It was known that the differential equation (eq.(1)), which deals with diffusion of each ion in mixed solutions of electrolytes, gave the results which agreed well with the observed phenomenological diffusion coefficients when it was solved numerically by trial and error method. In the present paper, the calculation is extended to find the relationship between diffusion coefficients of ions and thier properties, especially their charges and moblities. The results of the computation obtained were used to calculated values of R1/pq (eq.(2I)) which give the relative value of the apparent diffusion coefficients of i-ion in a certain solution to those in the standard electrolytes. In order to elucidate a tethephyca lmean in gs of the d ie ren tia lequa tion, the equatn was so Ved in terms of theapproximatin that the C0 ncentration sofio n distribute linearly m thed iu son layer. The calculation was mamly Carriedou tab out the solutions contain in gt WQ electrolytes with comm DnaniDn A SareSut, it bec ameevden t thatm the solution Conta in ingtwo electro lytes, the catonof largermob ility diu sesmore rapidly and that of smaller mob ilityd iu sesmore slow than that mtheso tioncontainings ing leelectrolyte (Fig 3, Fig.4), and that in mixed solution of and electro Iy tes, the di Vale nt Catin d ses Counter to concentration grad ient if the mob ilty of amon is relatively sm an (Fig.6, 9). Calcu1ated pgvalues a greed with ob served on es shownm tne llterature about the solutions of Sin gle electro Iy tes (Fig.1) and a lso With Qurexperimenta I Vauab Qut the mX eds. utiQns of two electrolytes KC MgCl, H, O and KHAsp-Mg(HAsp), -H, O, (Fig.2). The Haskell equation on the diffusion coefficient of an electrolyte was generalized by introducing correction factor which concerned with the concentration dependence on the activity coefficient (eq 20).

View full abstract

The kinetics of ion exchange adsorptions of Co(II)and Ce(III)at extremely low concentrations on the chelating resin, Dowex A-1, has been studied by using limited bath method.
The rate of ion exchange adsorption of Co(II)is dependent on the ionic strength of the solution, particle size of the resin, and reaction temperature. At higher ionic strength (O.05N O.1), the kinetics is controlled by particle diffusion of Co(II), whereas at l ower ionic one(0.001-0.01), sion is predominant. The diffusion coecient of Co(II)for the particle diffusion, calculated by the kinetic equation of Kressman Kitchner, increases from 5.36-10-9 to 8 81 10-gcm2 sec as the temperature is raised from 10 to 30C. The apparent activation energy is 4.05 kcalimol at ionic strength of 0.1.
The kinetics of ion exchange adsorption of Ce(III)is independent of the ionic strength and particle size of the resin, and does not obey the kinetic equation for film and particle diffusion.These results supPort the view th at the rate-deterining step of this reaction is chelate formation reaction between Ce(III)and iminodiacetic acid, the functional group of the resin. The rate constant is increased from 1.68-10'g te 6.78 10-3 sec-i as the temperature is raised from 10 to 30C, and the apparent activation energy is 13.6 kcal/mol at ionic strength of 0.1.

View full abstract

Fe203-Deposition onto polyester, nylon and cotton fabrics in solutions of various pH at an ionic strength of 1 10-S was discussed in terms of the potential energy of interaction between fabrics and Fe203 particles. The pH of the solution was varied with 0.1NHCl or 0.1NNaOH, and the ionic strength was adjusted to 1x10-3 by adding O.1mol/l NaCl. Zeta potential (C) of fabrics and Fe208 in soluions of various pH were meased by the method of streaming potential (Fig. 1, 2). Potential energies due to the interaction of dissimilar electrical double layers (Fig. 3) and the interaction of van der Waals' forces (Fig. 4) between Fe20s and fabrics were calculated by the theory of heterocoagulation for a sphere-fiat plate system.
Total potential energy between fabrics and Fe203 is negative or gives a quite small maximum in the region of pH value below 8, and it has a larger maximum value with increasing pH (Fig. 6). Relation between th.e amount of dqposition of Fe203 onto fabrics and the pH of the solution (Fig. 7) almost corresponds to relation'between the potehtial energy and the pH.'The greater the mtaximum of the potehtial energy, the smaller the deposition of Fe20s. Addition of a small amout of NasPsOiG to an alkaii solution markedly decreases the deposition of Fe20s onto fabris as compared with the pH effect of the solution. On the other hand, the addition of sodium dodecyl sulfate to an alkali so1ution has no remarkable effect on the deposition (Table 1).

View full abstract

The kinetics of hydrogen-oxygen reaction over zinc oxide catalyst was investigated in the temperature range of 240.v320 C. The catalyst was not poisoned with the reactant gases, and the presence of the product (H20)had no influence on the rate of the reaetien. The apparent activation energy was found to be 18 kcal/mol. The rate of the reaction was well expressed by the following equation r-k(Vmpt /(1-VIMPTI))2 Poe where k' ahd K are eonstants, PH and Po are pressures of hydrogen and oxygen respectively.
The experimental results can be explained on the basis of the mechanism assuming that hydrogen- oxygen dissociatively adsorb on the different sites of the catalyst surface and that the stfrface reactioh between H and OH or between two OH groups is the ratedetermining step of the reaction.

View full abstract

It had only been pointed eut in the previous paper that the difference in the stationary rate of the hydrogenation of acetene with varying alcohol used as the solvent must have been due to the difference in the rate eonstant, and that the rate ef the hydregenation had increased further in the range of the higher concentration of acetone as shown in Fig 1.
In this paper, detail of the change of rate constant was made clear by the investigatien of the effect of the addition of alcohol on the rate of the hydrogenation of acetone with Raney nickel and the rate equation was proposed, available over full range ef the concentration of acetone.
When an aicohol was added, the rate of the hydrogenation could be expressed as followsiIt was concluded that alcohols acted as poisons decreasing a part of the active sites for the hydrogenation of acetone as well as diluents aRd the difference in the stationary rate of the hydrogenatien, re(1-A), among alohels were due to the difference in the value of A ameng alcohols.
The rate of the hydrogenation of acetone could be expressed as fellows.

