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At least 19 records

Sensing a Changing Chemical Mixture Using an Electronic Nose

A method of using an electronic nose to detect an airborne mixture of known chemical compounds and measure the temporally varying concentrations of the individual compounds is undergoing development. In a typical intended application, the method would be used to monitor the air in an inhabited space (e.g., the interior of a building) for the release of solvents, toxic fumes, and other compounds that are regarded as contaminants. At the present state of development, the method affords a capability for identifying and quantitating one or two compounds that are members of a set of some number (typically of the order of a dozen) known compounds. In principle, the method could be extended to enable monitoring of more than two compounds. An electronic nose consists of an array of sensors, typically made from polymer carbon composites, the electrical resistances of which change upon exposure to a variety of chemicals. By design, each sensor is unique in its responses to these chemicals: some or all of the sensitivities of a given sensor to the various vapors differ from the corresponding sensitivities of other sensors. In general, the responses of the sensors are nonlinear functions of the concentrations of the chemicals. Hence, mathematically, the monitoring problem is to solve the set of time-dependent nonlinear equations for the sensor responses to obtain the time dependent concentrations of individual compounds. In the present developmental method, successive approximations of the solution are generated by a learning algorithm based on independent-component analysis (ICA) an established information theoretic approach for transforming a vector of observed interdependent signals into a set of signals that are as nearly statistically independent as possible.

Duong, Tuan↗

Computing Properties Of Chemical Mixtures At Equilibrium

Scientists and engineers need data on chemical equilibrium compositions to calculate theoretical thermodynamic properties of chemical systems. Information essential in design and analysis of such equipment as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical-processing equipment. CET93 is general program that calculates chemical equilibrium compositions and properties of mixtures for any chemical system for which thermodynamic data are available. Includes thermodynamic data for more than 1,300 gaseous and condensed species and thermal-transport data for 151 gases. Written in FORTRAN 77.

Mcbride, B. J.↗

Thermodynamic Calculations for Complex Chemical Mixtures

General computer program, CECTRP, developed for calculation of thermodynamic properties of complex mixtures with option to calculate transport properties of these mixtures. Free-energy minimization technique used in equilibrium calculation. Rigorous equations used in transport calculations. Program calculates equilibrium compositions and corresponding thermodynamic and transport properties of mixtures. CECTRP accommodates up to 24 reactants, 20 elements, and 600 products, 400 of which are condensed. Written in FORTRAN IV for any large computer system.

Mcbride, B. J.↗

Perturbation of the Maxwellian distribution in chemically reacting gas mixtures

Chemically reacting gas mixtures are considered for the case in which inelastic collisions occur significantly less frequently than elastic ones. The first approximation of the general solution of the Boltzmann equation is developed and is shown to contain an additional scaler term. The concentration, the mean mass velocity, and the temperature of the mixture are determined and the rate of reaction in the first approximation is formulated. Tables are presented which give reaction rate values obtained by both the first and second approximation for different activation energies. The tables show that the first approximation is sufficient for practical purposes for calculating the reaction rate.

Alekseyev, B. V.↗

Viscous shock layer solutions for turbulent flow of radiating gas mixtures in chemical equilibrium

The viscous shock layer equations for hypersonic laminar and turbulent flows of radiating or nonradiating gas mixtures in chemical equilibrium are presented for two-dimensional and axially symmetric flow fields. Solutions are obtained using an implicit finite difference scheme and results are presented for hypersonic flow over spherically blunted cone configurations at free stream conditions representative of entry into the atmosphere of Venus. These data are compared with solutions obtained using other methods of analysis.

Anderson, E. C.↗

Viscous-shock-layer solutions for turbulent flow of radiating gas mixtures in chemical equilibrium

The viscous-shock-layer equations for hypersonic laminar and turbulent flows of radiating or nonradiating gas mixtures in chemical equilibrium are presented for two-dimensional and axially-symmetric flow fields. Solutions were obtained using an implicit finite-difference scheme and results are presented for hypersonic flow over spherically-blunted cone configurations at freestream conditions representative of entry into the atmosphere of Venus. These data are compared with solutions obtained using other methods of analysis.

