bluuebunny/crossref_metadata_2025 huggingface dataset:
Molecular Structure and Rotational Isomerism of Some Fluorochloroethanes
Authors: Iwasaki Machio
Published: July 2006

In order to investigate the molecular structure and rotational isomerism, the electron diffraction camera having a rotating sector was designed and constructed and its application to some fluorochloroethanes was made successfully. The shortening of the C–F and the C–Cl bond by the substitution of atoms attached to one and the same carbon atom with other fluorine atoms was also revealed in fluorochloroethanes as well as fluorochloromethanes, although in the case of the C–Cl bond distance the inaccuracy of the data does not permit a definite conclusion to be drawn. It was definitly confirmed that there exist two rotational isomers, the trans (or Cs) and the gauche forms, in the vapor state for the molecules in question. The energy differences between the isomers and the azimuthal angles of the gauche form were determined and further discussed from the standpoint of intramolecular potential.

It was found that three fluorochloroethanes in question have almost equal and small energy differences in contrast to the remarkable variation in the case of chloroethanes. This is caused by the fluorine substitution which produces the decrease of the electrostatic part in the energy difference between the isomers.
The Crystal Structure of trans-Dibromo-bisethylenediamine-cobalt(III) Bromide Hydrobromide Dihydrate
Authors: Ooi Shun’ichiro , Komiyama Yoshimichi , Saito Yoshihiko , Kuroya Hisao
Published: July 2006

The structure of trans-dibromo-bisethylenediamine cobalt(III) bromide hydrobromide dihydrate has been determined by X-ray analysis. [Co en2Br2]Br·HBr·2H2O is monoclinic, a=10.98, b=8.18, c=9.46 Å, and β=113.2°, space group P21⁄c, two formula units in the cell. The structure consists of [Co en2Br2]+, [H2O···H···H2O]+ and Br−, and is isotype with [Co en2Cl2]Cl·HCl·2H2O. The complex ion has a center of symmetry. Two enantiomorphous ethylenediamine molecules, taking “gauche” configration, are coordinated to a cobalt atom. A cobalt atom is surrounded in a square coplanar configuration by four nitrogen atoms at distances 2.0 Å, and on a line approximately perpendicular to the plane of nitrogen atoms are two bromine atoms at distances 2.44 Å. The marked dichroism of the crystal is explainable in terms of the characteristic features in the arrangement of the complex ions in the crystal.
Study on Zinc Oxide-Chromium Oxide Catalyst. III. Promoting Effect of Chromium Oxide on Catalytic Activities for Methanol Synthesis and Decomposition
Authors: Ogino Yoshisada , Oba Masaaki , Uchida Hiroshi
Published: July 2006

The catalysts have been prepared from pastes of zinc oxide powder kneaded with chromic acid solutions of different concentrations. From the pastes two series of the catalysts have been produced, namely the one directly from the paste and the other from the solid, free of the liquid, in the paste. Only the results on the latter series can give the correct relation of the catalyst composition to the catalytic activity, which indicates the activity rising with the higher chromic acid contents to an asymptotic maximum at the Cr/Zn ratio of 0.5.

\qquadThecatalytic activity on the catalysts of different Cr/Zn ratios almost parallels the specific surface area of the catalysts, while the specific activity based on unit specific surface area of the catalysts changes in a far less degree than the change in activity per unit gram of the catalyst. These suggest an intercrystalline promoting effect of chromic acid. Moreover the closer investigation on the activity reveals that both the activation energy and the frequency factor of the reactions which are based on unit surface area show a downward tendency with the increasing Cr/Zn ratios asymptotically to their respective minimums of presumable zinc chromite spinel. This shows besides an intracrystalline promoting effect of chromic acid.

\qquadWithinthe range of the present study, hardly any effect of chromic acid addition undesirable to the selectivity in the synthesis has been found.
Dissociation Constants of Some Carboxylic Acids in Mixed Aqueous Solvents
Authors: Yasuda Motoo
Published: July 2006

Several authors determined dissociation constants of acids such as benzoic, succinic and azelaic acids in mixed solvents and reported that the dissociation constants determined in aqueous dioxane were higher than those determined in aqueous alcohols having the same dielectric constants. However, if the variation of the amount of water in mixed solvents is taken into consideration in calculating the dissociation constant, an acid has almost the same dissociation constant in various mixed solvents with the same dielectric constant.
Interaction Polarization of the Hydrogen Bonded Complexes
Authors: Kimura Ko , Fujishiro Ryoichi
Published: July 2006

The dielectric measurements for the system of benzyl alcohol-dioxane and that of phenol-dioxane, respectively, were carried out by using benzene as the solvent.

The induced polarization of the π-electrons in the latter system was evaluated based on some assumptions. From these, the additional moments due to delocalization were estimated and the weights of the structure III were evaluated for both systems.
Thermodynamic Studies on Cobalt Complexes. II. Solubility and Standard Free Energy of Formation of [CoA6]-type Salts
Authors: Mori Motoshichi , Tsuchiya Ryokichi , Okano Yasuhiro
Published: July 2006

The solubilities of hexamminecobalt(III) chloride, bromide, nitrate and perchlorate were measured at 10∼35°C. From the solubility measurements the relationships between the equilibrium constant of the solution and the temperature were calculated. The heats of solution calculated from these data agreed approximately with the values given in the literature and those calculated by using formulae of Kapustinski\v{i} and Fajans.

