Oxidationof iron(II)chloride with oxygen was studied in a stirred vessel with four baffle plates.
Since the concentration of oxygen in the bulk solution was nearly equal to that in the gas1iquid interface below O.1mol/10f iron(II)ch1oride and 1, 09-ion/1 f chloride ion, it was considered that the rate controlling step was the reaction in the bulk solution.
The reaction rates were independentof the concentration of hydrogen ion and iron(II)chloride, as far as the concentration of chloride ion was kept constant. The reaction rate was second order in the irort(ll)chloride concentration, and first order in the partial pressure of oxygen. The effect of chloride-ion concentration on the reaction rat was explain3 by assaming the formationof iron(II)chlorocomplex Empirical rate equation was derived from the experimental results,

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Synthesis of B-chloropivalic acid from methallyl, , chloride (3-chlbro-2rmethyl-1-ptopene) and carbon monoxide in hydrogen Huoride m, edium was st udied kirtet/lcally. Since tarry matter formed-at increased temperature and concentration, the favorable conditi ohs are confined te the reaction temperature below OOC and the charge mole ratio of methallyl ehlbride to hydrogen fiuoride less than O, 02. FQr example, 94 mol% yield of B-chlorepivalic acid was attained in 1.5hr under the conditions carbon monoxide pressure 15Q. atm, temperature 10C, the charge mole ratio O. Ol.
Rate 6quation, derived from.. the prqpQsed mechanism of carbon monoxide addition to the carbonium ioR foitned ftom Methallyl chloride in hydrogen fluoride, can explain quantitatively the'effects bf pressure and the charge mole ratio, The rate constants (atin-1, min-1), 1.68 10S (-10eC), 5.03 10-4 (-200C)i 2.02 10w (30eC), and the apparent a6tivation energy, 14kca1, mol1, have been obtained.

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The carbonylation of iodobenzene has been studied kinetically in the presence of catalytic amount of palladium chloride. ln the reaetion of iodobenzene and carbon monoxide under pressure in a methanol solution, the addition of a suMcient amount of pyridine makes the catalyst soluble to form a homogeneous solution, and facilitates the methyl benzoate formation under mild conditions.
Based on the assumption thatthe reaction involves methoxy and carbomethoxy-palladium cQmplexes, following rate equation has been derived
(CH80)PdC1(py)2+CO rl; (CH300C)PdCl(py)2
(cH, OOc)PdCl (py)d phl 13 L. PhCO2CHs + PdCII(py)2
kik2HPee(PdC12)o((Phl)e (Ester))
(1 kd(PdC12)gt) (k-I kiHPco k2((Phl)g (Ester))) kd(PdC12)c
Where kd-is rate constant of deactivation. This equation is in reasonabl. e, qgreement with the experimental results. The rate constants and the overall activation energyt have been determined to be kiH=8.16 10m2 a/tmpti, minFi, (H; Henry constant of CO), k.. i=O.185 min-i, k2=7.64 mol-i, 1, min-i, kd=31.7mol-i, 1, min-i at 1000C and E. =20.9kcal, mol-i, respectively.

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A set of rate equations for the pyrolysis of propane, where the cencentrations of free radical are eliminated was derived on the assumption that the rates of the initiation and termination reactiQns are much smaller than those of the propagation reactions. The rate constants of free radical reactions in the rate equations were estimated by Marquardt method from the product distribution in the pyrolysis of propane at temperatures from 700e to 7500C. The rate constant of deco position of propyl radical to propylene and hydrogen atom relative to that of decomposition to ethylene and methyl radical was O.797AvO.868. This value is cQmparable with the value of O.0775 in the literature, which was obtained experimentally from the phgto1ysis of aceto e, Similarly, the rate, constants of free radical reactions obtained, for example, from the iphotolysis can be compatied. with the results of pyrolysis.

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Silver bromide iodide emulsions with varying content of Agl were sensitized by L(NH4)21rC16(1), and the degree of surface sensitization increased with increasing ratio of intetnal/Surfape speeds of the primitive emulsions. (1) increased the surface speeds, and decreased the internal speeds of both cubic and octahedral AgBr grains. These phenomena caused by (1) were similar to those by sulfur sensitization. The degree of sensitization by (1) was the largest for the grains which were not sulfur-sensitized, decreased with increasing degree of sulfur sensitization, and at last became negligible. Since it is believed that sulfur sensitization increases photographic speeds by providing electron traps, it is suggested that (1) increases photographic speeds also by providing electron traps.

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The electirodeposition ofr tropper tfrom Cu(CF3COQ)2-CFpC90H-H2Q. bathN hgE.. be-eAnAn ptudigd in comparisQ. n KMith the results obtained in nonaqUeous bqtbs cgntainlng Cu(iCEsCOQ)2 ln the bath of Cu(CF3COO)2(100 g 1) CFsCOOH(Or l N) H20i bright and smooth deposits were obtained at 50 C in the current density range of 4.0 v24 A/dm2, while the current efiliciency of deposition was always 100%. ln such cases, it was found that the apparent anode eMciengy was fi tore than 100% in low cuirent density range. ln the aqueous bath'above mentioned, charge transfer was considered to be the rate determining step for the deposition in the current density range from 4.1 to 13 A/dm2.

