A Brewing Water Chemistry Primer
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Sounded like an endorsement to me:
...after a painful attempt to pass off a basic batch sparge as "partigyle brewing" (i'll rant about that elsewhere) at 35:53
Justin: ...would something like the 5.2 pH stabilizer you might put in your mash for the first runnings I wonder if it would stick around for second runnings and you might not have to worry as much
Palmer: Well you know it would help the second runnings if you added it to the second mash
Justin: OK
Palmer: ...to the reinfusion because a lot of what the 5.2 is is uh phosphates so it helps to replace the phosphates that are naturally in the malt and in the mash. Those have been rinsed out now with that first runnings, predominately rinsed out
Justin: Got it
Palmer: So now you are adding more phosphate back and it helps, does help restabilize the mash pH.
Magic8Ball
Well-Known Member
gbx said:
So you aren't too interested in his Water book then?
Why do I need to read a book when I can just relax, don't worry and dump in some 5.2 stabilizer? And if I'm brewing a "stout" I can dump in a bunch of carbonate to replicate "Dublin water" which Palmer was recently talking about during his water episode on the Beer Smith podcast.
Magic8Ball
Well-Known Member
It would be great if 5.2 stabilizer worked. I love the idea of such a simple product. Add it to the mash and Viola!, 5.2 mash. I also kinda like the idea of an entire book to explain Water Chem in all its glory. RA and ions, and all that H2O stuff. I get the strong feeling that I am going to be hearing Charlie Brown parent voices one chapter into it. "Now take Ions wahh wahh wah wa wa water...."
So what I really need is Yoppers Original Post, a ward lab's water report & thesaq's excel spreadsheet (version 9.4), wally mart RO water. Its worked so far for me.
You know GBX Ill skip the Water book too.
5.2 is mostly NaH2PO4. As such it is an acid (it has 2 protons it can yield up). Put it into DI water and that water's pH should go to about 4.8. Put it into a mash at pH 6 and it will release some protons. But it won't stabilize pH at desired mash pH because phosphate buffers don't stabilize near mash pH. If you want protons and you want to get them from phosphate compounds use phosphoric acid, H3PO4 which has 3 protons to give up. It won't stabilize pH either (for the same reason that 5.2 won't) but it will lower pH effectively without introducing appreciable flavor from the phosphate ion (because it takes less to do the job - each phosphate ion releases 1 and a fraction protons on average while 5.2 releases only the fraction) nor will it introduce any sodium.
John understands the chemistry well enough to refrain from endorsing 5.2. He also understands the broader world enough to refrain from condemning it as harshly as I do.
John understands the chemistry well enough to refrain from endorsing 5.2. He also understands the broader world enough to refrain from condemning it as harshly as I do.
I for one am very interested in the coming book from JP and Colin Kaminski. I know them both personally and both have been very helpful to me in my water chem issues, as has this forum. I'm positive my knowledge and understanding will be enhanced.
BTW, in terms of update. City water will be measuring pH in the main feeding my house today. Why? Becasue the pH of my water out of the tap is just under 5! I have to add about 60 gm of sodium bicarb to every 30 gallons of water to set my HLT values to 5.6 - 6.0. The water company says they target a pH of about 7.5, so something is clearly amiss. I will tell you that since I have set the pH of the HLT, all of the downstream values are near perfect (mash, pre-boil, post boil, post ferment). I am anxious to see what Public works comes up with.
NanoMan
BTW, in terms of update. City water will be measuring pH in the main feeding my house today. Why? Becasue the pH of my water out of the tap is just under 5! I have to add about 60 gm of sodium bicarb to every 30 gallons of water to set my HLT values to 5.6 - 6.0. The water company says they target a pH of about 7.5, so something is clearly amiss. I will tell you that since I have set the pH of the HLT, all of the downstream values are near perfect (mash, pre-boil, post boil, post ferment). I am anxious to see what Public works comes up with.
