8-61$
P814)(d))continued$
Calculated values of DEQ variables
Variable
Initial value
Minimal value
Maximal value
Final value
1
Ca
0.098
3.689E08
0.098
3.689E08
2
Cb
0.049
1.844E08
0.049
1.844E08
3
Cc
0
0
0.0150519
1.497E12
4
Cd
0
0
0.0089776
1.018E10
5
Ce
0
0
0.0496431
0.0496431
6
Cg
0
0
0.0477138
0.0477138
7
Cto
0.147
0.147
0.147
0.147
8
Cw
0
0
0.0496431
0.0496431
9
Fa
10.
7.43E06
10.
7.43E06
10
Fb
5.
3.715E06
5.
3.715E06
11
Fc
0
0
1.854
3.016E10
12
Fd
0
0
1.030757
2.05E08
13
Fe
0
0
9.999993
9.999993
14
Fg
0
0
9.611354
9.611354
15
Ft
15.
14.91758
29.61135
29.61135
16
Fw
0
0
9.999993
9.999993
17
k1
0.014
0.014
30.64368
30.64368
18
k10
0.014
0.014
0.014
0.014
19
k2
0.007
0.007
7.341E+07
7.341E+07
20
k20
0.007
0.007
0.007
0.007
21
k3
0.014
0.014
6.707E+04
6.707E+04
22
k30
0.014
0.014
0.014
0.014
23
k4
0.45
0.45
984.9755
984.9755
24
k40
0.45
0.45
0.45
0.45
25
ra
0.0003709
0.0625305
1.0E07
1.0E07
26
rb
0.0001855
0.0312653
5.002E08
5.002E08
27
rc
0.0003037
0.0238556
0.0236439
5.93E12
28
rd
6.723E05
0.0093009
0.0120515
3.804E10
29
re
0
0
0.0773459
1.004E07
30
rg
0
0
0.0627128
1.003E07
31
rw
0
0
0.0773459
1.004E07
32
Sae
0
0
5.205E+05
7.43E07
33
Scd
0
0
3.394658
0.0147083
34
Sdg
0
0
18.42613
2.133E09
35
T
300.
300.
550.
550.
36
V
0
0
1000.
1000.
37
Yc
0
0
0.4483122
4.059E05
8-62$
P814)(d))continued
Differential equations
d(Fa)/d(V) = ra
d(Fb)/d(V) = rb
d(Fc)/d(V) = rc
d(Fd)/d(V) = rd
d(Fe)/d(V) = re
d(Fw)/d(V) = rw
d(Fg)/d(V) = rg
d(T)/d(V) = 0.25
Explicit equations
1
k20 = 0.007
2
k10 = 0.014
3
k1 = k10*exp((10000/1.97)*(1/3001/T))
4
k2 = k20*exp((30000/1.97)*(1/3001/T))
5
k30 = 0.014
6
k3 = k30*exp((20000/1.97)*(1/3001/T))
7
k40 = 0.45
8
Ft = Fa+Fb+Fc+Fd+Fe+Fw+Fg
9
Cto = 0.147
10
Ca = Cto*(Fa/Ft)
11
Cb = Cto*(Fb/Ft)
12
Cc = Cto*(Fc/Ft)
13
Cd = Cto*(Fd/Ft)
14
Ce = Cto*(Fe/Ft)
15
Cg = Cto*(Fg/Ft)
16
ra = (k1*Ca*(Cb)^0.5 + k2*(Ca)^2)
17
rb = ra/2
18
re = k3*Cc
19
k4 = k40*exp((10000/1.97)*(1/3001/T))
20
Cw = Cto*(Fw/Ft)
21
rg = k4*Cd
22
rw = k3*Cc
23
rd = k2*(Ca)^2k4*Cd
24
rc = k1*Ca*(Cb)^0.5 k3*Cc+k4*Cd
