Chemosphere 286 (2022) 131562

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Diurnal photodegradation of fluorinated diketones (FDKs) by OH radicals

using different atmospheric simulation chambers: Role of keto-enol
tautomerization on reactivity
Pedro L. Lugo a, V.G. Straccia a, Cynthia B. Rivela a, Iulia Patroescu-Klotz b, Niklas Illmann b,
Mariano A. Teruel a, Peter Wiesen b, Maria B. Blanco a, *
a
(L.U.Q.C.A), Laboratorio Universitario de Química y Contaminación del Aire. Instituto de Investigaciones en Fisicoquímica de Córdoba (I.N.F.I.Q.C.), Dpto. de
Fisicoquímica. Facultad de Ciencias Químicas, Universidad Nacional de Córdoba. Ciudad Universitaria, 5000, Córdoba, Argentina
b
Institute for Atmospheric and Environmental Research, Bergische Universität Wuppertal, 42097, Wuppertal, Germany

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Predominance of enolic tautomers than

the keto form on the reactivity of fluo­
rinated diketones.
• Predominant addition of OH to the
double bond in the enol form of fluori­
nated diketones.
• Significant tropospheric ozone forma­
tion (POCP) for the fluorinated dike­
tones (23–34).
• Relative high acidification potentials
(AP) for the fluorinated diketones
(0.5–0.6).
• Short tropospheric lifetimes, about
hours, with negligible contribution to
global warming.

A R T I C L E I N F O A B S T R A C T

Handling Editor: R Ebinghaus Rate coefficients for the gas-phase reactions of OH radicals with a series of fluorinated diketones have been
determined for the first time at (298 ± 3) K and atmospheric pressure using the relative method and FTIR
Keywords: spectroscopy and GC-FID to monitor both reactants and references. The following values, in 10− 11 cm3 mole­
Diketones cule− 1 s− 1, were obtained for 1,1,1-trifluoro-2,4-pentanedione (TFP), 1,1,1-trifluoro-2,4-hexanedione (TFH) and
Fluorinated carbonyls
1,1,1-trifluoro-5-methyl-2,4-hexanedione (TFMH), respectively: k1(TFP + OH) = (1.3 ± 0.4), k2(TFH + OH) =
Keto-enolic tautomerization
(2.2 ± 0.8), k3(TFMH + OH) = (3.3 ± 1.0). The results are discussed with respect to the keto-enolic tautome­
In situ FTIR
SPME-GC-FID rization specific for β-diketones.
Reactivity Based on the present results, the tropospheric lifetimes of TFP, TFH and TFMH upon degradation by OH
radicals were calculated as 21, 13 and 8 h, respectively indicating that transport might play a role in the at­
mospheric fate of the studied compounds. Photochemical ozone creation potentials were estimated for TFP, TFH
and TFMH to be: 23, 29 and 34, respectively.

* Corresponding author.
E-mail address: m.belen.blanco@unc.edu.ar (M.B. Blanco).

