Barium titanate was successfully prepaxed threugh an aqueous reaction between Ba(OH)2and TiCl4. The dried materials had a cubic perovskite-type structure loosely crystallized. The heat-treatment promoted the crystallization and decrease in its lattice constant. The cubic phase was changed into the tetragonal one by firing at 1200 C. The firing at higher temperature enlarged the tetragonality and c/a became 1.0057 by firing at 1400 C. Although chemical analyses showed that it was almost stoichiometric, compound except that contained O.14wt%Na, it showed the existence of lattice defect because the density observed was considerably smaller than that of the calculated one. In comparison with barium titanate prepared by solid-state reaction between BaCO3 and TiO2, the barium titanate aqueously prepared had a low relative permittivity, a low Curie temperature, and broad peak width of dielectric anomaly at the transition point from ferroelectric to paraelectric phase. These characteristics were interpreted in terms of lattice defect, concentration of which was estimated from the difference between the observed density and the calculated one. The lattice defect seemed not to be due to a special ion deficiency, but to vacancies of all components of BaTiO3 with a vacancy ratio corresponding to the chemical formula.

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Absorption spectra of a merocyanine dye have been measured in aqueous solutions of anionic (NaC12S), cationic(C12TAC), and nonionic surfactant(C12(EO)7)under various conditions, and in the mixed solvents of water and organic solvents with different polarites. The spectrum of the merocyanine dye is highly sensitive to changes in the polarity of solvents aad, therefore, can be used as a sensitive probe toestimate. the polarity of solvent near the surface of surfactant micelle.
The transition energies, ET, and apparent dissociation constants, K, of the dye in micellar solutions were calculated from changes in the absorption maxima of the spectm. The difference between K and K (intrlnsic dissociation constant at the micell surface) has been interpreted in terms of the electrostatic potential ψ at the micelle surface where the dye is located. The values of ψ are -157, 33, and 12 mV for NaC12S, C12TAC, and C12(EO)7, respectively. The "effective" dielectric constants ε of the solvents near the micelle surfaces, estimated from the ε vs. ET plot(Fig.7), are 31, 72, and 78 for NaC12S, C12TAC, and C12(EO)7, respectively. These dielectric constants are in good agreement with the values expected from the Booth's theory of dielectric saturation. In addition, the mechanism of color changes ia micellar solutions has been discussed.

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The effects of the ultrasonication on the oxidation of Fe²⁺ and reduction of Ce⁴⁺ in O.8 N sulfuric acid soiutions were investigated. The ultrasonics of 400 kHz was found to be more effective than t, hat of 29 kHz. The rate of oxidation of Fe²⁺ increased with increasing its initial concentration up to 10^-3 mol/l and at the concentration reached the saturation value. The rate of reduction Ce⁴⁺ was independent of its initial concentration. An optimum power output was found in the oxidation of Fe²⁺, while in the reductien of Ce⁴⁺ the reaction rate was proportional to the power output. The ratio of the yield of Fe³⁺ to that ef Ce³⁺ at a given power output was 1.17. This value is much closer to the ratio of the G values of the same reactions with α -rays irradiation, G(Fe³⁺)/G(Ce³⁺)=1.43, than to that with γ -rays, G(Fe³⁺)/G(Ce⁴⁺)=6.33.

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Equivalent conductivity (A) of. EtOK in EtOH (Table 1) and second-order rate constant (k2)for the nucleophilic substitution of EtBr with EtOK in EtOH (Table 2) have been measured under pressure up to 1000 kg/cm2 at 45 C.
Volume change for the dissociation of EtOK in EtOH was found to be -39 ml/mol, calculated by using the observed pressure effect on A (Table 3, Fig.4). From the linear relationship between k2 and the degree of dissoeiation of EtOK (Fig.5, 6), the value of k1 at infinite dilutien for the nucleophilic substitution of EtBr with EtO- ion was estimated (Table 4). The volume of activation for this substitution reaction was determined to be -2.7 ml/mol (Fig.7).
The value of the volume of activation obtained agreed with that expected from the chargedispersed transition state proposed by Ingold.

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Cyclohexanone peroxide (CYP) which was regarded as one of the intermediates of the autoxldation of cyclohexane was synthesized, and the effects of atmospheres, solvents and fatty acids on the decomposition were studied.
The main decomposition product was cyclohexanone, and the decomposition rates were found to be proportional to the concentration of CYP(Figs.1 and 2).
The rates of the decomposition, k, were dependent on atmospheres and solvents, i. e., the rate constant decreased in the order of nitrogen> carbon monoxide> carbon dioxide> helium> hydrogen> air> oxygen and of acetic acid, cyclohexanone> cyclohexanol> chlorobenzene, 1dodecanol> n-dodecane> toluene, respectively(Table 1 and Figs.1 and 2). It should be noted that the yield of cyclohexanone was also dependenton the atmospheres.
A linear relationship exists between log k and the values of (D-1)/(2D+1)(D: dielectric constants of solvents), except for n-dodecane and acetic acid(Fig.3). The activation energy for the decomposition in cyclohexanol at 80-120 C was calculated as 13.8kcal per mole(Fig.4).
It was also found that the addition of the fatty acids caused the considerable acceleration of the decomposition and the rates were approximately proportional to the acidic strengths (Fig.5).
The activation energy for the decomposition in n-dodecane containing 3.8 mol% propionic acid at 80-120 was calculated as 18.1kcal per mol.

