Rheological properties of concentrated aqueous solutions of sodium silicate were studied by the use of a coaxial cylinder rheometer. The shear viscosity is almost Newtonian. The loss modulus G" is proportional to the angular frequency ω and the storage modulus G' to the square of angular frequency. Therefore, the viscRelastic behavior is characterized by the zero-frequency dynamic viscosity η_oand elasticity coefficient A_G, where η_o and A_G are defined by the following equations, respectively;
_??_
The relaxation time 'τ given by A_G/η_o increases with increasing the SiO₂ concentration. An increase in the mole ratio (n) of SiO₂ to Na₂O reduces the SiO₂ concentration above which the relaxation time shows a remarkable increase. The elastic effect in the viscoelastic behavior may be attributed to a chain-like configuration of aggregated sodium silicate molecules in the solutions.

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Thermodynamic quantities for the transfer of HC1 from water to water-1-propanol mixtures were determined at 25°C by the EMF measurements of the cell: glass electrode _??_ HCl in mixed solvents _??_ AgCl-Ag. The solvation process of monatomic ions was divided into two steps; (1) formation of a cavity in the solvent to accommodate the solute and ( 2 ) introduction of the soldte ion into the cavity, followed by the interaction with the solvent. The ion-solvent interaction was discussed on the basis of a discontinuous model in which the ion is surrounded by a local solvation layer immersed in the bulk solvent. The interaction energies between halide ion and polarizable dipoles for octaheargi configuration in water were calculated. In the transfer of H3O⁺ and Cl^-from water to water-1-propanol mixtures, changes in both the enthalpy and the entropy of the solvation layer give a maximum in a water-rich region of this solvent system. The characteristic maxima can be related to the enhancement of the hydrogen-bonded structure of the solvent.

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It was found that colored organosols were formed from various bivalent -metal soaps in organic solvents by heating at 110-180°C. Colors and turbidities of the organosols depended on the kinds of metals and solvents.
The mechanism of the org anosol formation was studied by measuring the change in the infrared absorption spectra of metal soaps and in the acid values of the solvents upon heatin g. Iwt afso und that the organosols were formed at the temperatures around which the acid val ue of the solvents sharply increased.The infrared absorption of the carboxyl group of the metal soaps in 1590-1600 cm^-1 disappeared and the new absorption of carbonyl group appeared in 1710cm^-1 after the formation of organosols. The fine particles were observed through an electr o n microscope after dilution and centrifugation of organosols, and were identified as oxides by X-ray analysis for copper organosol. These results indicate that the organosols are fine pa rticles of the metal oxide stabilized by the medium.

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The n-type SnO₂ optical transparent electrode (SnO₂OTE) was modified with the immobilized ruthenium complex membrane, and the photocell was composed of the modified SnO₂, OTE, platinium electrode and ethylenediaminetetraacetic acid disodium salt (ETA) as the electron donor in aqueous solution. Under irradiation, the continuous stable photocurrent was observed as a result of electron injection into the SnO₂, OTE modified with the ruthenium complex, Moreover, the effect of wavelength on the photocurrent during the irradiation was investigated, and it was recognized that the photocurrent gave a peak at the maximum region of the absorption and excitation spectra of the ruthenium complex.

