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The physical properties of single crystals of samarium monosulfide exhibit a first order semiconductor-to-metal transition near 6.5 kbar. However, thin films of SmS show only a gradual change in their properties on applying pressure and this renders the technical utilization of the material difficult. Several mechanisms have been proposed as the cause of the smoothing of the transition. They include intrinsic stress, impurities, grain size, improper stoichiometry, and porosity, all of which can be traced to the physical vapor deposition techniques employed in preparing the films. In contrast, chemical vapor deposition was employed in this study because previous work had shown that it could minimize these detrimental modifications in thin films. A new CVD system was tested using a volatile organometallic as the samarium source and reacting it with H₂S. The deposited films contained considerable amounts of oxygen as evidenced by structure analysis, and the origin was traced to the samarium organometallic. The reaction of oxygen-free samarium tricyclopentadienyl with H₂S as well as chemical transport are suggested for deposition of stress-free SmS thin films in future work.

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Ingeniero Civil Químico / En el presente informe se muestra el desarrollo del proyecto de la Clínica Alemana de Osorno, para reducir las emisiones de material particulado de su caldera, debido a las preocupantes condiciones de contaminación atmosférica de la ciudad. Con este objetivo, se exponen diversas tecnologías de control de material particulado, considerando aspectos técnicos, ambientales y económicos. Tras realizar las comparaciones pertinentes, se decidió enfocar el trabajo en el diseño de un depurador tipo Venturi, debido a que su incorporación lograría disminuir las emisiones a niveles adecuados, y sus características de operación y mantención son aptas para el caso de estudio. El diagnóstico de las emisiones actuales se construyó sobre las mediciones realizadas en la caldera, para caracterizar el material particulado y las condiciones de los gases emitidos. Con esta información, y aplicando un modelo matemático del depurador Venturi, fue posible definir las características adecuadas de su diseño. Según este modelo, además, se prevé la disminución de material particulado en las emisiones desde 930 mg/m3, medidos en los gases emitidos de la caldera sin su tratamiento actual, hasta 90 mg/m3 en las condiciones más adversas. Una vez diseñado el depurador, se dimensionaron los equipos secundarios necesarios para su funcionamiento, encontrándose diferencias significativas con respecto a los equipos similares instalados actualmente. En cuanto a la implementación del proyecto, se recomienda que se realice por fases, dando mayor prioridad a aquellos equipos cuyo reemplazo sea más simple y, con certeza, necesario. Una vez finalizada su implementación, es necesario mantener un registro de las variables adecuadas para verificar la eficiencia de la depuración. Finalmente, el costo de operación del proyecto, que involucra el consumo de agua y energía eléctrica, se estimó en CLP$ 640.000 mensuales. Por otro lado, el costo de inversión, que supone la compra de todos los equipos necesarios para el proceso de depuración, se estimó en CLP$ 17.050.000.

Submitted in fulfillment of the requirements of the degree of Master of Engineering, Durban University of Technology, Durban, South Africa, 2016. / Separation processes in the chemical process industries is dependent on the science of chemical thermodynamics. In the field of chemical separation process engineering, phase equilibrium is a primary area of interest. This is due to separation processes such as distillation and extraction which involves the contacting of different phases for effective separation. The focal point of this research project is the measurement and modeling of binary vapour-liquid equilibrium (VLE) phase data of systems containing ether-alcohol organic compounds. The VLE data were measured with the use of the modified apparatus of Raal and Mühlbauer, (1998). The systems of interest for this research arose from an industrial demand for VLE data for systems containing ether-alcohol organic compounds. This gave rise to the experimental VLE data isotherms being measured for the following binary systems: a) Methyl tert-butyl ether (1) + 1-pentanol (2) at 317.15 and 327.15 K b) Methyl tert-butyl ether (1) + 2, 2, 4-trimethylpentane (2) at 307.15, 317.15 and 327.15K c) 2, 2, 4-Trimethylpentane (1) + 1-pentanol (2) at 350.15, 360.15 and 370.15K d) Diisopropyl ether (1) + 2,2,4-trimethylpentane (2) at 320.15, 330.15 and 340.15K e) Diisopropyl ether (1) + 1-propanol (2) at 320.15, 330.15 and 340.15K f) Diisopropyl ether (1) + 2-butanol (2) at 320.15, 330.15 and 340.15K The data for all the measured binary systems investigated at these temperatures are currently not available in the open source literature found on the internet and in library text resources. The systems were not measured at the same temperatures because certain system isotherm temperatures correlate to a pressures above 1 bar. This pressure of 1 bar is the maximum operating pressure specification of the VLE apparatus used in this project. The experimental VLE data were correlated for model parameters for both the  and methods. For the method, the fugacity coefficients (vapour-phase non-idealities) were tabulated using the virial equation of state and the Hayden-O’Connell correlation (1975); chemical theory and the Nothnagel et al. (1973) correlation method. The activity coefficients (liquid phase non-idealities) were calculated using three local-composition based activity coefficients models: the Wilson (1964) model, the NRTL model (Renon and Prausnitz, 1968); and the UNIQUAC model (Abrams and Prausnitz, 1975). Regarding the direct method, the Soave-Redlich-Kwong (Redlich and Kwong, 1949) and Peng-Robinson (1976) equations of state ii were used with the temperature dependent alpha-function (α) of Mathias and Copeman (1983) with the Wong-Sandler (1992) mixing rule. Thermodynamic consistency testing, which presents an indication of the quality and reliability of the data, was also performed for all the experimental VLE data. All the systems measured showed good thermodynamic consistency for the point test of Van Ness et al. (1973) - the consistency test of choice for this research. This however, was based on the model chosen for the data regression of a particular system. Therefore, the combined method of VLE reduction produced the most favourable results for the NRTL and Wilson models. / M

The arrival of the North American Monsoon System (NAMS) terminates a presummer hyperarid period in the southwestern United States (U.S.), providing summer moisture that is favorable for forest growth. Montane forests in this region rely on winter snowpack to drive much of their growth; the extent to which they use NAMS moisture is uncertain. We addressed this by studying stable carbon and oxygen isotopes in earlywood and latewood from 11 sites along a latitudinal gradient extending from Arizona and New Mexico to Utah. This study provides the first regional perspective on the relative roles of winter versus summer precipitation as an ecophysiological resource. Here we present evidence that Ponderosa pine uses NAMS moisture differentially across this gradient. C-13/C-12 ratios suggest that photosynthetic water use efficiency during latewood formation is more sensitive to summer precipitation at the northern than at the southern sites. This is likely due to the fact that NAMS moisture provides sufficiently favorable conditions for tree photosynthesis and growth during most years in the southern sites, whereas the northern sites experience larger summer moisture variability, which in some years is limiting growth. Cellulose O-18 and C-13 values revealed that photoassimilates in the southern sites were produced under higher vapor pressure deficit conditions during spring compared to summer, demonstrating a previously underappreciated effect of seasonal differences in atmospheric humidity on tree ring isotope ratios. Our findings suggest that future changes in NAMS will potentially alter productivity and photosynthetic water use dynamics differentially along latitudinal gradients in southwestern U.S. montane forests.