The it band shape of the C=O stretching vibration of ethylhexanoate has beenmeasured in solutions of twenty-five kinds of solvent. It has been found that the half band width is closely correlated with the polarity of the solvent, which is represented quantitatively by the Taft's constantó for the substituent X- of the solvent molecule H-X. The band shapefactor which expresses the Gaussian character of the band has been defined as the ratio of the integrated band intensity evaluated by the Wilson-Wells method to that by the Ramsay method. This Gaussian band-shape factor is also correlated with the polarsubstitution constant ó of the solvent. On the basis of these results, the solvent effect on the CO= stretching band of ethyl hexanoate has been discussed, and it is concluded that the local interaction is more predominant than thebulk dielectric effect. Further, an empirical solvent parameter has been introduced in order to explain quantitatively the peak frequencies, the peak intensities, the half band widths, the integrated band intensities, and the Gaussian band-shape factors measured in various solutions.

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An oxygenated acetone solution of 5x 10-4 ∼ 10-3 molg eosin was irradiated in the visible region at -70° C and 0° C. Emission was observed as the temperature of the irradiated solutions was raised. The emission spectrum was identified with that of the fluorescence of eosin. It was proved from the measurement of the glow curves with raising the temperature that the emission resulted at least from two peroxides in the case of the irradiation at -70° C and from one peroxide at 0° C. It was concluded that the singlet oxygen was formedby the low tern-perature irradiation and reacted with acetone forming some peroxides and that the chemilumines-cence resulted from the decomposition of the: peroxides.

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For the purpose of investigating the energy transfer at the gas-solid interface in the catalytic oxidation of carbon monoxide on platinum, the accommodation coefficients (α) of carbon monoxide, oxygen, and carbon dioxide were determined by measuring the heat loss from the platinum ribbon at temperatures of 165∼ 544° C and under gas pressures of 1∼ 5× 10-2 Torr. For carbon monoxide, a is 0.652 at 165° C and decreases with increasing ribbon temperature to 0.615 at 291°C, but increases at higher temperatures. For oxygen, α is 0.471 at 165°C and decreases up to about 400° C, and then shows nearly constant value of 0.39. For carbon. dioxide, a is 0.482 at 165° C and decreases to 0.354 at 544° C monotonously. The temperature dependence of α can be explained as follows. Since carbon dioxide is not chemisorbed on platinum, the impinging gas molecules are adsorbed physically on a platinum surface and exchange their energywith the surface, and a decreases with increasing ribbon temperature. Carbon monoxide and oxygen are chemisorbed on platinum forming a layer at low temperatures, and most of the energy transfer takes place between the layer and the gas molecules physisorbed on it. At higher temperatures, the chemisorbed layer becomes unstable, and the energy transfer also takes place on the bear surface. Consequently, the temperature dependence of α deviates from that observed at low temperatures.

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Nickel catalyst for hydrogenation of organic compounds is usually prepared by precipitation method.
In this paper, we studied the precipitation process of nickel hydroxide. Then, some kinds of supported nickel catalysts were prepared from various nickel hydroxides, which were aged in various ways to give different properties. And we studied the physical structures and the characteristics of these catalysts.
Consequently, it was found that the precipitation process of nickel hydroxide resembled to that of magnesium hydroxide. Namely, in the first place, hydrated nickel, hydroxide Ni (OH), n H₂0, was obtained which was semicrystalline and appeared like a petal under electron microscope and in the second place, this precipitate was changed into nickel hydroxide crystal Ni(OH), which consisted of fine particles belonging to bluecite type. Several catalysts were prepared by kneading these two kinds of nickel hydroxides.
Asa result, nickel catalyst from bluecite type of nickel hydroxide changed by reduction in the following way: Ni(OH)2→ NiO→ Ni, and showed high activityfor hydrogenation of acetone. But in the case of catalyst obtained from Ni(OH)2. n H₂O, NiO chemically combined with the support and was hardly reduced tmetallic Ni. Consequently, it showed higher activity for aldor-condensation of acetonethan for hydrogenation of acetone.

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The ζ -potential of negative silver iodide sols in the presence of cyanine dyes such as 1, 1'-diethyl-2, 2'-cyanine chloride, bromide, iodide and 4nitrate, was measured, together with the amount of the dyes adsorbed on the silver iodidepowder suspended in the same medium as the sols were.
The ζ -potential increases rapidly with increasing dye concentration in a very low concentra-tion range (8x 10-8 -3x 10-7 mol/l). At higher concentrations, the ζ -potential increases slowly, reaching a constant value at 2∼ 5x 10-' mol/l (Fig.2). In the case of the bromide and iodide of the dye, however, the ζ -potential decreases gradually with the elapse of the time and approaches the value in the absence of the dye. The adsorption isotherm ofLangmuir type is obtained for the chloride, bromide and nitrate of the dye. As seen in Fig.3, however, the experimental points for the bromide salt vary widely. In the case of the iodide salt, the isotherm cannot be obtained, since the adsorption of the dye proceeds so long as the dye exists in the medium. These measurements were also made for the nitrate salt of the dye in the presence of gelatin, polyvinyl alcohol (PVA) or polyvinyl pyrrolidone (PVP). No influence of gelatin on the adsorption of the dye is recognized. PVA hindered the adsorption of the dye at low concentrations. In the presence of PVP, the amount of dye absorbed decreases. From these results, the adsorption behavior of the dyes on silver iodide was discussed.

