The effects of pressure on the visible absorption spectra of the complexes of cobalt(II) chloride in acetone solution were studied up to 8000kg/cm2 at room temperature by using a high pressure optical vessel with sapphire windows.
The following two kinds of equilibria are found to coexist:
CoC12(Ac)2 + 4Ac ↔ Co(Ac)62+ + 2Cl-(1)
CoC12(Ac)2 + Cl-↔ CoCl8(Ac)- + Ac(2)
where Ac denotes an acetone molecule. The former is an equilibrium between the species which have four and six coordination. The latter is an equilibrium between the species with different ligands, Which has not been observed in any kind of alcohol solution.
As log K1 exhibited curvature against pressure, quadratic functionality (6), which is most common now in use, and equation(7), Hamann's equation newly proposed, were applied to the relation. Both ef the results are shown in Fig. 3.
Since equilibrium (1) forms ions, ΔV1 is large negativevalue as expected from ion-solvent interaction. Also ΔV1 has rather large pressure dependence as listed in Table 1. While equilibrium (2) is scarcely affected by pressure.

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The acetone solution of cobalt(II) bromide is blue under atmosphericpressure at room temperature and the principal species is CoBr2(Ac)2, where Ac denotes an acetone molecule. The visible absorption spectra of cobalt(II) bromidein acetone solution measured under pressure up to 8000 kg/cm2 at room temperature showed that the following two kinds of equilibria coexist as in the case of cobalt(II) chloride.
CoBr2(Ac)2 + 4Ac ↔ Co(Ac)62+ + 2Br-(1)
CoBr2(Ac)2 + Br- ↔ CoBr3(Ac)- + Ac(2)
The value of ΔV1, the volume change of equilibrium(1), and ΔV2, that of equilibrium(2), are shown in Tables 2, 3.ΔV1 which is large with negative sign changes greatly with pressure. Whereas ΔV2 is small and scarcely depends on pressure. ΔV1 estimatedtheoretically from Eq. (II) is shown in Table 4 and Fig. 5.
Those results areconsistent with the facts expected from equilibria (1) and (2). In equilibrium (1) ionic species are formed and the coordination number increases with the shift to the right. On the other hand, in equilibrium(2) there is no change in the numberof charged species and in the coordination number on both sides.

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The sound velocity using sing-around ultrasonic velocimeter and density of aqueous α-heparin solution have been measured at various temperature. The amounts of hydration of α-heparin were calculated from the adiabatic cormpressibility. The values of hydration were 1.04-O.938 (X10-3 m3.kg-1 10-35C) for α-heparin sodium salt and O.647-O.704 (X10-3 m3.kg-1) for α-heparin ion, respectively. These amounts are about twice to five times as large as those of general mono, oligo and polysaceharides. The hydration of α-heparin scarcely depends upon temperature unlike general saccharides. These resultswere explained on the basis of the structure salting-out of the hydroxy and carboxylic groups by the N-sulphate and O-sulphate groups in α-heparin molecule.

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The effect of Zn on the reactivity of precipitated and heavy calciumcarbonate, which have different physical characteristics, was investigated usinga fixed bed. The calcination rate(%) of each calcium carbonate increased by the addition of 1 wt % of Zn within 5 min at temperatures from 800 to 1000 C. Those of heavy calcium carbonate increased exceedingly, particularly 20-25% in about 2min at 900 and 950 C. This effect was also confirmed by high-temperature X-ray diffractien. In the reaction of calcium carbonate with SO2 (15 vol % in air), the conversion rates of heavy calcium carbonate to calcium sulfate were greater than those of precipitated calcium carbonate to it in a few minutes at temperatures from 800 to 1000 C. The values of the latter were 10.1, 25.4 and 56.2% after 5min at 800, 900 and 1000 C, respectively, while those of the former were 62.7, 80.0 and 81.4%. By addition of 1 wt % of Zn, heavy calcium earbonate showed an increase of the conversion rate above boiling point of Zn.

