Reactor Design II-Fourth Year

Dr.Ali N.Khalaf

University of Basrah
College of Engineering
Chemical Engineering Department
Fourth Year
First Semester
Reactor design II

Chapter One
Non-Isothermal
Reactor Design

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1- 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 highest 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.
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. One must specify
the temperature at which to operate. Consider the elementary, reversible reaction

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 is given by
𝐶𝐴0 𝜏 𝑘𝑓
𝐶𝐵,𝑜𝑢𝑡 = …………………….. ……………….. (1)
1+ 𝜏 𝑘𝑓 + 𝜏 𝑘𝑟

We assume the forward and reverse reactions have Arrhenius temperature dependences
𝑑 𝐶𝐵,𝑜𝑢𝑡
with Ef<Er . Setting = 0 gives
𝑑𝑇

𝐸𝑟
𝑇𝑜𝑝𝑡𝑖𝑚𝑎𝑙 = 𝑘𝑟 𝜏(𝐸𝑟 −𝐸𝑓…………………….. ………………. (2)
𝑅 𝑙𝑛
𝐸𝑓

2- Influence of Temperature on Reactor Operation:

Because most reactions we not carried out isothermally, we now focus our attention on
heat effects in chemical reactors. The basic design equations, rate laws, and
stoichiometric relationships derived and used in Chapter 4 for isothermal reactor design
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are still valid for the design of non-isothermal reactors. The major difference lies in the
method of evaluating the design equation when temperature varies along the length of a
PFR or when heat is removed from a CSTR.
Thus, in a batch reactor, the temperature of the reaction mixture may change with time.
In a flow reactor, the temperature may change with time and position, or the feed and
effluent streams may have different temperatures. To account for these effects, reactor
analysis must include the energy balance.
The material and energy balance equations are a coupled set of equations that together
describe the performance of an ideal reactor. Typically, the energy balance is expressed
in terms of the reactor temperature, which may vary with space and time. The nature of
thevariations depends on the reactor type and mode of operation.
In perfectly mixed batch reactors, the temperature is the same at all locations in the
reactor, but changes with time as the reaction proceeds.

Sometimes the reactor is operated with heat transfer through the reactor walls, or via
heating or cooling coils inserted into the reactor. Adiabatic operation is also possible. In
a plug flow reactor, the temperature varies with axial position (i.e., in the direction of
flow) in the reactor. There may or may not be heat transfer through the reactor walls. In
a CSTR, the temperature is uniform everywhere in the reactor and is equal to the outlet
temperature. However, the inlet and outlet temperatures are different. There may ormay
not be heat transfer with the surroundings, either through the vessel walls or by heating
or cooling coils within the reactor.

There are three types of operation:

- Isothermal Operation.
- Adiabatic Operation.
- Non-isothermal Operation (with heat exchange).

Let’s calculate the volume necessary to achieve a conversion, X, in a PFR for a first-
order, exothermic and adiabatic reaction.

𝑑𝑉 𝑥 𝑑𝑥
Material Balance: = ∫0
𝐹𝐴𝑜 𝑟𝐴
𝐸
−
Rate Law:𝑟𝐴 =𝐴𝑒 𝑅𝑇 𝐶𝐴
Stoichiometry: 𝐶𝐴 = 𝐶𝐴𝑜 (1 − 𝑥 )
𝑑𝑉 𝑥 𝑑𝑥
Combine: = ∫0 𝐸
𝐹𝐴𝑜 −
𝐶𝐴𝑜 (1−𝑥) 𝐴 𝑒 𝑅𝑇

We cannot solve this equation because we don’t have x as a function of V or T. We

need another equation. That equation is Energy Balance Equation.
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3- Energy Balance for Batch Reactors:

The 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

𝐻𝑒𝑎𝑡 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 𝐻𝑒𝑎𝑡 𝑎𝑑𝑑𝑡𝑖𝑜𝑛 𝑜𝑟 𝑅𝑒𝑚𝑜𝑣𝑒𝑑

( )+( ) = (𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐻𝑒𝑎𝑡)
𝑏𝑦 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑏𝑦 𝐸𝑥𝑡𝑒𝑟𝑛𝑎𝑙 𝐹𝑙𝑢𝑖𝑑

……. (3)

T = reaction temperature K
Ta= External heating or cooling fluid or wall temperature K
A = heat transfer area m2
Cpi = specific heat kJ/Kmol
U = overall heat transfer kJ/s.m2.K
∆Hr=Heat of reaction per mole of A reacting

……………………… (4)

3.1 Isothermal operation:

Isothermal operation means dT/dt=0 and therefore T=T0 and

− 𝑉 𝑟𝐴 ∆𝐻𝑟 = 𝑈𝐴 (𝑇 − 𝑇𝑎 ) …………………………………. (5)

Heat generation = Heat removed

3.2 Adiabatic Operation:

For constant heat of reaction ∆Hr and constant volume

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………….…………………... (.6)

………….…………………... (7)

3.3 Non-isothermal batch reactor:

The general design material balance equation is still valid and may also be expressed in
terms of fractional conversion, x.

………….…………………... (.8)

This equation is solved with the energy balance equation

𝑁𝐶𝑃 = ∑ 𝜃𝑖 𝐶𝑃𝑖

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Note for constant Volume batch reactor use Cp, and for constant pressure batch reactor
use Cv.

Example 1:
Consider the reaction A → B, (–rA) = kCA, k350 = 0.65 min–1,(ΔHr) = 30(kcal/mol) in a
10liter batch reactor with initial concentration of A = 2 mol/l and temperature To = 350
K. Determine the heat transfer rate required to maintain the temperature at 350 K at95%
conversion
Isothermal operation means dT/dt=0T = To=350 K

Then:Qg=Qr

𝑄𝑔 = −𝑉𝑟𝐴 ∆𝐻𝑟
𝑄𝑞 = −𝑉𝑘𝐶𝐴 ∆𝐻𝑟 = −𝑉𝑘∆𝐻𝑟 𝐶𝐴𝑜 𝑒 −𝑘𝑡
Qr = –0.65 × 2.0 e–0.65t × 10 × 30
Qr = –390e–0.65t(kcal/min).
Since Q < 0, it shows that heat is removed from the system, which is undergoing
exothermic reaction.
The time corresponding to a 95% conversion for the first order reaction is determined
by

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The heat transfer rate (Qt≡95%) at 95% conversion is

Q = –390e–0.65 × 4.608
Q= –19.51 kcal/min
Example 2:
Consider the oxidation of carbon monoxide in an adiabatic constant-volume batch
reactor. If the reaction is assumed to be essentially irreversible; it is described by the
1
overall stoichiometry: 𝐶𝑂 + 𝑂2 → 𝐶𝑂2
2
The rate of reaction in the presence of water is given by a power law rate expression:

