Help me to understand chloride - sulfate ratio

[Alemental]

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

RO is very close to distilled. A little bit of minerals do slip past the filters, but it is very a tiny amount. For brewing purposes they are interchangable.
RO can be a lot cheaper too. The grocery store I go to has a dispensing machine where I can buy refills for $1.49 for 5 gallons. Some pet stores have it in bulk too. People use it to fill aquariums for exotic fish, sometimes a couple of hundred gallons at a time.

 

[Hermit]

RO is very close to distilled. A little bit of minerals do slip past the filters, but it is very a tiny amount. For brewing purposes they are interchangable.
RO can be a lot cheaper too. The grocery store I go to has a dispensing machine where I can buy refills for $1.49 for 5 gallons. Some pet stores have it in bulk too. People use it to fill aquariums for exotic fish, sometimes a couple of hundred gallons at a time.

I have RO at my sink. The local water has a web site but it doesn't list much. Just contaminates.....

 

[hexmonkey]

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.

LOL I just re-read what I posted last night and it doesn't even make sense to me now.

My original question was regarding this statement from earlier in the thread:

alkalinity increases RA, hardness decreases RA

Based on what I understand of hardness/alkalinity, I interpret that to mean:

Alkalinity increases alkalinity, carbonate decreases alkalinity

Whereas the first half is self-explanatory, I think the second half is a contradiction. SpanishCastleAle was saying that you need to decrease the RA to make lighter beers. But if you added carbonate, wouldn't that increase the pH and therefore the RA?

Am I totally backwards on this?

 

[MattHollingsworth]

No worries.

Simple:

To lower the pH:

Add calcium chloride, gypsum or dark malts. (Or lactic acid or acid malt.)

To raise the pH:

Add calcium carbonate.

The higher the pH, the higher the RA. High RA better for dark beers. Low RA better for pale beers.

 

[boredatwork]

In my opinion anything targeted towards homebrewing is going to be empirically stated. Meaning, I don't think anyone has sat down with chemistry equations to understand what is going on it beer. And I don't see why that would ever be considered as necessary. I don't even think Charlie Bamforth could or would do that.

My point is that these are things that have been "measured" through experience. So really the only way to understand it, or to verify it, is to try it yourself. I did for myself out of necessity, and now I can say that I have hard evidence (sitting in bottles) that Palmer's descriptions, at least of chlorides and sulfates, is real.

By the way - when it comes to water profiles, there are two intentions: mash pH, and flavor. The mash pH only applies to AG, but flavor profile applies to any brew method. An incorrect sulfate to chloride ratio can ruin even an extract beer.

 

[StAnthonyB]

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.

That Handbook link is incredible.... Thank you very very much.

 

[daveotero]

One question I haven't found a solid answer to...

Ignoring all other issues like mash pH and yeast nutrients, can the flavor effects of the chloride to sulfate ratio be adjusted after fermentation? Can I play with these levels in a finished beer?

Only issue I can think of would be possible salt solubility problems due to colder temperatures or beer pH. Precision measurements for only a pint of beer would be impossible on the home brewer scale, but this would be useful for getting a general idea of the flavor changes or adjustment in the keg or bottling bucket.

 

[Super64]

I'm going to bump this thread because I've been doing a lot of reading on water and its effects on brewing, which as usual, raise more questions.

Facts:

1. I, currently, am an Extract + Steeped grains brewer.

2. Town water is from 3 wells whose average values are as follows:
Ca = 4.87
Mg = 1.29
SO4 = 6.3
Na = 10.5
Cl = 18.4
CaCO3 = 33
Est pH = 5.85
Residual Alkalinity = 28.85

3. After punching these numbers under the "default values" of the calculator at brewer's friend the result is

Chloride to Sulfate Ratio = Highly Malty (18.4 : 6.3) or (2.9 : 1)
Alkalinity = Pale Ale (33)

I can't see a "highly malty" pale ale, unless you guys know of one.

