Although almost all studies on dispersed systems, including colloidal dispersions, suspensions, emulsions etc., are at present based on interfacial phenomena and interactions between neighboring particles, study of many characteristic phenomena of these systems, e. g, coagulation, osmotic pressure etc. requires statistical or thermodynamical treatments. Only a few attempts have so far been made to treat the coagulation as a many-body problem. In the present paper an attempt is made to generalize classical molecular thermodynamics for dispersion systems. This analysis shows that the general thermodynamic equation of state holds, when the system of dispersed particles is considered as a generalized phase; the dispersed system can be: described byusingmeasurable variables, e. g, temperature, volume (i. e. the available volume of the system of dispersed particles), number of particles etc. The stability, i. e. coagulation and coalescence, as well as osmotic pressure of the system can also be treated on this standpoint. It is thus shown that the osmotic pressure of a thermodynamically stable dispersed system is alwayspositive, and that a thermodynamically stable emulsion can beformed by the dispersed method onlyvia the spontaneous emulsification process. The present discussion can be extended topolydisperse systems by introducing generalized chemical potential of the phase.

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Adsorptivities of oligosaccharides (DP= 2-26) on five kinds of activated carbons with different pore-size distributions are examined in a dilute (-100 mg/l) solution at 30°C. The relationship between the adsorptivity and the degree of polymerization of oligosaccharides was dependent on the adsorbent carbon and showed a certain correlation with their pore-size distribution curves of the radius less than ca.100A (Fig.1 and 2). This. experiment suggests that these oligosaccharides are well adsorbed in the pores of the suitable size.
In addition, glucose and fructose, monosaccharides, showed lower adsorptivity than that of disaccharides, trisaccharides and others. The differences are large for the carbon with welldeveloped micro-pores. This fact is explained in terms of high solubility of monosaccharides in water.

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When a SO^2-H₂0-O^2-N2 'gaseous mixture was irradiated by electron beams of 1.5 MeV, 5O^2- waseasilyoxidized to H₂SO₄. Effects of CO, ODNO H₂O, and irradiation temperature on the radiation-induced _oxidation of, SO₂ were studied by measuring the. SO₂ concentration gas chromatographically. TheG(-O₂) increased greatly at the addition of a small amount of O^2-, and then decreasedgradually withan increase in the O^2- concentration, i. e., the G - SO₂ values were 0.9, 8.0, and 5.3 for the 0, 0.1, and 20% 0, concentrations at 100°C, respectively(Fig.4). The G(-O^2-) wasindependent of the H₂O concentration in the range of 0.89 to 8.4%(Fig.5). The G -ODdecreased with a rise in the irradiationtemperature (Fig.6) and anapparent activation energy of the oxidation reaction of SO₂ obtained was 0.2 kcal' mol-1. The effects of CO, NO, and O^2- on the G(-O^2-) showed that SO₂ was mainly oxidizec by OH and 10 and that the contribution of OH to the oxidation of SO₂ increased with ar increasein the 0, concentration (Table 1)The rate constants for the reactions of SO₂ witt OH and 0, obtained from competitive reactions of SO₂ with CO and O^2-, were 5.4 x10"cm8, mol-liseci and 5.0 x10"cms mot-1. sec', respectively.

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In the pulse technique in which a reactant and a poison are injected alternately into a reactor as pulses, the conversion of the reactant decreases with the amount of the poison injected. A theoretical analysis was carried out under the assumptions that the reaction occurs between two reactant molecules adsorbed on adjacent two active sites on a catalyst, and that the poison is adsorbed irreversibly at the rate proportional to the product of the concentration of poison in gas phase and the number of unpoisoned active sites and makes the adsorbed active sites inactive. The analysis shows that the concentration of active sites on the catalyst surface can be determined by the intersection method which employs points of intersection on the conversion rate vs. amount of poison curves for different amounts of the catalyst as in the case of the 1 st order reaction analyzed previously Kogyo Kagaku Zasshi, 71, 779, 1568 (1968). Another theoretical analysis was also carried out on a system in which mono- and bimolecular reaction proceed simultaneously. As a result of the analysis the ratio of reaction rate constants (k, Co/k, ) and adsorption rate constant of poison (r) have been found to be determined by the comparison between a plot of log YID/ against cumulative amount of poison injected and Fig.5 obtained from the theoretical analysis. It has been known that by the reaction of cumene on a silica-alumina catalyst at lower temperatures diisopropylbenzene is formed together with benzene and propylene. The pulse poisoning technique shows that diisopropylbenzene is formed by the reaction between two adsorbed molecules of cumene but not by the alkylation of cumene with propylene of free propyl group.

