Purification methods of tetrabenzo[a, cd, j, inz] perylene (TBP) synthesized from benzanthrone have been tested. Fluorescence characteristics of the purified TBP has been measured for purity tests.
Crude TBP was first treated with maleic anhydride and chloranil, and passed through columns of activated carbon and activated alumina. The TBP was, then, treated with metallic sodium in diethylene glycol, and once again passed through columns of activated carbon and activated re alumina. Further boiling in benzene and recrystallization in xylene for the treated TBP gave highly purified TBP with isoviolanthrene B and violanthrene B of less than 10-7 molimol of TBP.
The highly purified TBP showed fluorescence maxima at 486 nm and shoulders around 520 and 560 nm at room temperature. At temperatures placed in liquid nitrogen, the purified 'TBP had the maxima in the region of 490 to 493 nm and shoulders around 527 nm. Evaporated thin films of the highly purified TBP had fluorescence life from 16.0 to 21.6 ns, while impure TBP had the life from 8.9 to 26.4 ns.

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Reactivity of hydrogen contained in Raney nickel with ethylene was studied by using a tritium tracer. Hydrogen in Raney nickel was previously labeled with tritium and distinguished from hydrogen introduced during the hydrogenation reaction. The reactivity of the contained hydrogen was determined by measurement of the radioactivity of ethane produced in the hydrogenation. Ethylene reacted with hydrogen in Raney nickel for no suppry of hydrogen during the hydrogenation. However, when ethylene was hydrogenated by both hydrogen in Raney nickel and introduced hydrogen, over 99% of the ethylene reacted with the introduced hydrogen and hardly reacted with the contained hydrogen.

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A new thermographic sensor using thermal denaturation of egg albumin has been studied. As the thermal denaturation of solid egg albumin was extremely sensitive (being of 12 th order dependence on it) to the water content of egg albumin', the dry solid egg albumin was not denatured by heating it at 100°C for 3 hours.
It was found that the presence of urea or glycerol in the dry egg albumin brought about the thermal denaturation of egg albumin, and whose activation energy had enough value to keep a long shelf life of the thermographic sensor at usual conditions.
With added urea, the rate of thermal denaturation was of 6.4 th order dependence on the concentration of urea (whose weight ratio to the egg albumin being 0.2∼0.4) at 95°C and the apparent activation energy of the denaturation was 70∼92 kcal/mol. With added glycerol, the rate was of 16 th order dependence on the concentration of glycerol (whose weight ratio to the egg albumin being 0.3∼0.5) at 90°C and the apparent activation energy of the denaturation was 7083 kcal/mol.
The thermographic sensor was made by coating a mixture of egg albumin and such additives (urea or glycerol) onto polyester film. Fine relief image of dyed egg albumin was obtained by flash-exposing (Xe-flash, 2 msec, 3 J/cm²) to the thermographic sensor which contacted with a printed matter, followed by washing and dyeing processes.†Thermographic Sensor using Thermal Denaturation of Egg Albumin.

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For the improvement of the capacity of silver-silver oxide electrode as a positive pole in an alkaline battery, the effect of copper, zinc, yttrium, or tin salt, added to the electrolyte, on the redox behavior of the electrode was, investigated. The following results are obtained
(1) The capacity of the electrode dliring a charge and a discharge increased upon addition of copper, zinc, yttrium, or tin salt. Especially, the addition of yttrium salt was satisfactory. In any electrolyte with or without metallic salts, an intermediate, small maximal wave, occured in the first stage of a charge, did not disapeare and potential retention at the less noble potential than 0 V in the second stage of a discharge did not occur upon addition of any metallic salts.
(2) On the basis of the charge-discharge curves, current-potential curves, and electronmicrophotograph, fine grained crystals of active materials were considered to form by the adsorption of ionic or colloidal particle produced from the added metallic salt during a charge.
(3) The colloidal electrolyte due to yttrium was most satisfactory for the improvement of charge-discharge characteristics of silver-silver oxide electrode.

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A method has been studied of activating carbon catalysts for oxidation of iron(ll) ion in sulfuric, acid solutions by oxygen. Compounds sublimed or decomposed in thermal treatment were coated on the catalysts before their activation. Activated carbon catalysts with high catalytic activity were obtained with the compounds of high subliming or decomposing temperatures. Table 1 shows that the catalytic activity of the catalysts was also affected by the nitrogen content of the compounds coated on activated carbon. Ammonia generated during thermal decomposition increased the catalytic activity. Figs.4, 6, 7 and 8 show that variation in the catalytic activity with activation temperature was related to a change in weight loss of the catalysts on activation and that the variation was not affected either by change in specific surface area of the catalysts or embrace active sites increasing strongly on the weight loss in stream at 900°C.

