Water Adjustment Sanity Check

bolts · Sep 24, 2009

Brewing a Pale Ale (Mirror Pond Clone) Saturday, and looking at a water adjustment. I have Portland, OR water which has basically nil in it.

Recipe here: http://hopville.com/recipe/98778/american-pale-ale-recipes/cascade-pale---wip

Ca 1
Mg 1
Na 2
Cl 2
SO 0
HCO 9

Playing around with the EZ Water Adjustment site/spreadsheet I've got these additions (mash & boil) for the below target.

4 gallon mash & sparge (i'll fix that later)

3g Gypsum
3g CaCl
2g Epson Salt
2g Baking Soda

Adjusted Water

Ca 100
Mg 13
Na 38
Cl 98
SO 162
CaCO 86

RA 7

CL:SO ratio .6

Thoughts? Should I even mess with it? I want to boost the water beyond near-distilled and bring out the hops, but not overly so.

cactusgarrett · Sep 24, 2009

Regardless of WHATEVER style you are shooting for, you should adjust your water EVERY TIME. That's the closest to DI/RO source water i've ever heard of. But for an APA, that should fly.

ipscman · Oct 2, 2009

Actually I see some possible issues to consider:

I can look-up the page numbers if you like (for everything below) but one seemingly agreed upon fact is that you don't want high sodium (from the Na) mixed with high sulfates. They make a very bitter combination.

Secondly, when the calcium and bicarbonate mix, they precipitate out (some in the mash starting at temps around 158*F/70*C, but all in the boil). Each calcium ion precipitates out two bicarbonates. Translation, you have a net calcium level in your mash/boil of 100 - 43=57.

Then, when you move to the kettle you leave about 50% of the calcium behind in the spent mash grains. Now you have below 30 in the boil. Most sources suggest you need around 100 ppm for a good hot break and a residual going into fermentation of about 50 to encourage good yeast flocculation.

As Palmer says, "brewing beer is a robust system." You make beer anyway. Is a great hot break a must? No. But it may be a better beer if the calcium is high enough to accomplish what it wants to for you. That list includes:

- Mix with phosphates in malt to acidify wort and help adjust pH
- Calcium ions directly stimulate amylolytic enzyme activities during wort
production.
- Calcium ions directly stimulate proteolytic ensymes at lower temps
- CA ions protect a-amylase activity against inhibition by heat
(when you add strike water)
- This leads to increases in extract
- Can lead to an increase of endopeptidase activity at lower temperatures
- Wort runoff rate can be significantly increased
- Increased TSN
- Increased FAN
- Lower coloring effects during boil (less darkening)
- Precipitates oxalate in wort so you don't have beerstone build-up later
- Improved yeast flocculation
- Can lead to improved wort clarification, during maturation, leading to enhanced haze stability.

This is pretty damn complicated stuff. I'm still trying to figure it out but the simple truth seems to be we need a good 75-80 ppm calcium in our mash, and after the subtractions based on precipitations with our various bicarbonate levels, and after subtracting the 50% calcium left behind in the spent grains, we need a net of about 100 in the kettlle for maximum efficiency there and into the fermenter. I don't see how to do this without eliminating the bicarbonates first and then ensuring you have enough left to do the job.

I found that most German brewers add calcium to their wort for the above reasons. The Munich and Vienna profiles suggest very low calcium. Since the professional brew books all suggest these mimimum calcium numbers, I can only guess that most breweries around the world adjust their water accordingly. Like the German brewers, they understand their calcium needs and adjust them where necessary.

One interesting factoid: We read about high Burton-on Trent sulfate numbers...and many of us try to mimic them. However, studies on the chloride in actual UK beer shows that the choride levels are at least double those of the sulfate numbers - the exact opposite of what the water profiles show. Obviously, then, the Brits are adjusting their water to minimize their high sulfate numbers. Shouldn't we be doing the same, instead of blindly imitating their water profiles--profiles that they apparently don't use except as a base to correct?

The cloride to sulfate ratio looks fine.

I think George Fix said it well, "instead of using historical examples as a guide, the best strategy is to first make sure the technical requirements of the mash are met (i.e., a proper pH anf calcium requirements met) and then to adjust the mineral content by using the finished beer's flavors as the guide."

