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Mathematical
Modeling of
Chemical Processes

INPUT-OUTPUT MODEL

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Conservation Laws

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2-3

Conservation of Mass
 rate of mass  rate of mass   rate of mass 
 = − 
accumulation   in   out 

Conservation of Component i
rate of component i  rate of component i 
 = 
 accumulation   in 

rate of component i  rate of component i 

− + 
 out   produced 
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Development of Dynamic Models

Illustrative Example: A Blending Process

An unsteady-state mass balance for the blending system:

rate of accumulation   rate of   rate of  Pag

 = −  e 2-5
 of mass in the tank  mass in  mass out 

d (Vρ )
= w1 + w2 − w Eq. (1)
dt
where w1, w2, and w are mass flow rates.

The unsteady-state component balance is:

d (Vρx )
= w1x1 + w2 x2 − wx Eq. (2)
dt

The corresponding steady-state model

0 = w1 + w2 − w Eq. (2-4)
(3)

0 = w1 x1 + w2 x2 − wx Eq.(2-5)
(4)
Pag
e 2-6

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The Blending Process Revisited

For constant ρ , the equation (1) and (2) become:

dV
ρ = w1 + w2 − w Eq. (5)
dt

ρ d (Vx )
= w1x1 + w2 x2 − wx Eq. (6)
dt

Pag
e 2-7

Equation (6) can be simplified by expanding the accumulation term using the “chain
rule” for differentiation of a product:

d (Vx ) dx dV
ρ = ρV + ρx Eq. (7)
dt dt dt
Substitution of (7) into (6) gives:

dx dV
ρV + ρx = w1 x1 + w2 x2 − wx Eq. (8)
dt dt
Substitution of the mass balance in (5) for ρ dV/dt in (8) gives:
dx
ρV + x ( w1 + w2 − w ) = w1x1 + w2 x2 − wx Eq. (9)
dt
After canceling common terms and rearranging (5) and (9), a more convenient
model form is obtained:
dV 1
= ( w1 + w2 − w ) Eq. (10)
dt ρ
dx w1 w
= ( x1 − x ) + 2 ( x2 − x ) Eq. (11)
dt V ρ Vρ Page
2-8

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THREE IMPORTANT VARIATIONS OF THE

LIQUID STORAGE PROCESS

1. The inlet or outlet flow rates might be constant, for example, exit flow rate q
might be kept constant by a constant-speed pump.
2. The tank exit line may function simply as a resistance to flow from the tank,
or it may contain a valve that provides significant resistance to flow at a
single point. In the simplest case, the flow may be assumed to be linearly
related to the driving force, the liquid level, h = qRv, where Rv is the
resistance of the line or valve.
3. A more realistic expression for flow rate q can be obtained when a fixed
valve has been placed in the exit line and turbulent flow can be assumed.
Pag
The driving for flow through the valve is the pressure drop ∆P = P – Pa,
e 2-9
where P is the pressure at the bottom of the tank and Pa is the pressure at
the end of the exit line.

GROUP EXERCISE

Develop a model for this system that can be used to find h as

functions of time for any given variations in inputs.

Pag
e 2-
10

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Conservation of Energy
The general law of energy conservation is also called the
First Law of Thermodynamics. It can be expressed as:

rate of energy  rate of energy in  rate of energy out 

 = − 
 accumulation   by convection   by convection 

net rate of heat addition   net rate of work 

   
+  to the system from  + performed on the system  (2-8)
 the surroundings   by the surroundings 
   

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2-11

Stirred-Tank Heating Process

Stirred-tank heating process with constant holdup, V.

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Stirred-Tank Heating Process (cont’d.)

Assumptions:

1. Perfect mixing; thus, the exit temperature T is also the temperature

of the tank contents.
2. The liquid holdup V is constant because the inlet and outlet flow
rates are equal.
3. The density ρ and heat capacity C of the liquid are assumed to be
constant. Thus, their temperature dependence is neglected.
4. Heat losses are negligible.

Page 2-13

For the processes and examples considered, it is appropriate to make two

assumptions:

1. Changes in potential energy and kinetic energy can be neglected because

they are small in comparison with changes in internal energy.
2. The net rate of work can be neglected because it is small compared to the
rates of heat transfer and convection.

For these reasonable assumptions, the energy balance in can be written as

Eq. (12)

Uint = the internal energy of ∆ = denotes the difference

the system between outlet and inlet
) conditions of the flowing
H = enthalpy per unit mass streams; therefore
)
w = mass flow rate ( )
-Δ wH = rate of enthalpy of the inlet
Q = rate of heat transfer to the system stream(s) - the enthalpy
of the outlet stream(s)
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Model Development
An expression for the rate of internal energy accumulation can be derived
from Eq. (12) :

dU int dT
= ρVC Eq. (13)
dt dt

Suppose that the liquid in the tank is at a temperature T and has an

enthalpy, Ĥ .

(
Hˆ − Hˆ ref = C T − Tref ) Eq. (14)

where Hˆ ref is the value of

Ĥ at Tref. Without loss of generality, we assume
ˆ
that H ref = 0 (see Appendix B). Thus, Eq. (14) can be written as:

(
Hˆ = C T − Tref ) Eq. (15)

Model Development
For the inlet stream

(
Hˆ i = C Ti − Tref ) Eq. (16)

Substituting (15) and (16) into the convection term gives:

Eq. (17)

Finally, substitution of (13) and (17) into (12)

dT
V ρC = wC (Ti − T ) + Q Eq. (18)
dt Pag
e 2-
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Exercise

A perfectly stirred, constant-volume tank has two input streams, both consisting of
the same liquid. The temperature can vary with time.
Derive a dynamic model that will describe transient operation.

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2-17

Exercise

A completely enclosed stirred-tank heating process is used to heat an incoming

stream whose flow rate varies. The heating rate from this coil and the volume are
both constant.
Develop a mathematical model that describes the exit temperature if heat losses to
the ambient occur and if the ambient temperature (Ta) and the incoming stream’s
temperature (Ti) both can vary.
Notes:
ρ and Cp are constants.
U, the overall heat transfer coefficient, is constant.
As is the surface area for heat losses to ambient.
T > Ta (outlet temperature is higher than ambient temperature) Page
2-18

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Degrees of Freedom Analysis

1. List all quantities in the model that are known constants (or
parameters that can be specified) on the basis of equipment
dimensions, known physical properties, etc.
2. Determine the number of equations NE and the number of
process variables, NV. Note that time t is not considered to
be a process variable because it is neither a process input
nor a process output.
3. Calculate the number of degrees of freedom, NF = NV - NE.
4. Identify the NE output variables that will be obtained by
solving the process model.
5. Identify the NF input variables that must be specified as
either disturbance variables or manipulated variables, in Pag
order to utilize the NF degrees of freedom. e 2-
19

Degrees of Freedom Analysis for the

Stirred-Tank Heating Process Model:
dT
V ρC = wC (Ti − T ) + Q Eq. (18)
dt
3 parameters: V , ρ,C
4 variables: T , Ti , w, Q
1 equation: Eq. (18)

Thus the degrees of freedom are NF = 4 – 1 = 3. The process variables are

classified as:
1 output variable: T
3 input variables: Ti, w, Q

For temperature control purposes, it is reasonable to classify the three inputs as:
2 disturbance variables: Ti, w
1 manipulated variable: Q

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