Vapor-liquid equilibria using the Gibbs energy and the common tangent plane criterion

Phase thermodynamics is often perceived as a difficult subject that many students never become fully comfortable with. The Gibbsian geometrical framework can help students to gain a better understanding of phase equilibria. An exercise to interpret the vapor-liquid equilibrium of a binary azeotropic mixture, using the equilibrium condition based on the common tangent plane criterion (the Gibbs stability test), is presented in this paper. From a T-composition phase diagram for the mixture, the temperature is set at different values: above, intermediate to, and below the boiling temperatures of the pure components, to intersect different regions of the system. Students prepare an Excel spreadsheet where the Gibbs energy of mixing of the vapor and liquid mixtures are calculated and represented over the whole range of compositions and then, apply the Gibbs stability test to ascertain the aggregation state of the system and to calculate the VL phase equilibrium compositions. Finally, Matlab is used to generate the 3D Gibbs energy of mixing surfaces for both phases over the whole range of temperatures which facilitates the geometrical interpretation of the vapor-liquid equilibrium.

Stability test of modified repair options for San Pedro Breakwater, Los Angeles, California : coastal model investigation /

"July 1986."

Correlation of the liquid–liquid equilibrium data for specific ternary systems with one or two partially miscible binary subsystems

This paper presents the results of a liquid–liquid equilibrium data correlation for 11 ternary systems which have not been previously fitted using the NRTL model or, when they have, the results presented in the literature are inconsistent with the experimental behavior of the system. These ternary systems include mixtures with one or two partially miscible pairs. During the correlation process, new restrictions were imposed on the values for the NRTL binary parameters to ensure correct prediction of the total or partial miscibility for the binary pairs involved. In addition, topological concepts related to the Gibbs stability test have been applied in order to validate the results in the whole range of compositions.

Modelling liquid–liquid equilibria for island type ternary systems

Closed miscibility gaps in ternary liquid mixtures, at constant temperature and pressure, are obtained if phase separations occur only in the ternary region, whilst all binary mixtures involved in the system are completely miscible. This type of behaviour, although not very frequent, has been observed for a certain number of systems. Nevertheless, we have found no information about the applicability of the common activity coefficient models, as NRTL and UNIQUAC, for these types of ternary systems. Moreover, any of the island type systems published in the most common liquid–liquid equilibrium data collections, are correlated with any model. In this paper, the applicability of the NRTL equation to model the LLE of island type systems is assessed using topological concepts related to the Gibbs stability test. A first attempt to correlate experimental LLE data for two island type ternary systems is also presented.

Análise global da estabilidade termodinâmica de misturas: um estudo com o método do conjunto gerador

O cálculo do equilíbrio de fases é um problema de grande importância em processos da engenharia, como, por exemplo, na separação por destilação, em processos de extração e simulação da recuperação terciária de petróleo, entre outros. Mas para resolvê-lo é aconselhável que se estude a priori a estabilidade termodinâmica do sistema, a qual consiste em determinar se uma dada mistura se apresenta em uma ou mais fases. Tal problema pode ser abordado como um problema de otimização, conhecido como a minimização da função distância do plano tangente à energia livre de Gibbs molar, onde modelos termodinâmicos, de natureza não convexa e não linear, são utilizados para descrevê-lo. Esse fato tem motivado um grande interesse em técnicas de otimização robustas e eficientes para a resolução de problemas relacionados com a termodinâmica do equilíbrio de fases. Como tem sido ressaltado na literatura, para proporcionar uma completa predição do equilíbrio de fases, faz-se necessário não apenas a determinação do minimizador global da função objetivo do teste de estabilidade, mas também a obtenção de todos os seus pontos estacionários. Assim, o desenvolvimento de metodologias para essa tarefa desafiadora tem se tornado uma nova área de pesquisa da otimização global aplicada à termodinâmica do equilíbrio, com interesses comuns na engenharia química e na engenharia do petróleo. O foco do presente trabalho é uma nova metodologia para resolver o problema do teste de estabilidade. Para isso, usa-se o chamado método do conjunto gerador para realizar buscas do tipo local em uma rede de pontos previamente gerada por buscas globais efetuadas com uma metaheurística populacional, no caso o método do enxame de partículas.Para se obter mais de um ponto estacionário, minimizam-se funções de mérito polarizadas, cujos pólos são os pontos previamente encontrados. A metodologia proposta foi testada na análise de quatorze misturas polares previamente consideradas na literatura. Os resultados mostraram que o método proposto é robusto e eficiente a ponto de encontrar, além do minimizador global, todos os pontos estacionários apontados previamente na literatura, sendo também capaz de detectar, em duas misturas ternárias estudadas, pontos estacionários não obtidos pelo chamado método de análise intervalar, uma técnica confiável e muito difundida na literatura. A análise do teste de estabilidade pela simples utilização do método do enxame de partículas associado à técnica de polarização mencionada acima, para a obtenção de mais de um ponto estacionário (sem a busca local feita pelo método do conjunto gerador em uma dada rede de pontos), constitui outra metodologia para a resolução do problema de interesse. Essa utilização é uma novidade secundária deste trabalho. Tal metodologia simplificada exibiu também uma grande robustez, sendo capaz de encontrar todos os pontos estacionários pesquisados. No entanto, quando comparada com a abordagem mais geral proposta aqui, observou-se que tal simplificação pode, em alguns casos onde a função de mérito apresenta uma geometria mais complexa, consumir um tempo de máquina relativamente grande, dessa forma é menos eficiente.