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Glassy and crystalline substances in NaPOs-MoOg system with P/Mo ratios from O.1 to 300were prepared by heating of NaPOs glass and molybdenum trioxide mixtures at 580, 700, or 750gC. The products were smbjected. to paper-chromatograPhic analysis, X-ray diffractometric measurement, and IR spectrophotometitic measurement. The prodqcts prepared at 580eC with PIMo ratios from O.1to 3. contained crystallin6 sodiummolybdenum oxide phosphate(NaMo02PO4). Since the average chain length of condensed phosphates present in the products increased with increasing P/Mo ratio, it could be concluded that NaPO391ass reacted with molybdenum trioxide to form P-O-Mo linkage, Assuming that the glassy products with P/Mo ratios larger than 5.0 had P P, P-O, P-O-Mo, and Mo-O linkage C a theoretical treatment of the degree of polymerizatien of condens. ed phosphates has. been made and compayed, with the experimental data, and reasonable chemical structure of glasses in NaPOs-MoO5 system were concluded as MoO2(PO)2, MoO2(PO)g, or MoO2(PO) The absorption at 870N930 cm-i in IR Spectra of the products with P/Mo ratios smaller than 5.0 were conSidered to be due to P-O-Mo /stretching.

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A mixture of NaPO3 glass and tungsten trioxide or sodium tungstate with various. PIW ratios from O, 3 to 300 was heated at 10000C, . and the resulting melt was cooled r. aptd!y. All X-ray di raction peaks of the products of the NaPO3-WO3 system with P/W ratios from O 3to O.7 and those of the product of the NaPO3-Na2WO system with P/W ratio of O.3 are due to tungsten trioxide and sodium tungstate respectively, and the other products of both systems are. amorphous. lt was. revealed-by paper-chromatographic analysis that the average chain length of condensed phosphates present in the products increased with an increase of the P/W ratio. Therefore, it could be coneluded that NaPO3 glass reacts with tungsten trioxide or sodium tunqstate to form P O W linkage at 1000 C. The absorption near 900 cm-i in IR speetra of the products of the NaPO3-WOs and Na2WO systems may be attributed to, P-OW stretching. Assuming that the glassy products of the NaPOs-WOs and Na2WO4 systems with P/W ratios larger than 30 have P-O-P, P-O, P-O-W, and W-O linkages, a theoretical treatment of the degree of polymerization of condensed phosphate has been made and compared with the experimental data, and then reasonable structures of the products have been cdncluded as WO2(OP)2, WO2(OP)s, or WO2(OP)

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The effect on some properties of syAthetic dawsonite by thermal treatment were investigated by DAT, TG, X-ray di actometry, infra e4 spectroscopy and the measurements of speci c gravity, poresity, Specific surface area and adsorption of SO2 gas etc.
CO2 gas in synthetic dawsonite is slowly evolved by thermal treatment and its crystal structure collapses, By heating at 360 C, CO2 gas is completely dispersed and sodium aluminate gel (NaAIO(OH)2) is produced. At 650 C, CO2 gas and water of erystalli zation in synthetic dawsonite are evolved to form NaAIO2, which is very hygroscopic crystal. Sodium aluminate is recognized to be B-NaAIOi below 800 C, but it changes to r-NaAIO2 above 800C.
Synthetic dawsonite is hardly hydrolyzed, but its hydrolysis is promoted by increasing teMperature, The hydrolysis of calcination products give sodi, um aluminate solution and psendoboehmite or bayerite. On the calcination preducts up te 400 C, the adsorption. ability bf SO2 gas increase with the increase of CO2 gas removed.. The chemical adsorption become prevalent on the calcination products above 300eC.

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Hydrated alumina gel was synthesized by using the homogeneous precipitation method by urea and aluminum salts, and the change of constitution due te the heating ef product and the influence ef anion in case of synthesizing hydrated alumina gel were investigated by continuous pH measurement, differential thermal analysis thermegravimetric analysis and powder X-ray diffractien analysis.
In case of synthesizing hydrated alumina gel, a superior filterable granulaf substance was obtained when aluminum sulfate was used, on the other hand when aluminum chloride and aluminum nitrate were used, an inferior filterable gelform substance was obtained, and the pH value of the precipitates obtained was about 4 in the granular substance and about 7 in the ge1 orm substance.
When these products were thermally treated, the granular subs ance ch ngedl int alumina at 900 C and to alumina at 1150 C, while the ge1-form substance changed into alumina at 700 C and into alumina at 1150C.
From thdse results it was ade clear that the hydrated alumina ge16ynthesi ed by Using the homogeneous precipitation method h4s dif erent preperties dependlng on the starting materlaL

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The oxidation of nitrite by manganate and permanganate was investigated in 10. v2 mpl/l petassium hydroxide solution at 20. v80C. Permanganate oxidizes nitrite to nitrate by thc following equation.
NO2- +2MnO- +20H -. NQsin L+ 2 MnOs2in + H20
The rate of oxidation in 10 1 mo1/l potassium hydroxide is shown as follows.
d(NO2bdt) exp( 95, , (N, 2))
Our experiments reveal that nitrite is not oxidized, with manganate in an alkaline solution.

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In the flux action of soldering, it was found that the reaetion teek place between a metallic sulfate and molten Sn solder, which resulted in dissolution of a metal into molten Sn from metallic sulfate. ln seldering, the disselution of a metal inte solder from the base plate became remarkable at high tempreratuxe,
The present paper was concerned with the dependence ef Zn disselution from substrate into melten Sn, on the disselution of a rneta1 resulting from the reaction between a metallic sulfate and molten Sn,
The results obtained ware as follows,
1) The disselution of Zn from substrate into Sn soider was atccelerated by a sulfate of Ag, Ce, Cu or Ni.
2) ln such cases as the above, it was confirmed that Ag-Zn, Cu Zn, Co-Zn or Ni-Zn layer of alloy was produced,
3) A sulfate of Bi or Pb had little influence on the d3ssolutien ef Zn into Sn solder.
4) lt was considered that the dissolution of Zn from the substrate into Sn solder was aceelerated in the case ef dH decrease fer the alloying between Zn and a rental whereas the Zn-dissolution was hardly influenced in the case ef dH increase.
5) ln the case of a metal-Sn allOy solder instead of pure Sn, the disselutien of Zn from the substrate into Sn solder was accelerated by an alloying metql of Ag, while such an alloying metal as Bi or Pb suppresed the dissolution of Zn into the solder, i

