bluuebunny/crossref_metadata_2025 huggingface dataset:
Electron Diffraction Investigation on the Molecular Structure of 1,1,2-Trifluoro-1,2,2-trichloroethane
Authors: Iwasaki Machio
Published: July 2006

The molecular structure of 1,1,2-trifluoro-1,2,2-trichloroethane was investigated by means of the sector-microphoto-meter method of electron diffraction. The existence of the two isomeric forms, Cs and gauche was ascertained and the amount of the gauche form was found to be 76±7 per cent at 20°C. This corresponds to the energy difference of 270±250cal./mol., the gauche form being more stable than the Cs form. The interatomic distances were determined as follows: C–F1=l.379±0.021Å, C–F2=1.329±0.014Å, C–Cl1=1.747±0.027Å, C–Cl2=1.758±0.020Å and the equilibrium angle of the gauche form is 59.5±3.5°, where the C–C bond distance and the bond angles were assumed to be equal to the value of CF2Cl–CF2Cl and CFCl2–CFCl2 molecules, which have already been investigated by the present author.
Studies on Antibiotics and Related Substances. VIII. Syntheses of the Two Enantiomorphs of 5-Methylenecyclopentanone-3-carboxylic Acid
Authors: Kinoshita Mitsuhiro , Umezawa Sumio
Published: July 2006

1) The two diastereoisomeric mixtures (IIa and lIb) of 5-(dimethylaminomethyl)-cyclopentanone-3-carboxylic acid hydrochloride were synthesized from the two enantiomorphs of cyclopentanone-3-carboxylic acid by means of the Mannich reaction.

2) The two diastereoisomeric mixtures (IIIa and IIIb) of methyl 5-(dimethylaminomethyl)cyclopentanone-3-carboxylate hydrochloride were degraded to give methyl (+)- and methyl (−)-5-methylenecyclo-pentanone-3-carboxylates (IVa and IVb), which were hydrolyzed into (+)- and (−)-5-methylenecyclopentanone-3-carboxylic acid (Va and Vb), respectively.

3) It was found that IVa and IVb possess high potency against Staph. aureus and both Va and Vb show significant antitumor activities of the same extent.
Studies on Organic Reagents for Inorganic Analysis. V. m-Nitrophenylfluorone for the Spectrophotometric Determination of Zirconium
Authors: Sano Hirotoshi
Published: July 2006

The spectrophotometric determination of a micro amount zirconium, using m-nitrophenylfluorone, has been described. The method recommended here, which is carried out in 0.1 n hydrochloric acid solution, shows nearly fifty times the sensitivity of the alizarin red S method, about five times that of the quercetin method, and about 1.2 times that of the phenylfluorone method reported previously as the most sensitive reagent by the author and K. Kimura. The solution becomes stable enough to carry on the spectrophotometric determination by adding some cyclohexanol and ethanol, and no precipitation is found for the small amount of zirconium. Furthermore, the stability for increasing acidity in the solution is greater than that of the phenylfluorone method. The method is found to be suitable for the determination of 0 to 0.5 p.p.m. of zirconium. Transfer the sample solution (less than 10 ml.) to a 25 ml. volumetric flask. Then add additional acid to bring the acidity up to 1.0 n hydrochloric acid and 7.5 ml. cyclohexanol-ethanol (1:2) mixed solution, and 5 ml. ethanolic solution containing 3 mg. m-nitrophenylfluorone in that order. Adjust the volume to 25 ml., shake the solution, allow to stand for one hour, and read the absorbance of the solution with a spectrophotometer at 550 mμ with 1-cm. glass cells and distilled water as a control solution. Oxalate, fluoride, phosphate, titanium, germanium, iron(III) and antimony cause serious interference.
Changes of Dynamic Properties of Some Kaolin Minerals by Heat-treatment
Authors: Mochida Shigeru , Kawasaki Isao , Nishimura Yoichi
Published: July 2006

When kaolin mineral is heat-treated at a relatively low temperature region, its density has the minimum value between 500 and 800°C and the maximum at about 1000°C.

The value of dynamic properties of kaolin mineral increases slightly until about 800°C but increases rapidly beyond 1000°C to reach the maximum value. Then, the value is inclined to decrease rapidly beyond the temperatures, at which the maximum value is yielded. Similarly, the filling ratio also has the minimum value at about 800°C and increases rapidly beyond 1000°C to reach the maximum value. This indicates that when kaolin mineral is heat-treated at a relatively low temperature region, its dynamic properties have a close relation with its filling ratio. It is considered that these phenomena are due not only to the sintering of clay mineral by heat-treatment but also to the structural changes as shown in X-ray diffraction data.

The changes of dynamic and physical properties and of the structures of kaolin mineral heated in a closed vessel take place later than those heated in the open air. It may be due to the fact that the oxidation of the organic matters contained in kaolin mineral is oppressed in a closed vessel.
Heat of Solution of Methanolized Cellulose
Authors: Tsuda Yoshizo
Published: July 2006

The heat of solution of methanolysis residue of cellulose fibers was measured and then the difference in the cohesive energy of different samples was estimated. It was elucidated that the cohesive energy of methanolized cellulose corresponds to the experimentally evaluated lateral order.
Studies on Explosion Reaction of Ethylene Mixed with Oxygen or Air. II. On the Explosion Peninsula
Authors: Suga Masao
Published: July 2006

In the previous paper, the explosion limit of ethylene mixed with oxygen and with air by the “admission method” was presented. It was pointed out that the explosion peninsula lies in the region between the first and the second pressure limit of explosion. The results of observation in this region differ from those in thermal explosion.

