Process Modeling &

Simulation

Chapter 3:
Mathematic Models of Chemical
Engineering System

Chemical Engineering System

1. Series of Isothermal, Constant- Holdup
CSTRs
2. CSTRs with Variable Holdups
3. Two Heated Tanks
4. Gas-phase, Pressurized CSTR
5. Nonisothermal CSTR
6. Single-Component Vaporizer
7. Multicomponent Flash Drum
8. Batch Reactor
9. Reactor with Mass Transfer
10.Ideal Binary Distillation Column
11. Batch Distillation Column

1. SERIES OF ISOTHERMAL, CONSTANT-HOLDUP

CSTRs

-r= kCA

Product B is produced and reactant A is consumed.

A first-order reaction occurring in the liquid.
Assume that the temperatures and holdups (volumes) of the three
tanks can be different, but both temperatures and the liquid volumes are
assumed to be constant (isothermal and constant holdup).
Density is assumed constant throughout the system, which is a binary
mixture of A and B.

Thus the TCE for the first reactor is;

Likewise total mass balances on tanks 2 and 3 give

Where F is defined as the throughput (m 3/min)
CCE for reactant A;

 The specific reaction rates k, are given by the

Arrhenius equation

If the temperatures in the reactors are different, the ks are

different. The n refers to the stage number.
The volumes V, can be pulled out of the time derivatives
because they are constant. The flows are all equal to F but
can vary with time.
An energy equation is not required because we have
assumed isothermal operation. Any heat addition or heat
removal required to keep the reactors at constant
temperatures could be calculated from a steady state energy
balance (zero time derivatives of temperature).

The three first-order nonlinear ordinary differential

equations given in Eqs. (3.3) are the mathematical model
of the system.
The parameters that must be known are V1, V2 , V3, kl, k2,
and k3, .
The variables that must be specified before these
equations can be solved are F and CA,. Specified does
not mean that they must be constant. They can be timevarying, but they must be known or given functions of
time. They are the forcing functions.
The initial conditions of the three concentrations (their
values at time equal zero) must also be known.

If the throughput F is constant and the holdups and

temperatures are the same in all three tanks, Eqs. (3.3)
become

Where
with units of minutes. There is only one
forcing function or input variable, CA0

EXAMPLE:
Consider a system with 3 CSTRs in series previously
discussed. Given are;

Simulate the concentration profile of this reaction system

with step size, t = 0.1 min starting at t=0min to t=0.5min
by using explicit Euler method. (State your calculation
value to 3 decimal places)

Answer
TIME
(MIN)

CA1

CA2

CA3

0.000
0.100
0.200
0.300
0.400
0.500

0.400
0.450
0.495
0.536
0.572
0.605

0.200
0.200
0.203
0.207
0.213
0.220

0.100
0.100
0.100
0.100
0.100
0.101

2. CSTRs WITH VARIABLE HOLDUPS

If the previous example is modified slightly to permit the volumes in
each reactor to vary with time, both total and component continuity
equations are required for each reactor. To show the effects of higherorder kinetics, assume the reaction is now nth-order in reactant A.

Our mathematical model now contains six first-order nonlinear ordinary

differential equations.
Parameters that must be known are k1, k2, k3, and n.
Initial conditions for all the dependent variables that are to be integrated must be
given: CA1, CA2, CA3, VI, V2, and V3.
The forcing functions CAo(t) and Fo(t), must also be given.
Let us now check the degrees of freedom of this system.
There are six equations. But there are nine unknowns: CA1,CA2,CA3,VI,
V2,V3,F1, F2 and F3
Clearly this system is not sufficiently specified and a solution could not be
obtained.

What have we missed in our

modeling?
A good plant operator could take one look at the system and see what
the problem is.
We have not specified how the flows out of the tanks are to be set.
Physically there would probably be control valves in the outlet lines to
regulate the flows.
How are these control valves to be set? A common configuration is to
have the level in the tank controlled by the outflow, i.e., a level
controller opens the control valve on the exit line to increase the
outflow if the level in the tank increases. Thus there must be a
relationship between tank holdup and flow.
The f functions will describe the level controller and the control valve.
These three equations reduce the degrees of freedom to zero.

