Metal-ammonia solutions viscosity

From the meager data available, the observed analogy in the variation of the conductance in the methyl amine solutions with concentration and temperature with that in the ammonia solutions suggests a close similarity in the constitution of both solutions, as also do the optical data discussed in Part III-B. The observed conductance in methylamine solutions with concentration greater than 0.3M is smaller by about a factor of 100 than the conductance in the corresponding ammonia solutions. This can probably be explained by the smaller solubility of the metals in amine solutions. This would lead to a larger value for the number of methylamine molecules per atom of metal dissolved relative to ammonia solutions (about 6 in saturated sodium-ammonia solutions as compared to 23 in sodium solutions in methylamine). However, in very dilute solutions, the smaller value of the equivalent conductance in the methylamine solutions would have to be explained by differences in physical properties such as viscosity and dielectric constant of ammonia and methylamine. 

Soft silvery-white metal body-centered cubic structure density 0.531 g/cm3 burns with a carmine-red flame, evolving dense white fumes melts at 180.54°C vaporizes at 1,342°C vapor pressure 1 torr at 745°C and 10 torr at 890°C electrical resistivity 8.55 microhm-cm at 0°C and 12.7 microhm-cm at 100°C viscosity 0.562 centipoise at 200°C and 0.402 centipoise at 400°C reacts with water soluble in liquid ammonia forming a blue solution. 

The only satisfactory method for synthesizing hydrazine was devised by Raschig1 and involves the oxidation of ammonia by sodium hypochlorite in the presence of some such catalyst as glue or gelatin. The purpose of the catalyst is to raise the viscosity of the solution and to inhibit the effect, by adsorption, of traces of metallic ions which cause decomposition of the hydrazine formed.2 It is therefore advisable to use distilled water. Since free chlorine, if present in the hypochlorite solution, oxidizes ammonia to nitrogen, special care must be taken in the preparation of the oxidizing solution. The hypochlorite solution should be distinctly alkaline. %... 

Catalytic supercritical water oxidation is an important class of solid-catalyzed reaction that utilizes advantageous solution properties of supercritical water (dielectric constant, electrolytic conductance, dissociation constant, hydrogen bonding) as well as the superior transport properties of the supercritical medium (viscosity, heat capacity, diffusion coefficient, and density). The most commonly encountered oxidation reaction carried out in supercritical water is the oxidation of alcohols, acetic acid, ammonia, benzene, benzoic acid, butanol, chlorophenol, dichlorobenzene, phenol, 2-propanol (catalyzed by metal oxide catalysts such as CuO/ZnO, Ti02, MnOz, KMn04, V2O5, and Cr203), 2,4-dichlorophenol, methyl ethyl ketone, and pyridine (catalyzed by supported noble metal catalysts such as supported platinum). ... 

Some important examples of the application of N NMR spectroscopy in S-N chemistry include (a) investigations of the (NSCOj 3NSC1 equilibrium in solution and (b) identification of the S-N species present in solutions of sulfur in liquid ammonia. The half-width of N NMR resonances is dependent on the symmetry of the atomic environment as well as other factors, such as solvent viscosity. The values may vary from ca. 10 Hz for solutions of NS2" AsFe in liquid SO2 to >1000 Hz in metal-S-N complexes. However, the chemical shift range for S-N compounds is ca. 800 ppm, so that useful information may frequently be obtained despite the broad lines. Liquid SO2 is a particularly good solvent for N NMR studies of cationic S-N species, while liquid ammonia is well suited to investigations of S-N anions/ ... 

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