摘要:

THE Q U A RT I3 1iLY J 0 U It i”d A L OF THE CHEhIICAL SOCIETY OF LONDON. Nov. 20 1848. TVilliarn ,411en Millcr M.D. in the Chair. The following presents were laid on the table :-‘c AHEssay on the com-paratit e value of clifferent liincls of Coal for the purposes of illumination,” by A. Fj-fe N.D. presented by the autlior and Taylor’s Calendar of the Neetings of Scientific Bodies for 1848-49 also from the author. Messrs. Alexander Bain and Williani John Hay were duly elected members of the Society. The following letter and coniniuiiicatioiis were rend On trnces of Copper and Lead in the ashes of Cod hy J. ARTHUR EsQ., PHILLIPS i92 a Letter to Mr. TXnrington.-The writer having read with much interest a paper by Mr. Yaux in the Transactions of the Society in which was a list of coals containing traces of copper and lead recorded ivas induced to repeat the experiments on the ashes of some of the coals which had passed through his hands in counexion with ‘‘the Admiralty Coals Inyestigation ;” in no instance however was he able to detect the presence of the slightejt trace of either of those metals.Mr. Phillips’ experiments were made 011 the ashes of the following conls from Kewcastle viz. Carr’s Hartiey Xemastle aartley and North Percy I-Iartley ; these were followed by the examination of some specimens from Liver-pool viz The Laffak Rushy Park. The Johnson’s and Worthington’s Sir John and The Blackbrook Rushy Park. vo:,. TI. -NO. v. B RlR. RITJSPRATT OX THE TVignn Coals.The Balcaries Lindsay. Scotch Coals. The Eglington The Wellwood The Fordel Splint and Wallsend Elgin. FVeZsh ConIs. The Pontypool The Bedwas The Porthmawr The Ebbw Vale and Linoi Coals. An anthracite from Slievardagh in Ireland and a specimen of coal from Conception Bay Chili were also tried with the same results. It would therefore appear that although traces of copper and lead may occasionally occur in coal their presence is estremely rare in the districts above mentioned. In these experiments care was taken to employ water perfectly free from metallic salts as on examining the ordinary distilled water of the labora- tory some of it was found to darken slightly on passing a current of sulphuretted hydrogen through it ; no water was therefore employed which had not been prerionsly tested and ascertained to be free from traces of the metals.

ISSN:1743-6893    

DOI:10.1039/QJ8500200001

出版商:RSC    

年代:1850

数据来源: RSC

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RlR. RITJSPRATT OX THE MUSPRATT,ESQ. Analysis of BEack-ash Soda-ash &. by FREDERIC -Conducting the operations in an estensive Soda Manufactory have repeatedly to investigate the several processes in all their intricate relations and more especially to malyse the numerous products in order to arrive at the necessary quantities of the different sulistances that should be employed in the mixtures for the production of a black-ash that would yield when lixiviated the largest amouint of subcarbonate Gf soda. the fabrication of soda as in all other technological processes correct data can only be arrived at by ascertaining exactly the composition of the products. Some of my results are completed and as they may prove interesting to the Society I transmit them through my brother Dr.Muspratt. The analysis of black-ash being somewhat complex my mode of procedure is appended as it may facilitate the progress of others embarking in a similar field of research. I dissolved a weighed portion of black-ash in aqua regia boiled and filtered the solution. 1. The residue was weighed 011 a dried filter. It consisted of charcod and sand. 2. I evaporated the filtrate and digested the residue with hydrochloric acid ; filtered again and determined the amount of silica which remained. 3. 'l'he solution was treated with ammonia to precipitate the phosphate of lime niid peroxide of iron which were ignited and weighed. ANALYSIS OF BLACK-ASH SODA-ASH &C. 4. I treated the filtrate from 3 with oxalate of ammonia precipitating the lime from the amount of which I calculated its compounds with sulphur and carbonic acid.5. The filtrate was evaporated with sulphuric acid to obtain sulphate of soda and sulphate of magnesia from which after deducting the magnesia determined in the usual manner by dissolving the compound and pre- cipitating with phosphate of soda and ammonia I obtained the soda; and after calculating the quautity that existed in cornhination determined the amount of caustic soda. hother portion of the ash was treated with concentrated nitric acid and the sulphuric acid precipitated by means of nitrate of baryta. Water was then added to another weighed quantity of black-ash till all the soluble portion was dissolved. The solution was then measured into three parts and the chloride of sodium sulphate of soda and d-phide of sodium were respectiyely determined.The amount of carbonic acid was ascertained with the aid of Will’s apparatus ; an aqueous solution gave in the first instance the carbonic acid combined with soda and secondly the black-ash treated with an excess of chromate of potash yielded the total quantity of carbonic acid. ANALYSIS OF BLACK-ASH. Calculated 011 100 parts without charcoal and sand. Carbonate of soda . 17*1Sl 18.804 Caustic soda* . . 7.970 SA723 Sulphate of soda . 1.500 1.642 Sulphide of sodium . 0.900 0.985 Chloride of sodium . 2.600 2.846 Sulphide of calcium . 25.048 28.509 Carbonate of lime . 17.045 18.655 Caustic lime . . 8.355 9‘144 Peroxide of iron.. *> 3.817 4.1 78 Phosphate of lime . silicate of magnesia . . 1.4130 1.620 . 4.472 4.894 Silicate of soda Charcoal and sand . . 7.942 -99*280 1OO-C)QO * Since this analysis was read to the Society a paper on the products of the Soda Manufacture by hlr. John Brown has appeared in the Philosophical Magazine for January 1849 in which the author objects to the manner in which Unger and Rkhztrdson have stated their results with regard to the carbonate and caustic Soda. Their determinations appear to me most satisfactory as tbey represent the value of the coinpound obtained in the process of manufacture in the same way that one mould state the richness of a metal procured in the manufacture of prmsiate of potash. Did the B2 MR.THORXTON JOI3X I-IERiPATH 0s THE The abore resiilts justify the assumption that a double salt of sulphide of calcium and lime is formed wliich is insoluble in water whereas the sulphide of calcium is soluble. The method employed in analgsing soda-ash was siniilar to t,hat described with reference to black-ash it will therefore be unnecessary to repeat it. AN,1T,TC;TS OF SODA-ASH. Calculated 011 LOO parts n-ithout charcoal and sand. Carbonate of soda . . 77-08;? 78.428 4,881 4-961 Caustic soda . Sulphate of soda . 3.110 5.198 Sulphide of sodium 0.630 0.640 Carbonate of lime . 0.320 0.525 Pcroside of iron . 0.324 0.329 Carbonate of potash . 0°200 0.204 Cyanide of sodium . 0.012 0.013 Silicate of soda . . 2*400 2.442 Chloride of sodium 7.130 7.256 Sulphide of calcium . 0.200 0-20-1 I Charcoal and sand . 0.G59 98.95 1 100~000 It will be seen from the above analysis that the quantity of caustic soda is very small proying that the carboiiates generally employed may be dispensed with as the access of air performs their office sufficiently for general purposes. I haye also had occasion to examine niaiip specimens of pyrites both before and after ignition and have invariably found the burnt pyrites to contain its sulphur in the form of sulphuric acid most probably in the state of a basic salt. The mass is perfectly insoluble in water.

ISSN:1743-6893    

DOI:10.1039/QJ8500200002

出版商:RSC    

年代:1850

数据来源: RSC

摘要:

