Equilibrium properties of dense hydrogen isotope gases based on the theory of simple fluids

We present a new method for the prediction of the equilibrium properties of dense gases containing hydrogen isotopes. The proposed approach combines the Feynman-Hibbs effective potential method and a deconvolution scheme introduced by Weeks et al. The resulting equations of state and the chemical potentials as functions of pressure for each of the hydrogen isotope gases depend on a single set of Lennard-Jones parameters. In addition to its simplicity, the proposed method with optimized Lennard-Jones potential parameters accurately describes the equilibrium properties of hydrogen isotope fluids in the regime of moderate temperatures and pressures. The present approach should find applications in the nonlocal density functional theory of inhomogeneous quantum fluids and should also be of particular relevance to hydrogen (clean energy) storage and to the separation of quantum isotopes by novel nanomaterials.     

Dihydrogen carrier gases in gas-solid chromatography. Study of hydrogen weight and nuclear spin isomer adsorption

Summary A new version of gas-solid chromatography (GSC) of hydrogen isotopes and spin isomers which makes use of the adsorbable dihydrogen carrier gases (H₂, HD and D₂) is described. Major advantages of the new technique in comparison with conventional GSC with inert carrier gases are discussed. The new version of GSC was found to be a powerful tool for acquisition of the data necessary to design adsorption systems to separate hydrogen isotopes.     

Cryogenic Preconcentration of Hydrogen, Argon, Oxygen, and Nitrogen in the Gas Chromatographic Determination of Their Impurities in Volatile Inorganic Hydrides

A procedure is proposed for the cryogenic preconcentration of hydrogen, argon, oxygen, and nitrogen in the gas chromatographic determination of their impurities in volatile inorganic hydrides. It is shown that the recovery of impurity gases approaches 100%. The limits of determination of impurity gases in hydrides with the use of the proposed procedure and a helium ionization detector are 2 × 10^–6–3 × 10^–5mol %, which is 5–100 times lower than the results published previously. The results are given for the determination of hydrogen, argon, oxygen, and nitrogen in silane, germane, arsine, phosphine, hydrogen sulfide, hydrogen selenide, and ammonia samples.     

Experimental studies on the hydrogen isotope recovery using low-pressure palladium membrane diffuser

In this paper, we introduce a set of low-pressure palladium membrane diffuser designed to recover hydrogen isotopes from inert mixture gases. Several gaseous mixtures (D₂/Ar and D₂/He) with different deuterium concentration have been used for cleanup test of the low-pressure palladium membrane diffuser at 723 K. Effect of the composition of feed gas on the pressure of permeate side has been observed by gas chromatography (GC) and pressure sensor. With the feed flow rate of the mixture gases increasing, the D₂ permeate pressure is increasing as well. Decontamination factor (DF) of more than 1000 and recovery efficiency greater than 99.9% have been obtained by controlling the feed gas flow rate. The same palladium membrane diffuser was used to process helium-3 gas with more than 10% hydrogen isotope and about 0.3% tritium gas. The pure helium-3 (above 99.4%) with low content of hydrogen isotopes (about 0.084%) has been obtained. Recovery efficiency of all hydrogen isotopes is 99.5% above.     

Spektralanalytische Spurenbestimmung in hochreinen Silberhalogeniden unter Verwendung spezieller Auswerteverfahren

A method is given for the quantitative determination of trace elements in silver halides by spectral analysis down to concentrations of 0.01 ppm. A method of evaluation is described, which allows to use reference lines of different wave-lengths and density curves. For a rough estimation or in the case of low impurity concentrations two other methods are used taking the background as reference value.     

Reference materials for marine science

Summary The second edition of the catalog of reference materials suited for use in marine science, originally compiled in 1986 for NOAA, IOC and UNEP, has been recently completed. The catalog lists more than 900 reference materials from thirteen producers and contains information about their proper use, sources, availability, and analyte concentrations. The reference material matrices include ashes, airborne particulate matter, gases, oils, rocks and sediments, sludges, tissues and waters. Reference materials used for the evaluation of instruments and the determination of sample physical properties are also included. Indices are available for elements, isotopes and organic compounds, as are cross references to CAS registry numbers, and alternate names and chemical structures of selected organic compounds.     

