CHEMICAL ENGINEERING PROBLEMS 175

dT 1
MCp Å WCpT 0
dT
(A.19)
/ UA(Tsteam 0 T 1 ) 0 WCpT 1

Figure A.2 Series of tanks for oil heating. Note that the unsteady-state mass balance is not
needed for Tank 1 or any other tank, since the mass
in each tank does not change with time. The above
Problem 6: Heat Exchange differential equation can be rearranged and explic-
in a Series of Tanks itly solved for the derivative which is the usual
format for numerical solution.
Numerical Methods. Solution of simultaneous
first-order ordinary differential equations.
dT 1
Å [WCp (T 0 0 T 1 )
Concepts Used. Unsteady-state energy balances, dt
(A.20)
dynamic response of well-mixed heated tanks in / UA(Tsteam 0 T 1 )]/(MCp )
series.
Similarly, for the second tank
Course Usage. Heat Transfer.
dT 2
Å [WCp (T 1 0 T 2 )
Problem Statement. Three tanks in series are used dt
to preheat a multicomponent oil solution before it (A.21)
is fed to a distillation column for separation, as / UA(Tsteam 0 T 2 )]/(MCp )
shown in Figure (A.2). Each tank is initially filled
with 1000 kg of oil at 20!C. Saturated steam at a For the third tank,
temperature of 250!C condenses within coils im-
mersed in each tank. The oil is fed into the first dT 3
Å [WCp (T 2 0 T 3 )
tank at the rate of 100 kg/min and overflows into dt
(A.22)
the second and the third tanks at the same flow rate. / UA(Tsteam 0 T 3 )]/(MCp )
The temperature of the oil fed to the first tank is
20!C. The tanks are well mixed so that the tempera- Determine the steady-state temperatures in all three
ture inside the tanks is uniform, and the outlet tanks. What time interval will be required for T3 to
stream temperature is the temperature within the reach 99% of this steady-state value during startup?
tank. The heat capacity, Cp , of the oil is 2.0 kJ/kg.
For a particular tank, the rate at which heat is trans-
ferred to the oil from the steam coil is given by the Problem 7: Diffusion with Chemical
expression Reaction in a One-Dimensional Slab
Numerical Methods. Solution of second-order or-
Q Å UA(Tsteam 0 T) (A.18) dinary differential equations with two point bound-
ary conditions.
where UA Å 10 kJ min 01 !C 01 is the product of the
heat transfer coefficient and the area of the coil for Concepts Used. Methods for solving second-order
each tank, T is the temperature of the oil in the tank ordinary differential equations with two point
( !C), and Q is the rate of heat transferred in kJ/min. boundary values typically used in transport phenom-
Energy balances can be made on each of the ena and reaction kinetics.
individual tanks. In these balances, the mass flow
rate to each tank will remain at the same fixed value. Course Usage. Transport Phenomena and Reaction
Thus, W Å W1 Å W2 Å W3 . The mass in each tank Engineering.
will be assumed constant, as the tank volume and
oil density are assumed to be constant. Thus, M Å Problem Statement. The diffusion and simultane-
M1 Å M2 Å M3 . For the first tank, the energy balance ous first-order irreversible chemical reaction in a
can be expressed by single phase containing only Reactant A and Product
B results in a second-order ordinary differential
Accumulation Å Input 0 Output equation given by

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176 CUTLIP ET AL.

d 2CA k Course Usage. Separation Processes.

