The presence of “bound water” in oil-in-water emulsions containing nonionic surfactants was suggested by the determination of nuclear relaxation times of protons, T₁ and T₂, using liquid paraffin and carbon tetrachloride as the oil phases. An analysis on the basis of a rapidly exchanging bi-phase model suggested that the correlation time of the bound water was of the order of 2×10^-8-10^-7s and that the amount of the bound water per one gram of a surfactant increased up to about 90 mg (CCl₄-emulsion) and about 200 mg (liquid paraffinemulsion)respectively with the increase of the ratio water/surfactant in the emulsion (examined up to 50 g H₂O/g of surfactant, that is, 90% water). The bound water is considered to be formed by some interaction between water molecules and the hydrophilic moieties of the surfactants contained. The behavior of the bound water can be interpreted in terms of equilibrium between hydrated and unhydrated hydrophilic groups of the surfactants.

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Hydroformylation experiments of 1-hexene were carried out using MeCCo₃(CO)₉ [1], as a catalyst precursor. The reaction occurred after an induction period, with aldehydes produced. The ratio of normal to branched aldehydes formed was a little higher for [1] than for the CO₂(CO)₈ catalyst conventionally employed under the same reaction conditions. The catalytic properties of [1], however, were rather analogous to those of CO₂(CO)₈. The formation of CO₂(CO)₈, (350 nm) was evident from the UV spectral changes of the cluster solutions containing no 1-hexene. In addition, the increase in the intensities of IR bands of metal carbonyls, characteristic of CO₂(CO)₈, was observed in the solutions. The declusterification of [1] was apparent in the 1H-NMR spectra, where the decrease of the methyl peak (%δ3.20(C₆D₆), singlet) was observed. These data suggested that under the present reaction conditions [1] declusterified, at least in part, producing CO₂(CO)₈, which has catalytic activity for the hydroformylation of 1-hexene.

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As the first step in the research of the catalytic decomposition reaction of HI, which constitutes the hydrogen evolution stage in the NCLI Magnesium-Iodine thermochemical cycle, suitable catalysts for the reaction were searched. A flow method was used and HI was fed in the form of hydriodic acid (7.5 N) to obtain similar reaction conditions to those in the decomposition of HI included in the present cycle. A research of catalysts prepared from various transition metals (compounds) and r-alumina support by an impregnation method showed that supported platinum group metal (1 wt%)catalysts had good activities. Supported nickel and molybdenum (10 wt%) catalysts were found to show lower activities than those of the former. Furthermore, a research of catalysts prepared from one of the metals of platinum, palladium and nickel and from various supports (zeolites, hydrophobic supports, active carbon, and so on) showed that platinum/active carbon (1 wt%) and. active carbon itself had high catalytic activities. The platinum/active carbon catalyst (1.8g) was able to decompose HI to the equilibrium conversion, about 0.27mol of HI per one hour at 650K, while the active carbon catalyst (1.8g) attained the equilibrium conversion at a higher temperature of 720 K.

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It was found that chrolo complexes of Pd(II) or Cu (II) were fixed on the surface of SnO₂powders suspended in an aqueous PdCl₂-NH₄CI or CuCl₂-CH₃COONH₄ solution, accompanied by a release of H⁺ ions from the surface. The stoichiometry of the released H⁺ for a given amount of the fixed metal ions as well as the chemical analyses of the fixed surface revealed the formation of bidentate compelexes of the type [ (-O)2MCl₂]2- 2NH₄+ (M =Pd or Cu)where -O represents the oxygen atom of a hydroxyl group on the Sn02 surface. On heating in nitrogen atmosphere, the surface complexes decomposed in steps, losing first NH₄+ at 100-300° and then C1- above ca.300° as revealed by TG and chemical analyses. In a gaseous mixture of propene and oxygen, however, the Pd(II) complexes were easily reduced to metal Pd. The metallic Pd-fixed catalyst thus prepared was found to be much more active for propene oxidation than one prepared by the conventional impregnation method, and this was shown to be due to the higher dispersion of Pd in the Pd-fixed catalyst. It was also possible to fix both Pd (II) and Cu (II) complexes together on the SnO2 surface. In the resulting catalysts, the catalytic activity of Pd was found to be markedly promoted by the presence of Cu(II) ions.

