Infrared studies of matrix isolated sodium and potassium chloride and cyanide dimers

The infrared spectra of matrix isolated sodium and potassium chlorides and cyanides in different inert gas matrices were examined over the range 4000 cm^?1 to 33 cm^?1. A study of the effect of superheating the vapor species on the spectra has been carried out. Temperature cycling experiments have been pursued in an attempt to differentiate between bands due to monomers, dimers, and higher polymers. Isotopic frequency shifts were measured for a carbon-13 enriched sample of sodium cyanide and carbon-13 and nitrogen-15 enriched samples of potassium cyanide in the CN region. Symmetry force constants were calculated assuming a cyclic rhombic structure for the dimers. In the case of the cyanide dimer, the CN group of the molecule was considered as a halide atom. Finally a comparison is given between the symmetry force constants of the dimers of the alkali metal fluorides, cyanides and chlorides.     

Electrical properties of solid iodo mercurates resulting from the reaction of HgI2 with alcaline iodides

Potassium iodide solutions are currently used during the fabrication process of mercuric iodide based nuclear radiation detectors. However, KI treatment leaves the HgI₂ surface covered with a residual compound (namely the potassium tri-iodo mercurate) which has a significant influence on the surface properties and stability of mercuric iodide devices and therefore on the detectors characteristics. Looking for other solutions to etch mercuric iodide, we found it interesting to investigate the electrical properties of the compounds which may form when etching HgI₂ in NH₄I, NaI, and RbI. For this purpose, solid iodo mercurates with the cations ammonium, sodium, and rubidium, have been prepared by reacting HgI₂ with the solutions of interest. Study of the electrical properties of these samples and comparison with those of potassium tri-iodo mercurate ones, especially with respect to humidity, indicates noticeable stability differences in presence of water vapour. This could have interesting consequences on the surface cleaning of mercuric iodide. PACS 81.65.Cf; 81.10.Dn; 72.90.+y     

Sonochemical and sonophotocatalytic degradation of malachite green: the effect of carbon tetrachloride on reaction rates

A comparative study between the sonolytic, photocatalytic and sonophotocatalytic oxidation processes of aqueous solutions of malachite green was carried out in the presence of carbon tetrachloride, under a low power ultrasonic field (<15 W) and using titanium dioxide as a photocatalyst. The effect of a number of parameters such as ultrasonic intensity, TiO2 crystalline structure and the presence of CCl4 were studied using an inexpensive reactor. Enhanced rates of sonolytic degradation of malachite green in the presence of CCl4 were demonstrated. On the other hand, the simultaneous use of sonolysis and photocatalysis in the presence of CCl4 does not improve the degradation rate of malachite green in comparison with the one obtained using only sonolysis, but it makes possible a faster oxidative degradation of some reaction intermediaries. Finally, in air saturated solutions both processes, the sonolytic and the photocatalytic one, follow a first-order rate law.     

Effects of ultrasound on the formation of alpha-benzoylbenzyl cyanide from benzyl cyanide and alkylphenyl ketone from alpha-alkylbenzyl cyanide by potassium superoxide in the presence of crown ether

Ultrasound accelerates the formation of alpha-benzoylbenzyl cyanide and benzoic acid in the reaction of benzyl cyanide with potassium superoxide in the presence of 18-crown-6. Similarly, 4-methylbenzyl cyanide, 4-methoxybenzyl cyanide and 4-chlorobenzyl cyanide gave the corresponding alpha-(4-methylbenzoyl)-4-methylbenzyl cyanide, alpha-(4-methoxybenzoyl)-4-methoxybenzyl cyanide and alpha-(4-chlorobenzoyl)-4-chlorobenzyl cyanide in 25-43% isolated yields under the same reaction conditions. Benzoic, p-toluic, 4-methoxybenzoic and 4-chlorobenzoic acids were also formed in these reactions. No reaction was observed when the mixture was simply stirred. Reflux instead of sonication gave lower yields of the products. However, alpha-alkylbenzyl cyanide produced a high yield of the phenylalkyl ketones when stirred. Interestingly, the corresponding benzoic acid was not formed in these reactions. Possible mechanisms for the formation of alpha-benzoylbenzyl cyanide from benzyl cyanide and phenylalkyl ketones from alpha-alkylbenzyl cyanide are also proposed.     

