From the angular variation of X-band ESR spectra of Gd 011 in single crystals of La2Mg3. (NO₃) 12'24 H₂0 (LMN) and La2Zn3 (N08)12. 24 H₂0 (LZN) were measured at room temperature, 77°K, and 4.2°K, the spin Hamiltonian parameters were calculated. The spectra of Gd (III) in LMN and LZN showed similar angular variations at the measured temperatures. The zerofield splittings (or the largest spin Hamiltonian parameter, 1)2 of Gd 110 increased with decreasing temperature. The values of VI were larger in LZN than those in LMN. It was found that the variation of the values of b with temperature was similar to that of temperature dependence of the lengths of the crystal axes c and a of the double-nitrates. These facts indicate that in the double-nitrate crystals a linear relationship exists approximately between the lengths of the crystal axes and the zero-field splittings associated with the intensities of the crystal field on Gd 010 at each temperature. t Electron Spin Resonace of Gcl(ili) in Single Crystals of Some Lanthanoid (ifi) Double-nitrates,

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In order to study the purity of phenanthrene, the evaporated thin films of phenanthreneanthracene mixed crystals containing 10-3-10-9 mol/mol of pure anthracene (average life-time of fluorescence was 19.87 nec in the region of 380-500 nm) in phenanthrene (69.57 nec, at 360-450 nm) were prepared on quartz plates. Phenanthrene was prepared by treatment of commercial phenantrene with maleic anhydride and chloranil, and then with metallic sodium in absolute ethanol. It was finally purified by zone-refining. The fluorescence spectra were measured both at room and liquid nitrogen temperatures and the fluorescence life-times at room temperature.
The concentration of anthracene did not influence the wavelengths of fluorescence maximum peaks both at room and liquid nitrogen temperatures. However, the ratio of the intensity of fluorescence at 370 nm characteristic of phenanthrene to that at 410 nm characteristic of anthracene changed depending on the concentration of anthracene in phenanthrene in the region of 10-3-10-8 mol/mol.
On the other hand, the fluorecence life-times changed with the concentrations of anthracene in phenanthrene even when the concentrations were decreased to less than 10-8 mol/mol.
Therefore, it was concluded that the concentration of anthracene which is contained in phenanthrene as an impurity could be decreased to less than 10-8 mol/mol, by utilizing the method of preparation described here.

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The interaction of poly (methacrylic acid) (PMA) with added salts and surfactants were studied by means of viscometry.
The reduced viscosity of aqueous salt solution of PMA, which is a weak polyelectrolyte, increases rapidly in a highly diluted region and this behavior is contrasted to that of ordinary strong polyelectrolytes. This difference is attributed to the fact that the PMA chain expands with dilution due to the increase of the degree of dissociation of carboxylic group. Salt effect on aqueous PMA solutions was interpreted in terms of dissociation equilibrium of carboxylic group.
In the presence of surfactants, the lowering of reduced viscosity was observed regardless of the properties of hydrophilic parts of surfactants in a highly diluted region of PMA solution. Hydrophobic interaction between PMA and surfactants is predominant and overcomes the effect of dissociation, so that the polymer chain does not expand in low concentration range. Especially in the case of anionic surfactant, in spite of electrostatic repulsion it obviously binds onto the PMA chain judging from the viscosity change and a kind of mixed micelle is formed.

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The explosion limits of C, monoolefins and C, C, dienes mixed with oxygen were determined by use of the admission method at the temperature below 600°C and reduced pressure in the range of 40-50 vol % of olefin, in order to study the relationships between the molecular structure and explosion behaviour of olefinic hydrocarbons. The results were compared with those of C₂C4 olefins.
The isochores for the explosion limits of C₂C5 monoolefins and C, C, dienes were grouped into three classes as shown in Table 1. The three types of the classification were originally proposed by Townend in the case of hydrocarbons-air mixtures at high pressure. These were Type 1, 2 and 3 shown in Fig.6. The isochores of Type 1 were further 'subdivided into Type A and Type B on the basis of the thermal explosion theory.
The effect of substituents on the types of the isochores was discussed. It was suggested that the initial step in the explosion reaction of monoolefins below 480°C was the formation of cyclic peroxide by direct addition of oxygen to C=C bond. The types of the isochores were explained in terms of the type of aldehydes on the basis of the reaction mechanism proposed above.

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The exchange ability of alkali ion in β"-A1O₂ with hydroxonium ion or proton in water has been examined by means of chemical analysis, X-ray analysis and measurement of heating weight loss.
It has been clarified that alkali ion in β"-Al2O₂ was exchanged with hydroxonium ion in water at room temperature, but at high temperature of 300-1000°C it was exchanged with proton in steam.
β"-Al2O₂ replaced with hydroxonium ion was dehydrated at 200-300°C, and at 1200-1300°C, β"-Al2O₂ with proton released the proton to turn into α-Al2O₂. In order to clarify the relation between the exchange ability and the catalytic activity, further examination on the catalytic activity was carried out. The catalytic activity of the partially exchanged β"-Al2O₂ was smaller than those of both β-Al2O₂ which alkali ion content was less than the partially exchanged β"-A108 and the fresh β"-Al2O₂.
It follows that not only the alkali ion content of β"-Al2O₂ but also the exchange ability of alkali ion in β"-Al2O₂ influence the catalytic activity of β"-Al2O₂.