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The reaction of urea with diammonium imidobis(sulfate) (DIS) in the molten state under an atmospheric pressure, as well as the effect of ammonia on the formation of guanidinium ion(GH⁺) have been studied.
The bubbling of ammonia into the melt during the reaction led to a considerable increase of the yield of GH⁺, the suppression of side reactions, and favorable fluidity of the melt. The formation of GH⁺ was initiated at 180°. At a constant temperature and reaction period(1 h), the GH⁺ yield increased precipitously in a temperature range of 180-210°C, and gradually in a temperature range of 210-250_. At temperatures above 260°C, however, it showed, a steady decrease due to the decomposition of GH⁺ previously formed. The gradual_increase of the GH⁺ yield at 210-250_ may be due to the conversion of the 1, 3, 5-triazine-2, 4, 6(1 H, 3 H, 5 H)-trione (cyanuric acid) to GH⁺. The cyanuric acid was formed as a by-product at a previous stage. Small amounts of cyanuric acid, 6-amino-1, 3, 5-triazine-2, 4(1 H, 3 H)-dione (ammelide), 4, 6-diamino-1, 3, 5-triazine-2(1 H)-one (ammeline), and 1, 3, 5-triazine-2, 4, 6triamine (melamine) were also formed as by-products. Among them, ammelide and ammeline were separated as water-insoluble material in the form of a molecular compound (molecular ratio 1: 1). The reaction by bubbling of ammonia was found to be analogous to the reaction of urea with ammonium amidosulfate, since DIS was readily ammonolyzed to ammonium amidosulfate in the presence of urea at temperature as low as 160°

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The β-alumina crystals containing cations such as K⁺, Ag⁺, NH4⁺, Ca²⁺ and Sr²⁺ were prepared by ion exchange. Thermal decompositions of these ion exchanged β-aluminas and Na⁺-β-alumina were studied in various firing atmospheres (air, N₂ and Hv). The results obtained are summarized as follows:
(1) β-Aluminas containing monovalent cations, such as Na⁺, K⁺, Ag⁺ and NH4⁺, decompose finally to α-alumina. Na⁺⁺ and K⁺-beta;-aluminas transform directly to α-alumina. When NH4⁺- and Ag⁺-β-aluminas decompose at temperatures lower than 950°C, they transform to α-alumina through an intermediate phase with a structure similar to β-alumina (Figs.3, 4and 5)
(2) β-Aluminas containing divalent cations such as Ca²⁺ and Sr²⁺ decompose to α-alumina and magnetoplambite compounds in air atmosphere (Fig.3).
(3) The decomposition temperature of β-alumina is dependent on exchanged cations in [Na-0] layer, and rises in the order K⁺>Na⁺>Ag⁺>NH4⁺ for monovalent cations and Sr²⁺Ca²⁺ for divalent cations.
(4) The decomposition temperature of β-alumina is highly dependent on the firing atmosphere, and becomes higher in air, N₂ and H₂ atmosphere in this order.

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The growth of LaB₆ whiskers from a LaCl₃, -BCl₃-H₂ system was investigated on various materials with reference to their catalytic effects. Copper, Ag, Au, Fe, Co, Ni, Pd, Pt, Si, SiO2, and mullite porecelain were effective for the growth of LaB₆ whisker. The LaB₆ whiskers grew in the temperature range of 1100-1250°C on all the substrates examined. The LaB₆whiskers grew up preferentially in the <100> direction with a square cross-section. An exception was the growth on Fe where the whiskers developed preferentially in the <111>direction with a hexagonal cross-section. Small grobes were observed on the tip of LaB 6whiskers at the initial stage in the growth on Cu and Pt, suggesting that the LaB₆ whiskers on metal agents start to grow by a Vapor-Liquid-Solid mechanism. The growth rate of whiskers showed a maximum against BCl₃ concentration for mullite, Pt and SiO₂. The highest growth rate was ca.2.4 mm/h on Pt. The nucleation and growth of LaB 6 whisker were accelerated in the presence of SiHCl₃ in the reacting gas mixture.