MR THORXTON JOHX €IER.kPATH OX THE I.-Analyses of the Ashes of some Esculent Vegetables. By THORNTON ESQ. JOHNHERAPATXI At a period whcn so much attention is paid by scientific men both at home and abroad to the inorganic constituents of plants and when many of our chemists of the first standing are engaged in their analysis the detail of the results of some experiinental quantity of caiistic soda depend entirely on the excess of lime employed the carbonate and caustic soda might be readily calculated as well a3 the compound saIt of the suipbide of calcium. ASHES OF ESCULENT VEGETABLES. inquiries which I have lately instituted into the chemical constitu- tion of the ashes of some of our commonest esculent vegetables though few in number may not be thought uninteresting by the members of the Society; for although my recent experiments on this subject which I hare already had the honour of communicating to the Society would appear to shorn that we must not expect much benefit to result to physiology from the analysis of the inorganic substances contained in such a heterogeneous assemblage of parts as that which occurs in any separate organ of a plant still it cannot but be admitted by every chemist who may have witnessed the great improvements which have of late years been introduced in the cultivation of the soil that such analyses have proved and are still proving of the greatest assistance to the practical agriculturist in nuinerous ways and are of especial service in pointing out to him those particular substances which are most beneficial as manures for his crops.It was with this latter object in view that the following analyses wcre undertaken. All the specimens examined were particularly fine and in excellent preservation and were with very few exceptions obtained from the places in which they mere growing by myself; I was consequently enabled to ascertain every circumstance connected with their growth which it was necessary for me to be acquainted with. The greatest care was taken to remove all extraneous matters from the plant prior to burning. The processes followed in the preparation and analysis of the ashes have been already described in a former paper to the Society. 1.-SCURVY-GRASS (Cochleayia anglica).This vegetable as is me11 known although not ordinarily con-sidered as an article of food is occasionally resorted to as such by sailors after returning from long voyages or when suffering from scurvy produced by a deficiency of vegetable aliment. It has been found particularly beneficial to persons suffering under this disease and hence is derived its popular name. The plants the ashes of which were submitted to examination were fouud growing on the de'bris of new red sandstone-rocks near the banks of the river Avon which were occasionally submerged at high tide. a. 6440 grs. of the fresh specimen (entire) gave 740 grs. of dry vegetable matter which left upon incineration- 156 grs. of ash. b. 5000*00 grs. of fresh gave 574.70 grs. of dry plant which left 121.11 grs.of ash. JIR. THORNTON JOHN HERAPATH ON THE These experiments give 2.4222 as the mean per-centage of ash fsom the fresh and 21.0770 as that from the dry plant. Thesc ashes were found to consist in 100 parts of SOLUBLESALTS I. 11. ME 4N. Carbonic acid. 3.580 3.560 3.570 Sulphuric acid . 3.024 3,244 3.134 Phosphoric acid Potash . . traces. traces. traces. ooloo traces. 0.050 Soda . 7.710 7.764 7.737 Chloridc of sodium . 63.510 63.758 63.634 INSOLUBLESALTS Carbonate of lime . . 7.079 7.279 7.179 J magnesia . 1.093 1-471 1.282 Siilphate of lime . traces. traces. traces. Phosphate of lime (tribasic) 11.030 9.482 10.256 J? , magnesia . traces. traces. traces. Perphosphate of iron 0 0,503 0.779 0 6B1 Silicic acid .2.495 2.633 2.564 100.024 100.070 100.047 Deducting thc carbonic acid we obtain the following per-centage composition Sulphuric acid 3.383 Phosphoric acid . 5.433 Potash . . 0.054 Soda . 8.359 Chloride of sodium . . 68.701 Lime . . . 10.282 Magnesia . 0.658 Sesqui-oxide of iron . . 0.367 Silicic acid . . 2-763 100~000 11.-CELERY(Apiumgraveozens). a. 1555.0 grs. of the fresh young shoots gave 101.4 grs. of dry vegetable matter and left 17.1 grs. of ash upon incineration. 6. 4546.70 grs. of the same specimen gave 307.25 grs. of dry matter and 50.00 grs. of ash. from the fresh plant . I9996 Mean per-centage of ash { , ,) dried , . 16.2720 ASHES OF ESCULENT VEGETABLES. SOLUBLESALTS I. 11.MEAN. Carbonic acid. 7-967 8.407 8.187 Sulpburic acid . 0.957 0.983 0.970 Phosphoric acid . 6.419 6.423 6-421 I Potash . . 29.019 29.657 29.338 Soda . . . traces. traces. traces. Chloride of sodium. . 32-909 31.651 329280 INSOLUBLE SALTS Carbonate of lime . 7.310 7,652 7.481 , , magnesia . traces. traces. traces. Sulphate of lime . I) 99 >> Phosphate of lime (tribasic) 13.091 14.279 13.685 ? , magnesia . -Perphosphate of iron . traces. traces. traces. Silicic acid . 2.092 1.182 1.637 99.764 100-234 99.999 After the deduction of the carbonic acid the composition in 100 parts will be Sulphuric acid . 1.095 Yhosphoric acid . 14.390 Potash . 33.144 Soda . . traces. Chloride of sodium. 36.466 Lime . . 13,056 Magnesia .traces. Sesquioxide of iron . >> Silicic acid . . 1.849 IIL-SEA-KALE(Crambe maritima). I have analysed the ashes of this plant taken at two different periods of its growth; firstly those of the full-grown leaf and petiole; and secondly those of the young blanched sprouts; the plant in the meantime having been well manured with horse-dung. Soil.-Rich porous and sandy garden ground lying on the mill- stone-grit which contained a pretty large proportion of carbonate of lime. a. 1097.0 grs. of the fresh leaf &C. gave 113.4 grs. of dry vegetable matter and left 19*0grs. of ash upon incineration. JIR. THORNTOX JOHN HEBAPATH OK THE b. 1737.0 grs. of the same speciiiieii gave 179.0 grs. of dry matter and 30*00bgrs.of ash. &an per-centage of ash { from the fresh lcaf &c. . 1.732 ,y , dried , . 16.736 a. 1158.0 grs. of thc fresh young s;)routs gave 83~4grs. of dry vegetable matter and left upon incineration $998 grs. of ash. 6. 1737.0 grs. of the same speciincns gave 125.1 grs. of dry matter and 12.4447 gs. of ash. from the fresh young sprouts. 0.7108 Mcan per-centage of ash c , dried , 9.9490 9 Old plant. Young plant. SOLUBLE SALTS I. 11. Carbonic acid . . . 6.921 4.217 Sulphuric acid . . 15.157 21-848 Phosphoric acid . . . traces. 5.061 Potash . . 2.105 6.7'48 Soda . . . . . 20.800 23.584 Chloride of sodium . . 12.542 traces. INSOLUBLE SALTS Carbonate of lime. . . 27.168 3.615 ,) ,,magnesia . . some traces.Sulphate of lime . 1.515 traces. Phosphate of lime (tribasic) . . 12.105 30.710 ,,magnesia. . traces. traces. y l'crphosphate of iron . 1.582 traces. Silicic acid . . 0.105 4.217 100*000 100 000 Carbonic acid being deducted the following is the composition in 100 parts I. 11. Sidphuric acid . . 19.782 23.195 Phosphoric acid . . . 7.998 19.926 Potash . 2.594 7-164 Soda . 25.640 23.039 Chloride of sodium . . 15.462 traces. Lime . . 27.557 20*10Y Magnesia . . traces. traccs. Oxide of iron . 0.835 traces. Silicic acid . 0.129 &a77 100-000 100~000 ASHES 0%' ESCULENT VEGETABLES. The following are the analyses of two full-grown specimens of this vegetable. Tlzc first of these was taken from a piece of garden ground near Bristol the soil of which was similar to that described under No.111 and the other was found growing \iilcll on alluvium on the banks of the Avon which was daily overAoned by the river. They were both gathered whilst in flower. a. 285.9 grs. of the fresh cultivated plant gavc 72.1 grs. of dry vegetable matter which furnished upon incineration 4.38 grs. of ash. b. 714.7 grs. of the sanie specimen (fresh) gave 180.25 grs. of dry matter and 10.951 grs. of ash. Mean per-centage of ash from the fresh plant . 1.5321 ,J 9 dried ,J . 6.0748 u. 486.2 grs. of the fresh wild plant gave 175.0 grs. of dry vegetable matter and left 11-78 grs. of ash upon incineration. b. 1701.7 grs. of the samespecimen (fresh) gave 612.5 grs. of dry matter and 41.313 grs.of ash. . 2.4*220 Mean per-centage of ash { from the fresh plant 9 dried 6.7304 9 JJ Uncultivated Cultivated plant. plant. rl--A --7 SOLUBLE SSLTS I. 11. MEAN. r Carbonic acid . 14.636 13.902 14.269 4,861 Sulphuric acid . . 3.309 3.605 3.557 7-775 Phosphoric acid . 2.181 2.019 2.100 traces. Potash . 32,695 32.783 32.739 15.815 Soda . . . 2.719 Chloride of sodium. . traces. traces. traces. 20 514 , , potassium . 13-LO3 13.015 13.059 -INSOLUBLE SSLTS Carbonate of lime . 14.511 14.711 14.611 21.432 , , iiiagnesia . 2.617 Sulphate of lime . traces. traces. traces. traces. Yhosphate of lime (tribasic) 16.197 16.223 16.210 21.670 , , magnesia . traces. traces. traces. traces. Perphosphate of iron .0.412 0.500 0456 1.699 Silicic acid . 2.803 3-133 2.968 0.849 100*047 99.891 99.969 99*951 MR. THORNYON JOHN HERAPATH ON THE Deducting the carbonic acid the followiiig is tlie composition in 100 parts Cultivated Uncultivated plant. plant. Sulphuric acid . . 4.487 9,224 w Phosphoric acid . 12.357 12.812 . . 41.299 18.766 Potash. 0 Soda . . . -3.225 Chloride of sodium . . traces 24.337 I JJ ,) potassium . * . 16.473 . 21,332 28.081 Lime . Magnesia . . -1.479 0 # Oxide of iron . 0.308 1.069 Silicic acid . 3.744 1.007 100*000 100~000 I have likewise analysed the ashes of the young heads of asparagus ; such as were in a fit state for the table. The results of my analysis are as follows cc.1839.0 grs. of the fresh shoots gave 133.0 grs. of dry vegetable matter which left after incineration 14.95 grs. of ash. 6. 4597.5 grs. of the same specimen (fresh) gave 332.0grs. of dry matter and 37.37 grs. of ash. from the fresh plant . 0.8129 Mean per-centage of ash { 9) JJ dried ,J . 11.2400 SOLUBLE SALTS I. 11. MEAN. Carbonic acid. 3.925 4.101 4.013 Sulphuric acid . ' } 31.199 30.967 31.083 Phosphoric acid . Potash ' } 32.605 32.665 32.635 Soda . Chloride of sodium. , ),potassium . . po,09010.030 10.060 INSOLUBLE SALTS Carbonate of lime . 6.832 7.080 6.956 J ,J magnesia . -Sulphate of lime . traces. traces. traces. Phosphate of lime (tribasic) 14.040 14.052 14.046 JJ JJ magnesia . traces. traces. traces. Perphosphate of iron .0.209 0.203 0.206 Silicic acid . . 1.100 0.902 1.001 ASHES OF ESCULENT VEGETABLES. Sulphuric and phosphoric acids . . . 40.530 Potash and soda . . . 35.118 Chlorides of sodium and potassium . . . 10.825 Lime . . 12.331 Magnesia . . traces. Oxide of iron. . 0.119 Silicic acid . 1.077 100*000 V.-CAULIFLOWER (Brassica oleracea var. & botrytis). The specimens examined of this plant mere brought from Corn-wall where they are cultivated in the greatest perfection. Soil.-Somewhat loamy very rich and well manured. Q. 1800.0 grs. of the fresh plant (entire) gave 159.0 grs. of dry vegetable matter and furnished when incinerated 14-0grs. of ash. b. 9500 grs. of the same specimen gave 796.0 grs. of dry matter and 70.25 grs.of ash. v from the fresh plant . 0.7585 Nean per-centage of ash { , , dried , . 8.8151 SOLUBLE SALTS I. 11. MEAN. Carbonic acid. 3.914 3.914 3.914 Sulphuric acid . . l2*101 13.379 12.740 Phosphoric acid . 6.749 6.731 6.740 Potash . . 20.932 21.296 21.114 Soda . . 6.009 5.961 5.985 Chloride of sodium. } 7-269 7.05 1 7.160 , , potassium . INSOLUBLE SALTS Carbonate of lime . . 14.161 13.597 13.879 , , magnesia . traces. traces. traces. Sulphate of lime . . traces. traces. traces. Phosphate of lime (tribasic) 26.099 25-853 25.976 9 , magnesia . traces. traces. traces. Perphosphate of iron . 1.112 1.018 1.065 Phospha-te of alumina . )traces. traces. traces. ,Y , manganese . -Silicic acid .1-400 1.446 1.423 99,746 100.246 99-996 The carbonic acid being deducted the following is the composition of the ash in 100 parts NRa THORNTON JOHN IIERAPATH ON THE Sdphuric acid . . 14.158 Phosphoric acid . . 22.135 Potash . . 23.463 Soda . . 6-651 Chloride of sodium } 7-956 , , potassium . Lime . . 23.333 Magnesia . . traces. Oxide of iron . . 0.723 Alumina. . Oxide of manganese. }traces. Silicic acid . 1.581 100*000 VI.-KIDNEY BEAN (PhaseoZus nznzdti,Rorus). This vegetable together with all those subsequently examined grew on rich well-manured and drained sandy soils in the neigh-bourhood of Bristol lying 011 the niillstonc grit and new red sand-stone which contained considerable quantities of carbonate of lime and red oxide of iron with a very notable proportion of carbonate of magnesia.a. 12840 grs of the fresh young legunies gave 76.0 grs. of dry vegetable matter and left 8.11 grs. of ash upon incineration. 6. 1000*0grs. of the same gave 58.9 grs. of dry matter and left 6.305 grs. of ash. 0.6310 v Mean per-centage of ash } from the fresh legumes. > dried , . 10-6875 The ash Contained 9 SOLUBLESALTS Carbonic acid. 14.081 Sulphuric acid Phosphoric acid Potash . . . 3.378 1.553 36.103 Soda . . . - Chloride of sodium . 4932 INSOLUBLE SALTS Carbonate of lime . . 22-194 I9 , magnesia . 3.822 Sulphate of lime . traces. Phosphate of lime (tribasic) 11 -866 ,? , magnesia . traces. Perphosphate of iron .traces. Silicic acid . 2.071 100~000 ASHES OF ESCULENT VEGETABLES. Or calculated after deducting carbonic acid. Sulphuric acid . 4-553 Phosphoric acid Potash . . . 9.451 48.667 Soda . - Chloride of sodium . 6.648 Lime . . 25.337 Magnesia . 2.553 Oxide of iron . . traces. Silicic acid . 2.791 100~000 VII.-oN 10N (Allium saticum). 15974 grs. of the fresh root when dried a.nd incinerated left 8.71 -grs. of ash = 0.5453 per cent. The ash contained SOLUBLE SALTS Carbonic acid. . 12.169 Sulphuric acid . 4-821 Phosphoric acid . 2.181 Potash . . 35.132 Soda . some. Chloride of sodiuiii . 2.755 INSOLUBLE SALTS Carbonate of lime . 5.740 >9 J magnesia 6.886 Sulnhate of liiiie .none. P&ph& of lime (tribasic) 30.089 I> ),magnesia . . traces. Perphospliate of iron . . traces. Silicic acid . 0.224 99.997 Or calculated after deducting carbonic acid. Sulphuric acid . 5.900 Yhosphoric acid . . 19.668 Potash . . 43,001 Soda . sonic. Chloride of sodiuiii . 3.372 Lime . . 23.7'65 Magnesia . 4+Ql*li Oxide of iron . traces. Silieic acid . 0.280 100.000 IXR. THORUTON JOHN HERAPATH ON THE ~TII~.-CO;\lNON WHITE GARDEN-TURNIP (BraSSiCa T/7jIa). a. 1830.0 grs. of the fresh roots cut in thin slices gave 160.0 grs. of dry vegetable matter and left upon incineration 11.863 grs. of ash. 71. 1542.6 grs. of the same gave 134.87 grs. of dry matter and 9.998 grs. of ash. from the fresh roots .0.6481 Mean per-centage of ash { ,> ,> dried 7 . 7.4136 The ash contained SOLUBLE SALTS Carbonic acid. * 14.692 Sulphuric acid . 2.141 Phosphoric acid . 4.518 Potash . 39.146 Soda . Chloride of sodium . 11.936 INSOLUBLE SALTS Carbonate of lime . 3.287 J , magnesia . 4.046 Sulphate of lime . traces. Phosphate of lime (tribasic) 19.223 , , magnesia . traces. Perphosphate of iron . traces. Silicic acid . 1*011 100*000 Or calculated after deducting carbonic acid. Sulphuric acid . 2.619 Phosphoric acid . . 16.620 47.888 Potash . Soda . -Chloride of sodium . 14.601 Lime . 14.679 Magnesia . 2.357 Oxide of iron . traces. Silicic acid . 1-236 ASHES OF ESCCLENT VEGETABLES.IX.-SWEDE TURNIP OR RUTA-BAGA (Brassica campestris var. napo-brct ssicce). a. 2116.0 grs. of the fresh young roots gave 355.0 grs. of dry vegetable matter and left 26.05 grs. of ash upon incineration. b. 6348.0 grs. of the same gave 1065.0 grs. of dry matter and 78.15 grs. of ash. from the fresh roots . 1.2311 Mean per-centage of ash { , , dried 7.2817 , ?Y The ash was composed of SOLUBLE S4LTS I. 11. MEAN. Carbonic acid. 17.349 16,893 17.121 b Sulphuric acid . 3.196 3.534 3.365 Phosphoric acid . 6.897 7.891 7.394 Potash . 5 1.070 49.786 50.428 Soda . traces. traces. traces. Chloride of sodium . { 5.890 5.994 5.942 , , potassium . INSOLUBLE SALTS Carbonate of lime . 2.289 2.322 2.305 > , magnesia .2.589 2.452 2.520 Sulphate of lime . traces. traces. traces. Phosphate of lime (tribasic) 7.943 7.955 7.949 > , magnesia . 2.487 2.191 2.339 3 , alumina . )traces. traces. traces. J , manganese . I Perphosphate of iron 0.400 0.366 0.383 Silicic acid 0.087 0.062 0.074 -100.197 99.446 99.820 Yielding the following quantities in 100 parts after deducting the carbonic acid Sulphuric acid . 4.242 Phosphoric acid . . 15,890 Potash . . 62.631 Soda . . traces. Chlorides of sodium and potassium . 7.439 Lime . 6.922 Magnesia . 2.531 Alumina and oxide of manganese . traces. Oxide of iron . 0.251 Silicic acid . 0.094 1ci 3IR. THORNTON JOHN HEBIPATI-I ON THE X-BEET (Beta vulgaris). a.-1950.0 grs.of the sliced roots of the variety called the cr Long Red," when dried and incinerated "gave 19.22 grs. of ash = 0.9856 per cent. Composition of the ash SOLUBLE SALTS Carbonic acid . . 17.876 Sulphuric acid . G.082 Phosphoric acid . . traces. Potash } 39.016 Soda . Chloride of soditmi . 5*9m IXSOLUDLE SALTS Carbonate of liinc . . 15.609 Carbonate of magnesia . . 4.162 Snlphatc of hie . . traces. Phosphate of lime (tribasic) . . 11.293 >> , mag:nesia . .-I ,J , aluiiiina . . I traces Perphosphate of iron . . ) of b Phosphate of manganese . . 1 each. Silicic acid . .J 100*000 The composition calculated on 100 pwts after deducting the carbonic acid was Sulphuric acid . . 8.322 e Phosphoric acid .7.101 Potash .. ' } 53463 Soda . Chloride of sodium . 8.158 Lime . . . . 20.244 Magnesia . 2.712 Alumina Oxide of iron . traces , , manganese Silicic acid . 100~000 XL-RAD~SH(Raphanus sativus). a.-875.0 grs. of the fresh root gave 33.218grs. of dry vegetable matter and left 7.25 grs. of ash upon incineration. ASHES OF ESCULENT VEGETABLES. b.-6000*0 grs. of the same specimen gave 242.08 grs. of dry matter and 49.8 grs. of ash. Mean per-centage of ash { from the fresh roots 0,8285 , , dried , 20.0900 Composition of the ash SOLUBLE SALTS 9 Carbonic acid . 19.498 Sulphuric acid . 3.624 Phosphoric acid . none. Potash 18.919 Soda . 18.699 Chlorides of potassium and sodium 10-886 INSOLUBLE SALTS Carbonate of lime .6.994 , , magnesia . 1.814 Sulphate of lime . 0.134 Phosphate of lime (tribasic) . 17.634 , , magnesia . 1.396 Perphosphate of iron . 0.134 Silicic acid . . 0.268 100~000 Calculated composition after deducting the carbonic acid Sulphuric acid Phosphoric acid Potash . . . . . 4.840 11.916 24.739 Soda . . . . 24-45 1 Chlorides of potassium and sodium . 14.235 Lime . . . 17.608 Magnesia . Oxide of iron b . I . . 1.728 0.077 Silicic acid . 0 . 0.352 X1I.-CARROT(Daucus carota). a.-1010*0 grs. of the fresh roots of the variety called the “ Long Scarlet,” gave 133.0 grs. of dry vegetable matter and upon incine-ration 13*$85grs. of ash. b.-12625-0 grs. gave 1662.0 grs of dry matter and 1680462 grs.of ash. YOL. II.-R’O. v C MR. TIIOKNTON JOHN HERAPATIi ON TI-IK from the fresh root 1.3340. Mean per-centage of ash { , , dried , 10.1370. Composition of the ash SOLUBLE S-4LTS I. 11. MEAN. Carbonic acid 16-261 16.263 16.262 Sulphuric acid . 6.432 6.634 6.533 Phosphoric acid * 4.309 4.099 4.204 Potash . 13.001 14.005 13.503 Soda . . 23.909 23437 23.673 Chloride of sodium. . 7.321 7-301 7.311 INSOLUBLE SALTS Carbonate of lime . . 7.420 7.430 7.425 , , inagnesia . 2.241 2*227 2.234 Sulphate of lime . . traces. traces. traces. Phosphate of lime (tri-basic) . . 16,509 16.713 16.611 Phosphate of magnesia } traces. traces. traces. Perphosphate of iron . . Silicic acid .. . 2.205 2.195 2.200 99.608 100-304 99.956 The following is the composition in 100 parts aftcr deducting the carbonic acid Sulphuric acid . . . 8.239 Phosphoric acid . . 14.970 Potash . . 17.029 Soda * . 29.855 Chloride of sodium . 9.220 Lime . 16.523 0 Magnesia . . 1-341 Oxide of iron . 0 * . traces. Silicic acid . . 2-823 100~000 XIII.-PARSNIP (Pastinaca sativa). a.-1000*0 grs. of the fresh root gave 238.0grs. of dry vegetable matter and left upon incineration 14-12grs. of ash. 6.