Solvent effects on the visible spectra of xanthene dyes were studied in relation to the hydrogen bonding.
The xanthene dyes show a definite blue shift when the solvent is changed from DMA to water. In order to elucidate the shift, solvent effects on the visible spectra of Uranine and Eosin Y were studied. Although dielectric constant of solvent has little effects on the shift, the shift depends on the refractive index and the proton donating ability of the solvents. These facts indicate that the shift observed consists of two contributions, i. e., general solvent effect and hydrogen bond effect.
On the assumption that McRae's theory holds for such protic solvents as NMA and IPA, the shift due to the hrdrogen bond was estimated.

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Angular variations of X-band ESR spectra of Gd(ll ) in single crystals of Ln2M3il (N08)1224 H₂0 (where Ln (B) =La, Ce, Pr, Nd, Sm, and Eu; Mu =Co and Zn) were studied at room temperature. The observed spectra showed similar angular variations to those of Ln2Mg3(NO₃) /2° 24 H₂0 for each host lattice. A linear relationship was obtained between the zero-field splitting energy levels or the largest spin-Hamiltonian parameter VI and the lanthanoid contraction. It was found in most lanthanoid(11J) host lattices that b3 decreased with the decreasing ionic radius of the divalent metal ion M. The effects of the neighbor and host lattice, i. e. the [Mil (H₂0)]0 and [Ln(NO, ), ] in double-nitrate cystals, were qualitatively explained by a pointcharge model. The apparent spin-Hamiltonian parameters and zero-field energy levels of Gd(111) in double-nitrates were well-estimated.

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Nuclear magnetic resonace spectra, absorption spectra and relative fluorescence intensities have been measured of mixed solutions in H₂O and/or D20 of a nonionic surfactant, n-dodecyl hexaoxyethylene glycol monoether (abbreviated to Cl2E08), and a fluorescence dye, sodium distyryl biphenyl-2, 2'-disulfonate (abbreviated to FB). In the mixed solutions, the relative fluorescence intensity of FB remains constant below the CMC of Cl2E06, while it increases considerably with increasing concentration of Cl2E06 above the CMC and, at the same time, the absorption maximum of FB begins to shift to a longer wavelength. This fact suggests that the micelles of Cl2E06 play an important role, in the interaction between FB and Cl2E06 molecules. The chemical shifts of protons of these two materials in D20 have shown that the interaction between FB and Cl2E06 molecules takes place in the polyoxyethylene shell of the Cl2E06 micelle. The line-width of the NMR signal of the alkyl methylene protons of Cl2E06 becomes narrower when FB is added to the micellar solution, showing that the degree of motion of the alkyl chains in the micell core is changed owing to the interaction between the aromatic part of FB and the polyoxyethylen chain of Cl2E08.

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In order to elucidate the CO oxidation mechanism and the oxygen deficiency of the semiconducting BaTiO₃ (doped with La208-0.5 mol %), oxidation of gaseous CO by the adsorbed oxygen on these materials was studied by a pulse reactor.
The rates of the reduction of these catalyst by CO pulse and the consumption of CO in the first CO pulse by the surface Oxygen were expressed by a first-order equation for the normal pulse method. Apparent acti-V'ation energy for these reactions (about 13.8 kcal/mol) calculated from the temperature dependence of the rate constants almost agreed with that obtained by the integral flow reactor.
The rate of decrease -in the activity of oxygen by the repeated CO pulses calculated assuming differential conditions was expressed by the Elovich equation. The Elovich plots were divided into two segments at the conversion of the active oxygen 0.9. Apparent activation energies obtained from the Elovich plots varied with the conversion from 13.0 kcal/mol to 23.5 kcal/mol. Total amounts of active oxygen were 10-8 mol/g-catalyst. Reaction mechanism was explained by the Rideal mecbanism.
These results were supported by the fact that the conductivity of the catalyst in the mixed gas was larger than that in oxygen as reported in the preceding papers.

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The acidic behaviors of the nickel oxide-silica catalyst were studied focused on the acid sites and their structures. The total acidity of the catalyst was measured by n-butylamine titration method and the distribution of BrOnsted and Lewis acid on the catalyst surface was determined by infrared Spectra of pyridine adsorbed on the catalyst. Electronic reflectance spectroscopy was used to investigate the crystalline field symmetry of the nickel ion in silica gel. The following results were obtained.
1) The co-precipitated nickel oxide-silica catalyst gave larger acidity than the supported one, whereas, the maximum acid- strength was relatively weak (Ho= +1.5) in each catalyst (Table 1).
2) Acidity was increased remarkably by raising the evacuation temperature (Fig.3).
3) Acid sites, found on the nickel oxide-silica catalyst, were only Lewis acid type, which did not change into Brsted type by adding water (Fig.4, 5).
4) When the co-precipitated catalyst was calcined in air at 500° C, nickel ion occupied a site of octahedral or distorted octahedral symmetry in the silica gel (Fig.6, 7).
It was concluded from the results mentioned above, that there are vacant ligand sites of octahedral or distorted octahedral nickel ion on the catalyst surface acting as Lewis acid sites.

