bluuebunny/crossref_metadata_2025_split huggingface dataset:
Infrared Spectra of Acyclic Imides. I. Two Modifications of Diacetamide in the Crystalline State
Authors: Uno Toyozo , Machida Katsunosuke 
Published: July 2006

Abstract
Two crystal forms have been found for diacetamide (the form A and the form B). Infrared spectra of these two forms of diacetamide and diacetamide-d have been measured in the region 3600 to 400 cm−1 and many differences of absorption bands have been observed. It has been shown that these differences of absorption bands can be explained to result from rotational isomerism. The trans-trans planar structure of the –CONHCO–group has been proposed to correspond approximately to the molecular structure of the unstable form (the form B) of diacetamide. The frequency shifts of absorption bands on deuteration in the potassium bromide region has been discussed to give support to this interpretation. An assignment has been given to each absorption band in the potassium bromide region for the form A and the form B of diacetamide and diacetamide-d.
The Scattering of Beams of Alkali Atoms in Various Gases. II. Sodium Atom Beam in Non-reactive and Reactive Gases
Authors: Kodera Kumasaburo , Tamura Teijiro 
Published: July 2006

Abstract
Collision radii considerably larger than those of classical kinetic values have been obtained.Among the measured values of collision radii, that for neon is rather smaller and that for hydrogen is considerably larger than those obtained by the other investigators. For molecules of rather large molecular weight, relative sizes among them are reasonable but they increase with the resolving power of the apparatus used. These large values of radii and their increase with the resolving power may be explained by the existence of considerable mutual interaction such as Van der Waals’ force between colliding particles.
Kinetics of the Reduction of Selenious Acid by Sulfur Dioxide. II. Reduction in Acidic Solution with Sulfuric Acid
Authors: Hamada Keinosuke 
Published: July 2006

Abstract
(1) The reduction of selenious acid in sulfuric acid by sulfur dioxide is a reversible reaction, because the reaction has an equilibrium and the process of the reaction is in good accordance with the equation which expressed mathematically the reversible reaction, that is,
−d(a−p)⁄dt=dp⁄dt=k2(a−p)2−k2′p2
(2) Up to the present time the rate constant k2 of the forward reaction was derived by substitution of the experimental data for xmin the following equation,
k 2={2.303xm⁄2a(xm−1)t}×log[(x−xm)⁄{(2xm−1)x−xm}]
The general equation for k2, which does not depend on xm, has been obtained as follows,
k 2′=2.054×1015×[H+]2×exp(−E⁄RT)(E=22.5 kcal.⁄mol.)
The rate constant k2′ of the reverse reaction can be calculated by
k 2′=2.413×10−11×{1⁄(a2[H+]2)}×exp(−E⁄RT) (E=−8.06kcal.⁄mol.)
(3) It has not previously been reported that α selenium is dissolved in dilute sulfuric acid (below 85% by weight), as shown by the present experimental procedure.
(4) The results obtained from this study are useful in the recovery and refinining of selenium. Then application to the recovery and refining of selenium will be expressed in another succeeding paper.
Calculation on the Electronic States of the Acrolein Molecule by the Semi-Empirical Molecular Orbital Method
Authors: Inuzuka K\={o}z\={o} 
Published: July 2006

Abstract
It was found that the semi-empirical method proposed by Pariser and Parr can be applied to the n–π* transition as well as the π–π* transition in acrolein. In acrolein the (n, π*) triplet state is the lowest state. A weak band in the red side of the 0–0 band is a hot band and it is not the n–π* singlet-triplet transition band. The n–π* triplet band anticipated from calculation could not be found.
The Relation between Reactivity and Selectivity
Authors: Ogata Yoshiro , Tabushi Iwao 
Published: July 2006

Abstract
The proportionality between logpf and log(pf/mf) reported by Brown1) seems to express the proportionality between inter- and intramolecular selectivities. The standard rate constant k0 may be a measure for the reagent activity; the parallelism between 1/k0 and |ρ| or selectivity is observed in very limited reactions.
Mass Spectrometric Study on Adsorption of Water Vapor on a Graphite Surface
Authors: Inouye Hokotomo 
Published: July 2006

