MOLE BALANCE

General Balance
Rate of generation 
Rate of input of  Rate of output of    Rate of component j
     of component j due to   
component j 
 component j 
    Accumulate d 
into the reactor  from the reactor  chemical reaction  in the reactor 
    in the reactor   
 

• Above equation can be written for “A”.

• Rate does not mean change in any property with
time, but something transferred or consumed
per time. Can be constant/changing/uniform.
• What should be sign of third term?
• Can you write same equation for energy
balance?
 General Balance

• Consider a general stoichiometry

aA + bB cC + dD
• Fix the boundary condition
• Fix the component “A” (Limiting Reactant)
 Terminology
• a,b,c,d = Stoichiometric coefficients
• A,B,C,D = Components taking part in reaction
• j = A chemical component
• FA0, FA = Molar flow rates of components at the inlet and
outlet of the reactor, (moles/time)
• A0, A = Total volumetric flow rate at inlet and outlet of the
reactor, (liters/time)
• GA = Molar rate of generation due to chemical reaction,
(moles/time)
• rA = rate of reaction of component “j”, (moles/liter.time)
• V = Volume of the reactor, (liters)
• CA0,CA = Concentration of components at inlet and outlet of
the reactor (moles/liters)
• NA0,NA = Moles of components at inlet and outlet of the
reactor (moles)
• t = Time of chemical reaction (time)
• XA0,XA = Conversion of components at inlet and outlet of the
reactor
 BALANCE OF COMPONENT “j”
Rate of generation 
Rate of input of  Rate of output of    Rate of component j
     of component j due to   
component j 
 component j 
    Accumulate d 
into the reactor  from the reactor  chemical reaction  in the reactor 
    in the reactor   
 

• Mole of component “A” into the system between t and t+t  FA0 t

• Mole of component “A” out of the system between t and t+t  FAt

• Mole of component “A” generated in the system between t and t+t

 GAt

• Mole of component “A” accumulated in the system between t and

t+t  NA = (NA(t+t)-NA(t))
 BALANCE OF COMPONENT “A”
• Applying general balance equation between t
and t+t

FA0t FA t G A t  N A 

• Rearranging above equation and taking t0

dN A
FA0  FA  G A 
dt
What do we do with this term?
 Understand GA term
• Net rate of moles of “A” generated per unit
time can be given by
 moles   Moles 
+Ve : Products
GA    rA    V liters  -Ve : reactants
 time   liter .time 
 Understand GA term
G A1  rA1  V1
G A2  rA2  V2 • For the case n  V 0
  
 V
G Ai  rAi  Vi G A   G Ai 
   i 1 V 0
 r V A

G An  rAn  Vn V

n
  r dV
V 0
A

G A   G Ai
i 1
 BALANCE OF COMPONENT “A”

V
dN A
FA0  FA   rAdV 
V 0
dt

Master equation for any reacting system

carried in any type of reactor
 Design of ideal reactors
• Ideal isothermal batch reactor
• Ideal isothermal CSTR (Steady state condition)
• Ideal isothermal PFR (Steady state condition)
• Ideal isothermal Semi Batch Reactor

• Steady state if attained in reactor is

not an equilibrium !!!!
What if system in transient mode?
• Main purpose of studying transient behavior of
the system
– The calculation of the time required for the system to
approach to within 1% of the steady state
– Identifying the start up procedure that will reduce the
above said time
– Investigation of the type of products obtained during
the approach towards steady state
– Calculation of speed at which change or fluctuations
at the reactor inlet are transmitted to the outlet or to
any intermediate point in the system
 Sizing Reactor
• It is normal to calculate the size needed for a
certain reaction or separation to achieve desired
level of conversion or separation.

• The size is an important factor and it implies the

cost.
– Both capital and operating cost

• The bigger the reactor gets, the higher the price

 Design Algorithm
Start
Evaluate equations, solve, analyze
and final answer
General Mole Balance equation

Design Equation for reactor type

If no change in moles and no pressure drop
• Combine rate law and stoichiometry tables
Is –rA = f(CA) given? • Get Rate law equation

NO
Determine Rate Law Equation
Combine:
• Mole Balance & Design equation
Use Stoichiometry Tables • Rate law equations and tables
-P • Pressure Drop & Solve Then

Gas Phase with Pressure Drop

SIZING BATCH REACTOR
 Revisiting Batch
• If liquid Phase
– Change in density is neglected
• If gas phase
– No change in volume
– Vessel volume is fixed
• Assumptions
– Well mixed
– Reactants enter at the same time
– No side reactions
– Filling time may be neglected
– Isothermal Operation
 Stoichiometric Table
• Consider a liquid phase t=0
constant volume reaction: NA0, NB0, NC0, ND0,NI0
• aA + bB + iI  cC + dD + iI
• A + (b/a)B + (i/a)I  (c/a)C +
(d/a)D + (i/a)I

Because of reaction
at any time “t” t=t
NA0  NA
NA, NB, NC, ND,NI

• Based on species “A” as  rA  rB rC rD

  
Limiting Reactant a b c d
 Stoichiometric Table (Const. Density)
Initial  Change Final (Nj0 + )=Nj
Nj0
NA0 -NA0XA NA = NA0-NA0XA
NB0 -(b/a) NA0XA NB=NB0-(b/a) NA0XA
NC0 +(c/a) NA0XA NC=NC0+(c/a) NA0XA
ND0 +(d/a) NA0XA ND=ND0+(d/a) NA0XA
NI0 - NI=NI0
NT0 NT0=NA0XA(-1- NT=NT0
b/a+c/a+d/a) +NA0XA(-1-b/a+c/a+d/a)
Stoichiometric Table (Const. Density)
Final Nj Final Cj = Nj/V
NA = NA0-NA0XA CA = CA0(1-XA)
NB=NB0-(b/a) NA0XA CB=CA0(MB-(b/a) XA)
NC=NC0+(c/a) NA0XA CC=CA0(MC-(c/a) XA)
ND=ND0+(d/a) NA0XA CD=CA0(MD-(d/a) XA)
NI=NI0 CI=CI0
NT=NT0 +NA0XA(-1- CT=CT0 +CA0XA(-1-
b/a+c/a+d/a) b/a+c/a+d/a)
C j0
Mj 
C A0
 Practice Time
• Soap consists of the sodium and potassium salts of
various fatty acids such as oleic stearic, palmitic, lauric,
and myristic acids. The saponification for the formation
of soap from aqueous caustic soda and glyceryl
stearate is

