CHAPTER 1

Mole Balances

DR. MAZATUSZIHA AHMAD

 Contents
Learning Outcomes

Rate of reaction

General mole balance equation

Batch reactor

Continuous-stirred tank reactor (CSTR)

Plug-flow reactor (PFR)

Packed-bed reactor (PBR)

 Learning Outcomes

Week Topic Learning Outcome

1 Rate Law & Mole Balances It is expected that students are able to:

• Basic definitions • Write rate law, define reaction order

and activation energy for elementary
• General mole balance reactions.
equation
• Define the rate of chemical reaction for
• Batch, continuous and basic chemical reactor.
industrial reactors
• Write the mole balance equation to a
batch reactor, CSTR, PFR, and PBR.

• Describe reactors used in industries.

 Chemical Identity
A chemical species is said to have reacted when it has
lost its chemical identity.

The identity of a chemical species is determined by the

kind, number, and configuration of that species'
atoms.

3 ways a chemical species can lose its chemical

identity:
– Decomposition (example)
– Combination (example)
– Isomerization (example)
 Rate of Reaction
The reaction rate is the rate at which a species looses its
chemical identity per time per unit volume.

The rate of a reaction can be expressed as the rate of

disappearance of a reactant or as the rate of appearance of
a product.
Rate of reaction – the number of moles of A reacting
(disappearing) per unit t per V (mol/dm3.s)
Consider species A:

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
Example:
AB

If Species B is being formed at a rate of

0.2 moles per decimeter cubed per second,
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
• QUESTION 1
Consider the reaction
A + 2B 3C

in which the rate of disappearance of A is 5 moles of A

per dm3 per second at the start of the reaction.
At the start of the reaction
(a) What is -rA?
(b) What is the rate of formation of B?
(c) What is the rate of formation of C?
(d) What is the rate of disappearance of C?
(e) What is the rate of formation of A, rA?
(f) What is -rB?
 Rate of Reaction (Cont.)
RATE = SPEED
The RATE of a reaction is the SPEED at which a reaction
happens.

If a reaction has a low rate that means the molecules combine

at a slower speed than a reaction with a high rate.

Reaction rate (r ) is a function of concentration, for example

 rA  kC A(1 st
order reaction)
 rA  kC 2A(2 nd
order reaction)
k  specific reactionrate(time - )
• -rA Independent of reactor system ie batch, CSTR, PFR

• For a catalytic reaction, the reaction rate is written per

unit mass of catalyst basis:

Example :
-rA', = the rate of disappearance of species A on a per
mass of catalyst basis. (mol/s g catalyst).
General Mole Balance Equation
System volume, V

G
Fjin Fjout
[Rate flow in] + [Generation] – [Rate flow out]=[accumulation]

Unit: moles/time

A mole balance on species j at any instant time

, t, yields the following equation:

dNj
Fj in  Gj  Fj out 
dt
moles/time moles/time moles/time moles/time
 In generation out accumulation

Fjo Gj Fj dNj Eq. 1.1

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

Nj = represents the number of moles of

species j in the system
 General Mole Balance Equation
Gj = rjVj

moles/time moles/([Link]) volume

Generally, the rate of reaction varies

from point to point in the reactor:
V
G j   rjdV

The general mole balance equation:

dN
Fin   [Link]  Fout 
dt
From here, design equation
for different types of the
moles moles moles moles
.volume reactors can be developed.
time [Link] time time
Each reactor type will have a different
mole balance…
 Types of Reactors
Depending on loading/unloading of the reactor

Batch Semi-batch Continuous flow

Continuous stirred tank reactor (CSTR)

Plug flow reactor (PFR)/ Tubular

Packed bed reactor (PBR)

Types of Reactors (Cont.)
Continuous Flow

Batch CSTR

catalyst

Tubular/Plug Flow Packed bed

 Batch Reactor

For small-scale operation.

Testing new processes.
Manufacturing expensive products.
Processes difficult to convert to
continuous operation.
 Batch Reactor

Pfaudler’s Batch reactor

 Batch Reactor
Batch reactors has neither inflow nor outflow of reactants or
products.

