Alkalinity/pH and salts again!

[mabrungard]

Residual alkalinity is not really something a brewer should concern themselves with. Its alkalinity that ALL brewers should be aware of in their water supply. Its what has a profound effect on mashing pH.

I've seen that electronic alkalinity testing unit, but I don't think its the best way to go. Alkalinity tests kits used for aquariums are quite accurate and inexpensive. Get one of the colorimetric liquid test kits since they are more accurate than test strips.

There may be some inaccuracy in the original work on RA by Kohlbach, but there is no question that calcium and magnesium do produce an acidifying reaction in the presence of malt materials. While it may now be superseded by newer research, its good enough for use in most brewing applications.

 

[Peebee]

... I've seen that electronic alkalinity testing unit, but I don't think its the best way to go. Alkalinity tests kits used for aquariums are quite accurate and inexpensive. Get one of the colorimetric liquid test kits since they are more accurate than test strips. ...

That "Hanna" device I pictured earlier is a colorimeter device. Cheap, but not that "cheap"! I concluded the water was outside its range. But they didn't specify a minimum alkalinity it would work at. I do now understand low alkalinities can be difficult!

I was surprised the mini-titration kits (Salifert, popular aquarium choice) came up with consistent results. But that was pushing them using 4 or 8 times the sample to test. And they are a little tricky to use precisely. The only reason to suspect the Salifert as "good" (it was two years past its "best before" date!) was it returned results similar to professional analysis. Hanna (the most expensive) around 12-13ppm as CaCO3, Salifert about 7 ppm as CaCO3, Professional (2, sent away for) at 8ppm as CaCO3.

 

[Peebee]

I haven't finished my spreadsheet yet so can't offer it as a download. But I'm still working on it and this is a glimpse at it's guts ... the stuff I believe folk need protecting from and the purpose of this spreadsheet (it filters out the un-necessary stuff that brewers seem to waste so much time agonising over). Its typical over-the-top spreadsheet for me, I just can't help but play with the obscure features.

This isn't to post what I know about water, it's for anyone to point out what I've missed and suggest enhancements. I welcome any help with the project. If this fills a few minutes of anyones time I've done okay. If you don't make it past the next couple of sentences, That is what I expect!

Note the spreadsheet is a "pre-processor". It is not a water profile builder. And the narrative is tongue-in-cheek!

The "Foetid Mire" is my repository of stuff you don't want (but it might reveal useful information). It's been designed for low dissolved solids water (well under represented for brewing water calculators) and mainly for users bogged down in arcane "Hardness" stuff.

I've noticed far fewer Americans have to put up with the "Hardness" stuff. I've extended it some to cover more Sodium in the water as I believe this is more an issue for American brewers (municipal water softeners?). Its original intension was to wean UK homebrewers off RO Water and the like. Some of the water in America forces users to use it, but in the UK there is no need for it (But UK citizens like to copy America ... they always have!).

This snip shows some behind-the-scences stuff with hardness. It's all grey to discourage users wasting time with this stuff. I will repeat though, there are some folk who can do amazing things with "Hardness" and "as CaCO3", but the key word in that is some, ... most can't, but they can make lots of mistakes trying! I try to emphasis this by working here with Sodium "as" Calcium Carbonate (CaCO3) rock ... If that fails to illustrate the folly in using it, what will? (Well, I say "folly", but if careful it does work!).

The water being processed here is from Battle in the UK. Loads of Sodium, moderate alkalinity but otherwise fairly low Calcium. The report is terribly unbalanced. But I mess with it a little more:

A little lower than the previous screenshot: A proporton of the alkalinity is diverted away from being counted as "Hardness".What has been estimated (purely on a proportional basis) as "Sodium" salt. This is the most contaversial assumption but I could find nothing to suggest that anything other than a proportional basis was at work.

The result is a perfectly balanced report, not one with more temporary hardness than total hardness, or "negative permanent hardness".