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When 1, 3, 3-trimethylindilino-6'-nitrobenzopyrylspiran ([A]) in polymer matrix was bombarded with an electron beam (15 kV), two products were fomced: a blue ormagenta colored MD and yellow colored CD. The spectrum and stability of these products were affected more sharply by the matrix polymer than by photochromism. These phenomena were caused mainly by simultaneous change of [A] and polymer.
The polymers were polystyrene (PS) and polymethylmetacrylate (PMMA). The absorption spectra of [B] in PS were identical with those of the photoproduct (CB'D) by ultraviolet light of 365 nm. While these in PMMA did not seem to be the same as those of CB'D. And the efficiency of the formation of [C] in PMMA was higher than that in PS.
[B], [C] and [B'] returned reversibly to [A] by thermal decoloring reaction which was of first order. At room temperature, the rateconstant of decoloring reaction of CBD in PS was smaller than that of [B'] Onthe other hand the result in PMMA was opposite to that in PS. The activation energy (Ea) of decoloring reaction of [B] in both polymers were higher than that of [B']. And difference of E. between [B] and [B'] in PMMA were greater than that in PS.
Both polymers were not affected by the light of 365 nm, butupon bombardment, PS poly-merized with crosslinking and PMMA degradated to smaller molecules. The moleculas structure of PS changed little, but that of PMMA changed considerably and active radicals were formed. The differences between characteristicsof [B] in PS and those in PMMA were made clear. The aspect of [B]. in PS was not so modified as that in photoreaction but it was moderately changed in PMMA. The basic structure of [B] might be equal to [B'] and these differences dependedon a alteration of the polymer. The matrix effects of binding polymers on the cathodochromism might be more remarkable and dynamic than those on the photo-chromism.

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The stoichiometric equation of the photochemical reaction between acid chromateion and reducing agents such as ethanol and 2-propanol was obtained for the buffered aqueous solutions of ammonium dichromate and reducing agent, of which pH were about 4.5, 5.1 and 6.0.
In the dilute aqueous solution of dichromate ion, the photoactive species is acid chromate ion, HCrO4-, and by the irradiation acid chromate ion (Cr (VI)) is reduced to Cr (III) compound together with theformation of oxidation product of reducing agents.
The amount of unchanged acid chromate ion was measured by spectrophotometry and the oxidation product such as acetaldehyde or acetone was detected by gas chromatography. From these measurements it was confirmed that 1.5 moles of reducing agentswere oxidized against the consumption of one mole of acid chromate ion.
Thestoichiometric equation of the photochemical reaction, therefore, can be described as follows: H⁺ 2 HCr(11)04-+hP, 3 CH₃CH₂OH 2 CrOCOH₂++ 3 CH, CHO + 6 H₂O + 2 HCr(VI)04-+hP, 113 (CH₃)2CHOH 2 Cr2++ 3 (CH₃)2C0 + 6 H₂O

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Fablication of mica ceramics molded by the addition of phosphoric acid as binder from a mixture of fluor-phlogopite [F₂Mg₃(AlSi₃0₁₀)] and tetrasilicic mica [F₂KMg_2.5(Si₄0₁₀)] has been reported by the authors previously.
It was tried by solid phase reaction to obtain solid solution between those two mica, because the formation of solid solutions seemed to play an important role in the sintering characteristics of this ceramics.
The thermal expansion and interplanar spacings values were studied for reaction products with various tetrasilicic mica content by X-ray diffractometry. Results obtained were as follows.
(1) It was found that a complete series of solid solutions [F₂KMg_2.5+0.5x(Al_xSi_4-00₁₀)] was obtained, where x was 0 ≤ x ≤ 1:
(2) As the content of tetrasilicic mica in solid solutions increased, the cell dimension of them decreased. The variation in dimension of a and b axis was 1.39% and 0.45%, trespectively, between the end members. The cell dimension in the direction parallel to planar direction of silicate network changed remarkably.
(3) As the content of tetrasilicic mica in solid solutions increased, refractive indices of them decreased continuously between the end members.
(4) As the content of tetrasilicic mica in solid solutions increased, the thermal expansion values of solid solution for a and c axis decreased continuously between the end members.
(5) Apparent values of thermal expansion were obtained for b axis direction, because diffraction angle for (060) peaks could not measured precisely by the reason that 330 peaks interfered with (060) peaks.
(6) The existence of perfect solid solubility between the end members had great importance on sintering

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As a part of studies on multilayer adsorption phenomena of water vapor by hygroscopic inorganic salts, amount of water molecules adsorbed on sodium chloride powder and isosteric heat of adsorption were measured precisely. The isotherms obtained at various temperatures showed stepwise rises of the amount of adsorbed water after the completion of the second layer formation of water molecules., After 'slow increase up to the six layers, the amount of water adsorbed increased abruptly near the equilibrium pressure of water vapor of a saturated aqueous solution of the salt. The BET plots from the above isotherms gave straight lines between the relative pressure region from 0.03 to 0.17, and the value c was ranging from 26 to 46. The difference between the heat of adsorption for the first layer formation and that of liquefaction of water vapor was calculated to be 1.8-2.2 kcal/mol from c. By applying Halsey's equation, characteristic constant r was evaluated to be 0.87. As r is relatively small, the attractive force of the solid to water molecules is considered to be a long-range force. The isosteric heat of adsorption against coverage curve showed two peaks at 0 =1 and 2.5. After the three layers formation, the isosteric heat converged to a condensation heat of water on a saturated aqueous solution of the salt.

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Vapor pressure and density of sulfuryl diamide-ammonia system were measured between -10 and -30°C.
The vapor pressures for saturated liquid ammonia solutions of sulfuryl diamide were 248 mmHg at -10°C, 350 mmHg at 0°C, 485 mmHg at 10°C, 637 mmHg, at 20°C, respectively, and the densities of these saturated solutions were about 1.4. The vapor pressures, obtained for various concentrations of sulfuryl diamide-ammonia soultions (Tables 1 and 3), conformed to the simplified Clausius-Clapeyron equation, logp.=A/T+C, where p is vapor pressure, T is temperature in °K, and A and C are constants.

