Bismuth iodide and tetra-iodo bismuthate (III)
This experiment shows that iodide gives a black
precipitate when it is added to an excess amount of a solution of bismuth (III)
nitrate in dilute nitric acid. When more iodide is added, then the black
precipitate redissolves and an orange/red solution, containing the tetra-iodo
bismuthate (III) ion is obtained.
The two pictures below show the black precipitate with
excess bismuth (III) and the red solution with excess iodide.
When the solution with the orange/red iodide-bismuth
complex is diluted, then the black precipitate of bismuth iodide is formed
again, together with a white precipitate, due to hydrolysis of bismuth (III).
Apparently, the orange/red complex is not very stable and requires a moderately
high concentration of iodide and/or acid. On further dilution, the black
precipitate of bismuth iodide hydrolyses and more of a white precipitate is
formed. With this reaction, iodide is released again and this released iodide in
turn allows remaining non-hydrolysed bismuth to form the orange iodo-complex.
So, in practice, on dilution a complex equilibrium exists between the following
species:
- orange BiI4–
- black BiI3
- white Bi(OH)XY
Here, X and Y can be OH–, I– or NO3–.
When the black BiI3 hydrolyses, then free I– is formed and
this can form more BiI4–.
When the orange/red contents of the test tube is poured in
an erlenmeyer with approximately 60 ml of water, then first the liquid becomes
orange and turbid. Within a few seconds, the liquid turns black at the bottom
half part, where the highest concentration of bismuth and iodide is present.
The contents of the small erlenmeyer is poured in a larger
erlenmeyer with 300 ml of water. The total volume of liquid becomes
approximately 350 ml. In the large erlenmeyer, a dark turbid grey/yellow liquid
is obtained. This dark liquid however turns orange in approximately 10 seconds,
but it remains turbid. The black BiI3 hydrolyses to a white basic
bismuth salt in an orange liquid. In the picture below, the contents of the
large erlenmeyer is shown, approximately 30 seconds after pouring in the
contents of the smaller erlenmeyer.
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