MOLE BALANCES

1
OUTLINE
 Introduction
 Chemical Species

 Chemical Reaction

 Rate of Reaction

 General Mole Balance Equation

 Batch Reactor

 Continuous-Flow Reactors

 Industrial Reactors

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INTRODUCTION
 Application of Chemical Reaction Engineering

Waste treatment

Microelectronics Living system

Manufacturing of
Nanoparticles chemical &
pharmaceuticals

3
1. CHEMICAL SPECIES

What are chemical species?

 Any chemical component or element with a given
identity.
 Identity of a chemical species is determined by
the kind, number, and configuration of that
species’ atoms.
 Kind of species- methane, butene, butane

 Number of atoms- eg: CH4: 1 C, 4 H

 Configuration of atoms- arrangement of the

atoms
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 Can they be considered as different
SPECIES?

Kind: Same (Butene)

Number of atoms: Same (C4H8)
Configuration: Different arrangement

ANSWER: Yes. We consider them as two different

species because they have different configurations. 5
2. CHEMICAL REACTION
 Chemical reaction is any reaction when one or
more species lost their identity and produce a
new form by a change in the kind or number of
atoms in the compound, and/or by a change in
structure or configuration of these atoms.

HOW????
6
2. CHEMICAL REACTION
 Species may lose its chemical identity by:
1) Decomposition (by breaking down the
molecule into smaller molecule)
Eg: C ⇌ A + B
2) Combination (reverse of decomposition)
3) Isomerization ( neither add other molecule nor
breaks into smaller molecule)

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 It tells how fast a
number of moles of
one chemical species

rA
to form another
3. RATE OF REACTION, chemical species.

rA ,the rate of reaction: is the number of moles of A

reacting (disappearing) per unit time per unit
volume ( mol / dm3  s ).

rA , is the rate of formation (generation) of species A.

rA , is a heterogeneous reaction rate: the no of moles
of A reacting per unit time per unit mass of
catalyst
mol / s  g catalyst
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 L2-9

Review: What size reactor(s) to use?

Answers to this questions are based on the desired

conversion, selectivity and kinetics

Kinetics
Reactor type Conversion
& &
size Material & selectivity
energy
balances

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2-10

Review: 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  kCAn nth order in A
k1CA
 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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2-11

Review: Basic Molar Balance (BMB)

Fj0 Fj
Gj

System volume
Rate of Rate of Rate of Rate of
Rate of
flow of j - flow of j out + generation of j - decomposition =
accumulation
into system of system by chemical rxn of j
dNj
Fj0  Fj  Gj 
dt
 mol   mol   mol  d
 s   s   s   mol
      dt
If the system is uniform throughout its entire volume, then:
Gj   rj   V 
Moles j Moles generated
Volume
generated per = per unit time and
(m3)
unit time (mol/s) volume (mol/s•m3)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2-12

Review: BMB Equations

Fj0 Fj
Gj

System volume

In - Out + Generation = Accumulation

dNj
Fj0  F j G j 
dt
dNj
Fj0  F j rj V  uniform rate in V
dt
V dN j
Fj0  F j   rjdV  nonuniform rate in V
dt
Next: Apply BME to ideal batch, CSTR, & PFR reactors
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2-13
L2: Reactor Molar Balances &
Considerations
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.
 4. THE GENERAL MOLE BALANCE EQUATION
 A mole balance of species j at any instant time:

Rate of generation Rate of

Rate of flow Rate of flow
of j by chemical accumulation
of j into the of j out of
reaction within of j within
system the system
the system the system
(moles/time) (moles/time)
(moles/time) (moles/time)

In - Out + Generation = Accumulation

dN j
Fj0 - Fj + Gj =
dt
V
dN j
Fj0 - Fj +  r j dV = 14
0 dt
4. THE GENERAL MOLE BALANCE EQUATION
Consider a system volume :
System volume

Fj0 Gj Fj

General mole balance:

Fj0 - Fj + Gj = dNj/dt
In - Out + Generation = Accumulation
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THE GENERAL MOLE BALANCE EQUATION
Condition 1:
 If all the the system variables (eg: T, C) are
spatially uniform throughout a system volume:

