CHE 304 (Spring 2010) __________________
LAST NAM, FIRST
Problem set #2
For a first-order reaction, the following rate coefficients were found:
Temperature,C k,h1
38.5 0.044
53.1 0.301
77.9 1.665
DeterminetheactivationenergyofthereactioninkJ/mol.
Solution
Whenthesevaluesareplottedinadiagramoflnkversus1/T,withTindegreesKelvin,a
straightlineisobtainedwithslopeE/R,leadingtoanEvalueof82.4kJ/mol.
(2) There are two reactors of equal volume available for your use: one a CSTR, the other a PFR.
1
The reaction is second order ( rA = kCA2 = kCA02(1 X)2), irreversible, and is carried out
isothermally
A B
There are three ways you can arrange your system:
(a) Reactors in series: CSTR followed by PFR
(b) Reactors in series: PFR followed by CSTR
(c) Reactors in parallel with half the feed rate going to each reactor after which the exit
streams are mixed.
(d) State which system will give the highest overall conversion and which system will
give the lowest overall conversion.
Solution
C A0
C A1 C A2
(a) X1 = 0.382, X2 = 0.618
(b) X1 = 0.5, X2 = 0.634
(c) CSTR: X1 = 0.5
PFR:
X1 = 2/3
X1,ave = 0.5(0.5 + 2/3) = 0.5833
(d) State which system will give the highest overall conversion and which system will give the
lowest overall conversion.
System 2: highest conversion.
System 3: lowest conversion
1Fogler,H.S.,ElementsofChemicalReactionEngineering,PrenticeHall,1999
(3)1 The exothermic reaction
A B+C
was carried out adiabatically and the following data recorded:
X 0 0.2 0.4 0.5 0.6 0.8 0.9
rA mol/Lmin 10 16.67 50 50 50 12.5 9.09
The entering molar flow rate of A was 300 mol/min.
(a) What are the PFR and CSTR volumes necessary to achieve 40% conversion?
(b) Over what range of conversions would the CSTR and PFR reactor volumes be identical?
(c) What conversion can be achieved in a 10.5 L CSTR?
(d) What conversion can be achieved if a 7.2 L PFR is followed in series by a 2.4 L CSTR?
(e) What conversion can be achieved if a 2.4 L CSTRR is followed in series by a 7.2 L PFR?
(f) Plot the conversion and rate of reaction as a function of PFR reactor volume up to a
volume of 10 L.
Solution
(300)(0.4)
CSTR: V= = 2.4 liters
50
PFR:
V = 7.2 liters
(b) Over what range of conversions would the CSTR and PFR reactor volumes be identical?
For a feed stream that enters the reaction with a previous conversion of 0.40 and leaves at any
conversion up to 0.60, the volumes of the PFR and CSTR will be identical because the rate is
constant over this conversion range
0.6 dX FA0 ( 0.6 0.4 )
VPFR = FA0
0.4 r
= = VCSTR
A rA
(c) Therefore 70% conversion can be achieved in a 10.5 L CSTR.
(d)60%conversioncan be achieved if a 7.2 L PFR is followed in series by a 2.4 L CSTR.
(d) What conversion can be achieved if a 2.4 L CSTR is followed in series by a 7.2 L PFR?
90% conversion can be achieved if a 2.4 L CSTR is followed in series by a 7.2 L PFR.
(f) Plot the conversion and rate of reaction as a function of PFR reactor volume up to a
volume of 10 L.
X=0.1:.1:.9;Ai=X;
ira=[.1 .08 .06 .04 .02 .02 .02 .05 .08 .11];
Area=0;
for i=1:9
Area=Area+.5*(ira(i)+ira(i+1))*.1;
Ai(i)=Area;
end
Vol=300*Ai;
figure(2)
plot(Vol,X);grid on
xlabel('V(liter)');ylabel('X')
rate=1.0./ira(2:10);
figure(3)
plot(Vol,rate);grid on
xlabel('V(liter)');ylabel('Reaction rate (mol/L*min)')
(4) Consider an ideal batch reactor with the irreversible homogeneous reaction
1
A + 2B 3C + D
This liquid phase reaction has the rate equation
rA = kCA2CB CD-1
The reaction rate constant is k = 1.5 L/molhr at 350oK. The activation energy of the reaction is
100 kJ/mol. The initial concentrations are: CA0 = 2.0 mol/L, CB0 = 4.0 mol/L, CC0 = 0 mol/L, and
CD0 = 1.0 mol/L. We will neglect any reaction that takes place while the initial charge is being
added to the reactor, and while the reactor and contents are being heated to reaction temperature.
