How can I get the chalk to dissolve?

[klnosaj]

I started paying attention to my brewing water and after a lot of ****-ups I finally realized I need to begin with RO water and build the profile from there. My beers are better than they've ever been. But I'm stuck with a question that I surmise has been asked ten thousand times before:

how do I get the CaCO3 to dissolve?

 

[GilaMinumBeer]

http://braukaiser.com/wiki/index.php?title=Building_brewing_water_with_dissolved_chalk

 

[klnosaj]

http://braukaiser.com/wiki/index.php?title=Building_brewing_water_with_dissolved_chalk

oh my goodness...that article is way far over my head and contains suggestions far too elaborate for me to master. Thanks, though.

 

[GilaMinumBeer]

oh my goodness...that article is way far over my head and contains suggestions far too elaborate for me to master. Thanks, though.

"If you do not want to be bothered with the chemistry behind dissolving chalk you can safely skip ahead. "


You add it to water and carbonate it.

 

[klnosaj]

"If you do not want to be bothered with the chemistry behind dissolving chalk you can safely skip ahead. "


You add it to water and carbonate it.

Yeah, I read the entire article including the part you quote. I don't keg so I'm not about to rig something up just to carbonate chalk. Thanks for looking out, though.

 

[Quaker]

On my last batch I started adding any such minerals and salts directly to the mash. I really noticed a difference in taste which mean I'll back off a little quantity. Before that, I'd put them in my strike and sparge water directly. Then after running it over to the mash tun there were always leftovers still in the bottom which hadn't dissolved. The time and lower pH of the mash may help dissolve them more. Just speculating, but it was a significant difference for me. I put half in with my initial strike water and the other half after gathering first runnings, before by batch sparge water was added.

 

[GotPushrods]

I know this doesn't answer your question... but I would skip messing with chalk all together and use pickling lime (calcium hydroxide).

It dissolves easily and packs twice the alkalinity punch per weight as chalk. Be careful.

On the flip side, chalk isn't a bad idea for most people, since you will rarely NEED as much as the spreadsheet models tell you. The undissolved portion might actually help you mitigate the consequences of an imperfect spreadsheet model. Remember, even the best spreadsheets out there still have a much higher error when the grist gets darker. They usually estimate lower pH than reality, so go easy on the pickling lime.

FWIW I've never seen a pH as low as a spreadsheet predicts in a dark beer. (Measured with high quality, calibrated pH meters)

 

[ajdelange]

I
how do I get the CaCO3 to dissolve?

Several of the previous posts have hinted at the answer. In a word, you don't. Unless you are brewing beers with lots of dark malt (where 'lots' to me means to the point that I wouldn't like the beer) you probably don't need chalk. In the cases where you do need alkalinity because mash pH, as measured with a decent meter properly calibrated, tells you that the mash pH is too low you need to add alkali in some form. Chalk isn't the best form because to get it into solution in the way nature does, as a previous poster has suggested, is an elaborate process involving sparging with CO2 or pressurizing with CO2. Chalk just takes a long time to react. Adding it to the mash to the point where you get a pH reading you like probably means that about half of it is still undissolved. This will dissolve later as long as the mash/wort is exposed to it. A better choice is slaked lime (pickling lime) available in the canning section of super markets. Add very little of it very slowly while checking mash pH until it is in the proper range. Stir thoroughly.

 

[RCCOLA]

I'll +2 pickling lime. It raises pH without risk of adding flavors, unlike chalk or baking soda

 

[klnosaj]

Pickling lime it will be from now on. Thanks for all the recommendations.

 

[ValonaBrewing]

Dude, your tap water is the envy of brewers everywhere. Alkalinity: 25, hardness 14, calcium 3.8, chloride 4, sulfates 3.7. The stuff coming out of your tap was probably snow yesterday, why do you think you need RO water?

 

[klnosaj]

Dude, your tap water is the envy of brewers everywhere. Alkalinity: 25, hardness 14, calcium 3.8, chloride 4, sulfates 3.7. The stuff coming out of your tap was probably snow yesterday, why do you think you need RO water?

Because what's coming out of my tap is impossible to know on any given day. My water utility (EBMUD) releases data from last year's tests. There is significant variation seasonally and they don't test very often (I've spoken with a couple of engineers there). In other words, the water report is unreliable. Furthermore, I make several varieties of English style bitters which benefit tremendously from higher mineral content (especially calcium) and all of my beers floculate much better now that I have appropriate magnesium levels. I also make some "softer" beers like a Pils that benefit from a completely different water profile than some of the English styles.

Since I switched from EBMUD tap to RO my beer has gone from very good to insanely delicious. I'll never go back to tap.

