Adsorption isotherms for N₂, CO₂ and SO₂ on activated carbon, silica gel, and alumina have been measured over wide ranges of pressure and temperature, using a constant volume type adsorption apparatus which is capable of precise adsorption measurement with convenient manipulations at high pressure. It was found that, under the experimental conditions, amounts of adsorption of N₂ and SO₂ are increased monotonously with pressure, while an adsorption maximum was observed for CO, From the apparent amount of adsorption, the absolute (or true) amount of adsorption was calculated by assuming the equality of the volume of adsorbed phase to the pore volume of of the adsorbent. Several adsorption equations were examined to fit the absolute adsorption data, and it was found that multilayer type adsorption equation with small n-values was applicable to all of the gas-solid systems studied in the present work.

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Experiments of gas adsorption at high pressure were carried out with a constant volume type adsorption apparatus. The experimental conditions were as follows; [adsorbents]: activated carbon, silica gel, alumina, [adsorbates]: CH, , C₂H6, C₂H₄, [temperature]: 0∼75°C, [pressure]: 0.3∼155 atm.
Complicated adsorption isotherms which have their respective maxima at given pressures (and sometimes intercept each other) were observed for almost all cases for C₂1-16 and C₂H₄.
In all of the gas-solid systems employed in this work, the absolute amounts of adsorptions, which were calculated by assuming that the volume of the adsorbed phase was equal to the pore volume of the adsorbent, were found to be expressed by multilayer adsorption equations with small n-values, i. e., BET equation or Pickett's equation with small n-values.
Relations of the parameters of Pickett's equation, which fitted well the observed amounts of adsorptions, with the physical properties of the adsorbates and adsorbents were derived, and the resulting correlations among them were used to predict the apparent amounts of adsorptions. It was found that the predicted amounts of adsorptions agree fairly well (with approximately-20% deviation) with the observed values excepting the adsorption of N₂.

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Reaction scheme of oxidative dehydroaromatization, i. e., oxidation of lower olefins to aromatics over bismuth phosphate or stannic oxide catalysts, was investigated by comparing the products from various C3-C8 hydrocarbons. n-Butenes were mainly oxidized to butadienes, which were known to be formed via the allylic intermediate, and partially to aromatics and diolefins. The same distribution of products was obtained for three isomers of n-butenes. Isobutene was converted to 2, 5-dimethyl-1, 5- hexadiene and consecutively to p-xylene. From 1, 5-hexadiene, 1, 3, 5-hexatriene was formed together with benzene. Both cyclohexane and cyclohexene were converted to benzene and 1, 3, 5-hexatriene by parallel reactions, and their aromatization rates were relatively slow, while 1, 3-cyclohexadiene was readily de-hydrogenated to benzene. These results suggest that the reaction proceeds through several consecutive steps: (1) the oxidative dehydrogenation of olefins to allylic intermediates, (2) the dimerization of allylic intermediates to 1, 5-hexadienes, (3) the oxidative dehydrogenation of 1, 5-hexadienes to hexatrienes, (4) the cyclization of hexatrienes to 1, 3-cyclohexadienes, and (5) the aromatization of 1, 3-cyclohexadienes.

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Kinetics of the ethylene hydrogenation over a silica-supported copper catalyst was studied, together with the measurements of the adsorption of the reacting gases being examined during the hydrogenation.
It was found that the rate of hydrogenation is proportional to the square of the amount of hydrogen adsorbed on the surface of the catalyst, i. e. r=K(aPH/1+aPH), and that the activation energy of k is 5.8 kcal/mol.
From the experimental results, we have arrived at the conclusions that the hydrogenation occurs via a reaction of two weekly adsorbed hydrogen atoms with ethylene adsorbed strongly on an independent site and that weekly adsorbed ethylene and adsorbed hydrogen compete with each other.

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In order to reveal the catalytic properties of uranium oxide-alumina and uranium oxidesilica, various investigations on the structure of catalyst and the activity for catalytic oxidation of CO were performed.
The experimental results gave the following conclusions.
(1). As shown in Fig.3, the oxidative activity of the catalyst supported on silica is remarkably low, comparing with the catalyst supported on alumina. This is due mainly to the fact that uranyl compound used as a starting material for the catalyst preparation hardly decomposes to uranium oxide, contrasting with the case in which uranyl compound is supported on alumina.
(2) The reaction rates of CO oxidation by the catalyst supported on alumina or the catalyst without carrier can be expressed approximately as the first order with CO pressure and the zeroth order with 02 pressure. Apparent activation energy is nearly equal to be 25 kcal/mol for the former catalyst and 18 kcal/mol for the latter catalyst.
(3) The following reaction scheme has been postulated,
U308 + CO A > U307 + CO, (catalyst reduction step)
U307 + 1/2 02 --+ U808 (catalyst oxidation step)
i. e., the reaction proceeds by oxidation-reduction cycles, in which the catalyst reduction step is the rate-determining process.
(4) Generally speaking, alumina and silica trend to combine with uranium oxide or uranyl compound during the course of catalyst preparation. The catalysts calcined up to 500°C contains various chemical species of uranium, the catalytic activity levels of which are different. At present it was evident that the active components were limited only to uranium oxide on alumina and uranium oxide-alumina compound.

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The effect of firing conditions on the diffusion of sulfide ion in ZnS crystal was investigated by the measurement of the distribution of S, which was initially deposited as Zn35S on the surface of ZnS, before and after firing at 500-1050°C for 1 hr in various atmospheres such as in vacuum, He, H₂S, HCl and 0₂.
Little diffusion of 35S into ZnS was observed at 500°C in all cases. At 800°C, sulfide ion diffused at the similar rate in vacuum, He and HCl. The diffusion was slower in 0₂ due to the surface oxidation and in H₂S due to the atomic exchange reaction. At 1050°C the diffusion of sulfide ion was rapid. Though the amount diffused in vacuum and He decreased somewhat due to the sublimation of ZnS.
These results were discussed on the basis of the chemical reaction at the gas-solid interface and the sintering of ZnS particles. Mechanism of the effect of firing atmospheres on the diffusion of sulfide ion in ZnS crystal was proposed.

