A quick survey on Water Profiles

[cmac62]

If you'll accept my attempt at an explanation: ppm is [commonly] mg/L (parts-per-million itself is a poor term because it's not at all about "parts"). Different ions have different masses. So, to take an example with easy numbers, if the mass of A is 1mg and the mass of B is 2mg, at 2ppm you'd have one of B but two of A in a liter.

The other issue is different electric charges. If the charge of C is +1 and the charge of D is -2, you'd need two of C to create a neutral charge against one of D.

Milliequivalents (mEq[/L]) takes both the mass difference and charge difference into account and tells you how many actual parts you have which can react with other parts, hence equivalents. In analogy, if you need 4 screws to connect 2 pieces of wood, and you have 8 screws and 4 pieces of wood (2 equivalents), you know you can complete 2 connections, and don't have to worry about what the masses of screws or pieces of wood are.

I don't know why the E is capitalized, but the m is lower-case because it stands for "milli", and if you wrote it as equivalents-sans-milli it would usually be 0.0..x.

Thanks, that does make sense. Is that why Ca++ is listed, it has a ++ charge and requires -- to be equal?

 

[Silver_Is_Money]

Eq = Equivalent (= weight in grams whereby to balance/react with some other Eq Wt., charge + for charge -).

m = milli (or 1/1000)

mEq = milliEquivalent (= weight in milligrams whereby ....)

Another thing to consider with regard to ones best fantasy dream Water Profile is that it better balance perfectly on a +mEq/L for -mEq/L basis, or else it would make for a rather shocking experience. As fortune has it, all "real" water balances electrical charges perfectly. But dreamed up fantasy water mineralization almost never does, because almost no one ever thinks to balance it electrical charge for electrical charge (which means mEq for mEq or mEq/L for mEq/L). Fortune shines upon us yet again however, because a fantasy dream Water Profile that does not perfectly charge balance is factually not possible to construct in this, our very real world. So if you ever wondered why, try as you may, you can never reach your fantasy Water Profile dream via playing with and juggling seemingly endless variations upon variations with your minerals, wonder no more.

Yet another reason as to why to favor mEq over ppm (mg/L).

 

[Silver_Is_Money]

Those with regional water authority water reports which are averaged across more than one source, or that are 'seasonally' averaged, are out of luck. The mega-mistake is that people believe the fantasy printed "averages". Averaged water mineralization will not Cation/Anion mEq balance sans for a miracle of blind luck. The situation is much as for the post above. Whatever your real world water mineralization may look like, it will not look like the printed averages (even if by the miracle of chance ones averages derived water ppm's achieve Cation/Anion mEq charge balance).

 

[tracer bullet]

So if you ever wondered why, try as you may, you can never reach your fantasy Water Profile dream via playing with and juggling seemingly endless variations upon variations with your minerals, wonder no more.

I don't think this person exists.

 

[dmtaylor]

I don't think this person exists.

Hmm.... I do.

 

[Silver_Is_Money]

Still kinda not excited about the measurement units thing. All chemical reactions take place without regard to how we name or measure the units.

As for everything in life, an understanding of chemical reactions essentially boils down to this:

To get where one wants to go, one must first know where they are.

And thus mEq's.

 

[Silver_Is_Money]

As I see it the gist of the bashing and desire to place this science into the trash bin of rant essentially seems to derive from a desire to be spoon fed with all of the mEq based answers as to Water Profiling all at once. I can understand this. If the comfort zone of ppm (mg/L) based Water Profiles has been rocked, the immediate knee jerk reaction is to replace it with a fully evolved comfort zone of mEq based Water Profiles. But this (I.E., my perspective) is an evolving and yet falsifiable science which is at it's infancy (primarily with respect to home brewers levels of understanding, but certainly I would hope not with respect to the science labs of the major commercials), whereas the falsifiable science of ppm based Water Profiles has had nearly two centuries within which to evolve virtually unchallenged and become thereby in essence fully entrenched within the minds of those unawares as if it were a whim or faith based gospel. I'm merely attempting to crack open an mEq based door to potential advancement in the pursuit of Water Profile truth. The future in home brewing is yours to grasp. I'm old. My aim is to both enlight and offer tools to aid in this future. It will largely be the task of others to step through the now cracked open door for homebrewers to mEq based Water Profiling.

All (real) truth passes through three stages. First it is ridiculed. Second it is violently opposed. Third, it is accepted as self evident.

19th Century Philosopher Arthur Schopenhauer (with the word "real" seen in parentheses added by me).

