EXAMPLES OF MATHEMATICAL MODELS OF CHEMICAL ENGINEERING SYSTEMS 77

The method involves a simple iteration on only one variable, pH. Simple
interval-halving convergence (see Chap. 4) can be used very effectively. The titra-
tion curves can be easily converted into simple functions to include in the com-
puter program. For example, straight-line sections can be used to interpolate
between data points.
This method has been applied with good success to a number of pH pro-
cesses by Schnelle (Schnelle and Luyben, Proceedings of ISA 88, Houston,
October 1988).

PROBLEMS
3.1. A fluid of constant density p is pumped into a cone-shaped tank of total volume
HxR2/3. The flow out of the bottom of the tank is proportional to the square root of
the height h of liquid in the tank. Derive the equations describing the system.

F=K&- FIGURE P3.1

3.2. A perfect gas with molecular weight M flows at a mass flow rate W, into a cylinder
through a restriction. The flow rate is proportional to the square root of the pressure
drop over the restriction:
W, = K,,,/m

where P is the pressure in the cylinder and P, is the constant upstream pressure. The
system is isothermal. Inside the cylinder, a piston is forced to the right as the pres-
sure P builds up. A spring resists the movement of the piston with a force that is
proportional to the axial displacement x of the piston.
F, = K,x

PO
Pressure on the spring
side of the piston is
atmospheric.
W0-

FIGURE P3.2
 78 MATHEMATICAL MODELS OF CHEMICAL ENGINEERING SYSTEMS

The piston is initially at x = 0 when the pressure in the cylinder is zero. The cross-
sectional area of the cylinder is A. Assume the piston has negligible mass and fric-
tion.
(a) Derive the equations describing the system.
b) What will the steadystate piston displacement be?
3.3. perfectly mixed, isothermal CSTR has an outlet weir. The flow rate over the weir
as proportional to the height of liquid over the weir, h,,, to the 1.5 power. The weir
height is h, . The cross-sectional area of the tank is A. Assume constant density.
A first-order reaction takes place in the tank:
k
A - B
Derive the equations describing the system.

V t
CA hw

FIGURE P3.3

3.4. In order to ensure an adequate supply for the upcoming set-to with the Hatfields,
Grandpa McCoy has begun to process a new batch of his famous Liquid Lightning
moonshine. He begins by pumping the mash at a constant rate F, into an empty
tank. In this tank the ethanol undergoes a first-order reaction to form a product that
is the source of the high potency of McCoy’s Liquid Lightning. Assuming that the
concentration of ethanol in the feed, C,, is constant and that the operation is iso-
thermal, derive the equations that describe how the concentration C of ethanol in
the tank and the volume V of liquid in the tank vary with time. Assume perfect
mixing and constant density.
35. A rotating-metal-drum heat exchanger is half submerged in a cool stream, with its
other half in a hot stream. The drum rotates at a constant angular velocity w

TH
Hot temp

FIGURE P3.5
 EXAMPLES OF MATHEMATICAL MODELS OF CHEMICAL ENGINEERING SYSTEMS 79

(radians per minute). Assume TH and T, are constant along their respective sections
of the circumference. The drum length is L, thickness d, and radius R. Heat transfer
coefficients in the heating and cooling zones are constant (U, and U,). Heat capac-
ity C, and density of the metal drum are constant. Neglect radial temperature gra-
dients and assume steadystate operation.
(a) Write the equations describing the system.
(b) What are the appropriate boundary conditions?
3.6. nsider the system that has two stirred chemical reactors separated by a plug-flow
adtime of D seconds. Assume constant holdups (VI and V,), constant throughput
0
(F), constant density, isothermal operation at temperatures Tl and T2, and first-
order kinetics with simultaneous reactions:
h kz
A - B A - C
No reaction occurs in the plug-flow section.
Write the equations describing the system.

FIGURE P3.6

3.7. Consider the isothermal hydraulic system sketched below. A slightly compressible
polymer liquid is pumped by a constant-speed, positive displacement pump so that
the mass flow rate WI is constant. Liquid density is given by
P = PO + w - PO)
where p. , fl, and PO are constants, p is the density, and P is the pressure.
Liquid is pumped through three resistances where the pressure drop is pro-
portional to the square of the mass flow: AP = RWZ. A surge tank of volume V is
located between R, and R, and is liquid full. The pressure downstream of R, is
atmospheric.
(a) Derive the differential equation that gives the pressure P in the tank as a func-
tion of time and WI.
(b) Find the steadystate value of tank pressure P.