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A number of nickle(II) complexes of three types, NiL₂·2H₂O[a], NiL₂·H₂O[b] and NiL₂[c], were synthesized with 1-(p-substituted phenyl)-1, 3-butanediones (HL, L=p-XC₆H₄COCHCOCH₃, X =NO₂[1], COOH[2], COOCH₃, Br[4], Cl[5], H[6], NHCOCH₃[7], C₂H₅[8], CH₃[9], OCH₃[10] and OH[11]), and their configurations were studied by the magnetic and spectral measurements. The complexes of [1a]-[11a] were monomeric octahedral, and those of [1b]-[11b]and [1c]-[11c](except[7c]) were dimeric and trimeric octahedral in solid state or in chloroform (in which the complexes of [2] and [7] were sparingly soluble and could not be studied), while that of [7c] was square planar in solid state. In pyridine (the complexes of [4]and [7] were sparingly soluble and could not be studied) and in DMSO, the hydrates and anhydrides of all the complexes studied were converted to NiL₂.2 solv (solv=pyridine or DMSO) of the monomeric octahedral configuration. The v1 and v2 bands, observed in solid state, in chloroform, and in DMSO, shifted to the higher frequency side as the substituent becomes more electron donative. The v1 energy parameters, which correspond to the crystal field stabilization energy 10 Dq, indicate that the stability of these complexes increase in the order of [1]<[2]<[3]<[4]<[5]<[6]<[7]<[8]<[9]<[10]<[11].

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Products in an electric discharge of the hydrocarbon-ammonia-water vapor system have been studied previously. In the present experiments qualitative and quantitative analyses of the amino acids, formed when hydrocarbon (methane, ethane, ethylene or acetylene)-ammoniawater vapor-hydrogen sulfide system was submitted to an electric discharge or an ultraviolet (254 nm) irradiation, were investigated. In addition to this system, three experiments on an electric discharge were carried out with hydrocarbon-hydrogen sulfide system, with hydrocarbonammonia-hydrogen sulfide system, and with hydrocarbon-water vapor-hydrogen sulfide system, respectively. In the hydrocarbon-hydrogen sulfide system, the kinds of thiols and sulfides formed by an electric discharge were quite similar, even if any of the above hydrocarbons were chosen as a starting material. Hydrogen sulfide remarkably inhibited the formation of saturated and aromatic hydrocarbons. In the hydrocarbon-ammomia-hydrogen sulfide system and the hydrocarbon-water vapor-hydrogen sulfide system, amines, nitriles and aldehydes were formed by an electric discharge in gas phase. In the hydrocarbon-ammonia-water vapor-hydrogen sulfied system, an electric discharge produced thirteen amino acids and an ultraviolet irradiation produced eight amino acids. Two protein amino acids, containing sulfur, cysteins and methionine, were formed in these experiments. The yield of methionine in methane-ammonia-water, vapor-hydrogen sulfide system was higher than that in the other system.

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In the determination of strontium by atomic absorption spectrometry with a graphite furnace, suppression of strontium atomic absorption by coexisting chloride was observed. The chloride interferences were measured under the various conditions regarding (i) the kinds of chlorides, (ii) the concentration of chloride, (iii) the pH of the sample solutions, (iv) the addition of organic acid, (v) the ashing temperature, and (vi) the flow rate of sheathing gas. Two mechanisms for the chloride interference have been proposed based on the interactions between the chloride and strontium in the sample solutions and in the drying and ashing processes. The first arises from the chloride salts remaining until the atomization step and the interference can be eliminated by volatilizing the chlorides or converting them into other substances such as oxides before atomization. The another arises from the formation of strontium chloride which can be removed by addition of masking reagents. The tetraammonium salt of EDTA is quite suitable as an additive for the purpose because it is able to coordinate to both strontium and coexisting cations.