 

[ValonaBrewing]

Yes, i have ebmud water as well, as does pyramid and trumer pils. I've tested it with an aquarium test kit and found that the reported numbers line up pretty well. Its about as good as water gets, so im a little at a loss as to what could be going wrong. Are you removing the chlorimine before brewing with it?

 

[klnosaj]

Yes, i have ebmud water as well, as does pyramid and trumer pils. I've tested it with an aquarium test kit and found that the reported numbers line up pretty well. Its about as good as water gets, so im a little at a loss as to what could be going wrong. Are you removing the chlorimine before brewing with it?

The reported numbers vary. How can your test results line up other than to fall within a given (sometimes wide) range?

Meanwhile, there is absolutely nothing, imho, to recommend what Pyramid does. Furthermore, Pyramid is brewed at several locations across the country and two in the bay area. If they're not treating their water individually then each brewery is making a different beer.

My tap water has been fine for Pilsners. As I already said, it produces bland bitters, pale ales, exports, vienna style lagers, IPAs, ambers, schwarzbiers, French style farmhouse ales, and Belgian dubbels. The empirical data I've collected are unequivocal: Individual profiles make the beer better. I encourage you to try making a beer with water exactly as you want it and see if you notice a difference. I sure have.

 

[teddy4xp]

John Palmer recommends adding your minerals directly to your match. You dough in stir it up for a couple minutes and then add your minerals

 

[bigdaddybrew]

Carbonated water people. Brukaiser is putting his minerals in a bottle and carbonating. I use as little chalk as possible. I use baking soda while keeping my sodium less than 100. Then use a small amount of chalk if needed. Then dissolve the minerals in a one liter bottle of seltzer water or club soda, cap and shake until dissolved. Add this to your mash water. Note minerals are not dissolved until clear. Not sure why the dissolving chalk has been turned into such a mystery. You will be adding a little extra sodium etc. from the soda but it should have little impact. Keep in mind the extra quart of water you are adding. Hope this helps.

 

[ajdelange]

There is just no reason to ever use bicarbonate or carbonate in preparing brewing liquor. If you do go to the trouble to put it in and then adjust mash pH properly (to 5.4) 90% of the bicarbonate is gone. So why go to the trouble to put it in in the first place?

Well there is one exception. If you want to experience what a Munich, for example, brewer experienced you would then need to synthesize carbonaceous water. This is a bit of a bother as one must sparge with CO2 or use pressurized CO2. Both a big pain and when it is all over (i.e. in the mash tun) , all the bicarb (except 10%) is gone. If you need alkalinity then use lime. Much easier, more effective.

 

[bigdaddybrew]

When brewing a very dark beer with lots of roasted grains you will need water with lots of residual alkalinity or your mash PH will be too low. Baking Soda can handle most beers but you have to watch the sodium level. If you brew a particularly dark beer with lots of roasted grains you may need more alkalinity. Chalk is one way to add this.

Properly prepared brewing liquor should lead to a mash PH in an acceptable range without further adjustments needed. Especially if your use Bru n water or Ez water spread sheets before brewing. Or you can buy a PH meter and make adjustments while you lose heat in your mash tun. This works for many brewers especially if an exact PH is important to you. I prefer to prepare my brewing liquor in advance of brewing and leave the heat in my Mash tun cooler. But thats just me.

 

[GotPushrods]

When brewing a very dark beer with lots of roasted grains you will need water with lots of residual alkalinity or your mash PH will be too low.

I cannot off the top of my head think of a time I had to add alkalinity to a beer under 30 SRM. Rarely under 35. This seems to blow people's minds, but it's been my experience.

Of course my darker beers tend to get that way from roasted barley rather than something like crystal 120 (which actually lowers the pH more). Nevertheless I wouldnt assume anything. There will be times you will need alkalinity. But probably even more often, you'll need acid in a dark brown beer. It's weird at first, but trust your pH meter.

 

[bigdaddybrew]

There will be times you will need alkalinity. But probably even more often, you'll need acid in a dark brown beer. It's weird at first, but trust your pH meter.

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.

Of course I build brewing water from R/O because my well water has so much iron and I'm happy if the beer style and water match up and the predicted ph range is acceptable using the Bru n water spead sheet.

So far this has worked very well for me. Others have reported Bru n water to get pretty close when checking actual mash PH. So I am going on that. Plus the flavor and fermentability have been very good since I started building my own water.

Gotpushrods, do you use a water speadsheet? If so how close is it's predictions?

 

[ajdelange]

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.

 

[bigdaddybrew]

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.

 

[mabrungard]

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.

 

[bigdaddybrew]

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.

 

[ajdelange]

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.

 

[mabrungard]

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.

 

[ajdelange]

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).

 

[bigdaddybrew]

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?

 

[ajdelange]

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).

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.

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.

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.

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.

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.

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)

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.

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.

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.

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.

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).

 

[bigdaddybrew]

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.