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ON A MODIFIED FORM OF NITROMETER

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1. The gas may be readily washed by allowing potash solution to flow through the apparatus: this enables the measuring limb to be of small capacity, and capable of more accurate reading than is common with most nitrometers. In this case there is no fear of the potash solution becoming saturated with carbonic anhydride, and thus spoiling the com. bustion.

It has been our custom to keep a gentle stream of intervals.

FOR USE IN NITROGEN ESTIMATIONS BY potash flowing during a combustion, re-filling the cup at

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2. By working under considerably diminished pressure an even current of gas can more readily be maintained, and the risk of bursting the heated tube is lessened.

3. The gas may be drawn off for subsequent analysis. 4. It is usual in a combustion to first pass carbonic anhydride through the tube to drive out all the air, and the frequent testing of the gas to see if all the air is expelled necessitates in the ordinary Schwarz's nitrometer-the filling and emptying of the potash in the side limb, an operation which is entirely avoided in the use of the nitrometer now described.

The apparatus is not much more expensive than the ordinary form of nitrometer, and could readily be obtained from any instrument maker.

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B

For this purpose the special form of nitrometer to be described was designed. An extended experience with it has made manifest so many points in which it is superior, in our opinion, to other forms that it has been thought desirable to give a brief description of the apparatus. The construction of the nitrometer is simple and the diagram hardly needs further explanation.

In using the apparatus the nozzle of the tap B is kept immersed in the potash solution contained in the dish, and the tap is turned so that the potash is expelled through this nozzle by the incoming gas.

When it is desired to read the volume of the gas, the liquid in the two columns is brought to the same level by use of the three-way tap B.

The advantages gained by the use of this nitrometer over other forms, when indiarubber tubing is not used, may be briefly summarised as follows:

ON THE SYNTHESIS OF ALBUMIN. By ALFRED H. ALLEN.

THE announcement of Dr. Leo Lilienfeld at the recent International Congress of Applied Chemistry at Vienna, that he had effected the synthesis of albumin, will be re. ceived by chemists with considerably more scepticism than it has met at the hands of the professional paragraphists. The circumstances of the announcement are not such as to encourage implicit faith in the reality of the alleged discovery, but Dr. Lilienfeld may be the victim in this respect of the professional zeal of the reporter.

From the accounts which have hitherto come to hand, it appears that it is not true albumin of which Dr. Lilien. feld claims to have effected the synthesis, but "peptone," which is a very different thing. It is said to be produced by the condensation of glycocine (amido-acetic acid) with phenol, by means of phosphorus oxychloride. The reac tion is said to occur quantitatively and with great facility, allowing of the whole process being shown at the meeting. Further, Dr. Lilienfeld is said to have demonstrated, by the most conclusive tests, the absolute identity of his product with natural peptone, or-according to some accounts -with true albumin. Seeing how very ill-defined are the chemical tests for "peptone," and that more than one kind of peptone is recognised, this part of the account must be received with caution. Still more doubt attaches to the statement that Dr. Lilienfeld's product has the same elementary composition as natural peptone (or albumin). Seeing that natural albumin and peptone both contain sulphur as an essential constituent, and that Dr. Lilienfeld's process does not involve the employment of sulphur in any form, there seems to be a screw very loose somewhere.

Although the description of the mode of formation of Lilienfeld's body appears to negative the conclusion that he has effected the synthesis of either albumin or peptone, it by no means follows that he has not produced an albuminoid substance of great theoretical interest. He has undoubtedly been working in the right direction-in fact, his method may not improbably have been suggested by the interesting and ingenious suggestions of Dr. P. W. Latham (Croonian Lectures, 1886).

Commencing with the fact that by the reaction of hydrocyanic acid on aldehyd, cyan-ethylic alcohol,— CH2.CH(CN). OH,

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is formed, Latham points out that the cyan-alcohols are, as a class, very unstable bodies, readily undergoing change, and when treated with ammonia form unstable cyan-amides, which easily undergo condensation with formation of imido-nitriles and elimination of ammonia. Latham thinks these facts suggest the enquiry :-" Have we not in these cyanogen compounds substances possessing some properties that belong to living tissue, namely, those of undergoing intra-molecular change and also condensation? And, further, if from these substances we can obtain the various products which result from the disintegration of albumin, may not albumin itself be simply a compound made up of these elements?"

