bluuebunny/crossref_metadata_2025 huggingface dataset:
Ultraviolet Spectrophotometric Determination of Iron with Ethylenediaminetetraacetic Acid
Authors: Uzumasa Yasumitsu , Nishimura Masakichi , Seo Toshiko
Published: July 2006

A dilute solution of Fe3+—EDTA complex has a characteristic absorption peak at 260 mμ which is available for ultraviolet spectrophotometric determination of iron. An excess of disodium salt of EDTA was added to 0.1 m hydrochloric acid solution containing various amounts of iron as Fe3+ and the absorbance was measured with a Beckman DU spectrophotometer. A calibration curve for iron at 260 mμ was obtained and conformity to Beer’s law was found for concentrations up to 17p.p.m. of iron. The sensitivity of the method is 0.0065 γ/cm2.

The absorbance of Fe3+—EDTA solution decreases when irradiated by light, while it recovers when placed in the dark.

Fe3+—EDTA complex is stable in acidic medium, although its absorbance decreases rapidly below pH 0.5. The absorbance is also reduced on the alkaline side.

Hydrochloric, sulfuric, perchloric or acetic acid can be used in the determination. Nitric acid is used only when the concentration is kept in a certain limited value, this acid having the absorption maximum at 300 mμ and the minimum at 260 mμ.

Influence of the coexisting substances on the absorption measurement of Fe3+—EDTA complex was examined. Among the cations examined, alkalies and alkaline earths do not interfere. Cu2+, Hg2+ and Ti4+ interfere seriously when combined with EDTA, because their EDTA complexes show remarkable absorption in the ultraviolet region, which may suggest a new ultraviolet spectrophotometric determination of the metals.

After the work reported herein had been completed, the authors were informed of the work of Hill-Cottingham, who reports a somewhat similar study on iron complexes of EDTA and other chelating agents.
A Thermistor Method for the Determination of Velocity Coefficients of Vinyl Polymerization. V. The Effect of the Bulk Viscosity on the Velocity of Vinyl Polymerization
Authors: Miyama Hajime
Published: July 2006

The author measured the ratio of the propagation constant to the termination constant k/kt and the bulk viscosity η of the reaction system for the polymerization of methyl methacrylate and vinyl acetate by using the thermistor method and a special reaction vessel, which could be used as a viscosimeter, then compared the results of these measurements with the values kp and kt of vinyl acetate presented in the previous paper, and thus obtained the general formula for the relation between the bulk viscosity and kp or k. The obtained results are summarized as follows;

1) Throughout the total procss for the polymerization of vinyl acetate the rela-tion between the termination constant kt and η is expressed as follows, (k_t)_0/k_t=0.76+0.24[(η/η_0)^0.20+10^-8(η/η_0)^1.50]

In case of methyl methacrylate, the following formula is recommended which holds up to 22% conversion

(k_t)_0/k=0.83+0.17(η/η_0)^0.28

Where (kt)0 and η are the values of kt and η at conversion 0.

2) The propagation constant k and η in the polymerization of vinyl acetate are expressed as follows.

(k_p)_0/k=1+0.65×10^-6(η/η_0)

3) These results can be explained by the assumption that kt and kp are proportional to the diffusion constants of reacting molecules. Using the theory of Rabi-nowitch-Vaughan, we find some difficulties to explain our experimental results.
Microcolorimetric Determination of Organic Sulfur by the Tin(II)-Strong Phosphoric Acid Reduction Method
Authors: Kiba Toshiyasu , Akaza Ikuko , Kishi née , Taki Sachiko
Published: July 2006

A simple and rapid method for the determination of minute amounts of organic sulfur was established by using the oxidizing action of chromium (VI)-strong phosphoric acid and the reducing power of tin (II)-strong phosphoric acid. Organic sulfur was oxidized to sulfate by the former in a test-tube of fused silica and the sulfate was reduced to hydrogen sulfide by the latter in the same vessel. The hydrogen sulfide evolved was absorbed in zinc acetate solution and estimated colorimetrically by the ordinary methylene blue method. The absorbancy of the colored solution was measured at 655 mμ with a photoelectric colorimeter using 1-cm. cells. The sulfur content of the sample was estimated by comparing the absorbancy value with the standard curve prepared with sodium sulfate. Some organic compounds containing sulfur were analyzed by this method and satisfactory results were obtained. However, analysis of the miscellaneous organic substances such as biological specimens has not been undertaken and the problems for this purpose remain to be solved in future.
Determination of Critical Micelle Concentration of Detergent in Non-polar Solvent by Ultraviolet Absorption Spectra
Authors: Kitahara Ayao
Published: July 2006

The concentration dependence of the absorbance for the ultraviolet absorption spectra was measured for cyclohexane solutions of dodecyl ammonium benzoate and of octadecyl ammonium benzoate at 20±2 and 30±2°C. The break has been observed in the absorbance-concentration relationship. On the other hand, the relation between the amount of water solubilized into solutions and the concentration of the detergent showed us the values of the CMC. The concordance found between the value corresponding to the break of the absorbance and the assumed CMC obtained from solubilization makes the existence of the CMC more probable. The concentration of the monomeric molecule and the molar extinction coefficient of the molecule participating in micelle formation were calculated with use of a simple assumption.
Ionization Potentials of Some Organic Molecules. V. Heterocyclic Compounds Containing Nitrogen
Authors: Omura Itiro , Baba Hiroaki , Higasi Keniti , Kanaoka Yuichi
Published: July 2006

