illustrate the method and the degree of accuracy obtainable.

In conclusion, the Charlottenburg certificate costs only a few shillings; by its means reductions are made with the greatest ease, and, if the bore of the thermometer is a good one, the reductions are correct to o'o1°.

PROCEEDINGS OF SOCIETIES.

CHEMICAL SOCIETY. Ordinary Meeting, June 16th, 1898. Professor DEWAR, F.R.S., President, in the Chair. CERTIFICATES were read for the first time in favour of Messrs. Edward Gardner, 27, Thurlow Road, Hampstead, N.W.; Henry J. S. Sand, 2, Cantlowes Road, Camden Square, N.W.

A ballot for the election of Fellows was held, and the following were subsequently declared duly elected :

Harry Brearley; Arthur William Cowburn; Charles W. Tisdale Davies; Edwin Dowzard; A. Grant Russell Foulerton; Oswald Hamilton; A. Stanley Hemmy, B.A., M.Sc.; Robert Findlay Hislop; George Arthur Jarvis; Harry Lancelot Lee; William Lewins, B.Sc.; George Herbert Martin, B.A.; Charles James Meads; Leonard Myddleton Nash; Alex. MacGillivray Neilson; Edward John Russell, B.Sc.; Matthew Joseph Sheridan; Sigmund Stein, Ph.D.; Oscar Julian Steinhart, Ph.D.; Samuel Auchmuty Tucker, Ph.B.; Henry Trench Waller; Frank Edwin Weston; Edmund Thomas Whitaker, B.Sc.; William Ernest Wild, B.Sc.; William Williamson; Ernest Witham; Charles Arthur Wrench.

Of the following papers those marked were read:*86. "Preparation of a Standard Acid Solution by Direct Absorption of Hydrogen Chloride." By G. T. MOODY.

A very rapid and accurate method of preparing a standard acid solution consists in absorbing hydrogen chloride in water, determining the resulting increase in weight, and subsequently diluting to a suitable bulk. The absorption is conveniently carried out in a conical glass flask, having a capacity of about 80 c.c., and closed by a glass stopper. Through the stopper pass two tubes, one of which reaches nearly to the bottom of the flask and serves for delivery of the gas. From 2 to 4 grms. of the gas may be absorbed in 40 c.c. of water in three minutes, and if the necessary apparatus for generating hydrogen chloride is kept fitted, a standard acid solution can be prepared in less than fifteen minutes.

chlorofenchenephosphonic

acid, C10H14Cl PO(OH)2 (Trans., 1897, Ixxi., 1156), and describe the halogen derivatives of fenchone produced during its formation. The first action of phosphorus pentachloride on fenchene results in the replacement of the oxygen atom by chlorine, and production of two isomeric liquid substances, termed a- and B-chlorofenchene hydrochloride. These two isomerides cannot be separated by fractional distillation, but distil together at 105-110° under 16 m.m. pressure. The a-isomeride is, however, very much the less stable of the two, and loses hydrogen chloride very readily, even when distilled with steam, producing chlorofenchene. The B-isomeride is much more stable towards reagents, and does not lose hydrogen chloride by boiling with aniline; this elimination can be effected, however, by prolonged heating with zinc dust and glacial acetic acid, and chlorofenchene is obtained. Unlike the chlorocamphene hydrochlorides, B-chlorofenchene hydrochloride is completely decomposed by warming with strong sulphuric acid, and yields no substance analogous to camphenol.

Chlorofenchene, CroH15Cl, is a crystalline substance very like chlorocamphene in appearance. It boils at 80-83° under 16 m.m., and at 190-192° under the ordinary pressure. It is very soluble in alcohol, ether, benzene, light petroleum, chloroform, and carbon disulphide, the vapour of the last being sufficient to liquefy it. It has a specific rotatory power of [a] D = +35'92°. Chlorofenchene slowly reacts with phosphorus pentachloride, and chlorofenchene phosphonic acid is formed on treating the product with water.

