Hydroxyl radical reactions with halogenated ethanols in aqueous solution: Kinetics and thermochemistry

Article abstract of DOI:10.1002/kin.20301

Laser flash photolysis combined with competition kinetics with SCN- as the reference substance has been used to determine the rate constants of OH radicals with three fluorinated and three chlorinated ethanols in water as a function of temperature. The following Arrhenius expressions have been obtained for the reactions of OH radicals with (1) 2-fluoroethanol, k₁,(T ) = (5.7 ± 0.8) × 10¹¹ exp((-2047 ±1202)/T) M^-1 s^-1, (2) 2,2-difluoroethanol, k₂(T ) = (4.5 ± 0.5) × 10⁹ exp((-855 ± 796)/T) M^-1 s ^-1, (3) 2,2,2-trifluoroethanol, k₃(T) = (2.0 ± 0.1) × 10¹¹ exp((-2400 ± 790)/T) M^-1 s ^-1, (4) 2-chloroethanol, k₄(T) = (3.0 ± 0.2) × 10¹⁰ exp((-1067 ± 440)/T) M^-1 s ^-1, (5) 2, 2-dichloroethanol, k₅(T) = (2.1 ± 0.2) × 10¹⁰ exp((-1179 ± 517)/T) M^-1 s ^_1, and (6) 2,2,2-trichloroethanol, k₆(T) = (1.6±0.1) × 10¹⁰ exp((-1237 ± 550)/T) M ^-1 s^-1. All experiments were carried out at temperatures between 288 and 328 K and at pH = 5.5-6.5. This set of compounds has been chosen for a detailed study because of their possible environmental impact as alternatives to chlorofluorocarbon and hydrogen-containing chlorofluorocarbon compounds in the case of the fluorinated alcohols and due to the demonstrated toxicity when chlorinated alcohols are considered. The observed rate constants and derived activation energies of the reactions are correlated with the corresponding bond dissociation energy (BDE) and ionization potential (IP), where the BDEs and IPs of the chlorinated ethanols have been calculated using quantum mechanical calculations. The errors stated in this study are statistical errors for a confidence interval of 95%.

Full text of DOI:10.1002/kin.20301

Hydroxyl Radical Reactions
with Halogenated Ethanols
in Aqueous Solution:
Kinetics and
Thermochemistry
I. MOROZOV,1 S. GLIGOROVSKI,2 P. BARZAGHI,2 D. HOFFMANN,2 Y. G. LAZAROU,3
E. VASILIEV,1 H. HERRMANN2
1Semenov Institute of Chemical Physics RAS, Kosygin Str. 4, 119991 Moscow, Russia
2Leibniz-Institut fu¨r Tropospha¨renforschung, Permoserstraße 15, 04318 Leipzig, Germany
3Institute of Physical Chemistry, National Centre of Scientific Research “Demokritos,”
Aghia Paraskevi, Attiki GR-153 10, Greece
Received 21 December 2006; revised 21 May 2007, 23 October 2007; accepted 24 October 2007
DOI 10.1002/kin.20301
Published online in Wiley InterScience (www.interscience.wiley.com).
ABSTRACT: Laser flash photolysis combined with competition kinetics with SCN− as the
reference substance has been used to determine the rate constants of OH radicals with
three fluorinated and three chlorinated ethanols in water as a function of temperature.
The following Arrhenius expressions have been obtained for the reactions of OH r−ad1 ic−al1s
with (1) 2-fluoroethanol, k1(T ) = (5.7 0.8) × 1011 exp((−2047
1202)/T ) M
796)/T ) M−1 −1
790)/T ) M−1 s−1
s
s
,
,
,
(2)
2,2-difluoroethanol,
k2(T ) = (4.5
0.5) × 109
exp((−855
(3) 2,2,2-trifluoroethanol, k3(T ) = (2.0 0.1) × 1011 exp((−2400
(4) 2-chloroethanol, k4(T ) = (3.0 0.2) × 1010 exp((−1067 440)/T ) M−1 s−1
,
(5) 2,
Correspondence to: H. Herrmann; e-mail: herrmann@tropos.de.
Present address of S. Gligorovski: Laboratoire Chimie et Envi-
ronnement Universite´ de Provence, Case courrier 29, 3 place Victor
Hugo, 13331 Marseille Cedex 03, France.
Contract grant sponsor: European Commission, under the project
“Impact of Fluorinated Alcohols and Ethers on the Environment
(IAFAEE).”
Contract grant number: EVK2-CT-1999-00009.
Contract grant sponsor: North Atlantic Treaty Organization.
Contract grant number: CLG 983035.
Contract grant sponsor: International Association for the promo-
tion of cooperation with scientists from the New Independent States
of the former Soviet Union (NIS).
Contract grant number: 03-51-56-98.
Contract grant sponsor: Russian Foundation for Basis Research.
Contract grant numbers: 06-05-64646, 06-03-32836.
2008 Wiley Periodicals, Inc.
c
ꢀ

