Electron spin resonance of Gd(III)in single crystals of Ln₂Mg₃(NO₃)₁₂· 24H₂O (where Ln(III) denotes Ce(III), Pr(III), Nd(III), Sm(III), and Eu(III))was studied in X band at room temperature. A seven-line spectrum for H//Z as well as H//X and H//Y corresponding to Δ M=± 1 transitions, was observed for all these crystals. The angular variations of the observed spectra were studied and they showed the similar dependence for each host lattice. The experimental data fitted to the effective spin-Hamiltonian for C_3h symmetry. It was found that the empirical, linear, relationships exist between the magnitude of the Gd(III) zero-field splitting Parameter b and(i)the ionic radius of the host lanthanoid(III); (ii)the calculat6d value of< r²> of the host lanthanoid(III)wave function, which is concemed to lanthanoid contraction.

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ESR spectra of γ -irradiated starch, starch formate, glucose, sodium alginate, D-glucuronic acid, oxystarch and oxycellulose have been determined at room temperature. Characteristic spectrum of a doublet was obtained in case of starch, and of a singlet in sodium alginate. The spectra of oxystarch and oxycellulose were similar to each other and complicated. Upon heatipg the irradiated oxycarbohydrates at 100 C for 60min the spectrum changed to a broad singlet which may be considered to consist of two singlets having slightly different g-factors. The component of the esr signal that had disappeared on heating was similar to the doublet spectrum observed for the irradiated starch. The ehemical structure of the radicals produced in the irradiated systems was discussed referring also to the result of irradiated compounds of oxystarch-urea and of oxystarch-polyvinylalcohol.

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The surface tensions of various organic liquids having straight-chains were measured at O60 C. The following empirical relations have been obtained: σ=a-bt, a=c/Tb+d, and b=e/Tb +f, where σ is surface tension, t(C) is temperature, Tb(K) is normal boiling point of a compound, a and b are constants characteristicof each compound, and c, d, e, and f are constants characteristic of each homologous series. The values of o calculated by these equations agreed satisfactorily with the experimental ones.

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Fe2O3-deposition onto three different fabrics (polyester, nylon and cotton) in solutions of various electrolytes at a constant ionic strength of 1 10-3 was discussed in terms of the potential energy ef interaction between fabrics and Fe2O3 particles. The zeta potentials(ζ) of fabrics and Fe2O3 particles in the electrolyte solutions were measured by the method of streaming potential (Table 1, Figs.1 and 2). The potential energy due to the interactions of dissimilar eleetrical double layers (Table 2) and van der Waals' forces between Fe2O3 and fabrics were calculated by the theory of heterocoagulatien for a sphere-flat plate system. The relation between the maximum value of the total potential energy and the radius of Fe2Os particle is highly dependent on the type of the electrolyte added (Fig.3), The amount of deposition of Fe2O3 particles onto eaeh fabric (Table 4) decreases with increasing maximum value of the total poten, tia1(Table 3 and Fig.4)energy and FeaO3 having a radius of 0.1μ becomes to be not deposited onto fabrics at the maximum values of 80-1OOkT.

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Although N-dodecyl-2-pyrrolidone(D. P.) is almost insoluble in pure water, it dissolves clearly in aqueous solution of hydrochloric acid(HCI). The lowest concentration of HCI in which D. P. can clearly dissolve depends upbn temperature. It was found that there are two kinds of temperature of phase separatlon at a given concentration of HCI: the one is the temperature above which twophases appear, similarly to the cloud point observed for aqueous solution of nonionic surfactants; the other is the temperature below which two phases appear, similarly to the Krafft point observed for aqueotis solution of ionic surfactants.
It was concluded that D. P. in water forms N-dodecyl-2-pyrrolidone hydrochloride(D. P. HCl) in the presence of HCl, and gives a clear solution because of the hydroyphilic character of the latter. When the temperature is higher than the"cloudl point", phase separation occurs, with D. P. precipitating. These relations are shown in Fig.2. The enthalpy change of the hydroclhoride formation is calculated to be -0.88kcal/mol.
Surface tension of aqueous sblutionof D. P. was measured at various concentrations of HCl, and the results are shown in Fig.3. The adsorption of D. P. ontothe surface were examined on the basis of Langmuir s equation as shown in Fig.6. Criticahnicelle concentration(CMC), surface tension at CMC(γ cmc)and surface area of adsorbed molecule(A) changed remarkably with concentration of HCl near the "cloud point", as shown in Fig.7. It is, therefore, concluded that D. P. is changed to D. P. HCl near the "cloud point".

