The reason the oxide replica gives a more resolved image in electron microscopy than Formvar or collodium replica is because the small oxide particles (50-100 Å.) composing replica film are oriented according to the orientation of the metal crystals of substrates. The electrodeposited replica and sulphide film formed on metals give the resolved images in microscopy. This is explained in the same way as for oxide replica.
1. The empirical rule for the calculation of the activation energy previously proposed has been applied for some more complicated reactions. 2. For the addition reaction of halogen to ethylene the calculated values agree very well with the observed values, but for that of hydrogen the calculated value was somewhat greater than the observed. 3. For the atomic reactions involving sodium and halogen atoms the calculated values agree well with the observed under the appropriate assumptions. 4. The activation energies for the adsorption of hydrogen and ethylene on nickel have been calculated, and the initial rate of adsorption of ethylene calculated by the use of the obtained value of the activation energy was compared with the experimental value of Steacie and Stovel.
The activation energy for the activated adsorption of hydrogen on copper metal has been calculated by the use of the empirical rule previously proposed. The calculated value 19.4 kcal./mole agrees very well with the observed value 20 kcal./mole of T. Kwan. It has been concluded that hydrogen will be adsorbed more quickly on the surfaces (110) and (111) than on the surface (100) of copper crystal.
(1) A new thermodynamic relationship applicable to dilute solution of rigid rod-like molecules was derived, employing a lattice model. (2) Small deviation from Zimm’s result for rigid rod was discussed here, considering the effect of size and shape of solvent and solute. (3) Although quantitative discussion is impossible because of the difficulty of the estimation of the size of the submolecule, it may be said that the contribution of entropy of dilution to A2 (the second virial coefficient in osmotic pressure expression as power series in concentration) will be less for rigid rod-like molecules than for coiled molecules, and furthermore, the difference between such systems as cellulose derivatives in a series of solvents will be very small.
Considering the dynamic equilibrium of adsorption and desorption on the surface of water, Szyszkowsky’s equation is derived. Using the area of dye molecule calculated from the molecular structure, U0 and Γ2 are estimated to obtain the best conformity with the measurement of the surface tension. UΓ calculated by them is compared with the foam formation of these triphenyl methane dyes. Maximum observed in the foaming ability—concentration curve of methyl violet 5 B is explained by its large surface activity. The fact that the energy required to bring the unit area of dye molecule into the bulk solution is about 20 erg/cm.2 is justified using the correction of interfacial energy due to the fact that the thickness of the adsorption layer is nearly equal to the dimension of the range of molecular force.
The effect of various metallic ions on the pressure∼area curve of the monomolecular film of stearic acid spread on the surface of the solution was studied. It was found that they were classified into two groups; one involves those which make the film condense such as calcium, barium and magnesium and the other those which make it expand such as thorium, aluminum, iron, copper, zinc, mercury, cobalt and nickel. This classification was explained from the standpoint of molecular structure of the resulting metallic soaps. It was suggested that while the soap of the former metals has a simile structure the soap of the latter metals has a complicated polymeric structure. These structures were explained by the characteristic nature of metallic ions of two groups.
A relative rigidity of the monolayer of stearic acid on the surface of water containing various metallic ions was measured by the displacement of the glass thread. It was found, as was pointed out in the preceding paper, that metallic ions were classified largely into two groups, namely ions which render the surface film remarkably rigid and those without such effect. Those of the former group are thorium, aluminum, iron, copper, zinc, mercury, cobalt and nickel, while the latter group involves calcium, barium and magnesium. So-called expansion pattern of the film of stearic acid in the presence of these metallic ions was also studied, the result of which also confirmed this conclusion.
The interaction between the dyes dissolved in water and the monolayer of stearic acid spread on it was studied and discussed. It was shown that a remarkable expansion of the monolayer of stearic acid in the presence of phloxine and congo red was explained chiefly by the van der Waals adsorption, while that in the presence of basic dyes was explained chiefly by the ionic interaction. It was suggested that the interaction between basic dyes and stearic acid was analogous in some respects to the formation of soaps of such metals as thorium, aluminum, etc.
(1) Compounds ranging from violet black to puce in color, [Co(NH3)6]PbCl6, [Cr(NH3)6]PbCl6[Co(NH3)5H2O]PbCl6 and [Cr(NH3)5H2O]Pb Cl6 have been prepared, by mixing a solution of [Co(NH3)6]Cl3 etc. (in dil. HCl) and a solution containing H2PbCl6 and digesting them at 40° to 60°. (2) [Co(NH3)6]PbCl6 and [Co(NH3)5H2O]PbCl6 are diamagnetic and therefore it seems natural to consider these compounds as hexamminecobalt(III) chloroplumbate (II, IV) and aquopentamminecobalt(III) chloroplumbate (II, IV) respectively.