA0(1–X) for constant volume

So

X
dX
V  n A0 
0
kCA0 (1  X )

Taking out the constant terms from the integral:

X
n A0 dX
V
kCA0  (1  X )
0

Integrating and taking nA0 = CA00

C A0 0
V  ln(1  X )
kCA0

V 1
   ln(1  X )
0 k

Compare with batch system where this equals t.

18
 Application of the Design Equations for Flow Reactors

Topics:
 Application of the design equations for flow reactors
 Sizing reactors
 Comparison of reactors, variable volume

Learning outcomes:
 Size reactors given the molar flow rate of A, and the rate of reaction, –rA, as a function of
conversion, X.

Introduction
The aim of this part is to use the knowledge of the rate of reaction, -rA, as a function of
conversion, X, to size CSTRs and PFRs. If we remind ourselves of the design equations
involving conversion for the CSTR and PFR for the reaction A → B
:

X
n A0 X dX
CSTR V PFR : V  n A0 
(rA ) 0
 rA

It can be seen that the reactor volume varies as 1/–rA

Let’s look at some real data for an isothermal reaction with conditions:
T = 500K, P = 8.2 atm, nA0 = 0.4 mol/s

X –3
(–rA)(mol m s )
–1 3
(1/–rA)(m .s/mol)
3
nA0/–rA (m )
0.0 0.45 2.22 0.89
0.1 0.37 2.7 1.08
0.2 0.3 3.33 1.33
0.4 0.195 5.13 2.05
0.6 0.113 8.85 3.54
0.7 0.079 12.7 5.06
0.8 0.05 20 8

We can plot nA0/–rA (m3) as a function of X.

19
 Levenspiel plot

9
8
7
6
nA0/-rA

5
4
3
2
1
0
0 0.5 1

This is called a Levenspiel plot.

We can now apply this data to both a CSTR and a PFR

1. CSTR

How can we calculate the volume, V, of a CSTR to give 80% conversion?

From the data above when X = 0.8, 1/–rA = 20 m3s/mol

If we substitute these values into the CSTR design equation then we can determine the
volume:

n A0 X  mol   m3 s 
V  0.4  x 20 x 0.8  6.4m 3 or 6400 dm 3
 rA  s   mol 

The volume is equal to the area of a rectangle of height (0.4  20 = 8 m3) and base (X = 0.8)
on the Levenspiel plot:

8 m3
Levenspiel CSTR plot

nA0/-rA
V =6.4 m3

0.8
X

20
2. PFR

You will note that the design equation for the PFR contains an integral. The required volume
can therefore be determined from the area under the nA0/(–rA) curve.

X
dX
V  n A0 
0
 rA

Levenspiel PFR plot

nA0/-rA
V =2.165 m3

0.8
X
The integration can be performed using the trapezium rule (or Simpson’s rule) with known
data points. Alternatively count/estimate the area on graph paper. For this example the
volume is V = 2.165 m3 = 2165 dm3

PFR and CSTR Comparison

From the above example it can be seen that the CSTR volume required is greater than the
PFR volume for the same conversion and reaction conditions. Why is this?

The CSTR is always operating at the lowest reaction rate due to the low concentration
(perfect mixing assumption) and thus always operating at the lowest rate.

The PFR starts at a high rate and goes to a low rate and so overall is more efficient at
processing the reaction. This is true in general for all isothermal reactions (for the non-
isothermal case it is more complicated).

Reactors in series
Putting CSTRs in series reduces the volume required. An infinite number in series is
equivalent to a PFR.

Putting PFRs in series is the equivalent of a longer PFR.

21
Summary of design equations for ideal reactors
Differential Algebraic Integral
Batch dN A NA
dN A
 rAV t 
dt
NA0
 rAV
dX X
dX
N A0  rAV t  N A0 
dt
0
 rAV
CSTR n A0  n A
V
 rA
n A0 X
V
 rA
PFR dn A nA
dn A
 rA
dV
V 
nA0
rA
dX X
dX
n A0  rA V  n A0 
dV
0
 rA

22
 Rate Laws and Stoichiometry

Relative rates of reaction

Stoichiometric tables
Reaction rate, rate law
Reaction order
Rate limiting

Learning outcomes:
 Relate the rate of reaction to the concentrations of reacting species
 Write the relationship between the relative rates of reaction.
 Write a rate law and define reaction order.
 Write –rA solely as a function of conversion given the rate law and then entering
concentration.
 Set up a stoichiometric table for both batch and flow systems and express concentration
as a function or conversion.

