Rubidium carbonate, reactions, 339

Rubidium hydroxide is a stronger base than caustic soda or caustic potash. Its reactions are similar to theirs. Neutralization occurs with acids. Rubidium hydroxide absorbs carbon dioxide forming rubidium carbonate. 

Rubidium acid salts are usually prepared from rubidium carbonate or hydroxide and the appropriate acid in aqueous solution, followed by precipitation of the crystals or evaporation to dryness. Rubidium sulfate is also prepared by the addition of a hot solution of barium hydroxide to a boiling solution of rubidium alum until all the aluminum is precipitated. The pH of the solution is 7.6 when the reaction is complete. Aluminum hydroxide and barium sulfate are removed by filtration, and rubidium sulfate is obtained by concentration and crystallization from the filtrate. Rubidium aluminum sulfate dodecahydrate [7488-54-2] (alum), RbA SO 12H20, is formed by sulfuric acid leaching of lepidolite ore. Rubidium alum is more soluble than cesium alum and less soluble than the other alkali alums. Fractional crystallization of Rb alum removes K, Na, and Li values, but concentrates the cesium value. Rubidium hydroxide, RbOH, is prepared by the reaction of rubidium sulfate and barium hydroxide in solution. The insoluble barium sulfate is removed by filtration. The solution of rubidium hydroxide can be evaporated partially in pure nickel or silver containers. Rubidium hydroxide is usually supplied as a 50% aqueous solution. Rubidium carbonate, Rb2C03, is readily formed by bubbling carbon dioxide through a solution of rubidium hydroxide, followed by evaporation to dryness in a fluorocarbon container. Other rubidium compounds can be formed in the laboratory by means of anion-exchange techniques. Table 4 lists some properties of common rubidium compounds. 

An intimate mixture ot 274 grms. of rubidium iron alum, or 260 grms. of rubidium aluminium alum with 100 grms. of calcium carbonate, and 27 grms. of ammonium chloride, is heated in a nickel crucible to a dull red heat until ammonia vapours are no longer evolved, and then the temp, is raised to redness. The product is ground with a litre of cold water for 15 minutes filtered by suction and washed with 400 c.c. of water, added in small portions at a time. The combined sulphuric acid is precipitated by the addition of barium hydroxide, and the filtered liquid boiled while a stream of carbon dioxide is passed through the soln. If the soln. loses its alkaline reaction, and yet retains some calcium, a little rubidium carbonate must be added to precipitate calcium carbonate. The soln. is then treated with hydrochloric acid and evaporated. 

Rubidium Metarsenite, RbAs02, has been prepared8 by the action of arsenious oxide on rubidium carbonate in aqueous solution. It is a white amorphous powder which is converted to arsenate in aqueous solution and by the action of heat. The solution is alkaline in reaction. 

The basicity of cesium carbonate is strong enough to deprotonate tosyl amides [38]. Although lithium, calcium, and rubidium carbonates have also been examined for use of the same reaction for cyclization of ditosyl amide, they do not work efficiently compared with cesium carbonate (Scheme 2.23). Cesium carbonate is also important base for the preparation of calix[4]arenes and carcerands [39]. 

The results obtained are summarized in Table I. Chromatograms of aliphatic hydrocarbons, aromatic hydrocarbons, and fatty acids produced when potassium carbonate, rubidium carbonate, or magnesium carbonate was used as a promoter are presented in Figures 2, 3, and 4, respectively. The fatty acids obtained when a potential fatty-acid precursor (dodec-anal, 1-dodecanol, or 1-pentadecene) is added to a reaction are shown in Figure 5. The mass spectogram of the methyl ester of a n-Cs fatty acid (potassium carbonate- C used as promoter) is presented in Figure 6. 

Potassium carbonate (runs 4-97, 4-109, 5-24, and 5-44) and the similar rubidium carbonate (run 4-120) promoted the synthesis of fatty acids. The other carbonates, i.e., calcium carbonate (run 4-106), sodium carbonate (run 4-107), magnesium carbonate (run 5-27), and potassium chloride (run 4-114), did not produce fatty acids. Small amounts of fatty acids were obtained when potassium hydroxide (run 5-32) was used. However, some potassium carbonate was produced in situ in this reaction. 

