I just don't get water chemistry

[MaxSpang]

I'm trying. I really am. But I am getting very frustrated with this whole water chemistry thing. My brain is not comprehending how to accomplish what I want to accomplish. I would like to learn by a specific example.

Can anyone do me a favor and help me out with my next batch? I want to see what to add to get it to the right profile, and then I'd like someone to explain why/how they got to that point. It's a Saison, and it's 10 gallons. I want to start with RO water, and I want to add enough minerals to get the following target profile (I got it from here):

Ca+ 116
SO4 45
Mg+ 25
Na+ 101
Cl- 106
CO3 598

OR ANOTHER GOOD SAISON PROFILE! (I'm open to recommendations)


The grain bill is as follows:

Pilsen malt - 15 lb (1 degree L)
White Wheat - 5 lb (2.5 degrees L)
Munich Malt - 2 lb (17 degrees L)

Total Water needed = 16.73 gallons
Mash water = 7.32 gallons
Sparge water = 9.41 gallons



So... what do I need to add to get that target profile from RO water? And WHY do I need to do it that way?

I know I'm asking a lot here, so thank you in advanced. I literally just do not understand it. Every time I've tried I end up with all the proportions wacky.

 

[mabrungard]

That target profile is very unsuited for a Saison. That source is very dated and inaccurate. I suggest the following profile as a starting point for a Saison. The great thing is that starting with RO water is ideal for creating this profile.

Ca 35
Mg 9
Na 13
SO4 67
Cl 50
HCO3 -77

As you will notice, the bicarbonate value is actually negative. You will need to add acid to bring the mash pH into the preferred range. Please understand that this bicarbonate value may not be ideal for your grist and some adjustment up or down may be needed. You should recognize that Saison is a crisp and tart style and a low mash pH is recommended. I suggest that targeting a pH of around 5.2 to 5.3 would help accentuate the crispness and tartness of the finished beer.

 

[Hopper5000]

That's something that has confused me, why bicarbonate levels go negative/what is the reason for this? Is it just so you can lower your pH the the appropriate level?

 

[ajdelange]

That's something that has confused me, why bicarbonate levels go negative/what is the reason for this?

Bicarbonate levels never go negative. The lowest bicarbonate level you can have is 0 and this happens at low pH.

What can go negative is alkalinity. Brace yourself. Alkalinity is the amount of acid that must be added to a water sample to reduce its pH to 4.3 (or some similar number depending on how alkalinity is defined). It is a measure of the amount of acid required to convert nearly all the bicarbonate (and carbonate) in the sample to carbon dioxide which happens at pH 4.3. Because the relationship between bicarbonate content and alkalinity is a little tricky most spreadsheets and calculators simplify things and treat them as if they are proportional in particular as if bicarbonate = 61*alkalinity/50). That's a valid approximation for 6 < pH < 8.5 but not for pH values outside this region in particular not for the pH required to get negative alkalinity.

If you add enough acid to water to lower it's pH below 4.3 and present it to an analyst and request that he measure alkalinity he will, following the prescribed procedure, first check the pH. Seeing that is is below 4.3 he immediately knows that the alkalinity is negative. You wouldn't add acid to this sample to get the pH to 4.3, you'd have to subtract it which means that you would actually add a base to neutralize the acid it. The amount of base added to get to pH 4.3 (a positive number) is referred to as the 'acidity with respect to pH 4.3' but can be called alkalinity if the sign is reversed.

Is it just so you can lower your pH the the appropriate level?

It is quite perceptive of you to pick this up as the concept of negative bicarbonate is completely erroneous and therefore confusing. I guess what is intended here is that the water should have an alkalinity of (50)*(-77)/61. It would be much clearer if it were stated that the water should be taken to pH 4.3 and then 1.26 mVal of acidity beyond that added or that the alkalinity of the water should be -1.26 mVal (mEq/L). This means that 1.26 mL of N (normal, 1 N) acid should be added to each liter of RO water treated.

That is if -1.26 mVal is the right number.

Saisons are brewed with all kinds of water - it varies greatly. Given that probably the most methodical approach would probably be to follow the guidance in the Primer - just RO water and half tsp (2.5 g) calcium chloride/5 gal treated using 2-3% w/w sauermalz to set the mash pH. Doing this the mash pH should be checked and if it is appropriate you are fine. If too high, add more sauermalz, if too low, less. It is best to make these determinations on a small test mash rather than the whole length of the beer. Adjust the sauermalz based on your test mash findings. Each 1% w/w lowers mash pH by about 0.1 pH.

