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Computer program is described for numerical solution of chemical equilibria in complex systems by using nonlinear algebraic equations. Free-energy minimization technique is used.
The Brinkley, Huff, and White methods for chemical-equilibrium calculations were modified and extended in order to permit an analytical comparison. The extended forms of these methods permit condensed species as reaction products, include temperature as a variable in the iteration, and permit arbitrary estimates for the variables. It is analytically shown that the three extended methods can be placed in a form that is independent of components. In this form the Brinkley iteration is identical computationally to the White method, while the modified Huff method differs only'slightly from these two. The convergence rates of the modified Brinkley and White methods are identical; and, further, all three methods are guaranteed to converge and will ultimately converge quadratically. It is concluded that no one of the three methods offers any significant computational advantages over the other two.
The information about composition of aerosols has a great importance for monitoring and understanding of climate and environment dynamics. Such information can be obtained using situ measurements or chemical transport models. However, in situ sampling has limited spatial and temporal coverage, while estimations have large uncertainties. The present work enables the monitoring of aerosol chemical species from space-borne observations, providing observationally-based results with spatial and temporal coverage. Following the ideas of Schuster et al.(2005, 2009, 2016), we retrieve chemical composition directly from satellite observations without intermediate retrieval of the refractive index (in contrast with Schuster's approach). This approach is expected to reduce the influence of modeling uncertainties, and to provide additional constraints in situations where remote sensing observations do not have enough spectral sensitivity to refractive index. One of principal difficulties is the identification of an adequate model for linking refractive index to chemical composition. Therefore, the initial effort of this work has focused on identifying an optimal physico-chemistry to refractive index conversion model. With that purpose, we first tested the retrieval approach using a simplified volume-weighting model and updated by the Maxwell Garnett mixing model. This concept was incorporated into the GRASP algorithm designed to retrieve an extended set of atmospheric parameters from remote sensing observations. Then a series of sensitivity tests using synthetic data of POLDER/PARASOL were conducted, and followed by inversion of real PARASOL observations over Africa. The sensitivity tests showed that these two models allow the retrieval to distinguish amongst the assumed chemical species. Results obtained from real PARASOL data demonstrated good agreement with the optical characteristics provided by AERONET. In addition, the obtained patterns of chemical component distribution agreed with known physical expectations. We also compared the chemical composition retrievals to GOCART model simulations and obtained good consistencies.
Results are presented for a study in which high-precision instrumental neutron activation analysis was applied to determine the abundances of seven rare-earth and nine other elements in two grain-size fractions (90 to 150 microns and less than 20 microns) of eight soils from the Taurus-Littrow Valley floor and one Apollo 11 bulk-soil fraction with grain sizes of less than 1 mm. Compositional differences between the two size fractions of two valley-floor soils are examined, and mixing of soil components is investigated. It is found that a five-component mixing model describes very adequately the chemical composition of bulk soils with grain sizes of less than 1 mm as mixtures of local Apollo 17 rock types (basalt, anorthositic gabbro, noritic breccia), orange glass, and meteorites, but does not describe well the chemical compositions of the other two size fractions. A ten-component model is used to show that the compositions of those two size fractions can be well represented as mixtures of the five components if the mineralogy and chemical composition of the basalt component are allowed to vary in the size fractions.
