Solution Manual Elements of Chemical Reaction Engineering 4th Edition WWW - Elsolucionario.org 573 680

Solutions for Chapter 10 - Catalysis and Catalytic Reactors
PIO-I Individualized solution
PIO-2 (a) Example 10-1

(1) Pentane isomerization nP -pt--7 iP
Assume that Pt is the catalyst used.
Maximum f = 5 molecules/site/sec
Minimum f =3e-3 molecukes/site/sec
Maximum rate:
--rp = fD(_l __ ) %Pt
MWpt 100
-rp = 5(0.5)(_1_)_~ = 1.28*10-4 mo~

195 100 s geat
Minimum:
--rp = 3*10-3 (0.5)(_1_)_~_ = 7.69*10- 7 mol__
195 100 s geat
1
(2) SO2 +--0
2 2 --7 SO3
No turnover frequency is given so this rate law cannot be determined by this method
(3) H2 + C2 H 4 -~ C2H 6
Assume Cobalt is the catalyst.
--r = fD(_l _) %C~
H2 MWCo 100
Maximum:
f =100 molecules/site/sec
mol
--rH =100 ( 0.5 )( - 1 ) ---=0.00849---
1
2 58.9 100 s geat
Minumum:
f= 0.01
-rH =0.01 ( 0.5 ) -

1 ) 1 -7 mol
2
( 58.9 -----=8.49*10
100 s geat
PIO-2 (b) Example 10-2
10-1
(1) Cv = 1
Cr 1+ KrPr + KBPB
Ks = 1.39 Kr = 1.038
Pro = YroProtal = 0.3*40 = 12
For 60% conversion
Pr = Pro (1- X) = 12*0.4 = 4.8atm
PB =PTOX =12*0.6=7.2atm
Cv = 1 =_1_=0.063
Cr 1+(1.038)(4.8)+(1.39)(7.2) 15.99
6.3% of the sites are vacant
(2) X =0.8
Cros = .CvKrPr _ KrPr
CT Cr 1+ KrPr + KBPB
eros = (1.038)(1)(1-0.8) = 0.2076 =0 09
CT 1+(1.038)(1)(1-0.8)+(1.39)(1)(0.8) 2.3196 .
9% of the sites are covered by toluene
(3) Linearize the rate law to:

PH?Pr 1 KBPB KrPr
----=-+--+---
-r7 k k k
PIO-2 (c) Example 10-3

Increasing the pressure will increase the rate law.
p?
-r---T--R
A 7
l+KrPr
If the flow rate is decreased the conversion will increase for two reasons: (1) smaller pressure drop
and (2) reactants spend more time in the reactor.
From figure ElO-3.1 we see that when X =0.6, W =5800 kg.

PIO-2 (d) Example 10-4
With the new data, model (a) best fits the data
(a)
POLYMATH Results
Nonlinear regression (L-M)
Model: ReactionRate = k*Pe*Ph/(1 +Kea*Peat·Ke*Pe)
10-2
variable Ini guess Value 95% confidence
k 3 3.5798145 0.0026691
Kea 0.1 0.1176376 0.0014744
Ke 2 2.3630934 0.0024526
Precision
RA2 = 0,,9969101
R A2adj = 0 . 9960273
Rmsd =
0 . 0259656
variance = 0.0096316
(b)
POLYMATH Results
Model: ReactionRate = k*Pe*Ph/(1+Ke*Pe)

k 3 2.9497646 0.0058793
Ke 2 1.9118572 0.0054165
Precision
RA2 =
0 . 9735965
RA2adj = 0.9702961
Rmsd = 0.0759032
Variance = 0.0720163
(c)
POLYMATH Results
Model: ReactionRate = k*Pe*Ph/((1 +Ke*Pel"'2)
Variable Ini guess Value 95% confidence

k 3 1.9496445 0.319098
Ke 2 0.3508639 0 . 0756992
Precision
RA2 = 0.9620735
RA2adj = 0 . 9573327
Rmsd = 0 . 0909706
vari.ance = 0 . 1034455
(d)
POL YMATH Results
Model: ReactionRate = k*Pel\a*Phl\b

-k----
3 0.7574196 0 . 2495415
a 1 0 . 2874239 0.0955031
b 1 1.1747643 0.2404971
Precision
RA2 = 0 . 965477
R A 2adj = 0.9556133
Rmsd = 0 . 0867928
Variance = 0.107614
10-3
Model (e) at first appears to work well but not as well as model (a). However, the 95% confidence
interval is larger than the actual value, which leads to a possible negative value for Ka. This is not
possible and the model should be discarded. Model (f) is the worst model of all. In fact it should be
thrown out as a possible model due to the negative RII2 values.
(e)
POLYMA TH Results
Nonlinear regression (L·M)
Model: ReactionRate = k*Pe*Ph/((1 +Ka*Pea+Ke*Pe)ll2)

-3---
k 2.113121 0 . 2375775
Ka 1 0,,0245 0.030918
Ke 1 0 . 3713644 0 . 0489399
Precision
RA2 = 0 . 9787138
RA2adj = 0.9726321
Rmsd = 0 . 0681519
Variance = 0 . 0663527
(f)
POLYMATH Results
Model: ReactionRate = k*Pe*Ph/(1+Ka'Pea)

k 3 44.117481 7 . 1763989
Ka 1 101. 99791 16 . 763192
Precision
RA2 =·0 . 343853
RA2adj = -0 . 5118346
Rmsd = 0.5415086
Variance = 3 . 6653942
PIO-2 (e) Example 10-5

1
(l)X =1- klk
(l+kd t ) d
As t approaches infinity, X approaches 1.
10-4
large klta
(2) Second order reaction with first order decay.

dX ,W
- = - rA -
dt NAD
2
-rA '=ak'CA
a = exp[-kdt]
dX = Wk' C2 (1- X)2 exp[-·k t]
dt N AD d
AD
dX =k(I-X)2 exp[-ki]
dt
X k
1-- X = k(1-exp [-kd t ])
d
~. t... X =k-
as t -y m Imty -.--
l--X kd
X=J{d
1+ k/
/kd
(3) First order reaction with first order decay
dX Wk'
di- = ""N
CAD (1- X)exp[-kd t ]
AD
dX
- = k(l- X)exp[-kdt]
dt
InC~x)= ~ (I-exp[-kdtj)
t -7 infinity X = l-exp [ - ~]
PIO-2 (0 Example 10-6
10--5
Increasing the space time makes the minimum disappear. Decreasing the space time moves the
minimum to the left and the concentration is higher.
Increasing the temperature so that the rate constants are higher will cause the catalyst lifetime to be
shorter.
If tau =0.005 the minimum C A=0.607

If tau = O.Olthe minimum CA = 0.5088
PIO-2 (g) Example 10-7

(1) If the solids and reactants are fed from opposite ends,
da kda
--=- atW=We ,a=l
dW Us
C = kd~e
1 U
S
This gives the same expression for conversion as in the example.
(2) Second order decay

1
a=-----
kd W
1+---
Us
_~_= kC~oUs In(I+'5dW J

I-X kdFAO Us
1.24= (0.6)(0.075)2 US_In (1 + (0.7~)2~~?OJ

(0.72)(30) Us
Solve for Us by trial and error or a non-linear equation solver.
=
Us 0.902
(3) If G =2
dX 2 (l-x)2
F --- = kC ------a
AO dW AO (1+c X r
10-6
2
(
2£ (1 + £ ) In (1 - X ) + £2 X + 1+£)2 X = kC AOUS ( 1- exp [-kd W]J
e
I-X kdFAO Us
9X
12In(I-X)+4X +--=1.24
I-X
X =0.372
PIO-2 (h) Example 10-8

Uo = 0.025 Uo = 0.25
1 . 0 -,- - - - - - - - - - - - - - ,
0.8
~.'.""
0.6 L~J 0.6
0.4 0.4
0.2 0.2
"-",
0.0
4 z 6 8 10 0 2 4 z
6 8 10
Uo =2.5 Uo=25
1.0 1.0 .~
0.8
0.6
0.4
0.2
4
z
~-
6 8 10
0.0
~--'"".--=~
I) 2 4 z 6 8 10
PIO-2 (i)
For EA = 10 and Ed = 35, for first order decay we rearrange Eq 10-120 to:
In(l- kdotEd
EA
J
= Ed (!-'~J
R T To
=Ed
- ( ._---
1 1 J
R I'o T
lO-7
R 1 1 1
-In =---
Ed l-
kdOtEd 1'a T
EA
1'a 400
T= =--------~--------~
1+0.07948In( 1 )
1-0.00286t
PIO-2 (j) Individualized solution
PIO-3 Solution is in the decoding algorithm given with the modules
PIO-4
W+S,·.,.w·s
TBA.S,(.,.TBA + S
PIO-4 (a)
Surface Rm Limited
r
".Wl. =0
kA
C1,,.,,C,,.
'k, t
1 K
(~ V {"
~7EA·S ==-'j('-" ¥ . l '
== £\.1BAI..'nl.·1 L y, SInce K". ';;;;; 'TBA
D D
10-8
PIO-4 (b)
Adsorption of isobutene limited
rADl ;kAl [Cr - ::~] Cv •
Bey Ridea1 Kinetics
PIO-4 (d)
10-9
W .. S + 19S1HTBA+S2+S1
2
r
S
-= k
S
[' C C _.~1.BAKSC:~~'l=Y1l
'W·S2 1.$1
en == C V1 -+- CloSl
CT2 =c'V2'W-S2
+C
PIO-4 (e) Individualized solution

PIO-4 (0 Individualized solution
PIO-5 (a)
H..,+
..
C..,H
~ 4
H +E-4A
Bey Rideal.
E·S~4>A+S
E + S ii"~ E .. S • CE1OS :::: KE. PE. Cv

"
TS "" ks[ CE .. S PH]
CT""'CV+CE"S
f~ =C~~{-l:~~;l
PIO-5 (b) Individualized solution
PIO-5 (c)
02 +2S p 20·S Az +2S p 2A·S
C3H6 + O·S ---) C3H 5 0H.S B + A·S ---) C·S
C3 H 60H.S P C3 H 5 0H + S C·S---)C+S
-riJ = r's = k 3 PB C A • S
rAD =kA [ PAzCV2 -

C~'S]
KA
10-10
rAD =0
kA
CAoS = CV~KAPA
-rB = rS = k3PBCV~KAPA
re.s = kD [ Ce•s - P~~v] = kD [Ce.s - KePeCv 1

rcos =0
kD
CCoS = KcPcCv
Cr = Cv + CAoS + CCoS = Cv [1 +~KAPA + KcPc ]
k 3 Cr PB .JK:P:
-rB = rs = l+~KAPA + KcPc
PIO-6 (a)
A (butanol) ;: B (butene) + C (warer)
Possible meChanism:
7 .. ::::
,~..
K (PC . . . .K~·AS_:)
AA ,4 S
AA.
rs "" ks (CA.s Cs • CaoS CcoS Ks)
rDB =: knB (esoS . PB Cs/Kos)
C·S t:! c+s rDC;: klX {Ccs - Pc Cs/Kr:d

Assume stuface reaction controlling:
( ··a-s
' - PB
- -K Cs. -- PB K AS ('··S
DB
Pc Cs '" PC KAC (~-5

' == -K-
( ,<:'5
rx:
10-11
'- - (
·r,J - rs - k s! P,tK,Li·s -- KKK
.,! .. pgpc C;._.) -_ kS KAi·s
-'Zl'pA _. K Jl were
}!ePc h . K - KKK K
eq - S AA DC DE
\ S DB DC eq
site bala:lce: ('T == Cs +- CAS +- CBS + Ccs :;: Cs (l + KAA PA+ KAB PB + KAc Pc)
:. ···rA ;:: _.......

ks. KAA cf (P.A ~.........
F1l_ ......P~)
_ .. _ _ ._.
{I + P A K.A.A + PB K.A.B + Pc K A c)2
If PBO::: 0 and Pco == 0 , then
.; := ~2.!MS1!:M.;:: Is1 PM _.
AO {I -+ PAn KAA )2 1 -+ k2 Pio +- k3 PAO
This is consistent with the observation.
PIO-6 (b)
From r..iJ.c figure.
Point numb::::r 2 3 4 :; 6
~I: (_lmr~~) 0 0.275 0.5 0.77 0.77 0.5

AO hr'!b cat
PAC (arm) 0 4.5 27 54 112 229
.J.p-; . . 21.4
405 6 . 45 8..14 L2.06
·"fAO
10-12
At large PAl): -r~O =~.Ll'.~Q :;; ¥1... (_l_) ; using point 6: k, =(229) (0.5) ;; 114
k2 P~o K2 PAO k2"
At small P AO: . ;AO:= kl P AO ; using point 2: kJ :: 0061 = k2:::: 5.34xlO-4
.. rAO =..... _... 0. 061. ~ AO ............... ; so

1T 5.34x 10-4 PAo + k, P AO
Using point 3: k3 :: 7.05xIO· 2 = k3 = 3.19xlO-2

(The reason for the different
Using poim 4; k3 3. 19x 10,,2
Using rJOim 5;
:=
k3 "" L05x 10.2

} values of k, is from reading
the graph)
25.0·~ - - y "" 4.3103 + O.073937x R= 099583
20.0 -
lntercepb1/ko. 5 ::: 4.31

k::: 0.054
Slope := KA/kO'! = 0.074
KA ::: 0.32
J
o.0 '~'j"'.:"""'~ ····-~~i· .. ·~~ .. ·"':"·····':"· .. "':"."""';.... "1"..""":"...... ~ .... ~-.;" ..~-:"'--o:"' •• ~~\.' "';'-'''':''$''~''''"'~''''-i
o 50 100 P ISO 200 250

a
PIO-6 (C)
Find the percent of vacant sites
Pb and Pc "" 0 so that red llces to:
%vacant ::::: ._-_ 1..... - .. _.:;::: .........._....1__ ...__. =: 0.41

l+K AAPAO 1+0.01596*90
Find the percent of sites occupied by A and B. No B will have occupied any
sites at X : : : O. So;
KAAP
i''''1:." -_ .-..........
0/ A
_ . . _-._. -_ ...... 0.01595 ~90 -- 0-9
,. . . . . ,....._, ........,..................... . ,J
1 + K,<\,APA "1 -+- 0.01595" 90
PIO-6 (d) Individualized solution
----------------------------------------------------------------------
PIO-7
10·13
ME --'+ D}(fE + rhO
~ . -- ... _-----
100 300
The r.ue o~ formation ofDME is gream:r inirially. 11ris is a result of IJl(){e vacant siteS being
inirially available for reaction because water is not adsorbed on the sites. As time goes on
the equilibrium concenll:u:ion of Water sites is reached. WaI.C:J: is strongly adsorbed on this
catalyst.
Probable Mech;mism
ME+5 :;= ~fE·S

2ME· S""""1> W· S + DME t S
Assume Surface Reaction Controls
CME-S "" K/.u:. PME Cv

Cw.s == Kw Pv". Cv
PIO-8
Given: Kinetic r.:ue expression for the reduction of NO over :l solid catalyst:
kPNPC ~ == partial pressue NO

t" ;: """"""'""""---"--------
{I +- Kl PN+- K z Per Pe =: partial pressure CO
Assume that overall reaction is of the form
NO +CO "....,.t·N2 +COz

PIO-8 (a)
10-14
It is seen that neither Nz or C~ appear in the denominator. This infeIs that neither is
adsortxd on the catalyst, On the other hand. it can be infered that both NO and CO are
adsorbed on the surface. The squared denominaror suggests a dual site surface reaction of
the adsorbates of NO and CO. Therefore the following mechanism is proposed.
kA."i P,.. ;;;: P,vo

NO(g) + S <=: NO· S Pc::::: Pea
keN
CO(g) + S <=: CO· S '-1"0/ ;;;: k:cN [Pc Cs - Cco.s/KcN]
ks
NO • S + CO • S -1- ~ N2 + Cth + 25
With the surface reaction controlling
CNQ-S ;;;: KAN' PN Cs
4:o-S :: keN Pc Cs
Tuen CT :: Cs ,. CNQ.S + Cco.s :: Cs (1 +- KAN PN + Kc."'N Pc]
and therefore reaction is -rs:: ks CNo-S Cco-s:;; ks c..~ PN Pc KAN Ik"N
or.r$ ""!ss..!C~,~,,f~?s:.,gL with

k\ :: ks ct Km KeN
[1 +- K.~"I fIN + N.:N PcP Kl :;;KAN
K1=KcN
kJ Pc PN'
"'1"s :::: ---,.",,,-,,,--'- ' "--'-.--~,,-..-.
[l + K t PN + K2 PcJ2
PIO-8 (b)
Assume chat Pc »flN. Then Pc chattges very little during the course of the reaction
and remai.'1s consu.m,. A maximum in (-rs) rhen occurs. for a fixed value of PN at:
10-15
The rate of n::.action will. increase ..vim an inC're:l.Se in Pc until me: above value is reached.
• after which it '..vil.! decrease. It appears tbat there is an excess pressure which will mini:miz.e
reactOr YoiU!l'le .. Operating at excess pressure greater than t..'"tis value will. decrease (-rs), and
hence increase V. This analysis is exact if the catalytic reaCtor is a CSTR. If me reactor is
t:re:ued as PFR. the Cthical value of Pc is only approximarc. but the general observation is
qualitatively the same.
This analysis further assumes that the excess CO can be elimitmcd easily and economically
downstream from the NO converta'.
PIO-8 (C)
The conditions for which the rate law and mechanism are consistent are the
following.. DIe CO S surface reaction must be the rate limiting. P cdP NO must be
small. The mechanism must be a dual site mechanism (which it is).
PIO-9
Methyl ethyl ketone (MEK) is an important industrial solvent that can be plOduced {roll1lhc dehydrogenation
of outall·2-ol (Btl) over a zinc oxide catalysl
Bu·+MEK+ Hz
/i) 11 t C
The following data giving the reaction rate for MEK were obtained in a difterentialreactO! at 490°C,
_., - - - - , • - .,.... _,- -¥~~"'"
PBIt (atm) 0.5

l~\Iu: (atm) 5 o 2 0
PH, (atm) o o 1 0 10
_~;[J!:~ tIY1f:l!h x cat) 0.044 O(W) 0069 0060 0.043 0.059
PIO-9 (a)
Suggest a rate law that is consistent with the experimental data
From data sets 2 and 5
PBIi (aim)
l~HBK (atm) ()
PII , (atm) 0
(molf}! x g cat) 0 . 040 0..043
. __.:c:= ...._. __.__. -... _ .._ ....._..._......__ ._._ .........---.. - .... _ ... .
we can say that an increase in BlI partial pressure slightly increases the reaction rate.
10-16
Data Set 1 5
Pllu (aIm)
l~"le-K (aIm) 5 o
Pit, (aim) 0 o
0.043
we can see that the MEK partial pressure has little if no effect 011 the rate law.
...
DataSet..
-.-,.--,- ,,~ ~~ .. .,-.-~,.-~~.~" .. ..",.. ....
,~.~ " '"~ .. 4 6
PSlI (arm) 1 1
P.WEK (atm) 1 o
~/1 (aim) 1 10
r;~~!i .(~rl(){/ft~~JL ca~L ... 0.060 0.059
Is seems that the pattial pressure of Hz has no effect on the reaction rate.
If MEK and Hz are weakly adsorbed (or not adsorbed at all) we can proposed initially the following
.- r : : : r ::::: . . . . . kiP,
J ,
. ---.:..........
A B ItkP
2 A
But, from the complete data sel
"' .......... __ ............. .
Data Set '" ..•..•... __._ _ _ _ •.• _~
2
.•• _•• _...................... _-...-_._.'_.' _~
3 4
___ ••... __ ........................... _.• .·.M .. .. _____ ·_ ••·..."
~ ~
, ......... -.-~- ....... 6 . -.- .... .