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Hydrogenolysis of butylamine and butyronitrile on a Co-Mo-A1, 08 catalyst was studied with a continuous flow reactor at one atmospheric pressure. Conversion in hydrogenolysis and yields of dibutylamine, butyronitrile and hydrocarbons as well as change in contents of produ ced hydrocarbons with temperature were measured at various temperatures and contact times. In the hydrogenolysis of butylamine, dibutylamine was a primary product and butyronitrile a secondary one and hydrocarbons final one, as shown in Figs.4-7. At lower temperature the main species of hydrocarbons produced were butenes and butane but their fractions decreased with increasing temperature. At higher temperature propylene and propane were the main species as shown in Fig.3. Yields of hydrocarbons in the hydrogenolysis of butyronitrile were less than these in the hydrogenolysis of butylamine as shown in Fig.2, while change in con tents of produced hydrocarbons with temperature as shown in Fig.8 was similar to that in Fig.3. The equilibrium constants for and the conversions of the reactants in the reactions including nitrogen compounds were calculated as a function of temperature and were shown in Fig.9 and Table 1. A. reaction scheme was proposed, where butylamine and butyronitrile are adsorbed on the catalyst surface to form an identical species which hydrogenates and decom poses to give hydrocarbons and ammonia.

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In order to confirm the reaction scheme proposed in Part I and to obtain some information on the surface reaction mechanism, we studied the hydrogenolysis of butylamine isomers (n-, s-, i- and t-), dibutylamine and butyronitrile on a Co-Mo-A120, catalyst with the pulse reaction technique. The surface reaction rate constants for and the contents of hydrocarbons produced in the hydrogenolysis of butylamine, dibutylamine and butyronitrile were in good agreement with each other, as shown in Fig.4 and Table 1. While the rate constants of butylamine isomers differed, from each other as shown in Fig.5. The activation energy of tbutylamine (30 kcal/mol) was larger than the activation energies of the others (18 kcal/mol for s-butylamine and 23 kcal/mol for butylamine and isobutylamine). The ratio between the products, butene and butane, and the number of active sites on the catalyst in the hydrogenolysis of t-butylamine also were larger than those in the hydrogenolysis of the other amines as shown in Figs.6 and 7. This suggests that butylamine, dibutylamine and butyronitrile adsorb on the catalyst surface to form an identical adsorbed species which hydrogenate and that the adsorbed species of these three compounds and iso- and s-butylamines form amines diadsorbed at nitrogen and cr-carbon atoms, but adsorbed t-butylamine forms a monoadsorbed amine. Furthermore, the mechanism of conversion from adsorbed amines to hydrocarbon on the catalyst surface was proposed on the basis of the analysis of the surface reaction rate constants calculated from the activated complex theory.

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Vapor phase oxidation of styrene over various silver catalysts has been carried out by using a continuous -flow reacto. The products were styrene oxide (STO), carbon dioxide, water and a trace amount of benzaldehyde. For the synthesis of styrene oxide, most effective catalysts were the ones prepared with silver oxide, barium peroxide and fused alumina carrier mixed with water and then dried (Table 1). The effect of preparation method of silver oxide on the catalytic activity and the selectivity was studied with varying concentrations of silver nitrate and sodium hydroxide (Tables 2 and 3), at varying temperatures of solutions (Table 4) and in the mixing order of solutions (Table 5). In catalyst preparation decrease in the activity was observed in repetitive drying and wetting with water (Fig.1). Structural difference among these catalysts was not found by X-ray analysis. There was no definite relation between the activities for the oxidation of styrene and ethylene in these catalysts (Fig.2). Effects of the reaction temperature, the partial pressures and the contact time were studied (Figs.4, 5, 6 and 7). Carbon dioxide seems to be formed by the successive oxidation of styrene oxide in contrast to the oxidation of ethylene, because the selectivity of styrene oxide was almost 100% at short contact time. Dependence of the reaction rate on the partial pressure of styrene and results of competitive reaction with benzene, toluene or styrene oxide suggest the strong adsorption of styrene and the retardation of the reaction by styrene oxide (Fig.10 and Table 8) It was found that deactivation of the catalyst with time of use was due to the irreversibly adsorbed substance and that the activity was recovered by air flowing (Fig.3).

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In connection with the time-dependence of electrical conductivity, the stability of fluoritetype cubic solid solution at 8001500°C in air was studied for the ZrO^2-Y2O^2- samples (Y208: 6, -16 mol%) sintered at 2000°C.
After the samples were aged at 800°C (for 525 hours) 500°C (for 16 hours) and subsequently quenched in water, they were examined by X-ray diffraction. The cubic lattice constants of the samples aged at 800°C were slightly smaller than those of the samples aged at 1500°C. The thin sections of the samples containing 7, -14 mol% Y208 were examined by a polarization microscope using crossed nicols, after they were aged at 800°C (for 405 hours)'1500°C (for 20 hours) and subsequently air-cooled to room temperature in 5 minutes. Birefringent phases were detected in 7 and 8 mol% Y208 samples regardless of the aging temperatures.
From the experiments described above and previous data for the time-dependence of electrical conductivity at 800 and 1000°C in air, the following conclusions were obtained. Up to 9 mol% Y208, the polymorphic transition is dominant. The so-called cubic structure is present in the region of Y2O8 concentration not smaller than 9 mol%. In this region, the order-disorder transition is dominant, and the disordered phase transforms into the ordered phase at temperatures below about 1000°C.

