This paper describes quantitative analysis of a mixture of eugenol, cis- and trans- isoeugenol by gas-liquid chromatography with the thermal conductivity detector using silicone D.C. 550, D.O.S., Apiezone L., P.E.G. 1500 and 4000, and D.B.P. as the liquid substrates. The following results were observed. Every liquid substrate was used individually or in combinations of two or three. In the latter cases, the substrates were utilized in a mixed manner and in repeated coating with each of two or three substrates, resulting in the finding upon analysis that D.C. 550 and D.O.S. (mixed) gave excellent results. Twenty four samples of substrates were examined for retention time in the gas chromatograms in comparison with those of eugenol and cis- and trans- isomers of isoeugenol. Among them, carvone, acetyleugenol, diethyl phthalate, n-propyl cinnamate and showed different retention time as compared with those of homologues of eugenol. Thus these substrates indicated as usable, as the inner standard material in the quantitative analysis of gas chromatography. Upon analysis, acetyl eugenol showed migration of the acetyl group to isoeugenol in the sample, resulting in acetylisoeugenol. Carvone and n-propyl cinnamate were found as preferable rather than diethyl phthalate because of less tailing and shorter retention time in gas chromatograms. But carvone was apt to scale out in gas chromatograms even when used in low weight-ratios for a sample measured. Quantitative analysis of the sample prepared (eugenol : cis-isoeugenol : trans- isoeugenol=29.8:33. 8:36.4) was carried out within relative experimental errors of ±1.5%, using n-propyl cinnamate as an inner standard material. No transformation was seen between cis- and trans- isoeugenol in these analyzing procedures.
Sulfuric acid is formed by combustion of fuel containing small amounts of sulfur compounds. The present studies are mainly concerned with fuel additives, which is added to fuel in order to suppress formation of sulfuric acid. Lamp method (JIS K 2421) which determine thiophene in benzen was used to estimate the suppressive effect of various fuel additives. Various fuel additives were added in 2% concentrations to the fuel containing 16.915g of thiophene in 1l benzen-methanol mixture (volume ratio 1:4). The gas produced by burning 10 ml of fuel prepared as above was absorbed by 0.5 M-Na2CO3 aqueous solution and was determined for SO4-2 as BaSO4. Among fuel additives studied, phenols, phosphoric acid ester derivatives, and amines such as urea showed excellent suppressive effects on formation of sulfuric acid.
In the previous paper, the deterioration of frying oils was investigated by the practical frying test protecting the fat surface by means of metal float, and it was observed that oils were protected almost completely from oxidation and polymerization, but the increase of acid value was promoted on the contrary. Of the various factors affecting the rate of deterioration during deep fat frying, the effect of water to the deterioration can not be disregarded. A continuous heating system with controlled water supply, that is the continuous water-spraying and heating system, was developed as a model of commercial deep fat frying. As shown in Fig.-1, the condition of water-spraying, heating temperature and the depth of fat layer and so on, were controlled to maintain a stational vaporization of the discharged water. In the continuous water-spraying and heating system, soybean oil was tested and its chemical and physical changes were determined (Table-1). The effect of specific surface area exposed in air for the deterioration was examined by means of metal float (Fig.-24). As a result, it was observed that the ratio of viscosity increase of the deteriorated oil were proportional to the width of spesific surface area, where the increase of acid value was greater when fat surface was protected by means of metal float. These results were essentially the same with that of previous practical frying test. Accordingly, this continuous water-spraying and heating system is considered suitable as a model of commercial deep fat frying with the simplicity and good reproducibility.
In the catalytic reduction of sperm blubber oil with cadmium-alumina under high pressure hydrogen, conditions for production of unsaturated alcohols were investigated. This catalyst had excellent selectivity for the formation of unsaturated alcohols, but the less water in this reaction system, the higher temperature and the less cadmium content in the catalyst, the more non-alcoholic products were generated. It was considered that those non-alcoholic products were mainly formed by the dehydration of alcohols and were hydrocarbons containing carbon-carbon unsaturated bond at the terminal of molecule in addition to original unsaturated. Desirable conditions were found to be, for instance, partial pressure of water; 2O3O kg cm2, reaction temperature; 300°C and cadmium content in catalyst; approx. 30%. It seems that no appreciable increase in the rate of reduction can be expected under higher hydrogen pressure than those investigated, from the judgment of relation between the initial rate and fugacity of hydrogen. The catalyst prepared by precipitation method showed excellent duarability in activity and retardation in the formation of by-products such as hydrocarbons and trans isomers as compared with the catalyst prepared by impregnation method. So far as the present investigation, it has been recognized that only iron gave better results than original cadmium-alumina among the metals combined in this catalyst.
The changes of the contents of partial glycerides were investigated about rice bran oils of which the extent of hydrolysis was different. Namely, rice bran which was obtained immediately after the rice-cleaning was stored at 25°C and crude oils were extracted from eight bran samples taken up according to circumstances during storage of 18 days. Subsequently, acid value and hydroxyl value of the each oil were determined, and the amount of the mono-, di-, and tri-glyceride in them were determined further. The results showed that acid values and hydroxyl values of extracted oils were within 7.896 and 630, respectively, contents of mono-, and di-glyceride in them were within 12.5% and 613%, respectively ; the most part of monoglyceride was assumed as α-type and a small quantity of β-type was assumed in the early stage of the hydrolysis.
The two methods of synthesizing chlorohydrin stearate were compared and consequently it was revealed that the one step method using benzyltrimethylammonium chloride as the catalyst for the reaction between epichlorohydrin and stearic acid was superior to the two steps method, that is, the reaction of epichlorohydrin with sodium stearate followed by the reaction of hydrogen chloride. The spectra of the related compounds were also explained.
Alkylbenzene Sulf onate (ABS) concentration in the water of the Tama River was measured continuously from Oct. 1962 to Oct. 1966. The results obtained show that the ABS load has been increasing year by year, and that the Tama River has been heavily polluted by its branches into which the domestic sewage and industrial waste are flowing. Pollutant loads of the Nogawa and the Hirasegawa (the branches of the Tama River), considered to be heavily polluted, showed 5 times, 3 times and 2 times as much ABS, COD and NH3-N as those of the main stream of the Tama River.