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From: AHAHMA%kontu.utu.fi@ssyx.ucsc.edu
Subject: Re: quite mail list
Date: 19 Mar 90 13:13:21 GMT
>The "improvised plastic explosive", if it's the one I've
>heard of (and never made) is a potassium perchorate explosive.
>IT's made with bleach and white gasline, (I can post details if
>youre really interested.) Anyway, its nothing like as good
>as C4, and probably less stable.
>-Ford
Chlorates and perchlorates are really a good raw materials for these
improvised stuffs. They can always be made to explode, if mixed with
combustible materials and if the oxygen balance of the mixture is near
zero (+- 50 %). The combustible material can be almost anything, wheat
flour, soja oil or toilet paper will do fine.
The "improvised plastic" seems to be quite the same I have used a long
time ago. I only had sodium chlorate, but it worked just fine. As a
fuel I had PVC or polystyrene dissolved in a plasticizer(phtalates,
sebacates) or if I didn't have any plasticizer, I took xylene as the
solvent. The finished product looked similar to C-4, but wasn't even
nearly as effective. It did make a large puff of smoke and a bang, but
it was almost ineffective on, for example, stone or steel. This stuff
had also the same drawbacks as the fertilizer mixtures: a minimal
charge, in this case about 0,5 kg. The mixture was also relatively hard
to ignite, I had to take a small booster charge, the blasting cap alone
was not enough, i.e. the mixture was actually too stable.
If perchlorates are used (potassium or ammonium), the explosive will be
a lot more brisant than with chlorates and safer, too. Still, the
detonation velocity is under 4500 meters/second, which is not enough
for unconfined charges. Hence, chlorates and perchlorates can
effectively be used for mining purposes only, not for demolitions.
3P
From: glhurst@onr.com (Gerald L. Hurst)
Newsgroups: alt.engr.explosives
Subject: Re: Weed-killer Explosives
Date: 6 Apr 1996 04:27:30 GMT
In article <4k3npa$cik@red.paston.co.uk>, alwyn@paston.co.uk (Colin
Breame) says:
> Hi everyone, I don't know much. I've bought a tub of weed killer,
>mixed it with sugar but it don't explode. What am I doing wrong?
You're doing fine as long as it doesn't explode. I hope you didn't
mix the whole tubful.
> Iam doing 'A' level chemistry and according to what I have learnt, it
>should go BooM; only when I light it, it just burns very rapidly with
>a very smokey flame. On the lid it says it contains Sodium Chlorate &
>'fire depressant'.
It's the "A" level thing that explains it. The chemists who added
the suppressant have finished the "Z" level. The additive works well,
doesn't it?
> Can someone please give me some answers? What is this fire
>depressant? How do I remove it? Is it worth the hassle or is there
>an easier way of obtaining an oxidising agent? Help, Help, Help, ....
When you can snatch the suppressant from the chlorate, grasshopper,
it will be time to go boom.
Jerry (Ico)
From: "Lloyd E. Sponenburgh" <lloyds@fiscalinfo.com>
Newsgroups: rec.pyrotechnics
Subject: Re: PbO2 as anode material?
Date: 21 May 1996 13:09:56 GMT
Justin Lemire-Elmore <103167.1406@CompuServe.COM> wrote:
>Could anyone comment as to how the lead dioxide plate from
>a charged lead-acid battery would serve as the anode in a
>Cl -> ClO4 cell?
Sure can! Been there, worn the Tee-Shirt, lost the ball cap, and all that
rubbish.
Dr. H lent me a plate he'd salvaged to do just that. The results were
disappointing, but not unexpected.
The PbO2 is held in a grid of lead. The lead undercuts drastically during
electrolysis, and eventually dissolves completely, leaving a bucket full of
little PbO2 rectangles, and a nasty yellow solution of (supposedly) chlorides
of sommat... probably lead. (durr!)
LLoyd
Newsgroups: alt.drugs.chemistry,alt.engr.explosives,rec.drugs.chemistry,
rec.pyrotechnics,tw.bbs.sci.chemistry,sci.chem
From: B.Hamilton@irl.cri.nz (Bruce Hamilton)
Subject: Re: Making Potassium Chlorate
Date: Fri, 16 May 1997 17:54:46 +12
In article <863758726.893@dejanews.com>
TreeSQUIRL@ois.lemuria.com writes:
>I know that this question has been asked a million times aready.
Given that you've posted via Dejanews, how come you didn't find
one of the answers?.
>However, how can I make KClO3. And I don't want to order it.
Strike one...