NanoMan
It certainly seems so. Sounds as if some serious acid has gotten into your feed. This isn't carbonic acid (I don't think). I hope you will post again when you get the answer (if you do).
Well this is a bit of a problem. The City took a measurement at the hose in front of the house and got 7.1. Of course, that's good news as far as that goes. But now what? The logical conclusion is my meter is at fault. But, I recalibrate every (and during) each brewing session with pH standard 4 solution, the meter registers very close to 4 before I even hit the calibration cycle, and reads 4 when calibrated. I assume the standard solution is good as I go through a lot of it and am currently using a newly purchased bottle.
Yesterday, in anticipation of the city coming out, I pulled a sample from a hose bib (5.01) and from the kitchen sink (4.80); the hose bib does not go through the house water supply but comes off right after the meter. I then tested those samples with pH paper, and even added some bicarb to one of the samples to raise the pH. In all cases the paper roughly correlated to the digital meter reading.
5.0 is a lot different than 7.1 and I'm not willing to say "Oh, well..."
I suppose I could run the more involved calibration sequence using pH 7 solution (supposedly resets meter to factory settings). Beyond that, I got nuthin'! Somewhat frustrated, I must admit.
NanoMan
Yesterday, in anticipation of the city coming out, I pulled a sample from a hose bib (5.01) and from the kitchen sink (4.80); the hose bib does not go through the house water supply but comes off right after the meter. I then tested those samples with pH paper, and even added some bicarb to one of the samples to raise the pH. In all cases the paper roughly correlated to the digital meter reading.
5.0 is a lot different than 7.1 and I'm not willing to say "Oh, well..."
I suppose I could run the more involved calibration sequence using pH 7 solution (supposedly resets meter to factory settings). Beyond that, I got nuthin'! Somewhat frustrated, I must admit.
NanoMan
GotPushrods
Well-Known Member
If you're only doing a 1-point calibration, you can only be confident of your measurement at exactly 4. Anything above and below is out the window. If you aren't setting the slope, you can't extrapolate to any other value than the ONE you calibrated to.
You should use 4 and 7 buffers every time you calibrate.
You should use 4 and 7 buffers every time you calibrate.
Fair enough, although the one point calibration is the manufacturer procedure. I'll try that tonight and see what we get.
There's no real point in calibrating at both if the meter only has one calibration value that can change.
Also, I read your other posts. Most 1-point calibration meters I've seen calibrate with 7.0 solution. Does your manual say you can calibrate with 4.0 solution?
There are two calibrations with this meter (HM Digital). The quick calibration involves putting the meter in 4.0 solution, turning it on, holding the Temp F/C button until CAL flashes and then letting it calibrate. It always reads 3.9 to 4.1, and usually 4.0 after doing this.
The more involved method (which I don't recall the steps), uses 7.0 solution and is designed to reset to factory values. I've only had to use that once and usually it its because you've measured solutions of very different pH and it won't recalibrate at 4.
I will run that tonight and also measure the pH of both 4 and 7 standards. I also have a buddy who just bought one of these and we're gonna do a side by side.
What's confounding is, on the one hand I have tap water pH values that don't make sense (4.8 -5.0) and the City got 7.1, and on the other hand the meter reads the standard solutions correctly, roughly correlates with pH paper, and mash values are fairly close to what Easy Calc predicts, although my mashes always come in lower, typically by 0.5 - 0.7 pH units.
NanoMan
The more involved method (which I don't recall the steps), uses 7.0 solution and is designed to reset to factory values. I've only had to use that once and usually it its because you've measured solutions of very different pH and it won't recalibrate at 4.
I will run that tonight and also measure the pH of both 4 and 7 standards. I also have a buddy who just bought one of these and we're gonna do a side by side.
What's confounding is, on the one hand I have tap water pH values that don't make sense (4.8 -5.0) and the City got 7.1, and on the other hand the meter reads the standard solutions correctly, roughly correlates with pH paper, and mash values are fairly close to what Easy Calc predicts, although my mashes always come in lower, typically by 0.5 - 0.7 pH units.