First ionization potentials of the following substances were determined by a modified critical slope method. Pyridazine 9.86±0.05, pyrimidine 9.91±0.05, pyrazine 10.01±0.02, s-triazine 10.07±0.05, 2,3-lutidine 9.68±0.02, 2,4-lutidine 9.43±0.02, and 2,6-lutidine 9.57±0.02 eV. Interpretations of the results are given from the view-point that the ionization potentials of these compounds are largely determined by the non-bonding electrons at the N atom.
Relations among Bond Order, Force Constant and Bond Length for the C–C and the C–N Bond in Conjugated Molecules
Authors: Anno Tosinobu , Ito Mitsuo , Shimada Ryoichi , Sado Akira , Mizushima Wataru
Published: July 2006

A general equation correlating bond orders with bond lengths of bonds between any particular pair of atoms in the conjugated systems are proposed. To test this equation applications have been made for C–C and C–N bonds. Because of the scarcity of the calculated values of bond orders for C–N bonds in the literature, bond orders of several molecules containing C–N bonds have been calculated, It is shown that the order-length relation is in good agreement with experiments. A theoretical, although approximate, equation correlating bond lengths with force constants has also been proposed and applied to C–C and C–N bonds. From these relations the length and the stretching force constant of C–N double bond are estimated to be 1.295 Å and 9.1×105 dynes/cm, respectively, the former being in agreement with the value calculated from the covalent radii given by Pauling.
Spectrochemical Study of Microscopic Crystals. XIV. Absorption Spectra and Structure of Dibenzene-chromium(I) Iodide
Authors: Yamada Shoichiro , Nakamura Hiroji , Tsuchida Ryutaro
Published: July 2006

Polarized absorption spectra of [Cr(C6H6)2]I in the visible and the ultraviolet region were quantitatively determined by Tsuchida-Kobayashi’s microscopic method using a single crystal. Visible and ultraviolet absorption spectra in solution and an infra-red spectrum in potassium bromide disks were also determined.

From the results of the measurements, it was concluded that the electronic state of the benzene rings in [Cr(C6H6)2]I deviates greatly from the state of free benzene and that the π-electrons of the benzene rings are attracted remarkably toward the chromium ion to form firm linkages.
The Formation of Cellulose IV in the Viscose Spinning
Authors: Tsuda Yoshizo , Mukoyama Sadataka
Published: July 2006

The formation of cellulose IV in the viscose spinning process was investigated by the X-ray diffraction measurements. Zinc cellulose xanthate model filaments were regenerated at various temperatures and their X-ray diffraction diagrams were examined. It was observed that the formation of cellulose IV is remarkable when zinc cellulose xanthate is regenerated at the temperature above a critical temperature which lies between 80°C and 100°C. The mechanism of partial formation of cellulose IV in the viscose spinning process was elucidated as follows: when zinc cellulose xanthate formed in the first bath is regenerated at a sufficiently high temperature in the second bath, the formation of cellulose IV consequently results. The main factors involved for the formation of cellulose IV are higher temperature of the second bath and higher concentration of zinc sulfate in the first bath.
Studies on the Chemical Constitution of Agar-agar. XIX. Pyruvic Acid as a Constituent of Agar-agar (Part 3). Structure of the Pyruvic Acid-linking Disaccharide Derivative Isolated from the Methanolysis Products of Agar
Authors: Hirase Susumu
Published: July 2006

1. The structure of the acidic compound, isolated from the partial metha-nolysis products of agar in the previous work, has been investigated.

2. Methylation data have indicated that the structure of the compound is 4-O-4′, 6′-O-1″-carboxyethylidene-β-d-galactopyranosyl-3,6-anhydro-l-galactose dimethyl-acetal, the β-linkage being suggested on the basis of the optical rotatory behavior.

3. The structure assigned is also supported by the result of partial hydrolysis and periodate oxidation of the compound.

4. No information has been obtained as to the configuration of the carbon atom C1 of the ethylidene group in the molecule.
Stoichiometric Investigations of the Liquid State IV. Viscosity of Associated Liquid
Authors: Tyuzyo Kiyoshi
Published: July 2006

(1) It is concluded from analysis of viscous flow that associated liquid can be classified as follows.

The first kind: Associated bodies can be distinguished clearly from one another, owing to the strong hydrogen bond. Each associated body flows as a unit in the case of viscous flow.

Examples: saturated fatty acid, saturated aliphatic alcohol, hydrogen fluoride, hydrogen cyanide.

The second kind: There are no associated bodies which are distinguished clearly from one another, owing to the weak hydrogen bond. The liquid makes overall three-dimensional network structure. Hydrogen bond is destroyed in the case of viscous flow.

Examples: water, ethylene glycole, glycerin, ammonia.

(2) Influence of branching, polar group and ring upon activation energy of viscous flow of unassociated liquid is discussed.

(3) It is found that entropy of activation of viscous flow of unassociated liquid is constant and equal to ca. −2.9 E.U./mole with some exceptions.

(4) The method for calculating degree of association of associated liquid of the first kind from energy and entropy of activation of viscous flow is presented.

