Intermetallic compounds of TiFe, TiCo, Ti2Ni, TiNi, Ti2Cu, TiCu and TiCu, react directly with hydrogen to form the hydrides. The relative partial molar enthalpies of hydrogen for TiFeHo., and TiCoH05 determined from the dissociation isotherms (Figs.2 and 3) are -37 kcalfmol and -3.7 kcal/mol, respectively. Thus, the hydride of TiCo is more stable than that of TiFe. Like TiFeH, , a, stoichiometric compound of TiCoH, has a tetragonal structure with a =6.14 A, c=9.06 A. Below 270°C TiNi forms an interstitial hydride TiNiH"which is more stable than those of TiFe and TiCo, but at about 500°C it decomposes into TiFI, and TiNi3 at the hydrogen pressure of 130 atm. Similar decomposition reaction is also observed when Ti2Ni, Ti2Cu, TiCu and TiCu3 are hydrided. Ti2Cu, TiCu and TiCu3 decompose simply into TiFI, and Cu.

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Photochemical methylation of inorganic mercury in the presence of such colored solids as mercury(II) oxide, solid sulfur and mercury(II) sulfide has been investigated in aqueous acetic acid solutions of mercury(II) acetate.
The yields of methylmercury photo-produced in the systems of mercury(II) oxide, solid sulfur and mercury(II) sulfide when irradiated with a 20 W blacklight lamp were about 1O³, 1O² and 1O⁴ times, respectively, higher than that in the control solution without any supended solids. It was confirmed that in the mercury(II) oxide system mercury(II) oxide acted as the photosensitizer for the production of methylmercury, while in the solid sulfur system basic mercury(II) sulfate formed during the photo-reaction acted as an additional photosensitizer. In the mercury(II) sulfide system, mercury(II) sulfide solubilized rapidly in the dark coupled with the reduction of mercury(II) ions, and the resulting sulfur atoms photo-polymerized to give a milky white solid, "photosulfur", which acted as the primary photosensitizer. The"photo-sulfur"was converted further into basic mercury(II) sulfate through a similar process as in the case of solid sulfur system.
The phc4osensitized, methylation in these heterogeneous systems was supposed to occur via energy transfer from solids to the mercury(II) acetate molecule.

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The effect of the calcination on the pore structure of silica was investigated on the assumption that porous solids are the assemblies of fine elementary particles. Effective diffusion coefficients, D. of He and sorption isotherms of benzene at 0°C were measured with the commertial spherical silica samples which were heat-treated at 300-900°C. In the case of the sample, pretreated at 700°C, the shape of the experimental isotherm agreed with that of the capillary condensation isotherm. derived theoretically for the assembly model of spherical elemen- tary particles of simple. cubic lattice type (SC), (Fig.3). The ratio, PeI1 i. e.0°1 L, where D is the diffusion coefficient in the pore and 0°1 L the ratio of opening fraction to tortuosity factor, was also in good agreement with the theoretical value of 0.123 for SC model '(Table 2). In the case of the samples at higher temperatures, the -shapes of the isotherms were sirhaari although the sorption amount including the volume of the pore space. / and the, specifif surface area, . E, and DeID decreased with the heat treatment temperature. These experimentai values agreed approximate, ly with theoretical 0, X, and AID values, which calculated on the assumption that the elementary particles fused partly at their contact zones, keeping the SC arrangement in spite of a decrese in distance between the centers of particles (Fig.6). c These results proved the propriety of the assembly model of- elementari irartieles and the. motier of fusion at the contact zones in porous silica.

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Dehydrogenation of isopentane at temperatures ranging from 400 to 500°C was studied with active charcoal catalysis impregnated with Fe, Co, Ni and Cu. Discussion was made mainly about the effect and the role of added transition metals. The catalytic activities of active charcoals containing those metals were several times higher than that of active charcoal itself: However the selectivities were independent of the additives. The catalytic activity increased at first almost linearly with the increase in the metal content, but above a certain critical value the activity- did not depend on the metal content. Although the critical value varied by the element, the saturated activities depended little on the metal species added. The dehydro- genation of paraffin on active charcoal is composed of the abstraction of hydrogen atoms by active charcoal from paraffin and the desorption of hydrogen atoms from active charcoal as hydrogen molecules. When those metals were impregnated on other supports (silica gel, porous glass), they exhibited little catalytic activies for the dehydrogenation of isopentane. Therefore, the metals added to active charcoal were thought to accelerate the recombination and desorption of hydrogen atoms which were known to be the rate-determining step of the reaction on active charcoal.
This is understood as the reverse process of ordinay spillover phenomenon which is the diffusion of hydrogen atoms to a support through metallic particles on the support. The new phenomenon observed in this work may be called"reverse-spillover".

