The electronic spectra of dibenzofuran derivatives were observed. The spectrum of dibenzofuran has main peaks at 3O^2-.1, 287.1, and 249.7 nm in cyclohexane. They have been assigned to be Lb, L, , and B transitions respectively by using the results of solvent and substituent effects. The Lb band is short axis-polarized, shows blue shift in acidic solvents, and is most affected by the substituent at the 2-popition of dibenzofuran. The correlation of the wave number with the resonance parameter of substituent was expressed as v (kK) =33.10-4.17 The L. band is long axis-polarized, and is affected by the substituent at the 3-position of dibenzofuran. The correlation was expressed as v (kK) = 34.83 3.99.1a, 1 The Lb band of dibenzofuran and its analogues (fluorene, dibenzothiophene, etc.) were closely related to the p-orbital electronegativity of heteroatoms and the aromaticity of the five-membered ring. The interaction of oxygen with the aromatic ring was discussed.

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The viscosities of aqueous guanidinium salt solutions were measured at relatively low concentration at various temperatures. The viscosity B-coefficient of Jones-Dole equation and the activation energies of viscous flow for the guanidinium salt solutions were obtained and shown in Tables 1 and 4. The contribution of guanidinium ion to the activition energy of viscous flow was 20 cal/mol and the B-coefficients of guanidinium ion were O. O^2-8, 0. O^2-2 and O. O^2-9 at 10, 25 and 35° C respectively. However, as shown in Fig.5, these values become negative (-0.077 at 25° C) when the size effect of guanidinium ion, which is evaluated by Einsteins' viscosity equation for large solute particle, is taken into account. This means that the positive value of B-coefficient is mostly due to the contribution of hydrodynamic obstruction effect. Based on the above results, guanidinium ion was concluded to be a structure breaker ion.

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In order to clarify the mechanism of the acidity change due to compression, the surface acidities and the structures of calcium and cadmium sulfates compressed under various pressures were studied; for CaSO₄ the pressure was 0-3840 kg/cm² at 20, 65, or 85° C, and for CdSO₄ the pressure range 0-7000 kg/cm² at 50° C. It was observed that the surface acidities of both solids vary on compression. From the results of the powder X-ray diffraction, the DTA, and the infrared absorption studies, the relation between the acidity and the structural changes was discussed.

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The thermal stability of sodium, potassium, calcium, barium, zinc, cadmium, lead and silver hydrogen maleates in solid state was studied by the methods of TGA and DTA. All the metal salts exhibited an endothermic process accompanying a considerable loss in weight between 150C and 30C. During this process maleic acid was liberated and the resultant residue was the metal maleate except the cases of alkali and alkaline earth salts. Accordingly, it is concluded that the endothermic process corresponds to an ion exchange reaction between a metal ion and a hydrogen ion in the metal hydrogen maleate. The ion exchange took place perfectly for the heavy metal salts, but imperfectly for the alkali and alkaline earth salts. Particularly, in the case of alkali metal salts carbon dioxide was also formed partly by the decarboxylation of the carboxyl group. The mechanism of the ion exchange reaction in solid state is discussed from the viewpoint of the crystal structure of the metal hydrogen maleate. In the case of alkaline earth metal salts, the residues are stable intermediates, which include hydrogen maleate ions and maleate ions at a fixed ratio and give the characteristic X-ray diffraction patterns.

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It is known that there is a correlation between pla, and the electron density of nitrogen atom of amino compounds. However, this relation can be applied only for limited kinds of amino compounds.
In this paper, we calculated the dissociation model of several kinds of amino compounds (methylamine, ammonia, hydrazine, hydroxylamine, aniline and urea) by CNDO/2 molecular orbital method, on the basis of the following moael, in which d is 3.0 A and r is varied from 1. o A. to 2. A.
The minima of the total energy were obtained at r=1.1 A and r=1.9 A. It seems that the minimum at r=1.9 A corresponds to a state of (A-NH₂ H3+0) and that at r=1.1 A to (A-HN2+ +, H₂O). Interaction energy of each state U (A-NH₂. -H₂+0) and U (A-NI-12+.. H₂0) and the difference (4U) were calculated by Eqs. (1) and (5).
Excellent correlations between the 4 U and plCa values of the above amino compounds were obtained except for aniline. In the cases of hydrazine and urea, the influence of water mol- ecules coordinated with the amino group was considered.

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PVC char was prepared. by heat treatment of carbon residues, obtained by heating poly(vinyl chloride) powders with concentrated sulphuric acid at about 150° C, in a nitrogen atmosphere at 900° C for 2 hours. The activation reaction of the char with ammonia gas obeyed first order kinetics, having about 42 kcal/mol Of apparent activation energy in the range of 800° to 1000° C. From differential proe-volume distribution curves for the activated PVC chars, the increase in pore-volumes was observed mainly in the micropore regions and it was correlated with rather the weight loss than the temperature in the activation process. The change in the micropore volume in the chars estimated from Dubinin plot indicated that the micropores (dS30 A) were excavated and developed with activation up to the weight loss of about 50% and successively the transitional pores (30 A<d<300 A) were developed remarkably. It was found from electron microscopic observations that the char had well-developed macropores.

