It has been found that 5, 10-dihydrophenazine and 5, 6-dihydrobetizo[c]cinnoline were sta61e in polyvinylalcohol sheets, when they were produced by photoredgction ef phenazine and benzogc cinnpline in the sheets; whexeas. they were s. usceptible to og.idatign in liguid solutiQns, The ultraviolet absorption spectra of these compounds, were -measured, and'the'polarizatfon"'direction of each band was determined from the polarized absorption spectra. The observed 'results were compared with those of the MO calculatioRs. 5, 10-Dihydrophenazine has the X-axis polarized bands at 252 ahd 370 nm, and the Y-axis polarized band at 210 nm (X- and Yaxes are in the molecular plane, and are respectively perpendicular and parallel to the line connecting two N atoms). 5, 6-Dihydrobenzo[c]cinnoline has the X-axis polarized band at 316nm, and the band at 254 nm consisted of X- and Y-axes polarized bands overlapping to each other (X- and Y-axes are ih the rp, o, lecular plane, and are respectively paralle1 and petpendicular to the line connecting tw'o N atoms).

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A kinetic study of the hydrogenation of maleic anhydride over nickelcatalyst supported on kieselguhr was carried out, in order to elucidate the reaction mechanism and the reason why tetrahydrofuran or r-butyrolactone can not be obtained in high yield. The reactions were carried out batchwise under the following conditions temperature 180.y300C, pressure 120A 150 kg/cm2, and catalyst concentration 10 Wt%. Reactions of suecinic anhydride and succinic acid were alsostudied to con relementary processes.
Reactions from maleic anhydride and succinic anhydride appear to proceed through different reaction schemes above 2500C, At low temperatures, the production of succinic acid is thermodynamically favorabie, but succinic acid was not hydrogenated to 7-butyrolactone. On the other hand, at high temperatures, the production of polymeric residue was predominant owing to the double bond of maleic anhydride.
When the two-step hydrogenation method was applied, the yield of r-butyrolactone from maleic anhydride becameas high as in the case of the reaction of succinic anhydride. How, .ever, the tetrahydrofuran yield was very low even in this case.

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The hydrogenation of isoprene catalyzed by drack Fhas been studied at OCby use of a circulation reaction system. The dependencies of the pro d u ct composition o the amount of the catalyst and the react on time are reportgd
Two different types of reaction were found The proporti on of two reacYions varied depending on the amount of cat 1yst. With a small amount of catalyst, the reaction:pro eeded successively. Methylbutene is :mers wefe produced predorhinantly at the initial stage of r action, and then these ole ns changed to isopentane as shown in Fig, 2. When the amount of catalyst was increased, the reaction rate and the amount of isopentane at.the end of reaction increased as shQwn in Fig.1and the am .t of isopentane at the initial stage of reaction was larger thanthoseof 2-methyl-1-buteng and 3-methyl-1-butene as shown. in Fig.3,
In bothcases, the am un s of the every ole nic products increaSed lineary with the conversion of isoprene until it reaChed 80%.
In the reaction of thc successive type, theselectivities, S(m-n)=m-methy1 n-butene/isoprene reacted, calculated from the slopes of these straight lines were as follows;5(2-1)=0;.28, 5(2-2) 0.35, 5(3-1)=0, 28(equation 3). The steric hindrance of side-chain methyl gr pm y- notexist in the hydrogenation of isoprene, because, the selectivities for 3-methy1-1-butene. d2-methy1- 1-butene are nearly equa1. It is suggested that soprene is hydrogena ed vi ally intermediate on Pd-black.
Hydrogenation of olefinic products did not occur until isoprene reacted.about 80%as shown in Fig.5. Consequently the strength of adsorption of reactant and products in hydrogenation decrease I the sequence=isoprene methylbutene isopentane.
The hydrogenation rate of the thre601en.ic products decreased in the sequence of 3-methy1 1-butene 2-methylL1-butene 2-methy1-2-butene. This fact indicates that the steric hind ance of methyl groupexists in the hydrogenation of methylbutene isomers.

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The granuJated Raney nickel-catalysts were prepared by sintering the pressed mixtures of Raney nickel alloy powder (10 rv80 wt%o) with copper and aluminurn powder at 700.v800 C in hydrogen, and then by developing the sintered materials with NaOH aq. The catalytic activity was investigated by the vapor-phase hydrogenation reaction of acetone. The velocity for the hydrogen gas under pressure passing through the catalyst was measured at room tempera-'ture. Also, the pore distribution, pdre volume, surface area and mean pore radius of the catalysts were determined. ln the case of the catalysts prepared from the sintered materias containing 60% of the alloy at different temperatures, 7006C and 800eC, the aluminum dissolved with NaOH aq. was 33% and 6%, respectively, and the mean pore radius of the atalysts was o.7x10'2p and 6.95x10 2 pt, again respectively while the velocity for hydrogen, under pressure of 1.5kg/cm2, passing through the cataly.st sintered at 800 C was about twe times greater than that for the cagalyst sintered at 7000C (4-68x102 H2 ml/P V (ml.g"i) min). The catalyst sintered at soooCi not withstanding a sthall amount of the aluminum being dissolved, gave the maxim.um conversion Qf 74% as the hydrogenation activity in eomparison with 91% of that sintered at 7000C. These results suggested that the catalyst sintered at higher temperatttres had the pore strugture that allowed the reactants and products to pass easily through it and enlarged the catalytic activity.