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A new thermochemical hydrogen production process named "Sb-I-Ca process by modifying the "Sb-I process" previously proposed. The process consists five reaction steps.
4/3 Sb203 + 12→2/3SbI3 Sb204 (4)
2/3 SbI3 Ca0 →CaI2 + 1/3 Sb203 (7 c)
CaI2 + H2O→ Ca0 + 2 HI (6 c)
2 HI → H2 + 12 (2')
Sb204 → Sb203 + 1/2 02 (3')
In the "Sb-I process", a reaction step
1/2 Sb203(s) I2(s) H20(/) 1/2 Sb203 (s) + 2 HI (aq) (1) had been included, which turned out to have drawbacks due to low conversions and side reactions. It was found by preliminary experiments that such drawbacks could successfully be remedied when step (1) was replaced by above steps (4), (7 c), and (6 c). Step (4), a main side reaction of step (1), was found to proceed smoothly at temperatures above some 600 K. However, the produced SbI, could not be hydrolysed to give HI effectively even at 1300 K. So the two-step hydrolysis via reactions (7 c) and (6 c) was invented by introducing calcium compounds as reaction intermediates. As for the intermediates, magnesium and iron compounds whose iodides could be easily hydrolysed at high temperatures were also examined but neither were acceptable for step (7 c), thus leaving only the "Sb-I-Ca process" as an acceptable process.
Discussion was made on thermochemical features of this process.

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Feasibility of the following "Sb-I-Ca process"for the thermochemical. hydrogen production was studied by examining each of its reaction steps.
4/3 Sb208 + 12→2/3 Sb18+Sb204 (1)
2/3 Sb18+ Ca0→CaI2 + 1/3 Sb208 (2)
CaI2+H2O→ Ca0 + 2HI (3)
2 HI→ H2 + 12 (4)
Sb204→ Sb208 + 1/2 02 (5)
Reaction of pulverized diantimony trioxide with gaseous iodine [step (1)] proceeded to completion in about 2 hr at 723 K, and the produced solid diantimony tetraoxide was easily separated from gaseous antimony triiodide. The conversion level of step (2) reached about 75% in in 6 hr at 633 K when equivalent amounts of liquefied antimony triiodide and pulverized calcium oxide were allowed to react. The solid products, calcium iodide and diantimony trioxide, were separated by using the difference of solubilities in water. The reaction of molten, calcium iodide with water vapor [step (3)] was found to proceed smoothly in spite of the unfavorable thermodynamic data, and a 60% conversion of water vapor was attained at 1173 K in a helium gas stream. As to step (4), it is well established that 28% of hydrogen iodide dissociates at equilibrium at 1173 K. For the last step, the decomposition of diantimony tetraoxide was complted within 2 hr at 1273 K in a nitrogen gas stream. Based on these results, a flow sheet for this process was made. Estimation from it gave 30∼40% as an overall efficiency LUNT, (ηLHV)of this process when the recovery of heat was assumed to be 70∼80%.

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The mechanism of the reaction of urea with ammonium amidosulfate to form guanidinium ion upon fusion under an atmospheric pressure has been investigated.
Guanidinium ion(GH⁺) was formed together with sulfate ion at ca.200°C, and the conversion rate of urea to guanidinium ion reached 87% for the reaction of urea with ammonium amidosulfate (molar ratio 1: 4) at 230°C for an hour. On the basis of the infrared spectra of the reaction mixtures and the amount of ammonia evolved during the reaction, any intermediate reaction products such as ammonium ureidosulfate, formed between urea and ammonium amidosulfate, were not detected. Prior to the formation of guanidinium ion, the main reaction, viz., the deammonation of ammonium amidosulfate to form diammonium imidobis (sulfate) occurred.
The reactivity between ammonium amidosulfate and water or ammonium hydrogensulfate was also examined. Ammonium amidosulfate dose not easily hydrolyze even at such a high temperature as 170°C in contrast to diammonium imidobis(sulfate), which readily hydrolyzes at a low temperature. A mixture of ammonium amidosulfate and ammonium hydrogensulfate, both are the hydrolyzed products of diammonium imidobis(sulfate), brought about a rapid exothermic reaction to form diammonium imidobis(sulfate) and ammonium sulfate immediately after it melted at 119°C.
Judging from the experimental results, the reaction paths of the formation of guanidinium ion from urea and ammonium amidosulfate are expressed as follows:
2 NH₄S0₃NH_{2 4} NH(SO₃NH₄)₂ + NH₃
CO (NH₂) NH₂CN + H₃0 (slow)
NH(SO₃NH₄)₂ + H₂0→ NH₄S0₃NH₂ +NH₄HSO4 (fast)
2 NH₄S0₃NH₂+ NH₄HSO4 → NH(SO₃NH₄)₂+ (NH₄)₂SO₄ (fast)
NH₂CN + NH₄+→ GH+ (fast)