When sodium chlorofenchenephosphonate is treated with bromine water, it is decomposed quantitatively into sodium phosphate and chlorobromofenchene, C10H14CIBг; this is a colourless oil which boils at 113-114° under 11 m.m., but decomposes on boiling under atmospheric pressure. It has a specific gravity of 1.38039 at 16°, and a specific rotatory power of [a]D -8.42°. The halogen atoms cannot be eliminated by heating with aniline, with zinc dust and glacial acetic acid, or with sodium in methylic alcohol solution.

=

tion of Fenchone." By JOHN Addyman Gardner and *88. "Researches on the Terpenes. IV. On the Oxida.

GEORGE BERTRAM COCKBURN.

Fenchone is much more stable towards oxidising agents than camphor, but when oxidation does take place a much more complete breaking down of the molecule occurs. The authors have oxidised fenchone by prolonged heating on the water-bath with concentrated nitric acid (sp. gr. 14). The action was very slow, and after heating for a week, they found that only about 50 per cent of the ketone had been attacked. carballylic acid, dimethylmalonic acid, isobutyric acid, Isocamphoronic acid, dimethyltri. acetic acid, and nitrofenchone were isolated from the product of oxidation.

The isocamphoronic acid crystallised from ether and ethylic acetate in tabular plates melting at 163-164°, and is identical with the isocamphoronic acid obtained by Tiemann from campholenic acid. The yield was

8

CHEMICAL NEWS, July 1, 1898.

The dimethyltricarballylic acid melted at 155o, and on treatment with acetic chloride gave an anhydride melting at 139-141°. The triethylic salt was a colourless liquid and boiled at 172-174° under 19 m.m. pressure. The lead salt, (C8H906)2Pb3, was an insoluble powder. The yield of this acid was 30 per cent, and of dimethylmalonic acid 4 per cent of the fenchone oxidised.

Nitrofenchone is a colourless oil which distils at 146151° under 14 m.m. pressure, and on reduction with stannous chloride is converted into an amine.

The authors are of opinion that if Bredt's formula be accepted for camphor, these results, taken together with the production of camphopyric acid from fenchene without the intermediate formation of camphoic acid, and from camphene, are sufficient to establish the formulaCH-CHMe

CH2-CH-CMe

CH2

Me2

CH2 CH -CO

it appears that only one (the a') of the two possible forms of nitrocamphor is produced under all ordinary conditions, since the various substances described as isomeric nitrocamphors have been found by the author to have the same properties when sufficiently purified.

The product obtained by heating nitrocamphor (Proc., 1897, xiii., 169) has the formula C20H28N2O5, and is identical with a substance already described by Cazeneuve as nitrosocamphor (Bull. Soc. Chim., 1888, iii., I., 558); it appears to be an anhydride formed by the removal of the elements of a molecule of water from two molecules

of nitrocamphor, or rather of an isodynamic form of the latter which may be termed pseudonitrocamphor. This view finds support in the fact that the anhydride, like the salts formed from nitrocamphor, is strongly dextrorotatory, whereas nitrocamphor is lævorotatory; and that when heated or acted upon by alcoholic potash, it breaks up into camphorquinone and nitrous oxide, undergoing a change analogous to that which Nef has shown to take place on acidifying a solution of sodium v-nitroethane (Annalen, 1894, cclxxx., 263).

If pseudonitrocamphor be represented by a formula corresponding to that which Hantzsch and Schultze have assigned to pseudophenylnitromethane, rather than by an isonitro-formula such as Nef has proposed, it is obvious that the conversion of nitrocamphor into the isodynamic form would not affect the asymmetry of the carbon atom to which the nitro-group is attached :

N.OH

changes corresponds to the formation of from 5 to 10 per cent of the pseudo-form in solution.

