bluuebunny/crossref_metadata_2025_split huggingface dataset:
Vibrational Spectra of Triethylfluorosilane
Authors: Tanaka Toshio , Murakami Shigezo 
Published: July 2006

Abstract
The infrared and the Raman spectra of triethylfluorosilane have been measured, and the normal vibrations for the skeletal modes have been calculated by Wilson’s FG matrix method, using a simple Urey-Bradley force field and assuming point group C3v for the molecular symmetry. The skeletal vibrations have been assigned quantitatively on the basis of the normal coordinate treatment, and the hydrogen vibrations have been tentatively assigned. The vibrational spectra of this molecule have also been discussed in comparison with those of triethylchlorosilane and methyltrimethoxysilane.
The Spectrophotometric Determination of Anions by Solvent Extraction with Metal Chelate Cations. XIII. A New Method for the Determination of Picric Acid
Authors: Hayashi Shigehiko , Kotsuji Keiya , Sakurai Toshiyuki , Kimura Kenji , Yamamoto Yuroku 
Published: July 2006

Abstract
The solvent extraction method has been applied to the spectrophotometric determination of minute amounts of picric acid with the 2,2′-dipyridyl iron(II) chelate. The selectivity of the procedure is largely dependent on the pH of the solution. At pH 2.5 the extraction is selective for picric acid in the presence of nitrophenols.
The Chemical Behavior of Low Valence Sulfur Compounds. I. Oxidation of Elemental Sulfur with Compressed Oxygen in Aqueous Ammonia Solution
Authors: Shieh Mu-Chang , Otsubo Hiroshi , Okabe Taijiro 
Published: July 2006

Abstract
1) The oxidation of sulfur with compressed oxygen proceeds through the following sequence of steps: (a) The disproportionation of sulfur to both pentasulfide and thiosulfate. (b) The oxidation of pentasulfide to thiosulfate. (c) The oxidation of thiosulfate to sulfate and sulfamate through a series of complicated intermediates.
2) Sulfamate forms only in the decomposition of trithionate.
3) The over-all reaction of the oxidation is prompted by a rise in the temperature, an increase in the ammonia concentration, and the addition of transition metal ions, especially-copper ions.
The Benzene-Photosensitized cis-trans Isomerization of Butene-2
Authors: Tanaka Masahiro , Terao Terumi , Sato Shin 
Published: July 2006

Abstract
The benzene-photosensitized cis-trans isomerization of butene-2 has been investigated in the gas phase. The results have been discussed on the basis of a mechanism involving triplet energy transfer from benzene to butene-2.
The quantum yield measurements indicate that the reaction occurs at a very high efficiency. The triplet-benzene quenching efficiency of butene-2 has been shown to be considerably greater than that of the ground-state benzene.
The photostationary cis-to-trans ratio has been about unity, unlike the value obtained by Cundall et al. A mechanism which may explain the dependence of the ratio on the pressure and on the energy of the sensitizer has been suggested.
π-Electronic Energy Levels of o-Benzoquinone
Authors: Kuboyama Akira , Wada K\={o}ichi 
Published: July 2006

Abstract
The π-electronic energy levels of o-benzo-quinone have been obtained by using Pople’s SCF MO method, while the electron repulsion integrals have been obtained by the Pariser-Parr method. The absorption band near 360 mμ and the strong band which is thought to exist near 200 mμ have unambiguously been assigned to the first 1A1→1B2 and the second 1A1→1A1 transitions respectively. The calculated singlet excited energy levels are much higher than the observed levels. The reason for this has been examined by SCF MO calculations using modified values of various kinds of electron repulsion integrals and core integrals. It has been concluded that a satisfactory lowering of the calculated singlet excited energy levels cannot be expected unless values of the core resonance integrals (β) are used which are much modified from those generally used. Simple MO parameters for o-benzoquinone adequate to simulate the simple MO’s to the SCF MO’s have been obtained.
The Near-infrared Absorption Spectra of Lanthanide Chlorides Dissolved in Molten LiCl–NaCl–KCl Eutectic
Authors: Mamiya Masato 
Published: July 2006

