Lecture Notes :BASIC LAWS IN

MODELING
Principles of Formulation of model:
•Basis
•Assumptions
•Mathematical consistency of model
•Solution of the model equations
•Verification
 BASIC LAWS IN MODELING
Fundamental laws used in modeling:
Some fundamental laws of physics and chemistry are required for
modeling a chemical engineering system, used in their time
dependent form
1. Continuity equations
2. Component continuity equations
3. Energy equations
4. Equation of motion
5. Transport equations
6. Equations of state
7. Equilibrium relations
 BASIC LAWS IN MODELING
Continuity equations:
Total continuity equation (Mass balance). The principle of the
conservation of mass when applied to a dynamic system says:
[Mass flow into system]-[Mass flow out of system]
=
[Time rate of change of mass inside system]
Unit: The units of this equations are mass per time, e.g. Kg/s.
N.B. The right hand side of the above equation will be either a
partial derivative or an ordinary derivative of the mass inside
the system with respect to the independent variable time, t.
Ex.1:
Consider a tank of perfectly mixed liquid as shown below, into
which flows of liquid stream at a volumetric rate of F0 (m3/min)
and with a density of 0 (Kg/m3). The volumetric holdup of liquid
in the tank is V (m3) and its density . The volumetric flow rate
from the tank is F, and the density of the out flowing stream is
the same as that of the tanks contents.

F0 (t)
0 (t)
V (t)
 (t) F (t)
 (t)

PERFECTLY MIXED TANK

We want to write continuity equation for the above
system: Assumptions
• In this case input, output as well as hold up in the tank
are in liquid phase.
• This system is called a macroscopic system as the mass
balance is to be around the whole tank. (Microscopic
system the mass balance is for a differential element
inside the tank).
• [F0 0]-[F] = Time rate of change of [V]

d
[ F0 0 - F  ] = ( V )
dt

• The units of this equation are kg/min.

• Since liquid is perfectly mixed, the density is same
everywhere in the tank, and it does not vary with radial or
axial position, i.e. there are no spatial gradients in density
in the tank.

• That is why we can use macroscopic system, means

there is only one independent variable, t.

• Since  and V are functions of only t, an ODE is formed.

Ex.2:
Fluid is flowing through a constant diameter cylindrical pipe
sketched as below. The flow is turbulent and therefore we can
assume plug flow conditions i.e. each slice of liquid flows down
the pipe as a unit.

dz

 (t, z)
v (t, z)
z

Z=0 z z + dz Z=L

FLOW THROUGH A PIPE

Assumptions
• There are no radial gradients in velocity or any other
properties.
• Axial gradients can exist.
• Density and velocity can change as the fluid flows along the
axial or Z direction.
• There are now two independent variables: time t and position
Z.
• Density and velocity are functions of both t and Z:  (t, z) and
v (t, z).
• The system is here is microscopic system as the differential
element is located at an arbitrary spot Z down the pipe.
• The slice is dz thick and has an area equal to the cross-
sectional area of the pipe A m2.
Continuity equation of the system
• Time rate of change of mass inside system
�
( A dz )
�
t
• Adz is the volume of the system;  is the density.
• The units of this equation are kg/min.

Mass flowing into system through boundary at z

= vA
Mass flowing out of the system through boundary at z+ dz =

�(vA )
vA + dz
�z
The above expression for the flow at z + dz may be
thought of as a Taylor series expansion of a function f
(z) around z.
The value of the function at a spot dz away from z is

�� f � ( dz )
2 2
��
f�
f ( z + dz ) = f ( z ) + � � dz + � 2 � + ....
��z�
(z) ��z �(z)
2!