(a) How much time is required for the concentration of A to reach 0.10 mol/L if the reactor
run isothermally at 350oK? What is the concentration of C at this time?
(b) The reactor will be run isothermally at 350 oK. The concentration of A in the final product
must be less than 0.20 mol/L, and the molecular weight of C is 125. An average of 10
hours is required between the batches in order to empty and clean the reactor, and prepare
for the next batch. How large must the reactor be in order to produce 200,000 kg of C
annually (with 8000 hours per year of operation)?
(c) We want to produce 200,000 kg of C annually, with a final concentration of A of 0.20
mol/L or less. The only reactor available has a working volume of 1400 L. At what
temperature does the reactor have to be operated, if it is operated isothermally? Once
again, an average of 10 hours is required between batches to empty and clean the reactor,
and to prepare for the next batch.
Solution
(a)TimerequiredfortheconcentrationofAtoreach0.10mol/L.
ThefractionalconversionofreactantAisdefinedas
X=(NA0NA)/NA0
ThereforethenumberofmolesofAatanytime,t,isgivenby
NA=NA0(1X)
Wenowcreateastoichiometrictableforthisbatchsystem(A+2B3C+D).
Species Initialnumberofmoles,t=0 Numberofmolesatt=t
A NA0 NA=NA0(1X)
B NB0 NB=NB02NA0X
C 0 NC=3NA0X
D ND0 ND=ND0+NA0X
Total NT0=NA0+NB0+ND0 NT=NT0+NA0X
Forliquidphasereaction,wecanassumethevolume V [Link]
secondandthirdcolumnsoftheabovetablebyVyields
1Roberts,G.W.,ChemicalReactionsandChemicalReactors,Wiley,2006
Species Initialnumberofmoles,t=0 Numberofmolesatt=t
A CA0 CA=CA0(1X)
B CB0 CB=CB02CA0X
C 0 CC=3CA0X
D CD0 CD=CD0+CA0X
Total CT0=CA0+CB0+CD0 CT=CT0+CA0X
MakingamolebalanceforspeciesAyields
dN A
=rAV
dt
SinceNA=NA0(1X),wehave
dX
NA0 =rAV
dt
Substitutingtherateofreactiongives
dX
CA0 =kCA2CBCD1
dt
1
C B0 C D0
dX 2 X X
C CA01 C A0
CA0 dt =kCA02(1X)2CA0 A0
dX
=kCA0(1X)2(42X)(1+X)1
dt
(1 X )dX
=2kCA0dt (E1)
(1 X ) 2 (2 X )
Usingpartialfractionweobtain
(1 X ) 3 2 3
= + 2 +
(1 X ) (2 X )
2
1 X (1 X ) 2 X
Equation(E1)canthenbeintegrated
2
2kCA0t=3ln(1X)+ 3ln(2X)2+3ln(2)
1 X
2 X 2
2kCA0t=3ln + 2+3ln(2)
1 X 1 X
WhenCA=0.1mol/L,X=0.9,wehave
(2)(1.5)(2)t=3ln(11)+18+3ln(2)=12.8858
t=2.1476hr
AtthistimetheconcentrationofCis
CC=3CA0X=3(2)(0.9)=5.4mol/L
(b)Volumeofthereactortoproduce200,000kgofCannuallyforCA=0.2mol/L
WhenCA=0.2mol/L,X=0.8,wehave
(2)(1.5)(2)t=3ln(6)+8+3ln(2)=4.7042
t=0.784hr
Thetotalbatchtimeis
ttot=10+0.784=10.784hr
Thenumberofbatches,nb,peryearis
nb=8000/10.784=742batches/year
