Professional Documents
Culture Documents
Printable Version
Posts: 1803 As I found out that my planned project of making HClO4 requires vacuum and because our groundwater pump isn't connected
Registered: 16-8-2004 in winter (tap water is expensive here), I decided to do something different instead.
Location: Germany
Member Is Offline Sodium chlorite is a bleaching agent often used in industry because it doesn't attack the fibers (as does hypochlorite) and
produces no chlorinated organics. It is also used to produce in- situ chlorine dioxide, which is a disinfectant much more
Mood: No Mood environmentally friendly than chlorine.
NaClO2 can decompose exothermically when heated, and the silver and mercury salts of chlorous acid are violently
explosive, being interesting candidates for primary explosives.
This link outlines the production of sodium chlorite, basically, ClO2 is first produced from NaClO3, NaCl and H2SO4, this is
then purified and reacted with aqueous NaOH to which a reducing agent has been added (to avoid the formation of chlorate
which would otherwise occur).
I don't like this process because of the explosion hazard involved in handling the ClO2. The ClO2 is diluted with air in the
industrial process, but this is difficult in a home setup.
In a textbook, there was a remark that sodium chlorite could be produced by reducing sodium chlorate with oxalic acid. This
would of course be the best method, but nothing was said about reaction conditions.
Oxalic acid is always oxidised to CO2, so when there's CO2 evolution on mixing (and heating) solutions of oxalic acid and
NaClO3, it would be a success.
Chlorine Dioxide
Posts: 1036 I posted,about a year ago, that I successfully and safely produced Chlorine Dioxide in quantity by placing potassium chlorate,
Registered: 8-10-2003 oxalic acid, and sulfuring acid in a test tube then submerging the tube in hot water. Tthe CO2 from the oxalic acid safely
Location: closer to the dilutes the chlorine dioxide which I may add, has a seductive oxidizer smell
anode
Member Is Offline That is not even the exciting part! The reaction is ENTIRELY temperature dependent. So if you need to stop the gas flow, put
your apparatus in ice water. The reaction will resume when its gets warm again.
Mood: Strongly alkaline
According to one of my Inorganic Synthesis books, it is plausable to make sodium peroxide octahydrate from sodium
hydroxide solution and hydrogen peroxide at subfreezing temperatures. This mixture would definately reduce chlorine dioxide
to the chlorite.
I plan to redo my chlorine dioxide preparations soon. This time, I wish to reduce acidic chlorate with urea. I saw this in a
patent but which one I cannot recall.
Oh, just thought I would mention one important key factor. I believe the temperature response to my previous reaction was
largely based on temperature/solubility curves for both oxalic acid and potassium chlorate. Sodium Chlorate mixture may not
be as easy to control.
In the theater of life its nice to know where the exit doors are located.
Mood: No Mood
Mood: No Mood
I think it must be in the anhydrous state. Theoretic, can KNO3 be used instead of the NaNO3?
Posts: 492
Registered: 7-2-2004
Location: Mediterranean
Member Is Offline
Theory guides, experiment decides.
Mood: Quantized
I have seen camping water purifier tablets for sale which are 6% sodium chlorite. An expensive sourse, but noteworthy.
Posts: 2858
Registered: 18-11-2003
Member Is Offline
Mood: No Mood
Anyway, the reactoin that I posted needs 2.4% moisture according to the prep I pulled it from. ClO2 is fairly soluble in water,
slow addition of HCl to chlorate could result in a solution of ClO2 in water with NaCl, then add some base to get your chlorite,
as long as the temp is kept down and acid additoin slow you may get away without ClO2 gas being freely evolved.
I'm at my library right now and decided to look up preparations of sodium chlorite, these are abstracted from The
Posts: 2917 Encyclopedia of Chemical Reactions, Jacobson, copywrite 1948, Fifth Edition 1961, Vol II:
Registered: 13-7-2003
Location: Wisconsin Quote:
Member Is Offline
An aqueous mixture of a base and sulfur or an inorganic sulfurous compound reacts with chlorine
Mood: Anxious dioxide to form the chlorite of the base metal. The yield is high at room temperature.
6ClO2 + S + 8NaOH ---> 6NaClO2 + Na2SO4 + 4H2O
2ClO2 + Na2SO3 + 2NaOH ---> 2NaClO2 + Na2SO4 + H2O
An aqueous mixture of a base and a carbonaceous material such as carbon reduces chlorine
dioxide to the chlorite of the base metal in high yields at 20-50C.
4ClO2 + C + 6NaOH ---> 4NaClO2 + Na2CO3 + 3H2O
Chlorine dioxide is absorbed in a solution of hydrogen peroxide and sodium bicarbonate to form
sodium chlorite at room temperature in high yield. Also works with KHCO3 to form potassium
chlorite. The mol ratio of peroxide to bicarbonate is 1 to 2.
2ClO2 + 2NaHCO3 + H2O2 ---> 2NaClO2 + 2CO2 + O2 + 2H2O
2ClO2 + 2KHCO3 + H2O2 ---> 2KClO2 + 2CO2 + O2 + 2H2O
Of course these being better then just absorbing in straight NaOH due to that reaction producing almost an equimolar mixture
of chlorate and chlorite if done at medium temperature.