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The titled conversion has been studied over several nickel-supported catalysts. The reaction was carried out at a temperature range of 150-250°C under atmospheric pressure in a flow reactor.
Magnesia containing about 10-20 wt % of the metal was found to be the most active and selective catalyst for this conversion: silica-magnesia, silica-alumina, r-alumina and titania were inferior to magnesia. When a nickel-magnesia catalyst system was used, the major byproducts were mesityl oxide [ 1 ] diisobutyl ketone 1 2 and 2-propanol [ 3 ] depending upon the metal content of the catalyst: Decrease in [ 1 ]and increase in [ 2 ] and [ 3 ] were observed with an increase of nickel content.
Introduction of small amounts of propionic acid to the feed stream suppressed markedly the activity of the catalyst. Isobutyl methyl ketone was produced when magnesia layer followed by nickel-silica gel layer was used, or when a mechanical mixture of two layers was used as catalyst.
This ketone was not produced through the reaction of acetone with [ 3 ]. Therefore, the titled conversion over nickel-magnesia catalyst is suggested to proceed through the base-catalyzed condensation of acetone to I followed by the hydrogenation of the latter.

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The hydrocracking of cumene and the cumene-isopropylcyclohexane (IPCH) mixture on molybdena-alumina catalysts containing 5-46% MoO₃ has been studied under the hydrogen pressure of 50 atm at 400°C. The catalysts were pretreated with either H₂ or H₂S.
The hydrodealkylation of cumene to propane and benzene, the isomerization of IPCH to other C9-naphthenes, and the hydrogenolysis of IPCH to methane and naphthenes were observed.
The selectivity of the catalysts pretreated with H₂ was quite different from that of the catalysts pretreated with H₂S.
When the catalysts were pretreated with H₂, the isomerization prevailed for the catalysts containing below 12.5% MoO8, whereas the hydrogenolysis was predominant for the catalysts containing more than 20% MoO^2-. On the catalysts pretreated with H₂S, the hydrogenolysis was not observed, while the isomerization proceeded significantly.
The relationship between the selectivity of the molybdena-alumina catalysts for these reactions and the surface structure of the catalysts pretreated with H₂ or H₂S has been discussed.

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When a photochromic benzospiran compound (1, 3, 3-trimethylindolino-6'-nitrobenzopyrylspiran: [ A ]) in poly (vinyl chloride) (PVC) matrix was bombarded with an electron beam of medium energy (15 kV), only yellow species was formed. This is probably a product from a reaction between a metastable colored species ([ B ]) and a chlorinated component liberated from PVC.
Formation of [ C ] increased by the exposure to UV ray after the electron bombardment. This may be due to a reaction between the residual chlorinated component and B I formed by the post-irradiation. When the specimen was bombarded with an intesity of 10^-6 C/cm², the coloring reaction of [ C ] due to the post-irradiation followed a pseudo-first order kinetics in the initial stage, indicating that sufficient ammount of the residual component existed during the post-irradiation. This additional coloration of [C] was observed also in the air. This fact indicates that the formation of [C] is not affected by oxygen and that the liberated component is hydrogen chloride.
Since the post-irradiation intensifies recorded image, this process may be applied to an electron-beam recording system.

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Effect of exchangeable cations on the interlamellar complex formation between montmorillonite and poly (ethylene oxide) (PEO) or polyacrylamide (PAA) has been studied by treating homoionic bentonite (Na-, K-, Mg-, Ca-, or Ba-bentonite) suspension (1%) with PEO or PAA solution (0.2%).
X-ray diffraction patterns of PEO or PAA-treated bentonites revealed that interlamellar complexes containing one layer of the polymers in the interlamellar region of montmorillonite were formed except the case when K-montmorillonite was treated with PAA. The polymers adsorbed in the interlamellar region of alkali metal ion forms of montmorillonite were relatively easily desorbed by washing with water, whereas the polymers adsorbed in the same region of alkaline earth metal ion forms of montmorillonite were not desorbed. Differential thermal analysis indicated that the polyethylene oxides adsorbed on the alkaline earth metal ion forms of montmorillonite were thermally more stable than those adsorbed on the alkali metal ion forms of montmorillonite.
From the results obtained, the formation of interlamellar complexes between PEO or PAA and the alkaline earth metal ion forms of montmorillonite, which swell less easily than the alkali metal ion forms, may be explained by assuming the following adsorption process of the polymers onto montmorillonite from their aqueous solutions: considerably stable chelate polymers are first formed by the coordination of ether or amide groups of the polymers with exchangeable alkaline earth metal ions of montmorillonite, and then penetrate into the interlamellar region of montmorillonite in the form of a cationic polymer.