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Rates of weight decrease of crude granular carbon in boat have directly besn measured in steam flew at temperatures 650 to 8500C. Some of results are shown in Fig.1, where f= 1 VV/ We
On the basis of the structure of crude granular carbon, proposed in this Jeurnal92, 1086(1971) that it eonsisted of fine elemgntary particles of 20N30 ptm in diameter, arate equation (15) for weight decrease in activation has been derived with a simplified model shown in Fig.2, where the rate is proportional to the spheric. a! boundary area S of not yet activated part. As shown for some examples in Fig.3, Eq, (15) satisfies all experimental results and the slope of the straight line givesthe rate constant, kf. These values obtained are accumulated in Table1 and shown in Fig.4, in which kf vs. VVelF is considered to form one curve at a constant temperature.
Partial pressureg of components in outlet gas in the flow method using fixed bed have been determined fer two species of specimens as shown in Figs.5 and 6, where curves are calculated by Eq. (11), From considerations of material balance of consecutive reactions occuring in the reactor, de: noted by (I), (II)and (III), conversion of steam xH and relevant bmrned fraction of carbon xc are given by Eqs, (5) and (6), respectively. lnitial rate contstant kf calculated by Eqs. (12) and (15) from xa are shoWn by double circles in Fig.4. These values are two or three times larger in abscissa than those of the former method. These are reasonably attributed to the ratio of effective steam fluxes in two experimental method.
Eq. (23) has been derived by the conventional analysis 6f experimental data using L-H mechanism and it satisfies experimental results fairly well as shown for some examples in Fig.9 and gives rate constants k1 and ratio of adsorption coefficients Kco/K1 as shown in Table 5.

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ny A120s(S) and n-A120s(N) were prepared by thermal decomposi, tion of A12 SOD 3, 18 H20and Al(NOs)3, 9H20, respectively., The difference between the reactivity, of resulting op-A1203was examined in terms of the transformation to a-A120s and the fOrmation of ZnA120d.
By means of DTA and X-ray powder diffraction, it was observed that both T-A120s(S) and op-A120s(N) trans, formed to, a-AlaOs via e-AlaOs and the transformation temperature of opAl, O C(s)X ind T-A120s(N), aefined-asV the maxiniurb of DTA exothermic peak, was 1250 C arid 11000C, respectively. The higher transformation temperature of n-A12Qs(S) coqld be explajned by the stabilization of op-A120g(S) due to SO2 remained in it up to 12300C. ln the, present -experiments, however, a quantitative correlatien was not obtained between the ttansfpr, matiQn temperature and the residual. SO 2 content in n-A120s(S), which was estimated by, chemical analysis. On the other hand, the Washing, of op-A120s(S) with hot water, which e!iminated SO42nt existing on the surface, resulted in an increase in DTA exothermic peak height at 1250eC and no change in the peak temperature. ln the case of V-A1203(N), such an increase in peak height was not observed.
The rate of reaction of n-AlxOg with ZnO was measured and fitted to Jander s equation. The reaction rate constant (K) of T-AleOs(S) ZnO system, ZnA120di was found to be approximately ninety times as high as that of T-A120s(N) ZnO system at 7500C, This difference was mainly explained by the difference in radius of T-A1203 particles estimated by electron microphotographs and BET surface areas, and the very slight effect of residual SO 2 on the rate of ZnA120s formation was also observed.

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The reaction process between Ca00(PO4)5F2 and SiCl4 vapor uinder a vapor pressure of 501mmHg, which corresponds to the satuxated pressure at 450C, was studied and estimated as follows;
Caie(PO )6F2 gx/2 SiCl. Caie(PO )e(F2 pt C12x) x/2 SiF xgS l sOO (1)
ca (Po4)6C12 3/2 SiC14 3ca2P207 4cac12 3/2 sio2 ( 600 ) (2)
Cal (PO 6C13+2CaC1 6 CaapO Cl 1000 ) (3)
Ca2PO Cl 114 SiCk 112 CaAP207. CaC12 1/4 SiO2 (600ey900 C) (4)
Ca2P207+SiCli+SjO2, +CaC12 Amorphous phesphate ( 1: 8000C) (5)
The initial stage of the reaction process was alwaysReaction (1) at any tempetatures above 500°C. Through Reaction (1), ch1orine ion substituted fluorine ion, and then complete yt atilzaPiop, . of fluprine. result, ed. C, qig(PO4)6C12, interrpediate product, was decorppose. dA. tent. Ca2Pp7 through h3 116 g tw way T were mplex eac 2 (3) (4) a nd Reaction (3) at low and high tempdrati re tangess), t, p. s pectiVely
Ca2P 7 cha hged into an a: rriorphous p h Sphate (Reaction(5)) Thi amorphous at6ridl contained the phosphate ions with various Polymerization degtees, and had a e6Rsiderabl high solubility in an aqueeus solution of CaC12i
The reaetion rates. of. Re. action (1) and Reaction. (5) increased with the elevation of temperature, , whereas the rate of Reaction (4) gave, a maximu. m, value at about 7500C. The decomp6sition rate of Caie(PQD sC12 below 1.0000C was larger than tha, t above IQ, OOPP )