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The use of light for selective electroless deposition has been studied. UV light has been shown to effectively inhibite the electroless deposition of nickel if applied after sensitization. The electron microscopic observations in the different stages of the electroless plating process have been made. We have shown that the Sn (II) species can readily be photo-oxidized to Sn (IV) by exposure to UV light, and the Sn(N) formed inhibites the catalytic function. The unexposed regions sensitized with Sn (II) solution and activated with Pd (II) solution gave Pd (II) catalytic layers in which an electroless metal deposition took place. It was also found that very fine and dense catalytic layers were formed by the introduction of an additional immersion of the substrates in a silver nitrate solution between tin (II) chloride sensitization and palladium (II) choride activation steps. Thus, selective electroless deposits of metal on glass substrate were obtained by exposure through a quartz mask.

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The system SrMnO^2-_x was studied with gravimetric, quenching and X-ray diffraction techniques. The phase diagram was constructed for the temperature range of 900-1600°C and the partial pressure of oxygen from 1 to 6 X10-6atm. Phases found in this system were hexagonal a-phase at low temperatures, cubic 8-phase at high temperatures and SrMnO^2-.5 with braunmillerite structure. The transformation between these phases took place reversibly. The temperature of phase transformation increased with increasing partial pressure of oxygen. The oxygen deficits( x) in each phase increased with decreasing partial pressure of oxygen and with increasing temperature. The oxygen deficits increased approximately 0.14 when the aphase was transformed to the 8-phase. This increase of oxygen deficits was not affected by the temperature of phase tiansformation or the partial pressure of oxygen. The densities- of these phases as determind pycnometrically and by X-ray diffraction technique decreased with increasing oxygen deficits.
Defect models for SrMn08, were proposed to, explain:. the Poe- Txphase diagram. The formation of oxygen deficits was expressed by Eq., ( 1) in a-SrMnOs_x and by Eq. ( 2 ) in RSrMnOs_z as follow,

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The effect of mechanochemical treatment of original powder on properties of ceramics had been investigated by using polycrystalline barium titanate (BaTiOs) ceramics as an example.
When BaTiO₃ powder was ground to ultrafine particle (about 0.05, -0.1 p) by mechanical grinding, a remarkable distortion of its crystal lattice was found from X-ray diffraction patterns. Unstable BaCO, layer f ormed on the distorted surface by adsorbing CO, from air, and BaTi3O, and BaTi807 as Ti4+-rich phase formed within the layer as the result. Formation of the double layer gave a great promotion to the sinterability of the ground powder but it was difficult to inhibit the growth of crystal grain owing to its high reactivity. Whereas, when the ground BaTiO₃ was heated at 1000°C, the double layer disappeared rapidly and converted into stable BaTiO₃ layer again. The microstructure of sintered body, prepared by using the inactive ultrafine particle, consisted of the dense ceramics (above 94% of theoretical density)having uniform grain size of about 0.7, u and dielectric constant showed 6000-7000 at ordinary temperature and 10000-42000 at near Curie temperature respectively.
By the mechanochemical treatment of BaTiO, powder, it was possible to control particle size and its surface properties corresponding the period of grinding time and to prepare inactived ultrafine powder by further heating. This method could be applied to the control of microstructure of fine ceramics.

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Monoclinic yttrium phosphate, YPO₄H₂O, was synthesized by precipitating it from the mixed solution of yttrium chloride and orthophosphoric acid or phosphate at 20°C. Crystalline monoclinic yttrium phosphate was detected in the precipitate obtained from the solution at pH 1.2-3. The minute crystals showed prismatic habit. Amorphoups precipitate was obtained at higher pH than 3. At lower PH than 1, precipitation did not proceed. The chemical f ormula of the synthesized monoclinic yttrium phosphate was given by YP0O^2- H₂O. The unit cell parameters obtained from X-ray diffraction of a powder were as follows: a= 5.554 A, b= 15.050 A, c= 6.232 A, 8=115°02'. The differential thermal analysis curve of the synthesized monoclinic YPO₄H₂O showed an endothermic peak at ca.273°C. This peak was due to the change of monoclinic to tetragonal YPO, . The tetragonal YPO₄ was stable at 1800°C in an air.

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Silver, gold, barium, cerium, cobalt, chromium, cesium, europium, hafnium, lanthanum, rubidium, antimony, scandium, samarium, tantalum, terbium, thorium, uranium, and ytterbium in human stones were determined by nondestructive neutron activation analysis to study the behavior of trace elements in biological materials.
The samples (22 gallstones, 11 urinary calculi and one phlebolite) were irradiated for 12 or 47 hours with thermal neutrons in the TRIGA Mark II Reactor of Rikkyo University (flux: 5 X 10"nicm'isec). Gamma rays of the nuclides formed by (n, r) reactions were measured for 1000-40000 seconds after 6-90 days cooling by using a 4096 channel pulse height analyzer and Ge (Li) detector.
Contents of trace elements in human stones were almost as low as ppb or less and fluctuated largely. Therefore, it was difficult to find out definite relationships among the kinds of human stones from the statistical point of view. However, many trace elements tend to be more abundant in gallstone than in urinary calculus, and are more enriched in mineral stone and cholesterol pigment calcium stone than in cholesterol stone. The concentration ratios of trace elements in human stones to those in blood, which is a humour related to the human stone formation, were calculated and compared with those of previously reported heavy metal elements. Consequently, it was found that cobalt is concentrated to a considerable degree in process of the human stone formation, as is the case of Cu, Fe, Mn, Pb, and Zn.
From these results it was presumed that the abnormal metabolism of cobalt in human body is responsible for the formation of human stones.

