Allophane (Japanese colloidal earth) cosists of silica-alumina gel. This earth contains from 2 to 18 wt% of Fe₂O₃ as impurity.
If this impurity can be removed without impairment to its charactristic surface, we can expect to enlarge the utilization of this colloidal earth.
Applying the Jackson's method, which treats clay with a solution of sodium hydrosufite and sodium citrate, to Japanese colloidal earth, we studied the conditions for removal of Fe₂O₃ contained and in what state Fe₂O₃ exists.
In this study two kinds of samples were used, one of which contained 3.37 wt % Fe₂O₃ and the other 13.08 wt%.
The experiments were carried out by means of a batch-system reactor with a stirrer. We obtained the following results.
(1) Under the most suitable conditions, it is possible to remove 90 wt% of the Fe₂O₃ con tained.
(2) The optimum conditions are 60°C and 15 min as reaction temperature and time, respectively.
(3) In case a sodium hydrosulfite-sodium citrate solution is used, it is suitable to use 1 gram of the former per gram of the sample earth and 40 ml of the latter as in 0.3 mol solution.
(4) The states of Fe₂O₃ included in those colloidal earths were different from each other.

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In order to study the behavior of Se-Te-S crystals, the amorphous samples were crystallized at 120°C and the electric conductivity was measured as a function of temperature.
The electric conductivity of the samples containing 5 atom % of tellurium decreased slowly when the content of sulfur in selenium-tellurium increased to about 2 atom %, but increased sharply with increasing content of sulfur when the content it above 2 atom %. Furthermore, the conductivity again decreased sharply with increasing content of sulfur when the content is more than 10 atom %. On the other hand, the change in the conductivity of the samples containing 10 atom % or 15 atom % of tellurium became small in comparison with that of the samples containing 5 atom % of tellurium.
The decrease of the electric conductivity in the parts of the increasing content of sulfur seems to be caused by the formation of the peritectic of selenium-tellurium solid solution covered with sulfur.

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The solubilization of water in cyclohexane solutions of polyoxyethylene alkyl (C₆∼C₁₂) phenylether has been investigated as functions of temperature, the oxyethylene chain length and the hydrocarbon chain length of the solubilizer.
The maximum amount of solubilized water increases remarkably with the size of hydrophilic and lipophilic groups at the same optimum temperature.
The effect of mixing of sucrose myristate and sorbitan monolaurate as solubilizers on the solubilization of water in cyclohexane solution of C₂H₁₂C₆H₄O(CH₂CH₃O)_7.4H were also studled.

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The gas phase polymerization of propylene with AA-TiCl₃-AlEt₂Cl in the absence of solvent has been kinetically investigated. The stationary polymerization rate without solvent increased with increasing [Al]/[Ti] molar ratio and approached to that of the usual polomerization with solvent. The observed stationary polymerization rate (R) could be expressed by a function of molar ratio [A1]/[Ti], A, and propylene pressure, P, -as follows:
where K is a constant which depends on temperature. When n-heptane was admitted intermittently to the polymerization system in which n-heptane was absent initially, the stationary polymerization rate increased and finally reached that observed with solvent.
The observed kinetic behaviors of the polymerization without solvent have been explained on the basis of the supposition that the incomplete removal of the polymers transferred from the polymerization centers is responsible for the depression of the polymerization rate in the system without solvent.

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Disproportionation of propylene on several metal oxide catalysts was studied by means of a flow method. The effects of pretreatment of catalyst with various gases and of various supports on the reaction were investigated in order to clearify the formation of active centers of catalyst. The reaction was carried out at the temperature range from 100°C to 200°C on each catalyst activated 'previously with dry nitrogen gas, dry oxygen or dry hydrogen at 500°C.
It was found that WO³-γ-Al₂O₃ was the most active catalyst for this reaction, but selectivity was rather small. On the other hand, the activity of MoO₈-γ-Al₂O₃ was very high at the beginning of the reaction, but the activity decreased gradually with the reaction time. When the catalyst was pretreated with nitrogen, the activity was greatly different with the various supports, that is, MoO^3-SiO₂.Al₂O₃ was most active, and both MoO²-SiO, and MoO³-α-Al₂O₃ had no activity for this reaction. From these results, it seems that the activity of several supported MoO₃ was correlated with the acidity of these carriers.
By reducing all these catalysts with hydrogen before the reaction, the activity prominently increased, especially the activity of both MoO³-SiO₂ and MoO³-α-Al₂O₃ became almost equivalent to that of MoO³-γ-Al₂O₃.
From these phenomena, it is concluded that the active center of these catalyst is slightly reduced molybdenum oxide, and the acidic carrier plays a role in forming the active center during the pretreatment of catalyst, without directly participating in the reaction.

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Acrolein and acrylic acid were formed in rairly high yield by the oxidation of propylene over metallic palladium supported on active charcoal or silica gel in the presence of steam at 100∼160°C. This reaction temperature is much lower than that for transition metal oxide catalysts.
Besides acrolein and acrylic acid, carbon dioxide was formed. Acrylic acid anal carbon dioxide increased with reaction temperature, while the formation of acrolein reached maximum at 140°C. The rate of formation of acrolein and acrylic acid linearly increased with increase in steem pressure, whereas that of carbon dioxide had little relationship to steam pressure. The rate of achrolein (plus acrylic acid) formation was found to be represented by the following equation:
It was suggested that carbon dioxide and acrolein were formed on different sites of catalyst surface.

