The emisson spectra of the tetrachlorides of carbon, silicon, germanium, and t(y) under the controlled electron impact excitation (300 eV) were investigated.
The A-X transition of CCl was observed at 278-279 nm on the spectrum of CCl₄(Fig.1). The intensity of its photoemission was proportional to both the electron-beam current and the gas pressure (Fig.2); this indicates that CCl (A) was produced in an one-electron unimolecular process. The threshold energy of this band was found to be 15.5 eV; thus, the important process in the dissociative excitation of CCl (A) near threshold is one of those described in Table 1, i. e., (a), (b) and (c). Other lines and bands in Fig.1 were identified as C and CCl.
The spectrum of CCl₄ shows a broad band at 390, -650 nm and many lines of 0 and Cl(Fig.3). Its intensity relation to the electron-beam current and gas pressure (Fig.2) indicated that the broad band originated from a primary product and could be assigned to CCl₂.
The emission spectra of SiCl₄, GeCl₄, and SnCl₄ were similar to the spectrum of CCl₄ (Figs.4, 5 and 6). The intensity of the lines of the central atom increased as its metallic character increased. The bands of SiCl, GeCl and SnCl were also observed. Broad bands in the longer wavelength region could tentatively be assigned to SiCl₂, GeCl₂, and SnCl₂, respectively.

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The predominant tautomeric structures of some p-substituted benzoylacetones (p-RC₆H₄C0CH₂COCH₃, where R =N0₂, COOH, COOCH₃, Br, Cl, H, NHCOCH₃, C_2CH₅, CH₃, OCH₃, OH, NH₂) were estimated, and the substituent effects were investigated by means of IR, NMR and ultraviolet spectroscopies. The presence of the νc-o band at 1624-4590cm^-1 indicated predominance of the enol form over, keto form in the solid or neat liquid state. Linear relationship between νc-o frequencies and a, parameters was obtained with a positive slope in the region of the positive up, while, with a negative slope in the region of the negative a. The presence of intermolecular and intramolecular hydrogen-bonded species in chloroform solution, in which the concentration of the samples was adjusted to 1∼0.01mol/l, was confirmed by VOH band observed at about 3450cm^-1 and 3050cm^-1 respectively. The chemical shifts of OH protons were observed at-5.91∼6.92τ, and were dependent on the sample concentration in the range of 1 to 0.01 mol/l. This signal shifted to the lower magnetic field with increase of the strength of intramolecular hydrogen bond. The absorption band observed at 28-33x 10³cm^-1 is due to the π-π* transition of intramolecular hydrogen bonded chelate ring, and have a tendency to shift toward the higher frequency as the solvents become more polar. A simple Hiickel molecular orbital calculation suggests that the benzoyl carbonyl group is apt to be enolized.

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¹³C-NMR spectra of m- and p-substituted benzoic acids have been measured in DMSO and in 1 N NaOH aqueous solutions. On ionization of the carboxyl groups of these molecules, the carboxyl carbon and the ring carbon (C-1) to which the carboxyl group attaches show downfield shifts by about 6-8 ppm and 4-6 ppm, respectively. On the other hand, the carbons at ortho, meta and para positions show upfield shift by 0.5-2 ppm, 0.2 ppm and ppm, respectively (Fig.2).
The displacements of the chemical shifts for the carbons at ortho, meta and para positions due to the ionization were found to be well correlated with the differences in the total electron densities of the benzoic acids and their carboxylate ions obtained by CNDO/2 MO method (Fig.3). The ¹³C chemical shifts for the carboxyl carbon and C-1 move to downfield despite an increase in electron density.
These results suggest that, in benzoic acids, the displacements of the shifts for the carbons at ortho, meta and para positions are mostly influenced by electronic behavior on dissociation, whereas the shifts of the carbons of carboxyl and C-1 are affected by an electric field effect and changes in factors of paramagnetic term.

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By using the thermobalance specially designed for the experiments in an atmosphere of fluorine gas, the reaction of the activated carbon with fluorine has been kinetically investigated between 50 and 450° C at various fluorine partial pressures ranging from O.05 to 0.135 atm in argon. The activated carbon was prepared by treatment of charcoal with ammonia gas at 950° C. The reaction of the activated carbon with fluorine started to take place at room temperature. The weight of the activated carbon increased in fluorine linearly with temperature between 50 and 280° C due to the formation of graphite fluoride. Above 280° C the carbon lost weight, with the evolution of gasous fluorides. The weight increase was larger with more reactive carbons. In the range from 50 to 240° C, the reaction followed the logarithmic law, q=Klog(t+to) +A. The reaction rate was proportional to the fluorine partial pressure.
The change in pore structure of the activated carbon in the fluorination process was measured by nitrogen adsorption. The micropore-volme (d<30 Å) decreased with an increase in the degree of fluorination, but the transitional pore-volume (40 Å <<150 Å) increased. It is presumed from X-ray study that the activated carbon has a turbostratic structure simillar to graphite crystal, and that the layer distance increased in the initial step of the fluorination process. When over 50% fluorination was attained, the crystalline structure changed into graphite fluoride structure or a structure very close to it.

