bluuebunny/crossref_metadata_2025 huggingface dataset:
The Chelating Behavior of Catechol-4-sulfonate with Iron (III) Ion
Authors: Murakami Yukito , Nakamura Katsuyuki
Published: July 2006

Both potentionmetric and spectrophotometric measurements have been carried out in order to study the chelating tendencies of catechol-4-sulfonate with iron (III) ions in aqueous media at the ionic strength of 0.10 m. Even in the 3:1 (ligand to metal ion) system, the equilibrium of the titrating solution was established gradually, except in the lower pH range. When the amount of the ligand was not sufficient to satisfy the coördination number of the iron (III) ion, the titration system became complicated because of both the slow attainment of equilibrium in the chelate formation and the hydrolysis of the chelates.

The stability of the iron (III)-catechol-4-sulfonate was found to be slightly less than that of the corresponding iron (III)-Tiron chelates. The visible absorption spectral data indicated that Tiron and catechol-4-sulfonate produce similar ligand fields for the iron(III)ion.
The Ultraviolet Absorption Spectra and the Hydrolysis of \overset4P-\overset3P-\overset4P-Acid
Authors: Yoza Norimasa , Ohashi Shigeru
Published: July 2006

It has been found that \overset4P-\overset3P-\overset4P-acid in aqueous solutions shows characteristic ultraviolet absorption spectra, which vary remarkably with the pH change of the solutions. The spectra having absorption maxima at 226, both 205 and 230, 224, and 215 mμ can be assigned to P3O85−, HP3O84−, H2P3O83−, and H5P3O8 respectively.

The rates of the hydrolysis of the \overset4P-\overset3P-\overset4P– acid in the perchloric acid solutions have been determined by measuring the absorbance at 215 mμ. The hydrolysis follows the first order rate law. The hydrolysis products are \overset3P– and \overset4P-\overset4P-acid. The rate constant is in the linear function with the activity of perchloric acid. The activation energy has been estimated to be 16.6 kcal. per mol.
Remark on the Solvent Effects upon the Electronic Spectra of Naphthalene Derivatives
Authors: Mataga Noboru
Published: July 2006

The importance of the Franck-Condon principle in the solvent shifts of π-π* spectra has been discussed with reference to aniline and naphthylamines in alcohol and aqueous solutions. The blue shift of the absorption spectra and the red shift of the fluorescence spectra in these polar solvents have been interpreted in terms of the Franck-Condon destabilization energies, including the solute-solvent hydrogen bonding interactions and the dipolar interactions. In addition to this, the similarity of the electronic spectra of naphtholate ions to those of naphthylamines has been pointed out with reference not only to the absorption spectra but also to the fluorescence spectra.
Formaldehyde Resins. LXVI. The Base-catalyzed Reaction of Benzamides with Formaldehyde
Authors: Imoto Minoru , Kobayashi Mitsue
Published: July 2006

The mechanism of the reaction of the substituted benzamides with formaldehye in diox-ane-water (1:1) in the presence of sodium hydroxide has been studied kinetically. Equations 2 and 3 have been obtained. An electron-attracting group increased the rate of the reaction, while an electron-releasing group decreased it. The reaction rates fit Hammett’s equation. It was concluded that the SE1-mechanism is suitable for interpreting the results obtained.
The Application of Intermittent Illumination to the Bleaching of Dye. I. A General Consideration of the Method
Authors: Koizumi Masao , Usui Yoshiharu
Published: July 2006

The method of intermittent illumination by means of flashes of very short duration has been criticized, particularly with regard to the frequency and intensity of the flash. It has been concluded that when f0 (the fractional decrease of the starting substance per second due to the absorption of light) is less than 0.1, the kinetics for the steady illumination will hold within a few per cent. A model case in which a certain intermediate absorbs light and causes an addition reaction has been discussed.
The Application of Intermittent Illumination to the Bleaching of Dye. II. The Methylene Blue-Amine System
Authors: Kato Shunji , Usui Yoshiharu , Koizumi Masao
Published: July 2006

A new apparatus for intermittent illumination has been designed and applied to the system of methylene blue and trimethylamine. A frequency effect has been discovered and established to be genuine. Thus, when the frequency is raised, the rate constant for the buffered and for the non-buffered solution shows an increase of about forty percent, but in the former case, between 1 p.p.s. and 10 p.p.s., and in the latter one between 10 p.p.s. and 100 p.p.s.

If it is assumed that a certain intermediate X absorbs light and induces the additional reaction, the extinction coefficient of X ought to be 104∼105 in order to interpret the observed effect. Hence, it is likely that the intermediate in question is not an intermediate in true sense of the word, but the ground state dye in a slightly modified state.
The Solubilization of Oil-soluble Dyes by a Polysoap and a Monosoap
Authors: Tokiwa Fumikatsu
Published: July 2006

The solubilization of several oil-soluble dyes, 1-benzeneazo-2-naphthol (BAN) and three 1-nitrobenzeneazo-2-naphthols (nitro-BAN), by a polysoap and a monosoap has been studied by measuring the solubilizing power, the viscosity and the electrical conductance of the solutions of both soaps.

The polysoap is a better solubilizer than the monosoap. BAN was more solubilized than nitro-BAN at any given concentration of soap. The amount of nitro-BAN solubilized by the polysoap was increased in the order m-nitro-BAN>p-nitro-BAN>o-nitro-BAN, while the solubilization by the monosoap was in the order m-nitro-BAN>o-nitro-BAN>p-nitro-BAN. However, there appears to be no simple interpretation of the effect of the structure of dyes upon the solubilization. The addition of the dyes to the polysoap solutions decreased the viscosity, except for that of p-nitro-BAN at low concentrations of polysoap. p-Nitro-BAN produced an anomalous increase in the viscosity, the reason for this being not certain. In the case of polysoap, every solubilized dye produced a small increase in electrical conductance, but no significant difference among them could be found.
Studies on Mixture Dyeing. II. The Kinetics of a Mixture of Chrysophenine G and Sirius Red 4B
Authors: Sekido Minoru , Morita Zenzo
Published: July 2006

1) The single and mixture dyeing of Chrysophenine G (C.I. Direct Yellow 12) and Sirius Red 4B (C. I. Direct Red 81) have been examined kinetically.

