摘要:

T H E ANALYST. FEBRUARY, 1883. SOCIETY OF PUBLIC ANALYSTS. THE ANNUAL MEETING of this Society was held at Burlington House on the 17th January, Dr. Muter in the chair. The minutes of the previous meeting were read and confirmed. The Chairman read the following letter from the retiring President, Mr. Heisch :- GENTLEMEN, 79, MARK LANE, 17th Jan., 1888. On resigning into your hands the office to which you did me the honour of electing me two years since, my first duty is to express to you my unfeigned regret that during the last year the state of my health has been such as to prevent me, not only from working for the benefit of the Society in the manner I could have wished, but even from attending its meetings. The same circumstance must be my excuse for not beiag with you this evening, and also for not being able to address you even on paper at any length.I am glad to be able to congratuhte you on the continued prosperity of our Society and the continued usefulness of its work, as testified by the papers which have appeared in TEE ANALYST. While, however, we bave much cause for congratulation, we bave also cause for unfeigned sorrow, in the severe illness of our esteemed secretary, Mr. Maxwell Lyte, an illness which we have too much reason to fear will prevent his ever being with us again. Those who only knew him at our Sooiety will miss his genial face and manner, while those who, like myself, knew him more intimately, mourn the loss of an estimabIe man and a kind friend. For an account of the work done by the Society, I must, under the circumstances, refer you to the Council’s report.I have to thank you one and all for the uniform courtesy with which you have treated me during my term of office, and for the indulgence shown to my numerous shortcomings. I cannot concIude without expressing my satisfaction that the gentleman proposed as my successor will at last be placed in the position to which the long and eminent services he has done the Society so well entitle him. Heartily wishing the Society prosperity under his presidency, and trusting ere long to meet you with renewed strength, I remain, Gentlemen, yours most truly, CHAS. HEISCH. Dr. Duprd, in proposing a vote of thanks to the retiring President for his services daring the past year, said they were all very aorry to know of the cause that ke-pt him out of the chair that evening, but he had been very seriously ill for several months.Me. Heisch was one of the oldest chemists in London, and in fact was one of the original members of the Chemical Society, of whom there were only three or four now living. His age and the work he had done fully entitled him to be elected as President, and he (Dr. Dupre), had pleasure in moving a vote of thanks for his services. Mr. Dyer seconded the motion, which was carried unanimously. The Chairman moved a vote of thanks to the Chemical Society for the use of their rooms during the past year.14 THE ANALYST. A. HILL, M.D., F.C.S., F.I.C. Mr. Wynter Blyth proposed a vote of thanks to the Hon. Secretaries, and said that for the first time in the history of the Society that vote which they had always passed with such pleasure had a note of sorrow in it.They all condoled with Mr. Lyte in his long illness, and he but expressed the feelings of the Society when he hoped that in a little limo he would be restored to them again. He did not suppose lSlr. Lyte had been able to do much work during the year as ft Secretary, so that it had fallen chiefly upon Mr. Wigner. He hoped they would all pass that vote in the most cordial manner. Dr. Bostook Hill having seconded the motion, it was carried unanimously. Nr. Ashby and Mr. West-Knights were appointed Scrutineers to examine the voting papers, and they reported that the following were duly elected as Officers and Council for the ensuing year. Prdsidsn t , ! Other Blsmbers of Cozcncil, A.ASHRY, XB. LOND., F.R.C.S. Gc. W. WIGNER, F.C.S., F.I.C. C. HEISCH, F.C.S., F.I.C. Vies- Presidents. C. T. KINGZPTT, F.C.S., F.I.C. F. MAXWELL LYTE, F.C.S,, F.I.C. J. MUTER, Ph.D., M.A., F.C.S., F.I.C. M. A. ADAMS, F.R.C.S., F.C.S. A. H. ALLEN, F.C.S., F.I.C. Treasurer. C. W. HEATON, F.C.S., F.I.C. Hon. Secretaries. B. DYER, F.C.S., F.I.C. 0. HEHNER, F.C.S., F.I.C. The names of those Members of Council whose term of office has not yet expired, and who, oonsequently, do not retire this year, are- A, WYNTERBLYTH, M.R.C.S., F.C.S. A. BOSTOCK BILL, M.D., F.C.S., F.I.C. T. JAMIESON, F.C.S., F.I.C. , G. JARMAIN, F.C.S., F.I.C. Dr. Muter then vacated the chair, which was thereupon taken by llr. Wigner. Nr. B. Dyer and Mr. 0. HPhner took their pests as Honorary Secretaries to the Society. Vr.Wigner, having thanked the Societp for eleoting him to that position, delivered the following address :- It has been the cudom i n this Society ever since its foundation, for tho outgoing President to make a few remarkq summarising what has taken place during the previous year. This custom has unavoidably been broken through on tbe present occasion, owiug to the absence of our late President, Mr. Heisch, through illnesa, as explained in his letter just read. I an1 sure you will join with me in regretting the cause of Mr. Heisch’s absence, $8 also the fact that through this the duty of summarising the work has fallen upon me, as Preeident for the ensuing year. As regards the state of our Society, we have elected during the p a r 10 new members and 2 new associates. We havo lost by death 1 member, and by resignation 1 member and 1 associate, making our total membership at the present time 123 members and 19 associates. We are therefore gaining in numbers as well, I hope, as in the influence which as a Society we are able to exert on matters within our own special sphere. The member whom we have lost by death is Ur.R. G. Fraser, of Nova Scotia, He was of course but little known in this country, but on the other side of the Atlantic his name was well known, and he appears to have done a czonsiderrtble amount of useful work,l a --_ THEI ANALYST, especially in connection with the passing of the Adulteration Acts in Canada, and the ~ystematic adoption of a scale of limits and standards, which were in almost every respeot identical with those fixed by us here.AEI a Society, we are in a gomewhat stronger position financially than we were this time last year. We close the p a r as we have always previously done, without any liability, and have an increased balance at the bankers. I t is usual to judge of the work done by a society by the number of papers submitted to it and printed. In our case w e have had during the past year 30 original communica- tions, several of which have been not only of considerable interest, but of permanent value. For my own part I do not think that the important work which the Society has done is to be at all judged by such a test as this. I think that but for the action taken by as 8 body in urging on an uniform systematic mode of analyaes of samples of food, discredit would have been brought upon Public Andysts generally by the lack of uniformity, and by the fact that in numerous cases one analyst would have been brought to give evidence against another in order to show a variation of one or two per cent.in any given sample. Our co-operation one with another, and our influence as a Society, has greatly cheeked this evil, and while the good result may to some extent have been attained at the cost of making the standards or limits rather lower than in the opinion of some of us they ought to have been, yet that cost has been but a trivial one compared with the gain. The issue of this month’s number of THE ANALYST completed the second year of the qwtematio analyses of the principal water supplies.During that time nearly one thousand analyses were made and published, and the Council felt that the time had arrived for the Bociety to discontinue the work, and to leave it for those water companies or corporations who desire to see it extended t o make any arrangements they choose. It is, however, as well to put it on record that, as far as I know, not one analysis out of the one thousand has been paid for-they were, in every sense of the word, independent analyses. By the result of tbe ballot this evening I have vacated the post of joint hon. secretary, which I have held since the formation of the Society. For obvious reasons I do not go at any length into what has been done while I have been in that position. One thing, how- ever, is clear, and it should be well borne in mind, that it was ontirely owing to the exertions of this Society that the Sale of Food and Driigs Act was passed in suoh a form a# to be capable of being worked at all, and that had the whole of the recommendations which were suggested by the Society been adopted, we should have been spared the occasional failure of prosecutiona 011 technical grounds, and from the general diRgrace that results from the fact that, uotwithstanding the existence of such an Act; there is hardly any place in the world where (at least) milk adulteration is so prevalent a8 in London itself. The Scrutineers reported that Mr.A. P. stokes, Publict Analyst for Paddington, &c., had been duly elected a Member of the Society. Mr. J, G. ROSP, Assistant to Dr. Drinkwater, of Edinburgh, was proposed as an Associate. MI*. Hehner read a paper ‘’ On the Analpsis of Bees’ Wax-Part I., Yellow Wax,” and The members and several friends afterwards adjourned to the Criterion, Piccadilly, The next Meeting of the Society will be held at Burlington House, on Wednesday, the * Owing to the length of this paper me are compelled to hold over much other interesting matter, .--I_ ---_____-_ exhibited very numerous specimens of wax and its adulterants.*’ where the P-nnual Dinner was held, and a very enjoyable evening spent by those present. 14th February. sspecidly Dr. Hogg’s paper, ‘( On the Work Done by the Paris Munioipal Laboratory.”

