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Proper stoichiometric mixing of 22.4% MMS solution with 50% citric acid solution

• Proper stoichiometric mixing of 22.4...  Stephan2  11 years ago  8,754

PLEASE NOTE THAT THIS POST IS INCORRECT! I assumed that the precentages of the MMS and acid solutions were by volume but they are by WEIGHT! I have therefore posted a table with (hopefully) correct number of activator drops for a given number of MMS drops. I regret that I made a mistake and I hope you accept my appologies. Thanks also to SilverFox who put me on the right track. I'll leave the material still here for review and maybe in a month or so I will delete it. So please don't follow the instructions below and skip to my post on February 1st, 2010, in this thread.

Accurate Preparation of Chlorine Dioxide Solution

Presented is an analysis of the amount of chemical substances for the MMS solution and citric acid needed to get a stoichiometric accurate mix to produce chlorine dioxide. Wikipedia has for the definition of stoichiometry:

Stoichiometry (sometimes called reaction stoichiometry to distinguish it from composition stoichiometry) is the calculation of quantitative (measurable) relationships of the reactants and products in a balanced chemical reaction (chemicals). It can be used to calculate quantities such as the amount of products that can be produced with the given reactants and percent yield. First we look at the molecular masses of sodium chlorite and citric acid (looked up at Wikipedia). A molar mass Mmol is defined as the mass of one mole of substance in units of gm/mol; one mole has 6.022*1023 of molecules (or atoms), which is called the Avogadro constant NA. More precisely, NA is defined as the number of atoms in exactly 12 grams of the pure isotope 12C. The molar mass takes into account the fractions of natural isotopes found in nature.

Sodium Chlorite:  NaClO2     single valence

Molar Mass: MNaClO2  =  (23+35.5+32) g/mol ,   MNaClO2  = 90.5 g/mol

Citric Acid: C6H8O7   triple valence

MCitricAcid = 210.14 g/mol

Ratio:  210.14/(3*90.5) = 0.774

The molar mass is for the monohydrate form, which means each citric acid molecule has a single molecule of water added to it.

Sodium Citrate: C6H5Na3O7  triple valence

Molar mass:

MSodiumCitrate = 258.07 g/mol

Chemical reaction:

3 NaClO2 + C6H8O7 --> C6H5Na3O7 + 3 ClO2

Begin Edit 11/21/09: Silverfox pointed out the formation of chlorous acid, which can form when chlorine dioxide captures an electron to form a negative chlorite ion:

ClO2 + e- --> ClO2-, which then forms chlorous acid:

H+ + ClO2- -->  HClO2

Chlorous acid is unstable (Wikipedia) and will form hypochlorous acid and chloric acid:

2HClO2(aq) → HClO(aq) + HClO3(aq)

When ingested, the hypchlorous acid can react with the stomach hydrochloric acid (Wikipedia) and form chlorine gas (Wikipedia shows it the other way around, however the chemical reaction can reverse):

Cl2 + H2O $\overrightarrow{\leftarrow}$ HClO + HCl

or, hypochloric acid can form chloric acid (Wikipedia):

3HClO → HClO3 + 2 HCl

The chemical reaction chain of activated MMS is not trivial and one has to keep in mind that other, less disirable byproducts may be generated when ingesting activated MMS. (End edit 11/21/09)

By molar mass, one needs therefore three times as much sodium chlorite than citric acid. That means by actual weight, for each gram of sodium chlorite one would need about 0.77 grams of citric acid.

The density of sodium chlorite is 2.5 g/cm3 and the density of citric acid is 1.665 g/cm3.

By volume for each cm3 of sodium chlorite powder one would need 1.156 cm3 of

citric acid powder. So almost equal portions for each substance by volume.

MMS is made as a 22.4% solution by volume in water, the concentrated citric acid is made as

a 50% solution by volume in water. Therefore this is a bit more citric acid than needed. The

proper stoichimetric amount would be two drops of MMS solution for each drop of 50% citric

acid. Since the MMS solution is 22.4% and not 25%, there is a little more citric acid by volume.

The ratio 25%/22.4% is 1.12 vs. 1.156 for the optimum.

Within this accuracy two drops of MMS for each drop of concentrated (50%) citric acid should

be fine.

Note that for the 10% citric acid solution one would need to mix two drops of MMS solution with 5 drops of 10% citric acid solution!

According to Wikipedia, natural lemon juice contains 47 g/liter or 0.047 g/cm3 of citric acid. Bottled lemon juice is more concentrated. I think it is twice as concentrated as in the juice of a lemon, that is what I found on the web, so it should have about 0.1 g/cm3 citric acid.