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The rate constants of several important elementary reactions in the high temperature reaction of benzene and oxygen were determined by use of the shock tube method and computer simulations.
Benzene with or without oxygen which was diluted with argon, was heated behind the incident shock wave. The change in concentrations of biphenyl and carbon monoxide produced wall time were monitored, by measuring the UV absorption at 3060 A and the infrared emissron at 4.87 p. Experimental conditions were as follows. The temperature range was 1400, :: -480001C; the initial concentration of benzene was (1.1-5.5) X 10-7 mol/m/, and the ratio of oxygen to benzene was in the range from 0 to 1.
The reaction times, rci, , and rco, which were the times required respectively for the concentration of biphenyl and carbon monoxide to reach the certain values, were measured. Their dependencies on the initial concentrations of benzene and oxygen, and on the reaction temperature were determined.
By the numerical calculation, six elementary reactions were confirmed to be important in the early stage of the reaction. Among them, reaction (X),
(x) H + O^2- 0 + OH,
was well examined in the H₂-O^2- reaction,
and reaction (X), (x) C6H₅ + O^2- (C6HSO0) --.2 CO + H + C4H4, was studied in the previous paper. The rate constants of four elementary reactions, reaction (I) (N), were determined in this work as follows,

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The catalytic effects of Mg²⁺ and Li⁺ ions on the reactions of a NADH-model compound with a ketone have been studied electrochemically. Ethyl benzoylformate were used as a model substrate, and 1-benzyI-1, 4-dihydronicotinamide (BNAH) as a NADH-model compound. Ethyl benzoylformate exhibits two well defined, one-electron reduction waves in acetonitrile. In the presence of Mg²⁺ or Li⁺ ions, the potentials of these waves shifted towards more positive values owing to the ion-pair formation between the metal cations and the anionic species produced at the electrode. The anodic peak potential of BNAH shifted towards more positive values by the addition of the metal ions. This potential shift is attributed to the complex formation between BNAH and the metal ions. The charge-transfer process involved in the homogeneous redox reactions of BNAH proceeds via a complex like BNAH-metal ionethyl benzoylformate. It is concluded, on the basis of the redox potentials, that the effect of ion-pairing is the main factor in catalytic actions of metal ions.

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The reaction of diphenyl phosphite with several metal nitrates in acetonitrile at 80° C has been carried out, in order to study the behaviour of diphenyl phosphite in aprotic solvent. Diphenyl phosphite was nitrated in these systems. The nitration had the induction period which increased in the order
and also the initial rate of nitration decreased in the order
After the induction period, metal salt of oxoacid anion of phosphorus began to from. The bonding ratios of the metal ion to phosphorus in these phosphorus oxoacid salts, MT, were correlated with the initial rates of nitration mutually. The plot of the initial rates of nitra- tion against M/P showed a good linear relationship of positive slope. The length of induction period showed roughly linear relationship of positive slope with transformation rate of diphenyl phosphite in metal nitrate-diphenyl phosphite system.
On the base of these findings, an interpretation of the induction period on nitration of diphenyl phosphite was discussed.

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The sulfuric acid leaching of coarsely crushed manganese nodules has been carried out. Nodules of 0.7∼4.7 mm in size were leached with 0.5∼3.5 N sulfuric acid in the temperature range of 30° C to 90° C. The kinetics of copper and nickel leaching from manganese nodules were also discussed. The results are summarized as follows.
(1) The optimum leaching conditions for the crushed nodules of 3.4∼4.8 mm in size were 2.8∼3.5 N in sulfuric acid concentration, 500∼750 kg nodules per lc/ acid, and 30∼40 hours of leaching. Under these conditions, 76∼85 wt% of copper and 78∼86 wt% of nickel in the nodules were effectively leached out.
(2) The sulfuric acid consumptions were 0.0031-0.0039 kg-mol/kg nodules used.
(3) The rate-determining step of copper extraction was the diffusion of copper through the inside of and nodule. The diffusion constants were 2.5x 10² cm²/sec at 30° C, 4.1 X 10² at 50° C, 6.1 x 10^-8 at 70° C and 8.6 x 10^-8 at 90° C.
(4) When the leaching was conducted at lower temperatures and in smaller sizes of the crushed nodules, the nickel extraction was dominated by the leaching reaction step and the apparent activation energy of the reaction was 19.4 kcal/mol.
At higher temperatures, the rate of nickel extraction was dominated by the diffusion through nodules and the diffusion constants of nickel were nearly equal to those of copper.

