The behavior of an oily liquid material on a substrate of low energy surface has been studied from a stand point of surface chemistry. A sheet of polypropylene was used for making of low energy surface. Saturated fatty alcohols of C, to C₁₄, fatty acids of C₆ to C₁₁ and normal paraffins of C₁₁ to C₁₄ were used as oily liquid materials. The contact angle of an oil droplet on a substrate, surface tension of an oil and interfacial tension of an oil/water interface have been measured.
Experimental results showed that in air fatty alcohols showed behavior similar to that of fatty acids and that in water fatty alcohols behaved different from fatty acids. It is suggested that in water different polar groups of an oily material such as hydroxyl and carboxyl groups behave different from those of a fatty acid.
Contribution of dispersion and polar force components of surface tension of various oily materials were studied with measurements of contact angle and interfacial tension. Results showed that the dispersion force components of surface tension increased with increasing chain length of carbon of alkyl groups of oily materials and that the polar components were kept constant for more than six carbon chain length. The energy of interaction between polypropylene surface and oily materials has also been calculated.

View full abstract

Colloidal and interfacial behaviors of silver soaps have been investigated in organic liquids in a temperature range 50-150°C. When silver soaps were heated in vegitable oils various kinds of silver sols were obtained. Increase of iodine values of the oils lowered the temperature of formation of the sols and increased their stability. In refined liquid paraffin or nonpolar hydrocarbons, almost noreaction was observed at temperatures below 130°C, whereas in air oxidized liquid paraffin with -00H, -OH and=CO groups very stable sols were formed. In normal saturated alcohols, silver mirror appeared on glass or polar solid surfaces after f ormation of silver sol. Duration of the sol state increased with increasing carbon chain length of the soaps. In saturated fatty acids neither silver sol nor silver mirror was observed. However, in unsaturated acids with a long carbon chain such as the chain of oleic acid stable sols were obtained.
These experimental results suggest that (1) silver organosols are formed within reversed micelles of the silver soaps in polar media and that the sols are (2) stabilized by carboxylic radicals or polar molecules with long carbon chain.

View full abstract

The adsorption of SO₂ and NO on iron(III) hydroxide oxides (a-FeOOH, 1-Fe0OH, and r-Fe0OH) from mixed gases with H₂O, 0₂, and CO₂ of various compositions at 100°C has been determined by a flow method in order to elucidate the effects of coexisting gases on SO₂ and NO adsorption. The SO₂ adsorption was reduced by the coexisting CO₂, H₂0, and O₂ the amount of SO₂ adsorbed, for instance, from the gas composed of 1% S0₂-10% H₂O-5% O₂-10% CO₂-balance N₂ was 65-78% of that from the gas containing 1% SO₂-balance N2 (Table 1). In particular, CO₂ decreased the SO₂ adsorption on all kinds of the Fe0OH polymorphs tested, whereas H₂0 and O₂ did not considerably affect the SO₂ adsorption. The amount of NO adsorbed from a gas composed of 300 ppm NO-500 ppm S0₂-10% H₂O- 10% CO₂-1% O₂-balance N₂ was 9-13% of that from 300 ppm NO-balance N, (Table 2), showing that NO adsorption was strongly influenced by the coexisting gases. The NO adsorp- tion was apparently increased by the removal of H₂O and SO₂. CO, , did not affect the NO adsorbability of a-FeOOH. The influence of the coexisting gases on the NO adsorption was more obvious for T-Fe0OH than for a- and 8-Fe00H. The effects of coexisting gases were discussed in view of the surface structure of each FeOOH crystal and adsorption sites on the surface.

