,Oct., 1 9 1 8
T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y
The great mass of water-soluble dyestuffs contain moisture, partly loosely bound, and partly, and that I believe is the general rule, in the form of water of crystallization. It is interesting to observe the great tenacity with which even great quantities of water are retained by certain dyestuffs. This explains why the ordinary practice of drying organic compounds in a desiccator over sulfuric acid gives altogether too low figures for moisture when applied to dyestuffs. A sample of Wool Red 40 F lost in desiccator during 3 days z per cent in weight, while the same sample on drying to constant weight in an air oven a t 125’ C. showed a loss of I Z per cent. This could be illustrated by a great many examples. For purposes of determining the moisture content it generally suffices to place the dyestuff in an air oven held a t 125’ C., until constant weight is observed. The temperature of 125 C., or even higher, is generally tolerated by a dyestuff without any evidence of decomposition. It has been recommended to place the dyestuff for moisture determination in a tube through which a current of hydrogen or carbon dioxide is conducted while the tube is maintained a t a constant temperature by being surrounded by vapors of a suitable liquid, for example, boiling toluol. These precautions are as a rule quite unnecessary except when dealing with easily oxidized dyestuffs. O
DETERMINATION OF SODIUM CHLORIDE
When the dyestuff does not contain any halogen in the molecule or when it is not a hydrochloride, as in the case of basic colors, the salt determination is a simple matter. The general procedure is to mix the dyestuff intimately with from 5 to I O times its weight of C.P. anhydrous sodium carbonate and heat this mixture in an iron crucible gradually to a dull red heat turning the mass over occasionally with a steel spatula until complete charring or partial combustion has taken place. The crucible content is, after cooling, mixed intimately with pure potassium nitrate in the proper ratio to insure an easy flux and the placed in the crucible again, urhere it is cautiously heated until complete oxidation and fusion have taken place. The crucible content is then taken up with water, filtered, acidulated with nitric acid, and the sodium &loride determined in the usual manner with silver nitrate. When halogen is present in the molecule it must be determined separately and the sodium chloride calculated by difference. In the case of basic dyes like Methylene Blue or Safranine, I believe a direct titration of the dyestuff by means of a standard solution of an acid dyestuff, for example, Naphthol YeIlow according to Knecht or by titanous chloride according to Knecht and Hibbert would be advisable. The titanous chloride titration is altogether very satisfactory for a great many simple dyestuffs, but fails in the case of more complex azo dyes.
DETERMINATION OF SULFATE OF SODA
This is not as simple as the salt determination and calls for greater ingenuity. Sometimes a direct precipitation in the acidulated solution of the dyestuff gives a fairly pure barium sulfate. As, however, a great many dyestuffs form hard soluble barium salts, the precipitated barium sulfate is often more or less colored. This can be corrected by washing the precipitate with warm ammonium carbonate whereby the color lake is decomposed into the ammonium salt of the dye which passes through the filter and barium carbonate which can be removed by dilute acid. When the direct precipitation with barium chloride fails, it sometimes is a good plan to precipitate the dyestuff from its aqueous solution as thoroughly as possible with salt and determine the sulfate in the filtrate with eventual after-treatment with ammonium carbonate. In some cases when the dyestuff cannot be “salted out,” advantage can be taken of the fact that acid and basic dyestuff mutually precipitate one another. If, for example, the problem is to determine the amount of sulfate in Patent Blue or Acid Green a solution of a suitable basic color free from sulfates can be added to the solution of the acid color until a drop of the mixture placed on filter paper shows excess of the basic color. The condensation product is then filtered off and the barium sulfate precipitated in the filtrate. As a suitable basic color I prefer Chrysoidine, because it can be easily prepared free from sulfates. By these various methods a determination of the sulfate of soda present in the dyestuff can be secured without a very high degree of accuracy. DETERMINATION OF SULPUR AND SODIUM OR POTASSIUM
When the sulfate has been determined it is often of interest to determine the total sulfur present, including that residing in sulfonic acid groups. The fusion of ‘/z g. or less of the dyestuff with soda and niter is generally more satisfactory than the classical heating in a sealed tube with nitric acid according to Carius. The amount of sodium or potassium present in a dyestuff is easily found by moistening a small quantity of the sample in a porcelain or platinum dish, driving the sulfuric acid off by heating the crucible, and repeating this process until a perfectly white ash remains. This is then heated to a dull red heat and weighed as sodium sulfate. After the chemist has made the series of quantitative determinations mentioned it should be possible by piecing them together to form a correct picture of the true composition of the dyestuff before him.
