. photodegradation mechanism of N-alkylamides (N-methylformamide, N-methylacetamide, N-propylpropanamicie, and N-prclpylhexanamide) containing Fet1.₃ was studied mainly by means of ESR spectroscopy.
Examination o f I R and UV spectra revealed that amides coordinate to FeC13 through the oitygtn atoms. ' A charge-transfer absorption band was observed (λ_max 312 nm, ε= 4.3 X 1 0³)the -case of N-propylpropanamideFeC13. An ESR study determined structures of radic als generated by photo-irradiation of various kinds of amides containing FeCl₃. UV irrad iation gave rise to a trupture of the amide linkage to produce an acyl radical. The acyl radical was decarbonlated to become an alkyl radical (or hydrogen atom in the case of N-methylforn - amide). by_irradiation of visible light. When the alkyl radical was small (in such cases as N., methylformamide, N-methylacetimide, and N-propylpropanamide), an extraction of hydrogen -atom from other molecules occurred during annealing, and two kinds of other radic als were produced: a radical bearing an unpaired electron on a carbon atom adjacent to a carb ony l- group, - and an iminyl Tadical. Detection of the iminyl radical confirmed that a genera tion of ipline was jaccompanied with the formation of acyl radical at the initial process of UV irradiation.

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Photoconductive metal-free phthalocyanine was dispersed in a binder including phenolic resin and it was coated on commercial positive working type presensitized printing plates directly or after pre-coating of a thin PVA interlayer. The plate-making process consists of corona charging, image exposure, liquid toner development, the uniform UV exposure and alkaline development steps. The plate could be charged either positively or negatively to 217 or 220V, respectively. The incident energies required to discharge the photoreceptor to one-half of its maximum surface potential were170 and 200 erg/cm² when exposed by a xenon lamp for positively and negatively charged cases, respectively. The toner image formed on the photoconductive layer served as a good optical mask for the UV-exposure to the photopolymer. Both the photoconductive and photopolymer layers exposed to UV light were dissolved away by the aqueous alkaline solution and then plate was ready to be used for offset printing as well as the conventional presensitized printing plate. This electrophotographic printing plate exhibited a high resolving power over 25 lines/mm. We have also found out that electrophotographic printing plates consisting of a double layer a photoconductive layer and an alkali soluble photopolymer-have an excellent photosensitivity, a high resolution and a long-run capability suitable for the projection and laser plate-making.

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The behavior of a silver-silver oxide electrode in 4.7 molg KOH solution containing a small amount of either nickel(II) chloride or cobalt(II) chloride was examined by potentiostatic and galvanostatic methods. A scanning electron microscope was also used.
The following results were obtained: 1) The capacities of the electrodes measured by a galvanostatic method were appreciably increased by the addition of these chlorides.2) The coulombic areas under all the peaks in cyclic voltammograms increased with the addition of the chloride. Consequently, the electrode capacities determined by charge-discharge curves and current-potential curves increase in the presence of these chlorides.3) The formation of a fine crystal was detected in the electrodes with added chlorides by electronmicroscope. It has been concluded that the increase in electrode capacity caused by the addition of the chlorides is closely related to the formation of such finely crystalline substances: through the adsorptiondesorption process of colloidal particles in the presence of nickel( II) chloride; through the adsorption and electrolytic deposition-dissolution processes of ionized particles in the presence of cobalt (10 chloride..

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The anodic conversion process of electrolyte anions, which were incorporated in the oxide during anodization of aluminium in the solution of oxalic, malonic, and tartaric acid, was thermochemically simulated from the viewpoints of the oxide colour, photoluminescence (P L), and electron spin resonance (ESR) characteristics, and IR spectra by calcinating a mixture of hydrated alumina gel and each of the above mentioned carboxylic acid. The purpose of this paper is to confirm the validity of a model, explaining that the colouring (self-colouring), PL, and ESR characteristics of the anodic alumina films formed inthe solutions of lower aliphatic carboxylic acids are due to the presence of carbonized products of the incorporated . electrolyte anions. Alumina specimens obtained by the calcination could essentially reproduced the characteristics of anodically formed alumina in the corresponding solvents of different carboxylic acids. The results strongly support the validity of the carbonization model for the anodic conversion of incorporated electrolyte anions.