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Recovery of copper from a sulfuric acid leaching solution of manganese nodules was studied by using KELEX 100, LIX 64 N and LIX 70. Extraction of each metal from sulfate solution of Cu²⁺, Ni²⁺, Co²⁺ Fe³⁺, and Mn²⁺, and of Cu from a synthetic leaching solution (Cu 6, Ni 6, Co 0.15, Mn 1.5, Fe 15 g/l) were performed at a following conditions: pH; 0-9; solvent KELEX 100, LIX 64 N or LIX 70; phase ratio (0/A); 1-2; 30° C; contact time; 2, -60 min. In extraction from the single metal solution by KELEX 100, the extraction rate of Cu was faster than that of Fe, but the degree of extraction of Fe was higher than that of Cu at pH 0.5-, 1.5. However, at pH 2, the degrees of extractions of Fe and Cu were reversed and became 80 and 100%, respectively. In the case of LIX 64 N, both the rate and the degree of extraction of Cu were higher than that of Fe, and copper was extracted quantitatively at pH 6.5. In extraction of Cu from the synthetic solution by KELEX 100, a large amount of Fe was co- extracted with increasing contact time. Thus, the extraction percentage of Cu and (Fe/Cu)org. ratio were 93.2% and O.142, respectively, at 2 min. In the LIX system copper was extracted selectively and the degree of extraction of Cu and (Fe/Cu)org. ratio were 52.1% and 0.007. The degrees of extractions of Ni, Co, and Mn in both systems were low and the concentrations of these metals in loaded solvent were below O.3, 0.1, and O.1 mg//, respectively.

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The rate of heterogeneous reaction of oxygen and sulfites in aqueous solution (0.1 to O.5 mol/1) was investigated at temperatures between 25 and 55° C and pH between 1.7 and 7.0. The reaction rate of dithionate and sulfate formation was found to be zero-order with respect to sulfite concentration and proportional to the contact surface area (Figs.1-3). The reaction rate of dithionate formation was found to be the greatest in the pH range of 2.8-3.5, while dithionate was not formed above pH 6.0 (Fig.4). The apparent activation energies were 2.36 and 1.44 kcal/mol, respectively. The effects of additives in the pH range of 2.1, -7.0 were also investigated. Hydroquinone, alcohol and sodium thioisulfate reduced the rate of dithionate and sulfate formation, however, copper (II) sulfate increased the rate of dithionate formation remarkably (Figs.5-7).

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The effects of addition of setting modifiers, i, e., four kinds of accelerator and three kinds of retarder, together with asphalt-wax emulsion as waterproofing material on the waterresistance of set gypsum were investigated in order to elucidate the factors for improvement of the water-resistance. Water absorption, mechanical strength, and pore size distribution of specimens were measured and microstructure of specimens was examined by scanning electronmicroscope.
The results indicated that the accelerators had different effects on water absorption of set gypsum due to the different mechanism of acceleration, depending upon the type of accelerators, while the effect of the retarders depended considerably upon the pouring time (mixing time) of calcined gypsum paste. These effects were discussed in connection with the crystal state and microstructure of set gypsum. Water-resistance of set gypsum would be improved when the crystals of set gypsum are grown enough so as to give large average pore size and consequently to enhance the coating effectiveness of the waterproofing material and also to reduce the capillarity. Strength of set gypsum trends to lower with increasing in waterresistance.

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The kinetics of complexation reaction of nickel(II) ion with 8-quinolinol (HR) in the presence of nonionic surfactant, Triton X-100, Triton X-305, or Tween #20, has been studied by using stopped-flow technique over the ranges of pH 6.8-7.8, at 288-303K, and with μ= 0.1.
The rate of complexation reaction decreased with increasing concentration of a surfactant. This fact was explained in terms of the distribution of the solubilized HR between the micelle of the surfactant and the aqueous phase; because the concentration of HR, which reacted with nickel(II) ion, in the aqueous phase decreased with increasing concentration of the surfactant.
The reaction was of the pseudo-first-order with respect to the concentration of nickel (II) ion. Plots of the reciprocal of the pseudo-first-order rate constants (1/k'_0bs) vs. the concentrations of the surfactant gave a straight line having the same intercept on the ordinate (Fig.3). The conditional rate constant, k_0bs, which is independent of the surfactant concen- tration, was also obtained as a reciprocal of the intercept of each line. On the basis of the dependence of the reaction rate on the HR or of hydrogen ion concentration, it was found that the over-all 1:1 chelate formation reactions proceeded through the following two paths:
Ni²⁺ FIR NiR+ H⁺ Ni²⁺ R- NiR+
The rate constants, k_HR and _kR-, thus obtained are listed in Table 2: they are in good agreement with those determined by the solvent extraction method.
The activation parameters for these two reactions were determined and are listed in Table 3.

