Solubilities of Biuret have been measured in aqueous solutions of guanidinium and alkali metal salts at 25°C. The salting coedents(k₈)and the self-interaction coefficients(k₂) have been determined by plotting of the quantity{log(S₂⁰/S₂)}/C_a against(S₂-S₂⁰)/C_B, as shown in Figs.3 and 4.As shown in Table 1, the experimentally observed values of k₈ and k₂ were well accounted for by a modified Scaled Particle Theory by using of the values of 801K and 807K for the interaction parameters of the Biuret(ε₂/k)and the guanidinium ion(ε₃/k), respectively. The salting-in effects in the presence of various salts are caused by a large contribution from the negative values of interaction free energy terms.As shown in Fig.6, the k₈ values of the Biuret are closely related to the viscosity B-coefficients of the aqueous solutions of salts except lithium chloride so1ution, indicating that changes in the structure of water due to the addition of salts play an important role on the dissolution of Biuret.This structural effect was more significant for urea and guanidinium salts than for alkali metal salts.

View full abstract

Photochemical formation of silver hydrosols has been investigated by means of absorption spectrum, electron microscopy, and electron diffraction. In silver nitrate solutions containing various polymers or sodium dodecyl sulfate, silver sols were formed photochemically in the presence of chloride ion. It was assumed that photosensitive materials were colloidal silver chloride particles and that polymer or sodium dodecyl sulfate played a role of protector against colloidal silver particles.
In the mixtures of silver nitrate and polymers containing carboxyl groups, silver sols were formed photochemically in the absence of chloride ion, and then dark reaction succeeded. In this case, the formation of certain aggregates upon addition of silver ion to the solutions of polymers was confirmed by their viscosity and light scattering. In addition, silver carboxylate groups were found to take part in the photochemical reaction by their infrared absorption spectrurn. Consequently, photosensitive materials were assumed to be aggregates, e.g., micelles, of silver carboxylate groups.

View full abstract

Changes in activity of the catalyst caused by irradiation of neutron were studied by the hy-drogenation reaction of acetone. Residues such as aluminium and sodium in the catalyst, which might have an effect on the activity, were examined with radioactive analysis and electron spectroscopy for chemical analysis (ESCA). The activity of the catalyst increased a little by an irradiation of 7.0x¹⁷g/cm² of fast neutron on the catalyst, and decreased to 4.3% of the original value when it was sintered at 650°C for one hour in hydrogen atmosphere. The activity of the sintered catalyst was recovered to 15% of the original activity, about 3.5 times as mach as the activity of the sintered catalyst, by irradiation of neutron on it. On the other hand, residues in Raney nickel (1.26x^-3g/cm²·cat.) on a nickel plate were found to contain 1.02x^-4g/cm²·cat. of aluminium, mainly as aluminium oxide, and 8.4x^-8g/cm²·cat. of sodium. These substances were distributed inhomogeneously throughout the catalyst. Further, it was found that the quantity and distribution of the residues in the catalyst were little changed by sintering and by irradiation. These results suggst that the active centers for acetone hydrogenation seem to be formed not by the residues, but by lattice defects on the surface of the catalyst, which were vanished by sintering and generated by radiation damage.

View full abstract

The surface treatments of fibrous gypsum, i. e. needle-like crystal of αC_aSO₄4·1/2 H_2aO with various carboxylic acids and amines were studied. The reactions proceeded most effectively when acids or amines were added to gypsum immediately after the heat treatment (of gypsum) under vacuum (Table 1). The IR spectra (Figs. 3, 4) togather with the thermogravimetric analysis (Fig. 2) showed that the surface products with carboxylic acids and amines decomposed at 300-500°C and at 200-300°C, respectively. Adsorptions of water and hexane on gypsum before and after the treatment with butyric acid or butylamine, indicated that the surface reacted with acid was hydrophilic and organophobic in nature, while the surface reacted with amine was organophilic and hydrophobic (Figs. 5, 6). The configuration of the surface product is discussed on the basis of the IR spectra.