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Electrochemical reduction of phthalazine was investigated at a mercury electrode in N, Ndimethylformamide (DMF) Water and aqueous buffer solution.
Phthalazine showed a reversible 1.2-1.3-electron wave and a 2.7-2.8-electron wave in DMF medium containing 0.1 vol% H₂O, although many organic compounds show two oneelectron waves in aprotic solvents.
A series of experimental data suggests the following mechanisms for the electrode reaction of phthalazine in DMF-water.
In aqueous buffer solution, phthalazine underwent six-electron reduction to C6H4 (CH₂N1-1214+) 2 at pH 2.0-3.5, to C6H4 (CH₂NH₂) 2 at pH 3.5-6.5, four-electron reduction to C6H4 (CH₂NH₂) CH=NH at pH 6.5-9.0, and two-electron reduction to dihydrophthalazine at pH 9.0.
These mechanisms were supported by controlled potential coulometry and the UV spectra of the solution obtained after controlled potential electrolysis.

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Sodium sulfate in detergents was determined by high speed liquid chromatography employing a porous micro-spherical strong anion exchanger (TSK-Gel LS-222, 6 g) as a column packing material. Sulfate ion in the column effluent was detected as iron (III) sulfate complex which was formed by mixing color-producing agents containing iron perchlorate with the column effluent. The elution of inorganic and organic builders such as condensed phosphates and citrate, except sulfate, was greatly affected by the pH of the eluent as shown in Fig.3. Anionic surface active agents were strongly held by the anion exchanger and were not eluted. The sensitivity for the detection was influenced by the concentration of perchloric acid, iron (H) perchlorate and acetone in the color-producing agents (Figs.4, 5 and 6). The recommended conditions for the analysis were as follows analytical column: 5 mm I. D. x 50 mm, eluent: 0.1 moll/ nitric acid, analytical column temperature: 30°C, color-producing agents: 0.05 mol/l iron (III) perchlorate in 0.4 mol/l perchloric acid containing 30% acetone, flow rate: eluent 0.7 ml/min, color-producing agents 0.4 ml/min, detector: UV (330 nm). The calibration curve was linear within a range of 10-50 gg (Fig.7). Analysis of a standard detergent yield satisfactory results (Table 2). The proposed method was applied to the determination of sodium sulfate in several commercial detergents. The results agreed with those of conventional chelatometry as shown in Table 3.

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Acrylamide and N, N'-methylenediacrylamide were polymerized to give porous gels in wateralcohol diluents, in which methanol or ethanol served as an inert solvent for gels. Water soluble materials such as acetone, ethylene glycol oligomers, and dextrans were allowed to pass down the columns packed with the gels obtained to construct calibration curves. The gels polymerized in the diluents consisting of less than 24 vol% of methanol or ethanol exhibited identical calibration curves. However, when polymerized in the presence of 48 vol% of ethanol in diluents, the gels formed yielded a larger exclusion limit. The effect of the concentration of crosslinking agent in monomer mixtures was also tested in the 24 vol% ethanolic diluent system.
The increasing proportion of the crosslinking agent in total monomers resulted in gels, which were capable of eluting dextrans of molecular weight of 500000 and 2000000 at an elution rate of 15 ml.cm^-2.hr-1.

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Comparing the oxidation-reduction potentials of methyl-p-benzoquinones E0 with that of Na, S08 (Es.), the addition and the redox reactions of methyl-p-benzoquinones with Na₂SO^2- in acidic buffer solution were examined.
It was confirmed that under acidic conditions the redox reaction mainly proceeded when the difference (Eq Ess) was large and the addition reaction proceeded when the difference (Eq- E.) was small.
It was observed that these two reactions were influenced by the mechanism of the anodic oxidation of Na₂SO^2- and the addition reaction was sterically hindered by the methyl groups in cases of 2, 5-dimethyl-p-benzoquinone and trimethyl-p-benzoquinone.

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Antimony trialkoxide reacts with acetic anhydride to form antimony acetate and the alkyl acetate.
Sb (OR) 3 n Ac20 (RO) 8, Sb (OCOCH₃) n CH₃CO₂R
The reaction rates of eight antimony trialkoxides with acetic anhydride were studied by monitoring the decrease in the amount of acetic anhydride utilizing IR spectrometer. The reaction was found to be of second, order, namely first order in antimony alkoxide and acetic anhydride, respectively. The Taft equation was considered to be valid for the reactions with all the antimony trialkoxides except antimony tri-t-butoxide. The p* value was calculated to be about which 10. The results of these studies are consistent with a reaction mechanism involves electrophilic attack of the antimony on the ether oxygen of acetic anhydride.