Proximity ferroelectricity is a novel paradigm for inducing ferroelectricity in a non-ferroelectric polar material, such as AlN or ZnO that are typically unswitchable with an external field below their dielectric breakdown field. When placed in direct contact with a thin switchable ferroelectric layer (such as Al 1-x Sc x N or Zn 1-x Mg x O), they become a practically switchable ferroelectric. Using the thermodynamic Landau-Ginzburg-Devonshire theory, in this work, we perform the finite element modeling of the polarization switching in the compositionally graded AlN-Al 1-x Sc x N, ZnO-Zn 1-x Mg x O, and MgO-Zn 1-x Mg x O structures sandwiched in both a parallel-plate capacitor geometry as well as in a sharp probe-planar electrode geometry. We reveal that the compositionally graded structure allows the simultaneous switching of spontaneous polarization in the whole system by a coercive field significantly lower than the electric breakdown field of unswitchable polar materials. The physical mechanism is the depolarization electric field determined by the gradient of chemical composition “x”. The field lowers the steepness of the switching barrier in the otherwise unswitchable parts of the compositionally graded AlN-Al 1-x Sc x N and ZnO-Zn 1-x Mg x O structures. In the MgO-like regions of the compositionally graded MgO-Zn 1-x Mg x O structure, a shallow double-well free energy potential emerges. Proximity ferroelectric switching of the compositionally graded structures placed in the probe-electrode geometry occurs due to nanodomain formation under the tip. We predict that a gradient of chemical composition “x” significantly lowers effective coercive fields of the compositionally graded AlN-Al 1-x Sc x N and ZnO-Zn 1-x Mg x O structures compared to the coercive fields of the corresponding multilayers with a uniform chemical composition in each layer. A tip-induced switching further lowers the coercive field, enabling control of ferroelectric domains in otherwise unswitchable compositionally graded structures, which can provide nanoscale domain control for memory, actuation, sensing, and optical applications.
The chemical composition and morphology of Au x Co 1–x thin films and nanoparticles are controlled via a combination of cosputtering, pulsed laser-induced dewetting (PLiD), and annealing, leading to tunable magnetic and optical properties. Regardless of chemical composition, the as-deposited thin films and as-PLiD nanoparticles are found to possess a face-centered cubic (FCC) Au x Co 1–x solid-solution crystal structure. Annealing results in large phase-separated grains of Au and Co in both the thin films and nanostructures for all chemical compositions. The magnetic and optical properties are characterized via vibrating sample magnetometry (VSM), ellipsometry, optical transmission spectroscopy, and electron energy loss spectroscopy (EELS). Despite the exceptionally high magnetic anisotropy inherent to Co, the presence of sufficient Au (72 atom %) in the Au x Co 1–x solid solution results in superparamagnetic thin films. Among the as-PLiD nanoparticle samples, an increased Co composition leads to a departure from traditional ferromagnetism in favor of wasp-waisted hysteresis caused by magnetic vortices. Phase separation resulting from annealing leads to ferromagnetism for all compositions in both the thin films and nanoparticles. The optical properties of Au x Co 1–x nanostructures are also largely influenced by the chemical morphology, where the Au x Co 1–x intermixed solid solution has significantly damped plasmonic performance relative to pure Au and comparable to pure Co. Phase separation greatly enhances the quality factor, optical absorption, and electron energy loss spectroscopy (EELS) signatures. The enhancement of the localized surface plasmon resonances (LSPRs) scales with the reduction in Co composition, despite EELS evidence that excitation of the Co portions of a nanoparticle can provide a similar, and in some instances enhanced, LSPR resonance compared to Au. This behavior, however, is seemingly limited to the LSPR dipole mode, while higher-order modes are greatly damped by a Co aloof position. As a result, this observed magneto-plasmonic functionality and tunability could be applicable in biomedicine, namely, cancer therapeutics.
Atomic-force microscopy coupled with infrared spectroscopy (AFM-IR) deciphers surface morphology of thin-film polymer blends and composites by simultaneously mapping physical topography and chemical composition. However, acquiring quantitative phase and composition information from multi-component blends can be challenging using AFM-IR due to the possible overlapping infrared absorption bands between different species. Isotope labeling one of the blend components introduces a new type of bond (carbon-deuterium vibration) that can be targeted using AFM-IR and responds at wavelengths sufficiently shifted toward unoccupied regions (around 2200 cm –1 ). In this project, AFM-IR was used to probe the surface morphology and chemical composition of three polymer blends containing deuterated polystyrene; each blend is expected to exhibit various degrees of miscibility. AFM-IR results successfully demonstrated that deuterium labeling prevents infrared spectral overlap and enables the visualization of blend phases that could not normally be distinguished by other scanning probe techniques. The nanoscale domain composition was resolved by fast infrared spectrum analysis. Overall, we presented isotope labeling as a robust approach for circumventing obstacles preventing the quantitative analysis of multiphase systems by AFM-IR.