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Photochemical methylation of inorganic mercuric compounds such as mercuric chloride and mercuric acetate in aqueous acetic acid solutions has been studied and the mechanism of the reaction was discussed.
The rate of photochemical production of methylmercuric compound significantly differed between the two inorganic mercuric compounds when irradiated with a 20 W blacklight lamp, as shown in Fig.2. It was also found that the ultraviolet absorption curve of the mercuric acetate system extended to longer wavelengths as compared with that of the mercuric chloride system. Study of the wavelength dependence of the photochemical methylation by use of a monochrometer showed that a parallelism existed between the absorption wavelength and the effective wavelength for the photochemical reaction.
Gas chromatographic analyses demonstrated that the gas evolved during the photochemical reaction of the mercuric acetate system consisted mainly of carbon dioxide with minor amounts of methane and ethane. Therefore, photo-decarboxylation reaction, a cage reaction, is likely the main process.

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The mechanism of the reduction of nitric oxide with hydrogen over Fe2O3-γ -Al2O3 was investigated from the kinetic point of view. Two possible roles of hydrogen were tentatively considered. (1) Direct interaction with nitric oxide to form hydrogen-nitric oxide surface complex [Langmuir-Hinshelwood mechanism]. (2) Reducing action toward oxidized surface to complete catalytic sequence [redox mechanism]. The following experiments were carried out in order to elucidate the role of hydrogen.
The rate of reaction of nitric oxide with the reduced surface in the absence or presence of hydrogen was compared using pulse technique. As shown in Fig.1 and Table1, the rate at an extreme initial stage was unaffected by the atmosphere, i. e., helium or hydrogen.
The catalyst under working condition was found to be in oxidized state. The rate of reduction of the catalyst with hydrogen, 3x10-5mol/min g-cat, was almost the same as that of catalytic reduction of nitric oxide, 2x10-5 mol/min g-cat, obtained in a closed circulation system.
These findings clearly showed that the reaction was of redox type, which was well expressed by the rate equation proposed previously.

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Competitive oxidation of ¹³C-enriched ethylene and ethylene oxide over Ag-K2SO4-Al2O3catalyst was studied at 146-256 C in the range of O.1< Rp< 3 by a pulse technique, where Rp was the ratio of partial pressure of ethylene to that of ethylene oxide.
The isotope ratio of carbon in carbon dioxide produced was measured and fr (ratio of the amount of carbon dioxide formed from ethylene oxide to all amount of that produced) was determined by it. The value of fr increased with decreasing Rp, and Rp which gave fr> 0.5was easily attained in ethylene oxidation with integral reactor.
With increasing temperature, long contacting time and decreasing partial pressure of oxygen, fr increased and selectivity of ethylene oxidation decreased contrarily. From these results, the followings were confirmed: i) it was difficult to neglect the term of combustion of ethylene oxide in kinetics of ethylene oxidation, ii) the decrease in selectivity was attributable to reactivity of ethylene oxide.
A part of silver glycoxide, which remained on the catalyst surface during the competitive oxidation, was formed from ethylene directly. Based on this result and informations reported in our earlier papers, combustion intermediates of ethylene and ethylene oxide were estimated to be identical. lt was also comfirmed that the magnitude of fr was in the order of PdO> CuO> NiO> Au> Ag-wire> Ag-powder> Ag-K2SO4-powder and the catalyst had high selectivity which gave small value of fr.

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The hydrogenation of maleic anhydride over nickel-rhenium-kieselguhr catalysts (Re/Ni OO.15) was studied, in order to elucidate the correlation between the atomic ratio of Re to Ni an catalytic activity. The experiments were carried out for O.5 hrs at 250C, 50 kg/cm2 and for 2 hrs at 2500C, 120 kg/cm2. The concentration of catalyst was 5 wt%. The catalytic activity increased remarkably with increasing Re/Ni. The yield of tetrahydrofuran was 1.9wt % at Re/Ni=, 0, and 39, 9 wt% at Re/Ni=0, 15
It was confirmed by X-ray diffraction spectroscopy for these catalysts that rhenium entered into nickel crystal and formed the solid solution with it. The lattice distance of Ni(111) plane increased with increasing Re/Ni. A linear relationship was obtained between the catalytie activity, i. e., the yield of tetrahydrofuran, and the lattice diStance of Ni(111) plane.

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Correlatios between the dispefsion state of palladium on, zeolite Y and their catalytic activities were studied. Palladium catalysts on zeolite Y were prepared by calcinations of Pd(NH8)2+-NaY in a1r and subsequently reducing in hydrogon strea. An electron microscopy was used to determine the size distribution, the average diameter of palladium particles and the number of palladium particles per unit are. The fact was revealed that the size distribution of palladium particle was controlled by the calcination temperature. The catalytic activities of these catalysts for dehydrogenation of cyclohexane were reasonably interpreted in terms of the total surface area of palladium particles per unit area of zeolites. For oxidation of propylene In the presence of steam, however, this interpretation was not applicable. Some informations on the mechanism of agglomeration of palladium ions on zeolite Y were obtained by the use of differential thermal analysis and X-ray diffraction method.

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When a ZnO-resin layer coated on aluminum plate was dipped into NiC12 solution after light exposure, nickel deposited on the ZnO layer. The rate of metal deposition depenqgd on the eleciric cohductivity of Zno layer after the exposure. This phenomenon was applied to imaging. Effects df virious additives on the developing power of NiC12 solusion were. studyed, Activators or the additives which showed ti ositive effects (Table 1) were classified into two types. The activators of the first class, e. g., Na2S20s, . made the Ni dgpo. sition potential more noble as confirmed by the polarogram. Effects of the activators of the second. class, e. g., PdCl, were examined respect to their standard redox potentials and the work function of possibie deposite. The stafidard redox potential probably decreases the overvoltage fg. r Ni deposition on ZnO, since the activator in its reduced state is able to lower the overvoltage. The work function likely changes the surface potential barrier of ZnO through the electrical contact between ZnO and the deposit. Thus, the activation mechanism are different between the first and second types. Addiiion of both types of activators resulted in a additive accelera tion effect on the deVelepment.

