Catalysis of oxidative hydration of propylene was studied with metallic palladium catalysts. Among noble metals palladium was the only element which exhibited a considerable activity. The activity of supported palladium catalyst increased remarkably when impregnated on a support with a large specific surface area. It was shown that this increase was due to the increased dispersion of palladium metal on the support. Particle size of palladium which were measured by X-ray diffraction and carbon monoxide chemisorption distributed from 40 A to 1000 A. Within this range the specific activity increased with decreasing particle size of palladium. During the reaction, large amount of hydrogen was absorbed in palladium particles, forming j9-phase of palladium. This fact indicates that the direct abstraction of hydrogen from propylene by palladium metal took place. Active catalyst was obtained by reduction of palladium salt by hydrogen at high temperature followed by treatment with a mixed gas consisting of steam and air at about 200°C. Reaction was inhibited markedly when the catalyst contained halide ion. The effect, which decreased in the following order: Br^- Cr F-, was considered to be caused by the inhibition of chemisorption of water molecule which is the oxygen donor. Addition of such metal oxides as V205 and WO^2-, which accelerate the oxidation of palladium, increased the catalytic activity.

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Propylene was found to be catalytically oxidized in the presence of alcohols to form allyl ethers on supported palladium metal. While phenol and tertially alcohols produced corresponding allyl ethers selectively, primary and secondary alcohols produced esters and aldehydes, and ketones, respectively, and little ethers were formed. When small amount of alkali compounds was added to the catalysts, the fromation of by-products were suppressed and allyl ethers were formed selectively even from primary and secondary alcohols. Kinetic study showed that the reaction mechanism was similar to that of oxyhydration or oxyacetoxylation of olefins. Thus alcohols and propylene were considered to be activated through formation of alkoxide and ex-allyl intermediates, respectively. Added alkali compounds were thought to act as stabilizers of surface alkoxide complex.

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The influence of structural distortion and microscopically homogeneous mixing etc., given to powder material as mechanochemical effect by mechanical grinding, on velocity of solid state reaction have been studied in the system of BaCO^3-TiO^2-. When BaCO$ and TiO₂ (anatase) were ground independently in air or in vacuum and together in air, remarkable structural changes were not seen on X-ray diffraction patterns. Whereas, when both compounds were mixed and ground for 48 hours in vacuum (10-2 mmHg), the clear change into amorphous phase by distruction and the rapid growth of secondary particles by strong aggregation occurred between both distorted surfaces were shown. However, the formation of BaTiO, was not confirmed. The formation velocities of 13aTiO0 by heating the ground mixture of J3aCO₃ and TiO₂ were studied through the X-ray diffraction patterns at high temperature '(10°C/min) and it was found that the formation of BaTiOs were much accelerated by mechanochemical effect. The formation of BaTiO₃ started at 500°C and ended at 800°C in the case of the mixture ground for 48 hours in vacuum, while it began at 750°C and terminated at 1100°C in the case of the simple mixture without grinding. Arrhenius plots of some ground mixtures were expressed as a bended line, caused on the difference between reactivity of distorted BaCO₃ on the surface and that of undistorted BaCO₃ in the center of a particle.

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Reaction and properties of compounds in NE4N08-KNO^3-K2S0A-(NH, )2SO₄ system were investigated in order to study changes during storage of granular mixed fertilizers containing nitrate and sulfate. Among the samples of Table 1, S-1 tends to degrade while S-2 and F-1 cake. It has been found that a compound "B" NH4, (NO₃) 2SO₄ decomposes into nitrate and sulfate by heating at 80°C or 100°C under the presence of moisture as in the granulation and drying steps of the production (Table 2). During storage at room temperature, the nitrate and sulfate react to form "B" following the equations ( 1 ) and ( 2 ). The reaction ( 1), which col-respond to S-1, causes volume increase by 3.2% with heat emission resulting in the degradation of the granules. Minor volume decrease occurres with the reactions ( 2 ) and ( 3) which correspond to the samples 71 and S-2 respectively. Crystals of "B" formed on the surface of the granules of F-1 and caused the caking. A considerable amount of potassium chloride remained unreacted in the product of S-2; the chloride slowly reacted with ammonium nitrate during storage to form potassium nitrate and ammonium chloride resulting in the caking.

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The phase equilibrium relationship of Y2O^2-TiO^2- system in air was determined in the temperature range between 800°C and 1600°C (Table 1 and Fig.1). In this study, the coprecipitants of Y(111) and Ti(JV) hydroxides were used as the samples for temperature range below 1200°C, while the mixtures of Y208 and TiO^2- powders for higher temperature range. The samples were heated for 2-30 days, quenched in liquid nitrogen and analysed by X-ray diffraction. Four compounds, ce-Y2Ti05, 13-Y2TiO5, Y2Ti207 and fluorite type compound (YsTii_xO^2-x/20x/2) were identified in this system. The a-Y2TiO5 with orthorhombic lattice is stable below 1330°C. The 3-Y2TiO5 with hexagonal lattice, ao= 3.615 A, c0=11.838 A (Table 2), is stable between 1330°C and 1520°C, and at higher temperature it changes into fluorite type cubic solid solution. The solubilization of TiO₂ or Y2O^2- was observed neither a- nor 3-Y2TiO5. Only a small amount of TiO₂ and Y20, are soluble in cubic pyrochlore type (Y2Ti2Q7) below 1400°C, while above 1450°C, Y2O^2- is markedly soluble in it and the produced solid solution gradually changes its structure from pyrochlore to fluorite type. The lowest temperature at which the fluorite phase is stable is 1390°C, when the solution contains 43.7 mol % TiO₂ and its region becomes wide with increase of temperature.