This final report represents the completion of the three tasks under the purchase order no. SCPDE5620,1,2F. Chemical composition of gravitationally contracting, but otherwise quiescent, interstellar clouds and of interstellar clouds traversed by high velocity shocks, were modeled in a comprehensive manner that represents a significant progress in modeling these objects. The evolutionary chemical modeling, done under this NASA contract, represents a notable advance over the 'classical' fixed condition equilibrium models because the evolutionary models consider not only the chemical processes but also the dynamical processes by which the dark interstellar clouds may have assumed their present state. The shock calculations, being reported here, are important because they extend the limited chemical composition derivable from dynamical calculations for the total density and temperature structures behind the shock front. In order to be tractable, the dynamical calculations must severely simplify the chemistry. The present shock calculations take the shock profiles from the dynamical calculations and derive chemical composition in a comprehensive manner. The results of the present modeling study are still to be analyzed with reference to astronomical observational data and other contemporary model predictions. As far as humanly possible, this analysis will be continued with CRE's (Creative Research Enterprises's) IR&D resources, until a sponsor is found.
Martian photochemistry, chemical kinetics and composition, discussing effect of minor species
Arrays of broadly responsive vapor detectors can be used to detect, identify, and quantify vapors and vapor mixtures. One implementation of this strategy involves the use of arrays of chemically-sensitive resistors made from conducting polymer composites. Sorption of an analyte into the polymer composite detector leads to swelling of the film material. The swelling is in turn transduced into a change in electrical resistance because the detector films consist of polymers filled with conducting particles such as carbon black. The differential sorption, and thus differential swelling, of an analyte into each polymer composite in the array produces a unique pattern for each different analyte of interest, Pattern recognition algorithms are then used to analyze the multivariate data arising from the responses of such a detector array. Chiral detector films can provide differential detection of the presence of certain chiral organic vapor analytes. Aspects of the spaceflight qualification and deployment of such a detector array, along with its performance for certain analytes of interest in manned life support applications, are reviewed and summarized in this article.
Carbonate occurs at the Comanche outcrops in Gusev Crater on the basis of analyses made by the Mars Exploration Rover Spirit [1]. Taken together, mineralogical data from Spirit's Moessbauer (MB) and Mini-TES spectrometer and chemical data from the APXS spectrometer show that Comanche carbonate has an Mg-Fe-rich bulk chemical composition, is present at high concentrations, and is distributed throughout the outcrop and not just at the MB and APXS analysis location. The granular outcrop texture and the observation that it appears to be resistant to weathering compared with surrounding material [1] imply that the carbonate may be present as a cement. A hydrothermal origin for the Comanche carbonate was inferred by analogy with laboratory experiments and with a carbonate occurrence within the Bockfjord volcanic complex on the island Spitsbergen (Svalbard, Norway) [1]. The laboratory carbonates, synthesized by precipitation from hydrothermal solutions, have (MB) parameters and average bulk chemical compositions that are characteristic of Comanche carbonate. The connection to Comanche carbonate is only through chemical data for certain occurrences of Spitsbergen carbonates. In fact, the common average bulk chemical composition for these Spitsbergen carbonates, the synthetic carbonates, the Comanche carbonate, and also the carbonate globules found in martian meteorite ALH84001 is a chemical constraint consistent with a hydrothermal formation process for all the carbonates [e.g., 1-3]. We develop here a link between MB data for the Comanche carbonate from MER and MB data for certain Spitsbergen carbonate occurrences from laboratory measurements. We also obtained visible and near- IR spectra on Spitsbergen carbonates for comparison with martian carbonate detections made on the basis of CRISM spectral data, e.g., in Nili Fossae [4].
