The determination of mobile nitrogen in vanadium steels by the extraction method with hydrogen

Some slope-intercept and graphical solution methods are proposed for calculation of the molar absorptivity (?) and the overall formation constant (β_n) of a complex which forms exclusively in solution. The data required for applying these methods are obtained from points selected from one or more continuous variations curves. The validity and applicability of the methods proposed are demonstrated by appropriate examples.     

Determination of hydrogen in oxygen containing zirconium hydrides by the hydrogen evolution method

Summary Hydrogen absorbed by pure zirconium can be determined quantitatively with a precision of better than ±1.4 mg or 16 ml per g of the sample, if the latter is dissolved in HP solution, the volume of hydrogen measured, and eq. 5 with R=0 is applied. For hydrogen and oxygen containing solid solutions the residue (ZrO₂) left after dissolution has to be collected, weighed, and the full eq. 5 has to be used. The precision of such determinations is about ±16 ml hydrogen per g of the alloy. Oxygen containing samples, if the hydrogen is absorbed at elevated temperatures, always leave the oxygen in the form of ZrO₂ which is insoluble in dilute HF solution. However, if hydrogen diffuses into oxygen containing Zr at low temperatures (e.g. room) then it may happen that ZrO₂ of smaller grain size (especially in the -solid solution region) will dissolve completely in the acid and if so, applying eq. 5, will result in too small an amount of absorbed hydrogen. This is a definite limitation of the method.This investigation was supported by the U.S. Atomic Energy Commission [AT (11-1)-73, Project 5].     

Determination of microquantities of nitrogen in compounds containing fluorine by an automatic rapid nitrogen analyser

Summary It was observed that when the Heraeus automatic nitrogen analyser is used for organic fluorine compounds, the fluorine (particularly as the trifluoromethyl group) interferes. The cause and extent of the interference were established by mass spectroscopy; the cause is the formation of trifluoromethane and polytetrafluoroethylene. The interference was found to be eliminated by addition of potassium perchlorate as additive to the sample boat.

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Zusammenfassung Bei Verwendung des automatischen Geräts zur Stickstoffbestimmung von Heraeus zur Analyse fluorhältiger organischer Verbindungen stört das Fluor (besonders wenn es als Trifluormethylgruppe vorliegt). Ursache und Ausmaß dieser Störung wurden massenspektroskopisch untersucht. Die Ursache ist die Bildung von Trifluormethan und Tetrafluoräthan. Die Störung läßt sich durch Zusatz von Kaliumperchlorat in das Einwaageschiffchen beseitigen.

     

Determination of hydrogen in stainless steels by spark-source mass spectrometry

A spark-source mass spectrometric (SSMS) method capable of determining traces of hydrogen in micro-volumes of metals was developed by using a pointed metal probe technique. The hydrogen background was decreased to μg g^?1 levels by the combination of a method in which the sample in the ion source is baked under vacuum at 323–343 K for more than 25 ks and a liquid nitrogen or liquid helium cryogenic pump method. This method was applied to the analysis of austenitic stainless steels at μg g^?1 hydrogen levels, and the relative standard deviation was within 20% for samples with hydrogen concentrations ranging from 2 to 4 μg g^?1. The relative sensitivity coefficent was 2.3 (Fe=1).     

Determination of nitrogen in steels by alpha-induced prompt gamma-ray spectrometry

The prompt gamma-ray of 871 keV emitted during the bombardment of steels by 5 MeV alpha particles were used to determine nitrogen by means of the reaction¹⁴N(α, pγ)¹⁷O. The method is non-destructive, rapid and experimentally simple. It has a sensitivity of about 7 μg·g⁻¹. In the nitrogen concentration range of 10¹–10² μg·g⁻¹ the relative precision of the method is about 3%. The accuracy of the method compares with that of other nuclear methods. Presented at the 5th Symposium on Recent Developments in Activation Analysis, Oxford, 17–21 July, 1978.     

