Atmospheric Environment 35 (2001) 2169}2178

Release of iodine in the atmospheric oxidation of alkyl iodides

and the fates of iodinated alkoxy radicals
E.S.N. Cotter, N.J. Booth, C.E. Canosa-Mas, R.P. Wayne*
Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Rd., Oxford OX1 3QZ, UK
Received 27 June 2000; received in revised form 10 October 2000; accepted 18 October 2000

Abstract

This paper describes a study of the products of the Cl-atom-initiated oxidation of three alkyl iodides, RI"CH I,

C H I, and 2-C H I, carried out in synthetic air at atmospheric pressure and at room temperature. Fourier-transform
   
infrared spectroscopy was used to follow the decay of reactants and subsequent formation of products. The primary step
proceeds via two channels, one of which yields HCl and an iodinated alkyl radical, and the other I atoms and an alkyl
chloride. Quantitative analysis of the product yields, together with an assessment of the formation of HCl in secondary
processes, allowed the fractional branching into the two channels to be calculated. The channel yielding HCl from RI
constitutes a fraction 0.59, 0.93, and 0.68 for R"CH , C H , and 2-C H . The iodinated alkyl radical forms "rst
    
a peroxy, and then an alkoxy, radical in the presence of air. The "nal products CH O, CH CHO, and CH COCH were
   
observed as expected for the decomposition of these radicals with RI"CH I, C H I, and 2-C H I, and the fractions of
    
the alkoxy radicals fragmenting to the carbonyl compounds were 0.88, 0.57, and 0.86, respectively. Atomic iodine is
formed concomitantly with the carbonyl species, so that these fractions also indicate the yield of I atoms in the secondary
process. Alternative reaction pathways for the iodinated alkoxy radicals, in particular reaction with O , are evaluated

and discussed. The yields of I atoms in the primary and secondary steps, taken in combination with kinetic data, make it
possible to estimate the contribution of the Cl-initiated oxidation of the alkyl halides to I-atom production in the
atmosphere (and, making certain assumptions, the analogous contribution from OH-initiated oxidation). Radical-
initiated processes might augment the photolytic yield of I atoms from simple alkyl iodides: the maximum enhancements
lie between 5% (CH I) and more than 30% (2-C H I).  2001 Elsevier Science Ltd. All rights reserved.
  
Keywords: Alkyl iodides; Cl oxidation; Iodine; Fourier-transform infrared spectroscopy (FTIR); Reaction channels; Unimolecular
decomposition

1. Introduction by long-path di!erential optical absorption spectroscopy

The participation of I atoms and IO radicals in
atmospheric chemistry has recently received increased
attention (Wayne, 2000; Vogt et al., 1999). Chain pro-
cesses involving I and IO might play a minor part in
ozone loss in the troposphere. For example, at Mace
Head, Ireland, IO has been measured (Alicke et al., 1999)
 Present addres. British Antarctic Survey, Madingley Road,
Cambridge, CB3 0ET, UK.
* Corresponding author.
E-mail address: wayne@physchem.ox.ac.uk (R.P. Wayne).
(LP-DOAS) at concentrations of up to 6 ppt. The
observed amounts of IO are quite su$cient to have
a substantial in#uence on boundary-layer photochemis-
try: a mixing ratio of 6 ppt can increase the rate of
removal of O by as much as 70% over the ocean

and 10% over land. It has also been suggested that IO
radicals might in#uence NO and HO chemistry in the
V V
troposphere by forming IONO and HOI. Davis et al.