HYDROXYL RADICAL REACTIONS WITH HALOGENATED ETHANOLS
175
2-dichloroethanol, k5(T ) = (2.1 0.2) × 1010 exp((−1179 517)/T ) M−1
s
−1, and (6) 2,2,2-
trichloroethanol, k6(T ) = (1.6 0.1) × 1010 exp((−1237 550)/T ) M−1
s
−1. All experiments
were carried out at temperatures between 288 and 328 K and at pH = 5.5–6.5. This set of com-
pounds has been chosen for a detailed study because of their possible environmental impact as
alternatives to chlorofluorocarbon and hydrogen-containing chlorofluorocarbon compounds
in the case of the fluorinated alcohols and due to the demonstrated toxicity when chlorinated
alcohols are considered. The observed rate constants and derived activation energies of the
reactions are correlated with the corresponding bond dissociation energy (BDE) and ionization
potential (IP), where the BDEs and IPs of the chlorinated ethanols have been calculated using
quantum mechanical calculations. The errors stated in this study are statistical errors for a
confidence interval of 95%. ꢀ 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 174–188, 2008
C
the atmospheric aqueous phases. Reactive uptake into
cloud particles has been proposed as a possible signif-
icant loss process for trifluoromethanol under tropo-
spheric conditions [5]. Thus, the most likely sinks for
halogenated alcohols are deposition or chemical con-
version processes in the aqueous phase where an im-
portant first step of halogenated ethanols atmospheric
degradation could proceed by reaction with the OH
radical in aqueous solution.
INTRODUCTION
The ability of a chemical compound to create a green-
house effect in the atmosphere is caused by shielding
radiation being emitted from the earth surface in the at-
mosphere. Potential greenhouse gases may be charac-
terized by their greenhouse warming potential (GWP)
with the GWP being the ratio of the warming caused
by a substance to the warming caused by a similar mass
of carbon dioxide [1].
As another family of compounds, chlorinated alco-
hols (ChAs) attract interest as compounds for a com-
parison of their reactivity toward OH radical with that
of FAs of similar structure. ChAs are used in a wide
variety of industrial applications as solvents, additives,
and intermediates in chemical synthesis. They are also
generated by bacterial biotransformation or hydroly-
sis of widely employed halogenated ethanes [6,7]. In
particular, CHCl2CH2OH may be also generated by
the hydrolysis of the pesticide dichlorvos [8]. Gen-
erally, chloroethanols are considered to be toxic to
marine and terrestrial animals [9,10]. Furthermore,
the natural formation of organohalogen compounds
has been suggested to contribute to the atmospheric
budget [11]. In fact, the halogenation of hydrocar-
bons is well documented for nearly all-natural en-
vironments where the oceans represent the strongest
production source of organohalogen of biogenic ori-
gin. Most of the identified compounds in the maritime
environment are chloro-substituted hydrocarbons [12],
whereas in continental areas the bromine-substituted
organics are formed. Biogenic formation of fluoro-
organic compounds is of minor importance. Organoflu-
orine metabolites have been found in bacteria, fungi,
and higher plants [13–15].
Because of their capacity to destroy the ozone layer
and having high GWPs, various classes of industrially
produced halocarbon compounds such as chlorofluo-
rocarbon compounds (CFCs) and hydrogen-containing
chlorofluorocarbon compounds (HCFCs) are subject
to international regulations and have been phased out
from industrial production to a large extent [1]. There-
fore, the substitution of such compounds is an indus-
trial and environmental issue of huge importance.
Different approaches have been chosen to develop
compounds as alternatives to CFCs and HCFCs with
reduced effects on the environment.
Halogenated ethanols (HEs) have been suggested
as such alternative compounds [2]. The atmospheric
lifetime and the degradation pathways of such alter-
native compounds must be established to assess the
possible impact of the industrial application of HEs to
the atmosphere.
One of the ways that has been chosen is the use
of fluorine as the only substituent in the organic
compound since fluorocarbon oxidation products do
not seem to be able to catalyze stratospheric ozone
depletion. Thus, fluorinated alcohols (FAs) have re-
ceived attention as potential alternative compounds
[1], and a recent study of Selleva˚g et al. [2] investi-
gated the gas-phase reactivity of 2-fluoroethanol, 2,2-
difluoroethanol, and 2,2,2-trifluoroethanol.
Several experimental studies [2,16–19] have been
published on the gas-phase reactivity of OH radicals
toward halogenated alcohols, whereas much less infor-
mation is available for possible aqueous-phase degra-
dation reactions.
Because of their solubility [3,4], significant concen-
trations of FAs could be expected to be transferred to
International Journal of Chemical Kinetics DOI 10.1002/kin

176
MOROZOV ET AL.
Figure 1 Laser flash photolysis setup for the study of OH radical kinetics with halogenated ethanols in aqueous solution.
To better understand the atmospheric multiphase
oxidation process of HEs, in the present study the tem-
perature dependencies of the rate constants of the reac-
tions OH radicals with halogenated ethanols in water
were investigated using laser flash photolysis and a
competition kinetics method.
(99%), and 2,2,2-trichloroethanol (99%) (Sigma-
Aldrich, Seelze, Germany) were studied in the
aqueous phase by means of laser flash photolysis
combined with a competition kinetics method using
the thiocyanate ion (SCN−) as a reference system be-
tween 278 and 328 K (temperature uncertainty = 0.1
K) and at pH = 5.5–6.5.
Correlations between reaction rates and extra ki-
netic parameter, such as bond dissociation energies
(BDEs) or ionization potentials (IPs), have been used
successfully in the literature to better understand the
mechanism of a chemical reaction and to estimate un-
known reaction parameters, both in the gas phase [17]
and in the solution phase [20–26]. In the present study,
correlations of the observed rate constants and activa-
tion energies with calculated BDEs as well as IPs are
presented for the reactions of OH radicals with HEs,
and finally the atmospheric implications of the study
are discussed. As a part of the study, the C H and O H
bond dissociation energies at 298.15 K and the ioniza-
tion potentials of the ChAs are theoretically calculated
using density functional theory (DFT). Additional cal-
culations were performed for their fluorinated equiv-
alents to assess the accuracy of the reported values
by comparison with known experimental and previous
theoretical values, and furthermore examine the trends
in the calculated properties as a function of the molec-
ular structure.
All chemicals were purchased at the highest purity
available and used without further treatment. All solu-
tions were freshly prepared using a Milli-Q-water sys-
tem (Milipore, MI) as water source. The pH value was
adjusted, if necessary, with NaOH or HClO4 (Fluka,
Munich, Germany).
The reaction cell is a flow-through quartz vessel
(4.7-cm i.d., 7 cm long) that is thermostated by a
water jacket. An excimer laser (Lambda LPX 100)
has been used to generate OH radicals through the
photolysis of an aqueous solution of hydrogen perox-
ide (5 × 10−5 M) at λ = 248 nm (excimer laser gas
medium: KrF). The laser delivers an average energy of
150 mJ pro pulse that corresponds to an average OH
radical concentration of 1 × 10−7 M in the cell with
[H2O2]0 = 1 × 10−4 M.
The analytical light beam generated by a high
pressure Hg–Xe lamp (Hamamatsu E7536) is folded
through a reaction cell 12 times with a total
length of 84 cm, and it is fed to the detector, a
monochromator–photomultiplier combination (Zeiss
PMQ 2/Hamamatsu PMT 1P 28) connected to an oscil-
loscope (Gould 4050) and a computer. Further details
regarding the experimental setup can be found else-
where [24,25] and are shown in Fig. 1.
EXPERIMENTAL
Kinetic Investigations
The reactions OH radical with 2-fluoroethanol
(>90%),
2,2-difluoroethanol
(95%),
2,2,2-
Kinetic Competition Reference System. The proce-
dures for the kinetic measurements as well as the data
analysis have been described in detail previously [24].
trifluoroethanol (99%) (Fluorochem Ltd., Glossop,
UK), 2-chloroethanol (99%), 2,2-dichloroethanol
International Journal of Chemical Kinetics DOI 10.1002/kin

