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loses i t s brilliancy t o a considerable extent, although i t does not. become much lighter in color. T h e dyeings b y aluminum a n d tin mordants are decidedly changed b y this exposure t o light a n d weather. T h e dyeings b y chromium a n d iron mordants are sufficiently fast t o prove of practical value, assuming t h a t t h e coloring m a t t e r could be prepared cheap enough.” SZTMNARY A i i D C O X C L U S I O h - S
I-The q u a n t i t y a n d quality of t h e dyestuff present in Osage orange is almost identical with t h a t of fustic. 11-Osage orange m a y be employed as a dyewood in all cases where fustic wood is used at present. T h e yellows produced b y direct dyeing or b y aluminum a n d t i n mordants are too fugitive t o be of commercial value. B u t t h e orange-yellows, old gold, deep t a n , olive a n d chocolate shades obtained with chromium a n d iron mordants are equal to, if not better t h a n , those obtained with fustic a n d are of sufficient fastness t o be of commercial value. 111-A domestic source of a yellow dyemood has been found t h a t can advantageously replace a foreign material used a t present. The mill waste alone from t h e present manufacture of Osage orange amounts t o over 2 5 , 0 0 0 tons annually; a n d if this waste could be set down in t h e E a s t for $10 t o $12 per t o n i t is believed t h a t i t could compete successfully with fustic, b o t h from cost of production a n d quality of color produced on dyeing. PUREST PRODUCTS LABORATORY F O R B SERVICE, ~T u. s. 1)EPARTMEKT O F AGRIWLTURE iIii Cooperation n i t h the Cnirersity of Wisconsin1 I\IAnIsoN
A.4-D E S G I S E E R I S G C H E M I S T R Y
1-01. 6 No. 6
For some time i t has been obviously desirable t h a t both producer and consumer should have some idea (even though a rough one) of t h e amount of phosphate rock still unmined in t h e United States. Again and again disquieting reports have been spread t h a t our supplies of this mineral) so important t o t h e American farmer, were being rapidly depleted, a n d t h a t thereby t h e agricultural interests of this country would soon be seriously impaired. Alarm has also been caused by t h e fact t h a t several phosphate companies are on-ned b y European capitalists, a n d fears have been expressed t h a t foreign capital is seeking t o acquire control of t h e American deposits. I t has been urged even t h a t some legislation be enacted preventing t h e exportation of phosphate rock. I n order t o shon- t h e actual basis for such reports a n d whether or not there is a n y real need for curtailing foreign shipments of phosphates, t h e d a t a herein contained were collected a n d compiled with considerable care. The figures were obtained by correspondence a n d consultation with mine owners a n d operators, a n d b y direct obserl-ation a n d field investigations of t h e various deposits throughout t h e country. So little development work has been done in Kentucky a n d Arkansas t h a t t h e tonnages given for these states are thought not t o be close; t h e y are regarded, however, as ultra-conservative. T h e estimates given below are for rock grading from j S t o 78 per cent “bone phosphate of lime.” In t h e case of t h e lom-grade phosphate in t h e West and t h e mash heaps of Florida, t h e material is figured t o its equiralent in high-grade rock. TOE
THE RESERVE SUPPLY OF PHOSPHATE ROCK IN THE UNITED STATES B y W. E. W A G G A M A N ~ Received March 20. 1914
Xumerous estimates have been made from time t o time on t h e tonnage of phosphate rock available for f u t u r e use in this country. These estimates vary so widely t h a t little importance has been attached t o t h e m , a n d in m a n y cases t h e y can hardly be considered as anything more t h a n wild guesses. Owing t o t h e pockety nature of m a n y of our deposits of phosphorites or amorphous phosphates, careful surveys a n d thorough a n d systematic prospecting are necessary t o gain anything like an’ accurate knowledge of their value a n d extent. T h e expenses of such examinations are frequently not warranted a n d are seldom made except immediately before actual mining operations are begun. Again, much of t h e phosphate property has been acquired so cheaply t h a t only a superficial examination was necessary t o justify its purchase. Under such circumstances t h e owners of t h e land m a y have b u t a hazy idea of t h e amount of phosphate contained therein. On t h e other hand, some of t h e phosphate deposits, such as those in our western states a n d in certain p a r t s of Arkansas a n d Tennessee, are of such a character t h a t fair approximations of their tonnage might be made by careful surveys. 1
Scientist in Investigations of Fertilizer Resources
Utah, Idaho, I\-yoming and M o n t a n a : High-grade., . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2,500,000,000 High-grade equivalent of all grades.. . . . . . . . . . . . . . . . . . . i,500,000.000
f-i l.“rid --._-1 ..