25
Yc = Fc/Fa
26
Scd = if (V>0.0001)then (Fc/Fd) else (0)
27
Sae = if (V>0.0001)then (Fa/Fe) else (0)
28
Sdg = if (V>0.0001)then (Fd/Fg) else (0)
P814)(d))continued
)
)
$
)
P815)
(1)$ C2H4$$+$$1/2O2$$→$$C2H4O$ $ (2)$ C2H4$$+$$3O2$$→$$2CO2$$+$$2H2O$
007626.082.0 == TOIO FF
$
)
P815)(a))
$Selectivity$of$D$over$CO2$$$
D
F
S=
)
8-64$
P815)(a))
POLYMATH)Results
Variable initial value minimal value maximal value final value
W 0 0 2 2
Fe 5.58E04 1.752E10 5.58E04 1.752E10
r1e 0.0024829 0.0024829 3.692E10 3.692E10
r2e 0.0029803 0.0029803 8.136E10 8.136E10
Differential equations as entered by the user
[1] d(Fe)/d(W) = r1e+r2e
Explicit equations as entered by the user
[1] Finert = 0.007626
[2] Ft = Fe+Fo+Fd+Fu1+Fu2+Finert
P815)(b))
Changes$in$equation$from$part$(a):$
$ $
×
OEE
ORrr
dF ++= 21 3
1
$and$$
( ) 0=oFO
$
$ $
skg
mol
W
RO.2
001116.00093.012.0 =
×
=
$
$ $ 𝐹
!0=0.0093 10.12 0.06 =4.91𝐸04 𝑚𝑜𝑙 𝑒𝑡𝑦𝑙𝑒𝑛𝑒$
$
P815)(c))
Changes$in$equation$from$part$(a):$
$ $
EEE
ERrr
dF ++= 21
$and$$
( ) 0=oFE
$
8-66$
P816)(a))
See$Polymath$program$$P8-16.pol$
Calculated values of DEQ variables$$
Variable
Initial value
Minimal value
Maximal value
Final value
1
ConvC
0
0
0.8337198
0.8337198
2
ConvL
0
0
0.7379696
0.7379696
3
Ct0
0.0082791
0.0082791
0.0082791
0.0082791
4
Fc
0.0041152
0.0006843
0.0041152
0.0006843
5
Fc0
0.0041152
0.0041152
0.0041152
0.0041152
6
Fco
0
0
0.0342518
0.0342518
7
Fh
0
0
0.0383516
0.0383516
8
Fl
0.0018519
0.0004852
0.0018519
0.0004852
9
Fl0
0.0018519
0.0018519
0.0018519
0.0018519
10
Ft
0.0259671
0.0259671
0.0807757
0.0807757
11
Fw
0.02
0.0070028
0.02
0.0070028
12
k1c
3.0E+04
3.0E+04
3.0E+04
3.0E+04
13
k2l
1.4E+07
1.4E+07
1.4E+07
1.4E+07
14
Mc
0.6666673
0.1108536
0.6666673
0.1108536
15
Mco
0
0
0.9590499
0.9590499
16
Mh
0
0
0.0767032
0.0767032
17
Ml
0.333333
0.0873434
0.333333
0.0873434
18
Mw
0.36
0.1260502
0.36
0.1260502
19
P
1.
1.
1.
1.
20
R
0.082
0.082
0.082
0.082
21
r1c
0.2509955
0.2509955
0.0015102
0.0015102
22
r2l
0.3361048
0.3361048
0.0003587
0.0003587
23
T
1473.
1473.
1473.
1473.
