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
This is based upon the fact that when potassic iodide in excess is added
to a strong solution of a cupric salt in a faintly acid solution,
cuprous iodide is formed and an equivalent of iodine liberated.[56] The
iodine is measured by titrating with a solution of sodium
hyposulphite,[57] using starch paste as indicator. The iodine is soluble
in the excess of potassium iodide, forming a deep brown solution; the
hyposulphite is added until this brown colour is almost removed. Starch
paste is then added, and strikes with the remaining iodine a dirty blue
colour. The addition of the "hypo" is continued until the blue colour is
discharged. The end reaction is sharp; a drop is sufficient to complete
it.
As regards the titration, the process leaves little to be desired; the
quantity of "hypo" required is strictly proportional to the copper
present, and ordinary variations in the conditions of working are
without effect. The presence of salts of bismuth masks the end reaction
because of the strong colour imparted to the solution by the iodide of
bismuth. Under certain conditions there is a return of the blue colour
in the assay solution after the finishing point has apparently been
reached, which is a heavy tax on the patience and confidence of the
operator. This is specially apt to occur when sodium acetate is present,
although it may also be due to excessive dilution.
~The standard "hypo" solution~ is made by dissolving 39.18 grams of the
crystallised salt (Na_{2}S_{2}O_{3}.5H_{2}O) in water and diluting to
one litre. One hundred c.c. will equal one gram of copper.
The starch solution is made by mixing 1 gram of starch into a thin paste
with cold water, pouring it into 200 c.c. of boiling water, and
continuing the boiling for a minute or so. The solution must be cold
before use, and about 2 c.c. is used for each assay. It should not be
added until the bulk of the iodine has been reduced.
To standardise the "hypo," weigh up 0.3 or 0.4 gram of pure copper,
dissolve in 5 c.c. of dilute nitric acid, boil off nitrous fumes, and
dilute with an equal bulk of cold water. Add "soda" solution until a
permanent precipitate is obtained, and then 1 c.c. of acetic acid. This
should yield a clear solution. Fill an ordinary burette with the "hypo."
Add 3 grams of potassium iodide crystals to the copper solution, and,
when these are dissolved, dilute to 100 c.c. with water. Run in the
"hypo" solution rather quickly until the brown colour is nearly
discharged--_i.e._, to within 3 or 4 c.c. of the finish. Add 2 c.c. of
the starch solution, and continue the addition of the "hypo" a few drops
at a time until the tint suddenly changes to a cream colour. The blue
colour must not return on standing three or four minutes. Calculate the
standard in the usual way.
In assaying ores, the copper is dissolved and separated with
sulphuretted hydrogen as in the other processes, but the sulphide should
be washed more completely to ensure the absence of iron salts.
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