ISSN:0003-2654    

DOI:10.1039/AN8830800013

出版商:RSC    

年代:1883

数据来源: RSC

摘要:

ON THE ANALYSIS OF BEES’ WAX. PART I.-YELLOW WAX. BY OTTO HEHNXR, F. C.S., F.I.C. Head before the Society of Public Aiialysts on ths 17th January, 1883. ANALYSTS who have occasion to enquire into the subject of wax analysis cannot fail to be struck with the fact, that while very numerous ‘ 4 tests ” for the purity or otherwise of wax hiwe been published, no rutimal method of wax analysis is in existence : that is to say, no method founded upon the long-known chemical composition of that substance. As was the case, until recently, with fats, the complicated nature of the components seems to have deterred chemists from attacking the subject in a scientific manner. Whilst a certain value cannot be denied to many of the tests to which I have referred, the indications which they yield are most rague, and certttinly are quite incapable of giving quantitalive results.A special and solitary exception must be made in tho case of the research of P. Beoker (Corr. BZ. d . T’ereins Aizalyt. Chem., 2 ; 57). few samples of wax precisely according to Kottsdorfer’s method of butter titration, expressing the resixlts in percentages of KHO used. He showed that there existed a notable difference in the ntrutralising capacity of wax and a number of possible wax substitutes. In Pldosoph. Trumnctions, 1848, Sir Benjamin Brodie demonstrated that bees’ wax mainly consisted of cevoiic acid C2,H5701, m?yicine or ~idmnitats of m,yric,yle, Cr6Hgr0, C,H,,O, and a smaIl quantity of a fatty substance resembling margarine. To this fatty substance Lewy (Compt.rend. XX) gave the name esi*oZsine, although he did not much to elacidate its nature. Brodie determined the amount of cerotic acid in a sample of Surrey wax Ey precipitating the alcoholic solution of the sample by an alcoholic solution of lead acetate, waehing the precipitate with aloohol and ether, and calculating from it the amount of cerotic acid. He thus obtained 22 per cent. From a sample of Ceylon wax he did not, however, get any oerotic acid at all. According to John, Buchholz, and Brandes, no less than 90 per cent. of the wax are cerotic acid, Boudel and Boisaenot ststing the amount at 70 pe cent. Hess found only 10 per cent. Lewy states the peroentage of ceroleine to be about 4 to 5. The above include the whole of the statement8 which I ham been able to trace as to the quantitative composition of bees’ wax.It will be allowed that they are far from gatisfactory. I imagined that it should be possible to determine alkalimetrically in alcoholic solution the percentage of cerotic acid, and by saponification also that of myriche, quite analogoue to the well-known proceeding of Xottsdorfer. When I first took up this 6ubject the titration of free fatty acid in presence of fat was yet unknown, but in the meantime a great number of chemists have published methods effecting this object. I made same experimentg with known mixtures of palmitic acid and tallow, and found that the acid could with the greatest ease be titrated, phenolphthalein being the indicator, and that the amount of fat could also be obtained by boiling with an excess of alcoholic potash and titrating back with standard sulphurio acid.A mixture made of 43-49 per cent. of palmitic acid and 51*lil per cent. of tallow gielded 48-83 per cent. and 51*17 per cent. respectively, the neutrdiahg This chemist examinedTEE ANALYST. 17 capacity of the two substances baving been separaiely determined. It is needless, however, for me to enlarge upon these preliminary experiments, since it can be considered to be fully established by others, that fatty acids and fats can thus be readily estimated. In the case of wax, however, several difficulties present themselves. The f i a t consist8 in the extraordinary magnitude of the molecular weights of both cerotic acid and myricine the former being 410, the latter no less than 676.Each cubic centimetre of normal alkali, therefore, would neutralise as much as *41 of cerotic acid, and decompose *676 grm. af myricine. It was obvious that the titrations had, under these circumatances, to be made with the greatest possible care-a difficulty still enhanced by the dark colour of some of the exotic samples of wax, which gomewhat obacured the phenolphthalein indication. A further obstacle was found in the difficulty with which myricine saponifies, and a number of experiments had to be made with a view to ascertain whether this tiaponification-which in the case of wax has hitherto been affected with fusing potash-oould be completed at all in the dilute soliltions rendered necessary in quantitative working. The most serious consideration was, however, the sup& of really genuine wax.It would naturally be imagined, that if honeycomb were purchased as it comes out of the hive, and oneself separated from it in the usual manner the wax constituting the cell walls, the product would be genuine beyond a doubt. But tbis is not so. Very many bee-keepers suspend in the hives sheets of wax stamped on both sides with hexagons, to induce the bees to utilise the hexagonal ridges as ‘‘ foundations ” for the cells, thus ensuring the regularity of the comb. These foundatiom are obtained from certain dealers, some of whom warrant them to be composed of genuine wax, I have no doubt that genuine wax foundations are to be had, but tha two samples which I obtained were dstures in spite of the warranty, as will be seen from results stated further on.Pure wax does not appear to be quite so plastic as certain mixtures : this may be one reason for their compound nature ; but I suspect that since wax is dear, and fats and paraffin are cheap, the chief inducement is not of an ~ntirely unselfish character. As for 20 lbs. of honey a hive only yields one lb. of wax, it is also intelligible why Lgome bee-keepers are very liberal with the supply of foundation ” to the bees. Although generally a comb into which ‘( foundation I’ has entered can be distinguished from the more irregular pure comb, and although I have taken a11 possible care to exclude suspicious samples, 1 am not at all certain that the whole of the samples which I believed to be unmixed were absolutdy pure and free from admixture.The mode of procedure upon which I finally fixed is as follows :-Alcoholic potash solution is made from pure potash and from spirit which has been distilled from caustie alkali. Each C.C. should correspond to from -3 to *4 of normal acid. Two or three standardising experiments must be made, and the average taben. I reject all figures if they differ more than *02 c.c., aalculated for 10 C.C. of standard acid. From 3 to.6 grammerr of the wax are weighed on a watch-glass, transferred to a flask holding about 400 c.c., and heated with about 50 C.C. of methylated spirit distilled from alkali. When the wax is perfectly liquefied, alcoholicz phenolphthalein solution is added in not too small amount. The phenolphthalein solution must not be acid, as it generally is, but must be rendered pink by a few drops of alkali. The alcoholic potash solution is then added drop by drop, the mixture being kept well agitated until the pink colour is permanent.The volume is read off, and an oxcow of the aleoholic potash solution is run into the flask, 50 C.C. being thequantity I generally use. The whole ig then briskly boiled under a reflux condenser, for one hour. If any particle of wax hang above the level of the fluid on the side8 of the flask, shake well from time to time. After one hour tht solution should be dear, or very nearly go. The excess of potash is then titratfed back with standard sulphurio acid, the fluid being kept boiling. From the data thus obtained the free acid-calculated as cerotic acid, and the saponifiable substance-calculated as myricine, are obtained.The following are the results of samples either fused from comb by myself or obtained from bee-keepera direct :- 1.