4. Posts here and other places indicate us extract brewers are at the mercy of the water profile of the extract manufacturers.
( I am trying to get Muntons to provide this data)

So..

A. Don't worry, my water is so soft that I can make a pale ale with mild to moderate hoppiness or a great porter.

B. Everything but my Alkalinity is great, but I'm stuck using only distilled water.

C. Dilute my water by as much as 25% per batch, then build it back up by adding salts back in....

D. Use DME instead?

- Chemistry is not my strong suit.

 

[ajdelange]

You have lovely water - even the alkalinity is not that bad and that is easily dealt with by dilution with RO.

As an extract brewer you have far fewer concerns as the pH control aspect of water management has been taken care of for you by the extract manufacturer. That leaves flavor and really only one element of that is available to you and that is how much sulfate you use. That will effect the way the hops are perceived. The more sulfate you use the harsher, drier, sharper, coarser the hops bitterness will be. How much of this you want is entirely up to you and I always recommend that people brew the beer with no supplemental sulfate and then brew it again several times incrementally increasing it until they hit the level that gives them the beer they like best.

The chloride/sulfate ratio thing is something that was in a couple of papers written in the UK which found its way into the second edition of Handbook of Brewing. It has been grasped at as a possible way of simplifying brewing calculations and, of course, the relationship between SRM and RA is another. Wouldn't it be great if we could just dial in color, move a slider along a malty/hoppy ruler and come up with a water ion profile? Problem is we can't - you must learn what chloride and sulfate do independently* of one another and set their levels appropriately. Does anyone think that waters with 1 mg/L each sulfate and chloride, 10 mg/L sulfate and chloride and 250 mg/L sulfate and chloride will make beers that are essentially the same? That's what the ratio concept advertises. But common sense, and the experimental data given earlier in this thread show that it isn't that simple.

*They aren't probably completely independent. I don't want to get too hairy here but if we were doing principal components analysis on beer flavor and if the ratio criterion were valid chloride and sulfate would both be aligned with one of the principal components i.e. that PC would be of the form a*p[sulfate] - b*p[chloride]. I doubt very much this would turn out to be the case. OTOH I doubt that one would find one principal component 100% and sulfate and another 100% chloride either (if they were completely independent that would be the case).

 

[Super64]

Thanks Aj.

Your explanations have been very informative, as well as the rest of this thread.

I am posting the response from Muntons concerning their water report.

"Unfortunately I am unable to provide this information. We use a mix of borehole water, softened water and recycled water but the blend varies depending on usage. The 200g of water per kg of extract used would have little influence on the final beer when it is diluted with 2200g of your own water"

 

[ajdelange]

One question I haven't found a solid answer to...

Ignoring all other issues like mash pH and yeast nutrients, can the flavor effects of the chloride to sulfate ratio be adjusted after fermentation? Can I play with these levels in a finished beer?

I wasn't aware of this thread until it popped up to the top of the stack yesterday and so have been looking back over it.

It's easy to obtain an answer to this question simply by tasting a beer, shaking a little table salt into it and then tasting it again and repeating with gypsum or epsom salts. I think you will find the answer with respect to chloride is "yes". When I was a kid the blue collar workers in the bars did this as a matter of course with table salt. With the sulfate I don't know (I never saw shakers of gypsum on the bars in the dives I went into) but I expect the answer will be "no" as I think it is in the kettle where sulfate has its effect.

 

[ajdelange]

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)

Again, posted over a year ago but an interesting observation. Actually, these salts are the salts of a strong acid and a strong base. As such, they should give neutral (pH 7) solutions but that is based on theory that makes lots of assumptions. In fact they give solutions with basic pH but these solutions don't have any buffering capacity. Addition of small amounts of acid or base will cause dramatic changes in pH. The presence of the salt does have an effect but it is a minor one. pKa is an unfortunate choice of symbol for acidity as it is usually used to represent minus the log of the equilibrium constant for the dissociation of an acid e.g. HA + H2O <---> H3O* + A-. Salts separate into their cations and anions when dissolved but salts of strong acids and strong bases disassociate completely at any reasonable pH. One can calculate the theoretical pH of a mixture of an acid (such as hydrochloric acid) and a base (such as calcium hydroxide) from the pKa of the acid and the pKb (dissociation constant of the base) but AFAIK salts don't have pKa's (a real chemist might know). I think what they mean by this is the pH of a solution of the salt in DI water.

