bluuebunny/crossref_metadata_2025 huggingface dataset:
An Isotopic Exchange Reaction between Oxygen and Carbon Dioxide on Zinc Oxide
Authors: Titani Toshizo , Kiyoura Tadamitsu , Adachi Akira
Published: July 2006

Isotopic oxygen exchange reactions between carbon dioxide and zinc oxide, and between oxygen and carbon dioxide on zinc oxide, have been studied by the static method in the temperature range from 350 to 550°C. At any temperature carbon dioxide exchanges its oxygen atoms with those of zinc oxide rapidly. Within a few minutes after the initiation of the reaction, an isotopic equilibrium is established between the carbon dioxide in the gas phase and a certain part of the zinc oxide. It has been found that the, isotopic exchange between oxygen and carbon dioxide on zinc oxide takes place through the exchange between these gases and the oxygen atoms of the zinc oxide, that the limiting step is the exchange with oxygen, and that the carbon dioxide acts as an inhibitor of the exchange between oxygen and zinc oxide.
The Reaction of Ions in the Radiolysis of n-Butane in the Gas Phase
Authors: Miyazaki Tetsuo , Shida Shoji
Published: July 2006

The effect of ammonia in the radiolysis of n-butane has been investigated. In low pressure radiolysis, C3H8 and C2-products decrease upon the addition of ammonia while C3H6 increases. C4H8 increases sharply upon the addition of a small amount of ammonia, but it gradually decreases upon further addition. CH4 and H2 are not significantly affected by ammonia. These results have been interpreted in terms of the proton transfer reaction of ammonia with ions, and their rate constants have been estimated. The contribution of the excited ion to the C–C rupture has been concluded to be much more important than that of the excited molecule in low-pressure radiolysis.

In high-pressure radiolysis all the products from the C–C rupture, including CH4, decrease upon the addition of ammonia (or water).
The Determination of Micro Amounts of Polythionates. II. A Photometric Method for the Determination of Hexathionate by Means of Its Cyanolysis
Authors: Koh Tomozo , Iwasaki Iwaji
Published: July 2006

A photometric method for the determination of a small amount of hexathionate has been developed, a method depending on the formation of thiocyanate equivalent to the hexathionate, and on the determination of thiocyanate with an excess of ferric iron. A buffer solution is first added to a standard hexathionate solution in order that the pH of the mixed solution after the addition of the cyanide solution may be within an optimum range; otherwise the hexathionate undergoes alkaline decomposition as a result of the higher pH value caused by the addition of the cyanide. The conditions under which the reaction of hexathionate with cyanide is rapid and proceeds well to completion, have been established by varying the cyanide amount, the pH, the reaction time, and the temperature. Hexathionate can be determined by exactly the same procedure as that used for phentathionate.
Palladium(II) Complexes of β-Ketoamines Derived from Acetylacetone and Amines
Authors: Yoshida Emiko , Yamada Shoichiro
Published: July 2006

Numerous new palladium(II) complexes, Pd-(Aca.R)2, have been synthesized with β-ketoamines derived from acetylacetone and amines, where R represents methyl, ethyl, n-propyl, n-butyl, benzyl, phenyl, o-, m- and p-tolyl, and o, o′-xylidyl. It should be noted that when R denotes n-propyl or n-butyl, the palladium(II) complexes have been prepared successfully, although the free ligands can not be isolated in a pure form. This may be regarded as an example of the stabilization of a molecular configuration through co-ordination with a metal ion. The visible and ultraviolet spectra indicate that the palladium(II) complexes prepared in the present paper, which are considered to be square-planar in non-donor solvents as well as in the solid state, combine no additional pyridine molecules, even in pyridine. This is contrary to the previous observation that Ni(Aca.R)2 complexes combine two molecules of pyridine to form a sexaco-ordinated complex in pyridine.
The Formation Constants and the Rate Constants of the Electrode Processes of Thiocyanato-Indium(III) Complexes with the Dropping Mercury Electrode
Authors: Narusawa Yoshio , Hashimoto Jinzo , Hamaguchi Hiroshi
Published: July 2006

The formation constants,

Kj=[In(SCN)j(3−j)+]/[In3+][SCN−]j (j=1, 2, 3, 4), have been determined to be 50, 200, 120 and 1670 respectively. The electrode reaction proceeds as follows:

(1) At a higher ligand concentration ;

In(SCN)P(3−P)+ \ightleftarrows InSCN2++ (p−1) SCN−

(fast) (p=2, 3 and 4)

InSCN2++ 3e− + Hg → In(Hg) + SCN−

(rate constant (k1)B)

(2) At a lower ligand concentration:

InSCN2+\ightleftarrows Inaq3+ + SCN− (fast)

Inaq3+ + 3e− + Hg→ In(Hg)

(rate constant (k0)B

The rate constants, (k0)B and (k1)B at the standard potential are (0.64±0.16)×10−4cm./ sec. and (1.5±0.2)×10−4 (cm./sec.)/(mol./l.) respectively. The rate constant, k0f,h, at 0 V. vs. NHE was 4.77×10−12 cm./sec.
The Colloidal Behaviour of Ammonium Purpurate (Murexide) in an Aqueous Solution
Authors: Sangal Satendra P
Published: July 2006

By electrical conductance studies it has been found that ammonium purpurate behaves as a colloidal electrolyte and does not obey Beer’s law in concentrated solutions. The curve between the square root of the concentration and the molar conductance is not linear and resembles that of a colloidal electrolyte. The temperature of zero conductance has also been determined to be −20°C. The temperature coefficient per degree centigrade per hundred of the conductance at 35°C ranges between 0.86 and 1.65.
The Formylation of Amino Acids with Acetic Formic Anhydride
Authors: Muramatsu Ichiro , Murakami Masahiro , Yoneda Takahiro , Hagitani Akira
Published: July 2006

