The active hydrogen contents of color grade blacks ranged from O.273 10wS to O.974 10'S meq/m2, while those of rubber grade blacks were from O.075 10-S to O.149 10'S meq/m2. The active hydrogen contents increased, in general, by treatment with pyridine to remeve the tarry matter from the surface. However, those of some eolor grade furnace blacks decreased. The origin of active hydrogen can be attributted to the functional groups such as phenolic hydroxyls and carboxyls on the carbon black surface. The lewest ave. rage concentratien ef active hydrogen sltes on the surface of samples used here was 1/2200A2 and the highest one was 1/170A2. The heats f immersion of rubber grade and color grade blacks in water were found to be 80, v90 erg/cm2 and 120tv200 erg/cm2, respectively. The effect of pyridine extraction on the heat of immersion exhibited the same tendency as that on the active hydrogen content.
The heat of immersion changed lineary with the active hydrogen content. The energy contribution of the functional greups, which contained active hydrogen, te the heat of immersion in water was 34 kcal/mol. The slurry in water of the color grade furnace black, which contained the highest active hydrogen, was pH 2.83, and that of the rubber grade furnace black, which contained the lowest, was pH 8.69. lt was found that the more the active hydrogen content, the less the pH value. From these observations, it can be concluded that the interaction between the functienal groups which contain active hydrogen and water is the dissociation-hydration reaction and that the pH value is the concentration of protons released by the reaction.

View full abstract

The surface of silica wqs modified by the treatment with diazom-ethane in liquid phase. The modified silica was examined by differential thermal analysis, infrared speztroscopy, measurement of heat of immersion, water adsorptien measurement and so en. lt was shown by infrared spectra that methoxy group and polyethylene chain were formed on the surface with the diazomethane treatment. The surface organic species were held strongly to the surface and decomposed slightly at 4500C., The water adsorption capacity was greatly dezreased by the treatme t, however, heats of im ersion into water were slightly decreased. So, methoxy groups were considered to be able to interact with water by hydrogen bonding. Heats of immersion into organic liquids indicated that the electrostatic field strength of the surface was reduced by the treatment with diazemethane. The particles of the modified silica were repuisive each other and well dispersed in organic liquid.

View full abstract

Several P₂O₅-Al₂O₃ with various compositions were prepared by calcining hydrogels which were made by dropwise addition of NHPH to an aqueous selution of Al(NO3)3 and H3PO4 to adjust its pH at a given value (4 to 9). The acidity and surfage-grea of. "these binaryJ gxides weV deteimined to know their surface properties, together with X-ray diffraction and infrared stuties. The catalytic activities for the dehydration of n-butanol and the isomerization ef n-butenes were tested. lt was found that the acid amounts and specific surface areas decrease as the pH value of the solution increases frem 5 to 9, depending on the rat. io of P/Al-vyith. t. he in-aximum values (1.08 meq/g, 655 m2/g) obtained at PIAI=O.33. The acid strength (H) of the (PIAI 1.0) are 6500C are'generally amorphous. IR spectra suggested that the low P catalysts ifii-xtures oVf AIPOa and A1203, while the high P catalysts (P/Al 1.0) consist of pyrophos'ph. ate than P Al, refiecting no correlation with the total acid amounts.

View full abstract

It was found that despite the low activity trans-bis(triphenylphosphine)a-ary1(bromo)nickel(II)complex catalyzed selectively ethylene dimerization in the absence of Lewis acid at OOC under atmospheric pressure, and that its activity depended considerably on the solvent used, being enhanced especially in a certain solvent having halogen atoms such as chlorobenzene, methylene dichloride etc. On the other hand, the NMR chemical sthift of o-methyl of trans-bis(triphenylphosphine)o-toly1(bromo)nicke1(III)complex in its solution was discussed in terms of the paramagnetic anithotropyof the nickel(II)atom and, it was elucidated that solven, t molecule coordinated tothe nicke1(II)complex i: n its so1ution,

View full abstract

Hydrogenation ef benzene catalyzed by powdered tantalum monocarbide, which is known as a refractory material, was investigated at 25. v2800C by use of a microreactor.
The activity of tantalum carbide (TaC) was negligibly when evacuated at temperatures lower than 9000C, but it greatly increased by the evacuatien above 1000C. The surface area measured by krypton gas adsorpti was nearly constant(1.5 m2/9)regardless of the evacuation tempature, Carbon monoxide or exygen preadsorbed on thus-activated catalyst was found to depress the activity, which became zero by the addition of around 3 iee mole of oxygen per gram catalyst. This value shows that around 60%e of total surface area is effective as active sites, The catalyst poisoned with carbon monexid or oxygen was, however, completely reeovered by the evacuation'tat around 700 or 10000C, respeetevely.
These results suggest that the catalytic activation of powdered tantalum carbide produced by the evacuation at 10000C is attributable to the elimination of oxygen atoms

View full abstract

Dehydrative condensation of cyclohexanone and benzophenone with ammonia over thoria prepared from oxalate have been studied.
In the case of cyclohexanone, various products such as cyclohexenylcyclohexanone and some nitrogen-containing compounds were obtained at 365-410C while a trace amount of cyclohexanoneimine was detected.
Benzophenone condensed selectively with ammonia to form ketimine in high yield at 310v 4200C. Effects of temperature, feed rate, partial pressure of ketone and ammonia are shown in Figs.2-5. Yields of ketimine were reached, for example, 80.5% and 44.0% for O.3X10-2atm and 3.0X10-2 atm of ketone, respectively, in the presence of exess ammonia at 365C. A value of apParent equilibrium constant was estimated to be K=0, 035 0, 002 at 365C.
The selective condensation behavior of benzophenone with ammonia was attributed to the lack of a-hydrogen which was necessary to form aldol-type condensation products.