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The liquidus curve of the ZrO^2-Sc2O^2- 'system was measured from the cooling curve of a specimen by the specular reflection method with a heliostat type solar. furnace. Quenched specimens ftom the melt were investigated by X-ray diffraction techniques and a petrographic. microscope. The single phase of -ZrO^2- solid solution having the structures of tetragonal form, rhombohedral form I and rhombohedral form if were obtained by quenching the melt containing 6 to 8 mol % Sc2O^2-, 12 to 14 mol % Sc2O^2- and 16 to 22 mol % Sc2O^2-, respectively, and also the rhombohedral- form II was obtained by firing the specimen containing 18 to 20 mol % Sc2O^2- at 1700°C for 5 hours. The solubility limit of Sc2O^2- in the cubic ZrO^2- solid solution was located at 45 mol % Sc2O^2- and that of Zr' 0, in the Sc2O^2- solid solution was located at 26 mol % Zr0, . It was found that two rhombohedral phases in the quenched specimens from the melt were consisted of twinning 'crystals of various types under the microscopic observation.

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Mixed complexes containing purine bases and glycylglycine or glycine were synthesized. The binding sites of. metal in mixed complexes were. discussed in -terms of infrared-, visible an-d ultraviolet-spectra. Complexes studied are shown below Cu (Ade)2 H₂0, Cu (Adell) Cl2, Cu (AdeH)2Cl2.3/2 H₂0, Cu (CyH)2Cl2, Zn (Cy) Cl120, Zn (IsocyH)2Cl2, Cu (Isocy)2Cl2.2 H₂0, Cu (AdeH) GlyCl H₂0, Cu (Adell) GlyGly.2 H₂0, , Cu (CyH)GiyGlyn H₂0, Cu (Isocyll) GlyGly 2 H₂0.. 7 The study on binding sites of imetal in complexes revealed the evidence that copper combines at N(9) of purine in complexes, with amino, carboxyl and peptide groups. In the case of pyrimidine, copper was conside4=k1 to 'combine with either N(1) or N(3), maintaining the structure of glycylglycinecopper complexes.

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The complex of chromium (0) with 1, 2-dithionato has been prepared. The composition of this complex was confirmed by elemental analysis and the properties of the metal-sulfur bond of the complex were investigated by infrared and far-infrared spectra.. The charge transfer reactions of this complex were examined by electronic spectrum and polarography. From the elemental analysis of this complexes, the composition was found to be [Cr (S₂C_2C(C6I-15), ), ]. The method of preparation is described in this paper. Stretching frequencies of C=S bond in this complex were observed at 1165 and 1O^2-0 cm-', and the bands appeared at 420 and 355 cm-' were assigned to M-S perturb's stretching frequencies from the infrared and far-infrared spectra. Measurement of the magnetic susceptibility revealed that this complex was diamagnetic. To obtain polarogram, the rotating platinum electrode (diameter, 1 mm and rotation number, 600 rpm) was used as a working electrode. The obtained polarogram showed well defined waves (acetonitrile-dichloromethan 1: 1 mixed solvent and (C_2CH₅)4NClO^2-, the supporting electrolyte). Thus, the electrode reaction was found to be [Cr S₂C_2C (C0116) 2 3] e- Cr (S₂C_2C(C8F15)2) 31- (-0.052 V vs. SCE)In terms of the electronic spectra and the results of polarography, this complex was found to be the charge transfer one.

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Hexaisothiocyanatorhenate ion was prepared by the reaction of Rea, - with Sn TO and NH4SCN in hydrochloric acid solution. The complex anion was precipitated by tetraphenylarsonium cation and the salt analyzed for each component. Infrared spectra showed that the thiocyanato ligand bonded with the central rhenium atom in terms of the nitrogen atom in thiocyanic group and the same would be true for two intermediate complexes. Only the greenish yellow intermediate complex had a spectrum of Re=0 linkage at 960 cm. formation of the complex ion would occur in terms of the following series of reactions:As the usual photometric determination of rhenium is based on the optical absorption of the intermediate complex formed in equation ( 2 ), the rapid fading of color occurred in this determination would show an unstability of this intermediate complex.

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There are many archaeological amber objects found in Europe, and some attempts have been made to determine the provenance, of these ambers. In Japan, a few beads have been excavated from old tomb, but the provenances of these ambers are not known. In the present work, the authors investigated several methods of determination of provenance of Japanese amber artifacts, using scientific techniques such as elementary analyses, infrared spectroscopy and measurement of the melting point. In the study, the geological standard samples, offerd by some museums and laboratories were used. They were 'collected from main amber sources such as Kuji, Choshi, Mizunami and Kobe in Japan and Fushun in China. Other samples of unknown origin were; those from Todaijiyama Old Tomb in Nara prefecture and those from Nagaike Old Tomb in Kyoto prefecture. The results of elementary analyses are the following, in the archaeological samples, C:: 0 3034: 4 and in the geological standard samples, C: H: 0=25-484: 52--, 3O^2-: 4; here it is interesting to see that the archaeological samples show much less variation in composition with the geological samples. Each infrared spectrum of these ambers shows a characteristic pattern depending upon its provenance; our samples vary considerably in color and were obtained in different ways, but nevertheless, the spectra of amber from the same provenance show the same pattern. Therefore the authors strongly suggest that the best means of determination of the provenance of amber artifacts is to record the full spectrum of infrared absorption and to compare with that of standard samples. The archaeological amber samples from Todaijiyama Old Tomb and Nagaike Old Tomb were, found, to have the same provenance: Kuji in Iwate prefecture. From there results, it is concluded that there were trade links between Kinki district 'and Tohoku district the sixth century A. D.

