Thermal stability of peroxy acyl nitrates formed in the oxidation of C xF2 x +1CH2C(O)H (x = 1,6) in the presence of NO2

Article abstract of DOI:10.1021/jp4003593

The formation of C_xF_2x+1CH₂C(O)OONO ₂ (x = 1,6) from the photooxidation of C_xF _2x+1CH₂C(O)H (x = 1,6) in the presence of NO₂ was investigated. The infrared spectrum of C₆F₁₃CH ₂C(O)OONO₂ is reported for the first time, and thermal stability for both peroxynitrates at 295 K and 9.0 mbar is informed. Kinetic parameters (activation energy and pre-exponential factor) for CF ₃CH₂C(O)OONO₂ at 9.0 and 1000 mbar are: 108 ± 2 kJ/mol, 1.5 × 10¹⁵ and 114 ± 2 kJ/mol, 2.4 × 10¹⁶, respectively. A comparison is made between fluoro and hydrogenated peroxy acyl nitrates.

Full text of DOI:10.1021/jp4003593

Article
pubs.acs.org/JPCA
Thermal Stability of Peroxy Acyl Nitrates Formed in the Oxidation of
CxF2x+1CH2C(O)H (x = 1,6) in the Presence of NO2
Diana Henao,† Fabio E. Malanca,*,† Malisa S. Chiappero,‡ and Gustavo A. Arguello†
̈
†INFIQC (CONICET), Departamento de Físico Química, Facultad de Ciencias Químicas, Universidad Nacional de Cor
́
doba, Ciudad
́
Universitaria, 5000 Cordoba, Argentina
‡Departamento de Química, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Mar del Plata, Funes 3350 − Nivel +2
(B7600AYL)
ABSTRACT: The formation of CxF2x+1CH2C(O)OONO2 (x = 1,6) from the
photooxidation of CxF2x+1CH2C(O)H (x = 1,6) in the presence of NO2 was
investigated. The infrared spectrum of C6F13CH2C(O)OONO2 is reported for the
first time, and thermal stability for both peroxynitrates at 295 K and 9.0 mbar is
informed. Kinetic parameters (activation energy and pre-exponential factor) for
CF3CH2C(O)OONO2 at 9.0 and 1000 mbar are: 108 2 kJ/mol, 1.5 × 1015 and
114 2 kJ/mol, 2.4 × 1016, respectively. A comparison is made between fluoro
and hydrogenated peroxy acyl nitrates.
species due to their stability. Among them, peroxyacetyl
(CH3C(O)OONO2, PAN), peroxypropionyl (CH3CH2C(O)-
OONO2, PPN), peroxyisobutyryl (PiBN, ((CH3)2CHC(O)-
OONO2), peroxybutyryl (PnBN, CH3(CH2)2C(O)OONO2),
and peroxybenzoyl (C6H5C(O)OONO2, PBzN) nitrates have
been detected in the atmosphere.10−14 To provide information
about the thermal stability of the peroxynitrates formed by the
oxidation of FTAL 6:2 and CF3CH2C(O)H in the presence of
NO2, we prepared both and measured their decomposition rate
constants as a function of temperature and total pressure.
INTRODUCTION
■
The oxidation of telomeric alcohols (FTOHs), which have a
wide variety of industrial applications, leads to the formation of
fluorinated telomeric aldehydes (FTAHs, CxF2x+1CH2C(O)H)
and perfluorocarboxylics acids1 (PFCAs, CnF2n+1C(O)OH),
which are highly persistent in the environment and have been
found to be present in fauna from the Great Lakes2 up to the
Arctic.3 In particular, C6F13CH2C(O)H (FTAL 6:2) is formed
from the degradation of FTOH 6:2,4 whereas CF3CH2C(O)H
has been reported as the primary oxidation product of
CF3CH2CH2OH.5
EXPERIMENTAL SECTION
The UV absorption cross sections and the photochemistry of
FTAL 6:2 were studied6 as well as its reaction with both
chlorine atoms,4,7,8 for which the authors measured a rate
constant of (2.1 0.5) × 10−12, (2.8 0.7) × 10−12, and (1.8
0.2) × 10−11 cm3 molec−1 s−1, respectively, and OH radicals,4
with a reported coefficient of (2.2 0.3) × 10−12 cm3 molec−1
s−1. Its oxidation in the absence of NOx gives n-C6F13C(O)H,
CF2O, CO2, and CO as the only products. Chiappero et al.4
concluded that most of the reaction between CnF2n+1CH2C(O)
H and chlorine atoms occurs via abstraction of the aldehyde
hydrogen atom, not being substantially modified by the length
of the fluorinated CnF2n+1 group.