View full abstract

Active sites of nickel oxide for hydrogenation and isomerization of olefins formed by decomposition of nickel compounds in vacuo were studied with four differently prepared nickel catalysts.
The active sites are classified into three types (S_I, S_II, and S_III) according to the magnitude of specific activity per fatal dose of carbon monoxide. S_I is about 10³ times more active than sill for hydrogenation of ethylene, and S_II is about 10² times more active than Sin for both reactions. The S_III sites are found on nickel oxide prepared by air calcination of nickel nitrate and also on a sample prepared by vacuum decomposition of nickel hydroxide precipitated with ammonia. The Si sites are obtained on a sample prepared by precipitation with urea followed by vacuum decomposition at 450°C and the S_II sites are found on samples prepared from nickel carbonate and from the urea-precipitated hydroxide. The S_I site is considered to be a finely devided nickel metal specifically formed on urea-prepared sample, because a slight reduction with hydrogen reproduces an identical activity specifically on this sample, accompanied by the appearance of an ESR signal characteristic of ferromagnetic substance. The ASH site is considered to be a low valent nickel ion formed by removal of carbon dioxide.
In this way, it is shown that a highly active nickel oxide catalyst can be obtained by selecting the method of preparation.

View full abstract

The formation of ozone under silent discharge was investigated by changing an applied voltage under pressure of 1.0 to 1.7 kg/cm², discharge gaps of 1.4 to 2.4 mm, and gas flow velocities of 1.0 to 4/min by use of the electrodes coated with twenty kinds of metal oxide.
The results are as follows: (1) Both the yield of ozone and efficiency of its formation increased up to 20% by coating the electrode with iron (II) iron (III) or germanium oxide. (2) Coating with copper (II), nickel, or galium oxide showed negative effect. (3) In (1) and (2), the yield of ozone and efficiency of its formation were scarcely influenced by the reaction conditions (e.g., applied voltage, pressure, gas flow velocity, or discharge gap).
Therefore, the electrodes, whose surfaces being coated with metal oxides increased the efficiency of the formation of ozone.

View full abstract

The complexes, R₃NHVO(OH)Cl₂, R₂R'NVO(OH)Cl₂ and (R₃R'N)₂[VO(NCS)₂]H₂O, isolated from the organic phase after the extraction of vanadium(IV) in aqueous hydrochloric acid and thiocyanate solutions by benzene solutions of trioctylamine (R₃N) and tricaprylmethylam- monium chloride (R₃R'NCl), have been examined by the measurements of apparent molecular weights and magnetic moments, infrared and electronic spectrophotometry and electron spin resonance (ESR) spectroscopy. Simulated ESR spectra, calculated with the values given in Table 1, assuming axial symmetrical spin Hamiltonian with S=1/2, are in good agreement with experimental ones (Figs.1-3). In addition the observed values of the magnetic moments for the complexes R. NHVO.(OH)Cl₂ and R₃R'NVO(OH)Cl₂ (Table 2) are smaller than the spin-only value for vanadium 00, 1.73 B. M., implying that there are some spin-spin interactions. However, the value for the species (R₃R'N)₂[VO(NCS)₄] H₂O is analogous to the spin-only one. These facts also agree with their apparent molecular weights. Hence it is concluded that the former complexes exist as dimers, while the latter one is monomer, and the ESR spectra of those dimeric complexes are interpreted by assuming that the spin-spin interaction is not so much anisotropic. Furthermore the molecular parameters, estimated from the spectrophotometric and ESR data (Table 1, 3), suggest that the in-plane a bonding and out-of-plane π bonding are covalent in all complexes.

