T H E J O C R S A L OF I S D U S T R I A L A S D E - Y G I X E E R I S G C H E M I S T R Y
Sept., 1 9 1 3
t u r e at all times a n d a comparatively small rise in t e m perature produced a considerable change i n t h e a m o u n t of nitrogen fixed. T h e calcium equivalent t o t h e silica, as found b y analysis, in 4 p a r t s of t h e feldspar is equal t o 4.3 p a r t s of calcium carbonate. This proportion seems best suited in t h e fixing of nitrogen since smaller yields were obtained when t h e proportion of lime t o feldspar was increased or decreased beyond this limit. T h e same results were obtained starting with t h e oxide of calcium as with t h e carbonate. Only a very slight a m o u n t of nitrogen was fixed when a mixture of lime a n d carbon were ignited a t 1400’ in t h e absence of feldspar. T h e increase of fixation with time of ignition is shown in t h e following table, when J. p a r t s of feldspar, 2 p a r t s of carbon a n d 4 . 3 parts of calcium carbonate mere ignited for diffeqent lengths of time. T i m e of ignition Hours
. 2. . . . . . . 4........ 1. . . . . . . . 2 . . . . . .. . 1. . . . . . .
Potash Nitrogen fixed in volatilized in percentage of percentage of total feldspar aluminum in present taken feldspar 55,s 1.27 12.2
----
Temperature about 1200’ a b o u t 1200’
68.9
1.34
12.9
a b o u t 1200’
83.0
1 68
a b o u t 1400’
100.0
6 10
16 1 58.5
a b o u t 1400’
100 . o
7.44
71.5
Since t h e nitrogen in aluminum nitrid a m o u n t s t o j 1 . 6 per cent of t h e aluminum, i t follows t h a t t h e nitrogen fixed i n t h e last t w o experiments is greater t h a n w h a t would correspond t o t h e aluminum in t h e feldspar. K O direct experiments have yet been made t o determine i n w h a t form t h e nitrogen is combined, whether as nitrid or carbo-nitrid of silicon or aluminum. W h e n boiled with water t h e material gave off ammonia very slowly, a n d even slowly when boiled with sodium hydroxide solution although in this case t h e ammonia was evolved more rapidly t h a n when t h e digestion was made with water alone. E q u i p m e n t is now being installed t o carry on t h e experiments on a larger scale a n d at higher temperatures. I n t h e meantime i t was t h o u g h t advisable t o publish t h e preliminary results obtained. BUREAUOF SOILS U. S. DEPARTMENT OB AGRICULTURE WASHINGTON
THE LEACHING O F POTASH FROM FRESHLY CUT KELP B y A. R. hlER2.l
AND
J. R. LINDEMUTH2
Received June 27, 1913
Drift, kelp usually has a very low content of potash
729
or’ rather potassium chloride. It has been currently reported t h a t t h e loss of potassium chloride from t h e freshly c u t plant proceeds quite rapidly. Theoretically, there should be a distribution of t h e base between t h e plant a n d t h e water in which i t lies, a n d t h i s redistribution might reasonably be expected t o commence at once, a n d even t o be much augmented or accelerated because of t h e relatively high content of sodium chloride in sea water. This problem is one of considerable economic importance, since i t has been proposed in t h e harvesting of kelp as a raw material for t h e production of potassium salts, t o t o w t h e c u t kelp from t h e groves t o t h e landing a n d t h u s avoid lifting t h e material upon a barge or boat. I n order t o obtain some information a n d d a t a bearing directly on this economic question, Professor W. C. Crandall, of t h e Scripp’s Biological Station, a t L a Jolla, California, collected t w o large samples of M a c v o c y s t i s on a recent cruise of t h e y a c h t , “ i l g u x i ” , of t h a t station, towing these samples a n d taking subsamples from time t o time which were forwarded t o t h e laborat o r y of t h e Bureau of Soils, in Washington, for analysis. One of t h e large samples for t h e leaching espcrim e n t was collected n e a r Pt. Loma a n d t h e other near Coronado Island. T h e subsamples, on their receipt i n Washington, h a d commenced t o ferment. This fact, however, could not h a r e a n y particular influence on t h e d a t a here given. T h e tables which follow are self-explanatory. T h e analytical methods employed have been described i n THIS J O U R N A L , 4, 431 b y Turrentine, a n d acknowledgment is here made t o N r . T. C. Trescott, of t h e Bureau of Chemistry, who kindly made t h e nitrogen determinations for us. F r o m t h i s examination i t is evidently a m a t t e r of considerable difficulty t o obtain a fair average sample of wet kelp. I t also appears t h a t freshly cut kelp, when immersed in sea water, does n o t , at least at first, lose i t s potash content very rapidly. Attention is called t o t h e analysis of “ s e a lettuce” in Table 11. This is n o t a kelp b u t a rock weed rather common on t h e Pacific coast. Algae other t h a n t h e giant kelps have not usually shown a high potash cont e n t , b u t this analysis indicates t h a t t h e m a t t e r is worthy of further investigation. ’rhe difficulties t o be apprehended in harvesting rock weeds, however, d o not leave much promise for their economic importance a t present, even though t h e y should be found t o have a high content of potash or other valuable
TABLE I-SAMPLE TAKEN NEAR CORONADO ISLANDS No. lm.. ... . . . . .. 1ex. . . . . . . . . , , 1A.. . , . . , . . . . 1B... . . . , . . , , 1 c . ., . . . , . . . 1 D . . . ... . . . . . 1E.. , . . . . . . . . IF.. .. . . . . . . 1 G . ., . . , . . , . .
