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Old 03-18-2011, 03:24 AM   #91
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A little research reveals that there is more to calcium chloride than one at first might think. I've been looking at something in the form of prills from L.D. Carlson labeled simply "Calcium Chloride" and ACS grade Calcium Chloride Dihydrate from Hach. The first thing one notices about the prill form is that a solution of modest strength in DI water has a pH about 10. CaCl2 is a neutral salt (salt of strong acid and strong base) and so does not effect the pH of water in which it is dissolved. So there is something in this product besides calcium chloride. Whatever that something is it is considered (by ASTM E 449) to be calcium hydroxide and who is to say it isn't. IOW if I mix some sodium hydroxide with some pure calcium chloride and make a solution from the miz that solution is indistinguishable one I would make with equivalent amounts of calcium chloride, calcium hydroxide and sodium chloride. So the first thing one does in assaying a calcium chloride product is measure its alkalinity, call that calcium hydroxide and deduct the equivalent calcium from that available to chloride. More significant in the brewing application is that we often add calcium chloride to reduce mash pH. There will be a reduction because the amount of hydroxide is small but calcium chloride products like the L. D. Carlson one will not reduce it as much as we thought it would because we don't think about the hydroxide. There are other impurities as well such as chloride salts of sodium, potassium, magnesium, strontium etc. and, if there has been any exposure to air at all, water of hydration. The Hach material does not result in a high pH when dissolved - not because it is dihydrate but because, being ACS grade, it is free (for the most part) of impurities (except water of hydration which it picks up from the air if not as enthusiastically as the anhydride).

So if we buy something like the L. D. Carlson product should we consider it as the anhydride or dihydrate? And what about the pickle crisp? I don't think there is an easy answer. ASTM wants us to determine the amount of calcium chloride in an unknown by titrating against EDTA in order to find the calcium content. In other words, they want us to find out the calcium hardness of the solution. While their procedure is a little strange (addition of hydroxylamine hydrochloride and sugar) it is basically the same titration as is used for finding the hardness of water so those of you who have hardness kits could test calcium chloride with those.

I'm color blind so I don't see the end points of EDTA titrations very well and so have adapted a low range calcium test in which the test solution is dosed with special indicator and then an excess of chelant (EGTA which grabs calcium only). The amount of color change caused by the EGTA (difference between absorptions at 522 nm before and after addition) is proportional to the amount of calcium in the solution. After a lot of work building a calibration curve I measured the prills as being 78.8% calcium chloride and the dihydrate as being 59.2%. So again, it appears that the prills are the anhydride but with impurities andwater of hydration whereas the dihydrate clearly contains a fair amount of water of hydration beyond the 2. Note: it takes an analyst a few rounds to get comfortable with a new protocol just as it takes a brewer a few brews to get comfortable with a new technique (such as decoction mashing) so I don't have a lot of confidence in those numbers and I don't see that they are going to help in answering the broader question "How much calcium do I get out of a gram of calcium chloride". Pure anyhdrate is 36% calcium but it looks as if the product sold by L. D. Carlson can be as much as 20% stuff other than calcium chloride even after only relatively short contact with air. This implies that the material would be 29% calcium at the low end and 34 - 35% (based on specs for Dow Chemical's anhydrous product) at the top. Then there is the alkalinity aspect of this stuff.

If you really want to be certain, I suppose the better alternative is to get some of the dihydrate in ACS grade from a laboratory supply house but then we'd really want FCC grade for our beer (it is available).

It's probably best to just think of calcium chloride as being 29 - 35% calcium (with equivalent chloride attached) unless you have good reason to think it's dihydrate in which case reduce the range to 22 - 26%. After all is said and done I've used it in beer for years without being aware of any of this.

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Old 03-18-2011, 06:23 AM   #92
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AJ - I really appreciate the effort you have put into trying to answer this question.