-4965.2 grs. gave 1181.0 grs. of dry matter and 70.10 grs. of ash. from the fresh roots 1.4130. Mean per-centage of ash { , dried , 5.9340. ,> ASHES OF ESCULENT VEGETABLES. The ash contained SOLUBLE SALTS I.11. MEAN. Carbonic acid . . 14.062 14.264 14.163 Sulphuric acid . . . 4873 4.715 4.794 Phosphoric acid . 5.706 5.352 5.529 Potash . ’} 43.351 43.461 43.406 Soda . .. Chloride of sodium . 3.806 3.756 3.781 INSOLUBLE SALTS Carbonate of lime . . 7.760 7.820 7 790 , , magnesia . --Sulphate of lime . . traces. traces. traces. Phosphate of lime (tribasic) 17.509 17.691 17.600 , , magnesia . traces. traces. traces. Perphosphate of iron 2.915 2.899 2.907 traces. traces. traces. Silicic acid b ~. 99-982 99 958 99-970 Deducting the carbonic acid the following composition in 100 parts is obtained Sulphuric acid . . . 5.751 Phosphoric acid . . . 18,270 I Potash . ’ *} 52-670 Soda . 0. Chloride of sodium.. . 4.588 I Lime . . . 16.811 Magnesia . . traces. Oxide of iron . . . 1.910 Silicic acid 4 L . traces. 100~000 XIV. POTATO(Solanurn tuberosum). I have analysed the ashes of the tubers of five different varieties of this plant viz. A. the 4c White Apple,” B. the ‘I Prince’s Beauty,” C. the ‘< Axbridge Kidney,” D. the “ Maggie” or “ Maghie,” and E.the ‘‘ Forty-fold.” All of these were grown on the same soil and under precisely similar circdmstances. A. a.-913.0 grs. of the fresh tubers of this variety cut in thin slices gave 247.0 grs. of dry vegetable matter and left upon inci- neration 11.895 grs. of ash. b.-7675*0 grs. gave 2074.7 grs of dry matter and 99-997 grs. of ash. c2 MR THORNTON JOHS HERAPATH OX TIIF 13.a.-693.0 grs. of the fresh tirbers gave 202.6 grs. of dry vege-table matter and 7.320 grs. of ash. b.-1151*0 grs. gave 337.3 grs. of dry matter and 12.298 grs. of ash. C. a.-G24*4 gm. of fresh tubers gave 182.3 grs. of dry vegetable matter and 7.952 grs. of ash. b.-16$34 grs. gave 486.03 grs. of dry matter and 21.163 grs. of ash. 11. cr.-T48-0 grs. of fresh tnbers gaw 236.3 grs. of dry vegetable matter and 8.18’7 grs. of ash. b.-33GO 0 grs. gave 1062% grs. of dry matter and 36.832 grs. of ash. E. a.--5960 grs. of fresh tubers gave 132.0 grs. of dry vegetable mattcr and 5.25 grs. of ash. b.-l430.4grs. gave 317.0 grs. of dry matter and 12-6grs.of ash. The following tables give a coniparative view of the mean per-centage and composition of the ash from these five rarieties of the potatoe Nean per-centage of ash A.B. C. D. E. From the fresh tubers . 1.3029 1.0609 1.2709 1.0953 0.8808 , , dried , 4.8180 3.6304 4.3581 346.48 3.9750 Composition of the ash SOLUBLESALTS Carbonic acid . 21.059 16.666 21400 18.162 13.333 Sulphuric acid . . 2.774 4.945 3-244 5.997 6.780 Phosphoric acid . . 5.716 8.920 3.774 6.669 11.428 Potash . I . 58.467 54.166 55.610 55,734 53.029 Soda . traces. traces. traces. traces. traces. Chloride of sodium . traces. traces. traces. traces. 2.095 INSOLUBLESALTS Carbonate of lime . 0.844 2.019 3.018 1.954 2.286 , , magnesia. 3.530 0.273 1.257 2.565 0.570 Sulphate of lime . . traces. traces. 0.125 traces. traces. Phosphate of lime (tri- basic) .. 3.363 0.683 3.835 5.374 2.856 Phosphate of magnesia. 9.247 12.298 9.550 3.545 7.623 Perphosphate of iron Phosphate of alumina . , , manganese traces. traces. - traces. -I 0.062 -I traces. - traces. traces. traces. Silicic acid. . traces. traces. 0.125 traces. traces. 100~000100*000100~000 100~000 100~~00 -4SHES OF ESCULENT VEGETABLES. A. B. C. D. E. Sulphuric acid . . 3.615 6.007 4.329 7530 7,942 Phosphoric acid . . 17-222 20.831 14.892 14.363 20.677 Potash . . 69.688 65.823 70.590 69.985 62.118 Soda . . traces. traccs. traces. traces. traces. Chloride of sodium . traces. traces. traces. traces. 2.454 Lime . . 2.976 1.843 * 4.969 5.009 3.301 Magnesia . . 6.499 5-496 5.014 3.113 3.508 Oxide of iron .traces. traces. 0.043 traces. traces. L Alumina . . traces. -traces. Oxide of manganese --traces. Silicic acid . . traces. traces. 0.163 traces. traces. 100~000100*000loooooo 100~000100*000 If we consider attentively the results contained in the preceding pages we shall arrive at the following general conclusions 1. That the inorganic constituents differ both in proportion and composition in each of the crops examined. 2. That cultivation can to a very considerable extent modify and control the assimilative powers of plants for certain inorganic sub- stances. This is most decisively proved in the case of the potato plant (No. XIV) in which neither the proportion nor chemical composi- tion of the ashes from any two varieties are alike.True it is that there is in many respects a great resemblance to be detected in all of them but the differences are still much too great to be over-looked. It woiild be extremely interesting to ascertain by &sect experi- ment whether the various varieties of plants which occur naturally (and which therefore cannot be the result of cultivation) likewise contain different inorganic constituents as if such were proved to be the case it would in my idea go far to explain to us the cause of the formation of varieties in the vegetable kingdom which is at present except in a few instances an almost inscrutable mystery. This influence of cultivation on plants is of great practical impor- tance in agriculture for as the evident object of the farmer's endeavours is to obtain the greatest amount of produce from his land at the least possible expenditure of time and money so does it become necessary for him in order to effect this to ascertain the variety of the plant which is best suited to his soil; for by substi- tuting one variety for another he may often obtain as large a crop 3lR.THOBNTON JOHN HEEAPATH ON THE at as early a season and at the same time be enabled to effect a great ceononiy in the application of his manurcs. Hence also he must not take it for granted because one variety of a plant does not happen to succeed that therefore his land is not adapted for the cultivation of that particular vegetable ; for where one variety will utterly fail anothcr will often yield an admirable crop.Another remarkably good iiistance of the change produced by cultivation in the inorganic constitueiits of plants is exhibited in the two asparagus plants (No. IV) where it will be observed that the soda and lime-salts of the wild specimen (11) hare been to a very considerable extent replaced by potash-salts in the cultivated plant (I). These results would not however appear to be in accordance with the law or rather hypothesis recently advanced by Professor Liebig; namely that the sum of the oxygen in the bases in combination with the organic acids (which occur as carbonates in the ash) is constant in the same species of plant no matter what the nature of the soil may be upon which the individual specimens are grown ;for it will be seen that whilst the ashes of the cultivated plant contained 14.269 grs.of C02in the soluble salts = 5.1887 grs. of 0 in base 14,611 grs. of COz+CaO = 2,3370 , 7) Sum of oxygen 7.5257 those of the wild specimen on the contrary contained only 4.861 grs. of C02in the soluble salts = 1.7670 grs. of 0 in base. 2143.2grs. of' C02+CaO = 3.4290 , , 2.617 grs. of C02+&ifgo = 0.4940 , , 5.6940 01' nearly two per cent less in the total proportional of oxygen-a difference evidently much greater than can be attributed to the errors of analysis only. I intend however if my time will allow me to make a much more extensive series of experiments on this subject in the course of another year when I hope to communicate the results to the Society.3. That the principal and by far the most important constituents of root crops are the alkalies potash and soda which occur for the greater part free the remainder being in combination with sulphuric and phosphoric acids. They generally form from 43 to 71 per cent of the ash. It must not be imagined however that all the alkali which was ASHES OF ESCULENT VEGETABLES. estimated in the ash as carbonated existed in the living plant in combination with organic acids part of it was evidently produced by the decomposition of the nitrates by the carbon of the vegetable matter. In such large quantities in fact did the nitrates occur in the case of the radish (No. XI) that actual scintillations were observed to take place upon incinerating the dried plant.By a proximate analysis I found the dried roots to contain from 13 to 14 per cent of the mixed nitrates of potash and soda. 4. That in the potato (No. XIV) the lime except in one instance is greatly exceeded in quantity by the magnesia; sometimes even in the proportion of three to one. If we examine we shall see that this observation is likewise borne out by the experiments of other chemists. Thus Boussingault found the relation of the former to the latter earth to be as 1.8 to 5.4; and Daubeny in three analyses found respectively 2.71 3.67 and 2-54per cent of lime and 10.98 7-00 and 6.31 per cent of magnesia. In fact magnesia would appear to be necessary for the growth and well-being of the potato-plant as it has bcen observed that when it is not present in the soil in sufficient quantity the tubers rarely if ever attain their full development.5. That the akaline chlorides are present in greater or smaller quantity in all the crops examined. Although these sometimes occur to such an extent as to form more than half the entire weight of the ash I think it is a great question whethcr they perform any important part in the organism of the plant. Indeed judging from the mariner in which they arc observed to fluctuate in quantity in different specimens of the same plant I am inclined to believe that in the majority of cases (if me cxcept those plants of niarine origin such as the sea-kale asparagus &c. to which they are essential) they ought to be classed amongst those substances which from their extreme solubility are absorbed by the roots of plants and are thus carried into the system without being actually necessary either for their health or existence.In proof of this opinion Daubeny found in three analyses of the ashes of turnip-roots 5.4 per cent of chlo- ride of sodium in one and none in either of the others; and in the three specimens of potato-ashes before mentioned that gentleman found respectively 8.75 5.88 and 1.87 per cent of mixed chlorides I found in five analyses 2.454 in one and only traces in the other four. In the ashes of the roots of the carrot and parsnip Sprengel found 1.76 and 7.15 per cent of chloride of sodium; I found 9.22 and 4.588 per cent 24 ON THE ASHES OF ESCULEXT VEGETABLES.6. That in all young succulent shoots as in root crops the alka- lies and alkaline salts greatly exceed in quantity the insoluble earthy and metallic salts. I have already attempted to explain the reason of this iu a former paper. The sulphuric and phosphoric acids are also present in rather con-siderable proportion especially in the sea-kale and asparagus (Nos. I11 and IV) mherc they amount to from 40 to 43 per cent of the ash. The great relative increase of these acids and potash observed in the young as compared with the old plant of sea-kale was no doubt occasioned by the salts of the animal manure with which the former had been supplied. In order to render these analyses of practical utility to the farmer and horticulturist I have annexed a table showing the relative quan- tities of manure requisite for a ton weight of each of the vegetables examined in the fresh state; from which it will of course be easy for him to calculate by means of a simple rule-of-three sum the weight necessary to be applied to his land per acre for any particular crop.I need hardly say that these calculations do not pretend to any extraordinary accuracy ;they must only be considered as approxima- tions to the truth. TABLE SHOWING THE PROPORTION AND COMPOSITION OF THE MANURES REQUIRED FOR A TON WEIGHT OF THE PLlESH VEGETABLE GIVEN IN AVOIRDUPOIS POUNDS AND OUNCES. Sea-kale. Celery. Asparagus. Cauliflower Kidney Garden Swede I I entire bean turnip. turnip. Jl 1 I V J Young sprouts.plant. legumes. Roots. Pearl-ash .......... 1.96 10.84 { 5.6 Soda-ash . 10 HO) ..... 1.10 -}’lS2* Glauber’s salts (SO3,kaO ..... 14.3& 0.13 8.145 Xpsom salts (SO3 MgO c 7HO) ..... -Commonsalt ......... -1-15; 1,135 1.4- Lime ......--C~O Gypsum (~03 + i rroj ...... --Bone-earth ......... 6.9 6.125 3,134 7.8% 2.2; 4.4; 4*3$ c Carbonate of magnesia ....... -- Oxide of iron ........ -0.05 0.2 0.29 0.4 Silica ........ 0.11 0.64 24-11 26-73 174& 23.7$ Actual quantity of real inorganic constituents in same cr weight of freshvegetable ...... 15.2 1 21.12% 16.15 15.113 10.8 I Beet. Radish. Carrot. Parsnip.’ Potato Tubers Varieties. J White Prince’s Axbridge Maggie or Forty-1 Roots. apple. Beauty. kidney.Maghie. fold. L-l--Pearl-ash ...... 5.14 22.93 18.11 22-8f 19.14 15-33 Soda-ash ....... } 12.15 { !::$10.3 } ”p89’;” { --- Glauber’s salts ....... -0.12 5.5p 6.1 --- Epsom salts ....... 2.12 1.Sf 1.140 -5.4 3*10$ 2.14 4.6 4.1% I Common salt ....... 1.5 2.09 2.3 1.3 --0*6* Lime ........ -. -I I -I I I I Gypsum ........ 6.0 ---- Bone-earth ....... 2.7 5.0+ 7.12i 10.48 8.24 8.13 7.04 6.15 7*9f Carbonate of magnesia ..... --2.1* 1.1 1.6 -Oxide of iron ....... -0.8 --O*O$ -- Silica ........ 0.03 0.104 -0.03 - 25.7 20.05 33.154 36-76 38*1* 32-32 33-133 30.53 27’4$ -I--Actual quantity of real inorganic constituents in same weight of fresh vegetable ... 16.29 14-24 23.114 26-04 22.4 19.if 21*13$ 19*@ 16,134 MR WILLIAM SYKES WARD Dec.4 1848. The President in the Chair. Mr. Brodie presented a copy of his paper " Investigations of the chemical properties of Wax," to the Library; Mr. W. Sykes Ward preserited his Balance Galvanometer to the Museum. Messrs. E. Pon-tifex and Ralph Busby were elected members of the Society. The followirig papers were read On a Balance GaEvanomPter. BY WILLIAMSYKESWARD,EsQ.-No recognised method being known by which the working effects of various voltaic arrangements can be referred to a common standard it occurred to the author of this paper that this might be. more easily effected by means of a new form of galvanometer than by any other. The new galvanometer proposed consists of ti coil of covered copper wire in the form of a long parallelogram the ends of the wire being extended so as to form pivots on which the coil swings and which pivots also form the connections for the current to pass through the coil and its supports.To the coil are appended two short arms forming a kind of balance-beam to which small scale-pans are attached. The two poles of a horse-shoe magnet of moderate power are inserted within the coil so as to allow it a moderate range of vibration and the force of the current is measured by the weight in grains supported in the scale-paus The galvanometer is recommended on account of the facility with which coils containing various lengths of wire and of different thickness or resistance can be adapted and readily changed as most suited for any experiment and it is frequently found advisable to use a coil having about the same resistance as the other resistances of the circuit; although for general purposes it is most advisable to have two coils one consisting of 10 feet of copper wire of No.20 Birmingham wire guage of which 1 foot weighs 27.4 grains for estimating quantity and another of 100 feet of about No. 35 or -+th of an inch of which one foot weighs 97 grains for estimating intensity or electro motive force; the former wire may be covered with cotton ; the latter should be well but lightly covered with silk. The magnet should be so strong that the indications may be manifested by considerable weights ; but it should not be too highly or nearly saturated or charged with magnetism as its power would then be very liable to be impaired by use or by time.Several coils or bundles of wire similar to that of the moveable coils and of precisely the like resistance should also be provided. The coils are made most abantageously by winding the wire upon a parallelogram of wood about three inches long and half an inch thick and of about twice the width of the coil slightly tapering towards one side to facilitate the removal of the coil. A IaTer of the insulated wire is wound ON A BALANCE GALVANOMETER. upon the parallelogram and slightly cemented with shell-lac ; another layer of wire is then wound upon the first which is again cemented and so on until sufficient wire has been added. The coil being carefully removed from the block on which it has been formed two bent needles are attached to the sides to form pivots having the points of the needles a little above the centre of gravity of the coil which needles are adjusted by bending so that the coil may hang horizontally.The needles or pivots for the coils of thin wire answer best when made of platinum. Around the piyots a portion of the uncovered end of the wire is wrapped so as to dip into mercury placed in small conical holes in which the ends of the needles are supported. If magnets could with certainty be obtained of precisely the same power a standard pattern might be agreed upon for the coils and uniform instruments procured. The value of the indications can however readily be modified in weight by altering the length of the arms to which the scale-pans are attached; and it is proposed that the galvanometer be adjusted to a common standard by making a grain weight supported by the 10-feet coil the equivalent to 1 grain of zinc consumed in a single voltaic combination in one hour.The galvanometer may therefore be adjusted by employing a pair of elements the zinc of which has been weighed ; the circuit is then com- pleted with a galvanometer and allowing the action to continue for one hour or any convenient part of an hour from time to time the weights counterpoised by the current are observed and noted down an average being obtained by interpolation ; the zinc being taken out and weighed the ratio between the number of grains dissolved and the weight in the scale- pan will be ascertained.If this be a convenient number for reduction the galvanometer will be retained in its then state and the observations reduced or the arms of the balance which I ha%-e found may be fixed sufficiently by shell-lac are altered in length until the indications cor- respond-grain balanced for grain dissolved. This may be perhaps more easily understood by a practical example. A small arrangement of the nitric acid battery was used in which a sheet of platinum surrounded the porous cell and a narrow strip of zinc was placed within the cell. In the first instance the zinc weighed 114 grains. hm At 8 27 the galvanometer balanced 57 grains , 8 35 ,Y 54 JJ 9 8 40 1 58 93 ,) 8 50 $9 57 ,J $9 8 57 YJ 57 3 5) 283 , 311%.BALY OK THE; ACTION OF' The zinc then weighed 83 grains 31 having been dissolved thus the instrument instead of having balanced 62 grains on the average had only balanced 56.6 and therefore required adjusting either by altering the position of the magnet or altering the length of the arms of the balance which for this purpose consisted of two thin slips of brass each cemented with shell-lac on a thin piece of wood the piece of wood being cemented to the coil thus the small brass arm being warmed in the flame of a lamp the length of the arm from the pivot is easily altered without affecting the wrapping of the coil. It was also proved by experiment that within very considerable limits the weight balanced by the galvanometer may be relied on as indicating the quantity of current passing.The relative indications of the galvanometer and the voltameter mere likewise compared and the author arrive! at the conclusion that this form of galvanometer will give much more accurate indications than can be obtained from a voltameter in addition to the advantage it presents of affording results more immediately and interposing less additional resist- ance in the circuit.

