bluuebunny/crossref_metadata_2025 huggingface dataset:
Pre-oxidation by Iodine Monochloride—Potassium Hydroxide and Use of Iodine Monochloride End Point in the Determination of Hydrazine, Thiocyanate, Thiosulfate and Glucose
Authors: Sharma Bechu
Published: July 2006

The principle of hypoiodite (iodine monochloride + potassium hydroxide) pre-oxidation and iodine monochloride end point has been adopted to the determination of hydrazine, thiocyanate, thiosulfate and glucose. The availability of alternative standard titrating solutions (iodate, permanganate and ceric sulfate) and applicability over a range of reductant concentrations are essential features of this procedure.
On the d Orbital of the Sulfur Atom in Thiophene
Authors: Maeda Kôgorô
Published: July 2006

The influence of neighboring atoms upon the diffuse d orbital on the sulfur atom and the possibility of the participation in the hybridization were examined. It might be expected that, with respect to the sulfur atom in thiophene, the participation of d orbitals in the hybridization would take place to a greater extent than predicted by the direct application of free atom parameter by Slater’s rule, owing to the contraction by the perturbation of neighboring carbon atoms.
Theory on the Small Angle Scattering of Light to Determine the Shape, Size and Orientation of High Polymer Molecules in Flow
Authors: Nakagaki Masayuki
Published: July 2006

Small angle scattering of light by streaming flexible high polymer molecules is studied theoretically. It is concluded that the position at which the Zimm plot for infinite dilution cuts the ordinate does not change with the velocity gradient and is equal to 1/M. The initial slope of the Zimm plot, however, varies with the velocity gradient as well as the direction of the observation plane. The quantity g proportional to the initial slope varies with the rate of rotation Ω of a concentric cylinder apparatus according to the approximation equation:

(g/g_0-1)/Ω=A+BΩ

where g0 is the value of g at β=0, and A and B are parameters depending upon the direction of observation.

Now, when a quantity G:

(Remark: Graphics omitted.)

(where β is a quantity proportional to the velocity gradient, the proportionality constant being obtained from the value of A or B) is measured, the value of Gmax is equal to the length of the semi-major axis of the molecule, the observation plane for this Gmax being parallel to the direction of the major axis of the molecule, while the value of Gmin is equal to the length of the semi-minor axis of the molecule, the observation plane for this value being parallel to the direction of the minor axis of the molecule.

The pattern to be obtained by photographing the small angle scattering from a streaming solution of high polymer is discussed. The pattern is expected to be an ellipse, the orientation of the pattern is expected to be rotated by exactly 90° from the orientation of the molecule.
Biochemical Studies on Pearl. IX. Amino Acid Composition of Conchiolin in Pearl and Shell
Authors: Tanaka Shozo , Hatano Hiroyuki , Itasaka Osamu
Published: July 2006

Conchiolin, a kind of screloprotein, was isolated from the pearl and the shell of the pearl oysters. The amino acid composition of con-chiolin was determined by the chromatographic method with the starch column. Relatively large amounts of leucines, alanine, glycine and cystine were found in conchiolin.

Remarkable differences were found in the contents of phenylalanine, alanine and proline between conchiolin from the nacreous substance and that from the prismatic substance.
Chemisorption of Hydrogen on Zinc Oxide. I. Rate of Desorption and Adsorption Isotherm
Authors: Kubokawa Yutaka
Published: July 2006

The rate of desorption of hydrogen chemisorbed on zinc oxide was measured over a wide range of temperatures. The rate at a constant temperature was found to obey approximately the kinetics of the Elovich type. The activation energy of desorption was determined at various coverages, with the result that it increased with decreasing amount from at least about 10∼31 kcal./mol. and then remained constant. The heat of adsorption obtained from adsorption isotherms in the temperature range 300∼370°C was found to be 18 kcal./mol., being roughly constant. Meanwhile, from the isotherms at about 100°C, a heat of adsorption of 6∼8 kcal./mol. was obtained. Comparison between the activation energy of desorption and the heat of adsorption suggests that most part of hydrogen chemisorption on zinc oxide involves an activation energy, its highest value being estimated as 13 kcal./mol.
The Kinetic Study of Surface-chemical Reactions at Extremely Low Pressures. V. The Thermal Reaction between Water Vapor and a Tungsten Filament. Part V
Authors: Hamamura Takuya
Published: July 2006

1) Reaction probabilities above 1950°K are determined.

2) The ratio value O/W of the deposit increases with the rise of temperature.

3) The deposit having ratio value O/W greater than 3 appears colorless in transmitted light.

4) The colorless deposit is composed of tungsten trioxide and the ratio value O/W greater than 3 is ascribed to the production of hydrogen, not being accompanied by the weight loss of filament, since the ratio value is determined from the amount of hydrogen produced and the amount of weight loss of filament.

5) Water vapor decomposes and a part of the oxygen thus produced is taken up by the wall of the apparatus, and hence hydrogen is produced, not being accompanied by the weight loss of filament.

