Reactions of atomic and molecular ions with acetone, 1,1,1- trifluoroacetone, and hexafluoroacetone: An investigation of the effects of molecular structure on the dynamics and kinetics of ion-molecule reactions

A selected ion flow tube study of the reactions of a series of gas-phase atomic cations (S⁺, Xe⁺, O⁺, Kr⁺, N⁺, Ar⁺ and Ne⁺) and molecular ions (SF _n⁺ (n = 1-5), CF_n⁺ (n = 1-3), CF₂Cl⁺, H₃O⁺, NO⁺, N ₂O⁺, CO₂⁺, CO⁺, and N₂⁺) spanning a large range of recombination energies (6.3-21.6 eV), with acetone, 1,1,1-trifluoroacetone, and hexafluoroacetone has been undertaken with the objective of exploring the nature of the reaction ion chemistry as the methyl groups in acetone are substituted for CF₃. The reaction rate coefficients and product ion branching ratios for all 66 reactions, measured at 298 K, are reported. The experimental reaction rate coefficients are compared to theoretically calculated collisional values. Several distinct reaction processes were observed among the large number of reactions studied, including charge transfer (non-dissociative and dissociative), abstraction, ion-molecule associations and, in the case of the reactions involving the reagent ion H₃O⁺, proton transfer. 

Similarity solutions of a Becker-Döring system with time-dependent monomer input

We formulate the Becker-Döring equations for cluster growth in the presence of a time-dependent source of monomer input. In the case of size-independent aggregation and ragmentation rate coefficients we find similarity solutions which are approached in the large time limit. The form of the solutions depends on the rate of monomer input and whether fragmentation is present in the model; four distinct types of solution are found.

Ultra-Low Temperature Partial Oxidation: Detailed Kinetics, Safety, and Environmental Issues

The innovation in several industrial sectors has been recently characterized by the need for reducing the operative temperature either for economic or environmental related aspects. Promising technological solutions require the acquisition of fundamental-based knowledge to produce safe and robust systems. In this sense, reactive systems often represent the bottleneck. For these reasons, this work was focused on the integration of chemical (i.e., detailed kinetic mechanism) and physical (i.e., computational fluid dynamics) models. A theoretical-based kinetic mechanism mimicking the behaviour of oxygenated fuels and their intermediates under oxidative conditions in a wide range of temperature and pressure was developed. Its validity was tested against experimental data collected in this work by using the heat flux burner, as well as measurements retrieved from the current literature. Besides, estimations deriving from existing models considered as the benchmark in the combustion field were compared with the newly generated mechanism. The latter was found to be the most accurate for the investigated conditions and fuels. Most influential species and reactions on the combustion of butyl acetate were identified. The corresponding thermodynamic parameter and rate coefficients were quantified through ab initio calculations. A reduced detailed kinetic mechanism was produced and implemented in an open-source computational fluid dynamics model to characterize pool fires caused by the accidental release of aviation fuel and liquefied natural gas, at first. Eventually, partial oxidation processes involving light alkenes were optimized following the quick, fair, and smoot (QFS) paradigm. The proposed procedure represents a comprehensive and multidisciplinary approach for the construction and validation of accurate models, allowing for the characterization of developing industrial sectors and techniques.

Simulation of Delamination Propagation in Composites Under High-Cycle Fatigue by Means of Cohesive-Zone Models

A damage model for the simulation of delamination propagation under high-cycle fatigue loading is proposed. The basis for the formulation is a cohesive law that links fracture and damage mechanics to establish the evolution of the damage variable in terms of the crack growth rate dA/dN. The damage state is obtained as a function of the loading conditions as well as the experimentally-determined coefficients of the Paris Law crack propagation rates for the material. It is shown that by using the constitutive fatigue damage model in a structural analysis, experimental results can be reproduced without the need of additional model-specific curve-fitting parameters

Growth rate and vertical propagation of the initial error in baroclinic models

The present study investigates the growth of error in baroclinic waves. It is found that stable or neutral waves are particularly sensitive to errors in the initial condition. Short stable waves are mainly sensitive to phase errors and the ultra long waves to amplitude errors. Analysis simulation experiments have indicated that the amplitudes of the very long waves become usually too small in the free atmosphere, due to the sparse and very irregular distribution of upper air observations. This also applies to the four-dimensional data assimilation experiments, since the amplitudes of the very long waves are usually underpredicted. The numerical experiments reported here show that if the very long waves have these kinds of amplitude errors in the upper troposphere or lower stratosphere the error is rapidly propagated (within a day or two) to the surface and to the lower troposphere.

