A train of a. c. polarographic investigations on several anions, which depolarize the dropping mercury anode, was carried out. The experimental results of a. c. polarography of Cl−, Br−, I− and CN− generally agreed with the theoretical consideration based on the reversible electrode process. Namely, it can be concluded that Breyer’s polarogram shows the derivative curve of the ordinary polarogram and Fournier’s current of these anions is regarded as the mean of two current intensities at both the extreme potentials of the pulsing potential produced by the superposition of a small a. c. voltage on the ordinary d. c. potential. Thus the electrode processes of these anions are found to be reversible. And the possibility of the application to the quantitative determination of these anions was found in the proper concentration range.
An unreduced iron synthetic ammonia catalyst promoted with potash or potash and alumina was separated into two different sorts of powders (A and B). Some of their properties were mentioned in the previous reports. Their catalytic activities for decomposing ammonia mixed with hydrogen were studied at atmospheric pressure by a specially devised flow method. The results are: 1. Between about 400°C and 500°C and for the gas mixtures of several compositions, A powder is more active than B. 2. The actions of the gas mixture laden with water vapour over ice kept in a −7°C bath and of that with 0.4A% carbon monoxide are much the same in the rate and extent of poisoning as well as in the rate of recovering when the admixing of the poisoning gases is discontinued. As to the liability to the effects, one sort of powder scarcely differs from another. 3. Heating at 740°C for one hour has no effect. Heating at 830°C for one hour makes B powder less active and A powder also less active at first, but its activity before heating is soon recovered in the course of a run. 4. The activity of a potash-free alumina-promoted catalyst is not affected by adding before reduction a small amount of potashrich B powder.
1) The dilution effect on the pH change in a dilute solution and in the presence of sodium perchlorate was followed by a glass electrode. 2) A linear relationship is held between pH and −logC. The curves plotting pH vs. −logC run parallel with each other at varying ionic strengths, and the slope is nearly equal to 1/2 by which the most possible existence of Th(OH)+3 is pressumed. 3) The equilibrium constants for ion species, ThOH+3 and Th(OH)2+2, are calculated stoichiometrically from the data of hydronium ion concentration observed and the total concentration of thorium nitrate.
The dipole moments of 2,3-dichloro- and 2,3-dibromo-dimethylbutane were measured in carbon tetrachloride solution in the temperature range from −25° to +55°C, and in benzene solutions at 25°C. The moment was found to increase with temperature in carbon tetrachloride solution. Much higher values of moment were observed in benzene solutions. It was concluded from these experimental results that there exist two rotational isomers, the trans isomer with vanishing or a small moment, and the gauche isomer with a finite moment. The experimental result could be explained satisfactorily by the rotational isomer theory, but not on the assumption of only one potential trough at the trans position. By comparing the energy difference between the rotational isomers of these compounds with those of 1,2-dichloro- and 1,2-dibromoethane it was concluded that the electrostatic force plays an important role in the energy difference between the rotational isomers, whereas the potential barrier is mainly determined by steric repulsion. An explanation was presented to reconcile the result of our dipole measurement with that of Raman and infrared measurement, the two results being in apparent contradiction with each other.
A new method has been developed to permit accurate and rapid determination of oxidation values of organic compounds. The oxidation value of a compound can be readily obtained by determining the iodine produced from the reaction of the organic compound and potassium iodate in strong phosphoric acid. The iodine produced is absorbed into the sodium arsenite solution and the excess arsenite is titrated with the standard solution of iodine. The apparatus and procedures for this method have been investigated. According to the data obtained on some pure nonvolatile organic compounds, utilizing sample weights of 10 to 80 mg., it is indicated that this method is very accurate and an analysis can be accomplished as rapidly as in twenty to thirty minutes.