In the laboratory, it is practicable to obtain from these cyan-alcohols the corresponding amido-acids, glycocine, leucine, &c., and all the acids of the acetic and lactic series. Latham suggests that, if it were found possible to reverse the process, albumin might be built up theoretic ally from such constituents.

Latham further instances the well-known molecular tran position by which ammonium cyanate is converted into urea, and quotes Pflüger's remark that the great molecular energy of cyanogen compounds suggests that the functional metabolism of protoplasm by which energyis set free may be compared to the conversion of the energetic unstable cyanogen compounds into the less energetic and more stable amides. In other words, that ammonium cyanate is a type of living, and urea of dead, nitrogen, and that the conversion of the former into the latter is an image of the essential change which takes place when a living proteid dies.

In accordance with this view, the group -CO.NH- is dead nitrogen, and would, on becoming part of a living tissue, be transformed into = C:N.OH.

Cyanic acid, CNOH, is itself readily susceptible of polymerisation, with formation of cyamelide, C3H3N3O3. Latham points out that the glycines are capable of uniting with each other, glycocine being not improbably glycocine amidoacetate,—

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CHEMICAL NEWS,
Aug. 26, 1898.

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CN

HSOS.C

This suggestive formula contains C72H118N18022S, and differs only by H6 from Lieberkühn's formula for albumin, C72H112N18022S.

The discovery of lysine, lysatine, and trypsophan or protein-chromogen, necessitates some modification of the above formula, which, of course, cannot be regarded as more than an ingenious and highly suggestive arrangement, which might be of service as a working hypothesis.

Pflüger has observed, and Loew and Bokorny corroborated the fact, that living proteid matter in the cells of various algæ reduces silver from a dilute alkaline solution of the nitrate, but that dead protoplasm or proteid does not give the reaction. Hence it is suggested that a compound of aldehydic nature exists in living protoplasm. By the reaction of formic aldehyd with ammonia, aspartic aldehyd may be supposed to be formed, a body which, though unknown, has the same composition as leucine. and a sulphur compound, with elimination of water, the By its repeated polymerisation in presence of hydrogen following equation may be realised :

6C12H17N3O4+H2S+6H2=C72H112N18SO22+2H2O.

Grimaux (Compt. Rend., xciii., 771) has proposed to define proteids as nitrogenised colloids, which by hydrolysis split up into amidated acids, carbon dioxide, and ammonia." On heating aspartic anhydride to 130° with urea for two hours, Grimaux obtained a thick mass, completely soluble in boiling water to a gummy, highly colloid liquid, yielding highly gelatinous precipitates with acids, alkaline salts, magnesium and aluminium sulphates, solutions of iron, copper, and mercury, and with tannin. The jelly yielded by acetic acid dried up to a substance resembling dried albumin. It softened in boiling water without undergoing solution, but dissolved in caustic potash to a liquid giving a violet colouration with cupric sulphate.

CHEMICAL NEWS, Aug. 26, 1898.

}

Report of the Committee on Indexing Chemical Literature.

Of course it by no means follows, as Dr. Lilienfeld is reported to have said, that a synthetical product of the same ultimate composition as peptone will have the same food-value. This fact is familiar to the mere tyro; but it may be of interest to recall the case of quinine, the synthesis of which may any day be effected. Already two distinct basic substances isomeric with quinine have been prepared synthetically, but neither base has the physiological characters of true quinine. Sheffield, August 13, 1898.

SIXTEENTH ANNUAL REPORT OF THE COMMITTEE ON INDEXING CHEMICAL LITERATURE.*

99

Second edition. Smithsonian Miscellaneous Collections, No. 1076. City of Washington. 1897. Pp. 1247. 8vo.

This bibliography was first issued in 1885, and the second edition has been prepared at the request of the Smithsonian Institution. It embraces periodicals in every department of pure and applied science, including of course chemistry and chemical technology. The Chronological Tables give the date of publication of each volume of about 550 periodicals; they enable one to ascertain the date of a given volume in a given series of a given work, or to determine the number of a volume when the date only is given. The Library Check-List shows in what American Libraries, 133 in number, complete sets of the periodicals may be found. The second edition brings the date down to 1895; its publication has been delayed by the compilation of the Check-List, The periodicals catalogued number 8603.

