P6-10 (a)

Spect<::5 A:
de
--"-:r
dt -\
-ro. = ktC,-\
Species B:

Species C:
de c _ ..
--·c
dt
, , . . [Link] klC B
Pluggmg mto POLYMATH: gets the following,

ESI::!=[Link]~:§!: var~!!: !E!b,8:~1:.Y~!~ MaximUlll ..~ Minimum.'y~~ !'i~!. . ~

d(calldP::) "'rat t 0 1.00 a 100
ci{co) /0.( t) =z·o ca 1.6 1.6 5.7898e-18 6' .. 789Be .. 18
dice) Id{:::) =rc cb () 1.4556 0 n.6037
k,1-=.4 cc 0 0 .. 9963 0 () .9963
k2"'.{)1 kl 0.4 0.4 04 0.4
ra", . kl"ca k2 0.01 0.01 0.01 0 .. 01
rc"k2"cb ra ·0 64 ·2.'71592et8 -0.54 -2.71.S92e-18

. '"
rb"'k:;:'·ca· .. k2 "cb
·0 0, t"...
'" 1.00
I'C

rb
0
0.54
0.014556
O.6~
0
-O.OU2417
0.00603'1
0.006037

key
~Ca
. Cb
•.. ·Cc

P6-10 (b)
For CSTR, T = [Link]
First calculate kJ and k2 :

6-26
 k =[Link] (20'OOO(_1__ ~)J
2 P R 373 T

See Polymath program [Link].

POLYMA)'H Results
NLES Solution
Variable Value f (x) lni Guess
Ca 1 . 5268515 -6.446E-13 1.5
Cb 0.0319385 7.28E-14 o
Cc 0 . 04121 0 o
tau 0.5
T 760
k1 0 . 0958161
ra -0.146297
k2 2 . 580579
rb 0 . 0638771
rc 0.0824199

NLES Report (safenewt)

Nonlinear equations
[1] f(Ca) = tau*(··ra)-(1 . 6-Ca) = 0
[2] f(Cb) =tau*(rb)·Cb =0
[ 3] f(Cc) =tau*(rc)-Cc =0
Explicit equations
[1] tau = . 5
[2] T = 760
[3] k1 = 72*exp(-10000/(1 . 987*T))
[4]ra = -k1 *Ca
[5]k2 = 1457152*exp(-20000/(t.987*T))
=
[6] rb k1 *Ca-k2*Cb
[7] rc = k2*Cb

Cb vs" temperature

350E-02

3 . 00E-02 + - - - - . - - - - - -

2.50E-02
I
~ 2.00E02

---f------\--~
II
~
tl 1.50E·02

100E-02 I
5.00E-03 +-_________-+--_________ .0...._1
[Link]+OO--·-·-----.-·----··
o 200 400 600
------.-----------,-----J
800 1000 1200
temperature (K)

Therefore, CB is maximum at T=760K.

6-27
P6-10 (c)
(e) ?art is similar to part b except for two rate laws:
fA -k
- _II *('·s - kI
*('
'A

rB =k 1 *C-k
-,-\ -·1 *C B -k,;. *C a
Using those rate laws inPOLYThtlATH produce the following:

___
Eauations:
... .......-..,.,

d{ca) /d(t) ;::::r:-a

l!ti t ~a 1 ..~1::~
1.6
d(cb)Jd(tl=rb a
d(cc) Id(tl ::::e'C o
[Link]:: -_.
klr·=8.33e·S
k1£"'.OOOl
\ ..ti:::: -.
k2=2.78e-5

1\
r[Link]k2"cb
!.,2IJC
ra=klr""cb··klf"ca !\

[Link]
c"cco 0.808 J.

var:iable In,itial value Maximu.m value Minim1.4'11

-------.-'"'--- ....... ...........value -_-.-. _ _
_........ ............... -:inal
~--
----
value
.,. .......... _-, ...... .......
t 0 350000 0 350000
ca 1.6 1.6 0.436316 0.4.16316
cb 0 0.833237 0 0.5159
cc (J 0.647'784 0 0.64'1784
[Link] 8 3.3e·"05 S.33e··05 13. Be-OS 8 . 33e-OS
klf 0.0001 0.0001 0.0001 0.0001
k2 2.78e06 2.78e·06 2.78e-06 2.78e-·06
rc 0 2 _3164e-- 06 a 1.4342e·-06
ra -0.00016 6 _S7168e--07 ··0.00016 -6. 57168e-- 07
:r:b 0.00016 0.00016 --1.20632e··06 . 0' .7703 4e-... 07