Relative Rates of Reaction

Consider the following generic reaction:

aA + bB → cC + dD

or A + b/aB → c/aC + d/aD

So every mole of A consumed gives c/a moles of C

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

= c/a (–rA)

We can then write

–rA/a = –rB/b = rC/c = rD/d (Note signs)

E.g. 2NO + O2 → 2NO2

–rNO/2 = –rO2/1 = rNO2/2

If NO2 is being formed at a rate of 4 moldm-3s-1

Then rate of formation rNO = (–2/2) rNO2

= –4 mol dm–3 s-1

Rate of disappearance , –rNO = 4

Rate of disappearance, –rO2 = (–1/–2)rNO2 = 2

23
Stoichiometric tables for conversion
If we again consider
A + (b/a)B → (c/a)C + (d/a)D

We can express the number of remaining moles in the reaction vessel in terms of conversion
X in a stoichiometric table:

Species Initial Moles Change in moles Remaining moles

A NA0 –( NA0X) NA=NA0-NA0X
B NB0 –(b/a)( NA0X) NB=NB0–(b/a)NA0X
C NC0 (c/a)( NA0X) NC=NC0+(c/a)NA0X
D ND0 (d/a)( NA0X) ND=ND0+(d/a)NA0X
I (inerts) NI0 – NI=NI0
Totals NT0 NT=NT0+(d/a+c/a–b/a–1) NA0X

(d/a+c/a–b/a–1) =  Change in total number of moles per mole reacted (Note variable
volume reactions)

Concentrations can be determined by dividing by V.

Reaction Rate Equation or Rate Law

–rA depends on concentration and temperature
–rA = k(T)  f(CA, CB,…) k(T) rate constant
The rate constant is constant at each temperature.

The rate law must be determined experimentally

The common form of the rate law is:

–rA = kACA CB

 – order with respect to A

 – order with respect to B

Order of reaction – power to which the concentrations are raised in the rate law

Overall order of reaction: n =  + 

e.g. 2NO + O2 → 2NO2

–rNO = kACNO CO2

overall order n = 2 + 1 = 3rd order

2nd order w. r. t. NO
1st order w. r. t. O2

24
Units of k

k
concentration 1n
time

n=1 (mol dm–3)0 s–1 = s–1

n=2 (mol dm–3)–1 s–1 = mol–1 dm3 s–1

n=0 (mol dm–3)+1 s–1 = mol dm-3 s–1

An elementary reaction is one that involves a single step

e.g. H + Br2 → HBr + Br

rate = k[H][Br2]

The reaction order follows from the stoichiometric coefficients

Some non-elementary reactions have stoichiometric coefficients identical to the orders.

e.g. 2NO + O2 → 2NO2

rate = kACNO CO2

Some non-elementary complex, multistep reactions appear simple

e.g. H2 + Br2 → 2HBr

rate proportional to k[H2][Br2]1/2 free radical mechanism

Therefore the rate law and reaction order must be determined experimentally

Rate limiting reactions

If a reaction has several steps then the rate limiting (or rate determining) step is the slowest
reaction. (see series reactions later)

25
 Experimental Determination of Reaction Rate Information

Determining reaction order

Differential method of analysis
Pseudo-order rate laws
Integral method: 1st order irreversible, zero order, 2nd order
Method of initial rates
Method of half-lives

Learning outcomes:
 Determine the order of a reaction from concentration/time data using the differential
method.
 Prove a given reaction order from concentration/time data using the integral method for
zeroth, first and second order reactions.
 Determine the order of reaction using the initial rate of reaction.
 Show how measurements of the half-life can give reaction order.

Introduction
As stated in the previous lecture, it is essential to determine the reaction rate equation
experimentally. This lecture looks at several approaches to experimentally evaluating rate
data.

A. Determination of reaction orders by inspection

In some cases the reaction order can be determined by inspection:

Example 1.
[CA] 1.0 2.0 4.0 12.0
Rate 0.05 0.10 0.20 0.60

Rate doubles when concentration doubles

Rate = k[CA]1 1st order
Determine k using all data

Example 2.
[CA] 4.0 8.0 16.0 32.0
Rate 3.0 12.0 48.0 192.0

When concentration doubles, rate increases by factor of 4

Rate = k[CA]2 2nd order

Example 3.
[CA] 6.0 12.0 24.0 48.0
Rate 5.0 4.9 5.1 5.0

Changing the concentration, the rate stays the same

Rate = k[CA]0 zero order

Unfortunately it is not always so obvious

26
B. Differential Methods of Analysis

B 1. For rates dependent on the concentration of only one species

Another approach is to use differential methods. Start from the rate equation for an
arbitrary order, . (Remember that  can be non-integral)
dC 
 rA   A  k A C A
dt
Take the natural logarithm of both sides
 dC 
ln   A   ln k A   ln C A
 dt 
Plotting the left hand side against lnCA should enable the reaction order to be determined
from the gradient.

ln(–dCA/dt) Gradient = 

lnCA

In order to use this approach one must obtain –dCA/dt. There are several ways to do this.
For example:
a) Graphical or direct methods –CA/t
From a plot of concentration against time, the gradient at any time to can be
determined

