Consider a molecule weakly interacting with the external field, The change of any physical quantity of this molecule, in terms of the linear approximation to this interaction, is expressed as a commutator of two operators representing this physical quantity and interaction, respectively. lf we estimate the average value of this commutator, or the correlation function in space-time, in the lowest order (Hartree-Fock approximation), we obtain the result usually derived from the second order perturbation theery. ln the higher order approximation, say, taking into acount the electronic correlation, a technique of the many-body theory is effectively applicable. The above mentioned commutater is itself a retarded Green s function. To estimate this in terms of the systematic perturbation expansions, or diagramatically, we have to use the following procedures; first, the corresponding temperature Green s function is calculated, second, from it the desired retarded Green s function is obtained through analytical continuation. Actual calculation is performed up to the first order with respect to the electronic correlation.

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Equilibrium surface tensions of the aqueous solutions of sodium alkyl sulfates containing 8, 10, 12, 14 carbon atoms were elaborately measured at the air-solution interface by means of the Wilhelmy plate method at 300C, and the amounts of adsorption were calculated by using the Gibbs adsorption isotherm. lsotherm for adsorption shows the saturation at a concentration below the critical micelle concentration (CMC) of respetive solution. The concentration at which the adsorption was Saturated was defined as the saturated adsorption concentration (SAC). The logarithm of SAC held a good linearity against th6 number of carbon atoms (N)in the surfactants. lt was shown in the theoretical and experimental approaches that the molecular cross-seetional area in the region of saturated adsorption increases linearly with increase in N. The energy difference between the micelle formation in the solution and the adsorption at the air-solution interface was calculated as 47. l cal/mol per methy1ene group from the theoretical analyses. This value was in good agreement with one calculated from the theory of mic elle formation given by Shinoda and from the energy data of desorption for methylene group at the air-solution and oil solution interfaces. ln the Similarity to the characteristics of the CMC in the surfactant solution, the SAC may likely be used as a good measure to interpret the surface phenomena at the air-solution interface.

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For the purpoSe of studying the energy transfer between gas molecules and a solid surface in a mixture of gases, the heat loss from a piatinum ribbon was measured in the mixture of carbon monoxide, oxygen, and carbon dioxide under the pressure range of IAv4 10 2 mmHg. and at ribbon temperatures of 165 and 2280C. The heat loss in the mixed gas was found to be the sum of the heat losses measured separately for each gas. The result was explained as follows. ln the gas mixture, the surface of platinum was covered almost completely with a chemisorbed layer of carbon monoxide, and the impinging gas melecules were adsorbed physically on the layer and exchanged their energy with it. For carbon monoxide, the energy transfer and the accommodation coefficient in the rnixture should be identica1 to what in carben monoxide alone. Therefore, the additivity of the heat loss observed in this Study shows that the accommodation coeMcients of oxygen and arbon dioxide in the mixture were equal to those observed separately in each gas.

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The relation between the selectivity for isomerization reactions and the electronegativity of metal ions on ion-exchanged porous glass catalysts has been investigated using propylene oxide as a reactant which formed three isomerized products: propionaldehyde, acetone, and allyl alcohol on acid-base bifunctional catalysts. The influence of the surface hydroxyl group on the exchange of metal ion was examined by means of infrared absorpotion method. A possible reaction mechanism was discussed in terms of the reaction intermediates adsorbed on the catalysts.
Adsorption of propyiene oxide occured at an oxygen atom in epoxy ring on the acidic site, and at a B-carbon atom in propylene oxide on the basic site, while allyl alcohol was produced by concerted mechanism on the surface hydroxyl group and its conjugated base.
It could be concluded that the acid strength of metal ion. exchanged porous glass catalyst increased with increasing electron attracting force of exchanged metal ion and the selectivity for the isomerization reaction ef propylene oxide was dependent on the strength of acidic and basic sites on the catalysts.

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The effets of the addition of methyl methacrylate (MMA), methyl acrylate (MA) and acrylonitrile (AN) on the catalytic activity of TiC13-AIEtC12 for propylene polymerization have been studied. TiCls-AIEtC12 was inactive without additives. On the addition of MMA or MA to the system highly stereoregular polypropylene (1.1.=94N96%e) was obtained, although the activity was lower and less stable than that ef TiCls-AIEt2Cl. The system with AN was inactive for propylene polymerization.
On the basis of the kinetics of propylene polymerization with TiCls+{AIEtC12 MMA (or MA)}, it has been conc1uded that a complex formed from AIEtC12 and MMA (or MA), AIEtC12. MMA (or A12Et2Cl, MA), acts as an active cocatalyst for TiC13, while free MMA (or MA)acts as a poison for TiCls-surface. The active complexes evolved considerable amount of ethane and ethylene when they were mixed with TiCls at 830C, but inactive ones, AIEtC12 and AIEtC12, AN, did not. This result suggests that MMA and MA activate Al-Et bond. The polymerization activities of these complexes have been discussed in connection with NMR data of these additives.

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The vapor phase sqtalyt-ic-methylation of ev-picoline with methanol has been studied in a flow system using solid acid, base and acid-base catalysts over a range of temperatures fr6n1400 to 530 C under atmospheric pressure.
On Shes. e cat. a.1. ystsAthg 14. ajor. liquid-produ. cts obtained were 2, 6-lutidine along with small amounts of pyridine, B-picoline, 2, 4 and 2, 5-lutidines and 2, 4, 6-collidine. The Torder of the gatalytic qctivity wqs silica Tnagnesuzia silica-alumina kk T-alumina fluorinated rm T: al miKaV magnesium phosphate. Silica gel, magnesia and calcia were virtually inactive.

