Environ. Sci. Technol.
2005, 39, 1632-1640
Atmospheric Chemistry of Hydrazoic
Acid (HN3): UV Absorption
Spectrum, HO• Reaction Rate, and
Reactions of the •N3 Radical
JOHN J. ORLANDO* AND
GEOFFREY S. TYNDALL
Atmospheric Chemistry Division, National Center for
Atmospheric Research, Boulder, Colorado 80305
ERIC A. BETTERTON
Department of Atmospheric Sciences, University of Arizona,
P.O. Box 210081, Tucson, Arizona 85721-0081
JOE LOWRY AND STEVE T. STEGALL
National Enforcement Investigations Center, U.S. E.P.A.,
Denver Federal Center, P.O. Box 25227,
Denver, Colorado 80225
Processes related to the tropospheric lifetime and fate of
hydrazoic acid, HN3, have been studied. The ultraviolet
absorption spectrum of HN3 is shown to possess a maximum
near 262 nm with a tail extending to at least 360 nm.
The photolysis quantum yield for HN3 is shown to be ≈1
at 351 nm. Using the measured spectrum and assuming unity
quantum yield throughout the actinic region, a diurnally
averaged photolysis lifetime near the earth’s surface of 2-3
days is estimated. Using a relative rate method, the rate
coefficient for reaction of HO• with HN3 was found to be (3.9
( 0.8) × 10-12 cm3 molecule-1 s-1, substantially larger
than the only previous measurement. The atmospheric HN3
lifetime with respect to HO• oxidation is thus about 2-3
days, assuming a diurnally averaged [HO•] of 106 molecule
cm-3. Reactions of •N3, the product of the reaction of
HO• with HN3, were studied in an environmental chamber
using an FTIR spectrometer for end-product analysis.
The •N3 radical reacts efficiently with NO, producing N2O
with 100% yield. Reaction of •N3 with NO2 appears to
generate both NO and N2O, although the rate coefficient
for this reaction is slower than that for reaction with NO. No
evidence for reaction of •N3 with CO was observed, in
contrast to previous literature data. Reaction of •N3 with
O2 was found to be extremely slow, k < 6 × 10-20 cm3
molecule-1 s-1, although this upper limit does not
necessarily rule out its occurrence in the atmosphere.
Finally, the rate coefficient for reaction of Cl• with HN3 was
measured using a relative rate method, k ) (1.0 ( 0.2)
× 10-12 cm3 molecule-1 s-1.
Introduction
Over the past decade, demand for sodium azide (NaN3), the
principal active ingredient in automobile air bag inflators,
has rapidly risen to exceed 5 million kg per year (1). This has
Corresponding author phone: (303)497-1486; fax: (303)497-1411;
e-mail: orlando@acd.ucar.edu.
1632 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 39, NO. 6, 2005
greatly increased the potential for accidental environmental
releases and for human exposure to this highly toxic material.
Aqueous sodium azide is readily hydrolyzed to yield hydrazoic
acid, HN3 (pKa 4.7), a volatile substance that partitions
strongly to the gas phase (KH ) 12 M atm-1) under
atmospheric conditions (2). For example, even at concentra-
tions as low as 6.5 ppm (m/v) NaN3 in the aqueous phase
(pH 6.5) the gas-phase concentration reaches the threshold
limit value of 0.11 ppmv (as hydrazoic acid gas) so there is
interest in understanding the fate of atmospheric hydrazoic
acid. The problem of significant azide releases to the
environment is not a hypothetical one. For example, the town
of Mona, UT was evacuated in 1996 afer a tanker truck hauling
80 55-gallon drums of NaN3 overturned (1). The problem of
azide disposal will remain for decades, given the many
millions of kilograms of NaN3 that is currently being carried
by the nation’s automobile fleet (1).
Although the tropospheric fate of HN3 has not been the
subject of systematic study, sufficient data are available to
indicate that reaction with OH and photolysis are likely
tropospheric removal processes. Hack and Jordan (3) studied
the reaction of HO• with HN3 via the flash photolysis of H2O2/
HN3/He mixtures, with HO• detection via pulsed LIF and
reported a value for k1 of 1.3 × 10-12 cm3 molecule-1 s-1.
HO• + HN3 f products (1)
This would imply a tropospheric lifetime for HN3 of about
10 days (for a diurnally averaged [HO•] ) 106 molecule cm-3).
Reaction of O(1D) with HN3 appears to occur at essentially
the gas-kinetic rate, k ) (3.2 ( 1.0) × 10-10 cm3 molecule-1
s-1 (4), while values reported for the rate coefficient for its
reaction with Cl-atoms lie in the range (9-15) × 10-13 cm3
molecule-1 s-1 (5-8). Given the relatively large value of k1
and the higher abundance of OH compared to Cl and O(1D),
these latter two processes are not likely to be of any
atmospheric importance.
The UV spectroscopy and photochemistry of HN3 has been
studied in considerable detail (e.g., refs 9-34), although key
data for assessment of the importance of tropospheric
photolysis have yet to be obtained. McDonald et al. (18) have
reported absorption cross sections for HN3 throughout the
vacuum and near UV (100-325 nm). Vacuum UV measure-
ments by Okabe (115-210 nm) (19) and a single wavelength
determination at 193 nm (24, 25) indicate that these
McDonald et al. (18) data may be low by about 20%. Although
the McDonald et al. data do not extend beyond 325 nm and
indeed may be systematically low, they do indicate that
tropospheric photolysis of HN3 could be significant (pho-
tolysis lifetime ≈2-3 days).