In the present experiment, the following results have been obtained.

(1) The explosion peninsulas of ethylene-oxygen and ethylene-air mixtures lie approximately in the range of the same temperature and pressure limits as that of carbon monoxide-oxygen mixture.

(2) If ethylene concentration exceeds ca. 25% ethylene with oxygen, the explosion peninsula disappears.

(3) The induction period of explosion in the explosion peninsula is relatively longer than those of other thermal explosions.

(4) In the explosion within the explosion peninsula, the apparent activation energy estimated in accordance with Seme-noff’s theory is of abnormally high value. Merely from these facts, it is difficult to determine the explosion mechanism of ethylene-oxygen mixture, but it is possible for one to assume that the explosion within the explosion peninsula has a different mechanism from other thermal explosions.

If one refers to the studies of Neumann and Serbinoff, Norrish and Food, and Lewis on the explosion of methane-oxygen mixture, he will find that the explosion peninsula which is observed in the explosion limit of ethylene-oxygen or -air mixtures is not always related to the nature of ethylene itself. In other words, ethylene-oxygen mixture is decomposed into carbon monoxide first in the definite range of temperature and pressure. Furthermore, it is considered that carbon monoxide which is produced and accumulated in slow oxidation of ethylene, i. e., slow reaction, is ignited in the definite condition. Thus, if ethylene concentration is greater than the stoichiometric value crresponding to C2H4+3O2=2CO+2H2O, the oxygen which is required to oxidate this carbon monoxide is insufficient, and therefore the explosion peninsula disappears. The conclusion is a little too speculative, but it is considered that the explosion peninsula of ethylene-oxygen or -air mixtures originates in the oxidation of carbon monoxide which is accumulated in slow reaction.
Formation and Aging of Precipitates. XII. Studies on Types of Crystal Growth of Barium Sulfate by Dissolution in Water
Authors: Takiyama Kazuyoshi
Published: July 2006

The oval and rectangular crystals of barium sulfate precipitates seem to grow through the dendritic and perfect crystal growth processes, respectively. These particles dissolve in the process of diffusion washing. The oval particles dissolved slightly show the dendrite structure in them, and the rectangular particles dissolved slightly show the large steps around the particles. Thus these particles proved to have grown through dendritic and perfect crystal growth processes, respectively. The surface of the aged particles of both oval and rectangular crystals become stable by digestion in mother liquid; hereby the dissolution rate of inner parts of particles is faster than that of surface parts of them.
Rapid Colorimetric Determination of Selenium by the Tin (II)-Strong Phosphoric Acid Reduction Method
Authors: Kiba Toshiyasu , Akaza Ikuko , Hachino Hiroaki
Published: July 2006

A new procedure for a rapid determination of selenium has been devised by the present authors. Tin(II)-strong phosphoric acid, previously prepared by the authors, has a remarkable decomposing and reducing power, and selenium in various forms can be reduced to hydrogen selenide which is evolved as a gas from samples. Sulfur in various forms is reduced to hydrogen sulfide at the same time. Solid samples such as pyrite can be allowed to decompose rapidly by simple heating with the reagent in an atmosphere of hydrogen. The gas evolved is introduced into an absorbing solution of 5 n sodium hydroxide. Then, a small volume of 30% hydrogen peroxide solution is added. Thus sodium selenate and sodium sulfate are formed in the solution. After adding an excess of concentrated hydrochloric acid and boiling for about twenty minutes with a reflux condenser, the selenic acid is reduced to selenious acid, while the sulfuric acid remains unchanged. The solution is kept at 45°C for several minutes, and solutions of gum arabic and tin(II) chloride are added successively. The red color of the elementary selenium is measured at 372 mμ by a photoelectric colorimeter. The recovery of selenium is uniform even in the presence of large amounts of sulfur and iron. The analysis of selenium in pyrite was carried out by this procedure, and the results were in good agreement with those obtained by other methods.
Phenothiazine Derivatives. VII. Reactions of Phenothiazines with Sulfuryl Chloride and with Chlorosulfonic Acid
Authors: Fujimoto Manabu
Published: July 2006

Reactions of some phenothiazines with sulfuryl chloride and with chlorosulfonic acid were investigated. With sulfuryl chloride, phenothiazine (I), its 5-oxide (II), and 1,3,7,9-tetrachlorophenothiazine (III) gave the same product, 1,3,7,9-tetrachlorophenazathionium chloride (IV), which yielded the corresponding hydroxide VI by the action of aqueous sulfuric acid and of ethanolic potassium hydroxide. To establish the structural relationship of these substances, mutual transformations were carried out. Treatment of phenothiazine and of its 5-oxide with chlorosulfonic acid gave the inner salt VIII of 3,7-disulfophenazathionium hydroxide, which yielded the inner salt IX of 3-sulfo-7- (chlorosulfonyl)phenazathionium hydroxide by the action of thionyl chloride. Chlorosulfonic acid converted phenothiazine 5,5-dioxide into 3,7-disulf ophenothiazine 5,5-dioxide which was obtained also by the oxidation of the inner salt VIII with 30% hydrogen peroxide in acetic acid.
Action of Reducing Agents on Copper Phthalocyanine and its Chlorinated Derivatives
Authors: Shigemitsu Masahiro
Published: July 2006

Action of reducing agents on copper phthalocyanine and its chlorinated derivatives was studied, and it was found that, while copper phthalocyanine containing no chlorine did not suffer from discoloration, the color of its polychlorinated derivatives darkened. The discoloration, was most conspicuous when 13 to 14 chlorine atoms per phthalocyanine molecule were contained. The chlorinated copper phthalocyanine become stable towared reducing agents when it was exhaustively chlorinated.