If the dz is small the series can be truncated after the first

derivative term.
Letting f (z)= vA gives
�
f �(vA )
=
�z �z
Substituting these terms into equation of mass balance
gives

�( A dz ) �(vA )
= vA - [vA + dz ]
�
t �z
Canceling out the dz terms and assuming A is constant yield

 �(v  )
�
+ =0
�t �
z
Component continuity equations:
Component continuity equation (component balance). Chemical
components are not consumed like mass. If a reaction occurs
inside a system, the number of moles of an individual component
will increase if it is a product of the reaction or decreases if it is a
reactant .
So the component continuity equation of the jth chemical species
of the system:
[Flow of moles of jth component into system]-[Flow of moles of jth
component out of system] + [Rate of formation of moles of j th
component from chemical reactions]
=
[Time rate of change of moles of jth component inside system]
Unit: The units of this equations are moles of component per time.
Component continuity equations: Discussions
• The flows in and out can be both convective (due to bulk flow)
and molecular ( due to diffusion)
• We can have one component continuity equation for each
component in the system. e.g. if there are NC components,
there are NC component continuity equations for any one
system.
• However the one total mass balance and these NC component
balances are not all independent, since the sum of all the moles
times their respective molecular weights equals the total mass .
• In a given system we use total mass balance and NC-1
component balances.
• e.g. in a binary system , there would be one total mass balance
and one component balance equation is needed.
Ex.3:
Consider the same tank of perfectly mixed liquid as shown below,
into which flows of liquid stream at a volumetric rate of F 0 (m3/min)
and with a density of 0 (Kg/m3). The volumetric holdup of liquid in
the tank is V (m3) and its hold up . The volumetric flow rate from
the tank is F, and the density of the out flowing stream is the same
as that of the tanks contents. A chemical reaction (A to B) takes
place in the liquid in the tank. Component A reacts irreversibly and
a specific reaction rate k to form product, component B.

k
F0 (t) A �� �B
0 (t)
V (t),  (t),
CA0
CA, CB F (t),  (t)
CB0
CA, CB
PERFECTLY MIXED TANK
Assumptions:
• Let the concentrations of component A in the flowing feed
stream be CA0 (moles of A per unit volume) and in the
reactor CA.
• Assuming a simple first order reaction, the rate of
consumption of reactant A per unit volume will be directly
proportional to the instantaneous concentrations of A in
the tank.
Component balance on reactant A
Flow of reactant into system
F0C A0
Flow of A out of system
FC A

Rate of formation of A from reaction

-VkC A
The minus sign comes from the fact that A is being consumed,
not produced.
Units: The units of all these terms must be the same: moles of
A per unit time. Thus the unit of k in this system is t -1 as conc. is
moles of A per volume.
Time rate of change of A inside tank
d (VC A )
dt
Combining all of the above gives:

d (VC A )
= F0C A0 - FC A - VkC A
dt
Since the system is binary (component A & B) we could write
another component continuity equation for component B. Let
CB be the concentration of B in moles per unit volume.

d (VCB )
= F0CB 0 - FCB + VkCB
dt

N.B. The plus sign before the generation term since B

is being produced by the reaction.
Preferably, we use the total continuity equation since CA,
CB and  are uniquely related by the following equation,
where MA & MB are the molecular weights of components A
& B respectively.

M AC A + M B C B = 

N.B. Molecular weight is in mass per moles and concentration is

in moles per volume.
Ex.4:
Suppose we have the same macroscopic system as above except
that now consecutive reactions occur. Reactant A goes to B at a
specific reaction rate k1 but B can react at a specific reaction rate
k2 to form a third component C.
k1 k2
A �� � B �� �C
Assuming first order reactions the component continuity
equations for components A, B and C are as follows.
d (VC A )
= F0C A0 - FC A - Vk1C A
dt
d (VCB )
= F0CB 0 - FCB + Vk1C A - Vk2CB
dt
d (VCC )
= F0CC 0 - FCC + Vk2CB
dt
The component concentrations are related to density as
follows.
C

�M C
j= A
j j =

N. B. Three component balances could be used or we

could use two of the component balances and a total mass
balance.
Ex.5:
Instead of fluid flowing down a pipe as in ex. 2, suppose the pipe
is a tubular reactor in which the same reaction of ex. 3 (A to B)
takes place. As a slice of material moves down the length of the
reactor the concentration of reactant CA decreases as A is
consumed. Density , velocity v and concentration CA can all vary
with time and axial position Z. Still assume plug flow conditions so
that there are no radial gradients in velocity, density or
concentration. dz

 (t, z)
CAo (t) CAL (t)
v (t, z) k
A ��
�B
CA (t, z)