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The rate of complexation reaction between nickel(II) and 1-pyrrolidinecarbodithioate (PDT) in the presence of nonionic surfactant, Triton X-100, has been studied by a stopped-flow method over the pH range of 6.8∼8.0, and at 288∼303K.
Since the complexation reaction between nickel(II) and PDT is a precipitation reaction in aqueous solution, the rate of this reaction can not be followed by the measurement of absorbance. In the presence of nonionic surfactant, as the chelate of nickel(II) with PDT dissolved into micelle, the kinetics of this reaction could be studied with stopped-flow method.
The reation was of first-order with respect to nickel(II) ion and PDT, and independent of a hydrogen ion concentration. The surfactant did not have a direct influence on the rate of this reaction. On the basis of these results, it was found that the rate-determining step is the 1: 1 chelate forming reaction between nickel(II) ion and PDT ion (R):
The estimated rate constant, k= (2.60+ 0.03)x10⁴ dm^-1.mol^-1.s^-1 was in good agreement with that for dissociation of coordinated water molecule from nickel(II)ion.
The activation parameters of the rate-determining reaction were determined. The values are Ea (52.±0.8) kJ.mol^-1, ΔH^‡: (50.2±0.8) kJ.mol^-1, ΔF^‡: (47.7±0.2) kJ.mol^-1, ΔS^‡:(7.9±2.8) J.mol^-1.K^-1.

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Long absorption cell technique was applied to the cold vapor atomic absorption for the determination of nanogram level of mercury. The method of both reducing vaporization and direct heated vaporization coupled with long absorption cell has been developed for extra micro amount of mercury in biological and environmental materials.
Quartz absorption cells of 17 to 150 cm length have been tested at the most favorable experimental conditions (N2 flow rate: 0.6 //min, sample amount: 10 ml and the vibration time: 40 sec). Sensitivity was found to increase proportionally to the cell length and the detection limit of 0.02ng Hg was obtained with the 150 cm cell.
The determination of mercury in some standard reference materials (NBS SRM 1571, Orchard Leaves, SRM 1630, Coal and SRM 1642, Mercury in Water-Trace) were performed and the satisfactory values of mercury were obtained using this experimental systems. A furnace system for solid samples was designed and applied for the analysis of some standard reference materials with favorable results.
The simultaneous determination of organic and inorganic mercury at the nanogram levels was also performed, using the standard solutions prepared from ethylmercury chloride and phenylmercury acetate.

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Identification and determination of small amount of impurities in the commercial reagent grade benzoic acid were carried out by gas chromatograph-mass spectrometer. Impurities in benzoic acid were too small in quantity to identify directly by gas chromatograph and mass spectrometer. Therefore, enrichment of impurities by zone melting method was applied prior to subsequent GC-MS analysis.
Methyl benzoate, ethyl benzoate, methylbiphenyl isomers and toluic acid isomers were identified as impurities by their mass spectra. Identification were confirmed by chromatographic retention data of reference substances.
Multiple ion selector (MIS) was superior to the total ion current detector. Small amount of impurities in benzoic acid was determined sensitively and selectively without preconcentration by setting MIS to their characteristic fragments. For example, o-toluic acid, whose gas chromatographic separation from benzoic acid being umcomplete, was selectively determined by setting MIS at m/e =118. Minimum detectable amount for o-toluic acid was found to be 2x10^-11g and for other impurities 1x10^-11g.
The major organic impurities in benzoic acid were toluic acid isomers and amount was found to be 35∼155 ppm in several kinds of benzoic acid.

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The rate of thermal decomposition of 1, 4-diaryl-1, 4-dimethyl-2-tetrazene [1] was measured in five solvents by UV spectroscopy at the temperature ranging from 50 to 95° C. Rate constants (k_d) increased with the polarity of the solvents. The activation parameters were calculated based on the dependence on the temperature. A plot of ΔH against the solvent polarity parameter E_Twas found to be linear. The change in ΔS was compensated by a correspond- ing change in ΔH.
On the basis of the kinetic data, the influence of the solvent on the decomposition of [1] was discussed.