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In the course of the synthesis research into N3P3(NH₂)6. H₂O(I) as a fireproof material, it was found that a new adduct, N3P3(NH₂)6. HCl(II) was formed dependent on the experimental conditions. The reaction for the formation and the chracteristices of these compounds have been investigated.
The reaction between (NPCl₂)₃ and liquid ammonia has been completed within several hours in an autoclave with an electro-magnetic stirrer, and the rate of reaction was accelerated by the addition of dioxane as the solvent in this reaction system.
The ammonia involved in the reaction product was completely excluded under a reduced pressure, and the product was dissolved in water. The new adduct, (II) was precipitated by the addition of ethanol to the aqueous solution. The analyses of the typical products did not give the formula N3P3Cl6-(NH₂) but N3P3(NH₂)6HCl. Therefore, the formation reaction may be expressed by the following equation:
N₃P₃ (NH₂) 6 + 6 NH₄Cl N₃Pg (NH₂) 6 HCI + 5 NYI4Cl + NH₃
The equation was confirmed by the reaction between (I) and commercial ammonium chloride. The heat of reaction was 1.24 kcal/mol (endothermic). On the other hand, the addition of ethanol to a solution of the reaction product containing adequate ammonia gave the compound (II).
(I) and (II) were the white crystalline powder, and dissolved in water, but were insoluble in various organic solvents. These compounds showed their own IR absorption bands and distinct DTA curves. They were both converted to phospham through heating, which has an excellent flame resistance.

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Since Cu²⁺ is liberated by the following exchange reaction;
(DDC)²⁺Cu (chloroform) + Hg²⁺ (aq.)-(DDC)²⁺Hg (chloroform) + Cu²⁺(aq.)
(here, (DDC) 2Cu designates copper (II) diethyldithiqcarbarnate), He+ can be determined by titrating the liberated Cu³⁺ with EDTA.
After the addition of 10 ml of acetic acid-sodium acetate buffer solution (pH 3.00, 3.27) and 10 ml of 0.01 mol/l (DDC)²⁺Cu chloroform solution, the sample solution was shaken for about 5 minutes and allowed to stand for about 10 minutes. Then, a 10 ml portion of the aqueous phase was taken for. the chelatometric titration of Cu with 0.002 mol/l EDTA in the presence of PAN as an indicator. When the quantity of Hg²⁺ was small, all aqueous solutions were taken and titrated with 0.001 mol/l EDTA. Mercury, ranging from 0.0 to 14.85 mg, could be determined. The standard deviation was 0.012 and the variation coefficient was 0.24% at the Hg²⁺ level of 5.007 mg.

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A nondispersive vacuum ultraviolet photometer has been developed for continuously recording the concentration of two component gaseous or liquid systems. It is essentially a single-beam instrument using the nondispersion principle. The photometer measures the relative intensities in the wavelength range of 1650∼2000 A between the reference gas (N₂ or air) and the sample gas. The main apparatus consists of a deuterium discharge tube, a gas cell of 200 mm length withquartz windows, a photomultiplier, and a vacuum system. In the detection system a sodium salicylate plate is employed, and then the photocurrent at the detector is amplified and recorded. The ultraviolet light from the source is cut off by a fixed grating and a exit slit. Using this photometer, the following amounts (vol%) of gases could be determined: 0.0002∼0.5 of NO₂; 0.0005∼0.4 of NO; 0.006∼1 of 02; 0.09∼46 of CO₂; 0.0002∼0.12 of CH₂=-CH₂; 0.0001∼0.09 of CH₃CH=CH₂; 0.002∼1.3 of HC-CH; 0.08∼60 of CH₈CH₂CH₈; 0.00003∼0.05 of Cell, ; and 0.00003∼0.03 of C₆H₅CH₃. The coefficient of variation was less than 1 %. The deviation of the method was approximately ±4%. The precision of the photometer is comparable with that of a few other instrumental analyses. The method may be applied to the continuous analysis of chemical processes and toxic gases in the atmosphere.

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A nondispersive vacuum ultraviolet photometer, previously developed by the present authors, has been applied to the measurement of some inorganic salts and amino acids in aqueous solution. Quantitative analysis for a given component is achieved by simultaneous measurement of the relative intensity between the solvent (water) and the solute in the wavelength region about 1750∼2000 A. A cell was designated to 0.3 mm thickness and samples were determined by the compensation method. Using the method, the following amounts (mg/100 ml) of samples could be determind; 0.04∼14 of KSCN; 0.05∼16 of KMnO₄; 0.06∼20 of KBr and KI; 0.08∼30 of KNO₃; 0.08∼40 of K2Cr207; 0.2∼35 of (N1-14)6Mo7024; 0.2∼70 of KI03; 0.02∼7 of L-Phenylalanine; 0.08∼25 of L-Arginine; 0.2∼60 of L-Histidine; 0.3∼400 of L0.2∼200 of NaCl; Methionine; 0.3∼80 of L-Lysine; 0.5∼300 of Glycine; 0.5∼350 of LAlanine; 0.5∼200 of L-Threonine; and 0.7∼350 of L-Proline. The coefficient of variation was less than 1%, which tied with that obtained by the gls analysis. The deviation of the method was approximately ±4%. The photometer has been proved to be effective also for continuous analysis of two component liquid samples in the process streams and others.

