7

THE
FUNDAMENTAL
MASS,
ENERGY,
ANO
MOMENTUM
BALANCE
EQUATIONS

7.1 lntroduction
The number of types of reactors is very large in the chernical industry. Even for
the same operation, such as nitration of toluene, dilferent types are used: the
batch reactor, the continuous stirred tank, and a cascade of stirred tanks. Flow
reactors of the tubular type are used for such widely different processes as the
nitration of glycerine, the sulfonation of aromatics, or gas phase reactions like
thermal cracking or the nitration of paraffins. Flow reactors with fixed bed of
catalyst particles are used in the ammonia or methanol syntheses and in the
oxidation of xylene into phthalic anhydride. A series of such fixed bed reactors
is used in S03 synthesis or in hydrocarbon reforming. Reactors with fluidized or
moving beds are used for cracking hydrocarbons, for oxidizing naphthalene or for
oxychlorinating ethylene.
The modeling of chemical reactors, as it is conceived in the following chapters,
is not based on the externa! form of the apparatus nor on the reaction talcing place
in it, nor even on the nature of the medium-homogeneous or not. Focusing on
the phenomena taking place in the reactor reduces the apparent diversity into a
small number of models or basic reactor types. Tbe phenomena occurring in a
reactor may be broken down to reaction, transfer of mass, heat, and momentum.
The modeling and design of reactors is therefore based on the equations describing
these phenomena: the reaction rate equation, the continuity, energy, and mo-
mentum equations. Tbe form and complexity of these equations will now be
discussed, for introductory and orienting purposes, in general terms. Tbe equations
themselves are derived in later sections of this chapter.

347
7.1.a The Continuity Equations
The first step toward the answer to what the conversion of A in the reactor will be
consists of applying the law of conservation of mass on a volume-element of the
reactor, fixed in space:

Amount of
introuc_ed
Al -
[Amount of Al - [ Arnount
leain per
of Al
convrt
[ Amount of Al
= accum_ulted
[ per unrt time umt time per urnt time per umt time
I II III IV
(7.1.a-1)

In mathematical terms Eq. 7.1.a- l is nothing but the so-called continuity equation
for A. lf A reacts in more than one phase then such an equation is needed for each
of these phases.
The mechanisms by which A can enter or leave the volurne element considered
are: flow and-for those cases where the concentration is not uniform in the reactor
-molecular diffusion, in practice generally of minor importance, however. The
motion of a fluid, even through empty pipes, is seldom ordered and is difficult to
describe. E ven if the true detailed flow pattern were known the continuity equation
would be so complicated that its integration would be impossible. The crossing of
different streamlines, and mixing of fluid elements with different characteristics
that result from this crossing, are difficult points in the design of chemical reactors.
It is therefore natural to consider, for a first approach, two extreme cases: a first
where there is no mixing ofthe streamlines, a second where the mixing is complete.
These two extremes may be visualized with sufficient approximation by the tubular
reactor with plug flow and continuous flow stirred tank with complete mixing.
In a plug flow reactor ali fluid elements rnove along parallel streamlines with
equal velocity. The plug flow is the only mechanism for mass transport and there
is no mixing between fluid elements. The reaction therefore only leads to a con-
centration gradient in the axial flow direction. For steady-state conditions, for
which the term IV is zero the continuity equation is a first-order, ordinary dif-
ferential equation with the axial coordinate as variable. For non-steady-state
conditions the continuity equation is a partial differential equation with axial
coordinate and time as variables. Narrow and long tubular reactors closely
satisfy the conditions for plug flow when ihe viscosity of the fluid is-low,
Reactors with complete mixing may be subdivided into batch and continuous
types. In a batch type reactor with complete mixing the composition is uniform
throughout the reactor. Consequently, the continuity equation may be written
for the entire contents, not only over a volume element. The composition varies

348
THE FUNDAMENTAL MASS CHEMICAL REACTOR DESIGN349
with time, however, so that a first-order ordinary differential equation is obtained,
with time as variable. The form of this equation is analogous with that for the

