The mutual solubility of organic compounds and water is usualy depressed by the addition of inorganic salts, but it is enhanced by the addition of metal thiocyanates or metal iodides. In the present paper, the effect of sodium thiocyanate (NaSCN) and sodium chloride (NaCl) on the mutual solubility of 2-butoxyethanol (n-C₄H₉OCH₂CH₂OH)Water system and that of calcium thiocyanate Ca(SCN)0 on 1-butanol--water system have been studied. In the case of 2-butoxyethanol--water system, both upper and lower critical temperatures exist. fTwo phase region disappears in 2-butoxyethanolWater system at NaSCN concentrations more than 2.5 wt%.1-butanol and water completely mixes lower than 25°C in the presence of 10 wt% Ca. (SCN)₂. Two phase region disappears completely in the presence of 12.5 wt% Ca(SCN), . The increace of the mutual solubility of these systems is resulted from the enhanced solubility of water in 2-butoxyethanol or 1-butanol phase. The solubility of the latter in water does not change appreciably. It is found from the partition equilibrium studies that inorganic salts, such as Ca (SCN)₂ and NaSCN, which increased the mutual solubility, dissolved well in an organic phase, whereas NaCl which depressed the mutual solubility, dissolved preferentially in an aqueous phase.

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Faculty of Textile, Shinshu University; Tokida, Ueda-shi 386 Japan Streaming dichroism of aminoanthraquinone disperse dyes solubilized (1.2 × 10^-4 mol/l) in 25% aqueous solution of nonionic surfactant, polyoxy. ethylene (average degree of polymerization is ca.9.3) dodecyl ether, has been measured to investigate the mode of solubilization of waterinsoluble dyes. From the experimental results, it was inferred that 1, 4-diamino- and 1, 4-bis(methylamino)-anthraquinone were solubilized in the hydrophilic moiety of micelles, facing the longer axis of the molecule in the direction of the cylindrical axis of micelle (<45°) as possible and lying almost horizontally with increasing velocity gradient. On the other hand, 1-aminoand 1-(methylamino)-anthraquinone were proved to be solubilized in the hydrophobic core of micelles, the longer axis being nearly perpendicular to the micellar axis (>45°). In the concentration region of the surfactant below 20%, the solution showed negative streaming birefringence, but the dye solubilized did not exhibit streaming dichroism. This fact demonstrates that the formation of network by the interlinking of polyoxyethylene groups, which contributs positively to the streaming birefringence, is necessary for the orientation of micelles to cause the orientation of the solubilized dye and the streaming dichroism under the velocity gradient.

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A kinetic study on oxygen uptake on the surface of iron metal powder (1.3μ average diameter) in a mixed gas (6% O₂ and 94% He) at 300-700°C was carried out by means of a micro thermogravimetric analysis, and was compared with the growth rate of oxide whisker described in our previous paper².
Variation of oxygen uptake with time showed a rapid increase within first several minutes, and then a gentle increase with a monotonous elapse over more than two hours, and its increasing rate obeyed Elovich equation, d(ΔW)Idt=kexp (-α(ΔW)).
The initial rate, k, showed temperature dependencies of 24.5 and 9.7 kcal/mol, in the temperature ranges above and below 480°C, respectively. This boundary temperature corresponds to the temperature on which the amount of whisker growth attained maximum (4% of the total O₂ uptake), and it was considered that the supplying rate of iron ions to the root of whisker, where the reaction of whisker growth takes place, is decelerated by the acceleration of the formation rate of oxide film at above that temperature.
The increasing rate of oxide film thickness (y) obeyed a logarithmic rate law in a similar manner as the elongation rate of whisker length (l). The negative temperature dependence of the deceleration rate coefficient (α) was observed about y, but not observed about 1, and the increase of 1 consequently exceeded that of y at lower temperature.
On the basis of these facts, it was suggested that iron ions may be supplied to the reaction phase of oxide film formation mainly by the volumetric diffusion, and to the root of whisker by a certain short circuit diffusion such as dislocation diffusion, and also the root growth mechanism proposed in our previous paper was supported.

