Boiling to reduce bicarbonates

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Yooper

Yooper

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I just ordered my aquarium test kit (GH and KH) for alkalinity, and the pickling lime, I had to get it off of the internet as I went to multiple places and had no luck with either item. Anyway, I remember reading that boiling can reduce the alkalinity and I can rack off of the precipitates.

I'm dying to brew! It's been two months, and I don't want to wait for two weeks for my order to come. Can I guestimate the values of the alkalinity by boiling, knowing my water chemistry? I thought I remember someone saying something to that effect a while back.

My water chemistry is:

calcium 58
magnesium 26
sodium 9
CaC03 251
SO4 45
Cl 14
HCO3 207

If I could preboil my mash water, and simply use lactic acid to acidify my sparge, then I could be in business. Any help would be greatly appreciated!
 
Yes. Assuming CaCO3 251 means alkalinity in ppm as CaCO3 (and I can't imagine what else it could mean) you have 5 mEq/L alkalinity. You also have 58/20 = 2.9 mEq calcium. The rule of thumb is that you can get the smaller down to about 1 mEq. That means you can expect to drop 1.9 mEq calcium and the alkalinity will go down by the same amount to 3.1 or 155 ppm as CaCO3. The obvious way to improve on this is to supplement the calcium with calcium chloride and or sulfate. If you can get the calcium up to or above 5 meq/L (100 mg/L) then bicarbonate becomes the limiting factor and you can get it down to 50. If you don't want either additional sulfate or chloride then you can add acid and get the anion of the acid or dilute with DI. That's the simplest approach and the numbers you calculate are precise. Precipitation is a bit dicey.
 
ajdelange said:
Yes. Assuming CaCO3 251 means alkalinity in ppm as CaCO3 (and I can't imagine what else it could mean) you have 5 mEq/L alkalinity. You also have 58/20 = 2.9 mEq calcium. The rule of thumb is that you can get the smaller down to about 1 mEq. That means you can expect to drop 1.9 mEq calcium and the alkalinity will go down by the same amount to 3.1 or 155 ppm as CaCO3. The obvious way to improve on this is to supplement the calcium with calcium chloride and or sulfate. If you can get the calcium up to or above 5 meq/L (100 mg/L) then bicarbonate becomes the limiting factor and you can get it down to 50. If you don't want either additional sulfate or chloride then you can add acid and get the anion of the acid or dilute with DI. That's the simplest approach and the numbers you calculate are precise. Precipitation is a bit dicey.
Click to expand...

I can easily supplement with either CaCl2 or CaS04. To get the calcium above 5 meq/l, I will probably use a combo of them.

But what do you mean "precipitation is a bit dicey"?

My source for RO water completely disappeared while I was away for the winter! I can buy DI but at $1 a gallon (plus hauling it in separate jugs) I really don't want to.
 
Did you give up on buying an RO unit Yooper? There was some pretty good info in that thread you started. I've got super hard water. ~300 TDS from the tap. I'm looking for solutions myself. I've done the boiling thing and I think it's more trouble than it's worth. You'd be amazed how much stuff precipitates out of my water though :eek:
 
What I mean is that you never know exactly what is going to happen. All the calculations we do are based on thermodynamic equilibrium and a system in which precipitation is taking place is not in thermodynamic equilibrium. Furthermore, thermo doesn't tell you anything about how fast a reaction will take place. That is why you have to do a test after boiling or lime softening to see how well you did. Assuming 1 mEq per liter is probably going to get you close enough and whether you actually get 2 probably doesn't make that much difference. But dilution is much more predictable.
 
ajdelange said:
What I mean is that you never know exactly what is going to happen. All the calculations we do are based on thermodynamic equilibrium and a system in which precipitation is taking place is not in thermodynamic equilibrium. Furthermore, thermo doesn't tell you anything about how fast a reaction will take place. That is why you have to do a test after boiling or lime softening to see how well you did. Assuming 1 mEq per liter is probably going to get you close enough and whether you actually get 2 probably doesn't make that much difference. But dilution is much more predictable.
Click to expand...

Ah! Thanks for the explanation.

Since I need to brew, but can't get RO water any more, and am not inclined to carry 6 gallons of plastic jugs of distilled home, I think I'm committed to boiling.

If this was your water, and you were boiling to reduce the alkalinity, how much CaSo4 and/or CaSo4 would you add?