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The na re of the catalytic active sites of cationic zeolites(X, Y)for methylmigration of anisole was studied using flow reactor. The order of catalytic activities were as follows; RbX KX NaX=LiX at 3000C, RbY KY NaY LiY at 3500C, BaX SrX CaX MgX at 275eC, BaY SrY CaY MgY at 2500C. This result indicates that the cationic zeolites containing the stronger electrostatic field become more active, The same result except the cases of alkali metal X and MgX was also obtained by the comparison of electrostatic field and the catalytic activities determined by the temperature for 10% anisole conversion.
Upon addition of water, the order of increase of anisole conversion on alkali earth metal zeolites except MgX and MgY was equal to the order of electrostatic field strength Ba Sr(Ca). While that on alkali metal X was as follows; Li Rb=Na K. This result did not coincide with electrostatic field strength, but it had good correlation with the facility of decationation of alkali metal X.
The catalytic activity of NaX was decreased gradually as NaOH was annexed, and the addition ef water te NaX annexed with NaOH allowed anisole conversion to increase to a constant value, 11 mol %o, regardless of the amount of NaOH.

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The reaction of ethylene or propylene over alumina supported tungsten oxide catalyst has been investigated at 200eC, using a onventional closed circulation apparatus with reference to the nature of active site.
Formation propylene, butene and polymerized products were obserbed in the re. action of ethylene, in P propylene was assumed to be produced bytdispr opor-tion ation of ethyleRe witradsorbed butene formed by dimerization of ethylene. On the other hand, propylene gave ethylene and butenes in almost the same amount. This fact indicatcd that b. ot. h. were prodgceq thr6ugh disproportionation of propylene, Propylene also gave polymers which were retained on the catalyst.
According to the ehange of pretreatment temperature of the catalyst, both activity of the catalyst and distribution of the products changed remarkably. The activity of the catalyst fer the three types of reaction, i. e., disproportionation and polymerization of ethylene and disproportionation of propylene, was increased extensively by the evacuation above 400eC. Analysis by TPD method revealed that reduced tungsten appeared on the surface of the catalyst and it played a role of active site in these reactions.
A close relationship was obserbed between the activity of propylene polymerization and the amount of pyridine adsorbed on the catalyst. This result suggested that polymerization of propylene proceeded on acidic site of the catalyst.

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NaCl powder sample was prepared by the recipe mentioned in the previous paper. Water adsorption isotherms on the samples outgassed in the temperature range from 250C to 3600C and their surface area values were determined. Effect of the amount of presorbed water on the isotherms was also tested.
Each of the isotherms showed a stepped rise in the adsorbed amount at the vapor pressure forming two layers completely. ln the case of outgassing at 250C, reproducib!e isotherms were obtained for the repeated adserption up to forming three layers. The sample outgassed after ferming eight layers showed 20% decrease in the monolayer capacity. When the presorbed amount exceeded the amount necessary to form 2.7 layers, a surface area of the sample began to decrease.
The outgassing at temperatures above 200 C decreased the height of a stepped rise of the isotherm, and the subsequent outgassing at 250C 1owered the water adsorption ability. Corresponding to the above phenemena, the surface area of the sample more decreased by adsorbing water than that of the sample untreated.

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In p. xd, euax.. to olmhtain the fundamental data for separational and condensing processes in urea syntheses, the vapor-liquid equNibria for the ternary system of ammonia-carbon dioxide-water diere i stuaied froin 106 to M1400C at the pressure of 20 kg/cm2. And isothermal solubility curveS and the empirical equations te estimate the relation of the vaper-liquid equilibrium were, obtained.
The active t, y, coeficients in the liquid phase, ri, were expressed by the following van Laar 2-suflfix equations.
1 1, N (438, +45, , , xc, , xH, , )1(xNH, 4, 8, ., , +3, 74, xN, , )2 (, ) logTH, o=O. PO859x2NN, 3.3486 x2co, .7085 xNH, xce, /(xH, o+O.2675 xNH, 1.283xco, )2 (2)
From good agreement of the va1ues calculated by Eq. (1) and (2) with the experime. ntal results, ii was found that mole fractions in the vapor phase, y, are well estimated from those in the liquid phase, xi, in the experimental conditions.
The pa eters, (2i/P), which are equal t, ixs1 and are ecessary f, r the estlmati, n of the vapor-liquid equilibria, were given by the following simple equations.
log(zNN31P H3)rr=621/T-2.079.. (3) log(zH, o/POH, e)rr=1995/T-4.140 (4)
An it is shown that the relation between log(yNH3/yco2) and log(xNH3/xco3) has a linearity at the constant temperature.

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The flocculation behavior of particles iR two kinds of bentonite suspensions has been studied in the presence and the absence of polymer flocculants. Suspension A was prepared by dispersing bentonite in pure water and subsequent addition of iRorganic electrolytes such as Ca(OH)2 and CaCI2. Suspension B was prepared by dispersing bentonite directly in inorganic electrolyte solution.
Both the settling and the filtration rates of B were higher than those of A. An extreme difference of settling rate was found between A and B, The addition of polymer flocculant greatly increased settling and filtration rates, but the difference in flocculation behavior between A and B still remained. High settling rate (7 cm/min) was obtained with the addition of Ca(OH)2to 250 ppm Ca and Separan NP 20 to 2 ppm in the case of B (Fig, 7),
When kaolin, silica powder, pettery clay or silt rich clay containing no montmorillontite was substituted for bentonite, no appreciable difference was observed in the flocculatioR behavior between two kinds of suspensions. On the other hand, the flocculation behavior of suspensions of coal debris which contained considerable amounts of montmorillonite changed according to the preparation method of suspensions as was the case for bentonite (Fig.2 and Fig.3),
Above experimental results suggest that the addition of an adequate amount of inorganic electrolyte such as Ca(OH)2 to the water for dressing or washing of coal, gravel and the like containing montmorillonite facilitates the flocculation treatment of the waste eMuent from these processes through the resultant suppression of the swelling of montmorillonite.

