Oh yeah, I meant to ask: at what pH does tannin extraction become a concern when sparging? Or, is hitting the proper pre-boil pH the main purpose of acidifying sparge water?
Also, on the use of salts to acidify/bring down pH, it sounds like that is only viable during mashing, when chemical reactions are able to break down the salt and allow its components to interact with other chemicals in the mash (to put it very simplistically). Yes? If so, do similar chemical reactions occur if salts are added to the boil, or is the mash the only shot at affecting pH with salts?
Wow! I just tried the opposite experiment. I have used 300 ppm sulfate for about a decade in my APA’s and AIPA’s and I’ve really enjoyed them. But AJ kept harping that great PA’s could be made with much lower sulfate. So I tried it. Brewed my standard SNPA clone with 100 ppm sulfate instead of 300 ppm. I just took the dose of gypsum out to reduce the level to 100 ppm and left all the other ions at their regular levels.
The result is a fine beer and its quite clean and still bitter. But its immediately apparent that this beer doesn’t dry out in the finish like the previous batches have. That does reduce the overall bittering perceptions slightly and shifts the balance toward the malt. I have to say that it still came across as an APA, but the maltiness was off-putting. I’ve mixed in a little gypsum in the glass and the improvement was immediate (well, as soon as the gypsum dissolved). [/quote]
Wait, what did you just do there? :shock: You just put a bit of gypsum into finished beer? How scientific were you? For a pint, even half a gram would be what… +1,000 ppm sulfates? I have a homemade cascades APA with which I’d be interested to try this out, but I’d love to know how much I’m adding (to know whether I’m at 200 or 2000 ppm), and so how to “calibrate” my taste reponse.
I never felt like it made sense that the ratio was as important as (or more important then) the mineral concentration(s). If you have an awesome scale (as I do not), I’d implore you to better explore the Cl:SO4 flavor balance. For science!
It seems to me you could use John Palmer’s spreadsheet (can be downloaded from the bottom of this page http://www.howtobrew.com/section3/chapter15-3.html
) or some other water calc tool to determine how much a given weight of gypsum would add to 12oz of beer. I think 12 ounces of beer is approximately .1 gallon, so if I set “mash volume” on his spreadsheet to .1 gallon, then add .1 gram, it indicates that I will have added 147ppm of sulfate.
Of course, you’d need to add that to whatever the sulfate ppm of the finished beer is.
IMO - when acidifying sparge water the goal is optimum pre boil pH with a side benefit of never extracting tannins. Icky, I think you are getting it. Yes, only 2 times to use calcium to your advantage:
Calcium in the mash combines with malt phosphates to create phytic acid neutralizing alkalinity and thus pH.
Calcium in the boil has the typical reaction for reducing alkalinity and this continues to drive pH down which I consider a good thing. Remember all calcium was lost in the previous reaction to drive mash pH down so if you want to take advantage of this you must add calcium to boil.
Once you guys compare your homebrew with a commercial beer you will realize how far off you are. Also consider the pH scale is logarithmic…
I bought a $10 scale on ebay which is accurate to a tenth of a gram. I also use this for my hop additions and change it’s setting to ounces. One of the best investments I made in brewing.
Again, we’re covering a completely different topic but it’s not fazing me, so here goes: I have used calcium chloride and gypsum post-fermentation to fix a water problem I made earlier in the process. If I overdo the gypsum, I might take a pint of water and add 1 or 2 grams of calcium chloride to the water, boil it, let it cool and add it to the keg. I’ve done it with gypsum when the beer was too malty or lacked crispness. It works and it has improved beers for sure. I once made a spiced pumpkin ale that came out too dry which is not good for the style. I boiled some water with 4 ounces of brown sugar and added that to the cold, kegged and carbed beer. Boom, instant PERFECT spiced pumpkin ale. Now I don’t want to do A LOT of this but it really does work. It only works if you need to ADD something, clearly but it can be done.
zwiller, thanks for further clarification… again! Things are definitely kinda sorta starting to seem less slippery when I contemplate them . I assume any finished beer pH tests/comparisons should use uncarbed samples?
Very interesting about the finished beer additions, KL!
zwiller, you wrote back on the previous page about Ca not making it through the mash and into your kettle, which would mean that one must add all the salts to the kettle necessary to hit that golden rule of 50 ppm (for the yeast).
I wonder if that is true though. I vaguely recall reading (while drinking no doubt…) from one of the Water Gods (AJ or MB) that phosphoric acid actually did not appreciably precip out Ca in the mash, and for that reason, was fine to use as a pH adjuster to your mash water. This statement turned prior thinking on its head, for the “old” story was that phos acid would drop all your Ca out.
From that, I’d draw the rather lazy conjecture that the phosphates from the malt could not remove all the Ca either. And that even if all the Ca did precip out, some of it will still get rinsed out esp if you do a vigorous run off, such as with batch sparging.
then again i may be making all this up, so lay it on me. i’ve been assuming a significant portion of my mash salt additions make it to the kettle. i’ve not had any noticeable problems, but i’m still waiting to have that beer that’s so damn perfect, that i can only say, i must be ready to die because it can’t get any better than this…
[quote=“seajellie”]zwiller, you wrote back on the previous page about Ca not making it through the mash and into your kettle, which would mean that one must add all the salts to the kettle necessary to hit that golden rule of 50 ppm (for the yeast).