ISSN:1743-6893    

DOI:10.1039/QJ8500200004

出版商:RSC    

年代:1850

数据来源: RSC

摘要:

Mlt BALY OK THE; ACTION OF 11.-On the action of Baryta on Salicylic Elher. BY G. BALY,ESQ. One of the most interesting facts with which we have become acquainted by the investigations of M. Cahours,* is the remarkable decomposition which the oil of Gaultherin procumbens (salicylate of oxide of methyl) undergoes when subjected to the action of alkaline earths at a high temperaturc. On performing this experiment M. Cahoiirs obtained a fluid possessing all the properties of anisol a substance which he had previously discovered in acting with baryta upon anisic acid. Gaultheria oil and anisic acid are isomeric the composition of both these substances is expressed by the formula Cl H 06 but nobody can mistake the difference in their molecular arrange- ment and it was ccrtainly a startling result to see two such dissimilar compounds exhibiting the same behaviour when under the influence of powerful agents.The identity in the yroducts of decomposition of these isomeric bodies is by no nieans an isolated fact; several cases of a similar nature have since been observed. Anthranilic acid and nitrotoliiol are likewise isomeric and no two bodies coulcl present a more striking dissitnilarity in constitution ; nevcrtheless both these compounds * Ann. de Chimie et Phys. 3i.rne SEr. t. x. 1). 327. BARYT.4 Oh-SALICYLIC ETHER. when subjected to the action of heat undergo as pointed out by Drs. Hofmann and Muspratt,* exactly the same decomposition they are split into aniline and carbonic acid.In his mcmoir on gaultheria oil 31. Cahours mentions that salicylate of oxide of ethyl when acted on by baryta undergoes a similar decomposition to the methyl compound ; an oily liquid inso- luble in alkalies is produced carbonate of baryta remaining in the retort. It appeared extremely probable that the compound thus obtained was an analogue of phenol and anisol containing two more equivalents of carbon and hydrogen than the latter substance. &I.Cahours not having prosecuted this investigation Dr. Hofmann invited me to prepare the coinpound in order to establish its compo- sition by an analysis and study its properties. The salicylic acid used for the following experiments was pre-pared from gaultheria oil which readily yields this acid in a state of perfect purity.Salicylic acid is etherified with great facility. By distilling a mixture of salicylic acid alcohol and sulphuric acid I obtained the ether with all the properties M. Cahours mentions. The boiling point of the pure liquid was constant at 229O.5 C = (414O F.) a few degrees higher than the temperature specified by M. Cahours who found it to be 225O (4370 F.). The specific gravity of the ether is 1.097. On mixing pure salicylic ether with anhydrous baryta a very considerable evolution of heat takes place sufficient to effect complete decomposition iinless the experiment be made with sinall quantities at a time. In order to avoid loss it is necessary to add the ether drop by drop to the baryta until an increase of temperature is no longer observed on further addition.In this manner a dry solid compound of the ether with baryta is obtained corresponding evidently to the gaul- therate of baryta obtained by acting in the same manner on the methyl compound. On distilling this compound in a small glass retort a brownish yellow liquid passes over possessing a strong odour of phenol. The distillate thus obtained is a mixture of two liquids of which the one is soluble in potash and presents all the propertics of phcnol whilst the other is a liquid of an agreeable odour for which I propose the name of snlithol in order to indicate that it is formed from salicylic ether. Salithol is easily purified; for this purpose the crude product of the distillation is treated with a dilute solution of potash which yemoves at oace tlic odoirr of phenol that substance being dissolved leaving a yellow layer of oil on the top of the liquid.The oil is * Memoil c,f the Chemical Societ of I,on(Io;l Y. ii. p. 243. MR. BALY OW THE ACTIOS OF washed with water separated by means of a pipette dried over fused chloride of calcium and finally rectified. Salithol when pure is a colourless liquid of a very agreeable aro- matic odour. Its boiling point is l75O C. (3470 F.) An analysis, by combustion with oxide of copper gave the following results I. 0.1915 grm. of substance gave 0,5515 , carbonic acid and 1.1450 , water. 11. 0.1938 , of substance gave 0.5575 , carbonic acid and 0.1490 , water Per-centage composition I. 11.0 Carbon . 78-64! 78-45 Hydrogen . . 8-41 8.54 These numbers closely correspond with the formula c,,HlO 029 as may be seen from the following table Theory. Mean of experiments. -16 eq. of carbon . . . 96 = 78.68 78-49 10 , of hydrogen . . 10 = 8-19 8.47 2 , of oxygen . . 16 = 13.13 13.03 7 -1 , of Salithol . . 122 100.00 99.99 The formation of salithol is perfectly analogous to the production of phenol from salicylic acid and of anisol from anisic acid or salicy-late of oxide of ethyl. This will be evident from the following formulse C14 H C -f-2 BaO = 2 BaO CO 4-C, H R, *- Salicylic acid. Phenol. C16 H 0 + 2 BaO = 2 BaO CO + O, H 0, -’ - Anisic acid. Anisol. C, H, 0 + 2 BaO =2 2 BaO CO + C,,II, 0 Salicylic ether.Salithol. The simultaneous production of phenol arises from part of the salicylic ether being converted into salicylate of baryta when acted on by caustic baryta. BARYTA ON SALICYLIC ETHER. It is very probable that the progress of science will make us acquainted with an acid isomeric with salicylate of ethyl and belonging to the series of acids with six equivalents of oxygen of which salicylic and anisic acids are as yet the only members. An acid of this composition when distilled with baryta would evidently likewise be converted into salithol. I should have liked to control the formula of salithol by the study of some of its products of decomposition the difficulty however of obtaining it in sufficient quantity has prevented me from entering more minutely into the investigation.Chlorine acts very powerfully on salithol ; heat is evolved during the reaction and hydrochloric acid disengaged a viscid mass being produced which after standing for several weeks shewed a tendency to crystallize. Bromine forms in the same manner a heavy oily compound With salithol which solidifies after a few days to a hard crystalline mass soluble in boiling alcohol from which it crystallizes on cooling. The appearance of the crystals thus deposited as well as the results of several combustions indicated that the action of bromine gave rise to the formation of various compounds. It is very likely that a series of substitution-products like the following may be formed in this manner. The small quantity of material at my disposal did not admit of their separation by repeated crystalliza- tion.DINITRO-SALITHOL. Fuming nitric acid dissolves salithol producing a liquid of a beau-tiful violet colour which colour disappears completely on the appli- cation of heat. By ebullition the whole of the salithol is converted into a crystalline mass which is insoluble in water but dissolves in boiling alcohol from which it is deposited on cooling in needle-shaped crystals. These crystals likewise consist of various com-pounds; if however the ebullition with nitric acid has been continued for some time a product is obtained which after being washed with water and crystallized two or three times from alcohol seems to be nearly pure dinitro-salitbol.MR. JOHN MITCHELj ANALYSIS OF TKI By burning two products obtained at different times with oxide of copper in the above manner the following results ivere obtained I. 0.200grm. substance gave 0.316 , carbonic acid and 0.074 , water. 11. 0.282 , substance gave 0.452 , carbonic acid and 0*1015, water. Per-centage composition 1. 11. Carbon . 43.09 43.71 HydrogenThe formula . . 4-11 3.99 requires Carbon . 45.28 Hydrogen . . 3-77 The deficiency in the carbon probably arises from an admixture of trinitro-salithol. Unfortunately the last portion of rny substance being consumed I was prevented from repeating the analysis with a purer product.

ISSN:1743-6893    

DOI:10.1039/QJ8500200028

出版商:RSC    

年代:1850

数据来源: RSC

摘要:

MR. JOHN MITCHEL ANALYSIS OF TKI III.-Analysis of the Water supplied by the Humpstead Water-works Company. By JOHNMITCHEL, ESQ. The deep well water from Messrs. Conibe and Delafield’s Brewery has been analysed by Professor Graham and the water of the Artesian Wells at Trafalgar Square by Messrs. Abel and Rowney as well as that of the ‘I’hames by Mr. Clark but I am not aware that the waters supplied by the London Water Companies have yet been subjected to analysis. It was thought that such a series of analyses moulcl be an useful addition to thosc already cited not only in a scientific but also iri a sanatory point of view. The present communication the first of the series has reference to an examination of the water supplied by the Hampstead Water-works Company.The water was not taken direct from the works but analyzed as supplied to the house; the chief object being to ascertain whether the water in question possessed any power of taking up lead or zinc as I had been informed on the authority of a plumber in the neiphbourhood that such %as the case WATER SUPPLIED BY THE HAMIPSTEAD WATER-WORKS 33 with reference to the former metal I have found that as far as the water analyzed was concerned no perceptiblc action was exerted and I am the more iiicluced to believe this correct from the circumstance that several leaden cisterns have been for a great number of years continually subjected to its influeiicc and do not appear affected in the slightest degree. This may be in some measure explained by the comparatively large quantity of soluble sulphates contained in the water as it Bas been shewn by Dr.Christison that water containing even a small amount of sulphates is comparatively without action on metallic lead. The water is pumped continuously from a plain bore-hole at the Works in Pond Street Hampstead and is obtained partly from the sand and partly from the chalk. The specific gravity of the water at 58O F. is 1000.65 distilled water being 1000. Qualitative analysis exhibitccl the presence of magnesia lime potash and soda with sulphurie silicic and carbonic acids chlorine organic matter and a trace of phosphoric acid. A. Determination of the total amount of fixed constituents. Amount of n ater. Fixed residnc. Per-centage.I. 4000 grs. 2.284grs. 0.0571 11. 3500 , 2.002 ,) 0.0575 Mean 0.0573 B. Determination of sulphuric acid Amount of water. Sidphate of bar) ta. Per-centage of Sulphuric acid. I. 4000 grs. 1.136 grs. 0-0097524 Ir. 3581 , 133.1 , 0.009 7504 Mean 0.0097514 C. Determination of chlorine. Amount of water. Amount of chloride Chlorine per cent. of silver. I. 3524 grs. 2216 grs. 0.01555 11. 4120 ,> 2-590 , 0.01567 Mean 0.01566 D. Determination of the silicic acid. Amount of water. Amount of silicic acid. Silicic acid per cent. grs. 0.00040685 I. 8750 grs. 0-03.2 11. 10000 , 0.041 , 0~00041000 Mean 0.00040842 D MR. JOHN MITCHEL ANALYSIS OF THE E. a. Determination of the total amount of lime. Amonnt of water.Amount of carbonate Lime per cent. of lime. I. 7850 grs. 0.801 grs. 0.005717 ;11. 10000 , 1.020 0.005615 17lean 0.005666 A given quantity of water was boiled for half an hour the flask being so arranged that no evaporation could take place. The pre- cipitate formed was separated by filtration aiid the amount of lime in the precipitate and filtrate determined in the usual manner. 6. Estimation of lime in the precipitate. Amount of water. Amount of carbonate Per-centage of lime in the of lime. water as carbonate. 8000 grs. 0.438 grs. 0.003056 c. Determination of lime in filtrate. Amount of water. Amount of carbonate Per-centage of lime in the of lime. water as soluble salts. 8000 grs. 0.371 grs. 0.0025997 F. Determination of magnesia.Amount of water. Pyro-phosphate of Per-centage of magnesia. magnesia. 7850 grs. 0.505 grs. 0.002355 10000 , 0.644 , 0.002357 Mean 0,002356 G. Determination of the alkalies. Amount of water. Amount of chlorides of potassiurn and sodium. 10000 grs. 3475 grs. 8000 , 2.782 , a. Estimation of potash. Amount of water. Potassio-chloride of Per-centage of potash. platinum. 10000 grs. 1.313 grs. 0-0025335 8000 , 1.050 , 0.0025326 ~ Mean 0.0025330 6. Estimation of soda. Amount of water. Chloride of sodium. Per-centage of sods. 10000 grs. 3.074 grs. 0.0016193 2.450 , 0.0016232 >J MeaH 0.00162125 WATER SUPPLIED BY THE HAMPBCEAD WATER-WORKS. 35 H. Determination of carbonic acid. This was determined in the usual manner by the addition of a mixture of chloride of calcium and ammonia to a known weight of water.21000 grs. of water thus treated gave 8.21 grs. of precipitate which by the ordinary process yielded 1456 grs. of carbonic acid = 0.006938per cent. of that body in the water. In order to determine the phosphoric crenic and apocrenic acids and extractive matter 100lbs. of the water were evaporated to 2 lbs. giving 72 grs. of precipitate the filtrate and washings weighing 25000 grs. I. Determination of phosphoric acid in combination with lime. Amount of precipitate. Pyro-phosphate of Per-centage of magnesia. phosphoric acid. 17 grs. 1.016 grs. 0.000392 K. Determination of organic matter. a. Apocrenic acid. Amount of precipitate.Copper-salt obtained Per-centage of apocrenic acid. 22.2grs. 0.320grs. 0.00012005 b. Crenic acid. Amount of precipitate. Copper-salt obtained. Per-centage of crenic acid. 22.2 grs. 1.986 grs. 0.000237 c. Extractive matter. Amount of filtrate. Extractive matter. Per-centage of extractive matter. 10000 grs. 6-88grs. 0.0002457. According to the above results the water contains per imperid gallon in grains Carbonate of lime . 3.83250 Carbonate of magnesia 3.40830 Phosphate of lime . . 027672 Sulphate of lime . 442018 Sulphate of potash . . 3.27812 Sulphate of soda . 4.81130 Chloride of sodium . . 17*75814 Silica acid . . *28589 Crenic acid . . 016590 Apocrenic acid . 008403 Extractive matter . . 1.71990 Oxides of iron and manganese. * traces 4D04110 D2 DR HOPMANN ON THE ANILIDES. The ainouut of fisccl rcsicluc obtained by direct experiment was 49-11 grs. pcr gallon. The amount of pure carbonic acid in the water is 4.39 cubic inches in the imperial gallon.

