Mathematical Modeling of

CSTR and PFR for

Polystyrene Production
ChE 360 Project

Michael McEldrew

David Belias

Austin Goewert

David Kozak



5/1/2014





1
Table of Contents

Introduction .................................................................................................................................................. 2
Results ........................................................................................................................................................... 5
Mathematical Modeling of Polystyrene Formation using CSTR ............................................................... 5
Mathematical Modeling of Polystyrene Plug-Flow Reactor ................................................................... 12
Conclusion ................................................................................................................................................... 17
Appendix ..................................................................................................................................................... 18
Appendix 1 .............................................................................................................................................. 18
Appendix 2 .............................................................................................................................................. 26












2
Introduction
Modeling processes in chemical engineering often require the use of analytical mathematical
methods. Throughout the 360 course, various methods have been used to solve systems of ordinary and
partial differential system of equations. Each method contains its limitations. In this project, students
were required to utilize their problem solving skills to create the most effective model to represent the
system. Different mathematical methods were used with each reactor to obtain the most accurate
solutions.
The first problem involves a monomer reacting exothermically with an initiator to produce
polystyrene, which can be seen in Figure 1. A cooling jacket was run around a continuously stirred tank
reactor to control the temperature. Perfect mixing, constant volume, and constant properties were
assumed.


This problem had to be solved by modeling the mathematical equations from Figure 2. First, the
three steady states were evaluated with respect to the given conditions. The steady state analysis
involved using Newtons Method. Afterwards, these states were compared to the dynamic process at
two different reactor temperatures (350 K and 300 K). These changes were used to investigate the
effects of temperature change on the reaction. The dynamic process was evaluated using Eulers Explicit
method in which the stiffness value was found to be of magnitude one.
Figure 1: Continuous polymerization reactor (CSTR)
3


The second problem involved a jacketed plug flow reactor, which is diagrammed in Figure 3. The
main difference pertaining to the plug flow reactor was the lack of complete mixing within the reactor.
This reactor differed spatially from the CSTR and was thus described by the equations below in Figure 4.




Figure 2: CSTR equations
Figure 3: Continuous polymerization reactor (plug flow)
Figure 4: Plug flow equations

4
This problem was initially solved to find the reactor temperature along the reactor length steady
states. These values were calculated using the Finite Differences method. The second analysis for this
problem was to evaluate the startup process of the reactor to investigate the effects it had on the
steady state concentrations and jacket temperature. To solve for these equations, both Eulers Explicit
and Eulers Implicit methods were used.
Note: All calculations were done in Matlab. See the Appendix for all of the scripts.





















5
Results

Mathematical Modeling of Polystyrene Formation using CSTR
Steady-State Analysis:
The first problem posed for the CSTR reactor was to find the three steady state conversions that
the mathematical model produces. The given model for this reactor was a system of four coupled
differential equations, written for the initiator concentration, the monomer concentration, the reactor
temperature, and the cooling jacket temperature. The steady state parameter allowed the systems
differential equations to be transformed into a system of nonlinear algebraic equations. Newtons
method was used to solve this system of equations. Newtons method involves the formulation of the
Jacobian Matrix. In this problem, the Jacobian Matrix was a four by four matrix, consisting of the partial
derivatives taken with respect to each variable for each of the equations. The partial derivatives were
evaluated using Matlab, and then formulated into a matrix within the program created to perform
Newtons Method, which can be seen in Appendix 1. Once this program was able to run the correct
Newton iterations, the steady state solutions could be found. The problem stated that there would be
three steady state conversions: high, low, and medium. In order to find these different steady states the
initial guesses given to the program need to be altered accordingly. To find the high conversion, the
initiator and monomer concentrations have to be low, because a high conversion implies the
consumption of the reactants. Also, because the reaction is exothermic, the expected reactor and jacket
temperatures were guessed to be high for high conversion. To find the low conversion, the initial
guesses followed the opposite thinking. The concentrations of the initiator and monomer were guessed
to be high, because there would be less consumption of the reactants. The temperature of the reactor
and jacket were guessed to be low, because the less reaction would take place with a low conversion. To
find the medium conversion, the guesses would be somewhere in between the low and high conversion
guesses. It did take a number of guesses before the medium conversion steady state was found. The
initial guesses and the subsequent conversions that were produced are summarized in Table 1. The
actual steady state values for each conversion can be found in Table 2.

Conversion Initial Guess for
Initiator
Concentration
(mol/l)
Initial Guess for
Monomer
Concentration
(mol/l)
Initial Guess for
Reactor
Temperature (K)
Initial Guess for
Jacket Temperature
(K)
High Conversion 0.8009 0.002 0.5 400 360
Medium Conversion 0.2232 0.02 3 340 320
Low Conversion 0.0.0455 0.2 5 320 300



Conversion Steady State
Initiator
Concentration
(mol/l)
Steady State
Monomer
Concentration
(mol/l)
Steady State
Reactor
Temperature (K)
Steady State
Jacket
Temperature (K)
High Conversion 0.8009 0.0008 0.6927 406.2144 334.6012
Medium Conversion 0.2232 0.0615 2.7027 343.0869 312.1228
Low Conversion 0.0.0455 0.068 3.3245 323.1681 305.1681
Table 1: A summary of the initial guesses used to find each of the steady states for the CSTR model for producing polystyrene.
Table 2: The actual values found at each steady state using Newton iteration.
6
Once these steady state conversions were found, the stability of each was analyzed. Stability of
a steady state can be determined by calculating the eigenvalues of the Jacobian Matrix at the given
steady state. The eigenvalues at each steady state were found using the Matlab eig function. The
resulting eigenvalues define the stability of each steady state. For example, the eigenvalues calculated at
the high conversion steady state were all negative or complex numbers with negative real parts. This set
of eigenvalues implies that the high conversion steady state is stable and attractive. This particular
steady state is known as a stable focus. The eigenvalues produced for each steady state and the
corresponding stability analysis is summarized in Table 3.
Eigenvalue 1 Eigenvalue 2 Eigenvalue 3 Eigenvalue 4 Stability Attractivity Type of Critical
Point
Stiffness Value
High
Conversion
-0.0066 -0.0002
+0.0001i
-0.0002-
0.0001i
0 stable attractive focus 148.2183
Low
Conversion
-0.0367 -0.0881 -0.1026
+0.0060i
-0.1026 -
0.0060i
stable attractive focus 2.8004
Medium
Conversion
0.9879 -0.7216
+0.1936i
-0.7216
-0.1936i
-0.9318 unstable unattractive saddle 1.3222


As can be seen in Table 3, the medium conversion steady state was determined to be unstable, due to a
positive eigenvalue. This explains why the medium conversion steady state was initially hard to find. The
initial guesses needed to be especially close to the medium conversion steady state values. The stability
of these steady state values will be revisited later in the dynamic analysis of this CSTR reactor.
Dynamic Analysis:
The dynamic analysis of this mathematical model involved the solution of four coupled ordinary
differential equations. The method that was used to solve these differential equations was Eulers
Explicit Method. Euler's Explicit method is acceptable if the system is not stiff. Because each of the
ordinary differential equations is nonlinear, it is impossible to determine the overall stiffness of the
system. However, it is possible to get a very good estimate of the systems stiffness if it is evaluated
around each of the steady states. The stiffness of the system around each of the steady states was
determined using Equation 1.

|

|
|

|


If the stiffness value is close in magnitude to one then the system can be considered not stiff. If
the stiffness value is much greater than one, then the system is stiff. The stiffness values for each steady
state were low enough to consider the system as not stiff. The precise stiffness values can be seen in
Table 3. This stiffness evaluation allowed the analysis to proceed accurately with Eulers Explicit
Method. This method allows the ordinary differential equations to be discretized in space, creating a
large system of linear algebraic equations that can be solved explicitly. The low conversion steady state
Table 3: The eigenvalues and stability for each steady state conversion
Equation 1: equation for stiffness, where denotes an eigenvalue for a given state.
7
values for concentration and temperature were used as initial conditions for the dynamic analysis.
However, the feed temperature was set at 350 K, so the profile did not remain at the steady state
points. The program designed to run this dynamic analysis was created in Matlab and listed in Appendix
1. The maximum time for any dynamic process can be calculated by using Equation 2 below.

|

The maximum time step for the low conversion was found to be 11.35 seconds, but a time step
of 5 seconds was used. This ensures a more accurate dynamic analysis. After running the analysis, the
concentration and temperature profiles were plotted. The results for concentration and temperature
profiles can be seen in Figure 5.