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The adsorption of hydrogen and carbon monoxide by palladium supported on silicaialumina and the reaction of the adsorbed hydrogen with gaseous ethylene were investigated at 20° C. The desorption process of the adsorbed carbon monoxide was examined by means of the secondary isotherms, and it was found that CO is adsorbed in two states, strongly adsorbed CO and weakly adsorbed CO. The result of the co-adsorption of hydrogen and carbon monoxide shows that the main adsorbed species in the presence of both gases are strongly adsorbed CO and weakly adsorbed Ha (including dissolved H). The strongly adsorbed H is readily reacted with gaseous ethylene to form ethane quantitatively.

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Calcium 2-oxogluconate is one the widely used reagents for a cement admixture. It is apparent from the results of experiments that the setting time can be remarkably retarded through an addition of calcium 2-oxogluconate to the 8-CaSO₄ 1/2 H₂0 paste under a high alkalinity in the presence of Ca (OH) 2. The present investigation was initiated in order to solve the mechanism of reaction between 8-CaO^2-.1/2 H₂O, Ca (OH) 2 and calcium 2-oxogluconate. The solubility of 8-CaSO₄/2 H₂0 in aqueous solution of calcium 2-oxogluconate is approximately constant independent of concentration. For example, the solubility of total CaO in aqueous solution of calcium 2-oxogluconate involved 8-CaSO₄.1/2 H₂0, and the concentration of calcium 2-oxogluconate are placed in Total [CaO], and C in (mol/l), respectively.
Total [CaO] C 0. O^2-0
On the other hand, in any case of Ca (OH) 2, the solubility of Ca (OH) 2 in aqueous solution of calcium 2-oxogluconate is abnormally high. It is proportional to the concentration of calcium 2-oxogluconate.
Total [Ca (OH)2] t 2 C 0. O^2-1
These reasons are attributed to the soluble complex formation. Therefore, calcium complex has been formed by the combination of one CA²⁺ ion and 1 mol/l 2-oxogluconic acid. Further, the authors confirmed by the electro-conductivity as Well as the solubility. The formation of calcium complex is also supported by IR spectra.

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The addition of Ag20 was found to increase the availability of active material in the Positive plate (Ni (OH)2; 50, graphite; 35, polyethylene; 15) of pressed-type Ni-Cd storage battery and the authors studied the function of Ag20 on charge-discharge by means of current-potential curve obtained with Ag in aqueous pottasium hydroxide and atomic absorption spectrophotometry. The following mechanism was proposed;
(1) The discharge capacity of Ag2O is not contained in that of nickel electrode.
(2) Ag20 added to the positive plate changes into Ag by the reaction (Ag20 Ag) on discharging, and Ag changes into active Ag20 by the reactions (2 Ag + 2 0H- 2 AgOH + 2 eand 2 AgOH - Ag20 + H₂0) on charging. A part of this active Aga dissolves into electrolyte solution and dissociates according to the following equation: Ag20 Ag + Ag0-.
(3) Ag + will probably affects negative electrode and Aga- remaines in solution. But, amount of Ag dissolved from positive electrode, to which Ag20 is added in 10%, is very small even after 300 cycles.

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The conditions for forming KA1CO₃ (OH), from potassium aluminate solution by method of blowing CO, were examined and its physicochemical properties were investigated by X-ray diffraction analysis, thermal analysis, infrared spectrometry and electron microscopic observation etc.
KA1CO₃ (OH), was formed in almost 100% when there was a large amount of HCO^3- in potassium aluminate solution where alkali was neutralized and aluminate ion was present in a supersaturated state. Those conditions were satisfied when the molar ratio of 120/A1, O^2- of the potassium aluminate solution was 8-10, the reaction temperature 80-90° C, and CO, was blown into the solution sufficiently.
From the results of formation conditions and infrared absorption spectroscopic analysis etc, its rational formula was appropriate to represent KA10 (OH)HCO, . Carbon dioxde in synthetic KA10 (OH)HCO, was evolved by heating 320-400° C and lattice OH was dehydrated by heating 690-740° C to be KA1O^2- which was very hygroscopic crystal.
The activated energy of decarbonation was 64.1 kcal/mol. KA10 (OH) HCO, had a true specific gravity of 2.40 and was in a needleshaped crystal by electron microscopic observation.

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The study of ammonium sulfite leaching has been carried out with manganese nodules which were dredged at W 170° 21 and N 8° O^2- by the exploration party of Japan in the year of 1970. The nodules used were crushed to 150 mesh pass and leached in a small stainless tube having a capacity of 17 ml at 20-180° C. Under the best condition applied were able to be extracted 80-90% of metals. Manganese oxide in nodules quantitatively changed to manganese sulfite with the formation of ammonium dithionate. Owing to its insolubility, manganese sulfite produced during the leaching might have covered the surface of nodule particles, but was easily dissolved by air oxidation in water. Accordingly, the remaining metals in the residue were able to be recovered by secondary ammonium sulfite leaching. Thus, the total leaching degree of metals was over 90% by the two-step treatment.