Numerous photochemistry and photodissociation dy-
namics studies of HN3 have been conducted at wavelengths
ranging from 308 nm into the vacuum UV (e.g., refs 13-17,
19-34). The major photolysis products appear to be NH and
N2 at all wavelengths studied (13, 14, 20-27, 29, 30, 32-34),
although a minor process to form H and N3 has also been
observed at 193, 248, and 266 nm (28, 31-33):
HN3 + hν f HN• + N2 (2a)
f H• + •N3 (2b)
The HN• photoproduct is formed exclusively in the excited
a1∆ electronic state at long wavelength (λ g 248 nm) (25), in
keeping with spin conservation rules, although other elec-
tronic states (A,b,c) have been detected at 193 nm and below
10.1021/es048178z CCC: $30.25  2005 American Chemical Society
Published on Web 01/22/2005
(19, 21, 22, 25). A near-unity (φ ≈ 0.8) quantum yield for HN•
production near 290 nm has been reported (13), and unit
quantum yields are generally assumed at longer wavelengths.
Absolute quantum yields for H-atom formation have been
made at three wavelengths (28, 32): φ193 ) 0.14; φ248 ) 0.20;
and φ266 ) 0.04. No H-atom quantum yield data are available
at longer wavelengths, although H-atom production occurs
to at least 280 nm (33), and the energy threshold for this
process is near 325 nm.
Photolysis experiments at higher [HN3] and at higher total
pressures have also been carried out. Kodama (18), for
example, photolyzed mixtures of HN3 (6.6 × 104 ppmv) in ≈0
to 0.8 atm of Xe buffer gas at 313 nm. Chain reactions were
observed (ΦN2 ) 4.85; λ ) 313 nm) which were thought to
involve the reaction of the HN• photoproduct with additional
HN3, an unlikely path in the atmosphere. In earlier studies
of a similar nature, Beckman and Dickinson (11, 12) reported
ΦHN3 ) 3.6 (λ ) 190 or 254 nm).
Reaction with OH and photolysis of HN3 will result in the
formation of •N3 and HN• radicals, respectively. While HN•
is thought to react rapidly with O2 to give NO and HO• (35),
the atmospheric fate of •N3 is less certain. The most detailed
information regarding the reactivity of this species comes
from the work of Hewett and Setser (36). Using a discharge-
flow/LIF system, these authors reported that the reactions
of •N3 with NO, NO2, and CO all occurred with similar rate
coefficients (k3 ) 2.9 × 10-12 cm3 molecule-1 s-1; k4 ) 1.9 ×
10-12 cm3 molecule-1 s-1; and k5 ) 1.8 × 10-12 cm3 molecule-1
s-1). Thermodynamically accessible channels for these reac-
tions (based on ∆Hf(N3) ) 99 kcal/mol (33)) are given below:
•
N3 + NO f N2O + N2 (3a)
•
N3 + NO2 f 2NO + N2 (4a)
f 2N2O (4b)
f N2 + N2O + O• (4c)
f 2N2 + O2 (4d)
•
N3 + CO f NCO + N2 (5)
Given the relative atmospheric abundances of these three
reactants, reaction of •N3 with CO would thus dominate. No
products of these reactions were determined in the Hewett
and Setser study, although likely possibilities (channels 3a,
4a, 4b, and 5) were suggested. Reaction of •N3 with O2 was
found to be slow (36), k < 5 × 10-13 cm3 molecule-1 s-1,
although this upper limit is not nearly low enough to rule out
its importance in the atmosphere.
In this work, studies of processes related to the atmo-
spheric destruction and ultimate fate of hydrazoic acid are
reported, including measurement of (a) the UV absorption
spectrum of HN3 from 215 to 365 nm; (b) its photolysis
quantum yield at 351 nm; (c) the rate coefficient for reaction
of HN3 with HO•; and (d) the end-products of the reactions
of •N3 radical with O2, NO, NO2, and CO. Experiments showed
that the diurnally averaged tropospheric lifetime of HN3 is
about 1-2 days, with both solar photolysis and reaction with
HO• contributing about equally to its removal.
Materials and Methods
UV Absorption Measurements. The UV absorption spectrum
for HN3 was determined using a diode array spectrometer
system that has been described in detail previously (37, 38).
Measurements were made in a 90-cm long Pyrex absorption
cell equipped with quartz windows. The output from a
broadband D2 lamp is first collimated, then passes through
the absorption cell, and is focused onto the entrance slit of
a 0.3 m Czerny-Turner spectrograph (equipped with a 300
grooves/mm grating), which disperses the light onto a 1024-
pixel diode array detector (EG&G Model 1420). With this
configuration, each pixel is separated in wavelength by about
0.25 nm, providing coverage from about 220 to 450 nm with
a spectral resolution of 0.6 nm. The system was calibrated
in wavelength via interpolation between the positions of the
emission lines from a low-pressure mercury lamp. Spectra
were obtained from the summation of 100-200 exposures
of the diode array, each exposure being 0.2 s in duration.
Raw spectral data at each pixel, I(λ), obtained in the presence
of an HN3 sample, were converted to absorbance (base e) via
comparison with a spectrum, Io(λ), recorded with the
absorption cell evacuated, i.e., A(λ) ) ln {Io(λ)/I(λ)}. Absorp-
tion spectra were smoothed, and the smoothed data were
then interpolated in wavelength to obtain absorbance values
at 0.5 nm intervals.
Gaseous HN3 samples (for the UV measurements and all
other studies conducted herein) were obtained by gently
heating a mixture of approximately 1 g each of NaN3 and a
solid carboxylic acid (glycolic acid or stearic acid) (18, 19).
For the UV cross section measurements, the concentration
of HN3 in the absorption cell was determined by pressure
measurement, with the assumption that the gaseous samples
contained no impurities. Measurements of HN3 samples by
FTIR spectroscopy revealed no measurable impurities.
