Help me to understand chloride - sulfate ratio

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hexmonkey

hexmonkey

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In several podcasts on water chemistry, Palmer mentions that the pH isn't as important as the chloride to sulfate ratio. He has said that this is because the acidity of the grains will buffer most of the alkalinity of the water.

He goes on to say that the chloride to sulfate ratio has more to do with the flavor outcome of the final beer because chloride enhances malt character while sulfate enhances hops character.

But does this mean that a 50/50 ratio of chloride to sulfate will make an evenly balanced beer, all other things being equal? Or for that matter, is it a direct relationship from this ratio to the flavor profile (i.e., 60/40 Cl/SO4 = maltiness and 40/60 Cl/SO4 = hoppiness)?
 
I think that seems to be the case. I think it is interesting that he chooses "malty" and "bitter" as the descriptors. I am not sure I see those as definatively opposite. I think "bitter" vs. "sweet" might be better. Here is the only other reference to this I have seen:
Handbook of brewing - Google Book Search

I also wonder where this comes in. If it is simply perception only, then one could in theory just add some salt (CaCl2 or CaSO4) to the 2 pours of a beer and compare. I think I am going to try this soon.
 
hexmonkey said:
In several podcasts on water chemistry, Palmer mentions that the pH isn't as important as the chloride to sulfate ratio. He has said that this is because the acidity of the grains will buffer most of the alkalinity of the water.

He goes on to say that the chloride to sulfate ratio has more to do with the flavor outcome of the final beer because chloride enhances malt character while sulfate enhances hops character.

But does this mean that a 50/50 ratio of chloride to sulfate will make an evenly balanced beer, all other things being equal? Or for that matter, is it a direct relationship from this ratio to the flavor profile (i.e., 60/40 Cl/SO4 = maltiness and 40/60 Cl/SO4 = hoppiness)?
Click to expand...

"Ratio" does not imply 50/50. I don't know what the proper ratio should be, but it could easily be 2:1, 3:2, 10:1, or even 1000:1. All it means is that if you jack up one value, you should also jack up the other and vice-versa.
 
This is from his spreadsheet
The chloride to sulfate ratio is known to be a strong factor for the taste of the beer. A beer with a ratio of chloride to sulfate of 1-2 will have a maltier balance, while a beer with a chloride to sulfate ratio of 0,5-1 will have a drier, more bitter balance.
Click to expand...

How to Brew - By John Palmer - Residual Alkalinity and Mash pH

Spreadsheets at the bottom of the page, found this in the instructions section
 
conpewter said:
The chloride to sulfate ratio is known to be a strong factor for the taste of the beer. A beer with a ratio of chloride to sulfate of 1-2 will have a maltier balance, while a beer with a chloride to sulfate ratio of 0,5-1 will have a drier, more bitter balance.
Click to expand...
Hmmm, aren't those the exact same ratios? I would have thought 2:1 Chloride:Suphate = malty (actually, very malty) and 1:2 Chloride:Suphate = bitter (actually, very bitter). At least that's the way the spreadsheet works.

FWIW, it just so happens that the 'balanced' ratio is centered around '1'. So 1:1 Chloride:Suphate is considered balanced.

All it means is that if you jack up one value, you should also jack up the other and vice-versa.
Click to expand...
Not exactly...it just means that the two quantities are considered relative to each other. If you jack both of them up then you didn't change the ratio (or bitterness:maltiness)...you just added salts.
 
SpanishCastleAle said:
Hmmm, aren't those the exact same ratios? I would have thought 2:1 Chloride:Suphate = malty (actually, very malty) and 1:2 Chloride:Suphate = bitter (actually, very bitter). At least that's the way the spreadsheet works.

FWIW, it just so happens that the 'balanced' ratio is centered around '1'. So 1:1 Chloride:Suphate is considered balanced.


Not exactly...it just means that the two quantities are considered relative to each other. If you jack both of them up then you didn't change the ratio (or bitterness:maltiness)...you just added salts.
Click to expand...