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The hydrogen absorption and desorption characteristics of Ti_1-xLa_xCo(x=0.05∼0.5) alloys were investigated. The alloys can easily be activated and they react readily with hydrogen to form the hydrides Ti_0.95La_0.05CoH_1..4, Ti_0.9, La_0.1, CoH_01.3, Ti_0.75La_0.25CoH_0.8 and Ti_0.5La_0.5CoH_0.4(the hydrogen contents: 1.3, 1.1, 0.6 and 0.3 wt%, respectively) under the hydrogen pressure of 30 atm at 80°C. The dissociation pressure of these hydrides, P is dependent on the lanthanum content x by which the titanium is substituted. The value of log P increases gradually with increasing x.
The standard enthalpy change for the Ti_0.9, La_0.1, , Co-H₂, reaction, -14.3 kcal/mol H₂ is determined on the basis of the dissociation isotherms (Fig.5); this value is nearly the same as that for the TiCo-H₂, reaction. The temperature required to generate the dissociation pressure of 1 atm for Ti_0.9, La_0.1, CoH_1.3, (tetragonal structure) is 115°C, lower than 130°C for TiCoH_1.4. For Ti_0.9La_0.1, Co, only two hydrogen absorption-desorption cycles under the mild conditions perm it the alloy to be fully activated. The cycle is repeated 30 times but no variation in the hydrogen absorption-desorption capacity is observed.

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The adsorption of molybdenum (VI) on the chelating resin has been studied in the column process. The adsorption test was carried out using Dowex A-1, chelating resin containing iminodiacetic acid residues. Chelating resin was used in the sodium form. Adsorption of molybdenum on the resin was influenced by various factors such as pH values and molybdenum concentration in the test solution. At pH above 2.1, adsorption of molybdenum on the resin was increased with increasing the molybdenum concentration in the solution. On the other hand, at pH range O.9 to 2.1, adsorption of molybdenum was decreased with increasing the molybdenum concentration. Amount of adsorption of molybdenum showed approximately constant values at pH about 0.85, 2.1, and 5.5, respectively. When the pH range 0.5 to 0.9, amount of adsorption of molybdenum was the largest. The elution of molybdenum was accomplished by passing sodium hydroxide solution through the column. Sodium hydroxide solution was more useful eluent than hydrochloric acid solution for the elution of molybdenum from the chelating resin.

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The effects of chemical composition, annealing time and annealing temperature on the phase separation were studied for the Na₂O-B₂O₃-SiO₂-Al₂O₃-CaO glass prepared from volcanic ashes called Shirasu and other chemical reagents. The following results were obtained from morphological observations by means of scanning electron microscopy, pore analysis of mercury penetration and chemical analysis of porous glass produced by acid leaching of phase separated ones.
1) Phase separation was depressed by the increase of Al₂O₃ content and showed a tendency to form droplet structure, but CaO promoted phase separation significantly and interconnected structure was formed. Even a primary glass containing 15 wt%, of Al₂O₃ was remarkably phase-separated by the addition of CaO.2) The pore radius of porous gla ss became larger with increasing annealing time and ternperature. The relation between average radius r (Å) and annealing time t ( h ) at 700°C was
r=76.2 t ^1/2-53.4( 1 )
and that between r and annealing temperature T (K) at annealing time 24 h was
ln r =-E/2RT+42.8 ( 2 )
Apparent activation energy E for a diffusion or flow process was 143.2 kcal/mol.

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The cementation of nickel and cobalt has been carried out in acidic sulfate solutions. Highor middle-carbon ferromanganese, or iron powder was added to the solutions containing 2 g/l. of nickel and cobalt, maintaining pH of the solution at the constant value of 3, 4 or 5 during the cementation under nitrogen atmosphere. Nickel and cobalt ions were almost stoichiometrically cemented with middle-carbon ferromanganese and iron powders. The rate of the cementation depended upon pH, temperature and molar ratio of the reducing metals to nickel and cobalt ions.
The optimum co nditions for the cementation with iron were pH between 4 and 5, 1.5 -2.0molar ratio of iron to nickel and cobalt ions, and 80°C or above. Copper (II) ion in the solution accelerated the cementation-reaction sharply, especially at a lower temperature. However, a small amount of aluminum ion inhibited remarkably the cementation of nickel and cobalt with iron powder.

