Lecture 3

Chemical Reaction Engineering (CRE) is the

field that studies the rates and mechanisms of
chemical reactions and the design of the reactors in
which they take place.

1 Dr. Arkan Jasim Hadi

 Lecture 3 – Thursday 1/17/2013
 Review of Lectures 1 and 2
 Building Block 1
 Mole Balances (Review)
 Size CSTRs and PFRs given –rA= f(X)
 Conversion for Reactors in Series
 Building Block 2
 Rate Laws
 Reaction Orders
 Arrhenius Equation
 Activation Energy
 Effect of Temperature

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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
NA
NA
dN A
Batch dN A
 rAV t  rAV
dt N A0
t
CSTR FA 0  FA
V
rA FA
FA
dFA dFA
PFR
dV
 rA V 
FA 0
drA
V

FA FA
dFA dFA
PBR

 rA W  rA
3 Dr. Arkan Jasim Hadi dW FA 0
W
 a A  bB
 c C  d D
Choose limiting reactant A as basis of calculation

b c d
A  B
 C  D
a a a

moles A reacted
X
moles A fed

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 Reactor Mole Balances Summary
In terms of Conversion
Reactor Differential Algebraic Integral
X
X
dX
Batch N A0
dX
  r AV t  N A0 
dt 0
 rAV
t
FA0 X
CSTR V
 rA
X
dX dX
PFR FA0   rA V  FA0 
dV 0
 rA
X
X
dX
PBR F
dX
 rA W  FA0 
5 Dr. Arkan Jasim HadiA0 dW  rA
0
W
 Levenspiel Plots

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 Reactors in Series

moles of A reacted up to point i

Xi 
moles of A fed to first reactor

Only valid if there are no side streams

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 Reactors in Series

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 Rate Laws and Stoichiometry
3.1 Basic Definitions
A homogeneous reaction is one that involves only one phase. A heterogeneous reaction involves
more than one phase, and reaction usually occurs at, or very near the interface between the phases.
An irreversible reaction is one that proceeds in only one direction and continues in that direction
until the reactants are exhausted. A reversible reaction, on the other hand, can proceed in either
direction, depending on the concentrations of reactants and products relative to the corresponding
equilibrium concentrations. An irreversible reaction behaves as if no equilibrium condition exists.
3.1.1 The Reaction Rate Constant
The limiting reactant is usually chosen as our basis for calculation. The rate of disappearance
of A, - rA depends on temperature and composition. For many reactions it can be written as the
product of a reaction rate constant k and a function of the concentrations (activities of the
various species involved in the reaction:

The algebraic equation that relates - rA , to the species concentrations is called the
kinetic expre:ssion or rate law. However, for reactions in which the stoichiometric
coefficient is 1 for all species involved in the reaction, for example,

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3.1.1 The Reaction Rate Constant

The reaction rate constant k is not truly a constant, but is merely independent of the
concentrations of the species involved in the reaction. The quantity k is also referred
to as the specific reaction rate (constant). It is almost always strongly dependent
on temperature. In gas-phase reactions, it depends on the catalyst and may be a
function of total pressure. In liquid systems it can also be a function of total
pressure, and in addition can depend on other parameters, such as ionic strength
and choice of solvent.

It was the great Swedish chemist Arrhenius who first suggested that the
temperature dependence of the specific reaction rate, kA could be correlated by an
equation of the type

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 Arrhenius Equation
k is the specific reaction rate (constant) and is given by the Arrhenius
Equation.
where: kA  Ae  E RT

T  k  A
k
T 0 k 0
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T A  1013
Arrhenius Equation
The activation energy E has been equated with a minimum energy that must be
possessed by reacting molecules before the reaction will occur. From the kinetic
theory of gases, the factor gives the fraction of the collisions between molecules that
together have this minimum energy E