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Electrochemical oxidation of pyrrole was investigated in the aq.0.1 N sulfuric acid, BrittonRobinson buffer solution and aq. O.1 N potassium hydroxide solution at a platinum electrode. - 4-Pyrrolin-2-on, 5- (2-pyrroly1)-2-pyrrolidinone, 2, 5-bis(5-oxopyrrolidin-2-yl)pyrrole and pyrrole black were obtained as oxidation products at pH> 10 and pyrrole black was obtained at pH<10. The oxidation potential of pyrrole in 0.1N potassium hydroxide solution at a platinum elcctrode was +0.9 V vs. Hg/HgO. Cathodic polarogram of anolyte at a dropping mercury electrode was measured in the controlled potential electrolysis. In the early stage of oxidation, 4-pyrrolin-2-on and 5-(2-pyrroly1)-2- pyrrolidone was found and then 2, 5-bis(5-oxopyrrolidin-2-yl)pyrrole was detected in accordance with the progress of the electrolysis.

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Packed bipolar cell is suitable for the electrolysis of dilute solutions such as certain liquid wastes, because it is composed of numerous unit-cells situated among packed particles, resulting to increase effective electrode area, and consequently the reactant can rapidly take part in the reaction. Characteristics of this type of the cell were investigated in the case of the electrolysis of K₂ CrO₄ and KCN solutions under different conditions, with respect to particle material, particle size, and applied voltage.
Chromate ion was reduced to Cr(OH)₃ which deposited on packed particles. Cyanide ion was oxidized to CNO- or further, to CO₂ and N₂. When the electrolysis was carried out in the cell packed with activated carbon particles, the reaction rate and the power efficiency became higher than those in the conventional cell. As applied voltage increased, the reaction rate increased but the power efficiency decreased. Optimum particle size and applied voltage might probably depend' on the concentration of the solution.

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A high molecular weight lignosulfonate (LSA, [η]Vg NaCl=0.29 100 mug) was prepared by condensation of a lower molecular weight lignosulfonate ([η] =0.06) with formaldehyde. The experiment on the effect of LSA on the viscosity of dilute aqueous suspensions of Na^-, H^-, Ca^- and Al-ion and montmorillonite was carried out. For the Na-, H- and Ca-montmorillonite sys- tems, the viscosity number, η_sp/c, of the suspensions was increased by addition of LSA under the following electrolyte concentrations: at the ocncentration of NaCl above 0.06 N for Namontmorillonite system, at the concentration of HCl above 0.01 N for H-montmorillonite system and at the concentration of CaCl₂ above O.003 N for Ca-montmorillonite system. These results indicate that the particle association of edge-LSA-edge type by cross linking with LSA takes place. For the Al-montmorillonite system, the η_sp/c was decreased by addition of LSA at the concentration range of AlCl, from 1 × 10^-5 to 0.04 N. The results for the Al-montmorillonite system at the concentration range of AlCl₃ above 0.001 N may be explained by the fact that the formation of flat-LSA-flat association by cross linking with LSA contributes to the resulting decrease of the η_sp/c.

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Mixed-ligand complexes, [Cu(L) (en)] (L stands for malonate, succinate, maleate, and phthalate ions and en stands for ethylenediamine), have been identified in solutions containing various ratios of their constituents. The equilibriums of these mixed-ligand complexes with both bis(ethylenediamine)copper (II) and bis(dicarboxylato)copper (II) ions were investigated spectrophtometrically by varying the rations of the concentrations of the three complexes through pH adjustments. From the proportions of the three kinds of complexes found in the various solutions, stability constants (log K_m) of 14.63, 12.68, 13.69, and 13.43 were calculated for the mixed-ligand complexes containing malonate, succinate, maleate, and phthalate ions, respectively. From disproportionation constants (pK_s) the stability order among the mixed-ligand complexes was found to be phthalate> malonate > maleate > succinate.