Z=0 z z + dz Z=L

FLOW THROUGH A TUBULAR REACTOR

The concentration of A fed to the inlet of the reactor at Z=0
is defined as,

CA (t,0) = CA0 (t)

The concentration of A in the reactor effluent at Z=L, is
defined as,

CA (t, L) = CAL (t)

We now want to apply the component continuity equation
for reactant A to a small differential slice of width dz.
As mentioned earlier the inflow term can be split into two
types: bulk flow and diffusion.
Discussion:
• Diffusion can occur because of the concentration gradient
in the axial direction. It is less important than bulk flow in
most practical systems.
• Diffusive flux of A, NA ( moles of A per unit time per unit
area) is given by Fick’s law, where DA is a diffusion
coefficient due to both diffusion and turbulence in the fluid
flow (eddy diffusivity).
• DA has units of length per unit time.
�CA
N A = - DA
� z
moles of A m 2 moles of A 1
2
=
s.m s m3 m
The terms in the general component equation are as follows.
Molar flow of A into boundary at z (bulk flow and diffusion)

vAC A + AN A
Molar flow of A leaving system at boundary at z+ dz

�(vAC A + AN A )
(vAC A + AN A ) + dz
� z
Rate of formation of A inside system

- kC A Adz
Time rate of change of A inside system

�( AdzC A )
�t
Substituting all terms in the main equation

�( AdzCA ) �(vAC A + AN A )
= (vACA + AN A ) - (vACA + AN A + dz ) - kC A Adz
�t �z
 Dividing by Adz
C A �(vC A + N A )
�
+ + kC A = 0
�t � z

Substituting for NA

�
C A �(vC A ) � �
CA
+ + kC A = ( DA )
�t �z �z �z
Units: the units of the equation are moles of A per volume per
time.
Energy equation:
The energy equation of the system:
[Flow of internal, kinetic and potential energy into system by
convection or diffusion]-[Flow of internal, kinetic and potential
energy out of system by convection or diffusion] + [Heat added to
system by conduction, radiation and reaction]-[Work done by
system on surroundings (shaft work and PV work)]
=
[Time rate of change of internal, kinetic and potential energy inside
system]
Unit: The units of this equations are energy per time.
Ex.6:
Consider the same system of CSTR this time with a cooling coil
inside the tank that can remove the exothermic heat of reaction  (
cal per g moles of A reacted).
Normal convention is that  -ve for an exothermic reaction and
+ve for an endothermic reaction.

F0 (t) k
A ��
�B
0 (t)
CA0
V (t),  (t),
T0 CA, T
-Q F (t),  (t)
CA, T

CSTR with heat removal

The rate of generation (energy per time) due to reaction is
the rate of consumption of A times .

QG = -VC A k
energy energy 3 moles of A 1
= m 3
time moles of A m time

The rate of heat removal from the reaction mass to the

cooling coil is –Q (energy per time).
The temperature of the feed is T0 and the temperature in the
reactor is T in k.
 d [(U + K + f )V  ]
F0 0 (U 0 + K 0 + f0 ) - F  (U + K + f ) + (QG + Q) - (W + FP - F0 P0 ) =
dt

Where U= internal energy (energy per unit mass)

K=Kinetic energy (energy per unit mass)
f=Potential energy (energy per unit mass)
W=shaft work done by the system (energy per time)
P=Pressure of the system
P0=Pressure of feed stream
Unit: all terms are in energy/time in the energy
equation
Here no shaft work so W=0, inlet and outlet velocities are not
very high, the kinetic energy term is negligible.
Since elevations of inlet and outlet flows are about the same,
the potential energy term is small. Thus the above equation is
reduced to.

d ( VU ) P P0
= F0 0U 0 - F U + QG + Q - F  + F0  0
dt  0
= F0 0 (U 0 + PV
0 0 ) - F  (U + PV ) + QG + Q

Here V is specific volume in m3/kg

H or h = U+PV
N.B h enthalpy of liquid and H enthalpy of vapor
 For CSTR

d ( VU )
= Fo 0 ho - F  h + Q - VkC A
dt

As h=Cp T

d (VT )
C p =  C p ( FoTo - FT ) + Q - VkC A
dt