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The correlation between the reaction conditions in the oxidation ef ethylene and the "surface resides which remained during the oxidation over Ag-K2SO4-Al2O3 catalyst was studied. The amount of residues was determined by means of the oxidative desorption teichnique-that is, the catalyst after the reaction at 170-270 C was heated in helium and then in oxygen at 280 C. Further, the oxidative laesorption using igo-enriched oxygen was carried eut for the identification of surface residues. Gases releaVsed by this oxidative desorption were carhon dioxide and water. The amount of the irreversibly adsorbed carbon dioxide during the reaction was 14-16% of the total amount of released carbon dioxide. The amount of residues increased with reaction time up to a stationary value, and with partial pressure of ethylene oxide in the reaction products. Its maximum was observed at about 216 C. Moreover, the following results were suggested by the analyses of the results obtained,
1) The amount of residues depends on the extent of the irreversibly adsorbed oxygen,
2) The amount of residues has an excellent relation to the catalytic activity,
3) The residue other than carbon dioxide is a compound containing two ozygen atoms and an theylene molecule-probably glycol type,
4) Each residue occupies two active sites and decreases the catalytic activity

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The dependence of η on PC2H4O, PO2, PCO2 or PH2O was studied in the flow system at 230-280 C, where η was the magnitude of the deactivation due to C2H4O formed on silver potassium sulfate catalyst in the oxidation of ethylene. The muasurements of the amounts of surface residue under various reaction conditions were also carried out by the oxidative desorption technique at 280 C. The amounts of surface residue paralleled η. The decrease in the catalytic activity was, therefore, assumed to be caused by the accumulation of surface residue.
The following empirical equatiens for η were obtained by analyzing the data in the flow system:
i) η=k: for the deactivation induced by C2H4O.
ii) η=k: for the deactivation, which is retarded by 02 or H20, being represented as i.
iii) η=k :for the deactivation, which is retarded by CO2.
In these equations, k, m and n are empirical constants, whereas Kt is an adsorption constant. η 0 is the η when PC2H4O=0.05 atm and PO2=0.20atm.
As to the retarding action of O2 or H2O for the catalyst deactivation due to C2H4O, the following mechanism was suggested; 1) at first, adsorption of C2H4O seemed to repel oxygen from the adsorption sites but it competed, in turn, with that of O2 or H2O, since the adsorption sites were common.2) finally, the adsorption of O2 or H2O would occur dissociatively and consequently, the deaetivation was retarded.
CO2 would retard the catalyst deactivation probably by forming CO32- or CO3-, but its effect was small in comparison with that of O2 or H2O.

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The cathodic properties were studied on the zinc oxide powder layer contacted with aluminum in 2, 3, 5-triphenyl tetrazolium chloride (TTC) aq. solutien by measuring the phote induced electrical potental. The cathodic reaction formed 1, 3, 5-tripheny1 formazan red(TF) on the zinc oxide layer. The amount of deposited TF was proportional to the time integratgd. magnitude of the photo induced potential of the photosensitive couple of Al-ZnO (sensor) measured against a calomel electrode, since the amount of total charge consumed for TF formation was approximately proportional to the integrated potential. The rate of TF formation at the initial step was almost determined by the current flowing across the zinc oxide layer, but it was turned gradually te the diffusion contro1 of TTC on the surface.

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Magnesium highpolyphosphate coacervates were prepared by a reaction bet. ween cationexchanged aqueous solution of sodium metaphesphate and magnesium chloride solgtion.
Molar ratios of MgO/P2O5 in coacervates were distributed in the vicinity of O.8. The deviation of their ratios from the theoretical value 1.0 could be attributed to the coexistence of sodium ions. A paper chromatography test showed that at least 850% of phospsphate ions in the coacervates were in a highly polymerized from (n 8) and the rest were in a ortho form. A number average polymerization degree of the highpolyphosphate ions was determined to be 25-50 by an acid base titration.
Small amounts of the residual sodium ions brought about the formation of crystalline substance X besides mat gnesium tetrametaphosphate, both were the final products of a successive condensation reaction caused by the heat-treatment of the samples. On the other hand, a condensation process of a sodium-free coacervate coincided precisely with that of Mg(H2PO)2 2H2O. The appearance of characteristic PO2 and PO3 peaks in IR and Raman spectra suggested that substance X was a linear sodium magnesium polyphosphate with comparatively short chain length. Furthermore, X was proved to be disodium trimagnesium hexapolyphosphate (Mg3Na2P6O19) by a fact that only a substance having the composition of 3MgO Na2O 3P2O5 gave the same X-ray diffraction pattern as that of X.

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The effect of some anions on the flocculation of bentonite particles dispersed in calcium hydroxide solution has been studied with and without addition of polymer fiocculant. The anions studied were OH-, Cl-, CO3 2-, SiO3 2- and SO4 2-.
The addition of NaOH or NaCl increased both the settling and filtration rates of bentonite suspension. Particularly, great increase in the filtration rate was found in the case of NaOH. On the other hand, the effectiveness decreased in this order. Similar effects were observed in the presence of polymer fiocculants except sodium polyacrylate.
The outstandifig effect in the presence of OH- has been explained by assuming an edge to face flocculation of montmorillonite particles in addition to the well-known flocculation induced by compression of electrical double layer by electrolytes: the broken edge surface, which reicts firgt with OH-, is positively charged by the subsequent adsorption of Ca2+ and then edge to face flocculation occurs between the positively charged edge surface and the negatively charged flat face surface.