P6-10 (d)
Th isis similar to part d except for one rate law:
--"1 *C.... 8: -_ok . -2 *C"'c
rc -k'
Using that in POLTh1ATH produces the following:

6-28
 EqlJ.§!ci~~.:
d{ca)/d(t)=ra 2 ce: T
d(cb)/d(t)=:::b i
~ 5.:lC .!..
d(cc)/d(t);r;c
k[Link]=8 _33E!-'S
k1.f= _, 0001
k2:=2,78e--6
k2r=1.. 3 %-6
ra"k1:r:-·cb-· kIf'cd
rc'"'k2f*cb-·k[Link]*cc
r'b=kl f"ca '" klr 'cb-- k2 f "cb+k2.::'cc
to '" (), t:l!
.L
'" 350000

Variable
- --- ~~..s~,~! __ ::-al':l:~ 1:!~im1.l!:LvallJ.e Minim~ya1ue Final._y~!ue
t 0 150000 0 350000
Cd 1. 6 1 5 a,490306 0 490306
cb 0 0 833769 0 0.583662
cc 0 0.525032 0 0,526032

k1r 8,,33e,05 8 33e-05 8,33e'OS 8.33e05

kif 0.0001 () 0001 00001 0.0001
kl: 2,788 06 2 730 06 2. ii3e' 06 2.,78e-·06
k2: 1. 3%06 1. 3ge06 1 39806 L '3%,,1)6
::::d 0 oootS ··4 115738·-0'1 '·0 ,00016 --,4 .11573e .. 0 7
l:C 0 2 25569806 0 8.91396,0·-07
r;b 0, 00Gl6 0 GOO16 -1..124.93806 "4,, 79824eO)

P6-10 (e)
(e) Vlhen kl>l00 and k2<O.1 the concentration of B immediately shoots up to 1,6 and
then slO\vly comes back down. while CA drops off irnmediate1y and falls to zero. This is
because the first reaction is so fast and the second reaction is slower with no reverse
reactions.
When k2 ;:;;; 1 then the concentratlon of B spikes again and remains high, while very
little of C is formed.. This is because after R is fonned it will not got to C because the
reverse reaction is faster.
Vlhell k-2 ::::: 0.25, B shoots up, but does not stay as high because the second reverse
reaction is a slightly slower than seen before, but still faster than the forward reaction..

P6-11 (a)
InteImediates (primary K-phthalates) are fOlmed flOm the dissociation of K-benzoate with a CdCh catalyst
reacted with K-terephthalate in an autocatalytic reaction step:
A-~R~S Series
R + S -~ 2S Autocatalytic

C :::::~ = 1l0kPa =0 02moll dm'

AD RT (8.314 [Link]')( 683K) .
mol.K

6-29
Maximum in R occurs at t = 880 sec. See Polymath program P6-11-a. pol,

POLYMATH Results
Variable initial value minimal value maximal value final value
t 0 o 1500 1500
A 0,02 0.003958 0.02 0.003958
R 0 o 0,0069892 0.005868
S 0 o 0,0100382 0.0100382
k1 0.00108 0,,00108 0.00108 0.00108
k2 0.00119 0.00119 0.00119 0.00119
k3 0.00159 0.00159 0.00159 0.00159
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(A)/d(t) = -k1 *A
[2] d(R)/d(t) = (k1*A)-(k2*R)-(k3*R*S)
[3) d(S)/d(t) = (k2*R)-(k3*R*S)
Explicit equations as entered by the user
[1] k1 = 108e-3
[2] k2 = 1,1ge-3
(3) k3 = 1 ,,5ge-3

