Giichi Muto

Chromatographic behaviour of alkylbenzenes and alkyl benzoates on porous micro-spherical poly(styrene-divinylbenzene) gel

Abstract Homologous series of alkylbenzenes and alkyl benzoates were analyzed by high-performance liquid chromatography employing a porous micro-spherical poly(styrene-divinylbenzene) gel as the stationary phase with various proportions of methanol and water as the mobile phase. In each series of alkylbenzenes and alkyl benzoates, the elution order followed the order of increasing alkyl chain length. The capacity factors increased with increasing water content in the eluent, but decreased as the column temperature increased. The logarithm of the capacity factor for each homologous series was directly proportional to the carbon number. The reciprocal of the column temperature was also directly proportional to the logarithm of the capacity factor. The results might be explainable in terms of the theory of liquid-liquid partition chromatography.

The crystal structure of Tl-β-alumina

Abstract The crystal structure of Tl2O·11Al2O3 has been determined from three-dimensional X-ray data. The compound forms hexagonal crystals with a = 5.598, c = 22.93 A, and Z = 1 in space group P6 3 mmc . The structure has been refined by least-squares methods with anisotropic temperature factors to an R value of 0.063 for 351 independent reflections collected by diffractometry. The crystal is composed of alternate stackings of the spinel block and the ion-conducting layer, both of which are linked together by the covalently bonded corner-sharing O3AlOAlO3 tetrahedra along the c-axis. The occupational percentages of the mobile ion were determined from the Fourier synthesis and compared with those of Ag- and Na-β-alumina.

Separation of homologous alkylbenzyldimethylammonium chlorides and alkylpyridinium halides by high-performance liquid chromatography

Homologous series of alkylbenzyldimethylammonium chlorides and alkylpyridinium halides with C10-C18 alkyl groups were separated by high-performance liquid chromatography, employing porous micro-spherical poly(styrene-divinyl-benzene) gel as the stationary phase. The recommended conditions are as follows: column, 500 mm × 4 mm I.D.; mobile phase, 0.5 M perchloric acid in methanol; column temperature, 30°. The logarithm of the capacity factor for each homologous series was directly proportional to the alkyl chain length. The reciprocal of the column temperature was also directly proportional to the logarithm of the capacity factor of each constituent. The results might be explainable in terms of liquid-liquid partition chromatography.

Sensitive gas chromatographic determination of phenols as bromophenols using electron capture detection

Abstract Eight phenols, phenol, o -, m - and p -cresol, 2,3-, 2,5-, 3,4- and 3,5-xylenol, were converted into the corresponding bromophenols by reaction with bromine. The optimum conditions for the bromophenol derivative formation of 10 -8 mol of each phenol in 1 ml of ethanol were as follows: mol ratio (bromine/phenols), greater than 400; reaction temperature, room temperature; reaction time, 4 h. The minimum detectable amount of the bromophenols with an electron capture detector was about 0.01 ng, which is about 100 times less than the minimum detectable amount of the non-bromine-containing phenols.

The crystal structure of Rb-β-alumina

Abstract The crystal structure of Rb 2 O·11Al 2 O 3 has been determined from three-dimensional X-ray data. The compound forms hexagonal crystals with a = 5.600, c = 22.87 A, and Z = 1 in space group P6 3 mmc . The structure has been refined by least-squares methods with anisotropic temperature factors to an R value of 0.079 for 331 independent reflections collected by diffractometry. The mobile ion sites and their occupation percentages are discussed in relation to other β-alumina compounds. The covalently bonded corner-sharing O 3 AlOAlO 3 tetrahedra are discussed in relation to the ionic conduction phenomena.

