Kinetics of Y(III) stripping for the system Y/HCl/Cyanex 272-P507/heptane with constant interfacial area cell with laminar flow

Kinetics and mechanism of stripping of yttrium(III) previously extracted by mixtures of bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272, HA), and 2-ethylhexyl phosphonic acid mono-2-ethylhexl ester (P507, HB) dissolved in heptane have been investigated by constant interfacial-area cell by laminar flow. The corresponding equilibrium stripping equation and equilibrium constant were obtained. The studies of effects of the stirring rate and temperature on the stripping rate show that the stripping regime is dependent on the stripping conditions. The plot of interfacial area on the rate has shown a linear relationship. This fact together with the strong surface activity of mixtures of Cyanex 272 and P507 at heptane-water interfaces makes the interface the most probable locale for the chemical reactions. The stripping rate constant is obtained, and the value is compared with that of the system with Cyanex 272 and P507 alone. It is concluded that the stripping ability with the mixtures is easier than that of P507 due to lower the activation energy of the mixtures. The stripping rate equation has also been obtained, and the rate-determining steps are the two-step interfacial chemical reactions as predicted from interfacial reaction models.

Mass-transfer kinetics of ytterbium extraction with sec-nonylphenoxy acetic acid

The extraction kinetics of ytterbium with sec-nonylphenoxy acetic acid (CA-100) in heptane have been investigated using a constant interfacial area cell with laminar flow. The influence of stirring speed and temperature on the rate indicated that the extraction rate was controlled by the experiment conditions. The plot of interfacial area on the rate showed a linear relationship. This fact together with the low solubility in water and strong surface activity of CA-100 at heptane-water interfaces made the interface the most probable locale for the chemical reactions. The influences of extractant concentration and hydrogen ion concentration on the extraction rate were investigated, and the forward and reverse rate equations for the ytterbium extraction with CA-100 were also obtained. Based on the experimental data, the apparent forward extraction rate constant was calculated. Interfacial reaction models were proposed that agree well with the rate equations obtained from experimental data.

Preparation and characterization of PSt-b-PHEMA metal hybrids

The block copolymer polystyrene-b-poly[2-(trimethylsilyloxy)ethylene methacrylate] (PSt-b-PTMSEMA) was synthesized using atom-transfer radical polymerization (ATRP). The hydrolysis of PSt-b-PTMSEMA led to the formation of an amphiphilic block copolymer, polystyrene-b-poly(2-hydroxylethyl methacrylate) (PSt-b-PHEMA), which was characterized by GPC and H-1-NMR. TEM showed that the PSt-b-PHEMA formed a micelle, which is PSt as the core and PHEMA as the shell. Under appropriate conditions, the nickel or cobalt ion cause chemical reactions in these micelles and could be reduced easily. ESCA analysis showed that before reduction the metal existed as a hydroxide; after reduction, the metal existed as an oxide, and the metal content of these materials on the surface is more than that on the surface of the copolymer metal ion. XRD analysis showed that the metal existed as a hydroxide before reduction and existed as a metal after reduction.

Recent progress in the studies of endohedral metallofullerenes

This overview presents the recent progress in the area of endohedral metallofullerenes in the past several years. The important results have been summarized as follows: (1) Many metals including Group 3 metals, most of the lanthanide series elements, and Group 2 metals have been encapsulated into a fullerene cage to form mono-, di-, and trimetallofullerenes by using the arc-evaporation technique. (2) Some endohedral metallofullerenes such as Group 3 metals, most of the lanthanide series elements, Group 2 metals, and some of their isomers have been successfully isolated and purified by a two-step or several-step HPLC technique. By using high-temperature and high-pressure extraction with pyridine, Ln@C-80, Ln@C-82, and Ln2@C-80 for most rare-earth metals have been selectively extracted in high yield (about 1% of the saw soot) from fullerenes and other size metallofullerenes. (3) The endohedral nature of metallofullerenes such as Y@C-82, Sc2@C-84, and Sc@C-82 has been finally confirmed by synchrotron X-ray powder diffraction. The symmetries and the structures of metallofullerenes such as Ca@C-82(III), La-2@C-80(I-h), Sc-2@C-84(D-2d), and Sc-2@C-84(C-s) have been confirmed by NMR measurements. (Lb) The information on the electronic structures and properties of endohedral metallofullerenes has been obtained by various spectrometric means Such as EPR, W-vis-MR, XPS, CV. It is generally accepted that three-electron transfer is favorable when M = Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Lu but Sc, Eu, Sm, Yb, Tm, Ca, Sr, Ba prefer to donate two electrons to the fullerene cages. (5) Several chemical reactions of endohedral metallofullerenes have been reported in which reagents are disilacyclopropane, digermacyclopropane, diphenyldiazomethane, and trifluoroacetic acid. (6) Mass spectrometry provided the crucial evidence that led to the discovery of metallofullerenes in 1985 and has always played a key role in their identification and characterization, Ion-mobility measurements of gas-phase ions have obtained the information of structures and the formation mechanism of endohedral metallofullerenes. till Theoretical calculations on the endohedral metallofullerenes have made an important contribution to the studies on the symmetry of the cage, the position of metal atom(s) inside the cage, the number of electronic transfer between metal atom(s) and fullerene cage, etc. (C) 2000 Elsevier Science S.A. All rights reserved.