Anderson, E. C.↗

Laminar or turbulent boundary-layer flows of perfect gases or reacting gas mixtures in chemical equilibrium

Turbulent boundary layer flows of non-reacting gases are predicted for both interal (nozzle) and external flows. Effects of favorable pressure gradients on two eddy viscosity models were studied in rocket and hypervelocity wind tunnel flows. Nozzle flows of equilibrium air with stagnation temperatures up to 10,000 K were computed. Predictions of equilibrium nitrogen flows through hypervelocity nozzles were compared with experimental data. A slender spherically blunted cone was studied at 70,000 ft altitude and 19,000 ft/sec. in the earth's atmosphere. Comparisons with available experimental data showed good agreement. A computer program was developed and fully documented during this investigation for use by interested individuals.

Anderson, E. C.↗

Modeled Aerosol Optical Properties From Measurement-Based Mixtures of Chemical Species: Assessing the Impacts of Particle Morphology and Absorption

This report serves as the final report for the Colorado State University portion of this grant. The original grant was awarded to CSU under the direction of co-Principal Investigators Kirk Fuller and Sonia Kreidenweis. Upon Dr. Fuller's relocation to the University of Alabama - Huntsville, the major portion of the award was also relocated. The following summarizes only that work completed by Prof. Kreidenweis under her remaining award.

Kreidenweis, Sonia↗

A Multimodel Investigation of Asian Summer Monsoon UTLS Transport Over the Western Pacific

The Asian summer monsoon (ASM) as a chemical transport system is investigated using a suite of models in preparation for an airborne field campaign over the Western Pacific. Results show that the dynamical process of anticyclone eddy shedding in the upper troposphere rapidly transports convectively uplifted Asian boundary layer air masses to the upper troposphere and lower stratosphere over the Western Pacific. The models show that the transported air masses contain significantly enhanced aerosol loading and a complex chemical mixture of trace gases that are relevant to ozone chemistry. The chemical forecast models consistently predict the occurrence of the shedding events, but the predicted concentrations of transported trace gases and aerosols often differ between models. The airborne measurements to be obtained in the field campaign are expected to help reduce the model uncertainties. Furthermore, the large-scale seasonal chemical structure of the monsoon system is obtained from modeled carbon monoxide, a tracer of the convective transport of pollutants, which provides a new perspective of the ASM circulation, complementing the dynamical characterization of the monsoon.

Laura L. Pan↗

A Chemical Kinetic Mechanism for the Ignition of Silane/Hydrogen Mixtures

A chemical kinetic reaction mechanism for the oxidation of silane/hydrogen mixtures is presented and discussed. Shock-tube ignition delay time data were used to evaluate and refine the mechanism. Good agreement between experimental results and the results predicted by the mechanism was obtained by adjusting the rate coefficient for the reaction SiH3 + O2 yields SiH2O + OH. The reaction mechanism was used to theoretically investigate the ignition characteristics of silane/hydrogen mixtures. The results revealed that over the entire range of temperature examined (800 K to 1200 K), substantial reduction in ignition delay times is obtained when silane is added to hydrogen.

