Potassium dichromate

“ Unfortunately, bichromate of potash is not very soluble in water; one pint of water will not take up much more than three [Pg 47] ounces of this salt. Hence, though the solution of potassium bichromate is an excellent depolariser as long as it contains any of the salt, it soon becomes exhausted. When bichromate of potash is used in a cell along with sulphuric acid and water, sulphate of potash and chromic acid are formed, thus:—
From this we learn that before the potassium bichromate enters into action in the battery, it is resolved into chromic acid. ”

“ The alkaline chromates are soluble in water, those of most other metals being insoluble. By the addition of mineral acids, they are converted rapidly into bichromates. They are easily reduced in acid solution by sulphuretted hydrogen, and also by sulphur dioxide to chromium salts. The chromates are stable towards heat; they are poisonous, and may be recognized by the yellow precipitates they give with soluble barium and lead salts.
Potassium chromate, K2CrO4, may be prepared by neutralizing a solution of potassium bichromate with potassium carbonate or with caustic potash. ”

“ At 32° F. it is brittle, like glass; at 59° it is soft and malleable; at 144° it becomes liquid. Potassium is widely diffused in the vegetable, animal and mineral kingdoms. Some of the more important potassium compounds are caustic potash (the hydroxide) , the carbonate, the bicarbonate; also potassium chloride, bromide, iodide, nitrate (saltpeter) , sulphate, chlorate, cyanide etc. Of these iodide, bromide and chlorate are used for medicines, the others being employed more or less in the arts. ”

“ It is ground and stirred up with hot water, and sulphuric acid is added till a slight acid reaction becomes apparent, a sign that the neutral chromate has been converted into bichromate. Chalk is now stirred in to precipitate the ferric sulphate, and after a while the clear solution is run off into another vessel, where it is treated with carbonate of potassium, which precipitates the lime and leaves bichromate of potassium in solution. The solution is then evaporated to the crystallising point. This process, when carried out on a large scale, is very economical. ”

“ In 1807, Sir Humphry Davy discovered the metal potassium by subjecting moistened potash to the action of a powerful voltaic battery; the positive pole gave off oxygen and the metallic globules of pure potassium appeared at the negative pole. It is never found uncombined in nature. Now if potassium is heated in cyanogen gas (a gas procured by heating mercury) or obtained on a large scale by the decomposition of yellow prussiate of potash, a white crystalline body very soluble in water, and exceedingly poisonous, is obtained. ”

“ Those elements which unite with the utmost eagerness at ordinary temperatures, seem to become indifferent 272to each other when subjected to the extremes of heat and cold. Potassium unites fiercely with oxygen in the most familiar of all chemical experiments. Potassium is indeed a strange metal, for it is of such small density that a piece cast on a basin of water will float like a chip of wood. It has such avidity for oxygen that it will decompose the water to wrench the molecules of oxygen from those of hydrogen. ”

“ Carbonic ether, Carbonate of oxide of ethyl; Æther carbonicus, L. Prep. Fragments of potassium are added to oxalic ether, gently warmed, as long as bubbles of gas are formed; the excess of metal is removed from the semi-solid mass, some water added, and the whole distilled. The carbonic ether floats on the surface of the liquid in the receiver, and is collected, dried by contact with chloride of calcium, and rectified along with some potassium or sodium, till it ceases to yield acetate of potassa when acted on by caustic potassa. ”

“ Its aqueous solution gives a white gelatinous precipitate soluble in excess; a platinum wire moistened with the solution imparts a violet colour to the blowpipe flame;109 and chloride of barium gives a white precipitate insoluble in nitric acid.
Pur. When pure, its solution is not darkened by tincture of galls, sulphuretted hydrogen or ferrocyanide of potassium; neither does it give any precipitate with solution of nitrate of silver. Heated with caustic potassa, or quick-lime, it does not evolve fumes of ammonia. ”

