Acidic Salt Solutions

Salts That Yield Neutral Solutions Salts That Yield Acidic Solutions Salts That Yield Basic Solutions Salts of Weakly Acidic Cations and Weakly Basic Anions... 

Salts in which the cation acts as an acid and the anion does not act as a base form acidic solutions. A salt in which the cation is either the conjugate acid of a weak base or a small, highly charged metal ion and in which the anion is the conjugate base of strong acid form acidic solutions. Salts in this category include ... 

CH2CI-CO-CH3. Colourless lachrymatory liquid b.p. 119°C. Manufactured by treating propanone with bleaching powder or chlorine. It is used as a tear gas and is usually mixed with the more potent bromoacetone. chloro acids Complex chloroanions are formed by most elements of the periodic table by solution of oxides or chlorides in concentrated hydrochloric acid. Potassium salts are precipitated from solution when potassium chloride is added to a solution of the chloro acid, the free acids are generally unstable. 

Perhaps the simplest case of reaction of a solid surface is that where the reaction product is continuously removed, as in the dissolving of a soluble salt in water or that of a metal or metal oxide in an acidic solution. This situation is discussed in Section XVII-2 in connection with surface area determination. 

Figure C2.12.2. Fonnation of Br0nsted acid sites in zeolites. Aqueous exchange of cation M witli an ammonium salt yields tlie ammonium fonn of tlie zeolite. Upon tliennal decomposition ammonia is released and tire proton remains as charge-balancing species. Direct ion-exchange of M witli acidic solutions is feasible for high-silica zeolites.

Since carbonic acid is a weak acid, its salts are hydrolysed in aqueous solution ... 

In concentrated hydrochloric acid solution, the reaction is GeCl -p Cr [GeClj]-and salts of this anion are known. 

Lead(Il) chromate VI) is precipitated when a soluble chromate(VI) or dichromatelVl) is added to a solution of a lead salt in neutral or slightly acid solution ... 

When hydrogen sulphide is bubbled into an acidic solution of an antimony or a bismuth salt an orange precipitate, SbjSs, or a brown precipitate, BijS, is obtained. Bismuth(III) sulphide, unlike antimony(IIl) sulphide, is insoluble in lithium hydroxide. 

In acid solution, dichromates(VI) (and also chromates(VI) which are converted to dichromates) are reduced to chromium(III) salts ... 

These are similar to those of the alkali metals but are rather less soluble in water. However, calcium sulphide, for example, is not precipitated by addition of sulphide ions to a solution of a calcium salt, since in acid solution the equilibrium position... 

These are practically insoluble in water, are not hydrolysed and so may be prepared by addition of a sufficient concentration of sulphide ion to exceed the solubility product of the particular sulphide. Some sulphides, for example those of lead(II), copper(II) and silver(I), have low solubility products and are precipitated by the small concentration of sulphide ions produced by passing hydrogen sulphide through an acid solution of the metal salts others for example those of zincfll), iron(II), nickel(II) and cobalt(II) are only precipitated when sulphide ions are available in reasonable concentrations, as they are when hydrogen sulphide is passed into an alkaline solution. 

As esters are usually difficult to detect, this test is of considerable value. In general esters react when heated with hydroxylamine to give a hydroxamic acid (I). The latter gives a coloured complex (II) with ferric salts in acid solution. 

Physical properties. Majority are liquids except p toluidine and 1- and 2-naphthylamine. All are colourless when pure, but rapidly darken on exposure to air and light. All are very sparingly soluble in water, but dissolve readily in dilute mineral acids (except the naphthyl-amines, which are only moderately soluble in adds). They form colourless crystalline salts e.g., CjHjNH2,HCl) which are soluble in water these aqueous solutions usually have an add reaction owing to hydrolysis, and give the reactions of both the amine and the acid from which they are derived. Addition of alkali to the acid solution liberates the amine. 

When an amine, or a solution of its hydrochloride, is added to an aqueous solution of chloroplatinic acid, a salt of the base with the cliloroplatinic acid, of general formula BjiHiPtCle (where B is one molecule of the base) is formed and usually crystallises out, for these chloroplatinates hai e normally a rather low solubility in cold water. The chloroplatinate can be filtered off, dried, and then analysed by direct ignition, when only the metallic platinum ultimately remains. Knowing the percentage of platinum in the chloroplatinate, the molecular weight of the latter, and hence of the constituent base, can readily be calculated. 

Saccharic acid. Use the filtrate A) from the above oxidation of lactose or, alternatively, employ the product obtained by evaporating 10 g. of glucose with 100 ml. of nitric acid, sp. gr. 1 15, until a syrupy residue remains and then dissolving in 30 ml. of water. Exactly neutralise at the boiling point with a concentrated solution of potassium carbonate, acidify with acetic acid, and concentrate again to a thick syrup. Upon the addition of 50 per cent, acetic acid, acid potassium saccharate sepa rates out. Filter at the pump and recrystaUise from a small quantity of hot water to remove the attendant oxahc acid. It is necessary to isolate the saccharic acid as the acid potassium salt since the acid is very soluble in water. The purity may be confirmed by conversion into the silver salt (Section 111,103) and determination of the silver content by ignition. 