The activation energy is determined experimentally by carrying out the reaction at

several different temperatures. After taking the natural logarithm of Equation (3-2),

where:
E = Activation energy (cal/mol)
R = Gas constant (cal/mol*K)
T = Temperature (K)
A = Frequency factor (same units as rate constant k)
(units of A, and k, depend on overall reaction order)

it can be seen that a plot of In kA versus 1/T

should be a straight line whose slope is
proportional to the activation energy.
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 3.1.2 The Reaction Order and Rate Law
The dependence of the reaction rate -rA on the concentrations {of the species present, fn( Cj ), is almost
without exception determined by experimental observation. One of the most common general forms of
this dependence is the product of concentrations of the individual reacting species, each of which is raised
to a power, for example,
The order of a reaction
 
 rA  kC A C B (3-5) refers to the powers to which
the concentrations are
α order in A raised in the kinetic rate law
β order in B
Overall Rection Order, n  α  β

For example, in the gas-phase reaction

the kinetic rate law is  rNO  kC NO

2
CO 2

This reaction is second-order with respect to nitric oxide, first-order with respect to oxygen,
and overall is a third-order reaction. In general, first- and second-order reactions are more
commonly observed than zero- and third order reactions.
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3.1.2 The Reaction Order and Rate Law
The units of the specific reaction rate, k A , vary with the order of the
reaction. Consider a reaction involving only one reactant, such as

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3.1.3 Elementary Rate Laws
A reaction has an elementary rate law if the reaction order of each species is identical with
the stoichiometric coefficient of that species for the reaction as written.

for which the rate law is  rH 2  kC H 2C I 2

2A  B  3C
A reactor follows an elementary rate law if the reaction
orders just happens to agree with the stoichiometric
coefficients for the reaction as written.
e.g. If the above reaction follows an elementary rate law
 rA  k AC A2CB
2nd order in A, 1st order in B, overall third order

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 Building Block 2: Rate Laws
 Rate Laws are found from Experiments
2A+B3C
 Rate Laws could be non-elementary. For
example, reaction could be:
› Second Order in A
› Zero Order in B
› Overall Second Order
rA  k AC A2
rB  k B C 2
A

16
r 
Dr. Arkan Jasim Hadi
C k C
C A
2
 Relative Rates of Reaction
aA  bB  cC  dD
b c d
A B  C  D
a a a
rA rB rC rD
  
a b c d

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 Relative Rates of Reaction
2A  B  3C
mol
Given  rA  10
dm  s
3

rA rB rC
Then  
 2 1 3
 rA mol
 rB  5
2 dm  s
3

3 mol
rC  rA  15
2 dm  s
3

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 3.1.4 Reversible Reactions
All rate laws for reversible reactions must reduce to the thermodynamic relationship
relating the reacting species concentrations at equilibrium. At equilibrium, the rate of
reaction is identically zero for all species (i.e., -rA= 0). That is, for the general reaction

the concentrations at equilibrium are related by the thermodynamic relationship (see

Appendix C)

To illustrate how to write rate laws for reversible reactions we will use the
combination of two benzene molecules to form one molecule of hydrogen

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3.1.4 Reversible Reactions
The forward and reverse specific reaction rate constants, kB, and k-B respectively will be
defined with respect to benzene.
Benzene (B) is being depleted by the forward reaction

in which the rate of disappearance of benzene is

For the reverse reaction between diphenyl (D) and hydrogen (H2)

the rate of formation of benzene is given as

The net rate of formation of benzene is the sum of the rates of formation from
the forward reaction and the reverse reaction

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3.1.4 Reversible Reactions
Multiplying both sides of Equation (3-13) by -1, we obtain the rate law for the rate of
disappearance of benzene, -rB :

where

The equilibrium constant decreases with increasing temperature for exothermic reactions and
increases with increasing temperature for endothermic reactions.

Proof
At equilibrium,-rB = 0, and the rate law given by Equation (3-14) becomes

Rearranging, we obtain which is identical

to Equation (3-15).