CA
C

t

b) Fit a polynomial to the curve of C against t

This can easily be done in, say, Excel.
CA = a0 + a1t + a2t2 +…

27
Once the equation is known, it can be differentiated.

B2. For more complex reactions (dependence on CA and CB)

In these cases it may be necessary to simplify the system in order to determine the reaction
orders. We can use the approach of pseudo-order reactions or method of excess. If we take
the general rate equation for two species, A and B reacting with orders  and  respectively:

Rate = kCA CB

Using the differential method from above we have:

ln(rate) = ln k+ lnCA + lnCB

Now there are too many unknowns and so a simple log/log plot not possible. Now, if we keep
one of the reactants in large excess so then its concentration is effectively constant. In this
example if B is in large excess then
CBis constant

The rate equation then becomes:

Rate = k’CA where k’=kCB


This now looks like a simple first-order reaction rate equation and can be solved in the same
way as above. In this example it is called a pseudo-1st order reaction and k’ is the pseudo 1st-
order rate constant.
The value of  can then be found by repeating with different values of CB

So ln k’ = ln k + lnCB

B3. Method of Initial Rates

For other complex reactions e.g. reversible reactions, the above methods may not work so the
method of initial rates can be used.

A series of experiments is carried out at different initial concentrations CA0 and the initial
rate, –rA0 determined for each.

CA0
C

t

28
If the rate law is, rate = kCA0 then plot ln(rate) against lnCA0 enables the
determination of .

C) Integral Methods

Determining rates from C vs t data can be inaccurate and tedious so once the order is known,
or can be guessed then we can use the integrated rate equations. This method is used for
accurate k determination e.g. when k is required at different temperatures.

The aim is to generate linear plots of functions of CA vs t for 0, 1, 2 order.

a) 1st – order irreversible

CA0

CA

–rA = kCA

dC A
  kCA
dt
CA t
dC
C C AA  k 0 dt
A0

CA
ln  kt
C A0

ln(CA/CA0)

Gradient = k

29
In terms of conversion

–rA = kCA

in terms of NA = CAV

1 dN A N
 k A
V dt V

But NA = NA0(1–X) and dNA = –NA0dX so

N A0 dX k
   N A0 (1  X )
V dt V

Rearranging

X t
dX
0 1  X  k 0 dt
–ln (1–X) = kt
–ln(1–X)

Gradient = k

t
b) Zero order

dC A
 k
dt

Integrating with CA = CA0 at t = 0

CA0 – CA = CA0X = kt

CA0

CA

Gradient = –k

t
Time for complete disappearance of CA
t = CA0/k
30
Reactions are only zero order in certain concentration ranges – usually higher concentrations

Often determined by some other factor e.g. intensity of radiation for photochemical reactions
or catalyst surface area.

c) Second order

c.1 Second order with A

A + A → products

dC A
  kC 2A
dt
CA t
dC A
C C A2   k 0 dt
A0

1 1
  kt
C A C A0
1/CA – 1/CA0

Gradient = k

In terms of conversion, t

X
C A0 kt 
1 X

c.2 Second order with CA0 = CB0

Here CA = CB always and the same equations apply

1 1
i.e.   kt
C A C A0

c3. Second order with CA0 ≠ CB0

dC A
  kCA C B
dt

CA = CA0(1 – X) and CB = CB0 – CA0X and dCA = –CA0dX

31
Substituting

dX
C A0  k (C A0  C A0 X )(C B 0  C A0 X )
dt

Let M = CB0/CA0

dX
 kCA0 (1  X )(M  X )
dt

XA t
dX

0
(1  X )(M  X )
 kCA0  dt
0

Solution:

1 P Q
  Eqn. 1.
(1  X )( M  X ) (1  X ) ( M  X )
P( M  X )  Q(1  X )

(1  X )( M  X )

Multiply Eqn 1 by (1 – X)(M – X)

So 1 = P(M – X) + Q(1 – X)

1
If X = 1, 1 = P(M – 1) and P 
M 1
1
If X = M, 1 = Q(1 – M) and Q  
M 1

Substitute into equation 1:

1  1  1   1  1 
    
(1  X )(M  1)  M  1  1  X   M  1  M  X 

 1 1 
X X
dX 1
0 (1  X )(M  X )  M  1 0 1  X  M  X dX

1
  ln(1  X )  ln( M  X )0
X

M 1

1  (M  X ) 
 ln  ln M 
M  1  (1  X ) 

32
 1 (M  X )
 ln  kCA0 t
M  1 M (1  X )

