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Old 10-30-2012, 05:37 AM   #21
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Wow you must have some hard water if you acidify dark brown beers! I have been finding that using Bru n water spread sheet my dark beers have needed high alkalinity or they are predicted to have a very low PH.
Hard water actually reduces the need for acid as the calcium and magnesium react with malt phosphate to release protons. This is why RA = alkalinity - (Calcium + magnesium/2)/3.5.

I will also attest that I encounter mash pH of about 5.5. when I brew stout which comes in anywhere from 60 - 80 SRM. I too get the color from roast barley and don't use dark crystal malts.

I'll point out again that if you use chalk in preparation of brewing water and do it properly you will wind up with a solution that is super saturated with respect to either calcium carbonate and/or carbon dioxide as are most of the carbonaceous waters that home brewers erroneously think they must emulate to brew the beer of a particular city. When such a water hits the HLT the calcium carbonate they so laboriously loaded into their water precipitates - just as it did in the HLT of the brewer of yore who was forced to brew with the water the home brewer is trying to emulate. Thus but little of the bicarbonate reaches the mash tun in either case. That which does is immediately converted to carbon dioxide by the acids in the mash be they from dark grains, sauermalz or CRS. Thus brewers in the old days did not need the ridiculously high RA's that some of the spreadsheets used to demand (many of them are much more reasonable about this these days).

One should indeed not have to tweak his acid additions in the mash tun to get proper pH. The way to do this is to understand what is required of the water before one doughs in. This comes from experience but a mash tun pH check is always a good idea. This is how experience is gained and reinforced. But what of the first time you brew a particular beer? With enough experience you will know what to do. Until that level of experience is gained the best course is pH measurement on a test mash. Some fine tweaking will still be required but a test mash will get you closer than a spreadsheet. The spreadsheet can be used to guide you in making the test mash.
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Old 10-30-2012, 11:17 PM   #22
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My minerals addition are not precipitating when heated as they r not super saturated. Just a small chalk addition. And yes I assume they are being used up by the acids in the mash as intended to buffer the dark crystal and roasted grains in my porter. I would like to know the actual ph though.

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Old 10-31-2012, 12:47 AM   #23
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Big Daddy,

All the evidence from the homebrewers and probrewers I deal with indicates strongly that chalk does not provide any neutralizing capability in the mash unless the chalk is fully dissolved with CO2. I think you would be disappointed with this fact if you had a pH meter and checked its effect.

If you want to moderate the pH drop in your more acidic grists, you should consider pickling lime. It works.

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Old 10-31-2012, 01:05 PM   #24
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Mr. Brungard,
I love your spread sheet. A liter of seltzer is more than enough to dissolve a small chalk addition. Brewers made good beer before the invention of the PH meter. Hard water tastes a certain way and has a certain mouth feel. Maybe thats only important to me. Dissolve the minerals and put them in your RO water. Drink some. I't tastes full, almost sweet in a way. It's hard to describe. Or lets say it can't be done. Thats what I been told again and again. Is my ph dead on? Maybe not. Is the beer delicious? Yes. Do I want a ph meter? It's on the list.

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Old 10-31-2012, 02:04 PM   #25
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Judging from your comments in #20 and #24 I think there may be some confusion in your mind as to the distinction between hardness and alkalinity and/or between temporary and permanent hardness. Hardness refers (technically) to the presence of calcium and magnesium ions in solution. These are doubly charged cations and each one must be paired with two negative ionic charges in order to retain electrical neutrality. If the negative charges come from bicarbonate ions (which are, in potable water, responsible for alkalinity) then the hardness is said to be 'temporary'. In nature temporary hardness arises when water exposed to atomspheric or subterranean CO2 dissolves limestone. This is the process you mimic when you put chalk in a corny and pressurize with CO2. As the name suggests, this hardness is temporary - as soon as you heat the water (or add lime to it) the process by which it dissolved is reversed and most of the chalk falls back out of solution.

If, OTOH, you dissolve limestone (or magnesite) with hydrochloric acid or sulfuric acid the result is calcium (or magnesium) chloride or sulfate (the carbon dioxide in the limestone/magnesite flies off at this point). The resulting hardness is 'permanent'. You cannot precipitate it by boiling or lime addition (though you can get it with phosphate, for example).