A mixture consisting of 1% CO, 1% O2, 1% H2O, and 97% N2 (mole percentages) is

placed in a constant-volume batch reactor of 0.1 m3 volume at an initial pressure of 1
bar and an initial temperature of 700 K. Calculate the time required to achieve 99%
conversion of the CO, and calculate the pressure and temperature in the reactor at that
time.
∆Hr = - 4.513x103 J/molA
The table of Cv( J/mol.K) data is presented below

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Cv

Solution
The oxidation of CO is a highly exothermic chemical reaction, and, as the reactor is
adiabatic, the energy balance will be quite important. It is thus necessary to solve both
the mole and energy balance equations. We start the solution by considering the mole
balance equation. The mole balance equation for CO can be written in terms of the
concentration because the volume of the reactor is constant. The mole balance is:

First note that the number of moles of water, and hence the concentration, is constant
during the reaction, as water does not react and the reactor volume is constant. The
water concentration is given by

The initial concentrations of CO and oxygen can be easily calculated:

𝑋
𝑂𝑟 ∶ 𝐶𝑂2 = (𝐶𝐶𝑂 ))0 (𝛳𝑂2 − )
2
With these substitutions and resulting simplification, the rate equation becomes

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…………….... (A)

We first develop a stoichiometric table:

Substituting for XCO = 0.99, we calculate the total number of moles present to be 1.711
mol. The volume is unchanged; therefore, the pressure in the reactor is

 If we want to find the temperature at the end of reaction and the reaction time
only.

𝑁𝐶𝑃 = ∑ 𝜃𝑖 𝐶𝑃𝑖
At inlet 𝜃𝐶𝑂 =1 ∶ 𝜃𝑂2 =1∶ 𝜃𝐶𝑂2 =0 ∶
𝐽
𝑁𝐶𝑃 = ∑ 𝜃𝑖 𝐶𝑉𝑖 = 19.8 ∗ 1 + 17.13 ∗ 1 = 36.93
𝑚𝑜𝑙𝐴. 𝐾

𝟒. 𝟓𝟏𝟑 ∗ 𝟏𝟎𝟑
𝑻 = 𝟕𝟎𝟎 + 𝒙
𝟑𝟔. 𝟗𝟑
𝑻 = 𝟕𝟎𝟎 + 𝟏𝟐𝟐. 𝟐 ∗ 𝒙
𝑻 = 𝟖𝟐𝟏 𝑲

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0.99
0.172 𝑑𝑥
𝑡= ∫ −20131
3.37x109 0 ( )
e 700+122.2∗𝑥 (1 − 𝑥)(1 − 0.5𝑥)0.25
The above equation solved by Simpson Rule to find the reaction time.
𝑡 = 318 𝑠𝑒𝑐
 If we want to find the temperature and conversion as a function of time

The general energy balance equation is

For adiabatic operation Q = QRemoved=0. Then:

.

…………….... (B)

For batch reactor

…………….... (C)

Substitute Eq. (C) in Eq. (B) gives

𝑑𝑇 𝑑𝑥 𝑁𝐴𝑜 . ∆𝐻𝑟 . 𝑟𝐴 𝑈𝐴 (𝑇 − 𝑇𝑎 )
= −
𝑑𝑡 𝑑𝑡 (∑ 𝑁𝑖 𝐶𝑃𝑖 ) (∑ 𝑁𝑖 𝐶𝑃𝑖 )
𝐶𝐴𝑜 𝑑𝑥
𝑟𝐴 =
𝑑𝑡
The resulting equations (A, B and C) must be solved simultaneously with the mole
balance, to give the fractional conversion and reactor temperature as a function of time.
The solution of this system of coupled nonlinear ordinary differential equations is
performed numerically, using the Runge–Kutta method.

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Or the above equation may written in the finite form as below

∆𝑇 = 𝐶1 ∆𝑥 − 𝐶2 ∆𝑡 ( 𝑇 − 𝑇𝑎 ) Energy Balance …………….. (11)

∆𝑥 = 𝐶3 𝑟̅𝐴 ∆𝑡 𝑀𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝐵𝑎𝑙𝑎𝑛𝑐𝑒 ....…..… (12)

𝑟𝐴 = 𝑓 (𝑥, 𝑇) 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑅𝑎𝑡𝑒 ………….. .. (13)

𝑁𝐴𝑜 . ∆𝐻𝑟 𝑈𝐴 1
𝐶1 = ∶ 𝐶2 = ∶ 𝐶3 =
∑ 𝑁𝑖 𝐶𝑃𝑖 (∑ 𝑁𝑖 𝐶𝑃𝑖 ) 𝐶𝐴𝑜

A plot of the fractional conversion of CO as a function of time is shown in Figure 1.

The temperature increases as the conversion increases, which are the expected result,
because the reaction is exothermic and the reactor is adiabatic. The fractional
conversion reaches 99% after 318 s, at which point the temperature is 821 K.

Figure 1: temperature and conversion profile.

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4- Energy Balance for Flow Reactors (PFR and CSTR):
Since the reaction is non-isothermal, the temperature will vary along the reaction length
the temperature is related to conversion through energy balance equation:
For a flow reactor:

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.... (14)

This is the general energy balance equation for flow system.

5- Adiabatic Reactors (PFR and CSTR) with constant CP:

The starting equation at steady state is

.... (15)

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….............. (16)

And the conversion is:

…………………….............. (17)

………………………….............. (18)

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𝐸
−
𝑟𝐴 = 𝐴 𝑒 𝑅𝑇 𝐶𝐴𝑜 ( 1 − 𝑥 )

Or we can find the volume by integrating the design equation numerically

𝑥
𝑉 𝑑𝑥
=∫ −𝐸
𝐹𝐴𝑜 0 ∆𝐻𝑟
𝑅( 𝑇𝑜 + 𝑥
(𝐶𝐴0 (1 − 𝑥 )𝐴𝑒 ∑ 𝐶𝑃𝑖 𝜃𝑖
)

𝐹𝐴𝑜 𝑥 𝑑𝑥
𝑉=𝐶 ∫ ( −𝐸 )………………..…(19)
𝐴0 𝐴 0 ∆𝐻𝑟
𝑅( 𝑇𝑜 + 𝑥
∑ 𝐶𝑃𝑖 𝜃𝑖 (1−𝑋)
𝑒

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Example 3:

The elementary irreversible organic liquid phase reaction is carried out adiabatically in a
flow reactor. An equimolar feed in A and B enters at 27° C, and the volumetric flow
rate is 2 dm3/s and CA0=0.1 kmol/m3.
a) Calculate the PFR and CSTR volume necessary to achieve 85% conversion.
b) What is the maximum inlet temperature one could have so that the boiling point of
the liquid (550° K) would not be exceeded even for complete conversion?
c) Plot the conversion and temperature as function of PFR volume.
d) Calculate the concentration achieved in one 500 dm3 and in two 250-dm3 CSTRs in
series.
HA°(273)= -20 kcal/mol, HB°(273)= -15 kcal/mol, HC°(273)= -41 kcal/mol
CPA=CPB=15 cal/mol.K, CPC=30 cal/mol.K
k = 0.01 dm3/mol.s at 300° K, E =10000 cal/mol
Solution Part a:

A+B→C

𝐸
−
𝑘 =𝐴𝑒 𝑅𝑇

10000
−
0.01 = 𝐴 𝑒 1.897∗300

𝐴 = 4.27 ∗ 105 dm3 /mol. s

− 5271.481
5
Then 𝑘 = 4.27 ∗ 10 𝑒 𝑇

Volume of CSTR equals the area of rectangle VCSTR = 0.85 x 206 = 175 dm3
Volume of PFR equals the entire Area under the curve VPFR ~ 305 dm3

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Solution: Part b
What is the maximum inlet temperature one could have so that the boiling point of the
liquid (550 K) would not be exceeded even for complete conversion?

Solution: Part C
Plot the conversion and temperature as function of PFR volume.

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Solution: Part D
𝑉 𝑥
=
𝐹𝐴𝑜 𝑟𝐴
For one CSTR:
𝑉 𝑥
= − 5271.481
𝐹𝐴𝑜 2 2 5
𝐶𝐴𝑜 (1 − 𝑥) 4.27 ∗ 10 𝑒 300+200𝑥
𝑥 = 0.92

For two CSTR

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𝑥1 . 𝐹𝐴𝑜
𝑉𝐶𝑆𝑇𝑅 1 = − 5271.481 = 500
𝐶𝐴𝑜 2 (1 − 𝑥1 )2 4.27 ∗ 105 𝑒 300+200𝑥1
𝑥1 = 0.881
(𝑥2 − 𝑥1 ) . 𝐹𝐴𝑜 (1 − 𝑥1 )
𝑉𝐶𝑆𝑇𝑅 2 = − 5271.481 = 250
2
𝐶𝐴𝑜 (1 − 𝑥2 )2 4.27 ∗ 105 𝑒 300+200𝑥2

𝑥2 = 0.97

Example: 4
The reversible first-order gas reaction A⇋R is to be carried out in a CSTR. For
operations at 300 K the volume of reactor required is 100 liters for 60% conversion of
A. What should be the volume of the reactor for the same feed rate and conversion but
with operations at 400 K?
Data: kl= 1x103exp [-2416/T] min -1
∆Hr= -8000 cal/mol at 300 K
K = 10 at 300 K: Feed consists of pure A: Total pressure stays constant
Solution:

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Example 5:
The gas-phase reaction A +B→ C is carried out in a pilot plant tubular reactor at about
2 atm and 300oC. The feed rate is 0.120 m3/sec and feed is 40% A, what reactor volume
is needed for 95% conversion under adiabatic operation?
k=1.4x107exp (-7700/T) m3/mol.sec :∆Hr = -14000 J/mol : CPA = CPB= 15 J/mol.K
Solution:

∑ 𝛳𝑖 𝐶𝑃𝑖 =1*15+1.5*15=37.5 J/mol.K

14000
𝑇 = 573 + 𝑥 = 573 + 373.3𝑥
37.5

7
−7700
𝑟𝐴 = 1.4 ∗ 10 𝑒𝑥𝑝 𝐶𝐴𝑜 ( 1 − 𝑥 ) 𝐶𝐴𝑜 (1.5 − 𝑥 )
𝑇
0.4 ∗ 2
𝐶𝐴𝑜 = = 0.017𝐾𝑚𝑜𝑙/𝑚3
0.082 ∗ 573
𝐹𝐴𝑜 = 0.017*0.12 =0.00204 Kmol/sec

0.95
𝑉 𝑑𝑥
=∫ −𝐸
𝐹𝐴𝑜 0 ∆𝐻𝑟
2 𝑅( 𝑇𝑜+ 𝑥
(𝐶𝐴0 (1 − 𝑥)(1.5 − 𝑥) ∗ 1.4 ∗ 107 𝑒 ∑ 𝐶𝑃𝑖 𝜃𝑖
)

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0.95
𝐹𝐴𝑜 𝑑𝑥
𝑉= 2 ∫ ( −7700 )
1.4 ∗ 107 𝐶𝐴0 0 (1 − 𝑥 )(1.5 − 𝑥 ) exp
573+373.3𝑥
After the integration by Simpson Rule we can find the volume.
-------------------------------------------------------------

6- Flow Reactors with Heat Exchange:

The general energy balance for continuous flow reactors is given by

6.1- PFR with Heat Exchange:

A non adiabatic PFR exchanges heat with the surroundings. Several different designs
are used industrially. One possibility would be to impose a constant heat flux at the wall
of the reactor. Such a reactor may be constructed in different ways but the simplest
scenariois illustrated in Figure 2.
This design is very similar to a double pipe heat exchanger, consisting of two concentric
tubes with the central tube acting as the reactor and the surrounding jacket containing
the heat transfer fluid.

Fig.2:Jacket PFR-double pipe heat exchanger.

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When reactors are operated in the nonisothermal mode, the diameter of the reactor is
usually relatively small so that an effective rate of heat transfer can be achieved. Use of
a small reactor diameter can lead to a requirement of very long reactor length if a large
volume isrequired. Rather than have a single very long tube, a common design uses
multiple reactor tubes surrounded by a large shell containing the heat transfer fluid,
resembling a shell and tube heat exchanger. This type of arrangement is shown in
Figure 3.

Fig.3:Multi-tubular reactor used for non adiabatic operation.

Where (a) is heat exchange area per unit volume of the reactor,

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𝐴 𝜋𝐷𝐿 4
𝑎 = = 𝜋𝐷2 =
𝑉 𝐿 𝐷
4

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……... (20)

……... (21)

- Solving CRE Problem for Reactors with Heat Exchange:

.. (22)

…(23)

If the coolant temperature varies down the reactor we must add coolant balance:

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Heat Exchanger Energy Balance- Variable Ta Co-current
Coolant Balance:

….(24)

……………. (25)

….……………. (26)

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The above Equations (Eq.20 to Eq. 24)are the general form of the energy balance for a
PFR with external heat exchange. It may be written explicitly in terms of in terms of the
reactor length to give the temperature and conversion profile along reactor length

𝑑𝑉 = 𝐴𝑡𝑢𝑏𝑒 𝑑𝑧 𝐹𝑜𝑟 𝑀𝑢𝑙𝑡𝑖𝑡𝑢𝑏𝑒 𝑅𝑒𝑎𝑐𝑡𝑜𝑟…………………….. (27)