-HERTFORDSHIBE WAX. 13.7417 grm. used 2.82 0.0. KHO (10 C.C. = 444 N.S.*) to neutralise the free aoid. Total RHO added 49.96 c.c., titrated back with 16.97 0.6. N.S. Hence cerotic acid -5571 grm. or 14.35 per cent., and myricine 3.3124 grm. or 88*55; per cent. Total, 102.90. 3.7123 grm. used for acidity 8*90 C.C. KHO (strength as above), corresponding to Total alkali added 52.5 G.c., titrated back with 18.29 C.C. n. H,SO,. Hence used Cerotic acid 14.86 per cant., i?.-HERTFORDSHIRE a *5617 grm, oerotic acid. for saponification 4.72 N.S., equal to 3.1907 gims. myricine. myricine 85.95 per cent. Total, 100*81.3 .-HERTFOIt;DSBIRE. 3*2669 grm. used for cerotic acid 3.00 C.C. ale. EHO (10 0.c. = $918 C.O. N,f3), corresponding to 4819 grm. or 14.79 per cent. cerotia acid. TotaI solution used 50.96 C.C. = 19.97 C.C. N.S. Titrated back with 14.56 C.C. n, H,SO, = 4.23 C.C. useit for saponificalhn, indicating 24596 grm. or 87.76 per cent. myrictine. Total, 102.55 per cent. 4*-SUBBEY Not quite pure, but quantity too small to allow of clarification. 8.0490 prm. used 2 70 C.O. alc. KHO (10 C.O. = 3.616 LO. n. acid) for neutrdisation = e 9 8 C.C. N.S. = 4030 grm. or 13.22 per cent. cerotic noid. Total alo. KHO used 50.0 C.C. = 18-20 0.0. N.S. Titrated back with 13.34 O.C. n. acid : this gives 3.88 C.C. for rnyricine = 2.8229 grrn. or 86.02 per oent. myricine. TOM, 99-24 per cent.5.-LINCOLNSHIRE. 4.4012 grm. used for cerotic acid 4.05 0.0. 4116. KHO = 1.155 C.C. N.B. = -5965 grm. Total added 50 C.C. alu. KHO = 17.96 C.C. K.S. l'ilrated back with 10.77 O.C. Henco 5.74 0.0. wed for saponifying myricine, oorrespoiidiag to 3.8802 grm. or or 18.66 per cent. cerotic acid. n. H,SO,. 88-16 per oent. myricine. Total, 101.72. 6.-BUCKINOHA31. 3.9972 grm. gave *483 grm. or 14-64 per cent. cerotic acid and 87-10 per cent. myrioine. (The details of titration have been lost). 'I.--BUCKINGHAM, 8.7527 grm. ueed 8.89 C.C. ah. KHO for cerotic acid (10 C.C. = 8.696 O.C. N.S.) =: 1.437 C.C. N.S. = G894 grm. or 15.71 per cent. cerotic acid. Total taken, 60 C.C. alc. KHO = 18.48 C.C. n. acid. Titrated back with 12-10 0.0. n. acid = 4.942 C.C. used for myricine = 3.8408 grm.or 89.02 per cent. Total, 104.78 per cent. * N.S. = Normal Solution.THE ANALYST. I9 8.-HERTFORDSHIRE. 3.8979 grm. used for cerotic acid 3.97 C.C. alc. EHO (10 C.C. =: 3.71 6.c. n. acid) = 1.428 C.C. N.S. = 05855 grm. or lfj002 per cent. cerotic acid. Total alcoholic KHO taken 50.0 0.0. = 1856 c.c, n. acid. Titrated back with 12.00 C.C. acid. Hence 6.122 C.C. used for myricine = 3-6425 grm. or 88-83 per cent. Totaly 103.85 per cent. 4.0430 grm. used 2.30 C.C. alc, KHO (10 C.C. = 6.417 C.C. n. acid) = 1.476 C.O. N.S. = *6052 grm. or 14.96 per cent. cerotic acid. Total alkali taken 80 C.C. == 19.251 C.C. N.S. Titrated back with 12.40 C.C. n. acid. Hence used for myricine 5.376 C.C. = 3.6335 grm. or 89-87 per cent. Total, 104.83 per ctent. 9.-NEW FOREST. 10.-LINCOLN SHIRE.Made from oomb containing ‘( foundation.” 3.4210 grm. used 3.60 C.C. SIC. KHO (10 C.C. = 3.598 C.C. N.S.) = 1.293 C.C. N.S.) Total added 50-96 C.C. alc. KEO = 18-31 C.C. N.S. Titrated back with 12-36 C.C. Total, or -5301 grm. or 15-49 per cent. cerotic acid. N.S, Hence 4.66 C.C. N.S. uijed for myricine = 3.1502 grm. or 92-08 per cent. 107-67 per cent. The following samples were obtained from first-class druggists and merchants, and not fused down by myself :- 8.7727 gms. used 3.66 C.C. alc. KHO for cerotic acid (10 C.C. = 8.68 c,c. N.S.) = 1-347 c.c, N.S. = -6523 grm. or 14.64 per cent. cerotic acid. Total alc. KHO taken 50 C.C. = 18.40 C.C. n. acid. Titrated back with 12.17 C.C. N.S. Hence 4.888 C.C. used for saponification of myricine, corresponding to 3.3009 grm.or 87-49 per cent. myricine. 11. Total, 102.13 per cent. 12. 2.9963 grm. used 3.00 C.C. a h HHO = 1.104 C.C. N.S. = 04526 grm. or 15*1l per cent. cerotio acid. Total do. KHO taken 50 C.C. = 18-40 C.C. N.S. Titrated back with 13.35 C.C. Hence 3.948 C.C. used for myricine = 2.6674 grm. or 89.05 per cent. Total, 104.16 per cent. 8.1626 grm. used 2.75 C.C. alc. Kl30 (10 C.C. = 3.681 C.C. n. acid) = 1.012 C.C. N.S., or 04149 grm. or 13.12 per cent. cerotic acid. Total alc. KHO taken 50 C.C. = 18.405 C.C. N.S. Titrated back with 18.26 C.C. n. acid. Hence 4.133 C.C. N.S. used for myricine = 2-7939 grm. or 88.66 per cent. Total, 101.78 per cent. 4.4360 grm. used 6.76 C.C. a h KEIO (10 C.C. = 2.995 o,c. n. acid) = 1.722 C.O. N.S. or -7058 grm.cerotic acid = 15-91 per cent. Total taken 50 0.0. = 14.975 C.C. N.S. Titrated back with 7.53 C.C. n. acid. Henee 5-728 C.C. used for saponification of myricine = 3.8687 grm. or 87.21 per cent. of myricine. Total, 103.12 per cent. 495972 grm. used 4.56 C.C. alc. KHO = 1.363 C.C. N.S. = -5585 grm. or 12.15 per cent. cerotic acid. Total Ecolution taken 50 C.C. alc. KHO = 14975 C.C. N.S. Titrated back with 7.52 O.G. n. aoid. Hence 6.092 C.C. used for myricine, corresponding to 4.1182 grm. or 89.58 per cent. of myricine. Total, 101.78 per cent. 13. 14. 15.'to THE ANALYST. 16. 4.2222 grm. used 4.73 cc. alc. KHO = 1.417 c.c cent. cerotic acid. Total taken 50 C.C. alc. KHO = 14.975 C.C. N.S. Hence 5.478 C.C. used for myricine = 3-7031 grm. or 101.46 per cent.17. N.S. = 058097 grm. or 13.76 per Titrated back with 8.08 C.C. N.S. 87.70 per cent. myricine. Total, 4.5222 grm. used 5-21 C.C. alc. KHO (10 C.C. = 2.70 C.C. N.S.) = 1.428 0.0. N.S., Total alc. KHO taken 51 C.C. = 13-77 C.C. N.S. Titrated back with 6.78 C.C. n. acid. Total, 101.25 corresponding to a5834 grm. or 13.49 per cent. cerotic acid. Hence 5.567 C.C. mod for myricine = 3-7633 grm. or 87.76 per cent. per cent. IS. 4.2082 grm. used 5.48 C.C. alc. K3O (10 C.C. = 2.675 C.C. N.S.) = 1.466 C.C. N.S., or *6011 grm. or 14.28 per cent. cerotic acid. Total alc. KHO taken 50 C.C. = 18.375 C.C. N.S. Titrated back with 6.51 C.C. n. acid. Hence for myricine 5.899 0.0. = 8.6497 grm. or 86-73 per cent. myricine. Total, 101-01. per oent. The eighteen samples, the results of which are given above, are all English.The following are foreign waxeg, obtained direct from the importers :- 19.-UNITED STATES.-BROWN WAX. 2.9135 gin. used 2.91 C.C. alc. KHO (10 C.C. = 3.701 C.C. n. acid) = 1.077 c.c.N.S. Total alkali added 49*97 C.C. = 18.494 C.C. N.S. Titrated back with 18.62 C.C. N.8. Total 103.25 = -4416 grm. or 15.16 per cent. cerotfc acid. Hence for myricine 3-19? C.C. = 2.5668 gnn. or 88.09 per cent. myricine. per oent. SO.-WAGASCAR. 