(1996) have reported that, where reactive I concentra-
tions reached levels of 7 ppt in the upper troposphere,
a consequential shift in the HO /OH ratio occurred,

resulting in a 9% increase in atmospheric [OH].
Such enhancements would have important implications

1352-2310/01/$ - see front matter  2001 Elsevier Science Ltd. All rights reserved.
PII: S 1 3 5 2 - 2 3 1 0 ( 0 0 ) 0 0 4 7 9 - 9
2170 E.S.N. Cotter et al. / Atmospheric Environment 35 (2001) 2169}2178

for rates of OH-initiated oxidation of volatile organic CH X#O PCH XO , (6)

   
compounds.
A major source of I is the photolysis of alkyl iodides, in CH XO #NOPCH XO#NO , (7)
   
processes such as
CH XO #CH XO PCH XO#CH XO#O , (8a)
      
CH I#hvPCH #I. (1)
  PCH XOH#CHXO#O ,
The oxide radical IO is formed in the reaction of I with  
(8b)
O . Measurements of IO generally support this con-

clusion. For example, Alicke et al. (1999) found that the where X"Cl, Br or I. The branching ratio for reaction
IO follows solar radiation intensity very closely, with (8a) is &1 for most halogenated peroxyl radicals (Les-
concentrations below the level of detectability during the claux, 1997) so that this channel, or similar reactions with
night. Alkyl iodides are photolysed e$ciently in the other peroxy species such as CH O , are believed to be
 
troposphere, and most workers have based their calcu- the dominant alkoxy radical formation processes in the
lations of iodine production rates on the assumption that remote atmosphere where NO concentrations are rela-
reaction (1) and its analogues represent the only losses for tively low.
the iodides. However, we have recently shown (Cotter et Once formed, the alkoxy radical can react via one of
al., 2000) that attack initiated by OH and Cl could three pathways
account for 10}20% of the removal of the CH I. Quite
 CH XOPCH O#X, (9)
signi"cant concentrations of other alkyl iodides, includ-  
ing C H I, 1-C H I and 2-C H I, have also been found
      CH XOPHCO#HX, (10)
in the lower troposphere, and especially in the marine 
boundary layer (Rasmussen et al., 1982; Schall and CH XO#O PCHXO#HO . (11)
Heumann, 1993). In some of these cases, the OH- and Cl-   
initiated attack could add signi"cantly to (or even Earlier experiments have examined the products formed
dominate over) photolytically initiated oxidation. in the oxidation of halogenated compounds such as
If substantial fractions of the alkyl iodides released to CH Cl (Wu and Carr, 1999; Wallington et al., 1995),

the atmosphere are consumed by radical reactions rather C H Cl (Kaiser and Wallington, 1995; Shi et al., 1993)
 
than photolysis, it is evident that a quantitative assess- and CH Br (Orlando et al., 1996; Chen et al., 1995). In

ment of the source strength of I atoms requires a know- the case of the chloromethoxy radical, reactions (10) and
ledge of how much iodine can be released by secondary (11) were found to be competing processes over the tem-
steps following the initiation. This is the central problem perature range 264}336 K. The chloroethoxy radical has
that the present paper addresses. Iodinated alkoxy spe- also been extensively studied. Three-centre elimination,
cies are implicated in the liberation of atomic iodine, and reaction (10) with X"Cl, has been found to dominate
a more general goal of our work has been to establish a the decomposition of this radical, so that the main prod-
mechanism for the pathways of degradation of iodinated uct is HCl. This behaviour is in contrast to that of the
alkoxy radicals. To these ends, we have investigated, by brominated methoxy radical, which has been observed to
FTIR spectroscopy, the products of the processes predominantly undergo unimolecular decomposition,
analogous to reaction (9), to form Br and CH O. Reac-
CH I#ClPproducts, (2) 
 tion with O and elimination of HBr were found to be

