A calorimerter composed of a Dewar vessel and a Beckmann thermometer was constructed. By means of this calorimeter, the heat capacities of aqueous solutions of ethylene glycol, propyrene glycol, and butanediol were measured at 30° C. It was confirmed by the measurement of heat capacities of n-heptane that the errors due to the evaporation were negligible. The partial molar heat capacities at the infinite dilution were obtained for the respective solutes. The structural changes of water caused by the dissolution of these solutes were discussed,

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The dielectric constants of various organic liquids of straight-chain were measured between 0° C and 50° C. The following empirical relations have been obtained: log D= log α+d-bt, α=c/Tb +d, and b=e/Tb+f, where D is dielectric constant, t(° C) is temperature, Tb(° K) is normal boiling point of a compound, α and b are constants characteristic of each compound, and c, d, e, and f are constants characteristic of each homologous series. The values of D calculated by these equations agreed satisfactorily with the experimental ones.

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It has been well known that the zone refining operation could be improved by an effective stirring of melt-zone. A quantitative study on this stirring effect has been developed in this paper.
A new zone refining apparatus was designed which could stir the melt-zone by a device constructed of an electromagnet and a rotor (Figs.1 and 2).
The sample used in this experiment was a binary mixture of m-chloronitrobenzene and pchloronitrobenzene. A glass tube of 18 mm I. D. in which the sample was packed for 240 mm length was used as a container. The operational conditions were as follows: The zone travel rate (V) was fixed at 62, 74 or 94 mm/hr, the stirring rate was varied in a range 0∼200 rpm at each zone travel rate and the length of melt-zone was controlled at 20 mm.
The concentration profiles after a single zone pass showed an effectiveness of stirring (Figs.3, 4 and 5). The effective distribution coefficient was decreased exponentially as the stirring rate was increased (Fig.7). An effective distribution coefficient (k) and a stirring rate (r-rpm) could be related by an equation as:
where α is a constant. The equation proposed above gave a good agreement, with the experimental results within a restricted range (Fig.7).

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Effects of atmospheric gases on the change of the crystal structure or colour of various cadmium pigments in the course of heat treatment were studied. The samples used in this experiments were precipitates having the compositions of the following four kinds, that is, CdS, β-CdS, 2 CdSZnS and 1.5 CdS.(CdCO₃.Se). As atmospheric gases, dried oxygen of high purity, nitrogen and helium were used.
The precipitates of the various samples, after outgassing for 1 hr. under the conditions of 200° C and 10^-1 mmHg, were heat-treated at 400, 500, 600 or 700° C in atmospheric gases. The changes in the physico-chemical properties due to heat treatment, despite the difference in the compositions of the various samples, showed a similar tendency. The oxygen atmosphere which was active toward the pigments improved the crystallinity and increased the brightness of colour, while nitrogen and helium, inert atmosphere, had little effects.
Crystallization and β→α phase transition took place preferentially on the crystal surface and in fine particles.

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In this paper, changes in some particle properties and color of cadmium pigments by heat treatment were studied. Samples used in this study were precipitates of four kinds, that is CdS, β-CdS, 2 CdS. ZnS and 2 CdS .(CdCO₃. Se). The samples were heat-treated at 400, 500, 600 or 700° C for an hour, 5 hours or 25 hours. On the other hand, the other samples, with addition of 1 wt% sulfur powder, were heat-treated to study the effect of the atmospheric gas on sulfur addition.
Heat-treated samples were investigated by the measurement of X-ray diffraction, surface area, electron microscopy, spectral reflectance curve, and chemical analysis.
The results showed that the values of the content of hexagonal-form, particle size and color took the similar changes on heat treatment and a tendency for saturation after five hours. The effects on heat treatment were reduced by the addition of sulfur to the samples.

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The nature of the surface of silica was modified by the treatment with 1-butanol. The modified silica was examined by means of differential thermal analysis, infrared spectroscopy, water adsorption measurement, measurement of heat of immersion and so on. It was shown by the decrease in the intensity of O-H stretching vibration band as well as the appearence of C-H one that hydroxyl groups on the surface of silica were changed to butoxy groups. Moreover, the affinity of the modified silica to water was decreased, that is, the water adsorption capacity was much less than that of the original one. The values of the heat of immersion into water of the modified silica were reduced to about 50 to 70% of those of the original silica. The butoxy groups formed were slightly decomposed even when the modified silica was evacuated at 400° C.

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The pressure-area curve and specific evaporation resistance-pressure curve were measured for a-monostearin monolayer on the surface of aqueous 1 mol/l solutions of various electrolytes at 25° C, where surface active impurities in the electrolytes had been removed with activated carbon from the aqueous solutions. The pressure-area curve was little affected by the added electrolytes, except that there seems to exist a trend that the area of α-monostearin decreased slightly by the addition of uni-univalent electrolytes, such as LiCl, NaCl, KCl, KBr, KI and KSCN, while it increased slightly by uni-bivalent electrolytes, such as Na₂SO₄, or bi-univalent electro- lytes, such as CaCl₂, MgCl₂ and SrCl₂.
The effect of addition of various electrolytes on the specific evaporation resistance of α-monostearin monolayer on distilled water was studied. The electrolytes making water structure, such as LiCl, MgCl₂ and NaCl, increased the specific resistance, while electrolytes breaking water structure, such as KI, KBr, KCl, and KSCN, decreased the specific resistance. It was found that the specific resistance of a monolayer on electrolyte solution had a close correlation with the self diffusion coefficient of water in those electrolyte solutions. These facts were explained on the basis of the change in the mobility of water near the hydrophilic group of α-monostearin.

