Submicro methods for the analysis of organic compounds : The determination of hydroxyl groups

Various procedures were examined for the determination of organic hydroxyl groups. Conventional acetylation methods could not be used on the submicro scale, but the spectrophotometric method based on esterification with 3,5-dinitrobenzoyl chloride followed by extraction of the ester and colour development with alkaline acetone proved reasonably satisfactory for aliphatic alcohols. Acidic hydroxyl groups e.g. in phenolic compounds, were titrated accurately with 0.01 M tetrabutylammonium hydroxide in benzene-methanol solution in a pyridine medium ; visual end-points or potentiometricend-points with glass-silver or glass-in-stream platinum electrode pairs were used depending on the strength of the acidic group. Some differentiating titrations were possible. A general submicro bromination method for phenols was not feasible.     

Titrimetric determination of thiocyanate and thiosulphate ions by oxidation with iodine in alkaline solution

Thiocyanate (2.7-90 mug) and thiosulphate (4.5-90 mug) ions are oxidized by iodine in alkaline media to sulphate ions. After acidification, the excess of iodine is extracted into chloroform, and the iodide ions formed in the redox reaction subjected to an amplification reaction. Either a titrimetric or a spectrophotometric finish may be used. Each thiocyanate and thiosulphate ion results in the ultimate production of 19 and 24 iodine molecules, respectively.     

Molecular emission cavity analysis—a new flame analytical technique: Part V. The determination of some sulphur anions

An investigation of the MECA behaviour of sulphate, sulphite, metabisulphite, peroxodisulphate, thiocyanate, thiosulphate and sulphide ions, has shown that ng amounts of these anions may be determined in samples of a few μl. Metal ion interferences in the determination of sulphate and sulphite are removed by addition of phosphoric acid.     

The gas chromatography, thermal analysis and mass spectrometry of fluorinated lead β-diketonates Determination of traces of lead by the integrated ion-current technique

Preparative details for perfluoroalkanoylpivalylmethanes and their lead chelates are given. Thermal analysis, gas chromatography and mass spectral studies all indicate high thermal stability, but strong column interaction makes successful quantitative gas chromatography difficult. The integrated ion-current technique is applied to determine lead heptafluorobutanoylpivalylmethanate in the range 10^-9–10^-7 g of lead, but a lower detection limit of ca. 10^-14 g is indicated.     

Molecular emission cavity analysis : Part VII. The determination of cadmium

Cadmium salts give an intense cadmium atomic emission in the MECA cavity in a hydrogen-nitrogen-air flame. When a carbon or stainless steel cavity is used, 10–120 ng of cadmium in 5-μl samples can be determined. In the presence of sulphuric acid, anionic interferences are removed. Of the cations, only Fe(III), Cr(III), Mg and Sn(II) interfere seriously.     

The 1,2,4-triazolyl cation: thermolytic and photolytic studies

The generation of the 1,2,4-triazolyl cation (1) has been attempted by the thermolysis and photolysis of 1-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridinium tetrafluoroborate (2) and the thermolysis of 1- and 4-diazonium-1,2,4-triazoles, using mainly mesitylene as the trapping agent. Thermolysis of 2 gave mostly 1,2,4-triazole, together with 3-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridine, 4-(1,2,4-triazol-4-ylmethyl)-2,6-dimethylpyridine, and 4-(2,4,6-trimethylbenzyl)-2,6-dimethylpyridine. Thermolysis of each of the diazonium salts in the presence of mesitylene again gave mainly triazole together with very low yields of 1-(1,2,4-triazol-1-yl)-2,4,6-trimethylbenzene and the corresponding -4-yl isomer in about the same ratio. On the other hand, photolysis of 2 in mesitylene gave mainly 1-(1,2,4-triazol-1-yl)-2,4,6-trimethylbenzene. A photoinduced electron transfer from mesitylene to 2 has been observed and preliminary laser flash photolyses of 2 and the corresponding 2,4,6-triphenylpyridinium salt have been carried out. The observed transients are explained as arising from the first excited states of the pyridinium salts rather than from 1. Ab initio MO calculations are reported and indicate that the predicted electronic ground-state of the triazolyl cation is a triplet state of B1 symmetry with five pi electrons, which corresponds to a diradical cation (1c). Possible mechanisms for the formation of the various products are proposed.     

Redox reactions on columns

In a study of redox reactions on columns, the work of Cerrai and Testa has been extended. It has been shown that insolubility of the redox compound is the most important factor and that adsorptive forces play little or no part. A useful redox column method for the determination of iron and vanadium, which compares favourably with that using a Jones reductor column, has been developed. The redox potentials of several substituted hydroquinones have been measured.     

Preparative gas chromatography of volatile metal compounds-I Separation of aluminium, chromium and iron beta-diketonates

The analytical gas chromatography of a range of fluorinated and unfluorinated beta-diketonates of aluminium, chromium and iron has been studied m detail and conditions have been established for their complete separation; the complexes of trifluoroacetylpivaloylmethane show the best characteristics for this purpose. A range of liquid phases and column conditions have been considered and Apiezon substrates have been shown to give optimal resolution. The technique has been extended to a preparative scale with up to 0.1-g chelate samples, and the efficiency of the process demonstrated by the removal of 2% proportions of two metal complexes from a sample of the third. Implications of the technique for the purification of metals are discussed.