“ The discovery of potassium led to that of the true nature of what had been long familiar to chemists by the name of pure Potash, but which ought to 284 have been called the hydrat, for the pure alkali was not known until after the discovery of Davy. The experiments of MM. Gay Lussac and Thénard have shown this substance to be a Protoxide. It is difficult of fusion; it has a grey colour and a vitreous fracture, and dissolves in water with much heat. The Peroxide is procured by the combustion of potassium at a low temperature ”

“ A solution of chloride of lime marking 18° or 20° Baumé, is to be set upon the fire in a lead or cast iron pot, and when it begins to get hot, there is to be dissolved in it, a quantity of chloride of potassium sufficient to raise the hydrometer 3 or 4 degrees. It must be then concentrated as quickly as possible till it marks 30° or 31°, taking care that it does not boil over by the sudden extrication of oxygen. The concentrated liquor is set aside to crystallize in a cool place; where a deposit of chlorate of potash forms, mixed with chloride of potassium. ”

“ Fourthly, by mixing together various earths with the oxides of tin, iron, lead, silver, and mercury: a mode of manipulation suggested by the results of his previous experiments 299 on potassium, in which he found that when a mixture of potash and the oxides of mercury, tin, or lead, was electrified in the Voltaic circuit, the decomposition was very rapid, and an amalgam, or an alloy of potassium, was obtained; the attraction between the common metals and the potassium apparently accelerating the separation of the oxygen. ”

“ Chromate and bichromate of potassium give yellow precipitates insoluble in dilute nitric acid, and soluble in solution of potassium hydrate. Iodide of potassium gives a yellow precipitate, soluble in great excess by heat, and separating in small, brilliant, golden-yellow scales, as the liquid cools. A piece of polished zinc precipitates metallic lead in an arborescent form, hence called the lead tree. To prepare for these tests, a solid supposed to contain lead should be digested in nitric acid, when the solution, evaporated to dryness and redissolved in water, may be tested as above. ”

“ It is used in testing for metallic oxides and silica before the blowpipe. The crystals are sometimes used as a standard for phosphoric acid.
"Nessler's Solution."—Mode of preparation: Dissolve 35 grams of potassium iodide in 100 c.c. of water; dissolve 17 grams of mercuric chloride in 300 c.c. of water, and pour this solution into that of the iodide till a permanent precipitate is produced; make up to 1 litre with a 20 per cent. solution of potash; add mercuric chloride till a precipitate is again formed; allow to settle and decant. It is used for detecting ammonia. ”

“ The same analogies apply to phosphorus and carbon. His conclusion was mainly derived from the fact, that hydrogen is produced from sulphur and phosphorus in such quantities by Voltaic electricity, that he thinks it cannot well be considered as an accidental 313 ingredient in them: the presence of oxygen, he contends, may be inferred from the circumstance that, when potassium is made to act upon these bodies, the sulphurets and phosphurets so formed evolve by the action of an acid less hydrogen, in the form of compound inflammable gas, than the same quantity of potassium in an uncombined state. ”

“ The paper will be found covered with a solution of ordinary potash. If turmeric paper be used, the course of the potassium will be marked with a deep brown color.—Corollary. Hence, if you touch potassium with wet fingers you will burn them.
If a small piece of the metal be placed on a piece of ice, it will instantly take fire, and form a deep hole, which will be found to contain a solution of potash.
In consequence of its great affinity for oxygen, potassium must be kept in some fluid destitute of that element, such as naphtha. ”

“ Our pint of water would then occupy 1800 times its present volume.
Let us now give a striking and beautiful illustration of chemical affinity. We will throw into this tumbler a piece of potassium (symbol K) half as large as a pea. This interesting metal was discovered by Davy in 1807. Its affinity for O is very great. As soon as it falls upon the water it abstracts oxygen and forms potassium oxide (potash) , while the hydrogen and a small amount of volatilized K escape and are burned with a brilliant violet flame, on account of the heat evolved by the energetic chemical action. ”