■
Reagents. Samples of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-
1-octanal and 3,3,3-trifluoropropionaldehyde (TFPA,
CF3CH2C(O)H) were used as provided without any special
purification. Oxygen (5.0), nitrogen (5.0), and nitrogen
monoxide (5.1) were provided by AGA. Cl2 (>99%) was
prepared by dehydration of HCl, and NO2 (>99%) was
obtained from thermal decomposition of Pb(NO3)2.
Procedure. Gas samples were manipulated in a glass
vacuum line equipped with two capacitance pressure gauges. All
photolyses were carried out in a 5 L glass flask, using black
lamps (λ > 330 nm) to initiate the oxidation from chlorine
atoms.
Synthesis and Characterization. C6F13CH2C(O)OONO2.
Photolyses of mixtures containing C6F13CH2C(O)H (0.6
mbar), Cl2 (0.9 mbar), NO2 (0.9 mbar), and O2 (1000
mbar) were performed at 295 K. Their progress was monitored
at 0, 30, 50, and 75 min by transferring portions of the mixtures
to a long path infrared gas cell (optical path: 9 m) and
recording infrared spectra. It was stopped before the NO2 was
Kelly et al.5 have measured the quantum yield of the
photolysis of CF3CH2C(O)H, ϕ < 0.04 and its rate constant
with OH radicals (2.96 0.04) × 10−12 cm3 molec−1 s−1 and
chlorine atoms (25.7
0.4) × 10−12 cm3 molec−1 s−1. Its
oxidation in the absence of NO leads to the formation of
CF3C(O)H, CF3CH2C(O)OH, and CF3CH2C(O)OOH.5
When NOx is present, CF2O and CF3CH2C(O)OONO2 are
additionally formed.5,9
As it is well known, peroxyacyl nitrates (RC(O)OONO2) are
formed in situ by photochemical reactions involving volatile
organic compounds (aldehydes, hydrocarbons, ketones, etc.)
and nitrogen oxides, and they are also important reservoir
Received: January 11, 2013
Revised: March 25, 2013
Published: April 4, 2013
© 2013 American Chemical Society
3625
dx.doi.org/10.1021/jp4003593 | J. Phys. Chem. A 2013, 117, 3625−3629

The Journal of Physical Chemistry A
Article
completely consumed to shift the equilibrium ROONO2 ⇆
ROO• + NO2 to the peroxynitrate formation (see below).
After infrared analysis, the resulting mixture was collected by
passing it through traps at liquid nitrogen temperature to
remove oxygen excess. Subsequent distillation at 193 K allowed
elimination of carbonyl fluoride (CF2O), ClNO, and carbon
dioxide formed as photooxidation products. The remains were
kept with other different batches for further purification. They
contained peroxynitrate, C6F13CH2ONO2, and C6F13CH2C-
(O)H, three substances which are difficult to separate from
each other by trap-to-trap distillation under vacuum. Therefore,
to obtain the infrared spectra of C6F13CH2ONO2 and
C6F13CH2C(O)OONO2, we distilled in our three U-trap
system (233, 213, and 77 K) the mixture as much as possible
until every U-trap contained mostly one of each component.
From successive subtraction the spectra of both nitrate and
peroxynitrate were obtained. The content of the U-trap
containing mainly the peroxynitrate was transferred to the
infrared cell, and NO was added to study its thermal stability.