6) The reaction rate and the ratio value O/W of the deposit decrease with the increase of hydrogen pressure, since the oxygen taken up by the wall recombines with hydrogen to form water vapor.
Hydrogen Abstraction from Hydrogen Sulfide Molecules by Methyl Radicals
Authors: Imai Naomi , Toyama Osamu
Published: July 2006

Acetone has been photolyzed in the presence of the varied amounts of hydrogen sulfide in the temperature range from 50° to 140°C. From the analysis of the products at low conversions the initial rates of formation of carbon monoxide, methane and ethane have been determined, which, combined with the mechanism of acetone photolysis already established, give the values of k5/k31⁄2, where k5 and k3 are respectively the rate constants for the reactions CH3+H2S=CH4+HS and CH3+CH3=C2H6. Accepting k3=1013.38 mol−1 cc. sec−1 with zero activation energy as recommended by Shepp, the rate constant of the abstraction reaction is represented by k5=1011.4 exp (−2.6 kcal.mol−1/RT) mol−1 cc. sec−1.
Constitution and Solubility of Vitreous Phosphates and Slags
Authors: Ando Jumpei
Published: July 2006

The diffraction angle of center of X-ray halo of glasses composed of silica, phosphorus pentoxide, alumina, lime, magnesia, sodium oxide and ferrous oxide is principally determined by a ratio of the number of cations coordinated by six (or eight) oxygen ions to that coordinated by for oxygen ions.

Approximate ratio of the number of aluminum or magnesium ions which is coordinated by four oxygen ions to that of total aluminum or magnesium ions can be determined by measurement of X-ray halo using above relations.

Glass formation is closely related to oxygen ratio OR0. Solubility of vitreous phosphates and slags in n/2 hydrochloric acid or 2% citric acid is indicated by the ratios OR1, OR2 and OR3 all of which are calculated from chemical composition and above relations.
Determination of Methyl and Phenyl Groups in Methyl-Phenyl-Siloxane Polymer by NMR Spectroscopy
Authors: Kubota Tsutomu , Takamura Tsutomu
Published: July 2006

Proton spin resonance spectra were recorded for the three binary mixtures, benzene-dioxane, benzene-hexamethylsiloxane and dioxane-cyclooctaphenyltetrasiloxane whose mixing ratios were varied. The peak area due to resonating proton of methyl or phenyl group was found to be directly proportional for all systems to the number of protons which give the peak of respective groups over a wide range of recording conditions.

With the results obtained, the determination of methyl and phenyl groups in methyl-phenyl-siloxane polymer was carried out by the use of the inner reference method using dioxane. Siloxane polymer was mixed with dioxane and the spectrum was recorded for the mixture, the number of each group being calculated from the obtained peak area. The results were compared with those obtained from the infrared analysis and they were in good agreement within the experimental error.
The Volume Change on Formation of Water from its Ions
Authors: Tsujioka Akira
Published: July 2006

Values of the changes of volume on formation of water from the hydrogen and hydroxyl ions in aqueous solutions, at various concentrations at 20°C, have been calculated, by combining the data of volume change on neutralization of a strong acid with a strong base and those on dilution of electrolyte solutions. Furthermore, the dependence of the volume change on the concentration has been derived and checked with the calculated data. The volume change on formation of water from its ions at moderate concentrations at 20°C is given by the equation: ΔVF=23.52−3.10\sqrtC ml. per mole, where C is the concentration of ions in mol./1.
Studies on Organic Peroxides. V. Decomposition of Benzoyl Peroxide by Iron(II)
Authors: Hasegawa Shigeo , Nishimura Norio
Published: July 2006

An investigation of the rate of decomposition of benzoyl peroxide by ferrous ion in ethanol has been made. The rate of the reaction was linearly proportional to the concentrations of benzoyl peroxide and ferrous ion, in accordance with Haber-Weiss one electron transfer mechanism. But the apparent decomposition rate was of the first order. The Arrhenius equation was k1=2.2×1011exp(−14,210⁄RT)mol−1 1. sec−1.
Hydrogen Reduction of a Single Crystal of Nickel Oxide
Authors: Iida Yoshio , Shimada Kenzo
Published: July 2006

In the hydrogen reduction of a single crystal of nickel oxide, the rate of reduction does not always increase with an increase in the reduction temperature. In the range of 350 to 500°C the rate decreases with the temperature, and the rate is the lowest at 500°C. These facts are explained reasonably by the microscopical examination of the surface of the reduced nickel. It is concluded that the desorption of the water formed through the pores is a rate-determining step in the reduction of the single crystal of nickel oxide. The nickel formed on (100) plane of nickel oxide by the reduction has (100) plane as a preferential orientation.
Pyrolysis of Organic Compounds. I. Kinetic Study of the Pyrolysis of Toluene
Authors: Takahasi Makoto
Published: July 2006

Pyrolysis of toluene by the flow technique was carried out under various conditions, and the velocity was measured over the wide temperature range 737∼953°C at contact time 0.02∼0.3 sec. The relation of logk versus 1/T appears to be linear, but the more precise analysis shows a slight concave nature, and therefore activation energy tends to increase, as the reaction temperature is raised. Detailed investigation on its cause was made, and it is presumed that such an increase of activation energy with rise of temperature is mainly brought about by some competitive reaction, but not by experimental conditions. The present author considers that the involvement of ring-hydrogen reaction may compete with the reaction of fission of C–H bond of the methyl group, and such competitive reaction may modify the activation energy of the fission of the methyl bond of toluene, if the experiment is carried out over the wide reaction temperature range.
Dielectric Properties of Polypeptide Solutions. Measurement of the Dielectric Properties of the α-Helix by the Low Frequency Bridge Method
Authors: Wada Akiyoshi
Published: July 2006

The work described above has produced the following conclusions. (1) A large electric dipole moment correspoinding to the α-helix described by Pauling, Corey and Branson is found in EDC and dioxane.

(2) A linear relation between the electric dipole moment and the molecular weight in EDC suggests that the molecule is linear and not flexible.

