Diluted Hydrochloric Acid

Germanium, however, does not react with either dilute sulphuric or dilute hydrochloric acid, unlike tin, the next element in the group. 

Sulphur can be reduced directly to hydrogen sulphide by passing hydrogen through molten sulphur the reversible reaction H2 -I-S H2S occurs. In the laboratory the gas is most conveniently prepared by the action of an acid on a metal sulphide, iron(II) and dilute hydrochloric acid commonly being used ... 

This has been made in trace quantities by the action of dilute hydrochloric acid on magnesium plated with polonium. As expected, it is extremely unstable and decomposes even at 100 K,... 

Barium sulphite is soluble in dilute hydrochloric acid unlike barium sulphate which is insoluble. Hence this reaction, and the evolution of sulphur dioxide on addition of an acid, distinguishes a sulphite from a sulphate. 

The anhydrous chloride is prepared by standard methods. It is readily soluble in water to give a blue-green solution from which the blue hydrated salt CuClj. 2H2O can be crystallised here, two water molecules replace two of the planar chlorine ligands in the structure given above. Addition of dilute hydrochloric acid to copper(II) hydroxide or carbonate also gives a blue-green solution of the chloride CuClj but addition of concentrated hydrochloric acid (or any source of chloride ion) produces a yellow solution due to formation of chloro-copper(ll) complexes (see below). 

When titanium dissolves in dilute hydrochloric acid, a violet solution containing titanium(III) ions is formed. This solution rapidly decolorises acidified aqueous potassium permanganate at room temperature. Titanium(IV) chloride is a colourless covalent liquid completely hydrolysed by water. Titanium(III) chloride forms hydrated titanium(III) ions in water and disproportionates when heated in a vacuum. 

Disconnect the column, and remove the flask from the oil-bath. Add 25 ml. of dilute hydrochloric acid to the flask, shake the contents vigorously, and chill in ice-water, when crystals of benzhydrol will separate. (Occasionally the hydrol will separate initially as an oil, which ciystallises on vigorous stirring.)... 

In preparing an aqueous sol ution of a diazonium salt, such as benzene-diazonium chloride, it is usual to dissolve the amine in a slight excess (about 2 2 molecular equivalents) of dilute hydrochloric acid (or alternatively to dissolve the crystalline amine hydrochloride in i 2 equivalents of the acid) and then add an aqueous solution of a metallic nitrite. Nitrous acid is thus generated in situ, and reacts with the amine salt to give the diazonium compound. For a successful preparation of an aqueous solution of the diazonium salt, however, two conditions must always be observed ... 

To prepare the hydrochloride, add about i g. of aminoazobenzene to 200 ml. of dilute hydrochloric acid and boil until nearly all the solid material has dissolved. Filter hot and allow to cool slowly. Aminoazobenzene hydrochloride separates as beautiful steel-blue crystals filter and dry. If a small quantity of the powdered hydrochloride is moistened with water and a few drops of ammonia added, the blue hydrochloride is converted back to the yellowish-brown base. 

Prepare a mixture of 30 ml, of aniline, 8 g. of o-chloro-benzoic acid, 8 g. of anhydrous potassium carbonate and 0 4 g. of copper oxide in a 500 ml. round-bottomed flask fitted with an air-condenser, and then boil the mixture under reflux for 1 5 hours the mixture tends to foam during the earlier part of the heating owing to the evolution of carbon dioxide, and hence the large flask is used. When the heating has been completed, fit the flask with a steam-distillation head, and stcam-distil the crude product until all the excess of aniline has been removed. The residual solution now contains the potassium. V-phenylanthrani-late add ca. 2 g. of animal charcoal to this solution, boil for about 5 minutes, and filter hot. Add dilute hydrochloric acid (1 1 by volume) to the filtrate until no further precipitation occurs, and then cool in ice-water with stirring. Filter otT the. V-phcnylanthranilic acid at the pump, wash with water, drain and dry. Yield, 9-9 5 g. I he acid may be recrystallised from aqueous ethanol, or methylated spirit, with addition of charcoal if necessary, and is obtained as colourless crystals, m.p. 185-186°. 

To prepare a sample of the hydrochloride, add 0-5 ml. of the base to 10 ml, of dilute hydrochloric acid in an evaporating basin and evaporate to dryness, preferably in a vacuum desiccator. Recrystallise the dry residue from petroleum (b.p. 60-80°). The hydrochloride separates as white crystals, m.p. 90°. 

Whilst the solution is still hot, add dilute hydrochloric acid until the stirred solution is just acid to litmus, and then distil off as much ethanol as possible, using the water-bath. Now add more dilute hydrochloric acid to the residual hot solution until it is just acid to methyl-orange. The 5,5-dimethyl-cyclohexan-1,3-dione separates as an oil which solidifies on cooling. Filter the product at the pump, wash it with ice-cold water, and dry it in a desiccator. Yield of the pale cream-coloured crystals, 12 g. m.p. 136-145 (preliminary softening). 

