Nonisothermal Reactor Design— 11

The Steady-State Energy

Balance and Adiabatic
PFR Applications
If you can’t stand the heat, get out of the kitchen.
—Harry S Truman

Overview. Because most reactions are not carried out isothermally, we

now focus our attention on heat effects in chemical reactors. The basic
CRE algorithm of mole balance, rate law, stoichiometry, combine, and
evaluate used in Chapters 1 through 10 for isothermal reactor design is
still valid for the design of nonisothermal reactors; we only need to add
one more step, the energy balance. The major difference lies in the
method of evaluating the combined mole balances, rate law, and stoichi-
ometry when temperature varies along the length of a PFR or when heat
is removed from a CSTR. This chapter is arranged as follows:

• Section 11.1 shows why we need the energy balance and how it
will be used to solve reactor design problems.
• Section 11.2 develops the energy balance to a point where it can
be applied to different types of reactors. It then gives the end
result, relating temperature and conversion or reaction rate for
the main types of reactors we have been studying.
• Section 11.3 develops the user-friendly energy balances for
reactors.
• Section 11.4 discusses the adiabatic operation of reactors.
• Section 11.5 shows how to determine the adiabatic equilibrium
conversion and how to carry out interstage cooling.
• Section 11.6 closes the chapter with a discussion of the opti-
mum inlet temperature to achieve the maximum conversion for
adiabatic operation.

493
494 Nonisothermal Reactor Design Chapter 11

11.1 Rationale
To identify the additional information necessary to design nonisothermal reac-
tors, we consider the following example, in which a highly exothermic reaction
is carried out adiabatically in a plug-flow reactor.

Example 11–1 What Additional Information Is Required?

The first-order liquid-phase reaction

A → B
is carried out in a PFR. The reaction is exothermic and the reactor is operated adia-
batically. As a result, the temperature will increase with conversion down the length
of the reactor. Because T varies along the length of the reactor, k will also vary,
which was not the case for isothermal plug-flow reactors.

T k X

V V V

Calculate the PFR reactor volume necessary for 70% conversion and plot the corre-
sponding profiles for X and T.

Solution
The same CRE algorithm can be applied to nonisothermal reactions as to isothermal
reactions by adding one more step, the energy balance.
1. Mole Balance (design equation):
dX !r
------- " ---------A- (E11-1.1)
dV FA0
2. Rate Law:
!r A " kC A (E11-1.2)
Recalling the Arrhenius equation,

E 1 1
k " k 1 exp ---  ----- ! --- (E11-1.3)
R  T1 T 
we know that k is a function of temperature, T.
3. Stoichiometry (liquid phase): v " v0
C A " C A0 ( 1 ! X ) (E11-1.4)

4. Combining:

E 1 1
–r A " k 1 exp ---  ----- ! --- C A0( 1 ! X ) (E11-1.5)
R T
 1 T 
Combining Equations (E11-1.1), (E11-1.2), and (E11-1.4), and canceling the
entering concentration, CA0 , yields
dX (1 ! X )
------- " k--------------------- (E11-1.6)
dV v0
Section 11.2 The Energy Balance 495

Combining Equations (E11-1.3) and (E11-1.6) gives us

Why we need the dX E 1 1  1-------------

! X-
------- " k 1 exp ---  ----
- ! --- (E11-1.7)
energy balance dV R  T1 T  v0

We see that we need another relationship relating X and T or T and V to solve

this equation. The energy balance will provide us with this relationship.
So we add another step to our algorithm; this step is the energy balance.
5. Energy Balance:
In this step, we will find the appropriate energy balance to relate temperature and
T0 = Entering conversion or reaction rate. For example, if the reaction is adiabatic, we will
Temperature show that for equal heat capacities, C PA and C PB, and a constant heat of reaction,
∆HRx = Heat of #H°Rx , the temperature-conversion relationship can be written in a form such as
Reaction
CPA = Heat Capacity !# H%Rx
T " T 0 & -------------------- X (E11-1.8)
of species A C PA
We now have all the equations we need to solve for the conversion and tem-
perature profiles.
Analysis: The purpose of this example was to demonstrate that for
nonisothermal chemical reactions we need another step in our CRE algorithm,
the energy balance. The energy balance allows us to solve for the reaction
temperature, which is necessary in evaluating the specific reaction rate
constant k(T).