Letting X represent the conversion of sodium hydroxide

(the moles of sodium hydroxide reacted per mole of
sodium hydroxide initially present), set up a
stoichiometric table expressing the concentration of
each species in terms of its initial concentration and
the conversion X.
Reference: Foglar 4th Ed. Prob. 3.2
 Hint
• General Stoichiometry
3A + B 3C + D
• Make above stoichiometry on Per mole of
Limiting reactant.
• Assume reaction is occurring in Batch reactor
• Because of liquid phase Reaction is of constant
volume
• Water is present into the system because of
NaOH solution. So it can be considered as Inert.
 Problem (Can you design?)
• Having set up the stoichiometric table in Previous
Problem, one can now readily use it to
– calculate the concentrations at a given conversion. If
the initial mixture consists solely of sodium hydroxide
at a concentration of 10 mol/dm3 and of Glyceryl
stearate at a concentration of 2 mol/dm3, what is the
concentration of glycerine when the conversion of
sodium hydroxide is
– (a) 20%
– (b) 90%
 Stoichiometry Table (variable volume)
Final Cj = Nj/V
CA = CA0(1-XA)/(1+AXA)
CB=CA0(MB-(b/a) XA) /(1+AXA)
CC=CA0(MC-(c/a) XA) /(1+AXA)
CD=CA0(MD-(d/a) XA) /(1+AXA)
CI=CI0
CT=CT0 +CA0XA(-1-b/a+c/a+d/a) /(1+AXA)
 Batch Reactor
V
dN A
FA0  FA   rAdV 
dt
No flow in

No flow out

V V Perfectly mixed, so no
variation in the rate of
 rA dV  rA  dV  rAV reaction throughout the
reactor volume,take rA out of
6/17/2019 7:19 AM 23
integral
 Batch Reactor
dN A
 rAV
dt
And if the volume is not a function of time (constant)

d ( N A / V ) dC A
  rA
dt dt
6/17/2019 7:19 AM 24
 Integral form of design equation
(Constant Volume Reaction)
N Af t
dN A  dN   rAVdt
 rAV upon integration
N A0
A
0

dt N Af
dN A
t 
rV
N A0 A
But Literature says –rA
N Af N A0 C A0 X Af
dN A dN A dC A dX A
t       C A0 
N A0
 rAV N Af  rAV C Af  rA 0
 rA
 Integral form of design equation
(Variable Volume Reaction)
N Af t N Af
dN A
N dN A  0 rAV f dt  t  N rAV0 1   A X A 
A0 A0

dN A0 1  X A 
N Af N A0
dN A
t   
N A0
 rAV0 1   A X A  N Af  rAV0 1   A X A 
X Af
 dX A
X A0
N A0 dX A

V0 
X Af
 rA 1   A X A 
 C A0 
0
 rA 1   A X A 
Graphical Representation

Levenspiel Plots
 The Godfathers OF CRE

OCTAVE LEVELSPIEL H.SCOTT FOGLAR

CAN WE USE DESIGN EQUATION OF
BATCH REACTOR ANALYTICALLY?

1. How about first order reaction? (Unimolecular, irreversible)

2. How about second order reaction? (Unimolecular,
irreversible)
3. What if one of the reactants is excess?
4. How about nth Order reaction? (Unimolecular, irreversible)
5. How about variable volume reactions?
6. How about bimolecular second order reaction?
7. What if there are multiple reactions?
 First Order Reaction
• Given first order elementary reaction
-rA = kCA
• Calculate the time needed to achieve the final
conversion  XA = 90%
 First Order Reaction
• -rA = kCA
• According to design equation of Batch reactor

 k 1  X A 
dC A dX A
 kCA
dt dt
 CA 
 ln 1  X A    ln    kt
Accumulation Generation

 C A0 
 First Order Reaction
• Substitute all the values.
• You don’t need initial concentration!!!!
• Take k = 10-4 sec-1.
• According to equation

 ln( 1  0.9)
t 4
 23025 sec  6.9hr
10
 Second Order Reaction
• Given Second order elementary reaction
-rA = kC2A
t •XCalculate
A  0.9, C Athe
0  10 gmol / L, k  10 4
time needed to achieve the final
L / sec .gmol

t
conversion  0.X9A = 90%
 9000 sec  2.5hr
10 4

L / sec .gmol 10 gmol / L 1  0.9
Solve by your own!!!!

You have 1.5min time for

derivation

Ask for required data

 Comparison of reaction time
• Note rate constant values.
• Time of reaction decreases
• K value is adapted to rate of reaction:
– Must match dimensions (Time, concentration,
volume, moles etc.)
 Exercise
• We are planning to operate a batch reactor to convert A into R
in constant volume liquid phase batch reactor according to A
 R. The experimental data for rate of reaction for various
values of concentration are given in table. How long must we
react each batch for concentration to drop from CA0 =
1.3mol/lit to Caf = 0.3mol/lit

CA,mol/lit -rA, CA,mol/lit -rA,

mol/litmin mol/litmin
0.1 0.1 0.7 0.1
0.2 0.3 0.8 0.06
0.3 0.5 1.0 0.05
0.4 0.6 1.3 0.045
0.5 0.5 2.0 0.042
0.6 0.25
 Reference: Foglar 4th Ed. Prob. 4.1

Exercise
• It is desired to design a CSTR to produce 200 million pounds of ethylene glycol by
hydrolyzing ethylene oxide. However, before the design can be carried out it is
necessary, to perform and analyze a batch reactor experiment to determine specific
reaction rate constant, k. Because the reaction will be carried out isothermally, the
specific reaction rate will need to be determined only at the reaction temperature of
the CSTR. At high temperatures there is a significant by-product formation, while at
temperatures below 40°C the reaction does not proceed at significant rate;
consequently. A temperature of 55°C has been chosen. Because water is usually present
in excess, its concentration may be considered constant during the course of the
reaction. The reaction is first-order in ethylene oxide.

