L2b-1

L2b: Reactor Molar Balance

Example Problems
Fj0 Fj
Gj

reactor

Today we will use BMB to derive

reactor design equations. Your
goal is to learn this process, not
to memorize the equations!

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2b-2

Review: Basic Molar Balance BMB

Rate of Rate of
Rate of flow of j Rate of flow of
generation of j accumulation of j
into the system - j out of system + =
by chemical rxn in the system
[moles/time] [moles/time]
[moles/time] [moles/time]

dN j
Fj0 Fj Gj
dt

V
�rjdV

Fj0 Fj
Gj

System volume
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2b-3

Review: Batch Reactor Basic Mole Balance

• No material enters or leaves the reactor
• In ideal reactor, composition and temperature are spatially
uniform (i.e. perfect mixing)
• No flow in or out of reactor. Fj0 and Fj = 0.

Rate of generation of reactant Rate of accumulation of

=
A in reactor due to rxn reactant A in reactor
V dN j Batch Reactor
 rjdV 
dt Design Equation
Ideal (perfectly mixed)
dN j Ideal Batch Reactor
reactor: spatially uniform r V 
j Design Equation
temp, conc, & reaction rate dt

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2b-4

Review: CSTR Basic Mole Balance

• Continuously add reactants and remove products Fj0 Fj
• In an ideal reactor, composition and temperature
are spatially uniform (i.e. perfect mixing)
• At steady state- no accumulation
Accumulation = In - Out + Generation
by rxn V
0 = Fj0 - Fj +  rjdV
No spatial variation:
rj V
Ideal Steady State CSTR Design Equation:
Fj0 -Fj 0C A 0 - C A
in terms V 
-r j
( )
F j  C j (  ) �V 
-rA
in terms of
of flow concentration
 (upsilon)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2b-5

Review: Mole Balance – PFR

• Flow reactor operated at steady state (no accumulation per Δ)
• Composition of fluid varies down length of reactor (material
balance for differential element of volume DV
ΔV

FA0 FA
dN j
Fj0 - Fj + rjDV =
dt
lim Fj V  DV -Fj V
Fj - Fj  rjDV  0   rj
V V  DV DV  0 DV

dFj Ideal SS PFR

 rj
dV Design Eq.
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
Review: Mole Balance- Packed Bed
L2b-6

Reactor (PBR)
• Heterogeneous rxn: reaction occurs at catalyst particle surface
• Concentration gradient of reactant and product change down
length of the reactor
• Rxn rate based on the mass of catalyst W, not reactor volume V

dFj Similar to PFR, but expressed in terms of

 rj
dV catalyst weight instead of reactor volume

Units for the rate of a mol Units for the rate of mol
homogeneous rxn (rj) : s  m3 a catalytic rxn (rj’) : s  kg catalyst

So in terms of catalyst weight instead of reactor volume:

dFj
 rj ' where W is the weight of the catalyst
dW
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2b-7

Consider a reaction that occurs on a catalyst surface (a

heterogeneous rxn). How is the reaction rate r’j that is in terms of
the weight of catalyst related to the rate in terms of volume (r j)?
Hint: rj = x r’j What is x?

mol  mol  Rearrange to

3
 x  solve for x
sm  s  kg catalyst 
 mol  s  kg catalyst 
    x
 s  m3  mol 
 kg catalyst  catalyst weight Bulk catalyst
 3
  x   rb density
 m  catalyst volume
rj = rb r’j

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 Use your result from the previous question to derive a reactor design L2b-8
equation for a fluidized CSTR containing catalyst particles. The equation
should be in terms of catalyst weight (W) and the reaction rate for an
equation that uses solid catalyst. Assume perfect mixing and steady-state
operation of the CSTR.
What is the CSTR design equation? In - Out + Gen = Accumulation
dNj
Fj0 - F j rjV 
dt
Rearrange to put in terms of V
Fj0 - Fj 0
V
-rj