I'd really like to hear what you learn from your brew? We all learn from each other.

I'm on Oregon soft water too and have a German Pils and Munich Dunkel up next. With lagers it will be Thanksgiving before I know if I'm getting what I want.

PRIMARY SOURCES:
Priest, Handbook of Brewing, 2006
Briggs, Brewing: Science and Practice, 2004
Bamforth, Lewis: Essays in Brewing Science, 2006
Fix, Principles of Brewing Science, 1999
Various Zymurgy, Brewing Techniques, BYO issues addressing water modification

Kaiser · Oct 2, 2009

ipscman said:
Secondly, when the calcium and bicarbonate mix, they precipitate out (some in the mash starting at temps around 158*F/70*C, but all in the boil). Each calcium ion precipitates out two bicarbonates. Translation, you have a net calcium level in your mash/boil of 100 - 43=57.

That only happens if the pH is high enough for a strong carbonate concentration in the mash. It is the CaCO3 (calcium carbonate) that precipitates and not the calcium bicarbonate. During mashing and boiling the pH is low enough for the calcium carbonate to stay in solution. What is precipitating and removing calcium are calcium phosphates. This is a result of the reaction that lowers the mash pH if you have Ca in the mash.

I appreciate the time you took to list all the benefits of Calcium, but I dont fully agree with that list. I do acknowledge that Ca is important for break formation and beer clarification in general but my experiments and other sources have shown little impact of mash Ca levels on extract (efficiency) and enzyme activity. While it does stabilize a-amylase, that enzyme is plenty stable at mash temps and during dough-in. Even more so, the laboratory analysis of the extract potential of malts is done with distilled water.

While German brewers are allowed to add calcium to their water, I dont think many do. Soft water (low Ca and Mg) is by many regarded as the better brewing water. The few actual brewing water reports that I have seen were surprisingly low in Ca (below 30 ppm I think). I have yet to do side-by-side experiments with waters of different hardness but same RA to confirm this, but I dont think that all beers benefit from Ca levels as high as 100 ppm and higher.

Kai

ipscman · Oct 2, 2009

Hi kai,

Thanks for weighing in. I have learned a lot from you and wondered what your thoughts were on this subject.

I'm quoting sources (Priest, Handbook of Brewing, 2006) for the "Germans add calcium" and bicarbonate is precipitated out (Wotring, Zymurgy, 1995, Grain issue, pp. 33-37). However, I do not fully understand the data and was hoping someone like you would add your expertise.

I'm currently involved in a thread elsewhere (http://www.probrewer.com/vbulletin/showthread.php?p=46012&posted=1#post46012) where this is being discussed. There does seem to be a contradiction between theory and reality on its face.

Q1: Are you up for some experiments on this subject? You are a trusted source.

I have always been confused by Palmer's repetition of the common suggestion to raise your RA for dark beers when using Pilsner type water. I use "5.2" to address pH and add calcium and brewing salts to address the chloride to sulfate ratios. As I understand it the phosphate buffers in that product work with any grain bill and my experience thus far seems to validate that. Regardless of grist, my mash pH is 5.2. So I don't use salts to adjust pH. If I follow the brewing experts I need to have a residual amount of calcium AFTER I eliminate the majority of the bicarbonate/carbonate hardness. So,

Q2: If using 5.2 to address pH, what does the addition of bicarbonate actually do for the brew, taste, end result? Does it actually effect taste or mouthfeel somehow? It seems like you add it to get rid of it. What's the point (outside of pH adjustment)?

Q3: Is it, as I think I understand, something I can ignore with my soft water, regardless of beer style because my pH is addressed elsewhere?

Q4: Why is it we all want to Burtonize our water (high sulfates) for stouts, e.g., when Briggs' publication of the average ion content in the UK beer samples indicates that chlorides are double that of sulfate (p. 665). Doesn't that suggest that brewers there are adjusting their water to get away from the high sulfates?