P6-11 (b)
1) T= 703 K
3
CAO = 0,,019 mol/dm

Similarly,
k~ =3.3xlO- s- and k~ =3.1xlO-3 dm 3 Imol.s
3 1

Maxima in R occurs at around t =320 sec" See Polymath program P6·11·b i pol

POLYMATH Results
Calculated values of the DEQ variables
Variable initial value minimal value maximal value final value
t O O 1500 1500
A 0,019 3,,622E-04 0,,019 3,622E-04
R 0 o 0,,0062169 8,856E-04
S 0 o 0,0174625 0,0174625
kl 0 00264 0,,00264 0.00264 0.00264
k2 0.0033 0.0033 0,,0033 0.0033
k3 0.0031 0.0031 0,0031 0.0031
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(A)/d(t) = -k1 *A
[2] d(R)/d(t) = (k1 *A)-(k2*R)-(k3*R*S)
[3] d(S)/d(t) = (k2*R)-(k3*R*S)
Explicit equations as entered by the user
[1] k1 = 2,,64e-3
[2) k2 = 3,,3e-3

6-30
 [ 3 J k3 = 3,1 e-3

2) T = 663 K
CAO =0,19 moIJdm
3

k; = (1.08xlO-3 s-l)ex p ( (42600cal / mol)

(1.987callmol.K) 683K
(_I_-_I_)J
663K
= 0.42 X10-3 S-1

k~ 3 1
=0.4xlO- s-
k~ = 0.78xlO- dm
3 3
/ mol.s
See Polymath program [Link].

POLYMA Tn Results
Calculated values of the DEQ variables
Variable initial value minimal value maximal value final value
t 0 o 10000 10000
A 0.019 2.849E-04 0.019 2.849E-04
R 0 o 0.0071414 0.0012573
S 0 o 0,016889 0.016889
k1 4.2E-04 4.2E-04 4.2E-04 4.2E-04
k2 4.0E-04 4.0E-04 4.0E-04 4,OE-04
k3 7.8E-04 7.8E-04 7.8E-04 7.8E-04
ODE Report (RKF45)
Differential equations as entered by the user
l l ] d(A)/d(t) = -k1 *A
l2] d(R)/d(t) = (k1 *A)-(k2*R)-(k3*R*S)
[3] d(S)/d(t) = (k2*R)-(k3*R*S)
Explicit equations as entered by the user
[1] k1 = OA2e-3
[2] k2 =OAe-3
[3] k3 =0,,78e-3
Independent variable
variable name: t
initial value: 0
final value: 10000
0.020.------,-·------·-·-------,

0,004

2000 4000 t 6000 8000 10000

Maxima in R occurs around t = 2500 sec,

P6-11 (C)
Use the Polymath program from part Ca) and change the limits of integration to 0 to 1200, We get:
3
CAexit = 0.0055 moIJdm
3
CRexit = 0.0066 mol/dm

6-31
 CSexit = 0,0078 mol/dm'

P6-12 (a) P6-12 (b)

== -_(.7)(.1)
-riA
fIB :;;:: ....-
. mol
.....__ ... _:;;:: 0.023-""--,,,
3.3 dm 3 _$
r"ll
...
= 0 * ro_D =: 0-dm'
m<:t._
_s

1:,B ::: 0 * fj€ "" 0 m~l_..

dm' .s
P6-12 (c) P6-12 (d)
_ -riA _ (,7)(.1) , mol
f lC - "-""'- - -,,--- ::: 0,023 "·-1"
3 j <inr*s
_-2*r _,2(3)(50 1 (.I) _ mol
2D
f:c - - ...... -' -_..._--,. __.,_.- == -"Q,O(h2·"t--
3 3 dm' *5
lic =rJ £ ;:·-(.2)("049)( .51) = ··O.005-!~I_.,
dm' *5

P6-12 (e)
Ii" ::::: 0 '" liA =O..dmmol
·~--
3......-
*5
. mol
'iE ::: O~· li[Link] 0,:: -".
dm'·s
r,E ::: (.2)(.049)(.51):::;: [Link] ....!!!.ol
3
dm .s
P6-12 (I) P6-12 (g)
fA ::: --0.07 - 0.0026 : : : -0.0726 mol F,F
V=, . M-, . ~ .
.-~"
::::::~!{~·~~_: . ~:.~2
·"·fA
I[Link] 0.023 . . ,0.0052· 0.005 = O.0128 .... ~~~.
dm- .5 _ 100(3 ,0.1) _ 3
- ..,_. . _""' ...."........ ::::: 4000dm
0,0726
fD = 0.0078 ······0.033 == 0 OOll"""il:..?L
1
..
dm _s

P6-12 (h)
Mole balance: CAD ·- CA = (_. r A)r
Cc = (rc}r
CD = (rD)r
Rate law, rA = -[k"CA +~kWCAC~ ]

6-32
Solving in polymath:
SBID =I'B/rD = 247
See Polymath program P6-12··h. pol.