Gj = rj.V
moles moles
  volume
time time  volume

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THE GENERAL MOLE BALANCE EQUATION
Condition 2:
 If the rate of formation, rj of a species j for the
reaction varies with position in the system
volume:
∆V1
rj1 ∆V2
Fj0 Fj
rj2

 The rate of generation ∆Gj1:

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∆Gj1=rj1∆V1
4. THE GENERAL MOLE BALANCE EQUATION
 The total rate of generation within the system
volume is the sum of all rates of generation in
each of the subvolumes.
M M
G j   G ji  r ji Vi
i 1 i 1

 Taking the limit M∞, and ∆V0 and

integrating,
V
G   r j dV
18
0
TYPE OF REACTORS

out
Batch

REACTORS
Semi Semi

in
batch continue

Continuous
Flow
 L2-20
L2: Reactor Molar Balances &
Considerations
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.
5. BATCH REACTORS
 The reactants are first placed inside the
reactor and then allowed to react over time.
 Closed system: no material enters or
leaves the reactor during the time the
reaction takes place.
• 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 the conditions inside
 Advantage: high conversion the reactor (eg:
concentration, 21
temperature) changes
over time
 L2-22

Examples of Batch Reactor

Lab-Scale
Typical Commercial Batch
Batch Reactor
Reactor

Motor for agitation

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 5. BATCH REACTORS: DERIVATION
 Batch reactor has neither inflow nor outflow Fj0 Fj
of reactants or products while the reaction is
carried out:
FA0 = FA = 0

 General Mole Balance on System Volume V

V
dN A
FA0 - FA +  rA dV =
0 dt

dN A V
  rA dV
dt 0 23
5. BATCH REACTORS: DERIVATION
 Assumption: Well mixed so that no variation in
the rate of reaction throughout the reactor
volume: dN A Batch reactor
 rAV design
dt equation
 Rearranging:
dN A
dt 
rAV

 Integrating with limit at t=0, NA=NA0

& at t=t1, NAN=N A1, N A0
A1
dN A dN A
t1     24
N A0 rAV N A1  rAV
 Continuous Stirred Tank Reactor L2-25

(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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2-26

Examples of CSTRs

Laboratory-Scale Bioreactor

Pfaudler Inc.
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2-27

Basic Mole Balance for CSTR

Fj0 Fj
In - Out + Generation = Accumulation
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
 Fj F j   rjdV  0 Steady State CSTR
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

the outlet because
0  V State CSTR
 rj
Cj,exit = Cj,tank Design Equation
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2-28

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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
SUMMARY OF CSTR
DERIVATION
 General Mole Balance:

V
dN A
FA0 - FA +  rA dV =
0 dt
 Assumption:

1.steady state: dN
A
0
dt
2. well mixed: V
 rA dV  rAV
0
 Mole balance: FA - FA + rAV = 0
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F  FA0 FA0  FA design equation
V A  for CSTR
rA  rA
 6. CONTINUOUS-FLOW REACTORS: STEADY STATE
2. Plug Flow/Tubular Reactor
 Consist of cylindrical hollow pipe.

 Reactants are continuously

consumed as they flow down the

length of the reactor.
 Operate under steady state cond.

 No radial variation in velocity, conc,

temp, reaction rate.

 Usually used for gas phase reaction

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 L2-31

Plugged Flow Reactor (PFR)

Properties
• Also called a tubular reactor
• Cylindrical pipe with openings at
both ends
• Usually used for gas phase
reaction
• 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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2-32

Industrial PFRs

Polyethylene reactor:
• 16 inch inner diameter
• Operates at 35,000 psi & 600 °F
• Has a vertical orientation when in use
Courtesy of Autoclave Engineers of Snap-tite, Inc.
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2-33

Mole Balance – PFR

In a plug flow reactor the composition of the fluid varies from point to point
along a flow path. Consequently, the material balance for a reaction
component must be made for a differential element of volume ΔV
ΔV

FA0 FA
dN j
Fj0 - Fj + rjV =
dt
dN j Divide by V
Fj  Fj  rj V   Fj  Fj  rjV  0
V V V dt V V V  V