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Atomic absorption spectrophotometric investigations of calcium and magnesium, with airacetylene flame, were carried out by the use of Shimadzu Multichannel Atomic AbsorptionFlame Spectrometer, Model MAF-1, and fundamental conditions were examined with an aim of its application to the analysis of calcium and magnesium in water.
The condition recommended for calcium and magnesium determination were as follows, wavelength; 4227 A and 2852 A, hollow cathode lamp current; 11 mA and 10 mA, slit width; 0.05 mm and 0.05 mm, acetylene pressure; 0.3 kg/cm² and 0.3 kg/cm², air pressure; 1.4 kg/cm² and 1.4 kg/cm², respectively.
Coexisting elements except large amounts of silicon, aluminium, titanium and vanadium did not interfere the determination. Chemical interference could be minimized on calcium by the addition of 5000 ppm of lanthanum to the unknown and standard samples, same interference to magnesium could be minimized by the addition of 50 ppm of calcium.
The relative determinations were less than 4.7%, and the results were satisfactorily coincident with those obtained by other methods.

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When a sulfuric acid titanium (III) sulfate is irradiated by ⁶⁶Co γrays, titanium (III) is oxidized to titanium (IV) through the radiolysis producsts of water. The chemical dosimeter based on the decrease of titanous ion was investigated to measure continually and automatically a relatively large dose. The oxidized amounts of titanium (III) were determined amperometrically.
The dropping mercury electrode and Hg|Hg₂SO₄ reference electrode. were found to be stable to the irradiation of γ-rays. There was the linear relation having several crooks between the decrease of titanium (III) concentration and the quantity of irradiation. The G(Ti⁴⁺) value was independent of the initial titanium (B) concentration, sulfuric acid concentration, and irradiation intensity. The G value from the origin to the first crook was 5.76± 0.13 except the weak irradiation region. The measurable dose range increased with the elevation of the initial titanium (ll) concentration. When the solution of 42 mmol/l was used, the dose of 2 x 10⁶ rad could be measured. The sample solution was reproduced easily by the electrolytic reduction.

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Simple and rapid identification of a variety of commercially available polymerized materials was studied by means of pyrolysis-gas chromatography (PGC). Pyrolysis-gas chromatographic conditions such as pyrolysis temperature, column sort and operating conditions were unchanged throughout a series of measurement. Temperature programming operation was also adopted for better separation of the degradation products. The identification of a variety of polymers was made not only by the pattern of the pyrogram but also by the characterization of main peaks appearing on the pyrograms. The degradation mechanisms of some typical polymers were also discussed.

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A rapid and non-destructive method has been required for the determination of hafnium contents in zirconium. The time consuming nature of conventional analytical techniques has provoked the necessity of the investigation of fast neutron activation analysis of hafnium.
In the present paper, a method based on the measurement of short half-life isotope ^179mHf produced by the ¹⁷⁹Hf(n, n')^179mHf has been investigated. The use of Be-D neutrons has made it possible to avoid the interferences from oxygen, zirconium and other elements. Selenium was used as an internal standard material for assuring the precision of the analytical results.
The proposed method seems to be useful as an analytical procedure for hafnium determination in zirconium by fast neutron activation analysis.

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This apparatus was developed to study the solid-state reactions and physico-chemical changes involving absorption or evolution of gases, and structurally consists of a modified gas effluent analysis equipment and a high-precision gas mixer. The new apparatus is more useful in the fields of inorganic chemistry, organic chemistry, metallurgy, etc. than a conventional EGA equipment.
The sample is heated or cooled at the constant rate in a mixed flow of two or more different gases such as He-O₂, He-CO₂, Ar-H₂, etc. The changes in the composition of the gas passing through the reactor due to the decomposition or the gas-solid reaction are detected with high sensitivity by a thermal conductivity detector. The sample weight required for the usual measurement is 5∼50 mg. It is applicable to the range from room temperature to 1600°C and the gas flow of any mixing ratio (200: 1∼1: 200). Although the limits of determination are affected by the operating conditions, an evolution or absoption of 0.01-0.0001 ml of oxygen by the sample in the He-O₂ mixture can be detected.
This paper describes the following reactions as the applications of this apparatus: reduction of vanadium pentaoxide by hydrogen, thermal decomposition of calcium oxalate monohydrate, oxidation and reduction of iron oxide, formation and decarbonation of calcite, and hydrogenation and formation of uranium hydride.

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Distribution equilibria of three substituted anilines between N, N-dimethylformamide(DMF) and macroreticular sulfonic acid type ion-exchange resin, Amberlyst 15, has been investigated over a wide range of concentration. The reaction of the bases with the hydrogen resinate in DMF was regarded as acid-base equilibria which obey a classical mass law expression. The equilibrium constants(K) increased with an increase of acid dissociation constants of the bases in water and it was represented by equation log K=-0.85 + 0.752 pKa. On saturated sorption of the bases toward the resin in DMF, it was found that the degree of saturation of beses are related to pKa values and corresponds to 71% of the amounts of hydrogen ion in the resin for toluidine. This is considered to be the interaction between DMF and sulfonate group of the resin.
Application of these results to chromatographic separation on ion exchanger in nonaqueous media was examined. The separation of o- and p-chloroanilines and of o- and m-chloroanilines were successfully achieved by using DMF or n-butylamine-DMF mixture as eluants.

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Photochemical rearrangement of benzyl phenyl ether has been studied. The photolysis of benzyl ether in organic media gave o- and p-benzylphenols. phenol and bibenzyl. In the case of photolysis in isopropanol, the yields of o- and p-benzylphenols . and phenol were 28.5, 16.9, and 15.8%, respectively. The hydrogen-donating alcohols, such as menthanol, ethanol, isopropanol, and grycerol-isopropanol, were effective as solvents for the photorearrangement was not quenched by triplet quenchers. Yields of the rearrangement products decreased by the radical inhibitors, such as 2, 2-diphenyl-1-picrylhydrazyl and nitoro-sobenzene. On the other hand, the yields increased with the viscosity of solvents. These results suggest that benzyl phenyl ether in π, πlowest excited singlet state gives a radical pair, which couples in a solvent cage to form o- and p-benzylphenols.

