The double reduction waves of pure aquo tripositive europium ion, under various conditions, at dropping mercury electrode were studied. The effects of the variations in pH, the concentration of europium ion, the anion species of supporting electrolytes, and the concentration of gelatin as maximum suppressor, etc. were examined. The electrode reaction of the first wave was irreversible and one electron reduction, and that of the second wave was the irreversible or quasi reversible two electrons reduction. The half-wave potentials of the first wave and the second wave at pH 2.95 were as follows. (E_1)_1/2: -0.767 V. vs. S. C. E.(E_2)_1/2: -1.971 V. vs. S. C. E.where concentration of Eu3+ ion : 1.104 mM in 0.1 M LiCl and 0.01% gelatin medium.
(1) It was found, by means of the thermal and magnetic balance, that the decomposition temperatures of silver oxide and of silver oxide containing silver carbonate are 354 and 372°C, respectively. (2) The magnetic susceptibilities of metallic silver obtained by the decomposition and of silver oxide are −0.21×10−6and −0.48×10−6 units per gram at room temperature, respectively. Metallic silver is normally diamagnetic from room temperature to 1100°C. (3) Under the present experimental conditions, the rate of decomposition is represented by the equation dx⁄dt=aitbi for the whole course of the decomposition, where i is the subscript for each stage, and generally both ai and bi depend on the temperature. It is considered that nuclei are created at intervals as the reaction proceeds.
1) Reaction product vaporizes from the filament as tungsten trioxide and its colorless deposit is reduced with hydrogen liberated by the reaction. Consequently, the blue deposit having the mean apparent composition of WO2.80 can be obtained. 2) The WO3 deposit is reduced readily with atomic hydrogen down to WO2.80, but the reduction rate becomes appreciably slower at the lower oxidation state. 3) Oxygen is not contained in hydrogen. This suggests that WO3 is not formed by a reaction of tungsten with gaseous oxygen liberated by thermal decomposition of water vapor, but is formed directly by a reaction of tungsten with water vapor.
The isothermal rate of crystallization in polychlorotrifluoroethylene was measured at temperatures ranging from 172 to 190°C below the melting point by following the change of observed absorbance of crystalline band at 440 cm−1. The isothermal rate of crystallization and apparent induction time are dependent on temperature. The data on the kinetics of the crystallization are compared with the result of Avrami’s analysis. At temperatures between 190 and 185°C the nucleation process will be promoted by heterogeneities which exist in the melt. Between 184 and 178°C it will be mainly governed by homogeneous nucleation.
Ultraviolet absorption spectra of several nuclear substituted phenylureas have been measured with the attempt to study the electronic effect of the carbamide group, and the resonance stabilization in three dulcin isomers.
A procedure to obtain a general flow curve by falling-sphere method is presented. The shear stress SR and shear rate (du/dr)R at the equator of the sphere are given as & S_R=RΔρg/3 & (du/dr)_R=(3U_0/2R) & ×[1+2.5(dlogU_0/dlogR-2) & -(3/4)(dlogU_0/dlogR-2)^2] where Δρ is the density difference between sphere and fluid, R the radius and U0 the falling velocity of the sphere.
The two new compounds, N-salicylideneglycinato-aquo-copper(II) and sodium N-salicylideneglycylglycinato - cuprate(II) were prepared and investigated as to their structure. Their infrared, visible and ultraviolet absorption spectra together with those of some related compounds were measured and discussed.
The effects of phenylazo p-tolyl sulfone upon the polymerization of methyl methacrylate were examined. In the solutionpolymerization in benzene, the initial rate of polymerization was linearly dependent respectively upon the square root of the concentration of phenylazo p-tolyl sulfone and upon the concentration of methyl methacrylate. A unimolecular first order decomposition of phenylazo p-tolyl sulfone is suggeted as the initiating reaction of the polymerization. Dimethylaniline acted as an accelerator for this polymerization. In this case, the initial rate of polymerization was linearly proportional to the square root of each of the concentrations of phenylazo p-tolyl sulfone and dimethylaniline. A bimolecular reaction between phenylazo p-tolyl sulfone and dimethylaniline has been proposed for the acceleration of the polymerization.
The crystal structure of bis(glutaro-nitrilo)copper(I) nitrate has been determined by the two-dimensional Fourier method. It is tetragonal P\bar421c with two formula units in a cell of dimensions: a=8.25±0.01 Å and c=9.71±0.01 Å. The crystal consists of infinite two-dimensional networks of complex ion [Cu(NC–CH2–CH2–CH2–CN)2]nn+ and nitrate ions. A copper atom is tetrahedrally surrounded by four nitrogen atoms at a distance of 1.98 Å. Each glutaronitrile molecule is coordinated to two different copper atoms with nitrogen atoms at both ends and takes a gauche-gauche configuration with respect to the two C–C bonds. The nitrate ions lie perpendicularly to the c-axis. The trigonal nitrate ions seem to have statistical azimuthal orientations in the crystal and the apparent symmetry of the nitrate ion is \bar4. All the atoms in the group Cu–N–C–C lie approximately on a straight line. This fact and the observed carbon-nitrogen distance of 1.14 Å suggest that the bond character in the carbon-nitrogen group may essentially be expressed as C≡N.
