The extraction of rare earths using mixtures of acidic phosphorus-based reagents or their thio-analogues

The solvent extraction of rare earths from chloride solution has been investigated using mixtures of 2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester (HEHEHP, P507) and organophosphorus acids [di-(2-ethylhexyl)phosphoric acid (HDEHP, P204), isopropylphosphonic acid 1-hexyl-4-ethylocryl ester (HHEOIPP), bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272), bis(2,4,4-trimethylpentyl)monothiophosphinic acid (Cyanex 302), and bis(2,4,4-trimethypentyl)dithiophosphinic acid (Cyanex 301)]. Results show that the extractability of the selected extractants for rare earths decreases in the order: HEHEHP/HDEHP > HEHEHP/Cyanex 301 > HEHEHP/HHEOIPP > HEHEHP/Cyanex 302 > HEHEHP/Cyanex 272. A possible explanation of the different extractabilities is given based on the structure of the extractants. Furthermore, the possibilities of the separation of adjacent rare earths with these mixtures were investigated according to the extractabilities; the results show the possibility of separating the rare earths.

Conformational transition of DNA induced by cationic lipid vesicle in acidic solution: spectroscopy investigation

The conformational transition of DNA induced by the interaction between DNA and a cationic lipid vesicle, didodecyidimethylammonium bromide (DDAB), had been investigated by circular dichroism (CD) and UV spectroscopy methods. We used singular value decomposition least squares method (SVDLS) to analyze the experimental CD spectra. Although pH value influenced the conformation of DNA in solution, the results showed that upon binding to double helical DNA, positively charged liposomes induced a conformational transition of DNA molecules from the native B-form to more compact conformations. At the same time, no obvious conformational changes occurred at single-strand DNA (ssDNA). While the cationic lipid vesicles and double-strand DNA (dsDNA) were mixed at a high molar ratio of DDAB vesicles to dsDNA, the conformation of dsDNA transformed from the B-form to the C-form resulting in an increase in duplex stability (DeltaT(m) = 8 +/- 0.4 degreesC). An increasing in T-m was also observed while the cationic lipid vesicles interacted with ssDNA.

Catalytic oxidation of cyclohexene to cyclohexanone by a triple system in acidic aqueous acetonitrile medium

The catalytic oxidation of cyclohexene to cyclohexanone using Pd(OAc)(2)/HQ/FePc was investigated in an acidic aqueous solution of acetonitrile. The role of each component of this system in the oxidation of cyclohexene was explored by means of UV-VIS, IR, XPS spectroscopy and. cyclic voltammetry, respectively. Based on the experimental results, the mechanism of the oxidation of cyclohexene catalyzed by Pd(OAc)(2)/HQ/FePc was elucidated.

Electrochemical reactions of cyanocobalamin in acidic media

Electrochemical reactions of cyanocobalamin, CN-Cbl[Co(III)], were studied at glassy carbon electrodes in acidic media by means of cyclic voltammetry and differential pulse polarography. It was found that in pH 0 solution, CN-Cbl[Co(III)] exists mainly in the base-off form, {CN-Cbl[Co(III)]}(base-off). It can undergo a one-electron reduction and a follow-up chemical reaction to form {H2O-Cbl[Co(II)]}(base-off). The rate-constant k of the follow-up decyanation reaction is 0.022 s(-1). {H2O-Cbl[Co(II)]}(base-off) is further reduced to obtain H2O-Cbl[Co(I)]. (C) 1997 Elsevier Science S.A.

Adsorption of dodecatungstosilicic acid on to activated carbons from aqueous and acidic media

Heteropoly acids (HPAs), such as dodecatungstosilicic acid (SiW12), adsorb strongly on to activated carbons. The surface chemical properties of the activated carbons have a pronounced effect on the adsorption of HPAs. To obtain activated carbons with the desired surface chemical properties, modification with mineral acids has been applied. The adsorption isotherms of SiW12 from aqueous solution and various acidic media on to the various carbons have been studied. On the basis of the results obtained, an adsorption model for HPAs from acidic media is presented.

