The Tait equation,
V=V₀[1-Cln{(B+P)/(B+P₀)}]
is introduced for calculating the specific volumes of compressed liquids of halogenated hydrocarbons using the Tait parameters, B and C, which are based on the van der Waals type model. Here, V(cm³·mol^-1) is the molar volume of the liquid under the pressure P(Pa), and V₀(cm³·mol^-1) represents the molar volume of the liquid under the saturated vapor pressure P₀(Pa) at each temperature. The Tait parameters are given by
C=7.52×10⁵⁴μ²/TV₂²+0.0922
B=9.86×10⁸ΔE_b^VV_b⁵(V₀^-6-V_c^-6)-P_c
whereμ(C·m) is the dipole moment, P_c(Pa) the critical pressure, T_c(K) the critical temperature, ΔE_b^V; (kcalmol-1) the energy of vaporization at the normal boiling point, V_b(³·mol^-1) the molar volume of liquid at the normal boiling point, and V_c(³·mol^-1) the critical volume. The correlation of the Tait equation was evaluated the overall absolute average deviation of 0.12% for the 215 data points for seven kinds of halogenated hydrocarbons (CCl₂F₂, CHCl₃, ClCH₂CH₂Cl, CH₃CHCl₂, CHClF₂, CH₂Cl₂, CH₃Cl).

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The formation of neodymium yttrium fluoride oxide and its properties as an oxide ion conducting solid electrolyte were studied by means of the X-ray diffraction and electrochemical methods. Neodymium yttrium fluoride oxides with various compositions were prepared by heating appropriate mixtures of Y₂O₃ and NdF₃ at 1200°C for 2 h in an argon atmosphere (Fig.2). In the solid phase reaction, it was found that the anion exchange reaction between oxide and fluoride took place in the temperature range from 200 to 600°C to give YFO and NdFO, and then both of the simple metal fluoride oxides began to react with each other at about 900°C to produce neodymium yttrium, fluoride oxide (Fig.3). Two homogeneous phases were indentified to be the rhombohedral and the tetragonal neodymium yttrium fluoride oxide (Fig.6). The tetragonal phase was found to have a wide homogeneity composition and it was prepared from the starting mixture containing 58 to 78 mol% NdFa (Fig.7). As stoichiometric compounds, rhombohedral Y₂NdF₃O₃ and YNd2FaO₃ and tetragonal Y₂Nd2F₆O3 were obtained. A transition between the rhombohedral and cubic structures was observed at 530°C for the former two, but the latter was stable up to 1300°C even in air without a transition (Fig.5). The lattice parameters listed in Table 1 showed that the both crystal structures closely resembled the cubic. The electrical conductivity of Y₂Nd2F₆O₃ was measured by the AC method and determined to be 1.2 × 10-2 Scm^-1 at 650°C under a vacuum of 7 × 10^-1 Pa (around 10^-8 atm oxygen)(Fig.8). This value was about one hundred times higher than that of the pressed powder of yttriastabilized zirconia (Fig.11). The oxide ion transport number was calculated to be over O.85 by the oxygen gas concentration cell and electrolysis methods at 650°C (Fig.10 and Fig.12). Neodymium yttrium fluoride oxides wpuld be a useful material for a fuel cell and a sensor as an oxide ion conducting solid electrolyte.

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The ESR spectrum of the nitroxide radical, di-t-butyl nitroxide (DTBN), was investigated in aqueous solutions of the following surfactants: sodium 1, 2-bis(2-ethylhexyloxycarbonyl)ethanesulfonate (AOT), sodium dodecyl sulfate (SDS), sodium tetradecyl sulfate (STS), dodecyltrimethylammonium bromide (DTAB), hexadecyltrimethylammonium bromide (CTAB) and octadecyltrimethylammonium bromide (OTAB). The spectra were recorded as a function of surfactant concentration, temperature and radical concentration. The rotational correlation time and the coupling constant were obtained at 30, 33 and 50°C, in order to obtain some informations about the region of solubilization in the micellar unit. Ab ove the critical micelle concentration (CMC), the DTBN radical associates with micelles and the tumbling rate of the radical reduces as a result of the interactions with micelles. The solubilized DTBN is more associated with the polar surface than with the hydrocarbon portion of the micelles, as stated by others. The surfactants containing long alkyl chains, such as CTAB and OTAB, lead to a large immobilization of the DTBN radical. Moreover, there exhibited the splitting at the high-field line, which could be attributed to the radicals in" aqueous bulk and micellar phases. This is interpreted as reflecting a tighter packing of the composite soap molecules in the micelle. In the CTAB solution, a full resolution of the spectral lines was obtained at 35 GHz (Q-band), in contrast to the ones at 9.5 GHz (X-band). The spectrum was simulated by trial and error method to determine the partition of the DTBN between the two phases and the number of the radicals per smicellar unit. It was concluded that at most one DTBN radical dissolved in a micelle: the radical did not aggregate within a micelle. The line broadening was interpreted as being due to the exchange of the radical between the aqueous and the micellar phases.

