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Messages - thcipriani

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All Grain Brewing / Re: Water Profile for Oatmeal Stout
« on: September 24, 2010, 02:56:23 AM »
Quote from: mabrungard on Today at 10:22:48 AM
While chalk does contribute 105.8 ppm Ca, it also provides 158.4 ppm of CO3 (not HCO3).  The equivalent concentration of HCO3 is 322 ppm.  1 ppm of CO3 is equivalent to 2.033 ppm HCO3.  Although the chemical formula for chalk (CaCO3) says that its supplying CO3 to the solution, at the pH of typical drinking water, all the CO3 is immediately converted to HCO3 in solution. 
II know that carbonate chemistry in water in the presence of CO2 is complex, and I can't claim to really understand it, so I'd be glad to see an explanation of that statement.
Martin is referring to the concentration of CO3 expressed as an equivalent weight of HCO3 - this is the same concept as when you see on a water report your alkalinity expressed as "as CaCO3". That refers to the total sum of all alkalinity in your water expressed as an equivalent weight of CaCO3 - this helps determine the electrical balance of cations and anions in a given sample of water.

To express the concentration of a substance as an equivalent amount of substance you first find the mg/L (or ppm - they are equivalent measurements) concentration of the substance for which you are attempting to express as an equivalent weight of another substance. For the example above the concentration of CO3 is 158.4.

Then you must find the equivalent weight of that substance, in the above case the substance is CO3. The equivalent weight of a substance can be derived by dividing a compound's molar mass by the number of positive or negative electrical charges that result from the dissolution of that compound (or, more conveniently, just Google search, "Equivalent weight of x" and you can usually find it). In the case of CO3 the gram equivalent is 30.004 (roughly).

After finding the equivalent weight of the first substance you must find the equivalent weight of the substance in which you'd like to express the concentration of the first substance. In the case of HCO3 the equivalent weight is 61.016. Also, as an aside, CaCO3's equivalent weight is 50 - in case anyone was wondering.

Once you have all of these numbers the math is fairly easy:
A mg/L * A equivalent weight/B equivalent weight = ppm of A as B

The above example works like this:
158.4ppm CO3 * (61.016/30.004)=322.121530462605 ppm CO3 as HCO3

All Grain Brewing / Re: A little help with my Water Report
« on: September 19, 2010, 02:07:23 PM »
I brew AG, add Buffer 5.2 to all batches, Campden / Water filter for chlorine & batch sparge.
I'd be wary about the Buffer 5.2. The one thing that is known for certain is that there is some blend of monobasic and dibasic sodium phosphate that make up some portion of 5.2:
Which means you're going to be adding a hell of a lot of Sodium to every beer at the recommended dose of 5.2.

Also, if the only constituents of 5.2 are the phosphate salts (which seems like a safe assumption when you read phrases like, "5.2 is a proprietary blend of food-grade phosphate buffers" on Five Star's website) then 5.2 would not be a very effective buffer.

Monobasic sodium phosphate has a pKa of 7.2. In general a substance's buffer capacity is maximized at that substance's pKa. At a substance's pKa ±1 the buffering capacity of that substance is 33% less effective than at a substance's pKa. So monobasic sodium phosphate has a pKa of 7.2 and its effective buffer region is 6.2 to 8.2. According to Wikipedia (which is a great site that is highly accurate all the time and always will be forever) a blend of monobasic and dibasic sodium phosphate has a buffer region of 6-7.5 ( I don't think it's unreasonable to say that a buffer composed primarily of "food grade phosphate buffers" would be a buffer that would not be effective at a pH of 5.2. Chemistry 101 does not support Five Star's claims.

HOWEVER, if 5.2 is a buffer solution that is made with phosphates as a constituent with other buffers then it may work, although, anecdotally, I've yet to hear a scenario where someone with a reliable means of checking pH (a calibrated meter) has said that it works in both a Stout and a Pale ale. I'd be surprised to hear from that person.

All Grain Brewing / Re: Water Profile for Oatmeal Stout
« on: September 19, 2010, 01:27:15 PM »
This thread is great - we started with water that doesn't exist and a beer with an unknown SRM and we've figured out salt additions to achieve a mash pH with an accuracy of 1/100th of a unit. I see no problems with this logic.

