Lecture 2

Chemical Reaction Engineering (CRE) is the

field that studies the rates and mechanisms of
chemical reactions and the design of the reactors in
which they take place.

1 Dr. Arkan Jasim Hadi

 Lecture 2 – Tuesday 1/15/2013
 Review of Lecture 1
 Definition of Conversion, X
 Develop the Design Equations in terms of X
 Size CSTRs and PFRs given –rA= f(X)
 Conversion for Reactors in Series
 Review the Fall of the Tower of CRE

2 Dr. Arkan Jasim Hadi

Review Lecture 1
Reactor Mole Balances Summary
The GMBE applied to the four major reactor types
(and the general reaction AB)
Reactor Differential Algebraic Integral
NA
NA
dN A
Batch dN A
 rAV t  rAV
dt N A0
t
CSTR FA 0  FA
V
rA FA
FA
dFA dFA
PFR
dV
 rA V 
FA 0
drA
V

FA FA
dFA dFA
PBR
 dW
 rA W 
FA 0
rA
3 Dr. Arkan Jasim Hadi
W
Review Lecture 1
CSTR – Example Problem
Given the following information, Find V
3
0  10 dm 3
min   0  10 dm
min
C A0
V ? C A  0.1C A0
FA0  0C A0
FA  C A

Liquid phase
  0
FA   0CA

4 Dr. Arkan Jasim Hadi

Review Lecture 1
CSTR – Example Problem
(1) Mole Balance:
FA0  FA  0C A0   0C A  0 C A0  C A 
V  
 rA  rA  rA

(2) Rate Law:

 rA  kCA

(3) Stoichiometry:
FA FA
CA  
 0
5 Dr. Arkan Jasim Hadi
 Review Lecture 1
CSTR – Example Problem
(4) Combine:
 0 CA 0  CA 
V
kCA

(5) Evaluate:
C A  0.1C A0

10dm3
C A0  0.1C A0  101  0.1
V  min  3

0.23 min 1 0.1C A0  0.230.1 dm

900
V  391 dm3
6
2.3Hadi
Dr. Arkan Jasim
 Define conversion, X
In defining conversion, we choose one of the reactants as the basis of calcullation and then
relate the other species involved in the reaction to this basis. In most instances it is best to
choose the limiting reactant as the basis of calculation. We develop the stoichiometric
relationships and design equations by considering the general reaction
Consider the generic reaction:
a AbB
 c C  d D
The uppercase letters represent chemical species and the lowercase letters represent
stoichiometric coefficients. Taking species A as our basis of calculation, we divide the reaction
expression through by the stoichiometric coefficient of species A, in order to arrange the
reaction expression in the form
b c d
A B
 C D
a a a

Define conversion, X
moles A reacted
XA 
moles A fed
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 2.2 Design Equations
2.2.1 Batch Systems
• in most batch reactors, the longer a reactant is in the reactor, the more reactant is
converted to product until either equilibrium is reached or the reactant is exhausted.
• Consequently, in batch systems the conversion X is a function of the time the reactants
spend in the reactor.
• If NA0 is the number of moles of A initially, then the total number of moles of A that
have reacted after a time t is [NA0X]
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 consumed = moles of A fed . [
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑓𝑒𝑑
[𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 reacted = [NA0] . [x]
(consumed)]

Now, the number of moles of

A4hat remain in the reactor
after a time t, N A , can be
expressed in terms of NA0 and
X:
8 Dr. Arkan Jasim Hadi
 Batch
The number of moles of A in the reactor after a conversion X has been achieved is

When no spatial variations in reaction rate exist, the mole balance on species A for a
batch system reduces to the following equation:

This equation is valid whether or not the reactor volume is constant.

b c d
In the general reaction A B
 C D
a a a

reactant A is disappearing; therefore, we multiply both sides of Equation (2-5) by -1 to

obtain the mole balance for the batch reactor in the form

The rate of disappearance of A, - r A , in this reaction might be given by a rate law

similarDr.toArkan
Equation
Jasim Hadi
(1-2), such as -rA = kCACB
9
Batch
For batch reactors we are interested in determining how long to leave the reactants in
the reactor to achieve a certain conversion X. To determine this length of time, we
transform the mole balance, Equation (2-5), in terms of Conversion by differentiating
Equation (2-4),

with respect to time, while remembering that NAO is the number of moles of A
initially present and is therefore a constant with respect to time.