The purpose of the spreadsheet is to remove all the un-necessary "Hardness" confusion. but if its dealing with the un-necessary stuff correctly, it's getting the necessary stuff right too.



I'm currently trying to get some flexibility in the Alkalinity calculations. Note this spreadsheet calculates Alkalinity: It doesn't attempt to use reported Alkalinity from a different point in time (the problem with reports covering a number of reports taken at differing times and averaging individual bits of it so it's all out-of-sync).

I also want to incorpoate the stuff handed me by @Silver_Is_Money: I'm beginning to appreciate how useful that stuff could be. But that's for later, I just want it back doing most things right for now.

 

[VikeMan]

I'm just going to add a couple things here for future browsers. In brewing terms, Hardness and Alkalinity are not the same thing. And neither is a subset of the other. And neither is some sort of substitute for the other. They often go hand in hand, but not always. And knowing one doesn't allow you to determine the other without measurement.

Illustrative examples:
- Add some CaCl2 to distilled water. You now have hardness (from Ca++), without alkalinity.
- Add some NaHCO3 to distilled water. You now have alkalinity (from HCO3-), without hardness.

Both Hardness and Alkalinity matter to mash pH. (The Hardness matters because of the Residual Alkalinity phenomenon.)

Hardness is determined from Ca++ and Mg++, whether it's temporary, permanent, or (often) some of each.

 

[Peebee]

... Hardness is determined from Ca++ and Mg++, whether it's temporary, permanent, or (often) some of each.

Not entirely true. Temporary Hardness has more to do with Alkalinity and nothing at all to do (directly) with "Hardness". Just the sort of example of "Hardness" that reinforces my wish to see it disappear. Forever.

"Hardness" is a bag of rotten apples; someone with your excellent reputation shouldn't say anything that might be confused with you defending it. I would much rather be seen on the same side of the fence as you.


Whether "Hardness" matters, or "Residual Alkalinity", the subject I'm discussing pulls out before the question of "RA" raises its head. It covers what comes out of a tap ... no further.

 

[VikeMan]

Not entirely true. Temporary Hardness has more to do with Alkalinity and nothing at all to do (directly) with "Hardness".

Temporary hardness certainly is directly related to "hardness," in that hardness is one of the things that determines temporary hardness, and you can't have temporary hardness without having hardness in the first place. I agree that alkalinity is also a factor in computing temporary hardness, but my point is that alkalinity is neither permanent hardness nor temporary hardness. I thought from some of your posts in this thread that you were saying you can somehow use alkalinity in place of hardness. Perhaps I misinterpreted.

Just the sort of example of "Hardness" that reinforces my wish to see it disappear. Forever.

It can't really disappear forever. It affects mash pH.

"Hardness" is a bag of rotten apples; someone with your excellent reputation shouldn't say anything that might be confused with you defending it. I would much rather be seen on the same side of the fence as you.

I'm not "defending" hardness per se. It's a fact of life, and if you want to control mash pH, you can't ignore it, or rather, you can't ignore the levels of Ca and Mg that comprise it. If by "bag of rotten apples" you mean often misunderstood, ok, but we could say that about anything in the pH/mash pH/alkalinity/residual alkalinity realm.

Whether "Hardness" matters, or "Residual Alkalinity", the subject I'm discussing pulls out before the question of "RA" raises its head. It covers what comes out of a tap ... no further.

To be totally honest, I've read the thread a couple of times, and am not sure what your goal here is. Are you trying to come up with a pH predictor that doesn't need to know how much Ca and Mg are in the water? I think that's impossible, but I suspect that's not the goal, particularly because you say "what comes out of a tap ... no further." Are you simply saying that the term "hardness" confuses home brewers? FWIW, I haven't seen any mash pH calculators that even ask for a "hardness" number. They ask for Ca and Mg. And there's no need to even understand the concept of hardness to use those calculators.

 

[Peebee]

@VikeMan: Okay, I accept you in your roll as Devil's Advocate, but it'll take me a while to tackle those questions and I want me tea! Bit of an inconvenience all this time zone business ... when I get round to it it'll be tomorrow (at least).