C B0
for (M1) and 1
C A0

So if X, CA0, CB0 and t are known then can determine k

Plot ln(M – X)/M(1 – X) against t or substituting M = CB0/CA0,

C B C A0
ln  C B 0  C A0 kt
CB0C A

D. Method of Half-Lives

Half-life, t1/2: Defined as the time it takes for the concentration of the reactant to fall to half
its initial value.

dC A
Consider the rate law,   rA  kCA
dt

(For 2 or more reactants use the method of pseudo-order reactions)

Integrating with CA = CA0 when t = 0:

1  1 1 
t   1   1 
k (  1)  C A C A0 

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

From the definition of half-life, t = t1/2 when CA=1/2CA0

Substituting for CA:

2 1  1  1 
t1 / 2   
k (  1)  C A01 

Taking the natural log of both sides:

2 1  1
ln t 1 / 2  ln  (1   ) ln C A0
(  1)k

33
Plotting lnt1/2 against lnCA0 is equal to (1 – ) where  is the reaction order.

Slope = 1 – 

lnt1/2

ln CA0

Note that for 1st-order reactions the half-life is independent of CA0.

34
 Temperature dependence of reaction rates

Arrhenius equation
Collision theory
Transition state theory (Activated complex theory)

Learning outcomes:
 Determine the Arrhenius parameters (activation energy and pre-exponential factor) from
experimental data
 Describe the basis of collision theory and transition state theory and show how they can
account for the Arrhenius equation

Rate law –rA = kCACB

–rA depends on concentration, what about temperature dependence? k(T)

Big increase in k over a few degrees

Swedish chemist Arrhenius suggested the equation:

k = A exp(–Eact/RT)

A = pre-exponential factor or frequency factor (same units as k)

Eact = activation energy (J)
R = gas constant (8.314 J K-1 mol-1)
T = temperature (K)

This is the Arrhenius equation and A and Eact are the Arrhenius parameters.

Most reactions obey this relation but very accurate measurements sometimes show some
curvature indicating a slight temperature dependence of A and Eact.

Potential Eact
Energy

Reactants

Products
35
Example

k (s–1)  10–8 4.53 59.3 197 613

T (°C) 90 110 120 130

Find the activation energy and the A factor

Take natural logs of both sides

ln k = ln A – Eact/RT

Plot ln k against 1/T

k (s–1)  10–8 4.53 59.3 197 613

T (°C) 90 110 120 130
ln k –16.910 –14.338 –13.137 –12.002
T (K) 363 383 393 403
1/T  10–3 2.754 2.610 2.544 2.480

-12 --

ln k

-17 --

2.4
1/T  10–3 2.8

Slope = –17.86  103 K = –Eact/R

Eact = 8.314  17.85  103 J mol–1K–1.K
= 148 kJ mol–1

A must be found by calculation not extrapolation

Take one temperature

k = 4.53  10–8 s–1 at T = 363 K
Eact = 148 kJ mol–1 R = 8.314 J K–1mol–1

4.53 10–8 (s–1) = A exp(–148 103 (J mol–1)/8.314  363 (K))

A = 8.8  1013 s–1

36
Collision Theory

Assumes reaction occurs when molecules collide with energy greater than a critical minimum

Assumes:
 Molecules are hard spheres – no intermolecular interactions
 No internal structure

Calculate
 Total rate of collision of reactant molecules
 Fraction of successful collisions

Collision rate (per unit time per unit vol) is proportional to CACB

CA = Number of molecules per unit volume

Multiply by fraction of collisions (f) that occur with at least a KE Eact along the line of
approach.

Boltzmann distribution – probability that a molecule has a specified energy of at least Eact

f = exp(–Eact/RT)

T1
Fraction of
molecules
that have
between E T2
and E+dE T2 > T1

Eact
Kinetic energy

37
What is the fraction of collisions that have sufficient energy for reaction if Eact is 50 kJ mol–1
and the temperature is a) 25 °C, b) 500 °C?

a) f = 1.7  10–9
b) f = 4.2  10–4

Reaction rate is proportional to CACBe–Eact/RT

Compare to a second order rate law, rate = kCACB with k proportional to e–Eact/RT

k = A e–Eact/RT

A can be calculated from kinetic theory

1/ 2
 8kT  m A mB
A     with  
2
N Avo (reduced mass)
   m A  mB

 is the collision cross-section

NAvo is the Avogadro constant

Acalc still differs from Aexpt – must include steric factor, P

e.g. H2 + H2C=CH2 → H3C–CH3 P = 1.7  10–6

orientation of colliding molecules is important

Transition state theory

AB‡ (C‡ )transition state or activated complex

Potential Eact
Energy

A+B

Products

Reaction coordinate

H I H I H I
+ → → +

H I H I H I

38
Suppose that AB‡ is in equilibrium with the reactants and express abundance in terms of the
equilibrium constant K‡

A+B C‡

K‡= [C‡]/[A][B]

Suppose

Rate of formation of products is proportional to [C‡] = K‡ [A][B]