The free energy changes of formation of these complexes in the solid state were calculated for the first time. It is concluded from the results that the stability of these salts decreases in the following order:

& [Co(NH_3)_6]Cl_3>[Co(NH_3)_6](NO_3)_3>

& [Co(NH_3)_6]Br_3>[Co(NH_3)_6](ClO_4)_3
Therrnodynamic Studies on Cobalt Complexes. III. Thermal Dissociation of Hexamminecobalt(III) Chloride and Chloropentamminecobalt(III) Chloride
Authors: Mori Motoshichi , Tsuchiya Ryokichi
Published: July 2006

1. The thermal dissociation of hexamminecobalt(III) and chloropentamminecobalt(III) chlorides was studied. The heats of dissociation calculated from the the data of dissociation pressure determined are in good agreement with the values calculated from other sources.

2. The free energy change of dissociation of hexamminecobalt(III) chloride was calculated and by combining this value with the standard free energy of formation of that complex previously obtained, the standard free energy of formation of chloropen tamminecobalt(III) chloride in the solid state was determined.

3. The rate of the thermal dissociation of hexamminecobalt(III) and chloropentamminecobalt(III) chlorides was determined and the activation energies of the dissociation were calculated.
Normal Stress Effects in Polymer Solutions. I. Measurements in a Parallel Plate Instrument
Authors: Tamura Mikio , Kurata Michio , Kotaka Tadao
Published: July 2006

Results of some geometrical studies of normal stress effects in a parallel plate instrument have been discussed. The parallelism and the concentricity of two plates are necessary conditions for the quantitative measurement. The rotational velocity of a cup should be kept below about 70 rpm for the apparatus with the cup radii about 6∼8 cm. to avoid the influence of the centrifugal force. Accesses of manometer tubes with the diameter about 2 mm. cause no appreciable disturbances. The influence of side gap may also be neglected. With these experimental remarks, the normal stresses are obtained as a function of the rate of shear.

The applicability of the concentration-temperature superposition procedures has been tested with the data obtained here. They are partly valid in some limited range of variables.
Intramolecular Interaction between Hydroxyl Group and π-Electrons. II. Limitation of the Interaction by Chain-length in ω-Hydroxy-1-alkenes
Authors: Oki Michinori , Iwamura Hiizu
Published: July 2006

Infrared absorption was measured with five ω-hydroxy-1-alkenes in the 3 μ region, using an instrument of high resolution and the following results were obtained.

1) Intramolecular interaction between the hydroxyl group and π-electrons was found in allyl alcohol and in 3-buten-1-ol.

2) Interactions which occur in allyl alcohol and in 3-buten-1-ol may be of a different kind.

3) Higher homologs also possess two O–H stretching absorption bands but these bands can not be associated with the intramolecular interaction.
Polarography of Tetracyano- and Dithiooxalato-Nickelate(II) Complexes
Authors: Maki Nobufumi , Kida Shigeo , Tsuchida Ryutaro
Published: July 2006

1. It was verified polarographically that the reaction between the ions, [Ni(CN)4]2− and [Ni(C2S2O2)]2−, takes place and the mixed complex ion, [Ni(C2S2O2) (CN)2]2−, is formed in solution. The rate of the reaction was so great that the progress of the reaction could not be traced by the usual polarographic method. Meanwhile the wave of the oxalato-ethylenediamine copper(II) complex, [Cu en ox], the presence of which in solution had been verified spectrophotometrically, was not detected polarographically. That is to say, the polarographic method can be applied to detect the formation of the mixed complex, the coordinating bonds of which have a considerable covalent character, such as [Ni(C2S2O2)(CN)2]2−, but can not be applied to detect the mixed complex having ionic bonds.

2. The ion, [Ni(C2S2O2)2]2−, is reduced irreversibly in two steps at the dropping mercury electrode in the presence of 0.0032% Tween-80, when If potassium chloride solution was used as a supporting electrolyte. The heights of the two waves are not proportional to the concentration of the ion. The height of the wave for the unit concentration of the ion increases with the decreasing concentration of the ion.
The Kinetics of the Complex-forming Reaction between Nickel(II) and Ethylenediaminetetraacetate
Authors: Tanaka Nobuyuki , Sakuma Yasuhiko
Published: July 2006

The complex-forming reaction of nickel (II) with ethylenediaminetetraacetate (EDTA) was found to proceed in acetate buffers of pH 3.8 to 5.2 through four different reaction paths,

Ni2++HY3− \xrightarrowk1a NiHY−

NiOAc++HY3− \xrightarrowk1b NiHY−+OAc−

NiHY− \ightleftarrows NiY2−+H+

Ni2++H2Y2− \xrightarrowk2a NiH2Y

NiOAc++H2Y2− \xrightarrowk2a NiH2Y+OAc−

NiH2Y \ightleftarrows NiHY−+H+ \ightleftarrows NiY2−+2H+

The change in the polarographic diffusion current of nickel(II) at the rotated dropping mercury electrode was utilized to follow the decrease of the nickel(II) concentration in the reaction mixture after the initiation of the reaction. The rate constants of the reaction paths were determined at 0°C and ionic strength 0.2, with the results:

k 1a=1.06×104 mol−1 liter sec−1

k 1b=2.25×104 ”

k 2a=2.04×102 ”

k 2b=6.04×102 ”

These constants are much smaller than those of the corresponding reactions between copper(II) and EDTA.
Molecular Rotations of Glucides in Relation to their Structures. VII. Internal Conformation of O1α–Cm Bond in (OCH3)1α of Methyl α-d-Xylopyranoside and of Methyl β-l-Arabinopyranoside in Aqueous Solutions
Authors: Yamana Shukichi
Published: July 2006

By the author’s new method, the internal conformation of O1α–Cm bond in (OCH3)1α of methyl α-d-xylopyranoside and of methyl β-l-arabinopyranoside in aqueous solutions was presumed. At the same time, Isbell and Pigman’s data and Hudson’s data of [M]D20(W) of l-arabinoses were discussed.
On the Intramolecular Charge Transfer Spectra and Structure of Isomeric Aminopyridines
Authors: Mataga Noboru , Mataga Shizuyo
Published: July 2006