The ChemCam instrument [1] on the Mars Science Laboratory (MSL) rover will be used to obtain the chemical composition of surface targets within 7 m of the rover using Laser Induced Breakdown Spectroscopy (LIBS). ChemCam analyzes atomic emission spectra (240-800 nm) from a plasma created by a pulsed Nd:KGW 1067 nm laser. The LIBS spectra can be used in a semiquantitative way to rapidly classify targets (e.g., basalt, andesite, carbonate, sulfate, etc.) and in a quantitative way to estimate their major and minor element chemical compositions. Quantitative chemical analysis from LIBS spectra is complicated by a number of factors, including chemical matrix effects [2]. Recent work has shown promising results using multivariate techniques such as partial least squares (PLS) regression and artificial neural networks (ANN) to predict elemental abundances in samples [e.g. 2-6]. To develop, refine, and evaluate analysis schemes for LIBS spectra of geologic materials, we collected spectra of a diverse set of well-characterized natural geologic samples and are comparing the predictive abilities of PLS, cascade correlation ANN (CC-ANN) and multilayer perceptron ANN (MLP-ANN) analysis procedures.
A comprehensive review of current knowledge about the neutral gas atmospheres of comets is given, with emphasis on the task of deriving the chemical composition of the cometary nucleus. The discussion centers on the following major topics: photometric and spectrophotometric observations of the neutral atmosphere and its constituent neutral radicals, molecules, and atoms; excitation processes responsible for the observed emissions from the neutral coma; the parent molecules of the neutral radicals; the gas-phase chemistry likely to take place in the dense inner coma; dynamic models (both exospheric and hydrodynamic) of the neutral atmosphere; and the chemical compositions of comets. The primary conclusions reached on the basis of all the data considered are that: (1) the chemical composition of the dust component is most likely to be the same as that of the stream meteoroids which burn up on hitting the earth's upper atmosphere; (2) the dominant icy component in most comets is probably H2O; and (3) anomalous abundances of other volatile species are present in some comets.
The relationship between the chemical composition and the interlayer spacing (d002) of organic materials (OM's) is known for various terrestrial OM's. We improved this general trend by correlation with corresponding trend of natural solid bitumens (asphaltite-kerite-anthraxolite) up to graphite. Using the improved trend we identified bitumen analogs of carbonaceous chondrite OM's residued after HF-HCl treatment. Our laboratory experiment revealed that these analogs and, hence, structure and chemical composition of carbonaceous chondrite OM's are very sensitive to the HF-HCl treatment. So, usual extraction of OM from carbonaceous chondrites may change significantly structural and chemical composition of extracted OM.
Cosmogenic Ne-21 is used widely to calculate exposure ages of stone meteorites. In order to do so, the production rate P(21) must be known. This rate, however, is dependent on the chemical composition of the meteorite as well as the mass of, and position within, the meteoroid during its exposure to the cosmic radiation. Even for a mean shielding the production rates determined from measurments of different radionuclides vary by a factor of two. A method that can be used to determine exposure ages of meteorites that avoids shielding and chemical composition corrections is the -81-Kr-Kr-method. However, for chondrites, in many cases, the direct determination of production rates for the Kr isotopes is prevented by the trapped gases and the neutron effects on bromine. Therefore, this method was applied to four eucrite falls and then their 81-Kr-83-Kr-ages were compared to their cosmogenic Ne-21 and Ar-38 concentrations. The eucrites Bouvante-le-Haut, Juvinas, Sioux County, and Stannern were chosen for these measurements because of their similar chemical composition regarding the major elements.