Nuclear Data Uncertainty Propagation to Reactivity Coefficients of a Sodium Fast Reactor

The assessment of the uncertainty levels on the design and safety parameters for the innovative European Sodium Fast Reactor (ESFR) is mandatory. Some of these relevant safety quantities are the Doppler and void reactivity coefficients, whose uncertainties are quantified. Besides, the nuclear reaction data where an improvement will certainly benefit the design accuracy are identified. This work has been performed with the SCALE 6.1 codes suite and its multigroups cross sections library based on ENDF/B-VII.0 evaluation.

Evapotranspiration and crop coefficients of seedless watermelon

The research was developed in Fortaleza, CE (latitude 3 degrees 43`S, longitude of 38 degrees 32`W and altitude of 19.5 m). It aimed to determine the Evapotranspiration and the crop coefficients for the different stadiums of seedless watermelon (Citrullus lanatus, Schrad), using the water balance method in drainage lysimeter. The experimental unit consisted of four located drainage lysimeter in an area of 600 m(2). The culture Evapotranspiration (ETc) was determined by the method of the water balance, in a volume of soil control with depth of 0.45 m, whose humidity was monitored by tensiometers. The reference Evapotranspiration (ETo) was estimated by the method of the class A pan. The crop coefficients were obtained from the rate between ETc and ETo in the different stages. The ETc presented growing values from the vegetative stage to the fruiting stage, dropping straight away in the mature stage. The maximum value of kc was observed in the fruiting stage.

Ultrasound detection rate of single umbilical artery in the first trimester of pregnancy

Objective To determine accuracy of first trimester detection of single umbilical artery (SUA). Methods The number of vessels in the umbilical cord was examined in a prospective cohort of 779 singleton, low-risk, unselected pregnancies, in the first (11-13 weeks) and second (17-24 weeks) trimesters, using both power and color Doppler and after delivery, by placental histopathologic exam. Concordance between first and second trimester findings to postnatal diagnoses was compared by calculating kappa coefficients. Results There was medium concordance between the findings in the first trimester and the postnatal diagnoses (kappa = 0.52) and high concordance (kappa = 0.89) for the second trimester scan. Sensitivity, specificity, positive and negative predictive values for the findings in the first trimester were 57.1, 98.9, 50.0 and 99.2% and for the second trimester were 86.6, 99.9, 92.9 and 99.7%. Conclusion Sensitivity and positive predictive value of first trimester scan to identify an isolated SUA in a prospective unselected population was poor. Diagnosis of isolated SUA as well as a definitive judgment about the presence of associated anomalies would still require a scan in the second trimester. Copyright (C) 2011 John Wiley & Sons, Ltd.

Towards the clonal propagation of coconut

Past studies from our laboratory have shown that whole immature, or mature sliced, zygotic embryos are a very good starting explant for coconut somatic embryogenesis. The highest rate of somatic embryogenesis was obtained when certain polyamines were added into the culture medium as well as activated charcoal (AC) to absorb unwanted phenolics. These past studies also showed that the development and maturation of the somatic embryos produced could be improved by the addition of abscisic acid (ABA), alone or with one of several osmotically active agents, into the culture medium. In the present study this well characterised somatic embryogenic system for zygotic tissues is being modified and applied to somatic tissues. This recent approach should be a better method for the rapid production of clonal, true-to-type coconut palms. The present research approach is focused on young leaf section explants which have been found to be very responsive to callus production. Young leaf sections produced optimum callus when cultured on media containing 2,4-D (150 μM) and the amount produced could be increased by soaking the sections in sterile water (15 to 60 minutes) or ascorbic acid (15 to 30 minutes) prior to culturing. Further improvement in callus production, as well as a reduction in the time taken for callogenesis was obtained when casein hydrolysate and/or certain polyamines were added to the callus induction medium. The development of the somatic embryos was improved by using ABA and polyethylene glycol (PEG) in the maturation medium. Despite these initial successes in improving coconut somatic embryogenesis, further studies are now being considered to shorten the time to achieve somatic embryogenesis, to better germinate somatic embryos and to improve the rate of somatic seedling conversion into plantlets.

Predicting cave initiation and propagation

The most widely used method for predicting the onset of continuous caving is Laubscher's caving chart. A detailed examination of this method was undertaken which concluded that it had limitations which may impact on results, particularly when dealing with stronger rock masses that are outside current experience. These limitations relate to inadequate guidelines for adjustment factors to rock mass rating (RMR), concerns about the position on the chart of critical case history data, undocumented changes to the method and an inadequate number of data points to be confident of stability boundaries. A review was undertaken on the application and reliability of a numerical method of assessing cavability. The review highlighted a number of issues, which at this stage, make numerical continuum methods problematic for predicting cavability. This is in particular reference to sensitivity to input parameters that are difficult to determine accurately and mesh dependency. An extended version of the Mathews method for open stope design was developed as an alternative method of predicting the onset of continuous caving. A number of caving case histories were collected and analyzed and a caving boundary delineated statistically on the Mathews stability graph. The definition of the caving boundary was aided by the existence of a large and wide-ranging stability database from non-caving mines. A caving rate model was extrapolated from the extended Mathews stability graph but could only be partially validated due to a lack of reliable data.