4.3301 grm. used 3.87 C.C. alc. KHO, corresponding to 1.432 C.C. N.S. = *5872 grm. or 13.56 per cent. of cerotic acid. Total alkali added 50.03 C.C. = 18.516 C.C. N.S. Titrated back with 11.44 C.C. Therefore 5.644 C.C. used for saponification, equal to 3.8158 grm. or 88.11 per cent. of myrbine. Total, 101.61.S~.-XAURXTIUS.-BROWN. 5.1666 grm. took for cerotic acid 5.20 C.C. alc, KHO (10 C.C. = 8.16 C.C. n. acid) or 50 O.C. added for saponification. Titrated back with 7.41 C.O. N.8. Hence myricine 1.643 C.C. N.S. = *6736 grm. or 33.04 per cent. cerotio acid. took 6.747 C.C. = 4*5609 grm. or 88.28 per oent. Total 101*32 per cent. S~.-MAURITIUS.-DABK BROWN. 8.6639 grm. required 2.15 O.C. ale. KHO = 1.087 C.C. N.S. (10 C.C. = 5.106: H,SO,). Heme myricine -4467 grm. or 12.17 per cent. Total solution taken 40.26 C.C. = 20.553 C.C. n. H,SO,. Titrated back with 14.28 0.0. acid. Therefore used for saponification 5.186 C.O. = 3-5057 grm. or 96.68 per oent. myricine. Total, 10745 per cent. 23.-NAURITIUS.-Dmn BROWN. From same consignment as previous ample, but different in colonr.3.4758 grm. took 3.68 C.C. alc. KHO (10 C.C. = 3.16 C.C. N.S.) = 1.163 C.C. N.S. = 50 C.C. alp. KHO = 15.80 C.C. N.S. taken. Titrated back with 9.68 C.C. H2SO,. Total, *4768 grrn. or 13.72 per cent. oerotic acid. Hence used for myricine 4.937 C.C. = 3.3874 grm. or 96.02 per cent, myrioine. 100.73 per cent.THE ANALYST. 21 ~~ ~ 24 .-MA.URITIU S . 3.7777 grm, wed 2.47 C.C. alc. KHO (10 C.C. = 5.125 C.C. N.S.) = 1.266 C.C. N.S. Total alkali taken 40.17 C.C. = 20.587 C.C. N.S. Titrated back with 14-01 C.O. Hence, for saponification, 5,311 C.C. = 3.5902 grm. or 95.04 per cent, myricine. 54037 grm. took 5.40 C.C. ah. KHO (10 C.C. =5 3.16 C.C. N.S.) = 1.706 N.S., or 06995 grm. = 13.44 per cent. cerotic acid. Total taken 50.9 C.C. KHO = 16.08 C.C. N.S. Titrated back with 7.24 C.C.H,SO,. Hence, myricine used 7.184 C.C. = 4.8926 grm. or 92-67 per cent. Total 106.11 per cent. = *5189 grm., or 13.74 per cent. cerotic acid. n. acid. Total, 108*78 per cent. 2 5 .-MAURITIUS .--LIQHT BROWN. ~~~.-JAMAICA.-BRIGIIT YZLLOW. Did not saponify perfectly clear. 3.8378 grrn. took 1.98 C.C. alc. ICHO (10 0.0. = 6.377 C.C. N.S.) = 1.263 C.C. N.S. c *6177 grrn., or 13.49 per cent, cerotic acid. Total ~lcoholic ICHO taken 50 C.C. = 31.885 C.C. N.S. Titrated back with 25.79 C.C. acid. Hence, 4.832 used for myicine= 3-266 grm., or 85-12 per cent. Totd 98.61 per cent. 27. -JAIlAICA. Did not saponify quite clear. 4.8946 grm. used 5.40 C.C. alc. KHO (10 C.C. = 3.16 C.C. HzSOq) = 1.706 N.S. = -6995 grm., or 14.30 per cent. cerotic acid.Total taken, 50 C.C. =: 15-80 C.C. N.S. Hence, for myricine used, 6.214 C.C. = 4.1986 grm., or 85.78 per cent. myricine. Total, 100*08 per cent. J7198 grrn., or 13.44 per cent. cerotic acid. myricine used 7.149 0.0. = 4.8327 grrn., or 89.00 per cent. Total, 102.44 per cent. Titrated back with 7.88 C.C. EI,SO,. 28.-MOGADORE. 5.4298 grrn. took 6-10 C.C. alc. KHO (10 C.C. = 2.92 C.C. N.S.) = 1.781 C.C. N.S. z Total alkali taken, 50 C.C. = 14.60 N.S. Titrated back with 4-67 c,c. H,SO,. Hence, 2O.-MOGADORE. 3.1366 grm. required for acidity 2.08 C.C. alc. KHO (I0 C.C. = 5.125 N.S.) = Total KEO added, 3994 C.C. = 20.47 C.C. N.S. Titrated baek with 14.65 0.0. N.S. TotaI, 1.066 C.C. N,S. = -4371 grrn., or 13.93 per cent. cerotic acid. Hence, used for myricine, 4.753 C.C.= 3.2130 grrn., or 102.44 C.C. myricine. 11697 per cent. 30.--lWOGADORE. Very goft, intenaely acrid and hot. 3.4884 grm. required 2.16 C.C. alc. KHO = 1.107 C.C. N.8. for acidity, corresponding to 04539 grm., or 18.02 per cent. cerotic acid. Alcoholic KHO added 4046 C.C. = 20.684 C.C. N.S. Titrated back with 13.50 C.C. N.S. Hence, for myricino, 6.077 0.0. = 4*1080 grm., or 117-86 per cent. Total, 130.88 per cent. 4.8081 grm. took 6.50 C.C. alc. HHO (10 0.0. = 2.675 C.C. N.S.) = 1.739 C.C. N.S, = *7180 grrn,, or 16.55 per cent. cerotic acid. Total do. KHO taken, 50 C.C. = 18.375; C.C. N.S. Titrated back with 6-30 C.C. N.S. Myricine used 5.336 C.C. = 5.6071 grm., or 83.78 per cent. Total, 100.28 per cent. ~~.-MELBOURNE.-GREY WAX. ~~.--G~AMBIA.-D~K BROWN. 806286 grm. uged 1.92 C.C.ale. KHO (10 C.C. = 6.417 C.C. N.S.) = 1.232 C.C. N.S. = $051 grrn., or 13.92 per cent. cerotie acid. Alcoholic KHO added, 32 C.C. = 20.53 C.C. N.S. Titrated back with 14.51 c.c, N.8. Used for saponification, 4.79 G.C. = 3,2380 grrn., or 89.24 per cent. myricine. Total, 103.16 per cent.I THE ANALYST. ~~.-MELBOURNE.-PALE YELLOW. ._____ --- .--- ___ 32 3,2720 grm. took 2.53 c.e. ah. KHO (10 c.c, = 4-16 c.c.N.S.) = 1.052 C.C. NbSb = -4315 grrn,, or 13.18 per cent. cerotic acid. 41 C.C. alc. EHO = 17.056 C.C. N.S. taken. Titrated back with 11.76 C.C. Na8. Eence, 4.244 C.C. used for myricine = 2-8619 grrn., or 87.47 per cent. Total, 100-65 per cent. 3.5165 grm. used 2-69 c,c. alc. KHO (10 C.C. = 4.163 C.C. N.S.) = 1.12 c.c.N.S. = 3.9018 grm, took, for myricine, 5-356 C.C.N.S. = 3.6207 grrn., or 9279 per cent. ~C.-SYDNEY.-GREY WAX. *4592 grm., or 13.06 per cent. cerotic acid. myricine. Total, 105%! per cent. ~~.-SYDNEY.-PALE YELLOW. 3.7613 grm. used 2.90 C.C. alc. KHO = 1-207 C.C. N.S. = ~4949 grm., or 13.16 per cent. cerotic acid. 41 C.C. alc. KHO added = 17*068 C.C. N.S. Titrated back with 10.93 C.C. N.S. Hence, 4.931 C.C. were used for saponification, corresponding to 3.3334 grrns., or 88.62 per cent. myricine. Total 101-78 per cent. These results may be conveniently examined in two divisions ; samples 1-18, corn- prising samples from various English sources ; and 19-35, being exotic productions. If we exclude from Division I., No. 4, fused by myself from the comb, on account of the sample having been palpably impure with auspended matters which could not be aeparated, the quantity of wax being small ; and sample No.10, having been made from comb containing foundation,” it is at once seen that the figures fluctuated only between comparatively narrow limits. Only one of the samples contained less than 13 per cent. of free acid calculated as cerotic acid, four between 13 and 14, seven between 14 and 15, and four between 15 and 16, the ave~age amount of cerotic acid being 14.40 per cent. The saponifiable matter, calculated as myricine, was in one case leas than 86, in oue between 86 and 87, in six between 87 and 88, in four between 88 and 89, and in four between 89 and 84.6, the average being 88.09 per cent. In all cases is the sum of cerotic acid plus myricine Homewhat higher than 100, it reaching on the average 102.49.While these figures con- dusively prove that English bees’ wax coneists almost completely of cerotic acid and of myricine, they also corroborate the existence of a small quantity of a substance of lower molecular weight in wax, probably Lewy’s ceroleine, I thought it possible, that during the prolonged boiling of the alcoholic potash solution gome of the alkali might be neutralised by the silica of the glass, the quantity destroyed of course counting in the analysis as myricine, and thus bringing up the totals to upward of 100. But this is not the case, for in a blank experiment not the slightest diminution of strength could be observed after 50 C.C. of alcoholic potash had been kept briskly boiling for one hour.It must be oonsidered to be established by these results, that the composition of wax is not liabIe to the enormous variations which the figures quoted in an early part of this paper would lead to infer. On the contrary, ths relation between the amounts of cerote‘c acid and of myricine i s remarkabls for its constancy. The observation of Dumas and Milne- Edwards, who established that the wax is formed by the bees themselves, and is a true mima1 secretion, are indirectly borne out by my figures, for it seems highly improbableTHE ANALYST. 