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Crude phenanthrene(C14H10), extracted from coal-tar pitch, contains a small amount of anthracene, fluorene and carbazole as impurities. The most effective purification method was as follows. The crude hydrocarbon (10g) was heated in boiling maleic anhydride (100g) with chloranil (8g) as an oxidizing aget for about 4hrs. Hot benzene (150ml) was added to the reactian mixture, and the solution was boiled further for 1 hr. The benzene Iayer was separated and was heated at 80C with potassium hydroxide solution for 30 min. Then the benzene layer was separated again and the phenanthrene contained was collected after the solvent was eliminated by vacuum distillation. The phenanthrene (13g) was heatd in boiling absolute alcohol (100ml) and metallic sodium (1.7g) was added to this solution, which was further boiled for 3 hrs. After this, reactioh mixture was obtained by eliminating the solvent from the filtrate by vacuum distillation. The obtained phenanthrene was further purified by repeated sublimation and zone melting.
The fiuorescence spectra and wave length dependence of fluorescence life-time of phenanthrene in its solid state were very effective to detect impurities contained in this hydrocarbon. The fluorescence maxima of the high-purity phenanthrene at room temperature were at 370, 380 nm, and at liquid nitrogen temperatureat 355, 370 and 390 nm. And the fluorescence maxima of the impure phenanthrene were observed at room temperature and also at liquid nitrogen temperature at 395, 409 and 430 nm, but not at 370 mn.
The average fluorescence life-time of the high-purity phenanthrene was 62.5 n sec at room temperature, and it decreased to10-44 n sec when the sample was contaminated with a small amount of impurities.

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The viscosities of dilute suspensions in both pure and electrolyte-containing water of H-, Na-, Ca- and Al-montmorillonite were measured with the addition of lignosulfonate (LSA) of an average molecular weight of about 36000.
The limiting viscosity number [η] and the viscosity number ηsp/c (c=O.005 g-clay/ml) were determined and the influence of the added LSA on the modes ofparticle association in the clay suspensions was discussed. With respect to the dilute suspension of clay, it is possible to take [η] and ηsp/c for a parameter of the average shape factor of clay particles including the aggregates at infinite dilution and some arbitrarily chosen concentration of the clay, respectively.
The shape factor for all the systems of the suspensions except for both the Na-Water-8 and Na-NaCl-10 systems was decreased by addition of the LSA though there was difference in its degree. From the values of [η], ηsp/cand the data for the adsorption of the LSA on the montmorillonites, it is concluded that the effect of the LSA on the shape factor is mainly due to the decrease of the edge-to-face association of the clay particles by the adsorption of theLSA on the edge of the particles. And then, for the systems of Na-NaCl and Na-NaCl-10, Ca-CaC12, Al-AlCl3 and Al-Water, it seems that the formation of face-to-face assosiation is hindered by the added LSA.

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The ζ-potential, surface dye adsorption, and free energy of dyeing of poly(vinyl alcohol) fiber, Vinylon, in a cationic dye Methylene Blue solution (pH 10) have been determined. With increasing dye concentration, the sign of the ζ-potential of this fiber in a dye solution changed from negative to positive and the surface dye adsorption increased because of the electrostatic interaction between the fiber and the dye. The linear relations were found between ζ and log Cd (Cd; dye concentration) and the slope did not change with rise of temperature. The surface dye adsorption decreased with rise of temperature. Also the free energy of dyeing ΔG calculated from the slope of the ζ-log Cd curve, etc. decreased with rise of temperature. The heat of dyeing ΔH and the entropy of dyeing ΔS for this fiber were -9.7 kcal.mol-1 and -7.0 cal.mol-1.deg-1, respectively. It was suggested from the occupied area of this dye molecule adsorbed on the fiber at the maximum dye adsorption that Methylene Blue was incompactly adsorbed on the fiber.

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The binding state of adsorbed oxygen on nickel oxide catalyst, whichhas been calcined at 600C for 5 hours in air, has been investigated by means oftemperature programed desorption technique. The desorbed oxygen gives two peaks with maxima at 14-46C (peak I) and 150-180 C (peak II) in the range from 0 to600Cas shown in Fig.2 and Table 1. From the slope in Fig.3 the activation energiesofdesorption are found to be 9.0 and 27.4 kcal/mol for the peak I and the peak II, respectively. The results agree well with the distribution of oxidation power ofthe surface excess oxygen (Fig.4) which was determined by Uchijima et al.Itwas also supposed from the comparison of surface area with desorbed amounts of oxygenthat the surface Ni2+ ions of nickel oxide acted as adsorption sites of oxygen.
The desorption chromatogram of oxygen from nickel oxide, which has beencooleddown in helium after the treatment at high temperature for 30-50 hours inhelium, was also examined. And it indicated the production of adsorbed state of oxygen during quenching in helium. The longer the period maintaing in helium at O C was the higher the oxygen peak I became. The oxygen peak II was approximately constant within the limit of this investigation. These results suggestedthat even at OC the excess oxygen in lattice (or strongly adsorbed surface oxygen) diffused and rearranged onto the sites as adsorbed surface oxygen.