Pump

FIGURE P3.7

3.& Develop the equations describing an “inverted” batch distillation column. This
system has a large reflux drum into which the feed is charged. This material is fed to
the top of the distillation column (which acts like a stripper). Vapor is generated in a
reboiler in the base. Heavy material is withdrawn from the bottom of the column.
Derive a mathematical model of this batch distillation system for the case
where the tray holdups cannot be neglected.
 80 MATHEMATICAL MODELS OF CHEMICAL ENGINEERING SYSTJMS

3.9. An ice cube is dropped into a hot, perfectly mixed, insulated cup of coffee. Develop
the equations describing the dynamics of the system. List all assumptions and define

3.10. nterms.
6’ rsothermal, irreversible reaction

L// A
k
- B

J takes place in the liquid phase in a constant-volume reactor. The mixing is not
perfect. Observation of flow patterns indicates that a two-tank system with back
mixing, as shown in the sketch below, should approximate the imperfect mixing.
Assuming F and F, are constant, write the equations describing the system.

FIGURE P3.10

3.11.
he liquid in a jacketed, nonisothermal CSTR is stirred by an agitator whose mass is
ignificant compared with the reaction mass. The mass of the reactor wall and the
Qmass of the jacket wall are also significant. Write the energy equations for the
system. Neglect radial temperature gradients in the agitator, reactor wall, and jacket
wall.
reaction 3A + 2B + C is carried out in an isothermal semibatch reactor.
B is the desired product. Product C is a very volatile by-product that must
be vented off to prevent a pressure buildup in the reactor. Gaseous C is vented off
through a condenser to force any A and B back into the reactor to prevent loss of
reactant and product.
Assume F, is pure C. The reaction is first-order in CA. The relative volatilities
of A and C to B are aAB = 1.2 and am = 10. Assume perfect gases and constant
pressure. Write the equations describing the system. List all assumptions.

FIGURE P3.12

the equations describing a simple version of the petroleum industry’s impor-

cracking operation. There are two vessels as shown in Fig. P3.13.
is fed to the reactor where it reacts to form product B while depos-
 EXAMPLES OF MATHEMATICAL MODELS OF CHEMICAL ENGINEERING SYSTEMS 81

iting component C on the solid fluidized catalyst.

A + B + O.lC
Spent catalyst is circulated to the regenerator where air is added to burn off C.
C+O+P
Combustion products are vented overhead, and regenerated catalyst is returned to
the reactor. Heat is added to or removed from the regenerator at a rate Q.
Your dynamic mathematical model should be based on the following assump-
tions :

(1) The perfect-gas law is obeyed in both vessels.

(2) Constant pressure is maintained in both vessels.
(3) Catalyst holdups in the reactor and in the regenerator are constant.
(4) Heat capacities of reactants and products are equal and constant in each vessel.
Catalyst heat capacity is also constant.
(5) Complete mixing occurs in each vessel.

Product Stack gas

Reactor Rqwrrator
- - - - - - ,------
,------

_------
__----
__-----
_-----
_------
__----
__-----
_-----
_------

Air

Reactor reaction: A9 B+ A C 1

Regenerator reaction: C +O? P

FIGURE P3.13

3.14. Flooded condensers and flooded reboilers are sometimes used on distillation
columns. In the sketch below, a liquid level is held in the condenser, covering some
of the tubes. Thus a variable amount of heat transfer area is available to condense
the vapor. Column pressure can be controlled by changing the distillate (or reflux)
drawoff rate.
Write the equations describing the dynamics of the condenser.
82 MATHEMATICAL MODELS OF CHEMICAL ENGINEERING SYSTEMS

Cooling
water

shoe?l

FIGURE P3.14

3.15. When cooling jackets and internal cooling coils do not give enough heat transfer
area, a circulating cooling system is sometimes used. Process fluid from the reactor is
pumped through an external heat exchanger and back into the reactor. Cooling
water is added to the shell side of the heat exchanger at a rate F, as set by the
temperature controller. The circulation rate through the heat exchanger is constant.
Assume that the shell side of the exchanger can be represented by two perfectly
mixed “lumps” in series and that the process fluid flows countercurrent to the water
flow, also through two perfectly mixed stages.
The reaction is irreversible and fist-order in reactant A:
k
A - B

The contents of the tank are perfectly mixed. Neglect reactor and heat-exchanger
metal.
Derive a dynamic mathematical model of this system.

CA
T
FIGURE P3.15