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The fluoride film on copper surface fluorinated by fluorine gas and anode polarization in hydrogen fluoride solution has been studied by means of X-ray photoelectron spectroscopy, Xray diffractometry and scanning electron microscopy. The fluoride film is mainly composed of CuF₂ containing oxygen species such as Cu₂O. The films adsorbs oxygen and moisture on exposure to air and results in the formation of CuF₂⋅2 H₂O, which changes the transparent film to black. ESCA study shows that more oxygen than stoichiometry is included on the surface of the fluoride film. The ratio of O/Cu increases and that of F/O decreases when it is exposed to air. The fluorine species in the film is dissolved as fluoride ion when a sample is immersed into water, acid or basic solution. Under the condition of ESCA measurement, CuF₂ film is not reduced by X-ray irradiation but is reduced by Ar⁺ ion bombardment.

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A simple method has been developed for the determination of micro amounts of copper (II). It is based on the reduction of copper (II) to copper (I) with L-ascorbic acid, and on the spectrophotometric measilrement of an excess thiocyanate for the copper (I) with iron (III), after the removal of copper (I) thiocyanate precipitate yielded on addition of thiocyanate to the copper (I). The recommended procedure is as follows. Pipette 5 ml of sample solution containing copper (II) up to 158.9 μg in a 15-ml glass-stoppered tube, 0.5 ml of 0.05 mol/l Lascorbic acid and 1 ml of a formic buffer solution (pH 3.2), and then allow it to stand for 5 min. To this mixture, add 1 ml of 0.006% (w/v) himoroc solution as a coagulating agent and 1.3 ml of 2×10^-3 mol/l standard thiocyanate solution. After standing for 10 min, add about 1 ml of carbon tetrachloride, then shake the mixture vigorously by hand, and centrifuge i t in order to collect the precipitate of copper (I) thiocyanate formed on the interface between the aqueous and organic phases. Transfer a 5-ml aliquot of the aqueous phase to the other glass-stoppered tube, and add 2 ml of 1 mol/l iron (III) nitrate in 3 mol/l perchloric acid. Finally, measure the absorbance against distilled water at 460 nm.
The absorbances for copper (II) decrease with an increa se in the concentration of copper (II), b ut the calibration plot for copper (II)formed a straight line, and coincided with that for thiocyanate (expected graph) when the molar concentrations for copper (II) and thiocyanate were scaled as in Fig.2. In 11 results for a 5-ml aliquot of 2.5 × 10^-4 mol/l copper solution, the present method gave a mean absorbance value of 0.538 with a standard deviation of 0.002and a relative standard deviation of 0.3%.

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Ethylenediaminetetraacetic acid (H₄ edta) has been widely used as a chelating reagent because of its excellent complexing ability with many metal ions. In aqueous solutions, however, its chelates of the alkali metal ions are not sufficiently stable as to be applicable to analytical purpose. In this paper, the reaction of edta4- [(Et₄ N)₄ (edta) or (Bu₄ N)₄ (edta)] with Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Mg2⁺, Zn2⁺ and Pb2⁺ ions in N, N-dimethylf ormamide has been stu died by using the polarographic method. When edta^4- was added to the solution of alkali metal ions (Mt), they were precipitated as slightly soluble salts, whose compositions were M₄ (edta)as determined by the amperometric technique. When the mole ratio of edta^4-/M⁺ became larger than 1/4, the precipitates were dissolved again, and in the cases of Rb⁺ and, Cs⁺ ions, two reduction waves were observed at potentials more negative than the original waves. The limiting current of the first wave of the two waves increased with the increase of the mole ratio of edta^4-/M⁺ and then decreased: this is attributed to the reduction of M₃ (edta) and M₂ ( edta) ^2- ions formed in the course of dissolution of M₄(edta). The limiting current of the second wave of the two waves, on the other hand, increased with the increase of the mole ratio of edta^4-/M⁺ and reached a constant value at edta^4-/M⁺=1/1. These facts show that RV and Cs⁺ ions form 1: 1 chelates or compounds with edta^4-. In the cases of Li⁺, Na⁺and K⁺ ions, no reduction wave of 1: 1 compounds appeared. As for the bivalent metal ions (M²⁺), the precipitates M₂ (edta) were formed by the addition of edta^4-. They were dissol ved again with the increase of edta^4-, and the reduction wave due to 1: 1 chelates with edta^4-was observed in the case of Pb²⁺ ion.