To a mixture of 10 g. of the compound and 3-5 ml. of 33 per cent, sodium hydroxide solution in a test-tube, add 2-5 ml. of 50 per cent, chloroacetic acid solution. If necessary, add a little water to dissolve the sodium salt of the phenol. Stopper the test-tube loosely and heat on agently-boiling water bath for an hour. After cooling, dilute with 10 ml. of water, acidify to Congo red with dilute hydrochloric acid, and extract with 30 ml. of ether. Wash the ethereal extract with 10 ml, of water, and extract the aryloxyacetic acid b shaking with 25 ml. of 5 per cent, sodium carbonate solution. Acidify the sodium carbonate extract (to Congo red) with dilute hydrochloric acid, collect the aryloxyacetic acid which separates, and recrystallise it from hot water. 

Oxidation of benzoin with concentrated nitric acid or by catalytic amounts of cupric salts in acetic acid solution, which are regenerated continuously by ammonium nitrate, yields the diketone benzil ... 

Meihylamine hydrochloride method. Place 100 g. of 24 per cent, methyl-amine solution (6) in a tared 500 ml. flask and add concentrated hydrochloric acid (about 78 ml.) until the solution is acid to methyl red. Add water to bring the total weight to 250 g., then introduce lSO g. of urea, and boil the solution gently under reflux for two and three-quarter hours, and then vigorously for 15 minutes. Cool the solution to room temperature, dissolve 55 g. of 95 per cent, sodium nitrite in it, and cool to 0°. Prepare a mixture of 300 g. of crushed ice and 50 g. of concentrated sulphuric acid in a 1500 ml. beaker surrounded by a bath of ice and salt, and add the cold methylurea - nitrite solution slowly and with mechanical stirring and at such a rate (about 1 hour) that the temperature does not rise above 0°. It is recommended that the stem of the funnel containii the methylurea - nitrite solution dip below the surface of the acid solution. The nitrosomethylurea rises to the surface as a crystalline foamy precipitate. Filter at once at the pump, and drain well. Stir the crystals into a paste with about 50 ml. of cold water, suck as dry as possible, and dry in a vacuum desiccator to constant weight. The yield is 55 g. (5). 

Esters react witli hydroxylamine to form an alcohol and a hydroxamic acid, RCONHOH. All hydroxamic acids, in acid solutions, react with ferric chloride to form coloured (usually violet) complex salts ... 

Hydrolysis of a sulphonamide. Mix 2 g. of the sulphonamide with 3-5 ml. of 80 per cent, sulphuric acid in a test-tube and place a thermometer in the mixture. Heat the test-tube, with frequent stirring by means of the thermometer, at 155-165° until the solid passes into solution (2-5 minutes). Allow the acid solution to cool and pour it into 25-30 ml. of water. Render the resulting solution alkaline with 20 per cent, sodium hydroxide solution in order to liberate the free amine. Two methods may be used for isolating the base. If the amine is volatile in steam, distil the alkaline solution and collect about 20 ml. of distillate extract the amine with ether, dry the ethereal solution with anhydrous potassium carbonate and distil off the solvent. If the amine is not appreciably steam-volatile, extract it from the alkaline solution with ether. The sulphonic acid (as sodium salt) in the residual solution may be identified as detailed under 13. 

The essential basis of the scheme for the separation of water-soluble compounds is, therefore, distillation of (a) an aqueous solution of the mixture, (b) an alkaline (with sodium hydroxide) solution of the mixture, and (c) an acidic (with sulphuric oj phosphoric acid) solution of the mixture. The residue will contain the non-volatile components, which must be separated from inorganic salts and from each other by any suitable process. 

The residue (5) in the distilhng flask may stUl contain a water-soluble, non-volatile acid. Cool the acid solution, neutralise it with dilute sodium hydroxide solution to Congo red, and evaporate to dryness on a water bath under reduced pressure (water pump). Heat a httle of the residual salt (G) upon the tip of a nickel spatula in a Bunsen flame and observe whether any charring takes place. If charring occurs, thus... 

The weakly basic 2-aminothiazoles are most readily diazotized in concentrated solutions of oxygen containing acids such as sulfuric acid, 40 to 50% (322-326) fiuoroboric phosphoric acids (589) phosphoric acid (327, 328) and mixtures of phosphoric and nitric acid (74. 322, 323. 329-331). From strong acid solutions, solid diazonium salts can be isolated (34, 332. 333). 

Methyl free radicals, generated either by thermolysis of lead tetracetate in acetic acid solution (401) or by radical cleavage of dimethylsulfoxide by H2O2 and iron (II) salts (408), afford 2- and 5-methylthiazole in the proportion of 86 and 14%, respectively, in agreement with the nucleophilic character of alkyl free radicals and the positive charge of the 2-carbon atom of the thiazole (6). 

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