Flame-propagation rates in ammonia-air combustion at high pressure

The reluctance of ammonia to be ignited easily and the necessity to advance the spark for optimum performance in combustion engines led to this investigation. Ionization gap techniques showed that long induction times and slow flame speed were both contributors to the observed phenomena. The most important factor in determining combustion characteristics of ammonia was found to be the extent of predissociation prior to attempted ignition. There was evidence from combustion gas analysis that NO + was the probable most abundant ion contributing to succesful application of the ionization gap techniques, and that the NO + was probably produced in the pyrolysis of ammonia rather than by equilibrium reactions. © 1967 Combustion Institute.

Human exposure to particulate and gaseous pollutants in a bar.

There is increasing evidence of a causal link between airborne particles and ill health and this study examined the exposure to both airborne particles and the gas phase contaminants of environmental tobacco smoke (ETS) in a bar. The work reported here utilized concurrent and continuous monitoring using real-time optical scattering personal samplers to record particulate (PM10) concentrations at two internal locations. Very high episodes were observed in seating areas compared with the bar area. A photo-acoustic multi-gas analyser was used to record the gas phases (CO and CO2) at eight different locations throughout the bar and showed little spatial variation. This gave a clear indication of the problems associated with achieving acceptable Indoor Air Quality in a public space and identified a fundamental problem with the simplistic design approach taken to ventilate the space. Both gaseous and particulate concentrations within the bar were below maximum recommended levels although the time-series analysis illustrated the highly episodic nature of this exposure.

Analytical and Experimental Investigation of an Ammonia/Air Opposed Reacting Jet

The point-by-point properties of an ammonia/air opposed-reacting-jet flowfield are described by solving the governing partial differential elliptic equations. Analytical descriptions of the reacting flowfield are compared to experimentally measured profiles of temperature and composition. Calculated distributions of stream function, temperature and fuel mole fraction are also presented. © 1972, Taylor & Francis Group, LLC. All rights reserved.

DISSOLVED AND GASEOUS FLUXES OF CARBON AND NITROGEN FROM URBAN WATERSHEDS OF THE CHESAPEAKE BAY

Carbon and nitrogen loading to streams and rivers contributes to eutrophication as well as greenhouse gas (GHG) production in streams, rivers and estuaries. My dissertation consists of three research chapters, which examine interactions and potential trade-offs between water quality and greenhouse gas production in urban streams of the Chesapeake Bay watershed. My first research project focused on drivers of carbon export and quality in an urbanized river. I found that watershed carbon sources (soils and leaves) contributed more than in-stream production to overall carbon export, but that periods of high in-stream productivity were important over seasonal and daily timescales. My second research chapter examined the influence of urban storm-water and sanitary infrastructure on dissolved and gaseous carbon and nitrogen concentrations in headwater streams. Gases (CO2, CH4, and N2O) were consistently super-saturated throughout the course of a year. N2O concentrations in streams draining septic systems were within the high range of previously published values. Total dissolved nitrogen concentration was positively correlated with CO2 and N2O and negatively correlated with CH4. My third research chapter examined a long-term (15-year) record of GHG emissions from soils in rural forests, urban forest, and urban lawns in Baltimore, MD. CO2, CH4, and N2O emissions showed positive correlations with temperature at each site. Lawns were a net source of CH4 + N2O, whereas forests were net sinks. Gross CO2 fluxes were also highest in lawns, in part due to elevated growing-season temperatures. While land cover influences GHG emissions from soils, the overall role of land cover on this flux is very small (< 0.5%) compared with gases released from anthropogenic sources, according to a recent GHG budget of the Baltimore metropolitan area, where this study took place.

A contribution towards the performance and structural understanding of copper and nickel salts as ammonia stores

The ongoing depletion of fossil fuels and the severe consequences of the greenhouse effect make the development of alternative energy systems crucially important. While hydrogen is, in principle, a promising alternative, releasing nothing but energy and pure water. Hydrogen storage is complicated and no completely viable technique has been proposed so far. This work is concerned with the study of one potential alternative to pure hydrogen: ammonia, and more specifically its storage in solids. Ammonia, NH3, can be regarded as a chemical hydrogen carrier with the advantages of strongly reduced flammability and explosiveness as compared to hydrogen. Furthermore, ammine metal salts presented here as promising ammonia stores easily store up to 50 wt.-% ammonia, giving them a volumetric energy density comparable to natural gas. The model system NiX2–NH3 ( X = Cl, Br, I) is studied thoroughly with respect to ammine salt formation, thermal decomposition, air stability and structural effects. The system CuX2–NH3 ( X = Cl, Br) has an adverse thermal decomposition behaviour, making it impractical for use as an ammonia store. This system is, however, most interesting from a structural point of view and some work concerning the study of the structural behaviour of this system is presented. Finally, close chemical relatives to the metal ammine halides, the metal ammine nitrates are studied. They exhibit interesting anion arrangements, which is an impressive showcase for the combination of diffraction and spectroscopic information. The characterisation techniques in this thesis range from powder diffraction over single crystal diffraction, spectroscopy, computational modelling, thermal analyses to gravimetric uptake experiments. Further highlights are the structure solutions and refinements from powder data of (NH4)2[NiCl4(H2O)(NH3)] and Ni(NH3)2(NO3)2, the combination of crystallographic and chemical information for the elucidation of the (NH4)2[NiCl4(H2O)(NH3)] formation reaction and the growth of single crystals under ammonia flow, a technique allowing the first documented successful growth and single crystal diffraction measurement for [Cu(NH3)6]Cl2.