Transition state theory gives the proportionality constant as kBT/h

Where kB is Boltzmann’s constant and h is Planck’s constant
Rate of formation of products = kBT/h  K‡[A][B]

Compare with the rate law, rate = k[A][B]

k = kBT/h  K‡

Relation of the equilibrium constant in terms of standard reaction free energy (G = –RTlnK)

It follows that K‡ = exp(–G‡/RT) activation Gibbs free energy

Writing G‡ = H‡ – TS‡

We can conclude

k = kBT/h  exp(–(H‡ – TS‡)/RT)

= kBT/h  exp(S‡/R) exp(–H‡ /RT)

A can be equated with kBT/h  exp(S‡/R)

Transition state theory is applicable to solution as well as gas phase.

S‡ depends on the internal structure of the transition state

39
 Multiple Reactions

Reversible reactions
Parallel reactions
Series reactions

Learning outcomes:
 Write rate law expressions for multiple reactions.
 Derive an expression for conversion as a function of time for a reversible reaction and
show graphically how the rate constants can be determined.
 Derive expressions for concentration as a function of time for parallel reactions showing
how the rate constants can be determined graphically.
 Show how expressions for concentration as a function of time can be derived for series
reactions.

In many situations there is more than a single reaction occurring in the chemical reactor.
Multiple reactions commonly occur and some of these can be desirable or undesirable. One
of the objectives would be to design and operate the reactor such that the unwanted side
reactions are minimised. The types of multiple reactions we are going to consider are:
reversible, series and parallel reactions.

Irreversible:
A→ P

A+A→P

A+B→P

Reversible:
A R

Series:
A→R→S

Parallel:
A→ R
A→S

Reversible reactions
As an example of a reversible reaction consider the combination of two benzene molecules to
form one molecule of hydrogen and one of diphenyl:

k1
2C6H6 C12H10 + H2
k2

40
In reversible reactions, complete conversion cannot be achieved. All rate laws for reversible
reactions must reduce to the thermodynamic relationship relating the reacting species
concentrations at equilibrium. At equilibrium the reaction rate is zero for all species.

k1
A R
k2

The equilibrium constant is given by K = CR/CA

The rate equation (assuming an elementary reaction) can be written as:

dC A
 rA    k1C A  k 2 C R
dt

If we set up the stoichiometric table for this reaction:

t=0 t=t concentration at t

A CA0 –CA0X CA = CA0 – CA0X
R CR0 + CA0X CR = CR0 + CA0X

Where X is conversion with respect to A

These concentrations can be substituted into the rate equation:

dC A dX
  C A0  k1 (C A0 - C A0 X )  k 2 (C R 0  C A0 X )
dt dt

Setting M = CR0/CA0

Divide by CA0

dX
 k1 (1  X )  k 2 ( M  X ) Eqn 1
dt

At equilibrium:

dC A dX
0 and 0
dt dt

So
k1 M  X e
 Eqn 2 X e equilibriu m conversion
k2 1 X e

41
This can be rearranged to:

K M
Xe 
K 1

Substitute for k2 = k1(1 – Xe)/(M + Xe) Rearrange eqn 2 into eqn 1

dX (1  X e )
 k1 (1  X )  k1 (M  X )
dt (M  X e )

Multiply by (M + Xe)/(M + Xe)


k1
(1  X )(M  X e )  (1  X e )(M  X )
M  Xe


k1
X e  MX  X  X e M 
M  Xe

( M  1)
 k1 (X e  X )
(M  X e )

Integrating:

( M  1)
X t
dX
0 ( X e  X )  0 k1 M  X e dt

–[ln[Xe – X)]0X =

–ln(Xe – X) + ln Xe =

Xe  X
 ln( )
Xe

42
  X  ( M  1)
 ln 1    k1 t
 Xe  (M  X e )

Plot left-hand side (LHS) vs time

The expression can also be considered in terms of concentration:

X e  X C A0  C Ae  C A0  C A C A  C Ae
 
Xe C A0  C Ae C A0  C Ae

 C  C Ae  ( M  1)
 ln  A   k1 t
 C A0  C Ae  (M  X e )

An irreversible reaction is simply a special case of a reversible reaction with CAe = 0 or XAe =
1 or K = ∞

e.g. –ln(CA/CA0) = –ln(1 – X) = kt

From an experiment we can:

 Determine the equilibrium concentration, CAe

 Determine the equilibrium constant (K = CR/CA)
 Determine k1 ( and hence k2) from the slope

43
Parallel Reactions

These are also called ‘competing reactions’. The reactant is consumed by two different
reactions to give two different products. Product R may be the desired product whereas
product S is an undesired product
k1
A → R
k2
A → S

An example is the oxidation of ethylene to ethylene oxide

CH2=CH2 → CH2-CH2
O
CH2=CH2 → CO2 + 2H2O

The second reaction, leading to combustion products is the unwanted reaction.

