The osmotic coefficient, φ, of aqueous solution of sodium dodecyl sulfate(SDS) was measured with a vapour pressure osmometer(VPO) at 37° C, and the sodium ion activity, α Na+, was also measured with glass electrode (pNa meter). The degree of ionic dissociation of sodium ion from micelles determined withthese two methods agreed to be 0.213.
The osmotic coefficient, φ, of aqueous solutions of SDS decreased upon the addition of poly(vinyl pyrrolidone)(PVP) or poly(vinyl alcohol)(PVA), as shown in Fig.4, but the activity of sodiumion, α Na+, was little affected, as shown in Fig.5.
The activity, α Na+, of anion, DS-, was culculated from α Na+ and osmotic pressure, π. The anionic activity, α Ds-, of aqueous SDS solutions containing no polymer increased with SDS concentration and reached a maximum at 10 mmolii of SDS concentration, and then slightly decreased at higher concentrations. Thisbehavior of anionic activity of surfactant is the same as that of the anionic activity of sodium caprate shown by Ekwall et al. br
For the system containingpolymer, however, the maximum was not observed and the activity leveled off at higher concentration of SDS as shown in Fig.8. This means that, although DS anions form a complex with polymer, this complex formation does not affect the dissociation of sodium ion from SDS molecules. It wasconcluded that SDS anions bound to polymer form a micelle-like structure becausepolymer does not affect α Na+ value in spite of the complex formation.

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Dissolution rate of the monolayer of 1-monolaurin at constant area was obtained by measuring the decrease of surface pressure. Surface pressure of a monolayer, which had been compressed rapidly and held at a constant area, decreased linearly with the square root of elapsed time. Surface pressure-area curve of the spread monolayer of 1-monolaurin was obtained from the initial pressure obtained by the extrapolation to time zero. It was found that a monolayer of 1- monolaurin was in state a of liquid expanded film. Surface concen-tration corresponding to each surface pressure was calculated from the state equation of liquid expanded film of Jura and Harkins. Logarithm of surface concentration varied linearly with the square root of elapsed time. Adsorption isotherm was calculated by thetheory of Ter Minassian- Saraga for the dissolution rate of a monolayer.
It has been concluded that the spread monolayer of 1- monolaurin isequilibrated immedi- ately with the sublayer and then 1- monolaurin dissolved in the sublayer is transfered to bulk liquid by diffusion.

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The first step of the reaction design process is to create reaction equations. Reaction equations can be treated as the mathematical equations which show the relationship among the raw materials, sub materials, the main product and by-products. Therefore these reaction equations can be obtained by solving these mathematical equations efficiently. In this case a big digital computer is necessary because of a lot of computation.
We have developed a new algorithm of creating reaction equations in the case that the main product is designated but others are selectable from the given materials. The following is a rough explanation ofthe algorithm.
1. Find the elements which are contained in the main product and add the other elements
which are required to be included in the reaction equations.
2. Choose the materials which include all of the above elements from the given raw
materials, sub materials and by-products.
3. Combine these materials -and compute the reaction equations which satisfy the material
balance.
From the above explanation, the number of the combination of materials will increase rapidly as the number of given materials increase and eventhe big digital computer may not handle these computation.
Adding the very skillful technique, we have improved the above mentioned algorithm and made the computer possible to create the reaction equations by the program named HYPO. Fig.1 shows the rough flow chart of the HYPO program.
HYPO has been applied tocreate the reaction equations in which the main product was acrylonitrile. The number of the given raw materials, sub materials and by-products was 19. The execution time in this case of the HYPO program by IBM 360/50-H was about one minute.
The number of created reaction equations was 140 anamong these equations there were 21 reaction equations which were economically and chemically possible.
Furthermore four of them were found to have been industrialized in the worldalready

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Formation and decay process of ionic species in γ-irradiated 3-methylpentane glass con-taining a small amount of triphenylamine(TPA) were studied by esr, optical absorption and emission measurements at 77°K. Radical cations and radical anions of TPA and trapped electrons were produced inthe glass as ionic species.
In glass matrices, radical anions of TPA gave asinglet esr spectrum having a line width of 6 gauss, whereas cations of TPA gavea triplet esr spectrumhaving a hyperfine coupling constant of 14 gauss.
Decay rate of trapped electrons at 77°K obtained from the esr measurement was directly proportional to thatof radical cations obtained from the luminescence measurement, and both rates were not affected by the concentration of TPA. From the results, it was concluded that trapped electrons migrated in the glass at 77° K, and recombined with radical cations of TPA to form excited TPA molecules.

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Formation of complexes between Pd(II) salts and Ce(II) salts in acetic acid asstudied by means of UV spectrophotometry.
On addition of cerous acetate Ce(0Ac)3 to palladous acetate Pd(OAc)2 solution, a strong absorption band with a maximum at 342 nm appeared (Fig.1). The dependence of the ab-sorbance at 342 nm upon the molar ratio of Pd(II)Ce(III) suggested the formation of an equi-molar complex of Pd(OAc)2 and Ce(0Ac)3 (Fig.2). The equilibrium constant K, for the reaction was about 104.8(1/mol) at 25° C.
Addition of water or lithium acetate to the system caused an increase in the reaction rate(Fig.5, Fig.9), and a decrease in the equilibrium concentration of the complex (Fig.6, Fig.8). These facts suggest that the complex is formed mainly through two successive reactions: (1) formation of a intermediate X+Pd(OAc)3-from Pd(OAc)2, (where X+ denotes Li+, H3 0+, or Hsup 0Ac+), (2) reaction of theintermediate with Ce(0Ac)3. The kinetic data were found to beconsistent with theabove assumption.
In the presence of HCI, addition of Ce(OAc)3 did not change the absorption spectrum of the Pd(II) solution, but brown crystals with the composition of [PdCe(OAc)2 Cl3, 3H2 O]were separated from thesolution. Far-IR spectrum of the crystal suggests the complex has a chloride-bridged structure.