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Oxidation of Ethylene was studied in vapor phase over palladium sulfate-active charcoal catalysts. Major product was acetaldehyde and minor products were butenes and carbon dioxide. Palladium sulfate catalysts exhibited fairly high activities but they lost their activities fairly rapidly with the reaction time. The deactivated catalyst was reactivated by the treatment with concentrated nitric acid at the reaction temperature. While the catalytic activity increased with the increase in free sulfuric acid content in the catalyst up to about 10 wt %, above it, the activity decreased depending on a squre of the sulfuric acid concentration. The apperent activation energy of acetaldehyde formation increased with increasing sulfuric acid content from 8 kcal/mol (at sulfuric acid free) to 8.5 kcal/mol (at 100 wt % sulfuric acid based on active charcoal). The reaction order in the steam decreased with the increase in the sulfuric acid concentration from about 2.0 to zero. The effect of the sulfuric acid concentration on the apparent activation energy and the reaction order were interpreted on the basis of the hydrophlicity of the catalyst. The catalysis of the palladium sulfate catalyst was concluded as a redox system and it was found that the reoxidation step of the reduced palladium was slower than that of the palladium chloride catalyst. t Oxidation of Olefins with Metallic Salts-Active Charcoal Catalysts.

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With the object of investigating a role of hydrogen and oxalate ion in galvanostatic oxidation of Al in oxalic acid-triethanolamine solutions, pH and/or concentration dependence of bath voltage, microstructure of anodic film and C₂O⁴ content of the film were examined, while the chemical dissolution rate of the film influenced by these factors were also examined. In the bath with constant (COOH), content, HC_2CO^2-- concentration decreased with decreasing pH. Then the total area of pores increased with decreasing pH so that electric field near the surface of barrier layer decreased. Nevertheless, C_2CO^2- content of the film increased as pH decreased. Such pH dependence of C_2CO^2- content of the film was in agreement with that of HC_2CO^2-- adsorption. In the bath of constant pH, the total area of pores decreased as oxalate concentration was increased. In this case, C_2CO^2- content of the film was increased since HC_2CO^2-- adsorption was accelerated by the high oxalate concentration and the increased electric field near the surface of barrier layer. Anodic film was more easily dissolved as CiO, content of the film was higher and/or pH at the pore-base was lower, and so the bath voltage decreased as pH of the solution was lower and/or oxalate concentration was higher. From the results obtained, it was considered that the initiation of pore formation was the dissolution of film accelerated by the oxalate ion involved in the film.

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Potassium Ion Conduction in Potassium Beta Ferrites Takehiko TAKAHASHI, Katsumi KUWABARA and Yuji KASE Department of Applied Chemistry, Faculty of Engineering, Nagoya University; Nagoya-shi 464 Japan Potassium ion conduction in beta-alumina type potassium beta-ferrites was investigated. Dense products were obtained by prefiring K2CO^3-Fe2O^2- mixtures at 950°C for 10 hr and sintering them at 1350-1450°C for 1-3 hr. Cylindrical specimens of about 7 mm in diameter and 5-15 mm long were cut from the sintered bodies. Using A. C. impedance bridge at 10 kHz, the conductivities were measured in the range from room temperature to 500°C. Electronic and ionic conductions were examined by the use of D. C. polarization method and electrolysis, respectively. The sintered polycrystal having the composition of Fe2O^2-/K20 =6.0 was revealed to be a mixed conductor responsible for ca.1-2% ionic conduction and predominantly electronic one due to hopping of electrons between iron (II) and iron (ll) ions. Total conductivity of the specimen was 1 X 10° mho m^-1 at 300°C and the potassium ion conductivity was 1.5x 10-2 mho cm^-1 at the same temperature. In order to keep ionic conduction and to reduce electronic conduction, three oxides, such as ZnO, MgO or NiO, were doped in terms of the formula K20. (6x) Fe2O^2- MO (x = 0-1.0). Both total conductivity and rate of electronic conduction decreased with increasing x, and the potassium ion conductivities of the samples doped with ZnO (x =O.8), MgO (x = O.8) and NiO (x=1.0) were 1.8x 10-2, 5. Ox 10-3 and 3.5x 10-3 mho cm-' at 300°C, respectively, and electronic conduction became negligibly small. MO doping in terms of the above formula would be supposed to have the lowering effects on the concentra- tion of total iron and that of iron (II) ion in potassium beta-ferrites.