Abstract
Using a high temperature cell for molten salts, a spectrophotometric investigation in the near-infrated region form 0.8 to 2.6 μ and at temperatures from 400 to 800°C has been carried out with fourteen lanthanide chlorides dissolved in a LiCl–Nacl–KCl mixture of eutectic composition (49.0-17.3-33.7 mol%, m.p. 333°C. Praseodymium, neodymium, samarium, dysprosium, holmium, erbium, thulium and ytterbium have characteristic absorption bands in this region. Most of the near-infrated absorption bands of lanthanide chlorocomplexes have been compared to similar spectra obtained in molten nitrate media. However the several absorption bands have been found to be different in molten nitrate and chloride eutectics. Thus, the absorption bands of europium and terbium have been observed in nitrate, wheras their bands have not been found in chloride, and the absporption bands of praseodymium, samarium and holuium beyond the 1.4 μ range have been found to be located at different wavelengths. these solvent, for the ligand field affects the 4f-electronic energy levels of the above elements.
The absorption peaks of lanthanide ions decrease as the teperature increases, partly due to the change in the concetration of the ions associated with the volume change. However, all the characteristic absorption bands of lanthanide in the near-infrared region have stable molar absorptivities at a constant temperature. These absorption bands can be used for the investigation of chemical constitution and electronic structure, for anlysis and for other purposes.
Studies of Diarylalkanes. III. The Cleavage of Diarylmethanes under the Influence of Aluminum Chloride
Authors: Tsuge Otohiko , Tashiro Masashi 
Published: July 2006

Abstract
The reaction of several diarylmethanes (III –XII) with aluminum chloride under various conditions has been carried out in order to elucidate the effect of the substituent on the cleavage of diarylmethanes. It has been established that the bond between the aromatic ring and the methylene group is cleft and that the cleavage is affected by the relative basicities of the two aromatic rings in the diarylmethane as well as by the basic strength of the benzene derivative which is present in the reaction system.
A New Method of Analyzing Thermogravimetric Data
Authors: Ozawa Takeo 
Published: July 2006

Abstract
A new method of obtaining the kinetic parameters from thermogravimetric curves has been proposed. The method is simple and applicable to reactions which can not be analyzed by other methods. The effect of the heating rate on thermogravimetric curves has been elucidated, and the master curve of the experimental curves at different heating rates has been derived.
The applications of the method to the pyrolyses of calcium oxalate and nylon 6 have been shown ; the results are in good agreement with the reported values.
The applicability of the method to other types of thermal analyses has been discussed, and the method of the conversion of the data to other conditions of temperature change has been suggested. From these discussions, the definition of the thermal stability of materials has been criticized.
The Effect of Hydrogen-Bonding on the g-Value of Diphenyl Nitric Oxide
Authors: Kawamura Takashi , Matsunami Shoichi , Yonezawa Teijiro , Fukui Kenichi 
Published: July 2006

Abstract
The decrease in the g-value of diphenyl nitric oxide in hydrogen-bonding solvents has been examined. This decrease has been analyzed on the basis of Stone’s theory for the g-value of a π-radical. The decrease in the g-value has been shown to be caused mainly by the decrease in the odd-electron density on the oxygen atom and the increase in the energy difference between the odd-electron and lone-pair orbitals. We have also attempted to estimate the blue shift of the n-π* transition from the g-value.
The Kinetics of the Phosphate-catalyzed Epoxidation of Styrenes with a Mixture of Nitrile and Hydrogen Peroxide
Authors: Ogata Yoshiro , Sawaki Yasuhiko 
Published: July 2006

Abstract
The phosphate-catalyzed epoxidation of styrenes with a mixture of nitriles and alkaline hydrogen peroxide have been studied kinetical-ly in 75% methanol. The reactions satisfy third-order kinetics, being first-order in nitrile, hydrogen peroxide and styrene. The rate is essentially constant at various pH’s, while it increases with the increasing polarity of the reaction medium. The energy of activation is low (6–8 kcal.mol−1), and the entropy of activation is highly negative (−50 e. u.). The effect of substituent in benzonitrile is to give a Hammett’s ρ-value of 0.57, while that in styrene resulted in a negative ρ-value of −0.51. It is probable that the peroxycarbimidic acid (I), produced by mobile equilibria from nitrile and hydroperoxide ion, is stabilized by an intermolecular hydrogen bonding with the phosphate dianion, and that this species contributes mostly to the epoxidation of styrene in the following, rate-determining step.
Application of Electrostatic Models to the Colloidal Behavior of Plate-shaped Particles
Authors: Jordine E St A , Steel B J , Wolfe J D 
Published: July 2006

