1. The solubility of iso-amyl alcohol, n-butyl alcohol and benzene were determined by the titration using the surfactant, Tween 80. 2. In the case of iso-amyl alcohol and n-butyl alcohol, the relation between the turbidity and the quantity of solute in surfactant solution is linear, and the solubilitylimits are both lower than the solubilities in pure water in the dilute region of the surfactant. This makes the determination of their solubility easy and accurate both in pure water and aqueous solution of the detergent. 3. The above method cannot be applied directly for the determination of the solubility of benzene. Ethyl alcohol-Tween 80 mixture is used instead of Tween 80 to overcome this difficulty. 4. The solubilities obtained by this method are accurate enough compared with other methods, in the case of iso-amyl alcohol and n-butyl alcohol, possible error being estimated to be 0.4%. In benzene, the error is somewhat larger, but is in good agreement with the values of the literature.
A new spectrophotometric method suitable for the determination of a small amount of chloride using iron alum solution in nitric acid solution, and mercuric thiocyanate solution in a mixture of dioxane and alcohol solution has been established. The calibration curves conform to Beer’s law at concentrations up to 50 p. p. m. of chloride. The calibration curves are reproducible within ±1% for the range of 5-80 p. p. m. Cl− (Procedure A), and within ±0.05 p. p. m. for the range of 0.05-5 p. p. m. Cl− (Procedure B). As the calibration curves are affected by temperature, it is necessary to measure the absorbance always under the same conditions of temperature in order to achieve good accuracy. The colored solution is stable. A very small volume of the sample solution such as 5 cc. or 2.5 cc. is good enough for the determination. Interfering substances are few, because this method is carried out in acid medium. Br−, I−, CN−, SCN−, S2−, S2O32−, BrO3−, [Fe(CN)6]4− and [Fe(CN)6]3− interfere, but usually they are not present in natural waters in concentrations that would give a serious error. This simple method is suitable for rapid determinations, because it is unnecessary to control pH or filter the precipitate. It is suggested that this method can be widely applied to the determination of chloride in waters, rocks, etc.
A green compound is isolated from the concentrated solution obtained by the action of hydrogen peroxide on cobalt (II) ions in the presence of potassium bicarbonate, and the formula K3[Co(CO3)3]·3H2O is assigned to it on the basis of the analysis of the solid and of the absorption spectrum of the solution. A series of ammine-carbonatocobalt (III) complexes, K3[Co(CO3)3]·3H2O, blue (perhaps, cis) and violet(perhaps, trans)-K[Co(NH3)2(CO3)2]·H2O, [Co(NH3)4CO3]Cl and [Co(NH3)6]Cl3, are synthesized from the abovementioned green solution by means of successive substitution of carbonate ions by ammonia groups. Hexamminecobalt (III) tricarbonatocobaltate, [Co(NH3)6] [Co(CO3)3], is also obtained by adding a hexamminecobalt (III) salt to the green solution of tricarbonato-complex. Three complexes, K3[Co(CO3)3]·3H2O and blue- and violet-K[Co(NH3)2(CO3)2]·H2O, are probably to be regarded as new complexes and may be identified by their absorption spectra.
Two new compounds, H[Coedta]·4H2O and Na[Co(Cl) (edtaH)]·2H2O were synthesized, and their chemical formulae were confirmed by means of potentiometric titration and by examination of the infrared spectrum. The absorption spectrum of Na[Coedta]·4H2O in solution was measured to investigate the pH effect. The absorption curves in acid solutions (pH>2) were wholly identical with that in aqueous solution of the salt, but those of alkaline solutions (pH<10) wrre not identical and further showed deviation from Beer’s law. The absorption curves of Na[Co(NO2) (edtaH)]·H2O, Na[Co(Br) (edtaH)]·2H2O and Na[Co(Cl) (edtaH)]·2H2O were also measured. The first band for the chloro-complex and that for the bromo-complex occupied the similar position and shifted bathochromically as compared with the corresponding maximum for the common complex [Coedta]. These results may be explained on the basis of the so-called “spectrochemical series”. The absorption spectra of the complexes [Co(X) (edtaH)] were found to have two absorption maxima in the ultraviolet region. This phenomenon may be attributed to the “trans effect” of negative ions. By oxidation of an alkaline solution containing cobaltous and edta ions with hydrogen peroxide, a blue complex was produced. Although an attempt to isolate it ended in failure, existence of cobalt (III) complex containing hexadentate EDTA was assumed on the basis of the absorption spectrum.
