The transference numbers of K+ ion in aqueous KCI solutions have been dermined at high pressures up to 1500 kg/cm2 at concentrations from O.01 to O.1N at 25 C and at 0.02N at 15and 40 C by the moving boundary method. The movement ef the boundary was followed by the resistance measurement. Cadmium chloride was used as an indicator solution.
The transference numbers at infinite dilution at 25 C were calculated by the empirical equation of Longsworth. Transference number of K+ ion decreases with rising pressure in all cases. This decreasing tendency becomes weaker with increasing temperature. Besides, the transference number of K+ ion increases slightly with increasing temperature at 1500 kg/cm2 while it decreases with increasing tempreature at atmospheric pressure.
The ion-water interaetion of K+ ion is almost dominated by the electrostriction, while the ion-water interaction of Cl- ion involves the hydrogen bond in additien to the electrostriction. The hydrogen bond in the hydration shell of Cl- ion is probably broken with the increase in pressure and/or temperature as that in pure water. Thus the hydration of Cl- ion decreases slightly with the increase in pressure and/or temperature.

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In order to study of physico-chemical properties of Se-S crystals, the vitreous Se-S was crystallized at temperatures rangihg from 110 to 160 C and the temperature dependence of electric conductivity and Vickers hardness were measured.
the electric conductivity of Se-S crystals crystallized below 150 C decreased sharply when the content of sulfur increased up to about 6-7 atom %, but decreased slowly with increasing content of sulfur when the samples crystallized at 160 C or reheated at 160 C after the crystallization at 110 C. On the other hand, the hardness of Se-S. crystals crystallized at 160 C or reheated at 160 C decreased slowly with increasing content of sulfur, but that of the samples crystallized at 110 C decreased sharply when the content of sulfur became up to about 6 atom%.
By the X-ray diffraction analysis, it was found that a hexqgonal crystal structure with twice crystal lattice of selenium was formed when the samples containing more than 6-7atom% sulfur was treated below 150 C. Moreover, the structure of Se-S crystals reheated at 160 C was identical with that of selenium regardless of sulfur content.

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In order to clarify the formation mechanism of the chemical vapor concerning the vapor trantsport of ZnS crystal using HCl as agent, the sorption of HCl on the surface of ctystal and the diffusion of chlorid ion into the bulk of crystal were investigated.
Below 0.1atm of HCl, the amounts sorbed and diffused chloride ion increased exponentially with increasing pressure, but around 0.1atm, the amounts decreased suddenly, then increased again with incireasing pressure. By mixing He, the sharp decrease of the amounts of sorbed and diffused chloride ion around O.1atm was not recognized. Below O.1atm, the most of the diffused chloride ion was localized in the near surface of the crystal. Above O.1atm, the sintering of ZnS particles progressed remarkably and the chloride ion distributed uniformly throughout the bulk of crystal. On lengthening the firing time, the diffused chloride ion was segregated gradually on the grain boundaries of the crystal, then formed ZnCl2, which sublimed.
From these results, the formation mechanism of ZnCl2 at the gas-solid interface corncerning the chemical vapor transport of ZnS crystal was discussed.

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The hydrolysis of aliphatic diester is one of the typical competitive consecutive second-order reactions as shown by equations A + B - C + D and A + C - D + E, where B and C represent the di- and half-estdrs of aliphatic dicarboxylic acids, respectively. ln this investigation, several diesters i. e. diethyl succinate, diethyl adipate, diethyl suberate and diethyl sebacate were hydrolyzed and the rate constants k1 and k2 were obtained under the conditions of stoichiometricqlly equivalent amounts of reactants NaOH and diester in mixed solvents of water and dioxane.
The relationships between rate constants k1 and k2 and the number(n) of methylene groups separating two carboxyl groups were ebtained as follows: k1=a n-b and k2=c, 1O-d, n.
The experiments in the solvents with different dioxane-water volume ratios revealed that the effect of solvent composition on the reaction rates was negligible when the ratio is smaller than unity.
The attempt was made to measure not only NaOH concentration but diester and half-ester concentration by means of selective extraction. The diesters dissolved easily in n-hexane while the half-esters into aqueous solutibn. The results of measurement of diester and half-ester concentrations were nearly in acc6d with those calculated by use of rate equations obtained by foregoing procedure.

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The kinetics of oxidation reaction pf hydrogen over silica-supported platinum catalyst was investigated in the temperature range ef O-45 C and the pressure range of 10-150mmHg.
The kinetic behavior of the reaction depends on hydrogen pressure.
In the low pressure range (10-20mmHg), the kinetic order with respect to hydrogen is 1. O and a significant isotope of effect is observed. The apparent activation energy is 6. O kcal/mol.
In the high pressure range (20-150mmHg), the kinetic order is -0.5 and no isotope effect is observed. The apparent activation energy is 8. Okcal/mol.
The kinetic order with respect to oxygen is 1.0 regardless of the hydrogen pressure. The reaction is not retarded by the product during the reaction.
The experimental resuIts can be explained on the basis of the mechanism resulting from surfaee reaction between dissociatively adsorbed hydrogen and weakly bound oxygen molecules.