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Dithizonate (Hdz) and diphenylcarbazonate (Hdpc^-)-chromium(III) complexes were extracted into basic solvent(B) as solvated ion-pairs, CrL(B)₂(A)₂ with counter anion(A^-); where B=butyl acetate, isobutyl methyl ketone, isopentyl alcohol and trioctylphosphine oxide, and A=dodecyl sulfate ion(ds^-). Anions having long chain alkyl groups, such as ds- and dodecylbenzenesulfonate ion, were effective for the extraction of the complexes, but tetraphenylborate ion and naphthalenesulfonate ion could not extract them. Ion-pair extraction constants, K_ex=[CrL (ds^-)₂]. [CrL²⁺]^-1[ds^-]^-2, between water and butyl acetate phase were 10^10.70 and 10^11.07 for L=Hdz^- and Hdpc^-, respectively (at I=-0.1, 20°C). Equilibrium constants, β2, for solvation of the ion-pairs in dichloromethane, β2=[CrL(B)₂(ds^-)₂]₀^-1[B]₀^-2, were evaluated and a linear free energy relationship, log β_{2, Cr(Hdpc)2+}=logβ_{2, Cr(Hdz)2+}+ 0.60, was, demonstrated. The difference in the K_ex values between both chromium(III) complexes was discussed and mainly attributed to the difference in their β2 values.

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The reaction of phenol with various “ketone peroxides”, obtained from ketones and hydrogen peroxide in situ in the presence of acid catalysts, was investigated to obtain such benzenediols as catechol and hydroquinone in high yield. Both aliphatic and aromatic ketones were suitable for this reaction, and acid catalysts such as sulfuric acid, perchloric acid, sulfonic acids, sulfates and a mixture of clay and phosphoric acid were effective. In order to prevent further oxidation of benzenediols, the reaction was carried out using a large excess of phenol with respect to hydrogen peroxide. Since the formation of 2, 2-bis(hydroperoxy)-4-methylpentane was ascertained in the case of the reaction using isobutyl methyl ketone, this compound was considered to act on phenol as a strong oxidizing agent.

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α, β, β-Trifluorostyrene, α, α'-difluorostyrene and 1, 1-difluoro-2, 2-diPheiiyiethylene [1], were synthesized by the gas phase copyrolytic method of reactions. (1), (2) and (3), respectively.

C₆H₅CHClF+CHCIF₂→C₆H₅CF=CF₂+2HCl (1)
2C5H5CHClF→C₆H₅CF=CFC₆H₅+2HCl (2)
(C₆H₅)CHClF+CHCLF₂→(C₆H₅)2C=CF₂+2HCl (3)
The reactions were carried out in the presence of steam by a flow method in a spherical or tubular silica reactor under atmospheric pressure. Reaction temperature(°), total space velocity of gas (h-1 NTP), _ feed gas composition(molar ratio) and the product yield(%, based on the benzylidene chloride fluoride converted) were respectively as follows: for reaction (1), 750, 7966, CHClF₂: C₆H₅CHClF: H₂O=22.3: 2.6: 75.1, 52; reaction (2), 700, 7758, C₆H₅CHClF: N2: H₂O=19.2: 6.2: 74.6, 71; reaction (3), 750, 9030, CHClF₂: (C₆H₅)2CHCl: H 20=29.4: 5.4: 65.2, 18(based on the chlorodiphenylrnethane converted), The presence of excess steam in reactions(1) and (2) caused a considerable suppression of the formations of hydrogen fluoride, high boiling materials and/or by-products. Physical constants observed. for [1], benzylidene chloride fluoride[2], and (1, 2-diboromo-1, 2, 2-trifluoroethyl) benzene[3] Were as follows: [1], bp 91°/3 Torr, mp -18-16°, d₂O4 1.1547, n20D 1.5621; [2], bp 171.5°/760Torr, d₄ 1.185, n_D 1.5162; [3], bp 81-2°/8 Torr, d₂O4 1.8884, n_D1.5241.

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Solubility parameter of quaternary ammonium and phosphonium saIts, which are used as phase-transfer catalysts, has been measured by means of the gas chromatographic technique. The values of solubility parameter (δ) obtained fell in the range 8-19 cal 1/2. cm^-8/2 at 100°. Six out of 13 quaternary salts examined had the values of δ in the range 12-15 cal1/2. cm^-3/2and were found to be effective as a phase-transfer catalyst for two phase reactions. Equation, D(δ)=(δ-δw)²/(δ-δo)² is proposed to evaluate the hydrophile vs. lipophile balance of phase-transfer catalysts, where δ, δw and δO are the solubility parameters of phase-transfer catalyst, water and nonpolar organic solvent, respectively. The values of D(δ) calculated for phasetransfer catalysts in the benzene-water system were well correlated with their catalytic effects previously reported. The results showed that the values of δ and D(δ) were useful for the estimation of distribution of a phase-transfer catalyst between water and nonpolar organic solvents.