But I'll try to deal with the last comments now:

One of the things I like about this forum is users aren't so hung up on water "Hardness". Back over here (UK) new users are plagued with it. A really simple to understand subject ... water for brewing beer ... is transformed into a hideous subject by loading it with Hardness using bazaar contradictory units that occasionally get called "equivalents", but no-one says what they might be "equivalent" to? We've all been brought up with "Hardness". We know what it is 'cos Grandad talked about it. We expect it to be the answer to all our beer brewing problems. And what the hell is Alkalinity really? Etc. People don't know what they're doing, and listen to self-styled experts, some of whom have gone to the extreme lengths of learning how to spell "Hardness".

I took on this task because I have the time available to me and it does me good to feel a bit useful. I bought the subject onto this forum because I was after some answers that I wasn't getting from over my side. I'm not sure I can properly cover America with the work I'm doing because your water supplies are so very different (we mostly have surface runoff that never travels big distances, whereas you are on a vast continental sheet). We're just on the edge of a continental sheet and the few water-bores we have would look like the work of someone with a toothpick on your side.

So, I don't think "Hardness" confuses people. But you might be amused by some of their descriptions.

And lastly, ... here! You've turned your argument on its head. "I haven't seen any mash pH calculators that even ask for a "hardness" number". That is not playing nice.

 

[VikeMan]

One of the things I like about this forum is users aren't so hung up on water "Hardness". Back over here (UK) new users are plagued with it.

I wasn't aware of an obsession with Hardness in the UK. If it's being misunderstood and/or misused, well, I'm glad that doesn't seem to be an issue over here.

I took on this task because I have the time available to me and it does me good to feel a bit useful. I bought the subject onto this forum because I was after some answers that I wasn't getting from over my side. I'm not sure I can properly cover America with the work I'm doing because your water supplies are so very different (we mostly have surface runoff that never travels big distances, whereas you are on a vast continental sheet). We're just on the edge of a continental sheet and the few water-bores we have would look like the work of someone with a toothpick on your side.

I'm still not sure what your task is. Can you state the goal in 25 words or so?

And lastly, ... here! You've turned your argument on its head. "I haven't seen any mash pH calculators that even ask for a "hardness" number". That is not playing nice.

I don't think it's inconsistent at all, if that's what you mean here. The hardness matters a great deal. But fortunately, brewers don't have to compute it themselves or even understand it. The models use its components.

 

[Peebee]

Can you state the goal in 25 words or so?

Easy:

Remove all confusing reference to Hardness and "as CaCO3" from a water report. Express only the information needed ("ions", of concentration more than one part per million - ppm), which in the UK tap water is Calcium, Magnesium, Sodium, Chloride and Sulphate. The "artifacts" from pollutants, Nitrate and Phosphate, can come in useful (balancing). And "Alkalinity" as Bicarbonate, although it appears that can be calculated from the rest.

I seem to be successful at it too, there was an example higher up this thread .... >here<. The spreadsheet doing this is a "pre-processor", clearing a report of un-necessary drivel for entry into a "Brewing Water Profile Builder". Everything as ppm or mg/l (also Alkalinity represented as Bicarbonate but for this situation its quite all right to think it is Bicarbonate).

If that's too long, just the first sentence will do.

 

[Peebee]

Temporary hardness certainly is directly related to "hardness," ...

Hardness was once something that just interfered with creating a lather from soap. In more recent times (2-3 centuries) it came to mean multi-valent metal ions in water, chiefly represented by Calcium and Magnesium. Temporary Hardness came to be recognised as the same metal ions but associated with "carbonate and bicarbonate". It could be removed by boiling ("bicarbonate" forced to change to insoluble carbonate and precipitate out). Temporary Hardness is directly associated with Hardness in that it contains the same "multi-valent metal ions" (I'm sorry for saying nothing directly to do with Hardness). Indirectly because it gives the impression chalk or limestone causes Hardness (Temporary Hardness also gets called "Carbonate Hardness" or "KH"). Gets messy when "Carbonate Hardness" is associated with non-Hardness mono-valent metals like Sodium: Temporary Hardness is losing relevance and now gets clustered with Alkalinity (as Carbonate Alkalinity).