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Effects of cerium(III) salts on the reduction of palladium(II) salts with acetic acid, formic acid, acetaldehyde and ethylene have been studied. The decomposition of palladium(II) acetate was pseudo-first-order with respect to palladium(II) concentration (Fig.1) and accelerated upon addition of lithium acetate (Fig.2). This reaction was markedly inhibited by addition of cerous acetate even in the presence of large excess of lithium acetate (Fig.3). Similar effects were observed in the case of the reduction with formic acid, acetaldehyde and ethylene (Fig.4, 6). Apparent activation energies of the reactions with formic acid and ethylene increased in the presence of cerium(III) acetate (Fig.5, 7).
Addition of acetates of Ca(II), Ba(II), Zn(II), Cd(II), Co(II) and Mn(II) also inhibited the reduction of palladium(II) salts (Table 1, 2, 3). The magnitude of these effects was correlated with the electronegativity of the metals (Fig.9), and also with the wave length of the absorption bands of the equimolecular complexes of palladium(II) acetate and metal acetate (Fig.10).
This inhibiting effect was significantly reduced by the addition of lithium chloride for all metal acetates except cerium(III) acetate (Table 3).
It was suggested that effects of cerium(III) acetate were due to the stabilization of Pd(II) species by the formation of Pd(II)-Ce(III) complex.

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The isotopic mixing in nitrogen molecules over singly promoted iron catalyst (Fe-Al203) was carried out at 280-330°. The rate of displacement of adsorbed nitrogen was in agree- ment with the rate of isotopic mixing, suggesting that the adsorbed nitrogen is mostly dis- sociated.
The isotopic mixing over Fe-Al203 was much faster than over Fe and Fe-Al203-K20. But the isotopic mixing was retarded by the presence of hydrogen contrary to the result on FeAl208--K20 where hydrogen markedly accelerated the isotopic mixing. The hydrogen effect on the isotopic mixing over Fe-K₂0 was investigated at 400°C, and the accelerating effect of hydrogen was clearly observed.
From these facts, it is concluded that Al203 promotes the dissociative adsorption of nitrogen on iron but the rate is retarded in the presence of hydrogen, and K20 markedly promotes the dissociative adsorption on iron in the presence of hydrogen by the mechanism of N₂ 2NH

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Adsorption state of typical sensitizing dyes (9-methylthiacarbocyanine, methylene blue, 2, 2'- quinocyanine, and erythrosin) on various photoconductors (AgBr, ZnO, Ti02, S, CdS, and Se) have been studied in order to clear the mechanism of spectral sensitization in photoconductors. The dependence of the amounts of adsorbed dye upon both the electric charge of dye molecules and the kind of photoconductors play an important role in determining whether or not the dye molecules are adsorbed by the photoconductors. However, the independence of the amounts of adsorbed dyes upon neutral salts added suggests that interactions other than the Coulombic interaction also take part in the dye adsorption. Compared with the absorption spectra of methanolic dye solutions, the absorption bands in the reflection spectra of the adsorbed dyes were assigned to unaggregated and aggregated dye molecules. Shifts of the band peaks which were explained as due to the van der Waals' and Coulombic interactions between dye molecules and photoconductors were observed. t Studies on Mechanisms of Photographic Sensitivity, LXIII.

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In the solutions containing both oxygen and one of the metal ions La³⁺, Pr³⁺, Eu³⁺, Dy³⁺, Ho³⁺, Yb³⁺, a new polarographic reduction wave was observed at about—0.5 V vs. SCE. The variation of the height and half-wave potential of this new wave were investigated as f unctions of the concentrations of oxygen and the various metal ions. Controlled current electrolysis was used to obtain information about the reduction process on the mercury and platinum electrodes. The reduction products, prepared by electrochemical method, were found to be the superoxides and peroxides of lanthanoids, for the platinum electrode and mercury electrode, respectively. On the basis of the results obtained it can therefore be presumed that the disproportionation reaction occurs on the mercury electrode.

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Anodic oxidation of 1-phenylazo-2-naphthylamine(PANA) dissolved in acetonitrile in the presence of copper(II) salt has been studied. The purpose of this study was to elucidate the electrode reaction of coordinated organic ligand. This paper is the first one in a series of studies based on the same idea. The present reaction system was chosen because this system has been studied in some detail from the standpoint of autooxidation. The present study is composed of two parts, i. e., (1) the studies on the coordination compound formed between PANA and cupric ion in acetonitrile solutions by means of electrochemical as well as absorption spectral methods and (2) the studies on the product obtained by anodic oxidation and also by autooxidation with or without the presence of copper(II) salts. Polarographic studies indicated that one molecule of PANA coordinated to one copper(II) ion while spectral studies indicated that two molecules of the former coordinate to the latter. Although this discrepancy has not been solved yet, it is undoubted that a certain sort of complex compound is formed in the solution. As a result it was confirmed that PANA is oxidized anodically to form a triazole ring which is also formed by autooxidation when copper(II) acetate is present in the solution at a 100% current efficiency. Not only in the absence of acetate but in the presence of copper(II) perchlorate any triazole ring was not formed.