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Spinel-type ferrite film electrodes were prepared by thermally decomposing various metal nitrates' on a platinum substrate at 500-1150°C, and their physicochemical and electroche mical properties were investigated.'It was found that there exists a correlation between the oxygen -qvervoltage and the magnetic property of the electrodes. The oxygen overvoltage at 1m Acm^-2 decreased almost linearly with the increase of saturation magnetization at room temp erature and effective Bohr magneton of all the electrodes tested, except for a Pt/CoFe₂O₄ electrode. The kinetic analysis of the oxygen evolution reaction revealed that the second step, or chemical reaction of OH radical with OH^- ion, is rate-determining on the Pt/C0Fe₂O₄electrode whereas the first step, or discharge reaction of OH- ion to form OH r a d ical, is rate-determining on all the other electrodes. Accordingly, the above relationship between th e oxygen overvoltage and the magnetic property was explained on the basis of the difference i n - the rate-determining step of the oxygen evolution reaction and the stability of the reactio n intermediate or OH radical.

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Two TiO₂ samples (anatase) were treated with various normalalkyl amines (the number of carbon atom in the molecule: 3, 4, 6, 8, 12, 14, 16, and 18) and with several carboxyl i c acids (CI-18COOH, C F, COOH, and C61-1, COOH)a t 80°C for 1 h in benzene. Except for otadecylamine, the amounts of amine reacted with TiO2 heat-treated at 300°C were nearly constant, being in the range of 0.84-0.99 mmol/g TiO₂, regardless of the number of c a r b on atom in the molecule (Table 1). Assuming that the TiO₂ surfaces were covered b y the monolayer of alkyl groups, which were oriented perpendicularly to the surfaces, the surfa c e areas of TiO₂ occupied by amines were calculated to be about 110m 2/g TiO₂. This figure was considerably less than the specific surface area (150m ²/g TiO₂) determined by N₂ ad s o rp, tion. Infrared spectra were taken to further discuss on the bonds by which amines o r a cids should combine with TiO₂ surface (Fig.3).
The TiO₂ treated with amines having the h ydrocarbon chains longer than butylamine was dispersed in benzene more preferentially than in water, indicating that the hydrophilic surface of -no, was changed to be lipophilic by the amine treatment (Table 2). Among trea t m ent with the acids, only one with benzoic acid was effective for the surface modification.

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A new extraction method of chromateCE ion from chromite ore, based on a closed system under the hydrothermal conditions, was proposed. A microautoclave (10 cm₃) was used in the study.
High extraction ratios (nearly 100%) were achieved under the following conditions, concentration of NaOH solution; 7.5 moldm-3, extraction temperature; 400°C, duration of extraction; 20 min, atmosphere; 13 MPa of O₂ gas. The spinel structure of chromite ore remained in extraction residues. The residues at about 50% of extraction ratio were the mixture of MgFe₂O_4, MgCr₂O₄, Mg(OH)₂, and starting chromite ore. It was suggested that the extrac tion of chromate(V) ion proceeds by two reactions, which are shown as (Fe, Mg)Cr₂O₄ →MgFe₂O₄+CrO_42-, and MgCr₂O₄ Mg(OH₎2CrO₄2-. MgCr₂0₄ shown in the later eq uation is formed by the greater Mg content in the chromite ore compared with that of Fe. The final residues or chromite slag with less than 10% of residual Cr were almost the mixture of MgFe₂0₄ and Mg(OH)2. t Hydrothermal Extrac tion of Useful Elements from Various Ores. IL

