21.84

58.98

34'95

12'95

7. 37'05 The order of solubility of Nos. 5 and 6 is here not the same for the two reagents, whilst No. 7 shows an unexpected inferiority. Careful experiments with mineral phosphates precipitated in the laboratory, proved that this result was due, not to the origin of No. 7, but to its mode of preparation: hence, the manufacturer of precipitated phosphates can always check the value of his methods by ascertaining the solubility of the products in oxalate of ammonia and in acetic acid. Powdered bones freed from gelatine, animal charcoal, and bone-ash were next examined. Their solubility was likewise found to diminish in proportion to the elevation and duration of the temperature to which they had been submitted.

13.

14.

15.

Name of Sample.

Percentage of

Phosphoric Acid in the sample.

Phosphoric Acid Dissolved for

100 parts of

Phosphate present.

Phosphoric Acid Dissolved for 100 parts of

Phosphoric Acid present.

ACETIC ACID.

powder pale yellow

16. Agatised phosphate; hard; 34:50

present.

17. Concrete; soft; powder deep

yellow

18. Similar sample from another

mine

NEWS

24. Phosphorite (Nassau)

present.

present.

22. Phosphate of Ain (Bellegarde) 16.51

23. Rhone Valley (fossils of the 23.00 Gault)

3174

9'46

6'08

25. Coprolite (Cambridge).

Navassa phosphate

27. Nivernais phosphate

28. Apatite (Caceres, Spain) 29. Apatite (Canada)

trace

The phosphates of Bellegarde, of the Rhone, and Nassau, approach the type of the Ardennes nodules by their solubility in oxalate of ammonia and their insolubility in acetic acid. That of Navassa resembles the phosphates of the Garonne. Cambridge coprolite and Nivernais phosphate belong to the type of the bone products.

Oxalate of ammonia enables us to class phosphates in a series closely approximating to that of their relative assimilability. The action of acetic acid, less powerful and general, enables us to seize some distinctions which the oxalate fails to indicate.

It is evident that the agricultural value of phosphates for use in an undissolved state depends more on their solubility, and consequent assimilability, than on their percentage of phosphoric acid.

is rapidly repeated through the agency of the free carbonic acid, until the decomposition of the sulphate is complete. Among many experimental results, I will give the following;-Five grms. of the sulphate of potash, dissolved in carbonic acid water, to which was added 7 grms. of precipitated carbonate of baryta, after four and a half hours' shaking (being attached to a suitable piece of machinery), on testing showed not a trace of sulphuric acid, care being taken to wipe the neck of the bottle near the end of the stopper before pouring out the liquid.

Other experiments, varying in proportion, gave similar results. I tried to substitute the natural for the precipitated carbonate of baryta, but with very unsatisfactory results.

Directions for the Conversion of the Alkaline Sulphates into Tartrates, Oxalates, &c.-As the tartrate and oxalates of baryta are but very slightly soluble in water, we cannot form the alkaline salts of these acids by direct double

ALKALIES INTO THE CARBONATES, TARTRATES, &c., IN THE MOIST WAY.

By J. LAWRENCE SMITH.

HAVING had occasion more than once to convert small quantities of the sulphates of the alkalies into carbonates, I have for several years employed a process that has been found both certain and convenient: in some recent investigations it has been used, and as it has never been described it may not be unimportant to explain the nature of the process and its results. The agent used to produce the conversion is carbonate of baryta, made by precipitation: where precise results are required the carbonate should be prepared by carbonate of ammonia. The manner of producing the decomposition is as follows:Dissolve the sulphate of potash in water, using about 20 or 30 grms. of water to every gramme of the sulphate, and saturate the solution with carbonic acid by passing a current of carbonic acid into it; or, what is better, dissolve in the beginning the sulphate in water already saturated with carbonic acid; now add to this solution precipitated carbonate of baryta, in the proportion of about 1 of the carbonate to I part of the sulphate. It is always best, in adding the carbonate, to rub it up in a mortar with a little water, so as to form a thick cream, for by so doing it mixes well in the solution.