25 that a product consisting of a mixture of two substances could be obtained of such striking constancy if it were collected ready formed from the plant. The case is very similar to that of milk and butter, secretions which under normal circumstances are also subject to but little fluctuation in composition.In English wax the proportion of myricine to cerotic acid is 6.117 : 1. The fluctuations are much more considerable in the case of the exotic samples ; but I am very strongly of opinion that, although all allowance must be made for the fact that these foreign samples, coming as they do from all quarters of the globe, are doubtless derived from a great variety of different insects, the fluctuation is due more to man who collected the samples and put them into marketable form than to the insects who produced them. For this belief testifies the observation, that, while some of the samples of Mogsdore and Mauritius wax corresponded in composition with English samples, others showed s great increase in the saponifiable matter, calculated as myricine.The soft, smeary Nogadores were obviously mixed with some fat : some of the Mauritius specimenrr appeared burnt in process of melting out of the comb, And, lastly, it is not a little significant that the market price of the 4‘ normal ’’ samples is considerably above that of the specimens which gave excessive totals. I think I am justified to hold, that the analyses of the foreign samples strengthen the conclusions I have drawn from those of English wax. More evidence may be desirable, but this can only be obtained by the analysis of authenticated genuine samples so difficult to obtain. Meanwhile it will be well if I confine my observa- tions as to adulterations of wax and their detection to the home product* The organic substances, which may be, or have been known to be, used as adulterants of wax, may be conveniently grouped in three classes :- I,, Ban, substances ; XI*, NEUTRAL BUT SAPONIFIAB~ compounds ; and, III., Matters INDIFFERENT TO ALCIOHOLIU POTASH.The first olass embraces the Solid fatty acids, mainly palmitic and stearic, and the acids which constitute resin, particularly sylvic acid. The second group is made up of neutral solid glycerides-viz. : stearine and palmitine- of Japanese wax, spermaceti, and Carnauba wax. The only representative of the third division, for practical purposes, is paraffin. Solid alcohols of high molecular weight, such as cetylic or myricylic, would also belong to this class ; but, being non-marketable, they need hardly be taken into account.Now it is remarkable, and of the greatest importance to the analyst, that both compounds of which wax is composed possess a higher equivalent weight than any other substances belonging to the fatty acid series occurring in nature.* The molecular weight of cerotic acid is 410, that of myricyl palmitate 676. Stearine, indeed, has a molecular weight of 890, but containing the acid group C,,H,,O three times-its neutralisation-equivslent is only 296-7. In addition to this fact, there are no fatly csompounds available for the adulteration of wax possessing a higher number of carbon atoms than stearic acid-c,,H3,0,. There is, con- sequently, a very large differenoe between the molecular weights of cerotic acid, and especially of myricine, and any possible substitutes.CLASS 1.-Let us imagine, then, that a fatty acid-say steario-be used with * Excepting the fatty add recently discovered by Mr. Kingzett in cocoa butter.24 THE ANALYST. - bees' wax. The neutralisiag power would of course increase; but not only to an extent equal to the quantity added, but much more considerably, for 284 parts of stearic acid will count for as much as 410 parts of cerotic acid ; 1 per cent. of stearic acid would, therefore, be reckoned as 1.443 per cent. of cerotic acid ; whilst one of palmitic would correspond to 1.601 of cerotio acid. Since neither pure palmitic nor stearic acids are likely to be employed, but mixtures of these acids in variable proportion, I prefer to calculate that each per cent. of f a t t y acid, taking tlte same a3 CqH340a, i s equal to 1.518 of cerotic acid.Whilst by the addition of fatty acid the acidity would thus increase, the proportion of saponifiable matter (myricine) would be decreased in direct proportion to the quantity of fatty acid added. Thus, a mixture of five equal parts of wax and fatty acid would yield 83.10 per cent. of acidity cdculated as cerotic acid, and 44.04 per cent. of myricine. In the case of resin the conditions would be similar, although the differences would be less pronounced. Ordinary colophony mainly consists of sylvic acid, generally assumed to be C,H,,O, (equiv. 302), but from L number of experiments which I made on the neutral- ising capacity of two ordinary commercial samples, I find its cornposition more nearly to correspond with the more recent formula, C4T36405, the acid being taken as debzlsio (equiv.336). One grm. of resin neutralised respectively alc, KHO corresponding to 31038 and 3.046 0.0. normal solution. Hence the total equivalent of the substance is 329. One per cent. of resin would, therefore, if mixed with wax, be calculated as 1.246 per cent. of cerotio acid, whiIst it would depress the myricine, like fatty acids, in exact proportion to its amount. It need hardly be said, that by titration alone we measure only the total acidity, and do not distinguish between fatty acids or resin, although the amount of depression in the proportion of mgricine, in relation to the rising in the acidity, might furnish some indication as to the nature of the adulterant. I have made no experiments in this direction; but if the exact composition of the acid admixture had to be ascertained, no doubt the well-known method of Barfocd, depending upon the difference of the behaviour of fatty and resin soaps with ether-alcohol, would give the information desired.CLASS 11.-Coming to the second group of possible admixtures-namely, sapOnifiaI.de, neutral substances-the line of reasoning advanced in the oase of Class I. renders it evident that, if any neutral glyceride be added to wax, the percentage of saponifiable substanoe, calculated as myricine, must increase in a much larger proportion than the actual percentage of fat added. Taking the average between tri-palmitine and tri-atearine (molecular weights 806 and 890 respectivdy), we find that 282.8 parts of fat neutralise as much alkali on saponification as 676 parts of myricine; or, in other words, 1 part o f f a t will count as 2.891 parts of myricine.It will, of ccurse, cause a depression in the amount of cerotic Bcid directly corresponding to the quantity of admixture, Japan wax, stated to consist entirely of palmitine, would be indifitinguishable from ordinary fats, I thought it well, however, to verify the statements which are made in the text books in reference to the composition of this ourious substance. 