Thermodynamics and the intrinsic stability of lead halide perovskites CH3NH3PbX3

The role of thermodynamics in assessing the intrinsic instability of the CH3NH3PbX3 perovskites (X = Cl,Br,I) is outlined on the basis of the available experimental information. Possible decomposition/degradation pathways driven by the inherent instability of the material are considered. The decomposition to precursors CH3NH3X(s) and PbX2(s) is first analysed, pointing out the importance of both the enthalpic and the entropic factor, the latter playing a stabilizing role making the stability higher than often asserted. For CH3NH3PbI3 the disagreement between the available calorimetric results makes the stability prediction uncertain. Subsequently, the gas-releasing decomposition paths are discussed, with emphasis on the discrepant results presently available, probably reflecting the predominance of thermodynamic or kinetic control. The competition between the formation of NH3(g)+CH3X(g), CH3NH2(g)+HX(g) or CH3NH3X(g) is analysed, in comparison with the thermal decomposition of methylammonium halides. In view of the scarce and inconclusive thermodynamic studies to-date available, the need for further experimental data is emphasized

Changes in the architecture of fluvial deposits in the Paganzo Basin (Upper Paleozoic of San Juan province) : an example of sea level and climatic controls on the development of coastal fluvial environments

Paganzo Group exposures (Tupe Formation) in the Huaco area provide an excellent opportunity for assessing the role of sea level and climatic changes on the morphology and nature of coastal fluvial systems deposited in areas of limited tectonic activity. The paleogeographic position of Huaco, close to a coastal region within the Paganzo Basin, allows identification of the effects of sea level change on fluvial architecture. Despite the fact that the Huaco area was dominated by coastal fluvial systems, three marine incursions flooded this part of the basin during the Namurian, Early Pennsylvanian and Late Pennsylvanian respectively. During deposition of the Paganzo Group, climatic conditions evolved from glacial (Namurian) to hot and dry (Late Cisuralian). Five types of fluvial deposits were recognized on the basis of architectural element analysis, lithofacies distribution and type of fluvial bounding surfaces present. Fluvial system 1 (FS1) constitutes the lower part of the Tupe Formation and consists of stacked multi-storey channel-fill complexes formed on large braided alluvial plains dominated by channel-avulsion processes. FS2 consists of multi-storey channels alternating with floodplain deposits including coal beds and organic-rich mudstones. This fluvial system is interpreted as the deposit of an anastomosed network of sandy channels. FS3 occurs between the Early Pennsylvanian and Late Pennsylvanian marine transgressions and consists of sandstones and some conglomerates that form stacked channel complexes. Sporadically, very fine-grained sandstone and mudstone floodplain deposits appear as thin intercalations. FS3 likely formed on braided alluvial plains with channels dominated by transversal bars. FS 4 corresponds to an anastomosed fluvial system that was dominated by two types of braided channel belts that were separated by narrow floodplains. Finally, FS5 is composed of fining-upward cycles ranging from gravely sandstones at the bottom of channels to muddy floodplain deposits at the top. The whole FS5 succession was deposited by high-sinuosity meandering rivers. Detailed stratigraphic analyses clearly suggest that both, sea level and climate changes were first-order controls on fluvial system configurations. In this way, braided systems belonging to FS1 correspond to a low-accommodation system tract. Whereas, coal beds of FS2, which resulted from high water-tables, correspond to a high accommodation system tract that was likely associated with advanced stages of the Late Pennsylvanian transgression. A significant change in the nature of fluvial deposits took place prior to the Late Pennsylvanian sea level rise when braided fluvial systems (FS3) with very scarce floodplain deposits prevailed. Towards the top of the Late Pennsylvanian transgressive deposits, a high relief fluvial incision surface was carved into the underlying marine deposits. This surface was later mantled by anastomosed rivers (FS4) corresponding to low-accommodation deposits formed in a lowstand or during the early stages of the ensuing sea level rise. In later phases of this transgression, high accommodation conditions prevailed and fluvial sedimentation was dominated by high-sinuosity rivers (FS5). These fluvial deposits are considered as an inland equivalent to the shallow-marine deposits exposed in the neighboring Agua Negra Formation located to the west