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Using temperature jump method, rate constants of the following type reactions were obtained,
(M2 + is metal ion and L-, D- are L- and D-form of histidine anion). At 25° C and ionic strength of 0.1, rate constants were: nickel(II), k2= 4.1 X 10 mol-.1. sec-1, k_2= 0.059 sec-', k3=4.3 X 105 mol-1.1. sec-1, 2 k_3=0.027 sec-1; cobalt, k2 1.4 x 106 mol-l./ . sec-1, k2=5.7 sec', ks= 1.2 x 106 mol-1.1. sec-1, 2 k_3=2.9 sec'; zinc(JI), k2= 6.0 X 10' mol-l / sec-', k₂=190 sec', k3= 5.2 x 107 mol- .1. sec-1, 2 k_3=96 sec'; cadmium(II), k2 7 x 107 mol-l./ .sec-% k 2 4 × 103 sec' (the coefficient 2 of k, is the statistical factor).
The formation rate constants k2 and k, were equal within experimental error for nickel TO, cobalt10, and zinc(II), but 2 k, was about half of k2. The effect of optical activity of his- tidine on complexation reactions appeared kinetically on the dissociation reactions of bihistidine complexes. The results of formation rate constants agreed with the two step mechanism involving water dissociation from the inner hydration shell of the ion ML⁺.

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It is known that L-leucyl-L-tyrosine and D-leucyl-L-tyrosine show different pK values and stability constants with metal ions. To investigate kinetic effects of the optical activity of dipeptides, the rate constants of the following reactions were determined by temperature jump method
k1 Ni2++A- 4 NiA+ k2 NiA+ +A NiA2 k_ 2 (A= L-leucyl-L-tyrosine or D-leucyl-L-tyrosine).
The results, at 25° C and ionic strength of 0.15, were: L-leucyl-L-tyrosine, k, =2.2X 10 mol-'l'sec1, k_1= 1.3 sec', k2= 1.7 × 103 morl isec', k_2= 3.0 sec'; D-leucyl-L-tyrosine, k, 2.4 × 103 morl / sec', k_1=0.45 sec-1, k2-= 2.0 x 10' mol-1 /k2=2.4 sect. The value of formation rate constant k1 for D-leucyl-L-tyrosine is equal within experimental error to that for L-leucylL-tyrosine. But in dissociation reactions the value of k1 for D-leucyl-L-tyrosine was about one third of the value for L-leucyl-L-tyrosine. Kinetic stereoselectivity in complexation reactions of nickel(II) with these dipeptides appeared in the dissociation reaction of the complexes. These results were similar to the case of bi-histidine complexes of nickel(II), cobalt(II), zinc(II).

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The effects of C₂H₄0, H₂O and CO₂ on the. catalytic activity of silver promoted by potassium sulfate for the oxidation of ethylene were studied in the flow system at 250° C.
C₂H₄O deactivated the catalyst from its original active states to lower active state. H₂O and CO₂ retarded the deactivation by C₂H₄O. The retardation effect of H₂O was larger than that of CO₃.
From these results and the effects of high temperature taeatments of the catalyst, it was suggested that the stationary catalytic activity of silver under the reaction conditions might be given by the competition between the promotion of deactivation by C_2CH₄O and the retardation of deactivation by H₂O and CO, where C_2CH₄O, H₂O and CO₂ were the reaction products.

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A series of nickel oxide-alumina composite (1.3 atom ratio of Ni/A1) containing small amounts of platinum up to 10-2 weight per cent were retluced with hydrogen and the catalytic activity of each reduced nickel catalyst was compared for the vapour phase hydrogenation of benzene at temperatures of 100 and 150° C under atmospheric pressure. Incorporation of platinum was found to enhance the catalytic activity in proportion to the metal content, and to prevent the degradation of the activity with time in use.
Introduction of platinum also had affected the reducibility of the composite, and hence the activity of the reduced-catalyst. Thus, the platinized catalyst exhibited the same activity (cyclohexane yield of 9 per cent) as the none-platinized one at a lower temperature of about 40° for the preliminary reduction.
The rate of benzene hydrogenation was given by the first order kinetics in hydrogen over the two catalysts with and without platinum within the limits of this experimental conditions.

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The electrolytic reduction of oxygen in dimethyl sulf oxide (DMSO), N, N-dimethylformamide (DMF) and acetonitorile(AN) in the presence of lanthanoid ions and 0.05 molg NaCl04 was investigated with particular attention to the nature of electrolytic process in DMSO.
In these solvents, oxygen was reduced to an oxygen radical, 02-, which would readily pair with lanthanoid ions. The lanthanoid superoxide would in turn disproportion on the mercury electrode to form lanthanoid peroxide in DMSO.
Stable compounds of lanthanoid superoxide and peroxide of the formula M(02)3DMS0 (for the platinum electrode, in DMSO), M(02)3 (for the platinum and mercury electrodes, in DMF) and M2(02)3 DMSO (for the mercury electrode, in DMSO) have been prepared by the controlled current electrolysis. Their infra-red spectra are also reported.

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In concentrating sea water by the electrodialysis using ion exchange membrane, modification of calcium carbonate scale crystal, formed by either water decomposition or over-desalination, has already been known to be aragonite. In this report, the author studied the contribution of ions in sea water to the aragonite formation.
To the sodium chloride solution containing calcium and bicarbonate ions, magnesium, potassium and sulfate ions were added and the solution containing the same concentration as sea water was prepared. The concentrating experiment of this solution was carried out for about 100 hr by the use of the electrodialysis apparatus consisting of five unit cells of ion exchange membranes with 9 cm² in effective area.50-90% of chloride ion was introduced into the concentrated solution to realize over-desalination without accompanying water decomposition.
On the basis of the X-ray diffraction analysis and microscopic observation on the calcium carbonate scale deposited, the following conclusions were obtained.
(1) When sodium, chloride and sulfate ions coexisted, the scale formed was not aragonite but calcite (No.2, 3, 4, 5 and 13 in: Table 2, Fig.2 and Fig.3).
(2) When magnesium ion coexisted, aragonite of elliptical configuration, as in the case on sea water, was formed. This seemed to show dominating contribution of the ion to both modification and configuration of the scale crystal (No.1 and 6).
(3) When potassium ion coexisted, aragonite of rod-like configuration was formed, which was also observed when the amount of coexistent magnesium ion became low (No.7, 8, 11 and 12).
(4) When the scale was formed slowly, the ratio of aragonite existing in the scale to the coexistent potassium ion was nearly 1: 1, but when the scale was formed rapidly, it was almost 0: 1 (Fig.4).