3. TWO HEATED TANKS

Let us consider a process in which two energy balances are needed to
model the system.
The flow rate F of oil passing through two perfectly mixed tanks in
series is constant at 90 ft3/min. The density p of the oil is constant at
40 lbm/ft3, and its heat capacity Cp, is 0.6 Btu/lbm.F. The volume of the
first tank V1, is constant at 450 ft3, and the volume of the second tank
V2, is constant at 90 ft3. The temperature of the oil entering the first
tank is To, and is 150F at the initial steady state. The temperatures in
the two tanks are T1 and T2.
They are both equal to 250F at the initial steady state. A heating coil
in the first tank uses steam to heat the oil. Let Q1 be the heat addition
rate in the first tank.
There is one energy balance for each tank.

 Since the throughput is constant FO = F1 = F2 = F.

Since volumes, densities, and heat capacities are all constant, Eqs.
(3.10) and (3.11) can be simplified

Lets check the degrees of freedom of

this system.
The parameter values that are known are p, Cp, V1, V2, and F. The heat input to
the first tank Q1 would be set by the position of the control valve in the steam line.
Thus we are left with two dependent variables, T1 and T2, and we have two
equations. So the system is correctly specified.

TUTORIAL
Please refer handout.
1.Final Exam Oct 2004
2.Q2, Final Exam April 2011

ANSWER Q1
t(min)
0
1
2
3
4

T1
(C)
28
28.493
3
28.919
8
29.288
4
29.607
1

dT1/dt T2(C) dT2/dt

0.4933
28
0.4265 28.493
3
0.3686 28.985
5
0.3187 29.467
9
0.2755 29.934
0

0.4933
0.4922
0.4824
0.4661
0.4454

4. GAS-PHASE PRESSURIZED CSTR

-r1= k1CA1.5
-r2= k2CB

Assume :
Isothermal system, T = constant
System volume, V constant
Perfect gases apply

Page 37

d (dV )
around the vessel gives:
Vtotal mass

fFfbalance
oFooF
fF
f
o
dt

5. NONISOTHERMAL CSTR

A: PERFECTLY MIXED COOLING JACKET

Tutorial (Q5, Final Exam April 2008)

Refer handout given..
T

CA

TJ

f(T)

530.00

0.0302

0.5308

530.00

530.59

530.59

0.0311

0.5302

530.55

531.13

537.30

0.0444

0.5222

536.74

537.34

537.81

0.0456

0.5215

537.21

537.81

B: PLUG FLOW COOLING JACKET

Plug Flow: constant velocity of flow in every part of a system.

C: LUMPED JACKET MODEL

D: SIGNIFICANT METAL WALL CAPACITANCE

- Mass of metal walls and its effects on the thermal
dynamics must be considered.

Tutorial
Handout
Q3, Final Exam, Oct 2008
An endothermic reaction of reactant X to product Y is
carried out in
jacketed reactor. The reaction.

STEADYSTATE
MODEL
LIQUID-PHASE
DYNAMICS MODEL

LIQUID AND VAPOR

DYNAMICS MODEL
THERMAL
EQUILIBRIUM MODEL

SINGLE-COMPONENT
VAPORIZER
To describe these boiling systems
rigorously, conservation equations for
both the vapor and liquid phases are
needed.
The basic problem is finding the rate of
vaporization of material from the liquid
phase into the vapor phase.

 Let consider Liquefied petroleum gas

(LPG) vaporizer system.
Gas is drawn off

The liquid in
the tank is
assumed
perfectly
mixed
LPG is fed into a
pressurized tank to hold
the liquid level in the
tank. Assume LPG is a
pure component:
propane

the top of the tank

at a volumetric
flow rate, Fv
(forcing functions).
Heat losses and
the mass of the
walls are assumed
negligible
Heat is added at a
rate, Q to hold the
desired pressure in
the tank by
vaporizing the
liquid at a rate, Wv
(mass per time).