Most people do not like the taste of bicarbonate (put some baking soda in a glass, add some water and taste it) so it is fortuitous that establishment of proper mash pH causes most (90%) of bicarbonate ion to leave the mash (as CO2). However many do like the crisp, crunchy, salty, minerally, bitter qualities of hard water and some beer styles depend on this. If you are one of those that do like mineral then by all means have at it. But don't try to increase hardness with chalk. Use calcium chloride and calcium sulfate instead.

I think the folly of using chalk as a source of alkali has been pretty thoroughly discussed though lots of home brewers have used it (and ruined lots of beers with it) over the years.

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Old 10-31-2012, 03:49 PM   #26
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Mr. Brungard,
A liter of seltzer is more than enough to dissolve a small chalk addition. Brewers made good beer before the invention of the PH meter.
That is not a bad idea to use seltzer water for the carbonic acid content, but I'd be leery since some seltzer water also has other ionic content for flavor. I'm not sure if Club Soda is pure water either.

You are correct that brewers did make great beer before the pH meter, but they were typically limited to a sub-set of styles that were suited to their water.
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Old 10-31-2012, 04:06 PM   #27
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I'm not sure if Club Soda is pure water either.
Usually loaded with NaCl to sweeten it a bit (though you can now find 'low sodium' versions).
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Old 10-31-2012, 10:48 PM   #28
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I appreciate this discussion. The opportunity to learn from more experienced brewers is invaluable. Most posts just start with it can't be done.

What I kept reading is that chalk will work but can't be dissolved easily.

Seltzer water is usually just carbonated water but can be harder to find. I make my own carbonated RO water with a Sodastream Soda maker. Club soda will have about 200mg of sodium in a one liter bottle and a tiny additition of Bicarb to buffer it. This should make very little difference but should be accounted for if sodium is a concern. Try some club soda. Many people find it quite pleasant. Add some baking soda to a glass of water, too salty but it will buffer the acid in your stomach. Most people add a teaspoon to a glass. I have been adding about a tsp to 5 gallons.

I have read that as you lower the temperature of water, chalk actually becomes more soluble. The water can become saturated at that temp. When you heat the water gently, the chalk can remain dissolved and is said to be super saturated at that higher temperature, but still dissolved. Now when boiling a super saturated liquid you will cause a precipitation. This is one way to lower the alkalinity of hard water. Would a couple of grams of chalk dissolved in a liter of seltzer water added to 5 gallons of water be considered super saturated? I'm not seeing a precipitate when heating, only clear hot brewing liquor.

So the bicarb from the temporary hardness, the baking soda and the chalk dissolved with CO2, buffers the PH of the mash dissipating as CO2 and leaving sodium and calcium. That sounds good. I have been using a full benefit of minerals in my darker beers including calcium chloride and gypsum (permanent hardness) with good results, not even using the chalk, as I was repeatedly told you can't dissolve it.

It makes sense that the flavor has really been coming from the remaining sodium, chloride and sulphate all along and not the chalk or baking soda. I like Brown ales and an occasional porter. Not a fan of stouts really. I have been building this profile with RO water with good results. (actual mash ph unknown).
Ca 56
Mg 11
So4 75
Na 83
Cl 76
HCO3 210
ALK 172
Res. ALK 126
Using Bru n Water this profile is predicted to buffer my dark brown beers in an acceptable range. I have also used the dissolved chalk with less baking soda with similarly good results for very dark brown porter.

If you brewed two beers, identical in every way except one had a mash PH of 5.2 and the other a mash PH of 5.5, can you tell the difference?

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Old 11-01-2012, 05:44 AM   #29
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What I kept reading is that chalk will work but can't be dissolved easily.
If by 'works' you mean it works as an alkali, yes that it true.

