LECTURE II.-APPENDIX A.

DESCRIPTION OF THE SPECTRUM REACTION OF THE SALTS OF THE ALKALIES AND ALKALINE EARTHS.1

WE now proceed to describe the peculiarities of the several spectra, the exact acquaintance with which is of practical importance, and to point out the advantages which this new method of chemical analysis possesses over the older processes.

SODIUM.

The spectrum reaction of sodium is the most delicate of all. The yellow line Na a (see Chromolith. Table, No. 7), the only one which appears in the sodium spectrum, is coincident with Fraunhofer's dark line D, and is remarkable for its exactly defined form and for its extraordinary degree of brightness. If the temperature of the flame be very high, and the quantity of the substance employed very large, traces of a continuous spectrum are seen in the immediate neighbourhood of the line. In this case, too, the weaker lines produced by other bodies when near the sodium line are discerned with difficulty, and are often first seen when the sodium reaction has almost subsided.

The reaction is most visible in the sodium salts of oxygen, chlorine, iodine, bromine, sulphuric acid, and carbonic acid. But even in the silicates, borates, phosphates, and other nonvolatile salts, the reaction is always evident. Swan2 has already remarked upon the small quantity of sodium necessary to produce the yellow line.

The following experiment shows that the chemist possesses no reaction which in the slightest degree will bear comparison

1 From Kirchhoff and Bunsen's first Memoir on Analysis by Spectrum Observations (Phil. Mag. vol. xx. 1860).

2 Trans. Roy. Soc. Edin. vol. xxi. part iii. p. 411.

20000000

1 20000000

as regards delicacy with this spectrum-analytical determination of sodium. In a far corner of our experiment room, the capacity of which was about sixty cubic metres, we burnt a mixture of three milligrammes of chlorate of sodium with milk-sugar, whilst the non-luminous colourless flame of the lamp was observed through the slit of the telescope. Within a few minutes the flame, which gradually became pale yellow, gave a distinct sodium line, which, after lasting for ten minutes, entirely disappeared. From the weight of sodium salt burned and the capacity of the room, it is easy to calculate that in one part by weight of air there is suspended less than of a part of soda smoke. As the reaction can be observed with all possible comfort in one second, and as in this time the quantity of air which is heated to ignition by the flame is found, from the rate of issue and from the composition of the gases of the flame, to be only about 50 cub. cent. or 0.0647 grm. of air, containing less than 1 of sodium salt, it follows that the eye is able to detect with the greatest ease quantities of sodium salt less than of a milligramme in weight. With a reaction so delicate, it is easy to understand why a sodium reaction is almost always noticed in ignited atmospheric air. More than twothirds of the earth's surface is covered with a solution of chloride of sodium, fine particles of which are continually being carried into the air by the action of the waves. These particles of sea water cast thus into the atmosphere evaporate, leaving almost inconceivably small residues, which, floating about, are almost always present in the air, and are rendered evident to our eyesight in the sunbeam. These minute particles perhaps serve to supply the smaller organized bodies with the salts which larger animals and plants obtain from the ground. In another point of view, however, the presence of this chloride of sodium in the air is of interest. If, as is scarcely doubtful at the present time, the explanation of the spread of contagious disease is to be sought for in some peculiar contact-action, it is possible that the presence of so antiseptic a substance as chloride of sodium, even in almost infinitely small quantities, may not be without influence upon such occurrences in the atmosphere.

1 3000000

By means of daily and long-continued spectrum observations, it would be easy to discover whether the alterations of intensity in the line Na a produced by the sodium in the air have any connection with the appearance and direction of march of an endemic disease.

The unexampled delicacy of the sodium reaction explains also the well-observed fact, that all bodies after a lengthened exposure to air show the sodium line when brought into a flame, and that it is only possible in a few salts to get rid of the line even after repeated crystallization from water which had only been in contact with platinum. A thin platinum wire, freed from every trace of sodium salt by ignition, shows the reaction most visibly on allowing it to stand for a few hours in the air: in the same way the dust which settles from the air in a room shows the bright line Na a. To render this evident it is only necessary to knock a dusty book, for instance, at a distance of some feet from the flame, when a wonderfully bright flash of yellow band is seen.

LITHIUM.

