Anhydrous carbonates

Kinetic and thermodynamic parameters have been measured for the chlorination of simple aliphatic and aryl alkyl ketones in strong acid media by chloramine-B (sodium A-chlorobenzenesulfonamide). Catalysis of the monochlorination of acetaldehyde in anhydrous carbon tetrachloride by trichloroacetic acid, and by hydrogen chloride, are reported. IR and UV spectroscopy have been used to probe the reaction of acetaldehyde with trichloroacetic acid in carbon tetrachloride. " Two cyclic 1 1 intermediates have been identified, and are found to be in equilibrium. 

The precipitate is filtered and dried at 100°C. If an alkali metal carbonate is used instead of ammonium carbonate, a hydrated basic carbonate is obtained which upon heating with ammonium chloride at 150°C in the absence of air produces anhydrous carbonate. 

Hydrozincite is anhydrous carbonates. The crystalline system is monoclinic-prismatic with the space group C2/m. The structure is composed of Zn in both octahedral and tetrahedral coordination, in the ratio 3 2. The octahedral Zn atoms form part of a C6 type sheet with holes. The octahedral Zn atoms occur above and below these holes. The natural hydrozincite in our study consisted of three samples. Concentrations of potential luminescent impurities are presented in Table 4.13. The laser-induced time-resolved technique enables us to detect Pb center (Fig. 4.37). 

According to G. Kirchhoff and A. Bunsen, the evaporation of soln. of csesium or rubidium carbonates furnishes crystals of the hydrated salt. G. KirchhofE and R. Bunsen add that the crystals deliquesce rapidly in air, and when heated melt in their water of crystallization, and finally form the anhydrous carbonate as a white pulverulent mass, which rapidly deliquesces in air. The hydrated forms of rubidium and csesium carbonates have not been more closely investigated. 

The process recommended by Gay-Lussac, for the preparation of pure carbonate of soda, is also a good one, and lass troublesome than tire former. He washes the ordinary commercial crystals of this salt with cold water dissolves them in hot water, and cools tire solution rapidly by surrounding it with cold water, stirring it all tho time with a spatula, so that email crystals may be formed. These are to he collected on a funnel, and after the mothar-liquor has been drained off, washed with cold water till the drainings mixed with excess of nitric aofd no longer give a precipitate with nitrate of silver. The crystals are then to be dried, and when heated to low redness, the pure anhydrous carbonate remains. 

Properties,—Anhydrous carbonate of soda is white, translucent, of specific gravity 2 4049 it Ib very soluble, and much more so in hot than in cold water its reaction is alkaline, and its taste slightly caustic, much less so than the corresponding salt of potassa. 

In this method, the crystallized and anhydrous carbonates are mixod in such proportions as to leave a slight excess of water over what is necessary for the water of crystallization of the whole salt, when it is converted entirely into bicarbonate and carbonic acid is admitted to the bottom of the mixture by a tube proceeding from a pneumatic apparatus similar to a gasometer, so constructed that there can never be any waste of gas, The absorption is completed every twenty-four hours. 

The importance of hydrogen-containing species in knock reactions is strikingly shown in knocking combustion studies of carbon monoxide by Anzilotti and Tomsic (6). The presence of 1.4 mole % of water markedly lowered the knock resistance of nearly anhydrous carbon monoxide. Other studies show that water enters into the combustion reactions of carbon monoxide and contributes hydrogen to the intermediate combustion products 125). 

Chlorine (Note 1) is passed into 300 ml. of anhydrous carbon tetrachloride (Note 2) contained in a 500-ml. three-necked round-bottomed flask equipped with a mechanical stirrer, a dropping funnel protected from atmospheric moisture by a calcium chloride tube, and a gas-inlet tube equipped with a sintered-glass tip (Note 3). The amount of chlorine contained in the resulting yellow-green liquid, estimated volumetrically (Note 4), varies between 25 and 32 g. The gas-inlet tube is replaced by a calcium chloride tube, and the reaction vessel is cooled externally with ice water and protected from light by being covered with a towel. 

