Chemical Reaction Engineering

UNIT 4
Concept of parallel & series reactions
Parallel & series are the special cases of multiple
reactions.
Multiple reactions require more than one rate
expression to describe the progress of the reaction
and to measure the concentration of reactant as a
function of time.
Parallel reactions produce two varieties of products
viz., desired product and unwanted product. Our
objective is to maximize the amount of desired
product in the final mixture.
 Analysis of parallel reaction
Consider the decomposition of reactant ‘A’ by any
one of the two paths:

with corresponding rate equations (a1 = order of

desired reaction; a2 = order of unwanted reaction)
dividing the rate equations will help us to quantify
the amount of desired product (R) in product mixture

The above ratio should be as large as possible to

have maximum amount of (R) in the product.
Reactant concentration (CA) is the only factor in the
ratio which can be adjusted.
If a1>a2, desired reaction order is higher than
undesired reaction order, the ratio value is
proportional to reactant concentration.
More the value of CA , more is the amount of desired
product (R) in the final product mixture.
Product mixture contains 3 components namely: R, S
and un reacted ‘A’.
To maintain higher value for CA , use plug flow or
batch reactor, because in this reactors concentration
value decreases gradually not rapidly.
If a2>a1, undesired reaction order is higher than
desired reaction order, the ratio value is inversely
proportional to reactant concentration.
Thus a lower value of CA, will maximize the amount
of desired product R in the final mixture.
For this use a large mixed flow reactor to maximize
the desired product amount.
If a1=a2, desire reaction order = unwanted reaction
order, in this case ratio unaffected by type of reactor
but depends on k2/k1 (temperature dependent
term).
For reactions in parallel, the concentration level of
reactants is the key to proper control of product
distribution.
A high reactant concentration favors the reaction of
higher order.
a low concentration favors the reaction of lower
order, while the concentration level has no effect on
the product distribution for reactions of the same
order.
For favourable product distribution, use proper
contacting pattern between the 2 reactants.
 Best contacting pattern for parallel reactions
For non continuous operation with 2 reactants A&
B
For continuous flow operation with 2 reactants A&
B
To calculate the quantities of R and S two terms used
are “Instantaneous fractional yield of R” and “Overall
fractional yield of R”.
Instantaneous fractional yield of R is defined as

is a function of CA, and since CA in general varies

through the reactor, will also change with position
in the reactor.
Overall fractional yield of R is
Overall fractional yield = mean of the instantaneous
fractional yield
For plug flow is a continuous function of CA, thus the
mean of function is,

For a continuous function y = f(x) between the limit

x=a to x=b , the mean function value is
For MFR since the concentration is uniform at every
location inside the reactor, is also constant at every
location and it is like a discrete function.
Hence overall yield for MFR is,

Since values are same everywhere

φ1= φ2= φ3= φ4= φ5=…………. φn = φ
Thus the mean value is

In general for MFR,

Amount of R in product

Amount of S in product, CSf = (1-Φ) (CAo – CAf)

Amount of unreacted A, CAf = CAo – CRf – CSf
Problems on Parallel reactions
Instantaneous fractional yield of desired component is
Problems for practice
Next problem:
Irreversible first order reaction in series
2 ways of treating the reactant ‘A’ is:
formation and its concentration drops
Best reactors for series reaction
Problem No:1
• For the series reactions which contacting pattern can give high
concentration of intermediates:
• For plug flow or batch reactor,
• For mixed flow reactor,
Problems for practice

Problem No: 2
 Unit 5
Temperature and pressure effects
• The reaction temperature and pressure also
influence the progress of reactions.
• Thermodynamics gives two important information,

- the first being the heat liberated or absorbed

for a given extent of reaction,
- the second being the maximum possible
conversion
 Heat of Reaction from Thermodynamics

• The heat liberated or absorbed during reaction at

temperature T2, depends on the nature of the
reacting system, the amount of material reacting,
and the temperature and pressure of the reacting
system, and is calculated from the heat of reaction
(∆Hr)
• If heat of reaction is not known then it is calculated
using heat of combustion or heat of formation data’s.
• T1 = standard temperature = 25oC
Problem 1:
Problem:
Problem:
• For irreversible reactions, the rate always increases with temperature at
any composition, so the highest rate occurs at the highest allowable
temperature. This temperature is set by the materials of construction or
by the possible increasing importance of side reactions.

• For endothermic reversible reactions a rise in temperature increases

both the equilibrium conversion and the rate of reaction. Thus, as with
irreversible reactions, the highest allowable temperature should be used.

• For exothermic reversible reactions the situation is different, for here two
opposing factors are at work when the temperature is raised-the rate of
forward reaction speeds up but the maximum attainable conversion
decreases. Thus, in general, a reversible exothermic reaction starts at a
high temperature which decreases as conversion rises. Figure 9.5 shows
this progression, and its precise values are found by connecting the
maxima of the different rate curves. We call this line the locus of
maximum rates.
Conversion in adiabatic and non adiabatic reactors
• This figure illustrates the shape of the energy balance curve for both
endothermic and exothermic reactions for both mixed flow and plug flow
reactors.
• This representation shows that whatever is the conversion at any point in
the reactor, the temperature is at its corresponding value on the curve.
• For plug flow the fluid in the reactor moves progressively along the curve,
for mixed flow the fluid immediately jumps to its final value on the curve.
These are the adiabatic operating lines for the reactor.
• With increased inerts CP rises, and these curves become more closely
vertical. A vertical line indicates that temperature is unchanged as
reaction proceeds.
• The best reactor type, that which minimizes V/FAo is found directly from
this X, versus T graph. If the rate progressively decreases with conversion,
then use plug flow. This is the case for endothermic reactions.
• For exothermic reactions that have a large temperature rise during
reaction, the rate rises from a very low value to a maximum at some
intermediate XA, then falls.
END