The electrode behavior of Lao., La_0.5Sr_0.5CoO₃ and Ag electrodes on (Bi₂O₃ )_0.77(Y₂O₃)_0.23 film solid electrolytes were investigated by means of d. c. and a. c. measurements at the temperature range of 200∼500°C under N₂-20% O₂ gas mixture. The electrolyte polarization or iR drop can be distinguished from the electrode polarization using a a. c. method or a current interruption method with the aid of a reference electrode.
(Bi₂O₃)_0.77(Y₂O₃)_0.23 film solid electro lytes were prepared by the thermal decomposition method employing the ultrasonic technique and by the rf magnetron sputtering method. Both of these film electrolytes had noncrystalline bulk structure, but the sintered disk electrolyte had polycrystalline.
The electrode process is strongly influenced by the nature of the electrode/electrolyte interface. The d. c. and a. c. polarization properties for the La_0.5Sr_0.5CoO₃ electrode on the film electrolyte prepared by the thermal decomposition method were more favourable than those of the other electrode/film electrolyte systems.
On the La_0.5Sr_0.5CoO₃/film electrolyte prepared by the thermal decomposition method, the diffusion resistance of the reaction species along the interface plays an important role in determining the electrode kinetics. On the other hand, on the La_0.5Sr_0.5CoO₃/film electrolyte prepared by the rf magnetron sputtering method, another process, probably the diffusion of electronic species in the electrolyte is dominant.

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The adsorption behavior of anionic surfactants on four kinds of soils containing various amounts of humic substances was investigated. The anionic surfactants used are sodium (linear alkyl) benzenesulfonate (LAS), sodium a-olefinesulfonate (AOS) and sodium dodecyl sulfate (SDS). The adsorption rate of surfactants on humus soil is lower than that on soil clay and it takes longer time to attain the adsorption equilibrium in the case of humus soils. The equilibrium amount of adsorption is nearly constant and not affected by the content of humic substance in a concentration range higher than cmc at 25°C for the same kind of soil. In a concentration range lower than CMC, the adsorption behavior obeys the Freundrich's adsorption isotherm. The slope of the adsorption isotherm is smaller and adsorption amount is larger on the humus soil than the corresponding non-humus soil in the lower concentration range of surfactants but, in the cases of AOS and SDS, the slope of the adsorption isotherm becomes larger in a higher concentration range. This characteristic behavior is considered to result from the coexistence of humic substance in the soil. The result is tentatively explained as the adsorption or the ion exchange of negatively charged molecules of surfactant on the positively chargrd sites of silica-alumina structure of soil particles.

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The adsorption such anionic surfactants as sodium (linear alkyl)benzenesulfonate (LAS), sodium a-olefinsulfonate (AOS) and sodium dodecyl sulfate (SDS) onto soil clays such as kaolin, cericite and bentonite was investigated. The adsorption amounts are dependent upon the pH and the concentration of surfactant solutions, and decrease with an increase in pH from 3 to 7 at a definite concentration. The adsorption isotherm obeys the Freundlich equation at concentrations lower than cmc, and the adsorption amount goes up to saturated value in the neighborhood of the respective cmc value. In the case of the adsorption of SDS onto Ca-bentonite and acid clay, however, the adsorption amount increases abruptly in a concentration range lower than CMC. This anomalous behavior was analysed through the measurements of the cation-exchange property of the clay and the solubility of calcium dedecyl sulfate (CaDS). It was found that the concentration at which the adsorption amount rapidly increased nearly coincided with the solubility of CaDS, indicating that this anomalous behavior of SDS is interpreted as due to the coaguration-adsorption of CaDS onto these clays. This conclusion was supported by the DSC measurement and the X-ray analysis for the SDS-adsorbed Ca-bentonite.

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The ion transport mechanism through the liquid membrane containing dibenzo-18-crown-6as a carrier was studied, using the dialysis cell composed of a source phase, a membrane phase, and a receiving phase, whose solutions were circulated with a tube pump from each reservoir to each compartment in the cell. The distribution coefficients of potassium nitrate between the source phase and the membrane phase were measured and were ascertained to be proportional to the salt activities. The salt flux was proportional to the product of the distribution coefficient and the salt activity, that is, proportional to the second power of the salt activity In the source phase solution of a high salt activity, however, the salt flux approached to a constant value. The hydration deree of anion influenced the salt flux considerably, because the stability constants of the crown ether complex with the salt composed of a cation and a hydrophobic anion was very high. The salt flux was correlated with the lyotropic number of the anion. The hydration degree of the cation also influenced the salt flux. The flux of the slightly hydrated ion, such as cesium ion, was large, although the diameter of the ion was much larger than that of the crown ring. The stirring of the source phase, the membrane phase, and the receiving phase influenced the salt flux and the stronger the stirring, the higher the salt flux. The effect of the stirring of the membrane phase was very prominent because the profile of the concentration gradient in the membrane phase was changed by the stirring.