This operation is performed in a bottle that can be well corked with a cork or gum stopper; now agitate the bottle frequently, or, what is still better, attach it to a piece of machinery that will agitate the bottle. Many laboratories have such, and it is a very useful one in many experiments. In a longer or shorter space of time, the decomposition will be completed, pour the solution into a capsule and heat to the boiling-point; the solution will then contain only carbonate of potash.

The reaction is readily understood. The carbonic acid in the water dissolves a little carbonate of baryta, which is immediately re-precipitated in the form of sulphate, carrying down a portion of the sulphuric acid of the soluble sulphate, and replacing the same with carbonic acid; this

tartrate, &c., of baryta, as in forming the alkaline chlorides from the sulphates; but it is easily done by the following indirect process:

Add to the alkaline sulphates in solution, in a porcelain capsule, carbonate of baryta rubbed up into a thick cream, in the proportion of about 5 of the sulphate to 7 of the carbonate of baryta; heat the mass, and add, little by little, the requisite quantity of tartaric or oxalic acid. Solution of the baryta and precipitation of the sulphuric acid take place rapidly, and the decomposition is soon completed."

I have used this process of forming the bitartrates in the process of separating potassium, rubidium, and cæsium, that were in the form of sulphates.

The Carbonates of the Alkalies can also be formed by first forming these organic salts from the sulphates, evaporating the solution to dryness, and burning the residue; in fact, I frequently find it more convenient to convert the sulphates of the alkalies into the carbonates by this last instead of the first process. And, finally, I would remark that, where magnesia is present with the sulphates, this is also separated from the alkalies.— American Chemist.

PROCEEDINGS OF SOCIETIES.

CHEMICAL SOCIETY.
Thursday, June 19, 1873.

Dr. ODLING, F.R.S., President, in the Chair.

WHEN the minutes of the preceding meeting had been confirmed, and the donations made to the Society announced, the name of John Douglas, Esq., was read for the first time. For the third time, those of Messrs. Walter Odling, Archibald Kitchin, James Emerson Reynolds, and Robert Wild, who were then balloted for and duly elected. The first paper, by J. H. GLADSTONE, F.R.S., and

A. TRIBE, entitled "Researches on the Action of the CopperZinc Couple on Organic Bodies" (III. "On Normal and Isopropyl Iodides "), was read by Dr. Gladstone. The action of isopropyl iodide on the dry couple at 50° commences after a few minutes, gases are evolved, and the liquid residue in the retort, when strongly heated over a flame, evolves more gas, and at the same time a small quantity of a liquid distils over, apparently containing zinc-isopropyl. As it had been found that more zincamyl was produced from the corresponding amyl compound when the contents of the flask were distilled in vacuo, the same method was adopted with the isopropyl iodide; and in this case, also, the product obtained was considerably larger. Careful examination and analyses of the gases evolved showed that they consist of nearly equal volumes of propylene, C3H6, and hydride of propyl, C3H8. The two reactions, Zn+2C3H,I=ZnI2+C3H6+C3H8 and 2Zn+2C3H,I=ZnI2+Zn(C3H7)2, go on simultaneously at 50°, and when heated to 130° most of the Zn(C3H7)2 splits up into Zn+C3H6+C3H8. As was to be expected, the action of the couple on the iodide in the presence of water or alcohol gave propyl-hydride, C3H8, the action being more rapid with the alcohol. Experiments similar to the above were also made with zinc-foil and granulated zinc, but in both cases the action was very much more sluggish, and required a higher temperature than when the couple was employed. In the investigations with the normal propyl-iodide it was found necessary to heat the iodide with the dry couple to 80° before any action took place; at 109° the action was much more rapid, and but little gas was evolved. On strongly heating the product in a current of carbonic anhydride, a large quantity of zinc-propyl passed over, which, on rectification, distilled almost entirely between 146° and 148°. When pure, it is a colourless mobile liquid, slightly denser than water, and boiling at about 146°; exposed to the air, it takes fire spontaneously and burns with a white flame. The action of the couple on the normal iodide in the presence of water or alcohol yields propyl-hydride, but the action is much less energetic than in the case of the isopropyl compound. These results entirely agree with the evidence already existing of the comparative instability of the isopropyl compounds. The authors conclude with some additional notes on the couple, describing the most advantageous way of preparing it.