View full abstract

Aqueous suspensions, prepared by mixing solutions of FeSO₄, Na₂SnO₃ NaOH and NaNO₃, were subjected to aging at 70±0.5°C in order to form ferromagnetic precipitates. The precipitates thus obtained were examined by means of X-ray powder diffraction, chemical analysis and ⁵⁷Fe and ¹¹⁹Sn Mössbauer measurements. In alkaline suspensions, the hydroxides of Sn (IV) and Fe (II) ions are oxidized to the ferromagnetic and black particles with the spinel structure by selecting the concentrations of each metal ion and of excess NaOH in the suspension. The lattice constant of the particles of Fe_1-xSn_x0_4/3, increases with the increase of x reaching the value of 8.50Å at x=0.110. The ¹¹⁹Sn Mössbauer spectra of the Fe_1-xSn_x0_4/3 particles with x=0.045 indicate that all Sn (IV) ions exist at B sites in the spinel lattice.A further increase in X (x>0.110) results in the presence of nonferromagnetic particles of FeSnO(OH)₅ besides the ferromagnetic ones in the product.

View full abstract

Samarskite, a mineral consisting of rare-earth element, niobium (tantalum) and oxygen, contains such minor but essential elements as uranium, etc. As it is mostly in a metamict state due to its radioactivity its chemical formula and crystal structure are not yet established. A tentative chemical formula and a probable crystal structure of samarskite were proposed on the basis of hitherto reported data and some crystallochemical informations about related minerals. ( 1 ) The chemical formula was expressed as AB₂0₆(A =R. E., U, Ca, etc. ; B=N11; Ta, Fe, Ti, etc.) which was also expressed as AB0₄ depending upon the distribution of the componentelements among A and B sites. ( 2 ) The crystal structure of samarskite is based on α-PbO₂ structure, and is closely related to the structural group containing such ordered type as columbite, wolframite, and α-PbO₂, except a disordered type of distribution among A and B sites. Attempts to synthesize samarskite, having a similar strcture to that of a natural samarskite heated at 1000°C, were made. A product corresponding to so-called Ca-samarskite was also obtained.

View full abstract

The reactions of amines with 2-acetyl-6-methyl-3(2H)-pyridazinone [1] and 6-acetoxy-2-meth1-3(2H)-pyridazinone [2] were found to give the corresponding amides in good yields. The reactions of the Grignard reagents with [1] and [2] gave the corresponding alkyl methyl ketones.3-Chloro-2, 6-dimethylpyridazinium salt[3] prepared by the reaction of 2, 6-dimethyl-3(2H)-pyridazinone with phosphoryl chloride was allowed to react with several nucleophiles. Chlorination of alcohols with [3] afforded the corresponding chlorides in good yields. The reaction mixture of [3] with benzyl alcohol was treated with thiophenol or aniline to give the corresponding sulfide or N-substituted anilinein good yields. Esters, amines and acid anhydrides were also synthesized by the use of [3].

View full abstract

A series of polymethylbenzenes, polymethylnaphthalenes and some related compounds have been treated with thiocyanogen chloride in acetic acid at room temperature and the reaction products have been investigated. Tetramethylbenzenes and pentarnethylbenzene readily underwent nuclear thiocyanato-substitution to give the corresponding aryl thioeyanates as the sole product. No side-chain attack has been observed. Hexamethylbenzene and pentamethylanisole suffered side-chain substitution, giving a mixture of benzyl thiocyanate, isothiocyanate and chloride. The side-chain substitution exhibited a marked dependence on the polar effect of the substituent groups; with electron-releasing methoxyl group, the reaction occurred exclusively at the methyl group meta to the substituent group, while the reaction did not take place- with the compounds containing electron-attracting groups. A short irradiation of the reaction mixture led to an increase in the amount of benzyl chloride and isothiocyanate at the expense of benzyl thiocyanate; a part of benzyl isothiocyanate obtained was found to arise from the photoisome rization of the initially formed thiocyanate. Polymethylnaphthalenes underwent side-chain substitution exclusively on the methyl group at the α-position. The non-conventional process ofihiocyanato-substitution and isothiocyanato-substitution of arenes may be explained in terms of the S_N1′ mechanism, which assumes the electrophilic attack of thiocyanogen chloride on an arene to form arenium ion[9], which releases a proton from the activated methyl group Para to the site of attack to give a methylenecyclohexadiene intermediate [10]. The triene [10] undergoes a heterolytic fission ofthe C-S bond to form a benzyl cation/thiocyanate anion pair [11], which recombines at benzylic carbon atom either via C-S bond or via C-N bond, giving benzyl thiocyanate [12]and benzyl isothiocyanate [13] as the respective products.

