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The public are informed that on and after Saturday, November 6th, newspapers, magazines, books, and other printed publications (other than trade circulars) will not be sent forward to neutral European countries unless posted direct from the office of publishers or newsagents who have obtained permission from the War Office for this purpose. Persons desiring to send newspapers, &c., to neutral European countries should therefore give their orders for execution to publishers or newsagents who have obtained such permission. The Publisher of the CHEMICAL NEWS has obtained the required permission of the War Office, and he will forward copies direct from the Office to any neutral country on receipt of instructions. NEWS Quantitative Experiments with Fe and Ba. N/10 Thiosulphate required = 17'7 cc. 97 mgrms. Fe. =34 mgrms. Ba. 100 mgrms. Ba originally present .. 2. A similar experiment with 40 mgrms. of Ba :- boiled with a solution containing Ba. The loss in these cases can probably be explained by adsorption, but in an experiment, on the other hand, in which acetic acid and NaC2H3O2 were present, a much larger loss-in fact roughly a 50 per cent loss- was experienced. The most probable explanation of this would seem to be that in the presence of acetic acid the FePO4 is hydrolysed to a considerable extent on boiling. The PO4 ions would the FeCl3 formed would, in the presence of NaC2H3O2, be then react with the BaCl2 present, giving Ba3, PO4)2, while removed from solution as basic acetate. The Ba3(PO4)2, temporarily formed and soluble in acetic acid, would be precipitated during the boiling as BaHPO4, insoluble in acetic acid. Action of Na.C2H3O2 and Acetic Acid on FeCl3. The procedure in the following series of experiments was in each case as follows: Na2CO3 solution. (The sodium acetate solution used was 2/N and the acetate solution 4/N). ..=00128 grm.= 140 5 -7'5 mrgms. Ba. 3 140 ΙΟ 3 140 4 2 56 4 2 5.6 2 Yellow filtrate 98 mgrms. Fe. +28 =67 mgrms. Ba. =140 mgrms. Ba originally present.. Fe and Sr. 1. 56 mgrms. Fe, 60 mgrms. Sr, 6 cc. 0'5/N (NH4)2HPO4, I cc. 4/N acetic acid, and 8 cc. 2/N Na.C2H3O2. Boiled, filtered, and washed the precipitate. The filtrate gave a small precipitate of SrSO4 with H2SO4 and alcohol. The precipitate contained only a trace of Sr. 2. 56 mgrms. Fe, 150 mgrms. Sr, 8 cc. o'5/N (NH4)2HPO4, I cc. 4/N acetic acid, and 8 cc. 2/N NaC2H3O2. The filtrate gave a considerable amount of SrSO4. The precipitate gave a much smaller amount of SrSO, (one-third to one-quarter). The greater part of the Sr evidently remains in solution in contradistinction to Ba. Fe and Ca. 1. 112 mgrms. Fe, 60 grms. Ca. An exactly similar experiment to the last one. Tested for Ca with H2SO4 and 3 vol. of alcohol. In both cases a precipitate of CaSO4 was obtained, but that from the filtrate was by far the larger of the two. 280 *Diluted to two volumes. Examination of the above table shows clearly that if the amount of acetic acid in any particular case is too great to allow of the complete precipitation of the iron, the adThe results of these experiments show that the phos-dition of a further quantity of sodium acetate will not be phate separation as usually carried out is inaccurate in presence of Ba, and the same applies in a lesser degree to the presence of Sr and Ca. Consequently the alkaline earth metals must be removed before the phosphate, or recourse must be had to the alternative method of removing phosphate with tin and nitric acid before com. mencing the analysis of the iron group. The proportion of the Ba which remains with the FePO4 precipitate is too great to be explained by