Author Topic: Harshness - How much alkalinity is too much?  (Read 13454 times)

Offline thehorse

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Electrically Balanced Water?
« Reply #45 on: September 01, 2010, 06:16:12 AM »
So what happens if the water I put together isn't balanced?  Do some of the minerals fall out of the water?  Do I end up with water that isn't what I think?


Offline bluesman

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Re: Harshness - How much alkalinity is too much?
« Reply #46 on: September 01, 2010, 06:34:14 AM »
This is an awesome thread.  For all of those that have been giving the AHA forum a bad rap have not even bothered to read the AHA forum.

It makes me happy to hear statements like that.  This forum has a wealth of information and so many knowlegeable homebrewers.  This thread alone proves it IMHO.
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Re: Harshness - How much alkalinity is too much?
« Reply #47 on: September 01, 2010, 06:43:21 AM »
If used, the chalk (Calcium Carbonate) and baking soda (Sodium Bicarbonate) have to be added directly to the mash.
Due to poor solubility and the tendency to precipitate with boiling, it does not dissolve in the hot liquor (i.e. strike, infusion, or sparge water will contain less calcium and carbonate than you think because it will be precipitated and sitting on the bottom of the HLT).
All the other salts:  Calcium Chloride, Magnesium Sulfate [Epsom salt], Sodium Chloride [iodine free table salt], and Calcium Sulfate [gypsum] can be added directly to (and will dissolve in) the hot liquor.

Offline thehorse

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Re: Harshness - How much alkalinity is too much?
« Reply #48 on: September 01, 2010, 11:14:19 AM »
I guess I wasn't talking about the solubility of the solids I was putting into my brewing water but whether the water was ionically/electrically balanced and if it isn't what does that mean?


Offline tschmidlin

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Re: Harshness - How much alkalinity is too much?
« Reply #49 on: September 01, 2010, 11:55:25 AM »
Your water is automatically balanced ionically, it's not really possible for it not to be.  The salts you add are also balanced, so you'll still have a balanced system.

I think the question of ionic balance came up when reviewing someone's data on water from a certain city, where the balances of ions didn't make sense at a reasonable pH.  Real life water is balanced.  Water on paper, not always.
Tom Schmidlin

Offline thehorse

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Re: Harshness - How much alkalinity is too much?
« Reply #50 on: September 02, 2010, 08:47:31 PM »
I guess that's my point.  I calculate I need to add x grams of ingredient 1 and y grams of ingredient 2 according to a spreadsheet.  According to that same spreadsheet it isn't balanced but I add those ingredients anyway.

What happens, do some not dissolve?

Offline tschmidlin

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Re: Harshness - How much alkalinity is too much?
« Reply #51 on: September 02, 2010, 09:06:09 PM »
What spreadsheet are you using?  Does it say your water is out of balance without any additions?  What does it mean by "balance"?  Is there some formula it is using that you can past in here?
Tom Schmidlin

Offline thcipriani

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Re: Harshness - How much alkalinity is too much?
« Reply #52 on: September 02, 2010, 10:03:18 PM »
Quote
What happens, do some not dissolve?

Most salts will dissolve (with the exception of CaCO3 if the water becomes super-saturated for its pH). It wasn't my intention to be confusing when I said that your water profile is electrically unbalanced - what I meant is that the numbers that you posted here can not actually exist in real water with a reasonable pH. Your water does not correlate absolutely to the numbers for mg/L of ions in your water because it cannot.