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3.1.4 Reversible Reactions
Finally, we want to rewrite the rate of formation of diphenyl and hydrogen in terms of
concentration. The rate of formation of these species must have the same functional
dependence on concentrations as does the rate of disappearance of benzene. The
rate of formation of diphenyl is

Using the relationship given by Equation (2-20) for the general reaction

we can obtain the relationship between the various specific reaction rates, kB, kD :

Comparing Equations (3-16) and (3-17), we see the relationship is

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3.3 Stoichiometric Table
If the rate law depends on more than one species, we must relate the concentrations of the
different species to each other. This relationship is most easily established with the aid of a
stoichiometric table. For the general reaction

we shall take species A as our basis of calculation (i.e,, limiting reactant) and then
divide through by the stoichiometric coefficient of A,

in order to put everything on a basis of “per mole of A.

Next, we develop the stoichiometric relationships for reacting species that give the
change in the number of moles of each species (i.e.,A, B, C , and D).

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3.3 Stoichiometric Table
3.3.1 Batch Systems
As shown in figure 3-1 . At time t = 0 we will open the reactor and place a number of moles of
species A, B, C, D, and I (NA0, NB0 , NC0, ND0 and NI0 respectively) into the reactor.

That is, the number of moles of A remaining in the reactor after conversion X has been
achieved is
initially

remaining consumed

The complete stoichiometric table for the reaction

shown in Equation (2-2) taking place in a batch reactor
is presented in Table 3-2.

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25 Dr. Arkan Jasim Hadi
3.3 Stoichiometric Table
3.3.1 Batch Systems

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 3.3 Stoichiometric Table
3.3.1 Batch Systems
To calculate the number of moles of species B remaining at time t we recall that at time t the
number of moles of A that have reacted is NAOX. For every mole of A that reacts, b/a moles of
B must react; therefore, the total number of moles of B that have reacted is

Because B is disappearing from the system, the sign of the “change” is negative. NBO
is the number of moles initially in the system. Therefore, the number of moles of B
remaining in the system, is given in the last column of Table 3-2 as

The stoichiometric coefficients in parentheses (d/a+c/a-b/a-1) represent the increase

in the total number of moles per mole of A reacted. Because this term occurs often in
our calculations it is given the symbol 𝜹:
𝒅 𝒄 𝒃
𝜹= + − −𝟏
𝒂 𝒂 𝒂
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 3.3 Stoichiometric Table
3.3.1 Batch Systems
The total number of moles can now be calculated from the equation

The concentration of A is the number of moles of A per unit volume:

After writing similar equations for B, C, and D, we use the stoichiometric table to
express the concentration of each component in terms of the conversion X

We further simplify these equations by defining the parameter 𝚯𝒊 , which allows us to

factor Ni0 in each of the expressions, for concentration:
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3.3 Stoichiometric Table
3.3.1 Batch Systems

3.3.2 Constant-Volume Reaction Systems

Most liquid-phase organic reactions do not change density during the reaction, and
represent still another case to which the constant-volume simplifications apply. An
important exception to this general rule exists for polymerization processes
In gas-phase batch systems, the reactor is usually a sealed vessel with appropriate
instruments to measure pressure and temperature within the reactor

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3.3 Stoichiometric Table
3.3.2 Constant-Volume Reaction Systems

Example 3-4 Expressing Cj= hj(X)for a Liquid-Phase Reaction

Soap consists of the sodium add potassium salts of various fatty acids such as oleic,
stearic, palmitic, lauric, and myristic acids. The saponification for the formation of
soap from aqueous caustic soda and glyceryl stearate is

Letting X represent the conversion of sodium hydroxide (the moles of sodium

hydroxide reacted per mole of sodium hydroxide initially present), set up a
stoichiometric table expressing the concentration of each species in terms of its initial
concentration and the conversion X

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3.3 Stoichiometric Table
3.3.2 Constant-Volume Reaction Systems

Solution
taking sodium hydroxide as our basis, we divide through by the stoichiometric
coefficient of sodium hydroxide to put the reaction expression in the form

1 1
𝐴 + 𝐵→ 𝐶+ 𝐵
3 3
We may then perform the calculations shown in Table E3-4.1. Because this is a liquid-phase
reaction, the density 𝝆 is considered to be constant; therefore, V = V0