The formylation of amino acids with acetic formic anhydride has been studied. This anhydride is prepared by the reaction of acetyl chloride with sodium formate or, preferably, from ketene and formic acid. When various monoamino monocarboxylic acids are treated with acetic formic anhydride by a simple procedure and under mild conditions, N-formylamino acids were obtained in satisfactory yields.
Heats of Mixing for Binary Mixtures. II. The 1,3-Butanediol-Methylethylketone System
Authors: Takami Mitsumasa , Murakami Sachio , Fujishiro Ryoichi
Published: July 2006

The heats of mixing of 1,3-butanediol and ethanol with methylethylketone have been measured. The results obtained for these two systems have been compared with each other, and it has been found that there exist a considerable number of intramolecular hydrogen bonds of butanediol molecules in the ketone medium.

For the ethanol-methylethylketone system, the energy of the intermolecular hydrogen bond with ketone has been estimated to be about 4kcal. by using the thermochemical cycle; this value is nearly the same as those obtained for other monoalcohol-ketone systems in the previous paper.1)
Properties of the Dilute Solution of Poly-2-methyl-5-vinylpyridine
Authors: Miura Masaji , Kubota Yukio , Masuzukawa Teruaki
Published: July 2006

Nine fractionated samples of poly-2-methyl-5-vinylpyridine (PMVP) have been investigated by viscosity and light-scattering measurements at 25°C. In the range of the molecular weights from about 1×105 to 1×106, the following relationship between the intrinsic viscosity and the molecular weight in methanol has been obtained: [η] =0.80×10−4Mw0.76. The unperturbed molecular dimensions have been obtained using the recent theories of the solution behavior of high polymers. The results have been compared with those of other vinylpyridine polymers and polystyrene, and it has been found that the degree of the extension of PMVP is almost the same as those of the other polymers.
The Micelle Formation of Some Alkyl Sulfates in a Dioxane-Water Mixture
Authors: Shirahama Keishiro , Matuura Ryohei
Published: July 2006

The CMC values of three sodium alkyl sulfates with the number of carbon atoms 12, 14 and 16 in a dioxane-water mixture have been measured. The CMC-lowering effect of dioxane, especially appreciable in the case of sodium dodecyl sulfate, has been explained in terms of Shinoda’s equation. The CMC-raising effect of dioxane, which is the main effect in the case of sodium hexadecyl sulfate, has been explained by the decrease in the standard chemical potential, i. e., the free energy of transfer, ΔFtr, of the surfactant. An equation has been derived which expresses ΔFtr as a function of the dioxane concentration by applying Born’s equation and Hildebrand’s regular solution theory.
Electrolytic Thermocouple for the Determining Soret Coefficients and Heats of Transfer of Hydrochloric Acid
Authors: Ikeda Toshio
Published: July 2006

We have studied an electrolytic thermocouple formed by coupling two thermocells, consisting of electrodes of the same nature, and with different electrolytes, either hydrochloric acid or potassium chloride, but both of the same concentration; we have demonstrated that the Soret coefficient of hydrochloric acid relative to that of potassium chloride can be estimated from the initial thermoelectric powers of this electrolytic thermocouple, as long as the entropies as well as the heats of the transfer of the chloride ions may be assumed to be the same between these two electrolytes.

Agreements between calculations and observations have been roughly good in the range of concentration between 0.01 m and 1 m, though there are some uncertainties about the Soret coefficients of potassium chloride at higher concentrations. This method may have general applicability, particularly in the dilute region.
Thermal Decomposition of Acetaldehyde in the Presence of Hydrogen Chloride
Authors: Imai Naomi , Fujii Takeshi , Toyama Osamu
Published: July 2006

The thermal decomposition of acetaldehyde in the presence of hydrogen chloride has been investigated over the temperature range from 401 to 433°C. Hydrogen chloride, though it is not consumed, enhances the rate of decomposition to carbon monoxide and methane, thus acting as a catalyst. The rate law which holds when the [HCl]/[CH3CHO] ratio is sufficiently high is the same as that which holds in the absence of hydrogen chloride, being represented as k[CH3CHO]3⁄2 independent of the hydrogen chloride pressure. The most probable reaction scheme for explaining this rate law is CH3CHO+M → CH3+CHO+M (1), CHO → CO+H (2), H+HCl → H2+Cl (3), CH3+HCl → CH4+Cl (4), Cl+CH3CHO → HCl+CH3CO (5),CH3CO → CH3+CO (6), and Cl+Cl+M → Cl2+M (7), yielding the overall rate k11⁄2k5k7−1⁄2[CH3CHO]3⁄2. The Arrhenius expression obtained from the experimental results, k11⁄2k5k7−1⁄2=1013,0exp (−44000⁄RT) mol−1⁄2cc1⁄2 sec−1, is in harmony with those for k1, k5, and k7 available in the literature.
Surface Chemistry of the Polyamide Series. II. Effect of the Sarcosyl Residue on the Monolayer of Polyleucine
Authors: Yamashita Takuya , Isemura Toshizo
Published: July 2006

The effect of hydrogen bonding on the nature of poly-α-amino acid monolayers has been studied at air/water and oil/water interfaces with poly-l-leucine, poly-Dl-leucine, and the 3:1-, 1:1- and 1:3-copolymers of l-leucine with sarcosine.

Poly-l-leucine and poly-Dl-leucine have been found to give condensed monolayers on distillled water. The surface viscosity of poly-l-leucine was first detected at a larger area than its close-packed area. The strong interaction between polymer chains of polyleucine was suggested by these findings.