2) The affinity and the diffusion coefficient of each dye at 90, 85 and 80°C have been evaluated. The apparent activation energy of diffusion at a constant surface concentration has been calculated.

3) In the mixture dyeing, although the apparent diffusion coefficient of each dye became larger than that in the single dyeing, whose surface concentration was similar to that in the mixture dyeing, the dye with the smaller diffusion coefficient had a more profound effect on the diffusion of the dye with the larger diffusion coefficient than in the reverse case.
The Quenching Action of Pyridine and Quinoline on the Fluorescence of Naphthalene Derivatives
Authors: Miwa Takuji , Koizumi Masao
Published: July 2006

The quenching constants (k) of quinoline for the fluorescence of several substances in n-hexane have been determined. The values, obtained are as follows; they are independent of the frequency of the exciting light.

2-Naphthylamine 120 (20°C) 140 (40°C)

N,N-Dimethyl-

 2-naphthylamine 90 (20°C) 100 (40°C)

2-Naphthol 100 (21°C)

2-Naphthylmethyl-

 ether 53 (21°C)

The results clearly show that the hydrogen bond is not necessary for the quenching to occur, in contradiction to the mechanism proposed by Mataga for the case in which pyridine is used as a quencher.

To elucidate the mechanism, the quenching phenomena in the fluorescence of the above substances have been further studied in benzene and ethanol, using pyridine and quinoline as quenchers. The most notable finding has been that, in ethanol, pyridine can quench the fluorescence of 2-naphthylamine and N,N-dimethyl-2-naphthylamine equally well, the k value for 25°C being, respectively, 16 and 15.

A mechanism has been proposed which involves the charge transfer from fluorescer to quencher. When the quenching is considerable, the rate-determining step is the diffusion proces, irrespective of the molecular mechanism for the quenching.
Studies on the Complex Formation between Uranium and Thiomalic Acid
Authors: Mathur V K , Nigam H L , Srivastava S C
Published: July 2006

Uranyl ion has been found to form an orange-yellow coloured complex with thiomalic acid. Spectrophotometric measurements reveal a composition of 1:1 as UO2(II) : TMA in the complex, where TMA stands for thiomalic acid. Thiomalic acid is found to behave as a bidentate ligand with UO2(II) in this complex. This has been concluded by potentiometric method. Magnetic susceptibility measurements, however, show an anomolous magnetic behaviour. The formation constant logK, at fixed pH and ionic strength as calculated from the spectrophotometric curves, comes out to be 3.0±0.1 and the corresponding free energy of formation has been calculated as −4.2±0.2 at 25°C.
The Kinetics of Substitution Reactions Involving Metal Complexes. VII. Effect of Acetate Ions on the Reaction between Lead(II) and Zinc-Ethylenediaminetetraacetate Complexes
Authors: Tanaka Nobuyuki , Ogino Hiroshi
Published: July 2006

The effect of acetate ions on the substitution reaction between lead (II) and zinc-EDTA complexes has been investigated. The reaction was treated as to proceed through both hydrated metal ions and monoacetato complexes, and the rate equation was derived. The rate constants for six elementary reactions of which three involve the hydrated lead (II) ion and the others involve the monoacetatolead-(II) complex were determined at ionic strength 0.2 at 25.0°C. The values indicate that all the reactions proceeding through hydrated lead ions are faster than the corresponding reactions through monoacetato lead complexes. The results also suggest that the rate of the reaction through diacetatolead(II) complexes is much slower than those of the reactions through hydrated ions and monoacetato complexes.
Crystal Growth of Magnesium Oxide Prepared by the Thermal Decomposition of Magnesium Hydroxide
Authors: Kotera Yoshihide , Saito Tatsuo , Terada Matsuo
Published: July 2006

The particle size of magnesium oxide crystals prepared by the thermal decompositions of pure precipitated magnesium hydroxide and native brucite at various temperatures between 500 and 900°C has been measured by the X-ray line broadening method, and the effect of the calcination temperature and its duration on the crystal size of magnesium oxide has been examined.

It has been found that the particle size of magnesium oxide crystals increasese with the increase in the calcination temperature and that the rate of crystal growth obeys a different law between the earlier stage of the calcination process at a definite temperature and the later stage. It has also been found that the crystal growth of magnesium oxide proceeds proportional to tn, (t: time), where n is 1/6 for the later stage of the calcination of magnesium oxide from precipitated magnesium hydroxide at temperatures ranging from 700 to 900°C and 1/4 for the same calcination of that from brucite. The values of the activation energy calculated by Arrhenius plot are 17 and 32 kcal./mol. for magnesium oxide obtained from precipitated hydroxide and from brucite respectively.
A Synthesis of l-Proline from l-Glutamine
Authors: Itoh Tamio
Published: July 2006

1. Novel syntheses of optically active proline and ornithine from optically active glutamine are described.

2. Carbobenzoxy-l-glutamine esters were dehydrated to γ-cyano-α-l-carbobenzoxyaminobutyric acid esters with p-toluenesulfonyl chloride, phosphorous oxychloride or thionyl chloride.

3. Hydrogenation of γ-cyano-α-l-carbobenzoxyaminobutyric acid esters in aqueous solvent systems were effected by silk-palladium catalyst to yield mainly l-proline.

