Author Topic: Carbonate Hardness = Carbonate Alkalinity based on Source pH?  (Read 1529 times)

Offline mabrungard

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Re: Carbonate Hardness = Carbonate Alkalinity based on Source pH?
« Reply #15 on: April 13, 2018, 01:00:23 AM »
You are confusing CO3 with HCO3. If we were concerned with CO3, that value you mention would be correct. But Bru'n Water deals with HCO3 since that is the form of carbonate ion that we have at typical brewing pH.
Martin B
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Offline hackrsackr

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Re: Carbonate Hardness = Carbonate Alkalinity based on Source pH?
« Reply #16 on: April 13, 2018, 05:50:59 AM »
You are confusing CO3 with HCO3. If we were concerned with CO3, that value you mention would be correct. But Bru'n Water deals with HCO3 since that is the form of carbonate ion that we have at typical brewing pH.

In dealing with CaCO3 additions, isn’t your sheet inherently dealing with CO3 also? And doesn’t the CO3 from the chalk just pick up a H+ becoming the HCO3 species, because of the typical brewing pH (or availability of H+ ions)?

I don’t understand how 158 ppm of CO3 in distilled H2O could become 322 ppm HCO3 without the addition of more carbon or violating some laws of physics.

The reason I ask is because Kai’s water numbers use the 158 number when dealing with CaCO3 additions, which he then lists as HCO3.

http://braukaiser.com/wiki/index.php/Schwarzbier

If I put his salt additions, RO, and grist into your sheet I get more than double the bicarbonate he quotes, and absurdly high predicted mash pH. Like above 6.

Offline mabrungard

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Re: Carbonate Hardness = Carbonate Alkalinity based on Source pH?
« Reply #17 on: April 13, 2018, 12:11:30 PM »
Unfortunately, Kai's information is incorrect too. There is history behind that value when talking about chalk.

As you may have heard, it takes extraordinary measures to get chalk to dissolve in water. Unfortunately, that also applies to wort since wort doesn't have much of the 'strong' acid content needed to dissolve chalk. Brewers know that chalk doesn't provide the alkalinity that its chemistry says it adds and therefore the pH doesn't rise as expected.

With a -2 charge, you could expect carbonate to neutralize twice the acid content that bicarbonate can since it has a -1 charge (on an ion to ion basis). But carbonate does not dissociate completely in water or wort. To help account for that apparent deficiency, users assumed that the 158 ppm value should be applied instead of the 322 ppm value.

But in typical usage, chalk doesn't even provide the 158 ppm contribution to alkalinity. In fact, there is only a minor strong acid content in wort. Adding chalk to mash or wort typically only raises pH by about 0.1 unit...no matter how much chalk you add. While wort is clearly 'acidic' since its pH is below 7, the acids that drive the pH down are very 'weak'. They don't have the power to react with the carbonate in chalk.

The bottom line will always be: DON'T USE CHALK IN BREWING...IT DOESN'T WORK AT ALL!!!!!! 
Martin B
Carmel, IN

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Foam Blowers of Indiana (FBI)

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Offline bjanat

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Re: Carbonate Hardness = Carbonate Alkalinity based on Source pH?
« Reply #18 on: April 13, 2018, 12:13:47 PM »
Unfortunately, Kai's information is incorrect too. There is history behind that value when talking about chalk.

As you may have heard, it takes extraordinary measures to get chalk to dissolve in water. Unfortunately, that also applies to wort since wort doesn't have much of the 'strong' acid content needed to dissolve chalk. Brewers know that chalk doesn't provide the alkalinity that its chemistry says it adds and therefore the pH doesn't rise as expected.

With a -2 charge, you could expect carbonate to neutralize twice the acid content that bicarbonate can since it has a -1 charge (on an ion to ion basis). But carbonate does not dissociate completely in water or wort. To help account for that apparent deficiency, users assumed that the 158 ppm value should be applied instead of the 322 ppm value.