The evolving (yet ever replaceable with something better, as in falsifiable) truth value of mEq's lies at the heart of the science of Chemistry. ppm's and mg/L's are but means to deriving mEq's. ppm's are incomplete beginnings, and not complete ends. And as such they are (when not utilized whereby to seek completion) defective and unreliable as a means to ends.

 

[dmtaylor]

Heh. LODO enthusiasts think they are at phase three. Non-enthusiasts will never care so are still somewhere between phases zero and one. But I digress.

I think this discussion is still at phase zero. No one understands mEq enough to even have a discussion about it at all whatsoever. Any perceived ridicule is only due to lack of knowledge or care, nothing more. And we cannot all be educators on our own. It's a daunting task and not everyone is good at it. I'm not.

 

[balrog]

To get where one wants to go, one must first know where they are.

And "No matter where you go, there you are."
B. Bonzai

 

[tracer bullet]

Hmm.... I do.

OK then. I was pretty sure you just said you weren't big on water. My misunderstanding.

As I see it the gist of the bashing and desire to place this science into the trash bin of rant essentially seems to derive from a desire to be spoon fed with all of the mEq based answers as to Water Profiling all at once. I can understand this. If the comfort zone of ppm (mg/L) based Water Profiles has been rocked, the immediate knee jerk reaction is to replace it with a fully evolved comfort zone of mEq based Water Profiles.

I think you misunderstand. It feels like (choosing my words carefully), you start with something to the extent of how everyone trying to reach a particular water profile is an idiot. So we ask why profiles are bad, and what we should do instead. And you get defensive and won't say.

It's not what you say, it's how you say it. As mentioned before, I'm not scolding you. Just explaining that... you are highly regarded, and we'd love to learn from you, but so far that opportunity has been missed by a mile.

mEq is more important than ppm. Got it.

Now what? All the calculators, yours as well I believe, give pH and mineralization in ppm. And they have some indicators for various target profiles such as "hoppy, medium", yours as well. Other than knowing the calculators aren't perfect, or perhaps just suck and are useless if you are trying to go there, is there anything else for us to know?

All ears here, truly.

 

[whattabrau]

Thanks, that does make sense. Is that why Ca++ is listed, it has a ++ charge and requires -- to be equal?

Yes, either one -- (e.g. SO4-- ion) or two -'s (e.g. Cl- ion), hence Ca & 1xSO4 and Ca & 2xCl. (It's important to note that SO4 is indivisible in this context, i.e. the 4 in CaSO4 and the 2 in CaCl2 are not conceptually on the same plane)

Incidentally, while the atomic mass of Ca is 40.something, the equivalent mass is 20.something, which signifies that you need to have half as much for the same "oompf" (equivalents). However, for Cl the atomic mass is equal to the equivalent mass (due to the single -) so you have to have exactly as much as the "ooompf" you desire. In other words, if you divide the ppm (mg/L) of Ca by 20.something, you get mEq/L. And if you're wondering why ppm (10^-6) and mEq (10^-3) don't need scaling, it's because atomic mass is defined so that x moles of a substance will have a mass of x*atomic_mass grams (not kilograms cf. liters), so milligrams => millimoles => milliequivalents.

Hope that continued to make sense.

 

[Silver_Is_Money]

@tracer bullet : Again, the answer lies within my OP, wherein I stated:

Personally, I've made beer recipes that were CaCl2 forward, and then brewed essentially the same recipes in CaSO4 forward water and not truly noticed any difference.

And it seems that in a majority of their test cases, when Brulosophy has touched upon this subject (albeit willy-nilly) their blind to the changes audience of testers have generally concluded likewise. Where I perhaps erred in saying this as early on as I did was in not being more clear as to maintaining a requisite Ca++ mEq's level consistency.

I then moved immediately into looking at Cations as opposed to Anions with respect to where flavor differences may lie. And then I offered a link to a peer reviewed scientific study which has discerned that the very sense of taste itself revolves entirely around Calcium, which is a Cation.

And then I detailed as to why (in a world where some mash and sparge, and others mash only) the ppm's of Calcium alone are not sufficient (and rather are highly defective) in defining what is required for Calcium, whereas mEq's are fully sufficient.

As to calculators, one would hope that they internally convert ppm's into mEq's, and more importantly, do so correctly, whereby to deduce downstream solutions more correctly (which is another subject of contention in itself). But the point of educating is to provide the tools which will permit people to derive usable answers without the crutch of a calculator. In a world of complete dependence upon smart phones, this may seem highly confusing. But I've gone better than 25 years now without even owning a TV, let alone a smart phone.