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 Use your result from the previous question to derive a reactor design L2b-9
equation for a fluidized CSTR containing catalyst particles. The equation
should be in terms of catalyst weight (W) and the reaction rate for an
equation that uses solid catalyst. Assume perfect mixing and steady-state
operation of the CSTR. Need an equation that has
Fj0 - Fj
CSTR design equation: V W instead of V and –rj’
-rj
instead of -rj
Step 1: Come up with an equation that relates V to W (V=?W) &
substitute this equivalency into the CSTR design equation.
F - Fj
W � V  W Substitute W/ρb for V V  Fj0 - Fj � W  j0
rb  rb -rj
V rb in design eq: -rj

Step 2: Substitute an expression that relates –rj to –rj’ into the design eq:
mol mol
Units for rj: Units for rj’:
s�m3 s�kg catalyst

From the previous question: rj = rb r’j

W Fj0 - Fj W Fj0 - Fj Fj0 - Fj Ideal Fluidized

 �  Simplify: � W 
rb -rj rb rb -rj ' ( ) -rj ' CSTR Design
Equation
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2b-10
Use basic molar balance to derive a reactor design equation for a fluidized
CSTR containing catalyst particles. The equation should be in terms of
catalyst weight (W) and the reaction rate for an equation that uses solid
catalyst. Assume perfect mixing and steady-state operation of the CSTR.
In - Out + Generation = Accumulation
W dN j
Fj0 - F j  �rj ' dW 
dt
�mol ��mol � �mol � d
� �� � � ( kg)
� ( mol )
� s �� s � � kggs � dt
1. Simplify this expression. Things to consider: Is there flow?
Accumulation? Is the reaction rate the same everywhere in the reactor?
W dN j
Fj0 - F j  �rj ' dW  At steady state
dt
0
� Fj0 - F j rj ' W  0 Rearrange to get in terms of W

Fj0 - Fj Ideal Fluidized

� Fj0 - Fj  -rj ' W �  W CSTR Design
-rj '
Equation
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 The reaction A→B is to be carried out isothermally in a continuous-flowL2b-11
reactor. Calculate the CSTR volume to consume 99% of A (CA=0.01CA0)
when the entering molar flow rate is 5 mol A/h, the volumetric flow rate is
constant at 10 dm3/h and the rate is –rA=(3dm3/mol•h)CA2.
( )
Fj  C j (  ) 0 = 10 dm3/h = 
reactor
FA0=5 mol A/h FA=CA where CA = 0.01CA0

j dN
CSTR design eq: In - Out + Gen = Accumulation Fj0 - F j rjV 
dt
FA 0 - F A CA0 - C A  Substitute in: 0
�V �V  –rA=(3dm3/mol•h)CA2 & CA=0.01CA0
-r A -r A
CA0 - 0.01C A 0 Factor
CA0 ( 1 - 0.01)
�V  V
( ) 2
3 dm3 molgh ( 0.01) C A02 numerator ( 2
)
3 dm3 molgh ( 0.01) C A02

0.99 5 mol
� V= We know . FA 0 h =0.5 mol
( 3 dm3 molgh) ( 0.01) 
2 C C A0 =
CA0 What is CA0? A0 0 10 dm3 h dm3

�V 
(
0.99 10 dm3 h )
� V  66,000 dm3
( 3 dm3 molgh) ( 0.01) 2 ( 0.5 mol dm3 )
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 The reaction A→B is to be carried out isothermally in a continuous-flowL2b-12
reactor. Calculate the PFR volume to consume 99% of A (CA=0.01CA0)
when the entering molar flow rate is 5 mol A/h, the volumetric flow rate is
constant at 10 dm3/h and the rate is –rA=(3dm3/mol•h)CA2. CA0 = 5mol3h =0.5 mol3
( )
Fj  C j (  ) 0 = 10 dm3/h = 
reactor
10 dm h dm

FA0=5 mol A/h FA=CA where CA = 0.01CA0

dF dCA Substitute in: –r =(3dm 3
/mol•h)C 2
but
PFR design eq: A  rA �  rA A A

dV dV not CA=0.01CA0 until after integration!