• In the laboratory experiment, 500ml of a 2M solution of ethylene oxide in water was

mixed with 500ml of water containing 0.9wt% sulfuric acid, which is a catalyst. The
temperature was maintained at 55C. The concentration of ethylene glycol was recorded
as a function of time.
 Exercise
Time 0 0.5 1.0 1.5 2.0 3.0 4.0 6.0 10
Min
Con of 0 0.145 0.27 0.376 0.467 0.61 0.715 0.848 0.995
EG
Kmol/
m3

• For the given conditions obtained the kinetics

of the reaction.
• For a given kinetics determine the final
conversion for a batch time of 45min.
 Empty,
Cycle of a Batch Dirty,
Empty, Dirty, Ambient T Heat/Cool

Empty, Clean, Ambient T

Time tK
Time tc

Time tf Time th Time tR Time tE

Empty, Full, Dirty, Full, Dirty,

Full, Dirty,
Ambient T Heat/Cool
Clean, Heat/Cool
Ambient T Reaction
 Cycle Time
• A normal cycle goes as:
Cycle Time  t f  t h  t r  te  t k  tc

– tf : Time required to feed

– th : Time required to heat/cool before reaction
– tr : time required to carry out reaction
– te : time required to empty the reactor
– tk : time required to heat/cool after the reaction
– tc : time required to clean the reactor to make
ready for next batch
Cycle Time
• The fraction of time required to do the actual
reaction vs the total time Re action Time
Ratio 
– Must be near 1.0 as possible Cycle Time
– If near 0, then the time we spend is mainly to
“Prepare” the reactor for that specific reaction
• Not to mix the times when given in data
– Reaction time, feeding time, time needed to
clean, time required to heat, time spent in
maintenance etc.
 Exercise
• If
– tf : 25min
– th : 2hr
– tr : 6.7hr
– te : 23min
– tk :1.2hr
– tc : 30min
• What is the total cycle time?
• What is the fraction of time that reaction vs batch
time?
 How to obtain Volume of Batch
X
Reactor? t  Af
dX A
C A0   rA 1   A X A 
0

• There is no volume Term in the design equation.

• But one knows production capacity!!!!!!
• Production rate = 24 tpd.
• Design equation does not guide at what is
volume required to produce this quantity?
• For any value of conversion one can get only time
required to reach that value.
Sizing Batch Reactor

•What is time at XA = 1?

•How much time increases

from 50% to 60% conversion?

•How much time increases

from 95% to 99%?

•Give economical viable

size/conversion of the
reactor!!!!
 Sizing Batch Reactor
• Suppose I get t = 7hrs from graphical method,

• How to get volume of batch???????

 Sizing Batch Reactor
• Is 7hr total batch time or reaction time only?
• One has to add other timings for account for
batch time.
– Charging, heating, discharging, cleaning etc.
• For good management, suppose I take 60min as
remaining time.
• Total batch time = 8hrs/batch
• No of batches = 24 hrs a day/8 hrs = 3 batches
• Tones per batch = 24 tpd /3 = 8 tons/batch
• Volume of reactor = 8000kg/1000kg/m3 = 8m3
 Sizing Batch Reactor
• Which volume this value represents?
• How will you accommodate 8m3 of volume?
– Which shape?  cylinder, sphere, triangle, rectangle
– Diameter and Length
– Two options (Non engineering solutions)
• 1 nm diameter and what is length?
• Diameter of earth and what is length?
– What is thumb rule to get L/D?
• Value (0  100)  1
• Criteria (????)
SIZING CONTINUOUS REACTOR
 Stoichiometry Table for continuous
reactors

FA0 FA
aA + bB cC + dD
FB0 FB
FC0 FC
FD0 FD
FI0 Gas phase reaction moles changes FI
due to
liquid phase reaction •Non isothermal
•Isothermal reactions •Variable pressure
•Isobaric reactions •Variable volume
•Nature of reaction
Conversion in continuous reactors
• Definition of conversion
Moles reacted Moles reacted Time
Conversion  
Moles fed Moles fed Time
• FA0 = moles of reactant entering into the reactor
unit time (Inlet or Entry)
• FA = moles of reactant leaving the reactor unit
time (Outlet or Exit)
• FA0 - FA = moles of reactant reacted in the reactor
unit time (Within reactor)
FA0  FA
XA  FA  FA0 1  X A 
FA0
 Stoichiometry Table (Constant Density)
Initial  Change Final (Fi0 + )=Fi
Fi0
FA0 -FA0XA FA = FA0-FA0XA
FB0 -(b/a) FA0XA FB=FB0-(b/a)FA0XA
FC0 +(c/a) FA0XA FC=FC0+(c/a)FA0XA
FD0 +(d/a) FA0XA FD=FD0+(d/a)FA0XA
FI0 - FI=FI0
FT0 FA0XA(-1- FT=FT0
b/a+c/a+d/a) +FA0XA(-1-b/a+c/a+d/a)
Stoichiometric Table (Constant Density)
Final Ni Final Ci = Ni/V
FA = FA0-FA0XA CA = CA0(1-XA)
FB=FB0-(b/a) FA0XA CB=CA0(MB-(b/a) XA)
FC=FC0+(c/a) FA0XA CC=CA0(MC-(c/a) XA)
FD=FD0+(d/a) FA0XA CD=CA0(MD-(d/a) XA)
FI=FI0 CI=CI0
FT=FT0 +FA0XA(-1- CT=CT0 +CA0XA(-1-
b/a+c/a+d/a) b/a+c/a+d/a)
Fi 0 FA
Mi  CA 
FA0 
Stoichiometric Table (Variable Volume)
Assuming
Constant pressure
Isothermal condition

FA
CA    0 1   A X A 

FA0 FB 0 FT
C0  C A0  C B 0  ...    ... 
  