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Materials Research Laboratory, Nagoya Institute of Technology; Gokiso-cho, Showa-ku, Nagoya-shi 466 Japan Monazite (monoclinic cerium phosphate) was synthesized by precipitating it from the mixed solution of cerium (III) chloride and orthophosphoric acid at 50°C and in the pH range O.2-0.6. After aging for 28 days, monazite crystals showed platy habit at pH's O.2 and O.4, and prismatic habit at pH 0.6. Hexagonal cerium phosphate coexised with monazite at pH 0.6, but disappeared as the aging progressed.
The chemical formula of the synthesized monazite is given as CePO₄. The density is 5.16 g/cms. The unit cell parameters obtained from X-ray diffraction of powder are as follows; a= 6.787 A, b=7.O^2-9 A, c = 6.468 A, 8 =1O^2-°18'.

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The mechanism of the reaction between chlorate and chloride ion in sulfuric acid solution was studied.
By considering material balances and effects of coexistent ions in these systems, it was found that the species: concerned were chlorate ion, chloride ion, hydrogen ion, perchlorate ion, chlorine dioxide, chlorine and water, and that these reactions were represented by the following three equations.
ClO^2- + Cl- + 2 H⁺=ClO^2- + 1/2 Cl2 + H₂0 (1)
ClO^2- + 5 Cl- + 6 H⁺=3 Cl2 + 3 H₂0 (2)
3 ClO^2- + 2 11+=2 ClO^2- + ClO^2-- + H₂0 (3)
Based on the assumption of the reaction mechanism proposed in the previous reports by other authors, the elementaly reaction equations could be derived as shown below,
ki ClO^2- + Cl- + 2 H⁺ HOCl HClO^2- (a)
k2 HClO^2- + ClO^2- + H⁺ (b)
2 ClO^2- + H₂O b HOCl + ClO^2- ClO^2-- + HCl c HClO^2- Cl- H⁺ 2 HOCl d HOCl H⁺ -7-4-0 Cl2 + H₂O e
Experimental results, favored the appropriateness of these derived equations. The rate constant ratio kelk4 and k3/k3 (at 30°C) are 2.75 X 1O^2-, and 7.5 respectively.

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The copper (II) complexes of N, N'-bis(1-acetylethylidene)-m-phenylenediamine (1) and N, N'-bis(1-acetylethylidene)-p-phenylenediamine (2) were synthesized, and the structures of these complexes were estimated in terms of the data of infrared and electronic spectra and magnetic moments. The complex (3) of ligand (1) synthesized by the use of copper hydroxide or copper acetate seemed to be quasi-tetrahedral which is represented by (CuL), (L: CleHi8N2O^2-). The complexes (4) of ligand (2) synthesized by the use of copper hydroxide can be separated into several kinds of compounds by means of solubility differences toward organic solvents such as benzene, ethylene chloride, methylene chloride and chloroform. The complexes (4a) (4d) isolated were assumed to be polynuclear complexes represented by 142Cun, L (n=1-4) as a general formula. They are square planar in solid state, but seemed to rearrange into quasi-tetrahedron in chloroform. The composition of complex (4 j) of ligand C 2D synthesized by the use of copper acetate is represented by CIO. (0Ac), The structure of complex (4 j) can not be discussed in detail due to its insolubility in ordinary solvents.

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Atomic absorption spectrometry using a carbon tube atomizer was used for the determination of copper in sea water and sea water clam, and simultaneously the investigations of the applied carbon tube temperature (voltage), argon flow rate, calibration curve and the interference of diverse ions were carried out.
A constant absorption signal was observed at a carbon tube temperature (voltage) of above ca.2000°C (7 V). In the present determination the carbon tube atomizer was operated at a temperature (voltage) of ca.2500°C (8 V).
A constant absorbance of copper was observed at a lower argon flow rate than 2 l/min. However, when the argon flow rate became higher than 2 //min, absorbance of copper decreased, but the reproducibility of absorbance was excellent.
In the range of (2.5-15) x 10-"g of copper, a fairly linear calibration curves were obtained by the injection of 10 Ail of the copper solution whose concentrations were 0.O25-0.15 ppm. The sensitivity (1% absorption) was 4x 10-11 g and the R. S. D. was 2.8 per cent. The effect of salts on the peak absorbance of copper was studied with regard to the solution of copper (0.2 ppm) containing 100 or 1000 fold excess of salts. For 1000 fold excess, most salts interfered with it.
Copper content in sea water and sea water clam was determined by extracting copper into diisobutyl ketone as diethyldithiocarbamate. By this method, concentrations of copper in sea water, shell and soft tissues of the clam were found to be 0.0036-0.014, 0.15-0.38 and 0.43 .3 ppm, respectively. In the soft tissue such as liver, kidney and labial palps copper was found to be somewhat enriched.