Jachimowski, C. J.↗

Evolution of Interstellar Grains

During the past two decades observations combined with laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the raw materials from which planets, comets and stars form. Most interstellar material is concentrated in large molecular clouds where simple molecules are formed by dust-grain and gas-phase reactions. Gaseous species striking the cold (10K) dust stick, forming an icy grain mantle. This accretion, coupled with UV photolysis, produces a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. Ices in molecular clouds contain the very simple molecules H2O, CH3OH, CO, CO2, H2, and perhaps some NH3 and H2CO, as well as more complex species. The evidence for these compounds, as well as carbon-rich materials, will be reviewed and the possible connections with comets and meteorites will be presented in the first part of the talk . The second part of the presentation will focus on interstellar/precometary ice photochemical evolution and the species likely to be found in comets. The chemical composition and photochemical evolution of realistic interstellar/pre-cometary ice analogs will be discussed. Ultraviolet photolysis of these ices produces H2, H2CO, CO2, CO, CH4, HCO, and more complex molecules. When ices representative of interstellar grains and comets are exposed to UV radiation at low temperature a series of moderately complex organic molecules are formed in the ice including: CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), and R-C=N (nitriles). Several of these are already known to be in the interstellar medium, and their presence indicates the importance of grain processing. After warming to room temperature an organic residue remains. This is composed primarily of hexamethylenetetramine (HMT, C6H12N4), with lesser amounts of polyoxymethylene-related species (POMs), amides, and ketones. This is in sharp contrast to the organic residues produced by irradiating unrealistic interstellar ice analogs or thermally promoted polymerization-type reactions in unirradiated realistic ice mixtures.

Allamandola, Lou J.↗

Interstellar/Precometary Organic Material and the Photochemical Evolution of Complex Organics

During the past two decades ground-, air-, and space-based infrared spectroscopic observations, combined with realistic laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the raw materials from which planets, comets and stars form. Most interstellar material is concentrated in Large molecular clouds where simple molecules are formed by dust grain and gas phase reactions. Gaseous species striking the cold (10 K) dust will stick, forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. Ices in molecular clouds contain the very simple molecules H2O, CH3OH, CO, CO2, H2, and perhaps some NH3 and H2CO, as well as more complex species including nitriles and ketones or esters. The evidence for these compounds as well as carbon rich materials such as polycyclic aromatic hydrocarbons (PAHs), microdiamonds, and amorphous carbon will be reviewed and the possible connections with comets and meteorites will be presented in the first part of the talk. The second part of the presentation will focus on interstellar/precometary ice photochemical evolution. The chemical composition and photochemical evolution of realistic interstellar/pre-cometary ice analogs containing methanol will be discussed. ultraviolet photolysis of these ices produces H2, H2CO, CO2, CO, CH4, HCO, and more complex molecules. Infrared spectroscopy, H-1 and C-13 nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry demonstrate that when ices representative of interstellar grains and comets are exposed to UV radiation at low temperature a series of moderately complex organic molecules are formed in the ice including: CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), and R-C(integral)N (nitriles). Several of these are already known to be in the interstellar medium, and their presence indicates the importance of grain processing. After warming to room temperature what remains is an organic residue composed primarily of Hexamethylenetetramine (HMT, C6H12N4), with lesser amounts of polyoxymethylene related species (POMs), amides, and ketones. This is in sharp contrast to the organic residues produced by irradiating ices which do not contain methanol (unrealistic interstellar ice analogs) or thermally promoted polymerization-type reactions in unirradiated realistic ice mixtures. Here HMT is only a minor product in a residue dominated by a mixture of polyoxymethylene related species. The implications, for infrared astronomy and astrochemistry, of high concentrations of HMT in interstellar and cometary ices may be profound. The ultraviolet photolysis of HMT frozen in H20 ice produces the "XCN" band observed in the spectra of protostellar objects and laboratory ices, as well as carbon oxides and other nitriles. Thus, HMT may be a precursor of XCN in protostellar objects and a source of CN and CO in the tail of comets. Also, HMT is known to hydrolyze under acidic conditions to yield ammonia and formaldehyde as well as amino acids. Thus, HMT may have been a source of organic material delivered to the early earth by comets.

Allamandola, Lou J.↗

Viscosity and viscoelasticity of two-phase systems having diffuse interfaces

The equilibrium stability criterion for diffuse interfaces in a two-component solution with a miscibility gap requires that the interdiffusion flux vanish. If the system is continuously deformed, convective fluxes disrupt the equilibrium in the interface regions and induce a counter diffusive flux, which is dissipative and contributes to the apparent viscosity of the mixture. Chemical free energy is recoverably stored, causing viscoelastic phenomena. Both effects are significant.

Hopper, R. W.↗