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3.3.2 Constant-Volume Reaction Systems
Example 3-4 Expressing Cj= hj(X)for a Liquid-Phase Reaction

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3.3.2 Constant-Volume Reaction Systems
Example 3-5 What Is the Limiting Reactant? Having set up the stoichiometric table in
Example 3-4, one can now readily use it to calculate the concentrations at a given conversion.
If the initial mixture consists solely of sodium hydroxide at a concentration of 10 mol/L (Le.,
10 mol/dm3 or 10 kmoil’m3) and of glyceryl stearate at a concentration of 2 g mol/L, what is
the concentration of glycerin when the conversion of sodium hydroxide is (a) 20% ,and
(b) 90%?

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3.3.2 Constant-Volume Reaction Systems
Example 3-5 What Is the Limiting Reactant

Negative concentration-impossible!
Ninety percent conversion of NaOH is not possible, because glyceryl stearate is the
limiting reactant. Consequently, all the glyceryl stearate is used up before 90%of the
NaOH could be reacted. It is important to choose the limiting reactant as the basis of
calculation

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3.3 Stoichiometric Table
3.3.3 Flow Systems
The form of the stoichiometric table for a continuous-flow system (see Figure 3-2) is virtually
identical to that for a batch system (Table 3-2) except that we replace Nj0 by Fj0 and Nj by Fj
(Table 3-3). Taking A as the basis, divide Equation (2-1) through by the stoichiometric
coefficient of A to obtain

For a flow system, the

concentration CA at a given point
can be determined from FA and
the volumetric flow rate 𝜐 at that
point:

Definition of
concentration for 𝐹𝐴 𝑚𝑜𝑙𝑒/𝑡𝑖𝑚𝑒 𝑚𝑜𝑙𝑒
𝐶𝐴 = = =
flow system 𝜐 𝑙𝑖𝑡𝑒𝑟𝑠/𝑡𝑖𝑚𝑒 𝑙𝑖𝑡𝑒𝑟𝑠

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 3.3 Stoichiometric Table
3.3.3 Flow Systems
we now can write the concentrations of A, B, C, and D for the general reaction given
by Equation (2-2) in terms of the entering molar flow rate (FA0, FB0, FC0 , FD0), the
conversion X , and the volumetric flow rate, 𝜐.

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3.3 Stoichiometric Table
3.3.3 Flow Systems

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3.3 Stoichiometric Table
3.3.3 Flow Systems
For liquids, volume change with reaction is negligible when no phase changes are
taking place. Consequently, we can take
Then

However, for gas-phase reactions the volumetric flow rate most often changes during
the course of the reaction due to a change in the total number of moles or in
temperature or pressure. One cannot always use Equation (3-29) to express
concentration as a function of conversion for gas-phase reactions.
3.3.4 Volume Change with Reaction
In our previous discussions, we considered primarily systems in which the reaction volume or
volumetric flow rate did not vary as the reaction progressed. Most batch and liquid-phase and
some gas-phase systems fall into this category. There are other systems, though, in which either
V or 𝜐 do vary, and these will now be considered. A situation in which a varying flow rate
occurs quite frequently is in gas-phase reactions that do not have an equal number of product
and reactant moles. For example, in the synthesis of ammonia
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 3.3 Stoichiometric Table
3.3.4 Volume Change with Reaction
Individual concentrations can be determined by expressing the volume V for a batch system (or volumetric
flow rate 𝜐 for a flow system) as a function of conversion using the following equation of state:

in which V and NT are defined as before and

T = temperature, K
P = total pressure, atm (kPa; 1 atm = 101.3 kPa)
Z = compressibility factor
R = gas constant = 0.08206 dm3 .atm/gmol.K
This equation is valid at any point in the system at any time t. At time t = 0 (i.e., when
the reaction is initiated), Equation (3-30) becomes