(5) Association state of the first kind liquid is discussed in detail.
Hydrolysis of Carbohydrates in the Presence of Hydrochloric Acid or Acidic Ion-exchange Resins
Authors: Kaichi Sh\={o}z\={o}
Published: July 2006

Potato amylose and sucrose were hydrolyzed in the presence of hydrochloric acid or acidic ion-exchange resin catalyst. In hydrolysis of amylose at 65°C, the efficiency of resin catalysts was negligibly small as compared with that of hydrochloric acid. In hydrolysis of sucrose at 50°C, the efficiency of resin catalysts was less than that of hydrochloric acid and different according to their sizes. The relation between the average radius and the rate constant was obtained in a broader range than ever.
Rapid Determination of Inorganic Sulfur in Various Forms, Particularly in Sulfide Ores, by the Tin (II)-Strong Phosphoric Acid Reduction Method
Authors: Kiba Toshiyasu , Akaza Ikuko , Sugishita Nobuyuki
Published: July 2006

The procedure for the determination of sulfate sulfur using a new reagent, tin (II)-strong phosphoric acid, previously devised by the authors, has been extended to the determination of sulfur in other forms of inorganic compounds, e.g., sulfide ores (zinc blende, galena and pyrite), sulfides, thiosulfates, sulfites and thiocyanates. Two procedures of the analysis have been proposed by the authors : one, suitable for sulfide ores, sulfides, and sulfites, in which samples are treated directly with tin(II)-strong phosphoric acid to reduce the sulfur to hydrogen sulfide, and the other,, suitable for sulfites, thiosulfates, and thiocyanates, in which samples are previously treated with bromine water to oxidize the sulfur to sulfate, and the sulfate is reduced to hydrogen sulfide. The hydrogen sulfide evolved from the sample is absorbed in zinc acetate solution and titrated iodimetrically as usual. The rapidity and the simplicity of the original method are still retained in this case,, by which less than 30 milligrams of sulfur in the sample can be estimated within thirty minutes with good reproducibility.
On the Relation between Viscosity and Critical Micelle Concentration of Detergent Solutions. III. Relations between Micellar Molecular Weight, Viscosity and Critical Micelle Concentration of Detergent Solutions
Authors: Tyuzyo Kiyoshi
Published: July 2006

1) The following equation is found between association number (n) and critical micelle concentration (Cc in mol./1.) in detergent solutions

n=17.0×(1/C_c)^0.29

This relation holds, independent of an-ionic and cationic detergents and added electrolytes.

2) The following equations are found between micellar weight (Mm) and two kinds of intrinsic viscosity ([η1] and [η2]) already reported in the previous paper.

& logM_m=0.41{logn[η_1]}^2

& -0.39{logn[η_1]}+3.47

& logM_m=0.45{logn[η_2]}^2

& -0.91{logn[η_2]}+4.04

These relations are applicable, not only to ionic- but also to non-ionic detergents.

3) Discussions are made on the cause of characteristic behavior of viscosity at CMC. This phenomenon seems to be due to adsorption of detergent molcules to the wall of viscometer.
Phase Diagrams of Ca3(PO4)2-Mg3(PO4)2 and Ca3(PO4)2-CaNaPO4 Systems
Authors: Ando Jumpei
Published: July 2006

The small amount of magnesia contained in tricalcium phosphate replacing lime stabilizes β modification of the phosphate. However, a new compound Ca3Mg3(PO4)4 is formed below 1175°C when more than 0.6 mol. of MgO to 1 mol. of P2O5 is introduced into the phosphate. This compound is soluble in citric acid but less soluble in neutral ammonium citrate similarly as is serpentine-fused phosphate fertilizer.

In Ca3(PO4)2-CaNaPO4 system, a crystalline solution with α-rhenanite structure is easily formed within the range of 2.6 CaO· 0.4 Na2O· P2O5—2.4 CaO·0.6 Na2O·P2O5, and is furthermore stabilized by the admixture of calcium orthosilicate. This crystalline solution is highly soluble in both citric acid and citrate, composing a principal part of low-alkali calcined phosphate fertilizers.
The Crystal Structure of Bromodinitro-triammine-cobalt(III)
Authors: Komiyama Yoshimichi
Published: July 2006

The crystal structure of bromodinitro-triammine-cobalt(III) [Co(NH3)3(NO2)2Br] is monoclinic, with four formula units in a cell of dimensions; a=12.06Å, b=10.30Å, c=685Å and β=105.6°. The space group is C2h5−P21⁄n. The determination of atomic parameters was made by Fourier methods. The configuration of the complex molecule is described. One nitro-group is found to be in trans-position with respect to bromine atom and in cis-position to the other nitro-group.

The absorption spectrum of this complex was re-examined in aqueous solution.
Structural Variations of Kaolin Minerals
Authors: Takahashi Hiroshi
Published: July 2006

(1) The degree of crystallinity of kaolin minerals must be defined in relation to the degree of crystallinity in the internal randomness of the kaolin unit layer and that of the stacking randomness of kaolin unit layers. The X-ray diffraction data seem to reflect both internal and stacking variations.

(2) The relative degrees of crystallinity determined by the X-ray data and thermal data are consistent with each other in the series from kaolinite to fireclay. This holds also in the halloysite series. There is a continuous variation in the series from kaolinite to fireclay and also in the halloysite series. The X-ray data indicate that some of halloysites have a low degree of crystallinity, but the thermal data show a high degree of crystallinity. This means that in most cases the displacement in the series from kaolinite to fireclay is a one-dimensional displacement with respect to the b-axis, while the displacement in halloysite is a rotational displacement, that is, a two-dimensional displacement.

(3) The values of the base exchange capacity of kaolinite, fireclay and halloysite are correlated to the internal disorderliness of kaolin structure.

(4) The values of density of kaolin mineral samples nearly correspond to the degrees of the crystallinity with the exception of Kibushi-clay.

(5) The variety of shapes of kaolin minerals are determined in the relation of the two elements of the internal variation and the stacking variation.
Studies on the Cobalt(III) Complexes Containing Only One Chelate Ring. II. Syntheses and Properties of Monoethylenediamine-tetrammine-cobalt(III) Complexes, [Co en (NH3)4]X3
Authors: Shimura Yoichi
Published: July 2006

A new cobalt(III) luteo ion, [Co en (NH3)4]3+, has been prepared by the hydrolytic oxidation of [Co en (NH3)2 (NCS)2]+. The sulfate and the bromide of the new complex ion have been isolated. Several attempts to resolve the ion were unsuccessful.

