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Semibatch reactors can be operated under a variety of different scenarios. The operating
conditions are often dictated by the kinetics of the reaction. For example, when several
reactions occur in the vessel the rate of feed addition may be controlled to achieve a preferred product distribution by controlling the relative concentrations of reactants.
Alternatively, the rate of heat release may be the deciding factor. Regardless of the complexity, the analysis can be performed using the material described in this section as a
starting basis.

4.6 Summary
This chapter has shown how the energy balance equation is used to determine the
temperature in an ideal chemical reactor. The energy balance equation is always coupled
to the mole balance equation through the temperature dependence of the reaction rate
constants and the temperature dependence of the physical properties of the reacting fluid.
The energy balance equation is almost invariably a nonlinear equation, and with the coupling to the mole balance requires a numerical solution. When performing an energy balance, it is important to remember that both internal energies and enthalpies of reaction are
used. In many cases, the two are effectively interchangeable; however, in other cases, the
differences are quite significant.
The introduction of the energy balance into the reactor analysis problem can lead to
some interesting complexities, especially in the CSTR. In that reactor, even simple kinetic
expressions can result in the existence of multiple solutions for the mole and energy balance. In such a case, the reactor operation can exhibit unstable operation if the inlet conditions fluctuate. In this case, it is necessary to perform a transient analysis to determine the
operating point of the reactor.
The combination of the mole and energy balance equations can be used to solve for the
concentration and temperatures in any ideal reactor system, regardless of the number of
reactions and reactors, or the complexity of the reaction kinetics. If one starts from the
basic balance equations, it is possible to derive the appropriate system of equations and
then to solve them. The most important factor to remember is that the correct solution
depends on making the appropriate choices when deriving the equations.
PROBLEMS

4.1 An elementary second-order liquid-phase reaction occurs in a CSTR. The reactor has a volume of 1200L and is heated by a steam jacket.
A + B k
C ( rA ) = kCACB

The feed temperature is 27C, and the flow rate is 30L/min. The inlet concentrations of A and B are 2mol/L. The desired conversion of A is 60%.
a. Determine the reactor temperature required to achieve the desired conversion.
b. Determine the temperature of the steam in the jacket required to operate
the reactor at the temperature determined in part (a).

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Energy Balances in Ideal Reactors

Activation energy
Rate constant at 27C

10,000 J/mol
0.01725 L/molmin
41,840 J/mol A

HR (assume constant)
Heat capacity of mixture
Reactor heat transfer area
Heat transfer coefficient

4184 J/LK
6 m2
70 W/m2K

4.2 A tubular flow reactor is to be designed to produce butadiene from butene by

dehydrogenation (gas-phase reaction). The first-order reaction rate expression is
written in terms of the partial pressure of butene as
C 4H8 C 4H6 + H 2

(rC H ) = kPC H
4

mol/L h

The constant k has units of mol ( h L atm ) . The reaction is endothermic,

the reactor is often operated adiabatically; therefore, steam is often added to the
feed to provide thermal energy for the reaction. For this reactor, the feed is a
mixture of 10mol of steam for each mole of butene. The reactor pressure is 2atm
and the feed temperature is 650C. Values of the rate constant at different temperatures are given in the following table:
T(K)
k

922
11.0

900
4.90

877
2.04

855
0.85

832
0.32

Assume that the heat of reaction is a constant 1.1105J/mol butene. The heat
capacity of the feed stream may be considered constant at 2.1kJ/kg K.
a. Calculate the reactor volume for a 20% conversion of butene if the reactor is
operated isothermally at 650C with a total inlet molar flow rate of
11,000mol/h.
b. Determine the reactor volume for 20% conversion of butene for a total inlet
molar feed rate of 11,000mol/h in an adiabatic reactor.
4.3 A chemical plant is planning to install a reactor to produce ethanoic acid by the
hydrolysis of methyl acetate. The reaction is
CH 3 COOCH 3 + H 2O CH 3 CO 2H + CH 3 OH

The reaction is pseudo-first-order overall because of the excess of water

rCH3 COOCH3 = k [ CH 3 COOCH 3 ]

At 25C, the rate constant has a value k=3.51 103 min1, and at 35C,
k= 8.84 103 min1. A 1mol/L aqueous solution of methyl acetate resides in a
storage tank at 0C and will be pumped to the reactor at a rate of 30,000L/h.
The production rate of ethanoic acid is to be 8.64 tonnes/day, based on 24h a

