22,

Experiments on hygrometry at low temperatures are in progress at the National Physical Laboratory and at the Physical Laboratory of the University of Bristol.

Experiments on the storage of fruit have shown that by the employment of certain artificial atmospheres in the storage chambers, the life of the fruit may be greatly extended. A method of drying certain fruits which promises good results has also been worked out. The study of the respiratory metabolism of fruit at low temperatures, and of the oxidising enzymes responsible for the discoloration of certain fruits on injury has also been continued. The chemistry of the ripening process in fruit has been investigated with special reference to the changes in the pectin, and the limits of temperature within which the moulds commonly infest fruit in store will grow have been determined.

A

The work of the Oils and Fats Committee consists, in part, of investigations begun during the war at a time when there was the possibility of an acute conflict between the demands for oils and fats for human consumption on the one hand, and for the preparation of the glycerol needed for the manufacture of explosives on the other. process has been discovered which points to a successful synthesis of glycerol, and the physiological properties of fats in which glycerol has been replaced by other polyhydric alcohols have been determined. Experiments have been made on the production from linseed oil of an edible oil. The production of oils by vegetables has been studied, and an important monograph of the unsaturated monobasic acids related to fats has been completed.

The Canned Foods Committee have completed a report, which is now in the Press, on the methods of inspection of tins, and are continuing their work on the bacteriology and chemistry of canned foods.

Fish Preservation Committee.

of

Work under this Committee has not been on a scale commensurate with the importance of the subject, owing to the fact that the only plant available for experiments has been a small brine freezing plant, installed originally for demonstration purposes in the basement Billingsgate Market. Two research workers, Mr. G. Adair and Mr. J. Piqué, made experiments upon the rate of freezing fish in cold brine, upon the penetration of salt into the bodies of brinefrozen fish, and upon certain mechanical devices designed for the application of the process of freezing in brine to commercial practice. They made full use of the plant during the many months they worked there, until the total absence of daylight, the damp and the noise made them both seriously ill. The experiments at Billingsgate were supplemented by others carried out in the University Physiological Laboratory of College, London, by the kindness of Professor W. M. Bayliss, F.R.S.

In spite of difficulties, to which no description can do justice, Mr. Adair and Mr. Piqué have carried their investigations far enough to form the basis of an interim report upon the freezing of fish, which the Committee are now completing.

In addition to the work at Billingsgate, Miss I. H. Green has been engaged upon an intensive study of the bacteria which occur in herring. She has isolated, cultivated, and identified many species, and by so doing has laid a foundation for the further study of putrefactive change in these fish. In June, 1919, Miss Green visited North Wilson, of the Shields Ice and Cold Storage Shields, where, by the courtesy of Mr. George Company, she was able to make a special study of the bacterial changes in herring which had been treated in various ways. The chief results at which she arrived were :

Annual General Meeting, 10.30 am. Annual Dinner.

March 10.

Annual General Meeting, 10.30 a.m. May 4. Annual May Lecture, 8 p.m., by Prof. T. Turner, M.Sc., A.R.S.M.

Birmingham Local Section.

October 12. H. W. Brownsdon, M.Sc., Ph.D.
Chairman's Address.
November 16. Discussion upon "Hardness in
Non-ferrous Alloys."

December 14. W. R. Barclay, O.B.E. "Some War Experience in the Electro-deposition of Metals."

January 11, 1921 Ernest A. Smith, A.R.S.M. "Segregation in Non-ferrous Alloys." February 15, 1921. O. F. Hudson, D.Sc. "Bearing Metals."

March 22, 1921.

R. T. Rolfe. "Gun Metal."

January 28, 1921. Prof. C. H. Desch, D Sc., Ph.D. "60 40 Brass."

February 18, 1921. F. Rogers, D.Eng., BA., M.Sc. "Cracking in Worked Brass and other Metals."

March 18, 1921. W. Rosenhain, D.Sc., F.R.S. (Vice-President). "The Crystal Boundary." April 15, 1921 H. A. Greaves. "A New Non

ferrous Electric Furnace."