Abstract
Peak shapes in mass spectra obtained by voltage scanning using a mass spectrometer with such a modified ionization chamber as that described above are characterized by the places of formation and the initial kinetic energy of the ions. Thus, from the shape of the peak, one may be able to decide the place of formation of the ions and, though not so precisely, to estimate their initial kinetic energy.
When the method was applied to the ions formed by electron bombardment at a graphite surface covered with adsorbed water vapor, it was found that (1) H2O+ and HO+ were formed from residual or desorbed H2O only in the gas phase, (2) H2+, H+ and CO+ were formed both on the surface and in the gas phase, and (3) H+ which formed on the surface had the initial kinetic energy of about 10 V. These results will confirm the fact that the adsorbed water molecule is dissociated into adsorbed H2 and surface oxide of carbon that probably takes a configuration such that CO is adsorbed on the surface.
On the Fluorine Shift of Aromatic Fluorine Compounds
Authors: Yonezawa Teijiro , Fukui Kenichi , Kato Hiroshi , Kitano Hisao , Hattori Shuzo , Matsuoka Shinichiro 
Published: July 2006

Abstract
In order to make a quantitative analysis of the F19 magnetic shielding parameters in conjugated molecules, an extension of the idea previously proposed by Saika and Slichter is made. Calculations are carried out with respect to several fluorobenzene derivatives and fluorin-ated polycondensed aromatic compounds by using the molecular orbital method. The agreement of our calculated shifts with observed shielding data is almost satisfactory.
Electronic and Vibrational States of Acrolein
Authors: Inuzuka K\={o}z\={o} 
Published: July 2006

Abstract
The position, blue-shift and theoretical calculation3) of the state energy of the electronic transition of acrolein in 24241∼30294 cm−1region suggest that the transition is of the n−π* type. From the vibrational analysis of acrolein vapor spectrum, it is known that the vapor spectum of acrolein has four progressions corresponding to the C=O, C=C and C-C stretching, and skeletal bending frequency in the lower state.
Spectrophotometric Determination of Nitrite in Nitrate and Sulfate
Authors: Katsube Yukiteru , Uesugi Katsuya , Yoe John H 
Published: July 2006

Abstract
A simple procedure has been developed for the determination of trace amounts of nitrite in large amounts of nitrite and surlfate, with disodium 1-(4′-aminobenzeneazo)-2-amino-8-hydroxy-naphthalene-2′,6-disulfonate. The method is accurate and precise.
Electronic Spectra of Substituted Aromatic Hydrocarbons. I. Phenol and Aniline
Authors: Baba Hiroaki 
Published: July 2006

Abstract
The electronic spectra of monosubstituted benzenes are examined from the viewpoint of semi-empirical MO theory. To allow for electronic interaction, the simple LCAO method is refined in the light of purely theoretical procedure, configuration interaction being included. The refined method is particularly convenient for dealing with the spectra of substituted organic compounds.
The origins of the absorption bands for phenol and aniline are clarified on the basis of the calculated excitation energies, oscillator strengths and changes of charge distribution accompanying electronic transitions. The nature of the second excited state of aniline is discussed in detail, in connection with the problem of electron transfer.
Studies on d-Glucosamine Derivatives. VI. α-1-C-Phenyl-2-acetamido-2-deoxy-d-glucopyranoside and its Derivatives
Authors: Yoshimura Juji 
Published: July 2006

Abstract
The sirup obtained as a by-product with β-1-C-phenyl-2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-d-glucopyranoside by the action of phenylmagnesium bromide on acetobromo-d-glucosamine hydrobromide has been deacetylated and chromatographed to yield the α-anomer. Several α-derivatives have been described, among which, α-1-C-(p-nitrophenyl)-2-dichloroacetamido-2-deoxy-d-glucopyranoside which is a chloramphenicol derivative showed no antibiotic activities. The application of Hudson’s rules of isorotation to the anomeric compounds in this series is discussed.
Differential Thermal Analysis of the Systems Aluminum Soap-Hydrocarbon
Authors: Shiba Sukekuni 
Published: July 2006

Abstract
The phase behaviors of the system aluminum stearate, palmitate, and laurate-Nujol are studied by differential thermal analysis. Phase diagrams are obtained, and it is found for stearate and palmitate that soaps dissolve in hydrocarbon at the lower transition points of the soaps, and that the higher transition points disappear by addition of hydrocarbon. Differences in phase behaviors are found between laurate and other soaps. Some discussions are made on the colloidal structures of the dispersed systems aluminum soaps-hydrocarbon.
Studies on Metal Complex Species Using an Anion Exchange Resin, I. Derivation of Equations and Application to Mercury (II)-Nitrate Complex
Authors: Waki Hirohiko 
Published: July 2006