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The title reaction was studied over NiO-ZnO catalyst in order to elucidate its catalytic characteristics. The catalyst showed higher catalytic activity than the parent oxides, NiO and ZnO (Table 2). The activation energies of the reaction over NiO-ZnO (7.2 atm% Ni) and ZnO were 9.9 and 19.2 kcal/mol, respectively (Fig.5). The initial cis/trans ratios of 2-butene produced were about 5 for both catalysts (Table 2). A correlation was found between the concentration of the electron donating sites which was measured by means of TCNE adsorption and the rate of 1-butene isomerizatipn (Fig.6). X-ray and electronic spectroscopic studies indicated that Ni²⁺ ions of the most active catalyst (7.2 atm % Ni) exist in the solid solution of ZnO and NiO (Fig.1, 2).
It is proposed that the active centers for the isomerization of 1-butene are basic O^2- ions on the surface of the NiO-ZnO solid solution.

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The active sites on BeO were studied for the isomerization of n-butene and the alkylation of phenol in a flow reactor.
Below, 260° C of reaction temperature, BeO was active for the isomerization of 1-butene to cis-2-butene and the active sites are mainly basic. On the other hand, above 260° C, the isomerization to trans-2-butene was predominant. This catalytic action is remarkably different from those of alkaline earth oxides (MgO, CaO etc. ).
Main products from the alkylation of phenol were anisol, o-cresol, m+p-cresol and 2, 6- xylenol. In the temperature range of 300-400° C, the yield of anisol increased with the reaction temperature. o-Cresol, m+p-cresol and 2, 6-xylenol were obtained above 400° C (Fig.4). These results are quite similar to that of alkylation over active-Al2: 4 catalyst. Molar ratio of anisol/ o-cresol obtained was 3.71 at the initial stage. The yield of anisol was more strongly decreased by pyridine poisoning to BeO catalyst than that of o-cresol (Fig.5).
From these results, we concluded that BeO has hoth basic and acidic active sites.

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Dehyrogehation and dehydration reactions of 2-propanol and 1-butanol over three kinds of uranium oxide catalysts, UO₃, UsOs and UO₂, were investigated at temperatures near 2160° C using the pulse-reaction method.
As shown in Figs.1-4, conversion and selectivity showed complicated changes with repeated sample injections. In general, except for Fig.1, dehydration to olefin predominates in the initial pulses, but repeated sample injections result in a significant decrease in dehydration activity and an increase in selectivity for dehydrogenation. During the course of reaction, UO, and U505 catalysts were reduced to oxides of lower oxidation state. Thus, a stationary catalytic activity was, achieved after several sample injections.
The conversion data for the reaction of 2-propanol over UO₂ catalyst were found to be approximately expressed in the zero-th order kinetics. Since there was no essential difference in reaction rate between 2-PrOH and 2-PrOD, we postulated the rate-determining step to be an a-hydrogen elimination process. In this paper, it has been further noted that there is appreciable difference in catalytic activity and selectivity between uranium oxide and such heavy-metal oxides as WO^2-, MoO₃ and V205.

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The anodic and cathodic behavior of adsorbates formed on a bare Pt/Pt electrode during the open-circuit chemisorption of ethanol in 1 mol/l KOH solutions is described and discussed. It is found that a new-type surface species is formed under limited conditions.
Its behavior in potentiodynamic oxidation and reduction is different from that of any species of 0 or CH-a type so far reported; it is oxidized as easily as 0 type species, and is cathodically desorbable like CH-a type species. In the open-circuit chemisorption of ethanol, low temperatures favor the formation of this new-type species rather than of 0 type species and high ethanol concentrations favor the formation of CH-a type. When the temperature is ° C and the ethanol concentration is less than about O.01 molg, the adsorbates formed from ethanol are almost exclusively this new-type species besides adsorbed hydrogen atoms. In this case, the amounts of electricity expended in the oxidation of each of these two species are nearly equal, regardless of the time of open-circuit chemisorption. The anodic oxidation of this surface species in a blank 1 mol/l KOH solution gives acetate ion.
These facts, when considered in connection with the possible reactions in the open-circuit chemisorption of ethanol and the anodic oxidation of the adsorbates, lead to the following conclusion. In the open-circuit chemisorption of ethanol under the favorable conditions described above, two hydrogen atoms are released from one molecule of ethanol, resulting in acetaldehyde, the new-type species.

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Role of oxalate ion during anodic oxidation of Al under gelvanostatic condition in oxalic acid solution was investigated, examining the time dependence of bath voltage, microstructure of anodic film and C_2CO^2- content of the film. Electron microscopic observations indicated that a number of pores were developed in the film formed after a while of the start of electrolysis and was followed by the decrease of number and total area of pores. In the initial stage of electrolysis, C_2CO^2- content of the oxide film was slight, however oxalate ions migrated into the barrier layer as field potential became higher, and took part in the formation of film as ligands. During bath voltage arose linearly, the increase of C_2CO^2- content was observed. After the attainment of steady bath voltage, C_2CO^2- content became nearly constant. The distribution of anions in the wall of porous layer was examined. The wall of porous layer was found to consist of three parts, such as the outer part of layer containing relatively much C_2CO^2-, the intermediate part of layer containing a large quantity of C_2CO^2- and the inner part of layer containing a little. Such results were explainable in terms of the variations in electric field and the mobility of each anion in barrier layer. Further, it was found that C_2CO^2- content of layer increased, as temperature was lower and/or electrolyte concentration was higher.