11.2 The Energy Balance

11.2.1 First Law of Thermodynamics

We begin with the application of the first law of thermodynamics, first to a

closed system and then to an open system. A system is any bounded portion of
the universe, moving or stationary, which is chosen for the application of the
various thermodynamic equations. For a closed system, in which no mass
crosses the system boundaries, the change in total energy of the system, dÊ ,
is equal to the heat flow to the system, $Q, minus the work done by the sys-
tem on the surroundings, $W. For a closed system, the energy balance is
dÊ " $Q ! $W (11-1)
The $’s signify that $Q and $W are not exact differentials of a state function.
The continuous-flow reactors we have been discussing are open systems
in which mass crosses the system boundary. We shall carry out an energy bal-
ance on the open system shown in Figure 11-1. For an open system in which

Figure 11-1 Energy balance on a well-mixed open system: schematic.

496 Nonisothermal Reactor Design Chapter 11

some of the energy exchange is brought about by the flow of mass across the
system boundaries, the energy balance for the case of only one species entering
and leaving becomes

Rate of Rate of flow Rate of work Rate of energy Rate of

accumulation of heat to done by added to the energy leaving
of energy = the system – the system + system by mass – the system by mass
within the from the on the flow into the flow out of
system surroundings surroundings system the system
Energy balance dÊ sys
on an open
------------ = Q̇ – Ẇ + Fin E in – Fout E out (11-2)
dt
system
(J ' s) = (J ' s) – (J ' s) + (J ' s) – (J ' s)

Typical units for each term in Equation (11-2) are (Joule/s).

We will assume that the contents of the system volume are well mixed,
an assumption that we could relax but that would require a couple of pages of
text to develop, and the end result would be the same! The unsteady-state
energy balance for an open well-mixed system that has n species, each enter-
ing and leaving the system at its respective molar flow rate Fi (moles of i per
time) and with its respective energy Ei (joules per mole of i ), is

n n
dÊ sys
The starting point
------------ " Q̇ ! Ẇ & ! E iF i ! ! E iF i (11-3)
dt
i"1 in i"1 out

We will now discuss each of the terms in Equation (11-3).

11.2.2 Evaluating the Work Term

It is customary to separate the work term, Ẇ , into flow work and other work,
Ẇs . The term Ẇs , often referred to as the shaft work, could be produced from
such things as a stirrer in a CSTR or a turbine in a PFR. Flow work is work
that is necessary to get the mass into and out of the system. For example, when
shear stresses are absent, we write
[ Rate of flow work ]














n n
Flow work and
shaft work Ẇ " ! ! F iPṼi & ! F iPṼi & Ẇs (11-4)
i"1 in i"1 out

where P is the pressure (Pa) [1 Pa = 1 Newton/m2 = 1 kg·m/s2/m2] and Ṽi is

the specific molar volume of species i (m3/mol of i).
Let’s look at the units of the flow-work term, which is

F i ( P ( Ṽi
where Fi is in mol/s, P is Pa (1 Pa = 1 Newton/m2), and Ṽi is m3/mol.
Section 11.2 The Energy Balance 497

3
mol Newton m
F i ( P ( Ṽi [ = ] --------- ( ------------------- ( --------- " ( Newton ( m ) ( 1--- " Joules ' s " Watts
s m
2 mol s

We see that the units for flow work are consistent with the other terms in
Equation (11-3), i.e., J/s.
Convention In most instances, the flow-work term is combined with those terms in
Heat Added the energy balance that represent the energy exchange by mass flow across the
Q̇ " +10J/s system boundaries. Substituting Equation (11-4) into (11-3) and grouping
Heat Removed terms, we have
Q̇ " –10J/s n n
dÊ sys
Work Done by ------------ " Q̇ ! Ẇs & ! F i( E i & PṼi ) ! ! F i(Ei & PṼi) (11-5)
System dt
i"1 i"1
W˙ S " +10J/s in out