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The title reaction was studied at 0∼40°C in order to characterize the catalytic action of alkaline earth oxides. The catalytic activity at 32°C was found to be in order of MgO<Ca0= SrO= BaO (Table 1), the activation energies being 11.1, 11.5, 20.3 and 20.3 kcal/mol respectively (Table 2). In both cases of MgO and CaO, the surface. basicities at basic strength of pK_α+ 12.2 correlated fairly well with the catalytic activities (Fig.7, 8). The catalytic actions of Sr0 and BaO were remarkably different from those of MgO and CaO, long induction period being observed for the former catalysts but not for the latter (Fig.1). Adsorption experiments with O₂, H₂0 and CO₂ showed that the induction period appears by the adsorption of CO, and disappears by its desorption (Fig.2, 3). X-ray analysis (Fig.4), differential thermal analysis and infrared spectra (Fig.5), together with the observed basicities (Fig.7, .8), revealed that the active sites are associated with unstable crystal structure of unhydrated oxides. Infrared spectra of deuterated OH remaining on CaO showed that, when diacetone alcohol was adsorbed (Fig.9), a OD band at 2760 cm^-1 did not shift and a new band at 3650 cm^-1 appeared. It was concluded from these results that the active centers of CaO and MgO for the decomposition reaction are O^-2 ion of unstable crystal structure, but not the hydroxyl group on the surface of the oxides.

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A study has been made of the effect of reduction of a Fe₂O₃ catalyst doubly-promoted with Al₂O₃ and K₂O on its ability to catalyze ethylbenzene dehydrogenation. Reducing gases used were hydrogen, CH₃OH, HCHO and CO. Reducing temperatures were ranged from 400 to 530°C. Activity tests were carried out at 460∼500°C in a flow system.
Reduction by those gases caused to increase in the catalytic activity and selectivity of the catalyst. The most effective reducing agent was found to be CO (Fig.6). X-Ray analysis showed that iron existed primarily as Fe₃O₄ and γ-Fe₂O₃ in the reduced catalysts while as α-Fe₂O₃ in an unreduced one.
The catalytic activities of the reduced catalysts for styrene formation paralleled approximately with the content of crystalline γ-Fe₂O₃ rather than with that of crystalline Fe₃O₄ (Fig.7).

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Photoconductivity and spectroscopic properties of poly-N-vinylcarbazole (containig or not containing a small amount of monomer) treated photochemically with polyhalogenated hydrocarbons have been investigated. The absorption spectra of dyes formed by the photoreaction varied with the monomer content in the polymer. The treated polymers exhibited a markedly sensitized photoconductivity both in the ultra-violet and the visible regions. Lower sensitivity was observed for a mixture of non-sensitized polymer and the photochemical products from monomer and polyhalide.
In the treated polymers, photocurrents in the visible region were larger when the negative electrode was illuminated than when the positive electrode was illuminated. However, those in the ultra-violet region were larger when the positive electrode was illuminated, as well as in the untreated polymers.

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Tantalum phosphate was prepared by adding a conc. hydrochloric acid solution of tantalum pentachloride to an aqueous solution of phosphoric acid. After the gelatinous precipitate was allowed to stand for 25 hr in contact with the solution, it was separated, washed and dried. The tantalum phosphate which possessed the composition TaO₂, (H₂PO₄)_0.88, 6H₂0 is amorphous and chemically stable.
From acid-base titration curves, it was found that tantalum phosphate is a typical weak acid cation exchanger having the capacity up to 3.8 meq/g in an alkaline solution. Affinities of tantalum phosphate to alkali metal ions, increased in order Li⁺<Na⁺<<K⁺<Rb⁺<Cs⁺ similar to that in organic cation exchangers or zirconium phosphate. The value of separation factor between Na⁺ and K⁺ was greater than that of strongly acid organic cation exchanger under the same condition.
A tentative explanation for the cation exchange mechanism of tantalum phosphate was based on acid-base titration curves and infra red spectra: hydrogen ion produced by the dissociation of dibasic phosphoric acid group is exchanged by alkali metal ions in a relatively low pH solution.

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Chlorine substitution products of trimeric phosphonitrilechloride with alkoxides of α, α'- xylenediol P₃N₃Cl_x (X= 3 or 6) and P3N5Cl(6_2y)(OCH₂6F14H₂O)y (Y=1-. '3) were synthesized in dioxane.
Water vapor was detected by gas chromatography and polymers like plastics were obtained when P3N3(OCH₂6FleCH₂OH)6 ortho [l], meta [2] and para [3] were heated in the temperature range from 25°C to 150°C.
Then, 4 mole of water per 1 mole of [3] was found by weight loss method. Further, upon heating at about 200°C, formaldehyde was detected by gas chromatography.
It was found that a part of ether bond, -Cl-12-0-CH₂, changed into methylen bond, -CH, -. On the other hand, ring cleavege reaction occurred and polymers were obtained when P3N4Cl4 (0M-12-C6114: CH₂0) and P9N3Cl2(OCH₂6114H₂0)2 were heated at about 200°C, but no polymer was obtained with P3N3(OCH₂4-14H₂0)3.
However, CO= bond absorption (IR) was observed in polymers, as a result of oxidation of a part of methylen bond. These polymers were stable toward water. Polymers having chlorine ion were unstable against dilute H₂SO₄, HNO₃ or NaOH solutions, but they were stable toward flame. The thermal degradation of the polymers were studied by gas chromatography. It was found from the data obtained from a number of xylene, a little water and formaldehyde were detected at 320°C.

