06-17-04 04:33
No 513885
I found this little tidbit of information (1911 encyclopedia) that might be useful to someone somewhere. I didn't find this information posted anywhere on the hive or rhodium. I cleaned it up a good bit to make it readable, hopefully I didn't make any errors.
manganese dioxide - also called pyrolusite
Exists naturally as pyrolusite or by heating manganese carbonate to 260°C in the presence of air and washing the residue with very dilute cold hydrochloric acid. It is a hard black solid which readily loses oxygen when strongly heated, leaving a residue of Mn3O4.
potassium manganate
Manganates. These salts are derived from manganic acid H2MnO4. Those of the alkali metals are prepared by fusing manganese dioxide with sodium or potassium hydroxide in the presence of air or of some oxidizing agent (nitre, potassium chlorate, ect);
MnO2+2KOH+O2 __> K2MnO4+H2O
In the absence of air the reaction proceeds slightly differently, some manganese sesquioxide being formed;
3MnO2 + 2KOH __> K2MnO4 + Mn2O3 + H2O
The fused mass has a dark olive-green color, and dissolves in a small quantity of cold water to a green solution, which is, however, only stable in the presence of an excess of alkali. The green solution is readily converted into a pink one of permanganate by a large dilution with water, or by passing carbon dioxide through it:
3K2MnO4+2CO2 __> 2K2CO3+2KMnO4+MnO2
potassium permanganate
Permanganates are the salts of permanganic acid, HMnO4. The potasssum salt, KMnO4, may be prepared by passing chlorine or carbon dioxide through an aqueous solution of potassium manganate, or by the electrolytic oxidation of the manganate at the anode. It crystallizes in dark purple-red prisms, isomorphous with potassium perchlorate. It acts as a powerful oxidizing agent, both in acid and alkaline solution; in the first case two molecules yield five atoms of available oxygen and in the second case, three atoms:
2KMnO4+3H2SO4 __> K2SO4+2MnSO4+3H2O+5O;
2KMnO4+3H2O __> 2MnO2.H2O+2KOH+3O.
It completely decomposes hydrogen peroxide in sulphuric acid solution
2KMnO4+5H2O2 +3H2SO4 __> K2SO4 +2MnSO4+8H2O +5O2.
It decomposes when heated to 200-240°C:
2KMnO4 __> K2MnO4+MnO2+O2;
and when warmed with hydrochloric acid it yields chlorine:
2KMnO4+ 16HCl __> 2KCl +2MnCl2+8H2O+5Cl2.
Additional Useful Information: MnO2 is best freshly prepared but can be refreshed by treating with very dilute hydrochloric acid. When fresh or refreshed it is a mild oxidizer.
MnCO3 preparation from potassium permanganate is available at Manganese(III) Acetate (../rhodium /mangan
MnCO3 and MnO2 are readily available.
(Hive Bee)
06-24-04 22:02
No 515182
You mention when warming KMnO4 with HCl, chlorine is evolved, I actually think that might be dangerous to the newbee if he didn't expect it, I make Cl with a little KMnO4 and the 16% cold brick cleaner acid all the time and the amount of chlorine evolved is quite substantial, indeed I often have problems with a nasty brown liquid from the addition squirting out of my reaction bottles.
Is the brown liquid possibly dilute permanganic acid by any chance, it seems reasonable it would be formed, and making it this way would be preferable to using permanganic anhydride
A politician is like a baby's nappy, it should be changed often and for the same reason.
(Hive Bee)
06-25-04 11:53
No 515316
Yes, chlorine gas is quite dangerous. Mixing KMnO4 with HCl produces it vigorously.
What are the contents of the addition bottle? The usual dark fluffy stuff I have seen when KMnO4 is left standing tends to be MnO2 when the solution is basic. If the solution is acidic it is probably Mn+2 salt of an acid. Just about anything with a higher oxidation numbers is extremely unstable outside of the narrow neutral range.
Edit: Re-read your post ... since the solution is acidic the brown stuff is most likely MnCl2
(Hive Bee)
06-28-04 23:08
No 516065
"Edit: Re-read your post ... since the solution is acidic the brown stuff is most likely MnCl2"
Nope. MnCl2 is light pink in solution.
And for anyone working with anything involving KMnO4--be extremely careful. Boilovers can happen with very little warning. Never heat a solution containing KMnO4 unless you're watching it like a hawk and can dowse the sand in your sandbath.
This is in no way an endorsement of Birch reduction.
(Introspecter)
06-29-04 20:46
No 516344
This seems way too much when you can get a bottle of it for $8 from the same sources as always.
Rainbows & Butterflies Forever :)
(Hive Bee)
06-30-04 09:40
No 516514
MnCl2 is probably still the major constituent if the solution is acidic. Obviously a lot of other products can be mixed in but they won't be stable in an acidic medium. If insufficient HCl is present the chloride won't form and the result will be MnO2 and Mn2O3.
(Hive Bee)
06-30-04 09:45
No 516516
Potassium permanganate is not available everywhere or available in large quantities. It is however easy to prepare from chemicals that are readily available.
06-30-04 13:18
(Rated as: dumb question)
(Hive Bee)
06-30-04 18:17
No 516560
Anyone who has tried to filter MnO2 through a buchnel funnel hates KMnO4 like the plague. So why bother, other than that it's a nice project for tweakers?
(Hive Addict)
07-02-04 06:06
No 516871
500g containers of KMnO4 for ~$25 from local chemists, may be expensive if your looking at large qty's but how much do you want? its easily sourced from chem suppliers in larger qty's if need bee, no q's asked.
Whats the big problem?
AC, check your facts before giving advice to people. (...and preferably do it, with this kind of info, via PM).
Potassium Permannganate is a category 3 "illicit drug precursor" in Oz.
../rhodium /law/ill
.....fuck the shut up!