Multiple fills of the absorption cell were made, and measured
UV cross sections from the different samples were indis-
tinguishable. Sample pressures were varied between 0.5 and
4.1 Torr.
Photolysis Quantum Yield at 351 nm. The photodisso-
ciation quantum yield for HN3 at 351 nm was obtained by
subjecting HN3/O2 samples (about 1-1.5 Torr HN3 in 1 atm
O2 buffer gas) to multiple shots from a pulsed XeF excimer
laser (Lambda Physik Compex 102). The photolysis experi-
ments were conducted in a cylindrical Pyrex cell (25 cm long,
3.5 cm i.d.) equipped with quartz windows, which transmitted
about 80% of the 351 nm radiation. The laser pulse energy,
defined as the average of the energy before and after the cell
as measured with a pyroelectric power meter (Questek P9104),
was typically 90 mJ/pulse which corresponds to 1.6 × 1017
photons/pulse at 351 nm. Photolysis experiments were run
for about 3 h with the excimer operating at 8 Hz, resulting
in a total of roughly 105 laser shots. Pre- and postphotolysis
concentrations in the UV cell were determined by FT-IR
spectroscopy, using the environmental chamber/FT-IR spec-
trometer system described below. For prephotolysis mea-
surements, a calibrated (1 L) bulb was filled with the same
HN3 sample as the UV cell, and the contents of the calibrated
bulb were then swept into the chamber for analysis. Following
irradiation, the concentration of HN3 and photoproducts were
determined by first expanding the contents of the UV cell
into the calibrated bulb and then sweeping the bulb contents
into the chamber. Photolysis of HN3 leads to the production
of reactive NH radical. The effects of the subsequent
chemistry of these species (in particular, the formation of
OH and resulting consumption of HN3) was accounted for
in the analysis, as described in the results section. Control
experiments were also conducted in which the UV cell was
filled with HN3/O2 and left to stand for 3 h without irradiation;
no loss of HN3 was noted in these experiments.
HO• and Cl• Rate Coefficient Measurements and •N3
Reaction Product Studies. Rate coefficient measurements
and end-product studies were all carried out in an envi-
ronmental chamber/Fourier transform infrared spectrometer
system, which has been described previously (39). The
chamber is 2 m long, is constructed of stainless steel, and
has a volume of 47 L. It is interfaced via a set of modified
Hanst-type multipass optics to a Fourier transform spec-
VOL. 39, NO. 6, 2005 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 1633
FIGURE 1. Infrared absorption cross sections for HN3 measured in
this work. HN3 concentrations were determined manometrically in
a 1 L calibrated volume. Trace amounts of CO2 are evident in the
spectrum near 2350 cm-1.
trometer (Bomem DA3) operating in the infrared. The optics
were adjusted to allow sixteen traverses of the cell, thus
providing an observational path length of 32.6 m. Infrared
spectra were obtained at a spectral resolution of 1 cm-1 over
the range 800-3900 cm-1 from the coaddition of 150-200
interferograms, which required 2.5-3.5 min acquisition time.
Reaction mixtures were photolyzed through a quartz window
located at one end of the chamber using a Xe-arc lamp,
equipped with a Corning 7-54 filter, which provided radiation
in the 250-400 nm range.
For the HO• and Cl• rate coefficient measurements,
standard relative rate methodologies were employed (39).
For the HO• studies, ethene was used as the reference
compound, while HO• generation was from the photolysis of
methyl nitrite in the presence of added NO:
CH3ONO + hν f CH3O• + NO (6)
CH3O• + O2 f CH2O + HO2• (7)
HO2• + NO f HO• + NO2 (8)
Experiments were carried out in synthetic air at 700-720
Torr total pressure, with initial concentrations of species in
the chamber as follows: [CH3ONO] ≈ 4 × 1015 molecule cm-3;
[NO] ≈ 5.5 ×1014 molecule cm-3; [C2H4] ≈ 3.5 × 1014 molecule
cm-3; [HN3] ≈ (2-4) × 1014 molecule cm-3. Quantification
of ethene was done primarily using the strong absorption
feature centered at 950 cm-1. Quantification of HN3 was
accomplished using the absorption features at 2140 and 1150
cm-1. A calibrated infrared absorption spectrum for HN3 is
shown in Figure 1.
The heterogeneous loss of HN3 in the chamber was found
to be significant on the time scale of a typical relative rate
determination, and thus this process had to be corrected for.
Upon filling the chamber with the mixture just described,
the decay of HN3 and C2H4 was monitored in the dark for a
period of about 30 min, in the presence of UV light for another
25-30 min, and then again in the dark for a further 20-30
min. While C2H4 was found to be stable during the dark
periods, HN3 loss occurred with a first-order rate coefficient
in the range of (1-3) × 10-5 s-1. Some conditioning of the
cell with time was evident, as HN3 decays were typically faster
before photolysis than after. For determination of the relative
rate coefficient, HN3 loss during the photolysis period was
corrected by the average of the loss rate before and after
photolysis. The magnitude of the correction was about 20%.
1634 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 39, NO. 6, 2005
FIGURE 2. UV absorption spectrum (solid line) for HN3 measured
in this work. Data from ref 18 are given at selected wavelengths
(open circles). The action spectrum for HN3 near the earth’s surface
is shown in arbitrary units as the dashed line.
Control experiments showed that photolysis of HN3 was
negligible on the time scale of a typical kinetics run.
Similar methodologies were employed to determine the
Cl• rate coefficient, with Cl2 photolysis as the Cl• source and
both acetone and methyl chloride as the reference com-
pounds. These experiments were conducted in 700-710 Torr
synthetic air, with initial concentrations in the chamber as
follows: [Cl2] ) (3.8-5.8) × 1015 molecule cm-3; [HN3] )
(2.1-3.5) × 1014 molecule cm-3; [acetone] ) (4-5) × 1014
molecule cm-3; or [CH3Cl] ) (1.4-1.8) × 1015 molecule cm-3.
