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Author Topic: Sodium Chlorite & Sodium Chlorate - Reactions with Citric Acid - MMS - ClO2  (Read 9758 times)

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Kanga

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I have posted a similar question in the student forum and received some assistance, and hope it is not out of order to post this here.

I am interested in the substance known popularly as MMS (Miracle Mineral Supplement) which is a 28% Sodium chlorite solution which is reacted with citric acid to produce chlorine dioxide for use as a general disinfection, antibacterial and antiviral agent.

See here for information on MMS and the in vivo actions of chlorine dioxide http://www.bioredox.mysite.com/CLOXhtml/CLOXhome.htm

I have seen instructions on the net which purport to describe a method of producing sodium chlorite by the electrolysis of sodium chloride solution see here :-

http://www.ehow.com/how_5188671_make-sodium-chlorite.html

However other information on the net, and a reply in the student forum tells me the principle product of this process is sodium chlorate, not chlorite although perhaps some of the latter may be produced?

I have constructed the processing cell described above and after allowing the cell to run for several days on a 12V DC supply drawing about 200mA with about 400mg of NaCl dissolved in 1 liter of water, the gassing at the carbon electrodes ceased. It produced a solution which has obviously some free chlorine or chlorine dioxide being released from the slight smell of chlorine.

Reacting a few drops of the solution with 10% citric acid solution gives a noticeable smell of chlorine, possibly also chlorine dioxide, which I believe smells the same, although I appreciate it is very different  chemically from chlorine.

The intention is to be able to produce chlorine dioxide by the slow reaction with citric or acetic acid for use as described for MMS (see here http://jimhumble.biz/ )

My question is, as the main product of the electrolysis is sodium chlorate not chlorite, will the reaction of citric or acetic acid still produce chlorine dioxide, not just chlorine?

If so could sodium chlorate be used instead of sodium chlorite in the MMS (Miracle Mineral Supplement) applications to produce chlorine dioxide and hypochlorous acid?
The reaction with citric or acetic acid is apparently a slow one taking perhaps an hour or more and facilitates the ongoing production of chlorine dioxide in the stomach after the diluted mixture of up to 15 drops of MMS and an equal amount of 10% citric acid is ingested.

As explanatory background to this question. ClO2 has an electro potential of -0.93eV, which is less than that of the O2 molecule at -1.3eV. In vivo ClO2 does not harm normal body tissue which is accustomed to an oxygen rich environment, however most pathogens viral, bacterial, and parasitic, are anaerobic and prone to oxidation by ClO2, which is readily absorbed by the red blood cells.

MMS also produces hypochlorous acid in the stomach which is used by white cells (which also produce their own hypochlorous acid) to destroy pathogens as a normal part of the immune system function. The use of MMS/ClO2 has been extensively trialed in Malawi and Kenya for the treatment of Malaria with 100% success. It has also been found highly effective in the treatment of a wide variety of other viral, bacterial and parasitic conditions.

While sodium chlorite(MMS) is fairly easily available, it is not so easily available or cheap as common salt, which can be very easily electrolysed to sodium chlorate. If chlorine dioxide can be produced from the chlorate in a similar manner to the MMS(chlorite) process in vivo the availability of the process would be even more universal.

There are a number of US patents for various methods of electrolysing dilute NaCl solutions which claim spectacular therapeutic applications for the resultant electrolyte in disinfection of wounds and treatment of diabetic ulcers. It is probable that ClO2 is the active agent if such claims are valid, which suggests to me that chlorine dioxide may also be a by product of the electrolysis of NaCl solution, not only NaClO3. Is this so?

If you have read the description of the simple apparatus I used to electrolyse the concentrated NaCl solution, using graphite electrodes, can anyone advise how (if) the process could be varied to produce some NaClO2 along with the main product NaClO3?Perhaps by control or variation of solution initial concentration, temperature, voltage and or current, electrode material, time of reaction or addition of a catalyst?

I am aware of the usual industrial process for making Sodium chlorite from sodium chlorate, which was also referred to in the student forum, but this is not suitable, being too complex in the context considered.

If MMS could be made anywhere from electrolysed common salt solution and not even sodium chlorite would be needed as a basic material, the implications of that would be obvious to anyone who has an understanding of the potential uses of MMS.

I am not great at chemistry, actually an engineer, but please don't hold back with the reaction equations or explanations, I'll try to follow along.
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Borek

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I am interested in the substance known popularly as MMS (Miracle Mineral Supplement) which is a 28% Sodium chlorite solution which is reacted with citric acid to produce chlorine dioxide for use as a general disinfection, antibacterial and antiviral agent.

You may want to search forums for chloride dioxide. See for example

http://www.chemicalforums.com/index.php?topic=34557.0
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Kanga

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Perhaps I have unwisely risked the discussion of this question getting side tracked into ethical or medical matters by giving too much background information on the genesis of the actual chemistry question.

One of the references cited in response http://en.wikipedia.org/wiki/Chlorine_dioxide states in part:-

"Over 95% of the chlorine dioxide produced in the world today is made from sodium chlorate and is used for pulp bleaching. It is produced with high efficiency by reducing sodium chlorate in a strong acid solution with a suitable reducing agent such as hydrochloric acid and sulfur dioxide. " The same article goes on to describe a number of other reactions that produce chlorine dioxide.

