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At least 55 records · Page 3

Aluminum 26, Be-10 and Cl-36 depth profiles in the Canyon Diablo iron meteorite

We have measured activities of the long-lived cosmogenic radionuclides Al-26, Be-10, and Cl-36 in 12 fragments of the iron meteorite Canyon Diablo and have constructed production rate-versus-depth profiles of those radionuclides. Profiles determined using differential particle fluxes calculated with the LAHET code system are in good agreement with Al-26, Be-10, and Cl-36 experimental data, but the agreement for Cl-36 was obtained only after neutron-induced cross sections were modified. Profiles calculated with lunar particle fluxes are much lower than experimental Canyon Diablo profiles. The cosmic ray exposure ages of most samples are near 540 m.y.

Michlovich, E. S.↗

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.↗

Kinetics of the Reactions of O((sup 3)P) and Cl((sup 2)P) with HBr and Br2

A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of reactions (1)-(4) as a function of temperature. (1) O((sup 3)P) + Br2 yields BrO + Br((sup 2)P(sub 3/2)) at 255-350 K; (2) Cl((sup 2)P) + Br2 yields BrCl + Br((sup 2)P(sub 3/2)) at 298-401 K; (3) O((sup 3)P) + HBr yields OH + Br((sup 2)P(sub J)) at 250-402 K; (4) Cl((sup 2)P) + HBr yields HCl + Br((sup 2)P(sub J)) at 257-404 K. In all cases, the concentration of the excess reagent, i.e, HBr or Br2, was measured in situ in the slow flow system by UV-visible photometry. Heterogeneous dark reactions between XBr (X equals H or Br) and the photolytic precursors for Cl((sup 2)P) and O((sup 3)P) (Cl2 and O3, respectively) were avoided by injecting minimal amounts of precursor into the reaction mixture immediately upstream from the reaction zone. The following Arrhenius expressions summarize our results (errors are 2 sigma and represent precision only, units are cu cm/(molecule.s): k(sub 1) = (1.76 +/- 0.80) x 10(exp -11 exp[(40 +/- 100)/T]; k(sub 2) = (2.40 +/- 1.25) x 12(exp -10) exp[-(144 +/- 176)/T]; k(sub 3) = (5.11 +/- 2.82) x 10(exp -12) exp[-(1450 +/- 160)/T]; k(sub 4) = (2.25 +/- 0.56) x 10(exp -11) exp[-(400 +/- 80)/T]. The consistency (or lack thereof) of our results with those reported in previous kinetics and dynamics studies of reactions (1)-(4) is discussed.

Nicovich, J. M.↗

Kinetics of the Cl(2)P(J)) + CH4 Reaction: Effects of Secondary Chemistry Below 300 K

Absolute rate data for the Cl(2)P(J) + CH4 yields HCl + CH3 reaction have been obtained from 218 to 298 K by using the discharge-flow resonance fluorescence technique at I Torr total pressure. The result at 298 K is (10.1 +/- 0.6) x 10(exp -14) cu cm/molecule/s. The temperature dependence in Arrhenius form is (6.5 +/- 0.9 ) x 10(exp -12) exp[(-1235 +/- 34 )/T]. The errors given are one standard deviation; overall experimental error is estimated at +/- 15%. Because of the relatively large disagreement among earlier measurements at low temperatures, the results were examined for possible effects of non-Boltzmann spin distribution and vibrational excitation of CH4, secondary chemistry of CH3 radicals, and impurities in the CH4 source. There was no significant change in the observed rate constant when an efficient spin quencher, CF4, was added and estimates indicate that vibrational partitioning in CH4 should be at the ambient reactor temperature before the start of the reaction. The results were also independent of the source of Cl atoms (microwave discharge or thermal decomposition of Cl2) and whether CH4 was purified in-situ. However, the observed rate constant did depend on initial Cl atom concentrations and to a lesser extent on CH4 concentrations. Numerical simulations were used to assess the importance of secondary chemistry over a range of reactant concentrations

