Various phenomena of binary systems of (S) - (SSS), (S) - (PPP), (S) - (MMM) and (S) - (OOO) were examined by differential scanning colorimetry (DSC). 1) Endothermic and exothermic peaks obtained by measurement of the metastable and stable states of the binary systems by DSC were assignable to respective endothermic and exothermic peaks of the single component constituting the binary systems. Consequently, phase diagrams of the metastable and stable states can be prepared easily from DSC. 2) Metastable and stable states in the phase diagrams of these binary systems did not show solid solution. Consequently, these binary systems do not form solid solutions in the solid state and the modification points of the two components appear at different temperatures in the phase diagram. Similar phase diagrams were obtained for all these binary systems. 3) The two components constituting the system undergo transition separately, although the transition rate is strongly affected by the second component. Transition rate of (S) in the binary systems is markedly suppressed by (SSS) and (PPP), but accelerated by (MMM) and (OOO). On the other hand, the triglycerides in the binary systems are affected by (S), the transition rate of (SSS) becoming slower and that of (PPP) and (MMM) tending to become faster.
Polymorphism, temperature of phase transition, enthalpy, and entropy of 4 kinds of cis-monounc saturated monoglyceride (C16 : 1, C18 : 1, C20 : 1, C22 : 1) were clarified, and correlation between unsaturated and saturated monoglycerides was examined. 1) Monounsaturated monoglycerides have β, α, and sub-α type polymorphism but sub-α 2 was not observed even in C20 : 1. Transition rate was the slowest in C22 : 1 and the rate decreased in the order of C20 : 1, C18 : 1 and C16 : 1. The transition behavior of these was similar to that of saturated monoglycerides of below C12. 2) Temperature of phase transition, enthalpy, and entropy of modification examined by DSC tended to become higher with increase in the number of carbon atoms. The interval of transition temperatures |α-β| is wider than that |sub-α - α |. The enthalpy and entropy of cis-monounsaturated monoglycerides for β → smelt and α → melt are approximate to those of saturated monoglycerides for α → melt and sub- α → α transition. 3) Temperature of phase transition, enthalpy, and entropy of cis-monounsaturated monoglycerides were markedly lower than those of saturated monoglycerides, although the rate of their decrease was found to have a regular correlation between unsaturated and saturated monoglycerides. This regularity is considered to be correlated to the difference in the mode of hydrocarbon chain oriented in the crystal layer between saturated and unsaturated monoglycerides.
The effects of solid powders on the stability of O/W type emulsion were investigated. It was found that these effects reversed at an contact angle of ca. 60° of solid powders to benzene-carbon tetrachlo ride mixture as an organic phase. Solid powders with contact angle below 60°, Carbon black #55, Philblack-I, sulfur, were found to act as an emulsion breaker. While, solid powders with contact angle above 60°, iron, copper (II) oxide, cadmium sulfide, kaolin, were found to act as an emulsion stabilizer. The empirical equations relating the relative settling-rate constant k to the amount of added powder were obtained. For solid powders to act as an emulsion breaker, k=0.88 Wn where the values of n are 0.062, 0.10 and 0.17 for Carbon black #55, Philblack-I and sulfur respectively. For solid powders to act as an emulsion stabilizer, k=2.70 Wn', where the values of n' are -0.26, -0.30, -0.35 and -0.50 for iron, cupric oxide, cadmium sulfide and kaolin respectively.
A rapid method is described for the separation and determination of nonionic substances in detergents by use of a centrifugal chromatograph. The sample was placed on the center of a circular alumina disk and eluted with 300 ml of a mixed solvent, ethyl acetate/methanol (1 : 1, vol/vol), rotating the disk at 400 rpm. By this method nonionic substances such as alkyl poly (oxyethylene) ether and N, N-bis (2-hydroxyethyl) alkanamide in commercial detergents and shampoos were separated quantitatively within 10 min without the interference from coexisting anionic surfactants. The analytical results agreed with those obtained by the column chromatography on alumina.
The synthesis of lactic acid from 1, 1-dichloroacetone (DCA) was studied. Lactic acid was prepared by the hydrolysis of DCA with active charcoal powder catalyst under the milder conditions, H2O : DCA (mol ratio) =25 : 1, 180°C, in comparison with the reaction without catalyst. Alternatively, lactic acid was prepared by the alkali-acid treatment of DCA in 9397% yield. 2-Chloropropionic acid (CPA) was not detected in the reaction mixture and lactic acid was not yielded under the similar conditions. It seems that the intermediate in the lactic acid formation from DCA is not CPA, but a ketoaldehyde as cited in literatures.