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When a mixed gas of SO₂, 02 and H₂O is brought into contact with activated carbon, SO₂ is oxidized to H₂SO₄ and accumulates in the, carbon. The amount of H₂SO₄, into which SO₂ was converted, increased with time almost linearly until it reached 10 weight percent of the carbon in SO, base. In the region where the rate of oxidation reaction was constant, the effects of concentration of each gas and of temperature on the rate of reaction were investigated. The rate of the reaction showed a linear relation with SO₂ concentration in gas phase when the concentration was less than 0.01", but, after a gradual change, with increasing SO₂ con-centration, it became proportional to the square root of SO, concentration until it was over 1.0". The rate of the reaction was also proportional to the square root of concentration of O and H₂0. The apparent activation energy of this reaction was found to be from- to - kcal/mol. t Adsorption of Sulfur Dioxide on Activated Carbon in Flue Gas Desulfurization Process. III.

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In the previous paper, oxidation reaction of SO₂ on activated carbon was found to proceed at a constant rate until the amount of SO₂, accumulated in the form of H₂SO₄, reached 10 percent of the carbon, and the rate was found to be proportional to the SO₂ concentration in gas phase when the concentration was less than 0.01%. The present paper deals with the influence of particle size of the carbon, namely, influence of SO₂ diffusion in its pores upon the above rate of oxidation reaction.
Using the apparent rate constant measured for each particle size of the carbon, the effectiveness factor of the particle and the effective overall diffusion coefficient of SO₂ were determined. Influence of concentration of 02 or H₂O on the intrinsic reaction rate constant was also determined at various temperatures.
As a result, it was shown that the reaction rate for any particle size and for various concentrations of each gas at a certain temperature would be estimated, if the properties of the activated carbon, i. e., pore volume and pore size distribution, were known and the intrinsic reaction rate was measured at this temperature. t Adsorption of Sulfur Dioxide on Activated Carbon in Flue Gas Desulfurization Process. IV.

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The, , ization of copper phthalocyanine (Cu-Pc) and metal free phthalocyanine (ME-Pc) were udied by the ust of TGA, DriA, elementary analysis, IR rption 3pectrum. analysis, X-tay Iygis measurments of e ic resistance. Samples were h. pt-treated at several temperatures opt° 1 in Ar gas, act resultant powders were analysed by above methods. it was f a that the Cu-Pc was more thermo stable than the ME-Pc and gave high carbon It might be a, on the a ization of Cu-Pc and Mf-Pc that when the phthalocyanines were heat-tr, the in a a lar combinations occurred by losing hydrogen atoms from ip of the molecules before the radation of molecular structure a the phthalacyanine molecuks der to ar lc p link" - at a - ore, the structure of ca iced materials, stra y on the c-rystal structure of phthalocyanine

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Stability of sodium bromite was studied by means of DTA, TGA, X-ray diffraction, and chemical analysis.
Exothermic decomposition peak is observed at 109°C in DTA curve under the condition of constant elevating temperature (10°C/min), without any change in TGA curve.
Endothermic decomposition peak is also observed at 359°C, with about 22.4% weight loss on TGA curve.
The X-ray diffraction study and chemical analysis of these thermal decomposed material lead to the following conclusion. The decomposition at 109°C is disproportioned and expressed through equation (1), whereas the decomposition at 359°C is referred to equation (2).3 NaBrO₂ ‰2 NaBrO₃ NaBr (1) NaBrO₃ NaBr 3/2 02 (2)
This paper, moreover, has revealed that sodium bromite crystal is stable in dark and cool (less than 5°C) places and that the aqueous solution of sodium bromite is stable above pH 9.2.

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The chemical composition change of M2SO₄-V205 and M2SO₄-V204 systems (M=Li, Na, K and Cs) in various atmospheres of S02, air and S03-S02-02 mixtures derived from a 7% 50293% air mixture (about 90% conversion) was studied by means of differential thermal analysis, IR spectrometry, X-ray diffractometry and chemical analysis, and the relation between these behaviors and catalytic activities was discussed. The reduction of V205 by SO₂ (Fig.5 and 6) and the oxidation of V204 by air (Fig.7) were promoted by the M2SO₄ additives in the order (Cs)>(K)>(Na)>(Li). In V4+/Vtotai vs. M2SO₄/ V205 curves (Fig.14) obtained for M2SO₄-V205 systems in equilibrium with S03-S02-02 mixtures at 450°C, the maximum values of V4+/Vtotal were obtained in the range of M2504/ V20, =0.3-1.0 except Li2SO₄-V205 system. An amount of SO₃ absorbed in the M2SO₄ under the same condition, S03/M2SO₄ (mol ratio), was in the series (Cs)=4.02>1()=1.50>(Na)=0.86 >(Li)=0.20. When 2 M2SO₄-V205 (Fig.14) and 2 M2504-V204 systems (Fig.18) were in equilibrium with S03-S02-02 mixtures at 450°C respectively, the following V4+/Vtotal values were obtained for both systems; (Cs)=0.2, (K)=0.3-0.37, (Na)=0.4 and (Li)=1.0. From these results, it was estimated that M2SO₄ have the effect promoting the reduction of V20, and the oxidation of V204, and that SO₃ absorbed in M2SO₄ have the effect stabilizing the vanadium in the pentavalent state in the order (Cs)>(K)>(Na)>(Li). This order corresponded to the catalytic activity estimated from DTA studies in our previous paper. Li2SO₄ had no effect