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Investigations have been made on courses of gelation, dehydration and conversion of aluminum hydroxides during grinding, and some different results from the past informations were found.
Generally, grinding ability increases with decreasing sample weight. In the case of sample weight 2.0 g, gibbsite, Al(OH)₃, was easily converted into amorphous phase, indicated by X-ray, without occurring any mechanochemical dehydration and stabilized as gel-like-phase. This phase was dehydrated and converted into a-alumina through r-0-30 by heating at 800°C in spite of the aggregates of particle size 0.05 u. In the case of sample weight 0.5 g, gibbsite was reduced to particle size 0.02 At (maximum specific surface area 90.6 m2/g) and intermediate alumina as the resultant of mechanochemical dehydration was converted into ca-alumina through X-c. The crystal lattice of a-alumina, the final product of grinding, was considerably expanded and distorted by stress but gradually recovered by further grinding over 24 hours. By grinding in vacuum (10^-2 mmHg), gibbsite was directly dehydrated to a-alumina without forming any intermediate alumina and remarkably reduced to more fine particle; its specific surface area approached to a maximum 350 m²/g after 16 hours. Mechanochemical dehydration of bayerite, Al(OH)₃, and diaspore, AlOOH, were also discussed.
Surface activity of ground gibbsite was quantitatively determined by the acidity and basicity on the basis of indicator adsorption test. Especially, the highest acidity indicated 0.18 mmol/g at 400°C corresponding to the formation of r-alumina in the case of calcined gibbsite whereas indicated 0.60 mmol/g in the range from 6 to 12 hours corresponding to the formations of X

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Paper chromatographic behavior of manganese in the solutions of condensed phosphates of short chain lengths has been studied in order to identify the form of soluble manganese.. Three series of sodium phosphate solutions, ortho-, pyro-, tripoly-, containing manganese ion were prepared as sample solutions. The developed paper chromatogram was devided vertically in two, one half being used to revelate manganese by para-formaldehyde method and an other being used to revelate phosphate by heteropoly blue method. The positions of both revelation zones are important in connection with their chemical forms.
In the case of tripolyphosphate solutions containing manganese, a revelation zone of unknown phosphate appeared closely under the regular zone of tripolyphosphate and a zone of unknown manganese also appeared in the distant level from that of manganese (II) ion. From the fact that both unknown zones were developed in the same level on filter paper, the form of soluble manganese was estimated as a large complex ion coordinated tripolyphosphate. The complex ion was considerably stable in the solution of mole ratio (Mn²+P₂0₅) below 0.6 and its formula was estimated as [MnP₃0₁₀]^3- from Mn and P₂O₅ determinations of unknown revelation zones.
The manganese (II) ion was unstable in pyro- and orthophosphate solutions and manganese salts precipitated. However, the slightly soluted manganese was identified as a complex coordinated pyrophosphate in the pyrophosphate solution and as a simple ion of manganese (II) in the orthophosphate solution by the use of paper chromatography.

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It has been attempted to prepare Co 010-DTMA complexes by the reaction of [Co(DTMA)CO₃] with various amines (ammonia, ethylenediamine, propylenediamine, pyridine, 2, 2'-dipyridyl, 1, 10-phenanthroline) or with amino acids (glycine, L-alanine, 8-alanine, L-phenylalanine and picolinic acid). Reactions at various conditions, especially at different temperatures, have been examined in order to obtain isomers with the different modes of DTMA coordination. The electronic spectra, the infrared spectra and the NMR spectra of the prepared complexes have been taken and discussed in comparison with those of the complexes with known structure. From the results of these spectrometric measurements as well as the elemental analyses, the configuration of the complexes have been estimated. It has been inferred that
(1) the pyridine complex, [Co(DTMA)(py)₂ ](Cl0₄)₂, may have the trans or the fl-fac(N) configuration,
(2) the other amine complexes possibly have the 8-mer(N) structure,
(3) both the cis (O) and the trans (O) isomers had been obtained in the glycinato, L-alaninato, and L-phenylalaninato complexes,
(4) only the trans (O) isomers had been isolated in the 8-alaninato and picolinato complexes. It has been recognized that the trans (O) isomers occur at higher temperature than the cis (4) isomers when both isomers had been obtained (3).

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This papar deals with the results of the experimental work of the study on ³He bombardment on natural chromium target with the aim of production of ⁵²Fe in practical amount for medical use.
The excitation curves and thick-target yield curves were measured for the formation of"Fe and other by produced radioisotopes such as ⁵²Fe, ⁵⁵Fe, ⁵⁶Mn, ⁴⁸Cr, ⁴⁹Cr, ⁵¹Cr and ⁴⁸V, formed while bombarded with ³He particle up to 44 MeV. Also various conditions in the production procedure, especially the yield of"Fe and other byproduced radioisotopes under most adequate incident energy, were examined.
The method used was as follows The stacked metallic chromium plates (each of c/ 30 mm, 20-40 mg/cm²) was made into sufficient thick-target for the bombardment in the ranges of the incident particle energy in the cyclotron, followed by chemical separation of the iron radioactivities or undestructively, and the activities of relative long-lived products formed in each target were measured with calibrated scintilation counter and proportional counter. The excitation curve of ⁵²Fe shows a maximum of 5 mb near 35 MeV energy. The average thick-target yields of ⁵²Fe for 40 MeV incident energy is 50, uCi/gAhr and the ⁵⁵/⁵²Fe ratio is 0.07%.
It is a superior advantage for medical use that this ratio is very small in comparison with that for Q particles bombardment on natural chromium target.
Thus the production method of ⁵²Fe via the ³He-reaction on natural chromium proved to be superior to other possible reactions in its high yields as well as in other points.