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Graphite single crystals were grown by the solidification of the melt under high temperature and high pressure of 2 kb and 10 kb for the durations of about 1 sec and 0.5 sec, using a piston cylinder type high pressure apparatus. Spectroscopic graphite electrode rod (0.3 c X 17 mm, 1.8 qx 3 mm for the central part) was used as a starting material and a heater. In contains only a negligible amount of calcium.
Temperature calibration under high pressure was carried out by the use of a platinum platinum 13% rhodium thermocouple and based on melting points of platinum, molybdenum and tungsten wires. It was found that temperature was almost proportional to electric power input below 2000° C. Since it was uncertain whether this linear relation was able to be extra polated above 2000° C, the temperature was expressed in terms of the eleetric power-input (watt).
Most of large graphite single crystals with metallic luster were grown at the surface of graphite heater at 2 kb, 2500 watt and 10 kb, 3190 watt, with c-plane parallel to the direction of applied pressure. Crystals produced were platelets with maximum dimension of 2.1 mm in width and 0.25 mm thick. On the other hand, graphite single crystals smaller than 0.4 mm in width were mostly produced in the central part of the heater, and their basal planes were generally orientated in a direction normal to the applied pressure. It was found that the content of large graphite single crystals larger than O.2 mm in width incresed with the increase in temperature and time of treatment. The dimensions of graphite single crystals produced by the solidification from temperatures within a vapor phase region of carbon, were comparatively smaller than those of crystals from temperatures within a liquid phase region.
Smaller globules of graphites with maximum diameter up to 6 gm were formed at the surface of the basal planes of grown graphite single crystals above 2600 watt-2 kb or 3300 watt-10 kb. Results from X-ray diffraction of grown graphite single crystals indicated that crystals produced had lattice spacings close to the values of natural graphite given in the literature.

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The present paper deals with the distribution of trace elements and their chemical behavior in the head-water area of the Tama River using activation analysis.
The water samples were taken at 5 points in the main stream and 25 valleys flowing into it. The irradiated samples were made in the following ways: the elements inducing long life nuclides were prepared by evaporation to dryness and those inducing short life nuclides by coprecipitation method with Fe (OH), or Al (OH),
The activity of the irradiated samples were measured by 4096-channel PHA coupled with a Ge (Li) detector.
The analytical results are as follows: in the first place, the concentrations of Se, V, Co, As and Se were closely related to the geology of the areas through which the valley streams flow. Se content of streams which ran on the sedimentary rock formations was found to be 0. O^2- 0.09 ppb, whereas in streams on the igneous rock formations Se was not detected. Arsenic content of each streams on the igneous rock formations or the Jurrasic formations was found to be 0.6-1.4 ppb, whereas in strenms on the Cretaceous formations to be 1.7-2.3 ppb.
In the second place, Sb content had a close relation to the distance between the streams and the center of the metropolis rather than to the geology of the areas where the samples were taken, namely the shorter the distance, the higher became the Sb contents.

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The possibility of utilizing Pco2 electrode for the analysis of carbonates was investigated. After CO, was liberated by adding 0.1 N-HCl to a sample solution or to solid powder sample that was sedimented in water, concentration of CO₃2- in the resultant solution was measured by Pco2 electrode. The response of electrode was fast (90-120 sec), the slope of calibration curve was 60 mV at 33° C, and linear relationship between logarismic concentration of carbonic acid and the potential of Pco2 electrode was obtained.
Interferences of volatile acid such as H₂SO^2- or HNC, could be eliminated by oxidation of these acid with H₂O^2-. Following procedure is proposed for the determination of CO, in phosphate rocks and fluorite ores. The p9wder sample was taken in a 100 ml beaker, and 20 ml of water and 20 mi of 3% H₂O^2-0.1 N HCl reaction solution were added to the beaker and mixed.
A portion of the solution was injected to the cell by a syringe, and the potential of PCO₂ electrode was measured. The concentration of carbon dioxide was determined from the calibration curve obtained on the standard bicarEoaate solution. The analytical res ilts by the proposed method were in good agreement with those obtained by CHN analyzer method.

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The anodic polarographic behavior of ammonium diamminetetrakis(isothiocyanato)chromate (III) (Reinecke salt), which forms a slightly soluble salt with mercuric ion, was studied in water and in acetone-water mixture.
In an acidified aqueous solution of sodium perchlorate, Reinecke salt produced a two-step anodic wave, as shown in Fig.1. The half-wave potential of the first wave, which showed the charactaristics of the adsorption prewave, was about +O.21 V vs. SCE. The first wave height increased linearly with increasing concentration of Reinecke salt. However, when the concentration of Reinecke salt exceeded the critical value of 4 x 10-4 mol 'dm^-8, the first wave' height remained constant and the second wave (main wave) appeared at +O.34 V vs. SCE, as shown in Fig.4. The first wave height was proportional to the height of mercury column. The total wave height was proportional to the square root of the mercury column height. The relative temperature coefficients of the first and total wave heights were 1.16x 10-2 K-1 and 1.40 X 10-1 K. - at 25° C, respectively.
On the other hand, Reinecke salt in 1: 1 acetone-water mixed medium showed a single anodic wave, as shown in Fig.2. The limiting current was proportional to the square root of the mercury column height. Though the relative temperature coefficient of the wave height showed a relatively high value of 3.27 x 10-21C-i at 25° C, it was concluded that the wave was diffusion controlled current from the electrocapillary measurement (Fig.8) and that dependence of the current intensity on the mercury column height was present.
From the analysis of the polarographic waves (see Fig.9, 10 and 11), it was concluded that these anodic waves were produced by the formation of Hg [Cr (NCS), (NFI, ), ], at the surface of the dropping mercury electrode.

