2410 The Journal of Physical Chemistry, Vol. 82,No. 22, 1978 L. T. Molina and M. J.

Molina

Ultraviolet Spectrum of HOC1

Lulsa T. Mollna and Marlo J. Mollna"'

Department of Chemistry, University of California, Irvine, California 927 17 (Received May 8, 1978)

Publication costs assisted by the Natlonal Aeronautics and Space Administration

Gas-phase spectra of equilibrium Hz0-C120-HOC1 mixtures were measured between 200 and 450 nm. The
absorbances of mixtures prepared with different amounts of C120 and H 2 0 yield a value of -0.25 for the
equilibrium constant KeS. Measurements of the spectra of aqueous HOCl solutions give results similar to those
in the gas phase. The HOCl lifetime against photodissociation in the stratosphere is estimated to be -30 min.
This number is quite insensitive to the value of Keqdue to the near isosbestic behavior of HzO-C1zO-HOCl
mixtures in the 320-390-nm wavelength region. It is concluded that HOC1 will not play a significant role as
an inert chlorine reservoir in the stratosphere,

Introduction HOCl has indeed appreciable absorption cross sections

The stratospheric chemistry of halogenated compounds
has been the subject of numerous studies in the past few
years due to the potential perturbations to the ozone layer
that may result from the release of man-made halogenated
hydrocarbons. The chemistry of the most important
atmospheric trace species containing chlorine, such as HC1,
C10, and CIONO2,has been reviewed recentlya2It has been
suggested3+ that HOCl is an additional species which plays
an important role in the stratosphere, where it may be
formed by the reaction'>*
HOz + C10 HOCl + 02
-+ (1)
and destroyed by
HOCl + OH --H20 + C10
HOCl + 0 OH + C10
(2)
(3)
HOCl + hv -OH + C1
+ (4)
A significant fraction of the stratospheric chlorine
burden might indeed be found in the form of HOCl if
reaction 1 is fast and if reactions 2, 3, and 4 are slow. A
value of -4 X cm3 molecule-l s-l has been reported
recentlys for the rate constant for reaction 1, and the rates
of reactions 2 and 3 have not been determined yet. An
early measurement of the UV absorption spectrum of
HOCllO indicated the presence of a very strong absorption
band around 320 nm, but a more recent experiment by
Jaffe and DeMorell showed substantially lesser absorption
in that wavelength region. Nevertheless, the stratospheric
photodissociation rate (reaction 4) estimated with the data
of Jaffe and DeMore is sufficiently fast to make HOCl
unimportant as an inert chlorine reservoir. In contrast,
the theoretical calculations of Jaffe and LanghofP and of
Hirsch et as well as two unpublished experiments,"
indicated practically no absorption beyond 300 nm; if this
is the case reaction 4 would be unimportant as a removal
mechanism for HOCl in comparison with reactions 2 and
3.
We report here an investigation of the UV spectrum of
HOC1. This compound was prepared by mixing water and
dichlorine monoxide. In the gas phase an equilibrium
mixture is established according to the reaction
ClzO + HzO F! 2HOC1
(5)
The infrared spectrum of HOCl vapor has been charac-
terized using this equilibrium mixture13 and the three
recent UV spectral measurements referred to earlier
employed this same HOCl source. Our results indicate that
0022-365417812082-2410$01 .OO/O
beyond 300 nm, in qualitative agreement with the data
reported by Jaffe and DeMore.ll
Experimental Section
The absorption measurements were carried out with
Cary 219 UV-VIS double-beam spectrophotometer. The
minimum detectable change in absorbance was of the order
of 0.003 (i.e., 0.3% absorption). Two absorption cells were
employed for the gas-phase measurements: a 90-cm long,
5-cm diameter quartz cell with an optical path of 180 cm
folded with external mirrors; and a 10-cm long, 2.5-cm
diameter quartz cell. The long path cell was fitted with
two inlets, each one being connected to a separate vacuum
line. Except as indicated below, the cell walls were pre-
conditioned with Clz and C120 for all runs. One of the
vacuum lines was fitted with a stainless steel MKS ca-
pacitance manometer (0-10 torr range) and it was used to
admit a measured amount of C1,O vapor into the cell.
After recording a spectrum of the pure ClzO, water vapor
stored in a 12-L glass bulb was introduced to the cell using
the second vacuum line; the water vapor pressure was
monitored with a Wallace-Tiernan gauge, Model FA141.
Spectra of the mixture were recorded at successive time
intervals until the absorbance showed no further changes.
The spectrum of water vapor alone showed no significant
absorption throughout the 200-500-nm region, as expected.
A control experiment in which ClzO was replaced by Clz
indicated that under our experimental conditions mixing
with water vapor was essentially complete within 1 min.
The 10-cm cell experiments were carried out in a similar
manner; the cell was first attached to the Cl20vacuum line
and later to the water vapor line.
ClzO was synthesized by condensing C12 onto freshly
prepared, dry, yellow mercuric oxide and allowing the
mixture to react overnight at 193 K.14 Excess unreacted
Clz was removed from ClzO by distillation. The C120
purity was checked by measuring its UV spectrum; the
absorption cross sections agree reasonably well with those
reported by Lin.16 Our results are summarized in Table
I along with Lin's values for comparison.
Aqueous solutions of HOCl were prepared by admitting
a known amount of ClzO vapor into an evacuated glass
container, and condensing the vapor at 77 K. A measured
amount of deionized water was then added to the con-
tainer, and a UV spectrum was recorded after transferring
the solution to a 10-cm or to a 1-cm quartz cell. The HOCl
concentration was determined (1)from the known initial
amounts of ClzO and water, and (2) by iodometric titra-
0 1978 American Chemical Society
Ultraviolet Spectrum of HOC1 The Journal of Physical Chem;stry, Vol. 82, No. 22, 1978 2411

