Causticization

In early designs, the reaction heat typically was removed by cooling water. Crude dichloroethane was withdrawn from the reactor as a liquid, acid-washed to remove ferric chloride, then neutralized with dilute caustic, and purified by distillation. The material used for separation of the ferric chloride can be recycled up to a point, but a purge must be done. This creates waste streams contaminated with chlorinated hydrocarbons which must be treated prior to disposal. 

Most of the ethylene dichloride produced is utilized for the manufacture of vinyl chloride, which may be obtained from it by pyrolysis or the action of caustic soda. Large quantities are also used in anti-knock additives for gasoline. As a solvent It has been displaced by trichloroethylene and tetrachloroelhyJene. U.S. production 1978 4-75 megatonnes. 

Usually prepared on the large scale by caustic soda fusion of sodium naphthalene-1-sulphonate, but can also be obtained by high-temperature alkaline digestion of... 

Obtained by K.OH fusion of many resins. Prepared by fusion of m-benzenedisulphonic acid with caustic soda, also obtained to some extent in the NaOH fusion of o-and p-ben-zenedisulphonic acids. 

C7H6O2 Oily liquid of aromatic odour b.p. 196°C. (t is prepared by the action of chloroform and caustic potash on phenol (the Reimer-Tiemann reaction) or by the oxidation of the glucoside salicin. It is easily reduced to salicyl alcohol or oxidized to salicylic acid. 

The most important reaction of the sulphonic acids is their conversion into phenols by fusion with caustic alkalis. When they are fused with potassium cyanide, nitriles are obtained, e.g. benzonitriie from ben-zenesulphonic acid. 

The presence of these acids in crude oils and petroleum cuts causes problems for the refiner because they form stable emulsions with caustic solutions during desalting or in lubricating oil production very corrosive at high temperatures (350-400°C), they attack ordinary carbon steel, which necessitates the use of alloy piping materials. 

A first operation on the crude, desalting (washing by water and caustic), extracts salts (NaCl, KCl and the MgCb that is cdn eft4rdJt6 NaCl by the caustic), reduces acid corrosion as well as it minimizes fouling and deposits. /... 

The sweetening operation consists of converting the mercaptans to disulfides by air oxidation in the presence of a catalyst in a caustic environment. 

Aluminium is obtained on a large scale by the electrolysis of the oxide, dissolved in fused cryolite The oxide, occurring naturally as bauxite, AI2O3.2H2O, usually contains silica and iron(III) oxide as impurities. These must be removed first, since aluminium, once prepared, cannot be freed of other metals (which will be deposited on electrolysis) by refining it. The crude oxide is dissolved under pressure in caustic soda solution the aluminium oxide and silica dissolve and the ironflll) oxide is left ... 

A white gelatinous precipitate of aluminium hydroxide is obtained when an alkali is added to an aqueous solution of an aluminium salt. Addition of an excess of caustic alkali causes the precipitate to redissolve, the whole process being reversed by the addition of a strong acid the actual substance present at any time depending on... 

Silicon and germanium readily react with even very dilute solutions of caustic alkali. Silicon is so sensitive to attack that it will dissolve when boiled with water which has been in contact with glass ... 

The gas is passed through caustic soda solution to remove any sulphur dioxide or carbon dioxide produced in side reactions. Carbon monoxide is also obtained when an ethanedioate (oxalate) is heated with concentrated sulphuric acid ... 

Oxygen difluoride, OFj, is obtained when gaseous fluorine is passed through very dilute (27 ) caustic soda solution ... 

In ammoniacal solution (in which the ion [AgfNHjlj]" is formed) it is readily reduced to silver (see above) by many organic compounds. The use of silver nitrate for marking clothes depends on its reduction by the material to black silver. The reduction also occurs even when the neutral solution comes in contact with the skin, and a black stain is left. Thus solid silver nitrate rubbed on the skin leaves a black deposit and so is used in surgery as a mild caustic—hence the old name for silver nitrate of lunar caustic. 

Caustics The above formulae can only be valid as long as Eq. (9) describes a unique map in position space. Indeed, the underlying Hamilton-Jacobi theory is only valid for the time interval [0,T] if at all instances t [0, T] the map (QOi4o) —> Q t, qo,qo) is one-to-one, [6, 19, 1], i.e., as long as trajectories with different initial data do not cross each other in position space (cf. Fig. 1). Consequently, the detection of any caustics in a numerical simulation is only possible if we propagate a trajectory bundle with different initial values. Thus, in pure QCMD, Eq. (11), caustics cannot be detected. 

Fig. 1. Illustration of a caustic. Different trajectories sample the probability distribution. If they cross each other in position space, the transport or probability density is not longer unique and the approximation might break down.

Approximation Property Excluding caustics we can exploit the results of semiclassical approximation theory [19]. This leads to the following statement ... 

Theorem 2 (Thm. 4.2. in [6]). Let 4> initialli have width <5(0) < 5 and let e be small enough. Moreover, assume that caustics do not appear in time interval [0,rj. Then, the semiclassical wavefunctions and-ipQc approximate the TDSCF wavefunction ip up to an error of order 5 -F e, i.e.,... 

Referring to Thm. 1 we can conclude that—excluding caustics—QCMD (and QCMD bundles) approximates full QD up to an error of order 0(6- -e). These... 

Fig. 2. The BO model is the adiabatic limit of full QD if energy level crossings do not appear. QCMD is connected to QD by the semiclassical approach if no caustics are present. Its adiabatic limit is again the BO solution, this time if the Hamiltonian H is smoothly diagonalizable. Thus, QCMD may be justified indirectly by the adiabatic limit excluding energy level crossings and other discontinuities of the spectral decomposition.