View full abstract

The reaction of 3-buten-2-one (MVK) with aldehydes [1] in the presence of triphenylphosphine (TPP) as a catalyst was studied. In the reaction of MVK with isobutylaldehyde [1e], 4-hydroxy-5-methyl-3-methylene-2-hexanone [2e] was obtained. The reaction of MVK with various saturated aldehydes [1a]-[1h] gave 4-alkyl-4-hydroxy-3-methylene-2-butanones [2a]-[2h] in 34-90% yield. In the reactions of MVK with a, R-unsaturated aldehydes [1i]-[1l], 4-alkeny1-4-hydroxy-3-methylene-2-butanones [2i]-[2l] were obtained in a low yield and 3-methylene-2, 6-heptanone [3] was the major product. The reactions are considered to proceed through intermediacy of the phosphonium betaine which will attack the carbonyl carbon atom of the aldehyde as in the Aldol-type addition. Tri-p-tolylphosphine and 1, 2-bis (diphenylphosphino) ethane were also found to be effective asa catalyst for the Aldol-type addition of MVK to [1e].

View full abstract

A main factor to distinguish a redox reaction from an additional one was examined in by the system of reactions of benzoquinone with low-valence sulfur compounds (sodium thiosulfate (Na₂S₂O₃), sodium dithionite (Na₂S₂O₄), sodium disulfite (Na₂S₂0₅) and sodium dithionate (Na₂S₂0₆)). As in case of an interconversion of H₂S0₃, polargraphic study showed that H₂S₂0₄ existed in an oxidizable form in a strong acid solution and in a reducible form in a week acid solution. The pH regoin of a redoxreaction agreed with that of an oxidizable form and the pH region of an additional reaction agreed with that of a reducible form. It was considered from the above fact that the isomer of an oxidizable form participates in a redox reaction, whereas that of a reducible form participates in an additional one. The reaction of sodium dithionate with p-benzoquinone could not be observed.

View full abstract

The reaction of 1, 4-naphthoquinOne (NQ) and 2-methyl-1, 4-naphthoquinone (MNQ) with Na₂S0₃ has been examined by comaprison of the oxidation-reduction potentials of these quinones (E_NQ and E_MNQ) with that of Na₂SO₃ (E_ss). Redox reaction (Eq.(1)) did not practically proceed because of E_NQE_ss and E_MNQE_ss. NQ (or MNQ)+ HSO₃^- + H₂O =NH₂Q (or MNH₂Q) + SO₄^2- + H⁺ (1) where NH₂Q and MNH₂Q represent 1, 4-naphthalenediol and 2-methyl-1, 4-naphthalenediol, respectively. Addition reaction (Eq. ( 2 )) proceeded more slowly than the similar reaction of p-benzo-quinones. NQ (or MNQ) HSO₃^- =NH₂QS- (or MNH₂QS-) (2) where NH₂QS and MNH₂QS represent 1, 4-dihydroxynaphthalene-2-sulfonate and 2-methyl-1, 4-dihydroxy-3-naphthalene sulfonate, respectively. Main products other than NH₂QS and MNH₂QS were found to be dioxo-1, 2, 3, 4-tetra-hydro-2-naphthalenesulfonate in the reaction of NQ with Na₂SO₃ and 2-methyl-1, 2, 3, 4-tetra-hydro-2-tetrahydro-2-naphthalenesulfonate in the reaction of MNQ with Na₂SO₃. These products may be formed owing to E_NQE_ss and E_MNQE_ss.

View full abstract

Formation of dibenzyl ether in the phase-transfer-catalyzed reaction of benzyl chloride with aqueous sodium hydroxide was examined. Benzyl chloride and catalytic amounts of methyl-trioctylammonium chloride(TOMAC) in 50% aq. NaOH were .stirred at 70°C for 1 hour to form dibenzyl ether in 98% yield. The rate of formation of dibenzyl ether increased with increase of the concentration of aq. NaOH., TOMAC, tetrabutylammonium chloride and tetraoctyl-ammonium bromide were the most effective among the quaternary ammonium salts. Ammonium salts bearing the benzyl group and the phosphonium salts were less effective. The correspond-ing dibenzyl ethers were also obtained in good yield from the substituted benzyl chlorides under the same conditions. o-Methylbenzyl chloride was more reactive than p- and m-isomers.