NanoMan
The meter has to have numbers for slope and for offset. If it assumes offset then you would calibrate by varying slope using a pH 4 buffer. If it assumes slope then you would calibrate by varying offset using a pH 7 buffer. As has been noted this only works at or close to the pH of the calibrating buffer. As mash pH falls about half way between 4 and 7 meters which can only be calibrated with a single buffer are not suitable for use in brewing.
If the meter is stable there is a workaround. You can 'calibrate' it using the pH readings it gives you in 4 and 7 buffers and do some math. This is really trying to make a silk purse out of a sow's ear. It would be better to replace the meter with one that allows dual point calibration.
If the meter is stable there is a workaround. You can 'calibrate' it using the pH readings it gives you in 4 and 7 buffers and do some math. This is really trying to make a silk purse out of a sow's ear. It would be better to replace the meter with one that allows dual point calibration.
pH-200. Recommended by a professional brewer friend.
Hmmmmmm. Sounds like an A.J. DeLange article.
But perhaps what I'm really concerned about is calibrating at 7; the hot liquor water adjustment really becomes key and Easy Calc probably gets me pretty close from the grist/salt addition perspective?
Looking at its 'manual' it is clear that it adjusts offset only during the calibration process and not slope (there is no way you can set slope in a pH 7 buffer unless the isoelectric pH is other than 7). In any case you cannot accommodate the reduction in slope as the electrode ages. There is no way the meter can meet its advertized accuracy of 0.02 pH without adjusting slope and offset.
Hmmmmph. Not sure where this getting me. There are three different calibration methods: Factory Reset; Automatic Calibration, and Manual Fine Tune (going from memory here). I ran the factory reset and manual calibration. I got my "sow's ear" to where I could go back and forth between the two standards and it would read 7.00 in the7 and 4.01 in the 4. If that is true, then why isn't that good enough for what I'm measuring?
Otherwise, I need to find a better device.
Otherwise, I need to find a better device.
If you get, after calibration, a proper reading for the 4 buffer and a proper reading for the 7 buffer as adjusted for their temperatures (the actual pH values for the buffers as a function of temperature) are usually printed on the buffer package) then you are properly calibrated. The best way to check if you are properly calibrated is to read the standards after calibration over a time period. If you keep getting stable 4 ± temperature shift and 7 ± temperature shift then the meter is stable and properly calibrated.
A 'silk purse' meter will have you read both buffers as part of the calibration process and expect you to do this frequently. The procedure spelled out in you meter's manual does not do this. I cannot tell exactly what they are doing from the manual. At first blush it seems that they must be calibrating slope as you can do the calibration for any of three buffers and you can't get a slope measurement from pH 7 buffer. But I suppose it is possible that they could take a slope measurement when 4 or 10 buffer is used and an offset measurement when 7 buffer is used and store the data until they have one measurement at each of 7 and one or the other of 4 and 10. This is not the usual way of doing things but if it works to give stable, correct buffer check readings then it is valid.
A 'silk purse' meter will have you read both buffers as part of the calibration process and expect you to do this frequently. The procedure spelled out in you meter's manual does not do this. I cannot tell exactly what they are doing from the manual. At first blush it seems that they must be calibrating slope as you can do the calibration for any of three buffers and you can't get a slope measurement from pH 7 buffer. But I suppose it is possible that they could take a slope measurement when 4 or 10 buffer is used and an offset measurement when 7 buffer is used and store the data until they have one measurement at each of 7 and one or the other of 4 and 10. This is not the usual way of doing things but if it works to give stable, correct buffer check readings then it is valid.
Well, like I say, and like beer, go to the source. I spent about 20 minutes on the phone with a tech. He noted that the technology of this meter relies on Total Dissolved Solids (TDS) and their impact on conductance to obtain readings. As my water has very little TDS (31 mg/L on average), the meter will not be very accurate with that water (or distilled or RO, for that matter). He also suggested that calibrating the meter using a buffer in the pH range that you will likley measure is adviseable, e.g., buffer 7 for measuring foundation water. He opined that more than likely I should accept the city assessment of pH 7.1., and that the meter, calibrated using the 7 and 4 buffers, would be accurate for beer parameters (mash, pre-post boil, etc.).
