A Brewing Water Chemistry Primer

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According to Bru'n Water 1 gram in 10 gallons increases my calcium to 30.3 and my bicarbonate to 96.

The molecular weight of Ca(OH2) is 74.093 grams/mol. One gram is thus 1/74.03 = 0.013508 or 13.5 mmol. Ten gallons is 37.854 L so that's 13.5/37.854 = 0.35 mmoL/L. As calcium's atomic weight is 40 mg/mmol that's 14 mg/L. With 16 mg/L calcium already in the water adding 14 gets you pretty close to 30 so check on the calcium.

OTOH your water has alkalinity of 46 which at pH 7.3 corresponds to a bicarbonate content of 53.5 mg/L. Adding 1 gram of Ca(OH)2 will raise the pH to 10.58 and in so doing convert bicarbonate to carbonate. The solution will be saturated with calcium carbonate some of which may or may not precipitate. You are effectively doing 'lime treatment' of your water. Your bicarbonate goes down but your alkalinity goes up to 80 (assuming there is no precipitation) while the bicarbonate actually goes down to about 26.

Many of the spreadsheets and calculators convert alkalinity to bicarbonate by

bicarbonate = 61*alkalinity/50.

This is OK if the pH is below 8 or so but, as in this case where the pH is higher, it's not that simple.
 
The molecular weight of Ca(OH2) is 74.093 grams/mol. One gram is thus 1/74.03 = 0.013508 or 13.5 mmol. Ten gallons is 37.854 L so that's 13.5/37.854 = 0.35 mmoL/L. As calcium's atomic weight is 40 mg/mmol that's 14 mg/L. With 16 mg/L calcium already in the water adding 14 gets you pretty close to 30 so check on the calcium.

OTOH your water has alkalinity of 46 which at pH 7.3 corresponds to a bicarbonate content of 53.5 mg/L. Adding 1 gram of Ca(OH)2 will raise the pH to 10.58 and in so doing convert bicarbonate to carbonate. The solution will be saturated with calcium carbonate some of which may or may not precipitate. You are effectively doing 'lime treatment' of your water. Your bicarbonate goes down but your alkalinity goes up to 80 (assuming there is no precipitation) while the bicarbonate actually goes down to about 26.

Many of the spreadsheets an calculators convert alkalinity to bicarbonate by

bicarbonate = 61*alkalinity/50.

This is OK if the pH is below 8 or so but, as in this case where the pH is higher, it's not that simple.

I am starting to understand why you recommend gypsum or calcium chloride to increase calcium. It does not increase the alkalinity, like Ca(OH)2 does. I am still taking this all in, but that seems like adding the lime, would be counter productive to what I am looking to achieve.
 
Willum said:
I am starting to understand why you recommend gypsum or calcium chloride to increase calcium. It does not increase the alkalinity, like Ca(OH)2 does. I am still taking this all in, but that seems like adding the lime, would be counter productive to what I am looking to achieve.

Pretty much. Lime is useful when you actually want to raise the pH due to a mash pH you determine is too low. But that's about it, and such beers are fairly uncommon.
 
/brag - about to get a free 5 stage filter with RO from my pops - /brag.

Now I just need a PH meter
 
New to this (impressive) forum and came here by way of discovering the EZ Water Calculator (how that happened I can no longer recall). Hate to start with taking as opposed to giving, but in the EZ WC raised the question: Assuming the mash is set as to pH and ions based on salt additions, is that the end of it? Or, should one care about the final ppm of the various ions resulting from the sparge water as well? For example, Ca may be 136 ppm in the mash, but when the sparge water volume is added into the mix it drops to 68. Certain beer styles rely heavily on ions for flavor character (IPA and SO4, for example). Any input would be appreciated.


NanoMan
 
New to this (impressive) forum and came here by way of discovering the EZ Water Calculator (how that happened I can no longer recall). Hate to start with taking as opposed to giving, but in the EZ WC raised the question: Assuming the mash is set as to pH and ions based on salt additions, is that the end of it? Or, should one care about the final ppm of the various ions resulting from the sparge water as well? For example, Ca may be 136 ppm in the mash, but when the sparge water volume is added into the mix it drops to 68. Certain beer styles rely heavily on ions for flavor character (IPA and SO4, for example). Any input would be appreciated.


NanoMan

You've answered your own question. Use the PPM values after sparging to target the stylistic ion values to suit your tastes.
 