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The templet condensation of N-acetonylidene-N'-(o-aminophenyl) hydrazine (o-NH2C6H4. NHN=CHCOCH3) in the presence of nickel acetate in the mixed solvent of pyridine and ethanol (1: 10) yielded a new macrocyclic nickel complex([6, 15-dimethy1-5, 8, 9, 14, 17, 18-hexaazadibenzo[a, h]cyclotetradecene]nickel(II)) [2]. Central nickel of [2] could not be removed by following the treatments which were employed for the demetalation of the tetraaza-analogue of [2] ([6, 8, 15, 17-tetramethyl-5, 9, 14, 18-tetraazadibenzo[a, h]cyclotetradecene]nickel(II)): (i) suspending [2] in 7% HCl-ethanol and (ii) dissolving [2] in conc. sulfuric acid. Sulfonation of [2] in conc. sulfuric acid and in 20% oleum afforded mono-[2a] and disulfonic acid[2b], respectively. [2a] and [2b] dyed fibers of wool, silk, and nylon dark green shade. The fastnesses of the dyeings against washing and light were 5 and2-3, respectively.

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Polyelectrolyte complexes (PEC) were prepared by mixing the mixture of sodium dextran sulfate (DS) and (carboxymethyl)dextran (CMD) with [2-(diethylamino)ethyl]dextran hydrochloride (EA) in different order of mixing at various hydrogen ion concentrations. The molar ratios of SJI\T which describe the molar ratios of OSO₃, (DS)/N (EA) in each PEC thus prepared were estimated to be 0.29-1.21, and the content of CMD in the PEC formed at higher hydrogen ion concentrations was found to be less than that formed at lower hydrogen ion concentration (pH 11.0>6.5>2.0>1% HCl>4% HCl). The results of IR spectra, elemental analyses, the colorimetric reaction with Toluidine Blue, degree of swelling for water and solubity indicated that the structure and property of the PEC varied as the experimental conditions were changed. The molecular conformation and composition of the PEC differ from those obtained from CMC, PVSK and chitosan. It was suggested that the degree of dissociation and conformation of EA, CMD, DS change with hydrogen ion concentration; and that the intermolecular hydrogen bonds between the OH groups in the PEC break at above the hydrogen ion concentration of pH 2.0 to from the bonds between OSO₃H and OH groups.

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In order to obtain reactive ultraviolet absorbers with excellent fastness for washing, 2-iso-propenyl5-methyl-1, 3, 4-oxadiazole and 2 -isopropenylbenzoxazole were prepared and grafted onto cotton fibers by Pad-Cure method. The effect of grafting of the ultraviolet absorbing monomers on the photodegradation of cotton fibers was examined by changing the tensil strength. It was found that the decrease in the tensil strength of the grafted cotton fibers was remarkably retarded, and the protective effect was increased with the increase of grafting of the monomers.

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Sixteen samples of rain water were collected in constant volume sampling, 50 ml per 0.5 mm rainfall in Kobe area in 1976-1977, and NO₃^-, NO₂^- (162 samples) and other contaminants in the water were determined and compared with the concentrations of atmospheric pollutants, SOx, NOx and particulate NO₃-, and with meteorological conditions during the rainfall periods. The average concentrations of NO₃^--N and NO₂^--N in the water were 0.296 and 0.0095 ug/ml and the concentration of NO₃^--N gradually decreased with an increase in the amount of rainfall, whereas that of NO₂--N did not decrease. During the rainfall, NO in the ambient air increased apparently and particulate NO₃^- decreased rapidly. These results show that the total average ratio of NO₃^--N/NO₂^--N in rain water was 37.7 (118.6 in first fraction of rain)and was higher than the values previously reported (about 10). The NO₃^--N/NO₂^--N ratio increased with a decrease in pH, and suggested that the disproportionation reaction (N04-NO₂-NO₃^-) occurred in rain water, depending mainly on pH. It seems that NO₂^- in the rain water is formed primarily by the uptake of NO from ambient air, whereas NO₃^- is resulted from several processes, i. e. uptake of NO₂, HNO₃ and particulate NO₃^- from air, and oxidation of NO₂^- in rain water.

