The role of interfacial electrical conditions in detergency was investigated from the viewpoint of heterocoagulation. In detergent (sodium dodecyl sulfate) solutions containing various builders at constant ionic strength of 3.62 X 10-2, detergency of artificially soiled cottons varied with the types of builders (Table 1). Zeta potential (C) of the soiled cotton and suspended carbon originating from the soiled cotton showed various negative values (Table 2). Degreasing of the soiled cotton decreased the detergency markedly and c of each soiled contton and carbon soil became smaller negative. The maximum values of the total potential energy of interaction between the cotton and carbon (VT, max) as well as the energy differences between. VT, max and the energy at 5A of closest approach for the two substrates (VT, min) were calculated (Table 3). Large VT, max/VT, min ratio and VT, max favor detergency. These two values were large in the detergent solution containing Na5P3010, Na4P2O7 or NTA-3 Na. In the case of degreased soiled cottons, the ratio and VT, max were small even in the detergent solution containing Na5P3010. The stability parameter for heterocoagulation (OH), which relates linearly to VT, max, correlated with the ratio of VTx/ VT, min (Fig.2). In various detergent solutions, detergency increased with 0., and became constant at OH 2.0 x 10-2 (Fig.3).
Detergent builders and oily soil affect the interfacial electrical properties of the soiled cotton and the carbon soil, and change the detergency. This effect was explained by the potential energy between the two substrates.

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The relationship between the molecular structure and explosion behavior of various olefinic hydrocarbons was studied.
The explosion-limit pressures of C_2C5 monoolefins, C45 dienes, n-butane and isobutane mixed with oxygen were measured in the range of temperature from 500° C to 600° C in the case of 50-60 vol % or 90-95 vol % of oxygen. The effect of substituents on the explosionlimit pressures was examined.
In the case of 50-60 vol % of oxygen, the explosion-limit pressures of C_2C5 monoolefins were correlated with C=C stretching frequencies at 530° C to 600° C. Therefore, it is likely that the C=C bond plays a significant role in the explosion reaction. Direct addition reaction of oxygen to the C=C bond may be the first important step.
On the other hand, in the case of 90--95 vol % of oxgen, correlations were observed between the dissociation energies of C-H bonds at a position and the explosion-limit pressures of C_2CC4 monoolefins, n-butane and isobutane at 550° C to 600° C. It is suggested that a hydrogen abstraction ocurring at a position is the first important step. The reaction mechanism is speculated on the basis of these results.

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The rate of the solid state reaction between zinc and arsenic in powder form has been studied at temperatures of 150.400C under pressures of 2O^2-0 kbar. ZngAsg was formed. The rate was determined by measuring the amount of ZngAsa by a peak of the X-ray diffrac=tion pattern. The reaction time-yield curves could be clearly divided into two parts which consisted of the initial and the latter processes of the reaction.
It was assumed that the initial process of the reaction was phase-boundary controlled and was kinetically analogous to ordinary chemical reactions. The kinetic data were analyzed by the second-order rate equation. The apparent activation energy E and the activation volume 4Vf, th, i, iti, l p, , cess were e, tim, t, d t, b, 1012k, al!m, 1 d-0.3-0.5, m, respectively in the temperature range 150-300C.
It was concluded that the Iatter process was diffusion controlled in which the rate'was determined by the diffusion of zinc, because the rate of increase of reaction yields with time was retarded with increasing pressure. The kinetic data fitted the Diinwald-Wagner. diffusioa rate equation. The apparent activation energy E and the activation volume Gy for the diffusion process were estimated to be 9-12 kcal/mol and O.7-r1.4cm'/mol respectively in the temperature range 15O^2-50C.

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The electrode potentials of tantalum chlorides in an eutectic mixture of molten sodium and potassium chlorides were measured against a silver-silver chloride reference electrode. Potential of the reference electrode was referred to a chlorine electrode at the temperature range between 750 and 850° C.
In equilibrium state with Ta metal, Ta (N) +Ta=2 Ta (II) was considered at relatively low concentration of tantalum ions in the melt.
The standard potentials, D-rarra(11) and E° Tarracno and the redox potential, E° Ta(u)/Ta(Iv) were determined as follows:
- E° Tarracuivo(+)=.81+5.6 X 10-4 T/° K
E° Tafraavvvo(+)=.80+7.7 x 10-4 T/° K
E° 116. (11)/Ta(N)/Vo(+)=.79+9.8 x 10-4 T/° K
whare is absolute temperature.
The equilibrium-constant, K, of the reaction Ta (N) + Ta=2 Ta (II) in the melt was expressed in the following equation, log K=(13/ T) +0.54