4. By hydrogenation in the presence of Raney nickel in non-aqueous solvent, l-ornithine was obtained.
A Study of Metal Complexes of Analytical Importance. II. Complexes of Salicylaldoxime and C-Methyl-salicylaldoxime with Vanadium(V)
Authors: Nakamura Hiroji , Shimura Yoichi , Tsuchida Ryutaro
Published: July 2006

New complexes of salicylaldoxime (symbol: salmH2) and C-methyl-salicylaldoxime (symbol: Me-salmH2) with vanadium(V), [VO(OH)·(salmH)2] (A), [VO(O-Et)(salmH)2] (B), [VO·(OH)(Me-salmH)2] (C) and [V(OH)(Mesalm)2] (D) were prepared. A, B and C complexes were dark-colored, while the D complex was light-colored.

The absorption spectra of A and C in dimethylformamide were determined. Based on the measurements of the visible, ultraviolet and infrared absorption spectra of these complexes, the following conclusions were drawn:

1) In benzene complex A has the trans structure, while in dimethylformamide it has the cis structure.

2) Complex C has the same properties as A.

3) The esterification of A does not cause any remarkable change in color.

4) The great difference between, the color of C and that of D comes from the difference in the donor atoms of the ligand. In the former the ligands are coordinated as N, O-chelates, and in the latter, as O, O-chelates.
Vinyl Polymerization. LXX. Preparation of 3-(4′-Pentenyl)cyclopentene-1 and its Alternative Copolymerization with Maleic Anhydride
Authors: Imoto Minoru , Tsuda Kazuichi , Otsu Takayuki
Published: July 2006

3-(4′-Pentenyl)cyclopentene-1 (PCP) was prepared through the reaction of 1-pentenyl magnesium bromide and 3-chlorocyclopentene-1. An attempt was made for the polymerization and copolymerization of PCP. In the polymerizations by radical (azobisisobutyronitrile) and Ziegler [Al(i-Bu)3-TiCl4] initiators, a little brown methanol-soluble oil was obtained. By cationic initiator (BF3·OEt2), however, a trace of reddish brown polymer which did not dissolve in common organic solvents was formed.

PCP was copolymerized with maleic anhydride by the use of a radical initiator. When the monomer mixture ratio of PCP to maleic anhydride was varied, no change was observed in the copolymer composition (the proportion of PCP to maleic anhydride being 1 to 2). In the infrared spectrum of the copolymer, the absorption bands of the vinyl type double bond and the unsaturated cyclopentene ring of PCP disappeared in the copolymer, so it was to be assumed that both double bonds participated in the copolymerization to form glassy gelled pale-yellow copolymer. These results indicate that an alternative copolymerization took place.
Viscometric Studies of Solutions of Sodium Phosphates, Graham Salts and Vanadium-containing Graham Salts
Authors: Nakagaki Masayuki , Ohashi Shigeru , Minato Fumiko
Published: July 2006

The intrinsic viscosities of sodium orthophosphates, pyrophosphate, tripolyphosphate and Graham salts of relatively low molecular weight (lower than 10300) were measured. The relation between the intrinsic viscosity at 25.5°C and the average molecular weight measured by the end group titration was

[η]=6.9×10−4×M0.61

in a 0.035 n sodium bromide solution, and

[η]=0.0348+0.112×10−4×M

in a 0.07 n sodium bromide solution.

Vanadium-containing Graham salts (sodium vanadate-phosphate copolymers) seemed to be hydrolyzed immediately by the dissolution. The intrinsic viscosity of the solution was much smaller than that of sodium polyphosphate of the corresponding degree of polymerization.

The rate of the hydrolysis of branched sodium polyphosphate was proportional to the number of branchings, and the rate constant was 0.39 hr−1 at 25.5°C.
The Nuclear Magnetic Resonance Spectra of Olefinic Systems and the Substituent Effects. II. Methyl Esters of α- or β-Substituted Cinnamic Acids
Authors: Kasiwagi Hazime , Nakagawa Naoya , Niwa Jun
Published: July 2006

The proton magnetic resonance spectra with regard to methyl esters of α- or β-substituted cinnamic acids have been investigated from the viewpoint of the substituent effect. When the results are compared with the correlation obtained with ω-substituted styrenes, the trends are also explicable as being controlled by the polar nature of the substituents.
Kinetics of Hydrolytic Reaction Catalyzed by Crystalline Bacterial α-Amylase. II. The Influence of Solvent
Authors: Ono Sôzaburo , Hiromi Keitaro , Sano Yoshiki
Published: July 2006

The influence of methanol on the rate of the hydrolytic reaction of soluble starch catalyzed by crystalline bacterial amyloclastic α-amylase has been studied at 25°C and pH 6.0, over the methanol concentration of 0∼22.6% by weight.

The apparent Michaelis constant, Km, is independent of the methanol concentration, while the breakdown rate constant of the ES complex, k3, decreases with an increase in the methanol concentration.

The plot of logk3 versus the reciprocal dielectric constant of the solvent gives a straight line with a negative slope.

Various possible effects on the reaction rates caused by the addition of methanol have been examind, and it has been concluded that the dielectric constant effect is predominantly operative.

The results have been interpreted quantitatively on the basis of the electrostatic theory previously developed by one of the present authors. The results of calculation have been found to be consistent with the hypothesis that charge separation occurs in the glucosidic linkage to be hydrolyzed in the activated state of the ES complex.