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The authers investigated in which part of lecithin molecule, hydrophillic or hydrophobic part, copper-chlorophyll (Cu-chl) molecule interacts with it in the lecithin liposome-Cu-chl system. The longitudinal relaxation time (T₁) of water protons in the lecithin liposome system containing Cu-chi was measured by NMR. Increase in the reciprocal of T₁ was found to be linearly proportional to the amount of Cu-chi dispersed in the liposome. And this value equaled that of T₁ of copper chlorophyllin aqueous solution system. Furthermore the existence of the lecithin-Cu-chl complex was shown from measurement of the NMR spectra of lecithin-Cu-chl-CDCl₃ system. These results suggest that in the lecithin-Cu-chl complexes the porphyrin ring lies near protons of an N-methyl and apart from the neighbouring methylene and the end methyl group in that order, that is, exists in the hydrophillic part of the lecithin molecule.

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Fractional precipitation of metals in a artificial sulfuric acid leaching solution of manganese nodules has been carried out by using the calcarous deep-sea sediments of Pacific Ocean. The sediments were dredged at 170°50'(west longitude) and 10°18' (north latitude), and contained 93. 6% calcium carbonate. They were added little at a time into the artificial solution containing Fe(a) 5, Al 5, Cu 2, Ni 2, Co 2 and Mn 1 gii, at 30 and 90°C. The metal ions in the solution were precipitated in the order of Fe(III), Al, Cu, Ni, Co and Mn with the increase of pH of the solution. At pH 3. 0 and 90°C, 98. 2% Fe(II) and 20. 9% Al ions were removed from the leach. It was found that the sediments were more reactive than powdered limestone.

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The reaction of o-acetylbenzophenone[1] with phenylhydrazine hydrochloride gave 1-anilino5, 5'-diphenyl-3, 4: 3', 4'-dibenzo-2, 2'-dipyrromethene[3c] as a main blue pigment. On the other hand, [3] reacted with methyl- or benzylamine in the pregence of 1-hydroxy-3methyl-1-pheny1-1 H-isoindole[5] to give three deep blue pigments, [3d], [4] and [2d] or [3e], [4] and [2e], respectively. The structures of [3d], [3e] and [4] were found to be analogous to that of [3c]. Phenylhydrazine hydrochloride and S-methyl-L-cysteine which gave [3] when reacted with [1] liberated ammonia in the absence of [1] under conditions similar to those of pigment formations. On the basis of these experiments a mechanism for the formation of [3] is proposed as shown in Scheme 1.

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The title disproportionation originally reported by MgrAdi (Chem. Ber., 85, 104(1952)) has been reinvestigated under a variety of conditions using infrared and 'H-NMR spectroscopy. The claimed conversion of 5-chloro-7-iodo-8-quinolinol [1] to 5, 7-dichloro- [3] and -diiodo-8-quinolinols [5] could not be reproduced. On prolonged heating in acetic acid under reflux, however, 5-bromo-7-iodo-8-quinolinol [2] suffered a partial protodeiodination to give 5-bromo8-quinolinol [8], which then underwent a slow disproportionation to form 5, 7-dibromo-8quinolinol [4] Neither in this case C5J could be obtained. Acid hydrolysis of 7-bromo-8hydroxyquinoline-5-sulfonic acid [10] was found to give [8] by the facile migration of the bromine atom.

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Aqueous solution of phenol was allowed to react with molecular oxygen at a pressure less than 2.1 MPa, in the presence of copper (II) sulfate (280 and 560 mg/l as Cu²⁺) and at 130-220°C. The extent of decomposition of phenol at below 2.1 MPa was more than 95% upon heating it for 70 minutes at above 180°C. After the treatment, a transparent solution was obtained. The extent of decomposition at 1.1 MPa and above 180°C showed a tendency to decrease with increasing temperature because phenol probably reacted with oxygen in a gas phase. Phenol did not appreciably reacted in air at 2.1 MPa and above ca.200°C; the extent of decomposition was about 60%. The COD_mn values of the solution after the treatment were also measured.

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