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The catalytic reduction of NO with NH₃ at low temperatures around 150°C has been studied over several manganese dioxides derived from various sources of manganese carbonates and other materials. The relations between the catalytic activity and the conditions of the preparation of the catalysts were clarified by such methods as thermal analysis, X-ray diffraction, electron microscopic observation, measurement of surface area, pore volume (mercury porosimetry measurement) and measurement of NO conversion.
The order of the catalytic activity for NO conversion was as follows: Industrial grade pure MnCO₃ (IPM)>Industrial grade MnCO₃ (IM)>Natural Rhodochrosite>Granulated catalyst of calcined IPM>Granulated electrolysis r-MnO₂. The highest catalytic activity was observed with IPM calcined in the air at 350°C. The degree of NO conversion of IPM at 150°C was about 100% under the conditions of NO 500ppm, NH₃ 500 ppm, 02 3%, H₂O 10%, N2 balance, and S. V.5000 h^-1.
Highly active catalysts showed total pore volume of O.2-0.3 ml/g and pore volume of 0.10.2 mug for the particles with radius below 100 Å. In general, an increase in the pore volume (r<100 Å) and surface area, and relatively low degree of crystallinity of r-MnO2formed, led to higher activities. The x values in γ-MnO_x were 1.7-1.8.

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A study was made to prepare amorphous calcium carbonate by drying the gelatinous phase which precipitated from the reaction ofCaO-H₂O-CO₂-CH₃OH system. Formation region of the gelatinous phase, conditions for converting to amorphous phase from the gelatinous phase without any crystallizing and characteristics of the amorphous phase were investigated by means of X-ray diffraction, thermal analysis (TG-DTA), electron microscopic observation, chemical analysis, measurements of specific surface area and solubility.
The gelatinous phase was prepared by passing CO₂ at a flow rate of above 50 cm³/min into the suspensions containing less than 10 g CaO or 5 g Ca(OH)₂ in 100 cm³ of methanol. By rapid drying at 40°C under reduced pressure, the gelatinous phase converted to the amorphous phase. Also the gelation rate was accelerated with increasing flow rate of CO₂ and existence of water below 3 cm3. It seemed that the amount of CO₂ in the amorphous phase (stabilized at 230°C) was more than that of stoichiometric composition of CaCO₃ in order to absorb a small amount of CH₃O- and HCO₃- on the surface of CaCO₃ crystal nucleus. The amorphous phase converted rapidly to calcite by heating above 250°C but was stable under reduced pressure at room temperature over a long time. In comparison with ordinary calcium carbonate, the amorphous calcium carbonate has unique characteristics such as porous ultrafine particles (below 100 Å) and a high activity like converting rapidly to calcite with releasing partial CO₂ in water as a result of hydrolysis.