Performance of Plate Type Heat Exchanger as Ammonia Condenser

In this study, I experimentally analyzed the performance of a commercial semi-welded plate type heat exchanger (PHE) for use with ammonia systems. I determined performance parameters such as overall heat transfer coefficient, capacity, and pressure drop of the semi-welded PHE. This was analyzed by varying different parameters which demonstrated changes in overall heat transfer coefficient, capacity, and pressure drop. Both water and ammonia flow rates to the semi-welded PHE were varied independently, and analyzed in order to understand how changes in flow rates affected performance. Inlet water temperature was also varied, in order to understand how raising condenser water inlet temperature would affect performance. Finally, pressure drop was monitored to better understand the performance limitations of the semi-welded PHE. Testing of the semi-welded will give insight as to the performance of the semi-welded PHE in a potential ocean thermal energy conversion system, and whether the semi-welded PHE is a viable choice for use as an ammonia condenser.

Development of combined acidification and separation of slurry: effect on slurry fractions composition and gaseous emission

Doutoramento em Engenharia do Ambiente - Instituto Superior de Agronomia - UL

Stress in pacu exposed to ammonia in water

The present study evaluated stress indicators in pacu exposed to ammonia in water under the following conditions: without NH4Cl (0.00 g/L); with 0.0078 g NH4Cl/L; and with 0.078 g NH4Cl/L (pH 8.3 and 27 ºC). After the salt dilution the water flow was interrupted and reestablished in 24 hours. Sampling occurred prior to the addition of NH4Cl (control) and after 12, 24 and 48 hours. Glycaemia increased only in fish with the highest salt concentration when compared with group control, regardless of time, and at 24 hours, regardless of treatment. Plasma ammonia, highest in fish exposed to the highest NH4Cl concentration, decreased progressively up to 48 hours. Plasma chloride only decreased in fish not exposed to salt when compared with control and osmolality increased after 24 hours. Hematocrit (Ht), number and volume of erythrocytes and hemoglobin did not change when NH4Cl was added; Ht decrease was reported after 12 hours, but it was not followed by the other blood parameters. The results show tolerance of the pacu to ammonia in the environment.

Ammonia effects on proton conductivity properties of coordination polymers

Crystalline metal phosphonates are referred to as a type of structurally versatile coordination polymers [1]. Many of them contain guest molecules (H2O, heterocyclics, etc.), acidic sites and, furthermore, their structure can be also amenable for post‐synthesis modifications in order to enhance desired properties [2]. In the present work, we examine the relationships between crystal structure and proton conductivity for several metal phosphonates derive from multifunctional ligands, such as 5-(dihydroxyphosphoryl)isophthalic acid (PiPhtA) [3] and 2-hydroxyphosphonoacetic acid (H3HPAA). Crystalline divalent metal derivatives show a great structural diversity, from 1D to 3D open-frameworks, possessing hydrogen-bonded water molecules and acid groups. These solids present a proton conductivity range between 7.2·10-6 and 1.3·10−3 S·cm-1. Upon exposure to ammonia vapor, from an aqueous solution, solid state transformations are observed accompanied of enhance proton conductivities. The stability of these solids under different environment conditions (temperature and relative humidities) as well as the influence of the ammonia adsorption on the proton conduction properties of the resulting solids will be discussed.

Study of ammonia borane and its derivatives: Influence of nanoconfinements and pressures