(3) The critical frequency of the orientation polarization was elucidated by using an equivalent ellipsoid model and the equation for the rotatory diffusion constant derived from Perrin’s equation. This fact will support the conclusion of Doty, Bradbury and Holtzer that the α-helix is fairly rigid in the solution.

(4) In dioxane the α-helix can be found to be associated and to have a different distribution in molecular weight.
Thermodynamic Studies on Cobalt Complexes. V. On the Solubility and the Thermal Dissociation of Aquopentamminecobalt(III) Nitrate and Bromide, and on the Thermodynamic Stability of Monoacidopentamminecobalt(III) Complexes
Authors: Mori Motoshichi , Tsuchiya Ryokichi
Published: July 2006

1. By measuring the solubility and the dissociation pressure of aquopentamminecobalt-(III) nitrate, the standard free energy of formation of the salt and that of nitratopentamminecobalt(III) nitrate produced by the decomposition of the former in the solid state were determined.

2. In the same way the standard free energy of formation of aquopentamminecobalt(III) bromide and that of bromopentamminecobalt(III) bromide were determined.

3. On the basis of these results, the thermodynamic stabilities of three aquopentamminecobalt(III) complexes, several monoacidopentamminecobalt(III) complexes and their ions were determined.
Chemisorption of Hydrogen on Zinc Oxide. III. The Effect of Additions of Foreign Ions to Zinc Oxide
Authors: Kubokawa Yutaka
Published: July 2006

The hydrogen chemisorption on zinc oxide samples modified by the addition of foreign ions such as Li+, Al3+, and Ga3+ was investigated by measuring the rates of adsorption and desorption, and the adsorption equilibrium. The addition of foreign ions gave little or no effect on the maximum values of the activation energy for desorption and of the heat of adsorption, and the activation energies of adsorption in similar temperature ranges. On the basis of these results combined with the effect of oxygen treatment on this chemisorption on zinc oxide described previously, it was tentatively concluded that the variation in the features of hydrogen chemisorption caused by the addition of foreign ions is probably attributable to the change in a heterogeneity of the surface rather than that in the electronic state of zinc oxide. Finally, it was mentioned that the heat of adsorption of carbon monoxide at room temperature was also unaffected by such additions.
Dichroism of Dyes in the Stretched PV A Sheet. III. Direction of Absorption of Pinacyanol Iodide
Authors: Tanizaki Yoshié
Published: July 2006

1. Dichroism of pinacyanol iodide in the PVA sheet was observed in the region higher than 220 mμ, and at least sixteen absorption bands were recognized.

2. The relation of Rd to Rs was analyzed concerning some absorption bands, and it was verified that there are two groups of transitions, one existing along the long axis of the molecule, the other being at right angles to one another in geometry.

3. The absorption group at right angles to one another appears in the shorter wavelength region than about 340 mμ, and it was shown that this is due to the two orthogonal electronic transitions localized in the quinoline nuclei of the molecule.

4. The absorptions of the long axis of the pinacyanol molecule consist of two groups, each involving several bands and it was pointed out that the bands are distributed with nearly constant distance of 1500 cm−1 between adjacent one.

5. It was deduced that the molecule is not a planar and both quinoline planes are far from planar.

6. Sixteen absorptions mentioned above were reasonably classified in their relation to the transition direction or in their correspondence to the molecular structure.
Spectrochemical Study of Microscopic Crystals. XX1. The Dichroism of Tris(ethylenediamine)-cobalt(III) and -chromium(III)2
Authors: Yamada Shoichiro , Tsuchida Ryutaro
Published: July 2006

The dichroism in the visible and ultraviolet region has been quantitatively determined at room temperature by Tsuchida and Kobayashi’s microscopic method with a single crystal of d, l-[Co en3] Cl3·3H2O, d, l- [Co en3] Br3·3H2O, d- [Co en3] Br3·2H2O and d, l-[Cr en3] Cl3·3H2O.

It has been found that the [Co en3]3+ and the [Cr en3]3+ ion show a similar type of dichroism. For both the complex ions, the z-absorption is slightly stronger than the x-absorption in the wavelength region of the first absorption band and much weaker than the x-absorption in the region of the second absorption band.

The results of the measurements are discussed in relation to the electronic state and the optical rotatory dispersion of the complex ions.
On Some Dark-colored Chlorocuprates(I, II) and Related Compounds. I. The Method of Preparation and Some Properties
Authors: Mori Masayasu
Published: July 2006

A series of dark-colored chlorocuprates(I, II) of hexamminechromium(III) and hexammine-cobalt(III) have been prepared. The chemical composition and the color of these compounds have been found to change continuously with the composition of the mother liquor in which they were crystallized.
The Effect of Electron Transfer in the Electronic Structure of Benzyl Radical
Authors: Mori Yuji
Published: July 2006

The method of composite system was applied to the calculation of the electronic spectra of benzyl radical. The results are very similar to those in the previous paper and there is no important difference between these two results though the procedures of calculation are different.

The effect of electron transfer on the transition moments of lower bands of some radicals was discussed.
Reduction of Organic Compounds with Urushibara Catalysts under High Pressure. VIII. Reduction of Acetophenone, Especially with Urushibara Nickel Catalyst Prepared by Various Modified Methods
Authors: Taira Shin-ichi
Published: July 2006

Catalytic reduction of acetophenone with various Urushibara nickel catalysts was studied under high pressure. The U-Ni-A with a small amount of alkali was found to be the most useful. The U-Ni-CB and U-Ni-CA were also highly active as they were in case of the reduction of benzophenone. The activity of the U-Ni-A and U-Ni-B, prepared from preserved precipitated nickel, was the same as that of the catalysts obtained from the freshly prepared precipitated nickel. In addition, it was found that the recovered Urushibara nickel catalyst could be repeatedly used after a simple regeneration process especially in the form of U-Ni-A. Such a regenerated catalyst had practically the same activity as that of the normally prepared U-Ni-A.
Rates of Solvolysis of Di-p-toluenesulfoxycyclohexanes
Authors: Mori Nobuo
Published: July 2006

Rates of solvolysis of cis- and trans-1,2- and-1,4-di-p-toluenesulfoxycyclohexanes were measured at 99.8°C in methanol or in acetic acid. In all cases, the solvolysis was approximately of first order.