But in typical usage, chalk doesn't even provide the 158 ppm contribution to alkalinity. In fact, there is only a minor strong acid content in wort. Adding chalk to mash or wort typically only raises pH by about 0.1 unit...no matter how much chalk you add. While wort is clearly 'acidic' since its pH is below 7, the acids that drive the pH down are very 'weak'. They don't have the power to react with the carbonate in chalk.

The bottom line will always be: DON'T USE CHALK IN BREWING...IT DOESN'T WORK AT ALL!!!!!!
Thanks for that clarification. I never got the Brewer’s Friend calculator to make sense for the HCO3 part. I just ignore that part.

Offline hackrsackr

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Carbonate Hardness = Carbonate Alkalinity based on Source pH?
« Reply #19 on: April 13, 2018, 12:46:49 PM »
Unfortunately, Kai's information is incorrect too. There is history behind that value when talking about chalk.

As you may have heard, it takes extraordinary measures to get chalk to dissolve in water. Unfortunately, that also applies to wort since wort doesn't have much of the 'strong' acid content needed to dissolve chalk. Brewers know that chalk doesn't provide the alkalinity that its chemistry says it adds and therefore the pH doesn't rise as expected.

With a -2 charge, you could expect carbonate to neutralize twice the acid content that bicarbonate can since it has a -1 charge (on an ion to ion basis). But carbonate does not dissociate completely in water or wort. To help account for that apparent deficiency, users assumed that the 158 ppm value should be applied instead of the 322 ppm value.

But in typical usage, chalk doesn't even provide the 158 ppm contribution to alkalinity. In fact, there is only a minor strong acid content in wort. Adding chalk to mash or wort typically only raises pH by about 0.1 unit...no matter how much chalk you add. While wort is clearly 'acidic' since its pH is below 7, the acids that drive the pH down are very 'weak'. They don't have the power to react with the carbonate in chalk.

The bottom line will always be: DON'T USE CHALK IN BREWING...IT DOESN'T WORK AT ALL!!!!!!

Ok, but then why does your sheet give me such a high mash pH (6.2) from the chalk additions, if it doesn’t raise the pH that much (which I agree with)? Is the 322 number there just to keep the mEq/l balance even, but not affecting the predicted mash pH to the extent that 322 ppm HCO3 would (and I guess the Ca contribution would also be different).


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« Last Edit: April 13, 2018, 01:15:45 PM by hackrsackr »

Offline mabrungard

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Re: Carbonate Hardness = Carbonate Alkalinity based on Source pH?
« Reply #20 on: April 13, 2018, 02:51:17 PM »
Ok, but then why does your sheet give me such a high mash pH (6.2) from the chalk additions, if it doesn’t raise the pH that much (which I agree with)? Is the 322 number there just to keep the mEq/l balance even, but not affecting the predicted mash pH to the extent that 322 ppm HCO3 would (and I guess the Ca contribution would also be different).


If you read the comment that is attached to the chalk addition on the Water Adjustment sheet, you'll see that it says:

Chalk has limited solubility (about 50 mg/L) in water and wort
making it less suitable for adding alkalinity. 
DO NOT USE CHALK FOR BREWING UNLESS IT HAS BEEN
FULLY PRE-DISSOLVED INTO WATER WITH CO2.

If you're not doing that, then the calculations are worthless.

I'll restate the most important part of my previous message: DON'T USE CHALK IN BREWING
Martin B
Carmel, IN

BJCP National
Foam Blowers of Indiana (FBI)

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Offline mchrispen

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Re: Carbonate Hardness = Carbonate Alkalinity based on Source pH?
« Reply #21 on: April 13, 2018, 03:03:10 PM »
Somehow this reminds me of the kwasser? (chalk water) discussion with Aj a few years ago.



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Offline hackrsackr

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Re: Carbonate Hardness = Carbonate Alkalinity based on Source pH?
« Reply #22 on: April 13, 2018, 03:25:54 PM »
Ok, but then why does your sheet give me such a high mash pH (6.2) from the chalk additions, if it doesn’t raise the pH that much (which I agree with)? Is the 322 number there just to keep the mEq/l balance even, but not affecting the predicted mash pH to the extent that 322 ppm HCO3 would (and I guess the Ca contribution would also be different).