It was confirmed that the darkening of the color of pigments was caused by the change of chemical composition, not by the change of size and form of particles.
Protonation Effects on the Electronic Spectra of Pyrazine
Authors: Mataga Shizuyo , Mataga Noboru
Published: July 2006

The protonation effect on the electronic structure and spectra of pyrazine has been studied theoretically employing quantum mechanical calculation. Semi-empirical Hartree-Fock SCF MO’s for pyrazine interacting with two protons have been computed with two different methods, respectively.

i) Electrostatic potential due to proton has been added to the core potential in the total electronic Hamiltonian and nuclear attraction integrals which arise owing to the proton potential have been computed theoretically employing the usual Slater 2pπ AO’s.

ii) The doubly protonated pyrazine has been replaced by doubly charged pyrazinium ion and molecular integrals have been evaluated semi-empirically using valence state ionization potential and electron affinity of the N+ atom.

The calculated spectra with method i are in a very good agreement with the experiment. The calculation with method ii has led to a result which is in rather poor agreement with the experimental observation. On the basis of these results, some discussions about the protonation effect on the electronic structure of this molecule have been given.
The Formic Acid Rearrangement of 3,4-Dimethyl-1-pentyn-3-ol and 3-Isopropyl-4-methyl-1-pentyn-3-ol
Authors: Takeshima Tatsuo , Nagaoka Ken , Yokoyama Masataka , Morita Shigeki
Published: July 2006

The behavior of 3,4-dimethyl-1-pentyn-3-ol (II) and 3-isopropyl-4-methyl-1-pentyn-3-ol (III) toward formic acid was investigated. The carbinols, as in the previous report, were chosen as model ones in which the tertiary carbon atom is adjacent to the carbon atom carrying the hydroxyl group. Both carbinols gave a significant quantity of the respective aldehydes. These aldehydes were easily isolated on simple distillation.

II gave 3,4-dimethyl-3-penten-2-one (IIa) in 45% yield and 3,4-dimethyl-2-pentenal (lib), a new aldehyde, in 5% yield. Ill gave 3-isopropyl-4-methyl-3-penten-2-one (IlIa) in 55% yield and 3-isopropyl-4-methyl-2-pentenal (IIIb) in 6% yield. These carbonyl compounds were characterized. IIIb was hydrogenated to give 3-isopropyl-4-methylpentanal (IV) as the 2,4-dinitrophenylhydrazone.
Analysis of the Multi-azeotropes in Terms of the Zeroth Approximation
Authors: Yamada Ikuho , Yoshida Takatoshi , Kawase Osamu
Published: July 2006

Assuming the zeroth approximation for the vapor-liquid equilibrium in multicomponent systems the authors have analyzed multi-azeotropes, and the following results have been obtained.

1) For the condition of azeotropic formation in multi-component systems, Eq. 8 should hold for all combinations of n components.

2) The constancy of ωij is shown as Figs. 1 to 3.

3) Azeotropic composition effect upon temperature is given by solving Eq. 13, and the breaking temperatures are obtained by substituting Xi=1 or 0 into Eq. 13.

4) Azeotropic temperature can be deduced from Eqs. 2, 4 and 13.
Study on Zinc Oxide-Chromium Oxide Catalyst. IV. Dependency of Catalytic Activity on Catalyst Structure
Authors: Ogino Yoshisada , Oba Masaaki , Uchida Hiroshi
Published: July 2006

So far as catalysts made from pastes of zinc oxide powders kneaded with chromic acid solutions are considered, granules in the reduced ones are built up of extremely fine particles which usually are as small as individual crystallites of zinc chromite spinel as well as zinc oxide. The fine particles appear by way of the large particles of zinc-hydroxychromates in the raw catalysts. However, once the raw catalyst comes to contain a greater amount of chromic acid than that corresponding to zinc-hydroxychromate Iβ, the granules in the reduced one are composed of the larger particles, an individual one of which is an assembly of a number of the crystallites.

On the basis of the results available on the catalyst structures, the intracrystalline promoting action of chromium oxide can be explained from Cremer’s viewpoint of the compensation effect. The catalytic activity can be increased by adding an appropriate amount of acetic acid into the paste, the increase being nearly parallel to an increasing extent of the specific surface area. The increase by the addition, however, is expected only with the catalyst produced from the paste of a low chromic acid content.
The Role of the Cationic Group in Anionic Detergents
Authors: Kashiwagi Maresuke , Ezaki Heihachi
Published: July 2006

Various salts of dodecyl sulfate (DS) and alkylbenzene sulfonate have been investigated surface-chemically and from the viewpoint of their bulk properties. It was shown that these organic salts of DS occupy the same surface area as that of SDS, on the substrate of concentrated anmonium sulfate, independent of the nature of the cationic group attached to the sulfate anion. CMC values determined by two different methods (i. e., surface tension and foaming power) show practically the same value. These results are approximately in accord with the known principle that the number of carbon atoms in the molecule of the normal straight chain colloidal electrolyte of one particular class is the determining factor for the value of CMC, although a slight but definite shift in CMC value is observed with variation in substituting group. On the other hand, bulk properties such as viscosity and solubility are influenced remarkably by the substitution of cationic group in anionic detergents.
Polymerization of Aminoacetonitrile
Authors: Hanafusa Hidesaburo , Akabori Shiro
Published: July 2006

