ChE 345 REACTION ENGINEERING I

Problems - II

1. Kinetics data at 25 °C for the conversion of tert-butyl brom.ide to tert-butyl alcohol in a

solvent of 90% acetone and 10% ·water are given in the following table. The reaction is
t
(CH3 \ C Br + H2 O ➔ (CH3 COH + HBr what rate equation is consistem with the data?
1
Time, h
1
Concentration of (CHJ3 CBr, nıol lliter
o 1 0.1039
.)-, )
,., 1 -
1 0.0896
4.10 0.0859
6.20 0.0776
8.20 . 0.0701 1
i

10.00 0.0639 1

13.5 0.0529
18.3 0.0353
26.0 0.0270
30.8 0.0207

2. In order to study the photo chemical decay of aqueous brom.ine in bright sunlight, a small
quantily of liquid bromine was dissolved in water contained in a glass battery jar and placed
in direct sunlight. Th:e follmving data were obtained
/' 1O 20 30 40 50 60
2.45 1.74 1.23 0.88 0.62 0.44
Temperature: 25 °C
Determine whether the reaction rate is zero, first or second order in brom.ine and calculate the
reaction rate constant.

3. The liquid-phase reaction between trirnethylamine and n-propyl bromide was studied by
Winkler and Hinshelwood by irnmersing sealed glass tubes containing the reactants in a
constant-temperature batlı. The results at 139.4 °C are shown in Table. Initial solutions of
trimethylamine and n-propyl bromide in benzene, 0.2-molal, were mixed, sealed in glass
tubes,

Run t, min Conversion

1 13 11.2 ·-
2 ''.d.'
.) 25.7
3 59 36.7
4 1 120 55.2

and placed in the constant-temperature batlı. After various time intervals the· tubes were
removed and cooled to stop the reaction, and the contents were analyzed. T.ı-ıe analysis
depends on the fact that the prodL1 ct, a quatemary anınıoniunı salt, is completely ionized.
Hence the concentration of bromide ions can be estimated by titrn.tion.
From this information determine the fırst-order and second-order specific rates, k1 arıd k2
assuming that the reaction is irreversible over the conversion range covered by tbe data. Use
both the integration and tbe differential method, and compare the results. \Vlıiclı rate eqn3.ti:::ır:,
best fits the exoerimental data?
 4. The follovying data are obtained 2-t O °Cin a constant volume batch reactor using pure gas A.

Time, min. /O 2 4 6 8 10 j 12 1-ı4 i

,.Partial pressure of A. Mm Hg 760 1 570 450 390 320 275 1240 / 215 1
Find a rate equation which satisfactorily represents the following decomposition reaction.
A --- 2.5R

5. Dillon has studied the reaction betıveen ethylene bromide an potassium iodide uı 99°/4
methanol.
C 2 H 4 Br2 + 3KJ � C 2 H 4 ..ı.. 2K Br + KI 3
Given the data in the table below, detennine the second order reaction rate constant.
Use of a graphical integral method for determining the rate constant for a second order
reaction.
Data
Temperature 59.72 ° C,
Irıitial KI concentration is = 0.1531 kmole/m3
Initial C2� Br2 concentration is 0.02864 kmole/m3

time, t (ksec) Fraction dibrornide reacted

29.7 0.2863
40.5 0.3630
47.7 0.4099
..
.. 55.8 0.4572
62.1 0.4890
72.9 0.5396
83.7 0.5795

6. Given the following data, deterrnine the order of the reaction and specific rate constant.
A -? �rtıdı..ıd-s P0 (atın) 0.430 0.788 1.452 1.747
t 112 (sec) 860 470 255 212
Co,'1� rcwı\- vo\\J.i'Yıe. �a.t-c..\.ı 1<.e.o.c\-or f0ı-e.. A ı's us..e.A.
)
7. Suppose that a gaseous reaction between A and B is studied kinetically by making isothermal
measurements of the half-life period for several initial compositions of reactants. The results
for each of four different initial conditions are as follows:
PA0,mmHg 500 ! 125 250 250 1
P Bo, mmHg 10 1 15 10 20
(t1/2)B, rnin 80 ! 213 160 80
If the rate is first order witb respect to component A and second order with respect to B, what
is the nuınerical va]ue of the speci:fic reaction rate? ·

A+2B➔R
dCA
-rA =---=kCA CB
2
dt
Integrated form of the above rate expression:

(2CA - CB )1 cB -CB )
0 . 0 \ 0
CA, C3 = (') ("" _ C 2 iri .r, • Jı,r C
+ ln--- ı_ �, ,, 11,1. ,o, ı-1 = �-= 2
CBo CB CA C. B, \ "" �, ) � C. Ao
8. Jhe following_cl._ ata refer to a reaction that is believed to be of the second order in the forward
direction and of the first order in reverse. Initial concentrations of the two reactants were each
· L2 gmole/liter and there was no product initially. What is the equilibrium constant?"'Fındtne
. specific reaction rate constants.

