It is found that the coloring of caustic liquor produced by the ammonia-soda process is due to chromate in the milk of lime given to the sodium carbonate solution for causticization. But the solid caustic soda, even produced by the ammonia-soda process, contains a little chromate. The coloring of caustic liquor by chromate is found in products of all ammonia process makers in Japan. The existence of chromate not only gives the yellow color to the product, but also has an undesirable effect on viscose production in the rayon industry. Yellow-colored caustic liquor can be discolored by the addition of the reducing reagent. Refining by anion exchange resin is also effective, but there is a risk of the corrosion of the resin by the caustic liquor. As the chromate was identified in the caustic liquor, it was concluded that the abnormal wave of the polarogram caustic liquor was probably due to the hydrolysis current. By measuring the absorbancy of caustic liquor at the wavelength of 370 mμ, the chromate content can be nearly exactly determined. As much limestone contains a considerable impurities, it is not desirable to use the milk of lime for the purification of the brine in the electrolytic-soda process also.
Isoation of the amino acids constituting glumamycin, a new antibiotic, was effected. As a result, α(L), β-methylaspartic acid, besides L-aspartic acid was obtained as an acidic amino acid. In addition to L-valine, glycine, and L-proline, D-pipecolic acid was yielded as a neutral amino acid. Further, α, β-diaminobutyric acid was obtained as a basic amino acid and its structure was established to be α, β-diamino-n-butyric acid. For positive confirmation of the structure the acid was synthesized, and it was found that the N, N-dibenzoyl ethyl ester of the synthetic product and that of the basic amino acid derived from glumamycin were in complete agreement.
Investigation was made of the ether soluble part of glumamycin hydrolysate. After this oily substance was purified by distillation, the distillate corresponded to unsaturated fatty acid, having an epimerical formula C13H24O2. This unsaturated fatty acid was optically active and by oxidation with ozone gave an optically active saturated fatty acid C10H20O2 and malonic acid C3H4O4. Therefore, the fatty acid constituted glumamycin corresponding to 3-isotridecenoic acid.
For the purpose of measuring very small ion currents by the mass spectrometer, a secondary electron multiplier, using the dynodes of copper-beryllium, has been constructed and installed. The amplification by the electron multiplier of various supplied voltages to the conversion dynode was measured for inert gas ions, and the amplification factor and its variation with the supplied voltage to the conversion dynode was compared with both the activated and the electro-polished dynode. For the electron multiplier using the electro-polished dynodes, the amplification was roughly inversely proportional to the square root of the ion mass, while for the activated dynode this was not the case. The average yield of the secondary electrons impacted by electrons on the copper-beryllium dynodes was determined, using the values of γi which had been estimated by extrapolation of the data obtained in a previous study. The increase of the amplification factors of the electron multiplier due to the dynode activation was explained on the basis of an increase in γi and \barδ due to dynode activation, an increase to be attributed to the formation of beryllium oxide layers. In this study, an amplification factor of a 105 order for inert gas ions has been obtained with the electron multiplier constructed with dynodes made from activated copper-beryllium. By using this electron multiplier, ion currents of 10 −19 amperes are easily detectable with a mass spectrometer using a conventional D. C. amplifier.
By using a new molecular model and the new datum concerning the [M]D20(W) of α-D-isorhamnose, the ζOHζCH3 in the case of methyl pentose and the [M]D20(W) of β-D-isorhamnose, now unknown, were re-calculated. The obtained value of ζOHζCH3 was nearly equal to that in the case of substances which have a cyclohexane-ring. The new value of the [M]D20(W) of β-D-isorhamnose satisfies Hudson’s methyl glycoside rule.
The kinetics of the formation of calcium carbide in the solid state reaction of calcium oxide with carbon has been examined by using a thermobalance in the temperature range 1600 to 1800°C and at 50, 100 and 200 mmHg of carbon monoxide. The reaction ratio vs. time curves were parabolic in all experimental runs, and the reaction followed parabolic kinetics: (1−3\sqrt1−x)2=kt. On the other hand, the decomposition of calcium carbide as a successive reaction occurred from the specimen surface and was described as a zero-order reaction. As the reaction velocity depended strongly on the pressure of carbon monoxide, it is considered that the reaction rate is governed by the diffusion process of gas through the product layer, as well as that of solids into the solid and product layer.
The temperature dependences of the 79Br and 127I nuclear quadrupole resonance frequencies in 1,4-dihalogenocyclohexanes were investigated. According to Bayer’s theory (Eq. 8), the torsional frequencies were calculated by the use of the calculated moments of inertia and the experimental values of the temperature coefficients of the resonance frequencies at various temperatures. From a comparison of the torsional frequencies, the line of higher frequency at 77°K in cis-1,4-dibromocyclohexane may be assigned to the equatorial bromine nucleus. All the calculated torsional frequencies decrease with the increasing temperature. Such variation in the frequencies agrees with the variation obtained by Raman studies of various molecules in crystals. The resonance lines in the trans-compounds fade out at temperatures considerably below their melting points.