View full abstract

Mischmetal(Mm)-nickel-cobalt alloys MmNi_5-xCox (x =1.0-4.0) have been found to have the same hexagonal structure as those of LaNi₅ and MmNi₅. They react readily with hydrogen to form hydrides of MmNi_4.0Co_4.0, H_6.3, MmNi_3.0Co_2.0H_6.3, MmNi_2.5Co_2.5H_5.2, MmNi_5-xCo_2.5H_5.0 and MmNi_1.0Co_4.0H_3.3 (hydrogen content: 1.4, 1.4, 1.2, 1.1 and O.8wt%) under 60 atm hydrogen pressure at room temperature. Dissociation pressures of these hydrides are dependent on the content of cobalt, which substitutes partially for nickel, and log p decreases gradually with increasing content of cobalt. An enthalpy change -8.4 kcal/mol H₂ in the hydride formation is given for MmNi_2.5Co_2.5, and the dissociation pressure at 30°C yields 3.0 atm. The absorption rate of hydrogen for MmNi_5-x (x= 1.0-4.0) is getting lower than that for MmNi5 with increasing x, while the desorption rate of hydrogen remains constant when taking x→1. O. For MmNi_2.5Co_2.5 the hydrogen absorption-desorption cycles are repeated 30 times, but the variation in the hydrogen absorption-desorption ability has hardly been noticed. Mm_0.5Ca_2.5Ni_2.5Co_2.5 reacts with hydrogen to form the hydride of Mm_0.5Cao.0Ni_2.5Co_2.5H_4.5 (hydrogen content: 1.1 wt%). The enthalpy change -8.3 kcal/mol H₂ in the hydride formation is obtained, and the dissociation pressure of hydride at 30°C yields 3.8 atm. The hydrides of MmNi_2.5Co_2.5 and Mm_0.5Ca_0.5Ni_2.5Co_2.0 suited as a stationary hydrogen storage material.

View full abstract

The solid solution in the germanium fluor-phlogopite (KMg₃AlGe₃, O₁₀F₂)-fluor-tetragermanic mica (KMg_2.5Ge₄, O₁₀F₂) system has been synthesized by the melting method and the resultant solid solution has been investigated by X-ray powder technique and infrared spectra. Furthermore, refractive index, density, and thermal expansion of the solid solution have been examined.
The results are summarized as follows: (1) With increasing amount of fluor-tetragermanic mica (T-G-M) in the solid solution, the cell dimension of the solid solution increases linearly. This result agrees with Vegard's rule. It indicates that all compositions between germanium fluor-phlogopite and fluor-tetragermanic mica form complete and continuous solid solution (KMg_2.5+0.5xAl_xG_4-xO₁₀F₂, 0×2). (2) The rates of change in spacings of planes among the end compositions are 0.23, 0.22, and O.38% in the directions of a, b, and c^* axes, respectively. In the direction of c^* axis it changes remarkably. (3) Most of absorption bands in the IR spectrum of the solid solution are assigned to Ge-O vibrations. With decreasing amount of fluor-tetragermanic mica (T-G-M) in the solid solution, the new band is clearly observed near 615 cm^-1 and it becomes gradually strong. This band is considered to be due to Al-O-Ge vibration. (4) With increasing amount of T-G-M in the solid solution, the refractive index and density of the solid solution increase linearly with molar composition. (5) With increasing amount of T-G-M in the solid solution, the thermal expansions in each axial direction of the solid solution increase continuously.

View full abstract

Rhabdophane hexagonal form Ce_1-x, Y_xPO₄nH₂O (n=0. 5-1) was synthesized by precipitation from the mixed solution of CeCl, YCl₃ and H₃PO₄ (or orthophosphate) above 20°C. The amount of substitution of Y for Ce was in the range 0<x<0.22. Crystalline rhabdophane was detected in the precipitate obtained from the mixed solution at pH 1-3. The minute crystals showed needle-like shape. Amorphous precipitate was obtained at higher pH than 3. At the pH below 1, precipitation was not proceeded at 20°C. Rhabdophane was found to have zeolitic water. The amount of water increased from n=0.5 to 1 with increasing Y contents. The zeolitic water was dehydrated in the temperature range 190-225°C in air. Anhydrous Ce_1-x, Y_xPO₄ transformed from a hexagonal into a monoclinic form at above 500°C. This transformation was monotropic and sluggish. The monoclinic form Ce_1-x, Y_x PO₄ was the same as the mineral monazite.