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Preparation and properties of a new compound, urea molybdate, are described.
Urea reacts with molybdic acid in aqueous medium to give a white precipitate.
The compound is a white, anhydrous, crystalline powder. Chemical analysis and X-ray powder diffraction study reveals that the compound can be represented by H2Mo207e2CO(NH2)20r H2Mo30ige3CO(NH2)2, or by a mixture of these formulae. lt is semewhat soluble in water, dimethylsulfoxide, methanol and ethanol but is insoluble in various organisolvents.
Conductivity and molecular weight measurements of urea molybdate in dilute aqueous solutions show that the compound is completely disseciated into urea and molybdic acid in the medium. The density is 2.558 v2.571 g/cmg (at 250C) and refractive index (nD) is 1.769. vl.770. Urea molybdate is fairly stable up to about 200eC, but deomposes at 240. v2550C and changes completely into MoOg at 2900C, which is indicated by TG thermogram and DTA curve.

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Ten samples of glass fiber-phenol resin laminate with different glass content were carbonized at 1000, 1200, 1400 and 16000C in the atmosphere of inert gas and several properties of the carbonized products were examined.
Flexural strength of the samples, heat-treated at lower temperature than 1200C, increases with the elevation of glass content. But for samples, heat-treated at higher temperature than 140000, this tendency is less remarkable. Flexural strength samples with the same glass content deereases with the rise of heat treatment temperature (HTT),
True density and bulk density increase with elevation of glass content, but porosity has a reverse tendency.
Volume electric resistance of composites carbonized at 1000 C increases with the elevation of glass content, ancl for samples with the same glass content it decreases with the rise of HTT,
Photographs of the scan-ning electron microscope show that glass fiber begins to adhere each other at 14000C and otherwise adhesion between matrix and glass fiber is improved above 14000C, ln spite of these facts, flexural strength of carbonized samples decreases with the rise of HTT, This may be attributed to the fact that carbon atoms diffuse into glass fibers and make them brittle as described in the previous paper.

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Surface microstructures of synthetic emerald crystals grewn by the V20s fiux method, using the natural beryl seed, were studied by optical microscopy. Most of emerald crystals were synthesized at temperatures ranging from 1040 C to 10650C, keeping the temperature difference of 15 C between the seed and the nutrient.
In a case where growth rates for c, m and a-planes were faster than 10 2 mm/hr, growth hills on c, m and a-planes were found to exhibit hexagonal roundish rectangular and roundish slender rectangular shapes, respectively. ln a case of lower growth rates than 10ww2mm/hr, spiral growth patterns were observed on each plane..
As for c-plane, the growth pattern of hexagonal spirals was observed at a grewth rate of 2, o 10 3mmlhr, dodecagonal spirals at 3, o 10 3 mm/hr and circular spirals at 7 10-3 m hr. It was found that growth hills for c-plane showed a tendency to change their shapes from hexagonal to polygonal as the growth rate increased.
A roundish rectangular spiral was observed en m-plane at a growth rate of O.3 10-8 mm/hr, aroundish rectangular having a smaller radius of curvature at O.7 10 3mm/hr.
In a case of a-plane, similarly, a slender rectangular spiral was ebserved at O.4 10 S tnm/hr, a slender elliptic spiral at 1.1 10-S mm/hr. The average ratio of length to breadth of rectangles was about 1.7 for m-plane, and 3.8 for a-plane.
The hexagonal trapezoids were observed on c-plane. The diagonal length of the upper surface ef a hexagonal trapezoid was about 33 pt, and an orientation of hexagon was consistent with that of the mother emerald single crystal.

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The kineticsof extraction of nickel()from aqueous solution, using chloroform solution of 6 (2-thiazolylazo)naphthol(TAN), was studied spectrophotometrically in the pH range 5.8. v7.1and at an ionic strength pt=O.1.
In a su Lciently high sha: ki: ng speed region, the extraction was co: ntro11ed by a chemical reaction in the aq ueo us phase. The reaction wasof rst-order with respect tonicke1(), s order with respect to TAN and inversely, first-order with respect to hydrogen ion, which indicated that the formation of 1: 1 chelate in aqueous phase was the rate-determining step. The rate constant of this reaction was found to be 2.5 1061, mol-i, sec-i at 2980K.
The higher rateof the nicke1() TAN complexation reaction than t: hat of the reaction in similer nicke1()systems, already reported, was discussed in terms of a model in which the loss of the first water molecule, coordinated to nickel in the outer-sphere complex, was the rate-determining step. The influence of phosphate ion, added to the aqueous phase as a buffer agent, on the rate of extraction was expelled.
Th6 temperature dependence on the formation rate of the 1: 1 chelate was determined and thermodynamic data have been calculated. These values are E.: 13. O k al/mol, aH: 12.4kcal/mol, dF: 8.5 kcal/mol and AS: 13. O e. u.