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Flocculation behavior of homoionic bentonite (Na-, K-, Mg-, Ca-, and Ba-bentonites) particles in aqueous suspension (1.08%) in the presence of cationic, anionic, or nonionic polymer flocculants (1-100 ppm) has been studied.
Cationic polymer (polyethylene imine) flocculated any ion forms of bentonite suspensions. On the contrary, none of the ion forms were flocculated by anionic polymers (sodium polyacrylate and sodium salt of partially hydrolyzed polyacrylamide) except the alkaline-earth metal ion forms for which slight flocculation was observed with sodium polyacrylate (Table 2). Nonionic polymers showed a very powerful flocculating effect toward the alkaline-earth metal ion forms of bentonite suspensions. On the other hand, the alkali metal ion forms were not flocculated by polyacylamide and flocculated only slightly by polyethylene oxide (Table 3).
The roles of typical polymer flocculants for the flocculation of various ion forms of bentonite suspensions are discussed on the basis of the results obtained.

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The mineral component of bone or tooth is hydroxyapatite containing a small amount of carbonate ions. The crystallinity of biological apatites is one of the important factors which affect its chemical stability.
In this study, the cause of lattice imperfection of carbonate-containing hydroxyapatite has been investigated by means of variance and Fourier analyses of X-ray diffraction line broade- flings. The variance (i. e., mean-square breadth) of diffraction line profiles increased in proportion to carbonate contents in carbonate-containing hydroxyapatite. Among the factors which contribute to the variance, the"mistake"of lattice was much more effective than the crystallite size. For instance, about 90% of variance was effected by the mistake of lattice while only 10% was effected by the crystallite size, as shown in Table 4. In tooth enamel, there were more mistakes in direction of the a-axis than the c-axis.
These results lead to the speculation that the lattice imperfection of carbonate-containing hydroxyapatite or biological apatites are caused by the disorders in atomic arrangement due to substituted carbonate or other ions.

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The mineral component of bone or tooth is hydroxyapatite containing a small amount of carbonate ions. The crystallinity of biological apatites is one of the important factors which affect its chemical stability.
In this study, carbonate-containing hydroxyapatite resembled to tooth structure was synthesized and treated with various solutions which contain Sr", Ph", F-, PO₄8- or some other ions. The reaction products and their crystallinities were estimated by means of X-ray diffra- ctometry. The crystallinity was evaluated by the Fourier analysis of powder diffraction line profile.
The presence of fluoride ion was quite effective to increase the crystallinity of carbonatecontaining hydroxyapatite even in a low concentration. It was found that the improvement of crystallinity was mainly due to decrease of lattice imperfection and partially due to the growth of crystal. Phosphate ion restored lattice imperfection effectively according to the substitution for carbonate ion. It was found that the peak shift in the X-ray diffraction lines was caused by the reaction of carbonate-containing hydroxyapatite with diverse ions.
These results mean that fluoride ion at low concentration works effectively on the stabilization of tooth apatite and the recrystallization of fossil bone or tooth.

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The thermal behaviors of calcium sulfate anhydride at high temperatures above 1000°C, such as II CaSO₄4=t I CaSO₄ transition, CaSO₄⇔ CaO SO₃ decomposition and CaO-CaSO₄ eutectic phenomena, were investigated mainly by thermal analysis (micro-TG-DTA) under atmosphere of nitrogen gas.
Although several investigators had suggested that CaSO₄ CaO + SO. decomposition occurs after the termination of I CaSO₄ I CaSO₄ transition (transition temperature: 1180 °C), the decomposition of CaSO₄ really started around 1O^2-0°C. Therefore, CaSO₄ I CaSO₄ transition happened in the process of CaSO₄ decomposition. The cause was explained that the decomposition pressure of I CaSO₄ and that of I CaSO₄ did not differ so much because both have similar crystal structure and the tetragonal lattice of II CaSO₄ make possible to approach the cubic lattice of I CaSO₄ by anisotropic expansion before starting the transition.
The eutectic phenomena of CaO-CaSO₄ were confirmed by a broad endothermic peak around 1350° on the DTA curve. The eutectic composition was given as 18 wt % CaO and 82 wt % CaSO₄ from the variation in height of the eutectic peak by the addition of CaO to II CaSO₄. The eutectic crystal was also observed on scanning electron microscopy.
The activation energy for the decomposition of CaSO₄ was calculated as 90 kcal/mol from TG curve and that of ground li CaSO₄ was 80 kcal/mol. The activation energy was not so influenced by mechanochemical effect because the structural distortion given to the crystal grain of IL CaSO₄ disappeared rapidly at high temperatures above 1000°C.

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The reactions between phosphoric triamide and anhydrous MCl2 {M=Mn (II), Co (II), Cu (II), Zn (II), (as trace nutrients) or Cd (II) } in methanol were studied, and the products were examined by chemical analysis, X-ray powder diffraction method and IR spectroscopy, etc. New complexes, [M (PO (NH₂) 3) 2]Cl2 (1), were formed in the reaction of PO (NH₂) 8 with Mn (II) and Co (II) chlorides, and [Cd (PO (NH₂)8) Cl2] (2) with Cd (II) chloride. On the other hand, in the reaction with Cu (II) chloride, PO (NH₂), was obviously decomposed, giving Cu, (NH₂), Clex H₂O, Cu (NF18) 2Cl2 and a small amount of NII4Cl. An oily substance, of which the chief product seemed to be a Zn complex of PO (1\11-12) 8, was produced in the reaction with Zn(11) chloride.
Both the isolated complexes (1) and (2) are hygroscopic crystalline powders, soluble in water and methanol but insoluble in various organic solvent.
Their IR spectra and conductivities suggest that (1) is 6-coordinate complex, in which PO (NH, ), is bound to Mn (II) or Co (II) as a terdentate ligand through the N atom of amide, and that C_2Cj is complex, in which PO(NH₂), is bound to Cd(11) as a bidentate ligand through both the phosphoryl O atom and N atom of amide.
Finally, it was found that these complexes are less hygroscopic than PO(NH).