THE Committee on Indexing Chemical Literature respect-"Alkaloidal Estimation;" a bibliographical index of che-
fully presents to the Chemical Section its Sixteenth
Annual Report, covering the twelve months ending
August, 1898.

Works Published.

"A Bibliography of the Metals of the Platinum Group," -Platinum, Palladium, Iridium, Rhodium, Osmium, Ruthenium, 1748-1896. By Jas. Lewis Howe, Smithsonian Miscellaneous Collections, 1084. City of Washington, 1897. Pp. 318, 8vo.

This fine volume forms one of the most valuable and comprehensive indexes to an important field of chemical literature produced under the auspices of the Committee since its appointment in 1882. It shows on every page evidence of conscientious and critical skill; the author. and subject-indexes, with which the book concludes, are important features. Its workmanship and the method of presentation of data in type make Dr. Howe's volume a model.

"References to the Literature of the Sugar-Beet," exclusive of works in foreign languages. By Claribel Ruth Barnett. U.S. Department of Agriculture. Library Bulletin, June, 1897. 9 PP. 4to. This carefully edited contribution to the bibliography of a subject interesting to the chemist as well as to the scientific farmer, manifests the activity of the U.S. Department of Agriculture in its Library.

"A Chemical Bibliography of Morphine, 1875-1896." By H. E. Brown, under the direction of A. B. Prescott. Completed in "Pharmaceutical Archives," vol. i., No. 3.

A supplement carries the literature through 1897. The separates contain an index of authors.

"A Bibliography of the Metallography of Iron and Steel." By Albert Ladd Colby. Published in the Metallographist, vol. i., No. 2, pp. 168-178, April. 1898. This includes 188 titles, arranged alphabetically by authors, and numbered chronologically; it is reprinted, extended, and re-arranged from The Iron Age, Jan. 27, 1898, by the author.

"Review and Bibliography of the Metallic Carbides." By J. A. Mathews. Smithsonian Miscellaneous Collections, No. 1090. City of Washington, 1898. Pp.

32, 8vo.

Published by the Smithsonian Institution on recommendation of this Committee. Under each metal forming a carbide the author has given a brief synopsis of the chemical data with references to the literature on that subject. There is an author-index.

"A Catalogue of Scientific and Technical Periodicals, 1665-1895, together with Chronological Tables and a Library Check List." By Henry Carrington Bolton.

From Advance sheets of the Proceedings of the American Association for the Advancement of Science, August meeting, Boston, 1898. Communicated by H. Carrington Bolton.

mical research prepared from original literature for the Committee of Revision and Publication of the Pharmacopoeia of the United States of America, 1890-1900, by Paul I. Murrill under the direction of Albert B. Prescott. Ann Arbor, 1898.

A pamphlet of about sixty pages, not for sale. "The Review of American Chemical Research," edited by Arthur A. Noyes and published in the Journal of the American Chemical Society, completed vol. iii., in December, 1897. Two indexes, an author- and a subject-index, increase its value.

46

·

Mr. E. W. Allen, Acting Director of the Office of Experiment Stations, U.S. Departinent of Agriculture, in reply to inquiries, sends the following communication:During the past year we have completed volume ix. of the Experiment Station Record' (1897-'98). This, like former volumes, contains abstracts of and references to articles on the methods and results of work in agricultural chemistry published in this country and in Europe. During the past year the review of Russian scientific periodicals has been added. About 2000 cards of the Card Index of Experiment Station Literature have been issued during the past year, making a total of 16,000 cards in this index at present. In addition to several accounts of chemical studies of the nutrition of man, the Office has issued a ' Report of Preliminary Investigations on the Metabolism of Nitrogen and Carbon in the Human Organism with a Respiration Calorimeter of Special Construction,' by W. O. Atwater, C. D. Woods, and F. C. Benedict, the work being carried on in part by funds fur. nished by this Office. In this connection may also be mentioned a compilation of over 400 pages of metabolism experiments in which the balance of income and outgo was determined, made by W. O. Atwater and C. F. Langworthy, and issued from this Office. The bulletin is a in which the balance of one or more of the factors of indigest of about 3600 experiments with man and animals, come and outgo was determined. While this work may at first thought seem somewhat a field, it is chemical in its character as well as physiological, and has involved in some cases quite extensive chemical studies."

