The microanalysis of fluorine-containing organic compounds

Summary The method previously described for the micro-determination of fluorine in organic compounds by fusion with alkali metal in a nickel bomb followed by a thorium nitrate titration using a back-titration procedure, has been modified to meet the interferences caused by the presence of phosphorus and arsenic in the organic compound. The method ofOverman andGarrett for the removal of phosphate and arsenate ions by the addition of solid zinc carbonate was adapted for the quantitative removal of those ions. Difficulties in the determinations of carbon and hydrogen in fluoro-phosphorus compounds were overcome by mixing the samples with tungstic oxide.

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Zusammenfassung Die früher beschriebene Methode zur Mikrobestimmung von Fluor in organischen Verbindungen durch Schmelzen mit Alkalimetall in einer Nickelbombe und nachfolgende Titration mit Thoriumnitrat unter Verwendung eines Rücktitrationsverfahrens wurde weiter ausgearbeitet, um Störungen durch allenfalls anwesenden Phosphor oder Arsen zu vermeiden. Die vonOverman undGarrett angegebene Bindung von Phosphat und Arsenat durch Zusatz von festem Zinkcarbonat wurde zu einer quantitativen Entfernung dieser Ionen entwickelt. Schwierigkeiten bei der C-H-Bestimmung in fluor- und phosphorhältigen Verbindungen können durch Mischen der Probe mit Wolframoxyd umgangen werden.

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Résumé Les perturbations apportées par la présence du phosphore et de l'arsenic ont conduit à modifier la méthode antérieurement décrite pour le microdosage du fluor dans les composés organiques et qui comportait une fusion en présence d'un métal alcalin dans une bombe de nickel suivie par un titrage par le nitrate de thorium d'après une technique de dosage en retour. La méthode deOverman etGarrett pour l'élimination des ions phosphate et arseniate par addition de carbonate de zinc solide a été adaptée à l'élimination quantitative de ces ions. Les difficultés rencontrées lors du dosage du carbone et de l'hydrogène dans les composés simultanément fluorés et phosphorés ont été surmontées par le mélange des prises d'essais avec de l'oxyde tungstique.

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We wish to express our thanks to Dr.K. Sellars for the provision of samples and to Dr.J. C. Tatlow for his interest in this project.     

Photometric titration of small quantities of metals with ethylenediaminetetra-acetic acid

A commercially available photometric titration apparatus has been used for the determination ofAl, Ba, Bi, Ca, Cd, Co, Mg, Mn, Ni and Zn in the 4-20 mug range and of Hg in the 16-32 mug range. Pooled standard deviations (32 determinations) of between 0.09 and 0.15 mug were found for all the metals except Ba (0.20 mug) and Hg (0.44 mug, 24 determinations).     

The titrimetric determination of carbon dioxide with special reference to the determination of carbon in organic compounds

The titrimetric barium carbonate method for the determination of. carbon in organic compounds has been examined and the various sources of error are discussed. The carbon dioxide from the combustion of the sample is absorbed in excess baryta containing 20% (w/v) barium chloride and the excess is back-titrated with hydrochloric acid in the presence of o-cresolphthalein indicator.The value of this method in conjunction with the previously described determination of water with succinyl chloride, for the simultaneous determination of carbon and hydrogen is assessed     

Study of the competing chemical reactions in the initiation and spread of smouldering combustion in peat

Smouldering combustion of natural fuel layers such as peatlands leads to the largest fires on Earth and posses a possible positive feedback mechanism to climate change. In this paper, we use an experimental methodology to study the smouldering combustion of samples of peat under a wide range burning conditions. Vertical samples (30 mm deep and 125 mm in diameter) are ignited by radiation on the top free surface and the smouldering front propagates downward against a forced flow of oxidizer. By varying the oxygen concentration ([O₂]) and the ignition conditions we investigate the competing pyrolysis and oxidation reactions. A reaction framework with two regimes is consistently observed. The measurements show that a char species is formed by the competing pyrolysis and oxidation reactions in the first regime resulting in net char production and in the second regime char oxidation results in conversion of the char to ash. Lower mass loss rates and the larger residual mass at lower [O₂] suggest that a wider smouldering front is required to sustain combustion as the [O₂] is decreased. These results improve our understanding of smouldering phenomena and the role of the competing chemical reactions.     

Region-based SIFT approach to iris recognition

Traditional iris recognition systems transfer iris images to polar (or log-polar) coordinates and have performed very well on data that tends to have a centered gaze. The patterns of an iris are part of a 3-D structure that is captured as a two-dimensional (2-D) image and cooperative iris recognition systems are capable of correctly matching these 2-D representations of iris features. However, when the gaze of an eye changes with respect to the camera lens, many times the size, shape, and detail of iris patterns will change as well and cannot be matched to enrolled images using traditional methods. Additionally, the transformation of off-angle eyes to polar coordinates becomes much more challenging and noncooperative iris algorithms will require a different approach. The direct application of the scale-invariant feature transform (SIFT) method would not work well for iris recognition because it does not take advantage of the characteristics of iris patterns. We propose the region-based SIFT approach to iris recognition. This new method does not require polar transformation, affine transformation or highly accurate segmentation to perform iris recognition and is scale invariant. This method was tested on the iris challenge evaluation (ICE), WVU and IUPUI noncooperative databases and results show that the method is capable of cooperative and noncooperative iris recognition.     

Molecular emission cavity analysis : Part 12. Evaluation for gas chromatographic detection

Molecular emission cavity analysis (MECA) is shown to be useful for selective detection of sulphur or phosphorus compounds at the nanogram level in g.l.c. effluents. Introduction of a small oxygen flow into the cavity allows many other elements (e.g. Si, As, Sb, N, C) to be detected. The detection of microgram amounts of silylated amino acids is possible by measuring their SiO emission in the cavity at 580 nm.     

Application of the integrated ion-current technique to the study of rare-earth chelates

Several substituted acetylacetones have been prepared and reacted with holmium to give tris chelates of the form HoL₃. One of these chelates has been converted to a tetrakis chelate of the form NaHoL₄. The mass spectra of these compounds have been studied and the integrated ion currents at significant m/e values have been related to the amounts of metal chelates evaporated into the ion source of the mass spectrometer. The shape of the integrated ion-current curve is shown to give information about the nature of the evaporation process. When the β-diketone (L) is asymmetrical as in the case of 1,1,1-trifluoro-5,5-dimethylhexan-2,4-dione, the existence of geometrical isomers of the chelate, HoL₃, is reflected in the shape of the integrated ion-current curve, which shows fine structure. The results of mass spectrometric studies are compared with those of the sublimation and gas chromatographic behaviour of the metal chelates.     

Some observations on the precipitation of group II metals in qualitative analysis

Difficulties in the precipitation of Group II of the classical scheme of qualitative inorganic analysis are discussed. Three reagents for the destruction of permanganate and dichromate have been examined; hydrogen peroxide was found to be most suitable. Conditions have been established whereby As₂S₅ can be precipitated, thus avoiding the necessity for reducing As^V before passing hydrogen sulphide. A simple separation of the Group IIB elements, based on the stepwise precipitation of their sulphides from solutions of controlled acidity, is proposed.These modifications have been adapted to the procedures of Holness² and Holness and Trewick¹, for adjusting the acidity and for dividing the sulphide precipitates into the two sub-groups.