Activity coefficients of HCl in water-acetone mixture and thermodynamic quantities for the transfer of HCl from water to the mixed solvents at 25°C were determined by EMF measurements of the cell: H1⁺ glass electrode HCl in mixed solvent AgCl-Ag. These thermodynamic quantities were tentatively divided into the contribution of solvation layer consisting of solvent molecules reoriented to ions and that of the bulk region arising from the difference in dielectric constants, and the quantities of the latter were estimated from the electrostatic model by taking the value of 0.41 nm for the radius of solvated ion. The contribution of solvation layer to entropies and enthalpies of the transfer of HC1 from water to water-acetone mixture decreases with an increase in the concentration of acetone, but the contribution of solvation layer to free energies of transfer gradually increases, because of the quantities of the former being always larger than those of the latter. The thermodynamic quantities were discussed in terms of ion-solvent interactions as well as the structual changes of the solvents.

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Monodispersed microspheres(MS) of poly (methyl methacrylate) were prepared in cyclohexane with the dispersion polymerization method. The copolymer of dodecyl methacrylate and glycidyl methacrylate was used as a dispersant. The dispersion of purified MS in cyclohexane was very stable. It is considered that esterified glycidyl group of the dispersant is chemically bound to MS and its poly- (dodecyl methacrylate) moiety forms an adsorbed layer on MS. Potential energy between two MS particles was calculated by the Ottewill-Walker and Vold equations in order to estimate the effect of the adsorbed layer on the stability of the dispersion. V_max =10 k T was obtained froin the potential energy curve. The result was consi stent with the observation of the dispersion stability.
The adsorption of a disperse dy e, C. I. Disperse Yellow 7, and water-soluble dyes, C. I. Acid Blue 138 and C. I. Basic Violet 3, on the polymer MS was studied. The adsorption isotherm of the disperse dye. was divided into the reversible and irreversible adsorption isotherms. The isotherm was linear and the adsorption rate was fast in the former. On the other hand, the latter showed the Langmuir type and a slow rate. Water-soluble dyes were solubilized into water-solubilizing AOT [sodium 1, 2-bis(2-ethylhexyloxycarbonyl)ethanesulfonate] solutions in cyclohexane. The adsorption of the secondarily solubilized dyes was studied. Adsorptio n isotherms of 'both dyes were the Langmuirian. The amount of the adsorption decreased markedly with an increase of the amount of water salubilized in the AOT solution.

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Tris(oxalato)cobaltate(III) ion [Co(C₂O₄)₃]^3- decomposes thermally with the intramolecular electron-transfer reaction in acidic solutions of aqueous mixtures of ethanol, and produces the radical of C₂O₄- or CO₂- which is capable of inducing the reduction of tetranitromethane C(NO₂)₄ to trinitromethanide ion C(NO₂)₃- Both the rates of decomposition of tris (oxalato)cobaltate(M) ion and of formation of C(NO₂)₃- are accelerated with an increase in acidity and/or in an amount of ethanol in the binary solvent-systems. Kinetic studies are made under various conditions and the reaction mechanisms are discussed based on the empirical results obtained. All the experiments were carried out in a closed reaction-vessel to keep the concentration of tetranitromethane constant; because the concentration of tetranitromethane decreased by vaporization unless the vessel was covered.

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Treatment of Pt(O₂) (PPh₃), with hydrogen in benzene at 65°C gave a dark brown amorphous complex which exhibited a catalytic activity for hydrogenation of olefins. The complex was identified to be PtO (PPh₃) by means of elemental analysis, molecular weight determination, IR, mass, and ESCA spectra. The hydrogenation of styrene was of first order to the hydrogen pressure and to the Pt concentration and of zero order to the styrene concentration. The activation energy is 53.5 kJ ⋅mol^-11-Pentene has been found to undergo hydrogenation and isomerization with solvent effects: the hydrogenation rate decreases in the order THF>MeOH>MEK>toluene>CH₃CN and the selectivity for hydrogenation is THF>MEK>MeOH>toluene>CH₈CN. The addition of PPh₃ inhibited the hydrogenation bu t increased the selectivity for hydrogenation. The complex has no selectivity for olefin formation in the hydrogenation of conjugated dienes and acetylenes.

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(E)- and (Z) -3, 7-dimethy1-2, 6-octadien-l-ol ((E)- and (Z) -[1]) and 3, 7-dimethy1-6octen-1-ol were preferentially obtained respectively by hydrogenations of citral [2], which is a mixture of (E)- and (Z) -3, 7-dimethy1-2, 6-octadienal, and of citronellal [3]in the presence of the CoCl₂-modified Raney Co catalyst at 30-65°C under atmospheric pressure. When the hydrogenation of [2] was stopped at the consumption of 0.3 mol of hydrogen, more than 92% of the product was a mixture of (E)- and (Z) -[1]. The best selection (99%)was observed when 1-propanol was used as a solvent. The rates of hydrogenations of [2]and [3] were dependent on the sort of solvent. The effect of the solvent on the efficiency of hydrogenation rate was observed in the following order; methanol>ethanol>1-propanol>2-propanol.

