The kinetics of the gas-phase decomposition of the 2-methyl-2-butoxyl and 2-methyl-2-pentoxyl radicals

The kinetics of the title reactions have been studied by relative-rate methods as a function of temperature. Relative-rate coefficients for the two decomposition channels of 2-methyl-2-butoxyl have been measured at five different temperatures between 283 and 345 K and the observed temperature dependence is consistent with the results of some previous experimental studies. The kinetics of the two decomposition channels of 2-methyl-2-pentoxyl have also been investigated, as a function of temperature, relative to the estimated rate of isomerisation of this radical. Room-temperature rate coefficient data for the two decomposition channels of both 2-methyl-2-pentoxyl and 2-methyl-2-butxoyl (after combining the relative rate coefficient for this latter with a value for the rate coefficient of the major channel, extrapolated from the data presented by Batt et al., Int. J. Chem. Kinet., 1978, 10, 931) are shown to be consistent with a non-linear kinetic correlation, for alkoxyl radical decomposition rate data, previously presented by this laboratory (Johnson et al., Atmos. Environ., 2004, 38, 1755-1765).

Micellar and surface properties of a poly(methyl methacrylate)-block-poly(N-isopropylacrylamide) copolymer in aqueous solution

Critical micelle concentrations (cmc) of aqueous solutions of poly(methyl methacrylate)-block-poly(N-isopropylacrylamide) were determined at several temperatures by surface tensiometry. Below the lower critical solution temperature (LCST), the low Delta(mic) H-0 determined can be assigned to the PMMA block being tightly coiled in the dispersed molecular state, so that the unfavorable interactions of hydrophobic entities with water are minimized. Above the LCST the cmc value was found to increase; an anomalous behavior that can be directly related to the micelle-globule transition of the hydrophilic block. Interestingly, above the LCST the surface tension of relatively concentrated solutions was found to depend weakly on temperature not following the usual strong decrease with temperature expected for aqueous solutions. (C) 2007 Elsevier Inc. All rights reserved.

Reversible addition of CO to coordinatively unsaturated high-spin iron(II) complexes

Several new coordinatively unsaturated iron(II) complexes of the types [Fe(EN-iPr)X2] (E = P, S, Se; X = Cl, Br) and [Fe(ON-iPr)2X]X containing bidentate EN ligands based on N-(2-pyridinyl)aminophosphines as well as oxo, thio, and seleno derivatives thereof were prepared and characterized by NMR spectroscopy and X-ray crystallography. Mössbauer spectroscopy and magnetization studies confirmed their high-spin nature with magnetic moments very close to 4.9 μB, reflecting the expected four unpaired d-electrons in all these compounds. Stable low-spin carbonyl complexes of the types [Fe(PN-iPr)2(CO)X]X (X = Cl, Br) and cis-CO,cis-Br-[Fe(PN-iPr)(CO)2X2] (X = Br) were obtained by reacting cis-Fe(CO)4X2 with the stronger PN donor ligands, but not with the weaker EN donor ligands (E = O, S, Se). Furthermore, the reactivity of [Fe(PN-iPr)X2] toward CO was investigated by IR spectroscopy. Whereas at room temperature no reaction took place, at −50 °C [Fe(PN-iPr)X2] added readily CO to form, depending on the nature of X, the mono- and dicarbonyl complexes [Fe(PN-iPr)(X)2(CO)] (X = Cl) and [Fe(PN-iPr)(CO)2X2] (X = Cl, Br), respectively. In the case of X = Br, two isomeric dicarbonyl complexes, namely, cis-CO,trans-Br-[Fe(PN-iPr)(CO)2Br2] (major species) and cis-CO,cis-Br-[Fe(PN-iPr)(CO)2Br2] (minor species), are formed. The addition of CO to [Fe(PN-iPr)X2] was investigated in detail by means of DFT/B3LYP calculations. This study strongly supports the experimental findings that at low temperature two isomeric low-spin dicarbonyl complexes are formed. For kinetic reasons cis,trans-[Fe(PN-iPr)(CO)2Br2] releases CO at elevated temperature, re-forming [Fe(PN-iPr)Br2], while the corresponding cis,cis isomer is stable under these conditions.

The depression of tropical snow lines at the Last Glacial Maximum: what can we learn from climate and model experiments?

