Water Vapor Effect on the HNO3 Yield
J. Phys. Chem. A, Vol. 113, No. 42, 2009 11341
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of ꢀ (Figure 3 of ref 6), which contradicts to the zero intercept
required by a gas-phase mechanism. The observed increase of
the intercept with the decrease of temperature (Figure 6 of ref
6) could be explained, for example, by an Eley-Rideal
mechanism55 for heterogeneous reaction of adsorbed HO2 with
NO. At present, we have no explanation for these experimental
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However, such an intercept problem appears to be not specific
of the HO2 + NO reaction but is also common for nitrate
formation in reactions of NO with alkyl peroxy radicals, RO2.
Similar intercepts were observed by Atkinson’s group in their
studies of the pressure dependence of C5-C8 alkyl nitrate
yields,56-58 the most recent study of Aschmann et al.58 being
undertaken in particular to verify the pressure dependence for
pentyl nitrate obtained earlier.56 Accurate measurements of the
pressure dependence for both 2- and 3-pentyl nitrate yields over
the 51-774 Torr range gave straight lines with significant
intercepts, for which no explanations were given (corrections
for the contribution from secondary gas-phase reaction did not
eliminate them).58 Unfortunately, no information is available
on these intercepts as a function of temperature, as those
measurements were carried out only at 297 K. It is worth also
to mention, that in very recent investigations from our labora-
tory, apparent zero-pressure intercepts were also found in the
pressure dependences of nitrate formation in the lighter C2H5O2
+ NO and iso-C3H7O2 + NO systems.59 The nature of these
intercepts is not clear. First of all, it is necessary to note that
the intercepts under discussion are the result of extrapolation
to zero pressure and there is no evidence that the intercepts are
true or false, i.e., an artifact of extrapolation. The explanation
might be found in the complexity of the potential energy surface
of the HO2 + NO-HOONO-HONO2 system having several
potential wells. Zhang et al. suggested that the general picture
of the pressure dependence for nitrate formation yield in RO2
+ NO reaction can display a dual falloff curve, one falloff
corresponding to stabilization of the ROONO complex and
another one to stabilization of the RONO2 product.9 Unfortu-
nately, we cannot check this hypothesis, since our equipment
cannot operate at pressures below 70 Torr. So, there is a need
to examine low-pressure behavior of nitrates and HNO3 forma-
tion in RO2 + NO reactions using other techniques.
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In summary, we have presented substantial arguments against
important wall contribution to our measurements of the HNO3
yields, ꢀ, reported in our previous papers and the present one.
On the other hand, experimental facts such as the observed zero-
pressure intercepts of the pressure dependences of ꢀ cannot find
an explanation so far. The issue of the zero-pressure intercepts
needs to be solved by further experimental investigations at low
pressures (less than 50 Torr) as well as by theoretical studies.
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