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Adsorption process of lithium ion to amorphous hydrous aluminium oxide (a-HAO) was investigated by pH titration method with lithium chloride-lithium hydroxide mixed solution and X-ray diffraction analysis of a-HAO after pH titration. In the pH titration, the addition of hydroxide ion in amount from 0 to 4.0 mmol⋅^-1. gave no change to the pH of the solution and caused adsorption of lithium ion equivalent in amount to added hydroxide ion. X-ray diffraction analysis showed the formation of lithium hydrogenaluminate LiH(AlO₂)₂⋅5 H₂O (LHA) in the a-HAO after pH titration. These results showed that adsorption of lithium ion by a-HAO, wa8 related to a reaction which consumed hydroxide ion and formed LHA. In order to elucidate detail process of the reaction, changes of pH, aluminium concentration and lithium concentration of the isolution, respectively with time were determined. The pH ol the solution decreased in two stages. At the first stage of the pH decrease, the aluminium concentration increased whereas the lithium concentration did not change. At the second stige, the -lithium concentration decreased together with the decrease of the aluminium concentration. It was inferred that adsorption of lithium ion proceeded through dissolution of a-HAO and precipitation of LHA. Theoretical adsorption capacity calculated from the abov e formula for LHA and aluminium content in a-HAO was 4.7 m mol⋅g^-1 and agreed fairly well with observed value 4.0 mmolig-'.

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The kinetic studies of the decomposition of tris(oxalato)cobaltate(M) ion [Co(C₂0₄)₈]^3- were made in the binary solvents of water with methanol (MeOH), ethanol (Et0H), t-butyl alc o hol (t-BuOH), dimethyl sulfoxide (DMSO), and acetonitrile (AN) at an ionic strength of O.2 mol dm-3 and at 25--40°C. In all solvents the rate of decomposition of the cobalt(III) complex ion was described as d[[Co(C₂0₄)₃]₃-]= k _obs[[Co (C₂O₄)₃]^3-], where (1/2)kobs=k0+kh[H+]+k2h [H+]2 in the solutions of the neutral to acidic region. The values of ko, kh, and kth were determined under various conditions. The ko value was independent of the sorts of solven t of the binary-aqueous media, and also of the mole fraction of solvents. On the other hand, th e values of kh and km increased in the following order: t-BuOH<Et0H<Me0H<DMSO<AN at a mole fraction of 0.2, where the activation parameter s were determined for the each reaction path of ko, kh, and k2h. They were also dependent on the mole fraction of solvents u s e d and increased with an increase in the amount of the organic constitute. The activationent ropy aelΔ_h for the ko path was negative or very small if positive in all solvents, while ΔS_h and Δ_2h were, in general, very large in all solvents. The results obtained were discu s s ed in terms of (1) the permittivity of solvents, ( 2 ) the stability of the solvated proton (HSalv+), and ( 3 ) the stability of the proposed intermediate species with solvation.

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The strong basic anion exchange resin was prepared by the chloromethylation of diphenyl phosphonate-butyraldehyde condensation resin, followed by the amination of chlo rometyl group. The ion exchange capacity of the dry resin is 1.05 meciig and the time to reach an equilibrium, state was 10 to 15 m in. This resin showed selective adsorption for CrO₄^2-, MoO₄^2-and WO₄^2- ions. These ions loaded on resin were separated chromatographically from each other by sequential elution: Mo(U) was stripped by elution with 1.6% NaCl solution of pH 7.2, then Cr(VI) with 1.6% NaC1 solution of pH 7.8 and W(VI) with 1.6% NaCl-0.1 molg NaOH solution, respectively. The recovery of CrO₄^2-, MoO₄^2- and WO₄^2-ions was also investigated.