Soooooo, I guess I'll start there and see what happens. I'll assumethe starting water pH is 7. I'll also take a look at Palmers spreadsheet....
Soooooo, I guess I'll start there and see what happens. I'll assumethe starting water pH is 7. I'll also take a look at Palmers spreadsheet....
At this point I have to throw up my hands and say I have no idea as to how this thing works and am, therefore, eminently unqualified to offer any opinion other than that I think you should obtain a real pH meter for use in brewing. By a real pH meter I mean one that measures the chemical activity of the hydrogen ion irrespective of the conductivity of the solution.
This here horse ain't dead yet so we'll a keep a whippin' 'er!
Ran the manual cal procedure at the bottom of pg 4 for both solutions 7 and 4. Then back and forth between the two solutions. Only off by .03 at solution 4. Checked current mash. 5.58. EZ Calc predicted 5.58. Back to standard solutions and still accurate.
But I can't measure pH of water which totally doesn't make any sense! What a sow! The main issue with that is I want to set the HLT to pH 5.5.
NanoMan
I think I hear the final winnie......
Ran the manual cal procedure at the bottom of pg 4 for both solutions 7 and 4. Then back and forth between the two solutions. Only off by .03 at solution 4. Checked current mash. 5.58. EZ Calc predicted 5.58. Back to standard solutions and still accurate.
But I can't measure pH of water which totally doesn't make any sense! What a sow! The main issue with that is I want to set the HLT to pH 5.5.
NanoMan
I think I hear the final winnie......
Has anyone done a validation/calibration of the EZWater Calc spreadsheet? Seems to me it would be easy to do by mashing say a pound of grain in untreated (no salt additions) water and comparing the resulting mash pH with that predicted by the software.
I assume the software is based on a starting water pH of 7.0?
NanoMan
I assume the software is based on a starting water pH of 7.0?
NanoMan
It seems that how close you'd end up would depend on the pH of the base malt. They can very quite a bit (even among standard american 2-row). Rahr, for example, seems to be around 5.55 DI pH.
Estimating mash pH is a bit tricky not because the algorithm is complex but because the data required to feed the algorithm is at best very difficult to obtain and certainly impractical from the point of view that the work necessary to do a test mash is much simpler than the lab work required to get the requisite data. Mash pH is that pH which causes the protons contributed by adding acids or acidic acid malts to the mash to plus those produced by the reaction of malt phosphate and calcium/magnesium to exactly balance the protons absorbed by the alkalinity of the mash water plus those absorbed by malts which are not acidic. The details are set forth at
http://www.wetnewf.org/pdfs/estimating-mash-ph.html
None of the spreasheets in common use use this algorithm AFAIK but rather something that represents an approximation or simplification. I'm presenting it to MBAA this fall in Austin and the Palmer, Kaminski book discusses it.
Because the different spreadsheets use different models (different from this one and from one another) and make different assumptions about the buffering capacities of malts they all get different answers from one another and from the model at the wetnewf.
The website goes into the difficulties involved in obtaining malt data so that even were its model perfect (it is, I think, pretty robust but not perfect) it would not accurately predict mash pH.
The obvious question is 'How accurate do you need?' and then you can ask whether any of the popular models are accurate enough. It is going to depend on the beer and the material you use to make it. This is why a test mash, where possible, is always preferable to a calculated estimate.
http://www.wetnewf.org/pdfs/estimating-mash-ph.html
None of the spreasheets in common use use this algorithm AFAIK but rather something that represents an approximation or simplification. I'm presenting it to MBAA this fall in Austin and the Palmer, Kaminski book discusses it.
