Rubidium with methanol, reaction

The reactions of all the alkali metals with water, of cesium and rubidium with methanol, of cesium with ethanol, and of cesium with HC1 and with NH4Br have been examined. Figure 1 shows a typical oscilloscope trace, and Figure 2 shows a plot of log absorbance vs. time for this trace. The reaction is pseudo-first-order in metal (since solute concentration is ten or more times greater than metal concentration), and the overall rate constants and their order in solute are obtained by varying solute concentration. 

Methanol. Rubidium reacted with one methanol concentration, and two runs were made with cesium using several concentrations of methanol. While reaction times were comparable to those observed in the water reactions, several marked differences were apparent. In some cases two rates were observed, but the constants were not reproducible. More striking was the fact that the shapes of the traces themselves differed from picture to picture, and with dilute solutions seemed to indicate that an absorbing intermediate was formed. For these reasons we do not report any rate constants at this time. 

Metal Azides. Vapor with silver or sodium azide forms explosive bromine azide.10 Metals. Impact-sensitive mixtures are formed from lithium or sodium in dry bromine.11 Potassium, germanium, antimony, and rubidium ignite in bromine vapor.12 Violent reaction occurs with aluminum, mercury, or titanium.13 Methanol. Vigorously exothermic reaction on mixing the liquids.14 Nonmetal Hydrides. At room temperature, violent explosion and ignition occur with silane and its homologs15,16 and with germane.17... 

The trapped electrons were formed simply by depositing alkali metal atoms on ice or solid alcohols at 77°K. Studies were made of the reactions between sodium or potassium atoms and ice (HgO or D2O), methanol, ethanol, isopropyl alcohol, t-butyl alcohol or dodecanol. The reactions of caesium, rubidium and lithium with ice were also investigated. The deposits were highly coloured and the optical and e.s.r. spectra showed that the electron was no longer associated with the alkali metal ion but had been transferred completely to the solid matrix. 

In the 1920 s, E. MQller and his co-workers made a series of studies on the anodic oxidation of methanol, formaldehyde, and formic acid which represent the first extensive mechanistic investigation of these compounds, although the principles of electrode kinetics had not yet been formulated. Muller did not establish mechanisms for these reactions however, many of his observations have been later confirmed and his studies were among the first with a comparison of polarization curves on several noble metals including platinum, palladium, rhodium, iridium, osmium, rubidium, gold, and silver (cf. Figure 1). As was usual at that time, Muller discussed his results in terms of polarization, rather than in terms of current or reaction rate. 

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