The electric emulsification by the use of high voltages has been carried out to produce aerosols. However, , the present authors succeeded in producing directly O/W or WIO type emulsions by using fairly low voltages, during the course of studies on electrocapillary phenomena at oil/water interfaces. The critical voltage of emulsification E., i. e. the minimum voltage necessary to produce a continuous emulsification, had no direct relationship with the equilibrium interfacial tension r measured by the ordinary drop-weight method. Concentrations of inorganic electrolytes and ionic surface active agents in the oil and/or water phases had strong influences on Ee. The effect of the concentration of surface active agent, however, was found to be due primarily to its property as an electrolyte, the surface activity playing the secondary role. lt is the necessary condition for the electric emulsification that the specific conductivity of the discontinuous phase is higher than that of the continuous phase. Ne emulsification takes place when the latter is higher. Although the experiments were maiRly carried out in the waterlfuethylisobutylketone system, the same condition can be applied to other systems. For instance, mercury/water and liquid/air (aerosols) systems, for which most studies on electric emulsification were carried out, also satisfy this condition.

View full abstract

Synthesis of but-3-enoyl chloride from allyl chloride and carbon monoxide undet various pressure in a benzene solution has been studied kinetically in the presence of a catalytic amount of [rr-C3HsPdCl]2.
Based on the assumption of the reaction mechanism proposed in the previous reports by other authors, the rate equation has been derived as shown below:
[C3H5PdC1]2+2CO(1)Pt 2LC3H5PdC1(CO)
C8H5PdC1(CO)+CO(Z)Pt CH3 CHCH PdC1(CO)2
CH2=CHCH2PdC1(CO)2+CO(1) CH2 CHCH2COPdCl(CO)
CH2 CHCH2COPdC1(CO) 2. +CH2=CHCH2C1 CH2 CHCH2COC1+CH2=CHCH PdC1(CO)
(AC)
V=d CH CHCH2COC1
=2 2 3 2(A), 2c [AC]
E, kd AC (1+ 11)+Kak3, H2/2co
H; Henry co stant of CO, fco; Fugacity of CO.
Which is in reasonable agreement with the experimehtal results.
The equilibrium constants, rate constants, Henry constant at 100 C and the over all activa, tion energy have been determined to be K 23, K 0 13mol 1, 1, 3=1.6 102m 1 1 mi, 4=4.2n 1'i, 1, mi 1, H=2 60 10 3 mo1 1 1 atm and' Ea=10.8 k a1 or 1, respectivly.

View full abstract

The reactions of N-atom with C2H' proceeding in the flame and the glow have been studied using a chemiluminescence method. A fast flow, low pressure apparatus was used. The measurements were earried out at a velocity of 50. v70 cm. sec'i under a pressure of 2. v3 Torr in the reaction vessel and at room temperature. The initial concentration of N-atom was measured by the NO-titr, ation.
When C2H4 iS introduced into the stream of active nitrogen, a bright emission is observed at the mixing point. lncreasing the quantity of C2H', , this emission varies from grow to flame. Spectra ef the emission were the CN violet systeM (B2S"X2X"), the NH systems (A311-xS. S, cill-aid) and the N2 1 st positive band (BSIIg-ASX. "). The C2 Swan band(ASIIg w3n. ) and the CH systems (2d-2n, XE-2n)'were observed, too. lt was observed that the CN emission intensity had, twe maximum values with the increase of the concentration of CaH"introduced into the N-atom stream. From this result, it is known that this reaction has two stoichiometry faetors which suggest two different mechanisms. The stoichiometry ratio of Natom to C2Hs in the flame was 2 and that in the 910w was 20. n the former, the reaction scheme initiated by a H-atom proceeds as proposed by Herrons and in the latter, a ehain reaction in which the CN radical acts as a chain carrier takes place in parallel with H' fs scheme. The over-all rate constants of the reactions of N-atom with CaHs in the flame and the glow at room temperature were 3.13 10"M and 1.43 10-iS cmSemolecule"iesec-i, respectively.