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It's probably best to just think of calcium chloride as being 29 - 35% calcium (with equivalent chloride attached) unless you have good reason to think it's dihydrate in which case reduce the range to 22 - 26%. After all is said and done I've used it in beer for years without being aware of any of this.
For me, at least, this is "good enough for government work".
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Old 03-24-2011, 02:39 PM   #93
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Do the calculators (refering to THs, Bru'n, and Kai's) predict mash pH well when you brew; say, a ~10 SRM Maerzen with no crystal malts and no roasted malts? It's going to be just 10# Munich, 1.5# Dark Munich, and .5# Carafoam (technically a crystal malt but...should it be included as such where mash pH is concerned?). For example, Kai's calculator asks for the amount of roasted grain and for a predicted SRM; does it assume most of the color is from crystal malts if the SRM is 10 and the roast malt is 0%?

I'll likely just skip sauermalz and have lactic ready but I was just curious.

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Old 03-31-2011, 04:38 PM   #94
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Some spreadsheets are flawed because they allow or recommend the brewer to add too many or too much mineral to their brewing water. In addition, its impossible to assess if a particular water profile is actually what was used by brewers in those locals. In the case of Bru'n Water, I performed extensive research on the current and historic sources of water in those places and studied if the current water quality could still be applied to those historic water profiles. In many cases, the water source is still what it was. In others, the town has resorted to new sources and other means of deducing what the water profile was was needed. But, the bottom line is that water quality varies and a brewer should not be trying to dial in a profile to the nearest ppm. I'd say that getting within about plus or minus 10 ppm is plently good and within 20 ppm may be OK too.

I do think that a brewer should fuss a little bit, but not get too caught up in minutia. The Sulfate/chloride ratio is a good benchmark when both SO4 and Cl are low, but some spreadsheets lead you to believe that you can just add more of an ion and achieve an acceptable ratio. That is not true. In any case, the Cl should always be below 100 ppm and your beer is probably better off with either of these ions less than 100 ppm (its OK to have high SO4 if its a hoppy beer).

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Old 03-31-2011, 04:45 PM   #95
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Salt additions for ppm in your water is simple and easy (I mean its just inorganic aqueous chemistry). But how the interaction with the malt and the water profile effects mash pH is more complicated, depending on the malt itself, which is organic.

If you are interested in hitting pH values you must have a good pH meter (and take readings at the reference temp.). Only then can you tune in your system with your malts and your water. So, using sauermalt or lactic acid without a pH meter is shooting in the dark. Doesn't mean its going to make bad beer, but it doesn't mean its going to make good beer either.

If you are solely interested in salt additions to make hops pop or bring the malt forward stick with the spreadsheets. But know that salt additions have the potential to effect your mash pH, which can effect the quality of your beer in the end. If you think the salts may be messing with your pH, get a pH meter and use it every time you brew.

If you have soft water: dark beers (a lot of roasted malts) will be an issue in terms of pH being too low.

If you have high alkalinity water: light beers will tend to be a problem (too high pH)

***The last two lines are way over simplified***

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Old 03-31-2011, 05:10 PM   #96
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Quote:
Originally Posted by funkswing View Post
If you have soft water: dark beers (a lot of roasted malts) will be an issue in terms of pH being too low.

If you have high alkalinity water: light beers will tend to be a problem (too high pH)

***The last two lines are way over simplified***
Yes, you are right that they were oversimplified. The last line is correct, but the first line is wrong. Its not soft water that is the problem, its low alkalinity.

Brewers need to get hardness out of their concern. The main thing we need to concern ourselves with is alkalinity and the second thing is hardness. We wouldn't care about hardness at all excepting that it is a critical component in countering alkalinity (ie. Residual Alkalinity).
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Old 03-31-2011, 06:20 PM   #97
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Quote:
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Salt additions for ppm in your water is simple and easy (I mean its just inorganic aqueous chemistry).
It is very simple and easy as long as you stick to the salts of strong acids and weak bases e.g. sodium chloride, calcium sulfate, magnesium sulfate but as soon a bicarbonate gets involved (carbonic acid is a weak acid) and, if you are trying to estimate mash pH, phosphate (because malt contains a lot of phosphate) or control mash pH with phosphoric acid or lactic acid a level of complexity is added because pH has to be considered in all calculations. It's still not that complicated but the bookkeeping requirement goes way up and the complexity of spreadsheets goes up by a factor of, I'd say, 10.