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The selectivity for the ketonization reaction from the mixture of fatty acid, CH3COOH and C2H3COOH, on metal oxide catalysts (ZnO, CoO, SrO, r-Al2O3, Bi2O3, Nd2O3, La2O3, Fe2O3) and a possible reaction mechanism have kineticallybeen investigated.
That the catalytic selectivity for the formation of ethyl methyl ketone as asymmetric ketone on metal oxides shows a volcano-type correlation with respect to the heats of formation (-ΔH0 kcal/acetate-ion) of the corresponding metal acetates as is shown in Fig.4. The ratedetermining step of ketonization reaction is the decarbonylation process of an acid-anhydride intermediate produced from fatty acid ion and acyl cation.
In order to examine this step in further detail, the isotope effect for ketonization reaction has been studied by using CD3COOD and CH3COOD. The primary isotope effect was observed in the cases of Fe2O3, Bi2O3, and Al2O3 except for ZnO, CoO, SrO, Nd2O3, and La2O3. However, no isotope effect was observed when CH3COOD was used as a reactant.
It was also found by the use of deuterium isotope that the rate-determining stepof ketonization on Fe2O3, Bi2O3, and Al2O3 is the C-H bond cleavage process of an acid-anhydride intermediate.

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By the addition of KOH solution to FeSO4-Cr2(SO4)3 mixed solution, Fe(OH)2 was formed and it was oxidized to Fe3O4 by air. The heat treatment of formed Fe3O4 precipitate was carried out in vaccum (10-5 Torr) and in H2-H2O mixed gas (H2O/H2=2) at 200-500 C for 5 hrs.
The effects of the heating temperatureon particle size, surface area and pore structure (pore distribution, pore diameter, pore volume) were investigated by means of X-ray diffraction, electron microscopy and gas adsorption.
Addition of Cr(III) suppressed the particle growthof Fe3O4 and also increased the surface area remarkably.
By the heat treatment of the precipitate; 1) The particle growth of Fe3O4 occurred slightly at temperatures above 400 C, 2) The surface area changed with rise in temperature, that is, the area increased with temperature up to about 300 C and showed a maximum at this temperature. Above 300 C, however, the area decreased. The increase in surface area was caused by micropore (diameter lt 50 A) resulting from the removalof water contained, and the decrease was caused by the pore-widening process resulting from sintering of the precipitate at temperatures above 400 C, 3) The changes of particle size, surface area and pore structure were also affected by heating atmosphere.

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The prevention of oxidation of sodium sulfite solution was investigated. As an antioxidant of sodium sulfite solution, Span 80 (a nonionic surfactant of the type of sorbitan fatty acids ester) was extremely effective. In the case of sulfite solution containing such metal ions as Fe2+, Ni2+, and VO43-, it was necessary to use a masking agent or a precipitant of metal ions in addition tothe above-mentioned antioxidant, and sodium tripolyphosphate and Allon 10 H wereespecially useful for a masking agent and a precipitant respectively.

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The dissolution charactristics of several kinds of allophanes with different SiO2/Al2O3 mole ratie (i, e, g) Kiso-do, Terauchi-do, Kitakami-do and Osawa-do in NaOH solution were studied. The effect of SiO2/Al2O3 mole ratio and chemical composition of these allophanes on the synthesis of zeolite was also investigated.
The extraction fraction of alumina in allophane increased with treating time, while the extraction fraction of silica in allophane increased initially and then decreased rapidly.
Due to the low extraction fraction of silica-alumina and small SiO2/Al2O3 mole ratio (2), A-type zeolite was synthesized from Kiso-do and Terauchi-do. The content of the zeolite from Terauchi-do was 100%, Faujasite-type zeolite was synthesized without additional silica in cases of Kitakami-do and Osawa-do which showed higher extraction rates and larger SiO2/Al2O3mole ratio than Kiso-do and Terauchi-do.

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Our previous work revealed that the curve of the weight increase vs.time in the fluorination of graphite by fluorine gas consisted of four parts. The mechanism of the final part was studied in this paper by means of the thermobalance specially designed for fluorine gas. The flaky graphites from Madagnscar ores with the 800 μ of mean diameter were used for the sample. Experiments have been carried out under the fluorine pressure of 50, 100 and 200 mmHg in the temperature range from 500 to 600 C.
The relationship between the degree of transformation, x, and reaction time, t, was expressed by a modified Jander's equation, [1-(1-x)1/2]2=kt. The reaction rate, k, was proportional to square root of fluorine pressure. The apparent activation energy was found to be 26 ± 1kcal/mol. The reaction rate was depressed when the fluorination of graphite crystal proceeded about 6 μ from edge plane. The time required for the formation of final compound (C:F=1:1) depended upon the diameter of graphite particle. The experimental results indicated that the rate-determining point of the reaction lay in the transfer step of fluorine molecules through the fluorinated layer of the graphite.