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The effect of anions on the hydrolysis of aluminum ions has been studied to understand the roles of anions in the coagulation treatment of water with aluminum salts. A modified 8- quinolinolate extraction procedure reported earlier was used for the determination of mononuclear aluminum species in the presence of the polynuclear species. Anions can be classified according to their function into three groups: (1) those which have no effect on the hydrolysis of aluminum ions, (2) those which shift the optimum pH range for coagulation to the acid side, (3) those which shift it to the alkaline side. It is shown that anions of group 2 stabilize polynuclear aluminum species while anions of group 3 stabilize mononuclear aluminum species. Anions of group 2 exert a greater influence on the coagulation reaction. At high pH region (>7) anions have little effect on the hydrolysis equilibrium. The following solubility products were obtained:. precipitate Polynuclear hydroxo-aluminum sulfate Aluminum hydroxide solubility product [Al³⁺][OH^-]^2.68±0.04[S04^2-]^{0, 22±0.02}=10^-29.6±0.4(25°C, A=0) [Al³⁺][OH^-]³=10^-32.94±0.06(23±2°C, u=0.1) [Al(0H)4^-][H⁺]=10^-12.28±0.07(12 min.20°C. u=0.1)

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Studies were made to investigate fine dividing and structural change of Mg(OH)₂ crystal during grinding as an example of mechanochemical dehydration of hydrate crystals. The mortar of super hard alloy (WC-Co system) was especially used instead of agate mortar to avoid the reaction with silica for grinding.
In the case of grinding in air, Mg(OH)2 was rapidly converted into amorphous phase indicated. by X-ray and its weight increased considerably with time under the influence of H₂O and CO₂. The differential thermal analysis (DTA) curve of the ground material after 48 hours was quite similar to that of basic magnesium carbohate reported as 4 MgCO₃ Mg(OH)2.4 H₂O. In the case of grinding in the air removed H₂O and CO₂, Mg(OH)₂ also becam. e amorphous phase but no mechanochemical dehydration was found from the weight change. In the DTA curve of amorphous Mg(OH)2, a sharp characteristic exothermic peak appeared ' immediately after decomposition of the hydroxide due to recrystallization of MgO. In both cases, specific surface area of the ground materials approached to a maximum (60 m2/g) but gradually decreased after 24 hours by the formation of secondary particle.
In the case of grinding in vacuum (10-2 mmHg), MgO crystal was clearly found after 24 hours - as the results of mechanochemical dehydration with rapid conversion of the hydroxide into amorphous phase and the amount rised up to 55 % after 70 hours. With approaching to the limit of size reduction by grinding, the distorted and expanded crystal of MgO (lattice con: stant 4.2368A, crystallite size 100 A) should be mechanochemically equilibrated with amorphous Mg(OH)₂. In this case, the specific surface area became much larger than that of air grinding (200 m2/g after 70 hours). Surface activity of ground materials were discussed from the number of basic points.

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The effect af strontium fluoride on the synthetic process of zircon from silica and zirconia was investigated. Mixtures of various amount of silica, zirconia and strontium fluoride were heated in air and HF gas or SiF₄ gas atmosphere. The samples obtained were examined by X-ray diffraction method, X-ray diffraction at high temperature, infra-red spectroscopic method and differential thermal analytical method. The migration of various species were observed by tablet method.
The following results were obtained.
Strontium fluride accelerates the synthetic process of zircon from silica and zirconia. In this reaction process, strontium fluoride reacts with silica and zirconia to form amorphous intermediate compound containing these three component at about 1000°C. A weak and broad IR absorption band of this compound was recognized between 950 to 1100 cm^-1. As a result of formation of this intermediate product, the synthetic process of zircon was accelerated. Melting of this compound accelerates the reaction rate relating to the formation of zircon.

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Cobalt (II), nickel (II), copper (II), palladium (II), and platinum On complexes of N, N'- dimethy1-2, 6-pyridinedicarboxamide (abbreviated as mdpH₂) were prepared (Table 1) and studied on the structures by means of infrared, electronic, and pmr spectra and further magnetic susceptibilities were determined (Tables 2, 3, and 4, and Fig.5). The ligand mdpH₂ is poten- tially terdentate and coordinates through nitrogen atom of pyridine, and two oxygen or two nitrogen atoms of the amide group. The mode of coordination of the amide group is distin- guished by infrared spectra. The complexes prepared are classified as the following three types; A: MX2(mdpH₂) n H₂0 (M. Co, Ni, Cu and X, Cl, Br), M(mdpH₂)2(Cl04)2 2 H₂0 (M=Ni, Cu); B: M(NCS)2(mdpH₂)2 4 H₂0(M=Co, Ni), Co(mdpfl2)4(Cl04)2 10 H₂0; C: H[MCl(mdp)] (M. Pd, Pt). In the type A complexes, the ligand mdpH₂ is coordinated through the pyridine-N and the two amide-0 atoms. In the type B complexes, the ligand does not seem to be coordinated and it is only incorporated in the crystal lattice of the host metal salt, since any shift of the amide band and the band of the pyridine ring at 648 cm-1 from that of the free ligand is not observed. In the type C complexes, the amide groups are coordinated through deprotonated nitrogen, which is indicated by the two strong characteristic bands at ca.1600 and 1400 cm-', and the absence of v5_5. The structure of these complexes is square planar with the coordination of a chloride ion (Fig.6). No complex of this type was isolated except in the case of palladium and platinum.