Bottom line is that the minerals you put in your beer effect it in two major ways:

1. They are influential in setting mash pH
2. Just as when you add salts in cooking they have direct flavor effects.

If you don't get 1. right then there is no point in worrying about 2.

No spreadsheet out there, or ever going to be out there, can or will give you information about your mash pH that is nearly as good as what you get from a pH measurement. The model in the spreadsheet may be at the limits of human knowledge but it requires knowing the amount of every buffer in the system (water, base malt, specialty malts, sauermalz, added acid) and the pH of every buffer in order to predict mash pH accurately. You are lucky if you get a wort pH number from the maltster. So you have to rely on titration experiments done by guys like Kai to come up with an approximation. It makes sense in such a case to use a spreadsheet to estimate the mash pH and estimate the amount of acid to add but not to rely on those estimates for more than guidance. If you use a spreadsheet to calculate the amount of hot water to add to a mash to raise from protein to saccharification rest do you throw away your thermometer? Of course not. No one would think of it. Yet people blindly trust a spreadsheet's pH prediction. Until recently there was justification for this as pH meters were expensive and really finicky. Today that's changed and there is really, IMO, no reason why every brewer shouldn't own one.
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Old 03-31-2011, 06:24 PM   #98
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If by "primer water" you mean the water described in the OP of this thread (CaCl2 + dilution + pH control), then I think I will go for that to start, and get more sophisticated if it doesn't come out right.

You mentioned experimenting with how well the Bru'n Water spreadsheet predicts mash pH, but you didn't actually mention how good your results were. How accurate has it been?
Pretty accurate. My actual pH is almost always a little higher than the spreadsheets I've used predict but, as I learned from using Bru'n Water, the profile given to me by the water supplier is unbalanced (this is a very nice feature imo). Last weekend was a Maerzen (mostly Munich malt) that Bru'n predicted at 5.5 and I got 5.55. I'll take it.

I also really noticed the pH shift during the boil last weekend. AJ has mentioned that when using lactic or sauermalz, boiling doesn't induce a pH drop like if you hadn't used them. When using lactic/sauermalz, my post boil pH would usually be almost exactly the same as pre-boil. Last week (no lactic/sauermalz), it dropped from 5.55 to 5.46.
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Old 03-31-2011, 06:26 PM   #99
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Until recently there was justification for this as pH meters were expensive and really finicky. Today that's changed and there is really, IMO, no reason why every brewer shouldn't own one.
Hmm, I have been reading exactly that - that pH meters are expensive and finnicky. That's why I was reluctant to go out and get one. What should a good pH meter cost me?

And how do I do pH adjustments exactly? Stir the mash, leave it for 10 minutes, take a sample, if it's too high add more acid malt, if it's too low add chalk, then stir and repeat until the level is right?
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Old 03-31-2011, 06:31 PM   #100
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Quote:
Originally Posted by bernerbrau View Post
Hmm, I have been reading exactly that - that pH meters are expensive and finnicky. That's why I was reluctant to go out and get one. What should a good pH meter cost me?

And how do I do pH adjustments exactly? Stir the mash, leave it for 10 minutes, take a sample, if it's too high add more acid malt, if it's too low add chalk, then stir and repeat until the level is right?
I got the Hanna pHep 5 for ~$80, then you need two calibration solutions (4.01 and 7.01) and then an electrode storage solution. One nice thing about the pHep 5 is that you can just pour the storage solution in the cap then put the cap on. There is thread about 'Buying a pH meter' and Kai has a guide on his site as well.

Mine has been anything but finicky. Calibrates very quick and easy and is very easy to use but it's only been a few months.
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