Write down the rate equations for the two reactions assuming that they are both 1st order:

 k1C A  k 2 C A  k1  k 2 C A
dC A
 Eqn 1
dt

dC R
 k1C A Eqn 2
dt

dC S
 k 2C A Eqn 3
dt

The rate of disappearance of A is the sum of the rates of formation of R and S

If we integrate eqn 1:

CA
 ln  k1  k 2 t
C A0

We can see that the disappearance of A is determined by the sum of 1st order rate constants.
k1 + k2 can be determined from the slope:

–ln(CA/CA0)

Slope= k1+k2

44
t
What about R and S against time?

Dividing eqn 2 by eqn 3.

dC R k1

dC S k 2

Integrating:

CR Cs
k1
CR0dC R  k 2  dC
CS 0
S
CR
Slope = k1/k2
k
CR  CR0  1 C S  C S 0  CR0
k2

CS0 CS

From eqn 1 and eqn 2

dCR
 k1C A  k1C A0 exp[ k1  k 2 t ]
dt
CR t

 dC R   k1C A0 exp[k1  k 2 t ]dt

CR 0 0

C A0 1  exp( (k1  k 2 )t 
k1
CR  CR0 
k1  k 2

But CR0 = 0

C A0 1  exp( (k1  k 2 )t 
k1
CR 
k1  k 2

As

k1 k2
t  CR  C A0 and C S  C A0
k1  k 2 k1  k 2

45
 k1 > k2
CR
Ci

CS

CA

t
Product ratio: CR/CS = k1/k2

Yield

CR k1
YR   As t 
C A0 k1  k 2

CS k2
YS   As t 
C A0 k1  k 2

Selectivity
rR k1
SR/ S  
rS k 2

If, instead of being 1st order, the reactions are of order  then one product can be maximised
against the other.

dC R
 rR  k1C A 1
dt

dC S
 rS  k 2 C A 2
dt

46
The selectivity to be maximised is then:
r k
S R / S  R  R C A 1 2
rS k S


1 > 2

If the reaction order of the desired product R is greater than the reaction order of the
undesired product S then the reaction must be carried out with the concentration of A as high
as possible.

Gas phase – run without inerts and at high pressure

Liquid phase – keep diluents to a minimum

Use a batch or PFR as the concentration of A starts high.

2 > 1

If the order of the desired product R is less than that of the undesired product S then having a
low concentration of A is desirable.

Use a CSTR as the concentrations are kept at a low level

Effect of temperature

If we write the selectivity parameter in terms of the Arrhenius parameters:

k R AR
SR/ S   exp( [( E S  E R ) / RT ])
kS AS

where A is the pre-exponential factor (or frequency factor) and E is the activation energy.

ER>ES

kR increases more rapidly with temperature than kS so the selectivity can be maximised by
running at high temperature.

ER<ES

The reaction should be carried out at low temperature to maximise selectivity but not too low
that the desired reaction does not proceed.

47
 Series Reactions

Irreversible, series reactions are another example of multiple reactions:

A→R→S

There are many examples of this type of reaction chain such as:

E.g. 1 reaction of ethylene oxide (EO) with ammonia to form mono-, di- and triethanolamine
CH2-CH2 + NH3 → HOCH2CH2NH2
O
EO EO
→ (HOCH2CH2)2NH  (HOCH2CH2)3N

E.g. 2

C6H6 +Cl2 → C6H5Cl +Cl2 → ……→ C6Cl6

Write the rate laws for these general reactions assuming each is 1st order:

dC A
  k1C A eqn 1
dt

dC R
 k1C A - k 2 C R eqn 2
dt

dC S
 k 2CR eqn 3
dt

Initial conditions: CA0, CR0 = CS0 = 0

Eqn 1 gives

CA
 ln  k1t
C A0

CA = CA0 exp(–k1t) eqn 4

Eqn 2 gives
dC R
 k 2 C R  k1C A0 exp( k1t )
dt

This equation is a first order differential equation of the form:

48
 dy
 Py  Q with y = CR and Q = f(x)
dx

Use an integrating factor

exp(  Pdx ) here : exp( k 2 t )

Boundary conditions: t = 0, CR0 = 0

The solution is:

CR 
k1
k 2  k1

C A0 e k1t  e k2t 
Since CA0 = CA + CR + CS by stoichiometry

Then CS = CA0 – CA – CR

CS
CA

Ci

CR

To find CRmax differentiate and set dCR/dt = 0

ln( k 2 / k1 )
t max 
k 2  k1

Examples of concentration profiles in multiple reactions…..