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Watervaor ad80rption on NaCI and KaSOs P wder mixtures which were prepared under a vacuum of 10 6 Hg, has been investigated, Am unts r adsq s rfqre areas and X-ray diffr ction pattems were de erm ed the samples u der variOUs water vapor pressures.
The surface area and the capacity fawater adsorptl non the samPle be t I crease by presorbing water at relative vapor pressure above 0.34. The X-ray diffraction data of the mixture indicated that NaCI reacted with K2SO4 in the presence of adsorbed water as follws
NaCI K12SO4 KCI (Na, k)2SO2
The above stated increase of the surface area was interpreted to be caused by the microcrysstal de: position of rea6tion pro cts. The coverages of Water adsorbed on both s 1ts a the relat ve pressure of O.34 were estimated to be 2 Oon NaCr and 1 30 K3SO from the-water adsorption isetherms It 8 con3idered that these values cor respond to the e st thick ess of above solid reacti n n the salt 3urface,

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Absorption reactions of nitrogen oxides(NO3) in potassium manganate or permanganate solution and of nitric oxide on potassium permanganate crystal at 300-600C were studied. The Reactions in alkaline permanganate solution are
KMnO4+NO+2KOH=KNO2+K2MnO4+H2Q (1)
KMnO4+NO2+2KOH=KNO3+K2MnO4+H20 (2)
and following reactiens take place in a larger mole ratio of NOx/KMnO4 (1)
K2MnOA+2 NO =2 KNQ2+MnO2 (3)
K2MnO+2NO2+2KNO3+MnO2 (4)
These reactions also occur in a potassium manganate solution. The oxidation of nitrite with permanganate occurred immediately after the absorption if amount of KOH was insufcient.
2KMnOi+KNO3+2KOH=KNOs+2K2MnO+HaO (5)
2KMnOd+3KNO2+H20=3KNOs+2MnO2+2KOH (6)
In a neutral solution the oxidations proceed qpickly. The absorption reaction is expressed as follow,
KMnO4+NO=KNOg+MnO2 (7)
KMnO4+3NO2+H20=KNOg+2HNQ3+MnO2 (8)
Nitrogen, oxide was absorbed well in K2MnO crystal or a mixture of MnO2, and KOH at 300N600eC. A mixture of K2MnOd and KOH absorbed. at lower temperatures, and had the larger ability. t, o qbsbrb NQ per one mol. e K3MnOl, tha, n, K2MpOd alone did.

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The viscosities of melts of V205 and V20s-beryl(Cr3+)system were measured by a Broo: kfield type visc meter in the temperature range fr m 700 t 1070 The results with in a maximum error of 9% were oftained
The flows o th melts were found to be Newtonian above ca 880 C and non-Newtonian be1 w 870 q which vaXied.300 t 36 centip isesr The l garithms f vlscosity f both rnelts are plotted agdinst the reciprocal of absolute temperature in Fig 3a d 4 Two linear relationsof lo9 na 1/T were fo ti nd below ca, 870 c and above ca, 880, From the slopes of these linear relations, the energies of activation for viscousbowsof melts of V205 and V20 bery1(Cr3) system were 23.8 24.2kcal/m 1 be1 w-ca 870. C and 2, 0, 3, 4kca1/m l above ca.880C respectively.
The molar volume as a flow unit in V2O5 melt was calculated from Eyring's transition state theory, using the estimated entr py f activati n(dSdi several ca1/deg m 1), and assumed t be about 5 10 times la ger than a tolar volume of a unit cell of V20 below ca 870 C and ca.1 3 times abovea.880 C.

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The ability of complex formation between synthetic sodium taeniolite [NaMg2Li(SiPie)F2]and various amino acids (see Table 1) was studied. The experimental results revealed that complexes of sodium taeniolite and amine acid can be formed by putting sodium taeniolite powder into each aqueous solution of O.1 N amino acid solutions more acidified over the isoelectric points of amino acids by hydrochloutc acid.
The interplanar spacings of various complexesi prepared at pH=1 are listed in Table 3. The arrangement of amino acid molecules in the interlayer space is derived from the values fclearance space The structure of complexes with c-spacing of about 13 A can be explained by so-called single layer a-configuration arrangement, i. e. the molecular chains of amino acid lies parallel to silicate layers and there are one layer of organic molecules in interlayer space. These complexes are formed mainly due to cation exch. ange of interlayer sodium ions by organic cations of amino acid.
Thermal decomposition of complexes was investigated by high temperature X-ray diffraction and thermoba1ance. The results show that the interealated amino acid is stabilized by complex formation in respect to thermal durability. The formation of hydrogen taeniolite from sodium taeniolite by hydrochloric acid is also described.

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Various mechanisms to elucidate the binding of metal with nucleic acid base were conflicting chiefly about the binding sites of base.
We carried out IR and PMR measurements on Co(II), Ni(ll) and Zn(ll) complexes of bases, using 3-methyladenine, 3-benzyladenine and hypoxanthine and discussed the coordinating sites of bases.
We confirmed the existence of N-9 binding of Co(II) in 3-methyladenine complexes, by comparing it with 3-benzyladenine ZnCl(H20). The latter complex shows N-7 coordination of Zn in base.