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Tetraphenylborate ion was titrated in the presence of a neutral supporting electrolyte (such as sodium nitrate) with a silver nitrate solution by short-circuit amperometry using a rotating platinum wire electrode (1000 rpm) as the indicator and a reference SCE electrode. A O.004mol/1 sodium tetraphenylborate s 1ution in the prese ce f o.1 m 111 sodium nitrate was titrated accurately with a coefficient of variation less than O.1%. Surface active agent such as poly (vinyl pyrrolidone), triton X-100 and triton X-405 at the concentration less than O.0160. did not interfere with the titration.
A method for the determination of potassium ion was as follows. An excess of sodium tetraphenylborate solution was added to an aqueous solution of potassium nitrate at about 800C to form the precipitate of potassium tetraphenylborate. After the solution was cooled to room temperature, sodium nitrate (final concentration O.1 mol/1) was added as the supporting electrolyte, and poly(vinyl pyrrolidone) (O. Ol%)to prevent the potassium tetraphenylborate precipitate from reacting with silver ion. Then the residual tetraphenylborate ion was titrated.
This method is applicable to the determination of potassium in sea water. Firstly, the sum of the residual quantity of tetraphenylborate ion added and all of the halide ions were titrated, then all the halide ions were titrated with a silver nitrate solution for another a1iquot of the sample solution in order to estimate the quantity of potassium ions.

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In an aqueous solution of an equilibrium mixture of methylene glycols and polympethylgne xides with d ent 1 w m iecular weights, f rmaldehyde is kn wn t exist The p, lymeriza tV U nVVVde |rV6bM(rmP)ntThMnMdTits distribution Vhavd been studied by gel permeation chromatography xides with d ent 1 w m iecular weights, f rmaldehyde is kn, wn t exist The p lymeriza tV U nVVVde |rV6bM(rmP)ntThMnMdTits distribution Vhavd been studied by gel permeation chromatography end gr up analySis using near infrared spectr spc py H wever, the c e cient f va anee for th reProducibility of the GPC experiments was less than 50/o.
S Vuc-hV g reproduci5ility implies that the rate of depelymerization of the oligomers is much slower in THF than in water. but apparent values of P.

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Manganese(II)catalyses the hydrogen peroxideoxidation of aromatic amines such as phenetidine, P-anisidine, o-anisidi ne, etc, in aqueous carbonate so1utions, Cgbalt(II) and copper(ll) catalyse also the reaction in sodium bicarbonate (pH 8.4) and in ammonium carbonate solution (pH 9.3), respectively. This catalytic reaction was utilized to indicate the end'point of titration in the determinationof Mn(II)with EDTA.
The optimum of the catalytic action of manganese(II)ion was found to be limited to relatively high carbonate concentration (O.4 mol/1) and narrow pH ranges (between 8 and 9.5), The recommended procedure for manganese determination was as follows to about 50 ml portion of O.4 mol/l carbonate solution containing known amounts of EDTA, add 3 ml'of O.2% P phenetidine (or P-anisidine) and 1 ml of 3% hydrogen peroxide. Titrate the solution with manganese(ll) solution. At the end point, the solution turned deep orange immediately by the formation of quinoneimines.
this catalytic titration method was applied to determine zinc, cadmium, mercury and lead by'back-titrationof excess of EDTA with standard manganese(II)solution. The results were in good agreement with those obtained by the titrimetric method using BT or XO as metal indicator.
The catalytic titration of manga: nese(II)with o-dianisidine and o-tolidine was also investigated.

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The addition of methyl acrylate (2) to alloocimene (1) was investigated and four adducts were isolated by distillation, column and gas chromatograpy.
Thteir s a det on d b of NM: R speM. were as follows; methyl (2 uethyl 1-ppapenyl t-5dimethst-3-qyClohe)f-1r (3). t-2 2, y14. cdwthyl-3ptclptclelN1me-r-1-catrbcm!ptlasje di.
The small amount of isomer contained in both additious would not be produced by isomerization of the adducts, but by thermal equilibration between (1a) and (1b) in methyl acrylate.
It has been found that the reactivity for isomers is larger for (1a) than for (1b) in the addition of (2) and (1).

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The adducts of homoalloocimenol (1) with methyl acrylate (2) was qllgweq to reac. t, . apd the T ddli6-fsMMwere separated by gas chromatography, and identified as. methyl. tr2 .2: mA ethy.1-1 tus wpt @confirmed on the basis of NMR evidence.
iiM=fg-Tb6e n found that the addition reaction gave ortho adducts only and that the adduct have weak woody odor.

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The electroreductive coupling of ketones with nonactivated olefins was studied under various reactions conditions. When a mixture of a ketone with an olefin (mol ratio 1: 3 2) was electrolyzed in the mixed solvent of isopropanol and dioxane using carbon rod electrode, the coupling product was obtained in the highest yield. The mechanism of this electroreductive coupling reaction appears to involve the addition of the carbon radical species originating from one electrori reduction of the carbonyl group to the double bond of olefins.

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The photochlorination of a and r-3, 4, 5, 6-tetrachlorocyclohexene(BTC), which are the intermediates of r-1, 2, 3, 4, 5, 6-hexachlorocyclohexene (r-BHC) in the photochlorination of benzene, was studied i, n carbon tetrachloride, methylene chloride, 1, 2-dichloroethane and acetic anhydride at the temperature of 50. v 40"C. Based on the results summarized in Table 2, 3, and 4, it is concluded that the effect of temperature is small in the chlorinated hydrocarbons. T-BHC is obtained in 16%e yield from ev-BTC in methylene chleride and 1, 2 dichloroethane, while the yield is only 6%e in carbon tetrachloride. The BHC isomer ratios in the photochlorination of r-BTC was near!y the same in methylene chloride and in carbon tetrachloride, but r-BHC content increased in acetic anhydride to about 70%o at 300C, as compared to about 55%e in carbon tetrahloride at 10eC.1-Hydroxycyclohexyl hydreperoxide had little effect on the produced isomer ratio (a-BTC, Table 3).
Stereochemical courses of radical chlorination of a and r-BTC were interpreted in terms of Kanda's rate-controlling factor A, B and C (Fig.1).
It was inferred that the increase of r-BHC in the photochlorination of benzene in the presence of partially chlorinated aliphatic hydrocarbons and acetic anhydride is not due to the eMcient addition of chlorine to ev and r-BTC, but to the increase in ec and especially r-BTC.

