Scientific American Supplement, No. 441, June 14, 1884. eBook

This eBook from the Gutenberg Project consists of approximately 135 pages of information about Scientific American Supplement, No. 441, June 14, 1884..

Scientific American Supplement, No. 441, June 14, 1884. eBook

This eBook from the Gutenberg Project consists of approximately 135 pages of information about Scientific American Supplement, No. 441, June 14, 1884..

Experiments show that the quantity of peroxide deposited depends on the nature of the solution and the strength of the current.  In case of very feeble currents and slight acidity, its quantity is so small that it does not need to be taken into consideration.  If the lead solution is very dilute scarcely any current is observed, lead solutions per se being very bad conductors of electricity.

Faintly acid concentrated lead solutions give loose peroxide along with much spongy metallic lead.  Free alkali decreases the separation of peroxide; feebly alkaline solutions, concentrated and dilute, yield relatively much peroxide along with metallic lead, while strongly alkaline solutions deposit no peroxide.

Dried lead peroxide is so sparingly hygroscopic that it may be weighed as such; its weight remains constant upon the balance for a long time.  In order to apply the peroxide for quantitative determinations, a large surface must be exposed to action.  As positive electrode a platinum capsule is convenient, and a platinum disk as negative pole.  The capsule shape is necessary because the peroxide when deposited in large quantities adheres only partially, and falls in part in thin loose scales.  It is necessary to siphon off the nitric solution, since, like all peroxides, that of lead is not absolutely insoluble in nitric acid.  The methods of Riche and May give results which are always too high, since portions of saline solution are retained by the spongy deposit and can be but very imperfectly removed by washing.  This is especially the case in presence of free alkali.

The author has proceeded as follows:  The lead peroxide is dried in the capsule, and there is passed over it pure dry gaseous sulphurous acid in a strong current from a rather narrow delivery tube.  Lead sulphate is formed with evolution of heat; it is let cool under the exsiccator, and weighed as such.  Or he ignites the peroxide along with finely pulverized ammonium sulphite; the mass must have a pure white color.  After the conclusion of the reaction it is ignited for about 20 minutes.  The results are too high.  The proportion of actual lead peroxide in the deposit ranges from 94 to 94.76 per cent.  The peroxide precipitated from a nitric solution may, under certain circumstances, be anhydrous.  This result is due to the secondary influences at the positive pole, where the free acid gradually withdraws water from the peroxide.

The peroxide thrown down from alkaline solutions retains alkali so obstinately that it cannot be removed by washing; the peroxide plays here the part of an acid.  The lead nitrate mechanically inclosed in the peroxide is resolved by ignition into oxide, hyponitric acid, and oxygen; this small proportion of lead oxide does not exert an important influence on the final result.  The quantity of matter mechanically inclosed is relatively high, as in the precipitation of much lead peroxide there is relatively more saline matter occluded than when a few centigrammes are deposited.  The peroxide incloses also more foreign matter if it is thrown down upon a small surface than if it is deposited in a thin layer over a broad surface.  From numerous analyses the author concludes that in presence of much free nitric acid the proportion of water is increased; with free alkali the reverse holds good.

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Scientific American Supplement, No. 441, June 14, 1884. from Project Gutenberg. Public domain.