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As far as the studies on the cadmium content in varied natural water are concerned, only a few reports on varied natural water of mineralized zone are known, and none on ordinary varied river water. The purpose of the present investigation is to check the presence of cadmium in ordinary varied river water. Under these circumstances, the cadmium contents in varied river water collected at 117 sampling sites in Kyushu, Japan, were determined by the atomic absorption spectrophotometry combined with dithizone-chloroform extraction (Fig.1).
The results are summarized as follows:
(1) The geometrical mean for cadmium is 0.059μg/l, that for zinc is 4.96μg/l. The cadmium is always present in varied river water in an amount ranging from 0.02 to 0.16μg/l, and the difference in cadmium contents in various rivers is generally slight.
(2) As shown in Fig.4, clearly positive correlation is found between cadmium and zinc contents in the samples collected in mineralized zone, and the value of Zn/Cd is about 150. But such a correlation is not definitive for varied ordinary low polluted river water.
(3) In ordinary river water, it is generally supposed that cadmium in river water is due to cadmium already present in rain water.
(4) On the basis of the investigation on heavy metals in river water during ca.20 years at Umegafuchi along the Kotsuki River, zinc content in river water rapidly increases, with the growth of cities, while the same is not true for cadmium.

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A simultaneous determination of the mixture of a reversible or quasi-reversible and an 'irreversible species, whose reduction and oxidation potentials are close together, has been carried out by recording the semiintegral, m, of current against time, t, upon applying a pulse potential to the electrode. The semiintegral, m(t), of the current, i(t), is defined by
As an example, the simultaneous determination of Zn²⁺ and Ni²⁺ in 1.0 molii KCl was carried out by using a hanging mercury electrode. In the case of a reversible or quasi-reversible species, Zn²⁺, the semiintegrated current at the pulse time, t_p, was proportional to the concentration of Zn²⁺ in the range from 20 to 100 prnol//, and that at t=2t_pwas zero irrespective of concentration. In the case of an irreversible species, Ni", both semiintegrated current, m(t_p), at t=ti, and that, m(2t_p), at t=2 t_p were proportional to the concentration of Ni", and the latter was equal to half the former in all concentrations from 20 to 100 pmolii, It became clear that the simultaneous determination of Zn²⁺ and Ni²⁺ can be performed by evaluating the summation of the amount of both species from m(t_p) value and the amount of Ni²⁺ alone from m(2t_p) value of the na-t curve of the mixture. The similar investigation to determine Cu²⁺ and O₂ in 0.5 mol// HCl0₄ was performed by using a glassy carbon as an example of solid-plane indicator electrodes.

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Direct current and pulse polarography, by using a wall jet disk electrode as a working electrode, was utilized as adetector for liquid chromatography. The polarographic detector developed was constructed by using three-electrode: planar glassy carbon (working electrode), platinum tube (counter electrode), and saturated calomel electrode (reference electrode). Capability of this detector was evaluated by nitrobenzene in electro-reduction and aniline in electrooxidation.
The linear dynamic range between limiting diffusion current and concentration was about 1 × 10 (1 × 10^-9-1 × 10^-6 g) and the minimum detectable amount was 1.2×10^-9g for nitrobenzene and 1.9 ×10^-9 g for aniline.
The limit of detection of this polarographic detector was found to be similar as that of UV detector. The polarographic detector using electrochemical technique offers various applications. For instance, an accurate determination of electrochemically active compounds in multi-component substances can be possible.

