Measurements of the temperature dependence between 77 and 333 K of the infrared spectrum of cyclic octatomic sulfur are reported. It is suggested that the 23 micrometer Jovian feature is not due to 3 sub 8 and that the temperature dependence of the frequency of the 835/cm band of S sub 8 may be a useful temperature marker in planetary studies

Khare, B. N.

Sagan, C.

English

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CORNELL UNIVERSITY
Center for Kadiophysics and Space Research
1
ITHACA. N. Y. A
CRSR 632
-a_
ON THE TEMPFRATURF DEPF' ENCE OF POSSIBLE S8
IN}'RARED BANDS IN PLANETARY AT40SPHERES
B. N. Khare
AND
Carl Sagan
129 31 r^
V	 ^^
JUN 1970
RECEIVED
NASA STI FACILITY
INPUT BRANCH1,^^
V-
ON THE TEMPERATURE DEPENDENCE OP POSSIBLE S R INFRARED SANDS
IN PLANETARY ATMOSPHERES
BY
B. N. Khare. and Carl Sagan
Laboratory for Planetary Studies
Cornell Univer.sKy
Ithaca, New York 14853
Submitted Mober 1h, 1975
Revised MavQh 22, 1976
9
i
ABARACT
Mcasuremento of the temperature dependence between 77 and
333K of that infrared spectrum of cyclic octatomic sulfur nuggest
that the 23 Pm Jovian feature very tentatively identified by
Houck et al. (1975) is not due to 3 8 ; and that the temperature
dependence of the frequency of the 835 cm -1 band of S8 maylp a
useful temperature marker in planUary studies.
F.
Because of the high cosmic abundance of sulfur, it sh
be prr.senu in elemental or combin o form in many solar sysu.:t:
environments. Cyclic octat:omic : ul.fur, 5 8 , is produced in high
yield on ultraYolct• irradiation in a variety of reducing
atmospheres, and has been proposed as a constituent in the clouds
of Jupiter and other objects in the outer solar system (Khare
and Sagan, 1975). In addition, polymeric sulfur (linear or cyclic)
may possibly be present in the clouds of Venus (Hapke, 1975) and
on the surface of to (Wamsteker et• al., 1974; Panale et al., 1974).
The strongest permitted infrared transition of S 8 at wavelengths
short of 50 microns is in the vicinity of 469 cm-1 -- a frequency
in fair agreement with that of the strongest unidentified feature
In the Jovian infrared spectrum ( gouck et al., 1975). While there
is perhaps as much as a 10 cm -1 uncertainty in the frequency of
the Jovian band, it is displaced from the room temperature frequency
of the corresponding S 8 band by about 20 cm-1 . While Houck et al..
have expressed considerable caution about the reality of their>3
um feature, it still seems worth-while to investigate the temperaturo
dependence of nearby S 8 features, The temperature dependence of
infrared vibrational features of several other consti.tuerts of
potential i.nterost for planetary nNtronomy have boon measured (Smythe,
1975; Pink and Larson,• 1975; Kieffer and Smythe, 1974; Pollack and
Sagan, 1968) and are of potential utility in determining the temp-
eratures of planetary and satellite surfaces and cloud layers.
This possibility provides another motivation for measurementsof
the temperature dependence of the various infrared features of S8.
A few mg of Mallinekrodt sublimed sulfur was mixed with about
- 2
250 mg of Gal powder and a 13 mm diameter pellet wan prepared
according to the method described in our earlier paper (Khare and
Sagan, 1975). The pallet wan implanted in n bolo in amppov
block and al'fixod W.t.h a copper collar and an indium metal G-ring.
ll copper-constantan thermocouple was placed in thermal contact
with the copper block and less than 1 mm from the pellet. The
entire block was firmly attached, using a A& indium gasket to a
standard infrared research Dewar (Hoffman Laboratories, Newark, New
Jersey) equipped with Gal windows. Temperatures were mcusuredwit•'h
the mentioned thermocouple as welt as with another thermocouple
imbedded on the cooling block of the Dewar itself. Boiling water
and liquid nitrogen were employed in separate experiments to
achieve temperatures higher than tend significantly lower than room
tempertuve; and, i ' e the latter case, to reach temperatures which
are crudely comparable to those of the region of the Jovian atmosphere
observed near 23 Pm. Because of the energy provided by the infrared
spectrometer's Infrared source and because of thermal conduction,
equilibrium temperatures reached by the Gal pellet, as measured by
both thermocouples, were in the two experiments 333°K and 77°K
respectively. The highest temperature is -: 333 0 K  because the initially
boiling water is coolod by heatinn the dewar during; transit.
Temperatures at the beginning and On end of each:ran wereconstant
within 1 KO.
Infrared spectra were recorded on a Perkin-Elmer Modal 621 infrared
grating double beam spectrometer, purged with dry air, in the 200 to
4000 cm-1 region. The spectra were calibrated in wavelength using
an indene film (IUPIIC, 1961) and are believed to be accurate to + 1 cm-1
1
- 3 -
Over this temperature range, the 469 cm- 1
 band maintained a
constant ;roquency within the errors of moasurrmo= Changes
were observed in the frequency of the relatively wpak fraLure
whose room temperature band center is near 835 cm
-1 , This feature
has a broad absorption maximum which ;Hakes it difficult tospeeify
an exact band center. At 333°K the absorption maximum lies
between 834 and 845 cm-1 ; at 77°K, It lies between 852 and 855cm-1.
Other AS features at 243 cm-1
 335 cm-1 , and 1208 cm-1 seem likewise
to be temoerature-independent within a few cm -1 , a result consistent
with previous work (Seotb,rL al, 1964; Chantry, et; al., 1964;
Meyer, 1965; Anderson and Loh, 1969). The temperature variation
of the 835 cm-1 feature is consistent with the quantitativeresults
reported by ]Jeff and Walnut (1961). This absorption band is acombin-
ation band rather than a latti.ae fundamental. (Neffand Walnut, 1961).
An impression of the overall appenvance of the infrared spectra
at these two temperatures, as well as at .room temperature, is
provided in Figure 1.
We conclude that the 23 tam feature of Houck et a1. (1975),
If real, cannot be attributed to cyclic octatomic sulfur; but that
other features of S 8 , such as the band with a room temperature
central frequency of 835 cm-1 , may prove to be useful tomperature
calibrators if S 8 is unambiguously discovered in planetary ar,
satellite spectra.
While there remains no strong observationsal evidence for
polymeric sulfur on Jupiter, for the reasons we have already given
(Khare and Sagan, 1975) we still hold that it is a likely constituent
of the Jovian clouds.
i
^_	 a 3
..I
Acknowledrement
We arc eratofu.l to T.D. OoldVarb 1'or the loan of the infrared
Research Dowar ., and to RLchavd Zsllon, Jamou Houck and James
Pollack lbr helpful. cumnonto. ThIs work was nupportod 1n
part by NAAA Grant NOR 33010-101.
References
Anderson,
	
