Estimativa por DSC das entalpias de sublimação da etilenouréia e da propilenouréia: algumas correlações empíricas envolvendo amidas e tioamidas

By using DSC data, the enthaplies of sublimation for ethyleneurea and propyleneurea, are calculated as 84 and 89 kJ mol-1 respectively. Using the vaporization enthalpy values for dimethylethyleneurea and dimethylprophyleneurea, as obtained from literature, the empirical relation: Dcrg Hmo (1)/ Dcrg Hmo (2) = Dlg Hmo (1)/ Dlg Hmo(2) = constant, that relate sublimation or vaporization enthalpies of two different substances and of its methylated derivatives, is obtained. Correlations like that are found to another ureas and thioureas.

Desenvolvimento de um equipamento para avaliação do efeito do etanol na pressão de vapor e entalpia de vaporização em gasolinas automotivas

The quality of the gasoline utilized for fueling internal combustion engines with spark ignition is directly affected by the gasoline's properties. Thus, the fuel's properties must be in perfect equilibrium to allow the engine to perform optimally, not only insofar as fuel consumption is concerned, but also in order to reduce the emission of pollutants. Vapor pressure and vaporization enthalpy are important properties of a gasoline determining the fuel's behavior under different operating conditions in internal combustion engines. The study reported here involved the development of a device to determine the vapor pressure and the vaporization enthalpy of formulations containing volumes of 5, 15 and 25% of ethanol in four base gasolines (G1, G2, G3 and G4). The chemical composition of these gasolines was determined using a gas chromatographer equipped with a flame ionization detector (FID).

A correct enthalpy relationship as thermal comfort index for livestock

Researchers working with thermal comfort have been using enthalpy to measure thermal energy inside rural facilities, establishing indicator values for many situations of thermal comfort and heat stress. This variable turned out to be helpful in analyzing thermal exchange in livestock systems. The animals are exposed to an environment which is decisive for the thermoregulatory process, and, consequently, the reactions reflect states of thermal comfort or heat stress, the last being responsable for problems of sanity, behavior and productivity. There are researchers using enthalpy as a qualitative indicator of thermal environment of livestock such as poultry, cattle and hogs in tropical regions. This preliminary work intends to check different enthalpy equations using information from classical thermodynamics, and proposes a direct equation as thermal comfort index for livestock systems.

Evaluation of the enthalpy of formation, proton affinity, and gas-phase basicity of gamma-butyrolactone and 2-pyrrolidinone by isodesmic reactions

The knowledge of thermochemical parameters such as the enthalpy of formation, gas-phase basicity, and proton affinity may be the key to understanding molecular reactivity. The obtention of these thermochemical parameters by theoretical chemical models may be advantageous when experimental measurements are difficult to accomplish. The development of ab initio composite models represents a major advance in the obtention of these thermochemical parameters,. but these methods do not always lead to accurate values. Aiming at achieving a comparison between the ab initio models and the hybrid models based on the density functional theory (DFT), we have studied gamma-butyrolactone and 2-pyrrolidinone with a goal of obtaining high-quality thermochemical parameters using the composite chemical models G2, G2MP2, MP2, G3, CBS-Q, CBS-4, and CBS-QB3; the DFT methods B3LYP, B3P86, PW91PW91, mPW1PW, and B98; and the basis sets 6-31G(d), 6-31+G(d), 6-31G(d,p), 6-31+G(d,p), 6-31++G(d,p), 6-311G(d), 6-311+G(d), 6-311G(d,p), 6-311+G(d,p), 6-311++G(d,p), aug-cc-pVDZ, and aug-cc-pVTZ. Values obtained for the enthalpies of formation, proton affinity, and gas-phase basicity of the two target molecules were compared to the experimental data reported in the literature. The best results were achieved with the use of DFT models, and the B3LYP method led to the most accurate data.