348
THE FUNDAMENTAL MASS CHEMICAL REACTOR DESIGN349
plug How case. In the continuous How type, an entering Huid element is instan-
taneously mixed with the contents of the reactor so that it loses its identity.
This type also operates at a uniform concentration leve!. In the steady state, the
continuity equations are algebraic equations.
Both types of continuous reactors that were considered here are idealized cases.
They are important cases, however, since they are easy to calculate and they give
the extreme values of the conversions between which those realized in a real
reactor will occur-provided there is no bypassing in this reactor. The design of a
real reactor, with its intermediate level of mixing, requires information about this
mixing. The mixing manifests itself at the outlet of the reactor by a spread or
distribution in residence-time (the length of time spent in the reactor) between
fluid elements. Such a distribution is relatively easy to measure. The resulting
information may then be used as such in the design or used with a model for the
real behavior of the reactor. The design of nonideal cases along both lines of
approach is discussed in Chapter 12.

7.1.b The Energy Equation

In an energy balance overa vol u me element of a chemical reactor, kinetic, poten tia!,
and work terms may usually be neglected relative to the heat of reaction and other

Amount of heatl
Amount of heatl . [ Heat effet of l[ ariation of l
heat transfer terms so that the balance reduces to: V
added - out - the reaction = heat content
[ [
per unit time per unit time per unit time per unit time
I II III IV
(7. l.b-I)

The mathematical expression for Eq. 7 .1.b-1 is generally called the energy equation,
and its integrated form the heat balance. The form of these equations results from
considerations closely related to those for the different types of continuity equa-
tions. When the mixing is so intense that the concentration is uniform over the
reactor, it may be accepted that the temperature is also uniform. When plug
flow is postulated, it is natural to accept that heat is also only transferred by that
mechanism. When molecular diffusion is neglected, the same may be done for
heat conduction. When the concentration in a section perpendicular to flow is
considered to be uniform then it is natural to also consider the temperature to be
uniform in this section. lt follows that when heat is exchanged with the surround-

348
THE FUNDAMENTAL MASS CHEMICAL REACTOR DESIGN 349
ings, the temperature gradient has to be situated entirely in a thin "film" along the
wall. This also implies that the resistance to heat transfer in the central core is zero
in a direction perpendicular to the flow. This condition is not always fulfilled,
especially for fixed bed catalytic reactors-besides heat transfer by convective

348
THE FUNDAMENTAL MASS CHEMICAL REACTOR DESIGN 349
flow, other mechanisms often have to be introduced in such cases. Even here
it is necessary, in order to keep the mathematics tractable, to use simplified models,
to be discussed in later chapters.

7 .1.c The Momentum Equation

This balance is obtained by application of Newton's second law on a moving fluid

elernent. In chemical reactors only pressure drops and friction forces have to be
considered in most cases. A nurnber of pressure drop equations are discussed in
the chapters on tubular plug flow and on fixed bed catalytic reactors.

7.2 The Fundamental Equations ------------

7.2.a The Continuity Equations

The derivation of differential mass balances or continuity equations for the com-
ponents of an element of fluid flowing in a reactor is considered in detail in texts
on transport processes (e.g., Bird et al. [1]). These authors showed that a fairly
general form ofthe continuity equation for a chemical speciesj reacting in a flowing
fluid with varying density, temperature, and composition is:

ac. +V (C.u) +V J.= R.

- (7.2.a-1)
ot 1 1 1

If species j occurs in more than one phase such a continuity equation has to be
written for each phase. These equations are linked by the boundary conditions and
generally also by a term expressing the transfer of j between the phases. Such a
terrn is not included by Eq. 7.2.a-l since the following discussion is centered on the
various forros the continuity equations can take in single phase or homogeneous"
or, by extensin, in "pseudo-homogeneous" reactors as a consequence of the
flow pattem. Specific modeling aspects resulting from the presence of more than
one phase, solid, or fluid is illustrated in detail in Chapter 11 on fixed bed reactors,
Chapter 13 on fluidized bed reactors, and Chapter 14 on multiphase reactors.
The terrns and symbols used in this equation have the following meaning.
C is the molar concentration of species j (kmol/m3 fluid), so that oCiot is the
non-steady-state term expressing accumulation or depletion. V is the "nabla" or