FA0 M j  j X 
Cj 
 FA  0 1  X 
C A  C0  
 FT  C j  C A0
M j  j X 
1  X 
Stoichiometric Table (Variable Volume)

Final Ci = Ni/V
CA = CA0(1-XA)/(1+AXA)
CB=CA0(MB-(b/a) XA) /(1+AXA)
CC=CA0(MC+(c/a) XA) /(1+AXA)
CD=CA0(MD+(d/a) XA) /(1+AXA)
CI=CI0
CT=CT0 +CA0XA(-1-b/a+c/a+d/a) /(1+AXA)
 Stoichiometric Table (Variable Volume)
Assuming
Pressure and Temperature changes during reaction

FA FA0 1  X A  FA0 1  X A   T0  P   1  X A  T0  P 
CA        C A0    
  0 1   A X A   T  P0   1   A X A  T  P0 
FBFA0 M B  b a X A   T0  P   M B  b a X A  T0  P 
CB       C A0    
 0 1   A X A   T  P0   1   A X A  T  P0 
FC FA0 M C  c a X A   T0  P   M C  c a X A  T0  P 
CC        C 
A0 
  
 0 1   A X A   T  P0   1   A X A  T  P0 
FDFA0 M D  d a X A   T0  P   M D  d a X A  T0  P 
CD    
    C A0    
 0 1   A X A   T  P0   1   A X A  T  P0 
 Practice Time
• A mixture of 28% SO2 and 72% air is charged
to a flow reactor in which SO2 is oxidized
according to reaction
2SO2 + O2  2SO3
• Prepare a stoichiometric table for 1485 kPa
and 227C.

Reference: Foglar 4th Ed. Prob. 3.5

CSTR
Nomenclature
CSTR & Conversion
• Incase fresh feed entering to the reactor
– Input of A, moles/time = FA0
– Output of A, moles/time = FA = FA0(1-XA)
• Incase partially converted feed entering to the reactor
– Input of A, moles/time = FAi= (1-XAi)FA0
– Output of A, moles/time = FA = FA0(1-XAf)
• Moles/Time = (Moles/liter)*(Liter/Time)
• FA = CA*
• One can convert equation from molar rates to
concentration and finally to conversion.
• One can also introduce space time concept in the
design equation.
 CSTR
V
dN A
FA0  FA   rAdV 
dt
Steady state, no
accumulation,
Perfectly mixed

6/17/2019 7:19 AM 59
 CSTR

FA0  FA  rAV  0
The CSTR design equation gives the reactor volume V, necessary to
reduce the entering flow rate of species A, from FA0 to the exit flow rate
FA, when species A is disappearing at a rate of (-rA)exit

FA0  FA
V
(rA ) exit
6/17/2019 7:19 AM 60
 CSTR
• For the case of fresh feed entering to reactor

FA0 X A V XA
V  
(rA ) exit FA0 (rA ) exit
• For the case of partially converted feed
entering to the reactor
FA0 X Af  X Ai  V  X Af  X Ai 
V  
(rA ) exit FA0 (rA ) exit
 CSTR
• FA0 = CA0* and  = V/
V V 
 
FA0 C A0 C A0
• In form of concentration

V



C Ai  C Af 
C A0 C A0 (rA ) exit
 CSTR
• Final Form of Design Equation
V



 X Af  X Ai  C Ai  C Af 

FA0 C A0 (rA ) exit (rA ) exit
1 V VC A0 C A0 X Af
   
s 0 FA0 (rA ) exit
• Irrespective of whether constant volume or
variable volume
Graphical Solution
 Practices Problem 1
• Consider a first order chemical reaction
AB
• Inlet volumetric flow rate = 10dm3/min
• Outlet volumetric flow rate is same as inlet.
• Rate of reaction –rA = kCA where k = 0.23min-1
• If exiting concentration is 10% of the entering
concentration find the reactor volume.
 Practices Problem 2
• One liter per minute of liquid containing A and B (CA0 = 0.10
mol/liter, CB0 =0.01 mol/liter) flow into a mixed reactor of
volume V = 1 liter. The materials react in a complex manner
for which the stoichiometry is unknown. The outlet stream
from the reactor contains A, B, and C (CAf = 0.02 mol/liter, CBf =
0.03 mol/liter, CCf = 0.04 mol/liter), as shown in figure below.
Find the rate of reaction of A, B, and C for the conditions
within the reactor.
 Graphical Calculation
• Consider a first order chemical reaction
AB
• Is to be carried out in a CSTR. Species A enters
the reactor at a molar rate of 0.4mol/sec.
• Using data given in table below calculate the
volume necessary to achieve 80% conversion.
 Practices Problem 3
• Pure gaseous reactant A (CA0 = 100milli
mol/liter) is fed at a steady rate into a mixed
flow reactor (V = 0.1 liter) where it dimerizes
(2A  R). For different gas feed rates the
following data are obtained:

• Find the rate equation.

 Industrial Example 1
• Reaction of interest:
(CH3CO)2O + H2O → 2CH3COOH
A + B → 2C
• Mole Balance
 0 C A0 X  0 CC
V V
 rA rC
• Rate Law
– C B is constant and can be included in k
dm 3
 rA  k C A C B  kCA , k   1.97  10 4
mol  s

• Stoichiometry

rC  rA  kCA CC  2[C A O  C A ]

• Combine
 r  k C C  k C C  kC
A A B B0 A A

 r  kC 1  X 
A A0

C
V  1 dm
0 C 3

kC A

C
  C

k[C  C ]
exp
C
A0

V
 
 theory
k
X 
0

k 
X 1  k
1 X
 pH Cc X X
(mol/dm^3) (experiment) (theory)

2.630 0.988 .6613 .7519

2.612 0.990 .6622

2.551 1.009 .6707

2.498 1.040 .6842

2.503 1.033 .6812

• Solve
– We will use the experimental pH data and plug it into Cc to
determine the conversion (X).
– Cc was determined from the pH by a correlation between
the two.
 Industrial Example 2
• Consider the liquid phase cis-trans isomerization
of 2-butene which we will write symbolically as
AB.
• The first order (-rA=kCA) reaction is carried out in
a CSTR in which the volumetric flow rate, v, is
constant, i.e., v=v0.
– (a) Can you Sketch the concentration history?
– (b) Determine the reactor volume necessary to reduce
the exiting concentration to 10% of the entering
concentration when the volumetric flow rate is 10
dm3/min (i.e., liters/min) and the specific reaction rate,
k, is 0.23 min-1.
• Distributed parameter system
• Lumped parameter system
 INPUT OUTPUT
Input of A, moles/time = FA Output of A, moles/time = FA + dFA
Conversion of A = XA
PFR Conversion of A = XA + dXA