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The effect of lithium ion on the formation of active material from nickel plaque have heen studied at various temperatures by means of the current-potential curves obtained with polarized nickel electrode in alkaline solution and the electromicrophotograph of the surface of nickel electrode.
The results are summerized as follows.
( 1 ) As the temperature increases, the amount of active material formed from nickel plaque increases, but the formation of nickel-lithium compound becomes more rapid. Therefore, the oxidation of nickel plaque is disturbed at higher temperatures.
( 2 ) The increase in activity of OH- in LiOH with temperature is smaller than that in KOH.
( 3 ) The active material produced by repeated oxidation-reduction cycles reacts with lithium ion, resulting in shedding.
Because of such phenomenon, the over charge-discharge is not desirable when lithium ion is added to electrolyte solution.

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Ionic conduction in sintered oxides with hollandite type structure KxMgzi2Ti8_x/2016, which have tetragonal lattice and involve tunnels along the c axis, was investigated. Degree of sintering was defined by the ratio of apparent density of theoretical X-ray density. When K2CO₃, MgO and TiO₂ were fired at 1200° C for 5 hr after prefiring at 950° C for 10 hr, the degree of sintering reached 85-90%. From the results of the powder X-ray diffractions and fluorescence X-ray analyses and lattice constants, the composition range of tetragonal single phase was determined to be 1.6s x s 2. O. The tablets of about 11 mm in diameter and 2 mm in thickness were prepared from the sintered single phase and their A. C. conductivities at 10 kHz were measured using a pair of gold plate electrodes in the temperature range from 200° C to 400° C. The conductivities were found to increase from the order of 10-5 to 10-4 mho. cm-i with the decrease of x. The species contributing to the ionic conduction in the sintered specimens of single phase was clarified to be potassium ion by measuring the weight changes of the tablets before and after the electrolysis according to Tubandt's method. The relation between the potassium ion conduction and the hollandite type structure was discussed.

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Recovery of ammonia by sulfonyl diamide supported on silicate columnar particles (5 mmcfX 10 mm) has been studied.
The absorption amounts and breakthrough curves of ammonia by the absorption column (32 mm--'27O mm, absorber: 122.5 g) were determined under the following experimental conditions, concentration of ammonia in ammonia-nitrogen gas mixture; 20, 30, and 60%, temperature; 0, 10, and 20° C, superficial linear gas velocity; 0.2-1.5 cm/sec.
It was found that ammonia can efficiently be recovered by the absorption column in anhydrous state from the gas mixture of which the concentration of ammonia is relatively low.
Sulfonyl diamide-ammonia solution was also prepared by passing ammonia through the absorption column in which sulfonyl diamide was packed. The viscosity of resulting sulfonyl diamide-ammonia solution was about 9-11 x 10-2 P at 0-10° C.

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Raw material, SnO₂ powder mixed with graphite or tin powcer, was placed in a porcelain crucible and heated at 1200° C in an electric furnace for 2 hrs. Material containing 5 to 10 wt % of Sb208 was also used to obtain Sb-doped crystals. SnO₂ needle crystals were grn above the raw material.
It is supposed that SnO vapor was formed through the following reactions:
SnO^2- C (or 1/2 C) SnO + CO (or 1/2 CO₂) SnO^2- Sn 2 SnO
and SnO₂ crystals were subsequently deposited from the vapor phase with reoxidation of SnO.
It was found that suitable contents of graphite were 5 to 7 wt %, and those of tin were 25 to 30 wt %. The considerable influence of a gap width between crucible and lid on the growth of SnO^2- crystal was observed.
Undoped SnO₂ crystals which were colorless and transparent, were grown up to 50 x 0.06 X 0.06 mm, and Sb-doped ones which were grayish blue and transparent, up to 30 X 1 X 0.1 mm. Electrical resistivity of undoped crystals was 50 to 100 I2-cm at room temperature showing non-metallic conduction, and activation energy was 0.11 to O.15 eV. On the other hand, electrical resistivity of Sb-doped crystals was 2.4 10-3 Si-cm at room temperaturt showing metallic conduction, and the temperature coefficient of the resistivity was 2.3 x 10-6 S₂-cmi° C.

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The adsorption behavior of anionic surface active agents on chrysotile asbestos was investigated through the analysis of adsorption isotherm, preference property for dispersion, moving direction of electrophoresis and TG-DTA curves. Barberton chrysotile asbestos with the specific surface area of 67 ma/g and anionic surfactant, Aerosol-OT, were used for this study. Other surfactants were also examined for comparison.
It was revealed that the adsorption of Aerosol-OT has a two-step isotherm with adsorption maxima of 1O^2- mg/g and 200 mg/g at the equilibrium concentrations of 230 me and 1100 mg//, which may be interpreted by the formation of double layers in adsorption. The first layer is formed by the chemisorption of polar head of surfactant to the surface of chrysotile asbestos, therfore adsorbed molecules are oriented their polar heads facing to the surface of chrysotile asbestos.
The second layer is adsorbed physically on the first layer with polar heads directed towards the solution.
The surface of chrysotile asbestos with the adsorbed monolayer of surfactant in diluted solution is organophilic, and the surface with the double adsorbed layers of surfactant in high concentration solution is hydrophilic.
The adsorption of Aerosol-OT attains to its saturation at an aquilibrium concentration equal to the critical micelle concentration (CMC 2.5 mmol//) of the surfactant. The area occupied by adsorbed Aerosol-OT molecule is 50 A2.