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Low temperature deposition of pyrolytic carbon was attempted by the use of three isomers of dichloroethylene and two isomers of trichloroethane as a source. Any source showed higher deposition rate than 2.3 mg/cm². hr at 700°C. The relationships among the deposition conditions, deposition rate, and structure, and properties of the resulting pyrolytic carbon were investigated by using cis-1, 2-dichloroethylene as a source. The deposition began at 500°C and proceeded rapidly with rise in temperature until 900°C. The formation of undesirable by-products such as tar and/or soot also increased with rising temperature. The optimal conditions for the preparation of pyrolytic carbon were as follows: deposition temperature being 700°C, source concentration being 8-19 vol%, and gas flow rate being 460 m//min. Under these conditions the deposition rate was about 60 gm/hr and the amount of by-products was relatively small. The optical microstructures of the pyrolytic carbon changed from columnar to granular type with rise in deposition temperature and with heightening supply rate of a source. The specific gravity, Young's modulus, and specific resistance of pyrolytic carbon were 1.56-4.59, 0.7-1.8 x 106 kg/cm', and 3.0-5.5 X 10^-3ω, respectively; it showed a great adhesion to a surface of.

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Among copper(ll)complexes with salicylic acid, a monomeric, light blue complex, Cu (Hsal)₂H₂0[1] (sal=C₆H₄0000), and a light green one, Cu(sal) H20[3], have already been obtained in an aqueous solution, but conditions for the crystallization of these complexes have not been made clear. The present work was undertaken to clarify what complex species are crystallized out depending upon an initial concentration of copper(II) sulfate and temperature at pH 3.6 and a mole ratio of copper(ll) sulfate to sodium salicylate 1: 2, since the condition for the crystallization was not affected by the mole ratio. Below 50C, the complex [1] was crystallized irrespective of the concentration range of copper(ll), whereas above 50°C the complex [3] was obtained in the concentration of copper(II) above 0.13 mo1-1. In the higher concentrations ranging 0.15∼0.2 mol.l¹-^l Cu(ll) (<50°C), a bluish green complex Cu2 (Hsal)₄[2] was crystallized together with[3]. [2] has never been prepared up to date in an aqueous solution and was found to have a subnormal magnetic moment. Above 50°C a yellowish brown complex Cu(sal)H₂0[4] was obtained for<0.13 mol.l-¹ Cu(ll).[4] had the same formula as that of the complex [3] but was different in color.[4] was a new compound.

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An anhydrous monomer, Cu (Hsal), (sal= C₆H₄OCOO) [5], and a dimer, Cu, (Hsal), [6], have already been obtained by thermal decomposition of Cu (Hsal)₂4H₂O[1] by Inoue, et al. In the present work, formation conditions of [5] and [6] were reexamined in detail. Moreover, thermal decomposition processes of [2], [3] and [4] appearing in the preceding report were also studied by means of derivatography and the products identified by means of IR and reflection spectra, magnetic susceptibility and X-ray diffraction pattern.
[5] and [6] were prepared at the heating rate above 2°C min-1 and below 0.8 C-min', respectively. The products [7] and [9], which were obtained with the respective 1/3 mole of salicylic acid liberating from [5] and [6], were the different monomer species from each other in spite of the same formula. The products C 8 and [10], which were obtained by releasing additional 1/3 mole of salicylic acid from 7 and [9], respectively, were of the same monomer. The product [6] obtained by the thermal decomposition of [1] was identified as C 2 reported in the preceding paper. Anhydrous complexes, [11] and [12], obtained by the thermal decomposition of [3] and [4], were concluded to be different.