I think palmer is giving a ratio range. So a ratio of 1 and up to 2 will be more malty. a ratio of .5 to 1 will be more bitter.

so 50ppm chloride/100ppm sulfate will give you a ratio .5 and thus be in the bitter range. 200chloride/100sulfate gives you a ratio of 2, so thus in the malty range.
 
Sorry conpewter...I completely misunderstood you're first post. I thought you were giving the ratios themselves; i.e. 1:2 instead of the range of the value of the ratio; i.e. 1-2.
 
Beerrific said:
I also wonder where this comes in. If it is simply perception only, then one could in theory just add some salt (CaCl2 or CaSO4) to the 2 pours of a beer and compare. I think I am going to try this soon.
Click to expand...

Is this to say that perhaps the bitterness or maltiness could be adjusted after the fact with very small adjustments to the final beer? Or are these factors due to differing extraction rates of flavor compounds in the wort?
 
I have pretty hard water, so I generally avoid any salt additions.

But now, if I understand it well: even if I have lots od sulfates, and lots of chloride, as soon as they balance each other, they have neutral impact on taste. And, I can, for instance, add even more gypsum to move the balance towards sulfates and enhance hopiness?

Well, when I add gypsum I will increase Ca level as well as sulfates... can that be an issue?
 
What I do when my water is too hard or alkaline is to just dilute with Distilled/RO water to reduce the hardness and alkalinity and then 'rebuild' whatever I need. I almost always dilute to achieve a target alkalinity and then adjust the hardness after that (but that's with my water). If you want sulphates you could use a little Epsom Salt (MgSO4) and decrease the Gypsum a little...the Mg still increases hardness but not nearly as much as Calcium. But if you go for high-ish sulphates you should make sure the Sodium is low-ish...from what I've read you don't want high Sulphates and Sodium.

After I've diluted my water to my target alkalinity, typically the only salts required to get everything right are CaCl, Gypsum, and Epsom salt. I could just use CaCl and Gypsum but after the dilution I don't have quite enough Mg so I need the Epsom for that. So I add a tiny bit of Epsom to get my Mg back and then use the CaCl and/or Gypsum to get my Calcium and adjust the chloride:sulphate ratio. The Sodium content is very low.
 
SpanishCastleAle said:
If you want sulphates you could use a little Epsom Salt (MgSO4) and decrease the Gypsum a little...the Mg still increases hardness but not nearly as much as Calcium. But if you go for high-ish sulphates you should make sure the Sodium is low-ish...from what I've read you don't want high Sulphates and Sodium.
Click to expand...

From How to Brew - By John Palmer - Reading a Water Report :

The combination of sodium with a high concentration of sulfate ions will generate a very harsh bitterness. Therefore keep at least one or the other as low as possible, preferably the sodium.
Click to expand...

However, you should also keep Magnesium levels down (from the same page as above):

Magnesium is an important yeast nutrient in small amounts (10 -20 ppm), but amounts greater than 50 ppm tend to give a sour-bitter taste to the beer. Levels higher than 125 ppm have a laxative and diuretic affect.
Click to expand...
 
Thanks for posting those references hexmonkey. I should have mentioned that my Mg level after dilution is like 1-3 ppm and I'm only adding enough Epsom to get it up to 6-10 ppm. I've never even exceeded 12 ppm Mg. That's really the only reason I use the Epsom at all...just to prevent my Mg from being excessively low.
 
I have very high alkalinity, great for porters/stouts etc. I used to use almost all distilled water for my lighter beers and try to buidl up the profile from that.

Last time I did an IPA though I just used enough gypsum to get my residual alkalinity in the right range and get a lot of So4 to match Burton on Trent's water.

For malty lighter beers I'll still need to dilute I believe.
 