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Reduction of nitric oxide with hydrogen over various metal oxide catalysts supPortedon -alumina has been investigated using a conventional now microreacter at 420Cand under atmospheric pressure. Formation of nitrogen, nitrous oxide and1or ammonia was observed during the reduction, and the catalysts were classi ed into.two groups according to the selectivity, ie, (1)one, such as Pt, Pd, Cu and Ni, showed high selectlvity for ammQnia formation(2)another was e ective for nitrogenor nitrousoxide formation, and this group was further subdivided into(2-A)and(2-B) (2-A)Fe, Cr, selective for nitrogen formation, (2-B)Co, Metcoselective for nitrousoxide formatiQn(see Table 1). Moreover, nitrous oxide was foundto be an intermediate compound for nitrogen formation from nitric oxide over thecatalysts of group(2).
The reduction of nitric oxide over iren catalyst was kinetlcally investigated (see Fig. 4, 5), and it was shown that the reaction proceeded through redox pathway on the catalyst leq. (1)

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Cathodic current otenti I urves wereobtained for copper in cupric pyrophosphate solutions by using a rotating disk type electrode, where the effect of concentration polarizations was completely eliminated. For all solutions test'ed (Table 2), Tafel relations having a slope b of about -0.5V were observed in the potentikl region of -0.75Av-1V vs. SCE (Figs. 6 and 7). The exchange current-densities, ic for the copper depoSition reaction were obtained by extfapolatingthe.Tafel lines to the rest potentials which are considered to be the equilibrium potentials for the r'eaction (Table 3). lt was found that ig increases with increasing concentration of Cu(P2Q7)2.1'- ion but .decreases with the increase of.P207 ww ion concentrqtip.n for small concentrations of this ion (Figs. 10and 11). From the results of experiments, the following inechanism was proposed in which CuPiOi2L, produced by the dissociation of Cu(P207)26ew, is directly taking part in the electrode reactien.
Cu(P207)z6- pt CuP20, 2- + P207S-
CuP2072bu +2e - CuO + P20
Se bright deposits were alv ays obtained when the potential ismore ositive than 75V of the vs. SCE and the current is large, r thanabout iiof 5 mA!cm (Fig. 8). The value. cgrrent i2 cerresponding to the critical potential of -0.75 V increaunses with increagi-ng gonc.enr tfation of P207-i ln the range of iiivi2, , electrode surface is considered to be weak. ly adsorbed with pyrophosphate ions Which allow random or smooth deposition of metal atoms.

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To clarify caking mechanisin of water soluble inorganic salts, water adsorption isotherms for ground p6wder of NaCl, volume shrinkage of the powder bed and bending strength of compressed disks made of the powder during water vapor adsorbing process, were determined. And the relationship aniong the results obtained was discussed.
Each of the adsorption isotherms showed a step in theamount adsorbed at the vapor pressure, for completing tw no1ecular layers, When the samPle was exposed to epeated cycles of adsorbing water vapor in less than twomolecular layers and desorbing at room temperature, shape of the adsorption isbtherms approached to that of the sample prepared by recrystallization from its aqueous solution, This fadt suggests that, in the case of gfo und NaCl, migration of Na" and Cl" through the adserbed water layers oecurred already in the region not exc.eeding the two moledular layers, After the water vaper pressure exeeeded the value corresponding to the step, a part of the water adsorbed was released probab1y due to the surface area depression of the solid particlesi When the amount adsorbed exceeded three layers, a bending strength Qf tthe sample disk. increased considerably and the powder bed began to shrink. The changes in the three properties, .surface a rea, bulk volume of powder bed and bending strength, may beattributed to a cooperation of the following two processes. (1) The particles are aggregated by a cohesien forpe of the adsorbed water. (2) The adsorbed layersdissolve partially the particle surface, then some solids deposit onto the othersurface location of the particle.

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Hypochlorit6 and chlorite react in solution to form chlorate and therate of the reaction varies with the, pH of the solution.
We elucidated the mechanism of this reaction and determined the rate constants of two principal reaction steps.
The hypo chlorous.acid, which is produced through the hydrolysisof hypechlorite, reacts with the chlorite ion and liberates chlorine dioxide in the 1st step. ln the 2 nd step, the chlorine dioxide reacts with the hypechloriteien to form chlorate.
The rate of reaction in the 1st step depends greatlyon the pH of the solution, and the ncreasb.of pH retagds the liberation of chlorin dioxide, resulting-in a decrease in the over all reactlosn rate.
Therate equations for both steps are of 3 rd order. The rate constants are 1.9 105 and4.QxIO (molm2.IS.minmi) for the 1st and 2nd step, respectively.
Since the reaction system studied contained hypochlorite, hypochlorous acid, ehlerite, chlorate and chlorine dioxide, we established a satisfactory method for the determiRation of these eomponents, before starting above exPeriments,

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The reactions at 1400.C between rare eatths(III)vanadium(III)mixed oxides;RVO3(Rrare arth elements) and graphite were studied, The products were examined by X-ray diffraction nd weight gain due to oxidation.
when the mixed oxides except EuVO3 and graphite were mixed and heated at 1400C for n hour in vacuo, vanadium(III)ions were reduced by graphite quan, titatively to vanadium etal. The reaction equation was as follows when equimolar of graphite to RVOs was added;
Rvo3+c-1/3 RvO3+1/3 R208+2/3 v+co (1)
On the other hand, if EuVO3 and graphite were reacted, graphite acted as the reductant of europium(III)ions. In this case, Eu2VO4 arid EusViO7, in which Eu(n)ions were contained, were formediBoth, Eu2VOs and Eu3V207 were in the tetragonal systems, and they were decomposedto form EuVO3 at high temperatures as follows:
2Eu2VOs.EugV207+EuO t(2)
EusV207 .2EuVO, +EuO t (3)

