BANCROFT 
 LIBRARY 
 
 o- 
 
 THE LIBRARY 
 
 OF 
 
 THE UNIVERSITY 
 OF CALIFORNIA 
 
DEPARTMENT OF THE 
 
 UNITED STATES GEOLOGICAL SUE 
 J. W. POWELL DIRECTOR 
 
 IODINE 
 
 BY 
 
 T. 
 
 ABSTRACT FROM ''MINERAL RESOURCES OF THE UNITED STATES, 
 
 CALENDAR YEARS 1883 AND 1884 "-ALBERT WILLIAMS, JR., 
 
 CHIEF OF DIVISION OF MINING STATISTICS 
 
 WASHINGTON 
 
 GOVERNMENT PRINTING OFFICE 
 
 1885 
 
DEPARTMENT OF THE Iff JSBIOB 
 
 UNITED STATES GEOLOGICAL SURVEY 
 J. W. POWELL DIRECTOR 
 
 IODINE^ 
 
 BY 
 
 IDT. ,13 A. 
 
 ABSTRACT FROM "MINERAL RESOURCES OF THE UNITED STATES, 
 CALENDAR YEARS 1883 AND 1884" ALBERT WILLIAMS, JR., 
 CHIEF C/ DIVISION OF MINING STATISTICS 
 
 WASHINGTON 
 
 GOVERNMENT PRINTING OFFICE 
 
 1885 
 
IODINE. 
 
 BY DAVID T. DAY. 
 
 Domestic occurrences. Traces of iodides have been found, together 
 with chlorides and bromides, in the various salt wells, particularly those 
 of the West Virginia and Ohio district. At Saratoga, New York, traces 
 have been detected, but although the percentage of iodine in profitable 
 sources is extremely small, the occurrences in the United States will, 
 in all probability, remain entirely insignificant. Although iodine is not 
 produced in the United States, its important influence upon the bromine 
 industry, in which the United States holds first rank, makes a considera- 
 tion of the peculiar features of the iodine industry advisable. 
 
 Sources and mode of manufacture. Sea water and the South American 
 nitrate deposits have served as the only sources of iodine. The minute 
 trace of iodine in the former is concentrated by many varieties of algae, 
 so that these plants when perfectly dry contain from 0.0297 to 0.4535 
 per cent, of their weight in iodine, in the form of iodides of the alkali 
 metals (Stanford). Before the discovery of iodine by Courtois, in 1811, 
 these alga3 were collected on the shores of Ireland, Scotland, and Nor- 
 mandy, and their ashes ( "kelp," u varec " ) furnished a considerable part 
 of the soda and potash of that time. According to the report of Mr. 
 E. 0. Stanford (a) the production of kelp, that is, the ashes of several 
 varities of seaweed, amounted to 20,000 tons from the western islands 
 alone at the beginning of this century, and sold for 20 to 22 per ton. 
 The importation of barilla then began, and this, together with the 
 establishment of the Leblanc soda process, reduced the price of kelp to 
 10 per ton. Among the manufacturers of sodium salts from kelp was 
 Courtois, in Paris. His discovery of iodine in the kelp was made at a 
 time when theoretical discussions as to the elementary character of 
 chlorine subjected the properties of that substance to careful study, 
 and the analogous character of iodine led in an unusally short time to 
 a general knowledge of this element and its possible uses. It was ex- 
 tracted from kelp during the preparation of soda; but small quantities 
 fully satisfied the demand, so that its source was no more valuable than 
 before iodine was discovered. In fact the price of kelp sank gradually 
 to 2 per ton in 1831. Between 1841 and 1844, however, iodine was 
 applied to the manufacture of aniline dyes. In 1845 the production of 
 iodine began on a commercial scale, and kelp was again in demand. 
 
 a Chemical News, Vol. 35, page 172, 1877. 
 
IOBINE. 
 
 855 
 
 The imports to the Clyde increased from 2,565 tons in 1841 to 6,000 tons "" 
 in 1845. In the latter year there were four small works engaged in the 
 manufacture of iodine j in 1846 this number increased to twenty. The 
 kelp required was not the same ; formerly that yielding most soda was 
 needed, but this was poorest in iodides, which now became the im- 
 portant constituents. Moreover, it was foui^d that kelp richest in 
 iodine was also richest in potassium, which also was valuable ; potas- 
 sium chloride being worth 25 per ton. The following table gives the 
 imports of kelp into the Clyde for thirty-five years, and also the price 
 of iodine from the time of its industrial application up to the present. 
 The earlier figures have been compiled by Mr. Stanford, of Glasgow, 
 and the later prices of iodine have been furnished through the kindness 
 of Messrs. Powers & Weightman, of Philadelphia. 
 