View full abstract

The esterification of b6nzaldehyde has been studiedi over solid NaOH, NaOH-SiO2, A120s, SrO2, BaOz, SrO and CaO. The catalytic'activity was found not. only to closely relate with the basic properties, but also to relate, with the acidic proPerties (Fig., 6). lt was o. bserv. ed that two d-hYdrogens of benzyl groups of benzyl benzoate (major product) and benzyl alcohol (miner product) produced by the esterification of ibenzaldehyde-a-at were deuterat. ed. and t-hqt there The catalytic activity was was no hydrogen isotope effect(kH/kD=1, o, 2)(Figs, 1and 2), decreased by the addition of benzoic acid or phenol, but not by. the addition of benzene or cyclohexane' (Figs.3, 4 and 5). Thg amount of benzylE alcohol formed was increased by the addition of aliphatic alcohols (Fig.4).
On the basi's of the observed results, it has been concluded that the aetive sites for the esterification are metal bezylates and those for the formation of metal benzylate consist of both basic sites (surface OZ) and Lewis acid sites (Ca2" etc. ). The mechanism of the esterification has been N@discussed in detail and 'c'ompared, with those of Cannizzaro and Tishchenko reaction in homogeneous system,

View full abstract

IR spectra in the region from 1200 to 200 cm-i of the garnet selid solutions 1{Ys}[MgvMa, ](MsntvSiy)Ois (M=AIS", FeS", GaS", y=O. O te 2, 0) have been studied systematically and strongly localized group vibration of isolated tetrahedren er octahedren was feund. The spectra assigried to stretching vibratiofi, y3, of tetrahedra, AIOt, FeOa, and GaO4, splitted intothree bands in y=O, O co ositi n Qf each s 1id sdut n 3 bands f A10'degenerqted into two bands at y l O.5, but those of FeOi or GaO' degenerated into oRe band at y 41.5 (Tables 1, 2 and 3, Fig.1, 2 and 3). ys bands shifted toward lower frequency with increasing y value for AIO' (substituting octahedral AIS" by Mgg") but not remarkably for FeO4 or GaO4 (substituting octahedral Feg" or GaS" by Mg"") (Fig.4). From these results and the report of McDevitt, it is concluded that the frequency of ys vibration of tetrahedron is affected by the ionic radius, that is, ionic field strength of neighbeuring dodecahedral and octahedral cations. The similar frequency shifts were also evident in the case of ys bands of SiO' (Fig.5). The difference of degeneration tendeney of v3 bands between AIO' and FeOt or GaOd suggests that the bonding character of FeO, or GaOA differs from that of AIO': the interaction of FeO' or GaO' with the garnet lattice seems to be small comparing with that ef AIO'. The bands assigned to stretching vibration of oetahedron were 520, 474, and 438 cmmi for AIO6, 382 and 362 cm-i for FeOs, 466, 400, and 342 cm-i for GaOs, and 400. v350 cm'i for MgO6, respectively.

View full abstract

The heat of solution in water (endothermie)' and the hydration number, of twenty-six kinds of the cobalt( )cor 1exes andof ten: kinds of simple salts were determind at in nite dilution (250C) using micro calorimeter of twin-type and ultrasonic interferometer, respectively. The additive property held on both the heat of solution in water and the hydration number of the constituent ions. The hydrations number were as follows, Co(NHg)glg" 11, [Co(H20)(NH3)g]S"12, [Co(en)3]3' 14, [Co(NO2)(NHs)s]2" 16, [CoCl(NH, )s]2" 24, Co(COs)(NH3)'1" 21, [Co(gly)s]26, [Co(edta)] 18, [Co(NO2)a NHs 2]ww 23, [Co N Os d]'S, pt 33, Na" 5.1, K" 8.4, NH" 1.7, Clew 2.0, Br 4.3, lww 2.7, NOs 4.3. The heat of solution to 1 mole of hydrated water was.59 kcal for all the salts determined. h the case of cationic cobalt( )complexes, co plex ions with smaller electric charge had greater hydration numbers. For the complex ions with equal electric charge, the hydratidn numbers ef complexes tended to increase as an ionic radius of cationic complex inereased.

View full abstract

Conditions of formation for four types, A, B, C and D, of aluminum tetrametaphosphate, Al₄(P₄O₁₂)₃, were studied in the reaction of α -A12O3 or Al(OH)₃ with NH4H2PO4.
Type A is produced on heating α -A12O3 and NH4H2PO4 mixture above 750 C. Type B is easily obtained by heating α -A12O3 and NH4H2PO4 mixture at 500-550 C. Type C can be produced by heating α -A12O3 and NH4H2PO4 mixture at 600-700 C, but it is intermingled with type A or B. By heating 1-5% mixture of thus obtained type C in α -A12O3 and NH4H2PO4 at 525-575 C, pure type C is readily and reproducibly obtained. Type D is produced by heating a mixture of α -A12O3 and NH4H2PO4 in nitrogen stream or dry air at 500 C, while heating of this mixture in vacuum at 500-700 C gives type B as sole product. The type and yie1d of aluminum tetrametaphosphate formed greatly depend on the sort of aluminum compounds used as starting materials, molar ratio of the aluminum compounds and the phosphate, heating temperature and atmosphere.
IR spectra and thermal transformation of aluminum tetrametaphosphate were also discussed.