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The present paper is concerned with a e!ectrophotogr-aph wbich is pteve. loped in NiCla solution through the cell reaction of (ZnO/NiCl2/Al). The maximum image density was obtained from the neutral electrolyte solution containing O.7 mol/1 NiCl, 0.7. -2, 8 mol/1 NH4Cl and O. Ol mol/l Na2S2O2. The deposition efficiency of nickel was low in acidic solutions. Nickel was deposited from its ammine complex ion which was stable at pH higher than 6. Thiosulfate ion was effective to accelerate the nickel deposition below the cortcentration of 10g mol/1, A direct electron transfer from Al electrode to Ni2 seemed to occur rapidly in the solution containing thiosulfate ion above 10-8 mol/1. The potential between the alminum plate 2-iffbr Tla-xef and a calomel electrode was influencedh. She Cl-m. concept r4Sign Schqrgsult fiihY rm66 ascribed to the increase Qf thg act3yllty of AIS: i ign, The potential mentioned above bec stable in the solution with lew free NiN concentration.

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The experimental research was conducted to elucidate the mechanism of metallic iron formation during the reaction, between l mo1/l aqueous solutions of FeC12 and NaOH through filter paper.
The state analysis of iron in the precipitate was carried out to determine the metallic iron, iron compounds or ferrous hydroxide which were produced and consumed in the course of reaction.
From the results obtained, the formation of metallic iron was found. to be expressed as follows.
FeC12+2NaOH---Fe(OH)2+2NaC1 (10)
3Fe(OH)2---Fe+2g-FeOOH+2H20 (2)
In the case of inactive goethite, free energy for the process of Eq. (2)was estimated as dG2298=-3.9kcal/mol.
From the pH-potential diagram for Fe-H20 system, the electrochemical steps to form metallic iron were expect as the following.
3Fe(OH)2---3HFeO2-+3H+ (14)
2H: FeO2---2a-FeOOH+2e (16)
HFeO2-+3H+ +2e---Fe+2H20 (17)
Then an over all process through the steps of(14), (16)and(17)resulted in the reaction of Eq. (2), which suggested a kind of disproportionate reaction of ferrous iron.

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The hydrogen reduction of AsC13 to metallic arsenic have been studied kinetically. Under a dynamic flow condition, AsCls was passed through the reactor, and the HCI gas, formed by the 2AsCls+3H2---1/2 Asl3+6HCl reaction, was determined by pH measurement after solidifying unreacted AsC13 in a trap cooled with solid CO2 and alcohol.
The rate of formation of arsenic was calculated from the amount of formed HCI gas within unit time.. The apparent activation energy of this reaction was found to be 21.7 kcal/mol at 546-672C, or 38.2 kcal/mol at 672-795C.
The percentage of conversion of AsC13 was calculated from thermodynamic equilibrium of the hydrogen reduction. The experimental results agreed approximately with the calculated values when the temperature of the reactor was kept at 850C and mole ratio of AsCl3 to H2 was 1: 3.
The relationship between the percentage of deposition of arsenic in the presence of H2 and the temperaturp of arsenic depositing part ef the reaetor was clarified thcoretically, as the temperature affected seriously on the grewth of crystalline arsenic.
In practice, it is preferable to keep the temperature of reaction part of the reactor at 850C, and mole ratio of AsCl3 to H2 was 1: 3.0-4.5 and the temperature of atsenic depositing part at 350-400C.

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The solubility of sodium chromate in sodium hydroxide solution at 15, 25, 35, and 45C, and in methano1 so1ution at 25 apd 35C, was determined in connection with the separation process of sodium chromate from thereaction product of chromite with o1tesodium salt.
In the Na2CrO4-NaOH-H20 system, it has been found that the solubility of sodium chromate decreased a1ong a curve with several infiections with the increase of sodium hydroxide concentration Solid phases were Na2CrO4-10 H20, Na2CrO4-4 H30, Na2CrO4-11/2H20, Na3CrO4, NaCrO5-13H2O, and etc., but Na2CrOao10 H20 and Na4CrO6-13 H20 disappeared above 25C and above 35C respectively.
In the Na2CrO4-NaOH-CH30H-H2O system, the solubility of sodium chromate in the methanol solution markedly decreased with the increase of methanol concentration in the methanol concentration above 50%.
In the presence of 10-20% of 80diumhydroxide, the solubility of sodium chromate decreased to the extent of 1/4-1/10 as compared with the value obtained in the absence of sodium hydroxide. Solid phases were Na2CrO4-4H2O, Na2CrO4-11/2 H2O, and Na2CrO4.

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For precise quantitative analysis of gas chromatography using TC detector, constant carrier gas flow rate should be maintained. But two effects had been known to disturb the flow rate and produced errots in quantitative analysis. First, the effeet of difference in viscosity between the sample zone and the pure carrier gas; second, the effect of the carrier gas flow rate increase accompanied by the sample peak elution, due to the appearance of sample vapor from the stationaly phase, at the outlet column. The second effect was discussed theoretically by assuming peak shape to be triangle.
To diminish these errors, two methods were tested and compared them with the usual method (A); the two methods were the method (B) in which gradiently decreasing stationaly phase column (3 mmφ X75 cm) was connected between main eolumn outlet and detector, and the method (C) in which long empty delay tube (3 mmφ X75cm) was connected between main column and detector.
When the sample size increased, the percentage of the main peak integral decreased as if it were effected by non-linearity of the detector, as shown in Fig. IN4. But, the percentage was less affected by the sample size in the methods (B) and (C) than that (A), except the case of n-octane which had very short retention time.
It was found that the decrease in the percentage, as the sample size increases, in the usual method (A) was mainly due to the second effect from theoretical calculation.
The theoretical calculation for some cases showed that the error due to the second effect might reached a few percent in routine analysis as shown in Table 1.