Wang, J. J.↗

A Giant Radio Halo in a Low-Mass SZ-Selected Galaxy Cluster: ACT-CL J0256.5+0006

We present the detection of a giant radio halo (GRH) in the Sunyaev-Zel'dovich (SZ)-selected merging galaxy cluster ACT-CL J0256.5+0006 (zeta = 0.363), observed with the Giant Metrewave Radio Telescope at 325 MHz and 610 MHz. We find this cluster to host a faint (S(sub 610) = 5.6 +/- 1.4 mJy) radio halo with an angular extent of 2.6 arcmin, corresponding to 0.8 Mpc at the cluster redshift, qualifying it as a GRH. J0256 is one of the lowest-mass systems, M(sub 500,SZ) = (5.0 +/- 1.2) x 10(sup14) solar mass foud to host a GRH. We measure the GRH at lower significance at 325 MHz (S(sub 325) = 10.3 +/- 5.3 mJy), obtaining a spectral index measurement of alpha sup 610 sub 325 = 1.0(sup +0.7)(sub 0.9). This result is consistent with the mean spectral index of the population of typical radio halos, alpha = 1.2 +/- 0.2. Adopting the latter value, we determine a 1.4 GHz radio power of P(sub 1.4GHz) = (1.0 +/- 03) x 10(sup 24) W Hz(sup -1), placing this cluster within the scatter of known scaling relations. Various lines of evidence, including the ICM morphology, suggest that ACT-CL J0256.5+0006 is composed of two subclusters. We determine a merger mass ratio of 7:4, and a line-of-sight velocity difference of perpendicular = 1880 +/- 210 km s(sup -1). We construct a simple merger model of infer relevant time-scales in the merger. From its location on the P1.4GHz-L(sub x) scaling relation, we infer that we observe ACT-CL J0256.5+0006 just before first core crossing.

core crossing↗

Subsurface Cl-bearing salts as potential contributors to recurring slope lineae (RSL) on Mars

We report laboratory experimental results that support a brine-related hypothesis for the recurring slope lineae (RSL) on Mars in which the subsurface Cl-salts, i.e., hydrous chlorides and oxychlorine salts (HyCOS) are the potential source materials. Our experiments revealed that within the observed RSL temperature window TRSL (250–300 K), the deliquescence of HyCOS could occur in relative humidity ranges (RH≥22%–46%) much lower than those for hydrous (Mg, Fe)-sulfates (RH≥75%–96%). In addition, we demonstrated that the RH values kept by common HyCOS and hydrous sulfates in enclosures have a general trend as RH(sulfates) > RH(perchlorates) > RH(chlorides) (with same type of cation) in wide T range. It means that the required RH range for a Cl-bearing salt to deliquescence can be satisfied by a co-existing salt of different type, e.g., in the subsurface layers of mixed salts on Mars. Furthermore, we found a strong temperature dependence of the deliquescence rates for all tested HyCOS, e.g., a duration of 1–5 sols for all HyCOS at the high end (300 K) of TRSL, and of 20–70 sols for all tested HyCOS (except NaClO4·H2O) at the low end (250 K) of TRSL, which is consistent with the observed seasonal behavior of RSL on Mars. From a mass-balance point of view, the currently observed evidences on Mars do not support a fully-brine-wetted track model, thus we suggest a brine-triggered granular-flow model for the most RSL. Considering the recurrence of RSL in consecutive martian years, our experimental results support the rehydration of remnant HyCOS layers during a martian cold season through H2O vapor-to-salt direct interaction. We found that the evidences of HyCOS rehydration under Mars relevant P-T-RH conditions are detectable in a few minutes by in situ Raman spectroscopy. This rehydration would facilitate the recharge of H2O back into subsurface HyCOS, which could serve as the source material to trigger RSL in a subsequent warm season. The major limiting factor for this rehydration is the H2O supply, i.e., the H2O vapor density carried by current Mars atmospheric circulation and the diffusion rate of H2O vapor into the salt-rich subsurface in a cold season. In a worst-case scenario, these H2O supplies can support a maximum increase of hydration degrees of two for totally dehydrated HyCOS, whereas the full rehydration of subsurface HyCOS layers can be easily reached during a>30° obliquity period that has H2O vapor density 10× to 20× times the value of current obliquity. Overall, our results imply the existence of a large amount of Cl-bearing salts in the subsurface at RSL sites.