A new method has been developed to permit the rapid determination of nitrogen in organic compounds. The sample is decomposed with iodic acid-strong phosphoric acid reagent in a glass reaction vessel, and the liberated nitrogen is collected in an azotometer filled with potassium hydroxide solution by the flow of pure carbon dioxide. From the volume of the nitrogen thus collected the percentage of the nitrogen in the sample can be readily determined. This method is, so to speak, the wet modification of the Dumas method. For various types of compounds containing nitrogen, ammonium salts, amine, azo-compound, pyrrol, thiazole, etc., satisfactory results were obtained by means of this method. The nitrogen in a 10 to 50 mg. sample can be determined for thirty to forty minutes with a simple and inexpensive apparatus. But volatile compounds, nitro- or nitroso-compounds, compounds having purine, pyridine, quinoline, and other complicated rings, etc., can not give good results.
Variations of the surface area in the dissolution process were investigated on a Raney copper catalyst “No. 16” (for dehydrogenation of cyclohexanol) and a Raney nickel catalyst. It has been found that nascent bare atoms of copper or nickel formed at the initial step move rapidly, perhaps particularly in alkali solution, to reconfigurate the surface-structure to a more stable one. That is to say, the surface area reaches a maximum at an initial step, where only a small quantity of aluminium is dissolved out, then rapidly decreases to a stable value in spite of successive dissolution of aluminium. The rate of decrease is much greater than that recognized on reserving the catalyst in its dried state or in water. By calculating reliable “n” values, the number of adsorbed molecular layers on the surface area from the modified B.E.T. equation, it has been deduced that the average catalytic activity per unit area of the surface may be decreased in process of dissolution of aluminium.
The interaction of urea and potassium chloride with non-electrolytic polypeptide monolayers was investigated. The film of polypeptide was expanded considerably in the presence of urea in the substrate. The number of molecules was, however, not changed by the interaction with urea. The molecular weights of polypeptides determined by surface pressure measurement on the substrates with or without urea were the same. Whereas the co-area of the molecule was increased by increase of urea concentration in the substrate. Urea might be bound to the peptide linkages in backbone by hydrogen bonding and the formation of aduct seems improbable. Although potassium chloride affected the nature of electrolytic polypeptide film profoundly, it scarcely affected that of the nonelectrolytic polypeptide film. The interaction with urea was discussed in relation to the protein denaturation.
1) Hexamethoxy-, hexaethoxy- and hexaisopropoxy-disilane were prepared and characterized. 2) Dehydrochlorination at an elevated temperature was not suitable for the preparation. 3) A trace of chlorine compound contaminated in the product could be completely taken off by dry ammonia or pyridine. 4) Alkoxydisilanes could not be prepared by using pyridine throughout the reaction as an acid acceptor. 5) The volume of hydrogen evolved by the fission of alkoxydisilanes varied with the reagents.
The dielectric constant of pure dioxane was measured in the liquid and the solid state. The dielectric constants of dioxane solutions dissolved in various solvents were also measured. Using Clausius-Mosotti relation, the molecular polarization of dioxane was computed. The computed value was dependent neither upon the state (solid liquid, solution) nor upon the temperature, and agreed almost exactly with the value obtained from the measurement for the gaseous substance. The difference between the molecular polarization and the electronic polarization is ca. 4 cc. It seems natural to attribute this value to atomic polarization.
The preparation is described of 3-methyl-5-phenyl-2-pyrazoline,3-methyl-5-(4-nitrophenyl)-2-pyrazoline and their 1-phenyl, thiocarbamyl, N-phenylthiocarbamyl,N-benzoylthiocarbamyl, formyl, and acetyl derivatives which were to be tested for antituberculous activity.