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The phase diagram of sodium oxalate-ammonium hydrogencarbonate-water system and the double decomposition reaction
Na₂C₂O₄ + 2 NH₄HCO₃ + H2O⇔(NH₄)₂C₂O₄H₂O + 2 NaHCO₃
were studied. The crystal growth of ammonium oxalate monohydrate was also investigated to prepare ammonium oxalate monohydrate from sodium oxalate. Since the carbonation factor z (=OH^-/(OH^-+HCO₃^-)) was held at 0.84-1 during bubbling of carbon dioxide, it was considered that the degree of freedom of the system F is equal to unity. The phase diagram was elucidated under these conditions. The sodium oxalate-ammonium hydrogencarbonate-water system consists of four two-component systems, four three-compoment systems, and two four-component systems. One of the four-component systems is a congruent solution (Table 5, Fig.2). The utility ratio of oxalate (U_C2O4), which is expressed by the molar ratio of ammonium oxalate monohydrate precipitated to sodium oxalate added, was estimated for the four-component systems (Table 8). The maximum U_C2O4 attained 70.3% in the congruent solution at 30°C and it agreed well with the calculated value of 72.4%. The composition of solution and the stirring speed affected the crystal growth during the double decomposition reaction in the four-component systems (Table 9, Fig.3). An increase in the adding rate of feeds caused an increase in the number of spontaneous nuclei, resulting in the formation of small crystals (Table 10). Good separation was attained with a dried mixture and the content of sodium hydrogencarbonate in the ammonium oxalate monohydrate part decreased to about 10 wt%.

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The thermal decomposition of ammonium oxalate monohydrate has been investigated to produce oxamide used as a slow releasing fertilizer. Ammonium oxalate monohydrate is obtainable by the double decomposition of sodium oxalate and ammonium hydrogencarbonate. Powder samples prepared by mixing a certain amount of ammonium oxalate monohydrate with various amounts of phosphoric acid and/or, sodium hydrogencarbonate were placed in 50 cm' beakers covered with a watch glass and heated in a drying oven at 170-200°C for 1-6 h. The yields were increased from 30-35% to 68-78% in the presence of phosphorus(V)oxoacids or their salts and almost independent of the kinds of compounds (Table 1). Sodium hydrogencarbonate interfered the formation of oxamide, but in the presence of phosphoric acid the yields of oxamide were equal to those in the thermal decomposition without sodium hydrogencarbonate (Fig.4). In ammonia stream, the maximum yield reached 86.4% (Table 2). The optimum size was 32-48 mesh and the yield was 83.5% (Table 3). Phosphorus(V)oxoacids may behave as acid catalysts in the thermal dehydration because the yield increased in the presence of sulfates, heteropolyacids, or oxides (Table 4). The TG-DTA study revealed that the dehydration took place at lower temperatures than the decomposition of ammonium oxalate in the presence of catalyst (Fig.6).

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Tetraethoxysilane was allowed to react with 2, 2′-dihydroxyazobenzene derivatives in the presence of sodium or sodium ethoxide using Diglyme as a solvent to prepare chelate complexes of silicon in good yields.

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We have previously reported the effects of powder reductants (e. g., carbon black and sulfur) on flameless atomic absorption spectrometry of beryllium.
This report deals with the direct determination of beryllium oxide and the atomizing effect in flameless atomic absorption spectrometry using a graphite furnace in the presence of carbon black.
Beryllium oxide was ground to a powder (about 0.25-0.5 μm in particle size) with a titanium carbide mortar. The sample, a mixture of the powder and the carbon black, was di spersed in water by an ultrasonic agitator. The sample solution was taken 10 μl and directly introduced into the graphite furnace.
As the result, the dispersed sample solution exhibited absorption peak of 3 or 4 times higher than the standard solution in the same concentration. The addition of carbon black led to a stable dispersibility of the oxide and a reduced interference due to coexisting metal oxides. It was found that the effective amount of carbon black was about 1-2%.
It seems that the variation of sensitivity in the electric atomizing method is due to evapora tion- and volatilization-loss of salts in ashing, and the enhancement of absorption is controlled by the formation of heat-resistant substance such as metal oxide or metal carbide.
The sensitivity of beryllium oxide was O.52 ng/1% abs., and the coefficient of variation was 2.9% for the direct atomization of the oxide containing 5 ppb beryllium.