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The photochemical effect on the decomposition of solid potassium ethy enediaminetetraacetatomanganate (III)was examined by irradiating it with a mercury lamp(Toshiba SHL-100UV) at a distance of 15 cm. The principal mercury line spectra occurred between 250 and 600nm, below 300 nm the intensity was weak and it showed maximum at 546 nm.
Infrared spectra of K[MnEDTA]e2(1/2) H20 and the reaction products were L e4amined by the NujoFrtiull method. The spectrum of the chelate before irradiation indicated the pres. ence of'eoorainated carboxylic acid group band at 1680 cm i. However, the intensity of this bapd decreased markedly a ter irradiation, and a new band appeared at ab6ut 1610 cmi, due to the reductio: n-of the manga: nese(III)chelate to the manganese(II)1 According to Sievers and B-aMii-a r, b D, (Coo) chanW wh6h the ratio of metal ion charge to its radius is 3.6thg sqrpe was true for the change of manganese(III)to manganese(II)and the above mentioned shift of band was thus well explained. The 2349 cm th band shownl in the Fig.1 was due to the CO2 gas produced in the decompositon process.
The. ch-ange of the powder surface diffuse reflectance spectra of the chelate by irradiation is given in Fig.2. The spectrum of the initial chelate had peak maxima, one at 5PO nm and 6ther in the region lower than 330 nm. Aftet irradiation, both maxima dis-appeareq.
Tha process oV the photochemical decomposition may be shown by the following fashion.

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Coprecipitation behaviors of As(III), (V)and Sb(III)ions onto Fe(III)or aluminium hydroxide in both buffer solutions and sea water have been. studied. lt was found that As(V)and Sb(III)ions are quantitatively. coprecipitated on Fe(III)hydroxide from pH 6 to 9, and As(III)from pH 7 to 9. Coprecipitation Qnto aluminium hydroxide was quantitative for As(V)in the pH range from 5 to 9 b qt not for As(III) In sea water, almost he same behaviors in the buffer solution were obgerved for these three ions, except the fact that the coprecipitation of As(III), (V)became quantitative in the alkalione so1ution( pH 10)where the coprecipitation onto Mg hydrQxide took place. As a conclusion, these three ions tend to be removed into the sediment in the, hyd, rosp. here by the, coprecipitation process.

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Rapid separation ofnucleic acid. bases and aminophenol isom, ers using theconventiona strong cation exchange resin was investigated
The retention time of so 1utes was reduced by increasing the concentration of counter ion in the elueat and by add, ing ethanol to the eluent without decrasing the column g cie cy as the result of I nprovement of the selectivity The colu n ef ciency was found tgpb in higher with the ion exchange r sin of 6%degree of 6ss linking'than with that of 8%
The rapid separation of uracil, guanine, adenine and, cytgsine wa successfu1-with in Iess than.8niinutes. The oper ing condition was as fo 10w resin, AnnineX A 4(particle size, 17 2 ), 1umn, 91ass c 1umn f 150 mm 7mm d eluent 0 8 Pao1 CH3COONa, 2.5vo1%ethan.01, pH 4.8: ow rate, 2m min: column temperqture 7oeC AlsQ the separation of o, 3-and P-aminophenol was successful with in less than 15 minutes with the eluent of O.4mo1 KH2PO and20 vol%ethao1(pH 8, 84) The i: nlet column pressure was about 13kglcm2 in both cases

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The prbton NMR spectra of twelve m- and P-substituted thioformanilides in dimethyl sulfoxide were measured. The assignment to the rotational isomers (1) and (2) was med on the basis of the Hammett-type dependence of the iH chemical shifts of the thioamide group In the trans orm(1), the chemical shifts are correlated with the Yukawa-Tsuno s equation with the common r-value for both electron-donating conjugative and electronwithdrawing conjugative substituents (Eq. (3) and Fig.4). This result means that the aryl ripg exists in the same plane as that of the thioamide group (Fig.3), and that the aryl and the thioamide groups constitute an expanded conjugated system over the whole molecule.
In the cis-form (2), the chemical shifts of the thioformyl protons are correlated with the ae-val, ues (Eq. (5)). This corresponds with the model that the aryl and the thioamide groutps are obliged to be twis ted owing to the steric repulsion between the hydrogen atom of the aryl ring and the sulphur atom of the thioamide group, as is shown in Fig.3.
Thioformanilides provide us an example, in which substiuent effects are determined by a common Yukawa-Tsuno s equation for both electron-donating conjugative and electron-withdrowing conjugative substituents,

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The substitution reaction of alkyl halides with an anion exchange resin (Amberlyst A-26)has been accomplished by a batch procedure under various conditions.
It was found that the halogen atoms of alkyl halides can be readily replaced with the haiide or nitrite group of anion exchange resins in dipolar aprotic solvents such as dimethyl sulfoxide (DMSO) and N, N-dimethylformamide (DMF) at 300C. For example, in the reaction of ethyl, n-pro. pyl and n-butyl iodides with resin of nitrite form in DMSO, the degree of substitution I resin (Ri) was 98.1, 79.4 and 32.5% at 300C for one hour, respectively. ln the reaction of n-alkyl iodides with resin of bromide form in DMSO, the reac tivities were in the order: ethyl n-propyl n-butyl n-pentyl n-octyl. The relative reactivity of nucleophiles (halide groups of resin) for alkyl iodides can be expressed in the ihcreasing order as Fe Cle Bre
When the reaction was carried out by a column procedure, the degree of substihition and yield of product were fpitnd to be similar to those obtained by a batch. procedure.

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2-t-Butyl-5-methylanisole (TBMMA) is an intermediate for Musk ambrette, one of the artificial musks.
Methylation of m-eresol with methanol at 150 v1800C, and t-butylation of m-methylanisole with t-butanol or isobutanol at 70yv120eC were studied, The reaetion vessel used was a flowing stream system on a stationary catalyst bede As a catalyst, the strongly acidic eation exchange resin of macroreticular type was used.
It was found that t-butyl group was selectively introdu6ed in the positien ortho to the methoxy greup and para to the methyl group. The result is consistent with those of Carpenter", The yield in t-butyiation with t-butanol was 66 mol%, and selectivity was 80 mol%at 90 C (Fig.2, 3). With isobutanol, the yield was 45 mgl%e, and selectivity was 90 mol%at 1000C (Fig.4, 5).