Using λ 2536.5 excitation the Raman spectrum of single crystal of γ-glycine has been recorded for the first time. Thirty-nine Raman frequencies have been reported. Comparing the spectrum of γ-glycine with its infrared absorption spectrum and also with the Raman spectrum of α-glycine, proper assignments have been given to the internal frequencies. The lattice lines observed in Raman effect and infrared absorption have been satisfactorily accounted for.
Japanese acid clay, a montmorillonite-type one, exhibited a special affinity for cesium-137 from an aqueous solution. The phase epuilibrium of the adsorption was confirmed, and the Kd values were used to analyze the data. The Kd value of cesium was highest in pure water, but it was decreased by increasing the aqueous acid, alkali and salt concentration. When clay which had been treated at 400∼ 500°C was used, the Kd value increased two- or three-fold. This phenomenon corresponds to the formation of 10 Å c-axis spacing and the dispersion of the structural water of the clay. This peculiarity, however, appears only at a low cesium concenration, below 10−6 mol./l. At a higher cesium concentration, the adsorption of cesium depends simply on the cation exchange capacity of the clay; heat-treated clay showed a poorer adsorption. The adsorption of cesium from a fission products mixture was also simply examined.
The proton magnetic resonance spectra of triethylborane, trimethylamine-triethylborane, triethylamine-triethylborane, trimethylamine-trichloroborane and triethylamine-trichloroborane were recorded at room temperature using an NMR spectrometer operating at 40 Mc. The assignments of observed signals were made and the chemical shifts and spin coupling constants were evaluated. The extent of electron transfer from nitrogen to boron in ammonia-boranes is slightly greater than that in borazoles.
Effects of substituents on the characteristic bands of pyrones were examined in the infrared spectra. Ultraviolet spectra of various α- and γ-pyrones were recorded and the application of the spectroscopic results obtained, disclosed the problems of tautomerism and isomerism concering some of the pyrone derivatives.
Reduction using complex metal hydrides was carried out on monocyclic α-pyrones and benzo-γ-pyrone. It was established that generally the hydrogenolysis of the 1,6-linkage of an α-pyrone ring occurred. In benzo-γ-pyrone, carbon-carbon double bond and ketone were reduced. The effects of the substituents on the reactivity of α-pyrone were discussed.
a) The degree of cross-linking observed in films of fatty acid modified alkyd resins increases with the content of unsaturated acids. Moreover, cross-linking is not so effective in raising the Tg as the benzene ring, which has a larger cohesive energy. b) Both the Tg and the degree of cross-linking increase with the increase in the molecular weight of the prepolymer. c) The excess of glycerol employed in fatty acid-modified alkyd resin is effective in raising the Tg and encouraging the progress of the cross-linking. d) Generally, the cross-linking is not soon completed; as time elapses, the Tg rises, and the cross-linking progresses. No change in the Gh with the elevation of the Tg (baked film with the addition of a drier) is considered to be caused by the formation of polar groups by air-oxidation. e) In the early period of drying, a sub-glass transition caused by the unrestrained chain of the acyl groups is observed.
Poly(m-xylyleneadipamide) was synthesized by the polycondensation of m-xylylenediamine and adipic acid, and the resulting polymer was melt-spun to afford a mono-filament. The physical properties of the undrawn filament, the stretched filament, and the stretched and annealed filament were investigated. It was found that the dynamic mechanical behavior and the chemical property of the aromatic polyamide are intermediate between poly-s-capramide and polyethylene terephthalate.
The kinetics of the transition of anatase to rutile have been studied in the temperature range 750∼800°C by means of dielectric constant measurements. The kinetic data can be fitted reasonably well by the first order equation. The transition rate is significantly affected by the heating atmosphere and the flux, and the values of the activation energy show a significantly large difference in these cases. In an air or oxygen atmosphere the value of the activation energy in the transition of pure titanium dioxide is 110 or 116 kcal./mol. and 90 kcal./mol. respectively. When 1% of lithium chloride is added to the titanium dioxide, the value of the activation energy of the transition is 150 kcal./mol.
