Potassium Metabisulfite Question

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Bisulfite is thermally-unstable ion and it will decompose into sulfur dioxide (SO2) gas which leaves the boiling wort or water.
Do you have a source for this?

Lots of empirical evidence by low oxygen brewers has shown that bisulfite ion does NOT decompose during the boil.

I see that Sulfite somehow popped up in this metabisulfite thread.
The use of the word "sulfites" by wine makers refers to all three species in equilibrium that form when metabisulfite ion decomposes in aqueous solution, even though the SO3 is the only one actually called sulfite by a chemistry definition. Good luck getting anyone to use the correct chemistry nomenclature.
SO2•H2OH+ + [HSO3]-2 H+ + [SO3]2-

...
+1 on the trolling.
 
Wow this thread has definitely grown from the OP, into way more info than I expected! I’ll have to try and wrap my head around some of these terms everyone are discussing.
 
Lots of empirical evidence by low oxygen brewers has shown that bisulfite ion does NOT decompose during the boil.

Only literal thousand(s) of batches using sulfites, verified with sulfite testing strips and DO meters. ;)
 
ok- I get it. I just joined the forum. A lot of idiots out there who do the same and know very little. Maybe I’m one of those. Or maybe I have literally years of training on the subject and many others in brewing, biology, microbiology, general, organic, and analytical chemistry with actual degrees in these. How are you really to know? I do have all of those things. Let me introduce my experience- double major in biology and chemistry and a full medical degree with years of work at prestigious research universities in medical biological research and also worked in organic and analytical chemistry labs at the USDA.

Not only that, I’ve done everything I could to substantiate and support my assertions from way more valid sources than I have ever seen anyone do.

Personal attacks do nothing positive and labeling them as a troll does noting. Stick to the evidence and maybe learn something. Please, prove me wrong on what I have stated and maybe we can be friends and figure out something. Guess I’m too used to scientist discussions where the collegiality level is way higher.
RPh guy- I read the article you posted. It was a paper on methods on how to determine in a lab the presence of chlorophenols. It didn’t do any work to determine origin.

It looks like the sulfate discussion needs more evidence as well. I see no reason for HSO3 to decompose to gaseous SO2 through an acidic boil.
 
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Sodium metabisulfite is basically a sulfide SO2and a sulfite SO3
Not after you are doing a chlorine quenching process. It forms hydrochloric acid and sulfates.
https://dnr.wi.gov/regulations/opcert/documents/WWSGDisinfectionADV.pdfLet me add though that the SO2 component is not real world. When disassociated in water it reacts like 2 sulfites. Check out reactivity section here:
https://en.m.wikipedia.org/wiki/Sodium_metabisulfiteGoing the other way to get to SO2 takes a lot of energy or biochemical processes.
https://link.springer.com/chapter/10.1007/978-1-4757-9438-0_2
 
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Sodium metabisulfite is basically a sulfide SO2and a sulfite SO3
Not after you are doing a chlorine quenching process. It forms hydrochloric acid and sulfates.
https://dnr.wi.gov/regulations/opcert/documents/WWSGDisinfectionADV.pdf

Yes, I know. sorry I wasn't clear. The original question as about adding k-meta or Na-meta, and asking if it was boiling off. We got a bit sidetracked, and I wanted to be clear to the original questioner that we WERE talking about metabisulfite. That's all I was saying, and I apologize that it wasn't explained well.

The science is great, and we need to show it but I didn't want to look like we went off the rails.

WAY too many people who are new to brewing science mix up potassium metabisulfite and calcium sulfate (gypsum) when we say "sulfite" or "sulfate" and they are difference substances for different purposes. Many people new to winemaking, for example, will start a query with "my girlfriend has a sulfate problem- should I add it to my wine?" so I always want to be clear which substance we are talking about at the beginning.

Anyway, please carry on!
 
Sulfate or sulfites don’t boil off. If you insist on treating the chloroamines, which I doubt the need to do so because they are nonreactive anyway (unless in sufficient quantity to smell them, then I would trade off that for the added sulfates), please check out the link from Wisconsin dnr for water treatment for amount to add calculations. You’ll need to know how much is present though. Chlorine itself it much easier to remove either through activated carbon filtering or just letting it sit. That seems very practical to me as a basic protection with little more required than some forethought, ie fill up your HLT the night prior and let sit.