 Kelp imports into the Clyde, and price of iodine. 
 
 Years ending June 30 
 
 Kelp im- 
 ports. 
 
 Price of 
 iodine. 
 
 Years ending June 30 
 
 Kelp im- 
 ports. 
 
 Price of 
 iodine. 
 
 1841 
 
 Long tons. 
 2 5^ 
 
 Per pound. 
 $1.20 ' 
 
 1865 
 
 Long tons. 
 13 741 
 
 Jr&f pound. 
 $1 84 
 
 1842 
 
 1, 887 
 
 1.12 
 
 1866 
 
 8 858 
 
 2.40 
 
 1813 .. .. 
 
 1,965 
 
 1.44 
 
 1867 
 
 8 174 
 
 2 88 
 
 1844 
 
 3,263 
 
 2.88 ! 
 
 1868 
 
 8,116 
 
 3.04 
 
 1845 
 
 6 0;sG 
 
 7.46 
 
 1869 
 
 8 978 
 
 3 12 
 
 1846 
 
 3,627 
 
 5.34 
 
 1870 
 
 9,257 
 
 3.04 
 
 1847 .... 
 
 4 000 
 
 2.64 
 
 1871 
 
 9 384 
 
 3 44 
 
 1848 
 
 4 400 
 
 2 64 
 
 1872 
 
 10 049 
 
 8 If) 
 
 1849 
 
 4 731 
 
 2.64 
 
 1873 
 
 9 449 
 
 5 12 
 
 1850 
 
 11,421 
 
 2.56 
 
 1874 
 
 10 923 
 
 a3. 52 
 
 1851 
 1852 
 
 7,320 
 5,418 
 
 2.08 
 3.64 
 
 1875 
 
 8 643 
 
 62.94 
 a2 44 
 
 1853 
 1854 
 
 6,491 
 4,679 
 
 3.72 
 
 2.88 
 
 1876 
 
 
 62.25 
 al.92 
 
 1855 
 
 1856 
 
 5,826 
 6 349 
 
 3.20 
 3 28 
 
 1877 
 
 
 61.87 
 c3 28 
 
 1857 
 
 8,641 
 
 2.96 
 
 1878 
 
 
 c4 00 
 
 1858 
 
 8 123 
 
 2.52 
 
 1879 
 
 
 c4 48 
 
 1859 
 
 8,190 
 
 2.32 
 
 1880 
 
 
 d\ 92 
 
 1860 
 
 7 754 
 
 2.04 
 
 1881 
 
 
 d2 00 
 
 1861 
 
 9,722 
 
 1.68 
 
 1882 . 
 
 
 dl 60 
 
 1862 
 
 9 414 
 
 1 36 
 
 1883 
 
 
 dl 28 
 
 1863 
 
 14, 018 
 
 1.20 
 
 1884 
 
 
 di;20 
 
 1864 
 
 11,349 
 
 2.00 
 
 
 
 e2. 88 
 
 a Scotch. & Peruvian. c Combination. d Combination broken. e Recombination. 
 
 The extraordinary fluctuations in the price of iodine serve to indi- 
 cate the complicated conditions of oversupply, extended production, 
 combination of manufacturers, and open competition, to which an in- 
 dustry is occasionally subjected. During the early years of the manu- 
 facture the extended use of iodine, principally in the production of ani- 
 line dyes, caused sudden fluctuations in its price, while the price of the 
 raw material remained practically unchanged. This involved many 
 manufacturers in heavy losses, the profits under high prices usually 
 falling to speculators, while the manufacturer was left to sustain the 
 industry when prices were low. For this reason the number of manu- 
 facturers in Glasgow was reduced during 1873-1877 to about three, 
 producing in all from 50 to 60 tons of iodine from about 10.000 tons of 
 
856 MINERAL RESOURCES. 
 
 kelp. The production in Trance at this time was somewhat less, amount 
 ing to 40 tons, derived from 16,000 tons of inferior " varec " or kelp. 
 