View full abstract

The oxidative dehydrogenation of butene to butadiene was investigated over uranium exide and its mixed catalysts with Sb203, Bi203 or P20s. ln order to characterize the selectivity of catalysts containing uranium oxide, Mo-Bi binary oxide catalyst system was also studied.
U-Sb-O catalysts, in which atomic ratio of Sb to U was higher than 3 calcined at temperatures 800tv9000C, were found to be selective for butadieRe formation, The reaction rate over U-Sb-O catalyst was approximately of firg. t-order with respect to butene pressure and of zeroorder with respect to oxygeR pressure, Apparent activation energy of the reaction was nearly equal to 13 kcal/mol.
As Simons et al. have pointed out, a remarkable difference between U-Sb-O and Mo-Bi-O in catalytic selectivity was present and the former did not give any double-bond isomerization while the latter did, The inf, rmati, nsobtained in the experiment on dehydration and dehy. dr, ganation of 2-propano1, ver these catalysts have given a certain degree, f explanation of the above-mentioned differen, ce in catalytic selectivity. It would be considered that there was feasible re1ationship between catalytic selectivity and acid-base character of catalysts.

View full abstract

The photographic effects of phenosafranine (1) which acts as an electron trap and of 9methyl-thiacarbocyanine (2) which acts as a positive hole trap were examined by use of three kinds of silver bromide grains with different sizes. The blue speed of all grains studied were decreased by (1). While (2) decreased the blue speed of the coarse grain (O.5μ), but it increased that of the fine grain (O.17μ). lt is considered that the recombination is faster at the surface of the fine grain than at the surface of the coarse grain, as suggested in an earlier paper. The obtained result can be thus understood by the view that (2) causes the recombination process at the surface of the cearse grain, and prevents the rapid reeombination at the surface of the fine grain, acting as a positive hole trap which can be a weak recombination center. These results also suggest that there are two kinds of desensitization caused by dyes.

View full abstract

Effects of divalent metal ions (Hg2+, Cu2+, Pb2+, Ni2+, Co2+, Cd2+, Fe2+, Zn2+, Ba2+, Sr2+ and Mn2+) have been examined upon various types of emissions from AgBr and AgBrI grains in photographic emulsions at liquid N2 temperature. Only Hg2+ and Cu2+ whose redox potentials are the most positive and the second most positive decreased the phetographic speeds, the intensitles of the delayed parts of the emissions at 600nm m the AgBr and AgBrI grains and at 540 nm from the AgBrI grains. Only Hg2+ decreased the intensity of the total emission at 600 nm from the AgBr grain. These results have led to the view that Hg2+ and Cu2+ provide electron traps to the grains.

View full abstract

Zinc oxide powder in electrical centact with aluminum metal after exposed to exciting radiation exhibited the cathodic properties in 2, 3, 5-triphenyl tetorazolium chloride (TTC) aq. solution. The cathodic reaction on ziRc oxide accompanied a formation of 1, 3, 5-triphenyl formazan red (TF) and the aluminum disselved as the anode. The photosensors were prepared by coating the zinc oxide powder with a resin binder on an aluminum plate. The imaging properties of these sensors were studied under various conditions i. e. changing concentration of TTC, electrolyte composition, pH and temperature. The developing solution, containing about 1 wt% TTC and about 1 wt %o NaCl gave good image. The development was sensible to temperature, refleting the temperature dependences of the conductive memory and the dissociation of TTC. The optimum temperature was 200C. The reciprocity law held within 1X10-3and 50X10-3 joule/cm2 when the exposure time was from 1/30 to 1 sec.

View full abstract

For the preduction of extremely pure sulfur by means of distillation, volatile impurities such as arsenic should previously be removed.
Several adsorption methods have been tested for the removal of trace amounts of arsenic in sulfur.
Carbon, alumina, clay, a11 activated, molecular sieve and silica gel were used as adsorbent in the following methods; 1) treatment of sulfur dissolved in carbon disulfide with various adsorbents, 2) treatment of molten sulfur with various adsorbents, 3) distillation bf sulfur after treatment with various adsorbents, and 4) passing sulfur vapor through heated bed filled with various adsorbents.
Excellent results for the removal of arsenic were always obtained in these methods. The third method was the most effective, because arsenic can mostly and easily be removed.
The precedure of this treatment was as follows: the sulfur centaining 43 ppm of arsenic was taken into a distilling flask with 10 wt% of activated carbon or activated alumina. The flask was heated at 300, -v5000C and then sulfur was distilled in an inert gas under reduced or ordinary pressure.
The content of arsenic decreased te 1-, v2 ppm, which corresponded to 95, -v98600 removal.
Next, as a tracer 7aAs was added to sulfur containing l ppm of arsenic previously. The sulfur was distilled according to the above method and the amount of As in distilled sulfur was measured. The content of arsenic was reduced to O. OO1 ppm.

View full abstract

The products obtained by heating Bi20s, and Bi203 in the presence of carbon in a chlorine stream at various temperatures for 2 hrs were examined by chemical and X-ray analyses. The reaction between BiOCI, formed in the chlorination process of Bi20s, and chlorine was also examined.
The chlorination products of Bi20s, and BiOCI at various temperatures are shown in Fig.2. The reaction between Bi203 and chlorine occurs as early as at 25C to form BiOCI. Then the BiOCI reacts with chlorine to form BiC13. Below 400C, the reaction to form BiOCI mainly takes place. At higher temperatures than 400C, the reaction to form BiCls proceeds remarkably.
The chlorination products of Bi20s in the presence of carbon, and BiOCI in the presence of cdrbon at various temperatures are shown in Fig.3 and Fig.4, respectively. The reaction between Bi20s and chlorine in the presence of carbon also occurs as early as at 25C to form BiOCI. Then the BiOCI reacts with chlorine to form BiCI3. Below 250C, the reaction to form BiOCI mainly takes place. Above 300C, the reaction to form BiC13 proceeds remarkably because of the participation of carbon mixed in the formation of BiCls form BiOC

View full abstract

In order to study the surface ProPerties of active solid materials, the muen Ces of the structural distortion of che micany stable CaS04 on the surface ProPerties were investigated.
To control the structural distortion of CaS04, nelydivided crystal grain and distorted lattice, brought about by thermald ecomPos1t1on of gy Psumand by mechanical grind in gofhighly crystalline IICaSO4, were utilized. Structural distortion was expressed by lattice strain and erystallite size measured by X-ray diffraction. The course of structural distortion was divided roughly in two steps. ln the former step, rapid change of crystallite size occurred as found at the final stage of thermal decomposition and the early stage of grinding. Whereas, in the latter step, rapid change of lattice distortion occurred as found at the early stage of thermal decompositien and the final stage of grinding.
Properties relating to surface area such as adsorption, wetting and solid-acidity were influenced remarkably in the former step, whereas others relating to internal strain such as disselutien and hydration were influenced strongly in the latter step.
Although lattice strain and crystallite size of both calcined and ground ff CaSO' seemed to be appaiently the same, a considerable difference between both properties was found and it was explained in terms of structural difference of both particles observed by electron microscope.