( most users would buy it, it's only $30/500gms for the pure
laboratory grade, much cheaper for the commercial grade )
> I've tried the electrolysis methods but they didn't work.
Strike two...
( most chemists would have little difficulty producing it by
electrolysis of hot, concentrated, alkaline solution of KCl )
> I just what to know if there is a way to make it and with what and how.
Yes, using potassium chloride solution interacting with calcium chlorate,
and calcium chlorate is easily made by passing chlorine into hot calcium
hydroxide slurry.
> I'm familiar with a wide range of chemistry so don't worry about
>the understanding of it.
Oops, why did I bother, you apparently knew how all the time,
after all the above process is widely used to make it.
> I really want a method that works with out being in a lab.
Strike three..
( If you haven't got access to lab, and are familar with a wide
range of chemistry, you would be aware of the stupidity of
trying to make a cheap, flammable, strong oxidising agent,
such as KClO3 outside of a laboratory.)
>Please Respond!
Certainly, however I suspect you may become a self-correcting
evolutionary anomaly. Next time, please omit sci.chem, and
try more sympathetic groups.
Bruce Hamilton
Subject: Re: Electrolizing KC104
From: nreitzel@lonestar.jpl.utsa.edu (Norman L. Reitzel )
Date: Aug 24 1995
Newsgroups: rec.pyrotechnics
In article <41g4b2$b32@grouper.Exis.Net> lewisr@exis.net writes:
>I followed the instructions found in the common online file on making
>KC104 by electrolyzing potassium chloride (KC1) using carbon rod
>electrodes, piece of sheet steel, milk jugs, etc.
>
>Everything went well, I kept water level and electrical current at
>about 8-10 amps for the 5 days the procedure calls for. However, when
>I crystalized the resulting solution I saw only "cactus needle-like"
>KC103 crystals forming. A large amount of this material formed, about
>12-16 oz.
>
>I never saw "flat rhombic shaped, almost square" crystals indicative
>of KC104 crystalize out of solution as described in the article. I
>may have let the electrical current drop a bit low for a short period
>of time, but other than that I am stumped at my lack of success. I
>did not use the optional potassium chromate/dichromate.
>
>Any ideas from anyone on how to improve my success? Would continued
>electrolization of a KC103 rich electrolyte result in KC104?
Producing perchlorate from chlorate requires higher temperatures and a
higher anode current density than to produce chlorate. Generally, it is
a bad idea to try to combine the two steps into one run. I typically run
hot KCl in a chlorate cell and continuously crystallize by taking a
fraction of the electrolyte and cooling it to 0C. Then, for the
production of perchlorate, I saturate a cell with chlorate. I think that
the presence of KCl in the electrolyte prevents development of the proper
voltages -- that is, you won't make perchlorate until all the chloride is
converted to chlorate.
You're on the right track.
------------------------------------------------------------------------
Norman L. Reitzel, Jr. | "When you live beside the graveyard,
nreitzel@lonestar.utsa.edu | you can't cry for every funeral."
Blue Water Ventures, dba. | Russian Proverb
------------------------------------------------------------------------
Subject: Re: Separation of fire retardant
From: nreitzel@lonestar.jpl.utsa.edu (Norman L. Reitzel )
Date: Apr 08 1996
Newsgroups: rec.pyrotechnics
In article <4k1kvs$5g6@soap.news.pipex.net> rdicken@solo.pipex.com
(Robert Dicken) writes:
>This question has been asked before but I have never seen or fully
>understood the answers given. Sodium Chlorate in the UK, and maybe in
>the US as well, contains a fire retardant to minimise among other
>things its use in pipe bombs etc. I want to use it to make the fuel
>for a bottle type rocket. I'm at the same time use BP and want to
>compare the weight lifting abilities, i.e. power to weight ratios of
>the two.
>
>Firstly what exactly is the fire retardant and how does it work?
>Secondly is there a "relatively" easy way to separate the Sodium
>Chlorate out, in other words not in a fully equipped chemistry lab,
>that can give reasonable yields.
Retardants are ammonium phosphates, designed to cool the incipient
combustion by decomposition. These phosphates are also used in dry
chemical fire extinguishers.
"Separation" isn't the answer, as sodium chlorate is a PITA anyway. What
you want to do instead is to precipitate potassium chlorate, which is
relatively insoluble in water (as compared to sodium) and far less
hygroscopic. To this end, prepare saturated solutions of the sodium
chlorate and potassium chloride (plant store, "muriate of potash") in
water, and mix them. The potassium chlorate will precipitate nicely.