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In order to elucidate the catalytic properties of cation exchanged zeolites A, the isomerization of ethylethylene oxide (EEO) was investigated in a flow system at atmospheric pressure and 220 C. The reaction preducts were butyraldehyde(BA), ethyl methyl ketone(MEK), crotyl alcohol(CA)and n-butyl alcohol. The isomerization proceeded irreversibly and simaltaneouly. The ratio of (BA + CA) to MEK was about 40 regardless of the kinds of exchanged cation except AgA, indicating that the a-scission of EEO occured preferentially on all of the zeolites A. The catalytic activity and the acidic propeirty depended upon the kinds of exchanged cation. The activity of zeolites A which were heat-treated at 400 C increased in thg orqer of ZnA CdA MgA AgA CaA SrA LiA 4A, KA=O, and the acidity also agreed with this order. When the calcination temperature of zeolite A was in the range of 200 to 450 C, the activity and the acidity were constant although both of them decreased at the higher temperature. Good correlatiohs were found between the activity and the electronegativity of exchanged catien, and the acid amount (H0 4.8).
From the facts desctibed above, it may be concluded that the isomerization of EEO on cation exchanged zeolites A was catalyzed by the Bronsted acid sites and the moleculuar sieve action of zeolite A is responsible for selectivity of products.

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When benzaldehyde was treated at 120-200 C over BeO, MgO, CaO, SrO or BaO without any solvent, a large amount of benzyl benzoate and a very small amount of benzyl alcohol were found as the raction products. The time variation of the ester formation gave S-shaped curves including induction periods (Fig.1). After the induction period, the reaction obeyed the first order rate equation with respect to the concentration of benzaldehyde (Fig.3). The induction periods were shortened remarkably by the addition of benzyl alchohol (Fig.6). The catalytic activity was found to increase in order of BeO MgO CaO SrO BaO (Table 1)and the activation energy and entropy were 9.4 kcal/mol and -49 e. u. for CaO and 54 kcal/mol and 54 e. u. for SrO, respectively. A very good correlation was found between the catalytic activity and surface basicity measured by an indicator method (Fig.4). ln the case of CaO, the highest activity was observed for CaO obtained by calcining Ca(OH)2 at 400 C or by thermal decomposition of CaCO3 at 900 C (Table 2), theugh CaO obtained by calcining Ca(OH)2at 900 C did not show any activity.
On the basis of the observed results, it has been concluded that the active species of MgO and CaO are the metal alcoholates formed by the reaction of benzyl alcohol with the catalyst surface and the formation of the alcoholate is facilitated by the basic sites(O2- and OH-)on the surface. The reaction mechanism was also discussed.

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A series of new photosensitive polyesters with pendant cinnamic ester groups were prepared from glycidyl cinnamate(GC) and phthalic anhydride(PAH), maleic anhydride(MAH) and succinic anhydride(SAH) by the ring opening alternating copolymerization.
Copolymerization of GC and each of PAH, and SAH were carried out in organic solvents such as cyclihexanone and hexamethyl phosphoramide, or in molten states, Copolymerization of GC and MAH in molten state was not succeeded because of the gelatien of the reactant. It was observed that the GC-PAH and GC-SAH polymerized in molten state have higher viscesity than those obtained in organic solvents.
The polyester from GC and MAH containing 5 wt% of 5-nitroacenaphtene as a sensitizer has the same relative sensitivity as KPR. The rate constant of photocrosslinking of polyesters was 3.47 10-3 mol%-1 sec-1.

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Bright and adherent nickel depesits were obtained in a wider range of current densities from Ni(CF3COO)2-HCONH2 baths containing H3BO3, saccharin, sulfamic acid, urea, AlCl3 or NH4Cl, compared to Ni(CF3COO)2-HCONH2, bath without any additive.
The addition of H3BO3 in Ni(CF3COO)2-HCONH3 bath gave adherent nickel deposits in a wider range ef current densities.
The appearance of nickei deposits obtained from Ni(CF3COO)2-HCONH2 bath containing thiourea or saccharin was dull.
For tre electrodeposition ef nickel-from Ni(CF3COO)2-HCONH2-H3BO3-thiourea bath, the apparent current efficiencies on both cathode and anode were about 120% at 60 C and 70 C.
For the bath containing AlCl3 or NH4Cl the anode current efficiencies were high, and in the letter case the cathode current efficiency also high.
The rate determining step of the electrodeposition of nickel from Ni(CF3COO)2-HCONH2bath containing additives, except thiourea, was the charge transfer reaction at current densities ranging between O.9 and 4 A/dm2.
The activation overvoltage for hydrogen evolution on nickel was lewered by addition of H3BO3, sulfamic acid, chloride or thiourea into the CF3COOH-HCONH2 bath.

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The grain size of nickel deposits obtained from Ni(CF3COO)2-HCONH2 bath with additives was 30-170 A.
A strong(220) grain orientation was observed in nickel deposits obtained from Ni(CF3COO)2-HCONH2 bath containing H3BO3, sulfamic acid, urea, AlCl3 or NH4Cl, while bath containing thiourea gave the doposits with strong (111) orientation.
The surface Layer of nickel deposits obtained from Ni(CF3COO)2-HCONH3 bath containing H3BO3, sulfamic acid, chloride or urea, consisted of small grains, but those obtained from Ni(CF3COO)2-HCONH2 bath containing thiourea or saccharin consisted of a number of lumps.
In the bath containing thiourea, sulfur was co-deposited in the cathode as well as anode. Sulfur exsisted in nickel deposit was not a sulfiide, while it exsisted as NiSO4-6H20 in the anode after electrolysis.

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Aluminum nitride was prepared by arc discharge between aluminum electrodes in nitrogen atmosphere. The apparatus which had been shown by Long and Foster was improved in cooling way of eletrode to decrease oxygen content of the product. Fast neutron activation analysis revealed that the product contained oxygen as little as O.82% and the other impurities less than O. O1%. The oxygen content was decreased by heating the product in nitrogen atmosphere. When it was heated at 1800 C for 2.5 hours, the oxygen content was decreased as low as 1/5 of the initial value.
X-ray powder diffraction of the product gave sharp diffraction lines of aluminum nitride and its lattice constants were a=3.111, c=4.980. The spectra of arc flame showed neither the band system which indicated the presence of AIN molecule nor any unidentified spectrum in visible and ultra-violet region. The influence of nitrogen pressure in the range between 1atm and 10atm on the production rate of aluminum nitride was studied. The production rate increased as the nitrogen pressure inereased from 1atm to 3atm, but above 8atm it decreased as the pressure increased. From the thermal decomposition rate of aluminum nitride in nitrogen atmosphere, the apparent activation energy was calculated to be 127 kcal/mol.