View full abstract

3, 4-Dihydro-3-methoxycarbonyl-1 (2H)-naphthalenone [1] and 3, 4-dihydro-2-ethoxycar-bony1-1(2H)-naphthalenone [9a] were allowed to react with methylmagnesium iodide, and from their products 1, 3- or 1, 2-dialkylnaphthalenes and three naphthothiophene derivatives were synthesized. The reaction of the cyclic γ-keto ester [1] with methylmagnesium iodide yielded a mixture of the expected diol [2], keto alcohol [3], and 1, 2, 3, 4-tetrahydro-1, 1-dimethylnaphthalene-3-carboxylic acid [4a]. By heating [2] with sulfur, 3-isopropyl-1-methylnaphthalene [7a] was obtained. From [6], the product of the Grignard reaction with ester of [4a] by dehydrating and successive heating with sulfur, [7a] and 4, 5-dihydro-3, 5, 5-trimethylnaphtho[1, 2-b] thiophene [8] were obtained. By dehydration of [3] with formic acid, 3-isopropyl-1-naphthol [7b] was obtained. On the other hand, the cyclic β-keto ester [9a] reacted with Grignard reagent to yield the desired keto alcohol [10]. When it was dehydrated, α, β-unsaturated ketone [11a] was obtained. 2-Isopropyl-1-methylnaphthalene [7], 2-t-butyl-1-methylnaphthalene [7e], and 3, 3-dirnethyl-1, 3-dihydronaphtho[1, 2-c]thiophene [14] were obtained from [11a]. The melting point of picrate of [7a] was 105.5-106.5°C, but that shown in the literature is 84°C. In order to identify the hydrocarbon [7a], it was also synthesized from 4-methyl derivative of [9a], and in this synthesis 3, 5-dimethylnaphtho[1, 2-b]thiophene [15] was obtained as a by-product.

View full abstract

The mechanism of hydrodenitrogenation of carbazole on a prereduced MoO₃-Al₂O₃, catalyst was studied using a high pressure flow microreactor. The hydrodenitrogenation was carried out in xylene solution containing 0.25 wt% carbazole at temperatures of 270-340°C under conditions of total pressure of100 atm, weight hourly space velocity of 10 and hydrogen flow rate of 30 l/hr. Carbazole was hydrogenated through 1, 2, 3, 4-tetrahydrocarbazole succesively to perhydrocarbazole, which was denitrogenated to yield bicyclohexyl. The rate of denitrogenation increased with an increase in temperature. Et.hylbicyclo[4.4.0]decane and hexylcyclohexane were produced by isomerization and the ring opening reaction of bicyclohexyl above 300°C. The apparent activation energy for the rate of formation of bicyclohexyl was found tobe 30.3 kcal/mol.On the basis of the kinetic information, it is considered that hydrogenation of carbazole to perhydrocarbazole is in quasi-equilibrium at high temperatures and that the rate-determining step is hydrodenitrogenation of perhydrocarbazole.

View full abstract

An investigation was made on the number of branches in ethylene-vinyl acetate copolymers (EVAc) consisting of 42.2% or less by weight of vinyl acetate. The numbers of ethyl, butyl, pentyl and longer branches per 1000 carbon atoms of the main chain were determined quantitatively by ¹H- and ¹³C-NMR. Before the measurements of ¹³C-FT-NMR spectra, the optimum pulse parameters were examined from the measurements of ¹³C spin-lattice relaxation times of individual carbons in EVAc. It was found that the number of ethyl branches was within 5 per 1000 carbon atoms, and that the number of branches longer than butyl decreased from about 30 to8 per 1000 carbon atoms of the main chain with an increase in vinyl acetate content. The number of butyl branches predominated over the other types when the vinyl acetate content was 30% or less by weight, but was nearly equal to that of the pentyl and longer branches with the increase in vinyl acetate content. It was also found that ¹³C-NMR signals for the methine carbon coupled to butyl and longer branches and the methyl carbon of the ethyl branch were separated into two peaks by the contribution of an ajacent acetate substituent to their chemical shifts.

View full abstract

Methyl methacrylate (MMA) polymerized in terms of hydroxylamine-H₂O₂ redox system in water at 30°C. The rate of polymerization; was maximum aj pH 2.0. The mole ratio of reacted H₂O₂ to hydroxylamine was about 3 in the absence of MMA, whereas in the presence of MMA it was 1/2. At the beginning of polymerization, the decreasing rate of hydroxylamine in the presence of MMA was nearly equai to that in the absence of it. The nitrogen Content in a polymer was 1.43 g atom per mole of a polymer in a certain case. These results suggested that the reaction of hydroxylamine With H₂O₂ proceeds by means of free radical process and forms free radicals containing nitrogen ; this reaction rnechanisin was also discussed.