CaCO3 + 2H+ --> Ca++ + 2HCO3-

i.e. it absorbs protons (H+) to become the conjugate base, HCO3-. If you mean it reacts to release calcium ions - yes that is true too. The reason it is not effective as a means of adding calcium to water or in neutralizing acid in the mash is that the dissolution reaction is slow at normal mash acid concentration and pH. A dose is added (and most of the spreadsheets calculate a dose many times larger than is actually needed) and this is added to the mash but the reaction takes place so slowly that by the time the mash is over there is still lots of undissolved chalk left in the mash. The brewer reads a pH he likes and proceeds with the brew but that additional chalk keeps dissolving and reacting pulling mash pH too high and ruining the beer (it will be drinkable but not nearly as good as it could be if mash/wort pH is managed properly).

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Seltzer water is usually just carbonated water but can be harder to find. I make my own carbonated RO water with a Sodastream Soda maker. Club soda will have about 200mg of sodium in a one liter bottle and a tiny additition of Bicarb to buffer it.
No bicarb is added. Some of the dissolved CO2 is converted to bicarbonate. For example, if you carbonate pure water to the extent of 2 volumes the pH would be 3.7 and the water would contain 12 mg/L bicarbonate. One could, of course, add more but this would defeat the purpose.

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This should make very little difference but should be accounted for if sodium is a concern.
As I noted earlier the sodium chloride is there for taste. Without it the carbonated water tastes relatively flat and thin. The salt is in there for the same reason old timers put salt in their beer.

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Add some baking soda to a glass of water, too salty but it will buffer the acid in your stomach. Most people add a teaspoon to a glass. I have been adding about a tsp to 5 gallons.
I often advise people to put some bicarbonate in a glass of water and taste it before adding it to their brewing water. It tastes pretty bad to most people but I do have to say I find it particularly offensive. If you like it, then go ahead and do it but as I have pointed out, I think this is the third time, it will leave the water when mash pH of about 5.4 is established.


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I have read that as you lower the temperature of water, chalk actually becomes more soluble.
That is true. The solubility product (of calcite - the least soluble form) is 10^-8.45 at 20 °C but 10^-8.39 at 5 °C. This means that calcite is 10^0.03 = 1.07 (i.e. 7%) times more soluble at 5 than at 20.


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The water can become saturated at that temp.
The water can be saturated at any temperature. The water is saturated whenever {Ca}*{CO3--} = solubility_product and super saturated if greater.


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When you heat the water gently, the chalk can remain dissolved and is said to be super saturated at that higher temperature, but still dissolved. Now when boiling a super saturated liquid you will cause a precipitation.
Carbonaceous waters, especially from wells in limestone regions often leave the tap supersaturated with respect to chalk and/or carbonic acid or both. It often takes days for equilibrium to be reached unless something is done to hasten this. 'Something' usually consists of
1. Adding nucleation sites (some chalk)
2. Heating
3. Raising the pH
4. Adding additional calcium
5. Sparging with steam or air
6. Combinations of the above (such as adding lime which combines 3 and 4)


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Would a couple of grams of chalk dissolved in a liter of seltzer water added to 5 gallons of water be considered super saturated?
Assuming 'a couple' to mean 2 when added to a liter of water and dissolved with CO2 to pH 7 then the liter is supersaturated with respect to CO2 (0.16 atmospheres with the atmosphere itself at 0.0003 atm partial pressure of CO2) and chalk (saturation pH is 5.7 - we set for 7). Added to 5 gallons of pure water the solution is supersaturated WRT CO2 (0.01 atm) but not WRT chalk (saturation pH 7.8 and we set pH 7). Now because the water is super saturated WRT CO2 CO2 will leave it until the partial pressure of CO2 equals the partial pressure of CO2 in the atmosphere (0.0003 atm). At this point the pH will have risen to 8.52 which is well above the saturation pH and calcium carbonate will precipitate. This would, at room temperature, take a long time. Adding heat will accelerate the process and a precipitate will form.


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I'm not seeing a precipitate when heating, only clear hot brewing liquor.
Two grams of calcium carbonate in 5 gallons (105 mg/L) dissolved with CO2 to pH 7 yields water of, surprise, hardness 105 and alkalinity of 105. This is definitely super saturated but if you heat this water short of boiling, and don't provide nucleation sites it is possible for much of the carbonate to remain in solution. My well water is about at this level of hardness and somewhat less in alkalinity and doesn't appear milky or drop a precipitate unless I do the other things. However if I put a straight (no nucleation stuff) sample in a nephelometer pre-boil it reads 0.57 NFU and after a brief boil 1.97 NFU so the precipitate does indeed form. The particles are obviously tiny and will take forever to settle but settle they eventually will as equilibrium hardness and alkalinity with atmospheric CO2 are 50 and 50 each.

