Course Title : Process Control (PC)

CHE427
Chapter 2

Theoretical Models of Chemical

Processes

Resource Person
Tariq M. Raza
Week 2 CED-CUIL
1
Chapter 2 Today’s Ethical Discussion !
 Lecture Outline:
 What are mathematical models anyway (in their simplest forms)
and why they are needed simple examples ?
 Types of mathematical models
 Rationale for dynamic models
 Classification of models with pros and cons
Chapter 2

 Derivation of unsteady state/dynamic models

 General modeling principles
 Systematic approach for developing dynamic models
 Degrees of Freedom – Introduction and analysis with example
 Conservation Laws: Mass and Energy
 Application of conservation laws on blending process example
 …..
 What is a mathematical model:
A mathematical model describes and illustrates real-
life problems in mathematical terms n expressions.
It is usually simplified in the form of equations.
Chapter 2

A model in math is a simplified version of a real-

world system. It’s meant to help you understand how
a system works so that you can predict the future or
design solutions for it.

Mathematical models use equations to

simulate real-world situations, predicting
outcomes based on the interacting variables.
 Examples of mathematical model:
A simple example of a math model is Pythagorean
Theorem. It’s a very simple formula that you can use
to find the length of any side of a right triangle.
Chapter 2

From the very basic models like path followed by a

football after being kicked or a ball thrown upwards to
engineering n science world models like prediction of
weather conditions, global warming, flight simulation,
nuclear technology, space technology, biosciences,
population growth, financial market dynamics etc.
they all can be illustrated using mathematical models.
 Types of Mathematical models:
There are many different types of math models, but they
can be broken down into three main categories:

-Linear models -Non-linear models -Dynamic models

Chapter 2

Simple models use simple equations like:

Pythagoras theorem; a2 + b2 = c2
And complex models use complex equations like
Navier-Stokes equation i.e.
 Rationale for Dynamic Process Models:

Dynamic models can be used to:

1. Improve understanding of the process

Chapter 2

2. Train plant operating personnel

3. Develop a control strategy for new process

4. Optimize process operating conditions

 Classification of the models:
Models can be classified based on how they are
obtained:

1. Theoretical models are developed using principles

Chapter 2

of chemistry, physics, and biology.

2. Empirical models are obtained by fitting
experimental data
3. Semi-empirical models are a combination of
theoretical and empirical models. The numerical
values of one or more parameters in theoretical
model are calculated from experimental data.
 Theoretical Models
Advantages Disadvantages

They provide physical They tend to be

insight into the expensive and time-
Chapter 2

process behavior. consuming to develop.

They are applicable Models of complex
over a wide range of processes typically
conditions. include some parameters
that are not readily
available e.g., reaction
rate coefficients, physical
properties, heat transfer
coefficients.
 Empirical Models
Advantages Disadvantages

Easier to develop. They typically do not

extrapolate well.
Chapter 2

Need to be used with caution

for operating conditions not
included in experimental data
to fit the model.
The range of data is typically
quite small compared to the
full range of process
operating conditions.
 Semi-empirical Models
Advantages Disadvantages

They incorporate theoretical

knowledge
Chapter 2

Extrapolated over a wide

range of OCs.
Require less development
effort than Theoretical models
Consequently, widely used in
industry.
 Development of Dynamic Models

Illustrative Example: A Blending Process

Chapter 2

An unsteady-state mass balance for the blending system:

rate of accumulation   rate of   rate of 
    (2-1)
 of mass in the tank  mass in  mass out 
 d Vρ 
or  w1  w2  w (2-2)
dt
where w1, w2, and w are mass flow rates.

The unsteady-state component balance is:

Chapter 2

d Vρx 
 w1 x1  w2 x2  wx (2-3)
dt

The corresponding steady-state model was derived in Ch. 1 (cf.

Eqs. 1-1 and 1-2).
0  w1  w2  w (2-4)
0  w1x1  w2 x2  wx (2-5)
 General Modeling Principles
• The model equations are at best an approximation to the real
process.
• Adage: “All models are wrong, but some are useful.”
• Modeling inherently involves a compromise between model
Chapter 2

accuracy and complexity on one hand, and the cost and effort
required to develop the model, on the other hand.
• Process modeling is both an art and a science. Creativity is
required to make simplifying assumptions that result in an
appropriate model.
• Dynamic models of chemical processes consist of ordinary
differential equations (ODE) and/or partial differential equations
(PDE), plus related algebraic equations.
Systematic Approach for Developing Dynamic Models

1.State the modeling objectives and the end use of the

model. They determine the required levels of model
detail and model accuracy.
Chapter 2

2.Draw a schematic diagram of the process and label

all process variables.
3.List all of the assumptions that are involved in
developing the model. Try for parsimony; the
model should be not be more complicated than
necessary to meet the modeling objectives.
4.Determine whether spatial variations of process
variables are important. If so, a partial differential
equation model will be required.
Systematic Approach for Developing Dynamic Models

5. Write appropriate conservation equations (mass,

component, energy, and so forth).
Chapter 2

6. Introduce equilibrium relations and other algebraic

equations (from thermodynamics, transport phenomena,
chemical kinetics, equipment geometry, etc.).