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Introduction to Chemical Reactor Analysis

day operation. The reactor is to be an adiabatic CSTR and the feed is to be preheated in an electrical heater. The operating cost of the reactor (including capital cost allowance, stirring cost, pumps, etc.) is $1 a minute for each liter of
capacity (e.g., a 4L reactor costs $4 a minute, a 6L reactor $6 a minute, etc.).
Electricity costs $0.10 a kilowatt hour and the preheater is 90% efficient.
Determine the reactor volume which will minimize the production cost of ethanoic acid. Assume that the specific heat of the mixture is a constant equal to
4180J/kg K. The heat of formation data, H of ,298, are given below:
Methanol
Water

238.7 kJ/mol
286.0 kJ/mol

Ethanoic acid
Methyl acetate

484.4 kJ/mol
447.8 kJ/mol

4.4 The hydrogenation of aromatic compounds in an oil is carried out in an internal

recycle reactor at a constant hydrogen pressure. The recycle rate is sufficiently
high so that the reactor behaves like a CSTR. The reactor contains 20g of catalysts and is operated adiabatically. The rate function for the hydrogenation of
the aromatic compounds is
E
rHYD = raro = A exp
[Caro ] moles of aromatics/h gcat
Rg T

The oil has the following properties:

xf,aro

Mass fraction of feed that is aromatic

0.30

Mwt
CP

Average molecular mass of feed

Average heat capacity of oil
Heat of reaction of aromatics

210
1.75J/(g K)
2.0 105 J/mol

HR,aro

The values of the kinetic parameters are:

A = 1.3 1011 cm 3/h gcat

E
= 16,300 K
Rg

Oil is fed to the reactor at a constant rate of 0.5cm3/min. The temperature of

the feed stream is increased very slowly from 250C to 375C and then decreased
very slowly from 375C to 250C. Assume that the density of the oil is constant
at 0.85g/cm3 and that the hydrogenation of the aromatics is the only reaction.
The pseudo-steady-state approximation can be made for the slow changes in
feed temperature, that is, it can be assumed that steady state is achieved at all
feed temperatures because the changes in feed temperature occur very slowly.
Prepare a plot of fractional conversion of the aromatic content as a function of
feed temperature for the above changes in feed temperature.
4.5 The following reaction is carried out in an adiabatic plug flow reactor:

A+B C+D

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Energy Balances in Ideal Reactors

Calculate the maximum conversion that may be achieved if the feed enters at
27C. Only A and B are in the feed. The following data are available:
H R = 120, 000 J/mol
CP ,A = CP , B = CP , C = CP , D = 100 J/mol K
K e (equilibrium constant) = 500,000 at 50C
FA0 = FB0 = 10 mol/min

4.6 A first-order endothermic reaction is carried out in a constant-volume batch

reactor.
10, 000
1
A B the rate constant is: k = 0.20 exp
min
R
T

The enthalpy of reaction is 50,000J/mol. The reactor volume is 1m3 and contains 1000kg of mixture. There are initially 10,000mol of reactant A in the reactor. The reactor is heated to 400C, during which time 10% of the initial A reacts.
When the temperature reaches 400C, the reactor operates adiabatically. The
heat capacity of the mixture is a constant 2000J/kg K.
a. After the heating stops, how much time is required to achieve a final conversion of 70% of the A originally present before the heating started?
b. What is the final temperature in the reactor?
4.7 A first-order liquid-phase exothermic reaction

AB

is carried out in a batch reactor. There is no heat transfer through the reactor
wall. The reaction mixture is to be held at a constant 40C by the addition of an
inert coolant at a temperature of 25C. The flow rate of coolant varies with time
so as to maintain the reactor temperature at 40C. The following data are
available:
Heat capacity of all components
Density of all components

CP=2000 J/kg K (assume constant)

1000 kg/m3

Heat of reaction
Value of rate constant at 40C

H R = 200, 000 J/mol

1.0 104 s1

At time t=0, only compound A is present in the tank at a concentration of

8000mol/m3. The initial volume is 1.5m3.
a. Calculate the conversion of A 2h after the start of the reaction.
b. Calculate the rate of coolant addition 2h after the start of the reaction.
c. Calculate the total amount of coolant added after 2h.