2
Å CA (A.23)
dz DAB
Problem Statement. For a binary batch distillation
process involving two components designated 1 and
where CA is the concentration of Reactant A (kg
2, the moles of liquid remaining, L, as a function
mol m03 ); z is the distance variable (m); k is the
of the molar fraction of the component 2, x2 , can
homogeneous reaction rate constant (s 01 ); and DAB
be expressed by the following equation:
is the binary diffusion coefficient (m2 /s). A typical
geometry for Equation (A.23) is that of a one-di-
mensional layer which has its surface exposed to a dL L
Å (A.27)
known concentration and allows no diffusion across dx2 x2 (k2 0 1)
its bottom surface. Thus, the initial and boundary
conditions are where k2 is the vapor liquid equilibrium ratio for
Component 2. If the system may be considered
CA Å CA 0 ideal, the vapor liquid equilibrium ratio can be cal-
for zÅ0 (A.24)
culated from ki Å Pi /P, where Pi is the vapor pres-
sure of component i, and P is the total pressure.
dCA A common vapor pressure model is the Antoine
Å0 for zÅL (A.25)
dz equation, which uses three parameters, A, B, and
C, for component i, as given below, where T is the
temperature ( !C).
where CA 0 is the constant concentration at the sur-
face (z Å 0) and there is no transport across the
bottom surface (z Å L), so the derivative is zero. Pi Å 10[ A0 ( B / T/C ) ] (A.28)
This differential equation has an analytical solu-
tion given by The temperature in the batch still follows the
bubble point curve. The bubble point temperature
! is defined by the implicit algebraic equation which
cosh[L( k/DAB )(1 0 z/L)] can be written using the vapor liquid equilibrium
C A Å CA 0 ! (A.26)
cosh(L k/DAB ) ratios as

1. Numerically solve Equation (A.23) with the k1 x1 / k2 x2 Å 1 (A.29)

boundary conditions of Equations (A.24) and
(A.25) for the case where CA0 Å 0.2 kg mol Consider a binary mixture of benzene (Compo-
m03 , k Å 10 03 s 01 , DAB Å 1.2 10 09 m2 /s, and nent 1) and toluene (Component 2) which is to be
L Å 10 03 m. This solution should utilize an considered as ideal. The Antoine equation constants
ODE solver with a shooting technique and for benzene are A1 Å 6.90565, B1 Å 1211.033, and
employ Newton’s method or some other tech- C1 Å 220.79. For toluene, A2 Å 6.95464, B2 Å
nique for converging on the boundary condi- 1344.8, and C2 Å 219.482 (Dean [1]). P is the
tion given by Equation (A.25). pressure (mmHg) and T the temperature ( !C).
2. Compare the concentration profiles over the
thickness as predicted by the numerical solu- The batch distillation of benzene (Component 1)
tion of part 1 with the analytical solution of and toluene (Component 2) mixture is being carried
Equation (A.26). out at a pressure of 1.2 atm. Initially, there is 100
mol of liquid in the still, composed of 60% benzene
and 40% toluene (molar fraction basis). Calculate
Problem 8: Binary Batch Distillation the amount of liquid remaining in the still when the
concentration of toluene reaches 80%.
Numerical Methods. Solution of a system of equa-
tions comprised of ordinary differential equations
and nonlinear algebraic equations. Problem 9: Reversible, Exothermic,
Gas-Phase Reaction in a Catalytic Reactor
Concepts Used. Batch distillation of an ideal binary Numerical Methods. Simultaneous ordinary differ-
mixture. ential equations with known initial conditions.

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 CHEMICAL ENGINEERING PROBLEMS 177

The simple catalytic reaction rate expression for

this reversible reaction is

!
0r "A Å k C 2A 0
CC
KC " (A.31)

where the rate constant is based on Reactant A and

follows the Arrhenius expression
Figure A.3 Packed bed catalytic reactor.

Concepts Used. Design of a gas-phase catalytic re-

k Å (k at T Å 450! K)exp !
EA 1
0
R 450 T
1
" (A.32)

actor with pressure drop for a reversible gas-phase

reaction. and the equilibrium constant variation with tempera-
ture can be determined from van’t Hoff’s equation
with DC̃P Å 0
Course Usage. Reaction Engineering.
KC Å (KC at T Å 450! K)

! "
Problem Statement. The elementary gas phase re- (A.33)
DHR 1 1
action 2A S C is carried out in a packed bed reactor. 1 exp 0
There is a heat exchanger surrounding the reactor, R 450 T
and there is a pressure drop along the length of the
reactor (Fig. A.3). The stoichiometry for 2A S C and the stoichio-
The various parameters values for this reactor metric table for a gas allow the concentrations to
design problem are summarized in Table A.2. be expressed as a function of conversion and tem-
perature while allowing for volumetric changes due
to decrease in moles during the reaction. Therefore,
1. Plot the conversion (X), reduced pressure