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A small amount of water in volcanic rocks has been determined by the Karl Fischer method. The analytical apparatus consists of four trains, purifying train of nitrogen carrier gas, heating train of a combustion tube mounted in coil of high frequency induction furnace (3 kW, 400 kHz), oxidizing train for some volatile substances released from the sample, and measuring train of water by Karl Fischer titration apparatus. These trains are connected by a glass and copper pipes, as shown in Fig. 1.
The sample is weighed into a fused silica crucible and dried at 110° C for 3 hours. The crucible is placed into a carbon column and set at a center of the induction coil by using two supporting silica tubes, as shown in Fig.2. After passing the dried nitrogen gas to sweep water adsorbed in the apparatus, the carrier gas is introduced into Karl Fischer titration vessel. The water in the gas is absorbed into an anhydrous mixture of methyl alcohol and ethylene glycol (1: 1), and the mixture was titrated by Karl Fischer reagent (factor O.5 mg H₂0/m/). The blank of the gas passed through the apparatus is very low, amounting to about 4.1x1O^2- to 5.3 x 10-8 mg H₂0// of N2. Correction of blank is made at every measurement, because the volumes of the carrier gas used is very large. After a blank test, the sample is heated to 1300-1500° C in the constant stream of carrier gas by high freqency induction furnace. Hydrogen, carbon monoxide and sulfur compounds in volatile substances released from the sample are oxidized by the mixture of cupric oxide and palladium asbetos heated about 700° C. The water released into the carrier gas is determined by the same manner in which the blank test is carried out.
A small amount of water in volcanic rocks can be determined accurately by this proposed method. The precision is comfirmed to be 0. O^2- mg H₂0. The water released on heating a recrystallized copper sulfate was completely absorbed into the anhydrous mixture solution and titrated by Karl Fischer reagent. The recovery is 99.97%. The coefficients of variation of the results are O.16% for CuSO₄.5 H₂0, 0.28% for obsidian and O.14% for the geochemical rock standard JB-1.

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The reaction of 8-halo-a-alanine methyl ester hydrohalide (halogen=Cl, Br) in the presence of organic or inorganic base catalysts was studied.
As a result, unexpected a, a'-dicarbomethoxy divinylamine [6] was obtained in 50, -75% yield and neither 2, 5-dicarbomethoxy piperazine C 2 nor other expected compounds C3 D 5 were isolated.
The structure of C 6 was determined by IR, 'H-NMR, C-NMR and Mass spectra. Hydrogenation of C 6D gave a, a'-dicarbomethoxy diethylamine [11], 1 which was identified by IR and 'H-NMR spectra.

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2, 5-Distyryl-3, 6-bis (dimethylcarbamoyl) pyrazine derivatives C 3 J were synthesized by the condensation of 2, 5-dimethyl-3, 6-bis(dimethylcarbamoyl)pyrazine[1] with substituted benzal- dehydes C 2 in a t-BuOH-hexamethylphosphoric triamide-tetrahydrofurane mixture. The yields of [3] were found to be remarkably influenced by reaction temperatures, solvents, and substituent groups.
Most of C3J are bright yellow crystals and have strong greenish yellow fluorescences. When illuminated with ultraviolet rays of wavelengths of about 365 nm, the dioxane solutions of C 3J fluoresce with maximum wavelengths of about 4500 nm.
Compounds of [ 3 ] dye both of nylon and polyethylene terephthalate, but their fastnesses to light are undesirable.

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Treatment of p-nitrobenzyl chloride with benzyltriethylammonium hydroxide in the mixture of carbon tetrachloride and nitrobenzene was found to give a, a'-dichloro-p, p'-dinitrostilbene [3] in a 98% yield under the most favorable condition. Bis(p-nitrophenyl)acethylene C_2C and p, p'-dinitrostilbene [1] were obtained as byproducts. The yield of C3 J varied considerably with the molar ratio of nitrobenzene to carbon tetrachloride; in the the absence of nitrobenzene [3] was formed in a 25% yield, while in the absence of carbon tetrachloride [3] was not formed at all. The most favorable medium employed for the formatiom of [3] was found to be a 2: 1 mixture of nitrobenzene and carbon tetrachloride. Furthermore, C 3D was also obtained from p-nitrotoluene or nitrobenzene in the presence of carbon tetrachloride under similar conditions, and the formation of chloroform and hexachloroethane was confirmed in the reaction products.
These results suggest that the reaction proceeds through a radical mechanism, and provide strong support for the chlorine atom in a-position of [3] coming from carbon tetrachloride.

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On the methylenation of 1, 2-dihydroxy-4, 5-methylenedioxybenzene Cl ap, 1, 2-dihydroxy-3- methoxy-4, 5-methylenedioxybenzene C. / bj, 2, 3-dihydroxy-4-methoxyacetophenone Cl cp, 1, 2- dihydroxy-3- C/ dj, 1, 2-dihydroxy-4- C/ ep, 1, 2-dihydroxy-3, 4-dimethoxy-5- 1 fp, 1, 2-dihydroxy-3-methoxy-5- [l g], 1, 2-dihydroxy-4, 5-dimethoxy-3- [1 h]p, and 1, 2-dihydroxy-4, 5- methylenedioxy-3-allylbenzene C. / ij, in a noncatalyst heterogeneous reaction system, high purity methylenedioxy derivatives were obtained in good yields for a short reaction period using the cheapest methylenation agent, methylene chloride, in DMSO as a solvent, while concentra- tions of Cl a-0 had been regulated to be lowered in the reaction system according to a procedure devised by the present authors.

