Hot concentrated nitric acid oxidizes it to picric acid and oxalic acid, whilst on treatment with hydrochloric acid and potassium chlorate it yields chloranil (tetrachloroquinone).
The peroxide, Ru04, is formed when a solution of potassium ruthenate is decomposed by chlorine, or by oxidizing ruthenium compounds with potassium chlorate and hydrochloric acid, or with potassium permanganate and sulphuric acid.
Serullas and Roscoe; Davy and Stadion investigated chlorine peroxide, formed by treating potassium chlorate with sulphuric acid.
Davy also described and partially investigated the gas, named by him " euchlorine," obtained by heating potassium chlorate with hydrochloric acid; this gas has been more recently examined by Pebal.
For many years it had been known that a mixture of potassium chlorate and hydrochloric or sulphuric acids possessed strong.
Carius showed that potassium chlorate and sulphuric acid oxidized benzene to trichlorphenomalic acid, a substance afterwards investigated by Kekule and 0.
Potassium chlorate and hydrochloric acid oxidize phenol, salicylic acid (o-oxybenzoic acid), and gallic acid ([2.3.4] trioxybenzoic acid) to tri chlorpyroracemic acid (isotrichlorglyceric acid), CC13 C(OH)2 C02H, a substance also obtained from trichloracetonitrile, CC1 3 CO CN, by hydrolysis.
Potassium bichromate and sulphuric acid oxidize it to carbon dioxide and water; and potassium chlorate and hydrochloric acid to chloranil.
Thus neither a chlorate, which contains the ion C103, nor monochloracetic acid, shows the reactions of chlorine, though it is, of course, present in both substances; again, the sulphates do not answer to the usual tests which indicate the presence of sulphur as sulphide.
Manganese dioxide and sulphuric acid oxidize it to benzoic and o-phthalic acid; potassium chlorate and sulphuric acid breaks the ring; and ozone oxidizes it to the highly explosive white solid named ozo-benzene, C 6 H 6 O 6.
When treated with hydrochloric acid and potassium chlorate, no chlorinated quinones are obtained (M.
For the theory and elemental laws of electro-deposition see Electrolysis; and for the construction and use of electric generators see Dynamo and Battery: Electric. The importance of the subject may be gauged by the fact that all the aluminium, magnesium, sodium, potassium, calcium carbide, carborundum and artificial graphite, now placed on the market, is made by electrical processes, and that the use of such processes for the refining of copper and silver, and in the manufacture of phosphorus, potassium chlorate and bleach, already pressing very heavily on the older non-electrical systems, is every year extending.
The chlorine reacts with the caustic soda, forming sodium hypochlorite, and this in turn, with an excess of chlorine and at higher temperatures, becomes for the most part converted into chlorate, whilst any simultaneous electrolysis of a hydroxide or water and a chloride (so that hydroxyl and chlorine are simultaneously liberated at the anode) also produces oxygen-chlorine compounds direct.
Oettel, using a 20% solution of potassium chloride, obtained the best yield of hypochlorite with a high current-density, but as soon as II% of bleaching chlorine (as hypochlorite) was present, the formation of chlorate commenced.
The best yield of chlorate was obtained when from I to 4% of caustic potash was present.
With high current-density, heating the solution tended to increase the proportion of chlorate to hypochlorite, but as the proportion of water decomposed is then higher, the amount of chlorine produced must be less and the total chlorine efficiency lower.
In other words, each pound of chlorate would require an expenditure of nearly 5.1 e.h.p. hours.
Ammonium chlorate, NH 4 C10 3, is obtained by neutralizing chloric acid with either ammonia or ammonium carbonate, or by precipitating barium, strontium or calcium chlorates with ammonium carbonate.
For the oxyhalogen salts see Chlorate, Chlorine, Bromine and Iodine.
Lozenges of potassium chlorate are used in stomatitis, tonsilitis and pharyngitis, it can also be used in a gargle, to grs.
It readily forms addition products with chlorine and with hydrogen; the dichloride, C10H8C12, is obtained as a yellow liquid by acting with hydrochloric acid and potassium chlorate; the solid tetrachloride, C,o 11 8 C1 4, results when chlorine is passed into naphthalene dissolved in chloroform.