Aminoacetonitrile sulfate was heated with kaolin and/or Japanese acid clay at 120∼140°C for 5 hr. The presence of glycyl-glycine and glycyl-diglycine in the extract and the partial hydrolysate of this reaction product was confirmed by paper and column chromatography.
Hydrothermal Reaction of Aluminumtrihydroxides
Authors: Yamaguchi Goro , Sakamoto Kenichi
Published: July 2006

In saturated vapor, the aluminumtrihydroxides dissolve in the water and the velocity of dissolution of the trihydroxides becomes larger as the temperature rises. When this solution is supersaturated over the solubility of boehmite, transformation proceeds. The alkalinity and the boehmite added to the hydroxides accelerate the transition. The former makes easy the dissolution of trihydroxides, and the latter acts as the seed and accelerates the velocity of the crystallization of boehmite.
Distribution of Neptunium between TBP and Some Mineral Acids
Authors: Ishimori Tomitaro , Nakamura Eiko
Published: July 2006

Neptunium-239 is used as the tracer for studies on solvent extraction behaviors of neptunium in the following system:

1. Nitric acid solution and TBP.

2. Hydrochloric acid solution and TBP.

3. Sulfuric acid solution and TBP.

4. Perchloric acid solution and TBP.

Kd values are measured by combinations of scrubbing techniques and chemical treatments. In nitric, hydrochloric and sulfuric systems, neptunium gives three kinds of Kd, distribution ratio which could be assigned to oxidation states of (IV), (V) and (VI). On the other hand, in the perchloric system neptunium does not show Kd value which should be assigned to the oxidation state (IV).

Some of these results are compared with those of uranium, plutonium and other elements. In the nitric system, neptunium (VI) shows an acid dependence of Kd value similar to those of uranium (VI) and plutonium (VI). Kd values of neptunium (IV) and plutonium (IV) vary in almost the same way against the acid concentration of nitric acid. There is also a strong similarity between acid dependences of uranium (VI) and neptunium (VI) in the hydrochloric system.

Behavior of neptunium (V) are compared with those of protactinium.

Finally a simple method for isolation of neptunium from irradiated uranyl salt is stated.
The Crystal Structure of Bis(succinonitrilo)copper(I) Nitrate
Authors: Kinoshita Yukio , Matsubara Ikuo , Saito Yoshihiko
Published: July 2006

The crystal structure of bis(succinonitrilo) copper(I) nitrate has been determined by two dimensional Fourier method. It is monoclinic P2⁄a with two formula units in a cell of dimensions: a=11.62±0.03 Å, b=5.31±0.01 Å, c=9.53±0.03 Å and β=98.8°±0.2°. The crystal consists of nitrate ions and polymeric chains of the following composition:

(Remark: Graphics omitted.)

These chains run parallel to the a-axis-A succinonitrile molecule takes a gauche form with respect to the central C2–C3 bond. A copper atom is surrounded tetrahedrally by four nitrogen atoms with Cu–N distances of 1.96 and 2.02 Å. These facts are in close agreement with infrared spectral observations.

All the atoms in the group Cu–N–C–C lie almost on a straight line. This fact and the observed C–N distance of 1.14 Å suggest that the bond character in the C–N group may essentially be expressed as C≡N.
Studies on the Sapogenins of Dioscorea tokoro Makino. III Synthesis of Isorhodeasapogenin and Some Reactions of Tokorogenin
Authors: Morita Katsura
Published: July 2006

(1) Reduction of anhydrotokorogenin with lithium aluminum hydride led to a new dihydroxysapogenin, desoxytokorogenin; the structure 25D-5β-spirostan-1β,3β-diol was assigned on the basis of various reactions and theoretical considerations.

(2) Desoxytokorogenin, 25D-5β-spirostan-1β,3β-diol, was incidentally found to be identical with isorhodeasapogenin, the structure of which had so far been left unclarified.

(3) Identity of tokorogenic acid with isorhodeasapogenic acid was also confirmed.

(4) Tokorogenin was correlated with samogenic acid and yonogenin via a diosphenol, 25D-5β-spirost-1-en-2-ol-3-one, whose structure was unambiguously established.
On the Crystal Growth of Zinc Sulfide Phosphor
Authors: Otomo Yoshiro
Published: July 2006

(1) The zinc sulfide, before firing, is a large aggregate of crystallites with the crystal diameter of about 150 Å and contains about 8% of α-form.

(2) The crystal growth of zinc sulfide phosphor takes place at about 500°C regardless of whether there is flux or not, but the rate of the growth is much affected by the flux. Without flux, the crystal grows as step-wise piled layers, but, with flux, it grows isotropically showing no influence from the crystal symmetry. Concerning the above difference, there has been discussion, taking into account the density of kinks at the step-wise surfaces of crystals and the change of diffusion constant of zinc sulfide molecules adsorbed at the surfaces.

(3) The transition, α-form ↔ β-form, of zinc sulfide phosphor is rather easy, but becomes difficult without flux. Also, the transition is completed in thirty minutes of firing at 800°C with the flux of 2 wt.% of sodium chloride, but it is completed within ten minutes of firing at 1000°C.