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The kinetics of the substitution reactions of the iron(M)-complexes of N-(hydroxyethyl) ethylenediamine-N, NCY-triacetic acid (EDTA-OH), diethylenetriamine-N, N, N", N", N"-pentaacetic acid (DTPA) and glycoldiethyletherdiamine-N, N, NCY-tetraacetic acid (GEDTA) with indium (III) ion have been studied in the pH range 1.2-4.0 at 20°C and an ionic strength 0.1 adjusted with sodium perchlorate.
The reactions were followed spectrophotometrically by absorption at 260 mg bands in the spectra of the iron (111)-complexes. The initial rate of the forward reaction (R1) is expressed as. kf=k1i-k2[H⁺]+ks[H⁺]2 [FeX] for the EDTA-OH system, Rf=ki+k2[H⁺] [FeX] for the GEDTA system, and Rf=ki-Fk2/[1-1+]+ksiCH⁺i2 [FeH₂X]EIn3 for the DTPA system. The initial rate of the reverse reaction (R) is expressed as RT.={(ki-Ek4i[Ins+])+(k2+k5/Cins+1) EFI+J-F(ks+k5/Cin3) CH⁺Y}. [InX][Fes+] for the EDTA-OH system, Rr=(ki+k4/Cin3+J)+ (k2+k3[Ins+])/H+(k3-Fk6On3i)/CH⁺12. [InH₂X][Fe³⁺] for the DTPA system. Contribution of each reaction path to the over-all rate of the reaction was estimated. From the results, it was assumed that the forward reactions for the EDTA-OH and GEDTA systems proceeded through the dissociative paths in, which the rate-determining steps were the dissociative steps of the iron complexes and those for the DTPA system through the formation step of a binuclear intermediate complex. It was also assumed that the reverse reactions for the EDTA-OH and DTPA systems proceeded through the both paths. By measuring the absorbance at the equilibrium state, the logarithms of the concentration stability constants for the In 10-complexes of EDTA-OH and DTPA were found to be 20.2 and 29.6, respectively.

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A beautiful blue volcanic sublimate is found around the high temperature fumaroles (400°C) of Satsuma-iwei-jima Volcano. The identification of the mineral by the usual methods is difficult because it is amorphous (Fig.1) and is deposited as very thin films on alteration products. It is readily soluble in water giving a colloidal solution and can be extracted with organic solvents such as 1-butanol, ethyl methyl ketone, and ethyl acetate etc. The maximum absorption of the aqueous solution was found around 700 ma (Fig.2). The chemical properties agree well with those of synthetic molybdenum blue. From these facts, it is concluded that the blue sublimate is molybdenum blue. The 0/Mo atomic ratio of specimens purified by means of solvent extraction are within a range between 2.77 and 2.84 (synthetic: 2.84, 2.89).
Molybdenite is found inside the low temperature fumaroles (-200°C). It was identified by the X-ray diffractometry (Fig.3). The chemical analysis of a specimen shows Mo 52.7 %, S 35.3 %, and Si02 (impurity) 10.9 %.
Further, molybdenum contents of some volcanic rocks and volcanic gases in Japan were determined. The condensed water of the high temperature (>550°C) fumarolic gases of Satsuma-iwo-jima contains 0.3-7 mg Mo// (Table 5). On the other hand, molybdenum can not be detected in the gases of lower temperature fumaroles (Table 5) and in those of the other volcanoes (Table 6). Molybdenum contents of the volcanic rocks (17 samples) fall within a range between 0.5 and 3.4 pgig (Table 7).
From the above data and the results of the thermodynamic calculations (Table 9), the mechanisms for the formation of these minerals are presumed as follows: Molybdenum is transported by high temperature volcanic gas (>800°K) as its hydroxide or oxihalides to the oriffice of the fumaroles. Molybdeum blue is formed there by cooling and by increasing partial pressure of oxygen caused by mixing of air. Molybdenite is formed as a result of the reaction of hydrogen sulfide in the fumarolic gas with molybdenum blue which was dissolved and transported into the lower temperature fumaroles by rain water.

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A new method for the spectrophotometric determination of zirconium with methylxylenol blue (MXB) has been studied.
Zirconium produces a water-soluble red-brown complex with MXB and its aqueous solution has an absorption maximum at between 572 and 574 nm. The coloration is stable over the pH range from 1.5 to 1.9 and obeys Beer's law up to 1.4 μg. /ml of zirconium. The molar absorptivity of the complex and the sensitivity are 4.06 x 10⁴ and 0.0022 μg. Zr/cm², respectively, according to Sandell's expression. From these data, the following procedure is presented for the determination of zirconium.
The sample solution containing up to 35μg of zirconium is transferred to a 25 ml volumetric flask and pH is adjusted to 1.7 by the addition of 2.5 ml of buffer solution of sodium acetatehydrochloric acid. Then, 1 ml of 0.1% MXB solution is added. After making up the volume to 25 ml and allowing it to stand for 50 min., an absorbance is measured at 573 nm against a reagent blank.
The presence of twenty-two diverse ions such as alkali metals, alkaline earth metals, lead, zinc, chromium(III), manganese(II), cobalt, nickel and rare earth metals does not interfere with the determination. Arsenic (V), antimony (III), bismuth (III), hafnium, thorium and iron (III), however, interfere seriously.