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Eight bis (trifluoromethyl)naphthalenes [5] were synthesized by route A (for 1, 2-, 1, 3-, 1, 4-, 1, 5-, 2, 5-, 2, 6-, and 2, 8-derivatives) or route B (for 1, 5-, 1, 8-, and 2, 5-derivatives). The route A involves the following sequence: iodonitro- [1]→ (trifluoromethyl) nitro- [2]→ (trifluoromethyl) amino- [3]→(trifluoromethyl) iodonaphthalenes [4]→[5], while the route B involves direct conversion of diiodonaphthalenes [6] into [5].
Substitution of iodine for trifluoromethyl group was performed by the reation of the iodo compound [1], [4], [6] with trifluoromethyl iodide and copper powder in pyridine. The yields of the products were generally good except for the reaction of 1, 8-diiodonaphthalene, which gave bis (trifluoromethyl)naphthalene in a poor yield probably because of steric reasons. In this reaction, considerable amounts of (trifluoromethyl)naphthalene and his (trifluoromethyl)- binaphthyl were detected.

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Oxidation of ethylene in acetic acid catalyzed by combinations of palladium chloride, copper (II) acetate, lithium chloride and lithium acetate has been examined in a bubble column. The effects of teaction conditions, such as the partial pressure of ethylene and oxygen, catalyst compositions and temperature, on the rates of ethylene oxidation by Pd(II) and oxidation of Pd(0) were measured and the empirical rate expressions were obtained under the reaction conditions in which catalyst maintains initial activity.
The experimental selectivity defined as the ratio of the amount of vinyl acetate to that of ethylene absorbed under the conditions of steady activity of the catalyst agreed well with the value calculated by the above rate expressions.
In an attempt to improve the efficiency in use of Pd, an expression giving the reaction conditions under which the catalyst activity remains steady was derived from the empirical rate expressions together with the data on solubility of copper(I) chlpride in the reaction mixtures. The result is shown in Fig.9. The reaction conditions suitable for maintaining almost' initial activity of the catalyst were found to be higher concentration of LiCl, lower concentration of PdCl₂ and Cu(OAc)₂, lower ratio of ethylene to oxygen partial pressure, and lower temperature. As for lithium acetate, its lower concentration favored steady activity of the catalyst in the case of less than 1 mol/l, and the higher concentration was favorable for more than 1 mol/l.

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The liquid phase oxidation of 1, 2, 4, 5-tetramethylbenzene (TMB) was studied in acetic acid using high concentration of transition metal acetates as catalysts in the presence of bromide.
When transition metal acetates were used in amounts equimolar or more than TMB, the oxidation of TMB proceeded smoothly until TMB was completely consimed, resulting in the formation of pyromellitic acid in a high yield. Especially, when Co-Mn-Br or Co-Ce-Br was employed the yield was over 90%. Pyromellitic acid produced was isolated as the precipitate of metal pyromellitate. By the analysis of carbon monoxide and dioxide the complete oxidation of TMB was concluded to be negligible in this reaction.

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N-(Alkoxymethyl)pyridinium chlorides (AOP series) and N-alkylpyridinium chlorides (AP series) were prepared and their properties were compared. The samples obtained were identified by the elementary analysis, IR and NMR spectroscopy. The measurements of the physicochemical properties were carried out on aqueous solutions of AOP and AP series. Depression of the surface tension and durability of emulsification of liquid paraffin into dilute aqueous solutions of the AOP series were larger than in AP solutions at the same concentration. Thus the AOP series are more surface active than AP series. The slope of linear log CMC vs. alkyl chain length plots on AOP series was larger than that of AP series. Solubilization of a small amount of dyestuff was observed in dilute solution of AOP 14 at 30° C, while considerable amounts were solubilized in the highly concentrated AOP 14 solution. The amounts of sedi-, mented CaCO₃ in the dilute (<CMC) aqueous solutions of AP and AOP series decreased with the increase of the length of alkyl chains of the samples. When the concentration of both series were fixed above the CMC, the sedimentary curves of CaCO₃ showed aggregation in comparison with that of the water.