View full abstract

Kinetic studies were made on the reaction of elemental fluorine with petroleum cokes, heat-treated at various temperatures, by means of a thermogravimetric method.
The reactivity of the samples, heat-treated at 1800 and 1980 C, near at which graphitization of the coke proceeded rapidly, was the poorest, that is, the initiating temperature of weight increase was the highest and the reaction rate was the slowest. Up to 50% of weight increase of the samples, the rate of formation of graphite fluoride was proportional to the square root of fluorine pressure and the apparent activation energy was found to be 41.0 ± 1.5 kcal/mol, irrespective of the temperature of heat treatment of the samples. It could be considered that the rate-determining step of the reaction might be the dissociation of fluorine molecule absorbed on the carbon surface, since the energy value observed was not so far from the dissociation energy of fluorine molecule. The interlayer spacing of graphite fluoride prepared from the petroleum coke, heat-treated at 1980 C, was about 6.5 A and close to one of the crystalline graphite fluoride prepared from natural graphite.

View full abstract

The heated products of Nd2O3, Y203, and V203 at 1400 C in vacuo (-10-4mmHg) for an hour were studied through an analysis of X-ray diffraction patterns.
In the case of Y203-V2O3 system, only a stoichiometric perovskite type mixed oxide (YVO3)was formed.
In the, case of Nd2O3-Y2O3 system, a crystal belonging to C-type (Sc2O3-type)was formed, if the mole fractions of Y2O3 in the reaction mixtures were above 0.65, and mixtures of both A-type (La2O3-type) and B-type (Sm2O3-type)compounds wete formed, if the mole fractions of Y2O3 were less than 0.40.
When Nd2O3, Y2O3, and V2O3 were heated together lattice constants of the obtained perovskite type crystals were proportional to the mole ratios of Nd2O3 to Y2O3, if moles of Nd2O3 + Y2O3 were equal to moles of V2O3. If moles of Nd2O3 + Y2O3 were more than those of V2O3, Nd2O3 was incorporated more easily than Y203 into the perovskite type crystals.

View full abstract

Titanium nitride (TiN) was deposited on the graphite substrate from a gas mixture of TiCl4, H2 and N2. The influences of reaction temperature and reaction gas composition on the deposition rate and the surface appearance of TiN layer were investigated. The effect of various factors on the orientation of TiN deposit was a1so studied. Deposition was observed at temperatures above 700 C (Fig.5) and the weight of the deposit increased linearly with deposition time (Fig.2). The deposition rate increased with an increase in reaction temperature or the N2-TiCl4 mole ratio, but above the N2-TiCl4 mole ratio of 6 the rate nearly unchanged. The deposition rate was 8.1 μ /hr at the temperature of 1200 C and N2-TiCl4 mole ratio of 8. The (110) planes of the TiN deposit were developed in parallel with the surface of the graphite substrate by increasing the reaction temperature and N2-TiCl4 mole ratio (Fig.6). The size of crystal1ite deposited under the conditions of higher temperature and higher N2-TiCl4 mole ratio was larger than that deposited under lower temperature and lower N2-TiCl4 mole ratio (Fig.9, 10). TiN, deposited under the former condition showed a golden-yellow color. TiN whiskers of 8 to 40 micron in diameter and 0.5 to 2 mm in length were obtained under the fol1owing conditions: reaction temperature, 1220 C, N2-TiCl4 mole ratio, 8 and 10, TiCl4saturator temperature, 41 C, H2 flow rate, 5 ml/sec, reaction time, 90 min.