Combining the above with Equation (2-5) yields

For a batch reactor, the design equation in differential form is

10 Dr. Arkan Jasim Hadi

 Batch
Constant-volume batch reactors are found very frequently in industry.
For a constant-volume batch reactor, Equation (2-5) can be arranged into the
form

For batch-reactor systems in which the volume varies while the reaction is proceeding, the
volume may usually be expressed either as a function of time alone or of conversion alone, for
either adiabatic or isothermal reactors. Consequently, the variables of the differential equation
(2-6) can be separated in one of the following ways:

or

These equations are integrated with the limits that the reaction begins at time zero
(ie., t = 0, X = 0).
11 Dr. Arkan Jasim Hadi
 Batch
When the volume is varied by some external source in a specific manner (such as a car
cylinder piston compressing the reacting gas according to the equation V= V1+V2 sin ωt) the
equation relating time and conversion that one would use is

However, for the more common batch reactors in which volume is not a predetermined
function of time, the time t necessary to achieve a conversion X is

12 Dr. Arkan Jasim Hadi

 2.2 Design Equations
2.2.2 Flow Systems
Normally, conversion increases with the time the reactants spend in the reactor. For
continuous-flow systems, this time usually increases with increasing reactor volume;
consequently, the conversion X is a function of reactor volume V. If FA0 is the molar flow rate of
species A fed to a system operated at steady state, the molar rate at which species A is reacting
within the entire system will be FA0X.
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑓𝑒𝑑 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
[𝐹𝐴0 . 𝑋] = .
𝑡𝑖𝑚𝑒 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑓𝑒𝑑

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
[𝐹𝐴0 . 𝑋] =
𝑡𝑖𝑚𝑒
Then:

13 Dr. Arkan Jasim Hadi

 2.2 Design Equations
2.2.2 Flow Systems
Rearranging gives

The entering molar flow rate, FA0 in (mol/s), is just the product of the entering
concentration, CA0 in (mol/dm3), and the entering volumetric flow rate, ʋo in (dm3/s):

For liquid systems, CAo is commonly given in terms of molarity, for example, CAo= 2
mol/dm3. For gas systems, CAo can be calculated from the entering temperature and
pressure using the ideal gas law or some other gas law.
For example

14 Dr. Arkan Jasim Hadi

 2.2 Design Equations
2.2.2 Flow Systems
Example 2-I Using the Ideal Gas Law :to Calculate CA0
A gas mixture consists of 50% A and 50% inserts at 10 atm (1013 kPa) and enters the reactor
with a flow rate of 6 dm3/s at 300°F (422.2 K). Calculate the entering concentration of A,
CAO, and the entering molar flow rate, FA0.

The ideal gas constant is R = 0.082 dm3-atm/mol-K (Appendix B)

15 Dr. Arkan Jasim Hadi

 Cont's
Example 2-I Using the Ideal Gas Law :to Calculate CA0

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 CSTR
Consider the generic reaction:
a AbB  c C  d D

Chose limiting reactant A as basis of calculation:

b c d
A B  C  D
a a a

Define conversion, X
moles A reacted
XA 
moles A fed
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 CSTR

dNA
Steady State 0
dt

FA 0  FA
Well Mixed V
rA

 r dV  r V
A A

18 
Dr. Arkan Jasim Hadi
 CSTR
 Moles A  Moles A   Moles A
leaving   entering  reacted 
     
FA  FA0  FA0 X

FA0  FA   rAdV  0
FA 0  FA 0  FA 0 X 
V
rA
FA0 X
V
 rA
CSTR volume necessary to achieve conversion X.

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 PFR
After multiplying both sides of the tubular reactor design equation (1-10) by - 1, we
express the mole balance equation for species A in the reaction given by Equation (2-
2) as
dFA
  rA
dV
For a flow system, FA has previously been given in terms of the entering molar flow
rate FA0 and the conversion X :

FA  FA0  FA0 X
We now separate the variables and integrate with the limit V = 0 when X = 0 to obtain
the plug-flew reactor volume necessary to achieve a specified conversion X :
X
V 0 X 0 dX
V  FA0 
V V X  X  rA
0

PFR volume necessary to achieve conversion X.

20 Dr. Arkan Jasim Hadi
 PBR
The derivation of the differential and integral forms of the design equations for a
packed-bed reactor are analogous to those for a PFR

Integrating with the limits W = 0 at X = 0 gives

Equation (2-18) can be used to determine the catalyst weight W necessary to

achieve a conversion X when the total pressure remains constant.