24
V
0
0
0.417
0.417
$
Differential equations$$
d(Fc)/d(V) = r1c
d(Fl)/d(V) = r2l
d(Fw)/d(V) = r1c+7*r2l
d(Fh)/d(V) = 6*r1c13*r2l
d(Fco)/d(V) = 6*r1c10*r2l
1
T = 1473
R = 0.082
P = 1
k2l = 14000000
k1c = 30000
Ft = Fc+Fl+Fw+Fh+Fco
Ct0 = P/(R*T)
Fc0 = 0.00411523
Fl0 = 0.00185185
8-67$
P816)(a)$continued$
10
Mc = Fc*162
11
Ml = Fl*180
12
Mh = Fh*2
13
Mco = Fco*28
14
Mw = Fw*18
15
r1c = k1c*(Ct0*(Fc)/(Ft))*(Ct0*(Fw)/(Ft))
16
r2l = k2l*(Ct0*(Fl)/(Ft))*((Ct0*(Fw)/(Ft))^2)
17
ConvC = (Fc0Fc)/Fc0
18
ConvL = (Fl0Fl)/Fl0
)
$
Plot))of))Fl))vs))V)
8-68$
P816)(a)$continued$
)
Plot)of)Fw))vs))V)
$
Plot)of)Fh)vs)V)
8-69$
P816)(a)$continued$
)
Plot)of)Fco)vs)V)
)
P816)(b)$
W$$is$$the$$key$reactant$
YC$=$(dCC/-dCW)$$=$r1C/(r1C$-7*r2L)$$
$
8-70$
P816)(b))continued$
Now$$YL$=$$-dL/(-dW)$$=$$r2L/(r1C$–$7*r2L)$$$
The$$plot$is$as$follows$:$
$$
Overall$selectivity$$
2
/CO H
S
$=$$
2
CO
H
N
N
$$=$$ exit$molar$flow$rate$of$CO/exit$molar$flow$rate$of$H2$=$$$
CCO$|exit$/CH2$|$exit$$$$at$any$point$in$the$reactor.$
$
)
P816)(c)$Individualized$solution$
$
8-71$
P817)(a))
The$reactions$are$$$
(i)$$L$$+$$$3$W$$!$$$3$H2$+$$3$CO$$+$char$
-r2CH$=$$$$$k2ChCchCw
2$$$$$$$$$$$$$$$$$$$$$$;$$$k2CH$=$$1000$($dm3/mol)2/sec$
$
Calculated values of DEQ variables
Variable
Initial value
Minimal value
Maximal value
Final value
1
ConL
0
0
0.9899505
0.9899505
2
Ct0
0.2
0.2
0.2
0.2
3
Fch
0
0
0.0075887
0.0047166
4
Fco
0
0
0.0887476
0.0887476
5
Fh
0
0
0.1111269
0.1111269
6
Fl
0.0123
0.0001236
0.0123
0.0001236
7
Fl0
0.0123
0.0123
0.0123
0.0123
8
Ft
0.1233
0.1233
0.2493464
0.2493464
9
Fw
0.111
0.0446317
0.111
0.0446317
10
k1l
3721.
3721.
3721.
3721.
11
k2ch
1000.
1000.
1000.
1000.
12
r1l
2.406642
2.406642
0.0004728
0.0004728
13
r2ch
0
0.0997755
0
0.0048484
14
V
0
0
0.417
0.417
Differential equations
d(Fl)/d(V) = r1l
d(Fch)/d(V) = r2chr1l
d(Fw)/d(V) = 3*r1l+4*r2ch
d(Fh)/d(V) = 3*r1l10*r2ch
d(Fco)/d(V) = 3*r1l7*r2ch
Explicit equations
1
k2ch = 1000
2
k1l = 3721
3
Ft = Fch+Fl+Fw+Fh+Fco
4
Ct0 = 0.2
5
r1l = k1l*(Ct0*(Fl)/(Ft))*((Ct0*(Fw)/(Ft))^2)
6
r2ch = k2ch*(Ct0*(Fch)/(Ft))*((Ct0*(Fw)/(Ft))^2)
7
Fl0 = 0.0123
8
ConL = (Fl0Fl)/(Fl0)
8-72$
P817)(a))continued$
$
P817)(b))
$
8-73$
P817)(c)$SCO/Ch$
Let$$$S1$=$S~
CO/Ch$$$=$Fco/Fch$
The$plot$is$as$follows$
Yw$=$1$
and$Yl$=$(rl)/(rw)$=$$(r1l)/(3*r1l$+$4*r2ch)$
the$plot$is$as$follows:$
$
)
P817)(d)))
)
P818)(a)$Individualized$Solution)
P818)(b)$Individualized$Solution$
$
)
9-1$
Solutions)for)Chapter)9)–)Reaction)Mechanisms,)Pathways,)
Bioreactions)and)Bioreactors)
)
