Mole Balances

Chemical Reaction Engineering (CRE)

Chemical kinetics: chemical reaction rate & reaction mechanism
Reactor design
One of the most important field to determine whether a chemical process is
economically feasible or not
Various application of CRE principles
Waste treatment, microelectronics, nanoparticles,
Living system, manufacture of chemicals and
pharmaceuticals
Objectives
To describe and define the rate of reaction
To derive the general mole balance equation
To apply the general mole balance equation to the four most common types of
industrial reactors preliminary form of design equation
The rate of reaction, -r
A
How fast a number of moles of one chemical species are being consumed to
form another chemical species
Chemical species: any chemical component or element with a given identity
Identity of chemical species determined by the kind, number, and configuration of that species atoms
Ex, nicotine, cis-2-butene & trans-2-butene
Chemical reaction:
when a detectable number of molecules of one or more species 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
structure or configuration of these atoms
Rate of disappearance of species A
The number of A molecules that lose their chemical identity per unit time per unit volume through
the breaking and subsequent re-forming of chemical bond during the course of the reaction
Rate of reaction (homogeneous), -r
A
(mol/dm
3
s)
The number of moles of A reacting per unit time per unit volume
Rate of reaction (heterogeneous), -r
A
(mol/sg catalyst)
The number of moles of A reacting per unit time per unit mass of catalyst
Wrong definition for rate of reaction
Not rate of formation A but a mole balance for a constant volume batch system
NaOH + CH
3
COOC
2
H
5
CH
3
COONa + C
2
H
5
OH
Product stream rate = total feed rate
Operation at steady state
r
A
= 0
C
2
H
5
OH and CH
3
COONa are being formed from NaOH
and CH
3
COOC
2
H
5
at a finite rate
Rate equation (rate law) for r
j
an algebraic equation the is solely a function of the properties of the reacting materials
and reaction condition (conc. temp. pressure, or type of catalyst) at a point in the
system, which is independent of the type of reactor
General mole balance equation

If all the system variables are spatially
uniform throughout the system volume
Various reaction rate with the position
in the system volume
Total rate of generation for total system volume
that is divided into M subvolumes
Let M and V0:
Substitution for Gj
Batch reactors

F
jo
= F
j
= 0
Perfect mixing: no variation in the rate of
reaction throughout the reactor volume
Integral form of the mole balance
on batch reactor
Used for small-scale operation, for testing new
processes that have not been fully developed,
for manufacture of expensive products, and for
processes that are difficult to convert to continuous
operations
High conversion but high labor costs per batch,
the variability of products from batch to
batch, and difficulty of large-scale production
AB
Continuous-flow reactors

Continuous-Stirred Tank Reactor (CSTR)

Assumption: Steady state
Assumption: Well-mixed
Tubular reactor

Packed-Bed Reactor (PBR)

If negligible catalyst decay & no pressure drop through the reactor
Example 1
AB, the first order reaction is carried out in a tubular reactor in which the volumetric
flow rate is constant, i.e., =o
1. Concentration profile
As the species A is consumed, both F
A
and C
A
is decreased
C
A
=F
A
/
o
Concentration profile as a function of reactor volume
2. Derivation of equation relating V to C
AO
, C
A
, k, and
Mole balance on species A for a tubular reactor
Rate law
Constant volumetric flow rate
Industrial reactors

Liquid-phase reactions

Semibatch reactor
-Same disadvantages as the batch reactor
-Temperature control by regulation of the feed rate
-Capability of minimizing unwanted side reactions through the maintenance of a low
concentration of one of the reactant
CSTR
-Single or as a part of a series or battery of CSTRs
-Good temperature control (intense agitation)
-The lowest conversion of reactant per V among the flow reactors
Gas phase reactions

PFR
-Easy maintenance (no moving part)
-The highest conversion per V
-Difficulty in controlling temperature within the reactor
-Hot spot in exothermic reaction
PBR
-Heterogeneous gas-phase reaction
-The highest conversion per weight of catalyst among catalytic reactors
-Difficulty in controlling temperature within the reactor
-Channeling of gas flow, resulting in ineffective use of parts of reactor bed
Fluidized-bed reactor
-Analogus to CSTR (well mixing)
-Even temperature distribution throughout the bed
-Handle with large amounts of feed and solids
-Easy to replace or regenerate catalyst
-High cost of the reactor and catalyst regeneration equipment
Examples of gas phase industrial reactors

STTR (straight-through transport-reactor) & PBR for Fischer-Tropsch reaction
octane
olefin
ethylene
Water-gas-shift reaction
Summary

A mole balance on species j
Well mixing
The kinetic rate law for r
j
-Solely a function of properties of reacting materials and reaction conditions
-The rate of formation of species j per unit volume
-An intensive quantity
-An algebraic equation, not a differential equation