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A high speed liquid chromatographic technique was applied to the analysis of xanthene group dyes.
The separation and purification of 13 standard xanthene group dyes including fluorescein and its derivatives substituted with one, two, three and four halogen atoms (Cl, Br and I) were carried out by ion exchange and gelfiltration chromatography from commercial products and synthesized ones. Using these highly purified standard samples, several working conditions for rapid separation and determination of both main and subsidiary dyes, which differ in the substituted numbers of halogen, were found. Excellent separation was obtained by reverse phase chromatography using HITACHI GEL 3011 as column packing matter and methanol con- taining perchloric acid, water and acetonitrile as mobile phase. The reproducibilities and calibration curves of peaks obtained were satisfactory for the determination of xanthene group dyes in practical samples. Moreover, the application of this method to commercial products have brought on interesting informations.

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2-Amino-l-propanethiol (I M) was produced by the reaction either 2-amino-1-methylethyl hydrogensulfate (II E) or 2-aminopropyl hydrogensulfate (I E) with ammonium hydrogensulfide. The structure of the reaction product was identified as I M by comparison of their Rf value of TLC, IR and NMR spectra with those of the authentic sample of I M hydrochloride. The structure was further confirmed by the identity of their oxidation products with bis(2-aminoethyl) disulfide hydrochloride and 2-amino-1-propanesulfonic acid independently prepared.
Intervention of the same intermediate was suggested from the fact that the same product was obtained from both the starting materials, I E and E. Aziridinium ion (MAZ), formed via intramolecular participation of the amino group under elimination of hydrogensulfate from I E or II E, was assumed to be the intermediate and to be submitted to nucleophilic attack of the hydrogensulfide ion on the more electropositive and less hindered methylene carbon of MAZ to afford I M.

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The hydrolyses of phenyl esters catalyzed by telomer-type hydroxamic acids (THA) with various polymerization degree (n) were investigated by comparing them with those of these esters catalyzed by monomer-type hydroxamic acids (Cm) as an enzyme model concerning with a catalytic behavior.
C¹¹11₂₃CH (OH) - (CH₂-CH)_n-x-_z- (CH₂-CH) z-H
THA (n=10.3, 95.8, 431)
COONa CONHONa
H- (CH₂) m_₁-CONHOH Cm (m=6, 8, 10)
Among them, THA-I (n=10.3), which is water-soluble macromolecule and monomeric surfactant, was the most active catalyst for the ester hydrolysis in the presence of hexadecyltrimethylammonium bromide (CTAB).

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The condensation products of 3, 4: 9, 10-perylenetetracarboxylic dianhydride [1] with amines [4 a-e ](a; ammonia, b; methylamine, c; ethylamine, d; propylamine, e; butylamine) were spectroscopically determined. Under all reaction conditions, N-substituted 3, 4: 9, 10-perylenetetracarboxylic monoanhydride monoimides [2 a-e] (R=H, CH3, CH₂CF1₃, CH₂CH₂CH₃, CH₂, - CH₂, CH₂, CH₃, ) were obtained. As the reactions proceed, the yield of [2 a, -e] increased at an initial stage but decreased after reaching a maximum. This maximum yield of[2] was: [2 e]; 50-60%, [2 b]; 40-50%, [2 c]; 60-70%, [2 d]; 65-75%, [2e];80 85%. A long alkyl chain in amines appeared to be favorable for the increased formation of[2]
The kinetics of this reaction were also examined and discussed.

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In order to obtain a flame-retardant polymer, γ-induced polymerization of bis(2-chloroethyl) vinylphosphonate in the bulk system has been studied. In the steady state, polymerization rate is proportional to the first power of radiation intensity (Rp ∝ l1.0)The effects of various inhibitors on the polymerization support the radical mechanism. Chain transfer is responsible for the lower polymerization rate and lower molecular weights of the polymer. Monomolecular termination reaction appears to take place by the degradative chain transfer from the growing chain to the monomer. In contrast to a few previous studies for catalytic polymerization of this monomer, high molecular weight polymers have now been obtained at very large radiation dose, i. e. Mn, =16400 at 10 Mrad, and cross-linked gels have been formed at a radiation dose of 20 Mrad. When the monomer is polymerized by irradiation to high conversions, resulting polymer is considered to be further radiolyzed to form the polymeric radicals which in turn may cause chain-branching or cross-linking giving the high polymers and also the gel products.