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The oxidation of 1, 2- and 1, 4-dihydfoxyaromatic compounds proceeds readily in an alkaline solution via radical anions to give the corresponding quinones. However, the spectrophotothe aqueous alkaline solutiort was followed under ahaerobic i, conditiens in 6rder to find out intermediates, gen, erated in 1, 4-naphthale4edio 1, 4- naphthoquinone system. The absorptions appeared at higher wavelength as pH increased.., Absorptiq. n-spectra of three intermediates (Monoanien; 337 nm, Dia: ion; 351 nm, Radical. anion.; 389, 299 nm) were obserbed. ln the systeq t of p-benzqquin6ne-L-hydroquinene, absorptiQti. speetra of. s hrce species (Monoanion; 293 Diani, n; 319 Radical an in 430, 404, and 317 310 nm)were, ser ed inEthe simi1af conditions.

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Amin ations of aromatic su1fonates meno or disulfonate of benzene o-, m-, P-toluene, 4-c, 4rm-, 2-P-xyle, ne., P-ethylbenzene, 1-, 2-, 1, 5-naphth. alenp., , with, sodium amide in liquid ammonia have been studied.
When over two-fold moles of SOdium amide Were used at 80 C er above, the corresponding aromatic primary amines were obtained (Table 2) By gas chropgraphig qpalyses, any iso h amine whides might be fdrmed vria benzyne could not be detected (Table 5). This suggests that the amination is usual aromatie. nucleophilic, subst-itution (SN 2) given in equation (2) The effect of substituents and such reaction conditions as temperature, amounts of sodium amide or liquid ammonia on this reaction were also investigated.

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The reaction of 2-formy1-, 2-formy1-5- ethy1-, 2-acety1 rans, 2-formy1-and 2-acetylthiophenes with 2-benzothiazolylhydrazine in refluxing ethanol g4ve -t-he -corLrespgp. ding hyd-e azo-ngg kl)(X=Of R, =R, =H), (2)(X=O, R, =H, R, =CH, ), (3)(X=O, R, =CH, , R, =H), (4)

(X=S, Ri=R2=H) and (5) (X=S, Ri=CHs, R2=H)iJ Erom ea. ch hydrazope mixture, the E- and Z-isomers were separated by fractional recrystallization and column chromatography. The steric configurations of the E and Z-isomers were determined by NMR spectra and their spectral characters were investigated, Moreover, the photoisomerizations between the E-and Z-isomers were studie
ln the NMR spectra, the protons of the 3- and 4-positions of furan rings in (1 E). y(3 E)were shielded more than those of (Z Z). v(3 Z) and the NH protons in (IE), (2E) and (4E)were deshie1ded more than those of the corresponding Z-isomers. But no difference was observed in the NH protons between (3 E), (5 E) and (3 Z), (5 Z). The E- and Z-isomers were isomerized to each other under the irradiation by tungsten lamp at 25eC in a few organic solvents. The ratef constants ki for the isomerization, of (1 Z)tr(1 E) showed the solvent dependence; that is(EtOH CH8CN) k, (cl, -C6H, 2): but k, f(4 Z)(4 E)did not show remarkable solvent dependence. On the other hand, the solvent dependence of the rate constants-1 for the(E)Z isomerizations were opposite to the above tendency.

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3-Alkoxybenz [d]isothiazole 1, 1-dioxides(1)reacted with nucleophiles in two different types, A and B. The reacti n, f type A pr, duced 3-substituted be z, [d]is thiaz, le 1, 1dioxides(2)and alc6hols. On the other hand, the reacti n f type B produced saccharin (4)and the products(5) that are produced by a combinati n of nucleophiles and the alkyl groups in the alk, xyl groups of(1), The proportion of both reacti n types in which the reaction occurred depended upon the nature of uncleophiles employed. If a nuclephile possesses reaction occured depended upon the nature of nucle philes employed alow leaving reactivity, such as n-butylamin, e or phenyl carbani n the type A reacti n isothiazole 1, 1-dioxide(1a) aff rded N-methylsaccharin(8)up n treatment with tertiary aminca

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The syntheses of 3-azaacenaphthene (1), the compound which has an ethylene bridged ring at the 1 and 8-positions of isoquinoline, and its derivatives were studied. Ethyl 3, 4-dihydroisoquinoline1-acetate (5) was converted to the hydrochloride of 1, 2, 3, 4-tetrahydroisoquinoline-1acetic acid (9), then to 2 a, 3, 4, 5-tetrahydro-1-oxo-3-azaacenaphthene (10). Three methods were applied to a transformation of (10) to (1). During the$e synthetic processes, 2 a, 3, 4, 5-tetrahydro-3-azaacenaphthene (2) was also prepared.

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The reaction of 3-ch1 robqnzo[d]isothiazole 1, dioxide(5)with sodium alkyl c4rbon. ates (6) afforded N-alkoxycarbonylsaccharins(7), pseudosaccharin anhydride(8)and dialkyl pyrocarbonates (9). The proportions ef (7) and (8) in the products varied with the nature of alkyl groups in (6) the proportion of (7) decreased in the order of methyl ethyl ipropyl t-butyl, and that of (8) increased in the above erder. The mechanistic studies revealed that the reaction proceeded through 3-alkoxycarbonyloxybenz6[d]isothiazole 1, 1dioxide (10), which was produced in, itially by the reaction between (5) and (6). The pyrolysis of N-methoxycarbonylsaccharin (7a) gave N-methylsaccharin (13) and CO2, and that of Nethoxycarbonyl and N-isopropoxycarbbnylsaccharins (7 b and 7 c) yielded a mixture of saccharin (14), ethylene and CO2, and a mixture of (14), propylene and CO2., respectively.

