Untersuchung der Absorption der bei der Verbrennung phosphororganischer Verbindungen entstehenden P-Oxide mittels32P-markierter Verbindungen

Zusammenfassung Bei der Pyrolyse phosphor-organischer Verbindungen in Sauerstoffatmosphäre bilden sich P-Oxide, die die C,H-Bestimmung stören. Deren Verhalten im Verbrennungsrohr und ihre Absorption an geeigneten Kontakten wurden untersucht. Durch den Einsatz³²P- markierter Ausgangsverbindungen und Aktivitätsmessung des³²P sowohl durch die Wandung des Verbrennungsrohres als auch im zerkleinerten Füllungsmaterial war die laufende Bestimmung der durch die Kontaktschicht absorbierten Phosphormenge möglich. 30 verschiedene Absorptionsmittel wurden geprüft. Der Einfluß der Strömungsgeschwindigkeit des Trägergases, der Temperatur der Kontaktschicht, der Art der Verbrennung sowie der Anordnung des Verbrennungsrohres wurde untersucht. Die Absorptionsleistung der Kontakte ist stark von der Gasgeschwindigkeit abhängig.

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Investigation of absorption of the phosphorus oxides arising in the combustion of organophosphorus compounds by means of³²P-labelled substances

Summary In the pyrolysis of organophosphorus compounds in an oxygen atmosphere P oxides are formed which interfere with determination of carbon and hydrogen. Their behaviour in the combustion tube and their absorption on suitable contacts were investigated. By the use of³²P-labelled starting compounds and measuring the activity of³²P both through the wall of the combustion tube and in the comminuted filling material, continuous determination of the amount of phosphorus absorbed through the contact layer was possible. Thirty different absorption media were tested. The influence of the flow rate of the carrier gas, the temperature of the contact layer, the nature of combustion as well as the arrangement of the combustion tube was examined. The absorption efficiency of the contacts is highly dependent on the speed of the gas.

     

Über einige neue Bispirane

We have obtained four new bispirane systems in which both spiroatoms are vicinal atoms in cyclopropane or cyclobutane rings and in which the heterocyclic component has the basic structure of 1,4-dioxep-2-ene. We have shown that from two possibilities (bispiran, propellan) the general reaction leads only to a bispiran system. To the bispiran2 exhibiting the highest hyperchromism we ascribed the bispirocoplanar conformation (Fig. 1).

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Mit 3 Abbildungen     

Radiation reduction of Cr, Mo and W isopolymetalates in aqueous system

The radiation-chemical processes in aqueous solutions of dichromates, isopolymolybdates and isopolytungstates have been studied. The radiation reduction of Cr(VI) to Cr(III), Mo(VI) to Mo(V) and W(VI) to W(V) takes place. Molybdenum and tungsten blues are the products of the last two processes in acid solutions. The yields of reduction decrease significantly with the increase of pH. The mechanisms of the processes have been discussed. The photochemical reduction of Mo(VI) and W(VI) for the production of corresponding 5-valent states have been used to the study of their electron scavenging efficiencies. It has been shown that these efficiencies decrease in the order: Mo(V)>W(V)>Cr(VI)>Mo(VI)>W(VI).     

Separation of four platinum metals by anion-exchange in hydrobromic acid medium

Distribution coefficients of Pt, Ir, Pd and Rh in the systems Dowex 1 [Br^?]?HBr plus 0.0035M bromine and Dowex 1 [Br^?]?HBr plus 2% N₂H₄·HCl, were determined with the aid of radioactive tracers by batch equilibration for the resins of nominal cross-linking 2, 4 and 8, respectively. Column experiments showed that Dowex 1X4 should be used for separations because of the favourable dynamics of the column process. Elution conditions for the quantitative separation of both trace and milligram amounts of Ir?Pt, Rh?Pt, Pd?Pt and Ir?Pd?Pt mixtures are given. Some data on the effect of temperature upon the quality of separation are also presented.     

Investigation of arsenic speciation in oyster test reference material by multidimensional HPLC-ICP-MS and electrospray tandem mass spectrometry (ES-MS-MS)

Multidimensional (size-exclusion-anion-exchange-cation-exchange) liquid chromatography with ICP-MS detection was developed to produce a map of water-soluble species in an oyster test reference material. The presence of arsenobetaine, trimethyl(2-carboxyethyl)arsonium inner salt, arsenocholine, dimethylarsonic acid, tetramethylammonium ion, As(v) and two arsenosugars was demonstrated by ES-MS-MS. A previously unreported compound was isolated and identified by ES-MS-MS as 5-dimethylarsinoyl-beta-ribofuranose. Anion-exchange chromatography was optimized to produce a chromatographically pure peak of arsenobetaine (accounting for ca. 64% of all water-soluble As present) that was used to quantify this compound.     