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The thermal decomposition of carbonatopentaamminecobalt(III) chloride, [Co0CO₂(NH₃)5]ClH₂0, which contains CO₃2- as unidentate i ligand and carbonatotetraamminecobalt (l11) chloride, [CoCO₃(NF13)4] Cl, which contains CO₃2-as bidentate ligand were investigated by using simul- taneous thermogravimetry and differential thermal analysis (TG-DTA), IR spectra, gas analysis, and other methods.
In the temperature range 140-170° C, the pentaammine complex evolved equimolar H₂0 and 1/3 molar NH₃ and formed a thermally stable compound. The IR and UV spectra of this thermally stable compound indicated that most of the CO₃2- as unidentate ligand changed to bidentate ligand. On the other hand, the tetraammine complex was not decomposed at these temperatures.
At temperatures higher than 180° C, both of these complexes decomposed in the same fashion, i. e., an intermediate which contained 1/2 mol NH4+ per 1 mol of Co was formed at 230° C after the evolution of NH₃ and CO₂ gases, and at 280° C, Co20Cl2 and NH₃ gas evolved.
The thermal decomposition reaction of the pentaammine complex in the temperature rage 140^-280° C was expected to be as follows:
6 No0CO₂(N1-13)5 CI. H₂0 3 Co20Cli N2(g) + 6 CO₂(g-) 28 1113(g) 9 H₂0 (g)
In the temperature range 300-400° C, Cl2 gas was evolved from Co20Cl2 and then Co3O^2- was formed.

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Diethylamine-hydrochloride, ephedrine-hydrochloride and methamphetamine-hydrochloride were estimated by complexing the aliphatic secondary amines with copper, subsequent solvent extraction of the copper complexes into MIBK and final determination of complexed copper by atomic absorption spectrophotometry. Satisfactory results were obtained by analysing the sample by the following recommended procedure: One ml of the sample solution, 1 ml of O.5 N ammonia water, 1 ml of Cu" solution and 1 ml of carbon disulfide were mixed. The Cu in the mixed solution was controlled to less than, O.25 in terms of aliphatic secondary aminehydrochloride/Cu (mol/rnol) ratio. The mixed solution was shaken for 1 minute with 25 m/ of MIBK, and the solution was allowed to stand for 10 minutes. The. amount of copper in MIBK solution was determined by atomic absorption spectrophotometer.
Straight calibration curve was obtained in the concentration range of 1.1-6.6 pg-diethylamine-hydrochlorideimi-MIBK, 1.2-8.0 pg-ephedrine-hydrochloride/m/-MIBK and 1.9-0.8 Agmethamphetamine-hydrochloridefrni-MIBK. The percent recovery of aliphatic secondary amines ranged from 93.3 to 1O^2-.2%.
The respective presence of 4.5 times Pb, 1.4 times Fe, 3.0 times Mg, 3.8 times methylamine-hydrochloride, 3.9 times trimethylamine-hydrochloride, 5.3 times diphenylamine-hydrochloride, 160 times aniline-sulfate did not interfere the determination of ephedrine-hydrochloride.

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The extraction spectrophotometric determination of aluminum with pyrocatechol violet and ethyltridodecylammonium bromide has been investigated. The aluminum-PV-ETDA complex can be extracted into solvent such as, n-buthylacetate, benzene, toluene and xylene, but not into n-butanol, methylisobuthylketone, chloroform. The complex extracted into organic layer has an absorption maximum at 597 nm. When a mixed solution of aluminum and PV is shaken with ETDA in n-buthylacetate for 5 min at pH of the aqueous phase 6.0, the maximum extraction of the ternary complex is obtained. The distribution ratio of the complex into nbuthylacetate is 1.27x 1O^2-. Beer's law holds up to 1.3 ig aluminum per 5.0 m/ of n-buthylacetate. The molar absorption coefficient of the complex is 8.4 X 1O^2- cm-ol-at 597 nm. Compostion of the complex is estimated to be Al: PV: ETDA=.1: 2: 3 by the continuous variation method. Consequently it may be assumed that the ternary complex is a ion associa-Thioglycolic acid or hydrogen peroxide are available for masking of many metal ions, but chromium(lla), ironal, tin(W), . rare earth, thorium, vanadium(V), zirconium, molybdenum (V), tungsten(V), nitrate, perchlorate, citrate, fluoride and EDTA interfere the determination of aluminum seriously.

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A, sensitive extraction-spectrophotometric method is described for the determination of palladium.3-Furaldehyde oxime (3-FAO) reacts with palladium to form a light yellow chelate extractable with dichloromethane. The extract has an absorption maximum at 307 nm and shows a definite absorbance over the hydrochloric acid concentration of 0.160.36 N. Beer's law holds up to 15.5, ug-Pd in 10 ml of dichloromethane. The apparent molar absorptivity of the complex and the sensitivity are 6.97 X 1O^2- and 0.0015 pg-Pd/cma for log (4/) =0.001, respectively. The molar ratio of palladium to this reagent in the organic phase is estimated to be 1 2 by the continuous variation method. The recommended analytical procedure is as follows.
To the hydrochloric acid solution containing up to 15.5 fig of palladium, 2 ml of O.1% 3-FAO solution is added, and the concentration of hydrochloric acid is adjusted to O.35 N by adding 0.5 N hydrochloric acid, diluting to 40 ml with water, and allowed to stand for 10 minutes. Then, the complex is extracted for 5 minutes by shaking with 10 ml of dichloromethane. After standing for 10 minutes, the organic layer is separated and dehydrated with sodium sulfate. The absorbance of Pd-3-FAO complex at 307 nm is measured against the reagent blank. All of the forty-five diverse ions examined do not interfere this method.