I think that the recommendations of 5 times as much bottled lemon juice for each drop of MMS solution is on the low side. To calculate, we take the ratio of the concentration of MMS with that of the bottled lemon juice and multiply the result by the stoichiometric weight ratio of 1.3:

(0.224 * 2.5)/0.1 = 7.28

You need 7-8 drops of bottled lemon juice per drop of MMS solution.

Quick check for the 50% citric acid solution:

MMS is 22.4% in water, so the concentration is 0.224*2.5g/cm3 = 0.56 g/cm3.

50% citric acid has 0.5*1.665 g/cm3 = 0.833 g/cm3.

The weight ratio of two parts of 22.4% MMS to one part of 50% citric acid is therefore:

2*0.56 g/0.833 g = 1.345

The ideal weight ratio was 1/0.774 = 1.3 - close enough!

• Re: Proper stoichiometric mixing of ... Stephan2  11 years ago  6,125
This is a reply to # 1,525,565

Stephan

•
• Re: Proper stoichiometric mixing of ... TeAraAio  11 years ago  6,017
This is a reply to # 1,525,565

Kia ora Stephan
What a great job you did in figuring out all the percentages and chemical relations. In New Zealand Miracle-Mineral-Supplement comes as a 28% solution. How would I mix Miracle-Mineral-Supplement and citric acid then. The easiest way would be to have a mix that can be 1 drop Miracle-Mineral-Supplement with 1 drop citric acid . By the way, have you heard that some people are using Tartaric Acid. Supposedly it is less agressive and doesn't expell the stinky gas so fast, smile!

• Re: Proper stoichiometric mixing of ... Stephan2  10 years ago  6,032
This is a reply to # 1,541,935

The 22.4% NaClO2 solution was the result of other, small fractions of salts in the commercially available powder - I believe. 1/4 amount of the powder was mixed with 3/4 amount of water, so it should have been a 25% solution but due to the presence of other salts it ended up being 22.4%.

If you get a 28% solution, that is not so different from the 22.4% solution, so you can still use 2 drops of the Miracle-Mineral-Supplement for each drop of 50% citric acid . If you have the 10% citric acid solution, then for every two drops of Miracle-Mineral-Supplement you need five drops of the 10% citric acid solution.

Hope that helps!

Regards,

Stephan

• Re: Proper stoichiometric mixing of ... SilverFox  10 years ago  6,544
This is a reply to # 1,560,202

Hello Stephan,

Actually sodium chlorite powder is only 80% pure. The solutions are made up by weight. For example, if you take 25 grams of sodium chlorite powder and add it to 400 grams of water you will end up with a 6.25% solution by weight, but it will actually only have 5% sodium chlorite in it.

In the same way the 28%, by weight, solution is actually a 22.4% sodium chlorite solution.

When using citric acid to activate, the proper ration is 10:1 when using sodium chlorite and citric acid powder, 5:1 when using 50% citric acid , and 1:1 when using 10% citric acid. These ratios have been extensively tested and found to be the most effective way to activate sodium chlorite.

Your stoichiometric calculations are close, but you will have a more effective solution if you follow the proven ratios for activation. With billions of pounds of food at risk of spoiling if the ratio is not effective, I would suggest going with what has been proven to be the most effective.

Tom

• Re: Proper stoichiometric mixing of ... Stephan2  10 years ago  6,053
More
This is a reply to # 1,560,398

Actually, I think I got it all wrong! I assumed that the solutions were prepared by volume, however, as you pointed out, they are prepared by weight! I came to realize this today, when I tried to produce a table of number of drops for various acids and concentrations.

Please correct me if I am still wrong, but I now understand that the 22.4% Miracle-Mineral-Supplement solution is 22.4% NaClO2 + 5.8% NaCl (plus some other minor components) + 72 % H2O = 100% solution. Each percentage has to be taken by weight.

So, for example, a 100g solution contains 22.4g of NaClO2.

Now I have to calculate the same for the citric acid solutions and other acids, then calculate their molar concentrations (mol/liter) and take their valenzes into account, to finally determine the proper drop ratios between Miracle-Mineral-Supplement solution and, e.g., citric acid solution.

Stephan

• Re: Proper stoichiometric mixing of ... Stephan2  10 years ago  6,921
This is a reply to # 1,564,893

Tom,

I just did the calculation in Excel:

If one calculates the molarity of the 22.4% Miracle-Mineral-Supplement and the 50% citric acid solutions, then they are essentially exactly the same. Now if the valence would be also the same, then one would have to mix 1:1, however, the valence of citric acid is 3 and of Miracle-Mineral-Supplement (NaClO2) is 1, therefore you need 3 times as much from the Miracle-Mineral-Supplement solution by volume than you need for the citric acid to achieve a stoichiometrically balanced mix!

So for each drop of citric acid, three drops of MMS are required! I mean it probably doesn't hurt if you use more citric acid than needed if ingested, but for an oral rinse I would prefer not to have any excess acid.