CF3CH2C(O)OONO2. Mixtures of CF3CH2C(O)H (4.0
mbar), Cl2 (3.1 mbar), NO2 (3.5 mbar), and O2 (1000
mbar) were photolyzed and then distilled, as previously
described for C6F13CH2C(O)OONO2. This procedure permit-
ted the possibility of getting good quantities of this
peroxynitrate, with purity above 95% according to the IR
bands analyzed. Other authors have seen the IR peaks but have
not prepared bulk quantities.4 The infrared spectrum of
CF3CH2C(O)OONO2 (bands at 793, 1056, 1205, 1243,
1304, 1761, 1851 cm−1) is in good agreement with all of the
bands reported by Hurley et al. 2005,9 the first research group
to report such information.
of ClNO (around 1800 cm−1) and CO2 (667 cm−1) and the
appearance of peaks at 795, 1749 and 825, 1694 cm−1
corresponding to C6 F1 3 CH2 C(O)OONO2 and
C6F13CH2ONO2, respectively. Not even at 30 min was CF2O
detected as a product, which is in accordance with the high
NO2 concentrations still present in the system (see below).
Infrared spectra of peroxynitrate and nitrate were included for
comparison.
Table 1 lists the main peaks of the products identified in this
work together with those corresponding to hydrogenated and
Table 1. Comparison of Selected Wavenumbers for Similar
Peroxynitrates (RC(O)OONO2) and Nitrates (RONO2)
R
wavenumber (cm‑1)
peroxynitrate
νas(NO2)
δs(NO2)
reference
CH3
1741
1750
794
794
15
CF3CH2
C4F9CH2
C6F13CH2
CF3
9
1749
791
16
1749
795
this work
1761
793
17
nitrate
νas(NO2)
δs(NO2)
CH3
1672
1694
1695
1694
1748
854
826
18
CF3CH2
C4F9CH2
C6F13CH2
CF3
19
16
825
this work
788
20
fluorinated peroxynitrates as well as nitrates of similar
structures. As it can be seen, there is a clear-cut difference in
the wavenumbers for a fully hydrogenated peroxynitrate and a
fully fluorinated one, being the IR bands of the mixed
peroxynitrates always located between them. Note that the
band absorptions for νas(NO2) and δs(NO2) are similar for
both CF3CH2C(O)OONO2 and C6F13CH2C(O)OONO2
under the experimental resolution, indicating that the position
of the maxima is not affected by the length of the fluorinated
chain.
Thermal stability was determined by the addition of NO, in
the temperature range between 288 and 307 K, at 9.0 and 1000
mbar of total pressure. At 307 K, pressure dependence of the
rate constant was analyzed between 3.3 and 1000 mbar.
RESULTS AND DISCUSSION
■
Photooxidation Mechanism of C6F13CH2C(O)H in the
Presence of NO2. Figure 1 depicts the infrared spectra
obtained in the photooxidation of C6F13CH2C(O)H before and
30 min after irradiation and their subtraction showing the
resulting products. Observation of the whole infrared spectrum
of the products (middle trace in Figure) reveals the formation
The complete reaction mechanism according to the products
observed is shown in Scheme 1. The photooxidation of
Scheme 1. Mechanism of Photooxidation of
C6F13CH2C(O)H
Figure 1. Infrared spectra obtained in the photooxidation of
C6F13CH2C(O)H in the presence of NO2. From top to bottom:
before photolysis; after 30 min irradiation; products; C6F13CH2C(O)-
OONO2; and C6F13CH2ONO2. The last two traces correspond to
reference spectra.
3626
dx.doi.org/10.1021/jp4003593 | J. Phys. Chem. A 2013, 117, 3625−3629

The Journal of Physical Chemistry A
Article
⎛
⎞
⎟
⎠
C6F13CH2C(O)H is initiated by the attack of chlorine atoms to
the hydrogen atom of the aldehyde group to form
C6F13CH2CO• radicals (reaction 1)4
k−5[NO2]
k6[NO]
k5 = kobs 1 +
⎜
⎝
(7)
C6F13CH2C(O)H + Cl• → C6F13CH2CO• + HCl
The ratio k−5/k6 was taken from that determined by Zabel et al.