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Fluorapatite(FAp) was extracted with a boiling aqueous solution of aluminum chloride (wet precess), and treated hydrothermally with anhydrate or hexahydrate of the chloride (hydrothermal process). The product obtatined from the wet precess was heated at various temperatures and under water vapor pressures(dry preeess).
In the wet process, some part of the FAp sample was dissolved, and by adding NaOH to the solution, the dissolved phosphorus and fiuorine were precipitated as different substances from FAp above pH 4. The dry process principally consisted of dehydration, defluorination,

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Equilibrium of the reaction (NH₄SO₃)₂NH+NH₃ ↔ 2NH₄SO₃NH₂ in the production of ammonium imidobissulfate has beenstudied over the temperature range 180-250 C and under 10-60kg/cm2 ammonia pressure.
The equilibrium was approached from ammonium amidosulfate side, and the equilibrium composition was determined by direct analysis of the equilibrium mixture. The results are given in Table 1.
The equilibrium composition(wt%)at 230 C and under 30kg/cm2 ammonia pressure the optimum reaction condition for the produetion of ammonium amidosulfate was:
NH4SO3NH2 87.9, (NH4SO3)2NH 4.3, (NH4)2SO4 6.2
Equilibrium constants (K) at 453, 473 and 493 K were 698, 365 and 255, respectively. The enthalpy, free energy, and entropy differences evaluated from these values were Δ H=-12.58kcal mol-1, Δ G=-5.31kcal mol-1(493 K) and Δ S=-14.74cal deg-1 mol-1, respectively.

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Formation of ammonium sulfate in the production of ammonium amidosulfate by the reaction of (NH4SO3)2NH + NH3 - 2NH4SO3NH2 has been investigated over the range of 200-310 C and 2-30 kg/cm2 ammonia pressure.
Ammonium sulfate formed in the ammonolytic reaction was confirmed by X-ray diffraction, paper chromatography, and chemical analysis. The amount of ammonium suifate increases as the temperature and ammonia pressure are increased. Especially, it increases greatly above 250 C under 30kg/cm2 ammonia pressure, and at about 3000C under the same pressure, the chief product of the reaction is ammonium sulfate. A small amount of sulfur is also produced in the reaction, and this sulfur increases with increasing ammonium sulfate.
The mechanisum of the formation of ammonium sulfate is considered that the presence of ammonia promotes the dehydration of ammonium amidosulfate and ammonium imidobissulfate, and the yielded water reacts with above residual two substances to form ammonium sulfate. The overall reaction is given as the following equation.
Lower pressure reaction, at 230-280 C and under 2-5kg/cm2 ammonia pressure, was also investigated in connection with the production of amidosulfuric acid and ammonium amidosulfate.

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Decomposltion of benzyl hydroperoxide(BHP) catalyzed by copper chlorides was carried out in pyridine. Cuprous chloride was found to be very active for the decomposition of BHP through radical mechanism.
Cupric chloride, not so active as cuprous one, also decomposed BHP through radical mechanism under nitrogen atmosphere. However, in the presence of oxygen where the formation of active cuprous species was inhibited, BHP was decomposed not through radical mechanism but through ionic dehydration by pyridine. It was assumed that cupric chloride formed complex with BHP to accelerate its ionic dehydration. The formation constant of this complex seemed to be considerably small from the kinetic discussion.
Some discussions were also made conceming the behavior of the copper-pyridine system toward benzyloxy radical which was the intermediateof the radical decomposition of BHP.

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The kinetics of the substitution reactions of the iron(III)-complexes of N-(hydroxyethyl) ethylenediamine-N, N, N -triacetic acid (EDTA. OH), diethylenetriamine-N, N, N, N, N -pentaacetic acid (DTPA) with gallium(III) ion have been studied in the pH range 1.4-2.5 at 25 C and an ionic strength of O.1 adjusted with sodium perchlorate.
The reactions were followed spectrophotometrically at 260nm, the absorption peak of the iron(III)-complexes. The initial rate of the forward reaction (Rf) was expressed as
Rf=(k4+k5[H+]+ k6[H+]2) [FeX][Ga3+]/[Fe3+]
for the EDTA-OH system,
Rf=(k1+k2/[H+]+k3/[H+]2)[FeH2X][Ga3+]
for the DTPA system. The initial rate of the reverse reaction (Rr) was expressed as
Rr=((k1[Fe3+]+k4)+ (k2[Fe3+]+k5)/ [H+] + (k3[Fe3+] + k6)/[H+]2) [GaH2X]
for the DTPA system.
Rr=((k1[Fe3+] + k4)+(k2[Fe3+]+k5)/[H+]+(k3[Fe3+]+k6)/[H+]2)[GaH2X]
for the DTPA system.
Contribution orf ea6h teaction path to the over-all rate of the rection was estimated. It seems that the forward reaction for the EDTA. OH system proceeds through the dissociative path in which the rate-determining step is the dissociation of the iron cmplex, and that for the DTPA. OH and DTPA systems seem to proceed through both of thg paths.
By measuring the absorbance at the equilibrium state, the logarithms of the concentration stability constants at 20 C for the Ga(III)-complexes of EDTA-OH and DTPA were found to be 19.4 and 28.1, respectively.