7. Perform a degrees of freedom analysis (Section 2.3) to

ensure that the model equations can be solved.
Systematic Approach for Developing Dynamic Models

8. Simplify the model. It is often possible to arrange

the equations so that the dependent variables (outputs)
appear on the left side and the independent variables
Chapter 2

(inputs) appear on the right side. This model form is

convenient for computer simulation and subsequent
analysis.

9. Classify inputs as disturbance variables or as

manipulated variables.
 Intro. to Degrees of Freedom
Degree of freedom is a method of evaluating if a
given system has enough or too much
information to be solved.
Chapter 2

This analysis method allows for a quick

verification of if data provided is substantial or not

DoF is especially useful with multiple units, and

multi-variable systems that can often involve
complex and intricate calculations.
 Intro. to Degrees of Freedom (continued…)
The general formula used for DoF is:

DoF = no. of unknowns –

(no. of independent variables +
Chapter 2

no. of other equations)

DoF = 0  solvable system

DoF > 0  unsolvable system

(under-specified system)

DoF < 0  over-specified system

 Intro. to Degrees of Freedom (continued…)

2x + y = 7 underspecified
Chapter 2

2x + y = 7
DoF = 0
x + 3y = 11

2x + y = 7
x + 3y = 11 Over-specified
x+ y =4
 Intro. to Degrees of Freedom (continued…)

DoF = #unknowns – #indep. variables - #other eqs

DoF = #unknowns – #indep. balances - #other eqs

Chapter 2

#independent balances = #species in the system

Chapter 2
 Determination of Degrees of Freedom -Example
Chapter 2

Let’s solve these on the board and discuss in detail.

 Table 2.2. 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
Chapter 2

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
order to utilize the N degrees of freedom.
 Conservation Laws
Theoretical models of chemical processes are based on conservation
laws.

Conservation of Mass
 rate of mass  rate of mass  rate of mass 
Chapter 2

    (2-6)

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 

   (2-7)
 out   produced 
 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 
Chapter 2

net rate of heat addition   net rate of work 

   
  to the system from   performed on the system  (2-8)
 the surroundings   by the surroundings 
   

The total energy of a thermodynamic system, Utot, is the sum of its

internal energy, kinetic energy, and potential energy:
U tot  U int  U KE  U PE (2-9)
 For the processes and examples considered in this book, 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
Chapter 2

compared to the rates of heat transfer and convection.

For these reasonable assumptions, the energy balance in
Eq. 2-8 can be written as
dU int 
dt

  wH  Q  (2-10)
  denotes the difference
U int  the internal energy of
between outlet and inlet
the system 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)
 The analogous equation for molar quantities is,
dU int
dt

  wH 
  Q (2-11)

where H is the enthalpy per mole and w is the molar flow rate.

In order to derive dynamic models of processes from the general

Chapter 2

energy balances in Eqs. 2-10 and 2-11, expressions for Uint and Ĥ
or H are required, which can be derived from thermodynamics.

The Blending Process Revisited

For constant  , Eqs. 2-2 and 2-3 become:
dV
  w1  w2  w (2-12)
dt
 d Vx 
 w1x1  w2 x2  wx (2-13)
dt
 Equation 2-13 can be simplified by expanding the accumulation
term using the “chain rule” for differentiation of a product:
d Vx  dx dV
  V  x (2-14)
dt dt dt
Substitution of (2-14) into (2-13) gives:
dx dV
Chapter 2

V   x  w1 x1  w2 x2  wx (2-15)
dt dt
Substitution of the mass balance in (2-12) for  dV/dt in (2-15)
gives:
dx
V  x  w1  w2  w   w1x1  w2 x2  wx (2-16)
dt
After canceling common terms and rearranging (2-12) and (2-16),
a more convenient model form is obtained:
dV 1
  w1  w2  w  (2-17)
dt 
dx w1 w2
  x1  x    x2  x  (2-18)
dt V  V
 Example 2.1: Stirred Tank Blending Process

A stirred-tank blending
process with constant
liquid holdup of 2m3 is
used to blend two
Chapter 2

streams whose over

flow
densities are both
approx. 900kg/m3. The
density does not
change during mixing.
 Example 2.1: Stirred Tank Blending Process

a. Assume that the process has been operating

for a long period of time with flow rates of
w1=500 kg/min and w2=200kg/min and feed
Chapter 2

compositions (mass fractions) of x1=0.4 and

x2=0.75. What is steady-state value of x?

b. Suppose that w1 changes suddenly from 500

to 400 kg/min and remains at the new value.