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The reaction of phenylisocyanate with various substituted alcohols using 1, 4-diazabicyclo[2.2.2]octane(DABCO)as a tertiary amine catalyst or di-n-butyltindilaurate(DBTDL)as a metal catalyst, has been carried out in toluene. By comparing IR spectra of alcohols alone with those of alcohol-catalyst mixtures in toluene, an evidence was obtained which shows the complex formation between the alcohols and catalyst. It has been found that the urethane formation follows the second order kinetics in each catalyzed system and that[Cat]is proportional to the alcoholconcentration in the presence of DABCO and to the isocyanate concentration in the presence of DBTDL. On the basis of the complex formation between the alcohols and catalysts, it is apparent that the complex forming step is in equilibrium in the former case, and that the complex concentration is extremely low and the stationary state is applicable in the latter. The rate constants for the rate determining step in both cases were calculated. In regard to the substituent effect of the alcohols for the urethane formation, it has been found that Taft prime; s plot of against shows a linear relationship, and that the reaction is dominated by the polar and steric effects.

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The mechanistic studies of photochramism, thermochramism and piezochromism of the oxidation products of 2, 4, 5-triarylimidazoles and 2-arylphenanthro[9, 10-d]imidazoles revealed that these reversible color changes were due to dissociation of the oxidation products to radicals. In connection with the investigation, the structure and properties of the oxidation product of1, 4-bis(4, 5-diphenylimidazoly1-2)benzene[1], were studied.
By oxidation of[1]with lead dioxlde in benzene or oxidation of a potassium salt of the compound with finely ground powders of potassium ferricyanide in dioxane, an oxidation product, 3, 6-bis(4, 5-diphenyl-2H-imidazol-2-ylidene)-1, 4-cyclohexadiene[2]was obtained as deep greenish-blue fine prisms with a metallic luster. From studies with IR, UV, NMR spectra of the compound and the chemical reactions, it is concluded that[2] assumes predominantly the quinoid structure[2a] at room temperature in both solid and solutions and reversibly isomerizes to the biradical structure[2b]at elevated temperature.
The concentration of the biradical structure[2b]in a solid state at 200° C was estimated to be about 0.1% from the spin concentration. Failure to detect ESR signals attributable to a triplet state appears to independence of two unpaired electrons in the biradical structure.

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The manufacturing conditions of spherical activated carbon for water treatment were investigated. Activated carbon was prepared from three kinds of powdered bituminus coal, which was pelletized by the addition of sulfite-pulp waste, carbonized in a rotary kiln, and activated by steam in another rotary kiln. Adsorption properties and pore-size distribu-tions of the activated carbon prepared under different conditions of temperature, time, and source of crude coal were studied(Table1). These were compared with commercial granular activated carbons. Five kinds of solution containing acetic acid, phenol, methylene blue, sodium dodecylbenzene sulfonate, and 4-hydroxy, 3-methoxy synnamic acid were chosen for measurement of adsorption rate and adsorption equilibrium. Three kinds of crude Japanese coal show different carbonization charactor, but the adsorption properties carbons from these coal were almost the same(Fig.8). The same adsorption properties were found from the activated carbons which had been carbonized at 500∼1000°C(Fig.1, Table2). The yield of activated carbon was logarithmical proportion to time until 40% of the carbonized material. On the other hand, it was found that the yield does not decrease below 30% under the present conditions(Fig.2). The adsorption properties depend on the activation time, especially, it has great influence upon the adsorption of large molecules(Fig.3∼7). The treatment with HCI for removal of ash before or after the activation process has little effect on the adsorption properties(Fig.9, 10). Activated carbons prepared in the present study showed better adsorption properties than the two kinds of commercial one(Fig.11∼14).

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Etho-p-dodecylbecylbenzenesulfonamide as the nonionic surfactant was prepared by addi-tion polymerization of ethylene oxide with p-dodecylbenzenesulfonamide. The reaction products were separated into several components using column chromatography. The chemical structures of the components were determined by thin layer chromatography and IR and NMR spectra analysis. The average chain length of polyoxyethylene in the polymers were estimated by the NMR method. The specific gravity and the sirface tension in aqueous solution of these samples were determined. The emulsification, solubilizatian, dispersion, the wetting were also tested by usual methods. From these experimental results, the critical micelle concentrations of the samples were obtained and it was made clear that etho-p-dodecylbenzenesulfonamide was excellent as emulsifying, solubilizing and wetting agent.

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Equilibrium uptake of ten direct dyes on cellulose from aqueous alcoholic solutions has been determined at 50°C. The dyes used have two to five sulfonic groups.
Dye uptake decreases remarkably at first, passes through a minimum, and increases as the concentration of alcohol increases. Adsorption of dyes seems to be influenced by the propor-tion of alcohol in aqueous solution in two ways, as was pointed out by Hayashi and Yabe, one of which is a depressing action and the other an accelerating action. The larger the carbon number of an alcohol is and the less the solubility of a dye is, the more remarkable the both influencesare.
It is suggested from these results that, due to the reduction of the degree of dissociation of a dye by the increasing proportion of alcohol, the adsorption from a dissociated state decreases and that from an un-dissociated state increases.

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Adsorption Isotherm of Direct Sky Blue FF on cellulosic substrate from aqueous alcoholic solutions has been determined.
All the isotherms, irrespective of the kind of alcohol and temperatures, are described as a sum of the Langmuir type and the distribution type;
Y=K₁SX/(1+K₁X)+K₂X
where Y and X are the concentration of dye on the substrate and that in solutionrespectvely, K₁, K₂ and S are the constants.
K₁ decreases and K₂/K₁ increases at 50° C with increasing the concentration of ethanol. Both K₂ and S show minimum values at 40 vol% ethanol solution.
The existence of an adsorption minimum at the concentration of 40 vol% which was pointed out in the previous paper, is also verifiable by the constants derived from the analysis of the absorption isotherms mentioned above.
When the alcohol which behaves more'effectively on dye uptake is applied, both K₂ and K₂/K₁ give larger values, but K1 gives a smaller one.
These analysesseem to support the supposition that the proportion of alcohol in aqueous solution influences the dye uptake in two ways.