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Activity and selectivity of nickel catalysts in the reduction of NO with H2 was investigated. Eight nickel catalysts were reduced at different temperatures by hydrogen and used for the hydrogenation of nitrogen monoxide to yield N₂, N₂O and NH₃. These catalysts were reference catalysts of Catalyst Society of Japan, and were different in support material, nickel content and preparation method. The results are summarized as follows: 1) The maximum activity of Ni/SiO₂ catalysts were about one hundred times more active than that of Ni/Al₂O₃catalysts.2) Such effects as the starting material for the preparation of nickel catalysts, (nitrate or sulfate), and the preparing method, (impregnation or precipitation), on the catalytic activity are masked by the stronger effect of the supporting material.3) Reduction of nickel ion to metallic nickel is essential for the catalytic activity, but the amount of carbon monoxide absorbed is not a measure of the catalytic activity, though it may be a measure of the degree of reduction of nickel. Based on the fact that the selectivity to NH₃ is well correlated to the catalytic activity, a hypothesis is proposed that the catalytic activity for the hydrogenation of nitrogen monoxide is governed by the relative strength of the intteractions of H₂ and NO with nickel.

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A catalyst of ZrO₂/Al₂O₃ supported ammonium sulfate was found to be effective for the reaction of methanol to olefines (MTO). The catalyst formed 25% of ethylene, 18% of propylene, 9% of isobutane as well as 11% of oily products which were analyzed by NMR and GC-MS techniques to be mainly a mixture of polyalkylbenzenes.
Formation of ethylene and propylene started at 280°C, isobutane was formed at 300°C and the oily producte were formed at 320°C. This fact indicates that propylene is formed by homologation of ethylene, isobutane by decomposition of the surface species on the catalyst and alkylbenzenes by cyclization of the olefines.
Concerning the intermediate, it has been proposed that an acid site makes carbenium ion a key intermediate for the MTO, and our results seem to follow the intermediate. However, even Al₂O₃ supported aluminium sulfate (H⁰=1.5) produced a small amount of olefins, We therefore, postulated that a pair of active sites such as the protonic sites for the methyl cation formation and the other sites for the dehydrogenation of methyl groups bifunctionally proceeds the MTO.

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In order to examine the effect of halobenzenes on the activity and the selectivity of Raney cobalt catalyst, the pretreatment of R-Co was performed by stirring R-Co in decane containing halobenzenes at specific temperature, then a mixture of (E)- and (Z)-3, 7-dimethyl2, 6-octadienal was added, and hydrogenation was carried out at 50°C under the atmospheric pressure. The formation rates of (E)- and (Z)-3, 7-dimethy1-2, 6-octadien-1-ol were increased by the pretreatment of R-Co with halobenzenes. On the other hand, the formation rates of other products (3, 7-dimethyl-6-octen-1-ol, 3, 7-dimethyl-6-octenal, 3, 7-dimethy1-1octanol) were decreased by the treatment with halobenzenes. It was found that the effects of pretreatment mentioned above were enhanced with increasing the amount of added halobenzenes or of the temperature in the pretreatment. The effect of the substrate concentration on the formation rates of the products and the change in the amount of halobenzene during the pretreatment were also studied.

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In order to remove [Fe(CN)₆]^3- and [Fe(CN)₆]^4- from waste water, the reduction of [Fe(CN)₆]^3- with sulfite ion has been investigated in the presence of zinc ion which finall y precipitate the iron cyanide complexes as zinc hexacyanoferrate(II).
The reduction of [Fe(CN)₆]^3- was acceleraterl in the presence of zinc ion and the reaction rate was found to be the highest in the vicinity of neutrality. In this reaction, the coexistence of relatively large amounts of alkali metal or alkaline earth metal salts led to a retardation in the reaction rate in the presence of zinc ion. The remarkable effect of zinc ion can be explained by the transfer of electron between sulfite ion and [Fe(CN)₆]^3- in a transition state such as [SO₃-Zn-Fe^III₆]^3- bridged by zinc ion and the resultant formation of⋅SO₃^- radical. In the atmosphere, a pronounced autoxidation of sulfite ion took place simultaneously with the reduction of [Fe(CN)₆]^3-. This phenomenon was considered to support the formation of ⋅SO₃^- radical as an intermediate in the reduction of [Fe(CN)₆]^3-.
For the reduction of [Fe(CN)₆]^3- in the atmosphere, a combined use of sulfite and thiosulfate ions was recommended which brought about a great synergistic effect.