View full abstract

The preparation method of alkali-substituted β -alumina from Na β -alumina, the fusion cast brick, Marsnite U, of Asahi Glass Co., was described. Since direct ion exchange of Na ion in Na β -alumina with other alkali ions using alkali aqueous solution is inhibited by a water adsorbed on the surface of Na β -alumina crystal, Na ion in β -alumina was replaced, in the first place, by (H3O)+ through the immersion of Na β -alumina in concentrated sulfuric acid. When Na β -alumina powder of 1-2mm in diameter was treated with concentrated sulfuric acid at 240 C, the replacement of Na ion by (H3O)+ was not complete because of the formation of aluminum sulfate. When Na β -alumina powder finer than 325 mesh was used, the complete replacement was obtained by 20 minutes' treatment at 240 C. On the other hand, the replacement of (H3O)+ in β -alumina by K ion and Li ion through the immersion of H β -alumina in the saturated aqueous potassium or lithium hydroxide solution, was favorable with the treatment at 240 C for 2 hours. H- and alkali-substituted β -alumina obtained by the above described exchange reaction was identified by DTA, TGA and X-ray diffractometry.

View full abstract

Severa1: new coPPer(II)and, nic: kel(II)complexes of N, N'-bis(2-carboxypheny)oxamide (abbreviated as Hcpox) have been prepared (Table 1) ancl studied by means of magnetic susceptibilities, infrared and eleetronic spectra (Table 2). ln the diamagnetic square-planar complex, K2[Ni(cpex)]e3H20, the ligand is coordinated through carboxy-O and deProtonated amide-N atoms as the quadridentate 1igand (Formula A). The paramagnetic complexi Ni2(cpox)(py)6.3H20, has an octahedral structure bridged by cpox as shown in Formula B, whereas ligands are not coordinaced to nickel in [Ni(en)b][H2 cpox].3HaO. The copper complexes, Cu2(cpox)(NHs)ae4 H20 and Cu2(cpox)(A-A)enHiO (A-A=ethylenediamine, N, N-dimethylethylenediamine, 1, 3-prepanediamine or 2, 2'-bipyridine), are all magnetically subnormal, and bridging structures are suggested as shown in Formula B and C for them. Only the tetragonal complex, Na2[Cu(cpox)].4 H20, is magnetically normal, and its structure may be simiiar to Formula A.

View full abstract

Nicke1(II)and cobalt(II) complexesof imin, diacetamide(abbreviationidaaH2), Ni(idaaH2)2(CIO)2 and Co(idaaH2)2X2 X=Cl, Br, 1 and CIOP, were prepared and their infrar6d ana visibi'6diffuse-reflectance spectra were compared with those of Cu(idaaH2)2(CIOD2, the crystal structure gfA. which was already determined2). The coordination of the copper complex is presumed by a diffuse-reflectance spectrum (Table 2) to be distorted or elongated octahedron. M The infrired spectrum (Table 3) suggests that the two imino nitrogen and the two amide oxygen atoms of the two ligand molecules are situated in trans;, positions on the plane including th6 Vcopper atom. The-se results are supported by the crystal analysis While the crystal analysis suggests a weak bending between the copper and each of the remaining two amide oxygen atoms, the infrared spectrum does not give any evidence for coordination through these oxygen atoms. It is, thus, supposed that these oxygen atoms are cQordinated too weak1y to the copper atem to have any effect of coordination on molecular vibrations.
Similarly, the ligand acts as if bidentate in the infrared spectra of the nickel and cobalt complexes (Table 3). The diffuse-reflectance spectra show that the coordination around the nickel and cobalt atoms is octahedron but not necessa. rily regular. By these results the structure of these complexes seems to be similar distorted otahedron to that of the copper complex. To evaluate the extent of distortien, the crystal structure of the nickel complex is now under investigation by means ef X-ray diffractometry.