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Since January 1968, the continuous analyzer of formaldehyde, developed by the authors, has been operated at the National Aatoexhaust Monitoring Kasumigaseki Station in Tokyo.
This report presents summarized results of the measurement of formaldehyde from 1968 to 1976. It was observed that the hourly, daily, monthly, and yearly average concentrations were 1 to 73, 1 to 28.4, 3.1 to 19.1, and 4.6 to 10.5 ppb, respectively. Daily average concentration showed logarithmic normal distribution. Relationship between the daily and hourly average concentrations (daily maximum) was about 1 to 2. Daily maximum value was observed at ca. noonday and yearly maximum was found during June and August.

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The solubility of iodates of Mn (ll), Ni (ll) and Cu (ll) in N, N-dimethylformamide-water mixtures has been determined iodometrically at 20, 25 and 30°C.
The logarithm of the solubility of the sparingly soluble salts decreased almost linearly with the reciprocal of the dielectric constant of the solvents, as expected from the Born equation. The solvation radius of the iodates were computed with the observed data of the solubilities and the Born equation.

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A simple method for the determination of copper (ppb level) by the introduction of chelating resin into carbon tube atomizer was attemped. After the copper ion in the test solution (250 ml) has been adequately concentrated and 0.10 g of chelating resin (below 400 mesh) added, the resin was then separated from aqueous solution. Aliquots (10 Al) of resin-suspension, which was prepared by adding 5.0 ml of water to the above resin, were introduced into the atomizer. The optimum operating conditions are shown in Table 1. The calibration graph was linear up to 4.0 ppb of copper, and the relative standard deviation was 2.5% at 3.0 ppb level of copper.

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Six kinds of dithiocarbamate were determined with silver nitrate by the short-circuit am- perometric titration using a rotating platinum wire electrode (1200 rpm) and a mercury-mer- cury(ll) iodide electrode.
It was found that water-soluble dithiocarbamates (sodium dimethyldithiocarbamate, dimethyl- ammonium dimethyldithiocarbamate, sodium diethyldithiocarbamate, diethylammonium diethyl- dithiocarbamate, potassium dibenzyldithiocarbamate, and ammonium 1-pyrolidinecarbodithioate) could be titrated at a room temperature with silver nitrate standard solution in the presence of ammonia and Triton X-405. The recommended procedure was as follows: About 15 mg of dithiocarbamate was introduced into the titration cell. Ammonia and Triton X-405 were added to it until the final concentrations of them became 0.3 mol/1 and O.05%, respectively, then water was added to it up to 100 ml. The solution was titrated with 0.1 molfi silver nitrate solution amperometrically. Ten minutes was required to complete the whole procedure. Dithiocarbamates (ca.10-³ mol/l) were precisely determined within less than 0.2% of both relative error and coefficient of variation. The effects of various ions were examined and the methods used in the presence of interfering ions were shown.

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Solvent effect on the oxo reaction rate of propylene was examined using Co₂(C0)₈ and a small amount of pyridine as a catalyst. The initial rate of formation of butyraldehyde in the oxo reaction of propylene in polar solvents greatly decreased in the presence of pyridine. As a result, the maximal rate in diethyl ether was about 400 times minimal that in acetone. Also, similar result was obtained for the initial rate of gas absorption in hydroesterification. The decrease in these rates was correlated, to a certain extent, to the increase in dielectric constants of solvents.
The infrared spectra at-30°C of the catalyst system consisting of Co₂ (CO)₅ (2 mmol), pyridine (6.67 mmol) and diethyl ether indicated two characteristic bands, i. e., bridging carbonyl at 1850 cm^-1 and terminal carbonyl at 2000∼2100 cm^-1 with weak tetracarbonylcobaltate anion band at 1890 cm^-1 which was responsible for the drop of reaction rate. On the other hand, the spectra in acetone under the same conditions indicated no bands at both 1850 and 20O0∼ 2100 cm^-1 and only the strong band at 1890 cm^-1 was observed.

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The vapor phase oxidation of p-methoxytoluene to p-anisaldehyde has been studied. A V₂0₅-P₂0₅ catalyst scarecely exhibited an activity to give p-anisaldehyde. The activity of the catalyst was improved and continued for a long time by appropriate addition of CuO. However, the addition of CuO led to the increase of combustion products, and resulted in a drop in the selectivity to p-anisaldehyde. The addition of K₂SO₄ to V₂0₅-P₂0₅-CuO catalyst decreased combustion products and improved the selectivity.

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