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The present study aims at the establishment of a new"C-tracer method which consists of the"C-labeling of a particular carbon followed by the simultaneous determination of the positions and relative amounts of the labels in the products, using"C NMR spectroscopy.
The solvolysis of 8-arylethyl arenesulfonates (Scheme 1) has been examined by such a"C NMR tracer method, and the results were compared with those obtained previously by means of '4C- and D-tracer studies. In the parallel runs of phenethyl-a-C and -8-13C tosylates (IQ and Ip, respectively) under the same conditions, the ratios of aryl-rearrangement obtained from the relative intensities of characteristic peaks of a and R-CH, of the products (found no other than acetates) were in excellent agreement with each other (Table 2). The agreement appears to be rather better than that in the corresponding D-labeling studies. The results of the acetolysis (Table 4) and formolysis (Table 5) under various conditions generally agreed well with those of other tracer-analysis.
Thus the reliability and applicability of the present"C NMR technique as a quantitative tracer-analysis method were confirmed. The same technique can be applied directly to the product analysis of the reaction mixture at any stage of the reaction. Relative amounts of the four components in Scheme 1 were determined from relative intensities of their characteristic peaks to give the extent of the reaction and the aryl-rearrangement ratios in both the starting material and product, all at the same time (Table 6). The % rearrangement at complete reaction was found to vary widely with substituents, solvents, and added salts or nucleophiles. With respect to the substituent effect, logarithms of &Ski, values derived from the % rearrangement on the basis of Scheme 1 gave an excellently linear plot with unit slope against the log kik for the acetolysis of substituted neophyl brosylates (Fig.1).

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The reaction of diphosphorus tetraiodide with some activated secondary and tertiary alcohols has been investigated in the presence of tertiary amines by using diethyl ether or benzene as a solvent and the products have been characterized. At room temperature, in ether 1-ary-1- alkanols reacted smoothly with diphosphorus tetraiodide to give the corresponding iodides in good yields, while in hot benzene 1-aryl-1-alkenes were the only major product. Upon similar treatment, both 1, 2-diaryl-1-alkanols and 2-aryl-2-alkanols easily underwent dehydration, probably via the intermediacy of unstable iodides, to give trans-alkenes. In some cases the use of pyridine as a base led to the formation of significant amounts of N-alkylpyridinium iodides.1-Aryl-1-cyclopropyl-1-alkanols underwent ring-opening, giving homoallylic iodides in high yields: Both cis- and trans-1, 4-cyclohexanediols were converted into a mixture of the corresponding diiodide and 4-iodocyclohexene in moderate yields.

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When 1, 4-naphthoquinone was treated with rhodium (III) chloride in a refluxed ethanol for 20 hr under nitrogen, a white product was obtained along with a small amount of darkred chlororhodium complex. The product was identified as 4, 4'-diethoxy-1, 1'-dihydroxy2, 2'-binaphthalene on the basis of spectral data and elemental analysis. The structure of was further confirmed by the fact that Li was oxydized to well known blue dye (Russig Blue: 4, 4'=diethoxy-2, 2'-bi (1 H-naphthylidene) -1, 1'-dione) by relatively mild oxydizing agents such as lead (IV) oxide, iron (III) chloride, or oxygen,

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The reactionf 2, 2-dibuty1-1, 3, 2-oxathiastannolane [1b] and -dithiastannolane [1 c] with variousisothiocyanates[2]to afford the corresponding N-substituted iminocarbonates have been kinetically studied by infrared spectroscopy, and the results obtained were compared with those on the reportedreactionof 2, 2-dibutyl-1, 3, 2-dioxastannolane [1 a].
Both [/ a] and [1 b] are present as dimers in solution, and Cl a appears to react with 27as the dimer. Contrary to this, the reaction of [1 la] with [2] followed the kinetic equation, V= ka[i 13]"2[2], suggesting that the dimeric [/ b] dissociated to the monomer which then reacted with [2]. [1 c] is monomeric in solution and its reaction followed the second-order kinetics, V. k2[1 c] [ 2].
The relative rates for [1 a], [1 b], and [1 c] were -450, 1, and 0.05, respectively. Whereas their apparent activation energies were almost the same (1213 kcal/mol), the apparent activation entropies were 0.4((/ a)), 0.6 ((I b)), and 0.2 kcal/mol ((/ c)). Thus their rates are apparently controlled by their entropy factors. Taft's polar constant p* for the apparent reaction rates of [1 b] with various isothiocyanates was +1.2 in 1, 1, 2, 2-tetrachloroethane and +1.8 in tetrachloroethylene, while it was +0.8 for the reaction of [1 c]. The steric reaction constant 8 was +0.9([/ b]) and +1.4 ((.1 c)). These results suggest the nucleophilic attack of the organostannyl compounds with considerable steric hindrance. Finally, solvent effect by the chlorinated hydrocarbon used was found to be very weak.