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Fluorescent X-ray spectrometry has been developed for the-rapid analysis of fishery preducts. Samples of fishery preducts were hemogenized with a Patter's homegenizer and dried under an infrared lamp in a draft-chamber. After pulverized by mixer-mill, a portion of sample was compressed at 15 t/cm2, and subjected to the determination of metal elements by fluorescent X-ray spectrometry, The intensity ratio of K. or L. line of the e!ements to be analyzed to scattered lines near the fluorescent line was used to compenzation of matrix effect of fluorescent X-ray. The standard deation of ana1ytical data for each: metals was within 5%. The recoveries of cadmium, lead, and chromium, obtained by adding 20 ptg/g of these nietals were 95.0-1O6.0%, 93.5-101.5%. and 96.0-1O5.0% respectively. Detection limit was O.2-O.5ptg/g (fresh sample, measurement time; 10-1OOsec). This value can be improved by the elongation of measurement time. The results obtained by the proposed method agreed almost with those obtained by atomic absorption analysis, while pretreatent procedureof this method was far more rapid and simple than any other conventional ones.

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Hexafluoropropene dimer, a mixture (5: 1) of (1) and (2), was allowed to react with methanol and acetaldehyde in the presence of benzoyl peroxide, and the structures of the resulting products were determined by means of the ¹H and ¹⁰F NMR spectra. By the reaction with methanol three polyfluoroalcohols, (3 a) (erythre), (3 b) (three) and (4) were formed in the ratio of 2: 2: 1, and these were separated by rneans of preparative gas chromatography. With acetaldehyde, three po1yfluoroketones(9 a)(erythro), (9 b)(threo)and(10)were formed in the ratio of 6: 2: 3.
3, 5-Dinitrobenzoate of(3 a)and 2, 4-dinitrophenylhydrazone of (9 a) were obtained as crystalline compounds.
The relationship between the conformation of these products and the NMR spectra data was discussed.

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The cationic telomerization of styrene with aliphatic carboxylic acid chlorides was carried out in methylene chloride in the presence of metal chlorides. The products were treated with sodium bicafbonate, and alkyl styryl ketones (3) were isolated by distillation. The structures of (3) were confirmed by IR, NMR, MS, and microanalyses.
The reaction conditions were examined in order to obtain the best conversion of styrene to iesults of the reasons with various kinds of acid ehlorides are summerized in Table 4. This suggests that, in the case of linear carboxylic acid chlorides, longer alkyl groups give better yields of (3). By comparison of the reactivity of isomeric acid chlorides, for instance C5 or C6 acid chlorides, it can be seen that a-alkyl groups bring about decreases in both the conbersion of styrene to (3) and the ratio of (3) to the total products, indicating the existence of a steric effect in the reaction.

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The pylolysis of cobalt phthalocyanine (Co-Pc)and nickel phthalocyanine(Ni-Pc)was studied at several temperatures up to 1000C under argon atmosphere.
The sublimation of Co-Pc and Ni-Pc began at 500C, and the weight loss by sublmiation was larger for the latter compared. to the former. Both Co-Pc and NPc decomposed at about 750C with libeation of nitrogen and the metal and changed to carbonaceus structure at 800C The decomposition of Co-Pc was more conspicuous than that of Ni-Pc.
It is infeed from these experiments that the phtha1ocyanine is transformed into carbon structure from b-type structure by way of a-type structure.

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In order to obtain information on the decomposition of hydrocarbons in a microwave plasma jet, the temperature of the microwave argon-hydrogen plasma jet and its temperature during propane decomposition were measured using the thermocouple and the spectroscopic method. Under the condition of, the argon flow rate of 19.1 l/min, the hydrogen flow rate of 0.63 l/min and the output of 470 W, the mean temperature which was measured by the thermocouple reached 15800K at the center of the plasma jet. lt was dependent on the output and the argon-hydrogen mixing ratio but scarcely on the operating gas flow rate. During propane decomposition, it dropped to lower than 13000K under the conditions used. The excitation temperature of ArI was above 10000K, which was much higher than the gas temperature, suggesting that the microwave argon-hydrogen plasma jet is not in thermal equilibrium. The products distribution in the decomposition of propane in the microwave plasma jet was compared with that in the thermal decomposition of propane and the decomposition scheme in the former was proposed.

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Relationship between structure and catalytic activity of V-Sn-W oxide cata1yst for butene oxidation to acetic acid has been investigated bmeans of differential thermal analysis, IR-spectrometry, X-ray diffractometry and chemical analysis.
An optimum calcination temperature of the catalyst is found to be between 450 and 500C, and the calcined catalyst was a mixture of each pure oxide. The contribution of SnO2 and WOs to the activity is ascribed to the promotion of reactivity of oxygen in V20s and to the increase of surface area of the catalyst, respectively. In the absence of oxygen, butene reduces only V2O5 in V-Sn-W oxide to form V4O9, and values of V5+/VTotal (VTotal=V5 V4+)ip the catalyst approach to 0.65 with, reaction time of the catalytic oxidation of butene. These results suggest that the activity of the catalyst is effectively increased when both V2O5and V40g coexist in the catalyst.
Acidity of the catalyst has also been determined and found to be correlated with the extent of V2O5 reduction in the catalysts. The acidity is certainly responsible for the catalytic activity.