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In order to study the influence of the atmosphere on the sintering of magnesium oxide particles, the particles prepared by rapid decpmposition of magnesium oxalate in vacmo were sintered in water vapor of 20 mmHg at the temperatures from 500 to 900eC for various times ranging from one to ten hours. The features of this sintering system were described by measurements of the crystallite size, specific surface area, and lattice constant of the products,
Eaeh crystallite of the sintered magnesium oxide particles showed a cubic form (Fig. 1), aqd the degree of secondary agglomeration between them was relatively srilight(Fig. 6). The decrease of the specific surface area observed with the increase of the sintering time was an immediate consequence of the crystallite growth, andboth the phenomena could be treated in one kinetic equation (Equation (5)). The values of the apparent activation energy for the sintering were found to be 33.3.v36.lkcal/mol. It seems likely that the sintering in water vapor is acceleratedby increase of anion mobility due to repetition of the adsorption-desorption cycle of water molecules.
Aging of the sintered magnesium oxide particles upon exposure to the air was observed for 8 minutes to 2 years (Fig. 8, 9, and Table 1). lt was found that both lattice constants, and crystallite sizes were kept constant over the whole period, but the decrease qf the spe-cific suMrface area was already observed within 3 hours after exposure to the air. Through these measurements on aging, it is suggested that degrees of interaction of magnesium exide particles with water vapor vary during the lbng period of exposure, but the lattice constants of magnesium oxide particles are not affeeted by the degrees of interaction.

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The infrared spectra of (CHs)sGe-Mn(CO)if have been measured in the ;ggilo.n-of-2 2QQ"-v.60cm-i. and normal-@analyses have been made for three molecules, (CHs)gGerM n C9 s, ili G6-M nV(e'oV-)P, ;'5n'd' kT, 'Sl-Mn(coV), , on the basis of a modifigd I lrey-Bradley orce.-field Th, e ft-- i'nleih-6't'i6ri '66tweentVhe lv 6 mte't'al and' manganese atoms for the presens series of co-mpoynds iv'a's'-'f6und to be weaker than that of halogen analogues on the basis of the setof the fgrce c nsta K(M-Mn), K(Mn-C), and K(C-0) The three f rce constants f aseries f ana1 9- us c mpou ds, subjected t the n rmal coordinate analyses were cared wlth that f C18Sn Mfi(do'TjrmC: The' ploVt of the difference of K(M-Mn-) Coreqgh. cgmpgunds fr.om., that.of ClsS.n-MnlC ) agai he re ge g Mn-Cl re 4 tha he de eeof he e between the W b metal and manganese atoms and (2) the extent or strength of the metalmetal interaction, (a+rr), were controlled by ligands on N b metal atom, regardless of its componet metal atoms. t The Centrel of the Meta17Metal lnteractien in Coordination Cempounds by LigaRds. III

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The molecular and crystal structure of fac-tricyanotriamminecobalt(III), fac(Co(CN)8(NH3)3), has been determined by the three dimensional X-ray dataco11ected by means of the photographic method using FeK. radiation. The R valuewas finally reduced to O.11 by the block diagonal least-squares .analysis based on 473 visual date, The congplex cryStg11ized in the orthorhombic form with space group P 2i2i2i; a=9.95 A, b=11.05 A, c=6.58 A; Dm=1.74 g.cm 8, D. X73 g.cm S; Z=4.
Three nitrogen (ammine) and three carbon atoms were octahedrally coordinated to the central cobalt atom, forming the fac isomer. The average bond distances were as follows; Co-N(NHs) 2.01 A, Co-C 1.86 A, C-N 1, 18 A.

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The change of radioactivity ratio (gsNb/95Zr) as far as reaching theequilibrium value 2.18 was utilized for the fractionation of Inultiple contaminations produced by the fission products from different origins into each origin and its scale. The air borne dust used as the sample was contaminated by the debris. from a series of nuclear explosion tests carried out on 18 th Nov. 1971, 7 thJan. 1972 and 18 th May 1972 in People s Republic of China.
The simultaneous equation analysis on the growing of 5Nb from 95Zr, the decay of 95Zr and radioactivity ratios 95Nb/95Zr was performed. The results showed that each contribution rate of 5Zr originated from individual nuclear explosion test to the total radioactiVity of 5Zr in air borne dust cQuld be calculated with considerable accuracyand the rate of gsZr from the test on 7 th Jan. 19721 was the largest. Therefore, it was estimated that the contamination effect to air borne dust by the fission products of this nuclear explosion test was the largest. The age of the newestfission prpducts among the several nuclear fissions could be estimated successfully, when ratios were determined within about a hundred days after the nuclear fission and were observed twice at suitable intervals.

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A kinetic method has been presented for simultaneous spectrophotometric determination of germanium(N) and silicon(W) in their mixtures. This method was bqsed on- the difference in ieaction rates of formation of molybdenum blues which were produced by reducing the heteropoly acids of the two elements; it wasfound that the initial rate of gerrpanomglybdenun Slute formation was much lowerthan that of silicomolybdenum blue formation under certain conditions. Analysis of mixtures of germanium(N) and silicon(W) was accomplished by using the following equations:
[Ge]e (ptg/ml) = -2.31 ve+7.20 A
SiP u9/m, =1, 47, Ve-o, 58 A
where vc is the initial rate of molybdenum blue formation expressed in absorbance unit and A is the final absorbance of reacting solution at 700 nm. Results of analysis of mixtures containing O.50 v2.50 ptg/ml of germanium(va) and O.040.vO.200 ug/ml of silicon(W) are given inTable, 1. Silver, iron(III), vanadium(V), copper(II), phosphorus(V)and arsenic(V)ions interfered with rather seriously. lt was also found that O.12-vO.80 u/ml of silicon(V) could be determined in the presence of O.Ol ug/ml of germanium(W) by measuring only the initial rate of silic, omolybdenum blue formation (Table 2).