As another example, for 6% vinegar you need three drops of vinegar for each drop of MMS.

I have to see how I can upload an Excel spreadsheet or I have to upload an image of it. Important for me is that I did the math correctly! Do you have Excel? I could send you my spreadsheet so you may check it.

Stephan

• Re: Proper stoichiometric mixing of ... Stephan2  10 years ago  7,316   R
This is a reply to # 1,564,968

Updated Feb. 02, 2010. Thanks to SilverFox who pointed out that the citric acid activator is mixed by volume and the MMS solution by weight! In case that some vendors prepare the citric acid solution by weight, I present both in this table. The orange column shows the number of drops for citric acid solutions prepared with concentrations by volume, probably the most common.

I have compiled a lookup table for accurate stoichiometric number of activator drops for a given number of MMS drops and activator percentage used.

Please note that my earlier calculations were based on volume percentages of the solutions, which were incorrect! The MMS solutions are (or should be) prepared by 'weight percentage', while the citric acid solutions are prepared by 'volume percentage'. The other activator solutions are probably mixed by 'weight percentage'. At the bottom of the table I explain what is calculated in each row of the table.

 Units MMS Salt H2O Citric Acid Critric Acid Critric Acid Critric Acid Lemon Juice Vinegar Tartaric Acid Tartaric Acid HCl Molar Weight g/mol 90.5 58.443 18.02 210.14 210.14 210.14 210.14 210.14 60.05 150.09 150.09 36.46 Density g/cm^3 2.5 2.165 1 1.665 1.665 1.665 1.665 1.665 1.049 1.76 1.76 1.18 Valence 1 3 3 3 3 3 1 1 1 1 Concentration by Volume% %cm^3/cm^3 50.0% 10.0% Concentration by Weight% %g/g 22.4% 5.6% 72.0% 50.0% 10.0% 6.0% 6.0% 6.0% 50.0% 8.0% Density of Solution g/cm^3 1.20 1.25 1.04 1.02 1.00 1.03 1.28 1.01 Volume per g Solution cm^3/g 0.84 0.80 0.96 0.98 1.00 0.97 0.78 0.99 Molarity mol/L 2.96 3.96 0.79 2.97 0.50 0.29 1.00 0.41 4.25 2.22 Molarity*Valence mol/L 2.96 11.88 2.38 8.92 1.49 0.88 1.00 0.41 4.25 2.22 Drops 1 0.2 1.2 0.3 2.0 3.4 3.0 7.2 0.7 1.3 Drops 2 0.5 2.5 0.7 4.0 6.8 5.9 14.4 1.4 2.7 Drops 3 0.7 3.7 1.0 6.0 10.1 8.9 21.7 2.1 4.0 Drops 4 1.0 5.0 1.3 8.0 13.5 11.8 28.9 2.8 5.3 Drops 5 1.2 6.2 1.7 10.0 16.9 14.8 36.1 3.5 6.7 Drops 6 1.5 7.5 2.0 12.0 20.3 17.7 43.3 4.2 8.0 Drops 7 1.7 8.7 2.3 14.0 23.6 20.7 50.5 4.9 9.3 Drops 8 2.0 10.0 2.7 16.0 27.0 23.7 57.8 5.6 10.7 Drops 9 2.2 11.2 3.0 20.0 30.4 26.6 65.0 6.3 12.0 Drops 10 2.5 12.5 3.3 22.0 33.8 29.6 72.2 7.0 13.3 Drops 11 2.7 13.7 3.7 22.0 37.1 32.5 79.4 7.7 14.7 Drops 12 3.0 15.0 4.0 24.0 40.5 35.5 86.6 8.4 16.0 Drops 13 3.2 16.2 4.3 26.0 43.9 38.4 93.8 9.1 17.3 Drops 14 3.5 17.4 4.7 28.0 47.3 41.4 101.1 9.8 18.7 Drops 15 3.7 18.7 5.0 30.0 50.6 44.4 108.3 10.5 20.0
• Number of drops in orange coluum are for citric acid solutions that are prepared with concentration by volume. If in doubt: contact your vendor!
• Please round the numbers of drops up to the nearest integer!

• Please note the importance of the valence in the resulting number of drops!