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Several 8' (or 6')-substituted 4, 5, 6, 7-tetrachloroquinophthalone (2-[8(or 6)-substituted 2- quinolyl]-4, 5, 6, 7-tetrachloroindan-1, 3-dione) derivatives were synthesized by the condensation of 8 (or 6)-substituted 2-methylquinolines with tetrachlorophthalic anhydride. The effects of the substituents to the pigment properties of these derivatives were discussed.8'- (Chloro, bromo or hydroxy)-4, 5, 6, 7-tetrachloroquinophthalones were similar to Cadmium Yellow in color and had excellent pigment properties, being resistant to light, heat and organic solvents. Some contributions of an intramolecular interaction, for example, an intramolecular bifurcated hydrogen bond, induced by the substituent at 8'-position to the pigment properties were also discussed.

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New organic pigments, 4, 5, 6, 7, 10'-pentachloro- and 4, 5, 6, 7, 7', 10'-hexachloro[7', 8']benzoquinophthalone (2-[10-chloro (and 7, 10-dichloro)-benzo[h]quinolin-2-y1]-4, 5, 6, 7-tetrachloroindan-1, 3-dione) were prepared to get a substitute for Cadmium Yellow (CdS). These chlorinated 8'benzoquinophthalones were quite similar to CdS in color and had excellent pigment properties, being resistant to light, heat, migration and organic solvents.
A number of 2-[10-chloro (or 7, 10-dichloro)-benzo[h]quinolin-2-y1]-4, 5, 6, 7-tetrachloro (or bromo)indan-1, 3-dione and 2-[10-chloro (or 7, 10-dichloro)-benzo[h]quinolin-2-y1]-5, 6, 7, 8-tetrabromobenzo[ f ]indan-1, 3-dione derivatives were synthesized by the condensation of tetrachloro (or tetrabromo) phthalic and 5, 6, 7, 8-tetrabromonaphthalene-2, 3-dicarboxylic anhydrides with 10-chloro (or 7, 10-dichloro)-2-methylbenzo[h]quinolines. The contributions of the chemical structure and intramolecular bifurcated hydrogen bonding to pigment properties such as color, the resistance to light, heat, migration and organic solvents were also discussed.

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To determine the structures of anhydro bases derived from natural anthocyanins, pelargonin, peonin, malvin, and cyanin, ten model compounds in which the 4- or 7-hydroxyl group are replaced by the methoxyl group were synthesized. A comparision of the visible absorption spectra of these anhydro bases has shown that the anhydro bases of pelargonin, peonin, and cyanin have the 7-keto structures and that the anhydro base of malvin has the 4'-keto structure.
The pK-values of these flavylium chlorides lie below 3, showing that the red flavylium salt and the purple anhydro base are unstable in the pH ranges of cell sap of flower petals and that they change into the colorless pseudo base. In neutral and weakly alkaline media, the anhydro bases of cyanin type flavyliums formed complexes with boric acid and their λ_max shift- ed to the shorter wavelength.

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Cationic polymers containig triethylenediammonium (TDA) ring in their main chains as shown in formura I and II were prepared. From the mesurements of conductivity and Xray diffraction patterns of their 7, 7, 8, 8-tetracyanoquinodimethane TCNQ salts, the effect of polycations on the electric properties of the TCNQ salts were discussed.
The activation energies of conduction for the (I)-TCNQ simple salts were 0.2-0.3 eV regardless of the number of the methylene chains. The conductivity of these simple salts was dominantly affected by the TDA ring which has narrower interval between the cationic sites, rather than by the methylene chains. The (I)-TCNQ complex salts whose number of methylene chains were n=4, 6 showed higher conductivity than those of n=3, 5. The crystalinity of these TCNQ complex salts determined from their X-ray patterns showed the same tendency. From the results it was suggested that the structures of polycations affected on the arrangement of TCNQ molecules.

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Polycondensation of D-glucose with polyphosphoric acid (PPA) as a condensation agent in dimethyl sulfoxide (DMSO) has been studied in order to obtain a reaction conditions for obtaining the synthetic glucan in high yield and to elucidate the structure of the synthetic glucan. The colorless synthetic glucan was obtained in the highest yield of 41% by the reaction of 20 g of anhydrous D-glucose with 30 g of PPA in 50 ml of DMSO at 50° C for 7 hr.
The charactaristics of the synthetic glucan were as follows: the degree of polymerization being 81, [α] +62.5 (H₂O, c=1), and combined phosphorus 1.9%.
The structure of synthetic glucan was studied by the method of the periodate oxidation and the Smith degradation.
The periodate oxidation gave 0.78 mol/glucose unit of the consumed periodate (I0), 0.30 mol/glucose unit of the formed formic acid, and 0.15 mol/glucose unit of the formed formaldehyde.
The measurement of D-glucose and sugar alcohols by the method of Smith degradation gave D-glucose, glycerol, and erithritol in mol ratio of 1.00: 1.71: 0.27, respectively.
Above experimental results showed that the amount of the formic acid formed was relatively high when compared with the amount of the consumed periodate in the method of periodate oxidation and the amount of the glycerol formed was also high in the method of the Smith degradation.
The results suggested that the synthetic glucan has many non-reducing end groups and, therefore, many branched chains.