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Oxidation of olefins and the possible reaction intermediates over V-Sn-W oxide catalyst have been studied in order to elucidate the reaction scheme of acetic acid formation from olefins.
The main products from dthylene, propylene, butene, isobutene and butadiene are those which ate anticipated from apparent scission of double bonds of the elefins; acetic acid is obtained in good Yiald from propylene and butenes while the main products from ethylene and butadiene are carbon 30xides. Addition of steam in the oxidation of 1-butene increases the conversion of butenes and selectivity to acetic acid although it retards allylic oxidation and decomposition of acetic acid. Acetaldehyde is usually found in the oxidation of propylene, and butenes, and is not detected in the xidationof acetone and ethylmeylketon, e which are formed from isopropylalcohol and sr-bqtylalcohol, the possible intermediate, by oxidative dehydrogenation.
These results suggest that acetic acid is neither formed via dxidative scissien of the double bond nor oxidative hydration through alcohol and ketone, but is mainly formed from acetaldehyde which in turn is produced through direct reaction of the active oxygen species with tfie Carbonium ion resulted from the olefin on acidic sites of the catalyst.

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As for a study on the treatment of asphalt with metal chloride, the influence of paraffinic compounds on the increase of asphaltene content was pursued.
n-Dodecane was made a selection as paraffinic compounds and reacted at temperature 180-200C 200C using aluminum chloride as catalyst. Heavy oils procuced were isolated to n-pentane solubles (A) and insolubles (B). Comparison of NMR spectra of B and asphaltene of straight asphalt showed that B was asphaltene-like matter.
A was fractionated to three eluates (n-pentane eluate, benzene eluate and chloroform-methanol eluate) by alumina column chromatography and investigated by means of NMR, GC-Mass spectrometry, elementary analysis, molecular weight and structural parameters. Being based on these fractions, the process of production of heavy oils from n-dodecane was surmissed as Fig.7.
From these results, it was suggested-that paraffinic compounds of asphalt were possible to contribute to the increase of asphaltene content.

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The catalytic cracking of butane over silica-alumina was investigated at atmospheric pressure and 450-600C in a tubular flow reactor. The overall rate of reaction obeyed first-order kinetics for butane and the rate constant was
kl, 1 = 1.16 x 106 exp(-29780/RT) ml/g-cat sec
A set of stoichiometric equations was derived on the basis of the carbonium ion mechanism. Some reactions of coke formation were also assumed from experimental results of distributions of gaseous products, as well as the anlalysis of coke formed in the catalytic crackings of butenes, propylene, and ethylene at the same conditions with. that of buitane cracking.
From these stoichiometric equations, rate equations were derived. The optimum values of the rate parameters were calcdlated from the distribution of gaseous products in. butane cracking by the Marquardt method with an adjustable step size. These values wel1 explained the experimental results.

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Disproportionation reaction of toluene, cumene and n-propylbenzene on synthetic HX and HY zeolite catalysts was studied using a flow system over the temperature range from 200 to 500 C under atmospheric pressure.
The H-type zeolite catalysts have shown an induction period for the activation of catalyst, which was influenced by the reaction temperature (Tables 3 and 4, Fig.3) as well as by the structure of alkyl substituents on the benzene ring but not by LHSV (Table 2, Figs.1 and 2). The induction period was concluded to result from the formation process of disproportionation intermediates. Since the relative rate of disproportionation reaction of substituted benzenes was the following order, isopropy1 &gt; n-propy1 &raquo; methyl, the reactivity of alkylbenzenes was much affected by the stability of carbonium ion intermediates.
It was clarified that the disproportipnation of alkylbenzenes on the zeolite catalysts at relatively higher temperature proceeded not by the scission of alkylsubstituent cation from benzene ring but by the attack of &alpha; -phenylalkyl carbonium ion on the polarized part of another alkylbenzene, that is, via 1, 1-diphenylalkyl carbonium ion intermediate (Fig.4), as proposed by Pines and Streitwieser in the reaction at lower temperatures.

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The dark and/or photoconductivities of 16 substituted phenazines having methoxy, hydroxy, chloro, nitro, amino or t-butyl group at 1-, 2-, 1, 6- or 2, 7-positions of the phenazine ring have been investigated by using the "surface-type" and/or "sandwich-type", cells. As shown in Table 1, the resistivities at 20 C (p20) were higher than 10 14 ohm-cm. The energy. gaps ( &epsilon; )of the dark conductivities in the range from 2.0 to 2.3 eV were independent of the kinds and the positions of the substituents, although the longest wavelength band in the visible absorption spectra of the evaporated films changed With them. The photocurrent became larger by ihtroducing the substituents at 1, 6-pbsitions of the phenazine ring, the photocurrents of the 1, 6-disubstituted phenazines were 10 - 10 3 times larger than those of the other substituted phenazines, as shown in Table 4. When the substituent at 1, 6-positions was hydroxy or amino group, however, the photocurrents were not detected. The photocurrents of all phenazines decreased in oxygen, although that of anthracene increased. No correlation between the photoconductivity and fluorescence was observed. Furthermore, the spectral properties of the 1, 6-disubstituted phenazines were compared with those of the 2, 7-disubstituted phenazines, it was deduced that the t-butyl groups at 1, 6-positions adjacent to the lone-pair electrons of the nitrogen atoms of the phenazine ring interfered with the protonation of the lone-pair electrons with acetic acid.