It has not been found possible to isolate pseudonitrocamphor as yet. In the case of wa'-bromonitrocamphor, however, three different crystalline forms are known. The author is of opinion that the orthorhombic modification melting at 142°, which has a specific rotatory power changing from +189° to 40° in a 3·33 per cent benzene solution, is the pseudo-form, and that the tetragonal form melting at 186°, which has a specific rotatory power changing from -50° to -40°, is the pure normal ma'bromonitrocamphor. The third microcrystalline modification, melting at 126°, appears to be composed of the two isodynamic forms in the ratio of one part of the normal to about five of the pseudo-compound. Equilibrium is attained in solution by all the three modifications at a point corresponding to the presence of only about 4 per cent of the pseudo-compound; the fact that this form is nevertheless the one most readily obtained on crystallisation is not difficult to account for as it is much less soluble than the normal compound.

The author considers that important evidence of the independent existence of pseudonitrocamphor is afforded by the fact that solutions of nitrocamphor exhibit the phenomenon of multirotation hitherto observed only in the case of carbohydrates. This is true of wa'-bromonitrocamphor, in which the group -CH(NO2) CO- is also present, but not of a'a-nitrochlorocamphor, a'a-nitrobromocamphor, nor of the anhydride or salts obtained from nitrocamphor, from all of which the hydrogen atom contiguous to the nitro-group has been eliminated.

The camphornitrophenol which Cazeneuve obtained by the action of concentrated muriatic acid on nitrocamphor obviously represents a third form of isomerism, as it behaves as a saturated compound and shows phenolic Its behaviour is properties. not explained by the formula,

The

C⚫NO2 C8H14 || C.OH

proposed by Cazeneuve, since this represents it as being merely the enolic form of nitrocamphor. A change similar to that produced by hydrogen chloride occurs when benzoyl chloride acts on an alkaline solution of nitrocamphor, has suggested that the formation of camphornitrophenol the product being camphornitrophenol benzoate. Cazeneuve is due to the addition and subsequent loss of a molecular zoyl chloride acts in a similar way by forming an additive proportion of hydrogen chloride; it is possible that bencompound from which hydrogen chloride is subsequently removed. The author is engaged in studying camphornitrophenol as well as its isomerides with a view of determining their inter-relationships.

SPIVEY, M.A., and T. H. EASTERFIELD, M.A., Ph.D. *90. Cannabinol." By T. B. WOOD, M.A., W. T. N.

duced by the authors in favour of the homogeneity of Notwithstanding the experimental evidence already adcannabinol (Trans., 1896, lxix., 539; Proc., 1898, xiv., 66), further investigation has shown that the substance is a

mixture.

The crystalline acetyl derivative to which the formula C15H1802 was assigned (Proc., loc. cit.) is found by molecular weight determinations to possess the formula C23H2803, which has the same percentage composition. This conclusion is supported by the determination of the acetyl and by the examination of the other product of weight required for the formula C21H2602. Most of the hydrolysis, which has the composition and molecular samples of cannabinol examined have yielded about 20 per cent of the crystalline acetyl compound, together with an oily acetyl derivative containing a lower percentage of carbon.

The compound C21H2602 boils at 280-290° under 80 m.m. pressure. When dissolved in glacial acetic acid and treated in the cold with fuming nitric acid, it yields a bright yellow crystalline nitro-derivative, C2H23N308, which is more conveniently obtained by the action of nitric acid on cannabinol under similar conditions, the yield amounting to 20 per cent of the cannabinol used. This nitro-derivative melts at 160° with decomposition, has acid properties, and gives characteristic ammonium, potassium, and silver salts which are sparingly soluble in water, but dissolve easily in alcohol, and have the general formula C21H22N3O8M. The sodium salt is comparatively soluble and crystallises with four molecular proportions of

CHEMICAL NEWL July 1, 1898. water. On reduction, the nitro-compound yields a corresponding base. Hot fuming nitric acid oxidises the nitro-compound to nitrocannabinolactone (oxycannabin), a mixture of acids being produced at the same time. Amidocannabinolactone, CHINH2O2 (Proc., loc. cit.), has been diazotised and converted into a crystalline iodolactone, CH11102, which melts at 137.5° and can be sublimed. On removal of iodine from this compound by the action of sodium amalgam an oily lactone is

obtained.