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Dehydration of 2-propanol was investigated over various heteropolyacids having different central (hetero) and poly atoms and their salts. The order of the catalytic activity for acid form was as follows;
In the case of salts, those of alkali metals such as Cs, Na were more active than Cu and Ni salts.
It was demonstrated that deactivation took place when the heteropolyacid catalyst contained Mo or V, while no such deactivation was observed for H₃PW₁₂O₄₀ and H₄SiW₁₂O₄₀, which showed rather high activities. An oxygen treatment of the deactivated H₃PMo₁₂O₄₀ made the catalyst to regain the initial activity and the oxidized state, indicating that the deactivation was caused by the reduction. The substitution of H+ in HaPW₁₂O₄₀ with Na + resulted a decrease not only in the acid amount but also in the acid strength. The activity for the dehydration of 2-propanol decreased monotonously with the increase of the Na amount in NazH3_PW12040, but the activity for the isomerization of butene showed a complicated change as the amount of Na increased.
This different behavior in catalysis betw een the isomerization of butene and the dehydration of 2-propanol strongly suggests that the former reaction occurs only on the surface and the latter proceeds mainly in the bulk near the surface of the heteropolyacid.

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The ζ-potential of carbon black particles was measured in dispersion media, such as various aqueous solutions of acids, alkalis, alkali-metal chlorides, sodium halides, surface active agents and alkylamines. The ζ-potential of the carbon black particles was found to depend on the kinds of aqueous solutions and increase or decrease with an increase in the solute concentration of the aqueous solutions. A maximum or minimum point of ζ-potential against the solute concentration was occasionally observed on the graph. In the case of Emulgen (nonionic surface active agent), the c-potential was found to be constant. It was also found that the origin of the ζ-potential was related to both the magnitude of the surface charge density (σ) on the Stern layer and the position of the slipping plane in electrophoresis, because, with each dispersion medium, the correlation between σ and the concentration of the solute was positive. The magnitude of a was related to the density of the adsorbed ions on the surface of the samples and to the concentration of dissociated acidic functional groups on the particles. The position of the slipping plane generally lies in the diffusion double layer, but, in the case of a dispersion medium containing surface active agents or of alkylamines, its position is supposed to arise on the surface of the Stern layer. In this experiment, the effects of electroviscosity, surface conductance and dielectric polarization on the ζ-potential were neglected.

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Pyrolysis of amidophosphates was investigated by use of DTA, DSC, and TG. These three samples showed no difference in the pyrolytic behavior and decomposed thermally to liberate ammonia through an intermediate phase. The phase was found to be a determinate factor to control the pyrolysis. The mechanism of the pyrolysis was supported by the results of IR spectrum, X-ray diffraction pattern, and chemical analysis. A DSC operated isothermally indicates that the heat of pyrolysis increases almost linearly with increasing temperature in the ranges 443∼458 K for NH₄ salt, 427∼461 K for K salt, and 483∼517 K for Na salt. The heat and order of the pyrolysis were calculated on the basis of DSC curves. The pyrolysis is apparently the first-order reaction. The activation energies of the pyrolysis reaction in the above temperture ranges were estimated to be 208.6 kJ/mol for NH₄ salt, 157.0 kJ/mol for K salt, and 149.8 kJ/mol for Na salt.

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The effects of sulfate concentration, the composition of the solution, and additives which accelerate precipitation of nickel sulfide on the recovery of nickel and forms of sulfides have been investigated in order to recover Ni²⁺ from sulfuric acid leaching solutions by introducing ELS under atmospheric pressure. The percentage of precipitation of Ni²⁺ reached 86.4 % in a NiSO₄ solution (4.0 g Ni²⁺/dma). But in the presence of Na₂SO₄ (0.28 mol/dm³) or MgSO₄(0.25 mol/dm³), the recovery of Ni²⁺ increased to 99.1 and 98.1%, respectively. In th e case of Al₂(SO₄) (0.24 mol/dm3 as SO₄2-), however, the precipitation of Ni²⁺ remained at 86.3%and in addition, an induction period of 45 min was observed. These phenomena were interpreted as the progress of the sulfate complex formation and initial pH lowering by the hydrolysis of AP+. In the presence of CuSO₄, the precipitation was promoted and the precipitations of Ni²⁺ increased. Both Fe and Cu powders accelerated the precipitation and the induction period disappeared. On addition of Fe (2 gidma), Ni₃S₂ and Ni precipitated, whereas α-NiS, Ni, S₂, and α-Cu₂S were identified when Cu powder was introduced. By the addition of β-NiS and activated carbon, β-NiS was formed and the induction periods of 7∼8 mm were still observed. The calculated percentages of Ni²⁺ precipitation were agreed with the observed values, when the sulfate complex formation as well as pH buffer action of SO₄2- was considered in calculation.