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The vapor phase catalytic aminations of phenol or chlorobenzene, and the activity of catalyst of cation exchanged Y type zeolites were studied. In the amination of phenol, the order of the catalytic activity, at the temperature range from 350° C to 380° C, was HY>CaY>CuY, and the yield of aniline was from 11 mol % to 14 mol %. Effect of the amount of replaced Cu2was also investigated and the maximum yield of aniline was obtained at about 80% exchange degree of Cu²⁺. By the addition of aniline or pyridine to CuY, the yield of aniline was decreased to a constant value. By the addition of hydrogen chloride to NaY or CuY, the yield of aniline was increased. When hydrogen chloride was added too much, the yield of aniline was decreased because of a formation of coke.
In the amination of chlorobenzene, the maximum yield of aniline was 3.0 mol % at 250° C. Above 350° C, benzene was markedly produced. At the same time, it was observed that ammonia was markedly decomposed to hydrogen and nitrogen.
It was suggested that the amination of phenol was mainly promoted by BrOnsted acid sites of zeolites.

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5, 6-Dihydro-2, 4-dihydroxy-pyrimidine C 1 D, 5, 6-dihydro-4-hydroxy-2-mercapto-pyrimidine C 3 J and 5, 6-dihydro-2-ethylmercapto-4-hydroxy-pyrimidine C 4 J were prepared by the reaction of urea, thiourea and S-ethylisothiourea with methyl acrylate, respectively.2-Arylamino-5, 6- dihydro-4-hydroxy-pyrimidines [5 ad] were obtained by the reaction of C 4J with aryl amines (aniline, p-toluidine, p-anisidine and p-chloroaniline) 8-Arylguanidinopropionic acids C6 aclip were obtained by the hydrolysis of [5 ad].

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Bromination of phenalenone C 1 J or 2-bromophenalenone [2] gave 2, 6-dibromophenalenone C 3 D. The substitution at 6-position, which had long been accepted without conclusive evidence, was confirmed by the NMR spectrum and oxidative degradation of C 31 2, 6, 8-Tribromophenalenone C 4 j was obtained from Cl J by bromination in nitrobenzene at 80400° C in the presence of iodine and iron powder. The oxidation of C 4 J afforded 3, 5-dibromonaphthalic anhydride. When Cl J was brominated in boiling bromine by using iodine as a catalyst, 2, 6, 7, 8-tetrabromophenalenone C 5 J was obtained. The compound C5 J was oxidized to 3, 4, 5- tribromonaphthalic anhydride [15].
2-Aminophenalenone was brominated to 2-amino-3-bromo-[l0] and 2-amino-3, 6-dibromophenalenone C.11D by one and two moles of bromine, respectively. The latter compound was also obtained from 2-amino-6 -bromophenalenone [9].
The electronic spectra of phenalenones Cl-[5] and their conjugate acids CI c-[5 c] showed parallel spectral shifts according to the number of bromine atoms, with exception of a set of C 5 D and [5]. For [5] and [5], the deviation from the relationship can be attributed to steric effect of three neighboring substituents.

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The study on the distillation characteristics and the chemical composition of Khafji atmospheric residue was made to obtain the basic information on the composition of individual fractions, which is necessary for developing an effective hydrodesulfurization process or utilizing these materials in more useful energy form. The Khafji residue was fractionated into seven distillates up to 325° C at 2 x10-3 mmHg and one residue by molecular distillation. The distillates and the residue were separated into saturated and aromatic components by silica gel liquid-solid chromatography. The n-paraffin content in the saturated components was determind by the formation of insoluble urea complex of n-paraffin. The oily substance which did not participate in the urea complex formation was treated with acetone at 3° C, whereby branched paraffinic material was precipitated. The remaining acetone soluble component was regarded as naphthene. The aromatic components was separated into two fractions by an alumina gel column. A detailed structural analysis of thus separated fractions was carried out by means of proton magnetic resonance spectroscopy. The yield of the molecular distillate was about 65% to the atomospheric residue, and the relative quantities of the saturated and the aromatic components in the distillates were similar as a whole.

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D-Glucose has two anomeric isomers (a- and 8-type). In crystalline state, D-glucose is of a-type. When crystalline D-glucose dissolves in water, part of the dissolved a-D-glucose changes into 8-D-glucose. These properties of D-glucose exhibit an interesting phenomenon concerning the dissolution rate of crystalline D-glucose.
In this study, the author attempted to derive a basic equation for determining the dissolution rate of crystalline D-glucose after the solution has been saturated with a-D-glucose. Experiments were conducted at 10-30° C in order to verify the equation. As a result of the experiments, it was clarified that the dissolution process of crystalline D-glucose has two rate-determining steps of diffusion and mutarotation. With the aid of this basic equation and the results of the experiments, it was made possible to measure the solubility of a-D-glucose. The derived rate equation is as follows:
where
Tg=Total concentration of D-glucose at time t, K=Tan 0 of linearlized mutual solubility curve, Pe=Solubility of 8-D-glucose at equilibrium, 1=Forward rate constant of mutarotation, I=Reverse rate constant of mutarotation, b=intercept of linearlized mutual solubility curve.