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Vanadium (VI) reacts with Stilbazo to form a stable red colored complex at the pH between 6.2 and 6.7 in the presence of ascorbic acid.
The complex has absorption maximum at 510 mg and the color intensity is stable for 15 minutes, as far as ascorbic acid is present. The apparent molar absorptivity of this complex is found to be 5.4x10⁴; The concentration of vanadium corresponding to the absorbance(logIo/I)0.001 is 0.00093μg/cm³. By this investigation, it is concluded that 30μg of vanadiumin a 50ml of solutioncanbedeter- mininedby utilizing the formation of thiscomplex.
Aluminum, copper, iron(III), indium, titanium, zirconium, EDTA, citric acid and oxalic acid interfere seriousely with the determination.

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Dialkyl phthalates and dibutyl tin compounds are commonly used as plasticizers and stabilizers for PVC resin respectively.
The vapour phase photolysis of dialkyl phthalates in the presence of small amounts of HS were carried out to identify alkyl groups adjacent to the carboxyl, group. Then, phthalates (DBP, DOP) and dibutyl tin compounds (DBTM, DBTL) in PVC film were analyzed by solid state photolysis.
Super high pressure mercury arc was used as a light source, and the vopour phase photolysis of the phthalates were done with whole radiation of the arc, while the solid state photolysis were carried out with the ultraviolet rays transmitting through Toshiba UVD-25 filter (2500-4000 A). And the light was focussed on the sample (see Fig.1) and the irradiated area was as large as 80 mm2.
Hydrocarbons produced by photolysis were analyzed by gas chromatograph connected to the reaction system. The photolysis products from phthalates in the presence of small amounts of H2S showed a good correlation with the original alkyl groups adjacent to the carboxyl grgups as seen in Table 1.
DBP and DOP in PVC film produced 1-butene and 1-octene as main photolysis products through the molecular elimination reaction. (refer to formula 1) While n-butyl radical from the rupture of Sn-butyl bond was a main product of dibutyl tin compounds.
Small amounts of n-butane and 1-butene were also produced from DBP and dibutyl tin compounds as shown in Table 4. However, the ratios in peak area of n-butane to 1-butene were quite different from each other. Namely, in DBP, its ratio was about 0.16 and in dibutyl tin compounds, it is bigger than 1. The value between 0.16 and 1 showed the existence of both DBP and dibutyl tin compounds. The ratio in weight of DBTM to DBP in the sample film could easily be calculated from the next equation, y=3.8 x+0.16 where y is the ratio in peak area of n-butane to 1-butene produced and x is the ratio of DBTM to DBP added. DBTL could also be calculated using the similar equation.
DBTM and DBTL could not be recognized from their photolysis products as shown on a gas chromatogram. It results from the fact that the Sn-acid site bond are stable in this experi- mental condition.
Photolytic degradation combined to gas chromatographic analysis would be useful for the analysis of additives in polymers and the localization of these compounds can also be evaluated by this method.

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The reaction of diethyl malonate with formaldehyde in acetic acid in the presence of copper acetate gave a mixture of diethyl bishydroxymethylmalonate, diethyl acetoxymethylmalonate, and diethyl bisacetoxymethylmalonate contrary to the previous report that the product was diethyl hydroxymethylmalonate. Distillation of diethyl bishydroxymethylmalonate and diethyl acetoxymethylhydroxymethylmalonate in the presence of copper acetate afforded diethylmethylenemalonate in yields of 80%, and 70%, respectively. A reaction path has been proposed.

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A solution of e-caprolactam in aqueous hydrochloric acid was treated with sodium nitrite below 0C, and the resulting N-nitroso compound was decomposed at 60C. 'After conversion of the acids in the reaction mixture into the methyl esters, each component was separated by gas chromatography and identified by NMR and MS. As a result, the components were found' to be 5- and 6-chlorocaproic, 5-hexenoic, 5, 6-dichlorocaproic, 6-hydroxycaproic acids, capro-lactone, and a high boiling point mixture, the main component being Cl(CH₂)₅C00(CH₂)₅COOH. When hydrobromic acid was used in place of hydrochloric acid, the corresponding bromo compounds were obtained. The formation process and the yield of these compounds, and the effect of the acids were also examined.