The synthesis of fatty acids by a Fischer-Tropsch-type process as described in this chapter required the use of a catalyst (meteoritic iron) and a promoter. Potassium carbonate and rubidium carbonate were the only compounds evaluated which unambiguously facilitated the production of fatty acids. These catalytic combinations (meteoritic iron and potassium carbonate or rubidium carbonate) also produced substantial amounts of n-alkenes (in excess of n-alkanes) and aromatic hydrocarbons. A comprehensive study of the nonacidic oxygenated compounds produced in Fischer-Tropsch reactions (20,21) was not made. However, in the products analyzed (all promoted by potassium carbonate), long-chain alcohols and aldehydes were detected. 

Cesium reacts with water in ways similar to potassium and rubidium metals. In addition to hydrogen, it forms what is known as superoxides, which are identified with the general formula CsO When these superoxides react with carbon dioxide, they release oxygen gas, which makes this reaction useful for self-contained breathing devices used by firemen and others exposed to toxic environments. 

Alkyllithium compounds as well as polymer-lithium associate not only with themselves but also with other alkalimetal alkyls and alkoxides. In a polymerization initiated with combinations of alkyllithiums and alkalimetal alkoxides, dynamic tautomeric equilibria between carbon-metal bonds and oxygen-metal bonds exist and lead to propagation centers having the characteristics of both metals, usually somewhere in between. This way, one can prepare copolymers of various randomness and various vinyl unsaturation. This reaction is quite general as one can also use sodium, rubidium or cesium compounds to get different effects. 

Precipitate with aq. ammonia. Evaporate the soln. down to about 100 c.c., and filter the ot liquid so as to remove calcium sulphate. The cone. soln. is sat. with ammonium alum and allowed to stand for some time. The mixed crystals of potassium, rubidium, and oeesium alums and of lithium salt are dissolved in 100 c.c. of distilled water and recrystal-lized. The recrystallization is repeated until the crystals show no spectroscopic reaction for potassium or lithium. The yield naturally depends on the variety of lepidolite employed. 100. grms of an average sample gives about 10 grms. of crude crystals and about 3 grms. of the purified caesium and rubidium alums. For the purification of caesium and rubidium salts, see the chlorides. The mother-liquors are treated with an excess of barium carbonate, boiled, and filtered. The filtrate is acidified with hydrochloric acid, and evaporated to dryness. The residue is extracted with absolute alcohol in which lithium chloride is soluble, and the other alkali chlorides are sparingly soluble. 

Rubidium Arsenates.8—Rubidium Orthoarsenate, Rb3As04, is prepared by adding a solution of rubidium hydroxide to aqueous arsenic acid until the former is in excess. Very hygroscopic white lamellae of the dihydrate, Rb3As04.2H20, are deposited on evaporation. The salt absorbs carbon dioxide from the air and its solution is alkaline in reaction. When heated, the water of crystallisation is lost at 100° C. 

Rubidium chloride even slows the reaction, this is especially well seen within a time span of 1-3 hr after the start of the process (Fig. 2, curve 2). In this case the normal salt effect is likely to prevail over the effect of oximate ion pair separation due to substitution of the potassium cation by the rubidium cation. The addition of cesium carbonate during the first 1.5 hr does not much affect the rate of the formation of 2-phenylpyrrole. The accelerating effect of these additives becomes evident only 2 hr after the beginning of the reaction and gradually increases (5 hr later the yield gain of pyrrole is 7% as compared with a standard run, Fig. 2, curve 4) which seems to result from a slow rate of heterophase exchange process ... 

Potassium hydride, KH.—Moissan5 prepared the hydride by a method analogous to that employed by him for the corresponding sodium derivative, the excess of potassium being dissolved by liquid ammonia. Ephraim and Michel6 passed hydrogen into potassium at 350° C., and found the reaction to be promoted by the presence of calcium. The hydride forms white crystals of density 0-80. The vapour-tension for each temperature-interval of 10° between 350° and 410° C. corresponds with the values 56, 83, 120, 168, 228, 308, and 430 mm. respectively.7 In chemical properties potassium hydride resembles the sodium compound, but is less stable. Its stability is greater than that of rubidium hydride or caesium hydride. Carbon dioxide converts it into potassium formate. 

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