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The argentometric titration of azide ions by the short-circuit amperometric technique using a rotating platinum wire electrode (1000 rpm), and the differential titration of azide and halide ions have been studied. Potassium nitrate, sodium nitrate or sodium acetate is suitable for the supporting electrolyte. Azide ion in the presence of O. O^2-% gelatin can be determined at its concentrations from O.0001 to 0.01 moll/. The determination is the most precise at the concentration of 0.01 mol//; either the relative error or the variation coefficient is less than 0.1%. The whole procedure requires only 10 minutes.
A recommended procedure for the differential titration of azide and halide ions is as follows. Potassium nitrate and gelatin are added to a mixed solution of sodium azide and one of halides (sodium chloride, potassium bromide, and potassium iodide). The solution is diluted so that the concentrations are made 0.1 moll/ in potassium nitrate and 0. O^2-% in gelatin. The titration at the potential of SCE with 0.1 moll/ silver nitrate gives the sum of azide and halide ions. The content of latter can be found by titrating an aliquot of the sample solution up to the end-point for halide, the pH of which is previously adjusted below 2 with nitric acid. The relative errors are about 0.9% for 0.005 mol/l sodium azide and about 0.5% for 0.0O^2- mol/l sodium chloride.

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Simple, small and sensitive humidity sensor is developed for the selective determination of water vapor in various gas analysers used for effluent gas analysis and differential gas analysis. The sensing element consists of a base of aluminuim wire (1.3 mmsb), an oxide layer prepared by anodizing the base material in the sulphuric acid, an evaporated conductive coating of gold and lead wires (Fig.1). This element is placed in the glass or metal tube with a gas inlet and outlet.
Indication of water vapor concentration is given by the electrical properties (capacitance, registance and impedance) of anodized aluminum oxide layer. In this study impedance varia- tion of the sensor is measured by the circuit which consists of a volt meter, a known registance, an amplifier and an oscillator was employed (Fig.2). The sensor is neither affected by the presence of a wide varaity of other gases nor by the change of gas flow rate and has the rapid response time and good quantitativity.
This sensor can be applied for analyses and measurments of the phenomena involving water vapor and of the solid state reactions with evolution and absorption of water. As the example of its applications, the thermal decomposition of CaC_2CO^2-. H₂0 (Fig.6) and silica gel (Fig.7), and the reversible reaction of Ca (OH) 2= Ca0 FLO (Fig.8) were studied using this sensor as a detector of differential gas analysis.

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Reaction of 1- (p-nitrophenyl) -2- (2-quinolyl) ethyl acetate C 2 J with carboxylic acids gave quantitatively an elimination product, trans-2-p-nitrostyrylquinoline C 3 J. This elimination was studied kinetically by using six carboxylic acids as catalysts at 40° C in benzene.
Study of the effects of carboxylic acids (Fig.1) and of the initial concentration of C 2 (Table 3 and Fig.3) gav the following mechanism [eq. (6)]: At low concentrations of an acid, the reaction proceeds via two steps, the protonation of the nitrogen atom of [2] by monomeric carboxylic acids to give an ion pair intermediate [ 4 ], followed by the 2 type attack of the counter anion, carboxylate anion, on the 19-hydrogen to give trans-olefin [3].The latter step is rate-determining. At high concentrations of an acid, the reaction proceeds via dimerization of carboxylic acids, the protonation of quinolyl nitrogen atom and the attack of the carboxylate anion on the hydrogen. C4 D Reacts with another molecule of carboxylic acid to give a less reactive species C 5 J and the rate is decreased.
From the analysis of the step, C_2C RCO, H C4 [3] (Fig.3-8 and Table 4), it is conclused that the reaction proceeds through a specific acid-general base catalysis [eq. (16) and (17)]. The driving forces of this elimination are an activation of -hydrogen by the protonation with carboxylic acid to the nitrogen atom of 2 and the following attack of an appropriately strong base, carboxylate anion, on the β-hydrogen.

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In amide exchange reaction of sulfonyl diamide with amines, the reaction with primary amines under anhydrous condition gave monosubstituted products at first and then N, N'- disubstituted products. However, the reaction with primary amines under aqueous condition and with secondary amines in the absence of water gave mono-substituted products alone. These facts suggested that the reaction mechanism was not consisted of simple exchange between amine and amide group of sulfonyl diamide. The reaction process was proposed based on the isolated intermediates and the above mentioned facts were explained.
The first intermediates were N-monosubstituted sulfonyl diamides in the case of primary amines and sulfonyl diamide, and N, N'-disubstituted sulfonyl diamides in the case of secondary amines and sulfonyl diamide.
The formation of the second intermediates was limited to the reaction of sulfonyl diamide with primary amines in which N-monosubstituted sulfonyl diamides, the first intermediates, were able to condense bimolecularly.
1, 3-Disubstituted imidodisulfonyl diamide was isolated as an intermediate from the reaction under anhydrous condition, and 1-monosubstituted imidodisulfonyl diamide was isolated as an intermediate from the reaction under aqueous condition.
The former reacted with anhydrous primary amine into N, N'-disubstituted sulfonyl diamide easily. The latter reacted with aqueous primary amine into N-mono-substituted sulfonyl diamide.