Infrared spectra of matrix-isolated sodium and potassium cyanides

The infrared spectra of matrix-isolated sodium and potassium cyanides in neon, argon, krypton, and nitrogen matrices were examined over the range 4000 cm^?1 to 33 cm^?1. The effect of temperature cycling, which normally results in migration of trapped molecules to generate polymeric species, has been pursued. A careful study of the effect of superheating the vapor species on the spectra has also been carried out. By these means it has been possible to identify the bands in the spectrum due to monomeric and polymeric species. Isotopic frequency shifts were measured for a ¹³C-enriched sample of sodium cyanide and ¹³C- and ¹⁵N-enriched samples of potassium cyanide. From the measured isotopic shifts it was possible to determine the structure of these two compounds as being linear NaCN and KCN. Accurate force constants were calculated using the measured frequency values for the three fundamental vibrational modes of the different isotopic molecules of NaCN and KCN. Bands due to sodium and potassium cyanates were also identified in some of these systems. ¹³C and ¹⁵N isotopic frequency shifts were also observed for NaOCN and KOCN.     

氯化钠-十六烷基三甲基溴化铵体系分离富集-原子吸收光谱法测定湖泊沉积物中的镉

建立了碘化钾存在下氯化钠-十六烷基三甲基溴化铵体系分离富集-原子吸收光谱法测定湖泊沉积物中镉的新方法,最佳浮选分离条件为0.1mol.L-1HNO3、0.05mol.L-1KI、5.0×10-3mol.L-1CTMAC,NaCl用量为1.0%(W/V)。在最佳浮选分离条件下,镉的浮选率在94.1%—99.2%之间。合成样分离试验表明,体系能定量分离镉,而大量基体元素不被浮选。富集试验结果显示本法具有较好的富集效果,可明显提高测定的灵敏度。应用本法对湖泊沉积进行分离测定,结果满意。     

Ultrasound promoted N-alkylation of pyrrole using potassium superoxide as base in crown ether

Ultrasound accelerates the N-alkylation of pyrrole by alkylating reagents using potassium superoxide as base in the presence of 18-crown-6. A much lower yield of N-alkylated pyrrole was realized in the absence of ultrasound. N-alkylating reagents employed for pyrrole are methyl iodide, ethyl bromide, benzyl bromide, as well as acrylonitrile allyl cyanide and methyl acrylate. In an extension of this work, we have found that ultrasound was not necessary for the N-alkylation of indole and alkyl amine, such as diphenyl amine and piperidine with alkyl halides using our reagents. In all cases we observed that the 18-crown-6 catalyzed N-alkylation reaction gives higher yields of N-alkylated products than that without crown ether, when potassium superoxide was used as base. These observations are probably due to the potassium-crown complex which can be released when the reaction goes to completion.     

Conductance studies of NaCl, KCl, NaBr, NaI, NaBPh4, Bu4NI and NaClO4 in water + 2-methoxyethanol mixtures at 298.15 K

The electrical conductances of the solutions of sodium chloride (NaCl), potassium chloride (KCl), sodium bromide (NaBr), sodium iodide (NaI), sodium tetraphenylborate (NaBPh₄), tetrabutylammonium iodide (Bu₄NI) and sodium perchlorate (NaClO₄) in water (1) + 2-methoxyethanol (2) mixtures containing 0.01, 0.025, 0.05, 0.075, 0.10, 0.15 and 0.20 mol fractions of 2-methoxyethanol have been reported at 298.15 K. The conductance data have been analyzed by the Fuoss–Justice equation. The individual limiting ionic conductivities of Na⁺, K⁺, Bu₄N⁺, BPh₄⁻, I⁻, Cl⁻, and Br⁻ ions have been determined using the Fuoss–Hirsch assumption. The dependencies of the limiting molar conductances, Λ_o, and Walden products, Λ_oη, versus mixed solvent composition have been discussed.     

