Laboratory Exercise No.

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Mathematical Modeling of Chemical Processes

1. Objective:
The activity aims to model chemical processes in terms of ordinary differential equations.
2. Intended Learning Outcomes (ILOs):
The students shall be able to:
2.1 State modeling objectives.
2.2 Draw a schematic diagram of the process and label all process variables.
2.3 List all the assumptions that are involved in developing the model.
2.4 Write appropriate conservation equations (mass, component, energy and so forth.
2.5 Introduce equilibrium relations and other algebraic equations (from thermodynamics, transport
phenomena, chemical kinetics, equipment geometry, etc).
2.6 Perform a degrees of freedom analysis to ensure that the model equations can be solved.
2.7 Simplify the model by arranging the equations so that the dependent variables (outputs) appear on
the left side and the independent variables (inputs) appear on the right side which is convenient for
computer simulation and subsequent analysis.
2.8 Classify inputs as disturbance variables or as manipulated variables.
3. Discussion:
Mathematical model is a representation of the essential aspects of an existing system or a system to be
constructed which represents knowledge of that system in a usable form. It is a system of equations whose
solution, given specified input data, is representative of the response of the process to a corresponding set
of inputs.
Mathematical modeling is used to improve understanding of the process, to optimize process
design/operating conditions, to design control strategy for the process and to train operating personnel.
Dynamic models of chemical processes consist of ordinary differential equations (ODE) or partial differential
equations (PDE), plus related algebraic equations.
The classification of models include Linear vs. Non-linear, Lumped parameter vs. Distributed parameter,
Deterministic vs. Stochastic, State Space Models and Input-Output Models.
A systematic approach to developing dynamic models include State the modeling objectives, Draw a
schematic diagram of the process and label all process variables, List all the assumptions that are involved
in developing the model, Write appropriate conservation equations (mass, component, energy and so forth,
Introduce equilibrium relations and other algebraic equations (from thermodynamics, transport phenomena,
chemical kinetics, equipment geometry, etc), Perform a degrees of freedom analysis to ensure that the
model equations can be solved, Simplify the model by arranging the equations so that the dependent
variables (outputs) appear on the left side and the independent variables (inputs) appear on the right side
which is convenient for computer simulation and subsequent analysis and classify inputs as disturbance
variables or as manipulated variables.
Some of the fundamental laws of physics and chemistry in their general time-dependent form include the
following:
I. Continuity Equations
A. Total Continuity Equation (Mass Balance)
The principle of the conservation of mass when applied to dynamic system is
[Mass flow into the system][Mass flow out of the system] = [time rate of change of mass inside
the
system]

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 B. Component Continuity Equations (Component Balance)
Unlike mass, chemical components are not conserved. 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 decrease if it is a reactant. Therefore, the component continuity equation of
the jth chemical species of the system is

[ Flow of moles of jth component into the system ] [Flow of moles of jth component out the
system ] + [ rate of formation of moles of jth component from chemical reaction ] = [ time rate of
change of moles of jth component inside system ]

The unit of this equation is moles of component j per unit time. The flows in and out can be
both convective ( due to bulk flow ) and molecular ( due to diffusion ). One component
continuity equation can be written for each component in the system. If there are NC
components, there are NC component continuity equations for any one system. However,
the total mass balance and these NC component balances are not all independent, since
the sum of all moles times their respective molecular weights equals the total mass.
Therefore, a given system has only NC independent continuity equations. Usually, the total
mass balance and NC 1 component balances are used. In a binary ( two-component
system ) system, there would be one total mass balance and one component balance.