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Atomic absorption spectrometry of lead was studied by using a carbon tube flameless atomzer. The variables affecting sensitivity and reproducibility such as the inside dlameter of the tube, the inert gas and its flow rate, and sample inlection volume, as well as interference of diverse ions were investigated.
Each carbon tube having the inside diameter ranged from 2.5 to 5. Omm was made of the carbon rod with a length of 70mm and with a diameter of 6.35mm: Smaller bores gave higher sensitivity, but larger bores gave higher reproducibility and lower back grounds. In the present study, the tube with the inside diameter of 4.0-4, 5 mm was used.
The effect on the peak absorbance of an inert gas, which protected the carbon tube from atmospheric oxidation at high temperature, was examined. The ratioof the peak absorbance in argon, nitrogen and helium was 1 1 0.9, at the flow rate of each gas of about 0.4l/min. The peak absorbance of lead decreased as argon flow rate increased.
A fairly linear calibration curve was obtained in the range of(5-50)10-10g of lead with injection volume of 5μ l and argon flow rate of O.4l/min. The detection limit was 6.5 10-11g and the relative standard deviation, 2.8 per cent. Most cations, at 100 times as much as lead, scarcely interfered in the. determination of Iead, but several cations at 1000 times, seriously interfered. Lead content in sea water was determined by extracting it into diisobutyl ketone as diethyldithiocarbamate, injecting 10μ l of the organic phase and measuring the peak absorbance at thff wave length of 283.3 nm. With this: method, 1.7 8. Oppbof lead were found in the sea waters of Suruga Bay, Shizuoka Pref.

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DC and AC polarographic behavior of titanium(IV)-trans-cyclohexane-1, 2-diamine-N, N, N', N' -tetraacdtate (CyDTA) and N-(2-Hydroxyethyl)ethylenediamine-N, N, N' -triacetate (EDTA· OH) chelates was studied in detail. In acidic EDTA· OH solution and CyDTA solution, titanium(VI) chelate ion gave invariably a single well-defined, reversible polarographic wave, corresponding to the following one-electron reduction.
Ti(OH)nXn- + e + nH+ ↔ TiX- + nH2O
Ti(OH)nX1-n + e + nH+ ↔ TiX2- + nH2O (n=0, 1, 2, .....)
where X is CyDTA and Y shows EDTA· OH.
In the cace of CyDTA-titanium(IV) chelate, one hydrogen ion is involved at 1.3< pH< 3. O and two hydrogen ion involved at 3.0< pH< 5.5 in the ele ctrode reactioni In the case of EDTA· OH-titanium(IV)ehelate, one hydrogen ion is related to the electrode reagtion below pH 4. As the pH increased, polaregraphic wave became more irreversible, diffusion current decreased and the selution became colloidal in both cases.
From the relation between the half-wave potential and the concentration of hydrogen ion, chelating agent and electrolyte, the compositions and the dissociation constants of titanium(IV)- CyDTA, titanium(IV)-EDTA· OH chelates, and titanium(III)-CyDTA, titanium(III)-EDTA· OH chelates in solution were determined.

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Carbon-13 NMR speetra of 21 o-, m-, p-disubstituted benzenes and 12 polysubssitutgd benzenes have been measured in CDCl2 and d6-DMSO. The resonance lines were assigned on the basis of 1) the relative signal intenisity, 2) off-resonance decoupling technique, and 3) chemical shift of the homologous compounds.
Precise values of 13C chemical shifts of substituted benzenes were determined as shown in Tables 1, 2, 4 and 5.
The additivity of 13C chemical shifts of benzene ring carbons in substituted benzenes wgs examined.13C chemical shifts of o-, m- and p-disubstituted benzenes calculated from a simple additive rule were in good agreement with the observed values within 1 ppm. the modified additive rule was proposed for the calculation of 13C chemical shift of polysubstituted benzenes. By use of modified addittve rule, calculated chemical shift values of cresotic acids, polymethylsubstituted benzenes and polychlorosubstituted benzenes were in good areement with observed values with in 1 ppm.

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From the fact that hydroquinone gives p-quinone and hydrogen peroxide by air oxidation in alkaline buffer solution, it is expected that hydroquinone monosulfonate gives p-quinene monosulfonate and hydrogen peroxide by air oxidation under the same condition. But potassium p-benzoquinonesulfonate could not be detected by polarographic method with dropping mercury electrode. This result was due to the fact that potassium p-benzoquinonesulfonate reacted with OH- ion in buffer solution. It was presumed from the study of absorptign spectra and and polarographic data that OH- ion attacked the carbonyl carbon atom of p-quinone monosulfonate. The petassium p-benzgquinonesulfonate was reduced by the addition product of OH- ion to give hydroquinone monosulfonate.

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The MO calculations with CNDO/2 approximation have been carried out to elucidate the geometries and electronic properties of alkoxy1. and alkylperoxyl radicals and alkyl hydroperoxides: (a) The bond distance of C-O linkage in alkoxyr radicals fell in the range of 1.35-1.37A, and the larger the alkyl group attached to the oxygen atom the more the C-O bond distance became longer. (b) The distances of α O-β O bond in alkylperoxyl radicals and hydroperoxides were estimated to be 1.19A and 1.23A, respectively, and their bond angles of C-α O-β O were evaluated to be 111 and 109, respectively. (c) The ionization energies of the radicals were estimated Iarger than those obtained by the experiments, and the calculated g values of hydroperoxyl and methylperoxyl radicals (2.011 and 2.003, respectively) were in good agreement with that (2.015) resulted from the observations. Finally, some noticeable bond nature of the above radicals was discussed.