View full abstract

Linear phosphazene dichloride oligomers Cl(NPCI2)3n, PCI4(LPNC) were prepared by the reactipn of phosphazene dichloride trimer (NPC12)s with phosphorus pentachloride PCIs.
It was found by the chemical analysis that the hydrolysis of the terminal chlorine atoms in LPNC occurred more rapidly than the middle chlorine atoms contained in the linear molecule of LPNC.
The products obtained by the hydrolysis of the middle chlorine atoms of LPNC was HO[NHP(O)OH]sneP(O)(OH)2 (a).
Those products(a)were again hydrolyzed and became ammonium orthophosphate. The hydrolysis of LPNC was of first-order and the ca1culated activation energy was about 14kcal/mol.
The dissociation constant K and the free energy of dissociation dG of (a) were calculated to be K=7.0-7.4x10-8 and dG=2.9 kca1/mol, respectively.
Upon heating (a) the polycondensation reaction occurred evolving water and ammonia.

View full abstract

It was found that diamidophosphate eould be formed by the hydrolysis of trimeric phospherus niuide diamide in a sodium hydroxide selutien, and the identification of the hydrolysis produet with the PO(ONa)(NHs)2 prepared by Stokes' methed, the rate constant of the hydrolysis, the reaction mechanism and the behavior of NsPs(NH2)e in an acid solution were investigated.
In a 2 N NaOH solution NsP, NH2be was converted into PO(ONa)(NH2)2 by boiling it for 2hrs, An oily product was deposited by the addition of alcohol to the solution; as this had been separated from the mother liquor, it could be crystallized by the addition of alcohol,
The atemic ratio of P to N in the resulting products was exactly 1: 2; however, the Na content was more than that calculated for PO(ONa)(NH2)2. lt was confirmed, from the results of the paper chromatogram, the ion-exchange chromatogram, the X-ray diffraction pattern and the IR spectra, that the hydrolysis product and the PO(ONa)(NH2)2 obtained by Stockes' methed weite the same.
On the basis of the results of the chromatograms, NgPs(NH2)e was directly converted into PO(ONa)(NH2)2 by alkaline hydrolysis; no intermediates were found. The rate of the alkaline hydtolysis accorded with that of a first-order equation, and the activation energy of the reaction was 21 kcal/mol. On the other hand, NsPs(NH2)e in an aqueous acid solution was sucqessively hydrolyzed into ammonium orthophosphate via intermediates such as amidodiphosphates and amidophosphates.

View full abstract

The process of formation of faujasite type zeolite from allophane was studied by X-ray di-ffractiometry. The mixtures having various SiO2/A1203 molar ratios were prepared by adding silica gel to allophane, and these mixtures were heated with NaOH solution under atomospheric pressure. Then, a few kinds of zeolite were prepared. With the increase of the treating time, the A type zeolite was transformed into hydroxy sodalite either through the reaction Ior through the reactionII-III. With the increase of the SiO2/A1303 mo1ar ratio.
the reactionII IIItoo: k place instead of the reaction I. Faujasite type zeolite also was transformed into phillipesite type zeolite through the reaction process N with the increase of the SiO2/A120s molar ratio. When the SiO2/A120s molar ratip ef starting mixtures was low, A type zeolite or phillipsite or type zeolite were resulted. But urider the condition that the SiO2/A120s molar ratio was low, the A type zeolite formed was transformed into faujasite type zeolite with the increase of the treating time. The process of the formation of zeolites from allophane could be summarized as follow:

View full abstract

Nicke1(II)complexes with the Schif base ligand(H2L)derived from salicylaldehyde and bis(2-aminoethy1)sulfide have been prepared and characterized. NiL complexes obtained were generally octahedral, but under certain conditions, they were planar or trinuclear, In the reaction of NiX2(X=C1, Br)with the ligand(H2L), NiYX complex, where Y is(5alicylidene 2-iminoethy1)-2-aminoethylsulfide, was obtained by breaking of one NCH bond of the ligand (H2L). It was found that the ligand(L)of the octahedral NiL complexes is coordinated' through S, N, and O atoms. The NiXY complex is octahedral, in which Y, as a quadridentate ligand, and X are coordinated to nickel ion.

View full abstract

Compositions, stability constants, molar extinction coeMcients and stability pH ranges for lead(II)an, d coPPer(II)-complexes of, -ethylenediiminodi(o-hydroxyphenylacetic acid)(EHPG)have been determined spectrophotometrically.
The molar ratio of metal to ligand of each complex was 1: 1. On the basis of the absorption curves of the complexes of EHPG as well as ethylenediamine-N, N'-diacetic acid (EDDA)and the pH-absorbance curves, the following species would be assumed; firstly, doubly protonated chelate species MH2X, with two free phenolic hydroxyl groups, for lead(II)and copPer (II) at below pH's 6.0 and 3.6, respectively, and, secondly, at abeve these pH's a singly protonated and normal chelate species MHX, MX, with the metal-phenolate linkage, for both lead(II)and coppe: r(II).
The data observed were as follows; the logarithms of the stability constants at ionic strength O.10 adjusted with NaCIO' and 200C were 9.64, 14.57, 12.91, 20.15, 15.09 and 23.94 for PbH2X, CuH2X, PbHX, CuHX, PbX and CuX, respectively, the molar abserption coeMcients were 4.96 10S, 8.20 10S, 5.79 10S, 9.14 10S, 8.66 103 and 9.30 108 at the absorption maximum wavelengths of 273, 274, 280, 275, 292 and 292 nm, again respectively.