Dividing Equation (3-30) by Equation (3-31) and rearranging yields

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 3.3 Stoichiometric Table
3.3.4 Volume Change with Reaction
We now want to express the volume V as a function of the conversion X. Recalling the
equation for the total number of moles in Table 3-2

we divide through by NT0:

where yA0 is the mole fraction of A initially present. If all the species in the generalized
reaction are in the gas phase, then

Equation (3-34) is further simplified by letting

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 3.3 Stoichiometric Table
3.3.4 Volume Change with Reaction

Equation (3-32) now becomes

In gas-phase systems that we shall be studying, the temperatures and pressures are
such that the compressibility factor will not change significantly during the course of the
reaction; hence Z0 = Z. For a batch system the volume of gas at any time t is

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 3.3 Stoichiometric Table
3.3.4 Volume Change with Reaction

Equation (3-38) applies only to a variable-volume batch reactor. If the reactor is a

rigid steel container of constant volume, then of course V = V0.
For a constant volume container, V = V0 and Equation (3-38) can be used to
calculate the pressure inside the reactor as a function of temperature and
conversion.
An expression similar to Equation (3-38) for a variable-volume batch reactor exists for a
variable-volume flow system. To derive the concentrations of the species in terms of
conversion for a variable-volume flow system, we shall use the relationships for the
total concentration. The total concentration at any point in the reactor is

At the entrance to the reactor

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 3.3 Stoichiometric Table
3.3.4 Volume Change with Reaction
Taking the ratio of Equation (3-40) to Equation (3-39) and assuming negligible changes
in the compressibility factor, we have upon rearrangement

Gas-phase
volumetric flow
rate
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 3.3 Stoichiometric Table
3.3.4 Volume Change with Reaction

We can now express the concentration of species j for a flow system in terms of
conversion:

We will use this form of the concentration equation for multiple gas-phase reactions
and for membrane reactors. Substituting for Fj and FT in terms of conversion in
Equation (3-45) yields

Dividing numerator and

denominator by FT0 ,we
44 have
Dr. Arkan Jasim Hadi
 3.3 Stoichiometric Table
3.3.4 Volume Change with Reaction

where 𝑣𝑖 is the stoichiometric coefficient, which is negative for reactants and positive
for products. For example, for the reaction

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 3.3 Stoichiometric Table
3.3.4 Volume Change with Reaction
Example 3-7 determining Cj =hj (x) for a Gas-Phase Reaction
A mixture of 28% SO2 and 72% air is charged to a flow reactor in which SO2 is oxidized.

2𝑆𝑂2 + 𝑂2 → 2𝑆𝑂3
First, set up a stoichiometric table using only the symbols (i.e., Θ𝑖 , 𝐹𝑖 )and then prepare a second
stoichiometric table evaluating numerically as many symbols as possible for the case when the
total pressure is 1485 kPa and the temperature is constant at 227°C.

Solution
Taking SO2 as the basis of calculation, we divide the reaction through by the stoichiometric
coefficient of our chosen basis of calculation
1
𝑆𝑂2 + 𝑂2 → 𝑆𝑂3
2
Initially, 72% of the total number of moles is air containing 21% O2 and 79% N2

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 3.3 Stoichiometric Table
3.3.4 Volume Change with Reaction
Example 3-7 determining Cj =hj (x) for a Gas-Phase Reaction

To write concentration in terms of conversion, we must express the volumetric flow rate as a function of
conversion.

Recalling Equation (3-44), we have

Neglecting pressure drop in the reaction, P = P0, yields

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 3.3 Stoichiometric Table
3.3.4 Volume Change with Reaction
Example 3-7 determining Cj =hj (x) for a Gas-Phase Reaction

If the reaction is also carried out isothermally, T = T0 ,we obtain

The total concentration is

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 3.3 Stoichiometric Table
3.3.4 Volume Change with Reaction
Example 3-7 determining Cj =hj (x) for a Gas-Phase Reaction

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 3.3 Stoichiometric Table
3.3.4 Volume Change with Reaction
Example 3-7 determining Cj =hj (x) for a Gas-Phase Reaction

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 End of Lecture 3

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