 As early as 1885 the presence of sodium iodate was noticed in the 
 South American caliche (native sodium nitrate). The effort was made 
 by Thiercelin to extract the iodine from the mother liquors from sodium 
 nitrate by precipitating the iodine by means of acid sodium sulphite, 
 or, better, sodium nitrite, prepared by fusing the domestic sodium ni- 
 trate with one fifth its weight of charcoal. But the difficulty of drying 
 the iodine thus obtained by spreading on porous plates, and the fact 
 that frequently the greater part of the iodine existed as sodium iodide 
 and escaped precipitation, prevented active competition with European 
 iodine until Langbcin's method was introduced in the province of Tara- 
 paca, then belonging to Peru, but at present held by Chili. By this 
 method the mother liquors were treated with an excess of sodium sul- 
 phite or acid sodium sulphite, converting the iodate into hydriodic acid, 
 from which cuprous iodide was precipitated by copper sulphate and 
 sodium sulphite. In 1874 South American iodine was offered upon the 
 London market for 10J to 11 pence per ounce, against 13 pence for 
 Scotch iodine. The result was an active competition, soon resolving 
 into commercial warfare, which has exerted great influence upon the 
 industry. All through 1874 Peruvian iodine was offered at prices 
 about 20 per cent, btlow the Scotch product. At the beginning of 
 1875 both varieties sold for two-thirds the price of 1873, and the Pe- 
 ruvian iodine still led the way to lower^ prices, until at the close 
 of 1876 the price had fallen to 5f pence per ounce, and both sides 
 were ready to compromise or else give up the manufacture, which 
 now yielded little profit to either. In order to keep up the com- 
 petition the European method of producing iodine had undergone a 
 revolution. Formerly the custom was to allow seaweed to collect 
 during the winter months. It lay exposed upon the coasts until some- 
 times 90 per cent, of the iodine had been washed away from the 
 partially decomposed weed, before it was burned and shipped to Glas- 
 gow. Further, the weed was burned in long kilns made of loose 
 stone walls and turf; the burning seaweed here attained a very high 
 temperature. This part of the work was done by women and children ; 
 the men then raked the ash with iron " clats" until it formed a molten 
 slag. " During this laborious process," says Stanford, (i more than 50 
 per cent, of the iodine is often wasted, and a large amount of potash; 
 indeed, so intense is the heat that sufficient soda is volatilized to give 
 an intense monochromatic flame. The high temperature also enables 
 the carbon to deoxidize the alkaline sulphates to sulphides and other 
 sulphur compounds ; these become concentrated in the mother liquor, 
 and entail a large expenditure of oil of vitriol, and give rise to great 
 nuisance in the lixiviation." The first improvement, proposed in 1862, 
 was to subject the kelp to destructive distillation in closed vessels, by 
 which ammonia, acetic acid, naphtha, a considerable amount of illuminat- 
 
IODINE. 
 
 857 
 
 ing gas, and finally a variety of charcoal better than others for decolor- 
 izing, etc., were obtained. From this charcoal twice as much iodine 
 was obtained as from the kelp. This radical improvement was only 
 used on the islands of Tyree and North Uist until the competition with 
 Peru. The next improvement, proposed by Pellieux and Maze"-Launay, 
 consists in drying the fresh seaweed for four or five days, then allowing 
 it to ferment until decomposition begins. 'The object of the fermenta- 
 tion is to bring the seaweed into a condition in which no iodine will 
 be lost in burning. The sulphur compounds in the algae are converted 
 into alkaline sulphides; these decompose the organic iodine compounds 
 into alkaline iodides, which are not so easily volatilized. The water 
 formed during the fermentation is carefully saved on account of its 
 containing considerable iodine. The results of this process are very 
 satisfactory. The lixiviation of iodine from the kelp is double. First, 
 chlorides and iodides are extracted by cold water, then potassium sul- 
 phate by hot water. From the solution containing the iodides, iodine 
 is precipitated by potassium chlorate, which separates it from small 
 quantities of bromides. Before the end of the competition with Peru, 
 it is said that vessels were sent out to collect seaweed for this purpose 
 at times when the coast was bare. In March, 1877, a combination was 
 effected between the European and South American producers, and the 
 price set at 10J pence per ounce. This combination was of especial value 
 to the South American producers. It enabled them to erect new works 
 and gave an impetus to the trade which continued even after the com- 
 bination was broken in 1880. The price then fell to less than half, and 
 with continued competition had reached by November, 1884, 3J pence 
 per ounce, the same price which ruled in 1841, before iodine entered into 
 chemical manufactures. It was predicted in November that a combina- 
 tion would be formed and the price then go to 9 pence per ounce. The 
 prediction was fulfilled. 
 