Alian Wang↗

Probing the Atmospheric Cl Isotopic Ratio on Mars: Implications for Planetary Evolution and Atmospheric Chemistry

Following the recent detection of HCl in the atmosphere of Mars by ExoMars/Trace Gas Orbiter, we present here the first measurement of the 37Cl/35Cl isotopic ratio in the Martian atmosphere using a set of NOMAD observations. We determine an isotopic anomaly of -6 ±78‰ compared to Earth standard, consistent with the -51‰ to -1‰ measured on Mars’ surface by Curiosity. The measured isotopic ratio is also consistent with surface measurements, and suggests that Cl reservoirs may have undergone limited processing since formation in the Solar Nebula. The examination of possible sources and sinks of HCl shows only limited pathways to short-term efficient Cl fractionation and many plausible reservoirs of “light” Cl.

Exomars NOMAD↗

Thermomagnetic analysis of meteorites. I - Cl chondrites

Samples of all five of the known Cl chondrites have been analyzed thermomagnetically. The only magnetic phase found in four of the chondrites (Alais, Ivuna, Orgueil, Tonk) was magnetite containing less than 6% nickel. The Revelstoke Cl chondrite contains essentially Ni-free Fe3O4 as the predominant phase; however, a small amount of a thermally unstable iron compound (presumably FeS) is additionally present. Estimates of the weight percentage of magnetite, based on saturation moments, are: Alais, 5.3 plus or minus 0.4%; Ivuna, 12.2 plus or minus 0.9%; Orgueil, 11.9 plus or minus 0.8%; Revelstoke, 7.2 plus or minus 0.5%; and Tonk, 9.4 plus or minus 0.6%.

Larson, E. E.↗

The reaction Cl + H2CO yields HCl + HCO: Decreased sensitivity of stratospheric ozone to chlorine perturbations

The absolute rate constant for the reaction Cl + H2CO yields HCl + HCO was determined by the flash-photolysis resonance fluorescence method to be 7.5 plus or minus 0.9 (2 sigma) times 10 to the minus 11th power cu cm/molecule sec at 298 K and to have a negligible temperature dependence. This rate which is more than 2000 times faster than the rate of Cl + CH4 indicates that formaldehyde (H2CO) will compete significantly with methane (CH4) for the conversion of active chlorine in the stratosphere to the inactive reservoir HCl. Chlorine will thus be a less efficient destroyer of stratosphere ozone than previously believed. Ambient stratospheric ozone will depend less on the ambient chlorine amount and the predicted response to chlorine perturbations will be lessened. One-dimensional eddy-diffusion photochemical model calculations indicate a factor of 1.1 less sensitivity to chlorine than recently reported. For a steady-state CFM release at 1975 rates (750,000 tons/year) the eventual ozone depletion is now calculated to be 14%.

Stief, L. J.↗

Rate constant measurements for the reaction Cl + CH2O yields HCl + CHO Implications regarding the removal of stratospheric chlorine

The flash photolysis resonance fluorescence technique was employed to investigate the rate constant for the reaction Cl + CH2O yields HCl + CHO from 223 to 323 K. An Arrhenius fit of the data gives a rate constant equal to (1.09 + or - 0.40) x 10 to the -10th exp/-(131 + or - 98)/T/ in units of cu cm/molecule per sec. The results are compared to two very recent kinetic studies and are assessed in view of the reaction's role in disrupting the Cl-ClO stratospheric ozone depletion chain.

Anderson, P. C.↗

An explanation of the preferential formation of less stable isomers in three-body reactions - Cl + NO2 + M; ClO + NO2 + M

A realistic assessment of the potential depletion of stratospheric ozone due to manmade emissions requires a knowledge of the sources and sinks of the potential threat. The reactions ClO + NO2 + M yield products and Cl + NO2 + M yield products are of interest because they represent possible sink mechanism for both odd chlorine and odd nitrogen species. In this paper, the Troe method (1977) is used to calculate the low-pressure limit rate constants of the above three-body reactions. The result for the Cl + NO2 + M reaction is found to be in excellent agreement with the experimental finding of Niki et al. (1978), where both nitryl chloride and chlorine nitrate are products of the cited reaction. An explanation is proposed to account for apparent discrepancy between the measured rate constants for ClO + NO2 + M in the forward and reverse directions. Stratospheric implications are also discussed.

