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1.0 Batch reactor 02

1.1 The unsteady-state energy balance 02
2.1 Energy balance on unsteady state batch reactor 08

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1.0 BATCH REACTOR: A batch reactor is the simplest type of reactor
vessels used for chemical or industrial processes. A typical batch reactor
consists of a tank where chemical reactions occur. These tanks also have an
agitator and an internal heating or cooling system. Tank sizes range from
one liter to 15,000 liters.
Batch reactors are often used in the process industry. Batch reactors also
have many laboratory applications, such as small-scale production and
inducing fermentation for beverage products. They also have many uses in
medical production. Batch reactors are generally considered expensive to
run, as well as variable product reliability. They are also used for
experiments of reaction kinetics, volatiles and thermodynamics. Batch
reactors are also highly used in wastewater treatment. They are effective in
reducing BOD (biological oxygen demand) of influent untreated water.
A batch reactor has neither inflow nor outflow of reactants or products while
the reaction is being carried out.
This is an unsteady-state operation where composition changes with time;
however at any instant the composition throughout the reactor is uniform.
The reactants are initially charged into a container are well mixed and are
left to react for a certain period. The resultant mixture is then discharged.

Batch reactor
1.1 THE UNSTEADY-STATE ENERGY BALANCE
We start by deriving the user-friendly form of the energy balance that can be
easily used in making reactor calculations.
First Law of Thermodynamics

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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, dE, is equal to the heat flow to the system, SQ, minus the work
done by the system on the surroundings, SW. For a closed system, the energy
balance is
dEˆ=δQ−δW (1-1)
The δ’s signify that SQ and SW 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
balance on the open system shown in Figure.For an open system in which
some

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

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

(1-2)

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 now has n species, each
entering 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

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 (1-3)

We will now discuss each of the terms in Equation (1-3).

It is customary to separate the work term, W˙, into flow work and other
work, W˙s. The term W˙s, 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

(1-4)

where P is the pressure (Pa) [1 Pa = 1 Newton/m2 = 1 kg·m/s2/m2] and V˜i 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
Fi⋅ P⋅ V˜i
where F¡ is in mol/s, P is in Pa (1 Pa = 1 Newton/m2), and V˜i is in
(m3/mol). Multiplying the units of each term in (FiPV˜i) through, we obtain
the units of flow work, i.e.,
Fi⋅ P⋅ V˜i[=]mols⋅ Newtonm2⋅ m3mol=(Newton⋅ m)⋅ 1s=Joules/s=Watts
We see that the units for flow work are consistent with the other terms
in Equation (1-3), i.e./s.
In most instances, the flow-work term is combined with those terms in the
energy balance that represent the energy exchange by mass flow across the
system boundaries. Substituting Equation (1-4) into (1-3) and grouping
terms, we have

(1-5)

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The energy F¡ is the sum of the internal energy (Ui), the kinetic energy
(u2i/2), the potential energy (gzi), and any other energies, such as electric or
magnetic energy or light.
Ei= Ui+u2i/2+gzi+other (1-6)
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, in which case
Ei=Ui (1-7)
We recall that the enthalpy, Hi (J/mol), is defined in terms of the internal
energy Ui (J/mol), and the product PVi (1 Pa·m3/mol = 1 J/mol):
Hi=Ui+PV˜i (1-8)

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:
Fi Hi=Fi(Ui+PV˜i)
Combining Equations (1-5), (1-7), and (1-8), we can now write the energy
balance in the form

The energy of the system at any instant in time, Êsys, is the sum of the
products of the number of moles of each species in the system multiplied by
their respective energies. The derivative of the Esys term wrt time will be
discussed in more detail when unsteady-state reactor operation is considered
We shall let the subscript “0” represent the inlet conditions. The conditions
at the outlet of the chosen system volume will be represented by the
unsubscripted variables.

(1-9)

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Energy balance

2.0 We shall first concentrate on evaluating the change in the total energy of
the system wrt time, (dEsys/dt). The total energy of the system is the sum of
the products of specific energies, (dEˆsys/dt).of the various species in the
system volume and the number of moles, Ni (mol i), of that species

(2-1)

In evaluating Eˆsys, as before we neglect changes in the potential and kinetic

energies and substitute for the internal energy Ui in terms of the enthalpy Hi

(2.2)

We note the last term on the right-hand side of Equation (2-2) is just the total
pressure times the total volume, i.e., PV, and this term is virtually always
smaller than the other terms in Equation (2-2), and thus will be neglected†
we shall write all summations as
Σ=Σmi=1
unless otherwise stated.
When no spatial variations are present in the system volume, and time
variations in the product of the total pressure and volume (PV) are neglected,
the energy balance, after substitution of Equation (2-2) into (1-9), gives

(2-3)

(i)

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and differentiating eq (i) with respect to time, we obtain

(2-4)

Then, substituting Equation (2-4) into (2-3) gives

(2-5)

The mole balance on species is

(2-6)

Using Equation (2-6) to substitute for dNi/dt, Equation (2-5) becomes

(2-7)

This form of the energy balance should be used when there is a phase change.

(2-8)
Substituting for Hi and Hi0 for the case of no phase change gives us

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 (2-9)
Energy balance on a cstr or semi batch reactor
For liquid-phase reactions where ΔCP is usually small and can be neglected, the
following approximation is often made

Cps = heat capacity of solution

where CPc is the heat capacity of the solution. The units of the batch term (NAo CPs)
are (cal/K) or (J/K) or (Btu/°R), and for the flow term
Σ FiC pi =F A0C ps
the units are (J/s · K) or (cal /s · K) or (Btu/h · °R) .With this approximation and
assuming that every species enters the reactor at the same temperature T0, we have

(2-10)

2.1 ENERGY BALANCE ON UNSTEADY STATE BATCH

REACTOR.

The energy balance on batch reactors (BR) is found by setting the inlet and
outlet flows to zero, i.e., Fi0= Fi = 0.

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The energy balance on batch reactors (BR) is found by setting the inlet and
outlet flows to zero, i.e., Fi0= Fi = 0, in Equation (2-9)
(2-11)

Next we use the heat-exchanger energy balance to obtain Q., and realize
that the heat “added” to the batch reactor, Q., is just minus the heat
“removed” from the batch reactor, Q.rbQ.=−Q.rb neglecting shaft work we
get

(2-12)

If the heat capacities were given in terms of mass (i.e., Cp =

J/g. K), then both FA0 and NA0 would have to be converted to mass
For batch mA0Cpsm = NA0CPS
(g)(J/g⋅K) = (mol) J/(mol⋅K)=J/K

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and for flow m.A0CPsm=FA0CPS
(g/s)(J/g⋅K)=(mol/s)(J/mol⋅K) = J/K⋅s
However, we note that the units of the product of mass flow rate and
mass heat capacities would still be the same as the product of molar
flow and molar heat capacities (e.g., cal/s · K), respectively.
where the terms for heat generated, Q.gb, and heat removed, Q.rb, for a
batch system are
Q.gb=(−ΔHRx)(−rAV) (2-13)

(2-14)

Equation (2-12)is the preferred form of the energy balance when the
number of moles, Ni , is used in the mole balance, rather than the
conversion, X. The number of moles of species i at any X is

Consequently, in terms of conversion, the user-friendly form of the

energy balance becomes

(2-15)

Equation (2-12) must be coupled with the mole balance

Batch reactor mole balance .

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