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The electrodeposition of MnO, has been studied in sulfuric acid solution in the concentration range from 0.5 to 2 mol/l containing Mn²⁺ ion in the concentration range from 0.05 to 1 molfi. The polarization curves by a potential sweep method showed one oxidation wave at the sweep rate faster than 2 'NT/min and two waves at the slower sweep rate. One step wave was attributed to the oxidation of Mn²⁺ to Mn3+. With a decrease in the sweep rate, the deposition of Mn02 was observed and then it could be considered that the second wave appeared when Pt electrode changed to Mn02 electrode.
The current-time curves for a constant potential electrolysis showed an induction period, which became short with rise of the applied potential but long, reversely, above the potential 0.9 V (vs. Hg/Hg2SO₄/N-H₂504). The current increased with the Mn²⁺ ion concentration and the applied potential, but decreased at the Mn2 ion concentration of 0.5 m91// and at the potential more positive than 0.9 V.
From these results it is considered that Mn²⁺ is oxidized to Mng+ and that adsorbed Mns+ is disproportionated to MnO, and Mn²⁺.

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The electrolytic behavior of platinum in weakly-acidic aqueous solutions containing Na₂SO₄, NaNO₃, KNO₃ or KCl as electrolyte was investigated by means of cyclic voltammetry. The voltammograms obtained in these solutions were greatly different from those usually observed for strongly-acidic, neutral and alkaline solutions. Particularly, one reversible couple of oxidation-reduction currents was observed at about -0.5 V vs. SCE during the potential sweep of a platinum electrode in weakly-acidic solution. The appearence of this reversible wave which is attributable to the discharge of hydrogen ion under diffusion control was found to depend on the potential sweep range, sweep rate, kind of electrolyte, pH value and so on. A brief discussion was made on the suitable pretreatment methods of the electrode for evaluating the electrode reactions in these systems.

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Present work was done in order to get some informations on the mechanism of the catalytic Oxidation of SO₂, especially in it lower concentrations (0.1-1.5%), and to design the equipment for the removal of SO₂ from flue gases.
The initial oxidation rate was measured at a reaction temperature of 400-500° C, at SO₂ concentration of 0.1-4.5% and O^2- concentration of 0.4-5%. The experiments were carried out under the conditions where diffusion rate had no significant effect on the reaction rate. Experimental results are shown:
a) The oxidation rate increased with increasing partial pressure of oxygen (Fig.4, 5, 6).
b) The oxidation rate arrived at a certain value when the partial pressure of SO₂ increased, but further increase in partical pressure reduced the oxidation rate (Fig.7, 8, 9).
c) The position of the peak in the curve of oxidation. rate (Vs) vs. partial pressure of SO₂ (P5O^2-) was not influenced by partial pressure of oxygen (PO^2-), but changed with reaction temperature (Fig.7, 8, 9). Thus it is evident that the overall reaction rate was controlled by the reaction between the adsorbed SO₂ and adsorbed oxygen on the catalyst. The oxidation rate was expressed by the following equation.
Vs=kPo2Pso2/(1+KIPso2)2
The valence change between the tetravalent and the pentavalent state of vanadium in the mixture, V205-K2SO₄, was masured under the same conditions as steady state of the reaction, and the results showed that the value of V6+/(V5+ V4+) was not influenced by PO^2- but by P5O^2-.

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In order to obtain a physico-chemical data of synthetic fluor-phlogopite F21CMg9(A1Sis010) crystals at high temperatures, the chemical kinetics on their thermal decomposition in air was studied by means of thermogravimetric methods. The influence of crystal size upon the decom- position kinetics was particularly studied. Results obtained are as follows;
1) Isothermal weight loss of fluor-phlogopite powder less than 325 mesh was measured at 1305-1145° C. A single curve, showing a (fraction changed) vs. tito., (to., was the time needed for a = 0.5), was obtained which was fitted for any of the samples tested. It was decided from this fact that the same reaction mechanism might be considered under the present experimental conditions. The equation F(a)= a2 which was based on one-dimensional diffusion-controlled process showed the best agreement. From the Arrhenius plots of the rate constants an activation energy of 46 kcal/mol was obtained.
2) For 42-32 mesh sample the reaction appeared to be of the first-order F(a)=In(1). From the Arrhenius plots of the rate constants an activation energy of 43 kcal/mol was obtained, which was nearly the same value as for less than 325 mesh sample.
3) On the other hand, as the particle size of the sample varied from less than 325 mesh to 42-32 mesh, the activation energy (Ea, ) and the order of reaction (n) for the thermal decomposition of fluor-phlogopite varied successively from 31 to 106 kcal/mol and 1.3 to 4.7, respectively. The above data were obtained by Freeman-Carroll analytical method with constant heating rate of 10° C. The above results showed that the kinetics of thermal decomposition was influenced by crystal size. As the kinetic data obtained by Freeman method did not show the pure physico-chemical process, they showed the complex decomposition process as a whole.
4) The kinetics of thermal decomposition were obviously dependent upon the experimental conditions (crystal sizes and the methods of analysis). The difference of experimental conditions seemed to change the kinetics in appearance.