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The formation of fine vanadium nitride powders by a vapor phase reaction of VCl4-N1-13-1-12- N2 system was investigated between 700°C and 1200°C with emphasis on the effects of reaction conditions on the particle size and chemical composition. Oxidation resistance and thermal stability of vanadium nitride powders were also examined.
The reaction was performed by two methods concerning the mixing of reactant gases; (A) low temperature mixing (400-640°C) and (B) high temperature mixing (700-1100°C). The mean particle size and surface area of vanadium nitride powder prepared by method (A) were around 500 A and about 10 m2/g, respectively. Those values of vanadium nitride powder prepared by method (B) were around 100 A and about 70 m2/g, respectively. These vanadium nitrides showed a wide range of nonstoichiometry; atomic ratio NIV=0.96-1.64 (A) and NIV=1.55-1.87 (B). X-ray diffraction patterns showed that all nitride samples had NaCl- structure. The atomic ratio NIV decreased with the increase of reaction temperature or VCl4 or H₂ concentration, and increased with the elevation of NH₃ concentration. The lattice parameter decreased with the increase of NIV ratio. Density measurements showed that vanadium nitrides obtained had V vacancies.
The oxidation of vanadium nitride powders began at about 200°C in air. The nitride powders with atomic ratio N/ V 1 began to decompose at about 600°C under vacuum. On the basis of these results, the formation process of vanadium nitride particles was discussed.

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The hydrothermal reaction between calcium hydroxide and silica gel at the temperature range from room temperature to 80°C was investigated.
1) The admixed tablet of CaO/SiO₂=1/1 in molar ratio was heated in a small autoclave at the temperature range of 50-80°C. The initial reaction proceeded rapidly, and was followed by the slowdown of the reaction rate. The activation energy of the initial reaction was calculated to be 17 kcal/mol by use of the Jander's equation.
2) When silica gel was added to the saturated lime solution, its pH value decreased rapidly within several minutes, and then decreased slowly with the reaction time.
3) Contents of silanol groups in the silica gel estimated by adsorption quantity of methyl red in benzen solution and the reactivity of silica gel were decreased with the increase of treatment temperature.
4) The reaction between calcium hydroxide and silica gel in a grinding ball mill proceeded more rapidly than in a closed still vessel.
X-ray diffraction pattern and electron microphotograph revealed that the reaction products of above two grinding methods were different each other.

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Out of 47 thioureid derivatives synthesized, the title compound was chosen to perform a screenting test on the chelate formation with 66 metal ions. The formation of colored 0.14. elate, was visually observed for Pd2+, Cu", Pt4+, Au", Ru"and Ag+ in acidic media. The highest sensitivity was obtained for Pd chelate and the chelate formation was completed within five minutes at pH 2 at the room temperature. Conformity to Beer's Law is sufficiently good up to 4 ppm of Pd. The Pd chelate was readily extracted with chloroform and exhibited the maximum absorption at 280 and 320 nm. The excess reagent, causing an absorption beak tet 290 nm, could be removed by shaking with 1 moll/ NaOH solution, while the chelate remained unchanged. The molar absorption coefficient was 1.76 X 1O^2- (reference: -1-120) at 3210, nm and 2.40 x 1O^2- (reference: CHCl8) at 280 nm. According to Ringbom's plot, the optimum concentration range was 0.4 ppm for the 320 nm peak and 0.2, ppm for 280 n, m peak. Pretreatment of sample solution with perchloric acid was effective to reduce the interference of CI-, 0sO^2- or Rus and also to reduce the aging effect of the Pd solution of 10-3-4'0-4 mol/l.
The proposed procedure is as follows. Add several drops of perchloric acid to the sample solution containing up to 40, ug Pd and heat to almost dryness. Make up the solution nearly 10 ml and adjust the pH to about 2 with 1 mol/l NaOH solution. After adding 1 mi of the reagent solution (2 X 10-3 mol/l), extract the chelate by shaking with 8 ml of chloroform. Allow to stand for 5 minutes to fully separate the two layers. Then scrub the organic layer to remove the excess reagent with equal volume of 1 molg NaOH solution. Measure the absorbance at 280 nm in the chloroform as reference solution.

