QUIZ 2

•Rubber
  (cis-polyisoprene) decomposes in a
calorimeter bomb into gases products at
500oC. From the reaction data, the decrease
of its concentration (mol/L) follows this
expression
, where t is time in minutes
Determine the rate law of this reaction and
the unit of rate constant
1
 Exercise
• Tests were run on a small experimental
reactor used for decomposing NO2 in an
automobile exhaust stream. In one series
of tests, a nitrogen stream containing
various concentrations of NO2 was fed to a
reactor, and the kinetic data obtained are
shown in the following figure. Each point
represents one complete run. The reactor
operates essentially as an isothermal
backmix reactor (CSTR). What can you
deduce about the apparent order of the
reaction over the temperature range
studied?
• The plot gives the fractional
decomposition of NO2 fed versus the ratio
of reactor volume V (in cm3 ) to the NO2
feed rate, FN02,0, ,(g mol/h), at different feed
concentrations of NO2 (in parts per million 2
by welght.
 CRE1 flashback
Reaction rate
Power
-rA or –r’A
Chapter 1 Rate laws

Analyze data
Batch
Reactor
Equation

Continuous/ Flow Elementary/ Non-E

Stirred tank

𝑝 𝑞 𝑟
  𝐶 𝐶 𝐶
Tubular (
−𝑟 𝐴 =𝑘 𝐴 𝐶 ∝𝐴 𝐶 𝛽𝐵 𝐶𝐶𝛾 … − 𝑃 𝑄 𝑅
𝐾𝐶 )
  𝑑𝑁𝑖
Packed/fixed bed 𝐹𝑖 0 − 𝐹 𝑖+ 𝑟 𝑖 𝑉 = 3
Hollow 𝑑𝑡
 Mole Balance of
Reactive Unit
• GENERAL
dN j
Fj 0  Fj  rjV 
dt Batch?
• Stirred Tank Reactor (STR)
dN A
FA0  FA  rAV 
dt Continuous (CSTR)?
• Tubular Reactor
Plug Flow?
dN A
FA V  FA V V  rA V 
dt
Packed-Bed?

4
Chapter 2

Conversion
and
Reactor Sizing

5
 Objectives

Upon the completion of this chapter, students should be

able to:

• Define and compute conversion for any reactive unit

• Rewrite the design equations as the functions of
conversion
• Size the reactors based on the rate given as a function
of conversion

6
Conversions

Definition

7
 Conversions

Consider reaction
aA + bB → cC + dD

Using basis stoichiometric coefficients,

A is a limiting reactant

Thus, b c d
A B  C  D
a a a
So,
Conversion of A is Constant
volume only
moles of A reacted N A0  N A FA0  FA C A0  C A
XA    
moles of A fed N A0 FA0 C A0
8
Design Equations

9
 Design Equations:
Batch System
• To design a batch reactor that produce
 conversion a certain
of A in desired length of time,
From moles balances equation for batch system is
rAV = dNA/dt
Knowing that N A  N A 0  N A0 X

Thus, d  N A0  N A0 X  dX
rAV    N A0
dt dt
dX
 rAV  N A0
dt
If, V constant, V=V0,
 Design Equations:
Batch System
• Batch
  reactor design is based on the time
desired to get a certain conversion

• The volume of the reactor would be based
on the number of moles and initial
concentration, V=NA0/CA0

11
 Design Equations:
Flow System
• For continuous system, time is proportional with volume.
Thus, conversion for flow system is a function of volume, V
Fjo
FA = FA0 - FA0X
= FA0 (1-X)
Fj
where
FA = molar flow rate of A leaves system
FA0 = molar flow rate of A fed to the system
X = conversion of A

12
 Design Equations:
Flow System
• For CSTR , mole balance is:
V= (FA – FAo)/rj

Knowing that
FA = FA0 - FA0X

Thus,
FA0  FA FA0   FA0  FA0 X 
V 
rA rA
FA0 X
V
  rA  exit 13
 Design Equations:
Flow System
• For PFR, mole balance of A is ∆V
Fjo Fj
dFA/dV = rA ∆Gj
• For flow system; FA= FA0 –FA0X
• Differentiating; dFA = -FA0dX dFA
• Substitute into PFR’s mole balance;  rA
dV
dX
FA0  rA
dV
X
dX
V  FA0 
0
 rA
14
 Design Equations:
Flow System
• For PBR, mole balance of A is W ∆W W + ∆W
Fjo Fj
dFA/dW = r’A Gj
• For flow system; FA= FA0 –FA0X
• Differentiating; dFA = -FA0dX
dFA
• Substitute into PBR’s mole balance;  rA
dX dW
FA0  r ' A
dW
• In the absence of pressure drop, ∆P=0, we can integrate
it into; X
dX
W  FA0 
0
 rA 15
 Summary

dN A   V
 rAV
Batch dt
Limiting reactant
Nj 𝑋
dNA   𝑁 𝐴 0 𝑑𝑋
t    X= 𝑡 =∫
𝑉 ( −𝑟 𝐴 )
NAO
(rA )V 0