The Dissociation Energy of the New Diatomic Molecules SiPb and GePb

The diatomic molecules SiPb and GePb were for the first time identified by producing high temperature vapors of the constituent pure elements in a double-oven-like molecular-effusion assembly. The partial pressures of the atomic, heteronuclear, and homonuclear gaseous species observed in the vapor, namely, Si, Ge, Pb, SiPb, GePb, Pb2, Gen, and Sin (n=2-3), were mass-spectrometrically measured in the overall temperature ranges 1753-1961 K (Ge-Pb) and 1992-2314 K (Si-Pb). The dissociation energies of the new species were determined by second- and third-law analyses of both the direct dissociation reactions and isomolecular exchange reactions involving homonuclear molecules. The selected values of the dissociation energies at 0 K (D0 degrees) are 165.1+/-7.3 and 141.6+/-6.9 kJ/mol, respectively, for SiPb and GePb, and the corresponding enthalpies of formation (DeltafH0 degrees) are 476.4+/-7.3 and 419.3+/-6.9 kJ/mol. The ionization efficiency curves of the two species were measured, giving the following values for the first ionization energies: 7.0+/-0.2 eV (SiPb) and 7.1+/-0.2 eV (GePb). A computational study of the species SiPb and GePb was also carried out at the CCSD(T) level of theory using the relativistic electron core potential approach. Molecular parameters, adiabatic ionization energies, adiabatic electron affinities, and dissociation energies of the title species were calculated, as well as the enthalpy changes of the exchange reactions involving the other Pb-containing diatomics of group 14. Finally, a comparison between the experimental and theoretical results is presented, and from a semiempirical correlation the unknown dissociation energies of the SiSn and PbC molecules are predicted as 234+/-7 and 185+/-11 kJ/mol, respectively

Evaporation/decomposition behavior of 1-Butyl-3-Methylimidazolium Chloride (BMImCL) investigated through effusion and thermal analysis techniques

The evaporation/decomposition behavior of the ionic liquid 1-butyl-3-methylimidazolium chloride (BMImCl) was studied with various techniques, such as thermogravimetry (TG), Knudsen effusion mass loss (KEML), and Knudsen effusion mass spectrometry (KEMS), in order to investigate the competition between the simple evaporation of the liquid as gaseous ion pairs (NIP: neutral ion pair) and the thermal decomposition releasing volatile species. TG/DSC experiments were carried out from 293 to 823 K under both He and N2 flowing atmospheres on BMImCl as well as on BMImNTf2 (NTf2: bis(trifluoromethylsulfonyl)imide). Both ionic liquids were found undergoing a single step of mass loss in the temperature range investigated. However, while the BMImNTf2 mass loss was found to occur in different temperature ranges, depending on the inert gas used, the TG curves of BMImCl under helium and nitrogen flow were practically superimposable, thus suggesting the occurrence of thermal decomposition. Furthermore, KEML experiments on BMImCl (in the range between 398 and 481 K) indicated a clear dependence of the unit area mass loss rate on the effusion hole diameter, an effect not observed for the ILs with NTf2 anion. Finally, KEMS measurements in the 416–474 K range allowed us to identify the most abundant species in the vapor phase, which resulted in methyl chloride, butylimidazole, butyl chloride, and methylimidazole, which most probably formed from the decomposition of the liquid

The Dissociation Energy of the New Diatomic Molecules SiPb and GePb

The diatomic molecules SiPb and GePb were for the first time identified by producing high temperature vapors of the constituent pure elements in a double-oven-like molecular-effusion assembly. The partial pressures of the atomic, heteronuclear, and homonuclear gaseous species observed in the vapor, namely, Si, Ge, Pb, SiPb, GePb, Pb2, Gen, and Sin (n=2-3), were mass-spectrometrically measured in the overall temperature ranges 1753-1961 K (Ge-Pb) and 1992-2314 K (Si-Pb). The dissociation energies of the new species were determined by second- and third-law analyses of both the direct dissociation reactions and isomolecular exchange reactions involving homonuclear molecules. The selected values of the dissociation energies at 0 K (D0 degrees) are 165.1+/-7.3 and 141.6+/-6.9 kJ/mol, respectively, for SiPb and GePb, and the corresponding enthalpies of formation (DeltafH0 degrees) are 476.4+/-7.3 and 419.3+/-6.9 kJ/mol. The ionization efficiency curves of the two species were measured, giving the following values for the first ionization energies: 7.0+/-0.2 eV (SiPb) and 7.1+/-0.2 eV (GePb). A computational study of the species SiPb and GePb was also carried out at the CCSD(T) level of theory using the relativistic electron core potential approach. Molecular parameters, adiabatic ionization energies, adiabatic electron affinities, and dissociation energies of the title species were calculated, as well as the enthalpy changes of the exchange reactions involving the other Pb-containing diatomics of group 14. Finally, a comparison between the experimental and theoretical results is presented, and from a semiempirical correlation the unknown dissociation energies of the SiSn and PbC molecules are predicted as 234+/-7 and 185+/-11 kJ/mol, respectively

