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[Co [Copyright Friday, August 29, 1913. PAGE CONTENTS. Kegistered as [PRICE 44. ARTICLES: The Influence of Chlorine on the Determination of Nitrates by On the Nitrile of Fumaric Acid and the Preparation of Methyl Reactions of Ozone with certain Inorganic Salts, by Y. Yamauchi The Scientific Week .... ..... 97 98 99 100 101 ...... 107 CORRESPONDENCE.-Swedish Tar and Wood By-products...... 107 CHEMICAL NOTICES FROM HORRIGN SOURCES C. PASS AND SON, LIM., BRISTOL, Are Buyers of 108 LEAD ASHES, SULPHATE OF LEAD, LEAD SLAGS, ANTIMONIAL LEAD, COPPER MATTE, TIN ASHES, &c., ORES, DROSS, or RESIDUES, containing FIN, COPPER, LEAD, and ANTIMONY. PLATINUM Utensils. We supply all forms and sizes of Platinum Utensils and Apparatus for Chemical and Physical purposes. All our utensils are hammered to shape, tested, and finished in the best manner. All kinds of Platinum scrap bougn for cash or taken in exchange for new. DERBY and CO., Ltd, 44. Clerkenwell Road, London. 1.C. 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Earlier work at this laboratory on this question demon- | strated a marked influence of chlorine upon the amount of nitrates found (Stewart and Greaves, Journ. Am. Chem. Soc., 1910, xxxii., 756). Thus, it was found that if the soil solution contained even as low a concentration as 2.6 parts per million of chlorine in the soil extract less nitrates were found by this method than were actually present. The experimental data recently presented by Lipman and Sharp (Univ. of Cal. Publication in Agr. Sci., 1912, i., 12), although they are apparently not aware of this fact, confirm this conclusion. This may be seen by converting the results obtained in both cases to the same basis in order to make a comparison, since our results are reported as parts per million of chlorine in the soil extract, while Lipman and Sharp's results are reported as milligrms. of sodium chloride present. The results converted to the same basis, i.e., milligrms. of sodium chloride actually present in the portion of the solution used, are compared in Table I. TABLE I.-Influence of Ionic Chlorine on the Determination of Nitrates in Solution. 97 ionic chlorine has a marked influence on the determination of nitrates in the soil extract, and that in alkali soils this fact must be taken into consideration in determining the nitrate content. There is still another phase of this question, however, one which, so far as we are aware, has never been considered by previous investigators, and this is the influence of chlorine, which is not in the ionic form but is combined in the organic molecule, on the determination of the nitrate content of the soil extract. This is a question of considerable practical importance, since chloroform is frequently used to inhibit the action of bacteria in the soil extract. Especially is this so in case of the use of the lime method as proposed by Lipman and Sharp. In the use of this method, if chloroform be also used, it appeared to us that there is the possibility of the formation of ionic chlorine from the organic chlorine of the chloroform, and if present in sufficient quantities this would materially affect the value of the results obtained. The assumption that ionic chlorine would be formed by the action of calcium oxide on the chloroform seemed to be justified by the fact that is so well known, that potassium hydroxide does act on chloroform as indicated in the following equation: CHCl3 + KOH = HCOOK+3KCl+2H2O, with the production of ionic chlorine. This being the case why may not calcium hydroxide act in a similar manner, as follows: 2CHCl3 + 4Ca(OH)2 = (HCOO)2Ca +3CaCl2 + 4H2O ? If such a reaction did take place, the ionic chlorine formed would materially interfere with the determination of the nitrates. In view of the fact that we are aware that chloroform is used by some investigators with the lime method, it appeared to us that the question should be exhaustively studied. Therefore, varying amounts of chloroform were added to solutions containing 1 mgrm. of nitric nitrogen and I grm. of lime. These solutions were carefully worked up in a mortar, placed in a closed container, and allowed to stand over night. A portion of the solution was used the next morning to determine the ionic chlorine present, while in another portion the nitric nitrogen was determined. The results obtained are given in Table II. An examination of the data presented in Table II. Nitric nitrogen brings out two very important facts. First, that ionic found (per cent). 102 chlorine is liberated when lime and chloroform are mixed together, and that the quantity of chlorine liberated varies with the chloroform. Second, that the ionic chlorine formed interferes very greatly with the accurate determination of nitrates by the phenol disulphonic acid method. It may, therefore, be seen that determinations made by this method, where the solution has both chloroform and lime present, give results which may be less than one-half of what they should be. TABLE II.-Influence of Chloroform on Determination of the Nitric Nitrogen by the Lime Method. Ionic chlorine found, mgrms. loss. sodium chloride. Mgrm. 0'04 Ο ΟΙ 100 102 form nitrogen added. added. Cc. Mgrm. Nitric Thus, it may be readily seen that when only o'I mgrm. of sodium chloride was present in both cases all of the nitrates present could be easily determined. Lipman and Sharp, however, found that when o 25 mgrm. of sodium chloride was present, that only 90 per cent of the nitrates actually present could be determined, while we found that when 0.27 mgrm. of sodium chloride was present, only 90 per cent of the nitrates could be found. With a concentration of 1 mgım., Lipman and Sharp found only 70 per cent of the nitrate, while we, with 079 mgrm. of sodium chloride, found only 86 per cent of the nitrate. It is thus seen that Lipman and Sharp have confirmed, in a remarkable manner, the results obtained at this laboratory. It is seldom that investigators in separate laboratories get such concordant results. It is thus fully confirmed that |