Filter and dry. About 70% yield.
Finally -- why chlorates? Are you suicidal or just dumb? Professional
pyrotechnicians avoid chlorates like the plague they are. They are far
too unstable to use except in a very few exceptional circumstances. You
can convert sodium chlorate into sodium perchlorate by melting in a clay
(not graphite!) crucible at around 500 C, holding the melt for 20
minutes, and pouring carefully into a (large) pail of water to quench.
Evaporate, and Then do the potassium chloride trick, and you will have about
60% yield of potassium perchlorate -- MUCH better for darn near everything.
--
Norman L. Reitzel, Jr. | "When you live beside the graveyard,
nreitzel@lonestar.utsa.edu | you can't cry for every funeral."
Blue Water Ventures, dba. | Russian Proverb
Subject: Re: flash powder detonates??
From: glhurst@onr.com (Gerald L. Hurst)
Date: Dec 21 1996
Newsgroups: rec.pyrotechnics
In article <59fujl$1ua@bashir.peak.org>, billn@PEAK.ORG (Bill Nelson) says:
>Robert Goodman (robert.goodman@accbbs.com) wrote:
>: I remember talking to some other pyros, or posting something here about
>: it, and getting a corretion, but I don't remember what the correction
>: was. I seemed to recall reading that a type of slurry explosive was
>: made in situ (in mining, quarrying, whatever) by mixing slurries of
>: KClO4 and Al. Being wet, I imagined this mix had to be initiated by
>: some means other than lighting it. Therefore I inferred that a flash
>: mix must be able to detonate if initiated with a suitable shock wave.
>
>There are slurry explosives that use ammonium nitrate. They are usually
>not cap sensitive, but require a booster charge.
>
>I cannot think of any KClO4/Al, or any other perchlorate based slurry
>explosives. I don't even recall any Streetite/Cheddite type mixtures used
>in slurry explosives.
Chlorates and perchlorates were still used in US commercial explosives
during the early part of this century. Years ago, Roger Byers told me
that his father, Laud S. Byers, had a fluorishing business in chlorate
based explosives which ended when one of his employees blew himself
to pieces. Although there was suspicion of suicide, the incident was
said to have served for an excuse for a (herein unnamed) larger powder
company to bring pressure to outlaw chlorate explosives and thus
destroy a growing competitor.
I am not in any position to judge these events except to make the
observation that chlorate and perchlorate explosives continued past
that time to be used in other parts of the world, notably in the Eastern
block and Japan.
In the US slurry/emulsion field, perchlorates have been used in
moderation (e.g. at the 1% or less level) as sensitizers. If for no
other reason, perchlorate use is limited because of the relatively
high price compared with nitrates.
I once developed a high performance aqueous perchlorate-based liquid
explosive for shaped charge applications. The composition was never
used by the company for which it was intended. The formulation
"walked" to another company (which will also remain nameless) where
it was used for shaped cratering charges primarily in underwater
trenching. The velocity and energy of the explosive was impressive
but it would have been too expensive for general industrial use.
If you have PATR 2700, you will find references to Laud Byers at least
in connection with his plastic-cased shaped charges which became
known as "Boulder Busters" and were the first product of Kinetics
International before the invention of its namesake explosive,
"Kinepak." The original formulation used in the Boulder Busters was,
of course, not based on a chlorate explosive but instead on another
Byers invention, a nitrate-based material known as "Moleculite." The
Boulder Busters were later largely supplanted at Kinetics by the
Kinepouch, which is quite effective as a secondary blasting charge
because of the high brisance of the Kinepak and the intimate target
contact afforded by the flexible packaging.
Jerry (Ico)
From: ahahma@polaris.utu.fi (Arno Hahma)
Newsgroups: rec.pyrotechnics
Subject: Re: Prospective FAQ - Comments Please!
Message-ID: <1992Jun1.184200.506@polaris.utu.fi>
Date: 1 Jun 92 18:42:00 GMT
In article <1992May30.223253.4796@ousrvr.oulu.fi>
kempmp@phoenix.oulu.fi (Petri Pihko) writes:
>> Bic Schediwy writes on compositions containing ammonium chloride
>> and potassium chlorate:
>> >I'm guessing but I suspect that its stability depends on a lack of
>> >moisture.
>> >That is to say, for ammonium chlorate to form, moisture is required.