Assuming that mash pH comes into the right range (5.3 - 5.5 as determined by a properly calibrated meter) then proceed with the mash and ferment the beer. Now taste it. Then add some calcium chloride to the glass and taste it again. Better or worse? Do the same with sulfate. And with sodium chloride and magnesium sulfate if you want but just the calcium salts should give you all the information you need to adjust the salt additions to the liquor the next time you brew.

This KISS approach followed by experimentation with chloride and sulfate levels (always monitoring mash pH) should get you some very good beer. While you are enjoying that you can worry about the intricacies of brewing water chemistry though unfortunately you will be thrown a curve by things like 'negative bicarbonate'. Another similar confusing term is 'ppm as CaCO3'. Both are really trying to express alkalinity (which is in units of mVal or mEq/L and which can be positive or negative) in other terms which are supposed to be easier to understand. Both have some validity over a small range of pH (bicarbonate) or a larger one (ppm as CaCO3) and, when pH < 4.3, as both become negative and you can't have negative bicarbonate or negative calcium carbonate both muddy the water, so to speak.

 

[mabrungard]

Unfortunately AJ, you are missing the forest because of the trees. You speak of the validity of alkalinity going negative and I know you know that a positive alkalinity does equate to a bicarbonate content (within a certain pH range). Therefore, while you are correct that there is never truly 'negative bicarbonate' content, there certainly is an allegory that acid content can be translated to a negative bicarbonate content (or alkalinity demand) for a water.

Users of Bru'n Water will recognize that there is indeed a negative bicarbonate content that can be ascribed to brewing water and it is a valid way to describe the effect of acid addition.

I know it offends you, but its still workable and valid.

 

[ajdelange]

Unfortunately AJ, you are missing the forest because of the trees.

I don't think so. Let me explain why.

You speak of the validity of alkalinity going negative and I know you know that a positive alkalinity does equate to a bicarbonate content (within a certain pH range).

If I were to add 1 mEq of lime or lye or potassium hydroxide to a liter of DI water that water would have an alkalinity of (approximately) 1 mVal (mEq/L) or 50 ppm as CaCO3 or a "bicarbonate content" (calculated by the formula home brewers use) of 61 mg/L when in fact it contains no bicarbonate (nor calcium carbonate for that matter) whatsoever. Similarly, if I add 1 mEq of a strong acid to 1 L of DI water it would have an alkalinity of - 1 mVal or -50 ppm as CaCO3 or a "bicarbonate content" of - 61 mg/L even though it contains no bicarbonate or calcium carbonate whatsoever. What we are interested in here is a proton deficit or surfeit and we have names for those, respectively alkalinity and acidity (though we can consider acidity to be a negative alkalinity) and units for clearly and unambiguously expressing them. These are the mEq/L and mval. When a sample is submitted to a laboratory for analysis the pH is measured and the sample then titrated to a reference pH (acidity and alkalinity must be specified relative to a reference pH) with acid (alkalinity measurement: sample pH > reference pH) or base (acidity measurement: sample pH < reference pH). The alkalinity or acidity is the number of mEq of acid or base required to reach the reference pH per liter of sample. What has been measured is the proton deficit or surfeit wrt a particular pH and mEq/L (mVal) is the natural unit of alkalinity and acidity and these are the units used in water reports outside North America. In the US we use the proxy unit 'ppm as CaCO3' which is 50 times the alkalinity/acidity in mVal. This is done because if 100 mg of CaCO3 is dissolved in a liter of water using CO2 as the acid and bring the pH to 7 then the hardness and alkalinity of the water will both be about 100 ppm as CaCO3. This practice has confused a lot of people trying to understand how this stuff really works because what we are really interested in, when it comes for example, to attempting to predict mash pH is proton deficit or surfeit.

Therefore, while you are correct that there is never truly 'negative bicarbonate' content, there certainly is an allegory that acid content can be translated to a negative bicarbonate content (or alkalinity demand) for a water.

As indicated above, the 'proper' unit for alkalinity/acidity is the mVal. There are several other 'allegory' units abroad as well. The aforementioned 'ppm as CaCO3' which is 50 times the mEq/L expresses things in terms of the number of mg/L CaCO3 dissolved in a particular way. While use of this unit is to be deprecated for reasons alluded to above we are sort of stuck with it because in brewing we are ruled, in the US at least, by the MOAs of the ASBC and Standard Methods for the Examination of Water and Waste Water is incorporated into the MOAs by reference and those standards use ppm as CaCO3. In Germany °dH, in which the mEq/L are multiplied buy 2.804 are in common use and in France the °F in which the mEq/L are multiplied by 5. Martin seems to like to multiply by 61 and I'd like to propose the °AJ in which the mEq/L are multiplied by Euler's constant (0.57721).