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Solvent extraction of tin (N)-Pyrocatechol Violet chelate with tridodecylethylammonium bromide (TDEA) in xylene has been studied by spectrophotometric method. The tin (N)-PVTDEA complex can be extracted into organic solvents such as, benzene, xylene, nitrobenzene, carbontetrachloride, chloroform, and n-buthyl acetate, but not into n-butanol. The complex, extracted into organic layer, has an absorption maximum at 581 nm. When a solution containing tin (N) and PV, the pH of which has been adjusted to 3.6, is shaken with TDEA-xylene for 10 min, the maximum extraction of the ternary complex is obtained. The distribution ratio of the complex is 60.5. The molar absorption coefficient of the complex is 7.3x 10' cm^-1 o1-14 at 581 nm. Composition of the complex is estimated to be tin: PV: TDEA=1: 2: 2 by the continuous variation method. Consequently, it may be assumed that the ternary complex is an ion association system such as

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Ring-opening polymerization of monosubstituted ethylene oxides Cl J results in formation of polyether polyols with either primary C 2or secondary terminal hydroxyl group C3D, depen- ding on the mode of C-O-C bond cleavage.This end-group structure is significant, since it is closely related to the reactivity of polyols and affects the properties of polyurethane resin prepared from those polyols and diisocyanates. The application of NMR technique to the analysis of primary hydroxyl groups in polyol are studied in this paper when the hydroxyl is converted into urethane, and it proves to be a simple and convenient method. We also employed the time-average technique of NMR with a Mnemotron Computer of Average Transient to analysis of terminal unsaturation in polyols. It was revealed that poly (oxypropylene)glycol prepared by KOH catalyst contains substan- tially on or a small amount of primary hydroxyl, but more than 40% primary hydroxyl is found in polyether which was prepared by BF, --catalyzed, polymerization, and no matter what the polymerization catalyst is the amount of terminal unsaturation in the resultant polyethers increases by the molecular weight increase of polyether.

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The thermal decomposition of hydrazodicarbonamide in solid state has been studied. Thermal characteristics were examined by DTA and TG. The decomposition products were identified and estimated by pyrolysis gas chromatography, infrared and mass spectrometries. The decomposition proceeds initially in the solid phase and then in melts as the products increase during the decomposition. Overall reaction was endothermic. Main products were urazole and ammonia. Among others were small amount of nitrogen, isocyanic acid, carbon monoxide, biuret, semicarbazide, urea and negligible amounts of ammonium isocyanate. The kinetics of decomposition was evaluated by the gas evolution method over the range between 238°C and 248°C. The reaction was autocatalytic and its process was expressed by Prout-Tompkins equation. The apparent activation energy and the pre-exponential factor were 40.0 kcal/mol and 3.3 X 10" sec-1, respectively. On the bases of these results, following reaction mechanism has been proposed; the production of urazole by ammonium release from substrate and the subsequent reaction involving formed radicals.

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Oligomerization of butadiene was carried out in the presence of tetrahydrofuran at 40°C for 16 hr using Co compound-Alkali metal catalyst to produce a linear dimer 21 by 73°C/100 mmHg, in 51% yield. C_2C absorbed 3 mol-equivalent H, to give 3-methylheptane but was not identical with 5-methylhepta-1, 3, 6-triene, C 1 obtained by the reaction catalyzed by Co compound-A1R3. IR and NMR spectra of C 2 J and maleic anhydride adduct of C 2 J showed that C_2C was 3-methylhepta-1-trans-3-trans-5-triene. Other products were C 1, octa-1, 3, 6- triene, octa-2, 4, 6-triene and a trace of unknown dimer. By the fact that C 1 J and C 2 were produced equally at the first step of the dimerization reaction, but C 2 J finally became the main product and that C 1 J was isomerized to C 2 J by this catalyst, it was assumed that C 1 J was the initial product and then isomerized to C 2 under the reaction conditions. Octa-1, 3, 6-triene and 2, 6-dimethylocta-1, 3, 6-triene were also isomerized to octa-2, 4, 6- triene and 2, 6-dimethylocta-2, 4, 6-triene by this catalyst.

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The dimerization of isoprene was carried out by using the catalyst consisting of RhCl3 H₂0, CH₂COONa, and PPh, in ethanol at 30°C for 20 hr. Two products, C, 0H18 ([1]; by 61°C/40 mmHg, [2]; by 70°C/40 mmHg), were separated by gas chromatography. IR, NMR, and Mass spectra revealed that Cl J was presumably a mixture of 2, 3, 5-trimethylhepta-1, 5-diene C/ a and 2, 3, 6-trimethylhepta-1, 5-diene [1b], and that [2] was 2, 6-dimethylocta-2, 6-diene. The studies on the reaction products (Table 5) show that the amount of hydrogen used to hydrogenate the starting material was found to be nearly equal to that dehydrogenated from the starting material. Ethanol is considered to be dehydrogenated to give acetaldehyde, ethyl acetate, while isoprene and isoprene dimers are hydrogenated over Rh catalyst.

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The reactions of 1-halooctanes with ethylene oxide in N, N-dimethylacetamide in the presence of zinc halide were studied. Ethylene oxide was inserted into carbon-halogen bond of 1-halooctanes to form the 2-haloethoxy derivatives.1-Octyl acetate was formed as a byproduct. The reaction was carried out under various conditions in order to find an optimum condition. The yield of the insertion product was not influenced by the reaction temperature in the range of 110°C to 150°C and by the amount of catalyst. On the other hand, the amount of the acetate increased considerably with the rise of temperature and also with increasing ratio of solvent or catalyst to 1-bromooctane.2-Bromoethoxy derivative was obtained at the maximum yield, when the equimolar amount of solvent was used to 1-bromooctane.1-Octyl acetate was considered to be formed by the reaction of 1-halooctanes with N, Ndimethylacetamide. N, N-Dimethylformamide, N-methylpyrrolidone and hexamethylphosphortriamide were also found to be good solvents for the insertion reaction.

