=270. General Principles.=—By reason of the great cost of platinum
chlorid analysts have sought for a reagent of a cheaper nature and yet
capable of forming an insoluble compound with potash. Phosphomolybdic
and perchloric acids are the reagents which have given the most
promising results.[218] The principle of the method with the latter
salt is based on the insolubility of potassium perchlorate in strong
alcohol containing a little perchloric acid and the comparative easy
solubility of the other bases usually associated with potassium in
water. The French chemists have stated that magnesia, when present in
considerable quantities, interferes with the accuracy of the results.
Since in soil analysis considerable quantities of magnesia are often
found, this base, according to the French chemists, should previously
be removed when present in any considerable quantity, by the process
described in the first volume. Kreider, however, as will be seen
further on, working in the presence of magnesia, did not notice any
disturbing effects caused thereby. The method is applicable to the
common potash salts of the trade and with certain precautions to
mixed salts. As will be mentioned later on, sulfuric acid should be
previously removed and this is likely to introduce an error on account
of the tendency of barium sulfate to entangle particles of potash
among its molecules and thus remove them from solution. The barium
sulfate should be precipitated slowly and in a strongly acid (nitric or
hydrochloric) solution. The loss, which is inevitable, is thus reduced
to a minimum and does not seriously affect the value of the numbers
found. It is important to have an abundant supply of pure perchloric
acid, and as this is not readily obtainable in the market the best
methods of preparing it are given below. The method, while it has not
been worked out extensively, is one of merit, and seemingly is worthy
of fair trial by analysts. The process is by no means a new one, but
it will not be necessary to describe here its development any further
than to refer to the methods proposed by Serullas,[219] Schlösing,[220]
Kraut,[221] and Bertrand,[222] The method was fully developed by a
committee appointed by the French agricultural chemists in 1887.[223]
Wense has also described an improved method of estimating potash as
perchlorate after the removal of sulfuric acid and also a process of
preparing perchloric acid by distilling potassium perchlorate with
sulfuric acid in a vacuum.[224] He was also the first who proposed
the plan of rendering potassium perchlorate insoluble in alcohol by
dissolving a little perchloric acid therein.[225] The best approved
methods now known of preparing the perchloric acid and conducting the
analysis will be described in the following paragraphs.
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