TABLE I: Absorption Cross Sections of C1,O Vapor 10.0OLI I , I I , I I I I I I I j

1 0 z O u ,cmz 1OZ0a,cm’
A, nm Lin this work A, nm Lin this work
200 67.0 70.8 330 8.98 8.76
210 23.3 22.6 340 4.13 3.85
220 9.24 8.10 350 2.00 1.80
230 28.3 27.9 360 1.00 0.95
240 98.2 105 370 0.56 0.52
250 182 191 380 0.55 0.43
260 183 194 390 0.67 0.55
270 142 150 400 0.88 0.82
280 121 125 410 1.09 1.10
290 97.8 103 420 1.20 1.28
300 67.2 70.5 430 1.16 1.27
310 38.2 39.9 440 1.06 1.13
320 18.5 19.0 450 0.81 0.87
TABLE 11: Experimental Conditions for HOCl t \\
Vapor Spectra
PCl, 0, PH,O I [H201 o/
runa torr torr rci,oi,
1 0.078 17.0 220
2 0.230 17.0 74
3 0.175 13.8 79 X(nrn)
4 0.150 14.9 99
5 0.271 15.3 56 Flgure 1. Absorbance of an equilibrium Cl20-H20-HOCI mixture
6 0.610 6.4 10 corresponding to run 10 of Table 11.
7 0.290 14.9 51
8 0.480 15.2 32 spectra showed no observable changes after the first -0.5
9 0.483 14.4 30 h for as long as the mixture was left inside the cell (up to
10 0.535 15.4 29 -4 h).
11 0.580 16.7 29
12 0.890 15.0 17 For some of the exploratory runs (4 and 5 in Table I)
13 1.61 14.7 9 the cell walls were pretreated with HNO, vapor. In these
14 2.03 14.5 7 runs small amounts of OClO were produced after the
15 1.15 13.8 12 addition of water, the amount increasing with time (up to
16 3.17 12.3 4 - 1 % after 2 h). OClO is readily detectable by its very
17 5.03 6.5 1 strong, highly structured absorptions, but no trace of this
18 8.84 4.7 0.5
compound was observed when the cell walls were properly
a E = 180 cm for runs 1-14 and 10 cm for runs 15-18. preconditioned. No structure other than that attributable
to OClO was ever observed in the spectra (the maximum
tion;16 the two methods agreed within 1% , The amount resolution was 0.1 nm).
of Cl, impurity in the aqueous HOCl solution can also be
determined iodometrically;16it was not measurable in our Discussion
samples (Cl, < 0.5%). A test with AgNO, also indicated Lower Limits on HOCl Cross Sections in the 350-nm
negligible amounts of C1-. C10- solutions were prepared Region. The absorbance of an equilibrium mixture of ClZO,
by mixing solutions of NaOH and HOC1. HzO,and HOCl (reaction 5) in a wavelength region where
Results absorption by water is negligible can be expressed as
The experimental conditions characterizing each run are follows:
listed in Table 11; the initial water to dichlorine monoxide ’ 2+~ ~‘JHOCI(%)J1
A = ~ ‘ J C 1 2 0 ( [ ~-~6) 0 (6)
ratio, [HzO]o/[ClzO]o,ranged from 1:2 to 220:l. Runs 1-6
were exploratory, whereas runs 7-18 were carried out using Here, A is the absorbance defined as In (Io/I),q’s are
carefully purified C120 samples, stabilized baselines, absorption cross sections, [C1zO]o is the initial C120