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Methods for the spectrophotometric determination of aluminum and beryllium with methylxyle nol blue(MXB) have been studied.
Aluminum produced a water-soluble red-violet complex with MXB. The abserption maximum of the colored solution occured at 578N583 nm, and the absorbance was constant over the pH range from 2, 2 to 2.5. The relation between the absorbance of the complex and the concentration of aluminum was linear over the range of 8N35 pg Al/25 ml, and the sensitivity for Iog(1, /1)=O.OOI was O.OO16 ptg Al/cm2 at concentration of 20 ptg Al/25 ml. The mole ratio of aluminum and MXB was found to be 1:1 at pH 2.4 by the method of eontinuous variation. Among the forty-two diverse ions examined, gallium, indium, bismuth(III), scandium, thorium, iron(III), fluoride rand oxalate in, terfered with the determination, but the effect of iron(III) could be eliminated by the addition of ascorbic acid.
MXB reacted with beryllium to form a water-soluble red complex and its aqueous solution had an absorption maximum at 513N517 nm with a constant absorbance at pH 5.9, Ni6.5. The solution containing up to 10 ptg/25 ml of beryllium obeyed the Beer s law and the sensitivity of the determination was O.OOO8 x g Be/cm2 for log(1/1) =O.OOI. The mole ratio of beryllium to this reagent in the complex was 1 t 1. Many ions interfered with the determination, but some of them such as lead, b smuth(III), zinc, rare earth elements, iron(III)and cobalt could be masked by the addition of a small amount of EDTA. Alumi:num, thorium, chromium(III) and fluoride, however, interfered seriously.
As aluminum could be determined at pH 6.0 and at a wavelength 515 hm, consecutive determination, of aluminum and beryllivm has been also studied. A sample solution containing aluminum and beryllium was divided equally. From one solution, aluminum was determined at pH 2.4 and 580 nm. From another solution, beryllium was determined by the difference of absorbances at pH 6.0 and 515 nm, where the absorbances due to the two metal complexes were additive.

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A simple digital integrator for gas chromatography was designed, anddetails on the performance and the electrical circuits of the unit are described.
The voltage output, from gas chromatograph was invertedly amplified by 100times using ptA-741 type operational amplifier, then fed into the eharge-balancing type voltage-frequency converter and the output pUlse train was counted by integrated circuits (SN 7490 N) and displayed by 5 digit Nixie tubes.
As valleysenser type peak detector was also attached to the integrator, the display couldbe read from the memory of the integrals of the former peak, after recognition ofthe next peak elution.
On memorizing integrals bf the former one by hand and by means of push button switch operation, the display could be read from the, counter, as pules train was counted.
The circuit diagrams are shown irt Figs.2, 3, 4, and the linearity evaluation data of the voltagefrequency converter areshown in Table 1.
As for the gas chromatographic analysis, the preeision and reproducibility of the individual measurement were good, as shown in Table 2 andthecost of construction of the unit was about 1/20 that of the commercial one.

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A new quantitative analytical procedure of olefins in a mixture of hydrocarbons using hydroboration-methanolysis method is described.
After hydroboration of olefins in a mixture of hydrocarbons with diborane, methanol was added to decompose the excess hydrides. From the volume of hydrogen gas thus generated, the amount of olefins in the sample was calculated.
Although bromine, iodine and fluorescent indicator adsorption procedures are well known as analytical procedures of olefins, these are not applicable for colored samples. In addition, bromine and iodine methods usually give larger values than the theoretical values when aromatics and isoolefins are contained in samples tested. In contrast, it was found that the present method does not have such defects and gives moreaccurate data. The olefins in a thermal cracked oil of an atmospheric residual oil were analyzed by the method.
Finally, the determination of diolefin contents in a mixture containing monoolefins was proposed, based on the facts that fluorescent indicator adsorption technique analyzes diolefins, not as olefins but as aromatics, and that the present method gives all olefins as olefin contents.

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The synergism in the solvent extractions of LaS, GdS, and Yb3 wasstudied. Metal ion in aquous phase(NIO-S mol/1) w.as extracted into xYlene phasecontaining 2-theonyl-trifluoroacetone (TTA) and one of the drganic bases, such as tri-n-butylphosphine oxide (TBPO), tri-n-octylphosphine oxide (TOPO), tri-n-butylphosphate (TBP) and af- and T-picoline (ev-* and r-Pic.), of various concentrations. pH values of the aqueous phase was adjusted to 4.3 by adding acetate buffer solution and the extraction was performed at 600C.
The extraction percentage of each ion increased owing to synergistic effect of the above bases in the followXng order: La3 Gd3 Yb3 in M3 -TTA-TBP system. ln GdS -TTAbase system, thedrder was TOPO, TBPO TBP 7- and arPic. The coordinating acetate ion to the rare earth metal ion both in aqueous and organic solution was confirmed and its role in extraction reaction was clarified. For every ion studied, the extracted complex of M(TTA)2(CHsCOO)TBP was recognized in organic phase. For Lag and Yb3, complexes of another types as well as the above mentioned type were extracted becauseof their large or small ionic radii. ln GdS-TTA-Ric. system, Gd(TTA)sPic. was formed as extracted complex and there was no difference in the extraction behaviorbetween ev- and r-picoline. lt may be explained that picoline molecule dosenot co-ordinate to a metal atom in contrast, with TBP, which is a stronger electrondonor and forms direct bond to a metal atom.

