NO3:PO4-x conversion to vinegar

[tmz]

Scott,
There are a number of processes to look at( anaerobic digestion, acetogenesis, hydrolysis, fermentaion etc ;no one place I know of.
Polymers as in pellets are relatively large molecules/macromolecules that break down to monomers smaller parts via bacterial activity,hydrolysis IIRC. The monomers include sugars which in turn break down via a number of bacterial pathways to ethanol and acetic acid.
The polymers in pellets , monomers ,ethanol and acetic acid are all organics and thus all contain organic C.
I prefer to skip the breakdown of polymers and monomers and the byproducts produced and shorten the bacterial cascade involved in getting to acetate I don't personally want to add extra sugar along the way .
I think of it in an oversimplified fashion as : polymers to monomers/ sugars to ethanol to acetic acid to acetate.

 

[Aquarist007]

Scott,
There are a number of processes to look at( anaerobic digestion, acetogenesis, hydrolysis, fermentaion etc ;no one place I know of.
Polymers as in pellets are relatively large molecules/macromolecules that break down to monomers smaller parts via bacterial activity,hydrolysis IIRC. The monomers include sugars which in turn break down via a number of bacterial pathways to ethanol and acetic acid.
The polymers in pellets , monomers ,ethanol and acetic acid are all organics and thus all contain organic C.
I prefer to skip the breakdown of polymers and monomers and the byproducts produced and shorten the bacterial cascade involved in getting to acetate I don't personally want to add extra sugar along the way .
I think of it in an oversimplified fashion as : polymers to monomers/ sugars to ethanol to acetic acid to acetate.

I like oversimplified .. Thanks
I also think this explains the longer wait time with pellets as opposed to liquid carbon dosing
I wonder if the poet Nash was a reefer when he coined the phrase:
" candy is dandy but liquor is quicker":lol:

 

[tmz]

Nice touch Scott.
I like simple and brief; but that's not always easy to do.
Mark Twain once wrote a friend a long loquacious letter . He ended it by apologizing for it's length, explaining if he had had more time he would have written a post card.

 

[dartier]

Shermanator, those mystery peaks in the NMR would not be Methanol would they? If Methanol was present, would it be distinguishable from Ethanol?

I was curious about Methanol after reading about it in the Natureef threads. I ran across this thread in the RS forum http://www.reefcentral.com/forums/showthread.php?t=2442378. Curiously the RS Rep reply did not dispute there was Methanol in it, just that there were more ingredients than just Methanol.

I would have thought (as well) that Methanol would be too toxic to dose in your tank, which would be surprising if there is. More the pity, locally Methanol is $9.99 for 4L @99.9% methanol, and Vodka is $37.25 for 1.1L @40% ethanol. You got to love those sin taxes!!! :mad2:

Dennis

 

[JoshuaG]

Personally,I would not increase the dose. The nitrates are high and it may take months for carbon dosing to affect them very much particularly with continuous heavy feeding.

Thanks for the info, that is what Kevin at Red Sea said as well. I have maintained the 40ml a day and it is for sure helping, the cyano I had is going away and SPS are starting to show a little color now.

I am going thru a bottle a month tho so I might try and make the switch to the vodka/vinegar if I can figure out the correct dosage to match what I am doing now.

I am getting this growing in my sump in the area I dose, small clumps here and there this was the largest.

 

[Randy Holmes-Farley]

Shermanator, those mystery peaks in the NMR would not be Methanol would they? If Methanol was present, would it be distinguishable from Ethanol?

Methanol is easily distinguished from ethanol in an NMR. The small peak at 3.22 might be a small amount of methanol. If so, it is about 8% of the ethanol concentration.

 

[shermanator]

Methanol is easily distinguished from ethanol in an NMR. The small peak at 3.22 might be a small amount of methanol. If so, it is about 8% of the ethanol concentration.

Yeah, there is a tiny amount of methanol in there. And a tiny amount of isopropanol, too. I doubt either of these are intentional ingredients of NOPOX (they are likely byproducts from the fractional distillation for their source of ethanol).

I've also seen RedSea claim there were metals in there... There could be, but most useful metals are paramagnetic and would, if in a quantity approaching the organic substituents cause quite a disturbance to the NMR signal. Given that NOPOX is colorless it also rules out most metals. It would take an ICP analysis to know for sure. If there is any metal, I'd propose Zn(II) -- based on color and it's diamagnetic.

 

[dartier]

Methanol is easily distinguished from ethanol in an NMR. The small peak at 3.22 might be a small amount of methanol. If so, it is about 8% of the ethanol concentration.

Hmmm, 8% methanol? Do you think that using a substitute that had 10% methanol to 90% ethanol would be detrimental?

I found a local source that produces marine stove fuel that only contains ethanol and methanol, and $6.25 L sure beats $37.25 for 1.1L.

Dennis

 

[mindi]

Playing with fire..?

Playing with fire..?

Sorry

 

[shermanator]

Hmmm, 8% methanol? Do you think that using a substitute that had 10% methanol to 90% ethanol would be detrimental?

I found a local source that produces marine stove fuel that only contains ethanol and methanol, and $6.25 L sure beats $37.25 for 1.1L.

Dennis

No, it's less than 1% methanol. I'll post the exact amount later tonight but it's a byproduct of the ethanol they added (most likely).

 

[dartier]

I think Randy was suggesting that the amount of Methanol was 8% in comparison to the amount of Ethanol. So if the total volume contains 12% Ethanol, than 8% Methanol of the Ethanol would be .96% of the total volume would be Methanol.

Boy that sounded a lot easier to explain in my head. :sad2:

In any case I am looking forward to see the exact amount Shermanator.