Many aldehydes and ketones can be reduced directly by Clenimemen s method, in which the aldehyde or ketone is boiled with dilute hydrochloric acid and amalgamated zinc. />-Methylacetophenone (or methyl />-tolyl ketone) is reduced under these conditions to />-ethyltoluene. An excess of the reducing agent is employed in order to pre ent the formation of unsaturated hydrocarbons. 

During this period hydrogen chloride continues to be liberally evolved, and the product darkens considerably in colour. Now pour the product cautiously into 500 ml. of dilute hydrochloric acid and 100 g. of chipped ice in a separating-funnel, and shake the mixture thoroughly this operation removes the dark colour, and the toluene solution becomes yellow. Run off the lower acid layer, and extract the toluene three times with water. Finally dry the toluene solution over calcium chloride. 

The mixed bases are dissolved in dilute hydrochloric acid and sodium nitrite solution added. The aniline is thus diazotised and, if the mixture is subsequently boiled, converted into phenol. The solution is then made alkaline and steam-distilled, the quinoline passing over, while the phenol remains behind in the alkaline solution. 

Cool the reaction-solution, and pour it into a 250 ml. beaker, washing out the flask with ca. 50 ml. of water into the beaker. Chill the solution in ice-water and add dilute hydrochloric acid with stirring until the solution is just acid when spotted externally on to Congo Red paper. The arsinic acid rapidly separates. Filter at the pump, wash well with water and drain. (Yield of crude dry product, 7-5-8 o g. m.p. 200-203°.)... 

Sulphur. Moisten the centre of a filter-paper with lead acetate solution. Then add about 10 ml. of dilute hydrochloric acid to the residue in the evaporating-basin, and at once cover the latter with the paper. If zinc sulphide is present in the residue, the hydrogen sulphide evolved will give a definite daA brown coloration with the lead acetate paper. The presence of hydrogen sulphide can often be confirmed by its odour. 

Example. Dissolve 0 3 g. of benzoic acid in a minimum of hot water (about 70 ml.) and add 5% aqueous sodium hydro.xide until the solution is just alkaline to methyl-orange, then add i drop of dilute hydrochloric acid. Pour this solution of the sodium salt into a solution of 0 5 g, of benzylthiouronium chloride in 5 ml. of water, and cool the stirred mixture in ice-water. Filter off the benzylthiouronium salt which has separated, and recrystallise from ethanol con taining 10% of water cream-coloured cr> stals, m.p. i66 . (M.ps., pp. 543 545.)... 

Transfer 25 ml. of this dilute solution by means of a pipette to a conical flask, and add similarly 50 ml. of Ml 10 iodine solution. Now-add 10% sodium hydroxide solution until the liquid becomes pale yeilow in colour, and allow the solution to stand, with occasional shaking, at room temperature for at least 10 minutes. Then acidify with dilute hydrochloric acid (free from chlorine) in order to liberate the remaining iodine. Titrate the latter w ith Mho sodium thiosulphate solution, using starch as an indicator in the usual way. 

This tube is connected %vith rubber tubing of about 6 mm. bore to the carbon dioxide Kipp, via a wash-bottle containing sodium carbonate solution (to remove any dilute hydrochloric acid spray). It is very important, when the apparatus is in use, that there should be no constriction or bend in the rubber tube between the tap C and the wash-bottle. If these precautions are taken, a slow, e en, and easily controlled flow of gas can be obtained. 

Dilute hydrochloric or sulphuric acid finds application in the extraction of basic substances from mixtures or in the removal of basic impurities. The dilute acid converts the base e.g., ammonia, amines, etc.) into a water-soluble salt e.g., ammonium chloride, amine hydrochloride). Thus traces of aniline may be separated from impure acetanilide by shaking with dilute hydrochloric acid the aniline is converted into the soluble salt (aniline hydrochloride) whilst the acetanilide remains unaffected. 

Absolute diethyl ether. The chief impurities in commercial ether (sp. gr. 0- 720) are water, ethyl alcohol, and, in samples which have been exposed to the air and light for some time, ethyl peroxide. The presence of peroxides may be detected either by the liberation of iodine (brown colouration or blue colouration with starch solution) when a small sample is shaken with an equal volume of 2 per cent, potassium iodide solution and a few drops of dilute hydrochloric acid, or by carrying out the perchromio acid test of inorganic analysis with potassium dichromate solution acidified with dilute sulphuric acid. The peroxides may be removed by shaking with a concentrated solution of a ferrous salt, say, 6-10 g. of ferrous salt (s 10-20 ml. of the prepared concentrated solution) to 1 litre of ether. The concentrated solution of ferrous salt is prepared either from 60 g. of crystallised ferrous sulphate, 6 ml. of concentrated sulphuric acid and 110 ml. of water or from 100 g. of crystallised ferrous chloride, 42 ml. of concentrated hydiochloric acid and 85 ml. of water. Peroxides may also be removed by shaking with an aqueous solution of sodium sulphite (for the removal with stannous chloride, see Section VI,12). 