On the other hand, at both air/water and oil/water interfaces, the compressibility of the film is increased much more by the incorporation of the sarocosyl residue in the polymer chain. At the air/water interface, the films of 3:1- and 1:1- copolymers of l-leucine with sarcosine are of the expanded type, and the surface viscosities have first been detected at much smaller areas than their close-packed areas. These findings suggest that the interaction between polymer chains diminishes because of the decrease in the number of intermolecular hydrogen bonds.
The Oxidimetric Determination of Thioureas with Potassium Bromate
Authors: Singh Balwant , Verma Balbir Chand , Saran M S
Published: July 2006

Potassium bromate has been used as a redox reagent in the presence of potassium iodide for the visual and potentiometric determination of thiourea and its several alkyl and aryl derivatives in a sulphuric acid medium. In visual titrations, amylose, is used as a visual indicator, turning blue at the end-point. In the potentiometric method, a bright platinum wire is used as an oxidation-reduction electrode ; this is coupled with a saturated calomel electrode. The thioureas are oxidised to their corresponding disulphides with a single electron-change:

(Remark: Graphics omitted.)

This direct method is simple, accurate, instantaneous and widely applicable.

One of the present authors (B. C. V.) wishes to thank the Council of Scientific and Industrial Research, Rafi Marg, New Delhi, for the award of a Senior fellowship.
The Dielectric Properties of Some Alkyl Thiol
Authors: Kondo Seiichi
Published: July 2006

It has been concluded that both 2-methyl-2-propanethiol and 2-methyl-2-butanethiol are plastic crystals and that, in their highest temperature crystalline phases, molecules perform a rotational motion on the lattice sites. The intermolecular S–H…S hydrogen-bond, which might possibly exist in these phases, seems to be too weak to hinder the molecular rotation. Cyclohexanethiol does not seem to be a plastic crystal, probably because of its low molecular symmetry in the solid phase and its intermolecular hydrogen bond.
The Quenching Action of Benzoic Acid and Methyl Benzoate on the Fluorescence of Naphthalene Derivatives
Authors: Miwa Takuji , Koizumi Masao
Published: July 2006

1) The quenching action of benzoic acid (dimer) (BA) and methyl benzoate (MB) on the fluorescence of 2-naphthol (I), 2-naphthylamine (II), 2-naphthyl methyl ether (III) and N,N-dimethyl-2-naphthylamine (IV) in benzene and in cyclohexane has been studied.

2) MB has little or no quenching effect on the fluorescence of III and IV, whereas it shows a significant quenching action on I and II. The latter is due to the intermolecular hydrogen bonding between the fluorescer and the quencher (the H.B. mechanism).

3) BA shows quite a large quenching action on III and IV. All the results can be interpreted on the basis of a charge transfer mechanism for quenching (the C.T. mechanism).

4) The quenching action of BA is larger on I than on III, and larger on II than on IV, except for benzene solutions of II and IV, in which case the magnitudes are equal within the range of experimental error. These results has been discussed on the basis of a simultaneous occurrence of the C.T. and H.B. mechanisms.
Rearrangements of Tertiary Amine Oxides. XIII. The Reactions of p-Nitrobenzenesulfenyl Chloride with Pyridine-and α-Picoline N-Oxides
Authors: Oae Shigeru , Ikura Katuyata
Published: July 2006

In the reactions of both pyridine and α-picoline N-oxides with p-nitrobenzenesulfenyl chloride, the N–O bonds of the intermediate salts appear to cleave homolytically, and the p-nitrosulfinyl radical which arises from the homolytic cleavage of the N–O bond is considered to be so stable that only the secondary reaction products from the sulfinyl radical, and no heteroring-substituted products, were obtained.
A Phase Study of Sodium Soap - Sodium Silicate - Water Systems
Authors: Kimura Yasushi , Shimo Terunosuke , Sekiguchi Hitoshi
Published: July 2006

The Tc temperatures of sodium soap - sodium silicate - water systems, which are important but are usually neglected, have been determined using a silicate with an SiO2/Na2O weight ratio of 2.1, and six single soaps or their mixtures. It has been found that there is a characteristic tendency arising from the structure of the fatty acids of the soaps, saturated (higher or lower) and unsaturated (cis or trans). The Tc values of the saturated - fatty acid soap systems increase linearly in proportion to the silicate in the system. The Tc value curves of the unsaturated soaps are rather complicated. Their Tc values, while the contents of the silicate in the system are small, are relatively lower than those for the former, but when the silicate concentrations increase to relatively large amounts, the Tc values are elevated rapidly. This inclination is more remarkable for cis unsaturated soap than for the trans isomer.

In the system of the mixed soaps, there is a complex mutual effect. By the combination with a lower saturated-soap, the solubility of the higher saturated-soap is increased, and by the combination with a saturated soap, the tendency of unsaturated soap to salt out is substantially prevented. Consequently, the rising of the Tc curve for unsaturated soap becomes mild.

As a rule, the Tc values determined, therefore, are lower than those estimated from the Tc values for the ingredient soaps. It seems that, in order to increase the amount of builder which can be added to the soap of higher saturated-fatty acid, combination with a lower saturated-soap is suitable.

