Fluoride interference in the molecular emission of boron in water/methanol media

The fluoride interference on the molecular emission of boron in largely methanolic solutions introduced into flames is described. The magnitude of this influence depends on the methanol, boron and fluoride concentrations and on the apparent pH. The results are explained on the basis of gradual substitution of BO bonds by BF bonds.     

Quantum Interference Enhanced Chemical Responsivity in Single-Molecule Dithienoborepin Junctions

Providing a chemical control over charge transport through molecular junctions is vital to developing sensing applications at the single-molecule scale. Quantum-interference effects that affect the charge transport through molecules offer a unique chance to enhance the chemical control. Here, we investigate how interference effects can be harnessed to optimize the response of single molecule dithienoborepin (DTB) junctions to the specific coordination of a fluoride ion in solution. The single-molecule conductance of two DTB isomers is measured using scanning tunneling microscopy break-junction (STM-BJ) before and after fluoride ion exposure. We find a significant change of conductance before and after the capture of a fluoride ion, the magnitude of which depends on the position of the boron atom in the molecular structure. This single-molecule sensor exhibits switching ratios of up to four orders of magnitudes, suggesting that the boron–fluoride coordination can lead to quantum-interference effects. This is confirmed by a quantum chemical characterization, pointing toward a cross-conjugated path through the molecular structure as the origin of the effect.     

A study of the titrimetric potassium silicofluoride method for determination of silica in aluminosilicate materials

A critical study of the titrimetric potassium silicofluoride method for determination of silica reveals that quantitative precipitation of the sificofluoride is possible in 3.5-7.5N acid containing 1% sodium fluoride and >/ 12% potassium chloride. An aqueous wash solution (pH approximately 5.3) containing 0.1% sodium fluoride and 12% potassium chloride has been found ideal for washing the precipitate without significant hydrolysis even at 35 degrees C. The interference of large amounts of aluminium (up to 160 mg of Al(2)O(3)) is eliminated by precipitating the silicofluoride in 6-7.5N acid solution, the aluminium then forming practically no fluoro-complex, because of extensive protonation of fluoride. Interference by large amounts of boron (up to 160 mg of B(2)O(3)) is eliminated by precipitating silicofluoride with the minimum permissible potassium chloride concentration (12%) and washing with the aqueous wash solution at room temperature. Nitrazene Yellow has been used as a more sensitive indicator.     

Zur borbestimmung in silizium und germanium durch aktivierung mit protonen und deuteronen

The determination of boron via the nuclear reaction ¹¹B(p,n)¹¹C was studied in detail; the nitrogen reaction ¹⁴N(p,a)¹¹C interferes. Nitrogen also interferes deuteron activation via the nuclear reactions 10B(d,n)¹¹C and ¹¹B(d,2n)¹¹C, this interference must be attributed to the nuclear reaction ¹⁴(d,αn)¹¹C. Both interferences were investigated quantitatively. The conditions for the accurate determination of boron and for a simultaneous determination of boron and nitrogen by proton activation were established. An analytical method with chemical separation of the radioisotope ¹¹C was developed for silicon and germanium.     

Synthesis of Boron-containing Complexes of 1-(2-hydroxyphenyl)-3-phenyl-2-propen-1-one

Condensation of o-hydroxyacetophenone with benzaldehyde in alcohol in the presence of a triple excess of a sodium hydroxide solution leads to 2'-hydroxychalcone sodium salt. The latter was heated with boron trifluoride etherate in toluene to a 2'-hydroxychalcone boron fluoride complex in which the boron atom is coordinated to the carbonyl oxygen atom. The same complex was obtained by boiling of the o-hydroxyacetophenone boron fluoride complex with benzaldehyde in acetic anhydride.     

基于有机硼化合物的氟离子化学传感器的研究进展

有机硼化合物中硼原子空的pπ轨道使其作为路易斯酸能够选择性的结合氟离子,其与氟离子的结合破坏了硼中心与芳香取代基的pπ-π共轭,引起有机硼化合物光物理性质的变化。因此,有机硼化合物能够用作高选择性的氟离子化学传感器材料。本文从具有三芳基硼结构及硼酸或硼酸酯结构的这两类有机硼化合物出发,综述了它们在氟离子化学传感器领域的研究进展。     

An investigation of the reaction mechanism of copper fluoride carriers in the spectrochemical determination of boron and silicon

The reaction mechanism by which copper (II) difluoride dihydrate and copper hydroxy fluoride increase the sensitivity of boron and silicon in emission spectrochemical analysis has been studied with the aid of thermal gravimetric analysis. Both compounds decompose at relatively low temperature with the evolution of hydrogen fluoride. It is shown that when boron and silicon are present as their oxides, they are volatilised from the system and their removal coincides with the evolution of hydrogen fluoride. This supports the proposal that the increased sensitivity achieved in spectrochemical analysis is a result of volatile fluoride formation.     