V dNj V dNj
F j0  F j   ridV   rjdV 
dt dt

Assuming perfect mixing, reaction rate the same through the volume

dNj NA0 dNA

 rV or t1  
dt NA1 - rA V
•Consists of a tank with an agitator and
heating/cooling system.

•Generally of constant volume.

•Some are designed to maintain

a constant pressure by varying
the reactor volume.

•Contain ports for injecting reactants & removing

products,

• Can be outfitted with a stirring system.

• When using batch reactors, reactants are first placed

inside the reactor and then allowed to react over time.
Batch reactors are closed systems .
Typically, they are used for;

 Liquid phase reactions that require

a fairly long reaction time.
Example : beverage processes,
dairy industry.

Used when only a small amount of

product is desired (process is still in
the testing phase, or when the desired
product is expensive).

Example : pharmaceutical industry,

which requires consistent,
high quality results.
 ADVANTAGES DISADVANTAGES

• High conversions can be • High cost of labor per unit of

obtained by leaving reactants in production.
reactor for extended periods of
time.
• Difficult to maintain large
• Batch reactor jackets allow the
scale production.
system to change heating or
cooling power at constant jacket • Long downtime for cleaning
heat flux. leads to periods of no
production.
• Versatile, can be used to make
many products consecutively.

• Good for producing small

amounts of products while still in
testing phase.

• Easy to clean.
Continuous Flow Reactor
Continuous-stirred Tank Reactor

Pfaudler’s CSTR reactor

Continuous-stirred Tank Reactor
V dNj
F j0  F j   ridV 
dt

=0, operation in a steady state

A steady-state basis, where the conditions (C, T, rj identical

throughout the vessel) in the reactor don't change with time.

Assuming perfect mixing, so

 Reaction rate is the same through the volume.
 Conditions of exit stream are the same as in the reactor.

F j0  F j v jC j0  vC j
F j0  F j  rj V V or
 rj  rj
Continuous-stirred Tank Reactor
Assuming perfect mixing, so
 Reaction rate is the same through the volume.
 Conditions of exit stream are the same as in the reactor.

Thus the molar flow rate Fj is just the product of the

concentration, (Cj) of species j and volumetric flowrate, n

F j0  F j v jC j0  vC j
F j0  F j  rj V V or
 rj  rj
 Continuous-stirred Tank Reactor
• CSTRs are open systems, where material is free to
enter or exit the system,
• Consist of a tank, usually of constant volume, and a
stirring system to mix reactants together. Also, feed and
exit pipes are present to introduce reactants and remove
products.
• Reactants are continuously introduced into the reactor,
while products are continuously removed.
• Often used in biological processes, such as cell cultures.
• Often used in biological processes, such as cell
cultures.
• Fermentors are CSTRs used in
biological processes in many
industries, such as antibiotics and
waste treatment.

Industrial fermentor
Capacity – 3.0 L lab scale
capacity 500L
 Tubular /Plug Flow Reactor

Usually operates in steady state

Primarily used for gas reactions
Easy to maintain, no moving parts
Produce highest yield
Temperature could be difficult to
control, hot spots might occur
when the reaction is exothermix.
 Tubular /Plug Flow Reactor
No radial variations in velocity,
concentration, temperature, or reaction rate

Reactants Products

axial direction

Reaction continuously progresses along the length of the

reactor, so the concentration and consequently the reaction
rate varies in axial direction.

In the model of PFR the velocity is considered uniform and there

are no variation of concentration (and reaction rate) in the radial
direction.

If it cannot be neglected we have a model of Laminar Flow Reactor.