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The composition of V205-K2SO₄ catalysts during the oxidation of sulphur dioxide, especially in its lower concentrations (0.2%), wa sstudied by means of TGA, DTA, X-ray diffractometry and chemical analysis in order to get further informations on the mechanism of the reaction. It was found that it took more than several hours for the catalyst to reach the equilibrium composition in the reacting gas (Fig.3, 6). This was considered to be one of the several reasons that the oxidation of sulphur dioxide generally required a longer time to reach the steady state. The effects of temperature on the absorbed volume of SO, by the catalyst and on the V5+/(V5 +V4+) ratio were studied in the range between 320 through 520°C. Absorbed SO, volume and V5+/(V5 d-V4+) ratio changed greatly at the temperature range of 400∼450°C(Fig.4, 7), and these changes could be correlated with the change in the reaction mechanism which occurred at the above mentioned temperature range. The catalytic activity, the absorbed volume of SOS, and the V51/(V5H-V4+) ratio of the catalyst at working state were plotted against catalyst composition in temperature less than 450T. These plots had inflection points in the vicinity of K2SO₄/V205=1 (Fig.11, 12, 13). This fact suggests that a catalytic active substance may exist in an equal molecular ratio of K2SO₄ and V205, and that the mechanism of the oxidation of sulphur dioxide will be more complicated than the ever proposed theory that K2S₂0, and VOSO₄ were produced from K2SO₄ and V205.

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The nickel-glycine system showed three polarographic waves (Fig.1). The first and the second waves were observed at about-1.0 and -1.2 V vs. SCE, respectively when the glycine concentration was relatively low in a pH range from 5 to 8. As the glycine concentration increases, above the pH value of 8 the first wave disappeared and the third wave appeared at -.5 V. These three waves correspond to the reduction of nickel-glycinate complexes 1: 1, 1: 2 and 1: 3, respectively.
The second wave of nickel-glycinate complexes gave a kinetic current based on the dissociation reaction of Ni(gly), - to Ni(gly)2. The rate constant of the dissociation reaction was determined by means of Koryta's equation from the observed kinetic current and the stability constant of the Ni(gly)3- (log K3 = 3.21 from the pH titration). The value of the rate constant was 1.6 x 10 secl, at ionic strength of 0.1 and at 25±0.1°C, independent of hydrogen ion concentration.

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The suspension copolymerization of vinyl acetate with glycidyl methacrylate in the presence of diluents produced porous hydrophobic gels. By subsequent hydrolysis of the gels, porous hydrophilic gels suitable for use in gel permeation chromatography were made. The permeabilities were revealed by eluting water soluble materials, such as ethylene glycol oligomer and dextran covering a wide range of molecular weights, through a column packed with the gels. When alcohols and esters were used as diluents, excluded molecular weights increased gradually with the amounts of the diluents, and peaks of the elution curve were sharp. When hydrocarbons were used as diluents, a maximum value was obtained approximately at 50 percents by volume of diluents to the monomer by plotting excluded molecular weights against amounts of diluents, and peaks of elution curve were broader than those using alcohols and esters as diluents. By using small amounts of diluents, for example 10-20 percents by volume to the monomer, gels suitable to separate low molecular weight materials were obtained

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Oxidation of reduced palladium on active charcoal during the ethylene oxidation over palladium salts-active charcoal catalysts was studied. Effect of oxygen pressure on the reaction rate was determined from the rate of oxygen adsorption using the apparatus with constant volume and constant pressure equipment. Effect of oxygen pressure became evident only when its value was very little.
If we assume that the over-all reaction rate is determined in terms of the dynamic equilibrium between the oxidation of ethylene by palladium salts and the re-oxidation of reduced palladium compounds by oxygen, the conclusion, that the rate of re-oxidation is represented by the equation (01), can be derived from the analysis of experimental results, where K is the dissociative adsorption constant of oxygen. This suggests that the reduced palladium is oxidized by oxygen which is dissociatively adsorbed on active charcoal.
In the equation (01), κ2√K which is the measure of the re-oxidation activity, was found to vary with temperature, ethylene pressure and anions. The order of re-oxidation activity of palladium salts was Pd(NO₃)2>PdCl2>PdSO₄ under the same reaction condition.

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Department of Industrial Chemistry, Faculty of Engineering, Toyama University; Takaoka-shi, Toyama, Japan As a continuation of our studies on the synthesisn2 of a new heterocyclic system, 3-substituted-5-phenyl-1, 1-dioxo-5, 6-dihydro-1, 4, 2-dithiazine, by intramolecular Michael cycloaddition of N-(2-phenyl-ethene-1-sulfony1)-Ni-substituted thioureas, dithiocarbamates and 0-alkyl thio carbamates and on cleavage of the C-S bond of these heterocycles, we report here the reactions of N-(2-phenyl-ethene-1-sulfonyl)dithiocarbamates [1] carrying an active ce, i9 double bond. Fig.1 shows the outline of the reaction. Pyrolysis of the amine salts of [1] or reaction between amines and 2-phenyl-ethene-1-sulfonyl isothiocyanates [3] in acetone yielded 3-alkylamino-5- phenyl-ethene-1, 1-dioxo-5, 6-dihydro-1, 4, 2-dithiazines [5]. Desulfurization of [l] with alkaline H₂02 gave S-methyl N-(2-phenyl-ethene-1-sulfonyl)thiocarbamates [2]. Isothiocyanates [3] and isocyanates [4] were produced by pyrolysis of [1] and [2], respectively. The reaction of [3] and [4] with amines afforded N-(2-phenyl-ethene-1-sulfony1)-Ni-substituted-thioureas [6] and ureas [7], and with alcohols 0-alkyl N-(2-phenyl-ethene-1-sulfonyl)thiocarbamates [8] and carbamates [9], respectively.

