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At least 37 records · Page 2

Mass spectrometric investigation of the vaporization of sodium and potassium chromates: Preliminary results

Knudsen cell mass spectrometry was used to study the vaporization of sodium and potassium chromates. For both salts, the vaporization proceeds predominately by the reactions M2CrO4(c)=2M(g)+5/4O2(g)+1/2 Cr203(s) and M2CrO4(c)=M2CrO4(g) where M = Na or K. The distribution of the ions M(+), O2(+) and M2CrO4(+) in the measured mass spectrum was found to depend on the material used for the Knudsen cell, even for materials such as platinum and gold. In the case of sodium chromate, the decomposition reaction appears to be less important than the molecular vaporization reaction. A preliminary value of 72 kcal/mole at 1141 K was measured for the heat of the molecular vaporization reaction for sodium chromate. In the case of potassium chromate, it has not been possible to conclude which mode of vaporization dominates. For potassium chromate a value of 101 kcal/mole at 1173 K was obtained for the heat of the molecular vaporization reaction.

Stearns, C. A.↗

Uptake and Dissolution of Gaseous Ethanol in Sulfuric Acid

The solubility of gas-phase ethanol (ethyl alcohol, CH3CH2OH, EtOH) in aqueous sulfuric acid solutions was measured in a Knudsen cell reactor over ranges of temperature (209-237 K) and acid composition (39-76 wt % H2SO4). Ethanol is very soluble under these conditions: effective Henry's law coefficients, H*, range from 4 x 10(exp 4) M/atm in the 227 K, 39 wt % acid to greater than 10(exp 7) M/atm in the 76 wt % acid. In 76 wt % sulfuric acid, ethanol solubility exceeds that which can be precisely determined using the Knudsen cell technique but falls in the range of 10(exp 7)-10(exp 10) M/atm. The equilibrium concentration of ethanol in upper tropospheric/lower stratospheric (UT/LS) sulfate particles is calculated from these measurements and compared to other small oxygenated organic compounds. Even if ethanol is a minor component in the gas phase, it may be a major constituent of the organic fraction in the particle phase. No evidence for the formation of ethyl hydrogen sulfate was found under our experimental conditions. While the protonation of ethanol does augment solubility at higher acidity, the primary reason H* increases with acidity is an increase in the solubility of molecular (i.e., neutral) ethanol.

Michelsen, Rebecca R.↗

The Process of Developing a Multi-Cell KEMS Instrument

Multi-cell KEMS offers many advantages over single cell instruments in regard to in-situ temperature calibration and studies on high temperature alloys and oxides of interest to NASA. The instrument at NASA Glenn is a 90 deg magnetic sector instrument originally designed for single cell operation. The conversion of this instrument to a multi-cell instrument with restricted collimation is discussed. For restricted collimation, the 'field aperture' is in the copper plate separating the Knudsen Cell region and the ionizer and the 'source aperture' is adjacent to the ionizer box. A computer controlled x-y table allows positioning of one of the three cells into the sampling region. Heating is accomplished via a Ta sheet element and temperature is measured via an automatic pyrometer from the bottom of the cells. The computer control and data system have been custom developed for this instrument and are discussed. Future improvements are also discussed.

Copland, E. H.↗

Dissociation energies of some high temperature molecules containing aluminum

The Knudsen cell mass spectrometric method has been used to investigate the gaseous molecules Al2, AlSi,AlSiO, AlC2, Al2C2, and AlAuC2. Special attention was given to the experimental considerations and techniques needed to identify and to measure ion intensities for very low abundance molecular species. Second- and third-law procedures were used to obtain reaction enthalpies for pressure calibration independent and isomolecular exchange reactions. Dissociation energies for the molecules were derived from the measured ion intensities, free-energy functions obtained from estimated molecular constants, and auxiliary thermodynamic data. The bonding and stability of these aluminum containing molecules are compared with other similar species.

Stearns, C. A.↗

Vaporization and compatibility of SiGe radioisotope thermoelectric generators.

The limiting operating temperatures of SiGe thermoelectrics designed for extended operation are set by sublimation process of the elements and by considerations of their compatibility with the surrounding insulating elements. Mass spectrometric Knudsen cell and Langmuir vaporization modes of operation have been utilized in the study of the equilibrium vapor species and in the time evaluation of the sublimation process. Isothermal high-vacuum (1 ntorr) anneals of samples have extended observations to long-time spans. The time variations follow the formation of surface depletion layers due to disproportional rates of sublimation of the various species.

Staley, H. G.↗

Development and evaluation of die and container materials

Commercial high purity ultrafine Si3N4, Al2O3, and SiO2 powders were vacuum dried and stored under nitrogen in sealed containers. Extensive analysis of the chemical, physical, and morphological characteristics of these powders was performed. The interaction of molten silicon with fused quartz was examined in a Knudsen cell using a mass spectrometer. The solubility of oxygen at the melting point of silicon was calculated to be 1.78 times 10 to the 18th power atoms/cu cm, and the activity coefficients of oxygen and silicon monoxide, the major vapor species, were calculated to be 4.83 times 10 to the minus 24th power and 0.0000701, respectively.