Abstract
The method of images in dielectrics is applied to a model consisting of two infinite dielectric slabs and a point charge. When specific effects of the ions such as hydration energies are taken into account, the model describes the electrical aspects of the swelling of the clay minerals satisfactorily. In addition, a detailed theory of the mechanism of swelling is proposed and is shown to be favored by preliminary experimental studies of vermiculite.
Studies of the Liquid-Liquid Partition Systems. IV. The Solvent Extraction Study of Europium(III) Adduct Chelate Complexes with Six Acetylacetone Derivatives and Tributylphosphate
Authors: Sekine Tatsuya , Ono Masaru 
Published: July 2006

Abstract
The extraction of europium(III) in 0.1 m sodium perchlorate with acetylacetone, benzoylacetone, trifluoroacetylacetone, benzoyltrifluoroacetone, froyltrifluoroacetone and thenoyltrifluoroacetone in chloroform and the adduct formation of these metal chelates with tributylphosphate have been studied at 25°C.
It has been concluded that: (i) The β-diketones which have one trifluoromethyl group extract europium(III) better than those which have no trifluoromethyl group. The difference in the metal extraction with acetylacetone or trifluoroacetylacetone and the metal extraction with the homologues of these β-diketones seems to be mainly due to the aqueous chelate complex formation, (ii) A metal chelate with a β-diketone which has a trifluoromethyl group is a much better acceptor of tributylphosphate to form adduct complexes than a metal chelate with a β-diketone which has no trifluoromethyl group. (iii) The ability of the acetylacetone chelate or the trifluoroacetylacetone chelate to form an adduct is not very much changed by the replacement of the methyl group with a benzoyl, froyl, or thenoyl group.
Reactions of the Iodomethylate of N,N-Dimethylthiobenzamide with Nucleophilic Reagents
Authors: Mukaiyama Teruaki , Yamaguchi Tatsuaki , Nohira Hiroyuki 
Published: July 2006

Abstract
The reactions of the iodomethylate (I) of N,N-dimethylthiobenzamide with nucleophilic reagents have been examined. The iodomethylate I reacted with sodium ethylmercaptide and potassium cyanide to give N,N-dimethylbenzamide methylethylmercaptol and α-dimethylamino-α-methylthiobenzyl cyanide respectively. When primary amines and the monosodium salts of active methylene compounds were treated with the iodomethy late I, benzamidine hydroiodides and α-dimethylaminobenzylidene derivatives of the active methylene compounds were, respectively, obtained, and methyl mercaptan was eliminated. Further, it has been found that diamines, such as o-phenylenediamine, easily condensed with the iodomethylate I to yield such heterocyclic compoundsas 2-phenylbenzimidazole, while methyl mercaptanand dimethylamine were eliminated.
The Dipole Moments of Some Sesquifulvalene Quinones and Related Compounds
Authors: Katagiri Shigeyoshi , Murata Ichiro , Kitahara Yoshio , Azumi Hiroshi 
Published: July 2006

Abstract
The dipole moments of some quinone derivative of sesquifulvalene, the corresponding dione compounds and their several derivatives have been measured in benzene at 25°C. The moments of cyclopentene-3, 5-dione and indane-1,3-dione are in the same direction as the carbonyl resultant, the mesomeric moments being 0.4 D. and 1.3 D. respectively. On the other hand, the direction of the moments of sesquifulvalene-1, 4-quinone and its 2,3-benzo derivative is just reversed because of a large transfer from the seven-membered ring towards the five-membered ring, presumably towards the carbonyl groups. The incremental moments, the difference between the observed and the carbonyl resultant, in these quinones are 4.2 and 3.9 D. respectively, while the moments due to the transfer from the seven-membered ring are 4.7 and 5.2 D., suggesting that such a charge transfer is greater in benzo-sesquifulvalene quinone.
On the Competition of Homogeneous and Heterogeneous Chain Terminations in Heterogeneous Photooxidation Catalysis by Zinc Oxide
Authors: Ikekawa Akiko , Kamiya Mamoru , Fujita Yuzaburo , Kwan Takao 
Published: July 2006