Dennis

 

[Randy Holmes-Farley]

Assuming the peak at 3.22 or so is methanol, and assuming the numbers under the peaks are the integration, I divided 0.23 by 2.00 and then multiplied by 2/3 to correct for 3 protons in methanol to the two in ethanol next to the OH. That gave me 0.077 as the mole ratio of methanol to ethanol.

 

[Randy Holmes-Farley]

Hmmm, 8% methanol? Do you think that using a substitute that had 10% methanol to 90% ethanol would be detrimental?

I found a local source that produces marine stove fuel that only contains ethanol and methanol, and $6.25 L sure beats $37.25 for 1.1L.

Dennis

I do not know if methanol added to the aquarium is detrimental, but I don't see a reason to think it is beneficial relative to other organics, such as acetic acid or ethanol.

I've not generally be a believer that diversity in organics implies diversity in bacteria implies a benefit. It may be true, but I do not think it is obvious that it is desirable without some experimental evidence.

I agree that it is likely they used a denatured ethanol to avoid tax issues, and that may be the reason methanol is there.

 

[dartier]

I agree that it is likely they used a denatured ethanol to avoid tax issues, and that may be the reason methanol is there.

That is what I am thinking as well, and the reason I am curious about doing the same.

Looking back at my notes, I have your suggested recipe being 10 parts vinegar + 6 parts vodka + 4 parts RODI to get the equivalent of NOPOX. So diluting the stove alcohol at 4 parts alcohol to 6 parts RODI would produce a 80 proof vodka substitute.

This would mean that 30% of the final product would be from the alcohol, which would be a 40/60 alcohol to water ratio. That is 12% of the final product would be contributed from the alcohol, so the total Methanol would be 1.2% (assuming 10% methanol in the vodka substitute).

I have since located the MSDS from the manufacturer and it lists the methanol at 5-15% of the total volume (though their website splits the difference at 10%). So best case .6% methanol and worst case 1.8% methanol in the final solution.

This would be so much easier if I could get 1.75L of Vodka for $14 like TMZ

Dennis

 

[shermanator]

Okay, so NOPOX actually has 2.1% methanol.

For the methyl peaks of ethanol : methanol, the integrations are 2.97 : 0.23. So it's ~13 mol ethanol to 1 mol methanol, which is as Randy said. 40% ethanol is 0.68 mol ethanol, so there is 0.052 mol of methanol per 100 mL. That is 2.1 mL / 100 mL or 2%.

And to be perfectly complete, there is also 1.2% isopropanol in NOPOX.

I don't think either methanol or isopropanol are there for any biological reason. In lab, we have a bottle I just looked at of 90% ethanol that is denatured with 5% methanol and 5% isopropanol. I'm sure RedSea uses something similar for their ethanol source.

While it's probably fine to use a source of ethanol with 10% methanol (to save money), for everyone else looking to cheaply recreate NOPOX, there is no reason to add tiny amounts of methanol or isopropanol.

 

[dartier]

That is great news shermanator. Thanks for working out the actual methanol of NOPOX. At least it gives me comfort in knowing that I am not completely foolish for even contemplating using it.

I will still call the manufacturer to confirm that their MSDS is accurate and that there are no other unlisted ingredients.

Dennis

 

[dartier]

Well I am taking the plunge today and mixing up a DIY batch using the stove alcohol that I sourced earlier.

Since I am in Canada, and the taxes on alcohol would make using vodka almost as expensive as using the original N03P04-X, I will be using this product as my ethanol source http://www.thechandleryonline.com/product_info.php?cPath=218&products_id=3331. I called the manufacturer and confirmed that it is 90% Ethanol and 10% Methanol with the only other ingredient being Blue foodsafe colouring. I guess the colouring is mean't to be a visual que to the inebriated that it is not Vodka. :beer:

The formula that I have from Randy earlier in the thread is:

RHF version NO3PO4X = 10 parts vinegar + 6 parts vodka + 4 parts RODI

So I plan to use the following:

Vinegar: 100ml + 40% Alcohol: 60ml (24ml stove alcohol + 36ml RODI) + 40ml RODI -> 100ml vinegar + 24ml stove alcohol + 76ml RODI -> 4|1|3 or 1|.25|.75 (vinegar|alcohol|RODI)

My vinegar on hand is older, so I purchased a new 1L bottle. This should give me 2L of the final mixed solution. I am expecting to dose 10ml/day, so this would be a 200 day supply. Do you think 200 days is too long to expect it to maintain its potency?

Dennis

 

[dartier]

For anyone looking this up later, and using the stove alcohol substitute, I adjusted to using the ratios from post #48. This proved quite easy using the stove alcohol. That post suggests 1 part vinegar + 1 part 30% ethanol, so mixing 1L vinegar + 300ml alcohol + 700ml rodi gets you to the correct mixture.

Dennis

 

[Aquarist007]

For anyone looking this up later, and using the stove alcohol substitute, I adjusted to using the ratios from post #48. This proved quite easy using the stove alcohol. That post suggests 1 part vinegar + 1 part 30% ethanol, so mixing 1L vinegar + 300ml alcohol + 700ml rodi gets you to the correct mixture.

Dennis

Watching this with great interest
I'm dosing 10 ml vodka daily to a 250 gal system. How much of your dyi would I use to replace it?

 

[droog]

For anyone looking this up later, and using the stove alcohol substitute, I adjusted to using the ratios from post #48. This proved quite easy using the stove alcohol. That post suggests 1 part vinegar + 1 part 30% ethanol, so mixing 1L vinegar + 300ml alcohol + 700ml rodi gets you to the correct mixture.

Dennis

Any update Dennis? How much are you dosing now, and where are your No3/PO4. Fish still swimming?

-droog