Vapor phase composition as an indicator of thermal stability of the Sm, Eu, and Yb chlorides

The Sm, Eu, and Yb tri- and dichlorides were investigated by Knudsen effusion mass spectrometry. It was found out by the analysis of mass spectra and ionization efficiency curves that the vapor composition is complex due to the partial high temperature decomposition/disproportionation of the samples. Up to five vapor species were identified for both LnCl3 (LnCl3, LnCl2, Ln2Cl4, Ln2Cl5, and Ln2Cl6) and LnCl2 (LnCl3, LnCl2, LnCl, Ln, and Ln2Cl4). The quantitative evaluation of vapor composition was made. It indicates that the disproportionation of SmCl2 and EuCl2 is negligible in the temperature range studied whereas that of YbCl2 and the decomposition of SmCl3 and YbCl3 cannot be neglected.

Excited state properties of formamide in water solution: An ab initio study

We present ab initio quantum calculation of the optical properties of formamide in vapor phase and in water solution. We employ time dependent density functional theory for the isolated molecule and many-body perturbation theory methods for the system in solution. An average over several molecular dynamics snapshots is performed to take into account the disorder of the liquid. We find that the excited stateproperties of the gas-phase formamide are strongly modified by the presence of the water solvent: the geometry of the molecule is distorted and the electronic and optical properties are severely modified. The important interaction among the formamide and the water molecules forces us to use fully quantum methods for the calculation of the excited stateproperties of this system. The excitonic wave function is localized both on the solute and on part of the solvent.

Water–montmorillonite systems: Neutron scattering and tracer throughdiffusion studies

Designs for deep geological respositories of nuclear waste include bentonite as a hydraulic and chemisorption buffer material to protect the biosphere from leakage of radionuclides. Bentonite is chosen because it is a cheap, naturally occurring material with the required properties. It consists essentially of montmorillonite, a swelling clay mineral. Upon contact with groundwater such clays can seal the repository by incorporating water in the interlayers of their crystalline structure. The intercalated water exhibits significantly different properties to bulk water in the surrounding interparticle pores, such as lower diffusion coefficients (González Sánchez et. al. 2008). This doctoral thesis presents water distribution and diffusion behavior on various time and space scales in montmorillonite. Experimental results are presented for Na- and Cs-montmorillonite samples with a range of bulk dry densities (0.8 to 1.7 g/cm3). The experimental methods employed were neutron scattering (backscattering, diffraction, time-of-flight), adsorption measurements (water, nitrogen) and tracer-through diffusion. For the tracer experiments the samples were fully saturated via the liquid phase under volume-constrained conditions. In contrast, for the neutron scattering experiments, the samples were hydrated via the vapor phase and subsequently compacted, leaving a significant fraction of interparticle pores unfilled with water. Owing to these differences in saturation, the water contents of the samples for neutron scattering were characterized by gravimetry whereas those for the tracer experiments were obtained from the bulk dry density. The amount of surface water in interlayer pores could be successfully discriminated from the amount of bulk-like water in interparticle pores in Na- and Csmontmorillonite using neutron spectroscopy. For the first time in the literature, the distribution of water between these two pore environments was deciphered as a function of gravimetric water content. The amount was compared to a geometrical estimation of the amount of interlayer and interparticle water determined by neutron diffraction and adsorption measurements. The relative abundances of the 1 to 4 molecular water layers in the interlayer were determined from the area ratios of the (001)-diffraction peaks. Depending on the characterization method, different fractions of surface water and interlayer water were obtained. Only surface and interlayer water exists in amontmorillonite with water contents up to 0.18 g/g according to spectroscopic measurements and up to 0.32 g/g according to geometrical estimations, respectively. At higher water contents, bulk-like and interparticle water also exists. The amounts increase monotonically, but not linearly, from zero to 0.33 g/g for bulk-like water and to 0.43 g/g for interparticle water. It was found that water most likely redistributes between the surface and interlayer sites during the spectroscopic measurements and therefore the reported fraction is relevant only below about -10 ºC (Anderson, 1967). The redistribution effect can explain the discrepancy in fractions between the methods. In a novel approach the fractions of water in different pore environments were treated as a fixed parameter to derive local diffusion coefficients for water from quasielastic neutron scattering data, in particular for samples with high water contents. Local diffusion coefficients were obtained for the 1 to 4 molecular water layers in the interlayer of 0.5·10–9, 0.9·10–9, 1.5·10–9 and 1.4·10–9 m²/s, respectively, taking account of the different water fractions (molecular water layer, bulk-like water). The diffusive transport of 22Na and HTO through Na-montmorillonite was measured on the laboratory experimental scale (i.e. cm, days) by tracer through-diffusion experiments. We confirmed that diffusion of HTO is independent of the ionic strength of the external solution in contact with the clay sample but dependent on the bulk dry density. In contrast, the diffusion of 22Na was found to depend on both the ionic strength of the pore solution and on the bulk dry density. The ratio of the pore and surface diffusion could be experimentally determined for 22Na from the dependence of the diffusion coefficient on the ionic strength. Activation energies were derived from the temperaturedependent diffusion coefficients via the Arrhenius relation. In samples with high bulk dry density the activation energies are slightly higher than those of bulk water whereas in low density samples they are lower. The activation energies as a function of ionic strengths of the pore solutions are similar for 22Na and HTO. The facts that (i) the slope of the logarithmic effective diffusion coefficients as a function of the logarithmic ionic strength is less than unity for low bulk dry densities and (ii) two water populations can be observed for high gravimetric water contents (low bulk dry densities) support the interlayer and interparticle porosity model proposed by Glaus et al. (2007), Bourg et al. (2006, 2007) and Gimmi and Kosakowski (2011).