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Metal chlorides-catalyzed chlorination of a and 7-3, 4, 5, 6-tetrachiorocyclohexene (BTC) was studied in chlorinated aliphatic hydrocarbons. Yields of BHC isomers are shown in Table 1and 2. ec-BTC formed preferentially ev-1, 2, 3, 4, 5, 6-hexachlorocyclohexane (BHC) especially when SbCls was used as the catalyst. r BTC formed more ev-BHC than in the photochlorination. This trend would be attributed to increase in stearic hindrance caused by neighboring chlorine atoms in r-BTC.

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Substituted benzoyl peroxides of the types (P-XC6H'COO)2 and (m-XC6H4COO)2, where X=CsO, H3, H, C1, Br, or NO2, were decomposed in substituted benzenes in the presence of CuC12 at 80 C, and orientation, relative rates and partial rate factors for the aroyloxylation were determined. Plots of the logarithms of the partial rate factors of meta and para position$vs. ti" substituent constants yielded good straight lines, and the electrophilicity of p-XC6H'COO. (p value) was found to be in the following order; P CHsOCsHdCOO. (1.71) P CHsC6H"COO. (1.69) C, H, COOe(1.66) P-CIC, H4COO t(1.61) P-BrC6HdiCOOe(1.59) P-NO, C, H, COO. (1.43). p Value for the aroyloxylation with m-XC6H'COO e ranged from 1.62 with X=Br to 1.74 with X=NO, .
It was also found that in the aroyloxylation of anisole, benzene and chlorobenzene the yield bf the aroyloxylated product was always higher with P-XC6HaCOOe than with C6HsCOO. or m-XC6H4COO.. This finding suggests that the decarboxylation reaction of p-XC6H4COO. is reduced by contribution of resonance effeet!ofipara substituent'ewbX.

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Benzoxazolyl- and benzothiazolyl-azastilbene derivatives were synthesized in high yield by the cendensation of diethyl benzazolylpicolylphosphonates with aromatic aldehydes in the pres ence of sodium methoxide in dimethylformamide.
The phcsphonates were prepared by the reaction of the bromomethylbenzazolylpyridiRes and triethyl phosphite at 160eC for 5 minutes under a nitrogen atmosphere.
Absorption aRd fluorescence spectra of these aza-stilbenes: were measured in dimethylfolmalnide. The. fluoresgence unintensities of 4-(2-benzoxazolyl)-3-azastilbenes are eonsiderably stronger than those Qf 4-(2-benzQxazolyl)-2-azastilbenes, theugh the wavelength of abserptioh and fluorescence maxima and the absorption intensities are comparable. The absorption and fluorescence maxima of benzothiazolyl-3-azastilbenes are shifted to longer wavelength by 5tvlO nm compared with those of the corresponding benzoxazole derivatives, but the fuorescence intensities of the former are weak.

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The reactions of varieus imidazole and pyridine-carboxylic acids with phosphorus pentachloride in thionyl chloride were investigated. lt was found that the carbexyl group attached to ev-carbon with respect to unsaturated nitrogen atom could be converted to trichloromethyl group. Examples include the formations of 1-methyl-4-trichloromethyl-imidazole, 4, 5-di-tri chloromethyl-imidazole, 2-trichloromethyl-pyridine, 2-trichloromethyl-pyridine-4 and 5-earboxylic acid from 1-methyl-imidazole-4-carboxylic acid, picolinic acid, imidazole-4, 5-dicaTboxylic acid, pyridine-2, 4 and 2, 5 dicarboxyli acid, respectively. The reaction Mechanism for the conversion of arboxyl to trichloromethyl group was proposed.

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The vapor phase oxidation of mixtures of ethylene and benzene has been investigated with platinum metal catalysts supported on carriers. Reaction products were styrene, carbon dioxide, chlorobenzene (Cl from residual Cl in catalyst), benzaldehyde, phenel, acetaldehyde, and a trace amount of ethylbenzene. The order of metals with respect to initial activity for the formation of styrene was Rh Ir Pd Pt Ru, while that for the formation of carbon dioxide was lr Pt Pd Ru Rh under the same reaction conditions (Table 1). The order of the ratios of the activities for the formation of carbon dioxide to those of the formation of styrene among the metals was found to agree with those of the redox potential and of the work function of the metals. Changes of activity with reaetion time were examined with Rh, lr and Pd-catalysts (Fig.1). The effects of preparation conditions of Pd-catalyst on activity (Table 2, 3, Fig.2, 3, 4) were examined. The reaction pathes to the products (Table 4) as well as effects of oxygen pressure upon the rates of formation (Fig.5) were also investigated.
It is concluded that the active state of the catalysts for styrene formation is metal chloride and that for carbon dioxide, probably fermed by the complete oxidation of benzene, is metallic state.

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Thermal decomposition of 1-butene wa. s studied in a flow system under an atmospheric pressure, at temperatures ranging from 556 to 767CC, with residence times from O.05 to 18 sec and nitrogen/l-butene mole ratio of 15. Methane, propene, butadiene and ethylene were the major reaction products. Other produ ts were hydrogen, ethane, 1-pentene, 2-pentene, 3-methyl-1-butene and 1, 5-hexadiene. lsomerization to form 2-butene was also observed at lower temperatures.
The rate of decomposition obeys the first order rate equation with log k(sec-i)=13.1-59000/4.575 T. Both decomposition and isomerization can be accounted for by a free radical chain process. The experimentally observed product distributions as well as reaction rates are found to be in good agreement with those a1culated on the basis of the proposed chain scheme.