(4) It is probable that there is a metastable state of α-form at about 600°C, but it requires further consideration.
Studies on Antibiotics and Related Substances. VII. The Structure of Kanamycin
Authors: Umezawa Sumio , It\={o} Yukio , Fukatsu Shunz\={o}
Published: July 2006

Evidence is presented to show that both the two aminohexose moieties in kanamycin are directly joined to deoxystreptamine through hydroxyl groups by glucosidic linkages. Proof for the sites of attachment of the two aminohexose moieties rests on the periodate oxidation of the optically inactive 1,3-diamino-4,6-dihydroxy-5-methoxycyclohexane and its N-acetyl derivative which were obtained by the degradation of exhaustively methylated N-acetylkanamycin by acid hydrolysis followed by acetylation. Kanamycin is therefore represented by formula VII.
On the Reactivity of Amide Group of ε-Caprolactam Derivatives
Authors: Ogata Naoya
Published: July 2006

The dipole moments, infrared spectra and rate constants of hydrolysis of ε-caprolactam derivatives have been determined in order to elucidate the difference in reactivity. The great stability of N-methyl-ε-caprolactam is expected, due to the increase of reasonance of amide linkage. Ring dimer of ε-caprolactam is stable for hydrolysis due to the strong intramolecular hydrogen bonds and the reactivity of ring oligomers of ε-caprolactam increases as the ring becomes larger.
On the Dissolution of Na2O–CaO–SiO2 Glass in Acid and in Water
Authors: Tsuchihashi Shoji , Sekido Eiichi
Published: July 2006

(1) The first step in the attack of water on glass is the exchange reaction between the proton and Na+ on the glass surface. Sodium hydroxide thus produced in the boundary layer opens the Si–O–Si bond, and consequently silica passes into solution.

(2) When the exchange reaction between Na+ in glass and H+ in acid solution takes place, more metallic ions will be drawn out of the network owing to the influence of anions existing in the solution. Consequently more cations pass into the solution, while the silica network will be stabilized by acid so that the silica in the solution will be reduced remarkably.
Complexometric Titration of Rare Earth Elements. Dissolution of the Rare Earth Oxalate with Ethylenediaminetetraacetic Acid and Back Titration with Magnesium Sulfate
Authors: Misumi Seizo , Taketatsu Tomitsugu
Published: July 2006

The processes for dissolution of the oxalate and complexometry to determine the small amounts of rare earth rapidly and accurately, were studied. Crystalline rare earth oxalate was precipitated and filtered. The precipitate was dissolved completely with EDTA in alkaline solution and the excess of EDTA in solution was back titrated with standard magnesium sulfate solution. By this procedure, rare earth in the range of a content about 1 to 5mg., was determined rapidly with a good accuracy.
Bond Localization and the Hyperconjugative Effect in the Aromatic Carbonium Ions. II. Electronic Structures of the Carbonium Ions of Isomeric Xylenes
Authors: Morita Toshifumi
Published: July 2006

By means of the LCAO MO method, the π-electron energies of xylene carbonium ions are calculated, for all possible models, with respect to the positions of proton attack, on the basis of the bond localization hypothesis. It is indicated that the explanation of the basic behaviors of isomeric xylenes is impossible merely by the bond localization theory of their carbonium ions, and hyperconjugation should be taken into account.

It is indicated that, when the difference of hyperconjugation energies between protonated m- and p-xylene is about eight kcal./mol., the experimentally observed basic behavior of m- and p-xylenes is understandable.
Studies on Crystal Hydrates. VI. Thermodynamics of Dehydration of Crystal Hydrates. A New Criterion for the Continuous Zeolitic Dehydration. Capillary Condensation of Water Vapor into Exactly Uniform Pores and an Experimental Test of the Kelvin Equation. Case of Dl-Tris-ethylenediaminecobalt(III) Chloride Hydrate
Authors: Chihara Hideaki
Published: July 2006

A simple theory of the thermodynamics of hydrates is developed, which is able to show that the differential molar entropy of dehydration changes with the water content continuously if the hydrate undergoes zeolitic (continuous) dehydration. In this case the integral molar entropy of dehydration does not agree with the differential entropy. The same is true for the heat contents. For stepwise dehydration, on the other hand, both differential and integral entropies coincide in values. A new criterion, termed “entropy criterion”, is presented that if the differential entropy of the water of crystallization, obtained by subtracting the entropy of dehydration (determined by the pressure measurements) from the standard entropy of water vapor 45.1 e. u., differs greatly from 10 e. u., the hydrate should undergo zeolitic dehydration and should have water molecules weakly bonded to the crystal lattice, from which water can be removed without causing collapse of the lattice. This new criterion is equivalent to using the current “isotherm criterion”.

Dl-[Co en3]Cl3·nH2O (n≤4) presents a notable exception to both criterions in that the crystal undergoes zeolitic dehydration in spite of its entropy of dehydration and its isotherm indicating the stepwise dehydration. The failure of the criterions in this crystal is due to the extreme uniformity of pore structure of the hydrate. The Kelvin equation for calculating the pore radius (giving 5.8Å) from the dehydration isotherm is tested against the pore radius obtained by the X-ray crystal structure analysis (giving 2.9 to 3.4Å). It may be concluded that the Kelvin equation is considered to give only the order of magnitude for micropore size. This cobalt complex hydrate is one of the rarest examples having exactly uniform pores and the criterion for the type of dehydration here presented is still effective in most cases.
Intramolecular Interaction between Hydroxyl Group and π-Electrons. IV. Rotational homers of Alcohols and Shift of νO–H Absorptions in Phenyl Substituted Alcohols
Authors: Oki Michinori , Iwamura Hiizu
Published: July 2006

The authors observed symmetric νO–H absorptions for methanol and tertiary alcohols and unsymmetric bands for primary and secondary alcohols. The unsymmetric band was divided into two bands, assuming that the band is an overlap of the two symmetric bands. The idea of the rotational isomerism was successfully introduced for assigning the band and the following points were concluded.