dVr
ΔV
CA0 CAf
FA FA+dFA
FA0
A0 FFAfA
XA XA+dXA
XA0= 0 XAf

Disappearance of A by reaction, moles/time = (-rA) dVr

 PFR dVr

CA0 CAf
FA0 GA FAf
XA0= 0 XAf

V
• Volume at the start of disk is = V
• Volume at the end of the disk is = V + V
• Volume of the disk is = V
• The point properties are uniform inside the disk
• The differential rate of generation is = Gj
 PFR
• Inlet = Outlet + Generation + Accumulation
FA = FA + dFA + GA = 0
GA = (-rA)*V
– dFA =(-rA)*V
• For taking limit 0, one can go for
differential equation,
dFA
 rA
dV
 PFR
V
dN A
FA0  FA   rAdV 
dt
Steady state
This is the integral form. Often the
differential form is more useful. Take
the derivative with respect to volume
of each term.
6/17/2019 7:19 AM 78
 PFR
V
dFA0 dFA d  rA dV
  0
dV dV dV
Derivative of a
constant is just 0
rA

6/17/2019 7:19 AM 79
 PFR

dFA V
 rA FA0  FA    rAdV
dV
rA varies with “length”

dFA
 rA  k (T ) f [C A (  A , T , P)]
dV
6/17/2019 7:19 AM 80
 PFR
• FA = FA0(1-XA)  FA0 dX A
• dFA= -FA0dXA  rA
dV
• Upon Integrating above equation


XA V XA
dX A dV V dX A

0

 rA 0 FA0

FA0 C A0
 
0
 rA
 Design Equation of PFR


XA
V dX A

FA0 C A0
 
0
 rA

XA C Af
VC A0
V dX A dC A
 
0 FA0
 C A0 
0
 rA
 
C A0
 rA
• At what concentration does the reaction takes
place?
 What if feed is partially converted?
X Af
V  dX A

FA0 C A0
 
X Ai
 rA

• What is the difference between design

equations of batch reactor and plug flow
reactor?
 Design of PFR
X Af
V dX A
FA0
 
X Ai
m n
kCA C B
• Solution of above equation depends on two
conditions:
– Isothermal condition
– Non isothermal condition
 Analytical Solution
• Constant density system (Constant Volume)
– Zero order
– First order
– Second order unimolecular or bimolecular with M=1
• Variable Volume system
– First order
• Reversible reaction
– First order
– Second order
 What if system is Variable Volume?
• According to first principle model:
d C A   rA dV

CA 
1  X A  P
1   A X A  RT
• Deriving for nth order reaction:

 1   A X A  
n XA n
V 1  RT 
 
FA0 k  P 
 
0

 1  X A  
 dX A
Graphical Solution



 Practice Problem 1

Assume isomerization
is first order with k =
0.23 min-1

What volume PFR and CSTR are

required for 90% conversion and
10 L/min?
 Practice Problem 2
• Consider a first order chemical reaction
AB
• Is to be carried out in a PFR. Species A enters
the reactor at a molar rate of 0.4mol/sec.
• Using data given in table below calculate the
volume necessary to achieve 80% conversion.
Practice Problem 3
Practice Problem 4
 Practice Problem 5
• Under appropriate conditions, acetaldehyde
vapor reacts to give methane and carbon
monoxide by the reaction
CH3CHO CH4 + CO
• 0.1kg/s of acetaldehyde vapor is to be
decomposed at 520C and 1atm in a packed
tubular reactor. The reaction under these
conditions is known to be irreversible and second
order with respect to CH3CHO. The rate constant
k is 0.43 m3/kmol sec. What will be the volume of
reactor required (a) for 35% decomposition of
feed acetaldehyde, and (b) for 90%
decomposition?
 Deviation from PF Assumption
• Three deviations from uniformity over a cross
section which are postulated by PFA:
– The existence of temperature gradients at right
angles to the direction of flow, due to heat of
reaction.
– Diffusion from one fluid element to another, due
to turbulence or to the influence of packing
– The existence of velocity gradients normal to the
direction of flow.
 What if I don’t assume PF?
• Axial mixing is present.
• Radial mixing is not infinite
• Velocity profile is not flat.
• What are its consequences?
– Draw concentration profile
– CA is not uniform across the cross section
• One has to consider change in concentration in
two ways
– Convective mode (uCA)
– Diffusive mode (DdCA/dz)  Both radial and Axial
dC A d 2C A
u D 2
 kCA  0
dz dx
 What if I don’t assume PF?
• What if system is Unsteady state condition:
• Unsteady state Tubular Reactor without
assumption of Plug Flow
C A C A  CA
2
  C A 1 C A 
2
u  Da  Dr  2    rA
t z z 2
 r r r 

• Good project to solve above equation to get T

and C profiles.
 Analytical Solution (I order)
• With Plug flow assumption
X Af
V dX A
FA0
 
X Ai
kCA
  ln( 1  X A )

 kVCA0 
X A  1  exp     1  exp  k 
 FA0 
• Without Plug flow assumption (Axial Mixing
Model)
 1 uL 
4a exp  
D
a  1  k  
 uL  1  X A    2 D
 a uL   a uL 
1  a  exp 
2
  1  a  exp  
2

2 D   2 D
 Summary - Design Equations of Ideal Reactors

Differential Algebraic Integral

Remarks
Equation Equation Equation
dN j Nj Conc. changes with time
 (rj )V dN j
Batch
dt t  (rj )V
but is uniform within the
N jO reactor. Reaction rate
varies with time.

Conc. inside reactor is

F jo  F j uniform. (rj) is constant.
CSTR V Exit conc = conc inside
 (rj ) reactor.