C H I#ClPproducts, (3) minor reaction pathways for the brominated alkoxy rad-
 
ical. Since reaction (11) yields HO as a product, a fur-
2-C H I#ClPproducts (4) 
  ther reaction of potential importance in the system is
when the reactions were carried out in synthetic air at
CH XO #HO PCH XOOH#O . (12)
atmospheric pressure and room temperature. The iodides     
were chosen as important examples of the classes of Our experiments were designed to look for end products
compounds, and Cl-atom initiation was employed such as CH O, HX, CHXO, and CH XOOH in order to
because of the high reactivity of the iodides towards this  
investigate the relative importance of steps (9)}(11) for
species as well as the ease of generating it in our experi- the alkoxy radicals derived from our set of alkyl iodides,
mental apparatus. and thus to estimate the yield of I atoms from process (9).
Alkoxy radicals are key intermediates in the oxidation
of many volatile organic species, including halogen bear-
ing compounds. The formation of the alkoxy species can
2. Experimental
be illustrated in relation to Cl-initiated oxidation of
methyl halides
The experiments consisted of photolysing mixtures of
CH X#ClPCH X#HCl, (5) the alkyl iodide, molecular chlorine, and synthetic air
 
 E.S.N. Cotter et al. / Atmospheric Environment 35 (2001) 2169}2178 2171

Table 1 interfaced to a PC and the results analysed using a com-

Typical reaction conditions employed for the reaction of Cl mercial software package (ATI Mattson WinFIRST).
atoms with CH I, C H I and 2-C H I A Wilkes cell (volume 5.6 l; Te#on-lined) with a path
    
length of 11.25 m was employed. A rotary pump (Edwards
Compound [RI] [Cl ] Photolysis times
 GDR 1) was used to evacuate the cell, and the vacuum was
(molecule cm\) (molecule cm\) (min)
monitored using a Pirani gauge (Edwards PR10). The cell
CH I &4.0;10 &3.0;10 0}5 was purged constantly with a supply of nitrogen to remove

C H I
 
&2.0;10 &2.0;10 0}5 the e!ect of any possible leaks. Spectra were taken in the
2-C H I &1.0;10 &1.0;10 0}4 range of 400}4000 cm\; they were recorded by taking the
 
average of 300 scans at a resolution of 2 cm\, the data
Table 2 collection taking ca. 10 min. Calibrations for each reactant
Characteristic absorption peaks for reactants and identi"ed and product species were carried out where the compound
products was available commercially.
Reaction mixtures were photolysed for periods
Compound Absorption peak ranging from 0 to 60 s. Spectra were taken after each
(cm\) period of photolysis by allowing the mixture to expand
into the cell. Consumption of organic species was never
CH I 3006}2934
 more than &20% of the initial concentration. Table 1
1281}1207
shows typical concentrations and photolysis times used
C H I 1384}1308
  for each reaction. The reactants and products present in
3000}2935
762}729 the reaction mixture were identi"ed using the character-
2-C H I 1172}1123 istic absorption peaks outlined in Table 2.
 
HCl 3047}2706 The possibility of a dark reaction between Cl and

CO 2214}2061 each alkyl iodide was investigated by taking repeated
CH O 2932}2687 spectra over the time-scale of a typical experiment, but

1816}1659 without the lamps illuminated. Reaction was found to be
CH CHO 1801}1707 signi"cant only for 2-C H I; corrections were applied as
  
CH COCH 1811}1691
  described later. CH I and C H I have maximum
3056}2887   
absorption cross-sections at
&258 nm (Rattigan et al.,
2-C H Cl 1292}1238
  1997) so that photolysis of these compounds is not an-
654}599
CH Cl 1384}1308 ticipated to be a signi"cant loss process in our system,
 where the lamp output is con"ned to much longer
3000}2935
762}729 wavelengths. This supposition was tested by exposing
each iodide to the lamp radiation with Cl absent from

the mixture. No chemical change could be detected over
contained in a PTFE bag. Photolysis of the Cl yields Cl the time-scale of the normal experiments.