Recently, ammonia borane has increasingly attracted researchers’ attention because of its merging applications, such as organic synthesis, boron nitride compounds synthesis, and hydrogen storage. This dissertation presents the results from several studies related to ammonia borane. ^ The pressure-induced tetragonal to orthorhombic phase transition in ammonia borane was studied in a diamond anvil cell using in situ Raman spectroscopy. We found a positive Clapeyron-slope for this phase transformation in the experiment, which implies that the phase transition from tetragonal to orthorhombic is exothermic. The result of this study indicates that the rehydrogenation of the high pressure orthorhombic phase is expected to be easier than that of the ambient pressure tetragonal phase due to its lower enthalpy. ^ The high pressure behavior of ammonia borane after thermal decomposition was studied by in situ Raman spectroscopy at high pressures up to 10 GPa. The sample of ammonia borane was first decomposed at ∼140 degree Celcius and ∼0.7 GPa and then compessed step wise in an isolated sample chamber of a diamond anvil cell for Raman spectroscopy measurement. We did not observe the characteristic shift of Raman mode under high pressure due to dihydrogen bonding, indicating that the dihydrogen bonding disappears in the decomposed ammonia borane. Although no chemical rehydrogenation was detected in this study, the decomposed ammonia borane could store extra hydrogen by physical absorption. ^ The effect of nanoconfinement on ammonia borane at high pressures and different temperatures was studied. Ammonia borane was mixed with a type of mesoporous silica, SBA-15, and restricted within a small space of nanometer scale. The nano-scale ammonia borane was decomposed at ∼125 degree Celcius in a diamond anvil cell and rehydrogenated after applying high pressures up to ∼13 GPa at room temperature. The successful rehydrogenation of decomposed nano-scale ammonia borane gives guidance to further investigations on hydrogen storage. ^ In addition, the high pressure behavior of lithium amidoborane, one derivative of ammonia borane, was studied at different temperatures. Lithium amidoborane (LAB) was decomposed and recompressed in a diamond anvil cell. After applying high pressures on the decomposed lithium amidoborane, its recovery peaks were discovered by Raman spectroscopy. This result suggests that the decomposition of LAB is reversible at high pressures.^

High Pressure and Low Temperature Study of Ammonia Borane and Lithium Amidoborane

Hydrogen has been considered as a potentially efficient and environmentally friendly alternative energy solution. However, one of the most important scientific and technical challenges that the “hydrogen economy” faces is the development of safe and economically viable on-board hydrogen storage for fuel cell applications, especially to the transportation sector. Ammonia borane (BH3NH3), a solid state hydrogen storage material, possesses exceptionally high hydrogen content (19.6 wt%).However, a fairly high temperature is required to release all the hydrogen atoms, along with the emission of toxic borazine. Recently research interests are focusing on the improvement of H2 discharge from ammonia borane (AB) including lowering the dehydrogenation temperature and enhancing hydrogen release rate using different techniques. Till now the detailed information about the bonding characteristics of AB is not sufficient to understand details about its phases and structures. Elemental substitution of ammonia borane produces metal amidoboranes. Introduction of metal atoms to the ammonia borane structure may alter the bonding characteristics. Lithium amidoborane is synthesized by ball milling of ammonia borane and lithium hydride. High pressure study of molecular crystal provides unique insight into the intermolecular bonding forces and phase stability. During this dissertation, Raman spectroscopic study of lithium amidoborane has been carried out at high pressure in a diamond anvil cell. It has been identified that there is no dihydrogen bond in the lithium amidoborane structure, whereas dihydrogen bond is the characteristic bond of the parent compound ammonia borane. It has also been identified that the B-H bond becomes weaker, whereas B-N and N-H bonds become stronger than those in the parent compound ammonia borane. At high pressure up to 15 GPa, Raman spectroscopic study indicates two phase transformations of lithium amidoborane, whereas synchrotron X-ray diffraction data indicates only one phase transformation of this material. Pressure and temperature has a significant effect on the structural stability of ammonia borane. This dissertation explored the phase transformation behavior of ammonia borane at high pressure and low temperature using in situ Raman spectroscopy. The P-T phase boundary between the tetragonal (I4mm) and orthorhombic (Pmn21) phases of ammonia borane has been determined. The transition has a positive Clapeyron slope which indicates the transition is of exothermic in nature. Influence of nanoconfinemment on the I4mm to Pmn21 phase transition of ammonia borane was also investigated. Mesoporus silica scaffolds SBA-15 with pore size of ~8 nm and MCM-41 with pore size of 2.1-2.7 nm, were used to nanoconfine ammonia borane. During cooling down, the I4mm to Pmn21 phase transition was not observed in MCM-41 nanoconfined ammonia borane, whereas the SBA-15 nanocondfined ammonia borane shows the phase transition at ~195 K. Four new phases of ammonia borane were also identified at high pressure up to 15 GPa and low temperature down to 90 K.

Composting of different agro-food wastes: Effects of the phenolic and lignocellulosic fractions on greenhouse gases emissions

Currently, society faces a number of challenges related to the large amounts of organic wastes generated and accumulated by the increasing expansion of agroindustrial activities1. Most of these wastes are rich in lignocellulosic compounds, which represents a major fraction of all plant biomass (of above 90%), so, its degradation is crucial for global carbon cycle2. These organic wastes may be introduced directly on agriculture sector as soil organic amendment, however, these might contain phytochemicals, such as phenolic compounds which may introduce toxic effects to soil and to beneficial organisms. Transformation and degradation of these renewable organic wastes into composts (COMPOSTING) is a possible solution for these problems and an environmentally friendly processes that allows make use of natural resources efficiently3. The main potential handicap is generation and emission of greenhouse gases such as carbon dioxide (CO2 ), methane (CH4 ) and nitrous oxide (N2O) and another ones which may led serious problems like nitric oxide (NO) and ammonia (NH3) 4. For this reason, quantification of GHG emissions from composting and finding possible relations with the chemical and structural composition of the wastes used is crucial to the development of technologies for mitigating emissions and should help to make decisions concerning waste management.