>> >This guess is supported by Lancaster in a following sentence: "Formulations
>> >of this type employ a little pariffin oil to help exclude moisture and
>> >reduce sensitivity." Potassium chlorate is not considered hygroscopic
Your guess is quite correct, moisture is needed (see later for
experimental evidence). Once the reaction starts, it generates more
water, which in turn catalyzes the reaction further. As a result, the
reaction is autocatalytic at first. On the other hand, when the water
content raises high enough, the water will start cooling the mass. In
small amounts, the mass may or may not ignite by itself. With larger
amounts of the mixture, an autoignition is more probable, as with any
formulas with such a tendency.
>As a poster of the original formula, I have done some testing on the
>composition. The composition shows no signs of decomposition and no odour
>of chlorine is detectable after keeping it moist for two days (which would
>have indicated the formation of ammonium chlorate). The composition was not
>more sensitive to ignition after subsequent drying and did not show any
>unexpected behaviour. These tests were by no means thorough, but convincing
>enough for me.
For me, the tests are not convincing. I assume you have tested at room
temperature. The reaction is really slow at that temperature, I would
suggest it takes at least a week until it gets fast enough to be
detectable by your nose ;). How about making a test batch and
observing it for a longer time?
A mixture of sodium chlorate and ammonium perchlorate at 70 oC shows
absolutely no signs of decomposition for two and a half days. Then,
suddenly, an autocatalysis is observed and the reaction runs out of
control within a few ten minutes. The compounds were air dry at the
beginning. At the end of the experiment, the mixture was a wet mass.
The mixture did not ignite, but it developed large amounts of oxides
of chlorine (mainly chlorine dioxide), which would have ignited
practically anything organic. This time, there was nothing organic in
the vicinity.
You have tested with potassium chlorate, which is less reactive than
sodium chlorate. So, it is quite possible that the smoke mixture is
safe for a long time. The problem is: when it starts reacting, it does
so fast and suddenly. Moreover, the time until too fast a reaction
is more or less undetermined and depends heavily on initial
conditions, such as temperature and moisture. This is why I would not
keep chlorate/ammonium salt -mixtures any longer than absolutely
necessary. Ramming the mixtures into tubes is asking trouble after a
shorter random delay.
If the above mentioned mixtures are to be stored, it is a very good
idea to use a two-component resin as a binder. Such a resin will
greatly reduce the possibility of individual crystals getting into
contact with each other. The resin would also prevent air humidity
from getting into the mass.
>However, it has been reported that a composition with colophony resin as
>a fuel _does_ show signs of decomposition after moistening.
Probably due to an exothermic reaction between the resin and the
chlorine oxides. Such a reaction would also generate water to help the
initial decomposition more. Or may be the resin contains something
acidic and accelerates the decomposition of the chlorate.
>Possible explanations:
>It is _not_ universally true that _all_ combinations of ammonium salts and
>chlorates are dangerous (although many of them are). This is what the
>textbooks say, but I believe it is an overstatement.
It may be an overstatement, if considered over short periods of time.
But taking it as an overstatement for a month storage is not that
clear at all. It is probably not hazardous to make the
KClO3-NH4Cl-sugar -smoke and use it within a few days. Still, I would
not store that mixture, not to mention pressing or ramming it. Some
people have done that, but it does not mean it is safe. Pressing
chlorate-based mixtures is not a good practice anyway.
>What _is_ true is the hazardousness of solid ammonium chlorate. It can
>precipitate from a solution containing ammonium and chlorate ions, if
True. And even the concentrated solutions are really nasty, since they
generate different oxides of chlorine. Some of the chlorine oxides are
spontaneously explosive (I have had such an explosion once while
making chlorine out of sodium chlorate). Besides, the fumes are
extremely corrosive and poisonous - even gold is corroded by chlorine
oxides.
>Potassium chlorate is less soluble in water than ammonium chlorate.
>Ammonium chloride is less soluble in water than ammonium chlorate (although
>the difference is very slight at room temperature).
>Thus, no solid ammonium chlorate will be formed from the moistened mixture
>of the two salts under normal conditions. The products of the exchange
>reaction - ammonium chlorate and potassium chloride - are more soluble
Never say "no" in chemistry ;) !. Even if the reaction is not
favorable, there is certainly some ammonium chlorate present; who
knows in which form. A great majority of the reactions in chemistry go
over a thermodynamically unfavorable intermediate and still, such
reactions are known to happen. Take almost any organic reaction as an
example.
According to the law of mass action, more ammonium chlorate will be
formed as some decomposes. If the mass is moist, the formation of the
ammonium chlorate will be extremely fast (ionic reaction in aqueous
solution) and will not restrict the decomposition. If there are
organic fuels present, there will also be a lot of heat, which will
aid the dissolution of the reacting salts.
