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AND
B. DONN
USRA Visiting Scientist and Department of Engineering Physics, University of Virginia, Charlottesville, Virginia 22901
Ghormley (1967) and Bar-Nun et al. (1985), gas release other IR scan. This warming-recooling cycle was neces-
occurred in well-defined temperature regions and gas was sary to distinguish permanent spectral changes, caused
retained up to sublimation of the H2 0 itself. by irreversible physical changes in the ice, from spectral
An important extension of the previous work on gas changes simply due to different temperatures during an
trapping and release is to observe both the solid and the IR scan.
vapor phases on warming gas/H 2 0 ices. For this reason, Our radiation experiments on H2 0, CO/H 20, and C02/
we have carried out over a hundred experiments on four H2 0 ices comprise part of a study of the effects of ionizing
different ice systems, namely, H 2 0, Ar/H 2 O, CO/H 2 O, radiation (I -MeV protons) on the sublimation of cometary
and C02/H 20. Ices were warmed from 25 to 200 K with ices. The radiation exposure of each sample was -3.1 x
gas release being monitored by a mass spectrometer (MS) 1010protons cm-2 sec' for I hr so that the absorbed
and changes in the solid phase followed with an IR spec- dose (absorbed fluence) was essentially the same in all
trometer. By combining these two techniques, we have experiments. Experimental constraints prohibited de-
been able to correlate observations of gas release with tailed studies of gas sublimation below -70 K in radiation
changes in the solid ice. Finally, we have done some experiments and so we confine our discussion to tempera-
preliminary experiments using l-MeV proton irradiation tures above that value. In the future we hope to extend
to investigate possible effects of cosmic rays on cometary our work to lower temperatures.
ice sublimation. To our knowledge, only Kouchi (1990) Additional experimental details, including drawings of
has probed both the solid and the vapor states of cometary equipment and descriptions of the l-MeV proton source,
ice analogs, using electron diffraction and mass spectrom- have been published in Moore et al. (1983, 1988) and
etry. No one has reported results with our combination references therein. The interested reader should consult
of IR and mass spectral methods coupled with ionizing those papers for more information than can be provided
radiation. here.
RESULTS
EXPERIMENTAL
H20 Ices
Experiments began with the preparation of a gaseous
mixture at room temperature on a vacuum line and the It is well known that a film of amorphous ice is formed
mixture's deposition on a cold finger at 23-30 K. The when H20 is cooled directly from the vapor phase onto a
deposition rate was I gm/hr and the sample thickness was surface with a temperature below about 130 K (Hobbs
0.5 Am. The gas/H 2 0 ratio in the ice deposit was perhaps 1974). As the amorphous ice is warmed it crystallizes, first
somewhat higher than at room temperature in the vacuum into a cubic phase beginning around 140 K and then, at a
line because of H20 adsorption in the line. However, higher temperature, into a hexagonal phase. If the ice is
the good reproducibility of the results implies that the warmed still further it will eventually melt, although the
depletion of H2 0 was minimal. thin films in our experiments completely sublime first.
A grating mid-IR spectrometer (measured wavenumber IR spectra for amorphous and cubic H20 ice have been
accuracy about 4 cm- ', resolution about 2 cm ') served published many times, for example Hardin and Harvey
both for following the progress of a deposition and for (1973), Bergren et al. (1978), Leger et al. (1979), Hagen
recording IR reflectance spectra of samples from 200 to et al. (1981, 1982), and Fink and Sill (1982). In the
4000 cm-' (2.5 to 50 Arm). After deposition of an icy 200-4000 cm-' mid-IR region, absorptions around 3220,
sample, its IR spectrum was recorded to check its thick- 2200, 1600, and 800 cm-' all undergo changes in position
ness, using absorption coefficients (Wood and Roux 1982, and shape at the phase transition of amorphous water.