Get the mash pH right and you are pretty much free to 'salt to taste' beyond that. One thing you can do is add sulfate and chloride salts to finished beer to see if you think those additions improve or degrade the taste of the beer. If the former then add more either in the mash, to the sparge water or in the kettle. If the latter then figure out how, if possible, to remove the offending ion from your next batch.
 
Thank you both for the quck responses and the ideas. Gives me things to ponder.

NanoMan
 
Just to correct my understanding, using the Brun water spreadsheet to set up water profiles you select the region you want to emulate as far as sulfate, chloride and sodum, and you make minor adjustments in order to hit the right mash PH by adjustments.

I have essentially done this to a Hefeweizen a dunkelweizen, and a munich dunkel. the first two came out well, the 3rd is lagering and I am about to brew a Dortmunder export. in the spreadsheet it states a SO/Cl ratio of 2.5. So that tells me I need to bump up the chloride to get an appropriate ratio of 1.3 for this balanced malty/hoppy beer style. Should I really try and hit the 330 ppm sulfate amount or can I dillute it. Is the ratio more critical or high amount along with the ratio?
 
Just to correct my understanding, using the Brun water spreadsheet to set up water profiles you select the region you want to emulate as far as sulfate, chloride and sodum, and you make minor adjustments in order to hit the right mash PH by adjustments.

I have essentially done this to a Hefeweizen a dunkelweizen, and a munich dunkel. the first two came out well, the 3rd is lagering and I am about to brew a Dortmunder export. in the spreadsheet it states a SO/Cl ratio of 2.5. So that tells me I need to bump up the chloride to get an appropriate ratio of 1.3 for this balanced malty/hoppy beer style. Should I really try and hit the 330 ppm sulfate amount or can I dillute it. Is the ratio more critical or high amount along with the ratio?

I've never brewed a Dortmunder, so I can't provide specific numbers, but in general you want a lot of minerals in a Dortmunder.
 
I'm a beginner to water chemistry, but I sometimes use slaked lime when I simply can't get enough calcium any other way and don't want to resort to chalk. Pretty rare case though.
 
I've never brewed a Dortmunder, so I can't provide specific numbers, but in general you want a lot of minerals in a Dortmunder.
yeah. its pretty intimidating. So Since I was basiclly dilluting my existing profile to match munich's for the last few brews, then on the dortmunder profile it states a sulfate of 330ppm and Chloride 130ppm. going from 18/8 to 330/130 is pretty intense.
 
How much does sauermalz malt reduce the pH of the sparge? How does this affect the sauermalz strategy for pH reduction?

Sparging with high pH water is associated with higher tannin extraction, so I'd like to lower the sparge pH. At the same time, the sauermalz malt strategy will surely leave some residual acidity that will lower the sparge pH. Because of this, it seems wiser to use lactic acid for both the mash and sparge water, because then one doesn't have to estimate the residual acidity left in the sauermalz malt. Does this make sense? Is there any benefit to using sauermalz malt instead of bottled lactic acid if they are the same thing, but the latter is easier to control for sparging (using a graduated dropper)?

Question for A.J.:

You recommend in the original post that one dilute water with RO or DI if there is high alkalinity. Can one not simply combat this with acid? My city water profile is as follows:

Calcium (Ca ppm): 35
Magnesium (Mg ppm): 9
Sodium (Na ppm): 14
Chloride (Cl ppm): 27
Sulfate (SO4 ppm): 28
Alkalinity (CaCO3 ppm): 124
 
There wouldn't be any excess acidity because one uses only enough acid to overcome the mash water and malt alkalinity. Thus the pH of the runoff will start to increase as soon as sparge water is added. The question is 'how fast?' It is entirely possible that you will be able to sparge to the desired level of runoff extract without breaking pH 6 and without using acid in the sparge water. It is pretty clear that you have a better chance of having things work out this way with DI or RO water than you would with highly alkaline water from some other source. To be absolutely safe you can acidify the sparge water to pH 6 or a little below. It should be clear that no amount of dilution will cause the pH to drop below 6.

You can acidify mash with sauermalz or acid but you should not acidify sparge water with sauemalz and you especially should not compute the amount of sauermalz required to acidify the sparge water and then add that to the mash as this would cause the mash pH to go too low. The big advantage of sauermalz, IMO, is the 1% w/w per 0.1 pH rule. This means no calculations you can't do in your head. A secondary benefit is that sauermalz is a specialty malt and conveys some flavors which are, IMO, beneficial to certain styles of beer.