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The behavior of ion-exchange equilibrium of complex ions in the Fe³⁺-Cl^- and UO₂²⁺systems, particularly the average charge of complex ions within an ion exchanger has been investigated. During the ion-exchange equilibrium between the complex ions, the average charge will vary with the ligand concentration. Accordingly, in the first place, the ν-K correlation formula is derived for determinations of the average charge ( ν ) and the selectivity coefficient (K), and by substitution of the equilibrium concentration values at several points with different metal ion concentrations, a locus is drawn on the v-K plane and its crossing point is determined.
As the result, at Cl concentrations in the range of 3 to 8 mol. dm-3 at which Cl ions act as ligands for Fe+ and UO₂²⁺, the average charges of Cl complexes of Fe+ and UO₂²⁺ were found to be increased with an increase in the Cl concentration, namely changed from 1.3 to 2.0 valent for Fe³⁺ and from 2.0 to 3.6 valent for UO₂²⁺. These changes were much larger than the increases in the average charge of complex ions in solution. Also, for checking the validity of ν and K to be determined, measurements and investigations of v and K were conducted in a system in which complex formation is difficult, and the ionexchange absorption isotherm curve calculated from ν and K values determined was compared with the points measured.

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A highly sensitive and selective method for the determination of halocarbons, such as trihalomethanes, carbon tetrachloride, tri- and tetrachloroethylene, in drinking waters have been developed by gas chromatography mass spectrometry (GC/MS) using negative ion chemical ionization (NCI). Head space method was used for sample preparation, and 0.1 to 1 ml of head space gas was introduced into a GC/MS equipped with a DC-550 2 m-column. Methane was used as a reagent gas. The ionization chamber! pressure and ion source temperature were 0.2 Tort and 250°C, respectively. The mass fragmentograms were recorded at m/z 35(C17) and 79(Br-). These halide ions are generated effectively from halocarbons, and each component in ppt-level can be determined by using 1, 1, 1, 2-tetrachloroetfane as an internal standard. Results obtained by the proposed method were in fair agreement with those by GC-ECD. The determination limits of halocarbons were about 1-100 ppt with relative standard deviations of 2-10%.

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In order to examine the chemical structure of "sodium formaldehyde sulfoxylate" (Rongalite, NaHSO₂HCHO₁ H₂O), the IR and Raman spectra of the compound and the structurally related compounds such as sodium alkane(C₁-C₂)sulfonates, sodium aminometha. nesulfonate, sodium hydroxymethanesulfonate, sodium ethanesulfinate and sodium 1-propanesulfinate were measured in solid states and aqueous solutions (in the case of Raman spectroscopy).
A characteristic vibrational frequency table was made up for the SO2 symmetric and the C-S stretching vibrations from the obtained spectra. It was shown that the Raman spectra of sulfonates exhibited the strong bands attributable to the SO2 symmetric and C-S stretching in the 1080-1020 cm^-1 and 800-720 cm^-1 regions, respectively. In the case of sulfinates, the Raman bands corresponding to the above-mentioned vibrations were observed at lower wavenumbers; the SO2 stretching in the 990-950 cm^-1 and the C-S stretching in 720-650cm^-1 regions. "Sodium formaldehyde sulfoxylate" exhibited the strong bands at 995 and 727 cm-' due to the two vibrations in question. Thus, the results obtained here strongly suggest that "sodium formaldehyde sulfoxylate" has the sodium hydroxymethanesulfinate structure HO-CH₂-SO₂Na having the C-S linkage both in the solid states and aqueous solutions:

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Treatment of anthrone and 1-hydroxyanthrone with tris(dialkylamino)phosphines at 140°C for several days gave bis(9-anthryloxy) (dimethylamino)phosphine and 2-(dialkylamino)anthra [1, 9-de] [1, 3, 2]dioxaphosphorin, respectively. Similar reactions of anthrone with trialkyl phosphites yielded 9-alkoxyanthracenes and dialkyl phosphonates. Reactions of anthrone with tris(alkylthio)phosphines at 120°C for 2 days gave unexpected anthracene and 9-(alkylthio)anthracenes in good yield.