HYDROXYL RADICAL REACTIONS WITH HALOGENATED ETHANOLS
177
Briefly, OH is converted to (SCN)2−
imaginary vibrational frequencies were found for each
species, and the one with the lowest energy was se-
lected for the subsequent refinement by single-point
energy calculations at higher levels of theory. All vi-
brational frequencies were scaled down by 0.9723 to
compensate their overestimation by the B3P86/AUG-
cc-pVDZ level of theory [32].
The zero-point and the thermal energies at 298.15 K
were derived by considering the harmonic oscillator
and the rigid-rotor approximations. They were subse-
quently added to the absolute electronic energies, to
yield the absolute enthalpies for each species, and fi-
nally, the C H and O H bond dissociation energies.
The vertical ionization potentials of alcohols were cal-
culated as the difference between the absolute energies
of the parent molecule and its singly ionized radical
cation.
−→
←−
OH + SCN
SCNOH−
SCNOH−
SCN + OH−
(SCN)−2
(a)
(b)
(c)
(d)
−→
←−
SCN + SCN−
−→
←−
OH + Reactant → Products
The second-order rate constants (kd (M−1 −1)) are
s
be obtained from the following expression:
A0
A
kd [Reactant]
ka [SCN−]
= 1 +
(1)
where A0 is the light intensity absorbed by (SCN)−2 and
A is the variation of the intensity when the reactant is
added to the reaction solution. As the reference rate
constant (ka (M−1 −1)), the temperature-dependent
s
RESULTS AND DISCUSSION
Kinetic Investigations
rate constant reported by Chin and Wine [27] has been
used.
Five different reactant concentrations between
5 × 10−5 M and 8 × 10−3 M have been considered
for the linear regression analysis. For every single re-
actant concentrations, the absorption signals of eight
measurements were averaged. The errors given in the
present study represent statistical errors for a confi-
dence interval of 95% using the t-Student distribution.
In the literature, it is generally accepted that the reac-
tions of hydroxyl radicals with aliphatic compounds
proceed through the abstraction of the most loosely
bound hydrogen atom in the molecule with the forma-
tion of the corresponding alkyl radical. In the presence
of oxygen, the alkyl radical is then converted rapidly to
a peroxyl radical. The aqueous-phase chemistry of the
peroxyl radicals is very complex and has been reviewed
elsewhere [42].
Computational Details
As known from previous studies as well as calcu-
lated in the present work [2,16,17], the hydrogen atoms
with the weakest bond in HEs are localized in the CH2
group carrying the hydroxyl function.
All calculations were carried out with the Gaussian 98
programs suite [28], by using three DFT functionals in
combination with a variety of basis sets. The B3P86
functional [29,30] was employed in the calculation
of molecular geometries and vibrational frequencies,
as well as in the calculation of C H and O H bond
strengths [31,32]. Ionization potentials were calculated
by the B3LYP and B3PW91 functionals [29,33], which
have been shown to be sufficiently reliable for the cal-
culation of molecular ionic properties [34,35]. Sev-
eral kinds of basis sets were used (namely, variants
of the 6-311G basis set, denoted as 6-311++G(2d,p)
and 6-311++G(3df,2p) [36–38] as well as correlation-
consistent basis sets, denoted as AUG-cc-pVDZ, cc-
pVTZ, and AUG-cc-pVTZ [39–41]) to examine the
effects of the basis set size and the presence of dif-
fuse functions on the computational accuracy, and fur-
thermore to assure the convergence of the calculated
properties to a narrow range of values.
Reactions of OH with Fluorinated Alcohols. The
second-order rate constants obtained at five different
temperatures for the following reactions ((R1)–(R3))
are summarized in Table I, whereas Fig. 2 shows the
corresponding Arrhenius plots:
OH + CFH2CH2OH → CFH2CHOH + H2O (R1)
OH + CF2HCH2OH → CF2HCHOH + H2O (R2)
OH + CF3CH2OH → CF3CHOH + H2O
(R3)
A clear decrease in the rate constants is observed
with the increasing number of halogen atoms in
the molecule. The difference in the bond dissocia-
tion energy between the nonsubstituted parent organic
compounds, namely ethanol and halogen-substituted
ethanols (Table II) is reflected also in the difference
The geometry optimizations and vibrational fre-
quencies calculations were carried out at the
B3P86/AUG-cc-pVDZ level of theory for all species.
Several local minima (conformers) possessing no
International Journal of Chemical Kinetics DOI 10.1002/kin

