STATISTICAL THERMODYNAMICS OF POLYDISPERSE POLYMER BLENDS WITH STRONG INTERACTION

A statistical thermodynamics theory of polydisperse polymer mixtures with strong interaction between dissimilar components based on a lattice fluid model is formulated. Expressions for the free energy, equation of state, phase stability and spinodal for a polydisperse, binary polymer mixture with strong interaction are derived.

STATISTICAL THERMODYNAMICS OF POLYDISPERSE POLYMERS

A statistical thermodynamics theory of polydisperse polymers based on a lattice model of fluids is formulated. Pure polydisperse polymer can be completely characterized by three scale factors and the molecular weight distribution of the system. The equation of state does not satisfy a simple corresponding-states principle, except for a polymer fluid of sufficiently high molecular weight. The relationships between thermal expansion coefficient alpha and isothermal compressibility beta with reduced variables are also predicted.

High level expression, purification, and characterization of the shrimp antimicrobial peptide, Ch-penaeidin, in Pichia pastoris

Penaeidins, members of a new family of antimicrobial peptides constitutively produced and stored in the haemocytes of penaeid shrimp, display antimicrobial activity against bacteria, and fungi. Here, a DNA sequence encoding the mature Ch-penaeidin peptide was cloned into the pPIC9K vector and transformed into Pichia pastoris. The transformed cells were screened for multi-copy plasmids using increasing concentrations of G418. Positive colonies carrying chromosomal integrations of the Chp gene were identified by phenotype and PCR. When transformed cells were induced with methanol, SDS-PAGE and Western blotting revealed the production of a similar to6100 Da recombinant CHP (rCHP) expression product. Large scale expression revealed that rCHP was produced at 108 mg/L under optimal conditions in the highest Chp-producing P. pastoris clone. The antimicrobial activities of rCHP were studied by liquid phase analysis, which revealed that rCHP exhibited activities against some Gram-negative and Gram-positive bacteria, but had a relatively low activity against some fungi. Purification of rCHP by cation exchange chromatography and subsequent automated amino acid sequencing revealed the presence of four additional amino acids (YVEF) at the N-terminus that belonged to the cleaved fusion signal peptide; these residues may account for the observed decrease in antifungal activity. Together, these observations indicate that rCHP is an effective antimicrobial peptide that can be successfully produced at high levels in the yeast, and therefore may be a potential antimicrobial candidate for practical use. (C) 2004 Elsevier Inc. All rights reserved.

The electrochemical reduction reaction of dissolved oxygen on Q235 carbon steel in alkaline solution containing chloride ions

Cyclic voltammetry, electrochemical impedance spectroscopy, and rotating disk electrode voltammetry have been used to study the effect of chloride ions on the dissolved oxygen reduction reaction (ORR) on Q235 carbon steel electrode in a 0.02 M calcium hydroxide (Ca(OH)(2)) solutions imitating the liquid phase in concrete pores. The results indicate that the cathodic process on Q235 carbon steel electrode in oxygen-saturated 0.02 M Ca(OH)(2) with different concentrations of chloride ions contain three reactions except hydrogen evolution: dissolved oxygen reduction, the reduction of Fe(III) to Fe(II), and then the reduction of Fe(II) to Fe. The peak potential of ORR shifts to the positive direction as the chloride ion concentration increases. The oxygen molecule adsorption can be inhibited by the chloride ion adsorption, and the rate of ORR decreases as the concentration of chloride ions increases. The mechanism of ORR is changed from 2e(-) and 4e(-) reactions, occurring simultaneously, to quietly 4e(-) reaction with the increasing chloride ion concentration.