Also, "Wired" on the other thread indicates that his Dublin water profile is NOTHING like the ones we see so commonly in reputed brewing sources, to wit:

FAMOUS BREWING WATERS
SOURCE Ca Mg Na CO3 SO4 Cl
Antwerp [DeKonick] 90 11 37 76 84 57
Beerse region [Westmalle]41 8 16 91 62 26
Brugse [Brugs Tarwebier] 132 13 20 326 99 38
Brussels region 100 11 18 250 70 41
Burton-upon-Trent 1 268 62 - 280 638 36
Burton-upon-Trent 2 270 60 30 200 640 40
Burton-upon-Trent 3 295 45 55 300 725 25
Burton-upon-Trent 4 268 62 54 200 638 36
Chico [Sierra Nevada] 16-50 10-32 8-34 100est. 0-19 0-37
Dortmund 1 225 40 60 180 120 60
Dortmund 2 250 25 70 550 280 100
Dublin 1 119 4 12 156 53 19
Dublin 2 118 4 12 319 54 19

But Wired has only 20 mg. calcium. His response to the question about this contrast makes sense to me:

"My numbers come from the local water authority. There are three treatment facilities serving the Dublin area: Leixlip, Ballymore Eustace (mine), and Ballyboden.

None of them delivers water even remotely resembling the published profiles.

These standard profiles are truly mythological. I don't know who started it, but they have been copied and regurgitated endlessly in books, articles, and brewing software and have become Gospel because "experts" have reproduced them without actually checking their accuracy. Always consult your local authority."

Major thanks for visiting these questions, Kai. You are a gift to us all.

BTW, Priest's information is almost all from the typical professional brewing digests from around the world, Narziss, etc. His work is the update of Hardwick's tome published some years back.

General References:
Priest, Handbook of Brewing, 2006
Briggs, Brewing: Science and Practice, 2004
Bamforth, Lewis: Essays in Brewing Science, 2006
Fix, Principles of Brewing Science, 1999
Various Zymurgy, Brewing Techniques, BYO issues addressing water modification

Kaiser · Oct 2, 2009

ipscman said:
Thanks for weighing in. I have learned a lot from you and wondered what your thoughts were on this subject.

Thanks. And I didnt mean to sound smartassed, but this is a controversial subject with little definitive data.

I'm quoting sources (Priest, Handbook of Brewing, 2006) for the "Germans add calcium" and bicarbonate is precipitated out (Wotring, Zymurgy, 1995, Grain issue, pp. 33-37). However, I do not fully understand the data and was hoping someone like you would add your expertise.

To my recollection the 2 premier German brewing books (Narziss and Kunze) dont list minimum mineral levels like you find in Palmers book.

I'm currently involved in a thread elsewhere (http://www.probrewer.com/vbulletin/showthread.php?p=46012&posted=1#post46012) where this is being discussed. There does seem to be a contradiction between theory and reality on its face.

I read through some of that thread. Its a really good collection of data and opinions. I was surprised to how many home brewing texts/sources were referenced.

Q1: Are you up for some experiments on this subject? You are a trusted source.

Yes. I do plan to evaluate the effects of Ca in a beer at levels of 10 (my RO water), 70 and 140ppm. But at this point my plate is full with mash pH work that I want to publish in a few months.

The reason for that experiment is that, like you, I have conflicting information on how important Ca is in the brewing water. Even if I dont brew these beers on the same day I have the means of tightly controlling the brewing process and plan to asses factors like efficiency, lauter speed, break formation, clarity and others. As I see this late this year or early next yeast would be the earliest I can get this started.

I have always been confused by Palmer's repetition of the common suggestion to raise your RA for dark beers when using Pilsner type water.

The waters RA needs to match the grists acidity such that they settle at an appropriate mash pH. I agree with that.

I use "5.2" to address pH and add calcium and brewing salts to address the chloride to sulfate ratios. As I understand it the phosphate buffers in that product work with any grain bill and my experience thus far seems to validate that. Regardless of grist, my mash pH is 5.2. So I don't use salts to adjust pH. If I follow the brewing experts I need to have a residual amount of calcium AFTER I eliminate the majority of the bicarbonate/carbonate hardness. So,

I dont think that any professional brewer should use the 5.2 product. You should be able to control your mash pH through water modifications, acid addition and grist composition. I, and other brewers, have data that 5.2 does not do as good of a job as many believe. In particular it does not seem to buffer the mash at 5.2 but closer to 6.0. Have you tested your mash pH?

Q2: If using 5.2 to address pH, what does the addition of bicarbonate actually do for the brew, taste, end result? Does it actually effect taste or mouthfeel somehow? It seems like you add it to get rid of it. What's the point (outside of pH adjustment)?