Enhancement of sonochemical degradation of phenol using hydrogen atom scavengers

Sonochemical degradation of phenol was found to be enhanced in the presence of the volatile hydrogen atom scavengers CCl4 and perfluorohexane. The non-volatile hydrogen atom scavenger iodate did not enhance phenol degradation. The first order rate constant for aqueous phenol degradation in separate experiments using different sonochemical probes increased in the presence of 150 microM CCl4 from 0.014 to 0.031 min(-1) (probe 1) and from 0.022 to 0.061 min(-1) (probe 2). In the presence of <1.5 microM C6H14, the first order rate constant increased from 0.014 to 0.032 min(-1) (probe 1). Hydroquinone was the major observed reaction intermediate both in the presence and absence of hydrogen atom scavengers. Hydroquinone yields were substantially higher in the presence of hydrogen atom scavengers, suggesting that hydroxyl radical pathways for phenol degradation were enhanced by the hydrogen atom scavengers. These additives may be useful in improving pollutant degradation efficiency or improving synthetic processes that rely on hydroxyl radical as a key intermediate.     

Taking into account nonselective absorption of light in atomic absorption analysis

We propose a method for quantitatively taking into account nonselective absorption for systems in which the vapor phase contains a single molecular form: sodium and potassium chlorides and iodides. We identified the absorption bands using modern quantum chemistry methods. We have demonstrated good agreement between the experimental data and the calculations. We have tested the correctness of the method we developed for the example of determining known silicon and iron contents in potassium chloride and sodium iodide. Differences between the results obtained and the true elemental contents were random. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 397–400, May–June, 2006.     

Cyanine-based Fluorescent Probe for Cyanide Ion Detection

Cyanine-based probe-possessing indolium iodide and indole unit were synthesized in two-step with easy available raw material: a potential probe for the cyanide ion detection. The detecting ability of the probe was investigated and confirmed by a visual and instrumental approach. A noticeable color change from orange to colorless obtained only for cyanide ions and other added ions does not impart any changes visually and through UV and Fluorescence technique. To confirm the mechanism of sensing 1H-NMR recorded. From the result, the peak belonging to N-methyl displayed an upfield shift from 4.01 δ ppm to 2.74 δ ppm due to the disappearance of indolium iodide ion and the olefin protons peaks were shifted from 7.19 to 6.17 and 8.70 to 7.20 δ ppm confirms the nucleophilic addition of cyanide ion to the probe. Test kit from filter paper prepared for the real-time monitoring cyanide ion. The prepared strip is effective in detecting cyanide ion with a visual color change.

     

ZnS:Cu,Eu,Br粉末ACEL的老化

退火的处理方法对ZnS:Cu,Eu,Br粉末ACEL材料的老化性能有明显的改善,但处理时颗粒表面必须包有过剩的铜,否则将破坏发光性能。若用氰化钾洗去表面过剩的铜后,再进行包铜退火处理,发光亮度部分恢复,老化性能改善。我们认为处理后老化性能改善的原因,不是改善了发光中心的条件,可能是改善了Cu2S相的条件,因而抑制了离子的迁移。     

Treatment of cyanide containing wastewater using cavitation based approach

Industrial wastewater streams containing high concentrations of biorefractory materials like cyanides should ideally be treated at source. In the present work, degradation of potassium ferrocyanide (K₄F_e(CN)₆) as a model pollutant has been investigated using cavitational reactors with possible intensification studies using different approaches. Effect of different operating parameters such as initial concentration, temperature and pH on the extent of degradation using acoustic cavitation has been investigated. For the case of hydrodynamic cavitation, flow characteristics of cavitating device (venturi) have been established initially followed by the effect of inlet pressure and pH on the extent of degradation. Under the optimized set of operating parameters, the addition of hydrogen peroxide (ratio of K₄F_e(CN)₆:H₂O₂ varied from 1:1 to 1:30 mol basis) as process intensifying approach has been investigated. The present work has conclusively established that under the set of optimized operating parameters, cavitation can be effectively used for degradation of potassium ferrocyanide. The comparative study of hydrodynamic cavitation and acoustic cavitation suggested that hydrodynamic cavitation is more energy efficient and gives higher degradation as compared to acoustic cavitation for equivalent power/energy dissipation. The present work is the first one to report comparison of cavitation based treatment schemes for degradation of cyanide containing wastewaters.     