Analyses of simulations of the last glacial maximum (LGM) made with 17 atmospheric general circulation models (AGCMs) participating in the Paleoclimate Modelling Intercomparison Project, and a high-resolution (T106) version of one of the models (CCSR1), show that changes in the elevation of tropical snowlines (as estimated by the depression of the maximum altitude of the 0 °C isotherm) are primarily controlled by changes in sea-surface temperatures (SSTs). The correlation between the two variables, averaged for the tropics as a whole, is 95%, and remains >80% even at a regional scale. The reduction of tropical SSTs at the LGM results in a drier atmosphere and hence steeper lapse rates. Changes in atmospheric circulation patterns, particularly the weakening of the Asian monsoon system and related atmospheric humidity changes, amplify the reduction in snowline elevation in the northern tropics. Colder conditions over the tropical oceans combined with a weakened Asian monsoon could produce snowline lowering of up to 1000 m in certain regions, comparable to the changes shown by observations. Nevertheless, such large changes are not typical of all regions of the tropics. Analysis of the higher resolution CCSR1 simulation shows that differences between the free atmospheric and along-slope lapse rate can be large, and may provide an additional factor to explain regional variations in observed snowline changes.

Proper evaluation of the external convective heat transfer for the thermal analysis of cool roofs

Cool materials are characterized by high solar reflectance and high thermal emittance; when applied to the external surface of a roof, they make it possible to limit the amount of solar irradiance absorbed by the roof, and to increase the rate of heat flux emitted by irradiation to the environment, especially during nighttime. However, a roof also releases heat by convection on its external surface; this mechanism is not negligible, and an incorrect evaluation of its entity might introduce significant inaccuracy in the assessment of the thermal performance of a cool roof, in terms of surface temperature and rate of heat flux transferred to the indoors. This issue is particularly relevant in numerical simulations, which are essential in the design stage, therefore it deserves adequate attention. In the present paper, a review of the most common algorithms used for the calculation of the convective heat transfer coefficient due to wind on horizontal building surfaces is presented. Then, with reference to a case study in Italy, the simulated results are compared to the outcomes of a measurement campaign. Hence, the most appropriate algorithms for the convective coefficient are identified, and the errors deriving by an incorrect selection of this coefficient are discussed.

Identifiering av parametrar till ackumulatortanken Solus1050 från consolar - en metodbeskrivning

This report describes the work done creating a computer model of a kombi tank from Consolar. The model was created with Presim/Trnsys and Fittrn and DF were used to identify the parameters. Measurements were carried out and were used to identify the values of the parameters in the model. The identifications were first done for every circuit separately. After that, all parameters are normally identified together using all the measurements. Finally the model should be compared with other measurements, preferable realistic ones. The two last steps have not yet been carried out, because of problems finding a good model for the domestic hot water circuit.The model of the domestic hot water circuit give relatively good results for low flows at 5 l/min, but is not good for higher flows. In the report suggestions for improving the model are given. However, there was not enough time to test this within the project as much time was spent trying to solve problems with the model crashing. Suggestions for improving the model for the domestic circuit are given in chapter 4.4. The improved equations that are to be used in the improved model are given by equation 4.18, 4.19 and 4.22.Also for the boiler circuit and the solar circuit there are improvements that can be done. The model presented here has a few shortcomings, but with some extra work, an improved model can be created. In the attachment (Bilaga 1) is a description of the used model and all the identified parameters.A qualitative assessment of the store was also performed based on the measurements and the modelling carried out. The following summary of this can be given: Hot Water PreparationThe principle for controlling the flow on the primary side seems to work well in order to achieve good stratification. Temperatures in the bottom of the store after a short use of hot water, at a coldwater temperature of 12°C, was around 28-30°C. This was almost independent of the temperature in the store and the DHW-flow.The measured UA-values of the heat exchangers are not very reliable, but indicates that the heat transfer rates are much better than for the Conus 500, and in the same range as for other stores tested at SERC.The function of the mixing valve is not perfect (see diagram 4.3, where Tout1 is the outlet hot water temperature, and Tdhwo and Tdhw1 is the inlet temperature to the hot and cold side of the valve respectively). The outlet temperature varies a lot with different temperatures in the storage and is going down from 61°C to 47°C before the cold port is fully closed. This gives a problem to find a suitable temperature setting and gives also a risk that the auxiliary heating is increased instead of the set temperature of the valve, when the hot water temperature is to low.Collector circuitThe UA-value of the collector heat exchanger is much higher than the value for Conus 500, and in the same range as the heat exchangers in other stores tested at SERC.Boiler circuitThe valve in the boiler circuit is used to supply water from the boiler at two different heights, depending on the temperature of the water. At temperatures from the boiler above 58.2°C, all the water is injected to the upper inlet. At temperatures below 53.9°C all the water is injected to the lower inlet. At 56°C the water flow is equally divided between the two inlets. Detailed studies of the behaviour at the upper inlet shows that better accuracy of the model would have been achieved using three double ports in the model instead of two. The shape of the upper inlet makes turbulence, that could be modelled using two different inlets. Heat lossesThe heat losses per m3 are much smaller for the Solus 1050, than for the Conus 500 Storage. However, they are higher than those for some good stores tested at SERC. The pipes that are penetrating the insulation give air leakage and cold bridges, which could be a major part of the losses from the storage. The identified losses from the bottom of the storage are exceptionally high, but have less importance for the heat losses, due to the lower temperatures in the bottom. High losses from the bottom can be caused by air leakage through the insulation at the pipe connections of the storage.