High-grade equiT-alent High-grade equivalent Tennessee: High-grade equivalent South Carolina’ Hich-made ecruivalent Arkansas : High-grade equivalent Kentucky: High-grade equivalent
of all grades. . . . . . . . . . . . . . . . . . . of wash heaps, . . . . . . . . . . . . . . . .
..
of all grades.. of all e r a d e s . .
354,300,000 20,000,000 115,075,000
..
of all grades, . , , , . . , . of all g r a d e s . . .
10,000,000 ,
.,, ..,, ..
20,000,000
................
Total. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
500,000 10.5 19,875.000
T h e production of phosphate in 1912, according t o t h e figures of t h e United States Geological Survey, was as follows: TONS 1
Florida, . . . . . . . . . . . . . . . . . . . 2,406,899 Tennessee.. . . . . . . . . . . . . . . 423,33I(a) South Carolina.. , , . . , . , . , . . 131,490 Western s t a t e s . , . . . . . . . . . . . 11,61Z(b) Total . . . . . . . . . . . . . . . 2,973,332
( a ) Includes production of Arkansas. ( b ) Includes Utah, Idaho and Wyoming.
Even assuming t h a t there are t o be no new discoveries in. this country a n d t h a t t h e average consumption during t h e life of t h e phosphate fields will be three times i t s present consumption, there is sufficient to last for over I IOO years provided proper mining methods are employed a n d means for utilizing t h e lower grade material are devised. Another feature of t h e phosphate industry which in recent years has become of considerable interest t o t h e operator, t h e fertilizer manufacturer, a n d t h e farmer, is t h e growing use of raw ground rock phosphate for direct application t o t h e field. While the
J u n e , 1914
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
value of this material a s a fertilizer still seems t o be a n open question, many agronomists a n d agricultural chemists strongly recommend its use, supporting their recommendations by considerable d a t a obtained by actual plot tests. I n 1912 t h e annual consumption of raw ground phosphate rock, based on t h e amount marketed, was 48,365 tons. While this is less t h a n 1.29per cent of t h e t o t a l phosphate produced a n d only 4.01 per cent of t h a t marketed in t h e United States, t h e sale of ground rock is becoming quite a factor in t h e phosphate industry. BUREAU O F SOILS, WASHINGTON
DETERMINATION OF CARBON I N STEEL AND IRON BY THE BARIUM CARBONATE TITRATION METHOD' By J. R. CAIN
T h e disadvantages attending t h e use of weighed absorption tubes as means for accurately determining carbon dioxide obtained during t h e combustion of steels a n d irons are in p a r t as follows: 1-The elaborate precautions required t o prevent change of weight of t h e t u b e due t o gain or loss of moisture, necessitating complications in t h e purifying train before a n d after t h e furnace a n d t h e use througho u t t h e a p p a r a t u s of drying agents of t h e same hygroscopic power. 2-Difficulties in weighing large glass vessels caused b y electrical effects in wiping, b y buoyancy a n d b y changes in temperature between balance room a n d laboratory. 3-The necessity for maintaining constant conditions with respect t o t h e atmosphere within t h e t u b e , requiring sometimes a long period of aspiration after t h e combustion is completed. 4-The liability t o error from access of gases containing sulfur a n d chlorine, which may be formed during combustion of t h e metal or of t h e carbonaceous residue therefrom. 5-The difficulty of determining whether t h e increase in weight of t h e t u b e is due solely t o carbon dioxide. 6-The time lost in waiting for absorption tubes t o reach a condition of equilibrium before weighing. Those who have used absorption tubes for work requiring a high degree of accuracy know t h a t neglect of one or more of t h e precautions indicated above may easily occasion errors ranging from several t e n t h s of a milligram t o one or more milligrams. It is evident, too, t h a t if t h e complicated purifying train used with a n absorption t u b e gets o u t of order, or if t h e t u b e itself introduces error in some of t h e ways enumerated, it may often be a difficult m a t t e r t o locate a n d correct t h e trouble. It is not surprising, therefore, t h a t methods dispensing with t h e use of weighed potash bulbs, soda-lime tubes a n d t h e like are beginning t o be used extensively by steel analysis. Of such methods t h e weighing of t h e carbon dioxide in t h e form of barium carbonate precipitate directly or after conversion into have been much used, the 1 Published b y permission of t h e Director of t h e Bureau of Standards. Presented at t h e Cincinnati Meeting of t h e American Chemical Society April 6-10, 1914.