View full abstract

In(III)complex with gluconic acid las been studied by p 1ar graphic and potentiometric titration methods. The form of species present in the solution and its electrode reacti n have been determined and discussed.
The formation f this complex was recognized at ab ve pH=11.8. Therefore, the present study was carried o ut in the pH range from 12.2 to 13.0 and gluconate concentration range from 8x10-8. to 72.0x10-3 mo1/1 by po1arography. The two stepped wave in which the halfwave. potential of the first step was-1.22V and that of sec nd -1.56V vs SCE was obtained, re pectively. The current of the first step was kinetica11y-controlled, but that of the total steps was roughly diffusion-controlled. Koryta s equation for kinetic current of complex ions was applied to the a: nalysis for p 1ar grams of this complex.
The two 91uconate ions(GH4-)were bound to: ne indium(III)i n. The result of potentiometric titrations showed that three hydroxylions were attached to indium(III)ion The reacti n mechanism responsible for kinetic current would be given by
and the rate constant of diss ciation(k-mo-1 sec-) would also be expressed as follows:
where and denote the stability constants of In(OH) s and In(GH)2(OH) srespectively.
The cathodic r6duction processes would be speculated as f llows: for the rst step;
and for the second step;

View full abstract

Methods for the spectrophotometric determination of scandium and yttrium with methylxylenol blue (MXB) have been studied.
MXB reacts with scandium to form a water-soluble red-violet complex. The colored solution shews a maximum absorption at 585 nm and the constant absorbance over the pH range 2.32.7. The relation between the absorbance of the complex and the concentration of scandium is linear over the range of O.4Avl.6 ptg Sc/ml, and the sensitivity for log(lo/l)=O. OOI is O.0021 ptg Sc/cm2 at concentration of O.8 ptg Sc/ml. Scandium can be determined within 5e/o errors in the presence of twenty-six f. reign i. ns such as rare earth elements, lead, zinc, chromium(II),
Yttrium produces a water soluble blue complex with MXB in the presence of cetyltrimethy am-nioFfilaMm V-cTliloride (cTMAc) and its aque6us solution has an absorption. max-imu. m between 63'iMnt5nd 634 nm. Thle color at lon is stab16 over the pH range 6.6, -vg.3. The gbsorbance prga' gUrfed at 640 nm obeys Beer's law up to 1.8 ptg/ml of yttrium. The reaction is very sep. slttve masked by the addition of various masking agents. Beryllium, chromium(III), rhodium(III), scandium rare earth elements and phosphate, however, interfere seriously.
Consecutive determination of scandium and yttrium has been also studied, A sapaple dsolytion metal complexes are additive

View full abstract

For the rapid determination of sulfite ion, a potentiometric argentometric titrimetry using an iodide-ion selective membrane electrode was developed.
The optimum conditions for the argentometric titration of iodide ion in the presence of iQdine were determined. Sulfite ion was determined by titrating the iodide ion produced by the reaction with iodine.
The recommended procedure is as follows. After 10 ml of O.2N iodine-methanol solution and 1ml of 2 N sulfuric acid are mixed in a titration cell, a sulfite solution (e. g., O.1N, 10 ml) is added. The resultant solution is diluted to 100 ml with water and titrated potentiometrically with a silver nitrate solution.
Sodium sulfite, at the final concentrations ranging from O. OOOO1 to O, Ol N as iOdid9 iOPA vy. aE DeVeVr fi hbie Wilh afe1-a tl Jv-e-eff6 W i-eVssny Vt 6 arf O-2. s% and a coeffiicient of variatig. n (Cr Y, ')bVre stwebeffce-V6 Mf Triaige amounts of chloride, broniide, sulfate and carbonate ions did not show anY interference(Fig.5).
This meshode is applicable to the determination of suifur dioxide in chimney gases, . Analytical values obtained by this method were in good agreement with those obtained by the iodometric method previously reported.

View full abstract

Boric acid solution (O.1mol/l) was passed through a column packed with strong base anion exchange resin, Diaion SA 20 A in the fluoride form (O.8 cm2 45 cm or O.8 cm2 95 cm bed), and the band formed on the column was eluted with pure water.
The boric acid coRcentration in each fraction of the eMuent was determined by the acidbase titration with manitol. The atomic fraction of boron-10 in each fraction was determined by means of a Varian Mat CH 5 mass spectrometer, using the surface ionization method.
In these experiments, it was found that:
(1) Boron-10 was considerably enriched in the rear part of the band (e. g. aerr=1.06) and depleted in the frontal part (e. g. af=O.95).
(2) The boric acid charged on the colum was nearly completely eluted with pure water.
(3) Fluoride ion was scarcely detected in the eMuent (below 10-3 mol/1).
(4) The elution curve became sharper with the decrease of flow rate.
(5) The enriched amount of boron-10 increased with the decrease of flow rate, and with the elevation of column length and loading of boric acid.

View full abstract

Aqueous solution containing 5 mmol of boric acid was passed through a column packed with weak-base anion exchaRge resin, Diaion WA 21 in free base form (O.8 cm2 48 cm bed), and the borate band formed on the column was eluted with pure water. The boric acid concentration in each fraction of the effluent was determined by acid-base titration with manitol. The atomic fraction of the boron-10 in each fraction was determined by means of Varian Mat CH 5 mass spectrometer, using the surface ionization method.
In these experiments it was found that;
(1) Boron-10 was considerably enriched in the rear part of the band, and depleted in the frontal part (Fig.1).
(2) The beric acid charged on the column was completely eluted with pure water (Table 1).
(3) The elution curve was influenced effectively by operation temperature; the higher the temperature became (from 50C to 40C) the sharper the elution peak beeame (Fig.1, 6, 7).
(4) Boric acid concentration and flow rate gave a little influence on the elution curve; increase of boric acid concentration up to 1. Omol/1 and decrease of flow rate tended to give sharper elutien peak

View full abstract

The structures of the Meisenheimer-like complexes, produced by the reaction of some mononitrobenzene derivatives with alkoxide ion, were studied by measuring the IR and NMR spectra. The complexes were formed as red crystals by mixing o- or p-nitroanilines in dichloromethane with alkoxide ion in alcohol, but they decomposed rapidly as the solvent disappeared.
From studies on spectra, some informations about the structure were obtained.
(1)For Meisenheimer-1ike c, mplexes, IR absorpti, n bands due to C shifted t, 1, w wave number side and the broad band become cramped with decreasing NOs groups.
(2) The more unstable the complexes, the stronger is the intensity of stretching vibration bands due to NO2 groups and it vanished as the complexes became stable.
(3) The ring protons of Meisenheimer-like complexes shifted to high magnetic field side, NH2 sigRals to low field and OCHs signals to high field.
It was f, und that the str, ng and broad band characteristic, f keta1-1ike structure C, appeared at 1020, -vlO40 cm-i. Ring protons in Meisenheimer-like complexes appeared at T.=2.08and Tp=3.44. On the basis of facts, it could be strongly sugguested that the structures of the complexes were