Fj
dF j Concentration and
PFR dF j
 rj
V 
F jO
(rj )
hence reaction rates
vary spatially.
dV
 Design Equation in Terms of Conversion
REACTOR DIFFERENETIAL ALGEBRAIC INTEGRAL
FORM FORM FORM

X
dX
BATCH N AO
dX
 (rA )V t  N AO 
dt 0
 rAV

FAO ( X )
CSTR V
(rA ) Exit

X
dX dX
PFR FAO  ( rA ) V  FAO 
dV 0
 rA
 Levenspiel Plots
Plug Flow Reactor (PFR)

FA0
x x
(rA ) FA0
VPFR   dX
x 0
 rA

X
Continuous Stirred Tank Reactor (PFR)

FA0
(rA ) FA0
VCSTR [ ] [ X ]
(rA )

X
 Comparison of ideal reactors
• All possible mixing conditions between the
extreme of CSTR and PFR will fall in category of
real reactors.
• Design of stirrer and speed will affect the
approach of CSTR and feed condition and feed
injection will affect the approach of PFR.
• Don’t compare or relate Batch with CSTR and
CSTR with PFR.
– Lab beaker is batch reactor but with addition of tube
for inlet and outlet will make it a CSTR.
– PFR can be converted to CSTR by providing large
quantity of Recycle.
 Comparing CSTR Vs. PFR
• From practice problem we know that for same reaction
and conditions the volume of CSTR and PFR Varies.
• This is due to
– CSTR  Algebraic concept(b.h)
– PFR  Integral concept (area under the curve)
• When we use CSTR and PFR?
• You will need rate of reaction at all values of
conversion.
• Minimizing the volume is priority.
– Ignore the cost associated with engineering the project.
 CSTR Vs. PFR Sizing
• CSTR Volume (MinMax)

• PFR Volume (MinMax)

 CSTR Vs. PFR Sizing

FA0
 rA

CSTR Volume  Green

XA
PFR Volume Pink
 CSTR Vs. PFR Sizing
• Let’s check analytically how PFR reactor
volume changes with respect to conversion in
front of how CSTR reactor volume changes for
same conversion.
 Practice Problem 1
• The following reaction is to be carried out isothermally in a
continuous flow reaction
AB

• Compare the volumes of CSTR and PFR that are necessary

to consume 90% of A (i.e. CA=0.1 CAO). The entering molar
and volumetric flow rates are 5 mol/h and 10 L/h,
respectively. The reaction rate for the reaction follows a
first-order rate law:
(-rA) = kCA where, k=0.0001 s-1
[Assume the volumetric flow rate is constant.]
 Practice Problem 2
• Consider a first order chemical reaction
AB
• Is to be carried out in a PFR. Species A enters the
reactor at a molar rate of 0.4mol/sec.
• Using data given in table below calculate the
volume necessary to achieve 20% to 80%
conversion. Do analytical calculations only.
 Practice Problem 3
• Consider a first order chemical reaction
AB
• Is to be carried out in a PFR. Species A enters the
reactor at a molar rate of 0.4mol/sec.
• Using data given in table below calculate the
volume necessary to achieve 20% to 80%
conversion. Do graphical calculations only.
 Practice Problem 3

PFR volume for

20% conversion
40%
60%
80%
 Practice Problem 3

CSTR volume
for 80%
20%
40%
60%
conversion
 Conversion Vs Time
Green  CSTR
Red  PFR

XA

t
Compare conversion of PFR and CSTR for
constant density system for first order
unimolecular system.
Let’s Take
A = 0
n=1
Rate Law equation

 rA  kCA  kCA0 1  X A 
K = 0.5 sec-1.
For comparison take same volume and volume
flow rate
P = C = 
 Practice Problem 4
PFR CSTR
X AP
VP dX A VCC A0 X AC
C  
P 
0
 C A0 
0
 rA 0 (rA ) exit

 k P  ln 1  X AP  C 
X AC
k 1  X AC 
X AP  1  exp  k P 
k C
X AC 
1  k C
 Practice Problem 4
 0.5 1 2 4 6 8
XAP 0.221 0.39 0.632 0.864 0.95 0.981
XAC 0.2 0.333 0.5 0.666 0.75 0.8
 What if reaction is of second order?
• One has to go for general case
– M can be 1 or large
– Reaction can be of constant volume or variable
volume.
– Reactor can be CSTR or PFR
– Let’s check all cases together for comparing
reactors.
 CB 0
Mi  11
Second Order Reaction C A0

 rA  kCACB  kCA2 0 1  X A M  X A 

 rA  kC  kC 1  X A 
2 2 2
A A0

 P M 1   VP 
X AP
dX A
For PFR
C A0
 
 C A00  M 1
 
0
 rA

 C M 1   VC 

X AC
For CSTR  
C A0  C A00  M 1 (rA ) exit
 CB 0
Mi  11
Second Order Reaction C A0

 C A0VP   M  XA 
For PFR  P M 1    
1
ln  
 FA0  M 1 kCA0 M  1  M 1  X A  

 C A0VP 
 P M 1    
1 XA
 FA0  M 1 kCA0 1  X A

 C A0VC 
 C M 1    
XA
 FA0  M 1 kCA0 1  X A M  X A 
For CSTR

 C A0VC 
 C M 1    
XA
 A0  M 1
F kCA0 1  X A 2
 CB 0
Second Order Reaction Mi 
C A0
11

1  M  XA 
ln  
For PFR
 P M 1 
kCA0 M  1  M 1  X A  
 P M 1 1 XA
kCA0 1  X A

XA
For CSTR  C M 1 
kCA0 1  X A M  X A 
 C M 1 XA
kCA0 1  X A 
2
 CB 0
Second Order Reaction Mi 
C A0
11

For PFR  P M 1  1  X A ln  M  X A 
 P M 1 M 1X A  M 1  X A  

For CSTR
 C M 1  1  X A
 C M 1 M  X A
 CB 0
Second Order Reaction Mi 
C A0
11

• Considering
– Constant Volume
– Inlet Molar rate constant and same
– Inlet concentration constant and same
– Inlet volume rate constant and same
• Because of above condition
 M 1  V M 1
 M 1 V M 1
 CB 0
Second Order Reaction Mi 
C A0
11

For Fixed value of M=2

M XA (/)P (/)C
2 0.4 0.4315 0.375
2 0.6 0.3731 0.2857
2 0.8 0.2747 0.1667
2 0.9 0.1894 0.0909

For Fixed value of XA=0.9

M XA (/)P (/)C
1.5 0.9 0.3081 0.166
2 0.9 0.1894 0.0909
4 0.9 0.0758 0.0322
6 0.9 0.0476 0.0200
For Batch or PFR
For CSTR
Comparison of performance of N BMR with that of 1 PFR for
constant density first order reaction
Comparison of performance of N BMR with that of 1
PFR for constant density Second order reaction
 Conclusions
• Change in molar feed ratio away from unity
increases the capacity of a reactor for both
BMR and PFR.
• The effect is more pronounced at higher
conversion than at lower one.
• The effect is more pronounced in BMR than in
PFR.
• The A can also make difference in the
calculation.
Comparison for single reaction

 f  X A ,rA ,  A 
VBMR
VPFR
C A0 1  X A 
CA 
 rA  kCn
A 1  A X A

C 1  X A 
n n
 rA  k A

1   A X A n
 Comparison of CSTR and PFR
Consider the following rate equation :
1 dN A
 A
 r    kC n
A
V dt
For CSTR :
1 X A 1   A X A 
n
C A0 X A
m  
 rA  kC An 01 1  X A n
For PFR
 C A 0V  (1   A X A ) n dX A
XA
1
p 
 A0 
F