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The relationship between heating weight loss and structures of hydroxyapatite(HAp*)prepared by wet process was studied by thermal analysis(TG-DTA), X-ray diffractometry and scanning electron microscopic observation(SEM).
The reaction products, precip itated from aqueous solutions (H₃PO₄ or Na₂HPO₄+CaCl₂) of various pH's(3∼11) at 25, 50 and 100°C, contained about 3∼25 wt% of H₂O. From analysis of heating weight loss and X-ray diffraction patterns of the products, it is presumed that the amounts of H₂O in HAp* expressed as the value of n (HAp(H₂O)) depend on the reaction temperature, pH and concentration of the reagent in the reaction system. The approximate n values were 2 at 100°C, 4 and 6 at 50°C and 6, 8, 12 and 16(amorphous) at 25°C. The precipitates(n≅8, 16) formed at 25°C changed to the materials with n≅6 by the 1 day digestion in solution. From TG-DTA, H₂O of HAp* were mainly dehydrated step by step with unit of 1/2, 1, 2 and 4×N(N=1, 2, 3) mol H₂O.
Kissinger plots analysis revealed that the activation energy (ΔE¹; 1 st step) of dehydration process were 10, 13, 17, 20 and 25∼28 kcal/mol⋅H₂O, depending on the value of n. The lattice constant(c₀=6.84∼6.90Å) of HAp* changed with the value of n. SEM observation indicated that HAp* has a layer structure.
Experimental results s uggest that HAp*, prepared by wet process, has the lameller structure and has stoichiometric bound water in the form of interlameller water.

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Reverse osmosis of aqueous solution of sodium chloride(NaCl: 0.5 wt%) was studied using the six kinds of porous glass membranes with closed-end tubular form. These porous glass membranes had different amounts of colloidal silica deposited in the phase-separation structure. The higher the amounts of colloidal silica in the structure, the smaller the volume flux of water of the porous glass membrarane, and the greater the salt rejection value. The comparison of the pore distribution before and after the desalination experiment showed that the radius of the micropore, originated from the colloidal silica deposited in the micropore, was 2∼3n m at an early stage and the gradually grew to 12∼15 nm in the second stage. The p ore size at the first stage depended on the heat treatment temperature of the initial borosilicate glass. The micropore size gave an important effect on the desalination characteristics. The second stage micropore was originated from the phase-separation structure. The membrane life of the porous glass baked at 700°C prior to the experiment was remarkably long.

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For the reproducible built-up of stable monolayers of catena-μ-N, N'-bis(dodecyloxycarbonylmethyl)dithiooxamidatocopper(II) on a solid substrate from air-water interface, optimum conditions of the copper concentration in the aqueous substrate, of the piston-oil pressure, and of the dipping rate were determined by elemental analyses and the observation of interference colors of the films. In order to obtain the built-up films composed of equimolecular amounts of the ligand and copper (Table 1), and to reduce the amount of adsorbed copper ions beneath the monolayer, the appropriate copper concentration was found to be 1×10^-4 mol⋅dm^-3. Uniform films with a constant interference color were obtained when the piston -oil was adjusted to 20 mN⋅m^-1 and the dipping rate was controlled within a range of 35-700 mm⋅min^-1.
Anisotropy of the built-up film was examined by means of the polarized infrared spectra (Fig.3) and the electron diffraction patterns (Fig.5, Table 2). These data show that the framework of dithiooxamidatocopper(II) was oriented in the built-up films in parallel to the dipping direction in the film plane. This orientation may arise- from the relative flow of adjacent molecules so as to fill up the vacant due to the consumption of molecules induced by the transfer to the dipping plate. To elucidate the orientation a one-dimensional molecular model is recommended rather than a. two-dimensional model previously proposed.

