THE ANALYST. 409 ORGANIC ANALYSIS. Detection of Methyl Alcohol. H. Scudder and R. B. Riggs. (Jozm. Anzer. C'h~wz. Soc., 1906, xxviii., 1202-1204.)-0xidation of the solution by a hot copper spiral, subsequently testing for formaldehyde by heating with milk and HC1 containing Fe,CI,, is unreliable for the detection of methyl alcohol, 10 per cent. aqueous solutions of ethyl alcohol, acetic acid, and acetone, all giving reactions indistinguishable from that obtained with pure methyl alcohol. The following modification of the Sang% Ferribre-Cuniasse test shows 2 to 3 per cent. of methyl alcohol in ethyl alcohol. To 10 C.C. of the aqueous solution to be tested add 0.5 C.C. concentrated H,SO,, and 5 C.C. of a saturated solution of KMnO,, the temperature being maintained at 20' to 25' C.After two minutes add sufficient sulphurous acid to give a colourless solution, boil till free from SO, or acetaldehyde, and apply the resorcinol test for formaldehyde. The production of a pink ring is usually sufficiently characteristic to prove the presence of methyl alcohol, but the appearance of flocks, which can often be developed410 THE ANALYST. by standing for one or two hours and then heating the upper layer to boiling, affords positive evidence of its presence. The use of HC1 instead of,H,SO, in the resorcinol test prevents any darkening due to overheating or charring, but lessens the delicacy .of the reaction. W. H. S. The Formation of Formaldehyde in the Caramelization of Sugar. A. Trillat. (Bull. Xoc. Chim., 1906, xxxv., 681-685.)-0n heating sugar, traces of formaldehyde are given off even at 125" C., and at 150" C. the aldehyde is liberatea in greater quantity.Analyses of the vapours emitted at 200" C. showed the presence of 0.2 to 5.7 per cent. of formaldehyde, and the residual caramel contained up to 0.27 per cent. of polymerized formaldehyde, probably in the state of trioxymethylene. The amounts produeed were found to vary with the method of heating, the nature of the vessel, and the purity of the sugar. Experiments with five samples of commercial caramel showed that two were free from formaldehyde, whilst the others contained from 0.030 to 0.325 per cent. The author points out that this accounts for the antiseptic properties of caramel. Fresh urine, for example, treated with a sufficient quantity of caramel no longer putrefies.The Bacillus coZi comrnunis was destroyed by being left for fourteen hours in contact with a 10 per cent. solution of caramel. c. A. Rl. The Determination of Formic Acid by Potassium Permanganate. J. Klein. (Bey., 1906, vol. 39, p. 2640 ; through Chent. Ztg., 1906, XXX., Eep., 329.) -Grossmann and Aufrecht's recent paper on this subject has caused the author to refer to his method, published nearly twenty years ago. It consists in oxidizing formic acid in a boiling alkaline solution by means of potassium permanganate, then adding an excess of oxalic acid and dilute sulphuric acid, and finally titrating the excess of oxalic acid with permanganate. A. G. L. On the Determination of Malic Acid. H. Cantoni and M. Basadonna. (BuEE.SOC. Chim,, 1906, xxxv., 727-737.)---The determination of malie acid by oxida- tion with potassium permanganate in acid solution has yielded absolutely discordant results in the authors' hands, whatever modification of the method was employed. They have also obtained bad results with the various methods of precipitating the acid by means of lead acetate, the highest yield being 91.41 per cent. of the theoretical amount. I n their opinion, there is as yet no method capable of deter- mining malic acid in the presence of other organic acids, and they recommend the study of the solubility of rnalates in different solvents to find the basis for a reliable process. They themselves have determined the solubility of malatcs of the alkaline earths in water. The strontium salt is less soluble at 20" to 30" C., but much more soluble at higher temperatures than the calcium and barium salts, and its solubility increases enormously with the rise in the temperature.Calcium malate is the least soluble of the three salts at 35' C., and its solubility decreases with the rise in temperature. The barium salt is slightly more soluble in hot than in cold water (cf. ANALYST, xxxi., 300). C. A. M.THE ANALYST. 411 On Melezitose and Turanose. G. Tanret. (BUZZ. SOC. Chinz., 1906, xxsv., 816-825.)