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Anthraquinones which have the hydroxyl, acetoxyl, methoxyl and amino groups at 1, 4-positions were reduced by granulated tin-hydrochloric acid (method A), tin (II) chloridehydrochloric acid (method B), zinc dust-hydrocholoric acid (method C), lithium aluminum hydride in THF (method D), sodium borohydride in methanol (method E) and sodium dithionite-sodium hydroxide (method F) under standard conditions. Reduction of 1, 4dihydroxyanthraquinone (quinizarin) with the method A, B, or C gave 9, 10-dihydroxy-1, 2, 3, 4-tetrahydro-1, 4-anthracenedione(leucoquinizarin), and reduction with the method D, E, or F gave 1, 4-anthracenedione. Reduction of 1, 4-diacetoxyanthraquinone with the method A, B, C, or F yielded leucoquinizarin, and the method D or E gave 1, 4-anthracenedione.1, 4-Dimethoxyanthraquinone gave leucoquinizarin by reduction with the method A, B, or C, but reduction with the method D, E, or F yielded 9, 10-dihydro-1, 4-dimethoxy-9, 10anthracenediol, 1, 4-dimethoxyanthrone, and 1, 4-dimethoxyanthracene. Reduction of 1amino-4-hydroxyanthraquinone with the method A or B gave leucoquinizarin with a small amount of quinizarin, and the method C and E gave 9, 10-dihydroxy-1, 2, 3, 4-tetrahydro-1anthracenone, respectively. The method D yeilded 1-amino-4-hydroxyanthrone. Leucoquinizarin was obtained by the reduction of 1, 4-diaminoanthraquinone with the method A, B, or F but method C and E yielded 9, 10-dihydroxy-1, 2, 3, 4-tetrahydro-1-anthracenone and 1, 2, 3, 4-tetrahydroanthraquinone, respectively. In the case of reductions of 1, 2, 4-trihydroxyanthraquinone(purpurin), the method A, B and F eliminated one of the hydroxyl groups and gave both leucoquinizarin and 1, 3-dihydroxyanthrone, and the method C and E yielded 1, 4-anthracenedione along with leucoquinizarin. Reduction of 1, 2, 5, 8-tetrahydroxyanthraquinone(quinalizarin) with the method A, B, or F gave leuco derivative of quinalizarin, and the method D and F gave 5, 6-dihydroxy-1, 4-anthraquinone.

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Three microbial lipases were used to investigate the effect of solid fat index (SFI) of a triglyceride as a substrate on the fatty acid specificity of a lipase at 20°C. According to the increase of SFI, the fatty acid specificity had been developing more clearly, and the specificity almost unchanged in the range of the hydrolysis rate from 10 to 50%.
The linoleate moiety in a substrate was less susceptible to the enzymatic hydrolysis than the oleate moiety.

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The dependence of the concentration (C) on the ultrasonic velocity of polystyrenecyclohexane (PC) solutions, based on the static phase diagram for polymer solutions, was investigated in the frequency range of 1-4 MHz and in the temperature range of 34.6(θ: θtemperature) 57.5°C and the bulk moduli (E) of these solutions were determined. The point of phase transition was determined to be the deviation point from linearity of the ultrasonic velocity in the lower concentration region, which was in agreement with the overlap concentration of the polymer chain suggested by Daoud and Jannik.
Furthermore, the bulk modulus obtained was strongly dependent on the segmental density in the high frequency (MHz) range and the results were represented by the relationship of E-C^1.054 in the Sem i-dilu te region(II).

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Commercial photographic films in which densities of silver halide and thickness of emulsion layers were modified and silver halide particles isolated from the emulsion layer have been developed or printed out under various development conditions. The halo of developed silver, the spouting of developed silver from silver-gelatin envelopes, the swelling and splitting of the envelopes, and the rumples of the envelopes, , etc. have been newly found in the electron microscopic observation and the electron diffraction patterns of those developed silvers have been obtained. From these results it has been clarified that the developed silver having different shapes is in different states of crystallization and that the factors producing various states of crystallization are (1) the relationship between the rate of development depending upon the development conditions and the rate of diffusion of halogenide ions depending upon the structure of the emulsion layers and the intensity of the silver-gelatin envelopes, and (2)the translucent characteristics of the envelopes.

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Optimal conditions and mechanism of removal of ozone from air were investigated with alkaline earth peroxides. Efficiencies of the ozone removal with peroxides(CaO₂, SrO₂ and BaO₂) increased for sample air in high relative humidity. Hydrated peroxides (MgO₂·nH₂O, n≈0.5 and SrOO₂·8 HO₂O) showed very high efficiencies of removal of ozone, and the efficiency was not affected by the humidity. Ozone is considered to be converted to oxygen in the reactions with atomic oxygen and hydrogen, peroxide produced in the reactions between metal peroxide and water. The water molecule of hydrated peroxides is considered to be used for the decomposition of ozone, since hydrated peroxides show high removal rates of ozone over a wide range of humidity.