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Photo-oxidative decomposition of vinyl chloride was studied in the presence of chlorine (Cl₂) under UV irradiation with high pressure mercury lamp (100 W) at a room temperature. By photo-oxidation, in the presence of small amounts of Cl₂ ClCH₂CHO, HCHO and HCOCl are produced as intermediate products. In the presence of large amounts of Cl₂, the formation of ClCH₂CHO, ClCH₂C0Cl and ClCH₂CHCl₂ (TCE) was observed in the irradiated gas. The concentration of these products increases with increasing irradiation time, and these products disappear under further irradiation. The photo-oxidative decomposition increases with increas- ing molar ratio of Cl, to vinyl chloride (VC) (Cl₂/VC), and, provided Cl₂/VC <2, the rate is higher than that of the photo-oxidative decomposition of TCE in the case of Cl₂/TCE <1, while, provided Cl₂/VC >>2, the former rate is almost equal to that of TCE in the case of Cl₂/ TCE >>1. The ratio of conversion of Cl₂ to that of vinyl chloride becomes larger than unity, and the ratio decreases with increasing the conversion of vinyl chloride. The decomposition of both vinyl chloride and TCE scarcely takes place in the dark even in the presence of chlorine dioxide, while decomposition of them is accelerated remarkably by UV irradiation. Ozone also promotes the photo-oxidative decomposition of vinyl chloride in the presence of small amounts of Cl₂. On the basis of these results, a role of Cl₂ in the photo-oxidative decomposition of vinyl chloride was discussed.

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Reactions of trans-1, 2-, cis-1, 2-, trans-1, 4-, and cis-1, 4-dichlorocyclohexanes with antimony (V) chloride were investigated. Although the isomerization of cis-1, 2-dichloride does not occur and a decrease of this compound happens (Fig.2), the isomerization of other three dichlorides occurs. The yield of isomerized products of cis- and trans-1, 4-dichlorides are greater than that of trans-1, 2-dichloride. These different behaviors of the dichlorides were discussed in terms of their conformations. The distributions of cis-, trans-1, 3-, and-1, 4-dichlorides in the isomerized products occur irrespective of the starting dichloride or the reaction time (Table 1). Effects of solvent and temperature on these distributions were investigated. Mechanisms of the isomerization were discussed and it was suggested that carbonium ions, whose counter anion being hexachloroantimonate ion, should be the intermediates of the isomerization. The distributions of the products obtained by the isomerization were compared with those obtained by the isomerization due to the chlorination of cyclohexene with antimony(V) V chloride.

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As apart of series of investigation of the Wallach rearrangement, azoxy compounds having proton acceptable substituents were studied. The results obtained are as follows;
(1) The reaction of a-p-acetoamidoazoxybenzene [1], methyl a-p-azoxybenzenecarboxylate C 33 and a-p-(dimetylamino)azoxybenzene N-oxide (5) yielding the corresponding p-hydroxyazobenzenes depended on the acidic function of sulfuric acid added. In this reaction 8-pacetoamidoazoxybenzene [2] and methyl β-p-azoxybenzenecarboxylate 4 J were converted to the corresponding a-isomers.
(2) 2-Hydroxy-4'-(dimethylamino)azobenzene [10] was obtained as an ortho isomer in company with 4-hydroxy-4'-(dimethylamino)azobenzene as the result of the Wallach rearrangement of [5]. In this reaction, the ortho-para ratio was unity in each runs. A mixture of α-[12] and β-p-(dimethylamino)azoxybenzene [13] having the ratio 4/1 was also obtained.
(3) These reactions seemed to proceed via diprotonated intermediate to the oxygen atom of azoxy group and the para-functional group by the measurement of UV absorption curve.
(4) By treating amine oxide of p-(dimethylamino)azobenzene [6] with sulfuric acid, [9] was also obtained. It seems to be the first case that a tertiary amine N-oxide undergoes the Wallach rearrangement.