# $
(y), and temperature (T 1 10 03 ) along the
reactor from W Å 0 kg up to W Å 20 kg. 10X P T0
CA Å CA 0
2. Around 16 kg of catalyst, you will observe a 1 / 1X P0 T
‘‘knee’’ in the conversion profile. Explain why

# $
(A.34)
this knee occurs and what parameters affect it. 10X T0
3. Plot the concentration profiles for Reactant Å CA 0 y
1 0 0.5X T
A and Product C from W Å 0 kg up to W Å
20 kg.
and

Additional Information. The notation used here

and the following equations and relationships for Table A.2 Parameter Values for Problem 8
this particular problem are adapted from the text- CPA Å 40.0 J g01 mol01 K01
book by Fogler [2]. The problem is to be worked CPC Å 80.0 J g01 mol01 K01
assuming plug flow with no radial gradients of con- DHR Å 040,000 J g01 mol01 K01
centrations and temperature at any location within EA Å 41,800 J g01 mol01 K01
the catalyst bed. The reactor design will use the k Å 0.5 dm6 kg01 min01 mol01 at 450 K
conversion of A designated by X and the tempera- KC Å 25,000 dm3 g01 mol01 at 450 K
ture T, which are both functions of location within CA0 Å 0.271 g mol dm03
the catalyst bed specified by the catalyst weight W. T0 Å 450 K
The general reactor design expression for a cata- R Å 8.314 J g01 mol01 K01
FA0 Å 5.0 g mol min01
lytic reaction in terms of conversion is a molar bal-
Ua Å 0.8 J kg01 min01 K01
ance on Reactant A given by Ta Å 500 K
a Å 0.015 kg01
dX P0 Å 10 atm
FA 0 Å 0r "A (A.30) yA0 Å 1.0 (Pure A feed)
dW

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178 CUTLIP ET AL.

P
yÅ
P0

CC Å # 0.5CA 0 X
1 0 0.5X $y
T0
T
(A.35)

The pressure drop can be expressed as a differen-

tial equation (see Fogler [2] for details)

d# $P
P0
Å
0 a(1 / 1 X) P0 T
(A.36) Figure A.4 Well-mixed tank with heater and tempera-
dW 2 P T0 ture controller.

or
measured by a thermocouple as Tm ( !C), and the
dy 0 a(1 0 0.5X) T required heater input q (kJ/min) is adjusted by a
Å (A.37)
dW 2y T0 PI temperature controller. The control objective is
to maintain T 0 Å Tr in the presence of a change in
The general energy balance may be written as inlet temperature Ti , which differs from the steady-
state design temperature of Tis .
dT Ua (Ta 0 T) / r "A ( DHR )
Å (A.38) Modeling and Control Equations. An energy bal-
dW FA 0 ( ! ui CPi / XDC̃P )
ance on the stirred tank yields
which for only Reactant A in the reactor feed simpli-
fies to dT WCp (Ti 0 T) / q
Å (A.40)
dt rVCp
dT Ua (Ta 0 T) / r "A ( DHR )
Å (A.39)
dW FA 0 (CPA ) with initial condition T Å Tr at t Å 0, which corre-
sponds to steady-state operation at the set point tem-
perature Tr .
Problem 10: Dynamics of a Heated Tank The thermocouple for temperature sensing in the
with Proportional/Integral (PI) outlet stream is described by a first-order system
Temperature Control plus the dead time td , which is the time for the
Numerical Methods. Solution of ordinary differen- output flow to reach the measurement point. The
tial equations, generation of step functions, simula- dead time expression is given by
tion of a proportional integral controller.
T 0 (t) Å T(t 0 td ) (A.41)
Concepts Used. Closed-loop dynamics of a process
including first-order lag and dead time. Padé ap- The effect of dead time may be calculated for this
proximation of time delay. situation by the Padé approximation, which is a first-
order differential equation for the measured temper-
Course Usage. Process Dynamics and Control. ature.