3.1123 grm. of a pure sample of Japan wax were heated with alcohol. The solution was distinctly acid to phenolphthalein, alcoholic potash solution czorresponding to 0766 C.C. N.S, being neoesssry to produce a pink tint. Thig corresponds to -1935 grm., or 6.21.per25 ---_ --- ---_I_ THE ANALYST, cent, of palmitic acid. corresponding to 2.9295 grm., or 94.12 per cent. palmitine. 10.90 C.C. of N.S. were required for complete saponification, Total, 100*33 per cent. 3.6334 grm. of another, somewhat yellow, sample, ased for total acidity 2.693 C.C. N.S., oorresponding to -4334 grrn., or 12-93 per cent, of palmitic acid. For saponification, further 12.556 C.C. N.S. were used, equal to 3-3200 grm., or 91.58 per cent. palmitine. Total, 103.31 per cent. These results show that Japan wax contains, besides a saponifiable fat, a considerable percentage of free fatty acid. There can be little doubt, from the Batisfactory approach to 100 of the sum of both, that the mid, both free and combined, is really polmitio acid. free fatty acid and of fat, and there would be a rise in both cerotic acid and in myricine.An addition of Japanese wax to bees’ wax wodd, therefore, amount to addition of both Spermaceti constitutes the link between fats and wax, it being stated to consist mainly of cetyl palmitate, C,,H,,0,C,6€€330 ; but, according to Heintz, it also contains stertric, myristic, cochic, and cetio aoids, and the alcohole with 12, 14, 16, and 18 carbon atoms. 8.4443 grm. of a very fine specimen of spermaceti, treated in the manner described, were found to be quite free from uncombined acid. Alcoholic potash corresponding to 7-97 C.C. N.S. was used for saponification, equal to 3.7776 grrn., or 109.68 per cent. cetyl palmitate. Another specimen was also gee from acidity.4.3510 grm, used for saponification 9.875 per cent. N.S., corresponding to 4.7400 grm., or 108.94 per cent. cetyl palmitate. A third sample was very slightly acid, the acidity corresponding to 43. per cent. of palmitic acid. 8.6938 grm. used for saponification-after substraction of the volume neutralised by the free acid-8.475 C.C. of N.S., corresponding to 4.0780 grm., or 110*41. per cent. cetyl palmitate. It is evident, from these figures, that spermaceti includes a notable amount of one or more substances of lower molecalm weight than cetyl pahifate. Taking the average of the three analyses, the molecular weight of spermaceti is 437.6, instead of 480, corresponding to cetyl palmitate. Spermaceti lies, therefore, almost exactly in the middle between fat and myricine, the molecular weights being 282*8,437*6, and 676 respectively.* Carnauba wax has been but very little studied, and I cannot add much to the small amount of information available. According to Maskelyne, it contains free myricylic alcohol and several other similar alcohols, whilst Berard states it to contain free cerotio mid.The only Ecpecimen 1 tested showed distinct aoidity. 8,6783 grm. neutralised alcoholic potash equal to 0543 C.C. N.S. This would oorrespond to *2226 grm. or 6.09 per cent. of free cerotic acid. For saponification li*0!32 O.C. N.S. were used, corresponding to 8.4046 grm. or 92.58 per cent. of myricine. Total, 98.67 per cent. * The price of spermaceti being equal to that of the best qualities of wax, and superior to that of the lower qualities, renders its employment as a wax adulterant very doubtful.As, on the contrary, wax is not unfrequently mixed with spermweti in the manufactnre of sperm oandlee, the analyses quoted may here find 8 place.I 26 TEE ANALWT, As far as its behaviour with alcoholic potash is concerned, Carnauba wax therefore very closely resembles ordinary bees’ wax. Its physical properties are, however, so very different, its solidity and hardness being remarkable, that I believe it to contain compounds of higher molecular weight than ordinary wax. In the present state of our knowledge of this curious substance, material for the analytical distinction between it and bees’ wax is wanting. The great and somewhat embarrassing similarity in its neutralizing power and that of ordinary wax is, however, a matter of little coiisequence, as Carnauba couId hardly be used by itself as a wax adulterant. I t would serve rather for the purpose of hardening samples mixed with fats or other soft subatanoes.The different substances described in Class 11. saponify with different degrees of rasdiness. Fat, including Japan wax, breaks up very rapidly ; next comes spermaceti; Carnauba, wax much more slowly, its melting point being higher than the boiling point of the spirit I emplcyed. Ordinary wax is, in this respect, most tenacious of all. CLASS 111.-As to the repreaentative of the third class-inert substances--viz., paraffin, but little need be said. An addition of paraffin depresses both cerotic acid and myricine, their proportion not being altered.If the mixture contains nothing but wax and paraffin the deficiency between the amounts of cerotic acid plus myricine and i i i O may be taken as the percentage of paraffin. Its presence cannot well be overlooked during saponifiaation, paraffin being but little soluble in alcohol. It adheres to the sides of the flask in a characteristic manner. The specific gravity of the sample would also be lower than that of the pure wax. But it is quite easy to imagine mixtures of fatty acids, fat and paraffin, quiet devoia ot wax, yet giving on analysis, in the manner proposed, results identical with those yielded by pure wax. Thus a mixture of 9.48 per cent. of fatty aoids, 86.84 per cent. of fat, and 58.68 per cent. of paraffin would show on analysis 14-40 per cent.of cerotic acid and 88.09 of myricine. It becomes necessary, therefore, to estimate the paraffin directly, and not by difference. This purpose may be effected by heating a weighed quantity of wax with from five to times its bulk of sulphuric acid to about 130° C. Volumes of sulphurous acid are give off, the fluid frothing and rising considerably. The vessel in whioh this treatment i, accomplished must therefore be capacious. After about ten minutes heating the mr becomes almost solid. It is allowed to cool, the acid removed by washing with water ; !’ - residue is exhausted with ether, preferably in a Soxhlet tube. The paraffin thus obtainea is again treated with a little sulphuric acid, to remove a small quantity of wax which generally escapes destruction during the first charring process.It is again washed frc from acid and purified with ether. Having thus obtained the percentage of paraffin in any wax mixture, the composi- tion of 100 parts of the remainder may be readily calculated, as follows :- Let A be the percentage in the paraffin free mixture of free acidity, cahulated &I cerotio acid ; B the percentage of saponifiable matter calculated as myricine. Let X be the unknown percentage of cerotic acid, Y of fatty acid, Z of myricine, and W of fat in any mixture contsining fatty acid, fat and wax, either separately or all together,TEE ANALYST. 