Help me to understand chloride - sulfate ratio

[Donner]

a chloride to sulfate ratio of bitter.

why bitter and not 'very bitter' if you don't mind me asking.

 

[JLem]

Exactly. If you use Palmer's spreadsheet and can get the RA into your target area, then the pH of your mash should work itself out. For me, I have hard water, VERY hard water (I preboil to remove bicarbonate, but that's a separate topic). So I use Palmer's spreadsheet. If I'm doing something sort of pale like an IPA, I will dilute with about 50% distilled water. And this is on the spreadsheet too. I then add salts to achieve the correct RA and the correct chloride/sulfate ratio.

Looking at a spreadsheet I was working on last night for an IPA: the color of the beer is 9.2. Input that into the target color box and it gives me a RA range of -10 to 49. I aimed right for the middle, 19 for RA. I then input a 52% dilution rate with distilled water. This beer has a thin mash, lotsa water, so I input the 5.87 gallons of mash water, then add 4 grams of gypsum, 4 grams of calcium chloride and 2 grams of epsom salts on the spreadsheet. This gives me an RA of 19 and a chloride to sulfate ratio of bitter. You can go back and forth on the dilution rate and/or salts to nail the number where you want it.

The color of your beer affects the target RA because darker grains lower your pH. So if you make a darker beer, you can have a higher RA, if you have a lower color you need a lower RA. Salts lower pH, dark grain lowers pH, carbonate raises pH. It's about balancing these things.

Using this spreadsheet on the last 3 beers, I've nailed my mash pH each time without any stabilizer or anything and the beers have rocked. It's not *just* about the water, but it helps.

As linked on the first page of the thread, go to the bottom of this Palmer page for his spreadsheet:

http://www.howtobrew.com/section3/chapter15-3.html

So, what about for a partial mash? Is the RA adjustment only needed for the mash volume? But the Cl:SO4 ratio needs to be adjusted for the entire volume?

For example, say I only mash 4 pounds of grain in 1.5 gallons of water, but want to make a 5 gallon batch. I would add enough salts (e.g. CaCO3 and/or NaHCO3) to my (soft) 1.5 gallons of mash water to hit the necessary RA in the mash, but not worry about adding these same salts into the rest of the 3.5 gallons in the boil. Instead I would want to make sure that my CL:SO4 ratio was where I wanted it by adding the appropriate additions into the boil? Or does it matter?

 

[MattHollingsworth]

why bitter and not 'very bitter' if you don't mind me asking.

I've only used this spreadsheet on 3 beers so far. And one was an APA and I used "bitter" and LOVED the balance. And I typically don't like *very* bitter beers. Sure I'll try the "very bitter" balance at some point but I'm in no hurry.

 

[MattHollingsworth]

So, what about for a partial mash? Is the RA adjustment only needed for the mash volume? But the Cl:SO4 ratio needs to be adjusted for the entire volume?

For example, say I only mash 4 pounds of grain in 1.5 gallons of water, but want to make a 5 gallon batch. I would add enough salts (e.g. CaCO3 and/or NaHCO3) to my (soft) 1.5 gallons of mash water to hit the necessary RA in the mash, but not worry about adding these same salts into the rest of the 3.5 gallons in the boil. Instead I would want to make sure that my CL:SO4 ratio was where I wanted it by adding the appropriate additions into the boil? Or does it matter?

I think you should adjust your mash pH, yes, to get optimum results IN the mash. But if you're using extract, extract already has salts in it from wherever the mash was done to produce that extract. I personally wouldn't use salts to adjust extract beers. You can if you want, but I'd use a light hand with that as you're basically guessing about what's already in there. Jamil and John Palmer also say this, though I don't have a link for that. But with partial mash, my thought is that I would use some adjustments. Say I got half of my wort sugars from mashing, I would adjust at half of what I wanted in the final beer. If I could find out what was IN the extract, as far as salts go, I'd go further, but that seems unlikely. Otherwise, I'd adjust half of the water, basically.

But I don't do extract or partial mash, so don't really have a well founded opinion on the subject. Just what I read and hear.

