Of the following papers, those marked were read :

*290. "The Change in the Boiling points of the Trioxide and Tetroxide of Nitrogen on Drying." By HERBERT BRERETON BAKER and MURIEL BAKER.

As a result of a private communication from Prof. A.

found, on consulting their notebook containing the descrip-tion of the experiments on the vapour density of dried nitrogen trioxide (Trans., 1907, xci., 1862), two instances in which the liquid had failed to boil rapidly at 150. specimen of the liquid had fortunately been kept, which had been allowed to remain over phosphoric oxide for three

A

No. 8.

PROCEEDINGS OF SOCIETIES.

CHEMICAL SOCIETY.
Ordinary Meeting, November 21st, 1912.

Prof. PERCY F. FRANKLAND, LL.D., F.R.S., President, in the Chair.

THE PRESIDENT referred to the loss sustained by the Society, through death on November 9th, of Prof. John William Mallet, LL.D., F.R.S., of the University of Virginia, who was elected a Fellow on December 15th, 1857, and an Honorary and Foreign Member on March 2nd, 1911.

Certificates were read for the first time in favour of Messrs. Neil Kensington Adam, 21, Barton Road, Cambridge; Crellyn Colgrave Bissett, B.Sc., B. Met., 10, Claremont Place, Sheffield; Daniel James Davies, B.Sc., 177, Le Marchant Road, St. John's, Newfoundland; James Henry Edmondson, Newcroft, Urmston, Manchester; Ulick Richardson Evans, The Kier, The Common, Wimbledon; Alfred Leslie Howells, Bank Field, New Mill Road, Holmfirth; Peter Thomas Leitch, care of John Edgar, Esq., 176, West George Street, Glasgow; Thomas Joseph Nolan, M.Sc., 32, Newmarket, Dublin; Cornelius Theodore Pollard, B.Sc., 21, Wharncliffe Road, Broomhall Park, Sheffield; Siddons Siddons Wilson, 154, Burges Road, East Ham, E.; Bertrand Turner, B.Sc., 55, Golden Hillock Road, Birmingham.

Certificates have been authorised by the Council for presentation to ballot under By-law I. (3) in favour of Messrs. James Crawford Douglas, Christmas Island,

whole in liquid air, and two of these were placed in tubes containing nitrogen, dried by contact with phosphoric oxide. After six months' keeping the bulbs were broken, and the boiling point of the liquid at atmospheric pressure (757 mm.) was found to be 43°, instead of -2°, which is the boiling point of the ordinary liquid. On cooling the tube to +10°, green drops formed at once, showing that undissociated nitrogen trioxide was present. When a small quantity of nitrogen, dried by passing through a long column of phosphoric oxide, was admitted to the apparatus, the very small quantity of moisture which it contained produced vigorous dissociation, and the expansion blew out the stopper. It has also been found that dried nitrogen tetroxide could be kept at a temperature of +69° without boiling. The ordinary boiling point of this liquid is +22°. Further experiments on the boiling-points of dissociable substances are in progress.

By

*291. "The Tendency of Atomic Weights to Approximate to Integral and Semi-integral Values." By ERNEST FEILMANN. (Will be inserted in a subsequent issue). *292. "The Constituents of Taraxacum Root." FREDERICK BELDING POWER and HENRY BROWNING, jun. The material employed for this investigation consisted of the air-dried fresh roots of taraxacum (Taraxacum officinale, Wiggers). collected in the autumn from plants grown in England.

The root was found to contain an enzyme which slowly hydrolysed amygdalin, and an alcoholic extract of the root, when distilled with steam, yielded a small amount of a yellow essential oil.

From the portion of the alcoholic extract which was soluble in water the following compounds were isolated :(i.) p-Hydroxyphenylacetic acid, C8H8O3; (ii.) 3: 4-dihydroxycinnamic acid, C,H804; and (iii.) choline, C5H1502N. The aqueous liquid also contained a quantity of sugar, which apparently consisted chiefly of lævulose.

The portion of the alcoholic extract which was insoluble

Jan. 3, 1913

The degree of dissociation at a given concentration and the rate of dissociation with dilution depend on the nature of the solute and the solvent, a condition which is paralleled by the ionic dissociation of salts dissolved in various solvents. DISCUSSION.