preconditioned cell walls, etc. Figure 1 shows the ab- concentration, 1 is the optical path length, and 4 is the
sorbance recorded before and after adding water, for run extent of reaction. Equation 6 may be rearranged as
10. There are four isosbestic points in Figure 1: between
215 and 235 nm and between 330 and 390 nm, the ab-
A = (‘Jc1,o[ClzO]o)l + ( ~ ‘ J H O C I- ‘ J c I ~ o ) ~ ~ (7)
sorbance increases with the addition of water, but de- where the first term represents the absorbance of the pure
creases elsewhere; the same regions of increased and ClzO sample (it corresponds to the dashed line in Figure
decreased absorbance were observed for all runs. Also, the 1) and the second term represents the change in absor-
isosbestic points did not change during the course of the bance which occurs as a result of the addition of water (this
reaction, so that only one UV absorbing species appeared term corresponds to the difference between the two lines
to be formed at all times by the reaction of C1,O and H,O in Figure l),the assumption being that only reaction 5 is
(except for trace amounts of OClO in certain runs, as taking place so that no other UV absorbing compounds
discussed below). besides ClzO and HOCl are present in the cell. Equation
For run 6 the absorbance was still changing after several 7 permits the establishment of lower limits to the HOCl
hours. The water vapor pressure in this run (180-cm cell) cross sections in those wavelength regions where the
was comparable to that in runs 17 and 18 (10 cm cell), and absorbance increases upon the addition of water. In
yet the equilibrium rate was significantly faster for these particular
later runs; clearly the hydrolysis reaction is heterogeneous.
Whenever the water vapor pressure was above 12 torr, the gHOC1 2 ‘Jc120/2 330 nm < < 390 nm (8)
 L. T. Molina and M. J. Molina

-
Keq :
I \
_ -

Flgure 3. Atmospheric photodissociation lifetime of HOC1 at the earth's

surface corresponding to the spectra of Figure 2.

''
I 0
2 2 2
200 240 280 320 360 400 440 09
X (nm)
08
Figure 2. HOC1 vapor spectra calculated from data of Figure 1 for
different values of the equilibrium constant. 07

06
This inequality, in turn, can be used to estimate an upper
limit to the lifetime against photodissociation of HOCl in >. 0 5
the atmosphere; this upper limit is about 1h. The lifetimes 04
reported in this work were calculated in a simple manner
03
just for reference purposes; they refer to the inverse of the
photodissociation rate at the earth's surface for overhead 02

sun conditions. Values for the solar flux intensities were 01

taken from Leighton.17 The actual photodissociation rates 00
in the stratosphere will be somewhat larger due to in- 0 I 2 3 4 5 6 7 8 9 IO II 12 I3 14 1 5 1 6