ISSN:1743-6893    

DOI:10.1039/QJ8500200032

出版商:RSC    

年代:1850

数据来源: RSC

摘要:

DR HOPMANN ON THE ANILIDES. Dec. 13 1848. John 'I'liomas CaoIJer Tice-Pre&kmt in the Chair. Mews. John Blyth M.D. Y. JPusprrLtt J. H. Glaclstone Ph. D. James Napier James Mason aid Tl'illinm Reylin were elected Members of the Society. The following paper mas lead IT'.-Researches o?z the co/ucltiZe Organic Bases. BY DR.A. mT.I~OFhIANN Professor at the Royal College of Chemistry. IT. ANILIDES. In a short note,* communicated several years ago to the Society I pointed out the existence of sevcrd new aiiiline coinpouiids without entering ho.vvever into dctails respecting their properties and without giving the aiialytical data on which my statements were founded. A variety of other researches prevented me from conipleting the study of these snbstanccs and it was but of late that a new reaction 1 met with iii anothcr investigation conipellcd me to return to the subject.111 my paper on ~nelaniline,j-I mentioned that the result of the action of chloride of cyanogen on aniline is very materially influenced by the presence of even small quantities of water either in the aniline OF in the chloride of cganogen. Perfectly anhydrous aniline when exposed to the actioii of chloride of cyanogen pre- viously dried by chloride of calcium is entirely converted into hydro-. chlorate of melaniline in accordance with the formulz 2 (C12B N) + c N C1= C, Ell3 N, H C1, +w L-v-Aniline. Chloride of llpdrochlorate of CyanogPn. IIrlaniline. On separating the base by nicana of potash from the solution * hIenioirs of the Chemical Society vol.III. p. 26. -j-Quarterly Journal of the Chemical Society vol. I. p. 286. 1)R. HOFJIANS ON THE ANILLDES. of this hydrochloyate a mother-liquor is obtained which on evapora-tion yields scarcely a trace of organic matter. Action of chloride of cyanoyen on aniline in the presence of water. -If the action of chloride of cyanogeii on aniline takes place iii the presence of water a different deportment is observed. The mother- liquor from which the nielaniliiie has been separated by an alkali when concentrated by evaporation deposits on cooling slightly coloured acicular crystals the quantity of which is in direct proportion with the amount of water that has been present. By treating aniline with the aqueous solutioii of chloride of cyanogen obtained by passing chlorine gas into a solution of hydrocyanic acid in water the chief product of the reaction besides hydrochlorate of aniline corisists in the above-mentioned acicular crystals whilst only traces of melaniline are separated on the addition of potash.The acicular crystals as will be seen from the subjoined analysis are the anomalous cyanate of aniline or anilo-urea as the compound forinerly was briefly termed. ANILO-'CTRCd.-C A RB-4M I DE-CARBANILIDE. There is no difficulty in purifying the crystals of this substance. Treatment with animal charcod and one or two crystallizations from boiling water are sufficicn t to render thein perfectly colourless. The same compound is produced by mixing a solution of sulphate of aniline and cyanate of potash.After the lapse of some time the liquid becomes turbid and gradually solidifies into a crystalline mass consisting of the new substance and sulphate of potash nhich have separated by crystallization thc former being very soluble in boiling and but slightly soluble in cold watLr. A third method of preparing it consists in passing the vapour of hydrated cyanic acid (as obtdined in the distillation of cyanuric acid) into anhydrous aniline. This experiment however requires particular care; the liquid has to be kept as cool as possible. On passing a rapid current of cyanic acid gas into the base a very powerful evolution of heat takes place under the influence of which the newly-formed compound undcrgoes a further decomposi- tion a substance perfectly insoluble in water being formed to which I shall return in the cou:'sc of this paper.If the liquid has been exposed to a slow stream of gas it gradually solidifies into a crystal-line mass which when dissolved in boiling water deposits crystals of perfect purity on cooliiig. In most cases however a small quantity of the substance insoluble in water is likewise formed. The identity of these products was proved by the following analyses. D’B* MOFMANN ON THE ANILIDES. FOPthe analyses I. 11. and IV. the compound had been prepared by the action of moist chloride of cyanogen on aniline; analysis 111. refers to a product obtained by treating aniline with B current of cyanic acid gas.I. 0.3667 grm. of substance gave 0.8247 , , carbonic acid and 0.1995 , , water. 11. 0.2905 , , substance gave 0.6590 , , carbonic acid and 0.1610 , , water. 111. 0.2878 , , substance gave 0.6456 , , carbonic acid and 0.1595 , , water. N.0-2947 , , substance gave 0-4262 , , platinum. From them numbers the following per-centage composition i~ deduced I. If. 111. IV. c Carbon . . 61.33 61.86 61.17 Hydrogen . 6-04 6.15 6.15 -Nitrogen . * --20051 which leads to the formula c, H N2 02 as may be seen from the following table Theory. Mean of experiments. - 84 61-76 61.45 14equiv. of Carbon . 8 , , Hydrogen . 8 5.88 6.08 . 28 20.58 20-51 2 , , Nitrogen 2 11 1) Oxygen 16 11-78 -1 > , Ado-urea .136 100.00 The formation of anilo-urea in the preceding reactions is easily intelligible; whilst in the two latter cases it is produced either by the direct union of the constituents Aniline. Cyanic acid. Ado-urea. or by a process of double decomposition C,,H7N,HS04 + KC,NO,= C1,H,N2O,+ KS00 U Sulphate of Cyanate of Ado-urea. aniline. potassa. DR. HOFMANN ON THE ANLLIDES. we have in the former a transposition of the chloride of cyanogen with the elements of water in consequence of which hydrochloric acid and cyanic acid are formed 2 C, H N + C NC1 + 2H0 = C,,H,N,HCl -t-C14 H N 0 -v uw Aniline. Chloride of Hydrochlorate of Anilo-urea. Cyanogen. Aniline. The exchange of chlorine for oxygen in this case is remarkable; it does not occur in the presence of ammonia ;by saturating an aqueous solution of ammonia with chloride of cyanogen and subsequent evaporation I did not obtain crystals of urea.Anilo-urea is but sparingly soluble in cold water; boiling water dissolves it in large quantities; if the saturated solution be boiled with an excess of the substance the crystals fuse and sink to the bottom of the vessel in the form of an oily fluid. The compound is likewise very soluble in alcohol and ether. It can be boiled with dilute acids and alkalies without the slightest decomposition. I have repeatedly studied this reaction because at the first glance it appeared to point out the possibility of thus producing anthranilic acid -C, H8N 0,+ 2 HO = C14H N 0,+ NH,? w Anilo-urea.Anthranilic acid. I have not however been able to effect this transposition; both alkalies and acids when employed in concentrated solutions produce different changes. When boiled with a concentrated solution of potash or when heated with hydrate of potash anilo-urea yields aniline and ammo- nia carbonate of potash remaining in the retort C1 H8 N 0 + 2 (KO HO) = Cl H N + NH + 2 (KO CO,). v -Anilo-urea. Aniline. Anilo-urea dissolves in concentrated sdphuric acid without decom-position ;on heating the solution a brisk evolution of pure carbonic acid takes place the residue contains sulphate of ammonia and the conjugated sulphuric acid which &I. Gerhardt* obtained by the action of sulphnric acid on various anilides.’ The brown resi-duary liquid solidifies on the addition of water to a slightly reddish crystalline mass which may be purified by solution in boiling water and treatment with animal charcoal. A slowly cooling solution * Journal de Pharmacie 3 SCr. t. x p. 1. deposits splendid rhombic crystals of considerable size and remark-able lustre. The following equation illusti*atcs this transposition C14H N 0 + 3 H SO = C1211 N S O6 + 2CO + NH SO,. -v Anilo-urea. S u!phanilic acid. Although the behaviour of the acid produced in this reaction left no doubt respecting its identity with mil-sulphuric acid a sulphur determination was nevertheless made. 0.4268 grm. of the acid burned with a mixture of carbonate and nitrate of potash gave 0.5835 grm.of sulphate of baryta corresponding to 18.75 per cent. of sulphur. The formula c, H N s 0 requires the following values Theory. Experiment. -12 equiv. of Carbon . . 72 41.62 -7 , , Hydrogen . .7 4.04 -1 , , Nitrogen . . 14 8.09 I 2 , , Sulphur . . 32 18.49 18*75* 6 > J> Oxygen . 48 27.7'6 -1 , , Sulphanilic acid . . 173 100.00 The method by means of which I first obtained anilo-urea viz. the action of hydrated cyanic acid on aniline very naturally sug-gested the idea that this compound must be considered as an analogue of urea; as urea containing the elements C, II,. Urea . . h' 11 II C N 0 Anilo-urea . . (C1211,) PllT H H C2 N O, and hence the name under which I have described it. This mode of regarding it is however not supported by the chemical deportment of the compound; in anilo-urea we iio longer find a remnant of basic properties.I have vainly endeavoured to combine it with acids in order to produce conipounrls analogous to nitrate or oxalate of urea. The presence of these acids does not increase the solubility of the aniline compound in water and the crystals deposited * The slight excess of sulphur arose from the presence of a trace of sulphate in the carbouate used. DH. HOPMANN ON THE ANILIDES. on cooling retain no acid. My attempts to form a platinum-salt have likewise been unsuccessful. The formula of anilo-urea admits however of another interpreta- tion which is strikingly supported by experimental evidence.The following equation C, H N O,=NH, CO ;C, H6 N,CO shows that we may consider this substance likewise as a double com-pound of carbamide with its conjugated analogue. The existence of such double compounds is by no means isolated; in a Memoir on the metamorphosis of cyaniline which I intend shortly to present to the Society I shall have to describe a body of perfectly similar con-struction viz. a coinpound of oxamide with oxanilide correspond- ing in every respect to the preceding substance. Carbamide-carbanilide . . NH, co; c, 136 N Co Oxamide-oxanilide . . . NH, C 0,;C, H N C 0,. I was very curious to submit this idea to the test of experiment and was fortunate enough to meet with a reaction which leaves little doubt regarding the structure of anilo-urea or carbamide-carbani-Me as the substance more properly should be called.I found that when submitted to the action of heat this compound actually splits into its proximate constituents ; one of which the carbanilide is the principal product of the reaction whilst the other unable to exist at the temperature at which the separation takes place undergoes a further metamorphosis and can be recognized only in its derivatives. In submitting anilo-urea to the action of heat the substance fuses without decomposition ;on increasing howver the tenipcrature above thc fusing point torrents of ammonia are evolved while the liquid in the retort solidifies to a crystalline mass which again liquifies and ultimately distils on a further elevation of the temperature.If the process be interrupted as soon as the evolution of ammonia ceases and the solid begins to liquef? again the residue in the retort con- sists of carbanilide aid cyanuric acid. On treating this mixture with a large quantity of boiling water the whole of the cyanuric acid togcther with a small quantity of the other substance is dissolved. In order to obtain the cyanuric acid the aqueous solution is evapo- rated to dryness and the residue extracted with alcohol when car-banilide is dissolved and the acid remains in a state of purity. The properties of cyanuric acid are so marked that I have omitted to analyse the product ;its comportment with solvents and emitting also the well-known odour of cyanic acid when heated appearing quite sufficient to obviate all chance of mistake DR.HOFMANN ON THE ANILIDES The production of carbanilide of ammonia and of cyanurio acid in this reaction admits of an easy explanation if we recollect that carbamide is actually a submultiple of urea which as is well known when submitted to dry distillation is converted into ammonia and cyaiiuric acid. Two equivalents of the cornpound contain the elements of two equivalents of carbanilide and one of urea 2 C, H N 0,= 2 C13H6 NO + C N H O, -wv Carbamide-carba-Carbanilide. Urea. nilide. and the following equation exhibits the final results of the destruc- tion of carbamide-carbanilide by heat Carbarnide-carba. Carbanilide. Cyanuric acid. nilide. "he substance which I have described in the preceding pages claims some interest as the first conjugated amide which was discovered and as the first member of a class of compounds which has been enriched in so remarkable a manner by the investiga- tions of MM.Gerhardt and Laurent. CARBAMIDE-NITROCARBANILIDE. Before passing to the description of carbanilide itself I have to say a few words respecting a compound closely connected with the above double amide the existence of which I have pointed out in my Memoir on melanilhe.* When studying the action of chloride of cyanogen on nitraniline I noticed that along with basic dinitromelaniline a neutral substance was formed which separated in long yellow needles from the solution of the crude product of the reaction in boiling water.Analysis as might have been anticipated proved this body to be the double amide carbamide-nitrocarbanilide. 0.2706 grm. of substance gave 0.4575 , , carbonic acid = 46.10per cent of carbon and 0-1015 , ) water = 4.16 per cent of hydrogen. The formula requires the following values * Journal of the Chemical Society v. I p. 305. DfC. HOFMANN ON THE ANKLIDES. -Theory. Experiment. 14 eq of Carbon . . 84 46-40 46-10 7 , Hydrogen . .7 386 4.16 3 , Nitrogen . . 42 23.22 -6 9 Oxygen . 48 26.52 -1 , Carbamide -nitrocarbani- lide . . . 181 300-00 The formation of this compound will be evident from the foUowing equation Nitraniline. Hydrochiorate of nitraniline. Carbamide-nitrocarbanllide, L-,,..-J An analogous iodine compound is produced in the reaction of chloride of cyanogea on iodaniline along with diodomelaniline.I have not analysed this compound. CARBANILIDE. This substance is but very slightly soluble in water ; it dissolves more readily in alcohol and ether. The boiling alcoholic solution deposits on cooling beautiful satiny needles which have frequently a reddish tint from which they may be freed by recrystallization from alcohol with animal charcoal. It is inodorous but emits when heated a suffocating odour resembling that of benzoic acid. It fuses at 205O C. and distils without alteration. When speaking of the formation of ado-urea by passing the vapour of cyanic acid into aniline I mentioned that care must be taken to avoid the liquid getting very hot in order to prevent the formation of a secondary product I need scarcely say that this secondary product is nothing but carbanilide which may be easily separated from the accompanying compound.The nature of carbanilide being once understood other methods presented themselves for its preparation The simplest plan DR. HOFMANN ON THE ANILIDES. appeared to be a reproduction of the circumstances under which car- baniide was first obtained by 31.Regnault. On exposing phosgene gas,* the interesting chloride of carbonic oxide for the discovery of which we are indebted to Dr. John Davy to the action of ammonia the two gases solidified into a mixture of chloride of amiiioiiium and carbamide. 2 CO C1 + 2NH = NH C1+ NH, CO.This mixture admits of no complete separation of its two ingredients both compounds exhibiting about the same behaviour with solvents and it was by its reactions only that M. Regnault succeeded in establishing its true nature. The action of phosgene gas on aniline is perfectly analogous to that on ammonia and the products of the reaction being easily separable it affords a striking confirmation of &I. Regnault's original explanation of the phenomenon. Aniline when introduced into an atmosphere of phosgene gas solidifies at once into a crystal- line mixture of carbanilide and hydrochloratc of aniline. The process is attended with a powerful evolution of heat. 2 C, H N + 2CO C1= C, 13 N H C1 + C, H N CO. It suffices to extract the crude product of the reaction with boiling water when the hydrochlorate of aniline is dissolved carbanilide remaining which niaybe obtained in a state of purity by a single recrystailization from alcohol.This is certainlr the simplest manner of obtaining carbani1ide.j- The substances employed in the following analyses were partly obtained by this process (I. and II.) and partly by the action of cyanic acid on aniline (111. aid Ti.) Combustion IV was made with a product formed in the dry clistillation of anilo-urea. 1. 0.4270grm. of substance gave 1.1400 ,) ,)carbonic acid and 0-2200 , ,)water * The name phosgene gas was originally framed by Dr. Day on account of the remarkable manner in which solar radiation promotes the combination of carbonic oxide with chlorine.The co-operation of sun-light however is not absolutely necessary ; Dumas when studying the action of this cornpound on alcohol ascertained that the combitlation likewise took place in reflected light but nicch more s!owly ; I hate lately found that phosgene gas may be readily obtained by pasing carbonic oxide through boiling pentachloride of antimony which hy this treatment is reduced to the state of ter-chloride and this reaction affords e\ en a simple method of qualitatively ascertaining the presence of carbonic oxide in a misture of gases ; for the odour of phosgene gas is so peculiar that it cannot be mistaken by a person nho has once smelt it. .I. Care must be taken howe\er that the phosgene gas contain no free chlorine which gives rise to the formation of a chlorinated compound inipartins a violet colour to the carbanilide and can orilp be separated with Sreat dificolty.Dlt. HOPXANIV ON THE ANILIDES. 11. 0.3325 grin. of substance gave 0.9020 , , carbonic acid and 0.1'171 , , water. 111. 0*3019 , , substance gave 0.8182 , ,> carbonic acid and 0.1610 , , water. IV. 0,2534 , , substance gave 0.6812 , , carbonic acid and 0.1328 , , water. V. 0.4160 , , substance gave 0.3835 , , platinum. Per-ceiitage composition T. 11. 111. IV. V. Carbon . . 72.81 73.90 73-91 73.31 , Hydrogen . 5-72 5.90 5-92 5.82 -Nitrogen . --13.07 The forinula C, H NO = C, H6 N CO requires the following valnes Theory. Mean of experiments 7- 13 eq.of Carbon . . '78 73.58 73-48 6 , Hydrogen . .6 5.66 5-84 1 , Nitrogen . . 14 13.01 13-07 1 , Oxygen . -8 7.75 -1 , Carbanilide . . 106 100*00 The behaviour of carbanilide with both concentrated acids and alkalies agrees perfectly with the formula deduced by analysis. When boiled with concentrated sulphuric acid this substance is con- verted into sulphanilic acid pure carbonic acid being evolved. C, 11 N CO + 2 IISO = H SO C, H N SO, + CO,. L-Y-+ Carbanilide. Sulphanilic acid. Ebullition with concentrated potash solution or fusion with solid hydrate of potash gives rise to the formation of carbonate of potash while aniline distils over. C, H N CO + HO KO = C, H N + KO CO,. LdY-i +-Carbanilicle. Aniline. The same decomposition takes place although less perfectly even yitliont tbc assistance of potash if moist carbanilide is rapidly DR.HOFMANN ON TIfE ANILIDES. exposed to a high temperature and hence the invariable presence of small quantities of carbonic acid and aniline among the products of the distillation of anilo-urea if this substance has not been perfectly dried before the experiment. The peculiar decomposition which ado-urea exhibits under the influence of heat induced me to study the phenomena attending the dry distillation of the corresponding sulphur compound hydrosulpho- cyanate of aniline. Hydrosulphocyanate of aniline is easiIy prepared by saturating free hydrosulphocyanic acid with an excess of aniline. The acid used in my experiments had been prepared by decomposing sulpho- cyanide of lead by hydrosulphuric acid.On evaporating the solution of hydrosulphocyanate of aniline the compound separates in the form of deep red oily drops which only gradually solidify into a crystalline mass. In repeated operations I never succeeded in obtain- ing the salt perfectly colourless. Acth of heat on Hydrosulphocyanate of Aniline. Dry hydrosulphocyanate of aniline when exposed to the action of heat fused at a very moderate temperature and entered soon into a sort of ebullition torrents of hydrosulpburic acid and of sulphide of ammonium being evolved whilst on increasing the temperature a colourless oily liquid distillcd over solidifying in the water of the receiver to a semi solid crystalline mass.The residue in the retort is a slightly coloured resinous substance. In order to purify the cfystalline compound the whole distillate was subjected to another distillation. The liquid which now came over separated into two distinct layers of which the upper one contained a large quantity of hydrosulphuric acid and ammonia whilst the lower one consisted of pure bisulphide of carbon. The products of the dry distillation of hydrosulphocyanate of aniline are therefore an amorphous body remaining in the retort ammonia hydrobulphuric ucid bisulyhide of carbon and a crystalline substance which as the subsequent analysis will prove is a compound corresponding to carbanilide in which the oxygen of the latter is replaced by an equivalent quantity of sulphur a compound represented by the formula Cl H N cs for which I propose the name of XuZphocarbaniZide.The decomposition which hydrosulphocyanate of aniline under- goes when submitted to destructive distillation is perfectly analogous DR. HOFMANN ON THE ANILIDES. to that of anilo-urea. Two equivalents of the hydrosulphocyanate split into two equivalents of sulphocarbanilide and one equivalent of sulphocyanide of ammonium according to the equation 2 (C12H N H C N S) =2 (CISH6N C S,) +NH, C N S, L-V L vw Hydrosulpliocyanate of Sulphocarba-Sulpliocyanide of aniline. nilide. ammonium. Of course we cannot expect in a decomposition of this kind actually to separate the sulphocyanide of ammonium ;this compound like urea being unable to exist at the temperature at which the decomposition takes place.But there is no difficulty in tracing it in its products of decomposition. From the experiments of Professor Liebig we know that sulphocyanide of ammonium when exposed to the action of heat evolves ammonia hydrosulphuric acid and bisul- phide of carbon whilst a residue remains described by Liebig under the name of melam splitting on the further application of heat again into mellon and ammonia. Now I have mentioned already that the distil- late of hydrosulphocyanate of aniline along with sulphocarbanilide actually contains a large quantity of sulphide of ammonium and bisulphide of carbon. The residue in the retort seems to consist of mellon or melam mixed with a small quantity of an aniline com-pound.The comparatively small scale in which I had to work and the difficulty of purifying the mellon compounds prevented me from entering upon a more minute investigation. There is however but little doubt that the dry distillation of hydrosulphocyanate of aniline is illustrated by the above equa- tion. The preparation of sulphocarbanilide by the action of heat on the hydrosulphocyanate of aniline being rather a circuitous pro- cess I tried to obtain the same compound by means of a different method. The ready production of carbanilide by the action of phosgene gas on aniline appeared to point out the course to be pursued. There was but little doubt that the compound in question would easily be formed by submitting aniline to the influence of a sulphur compound analogous to phosgene gas.A substance of this kind is known but very imperfectly. In his remarkable paper on the con- version of bisulphide of carbon into the bichloride,* Dr. Kolbe states that the first product of the action of chlorine on bisulphide of carbon at high temperatures is the compound c s el. * Liebig’s Annalen Bd. XLV. S.41. DR. HOPMANN OH THE ANILIDES. The purification however of this substance appears to have been attended with so much difficulty that a very satisfactory analysis of it is still wanting. Before recurring therefore to this difficult and still doubtful reaction I tried whether sulphocarbanilide might not be formed by treating aniline with bisulphide of carbon. Action of Bisubhide of Curbon on Analine.Aniline and bisulphide of carbon may be mixed in every proportion. A mixture of this kind when left for some hours begins to evolve hydrosulphuric acid and gradually solidifies into a scaly crystalline mass which after purification is easily identified with sulphocarba- nilide. The reaction is represented by the following equation C, H N + CS = C, H6 N CS + HS. + v Aniline. Sulphocarbanilide. At the common temperature weeks are required for the completion of the process; with the aid of heat the conversion may be effected rapidly. The simplest plan is to fix a large Liebig’s condensor ver- tically into a flask containing the mixture which is gently heated for a day or two in a sand-bath over a gas flame. The presence of alcohol I find considerably accelerates the conversion.As soon as the evolution of hydrosulphuric acid ceases the digestion is inter-rupted and the crystals are freed from the remaining bisulphide of carbon by ebullition. One or two crystallizations from alcohol render them perfectly pure. The action of bisulphide of carbon on aniline presents a most remarkable analogy with the decomposition occurring in a mixture of the same compound with ammonia. The experiments of Zeise have proved that an alcoholic solution of bisulphide of carbon when saturated with ammonia is gradually converted into the same ammonium compound which hlr. Yorret long ago obtained by satu- rating his hydrosulphocyanic acid with ammonia viz. into sulpho- cyanide of ammonium.Xow sulphocyanide of ammonium although widely different in its chemical nature from sulphocarbanilide never-theless presents a striking analogy to this compound. Sulpho-cyanide of ammonium is a niultiple of sulphocarbamide. RTH, C N S = C If4 N S = 2 (XH, CS) The modes of production of sulphocyanide of ammonium and sulphocarbanilide thus become perfectly parallel as may be seen by the two following corresponding equations - DR. HOPMANN ON THE ANILIDES. NIT + c s = N €I, c s 3. II s. Sulpho-cyanide of animonium. C12II N + C S = C 11 N C S + H S. c,,J C7-J Aniline. S Lilphocarbanilide. For the following analyses the compound was obtained in different preparations. The product employed in the first combustion was formed in the dry distillation of liyclrosulphocyanate of aniline ; the other analyses werc made with the compound obtained by the action of bisulphide of carbon on aniline.I. 0.247’7grin. of substance gave 0.6219 , > carbonic acid and 0.1201 , , water. 11. 0.2891 , , substance gave 0.7253 , , carbonic acid and 0,1365 , , water. 111. 0.3259 , , substance gave 0.8120 , , carbonic acid and 0.1542 , , water. IV. 0,4593 grm. of suhstance gave 54.5 C.C. of moist nitrogen at 21O C. and Om 7596 Bar. Of the fo1lo;ving two sulphur determinations the first was made by gradually deflagrating a inivturc of the substance with nitrate of potash arid carbonate of soda. A siiiall qnantity of the compound having bezn volatilized in this opcratioii a sccoiid experiment was made in which the sulphocarbanilide was dissolved in fuming nitric acid which converts it into a substitution-body which is no longer volatile.The solution was evaporated to dryness and the residue deflagrated in the usual manner with nitre and carbonate of soda. V. 0.3809 grm of substance gave 0.3825 , , sulphate of baryta. VI. 0.4985 , , substance gave 0-5105 , , sulphate of baryta. Per-centage composition I. 11. 111. IV. v. VT. - Cahon HydrogenNitrogen . . . . . . 68.47 5-41 - 68-42 5-27 67.95 5.26 - -12.63 - I - Sulphur . . - - - - 13-67 14.04 VOL. 11.-so. v. E DR. EIOFMANN ON THE ANILIDES. the mean of which closely agrees with the values of the formula c, H N s as may be seen from the following table Theory.Mean. 13 equiv. of Carbon . . . 78 68.42 68-28 .6 5-24 5-28 6 , , Hydrogen 1 , , Nitrogen . . 14 12.29 12.63 1 , , Sulphur . 16 14-03 13.85 1 , , Sulphocarbanilide 114 100.00 100-04 Sulphocarbanilide is but slightly soluble in water it dissolves more readily in alcohol and ether the boiling solutions deposit the compound on cooling in beautifully iridescent plates of remarkable lustre. Sulphocarbanilide is distinguished by its bitter taste it is in fact one of the bitterest substances I ever met with. It has a peeinliar smell which becomes more perceptible on heating. It fuses at 140° C. (284OF.) and distils without decomposition. Dilute acids and alkalies have no action on sulphocarbanilide; when concentrated they decompose the compound and these decom- positions are analogous to the corresponding changes of carba-nilide.Sulphocarbanilide dissolves in concentrated sulphuric acid ; on gently heating this substance a brisk effervescence takes place carbonic and sulphurous acids being evolved ; the remaining solution solidifies on the addition of water into a crystalline mass of sulphanilic acid. The equation C,. H N CS + 2 H SO = C, H N S 0,+ CO + HS v -Sulphocarbanilide. Sulphanilic acid. illustrates the decomposition ; it is evident that the hydrosulphuric acid of this equation when coming into contact with concentrated sulphuric acid is decomposed with the formation of sulphurous acid and the deposition of sulphur. In fact on adding to the liquid a sufficient quantity of water to dissolve the sulphanilic acid a muddy solution is obtained from which a large quantity of free sulphur is deposited HS -I-H S04=2H0 + S -+ SO,.On fusing sulphocarbanilide with solid potash pure aniline distils a mixture of carbonate of potash and sulphide of potassium remaining in the retort -* DR. IIOFMAWN ON THE ANILIDES. C, H,N C S+2 (HO KO) = Cl,HP N + KS +KO CO,+HO. + -+ Sulphocar-Aniline. banilide. If instead of solid potash an alcoholic solution of that base be employed the reaction is considerably modified. In this case the oxygen is simply exchanged for sulphur sulphide of potassium and carbanilide being formed which crystallizes on cooling from the alkaline solution in long beautiful needles.C, H N CS+ KO = KS + C1 H N CO. -v Sulphocarbanilide. Carbanilide. The alcoholic solution of potash may be advantageously replaced by protoxide of mercury. Indeed on boiling an alcoholic solution of sulphocarbanilide with protoxide of mercury the red colour of the oxide at once disappears black protosulphide being deposited whilst carbanilide crystallizes from the solution. The rapid action of protoxide of mercury on the sulphur compound induced me to examine its behaviour with chloride bromide iodide and cyanide of mercury in order to form the corresponding chlorine bromine iodine and cyanogen compounds. These salts however are without action on sulphocarbanilide. The following table embraces the compounds the analysia of which I have communicated on the preceding pages.Carbamide-carbanilide NH CO; C, H N CO Carbamide-nitrocarbanilide NH, CO;C, { tb4 N CO Carbanilide . CIS H N co Sulphocarbanilide . c, H N cs