Stability analysis of power systems described with detailed models by automatic method

The power system stability analysis is approached taking into explicit account the dynamic performance of generators internal voltages and control devices. The proposed method is not a direct method in the usual sense since conclusion for stability or instability is not exclusively based on energy function considerations but it is automatic since the conclusion is achieved without an analyst intervention. The stability test accounts for the nonconservative nature of the system with control devices such as the automatic voltage regulator (AVR) and automatic generation control (AGC) in contrast with the well-known direct methods. An energy function is derived for the system with machines forth-order model, AVR and AGC and it is used to start the analysis procedure and to point out criticalities. The conclusive analysis itself is made by means of a method based on the definition of a region surrounding the equilibrium point where the system net torque is equilibrium restorative. This region is named positive synchronization region (PSR). Since the definition of the PSR boundaries have no dependence on modelling approximation, the PSR test conduces to reliable results. (C) 2008 Elsevier Ltd. All rights reserved.

Effect of disinfection and accelerated ageing on dimensional stability and detail reproduction of a facial silicone with nanoparticles

The aim of the present study was to evaluate the effect of disinfection and accelerated ageing on the dimensional stability and detail reproduction of a facial silicone with different types of nanoparticle. A total of 60 specimens were fabricated with Silastic MDX 4-4210 silicone and they were divided into three groups: colourless and pigmented with nanoparticles (make-up powder and ceramic powder). Half of the specimens of each group were disinfected with Efferdent tablets and half with neutral soap for 60 days. Afterwards, all specimens were subjected to accelerated ageing. Both dimensional stability and detail reproduction tests were performed after specimen fabrication (initial period), after chemical disinfection, and after accelerated ageing periods (252, 504 and 1008 hours). The dimensional stability test was conducted using AutoCAD software, while detail reproduction was analysed using a stereoscope magnifying glass. Dimensional stability values were statistically evaluated by analysis of variance (ANOVA) followed by Tukey's test (p < 0.01). Detail reproduction results were compared using a score. Chemical disinfection and also accelerated ageing affected the dimensional stability of the facial silicone with statistically significant results. The silicone's detail reproduction was not affected by these two factors regardless of nanoparticle type, disinfection and accelerated ageing. © 2012 Informa UK, Ltd.

Study of physical-chemical stability in contaminated conditioners by bacteria

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Microencapsulation of lycopene by spray drying: Characterization, stability and application of microcapsules

Microencapsulation can be an alternative to minimize lycopene instability. Thus, the aim of this study was to microencapsulate lycopene by spray drying, using a modified starch (Capsul (R)) as an encapsulating agent, and to assess the functionality of the capsules applying them in cake. The quantity of lycopene was varied at 5, 10 and 15% in a solution containing 30% of solids in order to obtain the microcapsules. These microcapsules were evaluated as to encapsulation efficiency and morphology and then submitted to a stability test and applied in cakes. Encapsulation efficiency values varied between 21 and 29%. The microcapsules had a rounded outer surface with the formation of concavities and they varied in size. The stability test revealed that microencapsulation offered greater protection to lycopene compared to its free form and it was observed that the microcapsules were able to release pigment and color the studied food system in a homogenous manner. (C) 2011 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Results of the IEA round robin on viscosity and stability of fast pyrolysis bio-oils

An international round robin study of the stability of fast pyrolysis bio-oil was undertaken. Fifteen laboratories in five different countries contributed. Two bio-oil samples were distributed to the laboratories for stability testing and further analysis. The stability test was defined in a method provided with the bio-oil samples. Viscosity measurement was a key input. The change in viscosity of a sealed sample of bio-oil held for 24 h at 80 °C was the defining element of stability. Subsequent analyses included ultimate analysis, density, moisture, ash, filterable solids, and TAN/pH determination, and gel permeation chromatography. The results showed that kinematic viscosity measurement was more generally conducted and more reproducibly performed versus dynamic viscosity measurement. The variation in the results of the stability test was great and a number of reasons for the variation were identified. The subsequent analyses proved to be at the level of reproducibility, as found in earlier round robins on bio-oil analysis. Clearly, the analyses were more straightforward and reproducible with a bio-oil sample low in filterable solids (0.2%), compared to one with a higher (2%) solids loading. These results can be helpful in setting standards for use of bio-oil, which is just coming into the marketplace. © 2012 American Chemical Society.