𝑑𝑉 = 𝐴𝑅𝑒𝑎𝑐𝑡𝑜𝑟 𝑑𝑧 𝐹𝑜𝑟 𝐷𝑜𝑢𝑝𝑙𝑒 𝑃𝑖𝑝𝑒 𝑅𝑒𝑎𝑐𝑡𝑜𝑟………………... (28)
𝜋𝐷2
𝑑𝑉 = 𝑑𝑧
4
𝒅𝑻 𝑨 . ∆𝑯𝒓 . 𝒓𝑨 𝑼𝒂 (𝑻 − 𝑻𝒂 )
= −
𝒅𝒛 𝑭𝑨𝒐 (∑ 𝜽𝒊 𝑪𝑷𝒊 ) 𝑭𝑨𝒐 (∑ 𝜽𝒊 𝑪𝑷𝒊 )
𝑭𝑨𝒐 𝒅𝒙
𝒓𝑨 =
𝑨 𝒅𝒛
𝒅𝑻 ∆𝑯𝒓 𝒅𝒙 𝑨 ∗ 𝑼𝒂 (𝑻 − 𝑻𝒂 )
= −
𝒅𝒛 (∑ 𝜽𝒊 𝑪𝑷𝒊 ) 𝒅𝒛 𝑭𝑨𝒐 (∑ 𝜽𝒊 𝑪𝑷𝒊 )
The above equation may written in the finite form as

∆𝑇 = 𝐶1 ∆𝑥 − 𝐶2 ∆𝑧 ( 𝑇 − 𝑇𝑎 ) Energy Balance …………….. (29)

∆𝑥 = 𝐶3 𝑟̅𝐴 ∆𝑧 𝑀𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝐵𝑎𝑙𝑎𝑛𝑐𝑒 ....…..… (30)

𝑟𝐴 = 𝑓 (𝑥, 𝑇) 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑅𝑎𝑡𝑒 …………….. (31)

∆𝐻𝑟 𝐴 ∗ 𝑈𝑎 𝐴
𝐶1 = 𝐶2 = 𝐶3 =
∑ 𝜃𝑖 𝐶𝑃𝑖 𝐹𝐴𝑜 (∑ 𝜃𝑖 𝐶𝑃𝑖 ) 𝐹𝐴𝑜

The three types of reactor operations yield different temperature profiles within the
reactor and are shown in Figure 4 for an exothermic reaction.

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Figure 4: temperature profiles for PFR in three different mode of operation.

6.2- CSTR with Heat Exchange:

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Figure 5: CSTR with heat exchange.

̇ =0 and 𝑸̇ = 𝑼𝑨(𝑻 − 𝑻𝒂 )
If 𝑾𝒔

Solving for x:

.………… (32)

Solving for T:

.… (33)

Example 6:
A second order, liquid phase reaction, A + B → C, is to be performed in a single-stage
CSTR. Given the following data:
1. Determine the size of the reactor required to achieve 85% conversion of A.
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Answer: V = 7.56 m3
2. Estimate the heat-transfer area needed to maintain the reactor temperature at 27oC.
Answer: A=3 m2
3. Calculate what the feed temperature must be if the reactor is to be operated
adiabatically at 27oC.
Answer: To = 8.8°C

Example 7:
Consider the reaction A → B, rA = kCA, k300= 0.05 min-1 , ∆Hr = -20 kcal/mole in a 10
liter reactor with CA0 = 2 moles/liter and To =300 K. At what rate must heat be removed
to maintain the reactor isothermal at 300 K for (a) a batch reactor at 90% conversion?
This is an isothermal reactor with r = 0.05CA. If batch, then

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Note, however, that the significance of heat removal or addition (Q positive or negative)
is quite different with the batch reactor, requiring a heat removal that varies in time, the
CSTR requiring a constant heat removal rate, and the PFR requiring a heat removal rate
that varies with position z in the reactor. These are sketched in Figure 6.

Figure 6:heat removal rate that varies with position z or t.

7- Multiple Steady States in a CSTR:

One of the interesting operating features of a nonisothermal CSTR is the existence of
multiple steady states under certain operating conditions. In a reactor with multiple
steady states, there is more than one set of steady-state operating conditions possible.
From a mathematical perspective, the existence of multiple steady states implies that
there is more than one solution (temperature and conversion) that satisfies the mole and
energy balance equations.
In the following, we use some graphical analysis to illustrate how multiple steady states
arise and the implications for reactor operation. A simple first order reaction with a
constant-density fluid is chosen for simplicity, but the principles may be extended to
more complex cases, with a concomitant increase in mathematical complexity.
For illustration purposes, consider a first-order reaction occurring in a nonisothermal
CSTR. The material balance equation is:
𝑉 𝑥
=
𝐹𝐴𝑜 𝑘 𝐶𝐴𝑜 ( 1 − 𝑥 )
This equation can be rearranged to give an expression for conversion of A:

𝑘𝜏
𝑥𝑀𝐵 =
1 + 𝑘𝜏
The steady-state energy balance written in terms of conversion and constantheat
capacity is given by Equation.

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Note that 𝑄̇ = 𝑈𝐴(𝑇 − 𝑇𝑎 )is positive if heat is added to the reactor, that is, when
(Ta>T). The above equation can be rearranged as follows:

.… (34)

……………………………………………… (35)

…… (39)

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Equation39 is a nonlinear equation. For a given set of operating conditions, the reactor
temperature is the only unknown value in the equation. However, owing to the nature of
the equation, it is possible that under some sets of operating conditions there will be
more than one solution to Equation 39.
The function G(T) represents the rate of heat generation in the reactor. The second
function isR(T) represents the rate of heat removal by heat transfer with the
surroundings and the rate of fluid removal from the reactor. Note that R(T) is a linear
function of temperature in this case because CP and ∆Hr are assumed to be constant. The
intercept of the straight line depends on, for example, the value of the reactor inlet
temperature. A typical behavior of the function R(T) at different inlet temperatures is
shown in Figure 7.

Fig.7: Variation of heat removal line with inlet temperature.

An increase in the value of the reactor inlet temperature simply shifts the line to the
right, while maintaining the value of the slope. The slope of the curve can be adjusted
by changing the value of (CP0(1+ κ). Also the linear energy line depends on the value of
κ as shown in Figure 8.

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Fig.8: Variation of heat removal line with κ (κ=UA/CP0FA0 ).

A plot of the generation function, G(T), verses T gives a sigmoidal curve because of the
exponential temperature dependence of the rate constant. The shape of the curve
depends in large part on the value of the activation energy. A typical plot is shown in
Figure 9.

.
Fig.9: Shape of the heat generation function at different reactor temperatures.

The shape of the curve depends also on the value of space time τ. A typical plot is
shown in Figure 10.
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Fig.10: Variation of heat generation curve with space-time.

