Phase diagrams for ternary systems of poly(oxyethylene) (n) hexadecyl ether-1-hexanol-water have been determined in order to compare those of inonic surfactant systems and know the influence of the oxyethylene chain length (n=5.5, 10, 20). It was found that phase areas were varied with an increase of oxyethylene chain length:
1) Normal and reversed micellar solution regions were extende d.
2) Various kinds of liquid crystal regions based on norm al micellar solution appeared.
3) Lamellar liquid crystal region became narrow and was finally analgamated in micellar solution region.

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The solution behavior of the mono-L-arginine and monopotassium salts of long-chain monoalkyl phosphates has been studied in order to see the changes in the solution state and in the association structure with the phase-transition phenomena. In the case of potassium hexadecyl hydrogen phosphate/water systems, three kinds of phase transition (coagel-gel, gel-liquid crystal, and the structure change of liquid crystal) were observed in the temperature range of 0-100°C from the DSC measurements On the other hand, only gel-liquid crystalline phase transition (Tc) was observed for L-arginine hexadecyl hydrogen phosphate/water systems.
In the case of mono-L-ar ginine salt system the three dimensional association structure, such as liquid crystal and gel, was easily formed from quite low concentration, and the gel retaining water existed as the stable phase down to 0°C at the temperatures below T. From the small angle, and wide angle X-ray diffraction, it was confirmed that the above gel phase had lamellar long range order and alkyl chain of monoalkyl phosphate was aligned in a hexagonal structure in each layer.
The following reasons for the above phen omena are supposed: L-arginine residue will be very bulky as the counter ion and the molecular interaction between the neighboring molecules is strong because of zwitterion formation with the dissociation of amino and carboxyl groups of amino acid residue.

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Chemical species of unreduced and reduced 12-molybdophosphoric acid (PMo₁₂) and their reaction have been investigated in concentrated aqueous and 50% water-dioxane solutions using ³¹P-NMR and polarography.
Phosphorus-31 chem ical shifts of α-PMo₁₂ and β-PMo₁₂ in the range of the degree of reduction among 0 and 4 were obtained in 50% water-dioxane as follows (Fig.13): α-PMo₁₂(0) 3.6 ppm, β-PMo₁₂(0): 3.3 ppm, α-PMo₁₂(II): 5.8 ppm, β-PMo₁₂(II): 6.6 ppm, α-PMo₁₂(lV): 4.6 ppm, β-PMo₁₂(IV):-12.9 ppm.
³¹P-NMR study clarified the isomerization and disproportionation behavior of unreduced and reduced PM012 in concentrated solutions (Scheme 1) and made it possible to estimate approximate half-life periods for each step (Table 1).
Isomerization of β-PMo₁₂(0) to α-PMo₁₂(0) was immediate in water (Fig.10) and rapid in 50% water-dioxane (half-life period: 5 h) (Fig.7).
The two-electron reduced product of α-PMo₁₂(0) in 50% water-dioxane was α-PMo₁₂(II)(Fig.11), while that in water was a mixture of α-PMo₁₂(0), β-PMo₁₂(II) and β-PMo₁₂(IV)(Fig.12).
This is attributed to the isomerization of first-formed α-PMo₁₂(II) to β-PMo₁₂(II) which disproportionates quickly to β-PMo₁₂(IV) and β-PMo₁₂(0), the latter of which is then reduced to β-PMo₁₂(II) or isomerizes to α-PMo₁₂(0) immediately.
β-PMo₁₂(IV) was the only stable species in four-electron reduced products of α-PMo₁₂(0)both in water and in 50% water-dioxane (Fig.1) since a-PMo12(1V) gradually isomerized to β-PMo₁₂(IV) (Figs.3, 4, 5). The following two routes are proposed for the reduction of α-PMo₁₂(0) to β-PMo₁₂(IV) in solutions.
Strong reducing agents such as ascorb in a ufficient amount take the former route (Eq. 1). However, even milder reducing agents incapable of reducing α-PMo₁₂(II) can produce β-PMo₁₂(IV)in water through the latter route(Eq.7).