T i m e exposed
;r:z
) fresh c u t
3 hrs. 6 hr5. 14 hrs. 1 7 1x5. 20 hrs.
Per cent Kz0 12.48 13.47 15.56 17.30 17.61 13.35 10 74 18.28 9.90
P e r cent Per cent P e r cent sol. salts org. m a t t e r ash 31.46 31.26 34.00 38.26 38.30 31.96 26.36 36.78 25.94
65.38 65.98 62.38 58.66 58.30 54.96 T0.66 60.86 70.18
3.16 2.76 3.62 3.08 3.40 3.08 2.98 2.36 3.88
1 Scientist in Soil Laboratory Investigations, Bureau of Soils, U. S. Dept. Agr. 2 Scientist in Fertilizer Investigations, Bur. of Soils, U. S. Dept. -4gr.
Per cent KC1 19.72 21.28 24.59 27.33 27.87 21.10 16.97 28.89 15.64
Per cent N 0.98 0.79 0.95 1.00 1,07 0 83 0.90 0.51 0.84
Per cent 1
0.16 0.14 0.13 0.13 0.06 0 10
0.13 0.13 0.07
Remarks Dried and sent b y mail Wet, sent b y express in j a r Wet, sent b y express in jar Wet. sent by express in j a r \Vet. sent b y express in j a r Wet, sent b y express in jar Wet, sent by express in j a r Stems only, dried a n d sent b y mail Leaves only, dried a n d sent b y mail
constituent, and t h e importance of t h e matterprobably lies in showing that their occasional O r
T H E JOL-R.!Z7ALOF IL‘\‘D17STRIAL 41.VD E S G I S E E R I S G C H E A I I I S T R Y
730
TABLE 11-SAMPLE No.
.. . . . . . ... .. .. 2c. . . . . . . . . 2 D . . . .. . . . . 2 E . . . .. . . . . 2F.. ... .. . . 2G. . .. . . . . . 2H. . . . . . . . . 21.. . . ,.. . . . 2J ... . . . .. . . 2 K . . . ... . . . 2L. . . . . . . . . 2 M . . . . . ... . 2 N . ..... . . . 2 0 . . .. . . . . . 2 P . . . .. . . . . 2Q. . , . . . . . . 2R. . .... . . . 2s......... 2 T . .. . . . . . . 2u. . . . . . . . . 2A.. 2B..
2V. . . . . . . . . 2W. . . . . . . , . 2 . . . . . . .. . . hl. P.. . . . . .
.
KzO
P e r cent sol. s a l t
Per cent org. m a t t e r
15.82 13.43 14.96 13.05 11.00 11.59 13,68 10.31 16.39 11.77 16.69 15.77 16.74 16.75 14.67 12.61 15.54 17.62 17.03 15.61 20.28 15.72 15.60 15.27 30.00
40.88 34.82 37.66 34.34 30.22 30.52 38.94 27.84 38.78 32.44 39.72 40 80 42.58 38.64 35.58 34.74 40.84 41.42 42.44 3i.80 46.28 38.80 39.24 34.52 57.10
47.32 56.54 52.76 60.12 62.52 59.92 50.56 62.38 53.30 60.54 54.22 45.88 45.36 55.28 58.12 55.46 48.92 49.48 44.50 54.42 43.96 51.44 48.74 57.42 32.76
Per cent
Time exposed None 3l/2 hrs. 15’/z hrs. 1B1/2 hrs. 211/2 hrs. 24l/2 hrs. 27l/z hrs. 39I/z hrs. 4Z1/2 hrs. 45l/2 hrs. 48’/2 hrs. 511/z hrs. 63I/z hrs. 66l/2 hrs. 72l/2 hrs. 75I/z hrs. 8 7 I / ~hrs. 901/z hrs. 93’/z hrs. 96I/z hrs. 99l/2 hrs. 11 ll,’z hrs. 13j1/2 hrs. 11 1 I / a hrs.
P e r cent ash 11.80 8.64 9.58 5.54 7.26 9.56 10.50 9.78 7.92 7.02 5.96 13.32 12.06 6.08 6.30 9.80 10.24 9.10 13.06 7.i8 9.76 9.76 12.02 8.06 IO. 1 4
presence in harvested kelp is not detrimental t o t h e value of t h e kelp. U.
s.