TheconcentrationofCis
CC=3CA0X=3(2)(0.8)=4.8mol/L
TheannualproductionofCis
742(batches/year)4.8V(mol/batch)0.125(kg/mol)=200,000(kg/year)
Thevolumeoftherequiredreactoris
V=449L
(c)Operatingtemperatureofa1400Lreactortoproduce200,000kgofCannuallyforCA=0.2
mol/L
TheannualproductionofCis
2.41400(mol/batch)0.125(kg/mol)8000(hr/yr)/ttot(yr)=200,000(kg/year)
ttot=16.8hr
Thereactiontimeist=16.810=[Link]=0.2mol/L,X=0.8,wehave
2kCA0t=3ln(6)+8+3ln(2)=4.7042
Thereforek=4.7042/(226.8)=0.17295L/molhr
TheArrheniusrelationshipcanbeusedtocalculatetherequiredtemperature
E
k(T)=koexp
RT
E
k(350)=koexp
350 R
k (T ) E1 1 0.17295
=exp = =0.1153
k (350) R T 350 1.5
Takingthenaturallogofbothsidesyields
E1 1
=2.1602
R T 350
ForE=100,000J/molandR=8.314J/moloK
1 1 1
=1.796104 =3.0367103
T 350 T
T=329.3oK
(5) The elementary gas-phase reaction 3
(CH3)3COOH(CH3)3 C2H6 + 2CH3COCH3
is carried out isothermally in a flow reactor with no pressure drop. The specific reaction rate at
50oC is 10-4 min-1 and the activation energy is 85 kJ/mol. Pure di-tert-butyl peroxide enters the
reactor at 10 atm and 127oC and a molar flow rate of 4.0 mol/min. Calculate the reactor volume
to achieve 90% conversion in a CSTR and a PFR.
If this reaction is to be carried out at 10 atm and 127 oC in a batch mode with 95% conversion,
what reactor size would be required to process (4.0 mol/min 60 min/h 24 h/day) 3600 mol of
di-tert-butyl peroxide per day? You can assume a downtime of 6 hr between batches for cleaning
and feed preparation.
Assume that the reaction is reversible with equilibrium constant KC = 0.025 mol2/L6 and calculate
the equilibrium conversion and then repeat the calculation for the CSTR and the PFR to achieve
95% of the equilibrium conversion.
Solution
Solution
(CH3)3COOH(CH3)3C2H6+2CH3COCH3
AB2C
Wenowcreateastoichiometrictableforthisflowsystem.
Species Feedratetoreactor Effluentratefromreactor
A FA0 FA=FA0(1X)
B 0 FB=FA0X
C 0 FC=2FA0X
Total FT0=FA0 FT=FA0(1+2X)
FA 0 X
FortheCSTR:V= ,whererA=kCA
rA
Thetotalconcentrationatanypoint,CT,andattheentrance,CT0,tothereactoraregivenby
FT P FT 0 P0
CT= = andCT0= =
Q ZRT Q0 Z 0 RT0
Assumingnegligiblechangesinthecompressibilityfactor,Z,wehave
FT P0 T
Q=Q0
FT 0 P T0
3Fogler,H.S.,ElementsofChemicalReactionEngineering,PrenticeHall
FT
ForisothermalsystemwithnopressuredropQ=Q0 ,therefore
FT 0
FA FA0 (1 X ) (1 X )
CA= = =CA0
Q Q0 (1 2 X ) (1 2 X )
Thereactionrateconstantkat127oCcanbeevaluatedwiththegasconstantR=8.314J/moloK
=0.08205Latm/moloK.