350
THE FUNDAMENTAL MASS
---------------- CHEMICAL REACTOR OESIGN 351
"del" operator. In a rectangular coordinate system, x, y, z with unit vectors Dx,
Dy, anda, the gradient of a scalar functionf is represented by Vf and the divergence

350
THE FUNDAMENTAL MASS
---------------- CHEMICAL REACTOR OESIGN 351
of a vector function v by V v. More explicitly:
of cf a
Vf = - li,
0X
+ -::;--
Oy
liy + - li=
Oz

iJv, Dti, Jv=

V V=- - i)z
OX + oy +-
u is the three-dimensional mass average velocity vector, defined by
N M.C.
u=
i= 1
--uj
Pr
(m/s)

where p 1 is the density of the mixture and u1 represents the velocity of molecules
of speciesj. The term V (Cju) thus accounts for the transport of mass by convec-
tive flow.
Ji is the molar flux vector for speciesj with respect to the mass average velocity
(kmol/m2s). When the flow is laminar or perfectly ordered the term V Jj results
from molecular diffusion only. lt can be written more explicitly as an extensin,
already encountered in Chapter 3, of Fick's law for diffusion in binary systerns, as

s, = -p1 Di.,v(;) (7.2.a-2)

where DJ., is the effective binary diffusivity for the diffusion of j in the multi-
component mixture. Of course, appropriate multicomponent diffusion Jaws
could also be used-for ideal gases the Stefan-Maxwell equation, as was done in
Sec. 2.c of Chapter 3. In Eq. 7.2.a-2 the driving force has been taken as moles of j
per total mass of fluid, for the sake of generality [J]. Toe term V Jj can also
account for the flux resulting from deviations of perfectly ordered flow, as en-
countered with turbulent flow or with flow through a bed of solid particles for
example, but this will be discussed further below.
R i is the total rate of change of the amount of j because of reaction -as defined
in Chapter 1, that is, r,.jr for a single reaction and 1 rx;jr; for multiple reactions.
The rxlJ are negative for reactants and positive for reaction products. The units of
R j depend on the nature of the reaction. If the reaction is homogeneous the units
could be kmol/m3s but for a reaction catalyzed by a solid preference would be
given to kmolfkg cat s, multiplied by the catalyst bulk density in the reactor.
From the definitions given it is clear that MjJj = L L
MJC,{u1 - u)= O,
while L M1Rj = O, dueto the conservation of mass in a reacting system. So, if
each term ofEq. 7.2.a-l is multiplied by the molecular weight M, and the equation
is then summed over the total number of species N, accounting for the re!ation
p1 = L MC1, the total continuity equation is obtained:

350
THE FUNDAMENTAL MASS
---------------- CHEMICAL REACTOR OESIGN 351
 i Jp
a t + V (p1u) = O (7.2.a-3)

350
THE FUNDAMENTAL MASS
---------------- 351
CHEMICAL REACTOR OESIGN
Thus, note that the usual continuity equation of fluid mechanics is also true for a
reacting mixture. Equation 7.2.a-3 can be used to rewrite 7.2.a-1 in a form that
is sometimes more convenient for reactor calculations. The first two terms can be
rearranged as follows:

where the last zero term results from the total continuity Eq. 7.2.a-3. This re-
sult suggests that (C/p1), molesj per unit mass of mixture, is a convenient and
natural variable. This is indeed the case, since (C}p1) is simply related to the con-
version (or extent), a variable frequently used in reactor design:
C. (CfP1) N.
---1 = (e' ) (C)p1)0 = N1 (C)p1)0
Pt iPJo iO

= (1 - x)(CjfP1)0 (7.2.a-4)
where N is the total number of moles of j present in the reactor and the index
zero refers to reactor-inlet values.
Combining these latter results with Eq. 7.2.a-l and Eq. 7.2.a-2 Ieads toan equa-
tion in terms of conversions:

P1( ;:+u Vxi) - V (p1Di,. Vxi) = - ()/i (7.2.a-5)