Determination of fluorine in boron-containing materials with a fluoride sensitive electrode

Summary The fluoride-ion selective micro-determination of fluorine in organic materials after closed flask combustion is an established technique. Interferences, due to complexation of the fluoride ion can occur, if the sample contains boron or fluorborate ion. This paper describes a method that avoids complexation of fluoride by combustion in a hydrogen-oxygen flame and absorption of the resulting H₂F₂ in alkali hydroxide solution. By this method, samples can be analyzed for fluorine without interference by boron. Some results of the analysis of pharmaceutical materials are given.

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Zusammenfassung Die Mikrobestimmung von Fluor in organischem Material nach Kolbenverbrennung mit Hilfe einer fluoridspezifischen Elektrode ist eine eingeführte Methode. Störungen infolge Komplexierung des Fluoridions können auftreten, wenn die Probe Bor oder Fluorborat enthält. Die vorliegende Arbeit beschreibt eine Methode, um diese Komplexbildung durch Verbrennung in der Knallgasflamme und Absorption des H₂F₂ in Alkalilauge zu vermeiden. Einige Analysenergebnisse pharmazeutischen Materials werden angeführt.

     

Kernresonanzspektrographische Untersuchungen im System Phenylphosphoroxydifluorid-Bor(III)chlorid

Zusammenfassung Phenylphosphoroxydifluorid reagiert mit Bor(III)chlorid bei Raumtemperatur zu Phenylphosphoroxydichlorid und Bor(III)fluorid, wobei Phenylphosphoroxyfluoridchlorid als stabiles Zwischenprodukt entsteht, das dann mit BCl₃ weiterreagiert.

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Phenylphosphonic difluoride reacts with boron chloride at room temperature to give phenylphosphonic dichloride and boron fluoride with phenylphosphonic fluoride chloride as a stable intermediate.

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Mit 5 Abbildungen     

Interaction of gallium, indium, thallium, germanium, tin, and lead with boron

Summary Investigations of the interaction of boron with gallium, indium, thallium, germanium, tin, and lead with boron showed that these elements do not form chemical compounds or solid solutions with boron.The absence of any interaction between these elements and boron is explained in the light of a discussion of the electronic structure and energy characteristics of the valence electrons of metals of the IIIB and IVB subgroups of the periodic system.Translated from Zhurnal Strukturnoi Khimii, Vol. 1, No. 4, pp. 458–463, November–December, 1960     

Determination of boron in materials by cold neutron prompt gamma-ray activation analysis

An instrument for cold neutron prompt gamma-ray activation analysis (PGAA), located at the NIST Center for Neutron Research (NCNR), has proven useful for the measurement of boron in a variety of materials. Neutrons, moderated by passage through liquid hydrogen at 20 K, pass through a (58)Ni coated guide to the PGAA station in the cold neutron guide hall of the NCNR. The thermal equivalent neutron fluence rate at the sample position is 9 x 10(8) cm(-2) s(-1). Prompt gamma rays are measured by a cadmium- and lead-shielded high-purity germanium detector. The instrument has been used to measure boron mass fractions in minerals, in NIST SRM 2175 (Refractory Alloy MP-35-N) for certification of boron, and most recently in semiconductor-grade silicon. The limit of detection for boron in many materials is <10 ng g(-1).     

Potentiometric determination of boron in silicon with an ion-selective electrode

A potentiometric method is proposed for the determination or boron in silicon, based on dissolution of silicon by treatment with hydrofluoric acid and ammonium fluoride in the presence of hydrogen peroxide, and conversion of boron to fluoroborate ion. The fluoroborate activity is measured with the Orion fluoroborate-selective electrode. Some important points, such as the effect of various interfering ions and the hydrolysis of fluoroborate ion, are described in detail. The method is applied to the determination of boron in silicon containing at least 10 p.p.m. of boron, with a relative standard deviation of ±4%.     

Interference-free atomic spectrometric method for the determination of trace amounts of germanium by utilizing the vaporization of germanium tetrachloride

Trace amounts of germanium can be determined by atomic spectrometry by utilizing the vaporization of germanium tetrachloride at ambient temperature. Using an intermittent or continuous flow reactor, the sample solution was mixed with concentrated hydrochloric acid to form volatile germanium tetrachloride which can subsequently be determined by atomic spectrometry. The conditions for the volatilization of germanium chloride were investigated in detail and rapid method for the determination of trace amounts of germanium in real samples was proposed. A detection limit of 0.5 ng ml⁻¹ (3σ_n−1) was obtained by using atomic fluorescence spectrometric detection and the precision found was 0.8% for a germanium concentration of l00 ng ml⁻¹. Atomic emission and absorption spectrometric methods were also tested. Owing to the high selectivity of the reaction, no interference was found in the determination. The method was applied to the determination of germanium in several standard and certified reference materials; the results obtained were in good agreement with the certified values.     

Fluorination of germanium concentrates with ammonium fluorides

New method for processing of germanium-containing raw materials to obtain germanium oxide was suggested and studied. The method is based on the fluorination of germanium-containing raw materials with ammonium fluorides, followed by a sublimation isolation of ammonium hexafluorogermanate, its dissolution, and precipitation of germanium oxide from solution. The thermodynamics of the process was calculated and its thermogravimetric analysis was made. The kinetics of germanium oxide fluorination by ammonium hydrodifluoride was experimentally studied. A technological scheme for processing of germanium-containing raw materials with ammonium fluoride was suggested.     