View full abstract

11-Arylbenzo[a]fluoren-11-ols [2] 11- (o-methylphenyl) -[2a], 11- (m-methylphenyl) -[2b], 11- (p-methylphenyl) -[2c] and 11- (2-methyl-1-naphthyl) benzo [a] fluoren-11-ol [2d] were synthesized by reaction of benzo[a]fluorenone [1] with a variety of arylmagnesium bromides or aryllithiums. Reduction of [2] with HI in acetic acid gave the corresponding 11-arylbenzo [a]fluorenes [3]. Both rotational isomers, ap-form of [2d] and 11 R, sc (or 11 S, + sc)- form of 11- (2-methyl-1-naphthyl) benzo[a]fluorene (3d) were isolated as stable crystals at room temperature.
The rotational barriers (δG) around the C_5P3-C_SP2 single bond in 11- (p-methylphenyl) benzo [a]fluorene [3a] were determined by means of the DNMR method R, sc (or 11 S, + sc)→11R, +ac (or 11S, ac) δG₁₄₀°C=19.7kcal/mol=19.4 kcal/mol, 11 R, +ac, 11 R, sc: δG₁₄₀°C=19.7 kcal/mol. Furthermore, the rates of isomerization for the process of [2d]ap→[2d]sp and [3d]+11R, ac (or [3d]11S, +sc)[3d] 11 R, +ac (or [3d] 11 S, ac) were measured at various temperatures on their NMR spectra, and the free energy values of activation for each process were obtained as δG₁₄₀°C=19.7kcal/mol=24.6 kcal/mol and δG₅₀°C=32.8kcal/mol=, respectively.

View full abstract

The Claisen rearrangement of allyl [o(or p)-substituted 1 phenyl] ethers was carried out in the presence of various solvents, and effect of the solvent on the rate of the rearrangement was investigated. No correlation was found between electron donating ability or basicity of solvents and the rate of the rearrangement. The rate acceleration effect obtained in the presence of aniline derivatives as a solvent was found to be proportional mainly to the sum of the dipole moment and hydrogen bonding ability of the solvents.

View full abstract

The reaction of isobutyraldehyde (IBA) with 1-buten-3-one (MVK) catalyzed by tributylphosphine (TBP) yielded 2, 2-dimethyl-5-oxohexanal [1] in 70% yield.4, 4-Dimethy1-2-cyclohexen-1-one [2], 4, 4-dimethy1-6- (2-me thylpropylidene) -2-cyclohexen-1-one [3]and 3-hydroxy-4, 4-dimethyl-1-cyclohexanone [4] were also formed as by-products. The reaction of dialkylacetaldehydes with MVK yielded 2, 2-dialkyl-5-oxohexanal [6]. The reaction of IBA with other vinyl compounds such as acrylonitrile, 1-penten-3-one, methyl acrylate promoted by TBP has also been examined. Trioctylphosphine was also found to be effective as a catalyst for the Michael type addition of IBA to MVK.
The results indicate that the Michael type addition involves formation of the phosphonium betaine intermediate_

View full abstract

A new basic optical resolving reagent is proposed. Optically active cis-N-benzy1-2-(hydroxymethyl) cyclohexylamine [2] was obtained by reduction of optically active cis-2-(benzamido)cyclohexanecarboxylic acid [1]which was prepared by preferential crystallization of its benzylamine salt. A number of racemic carboxylic acids, such as (±)-malic acid [3], (±)-a-methoxyphenylacetic acid [4], (±)-a-phenylpropionic acid [5], (±)-trans-2-phenylcyclohexanecarboxylic acid [6], (±)-trans-1, 2-cyclohexanedicarboxylic acid [7], and (±)-a-ureido-a-(2-thienyl) acetic acid [8] have been resolved by fractional crystallization of their diastereomeric salts with [2].