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The thermal properties of diammonium hydrogenphosphate have been studied by means of TG, DTA, DSC and high temperature X-ray powder diffraction technique. The β-phase phosphate was transformed at about 159°C into a high temperature phase with endothermic heat of transition of 3.21 kJ/mol. The X-ray diffraction pattern of the high temperature phase was slightly different from that of α- (NH₄) 2HPO₄. This phase was designated to be α'-(NH₄)₂ HPO₄, which was retained on cooling to room temperature without moisture. The β→α' transition point was considerably influenced by moisture content; it decreased to 143°C with 1% moisture and to 136°C with 3% moisture, respectively.

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Adhesive strength between graphite substrate and low temperature pyrolytic carbon (LTPC)deposited by heating graphite at 700°C from cis-1, 2-dichloroethylene. was investigated for four kinds of graphite. Three 'substrates having thermal expansion coefficients from 2×10^-6 to 4×10^-6/°C exhibited the good adhesive property to the LTPC deposited, while the LTPC deposi ted on the graphite with the thermal expansion coefficient.9×10^-5/°C peeled away easily. In the former case, the cleavage between graphite substrates and LTPC was not observed in the range of tension tester used, but only interlayer cleavage in the LTPC layer was observed at tensile stress of 180 kg/cm2 as the maximum value. This result indicates that the adhesive strength between the graphite substrate and LTPC deposited on it is over 180 kg/cm².
These adhesive strength were not influenced with the roughness of substrat e's surface and the thickness of LTPC layer. Discontinuance of deposition gave no influence to the structure and the properties of deposited layer, even though the substrate coated with the initial LTPC was cooled to room temperature in a stream of argon. prior to the succeeding deposition. On the other hand, the LTPC deposited on the initial LTPC layer after standing for a day- in contact with air peeled away easily. The big adhesive strength of LTPC to the graphite substrate and very small one to the LTPC layer exposed to air suggest the possibility of existence of other factors than the matching of thermal expansion coefficient between the substrate and the deposited layer.

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The effect of fluorides on vapor phase growth of Si₃N₄, whiskers was studied on the nitridation of the SiO₂-C-fluorides system in a flow of N₂ gas at 1350 and 1400°C. NaF, AIF8, CaF₂, NH₄F and Na₃AlF₆ were used as fluorides.
The addition of NaF, CaF₂ and Na₃AlF₆ to form fluorosilicate melts under the growth conditions were effective for the growth of SiaN, whiikers, but that of AlF₈, which could not form a melt, were ineffective. The amount of α-Si₃ N₄ whiskers formed at the inside of graphite cylinder tended to decrease, while the amount of β-Si₃N₄ whiskers formed at the outside of it to increase with the increase of the amount of fluorides. The addition of Na.. AlF, or AlF, promoted the growth of β Si₃N₄ and β-Sialon whiskers more preferentially than α-type.
The effects of fluorides on the growth of Si₃N₄ whiskers are estimated as follows: 1) to act as flux and accelerate the reaction of SiO, with C, 2) to evolute Si₃N₄ from fluorosilicate melts and thereby to promote the evolution of SiO gas, 3) to decrease the viscosity of silicate melts and to enhance the evolution of SiO gas.
As previously suggested, SiO gas w as considered to exist as an intermediate species in this vapor phase reaction. It is believed that higher Psio in quasi closed system of graphite cylinder with caps than that in open system without caps is more favourable for nitridation.
It was deduced that Si₃N₄ whiskers grew by direct deposition on the su bstrate through vapor-phase reaction of SiO with N₂ and CO, and/or by the precipitation from the supersaturated solution of SiO, CO and N₂ gas in fluorosilicate melts.

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The cobalt (III) complexes, CoL3, were synthesized with 1-(p-substituted phenyl) -1, 3-butanediones (HL, L=p-XC₆H₄COCHCOCH₃, X=NO₂[1], COOH[2], COOCH₃[3], Br[4], C1[5], H[6], NHCOCH₃[7], C₂H₅[8], CH₃[9], OCH₈[10], OH[11]), and were separated into the fac and mer isomers by column chromatography on alumina. The ¹H-NMR spectra of CH₃ and CH exhibited a single peak for the fac isomer, and three p2eaks for the mer isomer. The chemical shifts of CH₃ and CH protons in chloroform-d and benzene-d₆ were observed at 1.9-2.4 ppm and 5.9-4.3 ppm, respectively, and the substituent effect and solvent effect for both protons were investigated. The ligand field bands, v₁(³T_1g←¹A_1g) and v3(¹T_1g←¹A1_1g) shifted linearly to the higher frequency side as the substituents became more electro n donative. The stability of these complexes was found to increase in the order of[1]<[2]<[3]<[4]<[5]<[6]=[7]<[8]<[9]<[10]<[11]in terms of the crystal field splitting energy 10 Dq obtained from the ligand field bands.