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An amperometric titration was developed for the micro determination of iodate in periodate and was applied to the determination of hydroxylamine. The oxidation current of potassium iodide (titrant) was measured at +0.65 V vs. SCE with a rotating platinum electrode (2000rpm) as an indicator current. iodates in the presence of periodates were titrated with potassium iodide at about 10°C after periodates were masked with ammonium molybdate in the presence of hydrochloric acid. Hydroxylamine could be titrated similarly as it reacted with an excess of the periodate to produce the iodate.
The recommended procedures are as follows.
( 1 ) Determination of iodates in the presence of periodates. Both 5 ml of 5 × 10^-4 mol/l potassium iodate and of 10^-2 mol/l periodic acid are introduced into an amber glass titration cell (100 ml), and water is added to make the total voliime up to 50 ml. After 1 ml of 10^-1 mol/lammonium molybdate and 3 ml of 5 mol/l hydrochloric acid are added, the resultant solution is titrated with 10^-2 mol/l potassium iodide at about 10°C. Iodates (4 × 10^-5∼2 ×10^-5mol/l)in the presence of periodates (8 × 10^-6∼5 × 10^-3 mol/l) are determined with relative errors less than 1.4% and coefficients of variation less than 0.2%.
( 2 ) Determination of hydroxylamine hydrochloride. Ten milliliters of 10^-5 mol/l hydroxylamine hydrochloride are introduced into an amber glass titration cell (100 ml). After the pH of the solution are adjusted to 5∼6 with sulfuric acid or sodium hydroxide, 1 ml of 10^-1 mol/l periodate is added, and the solution is boiled gently for 3 minutes. Water is added to make the total volume up to 50 ml and then the reaction mixture is cooled rapidly to about 10°C. After the addition of 1 ml of 10^-1 mol/l ammonium molybdate and 3 ml of 5 mol/l hydrochloric acid, the resultant solution is titrated in the same manner as described in ( 1 ). A blank test is performed through the whole procedure. Hydroxylamine hydrochloride (3∼66, μg) is determined with a relative error and a coefficient of variation less than 0.2%. This method is rapid, simple. precise and especially suitable f or the determination of iodates with no interference of coexisting periodates. t Studies on Analytical Methods by Ampero metric Titration Using a Rotating Platinum Electrode. XLIV.

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The polarographic behaviour of Cd (II) ion in EDDA (OH)₂ (N, N'-bis (2-hydrOxyethyl) ethylenediamineN, N'-diacetic acid) solutions with metal ligand ratios of 0.5: 1, 1: 1, and 1: 5in the pH range from 3.12 to 8.77 was investigated. Those polarograms gave one or two well-defined waves by the experimental conditions employed. The first wave (-0.596 V vs. SCE, pH=4.05, the reciprocal slope of log-plot: 30.3 mV) was due to the reversible reduction of free Cd(II) ion. It was shown that the second wave (-0.958 V) for the reduction of the complex species, CdL or CdHL⁺ is irreversible and the limiting current is diffusion-controlle d (the reciprocal slope: 55.9mV, i_j ∝ h^1/2+_corr. )Formation of the complex species (ML) with a ratio of 1: 1 was confirmed from the data of the amperometric titrations. The dependence on pH for the half-wave potential of the second wave, showed that the complex species participating in the electrode reaction was changed from CdHL⁺ to CdL near pH= 4.4.
The electrode reaction mechanisms of the second wave are as follows;
pH≤4.4, CdHL⁺ + H⁺ + 2e Hg →_kj1 Cd(Hg) H₂ L (I)
pH>4.4, CdL+ 2e + Hg →_kj2 Cd(Hg) + L^2- (II)
where k_ji denotes the reaction rate constants. The stability constant, K_cdHL, was calculated to be 10^5.6 by using an equation proposed by Vlcek. The values of K_ji for mechanisms ( I ) and were also determined to be k_j1=6.9 × 10^-6cm/s and k_j2= 1.2 × 10^-6cm/s, respectively. T(IhIe)frequency dependence of the “cut-in” height in the oscillopolarogram was increased in the order of the complexes: <CdHL⁺: This was in the reverse order of the stability constant.