As can be seen in Figure 5a, the concentration of the monomer (green) begins at the initial
steady state concentrations and drops sharply. This shows that the monomer is reacting to form
polystyrene. The slight increase is due to the reaction of monomer slowing down, and fresh monomer
being added to the CSTR. Since fresh monomer is being added, and the reaction is not as large, the
monomer concentration in the reactor increases. Eventually, the addition of monomer is neutralized by
the polymerization reaction and a steady state concentration is reached. The initiator concentration
begins at the steady state value and after approximately five hours, the initiator concentration drops to
zero where it remains for the duration of the process. The initiator concentration drops at the same
time that the monomer concentration reaches a minimum. This is expected because once there is no
more initiator in the reactor, the consumption of the monomer for the polystyrene polymerization
reaction slows down. As a result, the addition of fresh monomer increases the monomer concentration
in the reactor. Eventually, no more reaction is taking place and the monomer concentration remains
Figure 5: a) Concentration of initiator (blue) and monomer (green) for low conversion values. b) Reactor temperature (blue) and jacket temperature (green).
8
steady as the flow rate in and out of the reactor are the same, so equal amounts of monomer are
entering and leaving. These concentrations are also affected by the reactor temperature. Although the
reactor is initially at a low conversion steady state, the warmer feed heats up the reactor enough to
force the reactor to a new, high steady state, at a conversion of 0.8509.
Figure 5b shows the reactor temperature (blue) and jacket temperature (green) profiles. At
about five hours, the reactor temperature reaches a maximum. It should be noted that this initial spike
in reactor temperature is most likely unsafe. In order to diminish this effect, a decreased jacket
temperature would be recommended to absorb some of the heat created by the initial spike in the
reaction. This increase in temperature is expected because the monomer concentration is at a
minimum at this point. The reaction is exothermic, so a large amount of heat is being produced, thus
increasing the reactor temperature. This also means that the monomer is being consumed in the
reaction, so its concentration will decrease drastically. Due to the increase in reactor temperature, the
jacket temperature also increases during this time. After this maximum, the reactor temperature begins
to decline due to decreased initiator concentration, and due to an influx of fresh feed that is now below
the reactor temperature. As the initiator is consumed, the system begins to reach a steady state, and
equilibrium is reached between the heat produced by the reaction and the heat transferred into the
cooling jacket. The jacket temperature also reaches a steady state at this time.
The process was then analyzed at the medium conversion steady state. The feed temperature
was changed to 300 K, so the dynamics could be analyzed. The maximum time step was analyzed using
Equation 2 shown above. The maximum time step was found to be 1.012 seconds, so a time step of 0.1
seconds was chosen. Figure 6 below shows the concentration and temperature profiles of this dynamic
analysis.











Figure 6: a) Concentration of initiator (blue) and monomer (green) for medium conversion values. b) Reactor temperature (blue) and jacket temperature (green).
9
Looking at Figure 6, it can be seen that the conditions result in a diminished reaction. The
reactor was initially at 343 K; however the feed entered at 300 K. The colder feed causes the reactor
temperature to decrease. The temperature of the reactor and the jacket then converged to new steady
state temperatures, which were much lower than the initial temperature. Since the reactor temperature
evolved to a much lower steady state temperature, a lower conversion ensued. A lower conversion
implies an increase in monomer concentration throughout the reactor, which can be seen in Figure 6a.
The initiator concentration increased slightly as the process continued, which was due to the feed
stream entering and adding more initiator. However, initiator was not being used up because reaction
was happening at a lower magnitude. Although the reactor is initially at the medium conversion steady
state the cold feed causes the reactor to move to a new, lower steady state, at a conversion of 0.0031.
The conversions for both of the dynamic analyses were plotted against the reactor temperature.
The results are displayed below in Figure 7 below.











Figure 7 shows two strands of a phase portrait, one for the reactor initially at the medium
conversion steady state (leftmost) and another for the reactor initially at the low conversion steady
state (rightmost). It can be seen that the leftward strand diverges from the medium conversion steady
state at 0.2232 to a much lower conversion steady state at around 0.0031. This lower conversion also is
accompanied by a decreasing temperature. On the other hand, the right ward strand is initially at the
low conversion steady state, but the influx of warm feed causes the reaction to accelerate and reach a
new steady state at a conversion of 0.8509. Although it was expected that perturbing the reactor by
adding feeds at different temperatures could result in the reactor moving to a new steady state, it was
unexpected that these steady states would not be the same as the ones found in the steady state
analysis. However, this dilemma is resolved when the conditions for which those initial steady states
Figure 7: Conversion versus reactor temperature for the low and medium conversion dynamic processes.
10
were calculated. In the steady state analysis of this system the feed temperature was taken to be
constant at 330 K, however, in the dynamic analysis above the feed was varied at 300 and 350, leading
to new steady states. In fact, most likely if the initial conditions for the reactor are varied then three new
steady states could be found for each of the altered feed temperatures.












The above phase plane portrait shows the steady state conversion tendencies for the CSTR
reactor at varying initial temperatures. This phase portrait was created for a feed entering at 330 K; the
same conditions as in the steady state analysis. As can be seen in Figure 8, the initial reactor
temperature will determine if the reactor will tend toward any of the three steady state conversions:
high medium or low. If the reactor temperature is initially greater than around 343 K the reactor will
most likely proceed to the high conversion steady state of 0.8009, and a temperature of 406 K.
However, if the reactor is initially below 343 K then the reactor tends toward the low conversion steady
state of 0.0455, and a temperature of 323 K. These two steady states are stable to slight perturbation of
initial reactor temperatures. This stability makes sense when the eigenvalues around these critical
points are revisited. The eigenvalues all had negative real parts, and there were imaginary parts in a
couple of them. This set of eigenvalues is distinctive for critical points that are known as stable focus
points. Stable focus points show characteristic spirals which can be seen for the high and low conversion
steady states. The last steady state is the medium conversion steady state, which appears in Figure 8 to
be unstable. There does seem to be one strand of the phase portrait that appears to converge to the
medium conversion steady state. This strand represents the dynamics of a reactor that begins at 343 K,
which is in fact the medium conversion steady state reactor temperature. This means that the only way
the reactor will converge to this steady state is if the initial conditions of the reactor are very close to
Figure 8: Phase-plane portrait of conversion at varying initial reactor temperatures for
a feed entering at 340 K.
11
the steady state conditions. When looking at the eigenvalues, this instability is expected, because one of
the eigenvalues is positive and real. Positive eigenvalues are characteristic of unstable critical points.
Overall, the dynamic analysis gave an insight to the importance of initial reactor conditions in
the convergence to steady states. Specifically, as the initial reactor temperature is lowered the low
convergence steady state becomes more favorable, but as the initial reactor temperature is increased
the high conversion steady state becomes more favorable. Also, this dynamic analysis displayed the
importance of feed temperature on steady state values. Specifically, as the feed temperature is
increased the reactor will converge to higher conversion steady states, but as the feed temperature is
lowered the reactor will converge to lower conversion steady states.



















12
Mathematical Modeling of Polystyrene Plug-Flow Reactor
Steady State Analysis:
The next analysis was performed on the same reaction, but a plug-flow reactor was used instead
of a CSTR. The initiator and monomer concentrations were again modeled using differential mass
balances. Energy balances were also performed on the reactor and jacket temperatures. Numerical
methods were used to simulate the steady state and dynamic process behavior of the reactor. Since the
reactor is no longer a tank, the concentrations and temperatures change with position. When modeling
the dynamic process, these values also change with time.
Steady-state concentrations and temperatures at each position in the reactor were solved using
the finite differences method. Specifically, centered differences were used to approximate the
derivatives, so an algebraic equation could be formed. This method is the one of the most accurate of
the discretization methods. Equations 3 and 4 show how the first and second derivatives were
transformed using centered differences method. This transforms the second order ordinary differential
equation into a system of linear algebraic equations.