Users of Bru'n Water will recognize that there is indeed a negative bicarbonate content that can be ascribed to brewing water and it is a valid way to describe the effect of acid addition.

If you are going to use one of the deprecated units you should, IMO, use the one that is accepted in the industry and not one you made up yourself. I also think you are obliged to point out that this number is not really expressive of bicarbonate content. If we say "alkalinity, ppm as CaCO3" the 'as' suggests that we are not really talking about CaCO3 content but are using this proxy to express proton deficit. Similarly if we say "alkalinity, °dH" or "alkalinity, °F" or even "alkalinity, °AJ" we know that we are talking alkalinity (proton deficit). But if we say "bicarbonate 77" that suggests that the bicarbonate content of the water is 77 mg/L. If you insist on using this unit you need to say "alkalinity, as bicarbonate".

I know it offends you, but its still workable and valid.

Given that you have perfectly good, unambiguous, exact units that do not depend on pH and are valid whatever the actual chemistry of the water why would you use anything else? A possible answer, though it still offends me, might be that 'ppm as CaCO3' is widely used in the US to express acidity and alkalinity and is accepted by ASBC and AWWA. But mg/L bicarbonate is not accepted in either of the industries (AFAIK - in fact I've never seen anyone express alkalinity/acidity 'as bicarbonate' before that I can recall) so why try to force it on home brewers? Is there some benefit to it that I'm missing?

I think those of us that have been dubbed experts should try to lead aspirants along the path of accepted practice. This does not mean being closed minded to new ideas but I'm afraid I just can't see any benefit to expressing alkalinity in units of mg/L of anything. "As calcium carbonate" or "as calcium oxide" isn't good either but at least there is precedent.

 

[ajdelange]

An additional note to the OP if he is still on board. Most of brewing water chemistry is pretty simple and requires only that one be able to solve problems like "Given that a pound of jellybeans contains 0.4 lbs of red ones and 0.6 pounds of blue ones how many pounds of the mix should be added to 50 pounds of M&M's to give an overall mix that contains 2 lbs of red jellybeans and 3 pounds of blue ones.

The exception to this is, of course, the subject under discussion here. The hard part of brewing water chemistry lies in being able to calculate the proton deficit or surfeit of water, malt, specialty malt, acids you add or base you add. If you want to understand this, and I'm not sure that is really the goal, then this is the part you will have to tackle. There are places on the web you can go for info on this (e.g. my site, wetnewf.org) or a chemistry text that deals with ionic equilibria (Henderson Hasselbalch equation) is a good place to start.

I suppose it goes without saying that this is also the critical part and it is thus very important that it is thoroughly understood. That's why I get crabby if the presentation of this aspect isn't crystal clear.

 

[aiptasia]

Alright, now that we're all thoroughly confused again, can we get back to the OP's question? What amounts of elements does he had to his distilled water to create the water profile he needs?

 

[ajdelange]

That has been covered. A half to one tsp CaCl2 per 5 gal plus 2-3% sauermalz w/w in the grist is a good starting point.

 

[MaxSpang]

I appreciate the replies, everyone! I'm not going to lie, this is pretty overwhelming.

So, going off of this:

Ca 35
Mg 9
Na 13
SO4 67
Cl 50
HCO3 -77

...what about this: http://www.brewersfriend.com/mash-chemistry-and-brewing-water-calculator/?id=KPFHZ3X

I added a pound of acid malt to get the pH at around 5.2. I also kept the HCO3 at 0 since I can't make it negative.

 

[mabrungard]

Your mistake is using the brewersfriend calculator. Bru'n Water shows you directly what the bicarbonate demand (negative bicarbonate) is with acid additions. Using acid malt is a rather imprecise option for acidification of the mash.

By the way, sulfate is a very important component in brewing a Saison since it helps dry the beer's finish. Adding only a dose of calcium chloride is not likely to help with that characteristic drying that is desired in this style.

 

[Obliviousbrew]

"Given that a pound of jellybeans contains 0.4 lbs of red ones and 0.6 pounds of blue ones how many pounds of the mix should be added to 50 pounds of M&M's to give an overall mix that contains 2 lbs of red jellybeans and 3 pounds of blue ones.