-The melezitose prepared by the author from Taschkent manna had a composition correspondiog with the formula CISHDSOI,',, 2H,!O, and did not lose the whole of its water of crystallization at 1300 to 135" C. Its optical rotation, calculated on the anhydrous sugar, was al) = + 89.3. When hydrolysed by means of a dilute acid, it yielded one molecule of turanose and one molecule of dextrose, the former being decomposed on further hydrolysis into one molecule of dextrose and one molecule of I~vulose, and not, as commonly accepted, into two molecules of dextrose.The turanose separated from the products of the restricted hSdrolysis of melezitose had the formula CI.LH23011, and was the first known isomer of cane-sugar. I t was very sweet and soluble in all proportions in water and methyl alcohol. I t s optical rotation was aD = + 71.8 (calculated 72.8). I t was fermented by beer-yeast, but only very slowly. From 5 to 10 per cent. of sugar remained unfermented in an experimenr; that was continued for five months.C. A. &I. Determination of Lead Number of Maple Syrup and Maple Sugar, A. E. Winton and J. L. Kreider. (Jozim. Anzey. Chem. SOC., 1906, xxviii., 1204- 1209.)-The proportion of lead in the precipitate produced by treatment of maple products with basic lead acetate solution is approximately constant, and furnishes a means of determining the presence of cane-sugar. For its estimation the authors recommend an indirect method, using a definite volume of standard lead subacetate, and determining the lead remaining in the solution after precipitation. Twenty-five grams of the material ic; weighed into a 100 C.C. flask, 25 C.C. lead subacetate solution added, and the volume made up with water to 100 c.c., the rxixture shaken, allowed to stand one hour, and filtered.Ten C.C. of the clear filtrate are diluted to 50 c.c., a moderate excess of H,SO, and 100 C.C. of 95 per cent. alcohol added, and the whole allowed to stand overnight. The precipitate is then filtered on a Gooch crucible, washed with 95 per cent. alcohol, dried at a moderate heat, ignited at low redness for three minutes and weighed, the difference between the amount of lead thus found and that present in 2.5 C.C. of the standard solution, when divided by 2.5, giving the '' lead ~tuvzbe~." The lead subacetate solution used is prepared by boiling for half an hour 430 grams lead acetate, and 130 grams litharge, with 1,000 c.c. water, and after cooling and allowing to settle, diluting the supernatant liquid to a density of 1-25. To a measured volume of this solution, 4 volumes of water are added, filtering if not perfectly clear.The lead number for maple syrup is found to vary from 1.19 to 1-77, the last figure being obtained with a poor quality, and that for maple sugar from 1.84 to 2-48, falling in the case of adulterated samples to as low as 0.10, and in one case 0.02. W. H. S. On a Method for the Separation of Cholesterol and Phytosterol. A. Windaus. (Chem. ZQ., 1906, xxx. , 101l.)-Cholesterol dibromide is difficultly soluble in i ) ~ mixture of glacial acetic acid and ether, a mixture of 50 c.c. of acetic acid and 50 C.C. ether dissolving only 0-6 gram of the substance at 20" C. Phytos- terol dibromide, on the other hand, is much more readily soluble, and, moreover, does not crystallize at all easily. The author proposes a method of separation based412 THE ANALYST.on these facts, and describes the treatment of mixtares of 4, 8 and 0.4 gram cholesterol with 4, 0.8 and 4 grams respectively of phytosterol, the mixtures being dissolved in each case in 10 parts of ether and treated with the same quantity of glacial acetic acid containing 5 per cent. of bromine. I n each case products were obtained which permitted of ready identification as cholesterol and phytosterol derivatives. The dibromides can be readily reconverted into the original alcohols by freatment with a reducing agent (zinc dust or sodium amalgam). A. G. L. The Action of Ozone on Oils and Fats. E. Molinari and E. Soncini. (Berichte, 1906, xxxix., 2735-2744.)-Ozone is absorbed quantitatively by unsaturated fatty acids, and the increase in weight corresponds with the ozone value calculated from the iodine value.Oils become very viscous under the action of the gas, and a good solvent for modifying the violence of the reaction has been found in hexane from petroleum, which can subsequently be easily eliminated by means of a current of ozone. The author has determined the ozone values of linseed, maize, castor, olive, and rape oils, etc., and has obtained results agreeing well with the iodine values. Linseed-oil, for instance, with an iodine value of 171 gave an ozone value of 30 a s against the theoretical 32.3. Pure oleic acid (iodine value 9G.03) absorbed ozone in the proportion of 1 molecule to 1 molecule (03). The ozonide was a viscous, almost colourless liquid, heavier than water, and decomposing without melting when heated above 90" C. Its elementary composition and molecular weight corresponded with the formula C,,H,,O,.When decomposed by dry or moist heat it yielded nonylic, azelaic, and two other fatty acids, and an oily product boiling at about 190" C. From a study of these decomposition products the authors conclude that the ozonide must have the constitutional formula- C H, [ C Ha] 7. CH - C H. [ C H,] 7. C 0 0 H '0.06 aud that oleic acid absorbs 3 atoms of oxygen when acted upon by ozone, and not 4 as asserted by Harries (Berichte, xxxviii., 1630). Xezo Xethod of Determining Oxom.