The basic substances were obtained from the hydrogenation products of the neutral by-products of acrylonitrile synthesis from acetylene and hydrocyanic acid. They were fractionated by distillation through a Stedmantype column. n-Butylamine and n-amylamine were isolated and identified as derivatives of phenylthiourea. On the basis of chromatograms, i.e., the paperchromatograms of hydrochlorides of amines and chromatograms of N-2, 4-dinitrophenyl-derivatives on the column of cation exchanger, the presence of seven amines, i.e., n-propyl-, n-butyl-, 2-methylbutyl-, n-amyl-, di-n-propyl-, n-heptyl-and benzyl-amines was confirmed and that of two primary heptylamines other than n-heptylamine, i.e., 2-methylhexyl- and 2-ethylamyl-amines, was suggested.
Polarized absorption spectra of Wolffram’s red salt, Pt(EA)4Cl3·2H2O, and a related compound, Pt(EA)4Br3·2H2O, EA being ethylamine, have been determined by Tsuchida-Kobayashi’s microscopic method in the regions covering from 2400 to 7500 Å. Both the compounds, which are supposed to be formulated by [Pt(EA)4][Pt(EA)4X2]X4·4H2O, have been found to show an absorption band that has not been observed with either of the components alone. Moreover, this band is strongly polarized along the needle axis. These relationships may be understood on the assumption that the crystals of these compounds involve infinite chains of ---X—PtIV—X---PtII---X—PtIV—X--- along the needle axis, X being chlorine or bromine. The new absorption at the longer wavelength may be considered as a charge transfer band along the infinite chains as assumed above.
Photobleaching of eosine in methanol, ethanol, isopropanol and n-butanol in vacuo was investigated and it was concluded that the primary process is the dehydrogenation of alcohols by the metastable excited eosine molecule. In the presence of oxygen, the photobleaching is suppressed completely, but the sensitized photoöxidation of alcohol takes place. When a small amount of oxygen is added to the evacuated alcoholic solution of eosine, the induction period appears, after which the photobleaching proceeds with almost the same rate as that in the evacuated state. Both the quantum yield for the consumption of oxygen during the induction period (γ) and that of the photobleaching in vacuo (k) were determined and the ratio γ/k was found to be ca. 3. This result and the reaction products detected (aldehyde in vacuo, acid and hydrogen peroxide in the presence of oxygen) were satisfactorily explained by the mechanism proposed by Bolland and Cooper. Further results somewhat important from the general standpoint of photobleaching of dye are : (1) The lifetime of the intermediate to be attacked by oxygen (which is most probably DH·) is not less than 10−2-10−3 sec. (2) The quantum yield for the primary process of the photobleaching D→D*→Dt(+RH)→DH·(+R·) in pure ethanol is ca. 10×10−4 at 20°C. (3) In pure ethanolic solution, the decomposition of dye by the interaction between DH· and R· practically does not occur.