[/quote]
Hmm. You may have just broke my brain with that one. If I use EZ_Water and I enter my mash additions (CaCl or whatever) it will tell me that my mash ppm for calcium is something (say, 84ppm) and that my overall ppm for calcium is something like 51 (mash+sparge) but that overall number is the 50ppm you’re looking for so I don’t think your statement holds water. I’m not disputing it just saying that it doesn’t feel right. Hopefully one of the waterheads will pop their head in here and 'splain that one. WHERE ARE THE ADULTS!?!?!?!?!? :lol:
I took a very unscientific approach to adding gypsum to my pint of APA. Twice. I don’t know how much I added, but probably on the order of 200-300 ppm (or less; could be much less) gypsum. Both times it definitely left an aftertaste, either bitter or astringent. It masked the malt to a small degree and/or left a bit of an dry/astringent/bitter feeling not present in the unaltered pint. I think I’ll give 300ppm sulfate a college try with my next AIPA.
Anyhow, apologies to Ken for hijacking his thread; lots to learn, here!
:cheers:
Back to calcium; take a look at the pictures on the earlier pages of the thread. Calcium will actually bind & precipitate out with the malt phosphates. I imagine that Martin has already taken this into account in his program–as it seems to do everything else–but i could be wrong.
Either way, Kai cites a report that less than 30% of the available calcium (technically 2/7ths) will react with the malt phosphates to reduce mash pH. I suppose what this means is that not all calcium added to your mash is going to precipitate out; some will end up in the boil kettle.
The way I read the Ca left in the mash thing is that any Ca that pairs off with (neutralizes) bicarbs is left behind. My guess is that you end up with -ppm for bicarbs if you add calcium in excess of what’s needed to neutralize all bicarbs. At that point, any calcium added would carry to the mash and any bicarbs added would be neutralized by/would neutralize some portion of excess calcium
This is a very novice, layman interpretation, though… pending verification or smackdown.
Don’t apologize. This has been a great discussion and I consider it to be “all-inclusive”. Whatever side topics seem relevant to this topic are welcome here.
Some of these posts are what get me to doze off though… when I talk with some of these guys like AJ, Martin or Kai, I ask them, “just tell me what to do… I don’t need to know the whys and hows… just tell me the best way to get there”. I’m a very by-the-numbers brewer. Do step 1. Do step 2. Why do we do that? I don’t know. Because AJ told us to do that. Do step 3, etc.
My wife thinks I’m crazy. We just went to Target and while she was picking out window treatments, I was loading the cart with gallons of distilled water because it was 72¢ or something. Sometimes I have dreams about calcium or mash temps or pH or some such thing. I occasionally wake up at 3am to pee and realize that I need to disconnect a force-carbing keg from the CO2 tank. This homebrewing thing is a sickness, do you hear me? A sickness! :lol:
Yes, the calcium content you start with in your brewing water does not all make it to the boil kettle. Some data from Sierra Nevada shows that they aim for 50 ppm Ca in their kettle and start with 85 ppm in the tun. That is a 40% loss of calcium, but I think it might be more appropriate to look at just the total loss (35 ppm). The calcium and phytin reaction is the major reaction, but there are others that precipitate calcium out of the water and wort.
The 50 ppm calcium standard seems to be well founded, but that does not mean that great beer has to be made with that level. There are plenty of examples of fine beers made with far less than 50 ppm. Its just that 50 ppm Ca offers several advantages to the home and craft brewer. Better yeast production and flocculation and better removal of oxalate are the important reasons. But a brewer can work around that need for high Ca. A bigger pitching rate solves the yeast production issue, filtering solves the flocculation issue, and better cleaning practices solve the beerstone (calcium oxalate) issue. So it can be done.
In my opinion, there is not a huge need to make sure there is at least 50 ppm Ca in the kettle. But it does appear that there is a need to have at least 35 ppm in the mash tun to perform all of those precipitation reactions that occur there. My research on the beerstone issue had already pointed to 40 ppm as a minimum Ca needed to help assure that beerstone problems were not going to be encountered in brewing. That 35 ppm Ca loss does seem to support that. That is why I’ve been advocating a minimum of 40 ppm Ca in the brewing water. The 50 ppm minimum that is more commonly quoted is just a welcome factor of safety for our brewing water. But, I’m not sure that our brewing needs 50 ppm Ca in the kettle. Sierra Nevada’s practice of providing 50 ppm in the kettle may or may not be ideal. However, I feel its safe to say that its not a requirement.
Thanks again to Martin. I remembered your 40ppm threshold from another discussion and now aim for somewhere between 40 and 50. I will say that I’m a clear-beer freak so the clarity factor resonates with me.