The electrostatic entropy of activation in the breakdown of the ES complex has also been estimated.
The Wetting of Paraffin by Aqueous Solutions of Fatty Alcohol Homologues
Authors: Tsunoda Teruo
Published: July 2006

The wettability of paraffin towards aqueous solutions of n-propyl, n-butyl, n-amyl and n-octyl alcohols has been studied. It has been found that the wetting isotherm which had been proposed by the present author and had been valid for the wetting of paraffin by an aqueous ethyl alcohol solution, could also be applied successfully to the present systems. The equations of state for the adsorbed films of these alcohols at the paraffin/aqueous solution interface were obtained. It was further shown that Traube’s rule holds for the paraffin/aqueous alcohol solution interface as well as for the air/solution interface. The adsorption energies found were 824 cal./mol. CH2 for the paraffin/solution interface and 656 cal./mol. CH2 for the aqueous surface.
The Infrared Spectra of O-Deuterated and O-Methylated Derivatives of Diacetyl Monoxime and Isonitrosoacetone
Authors: Kuroda Yoko , Kimura Masao
Published: July 2006

The infrared absorption bands due to the O=C–C=N–OH system have been investigated by the use of diacetyl monoxime, isonitrosoacetone, and their O-deuterated and O-methylated derivatives. All the bands observed have been reasonably assigned. So far as the infrared spectra are concerned, the degree of conjugation in the C=O bonds is between those of saturated ketones and α,β-unsaturated ketones. The degree of conjugation in the C=N bonds is greater than those of conjugated imines and of aldoximes containing a C=C–C=N group and is approximately equal to those of vic-dioximes containing an N=C–C=N group. Under the influence of conjugation, the N–O bonds have a greater double-bond character than those of unconjugated oximes. The bond character varies with the hydrogen bonding, the type of which is not –O–H…N=C, but –O–H…O=C. In general, the bands due to the C=N bonds of oximes are weak. However, they are intensified by deuteration and are intensified remarkably by methylation.
Studies of the Absorption Spectra of Azo Dyes and their Metalcomplexes.I. The Absorption Spectra of Phenylazoacetoacetanilide and its Related Compounds
Authors: Yagi Yoshiharu
Published: July 2006

Phenylazoacetoacetanilide and its related compounds have the hydrazone structure. The phenylazoacetoacetic acid ethylester, for example, forms an intramolecular hydrogen bond between a ketone group and a hydrazone group in the solid state and in non-polar solvents.

The electronic absorption spectra exhibit three groups of bands—A,B and C—D. The effects upon the spectra of the intramolecular hydrogen bond and of the π-p conjugation at the carboxylic acid amide group have been discussed.
Studies of the Absorption Spectra of Azo Dyes and their Metalcomplexes. IV. The Effects of Substituents on the Absorption Spectra of Chromium (III)- and Cobalt (III)-complexes of Phenolazoacetoacetanilides
Authors: Yagi Yoshiharu
Published: July 2006

The electronic absorption spectra of the series of metallized phenolazoacetoacetanilides have been investigated.

The substituent, in the o- or p- position to the M–O (M, central metal; O, phenolic oxygen) bond, generally alters the polarity of the M–O bond. On the other hand, the substituent, in the m-position to the M–O bond, i.e., the p-position to the hydrazone group, mainly contributes to the dπ-pπ interaction between the hydrazone group and the central metal atom.

The effects of such substituents upon the shifts of the A bands are more pronounced in the cobalt (III)-complexes than in the chromium-(III)-complexes, because the former complexes have the stable five-membered chelate rings involving the highly covalent Co–O (O, phenolic oxygen) bonds.
Magnetic Study of the Amino Group
Authors: Sriraman S , Shanmugasundaram D
Published: July 2006

The diamagnetic susceptibilities of several aliphatic and aromatic amines have been determined. The susceptibility contribution, of NH21+ is evaluated from the noninteracting aliphatic amines, and this value is used for calculation of χM of aromatic amines. The exaltations are attributed to the interactions in the system. An anomalous value for N3+ ion is obtained.
Kinetics of Hydrolytic Reaction Catalyzed by Crystalline Bacterial α-Amylase. III. The Influence of Temperature
Authors: Hiromi Keitaro , Takasaki Yoshiyuki , Ono Sôzaburo
Published: July 2006

The influence of temperature upon the Michaelis constant,Km, and on the breakdown rate constant, k3, has been investigated for the hydrolytic reaction of amylose catalyzed by crystalline Bacillus subtilis α-amylase at pH 5.85 (the optimum pH) over the temperature range from 6 to 40°C.

It has been found that logKm and logk3 increase linearly with a decreasing reciprocal absolute temperature 1/T in the lower temperature range below 25°C, while above that point they tend to flatten out. On the other hand, the plot of logk3⁄Km versus 1/T has been found to be linear over the whole temperature range studied. Apparent thermodynamic quantities have been calculated from Km, k3 and k3⁄Km and their temperature dependences.

The results have been examined kinetically in terms of two different mechanisms, the first assuming a three-step mechanism, and the second assuming the reversible denaturation of the enzyme molecule. It has been found that the former is reasonably consistent, but the latter is poorly consistent with the results.

By combining these findings with the previous data of solvent effect, the non-electrostatic part of the entropies for the reaction processes has been discussed.

The meaning of thermodynamic quantities obtained have been diccussed.
The Crystal Structure of Ethylenediammonium Chloride
Authors: Ashida Tamaichi , Hirokawa Sakutaro
Published: July 2006

The crystal structure of ethylenediammonium chloride has been determined. The crystal belongs to the monoclinic system with a=9.95, b=6.89, c=4.42Å and β=90.7°; the space group is P21/a. The unit cell contains two ethylenediammonium ions and four chloride ions. The ethylenediammonium ion occupies a center of symmetry and takes a transform; thus, the ethylenediammonium ion was found to be either a trans- or a gauche-form in the crystals, depending on the structures of the crystals. The bond distances and angles of the ethylenediammonium ion are: C–C 1.53, C–N 1.49Å and <CCN 109.8°. Three N–H…Cl hydrogen bonds (3.20, 3.22 and 3.14Å) make two-dimensional networks of the ions perpendicular to the c axis.
The Preparation of Trimethylamine Oxide Complexes and Some Infrared Studies
Authors: Kida Sigeo
Published: July 2006

Metal complexes of trimethylamine oxide with cobalt (II), zinc (II) and cadmium (II) have been prepared.