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The separation of rubidium isotopes (⁸⁵Rb and ⁸⁷Rb) was carried out at several temperatures by means of constant current electromigration in which a cation-exchange membrane of Hform was used as an electrophoretic supporting medium.
A membrane strip (homogeneous resin of cop olymer of styrenedivinylbenzene with sulfo groups, ashiplex CK-1) was placed in a migration apparatus (Fig.1), such that one end of the strip was immersed in an aqueous solution of sulfuric acid (catholyte) and the other end in that of rubidium salt (anolyte). A constant direct current was passed throulh the strip to move rubidium ions towards the cathode with a constant migration velocity. The sharp and stable boundary was maintained between the zones of H-form and of Rb-form during the course of the electromigration. The diffusion coefficient of rubidium ion in the cationexchange membrane was evaluated from Nernst-Einstein's equation (Eq. ( 1 )) using the data on the mobility of rubidium ion deduced from the velocity of the moving boundary and the voltage change during the migration; its values were 2.4×10^-6, 3.5×10^-6, 49×10^-6, and 6.9× 10^-6cm2/s, at 5, 25, 50, and 70°C, respectively.
When the migration distance of the bo undary reached 20 cm, the supply of the direct current was discontinued and the membrane strip was taken out of the apparatus and cut into fractions starting from the frontal end of the Rb-zone at a regular interval of 2.5 mm. For each fraction, the rubidium content and rubidium isotope ratio (⁸⁷Rb/⁸⁷Rb) were determined by flame photometric and mass-spectrometric analyses, respectively. The results of the isotopic 'analysis showed that the lighter isotope ⁸⁵Rb was enriched in the frontal part of the zone. Sv, the relative difference in migration velocity between ⁸⁵Rb and ⁸⁷Rb ions, was determ ined to be 0.77×10^-3, 0.85× 1010^-3, 1.11×10^-3, and 1.36×10^-3, at 5, 25, 50, and 70°C, respectively. The tendency of the increase in e, , with increasing temperature is consistent with the result reoprted by Bonnin et al. (Ref.3)) for the electromigration in a paper-strip medium. A theoretical equation for chromatographic separation of isotopes (Eq. ( 4 )) was applied to the Rb isotope enriched zone. The present Rb-isotopic fractionation plofiles were found to obey the theory quite closely except for the one at 70°C.

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We have previously reported on the direct determination of beryllium oxide in beryl by flameless atomic absorption spectrometry with the mixture of small amounts of powder samples and reductants such as carbon black. This report deals with atomizing effect of carbon black for the direct determination of molybdenum disulfide by flameless atomic absorption spectrometry, and then molybdenum in molybdenite was determined by this method as a practical analysis. Molybdenum disulfide was ground to powder forms (about 1 pm in particle size)by an automatic analytical grinder and a titanium carbide motor. A mixture of the powdered sample and carbon black was dispersed in water by an ultrasonic agitator.
As the results, the dispersed molybdenum disulfide solution exh ibited absorption peak 1.3times higher than the standard solution by the addition of carbon black. Moreover, a negative interference of silicon dioxide was suppressed with the carbon black.
The effect of carbon black was explained in terms of the improvement of the efficiency thermal decomposition of a salt and increase of the formation rate of refractory molybdenum carbide on ashing process. Also, carbon black seems to hinder recombination of molybdenum atom with coexisting elements due to its by electron-donating ability upon atomizing step.

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Selenic and Telluric acids were titrated potentiometrically with titanium(III) chloride solution by using Pt-Cu⋅Hg bimetallic electrodes in nonaqueous solvents such as N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), isopropyl alcohol (IPA) and the mixtures of these solvents.
It was found that selenic and telluric acids were titrated directly at room temperature in DMF solution without hydrochloric acid. The molar ratios of selenic and telluric acids to titanium (III) chloride was 1: 6. However, the corresponding reactions to SeO₄^2-→SeO₃^2- or TeO₄^2-→TeO₃^2- were not confirmed in the titration curve in DMF.
In the titration of selenic acid in mixed solvents of DMF and IPA in 1: 1 or 1: 2 ratio, two steps were observed. The first and the second steps were appeared on the titration curve at molar ratios of 1: 2 and 1: 6, respectively.
It was interpreted that the first step c orresponded to the intermediate reaction of SeO₄^2-→SeO₃^2-
Mixed solution of selenic and telluric acids were determined by the proposed method. Three steps were observed on the titration curve. It was interpreted that the first, second and third steps corresponded to the reaction of SeO₄^2-→SeO₃^2-, SeO₃^2-→SeO₃^2-Se(0), and TeO₄^2-→Te(0), respectively. Less than 5% of water gave no influence on the titration.

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Polymer film was prepared by the electrochemical polymerization of mercaptohydroquinone in the Britton-Robinson buffer (pH 5.0) containing 20 vol % Et0H on glassy carbon electrode. This modified electrode catayzed the oxidation of NADH in a weekly acidic or neutral solution and possessed excellent durability on successive electrochemical oxidation of NADH.
The peak current, on the catalytic oxidation of NADH (0.4mol⋅dm^-3) using the Britton-Robinson buffer (pH 6.35) increased linearly with the sum of quinone moieties in the polymer film ranging from 3×10^-9 to ca.8×10^-9 mol⋅cm^-2 and became a constant value (7.5μA⋅^-2, υ=3.3m⋅Vs^-1) above ca.10×10^-9 mol⋅cm^-2. This result showed that the oxidation of NADH occurs on only active sites (i. e. quinone moieties) in the neighborhood of solution phase and does not occur in the inner part of the film.