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The dyeing of poly(ethylene terephthalate) fibers heat-set at a constant length with Dispersol Fast Scarlet B in the presence of p-phenylphenol as a carrier wainvestigated. Accelerating effects of the carrier on diffusion rate of the dye was separated into two parts; effect A is caused by the presence of ihe carrier in the fibers and effect B is derived from the change of fine structure of the fibers due to carrier absorption.
The results are as follows. (1) Log(P₁/P₂), as a measure of effect A, decreased with the increase in heat-settingtemperature and its reciprocal was shown to be linearly related to the reciprocal concentration of the carrierwhere P₁, is the dye penetration coefficient on the normal carrier dyeing and Pthe dye penetration coefficient on the dyeing in the absence of the carrier usinthe fibers with carrier pretreatments and the following extraction. (2) Log(P₁/P₂), as a mesure of effect B, was less than log(P₁/P₂) and decreased with the increaase in heat-setting temperature, where Po is the dye penetration coefficient on the dyeing in the absence of the carrier using the fibers without carrier pretreatment. A linear relation was observed between log(P₁/P₂) and the contraction on the carrier pretreatments.

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Diffusion of disperse dyes in the four poly(ethylene terephthalate) (PET) fibers having different dyeabilities was investigated in relation to the segmental motion of the polymer.
(1) In the case of dyeing with C. I. Disperse Red 1 at various temperatures for 10 minutes, the figures which show S shape relations between dyeing temperatures and dye uptakes were obtained for each fiber. There was also observed a linear relation between the peak tempera- tures of mechanical loss tangent(main dispersion) and the inflection points of the above mentioned dye uptake-dyeing temperature relations. (2) The temperature dependence of the diffusion coefficients of C. I. Disperse Yellow 7, Orange 5 and Red 7 for the fibers obeyed the Williams-Landel-Ferry equation,
with the above mentioned inflection points as standard temperature, Ts. Here, T and aT are the temperature and the shift factor, respectively. (3) The temperature dependence of the diffusion coefficients of another azo dyes in the literature in PET films was also found to obey the above equation.

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The nitration of acenaphtylene, phenanthrene and anthracene by means of nitryl chloride as a nitrating agent has been studied. These reaction were carried out in carbon tetrachloride at temperatures between -5 and +5°C without using catalyst or light. In the cases of acenaphtylene and phenanthrene, the nitration reaction took place selectively and gave 1-nitroacenaphtylene [1] and 9-nitrophenanthrene[2] respectively. On the other hand, 9-chloro-10- nitro-9, 10-dihydroanthracene [5] was obtained from anthracene along with 9-nitroanthracene [6]. It is noted that nitryl chloride is a selective nitrating agent for acenaphtylene and phenanthrene and superior to the other nitrating agents for this purpose.

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Amorphous poly (ethylene terephthalate), (PET), film was stretched up to v=2, where v is draw ratio, and subsequently annealed at 60.5 and 62.2°C for 3 hours in a silicone oil bath, followed by quenching in ice water. Changes of the amorphous structure of PET during these processes were studied by density measurement, differential scanning calorimetry, IR spectroscopy and dielectric loss measurement and the following results were obtained.
(1) In the range of v=1∼1.5, density (d), fraction of trans segment (r), and glass transition temperature (Tg) decreased, while frequency at the maximum dielectric loss(finax) increases with increasing v.(2) In the range v=1.5∼2.0, d, r and Tr, increased and fm decreased with v, i. e., each of these quantities versus v just passed through a maximum or minimum at v=1.5. (3) By annealing, d, r and Tg increased and fmax decreased. (4) A differential scanning calorimetry (DSC) curve exhibited an endothermic peak around 340K°, which became less conspicuous with stretching and recovered the initial quantity by annealing.
It was concluded from (1)∼(4) that the free volume of amorphous PET increases in the initial stage of stretching, bbut recovers the initial quantity by annealing. It may be suggested that a weak structure exists within amorphous PET, which is destroyed by stretching but regenerated by annealing at temperatures below Tg.

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The column fractionation of polyethylacrylate ([η]=0.82, acetone, 30°C) with mixed θ solvents using acetone instead of ethanol as a solvent and water as a precipitant (Table 2, No.7, Fig.3, Table 3), and acetone instead of ethanol as a solvent and n-hexane as a precipitant (Table 2, No.8, Fig.3), respectively, were found to proceed efficiently. The range of the fractional temperature with mixed θ solvents was two times (Table 2, Fig.1), greater than that used ethanol as a θ solvent. The θ column fractionation using ethanol as a θ solvent was carried out in the same manner as the fractionation of Baker-Williams method and Desreux method already described, and that using acetone as a solvent and n-hexane as a precipitant (Fig.5) was also carried out. The depositional method of polymer to the glass beads has been investigated. The results of the fractionation due to the freeze drying method was the same as that due to precipitation deposition method (Fig. 6).

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Column fractionation was carried out to characterize column fractionation using ethylacrylate2-chloroethyl vinyl ether (95/5) copolymer as a sample and ethanol as a solvent. In BakerWilliams method the results of the fractionation (Fig.2, Table 1) were influenced by surface area of the glass beads per 1 gr. of the sample and by molecular weight of the sample. In Desreux method the exponential temperature elevation was advantage to save fractional time for a large amount of sample. θ Column fractionation showed higher efficiency than the method already described (Fig.5).