If you don't believe a water solution can burn, try boiling a
saturated solution of sodium chlorate and sugar, in stochiometric
proportions. It may be quite a surprise when the water clear solution
will start burning fiercely and melt your kettle (may be not, if the
kettle is made of stainless steel ;-).
>My conclusion:
>The original composition (based on either starch or dextrin) is reasonably
>safe,
Let me add: "if used as soon as prepared."
>There are several formulas, but I believe the military uses hexachloroethane
>in nearly all of its smokes. HC is a strange-smelling substance and the
There are basically two types of smokes: HC and phosphorus. HC smokes
are based on metal-HC -reaction. Phosphorus smokes usually consist of
red phosphorus, an oxidizer and a binder. Both are highly effective,
the HC smokes generate slowly and last long whereas the phosphorus
smokes give off most of their smoke within seconds.
>smoke is heavily irritating. Still, it's the best for them. The other
>ingredients are zinc powder, zinc oxide, naphtalene (in gray smokes) and
>occasionally titanium dioxide.
Some chlorinated polymers can also be used as the chlorine donor
instead of HC. But you are right, HC is the best, it gives more
smoke/mass unit than most materials. There are also smokes without HC
and metals and such smokes are even more effective than the
traditional ones. One of these is likely to be based on zinc oxide, an
ammonia donor (ammonium chloride, likely) and an energy donor
(possibly double base or AP composite powder).
> ___. .'*''.* Petri Pihko kem-pmp@ Mathematics is the Truth.
ArNO
2
From: ahahma@polaris.utu.fi (Arno Hahma)
Newsgroups: rec.pyrotechnics
Subject: Re: Self-igniting Molotov cocktails
Message-ID: <1991Sep6.151706.6182@polaris.utu.fi>
Date: 6 Sep 91 15:17:06 GMT
In article <22810208@hpcvaac.cv.hp.com> billn@hpcvaac.cv.hp.com (bill nelson) writes:
>dbetz@magnus.acs.ohio-state.edu (Drew Betz) / 5:31 pm Sep 4, 1991 / writes:
>>matches to the exterior of the bottle. The idea is that
>>when you toss the bottle, the glass shatters and the battery
>>acid ignites the sulfur on the matches. Could such a
>>thing work?!?
Yes, it probably will. The stronger the acid the more probably, i.e.
using concentrated sulphuric acid is advantageous and you do not
need 50 % of it in the mix, a few per cent will be enough.
This is a good example of the incompatibility of chlorates with acidic
compounds. The matchheads are made of potassium chlorate, antimony
sulphide, ground glass, possibly sulphur, and a glue, that is, of
a chlorate mixture. Chlorates + acids = chlorine oxides, that are
powerful oxidisers. Powerful oxidiser + combustibles = fire.
>I doubt it. There are far better ways.
Sure, but still, this one probably works, although there will be some
delay with battery acid.
>Bill
ArNO
2
_______________________________________________________________________________
_____ _____ _____
| |__| |__| | A. Hahma
| | Research Centre of the Defence Forces
|_________________| Department of Chemistry
| . | Laboratory of Propellants and Explosives
| . . | BOX 5
| . | SF-34111 LAKIALA
_| . . |_ Tel. +31-492177
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|_________________|
From: nreitzel@lonestar.utsa.edu (Norman L. Reitzel )
Newsgroups: rec.pyrotechnics
Subject: Re: Potassium chlorate from potassium chloride
Message-ID: <1994Jan22.155830.17406@ringer.cs.utsa.edu>
Date: 22 Jan 94 15:58:30 GMT
In article <CK04Jx.p3H@ns1.nodak.edu> lihke@plains.NoDak.edu (Robert Lihke) writes:
>>Yes, you can make chlorate. Hypochlorite + heat -> chlorate. You can
>>get at best about 40gm of chlorate per gallon of bleach. The reaction
>>is a well known disproportionation, and in fact is the key reaction in
>>producing chlorates by electrolysis.
>
>Wait a minute, that would mean that just by boiling bleach I would get a
>sodium chlorate solution and chlorine? BEcause the application I am
>looking into can use sodium chlorate just as well as potassium chlorate,
>but I'm rambling. Anyway, if what I said is not correct, please enlighten me.
