ON THE QUANTITATIVE ANALYSIS OF POTASSIUM AND SODIUM IN URINE. BY W. P. HERRINGHAM, M.D., F.R.C.P.

IN the course of a long series of experiments on urine involving the quantitative estimation of the potash salts contained in it, I bave found so many difficulties in the process, and so many fallacies in the methods given in text-books, that I think it worth while to describe that which I have been led to adopt, which is modified from that given in the latest edition of Neubauer and Vogell. Potassium is or may be present in the urine as chloride, sulphate, phosphate, and ethereal sulphate (Skatoxyl or Indoxyl potassium sulphate). The chlorides are volatile with heat when dry, and this produces the chief difficulties. Evaporate 100 c.c. of urine with about 5 grammes of ammonium sulphate to dryness, and fuse on a platinum capsule to a white residue. It is generally needful to add a drop or two of sulphuric acid to get this result. The white residue contains the salts as suilphates, possibly some as phosphates, and probably free phosphoric acid. Dissolve in boiling water to which a little HCl has been added. Add to it while boiling barium chloride gradually until no more barium sulphate is precipitated. This usually takes 60 to 80 c.c. of a standard solution of 30 5 grammes to the litre. Leave overnight and it will filter well. The filtrate contains the salts as chlorides or phosphates and free HCl with a little excess of barium chloride. Render alkaline with ammonia. The alkaline earths are precipitated as phosphates, and the liquid must be tested with barium chloride to see that no free phosphoric acid remains. Filter again. The filtrate contains the salts as chlorides, together with ammonium chloride, free ammonia, and baryta. Add caustic soda solution until the fluid is alkaline with fixed alkali. The baryta can now be fully precipitated with sodium carbonate and filtered off. The resultant filtrate contains the salts as chlorides, the excess of sodium carbonate, additional sodium chloride produced by the caustic soda, the excess of caustic soda and free ammonia. It must be now boiled and reduced in volume until the ammonia is driven off. Addition of HCI to neutralization then leaves sodium and potassium chloride,
1 Anleitung zur Q. u. Q. Analyse des Hars. 9te Aufl. Analytischer Theil von

Huppert, p. 455.

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and free CO2 which is driven off by boiling. After evaporating to about 100 c.c. add 30 to 50 c.c. of a 100/0 solution of platinic chloride, and evaporate almost to dryness. After cooling add alcohol which dissolves the sodium double salt, filter, dry at 100 C., and weigh, on an asbestos filter previously dried to a constant weight. The filtrate must be again tested with platinic chloride and left standing for 12 hours. Huppert advises the precipitation of the baryta by ammonium carbonate. This leaves ammonium chloride in the final solution and as ammonio-platinic chloride is as insoluble as the potassium salt, the ammonium chloride has to be expelled by evaporating the solution to dryness and heating the residue. I am satisfied that this cannot be done without loss of the potassium and sodium chlorides as well. I have never been able to recover within 4 per cent. of the whole amount of potassium in trials of this miethod, whereas by my own modification the error is less than 1 per cent. When there is much ammonium chloride present, and the heating is prolonged, the loss of potassium is much greater. If it be wished to estimate the sodium salts as well, the final solution of chlorides can be evaporated to dryness in a water-bath cooled in a desiccator, and the total of the two chlorides weighed. If standard solutions of the sodium carbonate and caustic soda have been used and the amount of each noted, the chloride derived therefrom can be calculated antd subtracted from the total. The original sodiuim chloride can then be calculated from the remainder by subtracting the potassium chloride calculated fhon the douible salt with platinum. The closer the quantities of the reagents are kept, the less difficulty will be experienced. Add only just enough HlI to dissolve the sulphates, and the ammonium chloride will be reduced; the same with the ammonia; to lessen these minimises the amount of soda requisite. The amount of sodium carbonate necessary depends upon the excess of barium chloride, which must therefore be kept as low as possible. If there is much excess of sodium salts two things must be remembered, first that if HCI is added to excess it will precipitate the sodium chloride, second that if platinic chloride is not added to sufficiency the addition of alcohol will also precipitate sodium chloride. Every addition of sodium salt needs an additional quantity of platinic chloride, but as the platinum can be recovered from filtrate and precipitate this adds very little to the expense of the analysis. The whole process is very lengthy and troublesome, but unless all these steps be carried out, no estimation of these bases is trustworthy.