That's a solid bit of work. Thanks. The info about different salts' salubilities especially- all is useful. Can't quite match it, but....
Allow me to retort
To a 500ml flask, ~60g of Cu/Ni 75%/25% alloy was introduced, which is about 1 mole, and 60g aq. HCl 370g/L (~33%) was added, followed by an additional 10g 98%sulfuric acid. The reaction was very slow with slight bubble formation over minutes, even with heating. The solution turned slightly green.
The heat was removed, and roughly 40g KNO
3 was then added to the vessel, and an additional 50ml H
2O. Most of the potassium nitrate dissolved, and gentle heat was re-applied such that the solution was barely refluxing. The solution quickly developed a greenblue colour which darkened over the next 3 hours to a drty coca-cola colour. When the vessel was removed from the heat and allowed to cool, a small amount of dirty white solid crystalline precipitate formed (NiCl
2?).
The heat was re-applied for another 3 hours, and then the vessel was allowed to cool and placed in storage for 3 days. Continued refluxing would have accelerated the process further, but was not possible at this time. When it was examined again the solution was a very dark dirty coca-cola, the alloy was mostly dissolved (~75%), and there were beautiful large blue crystals of copper sulfate forming, mostly on the alloy pieces. It may be that a significant amount of the copper has actually separated this way all by itself. They will be collected and weighed to explore this. There is also a dirty-white powdery crystalline sediment.
During heating additional water was added to replace that lost through evaporation, twice. After cooling additional water had evaporated, leaving around 125ml solution.
Additional heating will follow, after physically extracting the large CuSO
4.5H
2O crystals.
.............................................
Looking forward....
It would be interesting to preprare more than one catalyst type from this.
Having read the Urishibara prepration notes, an Al/Ni system- U-Ni-AB seems ideal, for the intended purpose, and the preference for producing primary amines by U-Ni-NH
3 is very cool indeed.
Also with interest it is noted, under U-Ni-C preparation (a more highly activated form) :
https://www.thevespiary.org/rhodium/Rhodium/chemistry/urushibara.html
"To reduce the particle size of the precipitated nickel, it is necessary to retard the velocity of the ion exchange reaction; that is, to retard the speed of deposition of nickel."
It strikes me that there is room for a lot of fleshing out here.
For example, How about this:
# preparing a U-Ni-BA aggregate, but using NH
3 as the base;
# preparing a U-Ni-BA aggregate, then further processing it as per U-Ni-C to increase activity;
# preparing a U-Ni-BA aggregate, but using NH
3 as the base; then further processing it as per U-Ni-C to increase activity...
and so on.
maybee someone can add to this.
The last one looks particularly cool. It takes a bit of extra preparation but the if end result is freely, economically available and achieves the desired effect, mercury can be replaced with something that's a bit too common to List.
If they ban Nickel, they'll have to ban lignin too.
It is also being considered, using some of the crude copper/nickel solution as-is, and investigating whether the competing precipitation of Cu and Ni also produces a reduced particle size and (depite the presence of the far less-active Cu variant) may very well produce an active product.
One of Ni catalyst letdowns is a less-than-perfect durability i catalytic activity- yet can be regenerated (or even somewhat revitalised with U-Ni).
For Further down the track, to test the catalyst.....
Some dill apiole is also being extracted from seeds; The expected oil qty will not be large, but should be enough for a couple of runs.