I still want the RO system- but Bob put the kibosh on that at least for now. Since it cost under $30 for the lime and GH/KH kit, that was ok. We actually have great tasting water, so trying to sell him on using it for coffee didn't sway him a bit. He looked at me like I was nuts. And my goldfish don't care about RO water- they are perfectly content in the water out of my chiller (well, chilled first, as boiling water would probably irritate them. :drunk:)
 
Your water report is pretty badly imbalanced so anything I do with it is at best very rough. If you were to add 3 grams of each of calcium chloride and calcium sulfate to each 5 gal. being treated that would bring calcium to 152 mg/L (7.6 mEq/L) sulfate to 133 and chloride to 116. Alkalinity would stay at 5.5 and would probably drop,upon boiling,
to 1 or maybe even a bit more because of the extra calcium. Being conservative you would drop 4.5 mEq/L alkalinity and 4.5 mEq Ca++ leaving 3.1 which is 62 mg/L which should be good for most beers.
 
ajdelange said:
Your water report is pretty badly imbalanced so anything I do with it is at best very rough. If you were to add 3 grams of each of calcium chloride and calcium sulfate that would bring calcium to 152 mg/L (7.6 mEq/L) sulfate to 133 and chloride to 116. Alkalinity would stay at 5.5 and would probably drop,upon boiling,
to 1 or maybe even a bit more because of the extra calcium. Being conservative you would drop 4.5 mEq/L alkalinity and 4.5 mEq Ca++ leaving 3.1 which is 62 mg/L which should be good for most beers.
Click to expand...

I think I might have understood most have that- so thanks for your patience with me as I take baby steps towards remembering my college chemistry! My next question then has to do with your specifics of "3 grams" of CaCl2 and CaSo4. Is that per batch, gallon, liter, etc? I'm sorry to be so thick, but I haven't a clue.

What is the report badly imbalanced? Not that it really means anything to me, but that's what I got from Ward's Labs a while back.
 
If you're looking for a good R/O unit, I bought one for my saltwater aquarium from this guy:

http://www.melevsreef.com/rodi.html

It worked really well. I don't have fish anymore, but I still have my unit. I think I'm going to start using it to craft better water for my brews. If I'm gonna do this (brewing), I may as well do it right. But I want to test with some R/O from the store to see if it really makes a big difference before I drop another $60 on a new set of filters to start using the unit again.
 
Yooper said:
What in the report badly imbalanced? Not that it really means anything to me, but that's what I got from Ward's Labs a while back.
Click to expand...

I don't have either the pH of the water or the pH they titrated to when they measured alkalinity so I have to assume values for those. Using 7 for the sample pH and 4.3 for the titration pH I calculate from the numbers you posted 5.425 milliequivalents of positive charge (form calcium, mgnesium and sodium) per liter and 6.352 mEq/L negative charge from chloride, sulfate, and bicarbonate. In real water those 2 numbers have to be equal as water does not carry a net ionic charge.
 
How precise to you have to be? I know from my own experience that I tend to try and hit fairly close, out of a desire to be able to do it, but when it comes right down to it, I also believe that I don't really HAVE to be that close to make good beer.
 
ajdelange said:
I don't have either the pH of the water or the pH they titrated to when they measured alkalinity so I have to assume values for those. Using 7 for the sample pH and 4.3 for the titration pH I calculate from the numbers you posted 5.425 milliequivalents of positive charge (form calcium, mgnesium and sodium) per liter and 6.352 mEq/L negative charge from chloride, sulfate, and bicarbonate. In real water those 2 numbers have to be equal as water does not carry a net ionic charge.
Click to expand...

Ah, I see. On their report, they said the pH was 8.2.
 
Homercidal said:
How precise to you have to be? I know from my own experience that I tend to try and hit fairly close, out of a desire to be able to do it, but when it comes right down to it, I also believe that I don't really HAVE to be that close to make good beer.
Click to expand...

Oh, I'm sort of methodical and a perfectionist. I'd like to say "close enough", but I'm just not wired that way. I'm also happy to be learning new things everyday- I think that's why I love brewing so much. I'm never really comfortable with the amount I know as there is always something new to learn every day for me.

This water thing has been great for me! We have excellent tasting water, but the lighter beers are NOT wonderful. I've noticed such an improvement in those lighter beers with just some simple water adjustments that I'm excited to try to learn more and more. I never thought I'd be working on reducing alkalinity with slaked lime, being excited to have a pH meter, and talking about water chemistry! It's like a new world of geekdom has been opened for me. :ban:
 
I hear ya Yooper. I'm kind of the same way. I love the challenge and learning about new things. I've been wanting to get into water chemisty for a while now, but I've been working on my own software and wanted to get that dialed in first. I think I'm about ready to take the wate plunge. If nothing else, I would love to be able to try a beer and then brew that exact same beer. Now, I've done a few clone recipes, and they were great, but they weren't the original. There's got to be more to it than just a simple ingredient list, mash temp and fermentation temp. I'm convinced that water is the missing link.
 
Yooper said:
Ah, I see. On their report, they said the pH was 8.2.
Click to expand...

We're still off by a country mile. In fact more so. I just checked the spreadsheet and noticed that I didn't check the "As S" box and I know Ward Labs reports "as S". You sure that sodium number isn't 69 instead of 9?

Up at the top of the page you will find a couple of numbers written as "cations/anions mEq/L 8.0/8.2" or something like that. This is their estimate of the imbalance. What are those numbers?
 
ajdelange said:
We're still off by a country mile. In fact more so. I just checked the spreadsheet and noticed that I didn't check the "As S" box and I know Ward Labs reports "as S". You sure that sodium number isn't 69 instead of 9?