Determination of melamine in dairy products by an electrochemiluminescent method combined with solid-phase extraction

An electrochemiluminescence (ECL) enhancement method combined with solid-phase extraction has been developed for the determination of melamine in dairy products. It was found that melamine in a strong base solution is able to enhance the ECL of Ru(bpy)₃²⁺ at glass carbon electrode. The optimum experimental conditions for the determination of trace melamine by ECL, such as scan mode and scan rate of the applied potential, the type of buffer solutions and their pH conditions, were investigated. Under optimized conditions, the enhanced ECL intensity was linearly proportional to the logarithm of melamine concentration in the range of 0.01-1.0 ppb, and the detection limit was 0.003 ppb. The method has been successfully demonstrated to determine melamine in dairy products including liquid milk, yogurt and milk powder samples. The relative standard deviations ranging from 5.3% to 11.2% and the recoveries from 95.2% to 102.4% were acquired by this method. A possible mechanism for the ECL enhancement effect was also proposed.     

Determination of oxygen in titanium by the micro bromination method

Summary A new micro bromination method is proposed for the determination of oxygen in titanium. The sample is mixed with carbon and treated with bromine at 825° C in a quartz boat, using argon as a carrier gas. The oxygen in the sample combines with the carbon to form carbon monoxide, which is then oxidized to carbon dioxide with hot copper oxide. The carbon dioxide is absorbed by a weighed absorption tube containing soda-asbestos. The bromine and titanium tetrabromide are removed by a cold trap cooled by dry ice and alcohol. To remove the last traces of bromine or bromine compounds, a soda tube and silvergauze heated to 650° are used. The method has been satisfactorily applied to the determination of oxygen in commercial titanium.

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Zusammenfassung Eine neue Mikromet-hode zur Bestimmung von Sauerstoff in Titan durch Bromierung wird vorgeschlagen. Die Probe wird mit Kohlenstoff gemischt und bei 825° C in einem Quarzschiffchen mit Brom behandelt, wobei Argon als Trägergas dient. Der in der Probe enthaltene Sauerstoff reagiert mit dem Kohlenstoff zu Kohlenmonoxyd, das dann über erhitztem Kupferoxyd zu Kohlendioxyd oxydiert wird. Dieses wird in einem gewogenen Absorptionsröhrchen an Natronasbest gebunden. Brom und Titantetrabromid werden in einer Falle mit Trockeneis und Alkohol ausgefroren. Zur Entfernung der letzten Spuren Brom oder Bromverbindungen dient ein auf 650° erhitztes Röhrchen mit Natron und Silberdrahtnetz. Das Verfahren hat sich zur Bestimmung von Sauerstoff in handelsüblichem Titan zufriedenstellend bewährt.

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Résumé Les auteurs proposent une nouvelle microméthode de bromuration pour le dosage de l'oxygène dans le titane. L'échantillon mélangé avec du carbone est traité par le brome à 825° C dans une nacelle de quartz sous courant d'argon utilisé comme gaz de transport. L'oxygène de l'échantillon se combine au carbone sous forme d'oxyde de carbone qui est oxydé en anhydride carbonique sur oxyde de cuivre à chaud. L'anhydride carbonique est absorbé et pesé dans un tube absorbeur rempli d'amiante sodé. Le brome et le tétrabromure de titane sont retenus dans un piège refroidi par le système glace carbonique-alcool. Les dernières traces de brome et de composés bromés sont éliminées à l'aide d'un tube à soude et d'une toile d'argent chauffée à 650°. La méthode a été appliquée avec succès au dosage de l'oxygène dans le titane commercial.

     

Determination of nitrogen by the method of Kirsten

Summary Experience with theKirsten method for the determination of nitrogen has shown that improved performance is obtained by omitting the temporary filling. A modified method is described which is simpler than the original, but which gives results of equal accuracy and precision.

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Zusammenfassung Erfahrungen mit der Methode vonKirsten zur Bestimmung des Stickstoffs haben gezeigt, daß es besser ist, auf die bewegliche Füllung des Verbrennungsrohres zu verzichten. Eine abgeänderte Methode wird beschrieben, die einfacher ist als das ursprüngliche Verfahren, wobei aber die gleiche Genauigkeit erzielt wird.

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Résumé L'expérience avec la méthode deKirsten pour la détermination de l'azote a avéré que le rendement est amélioré si la charge temporaire est supprimée. Une méthode modifiée a été décrite; elle est plus simple que la méthode originale tout en donnant des résultats aussi exacts.

