1. The molecular structure of cyanuric chloride and melamine were investigated by the electron diffraction. The following values were obtained by the analysis based on D3h symmetry of the molecules: C-Nr=1.33±0.02 Å, C-Cl=1.68±0.03 Å, and ∠Nr-C-Nr=125±3° for cyanuric chloride: C-Nr=1.34±0.01 Å, C-N0=1.37±0.03 Å, and ∠NrC-Nr=123±3° for melamine assuming No-H=1.04 Å, ∠C-No-H=∠H-N0-H=120°, and the coplanarity of all atoms. 2. Simple MO calculations were applied for both molecules as well as for sym-trichlorobenzene and sym-triaminobenzene. The resulted molecular diagrams were discussed together with the data obtained in the present experiment.
The relationship between layered water and coloration of some complexes between montmorillonite and benzidine or other similar compounds has been discussed, and it is shown that they may be divided into types according to the structures of organic compounds. The shrinkage and swelling of the layer distance of the complex caused by its dehydration and hydration are observed. The coloration of the monofunctional-complex is not so remarkable and that of the bifunctional-complex is remarkable. In the case of monofunctional-complex or the bifunctional-complex with benzidine, the amino-or hydroxyl-radical fixes on one side of the silicate layer, and then, when it is saturated with water, the water molecules get into the silicate layer. On the other hand, in the bifunctional-complex with paramine, as the amino- or hydroxyl-radical fixes on both sides of the silicate layers, the water molecules no longer get into it.
By studying the surface pressure-area and surface viscosity-area curves of the copolypeptide of L-lysine, L-phenylalanine and L-glutamic acid over a range of pH values and salt contents in the substrate, the following four distinct results were obtained: (1) When the concentration of potassium chloride in the substrate was kept constant (0.07 M/litre), the (A)F-pH curve has a minimum area region between pH 5.6 and 8.0 which is parallel to the pH axis and this region corresponds to the isoelectric band of this copolypeptide at this salt concentration. The width of this band was the function of the salt concentration; when the salt content was increased this band became wider. (2) When the pH’s of the substrates was kept constant (pH 2.2), the F-A curves were more expanded at low salt concentrations. This fact could be interpreted by the increment of surface pressure due to the free energy of the electrical double layer which is formed between the ionized groups of the monolayer (NH3+ ions) and the counter ions (Cl− ions). The values of surface potentials calculated from the F-A curves and from Gouy’s equation agreed with each other. (3) The surface viscosities became higher when the salt concentrations in the substrate at constant pH’s were decreased and became maximum at its isoelectric point. The surface viscosity depends markedly on the number of inter- or intra-salt-linkages between -NH3+ and COO− ions and not on the shape of each polymer molecule. (4) The (A)F-pH and (η)A-pH curves could be interpreted in terms of effective free charges and the number of salt-linkages.
1. A bomb calorimeter has been used for the measurements of the heats of combustion of the following five compounds at 20°C and at constant volume: dimethyl diethoxysilane, di-n-propyl diethoxy silane, diethyl silanediol, hexamethyl cyclotrisiloxane and hexaphenyl cyclotrisiloxane. 2. From these experimental results the corresponding heats of combustion and formation at constant pressure have been calculated, and the latter values were compared with the calculated values of the heats of formation derived from the data of the bond energies.
An apparatus for the measurement of dielectric constant in the gaseous state is constructed. The electrical circuit is a heterodyne double-beat type, the oscillators with a remarkably high frequency stability are constrcuted. By testing several types of gas cell, it was found that one of them (cell D) can be used satisfactorily for the present purpose. For the gas filling system, a modification of Groves’ method is employed. Using this apparatus dielectric constant measurement with an error of less than 0.5 per cent can be obtained. The dipole moment of 1,1-dichloroacetone was measured in this apparatus. The moment was found to increase with temperature. This increase is attributed to the increase of the more polar isomer (b), which coexists with the form (a). The energy difference of the two isomers was found to be about 800 cal./mole. This value is smaller than that of monochloroacetone, and the lowering of ΔE was considered to be due mainly to the reduced moment of the C-Cl bonds by mutual induction. It was thereby concluded that the energy difference in these molecules is electrostatic in nature rather than steric.
At first the rigorous and orthodox treatment of the polarographic electrolytic current due to the superposition of an alternating voltage upon a constant voltage is shown and the earlier polarographic studies, in which an alternating voltage is employed, are discussed. Next it is shown that in order to treat the a.c. polarography theoretically, we can profitably assume that the superimposed sinusoidal a.c. voltage is equivalent to the square-wave voltage of the same frequency. In a case when an a.c. voltage, is superimposed upon the usual d.c. voltage, the resulting current becomes a very complicated function of time. It can be shown, however, that the current is the algebraic sum of a.c. component and d.c. component, the latter of which is Fournier’s polarogram and the former Breyer’s polarogram. Some outstanding characteristics of both components are satisfactorily cleared up, and it demonstrated that in such a manner a rational and systematic explanation of a.c. polarography is given.
Fundamental circuit for a.c. polarography, in which a.c. polarogram with varying as well as constant amplitude is automatically registered, was shown. And the close relation between reversibility of electrode reaction and a.c. polarographic behaviour of depolarizers was experimentally verified and another applicability of this method was pointed out.
The d. c. and a. c. components of the electrolytic current observed a. c. polarographically, i. e. the Fournier’s and Breyer’s polarograms, are investigated experimentally for the reversible electro- reductions of cadmium and thallous ions. The result of the experiment shows convincingly the essential legitimacy of our theoretical conclusion.