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A spectrophotometric method of determination of scandium was studiedby the solvent extraction of scandium-xylenol orange chelate into xylene solution of ethyltridodecylammonium bromide (ETDA). The scandium-XO-ETDA complex was extracted into aromatic hydrocarbons such as benzene, toluene, xylene, but not into polar solvents such as, n-butanol, ethylacetate, methylisobutylketone, and nitrobenzene. The extracted complex had an absorption maximum at 520 nm. Its maximum extraction was obtained when the pH of the aqueous phase was adjusted to 6.O-6.7. The extraction rate of the complex was fast and equilibrium was attained by shaking for 10 sec. Beer's law was seen up to 7.0μg scandium per 5.0ml of xylene. The molar absorption coefficient of the complex was 2.7X104 cm-1.mol-1.l at520 nm. Composition of the complex was estimated to be Sc:XO:ETDA=1:1:2 by the mole ratio, continuous variation and mobile equilibrium methods, Consequently it may be assumed that the ternary complex was an ion association system with [ScHR2-]((ETDA+)2) structure, Triethylenetetramine and o-phenanthroline can be used for the masking of many metal ions, but the presence of vanadium, aluminum, beryllium, thorium, zirconium, uranium, bismuth, lanthanum, nitrate, perchlorate, citrate, EDTA interfered the determination seriously.

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Hydrophilic gels were prepared by the crosslinkage of poly(vinyl alcohol) in suspension state with epichlorohydrin. The permeabilities were determined by eluting water soluble materials, such as poly(ethylene glycol) and dextran, through a column packed with the gels. Excluded molecular weight increased with the decrease of poly(vinyl alcohol) concentration in the aqueous solution and reached to 2X106. A new preparation method of bead-shaped poly(vinyl alcohol) has been developed. The beads of pely(vinyl acetate) were hydrolysed stepweise. Atthe first step, the beads were hydrolysed mainlyi on the surface in aqueous solution of sodium sulfate and sodium hydroxide followed by the addition of a small quantity of methanol, and at the second step, mainly on the inside in the alkaline methanol. The molecular weight and saponification degree of resulted poly(vinyl alcohol) were 67000 and 98.8mol%, respectively. Another type of hydrophilic gel was prepared by the crosslinkage of bead-shaped poly(vinyl alcohol), Tolylenediisocyanate, hexamethylene diisocyanate and epichlorohydrin were used as crosslinkage reagent. These gels could be available for the separation of materials containing various molecular weights. Gel, prepared by the crosslinkage of poly(vinyl alcohol) in the suspension state, was suitable for the separation of polymer, the others for the separation of oligomers. The slope of the calibration curve, α, was affected by the preparation method of the gel.

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A method has been developed for the determination of manganese in sea water by neutron activation using Chelex 100 chelating resin as a pre-irradiation concentration agent.
Chelex 100 resin (O.5-1 g as wet basis) was Packed into a column (0.65 cmφ X10 cm) and purified by washing with 2N HNO3 and 2N NH4OH (see Table 1), and finally transformed into NH4-form by washing with O.1N NH4OH until pH of effluent became above 6.
Sea water (O.1-O.5l), previously filtrated with a O.45 μ pore-sized membrane filter, was passed through above column at a flow rate of within 1.5 ml/min te separate manganese from sea water. The resin was transferred into a polyethylene bag and dried in an electric oven at 75C for 10 hours and heat-sealed off.
The resin samples together with standards were irradiated with pneumatic tube system of JRR-2 reactor at a flux of 7X1013 n/cm2/sec for 20 minutes, After cooling for about 3 hours, the irradiated resin was slurried with water and transferred into a column previously packed with O.1g of Dowex A-1 chelating resin, then treated with 50 ml/g.wet.resin of 0.1NKNO3 to elute out the interfering nuclides such as 24Na and 82Br. The γ-activities from 56Mn in resin were counted with a Ge(Li) detector after cooling for about 5-6 hrs.
At present, the chemical yield of manganese was over 98%. And, the blank was 0.003μg/ g.wet.resin. The minimum determinable and detectable masses are thus presumed to be about 0.03 μg per 500 ml of sea water (10-fold of blank) and 0.006 μg per 500 ml of sea water (2-fold of blank), respectively.