1) Types I and IV show absorption bands at 3644∼3636 cm−1, type II at 3626∼3629 cm−1, type III at 3615∼3618 cm−1, type V at 3616∼3619 cm−1, type VI at 3608∼3611 cm−1, and type VII at 3613∼3617 cm−1.

2) The exception is dialkylphenylcarbinols which show the νO–H absorptions at about 3620 cm−1 and 3608 cm−1, the former being assigned to type III and the latter to type VII. This ruling-out may be attributed to the steric effect and the rotation around the CPh–Cα axis.

The steric effect on the integrated intensities and on the wave number where νO–H absorption falls is also discussed. The differences between types II and IV and between types III and VI were attributed to the existence of the intramolecular interaction between the hydroxyl group and π-electrons of the benzene nucleus. The same reason may cause allyl alcohol to show its main νO–H absorption at about 3620 cm−1.
Stability of Complexes of Several Carboxylic Acids Formed with Bivalent Metals
Authors: Yasuda Motoo , Yamasaki Kazuo , Ohtaki Hitoshi
Published: July 2006

Stability constants of the bivalent metal complexes formed with several mono- and dicarboxylic acids were determined at 25°C and ionic strength of 0.1. For monocarboxylic acids and several dicarboxylic acids having no double bond or forming larger chelate rings than six membered rings the following stability order held: Pb>Cu>Cd>Zn>Ni. It is very remarkable that lead showed the highest stability among bivalent metals.
The Effect of Chain Branching and Molecular Weight of Polyethylene on its Glass Transition Temperature
Authors: Tanaka K\={o}ji
Published: July 2006

A series of measurements by volume dilatometry were performed in order to know whether short chain and long chain branchings, and molecular weight of polyethylene affected the glass transition temperature or not. The glass transition temperature, Tg, was obtained from the intersection of two straight lines of volume-temperature curve and from the discontinuity of the curve obtained by plotting the volume temperature derivatives as a function of temperature. Tg lowered with the increasing amount of short chain branching and there seems to be a linear relationship between Tg and the degree of short chain branching. No appreciable effect of long chain branching on Tg was observed. Tg rose apparently with the increase of molecular weight, but the true rise of Tg was only less than 2°C as molecular weight increased from 10,000 to 50,000. The degree of cubic expansion above and below Tg increased generally as the amount of short chain branching increased.
Halogen Substitution in Liquid Sulfur Dioxide. I. Formation of Alkyl Halides from Alcohols and Halogens
Authors: Tokura Niichiro , Tada Ritsuro , Igarashi Ryoichi
Published: July 2006

The reaction between aliphatic alcohols and bromine in liquid sulfur dioxide at room temperature was investigated in order to obtain further information concerning the behavior of bromine in liquid sulfur dioxide. The reactivity of the alcohols increased in the order of primary <secondary<tertiary.

In addition to alkyl bromides, higher boiling bromides were also produced. The latter resulted from further elimination, dimerization and bromine addition. The rather complicated feature of the bromination is attributable to the presence of sulfur trioxide secondarily formed in the reaction mixture.
The Self-diffusion of Surface Active Agents in Nylon
Authors: Hayashi Makoto
Published: July 2006

The self-diffusion rates of sodium dodecyl sulfate, sodium tetradecyl sulfate, sulfuric acid and hydrochloric acid in nylon containing various amounts of each solute and their temperature dependence were measured by the surface radioactivity decrease method using 35S and 36Cl.

From the experimental results, it has become clear that the diffusion of the solute in nylon is important in the process towards the attainment of sorption equilibrium of these substances by nylon, and in this case the presence of water in nylon is necessary for the diffusion to take place appreciably. The diffusion coefficients were much smaller than those in their aqueous solutions.

The diffusion rates of the surface active agents depended little on the concentration in nylon compared with those of the inorganic acids. The diffusion rates of sulfuric acid and hydrochloric acid depended largely on their concentration in nylon. This will be due to a difference of the mechanism of diffusion between the former and the latter.

The activation energies of SDS and sulfuric acid for diffusion were considerably great and approximated to those of many substances in solid.
Investigation on Mixed Complexes. IV. The Formation of a Mixed Complex by Reaction of Tetracyanoniccolate(II) with Bis-(dithiooxalato)-niccolate(II)
Authors: Kida Sigeo
Published: July 2006

It has been concluded, by the spectrophotometric method, that 1) potassium bis-(dithiooxalato)-niccolate(II) and potassium tetracyanoniccolate(II) react in solution to form a mixed complex, [Ni(C2S2O2)(CN)2]2−, 2) in the case of palladium(II) and platinum(II), bis-(dithiooxalato)- and tetracyano- complexes do not react in solution, unlike the case of nickel (II), and 3) the dithiooxalate ion in the complex, [Pt(C2S2O2)2]2−, is replaced by the cyanide ion in solution, the tetracyanoplatinate(II) ion being formed, but the formation of the mixed complex, such as [Pt(C2S2O2)(CN)2]2−, is not certain.
The Kinetics of Substitution Reactions Involving Metal Complexes. IV. Reaction between Lead and Zinc-Ethylenediaminetetraacetate Complexes in Aqueous Solutions
Authors: Tanaka Nobuyuki , Kato Kiyoko
Published: July 2006