Adsorption of PMo12 and SiMo12 on activated carbon in aqueous and acidic media

In various acidic media, such as H2SO4, HCl, H3PO4, acetic acid of 3 M in hydrogen ion concentration, and pure acetic acid, the adsorption of heteropolyacids composed of molybdenum with the Keggin structures PMo12 and SiMo12 on different activated carbons is studied. In acidic media, the adsorbed amount of heteropolyacids is much higher than that in water. By considering the relation between adsorbed amount and the acid strength of the media, as far as SiMo12 and PMo12 are concerned, there exist different trends.

An acidic polysaccharide with xylose branches from Porphyra yezoensis

An acidic polysaccharide (PY3) was isolated from the hot water extract of the red algae Porphyra yezoensis by successive column chromatographies over DEAE-cellulose and Sephadex G-200. PY3 with an average molecular weight of 1.8x10(5) was demonstrated to be composed of galactose (Gal), 3,6-anhydrogalactose (3,6-AnGal), 6-OSO3-galactose (6-OSO3-Gal) and xylose (Xyl) in an approximate molar ratio of 25 : 15, 10, 1. In view of Smith degradation and methylation and on the basis of spectral evidence including those of IR, GC, GC-MS, and H-1 and C-13 NMR, the most probable repeating unit of PY3 could be proposed as [(1-->3)beta -D-Gal(1 --> 4)alpha -L-3,6-AnGal](3)-[(1 --> 3)beta -D-Gal(1 --> 4)alpha -L-6-OSO3-Gal](2) with a xylose moiety at the C-6 of one of every twenty-five beta -D-Gal residues. To our knowledge, PY3 was shown to be the first porphyran possessing occasional xylose branches.

Tide-influenced acidic hydrothermal system offshore NE Taiwan

Elemental sulfur and hydrogen sulfide emitted offshore of northeastern Taiwan known to local fishermen for generations, but never studied until recently, are found to have originated from a cluster of shallow (< 30 m depth) hydrothermal vents. Among the mounds is a massive 6 m high chimney with a diameter of 4 m at the base composed of almost pure sulfur and discharging hydrothermal fluid containing sulfur particles. The sulfur in the chimney has a delta(34)S= 1.1 parts per thousand that is isotopically lighter than seawater. A yellow smoker at shallow depths with such characteristics has never been reported on anywhere else in the world. Gas discharges from these vents are dominated by CO2 (> 92%) with small amounts of H2S. Helium isotopic ratios 7.5 times that of air indicate that these gases originate from the mantle. High temperature hydrothermal fluids have measured temperatures of 78-116 degrees C and pH (25 degrees C) values as low as 1.52, likely the lowest to be found in world records. Low temperature vents (30-65 degrees C) have higher pH values. Continuous temperature records from one vent show a close correlation with diumal tides, suggesting rapid circulation of the hydrothermal fluids. (c) 2005 Elsevier B.V. All rights reserved.

Adsorption and Corrosion Inhibition Behavior of Mild Steel by One Derivative of Benzoic-Triazole in Acidic Solution

A newly synthesized benzoic-triazole derivative 3,5-dimethylbenzoic acid [1,2,4]triazol-l-ylmethyl ester (DBT) was investigated as a corrosion inhibitor of mild steel in 1 M HCl solution using weight loss measurements, potentiodynamic polarization, SEM, and EIS methods. The results revealed that DBT was an excellent inhibitor, and the inhibition efficiencies obtained from weight loss and electrochemical experiments were in good agreement. Using the potentiodynamic polarization technique, the inhibitor was proved to have a mixed-type character for mild steel by suppressing both anodic and cathodic reactions on the metal surface. The number of water molecules (X) replaced by a molecule of organic adsorbate was determined from the Flory-Huggins, Dhar-Flory-Huggins, and Bockris-Swinkels substitutional adsorption isotherms applied to the data obtained from the gravimetric experiments performed on a mild steel specimen in 1 M HCl solution at 298 K.