Equipment and Software / Re: BernzOmatic O2 Flowmeter
« on: September 15, 2010, 12:35:02 AM »
Anyone have any thoughts or experience with using one of these:

in conjunction with a little red cannister?

All Grain Brewing / Re: A little help with my Water Report
« on: September 15, 2010, 12:14:51 AM »
That's odd. Even with those 2 numbers my calculations are a bit off of Ward Labs' - I got 6.210/5.818. I was using Nitrate As Nitrogen and SO4 as Sulfur, just like they do so beats me where I'm off. Either way you'll have to fudge your profile a little to glean any real insight.

Anyway, to your original question. I plugged in your numbers and I think a good place to start your adjustments for pale beers would be adding 4 grams of lime and 5 grams of calcium chloride for 5 gallons of treated water which should enable you to precipitate enough CaCO3 to brew a reasonably pale beer while keeping your Calcium levels high. Although I'd still recommend checking the pH in the mash and adjusting with acids based on the reading on your pH meter. My feeling (very scientific, I know) is that after adjusting with lime and CaCO3 you won't have to adjust your pH except for very pale beers.

Let us know how it turns out for you.

Equipment and Software / BernzOmatic O2 Flowmeter
« on: September 14, 2010, 03:55:16 PM »
I have the standard oxygen setup available from any of the major homebrew stores - it hooks to the red bernzOmatic O2 cylinders from the hardware store. I was wondering if anyone had been successful in finding a flow meter that worked with this setup or if anyone had any cheap way to upgrade to an O2 system that included a flow meter? Thanks.

All Grain Brewing / Re: A little help with my Water Report
« on: September 14, 2010, 05:27:21 AM »

looks like there is a slight cation/anion imbalance in your water report (you should see Cations/Anions, me/L at the top of your report - it should be somewhere in the neighborhood of 6.1 / 5.5 - but I could be off since I didn't get the Potassium or Nitrate levels from your report). This is typical of the quality of Ward's Labs reports. None of this is important...


Your water has a RA of 155.88 using Ward labs numbers, if we screw around with those numbers to balance Cations/Anions by upping the level of alkalinity until we reach 255 ppm as CaCO3 to bring the "water" to electrical neutrality the RA is around 185.88 ppm as CaCO3. The pH shift of a mash that uses your water and 100% base malt would be +0.31. That is to say if you brewed a 100% base malt beer with malt that was similar to the malt Kolbach used in his RA experiments in the 40s and 50s you might end up with a mash pH of almost 6.

Fortunately the hardness in your water is mostly temporary hardness and can be precipitated either by boiling and then removing the precipitated CaCO3 or by treatment with lime as outlined here:

Zymurgy / Re: 2011 Zymurgy topics
« on: September 10, 2010, 05:40:51 AM »
I would like to think that we could all agree that a "Ubiquitous AHA Forum Members in Banana Hammocks" issue would likely be what we'd NOT like to see in 2011.

Equipment and Software / Re: A Better Siphon
« on: September 10, 2010, 05:35:49 AM »
Quote from: tygo on August 21, 2010, 07:22:45 PM
Anyone use one of these?

Any thoughts on the product?
That's what I use, I love it.  It's super easy, and the stainless racking cane doesn't break.
+1. If you remove the sterile inline filter and use co2 at like 1psi (of course only in stainless and in better bottles - not glass) and you attach a liquid out (which would now act as a liquid in) to the end of the siphon hose you've made a complete, co2 blanketed, closed transfer system. The day I set it up was the day I stopped worrying about potential introduction of either o2 or bacteria.

I'm surprised no one has mentioned the old classroom standard heat sterilization with an oven method as outlined here:

as well as in other, likely more appropriate, sources.

I've heard it makes bottles more fragile, although I've never experienced it.

Clean your bottles with soap and water, final rinse with distilled water, cover opening with tin foil - bake at 350F for 2 hours - that's sterile. Plus it's cheaper than star san (if you've never taken intro econ and learned about opportunity cost).

Bonus points for pressure canning starter wort and antiseptically pouring into sterile e-flask - my yeast don't out-compete because they've never had to.