Interaction of groundwater with the serpentinized harzburgites of the upper mantle plays an important role in the geologic carbon cycle and serpentinization processes. Here, in this study, an intact serpentinized harzburgite with more than 60% lizardite from the Semail ophiolite in Oman was reacted with water at near neutral pH and low PCO 2 to observe its dissolution behavior and reaction path within the CaO-MgO-SiO 2 -CO 2 -H 2 O system at 20 °C and 30 bars. In the experiment, mass (i.e. H 2 O, ions) transfer is by diffusion and the selected temperature and pressure conditions mimic water-rock interactions at the shallow portions of most ultramafic rock hosted aquifers. Equilibrium activity-activity diagrams and thermodynamic data were used to compare the experimentally determined reaction path with the theoretical stability boundaries for minerals involved to investigate the evolution of bulk chemical composition, mineralogy, and water composition. The experiments demonstrated that (i) the water-rock interactions increased the pH of the aqueous phase from 5.9 to 7.5 over a period of 18 weeks; (ii) the dissolution of lizardite, orthopyroxene (enstatite), and clinopyroxene (diopside and augite) increased the concentration of Mg, Ca, and Si in the aqueous phase; (iii) the dissolution was incongruent with respect to Mg and Si, favoring Si release at pH > 6 due to (a) breaking of more reactive cation‑oxygen bonds that is consistent with the stoichiometry of magnesium for proton exchange reaction which favors a surface that is enriched in Mg at basic conditions, and (b) preferential dissolution of clinopyroxene Mg 1.30 Ca 0.52 Fe 0.06 Si 2 O 6 ; (iv) the aqueous phase was undersaturated with respect to carbonate (e.g. calcite, magnesite, and hydromagnesite) and hydrous (e.g. lizardite, chrysotile, brucite, and talc) minerals; (v) the bulk chemical composition and mineralogy of the intact serpentinized harzburgite matrix did not change; (vi) the thermodynamic data can successfully predict water-intact serpentinized harzburgite behavior if the water chemical composition can be constrained; and (vii) no detectable macroscopic form of damage (e.g. microcracks forming as a result of differential stress fields due to changes in volume during chemical reaction) was observed.
Nearly all rocks returned from the moon are readily divided into three broad categories on the basis of their chemical compositions: (1) mare basalts, (2) non-mare rocks of basaltic composition (KREEP, VHA), and (3) anorthositic rocks. Only mare basalts may unambiguously be considered to have original igneous textures and are widely understood to have an igneous origin. Nearly all other lunar rocks have lost their original textures during metamorphic and impact processes. For these rocks one must work primarily with chemical data in order to recognize and define rock groups and their possible modes of origin. Non-mare rocks of basaltic composition have chemical compositions consistent with an origin by partial melting of the lunar interior. The simplest origin for rocks of anorthositic chemical composition is the crystallization and removal of ferromagnesian minerals. It is proposed that the rock groups of anorthositic and non-mare basaltic chemical composition could have been generated from a single series of original, but not necessarily primitive, lunar materials.
Current remote sensing methods can identify aerosol types within an atmospheric column, presenting an opportunity to incrementally bridge the gap between remote sensing and models. Here a new algorithm was designed for Creating Aerosol Types from CHemistry (CATCH). CATCH-derived aerosol types—dusty mix, maritime, urban, smoke, and fresh smoke—are based on first-generation airborne High Spectral Resolution Lidar (HSRL-1) retrievals during the Ship-Aircraft Bio-Optical Research (SABOR) campaign, July/August 2014. CATCH is designed to derive aerosol types from model output of chemical composition. CATCH-derived aerosol types are determined by multivariate clustering of model-calculated variables that have been trained using retrievals of aerosol types from HSRL-1. CATCH-derived aerosol types (with the exception of smoke) compare well with HSRL-1 retrievals during SABOR with an average difference in aerosol optical depth (AOD) <0.03. Data analysis shows that episodic free tropospheric transport of smoke is underpredicted by the Goddard Earth Observing System- with Chemistry (GEOS-Chem) model. Spatial distributions of CATCH-derived aerosol types for the North American model domain during July/August 2014 show that aerosol type-specific AOD values occurred over representative locations: urban over areas with large population, maritime over oceans, smoke, and fresh smoke over typical biomass burning regions. This study demonstrates that model-generated information on aerosol chemical composition can be translated into aerosol types analogous to those retrieved from remote sensing methods. In the future, spaceborne HSRL-1 and CATCH can be used to gain insight into chemical composition of aerosol types, reducing uncertainties in estimates of aerosol radiative forcing.