Bicarbonates are for pH adjustment only. At mash pH most of the bicarbonate and carbonate will have been converted to carbonic acid. At beer pH only ~0.8% of the carbo stuff (carbonic acid, bicarbonate, carbonate) will be bicarbonate as most of the initial bicarbonate will have been converted to carbonic acid which then escaped as CO2

You should check out A.J. deLanges work on that subject. I have some stuff mirrored here: http://braukaiser.com/wiki/index.php?title=Foreign_Content but his site has more. It tends to be down a lot, though.

Q3: Is it, as I think I understand, something I can ignore with my soft water, regardless of beer style because my pH is addressed elsewhere?

Dont control pH with 5.2. Use the proper balance of water minerals.

Q4: Why is it we all want to Burtonize our water (high sulfates) for stouts, e.g., when Briggs' publication of the average ion content in the UK beer samples indicates that chlorides are double that of sulfate (p. 665). Doesn't that suggest that brewers there are adjusting their water to get away from the high sulfates?

I dont know. Im not familiar with brewing English beers and their brewing process. It could be that it is just a self perpetuating advice that has no solid foundation.

Also, "Wired" on the other thread indicates that his Dublin water profile is NOTHING like the ones we see so commonly in reputed brewing sources, to wit:

It is possible that the water has changed or a bad source has been copied over and over. Use the city water profiles as a guideline and not as the gospel. I checked out Munich recently and the current water report matches what has been reported as typical Munich water.

BTW, Priest's information is almost all from the typical professional brewing digests from around the world, Narziss, etc. His work is the update of Hardwick's tome published some years back.

They all pull from the same pool of papers. One of the reasons why I have been doing so many experiments is that I want to be able to see how some of these sometimes controversial subjects actually affect home brewing. If there is something that I learned in home brew forums, it is that if you argue against common wisdom, you better know what you are talking about and can back it up.

Kai

ipscman · Oct 2, 2009

Thanks for responding Kai.

One of the reasons I have over 50 books on brewing is because I find so much confusion in the homebrew groups. I hope to find more "professional" studies and answers. I've wanted to purchase Kunze for a long time but haven't quite popped for it yet at $200 from Siebel. [anyone got a clean used one they want to sell???] Can't find it anywhere else. I got Briggs from India for only $69. Amazon has it at $315. Spoiled me, I guess. I use all the typical home brew texts plus professional texts from Briggs, Bamforth, Lewis, Hough, Moll, Hardwick, DeClerck, Priest, Hornsey, Boulton, Fix, Goldammer, etc.

DeClerck said, "A distinction is frequently drawn in the industry between the theoretical man who tries to explain everything from a scientific point of view, and the practical man who relies on empirical knowledge and experience. A good brewer should be able to steer a middle course between these two."

I'm 60 so if I relied on empirical knowledge alone to answer all of my questions I will run out of time first! Thus the theoretical interest. However, I have brewed 23 batches in the past 9 months so lots of learning going on at that end as well with over 20 styles under my belt thus far.

DeLange!!!!!!!!!!!!!!!!!!!!! As I opened this post I am listening to a 4 hour mp3 from DeLange on water. Small world, indeed. In the midst of it a guy stands up and quotes from Dr. Lewis, emeritus professor at UC Davis. The gist was, hey you guys. All of your ingredients are pretty much the same...except for your local water. So brew with what you've got. it makes your beer unique.

Just to be clear, the numbers on Ca2+ came primarily from the 2006 edition of Handbook of Brewing edited by Priest, not Palmer. Cf below for some of them.

Some sources provided:

"German brewers tend to compensate low Ca2+ contents by additions to water post dealkalization." He seems to attribute this to a speaker named M, Eumann at a convention held in Singapore in 2000: Proc. 26th Convention of Asia Pacific Section of the Institute of Brewing.
http://books.google.com/books?id=TI...onepage&q=malting and brewing science&f=false # 47.

"Yeast flocculation is improved by Ca2+; most yeast strains require at least 50 mg/l for good flocculation." References 27, 29 & 30 at the same link above - number 28 is a reference to Narziss, BTW.

"Regarding protein precipitation: "It has been estimated that a minimum level of 100 mg/l Ca2+ ions is required for good-quality protein break formation." Reference at same link above, # 19.

