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NASA NTRS1976

A temperature dependence kinetics study of the reactions of Cl/2-P-3/2/ with O3, CH4, and H2O2

The temperature dependence of two chlorine atom reactions of considerable fundamental importance to stratospheric chemistry was studied using the technique of flash photolysis-resonance fluorescence. The reactions of interest were: (1) Cl + O3 yields ClO + O2 studied at 220-350 K, and (2) Cl + CH4 yields CH3 + HCl studied at 218-401 K. In addition, the reaction Cl + H2O2 yields HCl + HO2 was studied at 300 K. The corresponding rate constants are provided for the three reactions. The new rate data implies the need to revise downward by a factor of 2.4-3 the magnitude of the ozone perturbation due to the presence of ClO/x/ species in the stratosphere, predicted by earlier model calculations.

Watson, R.↗
NASA NTRS1988

Chemistry of the CO dimer at low temperatures

Researchers conducted a series of experiments on the chlorine-catalyzed photodecomposition of O sub 3 both in the gas and in inert solvents such as CF sub 4 and CO sub 2 in the temperature range about 190 to 225 K. The liquid medium was chosen in order to minimize possible surface loss of long-lived ClO dimer, and to aid in the stabilization of transient excited intermediates. The mechanism of dimer formation was as follows: (1) Cl sub 2 + hv yields Cl + Cl; (2) Cl + O sub 3 yields ClO + O sub 2; (3) ClO + ClO yields Cl sub 2 O sub 2. The experiments were done in cooled low temperature cells, with irradiation from an Osram high pressure mercury arc, filtered to remove radiation below 325 nm. Spectral analysis was by means of a Cary Model 2200 UV spectrometer. The principal objectives were: (1) to determine the lifetime of the dimer as a function of temperature; (2) to observe spectral changes in the mixtures which could be attributed to dimer or related products; and (3) to observe chemical or photochemical reactions of the dimer.

Demore, W. B.↗
NASA NTRS1999

Layered double hydroxide stability. 2. Formation of Cr(III)-containing layered double hydroxides directly from solution

Solutions containing divalent metal [M(II) = Mg2+, Zn2+, Co2+, Ni2+, Mn2+] chlorides and CrCl3 6H2O were titrated with NaOH to yield, for M(II) = Zn, Co, and Ni, hydrotalcite-like layered double hydroxides (LDHs), [[M(II)]1-z[Cr(III)]z(OH)2][Cl]z yH2O, in a single step, without intermediate formation of chromium hydroxide. Analysis of the resultant titration curves yields solubility constants for these compounds. These are in the order Zn < Ni approximately Co, with a clear preference for formation of the phase with z = 1/3. With Mg2+ as chloride, titration gives a mixture of Cr(OH)3 and Mg(OH)2, but the metal sulfates give Mg2Cr(OH)6 1/2(SO4) by a two-step process. Titrimetric and spectroscopic evidence suggests short-range cation order in the one-step LDH systems.

Non-NASA Center↗
NASA NTRS1972

Meteoritic and non-meteoritic trace elements in Luna 16 samples.

Two Luna 16 soils have been analyzed for Ag, Au, Bi, Br, Cd, Co, Cs, Cu, Ga, Ge, In, Ur, Ni, Rb, Re, Sb, Se, Te, Tl, and Zn. A meteoritic component similar to that in Apollo 11 and 12 soils seems to be present, corresponding to about 1.5 to 2% Cl chondrites or equivalent. It probably consists largely of micrometeorites. Three elements show strong enrichments compared to Apollo 11 and 12 soils: Cd (5 x to 200 x), Ag (5 x to 10 x), and Bi (3 x). Presumably these elements were brought in by Cd-Ag-Bi rich material, similar to that in Unit VI of Apollo core 12028.