atoms that react with the alkyl iodide. Reactants and
products were identi"ed, and their concentrations deter-
3. Materials
mined as reaction proceeded, by Fourier-transform
infrared (FTIR) spectroscopy.
The organic species and Cl were puri"ed using
A collapsible bag made of PTFE (Alltech) was used as 
repeated freeze}pump}thaw cycles. Formaldehyde was
the reaction chamber; its volume was &56 l. A bank of
produced by pyrolysing a degassed sample of parafor-
8 UV-A lights (Philips HP 3148/A; 40 W), whose spectral
maldehyde. Synthetic air was passed through two
output was centred on
&360 nm, was used to e!ect the
phosphorus pentoxide traps (P O ) to remove traces of
photolysis of Cl . The bag was kept in a dark chamber to  
 water vapour prior to #ushing the reactants into the
prevent any unwanted photolysis.
reaction chamber. Table 3 lists the materials used and
Mixtures were prepared by expanding a known con-
their purity.
centration of the reactants from a known volume into the
bag. Each mixture was made up to atmospheric pressure
using synthetic air at room temperature (298$2 K), and 4. Results and discussion
allowed to stand in the dark for 2 h before photolysis.
The pressures of the species of interest were recorded 4.1. CH3 I
using an electronic manometer (MKS Baratron, range
0}10 or 0}100 Torr). Fig. 1 shows typical infrared spectra of (a) the starting
The FTIR spectrometer (ATI Mattson Research Series materials; (b) the mixture after photolysis; and (c) spec-
1; deuterated triglyceride sulphate detector) was trum (b) after removal of the features in (a). The product
2172 E.S.N. Cotter et al. / Atmospheric Environment 35 (2001) 2169}2178

Table 3 spectrum of Fig. 1(c) clearly shows the characteristic

Materials used and their purity absorbances of HCl and CH Cl. There is, however, no

evidence for the formation of ICl. These observations
Material Supplier Stated purity seem to be consistent with the thermochemistry of the
(%) possible channels in the initial interaction of Cl atoms
with CH I:
Air (80% N , 20% O )
 
BOC 99.9 
CH I Aldrich 99.9 CH I#ClPCH I#HCl
  
C H I Aldrich 99
 
2-C H I
 
Aldrich 99  H"#2.3 kJ mol\, (13a)
HCl Aldrich 99# 
CO Aldrich 99.9 PCH Cl#I

CH O Aldrich 99.9
  H"!110.7 kJ mol\, (13b)
CH CHO

BDH 99 
CH COCH Aldrich 99.9#
  PCH #ICl
CH Cl

Aldrich 99.9 
2-C H Cl
 
Aldrich 99  H"#28.3 kJ mol\ (13c)


Fig. 1. Spectra of the reactants and products of the reaction of Cl atoms with CH I for (a) no photolysis; (b) after 130 s photolysis; and (c)

di!erence between (b) and (a).
 E.S.N. Cotter et al. / Atmospheric Environment 35 (2001) 2169}2178 2173

(Thermochemical data are taken from Atkinson, 1997;

Lide, 1994).
Reaction (13a) thus evidently occurs, so that the
secondary steps equivalent to reactions (6) and (8)}(12)
with X"I are

CH I#O PCH IO , (14)

   
CH IO #CH IO PCH IO#CH IO#O , (15a)
      
PCH IOH#CHIO#O , (15b)
 
CH IOPCH O#I, (16)
 
CH IOPHCO#HI, (17)

CH IO#O PCHIO#HO , (18)
  
CH IO #HO PCH IOOH#O , (19)
    
and could potentially yield the detectable (non-radical) Fig. 2. [HCl]![CO] as a function of ![CH I].

products CH IOH, CHIO, CH O, HI, and CH IOOH.
  
