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

Newton’s 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, there
are three directions : x, y, and z. Thus, three force balances can be written for any system.
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 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,
co
Into which flows a liquid stream at a volumetric rate of F o (ft3/min or m3/min) and with a density of ρ o
(lbm/ft3 or kg/m3). The volumetric holdup of liquid in the tank is V (ft 3 or m3) and its density is ρ. The
volumetric flow rate from the tank is F, and the density of the outflowing stream is the same as that
of the tank’s 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
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.
ABC
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 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 λ (Btu/lb.mol of A reacted or cal/g.mol of A
reacted ). The normal convention that λ 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 λ.
QG = - λVCAk
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 (ϕ) 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 ( Ṽ), determine the mathematical
model of this chemical process in terms of ODE by applying energy equation. Use Table 4d for
your answer.
e. Knowing that h or H is defined by
H or h = U + PṼ
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.
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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 (A pL) times
the density of the liquid ρ. 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: ECE 006 Laboratory Exercise No.: 3
Group No.: 2 Section: CH42S1
Group Members: Date Performed:
1. Cruz, Seanne Ednel Date Submitted: December 12, 2020
2. De La Cruz, Roel Ian M. Instructor: Engr. Crispulo G. Maranan
3. Dumoran, Francis D.
4. Galang, Arrissa Marie S.
5. Ganzon, Riobelle S.
6. Jaculba, Jewell Mae P.
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) d(ρV )/dt = ρinFin − ρoutFout

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

Term Mathematical Expression

Flow of A into the system Ff x CAo
Flow of A out of system F x CA
Rate of formation of A from reaction (dn/dt) = d(VCA)/dt

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

Term Mathematical Expression

Flow of B into the system Ff x CBo
Flow of B out of system F x CB
Rate of formation of A from reaction (dn/dt) = d(VCB)/dt

Table 2c. Mathematical model of CSTR having two components

Fundamental Physical /Chemical Law ODE

Component A continuity equation d(ρAV )/dt = ρ(A)inF(A)in − ρ(A)outF(A)out
Component B continuity equation d(ρBV )/dt = ρ(B)inF(B)in − ρ(B)outF(B)out
Total continuity equation (d(ρAV )/dt + (d(ρBV )/dt

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

Term Mathematical Expression

Flow of A into the system Ff x CAo
Flow of A out of system F x CA
Rate of formation of A from reaction (dn/dt) = d(VCA)/dt

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

Term Mathematical Expression

Flow of B into the system Ff x CBo
Flow of B out of system F x CB
Rate of formation of A from reaction (dn/dt) = d(VCA)/dt
Rate of formation of B from reaction (dn/dt) = d(VCB)/dt

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

Term Mathematical Expression

Flow of C into the system Ff x CCo
Flow of C out of system F x CC
Rate of formation of B from reaction (dn/dt) = d(VCC)/dt

Table 3d. Mathematical model of CSTR having three components

Fundamental Physical /Chemical Law ODE

Component A continuity equation d(ρAV )/dt = ρ(A)inF(A)in − ρ(A)outF(A)out
Component B continuity equation d(ρBV )/dt = ρ(B)inF(A)in − ρ(B)outF(B)out
Component C continuity equation d(ρCV )/dt = ρ(C)inF(C)in − ρ(C)outF(C)out
Total continuity equation (d(ρAV )/dt + (d(ρBV )/dt + (d(ρCV )/dt

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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 (ϕ) into the system by pO Fo (Uo + Ko + φO)
convection or diffusion
Flow of internal, kinetic, potential
energy out of system by convection or pf Ff (Uf + Kf + φf)
diffusion
Heat added to system by conduction, d(pV(U+K+φ) = pfFf(hf+Kf+φf) – poFo(ho+Ko+φo)+Qe+Qr –Wo
radiation, and reaction dt
Work done by the system on Wpv=FoPo-FfPf
surroundings (shaft work and PV
work) P here stands for Pressure
Rate of change of internal, kinetic and d(pV(U+K+φ) = pfFf(hf+Kf+φf) – poFo(ho+Ko+φo)+Qe+Qr – W
potential energy inside the system dt

