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NASA NTRS1995

Heterogeneous reactions of HNO3(g) + NaCl(s) yields HCl(g) + NaNO3(s) and N2O5(g) + NaCl(s) yields ClNO2(g) + NaNO3(s)

The heterogeneous reactions of HNO3(g) + NaCl(s) yields HCl(g) + NaNO3(s) (eq 1) and N2O5(g) + NaCl(s) yields ClNO2(g) + NaNO3(S) (eq 2) were investigated over the temperature range 223-296 K in a flow-tube reactor coupled to a quadrupole mass spectrometer. Either a chemical ionization mass spectrometer (CIMS) or an electron-impact ionization mass spectrometer (EIMS) was used to provide suitable detection sensitivity and selectivity. In order to mimic atmospheric conditions, partial pressures of HNO3 and N2O5 in the range 6 x 10(exp -8) - 2 x 10(exp -6) Torr were used. Granule sizes and surface roughness of the solid NaCl substrates were determined by using a scanning electron microscope. For dry NaCl substrates, decay rates of HNO3 were used to obtain gamma(1) = 0.013 +/- 0.004 (1sigma) at 296 K and > 0.008 at 223 K, respectively. The error quoted is the statistical error. After all corrections were made, the overall error, including systematic error, was estimated to be about a factor of 2. HCl was found to be the sole gas-phase product of reaction 1. The mechanism changed from heterogeneous reaction to predominantly physical adsorption when the reactor was cooled from 296 to 223 K. For reaction 2 using dry salts, gamma(2) was found to be less than 1.0 x 10(exp -4) at both 223 and 296 K. The gas-phase reaction product was identified as ClNO2 in previous studies using an infrared spectrometer. An enhancement in reaction probability was observed if water was not completely removed from salt surfaces, probably due to the reaction of N2O5(g) + H2O(s) yields 2HNO3(g). Our results are compared with previous literature values obtained using different experimental techniques and conditions. The implications of the present results for the enhancement of the hydrogen chloride column density in the lower stratosphere after the El Chichon volcanic eruption and for the chemistry of HCl and HNO3 in the marine troposphere are discussed.

Leu, Ming-Taun↗

NASA NTRS1995

Heterogeneous Reactions of HNO3(g) + NaCl(s) Yields HCL(g) + NaNO3(s) and N2O5(g) + NaCl(s) Yields ClNo2(g) + NaNO3(s)

The heterogeneous reactions of HNO3(g) + NaCl(s) Yields HCL(g) + NaNO3(s) and N2O5(g) + NaCl(s) Yields ClNo2(g) + NaNO3(s)were investigated over a temperature range of 223-296 K in a flow-tube reactor coupled to a quadrupole mass spectrometer. The implications for volcanic enhancement of the HCl and HNO3 column density in the lower stratosphere are discussed.

heterogeneous↗

NASA NTRS1966

Gas-induced orientations of vapor-deposited NaCl crystals on NaCl cleavage surfaces.

Residual gas influence on orientation of vapor deposited NaCl crystals

VAPOR DEPOSITION↗

NASA NTRS1979

The role of NaCl in flame chemistry, in the deposition process, and in its reactions with protective oxides as related to hot corrosion

Sodium chloride is believed to be the primary source of turbine engine contamination that contributes to hot corrosion. The behavior of NaCl-containing aerosols ingested with turbine intake air is very complex; some of the NaCl may vaporize during combustion while some may remain as particulates. The NaCl can lead to Na2SO4 formation by several possible routes or it can contribute to corrosion directly. Hydrogen or oxygen atom reaction with NaCl(c) was shown to result in the release of Na(g). Gaseous NaCl in flames can be partially converted to gaseous Na2SO4 by homogeneous reactions. The remaining gaseous NaCl and other Na-containing molecules can act as sodium carriers for condensate deposition of Na2SO4 on cool surfaces. A frozen boundary layer theory was developed to predict the rates of deposition. The condensed phase NaCl can be converted directly to condensed Na2SO4 by reaction with sulfur oxides and O2. Reaction of gaseous NaCl with Cr2O3 results in the vapor phase transport of chromium by the formation of complex Cr-containing gaseous molecules. Similar gaseous complexes are formed with molybdenum. The presence of gaseous NaCl was shown to affect the oxidation kinetics of Ni-Cr alloys. It also causes changes in the surface morphology of Al2O3 scales formed on Al-containing alloys.

