Alkali Metal- and Ammonium Picrate Extraction and Complex Forming Capabilities of d-Glucose and d-Mannose-based Lariat Ethers

The alkali metal- and ammonium picrate extracting ability of d-glucose- and d-mannose-based 15-crown-5 ethers and related lariat ethers was investigated in dichloromethane – water system. A heteroatom was waried in the crown ether containing a 4,6-O-benzylidene-α-d-glucopyranoside unit 6, (X=O), 2 (X=S) and 8a (X=NH). Extracting ability of the latter species (8a) was excellent (97–99%) in regard of all cations (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺ and NH₄⁺) examined, it was not, howewer, selective. Introduction of a side arm on the nitrogen atom of 8a decreased the extracting ability, but increased the selectivity. In this series of compounds (8b–f, 4), 4 with a pyridylethyl substituent allowed the extraction of sodium picrate in 72%. The glucose-based macrocycles 8a, 8e and 8f formed a stronger complex with the cations examined than the mannose-based analogues 9a, 9e and 9f, that can be explained by the all-gauche conformation of the former ones. It was pointed out that in the case of crowns with tertiary amine moieties, the basicity increases the quantity of the picrates extracted. According to complex forming measurements by FAB-MS, the best sodium ion selectivity was achieved by the γ-hydroxypropyl substituted lariat ether (8e). Possible structures of the complexes formed by the two types of monosacharides with sodium cation were evaluated by molecule modelling calculations.     

On-line delta(18)O measurement of organic and inorganic substances

A method for the automated sample conversion and on-line oxygen isotope ratio (delta(18)O) determination for organic and inorganic substances is presented. The samples are pyrolytically decomposed at 1400 degrees C in the presence of nickelized graphite. With the system presented organic as well as inorganic samples such as nitrates, sulphates and phosphates of 50-100 &mgr;g O can be analyzed for their delta(18)O values with a standard deviation usually better than 0.5 per thousand. Additionally, carbon isotope ratios of organic substances and nitrogen isotope ratios of inorganic nitrogenous compounds are available in the same sample run. Data for international and some inter-laboratory reference materials are presented to show the accuracy and reliability of the method. The effect of some additives on the CO yield was checked for substances which do not pyrolyze completely. Copyright 1999 John Wiley & Sons, Ltd.     

Flow reactor studies and kinetic modeling of the H2/O2 reaction

Profile measurements of the H₂/O₂ reaction have been obtained using a variable pressure flow reactor over pressure and temperature ranges of 0.3–15.7 atm and 850–1040 K, respectively. These data span the explosion limit behavior of the system and place significant emphasis on HO₂ and H₂O₂ kinetics. The explosion limits of dilute H₂/O₂/N₂ mixtures extend to higher pressures and temperatures than those previously observed for undiluted H₂/O₂ mixtures. In addition, the explosion limit data exhibit a marked transition to an extended second limit which runs parallel to the second limit criteria calculated by assuming HO₂ formation to be terminating. The experimental data and modeling results show that the extended second limit remains an important boundary in H₂/O₂ kinetics. Near this limit, small increases in pressure can result in more than a two order of magnitude reduction in reaction rate. At conditions above the extended second limit, the reaction is characterized by an overall activation energy much higher than in the chain explosive regime. The overall data set, consisting primarily of experimentally measured profiles of H₂, O₂, H₂O, and temperature, further expand the data base used for comprehensive mechanism development for the H₂/O₂ and CO/H₂O/O₂ systems. Several rate constants recommended in an earlier reaction mechanism have been modified using recently published rate constant data for H + O₂ (+ N₂) = HO₂ (+ N₂), HO₂ + OH = H₂O + O₂, and HO₂ + HO₂ = H₂O₂ + O₂. When these new rate constants are incorporated into the reaction mechanism, model predictions are in very good agreement with the experimental data. ©1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 113–125, 1999     

Flame acceleration and the transition to detonation of stoichiometric ethylene/oxygen in microscale tubes

Flame propagation in capillary tubes with smooth circular cross-sections and diameters of 0.5, 1.0, and 2.0 mm are investigated using high-speed photography. Flames were found to propagate and accelerate to detonation speed in stoichiometric ethylene and oxygen mixtures initially at room temperature in all three tube diameters. Ignition occurs at the midpoint along the length of the tube. We observe for the first time transition to detonation in micro-tubes. Detonation was observed with both spark and hot-wire ignition. Tubes with larger diameters take longer to transition to detonation. In fact, transition distance scales with the diameter in our 1.0 and 2.0 mm cases with spark ignition. Flame structures are observed for various stages of the process. Three types of flame propagation modes were observed in the 0.5 mm tube with spark ignition: (a) acceleration to Chapman–Jouguet (CJ) detonation speed followed by constant CJ wave propagation, (b) acceleration to CJ speed, followed by the detonation wave failure, and (c) flame acceleration to a constant speed below the CJ speed of approximately 1600 m/s. The current detonation mechanism observed in capillary tubes is applicable to predetonators for pulsed detonation, micro propulsion devices, safety issues, and addresses fundamental issues raised by recent theoretical and numerical analyses.     