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Unsaturated esters, nitriles and alcohols bearing a terminal double bond were oxymethylated with CO and H₂O at 170°C in the presence of iron carbonyl-amine catalyst, and the effect of the position of the substituents upon the competitive reactions at the double bond, hydrogenation and oxymethylation, was investigated. Acrylates and acrylonitrile were hydrogenated exclusively, but the formation of lactones or hydroxyesters was observed in the reactions from crotonate to 5-hexenoate. Examination of the product distribution proved that the ratio of the oxymethylated products increased in the order of the distance between the double bond and the ester group. The similar tendency was also found in the reactions of the unsaturated alcohols from allyl alcohol to 4-pentenol. In this case, the isomerization of allyl-type alcohol to aldehyde was presumed to play a principal role in the hydrogenation. Based upon some experimental evidences for its presence. in the reaction mixture, mononuclear hydridoirontetracarbonyl anion was considered to be an active species in the two reactions.

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Dypnone [3] undergoes BFs-catalyzed bond cleavages to form benzoic acid [1] and 2, 4, 6- triphenylpyrylium fluoborate [4] (A cleavage reaction) and acetophenone [2] (B cleavage reaction). As the other reaction product, 1, 1, 3-trimethyl-3-phenyl-hydrindene [7] which is a dimer ofα-methylstyrene [6] is obtained. Thus A cleavage reaction is verified.
Difference in activities of two BF3-water complexes (BF3H₂0 and BF32H₂10) for the two cleavage reactions (A and B) is examined. For A cleavage reaction, BF3-1-120 is remarkably active, but BF3.2 H₂O is not so. B cleavage reaction is much easier to be catalyzed than A cleavage reaction and is activated even by BF3, H₂0.

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In the course of the studies of biaryl syntheses of aromatic polycyclic hydrocarbons, the Ullmann condensation of 3- and 9-iodobenzanthrones were carried out. While 3-bromobenzanthrone gave 3, 3'-bibenzanthronyl [5] only in 13% yield, 3-iodobenzanthrone [3] gave [5] in 86% yield with the use of the same activated Cu powder.9, 9'-Bibenzanthronyl [4] (mp 399∼4O1°C) was obtained from 9-iodobenzanthrone [2] in 54% yield by the same procedure as [5]. Characteristic band at 336 nm in UV spectrum of [4] provides evidence for the presence of C-C bond between 9-positions of two benzanthrone nuclei. The ullmann condensation of equimolar mixture of [2] and [3] proceeded under the same reaction concition. The crude products were separated chromatographically to give new unsymmetrical diaryl compound, 3, 9'-bibenzanthronyl [6], in 22% yield, as yellow crystals (mp 388∼390°C). The structure was confirmed by IR and mass spectra, and satisfactory C, H analysis was obtained. The yield of [3] by direct iodination of benzanthrone with iodine and periodic acid was improved to 87% by the addition of small amount of H, SO₄.

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The rates of quaternization of substituted N, N-dimethylanilines with benzyl bromide were measured at 30, 45 and 60°C in dimetylformamide (DMF). The effect of substituents on the reactivity of dimethylaniline and the existence of linear free energy relationship were discussed.
The kinetic data are shown in Table 1. The rate constants k are in the range 0.203∼78.1 X 10-4 1 sec' (45°C) and increase with the electron repelling ability of substituents. The values of the activation energy E are 6.5-10 kcal/mol and the activation entropy are -42∼-60 e. u., and the isokinetic relationship is observed between them as shown in Fig.2. Hammett equation using a as substituent constants is given by log k=- 1.92 α -2.874 (45°C).
As shown in Fig.3 the deviations from the Hammett correlation are found for m-dimethylaminophenol and p-substituted dimethylanilines substituted with formyl, benzoyl, nitro and methoxyl groups at n-position. The deviations are considered to be attributed to the conjugative interaction between the reaction center and these substituents and to the solvent effect of DMF on the substituent constants of these groups.
† Kinetic Studies on the Quaternization of Tertiary Amines.

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Vapour-liquid equilibrium in isoprene (I)-cyclopentadiene (C) system, with and without solvent and the effect of dicyclopentadiene (D) on this equilibrium were studied under 760 mmHg pressure. From the data obtained for I-C-D system, the following relationships were obtained.
log cx=0.1664-0.1894 XI+ 0.1062 X12
log (riirc)=0.0765-0.1894 Xi+ 0.1062 X12
l/t=0.0295 xi+ 0.0246 x0+0.0102 xD where a, r, t and xt are relative volatility, modified activity coefficient, boiling point (°) and mole fraction of component i in liquid phase, respectively. X is the calculated mole fraction, assuming the 'system as a pseudo-two-components (I-C) one.
These equations show that a is seemingly not affcted, by component D and that t is most sensitive for the change of xi.
The suitableness of N-methylpyrrolidone, dimethylformamide or 2-methoxy-ethanol for a solvent was tested and found that the above order was opposite to it. The appropriate content of water in the solvent was 15 wt%.