21 Dr. Arkan Jasim Hadi

 Reactor Mole Balances Summary
in terms of conversion, X
Reactor Differential Algebraic Integral
X
X
dX
Batch N A0
dX
  r AV t  N A0 
dt 0
 rAV
t
FA 0 X
CSTR V
rA
X
dX V 
FA0 dX
PFR FA 0  rA
dV  0
 rA
X
X
dX FA0 dX
PBR
 FA 0   rA W 
22 Dr. Arkan Jasim Hadi dW 0
 rA
W
Example 2-2 Sizing a CSTR
consider the isothermal gas-phase decomposition reaction

(a) Using the data in either Table 2-2 or Figure 2- 1 , calculate the volume necessary to achieve 80%
conversion in a CSTR. (b) calculate the volume necessary to achieve 80% conversion in a PFR.(Le., X =
0.8).

The laboratory measurements given in Table 2-1 show the chemical reaction rate as a function of
conversion. The temperature was 300°F (422.2 K), the total pressure 10 atm (1013 kPa), and the initial
charge an equimolar mixture of A and inerts.

23 Dr. Arkan Jasim Hadi

 Cont's
Example 2-2 Sizing a CSTR and PFR

Therefore, we need to find the value of -rA (or reciprocal thereof) at X = 0.8. From
either Table 2-2 or Figure 2-1 we see that when X = 0.8, then

24 Dr. Arkan Jasim Hadi

 Cont's
Example 2-2 Sizing a CSTR and PFR

X
FA0 dX
(b) For the PFR, design equation is V 
0
 rA
For 80% conversion, we will use the five-point quadratic formula with ∆X = 0.2

25 Dr. Arkan Jasim Hadi What is the volume at x=0.2, x=0.4 and x=0.6???
Example 2-4 Comparing CSTR and PFR Sizes
It is interesting to compare the volumes of a CSTR and a plug-flow reactor (PFR) required for
the same job. To do this we shall use the data in Figure 2-1 to learn which reactor would
require the smaller volume to achieve a conversion of 60%: a CSTR or a PFR. The feed
conditions are the same in both cases.The entering molar flow rate is 5 mol/s.

26 Dr. Arkan Jasim Hadi

 For the same flow rate FA0 the plug-flow reactor requires a smaller volume than
the CSTR to achieve a conversion of 60%. This comparison can be seen in
Figure E2-4.1.
For isothermal reactions of greater than zero order, the PFR will always
require a smaller volume than the CSTR to achieve the same conversion.

27 Dr. Arkan Jasim Hadi

 Numerical Evaluations of Integrals
 The integral to calculate the PFR volume can be
evaluated using method as Simpson’s One-Third
Rule: (See Appendix A.4)
X
FA0 x  1 4 1 
V  dX  FA0    
1
0
 rA 3 
 A r ( 0)  rA ( X / 2)  rA ( X ) 
 rA ( X 2 )
1
 rA
Other numerical methods are:
1
 Trapezoidal Rule (uses two
 rA ( X 1 )
data points)
1  Simpson’s Three-Eight’s
 rA (0) Rule (uses four data points)
0 X1 X2
 Five-Point Quadrature
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Reactors in Series
Many times reactors are connected in series so that the exit stream of one reactor is the feed
stream for another reactor.
The relationships between conversion and molar flow rates for the reactor sequence shown in
Figure 2-2 are given by the following equations:
Molar Flow rate of species A at point i: FAi  FA0  FA0 X i
total moles of A reacted up to point i
Xi 
moles of A fed to first reactor
Only valid if
there are no
side
streams.

32 Dr. Arkan Jasim Hadi

Reactors in Series

33 Dr. Arkan Jasim Hadi

Reactors in Series
The volume for the third reactor, V3 is found by integrating Equation (2-15)
between the limits x1 and x2:

We will now use FAO calculated in Example 2-1 together with Figure 2-1 to size
reactors for the three reactor schemes,. The first scheme to be consiser two CSTRs
in series shown in Figure 2-3.
For the first reactor in which the rate of disappearance of A is –rA1 at conversion X1,
the volume necessary to achieve the conversion X , is

the volume necessary to increase the

conversion in reactor 2 from X1 to X2, was
derived previously and is given by
Equation (2-19):

34 Dr. Arkan Jasim Hadi

Reactors in Series
Example 2-5 ComparingVolumes for CSTRs in Series
For the two CSTRs in series, 40% conversion is achieved in the first reactor. What is the total
volume of the two reactors necessary for 80% overall conversion of the species A entering
reactor l? (If FA2 is the molar flow rate of A exiting from the last reactor in the sequence, FA2=
0.2FA0.).
For reactor1 we observe from either Table
2 -2 or Figure E2-5.1 that when X = 0.4,
then

35 Dr. Arkan Jasim Hadi

Reactors in Series
Note again that for CSTRs in series the rate –rA1 is evaluated at
a conversion of 0.4 and rate -rA2 is evaluated at a conversion of
0.8 The total volume is

The volume necessary to achieve 80% conversion in one

CSTR is

Notice in Example 2-5 that the sum of the two CSTR reactor volumes (364 L) in series is
less than the volume of one CSTR (555 L) to achieve the same conversion. This case does
not hold true for two plug-flow reactors connected in series.