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So the bicarb from the temporary hardness, the baking soda and the chalk dissolved with CO2, buffers the PH of the mash dissipating as CO2 and leaving sodium and calcium.
If it's dissipating it is not buffering. As I mentioned before the carbonic/bicarbonate system buffers at 6.38 (at 20 °C), not mash pH. Bicarbonate stresses the natural buffering of the base malt which without that stressor would be at 5.65 - 5.75 nominally depending on the malt. The stressor raises mash pH above what is desired.


Quote:
Originally Posted by bigdaddybrew View Post
That sounds good.
That sounds bad to me unless there is acid from dark malt trying to stress the buffer in the other direction (low pH). In those cases you need some alkali and bicarbonate will do. But so will OH- from lime. It seems simpler to me to add some lime to the water/mash in those cases but if you prefer to use chalk and CO2 that's fine.


Quote:
Originally Posted by bigdaddybrew View Post
If you brewed two beers, identical in every way except one had a mash PH of 5.2 and the other a mash PH of 5.5, can you tell the difference?
I've never gone as low as 5.2 but I can certainly attest that the difference between beers brewed at pH 5.4 - 5.5 are dramatically better than ones brewed at 5.6 - 5.7, at least for the styles I do (lagers, German ales).
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Old 11-01-2012, 12:19 PM   #30
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So to summerize. It can't be done. And if you try it it will ruin your beer. So don't try it.

I was making ok extract beer. But it was lacking something. My brews were tasting watery, lacking flavor, body, chill haze, high finishing gravities, off flavors, the usual new brewer problems. I did a lot of reading. Went all grain. Beer got better. Bought a fermentation fridge. Beer got better. Learned about yeast. Beer got better.

Later I decided to design my own water. Bought the various minerals...chalk, baking soda, salt, gypsum, calcium chloride. Followed Palmer's reccomendations for a general water profiles. Dissolved the minerals in carbonated water and added to RO water. My beer got significantly better. Later I found the Brunwater spread sheet and dialed it in even closer. Better flavor, no more chill haze, good fermentability. Damn good beer. When I buy a PH meter and make pickling lime or phosphoric acid additions will it be even better? If it fits the pattern I would have to say probably yes.

Take a glass of water. Add vinegar. Test the PH. Acidic. Now add baking soda. The baking soda reacts with the vinegar and as it buffers the acid you get CO2 (fizz) as it dissipates. If it's dissipating it's not buffering? Test the PH. Now it's higher. Sodium Bicarbonate buffers acid. Why wouldn't it work in a mash? I don't know.

Water, CO2, salt for flavor, and a little baking soda so it's not so sour. Club soda makes a nice drink. That's how they make it. I looked it up. Just a tiny amount of minerals.

Add a teaspoon of baking soda in 5 gallons of water, you might not even notice. I had 3 gallons of brewing water left over from a cream ale, small amounts of baking soda, calcium chloride, gypsum, and salt. I put it in the water cooler. My wife and kids didn't even notice. Mix a teaspoon of baking soda in a glass of water, of course it tastes bad but as stated above it dissipates as it neutalizes acids in the mash so why should the taste of baking soda in a glass of water prevent someone from brewing with it? I don't know.

Baking soda will neutralize a sour stomach. Eat a chalk tablet (Rolaids) and it will also buffer a sour stomach. Chalk and baking soda neutralize acid. Why won't it buffer acid if you disslove it first and add it to your mash? I don't know.

So I dissolve my minerals in carbonated water, add them to RO water and mash away. Brunwater says I'm in the PH ball park. Whats the actual PH of my mash? I don't know...yet. But I'm curious to know. What more can I say. Apparently I'm just not smart enough to understand why it shouldn't work. But damn the beer sure is good. Thanks again for your hard work Martin Brungard.

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