adsorption. Experiments show that in the absence of acetic acid only a very slight loss occurs when FePO4 or basic ferric acetate is tion. In general, 4-5 cc. of 2/N Na.C2H3O2 and 1 cc. of 4/N acetic acid in a volume of 60-70 cc. will ensure the complete removal of iron up to 140 mgrms. at least. In order to secure some definite information as to the behaviour of Ni, Co, and Mn in presence of Na.C2H3O2 and acetic acid, a further series of experiments was carried out. Action of Na.C2H3O2 and Acetic Acid on Ni, Co, and Mn | found to contain some Co, as shown by a light brown in boiling solution. coloration on making alkaline with NH4OH. (This observation holds good in the case of Ni also). 2. 145 mgrms. Co, I cc. 4/N acetic acid, and 6 cc. of 2/N NaC2H3O2. The precipitation was complete. Manganese. 1. 135 mgrms. Mn, I cc. 4/N acetic acid, and 6 cc. 2/N Na.C2H3O2. Heated to boiling and passed in H2S for three minutes. The solution remained clear, The experiments show that the precipitation of Ni and Co by means of H2S is complete in a hot solution containing 1 cc. 4/N acetic acid and 6 cc. 2/N Na.C2H3O2. If more than I cc. of acetic acid is present, then a propor tionately larger amount of Na.C2H3O2 must be added. Separation of Fe from Co and Mn in presence of 1. 56 mgrms. Fe, 6 mgrms. Co, 2 cc. 2/N (NH4)2HPO4, I cc. 4/N acetic acid, and 6 cc. 2/N Na.C2H3O2. Added a slight excess of FeCl3 and boiled to remove Fe and phosphate. The filtrate vas colourless and free from Fe. On passing H2S through the hot filtrate no precipitate appeared, but on adding 4 cc. of 2/N Na.C2H3O2 and again passing H2S a black precipitate of CoS was obtained in a few minutes. 3. 56 mgrms. Fe, 5 mgrms. Mn, 2 cc. 2/N (NH4)2HPO4, I cc. 4/N acetic acid, and 6 cc. 2/N Na.C2H3O2. After removing Fe and phosphate as usual heated the filtrate to boiling, passed in H2S, and then made alkaline with NH4OH. A buff coloured precipitate of MnS was at once obtained. To the solution containing the metal, (NH4)2HPO4 and a little NH4OH were added. The precipitated phosphate was then just dissolved in HCl. Na.C2H3O2 and acetic acid were added, the solution diluted to 60 cc. and boiled. 1. 60 mgrms. Ni, 2 cc. 2/N (NH4)2HPO4, I cc. 4/N, acetic acid, and 6 cc. 2/N NaC2H3O2. On boiling themgrms. solution became turbid and a small precipitate separated out. 2. 58 mgrms. Co, 2 cc. 2/N (NH4)2HPO4, I cc. 4/N acetic acid, and 6 cc. 2/N Na.C2H3O2. On boiling a violet coloured precipitate of cobalt phosphate separated out. 3. 60 mgrms. Ni, 58 mgrms. Co, 3 cc. 2/N (NH4)2HPO4, I cc. 4/N acetic acid, and 6 cc. 2/N Na.C2H3O2. On boiling a heavy violet precipitate of cobalt phosphate separated out, which dissolved almost completely on adding 2 cc. 4/N acetic acid. 4. 54 mgrms. Mn, 2 cc. 2/N (NH4)2HPO5, I cc. 4/N acetic acid, and 6 cc. 2/N Na.C2H3O2, On boiling manganese phosphate was precipitated in large quantity. It did not dissolve completely on adding 5-6 cc. of 4/N acetic acid and boiling. Action of H2S on Solutions of Ni, Co, and Mn in presence of Na.C2H3O2 and Acetic Acid. 1. 150 mgrms. Ni, 2 cc. 4/N acetic acid, 4 cc. 2/N Na.C2H3O2, water 60 cc. Heated to boiling and passed in H2S gas for two minutes. The filtrate had a green colour. Added 4 cc. 2/N Na.C2H3O2, heated to boiling, and again passed in H2S. Precipitation was incomplete. Again added 4 cc. Na.C2H3O2, boiled and passed in H2S. filtrate was colourless and free from Ni. The 2. 150 mgrms. Ni, 1 cc. 4/n acetic acid, and 4 cc. 2/N Na.C2H3O2. The filtrate was colourless and practically free from Ni. 3. 60 mgrms. Ni, 1 cc. 4/N acetic acid, and 6 cc. 2/N Na.C2H3O2. Complete precipitation. Filtrate colourless and free from Ni. 4. 