Abstract
1) The equations for determining the composition of a metal complex using an anion exchange resin have been derived by considering the complex formation equilibria in both the resin phase and the solution phase.
2) The method based on these equations was successfully applied to the investigation of mercury (II)-nitrate complex at various external nitrate concentrations by means of the sodium nitrate-sodium perchlorate mixed solution.
3) Mercury (II) adsorbed from a sodium nitrate solution exists in the form of Hg(NO3)3− at the external nitrate concentration of 0.5∼1 m, Hg(NO3)42− at 3∼5 m and a mixture of Hg(NO3)3− and Hg(NO3)42− at the middle of these concentrations, though no anionic complex appears to be present in an ordinary nitrate solution.
n−π Absorption Spectra of Some Aliphatic Aldehydes
Authors: Oshima Hiroko 
Published: July 2006

Abstract
The n-π absorption spectra of propionaldehyde, n-butyraldehyde and isobutyraldehyde were measured in various solvents and the effects of substituents and solvents on the n-π absorption spectra were investigated. For the former effect red shifts instead of blue shifts reported as the characteristic of n-π transitions were observed. The latter effect was studied using McRae’s equation. Hydrogen bonding between solute and solvent molecules is also considered.
Studies on the Chemical Equilibrium Lag during the Rapid Expansion through the Rocket Nozzle
Authors: Tsuchiya Soji 
Published: July 2006

Abstract
The pyrometer fitted for the temperature measurement of exhaust gas of the rocket, was constructed, and the exhaust temperature of the JP4-nitric acid rocket having 100 kg. of thrust, was observed. From the obtained exhaust temperature, it has been ascertained that the expansion of the gas through the present nozzle proceeds with chemical equilibria neither shifting nor frozen, and that relaxation occurs. From the approximate analysis of chemically relaxed flow, the relaxational process is assumed to occur at −(dt⁄dT)=3∼8×10−8 sec./deg., T\fallingdotseq2600°K and T\fallingdotseq10 atm.
Electron Paramagnetic Resonance Study of Diphenyl Nitric Oxide in Single Crystals
Authors: Deguchi Yasuo 
Published: July 2006

Abstract
Electron paramagnetic resonance experiments of diphenyl nitric oxide single crystals were performed. Variation of exchange narrowed line were measured by changing the magnitude of magnetic dilution in crystals. Angular variations of g-value and of hyperfine spectra were investigated. The value of the exchange integral in pure crystal and the spin density on 14N atom in the molecule were determined.
Polarographic Studies of Some Organo-sulfur Compounds. I. A.C. and D.C. Polarography of Potassium Thiobenzoate
Authors: Okamoto Koichi 
Published: July 2006

Abstract
The polarographically new sulfur compound, potassium thiobenzoate, was investigated, using A.C. and D.C. polarographs. Comparatively complicated three oxidation waves were observed in both polarograms.
According to the various investigations about the properties of these waves, it was found that the whole reaction was the oxidation of PTB to its disulfide, benzoyl disulfide. The 1st wave was mainly due to this oxidation reaction and the two others were mainly due to the adsorption and the desorption of PTB at the surface of D.M.E.
The reversible oxidation-reduction system consisting of PTB and benzoyl disulfide would not be expected owing to the adsorption and desorption processes that interfered with the normal oxidation of PTB to benzoyl disulfide, if the studies were done with a dropping mercury electrode.
Oxidation of Terpene Compounds with tert-Butyl Chromate. VII. Oxidation of d-p-Menthene-3
Authors: Fujita Kozo 
Published: July 2006

Abstract
On oxidation with tert-butyl chromate, d-p-menthene-3 gave d-carvenone as a main product and dl-p-menthen-3-one-5 as a by-product.
In this oxidation, it is found that, when an endocyclic double bond is in the position between C(3) and C(4) in monocyclic terpenes of p-menthane type, two active methylenes adjacent to the endocyclic double bond are selectively oxidized to carbonyls as in the case of the terpenes containing an endocyclic double bond in the position between C(1) and C(2), and that, between the two active methylenes, the one remote from the isopropyl group attached to C(4) is preferentially attacked rather than the other which is close to the same group.
A Study of Dehydration and Hydration of Oxalic Acid by Means of the Deuterium Exchange Reaction
Authors: Okazaki Nobukazu , Takemura Eiko 
Published: July 2006