     

Determination of inorganic anions in ethyl acetate by ion chromatography with an electromembrane extraction method

In this work, the determination of inorganic anions in slightly water-soluble organic solvents (ethyl acetate) was realized by ion chromatography (IC) with a novel-efficient electromembrane extraction method. From an 8 mL ethyl acetate sample, three inorganic anions migrated through the pores of a polypropylene hollow fiber membrane, and into deionized water inside the lumen of the hollow fiber by the application of 600 V. The transport was forced by an electrical potential difference sustained over the liquid membrane, resulting in electrokinetic migration of inorganic anions from the donor compartment to the acceptor solution. After the electromembrane extraction, the acceptor solution was analyzed by IC with a sodium carbonate-sodium bicarbonate eluent. The applied voltage, stirring speed, and extraction time for controlling the extraction efficiency were optimized. Within 10 min of operation at 600 V, chloride, bromide, and sulfate were extracted with recoveries in the range 76-110%, which corresponded to a linear range of 0.01-1 mg/L. The procedure was applied to the analysis of inorganic anions in a real ethyl acetate sample and expands onto other slightly water-soluble organic solvents.     

脉冲熔融-红外/热导法测定钛合金粉末微注射成形脱脂坯中氧氮氢

准确测定钛合金粉末微注射成形脱脂坯中氧氮氢含量对钛合金的粉末微注射工艺改进有很大指导作用。采用工业镍板经过表面打磨、酸洗、加工成固定质量的镍粒来代替市售的镍助熔剂,通过自制镍粒预先加入设备预脱气减少空白影响的方式建立了脉冲熔融-红外/热导法测定钛合金粉末微注射成形的脱脂坯中氧氮氢含量的方法。实验表明,镍粒助熔剂与石墨坩埚经二次脱气,可确保镍粒助熔剂的空白降至极低值以代替市售的镍篮、镍屑等助熔剂。钛合金粉末微注射成形脱脂坯采用振动磨形式加工至0.178 mm以下,镍粒的加入量为1.5 g,分析功率为5 300 W时,可以获得稳定准确的结果。采用实验方法对脱脂坯实际样品进行测定,其相对标准偏差(RSD,n=6)分别为0.080%～0.47%、0.28%～1.3%和1.6%～2.0%;采用加入钛合金标准样品进行加标回收实验,氧氮氢加标回收率分别在95.7%～104%、97.8%～100%及96.6%～103%。方法满足脱脂坯中的氧氮氢快速检测要求的同时,极大地降低了分析成本。     

微波消解-原子吸收法测定啤酒中的微量铝

利用微波消解-原子吸收法测定了啤酒中的微量铝。在密闭容器中采用微波、HNO3-H2O2消化制备试样溶液,然后在酸性介质中,铝与8-羟基喹啉生成1∶3络合物,通过甲基异丁基甲酮(MIBK)萃取,用氧化亚氮-乙炔火焰原子吸收法测定有机相中铝即可测定啤酒中微量铝。本法在0~500μg/L范围内呈良好的线性关系(R2=0.9991),可用于啤酒中微量铝的测定。     

Heats of atomization of some conjugated molecules containing nitrogen or oxygen by a novel semiempirical method

Heats of atomization for a range of conjugated molecules containing nitrogen or oxygen are calculated by a semiempirical method that combines some features of both the MO and VB theories. The π ground state of each conjugated molecule is represented as a linear combination of Kekulé structures. Unlike in the VB theory, each Kekulé structure is a determinant containing bond orbitals. Here experimental heats of atomization are reproduced approximately as well as by the more sophisticated SCF –MO approach. The use of this method is, however, much simpler since it amounts to a single diagonalization of a matrix of the order equal to the number of Kekulé structures only.     

ICP-AES法测定铸造铝合金中的痕量钙

采用ICP AES法研究铝轮毂用铸造铝合金中痕量钙的测定。以补偿法消除共存元素钛对钙的测定干扰。并运用铝基体工作曲线来消除铝基的影响,以提高分析的准确度。无需分离主体铝,方法的回收率在95.3%～105.5%之间,RSD≤5.5%。可满足铸造铝合金中钙质量分数大于0.001%的测定。     

Determination of nitrogen in an aluminium-killed steel by an isotope-dilution method using Al(15)N

Nitrogen in an aluminium-killed steel was determined by an isotope-dilution method using synthesized aluminium nitride enriched with (15)N. The results were in agreement with those obtained by chemical determination, whereas the vacuum fusion method with iron and platinum baths, and the isotope-dilution method using gaseous (15)N-enriched nitrogen, did not give accurate results.     