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The effect of the structure on the rate of dehydrochlorination was investigated by earring out the pyrolysis of chloroethanes on activated alumina and the elimination reaction of hydrogen chloride from chloroethanes with ethanolic sodium hydroxide. The reactivity of the pyrolysis on activated alumina was found in the following order: CH₃CCl3Cl-12ClCCl3Cl-13CHCl2CHCl2CClsCH₂ClCHCl2CH₂ClCH₂ClCHCl2CHCl2. On the other hand, the reactivity of the latter reaction was a different order: CHCl, CCl3CHCl2CHCl2CH₂ClCHCl, CH₂ClCCl3CH₃CCl9CH₂ClCH₂ClCH₃CHCl2.
For both reactions, the linear free-energy relationships were found to exist between the reactivities of chloroethanes and Taft's a constants. Negative p* values were obtained for the pyrolysis of chloroethanes on activated alumina, whereas in the case of the elimination reaction of hydrogen chloride from chloroethanes with ethanolic sodium hydroxide these values were positive. From the experimental results, these reaction mechanisms are discussed.

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N-Aryl-α, β, β-tetrafluoropropionimidoyl fluorides [2] were prepared by the reaction of hexafluoropropene with arylamines, such as aniline, p-toluidine and p-chloroaniline (Table 1). The fluorides thus obtained ([2 a], [2 b] and [2 c]) and 0 or S containing nucleophiles, such as methanol, ethanethiol, phenol and thiophenol, gave N-aryl-a, 8, 8, 8- tetrafluoropropionimidate esters and thioesters (Table 2).

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o-Acetylbenzophenone [1] reacted with methyl-[4], ethyl- [5] and benzylamine [ 6 ]in methanol in the presence of acetic acid to give red C 7 1 C30H₂0N2R2, and unstable blue pigments. On the contrary in the presence of concentrated hydrochloric acid, stable deep blue pigments C 8 1 (C_2C917110N2R2)+Cl were obtained from C 1 J and these amines, [4], [ 5 ] and [6]. In the absence of an acid bis72-alky1-3-phenyl-1-isoindoly11-methanes C 9D, C_2CH₂oN2R2, were, isolated instead of C 8 J which were obtained by addition of hydrochloric acid on [9]. On the basis of their spectra and chemical behaviors, the structures of these pigments were determined to be 1, 2-bis-[2-alkyl-3-phenyl-1-isoindolyl]-ethylene [ 7] and 1, 1'-dialky1-5, 5'- dipheny1-3, 4; 3', 4'-dibenzo-2, 2'-pyrromethenium chlorides [8], respectively, and the mechanism of their formation was proposed.

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Grignard reactions of alkyl glycidyl ethers (R-CH₂H₂, R =CH80-, C_2CH80-, i-C3H70-) were performed in diethyl ether or tetrahydrofuran, and effects of the substituent ( R) on direction of ring cleavage were investigated. Though steric factor of R showed the most significant effect, similarly to the reaction of propylene oxide, inductive effect also appeared to affect the product distributions. In the case of associated Grignard reagent (dimeric), abnormal ring opening increased as the strength of electron-withdrawing group increased. In the case of monomeric Grignard reagent, inductive effect on reaction path was also indicated by the relative amounts of two kinds of rearranged products. It was suggested that Grignard reaction of glycidyl ethers proceeds through different mechanisms with alterations in associations of Grignard reagents.
In all reactions oligomers were also obtained in 33-48% yield.

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The kinetic studies of the catalytic effects of pyridines on the coupling reaction of p-methyldiazobenzene to the 4-position of 1-naphthol have been carried out.
The catalytic effect of the conjugated acids of pyridines ( I ) was observed, along with that of the free bases of pyridines (II) (Table 3 and 5). The rate of the coupling showed a first order dependence on the concentrations of I and. The apparent catalytic constant of pyridines, k0, was found to be given by kc=k[py.][py.]+ k[Py. II] C[Py.91.1], where kt[py. ], k[py., H], c[py. ] and c[py. eq] denote the base catalytic constant of 71, the acid catalytic constant of I, the molar fractions of I and I, respectively.
The kinetic data turned out to be in satisfactory agreement with the BrOnsted catalysis equation, k[py. ]=GbKbP or k[py.01-1]=G9, K, , a, where 8 and a=0.25, Gb = 1.8 x 10 and G. = 5. Ox 108 (Fig.1). And also, these data were found to fit the Hammett equation for 3- and 4-substituents in pyridines, as being p=.4 for k[py. ], and p= +1.4 for k[py. e] (Fig.2).