Carbon dioxide. This gas is conveniently generated from marble and dilute hydrochloric acid (1 1) in a Kipp s apparatus it should be passed through a wash bottle containing water or sodium bicarbonate solution to remove acid spray and, if required dry, through two further wash bottles charged with concentrated sulphuric acid. 

Use the apparatus detailed in Section 111,20. Dissolve 100 g. (123 ml.) of methyl n-butyl ketone (2-hexanone) (Section 111,152) in 750 ml. of ether and add 150 ml. of water. Introduce 69 g. of clean sodium in the form of wire (or small pieces) as rapidly as possible the reaction must be kept under control and, if necessary, the flask must be cooled in ice or in running water. When all the sodium has reacted, separate the ethereal layer, wash it with 25 ml. of dilute hydrochloric acid (1 1), then with water, dry with anhydrous potassium carbonate or with anhydrous calcium sulphate, and distil through a fractionating column. Collect the fraction of b.p. 136-138°. The yield of methyl n-butyl carbinol (2-hexanol) is 97 g. 

Treat a small quantity of the bisulphite addition compound with 5 ml. of 10 per cent, sodium carbonate solution, and note the odour. Repeat the experiment with 5 ml. of dilute hydrochloric acid. 

Anilides. Dilute the acid chloride with 5 ml. of pure ether (or benzene), and add a solution of 2 g. of pure aniline in 15-20 ml. of the same solvent until the odour of the acid chloride has disappeared excess of aniline is not harmful. Shake with excess of dilute hydrochloric acid to remove aniline and its salts, wash the ethereal (or benzene) layer with 3-5 ml. of water, and evaporate the solvent [CAUTION ] Recrystallise the anilide from water, dilute alcohol or benzene - light petroleum (b.p. 60-80°). 

Dissolve or suspend 0 - 5 g. of the acid in 5 ml. of water in a small conical flask, add a drop or two of phenolphthalein indicator, and then 4-5 per cent, sodium hydroxide solution until the acid is just neutrahsed. Add a few drops of very dilute hydrochloric acid so that the final solution is faintly acid (litmus).f Introduce 0-5 g. of p-bromophenacyl bromide (m.p. 109°) dissolved in 5 ml. of rectified (or methylated) spirit, and heat the mixture under reflux for 1 hour if the mixture is not homogeneous at the boiling point or a solid separates out, add just sufficient alcohol to produce homogeneity. [Di- and tri-basic acids require proportionately larger amounts of the reagent and longer refluxing periods.] Allow the solution to cool, filter the separated crystals at the pump, wash with a little alcohol and then with water. Recrystallise from dilute alcohol dissolve the solid in hot alcohol, add hot water until a turbidity just results, clear the latter with a few drops of alcohol, and allow to cool. Acetone may sometimes be employed for recrystallisation. 

The above simple experiments illustrate the more important properties of aliphatic acid chlorides. For characterisation, the general procedure is to hydrolyse the acid chloride by warming with dilute alkali solution, neutralise the resulting solution with dilute hydrochloric acid (phenol-phthalein), and evaporate to dryness on a water bath. The mixture of the sodium salt of the acid and sodium chloride thus obtained may be employed for the preparation of solid esters as detailed under Aliphatic Acids, Section 111,85. The anilide or p-toluidide may be prepared directly from the acid chloride (see (iii) above and Section III,85,i). 

If the anhydride of an unknown acid is being used and the anilic acid does not crystallise after the mixture has been boiled for a short time, cool the solution, wash it with dilute hydrochloric acid to remove the excess of aniline, and evaporate the solvent the anilic acid will then usually crystallise. 

Add 4 0 g. (4 0 ml.) of pure anihne dropwise to a cold solution of ethyl magnesium bromide (or iodide) prepared from 1 Og. of magnesium, 5 0 g. (3-5 ml.) of ethyl bromide (or the equivalent quantity of ethyl iodide), and 30 ml. of pure, sodium-dried ether. When the vigorous evolution of ethane has ceased, introduce 0 02 mol of the ester in 10 ml. of anhydrous ether, and warm the mixture on a water bath for 10 minutes cool. Add dilute hydrochloric acid to dissolve the magnesium compounds and excess of aniline. Separate the ethereal layer, dry it with anhydrous magnesium sulphate and evaporate the ether. Recrystallise the residual anihde, which is obtained in almost quantitative yield, from dilute alcohol or other suitable solvent. 

Reflux a mixture of 1 g. of the ester, 3 ml. of benzylamine and 0 1 g. of powdered ammonium chloride for 1 hour in a Pyrex test-tube fltted with a short condenser. Wash the cold reaction mixture with water to remove the excess of benzylamine. If the product does not crystallise, stir it with a httle water containing a drop or two of dilute hydrochloric acid. If crystallisation does not result, some unchanged ester may be present ... 

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