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Slides Matbal 2up
Slides Matbal 2up
Rj
V
Q0
cj0
Q1
cj1
Conservation of mass
(
rate of
accumulation
=
of component j
rate of generation
of component j by
chemical reactions
rate of inflow
of component j
rate of outflow
of component j
(1)
Rj
V
Q0
cj0
Q1
cj1
Conservation of mass
d
dt
cj dV = Q0cj0 Q1cj1 +
Rj dV
(2)
d
dt
cj dV = Q0cj0 Q1cj1 +
Rj dV
Rate expressions
To solve the reactor material balance, we require an expression for the production rates, Rj
Rj =
ij ri
Rj
Batch Reactor
d
dt
cj dV = Q0cj0 Q1cj1 +
Rj dV
Because the reactor is well stirred, the integrals in Equation 2 are simple to
evaluate,
Z
Z
cj dV = cj VR
Rj dV = Rj VR
VR
VR
= Rj VR
(3)
Reactor Volume
(4)
Use Equation 3 rather than Equation 4 if the reactor volume changes significantly during the course of the reaction.
10
First-order, irreversible
A - B,
r = kcA
(5)
(6)
First-order, irreversible
t=0
(7)
12
First-order, irreversible
1
0.8
cA
cA0
0.6
0.4
k=2
0.2
0
k=1
k = 0.5
k=5
0
13
First-order, irreversible
The A concentration decreases exponentially from its initial value to zero with
increasing time.
The rate constant determines the shape of this exponential decrease. Rearranging Equation 7 gives
ln(cA/cA0) = kt
14
First-order, irreversible
1
k = 0.5
k=1
0.1
k=2
cA
cA0
0.01
k=5
0.001
0
One can get an approximate value of the rate constant from the slope of the
straight line.
This procedure is a poor way to determine a rate constant and should be
viewed only as a rough approximation (Chapter 9).
15
First-order, irreversible
(8)
First-order, reversible
(9)
(10)
17
First-order, reversible
-*- B
A)
(11)
k1
cA (0) = cA0
cB (0) = cB0
18
First-order, reversible
(12)
First-order, reversible
dcA
= acA + b
dt
Zt
Z cA
dcA
=
dt
cA0 acA + b
0
cA
1
ln(acA + b)
=t
a
cA0
cA = cA0eat
b
(1 eat )
a
First-order, reversible
cA = cA0e
(k1 +k1 )t
h
i
k1
(k1 +k1 )t
(cA0 + cB0) 1 e
+
k1 + k1
(13)
cB = cB0e
(k1 +k1 )t
h
i
k1
(k1 +k1 )t
+
(cA0 + cB0) 1 e
k1 + k1
(14)
21
First-order, reversible
cA (t)
0.8
0.6
cBs
0.4
cAs
cB (t)
0.2
0
k1
(cA0 + cB0)
k1 + k1
23
1
(cA0 + cB0)
1 + K1
K1
(cA0 + cB0)
1 + K1
24
Second-order, irreversible
A - B
(15)
2
in which the rate expression is second order, r = kcA
.
cA(0) = cA0
(16)
Second-order, irreversible
Separation works here
dcA
2 = kdt
cA
Z cA
dcA
2 = k
cA0 cA
Zt
0
dt
1
1
= kt
cA0 cA
Solving for cA gives
1
cA =
+ kt
cA0
1
(17)
Check that this solution satisfies the differential equation and initial condition
26
Second-order, irreversible
1
0.9
0.8
0.7
0.6
cA
0.5
cA0
0.4
second order
0.3
first order
0.2
0.1
0
The second-order reaction decays more slowly to zero than the first-order
reaction.