Equations 7.2.a-1 and 7.2.a-5 are in fact extensions of the continuity equations used
in previous chapters, where the flow terms were normally not present. These
somewhat detailed derivations have been used to carefully illustrate the develop-
ment of the equations of transport processes into forms needed to describe chemical
reactors. lt is seldom that the full equations have to be utilized, and normally
only the most important terms will be retained in practica! situations. However
Eqs. 7.2.a-l or 5 are useful to have available as a fundamental basis.
Equation 7.2.a-5 implicitly assumes perfectly ordered flow in that V (p1D,,. Vx}
is specific for molecular diffusion. Deviations from perfectly ordered fow, as
encountered with turbulent flow, lead to a flux that is also expressed as if it arose
from a diffusion-like phenornenon, in order to avoid too complex mathematical
equations. The proportionality factor between the flux and the concentration
gradient is then called the turbulent or "eddy" diffusivity. Since this transport
mechanism is considered to have the same driving force as molecular diffusion,
the two mechanisms are summed and the resulting proportionality factor is
called "effective" diffusivity, De. In highly turbulent flow the contribution of

352 CHEMICAL REACTOR DESIGN

molecular diffusion is usually negligible, so that D, is then practically identical
for ali the species of the mixture. Through its turbulent contribution, the effective
diffusion is not isotropic, howevcr. For more details refer to Hinzc [2].
Equation 7.2.a-5 now bccomcs:

P (aax/ + u. v,) = oax (PDe.x aox;) + oay (pD,.1 ax)a;

+ :Z (pDe,z ;)- (: )/j (7.2.a-6)

Whcn thc reactor contains a solid catalyst the flow pattern is strongly determined
by the presence of the solid. It would be impossible to rigorously express the
influence of the packing but again the flux of j resulting from the mixing effect
caused by its presence is expressed in the form of Fick 's law. Consequently, the form
of Eq. 7.2.a-6 is not altered, but the effective diffusivity now also contains the effect
of the packing. This topic is dealt with extensively in Chapter 11 on fixed bed
catalytic reactors. For further explanation of the effective transport coefficients
see Himmelblau and Bischoff [3] and Slattery [4].

7.2.b Simplified Forms of the "General" Continuity Equation

As already mentioned, the form of the fundamental continuity cquations is

usually too complex to be conveniently solved for practica! application to reactor
design. If one or more terms are dropped from Eq. 7.2.a-6 and or integral averages
over the spatial directions are considered, the continuity equation for each
component reduces to that of an ideal, basic reactor type, as outlined in the intro-
duction. In these cases, it is often easier to apply Eq. 7.1.a-l directly to a volume
element of the reactor. This will be done in the next chapters, dealing with basic
or specific reactor types. In the present chapter, however, it will be shown how the
simplified equations can be obtained from the fundamental ones.
lt is very common in reactors to have flow predominantly in one direction,
say z (e.g., think of tubular reactors). The major gradients then occur in that
direction, under isothermal conditions at least. For many cases then, the cross-
sectional average values of concentration (or conversion) and temperature might
be used in the equations instead of radial point values. The former are obtained
from:

354 ----------------
THE FUNDAMENTAL MASS CHEMICAL REACTOR DESIGN 353
where ( represents any variable, and Q is the cross section inside the rigid boundary
and dQ = dx dy. We can see that virtually ali the terms contain products of

354 ----------------
THE FUNDAMENTAL MASS CHEMICAL REACTOR DESIGN 354
dependent variables, and the first approximation that must be made is that the
average of the product is el ose to the product of the avera ges; for example,

/
\PU:
oxj)
a; :,e
< PU: >
J(xj>

In this case, the approximation would clearly be best for highly turbulent flow,
for which the velocity profiles are relatively flat. The discrepancies actually enter
into the effective transport coeffcients, which have to be empirically measured in
any event. Another approximation concerns the reaction rate term:
(R;{Ci, T)) ::::c Ri{(Ci), (T))
Thus, Eq. 7.2.a-6 becomes after integration over the cross section:

ot + < PU > J(xi>

< P > o(xj) oz =
2
< P De,z > o:<xj>
1
_ (Pi)
C
R
1 (7.2.b-l)
O
(!) (2) (3) (4)
where the velocity in the flow direction is represented by u. In the presence of pack-
ing a distinction would have to be made between the true local fluid velocity,
called the interstitial velocity (m/s) and the velocity considered over the whole
cross section, as if there were no solid, called the superficial velocity (m3 fluid/m2
cross section s). A so called "ene-dimensional rnodel" is now obtained. If the
convective transport is completely dominant over any diffusive transport, in
particular that in the flow direction-that is, the fluid moves like a "plug"-the
term (3) may be neglected, Assuming steady state conditions, the term (1) also
drops out, so that the simplified Eq. 7.2.b-l becomes (leaving out the brackets
for simplicity):