As to why calculators call for input in ppm's (mg/L's), if (as @dmtaylor has succinctly deduced) virtually no one at this stage of the game at the home brewing level even knows what an mEq is, there is little choice but to digress to ppm's. Hopefully at some future juncture this will change.

 

[Silver_Is_Money]

A brief, highly tentative, and preliminary (I.E., speculative) ballpark for ones mEq based mineralization schema might look something like this:

Czech Pilsner like styles: 5 mEq's of Ca++ ions per Kg. of grist
Stout or Porter like styles: 10 mEq's of Ca++ ions per Kg. of grist
German Pils like styles: 15-20 mEq's of Ca++ ions per Kg. of grist
British Bitter like styles: 20-30 mEq's of Ca++ ions per Kg. of grist
Various IPA like styles: 30-50 mEq's of Ca++ ions per Kg. of grist

Secondarily, one may wish to select at their choosing as to which Anion(s) (mainly here being Cl- or SO4--) they desire to introduce, as these will inherently be attached to the Ca++ within ones selection of minerals.

 

[dmtaylor]

FYI -- I must advise against pickling lime (CaOH2) for your Ca++ needs in most styles. Stick to the gypsum and/or chloride.

 

[Silver_Is_Money]

CaCl2 ~= 0.0555 grams per mEq of Ca++ (Calcium Chloride in the Anhydrous State)

CaCl2.2H2O ~= 0.0735 grams per mEq of Ca++ (Calcium Chloride in the Dihydrate State)

CaSO4.2H2O ~= 0.0861 grams per mEq of Ca++ (Gypsum, I.E., the Dihydrate State of CaSO4)

 

[hout17]

I think this is something interesting to pursue but in regards to my homebrew I would have to pass. My beer tastes good with ppm adjustments so it is moot to me.

Gordon Strong adjusts by taste from what I've read and isn't good tasting beer what we are really after?

I'd rather try some old farm house techniques than mess around with this lol.

What it boils down to is how far in to the weeds do you want to go?

Most people can make good beer by throwing some grains in the water they have without adjustments anyway.

 

[Silver_Is_Money]

Placing it all (preliminary and tentative as it is) within a single post for ease of reference and copying:

Czech Pilsner like styles: 5 mEq's of Ca++ ions per Kg. of grist
Stout or Porter like styles: 10 mEq's of Ca++ ions per Kg. of grist
German Pils like styles: 15-20 mEq's of Ca++ ions per Kg. of grist
British Bitter like styles: 20-30 mEq's of Ca++ ions per Kg. of grist
Various IPA like styles: 30-50 mEq's of Ca++ ions per Kg. of grist

CaCl2 ~= 0.0555 grams per mEq of Ca++ (Calcium Chloride in the Anhydrous State)
CaCl2.2H2O ~= 0.0735 grams per mEq of Ca++ (Calcium Chloride in the Dihydrate State)
CaSO4.2H2O ~= 0.0861 grams per mEq of Ca++ (Gypsum, I.E., the Dihydrate State of CaSO4)

 

[marc1]

Placing it all (preliminary and tentative as it is) within a single post for ease of reference and copying:

Czech Pilsner like styles: 5 mEq's of Ca++ ions per Kg. of grist
Stout or Porter like styles: 10 mEq's of Ca++ ions per Kg. of grist
German Pils like styles: 15-20 mEq's of Ca++ ions per Kg. of grist
British Bitter like styles: 20-30 mEq's of Ca++ ions per Kg. of grist
Various IPA like styles: 30-40 mEq's of Ca++ ions per Kg. of grist

CaCl2 ~= 0.0555 grams per mEq of Ca++ (Calcium Chloride in the Anhydrous State)
CaCl2.2H2O ~= 0.0735 grams per mEq of Ca++ (Calcium Chloride in the Dihydrate State)
CaSO4.2H2O ~= 0.0861 grams per mEq of Ca++ (Gypsum, I.E., the Dihydrate State of CaSO4)

Is your proposal to only include this in the mash, with sparge water being RO/Distilled?

Or is mEq/Kg for all the water in the brew?

Determining anion amounts based on mEq rather than ppm could be a "cleaner" way to look at things. The Ca++ contribution to flavor on its own is something new to me. It would be hard to tease apart from the anion contributions, though.

I think that I would be able to tell the difference between a high sulfate vs a high chloride beer, with Ca++ being the same between them, but I have not tested it. The dry sulfate flavor is easy to picture in my mind. The chloride flavor not as much, although I've tasted higher concentration solution and it's very minerally in a bad way.