View full abstract

2-phenoxy-1-phenyl-1-propanol(A), 1-phenoxy-1-phenyl-2-propanol(B)and3-phenoxy-1phenyl-2-propanol(C)were irradiated mt hepresence of1, 4-naphthoquinone, anthraqumone or xanthone and the irphoto-Cleavagereaction. fC-Cbond Were inVestigated
In the caseof A, benzaldehyde and phenetole were obtain edma 95% and 42% yield as the cleavage reaction products(gg. in the presence of anthraqmnone). on the other hand, benZylphenylether or phenylacetaldehyde was detected m the case of BorC. Thus, itwas presumed that m the case of B and C the photo cleavage reaction. ofC -CbondWas Caused by the interaction of these CarbQny1 CompoundS With the hydrQXy1 group Qfthe alcoho1m a similar manner in A.
In order to clarify the relatlonsmp between this cleavage reaction of C-Cbondandthe structure of alcohols, 2-phenoxy-1-phenolethano l, 2-phenoxy-1-cyclohexylethanol2 and 2cyclohexyl. xy-1-phenylethano 4 were irradiated in the presence of those carbonyl compounds. Theratio of the Conversion of alcoho 1 SWaSaSfQ1lows, 24--. -70: 43(mthe presence of an thraqumone). The amount of amsole formatn was 61% meach of the case. for2, but, benzaldd1ydewhichwasobtainedma82%yieldmthecaseof), was detected by only 2% mthecase of 4.
From these resuls, it was reasonab1y conduded that the 2-phenOXyethano1 p1ayed an im portant role on the photo-cleavagere action of the alcohol with the carbonyl compounds,

View full abstract

The reaction of phenyl glycidyl ether (PGE) with benzoic acid (BA) catalyzed by tertiary amines and quarternary ammonium salts has been studied. The reaction catalyzed by quarternary ammonium salts is in goed agreement with second-order kinetics, according to
-d[PGE]/dt=-d[BA]/dt=k, [PGE], [Cat. ]
The tertiary amine catalyzed reaction, especially at the beginning ef the reaction, proceeds at a slewer rate than the reaction in the presence of quaternary ammonium salts. ln the reaction of PGE with BA in the prescnce of tertiary amines, catalyst amines react with PGE to form quarternary ammonium carboxylate salts, which is the actual catalyst in this reaction. The strtcture of the alkyl groups of amines has a large influence on the catalytic activity. ln the case of quarternary ammonium catalyst, the structure of alkyl groups does no affect the catalytic activity, but the type ef aniori associated with quarternary salt is very important.

View full abstract

Reactions of N, N-disubstituted thioureas with 2-chlorobenzothiazole have been investigated.1, Nr-disubstituted. thioureas with various alkyl or cycloalkyl substituents reacted with an eduimolar amount of 2-chlorobenzothiazole in benzene or methylene dichloride as room-t. e. mWhen petrature in the presence of hydrochloric acid to produce oily-interpaed. iate pro. d. ucts. heated with an excess of aqueous 10% NaOH solution under reflux, the intermediaJtes afferded 2V, Nt-disubstituied carbodiimides corresponding to the thioureas used in ca.70%oiyields !g. ge. tber with a small amount of N, N-disubstituted ureas. After the separation of carbodiimides, alkaline solution was made acidic with dil. HCI to yield 2-mercaptobenzothiazole in 70, v80/o yield.

View full abstract

The Friedel-Crafts acylation of dibenzofuran (D) with substituted benzoyl chlorides (Xnt CGH4COCI) in the presence ef aluminium chloride in nitrobenzene or chlorobenzene gave 2acyldibenzofuran in the yield over 70%o and smali amount of the 3-acyl isomer or 2, 8-diacyldibenzofuran as byproducts. For example, the reaction of D with o-methoxybenzoyl chloride in the presence of alminium chloride in chlorobenzene at -140C for 4 hrs, gave 2-(o-methoxybenzoyl)-D (mp 108, vlO8.5'C, yield 80.3%) and 3-(o-methoxybenzoyl)-D (mp 135, v136'C, yield 1.2%o). The structure of the latter compound was identified by comparison with the authentic sample prepared by Fries reaction of 3-dibenzofuran carboxylic acid phenyl ester. Similarly, the same reaction of D with other susbstituted benzoyl chlorides gave the following results: (X substituent, acylating site of D, mp OC, yield %.)p-CI, 2, 156.5, v157, 68.9 and 2, 8-di, 203.5hv 204, trace; Cl, 2, 139.5-140.5, 70.9 and 3, 159-160, 17.6; o-C1, 2, 121.5-122, 70.2 and 3, 168, -v169, trace. The structure of these products were determined by means of spectroscopy or by comparison with authentic samples. Furthermore, the Friedel-Crafts reaction of monoacylderivatives with X-C6H4COCI was carried out to prepare some new 2, 8-diacylcompounds.

View full abstract

Several sm-polyfluorodiaminobiphenyls were prepared in order to obtain colnponents for her: mostable fluoroaromatic polyamides. With mixed acld 2, 2, 6, 6-(1)and 4, 4, 6, 6 -tetra uorobiphenyl(4)and 2, 2, 4, 4, 6, 6, -hexafluorobiphenyl(7)were: nitrated to the corresponding 3, 3-dinitro derivatives in good yields. Reduction of these dinitro compounds gave tetra-and hexa uoro-3, 3 -diaminobiphenyls, (3), (6)and(9).
By reductive rearrangement of 2, 2, , 6, 6(10)and 2, 2, 5, 5, -tetrafluoroazobe: nzene(12), 3, 3, 5, 5-(11)and 2, 2, 5, 5 tetra uorobenzidin, e(13)were obtained respectively. Tetrafluoroazobenzene (10)was prepared from, 2, 6-di uorolithiobenzene and 2, 6-di orobenzenediazonium tetrafluoroborate, while(12)was obtained by a1: kaline reductionof 2, 5--difluoro: nitrobenzene in dioxane, The reduction of 2, 5-difluoronitrobenze: ne in ethanol gave 2, 2 -diethoxy-5, 5, -di oroazobenze ne(14), which was rearranged to 5, 5-diethoxy-2, 2 -di orobenzidine(15).