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The polymerization of methyl methacrylate (MMA) initiated by chlorocarbonylbis(triphenylphosphine)iridium(I) (Ir complex) and organic halides in benzene was studied. The effect of combination of organic halides with Jr complex on the polymerization was studied, and it has been found that carbon tetrachloride (CCl₄), carbon tetrabromide, and bromoform show the polymerization ability. On the basis of the kinetic studies of the polymerization of MMA in benzene initiated by Jr complex and CCl₄ (low concentration), the rate of polymerization (Rp) was expressed by the following equation:
Rp=k[Ir complex]^0.5. [CCl₄]^0.5. [MMA] ^1.0
The apparent overall activation energy for the MMA polymerization by the use of this initiator was estimated to be 17.6 kcal/mol. The composition curve of the copolymerization of styrene with MMA by the use of this initiator agrees with that of the radical polymerization; the polymerization of MMA is inhibited by 1, 1-diphenyl-2-picrylhydrazyl and p-benzoquinone. On the basis, of the above results, the polymerization of MMA by the use of this initiator was found to proceed through a free-radical mechanism.

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To examine thermal degradation of polymers in detail, an improved fixed bed reactor, based on flow system, was constructed.
On this apparatus, it was possible to vary the factors affecting reaction such as degradation temperature, residence time, melting temperature of sample, sample feed rate, and grain size of heat carrier; further, the temperature gradient in the reactant and the secondary reaction of degradation products can be depressed.
Thermal degradation of polystyrene was studied by the reactor. When the temperature gradient in the reactant increased, the yield of styrene decreased and those of dimer and trimer increased (see Fig.8). When the degradation products could not be distilled easily, by-products, which did not correspond to the structure of polystyrene, increased (see Table 3). On the other hand, when normally operated, the degradation products of polystyrene were consist of only monomer, dimer, trimer, and heavy oily products (small amount), which corresponded to the structure of polystyrene.
Thus it was proved that the apparatus is successful for the elucidation of the thermal degradation mechanism of polystyrene.

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The atomospheric hydrogen sulfide at several ppb levels was determined by fluorometric method. This method is based on the fact that the presence of absorbed H₂S quenches the fluorescence of the FMA (fluorescein mercury (II) acetate) solution. The method shows high sensitivity and reliability, and is suitable for the measurement of H₂S at background levels. The range of determination of I-12S is from 0.1 to 10 ppb in sampling air volumes of 4l.Hydrogen sulfide is collected by passing the air through two bubblers, each containing 20 ml of 0.1 N NaOH. More than 95% of atmospheric H₂S can be collected by passing the air through two bubblers at the rate of 0.2 //min for 20 minutes.
In summer 1975, the fluorometric method was used to measure atmospheric H₂S at Hiyoshi, Yokohama. The result of these measurements is shown in Table 1. The average concentra- tion of H₂S during the sampling period was 2.7 ppb (1O^2- measurements). The interesting phenomenon, that the concentration of LS decreases during the daytime, was observed (Fig.2). The concentration of H₂S in the atmosphere, obviously relates to the weather conditions, temperature, humidity, and wind (Figs.3 and 4). Under retained air conditions, high concentrations of H₂S (4 or 5 times higher than the usual values) were measured (Table 3).

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Adsorption of complex anion composed of heavy metal ion (Hg²⁺, Cd²⁺, or Zn, 2, +; initial concentration: 1.0 ppm) and inorganic anion (CN-, SCN-, or I-) on activated carbon prepared from coal by steam activation has been stuaied.
From the adsorption of mercury(II) ion on activated carbon in the presence of cyanide or thiocyanate ion, cadmium ion in the presence of iodide ion, or zinc ion in the presence of cyanide or iodide ion, it was found that mercury(II), cadmium or zinc ion was easily adsorbed on activated carbon in the form of complex anion such as Hg(CN)₄^2-, Hg (SCN)₄^2-, Zn(CN)₄^2-, or ZnI₄^2-, respectively.
These results suggest that the complex anion of heavy metal ion has unexpectedly strong affinity for a surface of activated carbon.