A study of actinic cheilitis treatment by two low-morbidity CO(2) laser vaporization one-pass protocols

Therapeutic approaches to chronic actinic cheilitis focus on the removal or destruction of diseased epithelium. The CO(2) laser has become an important therapeutic alternative, achieving clinical resolution in around 90% of patients. Although many laser physical parameters have been reported, some are known for their low potential for scar induction without compromising the success of the results. The aim of this clinicohistological study was to compare the therapeutic responses to two low-morbidity protocols involving a single laser pass. A total of 40 patients with chronic multicentric and microscopically proven disease were randomly submitted to two conservative CO(2) laser protocols using a bilateral comparative model. The degree of histological atypia of the epithelium was determined in 26 patients both pre- and postoperatively for both protocols. Other histological phenomena were assessed in addition to this central analysis parameter. Clinical recurrence occurred in 12.5% of patients for each protocol, together with a significant reduction in the degree of epithelial atypia (p < 0.001), which was occasionally complete. However, no difference was found between the protocols (p > 0.05). Using these morphological parameters it was not possible to determine whether postoperative epithelial atypias in part of the sample were reactive or residual in nature. A few patients may show minor postoperative lesions. Due to their potential to achieve clinical and importantly microscopic resolution, the studied protocols may be used for mild through moderate dysplastic epithelium and clinically diffuse disease.

The measurement of Pitot pressure in high enthalpy expansion tubes

Expansion tubes operating at total flow enthalpies of 100 MJ kg(-1) or more have characteristical test times of 30-50 mus. Under these conditions, the response time of the Pitot pressure measuring device is critical when performing flow calibration studies. The conventional technique of using a commercial pressure transducer protected by shielding has not always proven to be effective, due to the relatively large (and variable) response time caused by the shielding. A device called the stress wave bar gauge has been designed and calibrated and shown to be an effective way to measure the Pitot pressure with a response time of only 2-3 mus.

Heat transfer and flow behind a step in high enthalpy superorbital flow

Heat transfer levels have been investigated behind a rearward-facing step in a superorbital expansion tube. The heat transfer was measured along a flat plate and behind 2 and 3mm steps with the same length to step height ratio. Results were obtained with air as the test gas at speeds of 6.76kms(-1) and 9-60kms(-1) corresponding to stagnation enthalpies of 26MJ/kg and 48MJ/kg respectively. A laminar boundary layer was established on the flat plate and measured heat transfer levels were consistent with classical empirical correlations. In the case of flow behind a step, the measurements showed a gradual rise in heat transfer from the rear of the step to a plateau several step heights downstream for both flow conditions. Reattachment distance was estimated to be approximately 1.6 step heights downstream of the 2mm step at the low enthalpy condition through the use of flow visualisation.

Skin-friction measurements in high-enthalpy hypersonic boundary layers

Skin-friction measurements are reported for high-enthalpy and high-Mach-number laminar, transitional and turbulent boundary layers. The measurements were performed in a free-piston shock tunnel with air-flow Mach number, stagnation enthalpy and Reynolds numbers in the ranges of 4.4-6.7, 3-13 MJ kg(-1) and 0.16 x 10(6)-21 x 10(6), respectively. Wall temperatures were near 300 K and this resulted in ratios of wall enthalpy to flow-stagnation enthalpy in the range of 0.1-0.02. The experiments were performed using rectangular ducts. The measurements were accomplished using a new skin-friction gauge that was developed for impulse facility testing. The gauge was an acceleration compensated piezoelectric transducer and had a lowest natural frequency near 40 kHz. Turbulent skin-friction levels were measured to within a typical uncertainty of +/-7%. The systematic uncertainty in measured skin-friction coefficient was high for the tested laminar conditions; however, to within experimental uncertainty, the skin-friction and heat-transfer measurements were in agreement with the laminar theory of van Driest (1952). For predicting turbulent skin-friction coefficient, it was established that, for the range of Mach numbers and Reynolds numbers of the experiments, with cold walls and boundary layers approaching the turbulent equilibrium state, the Spalding & Chi (1964) method was the most suitable of the theories tested. It was also established that if the heat transfer rate to the wall is to be predicted, then the Spalding & Chi (1964) method should be used in conjunction with a Reynolds analogy factor near unity. If more accurate results are required, then an experimentally observed relationship between the Reynolds analogy factor and the skin-friction coefficient may be applied.

