Physical and chemical properties of hydrogenated oils produced at equivalent levels of hydrogenation of a fatty oil are affected to a signficant extent by changes in operating variables in hydrogenation. Although the fatty acid composition of hydrogenated oil may be the primary factor which influences physical properties such as melting behaviours and consistency, the glyceride composition is more closely and directly correlated with these physical properties. Effects of the operating variables upon the fatty acid composition of hydrogenated oil have been dealt with in a number of reports, but their effects upon the glyceride composition are not yet well understood.
In this paper, two hydrogenation runs of an olive oil (I.V. 87.5) were carried out with 0.15% of a commercial nickel catalyst under different conditions, one under relatively selective (180°C, 1.0kg/cm², 200rpm) and the other under relatively non-selective (150°C, 3.0kg/cm², 500rpm) conditions. The hydrogenation was continued until the iodine value has fallen to about 62. Four samples of hydrogenated oils were taken at different stages of hydrogenation, the iodine values of the corresponding samples being approximately same for both runs. Each sample was analyzed for its softening point, S.F.I., trans'is-omen (%) and fatty acid composition. Further, each of the hydrogenated samples and the original oil was separated by argentation-TLC into five fractions. From the yield and fatty acid composition of each fraction, the proportions of four glyceride types, i.e., GS 3, GS 2 U, GSU 2, and GU 3 were calculated.
Results of the experiments indicate that the non-selective hydrogenation favors the formation of high melting glycerides of the GS 3 type at equivalent levels of saturated acid content and accordingly gives S.F.I.-curves with a relatively gentle slope. It is postulated that in the selective hydrogenation the adsorption and desorption of glyceride molecules on the catalyst surface take place very frequently and the more unsaturated glyceride molecules are preferentially hydrogenated as compared to the less unsaturated glyceride molecules, whereas in the non-selective hydrogenation the double bonds remaining in the molecules once adsorbed on the catalyst surface are likely to be hydrogenated more or less preferentially as compared to the unsaturated fatty acid groups of other glyceride molecules.

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In a continuation of the studies of this series, two hydrogenation runs of a cottonseed oil (I.V. 109.8) were conducted with a commercial nickel catalyst under different conditions, one under selective (0.2% catalyst, 180°C, 1.0kg/cm², 200rpm) and the other under non-selective (0.1% catalyst, 150°C, 3.0kg/cm², 500rpm) conditions. The hydrogenation was continued until the iodine value has fallen into 50 approx. Five samples of hydrogenated oils were taken at different stages of hydrogenation, the iodine values of the corresponding samples being approximately same for both runs. Each sample was analyzed with respect to softening point, S.F.I., trans-isomer (%) and fatty acid composition. Each of hydrogenated samples and the original cottonseed oil was separated by argentation-TLC into 5 to 8 fractions. From the yield and fatty acid composition of each fraction, the proportions of ten glyceride types, i.e., G-000, G-001, G-011, G-002, G-111, G-012, G-112, G-022, G-122 and G-222 were calculated. Further, each sample was subjected to permanganate-periodate oxidation, and the resulting azelao-glycerides, as their methyl esters, were analyzed by GLC.
Results of the experiments indicate that monoene-rich glycerides are predominantly formed in the selective hydrogenation, whereas relatively large amounts of fully saturated glycerides are formed in the non-selective hydrogenation. The slope of S.F.I.-curves for non-selectively hydrogenated samples is generally more gentle than that for selectively hydrogenated samples. The GLC-chart of the methyl esters of azelao-glycerides from the original cottonseed oil is well defined, but the charts from hydrogenated samples, especially those from selectively hydrogenated samples, show many unknown peaks besides those corresponding to known azelao-glyceride esters, presumably due to double bond migration during hydrogenation. As in the case with olive oil reported in the preceding paper of this series, it is postulated also in the case of cottonseed oil that in the selective hydrogenation the more unsaturated glyceride molecules are hydrogenated in preference to the less unsaturated glyceride molecules, whereas in the non-selective hydrogenation the double bonds remaining in the glyceride molecules once adsorbed on the calalyst surface are likely to be hydrogenated in some preference to the unsaturated fatty acid groups of other glyceride molecules.

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It is known that composition of positional and geometrical isomeric acids in hydrogenated oils varies with hydrogenation conditions, fatty acid composition of original oils and by catalysts.
In this paper, hydrogenation of an olive oil, oleic safflowerseed oil, safflowerseed oil and soybean oil were carried out with 0.15% of a commercial nickel catalyst under different conditions, one under relatively felective (180°C, 1.5kg/cm², 200rpm) and the other under relatively non-selective (150°C, 3.0kg/cm², 500rpm) conditions. The hydrogenation was continued until the trans- and cis-monoenoic acids came to a content which was able to be isolated by TLC. Samples of hydrogenated olive oils were taken at different stages of hydrogenation, the iodine values of the corresponding samples being approximately same for both runs. Each sample was analyzed for its trans-isomer % and fatty acid composition. Further, each methyl ester of hydrogenated samples was separated by argentation-TLC into saturated, trans-monoene, cis-monoene and diene fractions. Each sample of trans- and cis-monoenoic fractions was subjected to permanganate oxidation in acetone-acetic acid and relative amounts of isomers were calculated from GLC of dibasic dimethyl esters.
From the results of experiments it can be observed as follows. In the case of olive oil and oleic safflowerseed oil major double bond in cis-monoene retained its original position (Δ9) with both hydrogenation runs, and also the double bond in trans-monoene retained most its original position under non-selective conditions, but it was mostly migrated to the Δ10 position under selective conditions. In the case of safflowerseed oil and soybean oil the double bond in cis-monoene mostly retained at Δ9 and Δ12 positions in both runs, and trans-monoene contained chiefly Δ10 and Δ11 isomers in both runs.

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A foam-controlling method of a sodium linear alkylbenzene sulfonate (LAS) in hard water has been studied with sodium laurate as a foam-controlling agent and sodium tripolyphosphate or sodium nitrilotriacetate as a sequestering agent. In the presence of sequestering agent enough to sequester almost all the calcium ions in hard water, the test solutions exhibit high foaming profiles. With decreased concentration of the sequestering agent, however, the excess calcium ions, not sequestered, lead to the production of calcium laurate which destroys the foam of the LAS. Thus, foam-controlling of the LAS in hard water becomes possible by using the sodium laurate and the sequestering agents.

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This paper deals with the synthesis of α-irone from 2, 3-dimethyl-1, 3-butadiene and methyl acetoacetate. The reaction of 2, 3-dimethyl-1, 3-butadiene with methyl acetoacetate by the catalyst composed of palladous chloride and P-phenyl-1-phospha-3-methyl-3-cyclopentene gave 3-carbomethoxy 5, 6-dimethyl-5-hepten-2-one (1 : 1 adduct). From this ketone, α-irone was prepared by the combinations of standard synthetic reactions.

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