Laul, J. C.↗
NASA NTRS1999

Layered double hydroxide stability. 1. Relative stabilities of layered double hydroxides and their simple counterparts

Solutions containing di- and trivalent metal chlorides [M(II) = Mg2+, Zn2+, Co2+, Ni2+, Mn2+; M(III) = Al3+, Fe3+] were titrated with NaOH to yield hydrotalcite-like layered double hydroxides (LDH), [[M(II)]1-x[M(III)]x(OH)2][Cl]x yH2O, by way of M(III) hydroxide/hydrous oxide intermediates. Analysis of the resultant titration curves yields nominal solubility constants for the LDH. The corresponding LDH stabilities are in the order Mg < Mn < Co approximately Ni < Zn for M(II) and Al < Fe for M(III). The stability of LDH relative to the separate metal hydroxides/hydrous oxides is discussed.

Non-NASA Center↗
NASA NTRS2012

Searching for Organics Preserved in 4.5 Billion Year Old Salt

Our understanding of early solar system fluids took a dramatic turn a decade ago with the discovery of fluid inclusion-bearing halite (NaCl) crystals in the matrix of two freshly fallen brecciated H chondrite falls, Monahans and Zag. Both meteorites are regolith breccias, and contain xenolithic halite (and minor admixed sylvite -- KCl, crystals in their regolith lithologies. The halites are purple to dark blue, due to the presence of color centers (electrons in anion vacancies) which slowly accumulated as 40K (in sylvite) decayed over billions of years. The halites were dated by K-Ar, Rb-Sr and I-Xe systematics to be 4.5 billion years old. The "blue" halites were a fantastic discovery for the following reasons: (1) Halite+sylvite can be dated (K is in sylvite and will substitute for Na in halite, Rb substitutes in halite for Na, and I substitutes for Cl). (2) The blue color is lost if the halite dissolves on Earth and reprecipitates (because the newly-formed halite has no color centers), so the color serves as a "freshness" or pristinity indicator. (3) Halite frequently contains aqueous fluid inclusions. (4) Halite contains no structural oxygen, carbon or hydrogen, making them ideal materials to measure these isotopic systems in any fluid inclusions. (5) It is possible to directly measure fluid inclusion formation temperatures, and thus directly measure the temperature of the mineralizing aqueous fluid. In addition to these two ordinary chondrites halite grains have been reliably reported in several ureilites, an additional ordinary chondrite (Jilin), and in the carbonaceous chondrite (Murchison), although these reports were unfortunately not taken seriously. We have lately found additional fluid inclusions in carbonates in several additional carbonaceous chondrites. Meteoritic aqueous fluid inclusions are apparently relatively widespread in meteorites, though very small and thus difficult to analyze.

Zolensky, Michael E.↗
NASA NTRSDate not supplied

All-Climate and Ultrafast Rechargeable Aluminum Batteries Enabled By Ternary Eutectic Electrolytes

For Rechargeable Aluminum Batteries (RABs), electrolytes emerge as the most crucial and decisive component due to the following aspects: (i) Sluggish reaction kinetics due to high gravimetric density of Al (2.70 g/cm 3 vs. 0.53 g/cm 3 for Li) and high surface charge density, (ii) a limited safe potential window owing to moderate standard redox potential values. The state-of-the-art electrolytes in the field exhibits a limited stability window (<2.6V vs. Al/Al +3 ), leading to undesired side reactions, such as Cl 2 gas generation, and self-discharge in RABs. Exploration of RABs low-temperature performance is restricted by electrolyte limitations.

Raju Vadthya↗
NASA NTRS1985

p(2 x 2) and c(2 x 2) coverages of Cl and F on Ni(100), a comparison with O and S on Ni(100)

The rigid lattice adsorbate vibrational frequency normal to the surface, omega(e,r) and height above the surface, R(transverse), are computed for p(2 x 2) (0.25 ML) and c(2 x 2) (0.5 ML) coverages of Cl and F. These calculations show a small change in omega(e,r) and a small increase in R(transverse) with increased coverage. The bonding of Cl and F is compared to that found for O and S, both of which show a decrease in R(transverse) and O which shows a larger shift in omega(e,r).