Bartholin's Gland Cysts: Management with Carbon-Dioxide Laser Vaporization

OBJETIVO: Avaliar a eficácia, a taxa de recorrência e as complicações da vaporização laser com CO2 no tratamento dos cistos da glândula de Bartholin. MÉTODOS: Estudo retrospectivo com 127 pacientes que apresentavam cistos sintomáticos da glândula de Bartholin submetidas à vaporização laser CO2 na nossa instituição de janeiro de 2005 a junho de 2011. Foram excluídas todas as pacientes com abcessos da glândula de Bartholin ou com suspeita de câncer. Todos os procedimentos foram realizados em regime ambulatorial, sob anestesia local. A coleta dos dados foi feita com base na consulta do processo clínico, tendo-se procedido à análise das características demográficas, dos parâmetros anatômicos, das complicações intra e pós-operatórias e dos dados de acompanhamento. Os dados foram armazenados e analisados no software Microsoft Excel® 2007, e os resultados foram apresentados como frequência (porcentagem) ou média±desvio padrão. As taxas de complicações, recorrência e cura foram calculadas. RESULTADOS: A idade média das pacientes foi de 37,3±9,5 anos (variando entre 18 e 61 anos). Setenta por cento(n=85) delas eram multíparas. A queixa mais frequente foi dor e 47,2% (n=60) das pacientes tinham antecedentes de tratamento médico e/ou cirúrgico por abcesso da glândula de Bartholin. A dimensão média dos cistos foi de 2,7±0,9 cm. Foram verificados três (2,4%) casos de hemorragia intraoperatória ligeira e 17 (13,4%) recorrências durante um período médio de 14,6 meses (variando entre 1 e 56 meses): dez abscessos da glândula de Bartholin e sete cistos recorrentes, que precisavam de uma nova intervenção cirúrgica. A taxa de cura após um único tratamento à laser foi de 86,6%. Dentre as cinco pacientes com doença recorrente que foram submetidas a um segundo procedimento com laser, a taxa de cura foi de 100%. CONCLUSÕES: Na presente instituição, a vaporização laser com CO2 parece ser uma opção terapêutica segura e eficaz no tratamento dos cistos da glândula de Bartholin.

kinetic analysis of ester hydrolysis reactions considering volume and enthalpy changes due to mixing

Magdeburg, Univ., Fak. für Verfahrens- und Systemtechnik, Diss., 2012

Vaporization behaviour and some thermodynamic properties of the Pd-In, Pd-Pb, Pd-Sn systems

In this study, the vaporization behaviour of solid Pd-rich phases in the Pd-Pb, Pd-In and Pd-Sn systems was investigated by Knudsen-effusion-cell coupled with mass-spectrometry. The Pb, Pd, In vapor pressures [no Sn(g) has been detected in the vapor of Pd-Sn system] were evaluated in the temperatures range 1190-1563 K from the ion intensities measured over two-phases regions. Thermodynamic quantities were derived from vapor pressure data. In particular, for the Pd-Sn binary, the intermediate phase Pd7Sn2, the existence of which has been recently proposed, has been studied here for the first time. Furthermore, preliminary thermochemical data are presented for the diatomic intermetallic molecules PdSn and PdPb, which have been for the first time identified in the vapors in equilibrium over liquid solutions of appropriate composition at higher temperatures (1935-2025 K). (C) 2000 Elsevier Science Ltd. All rights reserved.