BCREACO F SOILS DEPARTMENT O F AGRICULTURE WASHINGTON
A POSSIBLE COMMERCIAL UTILIZATION O F NELSONITE B y WILLIAMH. W A G G A M A N ~
Received June 23, 1913
I S T R 0 D UC T I 0 S
I n Nelson County, Va., there are large bodies of rock locally known as Nelsonite which consist essentially of t h e two minerals ilmenite a n d apatite. The material is not only of scientific interest b u t in t h e light of some recent experiments performed in this laboratory may be of considerable commercial importance. The rock occurs in the foothills of t h e Blue Ridge near Roseland, Va., a b o u t 7 miles northwest of Arrington, a station on t h e Southern R. R., a n d 24 miles northeast of Lynchburg. According t o WTatson2 it is probably of pre-Cambrian age a n d occurs in dikes which a r e in places over 65 feet thick and 2,100 feet in length as exposed on t h e surface. T h e formation can be traced in a general northeast southwest direction Watson described i t a s “a hard for a b o u t ’ 7 miles. rock composed of granular white apatite a n d black ilmenite.” After weathering, however, t h e rock can be readily disintegrated a n d a more or less clean separation made of t h e two minerals by either of t h e methods described further on in this paper. ILMENITE
Ilmenite or titanic iron is a black crystalline mineral having feebly magnetic properties. I t has a specific gravitywhen pure of 4. j t o j . 0 a n d t h e following formula a n d composition: Titanium oxide (TiOz). . . . . . . . . . . .
FeTiOa
{ Iron protoxide (FeO) . . . . . . . . .
.
...
5 2 . 7 per cent 4 i . 3 per cent
According t o Dana,3 however, t h e ratio of iron t o Scientist in Fertilizer Investigations, Bureau of Soils, U. S. D e p t . Agr. “Mineral Resources of Virginia,” 1907, p. 300; “Economic Geology,” U. S. Geol. Survey, 1909, pp. 206-7. “A System of Mineralogy.” 1892, pp. 217-219. 1
2
NEAR PT. L O M A Per cent Per cent N KC1
Vol. j, No. 9
FROM
25 .oo 21.22 23.64 20.62 17.38 18.31 21.62 16.29 25.90 18.60 26.37 24.92 26.45 26.46 23.18 19.93 24.56 27.84 26.90 24.67 32.05 24.84 24.65 24.13 47.41
2.77 2.66 2.40 1.77 1.85 2.10 2.22 1.97 2.22 1.99 1.79 2.29 2.49 1.91 1.88 2.66 2.47 2.16 2.28 2.16 2.12 2.26 2.57 1.80 1.66
Per cent Remarks
I 0.18 0.19 0.15 0.15 0.16 0.14 0.24 0.14 0.21 0.22 0.19 0.22 0.21 0.19 0.19 0.22 0.19 0.16 0.20 0.10 0.20 0.23 0.27 0.18 0.06
W e t , sent in j a r W e t , sent in j a r Wet. sent in j a r W e t , sent in j a r Wet, sent in j a r Wet, sent in j a r Wet, sent in j a r Wet, sent in j a r Wet, sent in j a r Wet, sent in j a r Wet, sent in j a r Wet, sent in j a r Wet, sent in j a r Wet. sent in j a r Wet, sent in j a r Wet, sent in j a r Wet, sent in j a r Wet, sent in j a r Wet, sent in j a r Wet, sent in j a r Wet, sent in j a r Wet, sent in j a r W e t , sent in j a r Dried a n d sent b y mail Sea lettuce from Marrowstone Point
titanium varies widely corresponding t o t h e general formula RIFeTi03.NFe203. Ilmenite is rather widely distributed in nature, occurring in beds in gneiss and other crystalline rocks; also in small particles in many crystalline rocks a n d frequently associated with magnetite. It is used in t h e manufacture of ferro-titanium for the steel industry. I n 1911 there were j 1 . 1 7 tons of ferrot i t a n i u m imported i n t o this country valued a t $ 2 2 , 7 0 0 , which gives an average price of $443.61 per ton. APATITE
Apatite or phosphate rock is a brittle crystalline mineral which varies in color from almost white t o dark green-red a n d brown. There are two main varieties of this mineral; namely, chlor-apatite a n d fluorapatite, t h e latter being much more plentiful t h a n t h e former. The specific gravity of apatite varies from 3.17 t o 3 . 2 3 a n d t h e formula a n d composition of t h e two varieties according t o D a n a , are as follows: f P205 = 41.0 per cent Chlor-apatite, CaC1.Ca4(P04)3= CaO = 53.8 per cent C1 = 6.8 per cent P205 = 42.3 per cent Fluor-apatite, C a F . C a 4 ( P 0 4 ) 3 ={ CaO = 55.5 per cent IF = 3.8 per cent
1
r
Apatite, however, is seldom found absolutely pure a n d though widely distributed in n a t u r e does not often occur in minable quantities. On t r e a t m e n t with sulfuric acid i t yields a very high-grade superphosphate, a n d if i t were not for t h e fact t h a t t h e better deposits are rather inaccessible a n d t h a t careful picking or “cobbing” is necessary before a product sufficiently high-grade for t h e market is obtained, this mineral mould be more extensively used in t h e fertilizer industry. S E P A R A T I O N O F APATITE AND I L M E N I T E
4 t first sight t h e association of apatite a n d ilmenite in a rock would seem t o seriously affect t h e commercial value of both of these minerals. I n t h e manufacture