The electronic spectra and structure of isomeric amino-pyridines have been studied theoretically employing the general method for the study of a composite system. The calculated results correspond satisfactorily with the experiment, in general, and the nature of electronic transitions in these molecules has been made clear. Thus it is evident that there is no difficulty in assuming the amino-form of these molecules in interpreting theoretically their electronic spectra and structure.
Absorption Spectra of Dyes. III. On the Composition of Complexes Formed in Mixtures of Chlorazol Sky Blue FF and p-Nitroaniline→γ Acid in Aqueous Solution
Authors: Kobayashi Teruaki , Tanizaki Yoshié , Ando Noboru
Published: July 2006

1. The change in spectrum at 620 mμ of the mixture of Chlorazol Sky Blue FF and p-nitroaniline→γ acid in aqueous solution was measured in detail at room temperature, by varying the concentration of the component dyes.

2. On the assumption that the spectral change is due to the complex formation, the composition of complexes was discussed by comparing the observed and the calculated difference in optical density.

3. It may be supposed that a 1:1 complex occurs to a great extent over a range of low concentration of p-nitroaniline→γ acid as compared with that of Chlorazol Sky Blue FF, and that higher complexes are formed in the presence of an excess of the acid dye.
A Convenient Method for the Calculation of the π-Electronic Structures of Aromatic Derivatives
Authors: Nishimoto Kichisuke , Fujishiro Ryoichi
Published: July 2006

It was show that the set of vacant orbitals of the conjugated system would be a mirror image of that of occupied orbitals. Using this relation the calculation of the π-electronic structures of the aromatic derivatives are considerably simplified. As an example, the molecular diagrams of the benzene hydroxy derivatives were calculated.
Spectrochemical Study of Microscopic Crystals. XIX The Structure and Absorption Spectra of Fremy’s Salt
Authors: Yamada Shoichiro , Tsuchida Ryutaro
Published: July 2006

Absorption spectra in the visible and ultra-violet region have been determined at room temperature by Tsuchida and Kobayashi’s microscopic method with crystals of Fremy’s salt and related compounds. Infrared absorption spectra have also been measured with these compounds.

The results of the measurements are discussed in relation to the structure of the compounds. A steric condition, visible and ultra-violet absorption spectra and infrared spectra are found to be in best agreement with a structure having a peroxide grouping.
On the Mechanism of Oxidation by Cuprous Chloride, Pyridine and Air. I. The Properties of the Reaction
Authors: Kinoshita Keiz\={o}
Published: July 2006

(1) By aerial oxidation of aniline catalyzed by cuprous chloride in a pyridine solution, azobenzene of about 60% is produced. In this reaction, the actual oxidant may be considered “oxidant A” which is produced by aerial oxidation of cuprous chloride pyridine complex.

(2) Hydroxy cupric chloride pyridine complex, a reaction product of cupric chloride pyridine complex with a methyl alcohol solution of potassium hydroxide, has a similar catalytic activity.

(3) These two complexes are to be considered strong bases.

(4) These two complexes have a remarkable resemblance to each other.
The Aconite Alkaloids. XXX. On Lucidusculine
Authors: Suginome Harusada , Amiya Takashi , Shima Takeo
Published: July 2006

1. In lucidusculine the presence of a double bond had previously been assumed. Further, on the basis of observations of the infrared spectra of luciculine, lucidusculine diacetate and dihydrolucidus-culine diacetate, the presence of a terminal methylene group in lucidusculine was suggested.

Kuhn-Roth oxidation of mesoluciculine and of dihydromesoluciculine and ozonolysis of lucidusculine and of lucidusculine diacetate supported the suggested presence of a terminal methylene group. These results and the biogenesis of the aconite alkalodis show that the double bond in lucidusculine belongs to a terminal methylene groups.

2. The roots of Aconitum species from Shoya, Hidaka in Hokkaido, were divided into mother-roots and daughter-roots; the water-insoluble basic portions were obtained from both; lucidusculine and jesaconitine were isolated by the chromatographic method.
Vapor Pressure of Molecular Crystals. XIII. Vapor Pressure of α-Glycine Crystal. The Energy of Proton Transfer
Authors: Takagi Sadao , Chihara Hideaki , Seki Syûzô
Published: July 2006

Sublimation pressures of crystalline α-glycine were measured between 138 and 153°C by the effusion method. The pressure equation

logP(mmHg)=13.666-(6816.8/T)

fits well the experimental data. The heat, entropy and free energy (at 25°C) of sublimation were 31.18±0.49 kcal./mole, 49.33±1.17 cal./deg. mole and 16.47±0.60 kcal./mole, respectively. An energy cycle was constructed which correlates zwitterion and molecule in crystal and vapor states, and hydrated zwitterion and molecule in solutions. The observed heat of sublimation corresponds to the change in heat content in going from the zwitterioncrystal to gaseous molecules. The molecular configuration is more stable in vapor state. By using the experimental values of the heat of sublimation, the heat of solution of crystals into water and the temperature dependence of pKa in solution, with the help of the theoretical values of the lattice energy of the crystal, the following heat values were determined; the heat of proton jump in vapor, NH3+CH2COO− → NH2CH2COOH, −72 kcal./mole, the heat of proton jump in the crystal 7∼10 kcal./mole, hypothetical heat of sublimation of crystals composed of molecules 21∼24 kcal./mole, the heats of hydration of a zwitterion and a molecule −99.8 and −17.8 kcal./mole, respectively, the heat of solution of the hypothetical crystal to give a solution of molecular glycine 3∼6 kcal./mole, and the heat of self-neutralization in aqueous solution 9.7 kcal./mole. The negative quantities show that the processes are exothermic. It was shown that the proton transfer in a medium of large dielectric constant or in a strong crystalline field requires only a small amount of energy and its significance in chemical reactions and biochemical activities was suggested. Each of the derived heat values was examined by independent checks from different sources, except for the energies of proton transfer.
Studies on Crystal Hydrates. V. Zeolitic Dehydration of Dl-Tris-ethylenediamine-cobalt(III) Chloride Hydrate, Dl-[Co en3]Cl3·nH2O. Sorption and Desorption of Water Vapor. A Preliminary Study of the Dielectric Properties
Authors: Chihara Hideaki , Nakatsu Kazumi
Published: July 2006