If you read the comment that is attached to the chalk addition on the Water Adjustment sheet, you'll see that it says:

Chalk has limited solubility (about 50 mg/L) in water and wort
making it less suitable for adding alkalinity. 
DO NOT USE CHALK FOR BREWING UNLESS IT HAS BEEN
FULLY PRE-DISSOLVED INTO WATER WITH CO2.

If you're not doing that, then the calculations are worthless.

I'll restate the most important part of my previous message: DON'T USE CHALK IN BREWING
I get the importance of pH vs carbonate species. I’m just curious as to why your calculations are so high from chalk additions. Even fully dissolved with CO2 CaCO3, the alkalinity contribution is still significantly higher than Kai’s chalk experiments. If the calculations are worthless, then why do you include them? Oh, and...

I’LL USE CHALK IF I WANT TO,
Thanks!

Offline mabrungard

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Re: Carbonate Hardness = Carbonate Alkalinity based on Source pH?
« Reply #23 on: April 13, 2018, 06:05:47 PM »
I get the importance of pH vs carbonate species. I’m just curious as to why your calculations are so high from chalk additions. Even fully dissolved with CO2 CaCO3, the alkalinity contribution is still significantly higher than Kai’s chalk experiments. If the calculations are worthless, then why do you include them? Oh, and...

I’LL USE CHALK IF I WANT TO,
Thanks!

I apologize. I haven't made it clear that you are talking about two different anions. However, they do happen to have an equivalence. The 158 ppm of CO3 can be expressed equivalently as 322 ppm of HCO3. Both of those expressions result in the same amount of alkalinity.

PS: Kai's chalk experiments were flawed and even AJ Delange mentioned that to Kai. Kai was a real trooper and he often did interesting work. Unfortunately, he did get over his head occasionally.
Martin B
Carmel, IN

BJCP National
Foam Blowers of Indiana (FBI)

Brewing Water Information at:
https://sites.google.com/site/brunwater/

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Offline hackrsackr

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Re: Carbonate Hardness = Carbonate Alkalinity based on Source pH?
« Reply #24 on: April 13, 2018, 08:02:21 PM »
I get the importance of pH vs carbonate species. I’m just curious as to why your calculations are so high from chalk additions. Even fully dissolved with CO2 CaCO3, the alkalinity contribution is still significantly higher than Kai’s chalk experiments. If the calculations are worthless, then why do you include them? Oh, and...

I’LL USE CHALK IF I WANT TO,
Thanks!

I apologize. I haven't made it clear that you are talking about two different anions. However, they do happen to have an equivalence. The 158 ppm of CO3 can be expressed equivalently as 322 ppm of HCO3. Both of those expressions result in the same amount of alkalinity.

PS: Kai's chalk experiments were flawed and even AJ Delange mentioned that to Kai. Kai was a real trooper and he often did interesting work. Unfortunately, he did get over his head occasionally.
Yup I get that they’re two two separate species of carbonate. It’s the HCO3 equivalent of 158 ppm CO3 equating to 322 ppm. I’ve never seen that before. It appears you used the the ppm of HCO3 that equated to the 5.3 mEq/l value of the of the CO3.  Which makes sense (the use of that route for the hydroxide is also interesting).

The part that doesn’t make sense to me is that in Palmers water book he states that CaCO3 dissolved by CO2 is roughly equivalent to the HCO3 component of NaHCO3. Which is like 180 something ppm HCO3, which appears to be how Kai did the CO3 to HCO3 conversion... but that doesn’t make sense in terms of mEq/l ionic balance. So it was trying to correlate these two methods that wasn’t working (which makes sense if kais experiments are flawed).

The ionic balance way honestly makes more sense to me. It’s just the pH dependence and variance of the mEq/l values that makes it difficult to implement IMO.

Thanks, for understanding that I was joking with the caps lock. Wasn’t sure.