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A new method for spectrophotometric determination of gallium with methylxylenol blue (MXB) has been studied.
MXB reacts with gallium to form a water-soluble red-brown complex. The complex has an absorption maximum between 550 and 555 nm and shows a definite absorbance over the pH range from 1.2 to 1.5. Beer's law is obeyed up to 2.0ug/ml of gallium. The molar extinction coefficient of the complex and the sensitivity of the determination are 2.02x10⁴ and 0.0034 ug. Ga/cm² for log (N/)=0.001, respectively. The standard procedure for the determination is as follows.
A sample solution containing up to 50 sag of gallium is taken into 'a 50 ml Erlenmeyer's flask and the pH is adjusted to 1.4 by adding 10 m/ of buffer solution. Then, 3 ml of 0.1 % MXB solution is added and the volume is made to about 20 ml with water. After being kept for 30 min. in a water bath at 90°C, the solution is cooled with running water, transferred to a 25 ml volumetric flask, and diluted to the mark with water. The absorbance is measured at 553 nm against the reagent blank as a reference.
Among the thirty-five diverse ions examined, aluminum, arsenic(V), antimony(III), bismuth (lII), zirconium, thorium, iron (III) and palladium(II) interfere with the determination. But aluminum, zirconium and thorium can be masked by the addition of sodium fluoride, and the effect of iron (III) is eliminated by ascorbic acid.

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An ion-exchange chromatographic technique for the separation of small amounts of monoguanylmelamine in acetoguanamine by means of a stepwise elution from a 0.8 φ X 20 cm column of a strong-acid cation exchange resin, Dowex 50 WX4, in the sodium form is studied. As the eluant, Sφrensen's buffer solution consisting of glycine, sodium hydroxide and sodium chloride is used. An aqueous solution containing 100 mg of the sample is passed through the column. At first, acetoguanamine and its impurities are eluted with pH 9.9 buffer solution. The elution is continued until the absorption of the effluent at 255 nm is not appear. About 250 ml of the eluant is necessary for this. Then, monoguanylmelamine is eluted with pH 11.1-41.5 buffer solution as shown in Fig.3.150-250 ml of the effluent containing monoguanylmelamine is taken and adjusted to a certain volume by adding the buffer solution. The absorbance of the solution is measured at 255 nm. By this method, monoguanylmelamine in acetoguanamine can be determined down to 0.05%. This method is not interfered by the presence of diguanylmelamine, melamine, acetoguanamide, acetoguanide, cyanomelamine, ammeline and dicyandiamine which are present as impurities in the sample.

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After filtering AgSCN precipitate, which was formed by the addition of the known excess amount of Ag+ to the thiocyanate solution, (DDC)₂Cu carbon tetrachloride solution was added to the filtrate. Color intensity of the organic phase decreased as the followingexchange reaction proceeded between the excess Ag+ and (DDC)₂Cu.
Therefore, SCN- was determined through the estimation of Ag+, which was evaluated by the diminition of (DDC)₂Cu color in CCl₄.
The following procedure was recommended for the determination of 0-90ug of SCN-. The pH of the sample solution was adjusted to 4.7 with acetic acid-sodium acetate buffer solution, and 10 ml of 1.6x 10-4 mol//AgNO₃ solution was added. After standingfor about 20 minutes, AgSCN precipitate was filtered through a No.5C paper filter which was treated previously with AgNO₃ solution and was washed with water. The filtrate was poured into the separatory funnel (100 m/), the volume was made up to 60 ml and 10 ml of 0.8x10^-4 mol// (DDC)₂Cu carbon tetrachloride solution was added. Then, after shakingit for about 10 minutes and allowing it to stand for about 5 minutes, the absorbance of the organic phase was measured at 438 nm against the pure carbon tetrachloride solution.
The relationship between thiocyanate ion content, ranging from 0-90.6 jig, and its absorbance was linear and the apparent molarabsorptivitywas found to be 3.8 x 10⁴. The standard deviation and the variation coefficient at the SCN- level of 45.3 respectively. Atg were 3.7 x 10^-3 and 0.63%, respectively.

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Methyl methacrylate-grafted polypropylene fibers prepared by the vapor-phase simultaneous irradiation technique and the preirradiation technique were investigated by the use of differential scanning calorimetry. The DSC thermogram of the original polypropylene fibers showed two big endothermic peaks around the melting region. In the grafted fibers, the peak of the DSC thermogram at a lower temperature side disappeared and then the peak at a higher temperature side decreased with the elevation of grafting. The above tendency was more remarkable on the grafted fibers prepared by the simultaneous irradiation technique.
The degree of crystallinity of back-bone polypropylene, measured through the heat of fusion and the heat of crystallization, decreased considerably with the increase of grafting in the case of grafted fibers prepared by the simultaneous irradiation technique. But the decrease in the crystallinity was not so remarkable in the case of grafted fibers prepared by the preirradiation technique. The results of DSC measurement were compared with those obtained by the X-ray diffractometry.

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Orientation in the Friedel-Grafts acylation of 2-methoxydiphenylene oxide [1] was studied. Reaction of acetyl chloride with [1] in the presence of aluminium chloride in nitrobenzene at 20°C for 1 hr, according to the addition procedure of Bouveault, yielded 2-methoxy-3-acetyldiphenylene oxide quantitatively. Under the same experimental conditions, the reaction of benzoyl chloride with [1], gave 1-benzoyl (yield 19.2%) and 3-benzoyl derivatives (74.0%). The ratios of reaction products depend on the order of the addition of the reagents and also on the solvent used in this reaction. The difference in orientation in the acetylation and the benzoylation of I was tentatively explained in terms of the steric hindrance between the hydrogen at 9-position of I and the acylating agent.
2-methoxy-3-acetyl-D(diphenylene oxide) (mp 113-114°C or 124-125°C dimorphic forms), 1-benzoyl-2-methoxy-D(mp 114-115°C), 1-benzoyl-2-hydroxy-D(mp 134-135°C), 2-methoxy-3- benzoyl-D(mp 124-125°C), 2-hydroxy-3-benzoyl-D(mp 149-150°C), 2-hydroxy-8-benzoyl-D (mp 185.5-187°C).