Of these species, only CH O was detected. No evidence

was seen for absorption features of an alcohol, of CHIO represent the obvious chemical route since
(based on the spectrum of Barnes et al., 1995), or of k "7.3;10\ cm molecule\ s\ (DeMore et al.,
CH IOOH (spectrum assumed to have hydroperoxide 
 1997).
features similar to that of CH OOH presented by
 Carbon monoxide and HCl are produced in equal
Wallington and Japar, 1990). As explained earlier, chan- amounts in the secondary reactions (20) and (21), while
nel (15b) is not expected to be of importance for HCl itself is formed in both reaction (13a) and reaction
halogenated alkoxy radicals, so that the absence of (20). Since reaction (21) is the only source of CO, it can be
CH IOH is not surprising. However, the absence of
 used as a marker to indicate the extent of secondary
CHIO as well means that reaction (18) must be a minor production of HCl. Fig. 2 shows [HCl]![CO] plot-
channel at most. Furthermore, since HI is absent, ted as a function of ![CH I]. The slope of this "gure
reaction (17) must be unimportant. In the absence of 
gives k /k "0.59$0.04. Errors quoted for the slopes
reaction (18), HO cannot be formed in our system,  
 of this and similar plots include the precision of the
so that reaction (19) cannot yield hydroperoxide. instrument in measuring peak areas. A fully weighted
The conclusion to be drawn from our interpretation is linear regression analysis was used that allows for errors
that CH IO radicals decay exclusively via channel (16) to
 in both axes; the error on the slopes is quoted as the 95%
form the products CH O and I. That is, the branching
 con"dence limits.
ratio  for loss of CH IO in channel (16), de"ned by
 Similarly, the yield of CH Cl may be used to establish

"k /(k #k #k [O ]), appears to be unity on
     directly the fraction of the initial reaction between Cl and
the basis of the qualitative observations. We now turn to CH I that proceeds via channel (13b). Fig. 3 displays
quantitative assessment of . 
[CH Cl] as a function of ![CH I]. The slope gives
During the course of the experiments, [CH O]  
 k /k "0.32$0.05. Bilde and Wallington (1998)


increased at "rst with photolysis time. At higher conver- have previously examined the formation of CH Cl in this
sions, the concentration decreased, but CO, now 
reaction. Although they quote a yield of (20% in 1 atm
observed as a product, built up during this period. The of air, they also observe that yields increased to as much
observations indicate a secondary loss for CH O that
 as 80% at the highest concentrations of CH I used in

ultimately leads to the formation of CO. Diagnostic their experiments. Judging from the data presented,
experiments, in which CH O was expanded on its own
 yields at least as large as ours might be expected at the
into the bag and exposed to light over the time-scale of values of [CH I] used in our own experiments. Thus the
a typical experiment, failed to provide any evidence for 
results of our study seem broadly consistent with those of
photolysis, even when [CH O] exceeded the values for-
 Bilde and Wallington.
med in the experiments with CH I. Thus, the pair of
 Within experimental error, therefore, (k #k )/k
 

reactions is approximately unity, a result entirely consistent with
CH O#ClPHCl#HCO, (20) our earlier conclusion, based on both thermochemistry
 and the apparent absence of ICl, that reaction (13c) does
HCO#O PHO #CO (21) not contribute. Although it is possible that if ICl were
 
2174 E.S.N. Cotter et al. / Atmospheric Environment 35 (2001) 2169}2178
Fig. 3. [CH Cl] as a function of ![CH I].
 
Fig. 4. [CH O]#[CO] as a function of !0.6[CH I].
 
formed, it could be subject to loss by photolysis in our
system, there is thus no need to invoke its formation in
the "rst place.
It is now possible to calculate the value of
"k /(k #k #k [O ]). Assuming that all CH I
     
produced in reaction (13a) is ultimately converted to
CH IO (see earlier), it follows that
 PC H Cl#I
[CH O]
"  .
!(k /k )[CH I]
   

Our measurement from Fig. 2 gives k /k K0.6. We
 
therefore plot [CH O#CO] as a function of !0.6
 A sequence of reactions analogous to processes
[CH I] in Fig. 4. The slope of this "gure gives
 (14)}(16), and culminating in the step
"0.85$0.1, in agreement with our expectation from
the qualitative spectroscopic evidence that reaction (16)
Fig. 5. [product] as a function of ![C H I].
 
is the sole fate of the alkoxy radical CH IO in our

system.
4.2. C2 H5 I
The reaction of Cl atoms with both C H I and
 
CD CH I were investigated in order to examine any
 
preference for H (D) abstraction at the positions  or  to
the iodine atom. No DCl was detected in experiments
with the deuterated compound, suggesting that abstrac-
tion occurs exclusively at the -position. Fig. 5 shows
[HCl] as a function of ![C H I] (circles) and of
 