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Eight methoxynitrophenazines (Table 1) having a methoxy group at 1 or 2 position and a nitro group at 6-, 7-, 8- or 9-position of the phenazine ring ((l.6), (1.7), (1.8), (l.9), (2.6), (2.7), (2.8) and (2.9)) are prepared and their photocurrents are measured by illuminating the "surface-type" cell with a white light from a W-lamp under a nitrogen atmosphere at room temperature, The position of the methoxy and nitro groups is determined by measuring the IR, UV, NMR and Mass spectra of the methoxynitrophenazines and by considering their methods of formation. The photocurrents of 1-nitrophenazine (6) and 2-nitrophenazine (7)are compared with those of methoxynitrophenazines. The photocurrent (ip) increases with increase of the light intensity (I), thus satisfying log ip &prop; n log I. The n values are in the range of 0.5 to 1.0, as shown in Table 2. The magnitude of the photocurrents decreases by the order: (7) &gt; (1.7) &asymp; (2.8) &gt; (1.8) &asymp; (2.7) &gt; (1.6) &gt; (6) &gt; (1.9), (2.6), (2.9). The compounds of (1.9), (2, 6) and (2, 9) show no observable photocurrent. When the nitro group is located at &beta; -position of the phenazine ring, the photocurrent becomes larger owing to the electron-withdrawing property of the nitro group. On the other hand, the photocurrents of phenazines with the nitro group at &alpha; -position are extremely small. The photoconductivities of methoxynitrophenazines become lower in an atmosphere of air.

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The photocurrents of the substituted anthracenes, 1, 5-diacetylanthracene (2), 1-acetylanthracene (3), 9-acetylanthracene (4), 1, 5-dichloroanthracene(5), 1, 5-diethylanthracene (6), 1, 5-dimethoxyanthracene (7), 9-cyanoanthracene (8) and anthracene (1), were measured by using their "surface-type" cells in nitrogen. The compounds of (1), (5), (6), (7)and (8) showed the photocurrent spectra which corresponded to the absorption spectra of their evaporated films (Fig.1). In the cases of (2) and (3), however, the anomalous photocurrent apPeared in the threshold region of their absorption spectra. Especially, the anomalous photocurrent of (2) became larger (Fig.2). The appearance of the anomalous photocurrent was characteristic of anthracenes having the acetyl group at 1- and/or 5-position. The magnitude of the photocurrents of the 1, 5-disubstituted anthracenes was similar to that of (1). On the other hand, the photocurrents of the monosubstituted anthracenes were smaller than that of (1). Among the monosubstituted anthracenes, the compound (4) showed no photocurrent under the same conditions. Contrary to the results obtained in the cases of phenazines, the photoconductivities of the anthracene derivatives became better in air.

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Spontaneous polymerization was found to occur by heating 2-vinylpyridine (2-VP) at 50 C in the presence of poly (vinyl chloride) (PVC), and the mechanism of polymerization was investigated.
In this system, the polymerization was found to proceed according not to the so called "matrix" but to the radical mechanism initiated by peroxides in PVC. The rate equation obtained was Rp = k[2-VP] 0.6-0.8 [PVC]0.4-2.0, and differed from the conventional radical polymerization.
A kind of interaction between 2-VP and PVC was confirmed to exist from the results of copolymerization and homopolymerization studies in the presence of PVC, and more detailed analysis of the kinetic data.

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The radical species trapped in irradiated poly (vinylidene fluoride)(PVdF) were assigned by electron spin resonance(ESR). The films of PVdF were drawn by 400% at 45 C. The samples thus obtained had a crystal structure of the zigzag chain conformation, where the chains were aligned parallel to the drawing direction (Fig.2). The samples, which were sealed in ESR sample tube and evacuated, were irradiated with &gamma; -rays from Co-60 at 77 K. The ESR spectra were recorded at 77 K and room temperature. The ESR spectra obtained at 77 K after irradiation showed broad an, d diffuse pattern with several shoulders (Fig.10). After annealing the sample at room temperature for an hour, a resoluble pattern (Fig.3 and 4) consisting of a double sextet appeared. The radical responsible for the double sextet was assigned to the alkyl-type radical, -CH2-CF-CH2-, and the conformation was presumed (Fig.6). Upon annealing at 195 K after irradiation, the chain scission radical, -CH2CF2, was observed as a small portion of the trapped radicals.
When the sample irradiated at 77 K was stored for a long time at room temperature or annealed for a short time at high temperature in vacuo, the siglet spectrum remained (Fig.9). The singlet was stable in vacuo and was assigned to polyenyl radicals, -(CF=CH)-CH-.
The alkyl-type radicals and polyenyl radical easily reacted with oxygen to form peroxy radicals. Oxygen, molecules diffused into the crystalline regions and reacted with the trapped radicals. Therefore, when irradiation was performed in air at low does rate, these radicals were converted into peroxy radicals, which hindered the crossliaking reaction. The stability of the alkyl-type radicals and the reactivity with oxygen had relations to crosslinking and degradation.

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Poly (methylacrylate) (PMA) prepared by radical (PMA-R) or anionic (PMA-A) polymerization of methylaerylate was allowed to react with polyethylenepolyamine to obtain water soluble polymers. By means of foam treatment using these water soluble polymers, the removal effect of heavy metals was investigated.
Polyethylenepolyamines used were ethylenediamine (EDA), diethylenetriamine and tetraethylenepentamine and the best removal effect was obtained When PMA-EDA reaction product was used. More than 99.9% of cadmium was removed when the reaction product of PMA-A, containing EDA in the ratio of 1: 10 mol in dimethylformamide at 130 C for 7 hours, was used. The most effective result, was obtained in the pH range from 7.0 to 9.0 and the suitable concentration of PMA-EDA reaction product was 160-250 ppm at pH 7. More than 90% of lead, copper or zinc was removed.