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The dynamic viscoelasticity on nylon 6 fibers was measured, and the changes of tan 6 peak (a dispersion) by the drawing or heat-treatment in the range of 80. v120oC were investigated. By drawing, the temperature of tan 6 peak shifted to higher temperature, and its intensity showed the maximum at the draw ratio of two times and decreased thereafter with drawing. On the other hand, by hea treatment, the te perature of t n peak sifted to lower and its intensity increased.
The changes of tan 6 peak were also discussed in comparison with the fine structures, sqch as crystallinity, size of crystallites, and orientation factor of amorpheus chains and crystallites. It has become clear that, the behavior of a dispersion was decided by the density of network structure formed by crystallites and amorphous chains, and the degree of tension of amorphous chains.
In this case, it was suggested that the crystallites would act like crosslinking peints in crosslinked polymers and inhibit the motion of segments in amorphous regions. On this assumption, Shibayama's equation for relationship between T, and crosslink-density was applied to that between a dispersion temperature and network-density formed by crystallites and amorphous chains. The results were found to be satisfactory over the range of measured tem perature.

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Formaldehyde exists as an equilibrium mixture of lower polyoxymethylene glycols in aqueoussolution or as an equilibrium mixture of lower polyhemiformals in methanol solution. Formation of hemiformals in aqueous formaldehyde solution containing methanol was studied byeans of infrared and near infrared spectroscopy. The attachment, Hitachi Model ATR-2, which has a prism KRS-5, was used for observing attenuated total reflection, i. e., ATR spectra.
The weak band at 1190 cm-i was assigned to CHs rocking vibration of end methyl greups of lower polyhemiformals. The absorptions of the end methyl groups of all seven model compounds eccurred in the range 1200. v1180 cm-i.
The band at 1190 cmwwi did not appear in the spectrum of aqueous formaldehyde solution, but it appeared when methanol was added to the solution.
Furthermore, it was found that the calculated relative number of moles of bound water, which was consumed to form lower polyoxymethylene glycols, was almost equal to the sum of the relative number of moles of bound water and that of moles of the added methanol, when less than 11e/o of methanol was added to aqueous formaldehyde solution.
It seemed that formation of hemiformals occured easily in aqueous acid or alkaline formaldehyde solution when methanol was added to it.

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The fiow properties of aqueous solutions of sodium alginate (Alg) were investigated and nonlinear viscoelasticity was mainly examined. The peculiar flow properties of the aqueous solutions of Alg were compared with the existing theories for non-Newtonian flow of concentrated polymer solutions and the experimental results of the aqueous solutions of methylcellulose. The non-Newtonian behavior of aqueous solutions of Alg was ebserved at shear rates lower than that calculated from Graessley's theory. This peculiar phenomenon was investigated from the relation between Graessley's characteristic times and the intermolecular interactions which are affected by the behavior of Alg in solution as a polyelectrolyte.
A coaxial cylinder apparatus was onstructed to measure the normal stress in Couette flow. From the normal stress measurements, recoverable shear strain and fluid elasticity were obtained. As compared with aqueous solutions of methylcellulose, aqueous solutions of Alg showed remarkable fluid elasticity and behaved as Hookean body. ln aqueous solutions of Alg as well as so1utions of nonpolar polymers, the dynamic shear modulus was correlated with the normal stress difference in the low frequency and low shear rate regions, and the steady state shear compliance was inversely proportional to the second powers of concentration. The concentration dependence of normal stress coeMcient ceincided with that is predicted from Graessley's interpretation.

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N, N Bis(4, 5 dihydroxycarbonyl-1-naphthoyl) p-phenylenediamine dianhydride (BNPDA) was prepared by the solid phase condensation reaction of 1, 4, 5-naphthalene tricarboxylic anhydride with N, N diaetyl-p-phenylenediamine. Polyamide-imides were synthesized by the bulk polycondensation reaction of BNPDA with aromatic diamihes at high temperatures, and the reaction conditions were investigated. As aromatic diamines, p-phenylenediamine, benzidine, 4, 4 diaminodiphenyl methane, and 4, 4 diaminodiphenyl ether were used. The polymers obtained (1)N(4) were insoluble in organic solvents such as DMF, DMAc, and DMSO, and slightly soluble in conc. H2SO4. Reduced viScosities of polymers increased with rising reaction temperatures. Reduced viscosities of polymers obtained at 3000C were measured in conc. H2SO4solution at 30oa nd their va1 s were O.20 0.35.
In consequence of thermal analyses, it was found that these polymers are degraded at 400N 5000C in nitrogen.

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4, 4, -Biphenylene-bis(4, 5-dihydroxycarbony1-1-naphthoate)dianhydride(BEAH)was prepared by the melt-condensation reaction of 1, 4, 5-naphthalene tricarboxylic anhydride with 4, 4 diacetoxybiphen 1. polyester-imides were synthesized by the melt polycondensation reaction from this BEAH and, aromatic diamines. -Phenylenediamine, benzidine, 4, 4 diaminodipheny1methane, and 4, 4 diaminodiphe: nyl ether were used as aromatic diamines The polymets obtained were insoluble in organic so1vents such as DMAc and DMSO, and slightly soluble in conc. H2SO4.
In infrared spectra of polymers, an absorption band at 1735 cm 1 and two absorption bands at 1710 1715 and 1665 1670 cm-are assigned to C, O stretching vibrationof the ester bond and the imide ring And there are absorption bands at 3300 and 1650(shoulder)cm 1, which are assigned to N-H a d C=O stretching vibration of the amide, respectively, This suggests that a part of ester bonds in polymers were su ected toaminolysis and transformed into amide bonds.
Reduced viscosities of polymers were measured in O.5% conc. H S 04 solution at 30 C and their values were O.12 0.38.
In consequence of thermal analyses, it was found that these polymers are degraded at about 400 C in nitrogen.