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The extraction and determination method of cadmium at trace level concentration in seawater by carbon furnace atomic-absorption method was proposed by using lvol% Capriqu a t solution in xylene as extracting agent for trace amounts of cadmium and removing int e r ference from the matrix. Interference from matrices such as acids, salts, and metals on the extraction of cadmium was also studied. Cadmium in the organic phase was then stripped in 0.2 molf/perchloric acid solution and determined by carbon furnace atomic-absorption spectrom etry. The proposed method was applied to the determination of cadmium in seawa t e r samples. The results obtained by the proposed method were in good agreement with those obta i ned by the carbon furnace atomic-absorption method combined with chelate resin separation. Th e chemical species for the extraction of cadmium was studied. The species extracted could be formulated as follows: (R₃CH₃N)₂CdCl₄ (R = Octyl radical).

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The stability constants (logK_ad) for 1: 1 adduct formation of N icke(II)-dithizonate with unidentate (pyridine, isoquinoline and γ-picoline) and bidentate (2, 2'-bipyridyl) heterocyclic nitrogen bases were determined. In unidenate bases, log K_ad increased in the following order; pyridine<isoquinoline<γ-picoline, which followed the order of basicities of these base s. A linear free energy relationship was observed between log K_ad for pyridine and those for other unidentate bases in various solvents but was not observed between log K_ad for 2, 2'-bipyridyl and those for the unidentate bases. The adduct formation constants for 2, 2'-bipyridyl in various solvents were well correlated with E_T values, which were proposed as a micro measure of solvent polality.

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Half-wave oxidation potentials (volt vs. SCE) of several dialkyldithiocabamates, R₂NCS₂Na were measured at pH 9.14, where R represents methyl (O.37 V), ethyl (O.41 V), propyl (0.45 V), isopropyl (-0.48 V), butyl (-0.53 V) and isobutyl (-0.50 V), and R₂N represents 1-pyrrolidinyl (-0.40 V). Prior to these measurements, the pH range in which sodium dialkyldithiocarbamates were stable was ascertained by observing absorbance at 275-295 nm. When the half-wave potentials thus obtained were plotted against pKg values or against pK, values at the ionic strength of 0.01 for the corresponding dialkyldithiocarbamic acids, a linear relationship- was obtained in metlilyl, ethyl, propyl and butyl series. This relationship was interpreted by inductive effect of R groups and specific configuration of dithiocarbamate anions inc ontrtaosc ta rboxyHlaetrteeh. ec annonfoicram
_??_
were assumed to play an important role. This interpretation was supported by IR absorption spectral data.

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The rate of A1C18-catalyzed acylation of benzene with a series of alkanoic anhydrides was measured in 1, 2-dichloroethane. The reaction obeyed 5/2-order kinetics, first order in benzene and 3/2-order in the anhydrides, and the relative rates of the anhydrides fitted Taft's equation with ρ* of 3.91 and δ of 0.37. A sequence of reactivities, acetic>isovaleric>propionic>valeric>butyric>phenylacetic>cyclohexanecarboxylic>isobutyric anhydride, was observed at 30°C. Competitive benzoylation of kenzene with p-substituted benzoic anhydrides could be co rrelated well with Brown-Okamoto's σ+ constants. The substituent effect on the benzoylation with p-chloro-p'-substituted benzoic anhydrides, however, gave a confusing result. A probable mechanism involving the 1: 1 addition complex between A1C1₃ and acyl chloride as actual acylating agent, which was formed from an interaction between the carboxylic anhydride, and AlC1₃, was proposed and discussed for the acylation with the carboxylic anhydride in the presence of Aida.