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The pH- and thermally-induced conformational changes of copoly(L-lysine, DL-lysine) and copoly(L-lysine, L-ornithine) in various mole ratios in aqueous solutions were studied by means of the optical rotatory dispersion (ORD) and the circular dichroism (CD).
The helix-coil transition of these copolymers in aqueous solutions occurred at about pH 10, and the helix contents increased with increasing lysine content. Copolymers having helical conformation underwent an a 8 transition upon heating at 65° C.
The phenomena of the a 8 transition of these copolymers can be assumed that the helical parts existing in aqueous solution at 20° C changes into 8-form upon heating at 65° C.

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The pH- and thermally-induced conformational changes of copoly(L-lysine, L-leucine), copoly(L-lysine, L-alanine), and copoly(L-lysine, glycine) in various mole ratios in aqueous solutions were studied by means of the optical rotatory dispersion (ORD) and the circular dichroism (CD).
The copolymers with high lysine content brougt about the coil-helix transition with increasing pH. When the solutions of the a-helical copolymers were heated at 65° C, the copolymers transformed from a-helix into 8-form. However, in the case of the copolymers with high leucine and alanine content, the a 8 transition was not observed upon heating. The coilhelix transition of the copoly(L-lysine, glycine) took place at high pH with increasing glycine content.
These results indicate that leucine and alanine residues increase the stability of the lysine helix but the glycine residue decreases that of the lysine helix.

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The mechanism of the permeation of polymer solutions, used for Japanese paper making, through vinylon fiber bed was studied. The polymers used were Tororo-aoi mucilage (TA), sodium polyacrylate (NaPAA, M. W.3.56 X 10°) and polyethylene oxide (PEO, M. W.0.46, 3.54 X 10°).
The change of permeation rate caused by alternation in the porosity of fiber bed was characterized by the varieties of the polymer solution. The permeability coefficients calculated from the permeation rates of TA and of higher molecular weight PEO were significantly smaller than that calculated from water. As for TA, the results were appreciably explained in terms of a pore radius decrease in the bed which was due to the thicker immobile layer caused by the polymer adsorption on fiber surface. On the other hand, as for PEO, it was suggested that the decrease in permeability coefficients should depend not only on the adsorbed layer, but also on the viscoelastic properties of the polymer solution. In the case of NaPAA, such an immobile layer as governing the permeability was absent.

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The hydrolytic polymerization of cyclic dimer of e-caprolactam with phosphoric acid catalyst was studied.
As cyclic dimer has very high melting point (347-348° C), the initial reaction proceeded as a heterogeneous system. The conversion of cyclic dimer and the formation of e-caprolactam proceeded according to the zero-order kinetics and the both rate constants were directly proportional to the amounts of phosphoric acid and water. From the concentration of the amino-end groups of the formed polycaproamide and the data for conversion of cyclic dimer, it was found that the concentration of the amino-end groups in the reaction system was kept constant during the reaction. Therefore, it was presumed that the hydrolysis of cyclic dimer catalyzed by phosphoric acid proceeded rapidly and cyclic dimer polymerized with the resultant amino-end groups by the amide exchange reaction.
After the con version of cyclic dimer exceeded about 50%, the polymerization of cyclic dimer proceeded according to the first order kinetics in a homogeneous system and the rate constant was directly proportional to the amount of water.

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2-Amino-4-(nitroanilino)-6-(nitropheny1)-1, 3, 5-triazines were prepared by the nitration of suitable triazine derivatives.2-Amino-4-(aminoanilino)-6-(aminophenyl)-1, 3, 5-triazines were obtained by the reduction of the above dinitro-compounds. Poly (pyromellitamic acid-guanamine) [A] was prepared by the reaction of the above diamines with pyromellitic dianhydride. The details of the preparation are shown in Table 1. The preparation of poly (pyromellitimide-' guanamine) CBJ from [A] by heating it in vacuo was carried out and the details are shown in Table 2. CAD was soluble in DMSO, DMF and concentrated sulfuric acid, and C BD was soluble in concentrated sulfuric acid but insoluble in common organic solvents as shown in Table 3. The structures of [A] and [B] were confirmed by IR spectra shown in Fig.2. Thermal properties of CAD and C Bp, measured by means of TG and DSC, are shown in Fig.3, Table 4 and Table 5. Decomposition temperatures of [A] and [B] were 500, -550° C, respectively.

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3-(2-Vinyl)-6-methyl-4, 5-dihydropyridazinone C_2CJ, whose conjugation ability will be expect rather smaller than 3- (2-viny1)-6-methylpyridazinone [1] has been polymerized under various reaction conditions and the results were discussed in terms of the conjugation stability of the pyridazinone ring.
Cationic catalysts ware found to give homopolymer of [ 2 ] but not that of C / J. It was noted that the radical polymerization rate of C_2C J was rather lower than that of C / J (Table 1). Radical copolymerizations of C 2 J and C / D with styrene (St), methyl methacrylate (MMA), and acrylonitrile (AN) have been carried out and the average Q and e values were obtained as O.33 and .23 for 2 and O.54 and 0.54 for, respectively (Table [2]).
Hydrogen bonding parameters (r), using CH₃OD, were determined as 8.0 for 2 J and 9.6 for [2], respectively (Table 4). While, it was observed that Cl J was more effective than C 2 J in accelerating the nucleophilic reaction of sodium n-butyl malonate with n-butyl bromide. All these observations clearly suggest that the pyridazinone ring in Cl J is stabilzed by the effective ring conjugation among the carbonyl group, a pair of electrons on a nitrogen atom and the double bond in the ring.