6 mgrms. Ni, 1 cc. 4/N acetic, and 6 cc. 2/N Na.C2H3O2. Filtrate colourless and free from Ni. Cobalt. 1. 58 mgrms. Co, 1 cc. 4/N acetic acid, and 6 cc. of 2/N Na.C2H3O2. The filtrate was colourless after the first filtration and free from Co. When, however, the filtrate was passed through the same filter a second time it was 3. A similar experiment, with 56 mgrms. Fe and 54 Mn. MnS was precipitated in quantity on passing H2S through the filtrate and making alkaline with NHẠOH. The results show that the basic acetate separation of Fe and phosphate from Co and Mn is quite satisfactory under the given conditions, even when small amounts of the latter are present. Group II. of KCIO3. Evaporate to dryness. Dissolve in 4-5 cc. of water and divide into two portions. I. Neutralise one portion with NaOH, and add 1-2 cc. Remove and separate the metals of the copper and tin group by the method described in a previous paper (loc. of acetic acid and 1-2 cc. of strong KNO2 solution, and cit.). Group III. The solution, which will probably occupy about 100 cc., is now boiled to remove H2S, and concentrated to 20-30 cc. Add 5 cc. of bench H2SO4 (4/N), followed by 40-50 cc. of alcohol. Allow to stand for fifteen minutes and then filter, using the pump if necessary. Precipitate.-Sulphates of Ba, Sr, and Ca. Wash once or twice, transfer to a small beaker, and boil for ten minutes with 20 cc. of strong Na2CO3 solution. Filter off and wash the carbonates, dissolve in a few cc. of dilute acetic acid, and analyse according to the method previously described (loc. cit.). (Note.-If extreme accuracy is desired, it may be advisable to separate the Sr and Ca by the action of alcohol and ether on the anhydrous nitrates, since the solubility of SrSO4 is considerably increased by the presence of large amounts of Ca salts, and consequently very smail amounts of Sr are not precipitated by CaSO4). Group IV. Filtrate.-Contains Al, Cr, Zn, Fe, Ni, Co, Mn, Mg, Na, and K. Heat the filtrate on the water-bath until all the alcohol has been removed, and reserve a portion-say one-third-for the examination for Na and K. To the main portion add NaOH until a permanent precipitate is formed, then 2-3 grms. of Na2O2, and heat to boiling for a minute or two. Filter and wash. Filtrate. Fi. Contains NaAlO2, Na2CrO4, and NaZnO2, as well as most of the phosphate, if this is present. (It may of course contain K and Na, but as Na has already been added the solution is not available for examination for the alkalis). To the filtrate add several grms. of solid NH4Cl and boil. A white flocculent precipitate indicates Al. Filter, wash well, and confirm Al by the Co(NO3)2 test. The filtrate from the Al contains CrO4" and ZnO,". If the solution is yellow Cr is probably present. Acidify a small portion with dilute HNO3, add a few cc. of ether and a few drops of H2O2, and shake. A blue etherial layer indicates Cr. If Cr is present acidify the main portion with acetic acid, heat to boiling, and add BaCl2. Filter off the precipitated BaCrO4 and BaSO4, make alkaline with ammonia, and pass in H2S gas. A white precipitate indicates Zn). (If Cr is absent the filtrate from the Al is tested for Zn by simply saturating with H2S). Precipitate. P1. Fe(OH)3, Co(OH)3, Ni(OH)2' Ni(OH)3, MnO(OH)2, Mg(OH)2, and may contain small amounts of the phosphates of these elements. Dissolve the precipitate in a little HCl (using hot strong acid and KCIO3 if necessary), evaporate almost to dryness, and dissolve the residue in water. Test a small portion of the solution for Fe with K4Fe(CN)6, and dilute the main portion to 60 cc. Add Na2CO3 solution until a slight permanent precipitate forms; remove this by adding dilute HCI drop by drop, then add 1 cc. of 4/N acetic acid and 6 cc. of 2/N Na.C2H3O2, followed by FeCl3 until the mixture assumes a pale yellow colour. Boil for a minute and filter hot. Precipitate. P2.