Morphology, thermal behavior, and mechanical properties of PA6/UHMWPE blends with HDPE-g-MAH as a compatibilizing agent

A functionalized high-density polyethylene (HDPE) with maleic anhydride (MAH) was prepared using a reactive extruding method. This copolymer was used as a compatibilizer of blends of polyamide 6 (PA6) and ultrahigh molecular weight polyethylene (UHMWPE). Morphologies were examined by a scanning electron microscope. It was found that the dimension of UHMWPE and HDPE domains in the PA6 matrix decreased dramatically, compared with that of the uncompatibilized blending system. The size of the UHMWPE domains was reduced from 35 mu m (PA6/UHMWPE, 80/20) to less than 4 mu m (PA6/UHMWPE/HDPE-g-MAH, 80/20/20). The tensile strength and Izod impact strength of PA6/UHMWPE/HDPE-g-MAH (80/20/20) were 1.5 and 1.6 times as high as those of PA6/UHMWPE: (80/20), respectively. This behavior could be attributed to chemical reactions between the anhydride groups of HDPE-g-MAH and the terminal amino groups of PA6 in PA6/UHMWPE/HDPE-g-MAH blends. Thermal analysis was performed to confirm that the above chemical reactions took place during the blending process. (C) 2000 John Wiley & Sons, Inc.

Influence of interface on radiation effects of crystalline polymer - radiation effects on polyamide-1010 containing BMI

Aimed at saving the radiation dose required to crosslinking the polyamid-1010, BMI/PA1010 systems containing different amounts of difunctional crosslinking agent N,N'-bis-maleimide-4,4'-biphenyl methane (BMI) were prepared and the structure changes at the crystallographic and supermolecular levels before and after irradiation were studied by using WAXD, SAXS, and DSC techniques. It was found that by incorporation of BMI the microcrystal size L-100 is lowered due to the formation of hydrogen bond between the carbonyl oxygen of BMI and the amide hydrogen of PA1010 in the hydrogen bonded plane, and the overall crystallinity W-c is also decreased. The presence of BMI causes the crystal lamella thickness d(c) to decrease and greatly thickens the transition zone d(tr) between the crystalline and amorphous regions. As for the irradiated specimen, the maximum increments in the L-100 and W-c against dose curves decrease with BMI content, and the interception point D-i, at which the L-100 and W-c curves intercept their respective horizontal line of L-100/L-100(0) and W-c/W-c(0)=1, shift to lower dose with an increase in BMI concentration. In addition. the mechanism of the radiation chemical reactions in the three different phases under the action of BMI are discussed with special focus on the interface region. (C) 1999 Published by Elsevier Science Ltd. All rights reserved.

Morphology, thermal behavior, and mechanical properties of PA1010/PP and PA1010/PP-g-GMA blends

The modification of polypropylene (PP) was accomplished by melt grafting glycidyl methacrylate (GMA) on its molecular chains. The resulting PP-g-GMA was used to prepare binary blends of polyamide 1010 (PA1010) and PP-g-GMA. Different blend morphologies were observed by scanning electron microscopy (SEM) according to the nature and content of PA1010 used. Comparing the PA1010/PP-g-GMA and PA1010/PP binary blends, the size of the domains of PP-g-GMA were much smaller than that of PP at the same compositions. It was found that mechanical properties of PA1010/PP-g-GMA blends were obviously better than that of PA1010/PP blends, and the mechanical properties were significantly influenced by wetting conditions for uncompatibilized and compatibilized blends. A different dependence of the flexural modulus on water was found for PA1010/PP and PA1010/PP-g-GMA. These behaviors could be attributed to the chemical interactions between the two components and good dispersion in PA1010/PP-g-GMA blends. Thermal and rheological analyses were performed to confirm the possible chemical reactions taking place during the blending process. (C) 1997 John Wiley & Sons, Inc.