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Hydration number and heat of solution in water of eight kinds of tris(ethylenediamine)complexes of nickel(II), cadmium(II) and chromium(BI), six kinds of simple salts which mainly consisted of sulfates, seven kinds of chromium (III) complexes with ligand of different valency were determined at infinite dilution (25° C) using an ultrasonic interferometer and a micro calorimeter of twin-type. Those of two kinds of cobalt (It) complexes and of two kinds of bis(ethylenediamine)copper(II) complexes were also determined. The additive property held on both bydration number and heat of solution in water of the constituent ions. The average hydration numbers per gram ion were as follows [Ni(en)3]2+: 14, [Cd(en)3]2+: 22, [Co (C08)] (NH8)41+: 24, [Cr(en), ]3+: 18, [Cu(en), ]2+: 15, OH-: 5.6 mol.
But two values of hydration numbers, 7 and 16, were obtained for a sulfate ion. In the case of tris(ethylenediamine)complex ions with equal valency, those having larger ionic radius of the central metal had greater hydration number. Hydration numbers of [Cr(N1-13)O^2-]+ (12) were smaller than those of NrCl2(F120)41+ (16) and NrCl(NI-13), (H₂0)2+ (15), and greater than that of [Cr(NCS), ]3-. Thus the change in hydration numbers of chromium (l11) complex ions by the valency consisted with the case of cobalt (III) complex ions. The heat of solution in water of these electrolytes except for several sulfates at infinite dilution (25° C) were in good agreement with the value of.6 kcal/hydrated H₂O mol.

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Thermal decomposition of nickel, cobalt and iron(II) oxalate dihydrate in the atmosphere of air, nitrogen, argon or hydrogen was studied by differential thermal analysis, thermogravimetry, evolved gas analysis and chemical analysis with magnetic measurements.
Following the completion of dehydration, nickel, cobalt and iron(II) oxalate decomposed to give DTA peaks at 346°, 359° and 384° C in the nitrogen atmosphere, respectively. These decomposition temperatures in air were lowered by 8° C for nickel oxalate, 76° C for cobalt oxalate and 164C for iron(III)oxalate showing the prmoting effect of oxygen on, the decompositionA rapid heating of these oxalates in air gave the the decomposition products such as over 96 wt%of meta11ic nickel, a mixture of.85 wt% of CoO with Co3q, i mixture of CQ.70wt%Qf FeO wth Fe2O^2-. r cobalt ranging from 85 to 92 wt%and FeO over 93 wt%, respectively. The cotent of CO in the gas evolved by the decomposition was 2.5vol%for nickel oxalate and 48 vol%for cobalt oxalate, and in the case of iron(II)oxalate roughly equal volume of CO and CO₃was detected.
Under the ow of hydrogen, the formation of CH4 was catalysed in the cases of decomposi, Lion of nickel and, cobalt oxalate; catalytic ability of cobalt being superior to that of nickel. In the case of iron(III)6xalate, CHI was nt, s but threaaiori was seen t6 be prornted. From these results a probable process, of thermal decompositio as discussed.

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In order to obtain the fundamental data for separation process in urea syntheses, the vaporliquid equilibria for the quaternary system of urea-ammonia-carbon dioxide-water were measured between 100° C and 150° C at the pressure of 20 kg/cm² and the empirical equations to estimate the relation of the vapor-liquid equilibrium were obtained.
The activity coefficients in liquid phases, were expressed by a following Margules 2-suffix equation.
Good agreement of the calculated values by Eq. (1)and(2)with the observed values revealed that mole fractions in vapor phase, are well estimated from those in the liquid phase, x, at 20kg/cm over the temperature range from 100 to 150°C

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The study of sulfuric acid leaching has been carried out with manganese nodules which were dredged at W 170° 50, and N 10° 18, by the exploration party of Japan in the year of 1970. The nodules were crushed into different size fractions, and leached with O.1-2.0 N sulfuric acid between 30° C and 90° C. The leaching tests for the nodules heated preliminarily at 100-720° C for 3 hr in air were also carried out.
Results of the leaching of 50 mesh fraction with 0.5 N sulfuric acid revealed that copper in nodules was extracted more than 90% at 30° C and nickel more than 80% at 70° C, whereas less than 10% of cobalt was extracted even at 90° C. Therefore, copper, nickel and cobalt in nodules could be selectively separated by the control of leaching temperature.
The extent of copper and nickel leached were not affected by the variation of sulfuric acid concentration more than 0.5 N, but the leaching of iron was associated with an increase of sulfuric acid concentration.
Preliminary heating of nodules improved leaching of cobalt and manganese, decreased leaching of copper and made the separation among these elements become less selective.
Leaching with hydrochloric, nitric or perchloric acid showed almost the same results as those with sulfuric acid at 30° C. At 90° C, hydrochloric acid reduced manganese dioxide in nodules to manganese chloride.