The dehydration pressures of Dl-[Co en3]Cl3 ·nH2O (n≤4), were measured between 19 and 45°C at various water contents. The dehydration isotherm derived from the data is of type V of the BET classification with a constant pressure (2.85 mmHg at 25°C) region between n=2.5 and n=0.2, corresponding to the case of capillary condensation into pores of uniform size. The crystal lattice is stable after dehydration, showing the zeolitic nature of dehydration. The usual criterion of stepwise dehydration for the lattice-destructive dehydration does not apply to this type of crystal. The differential molar heat and entropy of dehydration have maximum values around n=2.7; this can be accounted for by the theory of cooperative phenomena. At very low water content, there is a possibility of rearrangement of atoms in the crystal as inferred by the entropy consideration. A preliminary study of the dielectric properties showed that the relaxation absorption occurs between −180°C and room temperature in the megacycle region with the activation energy for the relaxation about 7 kcal./mol. The dielectric loss due probably to the d. c. conduction was observed in the c-axis direction.
Studies on the Silk-Palladium Catalyst. II. General Properties
Authors: Izumi Yoshiharu
Published: July 2006

1. The silk-palladium catalyst was found to catalyze the hydrogenation of aliphatic C=C double bonds, aldehyde, nitriles and nitro groups directly attached to aromatic rings, azobenzene, and some oximino groups, but relatively weakly that of aliphatic nitro groups. The catalyst was completely inactive to aromatic C=C double bonds, aliphatic carbonyl (with the exception of α-ketoglutarate which was reduced to glutamate in the presence of ammonia), nitriles, and several oximes.

2. The catalyst, when used once, considerably increased its catalytic activity and this elevated activity persisted after several repeated uses.

3. Ethyl mercaptan was poisonous to the catalyst probably due to its combination with the active palladium atoms. Ferric and cupric ions inhibited the catalyst by forming chelate linkages with the carrier protein. The inhibition by these metal ions could be restored by ethylenediamine tetraacetic acid. Acetylation of the catalyst with acetic anhydride markedly reduced the activity, although the treatment of silk fibroin with acetic anhydride prior to the preparation of the catalyst gave a strongly active catalyst.
Intramolecular Interaction between Hydroxyl Group and π-Eelctrons. V. Electronic Effect in Arylcarbinols and a Preliminary Note on the Interaction in Benzylaniline Derivatives
Authors: Oki Michinori , Iwamura Hiizu
Published: July 2006

Absorption due to the O–H stretching vibration in the fundamental region was measured with fourteen benzyl alcohol derivatives to see the electronic effect of the substituent on the interaction between the hydroxyl group and the π-electrons and the following conclusions are deduced.

1) The nature of the interaction or the structure of the molecule which gives rise to the νO–H absorption at 3617 cm−1 is discussed and the interaction between the hydroxyl group and the π-electron on the carbon atom to which hydroxymethyl group is attached (structure III) is favored.

2) The consistency of the wave numbers at which two νO–H absorptions appear, gives further support to the idea that these absorptions originate in the existence of the two rotational isomers.

3) (Remark: Graphics omitted.) is in linear relation with Hammett’s σ values and the σ value of the m-benzyloxyl group is estimated as −0.204.

A similar phenomenon is also observed in the substituted benzylanilines.
The State of a Small Amount of Magnesium Contained in Calcareous Shells
Authors: Kitano Yasushi , Furutsu Tsuyako
Published: July 2006

An original method (Dissolution Method) for determining small amounts of magnesium contained in calcareous shells has been devised, and the state of magnesium has been determined by this method. As a result, it can be verified that small amounts of magnesium in calcareous shells are always contained as a solid solution of calcite and dolomite.
The Assignment of Infrared Absorption Bands of 1, 3, 5-Trichlorobenzene
Authors: Saëki Shinnosuke
Published: July 2006

The infrared absorption spectra of deuterated nd non-deuterated 1,3,5-trichlorobenzenes were measured in the vapor state from 5,000 to 400 cm−1. The results of our measurements allowed us the assignment of the fundamental bands of this substance by the aid of the product rule. As we could not observe all of the fundamental bands of this substance, the perfect application of the product rule was not possible. But we proved that our assignment did not conflict with the product rule.
The Reaction of Tropoids and Quinone Derivatives. I. Reaction of Several Tropolones and p-Benzoquinone-dibenzenesulfonimide
Authors: Seto Shuichi , Yamazaki Hiromi , Nishiyama Yukio
Published: July 2006

The reaction of tropolones with p-benzoquinonedibenzenesulfonimide was carried out and the following points were observed.

1) The 2′, 5′-dibenzenesulfonamidophenyl group enters the 5-position of the tropolone ring, similar to the case of phenol.

2) The reaction proceeds in the same way in the case of 4-isopropyltropolone, without interference of the isopropyl group.