The PRESIDENT, having thanked the authors for their valuable communication, enquired whether the copper took any part in the reaction, or whether alloys had been tried, to which Mr. Tribe replied that the copper had no direct action, and that brass had been tried by Dr. E. T. Thorpe, but was without effect.

The next paper, "On the Influence of Pressure on Fermentation" (Part II. "The Influence of Reduced Atmospheric Pressure on Alcoholic Fermentation "), was read by the author, Mr. HORACE T. BROWN, who, after referring to his former paper, proceeded to describe the methods employed, and the precautions necessary to ensure concordant results in ascertaining the amount of alcohol and carbonic anhydride produced by the fermentation of maltwort and solutions of cane sugar under diminished pressure. He prefers determining the carbonic anhydride by the loss of weight, or by absorption by potash and soda-lime, as being more accurate than the measurement of the gas evolved. A consideration of the tabulated results obtained in this way shows that diminished pressure retards the progress of the alcoholic fermentation in a remarkable way, although there does not seem to be any simple relation between them. It is certain, however, that under diminished pressure less sugar is decomposed than during an equal time at the ordinary pressure, and that the proportion of the carbonic acid to the alcohol produced is greater. This difference was not due to any injury of the yeast cells caused by the removal of the pressure, but appears rather to be an exemplification of Sorby's law, that pressure weakens or strengthens chemical affinity, according as it acts against or in favour

of the change of volume," since the author has proved that there is a decided contraction in volume during the alcoholic fermentation. The formation of acetic acid noticed in Part I. of this memoir the author finds to be derived directly from the sugar.

After the PRESIDENT had thanked the author in the name of the Society,

Mr. BEANES said he would like to hear from the author of the paper whether he had tried fermentation under pressure, because in July last he (Mr. Beanes), during some investigations on saccharine solutions, had occasion to place a sacccharine solution of 1050 sp. gr., while in a state of fermentation, under a pressure of 36 atmospheres for two days. He found, at the end of that time, on testing it, it marked 1030 sp. gr. ; while another portion of the same liquid, which had not been under pressure, marked o'996. He thought it peculiar that the same results, viz., a decrease of fermentation, as described by the author of the paper, should be obtained by a partial vacuum, while he (Mr. Beanes) had obtained the same result by an increase of pressure. A paper "On Cymene from Different Sources Optically Considered" was then read by the author, Dr. J. H. GLADSTONE, in which he communicated the results of his optical examination of the cymenes from various sources, recently described by Dr. C. R. A. Wright, which are practically the same for each, their specific refractive energy being o'55, and their mean refraction equivalent 751, the difference of the extremes not being greater than that usually observed between different specimens of the same hydrocarbon. This equivalent, calculated with the common refraction equivalents for carbon (5) and hydrogen (13), would give 68.2; thus all these specimens of cymene showed a higher equivalent characteristic of the great aromatic group. This is particularly interesting, as some of them were prepared from substances which do not exhibit this abnormal influence on light, affording additional evidence that the retarding power of the carbon in such bodies as these does not arise from any particular internal structure capable of being transmitted from one compound to another.

After the usual vote of thanks to the author, Dr. ARMSTRONG observed that Landolt had found that, although the refraction equivalent was too high in aromatic bodies when calculated from the empirical formula, yet if in the rational formula the ordinary value for carbon was taken for the substituted radicals, and a higher one for the C6 in the benzol nucleus, concordant results were obtained.

Dr. GLADSTONE replied that he believed he was the first to point out this, but at present, although it was true for certain compounds, more data were necessary to fix the value for the carbon in the nucleus.

Dr. C. R. A. WRIGHT said it was probable a correlation between this and other physical properties of bodies would be found, as, for instance, in the different amount of heat given out by isomeric hydrocarbons on combustion; although the results were at present incomplete, he had found this to be the case with those of the series CroH16.

