Reactor Technology IV

1. Introduction

Chemical Engineering is concerned with converting a raw material to a final product with a higher
economic value. The conversion requires a physical as well as a chemical process. The physical process
may be one of separation, purification, etc – this is done in the Chemical Technology course. In this
course we will consider the chemical process. The chemical conversion is carried out in a reactor. The
aim of the chemical engineer is to design a reactor to operate as efficiently/economically as possibly.
When designing a reactor the economics of the overall process must be considered – not just the cost of
the reactor section.

In designing a reactor one uses information from other areas of Chemical Engineering: thermodynamics,
chemical kinetics, fluid mechanics, heat transfer, mass transfer, and economics. Marrying all these fields
to obtain a well-designed reactor will the aim of this course.

TERMINOLOGY

1.1) Introduction:

Unlike total mass, chemical components are not conserved when a chemical reaction occurs – some
species are consumed while others are generated. Before defining the mole balance we consider a few
related terms.

Chemical Species: Any chemical compound or element with a given identity.

Identity: Kind, number, and configuration (spatial arrangement) of the atoms making up
the species.
Chemical Reaction: A chemical reaction is said to occur when a detectable number of molecules of a
species have lost their chemical identity to form a new species.
Chemical species can lose their identities via one of three ways:

Decomposition: where a molecule is broken down into smaller molecules, atoms, or atom
fragments.
Combination: where one molecule/atom combines with another molecule/ atom.
Isomerization: where a new species is formed simply by the change in configuration of
the atoms making up the species.
Homogeneous Reaction: A reaction that takes place in one phase alone.
Heterogeneous Reaction: A reaction that requires at least 2 phases to proceeds at the rate it does.
Reactors: A reactor is a vessel in which a chemical reaction occurs.
Irreversible Reaction: a reaction that proceeds only in one direction and continues in that
direction until the reactants are exhausted.
Reversible Reaction: a reaction that can proceed in either direction, depending on the
concentrations of reactants and products relative to their corresponding
equilibrium concentrations.
1.2) Some Types of Reactors:

1. Batch Reactor:

In this type of reactor, reactants are initially charged into the reactor and left to react for a certain period.
The resultant mixture is then discharged. This type of reactor results in an unsteady operation –
composition of a particular species changes with time. At any instant the composition/concentration is
uniform throughout the reactor.

2. Semi-Batch Reactor:
3.

Or

This type of reactor has either an input OR an output stream.

1.2.3) Continuous Reactors

1.2.3.1)

This reactor has both input and output streams. Since the reactor contents is well stirred the
composition of the output stream is equivalent to that of the composition within the reactor. This
type of reactor is also known variously as a continuous stirred tank reactor (CSTR), back mix
reactor (BMR), or mixed flow reactor (MFR). These reactors are normally run at steady-state.

1.2.3.2)

PIPE

This type of reactor consists of a cylindrical pipe or tube – it is therefore called a tubular reactor. It
is normally operated at steady-state. The flow of fluid through the reactor is smooth – there is no
element of fluid mixing with that before or after it. There is no radial variation in concentration –
element moves through reactor as a plug – therefore also called a plug flow reactor (PFR). The
reactants are continually consumed as they move down the reactor.
 4. Catalytic Reactors:

Fixed Bed Reactors Fluidised Bed Reactor

2) MOLE BALANCES

2.2) Rate of Reaction (rj):

Consider the reaction:

aA + bB  cC + dD

The rate of reaction for the above reaction is defined as the number of moles of species A reacting
(disappearing) per unit time per unit base. Since species A is a reactant, its concentration will decrease
with time. The symbol for the rate of reaction is consequently: -rA. The rate of the above reaction can also
be expressed in relation to other species involved in the reaction – if we consider species D, then the rate
of reaction is expressed as the number of moles of species D formed (generated) per unit time per unit
base. Since species D is a product, its concentration will increase with time. The symbol for the rate of
reaction is consequently: rD.

Note: -rA and rD are related by the stoichiometric equation. This will be discussed in more detail
in later sections.

The “base” mentioned above is dependent on the reacting system:- If the system is homogeneous then
the base is considered to be the volume of the reacting fluid. In fluid-solid systems the base could be one
of mass of solid, surface area of solids, or volume of solids.

The rate of reaction is a function of temperature and composition (concentration):

rj = f1(temperature)  f2(composition)
= [kA(T)] [f2(CA, CB, CC, . . . )

where k is referred to as the reaction rate constant.

Notes:
k is not strictly a constant – it depends on the temperature of the reacting system. This will be
discussed in more detail in a later section.
The rate expression is an algebraic equation.
2.3) Concentration Effects on Reaction Rate:

Before determining the form of the concentration term in a rate expression, we need to define certain
terms.

2.3.1) Elementary and Non-elementary Reactions:

The effect of concentration on the reaction rate is almost always determined experimentally. An
elementary reaction is one for which the rate expression can be obtained directly from the stoichiometric
reaction equation. If we consider the following reaction to be elementary:
aA + bB  cC + dD

then an expression for the rate of reaction could be:

-rA = k CAa CBb wrt species A
or
-rB = k’ CAa CBb wrt species B
or
+rC = k’’ CAa CBb wrt species C
or
+rD = k’’’ CAa CBb wrt species D

A non-elementary reaction is one where there is no relationship between the reaction stoichiometric
equation and the rate expression. Consider the following reaction:
H2 + Br2  2HBr
This reaction is considered non-elementary because its rate expression turns out to be

Molecularity and Order of Reaction:

The molecularity of an elementary reaction refers to the number of atoms, ions, or molecules involved
(colliding) in the rate-limiting step of the reaction. This has been found have values of one (unimolecular),
two (bimolecular) and sometimes three (termolecular).