Kohl, F. J.↗

NASA NTRS1988

Characteristics of injury and recovery of net NO3- transport of barley seedlings from treatments of NaCl

The nature of the injury and recovery of nitrate uptake (net uptake) from NaCl stress in young barley (Hordeum vulgare L, var CM 72) seedlings was investigated. Nitrate uptake was inhibited rapidly by NaCl, within 1 minute after exposure to 200 millimolar NaCl. The duration of exposure to saline conditions determined the time of recovery of NO3- uptake from NaCl stress. Recovery was dependent on the presence of NO3- and was inhibited by cycloheximide, 6-methylpurine, and cerulenin, respective inhibitors of protein, RNA, and sterol/fatty acid synthesis. These inhibitors also prevented the induction of the NO3- uptake system in uninduced seedlings. Uninduced seedlings exhibited endogenous NO3- transport activity that appeared to be constitutive. This constitutive activity was also inhibited by NaCl. Recovery of constitutive NO3- uptake did not require the presence of NO3-.

Non-NASA Center↗

NASA NTRS1983

Reactions of NaCl with Gaseous SO3, SO2, and O2

Hot corrosion of gas turbine engine components involves deposits of Na2SO4 which are produced by reactions between NaCl and oxides of sulfur. For the present investigation, NaCl single crystals were exposed at 100 to 850 C to gaseous mixtures of SO3, SO2, and O2. The products formed during this exposure depend, primarily, on the temperatures. The four product films were: NaCl-SO3; Na2S2O7; Na2SO4; and NaCl-Na2SO4. The kinetics of the reactions were measured.

Fielder, W. L.↗

NASA NTRS1984

Reactions of NaCl with gaseous SO3, SO2, and O2

Fielder, W. L.↗

NASA NTRS2000

Body Temperatures During Exercise in Deconditioned Dogs: Effect of NACL and Glucose Infusion

Infusion of glucose (Glu) into normal exercising dogs attenuates the rise in rectal temperature (Delta-Tre) when compared with delta-Tre during FFA infusion or no infusion. Rates of rise and delta-=Tre levels are higher during exercise after confinement. Therefore, the purpose of this study was to determine if Glu infusion would attenuate the exercise-induced excess hyperthermia after deconditioning. Rectal and quadricep femoris muscle temperatures (Tmu) were measured in 7 male, mongrel dogs dogs (19.6 +/- SD 3.0 kg) during 90 minutes of treadmill exercise (3.1 +/-SD 0.2 W/kg) with infusion (30ml/min/kg) of 40% Glu or 0.9% NaCL before BC) and after confinement (AC) in cages (40 x 110 x 80 cm) for 8 wk. Mean (+/-SE body wt. were 19.6 +/- 1.1 kg BC and 19.5 +/- 1.1kg AC, exercise VO2 were not different (40.0 - 42.0 mi/min/kg-1). With NaCl AC, NaCl BC, GluAC, and GluBC: Delta-Tre were, 1.8, 1.4, 1.3 and 0.9C respectively; and Delta-Tmu were 2.3, 1.9, 1.6, and 1.4C. respectively (P<0.05 from GluBC). Compared with NaCl infusion, attenuated both Delta-Tre and Delta-Tmu BC and AC, respectively. Compared with GluBC, GluAC attenuated Delta-Tmu but not Delta-Tre. Thus. with similar heat production, the mechanism for attenuation at bad body temperature with Glu infusion must affect avenues of heat dissipation.

Greenleaf, J. E.↗

NASA NTRS1976

Reactions of chromium with gaseous NaCl in an oxygen environment

Target collection techniques and high pressure mass spectrometric sampling have been used to study the formation of volatile chromium-containing species in the reaction of Cr2O3 with O2 and NaCl gases. Experiments were performed at atmospheric pressure as a function of chromium temperature, oxygen pressure, and NaCl gas concentration. The major chromium-containing vapor species were found to be (NaCl)x CrO3 gas, with x = 1,2, and 3, which are products of heterogeneous reactions on the surface. The kinetics indicate first order dependence on oxygen and sodium chloride pressures.

Stearns, C. A.↗

NASA NTRS1976

Reactions of chromium with gaseous NaCl in an oxygen environment

Target collection techniques and high pressure mass spectrometric sampling have been used to study the formation of volatile chromium-containing species in the reaction of Cr2O3 in the condensed state with gaseous O2 and NaCl. Experiments were performed at atmospheric pressure as a function of chromium temperature, oxygen pressure, and NaCl concentration. The major chromium-containing vapor species were found to be (NaCl)xCrO3, with x = 1,2, and 3, which are products of heterogeneous reactions on the surface. The kinetics indicate first order dependence on oxygen and sodium chloride pressures.