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The reactions of diethyl dibromomalonate [1] and 1, 3-diphenyl-2, 2-dibromopropane-1, 3- dione [13] with various sodium alkoxides were studied. The reaction of [1] with sodium ethoxide gave diethyl diethoxymalonate, diethyl carbonate [2], bromoform [3], ethyl dibromoacetate [4] and diethyl bromomalonate [5] D as main products. The reaction of [1] with the disodium alkoxides of 1, 2-diols gave the carbonic esters of the 1, 2-diols, [2], [3], [4] and [5] as main products. In the reaction of [13] with sodium ethoxide, ethyl benzoate, mandelic acid [15] and benzoic acid [16] were produced as main products. Finally, in the reaction of [13] with the disodium alkoxide of a 1, 2-dial, di- and mono-benzoyl esters of the 1, 2-diol, [15] and [16] were produced as main products. From these results, it is concluded that in the reactions of [1] and [13] with alkoxide ions, the main reaction is an attack of alkoxide ions to the carbonyl carbon of the substrates, and the substitution of bromine by alkoxide ions occurs as a side reaction.

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A kinetic study on the thermal rearrangement of 1-methoxy-bicyclo[3.2. O]hepta-3, 6-dien-2- ones [1] to give 3-methoxy isomers [2], has been made.5-Isopropyl-l-methoxy [15] and 3, 7-dimethy1-5-isopropyl-1-methoxybicyclo[3, 2, 0]hepta-3, 6-dien-2-ones [18] were synthesized by irradiation of the corresponding 2-methoxytropones [13] and [17]. The kinetic study was carried out in the temperature range from 140°C to 167°C for Cl 5J and from 175°C to 200°C for [18]. The rate of depletion of the starting materials was determined by measuring the proton area of the methoxy signal of [15] and [18] in their NMR spectra (see Table 1). Arrhenius plots for their earrangement are shown in Fig.2 to give the activation parameters in Table 2. There is little difference in the values of activation energy and entropy of activation between [15], [18] and 4-isopropyl isomer [1c]. From our observation, it seems difficult to discriminate between two previously proposed reaction paths, an antara-antara Cope rearrangement and a cancerted process which proceed vii cis, trans, cis-cycloheptatriene inter- mediate [11] In addition, another possible path in which the rearrangement takes place via a more preferred conformer of [11] such as [21] as the transition state is suggested.

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It was reported that every mono-alkali metal hydroxybenzoate turned into the corresponding di-alkali benzoate accroding to Eq. ( 1 ) at 360°C, except monopotassium salicylate. However, it has now been clarified by the microthermal and UV analyses that disodium phydroxybenzoate (P0B-Na₂) formed from Eq. ( 1 ) rearranges into salicylic acid (SA) and 4- hydroxyisophthalic acid (4-OIP) at above 300°C in CO, atmosphere and at still higher temperature in N2. The DTA curve of this rearrangement consists of three peaks. Two endothermic peaks are attributed to the formation of 4-01P and the evolution of gases from the thermal decomposi- tion of POB-Na₂, and one exothermic peak is due to the formation of SA. The formation of 4-OIP is accelerated with heating and the increase in CO, pressure. The reaction of Eq. ( 2 ) occurs in N, atmospheres, while the reaction of Eq. ( 3 ) takes place under CO, . The reaction of 4-0IP-Na3 with phenol and sodium phenolate also takes place at elevated pressures.

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The reaction of aromatic sulfonates (sodium benzene-, toluene- and naphthalenesulfonates) with sodium amide in monoalkylamines (R=Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, and cycloHexyl) has been studied. By the reaction of aromatic sulfonates with three-fold moles of sodium amide in excess monoalkylamines at 140-170°C, alkylarylamines and aromatic primary amines were obtained in the ratios of 8: 2-9: 1. The yields of alkylarylamines were about 60-90%. Dialkylamines were alsobtained by use of excess amounts of sodium amide at high temperatures. The effects of temperature, amounts of sodium amide and monoalkylamines, and kinds of alkyl groups in monoalkylamines were examined. This reaction seems to proceed as shown in equations ( 1 ) ( 4 ). Alkylarylamines were prepared with high selectivity and in good yields by means of two-step method which consists of ( 1 ) sodation of monoalkylamines at low temperatures below 110°C and ( 2 ) alkylamination of aromatic sulfonates at high temperatures between 140°C and 160°C.

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The orientation in the Friedel-Crafts benzoylation of 2- and 3-methyldibenzofurans was studied. The reaction of 2-methyldibenzofuran with benzoyl chloride and anhydrous aluminum chloride (mole ratio, 1: 1.5: 1.5) in nitrobenzene at 20°C for 1 hr, gave 8-benzoyl-, 7-benzoyl-, and 3-benzoyl-2-methyldidenzofurans in yields of 51.2, 3.0, and 3.0%, respectively. In the case of 3-methyldibenzofuran, 2-benzoyl-, 8-benzoyl-, and 7-benzoyl-3-methyldibenzofurans were obtained in yields of 56.5, 2.6, and 3.2%, respectively, under the same condition. The structures of these compounds were assigned as such by Comparison with authentic samples. The solvent effect on the reaction of 3-methyldibenzofuran was studied, and it was found that the selective substitution on the 2-position occurred in tetrachloroethane as solvent.