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Sulfonation of a- and m-nitrotoluenes in 30% oleum has been carried out at the temperature range of 20 to 100°C and the temperature effect on the isomer distribtion in the monosulfonation products has been examined by proton NMR analysis of the reaction mixtures.
In the sulfonation of o-nitrotoluene 2-nitrotoluene-4-sulfonic acid was the sole product (Table 4), while three isomeric sulfonic acids, 3-nitrotoluene-4-, 5- and 6-sulfonic acids, were obtained from the sulfonation of m-nitrotoluene (Table 5). The relative ratios of the latter acids were 6: 53: 41 at 20°C and 7: 47: 46 at 100°C, respectively. Addition of mercury (I) chloride to the reaction system resulted in a slight increase in the yields, but no significant effect was observed on the isomeric composition of the sulfonation products.

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The microstructure of ethylene-vinyl alcohol copolymer (EVA) was studied by carbon-13 nuclear magnetic resonance. It was found that the ethylene-vinyl acetate copolymer (EVAc), acetylated EVA, contains two kinds of side chain, acetoxyl short branches, originated from incorporated vinyl acetate, and alkyl short branchs, derived from incorporated ethylene. The contents of the branches in EVA containing about 30 mol% ethylene were 0.1/-0.2 mol% in acetoxyl unit and ca.1.0 mol% in alkyl units. It was also found that the amounts of 1, 2-diol, formed by the foreign combination in the course of polymerization, were 0.3, -4.4 mol% and decreased with iiiCreasing ethylene content of the copolymer. The amounts of 1, 4-diol, formed by other foreign combination were determined by carbon-13 nuclear magnetic resonance to be 3-4 mol% in the case of suspension polymerization and less than 1 mol% in the case of solution polymerization'.

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Amphiphilic cooligomers composed of 2-hydroxyethyl methacrylate (HEMA) and acrylamide were synthesized in order to clarify the - relationship between conformational change and hydrophobic interaction in comparison with HEMA-vinylpyrrolidone (NV P) cooligomers. The fluorescence intensity has been shown by the fluorometric analysis using auramine to increase with increasing HEMA composition in the HEMA-NVP system. In the HEMA-acrylamide system, the fluorescence intensity increased with HEMA composition when the mole fraction of HEMA was higher than 0.6. These results show that, as the formation of hydrophobic region is restrained by the amide groups in the cooligomer chains, the hydrophobic region is not formed until the HEMA composition becomes sufficiently high. Viscosity of HEMA cooligomers increased in the presence of sodium dodecyl sulfate (SDS), because the complex similar to a polyelectrolyte was formed with SDS by the hydrophobic interaction. The dependence of the viscosity increment on the HEMA composition is remarkably different in each system and the pattern similar to that of the fluorometric analysis was obtained. Thus the formation hydrophobic interaction and its functional occurrence are influenced by the structure of the hydrophilic groups as well as the content of the hydrophobic groups. The functional occurrence of the hydrophobic groups in amphiphilic cooligomers is prescribed by the aggregation state of the hydrophobic groups which is influenced not only by the content of hydrophobic groups but also by the structure of the hydrophilic groups.

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Prepolymers (1), (2) and (3) were synthesized by the reaction of poly (ethylene glycol diglycidyl ether) with a secondary amine (diethylamine, dipropylamine and dibutylamine, respectively) using a small amount of water as a catalyst.
The crosslinking reaction of prepolymer with cyanuric chloride took place in a Schotten-Baumann fashion to give a very stable product polymer in which hydrogen chloride produced in the reaction system was trapped by the amino groups of the polymer chain. The reaction of prepolymer C 3 with cyanuric chloride proceeded by a Menshutkin type mechanism. In the reaction of prepolymer C 2 with cyanuric chloride, the above two mechanisms were operative in competition. These reaction mechanisms were confirmed by NMR spectra of the products which were obtained by the reaction of monomeric analogs with cyanuric chloride. The reaction mechanisms and the structures of the crosslinked polymers depended on the basicities of the amino groups of the prepolymer.
The crosslinked polymers which were synthesized from the telechelic diamino dihydroxy prepolymers were more stable than those synthesized from a, w-diol-type oligomer.

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The reaction conditions were investigated to prepared the water-soluble cationic starch containing triethylammonium chloride group, and the flocculating ability of the product was examined in the kaolin suspension.
When potato starch (1 g) was treated with epichlorohydrin (10 ml) in 0: 2% 1-12SO₄ solution (10 ml) at 45°C for 24 hr, the degree of etherification (DE) of the product was about 0.4. The DE value increased and the yield decreased with repeating the reaction. The product showed the surface-active property.
When 2% aqueous solution containing 1 g of the etherified starch (DE= 0.6) was treated with triethylamine (1-6 ml) at 60°C for 1 hr, 42-40% of Cl in etherified starch was converted into triethyiammonium chloride group.
The titration curve of this cationic starch solution with HCl solution showed two steps.
This product showed a flocculating action in the kaolin suspension. The rate of sedimentation was about 6 cm/min on addition of 0.5% (based on kaolin) of the product to kaolin suspension.
The clarification of the kaolin suspension was satisfactory when 0.1% (based on kaolin) of the product was added to the suspension.

