Kenneth G. Kroenlein

ThermoData Engine (TDE): Software Implementation of the Dynamic Data Evaluation Concept. 9. Extensible Thermodynamic Constraints for Pure Compounds and New Model Developments

ThermoData Engine (TDE) is the first full-scale software implementation of the dynamic data evaluation concept, as reported in this journal. The present article describes the background and implementation for new additions in latest release of TDE. Advances are in the areas of program architecture and quality improvement for automatic property evaluations, particularly for pure compounds. It is shown that selection of appropriate program architecture supports improvement of the quality of the on-demand property evaluations through application of a readily extensible collection of constraints. The basis and implementation for other enhancements to TDE are described briefly. Other enhancements include the following: (1) implementation of model-validity enforcement for specific equations that can provide unphysical results if unconstrained, (2) newly refined group-contribution parameters for estimation of enthalpies of formation for pure compounds containing carbon, hydrogen, and oxygen, (3) implementation of an enhanced group-contribution method (NIST-Modified UNIFAC) in TDE for improved estimation of phase-equilibrium properties for binary mixtures, (4) tools for mutual validation of ideal-gas properties derived through statistical calculations and those derived independently through combination of experimental thermodynamic results, (5) improvements in program reliability and function that stem directly from the recent redesign of the TRC-SOURCE Data Archival System for experimental property values, and (6) implementation of the Peng-Robinson equation of state for binary mixtures, which allows for critical evaluation of mixtures involving supercritical components. Planned future developments are summarized.

ThermoData Engine (TDE): software implementation of the dynamic data evaluation concept. 6. Dynamic web-based data dissemination through the NIST Web Thermo Tables.

ThermoData Engine (TDE) is the first full-scale software implementation of the dynamic data evaluation concept, as reported recently in this journal. In the present paper, we describe the development of a World Wide Web-based interface to TDE evaluations of pure compound properties, including critical properties, phase boundary equilibria (vapor pressures, sublimation pressures, and crystal-liquid boundary pressures), densities, energetic properties, and transport properties. This includes development of a system for caching evaluation results to maintain high availability and an advanced window-in-window interface that leverages modern Web-browser technologies. Challenges associated with bringing the principal advantages of the TDE technology to the Web are described, as are compromises to maintain general access and speed of interaction while remaining true to the tenets of dynamic data evaluation. Future extensions of the interface and associated Web-services are outlined.

A MoS2-Based Capacitive Displacement Sensor for DNA Sequencing

We propose an aqueous functionalized molybdenum disulfide nanoribbon suspended over a solid electrode as a capacitive displacement sensor aimed at determining the DNA sequence. The detectable sequencing events arise from the combination of Watson-Crick base-pairing, one of natures most basic lock-and-key binding mechanisms, with the ability of appropriately sized atomically thin membranes to flex substantially in response to subnanonewton forces. We employ carefully designed numerical simulations and theoretical estimates to demonstrate excellent (79% to 86%) raw target detection accuracy at ∼70 million bases per second and electrical measurability of the detected events. In addition, we demonstrate reliable detection of repeated DNA motifs. Finally, we argue that the use of a nanoscale opening (nanopore) is not requisite for the operation of the proposed sensor and present a simplified sensor geometry without the nanopore as part of the sensing element. Our results, therefore, potentially suggest a realistic, inherently base-specific, high-throughput electronic DNA sequencing device as a cost-effective de novo alternative to the existing methods.

Sooting Behavior of Ethanol Droplet Combustion at Elevated Pressures Under Microgravity Conditions

Liquid ethanol is widely used in practical fuels as a means to extend petroleum-derived resources or as a fuel additive to reduce emissions of carbon monoxide from spark ignition engines. Recent research has also suggested that ethanol and other oxygenates could be added to diesel fuel to reduce particulate emissions. In this cursory study, the combustion of small ethanol droplets in microgravity environments was observed to investigate diffusion flame characteristics at higher ambient pressures and at various oxygen indices, all with nitrogen as the diluent species. At the NASA Glenn Research Center 2.2-second drop tower, free ethanol droplets were ignited in the Droplet Combustion Experiment (DCE) apparatus, and backlit and flame view data were collected to evaluate flame position and burning rate. Profuse sooting was noted above 3 atm ambient pressure. In experiments performed at the Japan Microgravity Center 10-second (JAMIC) drop shaft with Sooting Effects in Droplet Combustion (SEDC) apparatus, the first data that displayed a spherical sootshell for ethanol droplet combustion was obtained. Because of the strong sensitivity of soot formation to small changes in an easily accessible range of pressures, ethanol appears to be a simple liquid fuel suitable for fundamental studies of soot formation effects on spherical diffusion flames. The results impact discussions regarding the mechanism of particulate reduction by ethanol addition to fuels in high-pressure practical combustors.

Critical Evaluation of Thermodynamic Properties for Halobenzoic Acids Through Consistency Analyses for Results from Experiment and Computational Chemistry

Thermodynamic properties of the twelve monohalobenzoic acids are critically evaluated through the application of computational chemistry methods for the ideal-gas phase and thermodynamic consistency assessment of properties determined experimentally and reported in the literature, including enthalpies of combustion, enthalpies of sublimation, and enthalpies of fusion. The compounds of interest are the 2-, 3-, and 4-halo isomers of fluoro-, chloro-, bromo-, and iodobenzoic acids. Computations were validated by comparison with critically evaluated entropies and heat capacities in the ideal-gas state for benzoic acid, benzene, and some halobenzenes. Experimental enthalpies of formation for 2- and 3-bromobenzoic acids, measured by well-established research groups, are mutually inconsistent and further, are shown to be inconsistent with the computations and assessment in this work. Origins of the discrepancies are unknown, and recommended values for these compounds are based on computations and enthalpies of s...