On the Dumas determination of nitrogen

Summary Reactions in theDumas nitrogen determination method have been investigated. The presence of free oxygen in the combustion tube was found to cause retention of nitrogen oxides by the metal oxide catalyst. Nickel oxide was found superior to copper oxide because it allows the use of higher temperatures and does not liberate oxygen on heating, thus eliminating the retention error.A new method is described which uses automatic combustion and makes use of the reaction C + CO₂ = 2 CO at 1050° C and combustion with nickel oxide at 1000° C. The standard deviation of 20 analyses on known compounds carried out in direct succession was 0.045%.

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Zusammenfassung Einige bei der Stickstoffbestimmung nachDumas ablaufende Reaktionen wurden untersucht. Es wurde gefunden, daß die Gegenwart von freiem Sauerstoff im Verbrennungsrohr zu einer chemischen Bindung von Stickstoffoxyden an den Metalloxydkatalysator führt. Nickeloxyd eignet sich besser als Kupferoxyd, da es die Anwendung höherer Temperaturen ermöglicht und beim Erhitzen keinen Sauerstoff abgibt, so daß der obenerwähnte Fehler vermieden wird.Eine neue Methode wird beschrieben, nach der die Substanz durch Anwendung der Reaktion C + CO₂ = 2 CO bei 1050° C vergast und dann über Nickeloxyd bei 1000°C verbrannt wird. Die mittlere Abweichung bei 20 direkt nacheinander ausgeführten Analysen betrug 0,045%.

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Résumé On a examiné les réactions qui se produisent dans le dosage de l'azote par le procédéDumas. On a trouvé que la présence d'oxygène libre dans le tube à combustion produisait une rétention des oxydes de l'azote par l'oxyde métallique catalyseur. L'oxyde de nickel a été trouvé supérieur à celui de cuivre car il permet l'emploi de plus hautes températures et ne libère pas d'oxygène par chauffage, ce qui élimine l'erreur de rétention.On décrit une nouvelle méthode qui utilise la combustion automatique et fait usage de la réaction C + CO₂ = 2 CO à 1050° C et de la combustion avec l'oxyde de nickel à 1000° C. L'erreur standard sur 20 analyses de composition connue effectuées à la suite a été de 0,045%.

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With 7 figures.     

A combined μ-mercury reference electrode/Au counter-electrode system for microelectrochemical applications

Different types of mercury-based μ-reference electrodes (Hg/Hg₂SO₄/Na₂SO₄, Hg/Hg₂(CH₃COO)₂/NaCOOCH₃) have been developed following the concept of agar-based μ-reference electrodes. Mercury was electrochemically deposited onto a gold wire to form an amalgam. The corresponding mercury salt was formed electrochemically at the surface. This electrode can be inserted into a capillary that is filled with the electrolyte of interest. To simplify the handling of this μ-reference electrode, to reduce diffusion and to avoid leakage, the electrolyte was immobilised with agar. A 250-nm-thick gold layer on the outer surface of the capillary of the reference electrode served as counter-electrode. The electrochemical behaviour of reference electrodes and counter-electrodes were proven by micro-polarisation curves, electrochemical impedance spectroscopy, potential transients and cyclic voltammetry.     

Determination of desoxycorticosterone acetate using tetrazoliumsalt

Summary The colorimetric procedure for the determination of desoxycorticosterone acetate described byMader andBuck was investigated. In order to obtain reproducible results the determinations should be carried out at a determined alcohol concentration and in the dark and the measurements of the colors should be made a determined interval of time after the mixing of the solutions. A procedure is proposed.

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Zusammenfassung Das vonMader undBuck beschriebene Verfahren zur kolorimetrischen Bestimmung von Desoxycortioosteronacetat wurde nachgeprüft. Um reproduzierbare Ergebnisse zu erhalten, muß eine bestimmte Alkoholkonzentration eingehalten, die Farbreaktion bei Lichtabschluß durchgeführt und die Farbmessung nach Ablauf einer bestimmten Zeit nach dem Mischen der Lösungen vorgenommen werden. Eine genaue Arbeitsvorschrift wird mitgeteilt.

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Résumé On étudie le dosage colorimétrique de l'acétate de désoxycorticostérone décrit parMader etBuck. Afin d'obtenir des résultats reproductibles, les dosages doivent être effectués à une concentration déterminée de l'alcool, à l'obscurité et les mesures des colorations à des intervalles de temps déterminés après le mélange des solutions. On propose un mode opératoire.