View full abstract

By the thermal dec, mposition reactinof ethylenedinitri1otetraacetatomamaganate(III) complex (Mn(III)EDTA)and trans-1, 2-cyc1, hexyleedinitri1 tetraacetatomanganate(III) (Mn complex (III)CyDTA), manganese(III) ions in these complexes are reduced t, manganese(III) ions This PaPerM deals' with the chemical formula of the species which are Jformed by.. the thermal ae60rnposition reaction of these complexes. The experimental methods are 4s follews;
Afteorr the thermal decomposition reaction was completed, the reaction preducts were changed to Co(III) complexes, which were separated by the ion-exchange chr, matographic techpique t an anioriic, a hon-charged and a cationic part. Frem the anionic and the non-charged part, crystals were obtained and identified by elemental analyses, IR and visible absorption spectraReaction prodqcts in the cationic part were not identified because of a small amount of this part, These results are give in Tables 2 and 3 and Figs.3and 4 By this procedure, Co(III)EDTA, Co(III)CyDTA, ethylenedinitrilotriacetatocobalt(III)(Co(III)EDTRA)and trans-1, 2-cyclo hexylenedinitrilbtriacetatocobalt(III)(Cd(III)CyDTRA)60mplexesnwere confir ned. Gaseous products were identified by polarographic and gas chromatographic methods.
From these results, it was found that therma1 decomposition products of Mn(III)EDTA and Mn(III)CyDTA complexes in solid state contained EDTRA, CyDTRA, CO2, CO and HCHO. In addition to these, it was found that unchanged ligands (EDTA and CyDTA) still remained even after the complete red uction of Mn(III)in Mn(III)complexes to Mn(III). The am, ount of each part was determined and visible absorption spectra of Co(III)EDTRA and Co(III)CyDTRA complexes are given in Tables 4, 5 and Fig.5.
From this work, it is concluded that,
(1) The thermal decomposition reaction in solid state involves the intermolecular electron transfer reaction, and
(2)By the thermal decomposition reaction of aminopolycarboxylatemanganese(III)complex, new type of ligands such as EDTRA and CyDTRA may be produced.

View full abstract

The thermodynamic quantities associated with the formation of the complexes of tetraphosphate ion with Mg(II), Ca(II) and Sr(II)are determined and compared with those obtained brevious1y fer pyrophosphate and triphosphate complexes of these 41kaline-eart-b m-et-41-ions 1) The thermodynamic stability constants of the complexes of the types ML, MHL and MsL (where M, H and L are a metal ion, hydrogen ion and tetraphosphate ion, respectively)are evaluated from pH titration data obtained at various ionic strengths at 25C.2) The enthalpy changes associated with the fermation of the 1: 1 complexes (ML) at.25C are determinedmined by direct calorimetric method. From these values and the thermodynamic stability constantsi of the 1: 1 complexes, the corresponding entropy changes are calculated.
As shown in Table 2, the eomplex formation is always endothermic and entropieally favored. The dSe increases considerably with decreasing radius of the metal cations (r) and with increasing chain length of the polyphosphates (1). The dH, on the o-ther hand, depends only sligfitl y on both r and 1. All these results are explained in terms of present theories of metal c helate formation in aqueous solution.

View full abstract

A new determination method of cadmium by atomic absorption speetrophotometry was proposed.
The methQd was based Qn the extraction Qf th ion-pair, fQr, 4 bet we anion of cadmium iodide eomplex and zephiramine cation, with ethyl acetate. The cadmium concentration in the ethyl acetate was determined by atomic abserption spectrophotometry by the use of airacetylene flame.
To 50 ml of an aqueous sample solution in a saparatpry funnel weiie added l ml of 2 molll potassium iodide solution, l ml of the acetate buffer solutien (pH 4.6) and 10 ml of ethyl acetate. The mixture was shaken for 2 rninutes in order to extract the cadmium-iodidezephiramine ion pair into ethyl acetate.
After separating organic phase the absorbsnce was measured with air-acetylene flatme at 2288 A cadmium-line.
By this method, the cencentration range frem 2 to 40 ppb of cadmium in the aqueous sample solution could be determined accurately. The standard deviation was O.0025 and the variation coeMcient was O.98%e at the cadmium level of 30 ppb,
Copper interfered seriously with the determination of cadmium, but the considerabiy large amounts of many ether popular eations and anions did not interfere. The interference due to copper could be removed by masking it with thiourea,
This method was applied to the determinatien of cadmium in fresh water.

View full abstract

. Chromazurol S(ChS)reacted with beryllium(II)in the presence of hexadecyltrimethy1ammonium(HDTMA) salt to form a temary complex of blue coloration. The ternary complex was completely extractable into 1-bdtanol in the pH range from 6, 6 to 7.0 and it had an absorptio: n maximum at 596 nm. The absorbance of 1-butanol extract remained constant for many hours at room temperature. Under the optimum conditions of pH, reagent concentrations and the others, the absorbance of the extracted complex obeyed Beer's law over the concentration range up to 7umol uberyllium(II)in aqueous phase, and the gptimu: m concentration range of berylli. um(II)determination was betwee: n O.95 and 3, 3umol/1(Ringbom's plot), The molar absorptivity at 596 nm was 58500l, cm-1, mol-1 corresponding to Sande1Ps sensitivity i: ndex of O. OOOI5, ptg/cm2. The molar ratio of three components in the extracted species was estimated to be Be(II): ChS: HDTMA=1: 2: 4.