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Mercerization is a typical transfer reaction from cellulose I to cellulose II.
It was proved that this transfer resulted from the conversion of moleculer chain conformation from the Cell I type to the Cell II type and there were two chances for the above conversion in mercerization reaction. First, the crystallite of cellulose I fully relaxed and cellulose molecule hydrated before forming Na-Cell I. The hydration changed the chain conformation of the Cell I type into the more stable Cell II type, and resulted in the formation of the same Na-Cell I u as that obtained from Cell Na-Cell I II with the chain of the Cell I type regenerated cellulose 11 as a necessary consequence under any conditions of regeneration. Under the conditions of less relaxation of cellulose crystallite, that is, the crystallinity of the cellulose fiber was high and the reaction was carried out under fixed length, Na-Cell I had a tendency to be formed without passing the stage of fully hydration of cellulose. In this case, the chain conformation maintained- the Cell I type and Na-Cell II was formed. Na-Cell I and I 11 could be distiguished by the difference in the relative intensity among their meridional diffractions. Usually the mixture of them was formed. Second, the stage of regeneration of Na-Cell I i to cellulose by resulted from washing with cold water. After Na-Cell I I decomposed to cellulose, the moleculer chain of the Cell I type hydrated before forming the crystallite of cellulose and changed into the Cell II type, and resulted in the formation of crystallite of cellulose II. When Na-Cell I was regenerated under lower swelling condition at higher temperature, crystallite of cellulose was rapidly formed without passing the stage of hydration of the cellulose chain and the chain conformation maintained the Cell I type. Therefore, cellulose I could be Na-Cell I I regenerated by washing with hot water.

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7, 7, 8, 8-Tetracyanoquinodimethane (CQ) salts containing cation derived from piperadinium ring and p-xylene-cr, c-diy1 (p-xylylene) group were pnepared, and specific resistances p and activation energies Ea of cation-CQ salts were measured.
The p-valuse of simple salts were almost ca.107 ilm, and when neutral CQ(CQ° ) was added to simple salts, the p-values decreased markedly as follows; Series: I -CQ -CQ V -CQ N-CQ 111-CQ
P: 3.2 x 105 1.1 x 105 7.4 x1O^2- 81 44
The solubility of simple salts in N, 17' -dimethylf or mamide (DMF) and acetonitrile, which was important for the preparation of CQ complex salts, decreased as follows;
N-CQ It -CQ I v-CQ
As a result, decrease in the resistivity by adding CQ° molecules was considered to be caused by both piperadinium ring and, p-xylylene group. It was presumed that p-xylylene group was effective for keeping the distance between ionic sites, increasing solubility of CQ simple salt, and forming the complexes of CQ° and CQ 7 molecules, and piperadinium ring was effective for incresing electronic conduction by. controlling Lthe CQ° Q: arrangement against the cation.

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The ultrasonic absorption in aqueous solutions of poly (vinylpyrrolidone) (PVP) was measured at frequencies from 5 MHz to 130 MHz over the temperature range 10° C to 40° C. The molecular weights of PVP used were 1.0 x 1O^2-, 2.45 X 1O^2-, 4.0 X 1O^2- and 36 X 10.
A single relaxation process was observed over the molecular weight, temperature and frequency range investigated.
At frequencies below 7 MHz, the abnormal increase of ultrasonic absorption was found at about 30°C for the sample of M. W.36 x 1O^2-. Relaxation frequencies decreased with temperature rise in the range 20°C to 35° C and apparent activation energies became negative for all samples. These were explained by the dehydration of PVP.
At temperatures below 25° C and above 35° C, relaxation frequencies increased with temperature rise. Absorption maximum per wavelength 4, 11 Ic increased with increasing temperature and molecular weight.
The energy differences and activation energies were estimated from temperature change of absorption on the basis of two-state model.

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Macroreticular anion exchange resins were prepared by polymerization of polyfunctional quaternary ammonium salt monomers derived from amination of vinylbenzyl chloride with N, N, N', N'-tetramethylpolymethylenediamine such as tetramethylhexamethylenediamine. The suspension polymerization was carried out in a saturated NaCl aqueous solution at 60° C for 7 hours. A solvent mixture of CCl, -isooctane was used as a diluent at the volume ratio of 0.2-0.5 to total reaction mixt-6-e. Average diameter and volume of pores in resins had enlarged greatly with increasing concentration of the diluent in the reaction mixture. The ion exchange resins made from vinylbenzyl chloride with N, N, N', N'-tetramethylhexamethyl- enediamine showed a typical behavior as strong basic anion exchange resins. Salt-splitting capacity of these resins was 3.1 meq. /g-dry resin in R-Cl form and a coefficient of ion selectivity, K8, was 4.85. Amination of vinylbenzyl chloride with tetramethyl polymethylene diamine obeyed second-order kinetics, and activation energies for the amination was found to be 8.4-9.0 kcal/ mol in the case of aliphatic diamines. The polyfunctional quaternary ammonium salt monomer polymerized spontaneously even at lower temperatures below 5° C in a polar solvent such as methylalcohol or DMF. The spontaneous polymerization was neither prohibited nor retarded in the presence of radical inhibitor such as p-benzoquinone or p-t-butyl catechol.

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In order to introduce a new functionality to the polydiene rubbers (natural rubber, 1, 2- and 1, 4-polybutadiene), several methods for incorpotation of urethane structure and the elucidation of the reaction products have been carried out.
The reaction of rubber with ethyl urethane by means of BF3-etherate catalyst was not successful owing to the preferential formation of cyclized rubber. The reaction with N, Ndichloroethyl urethane, however, proceeded effectively without catalyst to afford the polymer containing j9-chloro-a- (N-chlorourethane) -sturucture (Table 1). N-Chlorourethanized rubber ( I ) thus obtained rapidly became insoluble by cross-linking on UV irradiation, whereas the rapid color formation, followed spectroscopically, was observed when ( I ) was irradiated in the presence of aromatic amines. The dechlorination of ( I ) was facilitated with reducing agents such as hydrazine to give 8-chloro-a-urethanized rubber (II), while the latter was also obtained by direct addition of N-chlorourethane to rubber under irradiation. Polymers bearing 2-oxazolidone and aziridine structures were also obtained by heating (Tr) and by treating (II) with alkali, respectively.