ISSN:1743-6893    

DOI:10.1039/QJ8500200036

出版商:RSC    

年代:1850

数据来源: RSC

摘要:

DR. SHERIDAN 3IUSPRATT Jan. 15> 1849. Cdonel Philip Yorke in the Chair. The following presents were announced :-“ On the Phosphoric Strata of the Chalk Formation,” by Messrs. J. &I. Paine and J. T. Way from the authors ; “ Report on the Ana1yvL.k of the Ashes of Ylailts,” Part III. by Nessrs. J. T.Way and G. Ogston from the authors. The followi iig cornmui~icationsmere read V.-On the Salts of Selepzzious Acid. By DR.SHERIDAN MVSPRATT Professor to the Livelyool College of C1hemisti.y. PRELININARY REMARKS. I undertook the investigation of the salts of selenious acid with the view of ascertaining whether they were analogous to those of sulphurous acid . Mitscherlich has remarked that the selenic and sulphuric acids are not only analogous in composition and in many of their pro- perties but that the similarity runs through their salts which resemble one another in chemical comportment constitution and form.We might infer from this that the selenites and sulphite; would be isomorphous sulphur and seleniuni being so analogous. In a former paper>* I mentioned the great similarity betmeen carbon and sulphur which also extends to the carbonates and sulphites. For nearly every carbonate I obtained a corresponding sulphite. The formulz of the three acids are appended in order to show their striking analogies Carbonic acid . . I GO Sulphurous acid . . 0 so Selenious acid 0 . SeO,. We see on referring to the above that they all contain the same amount of oxygen i. e. 2 equivs of oxygen united to cither carbon sulphur or selenium.Although I proved the isomorphism with regard to the first two my results with selenious acid are only in a few cases similar to those with sulphurous acid. One of the great cmses of this may be the persistency of the former and the instability of the latter. There were numerous difficulties to contend with in the preparation and analysis of the salts of this acid as will be hereafter mentioned. * Liehig’s hiii~alender Chemie Bmd I,. p. 239. ON THE 8-4LTS 03 BELENIOUS ACID. PREPARATION OF THE ACID. Selenium was dissolved in pure fuming nitric acid and the solution evaporated on a sand-bath to dryness. The nitric acid when added caused a most violent action large quantities of nitrous fumes being disengaged.The residue mas a white powder possess- ing a sour and styptic taste which heated on a sand-bath afforded as a sublimate most magnificent silvery-looking very long four-sided needles of selenious acid. This acid is also formed by acting upon selenium with aqua regia. The former method howcver is preferable. 9 Se + 6 NO = 9 SeO + 6 NO,. GENERAL PROPERTIES OF THE ACID AND SALTS. Berzelius has made allusion to many of the following properties of selenious acid and its salts. In some cases this illustrious Swede has not been sufficiently specific owing no doubt to the enormous number of facts he had to contend with in other departments of the Science. It is stated in Turner’s Chemistry,* ‘‘when su@hurous acid is added to a solution of selenious acid pure selenium is thrown down.” In the cold I could not obtain this reaction but when the two acids are mixed together and boiled a vermilion-coloured precipitate selenium separates.Strong hydrosulphuric acid decomposes selenious acid immediately in the cold an orange- yellow powder subsiding ; a sulphide of selenium. The preceding decompositions may be represented as follows SeO + 2 SO = Se + Z SO SeO + 2 HS = SeS + 2 HO. Hydrochloric acid has not the slightest effect upon selenious acid. Selenious acid is reduced when heated on charcoal before the blow-pipe the selenium imparting a beautiful blue colour to the flame. The fumes evolved are yellowish and ‘nave the smell of decayed horseradish ; a most characteristic test for the acid.The smell is so persistent that for days my clothes have retained it. This acid very seldom forms basic salts and then only with those metallic oxides which readily afford them with other acids. It easily produces a basic salt with oxide of copper in this respect materially differing from sulphuyous acid. On passing sulphurous acid into water holding oxide of copper in suspension a reduction takes place the sub-oxide of copper being formed. * Eighth Edition p. 265. DR SHERIDAN MUSPRATT 2 CUO + so = so + cu 0. When a selenite is heated in contact with any organic matter reduction inimediately occiirs ; great care has therefore to be exer- cised in the preparation of the salts not to allow any of the filtering paper to adhere to them.Charcoal reduces the salts immediately at a high temperature. If charcoal is fused with selenite of soda selenide of sodium and carbonic acid are obtained. +2 (NaO SeO,) + 3 C = 2 (Na Se) + 3 CO,. Chloride of ammonium distilled with a selenite affords selenium which condenses in the neck of the retort. The decomposition may be exhibited by the following equation 3 (NaO,SeO,) + 3 (NH,Cl) = 3 Se + 2 N + NH,O + 3 NaCl + 8 HO. Three equivalents of selenite of soda and 3 equivalents of chloride of ammonium contain the elements of 3 equivalents of selenium 2 of nitrogen 3 of chloride of sodium 8 of water and 1equivalent of oxide of ammonium. Selenious acid liquefies on exposure to the air. The neutral salts of selenious acid with potash soda and am-monia have a very caustic taste and react alkaline.They are extremely soluble in water. When aqueous selenious acid is neutralized by the alkalies and the liquid is treated with alcohol under certain circumstances an oily substance separates; this when kept for it long time becomes crystalline. Selenites of the alkalies are most difficult to prepare. They arc remarkably deliquescent and liable to undergo decomposition unless carefully dried over sulphuric acid. The neutral salts taste and react alkalinc. They dissolve with a slight reddish colour owing to a trace of reduced seleniuni; a remarkable circum-stance. Selenious acid ia extremely stable. When the crystals of the acid arc exposed to the air for weeks although they liquefy still I could not detect in them any selenic acid.How different is the case with sul- phurous acid which cannot be exposed to the air for an hour without a portion being converted into sulphuric acid. Sclenious acid accord- ing to Berzelius has a great tendency to form acid salts even in the relation of four of acid to one of base. I obtained a syrupy iiiass in one instance which when analysecl agreed with the statement above. I could not however obtain any qnadracid salt ON THE SALTS OF SELEWIOUS ACID. in a perfectly dry state. My intention in the present paper is to embrace all that is known respecting the selenites so that future investigators may have a full reference. I find as did Berzelius when an alkali is treated with selenious acid anti1 the liquid reacts neither acid nor alkaline that on evaporation crystals of a bisalt are deposited; a neutral salt remaining in solution.Rose has remarked that hyposulphite of ammonia only partially precipitates selenium in the cold; more is precipitated by boiling and still more on the addition of hydrochloric acid. In the cold the decomposition takes place extremely slowly if at all; on boiling however bisulphide of selenium is deposited-a large quantity is precipitated in the presence of hydrochloric acid SeO + Z (S 0,) = SeS + 2 SO,. When aqua regia is added to the bisulphide of selenium it is immediately decomposed. Boracic phosphoric and sulphuric acids expel selenious acid from its compounds at a high temperature.I employed sulphuric acid for this purpose in analysing the salts. Hydrochloric acid has not the slightest efect even when boiled with selenious acid; selenic acid however is reduced by it to the state of selenious acid SeO + HCl = SeO + HO + C1. Many of the salts of selenious acid lose their acid when heated; others part with only a portion and sowe do not evolve any as will be seen under the description of the various salts. SCLENITES OF POTASH. The neutral selenite is obtained by saturating carbonate of potash with selenious acid and evaporating quickly to dryness. I could not obtain the salt for a long time in a fit statc for analysis owing to there always being an excess of selenious acid. A definite salt is also extremely difficult to prepare 011 account of traces of selenium separating.Selenite of potash is remarkably soluble in water. It is almost insoluble in alcohol; but strange to say I could not precipitate it from its aqueous solution in a crystalline state by alcohol. An oily substance always appeared. It possesses a dis-agreeable taste is very alkaline to test-paper and deliquescent ; on which account great care has to be exercised in weighing the salt. 0.251 grms. salt gave 0.210 , sulphate of potash = 0.113 , potash leading to the fo'orniula KO SO,. Centesimally represented Theory. Exp. 1 ey. of selenious acid . 56 53.85 1 , of potash. . . 48 46.15 45.02 104 100~00 Biselenite of potash gives satiny-looking crystals.It is obtained by decomposing carbonatc of potash with an excess of selenious acid and allowing the solution to evaporate over sulphuric acid ;or by pre-cipitating the solution with alcohol in which menstruum the bi- selinite is only slightly soluble. The difficulty attending the prepara- tion of this salt is very great. Too much seleiiious acid must not be added to thc carbonate of potash or crystallization will never take place. When the liquid is made slightly acid the crystals are not more than two days in forming. Alcohol nearly always precipitates an oily liquid from the slightly acid aqueous solution which speedily howeever becomes crystalline. The crystals dried for eight days over suiphuric acid were analysed 0.894 grin. salt gave 8.351 , snlphate of potash leading to the forniula -KO SeO, +-130 SeO Theor!.Experiment. 2 eqs. of selenious acid . 118 66.272 1 , of potash . 48 28.402 28-05 1 , of water . 9 5.326 169 100-080 Biselenite of potash is analogous to the bisulphite of the sanic base KO SeO, -+ €10,SeO KO SeO, +1-10,SO,. On heating the biseleiiite iii a dry test-tube water first passes off and is followed by selenious acid. The whole mass then fwes to a red fluid which ultimately becomes colourless and on cooling solidifies into a fine crystalline mass soluble in water and pre- cipitable by alcohol. It is the neutral selenite of potash. ON THE SALTS OP SELENIOUS AClU. h most disagreeable odour of horseradish is evolved as the liquid reddens.The quadriselenite of potassa described by Berzelius-KO 4 SeO, or KO SeO, + 3 (HO SeO,) ? is not attainable in a fit state for analysis. This salt is styptic to the taste and when heated evolves most stifling funies. It is in a high degree deliquescent. SELENITES OF SODA. When carbonate of soda saturated with selenious acid is allowed to evaporate under a bell-jar the syrupy mass becomes filled with radiated crystals ; which will be subsequently described. The liquid gives a neutral salt on the addition of alcohol. This salt not being deliquescent is more easily obtained than the salt of potash. It was desiccated between folds of bibulous paper and then left over sulphuric acid for some days 0.400 grms. of salt gave 0.320 , sulphate of soda= 0.142 , soda agreeing with the formula NaO SeO,.Theory. Experiment. 1eq. selenious acid . . 56 63.63 1 , soda. . . 32 36-37 35.50 88 100~00 The above corresponds with the formuh for dry carbonate and sulphite of soda NaO CO NaO SO NaO SeO,. Selenite of soda heated in a test-tube gives off a mere trace of water thc salt fuses but does not suffer decomposition. Froin the aqueous solution I could not succeed in obtaining the neutral salt with water of crystallization. Biseleuite of soda forms acicular crystals. 0.2410 grins. oi salt gave 0.0251 , water. The annexed formula is deduced from the above NaO SeO, +' HO SeO + 2 aq DR. SHERIDAN MUSPRATT Represented in 100 parts Theory. Experiment.1 eq. of selenite of soda . 88 51 46 1 , , , , water . 65 38-02 2 eqs. , water-. 18 10.52 10.41 171 100.00 The biselenite does not suffer decomposition except at a very high temperature. On a sand-bath it parts only with its water of cfystallixation. At a red heat it fuses into a yellowish liquid water passing off with selenious acid; the neutral salt remains as a fine silvery-white crystalline mass. QUADRISELENITE OF SODA. I dissolved biselenite of soda in selenious acid and put aside the liquid to evaporate spontaneously. After some days needle-like crystals separated which were not very deliquescent When dried over sulphuric acid and analysed 0.862 grm. salt gave 0.241 , sulphate of soda = I-( 0.107 , soda. 0.804 grm. salt gave 11.{0.210 , sulphate of soda = 0.093 , soda. The preceding results agree closely with the followifig singular formula NaO SeO + 3 (HO SeO,) -+ aq. Theory. Experiment. I. 11. 4 eq. selenious acid . 224 76.712 1 , soda. . . 32 10-958 4 , water . 36 12-33 12.41 11.56 292 100.000 This salt fuses readily into a yellowish-red liquid evolving selenious acid and water while selenite and traces of selenate of soda remain. SELENITES OF AMMONIA. These salts are extremely difficult to prepare. I could not obtain a selenite of ammonia from an aqueous solution in a fit state for analysis ON THE SALTS OF SELENIOUS ACID. After a number of vain attempts alcohol was resorted to. SeIenious acid dissolved in alcohol and treated with ammoniacal gas afforded magnificent shining crystals which however were deliquescent.This salt is also obtained by dissolving selenious acid in strong aqueous ammonia and precipitating by alcohol. When a drop of strong ammonia is addcd to crystallized selenious acid combination imme- diately takes place great heat is evolved and particles of selenium some times separate . Selenite of ammonia is strongly alkaline to the taste and smells slightly of ammonia. It is very soluble in water-perfectly insoluble in ether 0.2505 grm. salt gave 0.25050 0.3100 , platinum = 0.31000 0*08141 , oxide of ammonium 0-08141 agreeing with the formula NH,O SeO,. Theory. Found. 1 eq. selenious acid . . 56 68.30 1 , oxide of ammoniuni 26 31.70 32-49 82 100.00 Selenite of ammonia hcated in a dry test-tubc gives off first water and ammonia then water and nitrogen while an acid salt condenses in the upper part of the tube; lastly large quantities of selenium sublime.The decomposition is represented in its several stages by the annexed equation. 5 (NH,O SeO,) = HO + 2 NH,O + 7 HO + 2 N +NH,O.2 Se-0, + 3 Se. Biselenite of ammonia does not deliquesce it is composed ac-cording to Berzelius as follows :-NH,O 2 SeO,. Its formula is probably NH,O SeO + HO SeO,? Quadriselenite of ammonia is not crystallizable. SELENITES OF BARYTA. Selenious acid produces no precipitate with solutions of baryta. By this reaction it is at once distinguished froni sulphurous acid. When neutral selenite of potash is added to nitrate of baryta decomposition takes place selenite of baryta is deposited in fine shinhg ~IUII~OSC crystals which are solulh in selenious nitric and hydroch!oric acids.From the acid solution the baryta is imme-diately precipitated by sulphuric acid. 0.308 grm. salt gave 0 271 , sulphate of baryta = 0.177 , baryta. Numbers agreeing with the formula Ba0 SeO Centesimally represented Theory. Berzelius. Experiment. 1 equiv. selenious acid . 56 42.42 42-07 -1 , barytes . . . 76 57.58 57.93 57.46 132 100*00 100.00 Biselenite of baryta is obtained by expelling the carbonic acid €rom the carbonate of baryta with seleiiious acid and allowing the liquid to evaporate spontaneously. It is with difficulty dissolved in water.Ammonia when added to it .precipitates the neutral salt. At a high temperature the biselenite evolves water and white fumes of selenious acid. SELENITES OF STRONTIA. These salts are obtained in a similar manner to those of baryta. Selenite of strontia is a white insoluble powder. It does not contain water. The following is its formula SrO SeO,. Biselenite of strontia does not crystallize. Its behaviour when heated corresponds to the acid salt of baryta. It is slightly soluble in water. SELENITES OF LIME. Carbonate of lime with selenious acid yields gritty crystals of selenite of lime. Berzelius has remarked the singular effect of this salt upon glass. At a red heat the tube is sometimes eaten through. A most remarltable characteristic of this ad a few other of thc salts of sclenious acid.Formula-CaO SeO The selenite of lime dissolves in selenious acid giving a biselenite which is very persistent in the air. ON TIIE SALTS OF SELESIOUS ACID. 61 When all the carbonic acid is e.ipellcd from carbonate of magnesia by selenious acid there reiliains a heavy neutral crystalline salt which dissolves in boiling wter and crystallizes from it in Aombic prisms. Selenite of magnesia heated over the lamp gives off only its water of crystallization. It fuses at a red heat in a glass tube corroding and passing through it like the selenite of lime. 0.209 grm. of salt strongly heated gave 0.056 , ,)water. Foxnula-MgO SeO 4-3 aq. Theory. Experiment. I 1 eq.Selenious acid . . 56 54.36 1 , Magnesia . . 20 19-42 -3 , Water . . 27 26.22 26.79 103 100.00 This salt is isoznoryhous with the sulphite and carbonate of the same base MgO SeO + 3 aq. MgO SO + 3 aq. 31g.0 CO + 3 aq. Selenite of magnesia dissolves in selenious acid yielding a biselenite precipitable in an unctuous state by alcohol. It is cxtreiiiely deliquescent. SELENITES 01' ALUhIINA. Alum is not precipitated by selenious acid. A selenite of an alkali however precipitates a selenite of alumina. Great care must be taken that the precipitant is nentral. Selenite of alumina is amorphous. When heated it gives off water and lastly all its acid. 0.197 grm. of dry salt gave 0.150 , selenious acid aiicl 0.046 , alumina.Theory. Esperiment. 3 eqs. Selenious acid . . 168 7'6.36 76-14 1 , Alumina . 52 23.64 23.36 Loss . . --50 220 I100.00 lOO*OQ 62 DR SHERIDAN MUSPRATT I also determined the water in the salt dried over sulphuric acid. 0.112 grm. of salt gave 0.012 , , water. Centesimally represented Theory. Experiment. 3 eqs. Seleiiious acid . . . 168 68-01 -1 , Alumina . 52 21-17 -3 , Water . 17 10.82 10.71 247 100*00 Formula-Al 0, 3 SeO + 3 aq. The composition of the selenite of alumina is greatly different from the sulphite as represented by the formula Al 0, SO + 4 aq. Biselenite of alumina is obtained when the above salt is dissolved in selenious acid. It is transparent and gummy to the feel. According to Berzelius it contains six equivalents of acid.Al 0, 6 SeO In all probability its composition is the following Al 0, 3 SeO + 3 (I10 SeO,) ? SELENITES OF GLUCINA. This selenite is in every way analogous to that of alumina the biselenite is extremely soluble and does not crystallize. SELENITE OF CHROIUIUM. This salt is obtained by decomposing the chloride of chromium by selenite of ammonia. It is a fine green amorphous powder. 0.3006 grm. salt gave 0.0980 , oxide of chromium. Formula-Cr 0, 3 SeO Theory. Experiment. 3 eqa. Selenious acid . . 168 67-74 -1 , Oxide of chromium . 80 32-26 32.60 248 100.00 Selenite of chromium dissolves in selenious acid giving on evapora-tion a green varnish. ON THE SALTS OF SELENIOUS ACID. SELENITES OF IRON.Metallic iron is not dissolved by selenious acid. Selenium is deposited on its surface in red flakes. Selenite of iron precipitates as a white powder from a mixture of an alkaline selenite and sulphate of iron. It becomes darker on exposure to the air and after some time partakes of a yellow colour owing to the forination of some sesquioxide. When the white precipitate is dissolved in hydrochloric acid a portion of selenium separates and sesquichloride of iron with selenious acid remain in solution. 4 (FeO SeO,) + 6 HC1 = Se + 2 (Fe Cl,,) + 6 HO + 3 SeO,. Biselenite of iron is formed by dissolving the selenite in selenious acid. When the liquid is boiled a brown powder separates con-taining selenite of the sesquioxide of iron with selenium.Selenite of the sesquioxide of iron falls as a white powder when selenite of ammonia is added to sesquichloride of iron. It is yellowish when dry and loses water in the heat becoming darker and as the temperature augments all its acid volatilizes 0.1015 grm. salt gave 0.0720 , selenious acid and water which agrees sufficiently with the formula Fe 0, 3 SeO + 4 aq. Calculated on 100 parts Theory. Experiment 1 eq. Sesquioxide of iron 80 28.16 -3 9 Selenious acid . . 168 59.15 4 , Water . * 36 l2*69{ 70'94 284 100.00 According to Berzelius the bisalt is formed when iron is dissolved in a hot mixture of nitric and selenious acids. The salt is deposited on cooling in green plates which contain water of crystallization. They are not soluble in water but dissolve readily in hydrochloric acid imparting a yellowish colour The formula for the salt is Fe 0,,3 SeO + 3 (HO SeO,) ? A basic salt is obtained when either of the two preceding salts is d-igested in ammonia the formula for which is 2 Fe 0,,3 ScO,.DR. SHERIDAN MUSPRITT SELENITES OF XIAPJC.lPJESE. I dissolved carbonate of manganese in selenious acid and obtaind a white gritty powder which readily fused to a dark liquid in a glass tube corroding it more even than the magnesia-salt. Sclenious acid sublimed and sesquioxide of manganesc with some selenium remained 05?00grm. salt fused with nitrate of potash gave 0.250 gri. selenate of baryta = 0.100 grm. sclenions acid. The formula is thereforc MnO SeO + 2 aq.Represented in 100 parts. Theory. Experiment. 1eq. selenious acid . . . 56 5090 5040 1 , oxide of manganese . 36 32.73 -2 , water . . . . . 18 16.37 -110 100~00 -This salt agrees in composition with the carbonate and sulphite of manganese MnO SeO + 2 aq. MnO CO + 2 aq. MnO SO + 2 aq. Selenite of mangancse is insoluble in water it forms a colourless solution in cold and a pink solution in hot hydrochloric acid TVith selenious acid it yields a soluble biselcnite. SELEXITES OF ArICKEL. The neutral salt falls as a greenish powder when selenite of potassa is added to sulphate of nickel. In its dry state the salt is white. Dried over sulphuric acid 0.207 grin. salt gave 0.019 , water. Numbers corresponding to the formula NiO SeO + aq.Calculated on 100 parts. Theory. Experiment. 1eq. selenious acid . . 56 54.36 -1 , oxide of nickel . . 38 36.89 7 1 , water . . . . . 9 8.75 9.1'7 103 100*00 ON THE SALTS OF SELENIOUS ACID Selenite of nickel dissolves in selenious acid with a greenish colour. The liquid on evaporation yields a gummy acid salt. SELENITES OF COBALT. The neutral salt procured by double decomposition is an insoluble rose-coloured powder. In all probability its composition is similar to the nickel compound. Carbonate of cobalt dissolves in selenious acid with a fine pink colour. The liquid on evaporation yields a magnificent transparent violet-coloured gum-an acid salt. This resinous substance when heated on a sand-bath g-ives off selenious acid which condenses on the sides ol the vessel in beautiful white needles.. SELENITES OF ZINC. Selenious acid does not precipitate salts of zinc; in combination with an alkali however it gives when added to sulphate of zinc white crystalline grains of selenite of zinc. When this salt is heated it evolves water but as the temperature augments the salt fuses to a yellow liquid which on cooling presents a fine crystalline striated appearance. At a white heat the niasx gives off selenious acid leaving a basic salt 0,0522 gun. salt gave 0*0087 , water. From which the following formula is deduced ZnO SeO + 2 aq. Represented in 100 parts Theory. Experiment. 1 eq. selenious acid . . 56 49.12 -1 , oxide of zinc .. . 40 35-08 -2 , water . . . . . 18 15.80 16.66 114 100*00 This salt corresponds to the sulphite of zinc ZnO SeO + 2 aq. ZnO SO + 2 aq. Selenite of zinc dissolves in selenious acid yielding an uncrystalli-zable biselenite. SELENITES OF CADXIUM. Selenious acid does not precipitate salts of cadmiurn. Selenite of ammonia gives with chloride of cadmium a white argillaceous looking TOL. II.-NO. Y* I? DR. SHERIDAN MWSPRATT precipitate. This becomes orange on exposure to the air. Selenite of cadmium contains no water It is soluble in selenious acid When heated in a test-tube it gives a sublimate of a yellowish-red colour. SELENITES OF COPPER. When biselenite of ammonia is added to a hot solution of sulphate of copper a dirty greenish-yellow precipitate falls which after some time becomes a fine bluish-green crystalline salt This compound dried over sulphnric acid acquires a beautiful bright blue colour.0.5260 grm. salt gave 0,2133 , oxide of copper. 0.0526 , salt gave 0-0018 , water and 0-0534grm. salt gave 11' { 0.0017 , water. The above results agree very closely with the formula 3 (CuO SeO,) + aq. Centesimally represented Theory. Experimernt. r I. 11. 3 eq. selenious acid . . . 168 56.56 -3 , oxide of copper . 120 40.40 40.55 -1 , water . . . 9 3-04 3.42 3.18 -7-297 100.00 This aalt does not dissolve in aqueous selenious acid. At a high tem- perature it first becomes brown lastly black parting with all its acid. A green basic selenite of copper is formed when selenite of ammonia is added to sulphate of copper.It is insoluble in water but dis- solves in ammonia. Freshly precipitated suboxide of copper combines with selenious acid producing a whitiah salt. The formula for which is Cu 0 SeO + aq.? SELENITEB OF LEAD. Selenious acid gives a white curdy precipitate with acetate of lead which is slightly soluble in water. The precipitate contains no water. It is with difficulty decomposed by sulphuric acid. When heated ON THE SALTS OF SELENIOUS ACID. very strongly it fuses into a yellowish fluid selenious acid sublimes and a basic salt remains. The formula for this salt is PbO SeO,. SELENITE OF SILVER. Berzelius analysed the selenite of silver.It is thrown down in the form of a white powder on the addition of aqueous selenious acid to nitrate of silver; it is fusible and at a red heat loses its acid and all its oxygen leaving metallic silver. When perfectly dry it is not blackened on exposure to light. It is slightly dissolved by cold more by boiling water is easily soluble in hot nitric acid from which it crystallizes in needles. The salt is obtained perfectly pure in this way. The formula for the salt is ,4gO Se02. SELENITES OF MERCURY. The selenite of the suboxide of mercury is obtained by adding selenious acid to a solution of subnitrate of mercury; also by double decomposition. It is a white powder insoluble in water. Heated in a tube it blackens water is liberated and a yellow powder sublimes.When the latter is heated it fuses into beautiful red globules which become of an orange colour on cooling ; in fact a series of cameleon- like changes occur with this salt. As the tube gradually cools splendent golden yellow crystals become visible. Caustic potash takes the selenious acid from the selenite. It dissolves in hydro-chloric acid giving chloride of mercury water selenious acid and selenium. 2 (Hg 0,SeO,) + 4HC1 = 4 (Hg Cl) + 4 HO + SeO + Se. Selenite of the protoxide of mercury is a white insoluble powder. The bisalt according to Berzelius is obtained by digesting the oxide of mercury for a long time in selenious acid. On filtering and eva- porating the filtrate prismatic crystals are deposited containing a large quantity of water.The salt fuses easily in its water of crystallization; as the heat is increased the selenite sublimes unchanged. Sulphurous acid preci- pitates from the selenite a mixture of sulphate of mercury and selenium 2 (HgO 2 SeO,) + 9 SO = Hg2 0 SO + 8 SO -i-Se. F2 $R. SHERIDAN MUSPRATT SELENITE OF LITHfA. This salt is obtained by double decomposition. It is deliquescent. When heated it fuses to a yellow liquid and on cooling solidifies into an opaque crystalline mass resembling mother-of-pearl. Selenite of lithia is soluble in selenious acid. SELENITE OF PTTHIA. Berzelius obtained the above as a white argillaceous precipitate which was insoluble in selenious acid. When dry it is a white amorphous powder which at first gives off water when heated and then acid.SELENITES OF CERIUill. Selenite of the protoxide of cerium is a white powder insoluble in water. A biselenite of the same oxide is obtained by dissolving the former in selenious acid. Selenite of the sesquioxide of cerium is a citron-yellow powder easily parting with its acid The biselenite is obtained by dissolving the above in selenious acid. When evapo-rated on a water-bath it leaves a yellow gummy mass which when heated loses water and becomes opaque and crystalline. It is soluble in water. SELENITES OF ZIRCONIA. The neutral salt is a white insoluble powder obtained by double decomposition. It loses its acid when heated and is soluble in selenious acid yielding an acid salt. SELENITES OF URANIUM.Selenite of uranium is a citron-yellow powder that gives off acid when strongly heated leaving a lower oxide; the bisalt yields on evaporation an opaque gum behaving like the selenite of the sesqui- oxide of cerium. The formula for this salt is U O, 3 SeO,. SELENITE OF ‘FIN. This salt is a white insoluble powder. It is soluble in hydrochloric acid from which solution it is reprecipitated by water. Heated it evolves first water selenious acid then sublimes and pure oxide of tin remains. The formula for the +y salt is SnOz 2 SeO ON THE SALTS OF SELENIOUS ACID. I have now described thc various compounds of this interest-ing acid. The difficulty of preparing the salts can only be known to the experimenter. Spontaneous evaporation or double decom- position is the best way to obtain the desired end.Alcohol can seldom be eniployed as a precipitant for it generally separates an oily liquid which becomes crystalline only in rare instances. The determination of selenious acid is very difficult ; fusion with nitrate of potash is the first step to convert the selenious into selenic acid which latter can then be precipitated by nitrate of baryta; selenate of baryta must not be burned in the filter as reduction readily takes place. To prevent loss when the selenate of baryta is perfectly dry it should be scraped from the filter into a weighed crucible and the filter burned over it. The selenites seldom correspond with the sulphites or carbonates; where such is the case the analogy has been noticed.The great stability of selenious acid has been previously discussed. Its salts when not deliquescent are most persistent. I shall close this memoir with a table of all the salts of selenious acid. Selenite of potash KO SeO Biselenite of potash . KO SeO,+ HO SeO Quadriselenite of potash . KO SeO +,3(HO SeO,) ? Selenite of soda . . NaO SeO Biselenite of soda . . NaO SeO + HO SeO + 2 aq. Quadriselenite of soda . NaO SeO,+ 3(HO SeO,) + aq. Selenite of ammonia . NH 0 SeO Biselenite of ammonia . NH 0 SeO,+HO SeO,? Selenite of baryta . . BaO SeO , , strontia . SrO SeO , , lime . . CaO SeO Biselenite of lime . . CaO SeO,+HO SeO ? Selenite of magnesia . MgO SeO + 3 aq. , , alumina . . Al 0, 3 SeO + 3 aq. Biselenit,eof alumina .Al 0, 3 ScO + 3 (HO SeO,)? Selenite of glucina . G1 0, 3 SeO -1-3 aq. ? , , chromium . Cr 0, 3 SOe . FeO SeO, , > Iron Biselenite of iron . . FeO SeO -l-HO SeO,? Selenite of the sesquioxide of iron . Fe 0, 3 SeO -I-4 as. Sesquiselenite of the sesquioxide of iron 2 Fe 0, 3 SeO Biselenite of the sesquioxide of iron . Fe 0, 3 SeO + 3 (HO SeO,)? Selenite of manganese MnO Se 0+ 2 aq. MR THORNTON Selenite of nickel . , , cobalt . , ? zinc , ) cadmium. . . , J copper . , , the suboxide of copper 3 , lead . , silver . . t , , the suboxide of mercury , , the oxide of mercury Biselenite of the oxide of mercury Selenite of lithia . , , yttria . , , the oxide of cerium .Biselenite of the oxide of cerium. J. IIERAPATH . NiO SeO + aq. . COO SeO + aq.? . ZnO SeO + 2aq. . CdO SeO . 3 (CuO SeO,) + aq. . Cu,O SeO + aq. ? . PbO SeO Ago SeO . Hg 0 SeO . HgO SeO . HgO SeO,’+ HQ SeO ? . LiO SeO . YO SeO . CeO SeO,? . CeO SeO,+ HO SeO,? Selenite of the sesquioxide of cerium. Ce 0, 3SeO ? Biselenite of the sesquioxide of cerium. Ce 0, 3SeO + 3(HO,SeO,)? Selenite of zirconia . Zr 0, 3 ScO , , uranium . U 0, 3 SeO 9 19 tin I * . SnO, 2Se0 All the preceding salts heated on charcoal before the blow-pipe impart a magnificent blue colour to the flame emitting the unmis-takeable and offensive smell of foul horse-radish. That many of them were obtained in definite crystals is due in a measure to the extreme coldness of the weather.It is valuable and interesting to ascertain the composition of the salts of some of those acids having ous for their termination. I purpose shortly communicating to the Society a paper on the Tellurites.