Because the different spreadsheets use different models (different from this one and from one another) and make different assumptions about the buffering capacities of malts they all get different answers from one another and from the model at the wetnewf.
The website goes into the difficulties involved in obtaining malt data so that even were its model perfect (it is, I think, pretty robust but not perfect) it would not accurately predict mash pH.
The obvious question is 'How accurate do you need?' and then you can ask whether any of the popular models are accurate enough. It is going to depend on the beer and the material you use to make it. This is why a test mash, where possible, is always preferable to a calculated estimate.
Ok, lemme see if I can extrapolate for practical usages. Each first time I brew a beer, I might want to measure the resultant pH of the mash prior to salt additions, excepting that I probably want to ensure at least 50 ppm Ca++ for enzymes and other reasons. Once I have the pH value, I can add salts (I would add to the mash) as might be needed for pH adjustment, favor profiles, etc.
This wouldn't be necessary each time I brewed this beer, assuming that after two or three batches the pH values were reasonably consistent.
Close?
NanoMan
PS Looking forward to Palmer and Kaminski's book and may have to visit Austin in the fall...
This wouldn't be necessary each time I brewed this beer, assuming that after two or three batches the pH values were reasonably consistent.
Close?
NanoMan
PS Looking forward to Palmer and Kaminski's book and may have to visit Austin in the fall...
Typically one has an idea as to what salt addition he wants to make either from a recipe, the use of a spreadsheet or, in the simplest case, the recommendation of this Primer (Post #1). He then, ideally, uses water treated with these salt additions with a pound or so of the grist he intends to mash and checks pH. pH is adjusted by the use of acid or base to the target and then the acid/base scaled up to the whole mash for the actual brew session. The actual mash should be checked too. If a test mash was done you should be pretty darn close and any tweaking/fine-tuning can be implemented by adding a bit more or less of something the next time the same beer is brewed.
With experience, you will know what to expect and all this process isn't necessary. A pH check will suffice and many experienced brewers don't even bother to do those.
drkwoods
Well-Known Member
mabrungard said:
Could you post a link to a system you recommend? Cheers!!
I understand the role of salts addition in affecting mash pH and beer flavor. But I'm not clear on whether there's also an effect of salts in the brewing water on getting a vigorous fermentation by the yeast. The total alkalinity of my local water is around 500 ppm, so I want to avoid it for an all grain beer that requires soft water. If I use RO water to which calcium chloride has been added as the only salt, will there be enough trace element ions present (potassium, iron, copper, etc.) to support healthy yeast metabolism? Certainly some trace elements are present in the grain and will be extracted during the mash and sparge, but I don't know if these quantities suffice for fermentation.
There are a lot of resources that discuss the mineral/nutrient requirements for yeast (Noonan, Palmer, White-Zainesheff, etc.). I wold consult those. I don't use RO water, but if I did, I would make sure I had minimal levels of calcium, zinc, etc.
Cheers!
NanoMan
I went ahead and purchased the Milwaukee 102 sold by MoreBeer and recommended by Kai Troster. Here is a comparison of data with the HM Digital PH200:
Both meters calibrated per instructions.
Assumptions: Calibration standard buffers are good. Base water pH is 7.1, per City testing at the house last week.
Mash Values:
Blond Ale: Milwaukee: 5.54 HM Digital 5.59 Water Sheet: 5.52
Pale Ale: Milwaukee: 5.65 HM Digital 5.62 Water Sheet: 5.52
Sparge Water (4 ml 10% acid) Milwaukee: 4.49* HM 4.06
* The Milwaukee seems to take take multiple cycles to read water values, but it does get there.
The HM Digital seems to have a major drawback in not being able to read pure water at all.
I've got 4 more beers to brew between now and Friday so I'll get more data. I'm gonna set the Water Sheets to a predicted mash of about 5.35. One of the beers is a stout so there will be a dark beer sample.
NanoMan
Both meters calibrated per instructions.
Assumptions: Calibration standard buffers are good. Base water pH is 7.1, per City testing at the house last week.