Development of radiochemical analysis of uranium isotopes in highly contaminated soil samples

An accurate and reliable analytical technique of uranium isotopes in highly contaminated soil samples was developed and applied to the IAEA reference samples. The conventional TBP method of uranium isotopes is insufficient to completely purify uranium from actinides such as plutonium and americium isotopes in highly contaminated soil samples. For overcoming the demerits of the conventional TBP extraction method, sample materials were decomposed with HNO₃ and HF, and uranium isotopes were purified by TBP extraction and anion exchange columns and extraction chromatography. Among the purifying methods of uranium, with a TRU Spec resin column after TBP solvent extraction, uranium was completely separated from the radionuclides in a highly contaminated samples. With the modified TBP extraction method, it was found that the concentrations of uranium isotopes were consistent with the reference values reported by the IAEA.     

Determination of oxygen in certain gases : Improved winkler method

An improved method is described for the determination of micro-amounts of oxygen gas in argon, carbon dioxide, helium, hydrogen and nitrogen by the Winkler. procedure. The technique is such that a mean standard deviation of ± 0.33 ppm oxygen with a reproducibility of ± 0.67 is obtained for gases varying in oxygen content from 1 to 30 ppm. The results are reproducible on a day-to-day basis. The reagent blank is equivalent to about 2.5 ppm with a deviation of 0.2 ppm. The method can be used for oxygen gas determination from 1 to 1.50 ppm. The accuracy of the method is ± 0.1 ppm for the lower range of oxygen concentrations.The method may also be extended to higher oxygen-containing gases, except that the oxygen determination is made by titration and smaller gas samples are used.     

Radiochemical analysis of uranium isotopes in soil and sediment samples with extraction chromatography

An accurate and simple analytical technique for uranium isotopes in highly contaminated soil samples was developed and validated by application to IAEA-Reference samples and environmental samples. For overcoming the demerits of the TBP extraction method, sample materials were decomposited with HNO(3) and HF and uranium isotopes were purified with an anion exchange resin and a TRU Spec resin. With the extraction chromatography method, hindrance elements were completely removed from the uranium fraction. The chemical yields with the extraction chromatography method were <10% higher than those with the TBP extraction method. The concentrations of uranium isotopes using the extraction chromatography method were consistent with the reference values reported by the IAEA.     

High-temperature elemental analysis and pyrolysis techniques for stable isotope analysis

A universal method for pyrolysis and elemental analysis, suitable for the online determination of deuterium, carbon, nitrogen and oxygen isotopes for organic and inorganic substances, is presented. The samples are pyrolytically decomposed in a high-temperature pyrolysis (HTP) system, at a temperature exceeding 1400 degrees C, in the presence of reactive carbon. The method is suitable for the analysis of stable isotope ratios from hydrogen, carbon, nitrogen and oxygen. The instrumentation and experimental procedure are simple and cost-effective. The reproducibility of the delta values for D/H is better than 3 per thousand, and for (18)O, (13)C (organic) and (15)N (inorganic) it is approximately 0.2 per thousand. The HTP system is suitable for solid and liquid samples and can use an autosampler for the samples. Results are presented for the isotopic composition of international reference materials and selected laboratory reference materials, which demonstrate the precision and accuracy of the method. Possible problems in the measurement of nitrates and their solutions are particularly discussed. The analyses of oxygen isotopes in selected geological samples (carbonates, silicate, biotite) are demonstrated.     

Isotopic processes in atmospheric chemistry

Trace gases are responsible for the atmospheric processes underlying air pollution and global change. Analysis of the distribution of stable isotopes in these gases is a way of gaining additional knowledge that may not otherwise be available. This approach requires knowledge of the isotopic signature of emissions sources and chemical reactions. This review focuses on the chemical physics of the processes underlying the distribution of stable isotopes in atmospheric gases.     