Solving for the steady state at each position along the reactor creates a boundary value
problem, so only boundary conditions were necessary to solve the problem. The left side boundary
conditions were Dirichlet boundary conditions, so no discretization was required. However, the right
side boundary conditions were Robin conditions, so the derivatives needed to be discretized using
Equation 3. For the space points between the boundaries, the derivatives were discretized as explained
above. In order to solve the problem, a super-matrix was setup that was size 4*N x 1. This allowed it to
be solved using the fsolve command in Matlab. The first N rows of the matrix corresponded to initiator
concentration, the next N were monomer concentration, and so on. The program that was created in
Matlab to solve these equations can be found in Appendix 2. The steady state concentrations and
temperatures that were calculated are displayed below in Figure 9.






13

















It can be seen in Figures 9a and 9b, that the initiator and monomer concentrations stay
relatively constant going from the left to the right side of the reactor. This means that the reaction is
not taking place, so the inflow of initiator and monomer are balanced by the flow out of the reactor.
Figures 9c and 9d show the temperature profiles of the reactor and jacket, respectively. The
temperature of the reactor begins at 330 K and decreases quickly to 295.9 K. The jacket temperature
begins at 295 K and increases to the equilibrium temperature of 295.9 K. These results show that this
process is basically a heat exchanger, with the jacket cooling the feed to a temperature of 295.9 K. The
jacket temperature is heated slightly up to the equilibrium temperature of 295.9 K. The lack of reaction
could be explained by the system being too stiff to be solved by the finite differences method. The
constants given for the model mostly likely are the root of this stiffness. Of the methods that have been
learned, none of them were able to solve a very stiff system accurately.

Figure 9: Steady state values of a) Initiator Concentration b) Monomer Concentration c) Reactor Temperature d)
Jacket Temperature with increasing position within the PFR reactor.
14

Dynamic Analysis:
The dynamic analysis of the plug flow reactor was then performed to model the behavior of the
system throughout time, as well as space. Both Eulers Explicit and Implicit methods were used to
numerically solve the resulting partial differential equations. To approximate the time derivatives, the
Explicit method uses forward differences, which can be seen in Equation 5.

It is acceptable to use this method for systems of nonlinear differential equations that are not
stiff.
On the other hand, the Implicit method uses backward differences, which is shown in Equation
6. It is used for nonlinear differential equations that are stiff.

Eulers Explicit method was used first to model the dynamic behavior of the reactor, and the
results for the concentration and temperature profiles are displayed in Figure 10.













Figure 10: The dynamic profiles of a) initiator concentration, b) monomer concentration, c) jacket temperature, d) reactor
temperature for the PFR polystyrene production analysis using Eulers Explicit method.
15


Figure 10a shows the initiator concentration profile. At initial time and the entrance of the
reactor, the concentration is at 8,698 mol/m
3
. Almost as soon the initiator enters the reactor, its
concentration drops very low. Also, as time progresses, the concentration at the entrance of the reactor
remains constant at its initial value. Inside of the reactor, the concentration goes to zero as time
progresses. Figure 10b highlights the same results for the monomer concentration. It begins at a
concentration of 588.8 mol/m
3
and drops very low when it enters the reactor. The concentration
profiles basically describe a reactor that is simply beginning to fill up with the feed. These results can be
explained by the shortness of this dynamic analysis. The model was only stable enough to describe the
system for about the first minute. Therefore, the reactor didnt have enough time to even fill the reactor
yet. The root of this problem is ones again stiffness. This system is too stiff to be solved using Eulers
Explicit method. The concentration plots show the reactor filling up with some initiator and monomer
towards the left side of the reactor, but the values never reach any substantial concentration toward the
right side of the reactor. The zero concentration values are not due to the reaction being able to
consume them at very high rates. Instead, the system is too stiff to use Eulers Explicit Method after the
first few minutes.
The constant concentration values can also be seen by the plots in Figures 10c and 10d which
show the reactor and jacket temperatures, respectively. The reactor temperature begins at 330 K at the
left boundary, but after around 45 seconds the left side begins to increase in temperature. If the
temperature profile were to continue in time, it would begin to oscillate, and eventually complex
numbers would begin to be found as solutions. Again, this diverging reactor temperature can be
attributed to system stiffness which causes error build-up and instability propagation. The jacket
temperature begins at 295 K at the left boundary, and increases throughout the reactor in time. Around
the same time the reactor temperature begins to increase rapidly, the jacket temperature starts to slope
upward as heat is transferred from the reactor to the jacket. The instability that can be seen in the
reactor temperature will have an effect on the entire system, and the model breaks down shortly after a
minute. All of these effects can be correlated to the instability of Eulers Explicit method when used for
stiff systems.
Since the system was too stiff to be solved by Eulers Explicit, the Implicit method was used in
order to decrease the error of the dynamic analysis and show profiles that ranged longer in time. The
results from this method can be seen below in Figure 11.




16





















Figure 11a shows the initiator concentration profile. At the inlet of the reactor at an initial
time, the concentration is at 588.8 mol/m
3
. As time progresses, the initiator concentration has a spike in
its value, and then it oscillates in time at a constant position within the reactor. These oscillations are
also due to the system being too stiff for this method to solve. Normally, stiff systems are solved with
the Implicit method, but even this system is too stiff. This same result can be seen in Figure 11b for the
monomer concentration within the reactor. Both the initiator and monomer concentration profiles
have the same shape and look very similar. As time and position within the reactor increase, the
Figure 11: The dynamic profiles of a) initiator concentration, b) monomer concentration, c) reactor temperature, d) jacket temperature for the PFR
Polystyrene production analysis using Eulers Implicit method.
17
concentration of initiator and monomer begin to increase, which means the reactor is being filled with
these materials. The concentrations remain relatively constant at the initial values as time elapses.
These results imply that no reaction is occurring, but this can be attributed to the very stiff system.
Due to the stiffness of the system, the plug flow reactor is simulated to act as a simple heat
exchanger. Figures 11c and 11d display the reactor and jacket temperature profiles. The reactor
temperature begins at its initial condition of 330 K and quickly decreases to 310 K. There is a sudden
increase in the temperature around 150 seconds, which is the same time the monomer concentration
spikes. The spike in the monomer concentration is due to system stiffness creating error build-up, which
causes the reactor temperature to spike. As a result, the jacket temperature has a sudden increase at
this same time because heat is being transferred from the reactor to the jacket. Eventually, both the
jacket and reactor temperature decrease to 295 K and 380 K, respectively, as time progresses. At the
inlet of the reactor, the temperatures are at their boundary conditions and at the first position within
the reactor, the temperature rapidly drops to 280 K and begins to oscillate. This can be seen the best at
longer time points as the process begins to reach steady state. Again, the Eulers Implicit method was
unable to solve this system accurately due to large system stiffness. The error associated with Eulers
Explicit Method is on the order of the time step squared. Eulers Implicit Method lowers this error to be
on the order of just the time step. Still, the system was stiff enough that this error was large enough to
accumulate and create oscillating and diverging solutions. In order to more accurately analyze the plug
flow reactor, a different method should be used to deal with the stiffness.

Conclusion
After analyzing both reactors for the production of polystyrene, more analysis needs to be
completed to determine the best reactor for the process. The CSTR had stable low and high conversion
steady states for the given parameters and conditions of the reactor. There was a medium conversion
steady state, but it was unstable, so these conditions would be very hard to obtain. Having a stable high
conversion steady state shows promise for this reactor to be used in production of polystyrene. Also,
this system had a very low stiffness ratio, so Eulers Explicit method could be used to numerically solve
the problem. As a result, a system of algebraic equations did not need to be solved, making the solution
easier to obtain. The mathematical model for this process was successful in obtaining a solution to both
the steady state and dynamic problems.
On the other hand, the plug flow reactor analysis did not yield useful results. The system was
extremely stiff, even for Eulers Implicit method. Steady states were obtained, but it was concluded that
the concentration did not change with position in the reactor. As a result, the reactor became a simple
co-current heat exchanger, with the jacket and reactor temperatures reaching an equilibrium. For the
dynamic analysis, the system was again too stiff to be solved by Eulers Explicit and Implicit methods.
Again, the results showed that no reaction was occurring and the jacket was cooling the reactor
contents. In order to more effectively analyze the process, a method could have been used that solves
18
very stiff systems. Overall, the CSTR analysis shows promise for this operation, but the PFR would need
to be more accurately analyzed or modeled to make a definite conclusion.