View full abstract

In order to develop a quantitative analysis of polyester components by NMR spectrometry, proton NMR spectra of a monobasic acid, 16 kinds of dibasie acids and 11 kinds of polyfunctional alcohols ordinarily used as the starting materials were measured, and the assignment of signals was discussed. The NMR spectra of 24 kinds of polyesters derived from the above raw materias were identified. The monoalcohol esters of acids and acetates of polyfunctional alcohols were prepared as a pure model compound of NMR spectrum, in order to make the functional groups of raw materials to bear a close resemblance to those of polyesters and to use the same suitable NMR solvent.
It was relatively easy work to assign the most peak to the acid components, because there are some of the proper proton signals in themselves. The spectra of each polyfunctional alcohols, particularly in the case of multiple components of the similar alcohol, overlapped respectively, then it was not so easy to identify. lt was necessary to confirm whether the alcohol component to be contained or not in the polyester sample by means of the other analytical procedure.
The chemical shift values of the acid and alcohol components divided from the spectra of polyesters were good agreement with the pure model compounds. lt was described that the quantitative analysis of polyesters should be done quickly and accurately.

View full abstract

The chlorination of dichlorobutenes gave a mixture of meso and dl 1, 2, 3, 4-tetrachlorobutanes. The chlorination reactions of trans-1, 4-dichloro-2-butene (tr-DCB-2) and 3, 4-dichloro-1-butene (3, 4-DCB-1) were carried i, out in order, to elucidate the effect of solvent, Qn the formation of the mese isomer..
When tr-DCB-2 was chlorinated in carben tetrachloride, both trans and cis addition to double bond occurred at the same time as a result of the free radical reaction and a mixture of meso and dl isomers was fdrmed. On the other hand, methylene chloride was favorable to the formation of the meso isomer. The ionic pathway dominated in methylene chloride because of its high polarity and the reactiton was exclusive trans addition.
The ratios of lhe meso to dl isomer in the chlorination of 3, 4-DCB-1 were approximately constant undethe various conditions.
The selectivity for the meso isomer in the photochlorination was found to be quite similar between two starting materials and was merely dependent on the solvent.

View full abstract

The chlorination of diethyl 1-hydroxyethylphosphonate, 1-hydroxybutylphosphonate, and α -hydroxybenzylphosphonate with thionyl chloride in the presence of pyridine gave the corresponding α -chloroalkylphosphonates in moderate yields. However, similar treatment of diethyl α -hydroxyphosphonates obtained from ketones and diethyl phosphite gave α, β -unsaturated phosphonates. Theses products were almost quantitatively converted into the saturated compounds by catalytic hydrogenation in ethanol using Raney nickel as catalyst. The results are given in the Table 1. This method seems to be useful for preparation of s-alkylphosphates which are di cult to obtain by the Mi6haelis-Arbuzov reaction and the Michaelis-Becker reaction.

View full abstract

The codimerization of styrene with ethylene or propylene using, palladium-containing catalysts was studied. It was found that three-component catalysts consisting of palladium salt, Lewis acid, and tertiary phosphine were effective for the codimerization and that the products of the codimerization using the three-component catalysts were different from those of the cq, dimerization using one-component catalysts such as PdCI2, (PdC12. PhCH=CH2)2, and PdC12. (PhCN)2. The codimerization of styrene and ethylene with the three-component catalysts such as (rr C3H5PdC1) BF3, Ph3P, (PdC12, PhCH=CH2) BF3, Ph3P, and(π -C3H5PdC1)2-AIC13-Bu8P gives 3phenyl-1-butene and 2-phenyl-2-butene as codimers, though it has been known that the codimerization with the one-component catalysts gives 1-phenylbutenes. The difference between the catalytic behaviors of the former and latter catalysts was investigated in detail. As a reaction mechanism for the codimerization by the three-component catalysts, a mechanism involving the formation of a palladium hydride as a catalytic active species is proposed.