CHEMICAL MARKETS OF SOUTH AMERICA B y 0.P.
805
I
YOPKINS, Washington, D. C.
CHEMICAL TRADE OF CHILE, PERU, AND BOLIVIA Received August 27, 1918
T h e prosperity of Chile, Peru, and Bolivia depends primarily upon t h e output of minerals, and in this respect t h e group differs radically from Argentina, Brazil, and Uruguay, which were examined i n connection with t h e t r a d e i n chemicals i n t h e September number of THIS J O U R N A L . Sodium nitrate, copper, a n d tin are supplied b y this group in enormous quantities a n d t h e value of these materials t o t h e war industries of t h e belligerent countries is so great that t h e exporting countries have for t h e past t w o years been enjoying a prosperity t h a t has transformed their whole economic life.
These countries are not, however, heavy importers of industrial chemicals. T h e market a t present is confined largely t o such articles as perfumery, medicines, paper, soap, a n d glass, a n d American manufacturers have succeeded i n increasing their sales of these lines as t h e result of t h e shutting off of European supplies. T h e opportunity of t h e future lies i n maintaining t h e advantage t h u s gained and developing t h e trade still further. As i n t h e previous review, there is a table showing t h e imports of each country, compiled from t h e original Spanish statistics, and more detailed tables showing t h e trade with t h e United States, based upon statistics published b y t h e United States Bureau of Foreign and Domestic Commerce.
T H E J O U R N A L O F I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Vol .
8 06
CHILE
The nitrate beds are the chief source of Chile’s prosperity. affording t h e country one of t h e most valuable natural monopolies in the world . Copper has also come into its own again as a result of war demands and is exported in great quantities . Agriculture a n d stockraising are second in importance only t o mining. a n d in recent years manufacturing has been developed rapidly. thanks t o plentiful supplies of iron. coal. and timber. efficient labor. and ample water power I t is safe t o assume t h a t Chile will consume increasingly great quantities of industrial chemicals. although it is a t present difficult t o estimate what proportion will be imported . American goods in general are highly esteemed. b u t have not been pushed so energetically as have the goods from certain other countries . Over $3.000. 000 worth of chemicals. pharmaceutical products. and perfumery was imported in 1913. and of t h a t total Germany furnished more t h a n a third. or more t h a n twice t h e amount supplied by t h e United Germany also had a n advantage in dyes. States paints. and inks. a n d maintained a striking superiority in paper and paper products . T h e United States supplied t h e bulk of t h e mineral oils . T h e statistics in t h e following table are based upon official Chilean figures for the calendar years 1913 a n d 1915 . t h e last normal a n d latest available war years. a n d serve principally t o show the extent of t h e market before t h e war and t h e manner in which i t was divided among t h e principal competing countries . The year 1915 shows a falling off all around from t h e normal year. as the country had not recovered from t h e depression and dislocation of trade t h a t followed t h e outbreak of hostilities . Since t h a t time t h e great demand for Chile’s minerals has brought in an era of prosperity t h a t has never been equaled in the history of t h e country.
.
.
CHILEAN IMPORTS OF CHEMICALSAND ALLIED PRODUCTS ARTICLES 1913 1915 . PRODUCTS . . . . .,._ CHEMICALSPHARMACEUTICAL . PERFUMERY $1,015, 861 $ 623, 200 Chemicals 1,688, 444 810, 782 Pharmaceutical products 336.740 125.093 Perfumery
.
................................ ................... ................................ TOTAL ................................. Germany ............................... United States........................... PAINTS. DYES. INKS......................... Germany ............................... United Kingdom ........................ United States ........................... EXPLOSIVES ................................. Germany ............................... United Kingdom ........................ United States ........................... VARNISHES ................................. United Kingdom ........................ United States ........................... INDUSTRIAL OILS............................ Germany ............................... United Kingdom ........................ United States ........................... CRUDEPETROLEUM .......................... United States ........................... NAPHTHA PETROLEUM. GASOLINE KEROSENE PARAFFIN. FOR INDUSTRIAL PUR~OSE ....... S United States ........................... PARAFFIN WAX............................. Germany ............................... United States ...........................