Properties of ethylene-propylene copolymer/PA-1010 blends using ethylene-propylene copolymer-graft-acrylic acid as a compatibilizing agent

The modification of ethylene-propylene copolymer (EP) has been accomplished by radical EP-graft-acrylic acid (EP-g-AA) has been used to obtain ternary PA/EP/EP-g-AA blends by melt mixing. Different blend morphologies were observed by scanning electron microscopy; the domain size of the EP-dispersed phase in the polyamide 1010 matrix of compatibilized blends decreased compared with that of uncompatibilized blends. It is found that EP-g-AA used as the third component has a profound effect on the mechanical properties of the resulting blends. This behavior has been attributed to serious chemical interactions taking place between the two components. Thermal analysis shows that some thermal properties of PA in compatibilized PA/EP/EP-g-AA changed because of chemical reactions taken place during the blending process. Wide angle x-ray diffraction measurements also confirmed this result. (C) 1996 John Wiley & Sons, Inc.

HE PHASE TRANSFER OF CO(II) CATALYZED BY 2,2 '-BIPYRIDINE AT THE WATER/NITROBENZENE INTERFACE

The chemical reactions coupled with the phase transfer of Co(Ⅱ) catalyzed by 2,2′ -bipyridine across the water/nitrobenzene interface have been observed by using cyclic voltammetry (CV). Coupled chemical reactions both in the organic phase or in the aqueus phase influence the CV behavior of successive complex phase transfer obviously and an irreversible phenomenon similar to that existed at the metal electrode/electrolyte solution interface was observed. For different complexes, the phase transfer mechanism...

东营凹陷幔源流体对原油生物标志化合物的影响研究

A large number of mantle-derived fluid activities occurred in the Dongying Sag. On the basis of the studies on the geochemical characteristics of these fluids in this sag, the spatial distribution of biomarkers in petroleum and their relationships with the parameters of mantle-derived fluids were studied, to reveal the influence of mantle-derived fluids on the biomarkers and to evaluate the reliability of these biomarkers when applied to oil-source correlation and maturity analysis. Most biomarkers used in oil correlation kept the characteristics of their sources during burial thermal evolution. Even some of them were not influenced by mantle derived fluids, such as the relative content of C27-C29 steroid（ααα20R）and C21/C23 tricyclic terpane. However, Pr/Ph and C35/C34 hopanes were sensitive to both heat energy and materiel input by the mantle-derived fluids. γ-waxnae/C30hopanes and C24 tetracyclic terpanes /C26 tricyclic terpanes responded only to thermal influence by mantle-derived fluids. They did not chemically reacted with the mantle-derived fluids. Fluorene series compounds reacted with hydrogen and / or carbon dioxide from the mantle. Mantle-derived fluids affected most maturity index. The huge thermal energy with mantle-devied fluids weakened the relationship between the maturity parameters and depth. Among them, pregnane/C27-29 steroid and Ts/(Ts+Tm) were more sensitive to the heat of the fluids. ααα20S/(20S+20R) took the second place. αββ/(ααα+αββ) and 22S/(22S+22R) were not thermally influenced by the mantle-derived fluid. Besides, the substance of mantle-derived fluids reacted with fragrants, hopanes or moretanoids and thus altered the values of MPI1, MPI2, MPR, C30 hopanes/(C30 hopanes + moretanoids) and alkyl-diben zothiophene/diben zothiophene. The thermal alernation of phenanthrene series and their spatial distribution show that the heat energy carried by mantle-derived fluids was not fierce but spread widely in Dongying Sag, which is favorable to hydrocarbon generation with little destroy. In sum, mantle-derived fluids affected biomarkers through thermal energy and chemical reactions and changed the values of oil-source correlation and maturity parameters in the deep-seated fault belts. Therefore, in the deep-seated fault belts, oil-source correlation should be restudied and the new parameters need to be explored.

