As what takes place in the titration of iron with chameleon is indicated by the following formula,

10FeO + 2KMnO = 5FeO + KO + 2MnO,

it appears, on making a comparison with the formula given above, that ten equivalents of iron correspond to three equivalents of manganese, and that there is thus required for three equivalents manganese as much chameleon solution as for ten equivalents iron. When we know the titration of the chameleon solution for iron, that for manganese is obtained by multiplying the former by (3 x 55)/(10 x 56) =0.295. If, for instance, one cubic centimeter chameleon solution corresponds to 0.01 gramme iron, the figure for manganese is 0.01 x 0.295 = 0.00295 gramme per cubic centimeter.

We can of course also determine the titration for manganese in a chameleon solution with the greatest certainty by titrating a compound of manganese with an accurately estimated content of it, for instance, a spiegeleisen or ferromanganese; the test is carried out in the following way: The substance, which is to be examined for manganese, is dissolved by means of hydrochloric acid. If the manganese, as in slags, be combined with silica, it is frequently necessary first to fuse the specimen with soda. Iron ores and refinery cinders may indeed, if they are reduced to a very fine state of division, be commonly decomposed by boiling with hydrochloric acid with or without the addition of sulphuric acid, but the undissolved silica is generally rendered impure by manganese, which can only be removed by fusion with soda.

The dissolving of the fused mass in hydrochloric acid does not need to be carried to dryness for the separation of the soluble silica, but the boiling, after the addition of a little nitric acid, is only kept up until the iron passes into perchloride and the manganese into protochloride. The quantity, which ought to be taken for the test, depends on the accuracy with which it is desired to have the manganese estimated.

Of ferromanganese and other very manganiferous substances, in which the manganese need not be determined with greater exactness than to 0.1 per cent., only 0.01 gram. is taken for a test; but of common pig, wrought iron, steel, iron ore, slags, etc., there is taken 0.5 to 1 gramme according to the supposed content of manganese and the desired exactness of the estimation. For instance one gramme iron, which has passed through a metal sieve with holes half a millimeter in diameter, is placed in a beaker 125 mm. in height and 60 mm. in diameter, and has added to it twenty cubic centimeters of hydrochloric acid of 1.12 specific gravity, which, with a well-fitting glass cover, is boiled for half an hour, in order that the combined carbon may be driven off in the shape of gas. After at least the half of the hydrochloric acid has been boiled away, there are added at least five cubic centimeters nitric acid of 1.2 specific gravity, partly to bring the iron to peroxide, partly to destroy the organic matters formed from the carbon, which might possibly be remaining and might tend to remove the color of the chameleon solution. The boiling is now continued till near dryness, when five cubic centimeters hydrochloric acid are added, after which the solution is boiled as long as any reddish-yellow vapors of nitrous acid are observed. When these have disappeared a drop of the liquid taken up on a small glass rod is tested with an newly prepared solution of red prussiate of potash (2 grammes in 100 cubic centimeters water), to ascertain whether there is any protoxide of iron remaining. First, when no indication of blue or green is visible, the test shows a pure yellow, it is certain that there are no reducing substances in the solution.

If a trace of protoxide of iron remains in the solution another cubic centimeter of nitric acid ought to be added and the boiling continued so long as any reddish-yellow vapors are visible, more hydrochloric acid also being added to keep the solution from being dried up. The process is continued in this way until two tests have given no reaction of protoxide of iron, when the solution is diluted with water; but no dilution should take place until the oxidation is complete, because in the course of it the solution ought to be kept as concentrated as possible. Silica, and graphite when it is present, need not be removed by filtration, if it is not intended to estimate them, or there be no fear that the graphite is accompanied by any humous substance, or that any oily, viscous compound has been deposited on the sides of the beaker. In the last mentioned case the solution should be transferred into another beaker, and filtered, if graphite be present. When the solution is evaporated to dryness, the remainder has five cubic centimeters hydrochloric acid added to it, and the liquid is then brought to boiling in order that the perchloride of manganese possibly formed during the evaporation to dryness may be reduced to protochloride, after which the solution is diluted with water till it measures about 100 cubic centimeters. To this is now added in small portions and with constant stirring as much of a saturated solution of bicarbonate of soda (thirteen parts water dissolve one part salt), that all the iron is precipitated, after which, when the escape of carbonic acid has ceased, the solution is diluted with water till it measures 200 cubic centimeters and is then ready for titration.

A large excess of bicarbonate ought to be avoided, because in a solution of pure protochloride of manganese it renders the liquid milky and turbid; the addition of more water, however, makes it clear. The solution of bicarbonate must be free from organic substances which may tend to remove the color of the chameleon solution. To ascertain this, the latter is added to the former drop by drop so long as the color is removed.

If it be desired to estimate the silica in the same test, the iron, as when it is analyzed for silica, may be also dissolved in sulphuric acid, and afterward oxidized with nitric acid, after which the solution is boiled to near dryness, so that the organic substances are completely destroyed. In order afterward, to drive off the nitric acid and get the manganese with certainty reduced to protoxide, the solution is boiled with a little hydrochloric acid. In this way the solution goes on rapidly and conveniently, but the titration takes longer time than when the iron is dissolved in hydrochloric acid, because the iron precipitate is more voluminous, and, in consequence, longer in being deposited. To diminish this inconvenience the solution ought to be made larger. In such a case the rule for dissolving is, one gramme iron (more if the content of silica is small) is dissolved in a mixture of two cubic centimeters sulphuric acid of 1.83 specific gravity and twelve cubic centimeters of water in the way described above, and boiled until salt of iron begins to be deposited on the bottom of the beaker. Five cubic centimeters hydrochloric acid are now added, and the solution tested with red prussiate of potash for protoxide of iron, and the boiling continued till near dryness, when all the nitric acid is commonly driven off. Should nitrous acid still show itself, some more hydrochloric acid is added and the boiling continued.

As in dissolving in hydrochloric acid and oxidizing with nitric acid the solution ought to be twice tested for protoxide of iron, even although at the first test none can be discovered. The silica is taken upon a filter, dried, ignited, and weighed. The filtrate is treated with bicarbonate of soda, and titrated with chameleon solution in the way described above. If the content of manganese is small (under 0.5 per cent.) it is not necessary to warm the liquid before titration; but in proportion as the content of manganese is larger there is so much greater reason to hasten the removal of color by warming and constant stirring toward the close of the titration.