Perhaps tasting equivalent dilute solutions of NaCl, KCl, and CaCl2 could help tease apart what the different ions do for flavor. They could be made with controlled cation mEqs and, separately, controlled anion mEqs.

 

[Silver_Is_Money]

Is your proposal to only include this in the mash, with sparge water being RO/Distilled?

Or is mEq/Kg for all the water in the brew?

Determining anion amounts based on mEq rather than ppm could be a "cleaner" way to look at things. The Ca++ contribution to flavor on its own is something new to me. It would be hard to tease apart from the anion contributions, though.

I think that I would be able to tell the difference between a high sulfate vs a high chloride beer, with Ca++ being the same between them, but I have not tested it. The dry sulfate flavor is easy to picture in my mind. The chloride flavor not as much, although I've tasted higher concentration solution and it's very minerally in a bad way.

Perhaps tasting equivalent dilute solutions of NaCl, KCl, and CaCl2 could help tease apart what the different ions do for flavor. They could be made with controlled cation mEqs and, separately, controlled anion mEqs.

1) As currently envisioned, mash only, with sparge being RO/Distilled. (with emphasis here upon "as currently envisioned"). Note that in this methodology, mEq's are independent of water volumes, and thus independent of process, such that no-sparge and the various of mash/sparge volumes of water and chosen mash thicknesses are irrelevant. Thus this methodology is not a "Water Profile" perspective at all.

As to the case for already mineralized source water however, mEq's would then need to be computed (summed) on an overall water basis whereby to remain consistent with the style guidelines as to mEq's with regard to finished beer mineralization levels.

2) At the generally moderate Anion levels used for most brews I believe it may prove difficult to discern between ones Anions, as witnessed for multiple of Brulosophy triangle tests. But just as for you, I also believe this perspective "may" change as Anion levels get really cranked up to the moon. (with emphasis upon "may").

 

[cire]

A brief, highly tentative, and preliminary (I.E., speculative) ballpark for ones mEq based mineralization schema might look something like this:

Czech Pilsner like styles: 5 mEq's of Ca++ ions per Kg. of grist
Stout or Porter like styles: 10 mEq's of Ca++ ions per Kg. of grist
German Pils like styles: 15-20 mEq's of Ca++ ions per Kg. of grist
British Bitter like styles: 20-30 mEq's of Ca++ ions per Kg. of grist
Various IPA like styles: 30-40 mEq's of Ca++ ions per Kg. of grist

Secondarily, one may wish to select at their choosing as to which Anion(s) (mainly here being Cl- or SO4--) they desire to introduce, as these will inherently be attached to the Ca++ within ones selection of minerals.

There were times when I too pondered this as a principle. I really don't wish to take sides here, but there were brewers before there were chemists. Did brewers used grains per gallon, and today ppm, because they were aware of limits to solubility, and knew they were different in water and wort? Equivalents are essential to check and confirm water balance and once understood do simplify many calculations, but there are work-arounds for most else using ppm.

The paper linked below long predates the work by Paul Kolbach, so revered by many and, I fear, to the exclusion of many equally important works on the influence of minerals in brewing liquor. This paper explains why mash pH is influenced by calcium but not by magnesium, though magnesium does influence wort pH. Other reasons too suggesting why pH prediction calculators may not work as hoped and expected by so many. But the main relevance to this thread is its inclusion of the subject of "Solubility Products", and solubility can be most simply measured in ppm. It's a long read, but that's because it covers the subject more widely than what we have of Kolbach's work.

https://onlinelibrary.wiley.com/doi/epdf/10.1002/j.2050-0416.1939.tb05961.x

 

[Silver_Is_Money]

Some very quick takeaways from what was on my part a cursory read through of the above linked 1939 published study.

1) Calcium reactions are generally said at several junctures to be stoichiometric in nature, meaning that Calcium's reactions on an mEq to mEq basis generally ring true. But due to various unknowns and complexities, the cut and dried (I.E., highly settled) nature of the work of Kolbach is seriously brought into question, and should never have been elevated to the unfalsifiable status of "settled science" in the first place. But at long last modern efforts of chemical research (science) are finally rediscovering this flaw in Kolbach's work on the impact of Calcium and Magnesium upon pH.

2) The impact of Magnesium as regards its hindrance of Calcium's downward effect upon pH during the mash is a good reason to either outright avoid, or otherwise attempt to minimize the use of Magnesium as regards mineral additions. We have to our favor that the negative impact of Magnesium upon flavor has long been known, and good practice has long called for it's minimization on a minerals added basis. We have also to our favor that various of acids (and sometimes bases) are generally favored over the use of Calcium as a means to pH adjustment.