![CD CH I] (squares). The overall (uncorrected)
 
yield of HCl was found to be virtually the same for both
compounds, the slopes of the plots being 0.93$0.10 for
C H I and 1.0$0.1 for CD CH I, again suggesting
   
strongly that the abstraction is exclusively of H in the
case of the deuterated compound.
The upright triangles in Fig. 5 show the yield for
formation of C H Cl in this system. The slope of the
 
least-squares line drawn through the points is
0.46$0.04. The observations thus suggest that the initial
interaction proceeds via two channels
C H I#ClPC H I#HCl, (22a)
   
(22b)
 
analogous to the two open channels in reaction (13), and
with k /k "0.46$0.04. By di!erence from the total
yield of HCl, it follows that k /k "0.47$0.14. As in
 
the case of CH I, there is thus a secondary source of HCl.

C H IOPCH CHO#I (23)
  
 E.S.N. Cotter et al. / Atmospheric Environment 35 (2001) 2169}2178
both liberates free I atoms, and generates the observed
product CH CHO. Fig. 5 includes (inverted triangles)

the yield data for this species. The slope of a straight line
forced through these points is 0.27$0.06. If there were
no losses of CH CHO, this result would suggest an

e$ciency of conversion of C H I to CH CHO of
   
(0.27$0.06)/(0.47$0.14)"0.57$0.20, apparently less
than unity. However, in reality the acetaldehyde reacts
with Cl atoms su$ciently rapidly (rate constant
7.6;10\ cm molecule\ s\; Atkinson et al., 1989) for
the reaction to act as a signi"cant loss process for
CH CHO. The secondary generation of HCl certainly
 

points to the occurrence of such a step, and a simple
numerical kinetic model is able to simulate well the
growth of both CH CHO and HCl.
 0.59$0.11, presumably in the unimolecular decomposi-
4.3. 2-C3 H7 I
The spectrum of the reaction products observed in the
reaction of Cl atoms with 2-C H I in synthetic air dem-
 
onstrates the presence of acetone. The main products
formed are evidently HCl, 2-C H Cl, and CH COCH .
   
As pointed out in the experimental section, the mixture of
2-C H I, Cl , and air undergoes a reaction in the dark
   suggested circumstantially by the absence of secondary
(2-C H I is consumed and 2-C H Cl is formed: no HCl
   
or CH COCH are produced in the dark). Even though
 
this reaction is slow compared with the photochemically
induced process, the extent is not insigni"cant over the
total times of exposure and measurement. Determina-
tions were therefore made of all concentrations in
unexposed test mixtures at the same time intervals as
measurements were made on illuminated samples in
order to apply appropriate corrections. Fig. 6 shows the
product yields, corrected in this way, as a function of
consumption of the starting reactant (also corrected for
the dark reaction). Relative yields of HCl and 2-C H Cl
 
Fig. 6. [product] as a function ![2-C H I].
 
2175
obtained directly from the slopes of the lines on this plot
were 0.68$0.14 and 0.34$0.12. As with the other
iodides studied, it appear that there are two accessible
channels
CH CHICH #ClPCH CICH #HCl, (24a)
  
PCH CClCH #I (24b)
 
for the primary interaction. The measured yields of HCl
and 2-C H Cl would be consistent with k /k K0.7
   
and k /k K0.3, so that there seems little leeway with
2-C H I as reactant for the secondary production of
 
HCl.
Acetone was formed with a relative yield of
tion of the alkoxy radical
CH CI(O)CH PCH COCH #I. (24)
   
Taken together with k /k "0.68$0.14, the yield
 
of acetone requires that virtually 100% of the
CH CI(O)CH radicals must react in process (24), and
 
that secondary losses of CH COCH are negligible (as
 
production of HCl).
4.4. Comparison of behaviour of the alkyl iodides and of
halogenated alkoxy radicals
Our experiments show clearly that the primary inter-
action between Cl and the alkyl iodides studied here
leads mainly to the formation both of HCl and of the
relevant alkyl chloride, but apparently not of the alkyl
radical. The organic compounds CH O, CH CHO and
 