creased solar flux intensities at short wavelengths and to x x io3

multiply scattered radiation, as discussed below.
Absorption Cross Sections as a Function of K,,. The
extent of reaction and, hence, the HOCl absorption cross
sections can be readily calculated from the measured
absorbances if a value for the equilibrium constant Keqfor
reaction 5 is assumed:
- [HOC1I2 -
(9)
Keq - [C120l[H2Ol ([C~ZOIO- ~ ( [ H z O I-O0
Figure 2 shows HOCl spectra corresponding to the data
of Figure 1 for various values of K,,.
The enthalpy of formation of HOC1, AH?, is not suf-
ficiently well characterized to permit a useful estimate of
Keq,8since an error of a few kcal/mol in AHf' is reflected
in an error in K,, of many orders of magnitude. On the
other hand, it is apparent from Figure 2 that the calculated
absorption cross sections in the atmospherically important
320-390-nm region are rather insensitive to the value of
K , due to the near isosbestic behavior of C120-Hz0-HOC1
mixtures in that wavelength region. Figure 3 shows values
for the atmospheric lifetime as a function of K,,, corre-
sponding to data of Figure 2; as expected, the maximum
lifetime in Figure 3 is somewhat smaller than the upper
limit of -60 min referred to earlier.
In contrast, the calculated HOCl cross sections in the
240-290-nm region depend strongly on the value of K,,.
A lower limit to K,, is obtained by assuming that HOCl
does not absorb light around 270 nm; this limit is 0.07 in
the case of run 10 (see Figure 2), whereas it is 0.15 for runs
15-18.
Estimate of K,, and CJHOC1. In principle both UH?Cl and
K,, can be determined by means of eq 6 and 9 with just
two absorbance measurements at a particular wavelength
carried out with different [C1z0]o/[H20]oratios. It is
Figure 4. Least-squares plots of the experimental data for K,, cal-
culations corresponding to runs 7-12 and 15-18 (eq 10).
convenient to first combine the two equations as follows:
Let
= 2aHOCl - uC120
[C12010 + [H,OIo
= (A/O - [C12010~cizo
[C12Olo[H2Olo
x =
( ( A / O- [c12010~c120)2
b = (1/6)(1 - 4/Keq)
Then
y=6x+b (10)
Plots of y vs. x , both computed from experimental pa-
rameters corresponding to runs 7-12 and 15-18 of Table
11are shown in Figure 4 (in runs 13 and 14, the absorbance
at short wavelengths was too large to be measurable).
Table I11 lists fJHm1and Keqcalculated from the slopes and
intercepts of the x-y plots; the lines are least-squares fits,
and the error limits refer to one standard deviation. As
expected, the error limits on Keqincrease considerably in
the near isosbestic regions (210-240 nm and >320 nm),
since at the isosbestic points the absorbance is indepenent
of KW The smallest standard deviations are found around
280 nm, where the cross sections are not changing rapidly
with wavelength and where the change in absorbance
between pure ClzO and CI20-H20 mixtures is largest.
Thus, K,, is unlikely to be smaller than 0.2 or larger than
0.35; the best value is -0.25.
Figure 5 and Table IV show, for Kw = 0.25, the average
values of the HOCl cross sections calculated as follows:
Ultravlolet Spectrum of HOC1 The Journal of Physical Chemistty, Vol. 82, No. 22, 1978 2413

TABLE 111: Equilibrium Constant and Absorption Cross I " " " " " " ' 1
Sections Calculated from Linear x-y Plots
A, nm 10%, cmz Kea
200
21 0
12.3 f 0.8
8.2 f 0.6 '$:
0.26 f 0.04
0.56
220 9.1 f 1.2 0.24!:T
230 13.3 t 0.7 0.37 z::: *0 1 k'
240 30.2 ?: 1.0 0.33 * 0.1
250 36.9 f 1.6 0.29 f 0.04
260 31.7 f 1.7 0.29 f 0.04

j
270 21.9 f 1.2 0.26 f 0.03
280 18.0 i. 1.0 0.25 f 0.02
290 16.8 ?: 0.8 0.28 f 0.03
300 13.0 f 0.7 0.24 f 0.03
310
320
9.9 f 0.3
6.7 * 0.2
0.27 f
0.31 *
0.03
0.07
10-2' , -;;:;:;:;:; ,