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To study the behaviors of trace elements in shells during the process of fossilization, sodium and manganese in shells belonging to Pelecypoda collected from Oligocene, Miocene, Pliocene, Pleistocene and Recent deposits in the northeastern Japan were determined by nondestructive neutron activation analysis.
The crystal-form of calcium carbonate and the shell structure have close connection with the manganese content in Recent shells, i. e., calcite type shells with foliated structure were higher in manganese content than aragonite type shells and calcite type shells with homogeneous or complex prismatic structure. Whereas, no significant difference in average content of sodium was observed between calcite and aragonite type shells, and the same is true for shells in fresh water and marine environments.
From Recent to Pleistocene, the sodium content of shells decreases greatly with decreasing residual organic matters in shells. And this trend becomes weak before Pliocene, whereas the manganese content in shells, especially calcitic shells, increases greatly with increasing age even before Pliocene. These results suggest that sodium was removed from shells together with decomposed organic matters and manganese was accumulated by adsorption in the remainders of shells from the surrounding water during the progress of fossilization of shells.

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The Beckmann rearrangement of the aliphatic ketone oximes, R(CH₃)C=NOH (R=Et [1]; n-Pr [2]; iso-Pr [3], iso-Bu [4]; t-Bu [5]), with various kinds of the catalysts was tried and the influence of steric bulkiness of alkyl group and the effect of catalysts were investigated. These data are shown in Table 2.
From these results, it was found that the migratory aptitudes of alkyl group in this reaction depend on the steric effect of alkyl group and the catalyst. In the cases of thionyl chloride and formic acid as the catalyst, only N-alkyl acetamides were yielded. On the other hand, when borontrifluoride-acetic acid complex was used, the migratory aptitudes were considerably deviated from the ratios of anti-alkyl form/syn-alkyl form of aliphatic ketone oximes in benzene (A1) or DMSO (A2) (see Table 1). In other cases, they nearly approach to Al or A2. This demonstrates that these catalysts are inactive for isomerization of the oximes during the reaction.

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The reaction of N-(ethoxycarbonyl)phthalimide (ECPI) with aniline was investigated. Two new reaction intermediates, N-ethoxycarbonyl-N'-phenylphthalamide (ring-opening adduct [1]) and 1-ethoxycarbonylamino-1-hydroxy-2-phenylisoindoline-3-one (isoindolone [2]), were isolated as stable compounds. These intermediates [1] and [2] were converted into N-phenylphthalimide [3] in a quantitative yield with the elimination of urethane at 150-480° C. The reaction of ECPI with aniline was markedly influenced by the temperature and the catalyst. In the neutral solution of tetrahydrofuran, the reaction gave [1] or [3] at room temperature or at a temperture above 60° C, respectively. In the presence of basic catalyst such as triethylamine and aqueous sodium carbonate, the reaction yielded the imide (3) selectively, whereas the iso- indolone (2) was obtained in the presence of such an acidic catalyst as aqueous acetic acid. From these results, it may be concluded that the reaction gives first the ring-opening adduct [1], which is subsequently isomerized to the isoindolone [2] and the latter compound [2] is finally converted into N-phenylphthalimide [3] with the elimination of urethane.

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For the purpose of obtaining good boundary-lubricating silicone oils, thirteen monomers containing fluorine were prepared. These were (fluoroaryl)methyldiethoxysilanes in which fluoroaryl groups were as follows: o-, m-, and p-fluorophenyl; o-, m-, and p-(trifluoromethyl)phenyl; 4- fluoro-3-, 2-fluoro-4-, and 4-fluoro-2-(trifluoromethyl)phenyl; 3, 4- and 3, 5-difluorophenyl; 3, 5- bis(trifluoromethyl)phenyl; and 4-(heptafluoroisopropyl)phenyl.
Preparations were carried out applying the Grignard reaction between methyldiethoxychlorosilane and corresponding fluoroarylmagnesium bromide or. iodide. The preparative methods for various fluorinated and fluoroalkylated bromo- and iodobenzenes which were used as starting material, were also described.

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The reaction of bis[4-(p-substituted anilino)-3-penten-2-onato]copper(II) [1] with benzoyl chloride has been investigated. The substituents are a: H, b: CHc: OCH8, and d: Cl. [1] reacted with benzoyl chloride(2.1 molar to C/D) in benzene at 20-25° C for 1-4.5 hours to give 3-benzoyl-4-p-substituted anilino-3-penten-2-one [2] (63-66% yield), 4'-substituted benzanilide [3] (trace), 3-chloro-4-p-substituted anilino-3-penten-2-one [4] (5'9%), and cuprous chloride. In the presence of pyridine (2.0 molar), the reaction of [1 a] or [1 c] with benzoyl chloride gave [2 a] or [2 c] in 82-L/85% yield and trace of [3 a] or [3c] together with dichlorobis (pyridine)copper [1] in place of cuprous chloride. The reaction of [1 c] with cupric chloride (2.1 molar) gave [4 c] in 10% yield and cuprous chloride. A mechanism for the reaction of [1] with benzoyl chloride is discussed.

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In order to make a detailed investigation on the hydrogenolysis of Hokkaido coals which have their special characteristics in the initial steps of the reaction, a batch autoclave study was made on the kinetics of the hydrogenolysis of seven Hokkaido coals of different ranks. The reaction rate was measured under rate controlling reaction conditions. The difference in coal hydrogenolysis reactivity was investigated quantitatively in relation to the various structural indices of the sample coals.
It was concluded that (1) the hydrogenolysis reaction of seven Hokkaido coals consisted of two steps: the rate of reaction in the first step was high while in the second step was low, and both reactions are of a first order with respect to coal remaining, (2) the reaction occurred for seven Hokkaido coals may be represented schematically as follows:
Coal Oil(S1) Asphaltene Oil(S₂)
(3) the rate constants of reaction in the first step decrease with increasing rank of coals, and are closely correlated with classification parameters (related to thermal reaction) such as fixed carbon content, volatile matter content and fuel ratio; on the other hand, the rate constants of the reaction in the second step may be considered to be correlated with the ether-oxygenbond in the remaining coal sample after removal of the constituents appeared in the reaction of the first step, and are not correlated with the rank of coals.