https://doi.org/10.1016/j.chemosphere.2021.131562
Received 1 April 2021; Received in revised form 5 July 2021; Accepted 13 July 2021
Available online 19 July 2021
0045-6535/© 2021 Elsevier Ltd. All rights reserved.
P.L. Lugo et al.
1. Introduction
Fluorinated diketones (FDKs) are extensively used in organic syn­
thesis of drugs, special dyes and coatings (De Rosa et al., 2015; Ilmi
et al., 2019; Isakova et al., 2010) and metallurgy, where they act as
chelating agents (Babain et al., 2002). Some of these applications im­
plies metal-organic chemical vapor deposition techniques that is a po­
tential source of air borne diketones (Bareño et al., 2020). Due to their
structure, possessing both C–F bonds and carbonyl moieties, they might
bear a significant global warming potential (GWP (Hodnebrog et al.,
2013)). While a series of hydrofluoroolefines, -ethers, -alcohols and
-ketones have been studied with respect to their atmospheric fate (ki­
netic and mechanistic information) and GWP values (Jiménez et al.,
2016; Mellouki et al., 2015; Paul et al., 2020; Wallington et al, 2004,
2015) for FDKs no data were yet reported.
Prediction of rate constants through structure activity relationships
(SAR) is a proficient tool for many substances those gas-phase reactions
with atmospheric oxidants cannot be investigated directly. The SAR
model developed by the Atkinson group in US (Atkinson, 1987; Kwok
and Atkinson, 1995) works quite well for some class of substances but
there are many exceptions, halogenated compounds being among them.
The inconsistencies result from missing an extensive kinetic data pool.
Therefore, the latest SAR development excludes estimation of rates for
the reaction of OH radicals with halogen or sulfur containing com­
pounds for which the information is relatively scarce (Jenkin et al.,
2018). Works as the present study contribute to refine and complete our
understanding of SAR models.
Beside the importance for the climate impact modelling and the
contribution to a comprehensive gas-phase kinetics data base, fluori­
nated β-diketones are of particular interest because of the keto-enolic
tautomerization specific for this kind of compounds. The existence of
this equilibrium is well known for 1,3-diketones and was described in
the liquid (Burdett and Rogers, 1964) as well as in the gas phase
(Nakanishi et al., 1977) while few reports exist on the influence of
electron-withdrawing substituents (halogen atoms) favouring the enolic
tautomer in solution (Bassetti et al., 1988; Lintvedt and Holtzclaw,
1966). Similarly, the OH initiated gas-phase oxidation of diketones was
extensively studied (Bell et al., 2006; Holloway et al., 2005; Messaadia
et al., 2015; Zhou et al., 2008), but, by best of our knowledge, no similar
information was ever reported for the fluorinated β-diketones.
In this work, we report for the first time the rate coefficients for the
reactions of OH radicals with a series of FDKs: 1,1,1-trifluoro-2,4-penta­
nedione (TFP), 1,1,1-trifluoro-2,4-hexanedione (TFH) and 1,1,1-tri­
fluoro-5-methyl-2,4-hexanedione (TFMH) as follows:
CF3C(O)CH2C(O)CH3 + OH → Products k1 (1)
CF3C(O)CH2C(O)CH2CH3 + OH → Products k2 (2)
CF3C(O)CH2C(O)CH(CH3)2 OH Products k3 (3)
+ →
The investigations were performed in two similarly built atmo­
spheric simulation chambers coupled with different analytical tech­
niques, in situ FTIR spectroscopy in BUW chamber (Wuppertal) and GC-
FID in LUQCA chamber (Córdoba) using two different photolytic sources
of OH radicals.
The kinetic data are used to infer the environmental implications of
the OH radicals-initiated oxidation of FDKs such as tropospheric lifetime
and photochemical ozone creation potential (POCP).
2. Experimental section
Kinetic experiments using the relative-rate method were conducted
in both the BUW chamber and the LUQCA chamber at (990 ± 15) mbar
of air and a temperature of (298 ± 3) K. Typical duration of the exper­
iments ranged from 10 to 35 min, with a 2 min period of homogenisation
before irradiation.
2
Chemosphere 286 (2022) 131562
2.1. BUW chamber
The BUW chamber consists of a 3 m long borosilicate glass cylinder
(45 cm inner diameter) closed at both ends by aluminium flanges, on
which various ports for gas and reactants supply and sampling and in­
struments monitoring physical parameters inside the chamber are
mounted. The reactor, with a total volume of 480 L, is surrounded by 32
evenly spaced fluorescent lamps (Philips TLA 40 W, 300 ≤ λ ≤ 450 nm,
λmax = 360 nm). The whole construction is encased in reflective steel
sheets and cooled with air. The homogeneous mixing of the reactants is
ensured by a magnetically coupled Teflon fan placed on the front flange,
inside the chamber. Between experiments the reactor is evacuated by a
double stage pumping system, a fore pump and a roots vacuum booster,
to an end vacuum up to 10− 3 Torr. Cleanliness is accomplished by filling
the reactor up to 200 mbar and evacuate to vacuum and repeating this
sequence until no absorption bands belonging to reactants or products
are present in the IR spectra.
The concentration-time profile of reactants and products are moni­
tored in situ using a multi-reflection White mirror system (2.80 ± 0.01 m
base length) mounted in the reactor and coupled to a Nicolet 6700 FTIR
spectrometer (MCT detector). The White system is operated at 18 tra­
verses which yields a 50.4 m path length. The IR spectra were recorded
in the 700-4000 cm− 1 spectral range with 1 cm− 1 resolution by co-
adding 30 interferograms over (30 ± 2) s. Typically, during an experi­
ment were recorded 15 spectra, the first 5 without irradiation.
In the BUW chamber the OH radicals were produced using the
photolysis of methyl nitrite (CH3ONO) in the presence of NO (Atkinson
et al., 1995):
CH3 ONO + hv→CH3 O + NO (4)
CH3 O + O2 →CH2 O + HO2 (5)
HO2 + NO→NO2 + OH (6)
2.2. LUQCA chamber
The LUQCA chamber, installed at the National University of Córdoba
has a similar design to the BUW chamber, being a borosilicate cylinder
sealed at both ends by aluminum flanges, but the dimensions and some
construction details differs. The cylinder, of 1.5 m length and 0.6 m
inner diameter, has a total volume of 405 L. Homogeneity of the gas
mixtures is ensured similar to the BUW chamber.
The glass cylinder includes, placed eccentrically at 5 cm of the bot­
tom and sealed tight between the aluminum flanges, a quartz made
cylinder of 1.5 m length and 0.1 m inner diameter that houses three low-
pressure mercury vapor lamps (Philips, TUV 40 W, λmax = 254 nm). The
quartz cylinder is open to ambient air allowing the lamps to be cooled by
a fan placed at one end.
Between experiments the reactor is evacuated by a fore pump.
Cleaning is achieved by filling the reactor up to 900 mbar and evacu­
ating under vacuum and repeating this sequence until no signals of the
compounds to be studied are present in the GC-FID.
Organic species were monitored by a gas chromatograph equipped
with flame ionization detection (GC-FID) Shimadzu GC-2014B, using an
Rtx-5 capillary column (fused silica G27, 30 m × 0.25 mm 0.25 μm). Gas
samples were collected from the 405 L reactor, using one of the sampling
ports on the front flanges, by solid phase microextraction (SPME). The
SPME technique involves extraction of analytes from the sample matrix
using a silica fiber covered with an absorbent polymer, followed by
thermal desorption of analytes in the chromatograph’s injection port.
The fiber composition was chosen according to the compounds studied,
namely Divinylbenzene/Carboxen/polydimethylsiloxane (DVB/CAR/
PDMS), provided by Supelco, (Bellefonte, PA, USA). The methodology
used was: irradiation of the mixture target + reference compounds for 1
min, sampling via SPME (exposing the fiber inside the reaction
P.L. Lugo et al. Chemosphere 286 (2022) 131562