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On the photolysis of ω-phenoxyacetophenone (PAP) in benzene solution containing triethylamine, the substituent effect was investigated.
In the case of PhCOCH2OC6H4-X(X=H, OCH3, Cl), the substituent effect on the conversion of PAP was generally small, except for 2- or 3-Cl substituted PAP. But the yield of phenols was affected by the character or position of X. In the case of Y-C6H4COCH2OPh (Y=H, OCH3, Cl), the Photolysis of PAP was accelerated by the substitution of OCH3 or l, and phenol was produced in a good yield.
Next the effect of added amines was examined. When aliphatic amines (di-n-butylamine, cyclohexylamines) were added, the photolysis of PAP was remarkably accelerated and phenol was obtained in a good yield. But, this accelerating effect on the photolysisof PAP was not observed by the addition of the primary, or secondary aromatic amine (aniline, N-methylaniline). N, N-dimethylaniline promoted exceptionally this photo-reaction, although the phenol formation was in low yield.

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In the oligomerization of ethyle:ne by Ni(acac)2-(C2H5)3Al2C13-P(C6H5)3 catalyst at a temperature higher than -10 C, a considerable amount of C6-olefins was formed together with C4-olefins (e.g., C4 40.6%, C6 43.8% at O C). Most of the C6-olefins consisted of 3-methyl-2-pentene (e.g., 82.9% at O C). The formation of the 3-methyl-2-pentene was found zero-conversion method was to be due toan insertion reaction of 2-butene to a nickel-ethyl bond. The effect of the basicity of tertiary phosphines on the formation of C4- and C6-olefins was discussedin terms of the above result.

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The reaction of α, β-unsaturated α-chloro-β-amino ketones with thiols was investigated and the structures of the products wereestablished. The reaction of 4-amino-3-chloro-3-penten-2-one [1], 3-amino-2-chloro-1-phenyl-2-buten-1-one [2] and 3-amino-2-chloro-1, 3-diphenyl-2-propen-1-one [3] with ethanethiol or p-substituted benzenethiols (substituent X : Me and NO2) in CCl4 under nitrogen atmosphere at room temperature gave 4-amino-3-ethylthio-3-penten-2-one [4a], 4-amino-3-p-substituted phenylthio-3-penten-2-one [5a], 3-amino-2-phenylthio-1-ptienyl-2-buten-1-one [8a] and 3-amino-2-phenylthio-1, 3-diphenyl-2-propen-1-one [9a], respeetively. The N-methyl and N-phenyl derivatives gave the corresponding products [4b], [5b, c], [6b], [7b], [8b, c] and [9b].
The effect of p-substitutent on nucleophilic reactivity of benzenethiols was elucidated. It was found that introduction of ethylthio or phenylthio group into α-position of enamino ketones resulted in a marked delocalization of π-electrons in the hydrogen bonded chelate ring. The enhanced stability of the chelate ring is rationalized in terms of the electron withdrawing resonance effect of S atom through pπ-dπ conjugation.

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The reactions of benzoic anhydride with excess benzene and naphthalene in the presence of cupric oxide have been studied under the influence of oxygen.
With benzene, the total yields of phenyl benzoate and phenol produced by the reaction of benzoic anhydride with benzene and by the decomposition of cupric benzoate, increased with increasing initial air pressure, up to the higest value of 26.1 mol% at about 3atm(260 C, 3hrs, cupric oxide/benzoic anhydride=1: molar ratio), and decreased. Similary with naphthalene, the higest yield of β-naphthyl benzoate produced by the reaction of benzoic anhydride with naphthalenewas found to be 13.9mol% at 1atm (250 C).
The results appear to indicate thatthe reaction of copper benzoate with aromatic solvents precedes its intramolecular reaction under the condition where the air pressure. is comparatively low (below 1atm).

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The complex layer of C6H5R-AlCl3-HCl system was used repeatedly for the disproportionation reaction of alkylbenzene (EtPh and i-PrPh) by substituting the upper hydrocarbon layers with fresh alkylbenzene after each reaction. In the reaction at 2 C, the amount of disproportionate product decreased with each run and was negrigible after several reactions. However, the bubbling of HCl caused the complex layer to recover its initial activity (Fig.1). Reacting at highertemperatures (20-50 C), the products increased gradually with temperature and a decrease of the products was not observed with each reaction at 50 C (Figs.2 and3). During each reaction, the constituents of the complex layer were maintained constant at 2 C, but were changed slightly toward higher temperatures (Table 1).
These results indicate that: (i) complex [1], postulated in our previous paper, did not initiate the reaction at 2 C without HCl (Eq.(2)) but (ii) the dissociation of complex [1] took place at higher temperatures and then the reaction proceeded without HCl along the Eq. (3) according to the "HSAB" rule.