27
A + B - C
r = kcAcB
(18)
(19)
(20)
(21)
cA0 cB0
(22)
29
(23)
Notice that if cA0 > cB0 (Excess A), the steady state
cAs = cA0 cB0
cBs = 0
nth-order, irreversible
n
The nth-order rate expression r = kcA
5
4.5
n=3
4
3.5
2.5
1/2
1.5
1
0.5
0
0
0.5
1.5
cA
2.5
32
nth-order, irreversible
A - B
n
r = kcA
dcA
n
= r = kcA
dt
This equation also is separable and can be rearranged to
dcA
n = kdt
cA
Performing the integration and solving for cA gives
cA =
n+1
cA0
+ (n 1)kt
1
n+1
n1
33
nth-order, irreversible
n1
(24)
in which
has units of inverse time.
n1
k0 = kcA0
34
nth-order, irreversible
1
0.8
cA
cA0
0.6
n=5
0.4
4
3
2
0.2
1
0
0
The larger the value of n, the more slowly the A concentration approaches
zero at large time.
35
nth-order, irreversible
0.8
cA
cA0
0.6
n=2
0.4
1
0.2
2 1
0
0
0.5
1/2
1/2
1
t
1.5
36
For n < 0, the rate decreases with increasing reactant concentration; the
reactant inhibits the reaction.
5
4.5
4
3.5
3
n=2
2.5
2
1.5
1/2
0.5
0
0
0.5
1.5
cA
2.5
37
Inhibition reactions are not uncommon, but watch out for small concentrations. Notice the rate becomes unbounded as cA approaches zero, which is
not physically realistic.
When using an ODE solver we may modify the right-hand sides of the material
balance
(
n
kcA
,
cA > 0
dcA
=
0,
cA = 0
dt
Examine the solution carefully if the concentration reaches zero.
38
A - B
k2
B - C
(25)
(26)
r2 = k2cB
39
40
k2 t
i
k1 h k1t
k2 t
+ cA0
e
e
,
k2 k1
k1 k2
(27)
41
42
1
0.8
cA (t)
0.6
cC (t)
cB (t)
c
0.4
0.2
0
0
A - B
k2
A - C
(28)
(29)
Assume the rates of the two irreversible reactions are given by r1 = k1cA and
r 2 = k 2 cA .
44
45
(30)
(31)
46
(32)
47
1
0.8
cA (t)
cC (t)
0.6
c
0.4
cB (t)
0.2
0
0
0.5
1.5
t
2.5
Notice that the two parallel reactions compete for the same reactant, A
The rate constants determine which product is favored
Large values of k1/k2 favor the formation of component B compared to C and
vice versa
49
There are several ways to define selectivity, yield and conversion, so be clear
about the definition you choose.
Point selectivity: The point (or instantaneous) selectivity is the ratio of the production rate of
one component to the production rate of another component.
Overall selectivity: The overall selectivity is the ratio of the amount of one component produced to the amount of another component produced.
Yield: The yield of component j is the fraction of a reactant that is converted into component
j.
Conversion: Conversion is normally defined to be the fraction of a component that has been
converted to products by the reaction network. Conversion has several definitions and
conventions. It is best to state the definition in the context of the problem being solved.
50
Qf
cjf
cj
Rj
51
= Qf cjf Qcj + Rj VR ,
j = 1, . . . , ns
(33)
52
If the reactor volume is constant and the volumetric flowrates of the inflow
and outflow streams are the same, Equation 33 reduces to
dcj
1
= (cjf cj ) + Rj
dt
The parameter
(34)
= VR /Qf
The steady state of the CSTR is described by setting the time derivative in
Equation 33 to zero,
0 = Qf cjf Qcj + Rj VR
(35)
Conversion of reactant j is defined for a steady-state CSTR as follows
xj =
Qf cjf Qcj
Qf cjf
(steady state)
(36)
A - 2B
r = kcA
the feed concentration of A is cAf = 2 mol/L, the residence time of the reactor
is = 100 min, and the rate constant is k = 0.1 min1.
1. Find the steady-state concentration of A in the effluent for the given feed.
2. Plot the concentration of A versus time for constant feed concentration cAf = 2 mol/L if
the reactor is initially filled with an inert so cA0 = 0 mol/L.
3. Plot the concentration of A versus time for constant feed concentration cAf = 2 mol/L if
the reactor is initially filled with feed so cA0 = 2 mol/L.