View full abstract

Activity sequences of variousoxide catalysts foro1e rioxidation and reactivities ofo1es were investigated. When the oxidation reactions of olefins, with less than six carbon atoms, were caGried out on various catalysts and cempared the amounts of products obtained, quantitative relationships are found in the partial oxidation, but net in the complete oxidation. lt is conglude-d that the active sites and the reaction mechanism are identical in the partial oxidation, but different in the complete oxidation, The amount of the partial oxidatieh' preduets is deL termined mainly by the number of active sites, which is affected by the poison of irreversibly adsorbed residue. The relationships between the amounts of the partial exidation preduets and ionization potentials ef the elefin or the diolefin indicate that the adsorbed residue may be the product, diolefin. A bismuth molybdate eatalyst of equiatomic ratio, whieh is known as one of the typical catalysts in olefin oxidation, possesses a speeial low activity in the methacrolein formation, etc. lt seems that this is caused by the characteristic poisoning over the catalyst.

View full abstract

The codimerization reaction of propylene with ethylene, on various solid catalysts containing nickel and r tungsten has been investigated under atmospheric pressure at the temperature range of 200N3900C. Both NiO-A120, and NiO-WO3-A120s were effective catalysts for codimerization of propylene with ethylene, while WO3-A120s was inactive On the basis of the results of the isomerization reaction of 1-pentene and isopentenes, it was suggested that the initial preducts formed by codimerization were mainly n-pentenes, and isopentenes were secondary products resuked from skeltal isemerization of n-pentenes.
Most of product was dimer in the reaction of ethylene or propylene over these catalysts.Their aetivities were as follows For ethylene: NiO-WO3-A120g NiO A120s WOs-A120s O For prepylene NiO-WOsi-A1203 WOs-A120s NiO-A120s.
Besides dimerization, both double bond shift and skeletal isomerization were also observed on these catalysts.

View full abstract

Catalytic activity tests were carried out by a flow system-over thg"zirco-nu.m phospl ate catThs"tl which wa's prepared from ZrO(NO₃)₂ and NaHPO₄. Acidity, DTA TGA curve low frequency infrared spectrum and xrray pattern of catalyst samples were measured to characterize the catalyst structure.
The conversion data of the reaction were arranged in the integral form of the zero-order kinetics and the apparent activation energy of the reaction was nearly equal to 22kcal/mol at low temperatures ranging from 170 to 230C and 9.1kcal/mol at high temperature above 230C. The catalytic activity and the acidity of catalyst showed a rough linier relationship and both of them exhibited the maximum values at about 400C in the calcination temperature ranging from 200 to 1000C. Lewis-type acid sites, formed by the removal of water from zirconium phosphate having a hydrate sturucture, would be a cause od an acidic property and an origin of catalytic activity.
The zirconium phosphate, showed a similar characteristic to alumina in catalysis, was not effective for the reactions such as polymerization of propylene or dealkylation of cumene.

View full abstract

In order to investigate the oxidation activities of zeolites (NaY, CaY, HY.) in which exchanged cations have no apparent oxidation-reduction ability as is seen for transition metal, the vapor phase oxidation of benzyl alcohol over these zeolites was studied.
It was found that the oxidation proceeded consecutively over NaY:CeHsCH20H-CeHsCHO -C6HsCOOH. The reaction order of the oxidation of benzyl alcohol to benza1dehyde was O.4 with respect to benzyi alcehol and was O.5 with respect to oxygen. The activation energy in the temperature range of 220-300C was 11kcal/mol.
The temperatures where the conversion of benzyl alcohol reached 3% were as follows HY:1950C, CaY:245C, NaY:265C. Therefore, the order of oxidation activity was HY>CaY>NaY. The yield of carbon dioxide was very low (O.43%).

View full abstract

Catalytic properties of nickel supported on stoichiometric titanium carbide in acetone hydrogenation have been studied at 150C.
Over the catalyst (I) which was rcduced with hydrogen after calcination in nitrogen isobutyl methyl ketone was formed as a minor product, whereas over the catalyst (II) which was reduced after calcination in air the ketone was formed predominantly along with a small amount of 2-propanol. X-Ray analysis showed the existence of nickel oxide in I in addition to metallic nickel and stoichiometric titanium carbide, whereas in asmall amount of titanium dioxide in rutile form existed in addition to the above species. Both nickel oxide on the carbide (III) and nickel on rutile (IV) exhibited some activity for the acetone hydrogenation; the main product was the alcohol over and the ketone over IV. Over unsupported nickel the ketone was not formed.
It is concluded from the experimental results that the catalyst systems which consisted of nickel with or without its oxide and titanium carbide with or without titanium dioxide caused the simultaneous formation of the alcohol and the ketone in the hydrogenation of acetone.

View full abstract

To elucidate the special catalytic action of metallic palladium in the partial oxydation of olefin, catalytic acetoxylation of propylene and n-butenes was investigated in acetic acid.
In the propylene aeetoxylation catalyzed by metallic palladium, allyl acetate (Pi) was a unique product, although isopropenyl acetate was also eo"produced over Pd-activated charcoal catalysts (Fig. 1). On the other hand, the acetoxylation reactions of n-butenes were rather complicated (Fig. 2). In this case, the products, resulting from the catalytic action of metallic palladium, were CH, =CHCH(OAc)CH3 (Bi), CHgCH=CHCH20Ac (Bi), cis as well as trans isomers of CH, =CHCH=CHOAc (Bs and B6), and an unidentified compound (B3), Their relative amounts were No.4 changed sensitively by the speies of n-butenes or the preparative method of the eatalysts (Table 1 and Fig. 3).
In the case of the formation of B1 and B4 from n-butenes as well as that of P1 from propylene, the rr-allyl mechacism is reasonably applicable to the main acetoxylation reaction, although side reactions should also be taken into aecount to explain the ompliated course oS the These are discussed in terms of the catalytic partial oxidation ofole110ver metallic palladium suspended in water.

View full abstract

Relationship between activity and structure of various U-Sb-O catalysts was investigated. As shown in Table 1, the catalysts prepared by the coprecipitation method and by the precipitation method showed high selectivity of acrolein formation, while the catalysts by the impregnation method were fQund inadequate to acrolein forlnation. The selectivity of U-Sb-O catalysts was infiuenced by the oxidation states of antimony oxides which were used as a srting materia1 o fthe cat alyst preparation. Sb20 was bett er than Sb20 . Although anys imple relationship between structure and activity was not obtained, the formation of USb30io duripg the course of the catalyst preparation was seemed to be:necessary in general for the apPearance of the surface was retarded by the presence of oxygen in the reaction system This retrdation effect of oxygen varied widely from catalyst to catalyst. As shown in Fig 5, ESR spectra of the catalysts at room temperature revealed the presenceof paramagnetic species such as U5O, or O. The presence of Oor O-was closely related tothe selective oxidation activity of the catalyst, whereas there was nodirect relationshp between the amount of Ull", and the catalytic actvity.