ISSN:1743-6893    

DOI:10.1039/QJ8500200052

出版商:RSC    

年代:1850

数据来源: RSC

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MR THORNTON J. IIERAPATH VL-On some newly discovered Substances from the African Guano Deposits. By THORNTON ESQ. J. HERAPATH Some time in the latter part of the ycar 1845 a paper was read before this Society by Mr. 3. F. Teschemaeher,* in which the author gives an account of the results of his analyses including a variety of substances which had been found in the guano deposits and in their vicinity. Besides those there described however I have lately had the opportunity of examining another which that gentleman does not ap-pear to have taken any notice of This substance which wax found * Mem. Chem. SOC. FC~. 111 part 16,p. 13. ON SOME NEW SUBSTANCES PROM AFRICAN GUANO. occurring in large crystalline masses or nodules in a cargo of guano from the island of Ichaboe on the western coast of Africa was sent to my father’s laboratory for examination by Mr.Ruxton of Swansea in January 1846 some of the parties to whom he had supplied the guano having complained to him of the presence of the crystals imagining them to be an adulteration. These crystals when purified from the adherent guano were found to be perfectly transparent and homogeneous but stained of a light yellowish-brown colour by the humic acid and extractive matters of the guano. They were ex-ceedingly frangible and did not effloresce upon exposure to the air ; they dissolved easily both in hot and cold water and the solutions gave with the soluble salts of silver a bright yellow precipitate which was almost entirely soluble in an excess of nitric acid.When boiled with a solution of potassa pungent fumes of ammonia were given off which gave a fugitive stain to moistened turmeric paper. Before the blow-pipe they intumesced turned black and gave off water and ammonia; by a further application of heat the carbo- naceous matters were burnt off and the residue fused into a transparent colourless glass which dissolved readily in boiling water giving a solution which yielded a granular precipitate when tested with anti- moniate of potash. The specific gravity of these crystals as determined by means of oil of turpentine was about 1.6151. An attempt was made to ascertain the primary form of the crystal but it was found impossible to do 60 from the rough irregular masses met with in the guano.By dissolving these however in boiling water and filtering the solution and crystallizing the salt was obtained in moderately large colourless prismatic crystals. Upon subjecting these to analysis the following results were obtained I. 10 grains of the salt when heated to redness lost 5.103 grs. of water and ammonia. 11. 10 grains when treated as before lost 5.243grs. in weight. 111. 5 grains when burnt with potash and lime by Varrentrapp and Will’s process gave 4.890 grs. of ammonio-chloride of platinum =Om377 grs. of ammonia. IV. 5 grains treated as before gave 5.078 grs. of ammonio-chloride of platinum = 0.391 grs. of ammonia. V. 10 grains when dissolved in water and the solution precipi- tated by neutral acetate of lead gave 20.331 grs.of phosphate of lead which when decomposed by sulphuric acid gave 22.938 grs. of sulphate of lead. MR. THORNTON J. HERA4YAT€i TI. 10 grains treated as before gave 19.549 grs. of phosphate and 21.867 grs. of sulphate of lead. VII. 10 grains gave 3.002grs. of chloride of sodium. VTII. 10 grains gave 2.905 grs. of chloride of sodium. These numbers give the following per-centage composition .. . I. TI. 111. TV. v. VI. 1-11. VIII. Mean. .. 34.291 34.360 .. .. 34.325 P } .. .. { *' Na .. .. *. .. 16010 15.494 15.752 7.540 7.820 .. .. .. .. 7.680 yH3}51-030 92.320 H I .. .. .. .. *. .. 42.243 which very closely corresponds with that of the arnmonio-phosphate of soda or microcosmic salt the formula for which is ..ia NIL,' Pi+ OH or according to Graham Na 0 NH 0 PO, H0-t-8HO. The original crystals contained the following constituents in 100 parts as Crystallized arnmonio-phosphate of soda . . 91.660 Organic matters (urates humates &c.) . . 1.956 Phosphate of potash . evident traces. Chloride of sodium . . . 0,521 Carbonatc of lime . . 0.280 Carbonate of magnesia . . traces. Phosphate of lime . . . 2.100 Silica sand &c. . . . 2.151 Water and loss . . 1.332 100~000 With regard to the manner of the formation of this salt it is extremely difficult to comprehend how such a compound as the ammonio-phosphate of soda could be produced by the decoinpositiori of a substance so remarkably deficient in the alkalies as guano. For unless we can conceive that there was in this case a peculiar aiid special source of the soda wc must of necessity adinit that it was obtained froin the decomposition of the chloride of sodium of the sea-water by the phosphate of ammonia of the guano.The resulting chloride of ammonium being either volatilized at the high tenipe-rature of those climates or from its extreme solubility dissolved out by the rain-water and carried into the sea or the lower strata of the guano deposits. We well know that chloride of sodium is capable ON SOME NEW SUBSTANCES FROM AFRICAN GUANO. of being decomposed by phosphate of ammonia at a high tempe- rature. May not this decomposition therefore also take place when the salts are in solution ? I think it very probable.This being the first instance in which the ammonio-phosphate of soda has been met with as a natural production I propose to class it amongst our minerals under the name of Stercode.”* I should have preferred to have given it that of Guanite as being more indi- cative of its origin but this has been already applied by Mi. Tesche-macher to the ammonio-magnesian phosphate another product of the decomposition of guano. I have also examined another salt which was met with in the same cargo of guano as the preceding to which it bore a very close resemblance both in physical and chemical properties. Like it it was frangible crystalline and readily soluble in water and gave off ammoniacal fumes when heated to redness or when treated with caustic potash; it also gave a yellow precipitate with nitrate of silver; but it differed from it in efflorescing upon exposure to the air and in not giving a precipitate with antimoniate of potash.The primary form of the crystal as nearly as could be determined from the few imperfect specimens in my possession was an oblique rhomboidal prism with a dihedral summit. Upon redissolving these in water and recrystallizing by spontaneous evaporation long acicular crystals were obtained which when dried between pieces of bibulous paper and subjected to analysis afforded the following results I. 2.131 grains of the crystals when heated to redness lost 1.034 grs. in weight of water and ammonia. 11. 1940 grains gave 6.039 grs. of amrnonio-chloride of platinum =0*465 grs.of ammonia. 111. 3.500 grains gave 10.539 grs. of phosphate bf lead which gave 11.786 grs. of sulphate of lead= 1.854 grs. of phosphoric acid. Or on 100 parts I. 11. 111. Water . -23.058 Ammonia }48*521{ 23.980 -23.980 Phosphoric acid -52.962 52.962 numbers which are very nearly equivalent to 1atom of ammonia 1 atom of phosphoric acid and 14 atoms of water. It may therefore be considered as the neutral phosphate of ammoniu. The excess of water was doubtlessly caused by the moisture which remained between the interstices of the crystals. It was therefore the same * From the Latin Stwcoro,” to dung or manure land. MR. JOHN film ASHLEY salt as that which had been previously examined by Mr. Tesche-macher but which he was prevented from analyzing quantitatively on account of the smallness of the quantity in his possession. In conclusion I should perhaps observe that the guano from which the above substances were obtained was exceedingly moist and possessed a very strong ammoniacal smell.

ISSN:1743-6893    

DOI:10.1039/QJ8500200070

出版商:RSC    

年代:1850

数据来源: RSC

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MR. JOHN film ASHLEY VII.-Analysis of Thames Water. By JOHNM.ASHLEY, ESQ. When we reflect upon the almost oountless uses to which the water of the River Thames is applied it creates some surprise that no accurate analysis of its waters should have appeared until the commencement of last year .* As no very certain knowledge of the composition af Thames water can be obtained by any other means than through the medium of a series of analyses of water taken at different places it is the intention of Dr. Hofmann to have these analyses conducted in the laboratories of the Royal College of Chemistry the present analysis formiug the second investigation of the series. The water analysed by Mr. Clark was obtained from Twickenham; that which I have used was taken from London Bridge on the 13th of October 1848 about half an hour after high water.It was a spring tide and the water was unusually muddy. The hour of the day was three o’clock P.M. The following data were observed Temperature of the water . . . 13O C = 55.4F. Temperature of the air . . . . 15O C = 59.0F. Specific gravity of the water. . . . l*OOOl. The qualitative analysis pointed out the presence of potash Bods lime magnesia alumina chlorine sulphuric acid silicic acid and organic matter. A very small amount of phosphoric acid was detected but it was in too minute quantity for estimation. After the evaporation of large amounts of water neither bromine iodiue nor manganese could be detected. The following experimental numbers were obtained by quantitative determinations.A. Determination of total amount of fixed constituents * Mr. Clark on Thames water Quarterly Journal of the Chemical Society vol. i. p. 155. ON THE ANALYSIS OF THAMES WATER. Amount of water employed. Amount obtained. Per-centage. I. 450.679 grm. 0.1859 grm. 0,041248 11. 564-5610 > 0.2%83 , 0*04(9438 Mean 0.040843 B. Determination of chlorine Amount of water employed. Amount of chloride Per-cent age of sodium obtained. of chlorine. I. 674.53 grm 0.1'737 grm. 0.006353 11. 419-66 , 0.1095 ,) 0.006478 Mean 0.006394 C. Determination of sulphuric acid Amount of water employed. Amount of sulphate Per-centage of of baryta obtained. sulphuric acid. I. 609-96grm. 0.0512 grm.0.002883 11. 703.181 , 0.0502 , 0 002452 Mean 0.002667 D. Determination of silicic acid Amount of water employed. Amount of silicic Per-centage of acid obtained. silicic acid. I. 1280*9110grm. 0.0227 grm. 0.000177 11. 1300*1560 ,> 0.0232 , 0.000178 ~ Mean 0*800177 E. Determination of lime and magnesia Amount of water employed. Amount of carbonate Per-centage of lime obtained. of lime. a. I. 1280*9110grm. 0.2651 grm. 0.011589 11. 1300.1560 , 0.2657 I 0.01 I444 Mean 0.011516 6. Determination of magnesia in filtrate from oxalate of lime Amount of water employed. Amount of pyro-phosphate Per-ceutage of magnesia obtained. of magnesia. I. 1280 9110 grm. 0.0527 grm. 0~000142 11. 1300.1560 , 0.0494 , 0.000140 Mean 0-000140 F.Determination of alkalies Amount of water employed. Amount of mixed chlorides obtained. 1. 2099.889grm. 0.3074 11. 2071°420 , 0.2936 $6 MR. JOHN Ma ASHLEY a. Determination of potash Amount of water employed. Per-centage of platinum Per-centage of and potassium obtained. potash. I. 2099.889 grm. 0.2494grm. 0*000228 11. 2071-4200 , 0*2040 , 0*000189 -Mean 0*000208 b. Determination of soda. Amount of water employed. Amount of chloride of Per-centage of sodium obtained. soda. I. 2099.889 grm. 0.2313 grm. 0.005881 11. 2071-4200, 0.2304 , 0-005918 ~-Mean *005899. 15309 grms. of the water were evaporated down to 801.47 grms. The precipitate which formed was separated and weighed 3.1115 grms. Determination of organic matter in the filtrate Amount of filtrate employed.Amount of organic Per-centage upon the matter burnt off. whole amount of water. I. 132980 grm. 0.0956 grm. 0.003763 TI. 136*2000, 0.0759 )) 0-00291 7 Mean 0.006656 Determination of organic matter in the precipitate iimount of precipitate Amount of organic Per-centage upon the employed. water burnt off. whole amount of water. I. 1,9350 grni.11. 0.4610 , 0.6407 grm.0.1471 , 0.006734 0.006479 ~- ~ 0-003340 Determination of carbonic acid At the time of collecting the water a syphon capable of containing 534 cubic centimetres of distilled water was filled twelve times and discharged into four bottles containing chloride of calcium and ammonia. The precipitate which had formed in all the bottles weighed 3.6067 grms.Amount of precipitate Amount of carbonic Amount calculated on employed. acid evolved. the whole precipitate. I. 0.4226grm. 0.1200 grm. 0.535662 11. 0.5144 , 0.1560 , 0.521 738 Mean 0.528700 Per-centage in the water 0.016495 ON THE ANALYSIS OF THAMES WATER From the analytical results the following composition of the water is deduced In 100 litres. In a gallon. (Grammes.) (Grains.) Sulphate of potash . . . . . -385 *2695 Sulphate of soda . . . . . . 4.436 3.1052 Chloride of sodium . . . . . 3.389 2.3723 Chloride of magnesium . . . . m114 $0798 Chloride of calcium* . . . . . 9.963 6,9741 Chloride of lime . . . 11.595 8-1165 177 01239 Silicic acid . . . . . . . Phosphoric acid .. . . . . . traces traces Alumina . . . . . . . traces traces Insoluble organic matter. . . . 6.656 4.6592 Soluble organic matter . . 3.340 2.3380 40.055 28.0385 Direct determination of fixed constituents 40.843 28.5901 Having deducted from the total amount of carbonic acid the amount required to combine with the lime the amount of free carbonic acid is 00005105 grm. corresponding to 27.1906 cubic centimetres in a litre or to 8.8076 cubic inches in an imperial gallon. The greatest difference between Mr. Clark’s analysis and my own consists in the variation in the amounts of soluble salts; the soluble salts found by hlr. Clark amount to only 6.3118 while I obtain as much as 18.287. A proportionate difference exists in the relative amounts of organic matter.My best thanks are due to Professor Hofmann for the many attentions and kindness that I have received from him during the above investigation. * On the principle of combining the strongest bases with the strongest acids in this analysis as well as in that of Mr. Clark chloride of calcium is enumerated along Mith sulphate of soda although we may assume that the constituents of these two salts are actually in solution in the form of sulphate of lime and chloride of sodium. MESS-R8. MAYER AKL) BRAZTER ON THE February 5 1849. Thos. Graham Esq. Vice-president in the Chair. A specimen of a phosphatic earth from the green sand formation of the south of England was presented by Mr. J. T. Herapath to the Society’s Musenm.This substance is now often substituted for bone-earth in the preparation of superphosphate of lime for agricultural purposes. It contains according to Mr. Herapath’s analysis traces. Organic matter . Silica with some silicate of alumina and 13.240 silicate of iron . .. Alkaline salt . ..traces. Carbonate of lime . 28.400 Y9 magnesia . traces. Sulphate of lime . 0.736 Phosphate of lime (tribasic) . 21-880 6C magnesia . traces. Perphosphate of iron . .. 211.760 Phosphate of alnmina . . . 7.032 Fluoride of calcium . traces. Water . 3.400 Lost . ... 0.552 100~000 The following paper was read