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Fine-grained barium titanate of high purity was synthesized through hydrothermal reaction using hydrous titanium dioxide and barium hydroxide as starting materials.
Yield and crystal structure of the product were affected by both the BaO/TiO₂ ratio of raw material and reaction temperature. The yield obtained at the BaO/TiO₂ ratio 1.0 and 500° C was as low as 92%, whereas it was almost 100% either at the ratio of more than 1.4 and 400° C or at the ratio of more than 1.6 and 300° C.
X-ray diffraction pattern of the product obtained at small BaO/TiO₂ ratio and low temperature showed a cubic perovskite-type structure with somewhat strained and expanded lattice. While, that of the product obtained at large BaO/TiO₂ ratio and high temperature showed a tetragonal perovskite-type structure, a stable phase at room temperature. In this work, crystallite size changed in the range between 90 and 615 A and grain size did in the range between 300 and 10000 A. It is noteworthy that fine grains of a tetragonal perovskite-type structure with the size below 200 A were obtained.
The reason why barium metatitanate, BaTiO₃, is formed as a sole crystalline product in this hydrothermal reaction was discussed.

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Na-fluor-tetrasilicic mica [NaMg_2.5(Si₄O₁₀)F₂](NTSM) was synthesized, and absorption of water molecules into its interlayer sites and free swelling on immersion in distilled water was studied. The interlayer spacing (001) of hydrated NTSM decreases discontinuously. with the release of interlayer water molecules. The single-layer hydrated form [d(100) = 12.34A], which is stable in air 20° C, R. H., dehydrates to anhydrous NTSM [d(001) = 9.56 A] at about 100° C. The octahedral Li+ substitution in the expandable fluormicas brings about the contraction of dimension of parameter b and the reduction in the degree of swelling.

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Method for the spectrophotometric determination of iron with 6-hidroxy-5-nitroso-1, 3- dimethyl-1, 2, 3, 4-tetrahydro-2, 4-pyrimidinedione (HNDU) has been studied. HNDU reacts with iron to form a water-soluble blue complex.
The Fe (II) -HNDU complex has an absorption maximum between 610 and 620 nm and shows a definite absorbance over the pH range from 5.5 to 6.8. Beer's law was followed up to 6 pg/m/ of iron (II), the molar extinction coefficient of the complex and the sensitivity of the determination being 1.55 x 1O^2- //molcm and 0.0O^2-6 pg/cm² for log (4//) =0.001, respectively. Presence of cobalt (II), copper (II) and citrate interfered with the determination. The molar ratio of iron (II) to HNDU has been confirmed to be 1: 1 by the mole ratio method.

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Separation parameters, viz., column efficiency, solvent composition, column temperature and sample loading capacity were studied, using spherical porous poly (methyl methacrylate) as a column packing material.
The porous polymer whose particle size was 20- 1 pm exhibited the column efficiency (HETP) of 1 mm, when methyl yellow was separated with the carrier (methanol) velocity of 0.5 cm/sec. Since the porous polymer had the specific surface area of 82 m2/g, its sample loading capacity was greater than that of pellicular type packing. High separation efficiency was obtained when methanol was used as a mobile phase. It was possible to reduce the retention volume and to improve the column efficiency by adding n-hexane to methanol mobile phase. The improved resolution was obtained by adding water to methanol mobile phase, although the retention volume increased logarithmically with water content. This separation was similar to that of reversed phase partition chromatography using octadecylsilane as a support material.
Using the porous polymer, rapid separation of dyestuffs, steroid hormones and its derivatives was possible. For example, estrone, estrone acetate and estrone benzoate were separated within 12 minutes with the carrier (methanol) velocity of 0.6 //min, under the inlet column pressure of 17 kg/cm² and at the temperature of 53° C, using a column of 500 mm long and 2.1 mm i. d.