330 4.4 f 0.1 0.39 :E:$ "$

TABLE IV: Absorption Cross Sections of HOCl
Vapor for K,, = 0.26
~~
"61 200 240 280 320 360 400 440
A, nm 10zou, cmz h , nm 1OZ0u,cmz A(nrn)
200 12.3f 0.9 330 4.1 t 0.3 Flgure 5. Absorption spectra of HOC1 and CIO-.
210 7.7 2 0.6 340 2.5 * 0.2
220 9.1 f 0.8 350 1.5 f 0.2 sample containing 5% Clz. The apparent HOCl cross
230 16.9 i 0.9 360 0.86 f 0.09 sections increase by -3% at 310 nm and by -40% at 380
240 27.8 f 1.5 370 0.47 f 0.06 nm. After correcting for the known amount of added Clz,
250 34.5 i: 1.5 380 0.30f 0.05
260 28.9 f 1.7 390 0.23f 0.03 the spectrum agrees with those of the C12-freeruns, and
270 21.3 f 1.0 400 0.22 f 0.02 an upper limit of -15% C12 is obtained by assuming that
280 18.1 f 0.8 410 0.24 f 0.03 HOCl does not absorb any light at 380 nm. The equivalent
290 15.9 A 0.6 420 0.25 f 0.03 upper limit for run 14 is 5% and for run 10 is -10% (with
300 13.4 f 0.6 430 0.22 f 0.02 Keq= 0.25); the atmospheric lifetime of HOCl calculated
310 9.7 f 0.3 440 0.18f 0.02 assuming this maximum amount of Clz present in run 10
320 6.6 f 0.2 450 0.15 f 0.02
is 55 min. In fact, the spectrum shown in Figure 1 (run
200-300 nm, runs 7-12 and 15-18; 300-400 nm, runs 7-18; 10) cannot be accounted for by any combination of ClzO
and 400-450 nm, runs 7-12 (we chose not to average the and Clz absorptions alone; the maximum atmospheric
very weak absorbances beyond 400 nm measured with the lifetime which can be obtained by changing Kw and 90 C12
10-cm cell). The error limits refer to one standard de- simultaneously is about 2 h.
viation. It is possible, in principle, that other species besides
Using our result K,, = 0.25 and thermodynamic data HOCl are present at equilibrium with Cl20 and H20,but
from a recent compilation by Watson,18 the enthalpy of in our opinion it is very unlikely for any such species to
formation of HOCl at 25 OC can be estimated to be about contribute significantly to the observed UV spectrum. The
-18.0 kcal/mol; the main uncertainty arises from AH?- C10- ion has a strong absorption feature around 290 nm
(ClZO). (see Figure 5), but its concentration in a gas phase mixture
Impurities in the Cl2O-H2O-H0Cl Equilibrium Mix- of C120 and H 2 0 must be insignificant, since even in
tures. In order to explain the discrepancies between the aqueous HOCl solutions it is less than 0.2%.19 An
HOCl spectrum reported by Jaffe and DeMore and the H,O-HOC1 adduct having a structure such as H,O+.OCl-
theoretical calculations, it has been suggested6 that might conceivably have strong absorption features;6
H20-C120 mixtures might contain Cl,, C10-, or H30+.0C1-, however, the linear behavior of the x-y parameters dis-
or that the ClzO absorption is not adequately accounted played in Figure 3 and the constancy of the isosbestic
for. points for a wide range of initial conditions are not
We have examined in some detail the likelihood of Cl, compatible with the presence of a strongly UV absorbing
contamination in our experiments. As discussed in the HOC1-H20 adduct or an HOCl dimer. The formation of
Experimental Section, the UV spectra indicate clearly that higher oxyacids of chlorine is also very unlikely; the
negligible amounts of Clz are originally present in the ClZO molecules HC102 and HCIOBare not known to exist in the
samples. Furthermore, our results indicate that no sig- gas phase and HC104has a very weak UV spectrum beyond
nificant thermal or photochemical decomposition of HOCl 270 nmS2O
occurs, since the spectra do not change after the initial Spectrum of Aqueous HOC1. Figure 5 shows the spectra
equilibration period. It could be argued that because of of aqueous solutions of HOCl and of C10-. The cross
some peculiarities of the walls a heterogeneous reaction sections of HOCl have been corrected for the C10- ab-