Moreover, in the case of the sodium laurate sodium oleate - water system, it has been shown that the mixing ratio of the two-single soaps influences the Tc value greatly.
The Mechanism of the Base-Promoted Rearrangement of N,N-Dichlorodiphenylethylamine to Desylamine
Authors: Oae Shigeru , Furukawa Naomichi
Published: July 2006

N,N-Dichloro -1,2-diphenylethylamine-1- 14C has been treated with sodium methoxide in methanol and then with hydrochloric acid to yield 14C-labeled desylamine hydrochloride Successive degradations have revealed that practically all the 14C activity was found in the carbonyl carbon. From the 14C distribution, it has been concluded that the reaction is essentially the same as that proposed for the Neber rearrangement, which involves the formation of the azirine ring intermediate.
The Structure of Hibaene
Authors: Kitahara Yoshio , Yoshikoshi Akira
Published: July 2006

The structure and absolute configuration of hibaene, a new diterpene isolated from the essential oil of the leaves of hiba (Thujopsis dolabrata Sieb. et Zucc.), have been presented.
Absorption and Fluorescence Spectra of Anthracene-s-Trinitrobenzene Complex Crystal
Authors: Tanaka Jiro , Yoshihara Keitaro
Published: July 2006

The electronic absorption and fluorescence spectra of the single crystal of the anthracene-s-trinitrobenzene complex have been measured, and the polarization property of electronic transitions has been discussed in terms of interaction between the no-bond structure, the charge transfer and the locally-excited state of anthracene.

It has been shown that molecules in a pair are displaced to a closer position after the excitation, whereby the mixing of the donor-excited level occurs more than in the ground state (Frank-Condon state), and the fluorescence involves a larger contribution from the in-plane transition of anthracene.
Organic Photochemical Reactions. I. The Synthesis of Substituted Oxetanes by the Photoaddition of Aldehydes to Furans
Authors: Toki Susumu , Shima Kensuke , Sakurai Hiroshi
Published: July 2006

The photochemical reaction of aldehydes (propionaldehyde and benzaldehyde) and furan have been studied in the liquid phase; two new compounds, oxetanes I and II have easily been produced with a high purity by this photo-reaction.

In the case of 2-methylfuran and propionaldehyde (or benzaldehyde), a mixture of oxetanes III and IV (or V and VI) has also been obtained.
Semiconducting Properties of Tetramethylammonium Polyiodides and the Irradiation Effect
Authors: Kawai Shichio , Kiriyama Ryôiti , Uchida Madoka , Kusabayashi Shigekazu , Mikawa Hiroshi
Published: July 2006

Measurements of the temperature-dependence of d.c. conductivity have been made with tetramethylammonium polyiodide in different crystallographic directions, perpendicular to and parallel to the nets of iodine atoms. The systematic increase in the number of iodine atoms from tetramethylammonium triiodide to tetramethylammonium enneaiodide is accompanied by a gradual increase in conductivity. The activation energy for the conductivity along the iodine net is determined mainly by the shortest distance between polyiodide ions. Such as in the case of crystalline iodine, hole conduction is predominant in polyiodide crystals. From the standpoint of structural considerations and the values of the activation energies, the fundamental process in the hole conduction seems essentially be the same in both polyiodides and solid elementary iodine.

The irradiation effects on the electrical conduction may be classified distinctly into two types: (i) the effects of irradiation which can easily be removed by annealing above about 30°C, and (ii) the effects which can not be overcome by heat treatment below 70°C. The conductivity increases on X-irradiation, indicating the production of some acceptor levels, while the conductivity decreases with γ-irradiation, a phenomenon which may be attributed to some sort of donor level formation.
The Kinetics of the Acid-catalyzed Transformation of Peroxybenzoic Acids to Acetyl Benzoyl Peroxides in Acetic Acid
Authors: Ogata Yoshiro , Furuya Yoshiaki , Aoki Keizo
Published: July 2006

It has been confirmed by paper chromatography that peroxybenzoic acid in acetic acid is transformed reversibly to acetyl benzoyl peroxide in the presence of a catalytic amount of sulfuric acid. The rate satisfies the first order equation for reversible reactions. The plot of the logarithm of the forward rate constant vs. the acidity function has given a straight line with a slope of −0.96. The rate decreases upon the introduction of an electronattracting group to the benzene ring of peroxybenzoic acid, the Hammett’s ρ-value being −0.37. A mechanism analogous to that postulated previously with peroxyacetic acid, which involves a rate-determining attack of protonated acetic acid on peroxybenzoic acids, is consistent with these facts.
Study of Nickel Oxide-Silica-Alumina Catalysts for Ethylene Polymerization. III. The Performance of the Catalysts in Ethylene Polymerization and Butene Isomer Formation and Its Dependence on the Nickel Oxide Content
Authors: Imai Hisao , Uchida Hiroshi
Published: July 2006

The activity of nickel oxide-silica-alumina catalysts in ethylene , polymerization and the selectivity in the formation of three n-butene isomers as the primary products have been studied by employing a series of catalysts with identical aluminum contents but different nickel contents. Also studied have been the changes brought about by nickel removal in the catalyst acidity and in the specific surface area.

In the series of catalysts studied, the specific activity, i. e., the activity per unit surface area of the catalyst, increases with the increasing nickel content of the catalyst, attaining a maximum at 3 atm.% nickel. When the specific activity is plotted against the difference between the specific acidity values observed before and after the removal of nickel, the plot falls approximately on the straight line obtained with a series of catalysts which are the same in nickel content but different in aluminum content. On the other hand, for all the catalysts used in the present and previous studies, the selectivity is more closely related to the Al/Ni ratio than to either aluminum content or nickel content.