55
2 mol/L
= 0.182 mol/L
1 + (0.1 min1)(100 min)
56
Parts 2 and 3
1
dcA
=
cAf cA kcA
dt
(38)
cA(0) = cA0
(1/+k)t
i
cAf h
(1/+k)t
1e
+
1 + k
(39)
57
Parts 2 and 3
2
cA (t) (mol/L)
1.5
cA0 = 2
0.5
cAs = 0.182
cA0 = 0
0
0
10
20
30
40
t (min)
50
60
70
80
Both solutions converge to the same steady-state even though the starting
conditions are quite different.
58
phenol + acetone
(40)
(41)
Phenol production
cAf
1 + k
(42)
60
Phenol production
cAf cA
cA
=1
cAf
cAf
xA =
k
1 + k
1 xA
k 1 xA
61
Phenol production
Qf xA
k(1 xA)
(26.9 m3/hr)(0.85)
(4.12 hr
)(0.15)
= 37 m3
62
The semi-batch reactor is a cross between the batch reactor and CSTR.
The semi-batch reactor is initially charged with reactant, like the batch reactor, but allows a feed addition policy while the reaction takes place, like the
CSTR.
Normally there is no outflow stream.
63
(43)
One may choose to operate a semi-batch reactor to control the reaction rate
or heat release during reaction by slowly adding one of the reactants in the
feed stream.
Compared to the batch reactor, the semi-batch reactor provides more complete use of the reactor volume in reactions such as polymerizations that
convert from lower density to higher density during the course of the reaction.
64
= Qf cjf Qcj + Rj VR
(44)
Equation 44 covers both the batch, CSTR and semi-batch reactors, depending
on how we specify Qf and Q.
If we multiply Equation 44 by the molecular weight of species j and sum over
all species we obtain,
d(
The term
cj Mj VR )
dt
= Qf
X
j
cjf Mj Q
X
j
cj Mj +
Rj Mj VR
(45)
we denote
=
ns
X
cj M j
(46)
j=1
66
The term
Rj Mj = 0
d(VR )
= Qf f Q
dt
(47)
Equation 47 is clearly a total mass balance, in which the total mass in the
reactor changes in time due to the inflow and outflow of mass.
Notice that chemical reactions play no role in the total mass balance.
67
For example, we could express the equation of state in terms of the partial
molar volumes as
X
cj V j = 1
j
69
cj Vj = 1,
ideal mixture
70
Constant density
Because the reaction mixture density, , is independent of composition, it
does not vary with time either and we can set it to the feed value,
= f
(48)
(49)
Constant density
dVR
= Qf Q
dt
Batch reactor. For the batch reactor, Q = Qf = 0. We can therefore conclude
from Equation 49 that a batch reactor with constant density has constant
volume.
CSTR (dynamic and steady state). If the outflow of the CSTR is regulated so
that the CSTR has constant volume, then we can conclude from Equation 49
that Q = Qf .
Semi-batch reactor. In the semi-batch reactor, the reactor is filled during
operation so Qf is specified and positive for some time and Q = 0. The
solution to Equation 49 then determines the change in volume of the reactor
during the filling operation.
72
Nonconstant density
Unknowns.
In the general case, consider the following variables to fully determine the
state of the reactor: T , P , nj , VR .
We also require the value of Q to specify the right-hand sides of the material
balances.
The set of unknowns is nj , VR , Q.
We therefore have ns + 2 unknowns.
Equations.
We have the ns equations from the component mole balances.
The equation of state provides one additional equation.
The final equation is provided by a statement of reactor operation.
73
in which fj is
P
P
dVR
j fj cjf
i fi ri VR
Q+ P
= Qf P
dt
j fj cj
j f j cj
fj =
and fi is
fi =
X
j
(50)
f
cj
X
ij fj =
ij
f
cj
cj Vj 1 = 0.