So reverting to one of my original questions:-
1. As the main product of the electrolysis (of NaCl solution) is sodium chlorate not chlorite, will the reaction of citric or acetic acid still produce chlorine dioxide, not just chlorine?

2. Is the electrolysis of a concentrated NaCl solution (400g per liter) likely to produce any sodium chlorite along with the main (sole?) product sodium chlorate?


and flowing from the above cited wikipedia article some additional questions:-

Is an acid such as 10% citric acid or say 5% acetic acid a sufficiently "strong" acid to produce chlorine dioxide from sodium chlorate in the manner quoted above using hydrochloric acid?
In such a process does the term "strong" imply a concentrated acid, or just refer to the type of acid?
If a dilute hydrochloric acid were used would the reduction reaction still occur, perhaps more slowly or with reduced efficiency or yield?


On the matter of the toxicity of chlorine dioxide, (and derivatives and organic by products in water treatment applications) one of the earlier responses indirectly led me to an excellent referenc which should be of interest to anyone concerned with the use of ClO2 in the MMS application. Particularly if the identified generally rather tenuous risks are contrasted with the virtual certainty of imminent death from a disease such as malaria!

http://books.google.com/books?id=WZj3khOKMaIC&pg=PA348&lpg=PA348&dq=chlorine+dioxide+ingestion&source=web&ots=dCir8H82TM&sig=9OTDKKvLFqs657OOa-9Q6M-eGRk#v=onepage&q=chlorine%20dioxide%20ingestion&f=false
« Last Edit: May 25, 2010, 03:26:06 PM by Kanga »
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Borek

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Perhaps I have unwisely risked the discussion of this question getting side tracked into ethical or medical matters by giving too much background information on the genesis of the actual chemistry question.

Could be. But to allow discussion on the chemistry we must make sure thread doesn't copy obviously incorrect information from doubtful sources.

On the matter of the toxicity of chlorine dioxide, (and derivatives and organic by products in water treatment applications) one of the earlier responses indirectly led me to an excellent referenc which should be of interest to anyone concerned with the use of ClO2 in the MMS application. Particularly if the identified generally rather tenuous risks are contrasted with the virtual certainty of imminent death from a disease such as malaria!

Before you can state something like that you should find results of a real research, published in the peer reviewed journal, showing that ClO2 is actually effective fighting malaria, and that necessary doses are low enough so that side effects are not worse than the disease itself. You call these risks tenuous because you compare carefully worded textbook written by someone understanding all possible nuances with hurra optimistic statements written by MMS zealot.
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Kanga

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For a moderator you seem very determined to concentrate your replies on the peripheral  aspects, and avoid the main questions on the chemistry that I am posing.

Hopefully someone will provide some answers to the chemistry questions highlighted in blue. I provided the background information on the geneses of the questions as just that, background.

There is no obviously incorrect material copied from other sources.

If you actually read the google book reference linked to you will find that the risks (of Chlorine dioxide ingestion in small quantities) which I refer to as tenuous are indeed that, very tenuous.  I have not copied anything from doubtfull sources, merely contrasted tenuous risks with the very real risk from an often fatal disease. There are a number of reports from doctors and health officials in Malawi and Kenya attesting to the effectiveness of the ClO2 treatment.
I don't wish to continue discussing the background issues, but you seem to be intent on attacking these matters, to the exclusion of dealing with the chemistry.

Why is it so?
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Borek

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I have nothing against discussion of the chemistry involved, if I am not addressing it that's because I have no knowledge on the subject detailed enough. I think I know where to look for this kind of information, but I am not going to drive to the library that is 30 km from here just to check if I am right.

At the same time it was you who brought MMS to the thread, and you are claiming things that were not proven, as if they were known for sure. AFAIK there is no correct study researching effectiveness of the ClO2 in treating malaria, reports that are not part of rigorous study are not a valid way of supporting such claims. Especially when these claims are extraordinary (after all, first M in MMS stands for Miracle, doesn't it?). Correct approach is a study with population large enough, double blind protocol and so on; such thing has been not done.

You would be surprised how often people come to scientific forums to ask questions about miracle cures they have read about on the internet or about miracle devices that let you increase mpg. Any thread in which these things are not correctly addressed from the very beginning just fuels their delusions and makes moderating forums even more tedious.

If you agree I can delete posts that are not on subject of the chemistry and edit your posts to remove unnecesary references to MMS, leaving just the chemistry part.
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1. As the main product of the electrolysis (of NaCl solution) is sodium chlorate not chlorite, will the reaction of citric or acetic acid still produce chlorine dioxide, not just chlorine?

2. Is the electrolysis of a concentrated NaCl solution (400g per liter) likely to produce any sodium chlorite along with the main (sole?) product sodium chlorate?