Acetone and methyl chloride were monitored primarily near
1220 and 1350 cm-1, respectively. For these experiments,
which could be conducted on shorter time scales than the
OH experiments, wall losses were found to be negligibly slow.
For studies of the products of the reactions of •N3, reaction
of Cl• with HN3 was used as the •N3 source reaction in most
cases:
Cl2 + hν f Cl• + Cl• (9)
Cl• + HN3 f •N3 + HCl (10)
In these experiments, mixtures of Cl2 (typically ≈4 × 1015
molecule cm-3) and HN3 (≈3 × 1014 molecule cm-3) were
photolyzed in 1 atm N2 in the presence of one or more
reactants (NO, NO2, CO, or O2). HO•-initiated oxidations of
HN3 were also carried out, involving the photolysis of
CH3ONO (≈4 × 1015 molecule cm-3), NO (3-5 × 1014 molecule
cm-3), and HN3 (2-4 × 1014 molecule cm-3). Further details
regarding reaction conditions for various experiments are
provided in the results section of the manuscript.
Chemicals were obtained from the following sources:
glycolic acid (99%, Aldrich), stearic acid (Chem. Service),
sodium azide (Sigma), Cl2 (Matheson, UHP), ethene (Linde,
C.P.), acetone (Sigma-Aldrich, 99.9+%, HPLC grade), methyl
chloride (Matheson), CO (Linde, CP grade), NO (Linde), NO2
(from reaction of NO with O2), N2 (boil-off from a liquid N2
Dewar), O2 (U.S. Welding, UHP). Methyl nitrite, CH3ONO,
was synthesized from the dropwise addition of sulfuric acid
to saturated solutions of sodium nitrite in methanol (40) and
stored in dry ice between uses. Gases were used as received,
while acetone was degassed by several freeze-pump-thaw
cycles before use.
Results and Discussion
UV Absorption Spectrum of HN3 Our HN3 UV absorption
spectrum is plotted in Figure 2, and the data are tabulated
TABLE 1: Ultraviolet Absorption Cross Sections for HN3
Measured in This Work
absorption absorption
wavelength cross section wavelength cross section
(nm) (cm2 molecule-1) (nm) (cm2 molecule-1)
215 3.61E-19 291 3.40E-20
217 2.89E-19 293 2.96E-20
219 1.97E-19 295 2.56E-20
221 1.39E-19 297 2.22E-20
223 1.01E-19 299 1.90E-20
225 7.49E-20 301 1.64E-20
227 5.75E-20 303 1.40E-20
229 4.88E-20 305 1.19E-20
231 4.60E-20 307 1.02E-20
233 4.61E-20 309 8.64E-21
235 4.63E-20 311 7.35E-21
237 4.73E-20 313 6.22E-21
239 5.09E-20 315 5.22E-21
241 5.62E-20 317 4.48E-21 FIGURE 3. Relative rate of decay of HN3 (after correction for
243 5.95E-20 319 3.74E-21 heterogeneous loss) versus that of ethene in the presence of HO•.
245 6.12E-20 321 3.12E-21
247 6.35E-20 323 2.60E-21 Some diffuse structure is evident in both our measurement
249 6.93E-20 325 2.17E-21 and that of McDonald et al. (18) in the 240-290 nm region.
251 7.54E-20 327 1.85E-21 As noted by McDonald et al., this structure can be attributed
253 7.65E-20 329 1.53E-21 to two 1600 cm-1 progressions offset from each other by
255 7.73E-20 331 1.26E-21 about 600 cm-1. They assigned the 1600 cm-1 mode to the
257 7.82E-20 333 1.08E-21 ν2 N-N-N asymmetric stretch in the upper electronic state
259 8.01E-20 335 8.72E-22 and the 600 cm-1 frequency to an upper state N-N-N
261 8.59E-20 337 7.43E-22
263 8.69E-20 339 6.57E-22 bending mode (most likely ν6).
265 8.34E-20 341 5.00E-22 HN3 Quantum Yield Determination at 351 nm. Using
267 8.21E-20 343 3.81E-22 the 351 nm absorption cross section measured in this work
269 8.06E-20 345 3.53E-22 (2.03 × 10-22 cm2 molecule-1) and the fractional loss of HN3
271 7.86E-20 347 2.82E-22 upon exposure to excimer irradiation (46% loss for 9 × 104
273 7.78E-20 349 2.35E-22 excimer pulses), the quantum yield for HN3 loss was
275 7.47E-20 351 2.03E-22 determined to be 2.14 ( 0.25 (uncertainties given throughout
277 7.00E-20 353 1.61E-22 this paper are 1σ). N2O, the only measurable photoproduct,
279 6.70E-20 355 1.08E-22
had an appearance quantum yield of 0.86 ( 0.15. These
281 6.34E-20 357 9.02E-23
283 5.74E-20 359 9.34E-23 observations are consistent with a near-unity (1.07 ( 0.15)
285 5.07E-20 361 5.27E-23 quantum yield for the primary photodissociation process
287 4.45E-20 363 4.76E-23 yielding HN•, coupled with subsequent loss of a second HN3
289 3.89E-20 365 3.57E-23 via reaction with OH:

HN3 + hνfHN• + N2 (2a)

in 2 nm intervals in Table 1. Uncertainties are estimated to
be (7% near the maximum of the spectrum (dominated by
the uncertainty in the measurement of the HN3 partial
pressure, with lesser contributions from uncertainty in
temperature and path length). Uncertainties increase at
longer wavelength (e.g., to about (20% near 360 nm) due to
increasing uncertainty in the absorbance measurement. The
spectrum shows a broad local maximum near 262 nm, and
the onset of a stronger maximum at wavelengths shorter
than 215 nm. Measurable absorption extends beyond 360
nm. The spectrum of HN3 has previously been measured
quantitatively by McDonald et al. (18) over the range 100-
325 nm. Their data (estimated from their Figure 3) are shown
at a few wavelengths in Figure 2. However, measurements
by Okabe (115-210 nm) (19) and Rohrer and Stuhl (193 nm
only) (25) suggest that the McDonald et al. data may be low
by about 15-20%. A similar discrepancy between our data
and those of McDonald et al. is also evident in Figure 2. The
scaling of the McDonald et al. (18) data suggested by Rohrer
and Stuhl (25) (by the ratio of the two 193 nm cross sections)
provides a cross section at 248.5 nm (6.8 × 10-20 cm2
molecule-1) that is within 2% of our data point at this
wavelength. Thus, a combination of the Okabe (19) data in
the vacuum UV (which agrees with the Rohrer and Stuhl (25)
data at 193 nm) with our longer wavelength data appears to
provide an accurate representation of the HN3 absorption
spectrum over the range 110-360 nm.