fj = Vj
fi = Vi
X
dVR
= Qf Q +
ViriVR
dt
i
76
Nonconstant density
VR , Q, nj ,
j = 1, . . . , ns
dnj
= Qf cjf Qcj + Rj VR ,
dt
Component balances:
nj = cj VR
Defined quantities:
(i) constant density: = 0
V =
i
j cj Mj
j = 1, . . . , ns
j ij Vj
j cj Vj = 1
Q = Qf +
i Vi ri VR
1. vol
VR = VR0
Q = Qf
VR = VR0
2. mass
VR = VR0
Q = Qf
P
dVR
= Qf (1 f /) + i V ri VR
i
dt
Q = Qf f /
3. Q
dVR
= Qf Q
dt
Q specified
P
dVR
= Qf Q + i V ri VR
i
dt
Q specified
77
Nonconstant density
VR , Q, nj ,
dnj
= Qf cjf Qcj + Rj VR ,
dt
Component balances:
nj = cj VR
Defined quantities:
j cj Mj
j = 1, . . . , ns
fi =
f
j ij c
j
f (c1 , c2 , . . . , cns ) = 0
Equation of state:
DAEs
1. vol
j = 1, . . . , ns
VR = VR0
ODEs
f (cj ) = 0
2. mass
VR = 0 VR0
f (cj ) = 0
3. Q
Q specified
f (cj ) = 0
VR = VR0
P
P
dVR
j fj cjf
i fi ri VR
= Qf P
Q+ P
dt
j fj cj
j f j cj
P
P
dVR
j fj cjf
i fi ri VR
= Qf P
Q+ P
dt
f
c
j j j
j f j cj
P
P
j fj cjf
i fi ri VR
Q = Qf P
+ P
j fj cj
j fj cj
Q = Qf f /
Q specified
Semi-batch polymerization
Consider a solution polymerization reaction, which can be modeled as a firstorder, irreversible reaction
k
M - P
r = kcM
79
Semi-batch polymerization
80
P = 1100 kg/m3
81
Semi-batch polymerization
(51)
M(0) = 0
82
Semi-batch polymerization
(52)
VR (0) = 10 m3
in which V = (1/P 1/M ) MM
83
To compute the polymer mass, we note from the stoichiometry that the mass
e P is
production rate of polymer R
e P = RM MM
R
dPe
e p VR = kcM MM VR = (kMM )M
=R
dt
(53)
84
Semi-batch polymerization
The text solves this problem analytically. Instead, lets solve it numerically.
Let t1 be the time that the reactor fills.
We need an ODE solver that is smart enough to stop when the reactor fills,
because we do not know this time t1. The ODE solver needs to find it for us.
dasrt is an ODE solver with the added capability to find the time at which
some event of interest occurs.
85
86
Operation 1.
87
Semi-batch polymerization
20
VR (m3 )
15
10
0
0
10
20
30
time (min)
40
50
Qf (m3 /min)
0.8
0.6
0.4
0.2
0
-0.2
1
0
10
20
30
time (min)
40
50
Figure 5: Semi-batch reactor feed flowrate for primary monomer addition (operation 1) and primary plus secondary monomer additions (operation 2).
89
6000
5000
monomer (kg)
4000
3000
2
2000
1000
0
10
20
30
time (min)
40
50
90
polymer (kg)
12000
10000
8000
6000
4000
2000
0
10
20
30
time (min)
40
50
91
Operation 2.
Because the reactor volume is constant, we can solve Equation 52 for the feed
flowrate during the secondary monomer addition
Qf = V kM
Operation 2 is also shown in the figures.
Notice the final polymer production is larger in operation 2 because of the
extra monomer addition.
92
93
By using the volume of the reactor more efficiently, the total polymer production increases 22.5%.
94
95
Given the plug-flow assumption, it is natural to take a thin disk for the reactor
volume element
Qf
cjf
cj
z
Q(z)
}|
{
Q(z + z)
Rj
cj (z)
cj (z + z)
z
z + z
96
= cj Q cj Q
z
z+z
+ Rj V
(54)
Dividing the above equation by V and taking the limit as V goes to zero
yields,
cj Q
cj
+ Rj
(55)
=
|{z}
|t
| V
{z }
{z } reaction
accumulation
convection
97
If the tube has constant cross section, Ac , then velocity, v, is related to volumetric flowrate by v = Q/Ac , and axial length is related to tube volume by
z = V /Ac ,
Equation 55 can be rearranged to the familiar form [1, p.584]
cj v
cj
=
+ Rj
t
z
(56)
98
Steady-State Operation
(57)
The product cj Q = Nj is the total molar flow of component j. One also can
express the PFR mole balance in terms of the molar flow,
dNj
= Rj
dV
(58)
99
(59)
RT X
Nj
P j
(60)
101
To evaluate the concentrations for use with the reaction rate expressions, one
simply rearranges Equation 59 to obtain
cj =
Nj
P Nj
P
=
Q
RT j Nj
(61)
102
M(0) = Mf
Mf
(63)
constant density
(64)
and the volumetric flowrate is constant and equal to the feed value.