Two kinds of active sites have been presented in order to explain the present observations. One kind of active site is the nickel acid site, which contributes to the polymerization of ethylene while facilitating the isomerization to some extent. The other site is the aluminum acid site in contact with the former; it contributes to the initial-bond shift.
Ferrocene-containing Polymers. IV. Polymeric Ethers as Intermediates in the Self-condensation of Ferrocenyl Carbinols
Authors: Neuse Eberhard W , Quo Edward
Published: July 2006

The acid-catalyzed polycondensation of ferrocenylphenylcarbinol Ic under controlled, mild reaction conditions gives rise to the formation of low-molecular, ferrocene-containing polymeric ethers, to which, on the basis of elemental analysis, infrared and NMR spectro-scopic data, the structure IIIf is assigned. Monomeric ether IIIc is isolated in addition under these conditions. In the presence of Lewis acids at elevated temperatures, ethers Illf continue to react, with the elimination of the ether bridge, to give polymers identical with the previously reported oxygen-free compounds IIc, which were obtained directly from Ic under more rigorous conditions. In the previous work, polymers IIIf containing an ether group were postulated as intermediates but were not isolated. The observed formation of such polymers under the present experimental conditions, coupled with their successful post-condensation to IIc, is thus in accord with the earlier mechanistic implications.
Effects of Pressure on the Chemical Properties of the Solid Surface. I. Surface Acidities of Some Compressed Sulfates and Bisulfate
Authors: Ogino Yoshisada , Kawakami Takeshi
Published: July 2006

Compression of potassium bisulfate and certain other metal sulfate has been shown to cause an increase in their surface acidities. This increase in surface acidity has been correlated with dehydration of the compressed sample, and X-ray diffraction studies have revealed that dehydration is accompanied by minor structural changes involving the formation of a less hydrated substance.

In those sulfates where compression produced little or no change in the surface acidity, the extent of the dehydration from the compressed sample was meager, and X-ray diffraction studies proved that neither the formation of a new substance nor a great change in the crystal structure resulted from the compression.
Infrared Spectra of Urea Complexes of Copper(II) n-Alkanoates
Authors: Kuroda Yoko , Sasano Akira , Kubo Masaji
Published: July 2006

The infrared absorption spectra of various urea complexes of copper(II) carboxylates were recorded and the assignments of observed frequencies have been carried out to various modes of vibration. On the basis of comparison of the observed spectra with those of related compounds, it is concluded that copper(II) carboxylate monoureas and hemiureas form dimer molecules in crystals as in copper(II) acetate monohydrate, that copper(II) formate bisurea dihydrate has a crystal structure bearing resemblance to that of copper(II) formate tetrahydrate, and that urea molecules in these urea complexes are involved in bonding by electrostatic forces or hydrogen bondings instead of being bonded to copper atoms by coordination bonds.
Studies of the Cage Effect of Solvents. V. The Photolysis of Azoethane in n-Heptane
Authors: Kodama Sukeya , Fujita Shin’ichi , Takeishi Junsuke , Toyama Osamu
Published: July 2006

The effect of a solvent cage on the photolysis of azoethane in n-heptane was investigated at 366 mμ, in the temperature range from −75 to 99°C. Among the gaseous products, nitrogen served as a measure of the azoethane decomposed. The other gaseous products were n-butane, ethane and ethylene; these three hydrocarbons accounted for ninety per cent of the decomposition at 0°C. The quantum yield of nitrogen was found to decrease with a lowering of the temperature. The value obtained at 0°C was 0.021. In the presence of a sufficient amount of styrene, which was used as a scavenger for ethyl radicals, the yields of the gaseous hydrocarbons were more or less reduced to constant values; from these the ratio of rate constants for the combination and disproportionation of the geminate ethyl radicals formed by the photolysis in a solvent cage was determined to be kcomb⁄kdisp=11.5exp(−371⁄RT). The fraction of ethyl radicals that reacted in these ways in the solvent cage, before escaping it, was dependent on the temperature; it decreased from 0.838 at −75°C to 0.467 at 99°C. In the absence of styrene, the reactions for ethyl radicals that escaped the original solvent cages were inferred to be hydrogen abstraction, addition, combination and disproportionation.
The Reaction between Phenol and Formaldehyde in Non-Aqueous Media. I. The Kinetics of the Reaction Catalyzed by Boron Trifluoride - Etherate
Authors: Murayama Shin’ichi
Published: July 2006

The papers of this series are kinetic studies of the reaction between phenol and formaldehyde in non-aqueous media; this reaction has, however, not been investigated as thoroughly as the reactions in aqueous media. During the course of the reaction, the reactants and products have been determined by gas chromatography. Within the range of low conversion, the overall reaction between phenol and methylal may be represented by:

(Remark: Graphics omitted.)

Moreover, the kinetic equation and the apparent activation energy have been estimated as follows :

\fracd[methel alcohol]dt=−\fracd[phenol]dt=\frack[phenol]2[methylal]0[catalyst]1[methyl alcohol]3 E\doteqdot18.6 kcl./mol.

At the same time, methyl phenyl formal is detected as an intermediate in the reaction system. Judging from these experimental results, it seems that the acetal exchange reaction, and the substitution on aromatics proceed concurrently and consecutively in the complex system.
The Reaction between Phenol and Formaldehyde in Non-Aqueous Media. II. The Behavior of Methyl Phenyl Formal in the Reaction Catalyzed by Boron Trifluoride - Etherate
Authors: Murayama Shin’ichi
Published: July 2006

Methyl phenyl formal (MPF) is one of the most important intermediates in the acid-catalyzed reaction between phenol and methylal in non-aqueous media. On the acidic decomposition of MPF itself, phenol and methylal are mainly produced, along with a small amount of methyl alcohol at the first step; at the same time, there exists an equilibrium state between the reactants and the products. At the second step, the phenol produced is gradually consumed, and the reaction eventually yields methyl alcohol and such condensation products of phenol as methoxymethylphenol and dioxydiphenylmethane. Thus, the acetal exchange proceeds faster than the substitution on aromatics. On the other hand, the acidic decomposition of MPF is retarded remarkably by methyl alcohol, considerably by methylal, and fairly much by phenol. This behavior of MPF can be explained by its interaction with the catalyst and the opposing reactions with it. As a result, the reaction of MPF can better be understood.
The Reaction between Phenol and Formaldehyde in Non-Aqueous Media. III. The Mechanism of the Reaction Catalyzed by Boron Tifluoride - Etherate
Authors: Murayama Shin’ichi
Published: July 2006