..................... ................................ ..‘. ........................ ... ............................... ...........................
SHEET AND PLATEGLASS
Belgium United States PAPER. CARDBOARD. AND MANUFACTURES OF Germany United States
3.041. 045 1.559. 075 1.044. 837 132. 292 492. 270 627. 347 763. 412 264. 009 326. 980 33. 508 285. 500 135. 630 85.687 77.978 922. 954 563. 841 180.482 14. 471 346. 010 148. 282 235. 932 390. 682 171.301 . 81. 182 62. 017 47. 190 52. 700 25. 357 1.079. 3 10 523. 830 166. 195 31. 463 439. 305 122. 616 456. 088 358. 988 4.405. 727 3,712.768 3.500. 395 2.640. 056
..
1.078. 253 1.061. 825 558.657 302. 887 143. 643 272. 880 151. 386 I . 030 3.581. 027 1,959.087 463. 573
~
633. 288 620. 592 612. 873 8.354 560. 329 72. 782 6. 347 42. 555 1.905. 781 241. 419 413. 164
No . I O
IO.
The extent t o which t h e present prosperity of t h e country has reacted upon the purchases of chemicals a n d allied products from the United States can be readily traced in the next table. in which gratifying gains are indicated for almost every item . T h e sales of American chemicals. drugs. and perfumery in t h e fiscal year 1 9 1 7easily surpass t h e German total previous ooo worth of business is t o t h e war . Over $1.000. noted for t h e “All other” group alone. and i t is regrettable t h a t further details are not available as t o t h e articles included in t h a t classification . The substantial gain in the imports of American dyes is an interesting a n d encouraging feature. as is t h e gain in receipts of American paper Certainly it should be possible t o retain much of this t r a d e when the war is over . ’ Details of the imports from the United States are shown in the following table. which is based upon o f i cia1 Americanstatisticsforthefiscalyears 1 9 1 4and 1917:
.
AMERICANPRODUCTS S O L D I N CHILE 1914 ARTICLES Aluminum and manufactures $ I . 938 Asphaltum and manufactures 50. 347 11. 231 Babbitt metal Blacking shoe paste etc 18. 506 117 Celluloid’and manuiactures 35. io; Cement. hydraulic Chemicals. drugs. dyes. etc Acids: 48. 277 Sulfuric 3. 415 All other IO. 663 Baking powder 25 1 Bark extract for tanning Calcium carbide 72. 289 1. 385 Copper sulfate 893 Dyes and dyestuffs Medicines. patent and proprietary 200. 918 840 Petroleum jelly. etc 77 Roots. herbs. barks Soda salts and preparations All other 68. 365 58 Clay. fire Explosives: 45. 220 Cartridges. loaded 107. 087 Dynamite 5. 270 Gunpowder 15. 134 Allother 40. 224 Glass and glassware 14. 808 Glucose Grease: Lubricating 78. 326 1.882 Soap stocks. and other India-rubber manufactures 139.256 .... Ink 121408 Leather patent 56;305 Metal iolish 68. 2 , 028 897 Naval stores Oilcloth and linoleum: 1.117 For floors All other 9. 855
................. ................. .............................. ..................... .................. .......................... . ................................ ............................... ............................ ................... ........................... ............................ ......................... ........... ........................ ........................ ................. ................................. ................................ . ......................... ................................ ............................... ................................. ......................... .................................... ............................... ..................... .................. ........................................ ............................. ................................ ................................ .................... ..................... nil-..... Animal ........ ............. Mineral : Crude ................................. Gas and fuel ............................ Illuminating ............................ Lubricating. etc ......................... Gasoline ................................ Other light .............................
.
.
......
$
1917 17.197 30. 090 61. 936 51. 145 8.285 112. 397 37. 827 71. 869 25. 674 21. 963 78. 296 38. 828 110. 644 305.611 20. 320 22. 014 21 1 . 691 1.038. 531 9. 340
74. 861 968. 765 10. 266 1.192. 023 290. 753 18. 182 121. 209 36. 184 714.571 391781 313.639 164. 4 . 848 136
.
. . . . . .
Vegetable : Cottonseed Linseed Other fixed Volatile Paints. pigments. etc Dry colors Ready-mixed paints Varnishes White lead Zinc oxide All other (including crayons) Paper and manufactures Paraffin and wax Paste Perfumery. cosmetics. etc. Photographic goods: Moton-picture films Other sensitized goods Plumbago and manufactures uicksilver
............................. ................................ ..............................