P9-1)(a))Example)91)$$
(i)$The$graph$of$Io/I$will$remain$same$if$CS2$concentration$changes.$If$concentration$of$M$increases$the$
slope$of$line$will$decrease.$
$
P9-1)(b))Example)92)$
(i)$It$is$a$constant$at$very$low$KM$
(ii)$Vmax$=$2$kmol/m3s,$$and$KM$=$0.04$kmol/m3$
$
$
P9-1)(c))Example)9-3$$
(i)$Infinity$
(ii)$Now$Curea$=$1$mol/dm3$and$t$=$15$min$=$900$sec.$
$ $ $$
9-2$
P9-1)(d))Example)94)$
$
P9-1)(e))Example)95))
(i)$YP/C$
(ii)$107$g/dm3$
See$Polymath$program$P9-1-e.pol.$
Calculated)values)of)the)DEQ)variables$
Variable initial value minimal value maximal value final value
t 0 0 24 24
Cc 2.0E04 1.276E04 0.002742 0.002742
Cs 5.0E04 5.0E04 4.5794959 4.5794959
mp 0 0 0.20716 0.20716
$
ODE)Report)(RKF45)$
Differential$equations$as$entered$by$the$user$
$[1]$d(Cc)/d(t)$=$rgrdvo*Cc/V$
9-3$
P91)(e))Example)95)Continued$
Explicit$equations$as$entered$by$the$user$
$[1]$rd$=$Cc*.01$
$[2]$Ysc$=$1/.08$
$[14]$mp$=$Cp*V$
$
(vi)$$
Change$the$cell$growth$rate$law:$
$
9-4$
P91)(e))Example)95)Continued$
$$$ $
$
Notice$that$uncompetitive$inhibition$by$the$substrate$causes$the$concentration$of$cells$to$decrease$with$
time,$ whereas$ without$ uncompetitive$ inhibition,$ the$ concentration$ of$ cells$ increased$ with$ time.$$
Consequently,$ the$ concentration$ of$ product$ is$ very$ low$ compared$ to$ the$ case$ without$ uncompetitive$
inhibition.$
$
(vii)$
Change$the$observed$reaction$rate$constant:$
$
$
All$other$equations$are$the$same$as$in$part$(v).$
Since$CP$is$so$small,$the$factor$
$
whether$CP
*$=$93$g/dm3$or$CP
*$=$10,000$g/dm3.$$Thus$the$
plots$for$this$part$are$approximately$the$same$as$the$plots$in$part$(v).$
$
P9-1)(f))Example)on)the)Professional)Reference)Shelf)R9.1$
For$t$=$0$to$t$=$0.35$sec,$PSSH$is$not$valid$as$steady$state$not$reached.$
9-5$
P91)(f))Continued$
POLYMATH)Results$
Calculated)values)of)the)DEQ)variables$
Variable$$initial$value$$minimal$value$$maximal$value$$final$value$
t 0 0 12 12
C1 0.1 2.109E04 0.1 2.109E04
C2 0 0 1.311E09 1.311E09
k4 9.53E+08 9.53E+08 9.53E+08 9.53E+08
k3 5.71E+04 5.71E+04 5.71E+04 5.71E+04
$
ODE)Report)(STIFF)$
$Differential$equations$as$entered$by$the$user$
$[1]$d(C1)/d(t)$=$k1*C1k2*C1*C2k4*C1*C6$
$
P9-1)(g))Individualized$solution))
$
$
P9-2)(a))The$key$for$decoding$the$algorithm$to$arrive$at$a$numerical$score$for$the$Interaction$Computer$
Games$(ICGs)$is$given$at$the$front$of$this$Solutions$Manual.$
$
P9-2)(b))Individualized$Solution$
$
P9-2)(c))
Applying$the$pseudosteady$state$hypothesis,$
$
9-6$
P9-3$
Burning:$
$
9-7$
P93)Continued$
$
$