(1994),24 who obtained a value of 0.64 for the CF3C(O)OO•
radical. They also gave limiting values (0.4 and 0.8) accounting
for the nature of the radical. The differences for the corrected
rate constants using as ratio 0.64 and the limiting values is less
than 4%, thus leaving the value chosen as a good
approximation.
(1)
which follows a series of typical reactions occurring when O2
and NO2 are present, leading mainly to peroxynitrate and
nitrate. The formation of the peroxynitrate is consistent with
the relatively high concentration of NO2, which reacts with the
C6F13CH2C(O)OO• radical.
The formation of C6F13CH2ONO2 needs some explanation,
however. C6F13CH2O• radicals could either react with either
NO2 or O2 or decompose (reactions 2−4):
The value obtained for k5 = 1.2 × 10−4 s−1 compares very
well with those of other peroxynitrates having a methylene
adjacent to the carbonyl group, that is, 1.5 × 10−4 s−1 for
25
CH3CH2C(O)OONO2 and our value of 1.6 × 10−4 s−1 for
•
C6F13CH2O• + O2 → C6F13C(O)H + HO2
(2)
CF3CH2C(O)OONO2 (see below). The characteristic peak at
1750 cm−1 was used to monitor peroxynitrate concentration
C6F13CH2O• + NO2 → C6F13CH2ONO2
(3)
and therefore determine kobs
.
C6F13CH2O• → C6F13• + CH2O
Thermal Decomposition of CF3CH2C(O)OONO2. The
temperature dependence of the first-order rate constant was
measured at two different pressures (9.0 and 1000 mbar) and
temperatures ranging from 288 to 307 K. The decomposition
(4)
but given the scarcity of direct measurements for rate constants
of long chain alkoxy radicals (>C4), those for reactions 2 and 3
have been assigned the values of 1 × 10−14 and 3 × 10−11 cm3
molec−1 s−1, respectively employing for the radical
C6F13CH2O• a similar strategy as that used by Sulbaek
Andersen et al.16 for the C4F9CH2O radical using the database
of Orlando et al.21 Within this assumption, reaction 3 is favored
under our experimental conditions. Furthermore, the formation
of nitrate is observed in the infrared spectrum of the products
shown in Figure 1, while the peak at 1777 cm−1 (corresponding
to C6F13C(O)H)4 is absent.
CFCH2C(O)OONO2 → CFCH2C(O)OO• + NO2
(8)
3
3
was carried out adding an excess of NO in the system sufficient
to titrate the peroxy radicals formed
CFCH2C(O)OO• + NO → CFCH2C(O)O• + NO2
3
3
(9)
The experimental values obtained are plotted in Figure 2 and
fitted with a linear regression to obtain the Arrhenius
The unimolecular decomposition of the alkoxy radical does
not compete effectively with reaction 2 at oxygen pressures
higher than 7 mbar,22,23 suggesting that formaldehyde will not
be formed. This agrees with the nonobservation of their
characteristic and intense infrared signals, which for our
experimental conditions would impose a detection limit of
5.3 × 10−4 mbar.
Thermal Decomposition of C6F13CH2C(O)OONO2. The
rate constant of the thermal decomposition of C6F13CH2C-
(O)OONO2 was experimentally measured at 9.0 mbar and 295
K. The peroxynitrate was introduced into the long path infrared
gas cell, NO was added, and total pressure was obtained by the
addition of N2. The thermal decomposition of C6F13CH2C-
(O)OONO2 leads to the formation of peroxy radicals and NO2
(reaction 5)
Figure 2. Arrhenius plot for thermal decomposition of CF3CH2C-
(O)OONO2. , 9.0 mbar; , 1000 mbar.
C6F13CH2C(O)OONO2 → C6F13CH2C(O)OO• + NO2
■
▲
(5)
which could recombine through reaction -5
parameters. Additional measurements of k8 at 307 K show
that the rate constant is dependent on the total pressure
(Figure 3), and even at 1000 mbar the behavior is similar to the
one shown for CF3C(O)OONO2 at 315 K.24
The Arrhenius parameters are presented in Table 2 and
compared with those of similar fluorinated and hydrogenated
peroxynitrates.