Table 1 2.4. Materials

Initial mixing ratios in [ppm] (1 ppm = 2.46 × 1013 molecule cm− 3) of each
species used in the experiments. The chemicals used in the experiments had the following purities, as
Compound BUW chamber LUQCA chamber given by the manufacturer, and were used as supplied: synthetic air (Air
[ppm] [ppm] Liquide, 99.999%), 1,1,1-Trifluoro-2,4-pentanedione (Aldrich, 99%),
1,1,1-Trifluoro-2,4-pentanedione 8.4–10.5 5.0–7.5 1,1,1-Trifluoro-2,4-hexanedione (Aldrich, 99%), 1,1,1-Trifluoro-5-
1,1,1-Trifluoro-2,4-hexanedione 7.4–9.2 4.4–6.6 methyl-2,4-hexanedione (Aldrich, 99%), Isobutene (Messer Griesheim,
1,1,1-Trifluoro-5-methyl-2,4- 6.8–8.5 4.4–6.6 99%), 1,3-butadiene (Aldrich 99%), Propene (Messer Griesheim
hexanedione
99.95%), Diethyl ether (Fluka, 99%), NO (Messer Griesheim, 99%) and
Isobutene 20.9–31.3 –
1,3-Butadiene 20.9–31.3 – H2O2 (Interox, 85% w/w). Methyl nitrite was synthesized by the drop­
Propene 20.9–31.3 – wise addition of 50% H2SO4 to a saturated solution of sodium nitrite in
Diethyl ether – 40.7–43.6 methanol and collected and stored in a cooling trap at – 78 ◦ C. IR spectra
NO 20.9–31.3 – of a gaseous methyl nitrite sample shown no impurities were present.
H2O2 13–15
The initial concentrations of each species are summarized in Table 1.
–
Methyl nitrite 20.9–31.3 –