The Question: Keep in mind that most of alkalinity comes from bicarbonate ion HCO3- and that this is disposed of when acid HAn with An representing the anion of the acid by

HAn + HCO3- ---> CO2 + H2O + An-

Thus every milliequivalent of bicarbonate removed by acid is replaced by 1 mEq of An-. In some cases this can be a benefit. For example, British brewers with low sulfate and chloride by high bicarbonate can replace the bicarbonate with sulfate and chloride ions from, respectively, sulfuric and hydrochloric acids. If, conversely, your water is high in sulfate, chloride and bicarbonate, neither sulfuric nor hydrochloric acid is a good choice for bicarbonate reduction. In such cases most brewers would probably use phosphoric acid as the phosphate ion is flavor neutral. Another popular choice is lactic acid but lactate is pretty strongly flavored and if a lot of bicarbonate has to be disposed of more lactate than is pleasing might be required.

The water cited has an alkalinity of 2.48 mEq/L. To get rid of most of it (2 mEq/L) would add 96 mg/L SO4-- if sulfuric acid were added or 70 mg/L chloride or some combination of less than those amounts of each totalling 2 mEq. Lactic and phosphoric amounts are a little harder to compute and it's late so I'm not doing it.

Another reason many favor dilution rather than acid addition is that if the source water is variable the amount of acid to be added is variable and can only be determined by measuring the alkalinity before each brew. A way around this is to simply add acid to the brewing water (no grains) until the pH reaches mash pH. That will get rid of about 80% of the alkalinity. Sierra Nevada does this, for example.

Remember that an important part of the primer is the KISS principle. Fiddling with acids, pH meters and alkalinity test kits is not part of the beginner's KISS approach.

Just to be sure the question gets answered the answer is not only yes, it can be done that way but that in fact many do.
 
The water cited has an alkalinity of 2.48 mEq/L. To get rid of most of it (2 mEq/L) would add 96 mg/L SO4-- if sulfuric acid were added or 70 mg/L chloride or some combination of less than those amounts of each totalling 2 mEq. Lactic and phosphoric amounts are a little harder to compute and it's late so I'm not doing it.

Thanks for the reply A.J. It's very much appreciated.

I brewed a 5.5 gal batch immediately after my last message, so I didn't have a chance to read your message. I added some gypsum and a touch of calcium chloride, as well as 4.5ml of lactic acid to the water before I heated it and added it to the MLT. The spreadsheet said I'd hit around 5.46 pH with those additions (water only), which, when combined with malt, would result in a 5.46 - 0.25 = ~ 5.2 pH. After draining that off, I then added enough lactic acid to the sparge water to also hit 5.46 (before hitting the grain). Therefore, the mash and sparge pH, before they hit any malt, were the same. Was this reasonable?

As an aside, I need to treat the mash and sparge water separately unfortunately. But in adding roughly the same amount of lactic acid per gal, the pH of both the mash and sparge water should be the same before being added to the MLT. Next time I may split the gypsum and calcium chloride additions similarly so the mash and sparge water will be identical.

I'll invest in a pH meter soon so I can dial the pH in. I'll also try some acidulated malt next time (for the added flavour complexity), which I have plenty of here, but haven't used because I figured lactic acid additions would be easier.

Any suggestions?

Edit: I'm just realizing now that adding that much acid is going to change the flavour of the beer. What should I have done differently to ensure that the sparge water's pH isn't too high (other than dilution)?
 
I decided to add all of my salts to the mash, approximating as close as possible total water (mash, sparge etc.).
Here are some results from brews this weekend, room temp pH, theoretical pH as calcualted by EZWaterCalc:

Theoretical pH Actual Mash pH Post boil pH Post Ferment pH OG
Brown Ale 5.5 5.62 5.15 TBD 1.059

Stout 5.55 5.98 5.36 TBD 1.064

Helles 5.4 5.34 5.23 TBD 1.052


The darker beers came out with higher pH and the Helles with lower. More data (i.e., more brews!) is needed.
 
Hmm.. I guess I am lucky..

All my water I got straight from the tap and the top-off water straight from the tap no boiling. No problems and beer so far tastes great.

That said our water is fairly soft and clean. I had aquariums and barely had to do anything to the water until after the fish were in it.
 
Hmm.. I guess I am lucky..

All my water I got straight from the tap and the top-off water straight from the tap no boiling. No problems and beer so far tastes great.