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Introduction to Chemical Reactor Analysis

4.8 Consider an adiabatic constant pressure batch reactor in which a second-order

gas-phase reaction occurs

A+BC

( rA ) = kCACB

The rate constant is independent of temperature and equals 0.01m3/mols.

The initial reactor temperature is 450K and the pressure is 100kPa. The initial
volume of the reactor is 1.0m3. The reactor initially contains 30% by volume A,
30% B, and 40% inerts. The heat capacity of the mixture is a constant CV=1000
J/kg K. The average molecular mass of the initial material is 30g/mol. The internal energy change on reaction is a constant UR=60kJ/mol. Calculate
a. The time required to reach 80% conversion
b. The reactor volume at 80% conversion
c. The reactor temperature at 80% conversion
4.9 Consider a constant-volume batch reactor in which a liquid-phase reaction
occurs. The reaction is a catalytic reaction (solid catalyst is used), and is represented by the following overall reaction, with second-order kinetics:

A + B C + D ( rA ) = kCACB mol of A/s kgcat

The kgcat term means kg of catalyst and concentrations are in mol/m3. The
reaction rate constant is given by the following expression:

2500 6
k = 1 10 5 exp
m /mol s kgcat
T
One cubic meter (1000kg) of a fluid solution containing 2000mol of A and
2000mol of B are placed in the reactor. At time zero, 10kg of catalyst is added to
the reactor and the reaction starts.
a. If the reactor is operated isothermally at a temperature of 100C, calculate
how much time is required to reach 80% conversion.
b. If the reactor is operated adiabatically, and the initial temperature of the
mixture is 27C, calculate the temperature of the reaction mixture when the
conversion is 80%.

H R, A = 50, 000 J/mol

Heat capacity of fluid=4000J/kgK

Heat capacity of catalyst=10,000J/kgK
4.10 Consider an adiabatic plug flow reactor in which a second-order ideal gas-phase
reaction occurs

A+BC
The reactor feed is composed of 40mol% A, 50mol% B, and 10mol% inert
material. The total inlet molar flow rate is 10mol/s. The reactor inlet temperature is 300K and the pressure is 101.325kPa. The reaction rate is

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Energy Balances in Ideal Reactors

( rA ) = kCACB mol/s m 3

12, 500 3
where k = 1 1013 exp
m /mol s

The concentrations are in mol/m3. The enthalpy of reaction at 298K is equal

to 50,000J/mol. The heat capacities are

A: 10J/molK, B: 5J/molK, C: 15J/molK, and inert: 15J/molK

The desired fractional conversion of A is 80%. Calculate the reactor volume

required.
4.11 Consider the reaction

A+BC+D

The reaction is zero order. That is, the rate equation is

( rA ) =

E
A exp

Rg T

where A = 5 109 mol/m 3s and

E
= 7000 K
Rg

The reaction is carried out in a CSTR of volume 0.02m3 that is operated adiabatically. The inlet molar flow rates of A and B are 0.20 and 0.25mol/s, respectively. The total mass flow rate is 0.40kg/s. The constant enthalpy of reaction is
600kJ/mol (of A) and the heat capacity of the feed stream is 4200J/molK
(assume constant).
a. Calculate the outlet conversion if the reactor is operated at 340 K.
b. Derive a general steady-state mole balance for A. The result should be an
equation which gives the outlet conversion of A as a function of outlet
temperature.
c. For adiabatic operation with an inlet feed temperature of 300 K, develop the
steady-state energy balance. The result should be an equation that gives
outlet conversion as a function of outlet temperature.
d. Plot the mole and energy balances and identify the steady-state solution(s).
e. Comment on the stability of the steady state(s) obtained in part (d).

References
Froment, G.B, K.B. Bischoff, and J. De Wilde, 2011, Chemical Reactor Analysis and Design, 3rd Ed.,
Wiley, New York.
Lee, H.H., 1985, Heterogeneous Reactor Design, Butterworth, London.
Thomas, J.M. and W.J. Thomas, 1967, Introduction to the Principles of Heterogeneous Catalysis, Academic
Press, London.
Westerterp, K.R., W.P.M. van Swaaij, and A.A.C.M. Beenackers, 1984, Chemical Reactor Design and
Operation, John Wiley & Sons, New York.