View full abstract

The formation of 11-oxo-11 H-isoindolo[1, 2-c][1, 2, 4]benzothiadiazine 5, 5-dioxide. (6)rst from o-aminobenzeResulsonamide (1) and phthalic anhydride (2) was investigated, The reaction intermediate of 2-sulfamoylphthalanilic acid (3) was synthesized by the ringwgpening addition of (1) with (2) at roointemperature. The thermal cyclodehydration of (3-) g-a. v. e (6) via the f oi ihe second inte-rmediate of N-(o-sulfamoylphenyl)-pbthajimidg (4)e Thre cyclodehydration of (3) with acetic anhydride at room temperature afforded (), whe. reAaS that vGith thi6nyl chloride- yrielded a mixturerof (4) and (6). The third intermedia-te -of-3(o-carbokyphenS1)-1, 2, 4-behzothiadiazine 1, 1-dioxide (5) was obtained by th cyclodghyd. ratign 6rmf (3) ifi hot aqu e6us sodium hydroxidb, whereas (6) was obtained by the rJeaction in the pres of a basic catalyst, such as r-piceline and tri-n-butylamine, at an elevated temperature, A probable reaction pathway was discussed.

View full abstract

6-Substituted--3-(2 -pyridyl)-1, 2, 4-triazin-5-ones were synthesized in good yields by -t je reaction of a-ket6 darbexylic acids, a-keto esters and ev-thiocarbamoyl ester with 2-pyridylamidrazone.
6-Methyl-3-(2 -pyridyl)-1, 2, 4-triazin-5-one (4 a) was obtained by th-e. rgacSign. of. py-ruvic acid or ts esier with 2-pyridylamidrazone, and 6-phenyl-3-(2 -pyridyl)-1, 2, 4-triazipr5-gng (4 b) Li ag similarly obtaineMd from phenylglyoxalic. acid. gr.. its e-stgr, . but th-e reac. tigKof diethyl iM esi-oVialate with 2Lpyridylamidrazone afforded 3-(2 pyridyl)-1, 2, 4-triazin-5-gn-e (.4d)
The reaction of ethyl thiono-oxamate with 2-pyridylamidrazone afforded 6-amino-31(2ft- hQ1n)5: 0neN (11a), which was cyclized on treatment with phostuphgr-us pep-tas. ulfi-. dpe. tAo. g Fe t-e fo -cyVcfe wl th i new ring system, 6-rnethyl-3-(2 -pyridyl)-(1, 3)-thiazolo(s, 4-e)(1, 2, 4)triazine (12).

View full abstract

It is known that in the oxo reaction of butadiene, oRe of the double bonds is usually hydrg t61iadfechn-s, lodion5s, and polyketones were also produced in additipn to the kngwn prg. du. cts, T-h e oxo feaction of butadiene and butene were compared under the same reactidion conditions: h n al ng sM itTTI g s uggested that the formation of ketones may be d. ue. to he c. o-ordinatiop., of 6-1-iiaie-n6M to aiyVl-cobalt-tricarbonyl to give rr-allyl complex and that the other steps of the reac ion would be common for the reactions of butadiene and butene.
itVfi e in6rhaSe in the amount of butadiene resulted in the increased conyersion toi k. etones. Th- Vf5-c-irm Ta-iSo supports the above mechanism. The structures pf she ketones whigh we. re iso "iaVte iYf roilfi ih6 ie action mixture well coincided with those of the ketones expected to be formed if the z-allyl complex mechanism would take place.
Cg-ketones and CA-ketones was achieved.

View full abstract

The liquid phase oxidations of p-xylene with cobalt ion as an catalyst and acetaldehyde as its promoter were carried out in various types of bubble reactors with different producibility of gas-liquid contact surface area. By comparison of the reactor performances, the following information was obtained.
Both the perforated plates and the rotary distributor accelerate the exidation of P-xylene, In the case of continuous operation, the rotary with the buMes is superior to that with the perforated plates which tend to be pluged by the sparingly soluble final product, terephthalic acid. At the moderate flow rate of acetaldehyde, the induction period ef the oxidation decreases with increasing flow rate, whereas acetaldehyde retards the reaction at the relative high flow rate.

View full abstract

As various organic compounds were oxidized by cobaltic acetate in acetic acid solution in the absence of oxygen, the influence of substrate specificity on the reaction mechanism and reactivity was investigated, The reduction rate of Co(III)in the oxidation of various substrate having electrons obeyed the following equation (Figs.2, 3, 5, 6 and 7):
d(C 1III) K. b, . (RHCo(M))2(C, (III))
Since this equation was similar to the rate equation of the oxidation of toluene and its homologue by Co(III), various compounds would beoxidized by cobaltic acetate via reversible one electron transfer process. Kebs, was not affected by CewH bond dissociation energy of substrate but would be correlated with the ceordinatien ability of substrate to cobaltic ion and with ionization potential of substrate (Tables 1, 2 and 3).

View full abstract

Cobaltic carboxylates oxidize toluene via a reversible one electron transfer process in acetic acid solution in the absence of oxygen. Lingands of cobaltic ion were found to have a very important role in the oxidation reaction. So we investigated the effect of ligands of cobaltic io n. NeutraI Iigands affectedonIy the activity Co(III)but anion ligands affected both reaction rates and reaction products. Strongly coordinated neutral ligands such as bipyridyl, pyridine or acetonitrile reduced the reduction rate of Co(III)(Table 1, Fig.6). Large anion ligands such as iso-butyric or pelargonic anion suppressed the oxidation by the reversible one electron transfer and were favourable to decarboxylation (Table 4).
Accordingly, the effect of ligands on the aromatic oxydation by Co(III)can be attributed to the steric factor rather than to the redox factor, and the rate determing step may be inner sphere complex fermation between toluene and cobaltic ion in one electron transfer process,

View full abstract

The nitration of toluene at O-1eC with nitric acid in the presence of various acids (aromatie sulfonic acids, ion-exchange resin, phosphbrus pentoxide and aluminum chloride, etc.) was investigated.
The nitration products catalyzed with various acids had the considerably higher ortho-para ratios (P/o) than that with the usual mix-acid (sulfuric acid-catalyzed). For example, the the P/o ratio of products were as follows, porous ion-exchange resin (Amberiyst 15): 1.44, Wphosphorus pentoxide: 1.34, P-xylene sulfonic acid; 1.06, 2, 4, 6-trinitrobenzene sulfonic acid: 1.04, m-benzene disulfonic acid: 1.08, toluene-2, 4-disulfonic acid: 1.05 and usual method (sulfuric acid): O.60 (Table 1).
Such an increase in P/o ratio may be attributed to the steric hindrance of methyl group on the attacking ion pair in the form of nitronium ion and bulky conjugate base (fer example Ar SOse e NO2b, ).