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Acrylamide, N, N'-methylenediacrylamide and styrene were block copolymerized in dioxane to give hydrophilic gels with macroporous structure. Water soluble samples such as acetone, ethylene glycol oligomers and blue dextran, were passed through the column packed with the gels and the calibration curves were prepared. The increase in the proportion of the crosslinking agent and styrene resulted in the gels with larger exclusion limit The crosslinking agent showed prominent effect to the result.
The monomer of the molar ratio of 0.14 for styrene to acrylamide containing 10.91 mol%of crosslinking agent gave the gels with exclusion limit of 1.26 × 10⁷, the degree of swelling (wet-ml/dry-g) of 3.38, the degree of bulkiness (dry-ml/dry-g) of 1.63 and the water regain (gfdry-g) of 2.22. The slope of calibration curve was gentle.
The gels copolymerized in dioxane-ethanol mixture, however, were fragile and gave no favorable mechanical stability and successful separation characteristics.

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The equilibrium and rate of solvent extraction of cobalt ion in aqueous solution (μ= 0.1)with 5-chloro-2-thiophenecarbaldehyde 2-benzothiazolylhydrazone (CTBH) in benzene have been studied at 25°C. The binding ratio of the complex was assumed to be 1: 3 (Co: CTBH) by the slope of distribution ratio against CTBH concentration, and the valence state of cobalt ion in the complex, which was measured by Evans' method, was +3. It was, therefore, concluded that the extracted complex was identified as the neutral chelate, CoR₃, where R represents dissociated CTBH. The distribution constant (log K'DC) of the complex between benzene and water was 2.23. The rate of the complexation reaction has been found to be first-order with respect to cobalt 00 ion and CTBH concentrations, and inverse first-order with respect to hydrogen ion concentration. From these results, the controlling reaction was assumed to be formation of 1: 1 chelate of cobalt (II) on with dissociated CTBH (R-) in aqueous phase. The rate constant for the reaction between cobalt (II) on and R. - was found to be 2.9×10⁶ mol^-1 ⋅dm³⋅ s^-1 at 25°C. The thermodynamic data for the reaction system were calculated. These values are Ea: 9.7kcal/mol, ΔH: 9.1kcal/mol, ΔG: 8.6 kcal/mol and ΔS:1.6 e. u. It was also assumed that the structure of the extracted complex was the octahe dral configuration.

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The equilibrium and rate of solvent extraction of copper (II) in 0.1 mol⋅dm-3 aqueous perchlorate media with 2-thiophenecarbaldehyde 2-benzothiazolylhydrazone (TBH) in benzene have been studied at 15-30°C. The plots of both log D'M vs. log[H+] and log D'M vs. log [HR]org showed straight lines with slope 2, where D'Mand [HR]og represent the distributi on ratio of copper and the TBH concentration in benzene, respectively. It was proved from the analysis of an electron spin resonance spectrum that the extracted copper (II) complex in benzene was paramagnetic. Consequently, the extracted species was assumed to be CuR2. The equilibrium constants of the copper (II) complex were determined; the extraction constant (log Kex), the distribution constant (log KDC) and the stability constants (log β1, log β2) were found to be 1.25, 2.45, 13.40 and 26.76, respectively. The rate of reaction w as found to be first-order with respect to the copper (II) ion and TBH concentrations, and zeroand inverse first-order with respect to the hydrogen ion concentration. On the basis of these results, the rate-determining step was assumed to be the formation of the 1: 1 chelate of copper (II) with TBH in aqueous phase. The formation reaction proceeds through two rea ction paths: the reactions of copper (II) with undissociated TBH (rate constant: 1.2 × 10⁴mol^-1 ⋅dm³⋅ s^-1) and with dissociated TBH (rate constant: 2.7 × 10¹⁰mol^-1 ⋅dm³⋅ s^-1). The temperature dependence of these rate constants was examined and the thermodynamic constants were calculated.

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Oxidation of α-longipinene[1] with lead tetraacetate gave an unidentified tertiary alcohol [2], longi-cis-verbenol [3], longi-trans-verbenol [4], longi-cis-R-crysanthenol [5], longiverbenone [6] longi-trans-β-ciysanthenol [7] 2β, 3β-dihydroxylongipinane [8], 4α, 8-dihydroxya-longipinene [9], and 4β, 8-dihydroxy-α-longipinene [10]. The structures were elucidated on the basis of chemical and spectral evidence. Compounds [4], [5], [7], [8], [9] and [10] are new sesquiterpene alcohols.

