(1) The adsorption of hydrogen on a copper catalyst containing 1% magnesia sintered at various temperatures has been investigated at 100° and 160°C, and compared with that on copper alone. The addition of magnesia increases markedly both the surface area and the rate of adsorption. The latter increase, however, is far beyond the increase in surface area. (2) The hydrogen adsorption per unit area of the copper magnesia catalyst is less than that on pure copper, and decreases with increasing heat treatment. The adsorption of hydrogen on magnesia powder is immeasurably small. The heat curves on differently heated catalysts do not agree with each other, but approximately do so if the effective area for hydrogen adsorption is taken into consideration. The adsorption heat for a low coverage is certainly greater on the magnesia added copper than on copper alone. (3) By aid of the electron diffraction study, it is concluded that the magnesia in the catalysts exists on the surface and forms microcrystal particles. Presumably, copper in the magnesia added catalyst is modified by the oxygen of the magnesia and irregular defects are formed on the surface in the presence of magnesia.
The low-temperature adsorption of non-polar gases (argon, oxygen, nitrogen and carbon dioxide) on cubic sodium chloride was investigated. The present results on the isosteric heats of adsorption for these four gases indicate that the non-uniformity of the surface considerably predominate in the low coverage region and the mutual interaction between the adsorbed molecules is also distinguished in the region of the comparatively high coverage. The entropies of the adsorbed materials (argon, oxygen and nitrogen) were experimentally determined and compared with the calculated values of the two-dimensional gas. These results show that the adsorbed molecules have the nature of the two-dimensional gas at least in the region of θ=0.3∼0.9. The present results indicate that the phase change (a gaseous film→a condensed film) of argon or oxygen may occur at about θ=0.9, but this fact is somewhat uncertain.
The absorption spectra were measured about a series of hexammine Ni(II) and tetrammine Pt(II) complexes having various amines as ligands. These amines were hydroxylamine, ammonia, ethanol-amine, methylamine, ethylamine and ethylenediamine. The results of the measurement indicate that the weaker the basic strength of an amine is, the more the absorption bands of the produced complex appear in the shorter wavelength. This fact was connected with crystal field theory, and the following rule was drawn: In the complex of a transition metal ion having an unsaturated d-shell, the weaker the basic strength of an amine is, the more stable the produced complex is.
The photobleaching of the evacuated aqueous solution of methylene blue by dint of tri-, di- or monomethylamine was studied. The reaction products were identified to be leuco dye and amine oxide, the former by a spectroscopic method and the latter by a chemical one. It was found that a long lived metastable intermediate is produced and this intermediate slowly returns to the original dye even in the dark. Furthermore it was found that this intermediate has its own absorption near infrared region. On the basis of the above observations, the following scheme was proposed for the reaction. (Remark: Graphics omitted.) in which the process IV can be neglected in the present experimental conditions. From the above scheme, ths following rate formula was derived which can represent all the experimental results satisfactorily. x=Ae^-(k+s)t+Be^-(k-s)t where x is the concentration of methylene blue.
The effects of various factors upon the photobleaching of methylene blue in the evacuated aqueous solution by means of mono-, di- and trimethylamine, were studied experimentally, and the result were analyzed by the rate formula presented in the preceding paper on the basis of the following scheme; (Remark: Graphics omitted.) The results obtained can be summarized as follows: k1 is written in the form; k1=k10[OH−][TA]I0. k2 and k3 are also proportional to [OH−] and they both increase monotonously with the light intensity and amine concentration. In addition, the photobleaching was examined in the presence of Fe+++ and Cu−−. It was found that in the case of Fe+++, k3 is much decreased while k1 and k2 are scarcely affected. The absorption spectra of the intermediate were observed more prominently than when no Fe+++ was present. From these results it was concluded that Fe+++ stabilizes the intermediate. In case of Cu++ some induction period was observed during which Cu precipitates, and its duration was found to be proportional to the concentration of Cu++. From these results it was tentatively concluded that Cu++ attacks the intermediate.
A mathematical proof is given that under a certain condition the static and localization theories become completely equivalent to each other in predicting the reactivities in ionic substitutions of the positions in a given even alternant hydrocarbon. The said condition is concerned with the coefficients of the powers in the expansions of the secular determinants for the residual molecules. It is shown by numerical calculations that the condition is fulfilled by almost all positions in 12 molecules treated. The change in total energy of π-electrons is given as a function of a coulomb integral, and a new quantity called partial polarization energy is introduced which is defined as a function of the π-electron density at a given position. Both are useful for relating the static quantity to the dynamic one. The latter is a new measure of a general nature for the reactivity of the position towards the ionic reagents.