The visible and the ultraviolet absorption spectra of all the members of the cobalt(III) ammine-ethylenediamine series have been measured and discussed.
Bond Localization and the Hyperconjugative Effect in the Aromatic Carbonium Ions. I. Absorption Spectra of Benzenium-,Toluenium-, and Mesitylenium- Ions
Authors: Morita Toshifumi
Published: July 2006

The semi-empirical LCAO MO treatment on the spectra of benzenium, toluenium, and mesitylenium ions have been carried out. Neither the localization nor the hyperconjugation of the H2–C bond with respect to the aromatic ring can explain the blueshifts of the experimental spectra by Reid with the increasing number of methyl substituents. If, however, benzenium and toluenium ions are assumed to be less hyperconjugated than mesitylenium ion, the spectroscopic behaviors of these aromatic carbonium ions are understandable. However, if the mesitylenium band is assumed to shift towards red compared with toluenium by the analogy of the case of protonated hexamethylbenzene and mesitylenium ion, whose absorption spectra have been measured by Kilpatrick and Hyman, our theoretical calculations will predict well the case of mesitylenium and toluenium ion in terms of both the bond localization and the hyperconjugation models. Unfortunately, however, the measurement on toluene in acid medium have not yet been made. Further the case of benzenium ion is yet open to question. Consequently we reserve making any distinct conclusions on these three aromatic carbonium ions.
A Method for the Fractionation of Oligopeptides Based on their Molecular Sizes
Authors: Narita Kozo , Fujiwara Sadao , Murasawa Shimako
Published: July 2006

A method to fractionate peptides based on their hydrated molecular sizes by the molecular sieve effect of sulfonic-acid type ion exchange resins, Dowex 50, is described. The behavior of some amino acids, peptides and partial protein hydrolysates towards molecular sieve is also studied. Various factors which control the fractionation of solutes by molecular sieve are discussed.
The Dipole Moments and Molecular Structures of Croconic Acid and Dimethyl Croconate
Authors: Washino Masamitsu , Yamada Kiyoyuki , Kurita Yukio
Published: July 2006

The dipole moments of croconic acid and dimethyl croconate were measured in dioxane and benzene solutions, respectively, as 9∼10 D and 5.7∼6.0 D. The moments of these molecules were calculated theoretically for several conceivable configurations by the method of molecular orbitals. The results confirm the structure presumed from evidences in organic syntheses. The accumulation of π-electrons on carbonyl oxygen is chiefly responsible for the large dipole moments, the effect being stronger in the acid. The hydroxyl groups of croconic acid lie in the ring plane, whereas the methoxyl groups are out of the ring plane to minimize the steric hindrance.
Magnetochemical Study of Cyanuric Acid, Melamine, and Some Derivatives
Authors: Matsunaga Yoshio , Morita Shiro
Published: July 2006

The magnetic susceptibilities of melamine, cyanuric acid, and eight of their derivatives were measured by the Gouy method. On the basis of the molar susceptibilities of the four compounds which have no tautomeric form, the constant for triazine was estimated at −36.5. It appeared that Gray and Cruickshank’s method gives too small an estimate for the isotropic part of the molar susceptibility in all cases and resonance with the zwitter-ionic structures brings about an increase of the isotropic diamagnetic contribution. With regard to cyanuric acid, the magnitude of the molar susceptibility seemed to be not inconsistent with the form containing a triazine ring. However, using Pascal’s second additivity rule we found that both the magnitude of the isotropic diamagnetism and that of the molar anisotropy favor the carbonyl form.
Investigation on Dissolving Pulp. XIV. Some Behavior of Wood Pulp and Cotton Linters in Phosphoric Acid
Authors: Koshizawa Tokumi
Published: July 2006

The average DP of cellulose dissolved into phosphoric acid of various concentrations has been determined by viscometry. The relations of average DP of dissolved part to the concentration of phosphoric acid are not the same in the three samples–dissolving sulfite pulp, prehydrolyzed sulfate pulp and cotton linters. The fact may be ascribed to the factors such as lateral order other than the degree of polymerization. The rate of hydrolysis of cellulose in 70% phosphoric acid at 20°C was also determined as to both cases of dissolved part and insoluble residue. The rate of hydrolysis of the dissolved part is almost independent of the kind of cellulose, while that of the insoluble residue greatly depends on the degree of swelling in the solution.
The Action of Hydrogen Bromide and Oxygen on Various Ethenoid Compounds. III. The Steric Effects of the Bromo Free Radicals Produced from Various Ethenoid Compounds on the Reactivities with Oxygen
Authors: Takahasi Makoto
Published: July 2006

The action of oxygen and bromine on β-methylcinnamic acid in benzene in the sunlight at room temperature caused an oxidative cleavage of the double bond, giving acetophenone and carbon dioxide, in addition to β-methylcinnamic acid dibromide. Similar experiments with cinnamic acid, atropic acid, p-methoxycinnamic acid, gave only dibromides either with or without introduction of oxygen.

Although a complete identification of the reaction products from the reaction of hydrogen bromide and oxygen on β-methylcinnamic acid was unsuccessful, it was found that a phenolic substance and a carbonyl compound were produced and that the formation of the phenol inhibited the progress of the reaction.