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The dehydrocyclization reaction of n-heptenes over a chromium oxide catalyst supported on alumina has been studied in the temperature range of 400-450C in a flow reactor to elucidate the mechanism of the dehydrocyclization. A small amount of n-heptadienes, which was yet much more than that of toluene was detected in the reaction at lower conversion of n-heptenes. Migration of the double bond in n-heptenes proceeded so rapidly in comparison with dehydrocyclizationreaction, that the equilibrium compostion of n-heptenes was attained before several per cent of n-heptenes were converted to toluene. No difference was observedin the initial rate of formation of toluene either from 1-heptene or 3-heptene. Results of the pulse reaction showed that the rate of fermation of toluene decreased in the order: methylcyclohexenes n-heptadiene n-heptenes n-heptane. The mechanism by way of n-heptadienes is preferred to the Twigg-type mechanism consisting of direct cyclization of n-heptenes.

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Although Co(III)acetate oxidizes aromatic compounds in acetic acid solution in the absence of oxygen via an electron transfer process, other metal acetates at higher valence state such as Mn(III), Cu(II) or Ce(IV) acetates show a very low activity in the oxidation of toluene. It has now been found that the activity of Co(III) in the oxidation is remarkably reduced by the addition of other metal acetates at lower valence state as well as at higher valence state. When the molar ratio of other metal acetates to Co(III)exceeds a certain value, Co(III) loses its activity for the oxidation of toluene. The order of inhibition effect is as follows.
Mn(II) Mn(III) - Ce(IV) Cu(II)
Visible absorption spectra suggest that inhibition effects by added salts are due to the formation of polynuclear complex between Co(III) and other metal acetates. However, metal combination Cu(II)-Co(III) which is quite inactive in the oxidation of toluene presents the same activity as that of Co(III) in the oxidation of α-methyl naphthalene. Accordingly, the lower activity in the oxidation of toluene of the polynuclear complexes of Co(III) with added salts can be attributed to a reduced redox pontential of the complexes compared to Co(III) acetate.

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The behavior of photofading of some anthraquinone, azo and quinophthalone disperse dyes, and coumarin derivatives on polyester or polyamide film hasbeen examined, The effect of Annellation on the fading and the mechanism of photofading reaction of these dyes and derivatives were discussed, 6, 7-Benzo(Annellation) derivatives of 1, 4-diamino- and 1, 4-dimethyl-amino-anthraqttinone were more resistant to photefading than the compounds that did not contain this configuration, 2-Hydroxy-1-naphthylazobenzene faded to light more rapid than the corresponding 2-hydrexyazobenzene. 3, 4-Benzo coumarin faded much less, and 5, 6-, 6, 7- and 7, 8-benzo derivatives faded more rapid than coumarin. The photofading of 5, 6- and 6, 7-benzoquinophthalones were more sensitive than that of quinophthalone. 5, 6-Benzo derivative faded much less and 6, 7-benzo derivative more rapid than the parent in hydroxyquinophthalone.

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The radical polymerization of vinyl acetate in the presence of acid components and carbonyl compound of Larix leptolepis was kinetically investigated by the use of a dilatometer.
In the radical polymerization of vinyl acetatebrought about by the addition of unvolatile organic acid and resin acid, the precise induction period was observed, but the addition of phenolic component and carbonyl compound. A proportional relation was observed between the induction period and the amount of unvolatile organic acid added. Also, from the retardating efficiency (k/k0), it was recognized that the addition of carbonyl compound and resin acid resulted in the promoting effect on radical polymerization, and the addition of unvolatile organic acid and phenolic component resulted in the retardating effect on it.
Based on the above result, it may be concluded that the inhibiting effect on radical olymerization in the presence of alcohol-benzene (1:2) extractives is due to phenolic component and unvolatile organic acid contained in it, while in the case of hot water extractives, unvolatile organic acid hasan inhibiting effect.