Bis-alkylsulfonylmethane did react with alkyl p-toluenethiosulfonate giving bis-alkylsulfonyl-alkylmercaptomethane. Bis-alkylsulfonyl-halogenomethane was found to react with metal alkoxide giving original bis-alkylsulfonylmethane. It was also found that bis-alkylsulfonyl-dibromomethane readily reacts with silver nitrate giving the monobromo-compound while its dichloro-analog resists in the same condition. The mechanisms of these reactions were discussed.
1) Addition reactions to the double bond of vinyltrimethylsilane were studied with hydrogen,bromine,chlorine,hydrogen bromide and iodide, and the properties of the products were given. 2) Vinyl-silicon bond was cloven by concentrated sulfuric acid but no reaction occurred with methanolic potassium hydroxide. 3) Reaction mechanisms of the above two reactions of vinyl, allyl or related unsaturated organosilicon compounds were discussed. A conjugated structure involving silicon-carbon double bond in which the silicon atom has an expanded valence shell was postulated for some of these reactions. Such a structure was further confirmed by the shift of νc=c in the absorption spectra of vinyltrimethylsilane. 4) Polymerization reactions of this compound were studied and the steric hindrance by a large trimethylsilyl group in the structural unit of the polymer was discussed, particularly concerning the absence of a high molecular weight polymer in the reaction product.
The relative intensity of fluorescence and the change of absorption spectra were examined when chitosan hydrochloride and other amine hydrochloride were added to the aqueous solution of uranine, eosine and erythrosine, which are all acidic and have no tendency to associate. It was found that in the case of uranine, the interaction between amino group and the dye ion is so strong that it directly influences the absorption band remarkably, and thence the interaction is commonly observed irrespective of whether the molecular weight of electrolyte is high or low. In the case of eosine and erythrosine there exists no such strong interaction between amino group and dye ion because the amino compound of low molecular weight produces no marked change in either fluorescence or absorption; a quite notable change is observed in the case of the amino compounds of high molecular weight; thus for example, the fluorescence at first drops and then recovers as the concentration is increased. The phenomena were interpreted as due to the concentration effect of dye ions gathered around the electrolyte ion by weak attraction. This interpretation is quite analogous to that already applied for basic dyes. There appeared, however, no metachromasy band and this was ascribed to the fact that the acidic dyes have scarcely any tendency to associate; thus our opinion put forth for the case of basic dyes, that the change of aggregation of dye ions is mainly responsible for metachromasy, was confirmed once more in the case of acidic dyes.
Levulinic and monochloroacetic esters are condensed by sodium amide or potassium tert.-butoxide to give the corresponding 2, 3-epoxy-3-methyladipic esters.n-Butyl (B), 2-ethylhexyl (O), and lauryl (L) alcohols were used as alcoholic components of these starting esters. Although the yields were poor, nine new esters, namely the B-B, B-O, O-B, B-L, L-B, O-O, O-L, L-O,and L-L 2, 3epoxy-3-methyladipates were obtained. As for condensing agents, potassium tert.-butoxide was the most excellent, and sodium amide gave also good results, while sodium ethoxide and methoxide gave no desired ester. These new esters would be able to be utilized as a stabilizing plasticizer for poly-vinyl chloride.
The freeze-thaw stability of synthetic latices obtained by the emulsion polymerisation of styrene, methyl methacrylate, methyl acrylate, vinyl acetate and acrylonitrile has been measured at the freeze-thaw cycles of −17.5°C and room temperature. It is found that the addition of ethyleneglycol and poly-ethyleneglycol into the latices increases the stability. The freezing point depression and the electrophoretic mobility of stabilized latices indicate the adsorption of stabilizing additives on the emulsion particles. Finally the adsorption of ethylene glycol and polyethylene glycol on the emulsion particles is determined directly. In consideration of these experimental results the freeze-thaw stability seems to be attained by the adsorption of additives on the emulsion particles.
As the result of the measurements of the interfacial pressure and potential of polyethylene terephthalate and poly-N-vinyl pyrrolidone at the air/water and oil/water interfaces, it is concluded that the ring groups in the main chain make the polymer molecule rigid even at the oil/water interface, while that in the side chain is not essentially different from the chain groups. The film of poly-N-vinyl pyrrolidone is relatively labile on the alkaline substrate.
Among the fused iron catalysts for the syntheses from water-gas, those containing Al2O3 and K2O as principal promoters behaved differently from those containing SiO2, MgO, and K2O as such. With the former, it was well known that the products rich in oxygenates were obtained when the synthesis could be carried out at low temperatures. In the present study, an addition of copper has proved to bring about an increase in oxygenates with a simultaneous decrease of the activity. A marked effect of copper on the yield of alcohols has already been realized at the addition of 0.25% of CuO into the catalyst, while no further remarkable effect has been easily observed with its increasing amounts. The observations of microscopic structures, such as the area, the chemisorption of CO2, and CO showed also considerable changes at this amount of addition. An excess amount of copper is liable to segregate along the grain boundaries and hence seems to contribute little for the promotion. By the addition of Al2O3 together with SiO2 besides the usual promoters such as CaO, K2O etc., a catalyst of the high activity, though of short durability, was obtained. In the product obtained with this catalyst at low temperatures, oxygenates have been extremely small, while those obtained by the additional operation at higher temperature are greater in amount. A particular promoting action, quite different from that of Al2O3, has been ascribed, to SiO2.