2.

3 The SO3 used in the manufacture of sulfuric acid is obtained

by the oxidation of SO2in the presence of an appropriate catalyst:
SO2 + 0.5O2 SO3
If one starts with a feed of the composition shown below,
determine the temperature at which the fluid must leave the
reactor if the equilibrium effluent composition corresponds to
95% conversion of the SO2 fed to the reactor.

Species (mol%)

O2 13.0

N2 79.0

SO2 8.0

The effluent pressure is 2 atm. At 600C the standard

Gibbs free-energy change for standard states of unit fugacity
is known to be 3995 cal/mol for the reaction as written
above. For the temperature range of interest, the standard
heat of reaction may be taken as a constant equal to 22, 650
cal/mol.

d[NO3] = k1[N2O5] k2[NO2][NO3] k3[NO3][NO2] k4[NO][NO3] 0 (G)

dt

Thus,
[NO3]SS = k1[N2O5]
k2[NO2] + k3[NO2] + k4[NO] (H)

The subscript SS re fers to a steady-state value.

Equation (H) also involves the concentration of a reaction
intermediate [NO]. If we make the steady-state approximation
for this species,

5.1 In their textbook, M. Diaz Pia and A. Roig Muntaner

(Quimica Fisica, Vol. II, pp. 10731074, Editorial Alhambra,
Madrid, 1976) reported the data below for the reversible
cistrans isomerization of 1,2-dimethyl cyclopropane. Test
these data to ascertain if they are consistent with a rate
expression that is first-order in both the forward and reverse
directions.

Cis kf trans
kr

If the data are consistent with the indicated rate expression,

determine values for kf , kr, and the equilibrium constant for
the reaction.
Time (s) Percenttrans
0 100
45 89.2
90 81.2
225 62.3
270 58.2
360 50.7
495 43.5
585 39.9
10,000 30.0
4.3 Experimental data for the catalytic decomposition of ozone in
the presence of nitrogen pentoxide follow the rate law:

r = k(O3)23(N2O5)23

The following mechanism has been proposed as an explanation

for these observations.

N2O5 +Mk1 k2N2O5 + M

N2O5
k3
k4

NO2 + NO3
NO3 + O3
k5 NO2 + 2O2
NO2 + O3
k6 O2 + NO

where N2O5
is an excited nitrogen pentoxide molecule and
M is any molecule. NO3 should be treated as an active intermediate.
Show whether or not this mechanism is consistent
with the experimentally observed rate expression.
Note that the stoichiometry of this reaction is given by

2O3 3O

and that there is no net consumption or production of species

M in any reaction.If the mechanism above is not consistent
with the experimental rate law, suggest an alternative mechanism
including reactions 1 to 4 and 6 that will be consistent.
(Note: It will not be necessary to introduce any chemical
species in addition to those used above. Consider only
bimolecular reactions.)