PU dxi = - (Pi) R
dz C 0

while the continuity Eq. 7.2.a-3 reduces to:

This last equation is simply integrated to give:

(p1u) = (p1u)0 = constant = G(kg/m2 s)
where Gis usually termed the "mass flow velocity." This result is then combined
with the continuity equation for species j, giving
dz
dx-
Uo- =

354 ----------------
THE FUNDAMENTAL MASS CHEMICAL REACTOR DESIGN 355
 1
- R1x-) - j\
jO e
(7.2.b-2) J

354 ----------------
THE FUNDAMENTAL MASS 356
CHEMICAL REACTOR DESIGN
One modification is normally made before performing the final integration step:

where F0 is the volumetric flow rate of the feed (m3 /s) and dV is a dilferential
element of reactor volume. lntegration now gives,
V
F0 = -Cio
J R{;j)
dx, (7.2.b-3)

_ -J
More often this equation is written in the form

dxj (7.2.b-4)
Fjo - R/xi)

whereby F ;0 = F0 Ci0 is the molar feed rate of speciesj (kmol/s). The last equation
is used to describe the plug fiow reactor.
Other simplified forms result when the entire reactor may be considered to be
uniform-operating under conditions of complete mixing, the idealized picture
of a well-mixed vessel. Here, one averages over ali the spatial directions so that
Eq. 7.2.b-l can be further integrated over z:

=} JfJ xjdxdydz

(For simplicity again, the overlines referring to mean vales, will from now be
left out.) Moreover, because of the assumption of complete uniformity, no effective
transport terms need to be considered. Note that the final coordinate direction
here refers to the fluid, which could be expanding, in contras! to the rigid boundary
assumed for x and y. A more general and more rigorous derivation using the
transport theorems of vector/tensor analysis has been given by Bird [5]. In the
batch case, when no fluid is entering or leaving the reactor, except at the time of
loading or unloading, Eq. 7.2.b-l, with the terms (2) and (3) zero, can be integrated
to yield:

(7.2.b-5)
or,
d
-(N-J0x) = -R-V
dt J J

354 ----------------
THE FUNDAMENTAL MASS CHEMICAL REACTOR DESIGN 357
since V(p 1/p 10)C0 = V0 C0 = N0, the total numbcr of moles ofj initially present.
N is related to N0 by N = N0(1 - x), so that finally one obtains:
dN
-' = R. V
dt J
(7.2.b-6)

or, in integral forro:

(J = f dN
RV
(7.2.b-7)

This is the mass balance equation for the batch reactor. The symbol t for "dock
time" is replaced here by the more usual symbol (J for "batch residence time."
For the continuous, completely mixed reactor, it is useful to start from the
reduced continuity equation in terms of concentrations, analogous to Eq. 7.2.b-l
(but with no diffusion term):
iJ(C) + o(uC) = R.
(7.2.b-8)
oc oz J

which yields, after integration over z and multiplication by Q:

d
-(VC.)
dt '
+ f d<F)
--dz
dz
= R V
' (7.2.b-9)

since

(uC.) = (F1) = (F'C)

J Q Q

where F' is the volumetric flow rate, m3 /s. If F. 0 and F., represen t. respectively,
the inlet and outlet flow rates of species j the following equation is obtained:
d N
--; = F .o - F ., + R (7.2.b-10)
V
1 1 1

Again, Bird [5] presents a more rigorous derivation, with the identical result.
Under steady-state conditions Eq. 7.2.b-10 reduces to an algebraic equation:
F., - F10 = R V (7.2.b-11)
which is the mass balance for the continuous fiow stirred tank reactor (CSTR).
lf Eq, 7.2.b-10 is multiplied by the molecular weight M, and summed on i.
a total mass balance is obtained:

THE FUNDAMENTAL MASS

356 358
---------------- CHEMICAL REACTOR DESIGN
 (7.2.b-12a)
dmt, - F' P,o - F' Pf.
o e

(7.2.b-12b)

THE FUNDAMENTAL MASS

356 359
---------------- CHEMICAL REACTOR DESIGN
where m, = L M1N1 is the total rnass, and mis the mass flow rate (kg/s). Equation
7.2.b-12 could also be obtained by integrating Eq. 7.2.a-3 over the volume. For
liquids, the density is approximately constant, and if the volume is fixed, Eq.
7.2.b-12 shows that the inlet and exit flows must be the same.