*91. "An Improved Form of Gas-analysis Apparatus." By WILLIAM A. BONE.

The author has devised an improved form of gasanalysis apparatus, suitable for all purposes where considerable accuracy in estimating small quantities of gases is required.

The apparatus consists essentially of—(1) A measuring vessel, A, made in one piece with a barometer tube, B. Both A and B are 700 m.m. long, and have the same internal and external diameters, viz., 15 and 17 m.m. respectively. B is very accurately graduated into millimetres. A and B are enclosed in a rectangular waterjacket, through which a stream of water at a constant temperature can be made to flow, and are connected by means of special steel joints and a steel tap to a movable mercury reservoir. (2) A laboratory vessel standing in a mahogany trough over mercury, into which the gases can be sent for absorption purposes. (3) An explosion vessel, similar to but rather larger than that of the Dittmar appa. ratus, in which all explosions are carried out.

The measuring vessel is provided with a three-way glass tap having two parallel capillary branches, one of which goes to the laboratory vessel, the other to the explosion vessel; the junctions are rendered vacuum tight by a device of steel faces and a clamp similar to that introduced by Regnault.

The moist gases are measured by bringing them to a certain constant volume in A, and then deducing their tension in terms of millimetres of mercury from the reading on the barometer, B. Since the gases in A are moist, and the "vacuum" in B is always kept saturated with water vapour, it is obvious that, provided the temperature of the water surrounding A and B remain constant throughout an analysis, none of the usual corrections for temperature, tension of water vapour, &c., need be applied to the analytical figures, as differences in readings on the barometer, under these conditions, correspond to differences in volume in the gases measured.

DISCUSSION.

Prof. MCLEOD thought that too much credit was ascribed to him for the gas-analysis apparatus, which was only a modification and simplification of that devised by Sir Edward Frankland. He had done away with the centre filling tube, so that a narrower glass cylinder which could be closed by an indiarubber plug was sufficient, thus avoiding complicated metal work; he had also lengthened the barometer, and thought that the author diminished the accuracy of his apparatus by making the barometer and measuring tube of the same length. All the stopcocks were made of glass, which seemed preferable to steel, as any leakage could be more easily detected and remedied. One small part of the apparatus he did claim, and that was the suspended globular mercury reservoir, and he was gratified to see that this simple device was in use in very many forms of apparatus in which mercury is employed.

Mr. G. N. HUNTLY said that he had been working for some time with a slightly modified form of the Frankland apparatus, in which the black glass points of Joly were used instead of lines etched round the tube. The accuracy of this method of reading is so great that a tube of I inch diameter can be used without loss of precision. The author's experience with the Dittmar-Lennox pipette did not agree with his own, as experiments made with a view of testing these pipettes showed that 5 c.c. of gas,

9

measured initially at atmospheric pressure, could be transferred backwards and forwards repeatedly without the readings on the barometer tube differing by more than O'I m.m., an accuracy of I in 7000. With careless working, transference tended, not to a loss of gas as the author suggested, but to a gain, minute, air bubbles being introduced apparently from the fingers.

*92. "Preliminary Note on the Action of Light on Acetylene." BY WILLIAM A. BONE and JOHN WILSON. Some time ago the authors noticed that acetylene undergoes a well-marked change on exposure to bright sunlight. Tubes of about 100 c.c. capacity, drawn out at each end and terminated by capillary glass taps, were filled at atmospheric pressure with pure lacetylene prepared from copper acetylide, and dried by passing through a concentrated solution of potassium hydroxide. Some of these tubes were exposed on the roof of the laboratory throughout June and July of last year, when the weather was particularly fine. After two or three days' exposure, a faint brown deposit was observable on the inside of the bulbs. This gradually increased in extent and thickness until, at the end of a fortnight, the tubes were entirely covered with a dark brown greasy deposit. The change was evidently due to the action of sunlight, for if a portion of the tube were screened from the light no deposit was formed over the area so protected, and, further, after the tube had become coated with the opaque deposit no further action was noticeable, even after prolonged exposure. Acetylene was decomposed to a less extent when exposed in tubes during August and September, 1897, than during the previous two months. The decomposition is independent of the presence of air, because acetylene mixed with its own volume of oxygen or nitrogen was exposed to sunlight for a very long period without any appreciable change occurring.