The order of a reaction refers to the powers to which the concentrations are raised in the rate expression.
For example, consider the following rate expression:
-rA = kA CA CB
This reaction is of order  with respect to component A, and of order  with respect to component B. The
overall order of the reaction is n, where n =  + .

Note: the order of a reaction (both with respect to a component and overall) need not be an integer.
The units for k are dependent on the order of the reaction:
Zero-order: -rA = kA
First-order: -rA = kA CA
Second-order: -rA = kA CA2
Third-order: -rA = kA CA3

Determine the dimensions of kA in each of the above cases.

Temperature Effects on Rates of Reactions

The rate law gives the relationship between reaction rate and concentration:

-rA = k(T) f(CA, CB,. . .)

where k is the reaction rate constant or the specific reaction rate.

k is not truly a constant – it is merely independent of the concentration of the species involved in
the reactor.

k(T) = Ae-E/RT

where A is the pre-exponential factor or frequency factor

E is the activation energy [J/mol; cal/mol]
R is the gas constant [8.314 J/mol K; 1.987 cal/mol K]
T is the absolute temperature [K]

The activation energy is determined experimentally by carrying out the reaction at several
different temperatures. Taking natural logs on both sides of the above equation:

ln K = ln (Ae-E/RT)
= ln A + ln e-E/RT
= ln A –E/R(1/T)
 ln k = -E/R(1/T) + ln A
y = a x + b

Hence a plot of ln k versus 1/T should be a straight line with slope = -E/R and an intercept = ln A

Ln A

Ln k

1/T

Reactions with activation energies are very temperature-sensitive – reactions with low activation
energies are relatively temperature-sensitive.
Rate Laws

A rate law describes the behavior of a reaction. The rate of a reaction is a function of temperature
(through the rate constant) and concentration.

1. Relative Rates of Reaction

Consider the following general reaction:

aA + bB  cC + dD
The rates of disappearance of the reactants and the formation of the products are not independent, but
are related as follows:

2. Power Law Model

3. Rate Constant, k

Is the specific reaction rate (constant) and is given by the Arrhenius Equation:

                           

 
Where:

E = activation energy (cal/mol)

R = gas constant (cal/mol*K)
T = temperature (K)
A = frequency factor (units of A, and k, depend on overall reaction order)
 The activation energy can be thought of as a barrier to the reaction. One way to view the barrier to
a reaction is through the reaction coordinates. These coordinates denote the energy of the system
as a function of progress along the reaction path. For the reaction

                                                        

the reaction coordinate is

                     
Progress along reaction path

We see that for the reaction to occur, the reactants must overcome an energy barrier E B. The
energy barrier is related to the activation energy, E. The barrier height is a result of

(1) the molecules needing energy to distort or stretch their bonds in order to break them and
to thus form new bonds,

(2) the as reaction molecules come close together they must overcome both steric and
electron repulsion forces, and

  (3) the quantum effects that can in some cases produce a barrier.

By increasing the temperature we increase the kinetic energy of the reactant molecules which can
in turn be transferred to internal energy to increase the stretching and bending of the bonds
causing them to be in an activated state, vulnerable to bond breaking and reaction. The energy of
the individual molecules follows a distribution of energies where some molecules have more
energy than others. One such distribution is shown below.
                                

where fdE is the fraction of molecules that have an energy between E and E + dE. The shaded
area represents the fraction of molecules that have an energy E or greater which is energy
sufficient to react.
You can tell the overall reaction order by the units of k
CA -rA Reaction Order Rate Law k
(mol/dm ) 3
(mol/dm *s) 3
zero -rA = k (mol/dm3*s)
(mol/dm3) (mol/dm3*s) 1st -rA = kCA s-1
(mol/dm3) (mol/dm3*s) 2nd -rA = kCA2 (dm3/mol*s)

4. Elementary Reactions

A reaction follows an elementary rate law if and only if the (iff) stoichiometric coefficients are the same as
the individual reaction order of each species. For the reaction in the previous example ( ),
the rate law would be:

If 2NO+O2    2NO2     then -rNO = kNO (CNO)2 CO2   if elementary! 

5. Non-Elementary Rate Laws

Example: If the rate law for the non-elementary reaction

is found to be
then the reaction is said to be 2nd order in A, 1st order in B, and 3rd order overall.  

6. Reversible Reactions
The net rate of formation of any species is equal to its rate of formation in the forward reaction plus its
rate of formation in the reverse reaction:
ratenet = rateforward + ratereverse
At equilibrium, ratenet 0 and the rate law must reduce to an equation that is thermodynamically consistent
with the equilibrium constant for the reaction.

Example: Consider the exothermic, heterogeneous reaction

At low temperature, the rate law for the disappearance of A is

At high temperature, the exothermic reaction is significantly reversible:
What is the corresponding rate law? Let's see.

If the rate of formation of A for the forward reaction (A + B C) is

then we need to assume a form of the rate law for the reverse reaction that satisfies the equilibrium

condition. If we assume the rate law for the reverse reaction (C A + B) is

then:                   

and:

The derivation for the above expression is given below:

The forward rate is:

And the reverse rate law is:

The net rate for species A is the sum of the forward and reverse rate laws:

Substituting for rfor and rrev:

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