Mean rate constants of the solvolysis increased in going from acetic acid to alcohol, and were enhanced by the addition of a small amount of alkali, in agreement with the behavior in solvolysis of primary alkyl tosylates.

The 1,2-isomers were not solvolyzed in acetic acid in 20 hr., and in ethanol containing EtONa in 0.02 mol./1., the ratio of kcis to ktrans was 5.6.

In the case of the 1,4-isomers, the ratio was ca. 0.5 in acetic acid, 0.9 in methanol without alkali, 1.1 in methanol with MeONa in 0.013 mol./1. and 1.6 in methanol with MeONa in 0.02 mol./1.
Organoboron Compounds. I. On the Reaction of n-Butylboronic Acid with Polyvinylalcohol
Authors: Kato Seiji , Tsuzuki Yojiro , Kitajima Shigenobu
Published: July 2006

It has been shown that PVA is partially esterified with n-butylboronic acid, giving products of the form of PVA (Remark: Graphics omitted.)B-n-Bu.

The esterification grade, Eg, of the products is estimated from the boron content. Eg increases with the increasing concentration of n-butylboronic acid used, the maximum Eg being 85.6%. Eg rises from 69.3 to 85.6% as the reaction temperature is elevated from 40 to 70°C.

On treating with n-butylboronic acid PVA shows new absorption bands 1190 and 1390 cm−1 in deeper infrared spectra, which are assigned respectively to –B–C and –B–O bonds. At the same time the OH stretching absorption band at 3280 cm−1 of PVA shifts to a higher frequency, and decreases in intensity with the increasing Eg.
Study on Metal Complexes of Analytical Importance. I. Vanadium Complexes of 8-Quinolinol and 2-Methyl-8-quinolinol
Authors: Nakamura Hiroji , Shimura Yoichi , Tsuchida Ryutaro
Published: July 2006

New complexes, [VO(OH)(CH3-oxin)2], [VO(OH)(CH3-oxin)2(OH2)2] and Na[VO(O)(CH3-oxin)2(OH2)2]·2H2O have been prepared and discussed in relation to the structures.

From experimental evidences of these complexes and of 8-quinolinol-vanadium complexes, we have concluded that the violet form of 8-quinolinol-vanadium complex has a cis configuration and that the red form has a trans one.
Rheological Properties of Hydrogels of Agar-agar
Authors: Arakawa Kiyoshi
Published: July 2006

A theological study was made for the hydrogels and the solution of agar-agar. The viscosity vs. concentration relation exhibits the character of polyelectrolyte. From the stress relaxation data obtained by a chainomatic balance relaxometer the following results were obtained.

1) The behavior of hydrogels of agar-agar is represented by the 6-elements mechanical model.

2) The activation energy of the secondary bond between agar-agar molecules which constructs the gel structure is 4.5∼6.6 kcal./mol.

Then, there was some discussion on the structure of the hydrogels of agar-agar.
On the Temperature Dependence of Spectra of Solvated Anions
Authors: Maruyama Akira , Shimoji Mitsuo , Niwa Kichizo
Published: July 2006

The effect of temperature on the ultraviolet spectra of solvated anions is examined experimentally and theoretically. The shift of the spectrum to the longer wavelength with increasing temperature can be explained in terms of the oscillator model of the solvent molecules. This corresponds to the increase of the ionic radii (or the radius of the cavity) with the temperature rise.
On Some Dark-colored Chlorocuprates(I, II) and Related Compounds. III. X-Ray Study and Reflectance Measurements
Authors: Mori Masayasu
Published: July 2006

The ionic species of Cu(II) in hexamminechromium(III) chlorocuprate(I, II) has been found to be a trigonal-bipyramidal [CuCl5]3− ion. Reflectance measurements have shown the existence of diffuse interaction absorption in some chlorocuprates(I, II) and chloroplumbates (II, IV). A strong charge transfer band of [CuCl5]3− was also found in the neighborhood of 2.7×104 cm−1 for hexamminechromium(III) chlorocuprate(I, II) and hexamminechromium (III) chlorocuprate (II).
Infrared Absorption Spectra of Water of Crystallization in Cobaltous Chloride Hexa- and Dihydrate Crystals
Authors: Gamo Itaru
Published: July 2006

The observed spectra of the water of crystallization were interpreted by the effects of coördination and hydrogen bonding. The total difference in the spectra of the two crystals wasexplained in relation to the difference in their atomic arrangements.
Absorptiometric Determination of Micro-amounts of Iron in Nuclear Grade Graphite and Urania-Graphite Fuel; Nitroso R Salt Method after Coprecipitation of Iron with Manganese Dioxide
Authors: Miyamoto Masatoshi
Published: July 2006