That said our water is fairly soft and clean. I had aquariums and barely had to do anything to the water until after the fish were in it.
You could run into problems if there is something in the water that likes your beer AND you store it a long time. I was ridiculed for saying this before but it would explain why people 'suddenly' have a favorite batch they have been nursing along suddenly 'go bad' on them. A few bacteria doubling under hostile conditions might take a long time to reach a detectable threshold level but the last doubling could appear to be quite sudden.
 
I was ridiculed for saying this before but it would explain why people 'suddenly' have a favorite batch they have been nursing along suddenly 'go bad' on them. A few bacteria doubling under hostile conditions might take a long time to reach a detectable threshold level but the last doubling could appear to be quite sudden.

OK but let's recognize that there are other things that cause beer stored for a long time to go bad:

1. Oxidation: Some of these reactions are slow. If the wort/beer is not in a reduced state when packaged and if oxygen is not excluded from the package then over time the beer may develop the (alas) familiar cardboard or other tastes.
2. Diacetyl: I keep beer for a long time because I brew large batches (and I do that so I'll have it around for a long time). Diacetyl forms after fermentation and lagering is, therefore, done over yeast so they can reabsorb it. Because I'm keeping the beer for a long time I lager in the package (kegs) and make sure there is plenty of yeast in there. Eventually the yeast die and are no longer able to remove diacetyl. Eventually (a year or more) the diacetyl starts to creep back up (the beers begin to taste caramel like). Don't really know the mechanism - is there still acetolactate in there converting to diacetyl with no viable yeast to pick it up?
3. Whatever happens to Weizen beer: This is probably the most extreme example. Weizen beer just can't be stored for more than a couple of months. I suspect the problem is oxidation by my Weizens are stored no differently that my lagers. I remember trying to explain (in my halting German) to a bunch of good Burghers who wanted to know if we had Weizen in the US. I said no because by the time it got over here it wasn't Weizen any more.

I have had infection in a keg (fortunately only one out of the 4 I typically fill) but it came up right away. The other problems (except 3) take more than a year in my experience.

In case you think that I am advising that boiling isn't necessary let me be clear that it is one of those things you can probably get away with omitting 99 times out of 100 but it isn't worth risking it.
 
1. Oxidation: Some of these reactions are slow. If the wort/beer is not in a reduced state when packaged and if oxygen is not excluded from the package then over time the beer may develop the (alas) familiar cardboard or other tastes.
.

Sorry as this is off topic for the water primer:) How fast does the classic cardboard oxidation take to form? I did an off flavours class and I noticed they used the seibel kit for the oxidation but for light struck they just set the beer out in the sun for the afternoon. Is oxidation fast enough that you could simply bubble pure O2 through a beer and then serve it a few minutes (or hours) later as an example of the oxidation off-flavour?

2. Diacetyl: I keep beer for a long time because I brew large batches (and I do that so I'll have it around for a long time). Diacetyl forms after fermentation and lagering is, therefore, done over yeast so they can reabsorb it. Because I'm keeping the beer for a long time I lager in the package (kegs) and make sure there is plenty of yeast in there. Eventually the yeast die and are no longer able to remove diacetyl. Eventually (a year or more) the diacetyl starts to creep back up (the beers begin to taste caramel like). Don't really know the mechanism - is there still acetolactate in there converting to diacetyl with no viable yeast to pick it up?

Last year I had 2 batches that seemed to increase in diacetyl and a batch that started to develop acetaldhyde after a couple months in the keg stored at 17-18C. I assumed I had some sort of baterial infection and have since replaced all my plastic and striped down my kegs and boiled all the rubber parts. I'm hoping its something as straight forward as an infection.
 
I can add the post ferment data now:

Brown Ale: pH 4.54 FG 1.016 Notes: Despite the high FG, the beer tasted remarkably dry, with the dark malts being very well expressed. All of the grain was home malted (not by me). Very pleased and a second batch is now fermenting (using commerical grains). Would like to see the finish pH down slightly.

Stout: pH 4.22 FG 1.018 Beer tastes excellent. Big (as in ciomplex), but dry with a firm bittering. Roast nicely expressed. Brewing again this weekend.

Helles: pH 4.52 FG 1.012. The beer tastes good, except that I perceive a slight minerally aspect. We'll re-evaluate post clarification and carbonation. Brewed again reducing the total calcium and using acid malt to attain lower pH (but hit only 5.51 as compared to 5.34 with the first helles). Final pH is still too high.

I've noticed that inthe 7 beers I have brewed using the EZCalc spreadsheet that with one exception (first helles) the mash pH always comes in higher than predicted. I plan to increase the addition of acid malt until I hit th target. My post ferment pH is greatly improved.