Problem Statement. A continuous process system

consisting of a well-stirred tank, heater and PI tem-
perature controller is depicted in Figure (A.4). The
dT 0
dt
Å ! T 0 T0 0 # $# $"
td
2
dT
dt
2
td
I. C.
(A.42)
feed stream of liquid with density of r (kg/m 3 ) and
heat capacity of C (kJ kg 01 !C 01 ) flows into the T 0 Å Tr at t Å 0 (steady state)
heated tank at a constant rate of W (kg/min) and
temperature Ti ( !C). The volume of the tank is V The above equation is used to generated the temper-
(m3 ). It is desired to heat this stream to a higher set ature input to the thermocouple, T 0 .
point temperature Tr ( !C). The outlet temperature is The thermocouple shielding and electronics are

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 CHEMICAL ENGINEERING PROBLEMS 179

modeled by a first-order system for the input tem- Table A.3 Baseline System and Control Parameters
perature T 0 given by for Problem 10
rVCp Å 4000 kJ/!C WCp Å 500 kJ min01 !C01
Tis Å 60!C Tr Å 80!C
dTm T 0 0 Tm
Å td Å 1 min tm Å 5 min
dt tm Kc Å 50 kJ min01 !C01 tI Å 2 min
(A.43)
I. C. Tm Å Tr at t Å 0 (steady state)
the system and control parameters in Table A.3 will
be considered as leading to baseline steady-state
where the thermocouple time constant tm is known. operation.
The energy input to the tank, q, as manipulated
by the PI controller can be described by 1. Demonstrate the open-loop performance (set
Kc Å 0) of this system when the system is
initially operating at design steady state at a
q Å qs / Kc (Tr 0 Tm ) temperature of 80!C, and inlet temperature Ti
is suddenly changed to 40!C at time t Å 10
(A.44)
Kc min. Plot the temperatures T, T0 , and Tm to
/
" (T 0 T )dt
t
steady state, and verify that Padé approxima-
tI r m
tion for 1 min of dead time given in Equation
0
(A.42) is working properly.
2. Demonstrate the closed-loop performance of
where Kc is the proportional gain of the controller, the system for the conditions of part 1 and
and tI is the integral time constant or reset time. the baseline parameters from Table A.3. Plot
The qs in the above equation is the energy input temperatures T, T0 , and Tm to steady state.
required at steady state for the design conditions as 3. Repeat part 2 with Kc Å 500 kJ min 01 !C 01 .
calculated by 4. Repeat part 3 for proportional-only control
action by setting the term Kc / tI Å 0.
5. Implement limits on q [as per Eq. (A.47)] so
qs Å WCp (Tr 0 Tis ) (A.45) that the maximum is 2.6 times the baseline
steady-state value and the minimum is zero.
The integral in Equation (A.44) can be conveniently Demonstrate the system response from base-
calculated by defining a new variable as line steady state for a proportional only con-
troller when the set point is changed from
80!C to 90!C at t Å 10 min. Kc Å 5000 kJ
d min 01 !C 01 . Plot q and qlim versus time to
(errsum) Å Tr 0 Tm steady state to demonstrate the limits. Also,
dt
plot the temperatures T, T0 , and Tm to steady
I. C. errsum Å 0 at state to indicate controller performance.
(A.46)
t Å 0 (steady state) REFERENCES
[1] A. Dean, Ed. Lange’s Handbook of Chemistry.
McGraw-Hill, New York, 1973.
Thus, Equation (A.44) becomes [2] H. S. Fogler, Elements of Chemical Reaction Engi-
neering, 2nd Ed. Prentice Hall, Englewood Cliffs,
NJ, 1992.
Kc
q Å qs / Kc (Tr 0 Tm ) / (errsum) (A.47) [3] R. H. Perry, D. W. Green, and J. D. Malorey, Eds.
tI Perry’s Chemical Engineers Handbook. McGraw-
Hill, New York, 1984.
[4] M. Shacham, N. Brauner, and M. Pozin, ‘‘Compar-
Let us consider some of the interesting aspects of ing Software for Interactive Solution of Systems of
this system as it responds to a variety of parameter Nonlinear Algebraic Equations,’’ Comput. Chem.
and operational changes. The numerical values of Eng., Vol. 20 (Suppl.), 1996, pp. S1329–S1334.

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