10.

37 Spring 2007 Homework 1

Due noon Wednesday, Feb. 14.

Problem 1. Airbags contain a mixture of NaN3, NaNO3, and SiO2. When the vehicle is in
a crash, the following reactions are initiated:

2 NaN3 Æ 2 Na + 3 N2

10 Na + 2 NaNO3 Æ N2 + 6 Na2O

Na2O + 10 SiO2 Æ glass

a) If 150 g of NaN3 are used in an airbag, how many grams of NaNO3 and SiO2 must be
included so that all of the sodium in the system can be safely sequestered as glass? Note
the sodium-containing compounds NaN3, Na, and Na2O are all dangerous and toxic.

b) The most important species for airbag performance in a crash are NaN3 and N2, so
there are two obvious definitions of conversion:

XNaN3 = (moles NaN3 reacted)/(initial moles NaN3)

and

XN2 = (moles of N2)/(total moles of N2 when all reactions are completed).

What units do XNaN3 and XN2 have? Does XNaN3 equal XN2? If not, how different could
they be?

There are three other related quantities, ξ1, ξ2, and ξ3, the extents of reactions 1,2, and 3.
Note that each ξ has units of moles. Write algebraic equations for each X in terms of the
ξ‘s.

c) Suppose that reaction 1 has a rate expression r1=k1/V (this reaction proceeds at a

steady rate as a reaction front moves through the solid NaN3), reaction 2 has a rate

expression r2=k2[Na][NaNO3], and reaction 3 has a rate expression r3=k3[Na2O]/V.

By the convention used in this course, all the r’s have units of moles/second/liter. Write
rN2, the rate of production of N2 per unit volume, in terms of r1, r2, and r3.

Write the equations for rate of change of the number of moles, dni/dt, for all the chemical
species (i=N2, NaN3, Na, NaNO3, Na2O, SiO2, glass).

d) Of course the volume of the airbag, V, is dramatically changing during the course of
the reaction due to the creation of a gas, N2, inside the bag. If the bag can expand fast
enough to so that the pressure inside the bag is similar to the pressure outside the bag, by
the ideal gas law one would expect:

V = Vo + VN * nN2

Cite as: William Green, Jr., and K. Dane Wittrup, course materials for 10.37 Chemical and Biological Reaction
Engineering, Spring 2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology.
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 and under this condition the bag would expand depending on the rate at which gas is
created:

dV/dt = VN * dnN2/dt

where VN is the molar volume of a gas at atmospheric pressure (~22 liter/mole) and nN2 is
the number of moles of N2 in the airbag. The initial volume of the airbag Vo ~70 cm3.

However there is a physical limit on how fast the airbag can expand. When an airbag is
expanded by gas pressure, the radius of the bag cannot grow faster than the speed of
pressure fronts in the gas, approximately the speed of sound:

dR/dt < csound

csound ~ 300 m/s in air.

so there is an upper bound on how fast the airbag can grow; for a spherical airbag:

dV/dt = 4π R2 dR/dt
so dV/dt < 4π (3V/4π)2/3 csound = (36πV2)1/3csound

So a reasonable approach to model this numerically is

if (V<Vo + VN*nN2)
dV/dt = (36πV2)1/3csound
else
dV/dt = VN * dnN2/dt
endif

Using a numerical ODE solver in Matlab, solve the coupled system of differential
equations for the n’s and V. Take k1~103 moles/s, k2~104 liter/mole-s, k3~105 liter/s.
Make and turn in a plot of XN2 vs. time, ξ3 vs. time and volume vs. time for the first 10
milliseconds of operation. Also, make and turn in a plot of volume vs. time for just the
first 0.1 milliseconds of operation. Does the volume vs. time behavior make physical
sense? If not, go back and modify your Matlab program to fix the non-physical dV/dt
behavior.

Submit your Matlab program(s) to the 10.37 the course website.

Cite as: William Green, Jr., and K. Dane Wittrup, course materials for 10.37 Chemical and Biological Reaction
Engineering, Spring 2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology.
Downloaded on [DD Month YYYY].
 Problem 2. One of the students in this class recently measured the reaction of vinyl
radical (C2H3) with ethene (C2H4), a reaction important in flames, pyrolysis, and
polymerization reactors. Vinyl radical absorbs purple light, so the amount of light
absorbed is proportional to the concentration of the vinyl radical. In each experiment the
student measured the time variation in the amount of purple light passing through his
constant volume sample using a photodetector. The voltage signal from the photodetector
is linearly related to the absorbance, which is proportional to [C2H3], so

Signal(t) = b + m[C2H3](t) Eq. (1)

where b is an uninteresting number related to how well the electronics baseline was
zeroed out before each experiment.

He performed similar experiments many times, each time with different initial
concentrations of ethene in the sample. From these experiments, he extracted the rate
constant “k” at various temperatures and pressures.

The reaction of interest is:

C2H3 + C2H4 Æ products

This reaction is very exothermic, so the reaction is essentially irreversible (i.e. when
equilibrium is achieved the vinyl concentration is too small to detect). You expect this
reaction to follow elementary-step kinetics, i.e.

-rC2H3=(k0 + k[C2H4])[C2H3] (Eq. 2)

k0 accounts for all other first-order loss processes of C2H3 in the experiment (e.g.
unimolecular reaction). Because the initial concentration of C2H3 is much smaller than
the concentration of C2H4, it is reasonable to assume that the concentration of C2H4 does
not vary significantly during each experiment. Therefore one expects a simple
exponential decay of [C2H3]:

[C2H3] = [C2H3]o e-t/τ (Eq. 3)

a) Write out the algebraic relationship between τ and k. Fit the measured signal for the
nth experiment Sn to this form:

Sn(t) = Bn + An exp(-t/τn) (Eq. 4)

Give expressions for An, Bn, and τn in terms of b, m, [C2H3]o, k0, k, and [C2H4]0,n. Which
of the three fit parameters An, Bn, and τn depends on k and [C2H4]0 ?

Cite as: William Green, Jr., and K. Dane Wittrup, course materials for 10.37 Chemical and Biological Reaction
Engineering, Spring 2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology.
Downloaded on [DD Month YYYY].
 b) Use Matlab to plot 1/τn vs. [C2H4]n, where τn is the exponential decay time constant
determined by fitting the data from the nth experiment. How can you use this plot to
determine the rate constant “k”?

Your assignment is to compute the rate constant “k” for the reaction of interest from the
student’s data, contained in files vinylethene1, vinylethene2, and vinylethene3 on the
10.37 course website. In each file the first column is the time in seconds, and the second
column is the measured signal Sn. The first dataset is for [C2H4]=6.7x10-4 M, the second
for [C2H4]=4x10-4 M and the third for [C2H4]=1.33x10-4 M.

Turn in the value of “k” you derived from modeling the student’s experimental data
(don’t forget to specify the units of “k”!), and also turn in plots comparing your model
predictions using this “k” with the experimental data.

Submit your Matlab program(s) to the 10.37 course website.

N.B. Notice that in this type of “pseudo-first-order” experiment, one can determine “k”
without knowing [C2H3]o, the calibration constant “m” relating the signal to [C2H3], what
the products of the reaction are, nor what the competing reactions are (that contribute to
k0). Because of these simplifications, this type of experiment is very widely used to
determine rate constants.

Cite as: William Green, Jr., and K. Dane Wittrup, course materials for 10.37 Chemical and Biological Reaction
Engineering, Spring 2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology.
Downloaded on [DD Month YYYY].