Abstract
The deuterium exchange reaction in the course of the hydration of anhydrous oxalic acid with heavy water vapor and subsequent dehydration of the product has been studied.
Two exchange mechanism have been suggested to be operative; the hydrate formation mechanism and the surface exchange mechanism. A distinction may be made between the two by the dependence of exchange reaction on the molar ratio of the reactants.
Anhydrous oxalic acid prepared by dehydration at 100°C takes part in the exchange reaction through hydrate formation; while, with the anhydrous acid prepared by dehydration in vacuo at ordinary temperatures, the surface exchange mechanism comes into play.
For the specimens of anhydrous acid prepared in vacuo, the molar ratio of oxalic acid in the surface to that of the bulk is estimated to be 0.6∼0.7 from the results of the deuterium exchange reaction. Dehydration of oxalic acid dihydrate in the vacuum of electron microscope yields amorphous anhydrous acid.
The recrystallization of amorphous anhydrous oxalic acid was studied by the use of deuterium exchange reaction as a measure of surface area. It has been shown that adsorbed water exerts catalytic effect on the recrystallization. The process is associated with small or zero activation energy. Anhydrous oxalic acid recrystallized in the presence of water has been identified with α-form.
Deuterium exchange reaction between unhydrated oxalic acid and hydrate water occurs in anhydrous oxalic acid partially hydrated with heavy water vapor. The rate of this exchange is practically independent of temperature. The reaction probably consists in the deuteration of the molecules in the interior of the anhydrate lattice.
Treatment of amorphous anhydrous acid with a small amount of water vapor causes a peculiar change in the rate of subsequent rehydration. There is a considerable retarding effect on the rehydration rate for a particular range of the amount of water vapor.
The Rearrangement of N-Deuterated Aromatic Amine Hydrochloride into its Ring-deuterated Analogue in the Solid Phase: The Rearrangements of o- and m-Toluidine Hydrochlorides and the Effect of Anions on the Rate of Rearrangement of Anilinium Salts
Authors: Okazaki Nobukazu , Okumura Akiko 
Published: July 2006

Abstract
The rearrangement of N-deuterated aromatic amine hydrochloride into its ring-deuterated analogues has been studied in the solid and the liquid phases with o- and m-toluidines, and studied kinetically with anilinium chloride and bromide at 173∼194°C and at 210∼225°C, respectively.
The ease of the rearrangement of the hydrochlorides in the solid phase is in the order,
o-toluidine hydrochloride
&gt;aniline hydrochloride
&gt;p-toluidine hydrochloride
which is the reverse of the order of the basic dissociation constants of the amines at 25°C. m-Toluidine hydrochloride is more reactive than o-toluidine hydrochloride.
The numbers of nuclear hydrogen atoms which take part in the rearrangement are, 2 in the solid phase and &gt;3 in the liquid phase rearrangement of o-toluidine hydrochloride, and for m-toluidine hydrochloride 3 and 4 in the solid and the liquid phases respectively. This result, taken in conjunction with the earlier ones with aniline and p-toluidine hydrochlorides, confirms the view that in the solid phase rearrangement the ortho and the para positions are exclusively deuterated, and in the liquid phase deuteration of the meta positions takes place.
The rearrangement of the anilinium salts is characterized by high activation energy (ca. 45kcal.) and large positive entropy of activation (ca. 15cal./deg.).
These results are reasonably interpreted by the intramolecular electrophilic mechanism.
A small difference of the activation energies between the rearrangement of the two anilinium salts (ca. 2 kcal.) may be explained in terms of the different polarizing effects of the halide ions on initial state and possibly also on the activated complex.
Hydrophile-Lipophile Balance Values for O/W Emulsions Stabilized by Nonionic Surfactants. I. Hydrophile-Lipophile Balance Values of Nonionic Surfactants Determined by Emulsification
Authors: Ohba Noriaki 
Published: July 2006

Abstract
The HLB values of several types of nonionic surfactants were determined by experiments in emulsification according to the concept of HLB suggested by Griffin.
The HLB values required to emulsify the mineral oil do not show a consistent value, although the values are limited within a narrow range.
The HLB values calculated according to the law of the additivity for the surfactant mixture, [HLB]a, and the values calculated by the equations proposed by Griffin, [HLB]calcd, were compared. The differences between these two values were most remarkable in the case of sorbitan fatty acid esters and became greater at the higher mole numbers of the ethylene oxide in the molecule, excepting polyoxyethylene sorbitan esters and polyethylene glycol stearates.
Some explanations were attempted for such differences and for the deviations from the assumed additive properties of the HLB system, in connection with the role or behavior of nonionic surfactants in emulsification.
Hydrophile-Lipophile Balance Values for O/W Emulsions Stabilized by Nonionic Surfactants. II. “Required Hydrophile-Lipophile Balance Values” of the Oil Mixture
Authors: Ohba Noriaki 
Published: July 2006