Scottish Local Section.

October 27. The Rt. Hon Lord Weir of Eastwood, P.C. (Member of Council). Address on "Some Notes on Foundries and Production."

November 9. J. A. C. Edmiston. "Fuel." December 14. Discussion on "Furnaces" (to be opened by Messrs. J. Stirling and J. Arnott). January 11, 1921. S. E. Flack. "Rolling and Extrusion."

February 8, 1921. G. H. Bailey, D. Sc., Ph.D. "Aluminium, Production and Uses." Annual General Meeting. Address by Mr. James Steven (ViceChairman, Local Section).

March 8, 1921.

NOTES.

BIRMINGHAM UNIVERSITY AND RESEARCH. Towards the appeal for £500,000 to maintain and develop the work of the University of Birmingham (which was formally inauguarated on Thursday last), £200,000 was promised. Mr. Austen Chamberlain, the Chancellor of the University, stated that the Government had this year given a million pounds to the Universities. He hoped they would be able to increase the amount next year by halfa-million. The Government recognised fully the splendid services rendered during the war by the Universities, and particularly on the Science side. The Government were prepared to back their opinion of the importance of University work. The Principal, Mr. Grant Robertson, declared that a University which was not carrying onresearch was a crippled educational organisation. Research paid. It gave a dividend in cash, and it paid ultimately in a general and heightened national efficiency. He believed that if more money had been put into the Universities for the ten years preceding 1914, that the war would have been shortened by two years.

BOARD OF TRADE ANNOUNCEMENT.—Mr. L. G. Killby has been appointed Secretary to the Empire Cotton Growing Committee. He is at present Superintendent of the Department of Technology, City and Guilds of London Institute. In 1904 at Oxford, he took his B.A. degree in the Honours School of National Science, with Ist Class Honours in Chemistry. He then became Demonstrator in Chemistry, and in 1907 was awarded the degree of B.Sc. (Oxon) for research work. He has been on the staff of the Department of Technology for 14 years. During the war Mr. Killby received a commission in the Army, and served in France as one of the chemists on water supplies in the Field, and was afterwards transferred to the Chemical Warfare Department of the Ministry of Munitions. He was mentioned in dispatches.

October 22, 1920

THE FARADAY SOCIETY AND THE PHYSICAL SOCIETY OF LONDON.—A General Discussion on "The Physics and Chemistry of Colloids and their Bearing on Industrial Questions" will take place on Monday, October 25. The following is the pro gramme:

2.30 to 4.

General Introduction "A Short Survey of the Physics and Chemistry of Colloids," by Prof. Dr The Svedberg, of the University of Upsala.

Discussion on "Emulsions and Emulsification.” Opener Professor F. G. Donnan, C.B.E., F.R.S. Mr. W. Clayton, M.Sc. will read a paper on "Emulsion Problems in Margarine Manufacture." Mr. S. S. Bhatuagar will read a paper on "Reversal of Phases in Emulsions and Precipitation of Suspensoids by Electrolysis-an Analogy."

4.30 to 6.15. Discussion on "Physical Properties of Elastic Gels." Openers : Mr. E. Hatschek, F. Inst. P., and Prof. H. R. Procter, D.Sc. Mr. S. C. Bradford will read a paper on "The Reversible So! gel Transformation.' Dr. J. O. W. Barratt, M.D., D.Sc., will read a paper on "The Structure of Gels."

8 to 10.

Discussion on “Glass and Pyrosols." Opener : Sir Herbert Jackson, K.B.E., F.R.S. Discussion on "Non-Aqueous Systems." (a) Nitrocellulose. Opener: Sir Robert Robertson, K.B.E., F.R.S. Mr. F. Sproxton will read a paper on "Non-aqueous Colloid Systems with special reference to Nitrocellulose." Dr. Guy Barr and Mr. L. L. Bircumshaw will read a paper on "The Viscosity of some Cellulose Acetate Solutions." (b) Rubber. Opener: Mr. B. D. Porritt, speaking on "The Action of Light on Rubber."