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In order to clarify the aspect of the hydrogenolysis of thioami des, thiobenzamide, octanethioamide, N, N-dimethylthiobenzamide and other thiobenzamide derivatives were hydrogenolyzed under the constant hydrogen pressure of 40 atm at 160-240°C for 90 min with molybdenum trisulfide as a catalyst.
In the hydrogenoly sis of thiobenzamide at 160-200°C and octanethioamide at 200-240°C, the corresponding thiol and nitrile were obtained as major products. In the case of hydrogenolysis of thiobenzamide di- and trimerized products, viz., 3, 5-dipheny-1, 2, 4-thiadiazole and 2, 4, 6-triphenyl-1, 3, 5-triazine were also formed as minor products. It was considered that the nitriles might be formed simply by the dehydrogensulfurization from these thioamides, except for N, N-dimethylthiobenzamide which has no nitrogen-hydrogen bond. It was found that the order of the easiness of thiol formation by the cleavage of carbon-nitrogen bond from these substrates is as follows: N, N-dimethylthiobenzamide> thiobenzamide > octanethioamide. This order is just opposite to that of nitrile formation by the cleavage of carbon-sulfur bond. The fact of the thiol formation is of interested in contrast with amine formation in the case of ordinary reduction methods using lithium aluminium hydride or aluminium amalgam. It was presumed that the di- and trimerized products were formed through the association of radicals which might be produced during the dehydrogensulfurization of, thiobenzamide.

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[in Japanese]

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A Major product of the Vilsmeier reaction on 3-methylgua iazulene was confirmed to be 2f ormyl-1, 3-dimethy1-4-(2-dimethylaminoviny1)-7-isopropylazulene, which was converted into 2-f ormy1-3-methylguaiazulene by hydrolysis under drastic conditions. A diformylated derivat ive (2-position of azulene ring and a-position of 7-substituent) was also isolated as a minor product. In addition to the homologues of these basic compounds, considerable amounts of the corresponding 2-formy1-3-alkylguaiazulenes were detected prior to the drastic hydrolysis in the reaction products from 3-ethyl- or 3-propylguaiazulene. A mechanism consistent not only with these chemical evidences, but also with the theoretical consideration is proposed.

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Since on the Friedel-Crafts alkylation of azulenes there are two kinds of negative factors, that is, rather low yield and isomerization of substituents, the reduction of 3-acylguaiazulenes prepared by the Vilsmeier reaction was studied under various conditions to obtain 3-alkylguaiazulenes. The reduction of 3-acyl-, especially 3-f ormylguaiazulene was surveyed comprehensively to reveal that by using LiAlH1₄, NaBH₄ or B₂H₆, or by the Meerwein-Ponndorf reaction 3-acylguaiazulenes gave only alcohols, which were easily dimerized or dehydrated spontaneously on standing. On the other hand, reduction of them by using combination of LiA1E1₄-AlCl₃or NaBH₄-AlCl₃, or by the Wolff-Kishner reaction gave 3-alkyl derivatives in good yields, especially in first case. The reduction of 2-f ormyl-1, 3-dialkylazulenes by the Wolff-Kishner reaction resulted in the formation of 1, 2, 3-trialkyl compounds but LiAlH₄-AlCl₃m ixture gave only alcohols due to a poor electron-donative character of 2-guaiazulenyl group in contrast with that of 3-isomer.

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The thermal decomposition of bis (2-ethylhexyl) phthalate (DEHP) and dioctyl phthalate (DOP)was carried out in a newly designed quartz flow reactor, capable of avoiding the secondary decomposition of the products (see Fig.1). The thermal decomposition conditions were as follow; the temperature range 250-500°C, residence time 2.2-8.4 s, molar ratio of nitrogen gas to sample 20.1. The thermal decomposition products of DEHP and DOP showed that the decomposition proceeded mainly by cis-elimination. The first order rate constants of the reactions were obtained as (see Fig.5-7);
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Acyloin type macrocycles (3) were synthesized by the intramolecular condensation of diesters (2) bearing poly(oxyethylene) chain. The macrocycles (3) were treated with G rignard reagents to give a new series of surface-active crown ethers (C-AC(m)).
Cloud point, critical micelle concentration (CMC), surface t ension at CMC (roma), and catalytic action on the reaction of 1-bromooctane with saturated aqueous alkaline metal iodides were examined for Cs-AC(m). The data were compared with those of linear poly (oxyethylene)nonionics (CS-n(m)) and of known crown ethers (4 )-(8) having the same number of carbon atoms in the alkyl chain and of hetero atoms in the ring. It was found that Cn-AC(m) had higher cloud point, higher CMC and lower roma than those of the reference crown ethers (Table 2). In these properties (Table 2) depending on the alkyl chain length and the hetero atom number (Fig.2 and 3), C-AC(m) were rather close to S-n(m). With respect to the catalytic action, Cn-AC(m) had high efficiency like the reference crown ethers, (4) and (7), and exhibited greater selectivity for alkaline metal ion species than that the other crown ether (Table 3).