49
50
51
 Design of Chemical Reactors

We have been looking at 3 'ideal' reactor types: batch, continuously stirred tank reactor,
CSTR (Continuous), Plug Flow Reactor, PFR (Continuous). From the mass/molar balances
for these we produced the following ‘design’ or performance equations:

Batch (constant volume) CSTR PFR

dC A n A0  n A dn A
(rA )   (rA )  (rA )  
dt V dV

The design questions are then:

 What size (volume) should the reactor be?
 How long do we have to wait to achieve the required conversion?

1. CSTR

Recall the assumption about ‘perfect mixing’

If the circulation time of a fluid element within the vessel is, say, 1/100 k of the average time
spent within the vessel then we can think of it as perfectly mixed.

V (m 3 )
Average time spent in vessel,   : mean residence time
 T (m 3 / s)

So, if the vessel is half empty it would take V/T to fill.

Note that this is only an average: actually there is a very wide distribution. A molecule added
at the inlet may be present at the next instant anywhere in the vessel, including the outlet.
Also some molecules have been in the vessel a very long time and have not found their way
out.

n A0  n A  T (C A0  C A )
(rA )  
V V

C A0  C A
 Note: constant V


C A0 X  C A0  C A 
In terms of X, (rA )  X   C A  C A0 (1  X )
  C A0 

Now replace (–rA) by the appropriate kinetics:

52
1st Order

C A0  C A
k1C A  CA uniform in vessel


so
C A0  C A 1  C A0  CA 1 k1
    1 or  X 
k1C A k1  C A  C A0 1  k1 1  k1

Dimensionless Damköhler number, Da = k1

CA 1 Da
 X 
C A0 1  Da 1  Da

These equations define the time, , necessary to achieve a certain conversion, X, (or change
in concentration, CA) for systems with rate constant, k1.

If we know then we can calculate T for a given V (i.e. a given reactor) and hence the
production rate.

Or, for a given production rate (mol A/s fed) at conversion (X or CA) then can calculate the
size of the reactor, V, required.

2nd order

C A0  C A
k 2 C A2 


k 2 C A2  C A  C A0  0

Solve quadratic equation taking the root with +ve CA:

1  4k 2 C A0  1
CA 
2k 2

CA 1  4 Da  1
 Da = k2CA0 (check dimensionless units)
C A0 2 Da

In terms of conversion, CA/CA0 = 1 – X

(1  2 Da)  1  4 Da
X 
2 Da

53
 2. PFR

dn A
(rA )  
dV

T m3/s
CAe
CA0 mol A/m3 V
nAe
nA0 mol A/s

nA= CAT

mol A/s = mol A/m3.m3/s

Constant density and hence T i.e.liquids

If gas flow has change in volume then T will change with distance, x i.e. in general T is a
function of distance, x and hence of V.

dC A
(rA )   T T constant
dV

1st order

CA V
dC A dC A k1 CA kV
(rA )  k1C A   T
dV
: CA0 C A 0  T dV
  : ln
C A0
  1  k1
T

or
CA CA
 exp( k1 )  exp(  Da)
C A0 C A0

In terms of X:

X  1  exp(  Da)

Compare with a batch reactor: t → (ie V/T)

54
2nd Order

CA V
dC A dC A k1
(rA )  k 2 C A2   T
dV
: CA0 C A2 0  T dV
 

CA
 1  1 1 kV
      2  k 2
 C A  CA0 C A C A0  T

C A0 CA 1 CA 1
 1  k 2C A0 and  or 
CA C A0 1  k 2C A0 C A0 1  Da

Da
In terms of X: X 
1  Da

3. CSTRs in series

The disadvantage of a CSTR is that it works at the lowest concentration in the range between
the feed and the product - hence at the lowest rate.

Split the volume of a single CSTR into 2 tanks:

CA1 cf
CA0 . CAe
CA1 CAe CAe CA0 CAe

The rate in the first tank will be higher than in the second tank (and in the single large tank)

Calculate the total volume (size) of reactor(s) necessary to achieve a given exit concentration
(conversion)

Consider a 1st order reaction only

a) Single reactor

55
 C Ae 1 1  T  C A0 
  so V1    1
C A0 1  k1 V1 k1  C Ae 
1 k1
T

b) Two reactors in series

Assume:
i) equal volumes (VTotal = 2V2)
ii) equal temperatures (hence equal k1)
iii) 1st order

CA0 CA1
V2 V2 CAe

C A1 1 C A0
 Eqn. 1. so C A1  Eqn. 3
C A0 1  V2 k V2
1  k1
1
T T

C Ae 1 C A1 C Ae
 Eqn.2. Note. 
C A0 V2 C A0 C A1
1 k1
T

Substitute Eqn. 3 into Eqn. 2

1/ 2
C Ae 1 C  1
 and  Ae  
C A0  V 
2
 C A0  V2
1  2
k1  1 k1
T
 T 

 T  C A0  
1/ 2 1/ 2
 C A0  V2
   1 k1 and V2     1
 C Ae  T k1  C Ae  


56
 2  C 1 / 2 
Total volume 2V2  T  A0   1
k1  C Ae  

In general, for N reactors, all of equal volume and equal temperature:

N T  C 1/ N 
total volume   A0   1
k1  C Ae  

For CSTRs in series as N → the performance tends to that of a PFR (which needs lower
volume for the same reaction.