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In order to investigate the effect of halogens in the regioselective cleavage of cyclopropane rings, difluoro, dichloro and dibromo derivatives of n, n-dihalobicyclo [n-3. 1. O]alkanes (n=6, 7 and 9) were hydrogenated with palladium-charcoal (Pd-C) or Raney nickel catalyst in methanol solution at room temperature under the atmospheric pressure. The effect of amines as additives was also investigated. When the difluoro derivatives were hydrogenated over Pd-C, the compounds with n=6, 7 and 9 were all cleaved exclusively at the condensed bonds to give the corresponding ring-enlarged products, whereas only the compound with n=6 was hydrogenolyzed by the use of Raney nickel to give the ring-enlarged products. The addition of amines retarded the hydrogenolysis and the retarding effect of amines increased in order of the adsorption strength of amines to the catalysts. The hydrogenation reactivity of dichloro derivatives in the Pd-C-catalyzed hydrogenation was relatively low and only the compound with n=6 was ring-enlarged. On the other hand, Raney nickel-catalyzed hydrogenation of dichloro derivatives, n=6, 7 and 9, proceeded smoothly in the presence of amines and th e C-Cl bond was cleaved to give monochlorocyclopropanes, accompanied by small amounts of methylcycloalkanes, respectively. Dibromo derivatives, n=7 and 9, were hydrogenolyzed at the C-Br bond over both Pd-C and Raney nickel in the presence of amines to give monobromocyclopropanes, accompanied by small amounts of methylcycloalkanes. These results may be explained by the differences in the contribution degree of the two factors: the strain of the cyclopropane ring caused by the substitution of halogens and the strength of the adsorption of halogens to the catalysts.

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A type zeolite was synthesized using a Shirasu-Na₂O mixture, prepared by heating Shirasu and NaOH at 300°C, and the effect of synthetic conditions on the particle size of th e final product and the rate of formation were studied.
The particle size of A type zeolite was well dependent on the synthetic conditions, the mean particle size, determined by SEM, ranging from O.27 to 1.94 ium. Seeding or aging was very effective to decrease the particle size particularly at low hydrothermal temperatures. In a case of no seeding and no aging, the higher the hydrothermal temperature, the smaller the, particle size of the product. Taking into account the exhaustion of nutrient in t he gel mixture, an equation was developed to describe the rate of formation, and applied to t h e 7 estimation of the crystal growth rate of A type zeolite. The rate of formation was changed greatly by the seeding or the aging, but the crystal growth rate was hardly changed. The rate of zeolite formation seemed to be affected mainly by the nucleation rate.

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In the reaction of diphosphorus pentaoxide (O'-form) with α-alumina (α-Al₂O₃), theconditions for formation of various aluminium phosphates (molar ratio of P₂O₅/Al₂O₃, heatingtemperature and time, water content of P₂O₅) were investigated by means of X-ray diffraction, DTA and TG.
( 1 ) The aluminium phosphates produced were orthophosphate AlPO₄ (berlinite, cristobaliteform), Al(H₂PO₄)₃ (C-form), triphosphate AlH₂P₃O₁₀(I-form), metaphosphate Al(P0₃)₃(A, B, E -form), and three unknown compounds. ( 2 ) AlPO₄ was easily formed at the molar ratio of P₂O₅/Al₂O₃(R) =1 and above 300°C; berlinite was obtained at the water content above 10%, while cristobalite-form was obtaind regardless of the water content of P₂O₅. Al. (H₂PO₄)₃ was formed at R=1, 200°C when the water content was more than 30%. AlH₂P₃O₁₀(I-form) was produced at R≥3, 300°C, and at 12-30% of the water content. Al(PO₃)₃ was formed at high temperatures (above 400°C); the B and E-forms were chiefly obtained at the low water content of P₂O₅(less than 10%), while the A-form was obtained independent_ of the water content of P₂O₅. ( 3 ) the reaction rate of P₂O₅ with α-Al₂O₃ was mainly influenced by the water content of P₂O₅ and the reaction was accelerated with an increase in the water content of P₂O₅. ( 4 ) In the reaction of P₂O₅ with α-Al₂O₃, polyphosphoric acid is considered to be formed at first by the hydrolysis of P₂O₅ and reacts with α-Al₂O₃ to produce various aluminium phosphates.

