Mole Balances

REEN 2001
 What type of reactor(s) to use?
in
Continuously Stirred
Tank Reactor (CSTR)

out

Plug flow reactor (PFR)

Well-mixed batch reactor
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 Which type of reactor to use?
• In reactor 1, the desired methanol product is formed via CO2 reacting
with H2, in a one to three (1:3) mole ratio,to produce methanol
(CH3OH) and water (H2O) using a catalyst with copper in a one to one
(1:1) ratio with zinc oxide (Cu/ZnO).
CO2 + 3H2 ↔ CH3OH +H2O

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 Chemical Reaction
• A detectable number of molecules have lost their identity and
assumed a new form by a change in the kind or number of atoms
in the compound and/or by a change in the atoms’ configuration
• Decomposition
• Combination
• Isomerization

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 Reactions
• A chemical species is said to have reacted when it has lost its
chemical identity.
• There are three ways for a species to loose its identity:

1. Decomposition CH3CH3 → H2 + H2C=CH2

2. Combination N2 + O2 → 2 NO
3. Isomerization C2H5CH=CH2 → CH2=C(CH3)2

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 Rate Law for rj
• rA: the rate of formation of species A per unit volume [e.g., mol/m3•s]
• -rA: the rate of a consumption of species A per unit volume
A + B → products −r A = kC A CB
1st order in A, 1st order in B, 2nd order overall
−r A = kC A n nth order in A
k1C A
− rA = Michaelis-Menton: common in enzymatic reactions
1 + k 2C A

rj depends on concentration and temperature:

 −Ea 
 RT 
-rA = A e C
A Arrhenius dependence on temperature
A: pre-exponential factor E A : activation energy
R : ideal gas constant T:temperature
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 Reaction Rate
• Reaction rate tells us how fast a number of moles of one chemical
species are being consumed to form another chemical species

• The reaction rate is the rate at which a species loses its

chemical identity per unit volume.

• The rate of a reaction (mol/dm3/s) can be expressed as either:

• The rate of Disappearance of reactant: -rA
or as
• The rate of Formation (Generation) of product: rP

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 Reaction Rate
Consider the isomerization
A→B
rA = the rate of formation of species A per unit volume
-rA = the rate of a disappearance of species A per unit
volume
rB = the rate of formation of species B per unit volume

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 Reaction Rate
EXAMPLE: A→B
If Species B is being formed at a rate of
0.2 moles per decimeter cubed per second, i.e.,
rB = 0.2 mole/dm3/s

Then A is disappearing at the same rate:

-rA= 0.2 mole/dm3/s
The rate of formation (generation of A) is:
rA= -0.2 mole/dm3/s

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 Reaction Rate of catalysed reactions
• For a heterogeneously catalysed reaction we refer to –r’A , which is the
rate of disappearance of species A on a per mass of catalyst basis.
(mol/gcat.s)

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 Reaction Rate - summary
Consider species j:
1. rj is the rate of formation of species j per unit volume [e.g. mol/dm3s]
2. rj is a function of concentration, temperature, pressure, and the type of
catalyst (if any)
3. rj is independent of the type of reaction system (batch, plug flow, etc.)
4. rj is an algebraic equation, not a differential equation
(e.g. -rA = kCA or -rA = kCA2)

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 Rate of reaction - exercise
• Consider the reaction:
A + 2B → C + D

If the rate of disappearance of A (-rA) is 4mol/dm3s, what are the rate

laws for the other components?

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 General Mole Balances
System
Volume, V

Fj0 Gj Fj

 Molar Flow  Molar Flow   Molar Rate   Molar Rate 

 Rate of  −  Rate of  + Generation  =  Accumulation
       
 Species j in   Species j out  of Species j  of Species j 
dN j
Fj 0 − Fj + Gj =
dt
 mole   mole   mole   mole 
  −   +   =  
 time   time   time   time  13
 Basic Molar Balance (BMB)
Fj0 Fj
Gj

System volume, V
Rate of Rate of Rate of
Rate of
flow of j - flow of j + generation of j - Rate of
decomposition =
into out of by chemical rxn accumulation
of j
system system

combine Nj: moles j in

system at time t
dN j
Fj − Fj + Gj =
0 dt
 mol   mol   mol  d
      (mol )
 s   s   s  dt

in - out + generation = accumulation

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 Rate of Rate of Rate of
Rate of
flow of j - flow of j + generation of j - Rate of
decomposition =
into out of by chemical rxn accumulation
of j
system system
dN j
Fj − Fj + Gj =
0 dt
 mol   mol   mol  d
      (mol )
 s   s   s  dt
If the system is uniform throughout its entire volume, then:
G j = rj V
Moles
Moles j
generated per
generated Volume
= unit time and
per unit time (m3)
volume
(mol/s)
(mol/s•m3)
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 Non-Uniform Generation
system

DV
Rate is rj1
within this Rate is rj2
DV volume within this
m V volume
G j = lim  rjDV =  rjdV
m→∞ i=1
DV→0

1
111
then G j =    rj (x, y, z ) dx dy dz
000
1 y
1 Plug in rj and integrate over x, y, and z
x
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 Basic Molar Balance Equations
Fj0 Fj
Gj

System volume

In - Out + Generation = Accumulation

dN j
Fj0 − F j +G j =
dt
dN j
Fj0 − F j +rj V = uniform rate in V
dt
V dN j
Fj0 − F j +  rjdV = nonuniform rate in V
dt