In the previous papers of this series, the reaction between phenol and methylal in non-aqueous media has been investigated by means of the experimental characterization of the kinetic system; a plausible reaction scheme has thus been presented. The object of the present paper is to make a mathematical characterization of the kinetic system, a kinetic equation has been obtained by calculation based on the probable reaction scheme; it has been found to be in good agreement with the kinetic equation obtained experimentally.
The Chemistry of Polyazanes. II. 1,8-Di-p-tolyl-3,6-diphenyl-1,4,7-octaaztriene
Authors: Minato Hiroshi , Oku Masayoshi , Chan Samuel Hung-Pui
Published: July 2006

1,8-Di-p-tolyl-3,6-diphenyl-1,4,7-octaaztriene (DTDPO) was prepared by the potassium permanganate oxidation of 1-p-tolyl-3-phenyl-1-tetraazene (TPT), and the kinetics and the products of the decomposition of DTDPO were investigated. The experimental results can best be explained by assuming a mechanism in which DTDPO decomposes homolytically to yield a nitrogen molecule and two triazenyl radicals, which then combine to form 1,3,4,6-tetraaryl-1,5-hexaazdiene; the latter is very unstable and decomposes quickly to yield substituted azobenzenes and phenyl and p-tolyl radicals. The rather slow rate of decomposition of DTDPO was also discussed.
Studies on Long Chain Alkyl Amides of Water-soluble Poly-α-amino Acids. III. The Association of Poly-Dl-alanine Dodecylamides in Aqueous Solution
Authors: Ikeda Shoichi , Maekawa Masakazu , Isemura Toshizo
Published: July 2006

Poly-Dl-alanine dodecylamide, prepared by the polymerization of N-carboxy-Dl-alanine anhydride with dodecylamine initiation at different anhydride-to-initiator ratios, ([A]/[I]), is soluble in aqueous hydrochloric acid solutions to form micelles. Its micellar properties at pH 2.0 have been investigated by means of hydrodynamic methods. The material prepared at [A]/[I] 5 has a critical micelle concentration around 0.2—0.3 g. dl−1, which can be detected by Archibald sedimentation measurements. The micelle has been determined by the Archibald method to consist of about 13 monomer molecules. The molecules in the micelle are hydrogen bonded intermolecularly to form a structure similar to the β-conformation. Hydrogen bonding between peptide groups is more important for the micelle formation than hydrophobic bonds between dodecyl groups. The materials prepared at [A]/[I] 15 and 20 associate into large micelles, consisting of about 320 and 240 monomers respectively, as deduced from the sedimentation and viscosity measurements. The micelles exhibit even a flow birefringence. The structure of micelles seems to be a disordered one composed of randomly coiled monomer molecules; intermolecular hydrogen bonding and hydrophobic bonding are cooperative in its stabilization.
The Chemistry of Polyazanes. III. The Reaction of Nitrosobenzene with Hydrazine and Phenylhydrazine
Authors: Minato Hiroshi , Fujisawa Takiko
Published: July 2006

The reaction between nitrosobenzene and hydrazine was studied. Aniline and nitrogen were found to be the products, but it was not certain whether or not phenyltriazene existed as an intermediate. Then the reaction between nitrosobenzene and phenylhydrazine was studied. The products were azoxybenzene, diphenylamine, benzene and nitrogen. The reaction between p-nitrosotoluene and phenylhydrazine yielded 4, 4′-azoxy toluene, 4-methyldiphenylamine, benzene and nitrogen. The mechanisms of these reactions were discussed on the basis of these findings.
Potentiometric Studies of the Reaction between Mercury(I) Nitrate and Sodium Arsenate
Authors: Bhatnager C S
Published: July 2006

The reaction between mercury(I) nitrate and sodium arsenate has been studied potentio-metrically at various concentrations, by both the direct and reverse methods, employing bright platinum foil as an indicator electrode in conjunction with a saturated calomel electrode. The end-points obtained from the sharp inflections in titration curves and pronounced maxima in dE/dV provide cogent evidence for the formation and precipitation of mercury(I) arsenate, Hg3AsO4, in the 8.2–9.4 pH range. The precipitation of the compound is almost quantitative. The reaction can be successfully used for the determination of Hg22+ or AsO43− ions in solutions at suitable concentrations and pH ranges.
The Decomposition of Formic Acid on the Intermetallic Compounds of 3d-Transition Metals
Authors: Suzuki Chiyoko , Matsuura Ikuya
Published: July 2006

The catalytic behavior of the intermetallic compounds of Cr-Co, Fe-Cr, Fe-Mo, Ni-V and Fe-V systems on the decomposition reaction of formic acid was studied by the usual static method and compared with that of some alloys and manganese. A zeroth-order decomposition reaction was observed throughout the catalysts employed and the adsorption of formic acid on the catalysts during the decomposition reaction approched to the saturation value under the experimental condition, i. e., under the pressure range of 10—20 mmHg, and at the temperature of 200—300°C. The activation energy of the reaction varied from 13.5 to 20.7 kcal./mol. for various catalysts. It has been also found that the activation energy of the reaction catalyzed by the intermetallic compounds increased with the ratio of the electrons in d- and s-bands to atom of the catalyst.
Normal Coordinate Analysis of Trigonal Bipyramidal XY5 Type Molecules
Authors: A. Condrate Robert , Nakamoto Kazuo
Published: July 2006