A slight contraction in volume was observed when tubes exposed during last summer were opened over mercury. A measured quantity of the gas sent into a Hempel pipette containing a freshly prepared ammoniacal solution of cuprous chloride was quickly reduced to about 2 per cent of its original volume. The residual gas, after treatment with dilute sulphuric acid, appeared to contain a fairly dense hydrocarbon absorbed by fuming sulphuric acid, mixed possibly with a small quantity of hydrogen; no saturated hydrocarbon could be detected.

The solid deposit on the side of the tube was removed by treatment with fuming nitric acid, in which it does not dissolve to any appreciable extent. On removal of the acid by filtration, irregular yellow plates remained. The derivatives of benzene and naphthalene, but without acid filtrate was carefully tested for the presence of nitro

success.

benzene, and could be heated at 270° without melting or The yellow plates were insoluble in hot undergoing any change; they apparently consisted of a very dense hydrocarbon or hydrocarbons.

of acetylene, and hope eventually to determine the nature The authors are working this summer on larger volumes of the products obtained.

(To be continued).

PHYSICAL SOCIETY. Ordinary Meeting, June 24th, 1898.

Mr. WALTER BAILY in the Chair.

PROF. CARUS-WILSON exhibited an apparatus to illustrate the action of two electric-motors coupled in such a way as to admit of their rotating at different speeds. The two shafts are placed in line, and each is fitted with a bevelwheel gearing into an intermediate wheel. The axis of the intermediate wheel is at right angles to the line of the motor-shafts, and is free to rotate in a plane at rightangles to that line. The motors can be made to rotate

CHEMICAL NEWS,

July 1, 1898.

II

CORRESPONDENCE.

THE NEW GASES.

To the Editor of the Chemical News. SIR,-If Mr. Droop Richmond is the gentleman who, six years ago, wrote an elaborate paper to announce the discovery of a new element-of which nothing has since been heard, he is certainly a high authority upon the new gases. But he has evidently not cured himself of the precipitancy of judgment he then displayed, otherwise he would not have committed himself to the groundless and utterly erroneous assumption that I had to wait for Rayleigh and Ramsay to learn about the classical experiment of Cavendish. I was acquainted with that before I left school.

It is satisfactory to find that this eminent authority does not upset or even seriously assail a single proposition advanced in the letter you did me the honour to publish. On the contrary, he concedes my main contention when he says that I "might wait a year or so, and give Professor Ramsay time to do the work he has mapped out for him. self." The whole point is, that he has not taken the time everyone was willing to give him, but has hastily announced results-some of which are already proved to be erroneous, and none of which have yet been made out with scientific precision. The Cavendish residue was declared to be argon; and argon, pace Mr. Richmond, was loudly and even angrily declared to be an element, notwithstanding the warnings of the judicious. residue is now declared to contain argon, krypton, neon, and metargon; but not one of the four has been any better made out than the famous Masrium that Mr. Richmond wrote of. There is nothing to show for them except spectral lines, some of which were noted years ago by Liveing and Dewar, and some by Moissan and Deslandres. Not one of the four thought of claiming the discovery of a new element, though all suspected its existence. Their procedure contrasts sharply with that of Professor Ramsay.

That

I am happy to be able to agree with Mr. Richmond on one point-that the real discoverer of argon is Lord Rayleigh. What he felt "as a physicist "I do not know, but I shrewdly suspect that he felt as a man more than than he has told the public. Whatever he felt as a physicist, he did not "associate himself with a chemist." It was the other way about; the chemist compelled Lord Rayleigh to accept a wholly unsought association with him. Lord Rayleigh, as he has told us himself, was directed by Professor Dewar to the experiment of Cavendish as the solution of his difficulty about the discrepant weights of nitrogen from different sources. But for that fortunate circumstance he would have lost more than the half share of the fruit of his admirably solid and accurate work.