Pure-component vapour pressures of heavy hydrocarbons containing nitrogen or sulphur using the UNIFAC group-contribution method

A group-contribution model for predicting pure-component vapour pressures, in part based on the UNIFAC method for vapour—liquid equilibria, has been extended to include hydrocarbons of molecular weights below 500 containing nitrogen or sulphur. Good representation is obtained for vapour pressure data in the region 10–2000 mmHg. In addition, the accuracy of the method is tested by prediction of heats of vapourization via the Clausius—Clapeyron equation. The predicted heats of vapourization agree with the experimental values within a few percent. In absence of experimental data, the model may be used to estimate vapour pressures and heats of vapourization for the category of compounds studied.     

Determination of carbon, hydrogen and nitrogen in inorganic compounds by means of an automatic organic elemental microanalyzer

The Hewlett Packard Model 185 CHN Analyzer, which is based on an automated modified Dumas combustion technique and was designed for the analysis of organic materials, has been applied to the determination of carbon, nitrogen and hydrogen in inorganic compounds.With minor modifications to the procedure routinely used for the organic analysis, the instrument has proved to be able to broaden its original application field giving in general good performances in the inorganic domain.A particular emphasis has been put in testing nitrates, carbonates, ammonium salts and different kinds of carbon. Till now it appears that the only materials really difficult to analyze are the refractory nitrides, carbides and carbonitrides.Finally some considerations have been made in respect of the determination of the percent weight composition of mixtures through their carbon, nitrogen and hydrogen content.     

Determination of aluminium in blood plasma or serum by electrothermal atomic absorption spectrometry

A carbon-furnace atomic absorption method is used to determine aluminium in blood serum or plasma, diluted (1 + 2) with purified water prior to injection (20 μl) into the furnace. Procedures are described to reduce contamination during sample collection, storage and preparation of samples. A study of the interferences of inorganic ions shows that the temperature programme developed minimises these, allowing the use of aqueous standards for calibration. Ashing at 1400°C, prior to atomisation, also removes non-specific background effects, and optical correction is not required. A sample throughput of 50 duplicate analyses per day is possible and the precision (between batch) at 24 μg Al l^-1 was 11.2% (n = 10) and at 340 μg Al l^-1 was 6.3% (n = 18). Down to 4 μg Al l^-1 can be determined. Reference values for a healthy population were 4.1–20 μg Al l^-1 (mean 10.2).     

Role of hydrogen peroxide in the synthesis of nitrogen heterocycle containing cobalt complexes

The reactions of Co(O₂CCH₃)₂·4H₂O with the sodium salt of p-toluene sulfonic acid (NapTS) and pyridine (py) or 4-methylpyridine (4mepy) in the presence of hydrogen peroxide in methanol led to the formation of [Co(py)₃(H₂O)₃](pTS)₂ or [Co(4mepy)₂(H₂O)₄](pTS)₂·MeOH, respectively. The coordination polymer [{Co(44′bpy)(H₂O)₄}(pTS)₂]_n (4,4′-bipyridine = 44′bpy) was obtained from the reaction of Co(O₂CCH₃)₂·4H₂O with 44′bpy in the presence of NapTS. The reaction of Co(O₂CCH₃)₂·4H₂O, 2,2′-bipyridine (22′bpy) and NapTS with hydrogen peroxide resulted in the formation of the dinuclear complex [Co₂(μ-OH)₂(μ-O₂CCH₃)(O₂CCH₃)₂(22′bpy)₂](pTS). Characterization of these complexes and the role of hydrogen peroxide in these reactions are discussed. Similar reactions with sodium sulfamate gave the mononuclear [Co(22′bpy)₂(O₂CCH₃)]NH₂SO₃·2H₂O complex and [Co₂(μ-OH)₂(μ-O₂CCH₃)(O₂CCH₃)₂(22′bpy)₂](NH₂SO₃).