RESUMEN

Understanding the fundamental mechanisms of chemical reactions is of great interest to scientists working in many fields as it enables the rationalization, prediction, and design of reactions. Many chemical processes involve the formation of short-lived reaction intermediates, most of which cannot be isolated and are challenging to detect. One such intermediate is the tetrahedral intermediate often proposed to be generated upon the reactions of acetyl chlorides with simple alcohols via an addition/elimination mechanism. However, the formation of this tetrahedral intermediate is a subject of controversy as it has not been detected. Furthermore, some kinetic evidence suggests the SN2 mechanism for this reaction. In the present investigation, a 266 nm pulsed Nd:YAG laser was used to evaporate and ionize reactants, reaction intermediates, and products in microdroplets of acetyl chloride and ethanol. A linear quadrupole ion trap mass spectrometer was used to detect the ions and collision-activated dissociation (CAD) experiments were employed for their structural characterization. The results demonstrate the formation of the protonated tetrahedral intermediate of the addition/elimination reaction. The protonated reaction intermediate was isolated and subjected to CAD, which resulted in the loss of water and ethylene, thus confirming its structure. These results demonstrate that the ethanolysis of acetyl chloride proceeds via an addition/elimination mechanism involving a tetrahedral reaction intermediate. However, the parallel occurrence of the SN2 mechanism cannot be ruled out.

RESUMEN

A significant drawback to ammonia borane as a hydrogen storage material is the production of ammonia gas during hydrolysis. As a possible solution, maleic acid is shown to be capable of fully promoting hydrolysis of ammonia borane while also preventing ammonia release in excess of single digit parts per million. The reaction is shown to be relatively insensitive towards common water contaminants, with seawater, puddle water, and synthetic urine resulting in hydrogen evolution comparable to that observed when using highly pure deionized water. A common cola beverage was also investigated as a potential water source, with results deviating from those observed when using the other water sources. The ability to use low quality water sources presents the option of acquiring water at the point of use, greatly increasing the energy density of the system during transportation. For each of the water sources being used, concentrations of ammonia in the gas products of maleic acid-promoted hydrolysis were found to be less than the lower detection limits of the employed analysis methods. Based on this reaction, a portable hydrogen reactor is reported and shown to be capable of on-demand hydrogen generation sufficient to power a proton exchange membrane fuel cell at varying loads without significant changes in system pressure. The overall power production system has substantial value in scenarios where electrical power is required but there is no access to an established electrical utility, with prime examples including disaster relief and expeditionary military operations.

Asunto(s)

RESUMEN

Complexation of amines with borane converts them to hypergols or decreases their ignition delays (IDs) multifold (with white fuming nitric acid as the oxidant). With consistently low IDs, amine-boranes represent a class of compounds that can be promising alternatives to toxic hydrazine and its derivatives as propellants. A structure-hypergolicity relationship study reveals the necessary features for the low ID.

RESUMEN

Imaging dynamic multiphase combusting events is challenging. Conventional techniques can image only a single plane of an event, capturing limited details. Here, we report on a three-dimensional, time-resolved, OH planar laser-induced fluorescence (3D OH PLIF) technique that was developed to measure the relative OH concentration in multiphase combustion flow fields. To the best of our knowledge, this is the first time a 3D OH PLIF technique has been reported in the open literature. The technique involves rapidly scanning a laser sheet across a flow field of interest. The overall experimental system consists of a 5 kHz OH PLIF system, a high-speed detection system (image intensifier and CMOS camera), and a galvanometric scanning mirror. The scanning mirror was synchronized with a 500 Hz triangular sweep pattern generated using Labview. Images were acquired at 5 kHz corresponding to six images per mirror scan, and 1000 scans per second. The six images obtained in a scan were reconstructed into a volumetric representation. The resulting spatial resolution was 500×500×6 voxels mapped to a field of interest covering 30 mm×30 mm×8 mm. The novel 3D OH PLIF system was applied toward imaging droplet combustion of methanol gelled with hydroxypropyl cellulose (HPC) (3 wt. %, 6 wt. %), as well as solid propellant combustion, and impinging jet spray combustion. The resulting 3D dataset shows a comprehensive view of jetting events in gelled droplet combustion that was not observed with high-speed imaging or 2D OH PLIF. Although the scan is noninstantaneous, the temporal and spatial resolution was sufficient to view the dynamic events in the multiphase combustion flow fields of interest. The system is limited by the repetition rate of the pulsed laser and the step response time of the galvanometric mirror; however, the repetition rates are sufficient to resolve events in the order of 100 Hz. Future upgrade includes 40 kHz pulsed UV laser system, which can reduce the scan time to 125 µs, while keeping the high repetition rate of 1000 Hz.

RESUMEN

Analysis techniques for determining gas-solid reaction rates from gas sorption measurements obtained under non-constant pressure and temperature conditions often neglect temporal variations in these quantities. Depending on the materials in question, this can lead to significant variations in the measured reaction rates. In this work, we present two new analysis techniques for comparison between various kinetic models and isochoric gas measurement data obtained under varying temperature and pressure conditions in a high pressure Sievert system. We introduce the integral pressure dependence method and the temperature dependence factor as means of correcting for experimental variations, improving model-measurement fidelity, and quantifying the effect that such variations can have on measured reaction rates. We use measurements of hydrogen absorption in LaNi5 and TiCrMn to demonstrate the effect of each of these methods and show that their use can provide quantitative improvements in interpretation of kinetics measurements.

RESUMEN

Mass and thermal diffusivity measurements conducted on Earth are prone to contamination by uncontrollable convective contributions to the overall transport. Previous studies of mass and thermal diffusivities conducted on spacecraft have demonstration the gain in precision, and lower absolute values, resulting from the reduced convective transport possible in a low-gravity environment. We have developed and extensively tested real-time techniques for diffusivity measurements, where several measurements may be obtained on a single sample. This is particularly advantageous for low gravity research were there is limited experiment time. The mass diffusivity methodology uses a cylindrical sample geometry. A radiotracer, initially located at one end of the host is used as the diffusant. The sample is positioned in a concentric isothermal radiation shield with collimation bores located at defined positions along its axis. The intensity of the radiation emitted through the collimators is measured versus time with solid-state detectors and associated energy discrimination electronics. For the mathematical algorithm that we use, only a single pair of collimation bores and detectors are necessary for single temperature measurements. However, by employing a second, offset, pair of collimation holes and radiation detectors, diffusivities can be determined at several temperatures per sample. For thermal diffusivity measurements a disk geometry is used. A heat pulse is applied in the center of the sample and the temperature response of the sample is measured at several locations. Thus, several values of the diffusivity are measured versus time. The exact analytic solution to a heat pulse in the disk geometry leads to a unique heated area and measurement locations. Knowledge of the starting time and duration of he heating pulse is not used in the data evaluation. Thus, this methodology represents an experimentally simpler and more robust scheme.