HN• + O2 f HO• + NO (11)
•
HO + HN3 f •N3 + H2O (1)
•
N3 + NO f N2 + N2O (3a)
net: 2HN3 + hν + O2 f 2N2 + N2O + H2O
The near-quantitative production of N2O during photolysis
(i.e., one N2O produced for every two HN3 molecules
consumed) is strong evidence for the near-quantitative
conversion of HN radicals into NO, since R3a appears to be
the only logical source of N2O in the system.
Our spectrum and quantum yield determination can be
convolved with solar flux data to calculate a theoretical
tropospheric photolysis rate constant for HN3 (jHN3, s-1). For
these calculations, diurnally averaged sea-level surface solar
flux data corresponding to a 40 °N, mid-summer day were
used (41). The retrieved action spectrum (dashed line, Figure
2) shows that maximum atmospheric photolysis is centered
near 320 nm. Integration under this curve, assuming a
quantum yield of unity for the entire actinic region, yields
an approximate 1/jHN3 lifetime of 2-3 days.
Preliminary experiments to directly determine the HN3
solar photolysis rate were carried out at the Denver Federal

VOL. 39, NO. 6, 2005 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 1635

Center. In these experiments, HN3/air mixtures (contained
in a Teflon bag) were exposed to solar radiation over the
course of 2 days, and the HN3 temporal profile was monitored
via FTIR spectroscopy. Although HN3 decay was clearly
observed during sunlight hours, these experiments are not
considered quantitative at this time due to the presence of
patchy cloud cover and the potential for HN3 loss via
unwanted processes (i.e, heterogeneous loss, reaction with
OH). Further experiments of this type, to provide a quantita-
tive comparison with the laboratory cross section and
quantum yield data, are planned.
Rate Coefficient for Reaction of HO• with HN3. The rate
coefficient for reaction of HO• with HN3 was determined
relative to the well-established rate coefficient for reaction
of HO• with C2H4 (8.2 × 10-12 cm3 molecule-1 s-1, 298 K, 1
atm total pressure (42, 43)).
HO• + HN3 f •N3 + H2O
HO• + CH2dCH2 + M f HOCH2CH2 + M
Relative rate data, after correction for heterogeneous loss
of HN3 as described earlier, are displayed in Figure 3 and
yield a rate coefficient ratio k1/k12 ) 0.48 ( 0.05. The
magnitude of the heterogeneous correction was on the order
of 20%. Incorporating a 10% uncertainty in k12, a value of k1
) (3.9 ( 0.8) × 10-12 cm3 molecule-1 s-1 is determined. We
also note that other species potentially reactive with HN3 are
generated in these experiments, namely O-atoms (via pho-
tolysis of NO2) and O3 (via recombination of O with O2). Both
of these species react slowly with HN3 (4, 35) and will not
contribute significantly to its loss.
Hack and Jordan (3) reported the only other measurement
of k1. They monitored the decay of HO• via pulsed laser-
induced fluorescence, following the flash photolysis of
mixtures of H2O2 and HN3 in He buffer gas. Their value, (1.3
( 0.2) × 10-12 cm3 molecule-1 s-1, is considerably smaller
than ours; reasons for this discrepancy are not obvious.
Similarities in the reactivity of HN3 and HBr might be
expected, given the near identical H-X bond strengths (369
kJ mol-1) in the two species (33, 42, 43) and the reasonable
correlation between HO• rate coefficients and H-X bond
strengths in the hydrogen halides (and pseudohalides). This
holds true in a qualitative way, with k1 being about a factor
of 2 lower than the rate coefficient for reaction of HO• with
HBr (42).
Using our value for k1 and a diurnally averaged tropo-
spheric HO• concentration of 1 × 106 molecule cm-3, the
lifetime for HN3 with respect to HO• reaction can be estimated
to be ≈2-3 days.
Rate Coefficient for Reaction of Cl• with HN3. Relative
rate data for R10 versus the two reference reactions, R13 and
R14, are shown in Figure 4.
