[Footnote: Read before the American Chemical Society, Dec. 16, 1881]


The element manganese having many peculiarities in its reactions with the other elements, is now extensively used in the arts, its combinations entering into and are used in many of the important processes; it is consequently often brought before the chemist in his analysis, and has to be determined in most cases with considerable accuracy. Many methods have been proposed for this, all of them of more or less value; those yielding the best results, however, requiring a considerable length of time for their execution, and involving so large an amount of manipulatory skill as to render them fairly impracticable to a chemist at all pressed for time, and receiving but a mere trifle for the results.

As I have had to make numerous estimations of manganese in various compounds, as a public analyst, I have been induced to investigate the volumetric methods at present in use to find their comparative values, and if possible to work out a new one, setting aside one or more of the difficulties met with in the use of the older ones. This paper is a part summary of the results. First, I will detail my process of estimation, then on the separation.

From all compounds of manganese, excepting those containing cobalt and nickel, the manganese is precipitated as binoxide; those containing these two elements are treated with phosphoric acid, or as noted under Separation.

A.--The Estimation. The binoxide of commerce, as taken from the mine, is well sampled, powdered, and dried at 100°C. 0.5 gramme of this is taken and placed in a 250 c.c. flask; in analysis the binoxide on the filter, from the treatments noted under separation is thoroughly washed with warm water; it is then washed down in a flask, as above, after breaking the filter paper; sufficient water is added to one-third fill the flask, and about twice the approximate weight of the binoxide in the flask of oxalate of potassa; these are agitated together. A twice perforated stopper is fitted to this flask, carrying through one opening a 25 c c. pipette nearly filled with sulphuric acid, sp. gr. 1.4, the lower point of which just dips below the mixture in the flask, and the upper end, carrying a rubber tube and pinch cock to control the flow of acid. Through the other opening passes a glass tube bent at an acute angle and connected by a short rubber tube to an adjoining flask, two-thirds filled with decinormal baryta solutions. These connections are all made air tight. Sulphuric acid is allowed in small portions at a time to flow into the mixture. Carbonic acid is evolved, and, passing into the adjoining flask, is absorbed by the baryta, precipitating it as carbonate. To prevent the precipitate forming around or choking up the entrance tube, the flask must be agitated at short intervals to break it off. The reaction so familiar to us in other determinations is expressed thus:


When no more carbonic acid is evolved, another tube from this last flask is connected with the aspirator, the pinch-cock of the pipette open, and air drawn through the apparatus for about half a minute, and thus all the carbonic acid evolved absorbed, or the flasks may be slightly heated. If danger of more carbonic acid being absorbed from the air is feared, and always in very accurate analysis, a potassa tube may be connected to the pipette before drawing the air through. The precipitate formed is allowed to settle, 50 c.c. of the supernatant solution is removed with a pipette and transferred to a beaker; 50 c.c. of decinormal nitric acid and some water is added with sufficient cochineal tincture. It is then titrated back with decinormal soda; from this is now readily deducted the amount of carbonic acid, and from that the MnO, holding in view that 44 parts of carbonic acid is equivalent to 43.5 of MnO or 98.87 per cent, and that 1 c.c. of the N/10 baryta solution is equivalent to 0.0022 grm. of CO.

If a carbonate, chloride, or nitrate, be present in the native binoxide, it must be removed with some sulphuric acid. This is afterward neutralized with a little caustic soda. This method yields the following results for its value in amount of manganese to 100: 99.91-99.902-99.895, and can be executed in about twenty minutes. Fifteen determinations can be carried on at once without loss of time, this, however, depending on the operator's skill. I have made many assays, and assays by this method with similarly excellent results.

Of the other methods, Bunsen's is acknowledged to be the most accurate, but is, of course, too troublesome to be used in technical work, although it is used in scientific analysis. Ordinary samples are not sufficiently accurate to allow the use of this method.

