Low‐Temperature Heat Capacities and Thermodynamic Functions of Some Palladium and Platinum Group Chalcogenides. II. Dichalcogenides; PtS2, PtTe2, and PdTe2

Heat capacities of platinum disulfide, platinum ditelluride, and palladium ditelluride were measured in the range 5° to 350°K. They show the normal sigmoidal temperature dependence with no evidence of transitions or other anomalies. The derived heat capacity equations were integrated. Values of Cp, S°—S0°, H°—H0°, and —(F°—H0°)/T are tabulated for selected temperatures. At 298.15°K the entropies are 17.85 cal gfw—1 °K—1 for PtS2, 28.92 cal gfw—1 °K—1 for PtTe2 and 30.25 cal gfw—1 °K—1 for PdTe2. Thermodynamic values have been estimated for other dichalcogenides and related chalcogenides of the platinum group metals.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/69847/2/JCPSA6-35-5-1670-1.pd

Thermophysical measurements on transition-metal tungstates I. Heat capacity of zinc tungstate from 5 to 550 K

Redetermination of the heat capacity of ZnWO4 after chemical removal of the ZnO phase from a previous sample has provided better values for chemical thermodynamic properties. At 298.15 K Cp, So, and -{Go(T) - Ho(0)}/T are found to be 27.44, 28.51, and 12.991 calth K-1 mol-1.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/22197/1/0000628.pd

Lars Vegard:key communicator and pioneer crystallographer

The Norwegian physicist Lars Vegard studied with William H. Bragg in Leeds and then with Wilhelm Wien in Würzburg. There, in 1912, he heard a lecture by Max Laue describing the first X-ray diffraction experiments and took accurate notes which he promptly sent to Bragg. Although now remembered mainly for his work on the physics of the aurora borealis, Vegard also did important pioneering work in three areas of crystallography. He derived chemical insight from a series of related crystal structures that he determined, Vegard's Law relates the unit-cell dimensions of mixed crystals to those of the pure components, and he determined some of the first crystal structures of gases solidified at cryogenic temperatures

Electronic, vibrational, and thermodynamic properties of ZnS (zincblende and rocksalt structure)

We have measured the specific heat of zincblende ZnS for several isotopic compositions and over a broad temperature range (3 to 1100 K). We have compared these results with calculations based on ab initio electronic band structures, performed using both LDA and GGA exchange- correlation functionals. We have compared the lattice dynamics obtained in this manner with experimental data and have calculated the one-phonon and two-phonon densities of states. We have also calculated mode Grueneisen parameters at a number of high symmetry points of the Brillouin zone. The electronic part of our calculations has been used to investigate the effect of the 3d core electrons of zinc on the spin-orbit splitting of the top valence bands. The effect of these core electrons on the band structure of the rock salt modification of ZnS is also discussed.Comment: 33pages, 16 Figures, submitted to Phys. Rev.

Peculiarities of phonon spectra and lattice heat capacity in Ir and Rh

A simple pseudopotential model is proposed, which allows the phonon spectra and temperature dependence of the lattice heat capacity of Ir and Rh be described with a high enough accuracy. A careful comparison of the calculated and experimental values of the lattice heat capacity is carried out, with the procedure of the identification of the phonon contribution to the heat capacity and determination of the characteristics (momenta) of the phonon density of states from the experimental values of the total heat capacity of metal at a constant pressure being described in detail. The results of the theoretical calculations explain, in particular, such peculiar feature of Ir and Rh, unusual for cubic metals, as a sharp (more than by a factor of 1.5) decrease in the effective Debye temperature with increasing termperature. The temperature dependence of the mean square amplitude of atomic displacements in Ir and Rh has been calculated. Basing on the band calculations the manifestation of the Kohn singularities in the phonon spectra of Ir are discussed.Comment: 15 pages, LaTeX2e, 12 figures in postscrip