Effect of different iodide salts on ionic conductivity and structural and thermal behavior of rice-starch-based polymer electrolytes for dye-sensitized solar cell application

Ionics - Biodegradable-based rice starch is used to prepare polymer electrolytes (PEs) using different iodide salts. Lithium iodide (LiI), ammonium iodide (NH4I), and sodium iodide (NaI) are used...     

A new method for functionalizing α,γ‐dinitro compounds at the β‐position: application to the cyclization of β‐alkoxy‐α,γ‐dinitro compounds

Treatment of 2,4‐dinitropentane with bromine and sodium methoxide in methanol, affords formation of an ether product, 2,4‐dibromo‐3‐methoxy‐2,4‐dinitropentane, in 59% yield as a mixture of three diastereomers. This observation has led to a general synthesis of 3‐alkoxy‐2,4‐dibromo‐2,4‐dinitropentanes, obtained in 75‐86% yield from 2,4‐dibromo‐2,4‐dinitropentane as the preferred reactant. 4‐Bromo‐2,4‐dinitro‐2‐pentene has been identified as an intermediate in these reactions. The nitroalkene has been isolated and undergoes conjugate addition with alkoxides to afford the same ether products after brominative work‐up. The nitroalkene undergoes conjugate addition with sodium azide to give 3‐azido‐2,4‐dibromo‐2,4‐dinitropentane in 38% yield as a mixture of two isomers in which the (R*,R*) isomer predominates. Sequential treatment of 2,4‐dibromo‐2,4‐dinitropentane with sodium methoxide followed by sodium iodide and acetic acid gives 3‐methoxy‐2,4‐dinitropentane in 63% yield, the overall product of simple methoxylation of 2,4‐dinitropentane. However, attempted complete debromination of 2,4‐dibromo‐3‐methoxy‐2,4‐dinitropentane with excess sodium iodide and acetic acid results only in monodebromination to give 2‐bromo‐3‐methoxy‐2,4‐dinitropentane in 86% yield. Likewise, 2‐bromo‐3‐ethoxy‐2,4‐dinitropentane is formed in 93% yield from the ethoxy analog. A mechanistic rationale is offered for condition‐specific removal of the second Br atom in these reactions. Treatment of 3‐methoxy‐2,4‐dinitropentane with potassium acetate/iodine in dimethyl sulfoxide affords formation of 4,5‐dihydro‐3,4‐dimethyl‐3‐methoxy‐4‐nitroisoxazole 2‐oxide in 30% yield as a single diastereomer. Conversion of 2‐bromo‐3‐methoxy‐2,4‐dinitropentane in 15% yield to 4,5‐dihydro‐3,4‐dimethyl‐3‐methoxy‐4‐nitroisoxazole 2‐oxide is also possible by using potassium acetate in dimethyl sulfoxide. The mechanistic pathways for formation of 4,5‐dihydro‐3,4‐dimethyl‐3‐methoxy‐4‐nitroisoxazole 2‐oxide apparently involve unstable 3‐methoxy‐1,2‐dimethyl‐1,2‐dinitrocyclopropane as the common intermediate. Similarly, 2‐bromo‐3‐ethoxy‐2,4‐dinitropentane affords 4,5‐dihydro‐3‐ethoxy‐3,4‐dimethyl‐4‐nitroisoxazole 2‐oxide in 13% yield. Copyright © 2013 John Wiley & Sons, Ltd.     

One pot synthesis and crystal structure of aluminosilicate mixed chloro-iodo sodalite

The crystal structure of different compositions of aluminosilicate mixed chloride and iodide sodalites was studied. The sodalites have been characterized by X-ray powder diffraction using Reitveld refinement in the space group P $ \bar 4 $ \bar 4 3n. FT-IR spectroscopy shows the successful enclathration of chloride and iodide anions in the β-cages of sodalite. Different sodalites are prepared under low temperature hydrothermal conditions in which zeolite A is used as starting material with variation of concentration of sodium chloride and iodide. The products obtained were washed with deionized water and dried overnight at 100°C. The increase in concentration of iodide shows that the Al-O-Si angle and distances in Na₈[AlSiO₄]Cl_2−x I _x sodalite (0< x ≤ 2) are modified considerably. X-ray diffraction study clearly shows variation in unit cell from 8.9241 to 8.9910? with increase in concentration of sodium iodide. IR study also shows pronounced shift in frequency with concentration of iodide. Amount of chloride and bromide was determined by potentiometry. SEM study shows cubic crystal morphology.     