As it can be observed, the activation energy for CF3CH2C-
(O)OONO2 decreases with total pressure (114 and 108 kJ/mol
at 1000 and 9.0 mbar, respectively). It can also be seen that
when an acyl-peroxynitrate is completely fluorinated (cf. rows 2
and 4) the activation energy increases beyond experimental
uncertainty. Nevertheless, if the CF3 group has a methylene
bridging the carbonyl moiety, the former conclusion is not so
C6F13CH2C(O)OO• + NO2 → C6F13CH2C(O)OONO2
(-5)
whose occurrence is prevented by the addition of NO, which
effectively traps the peroxy radicals formed via reaction 6
C6F13CH2C(O)OO• + NO → C6F13CH2C(O)O• + NO2
(6)
However, reaction 6 increases the concentration of NO2 in
the system, and reaction -5 begins to take significance as time
elapses. Therefore, the measured effective first-order rate
constant of decomposition (kobs) is lower than the genuine
unimolecular decomposition rate constant, k5, so that eq 7 is
required to obtain the genuine k.
3627
dx.doi.org/10.1021/jp4003593 | J. Phys. Chem. A 2013, 117, 3625−3629

The Journal of Physical Chemistry A
Article
atmospheric fate of C6F13CH2C(O)H is reaction with OH
radicals, leading to the formation of C6F13CH2C(O)OO•,
which in an environment with high NO2 concentrations could
give C6F13CH2C(O)OONO2. The high stabilities of
CxF2x+1CH2C(O)OONO2 (x = 1,6) that are similar to the
stability of the most abundant peroxynitrates in the atmosphere
(PAN, PPN), as Figure 4 shows, point out that the
peroxynitrates formed from telomeric aldehydes can act as
reservoir species for NO2 and peroxy radicals in the
atmosphere.
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: fmalanca@fcq.unc.edu.ar.
Figure 3. Pressure dependence of the rate constant for the thermal
decomposition of CF3CH2C(O)OONO2 (3.3 to 1000 mbar) at
constant temperature (307 K).
Notes
The authors declare no competing financial interest.
Table 2. Kinetic Parameters for Selected Peroxynitrates at
Different Pressures
ACKNOWLEDGMENTS
■
Financial support from CONICET, ANPCYT, and SECyT-
UNC is gratefully acknowledged.
total pressure = 1000 mbar
peroxynitrate
Ea (kj/mol)
A (s−1
)
ref.
REFERENCES
CF3CH2C(O)OONO2
CH3C(O)OONO2
114
113
116
119
2
2
2
5
2.4 × 1016
2.5 × 1016
7.2 × 1016
6.0 × 1016
this work
■
15
25
24
(1) Ellis, D. A.; Martin, J, W.; De Silva, A. O.; Mabury, S, A.; Hurley,
M. D.; Andersen., M. P. S.; Wallington, T. J. Degradation of
Fluorotelomer Alcohols: A Likely Atmospheric Source of Perfluori-
nated Carboxylic Acids. Environ. Sci. Technol. 2004, 38, 3316−3321.
(2) Martin, J. W.; Whittle, D. M.; Muir, D. C. G.; Mabury, S. A.
Perfluoroalkyl Contaminants in a Food Web from Lake Ontario.
Environ. Sci. Technol. 2004, 38, 5379−5385.
(3) Martin, J. W.; Smithwick, M. M.; Braune, B. M.; Hekstra, P. F.;
Muir, D. C. G.; Mabury, S. A. Identification of Long-Chain
Perfluorinated Acids in Biota from the Canadian Arctic. Environ. Sci.
Technol. 2004, 38, 373−380.
(4) Chiappero, M. S.; Arguello, G. A.; Hurley, M. D.; Wallington, T.
J. Atmospheric Chemistry of n-C6F13CH2CHO: Formation from n-
C6F13CH2COH, Kinetics, and Mechanisms of Reactions with Chlorine
Atoms and OH Radicals. J. Phys. Chem. A 2010, 114, 6131−6137.