Kitta and Kratschmer 1983) for v 3200 cm- '. The ice However, the mid-IR spectra of the cubic and hexagonal
was then warmed to 200 K, at 3 K/min, and mass spectral phases of ice are essentially identical (Bertie and Whalley
measurements were made every 6 sec at preselected mlz 1964, Bertie and Jacobs 1977).
values. A heater epoxied onto the back side of the cold In our work, we recorded the spectrum of amorphous
finger allowed the ice sample to be warmed independently H 20 ice immediately after deposition at 23 K and subse-
of the rest of the cryostat (Moore et al. 1988). quently at 23 K after thermal annealings up to 160 K. No
Once gas release as a function of temperature had been changes in IR absorptions were observed as the sample
measured, a second ice sample was prepared for IR study. was warmed to about 40 K kandthen recooled. Beyond
The spectrum of this ice was recorded at 23-30 K, fol- 40 K, gradual small changes occurred that were consistent
lowed by warming to some specific temperature, such as with the more detailed work of Hagen et al. (1981, 1982).
just past a region of gas release. After 15-20 min the The greatest changes in the IR spectrum were at the amor-
sample was recooled to the original temperature for an- phous-to-cubic phase transition for H20. As our spectra
328 HUL)SON AND DONN
COIH20 Ices
-10
Since our sublimation curves for CO/H2 O ices were
very similar to those of Fig. 2 for Ar/H 2 0 ices, they are E
0 (b)
7 1 c/H 2O =0.5
not shown here. The same variation of the amount of gas
released at different temperatures with the gas/H 20 ratio
of the ice was found. Also similar was the correspondence
n
U,
c-
-8
I J
release at even the lowest temperatures for CO sublima- -8 CO/ H2O =0.3 Ic)
tion, and CO retention up to the sublimation temperature
of the H2O itself. 9 L <+.,l.
1w
; ...........
'>.j, . -
The IR spectra of CO/H2 0 ices contained, in addition
to the H2O bands, a sharp line near 2140 cm-' corre- -9r
-10 - 2li tlt1t1+te { 0
sponding to the fundamental vibration of CO. The sys-
tematic changes in position and shape of the CO absorp-
40 60 80 100 120 140 160 180 200
tion upon varying either the CO/H2 0 ratio or the ice
TEMP (OK)
temperature (Sandford el al. 1988) were too small to be
reliably followed with our spectrometer. However, CO/ FIG. 3. Sublimation curves for 0 . 5 -Am films of'CO2/H2Oice mixtures
H20 ices did show changes in H 20 absorptions on deposited at 27 K.
warming similar to those seen in pure H2 0 and Ar/H 2 0
ices. When a CO/H 2 0 sample was warmed to a region
of gas release, known from mass spectrometry, IR
spectroscopy showed a drop in intensity for the CO Radiation Experiments
absorption. Because of its presence in all of our experiments, amor-
phous H2 0 was irradiated and its sublimation curve re-
C0 21H2 0 Ices corded after the radiolysis to serve as a point of reference.
We detected no differences between either the sublima-
Sublimation curves for three CO2 /H2 O ices are shown tion curves or the IR spectra of irradiated and unirradiated
in Fig. 3. Figure 3a for a 3/1 C0 2 /H 2 0 ratio is similar to pure H2 0 ice. In particular, the shapes and positions of
that described, but not shown, by Bar-Nun et al. 1985. the four IR bands of amorphous H20 were the same before
This ice gave an initial gas release beginning at -80 K and and after the irradiation, indicating that the radiolysis did
peaking at 98 K. A second, larger release peaked at 112 K. not cause crystallization of the ice.