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method abroad,l a n d t h e carbonate method in this country. Thus, of 6 2 prominent American laboratories (representing manufacturers, consumers a n d testing laboratories) 3 2 used t h e potash bulb, 24 weighed t h e carbon as barium carbonate, 3 titrated t h e excess of barium hydroxide, 2 used soda-lime tubes a n d one weighed a n absorption t u b e filled with barium hydroxide.2 It is evident, in estimating t h e carbon dioxide by weighing t h e barium carbonate precipitate, or t h e sulfate obtained from it, t h a t t h e difficulties mentioned above as peculiar t o weighed absorption tubes, except number four, are eliminated or minimized; access of sulfur trioxide would still t e n d t o cause high r e s ~ l t s . ~If, however, t h e barium carbonate is measured b y filtering i t off a n d titrating it against s t a n d a r d acid, due regard being had t o proper conditions for filtration a n d washing, there is no likelihood of error from a n y of t h e causes enumerated. T h e principle of this method is described in most s t a n d a r d text-books on quantitative a n d volumetric analysis, b u t there seems t o have been b u t little application in steel analysis. T h e purpose of this paper is t o show the special suitability of this procedure for accurate a n d fairly rapid steel analysis, taking up in order t h e sources of error or difficulty a n d t h e means of avoiding or minimizing these, a n d finally giving t h e results obtained b y a series of analyses of pure sugar a n d of Bureau of Standards analyzed irons and steels. Without further consideration it can be seen t h a t t h e adoption of this method a t once simplifies t h e purifying train required after t h e furnace; nothing a t all likely t o be present in t h e escaping gases can affect t h e results if we except finely divided oxides carried over mechanically a s t h e result of a very violent combustion. N o such oxides were noticed during this work or during t h e analyses of many other samples by different methods; if there is any reason t o suspect their presence, a simple filter macle by filling a U-tube with 20-mesh quartz, previously carefully washed with hydrochloric acid and water. will remove them. The points involving sources of error which were investigated were: (I) completeness of absorption of t h e carbon dioxide, ( 2 ) amount of washing necessary t o remove t h e excess of barium hydroxide, (3) solubility of barium carbonate in t h e wash water, (4) exclusion of extraneous alkaline substances. I n addition there were devised ( 5 ) means for t h e rapid filtration a n d washing of t h e barium carbonate with exclusion of carbon dioxide from t h e air. I-COMPLETEKESS O F ABSORPTIOS-This was established b y burning sugar in amounts giving approximately t h e weights of carbon dioxide obtained during steel analysis, comparing t h e percentages of carbon obtained with t h e theoretical. As a further check two 8-bulb Meyer tubes (shown in size in Fig. I ) 1 Bauer and Deiss, Probenahme und Analyse t o n Eisen und Slahl, 1912, p. 121. 2 D a t a communicated t o t h e author a s member of a technical committee
On 3 There is b u t little likelihood of SOz being produced in burning steel a n d iron. A n y small amounts of BaSOs resulting thereby would be removed by washing (see Sec. 5 on Filtration a n d Washing), t h e solubility of Bas02 being approximately 0.02 gram per 100 cc. of water a t 20' (Seidell, "Solubilities of Inorganic a n d Organic Substances," 1907).