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The reactions of some cyclic acetals, 2-phenyl-1, 3-dioxolane in particular, with Lewis acids were studied.
The reaction mixture of 2-phenyl-1, 3-dioxolane with BF, -diethyl ether was hydrolysed to give ethylene glycol benzyl ethers and 0-hydroxyethyl benzoate. The total yield of the products was nearly 90% based on 2-phenyl-1, 3-dioxolane. Almost equal proportions of the benzyl group and the benzoate group were always found in the products. Lewis acids, such as AlCl₃, SnCl₄, TiCl₄, FeCl₃, ZnCl₂, and POCl₃, and H₂SO₄ reacted similarly, in which cases, however, the yields of the product were small.
Based upon the effects, both on the yield and the products distribution, of the molar ratio (BF₃ -diethyl ether/2-phenyl-1, 3-dioxolane), the reaction time and the kind of the decomposition agent used, the reaction mechanism involved has been proposed to be as follows: the first step consists of the formation of the adduct of 2-phenyl-L3-dioxolane and BF₃; two moles of this adduct react with each other to form one mole of phenyldioxolanium cation and one mole of 2-benzyloxyethoxy anion; the hydrolysis of phenyldioxolanium cation gives -hydroxyethyl benzoate, while ethylene glycol benzyl ethers are derived from 2-benzyloxyethoxy anion.
2-Phenyl-4, 5-dimethyl-1, 3-dioxolane and 2-phenyl-1, 3-dioxane showed a similar ring-opening reaction, but 2-methyl-1, 3-dioxolane gave only polymeric compounds exclusively.

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1, 3-Dipolar cycloaddition reaction of methyl cis-[1] and trans-cinnamates [2] and p-substituted (NO₂, Cl, H, CH₃, OCH₃) trans-chalcones [3] with C, N-diphenylnitrone [4] and Nmethyl-C-phenylnitrone [5] was carried out to study the electronic effect of the carbonyl group and the substituents in dipolarophiles on the orientation of 1, 3-dipolar cycloaddition reaction.
Two kinds of cycloadducts were obtained in all cases except the reaction of [2] and pnitrochalcone with [4]. A comparison of NMR spectra of cyclic adducts and the products obtained by hydrogenation of the carbonyl group in the cycloadducts showed that the carbonyl group resides always on C-4 position of isoxazolidine ring formed. Namely, the 1, 3-dipolar cycloaddition reaction has high regiospecificity. Further, the fact that the numbers of isomers obtained are not more than two in every case supported the idea that 1, 3-dipolar cycloaddition reaction proceeded through one step mechanism.
The configuration of the products was analyzed by NMR spectroscopy and the relative rate of formation of isomers was studied to discuss stereochemistry of 1, 3-dipolar cycloaddition reaction of nitrones with 1, 2-disubstituted olefins.

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Formation of isoxazole by heating 5-acetoxy-2-isoxazoline is well known.To study this reaction further, 3-phenyl-5-acetoxy-2-isoxazoline [5], trans- [7] and cis-3-pheny1-4-methy1- 5-acetoxy-2-isoxazoline [8], 3, 4-diphenyl-5-acetoxy-2-isoxazoline [9], and 3, 5-diphenyl-4-acetoxy-2-isoxazoline [10] were synthesized by the reaction of benzhydroxamic chloride [1] with enol acetates. Among these, the reaction of [1] with 1-propenyl acetate is summarized in Table 1. Thermal analyses of 5-acetoxyisoxazolines by TGA and DTA are shown in Fig.1 and 2. The result shows that isoxazoline decomposed in the following order: C83 [5] [7], and [9] [10]. Kinetic study of [5] and [7] was carried out in anisol. The reaction is of the first order as shown in Fig.3. Activation energy and entropy were as follows: ΔE, [7], 40.8 kcal/mol ([5], 35.7), tIS, [7] +26.7 e. u. ([5], +11.5). From these results isoxazole formation reaction through elimination of acetic acid was clarified to proceed by E 1 mechanism.

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The isomerization reaction of terminal C6-olefins by Ni(acac)₂-Al₂(C₂H₅)₃Cl₃-PR₃ catalyst in toluene was investigated and the reaction mechanism is discussed. The ratio of catalyst was Ni:Al₂:P(PR₃=P(C₆H₅)₃)=1:20:10. The isomerization of 1-hexene (H-1), 4-methy1-1- pentene(4-MP-1), 2-methyl-1-pentene (2-MP-1), and 2, 3-dimethyl-1-butene (2, 3-DMB--1) proceeded rapidly at 0-20°C and an equilibrium state was attained easily. The catalyst showed a maximum activity at about 10°C. The order of reactivity of olefins was H-1 4-MP-1 2-MP1 2, 3-DMB-1. From the kinetic data for the isomerization of 2-MP-1, the initial rate equation, vo--=k[2-MP-1] [Ni(acac), ], was obtained for the over-all reaction. The apparent frequency factor and activation energy at 0-0°C were 10'3.4 //mol, min and 12.6 kcal/mol, respectively. By varying the p-substituent in tri-p-X-phenylphosphines, it was observed that an electronreleasing substituent lowered the reaction rate in the following order: p-X=Cl H CH₃ OCH₃. Based on the above results and available information, a reaction mechanism, in which the rate determining step is assumed to be the insertion of olefin into nickel hydride complexes, is considered for the reaction, and an attempt is made to account for the effect of the nature of olefins and phosphines on the reaction rate.