Appendix

Appendix 1
Problem 1.1 and 1.2 Code
%Finding steady states with Newton's Method and analyzing stability and
%stiffness

function [x]=project11(k) %k is the number of iterations used (1000)

%Below are the initial guesses used to solve for the low, med, and high
%conv steady states

%x=[0.2;5;320;300]; %Conv=0.0445 %Low Conv SS
x=[0.02;3;340;320]; %Conv=0.2232 %Int Conv SS
%x=[0.002;0.5;400;360]; %Conv=0.8009 %High Conv SS

Fs=0.1275; %feed solvent flow rate
Fm=0.105; %feed monomer flow rate
Fi=0.03; %feed initiator flow rate
Cma=8.698; %feed monomer concentration
Cia=0.5888; %feed initiator concentration
Ta=330; %feed temperature
V=3000; %reactor volume
Vj=3312.4; %jacket volume
Tjin=295; %inlet jacket temperature
rhoCp=360; %density of reacting mixture*heat capacity
Fj=0.131; %heat-conducting fluid flow rate
rhojCpj=966.3; %density of the heat conducting fluid*heat capacity
UA=70; %Global heat transfer coefficient*heat exchange area between the jacket and reactor
constituents
f=0.6; %initiator efficiency
dH=-16700; %heat of reaction
kdo=5.95*(10^13); %preexponential factor for dissociation
Ed=14897; %activation energy for dissociation
kpo=1.06*(10^7); %preexponential factor for propagation
Ep=3557; %activation energy for propagation
kto=1.25*(10^9); %preexponential factor for termination
Et=843; %activation energy for termination

%Calculation of the Jacobian for Newton's Method
%syms x1 x2 x3 x4
%F1=(Fi*Cia-(Fi+Fm+Fs)*x1)/(V)-(kdo*exp(-(Ed)/x3)*x1);
%F2=(Fm*Cma-(Fi+Fm+Fs)*x2)/V-(kpo)*exp(-Ep/x3)*x2*(2*f*kdo*exp(Ed/x3)*x1/(kto*exp(Et/x3)))^(0.5);
%F3=(Fi+Fm+Fs)*(Ta-x3)/V-
dH/(rhoCp)*kpo*exp(Ep/x3)*x2*(2*f*kdo*exp(Ed/x3)*x1/(kto*exp(Et/x3)))^(0.5)-UA/(rhoCp*V)*(x3-x4);
%F4=Fj*(Tjin-x4)/Vj+UA/(rhojCpj*Vj)*(x3-x4);


%J=[diff(F1,x1), diff(F1,x2), diff(F1,x3), diff(F1,x4);
%diff(F2,x1), diff(F2,x2), diff(F2,x3), diff(F2,x4);
%diff(F3,x1), diff(F3,x2), diff(F3,x3), diff(F3,x4);
%diff(F4,x1), diff(F4,x2), diff(F4,x3), diff(F4,x4)]

% J =[- 59500000000000*exp(-14897/x3) - 7/80000, 0, -(886371500000000000*x1*exp(-
14897/x3))/x3^2, 0]
19
%[-(302736000000*x2*exp(-17611/x3))/(57120*x1*exp(-14054/x3))^(1/2),- 10600000*exp(-
3557/x3)*(57120*x1*exp(-14054/x3))^(1/2) - 7/80000, - (37704200000*x2*exp(-
3557/x3)*(57120*x1*exp(-14054/x3))^(1/2))/x3^2 - (4254651744000000*x1*x2*exp(-
17611/x3))/(x3^2*(57120*x1*exp(-14054/x3))^(1/2)), 0]
%[ (7362883966293333135*x2*exp(-17611/x3))/(524288*(57120*x1*exp(-14054/x3))^(1/2)),
(4124864967111111*exp(-3557/x3)*(57120*x1*exp(-14054/x3))^(1/2))/8388608,
(14672144688014221827*x2*exp(-3557/x3)*(57120*x1*exp(-14054/x3))^(1/2))/(8388608*x3^2) +
(51738985631143251939645*x1*x2*exp(-17611/x3))/(262144*x3^2*(57120*x1*exp(-14054/x3))^(1/2)) -
7024281018808382541/46116860184273879040000, 4782489204295069/73786976294838206464]
%[ 0, 0, 3227401481264261/147573952589676412928, -
1876414528486709264373/30551497534877759386419200]


for j=1:k

F1=(Fi*Cia-(Fi+Fm+Fs)*x(1))/(V)-(kdo*exp(-(Ed)/x(3))*x(1));
F2=(Fm*Cma-(Fi+Fm+Fs)*x(2))/V-((kpo)*exp(-Ep/x(3)))*x(2)*(2*f*kdo*exp(-
Ed/x(3))*x(1)/(kto*exp(-Et/x(3))))^(0.5);
F3=(Fi+Fm+Fs)*(Ta-x(3))/V-dH/(rhoCp)*kpo*exp(-Ep/x(3))*x(2)*(2*f*kdo*exp(-
Ed/x(3))*x(1)/(kto*exp(-Et/x(3))))^(0.5)-UA/(rhoCp*V)*(x(3)-x(4));
F4=Fj*(Tjin-x(4))/Vj+UA/(rhojCpj*Vj)*(x(3)-x(4));

df1x1=-59500000000000*exp(-14897/x(3)) - 7/80000;
df1x2=0;
df1x3=-(886371500000000000*x(1)*exp(-14897/x(3)))/x(3)^2;
df1x4=0;
df2x1=-(302736000000*x(2)*exp(-17611/x(3)))/(57120*x(1)*exp(-14054/x(3)))^(1/2);
df2x2=- 10600000*exp(-3557/x(3))*(57120*x(1)*exp(-14054/x(3)))^(1/2) - 7/80000;
df2x3=- (37704200000*x(2)*exp(-3557/x(3))*(57120*x(1)*exp(-14054/x(3)))^(1/2))/x(3)^2 -
(4254651744000000*x(1)*x(2)*exp(-17611/x(3)))/(x(3)^2*(57120*x(1)*exp(-14054/x(3)))^(1/2));
df2x4=0;
df3x1= (7362883966293333135*x(2)*exp(-17611/x(3)))/(524288*(57120*x(1)*exp(-
14054/x(3)))^(1/2));
df3x2=(4124864967111111*exp(-3557/x(3))*(57120*x(1)*exp(-14054/x(3)))^(1/2))/8388608;
df3x3=(14672144688014221827*x(2)*exp(-3557/x(3))*(57120*x(1)*exp(-
14054/x(3)))^(1/2))/(8388608*x(3)^2) + (51738985631143251939645*x(1)*x(2)*exp(-
17611/x(3)))/(262144*x(3)^2*(57120*x(1)*exp(-14054/x(3)))^(1/2))-
7024281018808382541/46116860184273879040000;
df3x4=4782489204295069/73786976294838206464;
df4x1=0;
df4x2=0;
df4x3=3227401481264261/147573952589676412928;
df4x4=-1876414528486709264373/30551497534877759386419200;

DF=[df1x1 df1x2 df1x3 df1x4;df2x1 df2x2 df2x3 df2x4;df3x1 df3x2 df3x3 df3x4;df4x1 df4x2 df4x3
df4x4];
F=[F1;F2;F3;F4];
xo=x;
x=xo-(inv(DF)*F);
c=(norm((x-xo),1))/(norm(x,1));
if c<=0.00000001
break;
end
end
conv=((Fm*Cma)-((Fi+Fm+Fs)*x(2)))/(Fm*Cma)
lambda=eig(DF)
lambdamin=min(abs(lambda));
lambdamax=max(abs(lambda));
Stiffness=lambdamax/lambdamin
end


Problem 1.3 Code
%Simulation of dynamic process using Euler Explicit at low conversion
%steady state

function [xplot,Tplot,tplot,Xplot]=project13(k,dt,x1o,x2o,x3o,x4o,Xo)
20

%k is number of iterations (20000)
%dt is time step (5)
%Initial conditions are low conversion SS values
%x1o=0.068
%x2o=3.3245
%x3o=323.5557
%x4o=305.1681
%Xo=0.0455