CH COCH account for most of the loss of the
 
iodinated alkoxy radicals derived from CH I, C H I,
  
and 2-C H I, respectively. The formation of these
 
compounds is expected to be accompanied by the pro-
duction of an equal quantity of atomic iodine. Table 4
summarises the yields obtained for each product channel
for the iodides studied.
Bond energies in CH }X, where X"Cl, Br or I, are

approximately 349, 293, and 238 kJ mol\ (DeMore
et al., 1997). The ease of halogen atom elimination from
alkoxy radicals substituted by the di!erent halogens sug-
gests that the trend of decrease in bond energies must be
mirrored in the haloalkoxy radicals as well. Unimolecu-
lar decomposition becomes increasingly more favourable
as one proceeds down the series. For the analogous
chlorinated compounds CH Cl and C H Cl, reaction
  
with O and unimolecular decomposition to yield

HCl are observed as the dominant fates of the res-
pective alkoxy radicals (Wu and Carr, 1999; Kaiser and
Wallington, 1995; Wallington et al., 1995; Shi et al., 1993).
The decomposition of the brominated alkoxy radical is
2176 E.S.N. Cotter et al. / Atmospheric Environment 35 (2001) 2169}2178

Table 4
Summary of results

Compound Primary yield of HCl Primary yield of HCl Yield of RCl Yield of carbonyl Fraction of alkoxy radical
determined from HCl assessed from RCl compound fragmenting to carbonyl
measurements measurements compound #I

CH I 0.59$0.04 &0.7 0.32$0.05 0.52$0.10
0.88$0.14


C H I 0.93$0.10 &0.5 0.46$0.04 0.27$0.07 0.57$0.20
 
2-C H I 0.68$0.14 &0.7 0.34$0.12 0.59$0.11 0.86$0.25
 
Corrected for secondary production of HCl.

CH O#CO; the slope of Fig. 4 give "0.85$0.10.

Includes secondary production of HCl.
CH CHO.

Secondary production of HCl assumed negligible.
CH COCH .
 

accounted for almost entirely by the unimolecular 4.5. Atmospheric implications

decomposition to yield CH O and Br atoms (Orlando

et al., 1996; Chen et al., 1995). It is hardly surprising,
therefore, that the iodinated alkoxy radicals decompose
mainly to yield a carbonyl compound and an iodine
atom.
These ideas may be given more quantitative substance
by considering the heats of reaction of the various steps.
Atkinson and Carter (1991) have assessed the relative
importance of decomposition of alkoxy radicals and their
reactions with O in terms of the heats of reaction, H
 
and H  , for the two processes. They postulate that if
-
(H) ("H !H  )'179.9 kJ mol\, then reaction
 -
with O would dominate over unimolecular decomposi-

tion, while decomposition of the alkoxy radical would be
the dominant process where (H)(167.4 kJ mol\.
(Note that Atkinson and Carter considered only path-
ways corresponding to reactions (16) and (18) } which, in
any case, are the only ones we observe } and not reaction
(17)). In the case of CH IO, which can decompose in

reactions (16) or (17), or react with O in process (18),

a rough estimate of the enthalpies of reaction can be
obtained from the knowledge that the C}I bond is about
100 kJ mol\ weaker than the C}Cl bond, taken together
with the standard heats of formation calculated by Kaiser
and Wallington (1994) for CH ClO (!9.8 kJ mol\)

and CHClO (!182 kJ mol\). According to these
calculations,  H K!88, !37, and !160 kJ mol\