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An atomic absorption spectrophotometric method by using a carbon-tube flameless atomizer was proposed for the determination of trace amounts of cadmium, lead and copper. In this method, the use of dithizone-carbon tetrachloride extraction system was recommended for a pretreatment to remove interfering materials such as large amounts of alkali and alkaline earth metal salts. The extraction system has several features as follows. ( 1 ) Dithizone and the dithizonates are fairly stable. ( 2 ) Excess and deficiency of the reagent can be easily found from the coloration of organic phase. ( 3 ) Cadmium (≤0.04ug), lead (≤0.8ug) and copper (≤0.8ug) are quantitatively and simultaneously extracted in a pH range 5-10.5, even by using a large aqueous/organic phase volume ratio (Vw/ Vo) such as 50. ( 4 ) Consistent calibration curves are obtained for both fresh and sea waters.
The sensitivities for 1 % absorption of the method with the Vw/Vo, of 10, were 0.004 ppb for cadmium and 0.09 ppb for lead and copper. The coefficient of variations (10 replicate samples) was about 3% in each case. Most diverse ions which interfered with the determinations of cadmium, lead and copper in the case of direct injection of aqueous samples, gave no effect even when present in 1000-fold amounts, but cations such as zinc, copper and nickel at several tens times, interfered with the determination of lead.
The method was applied to the analysis of river and sea waters, and soil extracts.

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A multivalent ion can indirectly be determined in terms of a potentiometric analysis of an excess of a monovalent precipitant ion using an appropriate monovalent ion-selective electrode.
The precision of indirect method is described in relation to that of potential reading and that of added amount of precipitant. The optimum amount of monovalent precipitant was determined by the solubility products of the precipitates and by the precision of determination. on the basis of potential reading. The effect of added amount on the precision of determina- tion was discussed. Theoretical calculation showed that the precision of determination in terms of indirect calibration curve method is higher than that in terms of direct calibration curve method as the precision of potential reading decreases. The precision of indirect determination of sulphide ion based on portentiometry of silver ion using silver ion-selective electrode is statistically higher than that of direct determination of sulphide ion using sulphide ion-selective electrode.

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By using the spherical porous co-polymer of styrene-divinylbenzene (HrrAcm GEL 3010) as a column packing, rapid separation of steroid hormones such as testosterone, estrone, hydrocor- tisone, 11-deoxycorticosterone and its derivatives was achieved.
Resolution is improved by adding water to the methanol mobile phase. The retention time increases with the water contents in the methanol mobile phase and a linear relationship is obtained between the water contents and the logarithmic retention time. The separation is similar to that of reversed-phase partition chromatography using a octadecylsilane support material. The separation mechanism can be explained as follows. The methanol phase is formed on the porous polymer by selective sorption from the water-methanol mobile phase. Partition of the solutes to the methanol phase on the porous polymer increases because of its higher solubility to methanol than to the water-methanol mixtures.
11-Deoxy-17 a-hydroxycorticosterone and 11-deoxycorticosterone, which have the similar structure, can be separated within 8 minutes at 1 m//min of 10 vol % H₂O in methanol and 40°C of column temperature, using 500 mm long and 2.1 mm i. d. column.

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Thermal decomposition process of zirconium oxide chloride octahydrate (ZrOCl₂ 8H₂0) was investigated by changing the heating rate. Thermal equilibrium between sample and atmosphere was nearly achieved at the heating rate of 15°C/hr. On the basis of stoichiometric considerations of TG curves and its differential curves, chemical analysis of the decomposition products, and analyses of infra-red spectra and X-ray diffraction patterns, following stepwise thermal decomposition is proposed; (1) ZrOCl2 H₂O is dehydrated to produce ZrOCl2.4 H₂O, (2) dechlorination of ZrOCl2.3 H₂0 or ZrOCl2 H₂O proceeds and hydrated zirconium oxids comes out, (3) monoclinic zirconium oxide results above 850°C. In the thermal decomposition zirconium is not removed from the system.

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The equimolar mixtures of limonene or 2, 6-dimethyl-2, 7-octadiene and chlorinated acetic acids (monochloro, dichloro or trichloroacetic acid) was stirred for 1.5-46 hours from room temperature to 100°C with or without solvent (dichloroethane, benzene or water) and cation exchange resine.
Hydration of limonene furnished optically active a-terpineol with high conversion (86% at best) and selectivity. Similarly, hydration of 2, 6-dimethyl-2, 7-octadiene gave only optically active 2, 6-dimethyl-7-octen-2-ol with high conversion (76% at best).

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A model reaction of hardening process of urushiol which is a principal component of Urushi (Japanese Lac) was investigated.4-t-Butyl-1, 2-bonzoquinone and methyl linoleate were mixed and allowed to stand for 48 hours at room temperature. The reaction products were characterized by GC/MS, or first separated into six fractions by thin layer chromatography and characterized by IR, NMR, UV and MS spectrometries.
The results showed the presence of methyl 9- (2-hydroxy-4- (or 5-) t-butylphenoxy) -10, 12- octadecadienoate and/or methyl 13- (2-hydroxy-4- (or 5-) t-butylphenoxy) -9, 11-octadecadienoate, methyl 9- (2, 3-dihydroxy-5-t-butylphenyl) -10, 12-octadecadienoate, methyl 13- (2, 3-dihydroxy5-t-butylphenyl) -9, 11-octadecadienoate, methyl octadecatrienoates, 4-t-butylcatechol and dimers of 4-t-butylcatechol in the reaction products.
The results suggest that hydrogen abstraction from the methylene group between two olefinic double bonds of methyl linoleate by 4-t-butyl-1, 2-benzoquinone formed the conjugated radical and t-butyl-o-semiquinone radical, and that the compounds described above were formed by combination and disproportionation between these radicals.