水-盐-气天然流体的物理化学性质模拟与流体包裹体应用研究

Natural fluids with water-salt-gas are often found in every sphere of the Earth, whose physicochemical properties and geochemical behaviors are complicated. To study these properties and behaviors turns out to be one of the challenging issues in geosciences. Traditional approaches mainly depend on experiments and observations. However, it is impossible to obtain a large number of data covering a large T-P space of the Earth by experimental methods in the near future, which will hinder the advance of the theoretical study. Therefore, it is important to model natural fluids by advanced theoretical methods, by which limited experimental data can be extended to a large temperature-pressure-composition space. Physicochemical models developed in this dissertation are not only more accurate, but also extend the applied T-P-m region of the experimental data of the multi-fluid systems by about two times. These models provide the new and accurate theoretical tools for the geochemical research, especially for the water-rock interactions and the study of the fluid inclusions. The main achievements can be summarized as follows: (1) A solubility model on components of natural gases is presented. The solubility model on the systems of CH4-H2O-NaCl, C2H6-H2O-NaCl or N2-H2O-NaCl takes advantage of modern physicochemical theory and methods, and is an improvement over previous models whose prediction and precision are relatively poor. The model can predict not only the gas solubility in liquid phase but also water content in the gas phase. In addition, it can predict gases (methane or nitrogen) solubility in seawater and brine. Isochores can be determined, which are very important in the interpretation of fluid inclusions. (2) A density model on common aqueous salt solutions is developed. The density models with high precision for common aqueous salt solutions (H2O-NaCl, H2O-LiCl, H2O-KCl, H2O-MgCl2, H2O-CaCl2, H2O-SrCl2 or H2O-BaCl2) are absent in the past. Previous density models are limited to the relatively small range of experimental data, and cannot meet the requirement of the study of natural fluids. So a general density model of the above systems is presented by us based on the international standard density model of the water. The model exceeds the other models in both precision and prediction. (3) A viscosity model on common aqueous alkali-chloride solutions is proposed. Dynamic viscosity of water-salt systems, an important physics variable, is widely used in three-dimension simulation of the fluids. But in most cases, due to the lack of viscosity models with a wide T-P range, the viscosity of aqueous salt solutions is replaced by that of the water, giving rise to a relatively large uncertainty. A viscosity model with good prediction for the systems (H2O-NaCl, H2O-LiCl or H2O-KCl) is presented on the base of the international standard viscosity model of water and the density model developed before. (4) Equation of State applied in fluid inclusions. The best Equations of State in the world developed by others or us recently are applied in the study of the fluid inclusions. Phase equilibria and isochores of unitary system (e.g. H2O, CO2, CH4, O2, N2, C2H6 or H2S), binary H2O-NaCl system and ternary H2O-CH4-NaCl system are finished. From these programs and thermodynamic equations of coexisting ores, the physicochemical conditions before or after the deposits form can be determined. To some extent, it is a better tool.

内蒙古龙头山Ag-Pb-Zn多金属矿床成矿模式及找矿模型

The recent years research indicated that middle-south section of Da Hinggan Mountains metallogenic belt has two periods(Hercynian and Yanshanian) characteristics of metallogenesis, as well as the most of ore deposits in the area closely relate to Permian strata. Longtoushan ore deposit discovered in 2004 is an Ag-Pb-Zn polymetallic ore deposit born in Permian and located in the east hillside of the metallogenic belt, which has considerable resources potentials. It has important research value for its good metallogenic location and blank research history. Base on the detail field geology studies, the geology characteristics of "two stages and three kinds of metallogensis" has established. According to further work through geochemistry research including trace element, REE, S, Pb and Sr isotope, as well as petrography, microtemperature measurement, Laser Raman analysis and thermodynamics calculation of fluid inclusion, origin and characteristic of the ore-forming material and fluid has been discussed. And a new technology of single pellet Rb-Sr isochrones has been tried for dating its born time. Bae on above work, study of ore deposit comparison has been carried out, and metallogesis controlling factor and geological prospecting symbol have been summarized. Finally, metallogenic model and prospecting model have been established. According to above, the next step work direction has been proposed. Main achievement of the paper are listed as follow: 1.Longtoushan ore deposit has experienced two metallogenic periods including hot-water sedimentation period and hydrothermal reformation period. There are three kinds of metallizing phase: bedded(or near-bedded) phase, vein-shaped phase and pipe-shaped phase. The mian metallogenic period is hot-water sedimentation period. 2.Ore deposit geochemistry research indicated that the metal sulfides have charcateristic of hot-water sedimentation metallogensis, but generally suffered later hydrothermal transformation. The barite mineral isotope content is homogenous, showing the seabed hot-water sedimentation origin characteristic. Wall rock, such as tuff is one of metallogenic material origins. Both of Pb model age and Rb-Sr isochrone research older age value than that of strata, possibly for been influenced by hydrothermal transformation, and interfusion of ancient basis material. 3.There are two kinds of main metallogenic fluid inclusion in barite of the Longtoushan ore deposit, which are rich gas phase( C type) and liquid phase (D type). Their size is 2～7um, and principal components is H2O. Both kinds of fluid inclusion have freezing point temperature -7.1～-2.4℃ and -5.5～-0.3℃, salinity 4.0～10.6wt% and 0.5～8.5wt%, homogeneous temperature 176.8～361.6℃ and 101.4～279.9℃, which peak value around 270℃ and 170℃, respectively. Density of the ore-forming fluid is 0.73～0.97g/cm3, and metallogenic pressure is 62.3×105～377.9×105Pa. Above characteristic of the fluid inclusion are well geared to that of ore deposit originated in seabed hot-water sedimentation. 4.Through the comparison research, that Longtoushan ore deposit has main characteristic of hot-water sedimentation ore deposit has been indicated. Ore-forming control factor and prospecting symbol of it has been summarized, as well as metallogenic model and prospecting model. Next step work direction about prospecting has also been proposed finally.