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Reactions of hafnium tetraisopropoxide or its isopropylate with acetyl chloride and hydrogen chloride have been investigated and the following new compounds prepared: HfCl(0'Pr), PrOH; HfC4 (01Pr) 2 PrOH; HfCl3 (OtPr) iPrOH; and HfCl4 'PrOH. Both HfCl2 (01Pr) is PrOH and HfCl3 (OiPr) PrOH reacted with N, N-dimethylformamide (DMF) to give the corresponding 1: 1 adducts, HfCl2 (Cer) 2 MF and HfCl3 (OtPr) MF. On the other hand, HfCl(0Tr), PrOH did not react with DMF in the normal way, but underwent disproportionation to give rise to the formation of an adduct of the formula, HfCl2 (0Tr) 2MF. HfCl4.2 PrOH also reacts with DMF to give HfCl4 DMF. The infrared spectra of the DMF and adducts were measured; the carbonyl stretching frequency was shown to be lowered in the spectra of the adducts.

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Grignard reactions with 1, 2-epoxyoctane have been carried out in diethyl ether or tetrahydrofuran. The reaction mechanism was proposed by investigations of NMR spectrum in early reaction stage, kinetics and product distributions. Although the reaction mechanism was not simply defined theoretically because of existence of participations of several compounds (e. g. ROMgX-form etc. ), the reactions with dimeric and monomeric Grignard reagents were observed to follow a second-order and third-order rate equations, respectively, at conversion of 1, 2-epoxyoctane below 38 50%. These results were supported also by differences in product distributions. Thus, it was considered that the degree of association of the Grignard reagent (monomeric or dimeric) controlled the reaction processes. The dimeric reagent gave mainly " normal- " and " abnormal " ring cleavage products: 1- substituted-2-octanol and 2-substituted-1-octanol, while the monomeric one gave mainly " rearranged products ": 1-substituted-1-octanol and 2-substituted-2-octanol. The side reaction was also investigated which produced substituted octanols via halohydrin from 1, 2-epoxyoctane. In a case of even monomeric Grignard reagent, octanol distributions varied as the concentration of the reagent was changed. So it was found that mechanism was also modified by the concentration in this reaction.

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The relationships between physico-chemical properties of various organic compound solutions (Table 1) and detergencies or physico-chemical properties of the detergents (sodium linear alkylbenzene sulfonate, 20%; sodium tripolyphosphate (STPP) or an organic compound (a builder), 20%; sodium silicate, 5%; sodium carbonate, 3%; sodium sulfate, 42%; moisture, 10%) were studied in order to seek the satisfactory replacements for STPP which is known as the most important and the useful detergent builder. The detergents were examined for solubilization capacity (X1), the critical micelle concentration (X2), pH (X3), dispersion capacity (X, ), calcium ion sequestration capacity (X5), buffer index (X, ) and detergencies (D) at various laundering conditions. Builders were also examined for xs, x4, xs and x6, where the notation, x for a builder is referred to the corresponding X for the detergent. It was found the X1, X1, X3 and X, were not affected by the corresponding x, respectively (Table 2). On the other hand, X5=ax5-1-b (Fig.2) and X8=cx, -Fd (Fig.3), where a, b, c and d are constants. Thus, the relationships, D at 0.1% and 3.5°DH cc x, (Fig.4) and D at 0.1% and 3.5°DH cc "Ixis (Fig.5), indicate that the physico-chemical properties required for builders as replacements for STPP are calcium ion sequestration capacity and buffer index. It was clarified by the computer cluster analysis that D at various laundering conditions also relates to x5 and and that chelating agents and polyelectrolytes are better replacements for STPP than polymeric non-electrolytes and lower molecular organic salts (Figs.6 and 7).

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A series of nonionic surfactants (3 F) having partially fluorinated hydrophobe, n CY, (CH, ), , .0 (C_2C11, 0)H (m: 5, 7 and 11), were prepared by acid-catalyzed polyaddition of ethylene oxide (EO) to co-perfluoropropylalkanols. Some physicochemical properties of 3 F were examined in comparison with those of n-alkanol-EO (HC) and co-trimethylsilylalkanol-E0 (1 Si) acidcatalyzed adducts.1 Cloud point of 3 F was significantly lower than those of HC and 1 Si containing the comparable chain length of polyoxyethylene (see Fig.1).2 While CMC value of 3 F was remarkably lower than that of HC for the lowest member, the value was close to those of HC and 1 Si as the member increased (see Fig.3).3 Ability of lowering aqueous surface tension increased in the order HC1 Si3 F and increased with decreasing m among 3 F series (see Fig.2).4 Wetting efficiency (canvass disc test) increased in the order HC1 Si3 F (see Fig.4). The result, together with that previously described for co-perfluoropropylalkanesulfonates2, was discussed in terms of the orientation and packing state of the partially fluorinated surfactants adsorbed on aqueous surface and associated into micelle.

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1-Aminonaphthalene was obtained by the reduction of 1-nitronaphthalene with sodium sulfide in very low yield. To clarify the reason for the low yield of the amine, the residual byproducts were analysed with tic. It was found that bis-[1-aminonaphthyl-( 2 )]disulfide was a constituent of the residue and the others were supposed to be its polysulfide homologs, and these polysulfides were converted to bis-[1-aminonaphthyl- ( 2 ) ]disulfide as the reaction proce- eded. The behavior of the separated residue in sodium sulfide solution implies that these polysulfide amines existed as 1-aminothionaphthol- ( 2) in the solution. The yield of these byproducts was low on the reduction with sodium polysulfide. From the results of these studies, these by-products are seemed to be formed by nucleophilic substitution reaction of SH- or Sz2- on 1-nitronaphthalene.

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The reaction of bicyclic terpene alcohols, nopol(2-pinene-10-methanol) Cl J and isoborneol C 2, with paraformaldehyde (PFA) in the presence of acetic anhydride and sodium acetate was investigated, and three novel adducts were isolated by distillation and gas chromatography, respectively. Their structures were assigned on the basis of transesterification, their physical constants, IR, NMR and mass spectra as follows; nopyl acetoacetate C/ a, nopyl dioxymethyleneacetoacetate C/ b, nopyl trioxymethyleneacetoacetate 11 cD, isobornyl acetoacetate C_2C a, isobornyl dioxymethyleneacetoacetate C_2C b and isobornyltrioxymethyleneacetoacetate C_2C c. The reaction of PFA with C 1 yields 11 a, C/ bp and CI c in a ratio of 71: 20: 9, and the reaction of PFA with C_2C yields C_2C a, C_2C b and C_2C c in a ratio of 80: 15: 5.