POL YMATH Results

NLES Solution
var'iable Value fIx) lni Guess
Ca 0.0068715 -2.904E-10 3
Cb 0.9620058 -1 . 332E-15 o
Cc 0.5097027 --1,67E-08 o
Cd 0.0038925 -2.391E-08 o
Ce 0,2380808 1.728E-08 o
kd 3
ka 7
rb 0.0160334
ra -0.0498855
ke 2
rc 0,008495
rd 6,,488E-05
re 0,003968
tau 60
Cao 3

NLES Report (safenewt)

Nonlinear equations
[1] f(Ca) = Cao-Ca+ra*tau = 0
[2] f(Cb) = Cb - rb*tau = 0
[3] f(Cc) = Cc-rc*tau =0
[4] =
f(Cd) Cd-rd*tau 0 =
[5] f(Ce) = Ce - re*tau = 0

Explicit equations
[1] kd = 3
[~2]ka=7
[3] rb = ka*Ca/3
l4] ra = -(ka*Ca+kd/3*Ca*CcJ\2)
[5] ke =2
[6] rc = ka*Ca/3 - 2/3*kd*Ca*CcJ\2 ,. ke*Cd*Cc
[7] rd = kd*Ca*CcJ\2 - 4/3*ke*Cd*Cc
[8] re = ke*Cd*Cc
19] tau = 60
[10] Cao = 3

P6-12 (i)
For PFR and gas phase:
dF dF dF dF dFE =r
Mole balance: - - A-
dV
= rA - -B= r -.i:..·=r _D_=r __
dV B dV C dV D dV E

6-33
Rate law:

Stoichiometry:

FT =FA +FB +Fc +FD +FE

dy = -a FT
dV 2y FTO
Plot of CB and Cc are overlapping.
See Polymath program P6··12·i pol.

POLYMATH Results
Calculated values of the DEQ variables

Variable initial value minimal value maximal value final value

V o o 100 100
Fa 20 9 . 147E-04 20 9.147E-04
Fb o o 6 . 6638171 6.6638171
Fe o o 6 . 6442656 6 . 6442167
Fd o o 0 . 02012S8 0 . 0171261
Fe o o 0.0043322 0 . 0043322
y 1 0.9964621 1 0 . 9964621
Ft 20 13.330407 20 13 .330407
Cta 0.2 0.2 0.2 0.2
Ce o o 0 . 0993605 0.0993325
ka 7 7 7 7
kd 3 3 3 3
ke 2 2 2 2
Ca 0.2 1.367E-05 0.2 1 . 367E-OS
rb 04666667 3.191E-05 o 4666667 3 . 191E-OS
ra -1.4 -1..4 -9.S86E-05 -9.S86E-05
Cd o o 3 . 0E-04 2.S6E-04
Fta 20 20 20 20
re 0.4666667 -1.923E··05 0.4666667 -1 . 923E-05
rd o -7 . 012E- 05 8 . 653E-04 -6.742E-OS
re o o S . 908E-OS 5 . 087E-·05
alfa 1.0E-04 1.0E-04 1.0E-04 [Link]-04
X o o 0 . 9999543 0.9999S43

ODE Report (RKF45)

Differential equations as entered by the user

[1] d(Fa)/d(V) = ra
[2] d(Fb)/d(V) = rb
[3] d(Fc)/d(V) = rc
f 4] d(Fd)/d(V) = cd
[5] d(Fe)/d(V) = re

6-34
 [6] d(y)/d(V):::: -alfa*Ft/(2*y*Fto)