For the direction subsequently given to the work, Lord Rayleigh-as a physicist, and not a chemist-is responsible only indirectly and under compulsion.

I have the more pleasure in thus fully correcting my "inadvertence," which I regret, Sir, to see somewhat illogically charged against you, because Professor Ramsay, with his usual scrupulous fairness, has hastened to point out that both Lord Rayleigh and Mr. Travers have a large share in what has been done.-I am, &c., SUUM CUIQUE.

London, June 27, 1898.

SOURCES.

NOTE.-All degrees oftemperature are Centigrade unless otherwise expressed.

Comptes Rendus Hebdomadaires des Séances, de l'Académie des Sciences. Vol. cxxvi., No. 18, May 2, 1898. Researches on the State in which Silicon and Chromium occur in Siderurgical Products.-A. Carnot and M. Goutal.-The authors have already found that silicon and chromium combine with iron, manganese, and carbon; but the complexity of these compounds has necessitated further researches, which are here described. They also observed the existence of other compounds of silicon besides the silicide of iron, and these are now given with greater accuracy. Amongst other things, they conclude, from a number of experiments, that these siderurgic products contain two combinations of iron and silicon corresponding to the formulæ SiFe and SiFe2; further, when sufficiently rich in manganese they may contain a silicide of the form SiMn3. In the case of ferrochromes, there should be three molecules of carbide of chromium with one molecule of carbide of iron. Dimethylamido-diethylamido-orthobenzoyl and Orthobenzylbenzoic acids, and some of their Derivatives.-A. Haller and A. Guyot.-The authors state that the memoir recently published by M. Limpricht (Liebig's Annalen, ccc., p. 228) contains results already published by them (Comptes Rendus, cix.; Ber. der Deut. Chem. Ges., xxviii.; Bull. Soc. Chim., [3], vols. xv. and xvii., &c.), as well as other results since obtained. The paper is partly controversial, but a number of new compounds are described.

On the Radiations emitted by Thorium and its Compounds.-G. C. Schmidt.-The author points out that the paper recently read at the Academy by Mdlle. Curie on this subject was anticipated by his communication to the Physical Society of Berlin on Feb. 4, 1898. He now gives the values he obtained with citrate of uranium, nitrate of uranium, oxide of thorium, sulphate of thorium, and nitrate of thorium.

On Iodide of Glucinum.-P. Lebeau.-Already inserted in full.

New Reaction of Tertiary Alcohols and their Ethers.-G. Denigès.-To apply the method already described by the author (Comptes Rendus, cxxvi., p. 1145) to the tertiary alcohols, it is necessary to heat a few c.c. of the alcohol in question with a few c.c. of the mercuric reagent used for the ethenic carbides, viz., HgO, 50 grms.; H2SO4, 200 grms.; and water, 1000 grms. A more or less yellow precipitate is at once formed; it sometimes has a reddish tinge, varying according to the alcohol used. The present paper is confined principally to the best known ones, and those easiest to obtain; that is, trimethyl carbinol, and ethyl dimethyl carbinol, so as to show the identity of the derivatives obtained with these alcohols and the corresponding ethenic carbides. The ethers of the tertiary alcohols also react with mercuric sulphate when gently warmed, furnishing yellow mercuric compounds. The action is very distinct with the tertiary nitrite of amyl used in medicine.

Action of Alkalis on Ouabaine.-M. Arnaud.-The

alkalis do not hydrolyse ouabaine even when boiled, but give rise to a dehydrated derivative formed without splitting up and without the production of reducing sugar. The body formed is a monobasic acid, which decomposes the alkaline carbonates or the alkaline earths, and reddens blue litmus. Ouabaic acid, as it is called, is a yellowish white amorphous body, resembling gum; it is very soluble in water, slightly so in alcohol, but insoluble in ether. It melts at about 235°, decomposing and giving off a gas smelling of caramel. Its formula, deduced from the ana.