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To elucidate the effect of SO₂ on photochemical smog formation in atmosphere, the photochemical reaction occurred in SO^2-cis-2-butene system were studied in the gaseous phase.
It was found that SO₂ brought about the isomerization from cis-2-butene to trans-2-butene. Analysis, due to GC-MS methods, showed that ethyl methyl ketone and acetaldehyde appeared in the oxygen containing SO^2-cis-2-butene system, but acetaldehyde did not appear in the system without oxygen. The formation of carbon monoxide and of liquid-like particle(mist) was also observed in SO^2-cis-2-butene system irrespective of the presence of oxygen. However, carbon monoxide appeared faster in oxygen containing system than in the system without oxygen. Numerous liquid particles, probably consisting of some unknown polymers, were found in the reaction tubes containing both systems with and without oxygen. The formation of the particles occurred faster in the presence of oxygen than in the absence of it.
Finally, the role of oxygen in the photochemical reaction occurred in SO^2-cis-2-butene system was discussed.

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Studies have been made on the adsorption of iron OE, nickel (II), and copper (II) by tita- niutn(W), hydroxide. The adsorbent was prepared from acrylamide, N, N' -methylenediacry- lamide, and titnium(N) hydroxide. The adsorbed iron (III), nickel (II), and copper(II) were able to be eluted from the gel column by dilute hydrochloric acid (O.1-0.2 mol/l). The flow rate of samples, the effect of concentration on the adsorption, the recycle usage of the column, etc. were tested. It was found that the adsroption of iron (III), nickel(II), and copper TO tended to rise with decreaing concentration of adsorbents. The adsorption was quantitative when the flow rate was below 1.50 ml/min. The capacities of adsorption of iron (III), nickel (II), and copper(II) were 6.71, 2.09, and 2.88 meq/g, respectively. It seemed that the proposed method is applicable to the recovery of heavy metals. Also, it was expected that the gel composite adsorbent is a new packing agent for the chromatography.

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A single crystal of β-silver iodide was cleaved along the (0001) surface and then the cleaved surfaces were chemically etched. Upon observation with a metallurgical microscope, the etched pattern of (0001) surface entirely differed from that of (0001) surface. This difference can be explained in terms of the polarity of the β-silver iodide crystal which has a noncentrosymmetric structure.
Upon exposure to strong light, colloidal particles of plate-like silver iodide crystals in the state of aqueous suspension moved toward a light source or kept away from it. This anomalous behavior would also be attributed to the polarity of the silver iodide crystal.

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An expression of a reduced solubility curve (RSC) was derived from Hildebrand's equations (Eqs. (1)∼(3)) introducing a reduced temperature (θ= T/T_a, /T_a: critical temp.), eliminating the terms of solubility-parameters (δ1, and δ2), using a ratio (k= V2/V1, ) of molar volumes (V1 and V2). The RSC which expressed a correlation of θ and solubilities (x' and x'') of a binary system, depended only on the k value but not on δ1, δ2, V1 and V2. The value of k or x'' could be calculated approximately by Eq. (8) or (8') from the values of x' and x'' or k whithout the trial-and-error method. An application of RSC to a solid phase system was discussed, and using the empirical equations (Eqs. (8)∼(11)), the solid-solubility curve of MgO-CaO system estimated was in good agreement with observed data.

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Direct preparation of copper phthalocyanine (Cu-Pc) pigment was studied. A mixture of phthalic anhydride, urea, ammonium nitrate and catalytic amount of ammonium molybdate in decalin (decahydronaphthalene, mixture of cis and trans) was heated for 2 hours at 170-5° C to give 1-amino-3-iminoisoindolenine nitrate. After cooling the reaction mixture to 130° C, the mixture was treated with urea solution of copper (II) hydroxide and kept at the same temperature for 1 hr. The product was purified successively with ethanol, dilute hydrochloric acid, dilute sodium hydroxide solution and hot water and dried at 80° C.
The Cu-Pc thus obtained was of polymorphous metastable a-form with greenish blue color and with particle size of 0.3-4.5, um.
Decalin has proved to be an appropriate solvent for finely powdered Cu-Pc synthesis since the transformation of a-form Cu-Pc to β-form was very sluggish in this medium.

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The Prins reaction of alloocimene with formaldehyde proceeded smoothly in dichloromethane under reflux in the presence of acetic acid. The reaction products were mainly 2- (2- methy1-1-propeny1)-4, 5-dimethyl-5, 6-dihydro-2 H-pyran [2] and trans- or cis-4, 5-dimethy1-5- (4-methyl-1, 3-pentadienyl)-1, 3-dioxan, [3] or [4]. The stereochemistry of the dioxans, [3] and [4], was also discussed on the basis of the NMR spectra. The compositions of the products were dependent on the isomer ratio of alloocimene used.

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