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The pressure leaching of tungsten ores with ammoniacal ammonium phosphate solution was investigated at 160-220 C.
The experimental results are summarized as follows
(1) The tungsten extraction from scheelite and wolframite ores is 90 and 80%, respectively, under the optimum conditions viz. reaction temperature 200 C, reaction time 2hr, molar ratio of ammonium phosphate to tungsten in the ores: 8 and pulp density: 2g-ores per 8ml concentrated ammonia solution.
(2) As the solubility of phosphate in concentrated ammonia solution containing several %of ammonium tungstate is less than 200 mg-P205/l, most of the phosphate in the leachate can be removed by merely blowing gaseous ammonia into it.
(3) The ammonium phosphate method is inferior to the sodium carbonate one in the degree of the tungsten extraction, but has advantages that both ammonia and ammonium phosphate, which are decomposing agents, can be used circularly, and that the dissoiution, of silica can be suppressed.

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The effect of molybdenum oxide on the synthetic procpss of zircon from zirconia and silica was investigated. Specimens in powder form were heated at various telnpergtures in air or in vaccum, then cooled to room temperature. The products were examined by X-ray diffranction analysis at room and high temperature, and by DTA and IR spectroscopy.
The results are summarized as follows
1) Molybdenum oxide accelerates the formation of zircon from its component oxides.
2) Molybdenum oxide first reacts with zirconia form zirconium molybdate, Zr(Mo04)2
The formatien of Zr(MoO4)2 starts at 600 C and is completed at about 700 C, Zircon is formed simultaneously with the thermal decomposition of Zr(MoO4)2, accompanied by the vaporization of molybdenum oxide.
3) The reactive zirzonia formed by the decomposition of Zr(MoO4)2 contains a small amount of molybdenum oxide which might exist in a form of an unknown low temperature melting phase with zirconia. The formation of zircon see ms to be accelerated by the reaction of this low temperature melting phase with silica.

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The swelling of synthetic Na-taeniolite NaMg2Li(Si4010)F2 was investigated by X-ray diffractometry at a room temperature and high temperatures, TG, DTA and IR spectrometry. Results obtained were summarized as follows:
1) Na-taeniolite reacts with water, and X-ray diffraction spectra show that the interlayer spacing (OO1) expands discontinuously with water contents.
2) Four states, represented by hydrated phases with the basal spacings of 10.57, 12.26, 13.38, 14.96A, are observed for the process of the water uptake into interlayer sites.
3) The maximum crystalline swelling state for Na-taeniolite is a so-called two-layer hydrated type(14.96 A), and a one-layer hydrated type (12.26 A)is the most stable at a roem temperature and humidity (R. H.=60%),
4) The intelrlayer water in Na-taeniolite is liberated bglow 100 C. The activation energy and the order of reaction for the dehydration ef one-layer hydrated sample in air are about 15 kcal/mol and O.6, respectively.
5) It seems that the swelling of Na-taeniolite is mainly due to the high hydration energy of interlayer Na+ ion, rather than the interlayer attraction force. The values of thermal expansive coefficient perpendicular cleavage plane are about 2010-6 deg-1 for both nonexpansive taeniolite KMg2Li(Si4O10)F2 and Na-taeniolite, suggesting that the interlayer attraction force is neariy the same for both taeniolites.

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Palladium(II) complexes of N-(2-pyridylmethyl)-2-pyridylacetamide and N-[2-(2-pyridyl)ethyl]-2-pyridinecarboxamide, [PdLX]nH2O(X=Cl, Br, or I), have been prepared and their properties were studied by means of infrared and NMR spectra. These two ligands were coordinated with an amide-N and two pyridine-N atoms. The oxygen atom in the amide group, in which nitrogen was coordinated had still a coordination teudency as was shown by the addition of tris(dipivaloylmethanato)europium(III). The chemical shift due to 6-H of the pyridine ring varied with the coordinated halogen and. the reason of this was considered to be partly due to the spatial interaction of hydrogen with halogen.

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The boron consent in about 130 Japanese volcanic rocks ranges from 0.5 to 169 μ g/g (Table 2), as determined by a spectrophotometric method based on the extraction of methylene bluetetrafluoroborate ion pair. The arithmetic mean (A. M.) is 21 μ g/g and the geometric mean (G. M.) is 14 μ g/g The cumulative frequency distribution of boron deviates distinctly from lognormality (Fig.1a). The alkaline rocks (or the rocks from the region near the Japan Sea)have low boron content (A. M.=6.2, G. M.=3.7) and con be clearly distinguished from the others by statistical analysis. On the other hand, glassy rocks have high boron content (A. M.=52, G. M.=36). The distribution of boron in these two classes of rocks and in the other rocks obeys lognormality, respectively (Fig.2). There is a slight tendency that the boron content increases with increasing silica content in rocks. The relation is, however, not so clear as has been usually refered. The boron content has also no marked relationst to the eontents of other volatile components such as fluorine or chlorine. The distribution of the B/Cl ratio shows lognormality(Fig.3), but that of the B/F ratio shows two separate lognormal distributions. Each of them correspends to the rocks from the Japan Sea region (or the alkaline rocks) and the others (Fig.4).
Ultrabasic rocks analyzed have low boron contents as compared with volcanic rocks (Table 3). The boron content of usual rock forming minerals were found to be almost the same as that of volcanic rocks. Almost all of them were, however, water-soluble and can not be regarded as contained in their crystal structures (Table 5).