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Benzoyl chloride (BzCl) reacted easily with N, N-dimethylthioformamide (DMTF) to form an adduct, N, N-dimethyl(benzoylthio)methaneiminium chloride, which was smoothly decomposed with several neucleophiles to afford thiobenzoic acid (BzSH) together with other products.
When the above reaction was carried out in methanol, both the adduct formation and its decomposition proceeded to produce BzSH, benzoic acid (BzOH), and methyl benzoate (BzOMe). The yield of BzSH increased with increasing amount of methanol. Bz SH was obtained in 75% yield by the use of a large excess of methanol (20 molar equiv. to BzCl)at 0°C for 1 h.
In this reac tion, it is considered that the adduct formation was reversible but a polar solvent such as methanol deviated the equilibrium to the adduct side.
Similarly the reactions of p-substituted benzoyl chlorides with DMTF yielded the corresponding p-substituted thiobenzoic acids in high yields in the case of the electron-donating substituents, whereas electron-withdrawing groups increased the yields of methyl benzoate derivatives and decreased the yields of thiobenzoic acid derivatives.

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11, 11, 12, 12-Tetracyanoanthraquinodimethan (TCNAQ) has been prepared in high yield by direct condensation of anthraquinone and malononitrile using dry pyridine and molecular sieves. The intermediate in the formation reaction was found to be 10-(dicyanomethylene)anthrone. TCNAQ was readily hydrolyzed to 10-(dicyanomethylene) anthrone and anthraquinone under basic conditions. Although TCNAQ was stable against dilute H₂SO₄, treatment whith conc. H₂SO₄ gave a diamide [4], a partially hydrolyzed product. Reaction of TCNAQ with mercaptoacetic acid gave no reduction product, but reaction with NaBH₄ gave tetrahydro-TCNAQ [5]. The different reactivity of TCNAQ with reducing reagents from that of TCNQ can be explained in terms of nonplanar structure of TCNAQ as well as the difference of aromaticity between the benzene and anthracene units. In order to investigate the substituent effects on the properties, several TCNAQ derivatives substituted at the 1-or 2-position were prepared. A linear correlation between the reduction potentials and (σm+σp)/ 2 was observed. The reduction potentials show that TCNAQs are weaker acceptors than TCNQ.

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The optical resolution of substituted benzoic acid salts of (±)-2-anino-1-phenylethanol ((±)-APE) by preferential crystallization procedure has been inve stigated. The benzoic acids employed were 2-amino-, 3-amino-, 3-methyl-, 4-methyl-, 2-chloro-, 4-chloro-, 2-nitro-, and 3-nitrobenzoic acids, and benzoic acid. The racemic structures of the (±)-benzoates were examined by comparing their enthalpies of fusion of the (±)-benzoates with those of the corresponding ()-benzoates, the free energies of formation of racemic compound, and the binary phase diagrams of melting point. The results indicated that only (±)-APE salt of 3-aminobenzoic acid ((±)-3-AB salt) is a conglomerate and other (±)-benzoates form a racemic compound. The optical resolution of (±)-3-AB salt was carried out at 10°C in tetrahydrofuran. The (-)-3-AB salt with optical purity of about 90% was obtained wit h degree of resolution of about 60% by adding 0.02 g of seed crystals in a racemic solution with the degree of supersaturation of 200%.

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A quantum mechanical study has been carried out on the difference of the attacking position of acetone and mesityl oxide upon phenol to give bisphenol A and a chroman derivative, respectively. When the acetone molecule attacks the oxygen atom of phenol, the reaction is predicted to be reversible. When acetone attacks the para-position of phenol, the reaction becomes irreversible and leads to bisphenol A. When mesityl oxide attacks the oxygen atom of phenol, the intermediate undergoes a cyclization reaction which is irreversible. The HOMO's of the oxygen and ortho-carbon atoms of phenol are in phase with the LUMO's of the attacking carbon atom and carbonyl carbon atom of mesityl oxide, respectively.

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Noncatalytic reaction of Wandoan coal with tetralin was studied at temperature of 450°C and pressures of 20 to 60 MPa by continuous flow method. Liquefied products were analyzed by solvent-extraction method into mixtures of compounds as classified as unreacted coals, preasphaltenes, asphaltenes, and oils, and yield-time profiles with these classes of fraction were obtained as shown in Figs.2, 3, and 4. Two mathematical models that adequately describe the observed data were developed, and pseude-first-order rate constants for each of the mechanistic steps were calculated by nonlinear regression. The model involving all possible pathways for the formations of preasphaltenes, asphaltenes, and oils from pure coals was best fit to our experimental data. In practice, however, the model involving the lequential formation of these fractions as a simple series reaction scheme was reasonable to us in our liquefaction conditions. The results study showed rapid conversion of the pur e coalstO liquid products. Pressure effects on these steps were similar as described in a previo us paper, except the direct formation of oils from pure coals somewhat decreased with pressure. Effects of pressure on the formations of tetralin isomer 1-methylindan and naphthalene were also discussed.