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In cathodic scan pulse polarography (cspp) with the initial potential (E₁) of 0 V vs. SCE, oxidized dithiothreitol (cyclic disulfide form of dithiothreitol, OX-DTT) gave two cath odic waves of E_1/2=- 0.413 V and -1.05 V at 10^-4mol/dm³ a nd pH 4.5, corresponding to t he two DC polarographic waves of OX-DTT. In anodic scan pulse polarography (aspp) with E₁=-1.5 V, OX-DTT gave one cathodic wave at E_1/2=-1.05 V and one anodic wave at E₁ 12.0.44 V. The latter wave was attributed to anodic mercury dissolution by dithiothreitol (DTT)which was produced. at E₁=-1.5 V. In aspp with E₁ = -1.3 V, DTT gave one anodic wave at the same potential (E_1/2= -0.44 V). In cspp with E₁= 0 V, DTT at lower concentra tion (less than 10^-4mol/dm³) gave a peak-shaped cathodic wave with Ep =-0.475 V which was attributed to reduction of monolayer mercury salt of DTT. The appearance of a peak-shap ed wave, instead of a S-shaped wave, was explained as follows, i. d., the reduction c urrent after the application of pulse voltage decayed more quickly as the amplitude of pulse voltage was increased beyond the peak potential. At higher concentration of DTT, additional two peakshaped waves were produce at more positive potential. The lower limit of detection of DTT was ca.3x 10^-7mol/dma by cspp with d. m. e., but DTT as low as 10^-11mol/dm³ could be de tect-ed by cathodic stripping voltammetry with h. m. d. e. at 5 min pre-electrolysis time at 0 V. The cspp and aspp behavior of cysteine and cystine was essentially the same as that of DTT and OX-DTT.

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The weak basic anion exchange resin was prepared by the chloromethylation of diphenyl phosphonate-formaldehyde condensation resin, followed by the amination of the chloromethyl group. The ion exchange capacity of the dry resin was in the range of 0.50 to 1.35 meq/g, depending on the conditions of the amination. The 'optimum pH range for ion exchange was between 2.0 and 6.0 and the time to reach an equilibrium state was 10 to 15 min. This resin showed selective adsorption for CrO₄^2-, MoO₄^2- and WO₄^2- ions. Cr (VI), Mo (VI) and W (VI)adsorbed on the resin could be completely eluted with 0.5 mol/l NaOH solution. Using an acid solution as an eluent agent, only Mo (VI) could be stripped with 0.3 wt% H20^2-1.5 molf/ H₂SO₄solution. The separation of Cr (VI) and Mo (VI) and the recovery of Cr (VI) from the dilute solution (10^-3ppm) were also investigated.

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The isomerization of such unsaturated esters as dimethyl methylenesuccinate [1], dimethyl citraconate [2], dimethyl mesaconate [3], and alkylidenesuccinates [4], [5] by rhodium catalysts has been studied. Tris (triphenylphosphine) rhodium ( I ) chloride-tin ( II ) chloride dihy drate complex was a most effective catalyst. The catalyst isomerized [1] to its α, β-isomers at 100°C. A kinetic study revealed that the isomerization rates were second-order on ester and rhodium, and that those of internal olefins, [2] and [3], were unusually slow. Pseudo equilibrium compositions for the isomerization at 100°C were found to be 29% for [1], 3% f or [2] and 68% for [3] J respectively. Results of the isomerization catalyzed by the rhodium complex will be compared with those of the base-catalyzed isomerization.