Determine an expression for x(t) and plot it.
Let’s solve the problem, on the whiteboard and
discuss it in detail.
 Example 2.1: Stirred Tank Blending Process
c. Repeat part (b) for the case where w2
(instead of w1) changes suddenly from 200 to
100 kg/min and remains there.
Chapter 2

d. Repeat part © for the case where x1 suddenly

changes from 0.4 to 0.6.

e. For parts (b) through (d), plot the normalized

response xN(t),
xN(t) =
where x(0) is initial ss value of x(t) and x() is
final ss value, which is different for each part.
Chapter 2 Stirred-Tank Heating Process

Figure 2.3 Stirred-tank heating process with constant holdup, V.

 Stirred-Tank Heating Process (cont’d.)

Assumptions:

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

Chapter 2

temperature of the tank contents.

2. The liquid holdup V is constant because the inlet and outlet
flow rates are equal.
3. The density  and heat capacity C of the liquid are assumed to
be constant. Thus, their temperature dependence is neglected.
4. Heat losses are negligible.
 Model Development - I
For a pure liquid at low or moderate pressures, the internal energy
is approximately equal to the enthalpy, Uint  H, and H depends
only on temperature. Consequently, in the subsequent
development, we assume that Uint = H and Uˆ int  Hˆ where the
Chapter 2

caret (^) means per unit mass. As shown in Appendix B, a

differential change in temperature, dT, producesˆ a corresponding
change in the internal energy per unit mass, dU int ,

dUˆ int  dHˆ  CdT (2-29)

where C is the constant pressure heat capacity (assumed to be

constant). The total internal energy of the liquid in the tank is:

U int  VUˆ int (2-30)

 Model Development - II
An expression for the rate of internal energy accumulation can be
derived from Eqs. (2-29) and (2-30):
dU int dT
 VC (2-31)
dt dt
Chapter 2

Note that this term appears in the general energy balance of Eq. 2-
10.
Suppose that the liquid in the tank is at a temperature T and has an
enthalpy, Ĥ . Integrating Eq. 2-29 from a reference temperature
Tref to T gives,

Hˆ  Hˆ ref  C T  Tref (2-32)
where Hˆ ref is the value of Ĥ at Tref. Without loss of generality, we
assume that Hˆ ref  0 (see Appendix B). Thus, (2-32) can be
written as:

Hˆ  C T  Tref (2-33)
 Model Development - III
For the inlet stream


Hˆ i  C Ti  Tref  (2-34)
Chapter 2

Substituting (2-33) and (2-34) into the convection term of (2-10)

gives:

    
 wHˆ  w C Ti  Tref   w C T  Tref 
     (2-35)

Finally, substitution of (2-31) and (2-35) into (2-10)

dT
V C  wC Ti  T   Q (2-36)
dt
 Degrees of Freedom Analysis for the Stirred-Tank
Model:
3 parameters: V , ,C
4 variables: T , Ti , w, Q
1 equation: Eq. 2-36
Chapter 2

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
 Continuous Stirred Tank Reactor (CSTR)
Chapter 2

Fig. 2.6. Schematic diagram of a CSTR.

 CSTR: Model Development
Assumptions:
1. Single, irreversible reaction, A → B.
2. Perfect mixing.
3. The liquid volume V is kept constant by an overflow line.
4. The mass densities of the feed and product streams are equal
and constant. They are denoted by r.
Chapter 2

5. Heat losses are negligible.

6. The reaction rate for the disappearance of A, r, is given by,
r = kcA (2-62)
where r =  moles of A reacted per unit time, per unit volume, cA
is the concentration of A (moles per unit volume), and k is the rate
constant (units of reciprocal time).
7. The rate constant has an Arrhenius temperature dependence:
k = k0 exp(-E/RT ) (2-63)
where k0 is the frequency factor, E is the activation energy,
and R is the the gas constant.
 CSTR: Model Development (continued)
• Unsteady-state mass balance

Because r and V are constant, . Thus,

Chapter 2

the mass balance is not required.

• Unsteady-state component balance

.
 Assumptions for the Unsteady-state Energy Balance:

8.

9.

10.

11.

12.

42
 CSTR Model: Some Extensions
• How would the dynamic model change for:

1. Multiple reactions (e.g., A → B → C) ?

2. Different kinetics, e.g., 2nd order reaction?
3. Significant thermal capacity of the coolant liquid?
Chapter 2

4. Liquid volume V is not constant (e.g., no overflow line)?

5. Heat losses are not negligible?
6. Perfect mixing cannot be assumed (e.g., for a very
viscous liquid)?