Explicit equations as entered by the user

[1] Ft:::: Fa+Fb+Fc+Fd+Fe
[2] Cto:::: 0.2
[3] [Link] Cto*Fc/Ft*y
[4] k[Link] 7
[5] k[Link] 3
[6] k[Link] 2
[7] [Link] Cto*Fa/Ft*y
[8] r[Link] ka*Ca/3
[9] r[Link] -(ka*Ca+kd/3*Ca*CcA 2)
[1. 0 1 [Link] Cto*Fd/Ft*y ·40.
. V 60
[Ill Fto::::0 . 2*100
[12J r[Link] ka*Ca/3 - 2/3*kd*Ca*CcA 2·' ke*Cd*Cc
..
[13] r[Link] kd*Ca*CcA 2 - 4/3*ke*Cd*Cc
[lA] r[Link] ke*Cd*Cc
[15J al[Link] 0.0001
[16] X::::1-Fa/20

12

!l

>4

\I
0

(I.. !l$(f

#.,1124

(I,out

iJAltZ

1).• IlM

[Link] H)O
Il 41l V 6(1

P6-12 G) Changes in equation from PaIt (i):

dFc k diffilSe = 2 nun
. -1
dV = rc -Rc Rc = kdiffilSeCC

See Polymath program P6···12-j.po1.

6-35
 20r----------------------------, 0,020.--------------------------,

F~
16 0.016
lBJ
12

40 V 60 80 100 40 V 60 80 100

P6-13 (a)
m-xylene --> benzene + methane
A -->B +M
m-xylene --> p-xylene
A --> P
See Polymath program P613 . [Link].

POLYMA TH Results
Calculated values of the DEQ variables
Variable initial value minimal value maximal value final value
-
V
'-- o o 6000 6000
Fa 75 6.1072984 75 6.1072984
Fb o o 16.297198 16 . 297198
Fp o o 52.595503 52.595503
Fm o o 16.297198 16 . 297198
Fi 25 25 25 25
Ft 100 100 116.2972 116.2972
k1 0.22 0.22 0.22 0.22
k2 0.71 0 . 71 0.71 0.71
Cta 0.05 0.05 0.05 0.05
Ca 0.0375 0.0026257 0.0375 0.0026257
rl -·0.00825 -·0.00825 -5 . 777E-04 -5.777E-04
Cb o o 0.0070067 0.0070067
r2 -0.026625 -0 . 026625 -0.0018643 -0.0018643
Cp o o 0.0226125 0.0226125
Spb o o 3.2272267 3.2272267
tau o o 3 3
y o o 0,7634409 0 . 7634409
X o o 0.9185694 0.9185694

ODE Report (RKF45)

Differential equations as entered by the user

[ 1) d(Fa)/d(V) = r1 +r2
[2) d(Fb)/d(V)=-r1
[3) d(Fp)/d(V) = -r2

Explicit equations as entered by the user

[1) Fm = Fb
[2) Fi =25
[3) Ft = Fa+Fb+Fp+Fm+Fi
[4J k1 = ,,22

6-36
 [5] k2 = . 71
[6] Cto = . 05
[7] Ca = Cto*Fa/Ft
[8] r1 = -k1*Ca
[9] Cb = Cto*Fb/Ft
[ 10 ] r2 =-k2*Ca
[11] Cp = Cto*Fp/Ft
[12] Spb = Cp/(Cb+ . 0000001)
[13] tau = V/2000
[14] Y = Fp/(75 . 00000001-Fa)
[15] X = (75-Fa)/75

a l' =2.8 is necessary to achieve 90% conversion

10r--------------------------, 4.0 .-----------------------------,

0.8 3.2 . - - - . - - - -.....- - - . - - - -•.•.---.•- - - - -

0. 6 2t
I~ ~Pj
L6

0. 8 r........ .
0. 0
2tOO V 3600 4800 6000 0 1200 2400 V 3600 4800 6000

P6-13 (b)
CSIB \
FM =1"MV ~.? == rPV
:c
Mole Balances:

Rate La\vs.·
.,,"
"E .r -."1 - -.I ". . . ')
k :;:; k. exp.· ,,_.d
l ,0 R IT\.
946· ./