generates Clz only during the initial equilibration period. sorption using the acid ionization constant reported by
However, essentially identical spectra are obtained with Morris;lg the maximum correction is -3% (at 290 nm) for
cells of quite different surface to volume ratios, and except a 0.02 M HOCl solution. Our results agree well with those
for the appearance of trace amounts of OClO discussed of Fergusson et al.1° except beyond 400 nm, where our
above, different surface treatments again yield the same values are smaller by -50%. Absorption in the 200-
result. 350-nm region has also been measured by Friedman21and
In order to further investigate the effect of C12, we by Morrislg with similar results.
carried out an experiment (run 8 in Table 11) with a ClzO As shown in Figure 5, the solution and the vapor spectra
2414 The Journal of Physical Chemistry, Vol. 82, No. 22, 1978
9-
8-
7-
E non-methane hydrocarbon^.^^ It is unlikely, though, for
0 6-
- 5-
\
‘u)
Y Conclusions
0 4-
7 HOCl for spectroscopic studies. At room temperature the
3-
Si0 ~ 3 4 0 360 380 400 420 440
X,nm
Flgure 6. Contributions to the atmospheric photodissociation rate of
HOC1 for each wavelength interval.
are similar except that the former is blue shifted, a be-
havior which is typical of n-u* transitions for polar
moleculesaZ2Also, the weak 420-nm band observed in the
vapor spectra does not appear to be present in aqueous
solutions. The absorbances beyond 400 nm are rather
weak, but the discrepancy is outside experimental error.
The similarity between the two spectra indicates that
the absorbing species is the same in both phases. Fur-
thermore, previous workers employed different HOCl
sources for the aqueous solutions (e.g., Fergusson et al.
started with bleaching powder); the agreement with our
results shows that hydrolysis of Cl2O vapor indeed pro-
duces HOCl essentially free of contamination.
Comparison of HOCl Vapor Spectra. The early mea-
surements of Fergusson et al.1° are almost surely in error.
In the critical 300-380-nm region our cross sections are
smaller by a factor of 2-4 than those reported by Jaffe and
DeMore,ll and larger by more than two orders of mag-
nitude than the theoretical values given by Jaffe and
L a n g h ~ f f .To
~ our knowledge, all previous experimental
work (except that of Fergusson et al.) was carried out using
10-cm cells which provide marginal sensitivity to small
absorptions compared to our 2-m cell. The discrepancy
with the theoretical predictions cannot be explained easily;
however, the theoretical approach does not appear to be
well established, since, to our knowledge, no other theo-
retical calculations of UV spectral band shapes and in-
tensities have been carried out for molecules with more
than two atoms involving transitions to a repulsive state.
Stratospheric Abundance of HOC1. The photodisso-
ciation rate J for overhead sun at the earth’s surface
calculated with the data of Table IV is -4 X s-’.
Figure 6 shows the contributions to J for each 10-nm
wavelength interval; the absorption beyond 380 nm
contributes less than 15% to the overall rate.
Due to multiple scattering effects, species which have
significant absorption cross sections at wavelengths greater
than 290 nm have photodissociation rates in the lower
stratosphere which are 50-90% larger than calculated
assuming pure absorptioq2 thus, for HOC1, J 2 6 X
s-l in the lower stratosphere.
If photolysis is the dominant HOCl destruction
mechanism in the stratosphere, at steady state the rates
of reactions 1 and 4 are equal, and consequently
show [HOJ -
[HOCl]/[ClO] = k,[H02]/ J. Typical model calculations
2-6 X lo7 molecule ~ m in- the
range.2 Using a value of 4 x 10-l~
~ 20-40-km
cm3 molecule-l s-l for
