Cloudiness

The phase shift is measured by comparing the phase of the fluorescence with the phase of light scattered by a cloudy but non-fluorescent solution. 

It will be found that the first few drops of the lowest fraction are always cloudy, owing mainly to the fine film of water adsorbed on the glass surfaces within the column. 

When the correct solvent for recrystallisation is not known a procedure similar to that given on pp. 15-16 should be followed, but on the semi-micro scale not more than 10 mg. of the solid should be placed in the tapered-end test-tube (Fig. 29(B)) and about o i ml. of the solvent should be added from the calibrated dropping-pipette (Fig. 30(B)). If the compound dissolves readily in the cold, the solvent is unsuitable, but the solution should not be discarded. [In this case recourse should be had to the use of mixed solvents (p. 18). For example if the substance is very soluble in ethanol, water should be added from a calibrated pipette with shaking to determine whether crystallisation will now take place, indicated by a cloudiness or by the separation of solid.]... 

Aminoazobenzene is freely soluble in methylated spirit, although insoluble in water. For recrystallisation, therefore, dissolve the crude substance in boiling methylated spirit, remove from the water-bath, and then add water drop by drop until the solution becomes just cloudy owing to the separation of the solute replace the solution momentarily on the water-bath until the cloudiness disappears, and then at once remove the solution, and allow it to cool slowly. (Alternatively, the crude dry material can be reciystallised from carbon tetrachloride in the usual way.) Aminoazobenzene is thus obtained as yellowish-brown crystals, m.p. 126° yield, 5 g. 

The reaction with ethyl iodide is less rapid and it is necessary to warm the mixture gently until cloudy. On cooling, crystals of the ethiodide are formed, and after recrystallisation from methylated spirit have m.p. 84 . 

If no solid precipitate is obtained but the solution becomes cloudy, a low-melting or liquid phenol is indicated this will, of course, be revealed also by the characteristic phenolic odour. Transfer to a separating-funnel and extract with an equal volume of ether. Separate and dry with anhydrous sodium sulphate. Distil off the ether and identify the residue. 

The second indication is a faint smoke-like cloudiness in the zone of the tube which is being heated by the Bunsen this is readily visible as the interior of the tube is normally quite clear and bright. This is a later stage of development of the flash-back than the rise of pressure, already mentioned, and should be counteracted by moving the Bunsen immediately to the point of the combustion tube where heating was commenced. In either case the Bunsen should then be moved slowly forwards as before. A flash-back is attended by the deposition of carbon particles, carried back by the explosion wave, on the cold walls of the tube. Care should be taken that these are completely burnt off as the Bunsen is slowly moved forward again. 

At the end of 30 minutes treat the mixture in A as follows Dissolve 8 ml. of glacial acetic acid in 10 ml. of water, add 4 ml. of phenylhydra-zine and mix well in order to obtain a clear solution. Add this to the solution in A and mix thoroughly a slightly cloudy solution may be obtained, but this will clear on heating. Place the mixture in a boiling water-bath and note the formation of j ellow crystals of glucosazone after about 15 minutes. At the end of about i hour, cool, filter off the precipitate and identify as directed on p. 139. 

For methyl alcohol, two volumes of synthetic n-hexane, b.p. 68-6-69 0° (uncorr.), and one volume of the alcohol to be tested are mixed and the homogeneous mixture is cooled in ice until the appearance of a cloudiness. A thermometer is placed in the solution, which is allowed to warm gradually to the temperature at which the second phase disappears. The... 

Add 0 1 g. of the aldehyde in 5 ml. of 50 per cent, ethanol to 2 ml. of a 10 per cent, or saturated alcoholic solution of dimedone. If a precipitate does not form immediately, warm for 5 mintues if the solution is still clear at the end of this period, add hot water until the mixture is just cloudy and cool to about 6°. Collect the crystalline derivative and recrystallise it from methanol - water or ethanol - water. 

Use the procedure given under 2 for p-bromophenacyl esters. If the ester does not crystallise out on coofing, reheat the reaction mixture, and add small portions of hot water to the point of incipient cloudiness and allow to cool. 

Gyanoacetamide. Place 150 ml. of concentrated aqueous ammonia solution (sp. gr. 0-88) in a 500 ml. wide-mouthed conical flask and add 200 g. (188 ml.) of ethyl cyanoacetate. Shake the cloudy mixture some heat is evolved and it becomes clear in about 3 minutes. Stand the loosely stoppered flask in an ice-salt mixture for 1 hour, filter rapidly with suction, and ash the solid with two 25 ml. portions of ice-cold ethanol. Dry in the air the yield of pale yellow cyanoacetamide is 110 g. (1). Recrystallise from 190 ml. of 95 per cent, ethanol a colourless product, m.p. 119-120 , is deposited with practically no loss. 

To recover the free base, dissolve the hydrochloride in the minimum volume of boiling alcohol, add concentrated ammonia solution dropwise until a clear solution results and the blue colour has become fight brown. Add water carefully untU a cloudiness appears, warm on a water bath untU the cloudiness just disappears, and allow to cool. Yellow crystals of p-amino-azobenzene separate on coofing. 

