Chloride calcium

Calcium chloride is no longer in the top 50, but it is very high in the second 50 chemicals (see Chapter 13). Because it is an important by-product of the Solvay process, we will mention it here. Besides being a Solvay byproduct it is also obtained from natural brines (especially in Michigan). A typical brine contains 14% NaCl, 9% CaCl2, and 3% MgC. Evaporation 

CaCl2 produced in large quantities as a byproduct in chemical processes 

Applications of CaCl2 in the USA in 1994 38% for salting roads 18% as a dust-binding agent 20% for industrial purposes 12% in concrete manufacture 4% in crude oil extraction 8% for other uses 

Economic Importance. Calcium chloride is produced in large quantities as a byproduct in different chemical processes e.g. in the Solvay process or in the production of propene oxide in the chlorohydrin process, of which only a small part is processed to pure calcium chloride. In 1993 in the USA ca. 0.48 10 t (as anhydrous calcium chloride/ was produced mainly from natural sources (mainly subterranean brines and, to a lesser extent, dried out salt lakes in California). 

Manufacture Synthetic hydrated calcium chloride is produced from the calcium chloride containing-residual brines of the Solvay process by evaporation initially in vacuum, then at atmospheric pressure. Calcium chloride is also produced from waste acid by reaction with limestone. Anhydrous calcium chloride is obtained e.g. by evaporation in fluidized bed dryers or spray towers. 

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For concrete work in cold weather a specially rapid-hardening cement may be made by addition of calcium chloride to the cement. 

Dehumidification may be effected by cooling. Where small quantities of dry air are required dehumidification can be carried out using chemical absorbents, e.g. calcium chloride, phosphorus pentoxide, sulphuric acid, etc. 

The ammonia gas is used again and the only by-product, calcium chloride, is used to melt snow, prevent freezing of coal in transit and as an antidust treatment since it is hygroscopic and forms a solution of low freezing point. 

After drying over quicklime, calcium oxide CaO, the ammonia is collected by upward delivery. (N.B. Both of the common drying agents, calcium chloride and concentrated sulphuric acid, combine with the gas.)... 

If a compound has been recrystallised from petrol, benzene, etc.y some freshly cut shavings of clean paraffin wax should be added to the calcium chloride in (A) or to the sodium hydroxide in D, The surface of the wax absorbs organic solvent vapours (particularly the hydrocarbons) and the last trace of such solvents is thus readily removed from the recrystallised material. 

Cannot be used for alcohols, phenols or amines, with all of which it combines. Not advisable for acidic liquids, as ordinary calcium chloride always contains some calcium hydroxide owing to partial hydrolysis during preparation. Usually used for alcohols (see p. 88). Cannot be used for acidic compounds, nor for esters, which it would hydrolyse. 

Fig 23(A) shows an assembly for boiling a liquid under reflux whilst adding another liquid at a rate which can be clearly seen cf. preparation of acetophenone, p. 253). The outlet A allows expansion of the vapour content, and can be fitted with a calcium chloride or soda-lime tube. The outlet A can also be used for collecting a gas evolved during the reaction cf, preparation of acetylene,... 

Drying of crystals. Whenever possible crystals should be dried in a smdl vacuum desiccator containing a suitable desiccant. The latter depends upon the nature of the solvent used c/. p. 19). However for most purposes anhydrous calcium chloride is satisfactory. If a hydrocarbon has been used in the recrystallisation, a few thin fresh shavings of paraffin wax are efficacious. 

Pure Ether. Pure ether (entirely free in particular from water) is frequently required in the laboratory, and especially for the preparation and use of Grignard reagents. It is best prepared in quantity for classes by adding an ample quantity of granular calcium chloride to a Winchester bottle of technical ether, and allowing the mixture to stand for at least 24 hours, preferably with occasional shaking. The greater part of the water and... 

Required Ethanol, 50 ml. sulphuric acid, 10 ml. acetic acid, 50 ml. calcium chloride, 25 g. 

Run off the lower layer of bromide, dry it with calcium chloride (as in the above preparation of ethyl bromide) and finally distil the filtered bromide from a small flask, preferably through a short column. Collect the n-butyl bromide as a colourless liquid of b.p. 99-102°. Yield, 30 g. 

Lead formate separates from aqueous solution without water of crystallisation. It can therefore be used for the preparation of anhydrous formic acid. For this purpose, the powdered lead formate is placed in the inner tube of an ordinary jacketed cond ser, and there held loosely in position by plugs of glass-wool. The condenser is then clamped in an oblique position and the lower end fitted into a receiver closed with a calcium chloride tube. A current of dry hydrogen sulphide is passed down the inner tube of the condenser, whilst steam is passed through the jacket. The formic acid which is liberated... 

Both forms sublime very readily, even at room temperature a small sample on exposure to the air will completely volatilise in a short time, particularly on a warm day or if the sample is exposed to a gentle current of air. Hence the above method for rapid drying. A sample confined in an atmospheric desiccator over calcium chloride rapidly disappears as the vapour is adsorbed by the calcium chloride. A sample of the hexahydrate similarly confined over sodium hydroxide undergoes steady dehydration with initial liquefaction, for the m.p. of the hydrated-anhydrous mixture is below room temperature as the dehydration proceeds to completion, complete resolidification occurs. 

The acetone employed should be dried over calcium chloride for 2-3 days before use. The benzene should be similarly dried... 

Fit a 500 ml. round-bottomed flask with a dropping-funnel, and with an efficient reflux water-condenser having a calcium chloride guard-tube at the top. 

Aluminium isopropoxide can be obtained as a fine powder from technical sources. When the bottle has once been opened however, the stopper should be firmly replaced and covered with wax more conveniently, the stoppered bottle can be kept in an atmospheric desiccator over calcium chloride or sodium hydroxide, preferably in the dark. 

The benzene used in this preparation should be reasonably free from toluene therefore use a sample of benzene supplied by dealers as crystalUsable benzene, i.e.y one which crystallises readily when cooled in ice-water. It should preferably be dried over calcium chloride and, immediately before use, filtered through a fluted filter-paper. The pyridine should also preferably be dried over solid potassium hydroxide and redistilled. 

Place 0 5 ml. of the pyridine in a 200 ml. round- or flat-bottomed flask and add 34 ml. (30 g.) of benzene. Fit the flask with a reflux water-condenser, and then place it in a cold water-bath. If the experiment is conducted in a fume-cupboard, the top of the condenser can be closed with a calcium chloride tube bent downwards (as in Fig. 61, p. 105 or in Fig. 23(A), p. 45, where the outlet-tube A will carry the calcium chloride tube) and the hydrogen bromide subsequently allowed to escape if, however, the experiment is performed in the open laboratory, fit to the top of the condenser (or to the outlet-tube A) a glass delivery-tube which leads through a piece of rubber tubing to an inverted glass funnel, the rim of which dips just below the surface of some water... 

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