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Experimental studies were carried out, n the shifts, f L bands, f and substituted aniline and phenols upon aeetylation. ln aniline derivatives, the shift (ay) was bathochromic when the substituent X is an electron donor, while the shift was hypsochromic when X is an acceptor. ln both cases, the shifts was found to increase linearly with an increase in eleetron donating or accepting character of X. The main factor affecting the direction of the shift was considered tobe an extent of electron transfer from the amino nitrogen atom towards the benzene ring the larger the contribution of this electron transfer to the L.-state is, the more the hypsochromic shift becbmes large. Thus, the hypsochromic shift isascribed to a decrease in electron releasing tendency of the amino nitrogen towards the benzene ring upon Nacetylation. The band displaced to the red side upon N-acetylation has the nature of the CT band of acetamide rather than the L.-bancl of aniline. The large bathochromic shift of acetamide band upon N-phenylation was assumed to be related to the electronic interaction between carbonyl and phenyl groups.
In the cases of derivatives of phenol, the shifts could be accunted for only by the effect attributable to an increase in the apparent electronegativity of phenolic oxygen atom.

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It was found that carbon tetrachloride was stable on heating at 5000C and its pyrolysis above 8000G was accompanied by the carbonization of carbon tetrachioride. By using a con-ventional flow reactor, the reaction mechanisms were investigated on the assumption that the pyrolysis was an equilibrium reaction.
Experimental results suggest that the pyrolysis can be expressed by the following parallel reactions.2CC14 C2C14 + 2C12
2 CC14 C2C16 + Cl2
with the rate constants:
k1=5.97X 1O exp (-28500/RT) k8=4.03 x lO exp(-33000/RT) (g-mol/hr.ml.atom2)
The thermal chiorinolysis of tetrachioroethylene was carried out with the same apparatus. The initial rate constants of the formation of carbontetrachloride and hexachloroethane were given by the following equations, respectively.
log k2t=7.77-8550/T
log k5?=392O/T-7.37

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Sulfonamides[1], [2]and[3]reacted with dialkylthio6arbamoyl chlorides[4]to give Nsulf ony1-1, N -dialkylthiocarbamoylisothio reas[5] and N, 1 -di-sulfonyl-N, X, -dialky1-guanidines[6].The Iatter compounds were found to be desulfurizing condensation products from[5]and excess sulfonamides. The favorable conditions for the syntheses of these compounds were determined. Fou methyl p otons of[5]showed non-equivalent.chemical shift due tothe restricted rotation of these methyl groups around the two C-N bonds. Acid-cataly2ed hydrolysesof[5 a 1]gave sulfonylthioureas[7], while the isothioureas of[5 n q]were not hydrolyzed under the same conditions. Base-catalyzed hydrolyses of [5] yielded sulfonylureas [8].

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For a selective synthesis of s-P-butyltoluene by an alkylation reaction of toluene with 1-betene, optimal reactioni conditions and suitable catalysts have been found by the authors.
In this paper, the experimental results ofthe reaction in gas phase with the alumina boria catalysts using r-alumina as a base are reported. The conclusions may be summarized as follows:
1) r-aluminareacted with boric gcid to form strongly acidic centers, as well as with tyand X-alumina, developing activity of toluene alkylation. The total acid amount of the catalyst was distributed uniformly over the acid centers with acid strength Hg ranging from +7.1 to -8.2. The catalysts containing O -vlO wt% boria had much more weak acid centers and Lewis acid ones than those containing more than 15 wt% boria. At the boria contents more than 15 wt% the greater parts of the acid centers were strong acids, considered as Bronsted type, and the acid amount showeda maximum at 15 wt 9Zer boria and this maximum value increased with inCreasing calcina temperature Qf the catalyst,
2) The activity was attributed to the acid centers at strength H, ;-3.0, being directly proportional to its acid amount, When the reaction proceeded with sIight decrease in activity as a result of co:keformation, as may be seen from the above fact and the result shown in 1), the catalyst containing about 15 wt%boria showed the maximum activity that became higher as the calcination temperature increased.
3) At transient-state activity(about an hour after the start of run), the toluene conversions and s-butylto1uene(SBT)yields increased as the reaction temperature increased. While at stationary-state activity(five hours after the star of run)they decreased with increasing reac on temperature because of a cataryst decay. Alsg the isomer distribution of SBT at stationary-state activity was slightly dependent on reaction, condition, s, but independent of preparing conditions of the catalyst, and the SBT contained approxi:matly 20% of o-and m-isomer and 60% of p-one.

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The synthesis of t-butyl alcohol from isobutene were studied over several catalysts active for hydration of olefins. The reaction was carried out invapor phase under atmospheric pressure, using a conventional flow apparatus. Thefollowing order of the activity at 100N 160eC was found
H2so4-sio2 Hspo -sio2Fe2(so4), -sio2 Moos-A120s A12(so4)s-sio2.
It was found that the hydration of isobutene over H2SO4 proceeded about one hundred times faster than that of n-butene at 115eC.
The equilibrium constant (Kr, ) for the reaction was also obtained (T:absolute temperature).
3. 12x103
1ogK =T-8.93
On the other hand, the rate equation for the H2SO -SiO2 catalyst was expressed as follows,
k (PBPw-PAIKP)
r=1+KAPA
where reactien rate, k apparent rate constant, KA equilibrium constant of adsorption of t-butyl alcohol, 1 B, lbw, and it Apartial pressure of isobutene, water, and t-butyl alcohol, respectively. The apparentactivation energy for the reaction and the heat of adsorption of t-butyl alcoholwere 35.9 and 30.8 kcal/mole, respectively.
The reaction mechanism was discussed andthe Rideal mechanism could be deduced for the reaction over H2SO-SiQ2 catalyst.