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The needle-like ZnO prepared by gas-phase oxidation of zinc metal vapor was treated under 1.01×10⁵ and 1.3 Pa in the range of 20° to 350°C, and its excess zinc content and conductivity were measured. On the basis of these data, the comparison was made for the concentration of oxygen chemisorbed on the crystal surface and the nonstoichiometry between the needlelike powders and commercial, granulated powders by French process. The results obtained are as follows. ( 1 ) The needle-like ZnO has lower concentration of chemisorbed oxygen than the granulated ZnO. ( 2 ) The nonstoichimetry of the needle-like ZnO in vacuo increases remarkably with a rise of temperature, compared with that of granulated ZnO.
It was concluded that these results were due to the characteristic form and crystal surface of the needle-like ZnO.

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The needle-like ZnO was prepared by gas-phase oxidation of zin c metal vapor, and the adsorbed water on its surface was investigated by means of DTGA and active hydrogen analysis. Adsorbed state of water on the crystal surface was studied by comparing the needlelike powders with the granulated powders by French process. The, results obtained are as follows. ( 1 ) The proportion of water vapor evolved from the needle-like ZnO around 500°C (isolated hydroxyl) is less than that froth the granulated ZnO. ( 2 ) Around 400°C, it (doused hydrogen bonding hydroxyl) is almost equal to zero. ( 3 ) On the contrary, around 80°C, it is more than that from the granulated ZnO. This water is considered to be molecular type water on the crystal surface. ( 4 ) The amount of physisorption water on the needlelike ZnO is less than that on the granulated ZnO. This seems to be due to the lower concentration of surface hydroxyl on the needle-like crystal.

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The reactions of polyfluoroalkyl o-nitrobenzenesulfonates [1a-1d] with 1, 4-diazabicyclo[2. 2. 2]octane (DABCO) were investigated under the various conditions. The sulfonates ([1a] and [1b]) having shorter polyfluoroalkyl groups reacted with DABCO at 35°C in benzene to give 1-(polyfluoroalkyl)-4-aza-1-azoniabicyclo[2. 2. 2]octane o-nitrobenzenesulfonates ([2 a-I] and [2 b-I]) in high yields (93-94%). However, the reactions of the longer polyfluoroalkyl sulfonates ([1c] and [1d]) did not take place under the same conditions. At higher temperature (80°C), [1a-1d] gave 1-[2-[4-(polyfluoroalkyl)-1-piperadinyl]ethyl]-4-aza-1-azoniabicyclo[2. 2. 2]octane o-nitrobenzenesulfonates [3 a-I-3 d-I], without giving [2 a-I-2 d-I]. Aprotic solvents such as DMSO, DMF and sulfolane promoted the reaction of [1a] with DABCO even at room temperature (about 20°C), forming a mixture of [2 a-I]and [3 a-I].
The results of the reactions of ethyl p-toluenesulfonate and 2, 2, 2-trifluoroethyl iodide with DABCO were compared with those of [1a] with DABCO.
The quarternary ammonium cations and cluster ions were observed in secondary ion mass spectra (SIMS) analysis of the quarternary ammonium compounds prepared in these reactions and were useful for identification of these compounds.

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The catalytic hydroalumination of 1-alkynes such as 1-hexyne and 1-octyne with LiAlFl₄ has been investigated in the presence of Ti(cp)₂Cl₂ at 30°C. The hydrolysis of the hydroalumination products gave hexane or octane together with 1-hexene or 1-octene. The selectivity for 1-alkene produced by the hydrolysis of alkenylaluminum compounds increased up to 80-82% with an increase in the molar ratio of 1-alkyne to LiAlH₄([1-Alkyne]/[LiAlH₄]) (Table 1 Run 1-4). It was found that the steric bulk of alkenyl- and alkylaluminum hydride intermediates was responsible for the selective formation of 1-alkene (Table 1 Run 5 and 6). ¹H-and ¹³C-NMR spectra of the deuterolysis products with D₂O indicated that the main product in the hydroalumination of 1-alkynes with LiAlH₄ was 1-alumino-1-alkene ( 7 )(Table 2).