On the ground of these and other results which were described in the three preceding papers, the mechanism of the reactions of hydrogen bromide, bromine, and oxygen with ethenoid compounds is discussed.
Synthesis of Poly-(l-prolyl-l-leucyl-glycyl). An Attempted Synthesis of Model Collagen
Authors: Kitaoka Hidetoshi , Sakakibara Shumpei , Tani Hisaya
Published: July 2006

The two tripeptides, l-prolyl-l-leucylglycine (IV) and glycyl-l-prolyl-l-leucine (X), were synthesized, and IV was subjected to polymerization by the tetraethyl pyrophosphite, carbodiimide and p-nitrophenyl thioester methods, in which the most promising result was obtained by the pyrophosphite method. The highest molecular weight of the polypeptide which was obtained was about 6000 and the repetition of the original tripeptide unit in the polypeptide was confirmed by the end groups determination. The polycondensation reactions of both the tripeptides, IV and X, were compared in parallel runs by the tetraethyl pyrophosphite procedure, and the comparison showed that IV gave a better yield and a higher molecular weight product than X. X and poly-(l-prolyl-l-leucyl-glycyl), which was obtained from IV, contained firmly bound water in spite of the fact that IV contained no crystallization water.
Polarographic and Coulometric Studies of Tropolone
Authors: Tanaka Nobuyuki , Nozoe Tetsuo , Takamura Tsutomu , Kitahara Sadako
Published: July 2006

The current-voltage curves of tropolone were recorded at the dropping mercury electrode in buffer solutions of various pH’s containing no borate. One reduction wave was observed in the pH region of 2.2 to 4.0, two waves with nearly equal heights, in the pH region of 5 to 6 and one wave, in the solution of pH higher than 8. All waves except the second in the intermediate pH region were found to shift to negative potentials with the increase of pH of the solution by approximately 70 mV./pH. The number of electrons involved in the reduction was determined by the controlled potential coulometric method. One-electron reduction was confirmed for the first wave at lower pH’s, two-electron reduction for the two-step waves at the intermediate pH region and two-electron reduction for the wave at higher pH’s. The current-voltage curves which were recorded with the solution preliminarily subjected to the controlled potential electrolysis gave two new waves; one is anodic and the other, cathodic. The former decreased with time and the latter increased. This indicates that the reduction product of tropolone is unstable and changed gradually to the substance which gives the reduction wave. The diffusion coefficients of tropolone were calculated from the limiting current using the revised Ilkovic equation.
Studies on Polymerization and Depolymerization of ε-Caprolactam Polymer VI. On the Reaction Mechanism of the ε-Caprolactam Polymerization by Alkali Metal Compound
Authors: Yumoto Hirosuke , Ogata Naoya
Published: July 2006

The basic compound of alkali metal reacts with ε-caprolactam and gives at first N-alkali metal ε-caprolactam. It can cause the polymerization of ε-caprolactam. The boiling of the reaction phase is necessary for making the reaction proceed. The polymerization is especially rapid and reproducible in case of dispersing alkali metal compound colloidally in ε-caprolactam. It is supposed, therefore, that the solid surface of the catalyser is a very important factor in the polymerization.
The Crystal Structure of Bis( glutaronitrilo)copper(I) Nitrate
Authors: Kinoshita Yukio , Matsubara Ikuo , Saito Yoshihiko
Published: July 2006

The crystal structure of bis(glutaro-nitrilo)copper(I) nitrate has been determined by the two-dimensional Fourier method. It is tetragonal P\bar421c with two formula units in a cell of dimensions: a=8.25±0.01 Å and c=9.71±0.01 Å.

The crystal consists of infinite two-dimensional networks of complex ion [Cu(NC–CH2–CH2–CH2–CN)2]nn+ and nitrate ions. A copper atom is tetrahedrally surrounded by four nitrogen atoms at a distance of 1.98 Å. Each glutaronitrile molecule is coordinated to two different copper atoms with nitrogen atoms at both ends and takes a gauche-gauche configuration with respect to the two C–C bonds. The nitrate ions lie perpendicularly to the c-axis. The trigonal nitrate ions seem to have statistical azimuthal orientations in the crystal and the apparent symmetry of the nitrate ion is \bar4.

All the atoms in the group Cu–N–C–C lie approximately on a straight line. This fact and the observed carbon-nitrogen distance of 1.14 Å suggest that the bond character in the carbon-nitrogen group may essentially be expressed as C≡N.
Behavior of Surface Active Molecules at an Interface. II. Statistical Thermodynamics of Monolayers of Rod-Like Molecules
Authors: Nakagaki Masayuki
Published: July 2006

On the basis of the two-dimensional analogy of the method of McMillan and Mayer, the van der Waals constant A0 for monolayers of rigid rod-like molecules is calculated theoretically for the cases in which all molecules are (1) vertical to the interface; (2) lying flat upon the interface; (3) inclined by a constant angle θ0; and (4) orienting freely.