The infrared spectra of trimethylamine oxide and its complexes have been measured in the 1500 to 300 cm−1 range. Assignment of the observed bands has been made on the basis of the calculation of the normal vibrations of trimethylamine oxide.

The band at 950 cm−1 was found to be mainly contributed by the N–O stretching vibration, as was expected from the former investigations, but it was also considerably contributed to by the other mode of vibrations.

The metal-O stretching band was not found in the region of the present investigation; consequently, a rather weak bond was assumed to exist between trimethylamine oxide and metal ions.
Synthetic Resins Catalyzing the Racemization of Amino Acids. II. The Activity of the Resins
Authors: Toi Koji
Published: July 2006

1) A study has been made of the factors influencing the racemization of amino acids by resinous catalysts with structures partially similar to those of pyridoxal and salicylaldehyde.

2) The optimum pH of the reaction was about 10.5.

3) A rise in temperature resulted in an increase in the rate of the reaction.

4) The racemization reactions catalyzed by the resins required the presence of metal ions, and cupric ions were found to be most effective.

5) Of the amino acids tested, l-alanine was racemized most rapidly.

6) The resinous catalysts retained activity after repeated usage.

7) The racemization-activity of the resins was compared with that of pyridoxal.
Formaldehyde Resins. LXXVII. The Synthesis of Some Anthracene Derivatives as a Wavelength Shifter of a Plastic Scintillator
Authors: Imoto Minoru , Nakaya Tadao
Published: July 2006

Three anthracene derivatives, 9,10-di-m-xyl-yl-anthracene (II), 9,10-bis(4-methylbenzyl)-anthracene (III), and 9,10-bis(2,3.5,6-tetra-methylbenzyl)anthracene (IV), have been synthesized and their ultraviolet and fluorescence spectra measured. The shift of the spectrum to the longer wavelength by the presence of methylene groups between anthracene and benzene rings may be explained in terms of direct conjugation between three rings.

According to the spectra, these compounds are believed to be better second solutes of the plastic scintillator.
Brown Nitrosylpentamminechromium(III) Salts and Green Nitrosylpentamminechromium(III) Perchlorate
Authors: Mori Masayasu , Ueshiba Shigeru , Kawaguchi Shinichi
Published: July 2006

A new series of chromium ammines, i.e., nitrosylpentamminechromium(III) salts, were obtained by the reaction of an ammoniacal chromium(II) solution with sodium nitrite. The derivatives are usually reddish brown, but only the perchlorate is bright green. The infrared absorption spectra indicate that in the green perchlorate the rocking frequency of ligating ammonia is lower, while the stretching frequency of the nitrosyl group is higher than in the brown chloride. These results seem to show indirectly that the coordinate linkage is weaker in the green perchlorate.
A Simple Digestion Method for the Quantitative Analysis of Metal in Some Organometallic Compounds
Authors: Kohama Shigemi
Published: July 2006

A new, modified digestion method for the quantitative analysis of metal in various organometallic compounds containing silicon, tin and titanium has been developed by the use of ammonium nitrate as a new oxidizing reagent. It has been shown that this method can be carried out more rapidly and more accurately than the other known methods.
The Spectrophotometric Determination of Palladium(II) with Xylenol Orange
Authors: Otomo Makoto
Published: July 2006

A new, sensitive spectrophotometric method for the determination of palladium (II) by using xylenol orange as a color reagent has been described. The palladium-xylenol orange complex has an absorption maximum at 518 mμ. The effects of the concentration of perchloric acid and of the reagent have been investigated. In addition, various conditions, including the duration of heating, the stability of the color, and the effect of diverse ions, have been investigated. In a solution of perchloric acid (1.1 to 1.7 n), xylenol orange is a highly selective reagent for palladium, although it reacts with a number of metal cations in a slightly acidic or a neutral solution. Beer’s law is obeyed in the range from 0.2 to 4.0 p. p. m. of palladium at 518 mμ. The results of Job’s method and of the mole ratio method show a complex consisting of two molecules of the reagent to one palladous ion. The formation constant was calculated to be 2×1010.
The Radiation-induced Reactions of Benzene with Sulfur and Sulfur Compounds
Authors: Ando Wataru , Sugimoto Ken’ichi , Oae Shigeru
Published: July 2006

The irradiation of a benzene solution of sulfur gave thiophenol, diphenyl disulfide, diphenyl sulfide, hydrogen sulfide, hydrogen and some polymers. The formation of thiophenol and of hydrogen sulfide is considered to be initiated by the radiolysis of benzene, which gives phenyl and hydrogen radicals, which in turn combine with sulfur in succeeding steps.

However, the thiophenol formed is oxidized to the disulfide as the radiation energy absorbed in benzene transfers to thiophenol. The effect of the initial concentration of thiophenol and of the radiation dose has been measured. The relative stability of the S–H and C–S bond for radiation was about 1:200. The radiolysis of diphenyl disulfide or hydrogen sulfide in benzene were found to form thiophenol. In a kinetical study of the decomposition of thiophenol in benzene, 0.7 benzene molecule is excited by the 100 eV. of gamma rays absorbed, while the ratio between the energy transfer to thiophenol from excited benzene and the deactivation of excited benzene itself is about 100 to 1.
An Attempt to Convert Glycine Residues to Threonine Residues in Polyglycine
Authors: Furuyama Toshiyuki , Sakiyama Fumio , Narita Kozo
Published: July 2006