All possible reactor operating temperatures must satisfy both functions, G(T) and
R(T),such that the two functions have equal values. If both of the functions are plotted
on the same graph, the points of intersection of the two lines represent permissible
solutions to the reactor energy and mole balance equations. Figure 11 illustrates such a
graph. In this figure, a single G(T) curve is shown, which would correspond to specific
values of the kinetic parameters and enthalpy of reaction. Multiple R(T) curves are
shown, each of which corresponds to a different reactor inlet temperature, with all other
parameters the same.

Fig.11: Plot of a single heat generation curve and multiple heats removal curves

Consider first the R(T) line that corresponds to the lowest value of the inlet temperature.
This line is at the extreme left of Figure 10. This line intersects the G(T) at a single

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point, labeled 1 in Figure 11. This point of intersection corresponds to the only solution
to the mole and energy balance equations; thus this point represents the reactor
operating temperature. If the reactor inlet temperature is increased, with all other
conditions held constant, the R(T) line moves to the right. The sigmoidal G(T) curve is
not affected by the change in the inlet temperature because T0 does not appear in the
expression for G(T). The second R(T) curve from the left intersects the G(T) curve at
two points, marked with points 2 and 6,respectively. Both these points represent
possible operating temperatures for the reactor, the low- and high-temperature stable
operating conditions for this reactor. The next R(T) line in Figure 10 intersects the G(T)
curve at three points, labeled 3, 5, and 7 respectively.
Points 3 and 7 represent stable-steady states. Point 5 is an unstable steady state which
cannot be achieved in practice. Continuing to increase the inlet temperature, the next
R(T) curve illustrated has two stable steady states at 4 and 8, the final curve has a single
steady state at point 9.
The steady state that is realized in the reactor depends on either the initial conditions or
the history of the reactor as shown in Figure 12.

Fig. 12: Plot of CSTR stability diagram.

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Example 8:
Consider a first order adiabatic reaction in a CSTR with the following characteristics:

The rate constant k is expressed as k = exp (15.32 – 7550/T), sec–1.

Determine the operating points for both the mass and heat balance equations.
Solution:
The first order reaction is represented by (–rA) = kCA, and applying the material balance
and the energy balance Equations gives

𝑘𝜏
𝑥𝑀𝐵 =
1 + 𝑘𝜏

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τ= V/Qo = 15.0/0.05 = 300.0 sec.

7550
300 𝑘 300 𝑒𝑥𝑝(15.32 –
)
𝑇
𝑥𝑀𝐵 = = 7550
1 + 300 𝑘 1 + 300 𝑒𝑥𝑝(15.32 – )
𝑇
𝑇 − 298
𝑥𝐸𝐵 =
210
The figure shows that the steady state values are (XA, T) = (0.02, 300), (0.5, 362), and
(0.95, 410). The middle point is unstable and the last point is the most desirable because
of the high conversion

Example 9:
Determine the operating conditions in a CSTR for a first order exothermic reaction with
heat transfer under the following conditions:
Feed temperature, TO, = 350 K
Initial concentration, CAO= 1.0 mol/L
Temperature of the cooling medium, TC = K 350 K
Mean residence time, τ =1.0 min

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kJ
(–ΔHr)= 200kJ/mol.𝐶𝑝𝑜 = 1.0 : UA/FA.Cp= 1.0
mol.K
Reaction rate constant, k= exp (25 – 10000/T) min–1
Solution:

𝟏𝟎𝟎𝟎𝟎
−𝟐𝟎𝟎 ∗ 𝟏 ∗ 𝟏 ∗ 𝐞𝐱𝐩 (𝟐𝟓 – )
𝐓
𝑮(𝑻) = 𝟏𝟎𝟎𝟎𝟎 𝐤𝐉/𝐦𝐨𝐥
𝟏 + 𝟏 ∗ 𝟏 ∗ 𝐞𝐱𝐩 (𝟐𝟓 – )
𝐓
𝑘𝜏
𝑥𝑀𝐵 =
1 + 𝑘𝜏
10000
1 ∗ exp (25 – )
T
𝑥𝑀𝐵 = 10000
1 + 1 ∗ exp (25 – )
T

𝑼𝑨
𝑹(𝑻) = 𝑪𝒑𝒐 (𝟏 + 𝜿)(𝑻 − 𝑻𝟎 )𝜿 =
𝑪𝑷𝒐 𝑭𝑨𝒐

𝑹(𝑻) = 𝟏(𝟏 + 𝟏)(𝑻 − 𝟑𝟓𝟎) = 𝟐(𝑻 − 𝟑𝟓𝟎)𝐤𝐉/𝐦𝐨𝐥

Both G(T) and R(T) at varying effluent temperature. Figure below shows the profiles of
the heat generation and heat removal terms, and the intersections give the operating
conditions. The values of the fractional conversion XA corresponding to the
temperatures at the sepoints are given in the table below.

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Example 10:
The first order irreversible reaction A(l) → B(l) is carried out in a jacketed CSTR. The
feed contains A and an inert liquid in equimolar amounts, where FA0 = 80 mol/min.
What is the reactor temp when the inlet temp T0 is 450K?
UA= 8000 cal/min·K: Ta= 300K ∆HR=-7500 cal/mol:CpA = CpB =20 cal/mol·K
Cpi =30 cal/mol·Kτ=100 min : E=40,000 cal/mol: k=6.6 x 10-3 min-1 at 350K

Solution:

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Plug rate law into G(T) and simplify

Steady state temp G (T) =R (T) for T0 = 450K

Use design equation to get XA as an explicit equation:

The steady state temperature for T0 = 450K is 400 K

Then x=

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8-Adiabatic Equilibrium Conversion:
In an exothermic reaction, the value of ∆Hr is negative. Therefore, an increase in the
temperature decreases the value of K, with a concomitant decrease in the equilibrium
yield. A conflict arises between the need for a high temperature to maximize the
reaction rate, and a low temperature to maximize the conversion. For endothermic
reaction, equilibrium conversion increases with increasing temperature. A typical
equilibrium curve and temperature conversion trajectory for the reactor sequence is
shown in Figure 13.

For exothermic Reactions: As T increases, the equilibrium shifts to the left. i.e. both
K and Xe decreases
For endothermic Reactions: As T increases, the equilibrium shifts to the right. i.e.
both K and Xe increases

Fig.13: Equilibrium conversion and equilibrium constant for exothermic

and endothermic reactions.

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Figure 14 shows a typical equilibrium composition line that might be obtained for an
exothermic reaction. The line has an equilibrium conversion near one at low
temperature but the conversion decreases as the temperature increases. Now consider
the performance of two types of reactor, the adiabatic reactor and the isothermal reactor.
For a given set of operating conditions, the adiabatic reaction line governs the
relationship between the temperature and the fractional conversion. Assuming constant
∆Hr and CP, the energy balance equation is:

Fig.14:The equilibrium line shows the relationship between the temperature and conversion at
equilibrium for a specified starting composition. The adiabatic reaction line shows the maximum
conversion that can be obtained for adiabatic operation for a given inlet temperature. The isothermal
reaction line shows the best conversion for isothermal operation.