KC n 1
A0

0 1  X A 
n
 Comparison of CSTR and PFR
• Taking ratio of two reactor’s space time
    
n

 C A0V 
n
 
1 X
 
 
A A
X A
C 
n 1
A0 m

 A0  m
F
 X

  1 X A  
m
C 
n 1
 C A0V 

n

 A 1   A X A n 

A0 P
 dX A
 FA0  P  0 1  X A 
n
 P
• For same values of CA0 and FA0, we have three
parameters on RHS
– A, XA and n.
Comparison of CSTR and PFR
For cons tan t density   0
 X 
 A
n
 A0 m
 C n 1


 1  X A   m
when n  1
 C 
n 1
A0 p
 1  X A 1 n  1 
 
  n  1  p

 X 
 A
n
 A0 m
 C n 1


 1  X A   m
when n  1
 C 
n 1
A0 p
 ln 1  X A  p
 Comparison of CSTR to PFR
• For the same treatment rate (FA0) (V)m/(V)p is always larger
than 1 for n>0
– For n=0; Vm = Vp
• Fraction conversion has a large effect on the sizes of
CSTR/PFR
– For XA = 0; Vm = Vp
– Higher the value of XA; larger will be (V)m/(V)p
• Order of reaction has a significant effect on the sizes of
CSTR/PFR
– Higher the order of reaction, larger will be (V)m/(V)p
• Variation in fluid density has an effect on the sizes of
CSTR/PFR
– Higher the value of A larger will be (V)m/(V)p
 Comparison of CSTR to PFR
• PFR
– Concentration decreases gradually
– Rate of reaction is larger
• CSTR
– Concentration decreases at zero time
– Rate of reaction is lower
• n>0
VPFR < VCSTR
 Human Body as a System of Reactors
• You as a process engineer is given a job to prepare a
molecule for long enough time.
• Which variations will you try?
– Size/Type of reactor  more than 10000% variations
– Product distribution  No variations
Food

Small Intestine
Large
Mouth
Intestine
Stomach

What reactor type can we represent the various body parts with?
 Single pass conversion vs global
conversion
• Single pass conversion
– Conversion of one unit
Moles of ' A' reacted in the reactor
XA 
Moles of ' A' fed to the reactor
• Global Conversion
– Conversion is defined in terms of location
downstream rather than single reactor.
Moles of ' A' reacted up to point 2
XA 
Moles of ' A' fed at the start of the operation
 Possibilities
• Connected purely depending on the requirement of
conversion or process.
• PFR
– Series or Parallel
– Equal Size or Unequal size
• Large  Small or small large
Fun
• CSTR
– Series or Parallel
– Equal Size or Unequal size
starts
• Large  Small or small large
• PFR/CSTR
– Series or Parallel
here!!
– Equal Size or Unequal size
– PFR CSTR or CSTR  PFR
• Large  Small or small large
!
Possibilities
 Understanding
FA0  X A2  X A1 
XA = 0 XA = XA1 V2 
FA0 V1 FA1 (rA ) exit
PFR
CSTR
X A1
dX A V2

X Af
V1  FA0 dX A
 rA V3  FA0 
0
X A2
 rA

XA = XA2 XA = XAf
FA1  FA0  FA0 X A1 FA2 V3 FA3

FA2  FA0  FA0 X A2 PFR

FA3  FA0  FA0 X A3

 V3

V2

V1
 PFR in series
V1 V2 V3 Vj Vn

• All the reactors are of same size.

X A1
dX A
V1  FA0   rA
• As the design equation of PFR 0
X A2
dX A
V2  FA0 
 rA
• Applying summation for all the
X A1
X Aj
dX A
reactors V j  FA0 
X A ( j 1)
 rA

X A1 X A2 X Aj
V1 V2 Vj dX A dX A dX A

FA0 FA0
 .. 
FA0
 
0

 rA X A1  rA
 ..  
X A ( j 1)
 rA
 PFR in series
• Irrespective of number of reactors in series; kinetics of reaction will
not change:

X A1 X A2 X Aj
V1 V2 Vj dX A dX A dX A

FA0 FA0
 .. 
FA0
 
0

 rA X A1  rA
 ..  
X A ( j 1)
 rA

V1  V2  ..  V j X A1 X A2 X Aj
dX A dX A dX A
FA0
 
0
 
 rA X A1  rA
 ..  
X A ( j 1)
 rA
X Aj
V dX A
FA0
 
0
 rA
• J plug flow reactors in series with a total volume of V will give same
fractional conversion as a single plug flow reactor of volume V
FAO FA1
FA2
X=0
X=X2
X=X1 FA3; X=X3

FAO
-rA

X1 X2 X3
X
 PFR in series/parallel combination

XA0 XAf
FA0 FAf

• How will you distribute feed so that outlet molar rates

and desired conversion from both the streams D and E
will be same?
• Each branch must get some feed
• Two streams meeting at exit must have same level of
conversion.
PFR in series/parallel combination

• Total volume of stream ‘D’ = VD

• Total volume of stream ‘E’ = VE
• To have same value of conversion; feed must
be distributed according to V  V 
   
• CAD = CAE  F D  F E
• Feed Distribution will be
 FE   VD  40
       4 :1
 FD   VE  10
 Foglar chapter 2 prob 2.6

Practice Time
• Design volume V1 and V2 of the two PFRs in series as shown in
figure below for the given experimental data: take molar rate
= 0.4mol/s.
• To obtain same level of final conversion what is the volume of
single PFR required?
When will you use this type of
arrangement?
 Comparison of CSTR to PFR
• PFR
– Concentration decreases gradually
– Rate of reaction is larger
• CSTR
– Concentration decreases at zero time
– Rate of reaction is lower
• n>0
VPFR > VCSTR
 Comparison of CSTR to PFR