Cosmic-ray strangelets in the Earth's atmosphere

If strange quark matter is stable in small lumps, we expect to find such lumps, called ``strangelets'', on Earth due to a steady flux in cosmic rays. Following recent astrophysical models, we predict the strangelet flux at the top of the atmosphere, and trace the strangelets' behavior in atmospheric chemistry and circulation. We show that several strangelet species may have large abundances in the atmosphere; that they should respond favorably to laboratory-scale preconcentration techniques; and that they present promising targets for mass spectroscopy experiments.Comment: 28 pages, 4 figures, revtex

Characterization of volatile organic compounds and submicron organic aerosol in a traffic environment

Urban air consists of a complex mixture of gaseous and particulate species from anthropogenic and biogenic sources that are further processed in the atmosphere. This study investigated the characteristics and sources of volatile organic compounds (VOCs) and submicron organic aerosol (OA) in a traffic environment in Helsinki, Finland, in late summer. The anthropogenic VOCs (aVOCs; aromatic hydrocarbons) and biogenic VOCs (bVOCs; terpenoids) relevant for secondary-organic-aerosol formation were analyzed with an online gas chromatograph mass spectrometer, whereas the composition and size distribution of submicron particles was measured with a soot particle aerosol mass spectrometer. This study showed that aVOC concentrations were significantly higher than bVOC concentrations in the traffic environment. The largest aVOC concentrations were measured for toluene (campaign average of 1630 ng m−3) and p/m xylene (campaign average of 1070 ng m−3), while the dominating bVOC was α-pinene (campaign average of 200 ng m−3). For particle-phase organics, the campaign-average OA concentration was 2.4 µg m−3. The source apportionment analysis extracted six factors for OA. Three OA factors were related to primary OA sources – traffic (24 % of OA, two OA types) and a coffee roastery (7 % of OA) – whereas the largest fraction of OA (69 %) consisted of oxygenated OA (OOA). OOA was divided into less oxidized semi-volatile OA (SV-OOA; 40 % of OA) and two types of low-volatility OA (LV-OOA; 30 %). The focus of this research was also on the oxidation potential of the measured VOCs and the association between VOCs and OA in ambient air. Production rates of the oxidized compounds (OxPR) from the VOC reactions revealed that the main local sources of the oxidation products were O3 oxidation of bVOCs (66 % of total OxPR) and OH radical oxidation of aVOCs and bVOCs (25 % of total OxPR). Overall, aVOCs produced a much smaller portion of the oxidation products (18 %) than bVOCs (82 %). In terms of OA factors, SV-OOA was likely to originate from biogenic sources since it correlated with an oxidation product of monoterpene, nopinone. LV-OOA consisted of highly oxygenated long-range or regionally transported OA that had no correlation with local oxidant concentrations as it had already spent several days in the atmosphere before reaching the measurement site. In general, the main sources were different for VOCs and OA in the traffic environment. Vehicle emissions impacted both VOC and OA concentrations. Due to the specific VOCs attributed to biogenic emissions, the influence of biogenic emissions was more clearly detected in the VOC concentrations than in OA. In contrast, the emissions from the local coffee roastery had a distinctive mass spectrum for OA, but they could not be seen in the VOC measurements due to the measurement limitations for the large VOC compounds. Long-range transport increased the OA concentration and oxidation state considerably, while its effect was observed less clearly in the VOC measurements due to the oxidation of most VOC in the atmosphere during the transport. Overall, this study revealed that in order to properly characterize the impact of different emission sources on air quality, health, and climate, it is of importance to describe both gaseous and particulate emissions and understand how they interact as well as their phase transfers in the atmosphere during the aging process.</p

Positive feedback mechanism between biogenic volatile organic compounds and the methane lifetime in future climates