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Oxidation of propylene over mercuric chloride-active charcoal catalyst was studied in the presence of steam and air. The reaction proceeded catalytically only when active charcoal was used as a carrier. Main products were acrolein and carbon dioxide, and small amounts of acetone, 2-propanol and acetaldehyde were also formed. It is suggested by the dependence of reaction rate upon the partial pressures of components of feed gas and the effect of the amounts of supported mercuric chloride that the reaction proceeds through σ-complex and σ-ally1 complex. The reduction products of mercuric chloride formed during the oxidation reaction seem to be re-oxidized to mercuric salt by the catalytic action of active charcoal.

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It was reported by the authors previously that carbonyl compounds and diacetoxyl derivatives are formed by the oxidation of olefins with sodium bismuthate in acetic acid and in chloro acetic acid. In this paper, the reaction of 2-butenes with the same reagent has been investigated to reveal the reaction mechanism. Acetaldehyde and 2, 3-diacetoxylbutane have been formed as oxidation products from 2-butenes in benzene-acetic acid mixtures. Molar ratio of 2, 3-diacetoxylbutane to acetaldehyde has increased with an increase of reaction time and of a fraction of acetic acid in the solvent, while the molar ratio has not changed with varying initial concentrations of 2-butenes and sodium bismuthate. Small amount of water accelerates the formation of acetaldehyde, but prevents that of DA. These experimental results agree well with the assumed mechanism of the oxidation. It is moreover concluded that bismuth(V) acetate is formed by the reaction of sodium bismuthate with acetic acid.

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The present work is concerned with the test of Diamond's method for estimating a size distribution of aromatic planes in carbonaceous substances, by analysing the diffuse scattering of X-ray from non-crystalline substances containing small aromatic planes. The samples used are coal tar pitch in which condensed aromatic compounds (Pyrene, Perylene, Anthanthrone and Violanthrone) are mixed, 20% by weight, at temperatures below 300°C.
The 31 intensity values at 0.66 ≤ s ≡ 0.96Å-1(s=2 sin 0/λ) were measured and the layer size distribution was obtained by Diamond's method. The results show that layersize histograms for all samples have common shapes and peaks at size groups of 8.4Åand 10Å occuping 33∼39% by weight. A negative value was obtained for the proportion of carbon in layer size of 20 Å for all samples. The histograms show no quantitative variance of the proportion of size groups corresponding to the layer size of condensed aromatic compounds mixed in pitch. However, the mean layer size of samples increases linearly with the layer size of condensed aromatic compounds.
It is concluded that Diamond's method is not satisfactory enough in the accuracy to measure the distribution of aromatic layer size, but is applicable to obtain the mean layer size of noncrystalline carbonaceous substances.

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The conditions to prepare active carbon from brown coal were investigated. Brown coal used was Kashima, Taiheiyo or Yallourn. Experimental conditions were as follows, carbonization temperature: 600°C, activation temperature: 700∼900°C, activation time: 0.5∼15 hours, steam rate 1.3 g/hr, respectively. Specific surface area of Kashima or Taiheiyo coal showed a maximum at about 50% weight loss and decreased rapidly with further activation. Values of specific surface area were less than 500 m²/g. But specific surface area of active carbon from HCl treated Kashima or Taiheiyõ char increased monotonously with weight loss. Active carbons with specific surface area of 600 m²/g were prepared. Effect of activation temperature on specific surface area was negligible. The reactivity of HCl treated chars against steam was smaller than that of untreated ones. Yield of active carbon from HCl treated chars was higher than that from untreated chars under the same activation conditions. Specific surface area of Yallourn coal char was 400 m²/g which is about two times larger than other chars.
Active carbons with specific surface area of 900 m²/g were prepared from Yallourn coal.
The reactivity of brown coal against steam was much higher than that of bituminous coal.

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Phenol-formaldehyde resin was carbonized at 700°C and then activated with steam under fluidized conditions. The experimental conditions were as follows, activation temperature: 920°C; activation time: 2-5 hours; nitrogen flow rate: 5 //min; steam flow rate: 0.7 g-H₂0/ g-char, hr.
Specific surface area, pore size distribution, equilibrium adsorption isotherms and adsorption rate of methylene blue and sodium dodecylbenzene sulfonate (DBS) were measured for each active carbons.
More than 90% of pore volume consisted of pores smaller than 100Å in radius. Values of pore volume smaller than 100Å in radius were 0.379-0.978 ml/g.
The values of specific surface area of active carbon increased with decreasing weight and reached 2000 m²/g at about 75% weight loss. The reactivity of phenol-formaldehyde resin char with steam was lower than that of coal char.
Both equilibrium adsorption amount and effective pore diffusivity of methylene blue and DBS increased with activation. For the adsorption of methylene blue and DBS, the ratio of effective pore diffusivity to free diffusivity were of the order of 10-⁷-10-⁵ and 10-⁵-10-⁴, respectively.
Volume of pores smaller than 100Å in radius appeared to be very important for these adsorbates.
Active carbons whose specific surface area were more than 1500 m²/g showed higher adsorption properties than commercial ones.