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Isomerization of nerol in the presence of benzenethiol was studied. When nerol was heated at 80°C in the presence of a small amount of benzenethiol and a radical initiator, cis-trans isomerization and allylic alcohol-aldehyde isomerization occurred simultaneously to affo rd geraniol and citronellal, respectively. Generally, the cis-trans isomerization was much faster than the allylic alcohol-aldehyde isomerization, but the ratio of the two isomerizations was largely affected by the amount of benzenethiol and the kind of the solvent. The selectivity for citronellal was very high (>80%) based on the consumed alcohols. In the case of alkanethiol, only cis-trans isomerization occurred 'and no isomerization to aldehyde was observed. Isomerization of other, β, γ-unsaturated alcohols was also examined.2-Buten-1-ol and trans2-hexen-1-ol isomerized to the corresponding aldehydes, respectively, but 2-methyl-2-propenlol and 3-phenyl-2-propen-1-ol did not react under similar conditions.

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The hydrogenolysis of O- (3, 7-dimethyl-2, 6-octadieny1)-N, N-diethylhydroxylamine[1] to the corresponding alcohols (geraniol, nerol, citronellol) was studied with various transition metal catalysts. Remarkable differences in selectivity were observed between copper or iron group metals and noble metals. With copper or iron group metals, the hydrogenolysis of the aminooxy grop of oourred preferentially over the hydrogenation of the double bonds. With Ni or Co, the subsequent hydrogenation of 2, 3-olefinic bond of the formed alcohols took place accompanying with the hydrogenolysis of [1]. The catalytic activity decreased in the order; Ni >Cu≡ Co> Fe, and the selectivity for the formation of geraniol and nerol decreased in the order; Cu>Fe≡ Ni >Co. The selectivity for the formation of the corresponding alcohols was very high (>95%) with these catalysts. Copper was found to be an excellent catalyst for the selective synthesis of geraniol and nerol. With palladium, ruthenium, rhodium and platinum, the hydrogenation of double bonds occurred preferentially over the hydrogenolysis of the aminoxy group of[1]. After all double bonds had been saturated, the hydrogenolysis occurred to give tetrahydrogeraniol. The selectivity for the formation of tetrahydrogeraniol was very high with these catalysts. The activity of catalysts decreased in the order;

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Synthesis of N, N-diethylnerylamine [2] J by telomerization of isoprene and diethylamine was studied in detail. Instead of the expensive butyllithium catalyst, lithium halide and sodium metal were employed. Lithium diethylamide catalyst was prepared in situ by adding lithium chloride, sodium metal and conjugated diene or fused polycyclic aromatic hydrocarbon as a solubilising reagent of the metal to dietylamine at low temperature. Isoprene was then added to the catalyst solution. [2] was obtained in high yield, i. e. over 80%. The same results were obtained with lithium bromide and iodide. However, the above method was unsuccessful with lithium fluoride. These results are discussed on the basis of free energies of formation of alkali halides.

