I. The crystal structure of potassium bis(tricyanovinyl)amine. II. Nuclear magnetic resonance studies of alkali halide solutions. III. Elucidation of the intramolecular hydrogen bond in acetylacetone by the deuterium isotope effect on the chemical shift of the bridge hydrogen

Part I

Potassium bis-(tricyanovinyl) amine, K⁺N[C(CN)=C(CN)₂]₂^-, crystallizes in the monoclinic system with the space group Cc and lattice constants, a = 13.346 ± 0.003 Å, c = 8.992 ± 0.003 Å, B = 114.42 ± 0.02°, and Z = 4. Three dimensional intensity data were collected by layers perpendicular to b* and c* axes. The crystal structure was refined by the least squares method with anisotropic temperature factor to an R value of 0.064.

The average carbon-carbon and carbon-nitrogen bond distances in –C-CΞN are 1.441 ± 0.016 Å and 1.146 ± 0.014 Å respectively. The bis-(tricyanovinyl) amine anion is approximately planar. The coordination number of the potassium ion is eight with bond distances from 2.890 Å to 3.408 Å. The bond angle C-N-C of the amine nitrogen is 132.4 ± 1.9°. Among six cyano groups in the molecule, two of them are bent by what appear to be significant amounts (5.0° and 7.2°). The remaining four are linear within the experimental error. The bending can probably be explained by molecular packing forces in the crystals.

Part II

The nuclear magnetic resonance of ⁸¹Br and ¹²⁷I in aqueous solutions were studied. The cation-halide ion interactions were studied by studying the effect of the Li⁺, Na⁺, K⁺, Mg⁺⁺, Cs⁺ upon the line width of the halide ions. The solvent-halide ion interactions were studied by studying the effects of methanol, acetonitrile, and acetone upon the line width of ⁸¹Br and ¹²⁷I in the aqueous solutions. It was found that the viscosity plays a very important role upon the halide ions line width. There is no specific cation-halide ion interaction for those ions such as Mg⁺⁺, Di⁺, Na⁺, and K⁺, whereas the Cs⁺ - halide ion interaction is strong. The effect of organic solvents upon the halide ion line width in aqueous solutions is in the order acetone ˃ acetonitrile ˃ methanol. It is suggested that halide ions do form some stable complex with the solvent molecules and the reason Cs⁺ can replace one of the ligands in the solvent-halide ion complex.

Part III

An unusually large isotope effect on the bridge hydrogen chemical shift of the enol form of pentanedione-2, 4(acetylacetone) and 3-methylpentanedione-2, 4 has been observed. An attempt has been made to interpret this effect. It is suggested from the deuterium isotope effect studies, temperature dependence of the bridge hydrogen chemical shift studies, IR studies in the OH, OD, and C=O stretch regions, and the HMO calculations, that there may probably be two structures for the enol form of acetylacetone. The difference between these two structures arises mainly from the electronic structure of the π-system. The relative population of these two structures at various temperatures for normal acetylacetone and at room temperature for the deuterated acetylacetone were calculated.

High frequency wave propagation in the earth: theory and observation

The wave-theoretical analysis of acoustic and elastic waves refracted by a spherical boundary across which both velocity and density increase abruptly and thence either increase or decrease continuously with depth is formulated in terms of the general problem of waves generated at a steady point source and scattered by a radially heterogeneous spherical body. A displacement potential representation is used for the elastic problem that results in high frequency decoupling of P-SV motion in a spherically symmetric, radially heterogeneous medium. Through the application of an earth-flattening transformation on the radial solution and the Watson transform on the sum over eigenfunctions, the solution to the spherical problem for high frequencies is expressed as a Weyl integral for the corresponding half-space problem in which the effect of boundary curvature maps into an effective positive velocity gradient. The results of both analytical and numerical evaluation of this integral can be summarized as follows for body waves in the crust and upper mantle:

1) In the special case of a critical velocity gradient (a gradient equal and opposite to the effective curvature gradient), the critically refracted wave reduces to the classical head wave for flat, homogeneous layers.

2) For gradients more negative than critical, the amplitude of the critically refracted wave decays more rapidly with distance than the classical head wave.

3) For positive, null, and gradients less negative than critical, the amplitude of the critically refracted wave decays less rapidly with distance than the classical head wave, and at sufficiently large distances, the refracted wave can be adequately described in terms of ray-theoretical diving waves. At intermediate distances from the critical point, the spectral amplitude of the refracted wave is scalloped due to multiple diving wave interference.

