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(CCI,) SO,Cl* +H,S (CC1,) SOOH + HCl+S. Trichlormethyl
phurous acid. The decomposition of this acid and its salts by bromine and nitric acid is very striking ; the acid disappears and new insoluble compounds are formed.
The action of bromine is expressed by the following equation:
(CCI,) SO OH +Br, (CC13) SO2 Br + HBr. Trichlormethyl-sul
phon-bromid. and the action of nitric acid :
(CC1,)SOOH +NO,H = (CC1,)50,(NO,) +H,0 Trichlormethyl-sul- Nitric acid. Trichlormethyl-sulplionphurous acid.
nitrid. The trichlormethyl-sulphon-bromid is a white crystalline body of a faint acrid smel], insoluble in water but soluble in alcohol and ether. On the application of heat a part is sublimed without change while another part is decomposed. Ammonia dissolves it with evolution of nitrogen. 0.358 grm. yielded 0.313 sulphate of barium corresponding to
12:01 per cent S. 0:492 grm. yielded 1.158 grm. AgCl+AgBr and this mixture
yielded by reduction 0.808 Ag, which proportions corres
pond to 30.77 per cent Br, and 40:22 per cent Cl. The theory demands 12:19 per cent S, 40:57 per cent CI, 30:43
per cent Br.
When trichlormethyl-sulphurous acid is brought into contact with concentrated nitric acid, a violent reaction takes place and a blue oil is deposited which loses nitrous acid by contact with the air and is converted into a white crystalline body, the odor of which inflames the eyes and is very suffocating when inhaled. This is the trichlormethyl-sulphon-nitrid especially interesting in this, that a nitrid of an organic sulph. acid has been hitherto unknown. It is insoluble in water, soluble in ether and alcohol. Water added to the alcoholic solution precipitates it unchanged. It does not melt in boiling water but is volatilized with the steam. Ammonia dissolves it slowly with decomposition, alcoholic solution of caustic potassa decomposes it quickly. When it is treated with zinc and hydrochloric acid it disappears and is converted into sulphydrate of methyl and ammonia :
(CC1,)S0,(NO,) +18H =CH, SH +H,NCI+2HCl+4H,0 Trichlormethyl-sul
Sulphydrate of phon-nitrid.
methyl. 0:5285 grm. yielded 0:532 sulphate of barium and 0.973 AgCl,
corresponding to 13.83 per cent S and 46 12 per cent Či. Theory demands 14:00 per cent S and 46:61 per cent Cl.
On treating trichlormethyl-sulphon-chlorid with ammonia, trichlormethyl-sulphurous acid is formed in an unexpected manner, nitrogen is evolved and the chlorid is slowly dissolved. On evaporation broad tabular crystals are obtained. In the mother-liquor there remains chlorid of ammonium, some sulphate of ammonium and a certain quantity of this new compound. The crystals must be recrystallized with great care because at a moderate temperature an acid reaction sets in and a partial decomposition begins. These crystals show with bromine as well as with nitric acid the formation of the above mentioned bromid and nitrid. The action of the nitric acid is extremely violent.
By mixing with diluted hydrochloric acid and agitating with ether the above mentioned trichlormethyl-sulphurous acid is obtained 0:431 grm, yielded 0-911 grm. AgCl=52:24 per cent Cl. 0:668 grm. yielded 0.725 ammonio-chlorid of platinum=6.80 0.753 grm. yielded 0.894 grm. sulphate of barium=16:23 per
cent S. Theory demands 53:11 per cent CI, 6.98 per cent N, 15.96 per
cent S. The crystals are therefore the ammonium salt of the trichlormethyl-sulphurous acid and their formation can be expressed by the following equation : 3((CC1,)50,Cl) +8H, N=3((CC1,)SO,H,N) +2N+3H, NCI Trichlormethyl-sul.
Trichlormethyl-sulphite of phon-chlorid.
ammonium. On treating trichlormethyl-sulphon-chlorid with cyanid of potassium, evolution of cyanogen and hydrocyanic acid takes place and the potassium salt of trichlormethyl-sulphurous acid is formed :
(CC1,)SO,Cl +2K Cy =(CC1,)SO OK +KCI +2Cy But when the solution is hot and very concentrated, there is also another derivative of this acid formed, one atom of cl being replaced by one atom of OH.
(CC1,)SO OK+H,0=(CCI,OH) SO OK+HCI,
per cent N.
which latter decomposes another part of the cyanid of potassium.
A glance at the following formulas will show the relation between these new bodies and several others already known : Trichlormethyl-sulphon-chlorid (C C1,)S0, Cl (Kolbe). Trichlormethyl-sulphon-bromid (C CI,)so, Br. Trichlormethyl-sulphon-nitrid (CC1,380,(NO2). Trichlormethyl-sulphuric acid (CC1,)S0,0H (Kolbe.) Trichlormethyl-sulphurous acid (CC1, )SÓ OH. Methylsulphuric acid (CH,)SO,OH (Kolbe.) Methylsulphurous acid (CH, SO OH (Hobson.)
New York, January, 1869.