 

[MattHollingsworth]

I've only used this spreadsheet on 3 beers so far. And one was an APA and I used "bitter" and LOVED the balance. And I typically don't like *very* bitter beers. Sure I'll try the "very bitter" balance at some point but I'm in no hurry.

I should clarify that. I love IPAs, which *are* very bitter beers. But I typically like the IPAs that are not over the top and I don't like Imperial IPAs for the most part, for instance. I lived in Portland for 9 years and found a lot of the west coast IPAs to not be to my liking. For my own IPAs I scaled back a touch on the bittering especially to achieve a better balance. I wasn't using this spreadsheet in those days though and didn't take good notes on the water. So, now that I'm brewing again years later, I'll see what water I like over the course of the next couple of years as I tweak and fine tune it. But so far, so good. The 3 beers so far have been great.

Also, I typically like a softer bittering than some folks. When I see people saying first wort hops leads to too soft of a bittering, I don't agree. When I see people describe some hops as having too soft of a bittering note, I tend to want to try those hops.

Another thing to note about my comments about west coast IPAs here is that at the time, the Imperial IPA category didn't really exist. Rogue was the only one I remember see doing what they actually called an IIPA. I think people were pushing the IPA category itself towards the Imperial, which I'm not so into. I don't know if that's faded now and people go ahead and have regular IPAs and Imperial IPAs. And yeah, I already KNOW that the point of IIPA is not balance, like Pliny. But those beers just aren't for me.

 

[conpewter]

I have it dry hopping right now, I'll put it in the kegorator on Sat/Sun and give it a few days to carbonate then give some results.

Initial thoughts when I tasted it before dry hopping was that it gained some of the bitterness that I wanted. I will need to brew it again and get the efficiency I was looking for, and also add the gypsum in the mash and the boil instead of in the HLT.

Turned out to be a great beer, enough so that I didn't get a chance to bottle any of it because I drank it all :/ so unfortunately no competition results. Anyway I brewed up another IPA a week or so ago and did dilute with some distilled to knock my bicarbonates down (383 ppm HCO3, yikes)

 

[MattHollingsworth]

Turned out to be a great beer, enough so that I didn't get a chance to bottle any of it because I drank it all :/ so unfortunately no competition results. Anyway I brewed up another IPA a week or so ago and did dilute with some distilled to knock my bicarbonates down (383 ppm HCO3, yikes)

My bicarbonates are at 386, so we're in the same family of hard water! I've been preboiling and then diluting, with great results thus far. But I don't brew really super pale beers anyway. My APA was 8.7 SRM. Came out great with preboiled water, then diluted with 52% distilled water then salts added...

 

[conpewter]

My bicarbonates are at 386, so we're in the same family of hard water! I've been preboiling and then diluting, with great results thus far. But I don't brew really super pale beers anyway. My APA was 8.7 SRM. Came out great with preboiled water, then diluted with 52% distilled water then salts added...

Sounds good, how do you determine how much HCO3 and CA are precipitated out?

 

[MattHollingsworth]

Sounds good, how do you determine how much HCO3 and CA are precipitated out?

Going from memory here: I use the formula from Dave Miller's book, which states that for every 5 ppm of bicarbonate you precipitate out, you also lose 3 ppm of calcium. And you're limited in how much bicarbonate you can get rid of by your calcium, which is why some folks add salts before boiling to precipitate. I don't add salts before boiling. I don't want elevated chloride or sulfate and then zero calcium. That'd really make those sulfate and/or chloride numbers jump when it cam time to add salts to get the calcium back up. I'd rather just boil as is, then dilute.

I have 86 ppm of calcium in my water, so I figure I can lose 143 ppm of bicarbonate, leaving me with 243. I then dilute from there. I basically changed my spreadsheet to reflect this. So as a starting point, it reads 0 for calcium and 243 for bicarbonates, and it's been doing well for me. But I always aim right for the dead center average of the RA number.

For the brown ale I just did, though, I didn't preboil at all and just diluted a little because of the dark grain.

 

[conpewter]

Thanks Matt! I'll look into doing that instead of buying so much distilled water. The electric HLT makes pre-boiling rather inexpensive.

Do you need to decant the water off the precipitate immediately or can you just pre-boil then the next day use the water after re-heating to strike temp?