Table 4b. Mathematical model of CSTR with heat removal

Fundamental Physical /Chemical Law ODE

Energy equation d(pV(U+K+φ) = pfFf(hf+Kf+φf) – poFo(ho+Ko+φo)+Qe+Qr –Wo
dt

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

Fundamental Physical /Chemical Law ODE

Energy equation d(pVU) = pfFfhf – poFoho + Qe
dt

Table 4d. Mathematical model of CSTR with heat removal

(with some changes including specific volume)

Fundamental Physical /Chemical Law ODE

Energy equation
d(pVU) = pfFfhf – poFoho + Qe
dt

Table 4e. Mathematical model of CSTR with heat removal

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 (with some changes including specific volume and now enthalpy)

Fundamental Physical /Chemical Law ODE

Energy equation
d(pVU) = pfFf – poFo + Qe
dt

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) M = Aρ x h x ρ
Velocity of the mass of the liquid (v) V = F/Aρ

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

Term Equation
Hydraulic Force Hydraulic Force = Aρ x h x g/gc

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

Term Equation
Frictional force Frictional Force = Kf x h x V2
where V is the velocity

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

Fundamental Physical /Chemical Law ODE

Equation of Motion 1 d(AρLρ) = Aρρh(g/gc) - KfLv2
gc dt

dv/dt = gh/L x (Kf gc / ρ Aρ)V2

7.Conclusion:

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The conclusion for the course introduced here is an unmistakably current takeoff from the regular
programming way to deal with information obtaining and control. The refreshed lab course grabbed the eye
of the understudies from the principal analyze. Understudies' year-end assessments of the course
throughout the most recent quite a long while have reliably shown that they discover the course content
useful and straightforward, even the more modern projects. Understudies additionally report that utilizing
LabVIEW realistic writing computer programs is useful in making stream graphs. Despite the fact that the
understudies at first found the sheer number of symbols (more than 800) to some degree overpowering, the
methodical structure of the symbol introduction described this undertaking turn as less overwhelming and, for
sure, well close enough. Before the finish of the course, by far most of understudies can recall the symbols
they learned in the absolute first lab analyze they completed. Maybe in particular, this course can adequately
exhibit the manner by which discrete capacities identify with genuine cycles.

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.

9. Assessment (Rubric for Laboratory Performance):

TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES
RUBRIC FOR MODERN TOOL USAGE
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 (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: ECE 006 Section: CH42FB1 2nd Sem SY 2019-2020
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 constraints of
skills, and perform fails to apply these in modern
modern discipline- these in performing engineering tools
tools to specific performing discipline-specific and shows
perform a engineering discipline- engineering task. intention to apply
discipline- task. specific them for
specific engineering engineering
engineering task. practice.
task.
2. Demonstrate Fails to apply Attempts to Shows ability to Shows ability to
skills in any modern apply modern apply fundamental apply the most
applying tools to solve tools but has procedures in appropriate and
different engineering difficulties to using modern effective modern
techniques problems. solve tools when solving tools to solve
and modern engineering engineering engineering
tools to problems. problems. problems.
solve
engineering
problems.
3. Recognize Does not Recognizes Recognizes the Recognizes the
the benefits recognize the some benefits benefits and need for benefits
and benefits and and constraints of and constraints of
constraints constraints of constraints of modern modern
of modern modern modern engineering tools engineering tools
engineering engineering engineering and shows and makes good
tools. tools. tools. intention to apply use of them for
them for engineering
engineering practice.
practice.
Total Score
Mean Score = (Total Score / 3)
Percentage Rating = (Total Score / 12) x 100%
Evaluated by: Engr. Crispulo G. Maranan
Printed Name and Signature of Faculty Member Date

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