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When cellulose fibers are treated with conc. aqueous solutien of AcOK, washed with benzene and dried at 80 C, they give a new strong meridional diffractioh (I0) corresponding to (010) of cellulose I or cellulose II. However, 10 changes more and more into a new first layer diffraction with a spacing of 9.5A (11) with an increase in drying temperature. In addition, new equatorial diffractions appear at 160 C, though they are weak. The treatment with AcOK gives no change in the crystallinity of the Cellulose fibers, which indicates that the new diffractions are due to AcOK-cellulose addition product formed in the amorphous region of cellulose fibers.
It was found that the more perfect crystallite ofAcOK-cellulose was obtained by washing potassium-cellulose with acetic acid. Theunit cell is monoclinic with a=24.83A, b=10.32A (chain axis), c=8.83A and β=101.2 . Miller indices of I0 and I1 are (010) and (110), respectively. The intensity of Ii is extraordinary strong and depends on cellulose fibers used. This implies .that I1 results from both perfect crystallite and imperfect crystallite in amorphous region of fibers. It was calculated that the imperfect crystal structure giving only I1 in fact relative arrangement between (200) planes. This fact was confirmed by Fraunphfer optical diffraction photograms for the two-dimensional plane lattice models.
(200) plane of AcOK-cellulose corresponds to (101)plane of cellulose that shows sheet like unity during reactions of cellulose. Therefore, it is considered that the (200) plane lattice structure of AcOK-cellulose is based on, the (101) plane lattice structure of cellulose in amorphous region of fibers.
Intensity of I0 increases proportionaly with decrease of crystallinity of cellulose fibers used, It is believed that the (101) plane lattice structure, special type of crystal defect, is representative structure in amorphous region of cellulose fibers.

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The salts of cationic polymer containing piperidine, morpholine and tetrahydro-1, 4-thiazine ring in a main chain with 7, 7, 8, 8-tetracyanoquinodimethane(CQ) were prepared and their specific resistivities (p) and activation energies of conduction (Ea) were measured. A general structure formula of the salts wasshown as follows;

x:c, o, s, p=3, 6, q=0.0, 0.2, 0.4, 0.6, 0.8, 1.0
Minimum resistivities, pmin, of these eomplex salts were about 102Ω.cm in allsystems. The values were one tenth in comparison with n, m-Ionene-CQ type of complex salts and also Ea values were small. Resistivity, p of 3DMX-CQ (X:O, p=3, q=O.O) simple salt (2.2x103 Ω.cm) was very small, though the effect of dopedCQ0 for electric conductivity was not observed. But the doping effect of CQ0 for6 DMX-CQ (X:O, P=6) was remarkable for electric conductivity. It may be conjectured from these results that hetero-ring and oxygen atom play a role in the available arrangement of CQ for conductivit.
On the contrary, the degradation of CQ salt was promoted by the existence of polar group (oxygen, sulfur atom), whichmay be related to adsorption of moisture.

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Cationic polymers as shown in formula I, II, and III were prepared and electric conductivities of their 7, 7, 8, 8-tetracyanoquinodimethane(CQ) salts were investigated in relation with their stability and processing characteristics.
Simple salts Complex salts
p(Ω.cm)Ea(eV)p(Ω.cm)Ea(eV)[CQ0]/[CQ ]
I-CQ 2.1X105 0.17 68 0.12 1.0
II-CQ 1.3X105 0.32 2.1X103 0.24 0.5
III-CQ 3.4X105 - 1.1X103 0.16 0.3


The resistivity of I-CQ cemplex salt was markedly low. The solubility of II-CQ and III-CQ in dimethylformamide, dimethylsulfoxide etc. was much better than that of I-CQ. In addition, film-formingproperty of III-CQ was very good. On the contrary, the introduction of hydrophilic groups to the polymer chain promoted the degradation of CQ salts, that is, moisture as well as oxygen seemed to effect the degradation. The stability was thehighest in I-CQ and the lowest in II-CQ.

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cis-[Co(III)(en)2PVICl]Cl2, cis-[Co(III)(en)2NEICl]Cl2 (PVI:poly-(1-vinyl-2-methylimidazole), Pn=250, NEI: N-ethylimidazole) complexes were synthesized and the reduction of these complexes by FeEDTA2- was investigated. Especially, the effects of ionic strength and the addition of alcohdls were examined and the activation parameters (ΔF, ΔH, ΔS ) were measured.
With an increase in the ionic strength μ, log k (k: the pseudo first order rateconstant of the electron-transfer reaction) decreased linearly in relation to μ in the Co(III)-PVI system. It was noticed clearly from the result of the viscosity measurement that the conformational changes of the polymer complex gave a large influence on the reactivity. Furthermore, in the H2O-alcohol mixed solvent, an increase in the alcohol concentration accelerated the reaction and, when ethanol or 2-propanol was used in the Co(III)-PVI system, the maximum of k was observed. With a rise of the reaction temperature, the maximum point was shifted to the lower alcohol concentration. These phenomena were discussed in regard to the conformational changes of the polymer complex.