Evaluation of the analytical performance of inductively coupled plasma mass spectrometry for the simultaneous determination of major and minor elements in basic slags

The application of inductively coupled plasma mass spectrometry to the analysis of basic slags has been studied. A conventional dissolution-fusion procedure and a microwave digestion system were used for sample dissolution. Suitable selection of the analyte isotopes and the use of appropriate instrument settings and of internal standardization makes it possible to determine the major and minor elements in the same test sample dilution. Use of the omnirange device and low-abundance isotopes for the determination of the major elements is evaluated. The influence of the attack reagents is tested and the interferences caused by polyatomic ions are studied and corrected by applying elementary mathematical equations. For the major and minor elements considered, precision was found to be better than 1% (RSD). Results are presented for three basic slag reference materials and the agreement between the certified and found values shows the capacity of the method accurately to determine elemental concentrations in basic slags.     

Surface analytical investigation of the tritium getter ZrCO after exposure to various gases

ZrCo is a hydride forming material frequently investigated and proposed for storage and handling of hydrogen isotopes. It is of special interest for deuterium and tritium storage needed for the operation of a nuclear fusion reactor. An interaction of ZrCo powder with contaminant gases particularly during the thermal release of the hydrogen isotopes from the hydride at temperatures above 300 °C was found to cause a reduction of the reactivity of the powder. Consequently, a serious decrease of the hydrogen storage capacity occurs. From surface analytical investigations of ZrCo after exposure to the contaminant gases CO, CO₂, O₂, N₂, CH₄, and C₂H₄ it was concluded that CH₄, C₂H₄, O₂, or N₂ react predominantly with Zr, the principal hydride forming alloy component, to carbide, nitride, and/or oxide. The resulting decrease of the storage capacity is possibly due to either a reduction in the amount of unreacted Zr available for the formation of Zr hydrides or to a formation of a thick protective overlayer. CO or CO₂, which react mainly with the Co component but with Zr in surface near layers only, cause a less pronounced decrease in storage capacity.     

A photoplate calibration technique applied to the determination of hafnium in zirconium by SSMS

A photoplate calibration procedure is suggested for spark source mass spectrometry /SSMS/ with photoplate detection. The technique uses the Churchill two-line method applied to the two stable isotopes of copper. The calibration curve thus obtained is split into fragments and each fragment is approximated by a polynomial. The method was applied for the quantitative determination of Hf as impurity in zirconium sponge obtained from a pilot plant dedicated to the depletion of the hafnium content in zirconium by fractional crystallization.     

Uncertainty propagation through correction methodology for the determination of rare earth elements by quadrupole based inductively coupled plasma mass spectrometry

Determination of rare earth elements by quadrupole based inductively coupled plasma mass spectrometry (ICP-QMS) shows several spectroscopic overlaps from M⁺, MO⁺ and MOH⁺ ions. Especially, the spectroscopic interferences are observed from the atomic and molecular species of lighter rare earth elements including Ba during the determination of Eu, Gd and Tb. Mathematical correction methods, knowing the at.% abundances of different interfering isotopes, and the extent of formation of molecular species determined experimentally, have been used to account for various spectroscopic interferences. However, the uncertainty propagated through the mathematical correction limits its applicability. The uncertainty propagation increases with the increase in contribution from interfering species. However, for the same extent of total contribution, the overall error decreases when the interfering species are more than one. In this work, chondrite as well as a few geological reference materials containing different proportions of various rare earth elements have been used to study the contributions of different interfering species and the corresponding uncertainty in determining the concentrations of rare earth elements. A number of high abundant isotopes are proposed for determining the concentrations of various rare earth elements. The proposed isotopes are tested experimentally for determining the concentrations of different rare earth elements in two USGS reference materials AGV-1 and G-2. The interferences over those isotopes are corrected mathematically and the uncertainties propagated due to correction methodology are determined for those isotopes. The uncertainties in the determined concentrations of rare earth elements due to interference correction using the proposed isotopes are found to be comparable with those obtained by the commonly used isotopes for various rare earth elements.     

A pyrolysis/gas chromatographic method for the determination of hydrogen in solid samples

A method is described for the determination of hydrogen in solid samples. The sample is heated under vacuum after which the evolved gases are separated by gas chromatography with a helium ionization detector. The system is calibrated by injecting known amounts of hydrogen, as determined manometrically. The method, which is rapid and reliable, was checked for a variety of lunar soils; the limit of detection is about 10 ng of hydrogen.     