0.01CA0
dC A � dm3 � 2  dCA V
� �-3 C � �  �dV
� molgh �
dV �
�A
�
3
-3 dm molgh CA0 C A (
2
0 )
b
( )
b b b -n1 -n1 -1�b dx
REVIEW: 1
� n dx  �
for n≠1: a x
x-ndx � �
�x-n1
( -n  1) �
� �
b
-
a �2 
x�
a a -n  1 -n  1 a x �
a

 � -1 -1 � 10 dm3 h � 1 1 �dm3
� - V� � - � V
( �
-3 dm3 molgh � ) �
0.01CA0 CA0 � �
�
�
-3 dm
3 ��
�
molgh �
0.01( 0.5 ) 0.5 �mol

Much smaller V required to get same conversion in a PFR

� 660 dm3  V
than in a CSTR
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2b-13
The gas phase reaction A→B+C will be carried out isothermally in a 20 dm 3

constant volume, well-mixed batch reactor. 20 moles of pure A is initially

placed in the reactor. If the rate is –rA=kCA and k=0.865 min-1, calculate the
time needed to reduce the number of moles of A in the reactor to 0.2 mol.
DDDD dNj dNA Batch reactor
In - Out +Gen = Accum Fj0 - F j rjV  � rA V 
dt dt design eq
0 0
Need to convert to dCA/dt N
C A  A so NA  CA V
How is dCA/dt related to dNA/dt? V
dNA d dNA dC A dV dNA dCA Plug into
�  ( CA V ) �  V  C A � V design eq
dt dt dt dt dt dt d t
0
dCA dC A Plug in dCA Rearrange
� rA V  V � rA  rate law
� -k C A 
dt dt dt & integrate
b1 b
REVIEW: ln( x) �  ln( b) - ln( a)  ln �b�
� n dx  �
� �
a ��
for n=1: ax �a �
t dCA � -kt  ln CA Convert Cj � -kt  ln NA V � t  1 ln NA
CA
� -k �dt  � CA0 back to Nj/V -k NA0
0 CA 0 C A
NA0 V
min 0.2
Substitute in values for k, NA0, & NA � t  - ln � t  5.3 min
0.865 20
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2b-14
Polymath example problem 1-17

There are initially 500 rabbits (x) and 200 foxes (y). Use Polymath to plot the
number of rabbits and foxes as a function of time for a period of up to 500 days.
The predator-prey relationship is given by the following coupled ODEs:

dx dy
 k1x - k 2 xy  k 3 xy - k 4 y
dt dt

Constant for growth for rabbits k1= 0.02 day-1

Constant for death of rabbits k2=0.00004/(day∙number of foxes)
Constant for growth of foxes after eating rabbits k3=0.0004/(day∙number of rabbits)
Constant for death of foxes k4= 0.04 day-1

Also, what happens if k3=0.00004/day and t=800 days? Plot the number of foxes vs
rabbits.

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2b-15
Initially 500 rabbits (x) and 200 foxes (y). Predator-prey relationship is given by the
following coupled ODEs: dx
 k1x - k 2 xy
dy
 k 3 xy - k 4 y
dt dt
Constant for growth of rabbits: k1= 0.02 day-1
Constant for death of rabbits: k2=0.00004/(day∙number of foxes)
Constant for growth of foxes after eating rabbits k3=0.0004/(day∙number of rabbits)
Constant for death of foxes k4= 0.04 day-1
t= 0 to 500 days

• Make sure the “Graph” and “Report” buttons are checked above
• After typing in the 2 differential equations, conditions for t=0, constants,
and initial and final time pts, press the magenta arrow to solve
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2b-16

Polymath report:

Number of rabbits at
500 days

Number of foxes at
500 days

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2b-17

Polymath graph:

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2b-18
What happens if k3=0.00004/day and t=800
days? Plot the number of foxes vs rabbits.

• Make sure the “Graph” and “Report” buttons are checked above
• After changing t(f) to 800 and k3 to 0.00004, press the magenta arrow
to solve

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2b-19

Number of rabbits
at 800 days

Number of foxes at
800 days

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2b-20

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.