178
MOROZOV ET AL.
Table I Rate Constants Determined in the Present Study for the Reactions of OH with 2-Fluoroethanol (k1),
2,2-Difluoroethanol (k2), 2,2,2-Trifluoroethanol (k3), 2-Chloroethanol (k4), 2,2-Dichloroethanol (k5), and
2,2,2-Trichloroethanol (k6)
k × 108
k × 108
k × 107
k × 108
k5 × 108
k × 108
1
2
3
4
6
T (K)
(M−1 s−1
)
(M−1 s−1
)
(M−1 s−1
)
(M−1 s−1
)
(M−1 s−1
)
(M−1 s−1
)
288
298
308
318
328
5.3 0.7
5.4 1.8
6.3 1.1
9.2 5.3
12.0 1.0
2.1 0.5
2.8 0.7
2.9 0.8
3.0 1.2
3.2 1.7
5.4 0.9
8.5 2.5
10 4.0
13 8.0
15 5.1
7.1 0.5
8.6 0.7
9.6 1.5
10.8 2.1
11.1 1.1
3.6 0.7
3.9 0.8
4.6 1.0
5.6 0.6
5.6 0.7
2.2 0.3
2.4 1.1
2.8 0.5
3.5 0.9
3.5 1.5
observed in the rate constants (Table III). A value of
k2nd = 2.1 × 109 M−1 s−1 was reported for the reaction
of OH with ethanol in aqueous solution [24].
higher with respect to the other two FAs. Furthermore,
it represents the larger negative value measured for
reaction of OH with halogen-substituted organic com-
pounds in the aqueous phase.
Consistently, a difference in the BDE of about
10 kJ mol−1 corresponds to a decrease of 1 order of
magnitude of the rate constant for the reaction of OH
with 2-fluoroethanol and 20 kJ mol−1 in BDE corre-
sponds to a decrease by 2 orders of magnitude for 2,2,2-
trifluoroethanol. The large difference between the k1
and k2 appears to be not consistent with the calculated
difference in the BDE (cf. Table IV). Halogen substi-
tution in that case does not significantly change the
calculated C H bond strength in the CH2 group.
Therefore, the reason for the observed differences be-
tween k1 and k2 remains speculative. Also the obtained
activation parameters show some relevant differences
in the values of entropy of activation as can be seen in
Table II. The entropy of activation for the reaction of
OH with 2,2-difluoroethanol does not follow the trend
observed in the case of ChAs, and it is significantly
As most of the data presented in this work repre-
sent first measurements, a comparison with the liter-
ature is difficult. Walling et al. [20] determined first
the rate constant for the reaction of OH with 2,2,2-
trifluoroethanol using a steady-state method based on
a Fenton reaction at room temperature. The value re-
ported of k2nd = 2.3 × 108 M−1 s−1 is in rather large
disagreement, according to the cited authors the re-
action proceeds about 3 times faster than determined
here. An explanation for this difference has been al-
ready indicated by Yurkova et al. [43]. As discussed
in their work, in the presence of the Fenton’s reagent
Fe2+–H2O2 it is not clear whether the oxidation reac-
tion is initiated by a free hydroxyl radical or rather a
reactive complex iron intermediate, for example, fer-
ryl ion, FeO2+. Depending on the nature of the organic
Figure 2 Arrhenius plot for the reaction of OH with 2-fluoroethanol (ꢀ), 2,2-difluoroethanol ( ), and 2,2,2-trifluoroethanol
ꢁ
( ).
•
International Journal of Chemical Kinetics DOI 10.1002/kin

HYDROXYL RADICAL REACTIONS WITH HALOGENATED ETHANOLS
179
Table II Activation Parameters for H Abstraction Reactions by the OH Radical from Alcohols in Aqueous Solution
EA
(kJ mol−1
A
ꢀS‡
ꢀH‡
ꢀG‡
BDE (C H)
Compound
)
(M−1 s−1
)
(J K−1 mol−1) (kJ mol−1) (kJ mol−1) Reference (kJ mol−1) Reference
2-Fluoroethanol
2,2-Difluoroethanol
2,2,2-Trifluoroethanol 20
2-Chloroethanol
2,2-Dichloroethanol
2,2,2-Trichloroethanol 10
Ethanol
1-Propanol
2-Propanol
1-Butanol
17 10 (5.7 0.8) × 1011 –(28 4) 14.5
9
4
6
3
3
4
4
4
2
1
23 17 This work
25 26 This work
28 12 This work
22 10 This work
24 12 This work
25 13 This work
399.6
399.5
409.0
394.1
399.4
404.0
389
385
381
385
This work
This work
This work
This work
This work
This work
[24]
7
7
7
4
4
5
5
6
2
1
(4.5 0.5) × 109
–(69 8)
4.6
17
6
(2.0 0.1) × 1011 –(37 4)
(3.0 0.2) × 1010 –(53 3)
(2.1 0.2) × 1010 –(55 5)
(1.6 0.1) × 1010 –(58 4)
(1.0 0.1) × 1011 –(42 4)
(5.6 0.6) × 1010 –(47 5)
(6.3 0.3) × 1010 –(47 2)
(1.0 0.1) × 1011 –(42 1)
9
10
7
8
8
6
6
5
10
8
8
20 12
20 17
[24]
[24]
[22]
[22]
[24]
[22]
[22]
20
18
6
2
8
reactants, the latter reaction might significantly con-
tribute to the overall rate constant leading to an overes-
timation of the observed rate constant. The reactivity of
the Fe(IV) species FeO2+ is described in the literature
[44,45].
The second-order rate constants for the reactions of
OH radicals with the series of chlorinated alcohols
obtained as a function of the temperature are summa-
rized in Table I. To the best of the authors’ knowl-
edge, these values are the first temperature-dependent
measurements for reactions (R4)–(R6) in aqueous so-
lution. The Arrhenius plots are presented in Fig. 3, and
the derived activation parameters are summarized in
Table II together with the bond dissociation energies
of the weakest C H bond in the respective molecules.
The activation parameters have been calculated as pre-
viously described in [24].
Reactions of OH with Chlorinated Alcohols. In the
same range of temperature applied for the fluorinated
ethanols, the kinetics of the following reactions with
chlorinated alcohols has been studied:
In the case of 2-chloroethanol, the comparison with
a previous study performed at room temperature shows
relatively good agreement. In that study, Anbar and
Neta [21] determined the second-order rate constant as
k4 = 9.6 × 108 M−1 s−1 using γ-radiolysis to generate
OH + CH2ClCH2OH → CH2ClCHOH + H2O (R4)
OH + CHCl2CH2OH → CHCl2CHOH + H2O (R5)
OH + CCl3CH2OH → CCl3CHOH + H2O (R6)
Table III Aqueous and Gas-Phase Rate Constants of the Reactions OH Radicals with Small Linear Alcohols
k (298 K) Aqueous
k (298 K) Gas
No.
1
Compound
phase (M−1s−1
)
Reference
This work
phase (M−1s−1
)
Reference
2-Fluoroethanol
5.4 × 108
8.5 × 108
1.0 × 109
2.7 × 108
0.74 × 108
0.6 × 108
0.57 × 108
0.57 × 108
7.7 × 108
[2]
[19]
[2]
2
3
2,2-Difluoroethanol
2,2,2-Trifluoroethanol
2.8 × 108
0.8 × 108
1.8 × 108
2.3 × 108
This work
This work
[57]
[2]
[16]
[57]
[58]
[57]
[20]
4
2-Chloroethanol
8.6 × 108
9.6 × 108
3.9 × 108
2.4 × 108
3.2 × 108
4.2 × 108
2.1 × 109
3.2 × 109
4.1 × 109
This work
[57]
This work
This work
[57]
5
6
2,2-Dichloroethanol
2,2,2-Trichloroethanol
–
–
[57]
1.5 × 108
[20]
[24]
[24]
[22]
7
8
9
Ethanol
1-Propanol
1-Butanol
1.9 × 109
3.3 × 109
5.1 × 109
[47]a
[47]a
[47]a
a Data reported represent the average of existing literature values [47].
International Journal of Chemical Kinetics DOI 10.1002/kin