A multitude of biogeochemical feedback mechanisms govern the climate sensitivity of Earth in response to radiation balance perturbations. One feedback mechanism, which remained missing from most current Earth System Models applied to predict future climate change in IPCC AR6, is the impact of higher temperatures on the emissions of biogenic volatile organic compounds (BVOCs), and their subsequent effects on the hydroxyl radical (OH) concentrations. OH, in turn, is the main sink term for many gaseous compounds including methane, which is the second most important human-influenced greenhouse gas in terms of climate forcing. In this study, we investigate the impact of this feedback mechanism by applying two models, a one-dimensional chemistry-transport model, and a global chemistry-transport model. The results indicate that in a 6 K temperature increase scenario, the BVOC-OH-CH4 feedback increases the lifetime of methane by 11.4% locally over the boreal region when the temperature rise only affects chemical reaction rates, and not both, chemistry and BVOC emissions. This would lead to a local increase in radiative forcing through methane (Delta RFCH4) of approximately 0.013 Wm(-2) per year, which is 2.1% of the current Delta RFCH4. In the whole Northern hemisphere, we predict an increase in the concentration of methane by 0.024% per year comparing simulations with temperature increase only in the chemistry or temperature increase in chemistry and BVOC emissions. This equals approximately 7% of the annual growth rate of methane during the years 2008-2017 (6.6 +/- 0.3 ppb yr-1) and leads to an Delta RFCH4 of 1.9 mWm(-2) per year.Peer reviewe

Taxonomy, ecology and distribution of Juniperus Oxycedrus L. Group in the mediterranean basin using bioclimatic, phytochemical and morphometric approaches, with special reference to the Iberian Peninsula

Several studies have been conducted in the past to clarify various aspects of species in the genus Juniperus L. One critical group is Juniperus oxycedrus L., especially from the taxonomical point of view. For this reason, we have studied the ecology, taxonomy and distribution of the taxa in the J. oxycedrus group. From an ecological and distribution standpoint, in this work we use the ombroedaphoxeric index (Ioex) to explain the presence of Juniperus populations in ombrotypes that are not optimum for these taxa. The controversy over the taxonomy of J. oxycedrus subsp. badia (H. Gay) Debeaux and J. oxycedrus subsp. lagunae (Pau ex C. Vicioso) Rivas Mart. is clarified, and it is accepted as a valid name, J. oxycedrus subsp. badia. The phytochemical differences in essential oils (EO) are addressed and their similarities analyzed; greater similarities are observed between oxycedrus and badia, and between navicularis Gand. and macrocarpa (Sm.) Ball. species. The phytochemical, molecular and distribution differences allow J. oxycedrus subsp. macrocarpa (Sm.) Ball and J. navicularis Gand. to be maintained as species. The results obtained make it possible to establish the rank to which the taxa belong and allow clear discrimination between species in groups that are difficult to interpret. Ecological, bioclimatic, phytochemical and morphometric similarities allow us to subordinate the subsp. macrocarpa to the species J. navicularis.info:eu-repo/semantics/publishedVersio

Chemistry of new particle formation and growth events during wintertime in suburban area of Beijing : Insights from highly polluted atmosphere

The high frequency of new particle formation (NPF) events observed under polluted atmospheric conditions is still poorly understood. To improve our understanding of NPF and its effects, the particle number size distribution (3-1000 nm) and submicron particle chemical composition were measured from 4 November 2017 to 17 January 2018 in suburban Beijing. During this intense campaign, 22 NPF events were identified with a frequency of 29%, including 11 cases that occurred under "clean" conditions (C-NPF) and 11 cases that occurred under "polluted" conditions (P-NPF). The observed formation rate (J(3)) and condensation sink were 4.6-148.9 cm(-3).s(-1) and 0.01-0.07 s(-1), and the majority of NPF events occurred when the condensation sink (CS) values below 0.03 s(-1), indicating that condensation vapor likely constitutes the critical limiting factor for NPF events. The correlations between log J(3) and [H2SO4] that close to previous CLOUD experimental results in the majority of NPF events (68%) suggest the high nucleation rates (up to 100 cm(-3).s(-1)) would be attributed by the amines that enhancing sulfuric acid nucleation, while the reminding cases (32%) possibly attributed to the H2SO4-NH3 clustering mechanism, which is supported by the theoretical expectations for H2SO4 nucleation with NH3 simulated by the MALTE_BOX model. The observed growth rate varied from 4.9 to 37.0 mm.h(-1), with the dominant contribution (>60%) from sulfuric acid during the early phases of growth (similar to 4 nm), which was also sufficient to explain the observed Q(GR) for 50 nm)Peer reviewe