ART. XXXII.--Note on the structure of the Blastoidea; by
E. BILLINGS, F.G.S., Paleontologist Canada Geol. Survey.
The remains of the Blastoidea have as yet proved to be extremely rare in our Canadian rocks, only five small specimens—three of Pentremites and two of Codaster—having been collected up to the present time. While studying these with a view to their description I was led to investigate the structure of the order, especially with regard to the function of the summit openings. On combining the observations of other authors, whose views I shall give in detail in another paper,
I find that we have now sufficient data to establish the following points :
1. In the genus Nucleocrinus Conrad, there are sixteen apertures in the summit. Of these the large lateral aperture is both mouth and vent. There is no opening in the center of the apex where the mouth has hitherto been supposed to have its position. The ten so-called “ovarial orifices" are respiratory apertures. Between each two of these one of the ambulacral
grooves enters to the interior through a small pore which is a true ovarian orifice. There are thus ten spiracles, five ovarian orifices and one buccal and anal orifice-in all sixteen.
2. In Pentremites there are also five ovarian pores, in the same position. The mouth is not in the center, but in the larger of the five spiracles.
3. Codaster has no ambulacral pores in the so-called “pseudambulacral fields." The striated surfaces in the interradial areas are true Cystidean rhombs of the type of those of the genus Pleurocystites. These in Pentremites, Granatocrinus and Nucleocrinus are situated under the ambulacra where they constitute the tubular apparatus described by Roemer and others.
ART. XXXIII.-Notes on the occurrence and composition of
the Nodular Phosphates of South Carolina; by CHARLES U. SHEPARD, Jr., M D., Prof. of Chemistry in the Medical College of the State of South Carolina.
The belt of nodular phosphates appears to extend, more or less interrupted from the Wando and Cooper rivers, some fifteen to thirty miles above Charleston, in a south-southwesterly direction, parallel to the coast line, as far as St. Helena Sound and Bluffton, near Port Royal. As yet the precise area is unknown; no accurate survey having been made, although this want is daily felt by the community. It would be erroneous to suppose that there is a well defined stratum of any such extent as this area above mentioned; on the contrary, the bed appears only in patches, some of which, however, are many miles in diameter. On the Wando and Cooper rivers the nodules are found in comparatively small beds, generally but a few inches in thickness; still, limited deposits, one to three feet thick, have been reported 'in some localities of this neighborhood. On the peninsula between the Cooper and Ashley rivers, the deposit assumes the form of a well defined stratum, in many places attaining a thickness of eighteen to twenty-four inches, and underlying hundreds of acres, at an average depth of about three feet from the surface. The nodules vary in size from that of a walnut, to masses weighing two hundred pounds and over; they lie compactly together with but little marl between them. This marl is composed of 30 to 60 per cent carbonate of lime, a few per cent phosphates of iron, lime, and alumina,—the balance being chiefly sand and peroxyd of iron. At other points on the peninsula, the nodules rarely exceed a few lbs. in weight, and are sparsely distributed. The favorable localities lie east of Goose creek, near the Cooper river. The Ashley beds were the first discovered, are the best known, largest in extent, and most mined. This deposit extends, at an accessible depth, over, perhaps, one thousand acres, on both sides of the river; and running back from it for several miles in some places. The beds are quite accessible, not only on account of the depth of the Ashley river and their proximity to Charleston, but because of their lying close to the surface (generally within two feet) in a light soil which separates easily from the nodules on handling or washing. The nodules are of a yellowish-gray color, of less specific gravity than those elsewhere found, their surfaces but slightly irregular, and their composition tolerably uniform. The best beds lie on the river ten to twenty miles from Charleston; farther up stream, the nodules are found in a sandy soil, and become permeated with sand to the amount of thirty per cent and over, when the phosphates do not reach fifty per cent. On some plantations the bed of phosphatic nodules is over two feet in thickness; and the amount of marketable material produced from mining an acre may exceed twelve hundred tons. On the Stono and Edisto rivers there have been found but few rich deposits,—the stratum exhibiting continuity in but occasional spots. As a rule, the nodules lie deeper on these rivers than on the Ashley. Heavy deposits have been discovered on the flats in the neighborhood of St. Helena Sound, covering vast surfaces at little depth from the surface, occasionally forming a compact floor, or huge boulder-like masses on the bottom the creeks vhich intersect that neighborhood. Finally, on the Ashepoo river, at one locality in this neighborhood, the stratum has the appearance of an immense pavement, extending over hundreds of acres at a depth of three to six feet. It is with difficulty that the large masses (often several hundred weight each) can be pried apart, so closely are they wedged together,-having a smooth, glazed, upper surface, but irregular beneath. The masses moreover are often penetrated to considerable depth, sometimes perforated by round holes, which extend generally in a perpendicular direction. These cavities have a diameter of one-half to one inch. The phosphatic masses forming this floor are nine to twelve inches in thickness, and overlie a bed of nodular phosphates of smaller size, which extends down to the depth of twelve to fifteen inches below the continuous stratum. The whole deposit is imbedded in a tenacious clay, underneath which occurs a yellow-red marl. This marl is rich in shells and the bones of marine and land animals. It is composed, when air-dry, of nearly 70 per cent sand, 18 per cent carbonate of lime, and 5 to 7 per cent phosphates of lime, alumina and iron. It is reported that the nodules form in some limited localities a second layer, and as continuous as the top stratum, —underlying it at the depth of about one foot.
The phosphatic nodules and masses generally give on friction of their fresh surfaces, a peculiar naphthous odor. This property is, as a rule, the more decided, the denser the nodules; and is in direct proportion to the amount of organic matter contained in them. The impressions of numerous fossil shells of the Eocene period occur throughout the various phosphatic masses.
Composition.—The analyses given below are of hand specimens, taken at random from large quantities of the material of the different localities mentioned. They are not supposed to