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5-Methyl-furfral 2-benzothiazolylhydrazone (MFBH) was synthesized by condensation of 5- methyl-furfral with 2-hydrazinobenzothiazole, and applied to the spectrophotometric determina- tion of copper. The acid dissociation constant of the reagent is determined spectrophotome- trically in 50% dioxane-water (v/v) at 25°C under an ionic strength of O.1 and found to be 10
Copper (II) forms 1: 2 complex with MFBH. The complex is soluble in benzene but insoluble in water. It has an absorption maximum at approximately 405--415 nm in benzene, and can be extracted quantitatively into benzene in the presence of pyridine. The extraction needs shaking more than 7 minutes.
The outline of the procedure is as follows; Take the sample solution containing less than 12 mg of copper (II) in a 50 ml separatory funnel, add 2 rra of 10% pyridine solution and an acetate buffer solution, and dilute to 30 ml with water (the solution is adjusted to pH 6.5). Add 10.0 ml of 2.0 x 10-4 mol/l MFBH solution in benzene and extract the complex by shaking the two phases for 10 minutes. Measure the absorbance of the extract at 410 nm against the reagent blank.
The calibration curve was linear in the range of 0 to 12 Aug copper (II) in benzene. The molar absorptivity and the sensitivity for log (41 I) =0.001 001 were 5.8x 1O^2- //molm and 1.1 x1O^2- Aug Cu/cm², respectively.
Silver ( I ), cobalt (IC), mercury 00, icon (111), thiocyanate and citrate interfered with the determination, but the other common ions did not interfere.

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The argentometric titration of selenious acid by the short-circuit amperometric technique using a rotating platinum wire electrode (1000 rpm) vs. SCE, and the differential determination of alkali halide and selenious acid have been studied.
Selenious acid (0.00005-0.01 N) can be directly titrated with silver nitrate after adjusting the pH to 9.5-12.5 with sodium hydroxide. The precise determination is testified at the concentration range of 0.001-0.01 N; either the relative error or the coefficient of variation. being about 0.2%. The whole procedure requires only 5 minutes. The presence of sodium selenate does not interfere determination, but ammonium salts give serious interference.
A recommended procedure for the simultaneous titration of alkali halide and selenious acid. is as follows.
Triton X-405 is added to the aqueous solution of a mixture of selenious acid and one of alkali halide (potassium iodide, potassium bromide or potassium chloride) in a titration cell. The solution is diluted to 100 ml so that the final concentrations are 0.0005-4/ 001 N in selenious acid, 0.0005-M.001 N in alkali halide, and 0.O2 w/v % in Triton X-405. After the solution is titrated with O.1 N silver nitrate standard solution to the end point of alkali halide, sodium hydroxide is added to the same solution in order to make the pH about 10, and then titration is continued to the end point of selenious acid. The relative errors are about 0.2% for O.001 N potassium iodide and selenious acid, respectively. The whole procedure can be performed in 10 minutes.

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A high speed liquid (HL) chromatographic technique was applied to analysis of nonionic surfactant of ethylene oxide (EO) adducts.
Pattern analysis of EO adducts (ether and ester types) and polyethyleneglycol (in Fig.3, 4, 5 and 8) were carried out under the following conditions; Zorbax-SIL column: 2.1 mm i. d. x 25 cm, mobile phase: mixture of acetone and n-hexane (gradient rate, 5% acetone/min. ) temperature: 30°C, pressure: 1500 psi, detector: modified moving wire/flame ionization detector (temperature of evaporator: 70°C, N2 gas flow rate: 60 m//min. )
A sample was to be acetylized prior to HL chromatogram in order to decrease the adsorption on column. The mole distribution of E0 adducts in the range about 30 was estimated by the anlysis of HL chromatogram. Retention time was directly proportional to an E0 mole number. Alkyl group composition of the peak appeared on HL chromatogram was determined by introducing the elute to gas chromatography.

