Chemical and Biomolecular Engineering 142 Chemical Kinetics and Reaction

Engineering
Homework #5
Due Tuesday Oct 4th at 11am

1. The elementary, gas-phase, reversible reaction

A B + 2C
occurs in an isothermal, isobaric, steady-state membrane PFR with a forward reaction rate of
k1 and an overall equilibrium constant KC. The reactor is tubular with a constant cross-
sectional area. Pure A enters the reactor, and B diffuses out through the membrane.
Unfortunately, a small amount of the reactant A also diffuses through the membrane. The rate
of diffusion of species I through the membrane at any given point along the reactor is equal to
the constant i multiplied by the local concentration of species i. Plot the flow rates of A, B,
and C along the length of the reactor (from z = 0 to z = Lreactor).

Additional information:
k1 = 10 min-1
KC = 0.01 mol2/dm6
A = 1 min-1
B = 40 min-1
FA0 = 100 mol/min
0 = 100 dm3/min
Areactor = 2 dm2
Lreactor = 10 dm

2. Tests for decomposing nitrogen oxides in an automobile exhaust stream were performed on a
small differential flow reactor at steady state. In one series of the tests, a nitrogen stream
containing various concentrations of NO2 was fed to the reactor, and kinetic data thus
obtained are shown below. The figure shows the fractional decomposition of NO2 fed versus
the ratio of reactor volume V (in cm3) to the NO2 feed rate FNO2,0 (g mol/h) at different feed
concentrations of NO2 (in parts per million by weight).
 a) What does it mean to have a differential flow reactor? Why do you think the
equations describing the system may simplify to an algebraic form as in the case of a
CSTR, rather than the more complex differential equations typically used to describe
a PFR?
b) Estimate the dependence of the rate equation on the concentration of NO2 (the order
of the reaction in NO2). Please show your work.
c) Estimate the activation energy of the reaction using the data above. Show your work.

3. The irreversible, first-order (with respect to A) gas-phase reaction A B is carried out

isothermally in a fluidized catalytic CSTR operating at steady state and containing 50 kg
catalyst. Currently 50% conversion is released for pure A entering at a pressure of 20 atm.
There is virtually no pressure drop in the CSTR. It is proposed to put a PBR containing the
same catalyst weight directly after the CSTR, in series. The pressure drop parameter for the
PBR () is 0.018 kg-1. Please see equation 5-29 in your book for the meaning of . The particle
size is 0.2 mm, the bed porosity is 40%, and the viscosity is the same as that of air at 200C.
What will the overall conversion of the new system be?

4. The following liquid phase reaction is very thermodynamically limited with the reverse
reaction being much more favorable than the forward.
A+ B 2C
The rate law for this reaction can be written in the following manner:
2
= [ ]

The equilibrium constant K has a value of 0.05 and k has a value of 0.013 L/(molmin).
a. If a reaction vessel initially contains 10 mol/L of both A and B, what is the equilibrium
conversion?
b. The reaction is conducted in a batch reactor. The reactor volume is 12 L, and the initial
concentrations of A and B in the reactor are 10 mol/L and 20 mol/L, respectively.
Develop a set of algebraic and/or differential equations that completely describe the
system. Plot the concentration of all three species on the same plot for a time period of
5 minutes. What is the final concentration of each species?
c. You notice that C is very volatile compared to the other species and want to take
advantage of this. You go back to the batch design and now lower the pressure so that C
evaporates more readily. Assume that all of the C that is formed vaporizes and is
removed immediately via reactive distillation, using an inert sweep gas. Develop a set
of algebraic and differential equations to completely describe the system. Plot the
concentration of all three species on the same plot for a time period of 5 minutes. What
is the final concentration of each species? Use the values from (b) and the knowledge
that the molecular weight of C is 35 g/mol, and the liquid density is 1000 g/L
d. Now consider a scenario in which component C (MW 35 g/mol), the only volatile
component, is collected as distillate in a reactive distillation process where its partial
 pressure is maintained at PC = 5 atm using a back-pressure regulator. Given that it is the
only component in the headspace, its concentration CC in the liquid phase is governed
by Henrys law CC = HC*PC, where HC is the Henrys Law constant with value 5x10-2
mol/(L*atm). The density of the liquid phase is 1000 g/L. Plot concentration of each
species for this reactive distillation case.
e. Plot the conversion as a function of time for B, C and D on the same chart. Comment
on your results in no more than two sentences using Le Chateliers principle.