I´m confused how many jellybeans should I add to make an stout from RO wáter? Should I spik the M&M´s? can I add some skittles?

 

[ajdelange]

I´m confused how many jellybeans should I add to make an stout from RO wáter?

Six. Told you it was simple.

Should I spik the M&M´s?

Don't know what 'spik' means.

...can I add some skittles?

Only if you include Robitussin and Arizona Watermelon Fruit Juice Cocktail.

 

[ajdelange]

Your mistake is using the brewersfriend calculator. Bru'n Water shows you directly what the bicarbonate demand (negative bicarbonate) is with acid additions.

Trying to understand what negative bicarbonate means. 'Demand' suggests, by extension of the concept of BOD, COD, ..., that if I have a certain acid level in a solution that the 'bicarbonate demand' would be the amount of bicarbonate necessary to 'neutralize' that acid. So I turn to the original assertion that OP's water should have a bicarbonate 'demand' of 77 mg/L. This, I assumed, meant that the alkalinity of the water was -77/61 = -1.262 mEq/L which I assume I can realize by adding 1.262 mEq of strong acid to a liter of water thus obtaining a proton surfeit, with respect to any reasonable pH (<8? and approximately) because it is strong acid, of 1.263 mEq/L. Now if I add 1.262 mEq of strong base to this liter of water the acid is neutralized. But supposing I add the demanded 77 mg of bicarbonate ion (e.g. 84 mg NaHCO3) to this liter of water. The pH goes from 2.9 to 4.7. Is this neutralization? Suppose I add twice that much (154). The pH goes to 6.5. Is that neutralization? But suppose I add 84.5 mg/L bicarbonate. The pH then goes to 5.4, a reasonable mash pH. Is that neutralization? That's more like it but the point to be made is that proton surfeit, whether you choose to state it correctly in terms of mEq/L or scale it by some constant, must have a target pH associated with it (and, in fact, a source pH as well which, with sodium bicarbonate is about 8.3). The other point is that calling the proton surfeit bicarbonate demand is a bad choice because the bicarbonate that must be added is more than the 'bicarbonate demand'. One mmol of of a bicarbonate salt does not absorb 1 mEq of protons except when the end pH is < 4.

The reason bicarbonate isn't working here is because you are trying to express the proton surfeit of a strong acid in terms of the proton deficit of a weak base (bicarbonate). If you wanted to express the deficit as 'sodium hydroxide demand', i.e. in terms of a strong base, you would be fine. Or perhaps 77 vs 84 is 'close enough for government work'.

Calculating the proton surfeit of added acids is a good idea. Proper algorithms for estimating mash pH turn on exactly that concept. Expressing this surfeit in standard industry units, 'ppm as CaCO3' leads to some confusion but as everyone is familiar with this standard and knows that it is really code for mEq/L (divide by 50) it is not so terrible. Expressing the surfeit, especially if you call it 'bicarbonate demand' as mg/L bicarbonate is not a good idea as people might get the erroneous impression that adding that amount of bicarbonate would consume the acid. If everyone understood that it is really code for mEq/L (divide by 61) then it might not be so bad but you'd have to educate the community to this non standard terminology.

Using acid malt is a rather imprecise option for acidification of the mash.

It is, of course, a rule of thumb and actual pH shifts vs the 0.1 per % w/w will, naturally, depend on the buffering capacities (i.e. the proton deficits and surfeits) of the base and specialty malts and the proton deficit of the water but whereas I have seen reports of 0.08 and 0.09 vs. 0.1 but never any 'Wow, is that off base!' comments and as Weyermann has been publishing that number for years I suspect it is at least as good if not better than the estimated deficits and surfeits of the malts based on measurement and color as I understand the various spreadsheets estimate them. I have elsewhere posted that it is possible to get good malt buffering data but that the process is so laborious as to make it impractical to use that approach. One must, in effect, make 20 or 30 test mashes for each malt. Easier to do one test mash on the actual grist.

By the way, sulfate is a very important component in brewing a Saison since it helps dry the beer's finish. Adding only a dose of calcium chloride is not likely to help with that characteristic drying that is desired in this style.

Desired by whom?

If the goal is to win a ribbon in a competition and the BJCP style guidelines say that a dry, sulfate finish is desired then yes. If the OP likes beer with a dry sulfate finish then yes. If the OP does not, then no. That's why he should try it without sulfate first (unless he is more interested in ribbons than pleasing himself).

 

[MaxSpang]

I definitely want a dry saison.