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2, 3-Dicyano-1, 4-naphthoquinone [3], which is expected to be a strong electron acceptor, was obtained from 2, 3-dicyano-1, 4-naphthalenediol[2] using fumic nitric acid in a high yield (Fig.1). The reaction of [3]J with nucleophilic reagents, such as aliphatic amines, amides, pyridines and anilines, gave the products[4]∼[25] with a substituent in a cyano group position. The results are presented in the Table. Aniline and o- and p-substituted anilines gave compounds [11]∼[17] (N-substituent), in which a cyano group of [3] was replaced with the amino group of anilines. N-Substituted anilines gave compounds [18]∼[21] (C-substituent), in which a cyano group of [3] was replaced with the carbon at p-position of the amino group of anilines. According to the detailed investigation of the reaction of [3] with N, N-dimethylaniline, in ethanol [19] was obtained in a high yield, in acetonitrile [19] and Crystal Violet [31 a] were obtained, that is, the effect of solvents was observed. The reaction of [3] with diphenylamine yielded the c-complex [23a], which was transformed to be (C-substituent) by boiling in diglyme. The reaction of [3] with, 2, 6-xylidine showed solvent dependence and gave [24] (N-substituent) in THF, [25] (C-substituent) in methanol, respectively. According to the visible absorption measurements of these compounds, the bathochromic effect of the C-substituent was stronger than that of the N-substituent.

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The reactions of the free bases of aliphatic hydrazine derivatives with carbon disulfide were investigated in an aqueous sodium hydroxide solution. Aminoguanidine gave 2, 5-dimercapto1, 3, 4-thiadiazole (DMTD, 94%) and thiourea (50%). The result could be explained by the nucleophilic addition of the hydrazino group of aminoguanidine to carbon disulfide followed by the cleavage of the adduct into DMTD and cyanamide under the strong basic conditions. The latter was further converted to thiourea by the reaction with hydrogen sulfide. The reaction of other hydrazine derivatives such as thiosernicarbazide or semicarbazide gave DMTD under similar reaction conditions. The reaction of semicarbazide hydrochloride with carbon disulfide in pyridine at 45∼50°C for 4 h gave 1, 5-dicarbamoylthiocarbohydrazide (DCTH, 89%) via thermally unstable pyridinium semicarbazide-1-carbodithioate (PSDTC). When the reaction was stopped after 1 h, only intermediate PSDTC was isolated in 92% yield.

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The dyeing of polyester fiver with disperse azo dyes in tetrachloroethylene has been carried out to investigate the dyeing mechanism. Poly (ethylene terephthalate) was used as po lyester - x fiber, and following disperse azo dyes were empolyed: [type A]
From the measurements on adsorption isotherms and partition coefficients, thermodynamic parameters were derived such as the apparent affinity (-Δ^o_μapp), the standard heat of dyeing (-ΔH^o_dyeing), the change in standard entropy of dyeing (-Δ/S^o_dyeing), the change in standard free energy of solution (-ΔF^o_soln ), the standard h eat of solution (-ΔH^o_soln )and the change in standard entropy of solution (ΔS^o_soln). A linear relation On ship was found between -Δ/S^o_dyeing and Δ/H^o_soln, regardless of the type of the dyes and their substituents, while the relation between 4 S2yeing and 4S' oln. was almost linear for the type B dyes. Linear relationships were also obtained between -Δμ^o_app an. ΔF^o_soln . depending on the types of the dyes and the substituents of their coupling components. Furthermore, a linea r relationship between the square of dipole moment (μ²) and -Δ/H^o_dyeing was obtained fo r the dyes of type A. Based on these results, the structures of the dyes and their substituents w ere concluded to have important effects on the dyeing mechanism which was ascribed to p olar van der Waals' force.