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The hydrolysis of (-)-menthyl and (+)-bornyl esters of (±)-α-hydroxyacids was investigated on the corresponding diastereomers in acidic or basic media. The esters with mandelic acid whose steric configurations of the alcohol part and the carboxylic acid part were S and R or R and S, respectively, were hydrolyzed faster than the diastereomeric counterparts. Contrary to the cases of esters with mandelic acid, corresponding esters with atrolactic acid and 2- hydroxy-2-phenylbutyric acid were hydrolyzed slower than the diastereomeric counterparts. (±)-Pinacoly1 esters with (±)-α-hydroxyacids used here showed the same trends. The correlation of diastereo-differentiation with the steric configuration of the substrates was examined and the conformation of these esters at the transition state is proposed.

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With interest in the substitution reaction at a crowded position, the halogenation of 1- phenanthrol [1] was studied. The chlorination of [1] with SO₂Cl2 in AcOH afforded the 4-chloro [4] and 2, 4-dichloro compound [5] successively. On the bromination with Br₂ (1 mol) in CCl₄, [1] gave the 2-bromo compound [2], while in the presence of Na₂CO₃ it gave mainly the 4( ? ) -bromo isomer [3] When contacted with an acid, [3] isomerized to [2] with great ease, and because of this lability it was not purely isolated. From these facts the course of the bromination is assumed as follows:
The methyl ether of [2] was treated with n-butyllithium and dry-ice successively to yield the corresponding 2-carboxylic acid [7]. This acid was converted by the Curtius reaction into 1-methoxy-2-phenanthrylamine, which was also derived from an authentic 1-methoxy-2- nitrophenanthrene. The oxidation of [4] with CrO₃ gave 1, 4-phenanthrenequinone.
The high reactivity of the crowded 4-position in the chlorination was assumed to be due to steric acceleration in the addition-step.

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The reaction between benzoyl halide and heptafluoroisopropoxide ion, derived from hexafluoroacetone and fluoride ion, was thermodynamically controlled and gave unstable heptafluoroisopropyl benzoate at a low temperature such as 0°C (Table 1).
In contrast with this, the similar reaction with benzyl halide required a higher temperature, 80-85°C, and stable benzyl heptafluoroisopropyl ether was afforded in a good yield.
Other ring-substituted benzyl halides reacted under the similar condition, and p-methyl- and m- and p-fluoro-, chloro- and nitrobenzyl heptafluoroisopropyl ethers were obtained in the fair yields (Table 2).
On the basis of the '9F NMR chememical shifts of m- and p-fluoro derivatives, the σR° and σ1 values for CH₂0CF (CF₃)₂ group were determined to be -0.01 and+ 0.19 respectively.

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The fluorescence properties of the fluorescent probes, 4-methyl-7-anilinocoumarin (MAC) and 4-methyl-7-diethylaminocoumarin (MDC), have been found to be highly sensitive to environment change in the previous study of the solvent effect on their fluorescence spectra. In the present study the fluorescence spectra of the fluorescent probes in aqueous solutions of nonyl-C61-1, -(-CH₂CH₂0-)₁₀H (NP-10) were measured in order to develop a simple method for the determination of CMC of nonionic surfactants and to examine the solubillization mechanism of small molecules into micelle of the surfactant.
From results of the measurements, the CMC of the surfactant was determined accurately from the change of the fluorescence intensity. The solubillization curves of MAC, MDC, and dansyl amino acids (DNS-amino acid) into NP-10 micelle were also obtained from the change of the fluorescence intensity. In addition, the partition coefficients of the fluorescent probes between micellar phase and bulk aqueous phase could be obtained. The partition coefficients increase in the order: DNS-alanine DNS-leucine NDS-phenylalanine MDC MAC.
Each of the fluorescent probes solubilized in different regions of the micelle depending on their hydrophobicities. By comparison of the emission maximum of the probes in the micellewith that in various organic solvents, it was recognized that MAC solubilized in the region of the micelle whose polarity corresponds to 10 in units of dielectric constant, that is, hydrocarbon phase and that MDC solubilized in the region whose polarity corresponds to 28, that is, the region between hydrocarbon and polyoxyethylene phases and that DNS-leucine and DNS- phenylalanine solubilized in the region whose polarity corresponds to 38, that is, polyoxyethylene phase and that DNS-alanine lied at the surface of the micelle.

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A series of derivatives of 4, 4'-bis (monochloro-1, 3, 5-triazin-2-ylamino) -2, 2'-stilbenedisulfonic acid of the general formula ( 1 ) were synthesized by the condensation of 4, 4'-diamino-2, 2'- stilbenedisulfonic acid with 6-substituted 2, 4-dichloro-1, 3, 5-triazines as the reactive whitening fluorescent agents.
These compounds reacted with cotton in the presence of Na₂CO₃ to give fluorescent fabrics from which the fluorescent agents were not removed even by the treatments with hot pyridine and hot DMF.
While, in the reactions with nylon and silk, the presence of acetic acid was necessary for fixation of the whitening agents in good yields; in the reaction with nylon most of the agents fixed in above 80% yields to give intense fluorescent fabrics.
However, in the case of silk, fluorescences of the treated fabrics were very weak in spite of the high fixation yields, showing that these compounds are suitable for nylon and cotton, but are not applicable for silk.
In the case of cotton, it was found that the fluorescence intensity somewhat decreased while the light-fastness somewhat increased by the combination of these fluorescent agents with the fibrous material.

