Chemical effects induced by γ-irradiated Na2SO4 in aqueous ammonium nitrate

It is well known that paramagnetic centers are formed when Na₂SO₄ crystals are exposed to -radiation. The dissolution of such crystals in aqueous ammonium nitrate results in reduction of nitrate to nitrite. Various factors which influence the yield of nitrite are investigated. The yield of nitrite is found to vary with the amount of irradiated Na₂SO₄ added, the dose absorbed by Na₂SO₄ crystals, the storing period of the irradiated salt, photoannealing time, concentration of aqueous ammonium nitrate and particle size of the Na₂SO₄ crystals. The G(NO ₂ ^– ) value under optimum conditions of the conversion of nitrate to nitrite by irradiated Na₂SO₄ in aqueous ammonium nitrate is 0.009. The efficiency of energy transfer is 1.5%. The mechanism of reduction is based on the reactions of paramagnetic centers with nitrate ions.     

Low-pressure collisional narrowing in CO2

We report the observation of collisional narrowing of the Q branch of the Raman spectrum for the (000) → (100) transition in CO₂ at very low pressures. The minimum linewidth is reached at ≈250 Torr. An estimate for the difference in rotational constants of the (100) state and the ground state is obtained. The narrowing of the linewidth and the changes in line-shape are interpreted in terms of velocity changing collisions and rotationally inelastic collisions between the CO₂ molecules.     

Mathematical Correction for Polyatomic Isobaric Spectral Interferences in Determination of Lanthanides by Inductively Coupled Plasma Mass Spectrometry

The determination of lanthanides by Inductively Coupled Plasma Mass Spectrometry (ICP‐MS) is complicated by several spectral overlaps from M⁺, MO⁺ or MOH⁺ ions formed in the ICP. Especially, it is essential to avoid the spectral interferences from lighter lanthanide and Ba polyatomic ions on middle or heavier lanthanides. To tackle this problem, we have developed a mathematical correction method, which reduces all the spectral overlaps from oxide species of Pr, Nd, Ce and Sm over Gd, Tb, Dy and Ho, and Gd, Tb over Yb and Lu. It can also successfully correct the oxide and hydroxide interference of Ba over Eu. The effectiveness of the proposed the mathematical correction scheme is demonstrated for the USGS Standard Rock samples AGV‐1 and G‐2. The results show that the experimental data obtained by applying the mathematical correction scheme for lanthanides is in good agreement with the reported values, using pneumatic and ultrasonic nebulisation methods, for their ICP‐MS analysis.     

Lyoluminescence of luminol in aqueous amines

Lyoluminescence of luminol induced by -irradiated NaCl has been studied in aqueous amines. The emission spectra of lyoluminescence are recorded on 400 ASA Kodak film using a Fuess spectrograph. A broad continuous emission band appears in the visible region from 390 to 500 nm. The emission band showed two peaks centered at 430 and 470 nm. The 430 nm peak is more intense in secondary amines while the 470 nm band is more intense in primary amines. The mechanism of light emission is based on the comparative study of lyoluminescence, fluorescence and chemiluminescence of luminol in aqueous amines.     

Determination of calcium and iron in silicon and uranium silicide using ion chromatography

Two separate ion chromatography methods were developed for the determination of calcium and iron in silicon and uranium silicide. A cation exchange separation with conductivity detection was developed for Ca. A reversed phase column modified with 50 mM camphor-10-sulphonic acid was used for separating Fe. Iron was detected photometrically. Linear calibrations for Ca (0.1–10 ppm) and Fe (0.5–25 ppm) were performed. Limits of detections for Ca and Fe are 0.03 and 0.2 ppm, respectively. The precision of the methods are better than 2 % for Ca at 0.2 ppm and Fe at 2 ppm.     

One‐Step Multicomponent Self‐Assembly of a First‐Generation Sierpiński Triangle: From Fractal Design to Chemical Reality

A novel terpyridine‐based architecture that mimics a first‐generation Sierpiński triangle has been synthesized by multicomponent assembly and features tpy? Cd^II? tpy connectivity (tpy=terpyridine). The key terpyridine ligands were synthesized by the Suzuki cross‐coupling reaction. Mixing two different terpyridine‐based ligands and Cd^II in a precise stoichiometric ratio (1:1:3) produced the desired fractal architecture in near‐quantitative yield. Characterization was accomplished by NMR spectroscopy, mass spectrometry, and transmission electron microscopy.     

Efficient Synthesis of 1,4-Bis(5-aryl-1,3,4-oxadiazol-2-yl)-2,3,5,6-tetrafluorobenzenes

Russian Journal of Organic Chemistry - An efficient acid-catalyzed condensation between substituted benzohydrazides and 2,3,5,6-tetrafluoroterephthalic acid to form...     

Characterization of porosity in vapor-deposited amorphous solid water from methane adsorption

We have characterized the porosity of vapor-deposited amorphous solid water (ice) films deposited at 30-40 K using several complementary techniques such as quartz crystal microgravimetry, UV-visible interferometry, and infrared reflectance spectrometry in tandem with methane adsorption. The results, inferred from the gas adsorption isotherms, reveal the existence of microporosity in all vapor-deposited films condensed from both diffuse and collimated water vapor sources. Films deposited from a diffuse source show a step in the isotherms and much less adsorption at low pressures than films deposited from a collimated source with the difference increasing with film thickness. Ice films deposited from a collimated vapor source at 77 degrees incidence are mesoporous, in addition to having micropores. Remarkably, mesoporosity is retained upon warming to temperatures as high as 140 K where the ice crystallized. The binding energy distribution for methane adsorption in the micropores of ice films deposited from a collimated source peaks at approximately 0.083 eV for deposition at normal incidence and at approximately 0.077 eV for deposition at >45 degrees incidence. For microporous ice, the intensity of the infrared bands due to methane molecules on dangling OH bonds on pore surfaces increases linearly with methane uptake, up to saturation adsorption. This shows that the multilayer condensation of methane does not occur inside the micropores. Rather, filling of the core volume results from coating the pore walls with the first layer of methane, indicating pore widths below a few molecular diameters. For ice deposited at 77 degrees incidence, the increase in intensity of the dangling bond absorptions modified by methane adsorption departs from linearity at large uptakes.     

Comparative evaluation of three alpha-hydroxycarboxylic acids for the separation of lanthanides by dynamically modified reversed-phase high-performance liquid chromatography

The resolution for the three homologues of alpha-hydroxycarboxylic acids viz. lactic acid, alpha-hydroxyisobutyric acid (alpha-HIBA) and alpha-hydroxy-alpha-methylbutyric acid (alpha-H-alpha-MBA), was compared for the individual separation of 14 lanthanide elements under identical experimental conditions. Alpha-HIBA was found to be the best for separation of heavier lanthanides (Tb to Lu) while alpha-H-alpha-MBA led to a better separation for lighter lanthanides (La to Eu). All the 14 lanthanides were separated by gradient HPLC employing both alpha-HIBA and alpha-H-alpha-MBA so that there was reasonable resolution among all the peaks and the separation was completed in a short time.     

Power-law spatial correlations in arrays of locally coupled lasers

We investigate correlations of the intensity fluctuations of two-dimensional arrays of nonidentical, locally coupled lasers, numerically and experimentally. We find evidence of a power-law dependence of spatial correlations as a function of laser pair distance (or coupling strength) near the phase-locking threshold.