View full abstract

Catalytic oxidation of 1-butene l for a., 6etic acid was studied over vanadium oxide catalysts supported on silica in the presence of steam at temperature range of 200N300C.
Binary and ternary oxide catalyst systems containing SnO2, WO3 and TiOdii as the second or the thild componenntt exhibited selective formation of acetic acid, w, hile both activisy and selectivity wer6 poor in the absence of these promoters. The selectivity to qcetic acid -was dependent mainly on the reaction temperature and the catalyst compositig. n, but ip. depepde. pt of the Conversiori of butene. Over the catalyst of V-Sn-W (1: 1: 0.5) oxide on silica, acetic acid was produced with se1 vity, of 50-55% and 45-50%at 225. C and 250, respectively,

View full abstract

The catalytic oxidation of butenes was kinetically investigated in the presence of steam over the catalyst of V-Sn-W oxides on silica.
The apparent activation energy below 270A1280eC was greatly different from that above 270-280C, and acetic acid was mainly for formed below 270-280. C while COa and CO were the main products above 270. v280C. The reaction below 270 v280 C seemed to consist of parallel reactions to form acetic a. cid and carbon oxides, which were strongly inhibited by the product acetic acid. The inhibition was resulted from a competition with oxygeti for the same active site. The rate of oxidation of 1-butene was represented by the following equation:
γ =k Ko2Po2Pe4Hg/(1+Ko2Po2+KA e oMPA e oH)
(k: Rate eenstant, Po2, Pc4Hs, PAeoH: iPartial pressure of oxygen, 1-butene and acetic acid,
respectively, Ko2, KAoH Adsorption equilibrium constants of oxygen and acetic acid)
Validity of this equation was confirmed by the agreement between the experimental and the calculated values.
The rate determining step of this reaction was considered to be a surface reaction of adsotbed oxygen and physically adsorbed butene, and the apparent act, ivation energy of this step was calculated to be 9.8

View full abstract

In order to obtain basic data for the treatment of waste water from sulfur dye-dyeing process, the coagulation of sulfur dye solution was investigated by using (1) A12(SO)s. n H20, (2) FeC13.6 H20 and (3) FeSO e7 H20-Ca(OH)2 as coagulants. Sulfur Black B (C.1. Sulfur Black 1) was used after purification by means of dialysis with cellophane membrane. Satisfactory coagu1ation of the dye was observed by dosage of 10N30 mg/1 of these coagulants as metal ion. The optimum pH ranges in the cases of coagulants (1) and (2) were 5N6, and that of coagulant (3) was 9xvlO. Among the inorganic salts probably contained in ordinary waste water, the coexistence of NaCl and Na2SO4 showed relatively small effects on the dye coagulation. The coexistence of Na2COs increased the amounts of the coagulant (1). required for coagulation and Na2S20s protected the dye from coagulation with the coagulant (2) in acid solution. The coagulation in alkaline solution with the coagulant (3) was not appreciable affected by the salts described above. In case of (3), the effect of anionic surfactant of less than 80 mg/l on the coagulation was negligible.

View full abstract

Lozenge single crystals and circular ones both of them having a central hole have been grown with a low molecular weight poly(isobutylene oxide) (op, , /c: O.25) by cooling it slowly to room temperature from the melting at 200C under vacuo below 10m3 mmHg. As for the holes, they were located almost center of the crysta1s and their diameters measured at the bottom were in values of around O.5μ.
For the origin of the hole, it was shown that strength of Burgers vector of the crystal calculated on the basis of Frank s theory is of an agreeable value in comparison with the lamellae thickness measured from the shadow length of the replica pictures.
Some with concentric ring-like appearance among the circular crystals showed positive birefringence in the central area along the radical directions. They are nearly single crystal grown by helicoidal mechanism centered on a screw dislocation, which differ from a spherulite composed of lamellaei where the molecul-aTe chains arrayed tangentially to the radius by branching mechanism as usually known., On the positive birefringence, it was suggested en the basis of the orientation of the molecular chains in the crystals that the lamellae in the central area grew conically around the center and consequently the molecular chains in that area could be arranged parallel to the radius.

View full abstract

In this study, natural rubber vulcanizates which were deformed to variable strains were exposed to r-ray, and their chemorheological properties were examined by the stress reiaxation measurements in nitrogen atmosphere. The rate of relaxation decrcased with increasing extension ratlos.
The rate of the degradation which was caused by peroxyradicals produced in the presence of oxygen was too fast to observe the effects on extension ratios. In nitrogen atmosphere the rate of stress relaxation varied in proportion to the extention ratios, and the slope ef the proportional constant changed with crosslinking density. Further, the rate of stress relaxation of such vuleanizates seemed to be affected by the crosslinking structures, i. e., peroxide or sulfur crosslinking.
Nielsen has reported that the force of contraction was directly proportional to the degree of the orientation of polymer chains. The degree of orientation was inverse proportion to the relaxat ion rate. Thus, it was suggested that the decrease in rate of degradation in high extension ratios was not cagsed by the crystallization, but mainly by the orientation of polymer chains.
The oriented molecular chains were easily cut by r-ray irradiation, so-called by mechanochemical process. The produced macroradicals activated adjacent chains or recombined with other macroradicals. As a result, induced network increased and retarded the stress relaxation in large deformation.