Cl• + HN3 f •N3 + HCl
Cl• + CH3C(O)CH3 f CH3C(O)CH2 + HCl
Cl• + CH3Cl f CH2Cl + HCl
Least-squares analysis of these data yield the following
rate coefficient ratios, k10/k13 ) 0.44 ( 0.06 and k10/k14 ) 2.19
( 0.25. Although there is some discrepancy in the literature
regarding the value of k13 (values range from about (1.8-3.1)
× 10-12 cm3 molecule-1 s-1), recent data (39, 44, 45) are
centered at (2.2 ( 0.4) × 10-12 cm3 molecule-1 s-1. The value
of k14 ) (4.9 ( 0.8) × 10-13 cm3 molecule-1 s-1 seems to be
well established (42, 43). Combining these reference rate
coefficient data with our measured ratios yields values for
1636 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 39, NO. 6, 2005
(1)
FIGURE 4. Relative rate of decay of HN3 versus those of acetone
(solid circles) and methyl chloride (open circles) in the presence
(12) of Cl-atoms.
k10 of (0.97 ( 0.20) × 10-12 cm3 molecule-1 s-1 and (1.07 (
0.20) × 10-12 cm3 molecule-1 s-1, from which a final value
k10 ) (1.02 ( 0.20) × 10-12 cm3 molecule-1 s-1 can be obtained.
There are a number of determinations of k10 in the literature
(5-8), including one temperature-dependent study (8), all
obtained using flow tube methodologies. While there is very
reasonable agreement between the various room-temper-
ature measurements, which range from (9-13) × 10-13 cm3
molecule-1 s-1, these measurements were of an indirect
nature, involved substantial occurrence of, or correction for,
secondary reactions, and/or required modeling of fairly
complex reaction systems, and thus uncertainties on the order
of (25% typically apply. Our measurement of k10 via a
completely different methodology, one that should be free
of any complication from secondary reactions, provides
confirming evidence for a value of k10 of (1.0 ( 0.2) × 10-12
cm3 molecule-1 s-1.
As discussed above, similarities in reactivity between HN3
and HBr might be expected. As in the case of the reaction
of HO• with these two species, Cl• reacts more slowly with
HN3 than with HBr (5, 35), in this case by about a factor of
5.
Reactions of the •N3 Radical. A series of experiments was
carried out to determine the products of the reactions of •N3
with various species (itself, NO, NO2, CO, and O2) and to
determine semiquantitatively the rate coefficients or at least
the relative rates for these reactions. For convenience, results
obtained in our work and in previous studies are summarized
in Table 2.
The simplest experiments involved the photolysis of Cl2
(≈4 × 1015 molecule cm-3)/HN3 (≈2 × 1014 molecule cm-3)
mixtures in the presence of 700 Torr N2. Although HN3 was
efficiently destroyed in these experiments, the only product
(10) observed in the infrared was N2O with a molar yield of only
(3.1 ( 0.4)% (Figure 5, open circles). The small N2O yield
(13) observed possibly arises from the presence of small NOx
impurities in the chamber (reaction of NO2 or NO with •N3
(14) would eventually lead to N2O, see below). The lack of large
yields of observable products suggests the involvement of
•N self-reaction as an important removal process for N ,
3 3
resulting in the formation of N2, which is undetectable with
our apparatus:
•
N3 + •N3 f 3N2 (15)
Although the rate coefficient for R15 has not been firmly
established, it appears to be e 2 × 10-12 cm3 molecule-1 s-1
(36). Box model simulations of the experiments (conducted
TABLE 2: Summary of Available Data Regarding Rate Coefficients and Products for Reactions of N3 Radicals with Atmospherically
Relevant Species
reaction
reactant number rate coefficient (cm3 molecule-1 s-1)
NO R3 2.9 × 10-12 (ref 36)
NO2 R4 1.9 × 10-12 (ref 36); less than k3/3 (this work)
CO R5 1.8 × 10-12 (ref 36); less than k3/100 (this work)
O2 R25 <1 × 10-13 (ref 36); < 6 × 10-20 (this work)
FIGURE 5. Product yields observed from the Cl-atom-initiated
oxidation of HN3, plotted as a function of HN3 consumption. Filled
circles, N2O produced in experiments with NO added; open squares,
loss of NO in experiments with NO added; filled triangles, N2O
produced in experiments with NO2 added; open circles, N2O
production in the absence of added NOx. See text for detailed
experimental conditions.
using the Acuchem software package (46)) indicate that reac-
tion of Cl• with •N3 cannot be ignored under these conditions:
Cl• + •N3 f NCl• + N2 (16)
The fate of NCl• is not known in this system but may involve
formation of NCl3 a compound whose major IR absorption
bands (<800 cm-1) likely occur outside our accessible range.
NCl• + Cl2 f NCl2 + Cl• (17)
NCl2 + Cl2 f NCl3 + Cl• (18)
Finally, we note that in this case, where no reactive species
(NOx, CO) have been added to the chamber, the lifetime of
N3 may be sufficiently long (perhaps a few seconds, as
indicated by box modeling studies) to allow for some
heterogeneous removal at the chamber surface.
We conducted numerous experiments with NO, (0.7-
4.2) × 1014 molecule cm-3, added to the standard Cl2/HN3
mixtures. Experiments were conducted with either N2 or
synthetic air as the buffer gas at a total pressure of 700-720
Torr. The major product observed in these experiments was
N2O, with a molar yield of 91 ( 12%, independent of the
nature of the buffer gas (solid circles, Figure 5). This essentially
1:1 conversion of HN3 to N2O, observed under all conditions
in which NO was present, is consistent with the quantitative
occurrence of R3a:
Cl• + HN3 f •N3 + HCl (10)
•
N3 + NO f N2 + N2O (3a)
products
N2O + N2 (≈100%), this work
2NO + N2 (major, this work); 2N2O (<30%, this work);
N2 + N2O + O (<60%, this work); 2N2 + O2
(minor/negligible, this work)
NCO + N2 (speculative, ref 36)
N2O + NO, N2 + NO2, and/or N2 + NO + O (speculative)
Losses of NO were also measured. In N2 buffer, the loss
of NO was found to be identical to the N2O production (Figure
5, open squares), again consistent with the quantitative
occurrence of R10 and R3a. When air was used as the buffer
gas, losses of NO exceeded those of N2O, and NO2 production
was also observed. This extra conversion of NO to NO2 likely
results from the occurrence of the well-known (35) three-
body reaction, R19:
NO + NO + O2 f NO2 + NO2 (19)
Reasonable correspondence was obtained between the
loss of NO in air, corrected by the amount of NO2 formed,
and the observed N2O. Hewett and Setser (36) determined
a rate coefficient of k3 ) (2.9 ( 0.3) × 10-12 cm3 molecule-1
s-1. They surmised that N2 and N2O were the most likely
products of the reaction, a result now confirmed by the
experiments conducted herein.
