Provided that the depolarizer and the electrode reaction product are water soluble, the spherical diffusion equations are integrated. The boundary condition is so chosen that the three elementary processes, i. e., the diffusion of depolarizer, the electrode reaction, and the diffusion of the product, proceed in an equal velocity at the electrode surface. The result thus obtained can explain the essential rôle of the curvature of the electrode in some problems concerning the electrode reaction.
The formulas for the current-voltage curve of the reduction wave of the hydrogen ion under the various mechanisms of the overall deposition process were derived from the standpoint of chemical kinetics. The results on the various properties of the current-voltage curve,—the relation between the half-wave potential and the concentration of the hydrogen ion in the bulk of the solution, the property of the limiting current, and the log-plot analysis of the current-voltage curve—are presented. It is assumed throughout the present discussion that the processes at the electrode surface, including the diffusion process, are kept in a. stationary state, i. e., in a dynamic equilibrium. This assumption seems to be reasonable when the stationary and reproducible current-voltage curve is obtained at the dropping mercury-electrode.
The properties of the limiting current of the reduction wave of the hydrogen ion were studied in the system of dil. HCl in 0.1 N KCl solution. The relution between the limiting current and the concentration of the hydrogen ion in the bulk of the solution was linear, and the experimental relation between the limiting current and the height of the mercury reservior was interpreted by the revised Ilkovic equation. It was shown that the temperature coefficient of the limiting current is nearly equal to 1.0 % at 25° which is in agreement with the theoretical value computed from the revised Ilkovic equation. From these results it was concluded that the limiting current of the hydrogen ion obtained under the present condition is controlled by the diffusion process of the hydrogen ion.
The heats of sublimation of a series of condensed polynuclear aromatic hydrocarbons, 1rom anthracene (C14) to violanthrene (C34), were measured. It has been found that there is an additivity in the inner heats of sublimation among these compounds, i. e., as the number of carbon atoms in each molecule increases by one, the inner heat of sublimation increases by 1.51 kcal./mole.
(1) From the standpoint of chemical bond a new empirical rule for the calculation of entropy of polyatomic gas molecule has been proposed. It agrees with the observed value within the error of ±2 e. u., and includes monoatomic and diatomic molecule as a special case, and finally gives the upper limit of the observed value. (2) The abnormal depression of entropy from the standard of the present rule was interpreted as ring closure entropy and resonance entropy, and respective values were given for some typical substances. Closure entropy 20.9 e. u. of cyclohexane and resonance entropy 4.2 e. u. of benzene agreed well with the conclusion of Bremner-Thomas according to the atomic group method. (3) It has been shown that resonance entropy is so small that its contribution to the resonance free energy is neglisible compared with resonance energy. In special case, however, the contribution of the resonance entropy is about 10% of the resonance free energy, as in the case of carbon dioxide. (4) It has been shown that it is impossible to construct the true bond entropy, which is. additive and independent. But it is possible to build up the formal bond entropy, which is additive and not independent. (5) In order to show that the present rule includes naturally the atomic group method, some typical rules of the atomic group displacement method have been derived. (6) Under some assumptions the frequency factors of some simple chemical reactions have been computed by means of the present rule. The calculated values agreed with the observed, within 3∼l/6 times.
(1) Force-area relations for 2-phenyl-, 2-(α-naphthyl)-, 2-benzyl- and 2-(α-naphthomethyl)-n-fatty acids have been investigated. (2) Force-area curves are characteristic to each of the four series, showing that the length of alkyl chains in the molecules has only a minor effect upon the curves. (3) Influence of pH on the force-area curves, so far examined, is shown to be similar to other fatty acids. (4) It was concluded that the aromatic ring in the α-position of the fatty acids has such an orientation that the plane of the aromatic ring is placed perpendicular to the water surface. (5) Film properties seem to have no direct relation to the antibacterial activity of these compounds, and some of the regularities for the activity are discussed.
1. A torsion ring method using a suspension wire of low torsion constant was employed for the measurement of a surface viscosity and rigidity of aqueous solutions. 2. The mechanical behaviours of the surfaces of the solutions of saponin, polyvinyl alcohol, crystal violet and horse serum albumin aged for one hour were analysed and expressed using mechanical models. The corresponding rigidity and viscosity were estimated. 3. The mechanical models observed were the Newtonian flow, non-Newtonian flow, Maxwell model with Newtonian or non-Newtonian flow, Voigt model, and three para-meter model consisting of a series combination of a spring and a Voigt element.