View full abstract

The breakdown veltage ef n-butyl alcenol, cyclohexane and the transformer oil was measured during and after the irradiation with ultrasound. The breakdown voltage decreases with increasing irradiation of ultrasound and the effect of ultrasound is continued fer a few minutes after the irradiatien. The temperature dependence on the breakdown voltage ef the sample like cyclohexane, which shows a considerable temperature dependence before irradiation, becomes very small when irradiated with ultrasound lt was found that the low frequency ultrasound is mere effective than the high frequency ene Either the cirect or the indirect effect on cavitation may be the cause of the decrease in breakdown voltage.

View full abstract

The thermal deeom positi on prcess ef tuagsten tctrachleride and lower tungsten chlorides were studied bs means of spring halatace ig an argon atmosphere. The dispreportiematien psue of tungsten tetch oride ad ptgsten corides were easured by a Bo doa-typl man ometcr. Ga speeies prodllced by dispropertienatieg ef these tungsten chlorides were studied byDea:ns electronic spectrad sod spece were stdied by checal a alyss ad Xay diffractrometorv. Ir vvas confirmed that t nngs ten tetrachloride and ewer tMngsten chlorides disproportionated argon atm sphere as fell ws (WC WC WC 9) WW WC9 d WC1 WsW 9 O" the othef hand yrr hen tungsten tctrach1eride was heated i n a clased vese 1, it began te dispret 325 to give ngs peotahlodde and WC18. This p xluct(WCI, .5)began to dispr oponienate at 350 to gi ve tuagsten d ichleride and tungste n pentachleride when it as heat in argoR at nosdosed vesse1. The dispoportio ation pres e of 9 sten tetrahlotide and WC s.s were given as fo11ows:kgP (mm.kg)-112x 19. 1(3 400), for WCd 1ag Pais2(mm Hg) g44 x leS/T 145 (35() 450). fof WChr. FDn9e:resutshe fOwiag thergnOdyna .ic vaeS were obtained .SGe s13 1gS-75. s T caYm el sa5-v40, for 3 WCg s3=2 WCIsx s WC1s(g), 396 1Pt-53.1 Tao(350-450). for 2 WCI35=WWCnl(s).

View full abstract

The operating conditions of urea autoclave in the partial recycle process were determined by the optimum condition of the process, but by the problem of mategials for high pressure equipment, by-produced ammonium salts and biuret. We have analyzed the above conditions from the following points of view.
First, the optimum molar ratio of NH₃CO₂ in the total feed to autoclave was discussed from the point of equilibrium of urea synthesis and thermochemistry, and second, the optimum residence time of the feed into the autoclave was discussed from the points of reaction kinetics and economics of the whole process.
The results obtained in the above analyses are that the optimum NH₃CO₂ is about 4-5 and the optimum residence time is about half an hour. These two conditions are in very good agreement with those adopted in the actual plant. The reason to come to this conclusion consists in the existence of the maximum conversion with change of temperature and higher cost of utilities than that of investment.

View full abstract

In previous paper on fiux action of aniline hydfochloride for soldering, it was shown that the reaction of CuCl₂ and Cu-complex with molten Sn-Pb alloy solder and the dissolution of Cu into the solder played an important role in spreading of solder on copper plate.
In this paper, flux action of various metal salts for soldering has been studied from the view point of the reaction of the flux with molten Sn-Pb eutectic alloy solder and spreading of solder.
The flux action of metal salt may be considered as follow; Metal salt (metal benzoate and various metal stearates) reacts with molten SR-Pb eutectic alloy solder to give metal and Sn salts.
The metal dissolves immediately into the molten solder. The wetting of Sn-Pb solder on copper plate is improved by the reaction and the dissolution of the metal into molten solder. So, Sn-Pb alloy solder spreads well over copper plate.
And, the reactien of metal salts, with molten SR-Pb eutectic alloy solder may depend on the oxidation and reduction potentials of metal and the free energy (F) for a formation of metal stearate.

View full abstract

The kinetics of the substitution reactions of the lead(II) complexes of ethylenediamine-N, N', N'-tetraaetic acid (EDTA), N-(hydroxyethyl)ethylenediamine-N, N', N'-triacetic acid (EDTA OH), 1, 2-cyclohexanediaminetetraacetic acid (CyDTA) and diethylenetriamine-N, N, N', N", N"-pentaacetic acid(DTPA) with nickel(II) ion have been studied in a pH range 2.3 3.5 at 20 C and an ionic strength O.1 adjusted with sodium perehlorate.
The reactions were followed spectrophotometrically by absorption at the maximum absorption wavelengths of the lead complexes. The initial rate of the reaction (R) is expressed as Rr(k81Pb2) (24 Pb3DH)(PbX)(Ni2)for the EDTA, EDTA.OH and CyDTA systems, and R=(kik2/(H+)) (PbH2X)(Ni2)for the DTPA system.
Contribution of each reaction path to the over-all rate of the reaction was estimated. From the rsults, it was assumed that the reactien for the DTPA system proceeded through the step forming a binuclear intermediate complex, and those for the EDTA, EDTAeOH and CyDTA systems through both the former path and the dissociative path in which a rapid dissociative equilibrium preceded the formation of the nickel complex.

View full abstract

Amethod is described for the spectrophotometric determinationof.lanthanum, cerlum(III) prase dymium, ne dymium, samarium, eur pium, gad 1inium dysprosimh erbium thtilium, ytterbium (III) and lutetium with methylxylenol blue (MXB).
MXB reacts with lanthanoids to form water-soluble bluish-vio1et complexes and these aqueous solutions have their absorption maxima at 568-576nm. The pH range over which the co1oration is stable varies from pH 9.0-9.7(La)topH 6.8-7.3(Lu). The sensitivities (Sandell's expression) of the determination for each of lanthananoids are between 0.0037-0.0054ug/cm2.
On the other hand, lanthanoids react with MXB in the presence of cethyltrimethylammonium brmide(CTMAB) to form water-soluble blue complexes and the absorption maxima f these colored solutions appear within 630-650 nm. Maximum color developments are obtained in the pH 7-9. The reactions are quite sensitive and the sensitivities according to Sandell's expresslon are between 0.0017-0.0032g/cm2. Beer's law is obeyed for the complexes of lanthanum, cerium(III), praseodyum and neodyum at concentration up to L69/ml and for others up to 2.0ug/ml. As a result of investgation of the composition of praseodymium or gadolinium or lutetium comlex, the mole ratio of metal, MXB and CTMAB is esimated to be 1:2:3.