View full abstract

Aqueous solutions of partially acetylated pely(vinyl alcohols) (hereinafter is abbreviated as PVA-Ac) split into two phases above the cloud points. The cleud point curves, i. e., the liquid-liquid solubility curves of PVA-Ac vs. water has been determined. The cloud points were depressed by the added salts just as the aqueous solutions of nonionic surfactants. The cloud point curve of PVA-Ac-H20 system was influenced marked1y by the saponificatien degree but not infiuenced appreciabiy by the degree of polymerization of PVA-Ac.
It was found that the vapor pressure of water in aqueous solution of PVA-Ac stays nearly constant up to 40 wt% solution and then rapidly decreases. This fact is an impressed evidence that an aqueous solution of PVA-Ac is similar to the microscopic two phase mixture of water and water swollen polymer.
This system affords an interesting example that the dissolution proceeds by the orientation, arrangement and sti u: ture formation of water soluble polymers.,

View full abstract

The reaction of o- or p-cresol with formaldehyde in the presence of ammoniacal catalyst was followed by NMR. spectroscopy.
It was found that at an early stage of each reaction tribenzylamine was formed (see Figs.1and 2)followed by the formation dibenzylamine and oxazine compound.
The molecular weight of product calculated from NMR data was ab6ut 250 at the iRitiql stage of the reaction; then with the lapse of time it decreased gradually and again increased. nally. Cresol was more reactive than o-cresol.
As for the reactivity of e- and p-position of o-cresol in the reaction with ammonia and formaldehyde, it may be inferred from the data of IR and NMR spectra that the former was more reactive than the latter at the intitial stage of the reaction.

View full abstract

ln previous papers the number-average-structures of ammoniacal resols from xylenols and cresols have been studied usipmg NMR spectroscopy. This presents the mechanisms of formation of methylol group and compounds containing nitrogen using the previous data.
From, the NMR spectra of initial produt of reaction, the product might be considered to be tertiary-benzyl-amine, which gradually changes to secondary-benzyl-amino-oxazine in the 2, 4-xylenol. The primary-benzyl-amime could not be found in the products. lt was shown in previbus paper that secondary-benzyl-amine had catalytic action on the reation of phenols and formaldehyde.
In the case of 2, 6-xylenol which has a functionality on para-site, however, it s tertiarybenzyl-amine acted as the catalyst for the reaction and the reaction rate was considerably higher than that of secondary-benzyl-amine. lt was considered that the difference between the catalytic action tertiary- and secondary-benzyl-amine depended on the stability of their chemical structures in the reaction system.

View full abstract

The ethylenattt. on of pyrogallol with ethylene dichloride in the aprotic polar solvents, in the presence of cupric oxide or bronze, gave 2, 3-dihydro-5-hydroxy-1, 4-benzodioxin in a good yield. As a solvent DMSO was preferable to DMF.

View full abstract

4, 4'-Azoxytoluene was oxidized with sodium dichromatQ in sulfuric aeid, or with chromium oxide (W) in acetic acid to give P (P-tolyl-ONN-azoxy)benzoic acid (a-acid) and a small amount of p (p-tolyl-NNO-azoxy)benzoic acid (B-acid). The structural assignmentl of the products was made by means of NMR spectra of the methyl esters of ev and B-acid.

View full abstract

The hydrogehation of allyl a160hol with PdlCcatalyst suspended in ethanol was carried out in a stirred tank reactor at atomospheric pressure. The reaction system was approximately represented by two parallel reactions; (1) hydrogenation to propanol and (2) that to ptopionaldehyde, as shown in Fig.1.
Rate equations of paths (1) and (2) based on the'Langmuir Hinsheiwood mechanism were determined as Eqs., (1) and (2), respectively, by applying the methed of nonlinear least squares to the experimental results and taking into account the temperature dependency of the constant.

View full abstract