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The r-radiation-induced addition reactions of several silanes, HSiCl₂C₆H₅(Ph), HSiCl₃(Cl), HSiCl₂CH₃(Me), HSiCl(CH₃)₂(Me₂) and HSi(C₂H₅)₅(Et₃) to polyfluorocycloalkenes, (CF₂), , CC₁=CH [n=2 Cl], n=3 [2] and (CF₂)CCl=CCl n=2 [3], n=3 [C] were studied.
While the 2, 2-dihydropolyhalocycloalkylsilanes were obtained together with the corresponding 1: 1 adducts in the addition of silanes to [1] or [2], the addition to [3] or [4] gave both the dehydrochlorinated 1: 1 adducts and the 1: 2 adducts. The apparent reactivities of the polyfluorocycloalkenes and the silanes were found to be in the following orders, respectively:
C1D>C2>C3D>C4J (Et3)>>(Me₂)>=(Me)> (Cl)>>(Ph)
The direction of attack of the silyl radical on the unsymmetrical cycloalkenes and the reaction mechanisms were discussed.

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A study was made on the stability of plasma arc which becomes a serious problem when acetylene is produced by plasma jet for industrial purpose.
The stability of arc is closely related to the voltage of arc, the shapes of anode, the con-sumption rate of cathode, the flow rate of working gas, etc. This relationship can be under-stood by comparing the characteristics of power source with that of arc.
The heat loss from anode is independent of the voltage of arc but increases in proportion to the current of arc. Accordingly, the ratio of heat loss to the total energy becomes lower as the scale of power source increases. Based on the results obtained both from 60 and 500 kW apparatus, it is expected that in a larger apparatus, e. g.4, 000 kW, it will be possible to bring down the heat loss to the value of several percent of the total energy consumed. When the effect of raising the preheating temperature is further taken into consideration, it is pre-sumed possible to obtain the electric power consumption value of 8.5-9 kWh/kg-C21-12.

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Isopropylation of toluene with isopropyl-alkylbenzenes in the presence of AlCl3 or Aid, -CI-13NO2 complex as catalysts was studied to compare the results with those of isopropylation with isopropyl bromide.
The para-isomer content in the transisopropylation products of isopropyl-m-xylene and toluene in the presence of AlC13 was found to be more than 50%, whereas the value 23-34% was found in the isopropylation with isopropyl bromide.
In the presence of A1C13-CH3NO2, the para-isomer content in the reaction products depended on the structure of hydrocarbon used as transalkylation reagent: p-diisopropylbenzene>l, 2- dimethy1-4-isopropylbenzene > 1, 3-dimethyl-5-isopropylbenzene cumene > 1, 4-dimethyl-2-iso-propylbenzene=isopropyl bromide.
Thus, it was found that the hydride transfer mechanism plays a role in the transisopropylation reactions.
Competitive isopropylation of benzene and toluene with isopropyl-m-xylene using Alcl3- CH3NO2 was carried out. The relative rate kT/kb=5.0 was obtained.

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The thermal decomposition reaction of basic cupric benzoate has been studied in toluene. The reaction products were tolyl benzoates, cresols, phenyl benzoate and phenol. Tolyl benzoates appear to be produced by the reaction of basic cupric benzoate with the solvent (toluene), while phenyl benzoate is formed as a result of the decomposition of basic cupric benzoate.
The total yield (I) of tolyl benzoates and cresols increased with increase in temperature from 3.9 mol% (220C) to 14.2 mol% (280C) in 3 hr reaction. As compared with the reaction of cupric benzoate, the combined yield (I1) of phenyl benzoate and phenol was very small and they were detected only at the temperature higher than 260C. When the reaction time was prolonged, both yields (I) and (II) increased.
The molar ratio of (I) to (II) was found to increase, when the reaction temperature and time were decreased. It is concluded that the reaction of basic cupric benzoate has characteristically high selectivity in the reaction with the solvent.

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When the reaction of C₆H₅l and Br₂ were carried out in fused salt of alkali metal chloride system containing CuCl, halogen interchange reaction was mainly observed to give C₆H₅Br, but in the presence of of similar fused salt containing ZnCl₂, large amounts of C₆H₅Cl were obtained together with C₆H₅Br. Analogous halogen interchange reaction of C₆H₅Br with C12 in the presece of such fused salts gave Ca-WI along with small amounts of C₆H₄H₂ and C₆H₅Brcl₂.
When Ca-Ur was chlorinated by Cl₂ in the presence of C₆H₅NO₂ as radical inhibitor at 350C, halogen interchange reaction and chlorination were not prohibited in the presence of ZnCl₂, in fused salts, but the both reactions were prohibited in the presence of the CuCl.
Consideration from these results, reaction temperature and conposition of fused salts dominate the products distributions.
It was supposed that in fused salt containing ZnCl₂, the halogen interchange reaction proceeded mainly through an ionic mechanism and the halogenation reaction could be explained as a Friedel-Crafts type reaction. In the case of CuCl, the reaction seemed to proceed through a radical mechanism.

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Substituent effects in 1, 3, 5-triazine derivatives were measured by alcoholysis of chlorotriazine derivatives and by proton NMR spectra. The effects of substituents on methoxyl "C-H coupling constants were also measured. Using the substituent constants in, the Hammett equation was satisfied in several cases. However, large 'deviations were observed in the cases of phenyl and phenoxy substituted triazines. It seems that deviations are caused by the diamagnetic anisotropy -effect of phenyl group and by the inaccuracy of the substituent constant of phenoxy group.