Bauschlicher, C. W., Jr.↗
NASA NTRS1983

Chemical weathering and diagenesis of a cold desert soil from Wright Valley, Antarctica - An analog of Martian weathering processes

Weathering, diagenesis, and chemical alteration of a soil profile from the Dry Valleys of Antarctica are investigated as an analog to soil development within the Martian regolith. Soil samples from a soil pit one meter deep on Prospect Mesa, Wright Valley, are examined for their major element concentrations, water-soluble cations and anions, carbon, sulfur, and water concentrations, and related petrographic characteristics of weathering in a cold, dry environment. A petrographic study of the samples suggests that most silicate mineral and lithic fragments exhibit some degree of alteration. Chemical alteration occurs both in samples above and within the permanently frozen zone. The concentrations of water-soluble cations, for example, Na(+), K(+), Ca(2+), and anions, Cl(-), SO4(2-), NO3(-), are found to decrease significantly from the surface to the permanently frozen zone, suggesting a major movement of water-soluble species. It is also found that enrichments in secondary mineral abundances correlate with the water soluble ion concentrations. The formation of zeolites is seen throughout the soil column; these, it is thought, may be reservoirs for volatile storage within the regolith.

Gibson, E. K.↗
NASA NTRS1988

Chemistry of chlorinated species in the Antarctic stratosphere

The chemistry of Cl sub 2 O sub 2, the chlorine monoxide dimer, has been further investigated in order to better asses its potential role in catalytic ozone destruction cycles. The dimer has been generated in a flow system, in the 200 to 250 K temperature range, by using ozone and chlorine atoms as ClO precursors. The Cl-atoms are produced by a microwave discharge of either Cl sub 2, or of F sub 2 with subsequent addition of HCl. With this later scheme the dimer can be generated in the absence of Cl sub 2. The Fourier transform infrared spectra of the products clearly indicates the presence of two isomers, in agreement with earlier results (J. Phys. Shen., 91, 433, 1987). None of the observed IR bands can be attributed to a ClO-OClO adduct, since they all appear in the absence of any detectable amount of OCl. It is likely that the particles in the polar stratospheric clouds will have a relatively dilute nitric acid outer layer, even if the core is the nitric acid monohydrate, since the particles are in equilibrium with the ambient water vapor, which is present at levels of a few parts per million.

Molina, Mario J.↗
NASA NTRS1977

Kinetics of the reactions of ClO with O and with NO

The rate constants k1, k2, and k3 for the reactions Cl + O3 yields ClO + O2 (1), ClO + O yields Cl + O2 (2), and ClO + NO yields Cl + NO2 (3), respectively, were measured by the discharge-flow technique, in which chlorine atoms are added to a flow of O3 and either O or NO in a helium carrier gas. The conditions of the experiment were such that the steady-state concentration ratios of Cl to ClO are simply interpretable in terms of the rate constant ratios k2/k3 or k3/k1. These rate constant ratios were measured over the range 220 to 298 K and combined with the directly determined k1 value to yield k2 and k3. The results are: k1 = 2.12 x 10 to the -11th exp(-157/T); k2 = 3.38 x 10 to -11th exp(75 plus or minus 40/T); and k3 = 1.13 x 10 to the -11th exp(200 plus or minus 30/T) cu cm/sec.