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Bisphenol-type epoxide resins were cured with aliphatic α, ω-dicarboxylic acids in the presence of a tertiary amine as an accelerator, and were also cured with the tertiary amine as a curing catalyst. The relaxation behaviors of these three systems were studied by observing dynamic mechanical properties in relaxation with the structures of these cured resins. On the bases of these observations, β relaxation in the cured epoxide resin which contains a mobile group, such as hydroxy ether group, was interpreted as being composed of relaxation due to the mobile group and another relaxation of the cured resin without the mobile group. Gamma relaxation was attributed to the motion of the methylene linkage which consists of more than four carbon atoms.

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The kinetics of NO removal and aerosol formation from N₂-NO-NH₃-O₂ mixtures under the irradiation with a high energy electron beam (1.2 MeV) has been studied. The concentrations of NO and N₂O were monitored; in an essential time by means of the molecular absor ption spectrometry. The formation and growth of the aerosol were also monitored by observing the attenuation of 633 and 313 nm lights passing through the irradiated gas.
When NH₃ was added to the N₂-NO mixture, the G value of NO redu ction increased by around 2, and at the same time N₂O production was considerably accelerated. These increases are considered to be caused by the reaction of NH2 -radicals and H atoms, which may be produced from the reaction of NH₃ with primary active species such as N₂⁺ and N₂* . When the N₂-NO-NH₃-O₂ mixture was irradiated, some aerofol particles (NH₄NO₃) were formed. A simple model is proposed to explain the phenomenological kinetic behavior of the aerosol, and it is concluded that only a small fraction of the initial NO was converted to the aerosol.

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The adsoption of phosphate ions by a complex of titanium (IV) oxide monohydrate (metatitanic acid) and active carbon was investigated. A sulfuric acid solution of TiOSO4 (TiO₂ 250g, H₂SO₄ 1044 g /l) formed as an intermediate product during t he production of titanium ox ide ( IV) was used as a staring material for metatitanic acid. The complex was prepared by the following method: A suitable amount of the sulfuric acid solution of TiOSO₄ was mixed w ith active carbon. The mixture was heated to 180°C f or the removal of excess amount of sulf uric acid. The titanium(IV) oxide sulfate deposited on the active carbon was hydolyzed into metatitanic acid by washing with water, and the product was dried. A complex obtained u nder suitable conditions (5 m l TiOSO₄ solution/10 g active carbon) showed an adsorption cap acity comparable to that of a commercially available metatitanic acid (in Freundlich equatio n; q=kc^1/n, k was equal to 17-19 mg PO₄^3-/g adsorbent)., The amount of phosphate ion adsorb ed per unit amount of metatitanic acid contained in the complex was about ten times as large as that of a commercially available one. The complex adsorbed condensed phosphate ions. Th e slope of isotherm was 0.116 in the case of orthophosphate ion and 0.2 61 in the case of trip hosphate ion. By means of the active carbon as a carrier, the complex adsorbed Meth ylene Blue, iodine and phenol. The adsorption capacity of the complexes of these substanc es, however, decreased with the increase of the ratio of TiOSO₄ solution (ml) to the active carbon (g). In column tests, phosphate ion adsorbed on the complex were elluted with 2 N sodium hyd roxide, and the adsorbent was regenerated by an acid.

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The photoreaction of pyruvamide with 2, 3-dimethylo-2-butene in ethanol gave products [1], [2], [3], and [4] in a fairly high conversion. The products [1], [2], and [3], are 1: 1adducts of pyruvamide and 2, 3-dimethy1-2-butene, and [4], is a pinacol. In low conversion experiments in methanol, [2], J was exclusively produced. The ultimate quantum yield for the formation of [2], was 0.036. Stern-Volmer slope of 103.6 l mo^-1 was obtained by naphthalene quenching experiment. From this experiment, it was confirmed that [2] was formed via the triplet state of pyruvamide. From the dependence of quantum yield on alkene concentration and quenching experiment, the ratio of the rate constants of elementary processes was calculated.