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A new method for the determination of trace amounts of iron, copper, zinc, nickel and cobalt has been developed by the combination of solvent extraction and atomic absorption spectrophotometry. These metals produce water-insoluble complexes with 1-(2-pyridylazo)-2naphthol (PAN), which were extracted into methyl isobuthyl ketone (MIBK). Although the optimum pH ranges for the complex-formation with PAN were 3-5.5 for iron and 7-10 for other metals, these complexes were able to form by adjusting the pH of solution to 4-5, then raising it to 8-9, and extracted in MIBK simultaneeusly. These complexes were stable in MIBK for ten days. Lineat calibration curves were obtained up to 70 ppb. The coefficients of variation were 5% at 2 ppb for copper, 3% at 5 ppb for iron, and 6% at 5 ppb for zinc, nickel and cobalt.
Based on these data, following procedure was presented for the deterrnination of iren, copper, zinc, nickel and cobalt. Four hundred milliliters of the sample solution containing these metals up te 70 ppb are transferred to a 500 ml separatory funnel, and the pH is adjusted to 4-5 by 5 ml of an acetic acid-ammonium acetate buffer solution. After addition of 2 ml of O. O1 mol/l PAN solution, the solution is shaken for 3 minutes. Further, pH is adjusted to 8-9 by 3 ml of 6% ammonia solutien and the solution is shaken for 3 minutes. Then, 20 ml of MIBK are added and metal-PAN complexes are extracted by shaking for 2 minutes. The organic phase is subjected to the atomic absorption measurement following the condition shown in Table 1.
The presence of Pb(II), sulfate, thiosulfate, phosphate, pyrophosphate, ehloride, fluoride, or hydrazihe caused no interference to the determination. Even a small amount of cyanide and a large amount of nitrate interfered the determination (Table 5).

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Differential pulse pelarography has proved te be a very sensitive technique for trace analysdis. Parry et al. evaluated the theoretical current-potential relationship as a function of pulse amplitude and reported experimental verification of the theory.
We have studied the effects of pulse amplitude on peak current and peak half-width, beside the relationship between peak potential and half-wave potential and reexamined in detail the equation derived by them. The equation was found to be applicable for a reversible electrode process with both 3-electrode system and 2-electrode system.
It was observed, however, that the experimental values of an irreversible wave did not coincide with the theoretical ones. The peak half-width was larger and the peak current was smaller than that observed for the reversible wave. For the analytical application of the irreversible wave, greater pulse amplitude may increase the sensitivity without practical influence on peak half-width.
BTesides its high sensitivity, differential pulse polarography gfferied ope ggvantage of employing very dilute supporting electrolytes. At 10-6mol/l level of reducible species, the peak current obtained in 1 mmol/l supporting electrloyte agreed well with the theoretical value. However, the typical reversible reduction wave of 1 mmol/l Cd(II) in 0.01 mol/l KCl showed a curious behavior quite similar to the irreversible wave in which the peak half-width became smaller than the calculated value at 100 mV pulse amplitude. Under this condition, an approximately linear relationship existed between peak current and pulse amplitude either wite 3electrode system or with 2-electrode system.
Moreover, we have examined the influence of scan rate and the concentration of supporting electrolyte on the differential pulse polarographic wave and also evaluated the temperature coefficient of the peak current.

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A chromatographic elution pattern, an absorption spectrum or a NMR spectrum is obtained generally as an overlapping curve. Resolution of the overlapping curve into component curves would give some useful informations.
A derivative of logarithm of a Gaussian curve gives a linear function. The gradient and x-intercept of the liner function indicates a standard deviation and a center of the Gaussian function, respectively. Based on this Bhattacharya's method, we made a cemputer program for the curve analysis including an X-Y plotter.
An application of the program to elution patterns of THO, in gel chromatography, proved correspondence of a calculated curve with observed curves. Further application to an acidic protein, a basic protein or some proteins which might have characteristic interaction with gel, also proved the good fitness of the method.
From these results, any elution pattern of gel chromatography could be analyzed into the component Gaussian curves, when the conditions were kept proper.

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The effect of pressure on the thermal dehydration process of CuSO4, 5H2O has been investigated using thermobalance and DTA apparatus under nitrogen pressure in the range between 1 and 40 atm.
On the dehydration of four moles of coordination water, two peaks appeared at 1 atm and only one peak appeared above 4 atm on the DTG curves and three endothermic peaks appeared on DTA curves. The peak positions of DTG curves and one of three peaks of DTA curves shifted to higher temperature with the increase of pressure. This shift of peaks was observed at similar temperature both DTG and DAT curves, and the tempature was approximately the boiling point of water under each pressure applied. No peaks were observed on DTG curve that corresponded to the two unshifted peaks on DTA curves.
From examinations of these results, two unshifted peaks on DTA curves were attributed to the dissociation of coordination water and the shifted peaks on DTG and DTA curves to the evaporation of liquid water dissociated from the heated sample. The activation energies of these reactions were calculated by Kissinger's method.