Do you remember in chemistry when you'd have to balance a molecule based on its constituent ions electrical charge? That is electrical balance. All water has a neutral electrical charge - therefore every positively charged cation must have an equally negatively charged anion - that's why the formula for calcium chloride is CaCl2 and not CaCl - because Calcium must loose two electrons to achieve a full valiance shell of 8 e- and therefore has a positive charge of 2 (that's why I've been noting Calcium as Ca++). Chlorine, on the other hand, must gain an electron to have a full valiance shell of 8 electrons - and since electrons carry a negative charge that means the ion will carry a negative charge of 1 (since it has gained 1 electron [it's like adding -1 to 0 - you end up at -1 - think of loosing and gaining electrons as adding and subtracting negative numbers). All electrically neutral molecules must have a sum charge of 0 - therefore, since calcium carries a charge of positive 2 and chlorine carries a charge of negative 1 it takes twice as many chlorine ions to electrically balance 1 calcium ion. Water is like that only it's a whole bunch of those cations and anions. Examples of cations in water are calcium and magnesium while chloride and sulfate are anions. the total electrical charge of these ions must equal 0.

Your actual physical water (if we were able to perfectly measure all of its constituent anions and cations) is balanced - the numbers that you posted here as your water report are not balanced.

Water is like Descartes - it exists therefore it is electrically balanced. Starting with the numbers on the water report that you posted will give you a profile that is not "real" water on any spreadsheet because you are starting from something that is unbalanced and almost no spreadsheets out there test for electrical balance before they allow you to adjust your unbalance profile.

Nothing will happen, but you aren't brewing with the water that the spreadsheet has calculated. AJ Delange has a spreadsheet on his site that accounts for balance within a solution (and notifies you of imbalances with regard to atmospheric pressure and CaCO3 super saturation). That's the spreadsheet I typically use when looking at water. It's the Nearly Universal Brewing Water Spreadsheet available at http://ajdel.wetnewf.org:81 - I'd recommend reading the entire manual for that spreadsheet, available on that site - it's not the most intuitive spreadsheet in the world.
Tyler Cipriani
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Offline mabrungard

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Re: Harshness - How much alkalinity is too much?
« Reply #53 on: September 03, 2010, 06:14:09 AM »
Excellent discussion on this issue.  Sorry for the delay in my reply since I continue to see misinformation tossed about in the Forum.

I note that thcipriani has pointed out some inconsistencies that should be addressed.  He did correctly point out a flaw in the rule of thumb that I proposed between RA and SRM.  He pointed out that if you design a really dark beer, the required RA goes through the roof.  I was using the typical maximum SRM for beers of 40 that is described in the BJCP Style Guidelines.  With that color limit, the maximum RA that a brewer should need to use is about 180 ppm.  That is supported by all the water profile information from the world's historical brewing centers.  For instance, the brewing centers with alkaline profiles have RA's as follow:  Munich = 180, Dublin = 170, Edinburgh = 150.  Limiting the maximum RA used for brewing to 200 ppm is sound. 

Unfortunately, thcipriani goes on to say that the correlation between RA and SRM is tenuous at best.  Unfortunately he is quite wrong with that statement.  He did provide a couple of references from AJ and Kai that actually do provide a correlation between roasted malt acidity and their color.  Malt acidity consumes alkalinity in the mash, pushing the pH down.  He is correct that there is not a precise correlation between beer color and RA, but there is a loose correlation that is adequately described and accounted for by the rule of thumb where: RA = SRM x 4.5.  That correlation (along with a maximum RA of 200 ppm) will go a long way to correct the inappropriate correlations that exist out on the Web.

thcipriani goes on to say that the vast majority of water needs no adjustment.  That statement is quite incorrect.  The historical beer styles that grew out of the world's brewing centers are cases in point.  There is no way that a brewer in Dublin could EVER hope to brew a good pale beer with their water and conversely, there is no way that a brewer in Burton could ever brew a good dark beer with their water WITHOUT ADJUSTING THEIR RESPECTIVE WATERS.  The same thing applies to homebrewers where ever they are.  Their water is probably suited to a limited color range of beers and if they want to improve their beers that don't fall within that color range, they will have to adjust their water chemistry.  The only path to brewing a wide range of beers is to understand and adjust your water. 

Now there is a slight flaw in what I stated above. My statement for needing to adjust waters from Dublin or Burton to brew other color beers is overly simplified.  This is because there are many waters that already have too much ionic content and they cannot be adequately altered by ADDING minerals or acids to make them suited for brewing some styles.  Sometimes you need to forget about using your local water if it has too high an ion content and you will need to resort to using distilled or RO water.  This will help you avoid the alka seltzer or other odd flavored brewing results. 