RE haze formation and gushing as a result of oxalate precipitation, "It is recommended that 70-80 mg/l Ca2+ ions should be present during mashing to eliminate excess of oxalate during beer storage." Same link, references 18, 32, and 33. Briggs is included in this list.

"...may authors suggest that this pH control is best achieved by maintaining low alkalinity (bicarbonate content) in brewing liquor (less than 50 mg/l), plus sufficient Ca2+ to achieve the desired pH level (not less than 100 mg/l).
Because of the precipitation of Ca2+ in these pH control reactions, there is a considerable reduction in the calcium ion concentration during wort production; about 50 to 60% of the Ca2+ ions present during mashing (either present in mashing liquor, or as added salts, or derived from grist materials) will be lost with spent grains and trub." p. 116, no references given. Available at the above link = page backwards.

RE 5.2:
I tested it on a few batches and stopped because it was always about 5.2 (using the more expenisve hard pH papers instead of the flimsy paper ones). Now the obvious thing is I'm starting with Pilzen-like soft water with almost no bicarbonate-37, sulfate-4, chloride-11, calcium-10, magnesium-3. As I understand it the buffering power of the phosphates from the malt, coupled with calcium and the phosphates from 5.2 buffer out any alkalinity that any dark specialty malts I use might add, or the water I sparge with (batch sparge, BTW, and again, even second runnings remain at 5.2. What I like about this approach is (assuming it works consistently) that I've eliminated one major variable. My mash pH is a constant. Plus it is so damn easy. So far that seems to accurate.

I'll start testing it again but my next two brews are a German Pils and a Munich dunkel so not much likely to raise alkalinity there with my starting water.

I'm looking forward to your ongoing experiments and results. I started on the water journey because I blind-tasted a Pilsner Urquell and a Warsteiner Pils and much disliked the diacetyl of the Urquell and preferred the bitterness of the German Pils. That lead to the brewingnetwork water-ganza (12 hours listened to 3-4 times through).

At this point it seems to me that Fix was right. Focus on pH (your current focus) and address brewing salts for flavor. Don't try and imitate a brewing city profile. You will often be lead astray.

Learning and loving it. Think I'll have a beer!

Mark

P.S. I may go Reinheitsgebot (sp?) yet and use lactic acid for pH adjustment. I'm curious what might happen if I use a lower pH for the protein and beta rests (where appropriate) and a higher pH for the a-amylase rest. So much to learn. So little time.

Kaiser · Oct 2, 2009

ipscman said:
I've wanted to purchase Kunze for a long time but haven't quite popped for it yet at $200 from Siebel.

I got mine from Germany and it wasn't cheap. But worth it, at least for me.

DeClerck said, "A distinction is frequently drawn in the industry between the theoretical man who tries to explain everything from a scientific point of view, and the practical man who relies on empirical knowledge and experience. A good brewer should be able to steer a middle course between these two."

This is a nice quote and so true.

All of your ingredients are pretty much the same...except for your local water. So brew with what you've got. it makes your beer unique.

While I'm not a trying to copy water and beers exactly, I'd like to understand the effects that all the ingredients and brewing processes have so I can come up with my own perfect version of a beer that is bases on aspects of various beers from various places. Water is one part of that equation and as home brewers we are in the unique situation where we are not as bound to economics and making brewing water from RO is perfectly fine.

Just to be clear, the numbers on Ca2+ came primarily from the 2006 edition of Handbook of Brewing edited by Priest, not Palmer. Cf below for some of them.

I have to pick that up at one point. I hate to quote quotes of quotes if you know what I mean.

RE 5.2:

Click to expand...

I tested it on a few batches and stopped because it was always about 5.2 (using the more expenisve hard pH papers instead of the flimsy paper ones).

Those strips, if you are talking about the 4-7 colorpHast ones, have an error of -0.3 pH. We tested that a while back on a number of different strips from different brewers. Here are the results. I mean to add more, hence the "Work In Progress": http://braukaiser.com/wiki/index.ph...st_strips_for_pH_measurements_in_home_brewing

I have 2 new pH articles that may be of interest for you as well:

http://braukaiser.com/wiki/index.php?title=An_Overview_of_pH
http://braukaiser.com/wiki/index.php?title=How_pH_affects_brewing

Kai

Kaiser · Oct 2, 2009

If you want to follow the Reinheitsgebot you won't be able to raise the pH during the mash as salt additions can only be made to the water. I have done mashes where I started out with a pH of 5.7 to enhance ferulic acid release and then lowered it to 5.4 for the sacc rests.