Fs=0.1275; %feed solvent flow rate
Fm=0.105; %feed monomer flow rate
Fi=0.03; %feed initiator flow rate
Cma=8.698; %feed monomer concentration
Cia=0.5888; %feed initiator concentration
Ta=350; %feed temperature
V=3000; %reactor volume
Vj=3312.4; %jacket volume
Tjin=295; %inlet jacket temperature
rhoCp=360; %density of reacting mixture*heat capacity
Fj=0.131; %heat-conducting fluid flow rate
rhojCpj=966.3; %density of the heat conducting fluid*heat capacity
UA=70; %Global heat transfer coefficient*heat exchange area between the jacket and reactor
constituents
f=0.6; %initiator efficiency
dH=-16700; %heat of reaction
kdo=5.95*(10^13); %preexponential factor for dissociation
Ed=14897; %activation energy for dissociation
kpo=1.06*(10^7); %preexponential factor for propagation
Ep=3557; %activation energy for propagation
kto=1.25*(10^9); %preexponential factor for termination
Et=843; %activation energy for termination


to=0;
xo=[x1o;x2o];
To=[x3o;x4o];

Xplot=zeros(k,1);
xplot=zeros(k,2);
xplot(1,:)=xo;
Tplot=zeros(k,2);
Tplot(1,:)=To;
tplot=zeros(k,1);
Xplot(1,:)=Xo;
for j=1:k
x1t=x1o+dt*((Fi*Cia-(Fi+Fm+Fs)*x1o)/(V)-(kdo*exp(-(Ed)/x3o)*x1o));
x2t=x2o+dt*((Fm*Cma-(Fi+Fm+Fs)*x2o)/V-((kpo)*exp(-Ep/x3o))*x2o*(2*f*kdo*exp(-
Ed/x3o)*x1o/(kto*exp(-Et/x3o)))^(0.5));
x3t=x3o+dt*((Fi+Fm+Fs)*(Ta-x3o)/V-dH/(rhoCp)*kpo*exp(-Ep/x3o)*x2o*(2*f*kdo*exp(-
Ed/x3o)*x1o/(kto*exp(-Et/x3o)))^(0.5)-UA/(rhoCp*V)*(x3o-x4o));
x4t=x4o+dt*(Fj*(Tjin-x4o)/Vj+UA/(rhojCpj*Vj)*(x3o-x4o));

x1o=x1t;
x1=x1o;

x2o=x2t;
x2=x2o;

x3o=x3t;
x3=x3o;

x4o=x4t;
x4=x4o;

x=[x1;x2];
xplot(j+1,:)=x;

T=[x3;x4];
Tplot(j+1,:)=T;

21
tt=to+dt;
to=tt;
t=to;
tplot(j+1,:)=t/3600;

Xo=((Fm*Cma)-((Fi+Fm+Fs)*x2o))/(Fm*Cma);
Xt=((Fm*Cma)-((Fi+Fm+Fs)*x2))/(Fm*Cma);
Xo=Xt;
X=Xo;
Xplot(j+1,:)=X;
end
hold on
figure(1)
plot(tplot,xplot)
xlabel 'Time (hours)'
ylabel 'Concentration (mol/L)'
hold off

% hold on
% figure(2)
% plot(tplot1,xplot1)
% xlabel 'Time (hours)'
% ylabel 'Concentration (mol/L)'
% hold off

%hold on
%figure (3)
%plot(Tplot(:,1),Xplot)
%xlabel 'Reactor Temperature (K)'
%ylabel 'Conversion'
%hold off
end

Problem 1.4 Code
%Simulation of dynamic process using Euler Explicit at medium conversion
%steady state

function [xplot1,Tplot1,tplot1,Xplot1]=project14(k,dt,x1o,x2o,x3o,x4o,Xo)

%k is number of iterations (10000)
%dt is time step (1)
%Initial conditions are med conversion SS values
%x1o=0.068
%x2o=3.3245
%x3o=323.5557
%x4o=305.1681
%Xo=0.0455

Fs=0.1275; %feed solvent flow rate
Fm=0.105; %feed monomer flow rate
Fi=0.03; %feed initiator flow rate
Cma=8.698; %feed monomer concentration
Cia=0.5888; %feed initiator concentration
Ta=300; %feed temperature
V=3000; %reactor volume
Vj=3312.4; %jacket volume
Tjin=295; %inlet jacket temperature
rhoCp=360; %density of reacting mixture*heat capacity
Fj=0.131; %heat-conducting fluid flow rate
rhojCpj=966.3; %density of the heat conducting fluid*heat capacity
UA=70; %Global heat transfer coefficient*heat exchange area between the jacket and reactor
constituents
f=0.6; %initiator efficiency
dH=-16700; %heat of reaction
kdo=5.95*(10^13); %preexponential factor for dissociation
Ed=14897; %activation energy for dissociation
kpo=1.06*(10^7); %preexponential factor for propagation
22
Ep=3557; %activation energy for propagation
kto=1.25*(10^9); %preexponential factor for termination
Et=843; %activation energy for termination


to=0;
xo=[x1o;x2o];
To=[x3o;x4o];

Xplot1=zeros(k,1);
xplot1=zeros(k,2);
xplot1(1,:)=xo;
Tplot1=zeros(k,2);
Tplot1(1,:)=To;
tplot1=zeros(k,1);
Xplot1(1,:)=Xo;
for j=1:k
x1t=x1o+dt*((Fi*Cia-(Fi+Fm+Fs)*x1o)/(V)-(kdo*exp(-(Ed)/x3o)*x1o));
x2t=x2o+dt*((Fm*Cma-(Fi+Fm+Fs)*x2o)/V-((kpo)*exp(-Ep/x3o))*x2o*(2*f*kdo*exp(-
Ed/x3o)*x1o/(kto*exp(-Et/x3o)))^(0.5));
x3t=x3o+dt*((Fi+Fm+Fs)*(Ta-x3o)/V-dH/(rhoCp)*kpo*exp(-Ep/x3o)*x2o*(2*f*kdo*exp(-
Ed/x3o)*x1o/(kto*exp(-Et/x3o)))^(0.5)-UA/(rhoCp*V)*(x3o-x4o));
x4t=x4o+dt*(Fj*(Tjin-x4o)/Vj+UA/(rhojCpj*Vj)*(x3o-x4o));

x1o=x1t;
x1=x1o;

x2o=x2t;
x2=x2o;

x3o=x3t;
x3=x3o;

x4o=x4t;
x4=x4o;

x=[x1;x2];
xplot1(j+1,:)=x;

T=[x3;x4];
Tplot1(j+1,:)=T;

tt=to+dt;
to=tt;
t=to;
tplot1(j+1,:)=t/3600;

Xo=((Fm*Cma)-((Fi+Fm+Fs)*x2o))/(Fm*Cma);
Xt=((Fm*Cma)-((Fi+Fm+Fs)*x2))/(Fm*Cma);
Xo=Xt;
X=Xo;
Xplot1(j+1,:)=X;
end
hold on
figure(1)
plot(tplot1,xplot1)
xlabel 'Time (hours)'
ylabel 'Concentration (mol/L)'
hold off

%hold on
%figure(2)
%plot(tplot1,xplot1)
%xlabel 'Time (hours)'
%ylabel 'Concentration (mol/L)'
%hold off

% hold on
% figure (3)
% plot(Tplot1(:,1),Xplot1)
% xlabel 'Reactor Temperature (K)'
23
% ylabel 'Conversion'
% hold off
end



Problem 1.5 Code
%Phase-portrait of dynamic process
clear
clc

Fs=0.1275; %feed solvent flow rate
Fm=0.105; %feed monomer flow rate
Fi=0.03; %feed initiator flow rate
Cma=8.698; %feed monomer concentration
Cia=0.5888; %feed initiator concentration
Ta=330; %feed temperature
V=3000; %reactor volume
Vj=3312.4; %jacket volume
Tjin=295; %inlet jacket temperature
rhoCp=360; %density of reacting mixture*heat capacity
Fj=0.131; %heat-conducting fluid flow rate
rhojCpj=966.3; %density of the heat conducting fluid*heat capacity
UA=70; %Global heat transfer coefficient*heat exchange area between the jacket and reactor
constituents
f=0.6; %initiator efficiency
dH=-16700; %heat of reaction
kdo=5.95*(10^13); %preexponential factor for dissociation
Ed=14897; %activation energy for dissociation
kpo=1.06*(10^7); %preexponential factor for propagation
Ep=3557; %activation energy for propagation
kto=1.25*(10^9); %preexponential factor for termination
Et=843; %activation energy for termination



for x3o=300:2:360; %low conversion
x1o=0.068;
x2o=3.3245;
x4o=305.1681;
Xo=.0455;
dt=1;
k=100000;

to=0;
xo=[x1o;x2o];
To=[x3o;x4o];