An absorptiometric determination of micro-amounts of iron with nitroso R salt was satisfactorily applied to the routine analysis of nuclear grade graphite. An ashed sample is brought into a solution and the color of iron is developed by the reagent with the aid of hydroxylamine sulfate. Adjustment of pH to the optimum range is easily made by the addition of a definite amount of an acetate buffer. The intensity of the color is measured at 715 mμ. The range of the determination covers 2 to 75 p. p. m. when 1 g. of a sample is taken, the final volume being 25 ml. In the case of a sample of urania-graphite fuel, the ash is fumed with perchloric acid and a preliminary separation is made by coprecipitation with manganese dioxide which is produced by the oxidation of manganese (II) ion with hydrogen peroxide in a hot ammoniacal carbonate solution. The recovery of iron is quantitative and the removal of diverse ions is satisfactory. All of the uranium is also removed here. Contamination with foreign iron from a drill used for sampling and from the platinum or percelain crucibles used is negligible. The effect of diverse ions on the absorptiometry was also examined.
Some Observations on the Process of Dehydration and Rehydration of Gypsum by Means of Proton Magnetic Resonance
Authors: Saito Tatsuo
Published: July 2006

1) On the thermal dehydration in vacuo, the characteristic single sharp peak of proton resonance was observed for the specimens dehydrated at the temperature from 70 to 150°C.

It is assumed that this single sharp peak is attributed to the zeolitic water probably existing in the space of the crystal lattice of soluble anhydrite and that this zeolitic water can be interpreted as being a part of the water molecules which originate from dihydrate during the thermal decomposition.

2) Calcium sulfate hemihydrate was formed by the rehydration of gypsum dehydrated in vacuo. This hemihydrate showed the proton resonance spectrum corresponding to the signal of three spin type with an intensive center peak. This intensive center peak can be interpreted as an indication of the movable water existing in the space of the crystal lattice of hemihydrate.

3) This hemihydrate was considerably stable under the atmosphere of saturated water vapor. This was ascertained by the NMR measurements.
Silanes. Vibrational Assignments and Frequency Correlations
Authors: Janz George J , Mikawa Yukio
Published: July 2006

The status of knowledge relative to the vibrational assignments, molecular structure, and spectral data for a series of about one hundred silanes has been surveyed and is reported in brief tabular form. A scheme of simplified vibrational modes is discussed, and used to develop the assignment of fundamentals for some fifty five silanes. Some new assignments are proposed in the light of a correlation rule which has been developed. Tables of characteristic frequencies, and the best values for bond distances, based on this work, are presented.
Determination of Ortho-, Pyro- and Tripolyphosphate by the Use of α Small Column of Ion-exchange Resin
Authors: Ohashi Shigeru , Takada Shichiro
Published: July 2006

The authors presented the new rapid method for the determination of ortho-, pyro- and tripolyphosphate in the mixture by the use of a small column, 2.6 mm. in diameter and 60 mm. in height, of ion-exchange resin, Dowex 1–X4 (200∼400 mesh). The continuous-gradient elution method was applied and the paper micro-fraction collector was used. For example, by the use of 2 m potassium chloride of pH 4.5 as the stock solution, 100 μg. as phosphorus of each phosphate species can be separated by letting only 79 drops of the eluant flow. The quantitative data obtained by the present method were well coincident with the calculated values or the data obtained by the paper chromatography.
The Infrared Absorption Spectrum of 1, 2, 4, 5-Tetrachlorobenzene in Vapor State
Authors: Saëki Shinnosuke
Published: July 2006

The infrared absorption spectra of ordinary and deuterated 1,2,4,5-tetrachlorobenzenes were measured in the vapor state using the high temperature cell. For the results obtained by the measurements we proposed two possible assignments of the fundamental infrared bands, and made the discussion comparing these two tentative assignments. However, at present we have no experimental base upon which we can decide the superiority of one to the other. In order to solve this difficulty we are going to make an investigation of the spectra of these molecules in the far infrared region as well as the calculation of the exact force constants of the chlorobenzenes.
π Electronic Structure of Cinnamaldehyde
Authors: Inuzuka K\={o}z\={o}
Published: July 2006

State energies of the cinnamaldehyde molecule are calculated by the simple LCAO-MO method, including configuration interaction and assuming the C2v symmetry. The results of the calculation conform well with the observed absorption bands lying in the 2000∼3000 Å region. In cinnamaldehyde the 280 mμ band is assigned to the intramolecular charge transfer band. The B2− band which we could not find in spectrum of cinnamaldehyde may be covered under the charge transfer band which is greatly shifted toward the red as the result of extension of conjugation. In the region of the band IIc two peaks at 224 and 218 mμ represent two different transitions, respectively. The former is assigned to the B2+ type transition and the latter to the transition in the acrolein group.
The Chemical Reaction in Silent Electric Discharge. I
Authors: Morinaga Kihei , Suzuki Momotaro
Published: July 2006

1. The ozone yield Y from oxygen gas in the silent electric discharge in a Siemens ozonizer is proportional to the pulse current which was measured from an oscillogram where Y is referred to τ=0 value. The proportionality is valid independent of the gap distance d between electrodes and the effective area A of electrodes.

2. The above ozone yield Yi which is referred to τ=0 and further to unit pulse current is proportional to A/d.

3. The reason of the above relationship briefly discussed.
Mass-spectrometric Study on Ionization and Dissociation of Diethyl Ether by Electron Impact
Authors: Kanomata Ichiro
Published: July 2006

A mass spectrometric study on ionization and dissociation of diethyl ether has been carried out.

The M/e=31 ion is the most abundant among the ions produced by 75 eV. electron impact and the M/e=29, 59, 45 and 74 ions are abundant in this order next to M/e=31 ion.