There is obvious "cross-over" between the subjects of Carbonate Hardness and Carbonate Alkalinity. And with that confusion exists between the subjects. Solution: Do away with Hardness, it has nothing to offer, and concentrate on Alkalinity. America seems to be well down that route, but the UK (and other places in the world) seem reluctant to let go of it (Hardness).

With it can go "as CaCO3" too. Originally setup because Calcium Carbonate is blessed with some easy to remember numbers (50. 100, 40% "as" Ca, etc), great for pen & paper calculations, but we've got calculators and mobile phones now. "As CaCO3" just causes confusion, to the point homebrewers have been attempting to dissolve the real thing in water for years. It's not very obvious that "as CaCO3" for hardness includes Magnesium to. It amuses me to declare Sodium "as CaCO3" in the bowels of that spreadsheet I'm creating (where nobody needs to see it). Others can do amazing things with "as CaCO3" and Hardness, but they are rarities who really understand the subject: Most haven't a clue what to make of the confusing drivel it creates.

... It can't really disappear forever. It affects mash pH.

Calcium and Magnesium does have an indirect influence on mash pH, but the real ion concentrations cover that much better than Hardness and "as CaCO3".

... if you want to control mash pH, you can't ignore it ...

(Hardness that is) ... Yes you can! Calcium and Magnesium (etc.) may have little indirect influence on mash pH, but it doesn't need hardness to interfere with working it out ... Carbonate Hardness, or better, Alkalinity, on the other hand has loads to do with it.



Phew! Will that do as my detention essay? All because I incorrectly said Temporary Hardness has nothing directly to do with Hardness ... I fink the punishment was mean!

 

[VikeMan]

Remove all confusing reference to Hardness and "as CaCO3" from a water report. Express only the information needed ("ions", of concentration more than one part per million - ppm), which in the UK tap water is Calcium, Magnesium, Sodium, Chloride and Sulphate. The "artifacts" from pollutants, Nitrate and Phosphate, can come in useful (balancing). And "Alkalinity" as Bicarbonate, although it appears that can be calculated from the rest.

Sure, you can calculate (estimate) Bicarbonate from the rest, including pH, or without pH if you just want alkalinity "as bicarbonate." But why not use the bicarbonate and/or alkalinity numbers that are already on the report? And if it's expressed "as CaCO3," multiply by 1.22 (if the pH tool doesn't already do that for you). I'm not sure what new ground you're breaking (for US brewers anyway). And when a calculator doesn't ask for Hardness, who cares what its units are? Who is truly stumped by that? Again, USA perspective here.

As for banishing "as CaCO3" from water reports, good luck tilting at that windmill. These reports (the ones I'm familiar with, such as Ward Labs) were not originally designed for brewers, and there are very good reasons to express some things "as CaCO3" (or "as" other things) for scientific, agricultural, and industrial users. In the USA, the mistake I occaisionally see brewers making is misinterpreting (or rather not interpreting) "SO4 as S." Fortunately, that one doesn't affect pH, at least.

I seem to be successful at it too, there was an example higher up this thread .... >here<. The spreadsheet doing this is a "pre-processor", clearing a report of un-necessary drivel for entry into a "Brewing Water Profile Builder". Everything as ppm or mg/l (also Alkalinity represented as Bicarbonate but for this situation its quite all right to think it is Bicarbonate).

Again, yes, you can calculate/estimate Bicarbonate. But is it reasonable to expect that a user is going to add another spreadsheet to their process just to get essentially the same answer they would have got by multiplying a number from the report by 1.22 (if necessary)? Because in a water report (USA at least), Alkalinity is the only mash pH calculator relevant number expressed "as CaCO3."

