Reference: Chemical Reactor Design, Optimization and Scale Up by E.

Bruce Nauman

CHAPTER 5: THERMAL EFFECTS AND ENERGY BALANCES

5.1 Temperature Dependence 0f Reaction Rates

Most reaction rates are sensitive to temperature, and most laboratory studies regard
temperature as an important means of improving reaction yield or selectivity. Our
treatment has so far ignored this point. The reactors have been isothermal, and the
operating temperature, as reflected by the rate constant, has been arbitrarily assigned. In
reality, temperature effects should be considered, even for isothermal reactors, since the
operating temperature must be specified as part of the design. For nonisothermal
reactors, where the temperature varies from point to point within the reactor, the
temperature dependence directly enters the design calculations.

5.1.1 Arrhenius Temperature Dependence

The rate constant for elementary reactions is almost always expressed as

-E -T
k = k 0 Tm exp( ) = k 0 Tmexp( act ) (1)
RgT T

Where m = 0, ½, or 1 depending on the specific theoretical model being used. The

quantity E is activation energy, although the specific theories interpret this energy term
E
in different ways. The quantity Tact = has units of temperature (invariably K) and is
Rg
called the activation temperature. The activation temperature should not be interpreted
as an actual temperature. It is just a convenient way of expressing the composite quantity
E/Rg.

The case of m = 0 corresponds to classical Arrhenius theory; m = ½ is derived from the

collision theory of bimolecular gas-phase reactions; and m = 1 corresponds to activated
complex or transition state theory. None of these theories is sufficiently well developed to
predict reaction rates from first principles, and it is practically impossible to choose
between them based on experimental measurements. The relatively small variation in
rate constant due to the pre-exponential temperature dependence T m is overwhelmed by
 Tact
the exponential dependence exp( ) . For many reactions, a plot of ln(k) versus T-1 will
T
be approximately linear, and the slope of this line can be used to calculate E. Plots of
k
ln( m
) versus T-1 for the same reactions will also be approximately linear as well, which
T
shows the futility of determining m by this approach.

Example 1: The bimolecular reaction

NO+ClNO2  NO2 +ClNO
is thought to be elementary. The following rate data are available:

T, K 300 311 323 334 344

K, m3/(mol- 0.79 1.25 1.64 2.56 3.40
s)

Fit Equation (1) to these data for m = 0, 0.5, and 1.

k
Solution: The classic way of fitting these data is to plot ln( ) versus T-1 and to extract
Tm
k 0 and Tact from the slope and intercept of the resulting (nearly) straight line. Special
graph paper with a logarithmic y-axis and a 1/T x-axis was made for this purpose. The
currently preferred method is to use nonlinear regression to fit the data. The object is to
find values for k 0 and Tact that minimize the sum-of-squares:

S2 =  [Experiment - model]
Data
2

J (2)
=  [k j - k 0 T exp - Tact / Tj ]
m
j
2

j=1

Where J=5 for the data at hand. The results of this fitting procedure are:
 T k experimental k fitted
m=0 m = 0.5 m=1
300 0.79 0.80 0.80 0.80
311 1.25 1.19 1.19 1.19
323 1.64 1.78 1.78 1.77
334 2.56 2.52 2.52 2.52
344 3.44 3.38 3.37 3.37
Standard Deviation 0.0808 0.0809 0.0807
ko, m3/mol-s) 64400 2120 71.5
Tact, K 3390 3220 3063

The model predictions are essentially identical. The minimization procedure

automatically adjusts the values for k0 and Tact to account for the different values of m.
The predictions are imperfect for any value of m, but this is presumably due to
experimental scatter. For simplicity and to conform to general practice, we will use m = 0
from this point on.

5.1.2 Optimal Temperatures for Isothermal Reactors

Reaction rates almost always increase with temperature. Thus, the best temperature for
a single, irreversible reaction, whether elementary or complex, is the lightest possible
temperature. Practical reactor designs must consider limitations of materials of
construction and economic tradeoffs between heating costs and yield, but there is no
optimal temperature from a strictly kinetic viewpoint. Of course, at sufficiently high
temperatures, a competitive reaction or reversibility will emerge.

Multiple reactions, and reversible reactions, since these are a special form of multiple
reactions, usually exhibit an optimal temperature with respect to the yield of a desired
product. The reaction energetics are not trivial, even if the reactor is approximately
isothermal. One must specify the isotherm at which to operate. Consider the elementary,
reversible reaction
 
A B
kf
(3)
kr

Suppose this reaction is occurring in a CSTR of fixed volume and throughput. It is desired
to find the reaction temperature that maximizes the yield of product B. Suppose Ef > Er,
as is normally the case when the forward reaction is endothermic. Then the forward
reaction is favored by increasing temperature. The equilibrium shifts in the desirable
direction, and the reaction rate increases. The best temperature is the highest possible
temperature and there is no interior optimum.

For Ef < Er, increasing the temperature shifts the equilibrium in the wrong direction, but
the forward reaction rate still increases with increasing temperature. There is an optimum
temperature for this case. A very low reaction temperature gives a low yield of B because
the forward rate is low. A very high reaction temperature also gives a low yield of B
because the equilibrium is shifted toward the left.