3) In the case of tropolones with a substituent in 5-position, reduction of p-benzoquinone-dibenzenesulfonimide takes place.
Relations between Electronic Absorption Spectra and Spatial Configurations of Conjugated Systems. IV. Polyphenyls
Authors: Suzuki Hiroshi
Published: July 2006

The ultraviolet absorption spectra and the spatial configurations of polyphenyls have been briefly surveyed, and then the most probable spatial configurations of p-terphenyl and of o-terphenyl have been inferred from the spectra by application of the method analogous to the one for biphenyl in the first part of this series, resulting in the interplanar angle of about 10° for p-terphenyl and in that of about 43° for the o-isomer. Some related compounds have also been discussed. Further, it has been shown that the length of the “single” sp2–sp2 bond of the conjugated system depends on the extent of the π–π interaction across the bond, contrary to Dewar’s recent hypothesis.
Spectroscopic Study on the Living Polymers of Styrene, Butadiene and their Derivatives
Authors: Kuwata Keiji
Published: July 2006

The absorption spectra of the living polymers of styrene and its derivatives as well as of alkali benzyl have been measured from near infrared region to near ultra violet region, and they were compared. It has been concluded that these living polymers are the polymer anions having the groups of benzyl anion type at the end of a polymer chain. The living polymers of butadiene and isoprene have been separated as the intermediates of polymerization by metallic sodium, and their spectra have been measured. Comparing these spectra with that of allyl sodium, it has been concluded that the living polymer of butadiene and isoprene are the polymer anions having the groups of allyl anion type at the end of a polymer chain. The spectroscopic study on the block polymerization of isoprene with the living polymer of styrene has been carried out. The mechanism of polymerization has been discussed.
Alternating Current Polarization Titration with Two Hanging Mercury Drop Electrodes—Application to Chelatometric Titration of Cadmium
Authors: Kitagawa Toyokichi
Published: July 2006

Cadmium was titrated with the EDTA by the alternating current polarization titration with two hanging mercury electrodes and the factors which affect this titration were examined. As a result, it is clear that the end point is. indicated by the change of the mercuric ion con centration in the neighborhood of equivalence point. Pretreatment of the mercury drop electrode is not necessary. By this method, cadmium of 10−2∼10−3  m were titrated with a relative error of 0.9%.
A Molecular Orbital Theory of Saturated Compounds. I. Ionization Potential and Bond Dissociation Energy
Authors: Fukui Kenichi , Kato Hiroshi , Yonezawa Teijiro
Published: July 2006

The ionization potential and the bond dissociation energy of saturated compounds are calculated by Yoshizumi’s C–C bond skeleton method. With regard to ionization potentials, the calculated results are parallel to the observed values. In particular, for normal paraffins the parallelism is almost complete. For total electronic energies, the calculated results indicate a simple additivity rule in normal and cycloparaffins, and for bond dissociation energies an approximate agreement is obtained between the calculated and the observed values.

In spite of the rough approximation involved in the present treatment, it may be said that the results obtained are rather satisfactory.
Rate of Adsorption on a Heterogeneous Surface. Determination of the Distribution Function of Sites from Adsorption Rate Curves
Authors: Kubokawa Yutaka
Published: July 2006

A device to obtain the distribution function of sites from adsorption rate curves was worked out for the chemisorption for which desorption is negligible. It was then applied to the rate data of hydrogen chemisorption on chromic oxide gel and on ZnO·MoO3 with reasonable results.
Theory of the Influence of the Dielectric Constant on the Rate of Reaction in Solution with Application to Enzyme Reactions. II. Application of the Theory to Enzyme Reactions
Authors: Hiromi Keitaro
Published: July 2006

The theory of solvent effect developed in the preceding paper has been extended to include the enzyme reactions. The application to some typical model reactions which resemble the breakdown of enzyme-substrate complex has shown that the order of magnitude of experimentally observed effects can reasonably be accounted for by the theory.

Factors which may possibly influence rates of enzyme reactions by changing the composition of mixed solvents have also been discussed.
Amylose-Iodine Complex. III. Potentiometric and Spectrophotometric Studies
Authors: Kuge Takashi , Ono Sôzaburo
Published: July 2006

The amylose-iodine reaction has been studied in a wider temperature range than hitherto reported by both potentiometric and spectrophotometric methods.

The enthalpy change of the reaction obtained potentiometrically is −15.5 kcal. at 16°C, and appears to be independent of the chain length and the kind of parent starch of amylose.

The change of the absorptions of the amylose-iodine complex with temperature has been pursued at wavelengths of 650, 288 and 350 mμ, respectively.

The triiodide ion adsorbed on the surface of amylose causes an error in the spectrophotometric estimation of free iodine concentration. At the higher temperature, however, this error may be neglected, and the results obtained seem to be reliable.

The enthalpy change appears to increase with increasing temperature and −20.8 kcal. has been obtained at 50°C.
The Structure of Aureothin. X. Aza Derivatives of Aureothin, Isoaureothin and Desmethylisoaureothin
Authors: Yamada Kiyoyuki , Nakata Hisao , Hirata Yoshimasa
Published: July 2006

Aureothin (I), isoaureothin (II, R=CH3) and desmethylisoaureothin (II, R=H) reacted with ammonia in a somewhat drastic way, and gave aza-derivatives respectively, some properties of which are described. Of these, aza-desmethyl-isoaureothin was shown to be VI containing tautomeric α,γ-dihydroxypridine, on a basis of chemical and spectroscopic evidence.
Synthesis and Purification of Sexiphenyl for Scintillator
Authors: Nozaki Tadashi , Tamura Michiko , Harada Yuhei , Saito Kazuo
Published: July 2006

1) Mononitration of p-terphenyl is satisfactorily effected at 100 to 110°C in glacial acetic acid containing about 10% acetic anhydride and a trace of sulfuric acid, and 4-nitro- (ca. 60%), 2′-nitro- (20 to 25%) and 2-nitroterphenyl (15 to 20%) are obtained.