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The catalytic reduction (5% platinum on carbon carrier and under 1 atm of H2) of sterically hindered aromatic nitro compounds [1 ] (2, 3-dimethylnitrobenzene [1a], 2, 6-dimethylnitrobenzene [1 b], 1-nitronaphthalene [1 c] and 2-methyl-1-nitronaphthalene [1d]) with hydrgen was carried out in sulfuric acid-methanol solution at room temperature. The reaction products were the corresponding amino compounds [ 2] (2, 3-dimethylaniline C2 a], 2, 6-dimethylaniline [ 2] 1-naphthylamine [2]and 2-methyl-1-naphthylamine [ 2 d]) and 4-methoxy1-1amino compounds [ 3 ] (4-methoxy-2, 3-dimethylaniline [3 a], 4-methoxy-2, 6-dimethylaniline [3 b ], 4-methoxy-1-naphthylamine [ 3 c] and 4-methoxy-2-methy1-1-naphthylam ine [3 d]), respectively. [ 3 ] were considered to form in terms of the Bamberger-type rearrangement of arylhydroxylamines which are the intermediates formed in the catalytic reduction of [1] t o [2]. The maximum yields of[3 ]were [3 a] = 64%, [3 b ] =45%, [ 3 c ] = 6 8% and[ 3 d ] =55%, respectively, under the typical reaction conditions. The yield of [3 b ] increased to 72%by the addition of a small amount of dimethyl sulfoxide to a reaction medium.

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The analysis of albumin and r-globulin adsorbed on polyethylene surface was practiced by Fourier transform infrared ATR spectrometry (FTIR-ATR) with amide I band to establish the analytical method for the determination of the protein adsorbed on polymer surface.
1) The calibration curves of albumin and r-globulin were studied with the transmission spectrometry for the each deuterium solutions. The result was made clear that the integrated intensities of amide I bands of albumin and r-globulin per unit weight were same intensity (Fig.2).2) The change of adsorbed quantities of albumin and γ-globulin that was depended on rinsing condition after the contact of protein solutions with polyethylene surfaces was discussed by ATR method combined with the radiochemical analysis of 125I labeled albumin (Tables 1, 2). As results, the quantities were remarkably affected by the condition of the rinsing, and γ-globulin was more strongly adsorbed than albumin on polyethylene surface that had hydrophobic charactor (Table 2).3) The difference between the band countors of transmission and ATR spectra of amide I bands was indicated that the secondary structure of rglobulin was partially altered with the change from solution to adsorbed state. Namely, it was estimated that the secondary structure ofγ-globulin was changed from β-structure to randam structure (Figs.3, 4). It was proved that the FTIR-ATR method was important analytical method for the determination of adsorbed proteins on polymer surfaces.

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In the methanation of CO over Ni catalysts, such reactio ns as the Fischer-Tropsch reaction, shift reaction of CO with H2O formed (C0+H₂O→CO₂+H₂), methanation of CO, formed and disproportionation reaction of CO proceed simultaneously. In order to clear the relationships among these reactions, the methanation of CO and CO, over ex-Al₂O₃ supported Ni catalysts (Ni, Ni-Y, Ni-La, Ni-K) was studied either by a temperature programed reaction (TPR) method or at constant temperature. The experiments were carried out by using a flow type packed bed reactor under atmospheric pressure at 200-550°C. The following results were obtained: 1) Two kinds of ca rbonaceous species on the catalyst surface in the CO-H₂ system were detected by TPR method (Fig.6, 11), while only one of carbonaceous substance was found in the CO₂-H₂ system.2) The carbonaceous species found in the CO₂-H₂ system, which contributed to methanation, was concluded to be the same as one of the species found in the CO-H₂ system, indicating that the methanation of CO₂ proceeds through the formation of CO (Fig.7, 11).3) Another species found in the CO-H₂ system contributed to the Fischer-Tropsch reaction and inhibited the methanation of CO (Fig.1, 3, 9, 10).4) The third species was also found in the CO-H2 system at elevated temperatures. It was concluded that this species stemmed from the disproportionation reaction of CO and contributed to methanation at high temperatures (Fig.5, 9).