Synthesis Gas Generation by Chemical-Looping Reforming Using Ce-Based Oxygen Carriers Modified with Fe, Cu, and Mn Oxides

Chemical-looping reforming (CLR) is a technology that can be used for partial oxidation and steam reforming of hydrocarbon fuels. It involves the use of a metal oxide as an oxygen carrier, which transfers oxygen from combustion air to the fuel. Composite oxygen carriers of cerium oxide added with Fe, Cu, and Mn oxides were prepared by co-precipitation and investigated in a thermogravimetric analyzer and a fixed-bed reactor using methane as fuel and air as oxidizing gas. It was revealed that the addition of transition-metal oxides into cerium oxide can improve the reactivity of the Ce-based oxygen carrier. The three kinds of mixed oxides showed high CO and H-2 selectivity at above 800 degrees C. As for the Ce-Fe-O oxygen carrier, methane was converted to synthesis gas at a H-2/CO molar ratio close to 2:1 at a temperature of 800-900 degrees C; however, the methane thermolysis reaction was found on Ce-Cu-O and Ce-Mn-O oxygen carriers at 850-900 degrees C. Among the three kinds of oxygen carriers, Ce-Fe-O presented the best performance for methane CLR. On Ce-Fe-O oxygen carriers, the CO and H-2 selectivity decreased as the Fe content increased in the carrier particles. An optimal range of the Ce/Fe molar ratio is Ce/Fe > 1 for Ce-Fe-O oxygen carriers. Scanning electron microscopy (SEM) analysis revealed that the microstructure of the Ce-Fe-O oxides was not dramatically changed before and after 20 cyclic reactions. A small amount of Fe3C was found in the reacted Ce-Fe-O oxides by X-ray diffraction (XRD) analysis.

On the propagation rate of the chemical waves observed during the course of CO oxidation on a Ag/Pt(110) composite surface

We have analyzed the propagation rate of the chemical waves observed during the course of CO oxidation on a Ag/Pt(I 10) composite surface that were reported in our previous papers [Surf Interface Anal. 2001, 32, 179; J. Phys. Chem. B 2002, 106, 5645]. In all cases, the propagation rate v can be adequately fitted as v = v(0) + D-0/d, in which v(0) and D-0 are constants, and d is the distance between the reaction front of the chemical wave and the boundary from which the chemical wave originates. We propose that the surface species responsible for the formation of the chemical wave comes from two paths: the adsorption of molecules in the gas phase on the surface and the migration from the adjacent surface with different catalytic activity. v(0) corresponds to the contribution from the surface species due to the adsorption, and D-0/d to that of the surface species that migrates from the adjacent surface. The rate equation clearly suggests that the observed chemical wave results from the coupling between adjacent surfaces with different catalytic activities during the course of heterogeneous catalysis. These results, together with our previous reports, provide a good fundamental understanding of spillover, an important phenomenon in heterogeneous catalysis.

Novel chemical synthesis of Pt-Ru-P electrocatalysts by hypophosphite deposition for enhanced methanol oxidation and CO tolerance in direct methanol fuel cell

A novel method was developed to prepare the highly active Pt-Ru-P/C catalyst. The deposition of phosphorus significantly increased electrochemical active surface (EAS) area of catalyst by reduces Pt-Ru particle size. TEM images show that Pt-Ru-P nanoparticles have an uniform size distribution with an average diameter of 2 nm. Cyclic voltammetry (CV), Chronoamperometry (CA), and CO stripping indicate that the presence of non-metal phosphorus as an interstitial species Pt-Ru-P/C catalyst shows high activity for the electro-oxidation of methanol, and exhibit enhanced performance in the oxidation of carbon monoxide compared with Pt-Ru/C catalyst. At 30 degrees C and pure oxygen was fed to the cathode, the maximum power density of direct methanol fuel cell (DMFC) with Pt-Ru-P/C and Pt-Ru/C catalysts as anode catalysts was 61.5 mW cm(-2) and 36.6 mW cm(-2), respectively. All experimental results indicate that Pt-Ru-P/C catalyst was the optimum anode catalyst for direct methanol fuel cell.

Cyclic voltammetry for predicting oxidation process in heterogeneous catalysis

Catalytic reactions with different oxidation process were investigated and correlated to the electrochemical properties of the catalysts. The activity of suprafacial reaction is closely related to the area of redox peak, while that of the intrafacial one is to the match of redox potentials. Accordingly, it is supposed that cyclic voltammetry (CV) measurement could be a means for predicting the oxidation process in heterogeneous catalysis.