Abstract
The photooxidation catalysis of isopropyl alcohol on zinc oxide has been investigated with special reference to the chain termination, mechanism. It has been proposed that homogeneous and heterogeneous chain terminations, compete in this system. At a low concentration of zinc oxide, the homogeneous termination predominates, while at a high concentration the heterogeneous termination may come into play. As a result, a maximum may appear in the relation of the rate of oxygen uptake to the amount of zinc oxide present. With excess zinc oxide, chain reactions are suppressed, so no maximum may appear in the corresponding plot and the temperature coefficient should be very small. The experimental results have been found to be consistent with the expectations. The effect of doping zinc oxide on the photo-oxidation kinetics has been investigated and discussed, mainly on the basis of the data available on the formation and decomposition of hydrogen peroxide on doped zinc oxide samples.
It has been suggested that lithia-doped zinc oxide is more active than alumina-doped zinc oxide at higher temperatures because of the; accompanying hydrogen peroxide-initiated oxidation of isopropyl alcohol on the former, while it is less active at lower temperatures because, of the efficient decomposition of hydrogen peroxide, giving oxygen and water.
Kinetics of Methane Oxidation in Shock Waves
Authors: Miyama Hajime , Takeyama Tetsu 
Published: July 2006

Abstract
The mechanism of methane oxidation in reflected shock waves has been studied by measuring the induction period of the OH absorption and that of the pressure increase simultaneously, and also by using the single-pulse technique combined with gas chromatography.
As a result, it has been found under the present experimental conditions that the rate-determining step for the over-all reaction of the methane-rich mixtures with the ratio [CH4]/[O2]=6 is CH4 + O2→ CH3 + HO2, and that the rate-determining step for the over-all reaction of the methane-lean mixtures with the ratio [CH4]/[O2]=3/ 7 is CH2O + O2→ HCO + HO2. Also, the rate-determining step for the OH formation of the lean mixtures has been found to be CH3 + O2→ CH2O + OH under the present conditions. In the case of the intermediate mixtures with the ratio [CH4]/[O2]=1.5, the over-all reaction is considered to be controlled mainly by the reaction CH4 + O2→ CH3 + HO2.
The Spectrophotometric Determination of Anions by Solvent Extraction with Metal Chelate Cations. VI. A New Method for the Determination of Mercury(II)
Authors: Kotsuji Keiya 
Published: July 2006

Abstract
A new method for the determination of mercury(II) has been proposed. The method is based upon the solvent extraction of the associated complex formed between the 2,2′-dipyridyl iron(II) chelate cation and the tetraiodo-mercury(II) complex anion and upon the estimation of the absorbance belonging to the chelate cation in the organic phase. The interference of diverse ions is eliminated by using ethylenediaminetetraacetate as a masking agent.
Surface Chemistry of the Polyamide Series. III. Monolayers of Nylons from ω-Aminocarboxylic Acids at the Air/Water Interface
Authors: Yamashita Takuya 
Published: July 2006

Abstract
The surface films of a series of nylons prepared from ω-aminocarboxylic acids and with 2 to 11 CH2 groups per monomer unit (Nylons 3 to 12) have been studied at the air/water interface in order to investigate the correlation of the film properties with the numbers of CH2 groups. The film of Nylon 9 at the oil/water interface and that of polynonamethylene urea at the air/water interface have also been studied.
The film of Nylon 3 on the 40% ammonium sulfate subsolution was of the condensed type and the area occupied per residue was quite small, probably because of the especially strong hydrogen bonds between amide groups. On the other hand, the films of Nylons 4, 5 and 6 on 40% ammonium sulfate and that of Nylon 6 on distilled water were of the expanded type. These polymers might be spread in rather flexible states because of the effect of the increased number of CH2 groups.
Nylons 8 to 12 and polyurea gave condensed films on distilled water, their limiting areas per residue being much smaller than the areas calculated for the fully extended chains. The condensation of the films might be primarily caused by the increased van der Waals attractive force between hydrocarbon groups, as has been proved by the remarkable expansion of Nylon 9 film at the petroleum ether/distilled water interface. The small limiting areas of these polymer films have been interpreted by assuming that the hydrocarbon chains are folded near these areas. Nylon 7 was found to give an intermediate film between expanded films, such as Nylons 4 to 6, and condensed films, such as Nylons 8 to 12.
Interesting differences in the film properties of odd- and even-numbered nylons have been found with Nylons 8 to 12. Odd-numbered nylons occupied somewhat larger areas per residue than even-numbered nylons, and the maximum surface moments of the formers were higher than those of the latters. This is the result of the difference in shapes of the folded chains between the two series of nylons.
The surface viscosities of Nylons 8 to 12, with the exception of the last, were first detected at larger areas than the close-packed areas calculated for the fully-extended chains. The areas found for even-numbered nylons were much smaller than those for odd-numbered ones. This may be attributed to the difference in modes of hydrogen bond formation between amide groups.
A remarkable effect of the concentrated sulfuric acid subsolution on the film properties of Nylons 6 to 9 has been found, and interpreted as being due to the protonation to the amide linkages.
On Glumamycin, a New Antibiotic. VI. An Approach to the Amino Acid Sequence
Authors: Fujino Masahiko 
Published: July 2006