溶液浓度对CCl4费米共振的影响

测量了四氯化碳在苯中不同浓度的拉曼光谱,分析了不同浓度下四氯化碳v₁+v₄~v₃费米共振的变化。结果表明:随着浓度的降低,两费米双光谱强度比R增加,而频差Δ减小、费米共振耦合系数W减小、非谐力常数K增加。这种费米共振随浓度的变化是由溶剂效应引起的,即随着四氯化碳在苯中的浓度降低,其拉曼散射系数(光谱强度)增加,使两费米双线光谱强度增加而减弱了费米共振。     

Photodynamic Therapy for Cancer Cells Using Metal-Halide Lamps

New metal-halide lamps were developed and their effect on the efficiency of photodynamic therapy (PDT) for cancer cells, murine thymic lymphoma cells (EL-4), was investigated. 5-Aminolevulinic acid-induced protoporphyrin IX was used as a photosensitizer. The metal-halide lamps were made by introducing sodium iodide (Na lamp), lithium iodide (Li lamp), and sodium iodide-lithium iodide mixture (Na-Li lamp) into their discharge tubes. These lamps emitted light in the range of 550 to 750 nm and had specific emission peaks at 580 and 600 nm for the Na lamp, 580, 610, and 680 nm for the Li lamp, and 580, 610, and 675 nm for the Na-Li lamp. Changes in the survival rate of EL-4 with increasing irradiation time indicated that PDT efficiency of the lamps increased in the order Li lamp < Na lamp < Na-Li lamp. We also found that a dark interval during irradiation of the light with the Na-Li lamp enhanced PDT efficiency.     

Ultrasonic degradation of perfluorooctane sulfonic acid (PFOS) correlated with sonochemical and sonoluminescence characterisation

Sonolysis has been proposed as a promising treatment technology to remove per- and polyfluoroalkyl substances (PFASs) from contaminated water. The mechanism of degradation is generally accepted to be high temperature pyrolysis at the bubble surface with dependency upon surface reaction site availability. However, the parametric effects of the ultrasonic system on PFAS degradation are poorly understood, making upscale challenging and leading to less than optimal use of ultrasonic energy. Hence, a thorough understanding of these parametric effects could lead to improved efficiency and commercial viability. Here, reactor characterisation was performed at 44, 400, 500, and 1000 kHz using potassium iodide (KI) dosimetry, sonochemiluminescence (SCL), and sonoluminescence (SL) in water and a solution of potassium salt of PFOS (hereafter, K-PFOS). Then the degradation of K-PFOS (10 mg L⁻¹ in 200 mL solution) was investigated at these four frequencies. At 44 kHz, no PFOS degradation was observed. At 400, 500, and 1000 kHz the amount of degradation was 96.9, 93.8, and 91.2%, respectively, over four hours and was accompanied by stoichiometric fluoride release, indicating mineralisation of the PFOS molecule. Close correlation of PFOS degradation trends with KI dosimetry and SCL intensity was observed, which suggested degradation occurred under similar conditions to these sonochemical processes. At 1000 kHz, where the overall intensity of collapse was significantly reduced (measured by SL), PFOS degradation was not similarly decreased. Discussion is presented that suggests a hydrated electron degradation mechanism for PFOS may occur in ultrasonic conditions. This mechanism is a novel hypothesis in the field of PFAS sonolysis.     

原子吸收光谱法测定小白鼠脑组织中Na,K,Ca

本文利用空气－煤气火焰或空气－乙炔火焰原子吸收光谱法分别测定小白鼠脑组织中Na,K,Ca。样品用HNO3－KClO4体系消化。用LaCl3消除P对Ca的干扰，以CsCl作Na,K的消电离剂。共测定了4组46个不同代表性的样品，测定Na,K,Ca的相对标准偏差（RSD）分别为0.886%,0.691％和0.824%，加标回收率分别为100.6%,102.0%和98.4%。