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Elimination reactions of acetic acid from 1- (p-nitrophenyl) -2- (2- and 4-quinolyl) ethyl acetates (Cl a) and (bD) to give trans-2- and 4- (p-nitrostyryl) quinolines [C_2C a] and (_2C bp), respectively, have been studied kinetically in some aprotic solvents. The above eliminations were catalyzed by some carboxylic acids and acetate anion (as AcOM M=Na, Li). The catalytic power was in the order: acetic acid acetate anion, and Cl3CCO₂HCl2CHCO₂HClCH₂CO₂HPhCO₂HCH₃CO₂H. The rate for the carboxylic acid catalyzed elimination was expressed as v=k[RCO, H]o[Substrate], which suggests a general acid catalysis in the over-all reaction. The rate for (l a) was correlated with the electron donability LivE, (cm-') of solvent rather than the solvent dielectric constant D, however, that for C/ [3] showed different pictures. The effect of a common anion was observed for both substrates, and an increase in rate was observed for (1 I) for the acetic acid catalyzed elimination in dimethyl sulphoxide-water (22: 1, v/v) at 90° (C). The rate ratio r=k(Cla)11z(Cl b) was smaller than unity (i. e., the rate of Cl bp is higher than that of Cl ap) for the acetate anion (AcOM) catalyzed elimination, however, was larger than unity for the carboxylic acid catalyzed eliminations. The ratio r for the carboxylic acid catalyzed elimination decrease with increasing the acidity of carboxylic acids, the solvent dielectric constant D and the electron donability 4v, of solvent. The kinetic isotope effect, kH/kD, was measured for the carboxylic acid catalyzed elimination of [l a] in ethyl acetate at 50° C. The value of kiilkE, was larger than unity, which suggests a rate-determining elimination of j3-hydrogen. The value of kakp increases at first, thruogh a maximum, and then decreases with increasing the basicity of the attacking base on the 8-hydrogen. This is consistent with a transition state varying from E 1-like to E 1 cB-like.
From the above observations, a most possible mechanism involving a protonation by carboxylic acid on the nitrogen atom of Cl to give a tight ion pair C 5 and a solvent separated one (6) resulting from an interaction between the solvent molecule (s) and C 5 1 and the ratedetermining attack of carboxylate anion on the 8-hydrogen within (5) and C 6 to give trans-olefin (_2C) is proposed and discussed tentatively by assuming the steric models of the ion pairs.

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The photochemical reaction of p-benzoquinone and 1, 4-naphthoquinone in water was investigated.
The reaction products from p-benzoquinone in water were hydroquinone and benzene-1, 2, 4- triol, and those from 1, 4-naphthoquinone in water-acetonirtile (H₂0 2: CH₃CN 1) were 1, 4- na, phthalene diol and 1, 4-naphthoquinone dimer.
The quantum yield concerning the consumption of p-benzoquinone by 7r-z exciting irradiation in water was greater than that by n-x exciting irradiation (Table 2).
Although the photoreduction of quinones in alcohol ptoceed from the lowest n-z tripret state, the photoreduction of p-quinones in water proceed in the mechanism involving the both pathway: a) formation of anion radical by the electron transfer from OH- anion of water to n-a- excited state of quinone (Scheme 1), b) nucleophilic addition of OH- anion of water to rc-e excited state of quinone (Scheme 3).

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Photochemical addition of methyl phenylpropiolate [1 a] and 4-phenyl-3-butyn-2-one [1 b] to cyclic dienes was investigated. While the reaction with cyclohexa-1, 4-diene [2 n] gave a mixture of cyclobutene derivative and dicyclopropyl derivative (a [n.2 s -I-7r 2 s-1-7r 2 s-1-71.2 s] type product), the reaction with bicyclo[2.2.2]octa-2, 5-diene C_2C n-0 afforded selectively dicyclopropyl derivative (Table 1). The ratio of (cyclobutene derivative)/ (dicyclopropyl derivative) in the photochemical reaction with [2 n] and [2 m] were 0.61/0.39 and 1, respectively. This is a marked contrast with the ratio (1/-0) previously observed in the similar reaction of bicyclo[2.2.1] hepta-2, 5-diene [21]. The fact that the initial attack of an active species to C_2C generally comes from the exo-side may cause the remarkable advantage of Dr 2 s-Fr [2 s] type over [n- 2 s-F7r 2 s+n- 2 s+71- 2 s] type. On the other hand, in C_2C mi Dr 2 s-1-7r[ 2 sd-n- 2 s -Or 2 s] typ-2 reaction is dominant since the endo-attack of the active species is preferable. The competition of two types of reaction in the addition to (2 n) would be reasonable since the structure of [2 n] is nearly planar.