The kinetic study of the substitution reaction of lead ions and zinc-EDTA complexs in acetate buffer solutions has been carried out with the same procedure as that reported previously. Under the experimental conditions, the reaction is found to proceed simultaneously through three different reaction paths, and the rate constants for three elementary reactions of those reaction paths are determined at ionic strength 0.2 at 15 and 25°C. The heats of activation and the entropies of activation for the three elementary reactions are calculated.
Effect of Ionization on the Behavior of Insoluble Monolayers
Authors: Ikeda Shoichi , Isemura Toshizo
Published: July 2006

The effect of salt on ionized monolayers is treated with a model of “surface phase”, in which ionized groups of monolayers are dissolved uniformly. To obtain the distribution of diffusible ions between the surface and bulk phases, the method of membrane equilibrium and the λ-approximation are employed. The former method is a special case of the latter. The contribution of ionization to surface pressure is calculated thermodynamically. The results derived from the former method are found to be in complete agreement with those derived from the theory of diffuse double layer, if the thickness of surface phase is chosen as 2/κ and the electric potential of ionized groups is twice as high as the membrane potential. On examining two typically different monolayers, the former method reveals some contradiction, although it explains experimental data qualitively. The latter method, which is more general, can overcome the difficulty and gives reasonable values for surface pressure of an expanded monolayer. It is found, however, that even the λ-approximation is still unsatisfactory to describe the behavior of ionized monolayers in the range of area with which they are ordinarily concerned.
On Solvolysis of α-Phosphorus(V) Oxide
Authors: Shima Masako , Hamamoto Kazue , Utsumi Seiichiro
Published: July 2006

1. α-Phosphorus(V) oxide was allowed to react with water, with ethanol or acetone, both dry or mixed with water by adding the powder crystal directly into these liquids. The oxide was also brought in contact with water after being dispersed in diethyl ether or benzene mechanically.

2. The main final hydrolysis products formed in the following cases were tetrametaphosphoric acid by direct action of a large quantity of water, pyrophosphoric acid by anhydrous ethanol, tripolyphosphoric acid by ethanol with a low water content, and highpolyphosphoric acid by anhydrous acetone. Quick contact with water after the oxide has been dispersed in ether or benzene leads to the formation of a larger amount of tetrametaphosphoric acid when these solvents were dry, while the formation of an increased amount of highpolyphosphoric acid was the result when they contained trace quantities of water initially.

3. Separation, identification and estimation of various condensed phosphate species were executed by paper chromatography and colorimetric analysis.

4. Reaction mechanisms were postulated to explain these results. Special attention was given to the solvolytic opening of P–O–P linkages and the accompanying condensation process of phosphate radicals.
Behavior of Some Impurities in the Electro-refining of Iron
Authors: Oka Shumpei , Mukaibo Takashi , Aikawa Hirokazu
Published: July 2006

Phosphate ions were found to deposit themselves on the cathode like a cation. This phenomenon suggests the formation of a complex ion which has positive charges. The results on sulfur confirms the importance of washing which was pointed out by Schafer and Harr in achieving low values of total sulfur in the deposited metal. Silver was eliminated effectively by electrolysis, but it will be still difficult to remove zinc from iron by electrolysis.
Chemical Behaviors of the Intermediates Produced during the Reductive Photobleaching of Eosin in the Evacuated Alcoholic Solution
Authors: Uchida Kengo , Kato Shunji , Koizumi Masao
Published: July 2006

The effect of the addition of isopentane, n-hexane, benzene, cyclohexene, n-hexene and cyclooctatetraene was examined upon the rate of the reductive photobleaching of eosine in the evacuated alcoholic solution. It was found that the saturated hydrocarbons, benzene and COT retard the reaction more or less, COT being most prominent in its effect, while the hydrocarbons with a single double bond (cyclohexene and n-hexene) act, contrary to the authors’ expectation, as the promotors of the bleaching. The retarding effect of the first group was interpreted to be due to the deactivation of the T-state of dye ion by the added substances, but the promoting action of the second group could not be accounted for rationally on the basis of the above scheme. To fit the present results, therefore, a modified scheme was newly proposed in which a certain kind of molecular complex between Dt and RH is formed prior to DH.
Surface Tension and Spinnability of Molten Poly-ε-capramide
Authors: Ogata Naoya
Published: July 2006

Surface tension of molten ε-caprolactam and poly-ε-capramide has been measured by the method of maximum bubble pressure. Surface tension of ε-caprolactam at 252°C is 18 dyn./cm. and it is 16 dyn./cm. smaller than that of ε-aminocaproic acid (34 dyn./cm.). It is estimated from the Ramsay-Shields’ equation that the critical temperature of ε-caprolactam is 463°C. Surface tension of poly-ε-capramide of the polymerization degree \barP is given by the following equation.

γ=10^(0.0022\barP+1.53)+0.06(257-t)

The thread length of molten poly-ε-capramide has been measured by pulling up a glass stick and is represented by the following equation, where L (cm.) is thread length, R0 (cm.) radius of a glass stick, μ (poise) melt viscosity, γ (dyn./cm.) surface tension and V (cm./sec.) pulling rate:

L=4.13R_0(μV/γ)^1/2
Rapid Colorimetric Determination of Mercury by Tin(II)-Strong Phosphoric Acid Reduction Method
Authors: Kiba Toshiyasu , Akaza Ikuko , Kinoshita Osamu
Published: July 2006