Normal coordinate analysis has been carried out for trigonal bipyramidal XY5 molecules such as PF5, SbF5, PCl5 and SbCl5. It has been found that the simple Urey-Bradley force field does not provide satisfactory results for the bending modes of these molecules. The results have been improved considerably by introducing an interaction constant between equatorial and axial angle coordinates. In carrying out normal coordinate analysis, the repulsive force constants were first estimated from a Lennard-Jones type potential. Then the stretching and bending force constants were adjusted to fit the observed frequencies. Finally, the new interaction constant was introduced to minimize the errors in the bending frequencies. The force constants thus obtained are consistent through the four molecules studied. Some conflicting band assignments made by previous investigators have been discussed on the basis of the present calculations.
The Vibrational Assignment and Rotational Isomerism of n-Propyl Mercaptan
Authors: Hayashi Michiro , Shiro Yuji , Murata Hiromu
Published: July 2006

The infrared and Raman spectra of n-propyl mercaptan have been measured and vibrational assignments made with relation to the rotational isomerism. The normal vibration calculation has been carried out in a modified Urey-Bradley force field. In the gaseous and liquid states, TT and GT molecular forms have been confirmed to exist. An appreciable energy difference in the isomers has been found even in the liquid state. The TT form has a lower energy than the GT form. The CH2 hydrogen deformation frequencies of CH2CH2 groups in molecules similar to n-propyl mercatpan have been listed and discussed in relation to their molecular forms.
Studies of Calcichrome as a Spectrophotometric Reagent. I. A New Spectrophotometric Method for the Determination of Copper with Calcichrome and Its Basic Study
Authors: Ishii Hajime , Einaga Hisahiko
Published: July 2006

It was found that Calcichrome, which has been recently established as a reagent for the determination of calcium, forms a stable 1-to-1 complex with copper. Basic studies were carried out, in which the acid dissociation constants of Calcichrome and the apparent formation constant of the complex were determined to be pKa7=7.2, pKa8=11.5, and K=4.1×108 respectively. A new method for the determination of copper was also established.
Osmotic Pressure Measurements for Poly-p-Chlorostyrene Solutions
Authors: Takamizawa Kan’ichiro
Published: July 2006

Osmotic pressure measurements were made on poly-p-chlorostyrene fractions in toluene. Their intrinsic viscosities were measured in toluene, butanone, and chlorobenzene at 30°C. The intrinsic viscosity - molecular weight relationships of these systems were then evaluated for the monodisperse homologue by applying the proper correction for the heterogeneity in the sample. The unperturbed dimension of the polymer was estimated by the Kurata-Stockmayer method. A comparison of this estimate with that for polystyrene indicated that the chlorine atom at the para-position had no appreciable effect on the hindrance to the internal rotation of chain. The heat of the dilution of the polymer in toluene and chlorobenzene was also determined from measurements of the temperature coefficient of the osmotic pressure. It was endothermic in toluene and approximately zero in chlorobenzene. These results were then discussed in relation to the cohesive energy densities of the polymer and the solvents.
Influence of Metal Ions and of Metal Chelates on the Hydrolysis of α-d-Glucose 1-Phosphate
Authors: Murakami Yukito , Tanaka Michio
Published: July 2006

The hydrolysis reaction of α-d-glucose 1-phosphate has been studied in the presence of several metal ions and metal chelates at 40.0 and 60.0°C, in the pH range of 1.69–2.71, and at an ionic strength of 0.10 m (KNO3). The reaction rate was followed by the colorimetric method using a combination of the amidol reagent and 8.3% molybdate solution. Among the metal ions employed in this work, dipositive ions, such as manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) and uranyl ions, were observed to be nearly without effect on the rate of hydrolysis, while iron(III) and thorium(IV) ions demonstrated a negative catalytic effect. On the other hand, all the chelating agents employed tend to restore the reaction rate in reference to the corresponding metal-ion-effected reactions. With the 1:1 thorium(IV)-EDTA and the 1:1 iron(III)-EDTA chelate system, the rate was completely restored. Both iron(III)-kojate and thorium(IV)-Tiron chelate systems restored the reaction rate to a lesser extent. The roles of the chelating agents were discussed. The reaction mechanism in the presence of the catalyst species has been considered, and two possible mechanisms have been put forward for the present reactions.
Studies of the Photoreduction of Acridine in Ethanol by the Flash Technique
Authors: Kira Akira , Kato Shunji , Koizumi Masao
Published: July 2006

With the flash technique, the absorption spectra of the triplet state and of the semireduced form of acridine were observed, and the kinetics of the reactions involving these transient species was investigated. It was established that the photoreduction of acridine in the deaerated ethanol solution proceeds via two paths. One is a path via semireduced acridine; this path is strongly inhibited by the presence of oxygen, which efficiently oxidizes semireduced acridine. In the other path, the final product, acridan, is produced immediately after flashing, with no appreciable transient species being formed. The photoreduction by this path is not affected by the presence of oxygen. It may be presumed that this process is a molecular one between singlet acridine and alcohol. The reactive species in the former path also seems to be the singlet excited state instead of the lowest triplet state.
Aldehydes in Lake and Sea Waters
Authors: Kamata Eijiro
Published: July 2006

The vertical distribution of aldehydes in Lake Kizaki during summer stagnation is described. Aldehydes are found only in the hypolimnion, not in the upper aerobic water layers. The highest aldehyde content in three series of vertical samples is 0.11 mg./l. in terms of formaldehyde equivalents. It was shown by laboratory experiments that formaldehyde is rapidly decomposed in aerobic lake water, but very slowly in anaerobic lake water. In sea waters, aldehydes are not found in the surface water layer, and no systematic variation is noticed in the verticall distribution.
The Solvation of Ions in Liquid Sulfur Dioxide
Authors: Kondo Yasuhiko , Goto Tsutomu , Suo Isamu , Tokura Niichiro
Published: July 2006