Mr. THOLE agreed with the President that tartaric acid and its esters were undoubtedly associated, and that the degree of association would be influenced by racemate

and OSCAR LISLE BRADY.

Diphthalamic acids of benzidene, tolidine, and dianisidine are produced by the interaction of phthalic anhydride and the diamine at 100° in the presence of nitrobenzene. They condense with resorcinol in the presence of zinc chloride to give colouring matters of the formula

(where RH, Me, or OMe).

0:

он

These colouring matters are also obtained by heating a mixture of (i.) the diamine, phthalic anhydride, and resorcinol with zinc chloride; (ii.) fluorescein, the diamine, and the hydrochloride of the diamine; and (iii.) the di phthalimino-derivative of the diamine with resorcinol and zinc chloride.

On bromination they yield octabromo-derivatives which can also be obtained by heating eosin with the diamine and the hydrochloride of the diamine.

The reaction appears to be a general one, as it takes place when di- and tetra-chlorophthalic or succinic anhydrides are used instead of phthalic anhydride, and when diethyl-m-aminophenol is substituted for resorcinol. Con; densation takes place also with quinol, catechol, and pyrogallol, but in these cases the colouring matters produced are brown, and probably have a constitution different from the above.

DISCUSSION.

Dr. J. T. HEWITT drew attention to the interesting difference existing between the compound obtained by the authors and fluoresceinanilide. The latter was a colourless substance, and probably had a lactam constitution.

*294. "Viscosity and Association. Part III. The Existence of Racemic Compounds in the Liquid State." By FERDINAND BERNARD THOLE.

The application of the viscometric method to the solution of the problem of the existence of racemic compounds in the liquid state has been extended to a much wider range of substances, both in solution and in the fused state. The results obtained for viscosity and other physical properties have also been correlated.

In the present work the results obtained show that the majority of dl-liquids and solutions are merely conglomerates. Under this heading fall ac-tetrahydronaphthol, heptan 8-ol, octan-ß-ol, carvoxime, octyl hydrogen phthalate, and ethyl mandelate.

On the other hand, distinct evidence of the existence of a liquid racemate has been found with dimethyl and diethyl racemates and l-menthyl r-mandelate. To these may be added the cases of racemic acid and perhaps r-mandelic acid previously investigated.

In the cases where racemate existence in solution has been substantiated dissociation is very considerable, and increases with increasing dilution of the solution,

This point had, in fact, been brought out in a previous communication on this subject.

In reply to Dr. McKenzie's question as to the identity of solutions prepared from racemic acid and from equal quantities of the enantiomorphs, the author stated that this point had been tested and the identity of the solutions established. The menthyl mandelates had been investigated, both in the fused state and in solution in amyl acetate. Although this liquid was one of the least dissociating solvents, dissociation of the racemic solute was very considerable, and probably in dissociating solvents such as alcohol or water dissociation would be practically complete.

295. "Condensation of a-Keto-B-anilino-aß-diphenylethane and its Homologues with Phenylcarbimide and with Phenylthiocarbimide." By SIDNEY ALBERT BRAZIER and HAMILTON MCCOMBIE.

a-Keto-8-anilino-aß-diphenylethane and phenylcarbimide when heated together yield desyl-s-diphenylcarbamide (I.). This compound, on treatment with alcoholic hydrogen chloride, loses the elements of water, yielding 1: 3:45tetraphenyl-2 3-dihydro-2-glyoxalone (II.). The reaction has been extended also to the compounds in which aniline has been replaced by o-, m-, and p-toluidine, and by B-naphthylamine :

COPh CH Ph NPh CONHPh
I.

CPh•NPh || CPh•NPh III.

CS

thiocarbimide, resulting in the production of 1:3: 45The phenylcarbimide has also been replaced by phenyltetraphenyl-2: 3-dihydro-2-glyoxalthione (III,) and its homologues.

The glyoxalones and the glyoxalthiones were found to be very stable substances, unaffected by acids, alkalis, or phosphorus pentachloride.

The glyoxalones yield salts with picric acid, but not with hydrochloric acid. These picrates can be divided into two classes, namely, (1) those formed by the aniline, p-toluidine, and B-naphthylamine compounds are red, and consist of 2 molecules of the base combined with 1 molecule

I

of picric acid; and (2) those formed by the o- and m-toluidine compounds are yellow, and consist of the base and picric acid in equimolecular proportions.