View full abstract

Polymerization of vinyl acetate in benzene (0, 20, 30 and 50 vol%) was carried out at 30°C by using α, α′-azobisisobutyronitrile (AIBN) asan initiator and cumene as a chain transfer agent. The Tate of polymerization (Rp) decreased markedly with the increase in both benzene and cumene concentrations. The chain transfer-constant to cumene (Cs) changed a little with the change in benzene concentration. The rate constant of propagation (Kp) decreased with the increase in benzene concentration. The rate constant of hydrogen atom abstraction from cumene by the propagating radical of poly (vinyl acetate) (Kabs) was derived on the basis of the values of Cs andKp. The values of Kabs decreased with the increase in benzene concentration and were approkimately proportional to the values of Kp.

View full abstract

Synthesis of polymer containing amino-1, 3, 5-triazinering (guanamine structure) as a pendant by the reaction of ester group with biguanide was investigated by comparing it with a model reaction. Aliphatic carboxylic methyl ester gave N-phenylguanamine in a satisfactory yield when it was treated with phenylbiguanide in dimethyl sulfoxide (DMSO) over basic catalyst. Practically, guanamine was obtained in quantitative yield from such active ester as phenyl or pnitrophenyl acetate. Poly (methyl methicrylate)reacted with phenylbiguanide in DMSO over basic catalyst during a slow lapse of time to give a polymer containing approximately 40 mol% of triazine ring. Further, the almost complete conversion of polymers containing phenyl acrylates to triazine ring-containing derivatives occurred during a rapid time. It was found that various polymers having N-substituted acryloguanamine structure were readily prepared by means of the above synthetic procedure. An introduction of triazine ring to a polymer as a pendant decreased the flexibility of the polymer chain. Namely, softening and glass transition points increased considerably with increasing content of guanamine structure. And solubility of thecopolymer markedly changed. On the basis of these results, it became apparent that the above-mentioned properties are affected remarkably by the content of triazine ring and the structure or composition of a polymer.

View full abstract

A.sprucewood meal (40-80 mesh, extracted with alcohol-benzene) was digested with cooking liquors of SO₂-MgSO₄ as well as of Mg-base sulfite at temperatures of 127, 137 and 147°C, respectively. Some significant differences in the two cooking liquors were found from kinetic analyses of cooking reactions, i. e.delignification, sulfonation on lignin, and dissolution of carbohydrates.The interrelationship among the reactions was also discussed in detail. All the cooking reactions were analyzed by assuming that they were a first-order reaction with respect to the amount of the reactant, but the rate of each reaction was found to be different between at the initial and at the final stages. This fact might be attributed to the heterogeneity of the reactants and therefore, each reaction was analyzed once again dividing the wholeprocess into two parts ; the initial and the final reactions. Whereupon the reaction rates in either stages were adequately approximated by the first-order kinetics.The rate of delignification in the Mg-base sulfite liquor was higher than in the SO₂-MgSO₄liquor both at the initial and the final stages. The, difference in therate at the initial stage of two liquor systems was ascribed to the difference in the rate of the sulfonation which proceeded in the same period as the delignification proceeded. However, the initial rate of delignification was found to be proportional to that of the dissolution of carbohydrates in both systems. The dissolution of carbohydrates could also be presumed to give a great influence on the sulfonation of lignin. Such a close relationship between the reactions of lignin and of carbohydrates at an initial stage suggested that the progress of cooking reactions would appreciably be associated with a physical change of the wood cell structure.