3. Results and discussion

chamber) for 8 min and thermal desorption of the sample over 2 min in
the injection port. This sequence was repeated until the desired amount The rate coefficients for the reaction between OH radicals and 1,1,1-
of irradiation time was achieved. All determinations were carried out trifluoropentane-2,4-dione (TFP), 1,1,1-trifluorohexane-2,4-dione
under atmospheric conditions. (TFH) or 1,1,1-trifluoro-5-methylhexane-2,4-dione (TFMH) were
In the LUQCA chamber OH radicals were generated by the photolysis determined relative to the consumption of three reference compounds at
of hydrogen peroxide using the mercury lamps: (298 ± 3) K and (990 ± 15) mbar. For the experiments evaluated via
FTIR results, the absorption features centred at 1112 cm− 1, assigned to
H2 O2 + hv→2 OH (7)
ν(CF3), were used to determine the consumption of all FDKs. For refer­
ences, the absorption bands centred at 889, 913 and 908 cm− 1 were used
2.3. Relative-rate method for the quantification of isobutene, propene and 1,3-butadiene, respec­
tively. Using GC-FID, for each FDK experiment no signal overlap was
The relative rate technique relies on the assumption that both the detected and, in the chromatograms, only one peak was observed for
fluorinated diketones (FDK) and the reference compounds are removed each FDK (Fig. 1). The relative ratios kFDK/kref. of each experiment were
solely by reaction with OH radicals: obtained from linear regression analysis where the intercepts of each
regression line were found to be nearly zero. Table 2 summarises the
OH + FDK→Products (8)
experimental results obtained within this study. The relative-rate plots
OH + Reference→Products (9) according to equation (10) are shown in Figs. 2–4. No differences in
kFDK/kref were observed for different initial concentrations or a variation
The direct interaction of the compounds with the OH source chem­ of the total consumption during the experiments (21–40% for TFP,
icals and heterogeneous loss was observed for 5 min previous each 26–56% for TFH and 30–63% for TFMH, respectively).
irradiation and found negligible. Photolysis of the fluorinated diketones The following rate coefficients were determined by averaging the
and reference compounds in the absence of the OH sources was likewise values of the individual experiments:
found to be negligible. Therefore, the relationship between the rate
constants of the reference compound and the FDK can be expressed as: k1-FTIR = (1.3 ± 0.5) × 10− 11 cm3 molecule− 1 s− 1
{ }
kFDK
{ } k1-GC-FID = (1.3 ± 0.2) × 10− 11 cm3 molecule− 1 s− 1
[FDK]0 [Ref ]0
Ln = Ln (10) k2-FTIR = (2.3 ± 0.8) × 10− 11 cm3 molecule− 1 s− 1
[FDK]t kRef [Ref ]t
k2-GC-FID = (2.1 ± 0.8) × 10− 11 cm3 molecule− 1 s− 1

where, [FDK]0, [Ref]0, [FDK]t and [Ref]t are the concentrations of the k3-FTIR = (3.2 ± 1.1) × 10− 11 cm3 molecule− 1 s− 1
fluorinated diketones and reference compound at times t = 0 and t, k3-GC-FID = (3.4 ± 0.8) × 10− 11 cm3 molecule− 1 s− 1

respectively and kFDK and kRef are the rate coefficients of the reactions
(8) and (9), respectively.

Fig. 1. Chromatographic separation of (a) 1,1,1-Trifluoropentane-2,4-dione (TFP) and (b) diethyl ether (reference) under the experimental conditions of the pre­
sent study.