In a 1 litre round-bottomed flask provided with an efficient double surface condenser, place 40 g. (39 ml.) of aniline, 50 g. (40 ml.) of carbon sulphide CAUTION inflammable) (1), and 50 g. (63-5 ml.) of absolute ethyl alcohol (2). Set up the apparatus in the fume cupboard or attach an absorption device to the top of the condenser (see Fig. 11, 8, 1) to absorb the hydrogen sulphide which is evolved. Heat upon an electrically-heated water bath or upon a steam bath for 8 hours or until the contents of the flask sohdify. When the reaction is complete, arrange the condenser for downward distillation (Fig. 11, 13, 3), and remove the excess of carbon disulphide and alcohol (CA UTION inflammable there must be no flame near the receiver). Shake the residue in the flask with excess of dilute hydrochloric acid (1 10) to remove any aniline present, filter at the pump, wash with water, and drain well. Dry in the steam oven. The yield of crude product, which is quite satisfactory for the preparation of phenyl iao-thiocyanute (Section IV.95), is 40-45 g. Recrystalhse the crude thiocarbanihde by dissolving it, under reflux, in boiling rectified spirit (filter through a hot water funnel if the solution is not clear), and add hot water until the solution just becomes cloudy and allow to cool. Pure sj/m.-diphenylthiourea separates in colourless needles, m.p, 154°,... 

If the m.p. is not quite satisfactory, dissolve the o-nitroplienol in hot alcohol (or methylated spirit) under reflux, add hot water drop by drop until a cloudiness just appears, and allow to cool spontaneously. Filter off the bright yellow crystals and diy between filter paper. 

The acetone test reagent consists of a 0 1 per cent, solution of 2 4-dinitro-phenylhydrazine and is prepared as follows Dissolve 0-25 g. of 2 4-dinitrophenyl-hydrazine in 60 ml. of water and 42 ml. of concentrated hydrochloric acid by warming on a water bath cool the clear yellow solution and dilute to 250 ml. with water. The acetone test is considered negative when 5 ml. of the reagent and 4-5 drops of the distillate give no cloudiness or precipitate of acetone 2 4-dinitro-phenylhydrazone within 30 seconds. After a negative test is obtained, it is stron y recommended that the mixture in the flask be refluxed for 5-10 minutes with complete condensation and then to collect a few drops of distillate for another test. If no acetone is now detected, the reduction is complete. 

The liquid ammonia may be slightly cloudy, due to the presence of a little water this has no appreciable effect upon the yield. 

B. Mix 1 drop or several small crystals (ca. 0 05 g.) of the compound with 1 ml. of 0-5 V hydroxylamine hydrochloride in 95 per cent, ethanol and add 0-2 ml ot aqueous sodium hydroxide. Heat the mixture to boiling and, after the solution has cooled slightly, add 2 ml. of N hydrochloric acid. If the solution is cloudy, add 2 ml. of 95 per cent, ethyl alcohol. Observe the colour produced when I drop of 6 per cent, ferric chloride solution is added. If the resulting colour does not persist, continue to add the reagent dropwise until the observed colour pervades the entire solution. Usually only 1 drop of the ferric chloride solution is necessary. Compare the colour with that produced in test. 4. A positive test will be a distinct burgundy or magenta colour as compared with the yellow colour observed when the original compound is tested with ferric chloride solution in the presence of acid. 

Alternatively, use the following procedure in which triethylamine replaces potassium acetate as the basic catalyst. Place 2 1 g. (2-0 ml.) of purified benzaldehyde, 2 0 ml. of anhydrous triethylamine and 5 0 ml. of A.R. acetic anhydride in a 200 ml. round-bottomed flask, equipped with a short reflux condenser and a calcium chloride drying tube. Boil the solution gently for 24 hours—heating may be interrupted. Incorporate a steam distillation apparatus in the flask and steam distil until the distillate is no longer cloudy (about 100 ml.) and then collect a further 50 ml. of the distillate di ard the steam distillate. Transfer the residue in the flask to a 400 ml. beaker, add water until the vplume is about 200 ml., then 0 2 g. of decolourising carbon, and boil for a few minutes. Filter the hot solution, and acidify the hot filtrate with 1 1 hydrochlorioiaoid... 

Although it is sometimes encouraged in white wines, particularly barrel-fermented Chardonnay, this fermentation tends to lower fmitiness and be considered undesirable in other white wines unless acidity is too high. This is also tme for pink and light red wines. If it occurs after bottling, a gassy, cloudy wine results. In such wines, it can be avoided by careful attention to clarification or filtration sufficient to remove the bacteria, by adding SO2 at appropriate intervals as an inhibitor, or by pasteurization. 

Incipient hazes may not be removed at all by simple filtration. An array of fining procedures have been developed to achieve stable clarity in such cases. Fining agents ate substances that ate or become insoluble in wines, and, as they precipitate, adsorb or coptecipitation incipient sources of cloudiness. Ptopedy used, the fining agents themselves ate not retained in the wines and thein effect is subtractive rather than additive. 

The type of floe requited depends on the separation process which foUows, eg, rotary vacuum filtration requites evenly sized, smaU, strong floes that capture ultrafines to prevent cloth blinding and cloudy filtrates. The floes should not be subject to sedimentation in the vat or breakage by the agitator. 

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