The methods of reducing with iron and titrating this with chromate of potassa, etc., have given a constant average of from 98.60-99.01. These results are fair, but hard to obtain expeditiously.

Of the methods of precipitating the compounds of the protoxide and estimating the acid, that of the phosphate is by far the most accurate, titrating with uranium solution; 99.82 is a nearly constant average with me, much depending on the operator's familiarity with the uranium process.

The methods of Lenssen, or ferricyanide of potassium method, yields very widely differing results. I have found the figures of Fresenius about the same as my own in this case; that is from 98.00-100.10.

B.--On the Separation. First, from its soluble simple combinations with the acids or bases containing no iron or cobalt; if they are present, it is treated as is noted later. If sulphuric acid is present it must be separated by treating the solution of the compound with barium chloride and filtering. A nearly neutral solution is prepared in water or hydrochloric acid and placed in a flask. Here it is treated with chlorine by passing a current of that gas through it as long as it causes a precipitate and for some time afterward. It is then discontinued, the mixture allowed to deposit for a few moments, and about two-thirds of the supernatant solution decanted; it is mixed with some more water, and these decantations repeated until they pass away without reaction, or by filtering it and washing on the filter; it is then dissolved in hot hydrochloric acid, this nearly neutralized, a solution of sesquichloride of iron is added, and again treated with an excess of chlorine. After washing it is transferred to the flasks of the apparatus mentioned in the first part of this paper, and estimated. Myself and several others have found this always to be a true MnO, and not a varying mixture of protosesquioxide and binoxide, and will thus yield accurate results. This reprecipitation may sometimes be dispensed with by adding the iron salt before the first precipitation, but it of course depends upon the other elements present.

From Compounds containing Cobalt, Cobalt and Nickel, Iron and group III., together or with other elements.--Group III. and sesqui. iron are separated by agitation with baryta carbonate, some chloride of ammonia being added to prevent nickel and cobalt precipitation traces, and filtering. If cobalt is present we treat this filtrate with nitrite of potassa, etc., to separate it (that is, if it and nickel are to be separated and estimated in the same sample; but if they are to be estimated as one, or not separated, the treatment with nitrite, etc., is not used). The filtrate from this last is directly treated with chlorine. If nickel and cobalt are not to be estimated in this sample, the solution, as chlorides, is mixed with some chloride of ammonium and ammonia, then with a fair excess of phosphoric acid, a sufficient quantity more of ammonia to render the mixture alkaline. The precipitate formed is transferred to the filter and well washed with water containing NHCl and NHO, then dissolved in hydrochloric acid and reprecipitated with ammonia, filtering and washing as before. It is again dissolved in HCl and titrated with uranium solution, or decomposed by tin, as noted below, and the manganese precipitated as binoxide with chlorine, and determined. The latter method is hardly practicable, and I never have time to use it, as the titration and all together yields a value of 99.80 in most cases, if accurately executed.

From the bases of groups V. and VI. these are separated by hydrogen sulphide, from iron in alloys, ores, etc., and in general the iron is separated as basic acetate, and the manganese afterward precipitated with chlorine. Bromine is generally used in place of chlorine, the use of which chemists claim as troublesome; but in a number of examinations I have found it to yield more satisfactory results than bromine, which is much more expensive.

From the acids in insoluble and a few other compounds, chromic, arsenic, and arsenious acids, by fusion with carbonate of soda in presence of carbonic acid gas; borate of manganese is readily decomposed when the boracic acid is to be determined by boiling with solution of potassa, dissolving the residue in hydrochloric acid and precipitating the manganese as binoxide. This boiling, however, is seldom needed, as the borate is soluble in HCl.

From phosphoric acid I always use Girard's method of treatment with tin, using it rasped, and it yields much more accurate results with but little manipulation. When the other acids mentioned above are present in the compound, we treat it as directed there.

From silicic acid, by evaporation with hydrochloric acid.

From sulphur or iodine, by decomposing with sulphuric acid and separating this with baryta chloride.