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The preheated polystyrene has been analyzed by using a TG-DTA.
The preheating of a polystyrene was carried out in an isothermal batch reactor under nitrogen atmosphere. Experimental conditions of thee preheating were: temperature, 200, -320°C time, hr.
A TG-DTA was operated under definite conditions: sample weight, 8 mg; heating rate, 5°C/ min; I% flow rate, 30 milmin. The experimentalresultsindicated thatalineardecreasein activation energy (4 eE)occurred both in the first degradation stage at lower temperature (below 370°C) and in th sQond degradation stage at higher temperature (above 370°C) with increasing temperature and time of the preheating of a polystyrene.
However, in the case of the preheating below 320°C, a decrease in zIE for the first stage was more significant than that for the second stage (see Fig.4).
Thermal behavior of the preheated polystyiene is descussed in terms of these results, and it is concluded that a decrease in zIE for the first stage is attributed to an appearance of the trimer like compounds which are formed during an initial lowering of the molecular weight of a polystyrene.
On the other hand, it was formed that a decrease in zIE for the second stage was affected by both the constituents, which are stable toward heat and have, in the trimer like compounds and the initial mean molecular weight of the preheated polystyrene.

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Water-soluble poly (methacrylohydrazide) (PMH) was prepared by the hydrazinolysis of poly (methyl methacrylate) (PMMA) with hydrazine hydrate (HH), and the removal of heavy metals from an aqueous solution by the PMH was investigated. Removal was carried out by precipitation or flotation method. As PMH was found to form water-insoluble polymer complexes with heavy metals, especially with mercury, at various pH value, the removal of mercury from an aqueous solution could easily be carried out by the filtration of the precipitates. The highest removability was observed when PMH, prepared from PMMA (M. W.225 x 1O^2-) and HH, was added to Hg²⁺ solution in a molar ratio of 3-4 hydrazide groups to one Hg²⁺, and more than 98.5% of Hg²⁺ was removed from the aqueous solution containing Hg²⁺ (10 me). When excess PMH was added to the Hg2solution, it was found that the polymer complexes tended to redisperse into water. Introducing styrene, a hydrophobic group, into PMH prevented the redispersion of the precipitate. It was found that the selective removal of Hg"could be carried out by changing the pH of the aqueous solutions containing mercury and other metals.

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The chloride-formation reaction of metal oxides with HCl gas and the reverse reaction were studied to obtain the basic informations about the corrosion of materials, recovery of waste catalysts, minerals with volatilization of chlorides, and the catalytic mechanism of Deacon reaction or oxychlorination. The experiments were carried out by using a thermanobalance, , X-ray diffraction, and gas analysis under an atmospheric pressure and at 25-500°C. Inlet gases were 0-1.5% HCl-O-21% O^2-0 or 4% H₂0-N2 and etc., and the total gas flow rate was 500 N. ansimin for 80 mg of metal oxides and etc. (avarage diameter 0.16 mm). The metal oxides were mainly prepared by the precipitation reaction of metal salts with NaOH at 70 or 100°C
The following results were obtained:
1) The chloride-formation reactions are brought about by M0+2 HCl, -MCl2+H₂0 for MO (MgO, CaO, NiO, CuO, ZnO, PbO, HgO, etc. and by Mx0y +2 y MCl2+ y H₂0+ (y x) Cl2(Eq. A) for Mx0, , , (V205, Mn$0, Mn2O^2-, Co3O^2-, Pb3O^2-, PbO^2-, etc. ). Also, for Cu0 above ca.300°C, the reaction of CuO + 2 HCl CuCl+1-120+ (1/2) Cl2 occurs and A12O^2-, SiO^2-, Fe208, FesO^2-, ZrO^2-, CeO₂, WO^2- and etc. do not react under the present conditions.
2) The chloride formation reactions (Eq. A) are the combination of MsOy+ 2 x HCl x MCl2+ x H₂0+ (y) /2jO^2- and MCl2+ (y/2 x)°2---- (1/x) V1, 0, -1- Cl2 (Eq. B), which is the decomposition-oxidation reaction of metal chloride (MCI2) with O^2-.
3) The decomposition-oxidation reactions of chlorides in water vapor are given by MCl2+ (Y/x)120-- (1/x)Mx0v+ 2 HCl+ (Y/x) -11112 at lower temperatures and by MCl2+H₂0--M0 +2 HCl at higher temperatures. Also, in the mixtures of O^2- and water vapor, it is shown by MCl2+ (y-x) /2 X1O^2- + H₂0(1/X) MrOy + 2 HCl.
4) The catalytic mechanism of Deacon reaction (4 HCl+O^2-2 Cl2+2 H₂O) was elucidated in terms of the combination of Eqs. A and B.