Análisis del contacto entre las formaciones Vinchina y Toro Negro (Sierra de los Colorados, provincia de La Rioja, Argentina), sus implicancias tectónicas

En este trabajo se analiza la expresión estratigráfica y significado geológico de la superficie que separa a las formaciones Vinchina (Mioceno) y Toro Negro (Mioceno Tardío-Plioceno), las que afloran conformando la Sierra de Los Colorados (oeste de la provincia de La Rioja). El estudio se realizó mediante el levantamiento de 6 secciones detalladas, de norte a sur: quebrada de La Aguada, quebrada de Los Pozuelos, río de La Troya norte, río de La Troya sur, Campo Negro y quebrada del Yeso. La información reunida en estos perfiles permitió comprobar que el contacto entre ambas unidades queda definido por una superficie de incisión de alto relieve relativo que suprime, en algunos sectores, hasta un 25% de la Formación Vinchina. La superficie en cuestión forma un paleovalle en el sector norte (secciones de La Aguada y Los Pozuelos), se manifiesta como una superficie de incisión ondulada (con mínima supresión estratigráfica) en la parte central del área estudiada (secciones de río de La Troya sur y Campo Negro) y pierde relieve hacia el sur hasta transformarse en una superficie relativamente plana (sección de quebrada del Yeso). El análisis de los depósitos sobrepuestos a la superficie de incisión permitió la definición de cuatro secciones estratigráficas. La sección S1 está compuesta por conglomerados extraformacionales, aglomerados y brechas intraformacionales. En la sección S2 predominan conglomerados gruesos hasta finos, areniscas guijarrosas y areniscas gruesas siendo muy escasas las pelitas y areniscas muy finas. La sección S3 comprende ciclos granocrecientes formados por pelitas, areniscas y conglomerados. Finalmente, la sección S4 comprende pelitas y areniscas finas con limitada participación de conglomerados y areniscas gruesas. La sección S1 es interpretada como depósitos confinados bajo condiciones de bajo espacio de acomodación. La sección S2 también fue formada en condiciones de confinamiento pero dentro de un esquema de espacio de acomodación creciente. Finalmente, las secciones S3 y S4 indican la pérdida de confinamiento del sistema y el estado de máximo espacio de acomodación. La génesis de la superficie de incisión que separa a las formaciones Vinchina y Toro Negro es, en este trabajo, relacionada a las fases principales del ascenso del Famatina occidental

Estimations of isoprenoid emission capacity from enclosure studies: measurements, data processing, quality and standardized measurement protocols

The capacity for volatile isoprenoid production under standardized environmental conditions at a certain time (ES, the emission factor) is a key characteristic in constructing isoprenoid emission inventories. However, there is large variation in published ES estimates for any given species partly driven by dynamic modifications in ES due to acclimation and stress responses. Here we review additional sources of variation in ES estimates that are due to measurement and analytical techniques and calculation and averaging procedures, and demonstrate that estimations of ES critically depend on applied experimental protocols and on data processing and reporting. A great variety of experimental setups has been used in the past, contributing to study-to-study variations in ES estimates. We suggest that past experimental data should be distributed into broad quality classes depending on whether the data can or cannot be considered quantitative based on rigorous experimental standards. Apart from analytical issues, the accuracy of ES values is strongly driven by extrapolation and integration errors introduced during data processing. Additional sources of error, especially in meta-database construction, can further arise from inconsistent use of units and expression bases of ES. We propose a standardized experimental protocol for BVOC estimations and highlight basic meta-information that we strongly recommend to report with any ES measurement. We conclude that standardization of experimental and calculation protocols and critical examination of past reports is essential for development of accurate emission factor databases.JRC.H.7-Climate Risk Managemen