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In the previous paper, it was elucidated that the samples of Ohya-ishi powder had an effective adsorbability to aqueous Methylene Blue solution and the adsorbability increased with decreasing particle sizes of the samples and drastically decreased with increasing the temperature for heat-treatment.
In this report, causes for these phenomena were investigated. The Ohya-ishi powder was pulverized and classified for preparing the samples with different types of constituent mineral composition. The adsorbability of the samples was determined with ammoniacal nitrogen besides the aqueous Methylene Blue solution, and physicochemical characteristics of the samples such as mineral composition, etc., were determined by means of X-ray diffraction, chemical analysis, and cation exchange capacity, etc.
As the result, the following facts were found:
( 1 ) The samples having large particle sizes, for example, 80 meshes or larger, contained more rock-forming minerals such as a-quartz and labradorite. The Methylene Blue adsorbability of the powder smaller than 80 meshes depended on the iron contained in the samples.
( 2 ) There was no proportional relationship between the absorbability of ammoniacal nitrogen and the iron content of the samples.
( 3 ) With reference to the mineralogical investigation by Sudo el al, Methylene Blue molecules were mainly adsorbed by clay minerals contained in smaller particles.
It seems that the clay minerals swell as a result of adsorption of Methylene Blue molecules into the interlayers, while ammoniacal nitrogen is adsorbed by ion exchange sites on clinoptilolite contained in samples.
Generally, clay minerals are formed at a low temperature and under a low pressure. Therefore, these minerals have low hardness indices and have a tendency to pulverize into small particles. The causes for the phenomena, mentioned in the previous paper, could be interpreted from these mechanisms.

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Chloride ion contained in α-Fe₂O₃ powders has been effectively removed by heating in humid air without any changes in the surface areas of the powders. The Cl^- content in α-Fe₂O₃ decreased to O.10-0.045 wt% by heating at 300-560°C for 1.0 h in the air containing 28 wt% H₂O. The treated α-Fe₂O₃ revealed only a slight change in the specific surface area from 5.2 m2ig to 4.9 m2/g. The electron microscopic observation showed that no considerable sintering between the particles occurred in the calcination process.

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A water-repellent catalyst has been used for the reaction between liquid and gas. In the present paper, the observation was carried out on platinum particles supported on waterrepellent carriers such as poly(tetrafluoroethylene) (PTFE) using an electron microscope. It was impossible to observe the platinum particles smaller than -50Å by an scanning electron microscope(SEM). The platinum particles could be observed by transmission electron microscopic (TEM)examination with a thin film prepared by the ultrathin sectioning meth od. The size of the platinum particles prepared by the colloidal method was smaller than th at prepared by th e hydrogen reduction method.

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The reactions of fifteen alcohols with triphenylphosphine diiodide [1] have been investigated. The substitution of the hydroxyl group of primary saturated alcohols took place to give the corresponding iodides [3], in 64-99% yields, while the reduction of the hydroxyl group occurred in the reaction of a primary unsaturated alcohol, 3-phenyl-2-propen-1-ol, with [1] The reactions of secondary and tertiary saturated alcohols having an active hydrogen on the 8-position with [1] provided the elimination products, alkenes [5], in 61-82% yields. The secondary and tertiary alcohols having no 8-hydrogen gave the corresponding iodides C 3 as intermediates, which were reduced with hydrogen iodide produced, giving alkanes [4] as the final products, in 26-83% yields. The mixtures of [3], [4]and[5], and [4] and [5] were obtained from the reactions of 1-phenylethanol and 1-phenyl-1-propanol, respectively. In the reaction of 1-phenylethanol with [1], the yield of [4] increased at a higher temperature, since conversion from [3] to [4]was accelerated with the rising temperature. The addition of pyridine in the reaction of 1-phenylethanol with [1] decreased the yield of [4], whereas the yield of [5] was increased.

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