999 resultados para kinetic spectra


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Incoherent Thomson scattering (ITS) provides a nonintrusive diagnostic for the determination of one-dimensional (1D) electron velocity distribution in plasmas. When the ITS spectrum is Gaussian its interpretation as a three-dimensional (3D) Maxwellian velocity distribution is straightforward. For more complex ITS line shapes derivation of the corresponding 3D velocity distribution and electron energy probability distribution function is more difficult. This article reviews current techniques and proposes an approach to making the transformation between a 1D velocity distribution and the corresponding 3D energy distribution. Previous approaches have either transformed the ITS spectra directly from a 1D distribution to a 3D or fitted two Gaussians assuming a Maxwellian or bi-Maxwellian distribution. Here, the measured ITS spectrum transformed into a 1D velocity distribution and the probability of finding a particle with speed within 0 and given value v is calculated. The differentiation of this probability function is shown to be the normalized electron velocity distribution function. (C) 2003 American Institute of Physics.

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Fully relativistic calculations of radiative rates and electron impact excitation cross-sections for Fe X are used to derive theoretical emission-line ratios involving transitions in the 174-366 angstrom wavelength range. A comparison of these with solar active region observations obtained during the 1989 and 1995 flights of the Solar Extreme-ultraviolet Research Telescope and Spectrograph (SERTS) reveals generally very good agreement between theory and experiment. Several Fe X emission features are detected for the first time in SERTS spectra, while the 3s(2)3p(5) P-2(3/2)-3s(2)3p(4)(S-1)3d D-2(3/2) transition at 195.32 angstrom is identified for the first time (to our knowledge) in an astronomical source. The most useful Fe X electron density (N-e) diagnostic line ratios are assessed to be 175.27/174.53 and 175.27/177.24, which both involve lines close in wavelength and free from blends, vary by factors of 13 between N-e = 10(8) and 10(11) cm(-3), and yet show little temperature sensitivity. Should these lines not be available, then the 257.25/345.74 ratio may be employed to determine N-e, although this requires an accurate evaluation of the instrument intensity calibration over a relatively large wavelength range. However, if the weak 324.73 angstrom line of Fe X is reliably detected, the use of 324.73/345.74 or 257.25/324.73 is recommended over 257.25/345.74. Electron densities deduced from 175.27/174.53 and 175.27/177.24 for the stars Procyon and alpha Cen, using observations from the Extreme-Ultraviolet Explorer (EUVE) satellite, are found to be consistent and in agreement with the values of N-e determined from other diagnostic ratios in the EUVE spectra. A comparison of several theoretical extreme-ultraviolet Fe X line ratios with experimental values for a theta-pinch, for which the plasma parameters have been independently determined, reveals reasonable agreement between theory and observation, providing some independent support for the accuracy of the adopted atomic data.

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Derivative spectroscopy has been utilised for the determination of amphotericin in various biological matrices including plasma, serum, urine and brain tissue. Whilst these methods have all been shown to be suitable for the determination of the drug in these matrices it has been reported that the application fails in the case of highly icteric plasma, this being due to the presence of high concentrations (>50 mu M) of bilirubin. This paper details the application of ratio spectra derivative spectroscopy to overcome the interference of bilirubin with amphotericin in such situations.

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The kinetics of the water-gas shift reaction Were Studied on a 0.2% Pt/CeO2 catalyst between 177 and 300 degrees C over a range of CO and steam pressures. A rate decrease with increasing partial pressure of CO was experimentally observed over this sample, confirming that a negative order in CO can occur under certain conditions at low temperatures. The apparent reaction order of CO measured at 197 degrees C was about -0.27. This value is significantly larger than that (i.e, -0.03) reported by Ribeiro and co-workers [A.A. Phatak, N. Koryabkina, S. Rai, J.L. Ratts, W. Ruettinger, R.J. Farrauto, G.E. Blau, W.N. Delgass, F.H. Ribeiro, Catal. Today 123 (2007) 224] at a similar temperature. A kinetic peculiarity was also evidenced, i.e. a maximum of the reaction rate as a function of the CO concentration or possibly a kinetic break, which is sometimes observed in the oxidation of simple molecules. These observations support the idea that competitive adsorption of CO and H2O play an essential role in the reaction mechanism. (C) 2008 Elsevier B.V. All rights reserved.

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The mechanism for the formation of NH3 during the NO-H-2 reaction over Pt/ZrO2 was studied. Steady-state isotopic transient kinetic analysis was carried out with isotopic switching from (NO)-N-15-D-2 to (NO)-N-14-D-2, and the results revealed that formation of N-2 and N2O was associated with linearly adsorbed NO on the Pt surface, whereas ammonia formation was associated with NDx species adsorbed on ZrO2. The adsorbed NHx species were not observed on the surface of ZrO2 during NH3 adsorption. From transient kinetic experiments, the formation rates of NHx species and of gaseous NH3 agreed with each other, suggesting that the NHx species on ZrO2 was an ammonia intermediate. The NDx species did not react with D-2 directly, but H-D exchange occurred easily. The addition of H2O to the NO-H-2 feed gas enhanced the formation of NH3. In situ diffuse reflectance spectra and transient kinetic analysis revealed that H2O enhanced the conversion of NHx species to NH3.

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Highly charged ions have been used to study the sputtering of positive molecular fragments from mercaptoundecanoic acid and dodecanethiol self-assembled monolayers on gold surfaces. The samples were bombarded with Arq+ (42n+, and Cn+1O2H2n + 1+ from mercaptoundecanoic and H+, CnH2n+, and Cn+1H2n + 3+ from dodecanethiol. The proton yields were increased with larger charge state q of the highly charged ion (HCI) in both samples, scaling as qgamma, with gamma~5. The charge state dependence is discussed in terms of electron transfer to the HCI. The final yield of protons depends on molecular functional group characteristics, orientation on the surface, and reneutralization phenomena.

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The influence of ageing and cooking on the Raman spectrum of porcine longissimus dorsi was investigated. The rich information contained in the Raman spectrum was highlighted, with numerous changes attributed to changes in the environment and conformations of the myofibrillar proteins.

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An exact and general approach to study molecular vibrations is provided by the Watson Hamiltonian. Within this framework, it is customary to omit the contribution of the terms with the vibrational angular momentum and the Watson term, especially for the study of large systems. We discover that this omission leads to results which depend on the choice of the reference structure. The self-consistent solution proposed here yields a geometry that coincides with the quantum averaged geometry of the Watson Hamiltonian and appears to be a promising way for the computation of the vibrational spectra of strongly anharmonic systems.

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Water Research, 40 14 (2006) 2645.

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The kinetics of the acid-catalysed hydrolysis of cellobiose in the ionic liquid 1-ethyl-3-methylimidazolium chloride, [C(2)mim]Cl, was studied as a model for general lignocellulosic biomass hydrolysis in ionic liquid systems. The results show that the rate of the two competing reactions, polysaccharide hydrolysis and sugar decomposition, vary with acid strength, and that for acids with an aqueous pK(a) below approximately zero, the hydrolysis reaction is significantly faster than the degradation of glucose, thus allowing hydrolysis to be performed with a high selectivity in glucose. In tests with soluble cellulose, hemicellulose (xylan), and lignocellulosic biomass (Miscanthus grass), comparable hydrolysis rates were observed with bond scission occurring randomly along the biopolymer chains, in contrast to end-group hydrolysis observed with aqueous acids.