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In order to discuss the reaction process of coals treated with hydrogen, coal samples of Oyubari coal(C: 85.6%) and Taiheiy6 coal(C: 76.9%) were treated with hydrogen under mild conditions to avoid extensive degradation of the structural units. The changes in the chemical structure of benzene-solubles with changes of reaction temperature and reaction time were studied by high resolution nuclear magnetic resonance spectroscopy and elementary analysis. In addition, the chemical structure of the original coal substance was discussed on the basis of these results.
As a results, it was concluded that in the initial step of hydrogen treatment up to ca.20 wt% conversion, the size of aromatic rings in the structural units of benzene-solubles became gradually larger, and the internal surface area of benzene-insoluble g also increased with progressing conversion. From these results, in this particular step it was concluded that a part of the coal substance, in which an uneven distribbtion of aromatic rings was seen in the structural units, became benzene-solubles by distillation or decomposition. In the reaction process more than 20 wt% conversion, reaction products passed through the plastic state, and the internal surface area of benzene-insolubles decreased with progressing conversion. The size of aromatic rings in the structural units of benzene-solubles was nearly constant in spite of the progress of con- version. From these results, it was concluded that there was but a limited distribution of aromatic rings in the structural units of coal substance related to this reaction step.
From these results, it was demonstrated experimentally that the uneven distribution of aromatic rings in the structural units of coal was small in sub-bituminous coal (Taiheiy6 coal) and large in bituminous coal (Oyubari coal).

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The objective of this investigation was to determine the feasibility of ion flotation for the selective removal of Pb(II) from dilute aqueous solution, using the monoalkyl phosphates(AP). All the experiments were carried out in a cylindrical column, 42 cm in height and 6.5 cm in diameter (Fig.1).
The maximum degree of elimination of metal ion in dilute aqueous solution occurred at high pH(about 8-10), whereas he high degree of selectivity occurred at low pH (near 4) (Fig.6-10). From the acid aqueous solution containing Zn(II), Cd(II), Cu(II), Ca(II) and Pb(II), Pb(II). could be floated by sodium monostearyl phosphate, leaving the other cations in solution (Fig.14, 15). The scum(AP-metal complex) was normally prepared in 1: 1 molar ratio of AP: M, (II)(M: metal) at pH 4, (Fig.11, 12). By treatment with mineral acid, 95% of the AP and Trital ion were recovered from the scum. The order of stability of these AP-metal complexes was as follows: Pb>Zn>Cd>Cu>Ca (Fig.16).

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Fluorescent brightening agents, 1, 2-bis 5-methylbenzoxazolypethylene and its derivatives, are dimerized by uv light both in solution and in polymer film. With increase in concentration, the rate of the fading of the dye increases to a certain limit and then decreases. This tendency is more pronounced in polymer film, such as cellulose diacetate and polypropylene, than in ethanol and benzene solutions.
In this paper, behaviors of fading of the dye in solution and polymer film are discussed from the chemical kinetic point of view.
If diffusion of the dye is assumed to be restricted strongly in polymer film, rate of fading of the dye molecule will decrease with increasing distance from the irradiating surface. A rate law of fading under restricted diffusion is constructed and solved by assuming several initial conditions.
The calculations, however, show that restricted diffusion has no effect on the overall decay of the dye (Table 2).
Another rate law (equation (10)), constructed by assuming the retardation effect, can not afford a reasonable explanation of the observed decay curves.
On the other hand, the experimental results in solution and polymer film appear to be accommodated by considering the simultanious trans-cis photoisomerization and photodimerization, if steady state approximation for concentration of cis-isomer is assumed (Table 4). The decay in cellulose diacetate film is explained by assuming that the photoreaction proceeds in two phases: the one is discrete dispersion and the other assembly phase, and that considerable amount of the dye molecule is restrained in the former phase.
The kinetic parameters in solution and in polymer film are compared and discussed (Table 3).

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The interaction of poly(vinylpyrrolidone)(PVP) with amino acids and with their related compounds was studied by the measurement of the intrinsic viscosity, Pa of aqueous solution of PVP and by the determination of the amount, x, of amino acid bound to PVP per monomer unit using membrane equilibrium technique.
It was found that amino acid having both hydrophobic and hydrophilic groups, such as tryptophan (Try), combined with PVP to raise the [77] of the polymer (Fig.4). Notwithstanding the x of HCl-salt of Try. is larger than that of Na-salt, the [7i] of PVP in the latter solution is larger than that in the former, as shown in Fig.11. On the contrary, it was found that amino acid having polar groups, such as aspartic acid (Asp.) and glutamic acid (Glu), and their related compounds reduced the [V] of PVP and allowed to salt out the polymer, as shown in Figs.7 and 8. Dehydration of PVP by means of polar groups found in Asp. and Glu. became stronger as the neutralization with NaOH proceeded. The a, co dicarboxylic acids were found to have the same behavior as above which are shown in Fig.9. This effect was strengthened with the number of OH groups, e. g., in the order of succinic acid, malic acid and tartaric acid, as shown in Fig.7. Salting out effect was strongest for sodium oxalate, and this effect became weaker with increasing number of carbon atoms, n, in a hydrocarbon chain. The salts, whose n is larger than that of disodium azelaiate, raised the [77] of PVP as shown in Figs.9 and 10. The [n] of PVP became larger in the solution of monocarboxylic acid than in pure water, when chain length is larger than sodium valeriate. It was, therefore, concluded that cosolutes having a chain shorter than 3.5 units of methylene group per carboxyl group brought about shrinkage of polymer coil by dehydration and reduced the [77], but cosolutes having longer chain than the above raised the [77] because the cosolute combined with PVP and consequently the expansion of polymer coil occurred.