-
2 0.1 05 2 1
cat) 0.044 0.040 0.069 0..060 0.043 0.059
We can see that the reaction rate goes through a maximum
008
0. 07
006
«i
~ 0.05
S0 004
,5,
~ 003
...
- lii
002
001
0
0 0.5 15 2
PUu (lltm)
10-17
PIO-9 (b)
Suggest a reaction mechanism and rate limiting step consistent with the late law.
One possible mechanism is the following one
<-> A·S
(1) A r-S
(2) A S + S ,) B . S + C . S
(3) B S' "7 Bt, S
(4)C·S<)C+S
If the limiting step is #2 (irreversible surface reaction) and the others me at Pseudo Steady State (# L, 3and 4)
, kC A.) ("/V
.... fA ;;:: '2
A site's balance wHl yield
TherefOlC,
Solving tm Cv
(1
C" =
1 + P.K + + f~.
" I K3 K
.!
Substituting the expressions for Cv and CAS into the equation for -r' A
". r~ =.: k 2 C;\ sC" = k, K IPr\C..~ =,_,._~f..f<iZ.<l0.x,_,_. . . . . -;
(
1+ p. K + J>!L
il I K,
+!~.l-
K)4
which for the case of weak adsorplion of MEK and Hz reduces to
PIO-9 (c) Individualized solution
10-18
PIO-9 (d)
First we need to calculate the rate constants involved in the equation for -r' A in
part (a). We can rearrange the equation to give the following
fE;*+ jtp,
which is a linear equation with slope equal to YJk:' and intercept equal to Y.Jk:·' Shown below is the linear
regression we did using the problem data
7
"'-1..
6
I
V1
0
<;
5 ------i I
~
~ 4 (PaJr'~"Y{}5 = 2 7298l>flu + I 3362,
~ I ,,': 0 .9991
e::.'" 3 I
I 1
2
I
••• '.H
I
0 I f
0 05 15 2 2..5
Thus from the slope and intercept data

mol I
kl ::::: 0.56· .--._. and k2 ::::: 2.04 ---_.
h· gcat·cum atm
Thus,
The design equation for t.he PBR is
F ..cJ?i_. :::::--,'
AO dW II
From stoichiometry (gas phase)
C CA({i~-~~-\J¥ ~-
t1 :::::
From the reaction E:= 1+ L·· 1 _Assuming isobaric and isothermal operation and using ideal gas law
p,\ =PA{Li-)
Using equations 10 ..8-13,10-8-14 and 10-8·-16 together with Polymath we can solve for W at X::::: 90%..
10-19
See Polymath program P 109-d..pol.
POL YMA TH Results

Calculated values of the DEQ variables
Variable initial value minimal value maximal value final value
W o o 23 23
X o o 0.9991499 0.9991499
e 1 1 1 1
Paa 10 10 10 10
Pa 10 0.0042521 10 0.0042521
k1 560 560 560 560
k2 2.04 2 . 04 2.04 2.04
Faa 600 600 600 600
ra -12.228142 -68 . 5622 -2 . 3403948 --2 . 3403948
rate 12.228142 2.3403948 68 . 5622 2 . 3403948
ODE Report (RKF45)
Differential equations as entered by the user

[1] d(X)/d(W) = -ralFao
Explicit equations as entered by the user

[1] e=1
[2] Pao = 10
[3] Pa = Pao*(1-X)/(1 +e*X)
[4] k1 = 560
[5] k2 = 2 . 04
[6J Fao = 600
[7] ra = -k1 *PaI((1 +(k2*Pa))A2)
[8] rate = -ra
~ . mol mol
it should be mentioned that I, . :::: to . . ;;;: 600---
tlU min hr
1.0 --- 70
0.8 56
06 Q -12
0.4 28
0.2 1-1
'---_ _ _ _ _ _ _ _ "_ _ _ _ _ _ "~ _ _ .J

.0.0 (I
0.0 -1.6 9.2
\" 13.8 184 23.0 0.0 4.6 9.2 W 13.8 18.4 23.0

PIO-9 (0
10-20
Now consider the change in pressure:
Stoichiometry: P =C RT=C
AA A" (1-X }P
._--, -·..,RT
l+iX Po
Pressure: . "".dy_. . . =.·'n

".". - (1+ X )
dW 2y
Use these new equations in the Polymath program from part (d).
See Polymath program P 1O-9-f.pol.
POLYMATH Results
Calculated values of the DEQ variables
Variable initial value minimal value maximal value final value
W o o 23 23
X o o 0.9997919 0.9997919
Y 1 0.0746953 1 0.0746953
e 1 1 1 1
Pao 10 10 10 10
Pa 10 7.771E-05 10 7.771E-05
kl 560 560 560 560
k2 2.04 2.04 2.04 2.04
Fao 600 600 600 600
ra -12.228142 -68.584462 -0.0435044 -0.0435044
rate 12.228142 0.0435044 68.584462 0.0435044
alpha 0.03 0.03 0.03 0.03
ODE Report (RKF45)
Differential equations as entered by the user

[1] d(X)/d(W) = -ra/Fao
[2] d(y)/d(W) = -alpha*(1 +X)/2/y
Explicit equations as entered by the user

[1 J e = 1
[2J Pao=10
[ 3 J Pa = y*Pao*(1-X)/(1 +e*X)
[4] k1 = 560
[5J k2 = 204
[6J Fao = 600
[7 J ra = -k1 *Pa/( (1 +(k2*Pa) )1\2)
[ 8 J rate = ora
[ 9] alpha = ,,03
10-21
1.0 70
/,
08·
0. 6
56
42 [;J r:f.f{-
/
./!
/\ '}
I
04 28
/' I
...
~#'V,-/t7
<",,"'
\
0.2 14 ,,>P' ~ '"
" ",
\
\
0.0
0.0 9.2
W
13.8 1804 23,0
(I
0.0 4.6 9.2
\V
13.8 18.4 " "
23.0
PIO·IO (a)
Iso,ocrene +. Hydro gcn --? isCH)Ctanc
A -t. B
Discrirninarion of mcdds:
Assume 'fA ;: k C1 q q:
For runs 2 and J, 0 < a: < 1 ; 2 and 4, 0 < f) < 1 ; and 2 and 5 , ·1 < r < O. From
Perry's handbook, 5th cd". p. 4-8; the reaction is probably surface reaction rate con'Q'"olling.
Mechanism I (H. Alvord):

A+S+!A.S
B2+2S ~ 2B·S
A·S,2B·S;:! C·S+2S
C·S ;:! C+S
k fp;..
-rA, "'" _._., ..•,..._. '--,•..PB - PcfKuJ .... _-,._..
,_.,-""-,
Hence.
[1 +'KAP;..+KfPft+ KcPcP
Mechanism II (S. L Mullick):
A+S +! A.S
B+S ~ B.S
A·S+B·S f:!: C·S+S
C·S ~ C+,S
Hence, , _ k[P Ps - Pc/l<.,qJ

"1;.. - ...." ._..._, ...• "...• _...A
,••.•.- ." •.._
...... _ ••... , . , ....•.
[1 ,. K ... FA t· KB Ps -+- Kc PcP
10·22
From runs 2. 9 11. 12. P A:::: PB =Pc "" P. a plot of ~rA vs. P shows a parabollic
behavior. therefore we Mil drop the second term in the denominator for easy linearization.
Tne readers can calculate ~ value by Gibbs free energy change 4'1 this equation (up to 650
K. the reverse reaction is negligible)

Tne linearized regression model is:
Using given 12 data pointS to solve for these four unknowns:
y :::: 3.0 -+ 1.42 P A .;. 0.97 Pa -t. 1.42 Pc

The tinal results are:
-fA:: ...- .... ". 0..1113 P A Fg

_._-,,--,,-,,_.- _ ............... _ ...._"
(1 + 0.475 PAt 0322 PB .;. 0 . 414 Pcr
The comparison of the pen:emage error between the model and the experimental data are:
r
Run PA
r
(exp.) (~A.!:lit .5 (calc.) % elmr
Pa Pc expo
1 1 0 0..0362 :'5.26 0.0345 -4.8

2 1 1 1 0..0.239 647 0.0227 -4.7
3 1 :3 1 0..0390 8.77 0..0410 +5.0
4 3 1 1 o...Q351 9.25 0.0334 A.a
5 1 1 3 O.D114 9.37 0.0120 +5..7
6 I 10 0 0.0534 13,,69 0 . 0.505 -5.4
7 10 1 0 0..0310 17.96 0.0302 -2.6
8 1 1 10. 0.0033 lo.Al 0.00315 -4.5
9 2- 2 2 0..0380 10.26 0.0380 0
10. 0.2 0.2 0.2 0.0032 3.54 0.00288 ·9.8
11 0.1 0.1 0.1 0..0008 3.54 0.00089 +10.7
12 5 5 5 0.0566 21.02 0.0599 ....:.1:2 _
Isuml =59.2
avg. =4.9
PIO-IO (b)
Discussion: The readers may check the validity of mechanism L To reduce the
accumulation of error in calculations, the readers should have used ail data points and
solved all unblowns simultaneously. To get the maximum informacion of complex kinetics
of a reaction from the least runs, it is advantageous to do planned experiments such as
factOrial design .. (W. G . Humer. and A. C. Atkinson. Olem1cai Engin~~rin!!, p . 159. June
6. 1966).
A paper discussing chemical reaction rare equations from experimental data is in:
C. n. \Vare 11., Summer Compmer Simulation Conference. Proceedings. 1975, Pa.."t 1. p .
368.
10-23
PIO-IO (c)
0.2223 C~o (RTr {l-Xr / (l-O.SXY
··rA =.-....- - -..- - . - - . - - . - . - -................ --.-~.-.--'J-
r1 + CAOO ~T {(0.475 + 0..322 (I-X)} + OA14x}1-

l 1- .)x .
0 ..1 113 (RT CAot
-r!\ = ----. ~------
(l·.xF I {l-O.5Xr
..--.--.------..
. r 1 + c.:..o RT fO 79 7
. 1-0.SX \. ,
• 0383
.
x'\j2
'!
FAO::: 2.5 =::: i50 I~l
CSTR:
w;;;;;; 21.380 g ::::: 21.4 kg
w::; 1501
o 2:1l13J1.5J:i!·X(LL0.5 x)Z
~ 1 ..,..
11+' _. . . . . .,..2. . . . . . {O.797- 0..383 X)I~
l. 1 - 0 ..5 X 'j
10-24
w= . .- . ..J~Q
0.1113 x 2.25
1
0
x
G (X}dX
. 1..5 (0..797' - 0..383 Xl]2

[...1-.. + -.-----------. (1 - 0.5 xjZ
where G(X):= L.:Q~.X ___ . __.._._. . . _. . . . . . _. . .
(1- xf
x G{X)
0. 4.82 ~l
0 ..1 5.38 ~t
0.2 6.13
0..3
OA
05
0.6
7.16
8.66
11.00
IS.03
COO
:1
0
I) a.l 0':' c..J 0.4 as cu. 0:: lUI
0.7 23.15
0. 8 44 . 62 "
Using Simpson s rule.
area. under the curve ~ i 0
w:;: ..._____.J2!1_____. __ x. 10:;: 6000 g "" 6 kg

0.1113 x. 2.25
PIO-IO (d)
Consider the differential section between L and L + dL
In - Out + Generation"" Accumulation
r)C 4 ,L)Ar Pc-H······ t/J)dL == -.dl{"1· Arv{L)CJL)]

But: A1 v(L)C4 (L):= N)L).:::: f~ll(I ... X)
:. FAD f·:: TA pdl .. $) rA {Pd
Relating the expression fA to X and L :
;; lFo (l·X)
2 1
R, =-(2······
2 X)
:;: }Fo (l-X)
P __F
...:1.. _I...........
X_•.
Fc=FAOX == tFox l-Pr -2· . ·X
PA == PA ... 1:.:X. Pr Pc=-X-Pr

2·X 2-X
LetP=Pr,
10-25
From th.e Ergun equation. we: have:
All the things on R11S arc: constant. except far p
p=p,((L!x)
. :i = ~2X(~:)I~)gc%;;(1;1)l~50 ~-$)l: + [75 GJ
df. == 2.:X ~o where 6 0
=.!?Q.Q.. . . ~~:~?r.~. ~?,..0.,:d» 1: +- 1.75 G
dL 2P . Poge D? Q> L Dp
Let L" ",., L..... : p. =..P. . then: dE"", l-X.

L-des Po dL 2p·
\3:
where
$=04
( I'sO gmol.) (2 + 112}~.-,{---.JL"-.)