Sulfites tend to work more on bacteria in the presence of oxygen. It forms hydrogen peroxide and selectively kills microorganisms without peroxidase activity.
So that’s why it’s so important in winemaking. Take out the bacteria that spoil batches without hurting yeast too much.

https://www.ncbi.nlm.nih.gov/pmc/articles/PMC168295/
I personally don’t like the idea of adding sulfates/sulfites to beer. The boil takes care of the microbes before fermentation and the chlorine can be treated in other ways without the addition of sulphur, something usually not pleasant to smell, taste, and it can cause negative reactions (medical) to some individuals.
 
So I am new to this discussion and recently used some campden tablets to treat water before brew day at a ratio of 1 tablet per gallon after mistakenly reading the directions. It stated “Use as needed,1 tablet per gallon produces 30ppm of free SO2”. I didn’t realize until I listened to the Brülosophy podcast on this topic today and about how little it takes to treat for packaging. The beer is currently fermenting now and smells fine. What can I expect with this beer? Is that much SO2 a significant issue or is it even safe to drink? Im really bummed about it but mistakes happen.
 
So I am new to this discussion and recently used some campden tablets to treat water before brew day at a ratio of 1 tablet per gallon after mistakenly reading the directions. It stated “Use as needed,1 tablet per gallon produces 30ppm of free SO2”. I didn’t realize until I listened to the Brülosophy podcast on this topic today and about how little it takes to treat for packaging. The beer is currently fermenting now and smells fine. What can I expect with this beer? Is that much SO2 a significant issue or is it even safe to drink? Im really bummed about it but mistakes happen.
It likely all oxidized during the brewing process and aeration, into sulfate. Sulfate is perfectly harmless. In beer sulfate tends to increase the perception of bitterness.
 
Sulfate or sulfites don’t boil off. If you insist on treating the chloroamines, which I doubt the need to do so because they are nonreactive anyway (unless in sufficient quantity to smell them, then I would trade off that for the added sulfates), please check out the link from Wisconsin dnr for water treatment for amount to add calculations. You’ll need to know how much is present though. Chlorine itself it much easier to remove either through activated carbon filtering or just letting it sit. That seems very practical to me as a basic protection with little more required than some forethought, ie fill up your HLT the night prior and let sit.

Sulfites tend to work more on bacteria in the presence of oxygen. It forms hydrogen peroxide and selectively kills microorganisms without peroxidase activity.
So that’s why it’s so important in winemaking. Take out the bacteria that spoil batches without hurting yeast too much.

https://www.ncbi.nlm.nih.gov/pmc/articles/PMC168295/
I personally don’t like the idea of adding sulfates/sulfites to beer. The boil takes care of the microbes before fermentation and the chlorine can be treated in other ways without the addition of sulphur, something usually not pleasant to smell, taste, and it can cause negative reactions (medical) to some individuals.

Brewers add sulfites (in the form of potassium metabisulfite usually) to the brewing water to react with chlorine/chloramines to remove that from the water.
Chlorine compounds interact with malt (and later, with yeast) to form chlorophenols. You absolutely should NEVER brew with chlorinated water for those reasons.
Chlorine will off-gas, but chloramines do not. They need to be removed, as they also don't boil off in any sort of reasonable time.
 
Chlorine gas (Cl2) reacts with Oxygen to form hypochlorous acid which then reacts with a ton of stuff. (Hypochlorous acid - Wikipedia)
That’s how everything gets destroyed. This reacts with amines NH2, to form a vastly less potent reactor but one that still has antimicrobial action without as many side effects and longer effect. Chlorine and hypochlorous acid move into and out of solution based upon pressure and agitation. It’s very unstable. As such, simple sitting overnight or boiling for a short amount of time will eliminate most of the dissolved chlorine and the hypochlorous acid as the equation pushes from hypochlorous acid to gaseous chlorine and out of the solution.
Of course, sulfites can remove activated hypochlorous acid by forming hydrochloric acid and sulfate. This works on hypochlorous acid as well as chloroamines. But the chloroamines are not phenol reactive to an appreciable extent. Nor do they do much of anything to my knowledge except aminate. (So the idea that chloroamines are an easy and direct way to form chlorophenols is pretty difficult case to make as far as I can tell, although I’m still trying to learn as well but all evidence is to the contrary. Chlorine aka chloride is bound in an ionic chemical composition in the chloroamines, similar to table salt which is sodium and chlorine, Na + and Cl- .
I know plenty of pro brewers that do nothing more than fill their HLT the night before brewing to off gas chlorine with no deleterious effects.
 