View full abstract

The ethylene-hexafluoropropene (HFP) copolymers were synthesized both by batch-wise and continuous copolymerization processes under high pressure. By a batch-wise process (650-1385kg/cm², 115-155°C), no ethylene-HFP copolymer containing more than 50 mol% of HFP was obtained, and the azeotropic composition was 0.265. Under almost the same conditions (pressure, temperature and concentration of initiator), no homopolymerization reaction of HFP occured. The experimental data were analyzed according to the Barb's theory and the possibility of thepresence of the reactantsof 1 : 1 complex of ethylene-HFP during the reaction was presumed. The vulcanizability and elastic properties of the copolymers synthesized by a continuous process (1600-2000kg/cm², 160-200°C) were evaluated. It was found that the copolymers were not vulcanized with diamines but only with organic peroxides. The vulcanized copolymers containing 35mol% of HFP have the following characteristics as an elastomer : adequate heat resistance at 200°C and low compression set at high temperature, good oil-, chemical- and steam-resistance, excellent electrical properties, and favorable vulcanizability ofcomposed materials with other synthetic rubbers. The characteristics of the vulcanized copolymers were also compared with those of heat-resistant rubbers.

View full abstract

Water-soluble cationic polymers were prepared by the amination of poly (vinyl chloride) (PVC) with polyethylenepolyamine in N, N-dimethylformamide (DMF). The cationic flocculation effect of these polymers was studied by observing the supernatant suspension concentration in jar test of the kaolin suspension. The reaction temperature, reaction time, and amine concentration in the aminatin of PVC with polyethylenepolyamine influenced greatly the clarification effect of the cationic polymers obtained. The breakdown of the polymer backbone occured during the amination of PVC with polyethylenepolyamine. However, when PVC (1g) was treated with about 1 molar polyethylenepolyamine per unit structure of PVC in DMF (40ml) at 80°C for 20-30 hours, the resulted cationic polymers showed the excellent clarification effect to the kaolin suspensions. It was estimated by the results of IR-spectra and elemental analyses that cationic polymers obtained had the amine structure, conjugated double bond, carbonyl groups, oxidation products, and residual vinyl chloride structures.

View full abstract

Separation of monoamino monocarboxylic acids in binary aqueous solutions system containing L-alanine was carried out by reverse osmosis using DDS-cellulose acetate membrane, and the effects of hydrogen bonding of the added amino acids and their concentrations on the selective permeation of L-alanine have been investigated. Fourteen kinds of solutions consisting of L-alanine (1.0 × 10^-3 mol/l) and added amino acids (2.5 × 10^-4-4.0 × 10^-3 mol/l) of aliphatic, hydroxy-substituted, sulfur-containing, and aromatic types were tested.It was found that rejection of L-alanine was almost constant in the concentration range of the above acids (ca.1.0 × 10^-3-4.0 × 10^-3mol/l) in every respect of the system. But in certair system the rejection of L-alanine considerably increased at the concentration of the acids (2.5 × 10^-4mol/l)(Figs. 5-9) This increase in rejection of L-alanine (Δη1) was correlated with Taft's number (Σσ*) of each amino acid added (Fig. 12). Results revealed that when Taft's number of the added amino acid and that of L-alanine were close to each other, the rejection of L-alanine increased considerably, but when they were apart, the rejection of L-alanine was almost constant. This typical behavior was considered to be, due to the formation of adsorbed layer of amino acids on a surface of the membrane on the brsis of the experiment on a single system (Fig. 10). On the other hand in every respect of the system, the rejection of both L-alanine and added amino acids was higher in a binary system than that in a single system (Table 2, Fig. 11).

View full abstract

The factors being affected by ion transport of liquid membrane containing crown ether as a carrier were studied. Experiment on ion diffusion from salt solution to pure water across a liquid membrane was carried out. Dibenzo-18-crown-6 was used as a crown ether and ion species used in this study were potassium and sodium. Salt concentration, composition of salt solution, carrier concentration, membrane solvent, pH, counter ion, and additions to liquid membrane affected an ion transport. In particular, significant effects of counter ion, membrane solvent, and additions to a liquid membrane on ion transport were ascertained in this study.When hydrophilic anion was used as a counter ion, it minimized a flux, and when tetrachloroethane was used as a membrane solvent, a flux and the selectivity became significant in a chloromethane series solvent. When salicylic acid was added to the liquid membrane, a flux and the selectivity became pronounced due to its cation exchange property. The investigation on affecting factors would bring- about a prominent function of liquid membrane. When this liquid membrane separation was applied to sea water and brackish water, the selectivity became high due to a high concentration ratio of sodium to potassium and the presence of various counter ions.