 

[MattHollingsworth]

I use a 14 or so liter kettle on the stove, boil, then rack off with a stainless racking cane. I give it a good stir so the chalk crap settles in the middle, and rack off the side.

See this thread for pics and such:

https://www.homebrewtalk.com/f13/effectiveness-pre-boiling-water-remove-bicarbonate-134108/

 

[sudbuster]

I've seen references to John Palmer over and over in this thread. WTF is John Palmer when it comes to homebrewing? He doesn't know any more about it than we do. He's a metallurgist for crissake. He just likes to promote himself and write books for money. If I were wanting info on water chemistry I'd ask a chemist. If I were wanting info on welding, I'd ask John Palmer...........

 

[hexmonkey]

I've seen references to John Palmer over and over in this thread. WTF is John Palmer when it comes to homebrewing? He doesn't know any more about it than we do. He's a metallurgist for crissake. He just likes to promote himself and write books for money. If I were wanting info on water chemistry I'd ask a chemist. If I were wanting info on welding, I'd ask John Palmer...........

I'm not sure it works that way. Is metallurgy not a type of chemistry? Besides, by that logic, Jamil Z is full of crap and shouldn't be reliable either.

Here's a link to notes from Palmer's presentation on proteins and head retention at this year's NHC; tell me the person who made this doesn't know anything about homebrewing:
http://www.beertown.org/events/hbc/presentations/2009/John-Palmer-NHC2009-Proteins.pdf

 

[MattHollingsworth]

Nattering naybob of negativism!

;-)

Palmer's written some good information on brewing and regularly spends a lot of time trying to help other homebrewers. If he's "one of us", all the better. Don't see any reason to knock him.

Anyway, his spreadsheet works. The proof's in the pudding, er beer.

 

[Ketchepillar]

Ok, let's talk real numbers. I understand what Palmer and others are saying about the sulfate:chloride ratio, but it doesn't make sense when looking at classic brewing cities. If I'm not mistaken, he says balanced between "malty/sweet" and "dry/bitter" is 1:1, or equal quantities of each. So, 30ppm Chloride, 30ppm Sulfate or 150ppm Sulfate; 150ppm Chloride. Correct? Moving on then, looking at "classic" water profiles, I see London as 32ppm:34ppm-essentially 1:1, Pilsen 1:1, and various other less well known Belgian cities (Achouffe, Poperinge, Luik)at even, or slightly tilted to Cl-. And even some cities that have descriptions of being balanced to malty/sweet are still Sulfate balanced i.e.


"Munich

Ca+
109

Mg+
21

HCO3
171

SO4
79

Na+
2

Cl-
36

Oktoberfest
Munich - Although moderate in most minerals, alkalinity from carbonates is high. The smooth flavors of the dunkels, bocks and oktoberfests of the region show the success of using dark malts to balance the carbonates and acidify the mash. The relatively low sulfate content provides for a mellow hop bitterness that lets the malt flavor dominate." -from How to Brew
79:36 essentially 2:1

So what is the actual "balanced' range? What do you like to do? Where can I find good ratios for different styles? Is there really no difference between the same ratio at different levels (within reason), is 10ppm:10ppm really equal 150ppm:150ppm?

 

[jds]

First off, speaking as another metallurgist -- inorganic chemistry is a big part of the science, so there's no reason to think Palmer doesn't know what he's talking about. Secondly, regardless of his schooling, the guy has LEARNED more about brewing that most of the rest of us, and he communicates it well.

Secondly, what's everybody's understanding on making additions to the mash vs. the mash and sparge? My water is relatively soft (Denver), with a Cl/SO4 ratio biased toward the bitter side of things. I've been treating my mash water only, but I think that's still leaving me more biased toward chloride than sulfates.

So then, since I have to add hardness for anything darker than about 15 SRM, should I be adding hardness to the mash only and just adjusting sparge water for the Cl/SO4 ratio, or should I treat all the water for hardness too? It seems like the first is the way to go, unless I'm misunderstanding something, right?

Right?