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When so called dehydrating agent is added to an aqueous solution of polyvinylpyrrolidone (PVP), the behaviour of intrinsic viscosity, [η], of PVP is in three ways : (1) [η] increases because the agent is a solvent of PVP (e.g., methanol and ethanol). (2) [η] decreases monoto- nously with the amount of addend, and then PVP precipitates (e.g. electrolytes such as disodium carbonate). This behaviour is the same as the case where carbon tetrachloride is added to chloroform solution of PVP. (3) With amount of addend, [η] reaches a maximum, and then decreases to precipication of PVP (e.g., acetone and dioxane).
Effect of temperature on [η] is specific to chemical species and amount of precipitant in mixed solverit. When dioxane or acetone is used as the precipitating agent, [η] decreases with temperature at low concentration of precipitating agent. At higher concentration, however, the relation is reversed. Assuming the mixed solvent which shows no temperature effect on [η] as the solvent of standard condition, it was found that the relation between expansion factor, an, and temperature, T, is in accord with Flory's theory. Entropy parameter, Pi, and enthalpy parameter, k1, of dilution were found to be negative at low concentration of precipitating agent and at high temperature, but at high concentration of precipitating agent, these parameters were positive. It was concluded that 1 and IC k1 become negative by hydration of PVP, because of the evolution of heat of hydration and the orienting of water molecules to PVP.

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Fluorine substituted aromatic polyamides have been prepared by polycondensation of fluorinated m-phenylenediamines and isophthaloyl chlorides in dimethyl acetamide. In this experiment, 5-fluoro-, 2, 4- and 4, 6-difluoro- and non-substituted 1, 3-phenylenediamines as amine component, and 5-fluoro-, 4, 6-difluoro- and non-substituted isophthalic acids as acid component were used. The thermostability of these fluorine substituted aromatic polymers was evaluated by the thermogravimetric and the differential thermal analysis, and the results were compared with those of the fluorine-free poly(1, 3-phenylene-isophthalamide). It was found that the polyamides substituted ortho- or/and pa.ra-positions especially 4, 6-position on 1, 3-phenylenediamino group with fluorine increased the thermostability considerably. On the contrary, the polyamides containing 4, 6-difluoroisophthaloyi group. decreased the thermosta-bility. On the other hand, almost no effect on thermostability was found from the polyamide having a fluorine atom at the meta-position to amido or carbonyl groups on either phenylene-diamino- or isophthaloyl-group.
Further, two other kinds of fluorine-containing polyamides prepared from 2, 5-difluoro-1, 4- phenylenediamine and terephthalic acid, or 2, 2'-difluoro-4, 4'-diaminodiphenyl ether and terephthalic acid have been studied. It was found the former polyamide in which fluorine occupied the ortho-positions to NH brought a favorable thermostability, but in the latter in which fluorines substituted meta positions to NH, had no influence on the thermostability.

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Diallyl isophthalate (DAI) and diallyl terephthalate (DAI) were copolymerized with allyl benzoate (ABz) in bulk at 60°C, using benzoyl peroxide as an initiator.
In both copolymerization systems the rate of polymerization and the degree of polymerization of the copolymers tended to decrease with an increase in the mole fraction of ABz in the feed.
In the copolymerization of DAI with ABz the residual unsaturation of the copolymer was nearly constant, regardless of the feed molar ratio, while in the copolymerization of DAT with ABz it tended to increase with increasing the mole fraction of ABz in the feed.
The apparent monomer reactivity ratios obtained on the basis of the general copolymer composition equation were as follows: M₁, r₁, r₂; DAI, 0.69, 1.02; DAT, 0.77, 0.89.
On the other hand, for the copolymerization of DAI with ABz the following monomer reactivity ratios(MRR) were also estimated on the basis of the cyclocopolymerization mechanirn: 7-1=0.77 (MRR of the uncyclized radical), rc=0.52 (MRR of the cyclized radical), r₂=1.00(MRR of the ABz radical).
These results were discussed in connection with the results of the copolymerization of diallyl phthalate with ABz⁵.

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It was found that styrene was polymerized with chromous acetate (Cr²⁺)-systema as an initiator at 30°C in dimethylformamide(DMF).
Polymerization ability for various alkyl halides was in the following CCl₄ > CHCl₃ > CH₂Cl₂ > CH₃Cl, CHCl₂-CHCl₂ > CH₂Cl-CH₂Cl, C₆H₅CH₂Cl > C₆H₅Cl, CHl₃ > CHBr₃ > CHCl₃, CH₂Br-CH₂Br > CH₂Cl-CH₂Cl.
In the polymerization of styrene with Cr²⁺-CHCl₃ system, the rate of polymerization was found to be proportional to the concentration of styrene and to the square root of the concentration of Cr²⁺ and CHO, respectively and the apparent activation energy was 11.6 kcal/mol.
From the above results and the results of copolymerization of styrene with methyl methacry-late, it was found that the polymerization of styrene with this initiator system proceeded by radical mechanism and was initiated with alkyl radical formed from the halogen abstracting reaction of CHCl₃, with Cr²⁺.
The Cr²⁺-CHCl₃ system initiated the polymerizations of styrene and methyl methacrylate, but was ineffective for the polymerization of acrylonitrile and vinyl chloride.

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Adsorptive properties of m-aminophenol resins for various amines, such as ammonia, trimethylamine, triethylamine, n-tripropylamine, and n-tributylamine, contained in moist air at low concentration (0.7∼1.8 vol%), was dynamically measuied, in order to remove amines from air. Amines were completely removed by these adsorbents at the flow rate lower than 40 cm/sec and the break-through capacities were found to vary remarkably with the molecular weight, solubility into water existing in the resin phase, and the flow rate of amines. At the flow velocity of 3.36 cm/sec at room temperature, the break-through capacities of porous m-aminophenol resins for ammonia, trimethylamine, triethylamine were 2.0 to 2.5 meq. /g-dry resin, which tended to increase with pore size of resins. The effect of flow rate on break-through capacities was much less significant with highly porous resins (pore radius, larger than 1500 A). Static adsorption of ammonia was expressed by the Freundlich's type adsorption isotherm, and the heat of sorption calculated using Clausius-Clapeyron equation was 5 to 6 kcal/mol.