But the chloroamines are not phenol reactive to an appreciable extent.

Where is the evidence for this? I didn't see it in any of the links provided.
 
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I assume you mean this...
"Chloramine presents the significant advantage of virtually eliminating the formation of chlorination by-products and, unlike chlorine, does not react with phenols to create taste- and odour-causing compounds."

Yet, there is no data given as evidence, or any supporting citation . I'd put it's reliability on a par with all the textbooks @mabrungard mentions. Or actually, less, because the textbooks are brewing specific. I could easily read the above statement, in the context of a treatise on public water treatment methods, to mean that the reaction isn't significant in drinking water, i.e. where phenols are fairly low. But even if it means exactly what it says, it's still unsupported in that document.
 
I'd put it's reliability on a par with all the textbooks @mabrungard mentions. Or actually, less, because the textbooks are brewing specific.
I’m really not following you on this. Not sure how science is more correct in brewing textbooks than in technical science documents prepared for water management and industry professionals, chemistry textbook and articles. Phenols don’t preferentially react only to brewing.
So I’ve shown evidence, now show yours. I’ve done my research. I’ve earned my science degrees. Please show me an article that analyzes the production of chlorophenols from chloramines brewing or otherwise. Then make sure they show suitable reaction conditions with the correct precursors and environment. I’ve searched hundreds of articles and found no support and presented a chemistry explanation. If I’m wrong you should be able to respond in kind, with evidence and explanation.
 
I’m really not following you on this. Not sure how science is more correct in brewing textbooks than in technical science documents prepared for water management and industry professionals, chemistry textbook and articles. Phenols don’t preferentially react only to brewing.

That's not what I said. I said drinking water may have lower levels of phenols than a mash, and that the quoted sentence may have been in the context of low phenol level drinking water.

If I’m wrong you should be able to respond in kind, with evidence and explanation.

I didn't say you were wrong. I said you haven't proved your assertion.

There is a huge acceptance in the professional and homebrew communities of the assertion that chloramines form chlorophenols in the mash, and a huge amount of anecdotal evidence of people experiencing it. And it's in the textbooks. You, with your dissenting opinion, are the one with a duty to prove otherwise. You haven't.

So I’ve shown evidence, now show yours. I’ve done my research. I’ve earned my science degrees.

Your degrees don't count as evidence.
 
Some other things to keep in mind:
  1. Very few municipalities even use chloramine; the vast majority use chlorine.
  2. The amount of sulfite needed to remove both chlorine and chloramine is very small and the reaction products and negligible. So even if the sulfite is useless in the case if chloramine, it's still not hurting anything.
  3. Beer is a very complex medium that has a lot of enzymes that allow the transformation of otherwise unreactive substances.
 
What textbooks are you referring to specifically? It should be very easy for you to confirm your assertions with actual evidence.
Acceptance or practice does not mean correct or good science. Homebrewers do a lot of strange things that don’t really do anything and are based on false understanding and assumptions.
 
One example of a brewing textbook:
Kunze Technology Brewing and Malting 6th English Ed. p 90.

Sterilization by Chlorination
Hypochlorous acid is formed by introducing chlorine gas into water. [...]
The equipment costs are low but harmful products (adsorbable organic halide, chlorphenol, trihalogenmethane and others) are formed when the water contains organic substances or phenols.
 
What textbooks are you referring to specifically? It should be very easy for you to confirm your assertions with actual evidence.
Acceptance or practice does not mean correct or good science. Homebrewers do a lot of strange things that don’t really do anything and are based on false understanding and assumptions.

How many years have you been brewing? I've been a beer judge a long time, and have judged beers in competition that have chlorophenols. When inquiring into this, the brewers will mention that they brewed with tap water, but "low levels of chlorine". Many municipalities currently use chloramines, since they are more stable.

I understand that you know your stuff but maybe you haven't studied enough brewing science and texts to fully understand the interaction of chlorine compounds and the enzymatic activity of the mash, and/or the yeast's interaction during fermentation.