View full abstract

A method has been proposed for the spectrophotometric determination of microgram amounts of copper, after extraction of copper(II) from an aqueous solution into chloroform with 2-hydro xy-1-haphtaldehyde 2-benbthiazolylhydrazone(NBH) Various factors such as pH concentration of HNBH vo1ume ratio of two phases, shaking time, diverse ions, etc have been studied, and the optimum conditions for the determination of copper(II) have been established. The ratio of copper to HNBH has er of sample selution S n a 50 ml separatory funnel, and make the volume up to 20 ml with water. djusted to 5.3.v9.5 with acetate buffer solution, and then make the Extract the complex with 10.O m of chloroforme two phases for 5 minutes.After the phases have been sepa- bottle containing sodium sulfate, and the absorbance at 426 nm against the complexwhlch co1d be extracted The extracted coex had an ab- beenE, 60nfirmed to be o ntalnlng up to A linear relationship was found between the concentration of copper and the absorbance. The molar extinction coe cient and the se nstivity for 1o9(Icll)=O OOI were 2 2104 and 2 9 103pg Cu/ma, respectively. Several ions such as silver(1), cobalt(III), mercury(11), titanium('V), thiocyanate, tartrate and citrate interfered with the determination.

View full abstract

A chromatographic technique for the separation of carbazole by using a O.6 5cm column packed with alumina is studied Carbazele, whih is separated from large amounts of anthracene and interfering impurities by this technique, is determined spectrophotometrically by the color development with xanthydrol. Fifty milligrapas of the sample is dissolved in 10ml of o-dichlorobenzen. The sample solution is passed through the column, followed by 10 ml of e-dichloro- benzene. Then, carbazole is eluted with 5 ml of acetic anhydride. About 96tL of carb-azol e.ip anthracene can be recovered by this process. After 5 ml of glacial acetic acid is added, atcetic anhydride in the eMuent is hydro1yzed by the addition of 1.o ml of o.mo/l/of hydrochloric acid and standing for 30 minutes. Five ml of glacial acetic acid solution of xanthydrol (1 mg/ ml) and O.5 ml of conc. hydrochloric acid are added. The solution is heated at 800C fq, r 45-t 1minutes, dooled to room temperaure and diluted to 25 ml with glacial acetic acid. The ab- sorbance is measured at 570 nm against the reagent blank. By this method, .carbazQle in a.nthra- cene can be determined as far as O.Ol. This method is not interfered by the, p;esenee of phenanthrene, anthraquinene, acridine, naphthalene, diphenylene oxide, fluorene, ace'i qph, thepe and flueranthene, which are present as impurities in the sample

View full abstract

The extraction of aluminum(III)-Alizarin Red S(ARS)chelate with methyl isobutyl ketone (MIBK) in the presence of 1, 3-dibhenylguanidinium(DPG) salt has been investigated spectro-photometrically. The extracted species has an absorption maximum at abeut 525 nm, with a constant abserbance in the pH range from 5.5 to 5.9. For the absorbance of the association complex under the optimum conditions of pH, reagent concentrations and shaking time, Beer's gaw is obeyed up to 1.5 10"5 mo/1 aluminum in aqueous phase. The molar absorptivity is 2.90 10⁴l/mol cm at 525 nm. lt is found that the 1:2 aluminum-ARS chelate anion formS ion association complex of 1:2 molar ratio with DPG cation, and the complex is extracted from aqueous phase into organic phase.

View full abstract

A modified null-point potentiometry by the use of aR ion-selective electrode is.described. The procedure is as follows: An indifferent electrolyte is added to a sample solution, standard solution and diluent, in order to bring them to the same ionic strength and thus the activity coefficients of the test ions in all the solutions are identical. After the addition of the standard solution, whose volume and concentration are v, and C, , respectively, to the initial samplel'solution, whose volume is V, in which'the ion-selective electrode and reference electrode are immersed, the diluent, whose volume is v, is added. Prior to the addition of the standard solution, the cell emf of the sample solution is measured to be Ei. The cell emf, E3, after.each., addition of the diluent, is plotted aga.inst log(Vvs), and from this plot the volume, vd, of the added diluent corresponding to the equivalence Xpoint of Ei=Eg is obtained. Thus, the concentration, C, of the sa' mple solution is given by C=Cs vs/(vs vd) Data analysis for the evaluation of the equivalence point is easily accpmplished by the least squares method or by the three points method using three cell emfs (Ei, E3, and th6 cell emf after the addition of the standard solution). The concentrations of fluoride solutions ranging from to 5 10-5 molll are determi:ned wiarelative standard deviation of about o (mean). over the entire range exept the lowest concentration level. The least squares method shows a better precision than the thr.ee pQints

View full abstract

Cd(II) gave a one-stepped reversible wave at -0.776V vs. SCE in a mixed solution of sodium gluconate(0.1 mol/l), ammonia(0.6 mil/l) and potassium chloride(0.2 mol/l), while In(III) gave a one-stepped irreversible wave at -0.21 V vs. SCE in the same solutlon.
The half-wave potential of Cd(II) in 0.lmol/1 sodium gluconate solution shifted toward negatve value by the elevations of ammonia concentration from O.1 to 1 Mol/1. The same tendency was also observed when sodium gluconate concentration was increased from O.02:to O.2mo1 in the O.6mol/l ammonia solution.
Lingane's equation about the diffusion current of complex was applied to Cd(II)-gluconate-ammonia and the mixed ligand complex of Cd(II) was found to be (Cd(GHt(NH3)3)). But molar ratio of ln(III) complex was not clarified.
Calibration curve for simultaeous determination of Cd(II)and In(III)was obtained in the concentration range from 0.1 to 0.5 mol/l by D.C. polarography.
On the other hand, calibration cve for Cd(II) was obtained between 0 1 and 2 ppm by square wave polarography and 0.01 and 0.1 ppm by aodic stripping polorography with the aid of square wave polarographic technie. One hundred fold amout of In(III) did not interfer the determination of O.3 mmol/l Cd(III) by D.C. polarography. Furthermore, one thousand fold amount of In(III)did not interfer with the determination of 2 PPm Cd(II)by square wave polarography and OPPm Cd(II)by anodic stripping polarography with the aid of square wave pelarographic technique.