A typical adiabatic reaction line is shown in Figure 15 for an arbitrary value of T0. In the
reactor, both the temperature and conversion will increase along this line until the
equilibrium line is encountered at X2 and T2.

At this point, the rate is zero, and the temperature and composition of the process stream
remain constant for any additional reactor volume.

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Fig.15: The equilibrium conversion for adiabatic operation.

If the same reactor was operated isothermally, the vertical operating line shown in
Figure 14 would be obtained. As the temperature is constant, the fractional conversion
finally attained, equal to X1, and is higher than that achieved in the adiabatic reactor.
Isothermal operation may not be practical, and does not result in a minimum reactor
volume. It is possible to determine an optimal temperature progression along the reactor
so as to maximize the conversion for the minimum possible reactor volume.

Consider the diagram shown in Figure 15. This diagram shows lines of constant
reaction rate correspondingto set values of temperature and conversion. Each solid line
represents a locus of the set of temperature and conversion that give a specified value of
the rate. The top line corresponds to a rate of zero; in other words, the equilibrium line.
We have alreadyseen that the equilibrium conversion drops as the temperature rises. As
we move from the top to the bottom of the figure, the value of the reaction rate
increases. Note, however, that as the value of the reaction rate increases, the maximum
conversion achievable at that rate decreases.

This observation suggests a route for minimizing the reactor volume. One could start
the reaction at a high temperature to take advantage of the high rate at that temperature,
and then progressively lower the temperature to increase the equilibrium yield.
The dashed line in Figure 16 illustrates the type of temperature and conversion pathway
that must be followed to achieve this optimal design. This reactor design would require
a complex cooling pattern along the reactor length, which might not be practical.

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Fig 16: Each solid line in this diagram represents a constant value of reaction rate.

Higher conversions than those shown in Figure 16 can be achieved for adiabatic
operations by connecting reactors in series with interstate cooling. Inter-stage cooling
system consists of a series of reactors or catalyst chambers. In each of the reactor stages,
the temperature rises from inlet to outlet. Heat-exchangers (inter-stage coolers) are
placed between the reactor stages as shown in Figure 17, where the temperature is
reduced without affecting the composition of the process stream. The operating line of a
single-reactor does not naturally follow a trajectory that shadows the locus of maximum
reaction rates. By subdividing the reactor into a number of stages and removing heat
from the reaction mixture after each reactor stage, the temperature is forced lower
before the stream enters the next vessel. This allows working closer to the locus of
maximum rates (see Figure 16). Clearly the larger the number of steps, the closer the
trajectory of the system would approach the theoretical optimum. An inordinately large
increase in the number of inter-stage coolers, however, would tend to increase
construction costs. We would need to determine the optimum number of reactor stages.

Fig.17: Schematic diagrams of two reactors in series.

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8-Multibed Adiabatic Reactors for Equilibrium Limited Reactions:
For relatively fast reactions that are equilibrium limited, the adiabatic reactor is
commonly used in industry. As seen above, the adiabatic reactor experiences a
temperature rise that limits the conversion. Therefore, in applications where very high
conversions are desired, it is common to use multiple reactors in series, with cooling
between each reactor.

Consider, for example, an exothermic reaction that occurs in a series of adiabatic fixed
bed catalytic reactors. The operating path would be similar to the one shown in Figure
18.This plot shows the equilibrium line as a function of temperature and conversion. For
adiabatic operation, the temperature and conversion in the first reactor follow the
adiabatic reaction line denoted Bed 1. When the fraction conversion reaches a value of
X1, which is approaching the equilibrium line, the process stream is cooled by passing it
through a heat exchanger. As this is a catalytic reaction, no further conversion occurs in
this stage, as shown by the flat line. When the process stream is cooled by a
predetermined amount, the stream enters reactor number two, in which it undergoes a
further adiabatic reaction until the conversion is X2.

The stream is cooled as before, and then fed into the last bed, in which the conversion is
brought to X3. Using this strategy, a high level of conversion can be achieved using
adiabatic reactors. A diagram of the reactor that corresponds to Figure 18and Figure 19.
The exact number of beds and the degree of cooling between the beds depends on the
reaction involved and operating and capital costs.

Fig. 18: Multiple adiabatic reactors in series.

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Fig.19: Multiple bed adiabatic catalytic reactor with interstage cooling.

The most classic application of the multibed adiabatic fixed bed reactor is the oxidation
1
of sulfur dioxide 𝑆𝑂2 + 𝑂2 ⇋ 𝑆03 , equilibrium limited reversible reaction. This
2
reaction is used to make sulfur trioxide, which, when added to water, makes sulfuric
acid. Very high yields are desired (in excess of 99%), but the reaction is highly
exothermic and equilibrium limited. As a result the multibed approach has been
adopted, with typical industrial units having three or four beds.
Example 11:
For the elementary solid-catalyzed liquid-phase reaction: A ⇋ B .Make a plot of
equilibrium conversion as a function of temperature. Determine the adiabatic
equilibrium temperature and conversion when pure A is fed to the reactor at a
temperature of 300 K.
Additional information:CPA = CPB = 50 cal/mol.K :∆Hr = -20000cal/molA
Keq (300K) =100000

Solution:

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What conversion could be achieved in Example 5.10 if two interstage coolers were
available that had the capacity to cool the exit stream to 350 K? Also determine the heat
duty of each exchanger for a molar feed rate of A of 40 moles. Assume that 95% of
equilibrium conversion is achieved in each reactor. The feed temperature to the first
reactor is 300 K.
For an entering temperature of 300 K the adiabatic equilibrium conversion was 0.40.
For 95% of equilibrium conversion, the conversion exiting the first reactor is 0.38.

The first reactor:

The exit temperature from the first reactor is found from a rearrangement of Equation
(e):
𝑋𝐸𝐵 = 0.0025(𝑇 − 300)
𝑇 = 400 𝑋 + 300 = 400 ∗ 0.38 + 300 = 452 𝐾

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We now cool the gas stream exiting the reactor at 460 K down to 350 K in a heat
exchanger. The gas stream is then sent to the second reactor.

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Example 12:
The reversible conversion of A+B ⇋ C+D is carried out in liquid phase in a series of
staged PFR's with interstage cooling. The lowest temperature to which the stream may
be cooled is 300K. The feed is equal molar in A and B and contains no C or D. The
PFR's have a sufficient residence time to achieve 99.9% of the equilibrium conversion
in each stage. The feed enters at 300K and the reaction is carried out adiabatically. If
two reactors and one interstage cooler are used, what is the maximum conversion
(±O.05) that may be achieved after the second PFR?