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Reactor Molar Balances & Considerations
Fj0 Fj
Gj

reactor

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Review: Batch Reactors Properties
• Reactants are placed in the reactor, and
the reaction is allowed to proceed for
some amount of time
• Closed system- no addition of reactants
or removal of products during the
reaction
• Unsteady-state conditions- the
composition changes with time
• Ideal batch reactor- vessel is perfectly
mixed
• Concentration and temperature are
spatially constant, but NOT constant in
TIME
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 Basic Mole Balance for Batch Reactor
No flow in
In - Out + Generation = Accumulation
or out!
V dN j
X X
Fj0 Fj Fj −F j +  rjdV =
0 dt
0 0
V dN j Batch Reactor Design
→  rjdV =
dt Equation

If the reactor is perfectly mixed, the temperature, concentration, &

therefore the reaction rate are spatially constant:
dN j Ideal Batch Reactor
rj V =
dt Design Equation
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 Batch Reactor - Mole Balances
N A0
dN A
t= 
N A1
− rAV

NA

21 t
REVIEW: Continuous Stirred Tank Reactor
(CSTR) Properties
• Continuously add reactants and remove
products (open system)
• Inlet stream instantaneously mixes with
bulk of reactor volume
• Ideal batch reactor- assume perfect
mixing occurs in vessel
• Temperature and concentration are
uniform throughout space
• Composition of the exit stream is the
same as that inside reactor (CA,outlet =
CA, tank)
• Steady-state conditions- the reaction rate
is the same at every point and does not
change with time
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In - Out + Generation
Basic Mole
= Accumulation
Balance
F for
F CSTRj0 j

V dN j CSTR is at steady state

Fj −F j +  rjdV = (SS), so no change in
0 dt
moles j with time!
0
V
Steady State CSTR
→ Fj −F j +  rjdV = 0
0 Design Equation

A perfectly mixed CSTR has no spatial variations in reaction rate

→ Fj −F j +rj V = 0 Rearrange to put in terms of V
0

rj is measured at Fj −F j Ideal Steady State

the outlet because 0 = V CSTR Design
− rj
Cj,exit = Cj,tank Equation
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 Ideal SS CSTR Design Equation
Fj −F j
V= 0
− rj
Reactor volume required to reduce the entering flow rate of species j
from Fj0 to Fj at the outlet (and in the tank)
How do we determine the molar flow rate, Fj (units = mol/time)?
Fj = ( C j ) ( )
moles j  moles   volume 
=  
time  volume   time 
Cj: concentration of j : volumetric flow rate
Ideal SS CSTR design equation in terms of concentration:
C j0  − C j 
V=
−rj
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REVIEW: Plugged Flow Reactor (PFR)
Properties
• Also called a tubular reactor
• Cylindrical pipe with openings at
both ends
• Steady movement of material down
length of reactor
• Reactants are consumed as they flow
down the length of the reactor
• Operated at steady state:
• No radial variation in
temperature, concentration, or
reaction rate
• All fluid/gas elements have the
same residence time

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 Plug Flow Reactor - Mole Balances
DV

FA FA


V V + DV


 In  Out  Generation
at V  − at V + DV  + in DV =0
     
FA V − FA V + DV + rA DV =0
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 Mole Balance – PFR
ΔV

FA0 FA
dN j
Fj0 - Fj + rjDV =
dt
dN j Divide by DV
Fj − Fj + rj DV = → Fj − Fj + rjDV = 0
V V +DV dt DV V V + DV

0
− Fj lim
V + DV −Fj
Fj Fj dFj
→ V V +DV + rj = 0 →
V
= rj DV→0 = rj
DV DV dV
If we assume the PFR is ideal, the degree of completion is not Ideal SS PFR
affected by PFR shape, only by PFR volume Design Eq.
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 Plug Flow Reactor - Mole Balances
Differientiate with respect to V
dFA dFA
0− = −rA = rA
dV dV

 FA FA 0
dFA dFA
The integral form is: V = 
FA 0
rA
= 
FA
− rA

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 Packed Bed Reactors (PBR)
• Cylindrical shell, vertically oriented
• Often gravity-driven flow
• Heterogeneous reaction: fixed bed of catalyst
inside
• Reactants enter top and flow through the
packed bed of catalyst
• Concentration gradient of reactant and
product down the length of the reactor
• Reaction occurs on the surface of the catalyst
pellets
• Reaction rate is based on the mass of the
solid catalyst, W, not reactor volume V

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 Mole Balance- Packed Bed Reactor
(PBR)
dFj
= rj
dV

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

Rewrite the PFR design equation in terms of catalyst weight

instead of reactor volume:

dFj
= rj ' where W is the weight of the catalyst
dW
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 Mole Balances on Common Reactors
Reactor Mole Balance Comment
Batch dN j No spatial variation
= rj V
dt
CSTR Fj0 - Fj No spatial
V= variation, steady
-rj state
PFR dFj Steady state
= rj
dV
PBR dFj Steady state
= rj
dW

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 Reactor Mole Balances Summary
The GMBE applied to the four major reactor types
(and the general reaction A→B)
Reactor Differential Algebraic Integral No spatial
N A0 NA variation
dN A
Batch dN A
= rAV t=  − rAV
dt NA
t No spatial
variation,
CSTR FA 0 − FA steady
V =
−rA FA
state

PFR dFA FA
dFA
FA 0
dFA
 
Steady
= rA V = =
dV FA 0
rA FA
− rA state
V

FA FA 0 F
dFA dFA dFA A
 
PBR
= rA W = = Steady
 dW FA 0

rA FA
− rA state
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W
 References
• Kraft, ML, Chemical and Biomolecular Eng Department, U of Il –
Urbana-Champaign
• Fogler, HS, Chemical Eng, U of MI – Ann Arbor
• Fogler, HS. Elements of Chemical Reaction Engineering, 4th edition

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