The appearance potential measurement of these ions leads to the following conclusion. The ions are formed by the removal of one of the lone pair electrons of the oxygen atom in the molecule.

By considering the trivalent structure of O+ and by applying the bond energy additivity, which is adequate for hydrocarbons, to such an ionized dissociation process the producing processes of such ions can be satisfactorily revealed.

The stabilization energy for the formation >C=O+- structure is obtained as 54 kcal./mol. by such a calculation.
Proton Magnetic Resonanace Spectra of p-Cresol
Authors: Yamaguchi Ichiro
Published: July 2006

The proton magnetic resonance spectra of p-cresol in several solutions were measured. The concentration dependence of the resonance in methyl protons suggests no remarkable effect of the hydrogen bonding on methyl protons. The resonance in the hydroxyl proton shows characteristic concentration dependences which are ascribed to the dissociation of the associated molecule in benzene, chloroform and carbon tetrachloride solutions and to the formation of new hydrogen bonds with solvent in acetone, dioxane and pyridine solutions.The ring proton resonance spectrum is a single line in concentrated range whereas it is an A2B2 type spectrum in dilute range. The splitting of the spectrum in dilute solutions is ascribed to the change in the screening of the proton ortho to the hydroxyl group affected by the change in the intermolecular hydrogen-bonding situation. The shielding of the proton ortho to the methyl group appeared to be unaffected by the same change.
Nuclear Magnetic Resonance in Amino-group of Aniline Derivatives
Authors: Yamaguchi Ichiro
Published: July 2006

Concentration dependence of the chemical shift of amino protons in aniline derivatives in carban tetrachloride and acetone solutions were measured. The chemical shift of the amino proton in aniline derivatives is revealed to be clearly dependent on the existence of the ortho-methyl group. In carbon tetrachloride solutions, the concentration dependence of the resonance lines is slight, suggesting that the association of the solute molecules by hydrogen bonding is very weak. In acetone solutions, the dependence suggests hydrogen bond formation between solute and acetone. The base strength of aniline derivatives appeared to have no direct correlation with the magnitude of the chemical shift of amino proton in these compounds. The ring proton spectra of dimethyl aniline are slightly concentration dependent. The resonance in the ortho-protons appers to be displaced to a lower field on dilution and this tendency was ascribed to the change in the electrostatic field at the proton arising from the N–H bond moment change by hydrogen bond formation.
Infrared and Raman Spectra of Diethoxymethane and Diethoxymethane-d2
Authors: Nukada Kenkichi
Published: July 2006

Infrared spectra between 3000 and 280 cm−1 (vapor and liquid phases) and Raman spectra (liquid phase) of diethoxymethane (C2H5·OCH2OC2H5) and of diethoxymethane-d2 (C2H5OCD2OC2H5) were observed and the assignment of the spectra is presented with the assumption that these molecules take one form both in the vapor and liquid phases. In the assignment, that of the homologues such as dimethoxymethane, its deuterated compounds, methoxyethoxymethane and diisopropoxymethane, are taken into consideration.
Structure of Enteromycin. III. Structure of Demethoxyenteromycin
Authors: Mizuno K\={o}mei
Published: July 2006

The structure of dehydroxydihydrodemethoxy-enteromycin was assumed to be N-glycyl-3-aminoacrylic acid. From the fact that catalytic reduction of O-acetyldemethoxyenteromycin afforded acetic acid and glycyl-β-alanine, and that N-methyl- and O-methyldemethoxyenteromycin methyl ester have the partial structures, of N-(N-oxy-methyliminoacetyl)- and N-(O-methylhydroxyiminoacetyl) -, respectively, it was made clear that demethoxyenteromycin is an aldoxime having the structure of N-(hydroxyiminoacetyl)-3-aminoacrylic acid.
Oxidation of Ferrous Ions in Aqueous Solutions by Cobalt-60 Gamma Rays. II. Effect of Anions at High Dose
Authors: Hotta Hiroshi , Ohno Shin-ichi
Published: July 2006

The G(Fe3+) of air-free acidic ferrous sulfate solutions decreases gradually with the increase of dose due to the re-reduction of ferric ion produced. The decrement depends on the property of anion as well as sulfuric acid in the solution in the order of

Cl−>Br−>SO42−>F−

The relative reduction rate of ferric complexes is obtained in Table IV as a result of the estimation of respective complexes in the solution ; that is, ferric chloride and bromide complexes promote the reduction of ferric ion, and ferric sulfate and fluoride complexes suppress it.
Raman Spectra of p-Dichlorobenzene and p-Dichlorobenzene-d4
Authors: Saëki Shinnosuke
Published: July 2006

The Raman spectra of ordinary and deuterated p-dichlorobenzene were measured in solutions. The qualitative depolarization ratios of observed Raman lines were also measured by the two exposure method using the polaroid cylinders. On the basis of these results, the assignments of normal vibrations for these substances were determined. The assignments for the in-plane normal vibrations (species Ag and B3g) were verified applying the product rule.
Photoconductivity of Polycyclic Aromatic Compounds
Authors: Sano Mizuka
Published: July 2006

The voltage, light intensity, and temperature dependences for photocurrent in multi-ring compounds were studied as well as the photocurrent produced by the limited-area illumination. The photocurrent was found to be ohmic over the range of voltage employed. The photocurrent increased linearly with the intensity of light in the region of low light intensity, while it increased as the fractional power of the light intensity in the region of high intensity. The photocurrent increased with an increase of the temperature, and the activation energy of the photocurrent was found to be independent of the wavelength and the intensity of illumination.