Toluenesulfenyl chloride has been prepared by the action of chlorine on a solution of -toluenethiol or />-tolyl disulfide in anhydrous carbon tetrachloride.2,3 Benzenesulfenyl chloride has also been obtained by the interaction of hydrogen chloride and N,N-diethylbenzenesulfenamide 4 and by reaction of benzenethiol with N-chlorosuccinimide.6 A comprehensive review dealing with sulfenyl halides and related compounds is available.6... 

Although hydrates of rare earth carbonates at ambient temperature are well-known, their dehydration most likely leads to a series of basic carbonates. However, anhydrous carbonates of La, Ce, Pr, Nd, Sm, Eu, and Gd have been reported by Head and Holley,89 who carefully decomposed the hydrates by TGA and removed the theoretical amounts of water. 

Ethoxyphenyl Tellurium Trichloride3 To a vigorously boiling suspension of 9.0 g (30 mmol) 4-ethoxybeiizcne tellurinyl chloride in 50 ml anhydrous carbon tetrachloride is added a solution of 6.4 g (60 mmol) butyryl chloride in 5 ml carbon tetrachloride. The refluxing mixture is stirred for 1 h. On cooling, 4-ethoxypheny] tellurium trichloride precipitates. The precipitate is collected by filtration and recrystallized from acetic acid. The filtrate is stripped of the solvent and the residue distilled at atmospheric pressure. Butyric anhydride boiled at 198° yield 89%. 

Dibromophenoxatellurin 10,10-Dibromide4 In a 100 ml round bottom flask fitted with a reflux condenser bearing a calcium chloride drying tube, a magnetic stirrer, and a dropping funnel are placed 3.0 g (10 mmol) of phenoxatellurin and 15 m(of anhydrous carbon tetrachloride. 2.6 g (10 mmol) of finely ground iodine are slowly added to the stirred solution, the mixture is stirred for 5 h, and then 18.8 g (6 ml 118 mmol) of bromine are added dropwise to the stirred suspension of phenoxatellurin 10,10-diiodide. The mixture is heated under reflux on a water bath for 5 h, cooled, and the precipitate is filtered off and washed with carbon tetrachloride yield 5.3 g (86%) m.p. > 350° (from acetone). 

Dark-green Fire. One hundred and twenty parts of nitrate of potassium, 60 of washed flowers of sulphur, 45 of chlorate of potassium, 374 of anhydrous carbonate of sodium, 2 of pulverized charcoal, and 22.5 of stearine. 

To 800 grams of 15 per cent oleum is added, over a period of 10 minutes, 192 grams (1.0 mole) of finely powdered j3-naphthylamine sulfate which has been intimately mixed with 1 gram of anhydrous carbonate. The temperature should not be allowed to rise above 50°C. The reaction mixture is now tested for complete solubility in water and soda monosulfonation is usually complete in 15 minutes. The mixture is cooled to 40°, and 350 grams of 66 per cent oleum is added over a period of 15 minutes with continuous stirring. The sulfonation is continued for 1 day at 55°, then for an additional day at 85°. Under these conditions, the 2,5,7- and 2,1,5-naphthylaminedisulfonic acids, which are formed first, are converted to 2-naphthylamine-l,5,7-trisulfonic acid ... 

During this operation, stopcock a is closed and stopcock b is opened to the outside. Stopcock a is never opened to the outside unless the manometer indicates an excessive build-up of pressure in the system due to clogging in the traps. To prevent the mercury in the manometer from reacting with the gases in the system, a few milliliters of anhydrous carbon tetrachloride is placed on the surface of the mercury, as indicated in the diagram. A mercury bubbler may be attached to the open end of the manometer to serve as a safety blowout. 

Bromination of an olefin in the allylic position with N-bromoimides has become a valuable method for the preparation of unsaturated halo-genated compounds. In general, it consists in heating the unsaturated compound in anhydrous carbon tetrachloride under reflux with N-bromo-succimide (or N-bromophthalimide). As the bromination proceeds, suc-cinimide collects at the surface of the mixture. After the completion of... 

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