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Isoprene synthesis by the vapor phase condensation of form aldehyde with isobutylene over the boric acid catalysts was studied, and the useful carriers for boric acid were investigated. The effective carrier had to possess on its surface a functional group which was able to interact with boric acid. It was found that silica gel and silica-alumina were the excellent carriers of boric acid for the synthesis of isoprene (Fig.1).It was postulated that the active center of these catalysts was formed by the condensation of boric acid with the surface hydroxyl group of silica gel or silica-alumina.
On the silica gel carrier, ortho-boric acid was the most active among other forms of boric acid (Fig.2).It was found that the one pass yield of isoprene was more than 70 mol % (basedon formaldehyde) in the initial stage of the raction. However, the activity of the catalyst considerably decreased with process time (Fig.2), because the boricacid separated from catalyst system during the reaction.
On the silica-alumina carrier, boric acid anhydride was the most active in this reaction (Table 2).It wasfound that on this catalyst there was an apparent induction period for isoprene synthesis at the initial stage of the reaction. After this period, however, the one pass yield and selectivity of isoprene attained 58 mol% and 80 mol% based onformaldehyde, respectively. And these values were provided for the relatively long process time (Fig. 3-1, 3-2).

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An investigation on the relationship between the change of physical property of a purified tororo-aoi mucin solution on heating from 2 to 950C and astudy on the transition of the con- formation of mucin molecule under the same conditions were carried out.Viscosity, spinnability surface tension and transmittance of a tororo-aoi mucin solution remarkably decreased on heating above 600C. But, the changes of these properties of the mucin solution on heating below 600Cor on stirring were coxnpratively small.The complex of tororo-aoi mucin and iodine in the presence of Kl was formed on heating above 600C.The complex formation of the mucin with congo red in an alkaline solution also tested under thesame condition.
When the changes of viscosity, transmittance and color due to iodineof a tororo-aoi mucin solution in heating or cooling were compared withthose of these physical properties of some polymer solutions, it was found that, below 600C, tororo-aoi mucin molecule in aqueous solution formed an order structure whichwas weak junction zone structure, and above 600C, helix conformation.The transition of junction zone structure of the mucin to helix one on heating was irreversible.
On the other hands, the existence of junction zone structureof tororo-aoi mucin was identified by the X-ray diffractograms of the mucinpowder isolated from the aqueous solutions before and after heat treatment.
From the above facts, it was found that the change of the physical property of a tororo-aoi mucinsolution on heating above 600C occurred due to the transitionof week junctionzone structure of the mugin to heli one,

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The depolymerization of polycaproamide with phospho ic acid catalystand steam blowing were studied, Phosphoric aci was usually used as a catalyst forthe industrial depolymerization of po1ycaproamide because of the facts that it accelated the reaction at relatively lower temperature and formed less impuritiesthan other, catalysts. However, phosphoric acid had the disadvantage to decreaseits catalytic effect based on condensing at the depolymerization temperature, Theblowing steam decreased such disadvan, tage of condensing of phosphoric acid.
The dep1ymerizatin of polycapr aideu steam blwing and the presence of ph, sph, ricacid procceded accQrding to zero-order reaction. The rate of the formationofeycaprolactam was directly proportional to the amount of phosphoric acid in the catalytic depolymerizatio and to the endgroup concentration of polymer in thenon-catalytic one. For example the rate of e-caprolactam formation(R)at the temperatureof311.C is shown be1ow.
R=o, (85*[Hspoa wt%]+0.36*[-NH2, mmol/kg]*10 2)mol/grd-mol, hr
The apParent activation energy of the no -catalytic depolymerization was24.5:kcal/mo1.

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A new type, f, oligoamines, oligo(ethylenepiperazine)s HN-H(CH2CH2-N-N)n-H (5)- were prepared by reductive detosylation of the corresponding au, w-ditosyl derivatives (4)n.i-7 by using iso-amyl alcohol-Na system. 4, 4 -Ethylene-di(1-tosylpiperazine) (4)n.i was prepared by the reaCtion of 1-tosylPiperazine (2) with 1-tosyl-4-(B-chloroethyl)piperazine (3), and, following detosylation gave (5)i.-she compounds (4)n.2N7 were prePared stepwise by the reaction of (3) with piperazine or with (5) itws. The investigation of the protective groups of HN inthis synthesis and the preparation of mono-tosylated piperazine are also described.
Certain basic properties stich as melting points, solubilities in some solvents, the R/-values of thin layer chromatography and spectrographic propertiesof the oligom, ers obtained were investigated and discssed in terms of their chainlength. lt has become apparent that, when the number of the repeating units n exceeds 6 or 7, the oligomers are very alike to poly (ethylenepiperazine)(2) in physical properties.