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A new on-line NMR system to study moderately rapid kinetic phenomena has been constructed by the use of a floppy-disk drive system with a specially designed interface unit and softwares. This system has been applied to the study of the reaction of oxime formation from 2- furaldehyde and hydroxylammonium chloride in dirnethyl-d₆ sulfoxido at 24, 40, and 60°C. The reaction scheme is shown in Fig.2. An NMR spectrum of the reaction mixture is shown in Fig.3, and the time dependent change of each peaks are shown in Fig.4-6. The assignments are listed in Table 1.
It is found by the precise and simultanous measurement of the reaction rates of three cornpounds that the fraction of syn-2-furaldehyde oxime formed in the initial stage is O.85 relative to total oxime formation. It is estimated from the energy difference between the 2-furaldehyde rotamers that their relative populations are 0.66 and 0.34, It is suggested that the syn-2-furaldehyde oxime is formed from the s-trans rotamer of 2-furaldehyde and the anti-2-furaldehyde oxime is formed from the s-cis rotamer of 2-furaldehyde.

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The vapor phase rearrangement of cyclohexanone oxime for e-caprolactam catalyzed by mixed metal oxides was studied by using a flow reactor under atmospheric pressure. It was found that the most effective catalysts for this reaction were ZnO-WO, and Bi₂O₃-W₈ supported on silica-alumina among some mixed metal oxides examined (Table 1, 2). From the data shown in Figures 1, 2 and 3, the optimum preparation conditions of these catalysts were as follows: atomic ratio of Zn/W: 1/2 and that of Bi/W: 2/1, total amount of oxides: 1.5 mg-atom/g of support, calcination temperature: 800°C on Bi₂O₃-W₈. The optimum reaction conditions were as follows: temperature: 325°C on ZnO-W0s and 700 on Bi₂O₃-W₈. The optimum reaction conditions were as follows: temperature: 325°C on Bi₂O₃-W₈. The optimum reaction conditions were as follows: temperature: 325°C, and W/F: 300 g. hr/mol. The maximum yields of e-caprolactam were 87 mol% and 82 mol% on ZnO-WO₈ and BiPs-W₈ on silicaalumina catalysts, respectively (Fig.4, 5). These catalysts keep such a high activity for 12 hr, and the deactivated catalysts are recovered completely by the calcination at 350°C in an air.

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Direct chlorination of anthraquinone has been studied in detail to elucidate the reaction path and orientation of the reaction. Although it had been difficult to separate and analyze the chlorinated products of anthraquinone, almost complete separation of 26 chloroanthraquinones was effected by means of high-speed liquid chromatography. The reaction between anthraquinone and chlorine in the presence of catalysts such as iodine and palladium salts took place easily at 100°C in concentrated sulfuric acid to give a mixture of chloroanthraquinones. When I₂ was used as a catalyst, the reactivity of αposition of anthra- quinone was about five times higher than that of β-position. When palladium acetate was used as a catalyst, the reactivity of α-position was about ten times higher.
The rate of chlorination of 1-chloroanthraquinone was 2.1 times as high as that of anthraqinone, showing that the Cl-substituent enhanced the chlorination rate. The reactivity of anthraquinone nucleus toward chlorination increased with an increase of the number of Cl-substituent. Therefore chlorination could not be stopped at a desired stage and a mixture of anthraquinones chlorinated in various stages was always obtained even when a comparatively small amount of chlorine was used. In the chlorination of chloroanthraquinones o-, p-orienting effect of Clsubstituents was predominant, although an o-/p- ratio was changed with the kind of catalyst used.
Under the reaction conditions employed in the present study one ring of anthraquinone nucleus could not be substituted by more than two Cl atoms and tetrachloroanthraquinone was the final product.

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Oligomerization of a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA), by using 2-aminoethanethiol as a telogen, and photo-oligomerization of a hydrophobic monomer, styrene, by using p, p'-diisocyanatodiphenyl disulfide as an initiator, were carried out to obtain semitelechelic oligo-HEMA and telechelic oligo-styrene, respectively. Oligo-HEMA was allowed to react with oligo-styrene in DMF at 0°C to synthesize HEMA-styrene ABA type block copolymers.
Films of ABA type block copolymers, blendmers and random cooligomers, consisting of HEMA and styrene, were cast from DMF solutions. Their contact angles with water were measured. Remarkable differences were found in wettability among ABA type block copolymers, blendmers and random cooligomers. Those microstructures, i. e., size and geometry of hydrophilic and hydrophobic domains, were found apparently to differ from one another by the electron microscopic observation. It was considered that hydrophilic or hydrophobic functional occurence was influenced not only by the composition but also by the microstructures of the polymers.

