Determination of rhodium by thermal neutron activation analysis using g-ray spectrometry

Trace amounts of rhodium have been determined by thermal neutron activation analysis using both destructive and non-destructive methods. With a neutron flux of 10¹² n cm^-2 sec^-1 the lower limits of detection are about 0.1 μg and 0.01 μg, respectively. A rapid sodium-peroxide fusion followed by a pyridine extraction was used in the destructive method to separate the 4.4-mm ^104mRh from its matrix. The 44-sec¹⁰⁴Rh was used in the non-destructive method. Both radioactive isomers were measured by γ-ray spectrometry with a multichannel pulse height analyzer. The average time required per non-destructive analysis was 7 min while the chemical method averaged 20 min.     

Asymmetric synthesis via acetal templates. 12. Highly diastereoselective coupling reactions with a ketene acetal. An efficient,asymmetric synthesis of R-(+)-α-lipoic acid

TiCl₄ catalyzes the essentially quantitative coupling of chiral acetals $\text{1}$ with 1-$\text{t}$-butoxy-1-$\text{t}$-butyldimethylsilyloxyethene $\text{2}$ to generate β-alkoxycarboxylates in which the new asymmetric center is formed with excellent diastereoselection. β-hydroxycarboxylic acids of high ee result from removal of the chiral auxiliary. The procedure has been applied to the synthesis of R-(+)-α-lipoic acid $\text{10.}$     

The group extraction of noble metals with s-(1-decyl)-N,N'-diphenylisothiouronium bromide and their determination in the organic extract by atomic-absorption spectrometry

The distribution coefficients are given for the noble metals and associated base metals between S-(1-decyI)-N, N'-diphenylisothiouronium (DDTU) in diisobutyl ketone and aqueous solutions containing varying molarities of hydrochloric acid. DDTU is a satisfactory reagent for the extraction of noble metals as a group from most of the associated base metals. Base metals such as iron(III), tin(II), and selenium(IV), which are co-extracted, can be removed from the organic phase by washing with 0.1 M hydrochloric acid; this affects only the recovery of iridium. Although the noble metals cannot be recovered from the organic phase by back-extraction, direct measurement in the organic phase is possible in ths presence of zinc dibenzyldithiocarbamate added as a releasing agent. The final solution for analysis contains 6 mg of additive per 10 ml of solution.     

Spectrophotometric determination of osmium with 1-naphthylamine-4,6,8-trisulfonic acid

This investigation was undertaken to determine if the naphthylamine sulfonic acid-osmate (OsVI) reaction is suitable for a spectrophotometric determination of osmium. The 1-naphthylamine- 4, 6,8-trisulfonic acid osmate complex is water-soluble and forms a stable violet-colored system at PH 1 to 1.5 that is independent of reagent concentration. At 555 mμ the colored complex obeys Beer's law over a concentration range of 0.1 to 6.5 p.p.m. osmium and remains stable with respect to time and temperature. The effects of pH, temperature, reagent concentration, and diverse ions were studied. The nature of the organo-osmate complex in solution was studied by three techniques and the effect of temperature and pH on the rate of complex formation was determined. A procedure for the removal of osmium from all interfering ions was developed based on well known distillation techniques.A convenient, sensitive, reproducible and accurate method for the spectrophotometric determination of osmium has been developed.     

Thermodynamic properties of 1,2-dihydronaphthalene: Glassy crystals and missing entropy

Measurements leading to the calculation of the standard thermodynamic properties for gaseous 1,2-dihydronaphthalene (Chemical Abstracts registry number [447-53-0]) are reported. Experimental methods include oxygen combustion-bomb calorimetry, adiabatic heat-capacity calorimetry, vibrating-tube densitometry, comparative ebulliometry, and inclined-piston gauge manometry. 1,2-Dihydronaphthalene decomposed significantly when heated to temperatures above T = 480 K. Consequently, the critical temperature, critical pressure, and critical density were estimated. Standard molar entropies, standard molar enthalpies, and standard molar Gibbs free energies of formation were derived at selected temperatures between T = 250 K and 500 K. The standard state is defined as the ideal gas at the pressure p = p^° = 101.325 kPa. Standard entropies are compared with those calculated statistically on the basis of assigned vibrational spectra from the literature for the vapor phase. A large and near constant difference between the entropies calculated statistically and those determined calorimetrically was observed over the entire temperature range studied. Two glass-like features are observed in the heat capacity against temperature curve for the solid state, indicating that the crystals are disordered. A quantitative accounting for the entropy discrepancy is proposed based on possible molecular orientations of 1,2-dihydronaphthalene. Results are compared with experimental values reported in the literature.     

Finite element modeling of acousto-mechanical coupling in the cat middle ear

The function of the middle ear is to transfer acoustic energy from the ear canal to the cochlea. An essential component of this system is the tympanic membrane. In this paper, a new finite element model of the middle ear of the domestic cat is presented, generated in part from cadaver anatomy via microcomputed tomographic imaging. This model includes a layered composite model of the eardrum, fully coupled with the acoustics in the ear canal and middle-ear cavities. Obtaining the frequency response from 100 Hz to 20 kHz is a computationally challenging task, which has been accomplished by using a new adaptive implementation of the reduced-order matrix Padé-via-Lanczos algorithm. The results are compared to established physiological data. The fully coupled model is applied to study the role of the collagen fiber sublayers of the eardrum and to investigate the relationship between the structure of the middle-ear cavities and its function. Three applications of this model are presented, demonstrating the shift in the middle-ear resonance due to the presence of the septum that divides the middle-ear cavity space, the significance of the radial fiber layer on high frequency transmission, and the importance of the transverse shear modulus in the eardrum microstructure.     

A Theoretical Study of the Inner-Sphere Disproportionation Reaction Mechanism of the Pentavalent Actinyl Ions

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.     

Forensic comparative glass analysis by laser-induced breakdown spectroscopy

Glass samples of four types commonly encountered in forensic examinations have been analyzed by laser-induced breakdown spectroscopy (LIBS) for the purpose of discriminating between samples originating from different sources. Some of the glass sets were also examined by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Refractive index (RI) measurements were also made on all glass samples and the refractive index data was combined with the LIBS and with the LA-ICP-MS data to enhance discrimination. The glass types examined included float glass taken from front and side automobile windows (examined on the non-float side), automobile headlamp glass, automobile side-mirror glass and brown beverage container glass. The largest overall discrimination was obtained by employing RI data in combination with LA-ICP-MS (98.8% discrimination of 666 pairwise comparisons at 95% confidence), while LIBS in combination with RI provided a somewhat lower discrimination (87.2% discrimination of 1122 pairwise comparisons at 95% confidence). Samples of side-mirror glass were less discriminated by LIBS due to a larger variance in emission intensities, while discrimination of side-mirror glass by LA-ICP-MS remained high.     

Polypyrrole stretchable actuators

Here, we report a simple way to prepare stretchable polypyrrole (PPy)‐based actuator materials that can be operated over a wide dynamic strain range and generate useable actuation displacements and pressures. The stretchable actuators were prepared as a laminated composite of PPy and a gold‐coated roughened rubber sheet. By manipulating the corrugated surface of the rubber substrate, the stretchability of PPy was greatly improved. Gold‐coated rubbers could be stretched to 30% without significant change in electrical resistance. The corrugated PPy/gold/rubber laminates successfully showed ～1% of actuation strain even when prestretched to 24%. The actuation strains were smaller than for similar free‐standing PPy films and a detailed analysis of the effects of corrugation and of the rubber substrate are presented to predict actuation strain under various prestretch strains. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013