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Some organic compounds fluorescence intensely when dissolved in less-polar solvents or bound to proteins but have extremely low fluorescence intensity in aqueous solutions. When the fluorescence quantum yield, emission maximum, or emission band width are related to the polarity of the environment around the fluorescent species, these compounds can serve as probes for hydrophobic sites in proteins. To provide new types of the effective hydrophobic probe for investigation of hydrophobic regions in proteins and micelle of surfactants, the fluorescence of ten 4-methyl-7-substituted aminocoumarin in a variety of solvents has been measured. When the amino groups on the coumarin are anilino, diethylamino, and morphorino, the fluorescence of the coumarin derivatives is varied significantly with polarity of solvents and hence the compounds seem to be applicable as the hydrophobic probe. On the other hand, the primary and secondary alkyl aminocoumarins are inadequate for the hydrophobic probe. Among the coumarin derivatives 4-methyl-7-anilino coumarin (MAC) has extremely low fluorescence in aqueous solutions. In less-polar solvents, however, the fluorescence increases. The increase is remarkable especially in solvents whose dielectric constant is below twenty. Furthermore, the wavenumber of emission maximum changes as a function of polarity of the solvents. Therefore the fluorescence characteristics of MAC make this compound a new type of useful reagent for the hydrophobic probe. The fluorescence of MAC was measured in aqueous solutions of human and bovine serum albumin (HSA, BSA respectively) and the results of the fluorescence measurement were referred to the results of the above experiments. The binding sites of HSA and BSA for MAC are estimated to have such high hydrophobicity as 7-10 and 6-.9, respectively, in units of dielectric constant.

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It was found that among 7, 7, 8, 8-tetracyanoquinodimethane (CQ) salts of polycation containing piperazium ring in their main chains, whose structures are shown by the following formula, complex salts of PiX-CQ, Pi 3-CQ and Pi 5-CQ had vary low resistivity and whose p values were 22, 30, 60 SZm, respectively. From the correlation of the distances between ionic sites in polycation chain with their electrical conductivity, it was assumed that piperadinium ring made a contribution to the arrangement of neutral CQ molecule (CQ°) and CQ anion radical molecule (CQ') toward polycation matrix, and affected the mobility of conductive electron. This phenomenon was observed until the number of methylene groups within ionic sites was 5-6, but it vanished when the number was more than 8.

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The sorption process of methyl methacrylate (MMA) (Hydroxymethyl) acrylamide (MAM) 'copolymer (MMA/MAM= O.95/0.05 in mole ratio) was followed up by the decrease in Cpotential, estimated from the streaming potential, with time. The activation energies of sorption obtained from the Arrhenius plot of the rate constants (Fig.2) were z 1Ef= 6.6 kcal/mol for T Ts, and 4. q=6.83 kcal/mol for T Tg where TE, is the glass transition point of the copolymer (46.2C). Clearly, the sorption occurred below Tg proceeds as a strong hydration process due to the large negative value of zlEf. From the Arrhenius plot of the diffusion constants, obtained directly from sorption experiments, 4E (T Tg) was found to be 1.55 kcal/mol (Fig.4) and the amounts of sorption were 5 to 10 times as large as those of ordinary hydrophobic polymers (Fig.3). Large amounts of sorption and small positive values of z 1and 4E are seemingly due to the plasticization of water.

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On the basis of Smith's theory, the continuous emulsion polymerization of styrene was studied; monomer conversion, number of polymer particles and degree of polymerization in nonsteady stata region could be quantitatively explained. The validity of the proposed model was tested by the experiments conducted in a single stirred tank reactor at 60°C. The degree of polymerization in nonsteady state ragion could be explained in terms of the moment method proposed by Katz. The distribution function of degree of polymerization could also be explained in terms of j'-model proposed by Imoto.

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In order to study the electrostatic effect of polymer complex on its reactivity, the rate constants and the activation parameters for the electron-transfer reactions of cis-[Co (en)2L Cl]. Cl2 were determined L=QPVP: partially-quaternized-poly (4-vinylpyridine) by benzylchloride; PVP: poly (4-vinylpyridine); Py: pyridine. The reduction rates of Co 110-polymer complexes by ferrous sulfate were almost the same as that of Co (III) -Py complex (Table 2). The rate constants of the reduction by Fe(11)EDTA2- decreased in the following order: Co (M)-QPVP Co (BI)-PVPCo 10-Py (Table 3). An increase in degree of coordination and in that of quaternization brought about an increase in reactivity of QPVP complex (Fig.1). The acceleration for polymer complex was found to be due to a decrease in activation enthalpy and an increase in activation entropy. These results were interpreted in terms of the electrostatic attraction between FeEDTA2- and polymer metal complex, viz., a polycation. For QPVP complex the electrostatic effect was considered to be more pronounced by pyridinium cation situated on QPVP chain.