Xplot=zeros(k,1);
xplot=zeros(k,2);
xplot(1,:)=xo;
Tplot=zeros(k,2);
Tplot(1,:)=To;
tplot=zeros(k,1);
Xplot(1,:)=Xo;

for j=1:k
x1t=x1o+dt*((Fi*Cia-(Fi+Fm+Fs)*x1o)/(V)-(kdo*exp(-(Ed)/x3o)*x1o));
x2t=x2o+dt*((Fm*Cma-(Fi+Fm+Fs)*x2o)/V-((kpo)*exp(-Ep/x3o))*x2o*(2*f*kdo*exp(-
Ed/x3o)*x1o/(kto*exp(-Et/x3o)))^(0.5));
x3t=x3o+dt*((Fi+Fm+Fs)*(Ta-x3o)/V-dH/(rhoCp)*kpo*exp(-Ep/x3o)*x2o*(2*f*kdo*exp(-
Ed/x3o)*x1o/(kto*exp(-Et/x3o)))^(0.5)-UA/(rhoCp*V)*(x3o-x4o));
x4t=x4o+dt*(Fj*(Tjin-x4o)/Vj+UA/(rhojCpj*Vj)*(x3o-x4o));

x1o=x1t;
x1=x1o;
24

x2o=x2t;
x2=x2o;

x3o=x3t;
x3=x3o;

x4o=x4t;
x4=x4o;

x=[x1;x2];
xplot(j+1,:)=x;

T=[x3;x4];
Tplot(j+1,:)=T;

tt=to+dt;
to=tt;
t=to;
tplot(j+1,:)=t/3600;

Xo=((Fm*Cma)-((Fi+Fm+Fs)*x2o))/(Fm*Cma);
Xt=((Fm*Cma)-((Fi+Fm+Fs)*x2))/(Fm*Cma);
Xo=Xt;
X=Xo;
Xplot(j+1,:)=X;
end
hold on
figure (12)
pause(1)
plot(Tplot(:,1),Xplot)
xlabel 'Reactor Temperature (K)'
ylabel 'Conversion'
hold off
end

for x3o=300:2:360 %medium conversion
x1o=0.0615;
x2o=2.7027;
x4o=312.1228;
Xo=.2232;
dt=1;
k=100000;

to=0;
xo=[x1o;x2o];
To=[x3o;x4o];

Xplot=zeros(k,1);
xplot=zeros(k,2);
xplot(1,:)=xo;
Tplot=zeros(k,2);
Tplot(1,:)=To;
tplot=zeros(k,1);
Xplot(1,:)=Xo;
for j=1:k
x1t=x1o+dt*((Fi*Cia-(Fi+Fm+Fs)*x1o)/(V)-(kdo*exp(-(Ed)/x3o)*x1o));
x2t=x2o+dt*((Fm*Cma-(Fi+Fm+Fs)*x2o)/V-((kpo)*exp(-Ep/x3o))*x2o*(2*f*kdo*exp(-
Ed/x3o)*x1o/(kto*exp(-Et/x3o)))^(0.5));
x3t=x3o+dt*((Fi+Fm+Fs)*(Ta-x3o)/V-dH/(rhoCp)*kpo*exp(-Ep/x3o)*x2o*(2*f*kdo*exp(-
Ed/x3o)*x1o/(kto*exp(-Et/x3o)))^(0.5)-UA/(rhoCp*V)*(x3o-x4o));
x4t=x4o+dt*(Fj*(Tjin-x4o)/Vj+UA/(rhojCpj*Vj)*(x3o-x4o));

x1o=x1t;
x1=x1o;

x2o=x2t;
x2=x2o;

x3o=x3t;
x3=x3o;
25

x4o=x4t;
x4=x4o;

x=[x1;x2];
xplot(j+1,:)=x;

T=[x3;x4];
Tplot(j+1,:)=T;

tt=to+dt;
to=tt;
t=to;
tplot(j+1,:)=t/3600;

Xo=((Fm*Cma)-((Fi+Fm+Fs)*x2o))/(Fm*Cma);
Xt=((Fm*Cma)-((Fi+Fm+Fs)*x2))/(Fm*Cma);
Xo=Xt;
X=Xo;
Xplot(j+1,:)=X;
end
hold on
figure (12)
pause(1)
plot(Tplot(:,1),Xplot)
xlabel 'Reactor Temperature (K)'
ylabel 'Conversion'
hold off
end

for x3o=300:2:400 %high conversion
x1o=0.0008;
x2o=0.6927;
x4o=334.6012;
Xo=.8009;
dt=1;
k=100000;

to=0;
xo=[x1o;x2o];
To=[x3o;x4o];

Xplot=zeros(k,1);
xplot=zeros(k,2);
xplot(1,:)=xo;
Tplot=zeros(k,2);
Tplot(1,:)=To;
tplot=zeros(k,1);
Xplot(1,:)=Xo;
for j=1:k
x1t=x1o+dt*((Fi*Cia-(Fi+Fm+Fs)*x1o)/(V)-(kdo*exp(-(Ed)/x3o)*x1o));
x2t=x2o+dt*((Fm*Cma-(Fi+Fm+Fs)*x2o)/V-((kpo)*exp(-Ep/x3o))*x2o*(2*f*kdo*exp(-
Ed/x3o)*x1o/(kto*exp(-Et/x3o)))^(0.5));
x3t=x3o+dt*((Fi+Fm+Fs)*(Ta-x3o)/V-dH/(rhoCp)*kpo*exp(-Ep/x3o)*x2o*(2*f*kdo*exp(-
Ed/x3o)*x1o/(kto*exp(-Et/x3o)))^(0.5)-UA/(rhoCp*V)*(x3o-x4o));
x4t=x4o+dt*(Fj*(Tjin-x4o)/Vj+UA/(rhojCpj*Vj)*(x3o-x4o));

x1o=x1t;
x1=x1o;

x2o=x2t;
x2=x2o;

x3o=x3t;
x3=x3o;

x4o=x4t;
x4=x4o;

x=[x1;x2];
xplot(j+1,:)=x;
26

T=[x3;x4];
Tplot(j+1,:)=T;

tt=to+dt;
to=tt;
t=to;
tplot(j+1,:)=t/3600;

Xo=((Fm*Cma)-((Fi+Fm+Fs)*x2o))/(Fm*Cma);
Xt=((Fm*Cma)-((Fi+Fm+Fs)*x2))/(Fm*Cma);
Xo=Xt;
X=Xo;
Xplot(j+1,:)=X;
end
hold on
figure (12)
pause(1)
plot(Tplot(:,1),Xplot)
xlabel 'Reactor Temperature (K)'
ylabel 'Conversion'
hold off
end

Appendix 2
Problem 2.7 Code
%Solving the finite differences equations

function [z,xt]=project27SS(xg1,xg2,xg3,xg4,dS)

%dS is space step (0.1)
%guesses are the left side boundary conditions
%x1g=0.0005888
%x2g=0.008698
%x3g=330
%x4g=295

L=300;
N=L/dS+1;
z=zeros(N,1);
xo=zeros(4*N,1);
xo(1)=xg1;
xo(N+1)=xg2;
xo(2*N+1)=xg3;
xo(3*N+1)=xg4;

for i=2:N
z(i)=z(i-1)+dS;
xo(i)=xg1;
xo(N+i)=xg2;
xo(2*N+i)=xg3;
xo(3*N+i)=xg4;
end
%test=project21(xo);
xt=fsolve(@(xf) project27(xf,dS),xo,optimset('Display','off'));

%Solving the steady state for PFR

function F=project27(x,dS)

Fs=0.1275*1000; %feed solvent flow rate
Fm=0.105*1000; %feed monomer flow rate
Fi=0.03*1000; %feed initiator flow rate
rhoCp=360*10; %density of reacting mixture*heat capacity
rhojCpj=966.3*10; %density of the heat conducting fluid*heat capacity
27
UA=70; %Global heat transfer coefficient*heat exchange area between the jacket and reactor
constituents
f=0.6; %initiator efficiency
dH=-16700*10000; %heat of reaction
kdo=5.95*(10^13); %preexponential factor for dissociation
Ed=14897; %activation energy for dissociation
kpo=1.06*(10^7); %preexponential factor for propagation
Ep=3557; %activation energy for propagation
kto=1.25*(10^9); %preexponential factor for termination
Et=843; %activation energy for termination
L=300; %Reactor Length
d=30; %Reactor Diameter
v=(Fi+Fm+Fs)/((pi*((d)^2))/4); %axial fluid velocity
vj=5; %Axial heat-conducting fluid velocity
D1=5*(10^-6); %Initiator Diffusivity
D2=1.4*(10^-7); %Monomer Diffusivity
k=3.3; %Fluid thermal conductivity
kj=56; %Heat conducting fluid thermal conductivity
x1o=.0005888;
x2o=.008698;
x3o=330;
x4o=295;