I don't actually know if KNO3 can be used instead of NaNO3, but there seems no reason why not. I don't know much about
Posts: 756 this reaction, I only saw the equation mentioned and that's it. If you do the reaction in acidic aqueous solution, then I think
Registered: 17-6-2003 NOCl won't hydrolyse and will just fizz out (I assume its solubility depends directly on pH), and ClO2 will evolve as well (the
Location: London, the Land problem lies in separating the two ). Or, a nonaqueous solvent could be used.
of Sun, Summer and Snow
Member Is Offline
Quote:
Of course these being better then just absorbing in straight NaOH due to that reaction producing
almost an equimolar mixture of chlorate and chlorite if done at medium temperature.
Yeh all these seem decent and applicable. I will read the patents you stated in my leisure and sometime I will compare these
methods with my own method I stated previously
In the theater of life its nice to know where the exit doors are located.
chloric1 posted on 2-2-2005 at 09:59
International Hazard
Uh Yeh, I am not sure about that. A non-aqueous solvent commonly available would not stand up to these reaction
conditions. I guess if you where suicidal you could liquify NO2 to N2O4 for a solvent
In the theater of life its nice to know where the exit doors are located.
Quoted from Inorganic and Theoretical Chemistry by F. Sherwood Taylor - Ninth edition [Pg.715-716].
Posts: 492
Registered: 7-2-2004
Location: Mediterranean Quote:
Member Is Offline
Mood: Quantized ...Sodium chlorite is a powerful but stable oxidising agent, and is much used in bleaching cellulose
materials. The chlorites of some of the heavy metals have been prepared by precipitation.
The part of interest is the last sentence of the quote. Which heavy metal which in the presence of NaOCl would remain
unaffected and would precipitate as the chlorite?
Where does hypochlorite come in to this? Don't they mean precipitation from a soluble chlorite and the heavy metal nitrate?
Posts: 1745 Or what?
Registered: 7-5-2004
Location: Cornworld, Central
USA
Member Is Offline
Mood: Enhanced
When using the method Theoretic describe, which is the following reaction, NaOCl is produced.
NaNO3 + Cl2 --> NaClO2 + NOCl
I am interested in isolating the pure chlorite, isolating it from the mixture.
In the reference I found it states that the chlorite of a soluble salt, such as in this case the NaClO2, can be precipitated, say
with BaCl2 solution to form Ba(ClO2)2 which is most probably insoluble. What I wanted to know is if the heavy metal would be
affected by the NaOCl.
At the library today I found that the chlorites in solutions are thermally stable, to a certain extent, surely more than
hypochlorites (no values were given). Maybe the hypochlorite can be disproportionated to give the chlorate and the chloride,
and the chlorite ppted by some metal salts which does not ppt with the chlorate and chloride.
Esplosivo, NOCl (Nitrosyl chloride) is a gas! The Method you quoted gives pure Chlorite.
Posts: 1803
Registered: 16-8-2004 Yesterday I did a quick test: I mixed a spatula of NaClO3 with the same amount of oxalic acid, dissolved the mix in water and
Location: Germany heated it, nothing happened, no gas evolution.
Member Is Offline Even on addind a few drops of HCl, still nothing happened. So this doesn't work... thats bad, I will have to use ClO2.
Mood: No Mood
You're right, I'm sorry. I assumed that the reaction is carried out in aqueous conditions where NOCl would hydrolyse.
Anyways. To liberate the ClO2/CO2/CO mixture concentrated sulfuric acid is needed, which reacts with both the solid oxalic
acid and the solid chlorate - (The CO produced will react with some of the ClO2 being oxidised to CO2). This reaction is
mentioned in reference books as the production of ClO2 to reduce possible explosion hazards of the gas. Use solid
chemicals, not solutions. Like this it should work. Hope this helps.
Mood: No Mood I searched for more info, since the PATR reference seemed to suggest a way of getting to KClO2 without ClO2, but most
reference back to an Italian journal, I could only get its abstract as published in the London journal <a
href="http://pulse.altlist.com/images/chlorites-abstract.pdf">here</a>, which doesn't give what I was after.
Chemistry of Chlorites
Production of Sodium Chlorite
Silver Chlorite
Small Scale Generation of ClO2
Sodium Chlorite - Properties and Production
I didn't experiment further with chlorites, because I didn't want to risk destroying my glassware with a ClO2 explosion.
Posts: 1803
Registered: 16-8-2004 The articles you posted helped a lot. ClO2, when passed into NaOH/H2O2 mixture yields pure chlorite. H2O2 is too
Location: Germany expensive for industrial use, but perfect for us.
Member Is Offline I will use air as a carrier gas to dilute the ClO2 (instead of oxalic acid as a CO2 producer).
Air will be pumped throught a flask where conc. H2SO4 is reacted with NaClO3.
Mood: No Mood
The resulting air/ClO2 mixture will be passed through a washing bottle containing NaOH/H2O2 solution.
Mood: No Mood