180
MOROZOV ET AL.
Table IV Experimental and Calculated C H and O H Bond Dissociation Energies (in kJ mol−1) for Ethanol,
Fluorinated, and Chlorinated Ethanols
Bond
Experimentala
419.7 8.4
Calculated (This Study)
Calculated [31]b
CH2CH2OH H
CH3CHOH H
CH3CH2O H
430.0
396.0
433.7
425.0
399.6
463.9
428.7
399.5
452.5
409.0
462.3
420.9
394.1
447.4
412.8
399.4
456.3
404.0
458.7
424.4
391.0
438.3
415.2
392.5
450.5
418.1
390.7
456.9
397.8
467.2
436.0 4.2
CHFCH2OH H
CH2FCHOH H
CH2FCH2O H
CF2CH2OH H
CHF2CHOH H
CHF2CH2O H
CF3CHOH H
CF3CH2O H
CHClCH2OH H
CH2ClCHOH H
CH2ClCH2O H
CCl2CH2OH H
CHCl2CHOH H
CHCl2CH2O H
CCl3CHOH H
CCl3CH2O H
The calculated BDEs are represented as the average of the three most accurate theoretical values obtained at the B3P86/AUG-cc-pVTZ,
B3P86/AUG-cc-pVDZ, and B3P86/6-311++G(2df,p) levels of theory.
a From enthalpies of formation in [47,48].
b Bond dissociation energies calculated at the B3P86/6–311++G(3df,2p) level of theory, using molecular structures optimized at the
B3P86/6–31G(d) level, without taking into account of empirical corrections to the radical species energies.
the radicals and applied competition kinetics using the
reaction with ethanol as reference. The kinetic results
are collected in Table III.
stant for the reaction of OH with 2,2,2-trichloroethanol
that is two times larger than the value presented here.
Also, in this case the difference in the measured rate
constants might be explained as discussed for the re-
action of OH with 2,2,2-trifluoroethanol.
In contrast, Walling et al. [20] obtained a value
(k6 = 4.2 × 108 M−1 s−1) for the second-order rate con-
Figure 3 Arrhenius plot for the reaction of OH with 2-chloroethanol (ꢀ), 2,2-dichloroethanol ( ), and 2,2,2-trichloroethanol
ꢁ
( ).
•
International Journal of Chemical Kinetics DOI 10.1002/kin

HYDROXYL RADICAL REACTIONS WITH HALOGENATED ETHANOLS
181
Table V Experimental and Calculated Vertical
Ionization Potentials (in eV) for Ethanol, Fluorinated,
and Chlorinated Ethanols
Reactivity Comparison. The analysis of the activa-
tion parameters (Table II) shows similar values for all
the compounds. A more detailed description of how
the activation parameters have been derived can be
found elsewhere [24,46]. The rate constants for the
reactions of OH with ChAs appear to have the same
dependence on temperature as observed for the reac-
tion of OH with ethanol and other simple aliphatic al-
cohols with an average value of 10 kJ mol−1for the
energy of activation. A different trend is observed
in the case of fluorine-substituted alcohols. Whereas
2,2-fluoroethanol shows an activation energy close to
the chlorine-substituted alcohols, 2-fluoroethanol and
2,2,2-trifluoroethanol have significant higher activa-
tion energies.
Experimental
[49]
Calculated
(This Study)
Molecule
CH3CH2OH
CH2FCH2OH
CHF2CH2OH
CF3CH2OH
CH2ClCH2OH
CHCl2CH2OH
CCl3CH2OH
10.47
10.66
10.54
10.81
11.12
11.63
10.55
10.64
10.86
11.49
10.66
10.94
The calculated IPs are represented as the average of the
three most accurate theoretical values obtained at the B3PW91/cc-
pVTZ, B3LYP/cc-pVTZ, and B3PW91/6-311++G(3df,2p) levels
of theory.
When nonsubstituted alcohols and ChAs are con-
sidered, the entropies of activation indicate that similar
transition state structures can be expected within the
same groups of compounds. This does not apply in the
case of FAs, where a trend in the results is difficult to
identify.
energies of the radical species [32] to lower the de-
viation from the experimental values inferred from
the corresponding standard enthalpies of formation
[47,48]. The variation of all BDEs at these levels of
theory was small and never exceeded 4 kJ mol−1, in-
dicating that the calculated values have converged suf-
ficiently to a narrow range of accurate values. How-
ever, a negligible dependence on the size of the ba-
sis set was noted, and the accuracy of the calculated
BDEs was slightly improved by the presence of diffuse
functions. The average values of the empirically cor-
rected results at the three most accurate levels of theory
(B3P86/AUG-cc-pVTZ, B3P86/AUG-cc-pVDZ, and
B3P86/6-311++G(2df,p)) are shown in Table IV.
The largest deviation from experimental values is
ca. 10 kJ mol−1 for the H CH2CH2OH bond, and all
Theoretical Calculations
The most stable conformers of CH2ClCH2OH,
CHCl2CH2OH, and CCl3CH2OH, as well as of
their singly dehydrogenated radicals CH3–nClnCHOH
(n = 1, 2, 3), calculated at the B3P86/AUG-cc-pVDZ
level of theory, have been identified and their bond
lengths, bond angles, and the dihedral angles be-
tween the O C C/C C X (X = Cl or H) and
H O C/O C C planes are summarized and shown
in Fig. 4.
The absolute electronic energies for all species were
found to depend on the arrangement of the OH group,
as in fluorinated ethanols [31]. For CH3CH2OH and
CH3CHOH, there is a slight increase in the energy by
ca. 1 kJ mol−1 when the OH group is arranged toward
the CH3 group due to the unfavorable steric repul-
sions. On the other hand, for all ChAs and their OH
groups, there is a stabilization when the OH group is
facing Cl atoms, due to the attractive intramolecular
C Cl···H O interactions. The energy barrier of the
OH internal rotation depends on the degree of substi-
tution by chlorine atoms, reaching a maximum of ca.
13 kJ mol−1 for CCl3CH2OH.
remaining deviations are lower than 6 kJ mol−1
.
The ionization potentials of ethanol as well as FAs
and ChAs were calculated at 10 levels of theory, con-
sisting of the B3LYP and B3PW91 functionals and the
five basis sets discussed above. The mean deviation
from experimental values [49] was rather insensitive to
the level of theory, on the order of 0.12–0.20 eV. The
smallest deviations were presented by the B3PW91
functional, and the agreement with experimental val-
ues was slightly deteriorating by the presence of dif-
fuse functions in the basis sets. The average value
of the ionization potentials of the three most accu-
rate levels of theory (B3PW91/cc-pVTZ, B3PW91/6-
311++G(3df,2p), and B3LYP/cc-pVTZ) is shown in
Table V.
The C H and O H bond dissociation energies of
ethanol as well as fluorinated and chlorinated ethanols
were calculated at five levels of theory, all consist-
ing of the B3P86 functional in combination with the
basis sets AUG-cc-pVDZ, cc-pVTZ, AUG-cc-pVTZ,
6-311++G(2df,p), and 6-311++G(3df,2p), by taking
into account empirical corrections of the electronic
The average deviation of the calculated IPs from
experimental values is quite low, in the order of
0.03 eV. However, the comparison with the literature
data remains incomplete due to the lack of data for
CHF2CH2OH and CHCl2CH2OH.
International Journal of Chemical Kinetics DOI 10.1002/kin