The thermal circuits of the Argentera Massif (western Alps, Italy): An example of low-enthalpy geothermal resources controlled by Neogene alpine tectonics

This work presents geochemistry and structural geology data concerning the low enthalpy geothermal circuits of the Argentera crystalline Massif in northwestern Italian Alps. I n this area some thermal springs (50-60 degreesC), located in the small Bagni di Vinadio village, discharge mixtures made up of a Na-Cl end-member and a Na-SO4 component. The latter is also discharged by the thermal springs of Terme di Valdieri located some kilometres apart within the same tectonic complex. Both end-members share the same meteoric origin and the same reservoir temperature, which is close to 150 degreesC. Explanations are thus required to understand how they reach the surface and how waters of the same origin and circulating in similar rocks can attain such different compositions. Sodium-sulphate waters discharged at both sites, likely represent the common interaction product of meteoric waters with the widespread granitic-migmatitic rocks of the Argentera Massif, whereas Na-CI waters originate through leaching of mineralised cataclastic rocks, which are rich in phyllosilicatic minerals and fluid inclusions, both acting as Cl- sources. Due to the relatively low inferred geothermal gradient of the region, -25C/km, meteoric waters have to descend to depths of 5.5-6 km to attain temperatures of similar to 150 degreesC. These relevant depths can be reached by descending meteoric waters, due to the recent extensional stress field, which allows the development of geothermal circulations at greater depths than in other sectors of the Alps by favouring a greater fractures aperture. The ascent of the thermal waters rakes place along brittle shear zones. In both sites, the thermal waters emerge at the bottoms of the valleys, close to either the lateral termination of a brittle shear zone at Terme di Valdieri, or a step-over between two en-echelon brittle shear zones at Bagni di Vinadio. These observations attest to a strong control operated on the location of outlet regions by both brittle tectonics and the minima in hydraulic potential inside the fractured massif.

Estimating the value of the metal-ligand bond dissociation enthalpy<D> (M-L) for adducts using empirical equations supported by TG data

In this work is presented and tested (for 106 adducts, mainly of the zinc group halides) two empirical equations supported in TG data to estimate the value of the metal-ligand bond dissociation enthalpy for adducts: <D> (M-O) = t i / g if t i < 420 K and <D> (M-O) = (t i / g ) - 7,75 . 10-2 . t i if t i > 420 K. In this empirical equations, t i is the thermodynamic temperature of the beginning of the thermal decomposition of the adduct, as determined by thermogravimetry, andg is a constant factor that is function of the metal halide considered and of the number of ligands, but is not dependant of the ligand itself. To half of the tested adducts the difference between experimental and calculated values was less than 5%. To about 80% of the tested adducts, the difference between the experimental (calorimetric) and the calculated (using the proposed equations) values are less than 15%.

Termodinâmica estatística de líquidos com o método de Monte Carlo. II. O líquido clorofórmio

Thermodynamic properties and radial distribution functions for liquid chloroform were calculated using the Monte Carlo method implemented with Metropolis algorithm in the NpT ensemble at 298 K and 1 atm. A five site model was developed to represent the chloroform molecules. A force field composed by Lennard-Jones and Coulomb potential functions was used to calculate the intermolecular energy. The partial charges needed to represent the Coulombic interactions were obtained from quantum chemical ab initio calculations. The Lennard-Jones parameters were adjusted to reproduce experimental values for density and enthalpy of vaporization for pure liquid. All thermodynamic results are in excelent agreement with experimental data. The correlation functions calculated are in good accordance with theoretical results avaliable in the literature. The free energy for solvating one chloroform molecule into its own liquid at 298 K and 1 atm was computed as an additional test of the potential model. The result obtained compares well with the experimental value. The medium effects on cis/trans convertion of a hypotetical solute in water TIP4P and chloroform solvents were also accomplished. The results obtained from this investigation are in agreement with estimates of the continuous theory of solvation.

Determinação da entalpia de vaporização de líquidos pelo método do isoteniscópio de Smith e Menzies

This article proposes an experimental procedure to determine the enthalpy (and entropy) of vaporization of organic liquid compounds, by the Smith-Menzies (isoteniscope) method. The values of vapor pressure at different temperatures were obtained and ΔvH (and ΔvS) were graphically determined, using the Clausius-Clapeyron equation. The results for diethyl-ether, propanone, ethanol and n-hexane are in very good agreement with those from literature. A historical and thermodynamic discussion on equations that correlates vapor pressures and temperature precedes the experimental proposition.