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In order to determine the carbon skeleton of long chain fatty alcohol or acid which included around 30 carbons, a fast method for a micro amount of sample was established.
Fatty alcohol or acid was converted into hydrocarbon by vapor-phase hydrogenation in the presence of palladium catalyst, and carbon chain length of the hydrocarbon was determined by gas chromatography.
The catalyst used was acid-washed chromosorb G coated with palladium chloride neutralized with sodium carbonate. Alcohol was supplied as it was and acid was supplied in the form of methyl ester.
The hydrocarbon having one carbon less than original fatty alcohol or acid was obtained as main product under the reaction temperature 400C, and it was found that about 100, ug sample was more than sufficient for this purpose.
This method was recommended to determine the carbon skeleton of long chain fatty alcohol or acid_in natural waxes.

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The following quaternary ammonium salts were synthesized. CH3 R -14 -C112- Cl CH3 -NO2R; dodecy1-(sampleNo.1); hexadecy1-(No.2); octadecy1(No.3). The suroce active properties of the sesamples such as suface tension, viscosity, electrolytic conductivity, solubilization emulsification and wetting as well as antibacterial and antmusty properties were studied to give the following results.
The results obtained were as follows.
(1)Surface activities of these samples follow according to the order of sample3>2>1.(2).
Studies on the surface tension and electrolyticconductivity as a function of concentration of the samples indicated that CMC of samples2 and 3 were O.017 and O.0109/100ml, respectively.
(3)Sample lwas excellent as the antibacterial and antifungous agents; sample 2 was less activite and sample 3 was the least active of the three.

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The fluorescence characteristics in DMF and fading behavior on polyamide film of 3-(4'- aminopheny1)-7-aminocoumarin and related compounds have been examined.
The intensity of fluorescence of trans-4, 4'-diaminostilbene C/D, 3-phenyl-7-aminocoumarin [3], 3-(4'-aminophenyl)-coumarin C5D, 3-(4'-aminophenyl)-7-aminocoumarin [7] and 3-(4'- aminopheny1)-4-methy1-7-aminocoumarin increased about 1.7, 0.86, 133, 1.9 and 1.6 times respectively, by acetylation. The photostability to fading decreases progressively in the following order: [7]>[5]>[9]>[3]>[1]. The photostability of the acetyl derivatives in [1] [7] and [9] was better than that of the amino derivatives, but the reverse was observed in [3] and [5]. The photofading rates of [5], [7] and [9] on the substrate decreased with their increasing concentration. In the cases of [3] and 3-(4'-acetylaminopheny1)-coumarin, however, the rate increased with increasing concentration. From these observations, together with previous results, a superimposed contribution of coumarin and trans-diaminostilbene was discussed for 3-(4'-aminophenyl)-7-aminocoumarin.

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Polymerization of methyl methacrylate was carried out in the presence of wool fiber and organic solvents without initiators.
It was found that the polymerization was affected by different kinds of solvents with various compositions and that carbon tetrachloride among organic solvents used accelerated remarkedly the polymerization. In the presence of a small amount of carbon tetrachloride the conversion increased up to a theoritical yield. In the presence of carbon tetrachloride the polymerization of methyl methacrylate proceeded mainly inside wool fiber and weight increase of wool fiber was very high and attained to, more than 3500% under the favorable condition, and graft efficiency was also high. Conversion was very low when one among wool, water and carbon tetrachloride was missing.
On the other hand, in the presence of other solvents such as acetone, benzene and methanol the conversion was lowered, and the polymerization outside wool fiber proceeded more easily than inside.
The rate of polymerization in the system of wool, water and carbon tetrachloride was proportional to the amount of wool fiber, but independence of the amounts of water and methyl metacrylate.

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In an attempt to deepen the color shade and to improve light-fastness of polymeric azo dyes (named, polymeric dye E), which were prepared by reactions of poly (ethyl vinyl malonate) [l] with aromatic diazonium salts, new polymeric azo dyes (named, polymeric dye A) containing anilide groups were synthesized by coupling of polymer [3] which was obtained by reaction of [l] with aniline, with aromatic diazonium salts in the presence of sodium acetate in dimethylformamide. It was presumed by infrared spectra that polymer C3D was consisted of a terpolymer of vinyl malonanilate, ethyl vinyl malonate and vinyl alcohol, and that polymeric dye A was consisted of a terpolymer of vinyl mesoxylanilate arylhydrazone, ethyl vinyl meso- xalate arylhydrazone and vinyl alcohol. Both the amounts of vinyl malonanilate part in [3] and of chromophore (ArNH-N.) in polymeric dye A were estimated by nitrogen analysis. The following polymeric dyes were prepared, namely, aryl group -=C6I-1 yellow; 4-CH3C6H4, yellow; 3-CH3C6H4, orange-yellow; 2-CH3C6H4, yellow; 2-CH3OC6F14, orange; 4-C106I-14, orange; 4- CHP-2-NO, C, H3, orange; 2-CHs-5-NO2C61-13, brown; 4-C1-13-2-NO2C6H8, orange; aCH io--7, dark-brown; 8-C10H7, brown.
All of these products were bathochromic as compared with polymeric dye E, but the lightfastness was scarcely improved.

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The solubilities in tetrahydrofuran-water mixtures have been determined iodometrically at 25C for iodates of Ca(II), Sran, Ba(II), Mn(II), Co(II), Cu(II), Zn(II), Cd(II), and Ag(I).
The logarithm of the solubility of a sparing soluble salt decreased almost linearly with the reciprocal of dielectric constant of the solvent, as expected from Born's equation. Factors which cause the deviations from the linearity were discussed.