“ Potassium is one of the eight most abundant elements in the earth. It occurs as a primary constituent of most igneous rocks, [Pg 113] some of which carry percentages as high as those in commercial potash salts used for fertilizers. It is present in some sediments and likewise occurs in many schists and gneisses. Various potassium silicates—leucite, feldspar, sericite, and glauconite—and the potassium sulphate, alunite, have received attention and certain of them have been utilized to a small extent, but none of them are normally able to compete on the market. ”

“ Not an atom of potassium can be obtained unless the potassa be moistened; nor can any salt be decomposed except water be present. Sir Humphry says, it is required, to render the substance a conductor; but its operation is more recondite, and there is something mysterious and still unexplained in the uniform appearance of hydrogen and oxygen at the opposite poles, when far apart in water, and in all other cases of true polar electro-chemical decomposition. ”

“ Salts are formed when a “basis,” i.e., a metal oxide, replaces water. When potassium-acid sulfate is neutralized by sodium base, the acid-salt divides into Glauber’s salt and potassium sulfate, which proves the acid-salt to be a mixture of the neutral salt with its acid. Sodium-acid phosphate behaves quite differently. After neutralization by a potassium “base” (hydroxide) , the salt does not split up; a uniform sodium-potassium phosphate is obtained. Therefore, phosphoric acid is truly three-basic! ”

“ The oxidation of the potassium salt is effected as follows. 50 grams of the salt are dissolved in 21⁄2 litres of water, and to this is added a solution of 15 grams of potassium hydroxide. The mixture is heated to 100° on a water-bath, and when this temperature is reached, 110 grams of potassium permanganate are added. Heating is continued until the solution is decolorized, care being taken to prevent the evolution of free oxygen. ”

“ The natural decomposition of rocks containing potassium gives rise to various compounds of the element in all fertile soils. Its soluble compounds are absorbed by growing plants and built up into complex vegetable substances; when these are burned the potassium remains in the ash in the form of the carbonate. Crude carbonate obtained from wood ashes was formerly the chief source of potassium compounds; they are now mostly prepared from the salts of the Stassfurt deposits. ”

“ His object was twofold: to refute the hypothesis which assumed hydrogen as an element of potassium, and to ascertain the nature of the matter existing in the amalgam of ammonia, or the supposed metallic basis of the volatile alkali: a question intimately connected with the whole of the arrangements of chemistry. As to the former point, it is unnecessary to enter into farther discussion; and with regard to the latter, it is quite impossible to convey an adequate idea of the extent of the enquiry: there does not exist in the annals of chemistry a more striking example of experimental industry. ”

“ This shows that the molecule of potassium (like that of sodium, mercury, and zinc) contains but one atom. This is also the case with many other metals, judging by recent researches. [19] The specific gravity of potassium at 15° is 0·87, and is therefore less than that of sodium, as is also the case with all its compounds. [20] Potassium decomposes water with great ease at the ordinary temperature, evolving 45,000 heat units per atomic weight in grams. The heat evolved is sufficient to inflame the hydrogen, the flame being coloured violet from the presence of particles of potassium. ”

“ Diamond through your valuable publication, that I am, in common with many others, extremely indebted to him for his collodion, and would esteem it a favour if he would answer the following Queries, viz.:
1st. He says, in answer to a previous Query, that "nitrate of potassa" is not formed in his process. Now I wish to ask if (as the iodide of silver is redissolved in iodide of potassium) it is not formed when the plate is plunged into the nitrate silver bath, as the nitrate decomposes the iodide of potassium? ”

“ When the charge in a cylinder is exhausted, a fresh one is introduced by removing the plug, taking out the residue, and inserting a new supply of the mixture made up in a canvas bag. The operation is therefore continuous, and the metal obtained is nearly pure, as sodium does not exhibit the same tendency as potassium to form compounds with carbonic oxide.
Potassium and sodium are extremely soft metals; they are lighter than water, upon which they float, at the same time rapidly decomposing that compound by displacing half the hydrogen, which is set on fire by the heat. ”