A simple and rapid method for the determination of a minute amount of mercury in organic and inorganic compounds was established. This method uses the powerful decomposing and reducing power of tin(II)-strong phosphoric acids. In this method the sample is heated with the regent in the round bottomed flask in a current of carbon dioxide. The mercury vapor evolved is carried with the carbon dioxide into an absorbing vessel which is a separatory funnel containing 10 ml. of 0.1 n potassium permangnate solution and 10 ml. of 10% sulfuric acid. The mercury vapor is oxidized again to mercuric state and the ion is determined colorimetrically by the usual dithizone-chloroform method. After extracting the mercuric dithizonate with chloroform, the absorbancy of the organic layer is measured by a photeolectric colorimeter with a 517 mμ filter. Some organic compounds containing mercury and some inorganic mercuric compounds as mercuric chloride and mercuric and mercuric oxide were analyzed by this method in extremely low concentrations, and satisfactory results were obtained. This method may be applied to various kinds of samples without special pre-treatment.
Effect of Cupric Ion on Oxidation of Benzene Aqueous Solution by Cobalt-60 Gamma-rays
Authors: Hotta Hiroshi , Terakawa Akira
Published: July 2006

The effect of a cupric ion on the radiolysis of benzene aqueous solution can be interpreted by the following reactions of a cuprous ion produced in reaction Cu2++H=Cu++H+. That is, the larger yield of phenol than GW(OH) in the presence of oxygen is due to the increment of OH radical by reaction Cu++H2O2=Cu2++OH−+OH, and no precipitation in the absence of oxygen is due to re-hydrogenation by reactions Ph+Cu+=Ph−+Cu2+ and Ph−+H+=PhH, respectively.
Studies on Thixotropy. I. On the Thixotropic Gelation Process
Authors: Watanabe Takehiko
Published: July 2006

(1) In this system, in which the form of dispersed particles is plate- or rod-like, the thixotropic gelation generally proceeds in two steps.

(2) During the first step of thixotropic gel formation, a loose gel structure may be developed and a rigid gel structure in the second step.

(3) In the case of bentonite, the structural unit which contributes to the yield value of the gel in the first step is cross-linkage and that of the second is linear ribbon.

(4) In the case of vanadium pentoxide, the structural unit is cross-linkage both in the first and in the second step.
Catalytic Activity for Methanol Synthesis of Zinc Oxide-Chromium Oxide-Copper Oxide Catalysts and its Structural Dependency
Authors: Ogino Yoshisada , Oba Masaaki , Uchida Hiroshi
Published: July 2006

A preparative procedure in which copper oxide is introduced into the catalyst by a different way from the usual ones has presented the catalyst of high catalytic activity for the methanol synthesis. The catalyst owes its high catalytic activity to three structural factors, namely, a high catalyst bed density, a larger extent of specific surface area, and a great amount of oxygen loosely bond in catalyst oxides, among which the first factor plays the most important role. The last is effective in improving the specific catalytic activity based on unit surface area, and is in a close relation to the two states, A and B, of different catalytic activities.
The Formation Constants of Metal Acetate Complexes. II. Polarographic Determination of the Formation Constants of Acetatocopper(II), Acetatolead(II) and Acetatozinc(II) Complexes
Authors: Tanaka Nobuyuki , Kato Kiyoko
Published: July 2006

A new procedure for the determination of the formation constants of metal acetate complexes was developed. The procedure is based on the polarographic measurements of the sum of the equilibrium concentrations of the hydrated metal ions and the metal acetate complexes in the presence of an appropriate auxiliary complex forming substance and of the reference metal ions of which the formation constants of acetate complexes are known.

The procedure was applied to the study of acetatocopper(II), acetatolead(II) and acetatozinc(II) complexes, EDTA being used as an auxiliary complex forming substance. The overall formation constants KM(OAc)n (n=1 and 2) for these metal acetate complexes were determined at an ionic strength of 0.2 at 15, 25 and 35°C.
Studies on Thixotropy. II. On the Thixotropic Gel Structure of Bentonite
Authors: Watanabe Takehiko
Published: July 2006

(1) Discussions are carried out on the structure of the thixotropic gel of bentonite on the basis of the relation between the gel strength and the concentration, and the steric conditions of the junction point between two particles participating in structure.

(2) The gel strength is determined by the particular group of particles in the structure which acts as the structural unit.

(3) The particle group which plays the part of the structural unit is not limited to one kind but more than one may coexist in a system. The gel strength is determined by one kind of the particle groups according to the experimental method used.

(4) The structure of the thixotropic gel of bentonite is classified into two types according to the mode of association between particles. One of them is the structure in which linear ribbons, which act as structural units, are formed by the aligned particles linking each other at one point. The other is the structure in which linear ribbons are formed by the particles linking at two or more points on one straight line.
Chemisorption of Hydrogen on Zinc Oxide. II. Rate of Chemisorption and Heterogeneity of the Surface of Zinc Oxide
Authors: Kubokawa Yutaka
Published: July 2006

With respect to hydrogen chemisorption on zinc oxide, the dependence of adsorption rate on pressure and temperature was determined by an abrupt change of pressure or temperature during adsorption. The pressure dependence obtained on increasing pressure differed markedly from that on decreasing pressure, indicating that desorption can not be neglected. The apparent activation energy of slow chemisorption increased from 6 to 15 kcal./mol. as the temperature range becomes higher. Marked differences were found between the rates corresponding to equal amounts adsorbed in the two experiments where the times of contact with hydrogen were different. On the basis of these results, combined with the variation of activation energy of desorption with the amount adsorbed previously, it was shown that for this system the concept of the two types of chemisorption on a uniform surface can not be applied. Instead a postulate of a heterogeneous surface where the activation energy of adsorption and the heat of adsorption varies in the same direction was found to be able to explain all the results obtained.