0
 Fj lim
Fj Fj V  V F dFj
 V V V  r  0 
j V
 r V→0  rj
j j
V V dV
If we assume the PFR is ideal, the degree of completion Ideal SS PFR
is not affected by PFR shape, only by PFR volume Design Eq.
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
6.2 PLUG FLOW REACTOR
DERIVATION
 General Mole Balance:
V
dN A
FA0 - FA +  rA dV =
0 dt
 Assumption:

1.steady state: dN A  0
dt
V
FA0 - FA +  rA dV = 0
0

 Differentiate with respect to V:

dF dFA 34
0  A  rA ,  rA
dV dV
6.2 PLUG FLOW REACTOR
DERIVATION
dFA
 rA
dV
 Rearranging and integrating between
V = 0, FA = FA0
V = V1, FA = FA1
V1 FA1
dFA dFA
dV  V   r
rA 0 FA 0 A

FA1
dFA FA0 dFA
V1     35
FA 0 rA FA1  rA
 6. CONTINUOUS-FLOW REACTORS: STEADY STATE

3. Packed-Bed Reactor
(fixed bed reactor)
 Often used for catalytic process

 Heterogeneous reaction system

(fluid-solid)
 Reaction takes place on the surface

of the catalyst.
 No radial variation in velocity,

conc, temp, reaction rate

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6.3 PACKED BED REACTOR
DERIVATION the reaction rate is
 General Mole Balance: based on mass of solid
catalyst, W, rather than
dN A reactor volume
 A dW
'
FA0 - FA + r =
dt
 Assumption:
dN A
1.steady state: 0
dt

 A dW
'
FA0 - FA + r = 0

 Differentiate with respect to W:

dFA
 rA' 37
dW
6.2 PACKED BED REACTOR
DERIVATION
dFA
 rA'
dW
 Rearranging and integrating between
W = 0, FA = FA0
W = W1, FA = FA1

dFA V1 FA1
dFA
dW  W  
rA' 0 FA 0 rA'

FA1 FA 0
dFA dFA
W1     38
FA 0 rA' FA1  rA'
SUMMARY OF REACTOR MOLE BALANCE
Differential Algebraic
Reactor Integral Form Comment
Form Form

N A0
No spatial
dN A variations,
Batch dN A t1  
 rAV N A1  rAV
unsteady
dt state
No spatial
FA 0  FA
CSTR - V - variations,
 rA steady state
FA 0
dFA
PFR dFA V1   Steady state
 rA FA1  rA
dV
FA 0 39
dFA dFA
PBR  rA' W1   Steady state
dW FA1  rA'
 L2-40

Selection of Reactors
Batch
• small scale
• production of expensive products (e.g. pharmacy)
• high labor costs per batch
• difficult for large-scale production
CSTR: most homogeneous liquid-phase flow reactors
• when intense agitation is required
• relatively easy to maintain good temperature control
• the conversion of reactant per volume of reactor is the smallest of
the flow reactors - very large reactors are necessary to obtain
high conversions
PFR: most homogeneous gas-phase flow reactors
• relatively easy to maintain
• usually produces the highest conversion per reactor volume
(weight of catalyst if it is a packed-bed catalyze gas reaction) of
any of the flow reactors
• difficult to control temperature within the reactor
• hot spots can occur
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L2-41

Uses for Various Reactors

• Noncatalytic homogeneous • Ethylene polymerization
gas reactor (high pressure)
• Homogeneous liquid reactor • Mass polymerization of styrene
• Liquid-liquid reactor • Saponification of fats
• Gas-liquid reactor • Nitric acid production
• Non-catalytic gas-solid reactor • Iron production
– Fixed bed • Chlorination of metals
– Fluidized bed • Ammonia synthesis
• Fixed bed catalytic reactor • Catalytic cracking (petroleum)
• Fluid bed catalytic reactor • Hydrodesulphurization of oils
• Gas-liquid-solid reactor

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

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Packed-Bed Reactor at Sasol Limited

Chemical
INDUSTRIAL REACTORS

Fixed-Bed Reactor at British Petroleum (BP): 43

using a colbalt-molybednum catalyst to convert
SO2 to H2S
INDUSTRIAL REACTORS

Fluidized Catalytic Cracker at British Petroleum (BP): 44

using H2SO4 as a catalyst to bond butanes and iso-butanes
to make high octane gas