As to when I add salts. Everything (gypsum, CaCl2, chalk, MgSO4) is added at the mash. Sparge water is acidified to 5.5 using 10% phosphoric per Strong's book. I am also thinking about acidifying the mash water thusly as that might also help in lowering pH.

Cheers!
 
PS. Scrolling through earlier posts (prior to my joining the Forum) I see mention of a Water primer. What/where is that?

Cheers!
 
Acidifying the mash water to intended mash pH effectively reduces its alkalinity to 0. The graph at http://wetnewf.org/pdfs/alkalinity-reduction-with.html (which I originally posted here) shows the percentage alkalinity reduction as a function of target pH and original pH. Just remember that every equivalent of alkalinity removed is replaced my an equivalent of the anion of the acid.

The Primer is, in fact, this very thread.
 
Thanks again, AJ. FYI, the link to Alkalinity part I appears to be broken.

Cheers!

PS There is a spreadsheet referenced (see a post on 11-12-12). Can you (or anyone) advise what spreadsheet that is? Thanks!
 
Acidifying the mash water to intended mash pH effectively reduces its alkalinity to 0. The graph at http://wetnewf.org/pdfs/alkalinity-reduction-with.html (which I originally posted here) shows the percentage alkalinity reduction as a function of target pH and original pH. Just remember that every equivalent of alkalinity removed is replaced my an equivalent of the anion of the acid.



This is what Sierra Nevada is supposedly doing, setting all brewing water to 5.5?
 
Thanks again, AJ. FYI, the link to Alkalinity part I appears to be broken.
Thanks for the heads up on that. The thing has only been on line a couple of days and I've got lots to do.

There is a spreadsheet referenced (see a post on 11-12-12). Can you (or anyone) advise what spreadsheet that is? Thanks!
Probably Bru'n Water or EZ. Fits either.
 
This is what Sierra Nevada is supposedly doing, setting all brewing water to 5.5?

Quote from the linked page: "It has been reported that Sierra Nevada, consistent with the idea given here, treats all it's water to pH 5.5 with phosphoric acid. Chico water has average alkalinity of 76 ppm as calcium carbonate and pH which can be as low as 6.5 or as high as 7.9."

It was this rumor that got me thinking about the consequences of doing this. I think it's pretty smart.
 
sorry if im off topic but would it be wise to add calcium cloride to poland spring water for a BGSA? It is soft and low in minerals
 
I really appreciate all of this information and interaction. And to think I actually started down this road because I was trying to achive clarity!! I'm using my pH meter twice as much as my refractometer! i'm using the EZ for my spreadsheet and will continue to report out on my data. The biggest variable seems to be in estimating total water. Very hard to predict how much gets left behind in the tun. You don't know until it's drained. I'm getting better at predicting when to stop adding more sparge water.

Cheers!
 
I really appreciate all of this information and interaction. And to think I actually started down this road because I was trying to achive clarity!! I'm using my pH meter twice as much as my refractometer! i'm using the EZ for my spreadsheet and will continue to report out on my data. The biggest variable seems to be in estimating total water. Very hard to predict how much gets left behind in the tun. You don't know until it's drained. I'm getting better at predicting when to stop adding more sparge water.

Cheers!
You could just sparge until you hit your boil volume. There is nothing magical about the amount left in the tun.

I have a friend at a brewery that runs wort into the drain that most of us would brew with because all their stuff is high gravity. He would like to let home brewers come in to collect it but it would interfere with their schedule.
 
You could just sparge until you hit your boil volume. There is nothing magical about the amount left in the tun.

Wouldn't that make it difficult to approximate the various salt aspects, e.g., SO4-- for IPA, etc.? They would be diluted.
 
You could just sparge until you hit your boil volume. There is nothing magical about the amount left in the tun.

Wouldn't that make it difficult to approximate the various salt aspects, e.g., SO4-- for IPA, etc.? They would be diluted.
The ratios, ppm's. stay the same regardless of volume. I guess if you just want x milligrams in the kettle you could just add it to the kettle.
 
So I am going to be making my first batch this weekend using RO water and I just wanted to get some clarification what I should add. I will be making an BarleyWine, using 2-row,aromatic, crystal 30 and 80, and some rye. Its for a 5 gallon batch and according to beersmith, I am using 6.66 gallons of strike water and 3.42 gallons of sparge water. Does anyone have any good recommendations on what minerals to add. When it comes to the water adjusting, I am still completely lost.
 
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