Up at the top of the page you will find a couple of numbers written as "cations/anions mEq/L 8.0/8.2" or something like that. This is their estimate of the imbalance. What are those numbers?
Click to expand...

The top says:

pH 8.2
TDS Est 305
cations/Anions, me/L 5.4/5.5

ppm
Na 9
K 2
Ca 57 ( I had 58 above, a typo)
Mg 26
Total Hardness, CaC03 251
So4-S 15
Cl 14
Bicarb Hco3 228
Total alkalinity CaCo3 207
 
Ah, much better. If I assume titration end point is 4.5 I can get those numbers. So the alkalinity is 4.1 mEq/L and will drop 3.1 to about 1 which means the calcium hardness which would go to 7.6 mEq/L by the two additions would drop to 4.5 mEq/L (90 mg/L) after precipitation.
 
My water lacks everything but sodium and bicarbonate. I can't do any additions unless I use RO. Boiling to reduce would be great for me. I'll keep my eye on this thread and how your water turns out after boiling.
 
ajdelange said:
Ah, much better. If I assume titration end point is 4.5 I can get those numbers. So the alkalinity is 4.1 mEq/L and will drop 3.1 to about 1 which means the calcium hardness which would go to 7.6 mEq/L by the two additions would drop to 4.5 mEq/L (90 mg/L) after precipitation.
Click to expand...


If I understand you right (50% chance, I'd guess!) and looking at Kai's spreadsheet on reducing alkalinity by boiling, by adding 5 grams of CaCl2 and 5 grams of CaSo4 to 15 gallons of water, I can drop the calcium that I just added AND the alkalinity to "good" levels for many of my favorite beer styles.

I can only boil about 14 gallons and I need 14.5 for my brewing but I think .5 gallons of tap water or distilled water is doable.

AJ- thank you so much for all of your help. I appreciate the hand holding as I take baby steps.
 
I just wanted to report back that this worked beautifully!

But........I started with all the water I could fit in my BK (about 14 gallons) and ended up with a bit less than 12 gallons due to the heavy precipitate on the bottom. And, it's a real PITA, by the way! :drunk:
 
mbobhat said:
Not to change the subject (the fascinating world of water chemistry:drunk:)but how about trying an acid rest during the mash?
Click to expand...

I don't know- I haven't thought about it. My problem isn't hitting mash pH at all, so I don't know if it would be of any benefit to me.

My issue is the high bicarbonate level (alkalinity)- it has a flavor impact on my beer.
 
Ahh, I just realized who I was talking to...Yooper!!! Threw me off with the dominatrix pic instead of GB packers. I have done your oatmeal stout. Delicious!!!:mug:

You probably know more about brewing than most around here:)

But yea adding some calcium should help it precipitate out more.
 
You tricked me haha...but in laymans terms (we are all laymen, some are laywomen, and some are women dressed in black leather:rockin:)

There is a principle in chemistry that means you can move an equilibrium reaction one way or the other by adding more of one thing.

In this case it is the calcium. Add any one thing that is more to the left, and more on the right is formed. Of course adding heat helps precipitate it out, as well as to drive off the CO2.

Ca2+ + 2HCO3- → ↓CaCO3 + H2O + ↑CO2


Glad it worked for ya!
 
Since you've invoked Le Chatelier, lets not ignore the fact that removing a product also pushes the reaction to the right. That's why it is important to get the CO2 out. If you boil it is sparged out by steam but it is not necessary to boil if you sparge with something else such as air. Another trick that works is to rig a recirculating pump and spray arrangement.
 
Right you are sir about removing the CO2. Thanks for completing the principle.

I wonder if using the pickling lime, if there is a need to boil or maybe just use warm water? With the OH- from the Ca(OH)2 converting the bicarb to carbonates, you would remove all the bicarb and probably precipitate out some extra chalk in the process, right? Maybe just do a quick boil and then add the pickling lime to let sit in an insulated cooler with air circulating from bottom or the spray action you talked about?

Seems like a lot of energy to get out the carbonates by boiling. Your thoughts?

EDIT: I reread your above post, looks like you answered the question on whether you need to boil or not.
 
One of the big advantages of lime treatment (to the pro's anyway) is that no heat is required. In the lime reaction

Ca(OH)2 + Ca++ + 2HCO3- --> 2CaCO3 + 2H2O

as no CO2 is evolved there is no need to sparge it out. However, the solubility of CaCO3 decreases as the temperature is increased so there is a slight advantage to doing lime treatment at higher temperature. Nobody does, AFAIK, so the advantage can't be significant.
 
ajdelange said:
One of the big advantages of lime treatment (to the pro's anyway) i that no heat is required. As in the lime reaction

Ca(OH)2 + Ca++ + 2HCO3- --> 2CaCO3 + 2H2O

As no CO2 is evolved there is no need to sparge it out. However, the solubility of CaCO3 decreases as the temperature is increased so there is a slight advantage to doing lime treatment at higher temperature. Nobody does, AFAIK, so the advantage can't be significant.
Click to expand...

Today when I tried my first lime treatment, the water (and pH meter solutions) were all at 66 degrees.
 

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