The signs of the thermoelectric power as well as the polarity for the maximum photocurrent, and the experiment on the limited-area illumination indicated that the conduction in polycyclic aromatic compounds was due predominantly to electrons which were generated in the bulk of aromatic film.
Non-Empirical Calculation of the π-Electronic Structure of Cyclobutadiene Molecule by Valence Bond Method
Authors: Takekiyo Shozaburo
Published: July 2006

π -Electronic energy levels, probalities of the resonance structures, and bond orders of cyclobutdiene molecule have been calculated by the valence bond method on the bases of two ways, one is based on non-orthogonal atomic orbitals and the other on their orthogonali-zation. Calculated ionic characters are 21.517% (ground 1B2g state), 29.946% (first excited 1A1g state) in the former and 32.293%, 38.280% in the latter. Bond orders between neighboring carbon atoms are 1.445, 1.410 and 1.416, 1.385 respectively.
Studies on Tritium Labeled Compounds. IV. Preparation of Tritium Labeled Alanine by Means of Electric Discharge
Authors: Sato Yoshishige , Takahashi Tadao
Published: July 2006

To obtain tritium labeled alanine of a high specific activity by means of electric discharge, α-hydroximinopropionic acid was employed in place of alanine. After electric discharge, tritium labeled α-hydroximinopropionic acid was removed by ether extraction and the residue was chromatographed. Tritium labeled alanine was obtained with a specific activity of 4.4 μc./mg. which was two hundred times as great as that obtained by the use of alanine.
Thermodynamic Studies on Cobalt Complexes. VIII. Some Information about Diaquotetramminecobalt(III) Complexes and Thermal Dissociation of the Corresponding Chloride
Authors: Mori Motoshichi , Tsuchiya Ryokichi , Takemura Shuji , Matsuda Eisei
Published: July 2006

The visible and ultraviolet absorption spectra of diaquotetramminecobalt(III) perchlorate were measured and its decomposition process was discussed on the basis of the thermal analytical data.

The decomposition pressure of diaquotetramminecobalt(III) chloride was measured and the free energy of formation of aquochlorotetramminecobalt(III) chloride which was the product of the decomposition was calculated.

The infrared absorption and X-ray diffraction were measured for diaquotetramminecobalt(III) and aquopentamminecobalt(III) perchlorates and the relationships between the dimension of the unit cell and the coordinate bond strength, Co–N, were discussed.
Chemical Use of the Absorption of Soft γ-Rays, β-Ray-excited X-Rays and K-Capture X-Rays. I. Improvement in Fundamental Technique and Introduction of a Differential Absorption Method
Authors: Nozaki Tadashi
Published: July 2006

Studies for the improvement of fundamental techniques for the chemical use of the absorption of soft γ-rays, β-ray-excited X-rays and K-capture X-rays were undertaken. The exponential absorption curve, which is essential for the measurement of the accurate absorption coefficient and for many quantitative works, was obtained by the use of a proper detection method and the differential absorption technique, even in the presence of some photons having various energies. The relationship between the absorption coefficient thus obtained and the photon energy proved to agree with the theoretical result.
Physicochemical Studies on Cobalt Salts of Higher Fatty Acids. I. Preparation of Cobalt Soap by Metathesis
Authors: Kambe Hirotaro
Published: July 2006

As a method of preparation of cobalt soap, metathesis between alkaline soap and cobalt salt was investigated.

Cobalt stearate, palmitate and myristate were obtained in pink, blue and red forms according to conditions. Cobalt laurate in blue form was not observed.

Metathetic products were always pink at the beginning. If the system has a solvent ratio (solvent to water) higher than 1 : 1, and the solution after mixing is acidic, the color of soap will turn blue with stirring. It will change red later when left in the solution. The blue form could not be obtained with acetone or methanol as a solvent.

The speed of the color change became considerably slower with fatty acid of a shorter chain length.

In substitution reaction between stearic acid and cobalt acetate with a solvent ratio higher than 1 : 1, the same color changes were observed. But in this system the addition of some alkali suppressed markedly the color change, and at an exactly neutralized metathetic reaction the soap did not turn blue. Even in this case, when acetone was used instead of ethanol, the color change was observed, but the speed was very slow.
Physicochemical Studies on Cobalt Salts of Higher Fatty Acids. II Compositions of Cobalt Soaps
Authors: Kambe Hirotaro
Published: July 2006

Pink, blue and red cobalt stearates were analyzed and their compositions were determined. From these results, it has been confirmed that blue soap is anhydrate and red soap is dihydrate. The pink soap has a rather indefinite composition nearer to red soap. A mechanism of the color changes was proposed based on the inversion of the micelle structure under some circumstances.
Physicochemical Studies on Cobalt Salts of Higher Fatty Acids. III. Spectrophotometric Specifications of Colors of Cobalt Soaps
Authors: Kambe Hirotaro
Published: July 2006

The colors of three species of cobalt stearates were specified by I. C. I. chromaticity coefficients. Reflection spectra have been compared with each other, and it has been found that these colors are continuous in nature.

Pink soaps have dominant wavelengths in a wide range from 520c∼555c mμ and show small purities and large brightnesses. Red soaps have essentially the same dominant wavelengths as that of pink soaps at 530c∼540c mμ, but they show comparatively large purities and small brightnesses, because they are darker than pink soaps. They must be called magenta in color language.

Blue soaps must be called violet rigorously, for they show dominant wavelengths at about 450 mμ. They have larger purities and smaller brightnesses. Between blue and pink, many tones of color from violet to purple exist continuously. It is certain that these colors are related to each other.

