Feb. lo, 1876J 



NATURE 



293 



THE INDUSTRIAL APPLICATIONS OF 

 OXYGEN"^ 



T AVOISIER, who was the first to recognise in its widest 

 ■*-^ range the importance of oxygen, was also the first who 

 succeeded in making a practical use of it *' It is evident," he 

 writes, * ' ' that atmospheric air is not the best calculated means to 

 increase the effect of fire ; for, when a volume of air is conveyed 

 through the bellows to red-hot coals, three ( ?) parts of noxious 

 or at least useless gas are conveyed with every one part of the 

 useful kind of air ; consequently, if the latter could be employed 

 for combustion in its pure state, the action of the fire would be 

 greatly increased . Doubtless this idea has occurred to many others 

 before me ; indeed, I hear that M. Achard ^ has already tried the 

 experiment, but as yet a cheap and convenient apparatus is want- 

 ing." Lavoisier firet used the bladders of animals, which were 

 provided with cocks and tubes. " Then," continued he, " Imade a 

 hole with a knife from three to four lines deep in a large piece 

 of charcoal and placed in it six grs. of platinum. I then ignited 

 the charcoal through the blowpipe communicating with the enamel 

 lamp, uncocked my apparatus, and blew the pure vital air into 

 the cavity. The coal burnt very rapidly with detonation {such 

 as is produced by fusing saltpetre) and with dazzling brightness ; 

 in a few moments the platinum was fused to grains, which soon 

 tmited into a drop. The fusion was effected equally well when 

 using commercial platinum as when using that, which had been 

 deprived of its magnetic parts by the magnet Hitherto, it is 

 well known, platinum had been considered infusible." In the 

 course of the same year Lavoisier * improved his apparatus with 

 the assistance of 5leusnier, and soon became possessed of a 

 gasonieter consisting of two boxes greatly resembling, on a small 

 scale, the well-known reservoirs used in gasworks for holding 

 coal-gas. About the same time Saron had constructed two 

 blow-pipes (chalumeanx), one to furnish oxygen, and the other 

 hydrogen gas. 



^By their help Lavoisier did not succeed in melting platinum.' 

 However, at that time he and Saron had conceived the idea of 

 constructing an improved blow-pipe, in which the oxygen should 

 surround the hydrogen, and this led to the contrivance of the 

 oxyhydrogen blow-pipe, which has ever since been of such sub- 

 stantial service in the working of platinum and the soldering of 

 lead. 



No further attempts were made to fuse platinum by means of 

 oxygen until Deville and Debray ^ in 1857-1859 and the years fol- 

 lowing, published their excellent researches " On the platinum 

 metals," and brought the fusion of platinum into practice. The 

 soldering of platinum with platinum, and the manofacturing of 

 cast bars, were carried on on a large scale, first by Messrs. John- 

 son, Matthey, and Co., in London, and afterwards, though on a 

 smaller scale, by Herseus in Hanau, The experiments of 

 Debray and Deville were attended with one especial result, 

 the discovery of a fire-proof material for making furnaces and 

 crucibles. This is quick-lime, which had the further advantage 

 of retaining the heat as completely as possible. Besides, the 

 temperature was increased by conducting the flame from above, 

 directly, to the surface of the metal, and regulating the quantity 

 of oxygen and hydrogen as theory and practice suggested it To 

 melt 2 kilogs. of platinum, theory demands 55 litres oxygen and 

 110 litres hydrogen, while in reality more than one kilog. is fused 

 by these quantities, so that not 50 per cent, of the generated heat is 

 lost (a very satisfactory result). Their experiments were of still 

 greater importance for the history of oxygen industry, inasmuch 



' Translated, by i)ermission of ihe editor, from the ReportjOn the Deve- 

 lopment of Chemical Industry-, in conjunction with frienfis and fellow- 

 workers, by A. W. Hofmann. 



' " MemoJre sur un moyen d'augmenter considerablement Taction du feu 

 ctde la c&aleurdans les operations chimiques" (1782). CEuvresde Lavoisier, 

 iL, 425. 



^ Ihe above-mentioned work of Achard is to be found in the Memoirs of 

 the Berlin Academy of 1779, under the title, " Sur un nouveau moyen de 

 produire avec une tres-peute quantite de charbons une chaleur egale a cclle 

 qu'on pent produire par des verres et des miroirs ardents d'une grandeur 

 considerable." Achard decomposed saltpetre by heat in an earthenware 

 retort, and introduced the " dephlogisticated air" thus obtained into a pair 

 •f bellows, from whence it was conveyed into a charcoal furnace, where 

 some iron nails in a hessian crucible were rapidly reduced to fusion. He was 

 also of opinion that the introduction into badly ventilated rooms of gas pro- 

 cared in this way would cause the air in the same to be " dephlogisticated." 



4 Lavoisier, CEuvres ii., 432. 



5 Lavoisier, CEuvres li., 430. 



6 De\nlle and Debray. 1859, Ann. Chim. Phys. [3] Ivi. 385 ; DingL 

 I poL J. cliv. , 130, 199, 287, 383; in abstract Ann. Chem. Pharm. cxiv. 