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Adsorption of N4z-SOz mixtures and SOS, or NO₂ after equilibrium adsorption of NO₂ or as well as that of NO, NO₂, N20, SO₂, SO^2-, and water vapor on activated carbon was studied by, using a thermanobalance under an atmospheric pressure and at 150--400°C (mainly 150°C). Also the regeneration was studied at 150-900°C in a N2 stream and the analysis of &sorbed ks' was made.
Inlet gases were 0.5/ NO, (SO^2-, SOS, NO, or N20)-0, -5% O^2-10% H₂0-N2 and the total gas flow rate was 600 Nma/min for 150 mg of activated carbon with average dia. of 0.5 mm. As a result, the following information was obtained:
1) In the non-mixed system, SO₂ was adsorbed markedly and the order of apparent activity was SO^2-NO₂SO^2-; NO, N20 and H₂O were scarcely adsorbed.
2) In the NO^2-SO^2- system, SO₂ formed by the reaction of NO₂+ SO^2--4-NO-F SO, on activated carbon, was adsorbed predominantly and in the NO^2-SO^2- system, a considerable amount of white solid, probably nitrosyl disulfate, deposited at a low temperature, but in the presence of water vapor^ such a solid did not form.
3) Adsorption site of NO₂ differed from that of SOS.
4) At a high temperature-desorption, adsorbed NO₂ and SO₂ oxidized the activated carbon to form CO₂ and CO and resulted in a decay of carbon.

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2, 4-Pentadienenitrile and 4-methyl-2, 4-pentadienenitrile were found to afford the w-co coupled dimer along with some polymers respectively when they were warmed in acetonitrile at 50°C in the presence of anhydrous cobaltous chloride-zinc powder as a catalyst. A methyl group attached to the 8-position of the cyano group of the dienes in this reaction seems to affect the course of the dimerization and none of dimer from 3-methy1-2, 4-pentadienenitrile and 3, 4- dimethy1-2, 4-pentadienenitrile was obtained even under rather drastic conditions.

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The codimerization of ethylene with' propylene catalyzed by potassium was carried out at 130°C in heptane to give 1-pentene as a major product. Addition of carriers such as Cu, K2CO₃ and KCl powder increased the yield of 1-pentene as well as the reaction rate. Addition of potassium butoxide as an additive was effective but that of tributylamine was not so effective in the reaction in contrast to the case of potassium-catalyzed dimerization of propylene, in which both additives were effective. Octylpotassium was found to be a very effective catalyst for the selective formation of \J-pentene, and Potassium. -octyl chloride catalyst also gave a simmilar result.

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o-Acetylbenzophenone with reacted with methanediamine dihydrochloride and 1, 2-ethanediamine in alcohols in the presence of acetic acid to give deep blue pigments which were isolated as their hydrochlorides, C_2C91119 CHO H₂ClE [6 a] (n=1), [6 la] (n= 2). From [ 1 ] and 1, 3-propanediamine two deep blue pigments, C82Fl26N2Cl [6 c] and C351-137N4Cl3 7 were obtained under the similar conditions.
On the basis of their IR, NMR and MS spectra, the structures of [6 a, b, c] were determined as 1, 1'-methylene-, 1, 1'-ethylene- and 1, F-trimethylene-5, 5'-diphenyl-3, 4: 3', 4'-dibenzo-2, 2'-pyrromethenium chlorides, respectively. Compound 7 was also elucidated to be 1, 1-bis(3-ammoniopropyl)-5, 5'-diphenyl-3, 4: 3', 4'-dibenzo-2, 2'-pyrromethenium trichloride. A mechanism for the formation of 6 is proposed as shown in Scheme 1.

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Inspection of the color reactions between o-acetylbenzophenone 1 and twenty four amino acids present in proteins revealed that only the coloration with L-cysteine was analogous to that with human skin.
On the color reactions of [ I ] with S-methyl-L-cysteine and of in with L-cysteine, deep blue pigments, C821-1281\T2O^2-SR ([2 a] (R = Me) and [2 b] (R =H), respectively) were isolated. The structures of [2 a] and [2 13] were determined as 1- (1-carboxy-2-methylthioethyl)- and (1-carboxy-2-mercaptoethyl)-5, 5'-dipheny1-3, 4: 3', 4'-dibenzo-2, 2'-pyrromethenes, respectively, on the basis of their IR, UV, NMR and MS-spectra.

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A new method for the synthesis of 2-benzoy1-5-dimethylaminobenzoic acids [2 a-e] was investigated.
The condensation of 3-dimethylaminobenzoic acid with benzaldehydes gave 3-pheny1-6-dimethylaminophthalide[a-e], and on the oxidation of these phthalides with sodium m-nitrobenzenesulfonate in aq. NaOH, 2-benzoyl-5-dimethylaminobenzoic acids [2 a-e] were obtained. The oxidation with sodium m-nitrobenzenesulfonate gave better result than the ordinary oxidation with KMn0, , and the yields were more than 70%.
Furthermore, the reactions of [2 a-e] with aniline or 2-methylindole was also tried for the synthesis of some new 3, 3-diarylphthalides [3 a-se]. Characteristic color was observed when [3 a-e] was absorpted onto silica gel.

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