Equation 64 is used often for liquid-phase reactions.
104
constant flowrate
(65)
105
A - B + C
(66)
106
(67)
The volumetric flowrate is not constant, so we use Equation 60, which assumes an ideal-gas equation of state,
Q=
RT
(NA + NB + NC)
P
(68)
107
dNC
= RC = r
dV
d (NA + NC)
=0
dV
The stoichiometry does not allow the molar flow NA +NB or NA +NC to change
with position in the tube.
108
NA + NC = NAf + NCf
Rearranging the previous equations gives,
NB = NAf + NBf NA
NC = NAf + NCf NA
Substituting the relations for NB and NC into Equation 68 gives
Q=
RT
2NAf + NBf + NCf NA
P
109
NAf
2NAf NA
dNA =
NA
ZV
0
kP
dV
RT
110
kP
ln NA/NAf + NAf NA =
V
RT
RT
NAf [2 ln(1 xA) + xA]
kP
111
Qf
[2 ln(1 xA) + xA]
kAc
!
4
[2 ln(1 .35) + .35]
(2.5 cm)2
z = 1216 cm = 12.2 m
112
Multiple-Reaction Systems
The modeler has some freedom in setting up the material balances for a plugflow reactor with several reactions.
The most straightforward method is to write the material balance relation for
every component,
dNj
= Rj ,
j = 1, 2, . . . , ns
dV
nr
X
Rj =
ij ri,
j = 1, 2, . . . , ns
i=1
Hougen and Watson [3] analyzed the rate data for the pyrolysis of benzene
by the following two reactions.
Diphenyl is produced by the dehydrogenation of benzene,
k1
-*- C12H10 + H2
2C6H6 )
2B
k1
-*)
+ H
114
-*- C18H14 + H2
C6H6 + C12H10 )
B
k2
-*)
+ H
(69)
(70)
The reactions are assumed to be elementary so that the rate expressions are
cD cH
2
r 1 = k 1 cB
K1
cT cH
r2 = k2 cB cD
K2
(71)
(72)
115
Calculate the tube volume required to reach 50% total conversion of the benzene for a 60 kmol/hr feed stream of pure benzene.
The reactor operates at 1033K and 1.0 atm.
Plot the mole fractions of the four components versus reactor volume.
116
The rate and equilibrium constants at T = 1033K and P = 1.0 atm are given
in Hougen and Watson,
k1 = 7 105 L/mol hr
k2 = 4 105 L/mol hr
K1 = 0.31
K2 = 0.48
117
The mole balances for the four components follow from the stoichiometry,
dNB
dV
dND
dV
dNH
dV
dNT
dV
= 2r1 r2
(73)
= r1 r2
(74)
= r1 + r2
(75)
= r2
(76)
The initial condition for the ODEs are NB (0) = NBf and ND (0) = NH (0) =
NT (0) = 0.
118
The total molar flux does not change with reactor volume.
Q=
RT
NBf
P
(77)
The rate expressions are substituted into the four ODEs and they are solved
numerically.
The total conversion of benzene, xB = (NBf NB )/NBf , is plotted versus
reactor volume in Figure 8.
A reactor volume of 404 L is required to reach 50% conversion. The composition of the reactor versus reactor volume is plotted in Figure 9.
119
0.6
0.5
0.4
xB
0.3
0.2
0.1
0
0
200
400
600
120
1
0.8
yB
0.6
yj
0.4
yH
yD
0.2
yT
0
0
200
400
600
121
122
We have two continuous reactors in this chapter: the CSTR and the PFR.