Kai

conpewter · Oct 2, 2009

Wow thanks for this thread so far guys, I'm still learning about water chemistry and really enjoy these conversations. My current process is to adjust my RA to match what I expect my mash PH will need to be (based off of SRM, an approximation to be sure, but all I have atm). Then adjust the sulfate vs. chloride ratio for what type of brew it is. I've experienced the effect of low Ca (hazy/cloudy beer) so I do make sure to have enough of that.

One thing I'm confused about is the point of bicarbonates pecipitating out during the mash and boil, I thought as Kai mentioned that the PH is such that it won't percipitate out.

ipscman · Oct 2, 2009

Thanks for the comparison, Kai. Darn. Are you trying to get me in MORE trouble with my wife! Honest honey, there's this guy named Kai and he says these strips aren't good enough. In fact he told me (well actually Bobby from NJ) that I can get a good one for about $75. Well, no. That's not all. I have to get some really important accessories so it will be about $100. Yeah, I know I said I was done but...

Hmmm. I have four taps on one kegerator I built (Bobby was the inspiraton, BTW) and am in the process of setting-up a second one so I'll have 8 on tap. Of course the goal is a few more.

Someone told me you could save money doing this at home!

;-)

Mark

P.S. Maybe I'll just figure whatever the strips say, I need to add .3 at room temperature. Or, I can figure that whatever they say at room temp is actuall correct at mash temp, or... I'm getting a headache.

Bobby_M · Oct 2, 2009

My wife said she gives your wife permission to kick me in the nuts.

ipscman · Oct 2, 2009

Bobby, I'm howling out loud. "Why am I howling? Honest honey, it was Bobby. Yeah the guy in N.J., not the beer. Just had one...really. "

Speaking of nuts, what's really amazing, actually, is my wife has never tasted alcohol in her life. Total teetotaler. Has some inner ear balance issues on occasion so she just says, "No." But she is very supportive of my brewing. Just don't want to push her over the edge.

Bobby, your youtube stuff is phenomenol. Thank you so much for your hours and hours and hours of effort.

Hmmm. Now I'm looking at used DO meters on ebay. Always more toys. Then again, you probably MADE one with wire and duct tape. It would look real classy though.

;-)

Mark

ipscman · Oct 2, 2009

Just a quick note to Kai. My container of the 5.2 stuff says to use 1 tablespoon for 5 gallons. That is what I do. I believe you said you used 2 teaspoons in your experiment. A tablespoon is 3 teaspoons, not 2. Did they change their directions on the amount to use? I've had mine for about a year so don't know what prior packaging may have indicated.

I will be checking is as carefully as I can and get back to you with the results. We all learn together.

Mark

Back to the stir-plate.

ipscman · Oct 3, 2009

Hi Conpewter,

I've always enjoyed YOUR posts.

“…the boil…[to precipitate bicarbonate with calcium] and its removal will encourage the reaction to continue until either the bicarbonate or the calcium is consumed.

“Note that it takes a single calcium ion to remove two bicarbonate ions, and remember that you want to have 50-100 ppm calcium remaining in your water for mash activity.”
Zymurgy article, special GRAIN issue, 1995, p. 35 - by Ginger Wotring – author of the BJCP Water section to prep for the BJCP exam)

I could give you other sources but as I understand it from our BJCP guide and other sources, either calcium or bicarbonate will survive the precipitation process in the boil until one of them is gone. If there is boiling water (actually anything above 176*F starts the process) and calcium and bicarbonate it precipitates out to CO2, water and calcium carbonate, the chalky stuff in the bottom of the kettle. If pH has anything to do with it, it apparently doesn't have any affect at with the type of brews we do. But Kai may know different. I just know all the professional sources I have refer to the process and none of them seems to connect pH in the boil to THAT process. It does certainly apply to many other processes that occur in the boil, however.

At least that's my limited understanding at this point.

Appreciate your sig.