A. STEADYSTATE MODEL
The simplest model would neglect the
dynamics of both vapor and liquid
phases and relate the gas rate, Fv to the
heat input by:
v Fv ( H v h0 ) Q
where, H v enthalpy of vapor leaving tank(Btu/lb m or cal/g)
h0 enthalpy of liquid feed(Btu/lb m or cal/g)

B. LIQUID-PHASE DYNAMICS
MODEL
More realistic model is obtained if
assume that the volume of the vapor
phase is small enough to make its
dynamics negligible.
If only a few moles of liquid have to be
vaporized to change the pressure in the
vapor phase.
So, we can assume that this pressure
is always equal to the vapor pressure of
the liquid at any temperature (P = Pv

 (1) A total continuity equations

for the liquid phase,
Total continuity :
dVL

o Fo v Fv
dt

(2&3) The two controller

equations relating pressure to heat
input and the liquid level to feed
flow rate,QF0 falso needed.
F f
1( P )

2 (VL )

 (4) An energy equation for liquid

phase gives the
function of time).

temperature

(as

The liquid is assumed incompressible

so, Cp = Cv and internal energy, U is CpT.
The enthalpy of the vapor leaving the
vaporizer
is assumed to be simple form :
Energy
:
CpT +d(vV. T )
L
Cp
oC p FoTo v Fv (C pT v ) Q
dt

 (5) An equation of state for the vapor

is needed to be able to calculate density,
v from the pressure or temperature. The
perfect gases is
used.
State
:
MP
v
RT

(6) The vapor pressure relationship

gives the pressure in the vaporizer at
Vapor pressure :
that temperature
A
ln P
B
T

 From the system, we have 6

equations.
Unknown variables are Q, F0 , P,
VL , v and T.
Degree of freedom , 6-6 = 0.

C. LIQUID AND VAPOR

DYNAMICS MODEL

For the cases, if the dynamics

of the vapor phase cannot be
neglected (if we have a large
volume of vapor).
Total continuity and energy
equations for the gas in the tank
is needed.

 The expression for boiling rate, Wv in

term of pressure differential as driving
force
Wv K MT ( P Pv )
K MT is the pseudo mass transfer coefficient.

At some temperature, liquid boils

because it exerts a vapor pressure P
greater than the pressure Pv in the
vapor phase above it.
At equilibrium, P = Pv. If liquid and
vapor are in equilibrium, KMT is very

 Equations describing the system for

liquid phase:
Total Continuity :
dVL

o Fo Wv
dt
Energy :
d (VLU L )

o Fo ho Wv H L Q
dt
Vapor pressure :
P e A/T B
where, U L internal energy of liquid at temperature T
H L enthalpy of vapor boiling off liquid

 Equations describing the system for

vapor Total
phase:
Continuity :
d ( vVv )
Wv v Fv
dt
Energy :
d (Vv vU v )
Wv H L v Fv H v
dt
State :
MPv
v
RTv
where, U L internal energy of liquid at temperature T
H L enthalpy of vapor boiling off liquid
U v internal energy of vapor at temperature Tv
H v enthalpy of vapor phase

The systems have 10 variables.

Q, F0 ,VL ,Wv , T, Vv , v Tv , P and Pv
Equations: 10 equations
Liquid phase = 3
Vapor phase = 3
Boiling rate = 1
Controller equation = 2
total volume (VL + Vv) of tank = 1
Degree of freedom = 0

D. THERMAL EQUILIBRIUM
MODEL
For this case,
thermal equilibrium
between liquid and vapor is assumed to
hold at all times.
The vapor and liquid temperatures are
assumed equal to each other, T = Tv .
Eliminates the need for an energy
balance for the vapor phase. ~ sensible
heat of vapor is usually small compared
with latent heat effects.

d (VLT )
Cp
o FoC pTo Wv (C pT v ) Q
The simple
dt enthalpy relationships can be
used,

Tutorial (Final Exam, April 2007)

LPG is feed into a pressurized tank to hold the liquid
level in the tank. The pressure in the tank is maintained
by vaporising the liquid at a rate Wv(mass/time), and this
is done by adding heat at a rate Q. Heat losses and the
mass of the tank walls are assumed negligible. Gas is
drawn off the top of the tank at a volumetric flow rate, Fv.
The volume of the vapor is large and the rate of the
vaporization Wv is given as;
Wv=KMT (P-Pv)
given that KMT is the pseudo mass transfer coefficient. By
referring Figure 1, derive the equations that described the
behaviour of this single component vaporiser.

STEADYSTATE
MODEL

PRACTICAL MODEL
RIGOROUS MODEL

MULTICOMPONENT FLASH
DRUM
System for vapor-liquid with more than
one component.