Measurement of homogeneous reaction rate by concentration-step, controlled potential electrolysis

Abstract A concentration-step method was introduced to controlled potential coulometry for the study of chemical kinetics and was named concentration-step, controlled potential electrolysis. In this method, an amount of the reaction agent is added to the electrolytic solution which is maintained in a controlled potential condition and the current-time curve is measured. The current-time curve has a peak and the reaction rate is obtained by measuring the time when the current is maximum. To demonstrate the present method the reactions of ethylenediaminetetraacetato-ferrous complex and several oxidizing agents were studied and the pseudo first-order reaction rate constants were evaluated. The optimum range of the measurement was estimated to be 10−3–102 dm3 mol−1 s−1 and the rate constant of the reaction of potassium bromate and ethylenediaminetetraacetato-ferrous by this method was in fair agreement with that found by polarography.

Pattern display for characterisation of trace amounts of odorants discharged from nine odour sources

The odorants discharged from nine odour sources were classified into eight compound groups and were analysed by a systematic gas-chromatographic technique. The characterisation of trace amounts of the odorants was carried out by using the values for new proposed units (pOUm, pOUa, logOU, OUt and OU; all terms are dimensionless) based on the ratio of the detected concentration to the odour recognition threshold concentration. The graphical representation of these data is effective for rapid recognition of the whole state. A polar co-ordinate pattern display was also proposed for the explanation of the relationship between odour characteristics (odour quality and intensity) and chemical analysis data of the odorants responsible for each odour discharged from nine odour sources. The calculated pOUm and pOUa values of eight odorant groups were plotted on polar co-ordinate circular odour charts. These charts illustrated a characteristic pattern and it was found that the shapes and sizes of each odour chart could characterise the quality and intensity of each odour from the nine odour sources. This was confirmed by investigating examples of processes or factories belonging to the nine odour sources.

Gas-chromatographic determination of concentrations of trace amounts of 46 odorants prepared in air in a 10-m3 stainless-steel odour test room

The determination of the concentrations of trace amounts of 46 odorants prepared at odour threshold levels (in parts per billion) in air in a 10-m3 stainless-steel odour test room was investigated by gas chromatography using two pre-concentration methods, namely cold trapping with liquid oxygen and room-temperature adsorption trapping with porous polymer beads, such as Tenax-GC or graphitised carbon black coated with a small amount of stationary phase (SP-1000 + orthophosphoric acid)(0.3 + 0.3% on Carbopack B, 60–80 mesh). The 46 odorants tested were four sulphur compounds, ten lower aliphatic carbonyl compounds, an aromatic hydrocarbon, seven lower aliphatic mono-alcohols, eleven phenols, six lower aliphatic carboxylic acids and seven indoles. The recoveries of the odorants having boiling-points of less than about 150 °C were quantitative, but those having boiling-points of more than 160 °C gave recoveries of about 50%, except for the phenols, which had much lower recovery levels.

Analysis of Free Nucleic Acid Bases in Photographic Gelatin by Liquid Chromatography

AbstractA method of liquid chromatography was applied to the analysis offree nucleic acid bases in photographic gelatins. It was possible to analyse free nucleic acid bases in photographic gelatins without any pre-treatment of the sample gelatin solution.Highly restraining gelatins contained free nucleic acid bases, while low restraining or inert gelatins contained little of them. These free nucleic acid bases in gelatins were eliminated by an ion-exchange treatment. The pH dependence of physical retardance was changed by the treatment. The effect of free nucleic acid bases on the physical retardance was proved.

Analysis of Nucleic Acid Bases in Photographic Gelatins by High-Performance Liquid Chromatography (on Free Bases and Combined Bases)

AbstractA high-performance liquid chromatographic method was applied to the analysis of nucleic acid bases in photographic gelatins by a cation exchange resin. The sample photographic gelatin was hydrolyzed with hydrochloric acid. The contents of nucleic acid bases were calculated quantitatively from their calibration curves and the chromatograms of photographic gelatins. Highly restraining gelatins contained a relatively large amount of these bases, while lowly restraining or inert gelatins contained little of them. In highly restraining gelatins, the ratio of adenine to guanine was approximately 1: 1. It shows that highly restraining gelatins contained not only nucleic acid but also free nucleic acid bases and so on.