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Polyamides were prepared by the ring-opening polyaddition reaction of N, N'-bis(ethoxycarbonyl)pyromellitimide with bis(4-aininophenyl) ether (ODA) and other aromatic diamines in N-methyl-2-pyrrolidone (NMP). The preparation of high molecular weight polymer required high monomer concentration and a longer reaction time such as over 5 days at room temperature. When the reaction temperature was raised to 70° C, gelation was occurred due to the partial imidization of the resulting polyamide, along with the increase of the rate of polymerization. The polyamide having the highest viscosity was obtained from ODA among the aromatic diamines. Tetrahydrofuran was not satisfactory as reaction medium, because the polymer was precipitated from the reaction mixture during the polymerization. The polyamide solution in NMP showed good hydrolytic stability against the contact of water. DTA curve of the polyamide exhibited an endothermic peak at 160° C, which is attributable to elimination of urethane during polyimide formation. The behavior was also supported by TGA.

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Poly(hydrazino-1, 3, 5-triazines) were prepared by the meltpolymerization of 2, 4-dihydrazino-6- substituted (R')-1, 3, 5-triazines (R' =amino, dimethylamino, diethylamino, dipropylamino, dibuthylamino, methyl, phenyl) with 2, 4-diphenoxy-6-(N, N-disubstituted)amino (R2N-)-1, 3, 5-triazine(R= hydrogen, methyl, ethyl, propyl, buthyl). The intrinsic viscosities of the poly-hydrazino-1, 3, 5- triazines in formic acid at 30° C, ranged from 0.07-0.73 dug, except for the polymer which have the amino, group in 1, 3, 5-triazine ring. The intrinsic viscosities of the latter ranged from 0.01-0.06 dg. The lower value was considered to be due to 2-amino-4, 6-dihydrazino-or-diphenoxytriazine unit which contains three functional groups. The poly(hydrazino-1, 3, 5-triazines) were soluble in formic acid, acetic acid, sulfulic acid, nitric acid, hydrochloric acid, and ethylene chlorhydrin, but were insoluble in m-cresol and dipolar aprotic solvents. Polymers which have the amino or methyl group in 1, 3, 5-triazine ring showed poor solubility. The thermal stability of the polymers were measured in nitrogen by thermogravimetrie analysis and differential thermal analysis, and were found to decompose at 310-s340° C. IR spectra of model compounds i. e.2- (N, N-dimethylamino)-4, 6- (3, 5-bis(N, N-diethylamino)-2, 4, 6-triazinyl hydrazino) -1, 3, 5-triazine mp 1O^2-4O^2-° C, and 2-(N, N-dimethylamino)-4, 6-3, 5-bis(N, N-dimethylamino)-2, 4, 6-tria. zinyl hydrazino -1, 3, 5-triazine mp 142-144° C, were compared with those of the corresponding polymers. Their chemical structures were determined by NMR spectra.

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Radical copolymerizations of p-substituted phenyl allyl ethers and sulfides with acrylonitrile (M1) have been investigated. Plots of log 1/r, against a values gave the following results: p= -0.35 for phenyl allyl ethers and p=0.17 for phenyl allyl sulfides. Meanwhile, the Hammett p values for the chain transfer reaction of these ethers and sulfides toward polystyryl radical were calculated to be 1.28 and 0.08, respectively. From the results obtained, the nature of the transition states of the propagation and the chain transfer reactions are discussed.

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Kinetics of the copolymerization between the two diallyl esters of dicarboxylic acids are discussed in terms of cyclocopolymerization.
The copolymer composition equations are first derived from the extension of the kinetics of cyclocopolymerization, involving the copolymerizations of diallyl esters with monovinyl monomers2.
Next, they are applied to the copolymerizations of diallyl phthalate with diallyl isophtalate, diallyl terephthalate, and diallyl oxalate, and their results are discussed from the following stand- points, i. e., (i) evaluation of each rate constant ratio of elementary reaction by the use of the least square method, and (ii) check of the results obtained from the homopolymerizations or the copolymerizations of diallyl esters with monovinyl monomers.

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The vapor-phase graft-polymerization of methyl methacrylate onto poly(propylene) fibers was studied by a T-ray simultaneous irradiation technique and the weight increase during the reaction was followed by a spring balance. The sorption of methyl methacrylate onto poly(propylene) fibers approached to the apparent equilibrium after 60 to 180 minutes from the introduction of the vapor and the equilibrium sorption was lowered with rising the temperature. The sorption was augmented with the increase in the extent of grafting. The rate of weight increase of fibers due to the grafting reaction became larger with rising the reaction temperature, the vapor pressure of monomer and the irradiation dose rate. The grafting proceeded linearly with the irradiation time when the vapor pressure of monomer was low, but the acceleration was observed when the vapor pressure of monomer was high. The grafted fibers contained the large amount of the occluded homopolymer. The grafting reaction process, and the dependency of the rate of grafting on the temperature, vapor pressure, and dose-rate were well explained by taking into account of the increase in sorption caused with the increase in the extent of grafting.

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The Graft-copolymerization of methyl methacrylate (MMA) onto silk by tri-butylborane (TBB) was investigated in aqueous medium. It was found that the polymerization of MMA was accelerated in the presence of silk and the graft copolymer was obtained, while no grafting occurred in the absence of water. With rising temperature the rate of polymerization increased and the efficiency of grafting decreased. Both the percentage of grafting and the molecular weight of the polymer increased with increasing amount of silk. And also the percentage of grafting and the efficiency of grafting were increased by the pretreatment of basic amino acids. Glycidyl methacrylate and 2-hydroxyethyl methacrylate were also grafted onto silk, while no grafting was observed with other vinyl monomers. Amino acid analysis of hydrolysis products and their electron microscopic observation were made on the graft copolymers. On the basis of these results, the mechanism of grafting is discussed.