Investigation on the corrosion inhibitive effect of 2H-pyrazole-triazole derivatives in acidic solution

Four research methods, such as weight loss test, electrochemical techniques, adsorption isotherm, and quantum chemical calculation, were employed in this paper to study the inhibition efficiency (IE) and inhibition mechanism of three 2H-pyrazole-triazole derivatives, BHOT, FHOT, and CHOT in 1 M HCl solution for mild steel. Using the electrochemical technique, three inhibitors were proved to show a mixed-type character for mild steel by suppressing both anodic and cathodic reactions on the steel surface. The adsorption models of three compounds were established at different temperatures according to their adsorption isotherms. The results of the quantum chemical calculation method indicated that the adsorption sites of 2H-pyrazole-triazole derivatives were strongly centralized on benzene ring, triazole ring, or other substituents. All the results showed that the three derivatives were excellent inhibitors in I M HCl solution for mild steel.

Corrosion inhibition of mild steel in acidic solution by some oxo-triazole derivatives

The oxo-triazole derivative (DTP) was synthesized and its inhibiting action on the corrosion of mild steel in sulphuric acid was investigated by means of weight loss, potentiodynamic polarization, EIS and SEM. The results revealed that DTP was an excellent inhibitor and the inhibition efficiencies obtained from weight loss experiment and electrochemical experiment were in good agreement. Potentiodynamic polarization studies clearly revealed that DTP acted essentially as the mixed-type inhibitor. Thermodynamic and kinetic parameters were obtained from weight loss of the different experimental temperatures, which suggested that at different temperatures (298-333 K) the adsorption of DTP on metal surface obeyed Langmuir adsorption isotherm model. (C) 2009 Elsevier Ltd. All rights reserved.

The synergy between deformation and anodic dissolution of an austenitic stainless steel in acidic chloride solution

In corrosion medium, metals can deform under tensile stress and form a new active surface with the anodic dissolution of the metals being accelerated. At the same time, the anodic dissolution may accelerate the deformation of the metals. The synergy can lead to crack nucleation and development and shorten the service life of the component. Austenitic stainless steel in acidic chloride solution was in active dissolution condition when stress corrosion cracking (SCC) occurred. It is reasonable to assume that the anodic dissolution play an important role, so it's necessary to study the synergy between anodic dissolution and deformation of austenitic stainless steels. The synergy between deformation and anodic dissolution of AISI 321 austenitic stainless steel in an acidic chloride solution was studied in this paper. The corrosion rate of the steel increased remarkably due to the deformation-accelerated anodic and cathodic processes. The creep rate was increased while the yield strength was reduced by anodic dissolution. The analysis by thermal activation theory of deformation showed a linear relationship between the logarithm of creep rate and the logarithm of anodic cur-rent. Besides, the reciprocal of yield strength was also linearly dependent on the logarithm of anodic current. The theoretical deductions were in good agreement with experimental results.

Stress corrosion cracking of AISI 321 stainless steel in acidic chloride solution

The stress corrosion cracking (SCC) of LambdaISI 321 stainless steel in acidic chloride solution was studied by slow strain rate (SSR) technique and fracture mechanics method. The fractured surface was characterized by cleavage fracture. In order to clarify the SCC mechanism, the effects of inhibitor KI on SCC behaviour were also included in this paper. A study showed that the inhibition effects of KI on SCC were mainly attributed to the anodic reaction of the corrosion process. The results of strain distribution in front of the crack tip of the fatigue pre-cracked plate specimens in air, in the blank solution (acidic chloride solution without inhibitor KI) and in the solution added with KI measured by speckle interferometry (SPI) support the unified mechanism of SCC and corrosion fatigue cracking (CFC).

Aminic nitrogen-bearing polydentate Schiff base compounds as corrosion inhibitors for iron in acidic media: A quantum chemical calculation

Quantum chemical calculations based on DFT method were performed on three polydentate Schiff base compounds (PSCs) used as corrosion inhibitors for iron in acid media to determine the relationship between the molecular structure of PSC and inhibition efficiency. The structural parameters, such as the frontier molecular orbital energy HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital), the charge distribution of the studied inhibitors, the absolute electronegativity (chi) values, and the fraction of electrons (Delta N) transfer from inhibitors to iron, were also calculated and correlated with inhibition efficiencies. The results showed that the inhibition efficiency of PSCs increased with the increase in E-HOMO and decrease in E-LUMO-E-HOMO; and the areas containing N atoms are most possible sites for bonding the metal iron surface by donating electrons to the metal. (C) 2007 Elsevier Ltd. All rights reserved.