Lets compare their steady-state efficiencies in converting reactants to products.
For simplicity, consider a constant-density, liquid
k
n
r = kcA
A - B
(78)
For this situation, the steady-state PFR material balance is given by Equation 65
dcA
= r (cA)
d
123
Z cA
cAf
1
0
0 dcA
r (cA)
0
The area under the curve 1/r (cA
) is the total time required to achieve the
desired concentration change.
CSTR
1
0
r (cA
)
PFR
cA
0
cA
cAf
124
cAf cA
r (cA)
This result also can be interpreted as an area. Notice that this area is the
height, 1/r (cA), times the width, cAf cA, of the rectangle.
CSTR
1
0
r (cA
)
PFR
cA
0
cA
cAf
125
If 1/r (cA) is a decreasing function of cA, or, equivalently, r (cA) is an increasing function of cA, to achieve the same conversion, the PFR time (or volume,
VR = Qf ) is less than the CSTR time (volume).
The PFR reaction rate varies with length. The rate is high at the entrance to the
tube where the concentration of A is equal to the feed value, and decreases
with length as the concentration drops. At the exit of the PFR, the rate is the
lowest of any location in the tube.
Now considering that the entire volume of the CSTR is reacting at this lowest
rate of the PFR, it is intuitively obvious that more volume is required for the
CSTR to achieve the same conversion as the PFR.
126
If the reaction order is positive (the usual case), the PFR is more efficient. If
the reaction order is negative, the CSTR is more efficient.
PFR
1
0
r (cA
)
CSTR
cA
0
cA
cAf
127
The PFR achieves higher conversion than an equivalent volume CSTR for the
irreversible reaction with first-order kinetics
A - B
r = kcA
128
129
NA
VR
NA0
NA1
NA2
NA
VR
NA2
NA2
pure B
In the text, we show how to find the recycle flowrate so this system achieves
the PFR conversion.
130
This example was motivated by a recent result of Feinberg and Ellison called
the CSTR Equivalence Principle of Reactor-Separator Systems [2].
This surprising principle states:
For a given reaction network with ni linearly independent reactions, any
steady state that is achievable by any reactor-separator design with total
reactor volume V is achievable by a design with not more than ni + 1
CSTRs, also of total reactor volume V . Moreover the concentrations,
temperatures and pressures in the CSTRs are arbitrarily close to those
occurring in the reactors of the original design.
131
133
A - B
k2
B - C
(79)
(80)
r2 = k2 xB
The basic idea of the Gillespie algorithm is to: (i) choose randomly the time
at which the next reaction occurs, and (ii) choose randomly which reactions
occurs at that time.
1. Initialize. Set integer counter n to zero. Set the initial species numbers,
xj (0), j = 1, . . . ns . Determine stoichiometric matrix and reaction probability laws (rate expressions)
ri = kih(xj )
for all reactions.
3. Select two random numbers, p1, p2, from a uniform distribution on the interval (0, 1). Let the time interval until the next reaction be
te = ln(p1)/rtot
(81)
136
r1
r1 +r2
r2
r1 +r2
137
5. Update the simulation time t(n + 1) = t(n) + te. Update the species numbers
for the single occurrence of the mth reaction via
xj (n + 1) = xj (n) + mj ,
j = 1, . . . ns
138
If rtot is the total probability for reaction, ertot t is the probability that a reaction has not occurred during time interval te.
We will derive this fact in Chapter 8 when we develop the residence-time
distribution for a CSTR.
The next figure shows the results of this algorithm when starting with xA =
100 molecules.
139
xC
xA
60
xB
xj
40
20
0
0
140
Notice the random aspect of the simulation gives a rough appearance to the
number of molecules versus time, which is quite unlike any of the deterministic simulations.
Because the number of molecules is an integer, the simulation is actually
discontinuous with jumps between simulation times.
But in spite of the roughness, we already can make out the classic behavior
of the series reaction: loss of starting material A, appearance and then disappearance of the intermediate species B, and slow increase in final product
C.