Calcium and Magnesium does have an indirect influence on mash pH, but the real ion concentrations cover that much better than Hardness and "as CaCO3".

I'd say Calcium and Magnesium have a direct influence on mash pH. Do you say indirect because the Ca/Mg has to interact with phosphates from the malt? To me, that's just behind the scenes chemistry, just as salts dissociating into ions is. All "automatic" for the brewer. But it's quite true that Ca/Mg don't affect the pH of plain water. Also, I agree that the real ion concentrations (of Ca/Mg) are the thing that is useful (for the mash pH calculators), rather than Hardness "as CaCO3" (or as anything). Fortunately brewers can completely ignore that line on the water report, because the mash pH tool won't ask for it. When I do a water consult with a brewery, I include the original report numbers, followed by a pared down version with just the enries relevant to mash pH tools and/or to beer flavor, yeast function, etc. I don't do that to reduce confusion though. I do it because I then follow with a discussion of how each of those things affects mash pH and/or flavor (etc.).

(Hardness that is) ... Yes you can! Calcium and Magnesium (etc.) may have little indirect influence on mash pH, but it doesn't need hardness to interfere with working it out ... Carbonate Hardness, or better, Alkalinity, on the other hand has loads to do with it.

I gotta ask... do mash pH calculators in the UK actually ask for a Hardness number? As for Calcium and Magnesium having "little" influence on mash pH, I disagree. I have many recipes that use nothing but CaCl2 and CaSO4 to adjust mash pH.

 

[Peebee]

But why not use the bicarbonate and/or alkalinity numbers that are already on the report?

The original spreadsheet did. I was attempting to make it a choice, but it was creating difficult to iron out errors, so I stopped trying ... one less value to hunt down! The calculated values were close anyway, these analyses were working out about the same too, but with one big difference. They were never exactly the same. The reported values never balanced up. And the reason was all the reported values came from different times. Alkalinity was reported some three or four times more frequently than specific ions. The reports were averaged for each individual subject. The result was a total "report" that never actually existed at any point in time. So, neither did the Alkalinity match any particular report (There would be a Maximum set, a Minimum set, and an Average or Mean set).

By calculating the Alkalinity the result would be exactly balanced for a particular "contrived" set. In the case of single analysis results the difference was minimal anyway. It just made sense, or at least made as little sense as the actual reports.

Likewise, I calculate Hardness values too. Yes, the spreadsheet does use "Hardness" even if it's designed to eliminate it. As I've mentioned, UK water reports won't let go of Hardness (they are getting better) and some things can only be extracted from Hardness as a result. My own water has no specific analysis for Calcium, it must be extracted from Hardness analysis. So I get Calcium Hardness reported as CaCO3. The water company isn't unaware of the limitations and do provide a proper report of Magnesium, converting it the opposite way to "Magnesium Hardness" as CaCO3 () . They don't actually say "as CaCO3" either (This is their summary report, the don't publish hardness stuff in the full reports ... These are pretty good for the UK, some UK reports are dire):

Full and Summary were published about 4 months apart, the "Alkalinity" is way too high to match the Hardness analysis.

Is the purpose of the spreadsheet making sense now?



European water calculators are rare these days, we mostly use Amerian ones. European ones are typically handicapped with "Hardness" anyway. Historically it was a teaspoon of this, a tablespoon of that ...

[EDIT: Oh aye ... in case anyone notices, "Hardness [Magnesium] (mg/l)" is a misprint! 1.16x4.118=4.77 not 4.50.]

 

[Silver_Is_Money]

There are water reports which only indicate 'Total Hardness' (TH, as CaCO3) and leave you to guess as to Ca++ and Mg++. Thanks to initial work done by Kai Troester in this area, there is a method which makes a fairly decent (on average) guess as to these two ions. This method is derived as follows (wherein only that which is bolded in black at the end needs to be remembered):

First, convert whatever units your total hardness is reported in into units of ppm (mg/L) of total hardness "as CaCO3".

