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All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Materials Data on Cl2O7 by Materials Project

O7Cl2 crystallizes in the monoclinic C2/c space group. The structure is zero-dimensional and consists of four O7Cl2 clusters. there are four inequivalent O sites. In the first O site, O is bonded in a single-bond geometry to one Cl atom. The O–Cl bond length is 1.42 Å. In the second O site, O is bonded in a bent 120 degrees geometry to two equivalent Cl atoms. Both O–Cl bond lengths are 1.77 Å. In the third O site, O is bonded in a single-bond geometry to one Cl atom. The O–Cl bond length is 1.42 Å. In the fourth O site, O is bonded in a single-bond geometry to one Cl atom. The O–Cl bond length is 1.42 Å. Cl is bonded to four O atoms to form corner-sharing ClO4 tetrahedra.

36 MATERIALS SCIENCE↗
NASA NTRS1972

Tetraperchlorate of methane

The preparation of the tetraperchlorate of methane (TPM) was attempted. Displacement of halogen from carbon tetrahalides was accomplished with either CCl4 or CBr4 using the halogen perchlorates, ClOClO3, and BOClO3. Although the displacement process was successful, the generated carbon perchlorate intermediates were not isolated. Instead, these species decomposed to COCl2, CO2, and Cl2O7. The vigorous displacement reaction that often occurred required moderation. Fluorocarbon solvents and chlorine perchlorate were successfully tested for compatibility, permitting their use in these synthetic reactions. While the sought for moderating effect was obtained, the net result of the displacement of halogen from CX sub 4 substrates was the same as before. Thus only CO2, COCl2, and Cl2O7 were isolated.

Schack, C. J.↗
NASA NTRS2017

Oxychlorine Species in Gale Crater and Broader Implications for Mars

Of 15 samples analyzed to date, the Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) has detected oxychlorine compounds (perchlorate or chlorate) in 12 samples. The presence of oxychlorine species is inferred from the release of oxygen at temperatures less than 600degC and HCl between 350-850degC when a sample is heated to 850degC. The O2 release temperature varies with sample, likely caused by different cations, grain size differences, or catalytic effects of other minerals. In the oxychlorine-containing samples, perchlorate abundances range from 0.06 +/- 0.03 to 1.15 +/- 0.5 wt% Cl2O7 equivalent. Comparing these results to the elemental Cl concentration measured by the Alpha Particle X-ray Spectrometer (APXS) instrument, oxychlorine species account for 5-40% of the total Cl present. The variation in oxychlorine abundance has implications for their production and preservation over time. For example, the John Klein (JK) and Cumberland (CB) samples were acquired within a few meters of each other and CB contained approximately1.2 wt% Cl2O7 equivalent while JK had approximately 0.1 wt%. One difference between the two samples is that JK has a large number of veins visible in the drill hole wall, indicating more post-deposition alteration and removal. Finally, despite Cl concentrations similar to previous samples, the last three Murray formation samples (Oudam, Marimba, and Quela) had no detectable oxygen released during pyrolysis. This could be a result of oxygen reacting with other species in the sample during pyrolysis. Lab work has shown this is likely to have occurred in SAM but it is unlikely to have consumed all the O2 released. Another explanation is that the Cl is present as chlorides, which is consistent with data from the ChemCam (Chemical Camera) and CheMin (Chemistry and Mineralogy) instruments on MSL. For example, the Quela sample has approximately1 wt% elemental Cl detected by APXS, had no detectable O2 released, and halite (NaCl) has been tentatively identified in CheMin X-ray diffraction data. These data show that oxychlorines are likely globally distributed on Mars but the distribution is heterogenous depending on the perchlorate formation mechanism (production rate), burial, and subsequent diagenesis

Ming, Douglas W.↗
NASA NTRS1976

Extinction coefficients of chlorine monoxide and chlorine heptoxide

The ultraviolet and visible extinction coefficients of Cl2O and Cl2O7 were measured from 180 to 800 nm. The results are comparable in shape with literature values, but different in magnitude. The approximate extinction coefficients at the peaks of infrared absorption lines are also given.

Lin, C.-L.↗
NASA NTRS1979

The photolysis of chlorine in the presence of ozone, nitric acid and nitrogen dioxide

The following three systems were investigated: the Cl2-O3 system, the Cl2-O2-NO system and the Cl2-NO2-M system. In the first system, the reaction between ClO and O3, the reaction between OClO and O3, and the mechanism of the Cl2-O3 system were studied. In the second system, the reaction between ClOO and NO was investigated. In the last system, the reaction between Cl and NO2 was investigated as well as the kinetics of the chemiluminescence of the Cl-NO2-O3 reaction. In the first system, Cl2 was photolyzed at 366 nm in the presence of O3 within the temperature range 254-297 K. O3 was removed with quantum yields of 5.8 + or - 0.5, 4.0 + or - 0.3, 2.9 + or - 0.3 and 1.9 + or - 0.2 at 297, 283, 273, and 252 K respectively, invariant to changes in the initial O3 or Cl2 concentration, the extent of conversion or the absorbed intensity, I sub a. The addition of nitrogen had no effect on -phi(03). The Cl2 removal quantum yields were 0.11 + or - 0.02 at 297 K for Cl2 conversions of about 30%, much higher than expected from mass balance considerations based on the initial quantum yield of 0.089 + or - 0.013 for OClO formation at 297 K. The final chlorine-containing product was Cl2O7. It was produced at least in part through the formation of OClO as an intermediate which was also observed with an initial quantum yield of phi sub i(OClO) = 2500 exp(-(3025 + or - 625)/T) independent of (O3) or I sub a.

Stuper, W. W.↗