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The thermal behavior of the complexes of (Ni or Co) (TTA)2 (pyridine base)2 has been investigated. The thermogravimetric analysis (TG) and differential thermal analysis (DTA)were carried out on a thermobalance with 80-110mg samples at a scan rate of 5 C/min in air and in nitrogen atmosphere. Almost similar features were observed in the thermograms on all the complexes studied, which gave melt endotherms with none of weight losses and then decomposition exotherms with remarkable weight losses, Examination by TG showed that apparent losses in weight of the complexes started around 250 C and abrupt losses took place in 300-350 C in air and in nitrogen.
With the complexes of (Ni or Co) (TTA)2 (pyridine base)2, endothermic peaks were found to appear at elevated temperatures in order of a-picoline adduct B-picoline adduct pyridine adduct r-picoline adduct, which were adjacent temperatures of the melting-points of these complexes. Exothermic peaks appeared about 350 C in nitrogen and about 500 C in air for the nickel complexes, while they appeared about 350 C and about 450 C for the cobalt complexes respectively. Examinations showed that Ni(TTA)2 (r-pico)2 possessed the most thermally stable properties among the complexes studied.
Residues left in the sample vessel after thermal runs consisted mainly of the metal oxides in the case of air-flow, and mainly of the metal compounds, and meta1, carbon and sulfur in nitrogen-flow.
On heating in nitrogen atmosphere pyridine base complexes of the thenoyltrifluoroacetonate decomposed without displaying any stepwise elimination of definite mele of ligand molecules from the complexes, while the hydrated cbmplexes of thenoyltrifiuorcacetonate clearly shewed an elimination reaetion of tow mdles of water from each one mole of the compounds before they melted.

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Irradiation of a solution of benzaldehyde and a monosubstituted acetylene(n-butyl, t-butyl, n-propyl or phenylacetylene) in benzene with high presure mercury lamp gave 3-substituted 1-indanone (3-n-butyl (yield, 9.0%), 3-t-butyl (9.0%), 3rn-propyl (9.0%) or 3-phenylindanone (1, 4%o))" The reaction of benzaldehyde with phenylacetylene gave trans-ev-phenyleinnamaldehyde (16, 6%)and trans-benzalacetophenone (O.4%) in addition to the indanone (Table 1 and Equation 2) The following mechanism of the indanone, formation (Equation 5) was prpposed from the result of the reaction using deuterated starting compounds. (C6D5CHO3, n-C4H9C CD) or using an excess amount of benzaldehyde as a hydrogen donor. Additien of benzoyl radical (formed from the photochemical decomposition of benzaldehyde) to the monosubstituted acetylene gives a vinyl radical, which cyclizes to a cyclohexadienyl type intermediate by an intramolqcular, attack to the phenyl ring of benzoyl moiety. Then the therma11y allowed [1-5]sigmatropic rearrangement of hydrogen may give the enol of the 3-substituted 1-indanone. This mechanism was, confirmed by an independeht study in which benzaldehyde was allowed to react with n-butylacetylene in the presence of a radical initiator.
The photochemieal formation of trans-a-phenylcinnamaldehyde and trans-benzalacetophenone sugested the interrnediacy of the, corresponding oxetene derivatives. The differenee of the reaction pathway between phenylacetylene and the monoalkyl-substituted acetylene was explained in terms of the electron donating nature of the substitdent on the acetylenic bond. Phenylacetylene may be able to trap the electrophilic excited-state of benzalde hyde, whereas the monealkyl-substituted acetylene does not.

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. Two4-chlorQ entho e isomers (2)(bp 51 2 mmHg), (3)(mp 27)and 2-chloromentho: ne (4)(inp 8, 1. C)Wer-e dbtained by ch1, ti, n 6f(-)-menthone with equim, lar am, unts of gaseous ch1rine Or sulfufyl chlpride
similarly, two 1-chlorocarvomen, thon, e isomers, (11)(bp 98c/lo mmHg)and (12)(bp 93c/6: mmHg), 3-c: hlorocarvomenthone, (13)(mp 98 C)and 1, 3-dichlorocarvomenthone(14)(mp 68C)wer: obt3ined from(+)-caryoenthone(10).
In every case ch1orinatiQn occurred exclusively in the methine positions, The con gurations 'and co: nformations of these products were determined by their IR spectra, NMR spectra and ORD.
When sulfury1chloride was used in carbon tetrachloride, axial chlorine isomer(2)and equatori, 1ohlgrine isomer(3)(or(11)and(12))were produced in the ratio 2: 1(4: 1), independent of reaction temperature.
On theother hand, in the caseof gaseous chlorine the products were inf uenced by solvent and temperature. When acetic acid was used as a solvent at below 20, the products were nearly 6qaul amounts of(2)and(3)(or(11)and(12)).1: n the caseof carbon tetrachloride solven, chlorin, ation occurred in the -position in addition to the position.

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7-Chloro-1, 2-dihydro-5-phenylimidazo (1, 2-a) quinazoline (4 a) and 8-chloro-2, 3-dihydro-6phenyl-1 H-pyrimido (1, 2-a) quinazoline (4 b) were synthesized by several steps from 2-amino5-chlorobenzophenone (1).
6-Chloro-2 (B-hydroxyethylamino) 4-phenylquinazonline (3 a) was obtained from the., reactign The of2, 6-dichloro4-phenylquinazoline, which wasderived from (Z), with2-aminoethano!. cyclization of (3 a) catalyzed with POCIs and aqueous KOH gave (4 a) in-gogd ie. lg. C 6-chlero-2 (r-hydroxypropylamino) 4-phenylquinazoline (3 b) was cyclized to(4 b). It was confirmed that above cyclizations took place at the 1-positien of quinazeline ring, because (4 a) and (4 b) could be synthesized by the other route. Namely, 7-chlqro-4-m-ethy! s-phenylLl, 2, 4, 5 tettahydroimidaze (1, 2-a) quinazoline (8-aL) and 8-c-hlgro: 5Tmeth\lt: 6-phenyl-2, 3, 5, , 6-tetrahydro-(1H) pyrimido (1, 2-a)quinazoline (8 b) were derivrgq-fLrom (1), . an. d the eiii hination ofFmethdne from (8 a) and (8 b) with PBrs gave (4 a) and (4 b), respectiyely.