2) Sexiphenyl is formed in a fairly good yield (more than 40%) by the Ullmann condensation of 4-iodoterphenyl and copper.

3) Sexiphenyl is satisfactorily purified by repeated zone refining and vacuum sublimation. The final product melts at 428∼429°C to form an apparent liquid crystalline state and becomes tranparent at 543°C (475°C in literature). It contains an appreciable amount of neither iodine nor copper and can be converted into a fairly large single crystal to be used as scintillator.
Determination of Oxygen in Some Minerals Using Pyrite
Authors: Iwasaki Iwaji , Katsura Takashi , Yoshida Minoru
Published: July 2006

In the present paper a method for the determination of a very small amount of oxygen in an almost pure pyrite was proposed. From the results of the fundamental experiments on the reactions between the pyrite and the other minerals containing oxygen, it was ascertained that oxygen is completely liberated as sulfur dioxide and water vapor by heating in vacuo. The reproducibility of this method is fairly satisfactory, but there are no standard samples to examine the accuracy of this method. The results of the experiments indicate that this method could be used as a method for estimating the degree of oxidation of almost pure pyrites, for determining the amount of oxygen in some minerals, and in some cases for calculating the ratio of the oxygen containing compounds in their mixtures. Moreover, it seems possible to use this method for the determination of oxygen in a mixture of sulfides and oxides or sulfates of other metals than iron, and also oxygen in the metals. After the work reported herein had been almost completed, the authors were informed of the work, “The Sulfur Method of Oxygen Determination in Metals”, of Babko et al. who reported a somewhat similar study on the determination of oxygen in metals by using elementary sulfur instead of pyrite.
Vapor Pressure of Zinc in Tin-Zinc Binary Liquid Alloy
Authors: Niwa Kichizo , Yokokawa Toshio , Wada Harue
Published: July 2006

The vapor pressure of zinc in liquid tin-zinc alloys has been measured by Knudsen’s effusion method. Application of this method to liquid alloys has been found to be successful. Observed activity coefficients of zinc are discussed in relation to theoretical calculations. The deviation from the regular solution model has been interpreted in terms of the cellular approximation as well as the volume difference effect.
The Roles of Prolyl Residue in Polypeptide Monolayers. III. Surface Films of Gelatin
Authors: Ikeda Shoichi , Isemura Toshizo
Published: July 2006

Surface films of gelatin, which is very rich in l-prolyl and l-hydroxyprolyl residues, were examined on salt-free and 1 m potassium chloride solutions at three different pH’s by the measurements of surface pressure, potential and viscosity. They were found to spread incompletely but to be of expanded types. The incomplete spreading and the other properties of the films were regarded as a manifestation of the specific configuration of gelatin in films. The expanded nature of the films was attributed to the roles of prolyl residue in gelatin such as observed in polypeptides. The extent of expansion of the films appeared to give evidence to support the results from chemical analysis that a gelatin molecule is composed of a large amount of l-prolyl-l-hydroxyprolyl bonds. The behavior of gelatin films was adequately explained by assuming that the parts of cis  l-prolyl-l-hydroxyprolyl bond form the film and the parts of trans bond dissolve in aqueous subphase.
Non-stoichiometry of Nickel Oxide
Authors: Iida Yoshio , Shimada Kenzo , Ozaki Shunro
Published: July 2006

Nickel oxide obtained by heating nickel nitrate, carbonate and hydroxide at low temperatures exhibits a non-stoichiometric structure. An excess of oxygen decreases with an increase in the heating temperature of nickel salts. Concentration of Ni3+ determined by chemical analysis increases with the excess of oxygen. Densities of nickel oxide or activation energy of electrical conductivity decrease with an increase in the excess of oxygen, whereas lattice parameter does not vary. Isothermal change in electrical conductivity of nickel oxide shows that the decrease in vacancies may be attributed to the diffusion of vacancies to the crystal surface. The concentration of vacancies calculated from the density is higher than that from the concentration of Ni3+ ion. The disagreement may be attributed to the density measurement technique.
Studies on the Mannich Reaction. III. On the Formation of Piperidine Derivatives (3)
Authors: Uchino Norito
Published: July 2006

i) The addition of bromine to β-benzoylethylamine hydrochloride was studied. It was concluded that bromine molecule was added to β-benzoylethylamine hydrochloride in the form linking astride to the carbionium ion and the lone pair of electrons of the nitrogen atom, both of which were formed by prototropy.

ii) The bromine addition product of β-benzoylethylamine hydrochloride was treated with alkali for a little while to give N-bromo-β-benzoylethylamine which was very unstable and decomposed to give β-benzoylethylamine hydrobromide.
Selective Reduction of Phosphatides with Lithium Aluminum Hydride. I. Ovolecithin
Authors: Urakami Chieko , Okura Hirochika , Okada Mitsuko
Published: July 2006

The optimum conditions for cleavage of the fatty acid ester linkages in the lecithin molecule were found to be 20 min. at 10°C with the use of two moles of lithium aluminum hydride per mole of lecithin. The product formed under these conditions was identified to be l-α-glycerylphosphorylcholine when ovolecithin which was shown to be l-α-lecithin was used.