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Irradiation of trans-styryl- (/ A) and 2-methyl-trans-styrylsulfonamides [2 A] isomerized them to the cis-isomers (1 B) and C_2C [B], respectively. cis-Styryl- [4 B] and 2-methyl-cisstyrylsulfonylthioureas (5 B), and cis-styryl- [10] BD and 2-methyl-cis-styrylsulfonylisothioureas (11 B) underwent the Michael cycloaddition more slowly than the corresponding trans-isomers [4 A], (5 A), C[l0 A] and C[1 A] because of steric hindrance of a phenyl group. Electronreleasing methyl group on C-2 diminished the rate of the cycloaddition. The Michael cycloaddition of 4-phenyl-1, 3-butadienylsulfonylthioureas [ 6 ] and that of isothiourea C[2] were also studied. Relative rates of the cyclization of thioureas and isothioureas are as follows:
[4 A] [4 13] 6: [5 Aa]: (5 Ba)=3.07-3.53: 2.74-3.05: 1.23-1.33: 1.08: 1.00
Cl0: [II Aa]: C/O 133: [i/ Ba]=2.35. -2.69: 1.36-1.41: 1.00: 0.
trans- and cis-Thiourea and trans- and cis-isothioureas gave racemic Michael cycloadducts. Their steric courses were considered.

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The reactions of p- and p'-substituted N- (2, 2-diarylvinylsulfonyl) -N', O-dimethylisoureas [3] and -N', S-dimethylisothioureas [6] with bases afforded new intramolecularly rearranged. N- (2, 2-diarylviny1)-N, O-dimethylisoureas [ 7 ] and -N, S-dimethylisothioureas C/O, respectively. Compounds [l0] suffered easy hydrolyses to N- (2, 2-diarylviny1)-N-methylcyanamides and N-(2, 2-diarylviny1)-N-methylureas C/2 in the more moderate reaction conditions than those of [ 3 ]. The rearrangement requires an electron-releasing methyl group at N'position. The order of reactivity of C 3 and C 6 indicates that the rearrangement is retarded by electronreleasing p-substituents on benzene rings (ClHCH₃OCH₃).

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5, 6-Dihydro-1, 4, 2-dioxazines were prepared by the reaction of hydroxamic acids with vicdihaloalkanes and vic-dimesyloxyalkanes. The optimum reaction conditions and the effect of the leaving group (Cl, Br, OSO, CH, ) on the yield of dioxazines were investigated. The properties and analytical data were provided and discussed.
Dioxazines obtained from the reaction of hydroxamic acids with 1, 2-dibromo- or -dimesyloxypropane were found to be mixtures of 5-methyl and 6-methyl derivatives. Authentic 5, 6- dihydro-5-methy1-3-pheny1-1, 4, 2-dioxazine was prepared by an alternate route and its NMR spectrum was compared with that of the mixture obtained from the reaction of sodium benzohydroxamate with 1, 2-dibromopropane. The ratio of 5-methyl to 6-methyl derivatives was found to be about 2 in every reaction of this investigation.

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In the disproportionation of propylene or 1-butene the effect of addition of various metal oxides on the MoO^2-A12O^2- catalyst over the temperature range from 40° C to 140° C was investigated with a conventional flow system of fixed bed.
When alkali or Ti oxides were added to MoO^3-A12O^2-, the catalytic activity decreased with increasing ionic radius of added metal ion as well as amount of addition. The selectivity of propylene disproportionation at 40° C was higher than 99%, and increased further upon addition of alkali metal or Ti oxides. It was observed that in the case of 1-butene (C, '+ C6') selectivity, and C, '/C, ' ratio, correlate to ionic radius and electronegativity of added alkali and T1 oxides, and in the case of propylene C4'/C_2C' ratio as well as yield of 1-butene correlate in the same way. However, the effect of alkali earth and other metal (Pb, Bi, Ni, Co) oxides is apparently different from that of alkali and TI oxides.

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The manufacture of adsorbent from Japanese brown coal was carried out by treating it with aqueous NaOH solution. The so called NaOH treated coal was prepared by treating it with NaOH solution. The solution was consisted of 10 g NaOH and 60 ml water, in which 100 g brown coal whose size was 16-32 mesh was added. The reaction was carried out at room temperature for 180 minutes. After the reaction was completed, the product was repeatedly washed with water.
Although the above treated coal has an excellent quality as an absorbent, it still has a fault in elution of humic acid with deep brownish color when immersed in water for a while. In order to remove this fault, the NaOH treated coal was impregnated with NH4 CA²⁺ or etc. solution. It was found that these ions are excellent reagents for preventing of elution of humic acid. If 32 mg CA²⁺ was adsorbed per 1 g coal, no elution of humic acid was observed when the sample was immersed in NaOH solution at pH 8.5 for several weeks.
When the sample was immersed in 1000 ppm methylene blue solution for an hour, the amount of methylene blue adsorbed was found to be 95 mg/g. This value was lower than 150 mg/g, the value not treated with CA²⁺.
As the adsorbability of original coal was 18 mg/g, the NaOH treated coal with adsorbed CA²⁺, would be sufficiently available for actual waste treatment. The compressive strength of each piece of the sample is 300-1000 g. Discussion is given on these phenomena and results.