182
MOROZOV ET AL.
Figure 4 Optimized structures for the parent CH(3−n)ClnCH2OH ethanols and CH(3−n)ClnCHOH radicals (n = 1,2,3) at the
B3P86/AUG-cc-pVDZ level of theory. Bond lengths, bond angles, and important dihedral angles are also shown.
International Journal of Chemical Kinetics DOI 10.1002/kin

HYDROXYL RADICAL REACTIONS WITH HALOGENATED ETHANOLS
183
EA/kJ mol−1 = −(52 34) + (0.16 0.09)
Reactivity Correlations
·BDE(C H)/kJ mol−1 (n = 17; r = 0.69) (7)
Evans and Polanyi studied the existing relationships
between the thermochemistry of a reaction and the
activation barrier represented by the activation energy
EA, which for a given reaction is related to the heat of
reaction, ꢀHR, by the following equation [50]:
Furthermore, as can be seen from the plot and
Table II, the values of the energy of activation for 2-
fluoroethanol and 2,2,2-trifluoroethanol stay far from
the set of data as well as from the average value ob-
served for the reactions of OH radical with organic
compounds in the aqueous phase.
EA = a + bꢀHR
(2)
It has also been demonstrated [22–25] that equiva-
lent H atoms in the molecule will contribute to the same
extent to the observed rate constant. Thus, Eq. (4) can
also be rewritten as
where a and b represent empirical constants.
For a series of reactions that proceed through the
same reaction mechanism, it follows that a correlation
between the reaction enthalpy and the bond dissocia-
tion energy BDE (C H) of the weakest bond broken
during the reaction should exist:
ꢀ
ꢁ
k
log
= log kH
nH
ꢀ
ꢁ
aꢁ
bꢁ
ꢀHR ∼ BDE(C H)
(3)
=
log A −
−
· BDE(C H) (8)
RT
RT
As shown elsewhere [22–25], a correlation can be then
written
Using the data reported in Table VI, the corresponding
plot is shown in Fig. 6.
In this case, the following correlation is obtained
(Eq. (9)):
ꢀ
ꢁ
EA
RT
aꢁ
log k = log A −
=
log A −
RT
bꢁ
−
· BDE(C H)
(4)
ꢂ
ꢃ
log kH/M−1s−1 = (33 3)
RT
−(0.06 0.008) BDE/kJmol−1
(9)
The Evans–Polanyi plot in the form of energy of ac-
tivation (EA) against the bond dissociation energies
of the weakest bond for the investigated reactions of
OH with small aliphatic alcohols in aqueous solution
is presented in Fig. 5. Here, the bond strengths for the
C H bonds in the halogenated compounds that have
been calculated in the present work (cf. Table IV) have
directly been used.
with n = 11 and r = 0.98.
Gligorovski and Herrmann [25] presented a corre-
lation where an extended data set is considered for
reactions of OH radicals with organic carbonyl com-
pounds in the aqueous phase, using BDE values cal-
culated with the incremental method of Benson [51].
The reasonably good agreement between (Eq. (9)) and
the previous expression [25] allows the use of this em-
pirical relation also for the prediction of reactivity for
a wider selection of compounds including carbonyl
compounds and alcohols.
From the regression line of the Evans–Polanyi plot,
the following correlation can be obtained:
EA/kJ mol−1 = −(110 107) + (0.3 0.28)
· BDE(C H)/kJ mol−1 (5)
Equations (5) and (9) permit the estimation of
OH rate constants for H-abstraction reactions from
halogen-substituted alcohols in aqueous solution at
T = 298 K when measurements are not available. Fur-
thermore, the user must be aware of the uncertainty of
the obtained results due to the experimental and BDE
estimation errors.
Furthermore, the kinetic parameters for hydro-
gen abstraction reactions may be also empirically
correlated either with the number and nature of con-
stituent atom groups via additivity rules or with molec-
ular property values, such as ionization potentials
[52,53], leading to various structure–activity relation-
ships. As shown previously for OH radical gas-phase
reactions with halogenated ethanols [2], a correlation
with n = 10 and r = 0.65.
In Eq. (5), only the halogenated ethanols together
with four not substituted aliphatic alcohols are con-
sidered. The obtained correlation results are differ-
ent with respect to the available literature correlations
(Eq. (6) [22] and Eq. (7) [25]) for aqueous-phase re-
actions of OH radicals with oxygenated organic com-
pounds. Thus, the authors recommend to restrict the
use of Eq. (5) only for the estimation of kinetic data
for reactions of halogen-substituted alcohol with OH
in aqueous solution.
EA/kJ mol−1 = −(52 33) + (0.16 0.08)
· BDE(C H)/kJ mol−1 (n = 16; r = 0.75) (6)
International Journal of Chemical Kinetics DOI 10.1002/kin