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Separation between polynuclear aromatic hydrocarbons was achieved by supercritical fluid chromatographic method by using n-hexane and silica as mobile phase and stationary phase, respectively.
Experimental conditions were as follows; temperature: 230-259°C, pressure range: 17.580 kg/cm².
The retention time of triphenylene decreased with increase of pressure up to 40 kg/cm² at temperature of 250°C and increased slightly at the pressure higher than 40 kg/cm². Benzene, naphthalene, phenathrene, pyrene and chrysene were separated successively within 6 minutes; mobile phase velocity being 3 m//min, column temperature 250°C, column pressure 33 kg/cm², and 2 m long and 4 mm i. d. column packed with Corasil Oa Eight peaks were observed on supercritical fluid chromatography of coal tar within 20 minutes.

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Three kinds of gel beads of crosslinked vinyl alcoho-allyl alcohol copolymer were prepared, The frst gel was prepared by partial saponication of vinyl acetate-diallyl phthalate copolymer, that has been obtained by suspension polymerizaton. The excluded molecular weight increased with increasing the degree of saponication, and, its maximum value was about 52000. The second gel was prepared by crosslinking of vinyl alcohol-allyl alchool copolymer, that was obtained by perfectsaponi cation of vinyl acetate-diallyl phthalate copolymer, with epichlorohydrin. Its maximum value of the excluded molecular weght was about 100000. The third gel was prepared by hydrolysis of vinyl aceetate-diallyl phthalate copolymer, which was polymerized in the presence of adiluent, and subsequent cross In king With epichlorohydrin. In this case; cyclohexane was used as a diluent, which serves as a solvent fr vinyl acetate and diallyl phthalate and desnt dessolve the polymer The gel obtained was highly'porbus. The excluded molecular weight the gels increased with increasing volume of an, added diluent during polymer ization and its maximum excluded molecular weight was about 200000. It was shown that a series of gels of different degrees of crossIinking could be obtained by controlling saponi-catino of vlnyl acetate-diallylphthalate copolymer and the excluded molecular weight of the gel was larger than that of apoly(vinyl alcoho1)gel.

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For the radioactivation analysis of environmental specimens, such as biological and airborne particulate samples, a new group separation method using 1-pyrrolidinecarbodithioate extraction has been developed. A sample irradiated in an atomic reactor for 1 or 5 hours is dissolved with hot HNO^3-ELSO, mixture, and the resultant solution is adjusted to pH 3. O. Transition elements, expept manganese, are extracted into chloroform solution of pyrrolidinecarbodithioate, and manganese is then extracted from the aqueous solution of pH 7. O. The analyzed elements are separated into the following four groups; halogens are separated into the distillate of wet ashing procedure, biologically essential or toxic transition elements into the pH 3 extraction phase, manganese into the pH 7 extraction phase, and alkali, alkaline earth and rare earth elements into the residual aqueous phase. The elements in each phase are determined by gamma-ray spectrometry using a Ge (Li) detector.
Among the elements observed, no quantitative groupings could be performed on chromium, antimony and arsenic by the present procedure.
The best scheme of the group separation was based on the fundamental study on the behavior of the elements using radioactive tracers.
The validity of the method was demonstrated by analyzing NBS standard reference materials Orchard Leaves and Bovine Liver, as well as the airborne particulates collected in Kobe City, and by comparing the data obtained with those certified by NBS or with current literature data.

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The polarized absorption spectrum of 2-naphthaldehyde was measured in a stretched polymer film, and the direction of the polarization with respect to each electronic transition was determined. Next the rotational conformation of the aldehyde was discussed by comparison with the results of the PPP calculations, and it has been found that the conformation A in the equation ( 1 ) is more stable than B. The above results are also supported by the extended Hiickel calculations concerning the potential energy changes with respect to the rotation of the aldehyde group.

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The kinetics of the diazo-coupling reaction of p-methoxybenzenediazonium tetrafluoroborate with acetylacetone have been investigated in water, methanol, dimethyl sulfoxide, N, Ndimethylformamide, and acetonitrile. From the dependence of the apparent rate constant on solvent acidity, it was found that a reactive species of acetylacetone is a carbanion in each solvent. The rate constants of the reactions in dipolar aprotic solvents are considerably greater than those of the reactions in protic solvents. On the basis of the activation parameters of these reactions, the observed solvent effects are interpreted in terms of a difference in solvation toward a carbanion.
Furthermore, the rate constants of the coupling reaction of imidazole in which the imidazole anion is a reactive species have been measured in several non-aqueous media. The solvent effects in this case are similar to those of the reaction of acetylacetone.