The variation in the density and in the sound velocity with the concentration was measured in a liquid sulfur dioxide solution of electrolytes. The amounts of solvations and the volume changes which accompany the dissolving of the electrolytes were estimated. In liquid sulfur dioxide they were found to be considerably greater than those in water. The relations between the volume changes and the solvations were also discussed.
A New Mode of the Formation of the Meso-ionic Pyrido[2,1-b]-3,4-dihydro-4-oxothiazole: An Attempted Preparation of Pyrido[2,1-b]-3,5-dihydro-5-oxothiazole
Authors: Kato Hiroshi , Tanaka Kazuo , Ohta Masaki
Published: July 2006

The acylation of 2-mercaptopyridine gives S-acyl derivatives, which, on treatment with chloroacetic acid, give the title compound.
The Synthesis of Pyrido[2,1-b]-3,4-dihydro-4-iminothiazole Derivatives. A New Meso-ionic Heterocyclic System
Authors: Kato Hiroshi , Ohta Masaki
Published: July 2006

The action of acyl chlorides on 2-pyridylthioacetonitrile and related compounds gives the corresponding N-acylated pyrido[2,1-b]-3,4-dihydro-4-iminothiazoles and related compounds.
The Reaction of the Exo-cyclic Imino Group of “4-Thiazone Imine”
Authors: Ohta Masaki , Yoshida Kei , Sato Shigeru
Published: July 2006

In order to accumulate further information about the properties of meso-ionic compounds -with an exo-cyclic imino group, the reactivity of an exo-cyclic imino group of thiazone imine as compared with that of sydnone imine was investigated. Moreover, for the purpose of the pharmacological test, 2,3-disubstituted thiazone imine hydrochlorides and their N-acetyl derivatives were prepared.
Organic Sulfur Compounds. IV. The Reactions of Arylsulfonic Acids with Alkyl Chlorocarbonates
Authors: Yamamoto Asami , Kobayashi Michio
Published: July 2006

The reactions of p-toluenesulfonic acid salt with alkyl chlorocarbonates have been investigated and their mechanism discussed. The reactions were slow at low temperature, and the intermediates, sulfonic carbonic anhydrides, could be isolated. When heated, these mixed anhydrides decomposed to alkyl sulfonates and carbon dioxide. p-Toluenesulfonic acid-18O was prepared and its reaction with ethyl chlorocarbonate examined. All three oxygen atoms of the sulfonic acid were retained in the ethyl sulfonate formed. The reaction of isobutyl chlorocarbonate with silver p-toluenesulfonate gave a mixture of isobutyl- and s-butyl sulfonate. On the basis of these experiments, the mechanism involving the free alkyl cation has been proposed for the decomposition of the sulfonic-carbonic anhydrides.
Rearrangements of Tertiary Amine Oxide. XV. The Reaction of Heterocyclic N-Oxides with p-Nitrobenzenesulfinyl Chloride
Authors: Oae Shigeru , Ikura Katuyata
Published: July 2006

In the reaction of pyridine and α-picoline N-oxide with p-nitrobenzenesulfinyl chloride, the N–O bond of the intermediate salt appears to cleave homolytically, as in the case of N-oxide with p-nitrobenzenesulfenyl chloride, and the p-nitrosulfonyl radical which arises from the homolytic cleavage of the N–O bond is considered to be so stable that only the secondary reaction products from the sulfonyl radical, and no heteroring-substituted products, are obtained. It is the same in the case of unsubstituted benzenesulfinyl chloride.
The Simultaneous First- and Second-Order Esterifications of l-Menthol by Acyl Chlorides: Autocatalyses by Menthol in Acetonitrile and in Liquid Sulfur Dioxide
Authors: Akiyama Fuminori , Tokura Niichiro
Published: July 2006

The propionylation and p-methoxybenzoylation of l-menthol in various solvents have been studied. In chloroform, benzene, ethyl methyl ketone and carbon tetrachloride, the reaction follows the second-order rate law. However, in acetonitrile or in liquid sulfur dioxide, the rate follows the second-order rate law only at the initial stage of the reaction; thereafter it gradually deviates from the second-order type to the first-order one. Moreover, the first-order rate equations both in acetonitrile and liquid sulfur dioxide are dependent on the initial concentration of the alcohol; the over-all rates being expressed as:

Rate=k1°(AcCl)(ROH)0+k2(AcCl)(ROH)

where(ROH)0, (ROH), (AcCl), k1° and k2 are the concentrations of the alcohol at time zero and t, that of the acyl chloride at time t, the first-order rate constant and the second-order rate constant respectively.
The Studies of the Cage Effect of Solvents. VI. The Photolysis of Methylazoethane in n-Heptane
Authors: Fujita Shin’ichi , Kodama Sukeya , Toyama Osamu
Published: July 2006

Methylazoethane was photolyzed in n-heptane in order to study the effect of a solvent cage quantitatively; the results obtained were then compared with those for azomethane and azoethane previously studied. By using styrene as a scavenger for radicals, it was demonstrated that a large fraction (90% at −75°C and 58% at 100°C) of a pair of methyl and ethyl radicals formed by the decomposition of a molecule of methylazoethane combines to form propane or disproportionates to form methane and ethylene in an original solvent cage. The ratio of the rate constant for the disproportionation to that for the combination is small, and it decreases with a rise in the temperature, as was previously found for azoethane. The effect of the temperature on the yields of the products of cage reactions in the present work and in the previous work with azomethane and azoethane shows that the combination of ethyl radicals and the cross-combination of methyl and ethyl radicals in a solution require appreciable activation energies, even if that for the combination of methyl radicals is zero.