The theoretical equations thus obtained are used to discuss the orientation of molecules in gaseous films of myristic acid, tridecylic acid and lauric acid. As the results, it is concluded that the molecules of myristic acid and tridecylic acid are lying flat upon the interface in the gaseous film until the phase transition to a condensed film occurs. On the other hand, molecules of lauric acid are freely orienting when the area per one molecule is large, and the orientation becomes the more vertical, the more the monolayer is compresssed. The molecular orientations during this compression process were described quantitatively.
Vapor Pressures of Molecular Crystals. XIV. Sulfamide and Diacetylhydrazine
Authors: Takagi Sadao , Shintani Ryuichi , Chihara Hideaki , Seki Syûzô
Published: July 2006

The vapor pressures of crystalline sulfamide and diacetylhydrazine were measured between 347°K and 358°K and between 342° K and 353° K, with the results, logP=11.047−(5300⁄T) and logP=12.195−(5384⁄T), respectively. The heats of sublimation were found to be 24.25±0.24 kcal./mole and 24.63±0.39 kcal./mole, respectively. The hydrogen bond (NH···O) energies were evaluated by subtracting from the observed heat of sublimation the contribution of the dispersion energy (by Slater-Kirkwood formula) and the contribution of the electrostatic interaction energy. The latter contribution was obtained by adopting the point dipole model with the dipole moment 3.9 D (for sulfamide) and by adopting the point charge model with the charges ±2.002 e.s.u. at C and O atoms diacetylhydrazine). The NH···O energies were 4.7 kcal. and 3.0 kcaL., respectively. The electrostatic interaction in diacetylhydrazine is repulsive. Critical discussions are given on the significance of the hydrogen bond energy values obtained by various methods. The inter-relation between the lattice forces and the packing of molecules in the crystals is discussed on the basis of the calculation of separated contributions to the lattice energy and it is shown that the principal forces, acting between diacetylhydrazine molecules are the dispersion forces and the antiparallel arrangement of C = O dipoles in crystal is only a deceptive appearance. It is suggested that the nearest approaches in the linear systems OH···O and FH···F are 2.76 Å and 2.55 Å, respectively, unless very strong conjugation with the molecular network occurs. The NH stretching modes of vibration in sulfamide absorb at 3338 and 3248 cm−1.
Kinetics of the Selenium Dioxide-Catalyzed Hydrogen Peroxide Oxidation of Dimethylaniline in Aqueous Methanol
Authors: Ogata Yoshiro , Tabushi Iwao
Published: July 2006

The selenium dioxide-catalyzed oxidation of dimethylaniline with hydrogen peroxide was investigated kinetically at 40∼60° in 50∼95 volume % aqueous methanol. The rate of the consumption of hydrogen peroxide at constant acidity of the reaction mixture was expressed as

v=k[H2O2] [SeO2] [Dimethylaniline]+k′[H2O2] [SeO2]

The first term of this equation seems to correspond to the rate of a reaction between dimethylaniline and a complex (I) produced rapidly from selenium dioxide and hydrogen peroxide, while the second term corresponds mainly to a slow reaction between selenium dioxide and hydrogen peroxide to yield the complex (II) followed by a rapid reaction with dimethylaniline. The energy of activation was 11.7 kcal.

When perchloric acid was added to the reaction mixture, the pseudo-first-order rate constant with respect to hydrogen peroxide first increased and then decreased via a maximum, which was explicable by the assumptions of the dissociation of the intermediate and the protonation of dimethylaniline. Electron-releasing groups tended to increase the rate. An increase of the water content in the solvent methanol decreased the rate. There was no evidence for the radical mechanism under these experimental conditions.
Polarographic Studies of Metallic Complexes. III. Pentammine Series of Cobalt (III) Complexes
Authors: Maki Nobufumi , Shimura Yoichi , Tsuchida Ryutaro
Published: July 2006

1. Most of the cobalt(III) complex ions of pentammine series, [Co(NH3)5X](3−n)+, are reduced irreversibly in two steps at the dropping mercury electrode. The first diffusion current corresponds to the reduction, cobalt(III) → cobalt(II) and the second to the reduction, cobalt(II) → cobalt(0). The diffusion current and concentration were linearly related.

2. The polarographic stability of cobalt (III) complexes of the pentammine series increases in the following order of the ligands;

I−, Br−, Cl−, CrO42−, NCS−<NO3−

<N3−<SO42−<NO2−<C2O42−

<CH3COO−<NH3<OH2<OH−

<CO32−, HCO3−

(Supporting electrolyte; 0.5 F potassium sulfate).

The reverse of the order was found between carbonate and water molecule when 0.1 F potassium chloride was used as a supporting electrolyte. This order did not agree with that of the spectrochemical series of the pentamminecobalt(III) complexes.

3. In dilute perchloric acid the welldefined wave was obtained for aquopentamminecobalt (III) ion, [Co(NH3)5OH2]3+, while the ion gave a modified wave in the first reduction step in neutral supporting electrolyte, potassium chloride or potassium sulfate.
Studies on the Cephalin of Escherichia Coli
Authors: Kurokawa Masaharu , Hotta Kyoko , Yoshimura Tomoko , Makita Mitsuo , Hara Ichiro
Published: July 2006

The lipids were extracted from the crude toxic substances, isolated from Escherichia coli by Hosoya’s method. These lipids which were 7.2% of the crude toxic substances by weight, were fractionated by solvents. One of these fractions, that was soluble in diethyl ether and ethanol, contained 7.0% ethanolamine and 1.5% serine, and the other that was soluble in diethyl ether, but insoluble in ethanol contained 2.0% ethanolamine and 4.6% serine. There was no choline in any fraction. Average neutralization values of fatty acids in these two fractions were 194 and 239 respectively.
Experiments on Synthetic Mica Crystal Growing. Crystal Growing with Carbon Granule Resistance Furnace
Authors: Noda Tokiti , Sumiyoshi Yoshihiro
Published: July 2006

Synthetic mica crystal growing experiments were carried out with a graphite crucible and a well-sintered high-aluminous clay crucible in a carbon granule resistance furnace of 30 kg. melting capacity, specially designed for this purpose. In experiments with a graphite crucible, the melt often became supercooled and crystallized rapidly, to result in small crystals once crystallization started at the supercooled temperature. With a clay crucible, several experiments failed because of cracks in the crucible or because of corrosion of the crucible by the melt. Only with a well-sintered high-aluminous clay crucible and under the condition of small loss of fluorine and potassium in the melt were perfect large single crystals measuring about 5 cm. by 5 cm. formed even at a mean cooling rate of 2∼5°C/hr. in the range of 1360°C to 1300°C. The yield of large single crystals was very small, doubtless because only the few crystals which had formed earlier had enough time and space to be in contact with the melt and thus to grow to large size. If the growing crystals come into contact or collide with other growing crystals, the crystals are either prevented from growing further or become strained or bent. Consequently, for crystals to grow to a large size, they must be in contact with the melt for a long time without being disturbed by other crystals. This can be done when crystals grow in the same direction. It was found that the temperature gradient of 4∼5°C/cm. was necessary for crystals to grow in one direction.