View full abstract

Phenolic sesquiterpene elvirol, isolated from Elvira biflora (Compositae), was synthesized through a new synthetic route and was converted to dimethylisopropylnaphthalene.4- (2-Methoxy-5-methylbenzoyl) butyric acid, obtained from p-methylanisole by the Friedel-Crafts reaction with glutaric anhydride, yielded methyl 5- (2-methoxy-5-methylphenyl) hexanoate 13 13 in 3 steps.2-Methyl-6- (2-methoxy-5-methylpheny1)-2-heptene [5b] was obtained from [3b] by the Grignard reaction followed by dehydration. Elvirol, 2-(1, 5-dimethy1- 4-hexeny1)-4-methylphenol, [5a] was prepared by demethylation of [5b] with boron tribro- mide.
By heating with hydrobromic acid [5b] was cyclized to yield 4, 5-dimethyl-8-isopropyl-5, 6, 7, 8-tetrahydro-1-naphthol [9a], which gave 3, 4-dihydro-4, 5-dimethy1-8-isopropyl-1 (2H) - naphthalenone [10b] by heating with palladium-charcoal catalyst. Reduction of [10b] followed by heating with sulfur afforded 1, 8-dimethyl-4-isopropylnaphthalene (8b). The reaction of [5b] with other acid catalysts was also studied.
In order to identify the new hydrocarbon [8b], it was independently synthesized from pcymene. Similarly, 1, 5-dimethyl-4-isopropylnaphthalene [8a] and 1, 5, 8-trimethy1-4-isopropylnaphthalene [8c] were also synthesized. The hydrocarbons [8a] and [8b] solidified to show the melting points of 31-32°C and 32.5-33.5°C, respectively. The picrates of [8b] and [8c] had the wide melting point ranges.

View full abstract

Optically active trans-1, 2-cyclohexanedicarboxylic acid [1] obtained by preferential crystallization was converted into corresponding acid anhydride [2]. The reaction of (2) with DLamino acid such as DL-alanine [3a], DL-a-aminobutyric acid [3 b], DL-valine [3c], DL-phenylglycine [3d], and DL-methionine [3 e] gave respective diastereomeric amides [4]. Fractional crystallization and subsequent hydrolysis of [4] gave ID- and L-amino acids.

View full abstract

The structure and distribution of silicate ions in some faujasite type zeolites (Si/AIratio:1.20-2.65) were studied by the aid of the trimethylsilylation method. Zeolites having small values of Si/AI ratio (>1.90) consist mainly of orthosilicate and polysilicate ions which have average degree of polymerization of 9.3-17.0. On the other hand, zeolites having large value of the Si/AI ratio (<1.90) consist mainly of insoluble polysilicic acids which have three dimensional network.
Moreover, computer simulation of the aluminosilicate frameworks of these zeolites was tried using a faujasite model, and the orderness of Si and AI atoms constructing the frameworks was discussed. Mixing rate of Al ions into T1 site was found to increase with the Si/AI ratio.

View full abstract

Investigation on the thermal degradation of mixed polymers was carried out making use of the differential thermogravimetric method and the continuous flow reactor, which was the same as that used for the thermal degradation of polyethylene, polypropylene, and polystyrene in the preceding studies. In the present study, two or three of these polymers were mixed with together to obtain the mixed samples to be decomposed. Assuming a negligible mixing effect on the decomposition rate, a harmonic mean relationship exists between the decomposition rate of a mixed polymer and the individual rates of its constituent polymers for the continuous flow reactor.
As shown in Figs.6-10, close agreements are obtained between the observed rates of mixed polymers and the harmonic means of the individual rates of their constituent polymers, despite the DTG curves of the mixed polymers (Figs.1-5) demonstrate the mixing effect on the volatilization. Any particular products were not found for mixed polymers on a gaschromatographic analysis. Figs.11-14 show that the carbon number distributions of the mixed polymers are made by superimposing of the carbon number distributions of individual products of the constituent polymers.
The results of differential thermogravimetric and gaschromatographic analyses suggest that the mixing of polymers influences on the decomposition rate but not on the intramolecular reaction. Based on the results, the mixing effect on the decomposition rate is interpreted in term of a intermolecular radical transfer between different polymers.