A "Note on the Action of Bromine on Alizarin," by W. H. PERKIN, F.R.S., was then read by the author. Bromine does not act readily on dry alizarin; but, when the two substances are heated to about 170° with carbon disulphide, a brominated alizarin is produced, which, after crystallisation from glacial acetic acid, is obtained in tufts of orange-red coloured needles having the composition C14H-BIO4. It dissolves in caustic alkalies with a blue-violet colour, similar to that obtained with alizarin, and giving a similar absorption-spectrum. Bromalizarin dyes mordanted fabrics a redder violet with iron, and a browner red with alumina mordants, than is obtained with pure alizarin. Heated with acetic anhydride, it forms diaceto-bromalizarin, C14H5Br(C2H3O)204, a yellow crystalline substance.

After the usual vote of thanks, a memoir "On some Oxidation and Decomposition Products of Morphine Derivatives," by E. L. MAYER and C. R. A. WRIGHT,

D.Sc., was read by the latter. The authors state that, when apomorphine hydrochloride is heated with an excess of a solution of potassic hydrate, the precipitate at first produced is rapidly dissolved, and the solution acquires a dark colour, from absorption of oxygen. On acidifying it with hydrochloric acid and agitating with ether, a peculiar colouring matter is extracted; the ethereal solution, agitated with an alkaline solution, colours the latter grass-green, and on neutralising with hydrochloric acid indigo-blue flakes are precipitated, having the composition C40H34N2O7. Diapomorphine and deoxymorphine also yield this blue product when treated with potassic hydrate, but the "tetra" series and the monomorphine derivatives do not-the latter giving methylamine and pyridine, the "tetra" bodies methylamine only and no pyridine. A note to this paper, by Dr. Wright, gives the properties of some colouration products obtained as precipitates by the treatment of certain codeine and morphine derivatives with argentic nitrate and nitric acid. He mentions, as a remarkable fact, that the mother-liquors from which they had been deposited when distilled with caustic potash, yielded methylamine in the case of the morphine compounds, and none in the case of the codeine derivatives, although codeine is methyl-morphine.

Thanks having been returned to the authors for their paper, Mr. R. WARINGTON read his communication "On the Decomposition of Tricalcic Phosphate by Water." The author, after noticing that it had been observed long ago that the mono- and di-calcic phosphates are decomposed when boiled with water, drew attention to the fact that the tricalcic salt is likewise decomposed under similar circumstances. On boiling carefully-washed pure tricalcic phosphate with distilled water for two hours, the solution becomes distinctly acid, and on pouring off the water, and repeating the process ten or twelve times, a compound at last obtained which had the composition 3(Ca3P208) CaOH2O, corresponding to apatite, in which the fluoride or chloride of calcium is replaced by the hydrate. The author concluded his paper by some remarks on the solubility of tricalcic phosphate in cold

was

water.

The PRESIDENT then thanked the author for his paper, and for drawing their attention to the formation of this quasi-apatite.

Mr. WARINGTON, in reply to a question of Mr. J. NEWLANDS, said that the pure tricalcic phosphate was prepared from a solution of disodic phosphate, to which an equivalent of ammonia had been added by precipitating it with pure calcic chloride.

Dr. H. E. ARMSTRONG then read a paper entitled "Communications from the Laboratory of the London Institution" (No. XII. "On the Nature and some Derivatives of Coal-Tar Cresol," by H. E. Armstrong and C. L. Field. This investigation has for its object the comparison of the haloid and nitro derivatives of cresol and phenol; and for this purpose the authors converted the crude coaltar cresol, boiling between 190° and 205°, first into the sulphonic acids, and then into the corresponding potassic salts, of which they have succeeded in isolating two, viz., a sparingly soluble one, C,H,O(SO3K) +2 aq, and a very soluble salt, C,H,O(SO3K); the former of which yields a very difficultly soluble baric salt when precipitated with baric chloride, and is doubtless identical with Engelhardt and Latschinoff's paracresol-sulphonic acid. The motherliquors appear to contain a third salt, which has not yet been examined. Both these acids yield mononitro derivatives by the action of nitric acid, which are converted into dibromonitrocresols by treatment with bromine. When the crude cresol is acted on by dilute nitric acid, and the product distilled in a current of steam, crude nitrocresol passes over as a yellow oil, whilst a black residue is left in the retort. The oil readily yields a dinitrocresol melting at about 82°, and forming magnificent red potassium and sodium compounds; it is apparently identical with the dinitrocresol obtained by the action of nitrous acid on toluidine.