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Schiff bases containing the pyrrole nucleus were synthesized from 2-formylpyrrole and various amines and the reactions between the copper complexes containing such ligands and 2, 2-diphenyl-1-picrylhydrazyl were examined, When a monomer complex was considered, the more the π-conjugated system of constituent ligands spread, the larger the rate of reaction was. In general, the rates ofthe polymer complexes were smaller than those of the monomer complexes. Thus thesteric hindrance is important in these reactions. These reactions are consideredto proceed via the intramolecular electron transfer through the ligand, since the rates of reactions largely depend upon the molecular structure of ligand.
The activation energy of the reaction was directly proportional to the half wave potential of the reduction of the central cupric ion. In the case of polymer complexes, the redox potential of the central cupric ion was sensitively affected by the environment of the polymer chain.

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Both potentials and viscosities of the system of poly(methacrylic acid) (PMAA) and polyethyleneimines (PI) with different chain lengths were measured in aqueous solutions. The cooperative interaction between both components was discussed on the basis of the relationship between the stability of the complexes and the chain length of PI.
It was found that the interaction between PMAA and PI became stronger by increasing the chain length of PI, since the slopes ofthe potentiometric titration curves (PMAA by PI) were loosened gradually with the chain length of PI. Furthermore, the viscosity behavior of the system containing excess PI was characterized by the chain length of PI, so that the stability of the complex was closely connected with the chain length of PI. The viscosity of the complex solution was decreased with time. This result means that the complex seems to be in non-equilibrium state and to be stabilized with time. In these systems, the chain length of PI, that is, the cooperative interaction of binding sites, influenced the stabilization of the complexes positively.

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The electrolysis of a solution of N-vinylcarbazole and lithium perchlorate in acetic anhydride or acetonitrile by rectangular wave from current (5:1, RWC) resulted in the formation of poly(N-vinylcarbazole) in the anode compartment of a divided cell.
No polymer was obtained when various solvents other than acetic anhydride or acetonitrile were used.
The [η] values of the polymers formed by RWC were higher and their colorations were lighter than those of polymers formed by direct current (DC) under similar conditions.Obviously, the polymerization by RWC would be of overwhelming importance for the preparation ofpolymer ef high molecular weight and of light colored species.
UV and IR spectroscopic studies showed that more ester and acyl groups existed in the polymer formed in an acetic anhydride solution by RWC than by DC, and the structures of polymers formed in an acetonitrile solution were similar to those of the polymersproduced by the usual cationic polymerization, although a small amount of C=C groups existed, in the former polymers.
The presence of very active species in the electrolyzed solution suggested that acyl groups or hydrogen cations, which were produced by electrolysis of acetic anhydride or acetonitrile respectively, initiated the polymerization.
Moreover, it was assumed that the polymerization, initiated by electrolysis RWC proceeds via a cationic mechanism.

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The aqueous solutions of propane-oxygen mixtures under pressure, on irradiation with 60Co r-rays, yielded hydrogen peroxide, organic hydroperoxides, acetone, propionaldehyde, 1-propanol, 2-propanol, and hydrogen. The G values of these radiation products were determined under various irradiation conditions.
The formation of the oxygen-contained compounds was interpreted in terms of reactions of both hydroperoxy and organic peroxy radicals.
The formation of hydrogen suggested that the hydrogen atoms might be capable of abstracting hydrogenfrom propane in competition with addition to oxygen.

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In order to obtain the relationships between the conversion and the number average degree of polymerization and those between the conversion and theresidence time, the solution polymerization of methyl methacrylate (MMA) by azobisisobtyronitrile (AIBN) in benzene was carried out in a continuously stirred tank reactor (CSTR), using benzenethiol as the chain transfer agent.
It was found that the conversion increased as the benzenethiol concentration was increasedin the range of 8x10-4 to 3.2x10-8 (mol/l) and that the index of molecular weight distribution (Q=Pw/Pn) decreased as the benzenethiol concentration was increased.

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Polymers of isohexane were formed by the addition of antimony pentachloride to isohexane. In polar solvent the rate of this reaction was accelerated.Apparent activation energy was 4.0kcal/mol which was lower than that of ordinary porymerization.
The structure of the polymer was studied by IR and NMR spectroscopies, and the polymerization mechanism was discussed.

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