Altogether, the three different models discussed so far are interconnected as sketched in Fig. 2. Now, we can by-pass the problems connected to caustics For e being small enough QCMD is justified as an approximation of QD if we exclude energy level crossings and discontinuities of the spectral decomposition. 

Hydrolysis of Potassium Ethyl Sulphate. Dissolve about i g. of the crystals in about 4 ml. of cold distilled water, and divide the solution into two portions, a) To one portion, add barium chloride solution. If pure potassium ethyl sulphate were used, no precipitate should now form, as barium ethyl sulphate is soluble in water. Actually however, almost all samples of potassium ethyl sulphate contain traces of potassium hydrogen sulphate formed by slight hydrolysis of the ethyl compound during the evaporation of its solution, and barium chloride almost invariably gives a faint precipitate of barium sulphate. b) To the second portion, add 2-3 drops of concentrated hydrochloric acid, and boil the mixture gently for about one minute. Cool, add distilled water if necessary until the solution has its former volume, and then add barium chloride as before. A markedly heavier precipitate of barium sulphate separates. The hydrolysis of the potassium ethyl sulphate is hastened considerably by the presence of the free acid Caustic alkalis have a similar, but not quite so rapid an effect. 

CHjCHoOH + 4CI2 CCI3CHO 5HCI When chloral is treated with caustic alkali, fission of the C-C linkage occurs, giving chloroform and a formate ... 

Hydrolysis of Acetanilide. Anilides in general, such as acetanilide and benzanilide (p. 245), may be hydrolysed by caustic alkalis or by acids. Alkaline hydrolysis, however, is usually very slow, and therefore... 

Lithium aluminium hydride if carelessly manipulated may be dangerous for two distinct reasons. The material is caustic, and should not be allowed to touch the skin it is particularly important that the finely divided material should be kept away from the lips, nostrils and eyes, and consequently pulverisation in a mortar must be carried out with the mortar in a fume-cupboard, and with the window drawn down as far as possible in front of the operator. This danger from handling has however been greatly reduced, for the hydride is now sold in stated amounts as a coarse powder enclosed in a polythene bag in a metal container this powder dissolves readily in ether, and preliminary pulverisation is unnecessary. 

When benzaldehyde is treated with a concentrated caustic alkali solution, polymerisation occurs with the formation of benzyl benzoate, which then... 

Ketonic Hydrolysis. Hot dilute caustic alkalis or hydrochloric acid first hydrolyse off the ethyl group, and then remove carbon dioxide, a mono- or di-substituted acetone being thus obtained ... 

Physical properties. All solid except m -cresol, CH3CJH4OH, which is a liquid. All colourless when pure, but frequently slightly coloured due to atmospheric oxidation. All have in varying degrees a characteristic odour of carbolic acid. Phenol, the cresols and resorcinol have a caustic action on the skin. 

Tyrosine and cystine are colourless solids almost insoluble in water gfid in ethanol (tyrosine dissolves in hot water). They are readily soluble in dilute caustic alkali solution, in ammonia and mineral acids, but not in acetic acid. They are also classed as neutral ampholytes. ... 

Physical Properties, Colourless solid when pure, usually pale brown. Sparingly soluble in cold water, soluble in hot water soluble also in cold mineral acids and caustic alkalis. Dissolves readily in cold alcohol, and solution possesses a faint blue fluorescence. 

The molecular weight of many carboxylic acids which arc freely soluble in cold water (i.e., chiefly the aliphatic acids) can readily be obtained by titrating a known weight of the acids in aqueous solution with standard sodium or potassium hydroxide solution, using phenolphthalein as an indicator. To avoid the use of unduly large quantities of the acid, it is advisable to use Mj2 caustic alkali solution, and in order to obtain a sharp end>point, this alkali solution... 

The residue in the flask will contain the sodium (or potassium) salt of the acid together with excess of alkali. Just acidify with dilute sulphuric acid and observe whether a crystalline acid separates if it does, filter, recrystallise and identify (Section 111,85). If no crystaUine solid is obtained, the solution may be just neutralised to phenolphthalein and the solution of the alkali salt used for the preparation of a crystaUine derivative. This wiU confirm, if necessary, the results of hydrolysis by method 1. If the time factor is important, either method 1 or the product of the caustic alkali hydrolysis may be used for the identification of the acid. 

P Keto esters (t.g., ethyl ocetoacetate) are soluble in solutions of caustic alkalis but not in sodium carbonate solution. They give colours with freshly prepared ferric chloride solution a little alcohol should be added to bring the ester into solution. Sodium ethoxide solution reacts to yield sodio compounds, which usually crystallise out in the cold. Phenylhydrazine yields pyrazolones. They are hydrolysed by boiling sulphuric acid to the Corresponding ketones, which can be identified as usual (Section 111,74). 

It is frequently advisable in the routine examination of an ester, and before any derivatives are considered, to determine the saponification equivalent of the ester. In order to ensure that complete hydrolysis takes place in a comparatively short time, the quantitative saponi fication is conducted with a standardised alcoholic solution of caustic alkali—preferably potassium hydroxide since the potassium salts of organic acids are usuaUy more soluble than the sodium salts. A knowledge of the b.p. and the saponification equivalent of the unknown ester would provide the basis for a fairly accurate approximation of the size of the ester molecule. It must, however, be borne in mind that certain structures may effect the values of the equivalent thus aliphatic halo genated esters may consume alkali because of hydrolysis of part of the halogen during the determination, nitro esters may be reduced by the alkaline hydrolysis medium, etc. 

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