Studies in qualitative inorganic analysis. Part XXVI

Summary The preliminary tests for organic radicals, which are based on charring by strong heating or by hot concentrated sulphuric acid are examined. Even when both these tests are applied some organic acids escape identification. Two alternative procedures based upon oxidation of organic matter with potassium dichromate in dilute sulphuric have been examined. The first procedure involves a reduction of the dichromate ion to the distinctive green chromium(III) ion. This occurs with all organic radicals commonly encountered in qualitative inorganic analysis, except acetate and salicylate. Interference due to inorganic reducing agents is overcome by a preliminary oxidation with hydrogen peroxide. The second procedure involves decomposition of carbonates, bicarbonates, and cyanates with dilute sulphuric acid, followed by oxidation of organic matter with potassium dichromate in sulphuric acid to carbon dioxide, which is detected with lime water. Of the radicals commonly encountered in qualitative inorganic analysis only acetate gives a negative result.

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Zusammenfassung Die Vorprobe auf organische Anionen auf Grund ihrer Verkohlung durch kräftiges Erhitzen oder durch Einwirkung konz. Schwefelsäure wurde überprüft. Auch bei Anwendung beider Arbeitsweisen entziehen sich einige organische Säuren dem Nachweis. Zwei andere Verfahren auf der Grundlage der Oxydation des organischen Materials mit Kaliumbichromat in verd. Schwefelsäure wurden untersucht. Das erste führt zur Reduktion des Bichromats zu deutlich grün gefärbtem Cr(III) mit allen bei der anorganischen Analyse üblicherweise auftretenden organischen Anionen, ausgenommen Acetat und Salicylat. Störungen durch reduzierende anorganische Substanzen werden durch deren vorherige Oxydation mit Wasserstoffperoxid umgangen. Das zweite Verfahren sieht die vorherige Zersetzung anwesender Carbonate, Bicarbonate oder Cyanate mit verd. Schwefelsäure vor, wonach das organische Material mit Kaliumbichromat-Schwefelsäure zu Kohlendioxid oxydiert wird, das mit Kalklösung nachgewiesen wird. Von den in der anorganischen Analyse üblichen organischen Anionen gibt nur Acetat ein negatives Resultat.

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Résumé On examine les essais préliminaires pour radicaux organiques, fondés sur la carbonisation par chauffage à température élevée ou sur l'action de l'acide sulfurique concentré chaud. Même en appliquant ces deux modes de recherche, certains des acides organiques échappent à l'identification. On a étudié deux autres procédés susceptibles d'être utilisés. Ils reposent sur l'oxydation de la matière organique par le bichromate de potassium en milieu sulfurique dilué. Le premier met en jeu la réduction de l'ion bichromate en ion chrome-III vert caractéristique. Cette réaction se produit avec tous les radicaux organiques habituellement rencontrés en analyse minérale qualitative, sauf avec les acétates et les salicylates. On élimine l'interférence due aux agents réducteurs minéraux par oxydation préliminaire par l'eau oxygénée. Le second procédé met en jeu la décomposition des carbonates, hydrogénocarbonates et cyanates par l'acide sulfurique dilué, suivie d'une oxydation de la matière organique par le bichromate de potassium dans l'acide sulfurique, en gaz carbonique que l'on met en évidence par l'eau de chaux. Seul l'ion acétate donne un résultat négatif parmi tous les radicaux rencontrés habituellement en analyse minérale qualitative.

     

Tautomerism in the 5-pyrazolone series 1(H)-5-pyrazolones and indazolones

Structure (I) is shown to be the correct formulation for the compound hitherto considered to be the “azine” of ethyl acetoacetate; I rearranges to IV. Both IV, 1(H)-3-methyl, and 1(H)-3-phenyl, 5-pyrazolones and related compounds are shown to exist in the enolic form (VII) in the solid state and predominantly so in the solvents in which they are soluble. Similarly the indazolones are found to be represented exclusively by the enolized structure XII. The acetates of both series are reformulated where necessary on the basis of spectroscopic data, and the high frequencies found for the carbonyl groups in the IR are shown to reflect a lack of conjugation with the π-electrons of the heterocyclic ring.     

Tuning of the alpha-terthiophene radical cation coupling reaction using mixed micelles with varying charge density.

The photophysics and photochemistry of alpha-terthiophene (alphaT), compartmentalized in mixed nonionic/anionic micelles, have been investigated with focus on the influence of the micellar surface charge density on the formation of the radical coupling product alpha-hexathiophene (alphaH). By varying the ratio of nonionic-to-anionic surfactants, and assuming ideal mixing, the charge density of the mixed micelles was varied. From Poisson-Boltzmann calculations, performed using the cell model, the electrostatic potential and the counterion activity were estimated as a function of the distance from the micellar surface. Upon excitation, the triplet state of alphaT is formed, from which the alphaT radical cation can be formed by absorption of a second photon. The radical cation can form alphaH if it encounters another alphaT radical cation. Under the experimental conditions used, this implies that the alphaH formation only occurs if the compartmentalized radical cation is able to migrate from its host micelle to another micelle, either via the surrounding bulk or by fusion of two micelles followed by mixing of their contents before micellar fission. The formation yield of the radical cation depends on the charge density of the mixed micelle; a lower charge density, that is, an increased amount of nonionic surfactant, lowers the yield. The yield of the coupling product alphaH, however, does not follow the same trend. A maximum yield of alphaH is found at intermediate nonionic surfactant molar ratios. This behavior is understood in terms of the Poisson-Boltzmann simulation results and by comparing charge-density changes as a function of molar fraction with the changes in counterion activity. The alphaH yield is a result of the balance between an increased possibility of radical cation bulk migration and a lowered electrostatic stabilization of the radical.     

Effect of pressure and temperature on electrolyte conductance in 2-propanol

Equivalent conductances for tetrabutylammonium chloride, bromide, iodide, and perchlorate and lithium chloride were determined in 2-propanol at 10, 25, and 40°C over the pressure range 1 to 3,000 kg-cm^?2. The data are analyzed with the 1975 Fuoss-Onsager equation. The limiting equivalent conductances and association constants show the same level of precision as generally obtained in high precision conductance measurements at 1 atmosphere. The unusual association pattern observed for electrolytes in alcohols persisted up to the highest pressures used in this study.     

Meso-oxidation of some metalloporphyrins

Treatment of porphyrins with thallium(III) trifluoroacetate in the presence of trifluoroacetic acid results in uncontrolled oxidation at the macrocyclic meso-positions, presumably via radical processes. For example, a mixture of the thallium(III) α γ-dioxoporphodimethene (4a; R = Et), the αβγ-trioxo compound (3), and octaethylxanthoporphyrinogen (6) is obtained when octaethylporphyrin (1; R = Et) is oxidised in the presence of air. More controlled oxidation is achieved when the meso-trifluoroacetoxyporphyrin complexes (8a, b) or metallo-oxophlorins (7a, b) are treated with mild bases in air, the major products being metallo-αγ-dioxoporphodimethenes (4b, c).β-Hydroxy-α-oxophlorins (16) are isolated and characterised for the first time; aspects of the chemistry of this novel oxygenated porphyrin system are reported.