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Infrared spectra of deuterated crystalline modifications of cellulose were compared mutually.
In our previous works, it was considered that chain conformation in cellulose I family modifications (I, III_I and IV_I) was "bent", form, and that in cellulose II family (II, III_II and IV_II) was "bent-twisted" form. While, there was similarity in unit cell dimentions, with respect to the state of chain packing, among cellulose I, IV_I and IV_II, and cellulose II, III_Iand III_II.
Based on the similarity and the difference among their infrared spectra, the relationships between absorption band and crystalline structure were investigated. The results are summarized in Table 1. Crista11ine modifications in cellulose I and II family showed one and two OH stretching band, respectively, fitted to O 3 &rarr; O 5', intramolecular hydrogen bonds. This fact corresponded with that the chain conformation of "bent" and "bent-twisted" form had one and two kinds of O 3 &rarr; O 5', respectively.
It was considered that cellulose I and IV_I had O 6 - O5 O1 intermolecular hydrogen bonds between corner and center chain in unit cell, and this fact caused the week C1 groups stretching band at 859 cm-1, the strong CH2 bending band at 1430 cm-1 and the shift to the lower wave number side of O 3 &rarr; O 5' OH stretching band, on I and IV_I.
Wave numbers of O 3 &rarr; O 5' OD stretching band on cellulose I and II family were different between them and the same in each.

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6-Nylon fibres were metallated with Li, Na or K metboxide in methanol and the metallated fibres were allowed to graft-copolymerize with acrylonitrile(AN) in tetrahydrofuran(THF) or dimethyl sulfoxide(DMSO) by the anionic mechanism.
Concerining the metallation of the nylon, effects of reaction time, methoxide concentration and reaction temperature upon the alkali metal combination onto the nylon were investigated. The equilibrium amounts of alkali metals combined increased linearly with methoxide concentrations and in the order of Li &gt; Na &gt; K. The metallation reactions were endothermic and the reaction heats were in the order of Li &gt; Na &gt; K. The apparent activation energies obtained were in the order of Li &lt; Na &lt; K.
Concerning the graft-polymerization of AN onto the metallated nylons, effects of AN concentration, reaction time, alkali metal combination and reaction temperature upon the graftings were investigated in either medium of THF-AN or DMSO-AN. The graftings increased linearly with AN concentration in THF-AN medium, while they gave a maximum at AN 40-60 vol % in DMSO-AN medium. Apparent activation energies obtained were in the order of Li &lt; Na &lt; K in THF-AN medium, while in the order of Li &gt; Na K O in DMSO-AN medium.
The number average molecular weights ( Mn ) of the graft chains were measured, which were formed in DMSO-AN and separated after hydrolysis of the copolymers with 6 N HCI. From the calculated molecular weights and the measured ones, the following results were obtained: in the case of Li, initiator efficiencies were O.7-l.5 and Mn of the graft chains were 7000-llOOO, while in the case of Na or K, initiator efficiencies were 3-5 and Mn of the graft chains 2000-4000, provided that the initiator efficiency was the ratio of the calculated number average molecular weight to the measured one.

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Specific surface area of active carbons prepared from poly(vinyl chloride) (PVC), urea resin, melamine resin, furfuryl alcohol resin and phenol furfural resin was measured. Experimental conditions were as follows: Carbonization temperature: 600-700 C, activation temperature: 750-lOOO C and activation time: O.3-18 hours.
Reaction rate of carbon with steam was zero-order with respect to the carbon for wood charcoal, but it was first-order for carbonized materials from plastics (Fig.1, 2)
Active carbon could not be prepared from PVC carbon carbonized in a stream of nitrogen (Fig.5). Active carbons with specific surface area as high as 2000 m2/g were successfully prepared from PVC powder containing 5 wt % of zinc stearate (Fig.6). The maximum value of specific surface area of active carbon from PVC pipe was 570 m2/g (Fig.7).
Active carbons with specific surface area as high as 1300, 800, and 2200 m2/g were prepared from urea resin, me1amine resin and furan resin, respectively (Fig.8, 9).

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The rates of sorption of p-chloreaniline (PCA) onto sulfonic acid type ion-exchange resin were investigated in several organic solvents (methanol, ethanol, 1-propanol, 1-butanol, DMF, DMSO, 1, 2-dichloroethane, ethyl acetate and benzene). The rates of PCA sorption were found to be controlled by particle diffusion in the organic solvents used. The diffusion coefficient (D) of particle diffusion was dependent on the solvents used and resin structure O.57 10 -8 - 83 10 -8 cm2, min-1 for Dowex 50 WX8 and O.27 10 -6 - 3.76 10 -6 cm2, min-1 for Amberlyst 15.
The effect of solvents on the D of PCA in the resin particle of two resins was discussed in terms of solvent uptake of the resins and viscosity of the solvents.