.
................................ . ................................ ....................... ................................ ............................... ................................ ............... ..................... ............................ ...................................... ................... ....................... ..................... .................. ................................. .................................... Allother ................................. Sugar. refined ............................... Wax. manufactures of........................
17. 322 37.438
2 872
6 . 291
118.500 1 .365. 661 1 .028. 155 418. 279 166. 724 12. 412
67. 224 2.826. 963 399. 860 561. 225 97.955 462. 703
436. 672 2 . 598 11. 982 217
257. 948 31. 197 148. 343 14. 386
64 26. 829 IO. 712 725
27. 982 55.912 23. 520 14. 108 5. 632 1.188. 102. 737 139
~
......
22. 763 233. 603 92. 098 203 25. 437
577. 644 3. 599 51.844
5.268 18. 213 2. 297
......
13.904 46. 902 27.295 409
91. 330 16. 290 687 1. 145
127. 790 2 7 . 560 9 . 618 6. 687
Oct., 19x8
T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
Chile sent t o t h e United States about $45,ooo,ooo worth of sodium nitrate and a n equal amount of copper in 1917,and it would be a difficult matter t o overestimate t h e vital importance of these two materials t o the cause of the Allies. T h e $4,000,000 worth of iodine was another valuable contribution, as was the $z,ooo,c~oo worth of tungsten ore. T h e shipments of t i n ore and bismuth are t o be credited t o Bolivia, however, as they merely pass through Chile. The importance of Chile as a reservoir of war materials is made clear in t h e following table, which is based upon American statistics for the fiscal years 1914 a n d 1917: CHILEAN PRODUCTS SOLD I N THE UNITED STATES ARTICLES 1914 1917 Antimony ore... $ 8 $ 461,462 Bismuth 11,627 Bones, hoofs, horns.. 13,040 Chemicals, drugs, dyes, etc.: Argols 108,160 433.293 4.380.818 Iodine. crude or resublimed.. Potash: Nitrate. 77.720 Salts of.. 18i7.51 Soda, nitrate. 17,808,763 44,231,240 51,279 Allother Copper: Ore 1,974,429 4,840,321 Cohcenixates 40,764 2,645,973 M a t t e and regulus.. 2,004.898 35,779,947 Unrefined, black, etc. 2.501.685 Refined. in bars. etc.. 2.145.748 . . Glue and glue size’ 607 . 67;810 Hide cuttings, raw.. 3,841 India rubber, unmanufactured.. 392,624 Iron ore... 7,829 50,145 91,994 178.503 Lead ore Paper and products.., 7,640 Platinum.. 62,981 Tanning materials: Quebracho wood.. 37,445 Tin: Ore.... 2,708,373 Bars etc. 24,401 Tungsten-bearing ore. 2,013,411 Wax: Beeswax 36,975 157,212 Vegetable 8,063 Zinc, pigs. 485
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PERU
Mining a n d agriculture are t h e chief industries of Peru. T h e mineral resources are varied and extensive, including copper, gold, silver, lead, quicksilver, coal, bismuth, vanadium, tungsten, nickel, iron, sulfur, antimony, petroleum, salt, zinc, borax, cobalt, gypsum, asbestos, ocher, kaolin, molybdenite, manganese, magnesia, mica, peat, a n d various marbles. Copper is extensively worked a t present, with American capital heavily interested, b u t the silver output is also important, as i t has been since t h e sixteenth century. Few of t h e other minerals are produced in anything like important quantities, so t h a t i t can be safely said t h a t even today the mineral industry is only in its infancy. Considering the proportion of t h e country t h a t is either mountainous or desert, agriculture is surprisingly well developed, the principal products being sugar cane, cotton, coca, rice, and grapes. T h e total value of the crops of the country can be placed somewhere between 40 and 50 million dollars. T h e manufacturing industries are not well developed, although the output of the sugar mills is now considerable a n d the domestic supplies of cotton and wool have led t o t h e development of a prosperous textile industry. Industrial chemicals are not required in large quantities, but there is a steady demand for many of t h e finer chemicals. I n 1913 t h e imports of chemicals, drugs, medicines, and pharmaceutical supplies
807