(5) Kelly, T.; Bossoutrot, V.; Magneron, I.; Wirtz, K.; Treacy, J.;
Mellouki, A.; Sidebottom, H.; Le Bras, G. A Kinetic and Mechanistic
Study of Reactions of OH Radicals and Cl Atoms with 3,3,3-
Trifluoropropanol under Atmospheric Conditions. J. Phys. Chem. A
2005, 109, 347−355.
(6) Chiappero, M. S.; Malanca, F. E.; Arguello, G. A.; Wooldridge, S.
T.; Hurley, M. D.; Ball, J. C.; Wallington, T. J.; Waterland, R. L.; Buck,
R. C. Atmospheric Chemistry of Perfluoroaldehydes (CxF2x+1CHO)
and Fluorotelomer Aldehydes (CxF2x+1CH2CHO): Quantification of
the Important Role of Photolysis. J. Phys. Chem. A 2006, 110, 11944−
11952.
a
CH3CH2C(O)OONO2
CF3C(O)OONO2
total pressure = 9.0 mbar
peroxynitrate
Ea (kj/mol)
A (s−1
)
ref.
a
CF3CH2C(O)OONO2
CH3C(O)OONO2
108
106
107
2
1.5 × 1015
this work
15
b
CH3CH2C(O)OONO2
3
1.5 × 1015
25
a
Uncertainty for the activation energy of CF3CH2C(O)OONO2 was
calculated from the fitting of the experimental data points of the rate
constants used in the Arrhenius plot. Measured at 11.5 mbar
b
clear because the difference in activation energies becomes on
the order of the experimental uncertainty (cf. rows 1 and 3).
CONCLUSIONS
■
The results obtained have significant implications for under-
standing of the atmospheric oxidation mechanism of
C6F13CH2C(O)H, in the presence of O2 and NO2. The
(7) Sulbaek Andersen, M. P.; Nielsen, O. J.; Hurley, M. D.; Ball, J. C.;
Wallington, T. J.; Stevens, J. E.; Martin, J. W.; Ellis, D. A.; Mabury, S.
A. Atmospheric Chemistry of n- CxF2x+1CHO (x = 1,3,4): Reaction
with Cl Atoms, OH Radicals and IR Spectra of CxF2x+1C(O)O2NO2. J.
Phys. Chem. A 2004, 108, 5189−5196.
(8) Solignac, G.; Mellouki, A.; Le Bras, G.; Barnes, I.; Benter, Th.
Reaction of Cl Atoms with C6F13CH2OH, C6F13CHO, and C3F7CHO.
J. Phys. Chem. A 2006, 110, 4450−4457.
(9) Hurley, M. D.; Misner, J. A.; Ball, J. C.; Wallington, T. J.; Ellis, D.
A.; Martin, J. W.; Mabury, S. A.; Sulbaek Andersen, M. P. Atmospheric
Chemistry of CF3CH2CH2OH: Kinetics, Mechanisms and Products of
Cl Atom and OH Radical Initiated Oxidation in the Presence and
Absence of NOx. J. Phys. Chem. A 2005, 109, 9816−9826.
(10) Singh, H. B. Reactive Nitrogen in the Atmosphere. Environ. Sci.
Technol. 1987, 21, 320−327.
Figure 4. Atmospheric thermal lifetimes for CH3C(O)OONO2
(dotted line),15 CH3CH2C(O)OONO2 (dashed line),25 and
CF3CH2C(O)OONO2 (solid line).
(11) Roberts, J. M. The Atmospheric Chemistry of Organic Nitrates.
Atmos. Environ. 1990, 24A, 243−287.
3628
dx.doi.org/10.1021/jp4003593 | J. Phys. Chem. A 2013, 117, 3625−3629

The Journal of Physical Chemistry A
Article
(12) Grosjean, D.; Williams, E. L., II; Grosjean, E. Peroxyacyl
Nitrates at Southern California Mountain Forest Location. Environ. Sci.
Technol. 1993, 27, 110−121.