3) During the boil Magnesium ceases to act as a hindrance to the dropping of pH, and it's presence accelerates and magnifies pH drop across the boil.

4A) A lot of compounding factors are at play whereby to introduce roadblocks, and calculators at any level of internal math modeling sophistication and logical stoichiometric (I.E., mEq for mEq) accuracy and consistency clearly are not capable of properly juggling all of them.

4B) Short version: Some level of empiricism (mainly in the nature of educated guessing) must inevitably be tolerated, even when the presence of such is not generally desired, and the "ideal" is always upheld to be one whereby to strive in the direction of eliminating as much of it as is possible.

 

[mabrungard]

I’m hoping that the intelligent readers realize that ppm is a mass of material divided by a volume of solute. mEq or Eq is just a mass (okay, it also involves the ionic charge, but that disappears since we’re comparing the same salt in either comparison).

The reason that typical brewing software employs ppm (aka mg/L) is because water companies and labs report that way and it removes the volume of water from the calculation. The use of mEq or Eq isn’t easier, more correct, or better. It’s just different. It’s just another way of performing the same calculation.

 

[Silver_Is_Money]

I’m hoping that the intelligent readers realize that ppm is a mass of material divided by a volume of solute. mEq or Eq is just a mass (okay, it also involves the ionic charge, but that disappears since we’re comparing the same salt in either comparison).

The reason that typical brewing software employs ppm (aka mg/L) is because water companies and labs report that way and it removes the volume of water from the calculation. The use of mEq or Eq isn’t easier, more correct, or better. It’s just different. It’s just another way of performing the same calculation.

ppm means parts per million parts on a unit weight for unit weight basis. It is not a mass of material divided by a volume of solute at all. The concern for charges and charge balance looms large in chemistry, and it forms the very core of the science of chemical reactions (in conjunction with dissociation considerations). The charges do not simply magically vanish. They (in the form of electron orbital clouds) are critical to an understanding of chemistry at any level. And ppm does not speak to charges at all.

And worse, ppm and mg/L are not the same measure at all. We have traveled this path before.

Here's the deal. Eliminate Eq's and/or mEq's from your software completely and then detail to us as to how well it will function without considering them, or the charges they address. After all, ionic charge disappears.

 

[Silver_Is_Money]

When CaCl2 is added to water the density of the subsequent solution is altered from that of water. The density of the solution does not remain a nominal ~1.00000... g/CC, and as such ppm and mg/L are not equivalent (albeit that at very minute levels of CaCl2 dissociated within a large volume of water, it may seemingly appear that there is equivalence, particularly if you have heard a zillion times that they are equivalent). But continue adding ever more CaCl2 to water, and the disparity between ppm and mg/L soon looms large and becomes significant.

 

[Protos]

I've made beer recipes that were CaCl2 forward, and then brewed essentially the same recipes in CaSO4 forward water and not truly noticed any difference.

I started treating my water not so long ago, some 40 to 50 batches back. Having built and tried multiple water profiles, I've come to the same surprising conclusion: Very little difference if any.
What did really matter was controlling Bicarbonate and Alkalinity: better efficiency, harsh hop flavours gone. Changing various salt combinations though never resulted to me in a detectable difference. IDK, maybe I'm not sensitive enough to water salts. It's just all the same to me, whatever is the Cl:SO ration.

So now I just boil my overbicarbonated water and don't fiddle with salts anymore.
Except when I recreate a certain recipe to a tee, including its specific water.

 

[Silver_Is_Money]

I started treating my water not so long ago, some 40 to 50 batches back. Having built and tried multiple water profiles, I've come to the same surprising conclusion: Very little difference if any.
What did really matter was controlling Bicarbonate and Alkalinity: better efficiency, harsh hop flavours gone. Changing various salt combinations though never resulted to me in a detectable difference. IDK, maybe I'm not sensitive enough to water salts. It's just all the same to me, whatever is the Cl:SO ration.

So now I just boil my overbicarbonated water and don't fiddle with salts anymore.
Except when I recreate a certain recipe to a tee, including its specific water.

Such forthright honesty in the face of potential ridicule is to be commended.

 

[BrewnWKopperKat]

background: There's a new (to me) 'start page' for water over at the AHA web site (link). Following the links gets one to ...

There is a HomeBrew Con 2018 presentation (Putting Brewing Water in Perspective; link) where a pale ale was brewed with two different water profiles. The evaluations are worth a read. For those interested, there appears to be sufficient information in the PDF to reproduce the experiment. There's also an video (which I didn't look at while previewing links / content).