Another of the reactions studied by Hewett and Setser
(36) was the reaction of •N3 with CO, for which they reported
a rate coefficient of (1.8 ( 0.2) × 10-12 cm3 molecule-1 s-1
and proposed NCO and N2 as the most reasonable reaction
products. When standard Cl2/HN3/N2 reaction mixtures were
photolyzed in our chamber in the presence of CO, (3.5-7)
× 1014 molecule cm-3, only a very small (≈4%) yield of N2O
was observed. Although HN3 was efficiently consumed, no
change in [CO] was observed nor was any other product
detected. These findings are suggestive of a CO-catalyzed
recombination of •N3, via R5a, and R20 and/or R21, resulting
in large yields of undetectable N2:
•
N3 + CO f NCO + N2 (5a)
NCO + NCO f CO + CO + N2 (20)
NCO + •N3 f CO + 2N2 (21)
However, we present evidence below that suggests that
R5 may be considerably slower than reported by Hewett and
Setser (36). Thus, in these Cl2/HN3/CO/N2 experiments, it is
possible that NCO is not formed at all, and •N3 loss is
controlled by its self-reaction and/or its reaction with Cl•,
again leading to large yields of N2 or other undetectable
products. The trace yield of N2O in these experiments is again
likely the result of the presence of minor NOx impurities in
the chamber.
To assess the relative rate of the reaction of •N3 with NO
and CO, mixtures of Cl2 (≈3.5 × 1015 molecule cm-3), HN3
(≈3 × 1014 molecule cm-3), CO ((1-35) × 1014 molecule cm-3),
and NO (≈1 × 1014) were photolyzed in the chamber. The
initial [NO]:[CO] ratio was varied from 1:1 to 1:25. Given the
similar values for k3 and k5 reported by Hewett and Setser
(36), one would expect significant production of NCO via
R5a under all of these conditions, and essentially exclusive
NCO formation at the highest [CO]:[NO] ratios employed.
Reaction of NCO with NO, R22, is thought (47-50) to generate
near-equal yields of N2O and CO2.
VOL. 39, NO. 6, 2005 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 1637
 NCO + NO f N2O + CO (22a)
NCO + NO f CO2 + N2 (22b)
Thus, in our Cl2/HN3/CO/NO experiments, increasing the
ratio of [CO] to [NO] should result in an increase in the yield
of CO2, via R5a and R22b, and a concomitant decrease in the
yield of N2O. However, in no case was any CO2 production
or CO consumption observed in our experiments. Further-
more, yields of N2O remained high (g85%), indistinguishable
from those observed when only NO was added to the system.
Thus, we find no evidence for the production of NCO in this
system, and thus no evidence for the occurrence of a reaction
between •N3 and CO. From the lack of CO2 production in the
experiment with the highest [CO]:[NO] ratio, we estimate
that the value for k5 to produce NCO is at least 100 times
slower than the value of k3. It should be noted that this finding
is obtained under the assumption of approximately equal
rate coefficients for the two branches of R22, as reported in
refs 47-50. Should higher yields of N2O relative to CO2 be
the case, the picture would be blurred considerably (note
that R5a followed by R22a is indistinguishable from R3a). At
the very least then, our data are not consistent with the
combined results of refs 36 and 47-50. Given the substantial
evidence for CO2 production in R22 (47-50), obtained by
various independent investigators using different techniques,
it seems most likely that the value of k5 has been overesti-
mated in ref 36.
The next reaction studied was that of •N3 with NO2, for
which Hewett and Setser (36) reported a rate coefficient of
(1.9 ( 0.2) × 10-12 cm3 molecule-1 s-1. As noted in the
Introduction, multiple reaction channels are possible, leading
to the production of NO, N2O, N2, O2, and/or O-atoms. We
conducted three types of experiments which can provide
information regarding the rate coefficient and/or mechanism
of R4. First, standard Cl2/HN3 mixtures were photolyzed in
the presence of (1.7-2.8) × 1014 molecule cm-3 NO2 (“type
1” experiments). Second, experiments were conducted in
which both NO and NO2 were added to the standard Cl2/
HN3 reaction mixtures (“type 2”). Finally, experiments were
conducted in which HO• was used to initiate the oxidation
(“type 3”). While NO2 is not initially present in these “type
3” experiments, it is generated in the HO• source chemistry
(see R6-8 above) and thus its concentration builds up as an
experiment progresses. As shown in Figure 5 (solid triangles),
N2O was clearly a major product in the “type 1” experiments,
although its appearance profile is curved and its initial yield
is clearly less than unity. The production of NO was also
noted in these experiments, which could arise from the
photolysis of NO2 or from R4.
NO2 + hν f NO + O• (23)
O• + NO2 f NO + O2 (24)
In both the “type 2” and “type 3” experiments (i.e., when NO
is present in the initial mixture), the yield of N2O was near
unity, and its appearance profiles were found to be linear.