The "Digest of Metabolism Experiments" herein named forms Bulletin No. 45 of the Office of Experiment Stations, and constitutes a comprehensive bibliography of the subject.

The Committee chronicles the publication of the following bibliographies bearing more or less on chemical researches:

"Contributions to the Bibliography of Gold." By A.

Liversidge. Australasian Association for the Advancement of Science. Brisbane, 1895, 8vo. "Analyst " (The). The organ of the Society of Public Analysts. General Index to the Proceedings of the Society of Public Analysts, vol. i. (1876), and to the

122483

ICO

Estimation of Tin in Salts of Tin.

Analyst, vols. i.-xx. (1877-1896). Compiled by J. Cuthbert Welch. London, 1897. Pp. i.-181, 8vo. Arranged on the dictionary plan, authors, subjects, and cross-references in a single alphabet. "Bibliographie des Travaux Scientifiques" (Sciences Mathématiques, Physiques, et Naturelles), publiés par les Sociétés Savantes de la France. Par J. Deniker. Tome 1, part 2. Paris, 1897, 4to. Part I was published in 1895. Most important for original papers published in France. "Biographisch - Literarisches Handwörterbuch

zur

Geschichte der exacten Wissenschaften," von J. C. Poggendorff. Dritter Band (die Jahre 1858 bis 1883 umfassend). Herausgegeben von B. W. Feddersen und A. J. von Oettingen. Leipzig, 1897-98. Roy. 8vo.

This valuable addition to Poggendorff's well-known biographical dictionary is useful to chemists, inasmuch as it gives the titles of original papers by the principal chemists of the world published during the period speci

fied.

Works in Preparation and Reports of Progress.

"A Subject- and Author-Index to the first twenty volumes of the Journal of the American Chemical Society" is being compiled by Mr. Sohon, who expects to complete the MS. in December, 1898.

"A First Supplement to the Select Bibliography of Chemistry, 1492-1897," by Henry Carrington Bolton, is now going through the press. It will form a volume of the Smithsonian Miscellaneous Collections of about 600 pages.

CHEMICAL NEWS,
Aug. 26, 1898.

miques des Fibres Textiles," Paris, 1893, noted in our Thirteenth Annal Report.

Two unfinished manuscript indexes are at the disposal of persons willing to undertake their completion :-An "Index to the Literature of Carbonic Oxide," begun by the late Prof. William Ripley Nichols and continued by Prof. Augustus H. Gill; and an “Index to the Literature of Milk," begun by Prof. Clement W. Andrews.

As stated in previous reports, this Committee does not but leaves method and topic to be chosen by compilers; attempt to prescribe a fixed plan for volunteer indexers, the Committee does not seek to control the productions further than to insure work of high merit and to guard the interests of the Smithsonian Institution, which has Chemists willing to undertake the compilation of indexes agreed to publish manuscripts endorsed by the Committee. are requested to send their names and addresses, with a memorandum of the subject chosen, to the Chairman of the Committee (Cosmos Club, Washington, D. C.), who will furnish sample copies of indexes and other information. Committee:—

"A Second Supplement" to the same Bibliography, to ESTIMATION
contain chemical dissertations only, is well advanced,
about 8000 titles being already in hand.

Dr. A. C. Langmuir reports the completion of his MS.
"Index to the Literature of Zirconium."

Dr. C. H. Joüet reports the near completion of his "Index to the Literature of Thorium."

Mr. George Wagner reports progress on a "Bibliography

of Oxygen."

The manuscript of an "Index to the Literature of Thal-
lium, 1861-1896," by Miss Martha Doan, lately of
Cornell University, was submitted to the Committee,
through Prof. L. M. Dennis, and after critical ex-
amination it has been unanimously recommended to
the Smithsonian Institution for publication.
Dr. Alfred Tuckerman is engaged upon new editions of
his "Indexes to the Literature of the Spectroscope,
and of Thermodynamics," which are to be continued
to the year 1900. He also reports progress on the
"Index to the Mineral Waters of the World," the
printing of which has been delayed by mechanical
difficulties.

