Fast determination of the tin content in cassiterite ores by photon activation method

Photon activation analysis has been success-fully applied to the fast and non-destructive analysis of tin in cassiterite ores based on the 159.7 keV gamma line of^123mSn produced in the¹²⁴Sn/γ, n/^123mSn reaction. In order to improve the accuracy of analytical results, corrections for self-absorption and pile-up effects were performed. Under typical conditions /15 μA electron beam current, 15 MeV bremsstrahlung energy, 5 min irradiation time and 10 min measurement/ the sensitivity of the analysis is 10 ppm. The proposed method can be used for routine analysis of tin in geological samples.     

Syntheses and structures of mono-, di- and tetranuclear rhodium or iridium complexes of thiacalix[4]arene derivatives

The reactions of [Cp*MCl2]2(Cp*=eta5-C5Me5, M = Rh, Ir) with thiacalix[4]arene (TC4A(OH)4) and tetramercaptothiacalix[4]arene (TC4A(SH)4) gave the mononuclear complexes [(Cp*M){eta3-TC4A(OH)2(O)2}] and the dinuclear complexes [(Cp*M)2{eta3eta3-TC4A(S)4}] respectively, while the analogous reactions with dimercaptothiacalix[4]arene (TC4A(OH)2(SH)2) produced the tetranuclear complexes [(Cp*M)2(Cp*MCl2)2-{eta3eta3eta1eta1-TC4A(O)2(S)2}].     

A new-type photoreaction of a carbonyl compound: Part 2. Photoinduced ω-bond dissociation in p-halomethylbenzophenone studied by time-resolved EPR technique and laser flash photolysis

Photodissociation of the carbon-X (X = Br and Cl) bonds in p-bromo- and p-chloromethylbenzophenone (BMBP and CMBP) in solution were investigated by time-resolved EPR and laser flash photolysis techniques. BMBP and CMBP were found to undergo ω-bond cleavage to yield the p-benzoylbenzyl radical (BBR) at 295 K, and the quantum yields (Φ_BBR) were determined. The CIDEP signal originated from BBR formed upon decomposition of CMBP was obtained while that for BMBP was absent. By using triplet sensitization of acetone, the efficiencies (_BBR) of the CX bond fission in the triplet states of BMBP and CMBP were determined. The agreement between the Φ_BBR and _BBR values for CMBP indicates that the CCl bond dissociation occurs only in the triplet state. In contrast to CMBP, the cleavage of the CBr bond in BMBP upon direct excitation was concluded to be the event only in the excited singlet state without triplet formation, whereas the triplet state was also reactive for ω-bond dissociation. The rate of CBr bond dissociation seemed to be greater than that of intersystem crossing from the S₁ to the T₁ state. Schematic energy diagrams of the excited states of BMBP and CMBP were shown, and the reaction profiles were discussed from the viewpoint of the CX bond enthalpies.     

Analysis of organotin compounds by grignard derivatization and gas chromatography-ion trap tandem mass spectrometry

The determination of organotin compounds in water using gas chromatography-tandem mass spectrometry (GC-MS-MS) is described. Several organotin derivatives were synthesized by the reaction of organotin chlorides with Grignard reagents such as methyl-, propyl- and pentylmagnesium halides. After the optimization of the GC-MS-MS conditions, several derivatizations with the Grignard reagents were compared by evaluating the molar responses and volatilities of the derivatives and derivatization yields. As a result, the derivatizing reagent of choice is pentylmagnesium bromide. Calibration curves for the mono-, di- and tributyltins and mono-, di- and triphenyltins with pentylmagnesium bromide were linear in the range of 0.5-100 pg of Sn. The instrumental detection limits of six organotins ranged from 0.20 to 0.35 pg of Sn. The recovery tests from water samples (500 ml) were performed by using sodium diethyldithiocarbamate (DDTC) as a complexing reagent. Except for monophenyltin, the absolute recoveries of organotins from pure water at 200 ng of Sn/l were satisfactory. The recoveries calibrated by surrogate compounds (perdeuterated organotin chlorides) ranged from 71 to 109%. The method detection limits ranged from 0.26 to 0.84 pg of Sn (500-ml sample). This method was applied to the recovery of organotins from river water and seawater. The calibrated recoveries were between 90 and 122%.     