Zahniser, M. S.↗
NASA NTRS2010

Stable Chlorine Isotope Study: Application to Early Solar System Materials

A significantly large mass fractionation between two stable chlorine isotopes is expected during planetary processes In addition, in view of the isotopic heterogeneity of other light elements, the chlorine isotopes can potentially be used as a tracer for the origins and evolutionary processes of early solar system materials. Due to analytical difficulties, however, current chlorine isotope studies on planetary materials are quite controversial among IRMS (gas source mass spectrometry) and/or TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1-3]. Although a cross-calibration of IRMS and TIMS indicates that both techniques are sufficiently consistent with each other [4], some authors have claimed that the Cl-37/Cl-35 ratio of geological samples obtained by TIMS technique are, in general, misleadingly too high and variable compared to those of IRMS [3]. For example, almost no differences of Cl isotope composition were observed among mantle materials and carbonaceous meteorites by [3]. On the other hand, according to more recent IRMS work [2], significant Cl isotope variations are confirmed for mantle materials. Therefore, additional careful investigation of Cl isotope analyses are now required to confirm real chlorine isotope variations for planetary materials including carbonaceous chondrites [5]. A significantly large mass fractionation between two stable chlorine isotopes is expected during planetary processes In addition, in view of the isotopic heterogeneity of other light elements, the chlorine isotopes can potentially be used as a tracer for the origins and evolutionary processes of early solar system materials. Due to analytical difficulties, however, current chlorine isotope studies on planetary materials are quite controversial among IRMS (gas source mass spectrometry) and/or TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1-3]. Although a cross-calibration of IRMS and TIMS indicates that both techniques are sufficiently consistent with each other [4], some authors have claimed that the 37Cl/35Cl ratio of geological samples obtained by TIMS technique are, in general, misleadingly too high and variable compared to those of IRMS [3]. For eample, almost no differences of Cl isotope composition were observed among mantle materials and carbonaceous meteorites by [3]. On the other hand, according to more recent IRMS work [2], significant Cl isotope variations are confirmed for mantle materials. Therefore, additional careful investigation of Cl isotope analyses are now required to confirm real chlorine isotope variations for planetary materials including carbonaceous chondrites [5]. In order to clarify the stable chlorine isotope features of early solar system materials, we have initiated development of the TIMS technique at NASA JSC applicable to analysis of small amounts of meteoritic and planetary materials. We report here the current status of chlorine isotope analysis at NASA JSC.

Mala,ira. M/↗
NASA NTRS1997

Kinetics and Thermochemistry of ClCO Formation from the Cl + CO Association Reaction

Laser flash photolysis of Cl2/CO/M mixtures (M = N2, CO, Ar, CO2) has been employed in conjunction with Cl((sup 2)P(sub J)) detection by time-resolved resonance fluorescence spectroscopy to investigate equilibration kinetics in the reactions Cl((sup 2)P(sub J)) + CO ClCO as a function of temperature (185-260 K) and pressure (14-200 Torr). The association and dissociation reactions are found to be in the low-pressure limit over the range of experimental conditions investigated. In N2 and/or CO buffer gases, the temperature dependences of the ClCO formation and dissociation reaction rate constants are described by the Arrhenius expressions k(sub 1) = (1.05 +/- 0.36) x 10(exp -34) exp[(810 +/- 70)/T] cm(exp 6)/molecules(exp 2).s and k(sub -1) = (4.1 +/- 3.1) x 10(exp -10) exp[(-2960 +/- 60)/T]cu cm/(molecule.s) (errors are 2 sigma). Second- and third-law analyses of the temperature dependence of the equilbrium constant (k/k-1) lead to the following thermodynamic parameters for the association reaction: Delta-H(sub 298) = -7.7 +/- 0.6 kcal/mol, Delta-H(sub 0) = -6.9 +/- 0.7 kcal/mol, Delta-S(sub 298) = -23.8 +/- 2.0 cal/mole.K, Delta-H(sub f,298)(ClCO) = 5.2 +/- 0.6 kcal/mol (errors are 2 sigma). The results repported in this study significantly reduce the uncertainties in all reported kinetic and thermodynamic parameters.