amounted t o slightly more t h a n $I,OOO,OOO, which was divided fairly evenly among American, German, French, and English manufacturers, the Americans leading with $z91,000. I n 1916 the imports were of which American manufacturers nearly $I,~OO,OOO, furnished very nearly $I,ooo,ooo worth. American goods have always been in good demand in Peru, a circumstance t h a t is usually explained as being a natural consequence of extensive investments of American capital in t h e mining industries of t h e country. As will be seen in t h e following table, which is a compilation from official Peruvian statistics, none of the articles usually classed as chemicals is imported t o the extent of $ ~ O O , O O O annually; in fact, patent medicines are the only item exceeding $300,000 in value. It will be noticed, however, t h a t the American share of the imports has been substantially increased as a result of war conditions and there is no convincing reason why this business should not be retained and expanded when normal conditions are restored. Of t h e classes of goods t h a t can be considered as allied chemical products, “colors, paints, varnishes, oils, a n d gums” were imported in 1916 t o t h e extent of more t h a n $z,ooo,ooo, t h e United States having almost a monopoly of t h e trade. Mineral oils are t h e most important item in this group. Explosives a n d paper are both important, American manufacturers now dominating the market. The table is based on statistics for t h e calendar years 1913 and 1916, the last normal year and t h e latest available war year. These figures should be used only as a general guide in estimating t h e extent of the markets and t h e relative share of t h e principal competing countries in t h e trade. PERUVIANIMPORTS OF CHEMICALS AND ALLIED PRODUCTS ARTICLES 1913 1916 CHEMICALS, DRUGS,ETC. Acids: $3 60,103 Sulfuric $ ,5,;g; United Kingdom.. 20 60,083 United States 2,209 10,673 13,962 Tartaric. Germany 5,261 United States.. 31 6,942 Disinfectants, prepared. 24,536 35,715 3,205 Germany. United States.. 18,205 35,355 6 029 7,135 Glycerin. 2:468 260 United Kingdom.. 64 6,255 United States 348,950 327,343 Medicines, proprietary.. 108,037 54,763 France 162,078 236.749 United States.. 21,180 4,547 Methyl alcohol.. 21,180 Germany.. 4,544 Unitekl Kingdom.. 131,437 90,747 Quinine.. 49,790 8.972 France 2.229 34.008 United States 20,295 28.477 Soda ash 17,378 13,071 United Kingdom.. 1,165 15,263 United States 50,566 12,080 Soda, bicarbonate of... 2,551 6,159 United Kingdom.. 5,084 24,839 United States 36,608 67,629 Soda, caustic 25,980 8,319 United Kingdom.. 9.266 59.247 United States... 19,434 49,070 Sulfur., 10,740 12,635 Italy.. 29,855 .’ 292 United States 1,772,828 2,198,913 COLORS,PAINTS,VARNISHES,OILS, AND GUMS.. 420,371 820 Germany.. 277,591 301,602 United Kingdom.. 1,770,555 894,878 United States
.
................................ .................... ......................... ............................... ............................. ...................... ................... .............................. ......................... ................................ ...................... ........................... ................... ................................. ........................ ......................... ............................. ...................... ................................ ................................. ........................... ................................. ...................... ........................... .................... ...................... ........................... ............................. ...................... ........................ .................................. ................................. ........................... ............................. ...................... ...........................
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80 8
T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Vol.
PERUVIAN IMPORTS, ETC. (Concluded) ARTICLES 19 13 1916 $ 516,851 $ 938,582 EXPLOSIVES 886,390 United States,.. 201,221 325,512 755,816 Dynamite, e t c . . 160,317 755,816 United States,.. PAPER, CARDBOARD A N D OFFICESUPPLIES Total imports 914,862 1,312,900 France 54,044 74,980 Germany.. 403,723 10,000 United Kingdom.. 104,637 127,823 United States.. 234,000 787,851 Newsprint paper.. 189,386 307,641 Germany., 128,355 900 Norwav.. 5,621 Sweden 5 6 ; 894 United States 120; 490 78,897 Book and lithographic paper.. 749 33,734 Germany.. 23,790 15,964 United Kingdom.. 90,268 10,618 United States. SHEBT AND PLATEGLASS 28,781 53,889 Belgium.. 24,956 United Kingdom.. 1,158 4,542 199 47,025 United States...