Mark

Kaiser · Oct 3, 2009

I used the instructions on the webpage for the experiments. They say 2oz for a 5 gal batch.

As for precipitation of chalk in the wort boil, it won't happen b/c of the low pH. To precipitate temporary hardness, which chalk is once it is dissolved, the pH of the water needs to be able to rise. That rise happens when you drive off the CO2 through boiling. Because of the pH rise the carbo-balance shifts to carbonate and once there is too much Ca and carbonate present in the water it will precipitate as chalk. You can do the same by not boiling but adding slacked lime to the water. This treatment is more common.

This does not apply to a wort boil. Though CO2 might be driven off the pH is not rising (the opposite is true) due to the buffer capacity of the stuff in there. Mainly the proteins.

A.J. wrote a very nice article about that. It's very technical, but that's the one that "made it click" in my head. You can find it here http://ajdel.wetnewf.org:81/ (once it is up again) and it is called Alkalinity, Hardness, residual Alkalinity and Malt Phosphate.

BTW, I did find a reference in Kunze that states that you want at least 50ppm Ca in the water. I'm still curious how that aforementioned experiment will turn out.

Kai

ipscman · Oct 3, 2009

Hi Kai,

Thanks for looking up Kunze for us on calcium and for clarifying on pH and bicarbonate precipitation.

I checked the Five Star web site to see if maybe they changed their directions. Here is what I found:

Use 5.2 at a rate of approx. 2 oz. per 31 gallons of water used in your brew. Calculate the amount of water based on the total volume in the kettle (ex. 7bbl. Leaving kettle use 14oz. of 5.2). Place 5.2 in the mash tun while you are mashing in. If desired, dissolve in a small amount of water before adding to the mash.

2 oz is 56.7 grams. I divided 31 gallons by 5 gallons and came up with 6.2 5- gallon batches in 31 gallons. Dividing the 56.7 grams by 6.2 arrives at 9.15 grams for a 5 gallon batch.

The container says to add 1 Tblspn for 5 gallon mash. That is about 12.6 grams, or over 37% of what is recommended on the site. Definitely inconsistent.

I'm going to email them and see if I can get an answer for this discrepancy.

As you have many times in the past, Kai, you've expanded my horizons. I've looked at your posts on this subject elsewhere and I've learned enough to order some lactic acid (already have calcium carboate) and seriously consider a pH meter. Actually have a bid in on one. "Honey it's Kai's fault!"

With a guy like you around, no wonder our beer is improving.

Mark

I have over 40 favorite folders under Beer. One of them is titled "Kai." I did my first triple decoction because of your work. I bookmarked your photos on iodine tests, etc. I have the utmost respect and appreciation for your work. I'm a fan, listen to your podcasts on Jim Spencer etc. Eventually I'm sure I'll try some of the German specialty techniques you taught us.

Thanks for all Kai.

ipscman · Oct 3, 2009

I'm enjoying your pH research. I especially appreciate your ability to read German and include information from Kunze and Narziss (especially the 2007 edition of Kunze in German - we only have access to a 1996 edition in English which I assume is somewhat dated compared to the 2007 edition).

Anyway, here's my question. In your quote from Kunze:

"A commonly accepted optimal range for mash pH is 5.2 - 5.7 with 5.5 being optimal for starch conversion activity but many authors report wort and beer quality benefits if the pH is lowered into the 5.2 - 5.4 range [Kunze, 2007][Narziss, 2005]. Kunze in particular lists the following benefits for a mash pH as low as 5.2. Since it is a good and fairly comprehensive list I cited it here. Some of these benefits listed will be explained in the following sections [Kunze, 2007]"

Are the temperatures suggested to be taken at room temperature or mash temperature?

I notice you think it was room temp in Narziss' chart: "Because of that it can be assumed that all pH values given in that book were measured at room temp." from http://braukaiser.com/wiki/index.ph...iency_in_single_infusion_mashing#mash_results

I ordered a pH meter, lactic acid, etc. My wife didn't go ballistic. It's a good day.

;-)

Thanks Kai!

P.S. Do you know if the 2007 edition of Kunze in German is substantially updated from the 1999 edition we can get?