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Concentrations of gaseous NO_x and. particulate NO₃^- during (also, before and after) rainfall and those of NO₃^- and NO₂^-in rain water were measured in Kobe area in 1976-1977. The average concentration of N08-during rainfall decreased to about one-half its initial concentration by about 10mm rainfall and to about a quarter just after rainfall. This was explained from the fact that N0₃^- is contained mainly in large particules and is not produced in the air during rainfall since it is a secondary component in a photochemical reaction.
On the other hand, the NO concentration increased during rainfall, while 5-24% of gaseous SO_x was scavenged by rain. Especially, the concentration of NO_x increased by 9-31%, The increase in atmospheric NO concentration by rainfall in heavy automobile area was almost the same as that in non-automobile area. Therefore, it was concluded that this NO increase was due to chemical reactions, rather than meterological-geographical conditions and that, during rainfall, NO was apparently increased by suppression of photochemical NO loss. The increase of the concentration of NO during rainfall, at least partly, seemed to be resulted from the disproportionation reaction of NO₂ with rain water (3 NO₂ + H₂O = 2 HNO₃+ NO) since NO increased with increasing the amount of rainfall.

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The decmposition of ethanol was carried out on the ZnO-W0₃ catalysts. The phase structures of the active catalysts were investigated by powder X-ray diffraction analysis. Both the diffraction intensity of WO, and the activity for dehydration of ethanol decreased with the increase of the content of ZnO in the ZnO-W03 catalysts. The maximum dehydrogenation activity was observed on the catalysts containing 50-60mol% of ZnO, giving the maximum diffraction intensity of ZnWO₄. In spite of the existence of ZnWO₄, the catalysts containing less than 50mol% of ZnO were almost inactive for the dehydrogenation (Fig.1). The role of ZnWO₄ catalyzing the dehydrogenation of ethanol was briefly discussed.

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Pyrolytic precursors of coupling component can be applied to th ermally developable diazonium type systems.α -, β -, and γ-resorcylic acids and 2, 4-dimethy1-3, 5-bis(ethoxycarbonyl)pyrrole were chosen as a precursor. The 1 st order kinetic constants (k) and activation energies in the pyrolytic decomposition reaction of them were obtained according to Niwkirk's method. The temperature at which a tenth amount of γ-resorcylic acid (2, 6-dihydroxybenzoic acid)decomposed corresponded to the thermo-sensitivity of the system. It was concluded that the storage stability of the system could be estimated from the k value of a pyrolytic precursor at room temperature.

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Indene was effectively carboxylated with carbon dioxide under atmospheric pressure in the presence of potassium succinimide at room temperature to afford 1, 3-indenedicarboxylic acid in a considerable yield. Fluorene, acetophenone and cyclohexanone were scarcely carboxylated under these conditions, but carboxylated under increasing carbon dioxide pressure to give the corresponding monocarboxylic acids. Potassium phthalimide did not show the promoting effect so remarkably as potassium succinimide.

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The ozonolysis of indigo was investigated. Indigo[ 1 ] was ozo nated to isatin [ 2 ], from which isatoic anhydride [ 3 ] and a trace amount of “o-benzoylenequinazolone”(indolo[2, 1-b]quinozoline-6, 12-dione) [ 4 ]were produced. When indigo was ozonated in water, isatin and hydrogen peroxide[ 5 ] were produced. The reaction could be explained by the norm al ozonolysis mechanism of C=C double bond of indigo.

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The demethylation of 4', 5, 6, 8-tetramethoxyflavone with anhydrous aluminium chloride in anhydrous acetonitrile quantitatively afforded 5-hydroxy-4', 6, 8-trimethoxyflavone. When the solvent contained a small amount of water, the 5- and 6-methoxyl groups on the flavone were selectively cleaved to give 5, 6-dihydroxy-4', 8-dimethoxyflavone in a good yield. t Studies on Selective O-Alkylation and Dealkylation of Flavonoids. IV.

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