I appreciate all the help, but I would still like someone to tell me specifically what I should add and tell me why I am adding it. A giant wall of text isn't helping me understand this, unfortunately.

 

[Hopper5000]

Ya, sorry about that Max. I am partially responsible for the thread jacking on this one.

Water chemistry is somewhat complicated and I agree that it is overwhelming at first. I totally was overwhelmed and kind of avoided it for a while.

Different concentrations the elements important in brewing and their relationships with each other will impact some of the percieved flavors in your beer.

It's good that you are starting with RO water so that you can build whatever profile you want from there.

I use Bru'n water for my beers and use the standard color profiles because they aren't very extreme. I generally feel like with water chemistry less is more and you shouldn't over do it a lot.

Certain minerals that you add to beers can make it seem drier. I believe gypsum is one of them. There are general ranges for each of these minerals that are recommended for certain tastes that you are going for. Over doing or under doing these can cause harsh flavors and/or make yeast not perform as effectively as they can.

The profile for your Saison seems a bit too extreme for the style since it has pretty high bicarbonate levels which could potentially cause the mash pH to become too high and cause astringency.

 

[MaxSpang]

Ya, sorry about that Max. I am partially responsible for the thread jacking on this one.

Water chemistry is somewhat complicated and I agree that it is overwhelming at first. I totally was overwhelmed and kind of avoided it for a while.

Different concentrations the elements important in brewing and their relationships with each other will impact some of the percieved flavors in your beer.

It's good that you are starting with RO water so that you can build whatever profile you want from there.

I use Bru'n water for my beers and use the standard color profiles because they aren't very extreme. I generally feel like with water chemistry less is more and you shouldn't over do it a lot.

Certain minerals that you add to beers can make it seem drier. I believe gypsum is one of them. There are general ranges for each of these minerals that are recommended for certain tastes that you are going for. Over doing or under doing these can cause harsh flavors and/or make yeast not perform as effectively as they can.

The profile for your Saison seems a bit too extreme for the style since it has pretty high bicarbonate levels which could potentially cause the mash pH to become too high and cause astringency.

No worries. I really appreciate the help with all of this, seriously!

The only reason I grabbed that water profile was because it was the firs thing that came up when I googled "Saison water profile". I guess what I'm looking for is:

A) A good saison profile
B) A way to turn RO water into that profile
C) WHY it's a good water profile for a saison

 

[ajdelange]

I think this may be the third go but a good water profile for Saison is obtained by adding about half a tsp of calcium chloride to 5 each 5 gal of water treated. If you want the beer dry then do the saccharification rest at a low temperature (144 °F).

Now when you have finished brewing that beer taste it. Then add some gypsum to it and taste it again. This will tell you whether sulfate lends the 'dry' character you want or not. If it does, great. Brew the next time with some sulfate. If it doesn't then skip the sulfate next time.

I think I've also said you can make this complicated or you can make it simple. I did the complicated stuff for years and wound up doing things simply and a) life is easier and b) my beer is better.

You should have gathered by now that there are several 'good' water profiles for a Saison and that they differ appreciably. There are two reasons for this. One, that I also mentioned earlier is that Saison is brewed with waters that are appreciably different from one another. The other is that people have different tastes. There is no holy grail here. You will have to experiment.

A) A good Saison profile consists of half a teaspoon of calcium chloride in 5 gal of RO water treated or, if you prefer, 41 mg/L calcium and 73 mg/L chloride.
B) You turn RO water into water with that profile by adding 1/2 tsp CaCl2 per 5 gallons.
C) It is a good Saison water profile because it works for almost any beer. It may not be, to your tastes, the best Saison water profile but as I don't know your tastes I cannot recommend one better and neither can anyone else despite what they may tell you. 'I make a killer Saison' with this or that profile means only that someone made a Saison he liked with that profile. That fact should be taken into consideration and you might wish to use that fellow's recommendation instead of mine. It doesn't matter much what you do, within reason, as long as you are prepared to experiment.

You could also use 1/4 tsp each of calcium chloride and calcium sulfate. That would also be a good Saison profile. I haven't the temerity to tell you that this will make a better Saison than 1/2 tsp of CaCl2 because I have no way of knowing which you will like better. That is entirely up to you. I recommend that you start with 0 sulfate at first because lots of people find they really don't like sulfate. You may be one of them.

And it goes almost without saying that you will need to add a couple of percent sauemalz or other acid equivalent to your mash. This is necessary to set mash pH properly.