凝析油气藏描述及开发对策研究-以莫北2油气藏为例

Gas condensate reservoir research involves not only structure sediment reservoir liquid properties characterization but also the change of the temperature field, the change of the pressure field, the change of liquid phase and the reservoir sensitivity. To develop the gas condensate reservoir effectively .we must depict the static properties of the oil and gas system ,build exact and comprehensive parameter field, predict the rule of dynamic change and do the necessary reservoir characterization development plan dynamic prediction direct production. The MoBei Oil and Gas Field is the first gas condensate reservoirs which is found by the Xinjiang Oil Field Company in ZhunGaEr basin belly.it has deserved some knowledge after prospect evaluation, the MoBei Oil and Gas Field start development ,it is one of the important development blocks of Xinjiang Oil Field Company productivity constuction. During its development , it gradually appears some problems, such as complex oil and gas phase, great change of reservoir stretch .uncertain reservoir type and scale, controling its development strategy and plan difficultly. To deserve the high efficient development and long-term stable production of the gas condensate reservoir, it is necessary to characterize it systematically and form a suit of scientific development strategy. This thesis take the MoBei zone SanGongHe sand group reservoir as research object, applied advanced log techniques ,such as the nulear magnetism log ,MDT testing .etc. After comprehensive research of loging geology information, set up a suit of methods to identify oil gas water layer .these methods can identify the gas-oil level and the oil-water level. On the basis of reasonable development object system, according fine structure interpretation and structure modeling. build any oil water column height of the reservoir accurately. Through carefully analysis of the basic theory and method of reservoir seism prediction. optimize a reservoir inversion method .technique. software fitting the research region aiming strata, set up the GR field, porosity field, Rt field, impedence field .permeability field and initial oil saturation field, generating the base of quantity reservoir characterization. Discussing the characteristic of reservoir fluid and the movement and reallocating of muti-phase fluid in reservoir. And according the material of 100 soviet gas condensate reservoir ,build the recognition method and mode of gas condensate reservoir. Building the 3D geology model ,carry on the static and production evaluation, propose the development strategy and improve plan , provide the base of increasing reserves and advancing production and enriching the prospect development theory of the gas condensate reservoi

Calorimetric study of Wood alloy

The heat capacities of Wood alloy have been measured with an automatic adiabatic calorimeter over the temperature range of 80 similar to 360 K. The thermodynamic data of solid-liquid phase transition have been obtained from the heat capacity measurements. The melting temperature, enthalpy and entropy of fusion of the substance are 345.662 K, 18.47 J.g(-1) and 0.05343 J.g(-1).K-1, respectively. The necessary thermal data are provided for the low temperature thermodynamic study of the alloy.

FT-IR spectroscopic study of the oxidation of chlorobenzene over Mn-based catalyst

Adsorption and oxidation of chlorobenzene on Al(2)O(3), TiO(2)-Al(2)O(3), and MnO(x)/TiO(2)-Al(2)O(3) have been studied by in situ Fourier transform infrared (FT-IR) spectroscopy. At room temperature, chlorobenzene is only physisorbed on Al(2)O(3), TiO(2)-Al(2)O(3), and MnO(x)/TiO(2)-Al(2)O(3), and gives the same IR spectrum as that for liquid-phase chlorobenzene. On Al(2)O(3) no further interaction and reaction take place with treatment, at higher temperatures (up to 773 K), while phenolates are observed for TiO(2)-Al(2)O(3) and MnO(x)/TiO(2)-Al(2)O(3) at 773 K. When the adsorbed chlorobenzene coexists with oxygen, formates are detected for Al(2)O(3), while acetates are additionally observed for TiO(2-)Al(2)O(3) above 573 K. For MnO(x)/TiO(2-)Al(2)O(3), maleates are present at 573 And 673 K, while formates and acetates develop at 473 and 573 K. Almost all IR bands due to formates, acetates, and maleates disappear at 773 K, indicating that these oxygen-containing species are potential intermediates for the total oxidation of chlorobenzene.

Heat capacity and thermochemical study of trifluoroacetamide (C2H2F3NO)

The low-temperature heat capacities of trifluoroacetamide were precisely determined with a small sample precision automated adiabatic calorimeter over the temperature range from 78 to 404 K. A solid-to-solid phase transition, a fusion and a phase transition from a liquid crystalline phase to fully liquid phase have been observed at the temperatures of 336.911+/-0.102, 347.622+/-0.094 and 388.896+/-0.160 K, respectively. The molar enthalpies of these phase transitions as well as the chemical purity of the substance were determined to be 5.576+/-0.004, 11.496+/-0.007, 1.340+/-0.005 kJ mol(-1) and 99.30 mol%, respectively, on the basis of the heat capacity measurements. The molar entropies of the three phase transitions were calculated to be 16.550+/-0.012, 33.071+/-0.029 and 3.447+/-0.027 J mol(-1) K-1, respectively. Further researches of the thermochemical properties for this compound have been carried out by means of TG and DSC techniques. (C) 2000 Elsevier Science B.V. All rights reserved.