G :;:: t~ An fiA + Fso fiB) == hr gmol 4)".6.g,
AT T K. {fr..25:I\2 f~
4 12}
'"'''At: 9 T.......
G == J.,~ . ,.u.a.ll.•
T frZ hr
P :; (3 atm)
o
(14.1 ?E~,·) (1441 frZm:.) =63487 .lb.
attn ft2
(57 _Jh.,_.1 (3 ann)
p ;; C r m == (5ZJll.\ L := ._ _ _ _ •_ _ _ .Jbmcl.!........"." . . . ,....:.....__ .. _ _...
0-.'· lhmal J RT (0,7301 ft~..rurrL\1 [(lOO + 273.15)( 1.8 jJ OR
\ IhmoloR,
10-26
IiJ ;:: 0.4
Dp ;: (_1 in) U . . fL} :: _1 ft

16 \12in 192
&<: = 32.174 lli.!IL.JL

Ibr sect
(150 grnol) (2 + 112) .....1..-.. {..
G;:: (FAO rnA +- Fae mB) =. hr gmol ~5.).6 g
-JL-)
AT T 1L{n..2llj
4 12
f~
G=~ J.bm..
T f~hr
Po =(3 atm)(l1:r:iHl~f~~-) = 6348.7!i'
__ (57 ,.J.b-:-) (3 atm)

Po:; Cr m ={l~:n~lJh= (0,,7301 ..fy3 9trU~IL(20~:;3.15H~ .all oR
IbmoloR,
Po:: 0.2750 !wt

ft)
Ii (3 atID. 200°C);: 9.4719 x 10,3 cp (t Cg, ~. He) }

-~. PPROP
:: 8.6211 X 10.3 cp (all Ca)
(94719 X 1O·3j- 8.6211 x 10.3 ) " -4 Ibm

= !J. ;; ................- -..- -.........- - - - - cp 6.7197 x 10 -----
2 ft sec cp
x JQQQ..z..;;.
hI"
Il "" 002188~n.
ft ru"
10·27
where
• rAT p~ (1 . 1j» K P;
Let: a. "" - . -.. . -------
FAo
K~ =(KA + Ks) Po
Then: dX:= (1.- _ ••..... J!.:::..~_

ell f2-X ~K', K' xl1
lP:-+-l'1' 2 J
For a given T. we can solve the twO ODEs to get X(L *)., We need to guess T until X :::; 0,8.
For the rate cOnStaIUS. we use the solution of 6.10 (a)
K :::; 0 . 1118 - .... ~:::~! . .-.. .- ; KA"" 0.475 amr 1 ; KB = 0.322 atnl 1
gear'" hr • ~~.
Kc "" 0.414 atm l
K ·2-
- (0 ..~ TAO
" ..... ,4"7-
.) () .~~")}
.... ,.,.- ~ - • 149
.)-"'1..
a: := 85.958 T
10-28
~. =(5...5.ll x 1(J4 f2..hr.) (378.09 + .ll2.Ql) J1'm..
o T ll:xn . T f~ hr
~: == _Q 2191 _ 8,~;5:i
A FORTRAN program is written to solve the equations. The results show that any
numbers 6f tubes !oufiicient to allow the given flow rates with a positive pressure provides
more than enough catalyst for the desired conversion The problem as stated, therefore
has no solution. However, we can choose a ditIerent L, and it only changes the
dimensionless parameters.. With L = 20, the problem is still unsolvable
For L ::;: 10 ft , T:::: 2.16 rubes = 1-::::

In
0.46
Note: Using the modified program with
Dp ::;i~ in • II "" 9 . 05 x 10"3 cp
L""' 10 ft A:; 2.15 il'l2

=> X", 0.80 • p. == 0.7531
Using 1 1/2 in schedule 80 pipe (I.D. := 1..5 in) • A = 1.76715 in2 and me length to get
X "" 0 . 8 is impossible (p( < 0).
With 2 in schedule 80 pipe U.D. "" 1.939 in). A =- 2.952877 in1
This gives L "" 6.6Jft , X == 080 and p:::: 0.9113

1 1/2 in schedule 40 => A "" 2.03580 in2
L '" 1O.9~857 , X = 0 . 8 and P "" 0.6903
PI0-ll (a)
10·29
Assume a rate.,ljmiting step; start with surface reaction
A·S+S.....-··BS+H S
H·S ..... ·'H+S

~-~~~
Assume a rate·lit,wting step; start with surface reaction
.~4D. ::: 0
kAD
.:fl!2.. ::;; 0
knv
Find the expression for Cy
Combine all of those to get the following rale la\v suggestion.
CheckinO' to see if it fit>;, we see that for high P A' increases in P A cause decreases in
the rate. \Ve see that if PB or PH increase the rate will go down, which is consistent
with the rate law .
PI0-ll (b)
Now nsing POLYMATH's nonlinear equation regression we can find the values
for the parameters. We find that
k=O ..o0137
K·a = 4'16
• I
K B --._':>
0 ")-9
Kc::= 0.424
In the problem it is given that K.. . is 1 or 2 orders of magnitude greater than KB and
~: which is tme so this is a good auswc{.
10·30
"aXl:~OO T o ~Ii'c;;r "li;;;~
:;lAta
on
3.200 J. . [J Cdl;::~i <i), ~d
vat de
2 .... 00
t.600
0.8CC
0.000
Model: ,. azi<.""Pa..... ' 1 ~Kil ... P.a·Kb.Pb··l(h)(Pt')-2

~ "0.00137022 ICb .. 0.259382
Ka .. '+.7608'11 1<1'\ '" O. "t2359
? pOsatlv'@ r€'su::l,~ .. ls. :3 "eqatlv~ .... 5lC:luals. Sum o! squa r -E1'S '" 5.27033~-15
PIO-ll (C)
The estimates of the rate law parameters were given to simplify the search techniques to make sure
that it converged on a false minimum. In real life, one should make a number of guesses of the rate
lw parameters and they should include a large range of possibilities
PIO-12 (a)
Assume that the second reaction is the rate-limiting step.
Using PSSH, we know that
rS"'·H ",= 0
I 4'" = k1CS·u. lD4· sC·'V
10-31
Perform a site balance:
Combining all of these we find:
This rate law is consistent with the data. As the concentration gets larger, the
rate change gets srnaller which is consistent with the rate la\v as given.
PIO-12 (b)
No answer is right or wrong, but the points will probably be higher than
the ones given to see that the change in rate becomes even smaller.
PIO-13
Assume the rate law is of the form rD = kP::rl~O
ep 1+ KPVI1PO
At high temperatures K J,. as T i and therefore KP::rIPO «1
'[Yep = kPy~ [PO
'[Yep
--=k
Py~IPO
0.028
Run 1 ----2 =11.2
( 0.0.5)
Run 2 0.45 = 11.28

(0.2)2
7.2
Run .5 - - 2 = 11.25
(0.8)
At low temperature and low pressure

'[Yep = kP~TlPO
r
--.!l!L = k
Py~IPO
Run 1 .2. 004 = 0.4
(0.1)2
10-32
Run 2 0.015 = 0.375
(0.2)2
These fit the low pressure data
At high pressure KPv~1PO »1

_ kP~1PO _ k
rDep - KR2 - K
VT1PO
This fits the high pressure data
At PVTIPO = 1.5, r =0.095 and at P VTIPO =2, r =0.1
Now find the activation energy

At low pressure and high temperature k = 11.2
At low pressure and low temperature k =0.4
In(k2) = E(~._._L) = E(!2 -7;)

kl R 7; T2 R 7;T2
In(I1.2) _ E(~3-~~)
0.4 - R (473)(393)
E =7738
R
cal
E = 15375----
mol
PIO-14
r1"iD,. ::::: ks.~.s
1;;:; Iv + ft.s;::: iv(l+ K,fj)

~1; : Kp • Ii "" Kp Pfnp/PPI
_ ks Pr Kr
I'iiOt----···
1 + PI Kr
10-33
h-s:::; ~K[j~
f~.~, == 1:1:~'
ks Pr Kl
I'Ti(~ ;:; 'r::;:: P~ Kr
kPirIP I pp! kP;'TP

rno, =i~r~~;?-I-'i~)K =1>;1'" ~:P:;;;K
Low Pnn>: Rxn is second orrier
Since 1» K PfnpfPPl
High PIT!P:
Reac:tion is ze:ro order

High Tempermure Kr very smail such that
PIO-15 (a)
Using Polymath non-linear regression few can find the parameters for all models:
See Polymath program PI 0 15. po I.
(1)
POLYMA TH Results
Model: rT = k*PMl\a*PH2I\b

k 1 1 . 1481487 0.1078106
a 0,,1 0 . 1843053 0.0873668
b 0. 1 -0,,0308691 0,1311507
PreciSion
RA2 = 0,,7852809
RA2adj = 0,,7375655
Rmsd = 0,,0372861
Variance = 0,,0222441
a = 0.184 ~ = -0.031 k = 1.148
(2)
POLYMATH Results
10-34
Model: rT = k*PMI(1+KM*PM)
k 1 12.256274 2.1574162
KM 2 9,,0251862 1.8060287
Precision
R"2 = 0,,9800096
R"2adj = 0.9780106
Rmsd = 0,,0113769
variance = 0,,0018638
k =12.26 KM = 9.025
(3)
OLYMATH Results
Model: rT = k*PM*PH2/((1+KM*PM)A2)

k 1 8.4090333 18.516752
KM 2 2.8306038 4.2577098
Precision
R"2 =-4.3638352
R"2adj = -4.9002187
Rmsd = 0,,1863588
Vari.ance = 0.5001061
k =8.409 KM=2.83
(4)
POL YMATH Results
Model: rT = k*PM*PH2/(1+KM*PM+KH2*PH2)

k 1 101,,99929 4.614109
KM 2 83.608282 7.1561591
KH2 2 67.213622 5.9343217
Nonlinear regression settings

Max # iterations = 300
Precision
R"2 = -3,,2021716
R"2adj =-4 . 1359875
Rmsd = 0,,1649487
variance = 0.4353294
k =102 KM =83.6 KHZ =67.21
PIO-15 (b)
10-35
We can see from the precision results from the Polymath regressions that rate law (2) best describes
the data.
PIO-16
Using Polymath non-linear regression few can find the parameters for all models:
See Polymath program P1 0-·16.pol.
(1)
POL YMATH Results
Model: r = k*KNO*PNO*PH2/(1 +KNO*PNO+KH2*PH2)

k-- -1---
0 . 0030965 3 . 702E-05
KNO 1 57_237884 1.0353031
KH2 1 10l. 9967 2 . 2870513
Precision
R"2 = 0 . 9709596
R"2adj = 0 . 9645062
Rmsd = 5 . 265E·07
Variance = 4 . 436E-12
k = 0.0031 KNo = 57.23 KH2 = 102
(2)
•
POL YMATH Results
Model: r = k*KNO*PNO*KH2/(1 +KNO*PNO+KH2*PH2)
Variable Ini guess --Value

--- 95% confidence
k 0:1-- -4.713E-06 l.297E-05
KNO 10 -108.42354 4.9334604
KH2 1 1 . 046E-05 2 . 878E-05

Precision
R"2 = -9 . 6842898
R"2adj = -12 . 058576
Rmsd = 1. 01E-05
Variance = 1.632E-09
k = -0.00000471 KNO = -108.4 KH2 = 0..00001046
(3)
POLYMATH Results
10-36
Model: r = k*KNO*PNO*KH2*PH2/((1+KNO*PNO+KH2*PH2)"2)

k 0.1 5.194E-04 2 . 242E-04
KNO 10 13 .187119 7.659298
KH2 1 18.487727 7.7652667

Precision
R"2 = 0,,9809761
R"2adj = 0,,9767486
Rmsd = 4 . 262E-07
Variance = 2 . 906E-12
k = 0.000519 KNO = 13.19 KH2 =18.49

The third rate law best describes the data.
PIO-17 (a)
Mole balance:
-dX. . . . . =,_(-.,~)a
~ . .__ . . . . "
dW FAC
Rate law:
Decay laVor:
.4.':. =._ kdc:.~:A.

dW Us
Stoichiometry:
Evaluate the parameters:
8=.8
POLYMA'I11
~at.4:2E!.l. m tial ..y!!!!!

d(x) la{w} :::a* (··ra) Ifao o
d lal/d(w) ",··kd*a "ca!Us 1
kd:::9
fao=4000COO
10·37
Us=250000 (d; Nov 1:::.g ,. Sed Reac cor
k::::90
cao-= .. 8
Ca
eps'" 8 - x
ca=cao* (1. "xl f (l+eps*x)
50000
PIO-17 (b)
Mole balance:
{!~:,',4 == _(~dL
dlZ
Everything else is the same and we !Jt:cd to know"
V
r = ,., = 0.004
Ii;)
5 CS'ffi' s in Series
!~~!:~51 value
d(a)/d(c)~-kd·a·ca 1
d (ca) fa (t) ;ca4!t.au ( ( (1*ya4) I (l +'ca/eto) ) t tau'a *k;) 'ca/t.au O. 8
d(ca41/d (t) "ca.,3/tau'" ( ( (1+ya3) I (1+ca4/eto) ) • tau· a*k) *ca4/t Q 8
d(call/d(tl"cao/tau'" « (l'-yao) I {l+callcto» ttau*a"k}*caJ./t 0.8
d(ca2) lalt) "'cal.ita\'!- « (l+yal) I (lica2/cto» +tau*a"k) 'ca2/t 0,8
d (ea}) hilt) "ea2/tau- ( ( (1"'ya2ll (1+ca3/cto) ) +tatl'a"'k) 'ca3/t o. S
ko"'9
10-38
tau=O 004
cto;:l
k"'45 .... q
ca,0=0.8 Ca
--- x .
ya4=ca4/cto
yal;cal/cto
ya,2;::ca2/cco
ya3:;ca3/cto
x=Ccao .. ca)/cao
yao=cao/cto
to = 0, t 0.5
f
PIO-17 (C)
The only change from part (a) is the decay law:
'~='''k
dt d
aCA
r == . W··W
_. _.llll!L.•••.•_ .•
Us
cit =: ;~~~.
Us
da
w· _ _ _ • =kd(~a. _
_""'--~"_._
dW Us
Integrating:
In a = .k.CW
. .!L_.:i............+k
Us
W=:WM.AX@a=l
k =: _._kdCA!~~AX.
Us
a = exp(~l;~{~~~~~~J)
Equa!::~£Ef!:l .Ini:::!!::!. y~
d(x) Id(w) =a* ( . :raj Ifao o
k=.90
fao=40000DO tc) 'Moving<Sed Reactor (Count:er:::Ul:re.nt)
kd;;;;S LOOO
Us",250000 ~
TI
a 0""" "T"",
==50000
cao"" .. 8
Ca
.. -- x
Q.6CO
t
eps'='.8
ca=cao*(1.-x)/(l+eps"x) Q,100
l
.....
:ra",-·k"ca
a"'e:)Cp (kd*ca/Us" (w~=) )
PIO-17 (d)
10-39
To find the Time-Temperature Trajectory we need to use the following equation
for first·,order decay,
E r [ E' 1'1 I 'IT]

;;:k~~C~E:t 1 exp;_~RlT- 300JJ.
·r "'d
t
Since no initial temperamre \vas given, we assumed one of 300K This is the graph
of thar equation,
Temperature- Time
trajectory
1000
iii...
-800
::,;:
~ ..... 600
E f: 400
~ ;:) 200
o
o 0,1 0.2 0,3
Time (h)
PIO-I7 (e)
The two energy of activations are switched and this is {he new graph made,
Temperalure- Time
Trajectory
1000
:::J
iii-..800
. " ., ......... "'- J
¢i ~oo
E w400
0.
...
ill 200"
-
-.. - ------------
I-
()
The graph looks the same just the time is much smaller.
PIO-I8 (a)
10-40
For all of the parts, the mole balances and rate laws are the same, 'They are:
de",
---. =r v
dvV '" 0
'A::::: --·kaC",
Find the equation needed f()f a.
da
··--::::::kdaCA
dt
a:::::: exp(-.-kdC",t)
a:::::l when t=O
Assuming values for Vo. k, and ~ come up with the following graphs according to
the cases described,
E:...quat.i.23~!. y:!~ t.ia~.. ,.Y~!~
d(cb)/d(w)~rb*vo o
d{ca) Id{w) =ra*vo
vo=lO
(a) Cas. I @ t-1000
a=l. 1.000
ko=l
..... Ca
t=20 Cb 0 a-oC
_. a
k=l
!Ll!\CO
ra=,,·k*a*ca
~
50
3 .. 200' T
Q.~OO t:~- 0000 o~c '-"-'.,
Q."'OO
-
-..... ••..........~
--.---
-~.'"'~"'t-
Q ~cc
...... - ... -.-.~
o.aoo
..... -.-"'"'!
".. ., l
"*':"
KJ;;,X.
....... C,~
, Cll
- ill
10-41
PIO-IS (b)
Find the new equation for a:
,_!la...;;;:; k
dt d
a2 e i\
1
a:;;;::"···'·······
l+k d C A t
Using same values come up with these graphs:
~~.i,.?E.E_-' g~.t:::i~l,Y~l~~
d(cbl/d{w)~xb'vo o
dlcal/dlw)=ra*vo 1
vo",lO
(!:Ii Cc.:so I @ t~ 100e
kd"'.OOl
t",lOOO
k"'l e1;:;
a=11 (l+kd~ca*t)
-.~". a
(h) Cas,"" II @ t::;:80
Ca
Cb
a
10-42
{b) Case IE @ t=lG-
lSU
Ca
Cb
- a
PIO-18 (C)
Find the new equation for a;
__ .da = k aC
ilt d B
a;;;;; expC kd Cst)

The following graphs are made:
-_.__
Eouat.ions:.-
d(ca) Id(w) =:r:'a*vo
Ini~~~±,. y~:!~~
1.
d(cb) Id(w) '"l:'b*Vo o
vo=lO
kd=.OOl
t;;;;1000 Ie) Case I @ :-1000
k:::l
IOO::
a=;exp( ··kd*cb*t) ..... Ca
. cb
z:b;;;;:k"a"ca -a
J:·a",··k*a*ca
10-43
l.Oc:;
K~
ea
en
a
~ .. ooc -----
2.0ae
.......
".000
-~-.,-'''.-
6.~CC
....... ,. '.'---.~.~;-,.-~-.---;
B,.ooe JO .. OQC
(e) Case lXI @ ~-lO

1.0':::
KE'(
Ca :}"iJ!:n'!
cb
Q.
0... 600
c,.lIce
-:-
+
d.2{;!:!
J ;)GG
PIO-18 (d)
~'iaking a inlO a differential equation we come up with this:
, ,...4!!.. == kdCAG
dt
W
t :="
Us
. . . .,~a..", == .~:!,~~~..
dW U,
10-44
Equati.~". lnitia! va1.u~
d{ca)/d{wj=ra~vo 1
d(cb)/d(w)=rb*vo Q
d(a)!dtw)=·kd~a·ca/Us 1
vo",10
kd=.OOl (d) Case I
Us;1.0
~
k=l Ca
.th::::::k*a*ca Cn
.....- a
ra.t=:'""k*a 1rr ca
ld} CaSe: II
KEY
Ca
C.b
a
-+-~.~-
o~ $P~ 1 .00(/
K~X
-~.- .•..
(d)
- Case III
.... --.-.--.- ~-.- -....
.. .. '............ -
~- ,
Ca
Cb T
t
a r
~~----
(j.. QOO 1.
0 .. 000
,,,,m~-"'r'''''' ....
::.000 '.oeo .. 000
.., ..... ""~
::..:.+=:-...;. ··· ..-..;·~r..-·.-----i-';---
.... ... -,
~
a.ooo
~., ..... ~ .-~ ~ ... ,.",.,,~
=i
lo,ooe
PIO-18 (e)
10-45
Everything from part (d) is the same except for the decay law..
.~~ =-k.aC
dt 4'A
_ l~ttAX _. HI
t--_········,···,·
U,
dW
dt= - .....
Us
da ==: kJC, a
... .,..".".~ '-'-~'-
dW Us
Integrating:
In a =: ~:L~:'A t~ + k
Us
\'11 =- \V iv1A.'.: @ a == 1
~2::~t:iS'!?§~
d{ca)fd(w)"'ra~vo
d(cb)!d(w)"'rb~vo o
vo"d,O
kd"l
k=,001
'..mlOlx;;10
a"'exp(kd.*ca/UsX (W'wmax) )
:t:bmlk'-,a,*ca
"'0 '" 0, 10
......... --- ... ".. _- +-- . .. .. .. --1