3
P.L. Lugo et al. Chemosphere 286 (2022) 131562

Table 2 in the enolic tautomers. For the TFP-analogue structure pentane-2,4-

Rate coefficients for the reaction of OH radicals with TFP, TFH TFMH experi­ dione (acetyl acetone, Acac) is has been shown that in the gas-phase
mentally determined in this study. more than 90% of the compound are present in the enolic form at
FDKs Technique Reference kFDK/ kOH × 1011 (cm3 room temperature (Nakanishi et al., 1977). The enolic form is stabilized
kref molecule− 1s− 1) due to intramolecular H bonding between the OH moiety and the
TFP Isobutene a 0.29 1.5 ± 0.3 carbonylic oxygen. Zhou et al. (2008) investigated the OH radical
1,1,1-Trifluoro- ± 0.01 initiated oxidation of Acac in the gas-phase and showed that the iden­
2,4-pentanedione FTIR 0.29 1.5 ± 0.3 tified main products (acetic acid, methyl glyoxal and pentane-2,3,
± 0.01
b 4-trione) can be well explained by addition of OH to the C– – C double
Propene 0.44 1.1 ± 0.2
± 0.02 bond in the enol form. Burdett and Rogers (1964) determined the frac­
0.48 1.3 ± 0.2 tion of enol for a series of β-diketones via NMR spectroscopy in the liquid
± 0.02 phase. According to their results the fraction of enol is 81% for Acac and
Average 1.3 ± 0.5 97% for TFP, respectively. However, they do not differentiate between
GC-FID Diethyl 0.98 1.3 ± 0.3
ether c ± 0.04 1.3 ± 0.4
the various enol tautomers possible in the case of asymmetric
0.96 β-diketones.
± 0.03 Fig. 6 presents the region between 1000 cm− 1 and 2000 cm− 1 of the
Average 1.3 ± 0.3 FTIR spectra recorded for the title FDKs in the BUW chamber. In all cases
TFH Isobutene a 0.41 2.1 ± 0.3
it is obvious that the carbonyl absorption is dominated by absorption
1,1,1-Trifluoro- ± 0.01
2,4-hexanedione 0.42 2.1 ± 0.4 features centred on the range 1609–1616 cm− 1 and 1659 - 1664 cm− 1.
± 0.01 Only for TFH and TFMH small absorptions are visible as well around
FTIR Propene b
0.98 2.6 ± 0.4 1840 cm− 1. Based on text-book knowledge the absorption of the C– –O
± 0.02 stretching vibration in saturated, acyclic ketones should be located in
0.88 2.3 ± 0.4
the spectral region between 1705 and 1725 cm− 1. However, intra-
± 0.03
Average 2.3 ± 0.8 molecular H bonding and resonance effects in the enolic tautomers
GC-FID Diethyl 1.70 2.2 ± 0.4 would decrease the bond strength of the C– – O moiety and subsequently
ether c ± 0.07 1.9 ± 0.3 lower the frequency of its absorption band. Therefore, the infrared
1.45
spectra prove the predominance of the enolic tautomers for all investi­
± 0.04
Average 2.1 ± 0.8 gated species in the gas-phase. The features around 1840 cm− 1 suggests
TFMH Propene b
1.08 2.8 ± 0.6 that in the case of TFH and TFMH a small fraction of these compounds is
1,1,1-Trifluoro-5- ± 0.05 present as keto tautomer in the experimental system.
methyl-2,4- FTIR 1.18 3.1 ± 0.8 On the other hand, carbonyl absorption features are shifted to higher
hexanedione ± 0.13
frequencies when halogen atoms are in the α-position. For example, the
1,3- 0.45 3.2 ± 0.8
Butadiene ± 0.05 absorption band of the C– – O stretching vibration is shifted around 40
d
cm− 1 towards higher frequencies in the case of trifluoroacetic acid (TFA)
0.51 3.6 ± 0.7 compared to acetic acid. Thus, the twin-peak profile of the FDK’s
± 0.03
carbonyl absorptions likely results from the coexistence of both enolic
Average 3.2 ± 1.1
GC-FID Diethyl 2.53 3.3 ± 0.7
tautomers in the gas-phase with the band below 1700 cm− 1 being
ether c ± 0.12 3.5 ± 0.6 attributed to enol (b) (Fig. 5). This is also supported by the small shift of
2.67 the twin-peak features toward lower wavenumbers observed when
± 0.10 comparing the TFP spectrum to TFH and TFMH, which is consistent with
Average 3.4 ± 0.8
the increased inductive effect of the alkyl rest R. By assuming the ab­
a − 11
kisobutene+OH = (5.07 ± 0.51) × 10 cm molecule s− 1(Atkinson et al.,
3 − 1
sorption cross sections of C– – O bands in both enols to be similar, the
1997). ratio of their IBIs (= integrated band intensity) indicates rather a pref­
b
kpropene+OH = (2.63 ± 0.20) × 10− 11 cm3 molecule− 1 s− 1(Atkinson et al., erence for enol (a) for all three FDKs. This is in agreement with a study of
1997). Zahedi-Tabrizi and co-workers (Zahedi-Tabrizi et al., 2006) who
c
kdiethyl ether+OH = (1.32 ± 0.20) × 10− 11 cm3 molecule− 1 s− 1(Mellouki et al.,
concluded that, based on DFT calculations, enol (a) (according to Fig. 5)
2015).
d is slightly more stable than enol (b) in the case of TFP. However, the
k1,3-butadiene+OH = (7.00 ± 0.30) × 10− 11 cm3 molecule− 1 s− 1(Ghosh et al.,
2010). authors compared experimental and calculated IR spectra of gaseous
TFP and assigned the bands centred on around 1616 cm− 1 and 1661
cm− 1 to the symmetric and asymmetric C– – C–C–– O stretching rather
where the error represents a combination of the 2σ statistical error of the
than to the C– – O stretching of both enol tautomers. A mechanistic
mean and an additional 15% relative error to cover the uncertainties
investigation of the FDK’s gas-phase oxidation is therefore needed to
derived from the evaluation procedure. To the best of our knowledge
estimate the fraction of both enol tautomers.
there are no previous kinetic studies on FDKs and thus a direct com­
Table 3 compares the values calculated for the reaction of the
parison of the experimentally determined rate coefficients is not
different tautomers of the studied FDKs with OH using the AOPWIN™
possible. However, an excellent agreement is observed between the two
software (EPI Suite™, https://www.epa.gov/tsca-screening-tools/epi-s
detection methods for each of the investigated species.
uitetm-estimation-program-interface) to the experimentally deter­
The FDKs are, as stated in the introduction, β-diketones. Typical for
mined values. This employs the SAR premises elaborated by Kwok and
these compounds is the ability to rearrange the position of double bonds
Atkinson (1995). In the keto form, the reaction of the studied com­
in their molecules, exchanging one carbonyl moiety for an enol group.
pounds with OH radicals might occur via hydrogen atom abstraction at
This particular case of isomerism is called keto-enol tautomerism and
the –CH2– group enclosed between both carbonyl moieties and either
the resulting structures are named tautomers. Fig. 5 shows the possible
the terminal methyl, ethyl or iso-propyl group. The rate coefficients (at
tautomers formed in the keto-enolic equilibrium of FDKs in the gas
room temperature) for the keto form of TFP, TFH and TFMH estimated
phase, taking into account their asymmetric structure. The OH reaction
by AOPWIN™ are 0.18 × 10− 12 cm3 molecule− 1 s− 1, 1.31 × 10− 12 cm3
with these species may thus proceed either via H-abstraction in the keto
molecule− 1 s− 1 and 2.59 × 10− 12 cm3 molecule− 1 s− 1, respectively. The
form or addition of the OH radical to the double bond and H-abstraction
contribution of the addition of OH to the C– – C double bond to the