Because of the multiple pathways for conversion of NO2
to NO and the multiple potential sources of N2O, i.e., R3,
R4b, and R4c, a quantitative assessment of the rate coefficient
and branching ratios for R4 is not possible. However, through
box model simulations of the experiments, some conclusions
can be drawn. First, the less than unity yield of N2O early in
the “type 1” experiments clearly precludes channel (4b) from
being a major channel and precludes a dominant contribu-
tion from R4c. Simulations suggest an N2O yield from R4 of
about 40 ( 20%si.e., a branching ratio of no more than 30%
to (4b), or 60% via (4c), or some combination of the two.
1638 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 39, NO. 6, 2005
Second, although NO2 to NO conversion is dominated by
NO2 photolysis in many cases, some experiments suggest a
large yield of NO must be obtained from R4, and thus a large
branching to channel (4a) and/or (4c) is likely. (Note that
R4c can lead indirectly to NO via production of O-atoms
followed by the occurrence of R24). Third, nitrogen mass
balance arguments, which do not allow for large yields of N2
from R4, can be used to preclude a large contribution from
channel (4d). Finally, we conclude that the total rate
coefficient k4 is likely about a factor of 3 or more smaller
than k3, given that a unity yield of N2O was obtained in “type
2” experiments, even when the initial [NO2]:[NO] ratio was
as high as 4:1. Although not a unique solution, all experiments
conducted can be simulated reasonably well with k4a ≈ 6 ×
10-13 cm3 molecule-1 s-1 and k4b ≈ 2 × 10-13 cm3 molecule-1
s-1. Inclusion of a minor occurrence of R4c in the box model
with a compensatory reduction in k4a and k4b also provides
adequate simulations of the experimental results.
The last reaction studied was that of •N3 with O2, a reaction
for which Hewett and Setser (36) reported a rate coefficient
upper limit of 1 × 10-13 cm3 molecule-1 s-1. The reaction
appears to have three energetically favorable reaction chan-
nels
•
N3 + O2 f N2O + NO (25a)
f N2 + NO2 (25b)
f N2 + NO + O (25c)
Our experiments consisted of the photolysis of mixtures
of Cl2 (≈4 × 1015 molecule cm-3)/HN3 (≈1014 molecule cm-3)
in 750-1050 Torr O2/N2 diluent, with the O2 partial pressure
varied from 10 to 1000 Torr. The only product observed in
these experiments was N2O. Although its yield did increase
with O2 partial pressure (from about 8% at 10 Torr O2 to 30%
at 1000 Torr), this increase was less than linear in [O2],
suggesting that reaction of •N3 with O2 was not the source of
all of the observed N2O. From box model simulations of the
high [O2] experiments, under the assumption that all of the
N2O formed derived from R25, an upper limit of 6 × 10-20
cm3 molecule-1 s-1 was found for k25. This upper limit is not
dependent on the mechanism for R25, as each of the three
reaction channels listed above gave similar N2O yields in the
model simulations. The derived upper limit is however
somewhat dependent on the value used in the model for k15,
the rate coefficient for self-reaction of •N3 (faster removal of
•N via R15 requires a larger value for k
3 25 to generate the
observed N2O). While Hewett and Setser have reported an
upper limit for k15 of 1.5 × 10-12 cm3 molecule-1 s-1, the
upper limit we report for k25 still applies for values of k15 as
high as 10-11 cm3 molecule-1 s-1.
Atmospheric Fate of HN3. Due to its low Henry’s law
constant and moderate pKa, aqueous azide is easily trans-
ferred to the gas phase as hydrazoic acid (2). The data
obtained in this study show that removal of HN3 from the
lower troposphere will be controlled by photolysis and by
reaction with HO• with an overall lifetime of about 1-2 days.
This implies that a hydrazoic acid plume could be sufficiently
long-lived to be advected many kilometers downwind from
a spill, assuming that other more rapid sinks are not available.
Solar photolysis of HN3 and reaction with HO• will lead
to the production of the HN• and •N3 radicals, respectively.
Although these radicals are likely to have little further
atmospheric impact, it is interesting to consider their ultimate
fate, and thus that of the parent HN3. The HN• radical has
been shown to react rapidly with O2 to generate HO• and NO.
(35) The kinetic database for •N3 is, however, not sufficiently
mature to allow a confident assessment. The work conducted
herein, in conjunction with rate data from Hewett and Setser
(36), shows that reactions of •N3 with NO or NO2 (leading in
large part to N2O) may contribute. However, we are as yet
unable to rule out reaction of •N3 with either CO or O2 as
being of atmospheric relevance. Our work indicates that k5
may be considerably slower than measured by Hewett and
Setser, but given the typical atmospheric predominance of
[CO] over [NOx], R5 may still contribute. Even our upper
limit for k25 leads to a lifetime for •N3 with respect to O2
reaction of a few seconds, a time scale that is comparable
to •N3 removal by a few ppbv of NOx. Given the existence of
some discrepancies between our work and that of Hewett
and Setser (36), further direct (time-resolved) kinetic studies
of the •N3 radical, perhaps using tunable diode laser
techniques for product detection, would be productive.
Acknowledgments
The National Center for Atmospheric Research is operated
by the University Corporation for Atmospheric Research
under the sponsorship of the National Science Foundation.
The authors are grateful to Richard Ross and Jim Hoban
(U.S. EPA NEIC) for their assistance with the solar photolysis
experiments and to J.-F. Lamarque and David Hanson of
NCAR for their critical reading of the manuscript. One of us,
E.A.B., would like to thank to Ms. Diana A. Love, Director,
U.S. EPA NEIC, for providing financial and technical support
that made possible his sabbatical leave from the University
of Arizona.
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Received for review November 19, 2004. Accepted November
23, 2004.
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