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Poly(2-hydroxyethyl methacrylate) (PHEMA) shows amphiphilic nature. The effects of solvent composition and hydrophobic interaction on the conformational change of oligo-HEMA in a water-dioxane solvent were discussed. By the fluorometric analysis using auramine in a waterdioxane solvent, it was found that oligo-HEMA resulted in compact form due to the hydrophobic interaction between a-methyl groups in the solvent whose water content was more than 70 vol%. This hydrophobic interaction decreases with increasing dioxane, and oligo-HEMA chains expand. The hydrophobic interaction is destroyed by the addition of 30 or more vol% of diox- ane. Upon further addition of dioxane, oligo-HEMA chains gradually expand until 80 vol% dioxane and then contract. This shows that a water-dioxane (80 vol% dioxane) solvent has a strong affinity for both hydrophobic and hydrophilic groups of oligo-HEMA.
Water soluble HEMA-N-vinyl-2-pyrrolidone cooligomers were synthesized to clarify the behavior of oligomer chains in water or water-organic solvent. It was found that hydrophobic interaction markedly increased with increasing content of HEMA in cooligomer due to increas- ing density of hydrophobic groups.

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One of the authors has shown in his previous papers that by thermal decomposition of poly(barium or calcium methacrylate) (polymer salt) at 500°C five-membered cyclic ketones are mainly obtained. But it is not clear, how the main chain of the polymer is cut before complete decom, position.
It was confirmed that the molecular weight decreases remarkably when the polymersalt(barium) is heated in a nitrogen stream in the temperature range from 250°C to 330°C. The decrease in molecular weight is expressed by the following equation: 1/M-1/M₈=kt (Fig.3), indicating an occurrence of a random scission of the main chain of the polymer salt. The activation energy was calculated from the Arrhenius plot (Fig.4) to be 43.7 kcal/mol. The formation of anhydride structure, appeared partly when the polymer is heated for over 5 hr at 300°C, was not observed below 300°C.

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Dehydrochlorination of poly (ce-chloroacrylonitrile) was carried out by treating the polymer with triethylamine in N, N-dimethylformamide solution (concentration of polymer being 3wt%) at 60°C. Amount of triethylamine, expressed by molar ratio (C_2CI-15)3NNE-CH₂-CCl(CEN)-1, was 0.57, 1.14 or 2.28. The obtained seven samples, whose degrees of dehydrochlorination being 28.4-95.1%, were analyzed spectroscopically to study the structure of -E-CH=C(CE---N)in contained in the polymer. Ultraviolet and visible spectra of these samples showed seven absorption maxima in the range of 200--600 nm, each corresponding to a different number of conjugation n. The relation between Amax of IC-band and 71 was expressed approximately by the following equation: Arna. =-59 n+160 (nm) The characteristics of the main absorption bands of infrared spectra were as follows: The absorbance of 2200 cm^-1 band, assigned to CEN stretching vibration, was directly proportional to the degree of dehydrochlorination. The bands at ca.1500 cm^-1 were assigned to C=C stretching vibration and appeared at lower wave numbers with increasing n. It seemed that 1195 cm^-1 is the characteristic absorption band appeared only in a large n.

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The flow curves of aqueous solutions of sodium alginates, having four different molecular weights, were studied over a wide range of concentration, and their non-Newtonian behaviors were investigated.
The effects of the three kinds of added salts on the above behaviors were also investigated. Log-log plots of the zero-shear viscosity against polymer concentration are linear above the certain critical concentration, and its slope increases with increasing concentration of the added salts.
Bucehe's standard curve are fitted to the plots of vivo against γτ(η: viscosityat shear rate γ, η₀: zero-shear viscosity, τ: maximum relaxation time). Molecular weights (Mr), calculated. from the flow curves, agree well with the molecular weights (Mw), determined by the in- trinsic viscosity measurement. r increases with increasing concentration of polymer and salts.