These theoretical results applied to published amplitude data for P-waves refracted by the major crustal and upper mantle horizons (the Pg, P*, and Pn travel-time branches) suggest that the 'granitic' upper crust, the 'basaltic' lower crust, and the mantle lid all have negative or near-critical velocity gradients in the tectonically active western United States. On the other hand, the corresponding horizons in the stable eastern United States appear to have null or slightly positive velocity gradients. The distribution of negative and positive velocity gradients correlates closely with high heat flow in tectonic regions and normal heat flow in stable regions. The velocity gradients inferred from the amplitude data are generally consistent with those inferred from ultrasonic measurements of the effects of temperature and pressure on crustal and mantle rocks and probable geothermal gradients. A notable exception is the strong positive velocity gradient in the mantle lid beneath the eastern United States (2 x 10^-3 sec^-1), which appears to require a compositional gradient to counter the effect of even a small geothermal gradient.

New seismic-refraction data were recorded along a 800 km profile extending due south from the Canadian border across the Columbia Plateau into eastern Oregon. The source for the seismic waves was a series of 20 high-energy chemical explosions detonated by the Canadian government in Greenbush Lake, British Columbia. The first arrivals recorded along this profile are on the Pn travel-time branch. In northern Washington and central Oregon their travel time is described by T = Δ/8.0 + 7.7 sec, but in the Columbia Plateau the Pn arrivals are as much as 0.9 sec early with respect to this line. An interpretation of these Pn arrivals together with later crustal arrivals suggest that the crust under the Columbia Plateau is thinner by about 10 km and has a higher average P-wave velocity than the 35-km-thick, 62-km/sec crust under the granitic-metamorphic terrain of northern Washington. A tentative interpretation of later arrivals recorded beyond 500 km from the shots suggests that a thin 8.4-km/sec horizon may be present in the upper mantle beneath the Columbia Plateau and that this horizon may form the lid to a pronounced low-velocity zone extending to a depth of about 140 km.

Estudo termodinâmico da precipitação de parafinas em petróleos brasileiros

Um dos grandes desafios enfrentados pela indústria do petróleo é reduzir o impacto causado pela cristalização indesejável de hidrocarbonetos parafínicos de elevada massa molar em tubulações e equipamentos de produção. A cristalização de parafinas em petróleo é normalmente detectada através da determinação da temperatura inicial de aparecimento de cristais (TIAC), que pode ser estimada através de modelagem termodinâmica com base na composição do petróleo. Os objetivos deste trabalho são: estudar os principais modelos termodinâmicos adotados para descrever a precipitação de parafinas; verificar a validade desses modelos para os petróleos brasileiros e determinar qual modelo é o mais adequado para esses óleos. Para tanto, três formas de cálculo da razão entre as fugacidades das fases sólida e líquida e cinco modelos para calcular os coeficientes de atividade dos componentes em cada fase são aplicados aos dados de composição de vinte e três petróleos brasileiros. Os resultados mostram que o modelo ideal de múltiplas fases sólidas e o modelo de Escobar-Remolina geram valores bastante abaixo da TIAC experimental. Para os modelos de única fase sólida ideal, de Won e de Coutinho, foi possível observar que: a) a grande maioria dos erros é negativa; b) que estes se distribuem melhor em torno de zero quando se utiliza a correlação de Coutinho para o cálculo dos valores de i; c) os valores de erro médio para os modelos de Coutinho, de Won e ideal com única fase sólida se equivalem, qualquer que seja o modelo utilizado para o cálculo de i, exceto para o caso em que todos os compostos presentes na fase líquida podem precipitar; d) os valores obtidos através do modelo de Coutinho apresentam erro sistemático em relação ao modelo ideal de única fase sólida; e) as diferentes formas de se calcular a razão entre as fugacidades da fase sólida e líquida (i) influenciam fortemente a capacidade preditiva dos modelos, o que não era esperado; f) o perfil do primeiro cristal formado nos petróleos é influenciado pelas moléculas mais pesadas presentes nos resíduos, o que mostra a necessidade de se desenvolver metodologias precisas e robustas de caracterização de resíduos; g) a inclusão de uma estimativa para a composição dos resíduos efetivamente melhorou o desempenho dos modelos em petróleos médio; h) em petróleos pesados, houve um aumento do erro de previsão da TIAC devido à pouca ou nenhuma quantidade de parafinas nos resíduos desses óleos. A necessidade de uma melhor caracterização dos resíduos de petróleos é corroborada pelo fato da TIAC calculada pelos modelos ser, via de regra, mais baixa que a TIAC experimental e pela melhora no desempenho dos modelos quando se estimou a composição dos resíduos, em petróleos médios

Mode properties of off-axis one-sided hybrid resonator for novel high average power dual-slab laser

A novel dual-slab laser with off-axis one-sided hybrid resonator is presented. The mode properties of the hybrid resonator are calculated using a fast Fourier transform method (FFT). The influence of wavefront distoration on the output beam quality is considered. Results indicate that the novel dual-slab laser is better than the normal dual-slab laser with off-axis one-sided hybrid resonator.