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Cationic polymers of an integral type were prepared by successive Menschutkin reactions of N, N, N, N -tetramethylethylenediamine (TED) with P-xylylene dichloride (XDC) in the various reaction conditions, The chain length of the polymer was investigated by the intrinsic viscosity (T) measurement. The polymer which has desired chain length could be obtained by choosing the reaction conditions, while after the long reaction time, the final chain length was independent of monomer concentration though the reaction rate became fast at high monomer concentration. The propagation reaction proceeded even if the system became heterogeneous by the precipitation of the cationic polymer out of the solution, and the chain length increased gradually.
Considering the reaction rate and the solubility of the cationic polymer, it would be evident that raising the reactien rate is most effective when increasing on the chain leRgth is aimed, and that the solubility is the secondary importance.

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The polymerization of styrene (St) in the presence of sodium oleate was investigated in an aqueous system without any ordinary radical initiators. The reaction proceeded at 800C to give a stable emulsion of poly(St) which has an unusually high molecular weights.
St also pelymerized in the presence of sodium salts of saturated higher aliphatic carboxylic acids in the concentration range above their CMC. The polymerization rate ef St was independent on the carbon number of sodium salts of saturated carboxylic acids.
St polymerized remarkably in the presence of surfactants such as sodium linolate or sodium linolenate having internal double bond with cis configuration or sodium undecylenate having external double bond, but scarcely polymerized in the presence of sodium elaidate containing internal double bond with trans configuration.
In the presence of sodium linolate or linolenate, the polymerization of St would be initiated by the peroxide contained in surfactants, but the initiation mechanism of polymerization of St in the presence of sodium oleate was not clarified yet.

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The melting and crystallization behavior of poly(vinylidene fluoride) (PVdF) before and after irradiation has been observed by the use of a differential scanning calorimeter (DSC). Gamma irradiation was carried out with 6 Co at a dose rate of 1 MR/hr at ambient temperature. Electron beam irradiation was carried out with EBG at 2 MeV and at a dose rate of 2MR/pass by intermittent irradiation to prevent a rise in temperature by means of a shuttle conveyor.
Melting temperature (T.) and crystallization temperature(T.) were measured at the peak in the DSC thermograms. T. decreased with increaseing radiation dose. PVdF, irradiated in vacuum, gave mostly a simple and sharp peak.
On irradiation in air, more complex peaks were observed. These results indicate that the melting behavior is strongly affected by the presence of oxygeR during the irradiation. Depressions of T. and T, were the same fer gamma and electron irradiation in vacuum. On the other hand, T. depression of PVdF by the irradiation in air was smaller than that in vacuum, and a difference in melting peint depression between gamma and electron irradiation was also observed.
The peak at higher temperature corresponds to crystalline state where the degradation dqe, to irradiation is mainly preduced by the presence of suMcient oxygen near the film surface. While, the peak at lower temperature corresponds to crystalline phase where crosslinking mainly takes place by irradiation in the absence of oxygen at inner parts of the film similar to the vacuum irradiation, When crosslinks are introduced, defects would be produced in the crystalline lattice. The defects would cause a melting point lowering, the magnitude of which is larger than that produced by the scission of molecular chain in the crystalline phase on irradiation in air.
Both heat of fusion and crystallinity decreased with increasing radiation dose. About 1706. decrease of heat of fusion was observed after 200 MR irradiation. On the other hand, X-ray diffraction pro es did not change markedly. The decrease in the crystallinity, determined from X-ray diffraction, was 7fZe.

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The catalytic reduction of nitric oxide with thirteen hydrocarbons NO+4m+n 1 N2 + 2m was studied by using a flow reactor (inside diameter12.0 mm) 4mn 4m+n at atmospheric pressure and temperatures ranging from 27O to 5500C. The catalysts were five kinds of coprecipitated binary metal oxides of 50 mol composition and Girdler's barium promoted copper chromite, G22 (average diameter: 1.0 mm), all of which were reduced with hydrogen at 5500C before use. Inlet gas concentrations were 1% NO-0.09--.. -1.20%balanced with N2, and the total gas flow rate was 500 N cm3/min for the oxide catalyst of 1.000 g. Under these conditions, the activity sequence of catalysts for bensene was CuOAlP8 Fe2O3-Cr2O2 CuO-Gr2O3 Co3O4-A1203 Fe2O3-A1203 G 22. The reactivity sequence over CuO-A1203 catalyst was alkylbensenes benzene ethylene n-octane iso-octan n-hexane methane. on the basis of the above results together with the report by Ault and Ayen (A. I. Ch. E. Journal, 17, 265 (1971)), it would be deduced that an increase of carbon number resulted in an reactivity sequence was acetylenic olefinic aromatic paraffinic hydrocarbons for the same carbon number. The reactivity seems to decreased with decreasing saturation. Comparing hydrocarbons with carbon monoxide, the reactivity of the former was extremely inferior at lower temperatures, but the reverse was true at higher temperatures

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The activity of the NiO-A1203 catalyst for the codimerization was remarkably affected by the addition of metal oxides, viz., WOg, MoO3, V20fi, Cr20, Fe20g and CaO The correlation between the electronegativity of the added metal ions and the activity was firmly established (Fig.1). This might be onsidered that added metal ions retarded the oxidation state of Ni ions, and thus affected the atalytic activity. The moderate reduction of the catalyst with"hydrogen before the reaction also brought about more enhancement of the activity than the severe reduction er the fairly weak oxidatien (Fig.2). On the basis ef these results, nickel. with slightly lower valency contributed to the a tive site for the codimerization. Wos was found to give the most suitable valency state toward nickel for the codimerization reaction.