Robert,
That would be sodium chlorate and sodium chloride:
3 NaOCl --> NaClO3 + 2 NaCl
Trouble is, how do you intend to separate the chlorate? Consider
the following chart of solubilities at both high and low temperature:
Sol @ 20C Sol @ 100C
NaCl 35g/100ml 39g/100ml
NaClO3 79g/100ml 230g/100ml
NaClO4 209g/100ml 284g/100ml
KCl 34g/100ml 56g/100ml
KClO3 7.1g/100ml 57g/100ml
KClO4 .75g/100ml 22g/100ml
The most practical way to do the separation is to boil the hypochlorite
to disproportionate it to chlorate and chloride, then add saturated KCl
to precipitate the chlorate at 0C. In the commercial manufacture of
chlorates, nearly saturated brine is electrolysed, and then either
KCl is added to precipitate KClO3, -or- the solution is evaporated to
small volume to precipitate the NaClO3. However, in this case, there
is essentially no NaCl left in solution. Concentration when there is
twice as much NaCl as NaClO3 makes it tough to precipitate just the
chlorate. The hot/cold ratio means that you _could_ separate them
by repeated recrystallization - but why bother? Just use the KCl to
precipitate the chlorate as KClO3.
As for a source for KCl (Just in case you can't find it), check out
a ceramics supply place for Potash (K2CO3) - it's really cheap.
Dissolve it in hardware store muriatic acid, and use the solution
of KCl to add to the bleach.
I had the same problems you do, when I was your age. It's one of the
reasons that I'm a chemist today. Get creative. Visit garden stores
and DYI stores and read the lists of ingredients. You will find all
sorts of stuff that you "can't get". <g>
------------------------------------------------------------------------
Norman L. Reitzel, Jr. | "When you live beside the graveyard,
nreitzel@lonestar.utsa.edu | you can't cry for every funeral."
Blue Water Ventures, dba. | Russian Proverb
------------------------------------------------------------------------
From: nreitzel@lonestar.utsa.edu (Norman L. Reitzel )
Newsgroups: rec.pyrotechnics
Subject: Re: potassium chlorate
Date: 5 Oct 1994 17:14:29 GMT
Message-ID: <36umtl$bc6@ringer.cs.utsa.edu>
In article <1994Oct5.033220.26077@hpcvaac.cv.hp.com> billn@hpcvaac.cv.hp.com (bill nelson) writes:
>fernee@physics.uq.oz.au (Mark Fernee) writes:
>: : I was gently reminded by e-mail that this is indeed possible. The yield,
>: : by chemical assay, is about 97% potassium chlorate - if I recall correctly.
>: : The bulk of the impurity is HCl.
>: Yeow! I hope you meant KCl, not HCl. If the HCl concentration was
>: high enough you'd get the formation of chloric acid --> chlorine gas.
>I don't know. Maybe the person who sent me e-mail will respond. I have
>deleted the mail - so cannot double check. You might check Kirk and
>Othmer, who describe the production of potassium chlorate by electrolysis.
The impurity you get in purifying the "bleach" chlorate is indeed KCl.
This can be removed (mostly) by recrystalization, but you lose a lot of
the chlorate, also. And considering you end up with just over an ounce
per gallon of bleach, I think this entire method is incredibly stupid so
should DEFINITELY be included in the Cook Book publications.
Electrolytic production is entirely practical. There are some
difficulties involved, and some ways to get around them. By far the most
intractable problem is finding decent electrodes. The anodes (the
positive electrode) is in an exceptionally corrosive environment, and
metal electrodes like copper or iron are simply dissolved, with no
production of chlorate salts.
Commercial chlorate cells use either passivated titanium or lead dioxide
electrodes. Both of these are expensive and difficult to procure. It is
possible (in theory) to anodize a lead sheet electrode in sulfuric acid
(10%) to get a lead dioxide electrode, but they are very fragile if made
that way. I don't recommend it.
Carbon electrodes don't corrode, but they _erode_, because
of the action of singlet oxygen produced in the electrolyte. They can be
stabilized by impregnation with high molecular weight binders, but this
just slows down erosion, it doesn't prevent it. However,
since carbon electrodes are readily available (from #6 dry cells, for
example), they are often the choice of DIY chemists. They can be used
successfully if they are properly prepared. First, all of the zinc salts
must be entirely removed. This requires boiling in hot water for a few
hours, which also removes most of the manganese dioxide. They must then
be dried thoroughly in an oven and allowed to cool. The carbon should
then be impregnated with a binder. The two easily obtained binders are
safflower oil or better, linseed oil. The carbon should be soaked in the
oil for two or three days, removed and wiped off, and allowed to dry
(harden) for at least a week. Then, and this is quite important, the
surface must be lightly sanded with find sandpaper to make the carbon
adequately conductive.