Interesse, ideologia & incompetência: a guerra do Iraque e o segundo consenso de Washington

Este projeto continua a avançar o programa de pesquisa que relaciona desenvolvimento econômico e democracia: pretende-se neste projeto dar um passo adiante e examinar como a democracia, uma vez consolidada como fruto do desenvolvimento capitalista, se torna ela própria um fator de desenvolvimento, particularmente quando ela deixa de ser uma mera democracia de elites para se tornar uma democracia de sociedade civil, na qual o debate público passa a ser um elemento central.

Recuperação do cromo contido nas cinzas provenientes da incineração de resíduos sólidos das indústrias coureira e calçadista visando a obtenção de cromato de sódio (VI)

O processo de transformação da pele em couro envolve uma seqüência complexa de reações químicas e processos mecânicos, no qual o curtimento representa fundamental estágio, por propiciar à pele características como qualidade, estabilidade hidrotérmica e excelentes propriedades para uso. O sulfato básico de cromo trivalente é o agente curtente predominantemente empregado no curtimento de peles em todo o mundo. É produzido a partir do cromato de sódio, industrialmente obtido do minério de cromo. Consideráveis quantidades de resíduos sólidos contendo cromo são geradas pelas indústrias coureira e calçadista. Estes resíduos tem sido motivo de preocupação constante, uma vez que são considerados perigosos devido a presença do cromo. O processo de incineração destes resíduos é uma importante alternativa a ser considerada, em decorrência de suas características de redução de massa, volume e possibilidade de aproveitamento da energia térmica dos gases de combustão. O processo de incineração dos resíduos das indústrias coureira e calçadista dá origem a cinzas contendo cerca de 40% de cromo que pode ser submetida a um processo de recuperação. Este trabalho apresenta os resultados da pesquisa sobre a utilização das cinzas, provenientes da incineração dos resíduos sólidos da indústria coureira e da indústria calçadista, para a produção de cromato de sódio(VI). No processo de planejamento e de condução dos experimentos foram utilizadas as técnicas de Planejamento Fatorial 2k, Metodologia de Superfície de Resposta e Análise de Variância na avaliação da produção de cromato de sódio(VI). Os fatores investigados foram: temperatura, taxa de aquecimento, tempo de reação, vazão de ar e quantidade de dolomita. A partir das variáveis selecionadas identificaram-se como parâmetros importantes a temperatura e a taxa de aquecimento. As superfícies de resposta tridimensionais obtidas a partir dos modelos de segunda ordem ajustados aos dados experimentais, apresentaram o comportamento do efeito conjugado dos fatores temperatura e taxa de aquecimento sobre a variável resposta grau de oxidação, desde a temperatura de inicio da reação química até a temperatura limite utilizada industrialmente. As condições de operação do processo de produção de cromato de sódio(VI) foram otimizadas. Os níveis ótimos dos fatores de controle aplicados as cinzas dos resíduos da indústria calçadista, geradas em uma planta piloto com incinerador de leito fixo, com tecnologia de gaseificação e combustão combinadas, apresentaram um grau de oxidação superior a 96% para as cinzas coletadas no ciclone e de 99,5% para as cinzas coletas no reator de gaseificação. Os resíduos sólidos, as cinzas e o produto de reação foram caracterizados por análises químicas, fluorescência de raio-X, microscopia eletrônica de varredura e difração de raio-X.