High pressure studies on new chiral compounds exhibiting TGBA phase

Effects of high pressures on phase sequences of the two homologousn=16 andn=18 of the (3-fluoro-4 ((R) or (S)-methylheptyloxy) 4, (4-fluoro benzoyloxy) tolans) series have been studied. Both compounds exhibit the new twisted Smectic A phase called Twist Grain Boundary TGB_A phase. The high pressure experiments were performed by thermobarometric analysis. The order of the transitions (first or second) have been determined in respect to pressure and temperature. The pressure-temperature phase diagrams show that the TGB_A phase is stabilized by increasing pressure; an inducedN ^* phase appears under high pressure for n=18 leading to the observation of TGB_A-N ^*-I triple point.     

Rare earth impurities in high purity lanthanum oxide determined by neutron activation analysis

Individual rare earth impurities in high purity La₂O₃ (99.9%) have been determined by NAA after pre-separation of the matrix (La). The separation is carried out on an anion exchanger (Dowex 1×8) using different mixtures of methanol/nitric acid as eluants. The rare earth elements from Dy to Lu are eluted quantitatively using a 10% 1M HNO₃-90% methanol mixture, while the light rare earths from Ce to Gd are eluted quantitatively using a 10% 0.05M HNO₃-90% methanol mixture. La, which is retained on the column, is eluted using 0.1M HNO₃. The recoveries of the various rare earth elements have been checked using radiotracers and also by spiking the sample with known amount of elements, and the recoveries are found to be quantitative. Results obtained on a typical high purity lanthanum oxide are reported here.     

Photocrosslinking of functionalized rubber. II. Photoinitiated cationic polymerization of epoxidized liquid natural rubber

Low molecular weight epoxidized natural rubber has been crosslinked within seconds by UV irradiation in the presence of a triarylsulfonium salt. The photoinitiated cationic ring-opening polymerization was studied quantitatively by infrared spectroscopy and shown to proceed with surprisingly long kinetic chains in such solid medium. The high conversion (60%) needed for complete insolubilization, together with the presence of tetrahydrofuran structures, argue in favor of an intramolecular polymerization process involving neighboring epoxy groups. The photoinitiator concentration has a strong influence on the rate and extent of the reaction, as well as on the depth of cure profile. Because of an efficient dark process, close to 100% conversion was reached upon storage of the irradiated elastomer at ambient, with a concomitant increase of the gel fraction and the polymer hardness. The grafting of pendent acrylate groups onto the polymer chain leads to a three-fold decrease of the initial rate of polymerization of the epoxide. The photocuring of natural rubber bearing both epoxy and acrylate groups generates a dual polymer network which combines the properties of the two moieties. © 1995 John Wiley & Sons, Inc.     

Accuracy of free energies of hydration for organic molecules from 6-31g*-derived partial charges

Absolute free energies of hydration have been computed for 13 diverse organic molecules using partial charges derived from ab initio 6-31G* wave functions. Both Mulliken charges and charges fit to the electrostatic potential surface (EPS) were considered in conjunction with OPLS Lennard–Jones parameters for the organic molecules and the TIP4P model of water. Monte Carlo simulations with statistical perturbation theory yielded relative free energies of hydration. These were converted to absolute quantities through perturbations to reference molecules for which absolute free energies of hydration had been obtained previously in TIP4P water. The average errors in the computed absolute free energies of hydration are 1.1 kcal/mol for the 6-31G* EPS charges and 4.0 kcal/mol for the Mulliken charges. For the EPS charges, the largest individual errors are under 2 kcal/mol except for acetamide, in which case the error is 3.7 kcal/mol. The hydrogen bonding between the organic solutes and water has also been characterized. © John Wiley & Sons, Inc.     

Boride-based nano-laminates with MAX-phase-like behaviour

MAX-phases being usually composed of transition metals, group A elements and carbon/nitrogen are considered interesting materials for many applications because of their tremendous bulk modulus, “reversible” plasticity, and machinability. This is mainly due to their unique kind of bonding comprising covalent, ionic as well as metallic bonds providing “easy” planes of rupture and deformability due to the layered crystal structures.In transition metal boride systems, similar types of bonding are available. In particular the W₂B₅-structure type and its stacking variations allow the synthesis of strongly layered crystal structures exhibiting unique delamination phenomena.The paper presents ab initio calculations showing the similarities of bonding between the ternary carbides and the corresponding ternary or quaternary borides. Formation of boride-based nano-laminates from auxiliary liquid phases, from the melt as well as during sintering and precipitation from supersaturated solid solutions will be discussed by means of SEM and TEM studies. The role of impurities weakening the interlayer bonding will be addressed in particular. The pronounced cleavage parallel to the basal plane gives rise for crack deflection and pull-out mechanisms if the laminates are dispersed in brittle matrices such as boron carbide, silicon carbide or other transition metal borides.