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Disproportionation of propylene with isobutylene has been investigated over WO^2-SiO^2- catalysts. The experiments were carried out at a total pressure of about 1 atm and tempera tures of 450-500° C in quartz reactors.
The effects of interphase mass transfer on the reaction rates were significant, and the reaction appeared to be limited by external diffusion. When the runs were carried out on an impregnated WO^2-SiO₂ catalyst with the mixed feed in which the molar ratio of propylene isobutylene was unity, the ratios of initial rates of three primary reactions, propylene-propylene, propylene-isobutylene, and isobutylene-isobutylene metathesis, were 180: 70: 1 at 450° C, 130: 60: 1 at 475° C, and 80: 50: 1 at 500° C. These ratios do not agree with the ratios estimated by assuming that the reactions are completely limited by interphase mass transfer. To interpret these results, it should be considered that the effective surface area or the numbers of active sites of the catalyst are very small and effective surface areas for three primary metathesis are different each other. From the considerations of the rate ratios, the differences of apparent activation energies for the reactions, and steric factors of olefins, it may be presumed that the active sites of the WO^2-SiO^2- catalyst consist of the sites to promote all primary metathesis, the sites to promote propylene-propylene and propylene-isobutylene methesis, and the sites to promote only propylene-propylene metathesis.
From the results of runs with various feed ratios, it was recognized that isobutylene isobutylene metathesis was inhibited in the presence of propylene, whereas propylene-propylene or n-olefin-olefin metathesis was rather promoted in the presence of isobutylene.

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Kinetics of oxidation of 4-nitro-2-toluenesulfonate (NTS) to 4, 4'-dinitro-2, 2'-stilbenedisulfonate (NSS) in I-120-NaOH (A) and D2O-Na0D (B) were studied by means of proton NMR spectroscopy. The reaction in consecutive through 4, 4'-dinitro-2, 2'-dibenzyldisulfonate (NDS):
NTS NDS NSS.
The rates were expressed as follows.
I; lENTS1/dt=k I ENTSIOH-7
II; lENDS1/dt=k HENDSIOH-
In I, the rate in system B was larger than that in system A, and the isotope effect was expressed as kj, lkiH-=8.6 at 60° C.
In II, isotope effect was not observed.
On the basis of the results, it was suggested that the rate determining steps were deprotonation of NTS and NDS by hydroxide ion.
The increase of reaction rate with oxygen pressure (1 atm, 1/5 atm-1 atm Po) was not observed under the conditions, but at higher oxygen pressure (2-8 atm) sodium 2-formy1-5- nitrobenzene sulfonate was detected.

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The effects of reaction temperature and mercury (II) chloride on the ratio of the 2- and 3- sulfonated products (2-s/3-s) of the monosulfonation of 4-nitro (. /), 4-amino [ 2], 4-chloro [ 3] and 4-bromotoluens C 4 were studied by the NMR spectral analyses of their methyl signals [ 1 ]2-s: 8.05, [ 1] 3-s: 8, .40, [ 2] 2-s: 8, .17, C_2C 3-s: 8.50, C3 2-s: 8.13, (3) 3-s: 8, .36, [4] 2-s: 8, .15, [4] 3-s: 8.40 ppm from water as the internal standard.
In the sulfonation of 4-nitroluene with 20% oleum at 20° C to 120° C, the ratio (2-s/3-s) was almost constant at about 98/2 and mercury (11) chloride increased only the total sulfornation yield. In the sulfonation of p-toluidine C 2D, the ratio (2-s/3-s) gradually decreased from 74/26 at 20° C to 58/42 at 140° C.
In the sulfonation of 3 and C 4 D, C3D 2-s and (4) 2-s were obtained as a main products (68, 88%). The above value was not effected by mercury(II) chloride but the yield increased slightly.

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2, 4, 6-Tribromophenol (TBP) was found to be an effective photosensitizer for the photopolymerization of methyl methacrylate (MMA). The degree of polymerization of the product increased with increasing conversion of monomer even in low conversion. Polystyrene formed by the photopolymerization with TBP could initiate the polymerization of MMA, acrylonitrile and vinyl acetate. However, no cross-linked polymer was obtained. Photolysis of TBP in tetrahydrofuran gave 2, 4-dibromophenol and 4-bromophenol in the molar ratio 77: 23.
From the above results, it was concluded that TBP initiates the polymerization at the 2position to give the polymer containing 2, 4-dibromophenol residue and the polymerization is initiated again at the 2-position of 2, 4-dibromophenol residue in the polymer.