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The glow discharge reactions of acetonitrile and acrylonitrile with benzene and toluene were studied. Liquid products which have been determined quantitatively in this study include benzonitrile, benzylcyanide, o-, m-, p-tolunitriles, and propionitrile in addition to the products due to the glow discharge reaction of benzene and toluene.
Comparative results of the% yield (normalized to exclude polymeric products and gaseous products) of cyano substituted hydrocarbons are shown in Table 1 and 2.
The high % yield of cyano products in the reactions of acetonitrile and acrylonitrile with benzene suggests the production of active cyano species by one step fission.
Since the reaction of acrylonitrile with benzene gave a considerably higher proportion of polymeric products than that of acetonitrile with benzene, the % yield of the liquid products of the former was relatively lower than the latter.
The effect of flow rate ratio of reactants and the distance of electrode separation upon % yield of each product was also discussed.

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Reaction mechanisms of alkanes with SO₃ in 1, 2-dichloroethane were studied by measuring the amounts of SO₂ and sulfonic acids produced.
The mechanism of SO₂ formation by reduction of SO₃ with hydrocarbons is not simple, because the initial rate of SO₂ formation is not proportional to the first? order of SO₃ and hydrocarbon (Fig.3 and 4).
The rate of SO₂ formation increases with reactivity of the hydrocarbons, i. e. n-octane 2, 2, 4trimethylpentane 2-methylheptane. In the first step of the reaction, SO₃ is assumed to abstract hydride from the hydrocarbons producing SO₂ and the carbonium ions. The latter is transformed immediately into the olefins which reacted further with SO, to give unsaturated sulfonic acid (or sultone) and carbyl sulfate. In this way, sulfonation of n-octane produced principally disulfato-disulfonic acids while sulfonation of 2-methylheptane and 2, 2, 4-trimethylpentane gave unsaturated disulfonic acids in addition to disulfato-disulfonic acid.
The recovered hydrocarbons in these reactions were identical with the starting hydrocarbons.

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The structural analysis of C₉ acids (C₈H₁₅ BCOOH) produced by the carboxylation of isobutylene with carbon monoxide and water in the presence of BF₃-2 H₂O catalyst was carried out to give information on the formation mechanism of C₉ acids.
The main C₉ acids found in the early stage of the reaction had the following skeletal structures.
During the course of the reaction, the amount of C₉ acids having skeletal structures (B), (C), (D) and (E) gradually decreased and became almost negligible at the final stage of the reaction. The C, acids found in the final stage of the reaction mainly consisted of (A) type acid together with tertiary C₉ acids having structures other than (B)(E).
The C₉ acids might be derived from C₈ cations formed by the following paths.
The carboxylation of the C, cations would be a reversible reaction under the reaction conditions. The C₉ acids having structures (B)(E) appears to be comparatively unstable under the reaction conditions, and to decompose to trimethylacetic acid or to isomerize to the C, -acid having other skeletal structures.

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New polymeric red dyes were prepared in order to improve bleeding resistance of red azo pigments derived from Naphthol AS series.
First, poly[3]-hydroxy-2-naphth(m-methacrylamide)anilidej[4. ]as a polymeric coupling com ewas prepared bypolymerizationof 3-hydroxy-2-naphth(m-methacrylamide)e ofmethacrylyl anilid synthesized by the reaction of 3-hydroxy-2-naphth(m-amino)anilide [2]ih chloride. When the coupling reaction of pymer[4]with with aromatic diazonium chloride was carried out in aqueous alkali condition, polymeric dyes containing the azo groups were obtained. The content of the dye group was estimated by nitrogen analysis.
While, 4-arYlazo-3-hydroxy-2-naphth(m-isobutyrylamiqe)anilide as the authentic dye was synthesized by coupling reaction of 3-hydroxy-2-naphth(m-isobutyrylamide)anilide prepared from [2] and isobutyryl chloride, with aromatic diazonium chloride.
The polymeric dyes and authentic dyes containing the following groups were prepared,

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1-5, Honmachi 1-chome, Shibuya-ku, Tokyo Japan Metal-free phthalocyanine (H₂-Pc) was reduced with alkaline metals in liq. ammonia and the products were purified by Soxhlet extraction with tetrahydrofuran. The conditions of formation of four reduction products were studied by analysing the content of the alkaline metal atom contained in each product, and as a result, the relation between the stage of the reduction and the atomic ratio of alkaline metal used was established. The effect of three alkaline metals, Li, Na and K on the stage of the reduction revealed that the dianion, trianion and tetranion were isolated by the reduction of one mole of 1-12-Pc with 10 atoms of Li, Na, and K, respectively. The canonical structures of four reduction products of H₂-Pc were elucidated on the basis of their infrared spectra and other chemical and physicochemical properties.

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The drawing and heat-treatment in dimethylformamide or dimethylacetamide aqueous solution were performed for poly (metaphenyleneisophthalamide) films, and the most suitable conditions on the concentration, temperature of swelling solution and the time of treatment were decided. Under the suitable condition, the films were drawn to 6 or 7-fold of the initial length. The initial modulus and tensile stress at break of the high-drawn specimens increased to as much as 5 or 6-fold of those of un-drawn one, and the change of elongation at break with draw ratio showed a maximum value. When the drawn specimens were heat-treated, the initial moduli increased much more.
Above method for the drawing and heat-treatment can be made more easily than Du Pont's method, in which high-pressure steam is used. Also, changes in fine structure of the films by drawing or heat-treatment were investigated by optical and X-ray methods. From the results, it was clarified that the degree of orientation by optical method increased rapidly at the early stage of drawing, and changed gradually after the draw ratio 3. When the drawn specimens were heat-treated, the degree of crystallinity and orientation increased remarkably.