~. ~.
... ~ac 1> coo G: ace lC,;;;:~<';:
10-46
(€:) Case II
EEX
_. Ca
", Cb
- a
~-~~""il
a.ooo 'c_ooC
f;EY
- Ca
... Cb
_. a
O~2cn t,'T
I
-'
o~oo.c
i
~~:...:.:.::,;.~.:..:.r:~.:.::.:~::.:::.:
., . ,.,+ '¥ .... ~" ........ ' .. ~" .. -.'. ~~ ... ~, .......
... ~ _ . . . ,...". . ~ ~. . ~_ ....-.__ ._.......,
0,000 2 .. CO(; ~ .. boo :i" 10-:; a. 00;] tc,.o~~
PIO-19(a)
da =-k W-Ut
- s dW=Usdt
dt D
~__4..f!.. = =kD a =1-- kD~

dW dt Us Us
kDW t hen W =---=-=2.5
If 0=1--- U s ·5 kg
Us kD .2
!X = -TA =~(-rA (0)) = akC:~o (l_X)2

dW FAO FAO FAO
dX
dW
= (1- .~D J (1-
W
Us
kCAO
Vo
X)2
f dX = kCAO fl- kDW dW

(I_X)2 Vo Us
Activity is zero for W > 2.5 kg, so the catalyst weight only goes to the effective weight.
10-47
2
-x- -_-
kC-AO [
W -k-
DW-e ]_1(0.2)[
- 2.5- 0.2(2.5)2]_
-0.25
1- X Vo e 2U s 1 2 *0.5
X =0.2
PIO-19(b)
o ________ ______ ~ ~
o 2.5 5
PIO-19(c)
For infinite catalyst loading a = 1.
dX = kCAO (1- X)2
dW Vo
~=kCAoW=1
I-X Vo
X=0.5
PIO-19(d)
~= kC AO [W _ kDW2]
I-X Vo _ 2U,
-~=0.2[5-- 0 . 2*25]
1-0.4 2U, _
kg
Us =1.5-
s
PIO-19(e)
kDW
a=I----
Us
0=1- kDW_
Us
10-48
kg
Us =kDW=0.2*5=I.
s
PIO-19(f)
a =0 means there is no reaction is taking place. Activity can never be less than o.
PIO-19(g)
U=-U s
. da = kD when W =W;, a =1
dW Us
kW
a=-D-+C
Us
_kDW; C
I ---+
Us
a = kDWe +1- kDW;
Us Us
Now find We.
0= _kDWe.+ I·_.kDW;
Us Us
We = Us [kD"i. __ I]=.:~[:3*5
kD Us .2.5
-IJ a
We =2.5
dX.=(I_ kDW; +wJkCAo(I-xt \Ve \Vt

dW Us Vo
~=~~AO 1 - kDW; +W I-lW \\'

I-X Vo Jl 1 Us r
~ =~~AO [(W; -W.)(I- kDW; J+.W;2 --We
2
]
I-X Vo _ Us 2.
~ = 0.2 [( 5 - 2.5) (1- 0.2 *~.) + 25 - 6.25]

I-X 0.5 2
X
--=1.875
I-X
X =0.65
PIO-19(h)
$ = I60FAo X -lOU s
10-49
kDW
a=l---·
Us
dX =ka=k(l-!'DW]
dW Us
2
X =kW _ kk DW
2U s
To maximize profit, a maximum in profit is reached and so we set the differential of profit equal to
O.
. d$ =O=160F dX_ lO
dU s AO dU s
dX kk D W 2
dUs - 2U~
2
160F kk DW = 10
AO 2U2
S
8FAO kk DW
2
=U~
Us =~8FAOkkDW2 =~8(2)(.2)(.2)(25)
Us =4 k~
mm
PIO-19(i) No solution will be given
PIO-20 (a)
Stan with the mole balance for a balch reactor:
Rare lavv;
Decay law:
da
..-._-:z: k J a"'
(i t
Stoichiomeny:
Plugging those into POLYrvlATH gets the fc)llov,.ing program and the following
graph
10-.50
2~ti2.!~:L'
dlx)/dlc)=-rt"w!cto o
d{a}/d{ti~'kd~a~2 1
w=5
k;:=20
kd"'.l...6
"'~.-~ .... -
/,/
v=l :).&00
r //
2.;.082
T/
T=735 -1- /
p1:=pto·
rt"'·-kc·pt"a
(1 ··x)
tI
Tf
II
lltO=pt.o"v/ (R"T) Tl
-!---..... -- -".--.-----,.~-~ ....." ...............- ...................... f - - - - - - . - - j
n.ctio a. ::u;;;:: ..
::0 = 0,
.,...~
PIO-20 (b)
For the moving··bed reactor the mole balance now becomes:
dX .. /;
....-.-,:::;:;;-,,-~
dW FM)
The decay la\v nOw becomes:
da k"a"
."""'----:""....:::::... ........ .
dW Us
Everything stays the same.. Plug into POLThIl\TIl.
The conversion achieved is X:::: 0.266
Equas~~2.
d(x) Id(w)"'-!:t:./fao o
d(a) td (w) ", .. kd"*aA2/0s 1.
kt",,20
£ao,,600
l<d"1.. 6 ~!lE.;E.!,£
Us=:2 '" 50 50
pto:2
o 266;6 a loS:.5
0 02439·02 C .024.:130:
pt"'pto* (l"x) 20 20 2<'; 20
x·c,,····kc"pc·a fao 500 600 teD 600
1<;d ;; 1 6 ,
'NO'" O. We 50
5 1 Ii
2 2 ;;:
2
4tr'~68
·-.:10 --0 .7:5i4: ,~c
PIO-20 (C)
c) Increasing Us \vill get us a higher conversion" Looking at this summary table,
U. = 10 kglh and X :: 0.6
10-51
~labl~ ~SciaJ_val~~ Ml1XimillU._"~5!f.~ Mi:!i~'!!::1~ f_~,.y~l'le
\01 () 50 0 50
.,. ::. 1 o. : l l l l l 0 111111
x 0 O,SS9-i:iSS () CL 599686
f~o 600 600 600 600
kd 1.6 LoG ]',6 1.6
Us 10 :),0 10 10
kt 20 20 20 20
pta :2 :2 :2 :;:
pC :2 :2 0.e00625 0,800625
t't -40 -l. 77917 -4.0 --1.77917
PIO-20 (d)
For second-order decay:
For s:::: 25 keal/rno! and E 4

::::: 10 kcalimol:
Use tlris equation in Excel to generate the following graph:
Temperarur·c.. Time Trajectory Temper ature-Time Trajectory

£,-=10 lInd E;.;2S
r------- --.------- -, - ----------1

1600 , ...... ,.--.-.... --.,----...
~..
~ %500
soo
-- -----
-- ~ ~ -
i~
'"
'wo t-- -------------- -----------~
I
"]00 " , .... "' ....... ,." .......,....... .. .. ,. bOD
Q 100 400 o
'lime (h) tim" (h)
Use this equation in Excel to generate the above graph.
PIO-20 (e)
10-52
In part e, the only thing that changes from (b) is the decay law and the decay
constant:
2
da krJP/a
""-'"-=-..::......:....-
dW Us
ka = 0.2
Plugging into POLYMATH we get the following summary tables for Us:;:: 2 and 10
kglh . X:;:: 0.50 and 0.88 respectively. X will again increase as Us increases.
Eq'-J,a~ions.;. !ni tia1~1~~
d{x)/d(w)=-ra/fao o
d(al/d(wl=~kd"'pt~2"aA2/Us 1
kd;;;.2
u5=2 !.!'!±.ili!....yalue ~ ..~~ ~~.,.,~±~ fina:'_~
fac=600 w a so 0 So
0 502431 0 0.502431
kt=20 1. 1. O.lC411J5 0 . 104635
pt.o.:Z 0,,2 02 0.2 0. 2
pt"'pto" (l-x) Us :2 2 2
tao &00 600 sao 600
20 20 20 20
:2 :2 :;!
2 :2 0.9951.38 O.99Sl38
,,40 2.08253 -40 ··2.08253
f~g.!~l_Y~: \.I~ !,!,=immn.:2.!~~ ~2imt.:.r::...;;:alu~ fb~l.Y.§!;b~

\) 50 0 SO
o 08']5709 (I (I 37$'109
1 0553922 o 553922
kd 0 .. 2 0 2 02 0.2
uS 1() 10 10
€ao 600 600 600 600
kt 20 20 20 20
2 :2 Z ,/.
2; 2 0.248581 o 243581
.. 40 2.75389 -40 -2 _ 75389
PI0-21 (a)
A -7 B Elementary reaction with 1st order decay.
da
-=-k a
dt D
a = exp( -kDt)
PI0-21 (b)
10-53
t
The activity is never zero for first order decay. When a = exp (-kDt) there is no t such that a =O.
PI0-21 (c)
Mole balance:
dX= --r' A W = _
_ AW
-r'_ -r' W
_=_A._
dt N Ao CAOVO CAO Vo
Rate Law:
rA ' = -a [ --fA' (t =0) J
-rA '(t = 0) = klCA
Decay:
a =exp( -kDt)
Stoichiometry:
C A = C AO (1- X )
Combine:
dX W
dt- = exp( -kDt )kl (1-- X)~~-
In ( -1-)
1-·X
kW [ l-exp(-kD t)
= _ 1-
k Dv0
J
X=1-exp (_IsW
kDVO
[1-exP(--k t)JJ D
PI0-21 (d)
klW (0.2)(1)
-= =2
kDVO (0.1)(1)
X = l-exp( -2[ l-exp( -1)J) = 0.97
10-54
PIO-21 (e)
Decay rate increases more rapidly with temperature than does the specific reaction rate. Therefore,
conversion decreases with increasing temperature.
PIO-21 (1)
kjW (T) = 2exP[-1500(_1___1_)] =0.57
kDVO 310 400
k D= 0.lexp[2000(_~ __1_)] =0.53

300 400
X =l-exp( -0.57[1-exp( -5.3)J) =0.43
PIO-22 (a)
In order to get a high conversion the en.tering pressure should be as high as
possible since the rate is a sewnd order function of the pressure. U should be
kept low since the conversion is an indirect function of the flow rate.
PIO-22 (b)
11\e problem with such a low flow rate is that the activity will remain low
PIO-22 (c)
We (an use the same eCluations that are given in example 10,7 with a few
exceptions. For example the rate law, we use the one given in the problem:
I11e activity will be different because the equation given is different:
,,~:~, :;::; k naCcoke

da
..... , ....... ,..... kDaCcoke
.... ..
::;:,....... '""- ......•.... -. .---
dz U
To find the concentration of coke we use stoichiometry:
, == .~coke.
c'cot(.e RT
We fmd that the value that gives the best conversion (X;:::: 0.337) and nses the
whole reactor is U :;::; 7. See the following POLYMATH program.
10-55
:sq~aS~ .: Inicial ... :alu€
d(a} Id(z) =·~-kd"'a""'ccoke/U 1.
.)
d(x)idlz)=-ra/U/Cdo
cao~ 22-
kc.;;;;1.OO ;;; o 15 o LS
1 Q 00C2549';8 .a002S~34.g
kp=i;ne;;;:5~···5
o G 316731 a 33673:
ao.:;:?
cao (} 22 0 .. 22 0.22 :) 22
eps~1. ;Cd :00 100 leo 100
R=.OS2 k."1J::;-Z:;ne 5e: 05 5e-··CS 5,,-05
tlo 7 7 7
eps 1
pao=12
R o 082 032 0.082
:,;-no=80 T 67) 6"1:! 673
U=:Uo*(l"e;:>s·xl pao 12 12 12 12
pa=pao' (lox) I (l+eps'x) rho 80 Be 80 BO

~ 35711 ) 9.35712
pcoke"'pao~xl (I Teps • xl
P" L2 12 5.95425 s. 9S425
rapr ime=a' ( kpr ime 'p-,a ~2) p-coke o } 0.2288 0 ) 02"288
ccoke=pcoke/R/T .x:ap;:-i:ne ···0 0{)12 .~ . 51934~···O7 -·0.0072 -4 S1.934e'··O'l
ra:::rho""r:aprirne e·.:-ok~ 0 0547762 o .OS~7'162
·3.61547e·05 ··0 51G
PIO-22 (d)
To fmd this the only change necessary was the values for the k' s because
they change with temperature.
_ pr" ED (1
kD :;:: lOOeX 1 \'1'
! --R6ij-i)
..... ....I
The POLYlvlATH program below shows the results. The temperature is 485K
and the conversion is 0 . 637 _
10-56
Equations: Initia.l val~
d (x) !d(z} ;--ra!U/cao a
d(a}/diz}~-kd*a~ccoke/U 1.
cao;.22
Uo:;;2.5
R=.082
T"'48S
pao"'12
!'ho::30
kd=lOO-e>..'P (15000/1. 987· (1/673-1/T) l
kpri.me ::oSe-5*exp(30001l • .987* (l/673-·l/Tl)
U:;;Uo*{1. ... eps*x}
pa=pao" (I--x) I (l~eps"xl
pcoke"'pao*x/ (.l+·eps*x)
ccoke=pcoke/R/T
J:·apr.irne"'a* (-·kpri.me"'pa "2)
ra=;rho'raprime
'0 "" O.
:nit:ial_'ya1:!:!.! MaximlmLy!!ue Mi~i!!!..~l.,,~ UEill value

o 15 (} 15
o 0 6374aS 0 0 637285
1- () 605597 (} .605697
cao () .22 o 22 C.22 0 22
Uo ;J .5 2-5 2.5 2, S
eps 1 1 1
o 082 C.082 0 082 Q 082
485 485 485 4S5
12 12 12 12
80 80 80 80
)cd 1.29 ..31 1.29n 1.2932 1.2932
kprirr.e 2 .. 09558.-·05 .2 09558. 05 2.09558e-05 2.09558.-05
2.5 I 09121 2.5 4.09321
pa 12 L2 2.65841 2.65841
pcoke o 4.670& (} 4,6708
ecok. o 0.lL7445 0 0.117145
-(}. 00J01 763 -897021e-05 ·0.00301763 a 9703le-O!
···0.24141 -0 00711616 0.24141 -0 0071161&
PIO-22 (e)
10-57
To find the temperature-·time trajectory, use equation (10-119) and add C,o\<e
'iNhere necessary:
The following curve is generated from that equation.
o 0 . 005 01
Ime, t
·rO-
() 015
PIO-23 (a) ~ ... , , - '--'"" .... _ _ ..... ,,_..., , - - _................'T
I
·-·------·l ~-------.~--.- ..•.,.-""..............
I
t------------7
,.-......",
Design equation:
Assume W=lg r=FAoX

Cumene .... '" Propene + Benzene
(A) (R) (S)
FAD (lX) FAoX FAoX
The amount of cume:le hydroperoxide does not com:ribme SignL.+J.caIldy co the roml number
ofmo!es.
or X =:_:!2.
1 ··Ys
10-58
X .0204 .0165 ,0133 ,0107 ,00851 .OO563l .00311 .00241
a 1 .809 .652 .5145 .410 .276\ .182 .118
t 0 50 100 150 200 3001 400 500
-
1n a vs. t gives the best fit a "" c·-o.t
'Iberefore. decay is first order with decay constant of 4.27 x 10 3 (sec-I)
PIO-23 (b)
C :; FA"", ~AO (I-X)
A
U u
Assume no AP.. ...1L "" _ll. := ......