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The character of chemicals and allied products sold in Peruvian markets by American manufacturers can be determined accurately from t h e following table, which is based upon official American statistics for the fiscal years 1914and 1917: AMERICANPRODUCTS SOLD IN PERU 1917 1914 ARTICLES $ 17,605 Aluminum and manufactures.. 13,500 fl 4;,: Babbitt metal.. 19.896 4,526 Blacking, shoe paste, etc. 3,329 275 Candles 8,434 121 Celluloid and manufactures.. 109.902 125.367 Cement, hydraulic Chemicals, drugs, dyes, etc.: Acids: 21,274 4,679 Sulfuric. 103 31,729 All other 3,604 1,420 Baking powd er... 19,364 22,787 Calcium carbide.. 4,523 Copper sulfate 94.775 2,635 Dyes and dyestuffs.. 245,373 197,320 Medicines, ,patent and proprietary.. 245 7,497 Petroleum jelly, etc.. 5,317 Roots, herbs, barks.. 80,892 Soda salts and preparations.. 377,924 81,132 All other.. 143 5,475 Chewing gum Explosives : 17,508 47,577 Cartridges, loaded.. . . . 219,721 56,284 Dynamite. 45,925 Gunpowder.. 382,487 26,221 Allother 7,738 34 Flavoring extracts and fruit juices.. 156,485 18,986 Glass and glassware.. 3,347 468 Glue
................... .................................
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................................... ................................... ............................. ............................. ................................
.......................... ............. .......................... .......................... ................... .................................... ................................... .................... ................................... ................................. ..................................... ............... ........................... ........................................... ............................ .. ............ res ....................... Ink ............................................ Leather, patent. ................................ Lime ................................... Nava
....
.... ....
....
24,351 3,372 44 155 3:614 17,963
....
17,912 9,773 156,593 23,427 100,962 3,183
....................................... .......................... ...........................
22,795 495 17,966 1,726
34,257 4,807 32,923 17,535
..................................... ..................... ..................... ...................................
136
2,417
73;ji7 67,939 262,121
89,563 13,427 144,283 565
458 948 2,006 253
8,042 26,318 28,753 3,176
5,511 12,355
11,670 19.384 2;096 53,060 681,111 255,178 108,710
Rosin. Tar turpentine, pitch Turpentine, spirits.. Oilcloth and linoleum Oils: Animal.. Mineral: Gas and fuel Illuminating Lubricating, Allother Vegetable: Cottonseed. ................................ Linseed. , Other fixe Volatile. .............. Paints, pigments, etc.: Dry colors ........... .......... Ready-mixed paints. . .......... Zinc oxide.. . . . . . . . . . . . All dther (including crayo Paper and manufactures .... Paraffin and paraffin wax... Perfumery, cosmetics, etc. ....................... Photographic goods: Exposed motion-picture films. Other sensitized goods.. .... Plumbago and manufactures ......
.... ....
......................
.. .......
....
....
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So%et.. Allother. .................................... Stearin, vegetable. .............................. Sugar and molasses. Wax and manufactures.. ........................
.............................
....
2,189 80,745 22,745 44,791
....
7 * 773 19,682 16,822
6,868 15,069
85,555 13,408 4,752 109,489 5,458
12,324 477
....
12
855
IO,
No.