When polyglycine was reacted with acetaldehyde in liquid ammonia in the presence of metallic sodium, it was observed that 7∼9% of the threonine residues were formed from glycine residues. From the hydrolyzate of the modified polyglycine, threonine could be isolated by the aid of the O→N acetyl shift reaction. It was shown that the threonine thus isolated was 35.6% allothreonine.
Reduction of Hexamminechromium(III) Ions at the Dropping Mercury Electrode
Authors: Tanaka Nobuyuki , Ebata Kazuko , Satô Gen
Published: July 2006

The reduction of hexamminechromium(III) ion at the dropping mercury electrode has been studied in neutral and acid aqueous solutions. Hexamminechromium(III) ion gives no well-defined d. c. polarographic wave in an unbuffered neutral solution, whereas in an acid solution it gives a well-defined two-step wave, the first wave corresponding to the reduction of chromium(III) to chromium(II) and the second, to that of chromium(II) to chromium-(0).

The first wave of the d. c. polarogram obtained in an acid solution is diffusion-controlled and gives a slope of the log-plot close to that expected for a reversible wave. The a. c. and the Kalousek polarogram, however, are of the irreversible type. No chemical reaction involving hydrogen ions, ammonium ions or ammonia takes place preceding the electron transfer. Considering these results, the following mechanism is temporarily suggested for the reduction of hexamminechromium(III) ions at the dropping mercury electrode:

[Cr(NH3)6]3++e\ightleftarrows[Cr(NH3)6]2+[Cr(NH3)6]2++nH2O→[Cr(H2O)n(NH3)6−n]2++nNH3NH3+H+\ightleftarrowsNH4+
Ionic Charge Effect on the Reduction Potential of Inert-type Metal Complex
Authors: Tanaka Nobuyuki , Itabashi Eiki , Kyuno Eishin
Published: July 2006

Current-potential curves of various oxalato complexes of chromium (III) were obtained at the dropping mercury electrode in acid or neutral aqueous solutions. The reduction potentials that were defined as potentials at \barl=\barll⁄10 were found to shift to more negative potentials with an increasing number of oxa-lates coordinated. The ionic charge effect on the reduction potentials was discussed in connection with the electrostatic interaction between the reacting species and the electrode.
Oxidation of Alcohols by Cerium(IV). I. Oxidation of Methanol by Ceric Perchlorate
Authors: Muhammad S S , Rao K Vijayachander
Published: July 2006

The oxidation of methyl alcohol by ceric perchlorate in perchloric acid solution was studied at 13, 20 and 26°C. The stoichiometry consisted of two cerie ions for the oxidation of one molecule of methanol. While the rate of disappearance of ceric ions directly depended on the concentration of ceric ions, the dependence on methanol concentration was such as to suggest a ‘broken order’:

\frac−dCeivdt=\frack(Ceiv)(MeOH)1+k′(MeOH)

This rate also depended on the concentration of perchloric acid in such a way that at high acidity it became independent of it.

These data were explained on the basis of Duke’s mechanism for 2,3-butane diol-ceric perchlorate reaction, i. e. the oxidation of methanol by ceric ions proceeded via an intermediate complex between one Ce4+ ion and one methanol molecule. The formation of this complex was also proved independently by a spectrophotometric method. The kinetic data were further used to derive the true heat of formation of the methanol-cerate complex and the heat of hydrolysis of the cerie ions in aqueous perchloric acid.
Pyrolysis of Acid Amides. III. Pyrolysis of Cyanoacetamides and 2-Phenylacetamides
Authors: Mukaiyama Teruaki , Takei Hisashi , Koma Yasuo
Published: July 2006

The pyrolyses of cyanoacetamides, 2-phenylacetanilide, 2,2-diphenylacetanilide and 2,2,2-triphenylacetanilide have been studied. The pyrolysis of cyanoacetamides gave the corresponding isocyanates and acetonitrile. On the other hand, the pyrolysis of 2-phenylacetanilide and 2,2-diphenylacetanilide gave a small amount of phenyl isocyanate, along with various byproducts. The pyrolysis of 2,2,2-triphenyl-acetanilide, however, against expectation, did not give isocyanate; only a tarry product resulted.
Studies on the Disproportionation Reaction of Methylnaphthalene
Authors: Echigoya Etsuro , Watanabe T\={o}ru , Morikawa Kiyoshi
Published: July 2006

The effect of the addition of chromium oxide on the activity of silicon oxide-aluminum oxide for the disproportionation reaction of methylnaphthalene has been studied.

1) As the amount of chromium oxide added increased the yield of naphthalene increased, but the selectivity for this reaction decreased in the low temperature range of 45∼520°C. The 5 wt.%, chromium oxide added catalyst gave the best results.

2) It has been concluded, from the observation of X-ray and electromicrograph of the chromium oxide-added nalcat catalyst, that most of the chromium oxide added developed into large hexagonal crystals which had little activity and that the residue (about 30%), which is supposedly dispersed very finely, is probably responsible for the promotion of the catalytic activity.

3) It has been concluded from the analyses of the experimental data obtained that this disproportionation reaction can be expressed by the kinetic equation based on the surface reaction which is rate-controlling.
The Radiation Annealing of Phosphorus-32 with Cobalt-60 Gamma-rays for Several Neutron-irradiated Inorganic Phosphorus Compounds
Authors: Tanaka Kichizo
Published: July 2006

Radiation annealings with cobalt-60 gammarays have been investigated for several neutronirradiated inorganic phosphorus compounds. The group separation technique by one-dimensional paper-partition chromatography was adopted to separate chemical species containing phosphorus-32. The reduced species in the sodium and potassium orthophosphate salts and in the sodium pyrophosphate salt decreased upon gamma irradiation, and an increase in the retention was observed. However, the polyphosphate increased initially in the several orthophosphate salts.