L. T. Molina and M. J. Molina
k: and our calculated Jvalue, we estimate [HOCl]/[ClO]
< 0.5, so that HOCl is not likely to play a role as an inert
chlorine reservoir comparable to that of HC1. Other
possible sources of HOCl in the stratosphere include
heterogeneous hydrolysis of C10N02,zor hydrogen atom
abstraction by C10 radicals from formaldehyde or other
these alternate sources to be as important as reaction 1.
Gas-phase hydrolysis of ClzO provides a clean source of
Hz0-Cl20-HOC1 equilibrium mixtures are stable for
periods of at least several hours if placed in suitably
preconditioned glass containers. The equilibrium constant
Keyas well as the HOCl absorption cross sections can be
estimated by measuring the UV absorbance of equilibrium
mixtures prepared with different initial amounts of C1,O
and H20; our results indicate K,, i= 0.25, and corre-
spondingly AHHfO(HOC1)= -18.0 kcal/mol. The results of
various control experiments indicate that the measured
UV absorbance is not likely to be due to impurities.
The rate of photodissociation of HOCl in the strato-
sphere calculated from our absorption cross section
measurements is sufficiently large to make HOCl unim-
portant as a holding tank for chlorine. The corresponding
atmospheric lifetime is about 30 min, a number which
happens to be rather insensitive to the value of K because
of the near isosbestic behavior of H20-C1&HOC1
equilibrium mixtures in the atmospherically important
320-390-nm wavelength region.
Acknowledgment. We are grateful to Professor F. S.
Rowland for helpful discussions and to Mr. James Cook
and Ms. Sandra Mendez for technical assistance. This
work was supported by the National Aeronautics and
Space Administration, Grant NSG-7208, and by a Dreyfus
Teacher-Scholar Grant.
References and Notes
(1) Alfred P. Sloan Fellow and Dreyfus Teacher -Scholar.
(2) R. D. Hudson, Ed., “Chlorofluoromethanes and the Stratosphere“,
NASA Reference Publication 1010,Washington, D.C., 1977.
(3) S. S. Prasad, Planet. Space Sci., 24, 1187 (1976).
(4) G.Hirsch, P. J. Bruna, S. D. Peyerimhoff, and R. J. Buenker, Chem.
Phys. Lett., 52, 442 (1977).
(5) R. L. Jaffe and S. R. Langhoff, J . Chem. Phys., 66, 1638 (1978).
(6) S.S.Prasad, R. L. Jaffe, R. C. Whitten, and R. P. Turco, Planet. Space
Sci., in press.
(7) F. S. Rowland and M. J. Molina, Rev. Geophys. Space Phys., 13,
1 (1975).
(8) P. Warneck, Z . Naturforsch. A , 32, 1254 (1977).
(9) Two measurements were reported at the Fourth Biennlai Rocky
Mountain Regional Meeting of the American Chemical Society, June
5-7, 1978: (4.5 1.5)X lo-’*om3 molecule-’ s-I, by R. Stimpfle
R. A. Perry, and C. J. Howard, and (3.1& 0.7)X IO-’* cm3 molecule-i
s-’by J. W. Birks and T. J. Leck. Also, a value of (3.8f 0.5)X
lo-’* cm3 molecule-’ s-’has been reported by R. Reiman and F.
Kaufman (submitted to J. Chem. Phys.).
(10) W. G. Fergusson, L. Slotin, and D. W. G. Style, Trans. Faraday Soc.,
32, 956 (1936).
(11) See p 36 of ref 2; see also p 912 of ref 18.
(12) The two experiments are by R. Timmons and by I. C. Hisatsune, ref
33 and 34 of ref 5 above.
(13) R. A. Ashby, J . Mol. Spectrosc., 23, 439 (1967).
(14)C.J. Schack and C. B. Lindhal, Inorg. Nucl. Chem. Lett., 3, 387
(1967).
(15) C.L. Lin, J . Chem. Eng. Data, 21, 411 (1976).
(16) T. Moeller, Inorg. Syn., 5, 162 (1957).
(17) P. A. Leighton, “Photochemistry of Air Pollution”, Academic Press,
New York, N.Y., 1961,p 29.
(18)R. T. Watson, J . Phys. Chem. Ref. Data, 6, 871 (1977).
(19) J. C. Morris, J . Phys. Chem., 70,3798 (1966).
(20) L. Beaman, M.S. Thesis, University of California, Irvine, Calif., 1977.
(21) H. L. Friedman, J . Chem. Phys., 21, 319 (1953).
(22) L. T.Molina, S. D. Schinke, and M. J. Molina, Geophys. Res. Left.,
4, 580 (1977).
(23) P. L. Hanst, private communication.