296. "Influence of the Sodium Salts of Organic Acids on the Rate of Hydrolysis by Alkali." By GEORGE Senter and FRITZ BULLE.

The main results of the investigation are as follows:1. Sodium salts of organic acids, like the corresponding salts of inorganic acids, have only a slight effect on the rate of hydrolysis of ethyl acetate in alkaline solution.

2. Sodium salts of organic acids accelerate the hydrolysis of sodium bromoacetate by alkali to a still greater extent than do the salts of inorganic acids.

3. This effect has been traced, taking the case of sodium acetate as typical, to the intermediate formation of esters of sodium glycollate (for example, sodium acetylglycollate), which are hydrolysed by alkali as fast as they are formed. 4. From the extent to which the hydrolysis of ethyl acetate by alkali is retarded by monosodium salicylate, a provisional estimate of the second acid dissociation-constant of salicylic acid at 20° has been made,

Experiments have been carried out in aqueous and aqueous-alcoholic solutions with varying concentrations of sodium hydroxide, the corresponding values of the constant for a unimolecnlar reaction being determined by measurements of the rate of evolution of nitrogen. This kinetic investigation of the reaction has shown that in all probability the decomposition, except over a range from about o 05N- to o'3N-NaOH, will afford a method for the quantitative determination of hydroxyl ions, comparable to that which Bredig and Fraenkel have found for hydrogen ions in the decomposition of diazoacetic ester.

303. "Chlorides of the Mercurialkyl- and Mercurialkylaryl-ammonium Šeries, and their Constitution as based on Conductivity Measurements." By PRAFULLA CHANDRA RAY and NILRATAN DHAR.

The preparation of the following compounds was described:-(1) Mercurimethylammonium chloride, (2) mercuriisobutylammonium chloride, (3) mercuripiperazinium chloride, (4) mercuribenzylammonium chloride, (5) mercuribenzylmethylammonium chloride, (6) mercuribenzylethylammonium chloride, (7) mercuriethylenediammonium chloride, (8) mercuripyridinium chloride, (9) mercuripicolinium chloride, (10) mercurinicotinium chloride, (11) mercuripiperidinium chloride, and (12) mercurihexa methylenetetra-ammonium chloride. Although these salts are generally regarded as insoluble, they have been found to be sufficiently soluble to lend themselves to conductivity measurements. It is found that they all conform to the ammonium type of salts.

304. "Position-isomerism and Optical Activity; Halogen Derivatives of Methyl Dibenzoyltartrate." BY PERCY FARADAY FRANKLAND, SIDNEY RAYMOND CARTER, and ERNEST BRYAN ADAMS.

The preparation and properties of the dichloro-, dibromo-, and di-iodo-benzoyl derivatives of methyl tartrate were described. In each series the order of the rotatory power of the compounds, para>meta>dibenzoyl>ortho, is maintained. The rotations were determined in the fused state, and over a range of temperature from about 20° to 100°. The rotations as a whole diminish with rise of tem

perature, but the rotation of each of the ortho-compounds attains a maximum value below the melting-point, as already found by one of the authors in the case of ethyl dibenzoyl- and of ethyl and methyl di-o-toluoyl-tartrates. Incidentally, the anhydrides of p-chloro- and m- and p-iodobenzoic acids have been prepared.

305. "Reactivity of the Halagens in Organic Compounds. Part VII. The Formation of Intermediate Compounds in the Hydrolysis of Sodium Bromoacetate." By GEORGE SENTER and THOMAS JOHN Ward.

The effect of sodium acetate and of sodium formate on the rate of hydrolysis of sodium bromoacetate has been measured, and the intermediate formation of sodium salts of glycollic esters has been proved by comparison of the results with those to be anticipated on the view that consecutive reactions take place during the hydrolysis.

The rate of hydrolysis of acetylglycollic acid and of sodium acetylglycollate in neutral and alkaline solution, and the influence of neutral salts on the rates of reaction have been measured.

Evidence was adduced to show that during the hydrolysis of sodium bromoacetate in fairly concentrated solution the reaction proceeds mainly by means of the intermediate formation and hydrolysis of sodium bromoacetylglycollate.

.CO.

C6H4 *N [CH2]3'NH•CO-C6H,COH,

from the corresponding diphthalamic acid. The latter, moreover, even on cautious hydrolysis, suffers loss of both phthalyl residues.