View full abstract

¹³C-NMR spectra have been examined to obtain the structural informations on a series of alkyl-substituted β-diketones and we found correlation between chemical shift and substituent.
Structual formulas of β-diketones employed in our experiment are listed in Table 1 and ¹³C chemical shifts are given in Table 2.
Since most of those β-diketones are enolised at equilibrium state, satisfactory spectrum of the keto form could not be obtained except three compounds. Therefore, chemical shifts of enol carbons are discussed mainly here.
(1)The existence. of two forms of enol([1-A]and[1-B])is supposed to B-diketone, but we cannot observe their spectra. This fact suggests the rapid evchange between these two forms.
(2) the shifts of the enol carbons (C-2, C-3) decrease monotonously with the increased inductive (-I) effect of alkyl substituents. That is, the enol carbons of a molecule with two methyl groups resonate at the highest field, and those with two butyl groups, resonate at low field. The similar effect which appears in the mono ketone has been reported by several workers.
(3) The signal of the enolic methine carbon (C-1) appears in 90-lO2 ppM region. lt lies in -extraordinary high field compared with those of mono olefinic or aromatic carbons. ln chelate ring of enol form, lone-pair electrons on the oxygen atom could take part in rr-conjugation. This effect causes the increase of π-electron density of methine carbon to make them more shielded.
(4) Furthermore, an additivity is found in the observed ¹³C shifts of m.ethine carbon for each alkyl substituent. Chemical shifts of asymmetric β-diketones calculated from the value of symmetric β-diketone are in good agreement with the experiinental values as shown in Table 3.

View full abstract

The solvent effects on the photolysis of to-phenoxy-p-hydroXyacetophenone (3) and the related keto ethers were investigated.
These keto ethers decomposed photchemically either in non-polar or in polar solvents. The photo-dec sitin was facilitatd in p1ar s1vesuch asbutyl alcohle isoprpylalch.
The photolysis of keto ether (3) was rematikably accelerated in triethylamine, and phehol was gbtaed in good yield 1order to clarify the mecha nism of this photo-reaction, the effect of 1, 3-pentadiene or diphenyl disulfide was studied. lt was cencluded that the keto ether (3) in triethylaln undergoes photo-cleavage reaction its ether linkae, after its carbqnyl gloup of n, n triplet state abstracts the hydrogen from the solvent.

View full abstract

cis-4-Decenoic, cis-4-dodecenoic and cis-4-tetradecenoic acids were synthesized by the condensation of the corresponding alkqnals (Cs, Cs and Ce) with phosphorane (6) which were prepared from the reaction of phosphonium iodide (5) with sodium-methoxide in dimethylforinainide, as shown in the flow diagram of. the reaction sequence (Fig.1). The position kenoates were oxidized with KMnO according to Armstrong and Hilditch and also from their NMR spectra which showed an apparent strong doublet at r 7.65 and a multiplet centered at r 46AS. Airesence of "the broad absorptions centered at 720 cm-i and absence of the.absorptions at 965-970 crr in the IR spectra of'the title acids showed that their double-bo.r take the cis-configuration.
The physical constants of the title acids, their methyl esters, p-broinophenacyl esters and pphereylphenacyl esters were compared with those of the cis-4 alkenoic acids of the same carbon atoms which were previously separated from the seed oil of Litsea glauca Sieb.

View full abstract

The reaction of 2-methylnuorenone(3)or fluorenone(4)with 2-methyl-9 uorenyl lithium (5) or 9-nuorenyl lithium (6) 1ed-to three 2-methyl stIbstituted 9-hydroxy-9, 9bifluorenyls (7a, 7 b)and(7)1. The. compounds(7)were converted into three 9-bromo9, 9-bi-renyls(8 a), (8 band(8 c)), respectively, by passing dry HBr gas through the solution of (7)in acetic acid. The dehydrobromination of (8) was effected by alkali to give the red hydr carb ns 9, 9' biurenylidenes(9 a)and(9 c)The reac of (8) with hot aliphatic alcohols led to the several correspong 9a1koxy-9, 9bifl uoreny1S(10).urthermore, 9, 9-bifluorenyls(15 aand(15b))were bbained fro'the reduction df(9)AbyZn-dstand.
Both 2, 2 diethyl-9-hdr y-9, 9 u renyl(7c)and 2, 2'dimethy19-eth6xy-9, 9'bu reny1(10c-2)werefond tobe the mixture of threoand erythro isomrs, and 2 2'diethy1-9 9bfi uorenyl(15 c)was the mixture of racemic andneso isomers.

View full abstract

In the reactions of benzene in glow discharge, the polymeric materials were dbtained in glow column chromatography, napthalene and biphenyl were isolated and the presence of fluorene, phenanthrene and or anthracene, and biacenaphthylene was also estimated by the studies of the mass spectra of another spots. A yellowish polymer, obtained by means of the reprecipitation in methanol of the latter portion, was estimated to be a polymer having a skeleton of some condensed-ring compun ds, On the basis of its IR spectru. and its eleme ntary analysis.
The glow discharge experiments of both benzene water and benzene-Tmethanel were also undertaken. ln the former case, the presence of phenol and o, m p-cteole was confirmed along with that of products, obtained by glow discharge reaction of benzene, in terms of GLC analysis of liquid product and, in addition, benzyl alcchol was isolated in the latter case.

View full abstract

The isolation and structural elucidation of geometrical isomers of 24-dinitrophenylhydrazones(DNP) of seven unsymmetrically substituted benzophenones are described.
The reaction of benzophenones with 2, 4-dinitrophenylhydrazine by the usual procedure led to a mixture of E- and Z-isormers of the corresponding DNP's, which were then separated by fractional crystallization of using ethyl acetete as the solvent. The melting points together with some physical properties are summerized in Table1.