The cathodes (positive electrodes) can be iron or lead. They should not
be copper! If iron is used, the electrode needs to be removed from the
bath whenever the current is turned off, as it will otherwise corrode
rapidly.
The electrolyte is a saturated solution of brine (salt). pH control is
important, as it tends to become more basic rapidly as the cell is
operated. The electrolyte should be tested with a pH kit (which are
available at pool supply companies), and adjusted by adding hydrochloric
acid ONE DROP AT A TIME. This is important -- as was pointed out
earlier, too much acid will get you chlorine gas, which will mightily
annoy your neighbors and perhaps the local cops. Not to mention being
slightly deadly. The pH of the solution should be held between 6 and 7.
And it takes VERY LITTLE acid to do this.
Some manufacturers add a bit of potassium dichromate to the solution.
This is to help reduce corrosion of the metal parts of the cell, and does
not materially affect the yields of chlorate.
As current is run through the cell, hydrogen is evolved, along with a bit
of oxygen and a bit of chlorine. Ventilation is necessary -- too much
hydrogen is a good way to blow yourself up. The chloride ion in the cell
is converted into chlorate, SLOWLY. It takes a BUNCH of electricity to
convert, so you want to use as much current as practical. Most of the
people who have accomplished this have used battery chargers; I used a
plating power supply. You will need to run a cell at twenty amperes for
two days to get about 150g of potassium chlorate.
During operation, the cell will become warm or hot. This is helpful
unless it manages to heat all the way up to boiling. In any event, water
is lost from the cell, and should be replaced, using -distilled- water.
Just mark the level on the outside, and from time to time, add more water.
In order to separate potassium chlorate from the cell, you should filter
the electrolyte from the cell (it will have electrode crud in it) and
heat it to nearly boiling. Then prepare a saturated solution of
potassium chloride (muriate of potash, from garden supply place) by
dissolving as much as possible in some hot water. For four liters of
electrolyte, it is appropriate to prepare 500 ml of saturated potassium
chloride. Dump the two solutions together and bring the electrolyte to a
boil, and evaporate however much the volume of the potassium chloride
solution was. Then cool to room temperature. The potassium chlorate
will separate as fine crystals you can collect by filtration.
You can dump out the crud in the cell, wash it out with water, then dump
the processed electrolyte back in and start over. You should rinse the
chlorate crystals with ice cold water three or four times to get rid of
any residual salt, which tends to make the chlorate hygroscopic.
------------------------------------------------------------------------
Norman L. Reitzel, Jr. | "When you live beside the graveyard,
nreitzel@lonestar.utsa.edu | you can't cry for every funeral."
Blue Water Ventures, dba. | Russian Proverb
------------------------------------------------------------------------
Newsgroups: rec.pyrotechnics
From: nreitzel@lonestar.utsa.edu (Norman L. Reitzel )
Subject: Re: Grinding KClO4 and Sulpher
Message-ID: <1994Jun9.234748.10248@ringer.cs.utsa.edu>
Date: Thu, 9 Jun 1994 23:47:48 GMT
In article <2t7s7b$7uc@agate.berkeley.edu> Paul Glass <pglass@chop.isca.uiowa.edu> writes:
>
>mwest@netcom.com (Michael J. Westfield) writes:
>: I was grinding some home-made KClO4 with some sulfer and it went bang.
>:
>: Does this mean I have not removed all of the KClO3 or is this just as
>: sensitive a mixture as sulfer and KClO3?
>deleted.....
>
>Is there a test to detect small quantities of KClO3 as an impurity in
>KClO4??
To detect ClO3- in a solution containing ClO4-, use the following procedure:
Dissolve roughly 250 mg of the perchlorate in question in 50 ml of
distilled water. Add 3 drops of a solution of 4g potassium iodide in 30
ml of distilled water, then add 3 drops of dilute (1:3) HCl. A brown
coloration indicates the presence of chlorate. If 3 drops of an aqueous
sol of wheat starch is added, a dark color indicates the presence of
chlorate.
Without the starch, this test will detect chlorate down to about .3%.
With the starch, it is good for chlorate down to about .005%. Every
single sample of perchlorate I tested with starch showed positive for
chlorate -except- my bottle of Mallincrodt Analytical Reagent grade KClO3.
Be careful to run a blank on your HCl - this test is also sensitive to
hypochlorite, and at least one sample of "muriatic acid" that I have will
give false positives.
------------------------------------------------------------------------
Norman L. Reitzel, Jr. | "When you live beside the graveyard,
nreitzel@lonestar.utsa.edu | you can't cry for every funeral."
