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Xid-10123148 1
Xid-10123148 1
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
• Metcalfe IS, Chemical Reaction Engineering – A First Course, OUP 1997 (An
inexpensive, accessible book which goes deeper into the subject than this
introductory course)
• 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
6. Complex reactions
Reversible, parallel, 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.
A → products
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
reactants products
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:
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
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
7
Mole Balance applied to Batch Reactors
NA moles of A
nj0 = nj = 0
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
8
N A1
dN A
t1 rV
N A0 A
–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
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.
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
nj0 nj|V+V nj
nj|V
V V+V
V
Applying the mole balance:
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
V kCA k n n A
n A1 A1
n C
V ln A0 ln A0
k nA k CA
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
Chemical species
Stoichiometric
coefficients
13
Conversion in batch reactors
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 )
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
dN A
rAV
dt
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
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
Molar flow rate at which species A is reacting within the entire system is nA0X:
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)
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
Design equation
n A0 n A
V
rA
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.
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
Rearranging,
C A0 0 X
rA
V
C A0 X
rA
dn A
rA
dV
dX
n A0 rA
dV
X
dX
V n A0
0
rA
–rA = kCA
17
But CA = CA0(1–X) for constant volume
So
X
dX
V n A0
0
kCA0 (1 X )
X
n A0 dX
V
kCA0 (1 X )
0
C A0 0
V ln(1 X )
kCA0
V 1
ln(1 X )
0 k
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
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
19
Levenspiel plot
9
8
7
6
nA0/-rA
5
4
3
2
1
0
0 0.5 1
1. CSTR
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
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
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.
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
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.
aA + bB → cC + dD
= c/a (–rA)
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:
(d/a+c/a–b/a–1) = Change in total number of moles per mole reacted (Note variable
volume reactions)
Order of reaction – power to which the concentrations are raised in the rate law
24
Units of k
k
concentration 1n
time
rate = k[H][Br2]
Therefore the rate law and reaction order must be determined experimentally
25
Experimental Determination of Reaction Rate Information
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.
Example 1.
[CA] 1.0 2.0 4.0 12.0
Rate 0.05 0.10 0.20 0.60
Example 2.
[CA] 4.0 8.0 16.0 32.0
Rate 3.0 12.0 48.0 192.0
Example 3.
[CA] 6.0 12.0 24.0 48.0
Rate 5.0 4.9 5.1 5.0
26
B. Differential Methods of Analysis
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
27
Once the equation is known, it can be differentiated.
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:
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
CBis constant
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
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.
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
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
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
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
1 1
i.e. kt
C A C A0
dC A
kCA C B
dt
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 )
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
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 (M1) and 1
C A0
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 kCA
dt
1 1 1
t 1 1
k ( 1) C A C A0
1 C 1
t A0 1
kCA01 ( 1) C A
2 1 1 1
t1 / 2
k ( 1) C A01
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
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
k = A exp(–Eact/RT)
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
ln k = ln A – Eact/RT
-12 --
ln k
-17 --
2.4
1/T 10–3 2.8
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
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
Compare to a second order rate law, rate = kCACB with k proportional to e–Eact/RT
k = A e–Eact/RT
1/ 2
8kT m A mB
A with
2
N Avo (reduced mass)
m A mB
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
k = kBT/h K‡
Relation of the equilibrium constant in terms of standard reaction free energy (G = –RTlnK)
We can conclude
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
dC A
rA k1C A k 2 C R
dt
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
dX (1 X e )
k1 (1 X ) k1 (M X )
dt (M X e )
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 )
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 = ∞
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
CH2=CH2 → CH2-CH2
O
CH2=CH2 → CO2 + 2H2O
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
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?
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
dCR
k1C A k1C A0 exp[ k1 k 2 t ]
dt
CR t
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.
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.
Effect of temperature
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
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
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
Eqn 1 gives
CA
ln k1t
C A0
Eqn 2 gives
dC R
k 2 C R k1C A0 exp( k1t )
dt
48
dy
Py Q with y = CR and Q = f(x)
dx
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
ln( k 2 / k1 )
t max
k 2 k1
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:
dC A n A0 n A dn A
(rA ) (rA ) (rA )
dt V dV
1. CSTR
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)
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
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
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
CA 1 4 Da 1
Da = k2CA0 (check dimensionless units)
C A0 2 Da
(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= CAT
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)
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 2C A0 and or
CA C A0 1 k 2C 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.
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)
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
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
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
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
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
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
dN A
n A0 n A rA
dt
dX
Batch : N A rAV
dt
n A0 X
CSTR : V
rA
dX
PFR : n A0 rA
dV
No – go to 4
e.g. CA = CA0(1 – X)
N b
e.g. C B C A0 B 0 X
N A0 a
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.
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.
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
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 = 0.50 = 5 dm3 min–1
63