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To investigate the composition and light fastness of homopolymer of polymerizable group containing Naphthol AS series azo dyes, poly[4-arylazo-3-hydroxy-2-naphthoic m-methacryl- amidoanilides] were prepared from the homopolymerization of monomeric dyes synthesized by the coupling reaction of 3-hydroxy-2-naphthoic m-methacryla mideoanilide with aromatic diazonium salts. The polymeric dyes containing the following- aryl groups were prepared, namely, the aryl groups were: 2-CH₃0-5-(C₂H₅)₂NSO₂C₆H₃, 2-CH₃-4-ClC₆H₃, 2-CH₃0-5-C₆H₅CH₂SO₂C₆ H₄, 3-ClC₆H₄, C₆H₅.

It was proved from GPC analysis that the polymeric dyes possessed a broad distribution of molecular weight but main components in the polymeric dyes were tetramer-hexamer. And it was confirmed from visible and infrared absorption spectra that a content of keto tautomer in the polymeric dye decreased and a content of enol tautomer in the polymeric dye increased, as compared with that of the monomeric dye.
The comparison of light fastness of the polymeric and monomeric dyes were caraied out in MMA resin cast film and in baked melamine-alkyde paint, as a result, light fastness of the polymeric dyes were poor than that of the corresponding monomeric dyes. It was presumed as a reason that the poor light fastness was yielded from a change of the proportion of tautomer in the polymeric dye.

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The solid film of poly (γ-methyl n-glutamate) (PMDG) was obtained from its chloroform solution in which a-helix form is produced. During evaporation, chloroform was replaced by ether when the concentration of PMDG in chloroform was ca.30 wt %. This sample was drawn in various extensions at 25, 75, 104, 150 and 180°C. Both α(helical chain) and β(extended chain) were found in oriented PMDG. We have studied the relationship between the true stress and the true strain and also, the mechanism of the transformation from α-form to βform.
In order to study the relationship between mechanical behavior and structual variation, the molecular chain orientation and the fraction of α and β-forms were evaluated at various temperatures and elongations. The following results were obtained about the mechanism of α and βtransformation of solid PMDG. ( 1 ) A part of α-form in the original sample transforms into fl-forms by drawing after the orientation of α-form proceeds along the drawing direction. ( 2 ) The critical strain at which β-form appears, is dependent on the drawing temperature and increases with increasing temperature. ( 3 ) Also, the fraction of β-form depends on the drawing temperature as well as the magnitude of elongation, and is a function of relative magnitude of shear stress to cause the mutual slip of α-form and that required to transform α-form into β-form. ( 4 ) During the drawing made above the viscoelastic crystalline dispersion temperature (150-170°) at which the mutual and migrational slip of α-form predominates in the relaxation mechanism, α → β transformation is not observed.

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Photodegradable polymers containing carbonyl groups were prepared by copolymerization of styrene with benzylideneacetophenone or benzylideneacetone and the monomer reactivity ratio was determined for these copolymerization systems. The results are as follows: St (M₁) - BAPh (M₂) r₁=0.84 ± 0.05, r₂=0.02 ± 0.10; St (M₁)-BA(₂) r₁=1.76 ± 0.02, r₂= -0.1 ± 0.1. The structure of copolymers was analyzed by IR spectra. By applying the method of emulsion polymerization without initiators, new method of obtaining high-molecular weight copolymers was developed. The photodegradable behavior of the styrene-benzylideneacetophenone copolymers was traced in terms of molecular weight determination by GPC, UV and IR spectra after irradiation to their benzene solution with high-pressure mercury lamp. It was found that the decarboxylation occurs at side chains and at the same time the scission of main chains proceeds markedly in terms of the. Norrish II mechanism.

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Di (2, 4, 6-tribromophenyl) 4, 4'-azobis(4-cyanovalerate) [1] has two kinds of initiating groups, azo and tribromophenyl (TBP) groups. The thermal- and photo-polymerization of methyl methacrylate (MMA) by [1] have been studied in comparison with the polymerization by diphenyl 4, 4'-azobis (4-cyanovalerate) [2] or tribromophenylpropionate [3].
In the thermal polymerization, the rate of polymerization by [1] was equal to that by [2]. In the photopolymerization, it was proved that the rate of polymerization by azo group in [1] was equal to that by azo group in [2] while the rate of polymerization by TBP group was higher in [1] than that in [3].
The polymer prepared from the thermal polymerization by [1] intiated the photopolyme-rization of MMA, styrene or acrylonitrile. At the same time, the polymer due to photopoly-merization initiated the thermal polymerization of each monomer described above.