     

Orientation modulation of a synthetic polypeptide in self-assembled monolayers: a TOF-SIMS study

Structure and orientation of molecules are key properties of functionalized surfaces. Using time-of-flight secondary ion mass spectrometry (TOF-SIMS), here we investigate how to modulate these parameters upon the immobilization process varying the conditions of self-assembly. The molecule of interest, a template-assembled synthetic protein (TASP), consists of a central peptide ring with orthogonally arranged residues. Thioalkane chains allow the directed self-assembly of the molecule on a gold surface; four serine residues on the opposite side of the ring can be used as anchoring sites for various functional sensing molecules. The TASP conformation and its orientation in self-assembled monolayers (SAMs) play a central role for the accessibility of these serine residues. To study the influence of the self-assembly conditions, two series of samples were prepared. Pure TASP monolayers of different surface densities are compared to mixed TASP/alkanethiol monolayers prepared by sequential adsorption varying sequence and particular incubation times as well as by coadsorption modifying incubation times and TASP/alkanethiol mass ratios. Switching the TASP orientation from a state where the molecules are lying flat on the surface to an upright orientation turned out to be possible by inserting the TASP into a preformed alkanethiol monolayer of an appropriate surface density. This study demonstrates that TOF-SIMS is an excellent tool not only to investigate the surface composition, but also the molecular structure of functionalized surfaces.     

Stabilizers in automotive coatings under acid attack

To examine the action of acid atmospheric precipitation on the light stabilisers in automotive coatings two common clearcoat types (TSA and 2K-PU) blended with commercially available HALS and UVA were subjected to artificial weathering (Acid Dew and Fog test and Acid-free weathering test) and natural weathering outdoors in Jacksonville, FL. Tracing gloss and haze during weathering the test results showed that the influence of acid stress on the long-term performance of the clearcoats depended on the kind of the stabilisation system.     

Replacement of toxic mobile phases commonly used in high performance liquid chromatography of retinoids

Vitamin A isomers are usually separated and analysed by high performance liquid chromatography (HPLC) using an eluent mixture which contains organic solvents such as n-hexane or 1,4-dioxane. However, both are toxic, n-hexane causes a degenerating nerve disease, whereas 1,4-dioxane is supposed to be carcinogenic. In order to avoid preventive handling and potential hazards to health these solvents have been replaced by various mobile phases of n-heptane/tert-butylmethylether. The advantages are better baseline separation of the main retinol isomers and discrimination of even several di- and tri-cis-retinol isomers, low solvent consumption and no known risk so far to health.     

Bis[N-alkyl-NN-di(2-pyridylmethyl)amine]zinc(II) perchlorates display cis-facial stereochemistry in solid state and solution

N-Alkyl-N,N-di(2-pyridylmethyl)amines are ligands commonly used by supramolecular chemists in molecular recognition and sensing applications. The metal coordination complexes of these ligands, in particular those with 2:1 (ligand:metal) molar ratio, have not been sufficiently characterised in solution. In this work, bis[N-alkyl-N,N-di(2-pyridylmethyl)amine]zinc(II) perchlorates are characterised in both solid and solution phases, using X-ray crystallography and NMR spectroscopy, respectively. Only the cis-facial stereoisomer is observed. Density functional theory calculations support the thermodynamic preference for this stereochemistry, as in one representative case the gas phase energy of the cis-facial configuration is lower than those of the trans-facial and meridional configurations by 4.0 and 4.5 kcal/mol, respectively.     

Unerwartete Bildung von Monomesitylmolybdän(V,VI)-Verbindungen

Mesityl Oxo Molybdenum and Tungsten Compounds. II. Unexpected Formation of Monomesityl Molybdenum(V,VI) Compounds The synthesis of known MoO₂Mes₂ from MoO₂Cl₂ and MgMes₂ (1 : 1) in THF is accompanied by the formation of monomesityl molybdenum compounds. From ligand exchange and reduction arise [MesMoOCl₃]^– ( 3 a ) and [MesMoO₃]^– ( 3 c ). 3 a and 3 b crystallize in form of [(MesMoO₃)₂{Mg₂Cl₂(THF)₅}₂][MesMoOCl₃]₂(THF)₂, which has been characterized by X-ray structural analysis. In 3 two MesMoO₃ units are linked in a ring-like manner via magnesium ions. The anion 3 a , which possesses a distorted trigonal-bipyramidal arrangement, was also isolated as [Mg(THF)₆][MesMoOCl₃]₂ which was investigated by X-ray analysis. The reaction of MoO₂Cl₂ with MgMes₂ in a 1 : 0,5 ratio generates the compounds [Mg(THF)₄(MoO₃Cl)₂] and MoOCl₃(THF)₂. Reaction pathways which may lead to these compounds are discussed.