Next, it appears as if an aggregate average of all of the worlds fresh water sources indicates that "on average" roughly 72% of fresh waters "total hardness" is derived from Calcium, with roughly 28% from Magnesium.

MW of CaCO3 = 100.0869
MW of Ca++ = 40.078
MW of Mg++ = 24.305

100.0869/40.078 = 2.4973
100.0869/24.305 = 4.118

And since total hardness is the measure of combined Ca++ and MG++:
Total Hardness (as CaCO3) = 2.4973(Ca++) + 4.118(Mg++)

Therefore, on average:
Ca++ ~= (0.72*TH)/2.4973
Mg++ ~= (0.28*TH)/4.118

Example: A report indicates total hardness = 186 mg/L (as CaCO3), but it doesn't say what the mg/L values for Ca++ and Mg++ are:

Ca++ ~= (0.72*186)/2.4973
Ca++ ~= 53.6 mg/L
Mg++ ~= (0.28*186)/4.118
Mg++ ~= 12.6 mg/L

Our educated guess as derived from only total hardness is thus: Ca = 53.6 mg/L (ppm), and Mg = 12.6 mg/L (ppm)

*Note: You may find it necessary to convert Total Hardness as seen on your report from other 'units' to mg/L (ppm) 'units' first, before applying these simple (highlighted in black above) formulas.

 

[VikeMan]

Is the purpose of the spreadsheet making sense now?

Well, yes. Partially anyway. If your Ca/Mg numbers are in odd units (i.e. "as CaCO3") or not directly reported at all (Ca), of course you have to convert/compute them. But...a computed alkalinity estimate of 25.01mg/l instead of a reported average of 25.42mg/l? Is there a recipe where the predicted mash pH moves by even 0.01 as a result of that difference?

I'm starting to suspect that "academic exercise" may be a part of your motivation for this, and there's nothing wrong with that. I admit I could be wrong.

 

[Peebee]

I'm starting to suspect that "academic exercise" may be a part of your motivation for this, and there's nothing wrong with that.

I was going to vehemently deny that, but ... you might be right? I'm trying to stuff me head with academic stuff that it abruptly emptied itself of a few years ago. And thanks for picking out:

... a computed alkalinity estimate of 25.01mg/l instead of a reported average of 25.42mg/l?

... I'd forgotten I'd written that in this thread. Got me reviewing what I've said. Seems I'm doing a bit of repeating myself in this thread, but I think that's normal when getting older! But what I also said about those figures is instead of making me proud (what I calculated was virtually the same as what was reported), it made me suspicious! BTW, I draw a line at "parts-per-million" ... parts-per-billion (and fractions of ppm) is just "cloud-cuckoo-land".

But the overall motivation for doing this:

The original work was already done ... the "Defuddler" spreadsheet could fulfil its purpose of stripping a water report of all the junk it accumulates, the muddle of different units (some of which were imaginary), the confusion of mixing arcane methods into "new" (not that "new"!), the distortions created by Sodium salts even. It just put out the six ions (Ca, Mg, Na, SO4, Cl and HCO3) that any water calculator would be happy with.

What I came here for is a clue as to why and how low-alkalinity water dropped sharply in Alkalinity between where it was dosed to reduce pipe-corroding acidity (with calcium hydroxide) & tested, and the house tap (ultimately to figure why I find myself mashing-in at below pH5.0 despite using calculators to adjust the water).

I'm busy now trying to adapt the "Defuddler" with what I've gleaned recently and from here ... most notably from @Silver_Is_Money (i.e. "Cheat!", though he might not have meant it in the way I'm doing!). I'm also trying to establish the formula "[Total Alkalinity = ∑conservation-cations - ∑conservation-anions]" more centrally to the spreadsheet (automates "Bicarbonate" deduction and "balancing") and mEq/l units for calculation ('cos they're easy). Unfortunately, bringing the "Defuddler" into it is guaranteed to cause conflict and miscomprehension ... you know what I mean! (I promise to post the updated "Defuddler" here when it's better done).