One of my favorite quick reads on this is a short article by noted brewing water chemistry expert @ajdelange: Water Filters | MoreBeer That's more about removing chloramines and why/how, but it answers the questions on why it needs to be done.

And an except from "Water" by Colin Kaminski and John Palmer may be helpful: Removing Chlorine from Brewing Water | My Fermentation

I know you keep saying that chlorine doesn't impact the mash, but that doesn't make it so. Brewers know it does, our brewing textbooks (which I can't post, because they are books and not available online) tell us it does, our tastebuds tell it does, etc.
 
@barada83

@mabrungard is also a brewing water expert. You dismissed him, but maybe it's worth listening to him.

I know that homebrewers do indeed have some strange habits, but removing chlorine from brewing water isn't done because we have nothing better to do. It's because using chlorinated water makes beer taste bad, forming those chlorophenol off-flavors that are very distinctive.

You don't have to believe me. Try it. Brew an all-grain batch with chlorinated water, especially if the chlorine is in the form of chloramines. Brew one without. Taste them.
 
Just to clarify, in case it’s become unclear - chlorine should definitely be dealt with. It’s pretty easy too. You can do so though letting water sit, boiling, carbon filtration, or chemical treatment.

I don’t agree with the sentiment persistent in home brewing to chemically treat your water for chlorine and especially not for chloroamines if present. Adding sulfurous compounds to the complexity of beer as stated, can do no good. They don’t just disappear and sulfur is the basis for a lot of bad tastes, smells, and even health concerns. Treat it chemically as a last resort.
 
Adding sulfurous compounds to the complexity of beer as stated, can do no good. They don’t just disappear and sulfur is the basis for a lot of bad tastes, smells, and even health concerns.
You're way off the mark with these sentiments. A negligible amount of sulfate produced by dechlorination with sulfite will have zero effect on the beer.
 
You're way off the mark with these sentiments. A negligible amount of sulfate produced by dechlorination with sulfite will have zero effect on the beer.

And idiots like me actually ADD it to my beer in the forum of gypsum to enhance my highly bitter IPAs.
 
Yooper - Thank you for the links. A lot closer to what I am looking for versus you’re wrong and and a troll. I wonder why they weren’t posted sooner during my rambling phase. I really am trying to keep learning and if something isn’t making sense I’m going to keep pushing until I get it figured out.

If you add metabi in excess quantities you will get sulfate and residual sulfites. So sulfates are ok, can be good or bad depending on purposes. It should be part of the thought process at the very least as to the effects even from just an experimental and repeatable view in your brewing. Sulfites might not be the same. Beer is not typically high enough ph where it exists as sulfur dioxide which is volatile and could come out during a boil. Here is an article as it applies to winemaking Improved Winemaking: Sulphur Dioxide.

And one on sulfites Sources and Impact of Sulfites in Beer | MoreBeer


I still am missing one thing. How, and in mechanisms, chloroamines form chlorophenols. Can anyone help me answer this? Because if they don’t, then you really don’t need to worry about sulfites in the first place.
 
If you add metabi in excess quantities you will get sulfate and residual sulfites.


I still am missing one thing. How, and in mechanisms, chloroamines form chlorophenols. Can anyone help me answer this? Because if they don’t, then you really don’t need to worry about sulfites in the first place.

Correct- but we are adding minute quantities, and with the reaction that occurs, which is instantaneous, there is no residual sulfite to worry about.
https://www.homebrewtalk.com/threads/campden-tablets-sulfites-and-brewing-water.361073/
I'm NOT a chemist at all, but in one of my brewing chemistry classes, it was explained to me that the interaction between the enzymatic malt in the mash and the chlorine is what creates the precursors for the chlorophenols. I'm sure that you could find this info, but most of the really good papers/textbooks are behind paywalls so I don't have a quick and easy explanation.

The interaction with the yeast is very complex, and I barely understood it when it was taught to me and I'm way too far out of it to remember it, except "Chlorine, especially in the more stable form of chloramine, is bad for yeast". I imagine it's because chlorine will off-gas, while chloramines will not.
 
Yooper - Thank you for the links. A lot closer to what I am looking for versus you’re wrong and and a troll. I wonder why they weren’t posted sooner during my rambling phase. I really am trying to keep learning and if something isn’t making sense I’m going to keep pushing until I get it figured.