N=L/dS+1;
F=zeros(4*N,1);
F(1)=x(1)-x1o; %Left side boundary condition for initiator concentration
F(N+1)=x(N+1)-x2o; %Left side boundary condition for monomer concentration
F(2*N+1)=x(2*N+1)-x3o; %Left side boundary condition for reactor temp
F(3*N+1)=x(3*N+1)-x4o; %Left side boundary condition for jacket temp
for i=2:N-1
kd=kdo*exp(-Ed/x(2*N+i));
kp=kpo*exp(-Ep/x(2*N+i));
kt=kto*exp(-Et/x(2*N+i));
R=(((2*f*kd*x(i))/(kt))^2)^0.25;
F(i)=-v*((x(i+1)-x(i-1))/(2*(dS)))+D1*((x(i+1)-2*x(i)+x(i-1))/((dS)^2))-kd*x(i);
F(N+i)=-v*((x(N+i+1)-x(N+i-1))/(2*(dS)))+D2*((x(N+i+1)-2*x(N+i)+x(N+i-1))/((dS)^2))-
kp*x(N+i)*R;
F(2*N+i)=-v*((x(2*N+i+1)-x(2*N+i-1))/(2*(dS)))+(k/rhoCp)*((x(2*N+i+1)-2*x(2*N+i)+x(2*N+i-
1))/((dS)^2))-(dH/rhoCp)*kp*x(N+i)*R-((UA)/rhoCp)*(x(2*N+i)-x(3*N+i));
F(3*N+i)=-vj*((x(3*N+i+1)-x(3*N+i-1))/(2*(dS)))+(kj/rhojCpj)*((x(3*N+i+1)-2*x(3*N+i)+x(3*N+i-
1))/((dS)^2))+((UA)/rhojCpj)*(x(2*N+i)-x(3*N+i));
end
F(N)=D1*((2*x(N-1)-2*x(N))/((dS)^2))-(kdo*exp(-Ed/x(3*N)))*x(N); %Right side boundary condition
for initiator concentration
F(2*N)=D2*((2*x(2*N-1)-2*x(2*N))/((dS)^2))-(kpo*exp(-Ep/x(3*N)))*x(2*N)*((((2*f*kdo*exp(-
Ed/x(3*N))*x(N))/(kto*exp(-Et/x(3*N))))^2)^0.25); %Right side boundary condition for monomer
concentration
F(3*N)=(k/rhoCp)*((2*x(3*N-1)-2*x(3*N))/((dS)^2))-(dH/rhoCp)*(kpo*exp(-
Ep/x(2*N)))*x(3*N)*((((2*f*kdo*exp(-Ed/x(3*N))*x(N))/(kto*exp(-Et/x(3*N))))^2)^0.25)-
((UA)/rhoCp)*(x(3*N)-x(4*N)); %Right side boundary condition for reactor temp
F(4*N)=(kj/rhojCpj)*((2*x(4*N-1)-2*x(4*N))/((dS)^2))+((UA)/rhojCpj)*(x(3*N)-x(4*N)); %Right side
boundary condition for jacket temp
end
figure(1)
plot(z,xt(1:N))
figure(2)
plot(z,xt(N+1:2*N))
figure(3)
plot(z,xt(2*N+1:3*N))
figure(4)
plot(z,xt(3*N+1:4*N))
end


Problem 2.8 Code (Euler Explicit)
%Dynamic simulation for PFR using euler explicit
28


function [S,time,x1,x2,x3,x4]=project28exp1(dt,dS,tf)

%dt is time step (0.5)
%dS is space step (0.5)
%tf is the final time point calculated (61)

Fs=0.1275/1000; %feed solvent flow rate
Fm=0.105/1000; %feed monomer flow rate
Fi=0.03/1000; %feed initiator flow rate
rhoCp=360*1000; %density of reacting mixture*heat capacity
rhojCpj=966.3*1000; %density of the heat conducting fluid*heat capacity
UA=70; %Global heat transfer coefficient*heat exchange area between the jacket and reactor
constituents
f=0.6; %initiator efficiency
dH=-16700; %heat of reaction
kdo=5.95*(10^13); %preexponential factor for dissociation
Ed=14897; %activation energy for dissociation
kpo=1.06*(10^7); %preexponential factor for propagation
Ep=3557; %activation energy for propagation
kto=1.25*(10^9); %preexponential factor for termination
Et=843; %activation energy for termination
L=3; %Reactor Length
d=.3; %Reactor Diameter
v=(Fi+Fm+Fs)/((pi*((d)^2))/4); %axial fluid velocity
vj=0.05; %Axial heat-conducting fluid velocity
D1=5*(10^-10); %Initiator Diffusivity
D2=1.4*(10^-11); %Monomer Diffusivity


k=.033; %Fluid thermal conductivity
kj=.56; %Heat conducting fluid thermal conductivity

x1L=588.8;
x2L=8698;
x3L=330;
x4L=295;

x1o=0;
x2o=0;
x3o=330;
x4o=295;

NS=L/dS+1;
Nt=tf/dt+1;
x1=zeros(Nt,NS);
x2=zeros(Nt,NS);
x3=zeros(Nt,NS);
x4=zeros(Nt,NS);

for i=2:Nt
x1(i,1)=x1L;
x2(i,1)=x2L;
x3(i,1)=x3L;
x4(i,1)=x4L;
end

for j=2:NS
x1(1,j)=x1o;
x2(1,j)=x2o;
x3(1,j)=x3o;
x4(1,j)=x4o;
end
x1(1,1)=0;
x2(1,1)=0;
x3(1,1)=330;
x4(1,1)=295;

for t=1:Nt-1
for S=2:NS-1
29
dx1=-v*(x1(t,S+1)-x1(t,S-1))/(2*dS) +D1*(x1(t,S+1)-2*x1(t,S)+x1(t,S-1))/dS^2 -
x1(t,S)*kdo*exp(-Ed*x3(t,S)^-1);
dx2=-v*(x2(t,S+1)-x2(t,S-1))/(2*dS) +D2*(x2(t,S+1)-2*x2(S)+x2(t,S-1))/dS^2-
x2(t,S)*kpo*exp(-Ep*x3(t,S)^-1)*(2*f*(kdo*exp(-Ed*x3(t,S)^-1))*x1(t,S)/(kto*exp(-Et*x3(t,S)^-
1)))^(1/2);
dx3=-v*(x3(t,S+1)-x3(t,S-1))/(2*dS) + k/rhoCp*(x3(t,S+1)-2*x3(t,S)+x3(t,S-1))/dS^2 -
dH/rhoCp*x2(t,S)*kpo*exp(-Ep*x3(t,S)^-1)*(2*f*(kdo*exp(-Ed*x3(t,S)^-1))*x1(t,S)/(kto*exp(-
Et*x3(t,S)^-1)))^(1/2) - UA/rhoCp*(x3(t,S)-x4(t,S));
dx4=-vj*(x4(t,S+1)-x4(t,S-1))/(2*dS) + (kj/rhojCpj)*(x4(t,S+1)-2*x4(t,S)+x4(t,S-1))/dS^2
+(UA/rhojCpj)*(x3(t,S)-x4(t,S));
x1(t+1,S)=x1(t,S)+dt*dx1;
x2(t+1,S)=x2(t,S)+dt*dx2;
x3(t+1,S)=x3(t,S)+dt*dx3;
x4(t+1,S)=x4(t,S)+dt*dx4;
end