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The graft-copolymerization of N-vinyl phthalimide and N-vinyl succinimide toward preir radiated polyethylene film and the preparation of anion-exchange membranes from the resulting graft-copolymers were investigated.
Yukalon film (Mitsubishi Petrochemical Co. Ltd., thickness 0.05 mm) of high pressure poly ethylene was used and irradiated with T-rays from a cobalt-60 source to a total dose of 10.5 Mr in an air at room temperature.
The graft-copolymerization toward preirradiated polyethylene. film was carried out under several conditions and results are as follows: (1) The grafting was not influenced in the range from 3 to 45 days by the storage time of preirradiated polyethylene film. (2) The effect of atmosphere on the graft-copolymerization was large and the grafting remarkably reduced by the presence of air. (3) The influence of polymerization temperature was also large and the maximum grafting was obtained at 110° C.
Anion-exchange membranes were prepared by the hydrazinolysis of the resulting graft' copolymers, and the preparation and characteristics of the anion-exchange membranes thus ob tained were tested by the infrared absorption spectrum as shown in Figure 6 and some electro chemical data obtained are shown in Table 2.

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Formation constants for the complexes of poly(vinyl alcohol) (PVA) with bivalent transition metal ions, i. e. Co(II), Ni(II), Cu(II) and Zn(II) were measured by using the modified Bjerrum's method proposed by Gregor and co-workers in an aqueous solution of ion strength 0.1 at 25° C. The formation curves for Cu(II) and Zn(II) complexes showed that the each metal ion was coordinated by four hydroxyl groups involved PVA, while Co(II) and Ni(II)ion were coordi- nated by four above hydroxy groups (Fig.2). The stability constants, log k1, log k2 and log K increase in the order of Co(II)<Ni(II)<Zn(II)<Cu(II) in agreement with the Irving-Williams series for stability constants (Table 1). Thermodynamic parameters for the above reaction were determined by the Ringbom's method.

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The curing of epoxy resins with boron trifluoride-amine complexes (BFs-AC) or tetrafluoroborate-amine salts (BF, -AS) was studied by means of DTA.
The DTA thermogram showed, two exothermic peaks for BF, -AC and one peak for BF, -AS. The temperature Of the peak of higher temperature side for BF8-AC was almost the same as that of the peak for BF, -AS.
On the basis of the analysis made by IR and nitron-acetate methods, BF, -AC was found to react with equimolecular amounts of epoxy group, giving BF, -AS at the temperature of the peak of lower temperature side.
From these results, we suggest that BF3-AC reacts with epoxy resin in the BF3-AC-epoxy resin system to produce BF, -AS before curing, and the "true catalyst" of the curing for both 13F3-AC and BF, -AS systems would be the hydrogen atom located on the amine nitrogen in BF, -AS.

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In some solid particles/gas systems, reaction occurs first on the outer skin of each particle. The reaction zone then goes into each solid, leaving behind both converted and inert materials. This paper deals theoretically with the reaction time in such systems, where, the concentration of reactants is again made uniform throughout the particles in an arbitrary instant in the reaction process. The log-normal size distribution was assumed for these particles. The mathematical expressions for the reaction time were derived from the unreacted-core model. Digital computations were performed for the value of (ti-Ft2)jr, which was the total time needed to reach a given conversion F by the two reaction operations before and after the homogenization of all the particles. The value of (ti-Ft2)1I- was illustrated as a function of FIT in the Figures shown in the paper.
The value of (tr-F t2)ir when FfT*FiT was found less than or equal to that of (ti-Ft2)1s- when FfT=F1T. This fact suggests that the shortening of the reaction time is expected by homogenization.
The minimal value of (ti+ t2)/s- for an arbitrary, large F f7: decreased with increasing a in the range of a0.2. The double operation with the homogenization process in mid course was, therefore, more effective for shortening of the reaction time, as the extent of the size distribution of the particles increased within this range. This operation was, however, of little or no use in the system where the gas-film-diffusion controlled the rate of reaction in each particle (Case I) and whose a was near or equal to zero. It did not be applied in the system where no large FIT was required.
In order to complete the reaction quickly or to allow it to arrive at FIT (F1T<ca.1) in the shortest time, it is generally recommended to consume a half of the total reaction time in the first process.

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Solubility and tie-line equilibria are observed for the system 2-propanol-Water-aluminum sulfate at 5, 15, 25, 35° C. And crystal structure of aluminum sulfate in a state of equilibrium is investigated. Effect of temperature on the phase diagrams is very small. When the weight fraction of water in the mixed solvent is in the range from ca.0.941 to ca.0.811, the solubility of aluminum sulfate decreases with rise of temperature (Fig.3 and Fig.4)
Several methods of tie-line estimation in the literature are examined. The method proposed by Hand gave straight lines (Fig.5). But these lines are different in various temperatures. The method proposed by Nakamura also gave straight lines which were independent of temperature (Fig.6). Besides these, the method proposed by Major and Swenson is acceptable. The other method gave curved lines. Log plot of XB/Xc against XB/XA gaves straight lines. In the case of liquid-liquid equilibrium with solid phase (Table 1), the theoretical ratio of solvent to excess water is obtained by the solvent addition crystallization method. This method gives lower ratio with fall of temperature (Fig.8). The real ratio of solvent to excess water will be larger than the theoretical one.

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Hexachlororhodate0n, hexachloroosmate(N), hexachlororuthenate(V), and hexacl: iloroplatinate (N) decreased both surface and internal speeds of silver bromide emulsions, and increased surface speeds of silver iodobromide emulsions, although they decreased the internal speeds of the silver iodobromide emulsions, when they were added to the emulsions before coating. The degree of sensitization increased and that of desensitization decreased with the increasing ratio of internal/ surface speed of primitive emulsions: These results are consistent with the idea that the complex ions act as electron traps at the grain surface which are not necessarily efficient for latent image formation, since the surface speed is low owing to the capture of photoelectrons by internal sites in the case of grains with high ratio of internal/surface speed.