View full abstract

An activated carbon was prepared from residual carbon in tires pyrolyzed at 500°C for 30 min. The rubber of the tires used in this study had a composition of NR 80, SBR 20 and carbon black (HAF) 45 in weight respectively. The residual carbon was ground to a fine powder and granulated to particles in a size of 3.5-16 mesh. The sulfite pulp waste liquor was used as the binder. The activation of the granulated carbon was carried out in a stream of CO, gas at the temperatures of 800-900°C. The vertical activation reactor was made of a quartz glass tube, 400 mm in length, 40 mm i.d. It was observed that the reaction was apparently zero order with respect to the weight of carbon. The apparent activation energy was estimated to be 23 kcal/mol.
In order to investigate the properties of activated carbons prepared above, the adsorbability for Methylene Blue and benzene, the specific surface area, the pore size distribution and the compressive breaking strength were determined. It was clearly observed that the activated carbons obtained in this study had a particular feature in the pore size distribution. All of the activated carbons had a narrow pore size distribution centering at around 250å in radius. However, no considerable development of pores less than 100å in radius was observed. The mechanism of the activation has been discussed.

View full abstract

The adsorption of uranium from sea water by titanium (N) cellulose-xanthate or titanium (IV) starch-xanthate was investigated.
(1) The adsorption of uranium by the above adsorbents was rapid as shown in Figs.1 and 2.(2) The percentage of uranium adsorbed increased gradually with increasing amount of adsorbent (Figs.3 and 4). (3) The amount of uranium adsorbed was constant from sea water, whose pH values being 4, -8 (Fig.6). (4) When 1 gram of the adsorbent was suspended in 5 liters of natural sea water with constant stirring at 30°C for 3 days, 76.6% of uranium in sea water was recovered by titanium (AT) cellulose-xanthate and the adsorption of uranium was rapid during the first 1 day (Fig.9); while the percentage of uranium adsorbed by titanium (W) starch-xanthate was 77.9%.
These studies showed that the above titanium(N) polysaccharide-xanthates have the ability to adsorb a large amount of uranium from sea water.

View full abstract

Single crystals of MSb₂O₄ (M=Mn, Fe, Co, Ni and Zn) were hydrothermally synthesized. They have been found to be isomorphous, and precession photographs revealed that they belong to the space group of P 4₂/mbc or P4₂. X-ray powder diffraction pattern of FeSb₂O₄ is similar to that of natural schafarzikite. Density and chemical analysis data of the synthetic FeSb₂O₄ are different from those of natural schafarzikite reported by L. Tokody, whereas they are in accordance with the theoretical values based on the crystal structure analysis of natural schafarzikite. The DTA and TG of above compounds show exothermic peak and weight increase due to the change from MSb₂O₄ to MSb₂O₆ at a temperature range from 490 to 630°C.

View full abstract

Fading phenomena of a solution of bikel- (dimethylamino)dithiobenzinnickel (0) complex in 1, 2-dichloroethane were investigated in the presence of tetrahydrofuran as a radical generator. The decoloration proceeded as the first order reaction with respect to the concentration of the nickel complex and a half order with respect to the concentration of tetrahydrofuran. Effects of some antioxidants on the fading rates were also examined.

View full abstract

2, 3-Dihydro-1 14-benz ddisoquinoline [3] (58%) and 2, 3, 3 a, 4, 5, 6-hexahydro-1 H-benz-[de]isoquinoline [4] (69%) were formed and isolated as the corresponding hydrochlorides when 1, 8-naphthalenedicarboximide [1] was hydrogenated over the rhenium-black catalyst under hydrogen (125kg/cm²) at 200°C for 30 hr and at 225°C for 40 hr, respectively.

View full abstract

Previously reported data on the efficiency of removal of nitrogen monoxide and formaldehyde by magnesium peroxide (MgO₂/nH₂O, n=0.5) suggested that the hydrated water contained in peroxides plays a role for the removal reaction. In this study, basic research was made about the effects of hydrated water on removal efficiency, being apart from the engineering object to remove pollutants from an air. Commercially available hydrated strontium peroxide (SrO₂.8H₂O) was used as an absorbent, and its efficiency to remove nitrogen monoxide and formaldehyde was measured at various relative humidities; the following results were obtained: Peroxides of alkaline earth metals react with water vapor in the sample gas, to release atomic oxygen, but when hydrated water is present in the peroxide it serves as a substitute for the water in the sample gas. Therefore, when a hydrated peroxide is used for oxidative removal of pollutants, the sample gas is not in need of water vapor.

View full abstract