Three processes has been observed, the rate constants for these processes have been estimated, and two other processes have been suggested. The main process is the oxidation of the reduced species to phosphorus(V) species.

Radiation annealing have been studied for phosphates as a functions of the dose rate, the total dose of irradiation, and the temperature during gamma irradiation, it has been found that annealings are dependent upon the total dose and the temperature during irradiation and are independent of the dose rate. In orthophosphates and pyrophosphate, chemical species other than the parent species are easily annealed by gamma irradiation, whereas no detectable annealing has been observed in sodium orthophosphite or sodium hypophosphite.

In series of sodium and potassium orthophosphates, annealing was affected by the hydrogen content of the salts.
Spectrophotometric Studies of the Metallic Chelates of 2-Picolylamine. I. The Electronic Absorption Spectra of Some Nickel, Copper(II) and Cobalt(III) Chelates
Authors: Utsuno Shunji , Sone Kôzô
Published: July 2006

1) In addition to the nickel chelates (1:2 and 1:3) and copper chelates (1:2) already described by Sutton, it has been found that 2-picolylamine also forms 1:1 chelates (chlorides and sulfates) with these metals, which can be obtained in the state of crystals, and the chelate ions [Cu pic3]2+ of low stability, in solution.

2) A comparison of the electronic absorption spectra of all these chelates and two cobalt(III) chelates of 2-picolylamine with those of the chelates of ethylenediamine and 2, 2′-bipyridine has indicated that, in general, the spectrum of a 2-picolylamine chelate is intermediate between the spectra of the corresponding chelates of the latter two ligands; however, the similarity to the ethylenediamine chelate is more apparent in most cases.

3) Certain structural features of the 2-picolylamine chelates have been discussed on the basis of these spectral data.
Studies of the Photoreduction of Thiazine Dyes in Aqueous Solutions
Authors: Koizumi Masao , Obata Hiroshi , Hayashi Shigenari
Published: July 2006

Judging from the experiments performed in our laboratory, the photoreduction of dye without the addition of any reducing agent takes place only in thiazine dyes, and the reaction is particularly prominent when demethylation occurs simultaneously.

The reaction proceeds in the following way:

D+hν→D*

D*Dt

Dt+D→X (X=D−……D+)

(Remark: Graphics omitted.)

The part in parentheses is still doubtful. The above conclusion is consistent with the results of the flash experiment which will be described in a following paper. It has been proposed that some reducing agents attack Dt directly, while others attack the half-oxidized state.
The Absorption Spectra of Thiourea and Potassium Iodide on Nickel Metal
Authors: Suëtaka Wataru
Published: July 2006

The absorption spectra of thiourea molecules adsorbed on nickel surfaces in acid aqueous solutions have been observed by means of reflection cells. A new band did not appear in the observed region, but the intensity of the absorption band at 236 mμ decreased remarkably. The absorption spectra of potassium iodide have also been observed with reflection cells. For acidic solutions an absorption band at 226 mμ decreased in intensity and a new band appeared at 310 mμ, while for the solutions in pure water no change in the spectrum has been observed. The observed results have been discussed and a hypothesis of surface complex formation presented.
Electron Spin Resonance of Peroxy Radicals in Gamma-irradiated Polytetrafluoroethylene
Authors: Tanaka Hazime , Matsumoto Akira , Goto Nobuhisa
Published: July 2006

In the oriented sample of irradiated PTFE, the ESR spectrum of peroxy radicals consists of two singlets. One of them has an angular dependent g factor: g=2.0230−0.0165cos2ω, where ω is an angle between the orientation of the PTFE crystal and the direction of the magnetic field applied. This spectrum shows an asymmetrical profile in a powder sample. It has been interpreted in the light of the crystalline arrangement of PTFE. Additional peroxy radical, which gives an angle-independent ESR signal, is unstable at temperatures above 150°C.
A Geochemical Study of Selenium in Volcanic Exhalation and Sulfur Deposits
Authors: Suzuoki Tetsuro
Published: July 2006

Regarding selenium in volcanic materials collected at fumaroles of the Nasudake (36°07′N, 139°57′E) and the Kuju (33°07′N, 131°13′E) volcanoes, Japan, the following results have been obtained.

1) The selenium content in condensed water has no relation to that of sulfur and chlorine. The selenium content in certain sulfur deposits is strongly affected by the mode of occurrence, such as sublimation and solidification, as well as by the outlet temperature of the fumarole. The ratio of selenium to sulfur in both condensed water and sulfur deposit is related with gas temperature at the outlet of fumarole. The higher the gas temperature, the lower the degree of fractionation between selenium and sulfur.

2) The S/Se ratio in the original volcanic gases at Nasudake is close to 1.8×104, found in fumarolic gases with the highest temperature. The S/Se ratio in sulfur deposit is at least one-seventh that in condensed water.

3) Continuous observation over a short period (3 hr.) showed that the selenium content in condensed water varies considerably with time, while the sulfur content remains constant.
Vibrational Spectra of Tetracyanoethylene
Authors: Takenaka Tohru , Hayashi Soichi
Published: July 2006

The polarized infrared spectrum of a highly-oriented crystal of TCNE have been measured, tegether with the Raman spectrum of a sample consisting of several lumps of the crystals. The infrared spectra of the powedered solid, solution, and vapor have also been observed for comparison. Under the assumption of the Vh symmetry, the normal vibrations of TCNE have been calculated for the in-plane modes by the use of the GF matrix method. The basic UBFF, as well as the modified one containing cross terms between the C=C and C–C bonds, has been used as the potential function for this molecule. The frequencies calculated with the modified UBFF agree well with the observed values. The potential energy distributions have also been calculated, and the nature of the in-plane fundamental vibrations has been elucidated. The tentative assignments have been made to the out-of-plane fundamental vibrations and to the overtone and combination vibrations.
The Synthesis of Methylacetylene by the Pyrolysis of Propylene. I. The Effect of Pyrolysis Conditions on Product Yields
Authors: Sakakibara Yasumasa
Published: July 2006