If drum P < bubblepoint

P of feed at T0, some of
liquid will vaporize.
Liquid stream
at high T & P
flashed into a
drum

P0 is high
enough to
prevent any
vaporization
of feed at T0
and x0j

P is reduced
as it flows
through
restriction
(valve)

This expansion is
irreversible and occurs
at constant enthalpy

Gas is drawn off

through a control
valve whose steam
position is set by P
controller

Adiabatic conditions are

assumed (no heat
losses)

Liquid comes
off the bottom
of tank on level
controller

 The forcing functions in this system are

feed temperature, T0; feed rate, F; and feed
composition, x0j.
Density of liquid in the tank, L is
assumed to be known function of
temperature, T and composition, xj.
Density of vapor in the drum is known
function ofav T, composition, yj and pressure,
M P
v v
where M vav average molecular
P.
RT
weight of gas
M

av
v

NC

M j y j where M j molecular weight of

j 1

jth component

A. STEADYSTATE MODEL
The system which neglects dynamics
completely.
Pressure is assumed constant, and
the steady state TCE, CCE and energy
balances are used.
Vapor and liquid phases are assumed
to be in equilibrium.

Total Continuity :

o Fo v Fv L FL
Component Continuity :
o Fo
v Fv
L FL
x0 j av y j av x j
av
M0
Mv
ML
Vapor - liquid equilibrium :
y j f ( x j ,T , P )
Energy equation :
h0 o Fo Hv Fv hL FL
Thermal properties :
h0 f(x0 j ,T0 )

h f(x0 j ,T0 )

H f(y j ,T,P)

B. RIGOROUS MODEL
TRY !!

An equilibrium-flash calculation is made at each point in

time to find vapor and liquid flow rates and properties
immediately after the pressure letdown valve (using
same equations as in Case A).

 These two streams are then fed into

the vapor and liquid phases.
Vapor phase

TRY !!

Liquid phase

 For liquid phases,

Boiling rate :
Wv K MT ( PL Pv )
Total Continuity :
d LVL
FL' L' FL L Wv
dt
Energy :
d ( LVLU L )
L' FL' hL' Wv H L L FL hL
dt
CCE :
VL L x j
d
av
M
v

dt

'
'
F

L L x ' Wv y " L FL x
j
j
j
M Lav '
M vav ' '
M Lav

 For vapor phases,

Total Continuity :
d vVv
Fv' H v' Wv Fv v
dt
Energy :
d ( vVvU v )
v' Fv' H v' Wv H L v Fv H v
dt
CCE :
Vv v y j
d
av
M
v

dt

Fv' v
M vav '

State :

M vav Pv
RTv

y 'j

Wv
v Fv
"
y

yj
j
av
av
Mv ''
Mv

 Addition of
1)multi-component vapor-liquid
equilibrium equation to calculate PL .
2)NC-1 CCE for each phase
Controller equations relating VL to FL
and Pv to Fv .

FL f (VL )

Fv f ( Pv )

C. PRACTICAL MODEL
For cases that ignore the dynamics
of the vapor phase (as in case B:
Liquid-phase dynamics model).
The vapor is assumed to be always
in equilibrium with the liquid.
So, conservation equations are
written for liquid phase only.

Total Continuity :
d LVL
F0 0 Fv v FL L
dt
CCE :
VL L x j
d
av
M
L

dt

F0 0 x Fv v y FL L x
0j
j
j
M 0av
M vav
M Lav

Energy :
d ( LVL h)
0 F0 h0 v Fv H L FL h
dt

 The NC vapor-liquid equilibrium

equations, three enthalpy
relationships, two density equations,
molecular weight equations, and
feedback controller equations are all
needed.
total number of equations must
equal to total number of variables
All the feed properties or forcing
functions are given.

Tutorial (Q5, Final Exam Oct 2008)

A brine solution is to be evaporated in an evaporator to yield a
solution of 50% salt. The feed mole fractions of salt and water
are xso and xwo respectively with its density, o. The feed
temperature and pressure for the system are To and Po,
respectively. By considering a rigorous model (liquid and vapor
dynamics) for the evaporation process and with an aid of a
diagram,
a)Derive the total continuity equations for the vapor and liquid
phase.
b)Derive the component continuity equation for evaporated
water.
c) Derive the energy continuity equations for the vapor and liquid
phase of the system.