The isotopic composition of pore-water from Tournemire argillite (France): An inter-comparison study.

The determination of stable isotope contents of pore-water from consolidated argillaceous rocks remains a critical issue. In order to understand the processes involved in techniques developed for acquiring stable isotope compositions of pore-water, a comparative study between different methods was based on core samples of the Tournemire argillite. It concerns two water extraction techniques based on vacuum distillation and two pore-water equilibration techniques (radial diffusion in liquid phase and diffusive exchange in vapor phase). The water-content values obtained from vacuum distillation at 50 °C are always the lowest, on average 8% lower than the values obtained by heating at 105 °C and 17% lower than the values obtained by heating at 150 °C. The amounts of pore-water estimated from vacuum distillation at 105 °C and 150 °C and from radial diffusion method are in good agreement with those determined by heating. On the contrary, the vapor exchange method provides the highest values of water contents. Concerning stable isotope data, a good agreement was found between those obtained by equilibration techniques and those of fracture water, especially for 2H. Vacuum distillation at high temperature (particularly at 150 °C) also provided results consistent with data of fracture fluids. On the other hand, distillation at 50 °C provides a systematic depletion in heavy isotopes (about –20‰ for 2H and –2.7‰ for 18O) that can be modelled by an incomplete Rayleigh-type distillation process.

Diurnal variations in middle-atmospheric water vapor by ground-based microwave radiometry

Abstract. In this paper, we compare the diurnal variations in middle-atmospheric water vapor as measured by two ground-based microwave radiometers in the Alpine region near Bern, Switzerland. The observational data set is also compared to data from the chemistry–climate model WACCM. Due to the small diurnal variations of usually less than 1%, averages over extended time periods are required. Therefore, two time periods of five months each, December to April and June to October, were taken for the comparison. The diurnal variations from the observational data agree well with each other in amplitude and phase. The linear correlation coefficients range from 0.8 in the upper stratosphere to 0.5 in the upper mesosphere. The observed diurnal variability is significant at all pressure levels within the sensitivity of the instruments. Comparing our observations with WACCM, we find that the agreement of the phase of the diurnal cycle between observations and model is better from December to April than from June to October. The amplitudes of the diurnal variations for both time periods increase with altitude in WACCM, but remain approximately constant at 0.05 ppm in the observations. The WACCM data are used to separate the processes that lead to diurnal variations in middle-atmospheric water vapor above Bern. The dominating processes were found to be meridional advection below 0.1 hPa, vertical advection between 0.1 and 0.02 hPa and (photo-)chemistry above 0.02 hPa. The contribution of zonal advection is small. The highest diurnal variations in water vapor as seen in the WACCM data are found in the mesopause region during the time period from June to October with diurnal amplitudes of 0.2 ppm (approximately 5% in relative units).

Vapor deposition coating of fused silica tubes with amorphous selenium

A set of optimized deposition conditions for the inner wall coating of fused silica tubes with amorphous selenium was elaborated. The method is based on the vapor transport deposition of pure elemental selenium on a cooled substrate held at liquid nitrogen temperatures. Morphological and structural examination of the deposited layer was performed by optical microscopy and X-ray diffraction studies. Neutron activated selenium was used to monitor the deposition pattern and its stability under high gas flows. Monte Carlo simulations allowed the estimation of the different Se species composing the amorphous phase, at the given experimental deposition conditions. The versatility of the coating method presented in this work allows for the coating of tubes of different lengths and diameters, opening the way for several applications of amorphous selenium films in various fields.

Variability of mesospheric water vapor above Bern in relation to the 27-day solar rotation cycle

Many studies investigated solar–terrestrial responses (thermal state, O₃ , OH, H₂O) with emphasis on the tropical upper atmosphere. In this paper the Focus is switched to water vapor in the mesosphere at a mid-latitudinal location. Eight years of water vapor profile measurements above Bern (46.88°N/7.46°E) are investigated to study oscillations with the Focus on periods between 10 and 50 days. Different spectral analyses revealed prominent features in the 27-day oscillation band, which are enhanced in the upper mesosphere (above 0.1 hPa, ∼64 km) during the rising sun spot activity of solar cycle 24. Local as well as zonal mean Aura MLS observations Support these results by showing a similar behavior. The relationship between mesospheric water and the solar Lyman-α flux is studied by comparing thesi-milarity of their temporal oscillations. The H₂O oscillation is negatively correlated to solar Lyman-α oscillation with a correlation coefficient of up to −0.3 to −0.4, and the Phase lag is 6–10 days at 0.04 hPa. The confidence level of the correlation is ≥99%. This finding supports the assumption that the 27-day oscillation in Lyman-α causes a periodical photo dissociation loss in mesospheric water. Wavelet power spectra, cross-wavelet transform and wavelet coherence analysis (WTC)complete our study. More periods of high common wavelet power of H₂O and solar Lyman-α are present when amplitudes of the Lyman-α flux increase. Since this is not a measure of physical correlation a more detailed view on WTC is necessary, where significant (two sigma level)correlations occur intermittently in the 27 and 13-day band with variable Phase lock behavior. Large Lyman-α oscillations appeared after the solar super storm in July 2012 and the H₂O oscillations show a well pronounced anticorrelation. The competition between advective transport and photo dissociation loss of mesospheric water vapor may explain the sometimes variable Phase relationship of mesospheric H₂O and solar Lyman-α oscillations. Generally, the WTC analysis indicates that solar variability causes observable photochemical and dynamical processes in the mid-latitude mesosphere.