-Contains FePO4 and basic ferric acetate. Neglect. Filtrate. F2.-Co, Ni, Mn, and Mg as acetates. Heat to boiling and pass H2S through the hot solution for five minutes. If no precipitate forms add a little more Na.C2H3O2 solution (4-5 cc.), boil and pass in H2S. Filter and wash, but do not add any of the washings to the filtrate. Precipitate. P3.-NiS and CoS. [ZnS]. Dissolve in 2-3 cc. of concentrated HCl, with the addition of a crystal allow to stand. A yellow precipitate of K cobaltinitrite indicates Co. II. To the second portion add KCN solution (after neutralising with NaOH if necessary) until the precipitate first formed just dissolves, then add 4-5 cc. of 2/N NaOH and a few drops of Br water and boil. A black precipitate of Ni(OH)3 indicates Ni. (Note. If Zn has not been identified before it will generally be advisable to examine the precipitate of Co and Ni sulphides for it. This may be done as follows:Dissolve the mixed sulphides in HCl as above, evaporate to get rid of Cl, dissolve in water, and add NaOH in excess and boil. Cool and filter. If the filtrate contains any Zn as Na2ZnO2, saturate with H2S. A white precipitate of ZnS indicates Zn. The precipitate of CO(OH)2 and Ni(OH)2 is washed, dissolved in HCl, and tested as before for Co and Ni. Filtrate. F3.-Contains Mn and Mg as acetates. Make alkaline with NH4OH and pass in H2S. A fleshcoloured precipitate indicates Mn. The filtrate from the Mn contains Mg. Boil to expel H2S, add NH4CI, NH4OH, and (NH4)2HPO4; stir and allow to stand. A white crystalline precipitate of MgNH4PO4 indicates Mg. (Note. If the alkaline earth metals have been detected previously it may be advisable to remove traces of these which may be present in solution by adding a few drops of H2SO4 to remove Ba and Sr, and a few drops of NH4OH+ (NH4)2C2O, to remove Ca. The solution is then filtered and tested for Mg with (NH4)2HPO4. The portion of the original solution, after removal of Ba, Sr, and Ca, which was reserved for examination for K and Na, is treated as follows: : Add NH4OH, NH,Cl, and excess of H2S water, or pass in H2S gas, heat to boiling, add (NH4)2CO3, and filter. If Mg has been found to be present, add a volume of alcohol to the filtrate and a little more (NH4)2CO3, allow to stand for ten minutes, and filter off the MgCO3(NH4)2CO3. The filtrate is then evaporated to dryness, ignited to remove ammonium salts, dissolved in a few cc. of water, and examined for K and Na. If Mg is absent the treatment with alcohol is omitted and the first filtrate evaporated, ignited, and examined for K and Na. The examiration for Na and K may be made in the usual way-i.e., flame tests and formation of potassium cobaltinitrite, or recourse may be had to the method of Mathers and Lee, in which fluoboric and fluosilicic acids are used (Fourn. Am. Chem. Soc., 1915, xxxvii., 1515). The following analyses were carried out and proved to be quite satisfactory : Electrical Production of Nitrates.-A course of six lectures on "Electrical Production of Nitrates for Fertiilsers and Explosives" will be delivered at the University of London, University College, by E. Kilburn Scott, M.I.E.E., A.M.Inst.C.E., on Wednesdays, at 5.30 p.m., beginning January 26, 1916. The first lecture is open to the public without fee or ticket. The course is open both to members and non-members of the University; fee, £1 11s. 6d. Applications for tickets of admission to be made to WALTER W. SETON, M.A., D. Lit., Secretary, University College, Gower Street, W.C, |