Discussion on "Precipitation in Disperse Systems." Openers Dr. R. C. Tolman and Dr. R. S. Willows. Mr. J. N. Mukherjee, M.Sc., will read a paper on "The Origin of the Charge of a Colloidal Particle and its Neutralisation by Electrolytes." Mr. W. Clayton, M.Sc., will read a paper on "Coagulation of Inorganic Suspensions by Emulsions."

mose.

Discussion on "Cataphoresis and Electro-EndosOpener Professor A. V. Porter, D.Sc., F.R.S. Dr. W. R. Ormandy, F.I.C. will read a paper on "Some Practical Applications of Electro-Endosmose and Cataphoresis."

THE Secretary of the Department of Scientific and Industrial Research begs to announce that a license, under Section 20 of the Companies' (Consolidation) Act, 1908, has been issued by the Board of Trade to the British Electrical and Allied Industries Research Association, which has been approved by the Department as complying with the conditions laid down in the Government scheme for the encouragement of industrial research. The Association may be approached through E. B. Wedmore, Electrical Research Committee, c/o Electrical Development Association, Hampden House, 64, Kingsway, W.C.2.

NEWS

MAGNESITE AND SHELL-MAKING.-During the war magnesite was found useful in the manufacturing of shells, and now the Engineering and Mining Journal of New York reports that Mr. H. F. Weirum has been experimenting with ground magnesite as a substitute for lime in making egg shells. He finds that hens, fed on the ground magnesite produce a very superior grade of shell. Apparently the old bone-grinding machine used so often in hen yards will soon have to give way to packages of magnesite. As the Canadian Mining Journal says in reference to the matter. It is another example of how the old-established industries have been helped by the hunt for substitutes.

DEVELOPMENT OF ALCOHOL FUEL.-The Empire Motor Fuels Committee of the Imperial Motor Transport Council is dealing actively with the general conditions underlying production and development of alcohol for power and industrial purposes. It has recently appointed small Expert Committees to deal with: (a) The modification of Customs and Excise Restrictions in connection with alcohol; (b) By means of experiments, the best conditions for developing the alcohol engine and types of alcohol fuels-alone or in mixturefor the purpose; and (c) The very important subject of denaturation (or rendering alcohol unpotable). Good progress is being made with the work of all three Committees, but it is felt that members of the public who may have given special attention to the question of denaturation of alcohol should be invited to forward any suggestions for confidential examination and report by the Denaturation Committee. Any such communications should be addressed to Sir Charles Bedford, LL.D., D.Sc., Empire Motor Fuels Committee, 50, Pall Mall, London, S.W.1., marked "Denaturation," and will be treated as strictly confidential. Any suggestions which may prove practicable will remain the sole property of the proposer. It is essential that any proposals regarding denaturants should be made with the knowledge of the particular requirements of a satisfactory denaturant, viz. (a) Deterrent taste and smell; (b) Non-poisonous; (c) Must not be removable at a commercial cost; (d) Must be readily detectable in small quantities; (e) Must be readily mixable with the spirit; and (f) Must be inexpensive. It is, of course, exceedingly difficult to obtain any one substance which will conform to all these requirements, but the difficulty in practice has usually been overcome by using a combination of substances whose complementary action meets the requirements. It is inevitable that many suggestions will be made which fail to meet these requirements, but it is believed that a successful object will be attained by letting those interested know that there exists. a small expert body, acting solely in the public interests, which is prepared to examine confidentially any proposals regarding denaturants. In the event of any such suggestions proving workable, the inventor would be communicated with, and his interests fully safeguarded before proceeding to communicate the results to the Empire Governments concerned.-F. G. Bristow, Hon. Secretary, 50, Pall Mall, S. W.1.