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The role of the complexes of diphenylmethanimine (lm) with copper chlorides, CuClelm (1), CuCl e21m(2), CuC12elm(3) and CuC12.21m(4) in the oxidative coupling of lm has been studied.
Benzophenone azine (Az) was obtained in the yield of 70% at 1200C by the addition of cuprous chloride. Qxygen is necessary to form Az and in the atmosphere of nitrogen one obtain not Az but complex(Z). Cupric chloride was less effective for the formation of Az (yield 5%)
It was shown that complex(2) and (4) release lm reversibly to form (1) and (3), respectively. In reference to the formatiep of (1) by the thermal decomposition of (4), complcx (1) may be regarded as an effective intermediate for the formation of Az. The presumption was confirmed by the formation of Az from lm by the addition of the catalytic amounts of any of complexes (1)N(4), in which (1) is most effective (Table 3).
Complex(1) in chloroform solution absorbed oxygen to form complex(5), containing about two atoms of oxygen per (1) (Table 2). Although the atomic ratie of copper and chlorine in (5) is unity, the former is revealed to be divalent. ln the oxidative ceupling of lm in a condition of cucl/Im 1/1, complex(5)was obtained as a main product at the time when the free lm just disappeared. The continued supply of oxygen resulted in conversion (5) to Az. (Table 1).

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By gas chromatography and/or combination of gas chromatography and mass spectrometry, four phathalides, 5, 6-dimethylphthalide (DMP), 5-carboxy-6-methylphthalide (DMP-1-p), 5methyl-6Tcarboxyphthalide (DMR-1-m) and 5, 6-dicarboxyphthalide (DMR-ll) were identified ambng the oxidation products of durene.
The method of quantitative determination of these feuir phthalides by gas chromatography was also investigated. From the data obtained, area correction factors for gas chromatograms of these four phthalides were shown in Table 1 and determination results of various oxidation products were listed in Table 2.
The agreement between oxidation values calculated from equation A apd from volume of absorbed oxygen during the oxidation of durene as shown in Table 2 supported the reliability of the results.

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The oxidative reaction of hexamethylbenzene (HMB) with nitric acid was studied, and the hitherto unknown polymethylbenzenepolycarboxylic acids were isolated:. tetramethylphthalic anhydride, tetramethylisophthalic acid, 1, 3, 5 1, 2, 4 and 1, 2, 3-trimethylbenzenetriearboxylic acids.
When HMB was warmed with 50% nitric acid at about 80 C, tetramethy!phthalic anhydride and tetramethylisophthalic acid were initially pro du ed. The continued reaction led to the production of trimethylbenzenetriearboxylic acids, but only slight amount$ of dimethylbenzenetetracarboxylic acids were detected in the reaction mixture. Whereas tetramethylphtha1ic anhydride and tetramethylisophthalic acid were obtai n ed, pentamethylbenzoic acid, a possible precursor ef them, was scarcely produced. On the other hand, a yellow material extracted with ether from the initial reaction mixture contained bis (nitromethyl)prehnitene (CH3) Ce (CH2NO2)2, which was easily converted into the phthalic anhydride.

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Separation by gel permeation chromatography (GPC) and structural analyses of the GPC fractions were carried eut to gain an insight into the distribution of molecular weight, unit structure and molecular structure of coal and coal derivatives.
Pyridine, chloroformpe oleum ether-soluble(1)part of Akabira coal was fractionated by the preparative GPC procedure into 14 fractions. The degree of GPC separation was estimated on the basis of molecular weight determined by vapor pressure osmometry (VPO)and of analyses of molecular weight distribution measured by analytical GPC method for cach fraction. From these analytical data, it was clearly found that the fractiens obtained by preparative GPC were separated in accordance with their respective molecular size and were of considerable narrow molecular weight distribution.
The average struetural units of the individual fractions of preparative GPC were analysed by elementary analyses and by bonding types of hydrogen revealed by high resolution NMR. Using these structural parameter, the weight of average structural units (M(vs)) which were introdu ed as the new structural analysis were calculated There was a good agreement between the molecular weight estimated by VPO and weight of average structural units fer fractions No.5 to 14 having molecular weight under 400
On the, other hand, coRsiderable discrepancies were observed in the results from both estimations for fractions No.2 to 4 of molecular weight ever 450. Considering these results, it may be concluded that the compound of r, part with molecular weight higher than about 450 consists of approximately a dimer or trimer of unit strueture, while individual unit structures with varying magnitudes exist as melecular structures of the cempound with rnolecular weight lower than 400. The results of structural analyses of GPC fraction are in agreement with the chemical structure of the solute which were assumed on the elution volumes by GPC separatioR behavior.

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The complex formation between anthraquinone dyes and ethyl benzoate (EB) in carbon tetrachloride was investigated by paper chromatography. The equilibrium constants of the complex formation were calc. ulated from the following relation,
iog (itEllllii51kkif. fR iSllii2i Z Ki cA z K2.. cA2 El Ks. cAs
where Rt and Rfo are the Rf values of dyes in the eluent of CCI in the presence of EB and in lts absence, respectively. And are the sumsof equilibrium constants in each complex fermation of 1 1, 1 2, (dye EB), respectively. cA is the initial concentration of EB in the eluent.
Only a 1 1 complex was observed for the most dyes, and the dipole-dipole interaction between CO of dye and COO of EB was suggested by spectral investigation. A 1 1 and a 1: 2 complex were observed for the dye having phenolic OH, and this dye had much larger 2) Ki than the other dyes, due to the hydrogen bonding between the dye and EB.