The outlet concentration from the stirred tank, assuming constant physical properties and
bin = 0, is given by
k f a in t
bout = (4)
1+ k f t + k r t
We assume the forward and reverse reactions have Arrhenius temperature dependences
with Ef < Er. Setting dbout/dT = 0 gives

Er
Toptimal = (5)
R g ln[(Er - Ef )(k 0 )r t / E f ]

as the kinetically determined optimum temperature. The reader who duplicates the
algebra needed for this analytical solution will soon appreciate that a CSTR is the most
complicated reactor and Equation (5.3) is the most complicated reaction for which an
analytical solution for Toptimal is likely. The same reaction occurring in a PFR with bin = 0
leads to

a in k f (1 - exp[-k f + k r )t])
bout = (6)
kf + kr
Differentiation and setting dbout = dT = 0 gives a transcendental equation in Toptimal that
cannot be solved in closed form. The optimal temperature must be found numerically.

Example 2: Suppose
A 
kI
 B 
k II
C (7)
with k I = 108 exp(-5000 / T) and k II = 1015 exp(-1000 / T), h -1 . Find the temperature that

maximizes bout for a CSTR with t = 2 and for a PFR with the same 2-h residence time.
Assume constant density with bin = cin = 0:
2
c in k B tb in k A k B t a in
Solution: Use c out = + + with
a + k c t (1+ k B t)(1+ k C t) (1+ k A t)(1+ k B t)(1+ k C t)

bin = 0 for the CSTR to obtain

k I a in t
bout = (8)
(1+ k I t)(1+ k II t)
A one-dimensional search gives Toptimal = 271.4K and bout = 0.556ain. Convert Equation
b0 k B a0 k A k B b k a0 k A k B a0 k A k B
c =[c 0 - + ]e -k C t +[ 0 B - ]e -k B t +[ ]e -k A t
k C - k B (k C - k A )(k C - k B ) k C - k B (k C - k B )(k B - k A ) (k C - k A )(k B - k A )

to the PFR form and set bin = 0 to obtain

k I a in [exp(-k I t) - exp(-k II t)]

bout = (9)
k II - k I

Numerical optimization gives Toptimal  271.7 and b  0.760ain .

At a fixed temperature, a single, reversible reaction has no interior optimum with respect
to reaction time. If the inlet product concentration is less than the equilibrium
concentration, a very large flow reactor or a very long batch reaction is best since it will
give a close approach to equilibrium. If the inlet product concentration is above the
equilibrium concentration, no reaction is desired so the optimal time is zero. In contrast,
there will always be an interior optimum with respect to reaction time at a fixed
temperature when an intermediate product in a set of consecutive reactions is desired.
(Ignore the trivial exception where the feed concentration of the desired product is
already so high that any reaction would lower it.) For the normal case of bin ain , a very
small reactor forms no B and a very large reactor destroys whatever B is formed. Thus,
there will be an interior optimum with respect to reaction time.

5.2 The Energy Balance

A reasonably general energy balance for a flow reactor can be written in English as

[Enthalpy of input streams - enthalpy of output streams + heat generated by reaction -

heat transferred out] = accumulation of energy

and in mathematics as

d(VρH)
Qinρin Hin - Qoutρout Hout = vΔHR R - UA ext (T - Text ) = (10)
dt

5.2.1 Nonisothermal Batch Reactors

The ideal batch reactor is internally uniform in both composition and temperature. The
flow and mixing patterns that are assumed to eliminate concentration gradients will
eliminate temperature gradients as well. Homogeneity on a scale approaching molecular
dimensions requires diffusion. Both heat and mass diffuse, but thermal diffusivities tend
to be orders-of-magnitude higher than molecular diffusivities. Thus, if one is willing to
assume compositional uniformity, it is reasonable to assume thermal uniformity as well.
For a perfectly mixed batch reactor, the energy balance is

d(VρH)
= -VΔHR R - UA ext (T - Text ) (11)
dt

For constant volume and physical properties

dT -ΔHR R UA ext (T - Text )
= - (12)
dt ρC P VρC P

Suppose that there is only one reaction and that component A is the limiting reactant.
Then the quantity

-ΔHR ain
ΔTadiabatic = (13)
ρC p

gives the adiabatic temperature change for the reaction. This is the temperature that the
batch would reach if the physical properties really were constant, if there were no change
in the reaction mechanism, and if there were no heat transfer with the environment.

In matrix form,

d(aV)
= νRV (14)
dt

The design equations for a nonisothermal batch reactor include N + 1 ODEs, one for each
component and one for energy. These ODEs are coupled by the temperature and
compositional dependence of R. They may also be weakly coupled through the
temperature and compositional dependence of physical properties such as density and
heat capacity, but the strong coupling is through the reaction rate.

Example 3: Ingredients are quickly charged to a jacketed batch reactor at an initial

temperature of 25⁰C. The jacket temperature is 80⁰C. A pseudo-first order reaction
occurs. Determine the reaction temperature and the fraction unreacted as a function of
time. The following data are available:
V = 1m 3
A ext = 4.68m 2
U = 1100J / (m 2 s K)
ρ = 820kg / m 3
C p = 3400J / (kg K)
k = 3.7 ×108 exp(-6000 / T)
ΔHR = -108,000J / mol
a in = 1900.0mol / m 3

Physical properties may be assumed to be constant.