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In the synthesis of linear phosphazene dichloride oligomer [Cl-+PCl2=N-MPCl51+EPCl6]- (LPNC) the effects of molar ratio of the raw materials, the reaction time and the solvents on the yield were investigated.
LPNC was prepared by the reaction of phosphorus pentachloride (PCl5) with ammonium chloride (NI-I, Cl). Nitrobenzene (NB), sym-tetrachloroethane (TCE) or NB-TCE (1: 1) was used as a solvent.
The following results were obtained:
1. The yield of LPNC increased with increasing molar ratio of PCl5.
2. The cyclic phosphazene dichloride (CPNC) was not obtained at an early stage of the reaction and the rate of the reaction was faster with excess NI-14Cl than with excess PCl5.
3. The time required to reach 70% conversion was 3.5 hrs in NB-TCE (1: 1), 6 hrs in NB and 7 hrs in TCE and the reaction gave LPNC in the yield, highest in TCE and lowest in NB.

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The rate of isomerization of sec-butyltoluene (SBT) catalyzed by anhydrous aluminum chloride was studied in dilute toluene solution. Experimental conditions such as stirring speed, catalyst concentration, and so on, were chosen to avoid occurrence of the two phase system and the side reactions such as disproportionation.
The reaction kinetics was investigated as a pseudo-first order triangular system. Best fit values of the six rate constants were estimated by the Gauss-Newton method.
The Arrhenius plots of the rate constants gave concave curves, each of which was approximated by two straight lines. From this behavior of the rate constants, it was concluded that the mechanism of the isomerization of SBT was dependent on. reaction temperature. That is, at relatively lower temperature (2030° C) the isomerization occurs by the intramolecular 1, 2- shift mechanism and at higher temperature (35-50° C) by a competitive intermolecular alkyl transfer mechanism in which both, the !one through generating of sec-butyl cation from the protonated SBT and the other through carbonium ion chan alkylation-dealkylation, take place simultaneously.
The rate constants were re-estimated taking into account the above mechanism. The Arrhenius equations were then determined as follows:
k0=1.188x 10'9 exp (-29.67 x 10 I RT) min-1 for 20° C to 50° C; k 5.167x 109 exp (-7.783 x 1O^2-/R T), k0, =2.541x 1O^2- exp (092 x 1O^2-/R T) min-1 for 20° C to 30° C and kmp= 6.933 X 1017 exp (-27.48 x 108/R T) km =5.135 x 1019 exp (-30.41 x 108/R 71) min-1 for 35° C to 50° C.
The equilibrium constants, ICO₃ and Kom were independent of reaction temperature and K0=0.0667, 0.4410 and 34.00.

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The reaction between methylmercuric chloride and mercapto collector, such as alkylxanthates (KRX) and dialkyldithiophosphates (KRP), has been studied by means of polarography and potentiometric titration in relation to the removal of methylmercuric ion in aqueous solution.
Although methylmercuric chloride gave sparingly soluble, precipitate with xanthates, the composition of which was 1: 1, water soluble complex was also formed. The solubility products of the precipitates decreased, while the stability constants of the complexes increased, with increasing the number of carbon atoms in alkyl radical (Table 2). Similar behavior was noted in the case of dialkyldithiophosphates, though larger solubility products were given as compared to the xanthate system. The test to remove methylmercuric chloride by precipitation with amylxanthate showed the limited success; the residual concentration of mercury (several mg) was inevitable (Table 3). This residual concentration of mercury was in fairly good agreement with that of the complex formed, indicating that it is difficult to remove methylmercuric chloride by mercapto collectors to the level of " not detectable", differing from the case of inorganic mercuric ion where the formation of soluble complex can virtually be ignored.

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In order to examine whether the solubility parameter of surfactants would be determined by gas chromatography, the retention volume of various hydrocarbons was measured by using the surfactant as stationary phase at varying temperatures. The values of solubility parameter of surfactants could be obtained from the linear relation between 11, 31v, and the solubility parameter of the hydrocarbons, where Ms is the heat of solution of a hydrocarbon in a surfactant, v, the molar volume of the hydrocarbon. The values of the solubility parameter obtained agreed fairly well with the values published by Little and Singleterry, by Kertes, and by the present authors, except di- (2-ethylhexyl) sodium sulfosuccinate. The solubility parameter values of other various oil-soluble surfactants were obtained by this method.

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Changes in the surface acidity of silica-alumina which was compressed under various pressures, ranging from 0 to 10000 kg/cm² were measured using an indicator method. The surface acidity varied on compression, giving a maximum acidity at 5000 kg/cm of compacting pressure.

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Thoria-silica catalysts for the clehydrative condensation of benzophenone with ammonia were prepared from thorium nitrate and colloidal silica. Their physical properties are given in Table 1. Diphenylmethanimine was formed selectively over these catalysts at 280-450° C. Thoria-contents of 3-5% were sufficient to produce the active catalyst as shown in Fig.1. Crushing and attrition loss were minimized at the same region of ThO^2- contents (Table 1). Apparent equilibrium constant for the formation of diphenylmethanimine was estimated to be K=O.059.006 at 365° C for 3% ThO^2-SiO^2- catalyst.