, 78, and Debray, " Sur la production des temperatures elevees et sur la fusion du 

 ! platine," inthe "Lecons de Chimie professed en 1861." Paris, Hachette, 

 ; 1862. 



as they gave occasion for comparing the prices of different modes 

 of preparing it, and stimulated inquiry after cheaper processes. 

 These we may divide into chemical and mechanical, subdividing 

 the former again into continuous and intermittent processes. Up 

 to this time the following modes of preparation were in use, or 

 had been proposed. To begin with the oldest method of Priestley, 

 heating oxide of mercurj-, imquestionably the most costly and 

 the least adapted for practical purposes ; then Scheelc's method, 

 treating peroxide of manganese with sulphuric acid, which pro- 

 duces sulphate of manganese and oxygen. Through Berthier's re- 

 searches in 1822, this process has been superseded for manufac- 

 turing purposes by heating peroxide of manganese ; and, lastly, 

 we have to mention Bertholet's method, the heating of chlorate 

 of potassium. Notwithstanding its cost, the latter is constantly 

 used in the laboratory, because it is easy and requires little heat, 

 although it not unfrequently happens that a too rapid fusion 

 causes explosions. To obviate this inconvenience, the suggestion 

 has repeatedly been made of mixing peroxide of manganese 

 with the chlorate of potassium. 



More recent accidents, especially a fearful explosion which 

 took place in a pharmaceutical laboratory in Paris, induced 

 Debray and Boui^oin ^ to publish the precautions taken in De- 

 viUe's laboratory : peroxide of manganese, or what is easier to 

 obtain in a pure state, red oxide, Mn304, is added to the chlorate 

 of potassium in equal quantities, and the iron vessel containing 

 it exposed to heat in a charcoal furnace, so that the fire is lighted 

 firom above. Schwartz - also gives an account of some acci- 

 dents occasioned by using peroxide of manganese adulterated 

 with lampblack, and by inadvertence, even with sulphuret of 

 antimony ; and for that reason he recommends that all mixtures 

 for the production of oxygen be first tried by heating them on a 

 sheet of platinum. Alunck ' proposed adding oxide of iron, 

 which is more easily recognised, instead of peroxide of man- 

 ganese. Scheele's method of using peroxide of manganese and 

 sulphuric acid had this disadvantage : the glass vessels employed 

 were very liable to burst, through the solidifying of the sulphate 

 of manganese. To prevent this, R. Wagner * proposed to sub- 

 stitute bisulphate of sodium for sulphuric acid, thus forming an 

 easily fusible double salt, which would afford no danger of 

 breaking the retort when cooling. Pure peroxide of manganese 

 yields 18 per cent, by this treatmant, while heating it to red heat, 

 which resolves it into sesquioxide, yields only 12 per cent of 

 oxygen; nevertheless, the last method is the cheapest. Daville 

 and Debray = calculates its expense in proportion to the prices 

 of peroxide of manganese, which are as follows : — 



Per 100 kilogs. Per i cb.m. 



Romaneche 10 francs 4'86 francs 



Spain 16 „ 3-45 „ 



Pyrenees 18 „ 385 „ 



Giessen 29 „ 4*87 „ 



Italy 40 „ 5*98 „ 



The trifling value of the remaining sesquioxide, which (con- 

 taining iron) is of no use in the manufacture of glass, is not 

 here considered. 



The calculation dates from the time when the regeneration of 

 peroxide of manganese was an unsolved problem. Allowing 

 therefore the price of oxygen obtained firom peroxide of 

 manganese to vary between 3 "45 and 5" 98 fr., it is more than 

 twice as cheap as that which is procured from chlorate of 

 potassium, for which, according to Dupre,® the average price is 

 10 fr. 



As a much cheaper source, Deville and Debray now had re- 

 course to sulphtiric acid, which at a high temperature is de- 

 composed into water, sulphurous anhydride, and oxygen. " Retorts 

 of hard glass of a capacity of 5 litres are filled partly with 

 thin layers of platinum-foil or bits of tile and heated to a red 

 heat, whilst a thin stream of sulphuric acid is introduced. 



The escaping gases pass through a cooling contrivance to 

 condense the sulphuric acid, and afterwards through water to 

 remove the sulphurous acid gas. Thus, out of 2-435 kilogs. of 

 sulphuric acid of spec. grav. i"S27, 240 litres of oxygen were 

 obtained, and the price was calculated at I fir. per cb.m. By 



» Debray and Bourgoin, Ber. Chem. Ges., 1870 ; 240. 



2 Schwartz, " Breslauer Gewerbeblatt," 1865, No. 7 : Polzt Centralbl,, 

 1865, 12. 



3 Munck, Pohl's Lehrb, d. Tecknol., Wen, 1865 ; 186. 



4 Wagner, Jahresber., 1866 ; 198. 



5 Deville and Debray, Compt. Rend., li. 812 ; Dingl. pol. J., clix., 50. 



6 Dupre, Compt. Rend. Iv. 736. 



7 Deville and Debray, Compt. Rend. li. 823 ; DingL pol. J. cU.v. 50, in 

 Aii52. Ann. Chem. Pharrn. cx\-ii. 295. 