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Polymerization of methyl methacrylate was carried out in the system of trans-PtHCL PEt8X organic halides. Effectiveness of organic halides in combination with the platinum complex for the polymerization decreased in the following order:
CCI4 CHCI3 CH2C12; CHBr3 CHC13; CHC12-CHCI2 CJ32CI-CH2CL;
CH2Br-CH2Br CH2C1-CH2CI; t-C4H9C1 s-C4H9C1 n-C4H9CI;
C6H CH2C1 C8H5C1
From the kinetic studies of the polymerization in the system of trans-PtIICl(PEta)2 and carbon tetrachloride over the lower concentration range of carbon tetrachloride, the rate of polymerization, R, was expressed as follows:
R9= k[trans-PtHC1 (PEt3)2]05. [CC14]05.[MMA]19
The apparent overall activation energy for the polymerization in this system was estimated to be 8.4 kcal/mol. Inhibition of polymerization by p-benzoquinone and hydroquinone and the copolymerization characteristics suggested that the polymerization of methyl methacrylate in this system proceeded by a radical mechanism.

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Kinetic study on the reaction of 1, 1, 1-tris(hydroxymethYl)PrOPane2methYlmPhenYIene diisocyanate adduct(TPTDI) with polyethylene glycol was carriedout.
It was shown that in the reaction of TPTDI with large amount of n-butanol the reactivity of three isocyanate groups in TPTDJ was not affected by the change of the structure of TPTDJ which occurred during urethane formation.
In TPTDI-polyethylene glycol system, the reaction obeyed the second-order kinetics intheinitial stage of the reaction and apparent second-order rate constant increased as the reaction proceeded because of the catalytic effect of produced urethane.
The rate of urethane formation was expressed by the following equation including the catalytic term of produced urethane:
dx /x
where, dx/dt is the rate of urethane formation, a, b and x are initial concentration of iso- cyanate, alcohol and that of produced urethane, and ka and kb are rate constant noncatalyzed and that catalyzed by produced urethane, respectively.

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Reactions of polyethylene glycol(PEG) and ev, to-diol type ibutadieneoligomer(PBd) withtriphenylmethane-4, 4, 4-triyltriisocyanate(TTI) were examined.
It was found that in the reaction of TTI with large amount of n-butanol the reactivity of three isocyanate groups in TTI decreased as the reaction proceededdue to the change of structure of TTI which occurred during the urethane formation.
In TTI-PEG and TTI-ethylcellosolve systems, the initial second-order rate constant (ka) was independent of the initial concentrations of hydroxyl and isocyanate groups and TTI-PBd and TTI-n-butanol systems k.increased with initial concentration of isocyanate group being independent of the initial concentration ofhydroxyl group. This results suggested that in latter systems the eomplex, containing two isocyanate groups or two isocyanate groups and hydroxyl group (ternarycomplex), was formed, although in former systems urethaRe formation obeyed the mechanism proposed by Baker et al. However, in the reaction of TTI with large amount of n-butanol, ka did not depend on initial concentration of isocyanate groupand this suggested that two mechanism occurred competitively.

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The alkali hydro1yses of starch sulfates, cellulose sulfates, and sulfated poly(vinyl alcohols) (PVS) having various degrees of substitutions(DS) and the acid hydrolyses of PVS have been investigated kinetipa11y in aqueous solution from the stand point of polymer reaction.
In both acid and alkali hydrolyses, the rates of reactions did not follow the simple kinetic equation and the apparent rate constants decreased with a progress of the reaction.
For exelmple, the following equation could be used for the acid hydrolyses of PVS:
k(at 900C)=1.5*10 -4+3.02*10 SC*(DS)2, O (1/mol.sec)
Even in alkali hydrolyses, thereactivities decreased also with a progress of reaction. But the initial rate constants became signifigantly larger with decreasing DS in contrast to the acid hydrolyses.
These abnormal phenomena eould mainly be explained in terms of themutual interaction between the polymers and catalysts.
In acid hydrolyses, sulfate groups, existed in high density, reacted rapidly because of the adsQrptionof, catalyst(H ) caused by sulfate group. As the adsorptien effects decreased with a progress of reaction, the reactivities decreased gradually.
In alkali hydrolyses, sulfate groups, existed in low density, reacted rapidly because of the adsorption of catalyst OH caused by free hydroxyl group and the repulsion by sulfate group. Accordingly, the initial rates were large in sulfates of low DS. However, the distribution of residual sulfate groups became gradually heterogeneously (in a cluster) and the Teactivities decreased.

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Polycarbonate resin was carbonized at 6000C and then activated with steam at 800-1O500C for O.8N14 hours. The specific surface area and pore size distribution of the active carbons so prepared were measured.
The reactivity ofpolycarbonate resin char against steam was smaller than that of coconut shell char. The specific surface area of the active carbons increased with weight loss and reached 1800 m2/g, at 75% weight loss,
As the reaction of carbon with steam becomes diffusion-controlled above 1000eC, the activation does not proceed effectively to prepare active carbon of large specific surface area.
For activecarbons prepared above 1000 C, the micro pore volume decreased and transitional pore volume increased markedly, compared to active carbons prepared below 1000 C.
The active carbon from polycarbonate resin showed a good ability of adsorbing sedium dodecylbenzene sulfonate comparable to that of commercial carbons.