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Reactions between coals (Taiheiyo, Hongai) and hydrogen atoms were investigated in a discharge flow apparatus at various temperatures (Table 1) under 133 Pa. Coals were first heated under helium until dry distillation was substantially completed, and then irradiated with hydrogen atoms. The specific gravity, refractive index (Table 2), ¹H-NMR spectra (Fig.1), distillation behavior (Fig.2), Fl-MS spectrum (Fig.3) and gas chromatogram- were determined on liquid products (coal liquid) obtained by runs A∼C in Table 1. Coal liquid C was found to contain a larger amount of alkenes and aromatic compounds compared with those of A, although the ranges of their carbon numbers were nearly the same. The results of the reactions at higher temperature are summarized in Tables 4 and 5. The higher temperature of the heat treatment lowered the reactivity (A; B; D). The higher reaction temperature increased the proportion of the gaseous products (D; E; F). These results are closely related to the O-content and H/C atomic ratio of the heat-treated coals (Table 3). The main product of the gaseous hydrocarbons was mostly methane. No acetylene was detected. Products of the reaction at 600°C comprised about 90% of gaseous hydrocarbons rich in methane and ethylene, while coal liquid (10% of the products) consisted of a great amount of benzene, toluene and xylenes (Table 6).

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The Cannizzaro reaction in alkaline solution for benzaldehyde was studied in the presence of sodium dodecyl sulfate (SDS), dodecyltrimethylammonium chloride (DTAC), hexadecyl trimethylammonium chloride (CTAC), polyethylene glycol monooleyl ether (POMOE) and polyethylene glycol p-nonylphenyl ether (PONPE) at 40°, 50° and 60°C, respectively.
The kinetic and thermodynamic parameters of the reaction were evalu ated from the rate constant of the reaction for each surfactant.
In gelfiltration on a Cellulofine G CL-25 m column, micelles of surfactants at concentrations above the CMC behaved similarly to polymerizing systems. From the gelfiltration data, partition coefficients, molar concentration and concentration effects of solutes in micelle and bulk phases were calculated.
The results obtai n ed were as follows.1) Anionic micelle decreased the reaction rate, while cationics increased it.2) Linear relationships existed between E_a and ΔS_a and between k_obs and concentration of surfactants.3) Benzaldehyde and NaOH were strongly partitioned in micellar phase of the surfactants, especially in those of DTAC and CTAC.
POMOE and PONPE were uniquely partitioned with one of the reaction product (PhCOONa).4) From the kinetic data for bulk and micelle phases (kb and km), it was found that the reaction was accelerated principally due to electrostatic charge and concentration effect by the micelles, followed by lowering of the entropy of activation.

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Four kinds of 1-[2-(alkylamino)ethyl]-2-imidazolidinone [2] [alkyl: C12H25C, 141-129and C161433] were prepared by reactions of the corresponding 2-amino-2'-(alkylamino)diethylamine [1] with urea in good yields. Sodium salts of 3-[3-[2-(alkylamino)ethyl]-2-oxo-1imidazolidiny1]-1-propanesulfonic acids[3] were obtained from [2] and 1, 3-propanesultone with NaH as a catalyst.
The novel compounds obtained were purified through coloumns of anion- and cationexchange resins and identified by TLC, IR and elemental analyses.
Some surface-active and antimicrobial properties of the samples [3] were measured in aqueous solution. The results showed that these compounds were excellent as emulsifying, solubilizing and antimusty agents.

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Much effort and experience have been required for. perfuming detergents and soaps, since the aroma of odorants solubilized in surfactants can be differnt from that of the original blend. Previous papers described the solubilization of 4 pure perfume materials into sodium dodecyl sulfate (SDS) micelles and their aroma intensity. In the present study, details of the solubilization mechanism of the geraniol-geranyl acetate binary solution into the micelles, partial vaporpressure and concentration of aroma from the dispersed system were inve stigated by using the methods described in the previous papers. Geraniol molecules were solubilized into the palisade and hydrophobic-group layer of SDS micelles. On the other hand, geranyl acetate molecules were solubilized only into the hydrophobic layer. Number of micelles in the dispersed system increased in proportion to the amount of added geraniol until geraniol molecules filled the palisade layer. The amount of solubilized geranyl acetate increased with the number of micelles in the dispersed system. As geraniol molecules became solubilized into the hydrophobic zone, the solubility of geranyl acetate decreased. While the relative volatility of geranyl acetate to geraniol was quite low in the original blends, it became heightened in the dispersed system as the partial vapor pressure of geraniol decreased remarkably. Vapor components of the binary solutions solubilized in surfactant micelles differed from those of the original blend solution. The findings give an explanation for the characteristic property of the aroma of odorants solubilized in surfactants.