7.2.c The Energy Equation

Again reference is made to Bird et al. [l] for the rigorous derivation, in various co-
ordinate systems, of the fundamental energy equation. The following form, with
respect to a rectangular coordinate system, contains the phenomena that are of
importance in reactors:

I MjCjcpj( +u.
)
vT) = I (-AH;)r +V. (,l.VT) - I J;VH;
' )
+ Q,ad
(!) (2) (3) (4) (5) (6)
(7.2.c-l)
where e Pi is the specific heat of species j (kcal/kgC or kJfkg K), }. is the thermal
conductivity of the mixture (kcal/m.hrC or kJ/m.s. K) and the H1 are partial
molar enthalpies (kcalfkmol or kJfkmol). The respective terms arise from:
(l)change ofheat content with time, (2)convective flow, (3) heat effect ofthe chemi-
cal reactions, (4) heat transport by conduction, (5) energy flux by molecular dif-
fusion, and (6) radiation heat flux.
Other energy terms encountered with particular flow conditions are work of
expansion or viscous dissipation terms, primarily importan! in high speed flow;
externa] field effects, mechanical or electrical, can also occur. Since they usually
are of much Iess importance they will not be considered here. Heat radiation in the
reactor is often neglected, except in the case of fixed bed catalytic reactors operating
at high ternperatures, but then it is generally lumped with the heat conduction
and a few more heat transport mechanisms into an "effective" heat conduction
having the form of term (4) in Eq. 7.2.c-1. When this is done in Eq. 7.2.c-l and the
diffusion term (5) is neglected the result is:

; MJCJcpJe +u VT) = (-AH;)r, + :x (J.,.x :)

+:y(;.,,;)+ :z (J.,.,:) (7.2.c-2)

where J., is an effective thermal conductivity. Again, when there is more than one
phase, more than one energy equation has to be written and a transfer term has
to be introduced. For the same reasons as mentioned in Sec. (7.2.a), this has not

THE FUNDAMENTAL MASS

356 360
---------------- CHEMICAL REACTOR DESIGN
been done here and will be delayed to the specific cases discussed in the following
chapters.

THE FUNDAMENTAL MASS

356 361
---------------- CHEMICAL REACTOR DESIGN
7 .2.d Simplified Forms of the "General" Energy Equation
The "general" energy equation can be simplified in the same way as the continuity
equation. since the approximations introduced there are assumed to be equally
applicable here. But, whereas mass is generally not diffusing through the wall,
heat frequently is. In deriving the one-dimensional model by averaging over the
cross section, a boundary condition for heat transfer at the reactor wall has to be
introduced for this reason. This boundary condition is commonly written as:

(7.2.d-l)
Here n represents the direction normal to the wall, '.X,. is a convective heat transfer
coefcient, T.. is the temperature of the wall, and TR is the fluid temperature in the
immediate vicinity of the wall. The right-hand side of Eq. 7.2.d-l would be zero for
an adiabatic reactor. Equation 7.2.c-2 then becomes, when averaged over cylindri-
cal geometry, with diameter d,

(7.2.d-2)

An important point is that the z component of the condition term retains its
identity, in terms of averaged variables, but the x and y components are integrated
out with the wall boundary condition, Eq. 7.2.d-1, which is now written:

where T, is the temperature of the surroundings and U is an overall heat transfer

coefficient. The latter approximation actually locates the heat transfer with the
wall in a thin film. For the tubular reactor considered here, the heat conduction
in the z-direction is usually much smaller than the heat transported by convection,
and also it drops out for the complete mixing case.
Thus, the resulting equation is:

358
THE FUNDAMENTAL MASS
---------------- CHEMICAL REACTOR OESIGN 362
358
THE FUNDAMENTAL MASS
---------------- 363
CHEMICAL REACTOR OESIGN
For steady-state conditions Eq. 7.2.d-3 becomes, after multiplying by n = rrd,2/4
(and omitting the brackets):
dT
I mjcpj dz - n I (-t.H)r - rrd,U(T,. - T) = o (7.2.d-4)

J '

This is the energy equation for a single-phase tubular reactor with plug flow.
Note that Eq. 7.2.d-4 is coupled with the continuity equation, mainly by the
reaction terrn, but also through the heat capacity term on the left-hand side. The
latter is sometimes written in terms of a specific heat that is averaged with respect
to temperature and composition, that is, Li
rjcpj =
mcP.
A rigorous macroscopic energy balance is found by integrating over the entire
reactor volume:

mjcpJ dTt = FJ.o(HJ.o - HJ,e) + V (-t.H)r +

J J '
f 1t d, U(T,. - T) dz

(7.2.d-5)
which can also be found by a careful integration of Eq. 7.2.d-3 over the reactor
(see Bird [5]). Representing the interna! heat exchange surface of the reactor by
Ak, Eq. 7.2.d-5 reduces to:

(7.2.d-6)
for the batch reactor, or with FJ. = Fj.o + R V

(7.2.d-7)

for the continuous flow stirred tank reactor.

The following chapters deal in detail with ideal reactor types like the batch
reactor (Chapter 8), the tubular reactor with plug flow (Chapter 9), and the
continuous flow reactor with complete rnixing (Chapter 10). Deviations from
plug flow will be encountered in Chapter 11 on fixed bed catalytic reactors and
severa) degrees of sophistication will be considered there. The problem of modeling
nonideal and multiphase reactors will be developed in Chapter 12, while important
specific cases of fluidized bed reactors and of gas-liquid-solid reactors will be
discussed in Chapters 13 and 14, respectively. Each ofthese chapters starts from the
basic equations developed here or from combinations of these; correlations are
given for the mass and heat transfer parameters for each specific case; the opera-
tional characteristics of the reactors are derived from the solution of the basic
equations; and the performance of reactors in several industrial processes will be
simulated and investigated.

358
THE FUNDAMENTAL MASS
---------------- CHEMICAL REACTOR OESIGN 364
 Problems
7.1 Write Eq. 7.2.a-6 in terms of ;. the extent of the ith reaction per unit mass of the reaction
mixture, defined by

;= -
- -
N;o
})
I o
(krnol/kg)

7.2 Derive the steady-state continuity and energy equations and appropriate boundary
conditions for the tubular reactor with turbulent flow, corresponding to the various
situations represented in the following diagram (from Himmelblau and Bischoff [3]).
Axial and
radial
dispersion
coelficients
vary with
radius

Velocitv+ Temp. Out

rofile profile

) > ) }-
Only axial Concentration Ternp.
disperslon profile profile
considered flat flat

No disper5ion
in axial
direction

Ali interna! variations ignored

360
THE FUNDAMENTAL MASS 361
CHEMICAL REACTOR DESIGN
 The continuity equation for the first case is given by (in cylindrical coordinates):

se,
o:
c, + -r1 [e--or
u(r) = D,-, ,(rl--::--f
i}:
rD,.,(r)
ac,] + R,
cr
with boundary conditions

oC,{O, r)
u(r)C;o = u(r)C,{O, r) - D,.,(r) a;-
ec,
::=L oz' = O, ali r

iJC
r=O =O ali z
' '
ce.
r = R, a/= O, all z

7.3 Write ali the above equations in dimensionless fonn.

References
[l] Bird, R. B., Stewart, W. E., and Lightfoot, E. N. Transpon Phenomena, Wiley, New York
(1960).
(2] Hinze, J. O. Turbulence, McGraw-Hill, New York (1959).
[3) Himmelblau, D.M. and Bischoff, K. B. Process Analysis and Simulation, Wiley, New York
(1968).
[4] Slattery, J. Momentum, Enerqy and Mass Transfer in Continua, McGraw-Hill, New
York (1972).

(5] Bird, R. B. Chem, Enq. Sci., 6, 123 (1957).

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THE FUNDAMENTAL MASS 361
CHEMICAL REACTOR DESIGN