Is an acid such as 10% citric acid or say 5% acetic acid a sufficiently "strong" acid to produce chlorine dioxide from sodium chlorate in the manner quoted above using hydrochloric acid?
In such a process does the term "strong" imply a concentrated acid, or just refer to the type of acid?
If a dilute hydrochloric acid were used would the reduction reaction still occur, perhaps more slowly or with reduced efficiency or yield?





you need a good acid, like HCl, then a mix of Cl2 and ClO2 will form
no
strong acids are HCl, HNO3, H2SO4, HClO4, HSbF6, HCN5O2

« Last Edit: May 26, 2010, 05:38:44 AM by Borek »
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Kanga

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you need a good acid, like HCl, then a mix of Cl2 and ClO2 will form
no
strong acids are HCl, HNO3, H2SO4, HClO4, HSbF6, HCN5O2

I have conducted an experiment using the resultant electrolyte from the electrolysis of sodium chloride (sodium chlorate)and  mixed a small quantity with equal quantities of:-
1. 10% citric acid
2. Weak Acetic acid (in the form of vinegar)
3. Concentrated Hydrochloric acid  

All three acids cause a reaction where a gas smelling of chlorine is given off. As chlorine dioxide smells similar (identical?) to chlorine it isn't possible to say from this alone what the mix of gasses is.
The only superficially observable difference is that the HCl reaction immediately precipitates a white salt, and the reaction appears to be rapid, whereas the others proceed far more slowly.

The quoted respondent indicates that if I use a "good acid like HCl" then a mix of Cl2 and ClO2 will be given off, but as the other two acids also give of similar smelling gas, can any one further explain about how the type of acid will affect the generation of ClO2. The other products of the reaction are not important considerations.
I thank the learned respondent for his contribution on the chemistry.

This is a Q&A scientific forum, not an encyclopedia, surely every question posed or fact or opinion asserted does not have to be backed by citations of some prestigious "authority". When I do refer to the existence of supporting opinion it is responded to with racist derogatory remarks.
If African opinion is not to your liking go here :-

http://www.bioredox.mysite.com/CLOXhtml/CLOXhome.htm

to Thomas L. Hesselink, MD of Aurora, Illinois, one of many American and European doctors who are taking the background subject of my questions very seriously.


« Last Edit: May 26, 2010, 05:41:45 AM by Borek »
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Kanga

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If you agree I can delete posts that are not on subject of the chemistry and edit your posts to remove unnecesary references to MMS, leaving just the chemistry part.

I don't think there is any need or justification to edit or delete anything I have posted. The fact that I have given background information to the chemistry questions I posed on a subject with which you appear to have some disagreement hardly justifies any interference.

This is not an encyclopedia here surely, where every statement needs to be backed by citation of the most authoritative sources. When I have referred to the existence of supporting opinions from African sources, the response from others has been more racist than scientific. Therefor I have now also provided reference to the views of Thomas L. Hesselink, MD of Aurora, Illinois on the matter in addition.

Without your dwelling on it, the background briefing in my posting and the reasons behind my chemistry questions would have attracted little attention. You have forced me to defend my background briefing, without which I would have simply awaited some help on the chemistry questions and left it at that.

Perhaps the racist or derogatory remarks about African medical opinions posted is something to properly concern a moderator, rather than my backgrounding MMS to place my questions in some context.
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Note, sodium chlorate (NaClO3) with HCl gives mixture of ClO2 and Cl2
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Borek

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This is a Q&A scientific forum, not an encyclopedia, surely every question posed or fact or opinion asserted does not have to be backed by citations of some prestigious "authority". When I do refer to the existence of supporting opinion it is responded to with racist derogatory remarks.

I agree that these remarks were wrong and I have edited them out. At the same time we never allowed discussions of crackpottery on these forums, and it is not going to change.

Quote
Thomas L. Hesselink, MD of Aurora, Illinois, one of many American and European doctors who are taking the background subject of my questions very seriously.

This is not "one of many" as you suggest, you are simply quoting name listed on MMS site. All MMS sites are heavily crosslinked, and they are all owned by the same people, there is no support from others. That's a sure sign that MMS is a snake oil.

You are welcomed to continue discussion on chlorine chemistry, but any further mention of MMS will be not tolerated.
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Kanga

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Note, sodium chlorate (NaClO3) with HCl gives mixture of ClO2 and Cl2

Yes thank you that confirms another opinion.

Can you elaborate on the relative amount of each and if the proportions of each gas depends on reaction parameters such as the concentration of the HCl or the initial temperature, or is it a fixed quantity of each gas?

Also as the observed smell of the gasses given off when reacting with citric acid or acetic acid is subjectively similar, is ClO2 also produced in those reactions too?

As the Cl3  group from the sodium chlorate is being reduced to some Cl2 and some ClO2 am I correct in supposing that the electro valent equations may help show what is happening, and if so can anyone postulate such an equation?

I have read that CLO2 has a rather odd "three electron bond" structure that was described by Brockhurst I think it was in the 1930's with input from Linus Paulling, and that at the time the bond structure was a bit of a mystery. Has this been clarified since in a way which might help explain the dual gas formation, or why there may be a difference in the proportions of Cl2 and CLO2 depending on the "strength" of the reducing acid?
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