9. In the dimerization of butadiene ( 2B ➔ D ), measurements were made of the total pressure as

the reaction proceeded at 326° C and constant volume. A rate equation of the following form
will be assumed.
_dp=kPn
dt where P is the pa...rtial pressure of butadiene and the constants k and n will be found
by several methods. Total pressure measured at different times are given below.

10. The thermal decomposition of dimethyl ether in the gas phase was studies by measuring the
increase in pressure in a constant volume reaction vessel. Initial pressure is 468 mmHg and
the following data were obtained:

Assuming that önly ether was present initially and that the reaction
. (CH 3) 2O➔CH4+H2+CO' determıne · · ·
· fior the decomposıtıon. · the
ıs a rate equatıon un..
vı• ııat ıs
numerical value of the specific reaction rate?

3
11 ; Phthalic anyhydride (PAN) is produced by the partial oxidation of naphthalene in a fıxed-bed
· reactor with a V2 0 5 catalyst:

Set up a stoichiometric table for this reaction for an initial mixture of 3.5% naphthalene and
96.5% air (mo1%), and use this tablet o develop the relations listed below. P0 =lO atm. T0 =
500K

a) For an isotherrnal flow reactor in which there is no pressure drop, deterrnine each of the
following as a function of the conversion of naphthalene, XN

(1) The partial pressures of 02 and CO2

(2) The concentrations of 02 and naphthalene
(3) The volumetric flow rate v

b) Repeat part (a) when a pressure drop occurs in the reactor

c) If the reaction just happened to be first order in 02 and second order in naphthalene with a
value of kN of O.Ol mol2/dm6 .s, write an equation for -rN solely as a function of
conversion for parts- (a) aırd (b)

p T
Remember v=v0 (1 + c:x) - - 0

p Ta
l.atm
R = 0.082
molK

12., The gas-phase reaction

2 A+ 4B--. 2 C
which is first order in A and first order in B is to be carried out isotherrnally in a plug flow
reactor. The entering·volumetric flow rate is 2.5 dm3 imin and the feed is equimolar in A
and B. The entering temperature and pressure are 727 °C and 10 atm respectively. The
specific reaction rate at this temperature is 4 dm3 /gmol min and the activation energy is 15
000 cal/gmol. Pressure drop can be neglected.
Prepare the stoichiometric table.

a) What is the volumetric flow rate when the conversion of A is 25 %?

b) What is the concentration of A at the entrance to the reactor?
c) What is the rate of reaction at the entrance to the reactor (i. e. X=0)?
d) What is the rate of reaction when the conversion of A is 40%?
e) What is the concentration of A at 40% conversion of A ?
f) What is the value of the specific reaction rate at 1227 °C?

PO ( ) T
volumetric flow rate: v=vo -l+c:x-
p To
a) Evaluate the activation energy using these units
b) Transform the rate expressions into concentration units and then evaluate the activation
energy.
13 � A solution of an ester R COOR' is to be hydrolysed with an excess of caustic soda
solution. Two stirrcd tan.ks of equal size will be used. The ester and caustic soda
solutions flow into the first tank with a stream at a rate of 7 L/sec and with
concentrations of l 0-2 and l 0- 1 mol/L, respectively. The exit concentration of ester
from thc fırst to.nk is 0.004 mol/L. The reaction R COOR' + NaOH -> R COO Na+
R' OH is sccond order with a rate constant of 0.111 L/mol.s at the temperature at
which both tanks operatc.
a) Dcterminc thc conversions in fırst and second tanks
b) Calculatc the exit concentrations of ester and soda from the second tank and
also total conversion.

14-It is dcsired to model how long onc must wait to drive after having tall martini. In
USA, the legal intoxication limit is 1.0g of ethanol per !iter of body fluid. The
ingestion of ethanol into thc bloodstream and subsequent elimination can be modeled
as a serics. rcaction. Thc rate of absorption from the gastrointestinal tract into the
bloodstrcam and body is a fırst order reaction with a specific reaction rate constant of
J O h- 1 • Thc ratc at which ethanol is broken down in the bloodstream is limited by
rcgcnı.;ration ofa coenzymc. Consequently, the process may be modeled as a zero­
ordcr rcaction with a specific rcaction ratc of 0.192 g/h L of body fluid. How long
would a pcrson have to wait in the United States if they drank two· tall martinis
immcdiatcly aftcr arriving at a party?
Hint: Basc cthanol concentration on thc volumc of body fluid. Plot the concentration
of ethanol in thc blood as a funetion of time. The reaction can be modeled as
A-> B-> C
ı\dditional information:
Ethanol in a tali martini: 40g
Volumc of body fluid: 40L
· 15� A stage in thc production of propionic acid, C2HsCOOH, is the acidifıcation ofa water
solution of the sodium salt according to the reaction:

C2HsCOONa + HCI ► C2HsCOOH + NaCI

A+B --► C+D

a) The reaction rate may be present by a ·second order irreversible equation, fırst order
with respect to A and fırşt order with respect to B. Laboratory data on the rate of
reaction are given in the table. The temperature is 50 °C and the initial moles of
HCI and C2HsCOONa are the same. Using the given data, determine the specifıc ·
reaction rate.

b) Determine the size ofa batch reactor to produce propionic acid at an average rate of
12 ton/day, 20 minutes is required for charging the reactor and for cooling and
re�oving the products. Fin� conversion is to be 75% of the sodium propionate.
.
Inıtıal charge to the reactor wıll contaın 0.35 kmol ofC2H 5 COONa and 0.50 kmol of
HCI per !iter.

MA = 96kg/lanol, 1\ıfe = 36.5kg / kmol, Mr =74kf:lkmol

 .

16.

o o
il
· e- 0-C.�E; ©(C-0-C..H,
il

� CıHç Ori H.so,

©r C-OE
. C-O-C.1H9
il il
o o
n-buta.--ıol DBP
to
a.) Determiı...;,e tlıc ex.i"' conYersion in thc: av:ı.il::ı.ble 3 78_5 füer re:ıct r if you ,yere
produce 1814 tonf..,-e:rr.
· :ı..-y to
b) How m2.ny 3 785 liter re:ıctors oper:::.ted at 3 S "C in b:ıtch n9dc: would be neces _
% conversıon of
meet tlıe required production of ı S P ton in a 3 O day period for 8_
1-IBP. The required. time for fi.1liııg and oföer operntions is 3h.

}vf�P = 278 ;: -o L
-er

;:
· 17 � 1 Tne A <=>Bre\ ersible reaction t.2...1<:es place in a reactor system given below:
.c-1

CAo = 0.5 hnol l m 3 • The residence time in the CSTR is 6 times the residence time in
PFR The reaction reaclıes a conversion wb.ich is 30% of the equilibriurn conversion in
the CSTR. Cclculate the conversion at tlıe exit of tlıe PFR.

18- For the reactions in series A � R � S k1 = k1 Find the ma-,,:in11m1

concentration of R and when it is reached. If k1 =k2 =0.35/ı-ı �md
· CAo = 4mole ! !iter, find

a. The ma-,,:imum concentration of R.

b. When is it reached?
c. How long does it take ro convert 40% of A?
 19.

/ o"-
Hı -cr-ı� +Hıo

ı\ + B c:ıı:ıl)•SI ► C

b) For thc ::ı.bovc reactor \v:ith the sume initial concentration of ethylene oxide
c;ılcub'tc tlıc volume rcquired for 80% conversion of ethylene oxide.
Production rate of ethylcne gylcol is 100 ton per year. Mole cular ,veight of
cthylenc gylcol is 62 kg/lm10l. 1 year = 365 days and a time of 60 min is
rcquircd bctwccn b:ıtches for discharging, cleaning and recharging.

20. The rcvcrsible first order reaction of the form A .:;:::, B takes place in a constant
volume b::ttch rcactor operating at constant temperatur e. The initial
concentrations of A and B a.re 0.60 molc/Iiter and O. 15 mole/liter, respectiv ely. It
re quires 20 minutcs for ::t conversion of 25 % of A. Th e equil ibrium conversion of
ı-\ is S5 %. Calcul::ıtc the forwa.rd and reverse rate constants and the time re quired
to obtain a conversion of 50 %.

21. _The element::ı.ry �rrevcrsible aqueous-ph�se reaction A+B .-., R+S is carried out
ısotlıerma.lly as ıollows. Equal volumetnc flow rates of two liquid streams are
introduced into a 4-liter mix .ing tank. üne stream contains 0.020 mol A/liter, the
othcr 1.400 mal B/liter. The mixed stream is then passed through a 16-liter plua
flow rc:.ıctor, \Ve find some R is formed in the mixing tank, its concentration bein�
0.002 mol/liter. Assuming that the mixing tank acts as a mi.--:: ed flow reactor 1 find
the concentration of R at tlıe ex.it of the plug flow reactor as well as the fraction of
initial A th::ıt has been converted in the system.

.
Hınt :
. c·_,,
O,Q_Q
ınce -·-' = -- = -
1
�
C 0 l .➔ 70
:\ssume that C r,,, :::: constant and reaction is first order \\ith respect to A.