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Oxidative coupling polymerization of m-diethynylbenzene (MEB) was carried out in the presence of the copper(I) chlorideN, N, N', N'-tetramethylethylenediaminepyridine system in o-dichlorobenzene, nitrobenzene, diphenyl ether, quinoline, N, N-dimethylformamide, and dimethyl sulfoxide at 90°C (Table 1). The polymer obtained could be manufactured into a tough film by the solvent casting method when its solution viscosity in nitrobenzene at 160°C was more than 0.19η_sp/C. Copolymerization of MEB and p-diethynylbenzene (PEB) was carried out in o-dichlorobenzene and nitrobenzene at 95°C (Table 2). The copolymerization with monomer feed of 7.4 to 10 mol% of PEB proceeded without depositing a polymeric product to yield the copolymer with higher molecular weight in comparison with that of the homopolymer of MEB.
Thormal degrad ation behavior of the homopolymer of MEB and copolymer of MEB with PEB was examined by means of thermogravimetry and differential thermal analysis under air and nitrogen atmospheres. Both polymers exhibited a similar thermal stability and the copolymer was slightly more stable than the homopolymer (Figs.1 and 2).
Electrical properties of the homopolymer of MEB doped with v arious electron-accepting dopants such as tetracyanoquinodimethan (TCNQ) (Fig.3), bromine (Fig.4), iodine (Fig.4), and arsenic pentafluoride (AsF₅) (Fig.5) were studied. Conductivity of the undoped homopolymer of MEB was found to be 9.5×10-^-18 s/cm. It was found that conductivity of the doped polymers increased with the amount of the dopant and reached to 2.9×10^-9 and 2.81×10^-11 s/cm when TCNQ and AsF₅ were doped, respectively. The conductivities of iodine- and bromine-doped polymers were 5.5×10-15 and 5.0×10-1' sicm, respectively, when the halogen vapor was absorbed for 12 h.

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A new technique using copper(II) sulfate as absorbent for ammonia was developed in order to obtain an average concentration of ammonia in the atmosphere over a period of one month.
Ammonia is absorbed for one month by copper(II) sulfate and steam-distilled into boric acid solution for determination of ammonia by indophenol method. The concentration of ammonia in the atmosphere is calculated from the amount of ammonia in boric acid solution.
Absorption life of the absorbent is over one month, and ammonia captured in the a bsorbent is very stable for one month.
The concentration of atmospheric ammonia in Hiratsuka City was measured by this method for five months.

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A simple equation to estimate breakthrough time of organic solvent vapors on fixed beds of activated carbon was proposed. The basic equation was obtained from the mass transfer of organic solvent vapors from the gas stream to the carbon particles. Freundlich isotherm was applied to simplify it. Two parameters in the simplified equation was determined on basis of experimental and literature values. The calculated breakthrough times by the proposed equation were compared with reported and our experimental values. The calculated values were in good agreement with the literature values of 121 solvents and our experimental ones of 17 solvent vapors including the results of a previous report for benzene vapor in wide experimental conditions (10∼30 mm of bed diameter, 700∼40000 ppm of vapor concentration, 0.2∼15l/min of gas flow rate and 1∼4 g of the amount of activated carbon). The proposed equation was simple but calculated breakthrough times were shown to be in better agreement with experimental ones than the values by three reported equations.

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Photochemical reactions of trihalomethanes in aqueous H₂O₂ solution were studied at room temperature under the irradiation with a Vycor-filtered light from a low pressure mercury lamp. CHCl₃ did not decompose in air-saturated aqueous polution, but was converted to CO₂and HCl by the addition of H₂O₂ due to the reaction with OH radical formed by the photodecomposition of H₂O₂ at 254 nm. Photoirradiation of an Ar-saturated aqueous solution of H₂O₂ without CHCl₃ led to the formation of O₂. The quantum yield of the O₂ formation (Φ_O2)decreased and that of the CHCl₃ decomposition (Φ_-CHCl3) increased with inc reasing the concentration of CHCl₃. The sum of Φ_O2 and Φ_-CHCl3 was constant, indicating that two OH radicals are required for the decomposition of a CHCl₃ molecule in Ar-saturated aqueous solution. The simultaneous formation of CO and C_O2 occurred upon irradiation of several brominecontaining trihalomethanes (CHBr_nCl_(3-n) in the presence of H₂O₂. The yield ratio of CO to C_O2 was proportional to that of the numbers of quanta at 254 nm absorbed by trihalomethanes and H₂O₂. The bromine-containing trihalomethanes gave C_O2 exclusively by the reaction with OH radical as generated by Fenton's reagent or γ-radiolysis of N₂O-_O2-saturated aqueous solution.