View full abstract

The authors have studied t elucidate the constituents of the essential oil Thymus quinquecostaus Celak.
The essential oil was obtained by steam distillation of the plant's leaves and stems.
The essential oil was treated with 2 N 'sodium carbonate, then with 2 N sodium hydroxide solution, and was separated into the three parts neqtral, phenolic and carboxylic acid.
The resulting each part was investigated by means of golumn chromatagraphy, gas chromatography, infrared spectrum, mass spectrum, nuclear maghetic resonance spectrum and chemical method.
As a result, twenty kinds of compound were detected as the c.onJs tituents of Shis essentiaj oil a-pinene, B-pinene, campht ne liinonene, p-cymene, B-caryophyllene, humulene, r-cadi nene, B-bisabolene, bernylacet, ate, 'camphor, 3rectanone, dihydrocarvone, 3-hexen-1-ol, 1-octen-3-ol, terpinen-4-ol, bornedl, thYmol, 'carv, acrol and thymolmethylether.

View full abstract

A new bitter principle named pedunculoside (1), C, 6HssO, e, has been isolaged from the leaves of Uex oldhami Miq., llex Peduncutesa Miq. and llex retunda Thumb. The structure of (1), has been confirmed as the glucose ester of rotundic acid (30) in terms of alkaline hydrelysis.Acid hydrolys'is ef (1) gave mainly glucose and two acids A (3) and B (4). Acid A has been led to a diol diacetate (25), which was prepared from vanguerolic aeid (21), and acid B methyl ester (10) to methyl tomentosonate (23). i On the Bitter Principles ef Aguifolaeeae. 1.

View full abstract

A new bitter principle named sugereoside[1], C₂₆H₄₂O₈, has been isolated from the leaves of llex sugerokii Maxim. var. brevipedunculata. The structure of [1] has been confirmed as the glucoside of abbekutone [6] in terms of the hydrolysis with acid and emulsin.
Another bitter principle named ilesugerin [18] C₂₆H₃₂O₁₄ has been isolated from the leaves of llex sugerokii Maixim. var. longipedunceclata, a phenolic compound named sugeronin [24], which is a glycoside of p-hydroiysenzyl benzoate linking with glucose and xylose, has been isolated.

View full abstract

To elucidate the inhibiting effect of extractives of Karamatsu (Larix lePtolepis) on the radical polymerizasion of vinyl monomer within Karamatsu, the polymerization of vinyl acetate in the presence of extractives of Karamatsix was investigated by thd use of a dilatometer.
As a result, in the polymerization of vinyl acetate brought about by the addition of cold water hot water, alkali, ether, acohol benzene (1 : 2) and acetone extractives, the clear induetion peried was observed at 47C and 40eC, but in the case ef alcohol-benzene(1:2) and acetone extractives at 40eC.
Upon additionof cold and hot water extractives, a proponal relatin was observed between the induction period and' amount of extractives added. Also, as to the retardating effect, the retardating efficiency was evaluated from a ratio of k to kek where k is the rate constant of the reaction involving various extractive and ko is that not involving them and the order of the inhibiting effect on radical polymerization was as follows alkali extractivesther extractives lcohol-benzene (1 : 2) extraetivesaeetone extractives.

View full abstract

Glycidyl pyrrole (GP) was synthesized from pyrrole and epichlorohydrin (EPCH), and the polynierization of N-GP was studied. Pyrrole reacts with EPCH in the absence of solvent to yield 2-GP (6.5%) and 3-GP (1.6%). Pyrryl alkali metal salts react with EPCH to yield N-GP as a main product together with the polymer of N-GP. The maximam yield of N-substituted pyrrole (71.2%) was attainable in the reaction of pyrryl potassium with EPCH. The yield of 2-GP was below 1.3%.
Pyrryl magnesium halide reacts with EPCH to give 2-GP(1.3%), 3-GP(2.3%), 2, 3-diglycidylpyrrole(diGP) and 2, 5-diGP. These scattered products were obtained in very poor yield, because EPCH was mainly polymerized by the pyrryl magnesium halide present.
N-GP can be polymerized by potassium hydroxide, sodium methoxide and sodium phenoxide. Especially, sodium methoxide could initiate the polymerization of N-GP to yield poly-GP (88.9 %) and its molecular weight was determined to be about 2000.

View full abstract

In order to examine the copolymerizability of 2-allylpyrrole (2-AP) and the mechanism of the alternating copolymerization of 2-AP with fumaronitrile (FN), the synthesis and polymerization of 2-AP were studied.
It was found that there were definite relations between the Q and e values of comonomer and copolymerizability. Namely, the copolymerization occured when the Q and e values of the comonomer were large, the homopolymerization occured when the e value was small and Q value was large, the copolymerization was inhibited when both of the Q and e values were small.
Moreover, in the copolymerization between the e and e ValueS f curred wben the e and e yalues the ee vaftte was sma11 whenbf theQaad8er, in2-AP(M) with acryii1e(MD omer reaetiv'ty faxl t be r1.10rOm)..

View full abstract

In the copolypaerization of 2-vinylpyrrole(2-VPyrr Mi) with methylmethacrylate(M2), the monomer reactivity ratios were found to be rt=O, 69, r2=O, 066, and the Q and e values of 2-VPyrr were found to be Qi=5.53, ei=136 Similarly to the other ev-vinyl hetero-5-membered aromatic derivatives with large Q values, the Q value of 2-VPyrr was also larger than that of styrene, but the order of the resonance stability Q was not agree with that of the hetero-5-membered rings. ln the copolymerizadon of 2-VPyrr with fumarOnitrile(FN M2), the maximum rate of the copolymerization Rp(.ax) was appeared at the higher concentration ef 2-VPyrr. Then, the uneomplexed monomer considerably contributed to the alternate copolymerization. And the copolymer composition was (2-VPyrr)(EN) These led to the following propagation steps (1), (2) and(3).
The copolymerization of 2-(1-pyrrolyl)ethyl viRyl ether(PEVE) which is the itnconjugated vinyl monomer, with FN afforded alwqys 1:1 alternating copolymer, and its Rp(max) was appeared at the higher concentration of PEVE in the monomer feed.