Vo
F AU
no
(1+X)
-.~.- -
FAO
= V .::::: ( 1+X) vo
C A ::: £::,,!dl-~2 "" CAO l!:X)

, '1,)0(1 tX) (l+X)
PA := CA RT =: CAO L~.~Xl RT
(l+X)
Mass balance: F AO dX ::;: rdW
10-59
F AO = 2.0 rnol/Il"Jn :: 1/3 mol/sec
CAD '" 0,,06 kmoVm 3 == 0.06 mol/l
R =O . 082~!L
K'moi
T "" 273 + 420 :;; 693 K

k ::: 3.8xlO,·3 mol/g sec ann
Ct. ;: 4.27x 10--3 sec,·l
W =: 100 kg
Us := 10 kg/min:;; 1/6 kg/sec
Equation (l) becomes:
2ln (l·X) -+ X =: ,CAn;:~: . !!~[e· (~t~l11
. .. (O.06XO~082X69~~~.~.8~.~~~~!..P~J r L~,3~~J.Q..3:.:.1.9.0.9 \. 1
2m \ lX) -r X ::::: - -·. .···{I~) {4~'27}xl0.3 Iexp \ L J 11
3 .. 6
.. x == LOO
PIO-24 (a)
s ..:;. W +. CO2 : first order, irreversible..
. . da:;:;; k<:J. an C',!1 == k.i an

ill .">
··.fA =KaC A
10-60
- - --- - - - --------------- --------- - ---- - - --- -- - - -- - - - - - - - - - - -- - -- - - - - -- - - --------------------

For T :::::500K
o 20 60 80 120
X% 0.,7 0.56 0,4.5 0,38 0..29

l!1ntL\ 99,5 142 ~ 178.1 2..2L7 262.6 3443
, iI-X!
For T::::: 550 K
o 5 to 1.5 20 30 40
X% ,.-
1 .,
0.89 0,,69 0.51 0,42 0.33
, I
11ln 1·..... ·,1
q .. X!
\
.!9,,5 -
8 7 .....~ 111.8 1444 174.9 237.6 302.5
4W,.
I
3QQ
I
~
In(lJ(l-X) II +T=500K
OT=550K
=1
aJ..I---
G '-II.
t
They axe Straight lines ."" n=2

For TI "" 500 K : slope:: 2.04 {t'~'h }
z:::> ~I "" 0.02
[l~t]=O.Dl =('tKh
For T 2 ;: 550 K ; siope;::

,
6.325 } =:>
~=0.126S
{-c K)z ;; 0.02
&::..Jl.QL.: exn {-.!fLf.....L ~ _l_l}

K.st 0.1265 • 8.314 \550 5001
~1 = ~1exp {- ~ (i l )} == K.i t exp {- 88~f~4 ('s60)} = 0.02

K.it = 1.296 x 10 3
We want to maimain Ka = constant
10-61
K h"~1:a t) Ko :=
Ko exp {f (f~" t)} ~ Ko (1 + Ki t)
c;cpfE \f~"
. IR ,. l \JL 1 := v - t
To T I ,~
rE( 1 IJ\']
exptR't~-- j ,- 1
t :;;;;; ,---""""-""- ,---------"""""""--""""':,'" --,
Kd
I
""",..1
480 485 490 495 500
l"""",,,
PIO-24 (b)
Since the equation for the acivation is:
a='""'
1 + lcd'
we cannot find a time for which a:::: 0, because it is mathematically impossible. We can, however,
find a time at wbich the activity is small enough that it can be considered to be zero, The following
graphs show the activation for'the two temperatures given
Activity of catalyst
~ 0 B
> 06 ' .....·a (SaO)
::,";!Ii:",~i55~!
() 500 1000 1500
time (days)
10-62
The graphs show that for sao K, the lifetime is about 1100 davs and for 550 K
the lifetime is about 450 days. "
PIO-25
First we need to tlnd CAO '
. l!2_:::: 10
ETB
Y£TfJ =0.1
C "" !l§.tu.. = ~_~_~_03(~.1.J =0.065
AO RT (8.309)553
Start by guessing that the decay is fiIst order:
We were told that the reaction is zero order when the conversion is less than 0.75.
This is true at any time after 2 hours. We also need to fmd the denominator
as a function of conversion.
X =~:1!L~~.(~;t
CAO
CAO •.... C:<t ;: (~40X
So we graph this:
This is the graph that we get:
tn (1/cao*x» vs
time
i-~[~~·
o 5 10 15
Time (h)
As can be seen this graph is linear which means that the decay is first OldeL We
also know that the slope will be the decay law constant so kG :: 0.2024.
10-63
PIO-26 (a)
Mass balance:
Rate law:
Decay law:
.9a,. =':,~Q~
dW Us
Energy balance:
..Fa
:..-. (TA"'" T ) + {"fA '(
)·AH, Rx \)
dT
-_., ....... _...".=
Stoichiometry
k"'" 0.33 eXP[3777(.!- -- "~,,,) 1

450 T J
[' 1 \1
k,. :::: o.,olexP!7000( 1 "T""')!J
.) L 450 ,
Plug that into POL ThiA.TH and get the following program and answers Ug to get
maximum conversion will be 17 kg/g,
10-64
Equat;h2!'~.':'
a(al/d[wy=-kd"a/:J
d(x) la(w) ,,··ralfao Q
dlT) fa (w)" (Ua r (Ta"T) ... ! -::al ~ (··Dhrl) }! (U"cps+fao*C!;>d)

fao=5 .. 42
U;1 7
1'a=323 :;).. 27
Dr.rl=···80000 Y~E~2l.,~ ~~~~&... =:~.;.:i~ ~'!.:;:\'1t;..'!"._va:~ ~:!~ Y~1.~~ I2~; ...Y£t±~

,) so C SC
<;:p5=100
a v 2-::-1596 ;; 211536
cpa=40 o .>S~:2: 0 887222
Ed=7QOO "l' .So ~4~ .. 61,3 He 6{S 6:3
Er=) 777 f." 5.U 5.42 5.42 S <12

0 11 1J 1'1 17
cao".27
1'a n3 321 123 32}
eps=l Dhrl .. seooo ···3£]oao ··S()OOC .. 8;10000
U"-"'.8 c:ps 100 leo 100 .:CO
kd", . Ol-exp (Ed' (1/450-1/1') ) cpa. 40 40 40 40

Ed. fOCO loon 7000 7000
k:: .. 33 'exp (Er" (1/450···1/T} )
E:::; J r17 37Ti 3777 3';77
Cd"cao" {t··x)! U .. eps·x) cao 0.21 a 21 027 0 .. 21
eps l.
,;;"" O.S Q B OS oa
loa 0 O! 1.:,)4e·;. o.n 1.:"1401
0.,33 <I H;:a a B 4>" :~'j'lS
"ca Q,;n 0.27 C Ol61349 0,0161349
:a ,·0 069: ·0 C:Q;9:2S .. 0 l.4S41 ·".OISJ92S
PIO-26 (b)
Using the same program we can see that the maximum conversion is 0.887
PIO-26 (c)
Everything is the same except the energy balance:
dT Uaw ('fa . . . T) + hap(Ts _.- T) + (r.~ )(llH Rx )

........ ., •.. -~ .:.::: ....... - . -.....-...-......- ......... .......
~ -.--.- - .. ... ---- -
............... ,., .... "." ..... ............
dW FAOC pA
1<Ve also need an energy balance on the catalyst particles .
Choose values ofh and a!.. We fmd that Ts needs to be slightly Ingher
than l' in order to get a large conversion. The maximum conversion will
be different for each T5 that is \1se(i
CDPIO-A
10-65
Given: The catalytic oxidation of ethanol
CH3 CH 2 OH +}' O2 -1- C:FI3 eHO + H:cO

Denote: A[=]CH)CHzOH. B[=]0130IO, W[=] H20 , A'S[=]ethCfhO'S
Mecha111sm is belived to be the following:
,~
A + 25 t-, A-S +B-S fA =leA [pA C§ "' CA-s CH.s!K.J

(h + 23" f:! 20-5' -ro:= ko(P<4 (:-;, '" C~S'!Ko]
A·S +o-S' ""'T

~ B +OH·S' +$ 'TAO:::; kAo[CA'$ Co.s'· PE ({)ii-$" Cs/KAO]
OH·S' +H·S ~ W+S + S' rw = kw rLCoH-$" Cli-S - Pw Cs Cs,!KwlJ

It is given also that CH,s =CA,s
'''fa
i..o.;:O
A
:ro,=O
k.:,- cbs' ::: Ko Po: c~, or Cos,:: 'f~;p(;; c~.
" Pw Cs es, .. 'r?'-""--

LH-S "" -'K.;-" wltn
'0
(-{)H-S' CH-S;::; Y!'.A. .t' A Cs
PwCS'
COrV' c;;;;; -.-- ... - - -
.) Kw 'iKA,P A
CT;:; Cs + eH's + CA'S:::::; Cs [1 + HK;;"P;]

""" " I . . . . r . ,..--.-".--~ . -.,. Pw
('I "" e' ' ' g• + C,)-S' .;. (iJH-S':;::: (S\l+ YKo P Ch -+;: ~
L Kw yKA,PA
,
--lAO"""
r", PE c,:'.m.·s' Cs ."1' r----..,.------,,··, , Ps Pw Cs CS'
k.i\O i CA.S COS' ""--;::::--"1 = kAO 'i KA. PA Ko Po:: Cg (S· - - - -..;:~
1
!. I\..AO .: L Kw KAO 'i KA PA
r• . 'K"K"'C C - .I
_ ?-.AO 'i . A {) ·S·S·;
·"tAO - "" .........
.,-----
p A, ! Po" =--_._--. P-a Pw
.. -_ ...,,_._-_-._"'-",._-;
'I FA l. ". K", Kw KA,cdKoi
K""1.::= K;.. Kw K..,o {K;:;
~ kAO iKAK:(:; Cr C r [ PA -{pc}.- . !:~w J

···r AO _ ...,...._.........................................................:"''''.....''' ...,. , ...................... - ............... ~ ........,............·t.
{P;'l'l +. 2'1J{";A. PA.. . ] 1 + ·rKo--
....· Pc-:- t ----. Pw I
, . -'7. Kwf"KA P",J
Initially PB =:; Pw ::::; 0
10-66
(b) With reaction 3 irreversible, '·IAO::;;; kAO CA-S (:Os', Since A·S. H·S, OH-S' are created
(and desrroyed) only at the reaction swface. A stoidriomerric relationship existS between
(a)
The same equilibrium expressions for reactions (1), (2) and (4) exist as before:
(b)
PwCsC s'
CoH-S' C~i-S ::;;; -- , (c)
Kw
Expressions for Cr and C;. become
• ,y> PwCsCs
wIth K AP.4 (, S » ··--K··"·-""".,-",
IV
CT == Cs (1 + 2fKAPAJ
C~ ~ c~1+ rK~;o,;:- +fx'x]
10-67
Rate expression becomes:
···T
A
=- ...... -.. ..
CDPIO-B
We can first try to come up with a rate law for this data. We can see that as P E
increases the rate law also increases but slowly the amount by which it
increases becomes smaller this tells us this:
We can then see a similar thing happens as PH increases so:

I
""!A Fc!
"" ...,..,.....,..... _ .•... _ .......
1 +KUPH
Sin,ce both reactants are adsorbed the me(hanism must be a dual site, This
makes the rate law:
.~££"~JL_ ........
o::.,.".,.__
1 +KEPE +KBPH
We can then plug this into POLYMATH. and we then get the follOWing values
for k, KEf and KH •
k= 14.6
Kl) =2 . 63
KH =1.76
10-68
lO"'8
O~90C --,.
t
o. ~aa ~ cc.a!~ ... !.atec
vql~,,!i'"
0.320
C .. 1SC
c. ace ..J............ ~."..... ""t~-.-......... !~.t...

~II!
!
i
f
I!
tt
I!
J . ____ L.i . _. ._.
A . . __ . . _--- ~ ............J?-._ ...... _...fF. . . .
2 3 ~ e 6
nOd~t; rat"i"?;:;It;"O:e.Oh/~ t .... ·K€.')lfPE*+K~H(Ph) '~2
'" ~ 1 "I .. 53-.... :<" '" 1.75797

;(0/ '" 2.63'17!
1 PQ5t':l\li:" -rE'-SLdr;.;.atsl" 6 neq.,at!;\I(o 1"@$lOU.a!S .. Sum: of squaf9S:::: t,,"5236e~.06
CDPIO·C
(1) NzO + S ~ N20· S
N:zO • S -+ SiO • S ·4 Si0:2 -t. 25 + N2 (Rapid)
rSiOt ;:; ~ Pues PNf?

1 + KPN;;()
(3) dF -
-~:::::r a 'Plug Flow Reactor)
dV A
10-69
k P'AO (l·X) (SB-2X)/O + EX)2
'fA =---------:···-·--··{e- -2X}-'---
1 +- KB PA~:!L-·
(1 t· EX)
k P).o(1 . X}{SB .. 2X)

:; (1':; eX? ~. K~P:~-{~ -2X) (l'~ eX)
as. ; : ; 1..1.:.2::
3 . 68 -' .
.~ 0·7
E:; ('--'}~"-)(2 +- 2· 1- 2):; 0.25

11.;) + ).68
1~~------------------------.r--'
Slope =: K. == 0.7465
1:300
k'
1200
Inr.erceut
~
::;:; 1
k = 703
k::;:; L49xlO- 3 NmTotr'-rr.in
!!l.rorr~"ITlin 11 00
A K = Llx10 3 mTorr 1
~+---~~~--~--~---r--~--~
300 .00 500 600 "lOa sao 900 1000
~)(m TorT)
KB::;:; 1.1 x 10. 3 In Tou l KB PAl =(1.1 x 10.3)(157) -= .173

k ~o:: 1.49 x 10..3 (1.57)2::;:; 36.68 Nmin
-r* ; : ; 36.7 Nmin (3·9.?: ~lli:~L_ ...._._. . _._
A (1 +- .. 25X}2 +-.173 (3.07. 2X)(1 +ZSX)
FAO :::: 3.68 x 10 J gmok/min
-r* ;;::; {Nrrim}:: 4.4 X lO'-O r- (gmolel

A A (m2min)
a=:; 250 m2/rr.in
..Ya.. =:;
F IX ~ Ar-.....a under curve of X
dX
· YS. L
4
AD r r
I) A A
10-70
x ...YlI...
.r~(Nmin) .l/.r~(~) l/.~ (m2/gmolel FAO
V{m3 )
0 73.6 0.0136 3091 0
0.025 70.3 0. 0142 3235 79 . 1 00012
0.5 67.0 00149 3392 82.8 0.0012
0.1 60.8 0.0165 3739 1783 00026
0.15 549 0.0182 4139 196.9 0.0029
020 494 0.020 4545 217.1 0.0032
0.25 44.2 00226 5145 242.3 0 . 0036
0.30 39.3 0.0255 5784 273.2 0,,0040
0 . 35 34.7 0. 0288 6547 3083 0. 0045
OAO 304 00328 7465 350.3 00052
OA5 26.5 0.0378 8589 40L4 00059
0.50 22.8 0. 0439 9983 464.3 0.0068
-0.55 19.3 00517 il746 5431 0.0080
060 16.2 0.0617 14{)29 6444 0.0095
0.65 133 0.0751 17067 7774 0.0114
0.70 10.7 0.0936 21262 958 . 2 0.0141
0.75 83 001203 27338 1115 0.0179
0.80 6..2 0.01617 36760 1602 0.0236
Reacror Volume per wafer:;;; 9.8 x 104 m3/wafer

:. Number of wafers, n::::: V!9.& X 10 4
A plot of conversion X. vs. number. of wafers can be obtained
200 --..•. - - - - - - 80
60
c
ri
;;; "2"
; 100 40 :§
-0
ci
....~
';"
%
2Q
o 4"'"'"T-~--__,-...__1-..,.......,..........-+ 0
0.0 0 .. 2 0.4 O.S O.S 1.0
10-71
Tne thickness on mest! wafers C:l.l1 be obtained. from tb,e same plot,
Wafer#l ; X"" 0
or'A ;:;:: T3 .6 N'!nin
:. After 30 min: 12Q8~.
Wafer #50: X '" 0.52
.r~ "" 20 Nmin

:. After 30 tnl.'1: @ . b.
Wafer #110: X:: 0,78
-r~ :=; 6 Nmin
A
., .Aite:- 30 min: J 80 ,J.,
CDPIO-D (3/e CDPIO-E)
CDPIO-E
. ' letters were substituted for the sDecies in the
(a) For simDlicitv,
Droblem sta tement.
.
"
The late equations for each of the three steps in the m.ecnanism
is given below.
Equation.s 1 and 2. are substituted into equation. 3 because the

third step (the deposition step) is assumed to be the rate
l.imiting step, we want to find the rate law of the deposition, and
we have data for the deposition rate.
10-72
.cuso, remember that we have the relation below:
. 1
f v=· .
1+ KcP c
Substitute everything into the deposition rate law:
We now have to check if the above rate expression agrees with

experimental observations.
.. The rate of deposition is independent of AI' and 1h. .-YES
• At low partial
, .
tJressures of TiCI. and NFL,
, the deposition
appears to be first order in TiCl" and second order in
~n)--YES
• A.t high partial pressures of l'·Hi], th.!'! rate varies inversely

with TiCl,.·YES
(b) To determine the reaction rate parameters we must

:earrange the rate expression to a linear £onn . f
A plot of the experimental data is shown below.
:::::i',. ,'_. .". . ".__. . ". . _._. . . ._. _ ._.