The eighth communication was "On a New Tellurium Mineral, with Notes on a Systematic Mineralogical Nomenclature," by J. B. HANNAY. Whilst examining a specimen of arsenical iron pyrites, the author discovered in it some metallic tellurium, and also a substance in scales resembling specular iron ore. The latter, on examination, was found to contain arsenic, tellurium, and sulphur, in the proportions corresponding nearly to the formula Te2As2S7. After a few remarks on the want of a systematic nomenclature in mineralogy, the author calls the new mineral "arsenotellurite," proposing to name minerals according to the principal constituents-thus, for example, limestone would be "calcite ;" and when there are many minerals having the same principal constituents, to add a distinguishing prefix-thus, agate would be called "concentric ferruginous silicite," and so on. A long list of minerals, with the proposed new names, is appended to the paper.

The following paper, a "Note on Relations among the Atomic Weights," by J. A. R. NEWLANDS, was then read by the author:-In the June number of the Journal of the Chemical Society is a paper by L. Meyer, "On the Systemisation of Organic Chemistry," in which reference is made to M. Mendelejeff as having shown that certain properties of the elements appear "as a regular periodical function of the atomic weight, if the elements are arranged in the natural system, or according to the numerical values of their atomic weights." Now, in a paper read before this Society on March 1st, 1866, I showed that, when "the weights, a simple relation existed between them, those elements were arranged in the order of their atomic belonging to the same group standing to each other in a relation similar to that between the extremes of one or the same statement in the CHEMICAL NEWS, vol. x., p. 94, more octaves in music." I had also previously published and on other occasions. As my paper was not printed in the Journal of the Chemical Society, and therefore a question of priority may arise, I have to request, as a simple matter of justice, the insertion of this brief note in the Society's Journal.

paper on this subject in 1866 had not been published by The PRESIDENT said the reason why Mr. Newlands's the Society was that they had made it a rule not to publish papers of a purely theoretical nature, since it was likely to lead to correspondence of a controversial character.

The PRESIDENT then adjourned the meeting till after the recess, congratulating the members on the flourishing state of the Society and the number and importance of the papers which had been read there during the session.

CORRESPONDENCE.

ACETAMIDE AND ETHYLATE OF SODIUM.

To the Editor of the Chemical News. SIR,It is evident that Mr. Wanklyn does not know what he is talking about when he makes such a communication acquainted with the substance of my paper know that, as that which I read in your last number, p. 302. Those when sodium alcohol and acetamide are heated together, less than 5 per cent of the ammonia obtainable from acetdepends upon how far moisture gains access to the amide is given off, and that the amount of ammonia materials. The conclusions I arrived at were that perfectly dry acetamide and dry sodium alcohol yield no compound. This was not apparent from your reporter's ammonia of any kind, neither do they produce a new notice; I therefore ask you to be so good as to publish

this. I am, &c.,

King's College, London, June 22, 1873.

W. N. HARTLEY.

Comptes Rendus Hebdomadaires des Séances de l'Academie des Sciences, June 2, 1873.

Action of the Chief Derivatives of Amylic Alcohol upon Polarised Light.-I. Pierre and Ě. Puchot.Amylic alcohol has an action upon polarised light resembling that of a solution of sugar of 14 per cent, but of an inverse direction. The authors found, in all the experiments to which they submitted the pure amylic alcohol of fermentation, no indication of the second amylic alcohol pointed out by Pasteur. The action of ordinary amylic alcohol upon polarised light is increased one-third by the addition of about 6 per cent of water. Amylic alcohol, reproduced from its ethers, or obtained as the residue of an incomplete oxidation, does not appear to have undergone any appreciable modification either in the direction or the intensity of its action upon polarised light. This is not the case with its ethers, nor with the compounds formed under the oxidising influence of a mixture of sulphuric acid and bichromate of potash, along with the necessary amount of water. The first of these oxidation products, amylic aldehyde, turns the plane of polarisation in an opposite direction; in the same, namely, as would be produced by crystallised sugar. With the pure aldehyde this deviation is equal to that which would be produced by a solution of crystallised sugar at I per cent. Its degree of purity has a great influence on the extent of deviation. A sample of crude aldehyde, saturated with water, gave a deviation three times greater than does the pure substance. The presence of the water was, however, found not to be the cause of this increased action, since a sample of pure aldehyde saturated with water exerted a rotatory power decidedly inferior to that of the anhydrous aldehyde. The second product of oxidation, valerianate of amyl, (isomeric with the aldehyde above mentioned) causes a deviation in the same direction-but seven times greater-equal to that of a solution of crystalline sugar of 6.6 per cent. The results obtained with the amylic compounds are represented in the subjoined table; the sign + being attached to the deviations similar in direction to crystalline sugar, and

to those in the inverse direction :