Nicovich, J. M.↗
NASA NTRS1994

Ammonia on the prebiotic Earth: Iron(II) reduction of nitrite

Theories for the origin of life require the availability of reduced nitrogen. In the non-reducing atmosphere suggested by geochemical evidence, production in the atmosphere and survival of NH3 against photochemical destruction are problematic. Electric discharges and impact shocks would produce NO rather than HCN or NH3. Conversion of NO to nitrous and nitric acid (by way of HNO) and precipitation in acid rain would provide a source of fixed nitrogen to the early ocean. One solution to the NH3 problem may have been the reduction of nitrite/nitrate in the ocean with aqueous ferrous iron, Fe(2+): 6Fe(+2) + 7 H2O + NO2(-) yields 3Fe2O3 + 11 H(+) + NH3. We have measured the kinetics of this reaction as a function of temperature, pH, and concentrations of salts, Fe(+2), and NO2(-). Cations (Na(+), Mg(2+), K(+)) and anions (Cl(-), Br(-), SO4(2-)) increase the rate by factors of 4 to 8. Although a competing pathway yields N2, the efficiency of the conversion of nitrite to ammonia ranges from 25% to 85%. Nitrate reduction was not consistently reproducible; however, when it was observed, its rate was slower by at least 8X than that of nitrite reduction. If the prebiotic atmosphere contained 0.2 to 10 atmospheres CO2 as suggested by Walker (1985), the Fe(+2) concentration and the rate would have been limited by siderite (FeCO3) solubility.

Summers, David P.↗
NASA NTRS2020

Evidence for Adsorption of Chlorine Species on Iron (III)(Hydr)oxides in the Sheepbed Mudstone, Gale Crater, Mars

Ancient aquatic environments in Yellowknife Bay, Gale crater, Mars, could create favorable conditions for adsorption of chlorine compounds (perchlorate and chloride) on Fe (III) (hydr)oxides present in the Sheepbed mudstone, such as akaganeite and ferrihydrite. In this work, 5.2 mM ClO4− and 1.7 to 12 mM Cl− were adsorbed onto ferrihydrite and 5.2 mM ClO4− was adsorbed onto akaganeite at ultraacidic (pH 2–2.5), acidic (pH 3.8–4.5), and near‐neutral (pH 6.2–7.7) pH. Samples were characterized by evolved gas analysis and compared to the data collected for the Cumberland sample from the Sheepbed mudstone. Evolved gas analysis showed that ferrihydrite with 0.5–1 wt.% ClO4− adsorbed under ultraacidic and acidic conditions had a well‐resolved O2 peak at 306 °C due to the thermal decomposition of adsorbed ClO4−. All akaganeite samples with 0.5 wt.% adsorbed ClO4− had a weak peak at 312 °C tentatively assigned to decomposing perchlorate. Evolved gas analysis demonstrated that 0.5–2 wt.% Cl− adsorbed on ferrihydrite at ultraacidic and acidic pH was the main contributor to HCl evolved at >470 °C. Comparison with martian observations indicated that the temperature of the O2 peak originating from ClO4− adsorbed on ferrihydrite matched well with the thermal evolution of O2 from the Cumberland. Evolved HCl originating from Cl− adsorbed on ferrihydrite was within the temperature range of the high‐temperature HCl release from Cumberland (~770 °C). These observations suggest that ferrihydrite containing adsorbed ClO4− and Cl− could exist in the mudstone. Experimental results are consistent with adsorption at acidic pH < 4 environments through postdepositional water‐rock interactions of ferrihydrite with acid‐sulfate groundwater containing dissolved chloride and perchlorate.

T. S. Peretyazhko↗
NASA NTRS1997

Thermochemistry and Kinetics of the Cl+O2 Association Reaction

Laser flash photolysis of Cl2/O2 mixtures has been employed in conjunction with Cl((sup 2)P(sub 3/2)) detection by time-resolved fluorescence spectroscopy to investigate equilibration kinetics for the reactions Cl + O2 + O is in equilibrium with ClOO + O2 at temperatures of 181-200 K and O2 pressures of 15-40 Torr. The third-order rate coefficient for the association reaction at 186.5 +/- 5.5 K is (8.9 +/- 2.9) x 10(exp -33) cm(exp 6) molecule(exp -2) s(exp -1) and the equilibrium constant (K(p)) at 185.4 K is 18.9 atm(exp -1) (factor of 1.7 uncertainty). A third law analysis of our data leads to a value for the Cl-OO bond dissociation energy of 4.76 +/- 0.49 kcal mol(exp -1).

Nicovich, J. M.↗