Stability test and improvement of hydrogen analyzer with trace reduction detector

We previously developed an analyzer able to detect hydrogen concentrations of less than 50 cm3/1000 m3. The analyzer uses a carrier gas purifier and a low temperature separation column to remove impurities preventing measurement of low concentrations from the carrier and sample gases. It uses a trace reduction detector with a mercuric oxide bed to detect the concentration of hydrogen based on the reduction reaction of mercuric oxide with hydrogen. We have now evaluated the performance of the analyzer by carrying out a series of tests that measured the spectrum peak and the retention time. We used three sample gases with hydrogen concentrations of 5, 20, and 50 cm3/1000 m3 in nitrogen dilution gas. The measured peak was stable (it was within a relative standard deviation of less than 10%), and there was a linear relationship between the peak and hydrogen concentration. However, the retention time gradually shortened as the measurements were repeated. The shortening was reduced by warming the low temperature separation column used in the analyzer; it was not observed when we used a hydrogen sample gas diluted by helium instead of nitrogen. Using nitrogen as a dilution gas apparently shortens the retention time. We thus added an MS-5A separation column and a thermal conductivity detector. The nitrogen and hydrogen in the sample/carrier gas are separated, and the nitrogen is efficiently removed by switching the pass line to a release line after the hydrogen has been sent to the low temperature separation column. An analyzer using this "after-cut method" was able to stably measure infinitesimal hydrogen concentrations and was not affected by nitrogen in the sample gas.     

Complexation versus aggregation of indoles in glassy hydrocarbons

It is shown, on the basis of recent data on the aggregation phenomenon and of spectroscopic considerations, that alterations of the indole absorption and fluorescence spectra in glassy hydrocarbons at low temperatures and low concentrations are not due to a previously alleged aggregation. It is an impurity, probably water, which causes the solute complexation. This phenomenon can occur with many proton-donor solutes that are able to form a hydrogen bond with the impurity.     

Measurement of As,P, and S in the waste gases and water emitted from semiconductor processes by high-temperature hydrogen reduction gas chromatography

A quick, sensitive, and accurate method, high-temperature hydrogen reduction gas chromatography (GC) (1,2), for measuring arsenic (As), phosphorus (P), and sulfur (S) in the waste gases and water emitted from semiconductor processes is proposed in this paper. A high-temperature hydrogen reduction system that changes As, P, S, and their compounds into hydrides by atomic hydrogen has been designed. It is convenient to detect these elements in solid, liquid, and gaseous samples by high-temperature hydrogen reduction GC without pretreating samples. The lower detection limits of As, P, and S by this method are 0.01, 0.003, 0.02 mg/L, respectively, and the values of relative standard deviation are 6.2%, 8.6%, and 0.3%, respectively. Results determined by high-temperature hydrogen reduction GC are primarily accordant to those by conventional methods such as colorimetry and ion chromatography. The error statistics of this analysis method also show that high-temperature hydrogen reduction GC can be successfully used to determine trace As, P, and S in waste gases and wastewater emitted from semiconductor processes.     

A multidimensional gas chromatography method for the analysis of hydrogen sulfide in crude oil and crude oil headspace

Two‐dimensional heart‐cutting gas chromatography is used to analyze dissolved hydrogen sulfide in crude samples. Liquid samples are separated first on an HP‐PONA column, and the light sulfur gases are heart‐cut to a GasPro column, where hydrogen sulfide is separated from other light sulfur gases and detected with a sulfur chemiluminescence detector. Heart‐cutting is accomplished with the use of a Deans switch. Backflushing the columns after hydrogen sulfide detection eliminates any problems caused by high‐boiling hydrocarbons in the samples. Dissolved hydrogen sulfide is quantified in 14 crude oil samples, and the results are shown in this work. The method is also applicable to the analysis of headspace hydrogen sulfide over crude oil samples. Gas hydrogen sulfide measurements are compared to liquid hydrogen sulfide measurements for the same sample set. The chromatographic system design is discussed, and chromatograms of representative gas and liquid measurements are shown.