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Various acyclic α -halo-β -amino- and α -thiocyanato-β -amino α, β -unsaturated ketones were prepared and their structures were established. The reaction of 4-amino- or 4-monosubstituted amino-3-Penten-2-one [1], 3-amino- or 3-menosubstituted amino-1-phenyl-2-buten-X-one [2]and 3-amino- or 3-monosubstituted amino-1, 3-diphenyl-2-propen-1-one [3] with N-chloro- or N-bromo-suecinimides under nitrogen atmesphere at O-50 C gave 4-amino- or 4-monesubstituted amino-3-halo-3-penten-2-one (Cl [4 a - c] and Br [7 a - c]), 3-amino- or 3-monosubstituted amino-2-chlero-1-phenyl-2-buten-1-one[5 a - c] and 3-amino- or 3-monosubstitued amino-1, 3diphenyl-2-halo-2-propen-1-one (Cl[6 a - c] and Br[8 a - c]), respectively. The substituents on nitrogen are a: H, b: Me and c: Ph. The reaction of [1 a - c] and [2 a] with thiecyanogen at -15-O C gave 4-amino- or 4-monosubstituted amine-3-thiocyanato-3-penten-2-one [9 a - c] and 3-amino-1-phenyl-2-thiodyanato-2-buten-1-one [10 a].
From the IR and NMR spectral data, it was confirmed that an ec-hydrogen atom, of the enamino ketones was substituted by halogen or thiocyanaeo group, and these products were inferred to exist in the intramolecular hydrogen bonded enamino ketone form. The effect of the α -sabstituent on the hydrogen bonded chelate ring was also discussed.

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Several salts of imidobissulfuric acid have been used as a mild sulfonating agent. Under sulfonating conditions, these salts were first converted to the complexes of Lewis bases and sulfur trioxide, and then allowed to react with substrate. The sulfonation reaction was probably anticipated to be the exchange reaction between a constituent Lewis base in a sulfonating agent and a substrate whieh was another species of Lewis base, as shown in the equation(1):
B: SO3+B': → B': SO3 + B: (1)
Therefore, under sulfonating conditions, di(tertiary ammonium) salts of imidobissulfuric acid might apparently be converted to Lewis base-SO3 complexes and tert-amine-SO3 complexes should be formed as shown in the equation(2):
HN-SO3HR3N → R3N SO3 + H3NSO3H R3N (2)
The salts of trialkylamines, pyridine bases, and N, N-dialkylanilines were elxamined and the corresponding tert-amine-SO3 complexes were expectedly isolated except from the last salt, but the N, N-dialkyl sulfanilic acid was obtained from the salts of N, N-dialkylariilines. This upexpected result could be accounted for the property of N, N-dialkylapiline-SOs eomplex which was converted very easily to N, N-dialkyl sulfanilic acid upon heating.

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The electrolytic benzoxylation of N, N-disubstituted formamides, N-methyllactams, and cyclic N-methyl imides with benzoic acid has been studiedi with N, N-disubstituted formamides, the current efficiency for the formation of ester-amides decreased as bulkiness of the substituent increased. The steric effect of N-alkyl groups was conspicuous. ln the case of N-methylformanilide, electrolytic benzoxylation did not occur, and this fact might be due probably to the presence of ev-phenyl group to nitrogen atom. Electrolysis of formamides of eyclic amine and N-methyllactams at low current density gave ester-amides in high current effciency. In the electrolytic benzoxylatien of N-methylsuccinimide the correponding ester-amide was produced in very low yield, and the reaction did not occur at all in the case of N-methylphthalimide. Ester-amides had a benzoylexy group substituted at α -position to nitrogen atom. ln the case of N-methyllactams and cyclic N-methyl imides substitution occurred at N-methyl group. This fact shows that the benzoyloxy group does not attack the methylene group in a ring.

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The condensation reaction of p-, m- and o-hydroxybenzaldehydes ([2], [7] and [12]) with phenylacetic acid [1] in the presenee of Et3N-Ac2O was studied.
By the reaction of either [2] or [7] with [1], the isomers of both trans- and cis-α -phenyl(P- or m-) acetoxycinnamic acids, ([3A], [3B] or [8A], [8B]), were obtained respectively. On the other hand, the reaction of [12] with [1] gave trans-α -phenyl-o-acetoxycinnamic acid [13A] and 3-phenylcoumarine [15].
When the trans acids were heated under reflux in Et3N-Ac2O, [3A] and [8A] were converted into the equilibrium mixture of trans and cis isemers, respeetively, but [13A] was changed to [15].
Each acetoxy acid except [3B] was hydrelyzed to the corresponding hydroxy acid by treatment with aqueous NaOH, but the cis acid [3B] was converted into trans-p-hydroxy acid [4A].

