A text-book of assaying : $b for the use of those connected with mines.Beringer, C. (Cornelius)
Science
A text-book of assaying : $b for the use of those connected with mines.
Beringer, C. (Cornelius)
Assaying
~Indirect Titration.~--The action of permanganate of potash upon a
ferrous solution is one of oxidation, hence it is evident that if any
other oxidising agent is present it will count as permanganate. In such
a case the titration can be used (indirectly) to estimate the quantity
of such oxidising agent, by determining how much less of the
permanganate is used. For example, suppose that 1 gram of iron dissolved
in sulphuric acid requires 100 c.c. of standard permanganate to fully
oxidise it, but that the same amount of iron only requires 35.6 c.c. of
the same standard permanganate if it has been previously heated with 0.5
gram of black oxide of manganese. Here it is evident that 0.5 gram of
black oxide does the work of 64.4 c.c.[4] of the permanganate solution,
and that these quantities are equivalent; moreover, if 64.4 c.c.
correspond with 0.5 gram, then 100 c.c. correspond with 0.7764 which is
the standard. On theoretical grounds, and by a method of calculation
which will be explained further on (under the heading "Calculations from
Formulæ"), it can be found that if the standard for iron is 1 gram, that
for the black oxide will be 0.7764 gram.
The principles of these indirect titrations become clearer when
expressed in a condensed form. Thus, in the example selected, and using
the formulæ Fe = Iron, KMnO_{4} = permanganate of potash, and MnO_{2} =
oxide of manganese, we have:--
(1) 1 gram Fe = 100 c.c. KMnO_{4}
(2) 1 gram Fe = 35.6 c.c. KMnO_{4} + 0.5 gram MnO_{2}
.'. 100 c.c. KMnO_{4} = 35.6 c.c. KMnO_{4} + 0.5 gram MnO_{2}
(100-35.6) c.c. KMnO_{4} = 0.5 gram MnO_{2}
64.4 c.c. KMnO_{4} = 0.5 gram MnO_{2}
The iron does not enter into the calculation if the same quantity is
present in the two experiments.
An indirect titration thus requires three determinations, but if more
than one assay is to be carried on, two of these need not be repeated.
The standard is calculated in the usual way.
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