4
P.L. Lugo et al.
Fig. 2. Relative-rate plot of 1,1,1-trifluoropentane-2,4-dione.; error bars derived from experimental and evaluation errors.
Fig. 3. Relative-rate plot of 1,1,1-trifluorohexane-2,4-dione; error bars derived from experimental and evaluation errors.
overall rate constant is calculated similarly as 5.94 × 10− 11 cm3 mole­
cule− 1 s− 1 for enol (a) and 7.82 × 10− 11 cm3 molecule− 1 s− 1 for enol (b),
same for all three FDKs. By considering the magnitude of the experi­
mentally determined rate coefficients together with the gas-phase IR
spectra, there is a clear evidence that the OH initiated oxidation of the
FDKs is dominated by addition to the C– – C double bond of the enol
tautomers. Re-equilibrium between the tautomers is not expected to
play a significant role due to the much higher reactivity of the C– –C
double bond compared to the H atom abstraction in the diketone forms
and the large fraction of enol present in the gas-phase for all investigated
FDKs. Besides, re-equilibrium processes would result in non-linear
relative rate plots. Since this behaviour could not be observed for any
of the target species, irrespective of the level of consumption and the
detection method, this is a further evidence that re-equilibrium is not
important in the experimental system. However, one should note that
the tentative discrimination of both enol tautomers would be possible
solely in the carbonyl absorption region which cannot be used for the
evaluation due to the formation of high amounts of NO2 during the
5
Chemosphere 286 (2022) 131562
methyl nitrite photolysis. Therefore, the rate coefficients cannot be
assigned to one of the enol tautomers and reflect the overall enol reac­
tivity for each investigated system.
The experimentally determined rate coefficients are up to a factor of
6 smaller than predicted by AOPWIN™. In Table 3 we added, for com­
parison, the calculated and experimental data for pentane-2,4-dione
(Acac) as reported in former studies (Bell et al., 2006; Holloway et al.,
2005; Messaadia et al., 2015; Zhou et al., 2008). Given that the calcu­
lated kOH value for the enol tautomer of Acac is consistent with the
experimentally determined rate coefficients, the SAR approach seems to
reproduce generally the reactivity of the enol’s substitution pattern. This
suggests that the differences between the SAR calculation and our
experimental data are correctly attributed to the inaccuracy of the
estimated contribution due to the presence of halogen atoms, as
mentioned in the introduction.
According to literature data the bimolecular rate coefficient is in the
range (7.9–9.1) × 10− 11 cm3 molecule− 1 s− 1 for the reaction of OH
radicals with Acac (Bell et al., 2006; Holloway et al., 2005; Messaadia
P.L. Lugo et al. Chemosphere 286 (2022) 131562

Fig. 4. Relative-rate plot of 1,1,1-trifluoro-5-methylhexane-2,4-dione; error bars derived from experimental and evaluation errors.

Fig. 5. Keto-enol tautomerism of the fluorinated diketones (R = –CH3 for TFP, R = –CH2CH3 for TFH and R = –CH(CH3)2 for TFMH).

Fig. 6. Infrared spectra of the fluorinated diketones and acetyl acetone in the gas-phase.

et al., 2015; Zhou et al., 2008). Thus, our results show TFP to be a factor
of 6–7 less reactive than its hydrogenated analogue structure. This can
be rationalized in terms of the strong electron-withdrawing effect of the
–CF3 group yielding a decrease of electron density associated with the
olefinic bond. Consequently, the enol is expected to be less reactive to­
wards electrophiles. Given that inductive effects are attenuated with
distance from the reactive centre of the molecule, one would intuitively
expect enol (a) to be less reactive than enol (b) which is in agreement
with the SAR calculations. A rate coefficient of 1.3 × 10− 12 cm3 mole­
cule− 1 s− 1 (González et al., 2015) has been reported for the reaction of
OH radicals with 3,3,3-trifluoropropene which is thus about 20 times
less reactive than propene (Daranlot et al., 2010). Since the OH reaction
of this species proceeds solely through the addition to the C– – C double
bond one can assign the reduction of reactivity to the strong negative
inductive effect of the adjacent –CF3 substituent upon the C– – C double
bond. On the other hand, 2,2,2-trifluoroethyl methacrylate (Tovar and
Teruel, 2014) is less reactive towards OH radicals by a factor of about 2
compared to ethyl methacrylate (Blanco et al., 2006; Ren et al., 2019).
Given that rate coefficients are only slightly higher for ethyl methac­
rylate than for methyl methacrylate the influence of H atom abstraction