II. Energy Equation

The first law of thermodynamics puts forward the principle of conservation of energy. Written
for a general open system ( where flow of material in and out of the system can occur) it is

[ Flow of internal, kinetic, potential energy into the system by convection or diffusion ] [ Flow of
internal, kinetic, 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 the
system]

III. Equations of Motion

Newtons second law of motion states that force is equal to mass times acceleration for a
system with constant mass M.
F = Ma/gc
where : F = force, lbf ,
M = mass, lbm
a = acceleration, ft/s2 = dv/dt
gc = 32.2 ft/lbf.s2
In slightly more general form, where mass can vary with time,

where vi = velocity in the I direction

Fji = jth force acting in the I direction
The time rate of change of momentum in the I direction (mass times velocity in the I direction )
is equal to the sum of the forces pushing in the i direction. It can be thought of as a dynamic
force balance. Or more eloquently, it is called the conservation of momentum. In the real world,
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 there are three directions : x, y, and z. Thus, three force balances can be written for any
system. Therefore, each system has three equations of motion ( plus one total mass balance,
one energy equation and NC 1 component balances). The field of fluid mechanics makes
extensive use of the conservation of momentum.
IV. Transport Equations
V. Equations of State
VI. Equilibrium
VII. Chemical Kinetics
4. Resources:
Elementary Principles of Chemical Processes
Process Modeling, Simulation and Control for Chemical Engineers
5. Procedure:
1. Consider the tank of perfectly mixed liquid as shown below,

Into which flows a liquid stream at a volumetric rate of F o (ft3/min or m3/min) and with a density of o
(lbm/ft3 or kg/m3). The volumetric holdup of liquid in the tank is V (ft 3 or m3) and its density is . The
volumetric flow rate from the tank is F, and the density of the outflowing stream is the same as that
of the tanks contents. Determine the mathematical model of this chemical process in terms of ODE
by applying continuity equation. Use Table 1 for your answer.
2. Consider the same tank of perfectly mixed liquid that is used in Procedure 1 except that a chemical
reaction takes place in the liquid in the tank. The system is now a CSTR ( continuous stirred-tank
reactor ) as shown below :

Component A reacts irreversibly and at a specific reaction rate k to form product, component B.
A B
Let the concentration of component A in the inflowing feed stream be C AO ( 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 concentration of A in the
tank.
a. Determine the flow of A into the system, flow of A out of system and rate of formation of A from
reaction. Use Table 2a for your answers.
b. Determine the flow of B into the system, flow of B out of system and rate of formation of A from
reaction. Use Table 2b for your answers.
c. Determine the mathematical models of this chemical process in terms of ODE by applying
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 component continuity equation for component A and for component B. Determine also the total
continuity equation. Use Table 2 for your answers.
3. Suppose the same macroscopic system as above except that now consecutive reactions occur.
Reactant A goes to B at a specific reaction rate k 1, but B can react at a specific reaction rate k 2 to
form a third component C.
ABC
Assuming first-order reactions,
a. Determine the flow of A into the system, flow of A out of system and rate of formation of A from
reaction. Use Table 3a for your answers.
b. Determine the flow of B into the system, flow of B out of system, rate of formation of A from
reaction, and rate of formation of B from reaction. Use Table 3b for your answers.
c. Determine the flow of C into the system, flow of C out of system and rate of formation of B from
reaction. Use Table 3c for your answers.
d. Determine the mathematical models of this chemical process in terms of ODE by applying
component continuity equation for component A, for component B and for component C. Determine
also the total continuity equation. Use Table 3d for your answers.
4. Consider the CSTR system of Procedure 2 , this time with a cooling coil inside the tank

that can remove the exothermic heat of reaction (Btu/lb.mol of A reacted or cal/g.mol of A
reacted ). The normal convention that is negative for an exothermic reaction and positive for an
endothermic reaction. The rate of heat generation (energy per time) due to the reaction is the rate
of consumption of A times .
QG = - VCAk
The rate of heat removal from the reaction mass to the cooling coil is Q (energy per time). The
temperature of the feed stream is To and the temperature in the reactor is T (R or K)..
a. Determine the flow of internal (U), kinetic (K), potential energy () into the system by
convection or diffusion, flow of internal, kinetic, potential energy out of system by convection or
diffusion, heat added to system by conduction, radiation, and reaction, work done by the
system on surroundings (shaft work and PV work), and rate of change of internal, kinetic and
potential energy inside the system. Use Table 4a for your answers.
b. Determine the mathematical model of this chemical process in terms of ODE by applying
energy equation. Use Table 4a for your answer.
c. When there is no shaft work, W = 0. If the inlet and outlet flow velocities are not very high, the
kinetic energy term is negligible. If the elevations of the inlet and outlet flows are about the
same, the potential energy is small. With these changes, determine the mathematical model of
this chemical process in terms of ODE by applying energy equation. Use Table 4c for your
answer.
d. Noting that the reciprocal of the density is specific volume ( ), determine the mathematical
model of this chemical process in terms of ODE by applying energy equation. Use Table 4d for
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 your answer.
e. Knowing that h or H is defined by
H or h = U + P
Wherein h is the enthalpy of the liquid stream and H for the enthalpy of a vapor stream,
determine the mathematical model of this chemical process in terms of ODE by applying
energy equation. Use Table 4e for your answer.
5. The gravity-flow tank system provides an application of the equations of motion to a macroscopic
system. Referring to the figure below,