Example 2-6 Sizing Plug-Flow Reactors in Series

Using either the data in Table.2-2 or Figure 2-5, calculate the reactor volumes V1 , and V2 for the plug-
flow sequence shown in Figure 2-4 when the intermediate conversion is 40% and the final conversion
is 80%.The entering molar flow rate is the same as in the previous examples, 0.867 mol/s.

36 Dr. Arkan Jasim Hadi

Reactors in Series
Example 2-6 Sizing Plug-Flow Reactors in Series
Using either the data in Table.2-2 or Figure 2-5, calculate the reactor volumes V1 , and V2 for the plug-
flow sequence when the intermediate conversion is 40% and the final conversion is 80%.The entering
molar flow rate is the same as in the previous examples, 0.867 mol/s.

Solution

37 Dr. Arkan Jasim Hadi

 Reactors in Series
Example 2-6 Sizing Plug-Flow Reactors in Series

In this example, we shall use Simpson’s rule (see Appendix A.4) to evaluate the
integrals.

38 Dr. Arkan Jasim Hadi

Reactors in Series
Example 2-6 Sizing Plug-Flow Reactors in Series

∆𝑥 1 1 1
= 𝐹𝐴0 . [ + 4. + ]
3 −𝑟𝐴 0.4 −𝑟𝐴 0.6 −𝑟𝐴 0.8

39 Dr. Arkan Jasim Hadi

 Reactors in Series
Example 2-7 Comparing the Order of Sequencing Reactors
Calculate the individual reactor volume as well as the total reactor volume for each scheme in Figure 2-6
for the reaction data given in Table 2-2 when the intermediate conversion is 50% and FAo= 0.867 mol/s.

Solution

40 Dr. Arkan Jasim Hadi

Reactors in Series
Example 2-7 Comparing the Order of Sequencing Reactors

41 Dr. Arkan Jasim Hadi

Reactors in Series
Example 2-7 Comparing the Order of Sequencing Reactors

Scheme B will give the

smaller total reactor
volume for an
intermediate conversion of
50%.

42 Dr. Arkan Jasim Hadi

Reactors in Series
2.5 Some Further Definitions

Space Time. The space time,τ, is obtained by dividing reactor volume by

the volumetric flow rate entering the reactor:
Space time τ is the time necessary to process 1 reactor volume of fluid at
entrance conditions.
V

0
For example, consider the tubular reactor shown in Figure 2-10, which is 20 m long
and 0.2 m3 in volume. The dashed line in Figure 2-10 represents 0.2 m3 of fluid
directly upstream of the reactor.
The time it takes for this fluid to enter the reactor completely is the space time.
It is also called the holding time or mean residence time.

43 Dr. Arkan Jasim Hadi

Reactors in Series
2.5 Some Further Definitions
If both sides of the plug-flow reactor design equation (2-16) are divided by the entering volumetric flow
rate and then the left-hand side is put in terms of space time, the equation takes the form

The space velocity (SV), which is defined as

might at first sight be regarded as the reciprocal of the space time. However, there is a
difference in the two quantities' definitions. For the space time, the entering volumetric flow
rate is measured at the entrance condition, while for the space velocity other conditions
are often used. The two space velocities commonly used in industry are the liquid hourly
and gas hourly space velocities, LHSV and GHSV, respectively. The υ0 in the LHSV is
frequently measured as that of a liquid at 60 or 75"F, even though the feed to the reactor
may be a vapor at some higher temperature. The υ0 in the GHSV is normally measured at
standard temperature and pressure (STP).
44 Dr. Arkan Jasim Hadi
Reactors in Series
2.5 Some Further Definitions

For reactions in which the rate depends only on the concentration of one species [-rA= f (cA)]
, it is usually convenient to report -rA as a function of concentration rather than conversion.
We can rewrite the design equation for a plug-flow reactor [Equation (2-16)] in terms of the
concentration, CA ,rather than in terms of conversion for the special case when υ = υ0.

45 Dr. Arkan Jasim Hadi

Reactors in Series
2.5 Some Further Definitions

Differentiating yields

Valid only if υ = υ0

46 Dr. Arkan Jasim Hadi