Two new compounds, [Co(NH3)2(DCH3)2]Cl and H[Co(DCH3)2(NO2)2] have been synthesized as the first examples of tervalent-cobalt complexes of dimethylglyoxime-mono-methylether. Absorption spectra of the compounds and several bis-(dimethylglyoximato)-cobalt (III)-complexes in solution have been measured. The absorption curves of bis-(dimethylglyoximato)-cobalt (III)-complexes, generally, consist of three inflations and one maximum. The inflation in the visible region is the vestige of the first absorption band, and the two other inflations and one maximum in the ultraviolet region are the specific absorption bands which are due mainly to the dimethylglyoximate ions in coördination. As for the first absortion bands, the results of the measurements can successfully be elucidated on the basis of the spectrochemical- and hyperchromic-series found by Tsuchida et al. For NH4[Co(DH)2(NO2)2], is also the specific band originated from the nitro-groups in coördination remarkable. The isolated maxima on the curves of H[Co(DH)2Cl2] and H[Co(DH)2Br2] in the longer wave-length region are nothing but the first absorption bands which are shifted towards red owing to the bathochromic effect of the two halogenide ions. In the dibromo-complex, the third absorption band is conspicuous. It has never been recognized clearly in the other complexes with dimethylglyoxime. The absorption curves of bis-(mono-O-methyl-dimethylglyoximato)-complexes, as a whole, resemble those of corresponding dimethylglyoximato-complexes, but the bathochromic shift of the specific absorption bands from that of free ligand molecule amounts to a considerable degree in comparison with the cases of dimethylglyoximato-complexes. And this phenomenon is elucidated in connexion with the O-H-O hydrogen bonds. From comparison of the reactions for preparing the bis-(mono-O-methyl-dimethylglyoximato)- and bis-(dimethylglyoximato)-complexes, the high stability of the latter was discussed.
The specific coloration of the benzylamine type compounds in the ninhydrin color reaction is extended to other kinds of compounds. Alloxan resembles ninhydrin in its behaviour as reagent. The fact that the specific coloration reaction seems to be common to the benzylamine type compounds, is verified. However a few exceptions are observed as in the case of benzylaniline (17) and p-dimethylaminobenzylamine (18). The fact that the color change of these compounds in the usual paper chromatography is due to moisture in the air, is confirmed.
The effect of the addition of non-electrolytes to the ion exchange system has been studied. It has been found that the dielectric constant of the solution gives a profound effect on the ion exchange equilibrium and that in the case of lower concentrations of alcohol a linear relationship exists between the apparent free energy change and the reciprocal of the dielectric constant. A working equation has been proposed to account for the relationships between the free energy change, dielectric constant, ionic species and valency of exchangeable ion.
Dichroism of the crystals of trans-[Co(en)2Cl2]ClO4, [Co(en)2Cl2]Cl·HCl·2H2O and [Co(en)2Br2]Br·HBr·2H2O have been quantitatively determined by Tsuchida-Kobayashi’s microscopic method in the visible and ultraviolet regions. As to the dichroism of the trans-dihalogeno-complexes, the following relations have been induced. The first band splits itself into two component absorptions. One at the longer wave-length is polarized in the X-Co-X direction, and the other at the shorter wave-length is polarized in the Co-en plane. For the third and specific bands, the X-Co-X-absorption is bathochromic to the Co-en-absorption. On the basis of the above results, absorption spectra of several praseo-complexes in solution have been discussed.
The specific conductivity of aqueous solutions of potassium dodecyl sulfonate has been measured as a function of concentration in the presence and absence of solubilized benzene in the temperature range between 25 and 60°C. Below the critical concentration for the formation of micelles solubilized benzene has no effect on the conductivity. In the critical concentration range there is a marked effect which decreases with salt concentration and finally becomes negligible. The critical concentration decreases in the presence of solubilized benzene; this effect becomes more marked as the benzene concentration is increased. The critical concentration increases with increasing temperature both in the presence and absence of benzene. The experimental part of this work was done at George Herbert Jones Laboratory, University of Chicago, III., U. S. A. The author would like to express his hearty gratitude to Dr. M. L. Corrin for many fruitful discussions during his stay at the University of Chicago, and for personal communications after his return to Formosa.