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The dynamic properties of relatively concentrated aqueous sodium alginate solutions were measured over the frequency range from O.02 to 1.7 Hz. In the region of this frequency, dynamic viscosity is almost independent of frequency, but slightly depends on it with increasing concentration of added salts.
Log-log plots of dynamic viscosity against polymer concentration are a straight line whose slope being about 3.4, and these results are identical with that found in the previous study.
Time-temperature and time-concentration superpositions for dynamic loss moduli are applicable in the present case, and consequently, there is no change in the nature of relaxation mechanism in the ranges of variables (temperature, concentration, frequency, and salt concentration, etc.) used in this work. However, superposition is not satisfactory in the cases of added salt (O.2 mol/l).

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A high speed liquid chromatograph-fluorescence spectrophotometer (HSLC-FP) coupling device was used to analyze polycyclic aromatic hydrocarbons (PAH) in atmospheric pollutants. Atmospheric pollutants were collected on glass fiber filters using a high volume air sampler, and then polycyclic compounds in them were extracted by means of vacuum sublimation. The PAH extract was injected into the HSLC-FP, and the separAtion, identification and estimation of extracted PAH were performed by utilizing the coupling device.
The theoretical plate number of the Zorbax ODS column used was 5400 plates per 25 cm for benzo [a] pyrene. Some relations among several factors (composition of mobil phase, column temperature, and column pressure) and chromatographic data were described.
A useful technique for identification by the HSLC-FP coupling device was given. Flow of mobile phase was stopped when maximum of separated peak was recorded on the chart and fluorescence emission and excitation spectra for the compounds were measured to identify the unknown peaks.
Benzo [a] pyrene in atmospheric pollutants was determined by this technique.

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Isotherms and rates of adsorption of NO₂ as well as adsorbed species on 3 kinds of activated carbon in N₂, N₂ + H₂0 or N₂ + H₂0 + 0₂ atomosphere were investigated as a fundamental study for a removal of nitrogen oxides from exhaust gas. The temperature range was 50-125°C, and the concentration ranges of NO₂, H₂0 and 0₂ were 50-5000 ppm, 1.4-30% (relative humidity: 3.6-79%) and 2.5-40%, respectively.
NO₂ in N₂ is adsorbed as such, but in N₂ + H₂O as nitric acid. The content of adsorbed HNO₃ (y%) is expressed by the following equation: y=100-8.6 x^0.56, when the relative humidity (x%) is larger than 6 (Table 4, Fig.8). The adsorption isotherms are expressed by Freundlich equation (Fig.3, 4, 9, 10, Table 2, 5). The activated carbon with, large specific surface area has excellent adsorption capacity (Table 1, Fig.2, 9). The apparent adsorbed amount in N2 + H20 increases with increasing relative humidity (Fig.10). The adsorbed amount, converted to NO₂, is nearly equal to that in N2 when the relative humidity is 6.50%, but it decreases rapidly above 50% (Table 6). The adsorption rate is controlled by the intraparticle diffusion (Fig.5, 12). The intraparticle diffusivity is proportional to eight tenths power of the concentration of NO₂ (Table 3, 7, Fig.6), and scarcely different among 3 kinds of activated carbon. The effect of coexistence of 02 on the adsorption of NO2 could not be observed (Fig.13).

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The effects of compression pressure on the catalytic activities of powdered nickel-carbon catalysts were investigated. The highest catalytic activity for the dehydrogenation of isopropyl alcohol was obtained by compression at about 2000 kg/cm², regardless of the amounts of the supported nickel or the supporting method of nickel. A compensation effect was observed as expressed by In A =2.30 E +1.38, where A is the frequency factor and E is the apparent activation energy. It was found that the increases of the apparent rate constants were due to decrease in both A and E by compression at about 2000 kg/cm².