'TItanium Nitride fUm Deposition
Model Veriiication
1200000 ..1
f(x):;;.- L~l6l£"'l"-l: ... l.2167%ii.... s:

200000·
R,o\l OIl 9 91t98UE.l
Pal'b"2
10-73
1.
- = Y .... mtcrc:;pt :: 2.2168 x 10 l
.Jk.!' .
....!~~! . __'"
k. ::::: 2.035x 1O-1l_._
. em-· min· mT'
k.
•
,J
.
p~
1\..
.
== slope = 14 42
k~ :::; :'i . 505 X 10-5

rnT3
(c) The experimenrai data, when plotted with the rate law
deri,:ed
. in this
,
problem, form a straiO'ht
.... .::;
_ .
line .,..........
Thor'e''''''''''
.. """ ...-...;
ttV2 ;)roposed. Iri.eC.:1arusm may O€ used to describe ti'..2

depOSition or titarl:l;,rr~ ru::ride fi.lms.
CDPIO·F
Given: Ille dehydrogenation of ethyi benzt;';ne w st:;tTene:
E St +- H2
Quanur.lUve d::ua suggests re.lc:ion rare is of rhe fonn
Pj:;
-r;; a -'~",'" ,'\-_-p-~_ :-.";::--p"'-
.... . .,- where At, lu, A3 are consta..'1ts
1 '!'" "L E"" ."">3 St
T11t rJC~ that {orE) is independent of Hl suggesLS that me reaction is i.::reversible, and that Ii2
is not adsorbed on the c;:;,ralysr Sth'iace. Also, the aoove expression for (-TE) suggests that
both E and S~ are adsorbed on the su!face.". Try the following reaction scheme.
'E+S~·'}E.S
-fA::: kAlPECS· CE.sf'.r.<.A]
E "" S ·H· St .. S t 112
Sf • S ...;-)- SI t· S rs == ks fCE-s '. CSt-S PHJKsJ
I'D '" kD [CSt-S - Ps,CslKDl
10-74
To insure that PH2 does not appear-in the rate expression assume that the surface reaction
controls:
I~== 0 CE-S::: KA Cs PE
: == 0 Cst-s =C~~~f.
Then: CT Cs + CE-S + Cst-s :: Cs [ 1 + KA PE + ~~}
And ···rs =: ks [e E'S - Cst-s PHll ::; ks KA Cs [FE _ PSt PH! J
Ks J KAKS Ko]
~ith Ks »> 1, reaction can be considered ineversible, and its dependence on Pm drops.
kK",PE
out: ··rs :::;; ---..-------.. . where k;: ks Cr
1;. K. P~ + EsJ..
.-. e KD
Evaluation for k_ KA and Ko
Rearranging the nue expression: P e . "'" _1-. -+ fs. +_..f~....

-rs kKA k KokKA
with PS l ---1> 0, a oiot of ~. vs . PE should be linear with slope {1.} ..•.L. . ).

and interceot (- Since
. "'5 k · .kK A
only two points are given with Ps l ;::: 0, it is easy [0 solve analytically:
1 I 1.00 L415 x 10 3 ._+-_7.:;:..06;;;..;...·! .. .J

C-'·~21.~· O:Q.!=~"-·-· - 0.214 x 10 3 46.73 _.J
~\
( ··rsJl ==
k KA
+ l (P-)l and f!:E..\ == ....L_ +.1 (PE'"
k e \rsh k K." k I..
'P>:~ 'P~)
from aoove: 1..;:
k
{~._.jrs~L:;;:
(PEh" {PEIl
±6~.z' . 7iliJ."Z : :; 666 7 ~~~~~~!~~
0.01 1.0 . gmole
k :;;: 1.50 x 10..3. _.~?l:_

gm:;at-mm
10-75
ana,_.-;-.. - I\ - 1. (P)
1 _.. == (PlZ E 1 "" '706 '7 .. bOO.1
- - - - "" 40 _a..Wl-g:mcat-min
..- - : - - _ .
k KA -rs h k gmo!e
KA ::; 16.64 atm· l
Now, taking data points 1 and 3, in which PE is constant. the value ofKo k-KA a.ndhence
KD can be dete:n:ni.ned:
Forpoim L: (~)1 =k'k"'+~(Pdl

A
+J~~t~-A '-'-I)
Forpoim3: (PE) = .. L ... +1.(PEL +j~~tn ....

"IS 3 k KA k JJ Ko k KA
Substracting, and soiving for K~'h(~' noring mat (PE); "" (PEn
(PEB (( :~~l . Us),]

1.0 lo.166J~·i03 "i'4;51~'lo~31 cat ....
gIn lin
k K ... == ··-·(Ps-;;;~·lp·~;r~· =··················i~o·::·(rO··----··--~;jf-
KD =: 0.0075.34
.'. Rate expression is
0-
(a) (~vf\.V)E = 106..1 ---£.......
gmole
.. 1 grnole H..,O
Inen 8) = ._.: ---~.,--- . = 0..2
:;, grnole E
YEo=···_··L. =0.833 ; P""Po =OA15 ; XF=O . 60 ; 15=2·1=1 ; T=903"K

1 + 8,
.'. <:: = VE {} (5 = 0. 833 . FSl( = ~222.~~{.~ kg m::!)' "" 19.2 kg ~~!. = F~ eXt'
. . , day 10.4 . 1 kg day t.
~ R ....
PE "" C·E 1 = F:=RT
---"" ....__. = FE.COX)RT CE.{}RT(1-X}
...... _ .._ ......-.... -.--...• "" ........ YE...oP,,{l-X)
-.~ ............--............. ::::; •.. __..._,. .•............
1.) 1.>0{ I +EX} 1 +EX 1+€X
F, RT
PSt"" CstRT "" -~=u-'-- "" ·1)Ji:;€.-x)"·- '1+£X
FE-o X RT ., YE.oPo X
10-76
Rate expression for a.."lY X is:
0.025 [YE.~~X}]
~I"E ='''''--6"64" l~YE.oPJ 1-X'~1l';""=1""'32-'.7:""-'YE.-G-p--o""'X
1 + 1. - 1 ... eX j + -"," 'r'+ EX
Design expression for a C'.5TR (fluidized bed) is W =F~~F
w """ ~.5:Q_x..l..r,,,,,,,.!,,..:eXF,__ + 16.64 + p2.7 XF 1

0,,025 lYE.a Po (I,,,XF) l-XF j
:: _FS tt ~E,j",,,,,!,,.:tE:XE__ + 16,64 + 132.7]<F.1

0.025 XF lYE.O Po (I-XF) l-XF j
_ 19,2x103 gmoi 1 day i 1 +- 0.833 (OA5) , A 132.7 (0.45)1 1 day

- -,- daY-"·_'" x 0.025 iO~833 (0.415)(1~-:-45)''' 16,,64 + ---i:~45'--j x 24x~
W = 7,,06xl<r g
Cost"" 70.6 kg x Sk~' "" $T77
::>
(b) Plug flow reac.O!. expression for YE.O. FSr;> PEt PS~ and ·rE are the same as for the
CSTR, Tbe design equation is:
w =- __~St/._,.. !-,...._.L_., (-EX - [l+E]lnO-X]) + 10.64X + 132.7 (-X·, in (l"X)Jq;

00.5 X;: \YE.O Po f
W=-O""O·~:t'x__ "I:l_p_(.€XF'[l+eJll1[l"XF])' 16.64XF + 132.7[XF+ III (l-XF)]}

,-) F \Y::..O 0
w =1?:2.:.~~: ~~?,~. x.."" L"""".",,,,,, ,gm:~min

day 0,025 x 0.45 gInol
1-.833(.45) +- 1.833 In (1-A5) _ _ r" _ r _ I ."l~.",..
1""--"~08::;::;-YO-~""'-"""'''''''' 11.:l.64(O .... )}· b2"J l.o,45 + in (10.4))]1 x 24 *60 .-'
l ':UA .4'), , mm
W =2.71 x 1()4
Cost:: 27.1 x Sk:11 "", .5298

g
CDPIO-G
Given: reduction of CO with hydrogen over Ni catalysr:
10-77
Kineric given by: r ::;; - - - -PH~
0.0183 ---- (gmOle
- "Peo ClL.)
-------,-..-,-,
1 + 1,5 PH l gIn car-min
From the above expression:

1) The appearance orF2 in the denominator suggest that H2 is adsorbed on the surface.
2) T.ile fact ll:at CO does not appear in the der.ominator suggests that it. reacr.s as a gas
phase species"
3) 1be square f(x)t. dependence in the numerator suggests that Hz splits.
Therefore, suggested mechanism is:
kl
III + S -'J< Ih'S
f"··
Kl
• H2'S t- S _..:; 2H·S
(0-
k,
Ii·S + (X) CHO-S
;!.
14
CHQ..S + H·S C·S + H20 + S
... --..
" ~
ks
C·S 2Hz eXit -+ S , f', p>
".'," f5 '" K5 l c.c-s i-h -,- Pen, CsiK sl
~-
Remarks made in Chapter 5 of the text suggest thar reactlon 3 is rare cCEU'oiling:
CT::; C 5 -t, C:H,S+ Ce,g + CCHOS
-, -_ Cs
Lr -, 'I',1 ' Kl
"1"-
---7~,
• p}tz -,.. vKr K: Pi'£, -t PCE." POL PlhO 1
"'''''-''-:;'''''>' . , . , - - - - - - - - , - - - - - ,
l . Ks Pfh pit ~ Ks iKl K2 J
10-78
Kinetic expression becomes
Reaction is irreversible .'. let Ks _.+ QQ Then
with K1 PH~» "K 1 Kz Pit, we get
..,r3 "".,k;- __Pre

fK11G" CT Peo·
.m__ ' "Impbes that. at ml.l'l..\t;l<l.te pressures, most or~the
. This expt-esslon
~_,
_...l_
1 + Kl PHl
active sites are occupied by the Hz mole...."Ules.
(a) Design for a plug flow reactOr. Denote A[=] CO, B[=J Hz; then YAD. =0,25. YBO ;:: ~ , "
F· .
0.75. as := pE:a!2.;::; 'tyJ~Q. =:: 3, XF = 0.80
AU AD
F '0' Xc =; F("ll =: 2000 J1t". x ~ "" 125 lbrnol.

,'>. ."<4 day 16 Ib day
F AO := ill.l.bmQl.;:: 156.25l.1mml.
0.8 day day
DeSiEIl
_.
couation F,o
n
dX :; -L'~ dW or ~
}l{". =: f"U" dx.~
o
___ 0.0183 FA plf
-'A - - - - - . - ' . -..-.
1+L5PB
P A :;; CART == .~ AU ~!.:.o ·X) ;:;:)1 Ai) PH. (1- X)

1+t:.X 1+E.X
Pa "" CB RT = CAO R!J.~!!_:..,~~'!';::; fAO!!J~....:~~.~J;::; ~.lA{).!,O (I"X)

l+s:X I+eX l+eX
0.0183 [YM P.:~!:X.l1f3 YAO P'JJ~,~}r2 0.018313·ri'AO,~2J~~~Jrl2

.'. -rA;:::: .-••• " .. "." ..... _._l,_tX.".,,_.· t of EX ' __ ;:: _"",,,,,.,,,,,,,,,__, ,__,,,,-_.J...!:.eX _"~.'",'
1 + 1.5 fy~o Po (l;?C)1 I + LS[-Y~~~2.E~,~ll
~ I+eX . . l+eX 1
f 1 + 1.5 fd:'Ao.~2.i!-Xl1 )
____ ...."_. . ."l--1.±.~_JJ d.X
0.0183 1r[XAO Po (1- Xl 1312j
\ 1 + E;;X j
10-79
l
a~
~Vf..... == 1[L:LQ·25l?:J.312 +- 375 ri -0." 5X ]1I2 \ dX

FAo 0.0183 {'J(YAO pop!2 0 \t 1·· X J L I··· X . J
Tt:: integral can be solved using Si.'11pson's rule
Then f.~ f{X) d.X ::; ~(f{O)

3
+ 6i(O.2) + 2f{OA) + 4f(O . 6) + f{O.8)]
o
X I loX T1-O.25X 11.:Q~25X 11.q~Z;X + 3.75 (l;:q:~x:ri2 fOO

o I 1 I 1 I 1 4.150 1.000 4.750
-.2:2 I 0.8 ," 0.95 I 1.1875 4.974 ~....... L090 5.420
'lf4·To.·6 I
~-lj. .-~..-
0.8 0.2 1
0
••••••
0.9
m ·500
0.85 T}·125 ,I ........
0.8Q.. _ 4.000 _....
5.250 ..._==~=·:::I':":.:2~~2'::'5·.-_-+--::6';:".4";;;3';:'0-+--=-"";'-';';;;;"';';":;'
5.875 -r-...._..!.~45=.~8;;;;.5,,:;,64.;,,+~-+;;.,;.;.;;;:;.;..!
7.950 ........1 2.000--1LS.5OO
(0) Design of a CSTR
Desum cauanan
•• ' .F eXt'
IS W:;:; .~.:....
<f
..
~ -fA
\F _ 1'1171 .l. h.
£.lQl . G'"'l L-;J,'.
1;." •• ,
"un -454 p'mol
.;:,11 !
,\ .
cav
rv -- .I, _.oJ ~ ~,.. . X· x ".--.~~.-- ... X ...,---.....,.".;:. ....... __ ..,.
C.w.V.. £!IIlOi
~
Ibmoi'.AX;::'O·
L ... v mm
w == 3900 g
CDPIO-H
10-80
(a)
-r~
.
I
-r;
I / -r•
.
~
0
'A Fa ~.
Runs 1. 3. 6, 7 Runs 1.2.4 Runs 4 . .5

P", ..-...-.... .. t I
. . -rts = ,.--.;'''"'"-"".~""~ ~ . -. r. "" . . . . . . . -.-.-.----
1t· KA PA+-· ... • ~ 1+ KcP c +· ....
(b) Numerator: P A and Pa
Denominator: P A and Pc
Power of Denominator: 1
(c) Proposed Rate Law:
(d) To find the rate law parameters., reauange the rate law so
that it can be plotted as a Hne with the rate law parameters
as the slope and intercept of the line.
First, hold Pc constant and plot !'~~.!!. vs . Pi\

···r s
From the plot
K l+K P
Slope:: ." .....~" =: 5.2, y.- Intercept =----.!:.-£. =: 3..59
k k
10-81
Pa...~nett!rEvaluation v.rith Pa..rameter Evaluation 'W'ith
Pc=const.ant=2 atJ:n P;;t:;const..ant=l atIn
120 25 .-.--.. --.--.-.--------------.-..- ..........--........-
100 20
gO
'"
:::: 60
~
::~1 R..... 2 .= '9 999'9'~E -I J
-'i=--·--.,.-·----·-..'..·-·-T-......,..........·-,....---r-....,."""",-- . o "......--1"........... /" ... ·'!"T-,-.,-,.-··.....'f..,~~-~·~l"'f"'-r-r
0 1. 4 6 $ 12 14 16 18 20 o 1 2- :.> 4 5 " 7 8 9 10
Pa Pc
Second, hold P", constant and plot _~,\PB. VS. Pc

-.{ s
from plot below,
51 ope = .K,- 1 -'~'J'"

. -'-.. =ntJ~.J. v· ..· Imerc"'Pt :::: .1__....+K
__. . .~...P_.::. ~ )- '''i)-
. k J "'. k - . -".
Using the four equations above to soive for k, K A, and Ke,

we get:
mol
k :;;:: 2.60 . --·-·-----·-
gear· sec" atrn-
(e) A and C are adsorbed on the surface of the catalyst
(f) Proposed Mechanism:
c·s=c+s
The irrcver'sible reaction step was assumed to be the limitL'1g
step We check this mechanism and rate limiting step by
rearranging and combining the rate laws for each step. If the
mechanism is correct, we will obtain the rate law proposed in
pane
10-82
, .
k5
is much
·
smaller than kA and 1/ -- therefore
~/k
:::.r A. == .:r
k.
~ = 0
A C
··
A f ter 511 b stltullon, (~"v:;: . _ - " " -C"r - - - .-
1 + K... P A + Kc Pc
Next, substitute the above equations into the reactions step to get
Because this is the same as the rate law in part c, the rate law and
limiting step assumptions have been verified.
(g) Ratio of sites of A to sites of B at 80% conversion:
Conversion at whid\ the Hnmber of sites of A equal the number

of sites oi C:
X=(J76
CDPIO-I
10-83
a) To detemline the mechanism and rate-limiting step we must come up with the
rate law. Looking at the rate dependence of A we See that between runs 1 and
2. P A increases fTom 1 to 1000 attn while the rate law only increases from 1 to
1.5. This tells us that as A gets larger it changes the rate law a good deal less .
This tells us that A is both in the numerator and the denominator.
.... f ' - ..~1 .