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The three step alkaline hydrolysis of tris(2-acetoxyethyl)isocyanurate (TAEIC), tris(methoxycarbonylmethyl)isocyanurate (TMCMIC) and tris(2-methoxycarbonylenthyl)isocyangrurate (TMCEIC), and the three step reaction of tris(2, 3-epoxypropyl)isocyanurate (TEPIC) with either substituted benzoic acids or sodium thiosulfate have been investigated under various conditions.
The three rate constants have been determined by use of the general method of calculating the rate constants for a three-step consecutive-competitive second-order reaction of the type A+B → C+F, A+C → D+F, A+D → E+F
It was observed that in the hydrolysis of TAEIC and in the reaction between TEPIC apd substituted benzoic acids, the ratio of k1/k3 and k2/k3 were 3 and 2, respectively, whereas in the hydrolysis of TMCMIC and TMCEIC and in the reaction of TEPIC with sodium thiosulfate, the ratio were as follows; k1/k3> 3 and k2/k3> 2. The experimental observantion can be explained on the basis of the isocyanurate-ions or neutral molecules in the several steps.

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The catalytic behavior of tetracarbonyl(hydro)iron anion, which was prepared from ironpantacarbonyl and a tertiary amine in the presence of water or hydrogen under carbon monoxide pressure, was investigated in the reduction of five unsaturated compounds, methylvinyl ketone, methyl acrylate, ethyl methacrylate, methyl crotonate, and acrylonitrile. The time dependence of the reaction was followed by infrared spectra for the anion and gas chromatography for the reduction product, respectively.

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The dimerization reaction of isoprene was carried out in a number of binary solvent systems. When isoprene was added dropwise to a solution of sodium naphthalene in the binary se1vent system of tetrahydrofuran/benzene, a mixture of 2, 3, 6-trimethyl-1, 5-heptadiene (1) (790%), 2, 6-dimethyl-2, 6-octadiene (2) (1%), and 2, 7-dimethyl-2, 6-octadiene (3) (20%) was obtained in 50% yield.
When the reaction of isoprene with sodium naphthalene was carried out in the binary solvent system of tetrahydrofuran/toluene, the yield of dimer was poor and various ω -alkylation products of toluene were obtained in 80% yield. The reaction has also been extended to the other aromatic compounds such as ethylbenzene and xylehe.

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Hexamethylbenzene (HMB) was difficult to be oxidized with alkaline potassium permanganate solution, since HMB was insoluble in an aqueous alkaline solution. But, when HMB was warmed with 50% nitric acid for an short time, and then treated with aqueous potassium permanganate, the reaction occurred readily and dimethylpyromellitic acid was obtained. When HMB was warmed with 50% nitric acid for 1-2 minutes, a yellow material was produced, which was soluble in hot aqueous potassium hydroxide, though free from carboxylic acids. It contained a little amount of bis-(nitromethyl) prehnitene and several unknown compounds.
Further, the heat-stability of polyimide prepared by the reaction of tetramethyldimethylpyromellitate with 4, 4-diiaminodiphenylmethane turned out to be nearly equal to that of polyimide prepared from tetramethylpyromellitate.

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The electrical conductivity of phosphonitrilic compouuds was measured by DC method.
The room temperature resistivities of (PNR 2) 3 are in the range from 10 11 to 10 13(ohm, cm). The resistivity was remarkably dependent upon side groups, R. As a result, the order of the resistivities is shown below:

In thioamido phoshonitrilic trimer, the change of energy gap, Eo value, was observed in the range from 50 to 70 C, and usually E value was lower in the low temperature region than in high temperature one. In (PNS)n polymer marked polarization was hardly observed, and the values of resistivity and energy gap of the polymer were smaller than those of the trimeric phosphonitrilic compound. As there are more P=N conjugated double bonds and π electrons in the polymer than in the trimer, electronic conductivity will be predominant in the polymer The conduction was ohmic in the electric field strength from 500(V/cm) to 1000(V/cm).

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The reactions of phenol, novolak, and dihydroxydiphenylmethane with hexamine have been examined by differential scanning calorimetric analysis (DSC), thermogravimetric analysis (TGA), infrared (IR) spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy.
The results may be summarized as follews:
(1) Free phenol in novolak decreases the melting point of novolak and accelerates the gelation reation (Fig.1 Table 1).
(2) Free phenol reacts with hexamine to form the complexes (Reaction(1)). The decomposition and volatilization of a part of the complexes take place by heating to 120 C (Fig.2 Table 2).
(3) The reaction of novolak with hexamine was similar to that of phenol with hexamine, and these reactions lead to the dibenzylamine-type compounds via the above complexes mainly.
The methylene-crosslinked structure is partly formed in the region of 130-170 C, accompanied with both endothermic peaks at around 130 C and a sharp exothermic peak in the DSC curves (Reaction(2) Fig.1).
(4) Rate constants of the above reactions were calculated by assuming first-order reactions. The apparent activation energy was estimated to be about 20 kcal per mole by using the methods of Kissinger and Fava (Figs.4, 5 and 6 Table 4).

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The sorption pr6cess of ethyl methacrylate (EMA)-g1ycidyl methacrylate (GMA) copolymers having three different compositions was traced by ζ -potential change. The measurements were carried out at room temperature -about 80 C, encompassing the glass transition point (Tg) of the copolymer examined.
The rate constants of the sorption obtained from ζ -potentia1 (estimated from the streaming potential method) were compared with the diffusion constants obtained directly from sorption experiments.
The results are as follows:
(1) The rate constant, K, showed clearly the dependence of the sorption course upon the composition that is, the activation energy E 1 z (negative)below Tg increased and d E 2 z (positive)above Tg decreased with increasing GMA content (Fig.4).
(2) The dependence of the activation energies (E 1 s, and E 2 8) obtained from the diffusion constant, D, upon the composition was not clear (Fig.8), but at lower temperature (be1ow 30 C)the contribution of the hydration to sorption amounts appeared in 8/2 and 7/3 copolymers (Figs.6 and 7).