I did an experiment on this; same beer (mild), different salt levels - ratios (Cl:SO4 in mg/L) from 0:0, 1:5, 5:1, 2.5:2.5, and 5:5. The beer normally has 2.1:2.7. With the luxury of being able to analyse the beers, I can also say that they had the same acidity (~.05) and IBU (~2).

The consensus was that the beer with no salts had an almost oily aftertaste to it, the 5Cl beer was almost too thick/smooth, 5SO4 had a really strong bitterness, 2.5 equal was both smooth and had a full bitterness, and the 5:5 brew had an unpleasant aftertaste that tasted like minerals. These differences were easily detectable, and 6/7 people agreed in a blind tasting.

Chloride enhances sweetness and mouthfeel, sulphate complexity and detection of bitterness. Depending on your style (ie. more SO4 for bitters, more Cl for stouts), you can mess around with these accordingly. I'd say don't JUST add one or the other though - you need a bit of each to balance things out. Also, too much of both or either will cause weird tastes. Personally, I'd probably avoid ratios with a greater difference than 2:5.

Calcium has more to do with acidity and yeast metabolism than taste. More is better :D. Hope that helps!
 
@TheChemist:
Great experiment and well done: 5 batches, blind testing panel...
This is good evidence that this whole water adjustment really works!
 
Piotr said:
Well, when I add gypsum I will increase Ca level as well as sulfates... can that be an issue?
Click to expand...

Calcium is required in the mash to lower the pH, like the chemist says it is also involved in yeast metabolism. In addition its involved in aiding both protein flocculation during the boil and flocculation of the yeast post fermentation.

Ca in the range of between 50 and 200 ppm should see you right.
 
TheChemist - Great info. I was wondering if you know the actual concentrations of the 2 ions for this test (i.e. in mg/L). The reason I ask is because I am planning on manipulating this ratio to help my beers (in particular upping Cl content to increase body, mouthfeel) but I wanted an idea of the max amount of each salt you used. For example, when you say the 5:5 beer had a mineral aftertaste, this isn't with 5 mg/L of SO4 and 5 mg/L Cl was it? I would guess that the 5:5 refers to the ratio and not absolute levels. At any rate, if possible could you clarifiy this?

Cheers,

Greg

TheChemist said:
I did an experiment on this; same beer (mild), different salt levels - ratios (Cl:SO4 in mg/L) from 0:0, 1:5, 5:1, 2.5:2.5, and 5:5. The beer normally has 2.1:2.7. With the luxury of being able to analyse the beers, I can also say that they had the same acidity (~.05) and IBU (~2).

The consensus was that the beer with no salts had an almost oily aftertaste to it, the 5Cl beer was almost too thick/smooth, 5SO4 had a really strong bitterness, 2.5 equal was both smooth and had a full bitterness, and the 5:5 brew had an unpleasant aftertaste that tasted like minerals. These differences were easily detectable, and 6/7 people agreed in a blind tasting.

Chloride enhances sweetness and mouthfeel, sulphate complexity and detection of bitterness. Depending on your style (ie. more SO4 for bitters, more Cl for stouts), you can mess around with these accordingly. I'd say don't JUST add one or the other though - you need a bit of each to balance things out. Also, too much of both or either will cause weird tastes. Personally, I'd probably avoid ratios with a greater difference than 2:5.

Calcium has more to do with acidity and yeast metabolism than taste. More is better :D. Hope that helps!
Click to expand...
 
gregdech said:
TheChemist - Great info. I was wondering if you know the actual concentrations of the 2 ions for this test (i.e. in mg/L). The reason I ask is because I am planning on manipulating this ratio to help my beers (in particular upping Cl content to increase body, mouthfeel) but I wanted an idea of the max amount of each salt you used. For example, when you say the 5:5 beer had a mineral aftertaste, this isn't with 5 mg/L of SO4 and 5 mg/L Cl was it? I would guess that the 5:5 refers to the ratio and not absolute levels. At any rate, if possible could you clarifiy this?

Cheers,

Greg
Click to expand...