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Vapor-phase oxidation of toluene to benzaldehyde was investigated using Mo03-P200 catalysts with different P/Mo ratios and Mo03-P205-Xm On, (1: 0.2: 0.1) catalysts, where Xm0n was metal oxide. Addition of P205 in a proper amount to MoO₃ improved the activity, the stability, and the selectivity to benzaldehyde. Addition of Bi203 to the Mo0, -P205 system increased the activity, but when the Bi203 content was such that Bi/Mo 0.2, oxidation reactions of produced benzaldehyde to CO and CO₂ were accelerated. All the metal oxide additives, except for Sb203, increased the activity. The efficiency was in the order Sn02 Cr203 TzTi02 V205 A1203 Bi203 NiO Co203 Fe203. In addition, Sn02, Cr203, and TiO₂ were remarkably efficient for the activity stabilization. However, the additives which have a high efficiency for the activity increase showed a tendency to accelerate the consecutive oxidation of produced benzaldehyde to benzoic acid. A Study of the Catalytic Partial Oxidation of Hydrocarbons.

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The authors studied to make clear the constituents and the characteristic odor of the essential oil of Houttuynia cordata Thunb.
The essential oil was obtained by steam distillation of the plant's leaves and stems. The essential oil was treated with 2 N sodium carbonate solution, then with 2 N sodium hydroxide solution, and was separated into the three parts: neutral part, phenol part and carboxylic acid part.
The resulting each part was investigated by means of column chromatography, gas chromatography, infrared spectrum, mass spectrum and nuclear magnetic resonance spectrum and the chemical analysis.
Consequently, thirty two kinds of compound were recognized as the constituents of this essential oil: ca-pinene, camphene, j3-pinene, H-myrcene, limonene, 1, 8-cineole, ocimene, pcymene, terpinolene, 49-caryophyllene, humulene, leaf alcohol, linalool, terpinene-4-ol, 1- nonanol, 1-decanol, nerol, geraniol, l'-dodecanol, 1-tridecanol, nonanal, decanal, dodecanal, 3- keto-decanal, methyl n-nonyl ketone, methyl n-undecyl ketone, methyl lauryl sulfide, decanoic acid, thymol, carvacrol, o-cresol and p-cresol; and the authors have considered that the characteristic odor of
this plant may be due to methyl n-nonyl ketone, 3-keto-decanal, methyl lauryl sulfide and homologues of aliphatic alcohol.

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The Fehling reaction of nineteen kinds of 1-0-protected uronic acids showed that hexofuranuronic acids having a hydrogen atom at C-5 position were positive, but, pentofuranuronic, hexopyranuronic, and heptofuranuronic acids were negative.
As -the amounts of produced cuprous oxide increased with the reaction time, and any change could not be observed in the NMR spectrum by treating sodium 1, 2-0-isopropylidene-a-o-glucofuranuronate at 95°C for one hr under the same alkaline condition without cupric ions, it was concluded that the unsaturated hexouronic acids, formed by removal of the 1-0-protecting group through the cupric ion-catalyzed 8-elimination, revealed the reducing ability. As a part of testing compounds, methyl 5-0-acetyl-1, 2-0-isopropylidene-3-0-(p-toluenesulfony1)-α-D-glucofuranuronate [5], the corresponding amide [6], 5-deoxy-1, 2-0-isopropylidene-α-D-glucofuranuronic acid hydrazide [7], benzyl P-D-mannofuranosidurono-6, 3-lactone [8], the corresponding 2, 5-di-0-acetate (9), the corresponding uronic acid hydrazide [W], amide [11], and ethyl 3-acetamido-3-deoxy-1, 2-0-isopropylidene-α-D-ribofuranuronate [12] were newly synthesized from appropriate derivatives.

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The equilibrium amount and the rate of adsorption of a dispersed dye, Whitex were measured at 80°C for linear polyethylene(PE) films to discuss the correlation between the sorption properties and the molecular orientation in the amorphous regions.
The PE specimens which were drawn at 60°C in various draw ratios ranging from 1.0 to 10.0 were prepared for the subsequent dyeing.
In the comparatively earlier stage of the sorption, the rate of adsorption of Whitex obeyed Fick's law to result in the diffusion constant D. The diffusion constant D dropped remarkably with draw ratios, whereas the amount of equilibrium sorption Q∞increased monotonically.
These results were explained in terms of the following two points of view: 1 the increase in the energy of amorphous regions with molecular orientation and 2 the decrease in the free volume and the increase in voids with drawing.

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A diffusion method is proposed for establishing molecular weight distribution of a polymer. The principle of the method makes use of the fact that the diffusion constant of monodisperse polymers is dependent on their molecular weight, and the diffusion curve of polydisperse polydisperse polymer is thought to be the summation over all curves of the components. The diffusion curve obtained from the interferometric method is expressed mathematically with Fredholm's integral equation of the first kind which provides the necessary relationship of molecular weight distribution and the diffusion constant of each component. A few errors might be inherently induced even in the most accurate measurement of the curve. Therefore, a new evaluating process is introduced for the numerical analysis of the curve. The flow chart is shown in Fig.2.
The validity for the application of the method is examined by the diffusion measurement of polystyrene in ethyl methyl ketone solution by a Mach-Zehnder interferometer at a carefully controlled temperature. The distribution is determined for the especially prepared polymers whose distributions have been preliminary known. These experimental results support the validity or The justification of the present method. The method has an advantage that it does not require any calibration curves. In addition, a limitation involved in the method is also discussed.