View full abstract

The polymerization of methyl methacrylate(MMA) was carried out at 300C, by-c-yap-o(d.ipyridyl)cobalt(ir)orcomplex, which was obtained'by substituting a part of-the ligand in 90(CNs)gr with han inhibiting action of 1, 1-diphenyl-2-picrylhydradyl could be observed in the polymerizatiop 6'ac-G'6if'afidO t-ie monom6r re5ctivity ratio, r, o.s3 and r2o.4s, obtained.in the co-polymerization of MMA with styrene, it is suggested that the mechanism of this polymerizatign was a iadical type. The com'initiated the polymerization of MM..A in nitrogen.atmosphgre t.oo, Ei-i t'he 'citalytic activity of the complex decreased markedly. However, no polymerization has S 819taken place in the presence of air. The function of atmespheric hydrogen in this reaction was investigated manemetrically, and the absorption of hydrogen was observed in the process of polymerizatien.
It iwas considered that in the polymerization, as in case of (Co(CN)s)3ww, atmospheric hydrogen has taken part in the initiation of polymerization through the formation of hydrid cyano(dipyridyl)cobalt complex.

View full abstract

Both potassium tris(oxalato)cobaltate(M), KsCo(C20Ds) qnd po.tass.iym. tris(oxalato)fgyrate (III), KFe(C, q), can sensitize the phtP, lymerizati, nsf acrylamide in aque, us solutions, 6fftheMi-r kinetic behaviors are different from one another.
The rates of phtP1ymerizati, ns sensitized by the c, balt(III), mplex under irradiatin at 420UVr '6ToTdim aie giv-en'as follows R, klee'5(1-10ed)'5. This rgsult shows.the muyual eMimi'ha-ti'on of growWing polymer redicals. ln view of the low initiati-on efliciency of.the complex E-emay partly decay .sponta neo.usly aqd. pgrtly induce the decomposition 6Mi Ttfie coniplexT without the formation of radicals, besides-initiatipg the. polymgrization.
On the ther hand, the ph, t, P1ymerizations sensitized by the ir, n(III), mplex under irradiati5ff it'V42Vo him' rmchn be ini-tiated wi'thout any induction period, whereas e ratg decr.ea.sep with Vesu-iiingpFoTiyF iner while the Trate of decomposition of tbe compex ip, ittle, affected by perc, hl, o.r-i-9 rt rbiYN'be' conidered that the suppression of the r.ate.is attriPuted Sg the accgmulation acid. fxalat fer rate (III) resulting frm the dec p, sti, nf ferr icc, m pl ex, Moreover, it appears tVt-h'e-V66fiilileiJi16tards the polymerization at its higher concentrations even in aeidie selutions.

View full abstract

The vapor-phase graft-copolymerization of methyl methacrylate onto polypropylene fibers was studied by a pre-irradiatioR technique and the weight increase during the reactien was followed by a spring balance method. The grafting reacti was spressed with icreasing irradiation temperature. The rate of weight increase cf fibers due te the grafting reaction became larger with increasing vapor pressure'of menemer and pre-irradiation dese. The rate of grafting reaetien decreased with increasing grafting time in general, but the acceleration in rate was observed with decreasing grafting temperature. The grafted fibers contained almost no oeeluded homopolymers. The grafting reacticn process was we11 explained by taking into aceeunt of the increase in sorption caused by the increase in the extent of grafting.
The DSC measurement en the stepwise-annealed grafted fibers ghowed the effect ef grafted branch on the recrystallization.

View full abstract

Hydrolysis of N-vinyl-2-oxazolidorie (NVOx) in the presence of poly(methacrylic qcid) (PIMIAA)was D The rate of hydrolysis increased in the presence of PMAA thqn in its absenLce at the samepH values and could be represented by Michaelis-MenteR kinetics w-hich show the substrate (NVOx) saturation phenornena at high substrate concentrations. The effect of organic solvents on the hydrolysis of NVOx was studied.
Further, the influence for the addition of poly(vinyl pyrrolidone) (PVP) gf yarious rpolecular weight which ferm the complex with PMAA was examined. The rate of hydrglysis degreased witfi the a mout and molecular weight of PVP increased. The interaction of the substrate (NVOx) and PMAA was attributed to hydrophobic and hydrogen bonding. Thermodynamic parameters for the hydrolysis were estimated.

View full abstract

For the purpose of the improvements of Karamatsu wood, methyl methacrylate (MMA) was polymerized in the presence of Karamatsu wood(20-20-15 mm) by heating method and Karamatsu wood-plastic combination (WPC) was prepared.
The poly(methyl methacrylate)(PMMA) homopolymer whih was obtained in 42% yields, was removed by acetone extraction, and graft WPC was obtained in 10.9% yields.
The graft copolymer of lignin and PMMA was isolated by chlorine dioxide oxidation of the graft WPC which remained at the acetone extraction. The graft copolymer of holocellulose and PMMA was isolated by extraction with copper-ethylenedfamine solution from the graft WPC which remained at the extraction.
The graft copolymers were examined by infrared spectroscopy(IR) and differential thermalgas chromatography(DT-GC).
It was confirmed that PMMA graft-copolymerized onto lignin and holocellulose., The graft copolymer of lignin and PMMA in Karamatsu was 3.5%o (composition lignin (54, 3%) and PMMA (45.7%)). Also, the graft copolymer of, holocellulese and PMMA in Karamatsg. was 17.4%(hQlocellulose (48.2%) and PMMA (51.8%)). That is to say, 82.5% of the grafted'PMMA was onto holocellulose and 14.6% onto lignin in Karamatsu.
Furthermore, it was indicated that the degree of polymerization(DP) of PMMA which was'grafted onto lignin and holocellulose was considerably lower that than of the homopolymer(DP'17000).

View full abstract

The phase transition effeet of aqueous nonionic surfactants solution on the emulsion stability ef poly(alkyl, acrylates) during the polymerization was studied.
Using polyoxyethylene nonylphenyl ether (chain length, P), alkyl acrylates were polymerized in aqueous layer. A stable polymer emulsion was ebtained either below a eertain temperature or with nonionic surfactants having P values above a certain, limits. Especially at the suitable low temperature, a stable emulsion of poly(alkyl acrylate) was obtained even by the polyoxyethylene nonylphenyl ether of small P value which had not 'been used yet.
These phenomena are correlated to the dissolving phase of the nonionic surfactants solution.Aqueous solution of nonioni'c surfactants shows cloud point at a certain temperature. When the aqueous solution of nonienic surfactant contains alkyl acrylate monomer, the cloud point becomes lower than that ef the surfactant solution cnly, and by adding the monomer into the solution, the cloud point is gradually, depressed into a certain temperature and finally shows no decrease. This characteristic temp erature is ca11ed by the authors as "MeRomer Saturated C1oud Point" (MSCP). The M SCP values increase with the increase of the P values, and is useful to consider as the curve of MSCP versus P.
Emulsiohs stabilized with a nonicnic surfactant form a OIW type below the cloud point and W/O tYPe above the cloud point, so at the temperature lower than the MSCP, alkyl acrylates are polymerized with nonionic surfactants very much stably. And the relation between the MSCP and the P of the nonionic surfactants well defines about stable state condition at emulsion polymerization. Furthermore, by using the MSCP curve, it is easy to estimate the P value of the nonionic surfactants which has to be used in tl e emulSjon polymerization at a given temperature.