The concentrations were g/L x 10^-1. So, the 5:5 was .5g/L each - I wanted to see how far I could take it :p. To be fair, the water I was using had a decent salt content by itself, so you could probably play with those numbers a bit depending on your water. Sorry for the lack of precision.

If you're wanting to up mouthfeel, you could also just up your mash temp by a degree or so - though it's a different 'kind' of mouthfeel when you do that, if you know what I mean (not better or worse, just different).
 
Thanks for the update. I have been manipulating the mash temps to up mouthfeel, but I figured for some beers, manipulating the Cl levels would help even more. For example, I recently did an oatmeal stout with a mash temp of 69-70C (156-158F) that still seemed to be lacking a little on the mouthfeel and body side and so I was thinking that perhaps adding some CaCl2 would help. The water I'm using is high in sulfate (64 ppm) and low in Cl (4 ppm) for a ratio of SO4:Cl of 16! It's good for dry and hoppy beers, but no so much for full bodied beers like the aforementioned oatmeal stout. Anyway, based on your results, it would appear as though playing around with this ratio can definitely help me out.

Cheers,

Greg


TheChemist said:
If you're wanting to up mouthfeel, you could also just up your mash temp by a degree or so - though it's a different 'kind' of mouthfeel when you do that, if you know what I mean (not better or worse, just different).
Click to expand...
 
MattHollingsworth said:
Was this long enough ago that you've seen the final outcome? If so, what was your impression of the final beer?
Click to expand...

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.
 
This thread along with some other podcasts has motivated me to really do some research on this. I am going to have 3 groups of different Cl:SO4 ratios: 1 (balanced), 2 (balance towards malt), and .5 (maybe less, hoppy balance). The beer was brewed with a ratio of 0.7. I would really like to have brewed with water I built, but for this first set of experiments I will assume what the county water report is accurate. I used 5.2 in this beer, I hope that this does not effect the Cl or SO4.

I think I will use 2 beers for this: an IPA and a blond. Going to use a triangle test and mix IPA an blond to try to avoid palate fatigue. I would love to include a commercial beer in this mix, if I can find one where I can easily get the Cl:SO4 ratio used in the beer.

I would like to a get a tasting panel of 6. Anyone in ATL interested?
 
Okay okay okay...I have GOT to be missing something here becasue I am CON-FUSED.

I am trying to understand water and I'm just getting into it but I ran across something the perplexes me. I think I understand the chloride/sulfate ratio thing but what is with this residual alkalinity thing? Is there a correlation? Am I just that lost? Or...is it that RA has to do with mash pH while CSR has to do with flavor profile? How do they come together or do they?
 
Rottnme said:
Okay okay okay...I have GOT to be missing something here becasue I am CON-FUSED.

I am trying to understand water and I'm just getting into it but I ran across something the perplexes me. I think I understand the chloride/sulfate ratio thing but what is with this residual alkalinity thing? Is there a correlation? Am I just that lost? Or...is it that RA has to do with mash pH while CSR has to do with flavor profile? How do they come together or do they?
Click to expand...

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
 
MattHollingsworth said:
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.
Click to expand...

Great post, thanks!

It also looks as though you have proven what Palmer states about the pH being dependent on minerals concentrations.

This is still a bit over my head but I'm beginning to grasp it and I'm starting to get excited about putting some of this new knowledge into application.
 
MattHollingsworth said:
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
Click to expand...

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?
 
Donner said:
why bitter and not 'very bitter' if you don't mind me asking.
Click to expand...

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.
 
JLem said:
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?
Click to expand...

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 said:
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.
Click to expand...

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 said:
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.
Click to expand...

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)
 
conpewter said:
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)
Click to expand...

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...
 
MattHollingsworth said:
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...
Click to expand...

Sounds good, how do you determine how much HCO3 and CA are precipitated out?
 
conpewter said:
Sounds good, how do you determine how much HCO3 and CA are precipitated out?
Click to expand...

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.
 
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?
 

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