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The polymers containing harbituric acid (BA) structure were prepared by the reaction of crosslinked poly(chloromethylstyrene) with sodium 5, 5-diethylbarbituric acid, and poly(diethyl methylene-malonate) with urea. Further, diethyl methylenemalonate copolymerized with styrene, N-vinyl pyrrolidone and N-vinyl-2-oxazolidone. And the polymers containing BA structure were synthesized by the reaction of these copolymers with urea. Neighboring effects in these polymers were investigated. The adsorption of adenine by polymers thus obtained was examined.† Syntheses and Reactions of Functional Polymers.

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Japan wax is often bleached in the sunlight in the form of flakes or particles. In the midcourse of the bleaching process, they are usually melted and the concentration of colored materials unchanged in the particles is made uniform. This molten wax is, then, made again into particles, which are exposed to the sun and bleached furthermore. The midcourse melting of the Japan wax particles, called "nakani" in the works, brings about the shortening of the time required for bleaching. In this paper, we discuss theoretically the kinetics of the two bleaching reactions before and after nakani to obtain the reduction and suitableness of the total bleaching time.
Light intensity at the raw wax/bleached wax interface in a particle was considered to play an important role in the bleaching reaction. A simple, idealized model was, therefore, devised for the bleaching reaction in the particle, to set importance on the local light intensity in the particle. The Japan wax particles subjected to bleaching were dispersed with various size and the log-normal size distribution was assumed for these particles. Rate expressions for the two reactions were derived from the model and solved numerically for the total bleaching time with a digital computor.
The total time for the two bleaching reactions was found in our work to be almost always shorter than the time required for the same conversion by only a single bleaching reaction. This fact suggests the effectiveness in the range considered. It was found furthermore that the total bleaching time vs. coversion curve had a minimum. The minimal value of the total bleaching time is the optimal one. It was not recommended to expose the particles after nakani longer than the time spent for bleaching before nakani. As either the values of logarithmic standard deviation or molar absorptivity increased, the minimal bleaching time decreased in our work and consequently the nakani procedure became more effective.

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A treatment method of the phenolic wastewater which was exhausted from the reaction tank of a phenolic resin plant was investigated. The wastewater was dark purpuric red in color, and its pH was 13.8. The analyses of the wastewater showed that it contained 44000 ppm of the chemical oxygen demand (COD), and 18000 ppm of phenols. About 61% of the COD was precipitated by the neutralization with sulfuric acid (Fig.2). About 65% of the COD in the filtrate of this neutralized wastewater was rapidly removed by the adsorption with an activated carbon. The COD adsorption capacity of the activated carbon was attained to be about 100% by weight (Fig.3∼6). The wastewater became colorless, transparent water through the carbon treatment, and the best part of the residual contaminants was proved to be methanol, which was contained in the industrial formalin of a raw material of the phenolic resin. The used carbon was regenerated by the desorption with a small quantity of alkaline solution (Fig.7∼9), and could be reused (Fig.10). About 90% of the COD in this alkaline solution which was contained much more concentrated contaminants was precipitated by the neutralization with sulfuric acid. Therefore, it was shown that the phenolic wastewater which contained a large quantity of contaminants could be clarified through the treatment with acid and activated carbon. † Adsorbents and Ion-Exchange Materials from Coal.

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The present authors have succeeded in the observation of the effect of aggregate formation on infrared absorption spectra of dye molecules (2, 2'-quinocyanine) adsorbed on silver bromide, by use of an infrared spectrophotometer with a diffusive reflection attachment without pressing or crashing the dyed silver bromide powder. The infrared absorption spectrum of the adsorbed dye in J-aggregated form has been found to be identical to that of the dye crystal. This result suggests the physical adsorption of the dye on silver bromide. Small difference in absorption peaks around 800 cm-' between the adsorbed dyes in molecular state and in Jaggregated state has been attributed to the presence of physical interaction between dye molecules. † Studies on Mechanism of Photographic Sensitivity.

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A quantitative formation of hexamethyl-2, 4-cyclohexadienone was achieved by the oxidation of hexamethylbenzene with equimolar amount of peroxyacetic acid in the presence of excess boron trifluoride etherate. The amount of the catalyst required for the practical synthesis should be more than three mole, possibly due to the formation of a relatively stable complex between the catalyst and acetic acid or the dienone.
To a cold mixture of hexamethylbenzene(10mmol) and boron trifluoride etherate(44mmol) in methylene chloride was added a methylene chloride solution of peroxyacetic acid (11mmol) at 5°C. After a proper work-up, the dienone was obtained in 96% yield. This procedure is as effective as the peroxytrifluoroacetic acid method and is much more practical for a synthetic purpose.
Some other catalysts and peroxycarboxylic acids were also examined.

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The synthesis of naphthalic anhydride by autoxidation of acenaphthene in the liquid phase was studied. The effects of reaction temperature, time and oxygen pressure on the coversion of acenaphthene into naphthalic anhydride, and on the yield of naphthalic anhydride and acenaphthenequinone were examined. Naphthalic anhydride was obtained in 67wt% yield at 214°C under oxygen pressure of 30 atm for 2 hour.

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The direct hydration of myrcene[1] by the cation exchange resin(Amberlite IR 120) was studied. The hydrated products consisted of myrcenol[9], 1, 8-cineol[4] and 2, 6-dimethy1-5, 7- octadien-2-ol[M] along with other alcohols and unsaturated cyclic hydrocarbons(Table 1). From the results the reaction scheme is discussed. † The Reactions of Terpenoids.

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