 

[LeeF]

Secondly, what's everybody's understanding on making additions to the mash vs. the mash and sparge? My water is relatively soft (Denver), with a Cl/SO4 ratio biased toward the bitter side of things. I've been treating my mash water only, but I think that's still leaving me more biased toward chloride than sulfates.

So then, since I have to add hardness for anything darker than about 15 SRM, should I be adding hardness to the mash only and just adjusting sparge water for the Cl/SO4 ratio, or should I treat all the water for hardness too? It seems like the first is the way to go, unless I'm misunderstanding something, right?

Right?

You bring up a good point that I have asked in another thread. I've been reading about and making water adjustments since going to all grain a year ago. Now that I'm confident in my consistency, my plan is to make the same recipe and only tweak the water. One of my last batches was Ed Worts Haus Pale. A light APA should be a good starting point plus my wife loves it.

If anyone wants to do the same but with a different style(or same style) we could start a thread and share info. Having more than one palate of reference would be good. For everyone involved we should give our water profile and how we plan to adjust the water. With enough participants we could all do two batches of the same recipe and get a lot of good info.

 

[daveotero]

So what is the actual "balanced' range? What do you like to do? Where can I find good ratios for different styles? Is there really no difference between the same ratio at different levels (within reason), is 10ppm:10ppm really equal 150ppm:150ppm?

I'm wondering this also. My water is pretty soft and my chloride to sulfate Ratio favors bitterness.

CL :25
SO: 54
Ratio: .46

If I can add 50 ppm of chloride to achieve a 1:1 balance, would that be identical to a profile with ~300 ppm of each?

The other issue with soft water that I can see is the low levels incresses the potential for error. If my city water report is off by 10 to 20 ppm for either value it could seriously mess up the results. For those who might have have you water tested, was the report similar to the values form the city?

 

[Beerrific]

If I can add 50 ppm of chloride to achieve a 1:1 balance, would that be identical to a profile with ~300 ppm of each?

The other issue with soft water that I can see is the low levels incresses the potential for error. If my city water report is off by 10 to 20 ppm for either value it could seriously mess up the results. For those who might have have you water tested, was the report similar to the values form the city?

No, once you start to get up that high, you can start to taste the 'minerally' aspect. My water report is a 12-month average from the previous year, but tends to have low levels. I like to bump my numbers up to adjust for the fact that it could off on any given day.

I've seen references to John Palmer over and over in this thread. WTF is John Palmer when it comes to homebrewing? He doesn't know any more about it than we do. He's a metallurgist for crissake. He just likes to promote himself and write books for money. If I were wanting info on water chemistry I'd ask a chemist. If I were wanting info on welding, I'd ask John Palmer...........

This is such a ridiculous comment, I don't even know how to respond.

 

[Bobby_M]

I don't hold Palmer or Jamil up at any kind of god status and I'm sure they would humbly agree with that sentiment. However, they have done due research on the topics they write about. Jamil gets respect for the pure fact that he has won Ninkasi and he deserves it. In any case, everyone should question the facts as they are posed in all cases no matter who they originate from. Go ahead and read the references given at the end of How to Brew.

 

[SpanishCastleAle]

Secondly, what's everybody's understanding on making additions to the mash vs. the mash and sparge? My water is relatively soft (Denver), with a Cl/SO4 ratio biased toward the bitter side of things. I've been treating my mash water only, but I think that's still leaving me more biased toward chloride than sulfates.

So then, since I have to add hardness for anything darker than about 15 SRM, should I be adding hardness to the mash only and just adjusting sparge water for the Cl/SO4 ratio, or should I treat all the water for hardness too? It seems like the first is the way to go, unless I'm misunderstanding something, right?

That doesn't really make sense. If anything you'd add alkalinity to your water to make darker brews. You need a higher RA for darker brews and alkalinity increases RA, hardness decreases RA (better for light colored brews).

Some state that you don't need to treat the sparge water unless it's alkaline and you're brewing light-colored beers. I treat all the water for light brews and only treat the mash water for dark brews. But you're on the right track that during the mash it's only the pH we're concerned with (so alkalinity and hardness)...the chloride:sulphate ratio or any additions for flavor can go in later. I just do it all at the beginning.

 

[Alemental]

Secondly, what's everybody's understanding on making additions to the mash vs. the mash and sparge?

