It was not very easy to apply the methods of the laboratory to the
preliminary treatment of the residue in the factory. M. Debierne
investigated this question, and organised the treatment in the factory.
The most important point of his method is the conversion of the
sulphates into carbonate by boiling the material with a concentrated
solution of sodium carbonate. This method avoids the necessity of fusing
with sodium carbonate.
The residue chiefly contains the sulphates of lead and calcium, silica,
alumina, and iron oxide. In addition nearly all the metals are found in
greater or smaller amount (copper, bismuth, zinc, cobalt, manganese,
nickel, vanadium, antimony, thallium, rare earths, niobium, tantalum,
arsenic, barium, &c.). Radium is found in this mixture as sulphate, and
is the least soluble sulphate in it. In order to dissolve it, it is
necessary to remove the sulphuric acid as far as possible. To do this,
the residue is first treated with a boiling concentrated soda solution.
The sulphuric acid combined with the lead, aluminium, and calcium
passes, for the most part, into solution as sulphate of sodium, which is
removed by repeatedly washing with water. The alkaline solution removes
at the same time lead, silicon, and aluminium. The insoluble portion is
attacked by ordinary hydrochloric acid. This operation completely
disintegrates the material, and dissolves most of it. Polonium and
actinium may be obtained from this solution; the former is precipitated
by sulphuretted hydrogen, the latter is found in the hydrates
precipitated by ammonia in the solution separated from the sulphides and
oxidised. Radium remains in the insoluble portion. This portion is
washed with water, and then treated with a boiling concentrated solution
of carbonate of soda. This operation completes the transformation of the
sulphates of barium and radium into carbonates. The material is then
thoroughly washed with water, and then treated with dilute hydrochloric
acid, quite free from sulphuric acid. The solution contains radium as
well as polonium and actinium. It is filtered and precipitated with
sulphuric acid. In this way the crude sulphates of barium containing
radium and calcium, of lead, and of iron, and of a trace of actinium are
obtained. The solution still contains a little actinium and polonium,
which may be separated out as in the case of the first hydrochloric acid
solution.
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