184
MOROZOV ET AL.
Figure 5 Evans–Polanyi plot in the form of energy of activation (E /kJ mol−1) vs. bond dissociation energy (BDE/kJ mol−1).
A
This work ( ). Literature values ( ).
◦
•
does exist between the sum of the Pauling’s electroneg-
ativities (SPE) [48] and the logarithm of the measured
rate constants.
As shown in Fig. 7, a correlation (Eq. (10)) has
been obtained plotting the logarithm of the observed
rate constants as a function of the electronegativity of
the CX3 group.
The linearity of the plot suggests that the measured
rate constants correlate well with the empirically de-
rived electronegativity of the terminal methyl group.
It also reflects the decrease of the reactivity of halo-
genated ethanols toward the electrophilic OH due to
the electron-withdrawing effects of the halogen sub-
stituents. In addition, this linear relationship can be
used to determine the rate constants of those OH reac-
tions with HEs that have not been determined experi-
mentally.
log(k298/M−1s−1
)
= (11.4 0.9) − (0.27 0.08) · SPE (10)
A good correlation can be also obtained comparing
the aqueous- and gas-phase rate constants (Table III)
for the reactions of OH radicals with small HEs. The
linear relationship is shown in Fig. 8, and the following
where n = 7 and r = 0.96. The values of electronega-
tivities used to calculate the SPE are F (4), Cl (3), H
(2.1), and for C (2.5) [48].
Table VI Rate Constants (298 K) and for Equivalent Abstractable Hydrogen Atom (kH) for Reactions of the OH
Radical in Aqueous Solution
Compound
k (298 K) (M−1 s−1
)
n
k
H
(M−1 s−1
)
log k
H
Reference
H
2-Fluoroethanol
2,2-Difluoroethanol
2,2,2-Trifluoroethanol
2-Chloroethanol
2,2-Dichloroethanol
2,2,2-Trichloroethanol
Ethanol
1-Propanol
2-Propanol
1-Butanol
tert-Butanol
5.4 × 108
2.8 × 108
0.8 × 108
8.6 × 108
3.9 × 108
2.4 × 108
2.1 × 109
3.2 × 109
2.1 × 109
4.1 × 109
5.0 × 108
2
2.7 × 108
1.4 × 108
0.4 × 108
4.3 × 108
2.0 × 108
1.2 × 108
1.1 × 109
1.6 × 109
2.1 × 109
2.1 × 109
0.6 × 108
8.4
8.1
7.6
8.6
8.3
8.1
9.0
9.2
9.3
9.3
7.7
This work
This work
This work
This work
This work
This work
[24]
2
2
2
2
2
2
2
1
2
9
[24]
[22]
[22]
[22]
International Journal of Chemical Kinetics DOI 10.1002/kin

HYDROXYL RADICAL REACTIONS WITH HALOGENATED ETHANOLS
185
with HEs when the rate constant is known for one of
the two phases.
ATMOSPHERIC IMPLICATIONS
The atmospheric degradation of HEs is initiated by
radical reactions in the gas phase by OH and, possi-
bly, NO3 radicals, or halogen atoms. Selleva˚g et al.
[2] calculated the tropospheric lifetime of fluorinated
ethanols to be between 20 and 117 days considering
their gas-phase reactions with OH as the major sink.
The primary oxidation products, fluorinated aldehydes,
are suggested to be not harmful to the environment due
to their small atmospheric concentration in the sub-ppb
range. Secondary gas-phase products such as CHFO
and CF2O will be incorporated into droplet/aerosols
and hydrolyzed to give CO, CO2, and HF within days.
Aphotolyticdecompositionmightalsooccur;however,
Vasiliev et al. [54] ruled out this possible degradation
channel in the case of 2,2,2-trifluoroethanol.
The removal from the atmosphere through wet de-
position has been also suggested [3], and it has been es-
timated to account up to 30% for 2,2,2-trifluoroethanol
using a simple model, where the authors used a rather
high value as global average for liquid water content
(LWC) that might lead to an overestimation of the up-
take in cloud water. It must also be mentioned that no
liquid phase sinks are included though the atmospheric
lifetime of these compounds depends on OH concen-
trations and their reactivity in the different phases.
As reported above, FAs are relatively soluble in
water and they may be removed from the troposphere
by uptake in cloud droplets and further oxidized in
water droplets before the removal through wet depo-
sition processes. In-cloud processes should be taken
in account since CF3-containing FAs may lead to tri-
fluoroacetic acid (TFA) formation. With the possible
exception of TFA, the hydrolysis products are ubiqui-
tous, naturally occurring species that have little adverse
environmental impact.
Figure 6 Evans–Polanyi plot in the form of log k
H
(M−1s−1) vs. BDE (kJ mol−1). This work ( ). Literature
•
values ( ).
◦
equation can be written:
k
298,aqueous/M−1s−1 = (0.11 0.26) × 109
+ (0.84 0.12)k298,gas/M−1s−1
(11)
where n = 8 and r = 0.99.
The fact that the slope of Eq. (11) is close to 1 indi-
cates that the rate constants of aqueous-phase reactions
of halogenated alcohols with OH radicals are simi-
lar to the gas-phase reactions. However, for a detailed
comparison between aqueous- and gas-phase processes
phase-transfer parameters (e.g., Henry’s constant val-
ues) as well as radical concentrations must be consid-
ered. A more detailed discussion on this issue is given
in the next section. Equation (11) can be used alter-
natively to estimate the rate constant of OH reactions
For the evaluation of the tropospheric lifetimes of
substituted alcohols in the gas and aqueous phases,
lifetimes have been calculated using the measured
kinetic constants and available modeled OH radical
concentrations. The radical concentrations substan-
tially depend on the atmospheric environmental con-
ditions. Therefore, modeled maximum and minimum
gas- and aqueous-phase concentrations of OH rad-
icals for different atmospheric regimes (Table VII)
have been used for the estimation of the tropospheric
lifetimes in both phases. The radical concentrations
were derived from SPACCIM model [55] simulations
using a complex multiphase chemistry mechanism
Figure 7 Plot of the logarithm of the second-order rate con-
stants (log k/M−1 −1) vs. the sum of Pauling electronega-
s
tivities of the terminal CX3 (X = H-, Cl-, F-) group.
International Journal of Chemical Kinetics DOI 10.1002/kin