IO
Copper is easily t h e most important of t h e materials now shipped t o the United States by Peru, as t h e next table shows, t h e exports having been greatly stimulated by the war. Other important items are cane sugar, mineral oil, tungsten ore, and India rubber. The tin originates in Bolivia. The following table is compiled from American statistics for the fiscal years 1914 and 1917: PERUVIAN PRODUCTS SOLD IN THE UNITED STATES ARTICLES 1914 1917 Antimonyore ............................... $4 $ 5,378 Chemicals, drugs, dyes, etc.: Colors or dyes.. 6 456 2,930 Glycerin, crude. Soda, cyanide ............................. ...... 2,190 Copper: Ore..... 751,582 833,085 Concentrates. ...... . 60,778 Matte, regulus, e t c . . . 866 211 306 939 Unrefined, in bars, e t c . . . . . . . . . . . . . . . . . . . . . 6,597:499 20,684: 121 India rubber, etc.: Balata 4,400 Gutta-percha, ............................ ...... 1,275 India rubber.. ............................ 427,002 1,227 776 Lead.. ..................................... ...... 44:717 Oils: Crude mineral.. .......................... 506,535 261,039 Refined mineral: Benzine, gasoline . n a p h t h a . . . . . . . . . . . . . . . 867,020 1,395,453 ....................... ...... 146,514 All other.. 181,519 3,576,707 Sugar, cane.. . . . . . . . ........................ Tin: .. 18,115 Ore ................................ Bars, e t c . . ............................... 6.6 88 . . . . . . 1,073,001 Tungsten-bearing ore. ....................... Wax: Beeswax. ............................. 5,411 2,720 Zinc
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....................................... BOLIVIA
Bolivia's wealth lies in mineral deposits, and it is estimated t h a t more t h a n $ 2 , 0 0 0 , 0 0 0 , 0 0 0 worth of metals have been taken from t h e country since t h e coming of the Spaniards in the sixteenth century. Gold a n d silver were formerly recovered in immense quantities, but of t h e total mineral production of $ 2 7 , 0 0 0 , 0 0 0 in 1912, over $ 2 3 , 0 0 0 , 0 0 0 was tin. The silver output t h e same year was something more t h a n a million a n d a half, while the gold production was practically nil. Nearly $I,OOO,OOO worth of bismuth was recovered. which represents a large part of t h e world's production, As a source of t i n Bolivia is now second t o the Malay peninsula. The immense forests have not been exploited nor has agriculture been developed, although there are unlimited possibilities in t h a t direction. Aside from the reduction of t i n ore there is very little activity t h a t can be classed as manufacturing. Naturally there is little demand for chemicals or chemical products, but such imports as were recorded by the Government for I913 and 1915 are shown in t h e following table. There seems t o be little possibility of developing a trade in these lines in the near future. BOLIVIANIMPORTS OF CHEMICALS AND ALLIED PRODUCTS ARTICLES 1913 1915 $ 49,830 $ 5,273 CHEMICALPRODUCTS.. ........................... 19,356 232 Germany ............................ .:. 4,876 3,295 United States ................................. 162,704 88,075 PREPARED MEDICINES........................... 52,982 4,391 Germany.. ................................... 27,816 19,340 United States.. ............................... PERFUMERY AND COSMETICS.. .................... 58,295 12,735 Germany.. 390 17,291 United States,. ................................ 13,922 2,164 95,133 109.687 S O A P S . ................................... 61,737 55,373 United Kingdom.. ...................... 5,844 4,814 United States ........................... 20 870 127,619 PAINTS, DYES, VARNISHES,. ...................... 2 ' 847 61,811 Germany.. 2: 665 6.272 United States 312,090 446; 316 EXPLOSIVES .................................... 329 362,705 Germany.. 143,130 5,143 United States ~~
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THE JOURNAL OF INDVSTRIAL A N D ENGINEERING CHEMISTRY
Oct., 1918
BOLIVIANIMPORTS, ETC.(Concluded) ARTICLES 1913 I915 MINERALOILS AND THEIRDERIVATIVES.. . . . . . . . . . $ 86,403 $234,630 20,533 7,288 Germany 21,116 118,683 United States VEGETABLE OILS, EDIBLE.. 14,124 17,870 Italy 4,536 6,590 United States 521 4,048 OILS, OTHER.. 47,232 8,456 Germany ...................................... 14,823 48 11,146 6.254 United States.. SHEETAND F'LATE GLASS.. 46,664 18,337 Germany. 21,078 121 United States 5.129 9.437 GLASSWARE.. 103,845 2 1 , 518 Germany 53,500 3,232 United States 6,576 6,261 PAPER AND CARDBOARD (EXCEPT WALL PAPER). . . . . 167,391 91,012 Germany 70,353 6,598 United States.. 15.742 28.790 MANUFACTURE OF PAPER(EXCEPT BOOKS)... . . . . . . . 31,914 14,138 Germany 15,562 1,629 United States.. 414 1,516
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How the war has affected what little trade American manufacturers have with Bolivia can be ascertained from t h e following table, which is compiled from American statistics for the fiscal years 1914 and 1917: AMERICANPRODUCTS SOLDIN BOLIVIA ARTICLES 1914 1917 Blacking, shoe paste, etc. $ 1,136 $ 4,642 Candles .......................................... 3,841 Cement, hydraulic.. Chemicals, drugs, dyes, etc.: Acids 119 4,423 Calcium carbide.. 573 23,792 13,;;; Medicines, patent and proprietary . . . . . . . . . . . . . . . . . Soda salts and preparations.. 4.;t)i) Allother Explosives : 6,622 23,768 Cartridges, loaded Dynamite. ................................... 72,044 Gunpowder.. 12,556 .............................. 26 42,217 All other..