The problem of estimating the volatility of zero coupon bond interest rate

Financial literature and financial industry use often zero coupon yield curves as input for testing hypotheses, pricing assets or managing risk. They assume this provided data as accurate. We analyse implications of the methodology and of the sample selection criteria used to estimate the zero coupon bond yield term structure on the resulting volatility of spot rates with different maturities. We obtain the volatility term structure using historical volatilities and Egarch volatilities. As input for these volatilities we consider our own spot rates estimation from GovPX bond data and three popular interest rates data sets: from the Federal Reserve Board, from the US Department of the Treasury (H15), and from Bloomberg. We find strong evidence that the resulting zero coupon bond yield volatility estimates as well as the correlation coefficients among spot and forward rates depend significantly on the data set. We observe relevant differences in economic terms when volatilities are used to price derivatives.

A high-rate mimo receiver in an FPGA

This paper describes the hardware implementation of a High-Rate MIMO Receiver in an FPGA for three modulations, namely BPSK, QPSK and 16-QAM based on the Alamouti scheme. The implementation with 16-QAM achieves more than 1.6 Gbps with 66% of the resources of a medium-sized Virtex-4 FPGA. This results indicate that the Alamouti scheme is a good design option for hardware implementation of a high-rate MIMO receiver. Also, using an FPGA, the modulation can be dynamically changed on demand.

Credit markets and the propagation of monetary policy shocks

This paper analyzes the propagation of monetary policy shocks through the creation of credit in an economy. Models of the monetary transmission mechanism typically feature responses which last for a few quarters contrary to what the empirical evidence suggests. To propagate the impact of monetary shocks over time, these models introduce adjustment costs by which agents find it optimal to change their decisions slowly. This paper presents another explanation that does not rely on any sort of adjustment costs or stickiness. In our economy, agents own assets and make occupational choices. Banks intermediate between agents demanding and supplying assets. Our interpretation is based on the way banks create credit and how the monetary authority affects the process of financial intermediation through its monetary policy. As the central bank lowers the interest rate by buying government bonds in exchange for reserves, high productive entrepreneurs are able to borrow more resources from low productivity agents. We show that this movement of capital among agents sets in motion a response of the economy that resembles an expansionary phase of the cycle.

A Panel Data Investigation of Real Exchange Rate Misalignment and Growth

The paper investigates the role of real exchange rate misalignment on long-run growth for a set of ninety countries using time series data from 1980 to 2004. We first estimate a panel data model (using fixed and random effects) for the real exchange rate, with different model specifications, in order to produce estimates of the equilibrium real exchange rate and this is then used to construct measures of real exchange rate misalignment. We also provide an alternative set of estimates of real exchange rate misalignment using panel cointegration methods. The variables used in our real exchange rate models are: real per capita GDP; net foreign assets; terms of trade and government consumption. The results for the two-step System GMM panel growth models indicate that the coefficients for real exchange rate misalignment are positive for different model specification and samples, which means that a more depreciated (appreciated) real exchange rate helps (harms) long-run growth. The estimated coefficients are higher for developing and emerging countries.

Currency Forecast Errors at Times of Low Interest Rates: Evidence from Survey Data on the Yen/Dollar Exchange Rate

Using survey expectations data and Markov-switching models, this paper evaluates the characteristics and evolution of investors' forecast errors about the yen/dollar exchange rate. Since our model is derived from the uncovered interest rate parity (UIRP) condition and our data cover a period of low interest rates, this study is also related to the forward premium puzzle and the currency carry trade strategy. We obtain the following results. First, with the same forecast horizon, exchange rate forecasts are homogeneous among different industry types, but within the same industry, exchange rate forecasts differ if the forecast time horizon is different. In particular, investors tend to undervalue the future exchange rate for long term forecast horizons; however, in the short run they tend to overvalue the future exchange rate. Second, while forecast errors are found to be partly driven by interest rate spreads, evidence against the UIRP is provided regardless of the forecasting time horizon; the forward premium puzzle becomes more significant in shorter term forecasting errors. Consistent with this finding, our coefficients on interest rate spreads provide indirect evidence of the yen carry trade over only a short term forecast horizon. Furthermore, the carry trade seems to be active when there is a clear indication that the interest rate will be low in the future.