 

[Peebee]

Should put: In "Total Alkalinity = ∑conservation-cations - ∑conservation-anions" the sums are in equivalents (mEq/l seems a good choice), so you don't worry about valencies. If I don't put this I'll forget! I was already thinking there's something missing there; next step is I'm not thinking about it anymore.

 

[Peebee]

Ha! I might have been quiet, but I haven't stopped meddling with this spreadsheet! I should be able to post it later today. It's been a bit of a headache, because trying to modify a "finished" spreadsheet was creating a tangled cat's-cradle affair. I have an aversion to enabling the spreadsheet's "circular referencing", I know it would help me lots, but I then feel like I've failed. Some things from the original had to go; one being the option to use the reported "Alkalinity", now it will only calculate it ("as" Bicarbonate).

This is the output entering the numbers from a private report of my own water supply (at the tap):

The reported Alkalinity "as CaCO3" was "8", so the calculated is 14 (13.92 as CaCO3) so miles out? Hardly that! that's a difference of 6 mg/l "as CaCO3". The report didn't list "nitrate" either, the Public Report puts that as 3mg/l and that would have come off the the calculated Alkalinity amount. Silly numbers, I'll find something more substantial to test it on.

 

[Peebee]

Short delay posting the full spreadsheet due to an insignificant error that needed fixing (it wasn't insignificant if you ran in to it!). Meanwhile, this shows one of the objectives (the other objective, coping with high Sodium waters, was covered earlier in the thread):

It's the same water as in the last post (my water!), but the analysis is the public available one (two actually). And the spreadsheet is switched to "Adaptable" mode. Only relevant to water with low alkalinity that is "dosed" (with Calcium Hydroxide, or "Lime") at the water treatment works due to its natural acidity. [EDIT: "2003" on the posted report is a typo!]

It appears that that the Lime is consumed during the journey to the house tap, so the spreadsheet allows the cations to be "tweaked" to lower the Alkalinity to match this drop. It's a "kludge", but I could not find a suitable description of this phenomena. It is described in the narration that is associated with the spreadsheet ... a clip of which:

This tool allows minor tweaks to the "Conservation cations" to modify the Alkalinity. In reality the ion concentrations won't act in this way, but it's a "kludge" to mimic a real situation that has no obviously simple mechanism and has minimal (no) adverse affects on the water's mineral profile. The situation it is designed for the slow drop in alkalinity following "dosing" of the water with Lime to reduce acidity of moorland runoff. The delay suggests the water arriving at taps is much lower in Alkalinity than when tested at the Water Treatment Works.

The "kludge" may find other uses at a later date? Meanwhile, it's a "kludge" and therefore resides deep in the Foetid Mire! The results though are applied directly to the six top boxes if set to "Adapted" (the setting is easily reversed).

The kludge is only applied to cations that can be assumed to be associated with Alkalinity anions (e.g. bicarbonate). The impact on total cation concentrations is insignificant even though in this case all but 65.5% of affected cations have been "removed" (virtually that is). Original concentrations were Ca=22.39, Mg=1.16, and Na=6.86 (all mg/l). But Alkalinity dropped (virtually, or calculated) from 13.97 (mg/l as HCO3) to 9.15 (7.5mg/l as CaCO3), the average results from titrations and professional analysis.

The spreadsheet does this without taxing the user with all the "details". Hopefully it will fix the sub-pH5.0 mashes I'm getting (although I'm not experiencing any ill effects from mashing at pH4.9.).

 

[Peebee]

Ah ... short delays always turn into long delays. While getting this spreadsheet ready to post and going over the "documentation" (my tongue is permanently fixed in me cheek now) it became apparent that all this "calculated" Alkalinity stuff might be good at simplifying the spreadsheet, but it also alienated a load of potential users who had no proper "calcium" and "magnesium" analysis.

It's not uncommon, that first report I mention in my last post has no Calcium analysis. Hence, I need the second listed analysis (the "summary" ... it has all the naff "Hardness" babble).