Wills, R. R.↗

Preliminary evaluation of the role of K2S in MHD hot stream seed recovery

Results are presented for recent analytical and experimental studies of the role of K2S in MHD hot stream seed recovery. The existing thermodynamic data base was found to contain large uncertainties and to be nonexistent for vapor phase K2S. Knudsen cell mass spectrometric experiments were undertaken to determine the vapor species in equilibrium with K2S(c). K atoms and S2 molecules ere found to be the major vapor phase species in vacuum, accounting for greater than 99 percent of the vapor phase. Combustion gas deposition studies using No. 2 Diesel fuel were also undertaken and revealed that condensed phase K2SO3 may potentially be an important compound in the MHD stream at near-stoichiometric combustion.

Bennett, J. E.↗

Heterogeneous atmospheric reactions - Sulfuric acid aerosols as tropospheric sinks

The reaction probabilities of various atmospheric species incident on a bulk sulfuric acid surface are measured in order to determine the role of sulfuric acid aerosols as pollutant sinks. Reaction products and unreacted starting materials leaving a Knudsen cell flow reactor after collision at 300 K with a H2SO4 surface or a soot surface were detected by mass spectrometry. Significant collision reaction probabilities are observed on a H2SO4 surface for H2O2, HNO3, HO2NO2, ClONO2, N2O5, H2O and NH3, and on soot for NH3. Estimates of the contribution of heterogeneous reactions to pollutant removal under atmospheric conditions indicate that while aerosol removal in the stratosphere is insignificant (loss rate constants approximately 10 to the -10th/sec), heterogeneous reactions may be the dominant loss process for several tropospheric species (loss rate constant approximately 10 to the -5th/sec, comparable to photolysis rate constants).

Baldwin, A. C.↗

Real-time measurement of sodium chloride in individual aerosol particles by mass spectrometry

The method of particle analysis by mass spectrometry has been applied to the quantitative measurement of sodium chloride in individual particles on a real-time basis. Particles of known masses are individually introduced, in the form of a beam, into a miniature Knudsen cell oven (1600 K). The oven is fabricated from rhenium metal sheet (0.018 mm thick) and is situated in the ion source of a quadrupole mass spectrometer. A particle once inside the oven is trapped and completely volatilized; this overcomes the problem of partial volatilization due to particles bouncing from the filament surface. Individual particles are thermally volatilized and ionized inside the rhenium oven, and produce discrete sodium ion pulses whose intensities are measured with the quadrupole mass spectrometer. An ion pulse width of several milliseconds (4-12 ms) is found for particles in the mass range 1.3 x 10 to the -13th to 5.4 x 10 to the -11th g. The sodium ion intensity is found to be proportional to the particle mass to the 0.86-power. The intensity distribution for monodisperse aerosol particles possesses a geometric standard deviation of 1.09, showing that the method can be used for the determination of the mass distribution function with good resolution in a polydisperse aerosol.

Sinha, M. P.↗

Heterogeneous chemical reaction of chlorine nitrate and water on sulfuric-acid surfaces at room temperature

The use of H2SO4 as a catalyst for aerosol production of chlorine compounds in the chemistry of the antarctic stratosphere was investigated in laboratory trials. The experiments involved the gas surface collision rate of a molecule on a given surface during its residence time in a Knudsen cell in molecular flow conditions. Chlorine nitrate gas was made to flow through a chamber exposed to a container holding a 95.6 pct H2SO4 solution. Gas leaving the cell was scanned with a mass spectrometer. A sticking coefficient of 0.00032 was found for the chlorine nitrate, a value five times that previously reported.

Rossi, Michel J.↗

Antarctic ozone depletion chemistry - Reactions of N2O5 with H2O and HCl on ice surfaces

In a study concerning Antarctic ozone depletion, reactions of dinitrogen pentoxide with water and hydrochloric acid were studied on ice surfaces in a Knudsen cell flow reactor. The N2O5 reacted on ice at 185 K to form condensed-phase nitric acid (HNO3). This reaction may provide a sink for odd nitrogen, NO(x), during the polar winter, a requirement in nearly all models of Antarctic ozone depletion. The reaction of N2O5 on HCl-ice surfaces at 185 K produced gaseous nitryl chloride (ClNO2) and condensed-phase HNO3 and proceeded until all of the HCl within the ice was depleted. The ClNO2 which did not react or condense on ice at 185 K, can be readily photolyzed in the Antarctic spring to form atomic chlorine for catalytic ozone destruction cycles. The other photolysis product, gaseous nitrogen dioxide may be important in the partitioning of NO(x) between gaseous and condensed phases in the Antarctic winter.