Among many factors affecting the growth of crystals, the rate of cooling should be controlled to secure the rate of crystal growth at less than 0.06 mm./min. in order to grow perfect and flawless single crystals of mica.

Needless to say, a sufficient volume of melt is necessary to grow large crystals, i. e. a large quantity of melt gives more opportunity for large crystals to grow. Crystals measuring 5 cm. by 5 cm. were never obtained before the 30 kg. melting experiments were carried out.
The Density of the Poly cyclic Aromatic Compounds
Authors: Inokuchi Hiroo , Nakagaki Masayuki
Published: July 2006

The density (ρ) of the polycyclic aromatic hydrocarbons, from benzene (C6H6) to circumanthracene (C40H16), are correlated closely to the number of carbon atoms (N) included in the molecule. We may be expressed the relation as log (1⁄ρ−1⁄ρ∞)=−(1⁄2)log N+0.120, in which ρ∞ is the density of graphite, 2.26. The agreement of the computed values with the observed results is satisfactory. A trial to apply the equation to calculate the density of carbons is made with some success.
Electron Diffraction Investigation on the Molecular Structure of n-Butane
Authors: Kuchitsu Kôzo
Published: July 2006

The molecular structure of n-butane has been investigated by means of the sector-microphotometer method of electron diffraction. The least-square analysis of the radial distribution curve has been carried out both for modified and unmodified curves giving the internuclear distances as well as their mean amplitudes and the bond angles. The estimation of experimental standard errors has been made by examining various sources of errors. Important results are the following:

a) The average distance of the C–C bonds is 1.539±0.003Å.

b) The angle C–C–C is 112°9′± 9′, is considerably greater than the tetrahedral angle.

c) The position of hydrogen atoms is located with considerable accuracy; C–H=1.100±0.003Å and <C–C–H=110°22′±15′.

d) The mean amplitudes measured are in agreement with the calculated values within the limit of error.

e) The existence of rotational isomers, the trans and the gauche forms, are confirmed. The structure and the fraction of the isomers are determined. The result is consistent with the spectroscopic results.
Studies on the Sapogenins of Dioscorea tokoro Makino. IV. The Contents of Tokorogenin, Yonogenin and Diosgenin
Authors: Morita Katsura
Published: July 2006

(1) Improved isolation of tokorogenin, yonogenin and diosgenin from the rhizomes of D. tokoro Makino collected at Gotenba is described.

(2) The sapogenin contents in rhizomes of D. tokoro Makino collected in various districts in Japan were examined by means of chromatography.

(3) The sapogenin contents in rhizomes of cultivated plants of D. tokoro Makino were examined and it was found that the plants containing diosgenin as the major ingredient contain very small amounts of tokorogenin and yonogenin or lack them, while those containing large amounts of tokorogenin and yonogenin give only minute yields of diosgenin or lack it.
The Kinetic Study of Surface-chemical Reactions at Extremely Low Pressures. III. The Thermal Reaction between Water Vapor and a Tungsten Filament. Part III
Authors: Hamamura Takuya
Published: July 2006

Hydrogen hardly affected the reaction at lower filament temperatures or higher pressures of water vapor, but it decreased the rate of reaction at higher temperatures and lower pressures, as ascribed to the “clean up” of hydrogen by the filament.
Photometric Study on the Change of Basic Rhodochromium Ion to Basic Erythrochromium Ion in Aqueous Solution
Authors: Mori Masayasu , Ueshiba Shigeru , Yamatera Hideo
Published: July 2006

The conversion reaction of the basic rhodo ion to the basic erythro ion in an alkaline solution was found to be of the first order. The velocity constants at 10°, 15°, 20°C and 25°C were measured, and the energy of activation, the frequency factor and the entropy of activation calculated. The reaction velocity appeared to be somewhat diminished by higher concentration of sodium hydroxide. The absorption spectrum of unstable basic rhodo salt was derived from the kinetic data.
Studies on the Silk-Palladium Catalyst. I Preparation and Stability
Authors: Izumi Yoshiharu
Published: July 2006

1. The highest hydrogenation activity was obtained when the silk-palladium catalyst was prepared by boiling the silk fibroin fibers with 0.1% palladous chloride solution in 0.1 n acetic acid for 8 min. and then hydrogenating the resulting chelate.

2. The catalyst prepared as above was, however, devoid of the capacity of asymmetric catalysis, although the same catalyst prepared in distilled water (instead of dilute acetic acid) was able to achieve asymmetric reduction.