• Concentration by Weight Percentage = Weight of (single) Solute / (Weight of (all) Solute(s) + Weight of Solvent)*100%
• Concentration by Volume Percentage = Volume of (single) Solute / (Volume of (all) Solute(s) + Volume of Solvent)*100%

• Density of Solution = 1/(Concentration_1/Density_1 + Concentration_2/Density_2 + …) - formula used only for solutions mixed by weight

• Volume per Gram of Solution = 1/Density of Solution - formula used only for solutions mixed by weight

• Molarity = 1000 cm^3/L*Concentration/(Volume per Solution*Molar Weight) - formula used only for solutions mixed by weight
• Molarity = 1000 cm^3/L*Concentration*Density/Molar Weight - formula used only for solutions mixed by volume

• Molarity*Valence = Molarity * Valence

• Number of Drops = 1 through 15 for MMS, (Molarity*Valence of MMS) /(Molarity*Valence of Acid) for the activators (acids)

•
• Re: Proper stoichiometric mixing of ... SilverFox  10 years ago  5,854
This is a reply to # 1,564,968

Hello Stephan,

Yes, I have Excel.

While it is interesting to understand the theory, keep in mind that things change a little when it comes to actual use.

Activated solutions are quite acidic and are probably not the best thing for your mouth. We have had excellent results by simply adding NaClO2 to water and letting the acids in your mouth activate it as necessary. My dentist loves this solution and after about a year of testing it has shown remarkable results with no adverse effects. You want to end up with a solution that has 800 - 1000 PPM available ClO2 in it.

The downside of the mouthwash solution is that it requires and extended "swish" time of 30 - 60 seconds, with 60 seconds, or more, being more effective.

Tom

• Re: Proper stoichiometric mixing of ... Stephan2  10 years ago  5,922
This is a reply to # 1,565,549

Thanks again, Tom for your insights - that would explain why the CloSys toothpaste that my dentist uses in his pratice does not bleach. He also uses their mouthwash. Another brand is DioxiBrite. I used the Closys but his has saccharine in it, which I didn't like.

With a toothpaste that has sodiumchlorite in it, one may not need to use the Miracle-Mineral-Supplement for an oral rinse. However, I use the activted form also in my WaterPik - and it destroyed two of them - so I will try the unactivated Miracle-Mineral-Supplement solution, that will also keep my WaterPik alive. I like to use the WaterPik after flossing, to remove any loose food stuff.

I would highly recommend to rinse with the (unactivated) sodiumchlorite solution right after dental cleaning at the dentist. The plaque that has been removed are biofilms that host bacteria, and right after cleaning, the mouth is full of it. My dentist would give me homeopathic injections (I think Pleo-NOT and Pleo-X) into the gums for dental root health and before I started to rinse right after the cleaning, my glands would swell up, probably due to bacteria that were drawn into the gums by the injection needle!

• Re: Proper stoichiometric mixing of ... SilverFox  10 years ago  5,907
This is a reply to # 1,565,570

Hello Stephan,

High concentration ClO2 solutions goes through some plastic like a hot knife through warm butter... [smile icon]

Keep in mind that agitation activates sodium chlorite solutions. I think you would be better off using water in your water pik, and rinsing with a sodium chlorite solution afterward. This also follows standard operating procedures for using these chemicals. You clean first, then disinfect.

The studies I have reviewed indicate that adding a little sodium chlorite to tooth paste is not as effective as brushing your teeth, then rinsing with a sodium chlorite solution afterward. I have also noticed this when adding sodium chlorite to soap for a mild disinfecting wash. It seems to be much more effective to wash first, then disinfect.

It may be a problem of degrees. If you have very few problems with oral hygiene, the toothpaste with the sodium chlorite may be all that is needed. However, if your mouth tends to build up deposits, the stronger mouthwash solution is needed.

Tom

•
• Re: Proper stoichiometric mixing of ... SilverFox  10 years ago  5,887
This is a reply to # 1,564,893

Hello Stephan,

You are correct in that the NaClO2 solution is mixed by weight, but the citric acid solution is mixed by volume. You would have to weigh a measure of citric acid crystals to see if there is a difference between weight and volume.

You are also correct that 100 grams of Miracle-Mineral-Supplement contains 22.4 grams of NaClO2.

Tom

• Re: Proper stoichiometric mixing of ... Stephan2  10 years ago  5,975
This is a reply to # 1,565,543

The citric acid is mixed by volume? I feared that this would happen! Not all solutions are created equal...

Thanks again and especially for the fast response, so I can modify my table before too many users will read it.

I wondered about the other acids, I think these are all by weight. citric acid has a higher density than water, let's see how that plays out.

Stephan

• Re: Proper stoichiometric mixing of ... SilverFox  10 years ago  5,898
This is a reply to # 1,565,579

Hello Stephan,

When HCl is used, it is adjusted to 1.2 times the strength of the sodium chlorite solution, and is used in a 1:1 ratio. With Miracle-Mineral-Supplement at 22.4% NaClO2, the proper HCl solution would be 26.88%. Since a 5% NaClO2 solution is much safer to handle, the HCl concentration to use with this would be 6%. Since HCl is standardized at about 32% and is a solution, the dilution is done by volume.

Tom

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