Dr. Willem P. Jorissen, of Rotterdam, has undertaken to
bring down to date Prof. Albert R. Leeds' "Indexes
to Ozone and to Hydrogen Peroxide," first issued in
1880, and long since out of print.

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By MM. A. FROENKEL and J. FASAL.

THE authors have planned out a method for the estimation of tin which consists in precipitating this metal on aluminium, dissolving the two metals in hydrochloric

acid, and titrating the stannous chloride thus formed by

means of iodine or bichromate of potassium. But in this case it is indispensable to first of all neutralise nearly the whole of the hydrochloric acid. The method is as follows:

The solution of the salt of tin containing o'2 to 0'4 grms, of the metal is placed in a flask and a few drops of hydrochloric acid added, then from o'5 to 10 grm. of aluminium wire. This is gently heated, and the tin is precipitated after about half an hour. At the end of this time 10 cubic centimetres of concentrated hydrochloric acid are added, and the whole warmed until the complete solution of both the metals has taken place; this requires about filteen minutes. Bicarbonate of soda and Seignette's salt are added until the reaction is alkaline, It is then titrated with iodine.

This method, tried with a solution (A) containing 0'4317 grms. of tin, and on another solution (B) containing o'3988 grms of tin, gave the following results

I. 2.

Tin found

"

3.

A.

0'4105

0'4105 0'4038

B. 0'3866 0*3875

Monsieur Jules Garçon, chemical engineer (of 40 bis Rue Fabert, Paris), is about to publish an important contribution to the bibliography of technical che mistry, entitled Répertoire Universel de Biblio. To find the difference between the quantity of tin graphie des Industries Tinctoriales et des Industries actually existing in the solution and that found by Annexes." It is expected to form three large volumes. analysis, we dissolved 2.8302 grms. of pure tin in hydroIn the preparation of this immense undertaking the chloric acid, traversed by a current of carbonic acid. The author has examined 1800 works and III sets of volume of the solution was made up to 250 cubic centiperiodicals, the latter in 5000 volumes, besides 7000 metres, and 25 cubic centimetres of this solution were other articles and documents. Subscriptions (100 titrated in the manner already described. Another por. francs) may be sent to the publishers, Gauthier- tion of 25 cubic centimetres was taken and oxidised, then Villars et fils, Paris. M. Garçon is known as the precipitated either by sulphate of soda or by nitrate of author of the "Bibliographie de la Technologie Chi-ammonia; the oxide of tin was then weighed.

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The theoretical result should be 0.2830 grm. of metallic ON THE tin.

The method is therefore a sufficient approximation for commercial purposes, and more especially in comparative analyses.-Mitt. d. K. K. Tech. Gewerbe Museums in Wien, vol. vii., p. 227.

ON THE ESTIMATION OF LEAD AND
ANTIMONY IN TIN-FOIL.

By A. SEYDA.

ELECTROLYTIC SEPARATION OF
SILVER AND COPPER.

By N. REVAY,

THESE two metals may be separated one from the other by means of electrolysis, the silver salts requiring a slightly lower difference of potential than the correspond. ing salts of copper. The electrolysis can be effected either in acid solution or in a solution of double cyanides, A. Electrolytic Precipitation of Silver in Acid Solution.In the first experiment the electromotive force used was 13 to 1'4 volts. The silver was deposited in the spongy state; but this inconvenience can be avoided by heating the electrolyte to a temperature of 70° C.; the deposit of silver is even then not quite homogeneous, nevertheless it can be washed and weighed in this state. The electromotive force should not exceed 14 volt. To prevent the formation of peroxide, the solution should be kept strongly acid with nitric acid from the commencement of the reaction. The author has carried out experiments on solu. tions containing o'25 to 0'50 grm. of nitrate of silver, and practically equal quantities of crystallised sulphate of copper. Four separate analyses showed that the nitrate of silver used contained 63'43, 63°47, 63°45, and 63'35 per cent of silver. These results may be looked upon as being very accurate.