Using these equations and Polymath we find the optimal temperature is 1194 K. The maximum
concentration of p-xylene is 0.013 mol/dm3
See Polymath program P6·[Link].

pOLYMA THResul!§
NLES Solution
Variable Value f(x) Ini Guess
Ca 0 . 012197 7 . 15E-ll 0.0375
Cb 0 . 0122301 5 . 284E-12 o
Cm 0 . 0122301 5 . 284E-12 o
Cp 0 . 0130729 -3 . 069E-ll o
Cao 0.0375
tau 0.5
k10 0 . 22
E1 2 . 0E+04
R 1.. 987
k20 0.71
E2 10000

6-37
 Yp 0.5166557
T 1194
k1 2.0054175
rb 0.0244601
rm 0.0244601
k2 2.143628
rp 0.0261459
ra -0.050606

NLES Report (safenewt)

Nonlinear equations
[1] f(Ca) = Ca-Cao-ra*tau = 0
[2] f(Cb) = Cb-rb*tau = 0
[3] f(Cm) = Cm-rm*tau = 0
[4] f(Cp) = Cp-rp*tau = 0

Explicit equations
[1] Cao = .0375
[2] tau = ,,5
[3] k1o=,,22
[4] E1 = 20000
[5] R = 1.987
[6] k20 = .71
[ 7] E2 = 10000
[8] Yp = Cp/(.03750000001-Ca)
[9] T= 1194
[10] k1 = k1o*exp((E1/R)*(1/946-1/T»
[11] rb = k1*Ca
[12] rm = k1 *Ca
[13] k2 = k2o*exp((E2/R)*(1/946-1/T»
[14] rp = k2*Ca
[ 15] ra = -k1 *Ca·k2*Ca

-_._----------- ---------------------

P6-14(a)
50dm 3 PFn
Mole balance:
dCA f';\ deB .:::::::
f'13
,,~

<IV Vo dl T
dCc rc dev
dll [
Vo dV Uo
11(:£ ./ B tlOr Fp
=
dV Vo dV' =~~;

6-38
 Rate laws:
r . ' 1 ' 1 'U 1-- ~li £:;2

Fa ·2rVI l'F:"

l'c rlJ 1 I' [::2 . "21'1' 3

tn TO] 2TB2 I TF:)

'IE TE2

Til(} equation for [Link] conversion ur A is :

)( = .G. AU ----.
C-"I
C AO
See Polymath program P6-14··a. pol.

POLYMATH Results
No Title 08-01-2005, RevS 1.233

Calculated values of the DEQ variables

Variable initial value minimal value maximal value final value

- -----
t 0 0 50 50
Fa 15 0 . 2090606 15 0.2090606
Fb 20 1. 3440833 20 1.. 3440833
Fe 0 0 1 . 9655663 0.3535564
Fd 0 0 7 . 2554436 6 . 4570707
Fe 0 0 2.5920934 2 . 5920934
Ff 0 0 4.6265981 4.6265981
va 10 10 10 10
Caa 1..5 1.5 1.5 1.5
Cba 2 2 2 2
Ft 35 15 . 582463 35 15 . 582463
Cta 3.5 3.5 3.5 3.5
kd1 0 . 25 0 . 25 0 . 25 0.25
ke2 0.1 0.1 0. 1 0. 1
kf3 5 5 5 5
Ce 0 0 0 . 228291 0.0794128
Cd 0 0 1.. 4503322 1 . 4503322
Cb 2 0 . 3018965 2 0 . 3018965
Ca 1.5 0 . 0469574 1..5 0.0469574
rd1 1.5 0 . 0010699 1.5 0.0010699
re2 0 0 0.1004639 0.0068104
rf3 0 0 0.3632767 0 . 0095194
re 0 0 0.1004639 0 . 0068104
rf 0 0 0.3632767 0 . 0095194
rd 1..5 -0.042376 1..5 -0 . 0030314
ra -.1. 5 -1.5 -0 . 0215011 -0 . 0215011
rb -3 -3 -0 . 0116593 -0 . 0116593
re 1..5 -0 . 0962952 1..5 -0.0111585

ODE Report (RKF45)

Differential equations as entered by the user

6-39