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The general base catalysis and the primary salt effect on the coupling reaction of 1-naphthol with p-methoxy or p-methyldiazobenzene have been studied kinetically.
The rate of the coupling at 4-positiQn of 1ewnaphthol was found to be given by k, (base) (diazonium ion) (naphtholate ion), where base denotes monohydric phosphate ion, acetate ion, dihydric phosphate ion, water and pyridine (Fig.1). A linear relationship between the logarithms of k. and the disso iatien constant of the base was also found when monohydric phosphate ion, acetate ion, or dihydric phosphate ion was used as a base. The catalytic effect ef water was much smaller than that expected by the abeve relationship, while that ef pyridine was larger (Fig.2).
The rate of the reaction at 2-position of 1-naphthol was, on the other hand, almost independent of the concentration of a base except water (Fig.1).
The salt e ect suggested that the reaction took place between two ionic species, i. e., diazonium ion and naphtholate ion (Fig.3)i

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The removal of lignin in unbleached pulp washing waste water by the lime treatment was studied using the equipment of continuous flowprocess.
About 80% of lignin was removed by the lime treatment. The removal' of lignin was independent of initial lignin content and of lime dosage above 1 g/l. This result suggests that a part of lignin component is not removed by the lime treatment.
In the precipitation of dissolved alcium as carbonate, large particles which was identified to be calcite, were obtained at abeut pH 11. The seed clystals were effective in the precipitation of the large particles.
On the basis of these results, we devised the slurry recirculation carbo'nater-clarifier and set up the pilot plant. As the result of the continuous treatment test using the plant, the suspended solid in the eMuent ranged from 20 to 70 ppm at which linear velocity in the crarifier was 80 cm/hr.

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Bisoxadiazelones such as 2, 2 (1, 4-phenylene)bis (7) and 2, 2 tetramethylenebis-1, 3, 4-oxadiazolin5-one (8) were prepared by the reaction of the corresponding dihydrazide with phosgene. The salt consisted of 1: 1 tnole ratid of (7) and diamines were isolated by mixing the both compenents and characterized
Thermal polymerizations were carried out by heating either the above salts or equimolar mixtures of (8) and diamines. The powdery polymers thus obtained were soluble in dipolar aProtie solvents but insoluble in comtnon organic solvents. They showed an additional IR. absorption around 1700N1710 cm-i together with the C O s6rption (1630N1650 cm) of the expected acylsemiearbazide (CONHNHCONH) structure.
To confirm the unexpected structure mentioned above, the pyro1yses of the model compound and po1y(acylse: micarbazide)prepared m dihydrazide and diisocyanate were investigated It is conc1uded that bisoxadiazolone reacts with diamine to give poly(acylsemicarbazide) at first and then the structure changes partially to 3, 5, 6-trihydrotetrazen4-ene ty end structuice on prolonged heating. i

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P 1y neri ation of 3 (2-vi ny1) 6-methylpyridazinone(1)has bee ca ried out under various reaction conditions such as change of s 1vents, initiators, a n com, ono ers. No polymers of (1)was obtaihed in the presenlce of cationic and anionic catalYsts. It was noted that the radica1 P 1ymerizati n f(1)in benzene a d in dioxane proceeded heter gene usly to give a ge1-1ike polymer, perhaps built up via an thr e-dimensional propagati
0.54 and -0.54, respectively.
The coPo1ymerization of(1)with maleimide(MI)and maleic anhydride(MAh)have been carried out(Fig.7and 8). It has 1so beenobserved that in diQxane solution the heterogeneous polymerization occurred to yield a geHike product and that in DMF solutio the homo. geneous polymerization took place to give an alternating copolymer(Tab1e 7).

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The bulk polymerization of vinyl monomers was carried out in heterogeneous system, usihg the complex synthesized from ethylenediamine and cupric acetate or cupric chloride. lt was found that the polymerization by the complex o cured only when methyl methylate was used. The rate of poiymerization was larger in the presence of CCI than in the absence of CCI. The conversion was remarkably decreased with the addition of water. The polymerization was found to proceed through a free-radical mechanism.

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The free-radical polymerization of methyl methacrylate (MMA) in homogeneops phasf was kinetically investiga in benzene-ethanol solution, using the complex synthesizeq l from cupric acetate and rthylenediamine. It was found that the rate of polymerization(R) increased with the increasing amount of CCI. The rate equations could be expressed as follows;
sin the absence of CCIt; Rpsconstss (Cu(II)complex) (MMA)1 5
in the presence of CCIA:
R, censL(Cu(II) complex)O, 25(CCl₄) 25(MMA)i, 5
The overall activation energies in the absence of and in the presence of CC14 were estimated to be 15.0 and 14.3kcal/mol, respectively.

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The dehydrochlorination mechanism and flame retarding mechanism of poly(vinyl chloride) (PVC) containing sodium phosphates were studied by means of DTA, TG, X-ray diffraction, IR, ESR and gas analyses.
The following results are obtained;
1) HCI evolved from PVC reacts with sodium phosphates at about 210. v2500C except sodium hydrogen phosphate. The reaction products are sedium chloride and phosphoric a- D The formation of sodium chloride is largest and the evolution of hydrogen chloride is smallest in PVC containing sodium orthophosphate. Hence, sodium orthophosphate is most reactive against HCI among various phosphates.
2) The fiame retarding effect of phosphates is attributed both to sodium hloride which is a stable salt against heat and has the flame retarding effect at high temperature due to its physical property, and to phosphoric acid which may inhibit PVC to burn on its surface due tg becoming vitreous poly(metaphosphoric) acid which suppresses a good supply of oxygen that covers PVC.
3) Furthermore, the gas phase combustion may be also suppressed, since PVC which is covered with vitreous rrtetaphosphori acid burns only incompletely and produces non com b-ustible gas, fer example, carbon dioxide and arematic compounds. On the other hand, PVC alone produces combustible gas (low hydrocarbons) during c6mbustion. This fact is elucidated in the following table by indicating the ignition temperature and the activatibn energies for PVC containing phosphates.
4) The stability against heat is confirmed by the following results based on IR and ESR analyses
a) IR absorpticn bands of C O and C Care not observed at 240 C in PVC containing phosphates, while these bands are observed at the same temperature in PVC alone,
b) The temperature at which the ESR signal of polyenyl radical appears for PVC containing phosphates is higher than that for PVC alone. The evolution of polyenyl radical is suppressed in the case of PVC eontaining phosphates.