Tubular /Plug Flow Reactor
No radial variations in velocity,
concentration temperature, or reaction rate

Reactants Products

V dNj
F j0  F j   rjdV 
dt
=0, operation in
No accumulation 0 a steady state
 Design Equation for PFR
For every slice of volume:

F j| V  ΔV  F j| V dFj
F j0  F j  riV  0 ri  ri 
ΔV dV

From here, a volume required to produce given molar flow rate of

product can be determined.

dFj dFj Fj dFj F j0 dFj

rj  dV  V 
dV rj F j0 rj Fj - rj
 Tubular /Plug Flow Reactor
• Tubular reactors consists of cylindrical pipe, may be configured as
one long tube or a number of shorter tubes (range in diameter from
a few centimeters to several meters). The choice of diameter is based
on construction cost, pumping cost, the desired residence time, and
heat transfer needs.

• Operated at steady state.

• Reactants are continuously fed into the reactor from the left. The
reactants are continually consumed as they flow down the length of
the reactor. Unreacted reactants flow out of the reactor continuously.

• Concentration varies continuously in the axial direction through the

reactor. Consequently , the reaction rate
-rA = [kA (T)] [fn (CA)], thus, -rA vary axially.
• The changing reaction rate with respect to distance traversed; at the
inlet of tubular reactor the rate is very high.

• But as the concentrations of the reagents decrease and the

concentration of the product(s) increases the reaction rate slows.

Products

Reactants
 Packed-bed Reactor
Here the reaction takes place on
the surface of catalyst.

Reaction rate defined per unit

area (or mass) of catalyst.

–rA = mol A reacted/ s. g catalyst

 Packed-bed Reactor

W – catalyst weight coordinate

As in the PFR case, we can calculate design equation now in terms

of catalyst weight coordinate.

FA|W  FA|WW ' dFA

FA|W  FA|W  W  ri ' W  0 ri '  rA 
W dW
No accumulation = 0
 Packed-bed Reactor
FA|W  FA|W  W  rAW  0

No accumulation = 0

rAW  moles A mass of catalyst   moles A

(time)(mass of cataly st) time

F A|W  W  F A|W ' dFA

FA|W  FA|W  W  rAW  0 rA' 
W
rA 
dW
Reactor Mole Balance: Summary
Mole Balance Algebraic Integral
Reactor Comment
Differential Form Form Form

Batch • No spatial variations

dNA NA0 dNA
• Fin = Fout =0  rA V t1  
• V = constant dt NA1 - rA V

CSTR • No spatial variations

• Well mixed - const. F A0  FA
C, T, rxn rate. ― V ―
• No accumulation  rA
• Steady state
PFR • Steady state dFA F A0 dFA
 rA V1  
dV F A1 - rA
PBR • Steady state dFA F A0 dFA
 rA' W1  
dW F A1 - rA'
 Tutorial 1
The reaction
A →B
Is to be carried out isothermally in a continuous-flow reactor.
Calculate both CSTR and PFR reactor volume necessary to consume
99% of A (i.e., CA = 0.01CA0) when the entering molar flow rate is 5
mol/h, assuming the reaction rate –rA is:
(a) –rA = k with k = 0.05 mol/h.dm3
(b) –rA = kCA with k = 0.0001 s-1
(c) –rA = kCA2 with k = 3 dm3/mol.h
The entering volumetric flow rate is 10 dm3/h.
[Note: FA = CAν. For a constant volumetric flow rate v = v0, then FA = CAν0.
Also, CA0 = FA0 /ν0 = (5 mol/h)(10 dm3/h) = 0.5 mol/dm3.]
CSTR
Solution 1
FA0  FA
Mole balance: V
 rA

mol
Rate law:  rA  k  0.05
hr.dm3

mol
FA0  0.01F A0
5 0.99 
Combine: V  hr  99.0dm3
 rA mol
0.05
hr.dm3

Volume of the CSTR = 99.0 dm3

PFR
Solution 1
dFA
Mole balance:  rA
dV
mol
Rate law:  rA  k  0.05
hr.dm3
dFA
Combine:  k
dV
F V
1 A
  dFA   dV
k FA0 0
mol
5
1 hr
V   0.01F A0  FA0    0.99 
k mol
0.05
hr.dm3

Volume of the PFR = 99.0 dm3