A
l+K A PA
Looking at the rate dependence of B we see that between runs 1 and 3, PB
incleases fmm 1 to 4.5. This teUs us that the rate law is directly related to B .
..... r~ .- PB
Looking at the rate dependence of C we see that between runs 7 and 9 Pc

increases from () to 4 arm and the rate increases from 4.5 to 4.8. Also in these
luns we see that P A increases from 1 to 4 atm. So one of two things is Due either
Pc is both in the numerator and denominator or just in the denominator. Since C
is a product it will not be in the numerator in an ineversible reactkm.
···r I ,................................
"" .
A 1+ K c P:c
So the rate law becomes
With that rate law the following mechanisrn exists:
Adsmption
A + S'-1- A S
Snrface reaction
A S+ B(g» C· S
Dissociation
C ,S"'7 C+S
The surface reaction is the rate· limiting step.
10-84
b) In evaluating the parameters we can also see if our rate law is a good one.
Plugging into POLYMATH we can come up with the parameters.
~ .. aoo
r n
~
o QeqrEl'SS~01""I
~
~
n
~
4
r-ate llH0 d.ata
"t.eoc
1
[J C"I "'" at!>d
I y.all.u?
3.200 ,I I
! !
~
I
2.400
r,
'r I1 t
II !
I
I I
I'
!i II
LoSee
O.soo t n
2 :3 ~
I.
-ltJ· . . . ".u. . . . . .'ij,. . . . ·. ' . ·r
I
..,L . .
5
lL.
0;
iI I,
··..If·· ..
7 a
Model: rate=k~Cd.Pb/(l+Ka~~a~Kc.P~)
k 2 O.. GOO·H'il'ilS7 K" = 0.:;

Ka = 2.9SSaS
We find that the !ate law is a good one. k:::: 0'(>0045

K A =3
Kc= ..5
c) The best places to add points would be where Pc is changed, but P A and PB are
not changed.
d) No solution will be given.
CDPIO-J
:2 C2 Hs OH? C2 H5 0 C2 Us + rhO
(A) (E) (W)
A+S +:! A·S

II = kl (pA Cs- CA-slKt1
A-S + A-S ~ E·S + W·S r2 0:::; k2 [G,.$ - CE'S Cw.slKzl
E-S :;:: E +S f3 :::: k3 [CE-S . . PE CsJK3J
W·S ~!. w+S I"4 = k4. [Cw.s .. Pw CsJK4]
At steady srat.e r "" - ~~6. = r == rt =: 2r2 = 2r3 = 21'4

If swface reaction is controlling,
10-85
~:.== 0 = CA-S:; Kl P A Cs
:'" == 0
1<:2
C;::.S :::: !'.ECs.
~ K3
I4 == 0 CWo:) :::;:;!:w,. C;;i.
k4 Kl. r' ·'1
c·'r == c··;.·
.,s ' C. + ("·'·w·s -- ,{os .
Fe. . t· --.-..
C's,,i 1T' Kr 1 } ,A + .---;:-. Pw J
' R] K~.
C:; =---___._c;.r.____.
1 +- Kl PA +!I{ + .1.1:.
K, K4
')k I.... z p2 C~ PE pwell r, P- Pwl
- 2L l.\.l A·T - K,-K;K:-i klP.~ - ~-':
..... r ~ 2r2, :: ·····r""·"~-'-·-··"'--·--·······'·.. "···'·~· .. ·-::;;;,~ ........~~·"--:;-..::. ;::;: :::~~... . ., "' .........::..,., .....,........ ".__......._ ... "..:.~_ .. __.
111 +- K I PA .; JE + ~w 1~ I '1 .,- K··. P ,PE -+ Pw 12
. K3 K4J ." ATK3 . K~'j
where k :::: 2k z Ct Kl
Keq:;; K1 K2 K3 K4
Using points 9 and 13. PE "" 0 , Pw:: 0
... r == __...... ~!:1._

{l + Kl P,S:
°ll =:it i; +~£

r''''''''''
A I ' fl 1 (,... K
p at or "V r v'S . p-;..... produces a straight line "'1m sione 1 1,. and inteI"Ce')t __.L
A • 1/ k l: k
slope ={f =: 4.945 ... k "" O.04()9
interCept =:~. =: 85.59 •. K1 := 17 ..31
Using point H), P "" () .• ~=0.0399
klleck
U sing point 11. PE "" 0 = K4 =0.0368, dose enough

Using point 6, Pw "'" 0 = K3 "'" 0.659
Finally, using point 12 = K.,q "" 0.0975

__.J~i_..~g:~?§!'~_'!'~t
r=··. ....... 9._:.0_409 .........._.
) + 17.31 PA t· L517 PE ;. 25.05 PwF
Note: Keq may aiS{) be calculated using RT In K.,q "" ···ClCio.. Interested readers are
encomaged to check the goodness of fit of this rare law with the data .
---.-------------------------~-------------------------- --------.---------------
10-86
CDPIO-K
CDPIO-L
Rate law:
kCcoC ACCNaOH
-rAe;:: 2
(l+KAcCAd
Proposed Mechanism:
Pd + COi--'Pd· CO
-,-.-.~
Pd· CO + NaOn--Pd· CO" NaOH

--'''''''-7
AC+Pd -.~ AC·Pd
AC· Pd + Pd ,. CO· NaOH""--7C3H sCOOH + NaCl + 2Pd
Neither of the first two reactions can be limiting because they are reversible .
The rate step must be irreversible because there is no subtraction function in
the numerator.
We will first try the third equation as the ratelimit:ing step:
fA::::: kCYAC
Then
lACO _
""'-·-0
kACO
,~ACO:1':!aOU_ ;:: 0
k NaOH
Combine to find C"

Cv ;::..__ .. " ...,_. C{ ...""."_.... "...... ,... ~_
1+CcoKco + KCOKNa()HCCOCNAOH
This is definitely not what is supposed to be on the bottom of the rate law so
reaction 3 can not be rate-limiting.
Trying reaction 4:
r~ == k4CPdoACCPd<OoNaOH
CpeMe cannot be found so therefore this rate law is also not rate,·Umiting so
none of the mechanisms reactions agree with the rate law.
10-87
CDPIO-M
a) Start \!,lith a mole bahmce:
dX
--.::;;;;
Rare law comes next:
····r'A :::: kr a
Then the decay law:
do
.. :;;; ---k,
dt "
-YV'
t ::= .....
Us
da
dVV Us
'We then come up with the equation f()[' the profit:
Vvl1cre:
Then plug into POLThlATH and get the foilo\;villg program. The feed rate of
solids that gives a maximum profit is 4 kg/min .
•
~:!!S!-9.£§.' ~~....Y~1:::!::
d(a) Id(w) ,;;·}Cd/Us 1
d(x)/d(w);'ra/fao 0
fao",1
kd=2
Us=4
10 ··18 :).
;;.q~~l~~ . y.~i~'1£ ~~::nu..~" ..:5!:~~ !1i:1itt.UI~.-'y'alue ~_~~.L . Y~c;~~
l
fb=fao'x
a '; c ;;
P=1.601ffb~1.0~Us
x 0 75 0 73
fao
l<d - 2 2
1
:::-:1 ··c 5 -
£1:: 0 i5
"-'...
O. 75 "
? 4G OiJ "·40 SO
b) As seen above: X:::: 0.75 and a =.5
10-88
c) The only equation thai changes is the rate law:
.~~ --·k
dt - d
W,······W
I =::_.M:1!. __ .
U
··dW
dt =:: -_._-----
U
da
-~ ~.
kddW
. . ".. == ._.-. . . ". ,. . .-
dW U
Integrating we get this:
W::::; W MAX @ a == 1
k == l-,~!l~
U
a == 1- . ~£!{~Y.u.-\X_.:~J
U
~t;.i2r:::!;, In~~~al.'.:'5.1u~
d(x)/d{w)- ·ra/fao o
kr;;:;5
kd=2
Us=.8
wmax"'l
fbaif{x<11 thenlfao·x) eLse(l)
0.",1.£ (kd/Us* (w-m<Lx'·w) <1) ::hen (lMkd/Us" ('HmilXW) ) else (0)
P"'150*iblO"Us
o 1) G 8
1
'·3 :42 ·3 142

ra -·0
·s
\Ve find U:= 0.8 to ma.xirnize the profit X =:: I and a:: 0 exiting the reactor.
CDPIO·N
10-89
Design Equation: \V ="~~ . \O~_ For n en order kinetics .
(-J:,\ )a(t)
~<\ssume at t = 0, a(O) "" 1 and X "" I.
Now
FB(t)::::: FAoX(t);::: RON(t)
X(t) == _~O~Q '" _~:2~.~!2.

106 RON{D)
Second order kinetics and second order decay rate tIt the data very welL
J
l+k .t:::: . . . . .kC~
. . . . L __
d CAo-,C A
y == 0003x + 0.0855
Plot of - - A____ vs t:
C.A(J·- CA
-1.lnca; lExp
Data; i
i
() t "..........". .......~"" ................... ,._"~ .. _- ....... ..,...". .... """.".. ,__....._., _ _".. ,_, ....-.J
o 100 200 300 ~OO 500

t (h)
F.om the graph: intercept = 1j k =: 0.0835 ~ k ::::: 11.98
slope = kd J k "" 0003
(b) Activation Energies both for rate constant and decay constant can be estimated from the
temperatu,re·time trajectory
CDPIO-O
10-90
Given A -+ R + S
Batch constant volume I"Cactor, P mCI""....ases with time
NAO dX =a fa Wdt
Assume a = e..(lt
'0::;; kPA
:. PA=CART
C A ;::: NAG 0··2.9.;::: .~AO (I ·;.;.t =: eM (i-X)

V Va
:. NAO <.LX =We..(l' k CAO (1~X) RT dt
f. lC
dX.:;:; W k ~AO RT J. ea.: dt:;::;; (W.) k RT J.' eat dt
•
I-X NAo Vo '

o 0 0
· ~ Le~ dt wl=e ~ =(~-)k R1

.In(l.X) == ~ (le'<Xt),
a
Assume that there is very little deactivation in !he first. 10 sec
-In (i-X) =: ~.. (at) = ~t (for smail t)

Ct.
~:;:; ~ln ( .. lJ :lln{--L-) '" 3. T7 X 10.3 sec

t l-XI 10 1-0. 037
~=(~)kRT = k=dRT=i-~~%s-~~ioi
k = 6.63 x 10 5 sec 1
10-91
At t relatively large, e-<ll: = 0
~ -In (I-X)
-=
a
~ 3.37 10.3 ~.
-Ts;J =
X
a:= ~ (l>o~~l == ~'(1 5.18 x 10'" sect
" ,1a(1-X) "" 0.128 (i"-e-S.1ax1 o-'1t)
" TIle assUt~rprion of a firs;: order :e2.Ction kinetics and a order decay kinetics is
justified
CDPIO-P
cyc1opem:ane < fl·
coke
pemane
Batch mole balam:."e :
AsStL."Ile q :::;;; 2 a = ..............L.". ._
10-92
,
Ifn=O _I =_I_+5!t
X let k-c
#
Ifn::::l --1._ ;:;;: -L +.5t t

·In(l-X) lei kt'
X(%)
o 75 1.33 0.721! 0.333
20 7 .7 1.414 0.815 I OA15
~o. . . ,_. ;,,6 7. 11 ..46~33 0.902 II . ~;:~~--.J
_ ·
ou v 05 .., 1.076 O.653~1
.)8- '.~/· · ·"· · .__~/•. 80:,~j
F
!
112800
250
"'1
I
---S--4-
42
'-
i 2.381
_ I 1.245.__L_.Q;~E
._-_. __
1.498
1.836
._.
I L053
I . . 1.381
350 I 361 2.778 2.24T·--, 1.177
1--';'800--
500
I
I
I '4~023"'-'-
30 r-'
2i ',-"-'4.545
3.333
3.545 - ,
I 2.804 . . 2.333 --'
···'1200··T-~. ! 6.3 _ ....L··6.TITI. ~-

. ·_"';'·); . .~;':;_.; .___?'6'; ;; 'O_·-_-_-+.;...-_-_··_5_·.1_3_5_:=1---,
",,,l.
I
+lfX
<> -llln(l-X)
II1II (l-X)/X
f .
o
o
L.... ....~.~ ..... ~,~ .."'._.. "..... ~ ...._ ......... _ •.• ".. '"M_._ ......,
tOO ~ ~
.' . -~....--.
ICQ
.---
1=
...
From the above graph. a111ines are straight lines.. 'lberefore. q = 2 is a good assumption.
We need to ex.amine the data to see which value of n having ~:::: constant n=:O and n "" 2
At
will have similar behavior of ~ because:

At
8.= 1.._ 1
X X
n == 1 . Av.:;;.1 f.--L--l and.1t;;::"O min
'. l-In( l-X}J ...
~ :;;; 0.094; 0.087; 0.087; 0.084; 0.081 ; ........

. 0.0797
lit
At
Therefore. ay is deo:easing gradually. It is not a constant.

At •
10--93
For n =:; 0, n.:::2: ~r :::: 4 x 10-3 = constant.
6,
• If n::::{) :
_ _ QX, == !<::B_~~Q,
{lX)2 at
(l,Xr "ili.." ::: •... ,. L . . . . ;- --~Q.,.,.. t

. dX KR C AO KR c.-\o
n=2: Slope is negative. It is u.nr:::asonable
n:::{): ~. vs. t is a straight line.
10-94
<> dtldX
w =0.01 kg/m]
't
C W (0.03 krlifl){0'<)1 kg) k
= 22.-. '" ~_ ..................m... . . . :.......... .. _m 3 ... "" 20 _JL min
FAO 1.5 x 10 5 kmol/min {m3 )2
(b) The order of decay is q;;2

,
k
...Q. "" 4x 1(},3 =:> k: 3 x 10 3 mini
kA
(c) Moving bed reac~.or: F AO =2.~&!. ; X;;: 0.80
mm
* lia. :;: k' a2
d1: d
In moving bed: t =if where u == =

., .
Subsnrure mea equanon (1): ..
~~
dW' " = k.:!"
'1:1' a'"
. . ~.::;kd·dW
a2 u
10-95
SUDSritllIC in~o equation (2), vie have:
W :::::455 kg
(d) If u O - k~
= ) .---::".- w ==48 . 6 kg
ttl!.(l
CDPIO-Q
10-96
a) Mole balance:
Rate law:
Decay law:
Stoichiometry:
CA = CAtI (1" X)
CD = (~O(e8 + X)
d(x)/d(w)-.-'-ra)/fao o
d (ia) Id (w) ",·J<d"cb/U 1.
kd,:6,
1.. 000
faOi,:20 -, .. ,
:' ~
U;:8
k';350
cao=.l
f
ca"'cao"(1.·x)
, cb:cao * (thet.a +x)
r·a"·. ·k"ca ·CD
Wo '" o.
10-97
b) The only change is in the stoichiomeuy:
POL'{;v1ATIl
Initial v~~!:
d(xl Id(w) =a* (--ra) I£ao o
d(a) /d(w) =··kd*co/U 1
kd=6
fao=20 ! ~oo
U=S
i
K=3S0 T
cao::tl:"l, C "'0..'1
1
J...
theta::: 1.
alp= . Q38
ca=cao' (1"",), (l"alp~w)'·. 5
cb=cao* (theta+x)' (l--alp'w) ~O .. 5
ra="'k*ca*cb
Wo = 0, wf = 24
CDPIO-R
Curoene --, Propylene +- Benz.ene
(A) (k) (S)
a:s .I. .
fo
(a) We find a relationshipbetv.tcen a and C A
F X F
r '" -.~-
W = 2W . = F"-, (W:= 19)
.R.ill:Ll.:
t o 60 120 180
a 1 07.5 0,,594 0.491
CA o 0.01 (LOIS 0.0243
Run 2: PA ::::: 0.4 aL."'Il
t 0 100 200 300 400

a 1 0.833 0.733 0.65 0.583
CA 0 0.0057 0.0106 0.0148 0.0184
10-98
Plot of In a vs. C A gives a straight line passing thmugh the origin wirh slope a
(single ~te adsorbed. smface reaction controllingl
Iinitiairate are used, PR == P s = 0 and 1 » KAPA (adsolption is small at high temper.rture), then
fo"" kt'KAPA·
Using data at time zao from runs 1 and 2 : k~ K.<\ =: 3.2x1O-3
Hence, overall apparent rare law is

r = k~ KA e<t.c... P A ; k; KA "" 3.2x1O· 3
ex.::; 28.9
: : : - k:..:i amf{P A. PR, Ps) == -~ am P"A

Trym::::: -2
Since PAis almost constant. d~l.ring nms 1 and 2 (low conversion)
Run 1: ku PA. :;;; 5.767 x 10-3
Run 2: k<J P A = 1.769 x 10. 3
P A == i in nm 1 :::) ~:;:: 5.767 x 10.3
PA ;;:; OA ill run 2 :::) II "" L29
.
Kl KA "'" 32xlO·'
~:: 5.767xlO:;
11 ::::; 1.29
t L.'1 minutes
10-99
(c) Overall conversion = 0.60
(2.8 rr.oll:Jec cu...--nene j

\ 4.2 mollsec propene) L. "" 11.2 IT'.ol sec
1.4.2 IT'.o.llsec ber-.2e ne J
Cu:rnt!ne "'--t Propene -+ Benzene
(A) (R) (S)
COllIDosition at reactor oudet

.. YA: 2 &. =O?S
11.2'--
A ?
VR = Vs ""..::!.;;.""-." "" 0 315
.. - 11.2 "
Composition at reactor inlet. Fa :::: 7 + 3 :.= 10 mol/sec
FAo ~ 1 , 3(0.25) "" 1.75 YA "'" 0.775

FRO::::: 3(03'15) := Ll25 YR ;: 0.112.5
Fso =:; 3(0375) := LIZ5 Ys = 0 . 1115
Let Xf "" converS1on per pass
~rotal flovi at :r~aC7or outlet before the recycle sc"ea.,s is:
At a.llY point along the reactor:
Assurne that rate law in (b) is srill good fOr the mO\o'ing tx:d operation (may not be rIue in
practice because of the high conversion)

• ~.. k, KA PA
I'::::; a k, K.,., P A=:' .. .l..."•..•.•_-_..
, .. l+k.:!?A,t
Moving bed react()r: t """ l~;

F.,odX =rd W
lO~lOO
== ?_:15x5.7~~10-=~ (1,29+X.\O.Z9 W + _....1..7~. _._( 1.22+X.)
3.2xlO-'x2000 I-X J 3.2xlO-3 I-X
= 6.98 X 10.. 3 (1.2.2±Xj29 W + 2421 (122±X.)