Mash Values:
Blond Ale: Milwaukee: 5.54 HM Digital 5.59 Water Sheet: 5.52
Pale Ale: Milwaukee: 5.65 HM Digital 5.62 Water Sheet: 5.52
Sparge Water (4 ml 10% acid) Milwaukee: 4.49* HM 4.06
* The Milwaukee seems to take take multiple cycles to read water values, but it does get there.
The HM Digital seems to have a major drawback in not being able to read pure water at all.
I've got 4 more beers to brew between now and Friday so I'll get more data. I'm gonna set the Water Sheets to a predicted mash of about 5.35. One of the beers is a stout so there will be a dark beer sample.
NanoMan
There is more than enough nutrients in an all-grain wort that a decent pitch of yeast wont care if you meet the so-called minimum levels of calcium, zinc, etc. Those same homebrew books that cite minimum ion requirements all have a table with Pilsen's water profile that is far below all those levels. Would those original czech pilsners have been better or worse if the water met the guidelines?
The yeast performance is better with increased calcium, however I can confirm that the flavor of a Czech Pils will not be improved with more calcium. With proper practices, the lack of 'sufficient' calcium in wort can be overcome. Many of the mega brewers use water that has less calcium than desired in typical brewing. So it can be done.
I was reminded by my friends who were in Pilsen this week, that PU ferments in open fermenters. There would always be a low level of oxygen in the wort in fermentations at PU. Contrast that with the near zero level our typical ferments create in carboys or cylindroconicals. I need to find out if micro-oxygenation has an effect on calcium needs by yeast. Something to add to my 'to-do' list.
If you look at the list of benefits of calcium to brewing you usually find things like:
Reduction of mash pH
Protection of enzymes against heat
Clearer runoff
Better protein coagulation
Better yeast flocculation
Precipitation of calcium oxalate
Less silicate/polyphenol extraction
Less production of color
Beers that use low calcium are typically lagers that are acidified with sauergut or sauermalz. Most of the rest of the items have to do, ultimately, with beer clarity and as these beers are traditionally lagered for a long time those things that might not precipitate as well in the short term because of reduced calcium they eventually do settle out because of the long lagering times. One does not particularly want good flocculation with these beers because one wants to carry yeast in suspension over to the lagering vessel. Having pretty hefty yeast counts during lagering is required for effective removal of diacetyl and acetaldehyde. These beers tend to be darker in no small part because of decoction mashing but enhanced color from less calcium is something the brewer has to live with. No 3 and 4 SRM beers are produced (AFAIK) using this process. Protection of enzymes against heat is achieved in part because most of the enzymes are removed from the decoctions before they are heated.
Do they? I haven't been there in a long time but when we were ushered into the fermentation hall - large underground chamber with cold brine pipes suspended from the ceiling and hundreds of slightly inclined traditional wooden fermenters fixed to section of rail, those fermenters were empty. The beer is now fermented in more modern equipment. I assumed it is uni tanks but I don't know. We weren't shown the modern cellars.
A low level is desired except at pitching. This is insured, in an open fermenter, if the fermentation initiates promptly as the surface of the fermenting beer is quickly blanketed with CO2 which, as it is heavier than air, tends to stay put unless there are air currents to disturb them. Cellars for open fermentation are not designed to have strong air currents.
A carboy or unitank is full of air when it is filled. The same mechanism protects the beer one the CO2 starts to outgass. Of course once the air is fully displaced it is much harder for any O2 to reach the beer by diffusion in a carboy or unitank.
Yeast needs calcium beyond its effect on flocculation as a cofactor for some enzymes. There is plenty in the malt itself for that. The oxygen is added for sterol formation. Whether the enzymes in that pathway require calcium cofactor or not I don't know.
It is certainly possible to brew good beer with very low levels of calcium. I did it for years and still do though I now use a bit more because I want calcium oxalate precipitation to occur in the lagering vessel, not my plumbing. I've been through that once and once is enough.
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