3. The catalyst and its precursor chelate could be stored in dry state without any loss of activity.

4. The synthetic fiber, 6-Nylon, could be successfully used as the carrier in place of silk fibroin.
Dilatometric Study on Transition Phenomena of Various Polyethylenes with Different Degree of Chain Branching
Authors: Tanaka K\={o}ji
Published: July 2006

The specific volumes of various kinds of polyethylenes with the different degrees of short chain and long chain branchings were measured by volume dilatometry in the temperature range from −40° to 150°C, and volume-temperature curves were determined. Polyethylene having the higher degree of short chain branching had the higher specific volume at any temperature below the melting point. Above the melting point specific volumes of all the polyethylenes were equal at the same temperature. Melting point, crystallizing temperature, premelting point, and glass transition temperature were raised with the decrease of degree of short chain branching. The curvature of the curve showing premelting process grew large as the amount of short chain branching contained in the sample became small, and came to show the typical first order transition phenomenon.
The Photolysis of Acetaldehyde in the Presence of Hydrogen Sulfide
Authors: Imai Naomi , Toyama Osamu
Published: July 2006

Acetaldehyde has been photolyzed in the presence of hydrogen sulfide over the temperature range from 150 to 360°C. The initial rates of decomposition obtained under various experimental conditions are consistent with a mechanism which involves the reactions CH3+H2S=CH4+HS (6) and HS+CH3CHO=H2S+CH3CO (7) in addition to those established already for the photolysis of acetaldehyde alone. Analysis of the data on this basis gives a value of 4.0 kcal./mol. for the difference in activation energy E4–E6 where E4 refers to the reaction CH3+CH3CHO=CH4+CH3CO (4). This result, when combined with E4 = 6.8 kcal./ mol. found by Ausloos and Steacie, gives E6=2.8 kcal./mol. in excellent agreement with our previous value of 2.6 kcal./mol. obtained in the photolysis of acetone in the presence of hydrogen sulfide. As the temperature is lowered and the ratio [H2S] / [CH3CHO] increased, the importance of the combination of methyl radicals to ethane as the chain terminating step decreases, until it is replaced by the combination of hydrosulfide radicals. This is explained in terms of the relationship E7>E6.
Estimation of the Energy of Hydrogen Bonds Formed in Crystals. III. Amides
Authors: Aihara Ariyuki
Published: July 2006

The energies of hydrogen bonds formed in the crystalline state of thirteen amides and one amine have been estimated following the procedure proposed in a previous paper. The values of the energy of an NH···O bond can be estimated at about 4±1 kcal./mol. for the majority of compounds treated in this paper, except two lactams which show energy values as large as 6∼7 kcal./mol. A comparison was made between the energy values of NH···O and OH···O bonding using the data obtained by the author and other investigators.
Dichroism of Dyes in the Stretched PVA Sheet. IV. Absorption Spectra of Carbocyanines and Note on the Chemical Structures
Authors: Tanizaki Yoshié , Ono Hisataké
Published: July 2006

1. Dichroism of the electronic spectra over 220 mμ was measured for 1,1′-diethyl-2,2′-cyanine, -dicarbocyanine, and -tricarbocyanine iodide, and -4,4′-cyanine iodide, respectively, in the stretched polyvinylalcohol sheets under the stretch ratio of about 6∼10.

2. The correspondence of the transition directions of absorptions and the chemical structures, and the classification of the absorption bands were made into tables.

3. All the dichroic behaviors of the absorption bands could be interpreted by the transitions along the longitudinal axis of the molecule and by those, localized in the quinoline nuclei, of two directions at right angles.

4. It was confirmed that the second group absorptions correspond to the overtone of the first group ones. It was shown by the schematical potential curves that the systematic changes in the band distances in these groups with the variation of the methine bond number may be plausibly explained in connection with the vibrational states.

5. It was pointed out that a reasonable understanding for certain experimental facts in dichroism is given by regarding the molecular structures as follows; 1,1′-diethyl-2,2′-cyanine and -4,4′-cyanine are far from planar because of their particular great steric hindrance, and the other cyanines are strained by the successive addition of a peculiar twisting angle per methine bond.
Theory of the Influence of the Dielectric Constant on the Rate of Reaction in Solution with Application to Enzyme Reactions. I. Development of the Theory and its Application to Some Simple Systems
Authors: Hiromi Keitaro
Published: July 2006

A theory has been developed on the relationship between the equilibrium constant or the rate constant of a reaction and the dielectric constant of the solvent based on the Kirkwood’s model. It is applicable to equilibrium states or reaction processes in which ions or molecules having arbitrary charge distributions are involved, including enzyme reactions. The theory predicts that there is a linear relationship between the logarithm of the equilibrium or rate constant and the reciprocal of the dielectric constant of the solvent. The slope is determined by the new parameter L, termed the charge configuration function, and the radius of each species involved. L of a species is a function of the magnitudes and the relative positions of charges in it and its radius. Tables have been presented in order to facilitate the evaluation of L.

The applicability of the theory has been tested for the dissociation of carboxylic acids, the SN1 solvolysis of organic halides, and the acid and base hydrolyses of esters, amides and anilides, and the results are found to be satisfactory.

The influence of ionic strength on the theoretical expressions has also been discussed.
Studies on the Decomposition of Ammonia and Hydrazine by High Frequency Discharge
Authors: Takahashi Saku
Published: July 2006

1) The decomposition of both ammonia and hydrazine were carried out under high frequency discharge and the effects of frequency on the chemical reactions were investigated. The frequencies of electric current were 100 and 250 MC.

2) The effects of frequency appeared clearly on the decomposition of hydrazine: under 100 MC frequency discharge the decomposition was a 1st order reaction, while under 250 MC it was approximately zero order reaction, and the overall reaction was retarded moderately by the hydrogen produced in the course of the reaction.

3) As for the decomposition of ammonia, in any case, the reactions were retarded by hydrogen. Under 100 MC frequency discharge the reaction was 1st order, while under 250 MC it was a fractional order reaction.