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Water-soluble cationic polymers were prepared by the amination of the nitrile grougs in polyacrylontrile (PAN) in the absence of catalyst at high temperature. In order to see the cationic flocculation effect of these polymers he kaolin suspension was used. The flocculation effect was studied by observing the supernatant suspension concentration in jar test, the sedimentation rate and sedimentation volume by the use of test tube. The reaction temperature, reaction time, polymer concentration and amine concentration in the amination of PAN with polyethylenepolyamine influenced greatly the flocculation effect of the cationic polymers obtained. The best flocculation effect was obtained when PAN (O.5 g) was treated with about 1-3 mol polyethylenepolyamine (to nitrile grougs) in dimethylfolmamide (40-60 ml) at 130---150°C for 3-5 hours. It was estimated by the results of IR-spectra and elemental analyses that cationic polymers obtained had primary amide, secondary amide, imidazorine ring and residual nitrile groups. Cationic polymers which were obtained by the amination with diethylentriamine, triethylenetetramine or tetraethylenepentamine under most suitable condition gave the same flocculation effect. The maximum rate of sedimentation was 7.2 cm/min, when the amount of polymers was 0.016% of kaolin.

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Pyrolysis of r-ray irradiated poly (tetrafluorethylene) powder (PTFE) has been studied at temperatures from 200°C to 390°C in the presence of air. By heating, the weight decrease of the powder and the formation of gaseous CO₂ and CO were observed. The weight decrease of the powder increased with total dose of irradiation. r-Ray irradiated PTFE decomposed partly by heating above 250°C. By heating at 300°C, the degree of weight decrease increased with heating time and reached a constant value. While at 390°C, successive decomposition was observed. The melting point of PTFE was depressed by irradiation, while it did not change by heating. No change of IR spectrum of PTFE by irradiation and/or heating was observed. In the irradiated PTFE, stable peroxy radical was observed by ESR measurement at room temperature, but decreased by heating at 150°C and disappeared at 250°C. Upon preheating the irradiated PTFE above 200°C, the weight decrease of the powder at 390°C decreased remarkably. On the basis of these results, mechanisms of the pyrolysis and thermo-stabilization of the irradiated PTFE were discussed.

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Acrylamide (AM) was graft-copolymerized onto hydroxyethyl cellulose (HEC) whose molecular chains are rigid and whose extension in an aqueous solution is large. The HEC-AM graft copolymers were isolated from the polymerization products in terms of fractional precipitation. The flocculation ability of the graft copolymers toward kaolinite suspensions and the intrinsic viscosity C which is concerned with its extension in an aqueous solution were compared with those of polyacrylamide (PAM) which are now widely used as the macromolecular flocculants. The following results were obtained: 1 The flocculation ability of the graft copolymers was scarcely affected by a small number of the grafted PAM per one HEC molecule.2 The influence of pH-values and temperature on the flocculation was less with the graft copolymers than with PAM.3 The flocculation ability of the graft copoylmers increased with increasing molecular weight of the grafted PAM and more depended on the molecular weight than on the degree of grafting.4 When the molecular weight of the grafted PAM was nearly equal to that of PAM, the flocculation ability of the copolymers was nearly equal to or superior to that of PAM.5 As 77 3-values of the graft copolymers were larger than those of PAM, the extension of the copolymers in an aqueous solution _would be larger than that of PAM, when the molecular weight (Ma) of the cdpolymers was equal to that pf PAM. This would facilitate the bridging of kaolin particles by the flocculants and would he one of the reason why the flocculation ability of the graft copolymers was superior to that of PAM.

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A series of higher aminimides (I) with a general formula, RCH(OH)CHA (Me01^TCOR' (R: H, Cl --Cl4, - 14, R': ClCl5), were conveniently prepared in nearly quantitative yields by the Slagel method (Ref.8). Some properties of I were examined and compared with those of N, N, N-alkyldimethylamine-acylimides 1I) (Ref.3) and some conventional surfactants, . Melting points and Krafft points of I were slightly higher than those of II. However, I was generally more soluble in water at room temperature and also had the greater CMC value than II. Most of I prepared had a cloud point similar to that observed for polyglycol type nonionics. In analogy with IL the aqueous behavior of I was nonionics-like in many other aspects. I was remarkably surface active (see Table 3); for example, I containing R of n-C, and R' of n-C7 had the lowest aqueous surface tension of 22-23 dynes/cm at 25°C. I exhibited excellent wetting, emulsifying efficiency and high ability to solubilize an aromatic hydrocarbon. In thermal and photochemical stabilities, I was incomparably superior to II.

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The equlibrium and rate of adsorption of thirteen mono-substituted benzoic acids (Table 2) on granular activated carbons (Table 1) in aqueous solution were examined. The adsorption isotherms were conformed to the Freundlich equation (Figs.1'-'4, Table 3). Independently of the kinds of the carbon, Traube's rule was applicable to the adsorption of the m-substituted benzoic acids except isophthalic acid. The adsorption capacity regularly increased with decrease in the solubilities (Figs.1, 3). In the case of the o-substituted benzoic acid, Traube's rule was not applicable, and the adsorption 'capacity decreased in the following order of the substituents (Figs.2, 4). NH₂H Cl-18Cl OHNO₂ COOH at CR40.01-0.1 ClCH84HNH₂OHNO₂C0OH at CR40.1-4where CR is the ratio of the equilibrium concentration to the saturated concentration. It is likely that the adsorptivities of the o-substituted compounds are affected complicatedly by the ortho effects. In all cases, it seems that the carbon surface does not directly interact with the functional groups of the adsorbates, but with the aromatic ring. The adsorption rates were estimated by the intraparticle diffusivities, which little varied with the kinds of adsorbates at low concentrations. But in high concentrations, the diffusivities of the o-substituted compounds exceeded those of the m-substituted ones. It is suggested that the effective molecular radii of the o-substituted benzoic acids are smaller than those of m-substituted ones in aqueous solution.