Discussion has been presented as to two mechanisms possibly participating in the cleavage of glycerylphosphorylcholine, one involving a complex formation with the phosphoryl group and the other with the cationic nitrogen atom of the choline base.
Studies on the Mucilage of the Root of “ Tororo-aoi” (Abelmoschus manihot, MEDIC). II. Effect of Heating on the Colloidal Characteristics of the Mucilage
Authors: Inokawa Saburo
Published: July 2006

1) From electron micrographs it was observed that in the crude mucilage there exists a network structure, but its structure is broken by heating.

2) From sedimentation diagrams and electrophoresis patterns it seems reasonable to assume that in the purified fresh mucilage there exist very strong intermolecular forces like those in gel and these forces decrease markedly by heating.

3) It is conceivable that the degradation of the mucin macromolecule does not play an important role in the marked decrease of the elasticity of the purified fresh mucilage by heating.
Thermodynamic Studies on Cobalt Complexes. VI. Solubility of Nitropentamminecobalt(III), cis- and trans-Dinitrotetrammine-cobalt(III) and Trinitrotriamminecobalt(III) Complexes*
Authors: Mori Motoshichi , Tsuchiya Ryokichi , Fukuda Hiroshi
Published: July 2006

1. From the solubility of cobalt (III) nitroammine complexes the thermodynamic stability was found to decrease in the order, chloride>nitrate>bromide>perchlorate.

2. The free energy of solution of cis-dinitrotetramminecobalt(III) chloride is lower than that of the trans chloride. This fact is attributed to the abnormally large value of the entropy of solution of the former compared with the latter.

3. Between the free energy of formation of cobalt (III) nitroammine complexes and the number of coordinated nitro-groups there exists a linear relationship.
Synthesis of α,α′-Diaminodicarboxylic Acids
Authors: Toi Koji , Mori Kan , Izumi Yoshiharu
Published: July 2006

A systematic study was made on the synthesis of α,α′-diaminodicarboxylic acids mainly by amination of the corresponding α,α′-dibromo-dicarboxylic acids using succinimide as an aminating reagent and by condensation of diethyl acetamidomalonate with α, ω-dibromo-paraffin.
The Ion-Exchange Behavior of Some Neutral Amino Acids
Authors: Sen\={o} Manabu , Yamabe Takeo
Published: July 2006

The ion-exchange behavior of three kinds of neutral amino acids was examined and the following results were obtained.

1) The ion-exchange behavior of amino acids can be explained when the dissociation equilibrium of amino acids in the solution was taken into account.

2) The maximum adsorption of neutral amino acids on the ion-exchange resins takes place in a rather broad pH range at the iso-electric point.

3) The neutral amino acids are adsorbed more extensively on cation-exchangers than on anion-exchangers. Glycine is adsorbed most extensively and leucine is more adsorbed than alanine.
Syntheses of Peptides Containing Proline. I. Syntheses of Glycyl-l-prolyl-l-leucyl-glycyl-l-proline and its Related Compounds
Authors: Sakakibara Shumpei , Nagai Yutaka
Published: July 2006

Glycyl-l-prolyl-l-leucyl-glycyl-l-proline and its related compounds were synthesized for elucidating the substrate specificity of collagenase. In the synthetic study, almost all of the possible routes were tried and the yield. crystallizability and specific rotation of products were compared for each route. Peptides or their derivatives containing two proline residues in general were hydrophilic and hard to be crystallized, but it was found, that carbobenzoxyglycyl-l-prolyl-l-leucyl-glycyl-l-proline was an exceptional example of a readily crystallizable substance and a good substrate for collagenase.
Physical Properties and Crystal Structure of 2-Bromo-2, 3, 3-trimethylbutane
Authors: Koide Tsutomu , Kato Yoshihiro , Oda Tsutomu
Published: July 2006

2-Bromo-2, 3, 3-trimethylbutane gives a plastic crystal, which is optically isotropic and has a density of 1.31 g./cc. at 13°C. The X-ray data can be interpreted on the bases of a body-centered cubic lattice, having α=7.66 Å with two molecules in the unit cell. The symmetry interpretation gives a structure of disordered orientation of molecules. It was found, by means of optical and differential thermal analysis methods, that there is a phase transition at about −114°C, below which the crystal is of a lower symmetry.
Spectrophotometric Determination of Bismuth with Xylenol Orange
Authors: Onishi Hiroshi , Ishiwatari Nasumi
Published: July 2006

A method is described for the spectrophotometric determination of 10∼80μg. of bismuth with Xylenol Orange. The error is not likely to exceed ±10 per cent. The molar extinction coefficient of bismuth in 0.1 n nitric acid solution is 1.6×104 at 530 mμ. Instead of nitric acid perchloric acid or sulfuric acid may also be used. The interference of small amounts of zirconium, thorium, and iron can be eliminated by masking. Lead and thallium do not interfere with the determination of bismuth. A 1 :1 complex of bismuth with Xylenol Orange is suggested.
Studies on Polymerizaton and Depolymerization of ε-Caprolactam Polymer. VIII. The Solution Viscosity of Poly-ε-capramide of Super-high Degree of Polymerization
Authors: Ogata Naoya
Published: July 2006

The solution viscosity of poly-ε-capramide of a super-high degree of polymerization in 98% sulfuric acid has been investigated. A linear relation between log (ηsp/c) and c (g./ 100 cc.) is found for the alkali-catalyzed polymers of [η]>2.5, as expressed by the following equation.

log(η_sp/c)=0.05c+(0.33c+1)log[η]

The relationship between \barPn and [η] is expressed by the following equation.