I-X IX
With X::O > W=o
If X:: 0.542. using digital computer W :: 3.1 kg
CDPIO-S
a) i'vlole balance:
dX a * -r'
:::::: .................• .::! .
dW
rate law:
~r:4
, ::;: k'('',t
St.oichiometry:
Decay law:
da : : : ._kd. _. a
._............
dW Us
?.;:;;; (1 . . o:wt5
Po
5~ "'" (1--1OOa)05
0::::: 0.0099
rOl da kd dOO
'-'Jl -~- :::: 'i~!;' JodW
!:i..;:;;; 0.023
Us
10-101
POLYMATH
EguB!:ions-,.
d(x)/d(w)='~B'a/fao o
d(a) Id(wj ;-·kd*a I
kd" 023
fao:=:4 Yi:~X~2!~ :.c.':'tial val.l:.f! ~~,..:£,elue Minirnu:r:. ·,ta,l>.!.e £l!~h-y~lue
w l{W 100
k=.09 x {} 0 .75:;':51 C ,57161
cao::o2 a 0 :00251 C :)0259
a2.p= 0099 kc " D23 0 .023 0 023 C 023
tao
ca=cao*(I·x)*(1-alp·w)A.5
!<: 0 ~) 9 0 09 C 09 C 0'1
:t'a;;;-·:t',llca
CdO 2
0 0099 0.,0099 C 0099 C 0099
Cd 0 04.35678 0.04856"18
ra {L1S .. 0 004371.1 -0 13 '<Ii 00437:1
b) POLYMATH
J J2:) :-
ceo
CDPIO-T
Design Equation: FAn -1~ ~ a(WX·· r~)
RaleLaw: < ;;;:k'C A
Decay Law: (for sintering)
Stoichiometry:
Combine: dX. = _... ___ L .... ~:(l' X) dX

.=.,k' dW
dW l+!'AWu
Us 0
l{Ilx)~ ~:~;ln(l+ tt w J
1 1
From the problem statement a - ::::; ................. :.:::
'e.u, 1+1:< W 4
Us
Plugging in 100 kg fIx W, we can solve fort.:!

$
! .. := 3.43
1 X
10-102
CDPIO-U
The heat of activation is given in the problem as a function of the carbon
number so we can just graph that:
Heat of adsorption vs carbon

number
c: 80
~ 70
1:
o 60
~ 50 .
nI 40
'030
_ 20
<IS
~ 10
'r" 0 ............
'H ...... _ _ """ . . . . . . ........ ,' ........... , . , ' " ' ' . . . - - - - " . , . - - .- - _. . _ . _ . . . . . . . . . . .
o 10 20 30 40
Carbon number
To graph the activation energy we need to find its equation. It is the

Arrhenius equation.
k:;;:Ae- E/RT
Solving for E we get:
We know that as the temperature increases when n S; 15, the rate increases so
k still gets larger with greater temperature so E is still positive. When the
temperature increases when n > 15, the rate decreases so k decreases making E
negative So we can come up with some equation with the above equation
that fits this criteria and we can corne up with the following graph
Activation energy vs carbon

number
6 ....• _ .•_--........ -._.-......- ... _-_..........................._ ......................... ..
5
>-
0'1
:;; 4
.
c
3
o ---- ---.----~~ . .. . . . . .
10 20-·-·-----·3"e-
1 . -------.. -----....-.------.-.... ---.. --......- -... --....- ..- -..- - -.....•-.----
4
Carbon number
The reason for this unusual temperature dependence is due to the fact that
the higher the carbon number the less it wants to add another carbon
10-103
CDPIO-V
(a) a::: 0 at the end of the reac[Qr:
:;;:? Us = 1 kg/s
(b) For Us::: 0.5 kg/s:
a ~ 1 il~ W ~ 1 {nOoN;;} ;1 (04kg')w
Catalyst Activity vs. Catalyst Weight
W (kg)
When a::: 0, the catalyst is inactive. In theory a can be negative, but in reality, once the
catalyst is inactive there can be no further decrease in activity_
(c) For a catalyst feed rate of Us =0..5 kgls:
Mole Balance: F dX:;;:: a( . . r')

Ao dW A
Rate Law ; . r,A

k(·' (.,
:;;:: '"'A'S
Decay Law ; ..... ~~.. =.~:P. =g~~.~. . = 0.4 kg!

l. :;;:? a == 1·· OAW
dW Us 0.5 kgls
Stoichiometry: (Assume T = To, P z Po' and 1) "" 1) Q)
C\ =C s ==(~AoCl·X)
Combine:
FAG .~= (l.'.O.4W;{kC~,,(l . ." X)"]
(k6t}(i~)l+ t~w}w ~ (~Md~~~(W-2itw'l

10··104
(l~xr!'i: (w -~ w' J
From part (b) we know that the maximum catalyst weight (the point where a:::: 0) is 25 kg
We will find the conversion at this point:
(i?Xr QX~:i2'.{2.5 -$~:5) 2.5' )= 025

X=O.2
(d) To achieve 4()% conversion:
(l~Xl =~~:{ w .. ·ittw ' )

f~~~=O{5-fJ;5') =>
2.5
O.667 = 1
Us
lJ s := 7.5 kg/s
(e)
ForU'==:~'?xj=!'¥:( W- 2(!jW') =>
(i·~X) = (0.2)w:::: (0.2X5)= 1 =? X =0".50
CDPIO-W
Design Equation: N~:=<aW
So dt
RateLaw: ,
- fll ;;;;
k'C'z
-B
da
DecayLaw: ....• =k =0.05
dt D
a I
Jda =,0.05Jdt ~ a:: I,O.OSt

1 0
From tilL'> we can see that the maximum reaction time is 20 min, We will find the conversion at this point
Stoichiometry : (Assume constant volume)
ell "" ClIo(l···X)= ,~§2(1" x)

V
Combine: ,~?c. =~/(l:~:~:?~)~~Q_::_~Z~ =: ,~~~.!t! (1 ""' 0.05t Xl····, X l

~ V-N 80 V2
_~_:;_ :: ~/~l!!!_ (1 . . O.05t}it ~--~ :: Y!~l!!! (t _O.025t 2

)
(1" X Y V I " "X V
"'~, =~g:g!X!gX12 ('20 . . 0,025(20'f )= 1

I-X (1)
X=050
10-105
CDPIO-X
a) Mole balances:
.dF
. . . . _. = r
A dF.l!.:; r
___ dFJ.:,. = r
____
dW A dW B dW C
rate 1a'N5:
stoichiometry:
(
, F.. F4 (1- aW)Q5
= ..._ .. "" ...'-., ....... --....._,......
'-'tt V Vo
, Fa Fs (1-'aW)QS
CB "'" ."--,, := ...,....---..,........... "-,-,,.
V Vo
decay law:
da k a
"" ,.12"_,,
dw U,
Evaluate the parameteIs:
Plugging all of tllis into POLYMATH we can change values of Us. T, and Vo CP... . o)
that will give us the most of product B.
We find that at a tempcratllIe of 396K, a solids velodty of lOkg/s and <I gas volumetric velocity of
3
o 63'3 dm /s that con esponds to a p3ltial pressure of 5l 3 attn we can the maximum yield CO! B,
d (fa) fd (w) ""a

d(fb) Id (',") =,,10
d(Le) Idlw)=J::'c Y!f,~bl(;! ;:::'~E.~~:L..y;e t~~:; ~eXit~1f!E_yalue £!~imum :!~;~~ Eb~.~.,?:~±~~
100 0 leO
d(al/d(w)=kd'a/Us
fa Q 3813942 Q.0913942
Us"lO f;; .;) ,. 52'~43a 0 ;4t>631
T=396 Ec 0 0 . 4 n,,71- 0 '1l19 i:
alp=9 <lEO",3 1.93102 1 . 9Ji02
Vo= 633
Os 10 J,O 11 :0
390 396 196 39G
xci", oa'exp(~500011 937* (1/400·111') 41p o. 009S 0 .CO:iB 0 009'8 00093
k2= OJ..*e;<p{20000/1 ,987* (1/40Q··l/'.l'I) VQ n 633 0 631 0 633 0 6JJ
kl=, 02 'exp (lOOOOn 987* (1J400 .., 1 IT) ) kd 0 0661149 C.066:':'49 Q.00lil149 0 065::49
ca,;!;.i.:a~ (J..···alp""t..t) . . . 5/vo

k2 OO,i55S4 o .cp:nSSS4 0 00715554 0.00775554
kl Olj6Ln. 0,0116131 O,0176i3} ;) Ol"l6l·.H.
cb~fb~ (l·"alp*w) A ,SIva
c"" 1 S'191S 1 579"; S 0.0131646 0 01Bla~S
xa-;;:'-a*kl *ca
c".a .. 0 0278243
0 631)42
.. 0 0(10620401 .. ·0 .07.::6245
0 0991~46
rc~a'*k2'Jrcb .;}. ':;OO6:!O403
:cb= ··af!' (k2~ch-kl *ca)

,c 0 00641366 Q C01,4$'~02
d, 0 02 :82";8 0 02/'S246 "-0.0021742:3 •. 1) O;)O~nBi$2:
10-106
b) Using the same program we can find what it takes to get the most of C possible.
We find that at T:::; 396K, U,:;;;; 10, and vo:;;;; .03 we can get Imol Cis. P AO::::
1082.4 atm
~a£±~ ~~~~ ~~_~al:.!Z Minimu,tl1 v .. l" .. !:ir..al .. ~~;,!!!

0 100 0 lOO
'" 102629 .... 23 1 . G252ge.:n
fa 1. l
fb Q 0 SZ4487 a 135042"",:0
fc () 1 1
a 1 1 .9370:2 1 1.93702
Us 10 10 1.0 lO
l' 396 396 J96 390'
<>1.;;> 0 0098 0 .. 009S 0.0098 0 .. 0096
vo 0,03 0 0) 0 03 0,03
kd 0.05511.49 o .0651149 00;;61149 0.0661149
k2 0.00775554 0 .. 00715554 0 00175554 0.00775554
kl 0.0116131. 0 0176131. 0 .. 01'76131 {) 0176131
ca 33.33J3 J3 3333 1. 83'798e .. 23 4 .6379Se-23
ch 0 17 .. 26% 6. 36S55e-:.n
ra -0.581104 .. 1 65051" .. ·24 -0. 5871C4. -1 6505"113 .. ·14
:c 0 0 .. 13615 9 56332,,-::
rb o .5,s'1104 05971.04 '·0. C7!$781 ·9 55332 .. ":'2
c) To get the Time Temperature trajectory we can use the following equation to
create it:
This will give us the following graph:
Temperature~Time
Trajectory
1200 .-........ -.......... - ....... -..-----.--... --..-,,-.-............ -....... .
1000
...
1U
.;! 800'
lU -
d;Q. ::':::.600
E
1U
,-
400
...... __ _ __ -_._ ....
..................... ....... ....... ...-
I- 200-
o ...............-.. . . . . ..
o 5 to
Time {s}
d) For this we just add an energy balance We have to assume a heat capacity of the
catalyst since none is given Here it is assumed to be 100 J/kgcat
Plugging this into the POLYIvlATH gives the follow'jng program.
We find that the tempemture is 38SK, D, "" 10 kg/s and v 0 ;;::; 051 dmo/s. P AO =
62 . 4 atIll.
10-107
.Eq:..lationS,l,
d(fa)/d('w)=:r:a 1
d (fb) /d (w) ,,:tb o
d(fc)/d(w)=rc o
d(a)Jd(w)~kd'a!Us 1
d(1') Id(w) = (:::i;l~ (-16000) .. rh T (--32000» / (cp' (Us+'''cl+fbdc) 1 388
kd= 08*exp(15000/1. S87*(lJ4QG-I/T» ~ia::'l/;J ~.i-;~;._·...alue ~ v.al~~ P~nimumwvaL~~ f~-,"l.~b.~£
Us=10 100 Leo
c,,=lO() t
G g 1:,155 o 61.1.155
k2= Ol*exp(20000!1 987*(li400-1/T)} o 21532& o t) ,215328
kl'" 02*exp(lOOOQ/l 987* (1}400·,,1/1')} 40~O!,
alp=9,8e" 3 T 358 382 2.:.2

C 0446169
Vo~ 51 0.0332906
10 10 to :0
ca;:fa* (l-,alp'*w) . . . S/vo cp :,:<) lce 10;)
cb"fb*(l"alp'w)A Siva k:::! o 004Sn{)1 {) .C0459207 OC29~-!19 Q :)03}'0577
ta.:::::-.a,'*kl"'ca kl ':11J553 O~';553- O,(H085Z: 0,0111477
dlp ,0·098 o 0093 0098 () .. JOSS
t;'c=a "<k2 '"'cb
>10 o 31 5: 0 S: C ,$1
,;;, 3i5D}S 96{)'8 -0 Q~a':lS~ 0481:;.54
o 7;6.3935 :1 ,':694'1'2
:;c .,
-Q :3265'44 '''0,000'15307;5
0,001'73258
,·00255;.1\4 -C.00:)753076
o 00)139124
~, 18S:6~- 05
10-108

Solution Manual Elements of Chemical Reaction Engineering 4th Edition WWW - Elsolucionario.org 573 680

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Solutions for Chapter 10 - Catalysis and Catalytic Reactors

PIO-I Individualized solution

PIO-2 (a) Example 10-1

-rp = 5(0.5)(_1_)_~ = 1.28*10-4 mo~

-rH =0.01 ( 0.5 ) -

PIO-2 (b) Example 10-2

6.3% of the sites are vacant

9% of the sites are covered by toluene

(3) Linearize the rate law to:

PIO-2 (c) Example 10-3

From figure ElO-3.1 we see that when X =0.6, W =5800 kg.

Model: ReactionRate = k*Pe*Ph/(1 +Kea*Peat·Ke*Pe)

Model: ReactionRate = k*Pe*Ph/(1+Ke*Pe)

variable Ini guess Value 95% confidence

Model: ReactionRate = k*Pe*Ph/((1 +Ke*Pel"'2)

Variable Ini guess Value 95% confidence

Model: ReactionRate = k*Pel\a*Phl\b

Variable Ini guess Value 95% confidence

Model: ReactionRate = k*Pe*Ph/((1 +Ka*Pea+Ke*Pe)ll2)

Variable Ini guess Value 95% confidence

Model: ReactionRate = k*Pe*Ph/(1+Ka'Pea)

PIO-2 (e) Example 10-5

As t approaches infinity, X approaches 1.

(2) Second order reaction with first order decay.

PIO-2 (0 Example 10-6

If tau =0.005 the minimum C A=0.607

PIO-2 (g) Example 10-7

This gives the same expression for conversion as in the example.

(2) Second order decay

_~_= kC~oUs In(I+'5dW J

1.24= (0.6)(0.075)2 US_In (1 + (0.7~)2~~?OJ

PIO-2 (h) Example 10-8

PIO-2 (j) Individualized solution

PIO-3 Solution is in the decoding algorithm given with the modules

rADl ;kAl [Cr - ::~] Cv •

Bey Ridea1 Kinetics

PIO-4 (e) Individualized solution

E + S ii"~ E .. S • CE1OS :::: KE. PE. Cv

rAD =kA [ PAzCV2 -

re.s = kD [ Ce•s - P~~v] = kD [Ce.s - KePeCv 1

rs "" ks (CA.s Cs • CaoS CcoS Ks)

rDB =: knB (esoS . PB Cs/Kos)

C·S t:! c+s rDC;: klX {Ccs - Pc Cs/Kr:d

Pc Cs '" PC KAC (~-5

:. ···rA ;:: _.......

If PBO::: 0 and Pco == 0 , then

~I: (_lmr~~) 0 0.275 0.5 0.77 0.77 0.5

At small P AO: . ;AO:= kl P AO ; using point 2: kJ :: 0061 = k2:::: 5.34xlO-4

.. rAO =..... _... 0. 061. ~ AO ............... ; so

Using point 3: k3 :: 7.05xIO· 2 = k3 = 3.19xlO-2

k3 "" L05x 10.2

25.0·~ - - y "" 4.3103 + O.073937x R= 099583

lntercepb1/ko. 5 ::: 4.31

o 50 100 P ISO 200 250

Pb and Pc "" 0 so that red llces to:

%vacant ::::: ._-_ 1..... - .. _.:;::: .........._....1__ ...__. =: 0.41

ME+5 :;= ~fE·S

Assume Surface Reaction Controls

CME-S "" K/.u:. PME Cv

Model: ReactionRate = kPePh/(1 +KeaPeat·KePe)

Model: ReactionRate = kPePh/(1+Ke*Pe)

Model: ReactionRate = kPePh/((1 +Ke*Pel"'2)

Model: ReactionRate = kPel\aPhl\b

Model: ReactionRate = kPePh/((1 +KaPea+KePe)ll2)

Model: ReactionRate = kPePh/(1+Ka'Pea)

%vacant ::::: ._-_ 1..... - .. _.:;::: .........._....1 .... =: 0.41

w:;: ...___.J2!1_. x. 10:;: 6000 g "" 6 kg