A combined DFT and SCRF study of solvent effects on 4-methyl-3-penten-2-one

The IR spectrum of 4-methyl-3-penten-2-one is interpreted with the aid of normal coordinate calculations within the Onsager self-consistent reaction field (SCRF) model, using a density functional theory (DFT) method at the Becke3LYP/6-31G* level. The solvent effects on the geometry, energy, dipole moment, and vibrational frequencies of 4-methyl-3-penten-2-one in the solution and in the liquid phase are calculated using the Onsager SCRF model. The calculated vibrational frequencies in the liquid-phase are in good agreement with the experimental values. The solvent reaction field has generally weak influence. For the two main bands of C=C and C=O mixed vibrational modes, small frequency shifts (5-6 cm(-1)), but relatively large changes in IR intensities (up to 101 km mol(-1) in the liquid phase) are found. (C) 1999 Elsevier Science BV. All rights reserved.

UV Raman spectroscopic study on the synthesis mechanism of zeolite X

The synthesis of zeolite X is characterized by UV Raman spectroscopy, NMR spectroscopy, and X-ray diffraction. UV Raman spectra of the liquid phase of the synthesis system indicate that AI(OH); species are incorporated into silicate species, and the polymeric silicate species are depolymerized into monomeric silicate species during the early stage of zeolite formation. An. intermediate species possessing Raman bands at 307, 503, 858 and 1020 cm(-1) is detected during the crystallization ill the solid phase transformation. The intermediate species is attributed to the beta cage, the secondary building unit of zeolite X. A model for the formation of zeolite X is proposed, which involves four-membered rings connecting to each other via six-membered ring to form beta cages, then the beta cages interconnect via double six-membered rings to form the framework of zeolite X. (C) 2001 Elsevier Science B.V. All rights reserved.

Measurements of the heat capacity of an azeotropic mixture of water and n-butanol from 78 to 320 K

Molar heat capacities of n-butanol and the azeotropic mixture in the binary system [water (x=0.716) plus n-butanol (x=0.284)] were measured with an adiabatic calorimeter in a temperature range from 78 to 320 K. The functions of the heat capacity with respect to thermodynamic temperature were established for the azeotropic mixture. A glass transition was observed at (111.9 +/- 1.1) K. The phase transitions took place at (179.26 +/- 0.77) and (269.69 +/- 0.14) K corresponding to the solid-liquid phase transitions of. n-butanol and water, respectively. The phase-transition enthalpy and entropy of water were calculated. A thermodynamic function of excess molar heat capacity with respect to temperature was established, which took account of physical mixing, destructions of self-association and cross-association for n-butanol and water, respectively. The thermodynamic functions and the excess thermodynamic ones of the binary systems relative to 298.15 K were derived based on the relationships of the thermodynamic functions and the function of the measured heat capacity and the calculated excess heat capacity with respect to temperature.

Thermodynamic properties of ethanol and gasoline blended fuel

The heat capacities (C-p) of five types of gasohol (50 wt % ethanol and 50 wt % unleaded gasoline 93(#) (E50), 60 wt % ethanol and 40 wt % unleaded gasoline 93(#) (E60), 70 wt % ethanol and 30 wt % unleaded gasoline 93(#) (E70), 80 wt % ethanol and 20 wt % unleaded gasoline 93(#) (E80), and 90 wt % ethanol and 10 wt % unleaded gasoline 93(#) (E90), where the "93" denotes the octane number) were measured by adiabatic calorimetry in the temperature range of 78-320 K. A glass transition was observed at 95.61, 96.14, 96.56, 96.84, and 97.08 K for samples from the E50, E60, E70, E80, and E90 systems, respectively. A liquid-solid phase transition and a solid-liquid phase transition were observed in the respective temperature ranges of 118-153 and 155-163 K for E50, 117-150 and 151-164 K for E60, 115-154 and 154-166 K for E70, 113-152 and 152-167 K for E80, and 112-151 and 1581-167 K for E90. The polynomial equations of Cp and the excess heat capacities (C-p(E)), with respect to the thermodynamic temperature, were established through least-squares fitting. Based on the thermodynamic relationship and the equations obtained, the thermodynamic functions and the excess thermodynamic functions of the five gasohol samples were derived.

Pressure-induced amorphization and an amorphous-amorphous transition in densified porous silicon

Deb, S. K., Wilding, M. C., Somayazulu, M., McMillan, P. F. (2001). Pressure-induced amorphization and an amorphous-amorphous transition in densified porous silicon. Nature, 414, 528-530. RAE2008