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The initiation mechanism of radical polymerization resulted from the intiator system of triethylboron and oxygen was investigated by using a spin trapping technique. When 2- methyl-2-nitrosopropane (BNO) was used as a spin trapping reagent, both ethoxy and ethyl radicals were trapped as nitroxides which were obtained by the respective reactions of them with BNO (Figs.1 and 2). Similar results were also obtained when phenyl-N-t-butylnitrone (PBN) was used as a spin trapping reagent (Fig.3). From the effect of time of the reaction of triethylboron with oxygen and that of concentration of spin trapping reagent on the ESR spectra of the reaction mixture (Figs.4 and 5), it was concluded that ethoxy radical is producd initially and ethyl radical is formed through the subsequent reaction of ethoxy radical with triethylboron. This conclusion was also confirmed in terms of the result obtained by using 3, 5-di-t-butyl-4-hydroxyphenyl-N-t-butylnitrone (BHPBN), which can readily distinguish oxy-radical from carbon-radical, as a spin trapping reagent. Thus the ESR spectrum (Fig.6) due to a phenoxy radical formed by the reaction of BHPBN with oxy-radical was alone observed. From these results, the initiation mechanism of redical polymerization resulted from this system was discussed.

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Radical copolymerizations of methacrylic acid coordinated to pentaamminecobalt (III) complex (metal-complex monomer) with methacrylic acid (MAA) were carried out in an aqueous medium at pH 3 and at pH 7. It was found that the metal-complex monomer becomes incorporated into the macromolecules more easily at pH 7 than pH 3. This may relate to the electrostatic interactions between the reaction species (monomer and growing chain). It was also found that the metal-complex monomer can singly homo-polymerize at pH 3, although the product contains a certain amount of MAA units. This may be due to the redox reaction between the metal-complex monomer and one of the initiators (sodium thiosulfate). In terms of the date of monomer reactivity ratios, Q-e values and rate of copolymerization, the reactivity of the metal-complex monomer was discussed in connection with the effects of the transition metal contained in the conjugated system of the monomer.

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Microtacticities of the polymers obtained by radical copolymerization of methacrylic acid coordinated to pentaamminecobalt (III) complex (metal-complex monomer) with methacrylic acid (MAA) were studied. It was found that the macromolecules polymerized at pH 3 have much more isotactic sequences by the introduction of appropriate amounts (about 15%) of the metal-complex monomer. However, microtacticities of the polymers obtained at pH 7 are slightly affected by the introduction of the metal-complex monomer. From these results as well as Pddi/Pdi and A values, it was found that the penultimate effects play an important role in the determination of the steric configurations. At the same time, it should be considered that the electrostatic interactions between the reaction species (monomer and growing chain) also play a definite role in the determination of the microstructures from the fact that microtacticities are greatly influenced by the ionized state of the reaction species.

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The interaction between optically-active dansyl amino acids, a fluorescent probe, and bovine serum albumin (BSA) was examined by fluorescence and ultraviolet spectroscopy. The following results were found in this examination.
1) To one mole of BSA bind three moles of the dansyl amino acids. The dansyl amino acids are present in the region of high hydrophobicity in BSA.
2) The binding behavior of the optically active densyl amino acids to BSA is dependent on their optical isomers. The binding constants of D-isomers are larger than that of L-isomers. The difference in the binding constants of the optical isomers increase with increasing carbon number in the amino acid residue of the dansyl amino acids.
3) The differences in the binding constants of the optical isomers are not due to the binding of the optical isomers to different binding sites but to the different interactions between the optical isomers resulting from the mutual action of fluorophor of the dansyl amino acids based on the stereospecific factors and of the amino acid residues around the binding sites of BSA.

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The oxidation of ethylene 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 25-45° C in the diffusion controlling region.
The rate-determining step of the reaction was investigated over a wide concentration range of cupric chloride and was found to be carbonylation reactions.
The observed chemical absorption rates of ethylene were analyzed on the basis of the chemical absorption theory, and the carbonylation reactions were found to be of first-order with respect to ethylene or palladous chloride, to be reciprocal to second-order to chloride ion and to be zero-order to hydrogen ion.
It was found that the product (acetaldehyde) affects the absorption rate of ethylene gas.