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The absorption spectra of disperse dye in aqueous solution were changed by addition of the sodium salt of 2-naphthalenesulfonic acid-formaldehyde condensates (abbreviatted as 2-NSF). If all of the binding sites in polymer to a dye are assumed to be equivalent and independent of each other, and if the number of total binding sites is much larger than the number of occupaied sites, the apparent molar absorptivity (e. pp) is given by eap, =(sf-e. pp)/Pel/nK+Eb where ef and eb are the molar absorptivities of the free and bound dye respectively, P is concentration of the polymer, K is the intrinsic binding constant, and n is the number of the binding sites per one polymer molecule.
The binding constant (nK) were obtained from the linear plots of e, versus (ef-e )/P, and the thermodynamic parameters were calculated. All values of the changes in enthalpy were negative and the contribution of enthalpy was generally greater than that of entropy. The binding character of dye with 2-NSF was discussed,

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The sulfonylation reactions of naphthalene with phenylsulfonyl or Ptgsyl chloride in the presence of aluminum chloride in nitrobenzene have been stgdied kinetically.
It was found that the rate of the reaction is proportional to the coneentrations of three with the following mechanism.
RSO, Cl + AICI, . O, NCeHs t RSOkCl, AICIs + 02NC, H,
RSO2Cl. AICIs. RSO20, AICI, C
ArH+RSOstw, AICIS ArSO2R. AICIg+HCI
By the application of steady state approximation to the unst-ab. e intermadiate (RSO2ew. AICIP)in tr abo eM mechanism, rate equation can be expressed as follows.
Rate, f pr, duct frmati n
where
Dependence of rate constant on initial naphthalene concentration was interpreted in terms of the ratio k2/k-1.
Activation energies and activation entropies were aHptTigkcaiLmgi tiS =rr.9e u ancl respectively. d, H19kca1/m, 1, dS7e, u. for phenylsu1fonylation at, sylation

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A simple procedure for the alkylation of ev, B-unsaturated cyclic ketones has been developed to synthesize cis and trans-jasmones as well as dihydrojasmone. The alkylation reaetion was carried out with alkyl halides and powdered KOH in DMSO under an inert atomosphere below 30ec.
The yield in the alkylation of 3-methyl-2 yclopentenQne was about 40%e of the theoretical owing to side reactions, while 69. v92%o yields were atoained in isophorone and 3-methyl-2cyclohexenone.
The by-products of these reactions were also investigated.

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Graft copolymerization of styrene on PVC by Cr2"-ethanolamine complex Cr2" (EA) was studied in DMF at 50"C. Different rate equations of the copolymerization were obtained in the low and high concentrations of Cr2 (EA), as follows: R, oc[PVC]if2[Cr2 (EA)]Y2[St]t in low conc. [Cr""(EA) about O.8 10 "2 mol.1 ] R, oc[PVC] Cr2"(EA)"i[St]2 in high conc. [Cra"(EA) about 2, 0xlO-2 mol.1-i]
Kinetic study revealed that Cr2" (EA) contributed to the termination reaction of the copolymerization when the of Cr2 (EA) was high. Model compounds of PVC, e. g. n-butyl ehloride, 2, 4-dichloropentane, 2-chloro-2-ethylpentane and allyl chloride combined with Cr (EA) in the polymerization of styrene, and the initiation site along the PVC chain was assumed.
Results of fractionation of obtained polymers showed that the graft eMcieney was very high, almost more than 90%, and a large amount of gel was formed in the graft copolymer. The gel content in the graft copolymer decreased with increasing concentration of Cr2" (EA) which contributed to the termination reaction.

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The electrostatic effect of Cu(II)-partially-quaternized po1y(vinylpyridine)(QPVP)catalyst on the oxidative polymerization of 2, 6-xylenol was discussed in terms of the thermodynamic parameters of the catalysis and the shape of the QPVP complex. The intermediate complex is stable in the QPVP system from an ehthalpy point of view (Table 2), and the Cu(1)complex is considered to be relatively stabilized by the strain of the QPVP-chain due to the electrostatic repulsion (Fig.1). Activation entropy of the QPVP catalyst is large, and the larger entropy was observed in the QPVP complex having the more compact structure (Table 2, 3). ln the QPVP-catalyzed oxidation of p-phenylenediamine, the chelate tstructure of the QPVP complex was destroyed by the coordination of the substrate,

