Department of Chemical Engineering Spring, 2009

University of California, Santa Barbara

CHE 140A Problem Set No. 5

Due Tuesday, May 5, 2009

Problem 1: Fogler, 3-13(g), p. 136

The formation of nitroanalyine (an important intermediate in dyes called ‘fast
orange’) is formed from the reaction of ortho-nitrochlorobenzene (ONCB) and
aqueous ammonia. (See Table 3-1 and Example 9-2.)

The liquid-phase reaction is first-order in both ONCB and ammonia with k = 0.0017
m3/kmol ⋅ min at 188 °C with Eact = 11,273 cal/mol. The initial entering concentrations
of ONCB and ammonia are 1.8 kmol/m3 and 6.6 kmol/m3, respectively.

(g) What would be the corresponding CSTR reactor volume at 25 °C to achieve 90%
conversion at 25 °C and at 288 °C for a molar feed rate of 2 mol/min:
at 25 °C? V = _______
at 288 °C? V = _______

Problem 2: Schmidt, 2.5, p. 82

We want to hydrolyze 500 lb per day of an ester at an initial concentration of 5 M (the
ester has a molecular weight of 120 g/mol) in aqueous basic solution in a batch process,
and we need product that is 99% hydrolyzed. In benchtop experiments in a flask, we find
that 50% of the ester hydrolyzes in 15 min for initial ester concentrations of either 1 M or
5 M. We also find that, when we react for 8 h, all of the ester has hydrolyzed. It takes 1 h
to empty the reactor and refill and heat it to start another batch.
(a) What size of reactor will we need?
(b) What size of reactor will we need if we can tolerate 90% conversion?

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Problem 3: Fogler, 3-16(b), p. 137
Calculate the equilibrium conversion and concentrations for the following reaction:
(b) The gas-phase reaction
⎯⎯
→ 3C
A ←⎯
⎯
carried out in a flow reactor with no pressure drop. Pure A enters at a temperature of 400 K
and 10 atm. At this temperature, KC = 0.25 (dm3/mol)2.

Problem 4: Hill, 4.9, p. 122

Two alternative mechanisms have been proposed to explain the formation of gaseous
phosgene (COCl2) from carbon monoxide and chorine and the decomposition of
phosgene into these species:
Mechanism I:
k1
ZZZ
YZZ X
Cl2 k−1 Z 2Cl
k2
ZZZ
YZZ X
Cl + CO k−2 Z COCl

COCl + Cl2 ⎯⎯
k3
→ COCl2 + Cl
Cl + COCl2 ⎯⎯→ COCl + Cl2
k4

Mechanism II:
k1
ZZZ
YZZ X
Cl2 k−1 Z 2Cl
k5
ZZZ
YZZ X
Cl + Cl2 k−5 Z Cl3

Cl3 + CO ⎯⎯
k6
→ COCl2 + Cl
Cl + COCl2 ⎯⎯→ Cl3 + CO
k7

Derive reaction rate expressions for d(COCl2)/dt for both mechanisms. Can simple
kinetic measurements be used to determine which mechanism is ‘correct’? If not, what
might be done experimentally to determine which mechanism is preferred?

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Problem 5: Fogler, 4-5(a-e), p. 236
The liquid-phase reaction
A + B ⎯⎯
→C
follows an elementary rate law and is carried out isothermally in a flow system. The
concentrations of the A and B feed streams are 2 M before mixing. The volumetric
flow rate of each stream is 5 dm3/min, and the entering temperature is 300 K. The
streams are mixed immediately before entering.
Two reactors are available. One is a gray 200.0-dm3 CSTR that can be heated to 77 °C
or cooled to 0 °C, and the other is a white 800.0-dm3 PFR operated at 300 K that
cannot be heated or cooled, but can be painted red or black. Note k = 0.07
dm3/mol ⋅ min at 300 K and Eact = 20 kcal/mol.
(a) Which reactor and what conditions do you recommend? Explain the reason for
your choice (e.g., color, cost, space available, weather conditions). Back up your
reasoning with the appropriate calculations.
(b) How long would it take to achieve 90% conversion in a 200-dm3 batch reactor
with CA0 = C B0 = 1 M after mixing at a temperature of 77 °C?
(c) What would your answer to part (b) be if the reactor were cooled to 0 °C?
(d) What conversion would be obtained if the CSTR and PFR were operated at 300 K
and connected in series? In parallel with 5 mol/min to each?
(e) Keeping Table 4-1 in mind, what batch reactor volume would be necessary to
process the same amount of species A per day as the flow reactors while achieving
90% conversion? Referring to Table 1-1, estimate the cost of the batch reactor.