Data: ∆Hr = -40000 cal/molA: CPA = CPB = CPC=CPD=53.3cal/mol.K

Keq (300K) = 3.22x108 FAo = 5 mol A /min

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The first stage:

∑ 𝛳𝑖 𝐶𝑃𝑖 =1*53.3+1*53.3=106.6 cal/mol.K

106.6(𝑇 − 300)
𝑋𝐸𝐵 =
40000
𝑋𝐸𝐵 = 0.00266(𝑇 − 300)
𝑋𝐸𝐵 = 0.00266𝑇 − 0.798
This equation cuts the equilibrium curve at x=0.36 and T= 436 K

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The second stage:
106.6(𝑇 − 300)
𝑋𝐸𝐵 = 0.36 +
40000
This equation cuts the equilibrium curve at x=0.66 and T= 415 K
So the maximum conversion for this system is 0.66

The heat load for the interstage cooling is:

𝑄1 = 𝐹𝐴𝑂 (1 − 𝑋1 )𝐶𝑃𝐴 (300 − 436)
𝑄1 = 5 mol A /min(1 − 0.36)53.3cal/mol. K(300 − 436)𝐾
𝑄1 = − 23.196 Kcal/min

9-Optimum Feed Temperature:

We now consider an adiabatic reactor of fixed size or catalyst weight and investigate
what happens as the feed temperature is varied. The reaction is reversible and
exothermic. At one extreme, using a very high feed temperature, the specific reaction
rate will be large and the reaction will proceed rapidly, but the equilibrium conversion
will be close to zero. Consequently, very little product will be formed. At the other
extreme of low feed temperatures, little product will be formed because the reaction rate
is so low. A plot of the equilibrium conversion and the conversion calculated from the
adiabatic energy balance is shown in Figure 20.

Figure 20: Equilibrium conversion for different feed temperatures.

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We see that for an entering temperature of 600 K the adiabatic equilibrium conversion is
0.15, while for an entering temperature of350K it is 0.75. The corresponding conversion
profiles down the length of the reactor for these temperatures are shown in Figure 21.

Figure 21: Adiabatic conversion profiles for different feed temperatures.

We notice that the conversion and temperature increase very rapidly over short distance
(i.e., a small amount of catalyst). This sharp increase is sometimes referred to as the
"point" or temperature at which the reaction "ignites."
If the inlet temperature were lowered to 500 K, the corresponding equilibrium
conversion would increase to 0.38; however, the reaction rate is slower at this lower
temperature so that this conversion is not achieved until closer to the end of the reactor.
If the entering temperature were lowered further to 350 K, the corresponding
equilibrium conversion would be 0.75, but the rate is so slow that a conversion of 0.05
is achieved for the specified catalyst weight in the reactor. At a very low feed
temperature, the specific reaction rate will be so small that virtually all of the reactant
will pass through the reactor without reacting. It is apparent that with conversions close
to zero for both high and low feed temperatures, there must be an optimum feed
temperature that maximizes conversion. As the feed temperature is increased from a
very low value, the specific reaction rate will increase, as will the conversion. The
conversion will continue to increase with increasing feed temperature until the
equilibrium conversion is approached in the reaction. Further increases in feed
temperature for this exothermic reaction will only decrease the conversion due to the
decreasing equilibrium conversion. This optimum inlet temperature is shown in Figure
22.
For reversible, exothermic reactions optimize feed temperature to maximize XA.
High T0: moves XA,EB line to the right. Reaction reaches equilibrium fast, but low XA .
Low T0 would give high XA,e but the specific reaction rate k is so small that most of the
reactant passes through the reactor without reacting (never reach XA,e)

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Figure 22: Finding the optimum feed temperature.

10-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 highest 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. Ofcourse, at sufficiently high
temperatures, a competitive reaction or reversibility will emerge.
Multiple reactions, and reversible reactions, since these are special form of multiple
reactions, usually exhibit an optimal temperature with respect to the yield of a desired
product.
Example12:

Additional data

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 Reactor Design II-Fourth Year
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(–ΔHr) = 70000 J/mol; CP(stream) = 4.2 J/g.K : ρ(stream) = 1,000 gm/L;

Solution
The optimum temperature Topt is determined by Equation:

(1) The optimum temperature Topt is:

The minimum volume VR is determined by:

𝑋. 𝐹𝐴𝑜
𝑉=
(𝑟𝐴 ) 𝑜𝑝𝑡

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FAO = QoCAOTherefore, the volumetric flowrateQo is

(2) The minimum volume is determined by

𝑋. 𝐹𝐴𝑜
𝑉=
(𝑟𝐴 ) 𝑜𝑝𝑡

= 288.0 liter

3) The feed temperature TO for the adiabatic operation at theoptimal temperature Topt is
determined from

𝜃𝑖 𝐶𝑝 𝑖 (𝑇𝑜 − 𝑇𝑜𝑝𝑡 ) = − 𝑥. ∆𝐻𝑟

𝑥. ∆𝐻𝑟
𝑇𝑜 = 𝑇𝑜𝑝𝑡 −
𝜃𝑖 𝐶𝑝 𝑖
𝑇𝑜 = 278.3 𝐾 = 5.1 𝐶 𝑂

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Algorithm for isothermal reactors.(Source: Fogler, H. S. Elements of Chemical
Reaction Engineering

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Algorithm for nonisothermal CSTR design

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Homework Problems:

1 - An elementary second-order liquid-phase reaction occurs in a CSTR. The reactor has

a volume of 1200 L and is heated by a steam jacket.

The feed temperature is 27°C, and the flow rate is 30 L/min. The inlet concentrations of
A and B are 2 mol/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).

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

The constant k has units of mol (hrL.atm) −1. 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 10 mol of
steam for each mole of butene. The reactor pressure is 2 atm and the feed temperature is
650°C. Values of the rate constant at different temperatures are given in the following
table:

Assume that the heat of reaction is a constant 1.1 × 105 J/mol butene. The heat capacity
of the feed stream may be considered constant at 2.1 kJ/kg ⋅K.
a. Calculate the reactor volume for a 20% conversion of butene if the reactor is operated
isothermally at 650°C with a total inlet molar flow rate of11000 mol/h.
b. Determine the reactor volume for 20% conversion of butene for a total inlet molar
feed rate of 11000 mol/hr in an adiabatic reactor.

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3- The following reaction is carried out in an adiabatic plug flow reactor:

Calculate the maximum conversion that may be achieved if the feed enters at27°C. Only
A and B are in the feed. The following data are available:

4- A first-order endothermic reaction is carried out in a constant-volume batch reactor.

The enthalpy of reaction is 50,000 J/mol. The reactor volume is 1 m3 and contains1000
kg of mixture. There are initially 10,000 mol of reactant A in the reactor.
The reactor is heated to 400°C, during which time 10% of the initial A reacts. When the
temperature reaches 400°C, the reactor operates adiabatically. The heat capacity of the
mixture is a constant 2000 J/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?