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Owing to the similarity of the chemical properties, sulfur usually contains a small amount of selenium as an impurity. We attempted to concentrate selenium in sulfur by zone melting. Since the phase diagram reported by Ringer shows that the equilibrium distribution coefficient of selenium in sulfur is smaller than unity at the concentration of selenium up to about 60%, it is expected that selenium migrates with the molten zone. The experiments were carried out with sulfur samples containing various amounts of selenium. After passage of 20-40 zones at the travel rate of 0.73 cm/hr, no difference in the selenium concentration determined by Cheng's method was observed in the samples. For the purpose of making clear the reason why no segregation occured, the effective distribution coefficient at the selenium concentration of 1% was determined by Sue's method to be 1.15, which is unfavorable for the separation of selenium from sulfur.

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Hydrogenation of ethylene was investigated over a Pd-on-SiO^2-Al2O^2- catalyst. With repeated reactions, the apparent activation energy increased from 3 to 5 kcal/mol while the catalytic activity gradually decreased to a low steady value. For the catalyst with the steady activity, the rate of hydrogenasion was first order in hydrogen pressure and slightly negative order in ethylene. The catalyst pretreated with ethylene exhibited the low steady activity from the beginning of the reaction, but the activity of this ethylene-pretreated catalyst was recovered by an oxygen treatment to a level of the initial activity of the untreated catalyst. It is very likely that the irreversible adsorption of ethylene was responsible for the gradual, decrease in the catalytic activity during the repeated reactions.

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The interaction of lanthanum (111) ion with gelatin was studied by means of equilibrium dialysis and electrophoresis. Carboxyl groups of gelatin were blocked chemically by methylation and amino groups by acetylation, respectively. Fquilibrium dialyses of original and modified gelatins against lantha- num (111) ion at pH 6.0 showed that lanthanum (ll) ion was bound to carboxylate group of gelatin. Electrophoreses of original and modified gelatins with added lanthanum OH ion suggested that lanthanum (J11) ion was bound mainly to carboxylate groups of original and acetylated gelatins. An approximate value of the association constant, log km, between lantha- num (III) ion and carboxylate group in O.O^2-5 mol// acetate buffer solution was calculated to be 2.6 by assuming one to one interaction. The polarography of lead (II) ion in gelatin solutin containing lanthanum 010 ion showed that lanthanum 010 ion replaced lead 01 ion bound to gelatin. Since the latter ion is known to combine with carboxylate group (log km=1.6-2.4), this observation confirmed the above results.

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The arylaminations of aromatic sulfonates (sodium mono- or disulfonate of benzene, toluene, naphthalene and sodium metanilate) with sodium amide in aromatic primary amines (aniline, p-toluidine, 1-naphthylamine, p-anisidine and p-phenetidine) were studied. Corresponding diarylamines were obtained in good yields by the reaction of aromatic sulfonates with three-fold over moles of sodium amide in aromatic primary amines at temperatures of 185°C to 230°C. These aminations seem to be expressed by the equations ( 1 ) and ( 2 ). In these arylaminations, the formation of aromatic primary amines by the reaction of aromatic sulfonates with sodium amide was not observed.

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The pyrolysis of iron phthalocyanine (Fe-Pc) was studied in Ar gas up to 1000°C. The pyrolysis pattern of Fe-Pc was analogous to that of Co-Pc, but Fe-Pc was less thermo-stable than Co-Pc. On DTA, Fe-Pc showed endo-thermic reactions at 615, 645 and 690°C, and exothermic reaction at 770°C. In these, the endo-thermic reaction at 690°C was a new appearance that was not observed on Cu-Pc, Co-Pc or Ni-Pc, but the cause of this endo-thermic reaction was not clear. It seems that the iron in Fe-Pc promotes the growth of carbon structures of pyrolyzed Fe-Pc.

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The photocurrents of 3 H-phenothiazine-3-one C/ a, 3 H-phenoxazine-3-one Cl 151 2-hydroxyphenazine C/ cp, 5 H-benzo[ a ]phenothiazine-5-one C_2C a, 5 H-benzo[ a ]phenoxazine-5-one C_2C ID, and 5-hydroxybenzo a jphenazine C_2C c are measured by illuminating their "surface-type" cells with a white light under nitrogen at room temperature (Table 1). In all cases, the relationship between the photocurrents (ip) and the light intensities (I) is expressed by the following equation; ipoc/°. ".9 (Fig.1). The magnitude of the photocurrents becomes lower in the following order; Cl a Cl b C_2C a C_2C bp C/ cp C_2C cj. The change of the hetero, atom from S to 0 affects scarcely the magnitude of the photocurrents. The existence of oxygen in the conductive system results in the lowering of the photocurrents.

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The present investigation was undertaken, as a part of the programme concerning with the renovation of kraft pulp waste water, to remove colored constituents (mainly lignin) in the coustic extraction liquor of bleached pulp by lime treatment and to make clear the effect of activated sludge treatment on lime treatment. Lime treatment of the caustic extraction liquor resulted in about 70% reduction in lignin. The lignin removal by lime treatment of the effluent treated with activated sludge became about 10% higher than that of untreated one. The COD components, showing no absorption at 280 nm, were almost removed by activated sludge treatment. Addition of seed crystals to the carbonation tank was effective for decreasing the SS in the effluent from the settling tank of calcium carbonate and the SS became about 80 ppm when the original SS in the carbonation tank was more than 15000.

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Krypton was separated from its mixture with nitrogen at one atmospheric pressure by use of a thermal diffusion column of the hot-wire type and of an effective length of one meter. When the inner diameters (I) of the column were 15 and 10 mm, the time required to reach the equilibrium state was 10-15 min at a wire temperature of 400°C and an initial krypton concentration of about 50%. Degrees of separation at this state defined by q=[C(1 C)]/ EC' (1 C') were 125 and 180 when 0=15 and 10 mm, where C and C' denote the krypton concentrations at the bottom and top of the column, respectively. These qo values are very large and the corresponding equilibrium times very short in comparison to the cases of separa- tion between isotopic molecules, but this result can be explained in terms of the theory of the column.

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