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In a series of research work on curdlan type polysaccharide (CTP), the introduction of imidazole group was carried out to prepare the catalyst which was specific for the stereoselectivity. Imidazole introducing CTP(ImCTP) was prepared by adding 4 (5)-chloromethylimidazole into CTP-dimethylsulfoxide solution treated with sodium hydride. ImCTP exhibited swelling property in aqueous solution. It melted on heating and was insoluble above pH 10. The reduced viscosity of ImCTP solution became larger with decreasing concentration of ImCTP and smaller in O.01 molii sodium chloride or Tris buffer (pH 8.7) which showed a property of polyelectrolyte. Cupric ion coordinated with imidazole group in ImCTP to form metal complex. The values of log CIm1-1+ 1/[H⁺] were 0.18 and 0.75 at n=0.5 and 1.5.
Copper complex of ImCTP showed a catalytic activity and oxidized 3, 4-dioxyphenylalanine (DOPA) in the solution of pH 7.0-8.7 according to Michaelis-Menten kinetics. Zinc (II) and nickel (II) complexes did not exhibit the catalytic activity. The rate constant, k2, at pH 8.7 was higher than that at pH 7.0. Michaelis constants, Km, were about 10-5 molg. The oxidation reaction velocity of L-DOPA was completely in accord with that of DL-DOPA. It seemed that the structure of copper-ImCTP was not suitable for the stereoselectivity. Copper complex of imidazole group binding amylose was found exhibit the similar catalytic activity as ImCTP. It could be thought that one molecule of DOPA would bind with two atoms of copper, coordinated with imidazole groups in ImCTP, to be oxidized.

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Mechanical, dynamic mechanical and adhesive properties of bisphenol and glycol type epoxy resins cured with triethylene tetramine were studied.
Properies of these cured resins were affected by their crosslinking densities and their segmental structures between crosslinks. Glass transition temperature was determined by the above two factors and affected mechanical, dynamic mechanical and adhesive properties of cured resins.
The values of tensile strength, tensile modulus mechanical damping and tensile shear strength of the cured resins were nearly constant or changed slightly in the glassy and rubbery region but drastically in the transition region. Peel strength increased in rtabbery region but decreased in glassy region with increasing crosslinking density and the maximum value was obtained between these regions. Fracture mechanism of peel test changed from cohesive to adhesive fracture between these regions.

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The stereochemistry of five dimers derived from trans-1, 2-dibenzoylethylene [1], which has already been reported by Lutz et al., was reexamined on the basis of IR and NMR spectra since it seemed to be somewhat obscure.
On the other hand, the reduction of [ 1 ] with aluminum isopropoxide produced the substance [ 7 ] (mp 188-489° C), which had not been examined in detail, besides normal products, trans1, 4-dipheny1-2-butene-1, 4-diols. In this paper, determination of the structures of [7] and the substance [8] (mp 213-214T), which the author recently obtained by the reduction, was made on the basis of IR and NMR spectra, proving them to be dimers different from those above; and also the mechanism of formation of [7] was discussed.

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Syntheses of isoprene and its intermediates from 3-hydroxy-3-methylbutyl acetate [1], obtained by the radical addition of isopropyl alcohol to vinyl acetate, were studied. Pyrolysis of CI - gives 2-methyl-3-butene-2-ol [4] at a good yield. Acid-catalysed reaction of C over alumina affords principally isoprene, 3-methyl-3-butene-1-acetate [2] and 3-methyl-2- butene-1-acetate [3], suggesting one step synthesis' of isoprene (Fig.2). Isoprene has also been obtained by the dehydration of [4 ]and by the pyrolyses of [2] and [3].

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In the stereospecific polymerization of 1-butene, effect of addition of Et8A1 or EtAlCl₂ on the catalyst system Et2A1Cl-TiCl3 has been investigated. Addition of an appropriate amount of EtaAl to the catalyst system Et2A1Cl-TiCl3 increased the catalytic activity by the factor of about 1.5 without detriment to the stereoregulation of polymer, and the number of the active centres for the stereospecific polymerization was not affected by the amount of Et8A1 added in a limited range. When small amounts of EtAlCl₂ were added to the catalyst system Et2A1Cl-TiCl8, the negative effect of EtAlCl₂ on the catalyst activity was independent of Et2A1Cl/TiCI, ratios and the stereoregulation of polymer was not affected by the existence of EtAlCl₂.

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Strongly basic anion-exchange resins, Amberlite IRA-400 and IRA-900 of OH forms, were heated in water at 300° C for 3 hr. Trimethylamine and methanol were released and the number of moles of methanol was greater than the amount of increase in weak base exchange capacity. When strongly acidic cation-exchange resins, Amberlite IR-120 B and 200 C of H forms, were heated in water at 200° C, a stoichiometric relationship between the amount of decrease in exchange capacity and that of sulfate ions formed was observed. While, when these resins were heated at 300° C, exchange capacity decreased to zero, and most of sulfur which was originally present in the exchange groups remained in the residual resins.

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