I start with RO and add whatever salts are needed. For the mash, the salts are added right with the grain at dough in. For the sparge, I use straight RO water, and then add the salts directly to the boil kettle for the amount of sparge water needed to hit my preboil level. In the end, my mash and sparge water are identical, just as the mash and sparge water has traditionally been identical in the historic brewing cities.
The reason not to add salts to your sparge water is that some of them, calcium carbonate in particular, don't dissolve well into plain water, but will at the pH levels in the kettle.

 

[hexmonkey]

That doesn't really make sense. If anything you'd add alkalinity to your water to make darker brews. You need a higher RA for darker brews and alkalinity increases RA, hardness decreases RA (better for light colored brews).

I'm confused by your statement that "hardness decreases RA". Isn't hardness a measure of bicarbonate in the water? Can you have hard water with a low pH?

 

[MattHollingsworth]

From my understanding, "permanent" hardness is hardness derived from Calcium and Magnesium, while "temporary" hardness is derived from carbonate. Gypsum and Calcium Chloride lower the pH. Carbonate has the effect of raising it.

 

[jds]

If anything you'd add alkalinity to your water to make darker brews. You need a higher RA for darker brews and alkalinity increases RA, hardness decreases RA (better for light colored brews).

Yeah. Brain fart. Nice catch. I add alkalinity to my water for darker beers.

 

[hexmonkey]

From my understanding, "permanent" hardness is hardness derived from Calcium and Magnesium, while "temporary" hardness is derived from carbonate. Gypsum and Calcium Chloride lower the pH. Carbonate has the effect of raising it.

I'm not really sure if I'm reading this right, but according to wikipedia, CaCl2 has an acidity of 8-9?

http://en.wikipedia.org/wiki/Calcium_chloride

(under Properties in sidebar on right)
Acidity (pKa)
8-9 (anhydrous)
6.5-8.0 (hexahydrate)

Calcium sulfate (gypsum) has an acidity even higher:

http://en.wikipedia.org/wiki/Calcium_sulfate

Acidity (pKa)
10.4 (anhydrous)
7.3 (dihydrate)

 

[MattHollingsworth]

I'm not really sure if I'm reading this right, but according to wikipedia, CaCl2 has an acidity of 8-9?

http://en.wikipedia.org/wiki/Calcium_chloride

(under Properties in sidebar on right)
Acidity (pKa)
8-9 (anhydrous)
6.5-8.0 (hexahydrate)

Calcium sulfate (gypsum) has an acidity even higher:

http://en.wikipedia.org/wiki/Calcium_sulfate

Acidity (pKa)
10.4 (anhydrous)
7.3 (dihydrate)

Don't think that's important to know, personally. If you get your head around the basic concepts of what's going on, that's good enough.

 

[Hermit]

I start with RO and add whatever salts are needed. For the mash, the salts are added right with the grain at dough in. For the sparge, I use straight RO water, and then add the salts directly to the boil kettle for the amount of sparge water needed to hit my preboil level. In the end, my mash and sparge water are identical, just as the mash and sparge water has traditionally been identical in the historic brewing cities.
The reason not to add salts to your sparge water is that some of them, calcium carbonate in particular, don't dissolve well into plain water, but will at the pH levels in the kettle.

Is RO close enough to distilled to not worry about the numbers or does it really need to be tested?

 

[hexmonkey]

Don't think that's important to know, personally. If you get your head around the basic concepts of what's going on, that's good enough.

I'm not sure how that isn't important. If you're adding something to water that either increases or decreases its pH, shouldn't you know which one it does?

 

[MattHollingsworth]

I'm not sure how that isn't important. If you're adding something to water that either increases or decreases its pH, shouldn't you know which one it does?

I'm not saying it's not important to know what those salts do. I'm saying it's not important that you look up the exact information you posted from WikiPedia. If you can tell me what you're going to do with that information I'd be curious.

The basic stuff to understand has already been posted. Yes, salts lower the pH. I've said that before. Dark grains also lower the pH. Calcium Carbonate will raise it.

But you can also end up reading into this too far and lose sight of the basic idea behind this stuff.