CA0

Single PFR

Single BMR
CA
Volume through the reactor
Single BMR
Two BMR
Six BMR
 What is the
conclusion of last
three slides?
 Equal size CSTR in series
• Assume
– I order reaction
– Constant density reaction
– Equal size CSTR in series
– Same Volume rate so space time of will be same.
–  = 1 = 2 = …= i=…= N
 Equal size CSTR in series
Qualitatively:
CA0 When N  the behavior
Single PFR
of N equal size BMR will
be same as 1 PFR of
Four BMRs volume equal to total
volume of reactors in
series
N BMRs

Two BMRs
Single BMR
CA
Volume through the reactor
 Quantify the fact

• According to CSTR design equation:

C0  C1 C0  C1
1  
r kC1
C0
 1  k 1
C1
 Quantify the fact
C0 C0 C0 C1 Ci 1 C N 1
 1  k 1   
C1 C N C1 C2 Ci CN

 1  k 1 1  k 2  1  k i  1  k N 
C1 C0
 1  k 2
C2 CN
 C0

 1  k i N

Ci 1 CN
 1  k i
Ci
1  C0  N 
 1

  i    1
k  C N  
C N 1  
 1  k N
N  C0  N 
 1
CN
 N ,reactors  N i    1
k  C N  
 
 What if N?
 C  1 N 
N 0
 N ,reactors  N i     1
k  C N  
 
1  C0  N 
 1

  1
k  C N  
 N ,reactors    1
take  P
1 N
N

1  C0 
P

   1
k  C N  
 N ,reactors   P    Indertermi nent
P
Comparison of performance of N BMR with that of 1 PFR for
constant density first order reaction
 Equal size CSTR in series
• Assume
– II order reaction
– Constant density reaction
– Equal size CSTR in series
– Same Volume rate so space time of will be same.
–  = 1 = 2 = …= i=…= N
 II order
C Ai  kC   C A(i 1)
2
Ai i

 1  1  4 i kCA(i 1)
C Ai 
2k i
Positive root is only considered here.
This can be applied to all the concentration outlet of all
the CSTR.
Comparison of performance of N BMR with that of 1
PFR for constant density first order reaction
PRACTICE TIME
 Unequal size BMR in series
• Two possible arrangements:
– Larger CSTR followed by smaller CSTR
– Smaller CSTR followed by larger CSTR
• Two aspects of design:
– If set up is fixed calculate maximum possible
conversion from available volume
– If conversion is fixed  calculate minimum
possible volume required to achieve that
conversion
Unequal size BMR in series(Fixed Set up)

Normal sized BMR Bigger sized BMR Smaller sized BMR

 Unequal size BMR in series (Fixed Set up)
• Applying Design equation of CSTR:
V1 C0  C1 1  r1
 1  t1    
  r1  1 C1  C0
V2 C1  C2 1  r2
 2  t2    
  r2  2 C2  C1
V3 C2  C3 1  r3
 3  t3    
  r3  3 C3  C2

1  ri
 
 i Ci  Ci 1
Unequal size BMR in series (Fixed Set up)
 1 r
 
 i Ci  Ci 1
Unequal size BMR in series
• Prepare a graph of –r vs C.
• Equations derived in last slide for three
reactors look like equations of straight line
with the slope of -1/.
• From the equations it is very clear that one
can’t jump directly from reactor one to three.
• Let’s do this calculation on graph for any
general order reaction.
WHAT ABOUT VARIABLE VOLUME
REACTIONS?
Unequal size BMR in series (Fixed XA)

Fixed
 Unequal size BMR in series (Fixed XA)
• Suppose one want to get final conversion = 0.95
• Design equations of two different CSTR:
1 X A1 2 X A2  X A1
 and 
C A0  rA1 C A0  rA2
• The size of both the reactors depends on the
selection of intermediate conversion XA1.
• XA2 is fixed. Kinetics is known. CA0 is known.
• Make some calculations.
Unequal size BMR in series (Fixed XA)
XA1 XA2 1 2 V1 V2 V1+V2

0.4 0.95 Select

minimum
0.5 0.95 from this
One can select
0.6 0.95 appropriate values of k,
column.
n,  and CA0 for this
0.65 0.95 table preparation.

0.75 0.95
 Unequal size BMR in series (Fixed XA)
• Now preparing a plot of V1+V2 vs X1.

V1+V2

(V1+V2)min

X1,opt X1
 Correction

• Tabular values are discrete.

• So the graph will not give true minimum.
• Going for all the values of X1 will be very
tedious.
• Needs a easier but correct method to know
true value of minimum.
Let’s go back to school math

f(y) = x
M

dy y
 
dx x
Maximizing Area
 Conclusion
• Area will be maximized when ‘M’ is that point
where the slope of the tangent at ‘M’ will be
same as the diagonal of the rectangle.
• Depending upon shape of the curve, there may
be more than one or no best point.
• For the case of n>0, there always is just one best
point.
• The volume of the CSTR will be area of a
rectangle.
• In case of 1/-rA vs XA, So if one can maximize the
extra area above the curve so the area of CSTR
will be minimum.
 Conclusion
• The optimum size ratio for two BMR in series
depends on
– Kinetics of the reaction
– Conversion levels
• For the special case:
– n =1 two equal size BMR are best
– n >1 smaller one should come first
– n <1 larger one should come first
Reactors of different type in series
Reactors of different type in series
 Best Arrangement
• For a reaction whose rate concentration curve rises
monotonically (n>0) the reactors should be connected
in series.
– They should be connected such that outlet concentration
must be as high as possible if rate concentration curve is
concave (n>1)
• PFR  small CSTR  Large CSTR
– They should be connected such that outlet concentration
must be as low as possible if rate concentration curve is
convex (n<1)
• Large CSTR  small CSTR  PFR
• For the case where rate concentration curve passes
through maximum or minimum, the arrangement
depends upon the actual shape of curve.
• What ever may be the kinetics and the reactor system,
an examination of 1/-rA vs XA curve is a good way to
find the best arrangement of units.