GREY AND MALLEABLE CAST IRON TRADE.-On Thursday, September 30, the British Grey and Malleable Cast Iron Research Association was

formally brought into being at a largely attended meeting of ironfounders from all parts of the country, metallurgists, and industrial chemists. The headquarters are in Birmingham, and Mr. T. Vickers, C.E., Lincoln's Inn, Birmingham, is the Secretary. This is the second research association founded in Birmingham under the Government scheme, the other being in connection with nonferrous metals. Sir Frank Heath, K.C.B. (Government Department for Scientific and Industrial Research) explained the objects of the Association, mentioning that there are 2,796 iron foundries in Great Britain and Ireland, that the largest single county foundry area is Yorkshire with 408, and the largest single town foundry The area is Birmingham with 118 foundries application of science to industry said Sir Frank Heath, was really nothing more than an insurance against the evil effects of ignorance. The first incentive to new ways for competition they got from America. A research association founded in the United States had given promising results, and it was claimed they could make malleable castings of more than 50 per cent tensile strength than was possible in this country. Competition was, however, really nearer, for he learned that in Scotland there was an association of light castings manufacturers who had established a research laboratory. There was nothing corresponding to this south of the Tweed. It was essential that we should know precisely the quality and characteristics of pig-iron, and the proper constitution of the metal from which the casting was to be made. These were matters for scientific investigation. It was decided to form a Grey and Malleable Cast Iron Research Association, on the motion of Dr. L. Aitchison and Prof. T. Turner, University of Birmingham, and representing the Birmingham and Midland Section of the Society of Chemical Industry, pointed out that there were wide fields for research. It was not merely a question of the chemical composition of pig-iron, the effects of different rates of cooling, or impurities in melting, but also the effect of pressure during casting, the composition of sand, and the texture of sand apart from composition, and the amount of blast employed.

MANCHESTER COLLEGE OF TECHNOLOGY WAR MEMORIAL.-The War Memorial Committee, representing all present members of the College, graduate and undergraduate, propose to preserve in the College a permanent memorial which shall include the names of all former students of the College who were killed or who died on service during the late war. The provisional list, which is under amendment, comprises nearly one hundred names.

MEETINGS FOR THE WEEK.

Monday, October 25. Faraday Society land Physical Society, 2.30. (At Institution of Mechanical Engineers). Discussion: "Physics and Chemistry of Colloids and their Bearing on Industrial Questions."

Wednesday October 27.

Conjoint Board of Scientific Societies, 5. (Board Meeting).

Thursday, October 28.

Chemical Society, 8. "Fischer Memorial Lecture" by Dr. M. O. Forster, F.R.S., at the Lecture Hall of the Institution of Mechanical Engineers.

THE CHEMICAL NEWS.

VOL. CXXI., No. 3159.

A MODIFICATION OF SKRAUP'S QUINOLINE SYNTHESIS By EDWARD DE BARRY BARNETT, B.Sc., F.I.C.

THE yield of quinoline obtained when aniline is heated with nitrobenzene, glycerine, and concentrated sulphuric acid (Skraup, Monatshefte, i., 317, ii., 141; Walter, J. pr. Chem. [2] xlix., 549) is about 50 per cent. of that theoretically possible when calculated on the aniline used, but is only about 27 per cent of that theoretically possible with regard to the glycerine. The use of arsenic acid as an oxidising agent in place of nitrobenzene (Kneuppel, B., xxix., 709; D.R.P., lxxxvii., 334) although it leads to somewhat increased yields with reference to the aniline is even more extavagant in glycerine, as only about one-fifth of that used enters into the reaction. More recently, Druce (CHEMICAL NEWS, 1917, cxvii., 346) has described the preparation of quinoline from aniline stannichloride, glycerine, and sulphuric acid, and has stated that 50 grms. of aniline stannichloride yield 20 grms, of quinoline. These figures correspond to a yield of 80.5 per cent of that theoretically possible with reference to the aniline present in the stannichloride. The formation of a molecule of quinoline, however, requires the oxidising powers of a whole atom of tetravalent tin :

