Effect Magnesium

A further important reaction is the replacementot the Ca + ion in calcium carbonate by a magnesium ion. The latter is smaller, hence space or porosity is created in the mineral lattice by the replacement. The resulting mineral is dolomite and the increase in effective porosity can be as high as 13%. The process can be expressed as... 

Metallic sodium. This metal is employed for the drying of ethers and of saturated and aromatic hydrocarbons. The bulk of the water should first be removed from the liquid or solution by a preliminary drying with anhydrous calcium chloride or magnesium sulphate. Sodium is most effective in the form of fine wire, which is forced directly into the liquid by means of a sodium press (see under Ether, Section II,47,i) a large surface is thus presented to the liquid. It cannot be used for any compound with which it reacts or which is affected by alkalis or is easily subject to reduction (due to the hydrogen evolved during the dehydration), viz., alcohols, acids, esters, organic halides, ketones, aldehydes, and some amines. 

Solid magnesium must be absent to avoid the formation of diallyl via allyl magnesium bromide the insertion of a short plug of glass wool effectively removes any finely divided magnesium. 

To obtain a maximum yield of the acid it is necessary to hydrolyse the by-product, iaoamyl iaovalerate this is most economically effected with methyl alcoholic sodium hydroxide. Place a mixture of 20 g. of sodium hydroxide pellets, 25 ml. of water and 225 ml. of methyl alcohol in a 500 ml. round-bottomed flask fitted with a reflux (double surface) condenser, warm until the sodium hydroxide dissolves, add the ester layer and reflux the mixture for a period of 15 minutes. Rearrange the flask for distillation (Fig. II, 13, 3) and distil off the methyl alcohol until the residue becomes pasty. Then add about 200 ml. of water and continue the distfllation until the temperature reaches 98-100°. Pour the residue in the flask, consisting of an aqueous solution of sodium iaovalerate, into a 600 ml. beaker and add sufficient water to dissolve any solid which separates. Add slowly, with stirring, a solution of 15 ml. of concentrated sulphuric acid in 50 ml. of water, and extract the hberated acid with 25 ml. of carbon tetrachloride. Combine this extract with extract (A), dry with a httle anhydrous magnesium or calcium sulphate, and distil off the carbon tetrachloride (Fig. II, 13, 4 150 ml. distiUing or Claisen flask), and then distil the residue. Collect the wovaleric acid 172-176°. The yield is 56 g. 

Green coloration, present in many vegetable oils, poses a particular problem in oil extracted from immature or damaged soybeans. Chlorophyll is the compound responsible for this defect. StmcturaHy, chlorophyll is composed of a porphyrin ring system, in which magnesium is the central metal atom, and a phytol side chain which imparts a hydrophobic character to the stmcture. Conventional bleaching clays are not as effective for removal of chlorophylls as for red pigments, and specialized acid-activated adsorbents or carbon are required. 

Magnesium oxide is an effective nonsystemic antacid, ie, it is converted to the hydroxide. It does not neutralize gastric acid excessively nor does it hberate carbon dioxide. The light form is preferable to the heavy for adininistration in Hquids because it is suspended more readily. One gram of magnesium oxide neutralizes 87 mL of 0.1 NUCl in 10 min, and 305 mL in 2 h. 

The solvent, magnesium, and RX can have a deleterious effect on the preparation of the Grignard reagent. Some of the problems are a homocoupled product, formation of RMg02X, and noniaitiated reaction of RX with Mg. Therefore, proper preparation and handling of each component must be carried out. 

To minimize the effects of this difficulty, an initiator is frequentiy employed. Among the numerous suggestions in the Hterature, the most satisfactory industrial procedure is to retain a portion of the Grignard from the preceding batch and to add this portion to the initial ether charge. The purpose of this procedure is to eliminate residual water and to clean the magnesium surface. Once this initiator has been added, the hahde is added at a rate deterrnined by the temperature and the pressure in the reaction vessel. 

Sa.lts Salting out metal chlorides from aqueous solutions by the common ion effect upon addition of HCl is utilized in many practical apphcations. Typical data for ferrous chloride [13478-10-9] FeCl2, potassium chloride [7447-40-7] KCl, and NaCl are shown in Table 9. The properties of the FeCl2-HCL-H2 0 system are important to the steel-pickling industry (see Metal SURFACE TREATMENTS Steel). Other metal chlorides that are salted out by the addition of hydrogen chloride to aqueous solutions include those of magnesium, strontium, and barium. 

Acylation. Acylation is the most rehable means of introducing a 3-substituent on the indole ring. Because 3-acyl substituents can be easily reduced to 3-aLkyl groups, a two-step acylation—reduction sequence is often an attractive alternative to direct 3-aLkylation. Several kinds of conditions have been employed for acylation. Very reactive acyl haUdes, such as oxalyl chloride, can effect substitution directiy without any catalyst. Normal acid chlorides are usually allowed to react with the magnesium (15) or 2inc (16) salts. The Vilsmeier-Haack conditions involving an amide and phosphoms oxychloride, in which a chloroiminium ion is the active electrophile, frequentiy give excellent yields of 3-acylindoles. 

Under equiUbrium conditions, magnesium can contain as much as 12.7% aluminum in soHd solution at the eutectic temperature. However, the slow diffusion of aluminum to the grain boundary leads to a coring effect in primary crystals and a hard-phase magnesium—aluminum compound(17 12)... 

In neutral and alkaline environments, the magnesium hydroxide product can form a surface film which offers considerable protection to the pure metal or its common alloys. Electron diffraction studies of the film formed ia humid air iadicate that it is amorphous, with the oxidation rate reported to be less than 0.01 /rni/yr. If the humidity level is sufficiently high, so that condensation occurs on the surface of the sample, the amorphous film is found to contain at least some crystalline magnesium hydroxide (bmcite). The crystalline magnesium hydroxide is also protective ia deionized water at room temperature. The aeration of the water has Httie or no measurable effect on the corrosion resistance. However, as the water temperature is iacreased to 100°C, the protective capacity of the film begias to erode, particularly ia the presence of certain cathodic contaminants ia either the metal or the water (121,122). 

Fig. 14. Effects of iron (—), nickel (-), and copper (...) contaminant levels on the saltwater corrosion performance of magnesium AZ91 alloy containing...

J. E. HiUis, The Effects of Heavy Metal Contamination on Magnesium Corrosion Peformance, paper 830523, Society of Automotive Engineers, Detroit,... 

D. Hawke and K. Gaw, "Effects of Chemical Surface Treatments on the Performance of an Automotive Paint System on Die Cast Magnesium," Paper 920074, Society of Automotive Engineers International Congress and Exposition, Detroit, Mich., 1992. 

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