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2:;i$i
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809
AMERICAN PRODUCTS S O L D I N BOLIVIA(Concluded) 1917 ARTICLES 1914 Glass and glassware. .............................. $ 7,895 $19,469 Grease, lubricating.. .............................. 5,464 1,933 India-rubber manufactures. ........................ 31,618 5,024 Leather, patent.. ................................. 1,475 Oils: Refined mineral: Gasoline, etc.. ................................ 1,998 4,494 Illuminating.. ................................ 22,199 16,647 36,026 20,583 Lubricating, etc.. ............................. Naphthas, etc.. ............................... 1,998 59,797 Veeetable : 6,123 Cottonseed, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 2,353 Linseed ........................ ............. 233 6,862 187 Allother ..................................... Paints pigments etc.: Ready-mixed i a i n t s . . ........................... 2,647 1,236 White lead.. ...................... 23,688 7,095 ........... 66,405 ........................... 83,227 85,045 ........................... 720 3,685 1,830 Perfumeries, cosmetics, etc . . . . . . . . . . . .
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(.
Sugar, refined
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7,050 330 6
15,914 5,781 817
The statistics supplied by our own Government do not show many imports from Bolivia, as shipments are made from the Pacific and Atlantic ports of neighboring countries and consequently credited t o them. Of t h e nearly $3,000,000 worth of t i n ore imported into t h e united States during h + e. fiscal year 191,, practically all was credited t o Chile in our statistics. Such imports jumped t o $IO,OOO,OOO in 1918. Imports of bismuth were valued a t $196,000 in 19x7, of which $32,000 worth is credited t o Argentina, Chile, and Uruguay, and is obviously of Bolivian origin. The preliminary statistics for the fiscal year 1918 do not show imports of bismuth.
ORIGINAL PAPERS VALUATION OF RAW SUGARS BY W. D. HORNE
I n the sugar trade it has long been customary t o buy and sell raw sugars on their polarization, adopting usually a baeis of 96' for centrifugal sugars and 89' for muscovado and molasses sugars. For every degree above the basis a certain additional increase is paid, while for each degree below the basis a double deduction is made. This system, while based on practical considerations a n d having much t o recommend i t , is still far from satisfactory, because it does not take sufficient account of the many influences on refining of sugars introduced b y their endless variations. Efforts have therefore been made in recent years t o attempt a rough standardization of raw sugars on t h e part of some of the advanced manufacturers. Such methods consist of grading the sugars according t o the size of grain, hardness of grain, cleanliness of solution, odor, and reaction, as well as polarization and moisture, with perhaps some other determinations. Admirable as these efforts are, they still fall far short of what is desired, for they are based on assumptions which frequently are not borne out in practice and entirely overlook many important varia1 Read before the Division of Industrial Chemists and Chemical Engineers, 56th Meeting of the American Chemical Society, September 10 to 13, 1918.
tions in raw sugars which radically affect their value for refining purposes. It is the object of this paper t o direct attention t o the practical considerations involved in valuation of raw sugars for refining purposes a n d t o suggest some amplifications of the tests applied, with the .hope t h a t i t may lead to a full discussion of the subject and in the belief t h a t closer attention t o the points involved must inevitably lead t o greater efficiency of manufacture with a consequent decrease' of wasteful operation in both manufacture and refining. The refining value of a raw sugar depends upon its content of sucrose and the availability of t h a t sucrose, as modified by the nature and quantity of the impurities. The nature of the impurities will determine the ease of their separation from the sucrose during refining. Refining consists principally of ( I ) affination or washing the residual mother liquor of the raw sugar niassecuite from the solid grain of the sugar; ( 2 ) defecation and filtration, t o remove insoluble substances a n d some soluble impurities from the solution of the washed sugar or from the dilute washings; (3) decolorization boneblack or other means; (4) crystallization and separation of pure sugar from t h e other constituents. The response of any raw sugars t o tests for the first three of these operations can be determined readily