Let the length of the exit line be L (ft) and its cross-sectional area be A (ft 2). The vertical, cylindrical
tank has a cross-sectional are of A (ft2). The part of this process that is described by a force
balance is the liquid flowing through the pipe. It will have a mass equal to the volume of the pipe
(ApL) times the density of the liquid . This mass of liquid will have a velocity v (ft/s) equal to
volumetric flow (F) divided by the cross-sectional area of the pipe (A p). Plug-flow conditions and
incompressible liquid are assumed whereby all the liquid is moving at the same velocity, more or
less like a solid rod.
a. Determine the equations for the mass of the liquid (M) and velocity of the mass of the liquid (v).
Use Table 5a for your answers.

The amount of the liquid in the pipe will not change, but if we want to change the rate of outflow,
the velocity of the liquid must be changed. And to change the velocity or the momentum of the
liquid we must exert a force on the liquid.
The direction of interest is the horizontal, since the pipe is assumed to be horizontal. The force
pushing on the liquid at the left end of the pipe is the hydraulic pressure force of the liquid in the
tank.
b. Determine the equation for the hydraulic pressure force of the liquid in the tank. Use Table 5b
for your answer.

The only force pushing in the opposite direction from right to left and opposing the flow is the
frictional force due to the viscosity of the liquid. If the flow is turbulent, the frictional force will be
proportional to the square of the velocity and the length of the pipe.
c. Determine the equation for the frictional force due to the viscosity of the liquid. Use Table 5c for
your answer.

Substitute the hydraulic pressure and frictional force ( in this case, a negative force) in the general
form of the equation of motion where mass can vary with time.
d. Determine the ODE for gravity-flow tank system. Use Table 5d for your answer.

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Course: Laboratory Exercise No.:3
Group No.: Section:
Group Members: Date Performed: 11/25/17
KABILING, AMIELYN B.
Date Submitted:11/25/17
Instructor:

6. Data and Results:

1.
Table 1. Mathematical model of the tank having perfectly mixed liquid

Fundamental Physical /Chemical Law ODE

Continuity equation (mass balance)

2.
Table 2a. Component Balance on A of CSTR having two components

Term Mathematical Expression

Flow of A into the system Fo CAo
Flow of A out of system F CA
Rate of formation of A from reaction

Table 2b. Component Balance on B of CSTR having two components

Term Mathematical Expression

Flow of B into the system Fo CBo
Flow of B out of system F CB
Rate of formation of A from reaction

Table 2c. Mathematical model of CSTR having two components

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 Fundamental Physical /Chemical Law ODE
Component A continuity equation

Component B continuity equation

Total continuity equation

3.
Table 3a. Component Balance on A of CSTR having three components

Term Mathematical Expression

Flow of A into the system
Flow of A out of system
Rate of formation of A from reaction

Table 3b. Component Balance on B of CSTR having three components

Term Mathematical Expression

Flow of B into the system
Flow of B out of system
Rate of formation of A from reaction
Rate of formation of B from reaction

Table 3c. Component Balance on C of CSTR having three components

Term Mathematical Expression

Flow of C into the system
Flow of C out of system
Rate of formation of B from reaction

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 Table 3d. Mathematical model of CSTR having three components

Fundamental Physical /Chemical Law ODE

Component A continuity equation
Component B continuity equation
Component C continuity equation
Total continuity equation

4.
Table 4a. Different Terms and its Mathematical Expression in CSTR with heat removal

Term Mathematical Expression

Flow of internal (U), kinetic (K),
potential energy () into the system by
convection or diffusion