Work Done on The energy Ei is the sum of the internal energy (Ui ), the kinetic energy
System
( u2i ' 2 ) , the potential energy (gzi ), and any other energies, such as electric or
W˙ S " –10J/s
magnetic energy or light

u2
E i " U i & -----i & gzi & other (11-6)
2
In almost all chemical reactor situations, the kinetic, potential, and “other”
energy terms are negligible in comparison with the enthalpy, heat transfer, and
work terms, and hence will be omitted; that is
Ei " U i (11-7)
We recall that the enthalpy, Hi (J/mol), is defined in terms of the internal
energy Ui (J/mol), and the product PṼi (1 Pa(m3 /mol " 1 J/mol):

Enthalpy H i " U i & PṼi (11-8)

Typical units of Hi are
J Btu cal
( H i ) " ------------ or ------------------- or ------------
mol i lb-mol i mol i
Enthalpy carried into (or out of) the system can be expressed as the sum
of the internal energy carried into (or out of) the system by mass flow plus the
flow work:

F i H i " F i ( U i & PṼi )

Combining Equations (11-5), (11-7), and (11-8), we can now write the energy
balance in the form
n n
dÊ sys
------------ " Q̇ ! Ẇs & ! F i H i ! ! F iH i
dt
i"1 in i"1 out

The energy of the system at any instant in time, Ê sys , is the sum of the
products of the number of moles of each species in the system multiplied by
498 Nonisothermal Reactor Design Chapter 11

their respective energies. This term will be discussed in more detail when
unsteady-state reactor operation is considered in Chapter 13.
We shall let the subscript “0” represent the inlet conditions. Unsub-
scripted variables represent the conditions at the outlet of the chosen system
Energy Balance volume.
in n n
dÊ
Q̇ ! Ẇs & ! F i0 H i0 ! ! F iH i " -----------
sys
- (11-9)
. . i"1 i"1
dt
Fi0Hi0, Q FiHi,Ws

In Section 11.1, we discussed that in order to solve reaction engineering

out problems with heat effects, we needed to relate temperature, conversion, and
rate of reaction. The energy balance as given in Equation (11-9) is the most
convenient starting point as we proceed to develop this relationship.

11.2.3 Overview of Energy Balances

What is the plan? In the following pages we manipulate Equation (11-9) in

order to apply it to each of the reactor types we have been discussing: batch,
PFR, PBR, and CSTR. The end result of the application of the energy balance
to each type of reactor is shown in Table 11-1. These equations can be used in
Step 5 of the algorithm discussed in Example E11-1. The equations in Table
11-1 relate temperature to conversion and to molar flow rates, and to the sys-
tem parameters, such as the overall heat-transfer coefficient and area, Ua, with
the corresponding ambient temperature, Ta, and the heat of reaction, ∆HRx.
TABLE 11-1 ENERGY BALANCES OF COMMON REACTORS

1. Adiabatic ( Q̇ " 0 ) CSTR, PFR, Batch, or PBR. The relationship between conver-
sion calculated from the energy balance, XEB, and temperature for Ẇ s " 0 ,
constant C P , and #C P " 0 , is
i

Conversion in terms of temperature

)*i C P ( T ! T 0 )
i
X EB " -------------------------------------
- (T11-1.A)
!#H%Rx

End results of Temperature in terms of conversion calculated from the energy balance
manipulating the
energy balance ( !#H%Rx )X EB
T " T 0 & ---------------------------------- (T11-1.B)
(Sections 11.2.4, )*i C P
i
12.1, and 12.3)
For an exothermic reaction (–∆HRx) > 0

2. CSTR with heat exchanger, UA (Ta – T ), and large coolant flow rate

 UA 
F -------- ( T ! T a ) & ) *i C P ( T ! T 0 )
.
mc  A0  i

T
X EB " --------------------------------------------------------------------------------- (T11-1.C)
Ta !#H%Rx