View full abstract

Pyrogenic aqueous solutions were prepared from that containing 5fe250 partly caramelizing glucose or from the deionized water containing O.33 or 3.3ppm of bacto-lipopolysaccharide SL abortus equi. These aqueous solutions, which were found to be highly pyrogenic, were passed through ion exchange reg. ins, adsgrbents and hyperfiltration membranes to test the degtee of removal of pyrogens. Some of the macroreticular ion exchange resins and gelular anion exchange resins were effective tg some ex. tent for the removal of pyrogens (Table 3 and 5). Neither activated carbon nor synthetic adsorbents proved to be effective for the remeval 6f pyrogens. With regard to membrane permeation, the membranes used in this work were found to be very effectiye-for. the removgl o-f pyrogens (Table 4, .6 and 8). The reproducibility of these membranes used for the removal of pyregens was good.

View full abstract

The ultrasonic absorptions of polystyrene in toluene solution were measured by the pulse t t method in the, frequency range 1, v30 MHz and in the temperature range ON500C. The molecular weights of polystyrene samples used 2.1x103 (M. IM.; 1.06), 4.0x10S (1.10), 2.0x106 (1.30) and 3.0x105 (polydisperse).
The ulnrasonic absorptions of polystyrenes were represented by a single relaxation eqUation over the whole molecular weight and temperature ranges of this experiment.
In the higher molecular weight sides, the relaxation frequencies and their temperature changes were independent of the molecular weight. The ratio of the relaxation strength was consistent with that of the molecular weight and the unit of chain motion in polymer solutions was constant and independent of the molecular weight.
On the contrary, in the lower molecular weight sides, the temperature changes of the relaxation frequencies and relaxation strength were different from those in the higher molecular weight sides. This ultrasonic relaxation in the lower molecular weight sides was attributed to the motion of chain ends of polymer chains in the solution.

View full abstract

The poly erizati, n, f methy1 ethacrylate(MMA)initiated with the aque, us s, lution. f starch Was carried out in the presence of carbon tetrachloride or cupric ion. The eMciency of grafting of poly-MMA onto sEarch was assumed to amount. to 20N72%e 4L kineti. c.. study of Vhe polW o za ion was made and the tate of polymerization, R, , was obtained as follows:
R, =k[Starch]g, ti[MMA]i. O, o
The amount of reagent used is shown in bald face parenthesis. The reaetion order, 1. O--, shown in the term [MMA]I th g means that when [MMA] is not high, R, is proportio. nal tg [MMA] however T [MMA] exceeds a certain limit, R, becomes to be independent of [MMA].

View full abstract

2-Vinylpyridine was grafted anionically by and onto lithiated poly(styrene-co-p-benzylstyrene)having known molecular weight (M.) and the narrow-molecu1ar weight distribution. The yield in each run was about 100%o. The results of the M. measurement and the turbidimetric titration showed that the graft copolymer was the only product. On the assumption that the number of the branches of the graft copolymer is nearly equal to (anion number/molecule) of metallated polymer, M. of the branches of graft copolymer was calculated. Graft copolymers having knewn chemical composition, known molecular structure and multi-branches could be synthesized by the above-mentioned method.
The solubility and intrinsic viscositses ([T]) of graft copolymers depended on their molecular structure. [op] values of graft copolymers in benzene at 300C were smaller than those expected on the basis of their M. values. The intrinsic viscosities were affected mainly by M. of branches and M. of backbone, but hardly by the number of branches. The solubility of graft copolymers was higher than that of poly(2-vinylpyridine) and lower than that of poly(styrenecop-benzylstyrene) in a mixed solvent of 2-butanone and n-heptane. lt shows that backbone Segments protect the branch segments from precipitation. On graft copolymers having the same M. and the same chemical composition, the solubility of the graft copolymer having the higher M. of branches was lower than that of the graft copolymer having the smaller of branches.

View full abstract

Hydrolysis of N-vihyl-2-oxazolidone (NVOx) in the presence of polyacids, such as poly(acrylic acid) (PAA), poly(methacrylic acid) (PMAA) and poly(L-glutamic acid) (PLG) was investigated. The break in the presence of PMAA or PLG were observed at pH=5.1, v5.2, where the conformation of PMAA or PLG changes; no the break was observed in the presence of PAA, however.
The hydrolysis of NVOx was also examined in the presence of isotactic PMAA(PMAA), syndiotactic PMAA (s-PMAA) and atactic PMAA (a PMAA). lt was found that the rate of hydrelysis increased as follows;
i-PMAA s-PMAA s: a-PMAA
Furthermore, the salt effect on the hy, drolysis of NVQx ip thg. presenge gf. aceSic acid or PMAA was studied. The rate of hydrblysis increased by the addition of salt in the presence 6f acetic acid, while the rate decreased in the presence of PMAA. t Syntheses and Reaction of Functienal Pelymers. LXXVI.

View full abstract

The radiation-induced crosslinking, chain scission, and oxidation of poly(vinylidene fluoride) (PVdF) have been studied. The irradiation was carried out with r-rays and electron beams at ambient temperature under vacuum and in the presence of oxygen. The gel formation, solution viscosities, and number average molecular weight of the PVdF so treated, as well as the evolutien of hydrogen fluoride (HF) and other gases were measured. IR and UV spectra were also obtained.
When PVdF was irradiated under vacuum, the G value for crosslinking was O.6, vO.8. This was equal to the G value for chain scission (Table 1). Double bonds including polyenes were formed as a result of dehydrofluorination. The concentration of polyenes was, however, low and decreased with increase in the number of conjugated unsaturation. Polyenes 1enger than tetraene were hardly observable (Fig.6). The G value for the formation of HF was reduced from 3.5 to 3.0 when HF was removed with dry potassium hydroxide during irradiation (Table 3). This result suggests the accelerating effect of HF on the radiolytic dehydrofluorina tion of PVdF.
Oxygen accelerated the chain scission and dehydrofiuorination of PVdF (Figs.1, 3, 4, and Table 3). Those effects are dependent on dose rate and the thickness of samples. At high dose rate (electron beams), there was little effect, while the remarkable effect was obserVed at low dose rate; the thinner the sample the more the effect. Carbonyls such as acid fluoride and carboxylic acid were detected as the oxidatien products (Figs.8 and 9).
The reactieR mechanism is discussed in connection with the results obtained here and ESR