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In the mud of Minamata Bay from where the Minamata disease was originated, a large amount of mercury compound(s) has been deposited, and the majority of it has been estimated to be chemically inactive mercury (II) sulfides.
In this study, a mercury compound(s) hitherto unknown and soluble in dimethyl sulfoxide (DMSO) was detected from dried samples of the mud collected at the three locations of MinaInata bay and its properties were investigated.
The total mercury in the mud w as 44∼152μg/g, dry weight, in which the DMSO-soluble mercury accounted for 1.0∼4.6% of the total. Its percentage appreciably differed among the sampling locations. The DMSO-soluble mercury changed in amount during the passage of time, which was confirmed by the measurement of content of the reducible mercury i. e., the mercury directly reduced with tin(II) chloride. When separated on a reversed-phase column, the reducible mercury was eluted in the fraction nearby the void volume; this mercury compound was assumed to be a salt of inorganic mercury compound(s).
Utilizing the property of mercury(II) halide to form a comple x with halide ions in excess, a method has been established to analyze the mercury compound by ion-pair chromatography in the presence of the counter ion. By this method, the reducible mercury is confirmed as a mercury(II) halide. Since th emethylation of inorganic mercury is considered to take place through a soluble mercury(II) compound(s), a possibility is suggested that the reducible mercury found in this study may account for one of themercury compounds contributable to the methylation.

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Methylation reaction of phenethyl alcohol with dimethyl sulfate was studied in order to pursue the optimum reaction conditions for the synthesis of methyl phenethyl ether.
When a mixture of phenethyl alcohol, 50% aqueous solution of sodium hydrox ide dimethyl sulfate, benzene and a catalytic amount of tributylamine (TBA) was stirred at 40°C for 3 h, methyl phenethyl ether was obtained in 92% yield. The yield of methyl phenethyl ether increased as the amount of TBA was increased. Not only tertiary amines such as tributyland trioctylamine but also guar ternary ammonium chlorides such as tetrabutylammonium and trioctylmethylammonium chloride served as the most effective catalysts for this etherification.
In addition, four kinds of aromatic alcohols were also alkylated with dimethy l and diethyl sulfate to give methyl and ethyl ethers in a similar procedure.

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The reaction of 2- and 2(10)-pinene oxides, [1] and [2], in polar aprotic solvents or chloroacetic acids in the presence of synthetic zeolites was studied. In DMF, trans-carveol [8] was obtained as a principal component from [1] in 85% selectivity. In SF, myrtenol [6] was obtained from [2] in high selectivity (97%). Perillye alcohol [11] was obtained from [2] in 84% selectivity by the reaction with trichloroacetic acid in the presence of A-4zeolite.

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The spontaneous reaction of phenyl isocyanate with 1-butanol was carried out in various solvents. The second-order rate constants for urethane formation were correlated, to a certain extent, to the dielectric constant and the polarity parameter of solvents. Although it was investigated whether the rate constants have correlations to the solubility parameter and th e h ydrogen-bonding one of solvents, the existence of a well-defined linear relationship between them was not observed.

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Photopolymerization of methyl methacrylate and methyl cinnamate was carried out using benzoin ethyl ether (BEE) to yield light-focussing plastic rods with parabolic gradient of refractive index in the region near center axis. The gradient constant (A), which was measured by light tracing method, increased with the increase of BEE concentration. To improve the mechanical strength plasticizer was added, but most of general plasticizers caused the reduction of A value. However, the plasticizer which has a photoinitiating property did not. The mechanical strength of the plastic rods observed by the tensile properties showed maximum of 2.0 kg/mm2 at 7% addition of such a plasticizer.

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To expand the use of ceramic membrane, the ultrafiltration of return sludge has been carried out. The return sludge was obtained from two plants of activated sludge process. A membrane module, in which a tubular ceramic membrane was inserted, was set up for ultrafiltration. The values of volume flux through membrane were measured under different conditions of gauge pressure, feed velocity, and Mixed Liquor Suspended Solid (MLSS) of return sludge. The following results were obtained: ( 1 ) the volume flux was not influenced by gauge pri'ssure and MLSS: (2) the volume flux increased with increasing feed velocity. It was speculated from above results that a sludge layer might be formed on the surface of ceramic membrane under ultrafiltration. The volume flux was found to be recovered up to 81∼91% by washing with NaClO solution.

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A modified method for preparing gelatin from chrome-tanned leather pretreated with lime soak is proposed to improve the polluted sewage from leather industry. After liming for 3days, washing and pH adjustment, the limed leather was subjected to gelatin extraction for 3 h at 70°C. Gelatin was obtained in 40% yield and its quality was good: Viscosity 158 mp, gel strength 415 g, chromium 30∼70 ppm, calcium 0.8∼20. %. The chromium(III)content in the liming solution and wash water was less than 0.1 ppm and chromium(VI) was not detected.

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