Its also humorous that thcipriani goes on to state that if brewers are worried about their mash pH they should get a pH meter and then adjust their mineral or acid content.  He is espousing exactly the same thing that I'm stating with chemistry adjustment excepting that he is expecting a brewer to figure out what to do while potentially destroying a few mashes in the process.  I'm more of a knowledge-based guy and I think that most brewers can figure out this stuff with the help of properly written guidance.  My pH meter is a handy tool to have for double checking. But I found long ago that once you have figured out your water's characteristics, the pH meter will rarely be needed. 

I appreciate the reference regarding the chloride/sulfate balance.  I did read the reference that AJ posted on Brewing Network.  I also researched the author of the water section of the Handbook of Brewing that the balance was mentioned in.  Although the author, David Taylor, is an eminent brewing chemist and he worked at a number of fine breweries, I don't see a body of work in the brewing literature that suggest that he or others have actually researched and proven this.  In reading further in that Brewing Network thread, AJ also tends to dismiss the applicability of that chloride/sulfate relationship.  He suggests that maybe it works for English beers with English hop varieties.  I will reaffirm that the use of the chloride/sulfate ratio is certainly not appropriate when either the chloride or sulfate concentrations exceed 100 ppm. 

Regarding ionic balance, Tom Schmidlin is correct.  Water reports or water profiles may not be balanced, but the ionic balance in water is ALWAYS balanced.  Any imbalance in a water report is due to rounding error, detection error, or the presence of other ions that were not evaluated in the lab testing.  Minor errors (say 5%) between anion and cation milliequivalents are fairly typical for water reports. If you find more than that difference in the anion/cation balance, then you should be questioning the results. 

Regarding published water profiles for various world brewing centers, there are a bunch of water profiles published in a variety of texts and on the internet that are GARBAGE.  Even though it is printed in a book does not make it correct.  I have performed extensive research into the historic water sources and the water quality of those sources in resolving the appropriate constituents for those brewing center water profiles.  That information will be published in the future.
« Last Edit: September 23, 2010, 11:25:48 AM by mabrungard »
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Offline bluesman

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Re: Harshness - How much alkalinity is too much?
« Reply #54 on: September 03, 2010, 06:43:42 AM »
Martin...thanks for the water chemistry critique.  I have always believed water is self balancing otherwise there would be a precipitation of sorts.  Your knowlege of water chemistry in regards to brewing is a very valuable resource here.  I certainly appreciate your efforts.  I am interested in seeing your publication of historic brewing center water profiles.  This is very interesting information.  Hope to hear from you again. 
Ron Price

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Re: Harshness - How much alkalinity is too much?
« Reply #55 on: September 03, 2010, 08:41:36 AM »
Another big thanks to Martin, and I too look forward to your profiles.  I'm always curious about how and when "typical profiles" for various regions are derived and I hope you'll address that, too.
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Offline bonjour

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Re: Harshness - How much alkalinity is too much?
« Reply #56 on: September 03, 2010, 08:47:32 AM »
all I can say is wow, 

thanks Martin,  keep it up.

Fred
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Offline thcipriani

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Re: Harshness - How much alkalinity is too much?
« Reply #57 on: September 03, 2010, 11:39:29 PM »
Quote
He did correctly point out a flaw in the rule of thumb that I proposed between RA and SRM. He pointed out that if you design a really dark beer, the required RA goes through the roof.

The other obvious flaws being that your calculation cannot conceive of a negative RA value and that the calculation needlessly oversimplifies a complicated concept when many people have dedicated countless hours to developing applications to model non-ideal solutions.

Quote
Unfortunately, thcipriani goes on to say that the correlation between RA and SRM is tenuous at best. Unfortunately he is quite wrong with that statement. He did provide a couple of references from AJ and Kai that actually do provide a correlation between roasted malt acidity and their color.