Attempts on other lines to prepare benzoyl-ay-diaminopropane were also unsuccessful; but its synthesis was finally effected from benzamidine and ay-dibromopropane through 2-phenyl-1:4: 5: 6-tetrahydropyridine by the following steps:

C3H6Br2 CPh(:NH)NH, →

Benzamidine

N.[CH2]3'Br

CPh....NH,

Dilute aqueous → ammonia at 80°

NHz[CH2]3`NH COPh Benzoyl-ay-diaminopropane.

Its

2-Phenyl-1:45: 6-tetrahydropyrimidine, which has previously been obtained in an impure form as an oil by Pinner (Ber., 1893, xxvi., 2122) is a crystalline solid, melting at 72°, which is not very soluble in water. oxalate melts at 175°, and hydrogen oxalate at 180°. On benzoylation the base yields tribenzoyl-ay-diaminopropane, NBZ2 [CH23 NHBz (m. p. 144°).

Benzoyl-ay-diaminopropane crystallises in transparent prisms melting at 46°. It is readily soluble in water, and its oxalate melts at 196°. On benzoylation it yields s-dibenzoyl-ay-diaminopropane (m. p. 151°).

307. The Magnetic Rotation of Binary Mixtures." By FRÉDÉRIC SCHWERS.

density C, and of magnetic rotation Cr, there is a ratio Z In a binary mixture of liquids, between the changes of (rotation constant), which possesses as a whole the same properties as the ratio A (refraction constant) between the changes of density and those of refractive power Cn. The common points are :—

I. For a given system, Z is independent of the concentration.

2. The value of Z diminishes with the decrease of wave-length.

3. The value of Z is characteristic for each system, and follows some general rules, as, for instance :

(a) If we consider the mixtures of one liquid successively with the different terms of an organic series, Z decreases from the first term upwards.

(b) If we compare the solution of a liquid in water and in alcohol, we find a higher Z-value for the last-named solution.

(c) The values of Z in a carbon disulphide solution are much smaller (three to six times) than in the case of the corresponding aqueous solution; the mixtures with carbon disulphide are also particularly interesting, because they show that the general rules are the same, whether the mixture undergoes a dilatation or a contraction (aqueous mixtures).

4. In case the mixture undergoes electrolytic dissociation, Z increases with the dilution ( = ionisation).

The difference consists in the fact that Z is always smaller than A. For the aqueous mixtures examined, Z has the average value of one-third of A; but this cannot be regarded as a general rule, as it is only one-sixth for carbon disulphide mixtures.

CHEMICAL NEWS, Jan. 3. 1913

Elementary Chemical Theory and Calculations. By JOSEPH KNOX, D.Sc. London: Gurney and Jackson.

1912.

THIS is a really admirable little book which should be in the hands of every student of elementary chemistry. It contains a short discussion of the essentials of chemical theory, with carefully graduated problems for solution. The chapters are usually short, and there are plenty of worked examples to drive each point home. The laws of chemical combination are stated clearly and explained in detail, and discussions of the atomic and molecular theories follow. Methods of determination of molecular and atomic weights are particularly well explained, and students should benefit greatly by having a clear conception of them. Calculations based upon equations are put at the end of the book, and students who have worked through the 200 problems which precede them should have no difficulty in dealing with them. A thorough grounding in elementary chemical theory is to be obtained from the book, which can confidently be recommended for use in the higher classes of schools and in colleges.

A College Text-Book of Quantitative Analysis. By HERBERT RAYMOND MOODY, S.B. (M.I.T.), A.M., Ph.D. (Columbia). New York: The Macmillan Company. 1912.

THE author of this book believes that it is bad policy to allow the student who is beginning quantitative analysis to fall into pitfalls and make mistakes which lead to a great waste of time, and his special object has been to make his directions so clear and exact that even the beginner should be able to get quite accurate results in his first determinations. He certainly seems to have foreseen every possible cause of failure, and his lists of warnings and hints are copious. Throughout the book the experimental directions are annotated with explanations, printed in large tyre as footnotes, and there is very little excuse for the student to do unsuccessful work. He will be trained from the very first in accurate and careful habits, and if he is not allowed much freedom of thought and action, possibly quantitative analysis is to be regarded as a subject which does not aim so much at developing these characteristics as some other parts of his scientific work. The analyses described are comparatively few in number, but they include gravimetric, volumetric, and electrolytic processes. Of the latter only one method is described, but that is given in detail, while in the volumetric work the directions are particularly full and precise.