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Hydration and lead tetraacetate-oxidation of a mixture of δ- and 7-elemene ([1] and [2])were investigated. By hydration of a mixture of [1]and [2]with trichloroacetic acid, elemol [3] was obtained in high selectivity. A novel compound, c-3-isopropeny1-1-isopropyl4-methyl-t-4-vinyl-γ-1-cyclohexanol4was accompanied as a minor product. The configuration of hydroxyl group of [4] was confirmed by the variation in the contact shift of each proton using the shift reagent, Eu (dpm)³.Oxidation of a mixture of [1]and [2]with lead tetraacetate and subsquent hydrolysis gave 1-methy1-1-viny1-2-isopropenyl-4-(1-methyl-2-hydroxyethylidene)cyclohexane [5 a] and 1-methyl-1-vinyl-2-isopropenyl-4- (1-methyl-1, 2-dihydroxyethyl)cyclohexane [6a] which are new sesquiterpenoids. All of the compounds were found to possess a mild wood like odor.

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By treatment with copper powder in conc. sulfuric acid, 5, 5'-dichloro-1, 1'-bianthraquinone [1b] gave 8, 15-dichloro-7, 16-dihydrodibenzo[a, o]perylene-7, 16-dione [2b]. [ Under similar conditions, 5, 5''-dichloro-1, 1': 5', 1''-teranthraquinone [4], or 5, 5''-dichloro-1, 1': 5', 1'': 5'', 1''-quateranthraquinone 9D also afforded the corresponding cyclized product: 4, 15-dichlor o5, 16-dihydrodibenzo[fg, qr]dinaphtho[1, 2, 3-jk, 1', 2', 3'-uv]pentacene-5, 16-dione [6] or 15, 15'-dichloro-7, 7', 16, 16'-tetrahydro-8, 8'-bi (dibenzo[a, o]perylene) -7, 7', 16, 16'-tetrone [11]. Contrary to [2b], [6] or [11] was not so stable that the reverse reaction to yield [4 ] or [ 9 ] was detected even in the solid states. Upon irradiation, [2b], [6 ]or [11] cyclize d further to give 1, 6-dichloro-7, 14-dihydrophenanthro[1, 10, 9, 8-opqra]perylene-7, 14-dione [3b], 3, 12-dichloro-4, 13-dihydrodianthra[1, 9, 8-abcd, 1', 9', 8'-jklm]coronene-4, 13-dione C 8 or 6, 6'-dichloro-7, 7', 14, 14'-tetrahydro-1, 1'-bi (phenanthro [1, 10, 9, 8-op gra] perylene) -7, 7', 14, 14'tetrone [13], respectively. Direct synthesis of [8] from [4] was also studied.

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Copper ( I ) iodide dissolves in hot hexamethylphosphoric triamide (HMPA) to form a black solution, in which nonactivated aryl iodides readily underwent nucleophilic attack by benzenethiolate and benzeneselenolate ions, giving the corresponding diaryl sulfides and selenides in moderate to good yields. Without copper ( I ) salt, no substitution reaction took place. Under similar conditions, benzenetellurolate ion could also react with moderately activated aryl iodides to produce diaryl tellurides in fair to good yields. The present reaction provides a simple convenient route to unsymmetrically polysubstituted diaryl sulfides, selenides, and tellurides, which are laboriously obtained by the ordinary procedures.

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The reaction of 2, 3-diamino-1, 4-naphthoquinone [2] with potassium xanthogenate gave 2, 3-dihydro-2-thioxo-1 H-naphth [2, 3-d]imidazole-4, 9-dione [3]. Various 2- (2-oxoalkylthio)1 H-naphth[2, 3-d]imidazole-4, 9-diones [4a-k] were obtained by the reactions of [3] with a-halo carbonyl compounds. Compounds [4a-g] were synthesized in water and [4h-k ]were Obtained in the presence of the base using ethanol or water as a solvent. The reaction of [3] with bromoacetaldehyde diethyl acetal afforded sulfide [10], which was easily converted to 3-ethoxy-2, 3-dihydronaphth[2', 3': 4, 5]imidazo[2, 1-b] thiazole-5, 10-dione [11] in the presence of a trace amount of hydrochloric acid. The reaction of [3] with 1, 2-dichloroethane gave 2, 3-dihydronaphth[2', 3': 4, 5]imidazo[2, 1-b]thiazole-5, 10-dione [12] and dimeric compound [13]. The effects of the quinone carbonyl groups on the reaction and properties of these compounds are discussed.

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Tetracyclic azole compounds with an additional thiazole ring fused to naphth[2, 3-cnimidazole4, 9-diones were synthesized. Naphth[2', 3': 4, 5]imidazo[2, 1-b]thiazole-5, 10-diones [15a-k]and [13]-[15] were obtained by cyclodehydration of 2- (2-oxoalkylthio)-1 H-naphth[2, 3-d]imidazole-4, 9-diones [4a-k]. Polyphosphoric acid was used to effect cyclodehydration of [4a-g]. With acetic anhydride and pyridine, [4b] and [4h-i] were found to undergo acetylation and cyclization to form [5g] and [5i]. The reactions of [4j-k] with acetic anhydride gave [5j-k] in the absence of pyridine, but in the presence of pyridine they afforded [14b] and [15]. The effects of the quinone group on the reaction and properties of these compounds are discussed.