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Halogenation of enamino ketone-copper (II) chelates 1 with solid anhydrous copper (II)halides in benzene under nitrogen has been investigated. Three moles of copper ( II ) chloride were required for chlorination of his (4-anilino-3-penten-2-onato) copper (II) [1a]. The copper (II) chloride was almost quantitatively converted into copper( I ) chloride (No.5 in Table 1)and hydrogen halides were scarcely evolved. In the presence of a radical scavenger, [1a] gave 4-anilino-3-chloro-3-penten-2-one [2 a] in a lower yield obviously (No.2∼4). Copper (II)bromide gave a-bromo enamino ketones [3] in higher yields than copper(II) chloride under similar conditions (No.7 and 9, 11 and 13). On the basis of these results the reaction is postulated to proceed by ligand transfer from copper (II) halide to [1 ].

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An alternative method for carboxylation of the Grignard reagents was developed. Both aromatic and aliphatic Grignard reagents gave the corresponding carboxylic acids in moderate yields by the reaction with pentacarbonyliron followed by treatment with iodine-water. The secondary alkyl Grignard reagents gave the acids rather in low yields.

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Some Co₂(CO)₈-diphosphine catalysts were found to be effective for the hydroformylation of aClHlyPl Phacetate and allyl formate; the activity decreased in the order: diphos>cis -Ph₂PCH=CHPPh₂>Ph₂PC=CPPh₂> none >Ph₂PCH₂PPh₂ > PPh₃. Under the conditions employed, 4-acetoxybutanal was 80% or above of three isomeric aldehydes produced.

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N, N-Dimethyl-p-phenylenediamine was prepared in about 80% yield through the electroreduction of N, N-dimethyl-p-nitrosoaniline by 4.0 Fimol of electricity under a constant current density of 0.005 A/cm² in 10% H₂SO₄ aq. or 10% H₂SO₄ aq. -MeOH medium by using a stainless steel, carbon or platinum plate as a cathode electrode.

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Soft Brönsted acids such as phenols, naphthols or hydroxypyridines were found to catalyze the coupling reaction of 1-naphthol with 1-diazonio-2-naphthol-4-sulfonate. In contr ast, a hard acid such as acetic acid was not effective for the reaction. The kinetic data well agreed with the Brönsted equation k=1.3×10²¹ Ka^0.83. Mechanism of the reaction is discussed.

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The solubility parameter of solvent can be indicated a point in a three dimentional solubility parameter (δ_d-δ_p-δ_h) space. Regions of solubility are found for polymers when solubility data are plotted. These regions are not globular, but look like a crushed ball. When polymers were dissolved in many solvents, solubility region ' for polymers occupied a wide space in the three dimensional solubility parameter space. The volume of the region was called solubility index. The solubility for polymers were evaluated by the solubility index.

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Mixtures of barium acrylate-methacrylate were prepared by crystallization from an aqueous solution of acrylic and methacrylic acids in molar ratios ranging from 1/9 to 4/6. Thermal reaction of the above mixed salts in the solid state under reduced pressure gave four different dimers, dimethyl 2-methylene-4-methylglutarate [1], dimethyl 2-methylene-4, 4-dimethylglutarate [2], dimethyl 2-methyleneadipate [3] and dimethyl 2-methylene-5-methyladipate [4]. On the other hand, the mixed salts of magnesium, calcium and strontium gave dimers[3] and [4]. Dimers[1]and [3] were obtained in the yield of 12.8% and 3.9%, respectively, when the mixture with the molar ratio of 2/8 was heated for 3 h at 210°C. In the case of the strontium salt, [3] was obtained in 7% yield heating the equimolar mixture for 2 h at 220°C. The change of the crystal lattice measured by X-ray analysis showed that the lattice structure of the barium salt was not destroyed as a whole but that of the strontium salt was disordered by heating.

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