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The specific surface area and pore size distribution of the active carbons from phenolformaldehyde resin waste (PFW) were measured.
Activation reaction proceeded at relatively low temperatutes, e.g.at 6500C, because inorganicsubstances added to resin as fillers increased the reaction rate of, carbon withsteam. But, the specific surface area values of the active carbons were less than500 m2/g.
The specific surface area of inorganic substance obtained by burning active carbon to ashes at 800eC was 7.3m2 g. This value was negligibly smallcompared to that of the specific surface area of the active carbons. Therefore, as the ash contents decreased from 43.7 to 5.7% by treating the active carbonfromPFW with hydrochloric acid, the specific surface area increased from 462 to808 m2/g.
The reactivity of char against steam decreased by the HCI treatmentand favorable active carbons with specific surface area as high as 1400 m2/g weresuccessfully prepared.
In order to, prepare active carbons with large Specificsurface area, the treatment with hydrochloric acid was more effective before theactivation than that after the activation.
The active carbons prepared from HCI- treated chars showed higher adsorption ability for sodium dodecylbenzene sulfonatethan commercial active carbons.

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In c6nnecti n with th6 krecerit 'Bns f the ndamental' band f water regarding structure br6aking effect of petchlotate anion, change in the combination band of'water at'2100cm'-i has beert observbd as a function of perchlorate concentration. The optical density of 2100cm'-i band was decreased with the increasing 60ncentration, being accompanied by the increase in the optical density of the fundamental water, . band appearing at 3590 cmww' These are considered to be the strong evidence of the breaking of structure of water due to, perchlorate anion. But..nQ bapd was detected due to the hydrogen bond formation between water and perchlQrate anion., i n the wavelength range of 4000 to 600 cmpi and also the foundamental band dU6 to perch..lohafe was unaltered, implying that the interaction might be purely ionic.

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Dehydrogenation of methylcyclohe'xane on Ru-SiO2 catalysts was studied. Main products were methylcyclohexenes (three'isomers contained), benzene and toluene. ln the steady state (Fig. 1), the initial reaction rate [Eq. (2)], was examined in the reaction scheme shown in Eq (1). Thereaction orders for methylcyc1ohexenes formation were-1 0 7 and O 6 1 1with respect to hydrogen and methylcyclohexane, respectively (Table 1). As the rate constantsofmethylcyc1ohexenes formation corresponded to the CO-adso tio:n values(Fig 2), the active sites would more correlate.with the CO-adserbed sites than the metal dispersien on the support.

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Condensad6nof NaH2PO4, Na P207, .and Na5P3010 wa5 arr.ied o t i .a mixed o1 iQr of acetic acid and acetic anhydride 'inl a volume ratio of :1at 70oC, ahd it has been aPpeared that the condensation of orthophosphate to pyrophosphate and tripolyphosphate to .trimg-tabmuho'sphate are fast and that of nypyrbphosphate to tripolyphospha-te. is yg.ry slow.- the. effggt 6f 's6dium ion for the condensatioh of the, phosphates was examined by adding sodiunEl. bydro.x. ide or sodium aetate to the reaction system mentioned above'. lt'has' been cleared 'thatsodium ion the change of tripolyphosphate to trimetapho, s.phate.

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Studies of EPMA (Electron Probe Micro Analysis) profiles of the screw dislocation on the agate surface have not probably been made. The author measured the profiles acrossing the dislocation on a polished agate surface which hadbeen treated with uranium salt solution.The purpose of the application of uranium was to emphasize the dislocation features apd to reveal a germ stage of epitaxial growth of the radioactive element on the dislocation.
A topograph of thesubjected, area was measured by using secondary electron for the sake of. comparison of it with UM.line-profile.
The result obtained is as follows: the profiles showed remarkably heterogeneous deposition of uranium on the dislocation site

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The Beckmann rearrangement of aliphatic ketone oximes, R(CHs)C=NOH (R=Et (1); n-Pr (2); iso-Pr (3); iso-Bu (4)), with polyphosphoric acid (PPA), polyphosphate ester (PPE), and ester of phosphoric acid (2 P-5 R) was carried out and migratory ratios ((a)/(b) in eq. (1)) were determined, The results are shown in Fig.1, 2, and 3, respectively.
In Fig.1 and 2, the migratory ratios decrease with reaction time and nearly approach to the ratios of anti-alkyl form/syn-alkylform in benzene(A1) or DMSO(A2)except for (3) (See Table 1). From this fact, it has been found that PPA and PPE are inactive for isomerization of the oximes andanti-alkyl oximes rearrange faster than syn-alkyl ones. ln the case of (3), migratery ratios are smaller than Ai or A2. As acetonitrile is detected by GLC, it is presumed that fission has been occurred simultaneously with rearrangement in anti-alkyl oxime (eq. (3)). In the case of 2 P-5 R, all modes of the reaction arethe same as in above, except that the rate of fission is tnuch faster than that in PPA and PPE.
The reaction of anti-alkyl ketone oximes having a bulky grouphas been greatly influenced by the use of sterically demanding catalysts such asPPA, PPE, and 2 P-5 R.

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1-Methylimidazole-4, 5-dicarboxylic acid was found to give predominantly 1-methylimidazole-4-carboxyanilidd by reflux with aniline. Methyl 1-methylimidazole-4-carboxylate was prepared by hydrolysis of the anilide followed by esterifieation. This work presents a new synthesis of 1-alkylimidazole-4-carboxylic acid and its derivatives.

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The exothermic peak temperature (Tpk) in the DTA curve of PAN was examined on the basis of the oxygen concentration and the sample packing state (weight, particle size and packing density).
In nitrogen, the lowest TPK of ca. 2500C was obtained.
In the presence of oxygen, TPK shifted from lower to higher temperature side with increasing of oxygen content.In addition, the effect of the sample packing state became noticeable.The highest TPK was about 3100C.
From these evidences (Fig.4), it was possible to explain the large dispersion of reported TPK (25-.-3400C) was mainly due to the differences of the oxygen concentration and the sample packing state (therefore, the heat build-up T insample) in each experiments.

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