CSTR FA0  FA  𝐹𝐴0 𝑋

V 𝑉=
 (rA ) −𝑟𝐴
dFA F  𝑑𝑋 −𝑟 𝐴
dF A
Limiting reactant =
PFR  rA V   A 𝑑𝑉 𝐹 𝐴  0 𝑋
dV (rA ) 𝑑𝑋
F AO   X= 𝑉 =∫ 𝐹 𝐴 0
−𝑟𝐴
dFA FA  𝑑𝑋 𝑟 𝐴′ 0

 r A' W  dFA =−
PBR
dW F (rA' ) 𝑑𝑊 𝐹 𝐴0
 
𝑋
𝑑𝑋
16
AO
𝑊 =∫ 𝐹 𝐴 0
0 − 𝑟 𝐴′❑
Design
Applications

17
 Applications

The CSTRs and PFRs can be sized by:

• Given –rA with a function of conversion.

 rA  f  X 
• Construct Levenspiel plot by plotting either FAO/-rA or
1/-rA as a function of X.
• This plot is useful when –rA is difficult to solve

18
 Applications

X
FA0 X FA0
VCSTR  VPFR  dX
 rA 0
 rA

CSTR PFR

FA0 FA0
(rA ) (rA )

X X 19
• Irreversible reaction
1
 As X1,-rA0, thus, ∞ therefore
 rA
V∞
• Reversible reaction
 The max conversion is the equilibrium
conversion, Xe.
 As XXe,-rA0, thus, 1 ∞ therefore
 rA
V∞
20
 Reactor in Series
FAO
X1 X2
1 FA1 FA2
2
CSTR
PFR
X3
3
FA3

CSTR
Moles of A reacted up to reactor n
Xn 
Moles of A feed to first r eactor

 Valid with no side stream*

21
 Reactor in Series
FA0 X 1
V1 
1200 V3  rA1
1000 X2
FA0
V2  
-FAO/rA (dm3 )

800 dX
600 X1
rA
400
V2
200
V1
FAO  X 2  X 1 
V2 
0
0 X1 0.3 0.4 0.5 0.6
0.1 0.2 X2 0.7 0.8 0.85
X3
 rA 2
FAO  X 3  X 2 
Conversion, X

V3 
 rA3
22
 PFR in Series

FAO FA1
FA2
X=0
X=X2 FA3; X=X3
X=X1

Let us compare two scenarios

(i) Single reactor achieving X3

(ii) 3 reactors in series achieving
FA0/-rA
X3

• How is the total volume of 3

reactors in series related to
single reactor ??
23
X
 CSTR in Series
FAO
Can we model PFR as a series of
X=0 FA1
“n” equal volume CSTRs??
X=X1 FA2
FA3; X=X3
X=X2

Compare volume for the following 2

cases
(i) A single reactor achieving X3 FA0/-rA
(ii) 3 reactors in series achieving X3

How is the total volume of 3 reactors

in series related to single reactor ??
X 24
 The total residence time of the CSTR battery
approaches that of the PFR for large number of n.
26
Space Time and
Space Velocity

27
 Space Time and
Space Velocity
• The conversion of reactants in a chemical reactor is
directly related to the time that the chemical species
spend in the reactor.

• Two types of time-parameters are commonly used in

chemical reaction engineering
– space time
– residence time

• Space time is often used as a scaling parameter in

reactor design
28
 Definitions of Space Time
and Space Velocity
V

Space Time () : vo
Time required to process 1 reactor volume of fluid at inlet
conditions
vo
SV 
Space Velocity: V
• LHSV-Liquid Hourly Space Velocity
(liquid feed rate at 60 or75 °F)
• GHSV - Gas Hourly Space Velocity
(gas feed rate at STP)

Actual Residence Time: The time actually spent by fluid

inside the reactor.
Mean Residence
Time of Flow Reactor

30
 Summary
Differential Algebraic Equation Integral
Equation Equation

Batch
dX X
dX
N A0  rA V t  N A0 
dt - rA V
0

CSTR
FA0  X out  X in 
V
 (rA ) out
PFR
dX X ou t
dX
FA0  rA V  FA0  - rA
dV X in

PBR Xout
dX dX
FA0
dW
 rA' W  FA0 X - rA'
in
31
 Example

• A gas of pure A at 830 kPa enters a reactor

with a volumetric flow rate, v0 of 2 dm3/s
at 500 K. Calculate the entering
concentration of A, CA0 and the entering
molar flow rate, FA0. Assume A is an ideal
gas.

32
 Example 1: Sizing PFR

• Considering an isothermal gas-phase

isomerization, A→B. Determine the PFR
volume necessary to achieve 80%
conversion. The entering molar flow rate of
A is 0.4 mol/s.
X 0.0 0.1 0.2 0.4 0.6 0.7 0.8

-rA (mol/m3.s) 0.4 0.3 0.3 0.19 0.113 0.07 0.05

5 7 0 5 9
 Example 1 (Procedure
of solving)
• Process data
X 0.0 0.1 0.2 0.4 0.6 0.7 0.8

FAo/-rA (m3) 0.89 1.08 1.33 2.05 3.54 5.06 8.0

• Solve design equation

0 .8
FAO
V  dX
0
 rA
 Example 2:
Sizing CSTR
• The reaction described in Example 1 is to
be carried out in a CSTR. Calculate the
volume necessary to achieve 80%
conversion

35
 Example 3: Reactor in
series

• The isomerization of butane n-C4H10 → i-C4H10 was

carried out adiabatically in liquid phase and the data in
table below was obtained. The reactor scheme is also
shown. Calculate the volume of each of the reactors for
an entering molar flow rate of n-butane of 50 kmol/hr).
X1=0.2, X2=0.6 and X3= 0.65.
X 0.0 0.2 0.4 0.6 0.65

-rA (kmol/m3.h) 39 53 59 38 25
The End

37