Kinetic study of the decompositions involved in the thermal degradation of commercial azodicarbonamide

The transitions and reactions involved in the thermal treatment of several commercial azodicarbonamides (ADC) in an inert atmosphere have been studied by dynamic thermogravimetry analysis (TGA), mass spectrometry and Fourier transform infrared (FTIR) spectroscopy. A pseudo‐mechanistic model, involving several competitive and non‐competitive reactions, has been suggested and applied to the correlation of the weight loss data. The model applied is capable of accurately representing the different processes involved, and can be of great interest in the understanding and quantification of such phenomena, including the simulation of the instantaneous amount of gases evolved in a foaming process. In addition, a brief discussion on the methodology related to the mathematical modeling of TGA data is presented, taking into account the complex thermal behaviour of the ADC. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis,extraction, and adsorption properties of calix[4]arene‐poly(ethylene‐glycol) crosslinked polymer

Novel calix[4]arene‐poly(ethylene glycol) crosslinked polymer (CCP) has been synthesized by the polycondensation reaction between a p‐tert‐butylcalix[4]arene derivative and dihydroxyl capped poly(ethylene glycol) (DHPEG, M_n = 1000) catalyzed by neodymium tosylate. The hydrogel, consisted of 66.9% water and 33.1% CCP, can selectively extract aromatic organic molecules from aqueous solution according to the diameter of the guest molecules, which infers that the diameter of the calix[4]arene cavity is about 5.4 Å and the conformation of calix[4]arene units altered from cone conformation to 1,3‐alternate conformation during the polycondensation reaction. Furthermore, CCP can also adsorb naphthalene from gas phase, showing much higher capacity than active carbon does, which may have some potential applications in the field of separation and environment protection. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Surface adsorption of comb polymers by Monte Carlo simulations

This paper reports off-lattice Monte Carlo simulations of highly-branched comb homopolymers weakly adsorbed on a flat, featureless surface showing only covolume and dispersion interactions with the adsorbate. A minimal coarse-grained model, described by hard spheres connected by harmonic springs, was employed. The interaction energy of the adsorbed combs and linear chains is first discussed as a function of the molecular mass and of the number of beads in contact with the surface. The molecular size is then investigated as a function of backbone length and branching density at a fixed arm size. The apparent swelling exponents of the adsorbed combs are larger than those of the corresponding linear chains, and much larger than that of the free molecules. This result indicates a surface-induced stiffening of the comb backbone, further studied through the persistence length l_pers. It is found that l_pers increases upon adsorption over the free-molecule value, more so the larger is the branching density. Finally, the thickness of the adsorbed layer, the surface-induced molecular anisotropy and the molecular aspect ratio are investigated as a function of branching density and molecular mass.     

生烃化学动力学在川东北普光气田的应用

普光气田是四川盆地近期发现的规模最大、埋藏最深、资源丰度最高的气田。通过认识普光气田各个烃源岩层的贡献量、生烃关键期与构造演化的关系、油气成藏具体模式等，建立生烃化学动力学模型、标定参数，结合地区烃源岩参数和地史、热史资料，定量描述该地区的生烃过程及油裂解成气过程。认为：普光地区的主力烃源岩为下志留统泥岩；主要干酪根生油期为早二叠世末到早三叠世末期（距今286Ma至240Ma）；主要干酪根生气期为中三叠世（距今240Ma至230Ma）；主要气源是原油后期热裂解气，原油裂解成气的时间比较晚，主要油裂解成气期为早白垩世（距今144Ma至97．5Ma），从而决定了普光气田的成藏模式为“多期成藏，油气转化，晚期定位”。图2表3参33     

Accelerator Analysis of Tributyltin Adsorbed onto the Surface of a Tributyltin Resistant Marine Pseudoalteromonas sp. Cell

Tributyltin (TBT) released into seawater from ship hulls is a stable marine pollutant and obviously remains in marine environments. We isolated a TBT resistant marine Pseudoalteromonas sp. TBT1 from sediment of a ship’s ballast water. The isolate (10^{9.3 ± 0.2} colony-forming units mL⁻¹) adsorbed TBT in proportion to the concentrations of TBTCl externally added up to 3 mM, where the number of TBT adsorbed by a single cell was estimated to be 10^8.2. The value was reduced to about one-fifth when the lysozyme-treated cells were used. The surface of ethanol treated cells became rough, but the capacity of TBT adsorption was the same as that for native cells. These results indicate that the function of the cell surface, rather than that structure, plays an important role to the adsorption of TBT. The adsorption state of TBT seems to be multi-layer when the number of more than 10^6.8 TBT molecules is adsorbed by a single cell.     

Characterization of Thai limestone for desulphurization in a fluidized bed combustor

The objective of this study is to determine the chemical kinetics of desulphurization of Thai limestone in an atmospheric fluidized bed combustor (AFBC). The experiments, which employed the batch technique using the limestone samples from six major sources in Thailand, were performed in a laboratory‐scale AFBC. The results obtained were analysed and correlated in the form of apparent reaction rate and deactivation rate constants as a function of operating conditions of the furnace and their properties, respectively. The formulae derived from these correlations were kept as general as possible in order that they could be used as input parameters for the selected mathematical model of desulphurization in an AFBC that is suitable for practical use. The predicted results were in good agreement with the experimental data reported in the literature. Copyright © 2003 John Wiley & Sons, Ltd.     

Interaction of H2,n-butane and cis-2-butene with Pt and Pt In in NaY: a microcalorimetric study

Pt NaY and Pt In NaY adsorption properties have been compared by using probes like H₂, C₄H₁₀, 2-C₄H₈ and microcalorimetry. It appears that the addition of In to Pt does not change the initial heat of H₂ chemisorption but decreases the initial heat of butane and butene chemisorption.     

Quantum chemical SINDO1 study of vanadium pentoxide

An improved set of parameters for vanadium in the semiempirical quantum chemical SCF MO method SINDO1 is presented. It is shown that both the geometries and heats of formation of a number of vanadium-containing compounds calculated by this method are in good agreement with available experimental data. Model clusters of increasing size are used for the study of geometric and energetic properties of vanadium pentoxide. Both hydrogen atom and proton adsorption on the (010) surface of vanadium pentoxide and a subsequent formation of different oxygen vacancies have been investigated. Based on these computational results the reactivities of V₂O₅-surface oxygen atoms for adsorption are discussed.     

几种吸附式致冷新工质对的性能预测

应用吸附平衡基本理论对几种可能的吸附式致冷新工质对的性能进行了预测。结果表明，烷烃系列的低混点工质与沸石的配对体系是不可取的，而沸石－氨、活性炭－丙酮、活性炭－氨及活性炭－乙醇则是沸石－水、活性炭－甲醇体系的适宜的替代物。     

Methanol adsorption and dehydration on alkali metal exchanged NaY zeolites

FT-IR spectroscopy has been applied in a study of methanol adsorption on M^INaY zeolites (M=Li, K, Rb, Cs). Coordinatively and/or hydrogen bonded methanol was registered in the temperature range 300–473 K. Dehydration of methanol to dimethyl ether occurred at 573 and 623 K. It was found that the activity of the catalyst for methanol dehydration strongly depends on the kind of alkali metal cation, and well correlates the IR data relative to methanol adsorption.