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Hydrogenolysis of 6, 6-dichloro-1-methylbicyclo[3.1.0]hexane [1] catalyzed by Raney nickel in methanol solution has been studied under the ordinary pressure at 20C. Ring expansion took place during the reaction: 2-chloro-1-methylcyclohexene (3) was mainly obtained, together with small amount of 2-chloro-3-methoxy-3-methylcyclohexene [4] and 2-chloro-3-methoxy1--methylcyclohexene [5]. The ratio of [4] and [5] to [3] increased with increasing reaction temperature. exo-6-Chloro-1-methylbicyclo[3.1.0]hexane [2] was obtained in good yield without ring-expanded side product in the presence of ethylenediamine, whereas [2] was obtained with small amount of [3] in the presence of ethylamine and triethylenediamine. endoChloro isomer of [2] was not obtained under these conditions. These results were explained by two mechanisms, considering the adsorption strength of [I] and the effect of methyl group on the polarization of endo-chloro group.

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Association constant of vanadium (III) with sulfate ion was determined by measuring absorbance of vanadium OE in sulfuric or perchloric acid of various concentrations. Kvs04, - CVSO4+NEV3[SO42-1] at 25C has been found to be 29 through the photometric measurement at 400 nm under the following conditions: [V(III)]ltotai=8.2 mmol/l, [H+]=0.85 moIll, [H2SO4]=0.083, ---0.664molg and /i (ionic strength)=1.0, and to be 28 through the photometric measurement at 250 nm under the following conditions: EV(II)itotal=0.93, mmol/l, [H+]=0.92, [H2SO4]=0.0126 0.0766 mol/l and, u=1.0, . Moreover, the molecular extinction coefficients of V3+ and VSO4+ have been estimated in the regions of 230-280 nm and 350-700 nm.

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Samples are solidified with paraffin (mp 68-70C) to eliminate the effect of bubbles which decrease analytical precision. And the sulfur contents are analysed by the measurements of radiation intensity of sulfur.
Standard samples are prepared by the dissolution of TTD (Tetraethyl Thiuram Disulfide) in melted paraffin and then solidified by cooling. Linear calibration curve is given for sulfur. The relative standard deviation of measurements for ten samples is about 1% and the coefficient of correlation for chemical analysis is 0.999.
Solid samples are stable for repeated measurements.
Time required for the analysis of one sample is about 20 minutes.

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When the reaction 2(10)-pinene with methyl acryrate [2] or acrolein [3] was carried out in an autoclave at 170 to 180C, the corresponding 8, e-unsaturated compounds were obtained in 25% and 35% yields respectively.
The compounds, [4] and [7], were treated with lithium alminium hydride to give 2-pinene10-n-propanol[9].
Further, when the tosylate [11] of 9 was treated wsth lithium alminium hydride, 10-npropyl-2-pinene [12] was obtained.

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The reaction of 2-chlorocyclohexanones [A] (2-chlorocyclohexanone and 2-chloro-5-metylcyclohexanone) and 2-chloro-2-alkyl-cyclohexanones [B] (2-chloro-2-metylcyclohexanone, (-) 4-chloromenthone and (±)-1-chlorocarvomenthone) with anhydrous aluminium chloride at 120C under nitrogen has been studied. In the case of CAD, the most quantity of starting material was recovered and a trace amount of the corresponding dechlorinated cyclohexanone was obtained. On the other hand, [B] afforded the corresponding tx, fi-unsaturated ketone in over 60% yield.2, 4-Dichloromenthone afforded thymol under the. same reaction conditions. These results are interpreted as involving formation of the aluminium chloride complex. When pyridine was used instead of aluminium chloride, the corresponding x, 8-unsaturated IratnrIP wprp. nlurnvc nhtninpri from rAi And tm.

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Three bis(trifluoromethyl) dinitrobiphenyls were prepared by heating chloro- or iodo-nitrobenzotrifluorides with copper in DMF. Three bis (trifluoromethyl)-dinitrodiphenyl ethers were obtained by the reactions of chloronitrobenzotrifluorides with alkali Metal carbonates in aprotic solvents.
The dinitro compounds were reduced by tin and hydrochloric acid to give the corresponding diamino derivatives.
The diisocyanates, 3, 3'-(CF0)2-4, 4'-(NCO)2- and 2, 2'-(CF0)2-4, 4'-(NCO)2-biphenyl, 3, 3'-(CF3)2- 4, 4'-(NC0)2-, 2, 2-(CF3)2-4, 4'-(NCO)2- and 4, 4'-(CF0)2-2, 2'-(NCO)2-diphenyl ether, were obtained by the reactions of the amine derivatives with phosgen in glyme.

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The effects of stannic chloride and pyridine (0-0.2 mol/l) in the graft copolymerization of methyl acrylate onto ethylene-vinyl acetate copolymer initiated by benzoyl peroxide were studied. It was found that stannic chloride increased in the graft efficiency and in the graft yield, but pyridine decreased in the graft efficiency and the graft yield (Table 2). In the graft copolymerization with irradiation of ultraviolet (UV) light, stannic chloride increased in the graft efficiency but pyridine did not affect the graft efficiency (Table 3).

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