 The yield from South American deposits has been estimated as 
 follows : 
 
 Years. 
 
 Pounds. 
 
 1873 ... 
 
 30 000 
 
 1874 
 
 100 000 
 
 1875 
 
 alOO 000 
 
 1876 
 
 110 000 
 
 1877 
 
 200 000 
 
 1878 
 
 280 000 
 
 1879 
 
 350, 000 
 
 1880 
 
 380 000 
 
 1881 
 
 200, 000 
 
 1882' 
 
 < 680, 000 
 
 1883 
 
 1 C32, 000 
 C 6124,544 
 
 
 I c30, 000 
 
 a From 131 manufactories. 6 Chili. c Pern. 
 
 The processes have been markedly improved both in the methods 
 and arrangement of the plant. The plant at Peruaua, province of 
 Tarapaca (formerly in Peru), erected in 1881, cost $20,000, and yields 
 
858 
 
 MINERAL RESOURCES. 
 
 3,200 pounds of iodine each month. The sodium nitrate at this place 
 contains sodium ioaate, which according to the Gtinie Civil, 1884, may 
 in extreme cases amount to 50 per cent. The average mother liquor 
 contains : 
 
 
 Per cent. 
 
 Sodium nitrate 
 
 28 
 
 Sodium chloride 
 
 11 
 
 Sodium sulphate 
 
 3 
 
 Magnesium sulphate 
 
 3 
 
 Sodium iodate 
 
 * 22 
 
 "Water 
 
 33 
 
 
 
 
 100 
 
 As the iodine is present largely as sodium iodate, it is precipitated by 
 the old method of sodium acid sulphite. Very new and economical 
 methods are used for preparing this substance, in regard to which full 
 plans are given in Dingler's Polytechnische Journal, Vol. 255, page 299. 
 In Chili much of the iodine occurs as sodium iodide, and is exported as 
 cuprous iodide ; 117,330 pounds of this substance were exported in 1883. 
 
 Imports. The following table shows the imports of iodine into the 
 United States from 1867 to 1884 inclusive. The principal use of iodine 
 in this country is for making alcoholic tincture and iodine salts, princi- 
 pally potassium iodide. 
 
 Iodine imported and entered for consumption in the United States, 1867 to 1884 inclusive. 
 
 Fiscal years ending June 
 30 
 
 Crude. 
 
 Eesublimed. 
 
 Iodine 
 salts. 
 
 Total 
 
 Quantity. 
 
 Value. 
 
 Quantity. 
 
 Value. 
 
 1867 
 
 Pounds. 
 12, 347 
 18, 994 
 17, 241 
 27, 825 
 74,320 
 81, 437 
 48, 991 
 23, 861 
 26, 058 
 24, 913 
 50, 123 
 73, 687 
 31, 779 
 104, 703 
 162, 863 
 . 119, 952 
 140, 642 
 153, 550 
 
 $28, 013 
 55, 869 
 50, 625 
 70, 777 
 212, 195 
 292, 998 
 206, 783 
 89, 305 
 74, 357 
 55, 443 
 111, 494 
 230, 041 
 122, 571 
 501, 957 
 336, 998 
 213,311 
 162, 036 
 173, 251 
 
 Pounds. 
 3,199 
 5,527 
 5,882 
 2,233 
 956 
 258 
 10 
 2 
 54 
 
 $6,764 
 16, 178 
 18, 356 
 6,251 
 3, 499 
 2,166 
 87 
 16 
 171 
 
 
 $34, 777 
 72, 047 
 72, 570 
 77, 028 
 215, 694 
 295, 205 
 206, 870 
 89, 321 
 74, 531 
 55,443 
 111,494 
 230, 053 
 122, 571 
 501, 969 
 337, 676 
 214, 605 
 168, 016 
 173, 744 
 
 1868 
 
 
 1869 
 
 $3, 589 
 
 1870 
 
 1871 
 
 41 
 
 1872 
 
 1873 
 
 1874 
 
 
 1875 
 
 3 
 
 1876 .... 
 
 1877 
 
 
 
 
 1878 
 
 
 
 12 
 
 1879 
 
 
 
 1880 
 
 2 
 13 
 15 
 5 
 336 
 
 12 
 30 
 28 
 8 
 493 
 
 
 1881 
 
 648 
 1,266 
 5,972 
 (a) 
 
 1882 
 
 1883 
 
 1884 
 
 
 a Not specified.