The luminous ignited vapour of the lithium compounds gives two sharply defined lines; the one a very weak yellow line, Li ß, and the other a bright red line, Li a. This reaction exceeds in certainty and delicacy all methods hitherto known in analytical chemistry. It is, however, not quite so sensitive as the sodium reaction, only, perhaps, because the eye is more adapted to distinguish yellow than red rays. When nine milligrammes of carbonate of lithium mixed with excess of milk-sugar were burnt, the reaction was visible in a room of sixty cubic metres' capacity. Hence, according to the method already explained, we find that the eye is capable of distinguishing with absolute certainty a quantity of carbonate of lithium less than 10000000 of a milligramme in weight: 0.05 grm. of carbonate of lithium, burnt in the same room, was sufficient to enable the ignited air to show the red line Li a for an hour after the combustion had taken place.

9

The compounds of lithium with oxygen, iodine, bromine, and chlorine are the most suitable for the peculiar reaction; still the carbonate, sulphate, and even the phosphate, give almost as distinct a reaction. Minerals containing lithium, such as triphylline, triphane, petalite, lepidolite, require only to be held in the flame in order to obtain the bright line in the most satisfactory manner. In this way the presence of lithium in many felspars can be directly detected; as, for instance, in the orthoclase from Baveno. The line is only seen for a few moments, directly after the mineral is brought into the flame. In the same way the mica from Altenburg and Penig was found to contain lithium, whereas micas from Miask, Aschaffenburg, Modum, Bengal, Pennsylvania, &c., were found to be free from this metal. In natural silicates which contain only small traces of lithium this metal is not observed so readily. The examination is then best conducted as follows:-A small portion of the substance is digested and evaporated with hydrofluoric acid or fluoride of ammonium, the residue moistened with sulphuric acid and heated, the dry mass being dissolved in absolute alcohol. The alcoholic extract is then evaporated, the dry mass again dissolved in alcohol, and the extract allowed to evaporate on a shallow glass dish. The solid pellicle which remains is scraped off with a fine knife, and brought into the flame upon the thin platinum wire. For one experiment of a milligramme is in general quite a sufficient quantity. Other compounds besides the silicates, in which small traces of lithium require to be detected, are transformed into sulphates by evaporation with sulphuric acid or otherwise, and then treated in the manner described.

In this way we arrive at the unexpected conclusion that lithium is most widely distributed throughout nature, occurring in almost all bodies. Lithium was easily detected in forty cubic centimetres of the water of the Atlantic Ocean, collected in 41° 41' N. latitude and 39° 14' W. longitude. Ashes of marine plants (kelp), driven by the Gulf Stream on the Scotch coasts, contain evident traces of this metal. All the orthoclase and quartz from the granite of the Odenwald which we have

examined contained lithium. A very pure spring water from the granite in Schleierbach, on the west side of the valley of the Neckar, was found to contain lithium, whereas the water from the red sandstone which supplies the Heidelberg laboratory was shown to contain none of this metal. Mineral waters, in a litre of which lithium could hardly be detected according to the ordinary methods of analysis, gave plainly the line Li a even if only a drop of the water on a platinum wire was brought into the flame.1 All the ashes of plants growing in the Odenwald on a granite soil, as well as Russian and other potashes, contain lithium.

Even in the ashes of tobacco, in vine leaves, in the wood of the vine, and in grapes, as well as in the ashes of the crops grown in the Rhine plain near Wäghausel, Deidesheim, and Heidelberg, on a non-granite soil, was lithium found. The milk of the animals fed upon these crops also contains this widely diffused metal.s

1

It is necessary to say that a mixture of volatile sodium and lithium salts gives the reaction of lithium alongside that of sodium with a precision and distinctness which are hardly perceptibly diminished. The red lines of the former substance are still plainly seen when the bead contains 1000 part of lithium salt, and when to the naked eye the yellow soda flame appears untinged by the slightest trace of red. In consequence of the somewhat greater volatility of the lithium salt, the sodium reaction lasts longer than that of the other metal. I those cases, therefore, in which small quantities of lithium have to be detected in presence of large quantities of sodium salt, the bead must be brought into the flame whilst the observer is looking through the telescope. The lithium lines are often

1 When liquids have to be brought into the flame, it is best to bend the end of the platinum wire, of the thickness of a horsehair, to a small ring, and to beat this ring flat. If a small drop of liquid be brought into this ring, enough adheres to the wire for one experiment.

2 In the manufactories of tartaric the mother liquors contain so much lithium salts, that considerable quantities can thus be prepared.

3 Dr. Falwarczny has been able to detect lithium in the ash of human blood and muscular tissue by the help of the line Li a.

G