Biology and thermal requirements of Telenomus remus reared on fall armyworm Spodoptera frugiperda eggs

Este trabalho teve como objetivo estudar a biologia de Telenomus remus Nixon criado em ovos de Spodoptera frugiperda (J.E. Smith) em diferentes temperaturas. Com base no desenvolvimento do ciclo (ovo-adulto), foram determinados as exigências térmicas e o número de gerações dos parasitóides em temperaturas constantes. Inicialmente, ovos de S. frugiperda, com 24 horas de idade, foram submetidos ao parasitismo por T. remus, durante cinco horas, sendo então transferidos para câmaras climatizadas reguladas para as temperaturas de 15, 20, 25, 28, 31 e 35°C. A duração do ciclo (ovo-adulto) foi influenciada pela temperatura variando de 8,3±0,01 a 47,2±0,01 dias para fêmeas e 8,1±0,01 a 46,8±0,01 dias para machos de T. remus nas temperaturas de 31 e 15°C, respectivamente. A porcentagem de emergência (viabilidade) de T. remus em ovos de S. frugiperda também foi influenciada pela variação da temperatura, apresentando redução significativa apenas nas temperaturas extremas. Foi observada redução na viabilidade a 15°C e não houve desenvolvimento biológico do parasitóide a 35°C. A razão sexual de T. remus não sofreu influência da temperatura. em relação às exigências térmicas, a constante térmica (K) e temperatura base (Tb) foram maiores para as fêmeas de T. remus (158,88 graus dias e 12,52°C) quando comparadas aos machos (154,12 graus dias e 12,59°C). A estimativa do número de gerações anuais para T. remus para machos e fêmeas em condições de laboratório foi respectivamente 5,6 e 5,6; 16,9 e 17,3; 28,3 e 29,0; 35,1 e 36,0; 39,6 e 40,7 nas temperaturas de 15, 20, 25, 28 e 31°C.

Desenvolvimento de antenas de microfita e antenas DRA Broadband

The search for ever smaller device and without loss of performance has been increasingly investigated by researchers involving applied electromagnetics. Antennas using ceramics materials with a high dielectric constant, whether acting as a substract element of patch radiating or as the radiant element are in evidence in current research, that due to the numerous advantages offered, such as: low profile, ability to reduce the its dimensions when compared to other devices, high efficiency of ratiation, suitability the microwave range and/or millimeter wave, low temperature coefficient and low cost. The reason for this high efficiency is that the dielectric losses of ceramics are very low when compared to commercially materials sold used in printed circuit boards, such as fiberglass and phenolite. These characteristics make ceramic devices suitable for operation in the microwave band. Combining the design of patch antennas and/or dielectric resonator antenna (DRA) to certain materials and the method of synthesis of these powders in the manufacture of devices, it s possible choose a material with a dielectric constant appropriate for the design of an antenna with the desired size. The main aim of this work is the design of patch antennas and DRA antennas on synthesis of ceramic powders (synthesis by combustion and polymeric precursors - Pe- chini method) nanostructured with applications in the microwave band. The conventional method of mix oxides was also used to obtain nanometric powders for the preparation of tablets and dielectric resonators. The devices manufactured and studied on high dielectric constant materials make them good candidates to have their small size compared to other devices operating at the same frequency band. The structures analyzed are excited by three different techniques: i) microstrip line, ii) aperture coupling and iii) inductive coupling. The efficiency of these techniques have been investigated experimentally and compared with simulations by Ansoft HFSS, used in the accurate analysis of the electromagnetic behavior of antennas over the finite element method (FEM). In this thesis a literature study on the theory of microstrip antennas and DRA antenna is performed. The same study is performed about the materials and methods of synthesis of ceramic powders, which are used in the manufacture of tablets and dielectric cylinders that make up the devices investigated. The dielectric media which were used to support the analysis of the DRA and/or patch antennas are analyzed using accurate simulations using the finite difference time domain (FDTD) based on the relative electrical permittivity (er) and loss tangent of these means (tand). This work also presents a study on artificial neural networks, showing the network architecture used and their characteristics, as well as the training algorithms that were used in training and modeling some parameters associated with the devices investigated

Desenvolvimento de material compósito a base de raspa de pneu e látex para isolamento térmico

The process of recycling has been stimulated by the markets for several reasons, mainly on economical and environmental. Several products have been developed from recycled materials that already exist as well as several residues have been studied in different forms of applications. The greater majority of the applications for thermal insulation in the domestic, commercial and industrial systems have been elaborated in the temperature ranges between low to medium reaching up to 180oC. Many materials such as glass wool, rock wool, polystyrene are being used which are aggressive to the environment. Such materials in spite of the effectiveness in the retention of heat flow, they cost more and when discarded take several years to be absorbed by the nature. This way, in order to adapt to a world politics concerning the preservation of the environment, the present study was intended to develop a material composed of natural/biodegradable materials and industrial residues. The development of such a product in the form of a composite material based on tyre scrapes and latex for thermal insulation is presented in this research work. Thermal and physical properties of the tire scrapes as well as latex were studied in order to use them as raw materials for the manufacture of the intended composite to be applied as a thermal insulator in hot and cold systems varying between 0ºC and 200oC, respectively. Composite blankets were manufactured manually, in weight proportions of 1:1 (50:50%); 1:2 (33:67%) and 2:1 (67:33%) (tire scrapes: latex) respectively. Physical, mechanical and thermal properties of the composites were analyzed to obtain data about the viability of using the composite as a thermal insulator. The analyses carried out were based on standards ABNT, ASTM and UL. The maximum temperature obtained for the composite as a thermal insulator was 200ºC, which meets the range of applications that could be used as a thermal insulator in domestic as well as industrial purposes. The experimental results prove that the composite can be used as a thermal insulator on heated or cooled surface