Stearns, C. A.↗

NASA NTRS1977

Interaction of NaCl(g) and HCl(g) with condensed NA2SO4

The interaction of Na2SO4(l) with NaCl(g), HCl(g) and H2O(g) was studied in atmospheric pressure flowing air and oxygen at Na2SO4(l) temperatures of 900 and 1000 C. Thermomicrogravimetric and high pressure mass spectrometric sampling techniques were used. Experimental results establish that previously reported enhanced rates of weight loss of Na2SO4(l) in the presence of NaCl(g) are due to the reaction: Na2SO4(c) + 2HCl(g) = 2NaCl(g) + SO2(g) + H2O(g) + 1/2O2(g) being driven to the right in flowing gas systems. The HCl(g) is the product of hydrolysis of NaCl caused by small but significant amounts of H2O(g) present in the system. Thermochemical calculations are used to show that even with sub-ppm levels of H2O(g) present, significant quantities of HCl(g) are produced.

Stearns, C. A.↗

NASA NTRS1981

Investigation into the role of NaCl deposited on oxide and metal substrates in the initiation of hot corrosion

Morphological aspects of the conversion to Na2SO4 of NaCl deposits over the temperature range 500-700 C, in air with added SO2 and H2O. Progress of the reaction was observed by withdrawing samples at various times and examining them under the scanning electron microscope using EDAX to assess the extent of chloride to sulfate conversion. These initial results show that the conversion to Na2SO4 proceeds directly on the sodium chloride surface as well as on the surrounding substrate due to evaporation of NaCl from the solid particle. The mechanism of this reaction could involve reaction in the vapor to produce Na2SO4 which then deposits, alternatively Na2SO4 could form directly on the substrate surface due to direct reaction there between the vapors NaCl, SO2 and O2.

Birks, N.↗

NASA NTRS1983

The oxidation behavior of a model molybdenum/tungsten-containing alloy in air alone and in air with trace levels of NaCl(g)

Thermogravimetric, metallographic, and X-ray studies of a model alloy, Ni-(17 a/o)Al-(10 a/o)Mo+W, oxidized in dry air at 600-1200 C and in air with 10 ppm NaCl gas at 900 C, are reported. The alloy was melted under Ar and pretreated in flowing H2 for 24 h at 1300 C. Polished 1.3 x 1.3 x 0.2-cm specimens were washed and degreased prior to oxidation in a quartz tube within a furnace for up to 120 hr. The oxidation activation energy of the alloy is determined to be about 30 kcal/mole. The specimens oxidized at 900 C and hotter exhibited oxidized and nitrided phases covered by complex NiMoO4, NiWO4, and NiAl2O4 scales and a porous, nonprotective outer layer of NiO. The oxidation behavior is found to be determined by the formation and growth of the scale, especially the (Mo,W)O2 component. Al2O3 scale layers were not formed, and further runs with pure O2 or Ar-(20 percent)O2 ruled out an explanation of this phenomenon based on aluminum nitride formation. The oxidation was accelerated by the addition of NaCl gas, a finding attributed to the reaction of NaCl with external locally protective Al2O3 scales and with the internal(Mo, W)O2 layers.

Smeggil, J. G.↗

NASA NTRS1991

Heterogeneous reactions with NaCl in the El Chichon volcanic aerosols

Previous investigations of the effects of the 1982 eruption of the El Chichon volcano could not explain all the observations of changes in O3, HCl, NO and NO2 simultaneously without proposing unproven chemical reactions. Since reactions between solid NaCl and gaseous ClNO3 and N2O5 rapidly produce photochemically active chlorine species and solid NaNO3 in laboratory experiments, it is suggested that these reactions could have occurred with the NaCl observed to be present in the El Chichon sulfuric acid areosols. As a consequence, it is predicted that HCl should increase substantially, while NO(x) should decrease, in agreement with the measurements after the eruption. Ozone should be only slightly affected by these reactions. Reactions between solid NaCl and the acids H2SO4 and HNO3 might prove to be important, but sufficient evidence regarding their efficiency and the pressure of HNO3 in the aerosols is lacking.