-When ozone is passed through ordinary olein the increase in weight corresponds to the amount of the gas absorbed. C. A. M. On the Ozonides of Oleic Acid, C.Harries and C. Thieme. (Bei-icILte, 1906, xxxix., 2844-2846.)-I.n a previous communication ( A m . d. Chenz., 1906, 318) it was found by the authors that when ozone acted upon a solution of oleic acid in acetic acid or chloroform it yielded a viscous oil, which, when purified by being dissolved in acetic ether and precipitation by petroleum spirit, was a colourless product containing 4 atoms of oxygen. They now find that if this substance he washed with water and sodium bicarbonate solution and extracted with ether, it gives a product containing only 3 atoms of oxygen. They propose to term this normal oleic acid ozonide, and their former preparation oleic acid perozonide. Both ozonides yield the same products when decomposed by water, and the chief difference between them is that when equal quantities are boiled for the same lengthTHE ANALYST+ 413 of time with water a much more intense reaction for hydroxgen peroxide is obtained in the case of the perozonide.The formula assigned by the author to the normal ozonide is the same as that given by Molinari and Soncini (see preceding abstract). C. A. M. Notes on some Conifer Oils. R. E. Hanson and E. N. Babeoek. ( J o u r ~ Amcr. Chern. Soc., 1906, xxviii. 1198-1201.)--Several oils distilled by the authors from authentic materials have been examined with the following results : Oil of Black Spruce Hemlock (1) Cat Spruce, Cat Spruce, Red Spruce, 7, (2) leaves cones leaves Red Spruce, cones A m e r i c a n Larch Pitch Pine Red Pine Juniper Virginia leaves leaves j Juniper, Yield, Per Cent._ _ 0.57 0.4 0-46 0.103 0-25 0,204 0.38 0.149 0.001 0.001 0.18 0.9274 ati 19" 09238 7 , 15" 0.9273 ), 15' 0.9216 ) ) 15" 0.899 ) ) 15" 0.9539 ), 16" 0.8600 ), 15" 0.8816 7 7 15" i 0.8531 a t 20" I - 0.900 7 > 16" . - - Odour suggests limonene or dipentene Yellow colour, pronounced limonene-like odour Free borneol, 7-76 pel- cent. odour of bornyl acetate Golden-yellow colour, fir- balsam-like odour Remainder largely pinene Yellow colour, pungent odour Brownish - red colour, pungent and disagree- able odour Light yellow colour, juniper odour - W. H. S. The Phosphomolybdic Aeid (Welman's) Test for Vegetable Oils. B. Kuhn and G. Malfpaap. (&it. Untersuch. Nahr. Gcnussm., 1906, xii., 449-455.)-This test is qzite useless for detecting the presence of vegetable oils in oleo-margarine and in tallow, as these two fats themselves give a dark green coloration with the reagent, but it may be employed for the detection of vegetable oil in lard.With very few exceptions, lards do not give a coloration. The constituent of vegetable oils which gives the coloration is, apparently, a decomposition product of albumin ; it is non- volatile, easily oxidizable, and is readily removed from the oils by extraction with414 THE ANALYST. alcohol, but not with hydrochloric acid. Owing to the fact that this active constituent is destroyed by heat, direct sunlight and oxidizing agents, a negative reaction does not prove the absence of vegetable oils (cf. ANALYST, 1895, p. 62). w. P. s. The Analysis of Turkey-red Oils.W. Herbig. (Chem. I k u . Fett-?i. Haw- Ind. , 1906, xiii., 187-190, 211-213, 241-244).--There is considerable confusion in commerce as to the meaning of the term '' 50 per cent. Turkey-red oil," etc., when applied to these products, and to obviate this the author suggests that it shall invariably be taken to refer to the amount of total fat. He has made comparative experiments with different methods, and recommends the following simple method of determining the total fat and combined sulphuric acid : Ten grams of the sample are heated with 50 C.C. of water, and the resulting solution treated with 25 C.C. of dilute hydrochloric acid (strength not given), and boiled for three to five minutes. Whenxold it is transferred to a separating funnel, the flask being rinsed out with water and ether, and then shaken with about 200 c.c.of ether. The aqueous layer is drawn off, and the ethereal solution thoroughly washed three times with water, which will take from thirty minutes to an hour. The washings are added to the original aqueous layer, the mixture boiled to expel all ether, and the sulphuric acid precipitated in the usual way as barium sulphate. The ethereal solution is now concentrated by distillation at a low teniperature, the residue then transferred to a weighed beaker, and the rest of the ether allowed to evaporate spontaneously. Fi.nally $he fat is heated for a minute or so over a free flame (till no more bubbles appear), and is then dried for thirty minutes at 105" C., and weighed. Tables of experimental results are given in detail, and it is also shown that the results for the total fat obtained by decomposing Turkey-red oils with cold hydrochloric acid differ but slightly from those obtained by treating the oils with boiling acid.C. A. M. A Method of Distinguishing between True Albumin and Mucinoid Substance in Urine. L. Grimbert and E. Dufau. (Jounz. Y h n m . CIZZ"IYL., 1906, xxiv., 193-199.)