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The homologation of methanol to ethanol was carried out with the aid of the mixed transition metal catalysts containing cobalt in conjunction with iodide promoters under the compressed synthesis gas (H₂-CO). The Co-Ru system was found to exhibit a remarkable catalytic activity for homologation. The influences of reaction variables such as Ru/Co ratio, pressure, temperature, added iodide and solvents on the methanol conversion, the ethanol selectivity and the formation of by-products were examined in detail. Both the yield and selectivity of ethanol were significantly dependent on the Ru/Co ratio and the composition of synthesis gas. The yield increased with the charge ratio of RuCl₃⋅ n H₂O to Co₂(C0)₈(Ru/Co), reached a maximum and then decreased with larger ratio. The optimum ratio of Ru/Co varied slightly from ca. 0.2 to 0.4 when the temperature and the partial pressure of H₂ were decreased under the otherwise same conditions.
It was also found that ethers such as 1, 4-dioxane, THF, Methyl Cellosolve and Diglyme, served as a good solvent to give the higher yield (ca.60%) and selectivity (ca.80%) of ethanol.

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The oxidation of o-toluic acid was studied using cobalt (II) and bromide ions as catalyst in acetic anhydride, and the reactivity was compared with that in acetic acid. In acetic anhydride, phthalic anhydride could be prepared in one step but a large amount of 3-acetoxyphthalide was also produced (Fig.4). Acetic anhydride was hydrolyzed as the oxidation proceeded, and stoichiometry of the hydrolysis suggested that the overall oxidation formula in acetic anhydride could be expressed as follows (Eq. (1), ( 2)).
In acetic acid, phthalic acid was the mai n product and phthalic anhydride as well as phthalide was also detected in the products as intermediates to phthalic acid (Fig.5). It was observed that 86% of cobalt (II) acetate added as catalyst precipitated and the bromide ion was converted to the organic bromine when the oxidation was performed in acetic anhydride (Fig.7), but not in acetic acid (Fig.8 ). Bromoacetic acid was identified as the organic br omo compound formed in acetic anhydride. However, in the oxidation of o-xylene in acetic acid, the bromide ion was once changed to organic bromine at the initial stage of the oxidation, and then the ion was regenerated with the increasing concentration of o-toluic acid formed in the reaction system (Fig.9).

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Higher homologueso f (2-hydroxyalkydl)i m ethylammonio-N-acylimin(aems inimidesb) earing a macrocyclicp o lyetherg roup (Cn-AIC(m), n: 12 and 18, 7 12: 5 and 6) were synthesizedin the yields of 30∼ 40% from 1, 2-epoxyalkaneN, , N-dimethylhydrazinaen d 4 '- ( ethoxycarbonyl)benzo-crowne thers by the Slagel methodf or preparinga minimides( Scheme1 ).
Some surface a ctivep ropeitiesa nd effectivenessin phase transfer catalys is of Cn-AIC(m)werd examineda nd: comparedw ith those of several r eference compounds( Scheme2 ). The obtainedC nTAIC(m)w ere all solublei n water. While they had much lower critical micelle concentration( CMC)c omparedt o the correspondinga minimidest, heir cloud points (Cp) and CMCsw ere rather higher t han. that of the other crown ethers ( [3], [8] and [9]) hav ing the same allyl chain ( Figsi 1, 2 ). The CMC of Cn-AIC(m)d ecreasedm arkedly with, t he increaseo f n just in surface active aminimidesb, ut dependenceb oth on n and m was not apprbciablef or the Cp of C, MIC(m) (Table2 ).
With respectt o the catalytica, ction, Cn-AI C(m) were far more activet han t heir respective functionalm oieties ([2] and [4]). In comparisonw ith the referencec rown ethers, Cn-AIC (m) were most effective( eqiivalentt o [7] on reductiono f 2-octanonew ith aqueou sN aBH4(Table3 ), but their effectivehesws as rather moderate( closet o that of [9] in the substitution reactiono f 1-bromooctanwe ith aqueousa lkali metal iodide (Table4 ). On both the reaction, the efficiencyo f -en-AIC(m) increasedw ith the increasingn. These results were interpreted in terms of concertedc omplexationw ith two ligands ( aminimideand polyether ring) in.Cn-AIC(m) and of suitabilityo f the hydrophile-lipophilbea lance of the catalyst to the reaction phase.