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N, Y-bis(1-acetonylethylidene)ethylenediamine (AEH₂) complex of europium (U) chloride was prepared by adding acetone into a mixed methanol solution of EuCl2H₂0 and AEH₂ under nitrogen atmosphere at room temperature. Chemical analysis, conductance measurement, IR and UV spectra indicated that the formula of the complex is Eu(AEH₂)Cl2. The valency of europium was confirmed to be divalent from the magnetic susceptibility measurement. The complex is unstable in the presence of oxygen.

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The rare earth complexes with N, Y-bis(1-acetonylethylidene)ethylenediamine (AEH3) were prepared in methanol solution containing both chloride and perchlorate ions. Three mixed systems of rare earth chloride-rare earth perchlorate, rare earth chloride-sodium perchlorate and rare earth perchlorate-ammonium chloride were investigated. The products were chracterized to a new type complex, Ln2(AEH₂)5Cl4(Cl0O^2-), where Ln are La, Pr, Nd, Sm, Gd, Dy and Er.

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The reaction of nitrobenzene with polyamine cobalt (II) complexes in aqueous solution under nitrogen atmosphere was investigated. Polyamine in the complexes was ethylenediamine, di ethylenetriamine, triethylenetetramine or tetraethylenepentamine. Azoxybenzene was produced selectively. The products were in better yield when the molar of pplyamine to cobalt was 3: 1. Mechanisms for these reactions were proposed and discussed.

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Since red calcium-glyoxal bis(2-hydroxyanil) (GHA) complex is unstable in various solvent media, several experiments have been carried out to find appropriate condition for the quantitative color development. Absorbances of the reagent blank and calcium-GHA in 50% water25% ethanol-25% 1-butanol were measured at 0.35° C for 0-420 min. Satisfactory results were obtained when the solution, 0. O^2- N in sodium hydroxide, O.01% with respect to GHA and 50% with respect to the solvent mixture of ethanol and 1-butanol (1: 1), was kept at 0° C for 30-50 min before absorbance measurement.

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A fluorometric method for the determination of small amounts of anthracene in anthraquinone is proposed. The influence of large amounts of anthraquinone can be removed by the reaction with sodium dithionite alkaline aqueous solution due to the formation of anthrahydro quinone, which dissolves in alkaline aqueous solution.
About 10 ml of the sample solution dissolved in xylene (100, tig/m/) are taken in 50 ml separating funnel and 300 mg of sodium dithionite and 30 ml of O.5 mol/l sodium hydroxide solution are added. The air in the funnel is replaced with nitrogen. The mixture is warmed to 40° C for 10 minutes and shaken sufficiently for 15 minutes. After the aqueous phase is removed, xylene phase is dried with anhydrous sodium sulfate. The fluorescense intensity is measured at 4O^2- nm with excitation at 378 nm against 0.25 /Tim/ anthracene solution as reference standard. By this method, anthracene in anthraquinone can be determined down to O.01%. This method is not interfered with the presence of impurities, unless the amount is so large.

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The nitrations of naphthalene [1], fluorene [2], o-xylene [ 3 ], and trans-stithene [4] by means of metal nitrates or nitric acid in carboxylic anhydrides were studied. The formation of acyl nitrates from metal nitrates in the carboxylic anhydrides was ascertained by thermographic technique.
The isomer distributions did not depend on the nature of acyl groups in the nitrations of [1] and [2]. The reaction of [3] afforded 4-acyloxy-o-xylenes 17 a-6 in 25-43% yields along with 3-nitro- and 4-nitro-o-xylenes. Acetate ion in the reaction medium was found to be consumed for the formation of [7 a] in the reaction with propionyl nitrate.
trans-Stilbene underwent g-nitroacyloxylation with acetyl or propionyl nitrate to give threo1-acyloxy-1, 2-dipheny1-2-nitroet1iane.
In is reasonably concluded that the acyl nitrates formed under the present conditions behave like acetyl nitrate toward typical aromatic hydrocarbons.

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Poly (vinyl chloride) containing S-substituted polysulfide pendant (RSn-) has been found to be crosslinked even under weak T-irradiation of total dose of 6.5 X 1O-'3.8 X 105 R giving 18.1 9.7% gel. The crosslinking reaction may occur through the recombination of some radicals formed by the scission of S-substituted polysulfide pendants under r-irradiation. The recom- bination gives some crosslinkages (C-C, C-S, -C, m. 1) and polysulfide compounds of a low molecular weight e. g., (C6ll5CH₂)2S₂. The crosslinking is greatly accelerated in the poly(vinyl chloride) containing aromatic pendant (R: C6l-15-, C6H₅CO-) and more than 3 sulfur chains (n).

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The oxidation of 1, -butene known in industry as Wacker-process was studied from the standpoint of the chemical absorption theory.
The experiment was carried out in a stirred vessel with a flat gas liquid interface at 35° C in the diffusion control region.
The observed chemical absorption rates of 1-butene were analyzed on the, Joa. sis of the chemical absorption theory of m-th order irreversible reaction, and carbonylation reaction was found to be first-order with respect to 1-butene or palladous chloride, to be reciprocal to -firstorder to chloride ion and to be zero-order to hydrogen ion.
Then, the mechanism of the transformation of 1-butene alladous-π-complex to a-complex was assumed that r-complex was attacked directly by the hydrotcy group to form a-complex.

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