Propylene has been pyrolyzed in a flow system over a wide range of conditions (temperature, 800∼1400°C; contact time, 4.4×10−4∼2.3 sec.; pressure, 40∼160 mmHg) to find suitable conditions for producing methylacetylene (and allene) and for obtaining data concerning the distribution of pyrolysis products. Under proper conditions, the pyrolysis occurred without any appreciable production of tarry and carbonaceous materials. High temperatures (1200∼1300°C), short contact times (millisecond order; conversions below 30%), and low pressures (below l00 mmHg) were found to required for the good production of methylacetylene-allene. A methylacetylene-allene yield of 38 mol. per 100 mol. of propylene pyrolyzed was realized at 1200°C, 50 mmHg pressure (partial pressure of propylene, 40 mmHg), and 24% conversion (contact time, 1.7 msec.). The other gaseous products were found to be methane, ethylene, hydrogen, acetylene, 1-butene and butadiene, in decreasing order.
Isomerization of cis-Azobenzene in the Solid Phase
Authors: Tsuda Morizo , Kuratani Kenji
Published: July 2006

The thermal and photo-isomerizations of crystalline cis-azobenzene have been studied by infrared spectrophotometry in the temperature range of 36∼58°C, It has been found that the thermal isomerization follows Prout Tompkins’ law, and the values of k3 at 36, 50 and 58°C have been estimated. The Arrhenius plot of K3 is linear, and the activation energy of k3 is 31.3±0.3 kcal./mol. Pre-irradiation with a mercury lamp shortens the induction period, but it does not change the value of k3. On the other hand, the value of k3 is affected by the degree of grinding of azobenzene crystals. In this case, the activation energy is not altered by crystal grinding.

The photo-isomerization at 12°C, in contrast to the case of thermal isomerization, has no induction period. However, the trans→cis photo-isomerization does not occur even if the crystal is treated by X-ray or by γ-ray preirradiation.
Spectroscopic Studies of the Complex Produced by Trimethylaluminum and Diphenylamine
Authors: Kawai Makoto , Ogawa Teiichiro , Hirota Kozo
Published: July 2006

The reactive complex produced by the reaction of trimethylaluminum with diphenylamine has been studied by the ultraviolet absorption and proton magnetic resonance methods. The ultraviolet absorption of the complex has shown two bands, at 228 mμ and 274 mμ, in cyclohexane. Proton magnetic resonance spectrum of the complex has been shown to consist of two groups of peaks, with an intensity ratio of approximately 5:3 and with chemical shifts of 2.90 p.p.m. and 10.58 p.p.m. These shifts have been assigned to phenyl protons and methyl protons respectively. In the mixture of trimethylaluminum and the complex, an exchange of methyl groups occurs. The structure of the complex has been concluded to be dimeric through two nitrogen bridges, as is shown in formula II.
Infrared Spectra of Adsorbed Formic Acid
Authors: Ogawa Teiichiro , Kishi Kosaku , Hirota Kozo
Published: July 2006

The infrared spectra of adsorbed formic acid on zinc have been measured. Two bands have been found at 1570 cm−1 and 770 cm−1and assigned to the adsorbed formate anion.
Solvent Effect on the Rearrangement of Cyclohexanoneoxime-p-toluenesulfonate. The Ionizing Power of Liquid Sulfur Dioxide
Authors: Tokura Niichiro , Kawahara Tetsuyo , Ikeda Sachio
Published: July 2006

The Beckmann rearragement of cyclohexanoneoxime-p-toluenesulfonate has been carried out in various solvents and the results have been discussed. The rate in liquid sulfur dioxide is the fastest among the solvents examined. The plots of the logk vs. ionizing powers of the solvents are not linear. The electrophilic solvation of liquid sulfur dioxide on the p-toluenesulfonate anion is important if the reaction is to be carried out rapidly and if an intermediate bridged cation, an azacyclopropenium cation, is to be obtained.
The Transfer Coefficient of a Redox Process at Varying pH Values as Determined by the Faradaic Rectification Method
Authors: Agarwal H P
Published: July 2006

The transfer coefficient of 0.001 m quinhydrone in buffer solutions of various pH values has been determined by Faradaic rectification studies. The value of α at 29°C has been found to be 0.376 at pH 1.4, 0.389 at pH 2.1, 0.503 at PH 4.62, and 0.506 at pH 6.1. The transfer coefficients determined at various pH values, help us to understand the mechanism of electrode processes.
A Mass Spectrometric Investigation of Petroleum. III. The Determination of the Alkyl Side Chain Number on Aromatics in the High Boiling Range Fraction of Petroleum
Authors: Oshima Shozo
Published: July 2006

The cleavage mechanism of alkylbenzene and other compounds under electron impact has been studied. The following facts are evident. If the ion from the aromatic compound is formed according to β cleavage under electron impact, the carbon number of the alkyl side chain on the compound may be indicated by the following equation;

b=a(n−1)⁄n+1 (1)

where

b: the total carbon number of the alkyl side chain in the ion produced;

a: the total carbon number of the alkyl side chain in the original molecule, and

n: the alkyl side chain number.

If the ion is formed according to α cleavage, the equation will be:

b=a(n−1)⁄n (2)

The effects of the alkyl side chain number and the structure upon n values from Eqs. 1 and 2 have also been studied. From the study, a method has been devised by which the alkyl side chain number of aromatics in the high-boiling-range fraction of petroleum can be determined from the total carbon number of the alkyl side chain in the molecule ion and the carbon number of the alkyl side chain in the peak showing the most intense peak in the spectrum.