\barP_n=89[η]

The alkali-catalyzed polymer of a super-high degree of polymerization degrades slowly at room temperature in solid phase.
Proton Magnetic Resonance of Borazole
Authors: Ito Kazuo , Watanabe Haruyuki , Kubo Masaji
Published: July 2006

The proton and 11B magnetic resonances of borazole were recorded at room temperature. The proton magnetic resonance spectrum showed a 14NH triplet, a 11BH quartet and a part of 10BH septet. The broadening of multiplet structure was discussed and the peak heights of the multiplet components were explained in terms of the quadrupole relaxation of nuclei bonded to hydrogen. The chemical shifts and the spin coupling constants were compared with those of related compounds.
Alkylalkoxypolysiloxanes. IX. Methylethoxypolysiloxanes Containing the Trimethylsiloxy Group
Authors: Sakiyama Minoru , Okawara Rokuro
Published: July 2006

(1) Methylethoxypolysiloxanes containing the trimethylsiloxy group have been prepared.

(2) The infrared spectra of these compounds are discussed.
Spectrophotometric Determination of Traces of Boron in Thorium
Authors: Onishi Hiroshi , Ishiwatari Nasumi , Nagai Hitoshi
Published: July 2006

Procedure is described for the spectrophotometric determination of a few tenths of a part per million of boron in thorium oxide or metal. The sample was brought into solution with strong phosphoric acid. After diluting the solution with water, boron was separated by distillation as methyl borate, and finally determined by the curcumin method. The error is not likely to exceed ±0.1 ppm for 0.2∼1 ppm of boron.
Determination of Reducing Sugars by Means of Back Titration against Alkaline Copper Solution. I
Authors: Takahashi Masahito
Published: July 2006

A new volumetric method determining reducing sugars has been developed by titrating a boiling mixture of modified Fehling solution and sugar solution with a standard sugar solution. By the method the concentration of sugar solution can be determined rapidly with high degree of precision.

Errors caused by variables of analytical conditions automatically being corrected, the maximum degree of accuracy will be possible by this procedure even in an unskilled hand.

There are several advantages over Lane and Eynon’s method and other methods; the method is applicable over a wide range of sugar concentrations, especialy dilute solution, and in addition the difficulty in changing or washing a burette for a new solution, etc., is eliminated.
Biochemical Studies on Pearl. VIII. Occurence of Calcite, Aragonite and Dolomite in Pearl and Shell
Authors: Tanaka Shozo , Hatano Hiroyuki , Itasaka Osamu
Published: July 2006

The chemical compositions of the pearl and the shell of the Japanese pearl oyster were investigated from a crystallographical and biochemical point of view.

By the X-ray diffraction analysis, crystals of calcium carbonate in the nacre of pearl and in the nacreous layer of shell were determined to be aragonite, while those in the prismatic layer were shown to be calcite.

The state of chemical combination of minute amounts of magnesium present in the pearl and the shell materials was examined by a chemical method. In the nacreous substances, magnesium is present as dolomite, while in the prismatic material it exists as a solid solution of calcite and dolomite.

The state of crystals of calcium carbonate and magnesium carbonate occurring in the pearl oyster has been discussed with respect to the formation of the pearl and the shell of the pearl oyster.
Studies on Arsenic Trisulfide Glass
Authors: Matsuda Jiro
Published: July 2006

Arsenic trisulfide glass shows 70% of transmittance between 2 and 12 μ. This transmittance is somewhat insufficient for the optical cell in the infrared. Moreover, the chemical durability to alkali is very weak. These defects can be removed by proper coating on the surface. For instance, it can be of good use between 2 and 5.7 μ by using terylene film.

In thermal expansion, the transformation point of glassy arsenic trisulfide is nearly 170°C. In order to study what process of transformation occurs in the glass, the quenching method was applied. Some pieces of annealed glass were experimentally quenched at 180, 174, 164 and 153°C. Thermal expansion was measured on these quenched glasses.

Because of their various controls of expansion by temperature, glassy transformation at 170°C has no connection with transformation at the same temperature in arsenic trisulfide.
Phase Equilibrium on Liquidus Surface of the System 3CaO·P2O5–CaO·MgO·2SiO2–MgO·SiO2
Authors: Sata Toshiyuki
Published: July 2006

The phase relationship on the liquidus surface of the system 3CaO·P2O5–CaO·MgO·2SiO2–MgO·SiO2 was investigated by the usual quenching method. The three primary crystals are α- or β-tricalcium phosphate, diopside and forsterite, and the range of the lowest temperature is located at the center of this triangle (1277°C). From these results, it is found that this system should be considered as a partial system in the 4-component system 3CaO·P2O5–CaO·MgO·2SiO2–2MgO·SiO2–SiO2.
High Pressure Reduction of Organic Compounds with Urushibara Catalyst. VI. A New Type of Urushibara Nickel Catalyst
Authors: Motoyama Izumi
Published: July 2006

A new Urushibara nickel catalyst, U-Ni-BA, was prepared from nickel chloride and aluminum grains. This new catalyst was found to be highly active for the hydrogenation of aromatic nucleus, contrary to the older Urushibara nickel catalyst, U-Ni-A or U-Ni-B.

The preservability of the catalyst was examined: the precipitate, obtained by the reaction of nickel chloride with aluminum grains (or zinc dust), was kept for a long time in solvent or in dry state, and a similarly active catalyst could be obtained by digesting the preserved precipitate with aqueous caustic alkali.
Determination of Thallium(I) with Iodate in the Presence of Mercuric Ions and with Iodate and Permanganate via Bromide
Authors: Sharma Bechu
Published: July 2006

Oxidation of thallium(I) is carried out with iodate in the presence of mercuric ions using the amperometric D.S.E.P. Thallium is oxidized to thallium(III) and iodate is quantitatively reduced to iodide. The procedure is valuable because it gives correct determination for thallium(I) at a low acid concentration. Oxidation of thallium(I) with permanganate and iodate in hydrochloric acid via bromide is also found to be accurate and quantitative.