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Adsorption equilibrium of sulfur dioxide on the m-aminophenol resins with various pore structures was measured gravimetrically at the temperature range of 20∼60°C and equilibrium pressure up to 760 mmHg. Heats of adsorption were estimated as 14 to 15 kcal/mol using Clausius-Clapeyron equation. Apparent activation energy of adsorption of sulfur dioxide was calculated as 1 kcal/mol from Arrhenius plot. Adsorption capacity of the resins for sulfur dioxide was measured dynamically, by circulating sulfur dioxide (1.77% in N₂) over the resins at the flow velocity of 76 cm/min at ambient temperature and pressure, and was compared with that of macroreticular and gel type quaternary ammonium anion-exchange resins in the R-OH form. The adsorption capacity of highly porous resins for sulfur dioxide was 29 to 30 ml-STP/g-dry resin. Adsorption reached nearly equilibrium over the porous resin with ten minutes.

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Water-soluble cationic polymers were prepared by the aminolysis of polymethylmethacrylate (PMMA) with polyethylenepolyamine. The application of the polymer to cationic flocculation effect for kaolin suspensions was investigated. The flocculation effect was studied by observing the supernatant suspension concentration after 2 minutues in jar test and the sedimentation rate by the test tube.
The best flocculation effect was obtained when PMMA (M. W.3∼20 x 10⁵) were treated with 5∼10 mol polyethylenepolyainines (to ester groups) in dimethylformamide at 170∼180°C for 5∼7 hours. Diethylenetriamine, triethylenetetramine and tetraethylenepentamine gave similar efficiencies. The suitable concentration range to the 500 me kaolin suspensions was ppm and the supernatant concentration at the optimum dosage was below 40 mg/l. The cationic polymers are most effective in the pH range of 2.5∼8.5. The maximum rate of sedimentation was 5.25 cm/min, when the amount of the polymers was 0.004% with respect to kaolin.

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Cellulase-hydrolysis reaction of various cellulose materials treated with swelling agents were studied kinetically. Results are as follows:
1) The estimation of kinetic parameters by means of the weight loss due to cellulase-hydrolysis was not suitable for swollen pulps, because the Hofstee plots by this method were on the curved line which was expected to be straight theoretically. If we assumed that the deviation of the plots from straight line was experimental errors, incorrect results would be expected. Among the samples which showed great differences in weight loss, the number of cleavage-of glucsidic linkage should be selected in a suitable range to get satisfactory results To estimate the maximum velocity V and Michaelis constant K, in the Hofstee plots, ; t was recommended to use a derived theoretically from the weight loss of the sample.
2) As there was a certain relationship between the increase in accessibility and the decrease in Km, with swelling, the relative accessibility of unknown sample could be estimated by "trial and error" method. In our experiments, if we postulate the accessibility to be 0.20 for untreated sulfite pulp (SP), values of 0.27, 0.30 and 0.39 were obtained for 12% sodium hydroxide-, 85% ethylene diamine- and 30% Triton B- solution treated SP, respectively. These values appear to be related to the fiber saturation point of the samples.
3) According to the above concept, the effect of swelling of cellulose materials on cellulasehydrolysis could be interpreted in terms of the increase in amounts of accessible portion of the samples.
4) However, in comparison among cellulose materials from different sources, their differences should be due to other physical and chemical characteristics of each materials as well as their accessibilities.

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The reduction of nitrobenzene by NaBH₄ in the presence of various Co (III) complexes was investigated at 25°C in aqueous solution in nitrogen atmosphere. A nearly equimolar mixture of aniline and azoxybenzene was obtained from nitrobenzene in the presence, of Co(NH₃)₆³⁺ salts, except nitrate, and chloroammine Co (III) complexes. Upon the substitution of a portion of NH₃ ligands of Co(NH₃)₆³⁺ by NO₂^- or CN^-, the product varied to aniline for [Co(NO₂)₃ (NH₂)_6-x]^(3-x)+ and to azoxybenzene for [Co(CN)_x(NH₃)_6-x] ^(3-X)+. No reaction occurred, however, when completely substituted Co (NO₂)₆³⁺ or Co (CN)₆^3- was used. The main product was azoxybenzene in the case of Co(III) ethylenediamine complexes.

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Fe(II) ion exchanged molecular sieve 13 Y catalyst was found to have a fairly good selectivity for partial dehydrogenation of cyclohexane to cyclohexene in the presence of oxygen at 180°C. Some parts of cyclohexane converted was dehydrogenated to benzene. The products distribution profile suggested a reaction scheme of successive dehydrogenation. Several other metal ions, such as Co(II), Cu(II), Cr (III), loaded on the zeolite by an ion-exchange method showed the less activity and selectivity. Some activities for the reaction were also observed with the molecular sieve NaY and protonated type, but very little activity with a decationized zeolite.

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As particularities of the mechanochemical dehydration of MgHPO₄3H₂O, it was shown that the salt converted rapidly into amorphous phase without forming any crystals of anhydrate and pyrophosphate by grinding, and the ground salt had a sharp exothermic peak due to recrystallization of pyrophosphate in differential thermal analysis curves.
As the case of CaHPO₄2H₂O, the escape of water molecules and the destruction of hydrogen bonds progressed in parallel during grinding.

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Cr(C0)₆, Mo(C0)₆, and W(C0)₆ were analysed quantitatively by gas chromatography em-ploying a thermal conductivity detector in combination with a column packed with 30 x 300 mm 10% 1, 2, 3-tris(2-cyanoethoxy)propane on 60/80 mesh Diasolid M at column temperature 76°C, injection temperature 116°C and helium flow rate 30 ml/min.

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Tetrafluoro(Methyl Red)[4] has been prepared by azocoupling of diazotized tetrafluoroanthranilic acid[3] with N, N-dimethylaniline. The synthetic route has been improved to give 55% yield of [3] by three steps starting with tetrachlorophthalonitrile, through tetrafluorophthalonitrile[1] and tetrafluorophthalimide[2].
The visible absorption spectrum of the alkaline solution of [4] in ethanol was quite similar to that of the neutral solution, and slight bathochromic shift in the acidic solution, compared with that of unsubstituted. Methyl Red(Fig.1 and 2) was noted. These results indicate that [4] dissociates even in neutral solution into the carboxylate anion almost completely, and that the protonation on [4] in acidic solution is much more difficult than that on unsubstituted Methyl Red.