for reactions (16), (17), and (18), respectively, so
that the condition is satis"ed for reactions (16) and (17)
to dominate over (18). Our experimental evidence shows
that reaction (17) is of no importance, despite its
favourable heat of reaction. This example provides a
reminder that thermochemistry only states that a
reaction is possible; in our example, the complexity
of the process leading to elimination of HI is evidently
the factor that determines that the reaction will not
occur.
The aspect of our work of immediate relevance to
tropospheric chemistry concerns the release of iodine
atoms from the alkyl iodides. It is clear from the experi-
ments described in this paper that, for the alkoxy radical
CH IO derived from CH I, nearly 90% decomposes to
 
yield I atoms. The same is true for the alkoxy radical
produced in the oxidation of 2-C H I, and even in the
 
case of C H I the yield is nearly 60%. On the assump-
 
tion that attack of OH on the alkyl iodides proceeds
entirely via hydrogen abstraction, then these values also
represent the yields of I atoms from the atmospheric
oxidation of the iodides initiated by OH. Furthermore, if
the channel
RI#OHPR#HOI (25)
contributes to the primary interaction, then, in the atmo-
sphere, photolysis of HOI
HOI#hPI#OH (26)
will, in any case, produce an I atom, so that the quoted
yields then become lower limits.
As we have discussed previously (Cotter et al., 2000),
signi"cant amounts of the oxidation of the iodides may
also be initiated in the atmosphere by attack by Cl under
some conditions. The results obtained in the present
experimental study allow the fraction of such Cl-initiated
oxidation that yields alkoxy radicals to be calculated,
and thus for the yields of I from this source to be assessed
as well. The data of Cotter et al. for the rates of photoly-
sis, and OH-, and Cl-initiated oxidation, are used
together with the new results to construct Table 5. This
table thus provides a view of the rates of I-atom
formation in the photochemical and radical-initiated
degradation of alkyl iodides in the atmosphere. Tropos-
pheric concentrations of Cl are rather uncertain, and
 E.S.N. Cotter et al. / Atmospheric Environment 35 (2001) 2169}2178 2177

Table 5
Rates of release of atomic I in photolysis and OH- and Cl- initiated oxidation of selected alkyl iodides

First-order rate constants (s\)

Species Photolysis OH-initiated
Cl-initiated Cl-initiated

CH I 2.3;10\ 1.4;10\ 2.5;10\ 1.2;10\


C H I 2.8;10\ 6.8;10\ 1.4;10\ 4.3;10\
 
2-C H I 7.3;10\ 2.2;10\ 9.1;10\ 2.8;10\
 
Based on a 12 h, globally averaged photolysis rate (D.E. Shallcross, private communication).

[OH]"1.6;10 molecule cm\ (Prinn et al., 1995), 12 h daytime average. The rate constant for OH-initiated oxidation of each alkyl
iodide has been measured recently in our laboratory.
[Cl]"3.3;10 molecule cm\ (Wingenter et al., 1996), 5 h period from dawn.
[Cl]"1.0;10 molecule cm\ (Spicer et al., 1998), an early morning model prediction based on measurements of Cl .


appear highly variable. Nevertheless, the table demon-
strates that the radical-initiated processes might augment
the photolytic yield of I atoms by as much as 5% (CH I)
 Barnes, I., Becker, K.H., Starcke, J., 1995. The gas-phase infrared
and more than 30% (2-C H I) for the largest [Cl] cur-
 
rently thought reasonable.
Quite apart from this speci"c quantitative information
about the release of I atoms, our experimental results
provide further evidence about the atmospheric chem-
istry of halogenated alkoxy radicals. In particular, and in
accord with the postulates of Atkinson and Carter (1991),
the only reaction channel followed by the iodoalkoxy
radicals studied here is unimolecular decomposition
elimination of an iodine atom accompanied by the con-
comitant production of a carbonyl compound.
Acknowledgements
ESNC wishes to thank the Physical and Theoretical
Chemistry Laboratory, University of Oxford, for a grant
for fees and maintenance, during the tenure of which this
work was conducted. The authors also wish to acknow-
ledge grants from NERC (GST/02/1516) and the
European Commission (ENV4-CT97-0393) under the
auspices of which part of this research was initiated or
undertaken.
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