819 We know tbat X + 1.518 Y = A. 2 + 2.391 W = B. Z = 6.117 X. (3) x + Y + z + w = 100. (4) (1) (2) A-X From (1) Y = - 1.518 B--6.117 X From (3) Z = 6.117 X and from (2) and (8) W = 2-391 Substituting these values of Y, 2 and W in equation (4) we get A-X B-6*117 X + 6.117 x 4- 2,391 = 100.From this *+1.518 362.954-2 591 A-1*518 B or 14.161 We would thus obtain the percentage of cerotic acid. This, multiplied by 6.117, The real cerotie acid, subtracted from A, and the remainder divided by 1.518 gives the percentage of added fatty acid$. The real myricine, subtracted from B, and the remainder divided by 2.891, gives the percentage of fat. We thus obtain the percentage composition of the mixture, apart from any p a r a h it may contain. I t is then, of course, easy to calc~ilate the percentages obtained upon the The following analyr~es of mixtures will show tbat the above formuJs, based solely upon 2eoretical considerations, hold good in actual working.Allowance has of course to be made for the fluctuations in the composition of pure wax itself, for the fact that fatty acids re not likely to be mixtures of exactly equivalent parts of stearic acid and palmitic acid, nor fats of stearin and palmitine, as assumed in the formuls. The mixturss which I analped were, in composition, both qualitatively and qnanti- ,ively unknown to me. Only after the analyses and calculations mere completed were the igures compared with the percentages actually used in the preparation of the test samples. give the results without seleotion :- 4.2218 grm. of a mixture used 891 C.C. alc. RHO (10 C.C. = 8.16 C.C. N.S.) = 1.286 t.e. N.S., corresponding to *5067 grm., or 12.00 per cent. cerotic mid.60 c.0. added for total saponification = 15.80 C.C. N.S. Titrated back with 7-40 C.C. ience, 7*164 C.C. N.S. used for saponification = 4.8429 grm., or 114.72 per cent. myricine. x = X = 25*649--(.1689 A + 01073 B). urnishes the mypicine, the sum of both being the percentage of u'ux in the mixture. &%iifb hb*pm*. C~~~CULATED COMPOSITION. ... " * 11*30 } Wax 80.42 Cerotic acid Myrioine ... ... ... 69.12 Fatty acid' Fat ... ... ... 19.07 ... ... *46 } Fat 19.58 AUTUAL COXPOSITION. wax .I. ... ... ... ... 79 98 Card ... ... ... ... ... 20.02 100*00 -THE ASALYt3JT. - -_ - - - - - . - .- -_ - - ._ - 28 3,8590 grm. of another mixture used for acidity 2.00 0.0. alc. KHO (10 C.C. = 8.164 Total taken, 50 C.C. = 15-82 C.C. N.S. Titrated back with 5.43 C.C. N.S. Hence, C.C.N.S.) = 0633 C.C. N.S., corresponding to *2695 grrn., or 6.72 per cent, cerotic acid. used for saponification, 90757 C.C. = 6.5957 grm., or 170.92 per cent. of myricine. From these results the following composition Cerotic acid ... ... Myricine ... ... ... Fatty acid ... L.. ... Fat ... ... ... is calculated :- &I* } Wax 48.98 37.80 65.68 } Fat 56.08 ACTUAL COMPOSITIOX. Wax ... ... ... ... ... 41.50 Lard ... ..* ... ... ... 58.70 100~00 - 4*5019 grm, used 9.55 alc. KHO = 3.022 0.0. N.S., corresponding to 1.2390 grm., Total ale. KHO taken, 50 C.C. = 15.82 C.C. W.S. Titrated back with 7.94 C.C. N.S. or 28.80 per cent. cerotic acid. Hence, for saponification, 4.858 C.C. N.S. = 3.2840 grm., or 78.34 per cent. myricine. CALCULATED CONPOSITIO-U. ... * " 12'59 } Wax 89.60 * * ' Cerotic acid Fatty acid..Fat ... ... ... none ... Myricine ... ... 77.01 . ... 10*67 } Fatty acid 10.67 ACTUA~ COMPOSITION. Wax ... ... ... ... ... 89.86 Palmitic acid * * - ... ... ... 1 0 m 100 00 - 5.8126 grm. of sation. Hence 4.6076 grm, or 159*09 per cent. cerotic acid. 60 C.C. alc, KHO taken = 18 984 C.C. Titrated back with 7.27 C.C. N.S. Therefore used for aaponification 0476 C.C. N.S. = *3218 grm. or 9-71 per cent. myricine. mixture took 85.52 c.c, alc. RHO = 11*298 C.C. N.S. for neutrali- C~~CULATED COMPOSITION Cerotic acid .., ... 1.11 Myricine ... ... ... 6.82 Fatty acid ... ... 9089 Fat ... ... ... 1.21 wax ... ... ... ..* ACTUAL COBIPOSITION. 1 wax 7.95 1 Fatty acid 92.10 9% per cent. Fatty acid ... ... ... 90.78 - 100~00 8.6662 grm.took 12.70 O.C. alc. KHO = 4.018 C.C. N.S., corresponding to 1.6474 grm. or 46.19 per cent. cerotic acid.THE ANALYST. %9 Total taken 60 C.C. rtlc. KHU = 18W34 C.C. N.S. Titrated back with 9.65 c.a. N.S. Hence used for saponification 5.326 C ~ C . N.S. =3*6004 grm. or 100-96 per cent. myricine. CALCULATED COMPOSITION. ... . * * 7*01 } Wax 49.02 Cerotic acid Myricine ... ... ... 42.91 Fatty acid.. . ... ... 25-81 Fat ... ... ... 24.28 ACTUAI~ COMPOQTYON. Wax ... ... ... ... ... 49.68 Fatty soid.. . ... * m a ... ... 25.42 Fat ... ... ... ... ... 24.90 100*00 - M1 the above mixtures were free from pardiin. In the following mixtures paraffin was on saponification Been to be present. 3.7660 grm. used for acidity 12 59 C.C. alc. KHO = 3.988 C.C. N.S. = 1.6330 grm.or 43.86 per cent. cerotic acid. Total alkali taken 50 C.C. = 15432 0.0. N.S. Titrated back with 9.60 C.C. N.S. Hence 2.237 c.c, N.S. used for saponification, corresponding to 1.5122 grm. or 40.15 per cent. myricene. 5.1186 grm, furnished 1°3988 grm. of paraffin. Hence paraffin 27-83 per cent, The mixture free from paraffin would consequently have shown-Cerotic acid 59.66 per cent., myricine 55.25 per cent. From these figures the percentage composition of the mixture calculates as follows :- * ' * ''go I Wax 40.11 Cerotic acid ..* Myricine ... ... ... 42.21 Fatty acid ... ... ... 23-65 Fat ... ... ... none Paraffin ... ... ... 27-83 AUTUAI, COMPOSIT~ON. Wax ... ... ... ... ... 49.67 Fat ... ... ... ... ... nil. Paraffin ... . * . ... ... ... 26-68 100*00 Fatty acid... ... ... ... ... 23 80 - 8.4219 grm. yielded 4806 grm*, or 16-96 per cent. cerotie acid, and *7328 g;rm., or 2141 per cent, myricine, Tbe mixture contained paraffin, the presence of which wag evident both during saponification, and proved by the low sum of the percentages of cerotic acid plus myrioine, I did not estimate by direct experiment the percentage of paraffin ; but, secing that the proportion of acidity to myricine was in excess of that obtained innatural wax, I concluded that the mixture consisted of wax, fatty acid, and paraffin. 21.41 per cent. myricine correspond 5.50 per cent. cerotic acid. To Hence- Wax ... ... ... ... 24.91 per cent. Fatty mid ... ... ... 8.86 Paraffin ... ... ... ... 66.28 100*00 - ACTUAL COMPOSITION. Wax .. . . . . ... 26#01 ... 9'16 73.99 para-ffin candle. Fatty acid Paraffin ... ... 64.83 I 4.2589 grm. of a mixture gave *6719 grm., or 15.85 per cent. cerotic acid, and 2.3596 grm., OF 55.19 per cent myriciue. This calculated like the previous sample gives :- Cerotic acid My rioia e Fatty acids Paraffin ... Wax ... Fatty wid Paraffin ... ' * * ... 56.19 "02 } 64.21 per cent. wax. ... 4*48 ... 3191 100 00 - AUTUAG Comosirrox. ... 66.67 *.' ... 