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The Temperature dependence of dye penetration coefficients in the carrier dyeing, of polyethylene terephthalate fiber, with three kind of carrier, was investigated.
It was found that the temperature dependence of dye penetration coefficients is in accord with the Williams-Landel-Ferry equation which has been observed for diffusion coefficients in the, normal dyeing (without carrier),
where aT is the shift factor, p and ps are the dye penetration coefficients at absolute tempe, rature, T, and at the standard temperature, T, respectively.
The standard temperatures in the carrier dyeing were lower than those of the normal dyeing. The standard temperatures in the normal and each carrier dyeing were about 20°C higher than those of contraction under the same treatment.

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Sepiapterin was synthesized by the reaction of α-keto-β-hydroxybutyric acid and 7, 8- dihydropterin(Na salt) in the presence of zinc chloride. The reaction products were the mixture of two yellow compounds ((I) and (II)), which could be separated by chromatography on cellulose and Sephadex columns. Both compounds gave the same molecular formula, C₉H₁₁O₃N₅. From UV, NMR and ORD spectral data as well as chemical reactions, the structures of the compounds were proved to be 2-amino-4-hydroxy-6-(d, l-lacty1)-7, 8-dihydropteridine (I)and 2-amino-4-hydroxy-16-(1'-hydroxy-2'-oxopropy1)-7, 8-dihydropteridine (II). (I) was a mixture of sepiapterin and its stereoisomer (each, 50%) this was proved by the action of sepiapterin reductase.
The reaction of 7, 8-dihydropterin and a-hydroxyacetoacetic acid gave solely the compound (II).

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Diallyl phthalate (DAP) was copolymerized with vinyl chloride (VC) at 60°C, using 2, 2'- azobisisobutyronitrile as an initiator.
The rate and the degree of polymerization of the copolymer decreased markedly with an increase in the mole fraction of DAP in the feed.
The residual unsaturation of the copolymer increased with increasing the mole fraction of VC in the feed.
The following monomer reactivity ratios (MRR) were obtained on the basis of the cyclocopolymerization mechanism: r1=0.38 (MRR of the uncyclized radical), rc=0.33 (MRR of the cyclized radical), and r2=1.68 (MRR of the VC radical).

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3-Ethylideneacetylacetone (EAA) and diethyl methacryloylmalonate (MMD) have been copolymerized with styrene (St) and acrylonitrile (AN). The copolymerizations were carried out at 60°C. The monomer reactivity ratios of each of these monomer pair were determined. The reactivity ratios were:
From these results, the Q and e values for EAA and MMD were calculated as follows:
Q=0.028, e=0.91 for EAA
Q=1.45, e=0.97 for MMD

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Products from the reactions between carbonyl compounds and organomagnesium reagent obtained from methylene iodide and magnesium turnings were investigated. When benzaldehyde (50 mmol) was allowed to react with methylene iodide (50 mmol) and magnesium turnings (103 mmol) in ether for 2 hours under gentle reflux, styrene (29%), benzyl alcohol (22%), and 1-phenylethyl alcohol (5%) were obtained, accompanying the formation of considerable amount of tarry residue after distillation (Table 1). Other aldehydes and ketones also gave carbonylmethyle nated products [1], reduction products (alcohols) [2], and reductively methylated products [3] (Table 2). The formation of alcohols ([2] and [3]) and tarry matter appaers to limit the yield of the carbonyl-methylenated product [1].

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The r-ray-induced copolymerization of vinylphosphonyl dichloride (VPDC) with acrylonitrile (AN) was studied at 25 and -78°C, and the reaction mechanism was examined. The copolymerization proceeded by a free radical mechanism at 25°C, and the following reactivity ratios Q1 and e1 value for VPDC monomer (M₁) were estimated.
r₁=0.05, r₂=6.0
Q₁=0.87, e₁=2.7
On the other hand, the rate of copolymerization has a maximum point at about 30 mol% of VPDC monomer concentration at -78°C. In the Fineman-Ross diagram, the r₁ took a negative value, and moreover, the points shifted from the linear relation in the region from 70 to 0 mol% of VPDC monomer concentration.

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The reaction of dehydrochlorinated poly (vinyl chloride) (DHCl-PVC) with thiophenol in tetrahydrofuran(THF) was studied at 30∼170°C under nitrogen. Thiophenol was found to react mainly with allylchlorine of DHCl-PVC at temperatures lower than 120°C and with both double bond of DHCl-PVC and allylchlorine at 170°C. The effects of azobisisobutyronitrile and UV-irradiation were also investigated.

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Cotton fabrics were treated with hydroxymethylated 2-diethanolamino-(MDEL), 2-monoethanolamino- (MMEL) and 2-monoethylamino-4, 6-diamino-s-triazines(MMET) in the presence of Zn (NO₃)₂, and MgCl₂ as catalysts. The effects of the catalyst on the fabric properties were examined in comparison with those by the conventional pad-dry-cure technique.
The order of the crease recovery angle of the fabrics treated in the presence of either catalyst was MDEL > MMEL > MMET, and the orders of the tearing strengths, tensile strengths and elongations at breaks were MMET > MMEL > MDEL. In general, the Zn (NO₃)₂, catalyst gave slightly better effects than MgCl₂ on the properties of the fabrics.
Judging from the relationship between the crease recovery angles and the tearing strengths, the order of the resultant effect on the improvement of the properties of the treated fabrics was considered to be MDEL > MMEL > MMET in the presence of Zn (NO₃)₂ as catalyst, but MMEL > MDEL > MMET in MgCl₂. The effect of Zn (NO₃)₂, as catalyst on the balance between the improvement of the crease recovery and the retention of the strengths was slightly better than MgCl₂ in the fabrics treated with MDEL and MMEL, but the order was reversed with MMET.

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