View full abstract

Cellulose dinitrate (DNC), obtained by homogenous reaction, showed a broad X-ray diagram similar to cellulose trinitrate (TNC). The diagram did not become sharp by usual recrystallization, and it would be the imperfect crystallite of TNC containing unaltered QH groups uandomly and not DNC crystallite. The existence of DNC crystallite was alsgJ d-oubtful from the iewpoifit of the selective reactivity among three kinds ef OH groups in celluloser
In- previous work, it was considered that when OH groups. adjacent tg C2 anq Cg. are both nitrat- C glucose ring sheuld change from chair form (02 and Os, gauche) toL. h alfboat 6h-s6, the reactivity of either of OH groups adjacent to C2 or C3 would fairly be lowertha n the other because of the energy required to change a ring form.
B TNC treated with supTerheated water at 1500C, gave the new sharp X ray diagram with different from that of TNC(25.75 A). This fact suggested that glucose ring in DNC m 1ecule retained chair form.
The. unit cell f DNC crysta11 te was monoclinic(pseudoorthorhombic)with; 13, 62 A, b=10.32A, c=7.94Aand=90.

View full abstract

Crystalline structures of cellulose dinitrates and their saponification products derived frem various crystalline modifications of callulose were studied by means of X-ray diffractien method.
All cellulose dinitrates, derived from any crystaHine modifications of cellulose and recrystallized with s er heated water, gave the same X-ray diffractgraph. Different from trinitrate, there was not found crystalline modification of cellulose dinitrate resulting from crystalline structure of original cellulose. Amorphous cellulose dinitrates, which were derived from cellulose I family(1, I and V I)and not recrystallized, were sap ified to cellulose I and renitrated to cellulose trinitrate I, while those derived from cellulose family(, and N ll)were saponified to cellulose Ir and renitrated to cellulose trinitrate. It was shown that before recrystallization molecular configuration of each family remaind unchanged during nitratien and saponification processes. Recrystallized cellulose dinitrates were saponified te cellulose g and renitrated to cellulose trinitrate irrespective of the crystalline structure f riginal cellulose. Therefore, the skeletal chain conformation in cellulose dinitrate crystallite would be bent and twisted form similar to that of cellulose family, but in amorphous dinitrates derived from cellulose 1 family the skeletal chain conformation retalned bent form and changed to bent and twisted form in recrystallization process.
In infrared spectrum of cellulose dinitrates stretching mode of OH groups showed parallel dichroism. lt was considered that unaltered OH groups in cellulose dinitrate were those adjacent to Cs position forming intramolecular hydrogen bonds.

View full abstract

It has been: known that the vapo liquid equilibrium data for the system accompanied, by chemical reaction can be correlated by following equation:
where Kz is the vapor-liquid equilibrium ratio (yt/xt) for component i, T is the absolute temperature and At and Bt are constants.
Validity of the equation for the binary systems accompanied by hypothetical chemical reaction was examined by using the reported data in literature. Consequently, it was found that the equation can be applied for several systems. Constants At and Bt can be determined from one x-y-T datum for the binary system and boiling point data for pure substances which compose the system. Using these constants, x-y-T relation over all range for the binary system can be estimated. Above mentioned facts can be interpreted by censidering that the hypothetical reaction system is the reaction system in which the reaction is occurring very slowly.

View full abstract

The main reaction brought about by r-irradiation upon pyridiRecarboxylic and pyridine dicarboxylic acids in solid state was decarboxylation. As a rule, weakly bonded cqrboxy groyp would pieferentially be eliminated. Among three pyridinecarboxylic acids 2-pyridin-ecarboxylic acid w- decarboxylated by r-irradiation in the highest yield. ln 2, 3-pyridinedicarboxylic acid, G-value of decarbexylation at 2-position was greater than that at 3-position by a factor of three.

View full abstract

Effects of water on the formations of and H aggregates of 5, 5 dichloro-3, 3, 9-triethylthiacarbocyanine (1) and 3, 3Ldiethyl-thiacarbocyanine (II) absorbed on AgBr grains wbre examined by observing the J and H bands in their visible-range reflection spectra, Water accelerated that J aggregate formation of dye 1. However, water depressed the J aggregate formation f dye, while it accelerated the H aggregate formation of this dye. Discussi ns weae made on the factors influencing the dye aggregate formation. t Studies on Mechanism ef Photographic Sensitivity. LXXII.

View full abstract

The effect of ultrasonic wave on the electric conductivity of n-butyl alcohol and tert-butyl alcohol was studied under various conditions. The conductivity increased when the alcohols yi ere irradiated with ultrasonic wave while the dielectric constant decreased. The conductivity and dielectric constant reached the limiting values within 20 minutes. These ehanges were feund to be reversible. No appreeiable chemical change, breught about by ultrasonic wave, was observed by IR and NMR spectroscopy.

View full abstract

The phase diagrams of the systems PbO. Pb(S-Cr)04, 2 PbOePb(S-Cr)04 and 4 PbOePb(S-Cr)O, were investigated by means of DTA and X-ray powder diffraction. ln these systems, the formation of continuous solid solutions were confirmed. The following crystal data of basic lead chromates were obtained on the bas is of basic lead sulfates.

View full abstract

The preparation of basic aluminum chloride coagulants from clay was studied.
Clay calcined at 600 C for an hour was dissolved in(1)10% hydrochloric acid and (2) 1, 10r 2, 1 (eq.) mixture of hydrochloric and sulfuric acids with hydrogen ion which corresponded to iO% hydrochloric acid. To make the solution basic (1) hydrochloric acid was removed at the boiling point and(2)a part of sulfuric acid was precipitated as sulfates by adding BaCO3, CaCOs and Ca(OH)2 to the solution.
Coagulants prepared by these methods were subjected to coagulation test and proved to be effective in the lower pH region as coinpared with commercial BAC solution.

View full abstract