Estimation of the Lead.-Ten grms. of the foil are dis. solved in hydrochloric acid at 25 per cent, and a solution of nitric acid also at 25 per cent is added for the purpose of transforming the stannous chloride into stannic chloride, and to dissolve the antimony which remains unattacked by the hydrochloric acid. Drop by drop a solution of caustic soda at 25 per cent is added until the precipitate formed becomes re-dissolved. By maintaining the temperature at a point near boiling there is generally nothing but a slight opalescence left. We then add a small quantity of precipitated sulphur and treat with a current of sulphuretted hydrogen until the liquid takes a decidedly yellow tint. It is then allowed to stand for twenty-four hours, when the black precipitate is filtered off, washed with a solution of sulphide of sodium until a small portion of this clear liquid, acidulated with hydrochloric acid, gives a decidedly white deposit of sulphur. This washing requires a considerable time, but it is indispensable if we require the complete removal of the tin. The filter containing the moist precipitate is gently heated with nitric acid at 25 per cent, the solution is filtered, and the exhaustion with nitric acid repeated until a small portion of the filtered liquid no longer gives a black pre-berg the precipitation of the silver commences at 17 to cipitate with sulphurretted hydrogen.

The nitric solution containing all the lead is evaporated down with 20 cubic centimetres of sulphuric acid. The sulphate of lead is filtered and weighed in the usual

manner.

B. Electrolytic Precipitation in a Cyanide Solution.The separation based on this method was first suggested by Smith and Frankel. It was also experimented upon by Heydenrich and Frendenberg. In this case it is much more difficult to get a determined and constant electromotive force, as the difference of potential between the silver electrode and the solution varies considerably with the concentration of the silver salt and the proportion of cyanide of potassium in solution. According to Frenden

18 volts, while the copper is not deposited with an electromotive force lower than 2'3 to 2.4 volts; according to the present author, these last figures are a little too high. Experiments were made with an electromotive force of 16 to 18 volts at a temperature between 45° and 60°; the results obtained were very satisfactory. For six determinations made on electrolytes containing from 0'23 to 163 grms. of nitrate of silver he obtained 63.37 to 63'45 per cent of silver present in the salt used.

This method is preferable to the first one, inasmuch as it gives a more coherent metallic deposit. It gives better results still when the proportion of silver is high as compared with that of the copper present. On the other hand it is much less exact than the other method-to such an extent in fact, that if the copper is present in great excess it is precipitated the first.-Zeitschrift fur Elecktrochemie, vol. iv., p. 313, 1898.

Estimation of the Antimony.-Five grms. of the tin foil are thrown, a little at a time, into a mixture of 100 cubic centimetres of concentrated nitric acid and 25 cubic centimetres of water. The metastannic acid is treated with nitric acid at 25 per cent in a porcelain crucible and the mixture evaporated to dryness. The residue is dried on the water-bath. It is essential that the temperature of desiccation should not exceed 100° C., for the anhydrides of the oxides of tin and antimony do not appear to combine with soda. The still warm powder is thrown a little at a time into 60 grms. of caustic soda in a state of fusion. The melted mass is cooled to about 100°, broken up, and dissolved in 700 cubic centimetres of water. The cloudy liquid is cooled, and one-third of its volume of alcohol at 95 per cent is added, and the whole left for twenty-four THE ACTION OF SULPHUR UPON METALLIC hours. The precipitate is filtered by decantation, and the last portions washed on to a filter by means of a mixture of part of water to 2 parts of alcohol. Instead of washing the precipitate with dilute alcohol, an operation which always removes a small portion of the antimony, it is better to repeat the fusion with caustic soda a second time. The precipitate is dried at 100° and separated from the filter. The latter is cut up into strips and thrown into 10 grms. of melted caustic soda containing a small quantity of nitrate of soda. When the paper is entirely consumed we add the precipitate and proceed as before,

SODIUM.

By JAMES LOCKE and ALFRED AUSTELL.

AMONG the various investigations which have been pub. lished regarding the action of sulphur upon metallic sodium but one is of recent date. Rosenfeld (Ber. d. Chem. Ges., vol. xxiv., 1658), in a short article relating to the reactions of sodium, confirms the observations of Davy, Gay-Lussac, and Thenard, that the two combine with nearly explosive force, even at the ordinary tempera

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