The pale pink cobalt stearates obtained in aqueous methanol were specified in the same way.
Physicochemical Studies on Cobalt Salts of Higher Fatty Acids. IV. Ionic Nature of Cobalt Soaps, Revealed in Infrared Absorption Spectra and Magnetic Susceptibilities
Authors: Kambe Hirotaro , Mita Itaru
Published: July 2006

The infrared absorption spectra and the magnetic susceptibilities of red dihydrate and blue anhydrate of cobalt stearate were measured. The infrared spectra showed the existence of carboxylate ion in these soaps, and magnetic measurements confirmed that they are ionic in nature.

The magnetic moments of red and blue cobalt stearates showed that they are spin-free or ionic covalent complexes. The geometry of red soap is six-covalent octahedral, and that of blue is four-covalent tetrahedral. Structure formulas were proposed for them in correspondence with these geometries, but they may be improbable because of the existence of unstable rings of four members. Alternative formulas, in which a carboxyl group joins two cobalt ions, might be considered but have not yet been given.
The Beckmann Rearrangement of 1,2-Cyclohexane-dione Dioxime in Liquid Sulfur Dioxide
Authors: Tokura Niichiro , Tada Ritsuro , Yokoyama Kunio
Published: July 2006

Three different reagents, thionyl chloride, bromine and sulfur trioxide in liquid sulfur dioxide were reacted on 1,2-cyclohexanedione dioxime to yield cyclohexano[c]-1,2,5-oxadiazole, 1-aza-7-oximinocyclohepta-2-one and δ-cyanovaleric acid respectively. Only the bromine in liquid sulfur dioxdie effected the Beckmann rearrangement. Thionyl chloride caused a dehydrative condensation, as has been reported previously. Sulfur trioxide yielded a product resulting from a deoximative cleavage. The reasons for the different processes and the different products have been discussed.
The Raman Spectra of 1,3,5-Trichlorobenzene and 1,3,5-Trichlorobenzene-d3
Authors: Saëki Shinnosuke
Published: July 2006

The Raman spectra and the qualitative depolarization ratio of each line were observed for the solutions of 1,3,5-trichlorobenzene and 1,3,5-trichlorobenzene-d3. The assignments of Raman active normal vibrations of these substances were carried out from the results of these measurements. The assignments for species A1′ and E′ proved to be correct from the application of the product rule, showing a good accordance between theoretical and calculated ratios of products of the frequencies. However, the application of the product rule was impossible for species E″ because of unobserved frequencies.
Raman Spectra of 1,2,4,5-Tetrachlorobenzene and 1,2,4,5-Tetrachlorobenzene-d2
Authors: Saëki Shinnosuke
Published: July 2006

The Raman spectra of 1,2,4,5-tetrachlorobenzene and 1,2,4,5-tetrachlorobenzene-d2 were measured in their dissolved states in methanol and carbon tetrachloride. The depolarization ratio of each Raman line was also observed qualitatively by the two-exposure method, using polaroid cylinders. On the basis of these experimental results, the assignment of normal vibrations was determined. The verification of the proposed assignments by means of the product rule was impossible for most of the species because of some unobserved normal vibrations. But, for species Ag, good agreement was obtained between the theoretical and observed values of the product of the frequencies for each substance, and the correctness of the assignment was thus verified.
Visco-elastic Behaviors of Aluminum Soap-Hydrocarbon Systems. II. Aluminum Soaps in Nujol
Authors: Shiba Sukekuni
Published: July 2006

Dynamic visco-elastic behaviors of aluminum soaps from various fatty acids and aluminum stearates of different compositions in nujol were studied, using a forced oscillation rheometer. The systems behave always as typical visco-elastic bodies in a wide range of concentrations and temperatures. Aluminum palmitate, myristate, and laurate show properties similar to stearate, whereas caprate and caprylate show less effects on rheological properties. Optimum composition of aluminum stearate as thickener was obtained. Rheological structures in the systems were discussed and comparison of the results by static and dynamic measurements was made.
Studies on Dehydroalanine Derivatives. III. Formation of Amino Acids from Poly-dehydroalanine
Authors: Sakakibara Shumpei
Published: July 2006

Reaction of poly-dehydroalanine with various reagents such as potassium carbonate, potassium cyanide, benzyl mercaptane and acetonitrile were studied. In every reaction mixture, alanine, glycine, serine, threonine, glutamic acid, aspartic acid and several unknown amino acids were detected. Ultraviolet-radiation resulted in the liberation of greater amounts of glycine. It was observed that considerable amounts of aspartic acid, S-benzyl-cysteine and glutamic acid were formed in reaction mixtures of potassium cyanide, benzyl mercaptane and acetonitrile, respectively.
Absorption Spectra of Unstable Colored Intermediates from Picryl Chloride by the Action of Sodium Hydroxide
Authors: Abe Takehiro
Published: July 2006

The red solution prepared by adding sodium hydroxide to an aqueous picryl chloride solution containing a small quantity of ethanol, was relatively stable even at room temperature. The red solution showing the two bands at about 416 and 490 mμ, changed into the yellow solution showing the band similar to that of picric acid under the same condition. Accordingly, the 416 and 490 mμ bands may be due to the intermediate of Meisenheimer’s type in the process of the substitution reaction of picryl chloride to picric acid.

In the presence of sodium hydroxide, picryl chloride in ethanol as well as in acetone finally gave the absorption bands analogous to that of picric acid in water containing ethanol. The red solutions in ethanol and in acetone, therefore, would be due to the same intermediate.