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The reaction of acrylaldehyde with ethanol catalyzed by RhCls H₂O, PPhs and CH₃COONa yielded ethyl j3-ethoxypropionate Cl J (bp 38°C/45 mmHg, nr 1.4072) in about 50% yield at 70°C for 16 hr. By-products were ethyl propionate, f3-ethoxypropionaldehyde, propionaldehyde, 1-propanol and low molecular weight polymer of acrylaldehyde (Table 3).
Other et, 6-unsaturated aldehydes also reacted with various alcohols. The yields of alkyl hialkoxypropionates were affected by the steric effect of both alcohol and a, 0-unsaturated aldehyde and by the polarity of the alcohol.
The yield decreased in the following order:
Me0H EtOH> n-PrOH > n-BuOH CH₂=CHCHO>CH₃CH=CHCHO> CH₂=C (CH₃) CHO.
It was confirmed that C 1 was produced via 3-ethoxypropionaldehyde.

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In order to obtain fundamental data for commercial production of peracetic acid(PAA) by the oxidation of acetaldehyde(AcH) in the liquid phase, effects of various reaction conditions were studied, The oxidation reactions were perfromed at20C under atmospheric pressure in organic solvents.
Maximum yields of PAA and total peroxides(TPO) were obtained at around 75g/l of initial concentration of AcH regardless to the kind of solvents or presence of catalysts(Fig.3, 4), From the curves of initial rate of oxygen absorption at each concentration, reaction rate orders with respect to AcHc concentration with catalyst were 1.45, 1.0, 1.14 and 1.42 in the solvents of acetone, ethyl acetate, benzene and acetic acid, respectively(Fig.3, 5).Acetone and ethyl acetate were the best solvents for peracid production independent of using catalyst or not (Table1, 2).In many solvents such as toluen, the oxidation reaction did not proceed without catalysts, but addition of a little amount of Co catalyst promoted the reaction without an induction period(Table2). Generally, good yields of PAA and TPO were obtained when such solvents as accelerate the oxidation reaction were used.
Effects of the amount of catalysts were studied using Mn, Co and Fe-acetylacetonato as catalysts. A trace amount of the Mn catalyst decomposed the products and inhibited the oxidation, but maximum yields were obtained when O.1g/l of the Co catalyst or O.005-0.015g/l of the Fe catalyst were added(Table3). Some kinds of Co and Fe salts also gave PAA and TPO in high yields(Table4).

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When a stainless steel autoclave was used repeatedly in the oxidation of acetaldehyde (AcH) with oxygen in the absence of metal salt catalysts, a gradual increase of the selectivities of peracetic acid (PAA) and total peroxide (TPO) based on absorbed oxygen was observed. In order to make the stainless steel surface active for the formation of PAA, some kinds of treatments of the surface were tried. The reactions under pressure were carried out in the presence of SUS-32 stainless gauzes in an autoclave coated with Teflon resin which was thought to be ineffective on the oxidation.
As a result, it has been found that the treatment with acid solutions is effective as shown in Tables 1 and 3, but the treatment with alkaline solutions (Table 5) or the other methods does not activate the surface. The activity was decreased gradually with the thermal treatment of the activated surface (Table 4).
In X-ray and electron beam microanalysis, differences of compositions between both of treated and untreated surfaces were not detected. When electron microscopy was applied to the observation of the state of surfaces, a striped pattern due to small crystals was observed only on the surface treated with acid solutions (Fig.3), and surfaces treated by means of the other methods were similar to the untreated surface. It seems that the fresh surface which has been developed by a chemical etching is required for the oxidation of AcH with oxygen, and that the surface acts not as a source of metal ions which dissolve into liquid phase but as a solid state catalyst (Table 2).

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Condensation products derived from diphenic anhydride or its chloro derivatives with 1, 2-, 1, 8- and 2, 3-naphthylenediamines were studied.
New yellow perinone type pigments were preferably obtained by the condensation of diphenic anhydrides with naphthylenediamines in boiling quinoline, while perimidine type intermediates were formed by the reaction of these anhydrides with the diamines in boiling acetic acid.
The structures of these intermediates were determined spectroscopically.
The effect of chlorine substitution on shade of pigments was bathochromic. It was found from light- and solvent-fastness tests that the chlorine substitution has a favorable effect.

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New metallized isoindolinone pigments were studied. The pigments were efficiently produced by the reaction of bivalent metal salts with the compounds derived from 3, 3, 4, 5, 6, 7-hexachloroisoindoline-1-one and 2-aminopyridines in ethylene glycol or glycerol. Bivalent metal salts such as Co-, Ni-, Cu- and Zn-acetates were adapted for the formation of pigments.
The metal has a great influence on the shade of pigments, and their light-fastness were excellent (grade 7-8 by blue-scale). Each pigment was insoluble in ordinary organic solvents and alkaline solutions but decomposed to tetrachlorophthalimide by strong acids.