Reducing the CO2 /H2 O ratio to 0.5 and even lower caused It has been known for some time (Moore et al. 1983)
substantial changes in the relative amounts of gas released that proton irradiation of CO/HO ices produces CO,.
around 146 and 165 K. This is seen in Fig. 4, where the sublimation curves for
CO2/H2 O ices displayed six major IR absorptions, four unirradiated and irradiated CO/H 2 O ices (ratio = 0.14)
from H2 O and two from CO2 . As in the case of CO, small are compared, the latter showing both CO and CO, re-
systematic changes in the IR absorptions of CO2 , due to lease. From the preceding discussion on unirradiated CO/
variation of the CO2 /H2 O ratio or the ice's temperature H2 0 ice, it will be recalled that the relative intensities of
(Sandford and Allamandola 1990), were not studied. How- the two highest temperature CO releases are reversed as
ever, with C0 2 /H 2 0 ices we did search for, and find, the CO/HO ratio is decreased (Fig. 2). Figure 4 shows a
changes in the H 20 IR absorptions on warming similar comparable change brought about by ionizing radiation.
to those for pure H 20 ices. In all experiments, warming The radiation converts some of the CO in the ice into
a CO2 /H 2 0 sample to a temperature region known, from CO2 , effectively dropping the CO/H 2 O ratio and changing
mass spectrometry, to cause gas release, always reduced the relative intensities of the two highest temperature CO
the intensity of the two IR bands of CO2 in the solid. releases. In each case studied, an ice with some given CO/
330 HUDSON ANI) DONN
dola (1988), using only IR, find CO sublimation mainly in Our radiation chemical experiments on CO/H2 O and
temperature regions 1, IV, and V of our Fig. 2. The use CO2/H2O ices are also relevant to cometary science. In
of mass spectrometry allowed us to detect CO directly in our experiments, irradiated CO/H2 O ice produced CO2
the vapor state in those three regions but also in regions which was subsequently released at the same tempera-
11and III. Since we found that gas release in these regions tures as CO. This implies that the CO in a cometary
increased monotonically with the initial CO/H 2 0 ratio, it nucleus, when subjected to cosmic radiation, will produce
is not surprising that IR studies alone of a CO/H2 0 = CO2 and that the two gases can be released at the same
0.05 ice did not detect CO loss. temperatures. The statement of Feldman et al. (1986)that
In another extensive study, Sandford and Allamandola "it is likely that both species are released simultaneously
(1990) followed sublimation from C0 2 /H 20 ices by inten- during the [cometary] outbursts" is supported by our lab-
sity changes in the v2 IR band of CO2 (=2340 cm-'). oratory studies of cometary ices.
Our results agree with theirs, that CO2 release is strongly Much work remains in extending and quantifying our
dependent on the initial CO2 /H 2O ratio. Figure 3a shows sublimation experiments. In particular, our use of IR to
that a ratio of 3 gave CO2 sublimation beginning at almost aid in the interpretation of mass spectral results and mass
the same temperature as in pure CC 2 , namely -80 K. spectrometry to detect gas releases missed by IR is prom-
Some H 2 0 was carried off at this temperature as well. ising. There is also a need for more ice experiments involv-
However, as the initial gas concentration is dropped (Figs. ing ionizing radiation.
3b and 3c) the sublimation curves begin to resemble Fig.
2c for Ar/H 2 O, and CO/H 2 O, ices. In these cases it is HO ACKNOWLEDGMENTS
that is controlling gas sublimation at temperatures above
-80 K. The cometary implications of these results have Maria Moore is acknowledged for invaluable assistance with many
been discussed in detail (Sandford and Allamandola 1990). experimental problems. Raj Khanna of the University of Maryland is
thanked for discussions involving IR spectroscopy. L. Allamandola is
thanked for copies of useful papers (reprints and preprints) and espe-
IrradiatedIces cially for many comments which have improved this paper. A. Bar-
Nun's comments on an early draft of this paper are also acknowledged.
The significant results from our radiation experiments R.L.H. was supported by NASA grant NAG 5-952 and by an Intergov-
come from CO/H 2 O and CO2 /H2O ices. In both systems, ernmental Personnel Act Agreement. Eckerd College is acknowledged
IR spectroscopy and mass spectrometry provided evi- for a leave-of-absence to R.L.H. to carry out this research.
dence of chemical reactions and product sublimation. In
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