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A variety of 2-amino-4-(p-substituted phenyl) - and 2, 4-dipheny1-6-(vinyl or isopropeny1)1, 3, 5-triazines were readily synthesized in high yields by the reaction of benzimidoylguanidines and N-benzimidoylbenzamidine with unsaturated carboxylic acid chlorides.
The hompolymerization of these triazine monomers and the copolymerization with methyl naethacrylate were investigated in dioxane at 60°C using a, c'-azobisisobutyronitrile or a t 30°C using N, N-dimethylaniline-benzoyl peroxide as an initiator. Q values obtained were very large and negative e values were decreasedw ith increasing electron-releasinge ffect of p- (substituted phenyl) group. This could be related to a negative inductive effect and a conjugation of phenyl group with a double bond through the triazine nucleus.
On the other hand, the introduction of 2-am ino-4-phenyl- and 2, 4 -diphenyl-1, 3, 5-triazines to a polymer as pendants decreased the flexibility of the polymer chain, and softening point rised considerably with increasing triazine ring content. And copolymers containing 2, 4diphenyltriazine rings became readily soluble in nonpolar solvents such as benzene, carbon tetrachloride and chloroform, whereas copolymers containing 2-amino-1-phenyltriazine rings were soluble in polar solvents such as dioxane, N, N-dimethylformamide and acetic acid. From the above results, it was found that the interaction between aminotriazines of these polymers was less than that of the polymers containing guanamine structure (2, 4-diaminotriazine rings), and the rigidity and the hydrophobicity of aromatic rings attached to triazine rings reasonably affected the physical and thermal properties of the polymers.

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The copolymerization of sulfur dioxide with acrylic anhydride was carried out in N, N-dimethylformamide or dimethyl sulfoxide using AIBN as an initiator. Copolymer obtained was studied by IR-spectra and elemental analyses. The structure containing a closed ring unit, the SO₂ unit in the main chain and a small amount of CH₂. CH- group in the side chain was proposed. The thermogravimetry (TG) and the differential scanning calorimetry (DSC) were carried out on the copolymer sample in air. The melting point was not observed and DSC thermogram showed an endotherm at 170∼200°C.

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Allylbenzene (AB) was radically copolymerized with methyl acrylate, methacrylonitrile, acrylonitrile (AN), methyl methacrylate (MMA), and fumaronitrile (FN) in the presence of zinc chloride. The copolymerization with last two monomers did not take place unless zinc chloride was added. The AB-FN system gave an alternating copolymer. In the AB-AN and AB-MMA systems, apparent monomer reactivity ratio decreased with increasing concentration of zinc chloride added. The significance of the apparent monomer reactivity ratio for these copolymerization systems was studied from a kinetic point of view, and absolute monomer reactivity ratios were evaluated from the values of the apparent monomer reactivity ratio obtained experimentally: k11/k12=0.13, k11k13 = 5.1, k12/k13=39.4, k22/k21=1.05, k22/k23=0.85, and k21/k23=0.81 for the AB-AN system, and k11k/k12=0.024, k22/k21=0.91, k22/k28=8.57, and k21/k23=9.42 for the AM-MMA system, where M1, M2, and M3 represent free AN (or MMA), complexed AN (or MMA), and AB, respectively. Q and e values of AN and MMA complexed with zinc chloride were QAN ⋅ZuCl2=25; eAN⋅znCl2 = 2.61, QMMA⋅ZnCl2=68, and eMMA⋅ZnC12=2.36, respectively. The copolymerizations in the presence of other metal salts were also studied.

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Methacrylic acid (MAA) and ethylene dimethacrylate (EGDM) were found to be copolymerized by the aqueous solution of starch. Almost all the starch used was grafted by the crosslinked copolymer of MAA with EGDM. Sodium salt of the produced copolymer could adsorb water up to 620 times its weight. Thus the grafted starch with MAA and EGDM seems to be useful as a super water-adsorbent.

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Chemical modification of styrene-butadiene popcorn (SBP), a by-product in the production of styrene-butadiene rubber (SBR), has been made for its utilization. The cross-linking reaction of SBP with sulfuric acid in carbon tetrachloride resulted in an increase in cross-linking of SBP. The reaction products with' higher concentration of sulfuric acid swelled much less in benzene. A similar reaction using BF₃ Et₂O or SnCl₄ as an acid-catalyst gave no increase in cross-linking of SBP. Sulfonation, nitration and chloroxpethylation of SBP introduced the corresponding functional groups by 2∼3 mmol per 1g of SBP. Reduction of the nitrated SBP with SnCl₂ converted it into the amino-SBP, which showed the ion exchange capacity of 2.5meq/g. Moreover, reactions of chloromethylated SEW with potassium cyanide, followed by hydrolysis with sulfuric acid in aqueous acetic acid, led to the introduction of the carboxyl group in SBP.