Oxygen may be prepared by heating mercuric oxide; by strongly heating manganese dioxide and many other peroxides; by heating the oxides of precious metals; and by heating many oxy-acids and oxy-salts to high temperatures, for example, nitric acid, sulphuric acid, nitre, lead nitrate, zinc sulphate, potassium chlorate, &c. Potassium chlorate is generally used and the reaction is accelerated and carried out at a lower temperature by previously mixing the salt with about one-third of its weight of manganese dioxide, which acts as a catalytic agent.
The actual decomposition of the chlorate is not settled definitely; the following equations give the results obtained by P. F.
Those of the alkali metals are prepared by fusing manganese dioxide with sodium or potassium hydroxide in the presence of air or of some oxidizing agent (nitre, potassium chlorate, &c.); MnO 2 +2KHO+O=K 2 Mn0 4 +H 2 O.
The gaseous mixture, issuing from the latter, is washed with water in the usual condensing apparatus, to remove the 40 or 50 parts of hydrochloric acid left unchanged, and can then be immediately employed for the manufacture of chlorate of potash.
But most of the chlorine is utilized for the production of bleaching-powder, of bleach-liquor, and of chlorate of potash.
Chlorate of Potash.
- Formerly all chlorate of potash, as some is still, was obtained by passing chlorine into milk of lime, allowing the temperature to rise almost to the boiling-point, and continuing until the bleaching-solution, originally formed, is converted into a mixture of calcium chlorate and chloride, the final reaction being 6Ca(OH)2+6C12=5CaC12+Ca(C103)2+6H20.
On adding to this solution, after settling out the mud, a quantity of potassium chloride equivalent to the calcium chlorate, the reaction Ca(C10 3) 2 +2KC1=CaC1 2 +2KC10 3 is produced, the ultimate proportions thus being theoretically 2KC10 3 to 6CaCl2, though in reality there is rather more calcium chloride present.
When this solution is concentrated by evaporation and cooled down, about five-sixths of the chlorate of potash crystallizes out.
During these operations care must be taken lest a spark should produce the inflammation of the chlorate on contact with any organic substance.
Large quantities of potassium chlorate exposed to strong heat in contact with the wood of casks or the timber of a roof have produced violent explosions.
A little earlier the manufacture of potassium chlorate (on the large scale since 1890) had been brought to a definite success by H.
The electrolysis is carried on until about a quarter of the chloride has been transformed; it must be stopped at this stage lest the formation of hypochlorite and chlorate should set in.
This is filtered, washed, and then fused with caustic soda, when the sulpho-group is replaced by a hydroxyl group, and a second hydroxyl group is simultaneously formed; in order to render the formation of this second group easier, a little potassium chlorate or sodium nitrate is added to the reaction mixture.
At the same time he was working with Thenard at the improvement of the methods of organic analysis, and by combustion with oxidizing agents, first potassium chlorate and subsequently copper oxide, he determined the composition of a number of organic substances.
Nickel sesquioxide, N1203, is formed when the nitrate is decomposed by heat at the lowest possible temperature, by a similar decomposition of the chlorate, or by fusing the chloride with potassium chlorate.
The halogen of lower atomic weight can displace one of higher atomic weight from its hydrogen compound, or from the salt derived from such hydrogen compound, while, on the other hand, the halogen of higher atomic weight can displace that of lower atomic weight, from the halogen oxy-acids and their salts; thus iodine will liberate chlorine from potassium chlorate and also from perchloric acid.
As this oxide is a dangerous explosive, great care must be taken in its preparation; the chlorate is finely powdered and added in the cold, in small quantities at a time, to the acid contained in a retort.
A mixture of chlorine peroxide and chlorine is obtained by the action of hydrochloric acid on potassium chlorate, and similarly, on warming a mixture of potassium chlorate and oxalic acid to 70° C. on the water bath, a mixture of chlorine peroxide and carbon dioxide is obtained.