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The interaction of sodium dodecyl sulfate (SDS) with poly (N-vinylpyrrolidone) (PVP) or poly(vinyl alcohol) (PVA) were studied by the viscosity method and the membrane equilibrium method in aqueous solution.
The intrinsic viscosities [V] of PVP or PVA solution in the presence of SDS were determined at 37°C. The amounts (x) of SDS bound onto PVP or PVA were calculated from the titration data of the outer solution of membrane.
It was found that [77] and x increased with the increase in concentration of SDS to reach maximum and then decreased at higher concentration of SDS as shown in Figs.1, 2 and 3. There is a good correlation between [i7] and x in the case of PVP as shown in Fig.6, but in the case of PVA the correlation is poor because of the intramolecular hydrogen-bonding between -OH groups.
The isotherm of bound SDS as a founction of concentration of free SDS (ITO) is bellshaped as shown in Figs.2 and 3, but the isotherm as a function of activity of DS- anion (aDs--) is J-shaped as shown in Figs.4 and 5, because aDs- decreases at higher concentration of SDS.
It was found that a degree of dissociation of sodium ions from the complex (cep) decreased with m(o) as shown in Fig.7, and the relation between log (1-ap)/ap and logarithm of Na+- activity (log aNa+) was linear as shown in Fig.8.
The contribution due to the Donnan effect was estimated, but the difference between the data calculated by neglecting the Donnan effect and considering it was small, as shown in Fig.9, when mro was less than the critical micelle concentration (CMC).

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The polycondensation reaction of terephthalic acid (TPA) with ethylene glycole (EG) catalyzed by Sb₂O₃, or Ge0₃ were investigated.
The reaction rate depends on the R value which is described as follow:
P: ester value.
G: the moler ratios of EG and TPA is feed.
It was also found that the compounds of Sn and Pb were effective as co-catalysts in the polycondensation reaction catalyzed by Sb₂0₂

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Radiation induced graft copolymerization of acrylonitrile onto poly(vinyl chloride) fiber has been investigated. The effect of degree of swelling of the fiber and monomer concentration in the fiber on grafting was studied.
When the acrylonitrile monomer was applied as solution in n-hexane, n-heptane or cyclohexane, a maximum and a minimum of grafting was observed as the monomer concentration in the solution was increased. But such phenomena was not observed in the case of ethylacetate solution.
In order to understand such effect, several experiments were carried out, and it was concluded that a reasonable explanation can be given assuming the following two relationships.
(1) At constant degree of swelling, the grafting rate increases with the increase of monomer concentration in the fiber.
(2) At constant monomer concentration in the fiber, the grafting rate decreases with the increase of degree of swelling.

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In order to clarify the mechanism of the reaction of hydrophilic fiber with reactive dyes, the studies were carried out on the system of poly (vinyl alcohol) (PVA) and 2-substituted 4- amino-6-chloro-1, 3, 5-triazine as the model reaction. The reaction proceeded in dimethyl sulfoxide solution in the presence of sodium hydroxide aqueous solution. The reaction rate was determined by the ratio of the intensity of IR absorption band at 805 cm^-1 to that at 2900 cm^-1. It was found that the empirical reaction was of the first order and its rate was proportional to the concentrations of PVA, reactant and NaOH in the dilute solution, respectively, but the initial reaction rate decreased with increasing concentration of NaOH. Assuming the second order nucleophilic substitution, it was found that the relation between the reaction rate constant and the substitution constant in triazine derivatives obeyed the Hammett's rule approximately and Q=+2.8. The rate of initial reaction between PVA and the compounds having a substituent on p-position of benzene ring of 2-anilino 4-amino-6-chloro-1, 3, 5-triazine was found to be the following order, p-NO₂ p-Cl H p-CE3. It was also clarified that the effect of substituent of -s- triazine ring on the rate of the reaction of PVA with cyanuric chloride derivatives was dependent on its electron density.

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Poly (vinyl alcohol)(PVA)-copper (II) complexes were prepared in varying Tcu2+/THL (the ratio of the total concentration of copper (II) ion to the concentration of the ligand) ranges of higher than 0.15 in aqueous solution at ionic strength 0.1 and pH 10.5. In these Tco. /THL ranges, these copper (II) complexes precipitated; and the amounts. of precipitated complex polymers increased with increasing Tc, i2+/THL values. These precipitates were filtered off and after standing for 24 hrs EDTA was added to separate PVA-cuprous complexes (removal of cupric ion). These solutions were dialyzed to remove the excess reagents and dried on chromium plate at 30° C. The content of syndiotactic diad obtained by means of infrared spectra is slightly higher than that obtained from the complex in lower Teu2. /THL (Fig.4).

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Poly(ethylene terephthalate) film, Mylar C-25 (du Pont), was stabilized by water at 160° C for 1 hr, the condition of which proved to be the most severe and critical one. Disperse dyes and their model compounds, p-nitroaniline [1], p-aminoazobenzene [2], 1, 4-diaminoanthraquinone [3], C. I. Disperse Violet 8 (4) and C. I. Disperse Orange 13 [5], were used as the penetrants. Diffusion coefficients, D of the penetrants were determined by the cylindrical film roll method over the temperature range from 70° to 156° C. Diffusion of all the penetrants obeyed Fick's law. Diffusion coefficients decreased in the following sequence, [1][2][4][5], and accordingly with increasing molecular size. From the Arrhenius plot of log D (Fig.4), some breaks were found, which were ascribed two transitions having a wide region of transition. Transition (I), the glass transition of PET, occurred between 84° and 115° C, and transition 00 between 125° and 140° C. They were observed clearly and separately when the diffusion coefficients of penetrants were about 10-9-10-8 cm²/min. These results show that there is a close connection between the molecular motion of polymer chain and the diffusion of penetrants, i. e., the hole formation to bring about the penetrant diffusion in polymer determines the rate of diffusion. Corresponding to the distribution of relaxation time for the segmental motion of polymer chain, there may be a distribution of the hole size. As the penetrant can only diffuse through all the holes larger than the critical size of the penetrant, the size and distribution of holes may determine the diffusion coefficients. The apparent activation energies of diffusion Ed below transition temperature (I) and those above transition temperature (II) increased with increasing molecular size of penetrants. The values of Ed were always larger in I than in II.