CH,NH2+Sn(SO1)2+C ̧H ̧0,=

C,H,N+3H2O+SnSO ̧+H2SO, and consequently Druce's result is difficult to understand, as calculated on the tetravalent tin present in the stannichloride his yield is 161 per cent of that theoretically possible. It seemed superfluous to prepare the stannichloride and then to treat it with sulphuric acid, but a few experiments were made in which aniline was heated with glycerine, sulphuric acid, and stannic sulphate. These resulted in yields of quinoline corresponding to about 30 per cent of the theoretical provided only about the calculated amount of glycerine was used. If, on the other hand, a large excess of glycerine was employed, as in the experiments described by Druce, the yields of quinoline were very poor. The experiments with stannic sulphate were abandoned, however, as it was found that much better results were obtained when the cheaper ferric sulphate was employed. Even with this oxidising agent, however, yields exceeding 60 per cent of theory could not be obtained, and it seemed probable that the relatively poor yields were due to the destruction of the glycerine before quinoline formation had had time to take place. Experiments were therefore carried out in which (a) a great excess of glycerine was employed; (b) the glycerine was slowly dropped into a heated mixture of aniline, ferric sulphate, and sulphuric acid; (c) the reaction was carried out at 130°; (d) the sulphuric acid was diluted to 80 per cent strength. None of these modifications, however, resulted in any definite improvement in the yield. Experiments were also made in which an excess of boric acid was added in the hope that a boric

ester would be formed which would not be so readily destroyed by the sulphuric acid. This method has been very successfully used for the protection of hydroxyl groups during the preparation of hydroxyanthraquinones by direct oxidation (Bayer & Co., D.R.P., lxxix., 768; lxxxi., 244; lxxxi., 481; lxxxi., 956; lxxxi., 960-1-2, etc.), but in the case of quinoline formation the boric acid seemed to have no effect at all. It is probable therefore, that the relatively poor yields obtained are due not so much to the destruction of the glycerin as to the destruction of the aniline, and, in fact, it was found that aniline is fairly easily destroyed when heated with ferric sulphate and sulphuric acid at 140°.

When stannic sulphate was used as an oxidising agent the best results were obtained when aniline (50 grms.) was added to concentrated sulphuric acid (75 cmm.), the solution cooled and then the glycerine (50 grms.) and stannic sulphate (190 After heating on an oil-bath at grms.) added 180-190° for six hours, the melt was poured into water, unchanged aniline destroyed by the addition of sodium nitrite, the solution made alkaline, and the quinoline distilled off with steam. The yields obtained were about 30 per cent of the theoretically possible. In one or two experiments in which a large excess of glycerine (150 grms.) was used, hardly any quinoline was obtained. Much more satisfactory results were obtained when ferric sulphate was used as an oxidising agent, and in fact, it was found that the use of this oxidising agent provides by far the most convenient method of preparing quinoline in the laboratory, as the very violent reaction which often takes place when nitrobenzene or arsenic acid is used is completely absent, and no tar is formed. It is unnecessary to employ dry ferric sulphate, as ordinary calcined ferric oxide, which has been previously treated with sufficient concentrated sulphuric acid to convert it into the sulphate, gives equally good results. The following procedure was found to give yields of quinoline of 45 to 50 per cent of the theoretical.

One hundred gims. of aniline was dissolved in 150 cmm. of concentrated sulphuric acid, and the solution thus obtained added to 450 grms, of dry ferric sulphate, or to 180 grms, of calcined ferric oxide, to which 370 cmm. of concentrated sulphuric acid had been added an hour or two previously. One hundred grms, of glycerin were then added, and the whole heated for six hours on an oil-bath at 180-190°. Without cooling, the melt was then poured into water, made alkaline with caustic soda, and the quinoline and unchanged aniline distilled over with steam. The distillate was then made acid with hydrochloric acid, and aniline destroyed by adding sodium nitrite. After boiling for a few minutes, so as to destroy the benzene diazonium chloride, the solution was again made alkaline and distilled with steam. The quinoline was extracted from the distillate by shaking with benzene, the extract dried over solid, finely powdered caustic soda, and the benzene then removed by distillation.

A very rapid modification of the above process which gives somewhat better yields, about 60 per cent of the theoretically possible, consists in mixing 50 grms. of aniline with 65 grms, of glycerine, and 100 grms, of calcined ferric oxide, and then adding this mixture as quickly as possible to 150