It is a very powerful oxidant; a mixture of potassium chlorate and sugar in about equal proportions spontaneously inflames when touched with a rod moistened with concentrated sulphuric acid, the chlorine peroxide liberated setting fire to the sugar, which goes on burning.
The silver and lead salts are unstable, being decomposed with explosive violence at 100° C. On adding a caustic alkali solution to one of chlorine peroxide, a mixture of a chlorite and a chlorate is obtained.
Berthollet, and is best prepared by decomposing barium chlorate with the calculated amount of dilute sulphuric acid.
Potassium perchlorate, Kcio 4, can be obtained by carefully heating the chlorate until it first melts and then nearly all solidifies again.
The fused mass is then extracted with water to remove potassium chloride, and warmed with hydrochloric acid to remove unaltered chlorate, and finally extracted with water again, when a residue of practically pure perchlorate is obtained.
About 1839, on the recommendation of Graham, whom in 1837 he had accompanied to University College, London, he was appointed chemist at James Muspratt's alkali works in Lancashire; in connexion with alkali he showed that cast-iron vessels could be satisfactorily substituted for silver in the manufacture of caustic soda, and worked out improvements in the production of chlorate of potash.
The most important is potassium chlorate, KC10 3, which was obtained in 1786 by C. L.
The modern process consists in the electrolysis of a hot solution of potassium chloride, or, preferably, the formation of sodium chlorate by the electrolytic method and its subsequent decomposition by potassium chloride.
Soc., 1886, p. 141), the decomposition of potassium chlorate by heat is not at all simple, the quantities of chloride and perchlorate produced depending on the temperature.
Sodium chlorate, NaC10 3, is prepared by the electrolytic process; by passing chlorine into milk of lime and decomposing the calcium chlorate formed by sodium sulphate; or by the action of chlorine on sodium carbonate at low temperature (not above 35° C.).
Potassium chlorate is very valuable in medicine.
On heating, it begins to decompose at 260-265° C. Barium chlorate, Ba(C103)2, is obtained by adding barium chloride to sodium chlorate solution; on concentration of the solution sodium chloride separates first, and then on further evaporation barium chlorate crystallizes out and can be purified by recrystallization.
He also prepared potassium chlorate and attempted to use it in the manufacture of gunpowder as a substitute for saltpetre.
A saturated solution of potassium chlorate in strong nitric acid is added, and the mass evaporated to dryness.
The ore is treated as described in the cyanide method until the copper precipitated by the aluminium foil has been washed and dissolved in 5 cc. of nitric acid; then 0.25 gramme of potassium chlorate is added, and the solution boiled nearly dry to oxidize any arsenic present to arsenic acid.
5 of a gramme of pure iron wire in a flask, in hydrochloric acid, oxidizing it with a little potassium chlorate, boiling off all traces of chlorine, deoxidizing by one of the methods described above, and titrating with the solution.
In this process, the residues are boiled with a dilute sulphuric acid to which nitric acid and potassium chlorate are added in order to transform the element into selenic acid, H 2 Se0 4, which is then reduced to selenious acid, H 2 Se0 3, by boiling with hydrochloric acid, and finally to selenium by sulphur dioxide.
The substitution of potassium chlorate for pyrolusite is recommended when calcium chloride is present in the bittern.
It has been used in combination with potassium chlorate as a composition for matches to strike on any surface.
Phosphoryl trichloride or phosphorus oxychloride, POC1 3, corresponding to phosphoric acid, (HO) 3 P0, discovered in 1847 by Wurtz, may be produced by the action of many substances containing hydroxy groups on the pentachloride; from the trichloride and potassium chlorate; by leaving phosphorus pentoxide in contact with hydrochloric acid: 2P 2 0 5 +3HC1= POC13+3HP03; or by heating the pentachloride and pentoxide under pressure: 3PC15+ P205= 5POC1 3.
For example, on boiling an aqueous solution of a hypochlorite, a chlorate and a chloride results, part of the original salt being oxidized and part reduced: 3NaOC1= NaC103-2NaC1.
Further, certain cubic crystals, such as sodium chlorate and bromate, and also some liquids and even vapours, rotate the plane of polarization of the light that traverses them, whatever may be the direction of the stream.