Okay… Can I divert into a different direction that hopefully is still relevant? We know that darker beers would not be the same without their higher levels of bicarbonate (stout is made with high bicarb water, etc). In the past, I took the lower-bicarbs-are-better theory to a darker beer that was maybe 12-15 SRM. My bicarbs were lower and I also left the chlorides and sulfates lower (at their diluted levels) and ended up with a very bland, weak-tasting beer. Another local homebrewer commented, “Mmm, barleywater!”. I now understand that darker beers work better with higher levels of bicarb because the higher acid levels in the dark malts neutralize the bicarb more than pale malts would. But what happens when you have a darker beer made with lower-ion water? I hate to ask “what is the chemistry” but what was I experiencing in my experiment? Would my 12-15 SRM beer have been much better if I had the chloride and sulfate levels higher but still had the lower bicarb? I hope that’s clear. Cheers.
[quote=“Ken Lenard”]Thanks again to Martin. I remembered your 40ppm threshold from another discussion and now aim for somewhere between 40 and 50. I will say that I’m a clear-beer freak so the clarity factor resonates with me.
Okay… Can I divert into a different direction that hopefully is still relevant? We know that darker beers would not be the same without their higher levels of bicarbonate (stout is made with high bicarb water, etc). In the past, I took the lower-bicarbs-are-better theory to a darker beer that was maybe 12-15 SRM. My bicarbs were lower and I also left the chlorides and sulfates lower (at their diluted levels) and ended up with a very bland, weak-tasting beer. Another local homebrewer commented, “Mmm, barleywater!”. I now understand that darker beers work better with higher levels of bicarb because the higher acid levels in the dark malts neutralize the bicarb more than pale malts would. But what happens when you have a darker beer made with lower-ion water? I hate to ask “what is the chemistry” but what was I experiencing in my experiment? Would my 12-15 SRM beer have been much better if I had the chloride and sulfate levels higher but still had the lower bicarb? I hope that’s clear. Cheers.[/quote]
My answer, based on my understanding, is that your lower bicarb water in a darker beer (or a beer with a high amount of roasted malt) results in a sub-optimal mash pH (in this case, < 5.0 most likely), resulting in lower sugar extraction into the wort, and therefore resulting in a lower OG beer, all else considered equal. It would then be this “lower OG” end-result that produces your weak-tasting beer.
Assuming my premise is correct, if you were to add Ca++ ions into your hypothetical dark beer in an effort to introduce higher levels of chloride / sulfate (e.g, adding CaSO4, CaCl2), you’d end up with a pH even farther from optimum.
There may be additional chemistry going on in your hypothetical situation that would influence the flavor profile, but it’s not coming to me at the moment.
You went to the spot I was originally heading and that is this… I seem to notice that if I make a beer in the “amber range” from maybe 7 to 15 or so, those beers can benefit from a lower amount of bicarbonate in the water (they are smoother, cleaner, silkier, clearer) but you don’t want to make a beer in that color range with low/lower levels of sulfate or chloride because the beer ends up bland. I’m not sure I’m buying your lower-OG stance although I’m open-minded. This seems more like a beer with no snap, no punch, no flavor, no boom. What I realized was that I was following AJ’s advice to use soft water on a pilsner and applying that logic to darker beers (my mistake, no question). I am actually brewing right now and the recipe and other info is HERE
. The last time I made this beer I used 50% distilled but then got the chlorides and sulfates back up (while keeping bicarb down) and the beer was fantastic. But the issue remains: Darker beer, softer water, lower bicarb and the addition of more chlorides & sulfates can end up with a potentially low mash pH. My mash pH this morning looked slightly low. When I checked the sparge (batch sparge) then pH was correct and the preboil pH was perfect too. Thoughts?
To continue about SN in Brewing Better Beer Strong states ALL WATER at SN is adjusted inline with acid to a pH of 5.5. Mash, sparge, cleaning… ALL. This may explain why most of the Ca makes it to the kettle. For those of you not adding Ca to the kettle compare pH readings pre and post boil. Most likely it will not change. I prefer to see a nice drop. My research on Ca in the boil is 50ppm is required minimum but 100ppm being preferred by craft brewers for 2 reason clarity and pH drop. I think the germans acidify via lactic in the kettle for same effects. For the record, the pro brewers refer to this lower pH as shelf life/flavor stability. While this is technically true, the results just plain taste better too, which is whole point I’m trying to drive home.
With dark beers, once again pH is king and before you can adjust flavor ions you must dial in pH first. With dark beers you need to add alkalinity/bicarb to keep pH from getting too low as Andrew points out. I prefer baking soda for this, I find the sodium compliments the roasted grains and easy to work with. From there you can diddle with sulfate/chloride in the kettle. I would probably stick with gypsum since I use mostly english hops with dark beers and I think it works well with them.
That being said, if you’re hitting your pH’s etc and not digging the beer, water salt additions are no substitute for a good recipe or yeast strain. IMO these salt additions only really have like a 10% effect on total beer flavor all things equal. If your are not hitting pH’s then that’s a whole nother ball of wax.
Martin, what I’m taking away from this is that the less bicarb you have in your water, the more Ca will make it through the mash and into the kettle. Is that correct?
. I assume any finished beer pH tests/comparisons should use uncarbed samples?