I agree roasted malt is acidic; however, SRM is not indicative of the amount of roasted malt used in a mash - that's what I found in Kai's research; however, I guess you always find that for which you are searching. You have not offered any proof that there is any sort of strong correlation between SRM and and pH. Can you point to any studies thats conclusion is that mash pH can be predicted solely on SRM? It's like predicting the weather - I'm not arguing there is science to support that SRM has some correlation to mash pH. I'm arguing that if I test my mash pH I'm always right about my mash pH. If I use one of the available spreadsheets on the internet (especially if I'm starting with a profile that can't exist) I'm not going to be right 100% of the time. If I go outside and it's raining it doesn't matter what the weatherman says.

Quote
thcipriani goes on to say that the vast majority of water needs no adjustment. That statement is quite incorrect. The historical beer styles that grew out of the world's brewing centers are cases in point. There is no way that a brewer in Dublin could EVER hope to brew a good pale beer with their water and conversely, there is no way that a brewer in Burton could ever brew a good dark beer with their water WITHOUT ADJUSTING THEIR RESPECTIVE WATERS.

I never claimed that Dublin water needed no adjustment to brew a pale beer. I said that the majority of water needs no adjustment - extremes are exceptions. I don't think anyone would disagree with the statement that Dublin and Burton-on-Trent are very extreme waters. If there's a brewer out there with that kind of water then, yeah, they'll need adjustment - the 800ppm SO4 as the ion would be a good tip that your water is atypical.

Quote
Its also humorous that thcipriani goes on to state that if brewers are worried about their mash pH they should get a pH meter and then adjust their mineral or acid content. He is espousing exactly the same thing that I'm stating with chemistry adjustment excepting that he is expecting a brewer to figure out what to do while potentially destroying a few mashes in the process.

I'm glad I can humor you. I don't espouse anything with that statement other than a pH meter can give a brewer that's worried about their pH piece of mind. I think that once a brewer has a pH meter they'll be able to make informed decisions about which ions to add to their water to give them an appropriate mash pH and not blindly add salts and acids that needlessly destroy their mash by taking it out of the correct pH range. You seem to think that by measuring mash pH and adding CaCO3 or Lactic acid that it somehow ruins a mash when, in fact, adding a huge amount of CaCO3 without measuring your mash pH would do the same thing.

I really feel we're circling the same point - water's complicated and brewers need to be conscious of their pH. The difference here is that you espouse that a spreadsheet is highly accurate while I believe that a properly calibrated pH meter is the best tool.

Non-ideal solutions (like water) are complicated systems to model. If a brewer makes additions based on readings they get from a calibrated pH meter they're going to be right 100% if the time. If they use a spreadsheet, or worse yet, an oversimplified formula they could be wrong. I'm just asking brewers to look outside before they decide they don't need an umbrella.
Tyler Cipriani
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Offline thcipriani

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Re: Harshness - How much alkalinity is too much?
« Reply #58 on: September 06, 2010, 07:35:13 AM »
I emailed A.J. Delange and asked and asked him if he had any additional thoughts on this thread. I felt that almost everything he sent back was relevant to this discussion so here is his reply in its entirety:
Quote
Tyler,

Let me preface by saying thank you! I'm really gratified that someone is able to use this stuff.

Now, on to the thread.

I really think you and Martin have pretty much got it covered. There are a couple of points where you guys disagree a bit but they are almost philosophical.  One is on the correlation between beer color and RA. There is, of course, a correlation. Everyone knows that styles that originated in places where the water was hard tended to be darker. The question is as to how strong that correlation is. To determine that, of course, you have to have data and that's hard to get. The reason its hard to get is because you don't have good knowledge of either the SRM or the RA for a particular beer. If I were to try to determine what the correlation actually is I would have little choice except to use my own beers and that is hardly a subset which would result in an informative model as I do, for example, Bocks, which are darker than my ESB with water that has lower RA.