Abstract
To study the additivity of the HLB values of an oil mixture from its component and the characteristics of the oil mixture forming a component of the emulsion, the required HLB values of several oil mixtures were determined by means of the emulsification tests proposed by Griffin.
The oil mixtures examined in this series of experiments consist of two oils, one being a mineral oil of fixed components and the other an oil to be studied as the additive, which is added in varying ratios to the fixed-component mineral oil.
The additivity of the required HLB values in oil mixtures was shown to hold to some extent for the case of saturated fatty acids, n-fatty alcohols, and some acetylated esters. For the rest of the additives, the additivity is not valid.
The required HLB values of these additive oils were remarkably large in the case of fatty acids, alcohols and some acetylated esters, excepting the anomalous value for oleic acid.
The structural effects on the increase of required HLB values seem to be in the following order:
COOH&gt;OH&gt;COOR
Chemical Use of the Absorption of Soft γ-Rays, β-Ray-excited X-Rays and K-Capture X-Rays. II. Application to the Analysis of a Binary Alloy and the Determination of a Heavy Element in a Multi-component System
Authors: Nozaki Tadashi 
Published: July 2006

Abstract
The absorption phenomenon of soft γ-rays, β-ray-exited X-rays and K-capture X-rays was applied to the following two kinds of analyses (1) Analysis of solder (simultaneous determination of the composition of a binary system and the sample thickness), and (2) Determination of an element of high atomic number in a multi-component system). Two photon-beams of energies suitable for each purpose were chosen, and for the letter purpose the retionship between the absorption coefficient of an element and the photon-beam energy was used. The results were in good agreement with those obtained by usual chemical anaiysis.
On the Basicities of the Nitro-derivatives of Benzoanthrones
Authors: Handa Takashi 
Published: July 2006

Abstract
The basicities of the nitro-substituted benzoanthrones were measured. One nitro-substitution decreases the basicity of beazoanthrone by about two pK units, as in the case of nitrosubstituted aniline and anthraquinone. This is explained qualitatively not by the inductive effect but by the resonance effect of the nitro groups on the carbonyl group of benzoanthrone in such way as to estimate approximately the change of resonance energies in the cases of both hydrocarbons and their related quinones. The gradient of the straight line of pK plotted versus log(N∗N) in the case of nitro-substitution is greater than in the case of chlorosubstitution. This means that the contribution of the polarized structure in the ground state to resonance effect is greater in the case of the nitro-derivatives of benzoanthrone than in the case of the chloro-derivatives.
The Reaction of Carbon Monoxide with Organometallic Compounds. VI. Synthesis of Symmetrical Ketones by the Reaction of Carbon Monoxide with Organolithium Compounds
Authors: Ryang Membo , Tsutsumi Shigeru 
Published: July 2006

Abstract
The reaction of carbon monoxide with an organolithium compound at −70°C yielded symmetrical ketones.
Benzophenone (55%), 4,4′-ditolyl ketone (50%), di-n-butyl ketone (40%), di-n-amyl ketone (28%) and diisopropyl ketone (30%) were prepared by this new method.
A reaction path for the formation of ketones was discussed.
Electrolytic Process for the Preparation of Dianisidine Using Rotating Cathode Cell for the Reduction of o-Nitroanisole to Hydrazoanisole
Authors: Udupa K S , Subramanian G S , Udupa H V K 
Published: July 2006

Abstract
The technique of using rotating cathodes for electrolytic reduction of nitro compounds developed in this Institute earlier has now been extended to the study of the reduction of o-nitroanisole in an alkaline emulsion to obtain hydrazoanisole, which is subsequently converted to dianisidine by reaction with acid. The various chemical methods of obtaining hydrazoanisole as well as the previous attempts for obtaining the same by electrolytic reduction of o-nitroanisole are briefly reviewed.
The experimental technique adopted, the isolation of the product and the subsequent conversion of the hydrazoanisole to dianisidine are described.
Cathode potential has been measured at different current densities using lead deposited iron cathode under stationary and rotating condition of the cathode without the addition of nitro compound. The effect of the nitro compound addition on the cathode potential at different current densities has also been studied. The potential of a rotating cathode measured during the course of an experiment is graphically presented and the results discussed.