Treating a highly ionic suspension of Mg(OH)2 (from NaOH and MgSO4, as one preparation path, but do NOT use aqueous NH3 as the base as any residual
NH4SO4 contamination could form the highly unstable/explosive NCl3 upon chlorination) with Cl2. The Mg(ClO)2 formed is highly unstable
disproportionating readily into Mg(ClO3)2 and MgCl2 with very little heat or even treatment with air/O2 (so the answer is yes to your question if you
select the right hypochlorite!). Source: see "The Manufacture of Sulphuric Acid and Alkali: Ammonia-soda, various ..." by Georg Lunge, an online
googlebook, link: http://books.google.com/books?id=FnrTAAAAMAAJ&pg=PA669&a... . To quote from page 669:
"Now chlorine was passed into a milk of- magnesium hydroxide and water, at temperatures between o° and 100°. Even at 0°, together with magnesium
hypochlorite, much chlorate was formed, more than corresponding to half of the chlorine entering into the reaction. At 15° a little more chlorate was
formed, together with much hypochlorate, some of which was changed into chloride, with evolution of oxygen. In both solutions the hypochlorite is
easily converted into chlorate, not merely by heating to 50°, but even by prolonged agitation by a current of air at ordinary temperatures. At 70°
C, from the first mostly chlorate was formed, with a little chloride, produced by loss of oxygen. Hence magnesium hypochlorite in statu noscendi does
not possess much stability and is easily transformed into chlorate."
To form KClO3, add KOH and filter out the Mg(OH)2, or more traditionally, add KCl to the aqueous Mg(ClO3)2 and cool to separate out the Potassium
chlorate.
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For the more advanced path, add a touch of Acetic acid/acetate, NaCl and even sunlight to the brew. Some sources:
to quote a 2000 paper (link: http://pubs.acs.org/doi/abs/10.1021/ic991486r ):
"Acetic acid has a second catalytic role through the formation of acetyl hypochlorite, which is much more reactive than HOCl in the transfer of Cl+ to
ClO2- to form ClOClO."
Another article, "Effect of Chloride Ion on the Kinetics and Mechanism of the Reaction between Chlorite Ion and Hypochlorous Acid" link:
http://www.researchgate.net/publication/23141635_Effect_of_c... , to quote:
"Moreover, they found that acetate ion accelerates the formation of ·ClO2 enormously." and also "It was interpreted by a steady-state formation and
further reactions of acetyl hypochlorite. "
With respect to the role of chlorides in promoting chlorate formation, the authors states in the abstract, to quote:
"It is found that the presence of the chloride ion significantly increases the initial rate of ·ClO2 formation."
Cited reactions involving active chlorine species to accelerate the formation of a chlorate include:
Cl2O2+ H2O --> ClO3- + Cl- + 2 H+ (page 2 eq 5)
Cl2O2 + HOCl --> ClO3- + Cl2 + H+ (page 2 eq 8)
where Acetyl hypochlorite is expected in having a catalytic role.
Photolysis most likely proceeds along the following paths involving the species ·Cl, ·OH and ·ClO:
Cl2 + hv --> 2 ·Cl
2 ·Cl + 2 HOCl --> 2 ·OH + 2 Cl2 (g)
2 ·OH + 2 HOCl --> 2 H2O + 2 ·ClO (forming some Cl2O2)
Cl2O2 + HOCl --> HClO3 + Cl2(g)
where the presence of sunlight, free Chlorine and Hypochlorous acid are required in this particular chain.
Source: See for example "Photolysis of free chlorine species (HOCl and OCl- ) with 254 nm ultraviolet light" page 281 attached, and also Table 2, page
797 at http://www.geosci-model-dev-discuss.net/3/769/2010/gmdd-3-76... .
[Edited on 29-10-2013 by AJKOER] |
. I should have including the information I've
gathered and you're right on that, thank you for being patient with me, I've been a little angry with life lately. On an unrelated note, I'm quite
ecstatic that you replied to my post. I love your videos!
I might try this approach someday.