ChE 471

Fall 2009
Exam 1
Closed Book, Closed Notes, One crib sheet allowed

Problem 1
The decomposition of acetaldehyde ( CH 3CHO CH 4 CO ) is assumed to follow a multi-step
mechanism listed below.
CH 3CHO
CH 3 CH 3CHO

CH 3CO
k4

CH
3 CHO

(1)

CH 3
CO CH 4

k2

2CH 3

k1

k3

CH

(2)

CO

(3)

C2 H 6

(4)

Is the above mechanism compatible with the overall stoichiometry? ( Remember that CHO* and C2H6 are
present in infinitesimal quantities and can be neglected; and you can ignore their rates also since they do
not participate in a cyclic part of the mechanism).
a) Is this a catalytic or non-catalytic mechanism?
b) On the basis of the above mechanism, derive a rate expression for the rate of disappearance of
acetaldehyde. (Recall that propagation rate dominates over initiation rate)
c) Can the rate be expressed in terms of a power law model? What is the apparent order of
reaction.
d) What is the overall activation energy in terms of activation energies of the rate constants for
the individual steps? { For each step i=1,2, 3, 4 ki k0 e
i

Ei

RT

Hint: Use the PSSA and set the rate of the two active intermediates that participate in the
propagation steps (2) and (3) to be zero and remember that the rates of propagation steps (steps 2
and 3) are many times larger than those of the initiation step (1) or termination step (4), so the
latter ones can be neglected when compared to propagation step rates or their sums. However,
termination or initiation rates cannot be neglected when compared to the difference in rates of the
propagation steps as such difference could also be small.
Problem 2
You run a laboratory continuous flow stirred tank reactor (CSTR) in order to
determine the rate of reaction for an irreversible liquid phase reaction A products. The
volume of your CSTR is V = 1L and it is always full of liquid. The feed concentration of A is
always CAo = 1 (mol/L). You vary the volumetric flow rate Q (L/s) and, at each flow rate, you
determine the steady state concentration of A, CA, in the exit stream. The flow rate- exit
concentration pairs obtained are reported in the table below. All runs were performed at the
same constant temperature.
Data ( see back of page)

Q (L/s)____ 0.384
CA (mol A/L) 0.9

0.143
0.8

0.0348
0.6

0.0176
0.5

0.00210
0.25

You are told that the reaction can be represented by a power law form. From the above
information find:
a) the order of this irreversible reaction, and
b) the rate constant.
Clearly illustrate your approach.
Problem 3
A first order irreversible, gas phase decomposition A 2.5 P is carried out in a
constant volume, isothermal, batch reactor. The initial gas mixture contains 50%
inerts and 50% reactant A. In 10 minutes of reaction time the pressure in the
reactor increases by 60%.
a)
Find the rate constant.
b)
If we repeated the experiment with pure A what batch reaction time is
needed to achieve 99% conversion of A?
c)
Starting with pure A what space time is needed in a constant pressure,
isothermal plug flow reactor to achieve 99% conversion?
d)
What is the mean residence time in the plug flow reactor of part c)?
Problem 4
The reaction, A P, is autocatalytic with rate form given as:
R A 2C AC P ( mol / L min)

We want to design a reactor to make FP = 100 (mol P/min) at 90% conversion of A of the feed
that contains CA0= 1 (mol/L).
We want to minimize the total reactor volume needed to achieve the above production rate at the
conversion specified above. (To gain insight, plot the rate (or its reciprocal) as a function of
conversion in the conversion range from 0 to 0.9)
a) What reactor type or reactor combinations do you recommend and why?
b) What is the needed total reactor volume.
The production rate is

FP = FAo xAf

where xAf is the exit (or final) conversion.