A. and Y.	 T.	 Loh,	 (1969):	 Low tomperaLUre Haman
spoutrum of rhombic.	 aulfur.	 (:nn_	 .1. Ghom.	 4.7. , 879-884,
Chnntry, G. W., Anderson, A., and Grebbie, U. A. (1.964):
Par inieared spectrum of sulfur and selenium. 	 ctro -
chimica AcLa, 20, 1223-1224.
Canale, P. P., Johnson, T. V., and Matson, D. L.(1974): 	 Io:
A surface evaporite deposit.
	
Science 186, 922-925.
Pink, U. and Larson, 11. P. (1975): 	 remperattire dependence of
the water-ice spectrum between 1 and 4 microns: Application
to Europa, Canymede, and Saturn's rings.	 Icarus
 
23, 411-420.
Hapke, 6., Nelson, It., Woodman, J. If. and Barker, T. S. (1974)
U.V. spectroscopy of Venus: Evidence for an elemental
sulfur component of the clouds. 	 Hull.. Am. A stro. Soc, 6,
368-369
Ito ucIt, J. It. , Pollack, J. 8. , SahaacIt, 1) , Iteod, It. A. , and
Summers, A. (1.975):	 Jupatnr:	 Its infrared specLrum from
16 to 40 micrometers. 	 Science	 189, 720-722.
-6-
IUPAC Tables of Wnvenumbera for the CalibraL ,ioil of Infrared
Spectrometers, ( Butterworths, Inc., Wnshinl ; ton, D.C. 1961).
Khare, B. N. and Sagan, C. ( 197`i):	 Cyclic OvLaLomic Sulfur:
A possible infrar^ and visible chromophore in the clouds
of Jupiter.	 Science 189, 722-723.
Kieffer, It. It. and W. D, Smythe (]. 9 74):	 Frost spectra:
Comparison with Jupiter ' s satellites.	 Icarus 71, 506-512.
Meyer.,
	 B.,	 ed. (1965):	 " GlemenLal Sulfur ( IL's	 Chemistry	 and
Physics)", 1n. Lersclencu,	 Nvw York,	 p. 248.
Neff, 1). V. and Walnut, A. T. (1.961):	 Effect of temperature
on the intensity and structure of bands in the infrared
a1)ecLrum of rhombic sulfur. J. Chem. Ph,VS. 471 , 17L-3-1729.
Pollack, J. B. and Sagan, C. (1968): 	 The case for ice clouds
on Venus.	 Geophys. Iles. 73, 5943-5949.
Scott, D. W., McCullough, J. 1'., and Kruse, F. 11. (1964):
Vibrational assignment and force constants of S 8 From
a normal-coordinate treatment. 	 J. MOIec. S1)0. ctros ., ]_3,
313-320.
-7-
Smythe, 14. U. (1975):	 Spcctrn of hydrate Croats: 	 'Their
application to the outer solar uyntem. 	 Icarus 27, 421-427.
Wamsteker, W., Rogcra L. K. and Fountain, J. A. (1974): 	 On
the surface Composition of 10.	 Icarus 23, 417-424.
Figure CAntion
Figure 1: The trannminsion opectrum of Col pullets of .9
as a function of temperature. The feaLures nL 1611 am-1
and at 3450 cm-1 are due to outer impurities in Col.
The negative pealc at 2330 cm -1
 is due to absorption by
atmospheric CO 2 in the sample compartment in the reference
beam.	 The discontinuities near 2300, 2000, 1150, 630,
500 nod 295 cm-1 are instrumental artifacts due to changes
fn filLern or gratings and should be disregarded.
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On the temperature dependence of possible S8 infrared bands in planetary atmospheres

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