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ning sodium c bonate or sodium hydrogencarbonate were studied by meansof DTA, TG, X-ray diffraction and gas analyses.
The following results are obtained
1 Hydrogen chloride evolved from PVC easily reacted with sodium carbonate and sodiunt hydrogencarbenate at 200eC. The reaction of sodium carbonate or sodium hydrogencarbopate viith hydrogen chloride is expressed by Na2COs 2HCI=2NaCl H20 CO2. Sodium hydrogencareh changes into sodium carbonate at 200C which reacts with hydrogen. chloride, Sbdiuih hydrogencarbonate reacted with hydrogen chloride evolved from PVC more effectively than sodium carbonate.
2 It was observed that fresh sodium carbenate which was produced by the re. action, 2N gCOs=NaaCOs + H20 + CO2, was very active. However, fresh sodium cqrboinate became less react ve ag ainsrmt PVC when sodium hydrogenearbonate was decomposed at higher tem. penafu fe than at 2-2 OC, or when it was aged, These facts may be interpreted in terms-of the a-e 6rease in both of the effective strain and the specific surface area of fresh sodium carbonatet
3 The following table shows the lowest ignition temperature and the activation energy of igni tion for PVC alone and for PVC containing sodium carbonate. PVC a1 sodium 1 parts iiiff. iii6ffilElitioR teinp. ( ) 580 6Zg Arctivatien energy of ignition (kcal/mol) 12.3 12.1
The activation energy showed no effect on the flame retardation. The result is ipterpr-e-te-g in rmtbrmr ms of the fact t h at sodium carbonate reacted with hydrogen ehloride evolved frgm nPVC W-hi 6hM retarded the fiame in the gaseous phase as other halides did. However, thei fla-mg to physical re-effect on the ignition temperature was observed. This fact attributed property of sodium chloride produced,
4 fhe analysis of gaseous components in the thermal dgcopaposition of. PVC conta ning ethylene, ethane, sodfum carbonate revealed the facts that amount of both low hydrocarbons etc and aromatic compounds tended to decrease, and that a large-amount of carbon. dioxide evolved Evolution of them was caused by the reactien between sodium carbonate and hydro gen chleride evolved from PVC.

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The kinetics of oxidation of isobutylen, e with thallium(III)ion, were studied, because its reaction mechanism was of interest. The reaction was carried out in a stirred vessel with a flat gasliquid interface in a diffusion controlled region, because the reaction proceeded too rapid to be observed by ordinary kinetic method.
The observed absorption rates of isobutylene were tested by way of trial that the reaction to be any of (m n)th-order irreversible ones, and we found that it was of the first-order with respect to both isobutylene and thallium(III)ion.
The obsLerved absorption rates of isobutylene were further analyzed based on the assumption that the reaction was consecutive one consisting of complex formation, complex rearrangement and a complex hydrolysis, and we found that rr complex forming rea tion was irreversible,

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New photosensitive polymers, which had pendant crotonic ester group or acrylic ester group, were prepared from the cationic copolymerization of vinyloxyethyl crotonate (VECR) and vinyloxyethyl acrylate (VEA).
The copolymerization of VEA-styrene was not observed in toluene. The copolymerization of VECR styrene and VEA-styrene occured in methylene dichloride but the yield of the copolymer was poor. Whereas, the homopolymerization of VECR and the copolymerization of VECR and VEA with isobutyl vinyl ether and vinyloxyethyl cinnamate occured in toluene with the excellent yield.
The monomer reactivity ratio of 2-chloroethyl vinyl ether [Mi] to VECR [M2] was determined in toluene at 30 30C as ri=1.16, r2=O.84, respectively.
The relative photosensitivities of the polymers eontaining 5 wt % of sensitizer were from 50 to 280, assuming the sensitivity of KPR to be valued at 100.

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The photooxidation of 1, 1, 2-trichloroethane (TEC) to give chldroacetyl chloride (MCAC)and dichloroacetyl chloride (DCAC) in the presence of chlorine has been investigated under various conditions.
The rates of consumption of TCE and pf formation of MCAC and DCAC under the feed rates of chlQrine and oxygen of O.1 and O.05 mol/hr, respectively, are expressed as follows:
kT/min-i=2.16 exp(-4380/R T)
k cAc/min =2.24 10 exp(6320 RT)
k: DcAc/min"i=o.112 exp(-4150/RT)
The ratio of oxidation to chlorination increases with increasing oxygen pressure. The relation between these reaction rate constants and the oxygen pressure (Po, atm) at 50"C is given by the equation:
kT x Po, CAC/mi O.31.73 Po,

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5-Vinyl-2-norbornene (VNB) obtained as a nyco-dimer from the reaction of cyclopentadiene (CP) and butadiene (BD) rearranged easily to another co-dimer, 3 a, 4, 7 7 a-tetrahydroindene (THI). The stereochemical structures of these compouneds were determined by means of IR (Table 1) and NMR (Fig.1). When endo and exo-VNB were heated together or separately, ende-VNB rearranged to eis-THI, while exo-VNB remained unchanged (Table 2). ln this experiment, mutual isomerization between enae and exo-VNB was not observed. and dSF of the rearrangepaent were found to be 43.7kcal/mol and 20.3e. u. (130-170C), respec tively (Table 3).

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The hydration of 2-pinene (1), 2(10)-pinene (2) or 3-carene (3) with ehlorinated acetic acids afforded predominantly ev-terpineol (7). Especially (7) was obtained as a sole product when the reaction of (1) was conducted in the presence of water.

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3-(2-Hydroxyethyl)-2-oxazolidinone (HEOX) was prepared by treating ethylenecarbonate with 2-oxazolidinone. A polymer was formed by heating HEOX at 240 C with sodium hydroxide under nitrogen until the evolution of carbon dioxide ceased completely. The amount of evolved earbon dioxide, the change ef infrared absorption spectra and the hydroxyl content of the product were measured. These results indicate that the polymer is best represented by the poly(2-hydroxyethy1)ethyleneimine structure containing the urea-bond and the etherbond in the polymer chain. This polymer was insoluble in common organic solvents.

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Aromatic trichloromethyl compounds such as 4, 5-bis(trichloromethyl)imidazole, 1-methyl-4(trichloromethyl)imidazole-5-carboxylic acid, 1-methyl-4- (trichloromethyl)imidazole, ev-(trichloromethyl)-pyridine and benzotrichloride reacted with o-phenylenediamine or 3, 3 -diaminobenzidine, giving corresponding benzimidazole derivatives.

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