Kaiser · Oct 3, 2009

ipscman said:
Are the temperatures suggested to be taken at room temperature or mash temperature?
[/qoute]

I think at some point in the article I say that all pH values are room temp. I have been thinking about that for more than a year. Although I never saw any statement to that extend in the literature I believe that most pH numbers there are romm temp sample temperatures.

I'd love to get some confirmation on that.

P.S. Do you know if the 2007 edition of Kunze in German is substantially updated from the 1999 edition we can get?

Click to expand...

I wouldn't know. I only have the 2007 edition. But what we discuss here us pretty basic and should not have changed. The 2007 edition has likely some more updated brewing technology stuff.

Kai

Smellyglove · Jul 8, 2017

ipscman said:
Hi Conpewter,

I've always enjoyed YOUR posts.

“…the boil…[to precipitate bicarbonate with calcium] and its removal will encourage the reaction to continue until either the bicarbonate or the calcium is consumed.

“Note that it takes a single calcium ion to remove two bicarbonate ions, and remember that you want to have 50-100 ppm calcium remaining in your water for mash activity.”
Zymurgy article, special GRAIN issue, 1995, p. 35 - by Ginger Wotring – author of the BJCP Water section to prep for the BJCP exam)

I could give you other sources but as I understand it from our BJCP guide and other sources, either calcium or bicarbonate will survive the precipitation process in the boil until one of them is gone. If there is boiling water (actually anything above 176*F starts the process) and calcium and bicarbonate it precipitates out to CO2, water and calcium carbonate, the chalky stuff in the bottom of the kettle. If pH has anything to do with it, it apparently doesn't have any affect at with the type of brews we do. But Kai may know different. I just know all the professional sources I have refer to the process and none of them seems to connect pH in the boil to THAT process. It does certainly apply to many other processes that occur in the boil, however.

At least that's my limited understanding at this point.

Appreciate your sig.

Mark

This is a pretty old post, but I stumbled across something I'm trying to research a bit.

In the post I'm quoting it says that above 176F bicarbonate precipitates. I found someone quoting the same source (Zymurgy article, special GRAIN issue, 1995, p. 35 - by Ginger Wotring – author of the BJCP Water section to prep for the BJCP exam) on the probrewer forum, but the person there says it happens at 158F. Which one is correct? If it's 176 then it would happen in the boil, if it's 158F, it wil happen during mashing.

I read above that Kai Troester said that precipitation doesn't happen, while one the probrewer board they say it will happen during mashing, so if the water profile contains x amount of Calcium, and it is being "used up" to precipitate bicarbonate, the Calcium content of the boil, will be way lower than what the water started with, this is also due to calcium being held back by the grist during transfer, as far as I understood it from the probrewer board.

I spent several hours googling and trying to understand what is correct last night, but eventually had to call it a day.

Can someone please shed some light on this?

ajdelange · Jul 10, 2017

Precipitation can occur whenever [Ca++][CO3--] > 10^-8.45. Note the use of italics to emphasize that this condition only says that precipitation is thermodynamically feasible when it is met and not that precipitation will occur when it is met. The reaction is Ca++ + 2HCOs- --> CaCO3 + CO2 + H2O. LeChatelier's principle says that we can push the reaction to the right by
1)Adding stuff on the left i.e. increasing calcium or bicarbonate
2)Removing stuff on the right i.e. getting rid of the carbon dioxide or precipitated calcite with only the former being practical.

Increasing calcium is an old trick for aiding decarbonation and sparging the heated water with air or steam is done to get the CO2 out thus aiding the reaction. Increasing calcium increases the solubility product and increasing carbonate does this as well. The amount of carbonate is increased if the pH is increased and this is the idea behind lime (which is alkaline) treatment in which

Ca++ +2(OH)- + Ca++ + 2HCO3- --> 2CaCO3 + 2H2O

Thus precipitation can occur at any temperature provided the solubility product is exceeded and indeed occurs in the cold in lime treatment because of the enhanced calcium and the high pH lime addition creates. Conversely in the mash or boil the pH is low so that most of the bicarbonate remaining in the water gets converted to CO2 and escapes in that form. In the mash and boil we get precipitation of phosphate as the calcium salt rather than carbonate and we rely on the hydrogen ions released by this reaction to reduce the pH of mash and boil into the desired ranges. This does consume calcium but remember that malt contains a decent amount of it.

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