20-W average power, high repetition rate, nanosecond pulse with diffraction limit from an all-fiber MOPA system

In this article, we report an all-fiber master oscillator power amplifier (MOPA) system, which can provide high repetition rate and nanosecond pulse with diffraction-limit. The system was constructed using a (2 + 1) X 1 multimode combiner. The Q-Switched, LD pumped Nd:YVO4 solid-state laser wets used (is master oscillator. The 976-nm fiber-coupled module is used as pump source. A 10-m long China-made Yb3+-doped D-shape double-clad large-mode-area fiber was used as amplifier fiber. The MOPA produced as much as 20-W average power with nanosecond pulse and near diffraction limited. The pulse duration is maintained at about 15 its during 50-175 kHz. The system employs a simple and compact architecture and is therefore suitable for the use in practical applications such as scientific and military airborne LIDAR and imaging. Based oil this system. the amplification performances of. the all fiber amplifier is investigated. (C) 2008 Wiley Periodicals, Inc.

Welding of Al alloy plates using a novel high-average-power pulsed CO2 laser

A novel high-average-power pulsed CO2 laser with a unique electrode structure is presented. The operation of a 5-kW transverse-flow CO2 laser with the preionized pulse-train switched technique results in pulsation of the laser power, and the average laser power is about 5 kW. The characteristic of this technique is switching the preionized pulses into pulse trains so as to use the small preionized power (hundreds of watts) to control the large main-discharge power (tens of kilowatts). By this means, the cost and the complexity of the power supply are greatly reduced. The welding of LF2, LF21, LD2, and LY12 aluminum alloy plates has been successfully achieved using this laser. (c) 2005 Society of Photo-Optical Instrumentation Engineers.

Welding of Al alloy plates using a novel high-average-power pulsed CO2 laser

A novel high-average-power pulsed CO2 laser with a unique electrode structure is presented. The operation of a 5-kW transverse-flow CO2 laser with the preionized pulse-train switched technique results in pulsation of the laser power, and the average laser power is about 5 kW. The characteristic of this technique is switching the preionized pulses into pulse trains so as to use the small preionized power (hundreds of watts) to control the large main-discharge power (tens of kilowatts). By this means, the cost and the complexity of the power supply are greatly reduced. The welding of LF2, LF21, LD2, and LY12 aluminum alloy plates has been successfully achieved using this laser. (c) 2005 Society of Photo-Optical Instrumentation Engineers.

Ti:sapphire laser pumped high average power laser crystal Nd:GGG with high efficiency output

High-quality neodymium doped GGG laser crystals have been grown by Czochralski (Cz) method. Results of Nd:GGG thin chip laser operating at 1.064 μm pumped by Ti:sapphire laser operating at 808 nm were reported. The slop efficiency was as high as 20%.

Comparison of average larval fish vertical distributions among species exhibiting different transport pathways on the southeast United States continental shelf

Water currents are vertically structured in many marine systems and as a result, vertical movements by fish larvae and zooplankton affect horizontal transport (Power, 1984). In estuaries, the vertical movements of larvae with tidal periods can result in their retention or ingress (Fortier and Leggett, 1983; Rijnsdorp et al., 1985; Cronin and Forward, 1986; Forward et al., 1999). On the continental shelf, the vertical movements of organisms interact daily and ontogenetically with depth-varying currents to affect horizontal transport (Pillar et al., 1989; Barange and Pillar, 1992; Cowen et al., 1993, 2000; Batchelder et al., 2002).

Travel Characteristics of Marine Anglers Using Oil and Gas Platforms in the Central Gulf of Mexico

This study was designed to evaluate the travel characteristics of avid marine anglers off Louisiana in the Central Gulf of Mexico. It focuses on the complex marine travel patterns involving the extensive assemblage of oil and gas structures. In an intercept approach, marine recreationalf isherman were asked to identify near and offshore travel patterns on the day of the interview. Information was also solicited regarding how respondents selected and located fishing destinations as well as what method of fishing was undertaken that day. Petroleum platforms were a principal fishing destination, and platform anglers traveled an average distance of 75.5 km (40.7 n.mi.) to and from offshore fishing locations. In fishing an average of 6.5 platforms per trip, these anglers traveled about 21.3 km (11.5 n.mi.) between the first and last platform visited. Mean total distances for platform anglers were 96 km (51.8 n.mi). Travel distances for bay, nearshore, and bluewater anglers were also obtained.