141
142
xC
xA
600
xB
xj
400
200
0
0
143
xC
xA
2400
xB
xj
1600
800
0
0
144
We see the random fluctuations become less pronounced. Notice that even
with only 4000 starting molecules, the results compare very favorably with
the deterministic simulation shown previously.
Another striking feature of the stochastic approach is the trivial level of programming effort required to make the simulations.
The biggest numerical challenge is producing the pseudo-random numbers
and many well-developed algorithms are available for that task.
The computational time required for performing the stochastic simulation
may, however, be large.
145
146
cccDNA
nucleotides
nucleotides +
rcDNA +
rcDNA
(82)
cccDNA
(83)
amino acids
envelope
(84)
cccDNA
degraded
(85)
rcDNA
cccDNA
envelope
secreted or degraded
(86)
envelope
(87)
secreted virus
147
The reaction rates and production rates for Reactions 8287 are given by
r1
r2
r3
r4
r5
r6
k1 xA
k2 xB
k3 xA
k4 xA
k5xC
k6xB xC
R
r r4
A 2
RB = r1 r2 r6
RC
r3 r5 r6
(88)
148
Assume the systems starts with a single cccDNA molecule and no rcDNA and
no envelope protein, and the following rate constants
k =
xA
xB
0.025
xC
iT
1000
0.25
0
2
iT
7.5 10
(89)
6
(90)
149
cccDNA
20
15
deterministic
10
avg. stochastic
5
0
0
50
250
100
t (days)
150
200
rcDNA
200
150
deterministic
100
avg. stochastic
50
0
50
100
t (days)
150
200
150
10000
envelope
8000
deterministic
6000
avg. stochastic
4000
2000
0
50
100
t (days)
150
200
151
stoch 1
cccDNA
25
20
15
deterministic
10
5
stoch 2
0
0
50
100
t (days)
150
200
Figure 10: Species cccDNA versus time for hepatitis B virus model; two representative stochastic trajectories.
152
153
In fact, it occurs for 125 of the 500 simulations. So the average stochastic
simulation consists of 75% trajectories that fluctuate about the deterministic
trajectory and 25% trajectories that go to zero.
25
cccDNA
20
15
deterministic
10
avg. stochastic
5
0
0
50
100
t (days)
150
200
154
Summary
155
Summary
BATCH
constant volume
CSTR
constant density
d(cj VR )
= Rj VR
dt
dcj
= Rj
dt
PFR
steady state
constant flowrate
(92)
d(cj VR )
= Qf cjf Qcj + Rj VR
dt
(93)
dcj
1
=
(c
cj ) + Rj
dt
jf
(94)
cj = cjf + Rj
steady state
SEMI-BATCH
(91)
d(cj VR )
= Qf cjf + Rj VR
dt
cj
(cj Q)
=
+ Rj
t
V
d(cj Q)
dV
= Rj
dcj
= Rj ,
d
(95)
(96)
(97)
(98)
= V /Qf
(99)
156
Summary
We also have introduced some of the basic reaction-rate expressions.
first order, irreversible
first order, reversible
second order, irreversible
nth order, irreversible
two first-order reactions in series
two first-order reactions in parallel
two second-order, reversible reactions
157
Summary
158
Summary
We showed that the PFR achieves higher conversion than the CSTR of the
same volume if the reaction rate is an increasing function of a component
composition (n > 0 for an nth-order rate expression).
Conversely, the CSTR achieves higher conversion than the same-volume PFR
if the rate is a decreasing function of a component composition (n < 0).
Finally, we introduced stochastic simulation to model chemical reactions occurring with small numbers of molecules.
159
Summary
The stochastic model uses basic probability to compute reaction rate. A given
reactions probability of occurrence is assumed proportional to the number
of possible combinations of reactants for the given stoichiometry.
Two pseudo-random numbers are chosen to determine: (i) the time of the
next reaction and (ii) the reaction that occurs at that time.
The smooth behavior of the macroscopic ODE models is recovered by the
random simulations in the limit of large numbers of reacting molecules.
With small numbers of molecules, however, the average of the stochastic
simulation does not have to be equal to the deterministic simulation. We
demonstrated this fact with the simple, nonlinear hepatitis B virus model.
160
References
161