Effect of polymer microstructure on the docetaxel release and stability of polyurethane formulation

PurSil®AL20 (PUS), a copolymer of 4,4'-dicyclohexylmethane diisocyanate (HMDI), 1,4-butane diol (BD), poly-tetramethylene oxide (PTMO) and poly-dimethyl siloxane (PDMS) was investigated for stability as a vehicle for Docetaxel (DTX) delivery through oesophageal drug eluting stent (DES). On exposure to stability test conditions, it was found that DTX release rate declined at 4 and 40 °C. In order to divulge reasons underlying this, changes in DTX solid state as well as PUS microstructure were followed. It was found that re-crystallization of DTX in PDMS rich regions was reducing the drug release at both 4 °C and 40 °C samples. So far microstructural features have not been correlated with stability and drug release, and in this study we found that at 40 °C increase in microstructural domain sizes and the inter-domain distances (from ∼85 Å to 129 Å) were responsible for hindering the DTX release in addition to DTX re-crystallization.

Test of Emotion Comprehension: Exploring the underlying structure through Confirmatory Factor Analysis and Similarity Structure Analysis

Some decades of research on emotional development have underlined the contribution of several domains to emotional understanding in childhood. Based on this research, Pons and colleagues (Pons & Harris, 2002; Pons, Harris & Rosnay, 2004) have proposed the Test of Emotion Comprehension (TEC) which assesses nine domains of emotional understanding, namely the recognition of emotions, based on facial expressions; the comprehension of external emotional causes; impact of desire on emotions; emotions based on beliefs; memory influence on emotions; possibility of emotional regulation; possibility of hiding an emotional state; having mixed emotions; contribution of morality to emotional experiences. This instrument was administered individually to 182 Portuguese children aged between 8 and 11 years, of 3rd and 4th grades, in public schools. Additionally, we used the Socially in Action-Peers (SAp) (Rocha, Candeias & Lopes da Silva, 2012) to assess TEC’s criterion-related validity. Mean differences results in TEC by gender and by socio-economic status (SES) were analyzed. The results of the TEC’s psychometric analysis were performed in terms of items’ sensitivity and reliability (stability, test-retest). Finally, in order to explore the theoretical structure underlying TEC a Confirmatory Factor Analysis and a Similarity Structure Analysis were computed. Implications of these findings for emotional understanding assessment and intervention in childhood are discussed.

Finnish Dosimetric Practice for Epithermal Neutron Beam Dosimetry in Boron Neutron Capture Therapy

Boron neutron capture therapy (BNCT) is a form of chemically targeted radiotherapy that utilises the high neutron capture cross-section of boron-10 isotope to achieve a preferential dose increase in the tumour. The BNCT dosimetry poses a special challenge as the radiation dose absorbed by the irradiated tissues consists of several dose different components. Dosimetry is important as the effect of the radiation on the tissue is correlated with the radiation dose. Consistent and reliable radiation dose delivery and dosimetry are thus basic requirements for radiotherapy. The international recommendations for are not directly applicable to BNCT dosimetry. The existing dosimetry guidance for BNCT provides recommendations but also calls for investigating for complementary methods for comparison and improved accuracy. In this thesis the quality assurance and stability measurements of the neutron beam monitors used in dose delivery are presented. The beam monitors were found not to be affected by the presence of a phantom in the beam and that the effect of the reactor core power distribution was less than 1%. The weekly stability test with activation detectors has been generally reproducible within the recommended tolerance value of 2%. An established toolkit for epithermal neutron beams for determination of the dose components is presented and applied in an international dosimetric intercomparison. The measured quantities (neutron flux, fast neutron and photon dose) by the groups in the intercomparison were generally in agreement within the stated uncertainties. However, the uncertainties were large, ranging from 3-30% (1 standard deviation), emphasising the importance of dosimetric intercomparisons if clinical data is to be compared between different centers. Measurements with the Exradin type 2M ionisation chamber have been repeated in the epithermal neutron beam in the same measurement configuration over the course of 10 years. The presented results exclude severe sensitivity changes to thermal neutrons that have been reported for this type of chamber. Microdosimetry and polymer gel dosimetry as complementary methods for epithermal neutron beam dosimetry are studied. For microdosimetry the comparison of results with ionisation chambers and computer simulation showed that the photon dose measured with microdosimetry was lower than with the two other methods. The disagreement was within the uncertainties. For neutron dose the simulation and microdosimetry results agreed within 10% while the ionisation chamber technique gave 10-30% lower neutron dose rates than the two other methods. The response of the BANG-3 gel was found to be linear for both photon and epithermal neutron beam irradiation. The dose distribution normalised to dose maximum measured by MAGIC polymer gel was found to agree well with the simulated result near the dose maximum while the spatial difference between measured and simulated 30% isodose line was more than 1 cm. In both the BANG-3 and MAGIC gel studies, the interpretation of the results was complicated by the presence of high-LET radiation.