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The thermal degradatien process of poly(vinyl chloride) (PVC) was studied by means of thermal analyses (TG, DSC) and ESR in nitrogen atmosphere. No ESR signal appeared from the sample in the early stage of the dehydrochlorination of PVC in the temperature range from 150 C to 210 C. Thermal analyses detected two steps of dehydrochlorination in the temperature range from 2200C to 350 C for pure PVC sample, while one step of gradual dehydrochlorination appeared for PVC containing PbO. Experimental value of the second moment of ESR spectrum agreed with the theoretical value calculated fo, r iong pelyene radical whose C/H value is 12. This agreement indieates that the formatien of, polyene radieal by dehydrochlorination is ompleted about 350 C. lntensity increase and narrowing of ESR peak, observed in residue left above 420eC, may be attributed to the fermation of the ring structure. It was cenfirmed that the residue ef thermal decomposed PVC became liquid at (406 5 C). At this temperature, the residue was almost completely dissolved in organic solvents, such as CCIA, cyclohexane and THE i,

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For the purpose of enlarging the utilization of the two kinds of colloidai earths, we studied the adsorptlon of S Oa fro ai SO2 system by granulated earth To elucidate the surface structure of colloidal earth, we compared the results of there system with those for the adsorbents generaly used such as silica gel, alumina gel and acti ated carbons.
The experiment was carried out by using the fixed adsorption bed and the SO2 gas whose concentration was about O.2 vol% (2000 ppm).
The obtained results are as foilows;
1) The adsorption isotherm of SO2 gas-air system is of the Freundlich type and the following relations between C and X for each colloidal earth are found;
X e.070. Ce 20g(for Imaichi C. E.), X O.044. ii2(for Terauchi C. E.)
where C is the concentration of SOti gas (vol %) and X is the adserbed amount of SO2 gas (SO2 1).
2) Trmhe ntfollowing relations are also found between R. number and (H. T. U.)dG for each colloidal earth (R. number 300, mixed gas temperature=20 C, the adsorption column diameter 61 mm and column height=1.8 m):
(H. T. U.)oG O, e20. R.25 (for lmtaichi C. E, the concentration of SO2 (O, 25 vol %)
(H. T. U.)06 O. e30. R. C, 5 (fer Terauchi C. E., the concentration of SO2 (O.30 vel %)
3) Different behavior observed with the two colloidal earths may be ascribed to a difference in the Fe20s content of both earths.
4) lt is inferred that the surface of Terauchi colloidal earth consists of alumina gel, because its break-through-curve resembles that of alumina gel. A large adsorptien capacity of lmai hi colloidal earth appears to be ascribed to the presence of removable Fe20s gel on it.
5) Both colloidal earths, , especially lmaichi colloidal earth, are usefu1 for the desulfurization of SO air system

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The isemerization of ethylethylene oxide was studied over various metal salts at 200-300 C gsi-ng a flow reactor. The surface acidities of the catalysts were measured by the Hammett indicators.
The ratio of butylaldehyde to ethyl methyl ketene in the prcducts varied frem O.47 to 42. O qmong catalysts. The product distributions and the acid-base properties of the catalysts demonstrated that strong acid sites favored the butylaldehyde fo ation and that weak acid sites and basie sites favored the ethyl methyl ketene formatien. lt was concluded that the seleetivity is mainly determined by the different e in the adsorbed state of ethy16tylene oxide on acttve sites.

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The pelarographi behavior of cadmium, copper(II) and manganese(lI) in orthophosphate solution was studied qt ionic strength O.5 adjusted with sodium perchlorate.
The reversible two electron waves were obtained in the pH ranges from 2 to 10 for the cadmium and copper systems, and from 5.2 to 6.5 for the manganese system.
For the cadmium and copper systems three kinds of complexes, M(HPO4), M(HPO4)2, M(HPO4)s and for the manganese system two kinds ef complexes M(HPO), M(HPO), were observed, and their stability constants were calculated by DeFord-Hume s method. The logarithms f the overall stability constants at 25 were 3.0, 3.9, 5 for cadmium complexes, 4.7, 6.6, 7.5 for opper complexes and 2.9, 4.2 for manganese complexes.

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The precipitation polymerization of methyl methacrylate was carried out in cyclohexane using 2, 2-azobisisobutyronitrile as initiator. In terms of the qualitative analysis of the rate of polymerization, the decrease of termination rate constant kt during the polymerization can be expressed as follows:
where YT and m are parameters; X is conversion of MMA and kte is the initial value of kt. The parameters YT and m were determined and then conversion as well as number average degree of polymerization were calculated stepwisely. The obtained conversion-time curves are fit for the experimental values.

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Diallyl oxalate(DAO), diallyl succinate(DASu), and djallyl adjpate(DAA). were copolymerized with allyl benzoate(ABz) in bulk at 60, using benzoyl peroxide as an initiator.
The monomer reactivity ratios(MRR) based on cyclocopolymerization mechanism were obtained as follows:
where the values in pdi entheses de te the apParent MRR estimated from the general coolly mer co posltlon equations.

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