Just fixing that. I think I'm at the bare minimum of what you can build a complete brewing water profile from: "Total Hardness" (yak! But you can get useful stuff from it with a bit of imagination), Sodium (helps with the imagination!), Sulphate and Chloride. Anything less than four items and I think I'm beaten (at which point it's "just use it anyway". I know where I'm going with it, but will it work?

 

[Peebee]

Sorry for the delay posting a "finished" spreadsheet (i.e. one "finished enough to stand alone while I make it do something else). I'm just polishing up the instructions at moment (there's not many, it was my intention to make it "hands-off").

It's ironic that having driven out the need for "Hardness", I've then had to get it back to cover those less common instances where no Calcium and Potassium Magnesium figure has been published and only an existing "Hardness" figure offers the possibility of building that information (far better if someone produced the information without wrapping it up with "Hardness").


But don't worry about this project's aim of losing "Hardness" forever, and it's artificial side-kick of "as CaCO3" that can go with it. This arcane artificial structure (I mean "Hardness"!) has nothing of value to offer brewers except confusion and miscomprehension. It'll no doubt continue to be used to work out solutions to lime-scaling in boilers and pipes, and by those few brewers who can follow it ... but for everyone else it isn't telling you what you think it is.

Whatever purpose you can apply "Hardness" to in brewing beer, you can find an up-to-date alternative that is easier to learn, easier to deploy, far more accurate, and less likely to trap you in some fantasy world.


I've always been impressed that Americans don't seem to be so hung-up on "Hardness". Talking about "Alkalinity", Bicarbonate, and other real-world brewing water topics. Well, keep it up and don't be diverted by these characters chatting about the greater good of soapsuds bound "Hardness".


Humm, I don't appear to be in good mood today?


[EDIT: Correction: Put "Potassium" where I meant "Magnesium".]

 

[Peebee]

There are water reports which only indicate 'Total Hardness' (TH, as CaCO3) and leave you to guess as to Ca++ and Mg++. Thanks to initial work done by Kai Troester in this area, there is a method which makes a fairly decent (on average) guess as to these two ions. This method is derived as follows (wherein only that which is bolded in black at the end needs to be remembered):

...
Therefore, on average:
Ca++ ~= (0.72*TH)/2.4973
Mg++ ~= (0.28*TH)/4.118

...

Thanks! This is incorporated in my spreadsheet now. Didn't take much 'cos it already had a 7:3 division which just needed changing to 7.2:2.8 plus an acknowledgment.

Haven't sorted the pH stuff yet but I have ideas. It'll have to wait until after I finish this ongoing stuff.

 

[Peebee]

Here go: To make up for my outburst against "Hardness", I've dragged this from another of my posts on another forum:

Illustrates what lies outside of "Hardness's" envelope. All the stuff that can be attributed to non-Hardness cations (Sodium, Potassium, etc.). Including the "Alkalinity" that didn't get counted because it's not: "Carbonate Hardness", is another kind of "Alkalinity", can be attributed to non-Hardness cations, etc.

These "exemptions" don't amount to much normally. But when not "normally" they can be a big deal. And if you've got ion-exchange going on ...

[EDIT: Minor alteration to diagram to make it clearer.]

 

[Peebee]

This is the same diagram as above without all the "Hardness" babble:

Clear demarcation of Magnesium and Calcium. Clear inclusion of non-Hardness Cations. Alkalinity as "Total Alkalinity" not "Carbonate Alkalinity" that can be associated with multi-valent anions; and "the rest" of Alkalinity seperately. Somewhat clearer than mixed up with all that "Hardness" babble?

This might explain why I draw the different ions in vertical columns? The ions are also illustrated as if they are the same as each other (equivalents) using the natural balance of cations and anions in surface water to draw connections between ions and Alkalinity that might otherwise not be suspected.

I'm often accused of making things over-complicated. But who's being the most complicated in this instance? "Hardness" has its place, but do yourself a favour and just be sure you leave Hardness where it is and don't mix it up with other ways of doing things.