Solution: The component balance for A is

da
= -ka
dt

FIGURE 5.1 (a) Temperature and (b) fraction unreacted in a nonisothermal batch
reactor with jacket cooling.
and the energy balance is

dT -ΔHR R UA ext (T - Text ) ka UA ext (T - Text )

= - = ΔTadiabatic ( )-
dt ρC p VρC p a in VρC p

where Tadiabatic = 73.6K for the subject reaction. The initial conditions are a = 1900 and T
= 298 at t = 0: The Arrhenius temperature dependence prevents an analytical solution.
All the dimensioned quantities are in consistent units so they can be substituted directly
into the ODEs. A numerical solution gives the results shown in Figure 5.2.

The curves in Figure 5.1 are typical of exothermic reactions in batch or tubular reactors.
The temperature overshoots the wall temperature. This phenomenon is called an
exotherm.

5.2.2 Nonisothermal Piston Flow

Steady-state temperatures along the length of a piston flow reactor are governed by an
ordinary differential equation. Consider the differential reactor element shown in Figure
5.2. The energy balance is the same as Equation (10) except

FIGURE 5.2 Differential element in a nonisothermal piston flow reactor.

that differential quantities are used. The ρQH terms cancel and z factors out to give:
d(ρQH) dH dH
= ρQ = ρA c u = -ΔHR RA c - UA 'ext (T - Text ) (15)
dz dz dz

Unlike a molar flow rate—e.g, aQ —the mass flow rate, ρQ , is constant and can be brought

outside the differential. Note that Q = uA C and that A 'ext is the external surface area per
unit length of tube. Equation (15) can be written as

dH -ΔHR R c UA 'ext
= - (T - Text ) (16)
dz ρu ρuA c

With a constant, circular cross section, A 'ext = 2πR (although the concept of piston flow is
not restricted to circular tubes). If CP is constant,

dT -ΔHR R 2U
= - (T - Text ) (17)
dz uρC P R uρC P
This is the form of the energy balance that is usually used for preliminary calculations.

Example 4: Hydrocarbon cracking reactions are endothermic, and many different

techniques are used to supply heat to the system. The maximum inlet temperature is
limited by problems of materials of construction or by undesirable side reactions such as
coking. Consider an adiabatic reactor with inlet temperature Tin. Then T(z) < Tin and the
temperature will gradually decline as the reaction proceeds. This decrease, with the
consequent reduction in reaction rate, can be minimized by using a high proportion of
inerts in the feed stream.

Consider a cracking reaction with rate

R =[1014 exp(-24,000 / T)]a,g / (m3 s)

where a is in g/m3. Suppose the reaction is conducted in an adiabatic tubular reactor

having a mean residence time of 1 s. The crackable component and its products have a
heat capacity of 0.4 cal / g K and the inerts have a heat capacity of 0.5 cal / g K ; the
entering concentration of crackable component is 132 g/m3 and the concentration of
inerts is 270 g/m3; Tin = 52 ⁰C. Calculate the exit concentration of A given
ΔHR = 203cal / g Physical properties may be assumed to be constant. Repeat the
calculation in the absence of inerts.

Solution: Aside from the temperature calculations, this example illustrates the
systematic use of mass rather than molar concentrations for reactor calculations. This is
common practice for mixtures having ill-defined molecular weights. The energy balance
for the adiabatic reactor gives

dT -ΔHR R ka
= = ΔTadiabatic ( )
dt ρC P ain
Note that  and C P are properties of the reaction mixture. Thus,

ρ = 132+270 = 402g / m3 and CP = [0.4(132)+0.5(270)]/ 402 = 0.467cal / g K . This

gives ΔTadiabatic = -142.7K . If the inerts are removed, ρ = 132g / m3 , CP = 0.4cal / g K , and

ΔTadiabatic = -507.5K

Figure 5.3 displays the solution. The results are a out = 57.9g / m 3 and Tout = 464.3ο C for the

case with inerts and a out = 107.8g / m 3 and Tout = 431.9ο C for the case without inerts. It is
apparent that inerts can have a remarkably beneficial effect on the course of a reaction.
FIGURE 5.3 Concentration profiles for an endothermic reaction in an adiabatic reactor.

In the general case of a piston flow reactor, one must solve a fairly small set of
simultaneous, ordinary differential equations. The minimum set (of one) arises for a
single, isothermal reaction. In principle, one extra equation must be added for each
additional reaction. In practice, numerical solutions are somewhat easier to implement if
a separate equation is written for each reactive component. This ensures that the
stoichiometry is correct and keeps the physics and chemistry of the problem rather more
transparent than when the reaction coordinate method is used to obtain the smallest
possible set of differential equations. Computational speed is rarely important in solving
design problems of this type. The work involved in understanding and assembling and
data, writing any necessary code, debugging the code, and verifying the results takes much
more time than the computation.

5.2.3 Nonisothermal CSTRs