1,4-dioxane as a solvent in spectroscopy and photochemistry

Commercially available 1,4-dioxane, even of spectroscopic grade, contains various impurities that arise mostly from reaction of the solvent with oxygen. Aspects relevant to the spectroscopy and photochemistry of the dioxane/oxygen system are discussed. Methods of purification and storage of the solvent are presented.     

Generation and reactions of substituted phenide anions in an electrospray triple quadrupole mass spectrometer

Substituted benzoic acid anions undergo decarboxylation in the medium-pressure region of an electrospray ion source yielding in most cases the correspondingly substituted phenide anions in high yield. The location of the anionic center is specified by the position of the carboxylic group. The only exceptions are compounds with substituents containing acidic hydrogen atoms, like OH and NH(2) groups. For such compounds, either an intra- or an intermolecular (mediated by the molecules of methanol or water) proton transfer from the more acidic position to the benzene ring is observed. The generated anions can be selected using the first quadrupole for studying their ion-molecule chemistry in the second quadrupole of a triple quadrupole mass spectrometer. Their reactions with CO(2), O(2), CH(3)COCH(3) and CCl(4) may serve as typical examples. The general applicability of this method for the generation of phenide anions has been confirmed on three different mass spectrometers. Experiments performed using carboxylic acids other then benzoic acid and its derivatives show that this method is not limited to phenide anions and can be used for the generation of a much wider range of carbanions in the gas phase.     

Controlled Rate Thermal Analysis of Hydrated Borates

Quasi-isothermal-isobaric analysis was applied as a main method for investigation of thermal decomposition of borates. The structural mechanism of the dehydration and dehydroxylation of selected borates is considered. It has been found that they consist of two independent stages: formation of gaseous water molecules localized into the structural framework and their release. The internal pressure of gaseous water molecules is the factor influencing the course of these processes. The strengths of the chemical bonds of the components and the freedom of their displacement also determine thermal stability of hydrated borates. This revised version was published online in July 2006 with corrections to the Cover Date.     

Studies of surface properties of Na- and La-montmorillonites

This paper presents possible applications of thermal analysis, sorptometry and porosimetry to study physico-chemical properties of Na- and La-montmorillonite samples, especially for determination of total surface heterogeneity. The quasi-isothermal thermogravimetric (Q-TG) mass loss and its first derivative (Q-DTG) curves with respect to temperature and time obtained during programmed liquid thermodesorption under quasi-isothermal conditions have been used to study adsorbed layers and heterogeneous properties of the Na- and La-montmorillonites. Calculations of the desorption energy distribution functions by analytical procedure using mass loss Q-TG and differential mass loss Q-DTG curves of thermodesorption under quasi-isothermal conditions of polar and non-polar liquid vapours preadsorbed on a material surface are presented. Parameters relating to porosity of samples were determined by sorptometry, mercury porosimetry and atomic force microscopy (AFM). From nitrogen sorption isotherms from sorptometry and porosimetry methods, the fractal dimensions of montmorillonites have been calculated. Moreover, a new approach is proposed to calculate fractal dimensions of materials obtained from Q-TG curve; this is compared with values obtained by the above methods. The total heterogeneous properties (energy distribution function and pore-size distribution functions) of samples studied were estimated. The radius and pore volume of the tested samples calculated on the basis of thermogravimetry, sorptometry and porosimetry techniques were compared and good correlations obtained.     

Properties and analytical application of chlorpromazine picrate

In neutral medium, picric acid (PA) reacts with chlorpromazine (CPM) hydrochloride with the formation of an orange compound, sparingly soluble in water, of molar ratio PA:CPM = 1:1. The compound is thermally stable up to a temperature of about 200 degrees C. The m.p. (178 degrees C) can be used for identification of picric acid as well as of chlorpromazine hydrochloride. Chlorpromazine picrate is extracted quantitatively with benzene, and the extract can be used for colorimetric determination of chlorpromazine hydrochloride. Beer's law is obeyed in the CPM concentration range 10-60 mug/ml.