You essentially kicked open the door of the church and yelled.. god doesn’t exist. What did you expect to happen?

There are many learned people around here with a massive amount of combined brewing experience, which would be helpful to that learning thing you mentioned. And much like it was in school, works best if you listen more and argue less.
 
The original question:

So I have read some, probably not all, threads on PM/campden tabs being used to rid tap water of Chloramines. My question is if you add too much does the excess get boiled off or will there be residual yeast killing compounds still in the wort after the boil that would not allow fermentation after pitching the yeast and kill them?

The thing with forums is that we try to answer a question. This is the Brew Science forum, so of course we try to give answers that have a scientific basis and that often generates discussion and more questions.

But still, the idea is to answer the question, which was answered in the very next post:

Excess metabisulfite is decomposed during the boil, so you don’t need to worry for your yeast. However, you don’t want to overdose since it adds ionic content that may not benefit the beer.

Yooper - Thank you for the links. A lot closer to what I am looking for versus you’re wrong and and a troll. I wonder why they weren’t posted sooner during my rambling phase. I really am trying to keep learning and if something isn’t making sense I’m going to keep pushing until I get it figured out.

I still am missing one thing. How, and in mechanisms, chloroamines form chlorophenols. Can anyone help me answer this? Because if they don’t, then you really don’t need to worry about sulfites in the first place.

We are all here to learn (I learn every day), but we don't want to take away from the OP's question. If we want to discuss chlorophenols in great detail (or have a 'rambling phase') please start a new thread/question. Thanks!
 
I appreciate that Barada83 is a learned person. While I have a Masters in Environmental Engineering that included intense study of all things water and wastewater, I was quickly humbled decades ago when I tried to assert my knowledge without understanding the MORE complex chemistry of brewing. I was schooled on the subject through interactions such as this forum and I learned beyond my engineering training and experience. Not all the 'truths' from medicine and biology are likely to apply to brewing (or more correctly, there is more to this subject than you realize).

Regarding the degradation of bisulfite to sulfur dioxide, there are plenty of sources that attest to this phenomena. Sodium sulfite is a daughter product of sodium metabisulfite and it represents what is present in our water and wort solutions. This resource confirms that heating does drive off SO2: https://www.southernionics.com/pdf/pb/Sodium_Bisulfite_40.pdf
 
This resource confirms that heating does drive off SO2: https://www.southernionics.com/pdf/pb/Sodium_Bisulfite_40.pdf
This resource provides no data about how much SO2 is driven off. Are there any sources that do?

It's important to consider the pH. The average pH of the solution in that document is 4.0. In comparison, the fraction of sulfite species present in wort (pH 5.4) as volatile sulfur dioxide is more than 1 order of magnitude smaller.

The chemistry shows that over 99.97% of the sulfite in wort is ionized and therefore not volatile (using a pKa2 of 1.81).
The mechanism by which sulfite breaks down in wort is oxidation, not evaporation. For anyone using sulfite just for chlorine/ chloramine removal, any residual sulfite will oxidize to sulfate immediately upon mash-in by reaction with oxygen radicals.

This matches extensive low oxygen brewing experience, which provides ample anecdotal evidence that sulfite is not driven off during the boil, at least not entirely. I'm working on a reliable testing method so I can provide scientific data for this.
 
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“The chemistry shows that over 99.97% of the sulfite in wort is ionized and therefore not volatile (using a pKa2 of 1.81).”

That’s exactly right. There’s a resource I posted a few posts previously discussing sulfites in wine making which is dealing with other a much more acidic environment in which the reaction equilibrium pushing the aqueous sulfites towards the less soluble hydrogen disulfide.

One of the more interesting ways to get rid of sulfites / sulfides described in the article Was to spray against the side of a vessel causing a better exchange condition for a dissolved gaseous compound to come out of solution. But with beer being way less acidic, it is also way more soluble in water. (There’s a telling chart that goes through the status of sulfite through the ph range).

Now, with reaction equilibrium and the availability of hydronium ions in the system, there WILL be Sulfur dioxide in the solution that can gas off. Just not much.

I don’t like being called a troll is all. Brewing is more complex than anyone realizes. Sometimes we all are wrong. Me included.
 
I'm using a blend of county and RO water. Do I calculate the amount of potassium meta bisulfate needed based only on the amount of county water in the blend?
 
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