(13) Williams, E. L., II; Grosjean, D.; Grosjean, E. Ambient Levels of
the Peroxyacyl Nitrates PAN, PPN and MPAN in Atlanta, Georgia. J.
Air Waste Manage. Assoc. 1993, 43, 873−879.
(14) Flocke, F. M.; Weinheimer, A. J.; Swanson, A. L.; Roberts, J. M.;
Schmitt, R.; Shertz, S. On the Measurement of PANs by Gas
Chromatography and Electron Capture Detection. J. Atmos. Chem.
2005, 52, 19−43.
(15) Bridier, I.; Caralp, F.; Loirat, H.; Lesclaux, R.; Veyret, Bernard;
Becker, K. H.; Reimer, A.; Zabel, F. Kinetics and Theoretical Studies of
the Reactions CH3C(O)O2 + NO2 + M ⇆ CH3C(O)O2NO2 + M
between 248 and 393 K and between 30 and 760 Torr. J. Phys. Chem.
1991, 95, 3594−3600.
(16) Sulbaek Andersen, M. P.; Nielsen, O. J.; Hurley, M. D.; Ball, J.
C.; Wallington, T. J.; Ellis, D. A.; Martin, J. W.; Mabury, S. A.
Atmospheric Chemistry of 4:2 Fluorotelomer Alcohol (n-
C4F9CH2CH2OH): Products and Mechanisms of Cl Atom Initiated
Oxidation in the Presence of NOx. J. Phys. Chem. A 2005, 109, 1849−
1856.
(17) Kopitzky, R.; Beuleke, M.; Balzer, G.; Willner, H. Properties of
Trifluoroacetyl Peroxynitrate CF3C(O)OONO2. Inorg. Chem. 1997,
36, 1994−1997.
(18) Stanton, J. F.; Flowers, B. A.; Matthews, D. A.; Ware, A. F.;
Barney Ellison, G. Gas-Phase Infrared Spectrum of Methyl Nitrate. J.
Mol. Spectrosc. 2008, 251, 384−393.
(19) Li, S. Fourier Transform Infrared Absorption Spectroscopy and
Kinetics Studies of Gas Phase Small Molecules. Ph.D. Thesis, National
University of Singapore, 2006.
(20) Sander, S.; Willner, H.; Oberhammer, H.; Arguello, G. A.
̈
Trifluormethylnitrat, CF3ONO2. Z. Anorg. Allg. Chem. 2001, 627,
655−661.
(21) Orlando, J. J.; Tyndall, G. S.; Wallington, T. J. The Atmospheric
Chemistry of Alkoxy Radicals. Chem. Rev. 2003, 103, 4657−4689.
(22) Nielsen, O. J.; Gamborg, E.; Sehested, J.; Wallington, T. J.;
Hurley, M. D. Atmospheric Chemistry of HFC-143a: Spectrokinetic
Investigation of the CF3CH2O Radical, Its Reactions with NO and
NO2, and the Fate of CF3CH2O. J. Phys. Chem. 1994, 98, 9518−9525.
(23) Mogelberg, T. E.; Nielsen, O. J.; Sehested, J.; Wallington, T. J.;
Hurley, M. D. Atmospheric Chemistry of HFC-272ca: Spectrokinetic
Investigation of the CH3CF2CH2O2 Radical, Its Reactions with NO
and NO2, and the Fate of CH3F2CH2O Radical. J. Phys. Chem. 1995,
99, 1995−2001.
(24) Zabel, F.; Kirchner, F.; Becker, K. H. Thermal Decomposition of
CF3C(O)O2NO2, CClF2C(O)O2NO2, CClFC(O)O2NO2 and CCl3C-
(O)O2NO2. Int. J. Chem. Kinet. 1994, 26, 827−845.
(25) Kirchner, F.; Mayer-Figge, A.; Zabel, F.; Becker, K. H. Thermal
Stability of Peroxynitrates. Int. J. Chem. Kinet. 1999, 31, 127−144.
3629
dx.doi.org/10.1021/jp4003593 | J. Phys. Chem. A 2013, 117, 3625−3629