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In order to obtain some fundamental informations on the solvent dyeing for nylon 6, the diffusion behaviors of C. I. Disperse Orange 3 and Violet 1 within a sheet of nylon 6 from normal alcohols as a medium have been investigated by means of microspectro-photometric method.
The diffusion behaviors of these dyes are very similar each other.
The larger the carbon number of a normal alcohol is, the larger both the activation energy and the frequency factor of diffusion are. That is to say, the diffusion is accelerated by decreasing the carbon number from the view point of activation energy, and by increasing it from the activation entropy.
Water used as a medium for comparison shows the intermediate behavior between ethanol and 1-propanol.
These results correspond well with Tg of the substrates swollen in each medium, and also they can be explained qualitatively in relation to the activation energy and the heat of dyeing.

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7, 7, 8, 8-tetracyanoquinodimethane (CQ) salts of polycations ( 1 ) containing cyclohexane ring in the main chain were synthesized. From their specific resistances ( P ) and activation energies of conduction (E. ), the effect of cyclohexane ring on the electronic conduction was discussed.
The remarkable decreases in p- and Es-values continued by the addition of neutral CQ molecules (CQ°) to CQ simple salts so far as [CQ°]/[CQ] became 1.0 in ( I ) -CQ salts. The values of p and Ea at [CQ°]/[CQ] = 1.0 were 20---85 S1m and 0.075-0.085 eV, respectively, and these values were smaller than those of any other polycation-CQ salts.
From the comparison of these results with those of other polycation-CQ salts, it was considered that the ionic sites in the main chains of polycation were fixed and the distances between ionic sites were maintained by introducing the rigid skeletal constructions such as cyclohexane rings in the main chain of polycation and that charge transfer complex of CQ° and CQ 7 molecules was easily formed, bringing about an increase of mobility in electronic conduction.

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The catalytic reduction of nitric oxide with carbon monoxide (NO+ CO -+ 1/2 N2 + CO₂) was studied using a flow reactor (inside diameter: 12.0 mm) under atmospheric pressure and at 120-550°C (mainly 550°C). The catalysts used were about sixty kinds of coprecipitated metal oxides, Girdler's copper chromite, G-13 and barium-promoted copper chromite, G-22 (average. diameter: 1.0 mm). They were reduced with hydrogen at 550°C. Inlet gas concentration was 500 ppm, 1% NO-1.05-10% CO-0-2.5% O^2-10.4% H₂O-remaining N2, and the total gas flow rate was 500 or 1000 Ncms/min for 250 mg of oxide catalyst.
In the presence of H₂0 and O^2-, NH₃ was considerably formed by the side reactions, CO+H₂0 CO^2-1-H₂ and NO + 5/2 H₂ NH₃+H₂0, and also the rate of C0+1/2 O^2- CO₂ reaction was higher than that of NO +CO 1/2 N2+CO₂ reaction over almost all catalysts.
Based on the above results, the active catalysts and the reaction conditions to retard markedly the occurrence of NH₃ and to make the steady operation possible were found. These catalysts were 5 mol % CuO-5 mol % Co3O^2--90 mol % MgO, 25 mol % CuO-25 mol % Co3O^2--50 mol % MgO, 25 mol CuO-25 mol % Co3O^2--50 mol % Al2O^2- and etc. The desirable condition for the system containing several hundred ppm of NO was to use more CO by several % than the stoichiometric requirement for C0+1/2 O^2- -+ CO₂ reaction, to keep the operation temperature at around 550°C, and to adjust the appropriate space velocity (At the lower space velocity below about 40000 hr', the amount of NH₃ formed became negligible).