186
MOROZOV ET AL.
Figure 8 Plot of the measured aqueous-phase rate constants for the reaction of OH radicals with a series of linear alcohols vs.
the corresponding gas-phase rate constants at 298 K. Numbering refers to Table III.
RACM-MIM2(extended)/CAPRAM3.0i [56]. Model
simulations have been performed for three scenarios.
These are anthropogenic polluted (urban), continental
background (remote), and marine tropospheric regimes
based on radiation conditions of 19 June (summer sol-
stice, 45◦N). The derived minimum and maximum OH
concentrations correspond to nighttime and daytime
conditions, respectively. The both aqueous-phase con-
centrations summarized in Table VII correspond to
cloud-free conditions at 90% relative humidity level
(deliquescent aerosol particles) and in-cloud condi-
tions (cloud droplets) and represent the total concentra-
tions as integrated of the aqueous particle/cloud droplet
spectrum.
In Table VIII, the atmospheric lifetimes for the three
scenarios using the concentration of OH radicals as in
Table VII are then reported.
As can be seen in Table VIII, halogenated alcohols
are processed faster in the aqueous phase than in the
gas phase. It should be noted that the aqueous-phase
lifetimes are in most of the cases 2 orders of magnitude
smaller than the corresponding gas-phase lifetimes.
However, the calculated lifetimes do not account for
the relative distribution of the considered compounds
between the gas and aqueous phase. At present, the
missing Henry’s constant values for the halogenated
alcohols do not allow more precise conclusions of the
fate of HEs, but the kinetic data obtained here sug-
gested clearly that the aqueous-phase processes can
establish important sinks for HEs in the troposphere.
SUMMARY
The kinetic investigations presented here support the
view that OH radicals react with saturated organic
compounds through the abstraction of the hydrogen
atom with the weakest bond dissociation energy in
the molecule. In the case of the halogen-substituted
ethanols, the kinetic and theoretical results indicate
that the H atoms abstracted are the ones bonded to the
Table VII Modeled Concentrations of OH Radical in the Gas Phase as well as Aqueous Phase (Cloud Droplet and
Deliquescent Particle Conditions; See Text)
A
B
C
Scenario
Gas Phase (molec. cm−3
)
Cloud Droplets (mol L−1
)
Wet Particles (mol L−1
)
Remote scenario
Min.
Max.
Min.
Max.
Min.
Max.
1.2 × 105
4.2 × 105
1.2 × 106
3.3 × 106
1.5 × 105
1.5 × 106
1.0 × 10−14
5.0 × 10−14
5.0 × 10−14
5.3 × 10−12
5.0 × 10−16
1.0 × 10−14
4.0 × 10−13
3.6 × 10−12
1.0 × 10−14
6.0 × 10−14
5.0 × 10−14
8.0 × 10−13
Marine scenario
Urban scenario
International Journal of Chemical Kinetics DOI 10.1002/kin

HYDROXYL RADICAL REACTIONS WITH HALOGENATED ETHANOLS
187
Table VIII Calculated Lifetimes of Halogenated Ethanols Based on Modeled Gas- and Aqueous-Phase OH Radical
Concentrations (Table VII) for Three Different Tropospheric Pollution Conditions (Remote, Marine, Urban)
Lifetime,
Remote
Lifetime,
Marine
Lifetime,
Urban
Conditions
Conditions
Conditions
Compound
A
B
C
A
B
C
A
B
C
2-Fluoroethanol
Min.
Max.
Min.
Max.
Min.
Max.
Min.
Max.
Min.
Max.
Min.
Max.
Min.
Max.
18
63
61
210
270
930
21
75
–
–
0.43
2.1
0.89
4.5
1.4
7.2
0.26
1.3
0.59
3
0.7
3.5
0.14
1.3
0.3
2.7
0.48
4.3
0.09
0.78
0.2
1.8
0.2
2.3
6.3
7.8
21
34
93
2.7
7.5
–
0.004
0.43
0.008
0.89
0.014
1.4
0.002
0.26
0.006
0.59
0.007
0.7
0.001
0.11
8.6
51
18
110
29
170
5.2
31
12
71
14
84
5
50
17
170
75
750
6
60
–
–
2.1
43
4.5
89
7.2
140
1.3
26
3
59
3.5
70
0.55
11
0.64
10
1.3
21
2.2
35
0.39
6.2
0.89
14
2,2-Difluoroethanol
2,2,2-Trifluoroethanol
2-Chloroethanol
2,2-Dichloroethanol
2,2,2-Trichloroethanol
Ethanol
–
110
390
8.7
30
14
39
1.1
3.0
31
310
2.4
24
1.1
17
0.17
2.6
2.1
0.04
0.33
0.1
0.55
2.2
13
All the lifetimes are expressed in days.
A, B, and C refer to the OH radical concentrations reported in Table VII for the corresponding scenario.
carbon atom carrying the alcoholic function. Compu-
tational methods have been applied for the estimation
of bond dissociation energies and ionization potentials
of halogenated ethanols.
Three different reactivity correlations have been ob-
tainedandcanbeappliedfortheestimationofunknown
rate constants with focus on reactions of OH radicals
with halogen-substituted alcohols in aqueous solution.
The comparison between the gas- and aqueous-phase
rate coefficients for the investigated compounds shows
that solution processes are competitive, and they should
be included in environmental assessments on halo-
genated ethanols.
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