Safflower oil samples containing different amounts of the water dissolved in the oil were prepared and the influence of the water content on the autoxidation was investigated by measuring the peroxide value (POV) before and after the autoxidation in oxygen or air for 110h at 50°C. In the autoxidation in oxygen, the influence of the water content may be discussed on the following two cases. The first case covers a range in which the water content is 20900ppm. In this case, the changes of POV decreased with decreasing amount of the water dissolved in the oil. The POV after autoxidation was 24.1 for the sample of 20ppm H2O and 41.5 for that of 244ppm H2O. But POV gradually rised in the range from about 200ppm to about 900ppm. The second case covers a range in which the water content is 9001815ppm. The POV after autoxidation was 42.3 for the sample of 948ppm H2O and 57.8 for the sample of 1815ppm H2O. If it is assumed that the water comprises the hydrogen-bonded water and the free water, the POV seems to increase in proportion to the amount of free water. In the autoxidation in air, the influence of the water content may be grouped into two cases; one covering a range in which the water content is 10266ppm and the other covering a range in which the water content is 2661518ppm. In the former case, the changes of POV decreased with decreasing amount of the water dissolved in the oil. The POV after autoxidation was 0.8 for the sample of 10ppm H2O and 4.6 for that of 266ppm H2O. In the latter case, the POV after autoxidation was 4.6 for the sample of 266ppm H2O and 8.3 for that of 1518ppm H2O. The rate of autoxidation in air was markedly smaller than that in oxygen.
Contrary to the Miklukhin's report that dialkyl dithiophosphoric acid and its salts do not have an exchange reaction with elemental sulfur, it was found that such exchange reaction did occur under our experimental conditions. The reaction was the second order for the concentration of dialkyl dithiophosphoric acid (or its derivatives) and the first order for sulfur concentration. The rate of reaction depended on the structure of the reactant compounds and the solvents. The rate was very small in the solvents containing ethanol. The eight-membered ring sulfur decreased in the system during the reaction, though the total amount of sulfur was constant. From the above experimental facts, it was concluded that an amphoteric polysulfide ion was produced by the reaction of elemental sulfur and dialkyl dithiophosphoric acid (or its derivatives). Therefore, it was proposed that the sulfur exchange does not occur by a bimolecular reaction between dialkyl dithio-phosphoric acid (or its derivatives) and elemental sulfur, but the exchange of sulfur is accomplished by the reaction of the amphoteric polysulfide ions formed and the other acid molecules (or the other derivative molecules).
The solubilites of oxygen in aqueous solutions of surface active substances and related compounds were determined by the gas chromatographic method. For quaternary alkyl ammonium bromides and sodium alkanoates having no micelle-forming ability, the solubilities decreased linearly with increasing concentration. On the other hand, for the surface active substances having micelle-forming ability, the solubilities decreased initially and increased after the critical micelle concentration. On the basis of the relationship between the solubility and the carbon number n for the solutions of sodium alkanoates, CH3 (CH2) nCOONa, the contribution of the polar dissociated group to the oxygen solubility was distinguished from that of the methylene group of alkyl chain and the real contribution of the former was estimated. It was also revealed that the existence of ionic group decreased the solubility by the salting-out effect and the introduction of alkyl group increased the solubility by the hydrophobic interaction. This conclusion is supported from the thermodynamic analysis on the oxygen transfer from pure water into aqueous solutions of surfactants.
The following vicinal diols R1CH (OH) CH (OH) R2 (R1, C10H21C20H41; R2, H, CH3C9H19, R1+R2=C12H25, C14H29, C16H33, C18H37, C20H41) were prepared and their antifoaming powers were determined in order to clarify the relationship between their molecular structure and the antifoaming properties. The ethylene oxide adducts of these diols were also prepared and examined. The antifoaming powers were determined by the Ross and Miles method for the aqueous solution of sodium dodecylbenzene-sulfonate as a foaming agent. These were expressed as functions of immediate reading of foam height (foam production) and reading of foam height after 5min (foam stability), and the concentration of diols.The results of these experiments were shown in Fig.-126. It was found that the antifoaming properties of the vicinal diols were dependent upon their molecular weights and the position of two hydroxyl groups in the molecules. (1) Tetradecanediols, hexadecanediols, and octadecanediols showed excellent foam inhibiting proper-ties; the antifoaming powers of the vicinal diols increased in the order C14_≈_C16_≈_C18>C20>C22>C12>C10>C8_≈_C6. (2) The antifoaming powers of decanediols and dodecanediols were greater when the two hydroxyl groups were located near the center of an alkyl chain, but those of the symmetrical diols were not great. On the other hand, the antifoaming powers of tetradecanediols and hexadecanediols were not affected by the position of two hydroxyl groups (Fig.-26). (3) The introduction of 12 molecules of ethylene oxide to these diols improved their antifoaming powers considerably.
This paper presents a study of separation and determination of a mixture detergent grade linear alkylbenzenesulfonate (LAS) and alkanesulfonate (SAS). By alkali fusion treatment, LAS and SAS were converted to alkylphenols and olefins, respectively. These derivatives were readily separated by silica gel column chromatography. The first fraction n-hexane contained olefins and the second one (ethyl ether) contained alkylphenols. The distribution of carbon chain length of these derivatives was determined by gas chromatography on an OV-101 glass capillary column. Gas chromatographic data agreed well with those of the starting materials. The molar ratio of LAS to SAS was determined by NMR spectroscopy after these compounds were converted to the corresponding methyl esters.
Water-soluble polymers were prepared by the reaction of poly (methyl acrylate) (PMA) with thiols such as α-thioglycerine (TG), 2-mercaptoethanol (ME) or 2-mercaptoethylamine (MEA) in the presence of sodium hydroxide. These polymers reacted with copper (II) ion in a dilute aqueous solution to form complexes which had a good foaming ability. The visible spectra of these complexes changed slightly with pH. Copper (II) ion was removed efficiently from the aqueous solution by means of foam treatment around pH 7 at which the complex solution gave absorption maximum. More than 97% of copper and more than 99.9% of nickel, cobalt, manganese and cadmium were removed by the foam treatment.
γ-Jasmolactone and its related compounds were prepared from succinic anhydride, glutaric anhydride, and furfural as the starting materials. For example, (Z) -4-oxo-7-decenic acid (4) was obtained from succinic anhydride (3) and (Z) -3-hexenylmagnesium bromide (2) in 26% yield. Compounds (4) was reduced with sodium borohydride followed by cyclization to give γ-jasmolactone in 70% yield.
In the presence of quercetin the antioxidative effect of 15 amino acids on the oxidation of lard were examined by using active oxygen method (AOM). None of the amino acids without quercetin in the system had the antioxidative activities for lard. In the presence of quercetin, methionine showed the remarkable antioxidative activities and the other 7 amino acids (leucine, asparagin, glutamic acid, cysteine, histidine, ornithine and lysine) had a little antioxidative effect for lard.