Reaction of hydrogen peroxide with titanium(IV) has been investigated over the range of pH 0 to 13. Below pH 2 this reaction gives orange-colored ion-species, [Ti(OH)2(H2O)(H2O2)]2+ or (TiO2·-aq)2+. In the range of pH 3 to 6 formation of a yellow species is observed and its chemical formula is presumed to be [Ti(OH)3(H2O2)]+. Existence of a species different from the above is indicated by the pale yellow color observed in the region of pH 7 to 9. This species is very unstable unless a large excess of hydrogen peroxide is present, and its chemical formula is presumed to be [Ti(OH)3(OOH)]0. At higher pH values (10<pH), the reaction mixture is colorless, and presumably contains [Ti(OH)2(O2)2]2−. All the tentative formulae of these species are based on the composition of isolated salts, the absorption spectra of the solutions etc. A solution containing [Ti(OH)2(H2O)(H2O2)]2+ remains unchanged but a solution containing [Ti(OH)3(H2O2)]+ gives a yellow precipitate TiO(OH)(OOH), and one containing [Ti(OH)3(OOH)]0 or [Ti(OH)2(O2)2]2− gives a pale yellow compound (Remark: Graphics omitted.) at room temperature or more quickly when heated on a water-bath. The precipitation reaction of (Remark: Graphics omitted.) is taken advantage of in a new volumetric analysis suited for determination of titanium in quantities of the order of 10 mg.
(1) The rate constants, the activation energies and the entropies of activation of the reaction of benzyl chlorides with tertiary amines in benzyl alcohol were determined. (2) In the single stage process for the bimolecular nucleophilic substitution, the polar effects of the substituents are not clearly shown. (3) Both steric and solvent effects play important roles on the reaction studied in this experiment.
The photoreaction of eosine has been studied in ethanol-water mixture in vacuo. Irradiated solution showed a gradual spectral shift towards shorter wavelengths. Analyzing the spectra and applying the chemical method, it was found that the spectral shift is due to the production of uranine. The rate of disappearance of eosine increases with rising concentration of ethanol until 20 vol. per cent, at which it reaches its maximum and constant value, which is the same as that in pure ethanol. The primary processes of the aerobic photo-bleaching of eosine in aqueous solution were discussed and it was concluded that the process must be D^t+O_2→D···O_2\xrightarrow\mathitH2O···prod. (iii)
The partition equilibrium was investigated in relation to the steam-blowing and stripping, during and after the hydroperoxidation of cumene, and the following results were obtained. 1. Equilibrium constant K does not depend on the concentration of CHP within the limit of experimental error, but it depends on the temperature. 2. The partition constant, K approximately satisfies the following formula, K=1.3_4×10^-4e^1580/T. 3. The heat of transference of 1 mol. of cumene hydroperoxide from cumene solution into water under the equilibrium condition, was determined as 3.16 k cal./mol.
Three new compounds, bis-(γ-aminobutyrato)-copper(II), bis-(δ-aminovalerato)-copper (II), and tetrakis-(ε-carboxyamylamine)-coppe(II) perchlorate, have been prepared. The first and the second compound belong to the bis-(glycinato)-copper(II) type, having a 7-and 8-membered ring, respectively. The last compound has a structure of ammine-derivative complex. In all cases preparations were carried out in non-aqueous media such as ether and chloroform. It has been concluded that the 8-membered ring is the highest ring for the formation of metal chelate compounds, so far as the copper(II) complexes of ω-aminocarboxylic acids are concerned. Stability of higher chelate rings was considered as the functions of steric constraints and electronic influences which may be induced with the separation of the two functional groups.
Optical properties of ZnS: (Cu+Mn) phosphors have been extensively studies with the purpose to investigate the phenomena of sensitized luminescence in photoconductive phosphors. Spectra of emission, absorption and axcitation, thermoluminescence and photo-conductivity were measured. It was confirmed from the measurement of excitation spectra that the manganese emission is really sensitized by coper behaving as a sensitizer. Some interesting phenomena ascribe to this sensitization were found in the measurements of thermoluminescence and photoconductivity. The mechanism of the sensitization was discussed exhaustively. It appears reasonable to conclude tentatively in the present situation that the resonance transfer rather than the photoelectron transfer is the predominant mechanism.