The effect of the concentration on the absorption spectra of condensed polycyclic aromatic hydrocarbons and their related carbonyl derivatives in concentrated surfuric acid was studied in the concentration range from 10−6to 10−3 mol. per liter. The free energies and heats of formation of these associates were also measured. In the case of the dibenzopyrene molecule in 96 per cent sulfuric acid, it is observed that various kinds of association, such as 8, 16 etc., were obtained in successive steps with the increase in the concentration of the solute, while in the case of carbonyl derivatives, only one kind of associate was observed, the number of degree of association of which was observed to be 2, 4 and 16. In the case of dibenzopyrene in 96 per cent sulfuric acid, where it is believed to be doubly protonated, the cause of association might be explained by the dispersion effect, while the blue-shift of the absorption peak of the monomer is clearly observed in successive steps succession with the increase in the concentration of the solute. However in the case of carbonyl derivatives and dibenzopyrene in 86 per cent sulfuric acid, where they are singly protonated, it is observed that they do not show any blue-shift of their absorption peaks but a lowering of the extinction coefficient. As is illustrated in Table I, their experimental heat of association may possibly not be explained by the dispersion effect alone. It may be necessary to take into consideration some kind of hydrogen-bonding between the carbonyl oxygen atoms and the proton.
1. The single and mixture dyeing of Benzopurpurine 4B (C. I. 23500) and Sky Blue 6B (C. I. 24410) were examined kinetically. 2. The diffusion coefficient of each dye decreased with a decrease in the surface concentration. The apparent activation energy of diffusion at a constant surface concentration was evaluated. 3. In mixture dyeing, the dye distributions in the substrate were considerably different from that in the single dyeing, but there was good agreement between the dye distributions experimentally determined and those theoretically calculated in terms of the thermodynamics of irreversible processes. 4. The interaction between two dyes in the substrate increased with an increase in the sodium chloride concentration in the dye bath and with a decrease in the temperature.
The hydrogenation of ethylene and benzene on two series of copper-nickel alloys, i. e., massive alloys prepared physically and granular alloys prepared chemically, was carried out in order to determine the cause of the disagreement of the catalytic activities which have been found in these alloys. The adsorption of hydrogen on granular alloys was also examined to learn the heat of adsorption and the amount adsorbed; the results were compared with the activities of the alloys. The activities of massive alloys may be interpreted by the Dowden theory, but those of granular alloys could not. The activities of granular alloys were interpreted in connection with the concentration of nickel at the surface, which can be considered to be different from that in the interior. It was concluded that the amount of hydrogen adsorbed, the heat of adsorption, and the catalytic activity of granular alloy are related to the concentration of nickel at the surface.
1. The acid dissociation constants of benzylamine-N, N-diacetic acid, and the stability constants of its chelates with Cu(II), Ni(II), Pb(II), Zn(II), Co(II), Ca(II) and Mg(II) at 25°C and 0.1 ionic strength, have been determined by the pH titration method. 2. o- and p-Nitrobenzylamine-N, N-diacetic acid have been newly synthesized from the corresponding benzylamine. 3. The acid dissociation constants of the above two ligands, and the stability constants of its chelates with Ca(II) and Mg(II), have been determined at 25°C and 0.1 ionic strength.
On the basis of the experimental concentration and temperature profiles for one of the synthesis runs, the experimental rate curve has been drawn on a chart in which lines of constant conversion with reaction rates are given as ordinates and temperatures as abscissa. In a step by step calculation of the temperature profiles from the experimental profiles by the use of a set of analytical solutions of the heat balance equation, which includes the respective constant reaction heat terms given by the step by step distribution plot, the heat transfer coefficients are conveniently chosen to match the calculated profiles with the experimental ones. Taking the heat transfer efficiencies thus obtained into consideration, a comparison of the experimental rate curve with the maximum rate curve on the afore-mentioned chart discloses that, for attaining an efficient performance of the reactor, not only should the heat transfer referred to the outer tube surface be improved, but also the temperature rise in the catalyst bed should be controlled by a suitable means.
As an extension of previous work, the study of chemisorption by desorption rate measurement was carried out for carbon dioxide adsorbed on zinc oxide and nickel oxide, and also for carbon monoxide adsorbed on nickel oxide. For the chemisorption of carbon dioxide, the activation energy of the desorption was increased with the decreasing amount adsorbed from 16 to 40 kcal./mol. on zinc oxide and from 7 to 30 kcal./mol. on nickel oxide. In the case of the chemisorption of carbon monoxide, where the two types of chemisorption are seemingly operating, the activation energy of the desorption for the reversible type ranged from 5 to 18 kcal./mol. A method of distinguishing these two types of chemisorption from the behavior on desorption has been proposed, for it has been found that there are two types of chemisorption for the carbon dioxide-zinc oxide system. From the effect of oxygen treatment at high temperatures on the chemisorption, it was concluded that the effect of the surface barrier, emphasized by Hauffe and others, seems to be only of secondary importance in the above system.