Blue Water Ventures, dba. | Russian Proverb
------------------------------------------------------------------------
Newsgroups: rec.pyrotechnics
From: nreitzel@lonestar.utsa.edu (Norman L. Reitzel )
Subject: Re: Grinding KClO4 and Sulpher
Message-ID: <1994Jun8.235325.12038@ringer.cs.utsa.edu>
Date: Wed, 8 Jun 1994 23:53:25 GMT
In article <mwestCr2FGz.AAw@netcom.com> mwest@netcom.com (Michael J. Westfield) writes:
>I was grinding some home-made KClO4 with some sulfer and it went bang.
>
>Does this mean I have not removed all of the KClO3 or is this just as
>sensitive a mixture as sulfer and KClO3?
>
>The total weight of the experiment was less than 5 grains so I was not
>in any great danger. I wanted to test if my KClO4 was pure and either
>it isn't or this is not a good test.
>
>I doubled crystalized the KClO4 but I didn't wash the crystals in cold
>water. I am hoping that this is the problem and the test is valid.
>
>If you have any experience with verifying that a sample of KClO4 is pure
>I would like to know your method.
Having a perchlorate explode when ground with sulfur is not uncommon. It
certainly isn't a test for chlorate versus perchlorate. An easy way to
compute the purity of your perchlorate/chlorate is to use the boiling
point elevation of water to determine it's molecular weight. See any
first year chemistry book on how.
If you haven't ANY chemistry books, I can post the method in a couple of
days, when I get back from vacation. To where my books are.
------------------------------------------------------------------------
Norman L. Reitzel, Jr. | "When you live beside the graveyard,
nreitzel@lonestar.utsa.edu | you can't cry for every funeral."
Blue Water Ventures, dba. | Russian Proverb
------------------------------------------------------------------------
From: sfaber@cbnewse.att.com (steven.r.faber)
Newsgroups: rec.pyrotechnics
Subject: Re: Reactions
Keywords: chlorates,sulfur,aluminum,safety,purity
Message-ID: <1991Feb7.204637.8458@cbnewse.att.com>
Date: 7 Feb 91 20:46:37 GMT
In article <1991Feb5.152208.28660@kodak.kodak.com>, ornitz@kodak.kodak.com (Barry Ornitz) writes:
> In article <11916@darkstar.ucsc.edu> wordup@ucscb.UCSC.EDU (60187000) writes
>>However, I do believe potassium chlorate is still used in some foreign
>>countries (china). This is the same stuff contained in the firecrackers we
>>blew up when we were kids; I have yet to see a firecracker spontaneously
>>explode.
>
> Most firecracker compositions use potassium PERchlorate with aluminum and
> antimony sulfide. This sulfur containing compound is much safer than raw
> sulfur. I have never known of a commercial firework manufacturer to use
> potassium chlorate in his firecracker compositions. [Well, a few years ago
> an illegal cherry bomb/M-80 factory here in Tennessee blew up killing a large
> number of people. The fire inspectors found records of potassium chlorate
> shipments as well as perchlorate. It was speculated that both oxidizers were
> used leading to the explosion.]
Did you ever analyze any firecrackers? All the Chinese flashcrackers
I tested (not M-80s) use potassium chlorate, and I am pretty sure sulfur
also, although I don't remember if I tested for sulfur vs antimony
sulfide.
In a lecture by J. Conkling (professor and researcher on pyro. mentioned
here on the net before) he gave a formula for flashcrackers containing
potassium chlorate, aluminum, and sulfur and said he would'nt
touch the mixture himself but the chinese have been making
millions of them safely for years. I was a little surprized at
his aversion for the mix also since I had made hundreds of salutes
using the chlorate, sulfur, and magnesium and Al powder as a kid
without incident. I found that a KCl03, Mg, S mix M-80 type salute
would go bad after a couple weeks of stewing in its
juices(moisture). It would not get sensitive, but would burn more
slowly. The sulfur and Mg would react with water vapor to give H2S
which I detected from blackened Pb acetate paper. Maybe with the
reducing properties of Mg absent, using Al, that acid build up could
be a problem. My KCl03 may have been stabilized with some bicarbonate
as mentioned by Weingart which would reduce the problem.
There is also a factor of what type of sulfur is used.
Flowers of sulfur (sublimed) contains the monoclinic form which
is more active in the above regard than is the rhombic form (can
be made by heating the other forms for a period of time) which is
the recommended form for pyrotechnics. Do any of you have a source
or use the rhombic allotrope in your mixes?
Steve
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