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The catalytic dealkylation of toluene with steam and hydrogen (C71-18+ 2 H₂0 C, H, +CO, +3 H₂, C7I-18+ H₂0 C6H6+CO +2 H₂, C71-18+H₂ C6H6+CH4) were studied by using a flow reactor (inside diameter: 16.0 mm) under an atmospheric pressure and at 350-550°C.
Noble metal (Rhodium, Platinum, Palladium, etc.) catalysts supported on Al2O^2-, SiO^2-Al20, or etc. were prepared under different conditions and compositions. Mol ratios of inlet gases were 1.39-10.0 (mainly 5.0) (steam/toluene) for toluene-steam system, 0.5-5.0 (mainly 2.5) (hydrogen/toluene) for toluene-hydrogen system, and 1.39--6.0 (steam/toluene) as well as 1.0-3.0 (hydrogen/toluene) for toluene-steam-hydrogen system. The feed rate with reference to toluene was 1.265 x 10-5 mol/sec=17.0 Nm3 (g) /min mainly per 0.50 g of the catalyst. As a result, O.3% Rh-0.3% Pt-a-Al208 catalyst prepared by the method described below was found to be an excellent one in activity, selectivity and durability for above dealkylations at 400-450°C.
A-Al2O^2- was prepared by precalcination of commercial r-Al2o3 for an hour at 1100°C before impregnation of rhodium (III) chloride and chloroplatinic acid. After impregnation the catalysts were calcined for 3 hours at 600°C.

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The rates of transformation from a to 3 form of copper phthalocyanine crystal during heat treatment were examined in various atmospheres by using an apparatus which enabled simultaneous measurement of high temperature X-ray diffraction and differential thermal analysis. The ambient gases examined were He, O^2-, NH, , FI, S and HCl.
The rate of transformation in NH₃ was higher than that in He, but it was lower in O, and especially in 1125 and HCl. It was found that all the ambient gases except He were absorbed considerably by the crystals. These facts suggest that the rate of transformation is influenced by the absorption of the gas into the copper phthalocyanine crystal.

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The extraction kinetics of nickel (II) ion from aqueous solution to chloroform solution of 2- (2-thiazolylazo) -4-methylphenol (TAC) was studied. The rate of extraction was controlled by the 1: 1 chelate formation reaction which proceeded by two reaction paths in aqueous kRphase: ( 1 ) Ni2+ R- NiR+, ( 2 ) Ni2+ HR 1, NiR+ H+. The estimated rate constants, kR, - and kHR, are 2.2x 104 and 3.3x 102 ismol-'ec- respectively. The temperature dependence of these reactions were determined and thermodynamic data have been calculated.

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Kinetic studies on the decomposition of several 1-aryl-3, 3-dialkyltriazenes have been carried out in aqueous acidic solutions. The reaction was found to be of first-order with respect to both triazene and oxonium ion. The substituents in phenyl group were found to correlate with Hammett's a-constants. The basicities of triazenes were determined on the basis of the kinetic results. The effects of substituents in amine component on the rate of reaction are also discussed.

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The reaction of triphenylboroxine with diethyl ethylidenemalonate in the presence of bis (ethoxycarbonylacetonato) copper (II) was investigated. When the reaction was carried out in pyridine, copper powder precipitated and copper (I) pentaborate-pyridine (1/6) crystallized. From the filtrate, benzene (69.7%), biphenyl (13.9%) and 1-phenylethylmalonic acid (7.5%) were obtained. Several of by-products were also identified and the results were summarized in Table 1. Possible pathways for the formation of these products were illustrated in Figure 1. The formation of biphenyl and 1-phenylethylmalonic acid was explained by a radical mechanism. By use of a large excess of diethyl ethylidenemalonate as solvent, 1-phenylethylmalonate was obtained in a 55.7% yield.

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trans-Perfluoro-4-methyl-2-pentene [D-1], a dimer of hexafluoropropylene (HFP), was prepared by passing HFP through KHF2-DMS0 system at the ordinary pressure and temperature, followed by separating from trimers. By heating with KF in sulfolane, the dimer [D-1] was most effectively converted into the thermodynamically more stable isomer, perfluoro-2- methy1-2-pentene [D-2].

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The dehydrogenation of sesquiterpene alcohols, such as longibolneol, longifenchyl alcohol, isolongiborenyl alcohol and longihomocamphenilol was investigated, over the catalyst systems composed of copper and zinc.
The selectivity to oxo compounds obtainable from above experiments, was mainly dependent on the reaction temperatures, and desired oxo compounds were prepared easily in 94-98% yield, when the reaction was carried out at 291-315°C and under 25-35 mmHg.
The oxo derivatives obtained import wooden odor.

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The adsorption capacities of polyethylene glycol (PEG) whose molecular weights being 200-20000 were investigated at 25°C. The adsorptivities of PEG whose molecular weights being smaller than 1000 increased with increasing molecular weights due to a decrease in affinity for water. The adsorptivities of PEG whose molecular weights being 1000-7000 were almost the same, but the adsorptivity of PEG whose molecular weight being 20000 became very small due to a molecular sieving effect of activated carbon.

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