Chang, J. S.↗

Volatile element chemistry in the solar nebula - Na, K, F, Cl, Br, and P

The results of the most extensive set to date of thermodynamic calculations on the equilibrium chemistry of several hundred compounds of the elements Na, K, F, Cl, Br, and P in a solar composition system are reported. Two extreme models of accretion are investigated. In one extreme complete chemical equilibrium between condensates and gases is maintained because the time scale for accretion is long compared to the time scale for cooling or dissipation of the nebula. Condensates formed in this homogeneous accretion model include several phases such as whitlockite, alkali feldspars, and apatite minerals which are found in chondrites. In the other extreme complete isolation of newly formed condensates from prior condensates and gases occurs due to a time scale for accretion that is short relative to the time required for nebular cooling or dissipation. The condensates produced in this heterogeneous accretion model include alkali sulfides, ammonium halides, and ammonium phosphates. None of these phases are found in chondrites. Available observations of the Na, K, F, Cl, Br, and P elemental abundances in the terrestrial planets are found to be compatible with the predictions of the homogeneous accretion model.

Fegley, B., Jr.↗

Temperature dependence of the hydrogen atom abstraction reactions of Cl/+/ and HCl/+/ with H2

Rate constants are reported for the reactions of Cl(+) and HCl(+) with H2 over the temperature range 150-400 K. The Cl(+) reaction has a positive temperature dependence that follows the Arrhenius form k1 = A exp(-169/T). The reaction of HCl(+) has a negative temperature dependence that follows the form k2 = AT to the -0.6 power. The implication of these results for interstellar chemistry is commented on. Schematic potential surfaces for the reactions are suggested.

Cates, R. D.↗

Formation of the Cl I line at 1351 A in the solar chromosphere

The formation of the multiplet containing the Cl I 1351 A line is investigated due to the unusual brightness of this line. It is determined that this line is formed via a fluorescence effect driven by the 1335 A line of C II. Non-LTE calculations including this effect are found to agree with the observed line intensity. It is shown that the 1347 and 1363 A lines of Cl I do not benefit from this effect and they are predicted to be approximately 100 times weaker.

Shine, R. A.↗

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.↗

Reaction of atomic bromine with acetylene and loss rate of atmospheric acetylene due to reaction with OH, Cl, O, and Br

The first-order, diffusion, and bimolecular rate constants for the reaction Br + C2H2 yields C2H3Br are evaluated. The rate constants are measured at 210, 248, 298, and 393 K and at pressures between 15-100 torr Ar using flash photolysis combined with time-resolved detection of atomic bromine via Br resonance radiation. It is observed that the reaction is not affected by pressure or temperature and the bimolecular constant = (4.0 + or - 0.8) x 10 to the -15th cu cm/sec with an error of two standard deviations. The C2H2 + Br reaction rates are compared with reactions of C2H2 with Cl, OH, NH2, and H. The loss rates for atmospheric C2H2 for reactions with OH, Cl, O, and Br are calculated as a function of altitude.

Payne, W. A.↗

Neonlike Ar and Cl 3p-3s emission from a theta-pinch plasma

Time-resolved extreme-UV emission from sixteen 3p-3s transitions, some of the type in which lasing has been demonstrated in heavier elements, is measured for neonlike Ar(8+) and Cl(7+). These observations are made on a hydrogen theta-pinch plasma with a 5 pct admixture of argon or freon (for Cl). Fourteen 3d-3p spectral lines are also detected. The measured intensities are compared to theoretical predictions. There is no evidence of anomalously intense lines originating on 2p5 3p J = 2 upper levels compared to J = 0, as observed in gain experiments.

Elton, R. C.↗