Abstract
To elucidate the amino acid sequence of glumamycin, glumamycin and DNP-glumamycin have been partially hydrolyzed with hydrochloric acid, and various peptides have been isolated by column chromatography on ionexchange resin or talc-celite, paper chromatography and paper ionophoresis. From the structures of the peptides, two possible structures (A and B) for glumamycin have been presumed.
Photolysis of Acetaldehyde in the Presence of Deuterium Sulfide. Deuterium Atom Abstraction from Deuterium Sulfide Molecules by Methyl Radicals
Authors: Imai Naomi , Dohmaru Takaaki , Toyama Osamu 
Published: July 2006

Abstract
The photolysis of acetaldehyde in the presence of deuterium sulfide has been investigated over the temperature range from 200 to 300°C, in order to determine the rate constant for the deuterium atom abstraction from deuterium sulfide molecules by methyl radicals. The effect of deuterium sulfide addition is similar to that of the addition of hydrogen sulfide previously studied. The results obtained with low concentrations of deuterium sulfide can be explained by the following reaction scheme: CH3CHO+hν→CH3+CHO (1), CHO→ CO+H (2), H+CH3·CHO→H2+CH3CO (3), H+D2S→ HD+DS (4), CH3+CH3CHO→ CH4+CH3CO (5),CH3+D2S→CH3D+DS (6), DS+CH3CHO→ HDS+CH3CO (7), CH3CO→ CH3+CO (8), and CH3+CH3→ C2H6 (9). The rate equation derived from the scheme, −d[CH3CHO]/ dt=k5k9−1⁄2Ia1⁄2[CH3CHO] + k6k9−1⁄2Ia1⁄2[D2S], is in agreement with the results. The application of this rate equation leads to k6⁄k5=2.0exp(3000⁄RT), and to k6=1011.6exp(−3800⁄RT) mol−1 cc. sec−1, if k5=1011.3exp(−6800⁄RT) mol−1 cc. sec−1, as has been reported by Ausloos and Steacie. On reinvestigating the effect of hydrogen sulfide addition, it was found that k6′⁄k5=1.5exp(4150⁄RT), where k6′ refers to the CH3+H2S→ CH4+HS (6′) reaction. We thus obtain k′6⁄k6==0.75exp(1150⁄RT).
Amylose-Iodine Complex. IV. The Complex in Dimethyl Sulfoxide-Water Mixtures
Authors: Ono Sôzaburo , Watanabe Takehiko , Ogawa Kozo , Okazaki Nobuhiko 
Published: July 2006

Abstract
The temperature at which the blue color due to the formation of amylose-iodine complex fades completely has been determined with a system of amylose and iodine dissolved in dimethyl sulfoxide-water mixtures. This temperature rises with the increase in the concentration of iodine in mixtures, and also with the increasing concentration of water in the mixed solvents.
The spectrophotometric results show that the nature of the amylose-iodine complex in a dimethyl sulfoxide-water mixture is similar to that of one in water, and that the triiodide ion or a chemical species similar to the ion, i.e., the polyiodide ion, contributes to the formation of the complex.
The viscometric studies show that the amylose molecule takes a deformed helix conformation prior to the formation of the blue iodine complex and that this conformational prerequisite to the complex formation is fulfilled when the water concentration in a dimethyl sulfoxide-water mixture exceeds a critical value.
These results stated above may indicate that the triiodide (polyiodide) ion plays the part of “stabilizer” for the fixation of iodine molecules within the helically-wound chain of the amylose molecule when the amylose exists primarily as a deformed helix in solution.
A Spectrophotometric Study of Xylenol Orange as a Color Reagent for Beryllium
Authors: Otomo Makoto 
Published: July 2006

Abstract
The red color produced by adding a xylenol orange solution in excess to a beryllium solution has been studied spectrophotometrically in order to ascertain the optimum conditions for the determination of beryllium. The absorption curve of the colored system shows an absorption maximum at 495 mμ when measured against a reagent solution of pH 5.8. Beer’s law is obeyed over the range up to 6 μg of beryllium. The composition and the apparent formation constant of the two different complexes have then been obtained by applying some spectrophotometric techniques. Beryllium forms a 1 to 1 complex with xylenol orange below pH 5; it gives, however, mixture of 1 to 1 and 1 to 2 complexes at higher pH values.