ISSN:1743-6893    

DOI:10.1039/QJ8500200074

出版商:RSC    

年代:1850

数据来源: RSC

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MESS-R8 MAYER AKL) BRAZTER ON THE VIII.-Analyses of the mineral constituents of the Flax plant and of the soils on which the plants had been grown. By J. E.MAYERai2d J S. BRAZIER, E~QRS. The daily increasing extent to which flax is cultivated by the farmer necessarily directed the attention of chemists to the analysis of this plant soon after the importance of the mineral constituents strangely neglected for a considerable period had been generally acknowledged by the scientific agriculturist. We owe to Sir Robert Kane two excellent papers containing the analyses both of the ashes of different specimens of flax and of the soils on which they had been cultivated.* These specimens had been grown principally in Belgium and Holland where the greatest care is taken in preparing and manuring the land.The analyses which we intend to communicate in the following pages were made with * Philosophical Magazine vol. XXXI. p. 43. MINERAL CONSTITUENTS OF THE FLAX PLANT. different specimens of Russian growth. They were supplied to us by Dr. Hofmann,* under whose guidance we have worked throughout. The localities from which we have obtained our specimens of Flax are the Russian districts known as Esthonia or Estland Livonia or Lievland Courland and Lithuania. The first of these districts with the second and third mentioned are situated on the eastern shores of the Baltic; the fourth Lithuania is the only inland country. These countries extend from 48O to 60° north latitude and from ZP to 28O east longitude.The plan we adopted for the preparation of the ash was the following :-A handful of stems after being inflamed were held over a porcelain dish and allowed to burn gently. The ashes collected in the dish by this process in one or two instances were remarkably white; however in order to free them still more from the remaining carbon they were placed small quantitiea at a time in a platinum dish over a gentle gas flame. In this manner also the sulphides formed in the process of combustion were entirely reconverted into sulphates. This conversion was proved by experiment previous to analysis. In order to hasten the latter part of the process the Lithuanian and Estland ashes were burned with protoxide of mercury. The general analyses were performed in the usual manner :-the experimental numbers in Table I.shew the quantities of substance employed the results from which are exhibited in Table 11. * I am indebted for these specimens to the kindness of Mr. Arthur Marshall of Leeds who had them sent from Russia for analysis being originally intended to supply the material for a continuation of Sir Robert Kane’s researches; and it was only in consequence of Sir Robert’s other avocations preventing him from following up the investigation any further that Mr. Marshall sent them to the Laboratory of the Royal College of Chemistry.-Dr. A. W. Rofmann. TABLE I. Lievland. Courland. Lithuanian. Estland. I. 11. I. 11. I. 11. I. 11. I r-A-1 grin. grm. grm. Fm. grm. grm. grm. grm.Quantity of ash employed for the 4.7076 4.6640 5.3100 1.2953 6.1526 5.8256 4.4630 general analysis ... Whole amount of the hydrochloric 324.0300 ,97.59 50 293,495 293495 24 2.56 20 06.9200 acid solution .... -A-7 Hydrochloric acid solution em-.} ployed for the alkalies . 17.5040 16.84 15 24.2960 27.4094 28.8473 28.1370 20,3340 I 239870 1Iydrochloric acid solution em-ployed for sulphuric and phos- { ;;:;;;;] 30,7767 26.6230 27-4080 28,0232 22.7 7 3 0 phoric acids ....1 { 22.6950) 1 23*0280 Hydrochloric acid solution for 25.4352 sesquioxide of iron lime and 30.2702 30.7767 { ;EE} magnesia .... 31.7940 27.5790 Quantity of ash employed for the 2.0813 1.3249 -8360 ........... 1.0017 ....... estimation of chlorine . . Quantity of ash employed for the -8532 *8875 -7023 -8097 -8017 -7450 .!I680 -8418 estimation of carbonic acid .} Quantity of the plant dried at 1000 C.for the estimation of the 6.0140 5.4247 1.4571 ........... 3.3575 ....... 2.4930 ............ amount of ash. ... I TABLE 11. 2 ? c Lievland. Courland. Lithuanian. E stland. I. 11. I. 11. I. TI. I. 11. grm. grm. grm. gmi. grm. grm. grm. Srm. Silicic acid . . . . . . . 0.3098 0.3260 0.3590 0.0868 0.2850 0.2597 0.2010 .. .. Sandand charcoal . . . . . 0,3240 0.0128 0.1485 0,0331 0.0750 0.0689 0.1145 .. .. Mixed chlorides of potassium and sodium . 2.6678 2.6492 2.8690 2.8736 3.127!1 3.1203 2.3332 2.3349 Bichloride of platinum and potassium . . 8.7439 8.6829 8.1660 8.1734 8.8082 8.7819 5.3430 5.3521 Chloride of sodium .. . . . .. .. .. ,. 0.3778 0.3797 0.4407 0.4409 0.7030 0.7001 Sulphate of baryta for sulphuric acid . 0.6369 0.6382 0 7222 0,6692 0.4299 0.5047 0.5424 .. .. Pyrophosphate of magnesia for phosphoric acid 0.6492 0.6504 0.5512 0.5601 1.0257 1.0394 0.9710 0.9813 Phosphate of sesquioxide of iron . . . 0.1338 0.1333 0.1477 0.1413 0.1513 0.1459 0.1252 0.1301 Q Carbonate of lime . . . . . I -4451 1.4314 1.5998 1.9077 1.9832 1.9955 1.8913 1.8814 Pyrophosphate of magnesia for magnesia . 0.8028 0.7324 0.9046 0.8801 0.8818 0,9592 1.3006 1.2817 Chloride of silver . . . . . 0.0409 0.0277 0.0320 .. *. 0.0692 .. .. 0.0437 .. .. Carbonic acid . . . . . 0.1500 0.1550 0.1300 0.1500 0.1 830 0.1700 0.0750 0.0650 Amount of ash left on incineration . . 0.2532 0.2240 0.0530 .... 0.0773 .. .. 0.1020 .. .. MESSRS. MAYER AND BRAZIER ON THE These numbers correspond to the following composition per cent. I.-LIEVLAND FLAX ASH. The stems upon incineration gave in average 4.1292 per cent of ash. Composition of the ash directly found I. 11. MEAN. Potash . . 35.0670 34.8588 34,9629 Lime . 17.1 892 17.1833 17.1 862 Magnesia . Sesquioxide of iron. Chloride of potassium Phosphoric acid . Sulphuric acid . Silicic acid . 6.2197 0.9235 1-0849 8.8048 4.5097 6-5812 6.3278 0.9286 1.0201 8-8224 4.6012 6.921G 6.2738 0,9260 1.0525 8-8136 4.5554 6.7514 Carbonic acid . 17.5914 17.4648 175281 Sand and charcoal . 0.6788 0.3425 0.5 106 98.6502 98.4711 98,5605 The above numbers after deducting sand and charcoal which are considered but as accidentally present and also carbonic acid give the following composition per cent Potash .. 4(3.42 Lime. . . 21-35 Magnesia . Sesquioxide of iron . Chloride of potau ' *slum. Phosphoric acid . . Sulphuric acid . Silicic acid . ~I.-COURLAND FLAX 7.79 1.15 1-31 . 10.94 . 5.66 8-38 100~00 ASH. The stems upon incineration gave in average 3.6358 per cent of ash. Composition of the ash directly found I. 11. MEAN. Potash . 29.6786 29.5988 29.6387 Soda . 2.9640 2.9433 2.9536 Lime . Magnesia . Sesquioxide of iron Manganese . Chloride of sodiumPhosphoric acid . . . . 20*1184 6.1111 0.9038 trace 1.3562 6.5948 20.0355 6.2123 0.8646 trace 1.5562 6.7027 20.0769 6.1617 0-8842 trace 1.5562 6.6487 Sulphuric acid .Silicic acid . 4-6647 6.7027 4.3220 6.7604 4,4933 6.7316 Carbonic acid . . 18.5106 18.5253 18.5179 Sand and charcoal. . 2.5559 2.7966 2.6762 100.3608 100.3177 100.3390 MINERAL CONST$TUENTS OF THE FLAX PLANT. Per-centage after dedncting sand charcoal and carbonic acid Potash . . . . Soda. . Lime. . . Magnesia . Sesquioxide of iron . Chloride of sodium . Phosphoric acid . . Sulphuri; acid . Silicic acid. . . III.-LITHUANIAN FLAX 3744 3.74 25.39 7.71 1.13 1*94 8.31 5.89 8.45 10@00 ASH. The stems upon incineration gave in average 2.3023 per cent of ash. Composition of the ash directly found I. 11. MEAN. Potash . . . 27.5459 27.4770 27,5114 Soda .2.3055 2.3065 2-3060 Lime . . . 18-0526 18.1648 18.1087 Magnesia . 5.6794 5.5154 5.5974 Sesquioxide of iron . 0.7991 0.7710 0.7850 Chloride of sodium . 2.8115 2-8115 2.8115 Yhosphoric acid . . 10.5868 10.8972 10.7420 Sulphuric acid . 2.6755 2.8137 2.7446 Silicic acid . . 4,6346 4.4532 4.5439 Carbonic acid . . 22.8302 22.7272 22.7787 Sand and charcoal. . 1.2190 1.1828 1~2009 99.1401 99.1203 9901301 Per-centage after deducting sand charcoal and carbonic acid Potash . . Soda. Lime. . Magnesia . Sesquioxide of iron . Chloride of sodium . Phosphoric acid . Sulphuric acid . Silicic acid. + . 36.61 3.06 24-09 7-45 1004 3.75 . 14.30 3-65 6.05 100*00 62 MESSRS. MAYER AND BRAZIER ON TI-IE IV.-ESTLANDFLAX ASH.The stems upon incineration gave in average 4.0914 per cent of ash. Composition of the ash dircctly found r. IT. MEAN. Potash 23.1083 523-0432 23.0757 Soda . 7.5111 7.5323 7.521'? Lime . . . 23,8567 23.6070 23.7318 Magnesia . . 10.6274 10.4718 10.5496 Sesquioxide of iron . 0.9115 0.9363 0.9239 Chloride of sodium . 1.5069 1.5069 1.5069 Phosphoric acid . . 13.8098 13.9642 13.8870 Sulphuric acid . 4.1678 4.1678 4.1678 Silicic acid . 4.4815 4.48 15 4.4815 Carbonic acid . 7.7559 7.7215 7-7387 Sand and charcoal . 2.5878 2.5878 2-5878 100.3247 100.0203 100.1724 Per-centage after deducting sand charcoal and carbonic acid Potash . . 25.70 Soda . 8.37 Lime. . 26.41 Magnesia . . 11.74 Sesquioxide of iron 1-0.2 Chloride of sodium .1.67 Phosphoric acid. . 15.47 Sulphuric acid . 4064 Silicic acid. 4-98 100*00 From the foregoing analyses the following comparative table has been made from which it will be readily seen in what points the ashes of these different specimens agree in composition. Lievland. Courland. Lithuanian. Estland. I. 11. 111. IV. Potash . . 43.42 37-44! 36.61 25.70 Soda . I 3-74 3-06 8.37 Lime . . 21.35 25.39 24.09 26.41 MagnesiaSesquioxide of iron . Manganese . Chloride of sodium . Phosphoric acid . Sulphuric acid. . Silicic acid . , !,potassium e . . 7.79 1.15 I -1.31 10-94 5.66 8.38 7.71 1.13 trace. 1-94 8-31 5-89 8.45 - 7.45 1*04 3-75 14.30 3.65 6.05 - 11-74 1.o2 1-67 15*47 4.64 4.98 - 100~00 100~00 1oo*oo 100~00 MINERAL CONSTITUENTS OF THE FLAX PLANT.85 We also append in a tabular form the results of Sir R. Kane’s analyses of this plant taken from his paper read before the Royal Dublin Society on the 6th of April 1847. To facilitate comparison we have re-calculated these analyses after deducting the carbonic acid. A B CD Courtrai An twerp District. District. * 5 + a -I-Potash . 9-69 30.62 26.67 28.62 21.35 11.78 6.60 Soda 24.1 6 none. 16.88 0.48 12.65 11-82 6 61 Lime 19.37 22 04 22.15 21-19 21.30 14.85 23-67 Magnesia . 4.34 4.45 4-70 4 05 3.50 9.38 4 21 Sesquioxide of iron 5.66 2.03 1’31 2.53 2.74 > 14.10 It Alumina . 0.56 0.58 0-86 , , 1.67 7.32 i9 ?* Manganese . trace. trace. trace. , ? 1.12 19 it Yi ?Y Sulphuric acid 7.93 8-33 8-18 13.43 11.22 3.19 9.30 Phosphoric acid 14.10 15.78 10.66 12-19 12.82 13.05 7-29 Silicic acid .3.85 4.54 3.20 3.36 6.18 25.7 1 0.94 Chloride of sodium 10.34 11.63 5 49 14-15 6 57 2 90 26.15 100~00100*oo too 00 100 00 LOO 00 100~00100.00 On comparing the results of our analyses with those of Sir Robert Kane we find at once that the general features of both are identical although as might be expected discrepancies present themselves respecting the individual constituents. In the ashes both of the Belgian and of the Russian specimens we meet with a very large amount of alkali (nearly 40 per cent) the quantity too of phos-phoric acid is very considerable (from 10 to 15 per cent). Our analyses then furnish a further proof that flax must be classed among the most exhausting crops for the amount of valuable mineral substances which we remove from the soil in this plant considerably exceeds the quantity which is generally extracted from it in the form of wheat or corn.From a statement of Mr. Mac Adam,* it appears that one rood of land yields about 12.7 cwt. of recently-pulled flax plant. If we take this number as tbe basis of calculation and the average per- centage of ash at 3.53 lbs. of alkalies at 39.58 Ibs. and of phosphoric acid at 12.51lbs. we find that a flax crop removes from a rood of land not less than 12.21 lbs of alkalies and 5-94lbs. of phos-* Royal Agricultural Journal vol. VIII p. 361 RIESSRS. MAYER AND BRAZIER ON THE phoric acid; on the other hand we have learnt froni the researches of Mr.Way,* that a rood of land which has served for the cultiva- tion of wheat loses (an average taken from a great number of analyses) about 7.5 lbs. of alkali and 6.9 lbs. of phosphoric acid. These figures show that the amount of phosphoric acid in the flax crop closcly approaches that of the wheat whilst the lattcr extracts only about half the quantity of alkali which we find in the former. Hence it would appear that a flax crop is at least as exhausting as a crop of wheat. There is however one striking point of dissimilarity between the cultivation of wheat and that of flax and we are indebted to Sir Robert Kane for having for the first time brought this point under the notice of the farmer in a forcible manner-viz that while the mineral ingredients which we remove from our fields in wheat or cerializ in general become constituents of food and enter in this manner into a circulation from which even under very favourable circumstances they return to the soil only after the lapse of some time; the woody fibre of flax as a necessary preliminary to its being used by man is separated to z1 considerable extent from those very mineral substances which are so essential for its successful growth.This mineral matter when economized in a proper manner by the farmer may be returned to his field to keep up the equilibrium of its fertility. The vegetation of the flax plant rcscmblcs in this respect the growth of the Sugar-cane from the culture of which we expect a material consisting entirely of atmospheric constituents.The in- organic substances taken up by the plant are only instruments used in its production which should bc as carefully preserved as tools in a manufactory and will then do further duty iii promoting the elabo- ration of future crops. The analysis of the flax ash suggests a few remarks respecting an interesting feature in the nature of ashes generally which was first noticed by Professor Liebig in his celebrated Agricultural Chemistry. On comparing the composition of the ashes of specimens of the same plant cultivated under different circumstances he observed that notwithstanding very considerable discrepancies in the constitution the entire basic power of the different bases united with a certain class of acids for instance the organic acids remained constant for different specimens of the same plant or in other words the basicity of an oxide being measured by its oxygen the total amount of oxygen contained in the bases forming organic * Royal Agricnlturd Journal vol.VII. p. 593. MINERAL CONSTITUENTS OF THE FLAX PLANT. Quantity of basic Quantity of basic Name of the ash. -oxyge;l in 100 Name of the ash. oxygen in 100 parts. parts. ~ ~~ Heestert . . . 16.95 Lievland 16.80 Escamaffles . . . 14.00 Courland 17.89 HammeZog . . 17.71 Lithuanian 17.12 Unknown district . 13.36 Estland 17.86 Holland . . . 15-83 Dublin . . . . 16.36 Mean 17.42 Armagh . . . 15.68 b I Mean 15.68 The composition of several wheat-ashes as resulting from Mr.Way’s analysis likewise appears to be favourablc to this view.* Specimen No. 1. Hopeton wheat . . . . 11.64 per cent. > No. 2. Creeping wheat . . . . 11-52 , , No 3. Red straw white wheat. . 11.02 , , KO.4. Hopeton wheat No. 2 . . 11.9% , , No. 5. French wheat . . . . . 12.59 , , No. 6. Egyptian wheat. . . . . 12-19 , , No. 7. Odessa wheat . . . . . 12 08 , , No. 8. Marianople wheat. . . . 14-46 ) , No. 9. Hopeton wheat No. 3 . . 12-89 , , No. 10. Red straw white wheat. . 11.53 , 9 No. 11. White wheat . . . . . 12-24 ,) Mean 12-19 The argument however drawn from these ashes is of minor importance the discrepancies in their composition bcing far less conspicuous than in the former cases.The number representing the basic power of the sum of the metallic oxides in the ash varying within trifling limits it is but a * Royal Agricutural Society Journal vol. vii. p. 666. MESSRS. MAYER AND BRAZIER ON THE natural consequence that we should likewise find a certain constancy in the acidity of the total amount of acids. Without going into detail a glance at the tables will shew indeed that a replacement of the acids occurs to a certain extent. Whenever the amount of carbonic acid which represents the organic acids diminishes we find the quantity of inorganic acid as sulphuric and phosphoric increases and vice versa”. Our attention was nest directed to the soils upon which the different specimens of flax had been grown samples of which through the kind- ness of Mr.Marshall had likewise been forwarded to Dr. Hofmann. These soils all gave a brownish colour to boiling water owing to a portion of the organic matter being soluble in that menstruum. The following table shews the behaviour of these soils with solvents 1 1 Lievland. ICourland.1 Lithuania. Estland. -0.0864 0 1700 0 1528 0.1497 Soluble in water. Inorganic matter . 0.2290 0.3125 0.4578 }Organic matter. . ---0.4417 1 Total . . . 0.3154 0.4825 0 5945 0.6075 Soluble in hydrochloric acid . . . 7.2596 6.9166 7 2433 8,7119 Insoluble residue . . . . . 92.4250 92.6009 92.1622 90.6806 100~0000100*0000 100 0000 I 100~0000 The following tables contain the details of the individual deter- min at ions :-TABLE I.Lievland. Courland. Lithuanian. Estland. 8l-m. Bm. Quant,ity of soil employed for grm. grm. general analysis . . . 20,0480 22.3010 18.5560 22.9480 Amount of the hydrochloric solu-tion . . . . . 270-0400 232.3550 324.12 50 263.98 Hydrochloric solution for alkalies 64.1800 67.4600 74.3800 56,1600 Hydrochloric solution for sul-phuricacid . . . 58-0350 65-2700 69.9400 45.53 Hydrochloric solution for phos-phoric acid sesquioxide of ;;:;;;; 69.7700 75.9 150 ( 88.7600 iron alumina lime and mag- j L 50.9400 nesia Hydrochloric solution for the sesquioxide of iron . . . 23.8400 46.9195 60.7950 22.1800 Quantity of soil for chlorine . 13.2600 11.3701 11.6611 14.4 190 Quantity of soil for total amount of organic matter .. . 7.5850 4-9i3a 5.6485 7.3205 Quantity of soil for total amount soluble in water . . . 164.8400 205.1700 228.2350 104.6100 MINERAL CONSTITUESTS OF THE FLAX PLANT. TABLE 11. Lievland. :ourland. Lithuan. Estland. Residue . . . . . . . 18.5 29 4 20.7465 1'i.1003 20.8094 Mixed chlorides of potassium and sodium . 0.1684 0.1757 0 1839 0.1 738 Bichloride of platinum and potassium. . 0.5217 0.3758 0.5255 0.4419 Chloride of sodium . . . . . 0.009 1 0.0609 0.0236 0.0388 Sulphate of baryta for sulphuric acid . . 0.0999 0.0543 0.0784 0.8897 Pyrophosphate of magnesia for phosph. acid 0.0448 0.0190 0.0234 0.0577 Sesquioxide of iron and alumina . . 0.6214 0,9477 0.9864 0.9250 Sesquioxide of iron . . . . . 0.3624 0.5300 0.5911 0.4537 Carbonate of lime .. . . . 0.1504 0.3113 0.1494 0.3237 Pyrophosphate of magnesia for magnesia . 0.1103 0,1075 0.0918 0.2228 Chloride of silver for chlorine . . . 0.0150 0.0071 0.0123 0*0280 Amount of soil left after ignition . . 7,2120 4.7150 5.4031 6.9645 From the former tables we obtain by alculati n the dlowing amounts of constituents of 100 parts in the soils :-Lievland. Courland. Lithuan. Estland. Potash . . . . . 0.5011 0.3241 0 5466 0.3726 Soda Lime . . . . . . . . . . ..o&i 0.1320 0.7816 0 0152 0.4980 0 0480 0.7955 Alumina . . . . . Magnesia . .. . 0,2006 1.1919 0.1304 1.8731 0.1 805 2.1418 0.3619 2.0102 Sesquioxide of iron . . . Manganese . . . . Chloride of sodium . . . 1.8076 trace. 0.0455 2.3767 trace. 0.0247 3-1900 trace. 0.0421 2.0206 trace. 0-0790 Srilphuric acid .. . Phosphoric acid . . . Organic matter . . . Insoluble residue after deduct- ing organic matter . . 0.1539 0.1399 4.7176 91.0634 0.0880 0.0538 4.0300 89.4872 0.1206 0.0805 4.3442 88.4 724 0.1618 0.1597 4.8630 88.2364 I 100-1966 99.3016 99.66 19 99.1087 The insoluble residue constituting the greater portion of the soil was fused with carbonate of potash. The following are the experi- mental numbers :-~ ievland. Courland Lithuania. Estland. Amount of residue employed . . . 0.9790 1.2955 0.8620 0.9780 Amount of hydrochloric acid solution ob-tained . . . . . . . 82.35 213.9450 270.3 300 91.9300 Amount of hydrochloric solution for the determination of sesquioxide of iron and 17.11 26.9730 29-58 35 30.1800 alumina . . . . . .i Amount of hydrochloric solution for the determination of lime . . . . .a 27-7520 26 0968 26.1700 90 MESSRS MAYER AND BRAZIER ON THE FLAX PLANT. Amount of silicic acid obtained . . Amount of sesquioxide of iron and alu-o.0260 o.0106 o.oo23 o.0210 mina obtained . . . . .)1.. 1 1 1 Amount of carbonate of lime obtained . 0.0061 0.0015 0-0120 The insoluble residnes upon calculation yield the following results per cent. 1 I 1 I Lievland. Courland. Lithuania. Estland. Lime . . . . traces. 1.8727 0.8778 2.0120 Alumina . . . . 11.6270 6.1145 2.2452 5.7549 Sesquioxide of iron . . traces. traces. traces. traces. Phosphoric acid . . traces. traces. none. traces Silicic acid . . . 79.3424 81.5000 85.0938 80.5676 I 90.9694 I92.6224 In all the four soils we find comparatively speaking considerable quantities of alkali especially potash and also of phosphoric acid.They closely resemble the Belgian soils analysed by Sir Robert Kane as may be seen from the tables,which we borrow from SirRobert's paper --. Potassa .....0.160 0.123 0-068 0.151 0.583 b Soda .......0.298 0.146 0.110 0.206 0.306 Lime ... . .. .0.357 0.227 0.481 0.366 3.043 Magnesia ......0.202 0.153 0.140 0.142 0.105 Alumina ......2.102 1.383 0.125 0,988 5.626 Sesquioxide of iron ...3.298 1.663 1.202 1.543 6.047 Manganese . ....trace trace a trace no trace trace ..0.017 0-030 0.067 0.009 0.023 Chloride of sodium Sulphuric acid .. . .0.025 0.017 0.013 0.026 0-023 Phosphoric acid . . . 0.121 0.152 0.064 0.193 0.159 Organic matter not driven off at loo*per cent .i 3.123 2.361 4.209 3.672 5.841 Clay ......#14.920 9.280 5.760 4.400 17.080 Sand ......(175.080 84.065 86.797 88.385 60.947 -_I---199.600 99.975 100.081 99.783 In conclusion we beg to express our warmest thanks to Dr.Hofrnann for his instruction and valuable advice during the prosecu-tion of these analyses and for the uniform kindness we have at all times experienced at his hands. 1-

ISSN:1743-6893    

DOI:10.1039/QJ8500200078

出版商:RSC    

年代:1850

数据来源: RSC