5- A first-order liquid-phase exothermic reaction A → B 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 40°C by the addition of an inert coolant at a temperature of 25°C. The
flow rate of coolant varies with time so as to maintain the reactor temperature at 40°C.
The following data are available:

At time t = 0, only compound A is present in the tank at a concentration of8000 mol/m 3.

The initial volume is 1.5 m3.
a. Calculate the conversion of A 2 h after the start of the reaction.

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b. Calculate the rate of coolant addition 2 h after the start of the reaction.
c. Calculate the total amount of coolant added after 2 h.

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

phase reaction occurs
A + B → C (−rA ) = kCACB
The rate constant is independent of temperature and equals 0.01m3/mol ⋅ s.The initial
reactor temperature is 450 K and the pressure is 100 kPa. The initial volume of the
reactor is 1.0 m3. The reactor initially contains 30% by volume A,30% B, and 40%
inerts.The heat capacity of the mixture is a constant CV = 1000J/kg K. The average
molecular mass of the initial material is 30 g/mol. The internal energy change on
reaction is a constant ∆Hr= –60 kJ/mol. Calculate

a. The time required to reach 80% conversion

b. The reactor volume at 80% conversion
c. The reactor temperature at 80% conversion

7- Consider an adiabatic plug flow reactor in which a second-order ideal gas-phase

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

The concentrations are in mol/m3. The enthalpy of reaction at 298 K is equal to −50000
J/mol. The heat capacities are
A: 10 J/mol . K, B: 5 J/mol .K, C: 15 J/mol. K, and inert: 15 J/mol. K
The desired fractional conversion of A is 80%.
Calculate the reactor volume required.

8- The elementary, reversible gas phase reaction A⇋ B is to be carried out in a CSTR

with heat exchange. Pure A is fed to the reactor. The heat exchange coil in the reactor is
maintained at 400K. The rate coefficient is known at 400K, but heat of reaction is
unknown.

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A) Calculate the conversion (X) if the steady state CSTR is operated at 450K.
B) Calculate the heat removal rate R (T) at this temperature.
C) Calculate the heat of reaction (∆Hr).
9- A first-order, reversible reaction A⇋ B is taking place adiabatically. The equilibrium
constant at 400 K is 3 and the heat of reaction, which can be assumed constant, is –50
kJ/mole. Pure A with a specific heat of 100 J/mole-K (which is the same as that of B)
enters the reactor at 300 K. The equilibrium conversion as a function of temperature is
plotted in the figure shown below.
1.2

1
Equilibrium Conversion

0.8

0.6

0.4

0.2

0
300 350 400 450 500 550 600 650
Temperature

a. Show the equations that were used for constructing the plot shown.
b. What is the maximum conversion that can be achieved, if the reactor is operated
adiabatically?
c. If two adiabatic reactors are used, with inter-stage cooling, and if the first reactor exit
stream is cooled to 350 K, what maximum conversion can be achieved in the second
reactor? What would be the exit temperature from this second stage?

10 -A first-order irreversible liquid-phase reaction ( A  B ) is taking place in a CSTR .A

enters the reactor at 300 K at a concentration of 3 mol/liter. The reactor volume is 18
liters and flow rate of pure A is 0.06 liters/s. Other parameters are:

H Rx
0
 5000 cal/mole, C pA  C pB  30 cal/mole  K
7550 -1
k  exp(15.32  )s
T

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The heat generated term given by (H Rx  X ) is plotted in the figure shown
0

6000

5000
Heat Generation Function

4000

3000

2000

1000

0
250 300 350 400 450
Temperature (K)

1- For the conditions given, determine the number of steady states, and the
Conversions and temperatures at these steady states.
2- What is the minimum incoming temperature at which multiple steady states are
possible?
3- What is the maximum incoming temperature above which only one steady state
occurs?

11-Ascertain whether the following exothermic reaction: 2A ⇋2P (k1 and k1 at 80°C)
could be carried out in the reactor shown below:

Calculate the volume and heat removed from the CSTR and the PFR. Do the
magnitudes of the heat being removed appear feasible? Why or why not?
Data:

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12-The ester of an organic base is hydrolyzed in a CSTR. The rate of this irreversible
reaction is first-order in each reactant. The liquid volume in the vessel is 6500 L. A
jacket with coolant at 18°C maintains the reactant mixture at30°C. Additional data:

The average heat capacity is approximately constant at 1.0 kcal L-1 °c- 1
.
(a) What is the conversion of ester in the reactor?
(b) Calculate the rate at which energy must be removed to the jacket to maintain 30°C
in the reactor. If the heat transfer coefficient is 15 kcal/sec. m2 K, what is the necessary
heat transfer area?
(c) If the coolant supply fails, what would be the maximum temperature the reactor
could reach?

13-A reaction is carried out in an adiabatic CSTR with a volume of 10000 L.The feed
solution with reactant A, at a concentration of 5 M, is supplied at 10L/ s. The reaction is
first-order with rate constant:

(a) Calculate the reactor temperature and exit concentration for feed temperatures of
280, 300, and 320 K.
(b) To maintain the reactor temperature below 373 K, a well-mixed cooling jacket at
290 K is used. Show that it is possible to get 90 percent conversion in this reactor with a
feed temperature of 320 K.

14- The reversible, first-order reaction shown below takes place in a CSTR.

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(a) For a reactor space time of 10 min, what is the conversion for a 300 K operating
temperature? What is the conversion at 500 K? (Remember: the equilibrium constant
depends on temperature.)
(b) If the feed temperature is 330 K and the feed concentration is 5 M, what is the
necessary heat-removal rate per liter of reactor volume to maintain 300 K operating
temperature?

15- The reaction A + B ⇋ C + D is carried out adiabatically in a series of tubular

reactors with interstage cooling as shown in the figure below. The feed is equimolar in
A and B and enters each reactor at 27oC.
The heat removed between the reactors is -87.5kcal/min.
(a) What is the outlet temperature of the first reactor?
(b) What is the conversion of A at the outlet of the first reactor?
(c) Is the first reactor close to equilibrium at the exit?

State any assumptions that you make while solving the problem.
Data:

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16-A liquid phase exothermic reaction A →B is carried out at 358K in a 0.2 m3 CSTR.
The coolant temperature is 273K and the heat transfer coefficient (U) is 7200
J/min·m2·K. What is the heat exchange area required for steady state operation?

CPA =CPS=20 J/g•K CA0= 180 g/dm3 υ0= 500 dm3/min T0= 313 K
ρ= 900 g/dm3 ∆H°RX(T) = -2500 J/g E=94852 J/mol·Kk(313K)= 1.1 min-1
Answer: A=227.4 m2

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