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I₃Sn-Mn(CO)₅ has been synthesized bythe reacti, n, fCl3Sn-Mn(CO)5 withNalinTHF, The IR and lase rRaman spectra of I₃Sn-Mn(CO)₅ have been measured, A linear relationship between the Sn-Mn stretching wave number and the electronegativity of X was observed for a series of X8Sa-Mn(CQ)6 compounds(X=Cl, Br, andI), An efect of X on the Sn-Mn bonding nature was discussed based on the CO and MnC stretching frequencies.

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Selenocyanate ion in a neutral supporting electrolyte (such as potassium nitrate) was titrated with a silver nitrate solution by the use of short-circuit amperometry using a rotating platinum wire electrode (1000 rpm) as an indicator electrode and SCE as a reference electrode.
It was found that selenocyanate ion could be titrated at the concentration range of 0.01, 0.00001 moll and a 0.001 molg selenocyanate solution was titrated most precisely with the relative error and the coefficient of variation of less than 0.1%.
A method for the determination of a mixture of selenocyanate and cyanide ions was as follows: The sum of selenocydnate and cyanide was titrated similarly for an aliquot of the sample solution. Another aliquot of the same solution was titrated to the end point of seleno- cyanate after masking cyanide ion with excess formalin and adjusting the pH to 6 with the dilute nitric acid.

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The determination of cadmium in unpolished rice has been made by an atomic absorption spectrophotometric method. This work involved the extraction of cadmium with n-butyl acetate solution of dithizone and the measurements of absorbances of the extract.
The trace amounts of cadmium in unpolished rice ranging from 0.07 to 0.19 ppm was determined with satisfactory reproducibility and without interferences with other heavy metals. The recommended procedures are as follows: The test solution is taken into a separating funnel together with 5 m/ of acetate buffer solution (pH 5.3) and 10 ml n-butyl acetate solution of dithizone solution is added. The extract is sprayed into the flame of an atomic absorption spectrometer. For example, the standard deviation was 0.0O36 for the mean absorbance of 0.426 during 5 runs, the coefficient of variation being 0.8%.

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The acid catalyzed ring opening of trans-stilbene oxide was investigated in DMSO, DMF, THF, and dioxane and the products, meso and dl-hydrobenzoins and diphenylacetaldehyde, were determined. In the solvents of high polarity, inversion of configuration was observed in most products, and the opposite was true in the solvents of low polarity. There was no direct relation between rearrangement products and polarity of solvents.

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The reactions of resorcinol with isoprene gave prenylresorcinols ([1] and [2]), 2, 2-dimethylhydroxychromans ([3] and [4]), 2, 2-dimethylhydroxyprenylchromans ([5] and [6]) and dichromans ([7] and [8]). The fair amounts of the products in which the prenyl group was attached to 2-position of resorcinol were obtained under suitable conditions.
On the basis of the results under various reaction conditions, the reaction schemes were discussed.
The dehydrogenation of compound [8] with DDQ(dichlorodicyanobenzoquinone) gave chromene [9] and dichromene [10].

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γ-Induced addition of dimethyl, diethyl, and di-n-propyl phosphites to vinyl acetate yielded the 1: 1 and 1: 2 adducts. Similar addition of dimethyl phosphite to allyl acetate gave the 1: 1 adduct. Dimethyl 2-acetoxyethylphosphite and dimethyl 3-acetoxypropylphosphite thus obtained as the 1: 1 adducts were pyrolyzed to yield dimethyl vinylphosphite and dimethyl allylphosphite, respectively. However, diethyl and di-n-propyl 2-acetoxyethylphosphites gave complicated pyrolytic products, ethylene and propylene, respectively, besides acetic acid.

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Photodegradation of 4, 4'-bis(1, 3, 5-triazin-2-ylamino) stilbene-2, 2'-disulfonate derivatives was studied both optically and chromatographically.
The results are as follows.1) The trans-form of each derivative is isomerized to the cis-form in ca.70% yield by irradiation of UV-light (>300 nm). A trans-cis equilibrium is established.2) The CF-plots in these photo-degradation have positive slope.3) Through prolonged irradiation of UV-light, each equilibrium mixture (probably the cis-form is responsible) is degraded gradually to NH₃, SO₄2-, HS0, -, CO₃2-, and organic acid residues, which may suggest complete decomposition of the molecule.

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A new separation and concentration method of traces of Au, Hg, Pt and Pd in silver, copper and lead metals using sulfur as collector is described. One ml of radioactive standard solution and 0.05-3 ml of (NH4)2S solution (Assay (as S): minimum 0.6%)were added to 35 ml of 0-5.5 HNO₃ solution containing 0.5 g (as metal base) of matrix element. Then, sulfur was produced by the following two procedures. (1) Rapid decomposition method: To the solution heated previously, 10-12 ml of conc. HNO₃ was added with stirring. (2) Slow decomposition method: 10-12 ml of conc. HNO₃ was added to the cold solution and the solution was heated with stirring.
The yield was determined by the measurement of r-activity with a 3 95x 3 NaI(T1) or 41 ml GOLD detector coupled to a multi-channel pulse height analyser. Test results: Better recovery and reproducibility were obtained by the former method. Optimum amount of (NH4)2S solution to be added was about 0.5 ml. Presence of excess of HNO₃ and HCl showed the tendency to decrease the concentration factor and recoveries of trace elements.
Au, Hg (in silver, copper and lead) and Pt (in copper) were collected almost quantitatively in sulfur. Recoveries of Pt (in lead) and Pd (in copper and lead) were not quantitative but reasonably high. Recoveries of Ag, Ir, Sb (in silver, copper and lead) and Pd (in silver) were low. Behavior of Hg in silver was interesting, because although Hg did not co-precipitate with Ag2S, it was collected almost quantitatively in sulfur.

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