The Effect of the Labrador Current upon the Surface Temperature of the North Atlantic and of the Latter upon Air Temperature and Pressure over the British Isles. By M. W. CAMPBELL HEPWORTH, C.B., R.D. Geophysical Memoirs, No. I. Published by the Meteorological Office. 1912.

THE author of this monograph has previously made a comparison of the changes in the strength of the Trade Winds of the Atlantic during each of the five years 1902-6, and of the changes in the Surface Temperature of the North Atlantic in the years 1903 7. From these comparisons it appeared that deviations from the average strength of the two Trade Winds during a series of months, or even during one month, were reflected in deviations from the normal in the average distribution of surface temperature in the North Atlantic in the corresponding series of months in the succeeding year.

For the purposes of comparison two zones were selected in the North Atlantic, the one lying between Florida Strait and Valencia and the other between that Strait and Cape Race, and the author has now shown that the encroachment of the Labrador Current is one of the most

9

potent causes which tend to modify the influence of the Gulf Stream upon the temperature of the North Atlantic. Also the increased activity of the current in the five years from 1903-7, manifested by an increase of ice in the North-Western Atlantic, was generally followed by a diminution in temperature of the surface water in the FloridaValencia zone. Moreover, a fall in sea-temperature is often associated with a corresponding fall in air. temperature at the Valencia, Sumburgh Head, and North Shields meteorological stations; and, in winter, with an increase of pressure. Also a rise in sea-temperature is accompanied by a rise in air-temperature, and, except in summer, with a diminution of pressure. The temperature of the sea is also lowered by the Labrador Current in another way. When the current encroaches upon the stream, where the two meet the course is diverted, and the stream flows north-eastward in a less northerly direction, so that the northern portion of the ocean is deprived of much of the warming influence of the stream from the south.

Isles is modified by changes in the surface temperature of In the author's opinion air temperature over the British

the North Atlantic in three ways:-(1) By winds from the sea; (2) by the influence of sea temperature upon the paths of depressions that influence the wind and weather; (3) by a diminution of cloudiness. When the surface temperature of the north-eastern part of the North Atlantic is much below the average, atmospheric pressure over the Iceland-Faroe region has a tendency to increase, and centres of depression, passing over the British Isles, bring much cloudiness and rain. On the other hand, if the Gulf Stream is following its normal or a still more northerly ward or northward of these islands, and mild southcourse, the centres cf Atlantic depressions pass to the westwesterly types of weather or anticyclonic conditions prevail.

The diagrams from which these conclusions are drawn are reproduced in the monograph, which is an important contribution to our knowledge of the conditions which influence the effect of the Gulf Stream upon the tempera

ture of the North Atlantic.

Treatment of Effluents from Dyehouses and Textile Factories. By J. H. GARNER, B.Sc. Leeds and London: The Electric Press.

THIS book contains the prize essay to which the Silver Medal of the Society of Dyers and Colourists was awarded, and which was originally published in the Journal of the Society in the early months of the current year. The essay gave an outline, with diagrams and plans, of methods of treating the liquid refuse from the textile trades so that it may safely be allowed to flow into rivers and streams without deleterious effects, and also of processes of extracting valuable by-products; for example, from woolwashing refuse. The author was fortunate in being able to obtain access to many purification works, and to carry out analyses in the Laboratory of the West Riding of Yorkshire Rivers Board, and the essay, while not going into very great detail, gives a clear summary of some of the apparatus and methods used in purifying effluents.

Festschrift W. Nernst zu seinem Fünfundzwanzigjährigen Doktorjubiläum gewidmet von Seinen Schulern. ("Memoir Dedicated to W. Nernst by his Pupils in Celebration of the Twenty-fifth Jubilee of his Doctorate"). Halle-a.-S.: Wilhelm Knapp. 1912.

THE papers composing this book have been contributed by a number of Prof. Nernst's pupils, whose activity in research is the best possible tribute to his inspiring teaching. They are written mostly in German, with a few exceptions in English or Italian, and deal with a wide range of subjects in physical and inorganic chemistry. It would perhaps be invidious to select for special mention any articles from so many of such excellence, and the book is a remarkable achievement from many points of view.