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The polymerization of methyl methacrylate(MMA) by iron(III) nitrate in aqueous solution containing a surfactant under a nitrogen atomosphere at 30°C was investigated. The effective surfactants for the polymerization were of the nonionic type as follows; Tween series (except Tween 85), Brij 35, and Triton X 405. The polymerization was hindered by the addition of 2, 2-diphenyl-1-picrylhydrazyl, 1, 4-benzoquinone or a small amount of oxygen. The copolymer composition curve for the copolymerization of MMA with styrene agreeded with that for the ordinary radical mechanism. On the basis of these results it was considered. that the polymerization of MMA was proceeded through a radical mechanism. The polymerization of MMA by iron(III) chloride, iron(III) sulfate or ammonium iron(III) sulfate was found to proceed through the same mechanism.

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The blood-compatible segmented polyurethaneurea (SEUU) derived from triblock copolymer containing oxytetramethylene units and oxyethylene units was developed as a raw material for such biomedical uses as artificial organs. SEUU was synthesized by the prepolymer method, i. e., hydroxylterminated poly(oxyethylene)-poly(tetrahydrofuran)-poly(oxyethylene)triblock copolyether (HT-ETE) was allowed to react with 4, 4'-diisocyanato diphenylmethane (MDI), followed by the addition of ethylenediamine (ED) to yield the SEUU. The HT-ETE was prepared by anionic polymerization, and the content of oxyethylene in the HTETE was changed from 12 to 33 mol% in order to study the effect of the hydrophilicity. The antithrombogenicity of the SEUU was evaluated by the Lee-White clotting test, the platelet adhesion test and the short-term implantation into canine peripheral veins. The tensile tests of dry and wet films of the SEUU were carried out to evaluate the mechanical properties. As a result, the SEUU was found to exhibit more excellent mechanical properties and antithrombogenicity than the segmented polyurethaneurea based on poly(tetrahydrofuran)without oxyethylene units.

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Polyelectrolyte complex membranes consisting of chitosan, methyl glycol chitosan and poly(vinyl sulfate) have been prepared. The membranes prepared in high hydrogen ion concentration were stable in alkaline and acidic solutions. The transport behavior of alkali metal ions through these membranes was much effected by the hydrogen ion concentration which played the role of a driving force. It was suggested that the affinity of the carrier and the degree of changes in the chemical and physical properties of the polyelectrolyte complex membrane with the hydrogen ion concentration controlled the active and selective transport through the membrane.
When the poly(styrenesulfonate) and the poly(styrenesulfonic acid) as the materials of large ionic size were used instead of HCl and NaCl as the materials of small ionic size in this experiment, the velocity of transport of Na⁺ and the transfer ratio through membrane at 30°C were much larger than those with HC1 and NaCl and the time for the transfer was also elogated. However, little difference in selective transport of K⁺ and Na⁺ was observed.

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Dust originating in China continent is transported to Japan every spring. It is the wellknown Kosa (“yellow sand”) phenomenon. We collected samples of Kosa suspended in the atmosphere at five sites in Japan, Nagasaki, Okayama, Nagoya, Niigata, and Yokohama, in 1980 and 1981. The chemical composition and size distribution of these samples were measured in order to investigate the origins and physical and chemical properties of Kosa.
In 1980, remarkably big Kosa phenomena were observed twice, in April 20-23 and May 5-7, in Japan. During these Kosa periods, coarse particle (>2 μm) concentration in the atmosphere was more than 200 μg/m³, 4 to 7 times higher than that during non-Kosa periods. Therefore the size distribution of Kosa transported was predominantly coarse mode.
As the result of elemental analysis of Kosa samples by X-ray fluorescence methods, it was found that the concentrations of soil-origin elements such as Al, Si, K, Ca, and Fe in coarse particles were greatly increased during Kosa periods, but those of anthropogenic elements such as Cu, Ni, Zn, and Pb were remained unchanged. Judging from the high concentration of Ca in Kosa samples, the origin of Kosa seems to be deserts of Taklamakan and Gobi, whose soils are enriched with Ca.
An interesting fact was also found during Kosa periods, that is, the concentration of particulate sulfur in coarse particle increased, but that in fine particles decreased. However, the size distribution of sulfur in the atmosphere was usually fine mode during non-Kosa periods. The decrease of sulfur dioxide in the atmosphere was also observed during Kosa periods at each sampling sites. It can be explained by the meteological factor that a strong air flow from the moved air mass is generally occurred during Kosa periods. The increase of sulfur in coarse particles observed during Kosa periods is considered to be due to the finding that the transported Kosa itself contains much sulfur because the desert soil is abundant in CaSO₄ by calcification.