dx1=D1*(-2*x1(t,NS)+2*x1(t,NS-1))/dS^2 -x1(t,NS)*kdo*exp(-Ed*x3(t,NS)^-1);
dx2=D2*(-2*x2(t,NS)+2*x2(t,NS-1))/dS^2 -x2(t,NS)*kpo*exp(-Ep*x3(t,NS)^-1)*(2*f*(kdo*exp(-
Ed*x3(t,NS)^-1))*x1(t,NS)/(kto*exp(-Et*x3(t,NS)^-1)))^(1/2);
dx3=k/rhoCp*(-2*x3(t,NS)+2*x3(t,NS-1))/dS^2 -dH/rhoCp*x2(t,NS)*kpo*exp(-Ep*x3(t,NS)^-
1)*(2*f*(kdo*exp(-Ed*x3(t,NS)^-1))*x1(t,NS)/(kto*exp(-Et*x3(t,NS)^-1)))^(1/2) -
UA/rhoCp*(x3(t,NS)-x4(t,NS));
dx4=(kj/rhojCpj)*(-2*x4(t,NS)+2*x4(t,NS-1))/dS^2 +(UA/rhojCpj)*(x3(t,NS)-x4(t,NS));
x1(t+1,NS)=x1(t,NS)+dt*dx1;
x2(t+1,NS)=x2(t,NS)+dt*dx2;
x3(t+1,NS)=x3(t,NS)+dt*dx3;
x4(t+1,NS)=x4(t,NS)+dt*dx4;
end
[S,time]=meshgrid(0:dS:L,0:dt:tf);

figure(9)
surf(S,time,x1)
figure(10)
surf(S,time,x2)
figure(11)
surf(S,time,x3)
figure(12)
surf(S,time,x4)
end


Problem 2.8 Code (Euler Implicit)
%Dynamic simulation for PFR using euler implicit


function [z,time,x]=project28imp(dt,dS,tf)

%dt is time step (5)
%dS is space step (0.2)
%tf is the final time point calculated (800)

Fs=0.1275/1000; %feed solvent flow rate
Fm=0.105/1000; %feed monomer flow rate
Fi=0.03/1000; %feed initiator flow rate
rhoCp=360*1000; %density of reacting mixture*heat capacity
rhojCpj=966.3*1000; %density of the heat conducting fluid*heat capacity
UA=70; %Global heat transfer coefficient*heat exchange area between the jacket and reactor
constituents
f=0.6; %initiator efficiency
dH=-16700; %heat of reaction
kdo=5.95*(10^13); %preexponential factor for dissociation
Ed=14897; %activation energy for dissociation
kpo=1.06*(10^7); %preexponential factor for propagation
Ep=3557; %activation energy for propagation
kto=1.25*(10^9); %preexponential factor for termination
Et=843; %activation energy for termination
L=3; %Reactor Length
30
d=.3; %Reactor Diameter
v=(Fi+Fm+Fs)/((pi*((d)^2))/4); %axial fluid velocity
vj=.05; %Axial heat-conducting fluid velocity
D1=5*(10^-10); %Initiator Diffusivity
D2=1.4*(10^-11); %Monomer Diffusivity
k=.033; %Fluid thermal conductivity
kj=.56; %Heat conducting fluid thermal conductivity
x1L=588.8;
x2L=8698;
x3L=330;
x4L=295;


N=L/dS+1;
Nt=tf/dt+1;
xo=zeros(1,4*N);
xo(1,1:N)=0;
xo(1,N+1:2*N)=0;
xo(1,2*N+1:3*N)=330;
xo(1,3*N+1:4*N)=295;
x=zeros(Nt,4*N);

for j=2:Nt
x(j,1)=x1L;
x(j,N+1)=x2L;
x(j,2*N+1)=x3L;
x(j,3*N+1)=x4L;
end
x(1,:)=xo;
for t=1:Nt-1
xt=fsolve(@(xf) xf-xo'-dt*(spacefn(xf,dS)),xo',optimset('Display','off'));
x(t+1,:)=xt';
xo=xt';
%xplot=xo;
end

function F=spacefn(x,dS)

Fs=0.1275/1000; %feed solvent flow rate
Fm=0.105/1000; %feed monomer flow rate
Fi=0.03/1000; %feed initiator flow rate
rhoCp=360; %density of reacting mixture*heat capacity
rhojCpj=966.3; %density of the heat conducting fluid*heat capacity
UA=70; %Global heat transfer coefficient*heat exchange area between the jacket and reactor
constituents
f=0.6; %initiator efficiency
dH=-16700; %heat of reaction
kdo=5.95*(10^13); %preexponential factor for dissociation
Ed=14897; %activation energy for dissociation
kpo=1.06*(10^7); %preexponential factor for propagation
Ep=3557; %activation energy for propagation
kto=1.25*(10^9); %preexponential factor for termination
Et=843; %activation energy for termination
L=3; %Reactor Length
d=.3; %Reactor Diameter
v=(Fi+Fm+Fs)/((pi*((d)^2))/4); %axial fluid velocity
vj=.05; %Axial heat-conducting fluid velocity
D1=5*(10^-6); %Initiator Diffusivity
D2=1.4*(10^-7); %Monomer Diffusivity
k=.033; %Fluid thermal conductivity
kj=.56; %Heat conducting fluid thermal conductivity
x1L=588.8;
x2L=8698;
x3L=330;
x4L=295;


N=L/dS+1;
F=zeros(4*N,1);
F(1)=x(1)-x1L; %Left side boundary condition for initiator concentration
F(N+1)=x(N+1)-x2L; %Left side boundary condition for monomer concentration
31
F(2*N+1)=x(2*N+1)-x3L; %Left side boundary condition for reactor temp
F(3*N+1)=x(3*N+1)-x4L; %Left side boundary condition for jacket temp
for i=2:N-1
kd=kdo*exp(-Ed/x(2*N+i));
kp=kpo*exp(-Ep/x(2*N+i));
kt=kto*exp(-Et/x(2*N+i));
R=(((2*f*kd*x(i))/(kt))^2)^0.25;
F(i)=-v*((x(i+1)-x(i-1))/(2*(dS)))+D1*((x(i+1)-2*x(i)+x(i-1))/((dS)^2))-kd*x(i);
F(N+i)=-v*((x(N+i+1)-x(N+i-1))/(2*(dS)))+D2*((x(N+i+1)-2*x(N+i)+x(N+i-1))/((dS)^2))-
kp*x(N+i)*R;
F(2*N+i)=-v*((x(2*N+i+1)-x(2*N+i-1))/(2*(dS)))+(k/rhoCp)*((x(2*N+i+1)-2*x(2*N+i)+x(2*N+i-
1))/((dS)^2))-(dH/rhoCp)*kp*x(N+i)*R-((UA)/rhoCp)*(x(2*N+i)-x(3*N+i));
F(3*N+i)=-vj*((x(3*N+i+1)-x(3*N+i-1))/(2*(dS)))+(kj/rhojCpj)*((x(3*N+i+1)-2*x(3*N+i)+x(3*N+i-
1))/((dS)^2))+((UA)/rhojCpj)*(x(2*N+i)-x(3*N+i));
end
F(N)=D1*((2*x(N-1)-2*x(N))/((dS)^2))-(kdo*exp(-Ed/x(3*N)))*x(N); %Right side boundary condition
for initiator concentration
F(2*N)=D2*((2*x(2*N-1)-2*x(2*N))/((dS)^2))-(kpo*exp(-Ep/x(3*N)))*x(2*N)*((((2*f*kdo*exp(-
Ed/x(3*N))*x(N))/(kto*exp(-Et/x(3*N))))^2)^0.25); %Right side boundary condition for monomer
concentration
F(3*N)=(k/rhoCp)*((2*x(3*N-1)-2*x(3*N))/((dS)^2))-(dH/rhoCp)*(kpo*exp(-
Ep/x(3*N)))*x(2*N)*((((2*f*kdo*exp(-Ed/x(3*N))*x(N))/(kto*exp(-Et/x(3*N))))^2)^0.25)-
((UA)/rhoCp)*(x(3*N)-x(4*N)); %Right side boundary condition for reactor temp
F(4*N)=(kj/rhojCpj)*((2*x(4*N-1)-2*x(4*N))/((dS)^2))+((UA)/rhojCpj)*(x(3*N)-x(4*N)); %Right side
boundary condition for jacket temp
end
[z,time]=meshgrid(0:dS:L,0:dt:tf);
figure(5)
surf(z,time,x(1:Nt,1:N))
figure(6)
surf(z,time,x(1:Nt,N+1:2*N))
figure(7)
surf(z,time,x(1:Nt,2*N+1:3*N))
figure(8)
surf(z,time,x(1:Nt,3*N+1:4*N))

end