Tolbert, Margaret A.↗

Heterogeneous interactions of chlorine nitrate, hydrogen chloride, and nitric acid with sulfuric acid surfaces at stratospheric temperatures

The heterogeneous interactions of ClONO2, HCl, and HNO3 with sulfuric acid surfaces were studied using a Knudsen cell flow reactor. The surfaces studied, chosen to simulate global stratospheric particulate, were composed of 65-75 percent H2SO4 solutions at temperatures in the range -63 to -43 C. Heterogeneous loss, but not reaction, of HNO3 and HCl occurred on these surfaces; the measured sticking coefficients are reported. Chlorine nitrate reacted on the cold sulfuric acid surfaces, producing gas-phase HOCl and condensed HNO3. CLONO2 also reacted with HCl dissolved in the 65-percent H2SO4 solution at -63 C, forming gaseous Cl2. In all cases studied, the sticking and/or reaction coefficients were much larger for the 65-percent H2SO4 solution at -63 C than for the 75-percent solution at -43 C.

Tolbert, Margaret A.↗

Heterogeneous chemistry related to Antarctic ozone depletion: Reaction of ClONO2 and N2O5 on ice surfaces

Laboratory studies of heterogeneous reactions of possible importance for Antarctic ozone depletion were performed. In particular, the reactions of chlorine nitrate (ClONO2) and dinitrogen pentoxide (N2O5) were investigated on ice and HCl/ice surfaces. These reactions occur on the surfaces of polar stratospheric clouds (PSCs) over Antarctica. One reaction transforms the stable chlorine reservoir species (ClONO2 and HCl) into photochemically active chlorine in the form of HOCl and Cl2. Condensation of HNO3 in the reactions removes odd nitrogen from the stratosphere, a requirement in nearly all models of Antarctic ozone depletion. Other reactions may also be important for Antarctic ozone depletion. Like the reactions of chlorine nitrate, these reactions deplete odd nitrogen through HNO3 condensation. In addition, one reaction converts a stable chlorine reservior species (HCl) into photochemically active chlorine (ClNO2). These reactions were studied with a modified version of a Knudsen cell flow reactor.

Tolbert, Margaret A.↗

Fiber coating/matrix reactions in silicon-base ceramic matrix composites

The Knudsen cell technique and coupons of carbon coated Si3N4 and BN coated SiC were employed to study the possible reactions at the SiC/C/Si3N4 and SiC/BN/SiC interface. Carbon reacts with Si3N4 to form gaseous N2 and solid SiC. Solid SiC acts as a physical barrier to the reaction, which prevents the generation of high N2 pressure predicted from thermochemical calculations. Thus, deleterious effects of the reaction to the composite are limited. Limited reactions between BN and C-rich SiC was observed. However, the vapor pressure was so low that it is not likely to cause any interfacial instability. The predicted formation of a BN-C solid solution was not observed.

Lee, K. N.↗

Geochemical aspect of impact cratering: Studies in Vernadsky Institute

Studies of the geochemical effects of impact cratering at the Vernadsky Institute in collaboration with the Institute of Dynamics of Geospheres, Moscow State University, Leningrad State University, and some other institutions were fulfilled by several approaches. At the initial stage, three approaches were used: (1) experimental studies of high-temperature vaporization of geological materials (basalts, granites, and so on) in vacuum that was considered as a model of behavior of impact melt and vapor; (2) search of impact-induced geochemical effects in the rock from terrestrial impact craters; and (3) studies of samples of lunar regolith. The next stage of the studies included experiments on quasi-equilibrium vaporization of geological material in Knudsen cells. The results of this investigation are discussed.

Yakovlev, O. I.↗

Thermodynamics of iron-aluminum alloys at 1573 K

The activities of iron (Fe) and aluminum (Al) were measured in Fe-Al alloys at 1573 K using the ion-current-ratio technique in a high-temperature Knudsen cell mass spectrometer. The Fe-Al solutions exhibited negative deviations from ideality over the entire composition range. The activity coefficientsγ Fe, andγ A1 are given by the following equations as a function of mole fraction (x Fe,x Al): 0<χA1<0.4 ln(γ(Fe))=−4.511(±0.008)χ^(2)(A1) ln(γ(A1))=−4.462(±0.029)χ^(2)(Fe) +0.325(±0.013) 0.6<χ(A1)<1.0 ln(γ(Fe))=−4.065(±0.006)χ^(2)(A1)+0.099(±0.003) ln(γ(A1))=−4.092(±0.026)χ^(2)(Fe)+0.002(±0.001) The results showed good agreement with those obtained from previous investigations at other temperatures by extrapolation of the activity data to 1573 K.

Jacobson, Nathan S.↗

Chemical Reactions in the Processing of Mosi2 + Carbon Compacts

Hot-pressing of MoSi2 powders with carbon at high temperatures reduces the siliceous grain boundary phase in the resultant compact. The chemical reactions in this process were examined using the Knudsen cell technique. A 2.3 wt pct oxygen MoSi2 powder and a 0.59 wt pct oxygen MoSi2 powder, both with additions of 2 wt pct carbon, were examined. The reduction of the siliceous grain boundary phase was examined at 1350 K and the resultant P(SiO)/P(CO) ratios interpreted in terms of the SiO(g) and CO(g) isobars on the Si-C-O predominance diagram. The MoSi2 + carbon mixtures were then heated at the hot-pressing temperature of 2100 K. Large weight losses were observed and could be correlated with the formation of a low-melting eutectic and the formation and vaporization of SiC.

Jacobson, Nathan S.↗