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Considering the influences of mercury emitted to the atmosphere, it is important to evaluate the mercury movement in atmospheric environment at various regions in the world. In this report, the movement was investigated quantitatively on the basis of data obtained in Niigata Prefecture. The method is applicable in other regions.
Mercury exists mainly in the gaseous form in the atmo sphere, and its quantity in the atmosphere of Niigata Prefecture (Area: 1.26×10⁴ km²) is estimated to be about 200 kg. The mercury emission from anthropogenic sources is estimated to be about 900 kg per year by measuring both the mercury concentration in exhaust gases from major factories and the volume of g ases exhausted and/or by measuring both the mercury concentration in fuels a nd ingredients and their annual consumptions. The mercury emmission from natural sour ces is estimated to be about 50 kg per year, including the volcanicflumarolic activity (40 kg/y)and the evaporation from the ground and water surface (10 kg/y). So, the total mer cury emission to the atmosphere is estimated' to be about 950 kg per year in Niigata Pref ecture. On the other hand, the total mercury removal from the atmosphere is estimated to be about 310 kg per year, including the deposition due to precipitation (180 kg/y), the uptake by plant leaves (100 kg/y) and the local deposition near point emission sources (30 kg/y). Consequently, the emission to the atmosphere is in excess of the removal in Niigata Prefecture.

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A method was investigated for the selective determination of organic arsenic compounds such as methylarsonic acid (MMAA) and dimethylarsinic acid (DMAA) in river water by using hydride generation atomic absorption spectrometry. Inorganic arsenic, MMAA and DMAA in a sample are reduced to arsine, methylarsine and dimethylarsine, respectively, by an addition of NaBH₄. The arsines generated from the sample are collected on a liquid nitrogen cold trap, and separated by heating the trap due to their different boiling point. The arsines vaporized from the trap are carried to a quartz furnace and analyzed by atomic absorption spectrometry.
The good separation of methylarsine and dimethylarsine was accomplished by using 15% OV-3 on Chromosorb W 60/80 mesh as a packing material. The elimination of interferenc es due to foreign ions was investigated and the use of ethylenediaminetetraacetic acid (EDTA)and tartaric acid was very effective for the MMAA and DMAA determination. The detection limits by this method were 3 ppt for MMAA and 6 ppt for DMAA with a 200 ml sample solution. The coefficient variation for replicate determinations of 10 ng MMAA and DMAA were 3.5% and 3.0%, respectively. Therefore this method is suitable for the determination of MMAA and DMAA at trace levels in river water.
The concentrations of arsenic compounds(As(M), As(V), MMAA and DMAA) at 29 sampling sites in Tone river were determined. The average concentration was 1.57 (0.18-5.88) ppb for As(V), O.61 (0.16-3.31) ppb for, As(III), 21 (8-77) ppt for MMAA and 40 (11-140)ppt for DMAA. It was found that more than 97% of arsenic in the river water was inorganic arsenic and a few organic arsenic existed as MMAA and DMAA. However, high concentration of organic arsenic (77 ppt MMAA and 140 ppt DMAA) was observed at Kasumigaura, and organic arsenic occupied 10% of total arsenic. Thus the increase of organic arsenic observed at Kasumigaura might be due to the methylation of inorganic arsenic by the eutrophication of lake.

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A measurement of the rest potential on a platinum electrode in 1 mol/dm³ sulfuric acid solution has been carried out to develop a convenient analytical method of ethanol in liquor. There was a linear relationship between the rest potential and the logarithmic e thanol concentration in addition of few drops of ethanol into sulfuric acid solution, although slopes of the linear line were different from each other. In this investigation its linear relationship was 'satisfactorily applied to ethanol analysis in liquor.

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This paper describes the influence of extraction pH on the yield and the quality of gelatin extracted from chrome-tanned leather treated with lime. Gelatin could be extracted from the solution of pH below 4 and above 7, whereas could not be extracted at the pH range of about 4-7. The yield was related to the thermal denaturation temperature of the lime-treated leather in the solution. The molecular weight of gelatin extracted at pH above 7 was high, while that of gelatin extracted at pH below 4 was low.

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