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The equivalent conductance of higher tetraalkylammonium perchlorates was measured in hexamethylphosphoric triamide (FIMPA); the values obtained for NH₄, ⁺ tetraheptylammonium ion (n-Hep₄N⁺), tetradecylammonium ion (n-Dec₄N⁺), tetradodecylammonium ion (n-Dod₄N⁺), trioctylpropylammonium ion (TOPN⁺), trimethyldodecylammonium ion (TMDN⁺), tetradecyldimethylbenzylammonium ion TDDBN⁺ and hexamethylenepiperidinium ion (5N6⁺) were 21.2₀, 20.8₀, 21.0₅, , 22.9₂, 20.7₅, 18.0₀, 20.8₀ and 22.7₂ cm²Ω^-11mol^-1, respectively.
These values together with the data for Me₄N⁺, Et₄N⁺, n-Pr₄N⁺, n-Bu₄N⁺ and n-Hex, N⁺ in HMPA solution' indicate that Et₄N⁺ is the smallest in the effective radius calculated from the Stokes' law and TMDN⁺ is the largest in the tetraalkylammonium ions examined. The value for n-Dod, N⁺ is much the same with the value for Me₄N⁺. The value for 5 N 6⁺ is between the value for Me₄N⁺ and that for n-Pr₄N⁺. The solvation number obtained from the effective radius is 1-2 for NH₄⁺

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The combination of triPhenylphosphine and carbon tetrachloride has been utilized widely for the chlorination of alcohol under mild conditions. The presence of sodium iodide in this reaction system provides a convenient route for the synthesis of primary and secondary alkyl iodides (Table 1). Primary alcohols reacted smoothly within 1.5 hr at ambient temperature to afford the corresponding iodides in excellent yields. Iodination of secondary alcohols required somewhat higher temperature and longer reaction time, but no significant amount of rearranged or chlorinated products was formed (less than 3%).

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[1-(Trifluoromethyl)tetrafluoroethoxy]acetonitrile, which was derived from chloroacetonitrile and hexafluoroacetone with potassium fluoride, was hydrolyzed easily to give the corresponding amide [4] and acid (5).
The solubility and pK_a of [1-(trifluoromethyl)tetrafluoroethoxy]acetic acid 5 were determined as 1.34 al and 2.83, respectively, showing that (5) is much less soluble in water than chloro- and cyanoacetic acids with similar acidity.143

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Lanthanoid(BI) phthalocyanine complexes were synthesized by the exothermic reaction by phthalonitrile with various lanthanoid chlorides. The products consisted of the plane ([I] type) and sandwich ([II] type) structure complexes. Increasing the radius of lanthanoid ion, the yield of [I] type complexes decreased, while that of [II] type complexes increased. This tendency is considered to be due to the acceleration of the reaction from [I] to [II] type complex with increasing the radius of lanthanoid ion. In neodymium and praseodymium complexes, the yield of [I] type complexes decreased extremely and [II] type complexes were formed predominantly.

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1, 1'-Diary1-3, 3'-bi(pyrrolo[2, 3-b]quinoxalinylidene)-2, 2'-diones [4] (isoindigo analogues) have been synthesized in three steps. (1) N-Aryl substituted dichloromaleimides [2] were prepared by the reaction of dichloromaleic anhydride [1] with aromatic amines in refluxing acetic acid for one hour. (2) The reaction of [2] with o-phenylenediamine in Methyl Cellosolve at 60-70°C for 2 hours gave 1-aryl-3-chloropyrrolo[2, 3-b]quinoxalin-2(4H)-one [3]. (3) Dehydrochlorination of [3] in DMF afforded 4 J as red to reddish brown powders.
Compounds [4] are soluble in H₂SO₄ with bluish color, but are sparingly soluble in organic solvents. They have excellent thermal resistance. The structure of the product obtained by the reaction of [1] with aniline was also examined.

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