Resumen Este trabajo trata sobre la comparación de la asignación teórica del espectro vibracional de DADP con los desplazamientos experimentales por marcación isotópica. Para ello, se sintetizaron los isotopómeros DADP-C4 y DADP-C2, los cuales son isotopómeros parcialmente marcados. DADP-C4 y DADP-C2 fueron sintetizados a partir de acetona marcada isotópicamente en los átomos de carbonos del grupo metilo y carbonilo, respectivamente. La acetona y los compuestos isotopómeros de DADP fueron caracterizados usando espectroscopia Raman e Infrarroja. Las asignaciones teóricas fueron tomadas de estudios previos sobre la distribución de energía potencial de un modo vibracional, el cual proporciona una aproximación a las coordenadas internas relacionadas con cada banda vibracional. La marcación isotópica selectiva nos permitió acercarnos a la dependencia de cada banda, debido a que, la energía de una vibración molecular depende también de la masa recíproca de los átomos involucrados. En general, los resultados mostraron que algunas bandas asignadas experimentalmente no coinciden con las asignaciones teóricas mediante simulaciones mecánicas cuánticas.

Abstract This work deals with the comparison of the theoretical assignment of the DADP vibrational spectrum with the experimental displacements by isotopic labeling. For this, the DADP-C4 and DADP-C2 isotopomers were synthesized from acetone labeled isotopically in the methyl and the carbonyl carbon atoms, respectively. The acetone and DADP-isotopomer compounds were characterized using Raman and infrared spectroscopy. Theoretical assignments were taken from previous studies on the potential energy distribution of a vibrational mode, which provide an approach to the internal coordinates related to each band. The selective isotopic labeling allowed us to approach to the dependence of each band, because the energy of a molecular vibration also depends on the reciprocal mass of the atoms involved. In general, the results showed that some bands assigned experimentally do not coincide with the theoretical assignments by quantum mechanical simulations.

Resumen Los ácidos húmicos se producen por la descomposición de la materia orgánica de los suelos y por la oxidación de carbones minerales. En este estudio se analizó mediante superficies de respuesta el efecto de la oxidación en la extracción de ácidos húmicos de un carbón colombiano. Las variables de oxidación estudiadas fueron las siguientes: tamaño de partícula (0,063, 0,106 y 0,150 mm), concentración del agente oxidante (permanganato de potasio (KMnO4): 0,010, 0,020 y 0,050 M) y tiempo de oxidación (30, 60 and 90 minutos). El grado de oxidación se verificó con espectroscopia infrarroja. La oxidación incrementó los grupos oxigenados en la matriz carbonácea debido, principalmente, a la oxidación de componentes alifáticos. Se obtuvieron porcentajes de extracción superiores a 24 % al usar partículas de 0,063 mm y KMnO4 con 0,020 M. © 2017. Acad. Colomb. Cienc. Ex. Fis. Nat.

Abstract Humic acids are produced by decomposition of organic soil material and from oxidation of mineral coals. In this study, the effect of oxidation and the yield of humic acids extracted from a sample of Colombian mineral coal were studied by response surface methodology (RSM). The variables used were: particle size (0.063, 0.106 and 0.150 mm), concentration of the oxidizing agent (KMnO4: 0.010, 0.020 and 0.050 M) and oxidation time (30, 60 and 90 minutes). The degree of oxidation was verified by infrared spectroscopy. Oxidation increased oxygen groups in the carbonaceous matrix, mainly due to oxidation of aliphatic components. Extraction yields above 24% were obtained with 0.063 mm particle size and 0.020 M KMnO4. © 2017. Acad. Colomb. Cienc. Ex. Fis. Nat.

Resumen Las hidrotalcitas tienen un alto impacto en el desarrollo de nuevos materiales y en avances tecnológicos en áreas como catálisis y química ambiental. Un aspecto de vital importancia es la temperatura del colapso de la estructura HTLc, ya que de esta dependen las propiedades de los sólidos obtenidos. En este trabajo se estudió el comportamiento térmico de hidrotalcitas de níquel-aluminio y se determinó la Ea asociada al colapso y formación de NiO. Se observó que la mayor interacción entre iones carbonato y grupos OH ocurre a 250 °C, temperatura en la cual desaparece la estructura HTLc. El sólido N0,75A0,25 requirió menos energía para que ocurriese el colapso, debido a la mayor distancia entre las láminas. El material N0,66A0,33 necesito más energía para que ocurriese la formación del óxido de níquel, lo que se debe a que el mayor contenido de Al3+, desfavorece el crecimiento de las partículas iniciales de NiO.

Abstract The synthesis and use of materials as hydrotalcites have a high impact on development of new materials and technological advances, applied in areas such as catalysis and environmental chemistry. An aspect of vital importance is the temperature of collapse of the HTLc structure, because from this fact depend the properties of solids obtained. In this work was studied the thermal behavior of nickel-aluminum hydrotalcite, and determined the Ea associated with the collapse and formation of NiO. It was observed that the greater interaction among carbonate ions and OH groups occurs at 250 °C, temperature at which the collapse of the HTLc structure occurs. The solid N0,75A0,25 requires less energy to collapse, which is due to the greater distances between the positive sheets. The solid N0,66A0,33 need more energy for the formation of NiO, which is due to higher content of Al3+, disfavoring the growth of the initial particles of NiO.

In this paper, two models of humic acids, the Temple-Northeastern-Birmingham (TNB) and Kolla models, were studied. Also, the complexation reaction of the structures formed by the interaction of the TNB and Kolla models with Al3+, Ca2+, Mg2+, Zn2+, K+ and NH4+ cations, common in agricultural soils, was studied. These calculations were made for the complexes, at PM6 and DFT / LANL2DZ level of theory, both in vacuum and in aqueous medium. We found a strong affinity between Kolla and TNB models, and Al3+, Ca2+, Mg2+, Zn2+, K+ and NH4+ cations, influenced by the solvent that affected the interaction sites; the solvent increased the rate of reactivity and affinity for the cations in nucleophilic regions and decreased it in electrophilic regions of the structures. Calculations of molecular electronic potential, MEP and atomic charges, the local smoothness, Fukui functions and the HSAB principle adequately described the HA/cations interactions which were affected by the number of hydrogen bonds. The most reactive sites were the hydroxyl, phenolic, carbonyls oxygens and nitrogens at both vacuum and aqueous medium, especially carbonyl oxygens. These results are consistent with the properties of HA that make them attractive as components of agricultural soils.