E 1 1 85,000 1 1
k2=k1exp =104exp =0.0443min1
R T1 T2 8 .314 323 400
Theinitialditertbutylperoxide(A)concentrationat10atmand127oCisgivenby
PA0 10
CA0= = =0.305mol/L
RT ( 0.08205)( 400)
ThevolumeoftheCSTRisthen
FA0 X FA0 X (1 2 X ) (4.0)(0.95)(1 1.9)
V= = = =16,312L
kC A kC A0 (1 X ) (0.0443)(0.305)(0.05)
X dX
ForthePFR:V=FA0 0
rA
(1 X )
SinceCA=CA0 ,wehave
(1 2 X )
FA0 X 1 2X FA0
V= dX= 2 X 3 ln( X 1) 0X
kC A0 0 1 X kC A0
FA0 X 1 FA0
V= 2 X 3 ln( ) V= [2X3ln(1X)]
kC A0 1 kC A0
4.0
V= [20.953ln(1.95)]=2,098L
(0.0443)(0.305)
Forthebatchreactor,thereactiontimetoachieve95%conversionisgivenby
V dX
t=NA0 0
rAV
IfweassumeconstantvolumeV=V0thenthepressurewillincreaseforisothermalsystemand
N N A0 (1 X )
CA= A = =CA0(1X),wehave
V V0
V dX 1 X 1 1
t=CA0 0 = 1 X dX= k [ln(1X)]
rA k 0
1
t= [ln(1.95)]=67.6min
0.0443
Thetotalcycletimeisthentc=67.6+660=428min.Thereforewehave2460/4123runs
[Link]
NA0=3600/3=1200moles
Thebatchreactorvolumeisfinally
N A0 1200
V= = =3,935L
C A0 0.305
Calculatetheequilibriumconversion
Forthereaction
AB+2C
WehaverA=kfCAkbCBCC2
2
kf
C C
AtequilibriumrA=kfCAkbCBCC =0KC=
2
= B C =0.025
kb CA
( XC A0 )( 2 XC A0 ) 2
=0.025
(1 2 X ) 2 C A0 (1 X )
WithaninitialconcentrationCA0=0.305mol/L,wehave
X340.3052=0.025(1+2X)2(1X)
TheabovenonlinearequationcanbesolvedwiththeMatlabfunctionsolve
solve('x^3*4*.305^2-.025*(1+2*x)^2*(1-x)')
TheresultisX=Xeq=0.512.For95%oftheequilibriumconversionX=0.95Xeq=0.4864
FA 0 X
V=
rA
rA=kfCAkbCBCC2=kf(CACBCC2/KC)
(1 X ) kf X X2
rA=kfCA0 CA0 (2CA0)2
(1 2 X ) KC (1 2 X ) (1 2 X ) 2
C A0 1 4C A0 X 3
2
rA=kf (1 X )
(1 2 X )
K C (1 2 X ) 2
0.305 1 (4)(0.305) 2 (0.4864)3
rA=0.0443 (1
0.4864)
1 2 0.4864 .025 (1 2 0.4864) 2
rA=5.0351104mol/L
TheCSTRvolumeisthen
FA 0 X (4.0)(0.4864)
V= = =3,864L
rA 5.0351104
X dX C A0 1 4C A0 X 3
2
ForthePFR:V=FA0 0 whererA=kf (1 X )
rA (1 2 X )
K C (1 2 X ) 2
X dX
WecanusetheMatlabfunctionquadtonumericalintegrateFA0 0 .TheMatlabfunction
rA
FA 0
pfrvol iswrittenwithf= asfollows:
rA
function f=pfrvol(x)
k=.0443;cao=0.305;Kc=.025;
ra=k*cao*(1-x-(4*cao^2*x.^3)./(1+2*x).^2/Kc)./(1+2*x);
f=4.0./ra;
[Link]
0.4864
functionquadtointegrate fdX .
0
>> quad('pfrvol',0,0.4864)
ans =
5.6867e+002
ThereforethevolumeforthePFRis569L.
(6) Equilibrium with respect to the reaction
4
A(g) + B(g) = C(g)
will be studied by measuring the volume change accompany the reaction. The temperature and
pressure are held constant and the initial volume and the final volume of the reacting system are
recorded. Three tested were made and are summarized in the table. Has equilibrium been
established? If so what is the value of K?
Initial composition Volume (cm3)
P(mmHg) yA yB yC Initial Final
500 0.5 0.5 0 200 150
600 0.333 0.667 0 300 233
600 0 0 1.0 200 293
Solution
K = 4.5914
Ks are constant for the three cases: equilibrium has been established.
(7) Run Murder Mystery ([Link]
You will find the program Murder Mystery in the CHE 304 distribution folder, then
Kinetics, then click on [Link]. Turn in the last page of the program with performance
number.
4Kyle,B.G.,ChemicalandProcessThermodynamics,PrenticeHall,1999