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A method for the determination of the total photochemical activity of hydrocarbons has been investigated. The electric discharge was carried out in O₂/He gas to produce atomic oxygens using a 2450 MHz microwave generator. The discharged gas was introduced into a chemiluminescence reactor through an orifice, and made to react with hydrocarbon gases. A. monochromator, a photomultiplier tube cooled thermoelectrically, and a photon counting systern were employed to measure the intensity of the chemiluminescence. The typical operating conditions suitable for the measurement of the total photochemical activities were as follows: O₂ concentration of discharged gas (O₂/He) 1.0%, flow rate of discharged gas: 100 cm³. min^-1 flow rate of hydrocarbon gas: 60cm³imin^-1, pressure at discharged section: 10 Tom pressure at chemiluminescence section: 1.5 Torr, the microwave output: 15 W.
Active species such as OH, O, HO₂, and O₃ are known to play an important role in the process of the smog formation. Both OH and O are noted because of their remarkable reactivities with hydrocarbons, and a search is made for the ralationship between the rate constants in the reactions of the hydrocarbons with these species. It is proposed that the photochemical reactivities of the hydrocarbons may be represented by the reaction of O atoms with hydrocarbons. The. photochemical activities were obtained by the measurement of OH emission intensity at 3089Å from the reaction. Examination of the relationship between the rate constant and the emission intensity indicates, in the case of [O]Δt0.7<10^-12 molcmas, that the hydrocarbons of Kox < 1< 10¹³ cm³imol^-1 s^-1 yield the emission intensities corresponding to the photochemical reactivities. The [O] is the concentration of atomic oxygen, and Δt is the time in which the reactant gases traversed the incident window of a flexible UV light guide, which was mounted in the chemiluminescence section of the reactor.

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The photochemical reactions of ammonia with nitrogen monoxide in N₂ and in O₂-N₂mixture were studied under UV irradiation with low pressure mercury lamp through spectrosil quartz at room temperature and under the atmospheric pressure. NH₃ in N₂ decomposed slowly to form N₂ and H₂ through H₂NNH₂. The decomposition of NH₃ was accelerated remarkably by the addition of NO into the mixture of NH₃-N₂. A stoichiometric equation 2NH₃-1-2 NO=2N₂-FH₂+2 H₂O was set up on the basis of the relation between the amount of decomposed NH3, NO and formed H₂. A small amount (4% of decomposed NO) of N₂O was formed as a side product. The NH₃ decomposition was accelerated by O₂. Nitrogen, N₂O and NH₄NO₃ formed in quantity accompanied by a small amount of NH₄NO₂ in the photochemical reaction in the NH₃-O₂-N₂ mixture. NH₃ decomposition was not appreciably accelerated by the addition of NO, but the increase in NH₄NO₂ and N₂ formation and the decrease in N₂O formation were observed. The decomposition rates of NH₃ and NO in NH₃NO-O₂-N₂ incresed by the increase of O₂ concentration. The initial rate of NO decompsition in 0₂(20%)-N₂ was 1.7 times of that in N₂, while NH₃ decomposition rate was 2.7 times. The amount of decomposed NH₃ was 1.6 times larger than that of NOz in O₂(20%)-N₂.

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An experimental investigation was made to examine the possibility of shortening the time required for the determination of solid acidity (several days) by the Benesi method by particle size control. The time needed for obtaining constant acidity values for silica-alumina and alumina is extremely reduced to below one day when the sample particle is made smaller (less than 325 mesh), and the acidity obtained after stabilization is not affected by the particle size. The particle size must be as small as possible to shorten the time required for the titration. This effect is attributable to the slow desorption of amine molecules once adsorbed on the outer surface sites followed by migration to the inner sites of particle.

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The indigo carmine method employed for the determination of dissolved oxygen has been improved. An NH₄Cl-NH₃ buffer was used as a diluent for the sample solution so that a wide range of the dissolved oxygen concentrations could be determined. The reduced indigo carmine was prepared in a graduated syringe and the diluent and a pre-determined quantity of the electrolyte solution containing the dissolved oxygen was subsequently introduced into the syringe. The final pH of the solution thus obtained lay between 8 and 9. The oxidation of the indigo carmine with the dissolved oxygen occurred almost instantaneously and re-reduction of the indigo carmine color so produced by any excess n-glucose present in the solution did not occur for about 30 min at an 'initial glucose/indigo carmine weight ratio of 0.5. The concentration of the re-oxidized indigo carmine was estimated by measuring absorption at 620nm. This improved technique shows excellent reproducibility and accuracy in the determination of the dissolved oxygen over a wide range of electrolyte C oncentrationsi n spite of the diluent being used. The technique has been applicable not only to aqueous solution but also to organic solvent.

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Diphenyl- and methylphenylcyclopropenones reacted easily with alkane- or arenethiol in the presence of potassium hydroxide in ethanol at room temperature to give ring opened 1: 1addition products, 2-propenethioate derivatives in 31∼82% yields. The reaction in the presence of excess amount of thiol yielded 1: 2 addition product via Michael addition.

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The change in the fine structure of the cellulose gel biosynthesized by Acetobacter zylinum with time was studied by means of electron microscopy. It was found that in the process of time, the inhomogeneous distribution cellulose chain arised in the vertical direction against the long axis of the amorphous fibril initially and finally many microscopic fibrils with the width of about 40∼50 Å appeared simultaneously in the amorphous fibril. This microscopic fibril corresponds to the elementary fibril reported in the previous paper. It was also found that the bacterial cellulose microfibril is composed of the microscopic fibril.

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