The crystal structure of bis(adiponitrilo)-copper(I) nitrate has been determined by the two-dimensional Fourier method. It is orthorhombic Pnnn with two formula units in a cell of dimensions: a=9.41±0.02 Å, b=13.73±0.02Å and c=5.85±0.01 Å. The crystal consists of infinite three-dimensional networks of complex ion [Cu(NC–CH2–CH2–CH2–CH2–CN)2]nn+ and nitrate ions. A copper atom is tetrahedrally surrounded by four nitrogen atoms at a distance of 1.98 Å. Each adiponitrile molecule is coordinated to two different copper atoms with nitrogen atoms of both ends, forming a planar zigzag configuration of methylene groups. Thus the copper atoms and the ligand molecules form a complicated threedimensional 4-connected network. The nitrate ions lie perpendicularly to the a-axis. The trigonal nitrate ion seems to have statistical azimuthal orientations in the crystal and its apparent symmetry becomes 222. All the atoms in the group Cu–N–C–C lie approximately on a straight line. This fact and the observed carbon-nitrogen distance of 1.13 Å suggest that the bond character in the carbon-nitrogen group may essentially be expressed as C≡N. On the basis of the structures of this and the other related complexes, some remarks have been made on the mechanism of cuprous ion dyeing of polyacrylonitrile fibers.
Electronic structures of o-benzoquinone, β-naphthoquinone and phenanthrenequinone were studied with the simple MO method, using the same integral values as those adopted in the self-consistent MO calculation for o-benzoquinone. As for charge distributions, the negative charges of oxygen atoms slightly increase in the order of o-benzoquinone, β-naphtho-quinone, and phenanthrenequinone. The calculated dipole moments (6.6, 9.5 and 8.4 D for o-benzoquinone, β-naphtho-quinone and phenanthrenequinone, respectively) seem a little greater than the experimental values. As for bond orders, reasonable results were obtained. The calculated results predict the existence of a doublet with a large splitting constant (ca. 4.5 gauss) in the hfs of the electron paramagnetic resonance absorption of β-naphtho-semiquinone ion. Three problems concerning the near UV absorption bands [1) the similarity among the π–π transition bands of the three o-quinones, 2) the relative magnitude of the n–π transition energy of o-benzoquinone, β-naphtho-quinone, and phenanthrenequinone, 3) the effect of the electron-donating group on the π–π transition bands of o-benzoqui-none and β-naphthoquinone] can be clearly explained by the calculated results, as in the cases of the p-quinones.
On the basis of the two-dimensional analogy of the method of McMillan and Mayer, the van der Waals constant A0 for monolayers of rigid rod-like molecules is calculated theoretically for the cases in which all molecules are (1) vertical to the interface; (2) lying flat upon the interface; (3) inclined by a constant angle θ0; and (4) orienting freely. The theoretical equations thus obtained are used to discuss the orientation of molecules in gaseous films of myristic acid, tridecylic acid and lauric acid. As the results, it is concluded that the molecules of myristic acid and tridecylic acid are lying flat upon the interface in the gaseous film until the phase transition to a condensed film occurs. On the other hand, molecules of lauric acid are freely orienting when the area per one molecule is large, and the orientation becomes the more vertical, the more the monolayer is compresssed. The molecular orientations during this compression process were described quantitatively.
The dielectric constant for the mixture dichloroethane-carbon tetrachloride was calculated by making use of a model proposed by Onsager, Fujishiro and Schlote. The calculated values agree rather well with the experimental. The higher the temperature is, the better is the agreement. The dielectric constants of other mixture such as dichloroethane-cyclohexane, dichloroethane-benzene and dichloroethane-carbon disulfide were also measured only at 25°C and compared with one another. The coincidence of the theoretical values with the experimental was obtained in the following order; carbondisulfide, benzene, carbon tetrachloride and cyclohexane.
Sublimation pressures of a number of organic molecular crystals were measured by a viscosity gauge. The heats of sublimation of these compounds were examined in relation to their molecular structures, and it was concluded that an additivity rule could be applied to the lattice energies of these crystals as a first approximation.
Stress relaxation curves were obtained for the gels of the polyvinyl alcohol-conga red-water system in the temperature range, 15∼60°C, by means of a chainomatic relaxometer. The molecular weight of polyvinyl alcohol was 8.5×104, and gels of 15.0 and 17.5% were used, where the concentration of congo red was adjusted to be 1/10 of that of polyvinyl alcohol. Master relaxation curves were obtained for each concentration over the range, 10−2∼109hr, and relaxation spectra were calculated by the second order approximation. The following results were obtained. 1) The logaT vs. T relation gives a single curve for two concentrations, and does not obey the equation of WLF form, Also it has characteristics similar to that of agar-agar gels. 2) The apparent activation energy is kept constant to be 42 kcal. below about 43°C, and above this temperature it sharply increases with temperature. 3) The reduction on concentration to a single composite relaxation curve seems to be possible in rough approximation.
1. The heats of combustion of lower members of methyl- and ethyl-methoxy-polysiloxanes have been measured at 20°C and constant volume, and the corresponding heats of combustion and formation in isobaric process have been calculated. 2. The bond energy term in structural unit of (Remark: Graphics omitted.) has been calculated from the heat of formation, and it has been found that its value increases with the polymer sizes of the members. Finally, the (Remark: Graphics omitted.) has been compared with that expected from the additive law of bond energy, and the lowering of bond energy in these molecules has been discussed in view of the resonance effect.
The state of formic acid adsorbed on silica and alumina has been studied by a combined method of nuclear magnetic resonance and infrared absorption. The adsorbed formic acid in a monomolecular layer has been found not to be dissociated in the case of silica, but to be dissociated in the case of alumina.
A compound between aluminum oxide and aluminum nitride can be produced in a reductive atmosphere above 1650°C. A new spinel formula AlN–Al2O3 should be adopted instead of the previous one Al2O–5Al2O3 or Al3O4. The physical constants of AlN-Al2O3 are as follows: crystal structure Fd3m, Z=8, a=7.940 Å; density 3.78g./cc.; dielectric constant 23.8; refractive index 1.80; magnetic susceptibility −0.34×10−6/g