Progress towards nanoengineered energetic materials

Given the constraints on typical bond energies and the commonality of final products produced from combustion of CHNO based energetic materials, the possibilities for further increases in stored potential energy and thermodynamic performance from these classes of materials are limited. Thus, modulating the energy release to achieve efficiency and effectiveness for desired applications is of great value. Investigation of nanomaterials as energetic materials began more than twenty years ago with much of the interest to increase reaction rates and reduce sensitivity. During this period, research on energetic nanoparticles was devoted to reducing the loss of energy density with metallic materials due to the naturally occurring oxide passivating layer, managing their high surface area preventing high loadings in solids, minimizing particle-particle interactions making dispersion in the gas-phase difficult, and understanding combustion mechanisms. As an outcome, novel synthesis methods of producing nanocomposites, and new fields of applications, such as micro-pyrotechnics, have developed. Yet, the research community is only beginning to understand how to manipulate and build energetic materials at the nanoscale, and what designs are optimal for desired functions. Furthermore, recognizing the difficulties for increased energy density and reduced sensitivity, the development of multifunctional and smart nanoenergetic materials is currently being researched to enable control of energy release rates and material sensitivity on demand. This research is being advanced by assembly of nanoengineered energetic materials to bulk scales by additive manufacturing, the development and application of combustion diagnostics that resolve nanometer and micron scales, and ab initio quantum chemistry and molecular dynamics calculations. The challenges that have been confronted and the directions of continuing research on nanoenergetics are presented and discussed.     

Realizing microgravity flame spread characteristics at 1 g over a bed of nano-aluminum powder

Nanoscale aluminum (nAl) powders demonstrate relatively fast counter-flow flame spread rates compared to typical fuels such as Poly(methyl methacrylate) or cellulose at similar conditions. This allows for the dominant forward heat transfer mechanism to be through the solid fuel at higher applied oxidizer velocities, and flame structure characteristics typically observed in microgravity to be realized at 1 g conditions. Because of the porosity of the nAl powder, the gaseous oxidizer can diffuse into the bed and reactions within the solid phase become important. Using an energy balance applied to only the solid phase, an analytical model is developed which predicts the experiments for flame spread over a nAl bed. Moreover, an explanation for fingering phenomenon is established based on the effective Lewis and Damköhler numbers. This allows for an explanation of why flame spread over a bed of nAl will demonstrate this fingering instability in a quiescent, 1 g environment without a top plate to hinder buoyant flows.     

AP/(N2 + C2H2 + C2H4) gaseous fuel diffusion flame studies

Counterflow diffusion flame experiments and modeling results are presented for a fuel mixture consisting of N₂, C₂H₂, and C₂H₄ flowing against decomposition products from a solid AP pellet. The flame zone simulates the diffusion flame structure that is expected to exist between reaction products from AP crystals and a hydrocarbon binder. Quantitative species and temperature profiles have been measured for one strain rate, given by a separation of 5 mm, between the fuel exit and the AP surface. Species measured include C₂H₂, C₂H₄, N₂, CN, NH, OH, CH, C₂, NO, NO₂, O₂, CO₂, H₂, CO, HCl, H₂O, and soot volume fraction. Temperature was measured using a combination of a thermocouple at the fuel exit and other selected locations, spontaneous Raman scattering measurements throughout the flame, NO vibrational populations, and OH rotational population distributions. The burning rate of the AP was also measured for this flame’s strain rate. The measured eighteen scalars are compared with predictions from a detailed gas-phase kinetics model consisting of 105 species and 660 reactions. Model predictions are found to be in good agreement with experiment and illustrate the type of kinetic features that may be expected to occur in propellants when AP particles burn with the decomposition products of a polymeric binder.     

Flow reactor studies of methyl radical oxidation reactions in methane‐perturbed moist carbon monoxide oxidation at high pressure with model sensitivity analysis

New rate constant determinations for the reactions CH₃ + HO₂ → CH₃O + OH (1) CH₃ + HO₂ → CH₄ + O₂ (2) CH₃ + O₂ → CH₂O + OH (3) were made at 1000 K by fitting species profiles from high‐pressure flow reactor experiments on moist CO oxidation perturbed with methane. These reactions are important steps in the intermediate‐temperature burnout of hydrocarbon pollutants, especially at super‐atmospheric pressure. The experiments used in the fit were selected to minimize the uncertainty in the determinations. These uncertainties were estimated using model sensitivity coefficients, derived for time‐shifted flow reactor experiments, along with literature uncertainties for the unfitted rate constants. The experimental optimization procedure significantly reduced the uncertainties in each of these rate constants over the current literature values. The new rate constants and their uncertainties were determined to be, at 1000 K: k₁ = 1.48(10)¹³ cm³ mol⁻¹ s⁻¹ (UF = 2.24) k₂ = 3.16(10)¹² cm³ mol⁻¹ s⁻¹ (UF = 2.89) k₃ = 2.36(10)⁸ cm³ mol⁻¹ s⁻¹ (UF = 4.23) There are no direct and few indirect measurements of reactions ( 1 ) and ( 2 ) in the literature. There are few measurements of reaction ( 3 ) near 1000 K. These results therefore represent an important refinement to radical oxidation chemistry of significance to methane and higher alkane oxidation. The model sensitivity analysis used in the experimental design was also used to characterize the mechanistic dependence of the new rate constant values. Linear sensitivities of the fitted rate constants to the unfitted rate constants were given. The sensitivity analysis was used to show that the determinations above are primarily dependent on the rate constants chosen for the reactions CH₃ + CH₃ + M → C₂H₆ + M and CH₂O + HO₂ → HCO + H₂O₂. Uncertainties in the rate constants of these two reactions are the primary contributors to the uncertainty factors given above. Further reductions in the uncertainties of these kinetics would lead to significant reductions in the uncertainties in our determinations of k₁, k₂, and k₃. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 75–100, 2001     

Evaluation of the rate constants in chemical reactions

This article is concerned with the application of a new method to recover the rate constants in chemical reactions. The method is based on treating the unknown parameters as time dependent. With appropriate experimental data the unknown rate constants are guided from an arbitrary initial condition to their true value at a final time. An explicit equation describing the time evolution of the parameters is obtained by minimizing the error along the trajectory. The method leads to an iterative algorithm which is described in detail. Numerical results with the method indicate that accurate estimates of the rate constants can be obtained directly from experimental data. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 151–159, 1998.