The preparation of two mixed salts, 2D-[Co en3]Cl3·NaCl·6H2O and 2L-[Co en3] Cl3·NaCl·6H2O is described. The space group is P3, with one formula unit in a cell of dimensions: a=11.47±0.03 Å, c=8.06±0.02 Å. However, the structure has the pseudo space group P63. By evaluating the functions ρ(XY) and ρ(YZ), projections of the structure on two crystal-lographic planes were obtained. A kind of twinned structure was proposed to get a better agreement between the observed and calculated intensities. The structure shows very close resemblance to that of D,L-[Co en3]Cl3·3H2O. A sodium ion is octahedrally surrounded by six water molecules, with Na ···O distances of 2.62 Å. The whole structure is ionic consisting of the ions [Co en3]3+,[Na(H2O)6] and Cl−.
Dipole moments of 4-chloro-2-hydroxybenzaldehyde, 5-chloro-2-hydroxybenzaldehyde, 5-methyl-2-hydroxybenzaldehyde, p-chloroacetophenone, p-nitroacetophenone and 5-chloro-2-hydroxyacetophenone were measured in benzene solutions. Their values are 2.31D, 1.37D, 3.32D, 2.40D, 3.29D and 1.79D, respectively. The components of the dipole moments of salicylaldehyde and o-hydroxyacetophenone, which were evaluated from the components of the moments of phenol, benzaldehyde and acetophenone, do not agree at all with the components that satisfy the observed moments of salicylaldehyde and o-hydroxyacetophenone and their derivatives. The magnitudes of the discrepancies are about 1.1D in the x-direction for salicylaldehyde, about 2.3D in the x-direction for o-hydroxyacetophenone, and almost 0.0D in the y-direction for both compounds. It was concluded that the charge migration was caused from the hydroxyl oxygen to the carbonyl oxygen by the intramolecular hydrogen bonding.
A semi-empirical MO method proposed by Pariser and Parr was extended, taking account of the non-bonding electrons at the heterotoms explicitly as well as π-electorns. The electronic states of p-benzoquione were calculated neglecting cinfiguration insteractions.
(1) The reactions of hydrogen chloride with copper, nickel and copper containing 1% nickel, and the observation by means of an electron microscope were carried out to determine the state of the nickel contained in the copper-nickel catalyst. (2) The numbers of copper ion gained from the copper-nickel catalyst per g., after the reaction with hydrogen chloride, increase with the amount of consumption of hydrogen chloride used, whereas that of nickel ion is in the range of 1019–1020/ g., practically constant, independent of the amount of the consumption of hydrogen chloride. (3) The electron micrograph shows that the copper-nickel catalyst has a conspicuously rough surface, and many particles of several hundred angstroms in diameter are scattered on the surface of the catalyst. (4) The results of the hydrogen chloride reaction experiment suggest that about 3% of the total amount of nickel contained in the catalyst exists adhering to the surface of the catalyst, in the state of metallic nickel particles. (5) The ratio of the total surface area of nickel particles on the surface of the catalyst to the total surface area of the copper-nickel catalyst is given as 17%, by the calculation using the assumption that the size of the nickel particle is the same as that of the pure nickel catalyst prepared in the same way.
(1) The adsorption of hydrogen on copper, nickel and copper-nickel (containing 1% nickel) catalysts, prepared from the nitrates of copper and nickel were observed in the range of 100° to 130° or 120°C. (2) The shrinkage of surface with increase of reduction temperature was smaller for copper-nickel catalyst than for pure copper catalyst. (3) The rates of adsorption of hydrogen on copper and copper-nickel catalysts were far smaller than that of nickel; and the adsorption amount per unit area was the greatest for copper-nickel catalyst, while that of nickel catalyst was the smallest among the three. (4) The differential heats of adsorption of hydrogen at near zero coverage were given as 10.6kcal. both for copper and copper-nickel catalysts, and 24.2kcal. for nickel catalyst. (5) On the basis of the coincidence of the adsorption heats of copper and copper-nickel catalyst, it is suggested that the nickel paarticles supposed to exist on the surface of the copper-nickel catalyst may be covered with copper atoms.
From the spectral change of π band, caused by the association of azobenzene solubilized in aq. surfactant solutions, we have reached the conclusion that in a certain wide range of surfactant concentration, the micellar concentration is constant and only the number of surfactant molecules forming every micelle increases with increasing surfactant concentration. These values of the number of micellar molecules, obtained by spectral method, are in good agreement with those reported previously, in low concentration of surfactants.