Flow of internal, kinetic, potential

energy out of system by convection or
diffusion

Heat added to system by conduction,

radiation, and reaction

Work done by the system on

surroundings (shaft work and PV
work)

Rate of change of internal, kinetic and

potential energy inside the system

Table 4b. Mathematical model of CSTR with heat removal

Fundamental Physical /Chemical Law ODE

Energy equation

Table 4c. Mathematical model of CSTR with heat removal (with some changes)

Fundamental Physical /Chemical Law ODE

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 Energy equation

Table 4d. Mathematical model of CSTR with heat removal

(with some changes including specific volume)

Fundamental Physical /Chemical Law ODE

Energy equation

Table 4e. Mathematical model of CSTR with heat removal

(with some changes including specific volume and now enthalpy)

Fundamental Physical /Chemical Law ODE

Energy equation

5.

Table 5a. Equations for mass of the liquid (M) and velocity of the mass of the liquid (v)

Term Equation
Mass of the liquid (M)
Velocity of the mass of the liquid (v)

Table 5b. Equation for the hydraulic pressure force of the liquid in the tank

Term Equation
Hydraulic Force

Table 5c. Equation for the frictional force due to the viscosity of the liquid

Term Equation
Frictional force

Table 5d. Mathematical Model for gravity-flow tank system

Fundamental Physical /Chemical Law ODE

Equation of Motion

7.Conclusion:

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Mathematical model is a representation of the essential aspects of an existing system or a system to be
constructed which represents knowledge of that system in a usable form. It is a system of equations whose
solution, given specified input data, is representative of the response of the process to a corresponding set
of inputs.
In this experiment, we design control strategy for the process and we train operating personnel. We also
used dynamic models of chemical processes consist of ordinary differential equations (ODE) or partial
differential equations (PDE), plus related algebraic equations.

8. Further Readings:
Seborg Dale E., Edgar, Thomas F., and Mellichamp Duncan A. (2004). Process Dynamics and
Control. Singapore: Wiley.
Knopf, F. C. (2012). Modeling, analysis and optimization of process and energy systems.Hoboken,
New Jersey: John Wiley and Sons.
Velten, K. (2009). Mathematical modeling and simulation: introduction for scientists and engineers.
Singapore: Wiley-VCH.

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9. Assessment (Rubric for Laboratory Performance):
TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES
RUBRIC FOR MODERN TOOL USAGE
(Engineering Programs)
Student Outcome (e): Use the techniques, skills, and modern engineering tools necessary for engineering practice in
complex engineering activities.
Program: Chemical Engineering Course: CHE 506 Section: _______ ____Sem SY ________
Performance Unsatisfactory Developing Satisfactory Very Satisfactory Score
Indicators 1 2 3 4
1. Apply Fails to identify Identifies Identifies modern Recognizes the
appropriate any modern modern techniques and is benefits and
techniques, techniques to techniques but able to apply these in constraints of modern
skills, and perform fails to apply performing discipline- engineering tools and
modern tools discipline-specific these in specific engineering shows intention to
to perform a engineering task. performing task. apply them for
discipline- discipline- engineering practice.
specific specific
engineering engineering task.
task.
2. Demonstrate Fails to apply any Attempts to Shows ability to Shows ability to apply
skills in modern tools to apply modern apply fundamental the most appropriate
applying solve engineering tools but has procedures in using and effective modern
different problems. difficulties to modern tools when tools to solve
techniques solve solving engineering engineering
and modern engineering problems. problems.
tools to solve problems.
engineering
problems.
3. Recognize the Does not Recognizes Recognizes the Recognizes the need
benefits and recognize the some benefits benefits and for benefits and
constraints of benefits and and constraints constraints of constraints of modern
modern constraints of of modern modern engineering engineering tools and
engineering modern engineering tools and shows makes good use of
tools. engineering tools. tools. intention to apply them for engineering
them for engineering practice.
practice.
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 Total Score
Mean Score = (Total Score / 3)
Percentage Rating = (Total Score / 12) x 100%
Evaluated by: Engr. Crispulo G. Maranan June 31, 2017
Printed Name and Signature of Faculty Member Date

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