6
P.L. Lugo et al. Chemosphere 286 (2022) 131562

Table 3 Table 5
Comparison of calculated and experimentally determined rate coefficients POCP values calculated in the present work.
values in cm3 molecule− 1 s− 1 for the reaction of OH radicals with FDKs. VOCs εPOCP
Compound Tautomer kH- kaddition koverall kexperimental
Ethene (reference value) CH2=CH2 100a
× × 1011 × 1011 × 1011
abstraction
2 Acac CH3C(O)CH2C(O)CH3 62b
10
TFP CF3C(O)CH2C(O)CH3 23b
TFP keto form 0.179 0.000 0.018 1.3 ± 0.4b TFH CF3C(O)CH2C(O)CH2CH3 29b
enol (a) 0.242 5.944 5.968 TFMH CF3C(O)CH2C(O)CH(CH3)2 34b
enol (b) 0.276 7.821 7.849 a
(Derwent et al., 1998); and c this work.
TFH keto form 1.308 0.000 0.131 2.2 ± 0.8b
enol (a) 1.371 5.944 6.081
enol (b) 1.241 7.821 7.945 In order to estimate tropospheric lifetimes for reactive gases not only
TFMH keto form 2.593 0.000 0.259 3.3 ± 1.0b
the chemical transformations but also the meteorology and geographical
enol (a) 2.656 5.944 6.210
enol (b) 2.415 7.821 8.062
location of the emission sources should be considered. However, since it
Acac keto form 0.730 0.000 0.730 8.7 ± 0.7c is difficult to comprise these conditions at all times, for practical reasons
enol form 0.380 7.821 7.859 it is useful to calculate an approximate tropospheric value. Thus, for
a
TFP: 1,1,1-trifluoro-pentan-2,4-dione; TFH: 1,1,1-trifluoro-hexan-2,4-dione; reactive species those lifetimes are under 1 day (calculated as above) an
TFMH: 1,1,1-trifluoro-hexan-5-methyl-2,4-dione; Acac: Pentane-2,4-dione. average daytime [OH] of 2.5 × 106 molecule cm− 3 is used together with
b
this work, errors as above: 2σ statistical error of the mean and an additional the rate coefficient at 298 K (Calvert et al., 2011). This suggest a
15% relative error; c average between reference data (Holloway et al., 2005), non-uniform mixing for these fluorinated diketones in the troposphere
(Zhou et al., 2008), (Messaadia et al., 2015), error propagation method. and hence no significant contribution to global warming is expected
(Hodnebrog et al., 2013). However, if in the atmospheric oxidation of
the fluorodiketones products conserving CF3 moieties are formed, they
Table 4 might be less reactive possessing a higher GWP than the parent
Atmospheric lifetimes of the FDKs studied
compounds.
regarding to the reaction with OH radicals.
Also of importance for the environmental impact is the acidification
FDKs ƮOH (Hours) potential (AP) every airborne compound containing heterogeneous
TFP 21 atoms possesses (de Leeuw, 1993). Accordingly, values of 0.62, 0.57 and
TFH 13 0.53 are calculated for TFP, TFH and TFMH, respectively. The reference
TFHM 8
value is 1.00 for SO2, hence these results appear quite high. This in­
dicates that these fluorinated carbonyl compounds (FDKs) and their
on the overall rate coefficient is negligible. Hence, a significant reduc­ atmospheric degradation products could be involved in "acid rain"
tion of the C–– C double bond’s reactivity was already observed due to a events with the known consequences for deteriorating water and soil
more distant –CF3 group and one would expect enol (b) of the TFP quality and subsequently affecting the biota and human health (Bouw­
system to be much less reactive than Acac as well. However, besides that man et al., 2002; Granados Sánchez et al., 2010; Huang, 1992). How­
the (-I)-effect of –CF3 substituent reduces the reactivity of the TFP sys­ ever, since the time scale between emission and wash out as acidic
tem comparative to acetyl acetone no further statement can be gained species is not known, these values should be regarded as upper limits for
from the experimentally determined rate coefficient without discrimi­ the acidification potential of the studied compounds.
nation between the individual contribution of both enol tautomers.
No similar information is available for non-halogenated analogues of 3.1.2. Estimated photochemical ozone creation potentials (POCP)
TFH and TFMH. The present work indicates that tautomerism has an Ozone formation in the troposphere is related to health problems
impact on the reactivity of the studied fluorinated β-diketones and hence (Vinikoor-Imler et al., 2014) and damage to vegetation (Ghude et al.,
further investigation are necessary to decipher the ratio between the 2014). As part of this study, the photochemical ozone creation potentials
individual tautomers in the gas phase. were estimated for the three fluorinated diketones, employing a method
designed by Derwent et al. (1998) and Jenkin (1998). The method
correlates the ozone creation potential to the FDKs OH reactivity relative
3.1. Atmospheric implications to ethene by the following equation:

3.1.1. Tropospheric lifetimes, global warming potential and acidification
potential
Calculated tropospheric lifetimes of the FDKs studied in this work
with respect to reaction with OH radicals are given in Table 4, consid­
ering a 24-h average OH concentration of 1 × 106 molecules cm− 3
(Atkinson et al., 1997).
These values indicate that atmospheric transport of the fluorinated
carbonyls cannot be excluded, although the area of impact and how far
away from the emission sources they travel cannot be estimated solely
from the actual data. On the other hand, in coastal regions the con­
centration of Cl atoms can be higher than 1 × 104 atoms/cm3 (Wing­
enter et al., 1996) and also anthropogenic sources such as brick and
ceramic industries, water treatment plants, etc. (Wang et al., 2009,
2019) increases locally the level of chlorine atoms which could
contribute to the degradation of these compounds. More, the enolic
structure might also favour the reaction with ozone. Further investiga­
tion on the gas-phase reactions of TFP, TFH and TFMH with other at­
mospheric oxidants ozone, chlorine atoms and NO3 radicals are under
development.
εPOCP = α1 × γs × γβR (1 − α2 × nC ) (11)
In equation (11) ε POCP
is the estimated photochemical ozone creation
potential, α1, α2, β, γS and γR are parameters we calculated combining
the rate coefficients determined in this work with the information given
in Jenkin (1998) and the last IUPAC recommendation for the rate co­
efficient for the reaction of C2H4 with OH. Table 5 shows the calculated
values for TFP, TFH, TFMH and Acac, for comparison.
In the case of TFP and Acac the estimated POCPs reflect the
decreased reactivity toward OH radicals induced by the presence of
fluorine. In order to make a sound evaluation of the contribution of FDKs
to the formation of tropospheric ozone a more thorough analysis is
needed to include their reactivity toward ozone as a consequence of the
enol tautomerism.
4. Conclusions
This work reports the first determination of the rate constant co­
efficients for the gas-phase reaction of OH radicals with 1,1,1-trifluoro-

7
P.L. Lugo et al.
2,4-pentanedione (TFP), 1,1,1-trifluoro-2,4-hexanedione (TFH) and
1,1,1-trifluoro-5-methyl-2,4-hexanedione at room temperature and at­
mospheric pressure. The measurements performed using IR spectros­
copy indicated that the keto-enolic tautomerization takes place for all
studied compounds in the gas-phase, the enolic forms where the OH
moieties are vicinal to the –CF3 group being probably predominant.
Under the experimental conditions of this study was not possible to
discern between the rate coefficients of the individual tautomers.
The lifetime durations calculated upon the present results indicate
that transport might play a role in the atmospheric fate of the studied
compound, but no major contribution to global warming is expected.
The relatively high POCP values estimated for FDKs, suggest that they
might contribute to the formation of tropospheric ozone or smog. The
upper limits estimates calculated for their acidification potential suggest
that FDKs are involved in acid rain events.
Further investigations to include the products formed in the reaction
with OH radicals and comprehensive analysis of the gas-phase reactions
with other oxidants as ozone, chlorine atoms and NO3 radicals are still
needed in order to understand the implications related to the presence of
FDKs in the atmosphere.
Author contribution
María Belén Blanco and Mariano Teruel: Conceptualization. Niklas
Illmann and Iulia Patroescu-Klotz: Methodology and Validation. Pedro
Lugo, Vianni Straccia and Cynthia Rivela: Investigation. Pedro Lugo,
María Belén Blanco, Niklas Illmann and Iulia Patroescu-Klotz: Writing-
Original draft preparation. Peter Wiesen and María Belén Blanco:
Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors wish to acknowledge to EUROCHAMP 2020, FonCyT,
CONICET and SECyT, UNC, Argentina. P. L. L. G and V. S. C wish to
acknowledge to CONICET for a doctoral fellowship and support. M. B. B.
and C. B. R. wish to acknowledge to Alexander von Humboldt Founda­
tion for the support.
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