29.20 4*13 } 53438 per oent. paraffin candle. It must be remarked, in reference to the two last analyses, that it is not legitimate generally to take the percentage of paraffin by difference, for in the simultaneous presence of both fat and fatty acids the saponifiable matter could not simply be taken to be myricine. I hope, then, to be justified in believing that I have established, by crucial and careful experiments, that, both the line of argument adopted, and the formnls developed by me, are substantially correct, my researches furnishing a rapid and moat simple method for the analysis of yellow wax, the results obtained giving at once information as to the nuturd of the additions and their guantities.Physical indicathns and especially estimations of specific gravity should not, however, They may both corroborate the analytical results and lead to the detection be disregarded. of substances liable to be overlooked. Thus, while paraffin and fat are lighter than wax, fatty acids are somewhat, and resin is much, heavier ; an abnormally low specific gravity would cause us at once to look after the former, and unusually high gravity after the latter.In the case of resin such an indica- tion ia especially valuable, as without a hint its presence would be liable to be overlooked &nd its quantity bo be dated in terms of fatty acid.The following specificr gravities relate to samples previously referred to in this paper :- WAX. Sample 1 *9656 ,, 2 *9656 Japan WBX, 1 ... ... ... 099 93 ,, 3 *9663 ,, 2 ... ... ... -9953 ,, 5 -9655 Spermaceti, 1 ... ... ... -9162 ,, 7 09671 Carnauba wax ... ... ... 1*0011 ,, 8 9673 Resin ... ... ... 1.0865 ,, 12 *9655 Paraffin.. . ... ... ... *9171 ,, 16 9675 Fatty mids ... ... ... 1.002 ,, 26 09673 ,, 26 *9637 ,, 27 09655 ,, 29 *9628 ... The following are instances of undoubtedly adulterated samples of wax :- Sample of 6 6 cornb$ou9zda#ion" : 3*7550 grm.gave *3136 grm. or 8.35 per cent. of cerotic acid, and 1*3386; grm. or 35*67 per cent. of myricine. Contains much paraffin, Assuming the absence of fat the composition of the sample calcnlatee as follows :- Ceroticr acid ... Ii'83 } 4 1 W per cent. wax. My ricine ... 36.67 Pitty acid ... 1.66 . Paraffin ... ... 56.84 -- 100*00 Another specimen of '' foundation " : 4.2764 grm. gave *7929 grm. or 18.54 per cent. cerotio acid, and 5*13'7S grm. or 73.86 per cent. myricine. Contains paraffin. Composition calculated as above. Cerotic acid ... 11.99 85.35 per cent. wax, Mydcine ... 75-36 f Ftlttv actid ... 4-31 Paralfin . . ... 10.84 - 100*00 It is noteworthy, that, generally, when paraffin is admixed with wax, the acidity will be found increased, as in the two previous samples: that is to say, cdulteration with paraffin is almost invariably accompanied by admixture with fatty acids. I have no doubt that the explanation is found in the fact, that pure paraffin but rarely occurs in retail commerce, all paraffin candles contaking a variable proportion of free fatty acid, added to diminish the transparency of the pure hydrocarbon.When I examined some of the test mixtures referred to, I was at first somewhat puzzled by finding added fatty acid, whilst I wag informed that none had been admixed. It was soon found, however, that the paraffin candle employed in the preparation of' the mixtures contained no less than 12.4 per cent. of fatty aoid. A light yellow rrample of wax, L 6 warranted genuine " by the vendor, gave 10.47 per cent.cerotic acid and 69.30 per cent. myricine. From thia it follows that the sample con- sisted of Wax ... .*. ... ... be. 79.77 P&r&ffin ... ... ... ... *** 20.23 100*00 -32 THE ANALYST. In this case the proportion of cerotic acid to myricine is practically normal. Another sample, obtained by purchase, gave cerotic acid 18.15, mgriche 118.97 per cent, It was free from paraffin. CALCULATED COMPOSITION. Wax ... ... ... ... 70.60 per cent. Fatty acid ... ... ... 5.42 Fat ... ... ... ... 24.38 lO0.40 - In conclusion, I would provisionally warn analysts not to adopt the figures constituting the basis of this paper in judging of' tho composition of bleached wax. It is quite possible -indeed, I haye every reason to believe--that the changes due to some of the bleaching processes aiter the composition of the wax more deeply than is generally supposed.Unfortunately, it is still much more difficult to procure absolutely genuine samples of white wax than of the crude yellow product. I have much pleasure in acknowledging the valuable help given me duriug the progress of this laborious and extended investigation, by my friend, Mr. B. Halford, RSc., and my pupils, Messrs. C. A. Smith and G. Borrett; also to a number of friends, who have moat kindly supplied me with most of the pure samples of wax referred to in this paper. The President, in thanking Mr. Hehner for his paper, said that many of the combs received from America were entirely artificial. Dr. Muter said that paraffin was practically the only wax adulterant used.As to specific gravity his experience was that a wax containing paraffin had a low speoific gravity, and when fatty acids had been added, as well as paraffin, the fatty acids did not much affect the gravity. He had sometimes come wonderfully near in mixtures of wax and paraffin with the gravity alone. Dr. Dupr6 said he congratixlated the Society on beginning the new year with such an interesting paper. The specific gravity wa,s taken as solid, What precautions did Mr. Hehner take to see that he always got a solid lump, and that his alcohol with au hour's boiling did nut a&& the btandsrd ? Koettstorler, when he first introduced his method, boiled two quantities of alcohol, one with which he saponified and the other blank, and he came to the aomlusion that the boilingdid affect the alcohol. Mr. Kingzett said he felt how wide a field thcre was for research on tbe subject. In his own investigation into cocoa butter, he had found two most interesting compounds-one with the highest molecular value known. He should like to have the opportunity of investigating some of those as to which Mr. Hehner had given them such valuable informa- tion. Mr. Hehner, in reply to the last question, said wax had to be boiled a long time before any result was obtained. If wax were boiled for ten minutes only, the resin is said to be dissolved out, and the wax was not attackod. As to Dr. Muter's remarks, he (Mr. Hehner) would take the specific gravity as a kind of indication, but he would not rely on that as to the composition of a sample. Supposing a normal gravity were obtained, the sample might yet be a considerably adulterated one; or, supposing the gravity was too low, it did not follow that panffin had been added. He entirely dissented from the statement that paraffin was the only adulterant, but it wag no doubt used more than anything else. It might be added to wax without it showing physically, the structure and colour of the mixture differed but little from those of pure wax, while if a little €at were added it made the substance greasy. In fact, he had found one sample adulterated with fat. Referring to Dr. Dupre's remarks, he had only made one blank experiment of boiling alcohol for an hour with alcoholic potash. He had simply taken ordinary methylated spirit to which a considerable quantity of alkali had been added. He distilled it over so that it was absolutely free from acids. He made all his alcoholic potash in thrtt way. He never used ordinarp spirit because it ooloured too yellow with potash. AS to taking the gravities, if the substance were filled in a sufficiently sized tube, the cavity was not wide enough to suck in any air. If large quantities like those he took were worked on, the influence of bubble8 waa redwed to a minimum. I hope very soon to recur to this subject. There were two points he wished to refer to. What was the result of saponifying bees' wax with aqueous potash 3

ISSN:0003-2654    

DOI:10.1039/AN8830800016

出版商:RSC    

年代:1883

数据来源: RSC