View full abstract

Catalytic liquid phase hydrogenation of benzaldehyde te obtain benzyl alcohel over PdCcatalyst suspended in ethanol in a stirred vessel was studied to evaluate the resistances to the mass transfer and the chemical reaction at the catalygt surface. If the diffusion of hydrogen was rate controlling, the relations between the resistances of two liquid films surreunding the bubles as well as the soJid particles. and operating variables (gas flbw rate, rate of stirring and catalyst loading) were obtained as shown in Figs. 2 and 3. The results were.comparable with those obtained by the previous worker whieh are tabulated in Table 1.
To obtain an adequate rate equation for the chemical reaction by assurning Langmuir-Hinshelwood model, the effeetw of the concentration of benzaldehyde and dissolved hydrogen on the initial rate were measured as whown in Figs 4 and 5 under the condition of elimination of mass transfer resistance. Among the three rate equations which were not considerably different in the sum of squares of the residuals obtained by use of the methods of linear and nonlinear least squares, Eq. (4) was selected as the most adequate-rate equation by an inspection of the resonab1e temperature dependency on the Lconstants in the rate eguation as shown in Fig. 6, Validity of this equation is confirmed by the agreement between the experimental and caleulated values as shown in Figs. 4 and 5.

View full abstract

For the purpese of studying the energy transfer between reacting gas molecules and a solid surface when the catalyti reaction takes place on the surface, the heat loss from the platinum ribbon was measured in the stoichiometric mixture of CO and O₂ under pressures in the range of 1-4x10^-2 Torr. and at ribbon temperatures of 291 and 358C. lt was found that the accommodation coefficients of both CO and O₂ stayed equal to shese observed separately in each gases through the heterogeneous catalytic oxidation of CO.

View full abstract

Oxidation of some propylene derivatives were studied over stannic oxide-bismuth oxide catalyst, which is active for oxidative dehydroaromatization of olefin to aromatics. From allyl chloride and allYl bromide, benzene was obtained through dehalogenation, dimerization and aromatization. Halobenzenes, however, were formed only in a very small amount, unexpectedly. Allyl alcohol and allyl amine were easily dehydrogenated to acrolein and acrylonitrile, respectively. ln the case of acetone or 2 bromopropylene, no partial oxidation were observed but complete oxidation.

View full abstract

Effects of various aluminum salts used in preparation of aluminum phosphate catalysts on the catalytic properties have been investigated Aluminum phosphates gbtained frolFn nitgate and chl ride((1)and(2))had higher acid am unts and larger sface areas than aluminum phosphate obtained from sulfate (3), but some-o.fL (3). sbgwed.higher. catqlytic.agtiviy foi-bufanol dehydration than'(1)and(2) Over (1) and (2) ether rather than olefin formed 858 in the early stage of the reaction, while over some of (3) olefin formed selectively For the formers, the ratios ofl to 2-butene and cis to trans-2-butene were higher than the equilibrium values, whereas for the latter those ratios decreased as the conversion increased t Studies on Catalysis by Metal Phosphates. IV.

View full abstract

Properties of thoria obtained by thermal de60mposition of thorium nitrate and oxalate were studied. Thorias from nitrate were dense aggregate like crushed glass about 50 pt in size, while those from oxalate were obtained in powdered form smaller than 2.5 pt. A photograph(400)is given in, Fig.4. The strongly heatednitrate in mue for 3hr gave thia with a particle density of 7.9Av9.3 g/cms. Thoria from oxalate galcined under the same conditions was 3.2/v3.7g/cmS, indicating porous structure. No difference were observed in crystallite size by X-ray powder data. DTA-TGA curves are given for boths alts in Figs. 1 and 2.

View full abstract

The lanthanoid complexes with N, N'-bis(aceto nylethylide ne)ethylenediaine(AEH2)were synthesized by the new method using mixed olvent (methanol/acetone) at room temperature.The complexes were characterized by chemical analyses, IR spectra, and X-ray powder diffraction analyses. As to La and Gd complexes, these results were different from those reported by Dutt et al.2. La formed a different complex from other light rare earth complexes, La2(AEH2)sC16 2H20. Gd formed the same type of complex as light rare earth complexes, Gd(AEH2)2Cls. MetaNigand stretching vibrations were observed at 406A 429 cm-i. These absorption frequencies increased in the order of the atomic number of metal ions.

View full abstract

The photochemical reaction of acetone with maleic anhydride yielded oily materials as well as oxetane compounds and maleic anhydride dimer. The distillation of 'the oils under redueed pressure gave pale yellow distillate which solidified on standing into a white and elastic polymer.The structure of the polymer was investigated. The oils underwent the thermal decomposition giving volatile materials which reacted by radical mechanism to give a polymer containing an ether linkage and m aleic anhydride group in the chain. Maleic anhydride was also attached to the main chain as a side group by forming an ester linkage.

View full abstract

It was previously reported that acetophenone was produced in good yield from the photolysis of 2-phenoxy-1-phenylethanol(PPE) with benzophenene, but, in the case of 2-(p-methoxyphenoxy)-1-phenylethanol(MPPE) with benzophenone, preferential product was benzaldehyde.
In order to elucidate the mechanism of benzaldehyde formation, the rate constant kr was determined and the deuterium isotope effect was investigated. ln the case of benzephenone-PPE, the value of kr, was 3.6-10⁶ l.mol^-1sec^-1 (the isotope effect=conversion of PPE -d/conversion of PPE, 0.50). On the other hand, in the case of benzephenone-MPPE, a remarkably large kr value was obtained (1.4 10g) and the isetepe effect (ceftversion of MPPE-d/conversion of MPPE)was scarcely observed (1.1).

View full abstract