Climatic Feedbacks and Desertification: The Mediterranean Model

Abstract Mesometeorological information obtained in several research projects in southern Europe has been used to analyze perceived changes in the western Mediterranean summer storm regime. A procedure was developed to disaggregate daily precipitation data into three main components: frontal precipitation, summer storms, and Mediterranean cyclogenesis. Working hypotheses were derived on the likely processes involved. The results indicate that the precipitation regime in this Mediterranean region is very sensitive to variations in surface airmass temperature and moisture. Land-use perturbations that accumulated over historical time and greatly accelerated in the last 30 yr may have induced changes from an open, monsoon-type regime with frequent summer storms over the mountains inland to one dominated by closed vertical recirculations where feedback mechanisms favor the loss of storms over the coastal mountains and additional heating of the sea surface temperature during summer. This, in turn, favors Mediterranean cyclogenesis and torrential rains in autumn–winter. Because these intense rains and floods can occur anywhere in the basin, perturbations to the hydrological cycle in any part of the basin can propagate to the whole basin and adjacent regions. Furthermore, present levels of air pollutants can produce greenhouse heating, amplifying the perturbations and pushing the system over critical threshold levels. The questions raised are relevant for the new European Union (EU) water policies in southern Europe and for other regions dominated by monsoon-type weather systems

Isoprene and monoterpene fluxes from central amazonian rainforest inferred from tower-based and airborne measurements, and implications on the atmospheric chemistry and the local carbon budget

We estimated the isoprene and monoterpene source strengths of a pristine tropical forest north of Manaus in the central Amazon Basin using three different micrometeorological flux measurement approaches. During the early dry season campaign of the Cooperative LBA Airborne Regional Experiment (LBA-CLAIRE-2001), a tower-based surface layer gradient (SLG) technique was applied simultaneously with a relaxed eddy accumulation (REA) system. Airborne measurements of vertical profiles within and above the convective boundary layer (CBL) were used to estimate fluxes on a landscape scale by application of the mixed layer gradient (MLG) technique. The mean daytime fluxes of organic carbon measured by REA were 2.1 mg C m^−2 h^−1 for isoprene, 0.20 mg C m^−2 h^−1 for α-pinene, and 0.39 mg C m^−2 h^−1 for the sum of monoterpenes. These values are in reasonable agreement with fluxes determined with the SLG approach, which exhibited a higher scatter, as expected for the complex terrain investigated. The observed VOC fluxes are in good agreement with simulations using a single-column chemistry and climate model (SCM).\ud \ud In contrast, the model-derived mixing ratios of VOCs were by far higher than observed, indicating that chemical processes may not be adequately represented in the model. The observed vertical gradients of isoprene and its primary degradation products methyl vinyl ketone (MVK) and methacrolein (MACR) suggest that the oxidation capacity in the tropical CBL is much higher than previously assumed. A simple chemical kinetics model was used to infer OH radical concentrations from the vertical gradients of (MVK+MACR)/isoprene. The estimated range of OH concentrations during the daytime was 3–8×10^6 molecules cm^−3, i.e., an order of magnitude higher than is estimated for the tropical CBL by current state-of-the-art atmospheric chemistry and transport models. The remarkably high OH concentrations were also supported by results of a simple budget analysis, based on the flux-to-lifetime relationship of isoprene within the CBL. Furthermore, VOC fluxes determined with the airborne MLG approach were only in reasonable agreement with those of the tower-based REA and SLG approaches after correction for chemical decay by OH radicals, applying a best estimate OH concentration of 5.5×10^6 molecules cm^−3. The SCM model calculations support relatively high OH concentration estimates after specifically being constrained by the mixing ratios of chemical constituents observed during the campaign.\ud \ud The relevance of the VOC fluxes for the local carbon budget of the tropical rainforest site during the measurements campaign was assessed by comparison with the concurrent CO2 fluxes, estimated by three different methods (eddy correlation, Lagrangian dispersion, and mass budget approach). Depending on the CO2 flux estimate, 1–6% or more of the carbon gained by net ecosystem productivity appeared to be re-emitted through VOC emissions