Example

57
 CSTR vs PFR: Concentration
1st order reaction

1.0

0.8

0.6
CA/CA0

CSTR

0.4

PFR
0.2

0.0
0.01 0.1 1 10 100 1000
Da(=k1)

CA 1 CA
CSTR (1st order)  PFR (2nd order):  exp(  Da)
C A0 1  Da C A0

CSTR Reactor: Concentration

1.0

0.8

0.6
CA/CA0

2nd order

0.4

1st order
0.2

0.0
0.01 0.1 1 10 100 1000
Da (=k1 or k2CA0)

CA 1 CA 1  4 Da  1
1st order:  2nd order: 
C A0 1  Da C A0 2 Da

58
 CSTR vs PFR: Conversion
1st order reaction

1.0

0.8
PFR

0.6 CSTR
XA

0.4

0.2

0.0
0.01 0.1 1 10 100 1000
Da (=k1)

Da
CSTR: X  PFR: X  1  exp(  Da)
1  Da

CSTR Reactor: Conversion

1.0

0.8

1st order
0.6
XA

2nd order
0.4

0.2

0.0
0.01 0.1 1 10 100 1000
Da (=k1 or k2CA0)

Da (1  2 Da)  1  4 Da
1st order: X  2nd order: X 
1  Da 2 Da

59
Design Structure for Isothermal Reactors

1. The general mole balance equation:

dN A
n A0  n A  rA 
dt

2. Apply the mole balance to specific reactor design equations:

dX
Batch : N A  rAV
dt

n A0 X
CSTR : V 
 rA

dX
PFR : n A0  rA
dV

3. Is –rA = f(X) given?

Yes – Evaluate algebraic (CSTR) or integral (PFR) equations

No – go to 4

4. Determine the rate law in terms of the concentration of reacting species.

e.g. –rA =kCACB or multiple reactions

5. Use stoichiometry to express concentration as a function of conversion:

e.g. CA = CA0(1 – X)

N b 
e.g. C B  C A0  B 0  X 
 N A0 a 

6. Combine 2, 4 and 5 to determine rate law –rA = f(X)

7. Evaluate mole balance/rate law/stoichiometry by one of the following:

Analytically
Graphically
Numerically

60
Algorithm for solving problems

1. Write out the problem statement. Include information on what you are to solve, and
consider why you need to solve the problem.

2. Make sure you are solving the real problem as opposed to the perceived problem. Recast
the problem statement if necessary.

3. Draw and label a sketch. Define and name all variables and/or symbols. Show numerical
values of variables if known.

4. Identify and name

A. Relevent principles, theories and equations

B. Systems and subsytems
C. Dependent and independent variables
D. Knowns and unknowns
E. Inputs and outputs
F. Necessary (missing) information

5. List assumptions and approximations involved in solving the problem. Question the
assumptions and then state which ones are the most reasonable for your purposes.

6. Check to see if the problem is either under-specified or over-specified. If it is under-

specified, figure out how to find the missing information. If over-specified, identify the extra
information that isn't needed.

7. Relate problem to a similar problem or experience (compare to an example problem in

lecture or in the book).

8. Use an algorithm (e.g. reaction engineering)

A. Mole Balance
B. Rate Laws
i. Kinetic
ii. Transport
C. Stoichiometry
i. Gas or liquid
ii. Pressure drop

D. Combine

61
9. Develop/derive/integrate and/or manipulate an equation or equations from which the
desired variable can be determined.

10. Substitute numerical values and calculate the desired variable. Check your units at each
step in the solution to find possible

11. Examine and evaluate the answer to see it makes sense. Is it reasonable, considering the
problem statement? Does it consider safety and ethical issues?

62
Example

The elementary, liquid-phase, irreversible reaction

A+B→C

is to be carried out in a flow reactor. Two reactors are available, an 800 dm3 PFR that can
only be operated at 300 K and a 200 dm3 CSTR that can be operated at 350 K. The two feed
streams to the reactor mix to form a single feed stream that is equimolar in A and B, with a
total volumetric flowrate of 10 dm3/min. Which of the two reactors will give the highest
conversion?

Additional information:
At 300 K, k = 0.07 dm3 mol–1 min–1
E = 85000 J K–1 mol–1
CA0 = CB0 = 2 mol dm–3
A0=B0 = 0.50 = 5 dm3 min–1

63