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The viscoelastic properties of dilute aqueous solutions of sodium alginate (Alg) at ultrasonic frequencies were investigated by means of a torsional method with crystal resonators, The new type resonators, such as a huge crystal resonator and a jointed resonator used in this study, enabled us to cover the frequency range from 26 kHz to 131 kHz.
Since the association of water molecules, which are dissociated in the presence of Na+ ions, influences the affective electric resistance in a dilnte aqueous solution of polyelectrolyte, this effect was taken into consideration in the calculation of the mechanical impedance.
In order to examine the configuration of polymers in solution, the complex intrinsic rigidity which was obtained experimentally by extrapolation to zero concentraion should be quantitatively compared with these calculated from the existing molecular theories at infinite dilution. However, the G /c, (G - 5)/c, and (n0-na)/c values of the dilute aqueous solution of A1g changed nonlinearly and abruptly with dilution, so that the Fuoss-Strauss equation was used to obtain the intrinsic values.
In a dilute aqueous solution of Alg, polymer chains are assumed to take an extended stringlike configuration by the electrostatic repulsion between molecular chains, therefore the measured values and their frequency dependences could not be predicted by any of the existing theories. However, when the electrostatic repulsion was depressed by the addition of NaCl, the experimental values approached the theoretical curves according to the Rouse theory for a random coil polymer.

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The popcorn polymerization of vinyl acetate (VAc) has been studied. In the following experiments, popcorn polymerizations were carried out under nitrogen at 55 C. Popcorn polymers of VAc-ethylene glycol diacrylate (EGDA) and VAc-ethylene glycol dimethacrylate (EGDMA) were prepared (Table 1). The polymerizability of VAc in this system was investigated by using various popcorn seeds(Table 2). The rate of popcorn growth of n-butyl methacrylate (n-BMA) (using VAc-EGDMA popcorn seeds treated with heating in n-hexane-CCl4 or benzene-CCI4) was measured dilatometrically (Fig.1). Popcorn polymers of VAc-, vinyl propionate-, vinyl butylate-, vinyl valeriate-EGDA, VAc-EGDMA, VAc(using n-BMA-EGDMA popcorn seed) and n-BMA(using VAc-EGDA popcorn seed) were hydrolyzed in aqueous 10%NaOH-acetone solution, and the water-acetone-insoluble part(S1) was measured (Table 3-6).
The above experiments indicated that: (1) the popcorn polymerization is initiated with the small amount of radicals contained in the popcorn seed, (2) the net-works in the popcorn seed or formed during polymerization play an important part in the popcorn polymerization, and (3) popcorn polymerization of VAc, the chain-transfer of radicals to main- and side-chains of polymers occurs to give new bridges therefrom.

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The formation reactions of polyion complexes between polycations carrying, charges in the chain backbone and polycarboxylic acids (e. g., polymethacrylic acid, polyacrylic acid and polyitaconic acid) were studied by means of potentiometric titration. In these systems polycations release much more hydrogen ions than low molecular weight cations, so it was found that the chain lenght, i. e., the numder of charged sites, played an important role in the complexation. By using different polycarboxylic acids, it was shown that, in addition to the Cou1ombic forces, the hydrophobic bonds also influenced complexation. The n' value of the Henderson-Hasselbaeh equation, which shows the parameter of the intramolecular interaction of polymethacrylic acid, was found to be 2.3. However, this value decreased to 1.4 when the polycations were added to the polymethacrylic acid solution. This phenomenon shows that the electrostatic repulsion between neighboring dissociated carboxylic groups is diminished efficiently by the complexation. From these results, it is assumed that the dissociation constant and hydrophobicity of polymer chains control the ability of complexation.

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The meehanism of the formation of polyion complexes between polycations carrying charges in the main-chain and polycarboxylic acids (e. g., polymethacrylic acid, polyacrylic acid and polyitaconic acid) were studied by potentiometric titration, conductometric titration and viscosity measurement. The compositions of the complexes were found to be controlled by the degree of the dissociation of the polycarboxylic acids. Polycarboxylic acids usually dissociate only in a few percents at a concentration range of 10 -4 - 10 -3 mol/l, while the degree of dissociation were increased up to about 20%in the prefence of the polycations. The composition of the polyion complexes which were obtained from the polyanion and polycation solutions was in a ratio about 5: 1 of the repeating units of the ionic sites, i. e., [polycarboxylic acid]/[polycation]. When the degrees of dissociation of polycarboxylic acids were increased by addition of alkaline solution, the compositions of the complexes were found to be equimolar.
From these results, it was assumed that the polyion complexes which were formed in these systems could take any forms from loop to ladder succesively and arbitrarily.

