THERMOCHEMISTRY

Author: VALENCIA ALVAREZ JOSE LUIS.
Year: 2005.
University: VIGO [www.uvigo.es].
Place of defense: FACULTAD DE CIENCIAS DE ORENSE.
Place of preparation: FACULTAD DE CIENCIAS DE ORENSE.

Summary: It has perfected a modification of the procedure for measuring the density with densímetro high pressure Anton For DMA 512 P that optimizes the operation of the experimental device. It has conducted a survey of the results of the density from four different calibration procedures. With calibration classic, has been experimentally determined the densities of the pure liquids following: hexane, nonane, dean, undecano, dodecano, tridecano, tetradecano, hexanol, butanol and toluene and have been compared with values from the literature. The measures have been carried out at intervals of temperature [283.15-323.15] Ky. pressure [0.1-60] MPa. It has developed a calorimeter Micro DSC n Setaram to work at high pressures. To this end have been designed and built some cells that help to measure the pressure of 70 MPa. Moreover has developed a line of high pressure which consists, among other things, a pressure generator and a buffer size, and has proposed a calibration procedure. The differential scanning method has been experimentally determined capacities isobaric heat per unit volume of the pure liquids following: hexane, nonane, dean, undecano, dodecano, tridecano, tetradecano and hexanol. The measures have been carried out at intervals of temperatures and pressures [283.15-323.15] K [0.1-60] MPa, respectively. By combining the capabilities isobaric heat per unit volume and densities have been calculated heat capacities isobaric molars and has been compared to existing data in the literature. It has been estimated uncertainty through two techniques for processing errors. It has become a methodology that from data density and molar isobaric heat capacity, it produces the following properties from the compressibility isotherm, expansividad thermal isobaric, the compressibility isentropic and the ability heat isocórica.

Author: TEMPRADO MORENA MANUEL.
Year: 2005.
University: COMPLUTENSE DE MADRID [www.ucm.es].
Place of defense: FACULTAD DE CIENCIAS QUÍMICAS.
Place of preparation: INSTITUTO DE QUÍMICA FÍSICA ROCASOLANO, CSIC.

Summary: In this thesis has conducted a study thermochemical, calorimétrico and computational a series of derivatives thiophene (acid 2-tiofenocarboxílioc [527-72-0], acid 3-tiofencocarboxílico [88-13-1], 2-acetiltiofeno [ 88-15-3], 3-acetiltiofeno [1468-83-3], acid 2-tiofenoacético [1918-77-0], acid 3-tiofenoacético [6964-21-2], 2-tiofenoacetato demetilo [19432-68 -9], 3-tiofenoacetato demetilo [58414-52-1] and 2.2 'bitiofeno [492-97-7]) and sulfones and sulfóxidos derivatives tiano (tiano sulfone [4988-33-4], tiano sulfoxide [4988-34-5], 1,3-ditiano sulfoxide [16487-10-8], 1,3-ditiano sulfone [55337-75-2], 1,4-ditiano sulfone [139408-38-1] 1.3-oxatiano sulfone [109577-03-9] and 1,4-oxatiano sulfone [107-61-9]). The experimental techniques have been used calorimetry combustion technique outpouring of Knudsen, correlation by gas chromatography and differential scanning calorimetry. The computational study has been carried out ab initio calculations conducting high-level protocols calculation G2 and G2 (MP2). Collected data has been made a correlation teoría-experimento, has done an analysis of the difference between energy derivatives substituted thiophene at positions 2 and 3 and has analyzed the difference between energy isomers of tiano according electrostatic effects, electronic and estéricos. Additionally, a study has been made termofísico of phase transitions, polymorphism and heat capacities depending on the temperature for all compounds.