Detection and Determination of Sulphate of Lead in Commercial Chromates of Lead.-E. Duvillier.-The methods used to decide on the purity of a chromate of lead do not indicate whether sulphate of lead be present or absent. The author heats gently, in a flask of sufficient size, I part of the sample of chromate with 2 to 3 parts of nitric acid at 1'420° sp. gr., I to 2 parts of water, and of alcohol. The reaction is very strong, and must be moderated by reducing the heat. When the violent action has subsided, heat is still applied till all nitrous fumes have disappeared. In the flask will be found a violet liquid-a mixture of nitrate of lead and nitrate of chrome-and a white precipitate of nitrate of lead, along with which sulphate of the same metal may be present. Water is added and the whole boiled. If no sulphate is present the whole dissolves; but otherwise To determine its sulphate of lead remains insoluble. amount the whole is evaporated to dryness to expel nitric acid, and the products of the oxidation of alcohol, care being taken not to heat so strongly as to decompose the nitrate of chrome. On treating the residue with water the sulphate is left undissolved. This method is applicable

to all chromates.

Action of Nitric Acid upon Chromate of Lead.E. Duvillier.-In allowing nitric acid, diluted with 1 to 2 volumes of water, to act at the boiling-point upon pure chromate of lead the liquid took the colour of chromic acid, and preserved it on cooling, although the bulk of the chromate of lead remained unchanged. On concentration crystals of nitrate of lead were deposited. The mother-liquor evaporated to dryness yielded a solution of chromic acid nearly pure, but representing a very small part only of the chromic acid present in the quantity of chromate employed. The action of the nitric acid is, therefore, analogous to its behaviour with chromate of baryta. With the latter, however, the amount of water is immaterial, whilst if water be added to a solution of chromate of lead in nitric acid this salt is precipitated. On treating the chromate of lead with double its weight of nitric acid we obtain a solution of chromic acid containing only 2 per cent of lead oxide. Nitric acid, therefore, resolves chromate of lead into chromic acid and into nitrate of lead, which is precipitated at a boiling heat in presence of the excess of nitric acid employed.

On a Base Isomeric with Piperidine, and on the Nitro Derivatives of the Hydrocarbons of the Formula C2mH2m.-H. Gell.-Meyer and Stuber have lately prepared isomeric compounds of the nitrogenous ethers formed by wood-spirit, alcohol, and oil of potatoes. These new substances behave like nitro derivatives of hydrocarbons of the general formula C2mH2m+2. This discovery of these compounds tends to disprove the essential difference which had been assumed between these carbides and those of the aromatic series, CamH2m-6, the only group whose nitro derivatives were known. The author endeavoured to obtain analogous compounds of another family, still resulting from the substitution of an equivalent of hyponitric acid for one of hydrogen. He sought to prepare the nitro derivatives of the hydrocarbons C2mH2m. Having added to nitrethane the quantity of potassa dissolved in alcohol necessary for its transformation into potassic nitrethane, it was placed in contact with an equivalent of iodide of allyl. On adding water to the filtrate an oily liquid was obtained which could not be purified for analysis as it was decomposed on volatilisation. On treating it with hydrochloric acid and fragments of zinc the insoluble oil disappeared, and on distilling the residual liquor with an excess of potassa a colourless liquid was obtained which, on the addition of some fragments of potassa, gave an odour of piperidine. The new substance differs from that base in several important respects. It boils at 85°, and its isomer at 106°. It is soluble in water and alcohol, and combines energetically with acids. If poured upon bisulphide of carbon it gives rise to a brisk reaction, but the liquid does not crystallise