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The consecutive hydrogenation of liquid phenylacetylene over platinum supported spherical alumina has been studied in order to evaluate the effect of diffusion on the selectivity of the reaction.
The first step and the second step for consecutive reactions were of zero order with respect to phenylacetylene and styrene concentrations, and were of first and 0.87 order with respect to hydrogen concentration, respectively.
The selectivity (Y) in hydrogenation was defined as the ratio of formation rate of ethylbenzene to styrene. The selectivity was represented as follows: Y=(1 Yo 1)1. Where, Q indicates the resistance ratio of the extraparticle diffusion to the overall diffusion.
Yo (Q--=0) was found to be: Yo=v(71c.)031
in which, v (kodko2) is the ratio of two rate constants, 77 means the effectiveness factor of the catalyst, and CH is the hydrogen concentration at gas-liquid interface.
It was found that the selectivity decreases with the increasing intraparticle or extraparticle diffusion resistance. When the intraparticle diffusion is the rate controlling step, the selectivity is remarkably affected by the amount of platinum supported on the alumina.

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3-(p-Methoxycarbonylphenoxy)propionitrile (MPPN) was prepared by the cyanoethylation of methyl p-hydroxybenzoate (MPOB) at 100-150°C in the presence of strong bases (Triton B, Na) in an autoclave.
MPPN was converted to methyl 3-(p-methoxycarbonylphenoxy)propionate (MMPP) by the reaction with dry gaseous hydrogen chloride, and then with water in methanol. MMPP was also obtained in good yield by the reaction of MPOB with methyl acrylate in the presence of sodium.
The corresponding dibasic acid was obtained by the hydrolysis of MMPP in conc. hydrochloric acid. However, by the hydrolysis of MMPP in an alkaline medium, p-hydroxybenzoic acid was obtained.

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An ultraviolet spectrophotometric method for the determination of trace amounts of anthracene in anthraquinone is studied. The method is based on that anthracene is separated by extraction with n-heptane after the sample is reduced and dissolved with sodium hydrosulfite alkaline aqueous solution. One gram of sodium hydrosulfite, 30 ml of 0.5 mol/l sodium hydroxide solution and 100 mg of the sample are added into 50 ml separating funnel. The air in the funnel is replaced with nitrogen. The solution is warmed to 45° C and shaken until anthraquinone is dissolved. After 15 ml of n-heptane is added, the mixture is shaken sufficiently, and then the aqueous phase is removed. To remove the remaining anthraquinone, n-heptane phase is shaken once more with 30 ml of sodium hydroxide solution containing 300 mg of sodium hydrosulfite. Anthracene is determined by the difference between the absorbance at 375 nm and that at 385 nm.

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The determination of the binary system samples which are difficult to analyze in ordinary gas chromatography was carried out by photolysis-gas chromatography, using the vapor phase photolysis in the presence of small amounts of H₂S as a radical scavenger.
The five binary system samples shown in Table 1 were chosen as typical examples.
Super high pressure mercury arc was used as a light source, and the photolysis products were analyzed by gas chromatograph in the same manner as reported before.
In each system, the plot of the molar ratio of the two components against the molar ratio of the photolytic products (2, 3, 5 in Table 1), or the plot of the partial pressure of a component against the amounts of products (1, 4 in Table 1) gave straight lines.
No mutual interferences of the components were found in the photolysis reaction.

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The oxidation reaction of eugenol catalyzed by palladous chloride-cupric chloride under oxygen flow gave 1-(4-hydroxy-3-methoxypheny1)-2-propanone in 30-35% yield. The analogous reactions under various conditions were examined.

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Effect of hydrogen chloride on benzoyloxylation of aromatic compounds with CuCl2-benzoyl peroxide has been studied. The decomposition of benzoyl peroxide in aromatic compounds in the presence of catalystic amounts of CuCl2 (less than 0.1 molar ratio to the peroxide) produced aryl benzoate in small yields.
The finding of the present study was that the addition of a small amount of hydrogen chloride to the reaction mixtures brought about a remarkable increase in the yield of aryl benzoate and a remarkable decrease of biaryl. Mixed copper(II) salt and C, H, COOCuCl could not be detected in the reaction mixtures conducted in the presence of hydrogen chloride. These findings may be interpreted in terms of the regeneration of the effective catalyst, CuCl, which is promoted by the added hydrogen chloride ;
CuH₅COOCuCl HClC, H, COOH CuCl₂

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The solution polymerization of methyl-methacrylate (MMA) in cyclohexane was carried out to study the mechanism of the precipitated polymerization. The autoacceleration effect appeared from the initial stage of the polymerization and the smaller the concentration of monomer the more remarkable was its effect. As to the distribution of the chain length, there were two clear peaks and as polymerization proceeded, the peak of the low degree of polymerization was disappeared. These experimental results suggest that to make clear the mechanism of the precipitated polymerization analyticaly, it is effective to divide the reaction into two parts and to treat separately, namely the reaction in liquid phase and in solid phase.

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During the study of a behavior of orthophosphoric acid in an aqueous solution of orthophosphoric acid-cyanamide, a particular phenomenon was found that formation of condensed phosphoric acid was observed in an aqueous solution of orthophosphoric acid by the addition of cyanamide to the solution.
Then, a newly prepared aqueous solution containing 15% of orthophosphoric acid and 17% of cyanamide was taken as a sample and an experiment to confirm the formation of condensed phosphoric acid was carried out.
In this experiment, a paper chromatograph was used and comparison of the Rf value of the sample solution obtained and that of the authentic sample was performed along with identification, and the formation of condensed phosphoric acid in the aqueous solution of orthophosphoric acid-cyanamide has been confirmed.

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