Data of nitrate and phosphate detrminations have been selected from those of the ZunanKuroshio observations which were made from January, 1950 to February, 1951, and their seasonal variations were investigated with reference to N/P ratio. As a result, it was proved that no change was recognised in deep layers (400-800 m.) at Station 6 (in the main current of the Kuroshio) throughout the period, but deviations from Cooper’s normal ratio were found in surface and subsurface layers. The cause of these deviations may partly be due to the decomposition processes of dead marine organisms.
An X-ray diffraction study of crystals of dichloro-aquo-triammine-cobalt (III) chloride eads to a hexagonal unit of structure with a=7.37 A. and c=8.75 A., containing two formula units in it. The most probable space group is D6h4−C6/mmc. For an accurate determination of the structure, the method of three dimensional Fourier series was used. The determined structure is most easily described as NiAs type, consisting of [Co(NH3)3H2OCl2]+ and Cl− ions. Two chlorine atoms are coordinated to a cobalt atom in trans-positions with respect to each other, each being 2.33 A. from the cobalt atom. The Cl-Co-Cl direction being parallel to the c-axis, the octahedral complex ions seem to have statistical azimuthal orientations in the crystal and the apparent, symmetry of the complex ion is D3h− 6m2. Such an arrangement of the complex ions in the crystal may well account for the marked red-blue dichroism of the crystals.
The crystal structure of trans-dichlorodiethylenediamine-cobalt (III) chloride hydrochloride has been determined using the rotation method (Fe Kαλ=1.937 A.). The substance crystallizes in a monoclinic lattice with two formula units in the unit cell, the dimensions of which are a= 10.68 A., b=7.89 A., c=9.09 A. with β=110°26. The determined structure seems most easily described as consisting of layers of [Coen2Cl2]+ ions parallel to the plane (100) and those of Cl−, H2O and H+. Two chlorine atoms are co-ordinated to a cobalt atom in trans-positions. The line joining them is perpendicular to the plane in which four nitrogen atoms are found to lie. The dimensions of a complex ion are given. The water molecules probably form a group [H2O···H···H2O]+ together with a proton, O···O distance being 2.66 A. These groups are located between them. The dichroism of the crystal is, discussed on the basis of the determined structure.
The free energy expression derived by Scott for the polymer-mixed solvents system are refined and amplified, removing the assumptions which are not always applicable to the actual cases, although it was introduced by him for the sake of simplicity. Owing to scantiness of the available data and to difficulties of exact, calculation, the phase diagrams of the system using the results obtained are not given here. Determination of plait points and the problems in the osmotic pressure measurement in mixed solvents will be discuss d elsewhere. Here, we confined ourselves to formulate the free energy expression for various systems also involving the systems in which one or two of the constituents are associated liquids as a special case where the assumption (b) is far from true. Application of the result obtained to some problems-in viscosity, osmotic pressure, and swelling phenomena will be presented in the following-articles. This paper was presented at the Annual Meeting of the Tokyo Institute of Technology, where the treatment of associated liquids was discussed with particular reference to the applicability of the above methods to the thermodynamic problems of association. In the writer’s opinion, the generality of the thermodynamic function derived here in the application to equilibria involving transformation between various “polymeric” species of the associated liquid may be accessible when the volume effect of the associated liquid on the entropy term in these systems must be encountered. Obviously the Flory-Tobolsk y-Bratz treatment is applicable only to the linear “polymer” such as alcohol, and we may go too far to say that our treatment is also-applicable to the three dimentional “polymer”-Our treatment is supposed, however, to be not far from true even in such a case, since the entropy of mixing in the above systems containing associated liquids as one or two components was formulated on the assumption that the submolecules of the “polymer” are distributed at random, i. e., this corresponds to the Bragg-Williams approximation.
(1)An expression for the melting points of the inorganic compounds of type MXOn has been obtained as, T·(α_+-α_-)^1/6=a-b·(r_-/r_+), and the values of a and b have been given, where T is the melting point in absolute temperature, α+ and r+ are the polarizability and the ionic radius of the cation M+, res-pectively, and α−, r− are the polarizability and the ionic radius of the ion X(2n−1)+ respectively. (2) Considering the results of the practical calculation, the values given by Goldschmidt are to be adopted for the formula as the polar -izabilities and ionic radii, and those given by Fajans and by Pauling are less satisfying in some cases. It is probably due to the fact that the Gold Schmidt’s values correspond to the ions in the solid and those of Pajans and of Pauling to the free ions. (3) This formula will be useful for the ex-amination of the known values of the melting points and for the estimation of the unknown data. (4) It is very important that ‘melting point’ is presented as a function of the variables characteristic for atoms, such as ionic radius and polarizability of atoms.
From the results of a further study of corbisterol by bromination, reduction and ozonolysis of corbisteryl acetate and absorption spectrum of corbisterol, the structure of corbisterol is believed to be 5, 7, 22-triunsaturated C29-sterol.