The phase transition of the polymorphic forms in the binary system, tristearin-tripalmitin, has been studied by X-ray diffraction. (1) The lowest melting form α was obtained by melting and chilling the mixtures, and the next form β' and β was obtained by transition form α-form. All three forms in this binary system formed solid solutions of which long spacings varied with composition of the system. (2) Using the continuously variable specimen-temperature devise, it was observed that α-form in this system transformed into subα-form at -50°C or so and that this phase trasition was reversible. (3) Using the same devise, X-ray diffraction pattern of β' and β-forms at elevated temperature was obtained up to its melting point. It was observed that the specific lattice spacing in β' and β-forms changed at elevated temperatures and authors called β' and β at near its melting point as β'* andβ* respectively. This β'* and β*-forms transformed reversibly into β' and β near at room temperature. (4) Using the same devise, it was observed the α-form transformed into β* in the pure glyceride by heating. In the solid solution, it was concluded that α-form transformed into β'* (or β'), deformed β*, and β* successively. It was suggested that the deformed β* might be imperfectly β* in which the specific crystal face of β* yet developed. It would be concluded that the intermediate pattern named by Hoerr was attributed to mixture of β'* and deformed β*. (5) The value of side spacings of each polymorphic form is summarized as follows : (1) β 4.58, 3.85, 3.69Å (room temp.) β* 4.58, 3.85, 3.75Å (near its mp) It is observed that the last lattice spacing often changed a little in the solid solutions. (2) deformed β* 4.58, broad 3.8 Å (near its mp) (2) β' 4.19, 3.80Å (room temp.) β'* 4.19, 3.85Å (near its mp) (4) α 4.14 Å (room temp.) sub α 4.12, broad 3.7 Å (below -50°C)
Phosphorylcholine (PC), phosphorylethanolamine (PE), glycerylphosphorylethanolamine (GPE) and glycerylphosphorylcholine (GPC) exhibited antioxidant activities in a concentration range from 0.01 to 0.04% in unsaturated fatty acid esters, and these compounds as well as β-glycerylphosphoric acid (β-GP) and tributyl phosphate (TBP) showed synergistic activities with hydroquinone. The infrared spectrum of methyl linoleate (MeL) containing 0.03 % of GPC showed the same characteristic absorption bands as those observed in the case of β-GP and TBP added to the same substrate. These results suggest that a mechanism for the antioxidant activity of GPC also involves an interaction of the PO group possibly with the α-methylene group of the MeL molecule. Accordingly, a mechanism for the synergism shown by GPC, β-GP and TBP with hydroquinone and that reported by Olcott for lecithins and inositol phosphatides with ethoxyquin may not conform with the general concept that phosphate esters act as hydroperoxide decomposer.
Chemical and physical changes of soybean oil were determined after treated in the continuous water-spraying and heating system reported in previous paper and in the continuous heating without water, and the type of deterioration were compared between the both systems (Table-1, Fig.-15). In the presence of water, remarkable changes were observed in the increase of acid value, monoglyceride content and hydroxyl value. In parallel with this, a noticeable colour development were also observed. In the absence of water, however, these changes were very small. These facts indicate that the hydrolysis should not be disregarded in heating of frying oil in the existence of water. On the other hand, thermal oxidative changes in the presence of water about two times greater than without water. However, the effect on promotion of the thermal oxidation was considered as the increase of fat surface exposed in air by the physical agitation of oil during the boiling of discharged water. Accordingly, it was concluded that the major difference of deterioration of frying oil between continuous water-spraying and heating system and continuous heating system without water was the hydrolytic deterioration.
Surfactants (C9H19·C6H4·O· (CH2) 3·SO3Na, C9H19·C6H4· (OC2H4) n·O· (CH2) 3·SO3Na) having propane sulf onate group were prepared from nonylphenol and polyoxyethylene nonylphenol ethers (n =2.7, 6.0, 7.6, 11.2, 13.6, 15.4). Surface active properties in their aqueous so were examined f o rsurf ace tension, foaming-, penetrating-, emulsifying powers, hard water resistance, Krafft point and cloud point. In general, the propane sultone derivatives exhibited excellent solubility, foaming power and hard water resistance, but surface tension was inferior than polyoxyethylene nonylphenol ethers (n=7.6, 13.6) and dodecylbenzene sulfovate. The relationships between the surface active properties and the length of the ethylene oxide chain in the propane sultone derivatives were as follows : (1) Favorable foaming power, penetrating power and surface tension were exhibited by the propane sultone derivatives containing 0 to 6 moles of the ethylene oxide chain. (2) Superior emulsifying power was shown by the propane sultone derivatives containing 10 to 13 moles of the ethylene oxide chain. (3) All propane sultone derivatives having the ethylene oxide group showed excellent hard water resistance.
The oils were obtained from the above mentioned fish by the ether extraction. The properties of the oils (Table-2) and the components of the fatty acids (Table-37) were examined. Iodine value of the above mentioned oils had, in general, 120160. From the result of the gas chromatography of the methyl esters of the fatty acids obtained from those oils, there were not distinct differences on the compositions among the body, internal organs and liver oils. The fatty acids were composed of C10C22 saturated and C12C22 unsaturated (higher unsaturated C20 and C12) acids.
Cupric oleate and various kinds of hydroxycarboxylic acid, or dicarboxylic acid, were added to olive oil and were kept at 50°C for 96 hours. Antioxidation effect for the oil was observed for citric, malic and tartaric acids. Concurrent use of these hydroxycarboxylic acids with antioxidant gives far greater antioxidation effect than solitary use of the antioxidant. Titration curves also proved that such acid as lactic and glycolic acids having weak metal blocking ability tended less in the chelate formation, and that the acid which has strong metal blocking power such as citric, malic, tartaric and oxalic acids was strong in the chelate formation tendency.
Purified mono and di-2-ethylhexyl phosphates and their mixtures were prepared. Alcoholic solutions thereof were titrated with alcoholic KOH solution by an automatic recording titrator. Contents of mono and dialkylphosphates were determined from the differential curves.