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The effect of phase transfer catalyst, emulsifying agent or agitating speed on the oxidation reaction of 1-octene by KMnO₄ was investigated in a heterogeneous liquid-liquid system. In the system without catalyst and emulsifying agent the obtained kinetics of the oxidation is as follows:
r=koNi. ocAincBit3
where, r=Rate of reaction (mol//in), ko=Constant (mol6//6. minpm), N=Agitating speed (rpm),
CA=Concentration of 1-octene (mol/l), CB=Concentration of KMnO^2- (mol//).
Fig.4 and 5 show that the rate of the reaction is proportional to the surface area of drops. The effect of three compounds as phase transfer catalyst was investigated qualitatively and quantitatively. Addition of tetrabutyl ammonium bromide or ethylhexadecyldimethyl ammonium bromide does not increase the rate of reaction, but addition of tributylhexadecyl phosphonium bromide alone increases it. This catalyst was confirmed experimentally to work effectively as a phase transfer catalyst. Addition of sodium stearate or sodium laurate accelerates the rate of reaction remark/ably. The kinetics obtained is as follows:
r=k2CACBm where, k2=Rate coastant (11"/mol11snin).
Fig.12 and 13 show that the rate constant k2 depends on agitating speed and concentration of emulsifying agent.
Fig.11 shows that the emulsifying agent increases the rate of reaction more than the phase transfer catalyst. Emulsification may cause the marked change in surface area and in controlling step of the reaction.

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The degrees of sensitization of octahedral AgBr grains by halogen acceptors (acetone semicarbazone and sodium nitrite) increased as the size of the grains decreased. In fine grain (0.2 μ) AgBr emulsions, the sensitization by the halogen acceptors and sulfur sensitization were competitive. These results have been thought to support the view that sulfur sensitization in fine grain AgBr emulsions is in part due to the halogen acceptance of Ag2S specks formed during digestion.

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Single crystals of Cu₃TiO₄ were grown by charging the Cu₃TiO₄ powder in a platinum crucible of either 70 mm long and 8 mm in diameter or 70 mm long and 20 mm in diameter, sealing the crucible with contents, lowering it into furnece of 1050° C at verious speed between 40 and 2.5 mm/hr.
Single crystal of maximum dimention of 5.8 X 5.0 X 4.8i mm was obtained at the lowering speed of 2.5 mm/hr. Electrical conductivities of these single crystals were measured by two-probe method. The anisotropic electrical conductivity is d (c) = 4.0 x 10-7 (1/12-cm) and (//c) =4, 4 X 10- (1/0-cm) at 200° C. Activation energy is E (Ic) = 0.40 (eV) and E (11c) = 0.49 (eV).

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ESR spectra of Cu (acac)₂ in various cyclic ethers (or sulfides) -chloroform systems were observed, and the shifts in g11 and IA/11 parameters were attributed to the formation of the 1: 1 Cu (acac) 2-Lewis base adducts. The magnitudes of the shifts in the ESR parameters are correlated with the basicities of the ethers and sulfides, and a fairly good linear relation was obtained among them. With the aid of visible absorption spectroscopy, the existence of the 1: 1 adduct was verified by observing an isosbestic point in the spectra of ternary Cu (acac)₂ - chloroform-THF system.

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Properties of active carbon prepared from sulfuric acid sludge a waste in petroleum refining have been investigated.
Steam activation of the carbonized sulfuric acid sludge led to remarkable development of transitional pore volumes in the range of pore radii from 100 to 300 A at activation losses above 52.8%.
The carbons from sulfuric acid sludge showed high adsorption abilities both in gas phase and in aqueous solution.

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Iodine-catalysed reactions of 1, 4-diol monoacetates [1] were studied. Elimination of acetic acid and water from C proceeding stoichiometrically, gave substituted tetrahydrofurans [2] (2, 2-dimethyltetrahydrofuran, 2, 2, 3-trimethyltetrahydrofuran, 2, 2, 4-trimethyltetrahydrofuran, and 1-oxaspiro[4, 5]decane) and olefins [3] and [4], respectively. The reaction of [1] in the presence of water produced only [2] in high yields without the formation of olefins.

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A new method of optical resolution of (±)-menthol is proposed. (+)- or (-)-N-Benzoyltrans-2-aminocyclohexanecarboxylic acid C was converted into corresponding acid chloride [2]. The reaction of [2] with (±)-menthol gave diastereoisomeric ester [3]. Fractional crystallization and successive hydrolysis of [3] gave pure (+)- and (-)-menthol in 73-75% yields.

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The study of the oxidation of propylene in liquid phase in terms of Wacker-process was carried out experimentally in liquid. iet column.
The average absorption rate of propylene in liquid jet column, calculated by using the reaction rate constants obtained in an agitated vessel, was in good agreement with that obtained experimentally.
It was found that this reaction can be treated as chemical absorption accompanied by simultaneous reversible pseudo-first order reaction and that the constant rate of gas absorption obtained in an agitated vessel can be considered to be that of initial absorption.

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