Avaliacao de dados de secagem de suspensoes de polpas de frutas em leito de jorro com alimentacao intermitente

The objective of this work was the development and improvement of the mathematical models based on mass and heat balances, representing the drying transient process fruit pulp in spouted bed dryer with intermittent feeding. Mass and energy balance for drying, represented by a system of differential equations, were developed in Fortran language and adapted to the condition of intermittent feeding and mass accumulation. Were used the DASSL routine (Differential Algebraic System Solver) for solving the differential equation system and used a heuristic optimization algorithm in parameter estimation, the Particle Swarm algorithm. From the experimental data food drying, the differential models were used to determine the quantity of water and the drying air temperature at the exit of a spouted bed and accumulated mass of powder in the dryer. The models were validated using the experimental data of drying whose operating conditions, air temperature, flow rate and time intermittency, varied within the limits studied. In reviewing the results predicted, it was found that these models represent the experimental data of the kinetics of production and accumulation of powder and humidity and air temperature at the outlet of the dryer

Criação da matéria em cosmologias com velocidade da luz variável e eletrônico não-linear

In this work we obtain the cosmological solutions and investigate the thermodynamics of matter creation in two diferent contexts. In the first we propose a cosmological model with a time varying speed of light c. We consider two diferent time dependence of c for a at Friedmann-Robertson- Walker (FRW) universe. We write the energy conservation law arising from Einstein equations and study how particles are created as c decreases with cosmic epoch. The variation of c is coupled to a cosmological Λ term and both singular and non-singular solutions are possible. We calculate the "adiabatic" particle creation rate and the total number of particles as a function of time and find the constrains imposed by the second law of thermodynamics upon the models. In the second scenario, we study the nonlinearity of the electrodynamics as a source of matter creation in the cosmological models with at FRW geometry. We write the energy conservation law arising from Einstein field equations with cosmological term Λ, solve the field equations and study how particles are created as the magnetic field B changes with cosmic epoch. We obtain solutions for the adiabatic particle creation rate, the total number of particles and the scale factor as a function of time in three cases: Λ = 0, Λ = constant and Λ α H2 (cosmological term proportional to the Hubble parameter). In all cases, the second law of thermodynamics demands that the universe is not contracting (H ≥ 0). The first two solutions are non-singular and exhibit in ationary periods. The third case studied allows an always in ationary universe for a suficiently large cosmological term

Solid-liquid transition in Nb powder determined by third harmonic susceptibility

Measurements of the third harmonic of the AC-susceptibility were employed to determine the boundaries of the linear regime of the magnetic response of Nb powder. Non-linear contributions to the magnetic response reveal the occurrence of a structured phase, disappearing as the vortex lattice melts to the liquid state. A systematic study of the third harmonic was conducted to determine how its onset temperature depends on experimental parameters, such as the frequency and amplitude of the excitation field. The melting line (ML) has been extracted from the onset temperature measured at low-frequencies and low-excitation fields in the presence of DC magnetic fields. The study indicates that the ML can be described by a 3D vortex-glass model, except at lower fields, where the system experiences a depinning crossover, and the best description of the experimental data is provided by a 3D Bose-glass model. (c) 2008 Elsevier B. V. All rights reserved.

A preliminary trial comparison of several anesthetic techniques in cats

The aim of this study was to investigate the effect of several drug combinations (atropine, xylazine, romifidine, methotrimeprazine, midazolam, or fentanyl) with ketamine for short term anesthesia in cats. Twelve cats were anesthetized 6 times by using a cross-over Latin square protocol: methotrimeprazine was combined with midazolam, ketamine, and fentanyi; midazolam and ketamine; romifidine and ketamine; and xylazine and ketamine. Atropine was combined with romifidine and ketamine, and xylazine and ketamine. Temperature, heart rate, and respiratory rate decreased in all groups. Apnea occurred in 1 cat treated with methotrimeprazine, romifidine, and ketamine, suggesting that ventilatory support may be necessary when this protocol is used. Emesis occurred in some cats treated with alpha(2)-adrenoceptor agonists, and this side effect should be considered when these drugs are used.