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Poly(N^ε -benzyloxycarbonyl, N^ε -p-methylbenzyl-L-lysine) (1) and poly(N^δ -benzyloxycarbonyl, N^δ - p-methylbenzyl-L-ornithine) (2) were prepared by the N-carboxyanhydride method. The protected polymers were converted into poly(N^ε -p-methylbenzyl-L-lysine) (3) and poly(N^ε -p-methylbenzyl-L-ornithine) (4) through debenzyloxycarbonylation with hydrogen bromide. The conformation of the four polypeptides was studied by means of infrared (IR) spectra, X-ray photographs, optical rotatory dispersions (ORD), and circular dichroisms (CD). The presence of the α -helical conformation in (1) and (2) was confirmed by X-ray photographs and by their IR spectra. The results of the ORD and the CD measurements suggested that these protected polymers had a right-handed α -helix structure in chloroform and in 2-chloroethan. The breakdown of the helical conformation for (1) was found to occur at 7% dichloroacetic acid, and for (2) at 8% dichloroacetic acid in a chloroform-dichloroacetic acid mixture. In the pH range 3.0-7. O i. q., mixtures of water and alcohols (1: 1), the deprotected polymers had a random coil structure. However, when pH was increased to more than 7.0, the spectra gradually changed into α -helix structure. These polymers predominantly took the α -helix structure at about pH 7.5.

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The self-condensation of cyclohexanone (1) and its methyl substituted derivatives was investigated under pressure of 20-50 kbar and temperature of 160-300 C without solvent and catalyst. It was found that (1) yielded 2-cyclohexenylcyclohexanone (2), 2-cyclohexylidenecyclohexanone (3), 2, 6-dicyclohexenylcyclohexanone (4) and dodecahydrotriphenylene (5). (5) was a main product at high pressure and high temperature. While 2, 2'-methyl-(2methylcyclohexenyl)-cyclohexanone (7) was obtained from 2-methylcyclohexanone (6). The reactivity of 2, 6-dimethylcy clohexanone was also examined and no product was obtained under pressure of 20-50 kbar and below the temperature of 250 C.
This condensation seems to occur in liquid state and to proceed through a series of aldol condensation followed by dehydrations. This scheme was confirmed from pressure effects, but the mechanism of this condensation cannot be explained merely by pressure dependence of auto-protolysis.

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Ethyl methyl ketone flowing through a layer of neutral alumina undergoes self-condensation on the methyl group to 5-methyl-4-hepten-3-ope at room temperature. By using the same method, acetophenone forms dypnone, and diethyl ketone forms 4-methyl-5-ethyl-4-hepten-3one, but self-condensation of propiophenone does not proceed (Table 1). In the same manner, ethyl methyl ketone, acetophenone and diethyl ketone condense with benzaldehyde to form benzalmethy1 ethyl ketone, chalcone and 2-methyl-1-phenyl-1-penten-3-one, respectively. Propiophenone does riot condense with benzaldehyde (Table 2). As mentioned above, aluminacatalyzed aldol condensation occurs by attack of the carbonyl group on the less hindered α carbon atom. According to Abbott's and Harries's reports, ethyl methyl ketone undergoes aldol condensation on the ethyl group with acid catalysts. On the other hand, the same ketone undergoes aldol condensation on the methyl group with basic catalysts. From these results described above, it is concluded that the, active site of alumina for the aldol condensation is the base site.

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Several experimental results for the liquid penetration through filter paper may be classified into the ideal and non-ideal types. The square law or the parabolic flow law is strictly applicable on the ideal type. Some of the non-ideal types can be brought into the ideal one by correcting only the penetrating distance by an amount of h o estimated according to the authors' method. The validity of above assumption was confirmed from the linear relation between positions of the origin of measurement and correcting values (h0) on the penetrating distance.

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The reaction of boron trifluoride-methanol reagent with trans-3-decenoic acid was studied.
Reaction products were isolated by means of distillation, column and gas chromatography. Their structures were determined by IR, NMR, MS spectra and chemical analyses.
In this experiment, the following compounds have been identified: methyl trans-4-decenoate (1), methyl trans-3-decenoate (2), methyl 4-methoxydecanoate (4), methyl 5-methoxydecanoate (5), 4-decanolide (6) and 5-decanolide (7).

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The reaction of several dithiocarboxylic acids with 2, 4-dinitrochlorobenzene was investigated. The dithio acids with α -hydrogen reacted with 2, 4-dinitrochlorobenzene to give 2, 2', 4, 4'tetranitrodiphenyl sulfide. Whereas, the dithiocarboxylic acids without α -hydrogen on carbon atom gave 2, '2', 4, 4'-tetranitrodiphenyl disulfide, and those without α -hydrogen on nitrogen atom gave dinitrophenyl ester of the dithiocarboxylic acids.

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Two new heterocyclic compounds, 3-ethoxycarbonyl-5-azaacenaphthene-1, 4(5H)-dione-1ethylene acetal (1) and 3-ethoxycarbonyl-5-azaacenaphthene-1, 4(5H)-dione-1-ethylene dithioacetal (2), were synthesiized from 4-nitroindan-1, 3-dione via 4-ethoxycarbonylacetamidoindan1, 3-dione-1-ethylene acetal (5) and -1-ethylene dithioacetal (7), respectively.

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Six tetrafluoroisoindolinone pigments (4) (No.1-6) were prepared by condensation of tetrafluorophthalimide (1) and aromatic diamines (F3). The properties of these fluorinated pigments (4) were compared with those of corresponding tetrachloroisoindolinones (5). In general, the colors of the fluorinated pigments were more hypsochromic and the fastness to light and solvents was inferior to these of the chlorinated pigments.

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The transimination, XCH=N-CH2Y(I) - XCH2-N=CHY(II), was investigated polarographically. In a weak alkaline solution, the rearrangement from I (two one-electron reduction waves) to II (one two-electron reduction wave) was found in the reaction of N-methyl4-formylpyridinium iodide with glycine. On the other hand, the reaction of N-methyl-4aminomethylpyridinium perchlorate with glyoxalic acid resulted only in the formation of II. In connection with transimination, two oxidation waves appeared. The negative one, having a corresponding AC polarographic wave, seems to correpond to the oxidation of the I -carbanion, and the other to the oxidation of II.

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