Michelangeli, Diane V.↗

NASA NTRS1994

Heterogeneous Reaction of ClONO2(g) + NaCl(s) to Cl2(g) + NaNO3(s)

The heterogeneous reaction of ClON02 + NaCl yields Cl2 + NaNO3 (eq 1) was investigated over a temperature range 220-300 K in a flow-tube reactor interfaced with a differentially pumped quadrupole mass spectrometer. Partial pressures of ClON02 in the range 10(exp -8) - 10(exp -5) Torr were used. Granule sizes and surface roughness of the NaCl substrates were determined by using a scanning electron microscope, and in separate experiments, surface areas of the substrates were measured by using BET analysis of gas-adsorption isotherms. For dry NaCl substrates, both the decay rates of ClON02 and the growth rates Of C12 were used to obtain reaction probabilities, gamma(sub l) = (4.6 +/- 3.0) x 10(exp -3) at 296 K and (6.7 +/- 3.2) x 10(exp -1) at 225 K, after considering the internal surface area, The error bars represent 1 standard deviation. The Cl2 yield based on the ClONO2 reacted was measured to be 1.0 +/- 0.2. In order to mimic the conditions encountered in the lower stratosphere, the effect of water vapor pressures between 5 x 10(exp -5) and 3 x 10(exp -4) Torr on reaction 1 was also studied. With added H20, reaction probabilities, gamma = (4.1 +/- 2.1) x 10(exp -3) at 296 K and (4.7 +/- 2.9) x 10(exp -3) at 225 K, were obtained. A trace of HOCl, the reaction product from the ClON02 + H20 yield HOCl + HN03 reaction, was observed in addition to the C12 product from reaction 1. The implications of this result for the enhancement of hydrogen chloride in the stratosphere after the El Chichon volcanic eruption and for the marine troposphere are discussed.

Timonen, Raimo S.↗

NASA NTRS1996

Repartitioning of NaCl and Protein Impurities in Lysozyme Crystallization

Nonuniform precipitant and impurity incorporation in protein crystals can cause lattice strain and, thus, possibly decrease the X-ray diffraction resolution. To address this issue, a series of crystallization experiments were carried out, in which initial supersaturation, NaCl concentration, protein purity level and crystallized fraction were varied. Lysozyme and protein impurities, as well as sodium and chloride were independently determined in the initial solution, supernatant and crystals. The segregation coefficients for Na(+) and Cl(-) were found to be independent of supersaturation and NaCl concentration, and decreased with crystallized fraction/crystal size. Numerical evaluation of the extensive body of data, based on a nucleation-growth- repartitioning model, suggests a core of approx. 40 microns in which salt is incorporated in much greater concentrations than during later growth. Small crystals containing higher amounts of incorporated NaCl also had higher protein impurity contents. This suggests that the excess salt is associated with the protein impurities in the core. X-ray topography revealed strain fields in the center of the crystals comparable in size to the inferred core. The growth rates of crystals smaller than 30-40 pm in size were consistently 1.5-2 times lower than those of larger crystals, presumably due to higher chemical potentials in the core.

Vekilov, Peter G.↗

NASA NTRS1961

Neutralization of Hydroxide Ion in Melt-Grown NaCl Crystals

Many recent studies of solid-state phenomena, particularly in the area of crystal imperfections, have involved the use of melt-grown NaCl single crystals. Quite often trace impurities in these materials have had a prominent effect on these phenomena. Trace amounts of hydroxide ion have been found in melt-grown NaCl crystals. This paper describes a nondestructive method of neutralizing the hydroxide ion in such crystals. Crystals of similar hydroxide content are maintained at an elevated temperature below the melting point of NaCl in a flowing atmosphere containing. dry hydrogen chloride. Heat treatment is continued until an analysis of the test specimens shows no excess hydroxide ion. A colorimetric method previously described4 is used for this analysis.

Otterson, Dumas A.↗

NASA NTRS1973

Measurements of the dielectric properties of seawater and NaCl solutions at 2.65 GHz.

Measurements at 2.653 GHz of the dielectric properties of seawater samples collected over the world's oceans and NaCl solutions over the concentration range from 0.3 to 0.7 N have been made over the temperature range from 5.5 to 24 C to an accuracy of 0.2% in the real part of epsilon and 0.4% in the imaginary part of epsilon. The measurements demonstrate that the dielectric properties of seawater can be determined from its chlorinity alone but are substantially different from those of the 3.35 wt % NaCl solution, which has been taken in all previous work as a model for seawater. The data are presented in a form that is well fitted by a linear dependence on chlorinity. The accuracy of the measurements removes the uncertainty in the dielectric properties of seawater as a significant source of error in S-band radiometric determination of ocean surface temperature.

Ho, W.↗