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Assignment # 2 (Subject: Ch.E.

303 CRE) (Due Date: 21Dec 2015)


Solve the following five numerical Problems
1. Leyes and Othmer studied the formation of butyl acetate in a batch operated reactor at 100C, with
sulfuric acid as catalyst. The original feed contained 4.97moles butanol/mole acetic acid, and the
catalyst concentration was 0.032% by weight H 2SO4. The following rate equation was found to
correlate the data when an excess of butanol was used:

r A=k [ A ]2
Where [A] is the concentration of acetic acid, in g-mole per milliliter, and r is the rate of reaction, in gmole of acid disappearing per milliliter per minute. For a ratio of butanol to acid of 4.97 and sulfuric acid
concentration of 0.032% by weight, the reaction velocity constant was
k = 17.4 ml/(gmol)(min)
Densities of mixtures of acetic acid, butanol, and butyl acetate are not known. Reported densities for each
of the three compounds at 100C were
Acetic acid = 0.958 g/ml
Butanol = 0.742
Butyl Acetate = 0.796
Although the density of the reaction mixture varies with conversion, the excess of butanol reduces the
magnitude of the change. Therefore, as an approximation, the density of the mixture was assumed
constant and equal to 0.75b/ml.
a. Calculate the time required to obtain a conversion of 50%
b. Determine the size of reactor and original mass of reactants that must be charged to the reactor in
order to produce ester at the average rate of 100lb/hr. only one reactant will be used, and this unit
will be shut down 30min between batches for the removal of product, cleaning and startup.
Assume that the reaction mixture is well mixed.
2. In the presence of water and hydro-chloric acid (as a catalyst) the rate of esterification, in gmol/(lit)
(min), of acetic acid and ethyl alcohol at 100C is given by

r 2=k [ H ] [OH ]

k = 4.76 x 10-4 lit/(gmol)(min)

The rate of the reverse reaction, the hydrolysis of the ester in the same concentration of catalyst, is

r '2=k [ E ] [W ]

k = 1.63 x 10-4 lit/(gmol)(min)

CH3COOH + C2H5OH CH3COOC2H5 + H2O


The reaction is reversible with k as forward rate constant and k as reverse rate constant.
a. A reactor is charged with 100 gallon of an aqueous solution containing 200 lb of acetic acid, 400
lb of ethyl alcohol, and the same concentration of HCl as used to obtain the reaction velocity
constants. What will be the conversion of acetic acid to ester after 120 min of reaction time? The
density may be assumed constant and equal to 8.7 lb/gal; neglect the water vaporized in the
reactor.
b. What is the equilibrium conversion?
3. The homogeneous reaction between sulfur vapors and methane has been studied in a small silicatube reactor of 35.2ml volume. In a particular run at 600C and 1atm pressure the measured quantity
of carbon disulfide produced in a 10min run was 0.10g. Assume that all the sulfur present is the

molecular species S2. The sulfur vapors S (considered as S2) flow rate was 0.237gmol/hr in a steady
state run.
a. What is the rate of reaction, expressed in g moles of carbon disulfide produced/(hr)(ml of reactor
volume)?
b. The rate at 600C may be expressed by the second order equation

r=k p CH 4 p S 2
Where p is the partial pressure, in atmosphere. Use the rate determined in (a) and this form of rate
equation to calculate the specific rate constant in units of g mol/(ml)(atm 2)(hr). The methane flow rate
was 0.119 g mol/hr, and the H2S and CS2 concentration in the reactants were zero.
c. Also compute the value of k without making the assumption that the rate is constant and that
average values of the partial pressure may be used; that is, consider the equipment to operate as
an integral, rather than a differential, reactor. Compare the results and comment on the suitability
of apparatus as a differential reactor.
4. Consider the following reaction for your calculation
CH4 + 2S2 CS2 + 2H2S
A flow reactor consisting of a 1-in. stainless steel pipe 6 in. long and packed with inert rock salt is used to
study the noncatalytic homogeneous reaction.

4
S +CH 4 2 H 2 S+CS2
b b
The measurements are carried out at atmospheric pressure in the vapor phase at 600C. from available data
on the rate of dissociation of sulfur species, it is reasonable to assume that the reactions

S8 4 S2
S 6 3 S2
are very fast with respect to the combination of sulfur vapor with methane. Accordingly, assume that S 8,
S6 and S2 are in equilibrium. The void volume, measured by benzene displacement, was 35.2ml. The
conversion x of methane to carbon disulfide was measured for various flowrates and initial reactants
ratios, and the results are shown in the following table. S 2 represents the total amount of sulfur vapor
present, expressed as S2. Hence

S 2=N S 2+3 N S 6 +4 N S 6
Where the N values are the number of moles of each sulfur species.
Run

Flow rate (g mol/hr)


CH4
S2
CS2

Reactant ratio, (moles S2 / moles CH4)

Conversion

55
0.02975
0.0595
0.0079
2
0.268
58
0.0595
0.119
0.0086
2
0.144
57
0.119
0.238
0.0078
2
0.066
59
0.119
0.238
0.0072
2
0.060
56
0.238
0.476
0.0059
2
0.025
75
0.0595
0.119
0.0079
2
0.133
76
0.02975
0.0595
0.0080
2
0.269
77
0.119
0.238
0.0069
2
0.058
78
0.0893
0.0893
0.0087
1
0.0975
79
0.119
0.0595
0.0096
0.5
0.0807
Assuming, first, that the only species of sulfur exists is S 2, test the assumptions of first and second order
rate equations with experimental data.
Repeat part (a) with the assumptions that S 2, S6, and S8, are in equilibrium but that only S 2 reacts with
CH4.
Using second order rate expression, determine which assumption regarding the reactive sulfur species
best fits the experimental data.
5. Eldridge and Piret have investigated the hydrolysis of acetic anhydride in stirred-tank flow reactors
of about 1800cm3 volumes at temperatures from 15 to 40C. Their experimental results for several
volumetric flow rates are shown in the following table. Independent determination by these
investigations from other experiments in batch-operated reactors resulted in the following first order
equations for the rate of reaction in g moles/(cm3)(min):

r=

0.0567C at 10 C
0.0806C at 15 C
0.1580C at 25 C
0.380 C at 40 C

Where C is the concentration of acetic anhydride, in g moles/(cm3).


Entering anhydride concentration,
moles/cm3
2.1 x 10-4
1.4 x 10-4
1.37 x 10-4
1.08 x 10-4
0.52 x 10-4
0.95 x 10-4
0.925 x 10-4
1.87 x 10-4
2.02 x 10-4

Volumetric feed rate,


cm3/min
378
582
395
555
490
575
540
500
88.5

% hydrolysis of
anhydride
25.8
33.1
40.8
15.3
16.4
55
55.7
58.3
88.2

Temperature
(C)
15
25
25
10
10
40
40
40
40

For each run compute the % of hydrolysis and compare it with observed values in the table. In all cases
feed temperature is the same as the temperature of the reaction mixture. Since the concentrations are low
the density of the solution may be assumed constant.

The following reaction can be considered for calculation


(CH3CO)2O + H2O 2CH3COOH