-A little of the filtered urine is allowed to run from a narrow pipette on to a few C.C. of a solution of 100 grams of citric acid in 75 C.C. of water. When only mucinoid substance is present, a more or less nebulous zone is formed near the juncture of the liquids, attaining its maximum intensity after the lapse of one or two minutes. On the other hand, urine containing only pathological albumin (even as much as 6 to 8 grams per litre) gives no such turbidity.Again, when the urine is allowed $0 flow on to the surface of nitric acid (Heller's reaction), pathological urine produces a sharp ring at the contact-zone, whilst mucinoid substance gives no ring, but a, turbidity above the zone of contact. I n the case of urine containing both substances, the ring and turbidity will both appear, with a clear zone between them. When Heller's reaction gives a positive result, it will be necessary to confirm by other tests the nature of the proteid found. C. A. M. Note on the Analysis of Hungarian Leather. F. Jean. (dnn. de Chinz. Anal., 1906,, voL 7fl, pp. 361-363.)-Tne commissariat of the French Army requiresTHE ANALYST.415 the white skins intended for military accoutrements to contain not more than 10 per cent. of water, from 10 to 15 per cent. of alum, 5 per cent. of sodium chloride, and 25 to 33 per cent. of grease. By " alum " is understood potassium aluminium sulphate containing twenty-four equivalents of water. Three samples of such leather examined by the author gave the following results : Water (loss at 105" C.), 25.4 to 26-2 ; fat, 21.5 to 23.6 ; sodium chloride, 4-1 to 5.6 ; sulphuric acid (SO,), 6.7 to 9.3 ; water in ammonium sulphate, 0.25 to 0.31 ; ammonia, 0.47 to 0.49 ; alumina, 2.4 to 3.9, and hide substance (N x 5*62), 32.7 to 36.3 per cent. Calculation of the amount of ammonium alum (containing twenty-four equivalents of water) : (1) from the amount of alumina; (2) from the total sulphuric acid; and (3) from the ammonia, gave the following figures : 1 2 0 Pcr Cent.Per Cent. Per Cent. From the alumina ... ... 21.5 26.7 34 ,, sulphuric acid . . . ... 19.19 19.54 26-29 ,, ammonia ... . .. 12-78 12.60 15-77 The author's explanation of these discordant results is that in hides whitened with alum and salt the aluminium is no longer present in the form of alum, but that there has been dissociation of the salt into a more or lass basic aluminium sulphate fixed by the hide, with partial elimination of ammonium sulphate in the baths. I t will be necessary for the military specifications to be modified, since ordinary alum has now been generally replaced by ammonium or sodium alums in the preparation of Hungarian white skins. C.A. M. On the Balsam of Hardwiekia Pinnata. G. Weigel. (Phnrm. Ccntralh., 1906, vol. 47, p. 773; through C'lzem. Ztg., 1906, xxx., Rep., 345.)-This East Indian balsam appears capable of replacing copaiva balsam in the painting of porcelain, varnish-making, etc. The balsam contains 48.5 per cent. of ethereal oil and 51.5 per cent. of resinous bodies (48.3 per cent. saponifiable and 3.2 per cent. unsaponifiable). A. G. L. The Determination of the Calorifie Value of Liquid Fuels by Means of the Junker Calorimeter. E. Glinzer. (Zeits. angezo. Ghem., 1906, xix., 1422.)- The author mentions the excellent results obtained by means of the Junker calori- meter in the case of gaseous fuels, and its increasing application to liquid com- bustibles. Under special conditions oils with a boiling-point of even 400" C. may be burnt in it, and in the ordinary way the calorimeter may be used for oils with a boiling-point not exceeding 250' C. For such oils the burner shown in the figure is used, the principle of the burner being similar to that of the well-known "Primus" burners for gasolene and petroleuni. The burner is suspended from one arm of a, balance, and nearly balanced by weights placed on a scale-pan depending from the other arm. The oil-vapour is then lighted, the nozzle placed in the calorimeter, the water is turned on, and the temperatures of the in-going and out-coming water are allowed to become constant. When so much oil has been burnt that the burner is exactly balanced, a small weight (10 or 2C grams) is placed in a small scale-pan below the burner so as to depress the latter, and the experiment is continued until the416 THE ANALYST, burner is again in exact equilibrium, showing that a quantity of oil corresponding to the added weight has been burnt. The water passing through the calorimeter during this time is, of course, collected and measured. A. G. L.