The other approach is to look at beers for which I have measured the SRM that are brewed in cities for which I have a water profile. For example Guiness and Dublin and Bass ale iand Burton. Trouble with that is that Guiness is not brewed in Dublin any more and Bass isn't brewed in Burton either. But PU is brewed in Pilsen and Kölsch in Köln so we are perhaps not all wet if we assume that Guiness is still brewed with a Dublin-like profile and Bass with a Burton-like profile (which it clearly isn't - modern Bass isn't anything like as minerally as an ale brewed with "traditional" Burton water). The other problem is, of course, that I have about 6 mineral profiles for Burton. You all have been commenting on the fact that most published profiles are hooey and indeed so are most of these (I think 2 balance fairly well) and the range of RA's is -13 - 85 for the two profiles that balance. Caveats aside, I took 17 beers and did the correlation. It shows that the relationship between SRM and RA is RA = 5.6 + 1.05*SRM. This would predict that, for example, my 70 SRM Irish stout should be brewed with water of RA 80. This is certainly more reasonable than the 300 some number that the popular spreadsheets come up with but we still haven't looked at the tightness of fit. That's measured by "Pearsons r", a measure which indicates how much of the variation in observed data comes from the model (the model here is RA = 5.6 + 1.05*SRM). For the data I played with r = 46%  (100% means the model is perfect, 0% means there is no correlation whatsoever between SRM and RA). So the correlation is there but it is weak. If this were a game where you tell me the SRM and I bet on the RA predicted by the model I wouldn't take the bet!

I think what John did when he first came up with these was get data from brewers about water treatment and grain bill. I believe he calculated RA and color from this data and then did the regression. I'm pretty sure about the color part because I remember seeing a comment in a post of his concerning which color model he used. I'm not so sure about the RA. Whatever he did the resulting slope defies common sense (and he acknowledges this).

So given all the pitfalls of the curve fit approach (and who said it had to be linear?) I recommend that the spreadsheet developers take this "feature" out of their spreadsheets.

Imbalance seems to be another question that didn't seem quite resolved. You all said it without saying it explicitly: imbalance represents a measure of the quality of a water report. If the report exhibits large imbalance that means errors were made in measurement, the sample changed while the measurements were going on, bicarbonate was calculated incorrectly from alkalinity, ionic strength was ignored, or some relatively prevalent ion or ions were not measured. The way I often put it is to say that mother nature cannot make imbalanced water and neither can you so if you are trying to match an imbalanced profile you will not succeed.

Finally, the philosophy of owning a pH meter: Given all the variables I do not believe it is possible to accurately predict mash pH and that, therefore, it is essential that you measure it to see if your treatment and grist formulation combine to land you in the right pH range. But I agree that once you have determined that they do you should come back to pretty close to the same pH every time you brew a particular beer and don't really need to check pH. Being the sort I am I do and I also check at the return of each decoction, out of the kettle and throughout the course of the ferment. I don't advocate this for everyone but those pH readings are like familiar landmarks on the road home to me. Each time you see one in the right place you are further assured that your journey will come to a successful end.

Now one thing that has not been mentioned (or emphasized)  is that most beers will require the addition of acid in some form to reach proper mash pH. For German/continental brewers this is sauermalz or sauergut (i.e. lactic acid). For British brewers it is "Carbonate Reducing Solution" (a mix of sulfuric and hydrochloric acids).

Hope this is of some help. Feel free to quote it if you like.

Cheers, A.J.
Tyler Cipriani
Longmont, CO

Offline mrcceo

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Re: Harshness - How much alkalinity is too much?
« Reply #59 on: September 06, 2010, 08:25:42 AM »
I want to echo Dean's earlier comment that this is the best thread I think I've ever read. I have been following it since it started and it has morphed into something which is quite exceptional.  I have my own pragmatic approach as to how to deal with water chemistry and this discussion has helped to confirm my theories.

P.S You just can't get this type of dynamic exchange on TT.  Hopefully this thread will demonstrate the value of this forum and change some minds.