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The phase diagram of the Agr-Kr-H O system at 30eC has been ebtained. A new compound wess isolested and its chemical formula was cletermined to be 2 Agl i KI.2 H O. By means of X-ray diffractometric analysis, the compound was found to belog to the orthorhombic dydtem with cell constants a=9.70, b=15.16, and c=7.20, and Z=4.

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Sb(III) complexes were formed upon mixing Sb(III) ion with gluconate ion and gave rise to the two-stepped wave, whose half-wave potential of the first steps was -0.15 V (anodic wave)and that of the second -1.15 V vs. SCE (cathodic one).
Cu(II)ion, however, did not react with gluconate ion in a solution containing 0.1mol/l sodium gluconate and 0.2 1 mo1/l ammonia, and gave two-stepPed wave of Cu(II)-ammine complexes.
{(E, i, ), =-0.23 V, (E, /, ), =-0.43 V vs. SCE} In view of a great difference between Cu(II)and Sb(III)ves, it was possible to determine Cu(II)on in the presence of Sb(III) anodic stripping po1arography with square wave techniques.
Calibration curves were obtained by measuring the wave height of the second step for Cu ion whose concentration was raising from 0.0l to 0.1 ppm in O.1 mol/1 sodium gluconate, 0.4 mo1/l ammonia and 0.4 mol/l KCI medium. Up to 100PPm of Sb(III)ion, Sb(III)ion did ot interfere the determination of Cu(II)ion, whose concentration was 0.1 PPm.

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The addition of acrylaldehyde (2) and allylalcohol (3) to alloocimene (1) (mixture of (4E, 6E)-(1 a) and (4E, 6Z)-alloocimene (1 b)) was investigated.
In the case of addition of (2) to (A, the four possible acrylaldehyde adduts were isolated and their structures(t-2-(2-methyl-1-prQpeny1)-4, 5-dimethy1-3-cyclohexene- 1-carboxaldehyde (4), t-2-(2-methyl-1-propenyl)-4, c-5-dimethyl-3-cyclohexqne-r-1-carboxaldehyde (5), c-2-(2-methyl1-propenyi)-4, t-5-dimethyl-3-cyclohexene-r-1-carboxaldehyde (6), c-2-(2-methyl-1-propenyl)-4, c-5-dimethy1-3-cyclohexene -1-carboxaldehyde(7))were established chieflyon the basis of COmparisons of their reduction products with the authentic samples of tww2w(2-methyl-1-propenyl)4)t-5-dimethyl-3-cyclohexene-r-1-methanol(8), t-2-(2-methyl-1-propenyl)-4, c-5-dimethyl-3cyc1ohexene-r-1-methano 99, -2-(2-methy1-1-propenyl)-4, t-5-dimethy1-3-cyclohexene- -1- ethanol(10)and -2-(2-methy1-1-propenyl)-4, c-5-dimethy1-3-cyclohexene-1-methanol(11)
OR the other hand, in the case of addition of (3) to (1), their structures ((8), v(11)) were established by means of a same methode as before. (4)N(7) and (8). Nt(11) have a mild wood-like odor.

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Reaction of thiols RSH (R=i-CsH7, tert-C'Hg, CizH2s and p CH3C6H) with nickelogene giave They the corresponding thiolate derivatives of nickelocene with the formula of (CsHsNisR)2were blac- shin crystals with moderate stability, and solub1e in most orgapic solvep. ts. Products with oiygeri-containing thiols (R=HOCH2CH2 and HO2CCH2) were black crys-talline mass with the f=of (CsHsNiSR).. They were fairly unstable, particularly in solution, atid gave insoluble and infusible black mass on standing.
ReVaction of nickelocene with methanol in inert solvents in the presence of oxygen gaye red liquid and analytical data, f the pr duct are in go, d agreement with thoseof the. mofio-methoMxy of derivative of nickelocene. Analogous reaction with p-benzoquinone quantitatively gave an equimolar adduct as brown powder.

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The reaction of poly(vinyl bremide) (PVB) with a large excess of anilline proceeded asi a homogeneous reactioh. Aniline was much more easily introduced in polymer cabins in the For instance, reacti6n system of PVB-aniline than that of poly(vinyl ch-loridg). (PVC)-gnil ne. tb compar in the reaction system of being kept at 80 C for 48 hours, the introduction rate of aniline to PVB was about 20 times faster than that to PVC.
The reaction PVB with aniline was, at first, substitutional reaetion between bromine atom te b Cand aniline, and dehydrobromination. But the reaction proceeded further, the rate of fgriirxa" iMion of th6 double bond was found to be decreased again. in this fact, it was suspected that the additive reaction of aniline to polymer was occured.
The reaction of PVB with anilline gave N substituent at 80 C and 1090C, but the same reaction at 1500C, over 12 hours gave Ar-substituent. As the reaction time i-ncreased, the rdte of formation of Ar-substituent increased, but that of N-substituent decreased.

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Feur bisamide-anhydrides (BAAH) were prepared by the solid phase or melt condensatien reaction of 1, 4, 5-naphthalene tricarboxylic anhydride with arematic diacetanides. Polyamideimides (PAI) were synthesized by the bulk polycondensation reaction of these BAAH with 4, 4 diaminedipheny1 methane or 4, 4 diaminodiphenyl ether. Reduced viscosities of obtained PAI were in the range of O.24. vO.74 in O.5 e conc. HiSOe solution at, 30 C. PAI ebtained from BAAH containing CH2 or had higher, viseosities'than those ebtained from BAAH containing.
In consequence of thermal analyses, it was found that these polymers are degtaded at 4dro, y 4850C. t The Syntheses of Pelymers Using 1, 4, 5-Naphthalene Triearbexylic Anhydride. II.

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