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Iron-protoporphyrin chloride was allowed to bond to such a polymeric derivative as poly-4- vinylpyridine (PVP) or poly-1-vinyl-2-methylimidazole (PVMI) in various solvents and the interaction between the above hemochrome and molecular oxygen (O₂) was examined in com- parison with the analogous monomeric complexes.
The equilibrium constants in the complexation between heme (Fe2+) and the following axial ligands are as follows: pyridine; 51.3 (//mol), imidazole; 45.5 (l/mol), PVP; 1.14 X 1O₂ (l/mol), PVMI; 2.55 x 108 (l/mol). This result indicates that a polymeric hemochrome is more stable than a monomeric one.
It is known that a central iron ( II ) ion is immediately oxidized, when a Fe ( II ) protoporphyrin complex is exposed to O₂ in an aqueous solution. However, since the oxidation of the polymeric complex retarded under an appropriate condition, the stable oxygen complex formed and then the reversible oxygenation could occur. In addition, the oxygenation rate of the polymeric complex was higher than that of the monomeric complex and the degree of saturation of oxygen of the polymeric complex was approximately 100%.

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The most suitable conditions for the regeration of the granular activated carbons which adsorbed various amount of contaminants containing nitro- or chloro-benzene, toluene and intermediate products of dye were investigated. The spent carbons were heated in pure N₂or in the mixed gases of N₂ and 10% steam or 2% O₂. The pore distributions and the adsorp- tivities of the regenerated carbons were compared with those of the virgin carbon. The suitable conditions are greatly dependent on the adsorbed amount. The spent carbon which adsorbed 15 wt % contaminants was able to regenerate well at 950° in N₂ or at 800° in N₂+10% steam. The spent carbon which adsorbed 20 wt % contaminants was not able to regenrate in N2, but it was able to regenerate at 850° in N₂+10% steam. The spent carbon which adsorbed 26 wt % contaminants was not able to regenerate well under any condition. The pore distributions and the adsorption capacities of the regenerated carbons were able to make equal to those of the virgin carbon. The micropore changes into large pore, and the yield is law at a higher temperature than that at which the suitable conditions are fulfilled.

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The bulk polymerization of isobutyraldehyde was studied at 17-32°C and 5700-7700 kg/cm² to determine the ceiling temperature. The ceiling temperature which was determined by extrapolating the yields under various reaction conditions to the zero yield increased from 17°C at 5680 kg/cm² to 32°C at 6560 kg/cm².
The thermodynamic quantities of the polymerization were determined from the volume change of the polymerization and the pressure coefficient of the ceiling temperature. At 25°C and 6160 kg/cm², the heat of the polymerization was -3.3 kcal/mol and the corresponding entropy change was -11e. u.

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The thermal properties of hydrated alumina prepared by the homogenous precipitation method was compared with ordinary hydrated alumina. The latter was a gibbsite as determined by the X-ray powder diffractometry and differential thermal analysis.
After the heat treatment at 900° for a long period, the surface area of alumina from hydrated alumina precipitated by the homogenous method did not decrease, while that from gibbsite decreased remarkably. The surface area of the former was 80 m2/g and that of the latter was 10 m2/g by the that treatment at 1000° for 24 hr.
These results show that alumina from alumina hydrate precipitated by the homogenous method is thermally more stable than that of alumina from gibbsite at heat treatment below 1000°.

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Precise determination of sodium azide (0.3-65 mg) is achieved by the titration with standard thiosulfate solution after the addition of accurately measured volume of iodine-iodide solution. Either the relative error or the coefficient of variation is less than 0.1% when sodium azide is sampled about 65 mg. The whole procedure requires only 10 minutes.
The recommended procedure is as follows. Measure accurately 10 ml of 0.2 N iodine-iodide solution into a titration cell and immediately add 30-70 mg of sodium azide and water to bring the volume to 100 ml. Titrate amperometrically with 0.1 N sodium thiosulfate using a rotating platinum wire electrode at the potential of SCE. Perform a blank run.
Although this titration can be made either by potentiometric or indicator titrimetry, the best result is obtained by the proposed method.

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According to the theoretical prediction of D'Arcy's and Poiseulle's law, the flow rate of fluid in pores must be directly proportional to the pressure difference across the bed or tube within the laminar flow region. However, the experimental results show that the extrapolation of the plots of flow rate against pressure difference does not pass through the origin of coordinate, though there exists a linear relation between them. The intersections on abscissa have the value between O.1 and 0.2 g/cms for gas permeation irrespective of the packed material in column, even in case of open capillary tube. Several experimental results and modified formula for permeability are presented.

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The nitration of 1-phenanthrol [1] was investigated in relation to the reactivity of the sterically hindered 4-position. Thus, [1] was treated with 65% HNO₃ (1 mol) in AcOH at 45°C for 2 hours yielding 2-nitro- [ 2] (40%), 4-nitro- [3] (trace), and 2, 4 -dinitro-1-phenanthrol [4] (20%) and 1, 4-phenanthrenequinone (5%).
To confirm the structure [2] was reduced with IN.2-14-Pd/C to 2-amino-1-phenanthrol followed by the oxidation with CrOs to give 1, 2-phenanthrenequinone. An authentic sample of [3] was obtained from 4-chloro-1-phenanthrol by the reaction with NaNO₂ in DMF. The further nitration of [ 2] and[3] gave [4] as the common product. When refluxed in an HBrAcOH solution, [3] isomerized to [2], but at a temperature below 90°C the isomerization reaction did not take place.

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