View full abstract

The behavior of sea salt particle in urban air has been investigated based on size-distribution and concentration of water-soluble sodium or chloride ion in atmospheric aerosol. Air sample was collected by using an Andersen sampler at a certain site of Nagoya city about 10 km north of a coast. The size-distribution for each ion was usually a bimodal type being derived from natural and artificial sources. From the results of the observed seasonal change in size-distribution and in concentration of each ion, Na+ ion in the coarse particle size range (>2μm) was found almost to be due to sea salt particle. The predicted concentrations of sea salt particle in urban air in summer and in winter were about 3 and 1 iugims, respectively, and correlated with a transportation of sea salt particles in terms of the seasonal wind. The contribution of sea salt particle to urban aerosol (about 2-6%) was smaller than that of soil particle (about 20-40%). The Cl^-/Na⁺ concentration ratio in the coarse particle size range was approximately equal to 1.8 in winter, indicating the composition of sea salt particle in urban air was the same as that of sea water.On the other hand, theremarkable chlorine loss from sea salt particle was observed in summer, and the calculated chlorine loss was assigned to the observed concentration of NaNO₃ particle. It was suggested that the chlorine loss would beresponsible for the reaction between NaCl particle and HNO₃-vapor to form NaNO₃ particle and to emitHCl in an atmosphere.

View full abstract

Trialkoxy- and tris(alkylthio)arsines reacted with acetic anhydride and gave dialkoxy- or bis(alkylthio)arsenic acetates and alkyl acetate or S-alkyl thioacetate, respectively. Measurements of the rate of the substitution reaction were performed by monitoring the decrease in the amounts of acetic anhydride by using of IR spectrophotometry. The effect of the substituents on the rate constants was analized statistially. The analysis showed that Taft's equation held for these reactions and that the reaction constant ρ* calculated was positive in the both reactions. The reaction constants of the arsenic compounds were smaller than those of the amtimony compounds. The effectof the solvent polarity on the rate constants for the arsenic compounds was found to be opposite to that for the antimony derivatives. These results suggest that the electrophilic attack of the arsenic atom on the ether oxygen of acetic anhydride is the rate determining step, but the interaction of the carbonyl group of acetic anhydride with carcogen atoms of the alkoxides or alkanethiolates is also involved in the rate determining step.

View full abstract

Disproportionation reaction of toluene over alkali metal (Na or K)-graphite or alkali me-tal-metal chloride (MgCl₂, BaCl₂, CaCl₂, FeCl₃, or PdCl₂)-graphite catalyst was studied. It was found that K-graphite catalyst was more active than Na-graphite one, and that m-xylene was fairly and selectively formed over Na-graphite catalyst or Na-BaCl₂-graphite one.

View full abstract

The reaction of 2, 2′, 4, 4′-tetrachloroazoxybenzene (TCAB) with a few proton acids gave 2, 2′, 4, 4′-tetrachloroazobenzene as a main product together with a small amount of o-hydroxyazo compound in every case. The same amount of a azo or o-hydroxyazo compound was also obtained in the photo-Wallach rearrangement of TCAB. In the Wallach rearrangement of azoxybenzene and its chloroderivatives when 78% sulfuric acid was used as a solvent, the more the chlorine atom, the slower was the reaction of polychloroazoxybenzenes.

View full abstract

More than 90% of the ester groups of the ethylne-t-butyl methacrylate (E-TM) copolymers were pyrolyzed in a few minutes at a temperature above 300°C, and the ethylene-methacrylic acid copolymers were obtained. The activation energy for the reaction was determined as 32.6 kcal/mol. When zinc acetate up to 35 mol% based on the ester groups was blended with the E-TM copolymers at temperatures of 260 to 310°C by means of an extruder, the ionomers were formed by stoichiometric ionic cross-linking reaction. The added zinc acetate accelerated the pyrolysis reaction of the ester groups. Adhesive bond characteristics of the ionomers containing ester components obtained abovewere studied. The ester components were found to contribute both to the adhesive bonding at low temperature and to the increasing of adhesive substrate.

View full abstract

The deposits in heat exchangers or air preheaters by the use of flue gas from oil- and coal-fired boilers after NO_x removal by ammonia were found to contain various iron and aluminum ammonium sulfates, indicating that ammonium hydrogensuifate and sulfuric acid, which were condensed from the gas on cooling, reacted with the heat exchanger material and flyash. A compound previously unknown was detected with the composition of Fe(NH₄)H. (SO₄)₂.H₂O. The formation reactions of those compounds were discussed. The effects of the deposits on the heat exchanger operation were suggested.

View full abstract