 

[jsmith32]

Wow, the amount of information in this thread is immense. Thank you very much to all who have contributed.

Regarding chloride to sulfate ratio, my current situation with my local water supply is as such:

15 ppm - Cl
30 ppm - SO4
Cl/SO4 = 0.5

Even at these relatively low levels, is the Chloride to Sulfate ratio just as significant as when the Chloride and Sulfate are at much higher levels (say, for example, five times greater, Cl = 75, SO4 = 150 ppm)?

Sorry if this question was answered earlier.

Thanks in advance,

Jason Smith

 

[ajdelange]

Think about this. Common sense is enough to answer the question. Then see #69 in this thread.

 

[jsmith32]

I'm simply asking if there are reasonable real-life lower and upper bounds to this ratio. I'm not a chemist, but I am guessing that if you have exceedingly low amounts of chloride & sulfate (e.g. 10 parts per billion), I assume that other elements will render this ratio insignificant. In the other direction, if you have exceedingly high amounts of chloride & sulfate (e.g. 1000 parts per million), I figure the beer may be undrinkable.

Do you not agree?

 

[ajdelange]

I'm simply asking if there are reasonable real-life lower and upper bounds to this ratio. I'm not a chemist, but I am guessing that if you have exceedingly low amounts of chloride & sulfate (e.g. 10 parts per billion), I assume that other elements will render this ratio insignificant. In the other direction, if you have exceedingly high amounts of chloride & sulfate (e.g. 1000 parts per million), I figure the beer may be undrinkable.

Do you not agree?

I absolutely do agree. You don't need to be a chemist or even a brewer to figure this out. Common sense is sufficient as you have demonstrated.

 

[flipper51]

While it is fairly obvious that there are upper and lower limits on the usefulness of the ratio concept, is anyone willing to hazard a guess where the limits begin? That is, at the extreme numbers jsmith threw out there (I assume he said pp billion intentionally) I would agree that it's obvious the ratio is meaningless on the low end and irrelevant at the high end because the beer would be suitable for de-icing sidewalks.

Chemist's experiments described on page 2 suggest 1:1 ratios with 0 ppm were bland, 250 ppm decent (no comment on quality, just that it was balanced), and 500 ppm unpleasant. It would be great if someone could do this with smaller numbers, like 10, 50, and 100 ppm, at Cl:SO4 ratios ranging from .5 to 2.

For my situation, I have been brewing for years with a Cl:SO4 of 1.89, and would like to hold that constant while I experiment with water additions. However, that ratio is built of only 17 ppm Cl to 9 ppm SO4, so I wonder if it really matters much.

 

[ajdelange]

The basis for the ratio idea came from some testing done with panels in the UK. The relevant papers are listed in the references for the water chapter in the second edition of Brewing Handbook. I'd try to get copies of those before undertaking tests. Meaningful tests would be difficult for home brewers. We are talking about subjective impressions here and those are very hard to quantify. This makes it hard to design an experiment and beyond that there are the difficulties associated with double blind testing, the size of panels, statistical significance, coefficients of variation, repeatability etc.

 

[jsmith32]

Thanks again for your responses.

The reason for my curiosity is because the results of my latest batches of beer were good, but considerably more bitter than I had expected. While there are numerous factors that definitely could have caused this, I'm exploring my chloride/sulfate ratio (which as I mentioned is currently 15/30 = 0.5) as one of the possibilities.

I really don't want to add much in the way of brewing salts, as my tap water is actually pretty decent brewing water, but for my next batch, I'm thinking about adding maybe 40-50 ppm chloride to my water via calcium chloride and using the identical recipe and procedure to see if it makes a huge difference.

Thanks again.

Jason Smith