Indirect atomic-absorption determination of boron by solvent extraction as tris(1,10-phenanthroline)cadmium tetrafluoroborate

An indirect atomic-absorption method for boron has been developed. Boric acid is converted into tetrafluoroborate and extracted into nitrobenzene with Tris(1,10-phenanthroline)cadmium(II). The cadmium in the extract is determined by its atomic-absorption at 228s>d8 nm. A fivefold molar excess of the cadmium chelate is necessary for the extraction from pH 4>d3-6>d0 medium. The sensitivity for boron is thus made about the same as that of cadmium, 0>d005 ppm. Metal ions that react with fluoride or phenanthroline interfere. A procedure is described for determination of boron in steel.     

Stabilization of germanium(ii) by complex formation in iodimetric titration of germanium

Four factors are important in the reduction of germaniuin(IV) by hypophosphite, namely, proper acidity, temperature, proper concentration of complexing ligand, and time of heating. The complexing ligand is needed to stabilize the germaium(II) ions. Halides, with the exception of fluoride, and phosphate are good complexing ligands for germanium. Tin is quantitatively reduced and titrated under the same conditions. Many foreign ions do not interfere, so that prior separation of germanium can often be avoided. Successful results are presented for titrating germanium in the presence of many metals and for direct determination of germanium in actual samples. Germanium after reduction may be titrated with an iodate solution potentiometrically. The formal oxidation potentials of some germanium half-reactions were estimated and used to interpret the stabilization of germanium(II) by complex formation. Phosphoric acid is recommended as the reduction medium.     

离子色谱-电感耦合等离子体质谱测定保健品中无机锗和锗-132

建立了离子色谱-电感耦合等离子体质谱法( IC-ICP-MS)测定液体保健品中无机锗和β-羧乙基锗倍半氧化物(锗-132)的方法,对液体或可溶于水的样品可以直接或稀释后进样.硒元素可能会带来干扰,可以选择72Ge作为定量同位素来避免.方法中无机锗和锗-132的定量限均为1.0μg/L,RSD均小于4.4％.对实际样品进行加标,无机锗回收率为91％～92％,锗-132回收率为104％～107％.样品的测定结果和湿法消解-电感耦合等离子体质谱检测出的结果相吻合.     

An indirect method for the spectrofluorimetric determination of trace amounts of germanium after extraction as an ion association complex with rhodamine B in the presence of chromotropic acid

A highly sensitive and selective spectrofluorimetric method for the determination of 0.05-2.00 mug germanium is described. Germanium is treated with chromotropic acid at pH 2.5 and the resultant anionic complex is extracted as an ion pair with rhodamine into toluene. Addition of butanol to the organic extract releases the fluorescent dye and facilitates its measurement at 570 nm after exciting at 540 nm. The method provides a detection limit of 0.003 mug ml(-1) and is virtually free from interference from extraneous ions. The relative standard deviaiton is 2.9% for ten determinations of 1.0 mug germanium. The method has been applied to the determination of germanium in various ores, minerals and rock samples.     

Molecular emission cavity analysis (meca)—a new flame analytical technique: Part III. The determination of boron

Two highly selective methods are described for the determination of boron by molecular emission cavity analysis. In one, boron (>0.1 p.p.m.) is extracted as its 2-ethylhexane-1,3-diol chelate into methyl isobutylketone; 5-80 ng of boron in 5 μl of the extract is determined by injection into the MECA cavity. In the other, boron (2-30 μl) is converted into volatile methyl borate, and carried into the rear of the cavity by a stream of nitrogen. In both methods, the emission intensity at 518 nm, stimulated by a hydrogen-nitrogen-oxygen flame, is measured. Of the other ions tested, none interfered in the volatilization procedure, and only fluoride ( ? 100 mg) interfered in the extraction method. The precision is ±4%.     

Direct determination of parts-per-billion levels of germanium in botanical samples and coal fly ash by graphite furnace atomic absorption spectrometry

 Parts-per-billion levels of germanium can be determined directly by graphite furnace atomic absorption spectrometry (GFAAS) using palladium plus strontium as a mixed modifier resulting in pyrolysis temperatures up to 1400 °C without loss of germanium. At this temperature the matrix effect including the most troublesome sulfate interference can be eliminated. Palladium plus strontium nitrate is advantageous compared to palladium alone or palladium plus magnesium nitrate; an amount of 15 μg of sulfate does not show any interference on the determination of 1 ng of germanium. The method was successfully applied to the determination of ng/g levels of germanium in botanical samples and coal fly ash after thermal decomposition of the samples in a mixture of acids using a pressure bomb. The results were consistent with the reference values given for botanical samples and coal fly ash with a recovery range of 96.4∼103.4% Received: 16 September 1996/Revised: 10 December 1996/Accepted: 14 January 1997