Berry phenolics: isolation, analysis, identification, and antioxidant properties

The main objectives in this thesis were to isolate and identify the phenolic compounds in wild (Sorbus aucuparia) and cultivated rowanberries, European cranberries (Vaccinium microcarpon), lingonberries (Vaccinium vitis-idaea), and cloudberries (Rubus chamaemorus), as well as to investigate the antioxidant activity of phenolics occurring in berries in food oxidation models. In addition, the storage stability of cloudberry ellagitannin isolate was studied. In wild and cultivated rowanberries, the main phenolic compounds were chlorogenic acids and neochlorogenic acids with increasing anthocyanin content depending on the crossing partners. The proanthocyanidin contents of cranberries and lingonberries were investigated, revealing that the lingonberry contained more rare A-type dimers than the European cranberry. The liquid chromatography mass spectrometry (LC-MS) analysis of cloudberry ellagitannins showed that trimeric lambertianin C and sanguiin H-10 were the main ellagitannins. The berries, rich in different types of phenolic compounds including hydroxycinnamic acids, proanthocyanidins, and ellagitannins, showed antioxidant activity toward lipid oxidation in liposome and emulsion oxidation models. All the different rowanberry cultivars prevented lipid oxidation in the same way, in spite of the differences in their phenolic composition. In terms of liposomes, rowanberries were slightly more effective antioxidants than cranberry and lingonberry phenolics. Greater differences were found when comparing proanthocyanidin fractions. Proanthocyanidin dimers and trimers of both cranberries and lingonberries were most potent in inhibiting lipid oxidation. Antioxidant activities and antiradical capacities were also studied with hydroxycinnamic acid glycosides. The sinapic acid derivatives of the hydroxycinnamic acid glycosides were the most effective at preventing lipid oxidation in emulsions and liposomes and scavenging radicals in DPPH assay. In liposomes and emulsions, the formation of the secondary oxidation product, hexanal, was inhibited more than that of the primary oxidation product, conjugated diene hydroperoxides, by hydroxycinnamic acid derivatives. This indicates that they are principally chain-breaking antioxidants rather than metal chelators, although they possess chelating activity as well. The storage stability test of cloudberry ellagitannins was performed by storing ellagitannin isolate and ellagitannins encapsulated with maltodextrin at different relative vapor pressures. The storage stability was enhanced by the encapsulation when higher molecular weight maltodextrin was used. The best preservation was achieved when the capsules were stored at 0 or 33% relative vapor pressures. In addition, the antioxidant activities of encapsulated cloudberry extracts were followed during the storage period. Different storage conditions did not alter the antioxidant activity, even though changes in the ellagitannin contents were seen. The current results may be of use in improving the oxidative stability of food products by using berries as natural antioxidants.

Avaliação de gases efeito estufa na cidade do Rio de Janeiro

O presente trabalho teve como objetivo a validação de uma metodologia de amostragem para GEE Gases do Efeito Estufa, com a utilização de seringas e análise por cromatografia de fase gasosa com múltiplos detectores. O trabalho se dividiu em duas etapas. A primeira etapa consistiu em um teste de estabilidade avaliando o meio de amostragem proposto, a seringa, e comparando-o a dois meios de amostragem convencionais canister e bolsa de teflon -, utilizando uma amostra padrão de GEE. A segunda etapa foi a aplicação desta nova metodologia de amostragem na cidade do Rio de Janeiro, buscando a avaliação da concentração dos GEE em diferentes bairros da cidade e a correlação destas com dados meteorológicos e características da localização dos pontos amostrados. Nestas amostragens realizadas na cidade do Rio de Janeiro obteve-se uma média de 536 ppmv, 2,04 ppmv e 274 ppbv, para o CO2, CH4 e N2O, respectivamente, que foram os GEE analisados. Foi possível neste trabalho verificar o grau de correlação dos GEE estudados com variáveis meteorológicas, bem como com outros poluentes já legislados e participantes de monitoramento contínuo. As conclusões alcançadas foram que a nova metodologia proposta para amostragem de GEE é viável devido ao seu bom desempenho no teste de estabilidade, ao baixo custo do material empregado e à praticidade do mesmo, e que as concentrações dos GEE avaliados na cidade do Rio de Janeiro encontram-se superiores às concentrações indicadas como médias globais para os mesmos. Apontando desta forma, a necessidade de um monitoramento contínuo destes de forma a contribuir para a tomada de ações de mitigação dos GEE