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The equivalent conductances of alkali, alkaline earth, and tetraalkylammonium perchlorates were measured in dimethylacetamide (DMA); the values obtained for Li+, Rb+, Cs+, Ca2+, Sr2+, Ba2+, Me4N+, Et4N+, Hex4N+ and tetradecyl-dimethyl-benzyl-ammonium (TDDMB) ion were 21.3 4, 25.1 4, 26.4 1, 42.0 2, 41.6 8, 41.6 0, 34.8 5, 33.1 6, 18.81, and 18.6 0, respectively.
Therefore, the Stokes law radius of a monovalent cation is the smallest for Me4N+ and the largest for TDDMB ion. The solvation number obtained from the effective ionic radius of Robinson and Stokes is 2-3 for alkali ions except Li+ and approximately 4 for alkaline earth ions and Li+.

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Generally, the acidity and the basicity of the solid catalysts have been measured by Benesis'method. But by this method, the acidity and basicity of the colored catalyst, such as chromia, or the basicity of the white catalyst having strong acid, such as silica-alumina could hardly be measured. However, the acidity and the basicity of the above mentioned catalysts, chromia and silica-alumina, could be measured by the new titration method using a small amount of the white acidic (basic) solid oxides colored with the indicators on their surfaces.

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Effects of cadmium ion (Cd2 ) upon spectral sensitizations by 3, 3 -diethyl-thiatricarbocyanine (1) and phenosafranine (2) were studied. After Cd2 was added to tabular AgBr emulsions, they were digested at 50 C for 30 minutes. The spectrally sensitizing ability of (2) expressed by the ratio of minus-blue to blue speed of the dyed emulsion was improved by the addition of Cd2, whereas that of (1) was not. This result is considered to support the modified electron transfer mechanism for spectral sensitization proposed by the present author.

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In emulsions composed of octahedral AgBr grains(about O.7 μ in size), the decrease of photographic speed inherent in the AgBr grains (i. e., desensitization) caused by 3, 3-diethyl-9-methylthiacarbocyanine bromide was accelerated by sulfur sensitization, and depressed by reduction sensitization. These results are consistent with the widely accepted mechanism of sulfur sensitization, and also with the mechanism of reduction sensitization of the octahedral AgBr grains proposed by the present author.

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The electric conductivity of aqueous solutions of formic acid, acetic acid, propionic acid, hydrochloric acid, sodium chloride, sodium formate, sodium acetate, and sodium propionate was measured under the irradiation of ultrasonic wave. The conductivity increased and reached a limiting value within ten minutes. This change was found to be reversible. It was confirmed that the increase of conductivity was larger than that due to the rise in temperature caused by ultrasonic irradiation. In the case of hydrochloric acid, a pronounced increase of conductivity was observed. It seems that the protonic transition is affected more effectively by ultrasonic wave than the Stokes type migration.

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The distribution coefficient (Kd) of aminobenzenesulfonic acidisomers on several anionexchange resins was determined and possibility of the chromatographic separation was investigated. As expected from Kd value, o-isomer was easily separated from other isomers with Dowex 21K using O.2mol/l sodium chloride as eluant, whereas mutual separation of m- and pisomer was achieved only at lower pH such as 2 with dilute hydrochloric acid as eluant, m-isormer being eluted faster than p-isomer. Thus separation of the isomers with an anionexchange resin is considered to be possible under an appropriate condition, as shown in Fig.2.

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Formation of β -isopropylnaphthalene by the transisopropylation from isopropyl-substituted benzenes to naphthalene in the presence of AlCl3 was studied.
A mixture of diisopropylbenzene, naphthalene and AlCl3 (molar ratio 2: 1: 0.2) was allowed to react at 60-90 C for 6 hrs, and isopropylnaphthalene (β -isomer 78.8%)was obtained in 36% yield. The yield decreased in the order: diisopropylbenzene, ρ -cymene > cumene.

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Synthesis of unsymmetric N, N> -disubstituted amidinoformic acid (7) by the reaction of N-substituted derivative (2) with amines at an elevated temperature was unsuceessful due to easy decarboxylation of (2), however, (7) was smoothly obtained by condensation of N-substitutedthiooxamidic acid (6) with amines in methanol at a room temperature in the presence of mercuric oxide. Compound (6) was obtained by condensation of potassium thiooxamidate (1)and amines in a large amount of water, and successive extraction of the acidified reaction mixture with ether.

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The vinyl Po1ymerizations initiated by the system of dibuty1tin dilaurate (DBTDL) and carbon tetrach1oride(CCI4), or DBTDL and cupric ion(Cu(II))were carried out in the presence of water. It was found that the fomer system accelerated the polymerization of methyl methacrylate (MMA), acry1onltrile and styrene, but the latter system promoted selectively the polymerization of MMA. The polymerization conversion was not related to the oxidation-reduction Potential of metalic ion. There was the optimal amount of CCI4 or Cu(II) in the presence of Water and consequently, the maximal po1ymerization conversion was recognized. In the system of DBTDL, CCl 4 and water, the addition of water did not practically influence the polymerization.
Moreover, the polymerizations with both system were confirmed to proceed through the radical mechanisms and the overall activation energies (E) were found to be as follows:
DBTDL-CCl4-H20 system E=11. Okca1/mo1.
DBTDL-Cu(II)-H2O system E=14.6kcal/mo1.

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