Beer Recipes / Re: Gluten Free recipes
« on: September 10, 2010, 04:48:46 AM »
It may well be worth while to look into brewers clarex/clarity ferm - I don't know enough about it to have an opinion on the stuff, but I have heard enough chatter that involved both brewers clarex and gluten reduction to know there is a supposed linkage.

White labs recently began selling clarity ferm as a beer clearing enzyme for homebrewers.

All Grain Brewing / Re: Controlling pH
« on: September 08, 2010, 04:28:31 AM »
What is the range you want to keep the pH in?
I asked that exact same question of A.J. Delange not 2 days ago. Hopefully he won't mind me sharing his answer here because it was the most interesting answer I've gotten on the subject. First, let me share my question since I felt I had to justify asking this question in the first place:
I do have one additional question for you since I have you ear (or, I guess, your eyes) for the moment. Even though its a very simple question (one that I'm almost embarrassed to ask) it's a question that I'd kick myself if I didn't ask. Here are a few quotes that explain my confusion:

Kai Troester, :
many authors report wort and beer quality benefits if the pH is lowered into the 5.2 - 5.4 range [Kunze, 2007][Narziss, 2005].
Any mash pH between 5.3 and 5.8 should be sufficient for most mashes
A mash pH between 5.2 and 5.5 is well suited for infusion mashes

Kai Troester,
optimal mash pH range of 5.4-5.7 (when measured at room temperature)

John Palmer, Zymurgy, Volume 21, No 4, July/August 2008, pg 32
For best results for all [sic] beer styles, the mash pH should be 5.1 to 5.5 when measured at mash temperature, and 5.4 -5.8 when measured at room temperature.

Really, what is the optimum target for the pH of a sample from a mash that has been cooled to 77F? I have been targeting 5.4 since it seems to be acceptable no matter what source you view, but I really don't have any idea. I know that there is a pH difference between hot and room temperature samples but is there some difference between samples that have never been heated vs. samples that are heated and then cooled?

A.J.'s reply was:
That's a very good question but one that does not, unfortunately, have an answer. When asked I usually tell about the Jean DeClerck Chair, given every two years by, the Catholic University of Louvain (jointly, by the Flemish and Wallon schools into which the original split). The year I attended the session was titled "The pH Paradox". Over three days of presentations the subject of pH in brewing gone over with respect to mash, stability, flavor, colloids etc. The title was chosen, of course, because even in a single area, such as mash pH,  there is range of workable pH's. As you well know alpha amylase is most active at one pH while beta is most active at another. Which pH is the "best" for any particular beer is, IMO, only determinable by repeatedly brewing the beer at various pH's and seeing what produces the best beer. This is, of course, what a commercial brewer does either explicitly, by taking measurments, or implicitly by changing the amount of acid he adds to the mash and tasting. Anecdotal evidence is not the best way to draw a conclusion but I will say that the biggest single improvement in my brewing in the last 5 years or so came when I started actively controlling pH to between 5.3 and 5.4 (room temperature) rather than just monitoring it.

As to your other questions I'll go with the only one I'll be able to answer with any level of certainty:
I've heard you add baking soda or salts (gypsum)  to change it. Which one does which?
Baking soda (the HCO3 in baking soda) raises pH, gypsum (the Ca++'s reaction with malt phosphates [Hydrogen Phosphates, mainly, according to Fix]) lowers pH in the mash.

All Grain Brewing / Re: Recipe scaling
« on: September 08, 2010, 04:17:34 AM »
I feel that gallons per hour is the only righteous way to keep track of my boil-off rates since, given the diameter of my kettle and the intensity I like to see in my boil, I tend to boil off 1 gallon per hour regardless of whether there are 7 gallon of wort in my pot at the beginning of that hour or 7.5 gallons of wort in that pot. Obviously 1 gallon is a different percentage for every batch size depending on whether I'm doing a 90min boil (and I start with 7.5 gallons) or a 60min boil (and I start with 7 gallons). I think the only time I've ever seen anything that I felt was substantial that quoted boil off as a percent was:
The most widely used indicator is the percent evaporation that takes place in the boil (Narziss, 1992). With standard boiling systems, a general rule is that the volume reduction be at least 7%. However, it has been show that evaporation rates above 12% may produce level 2 heterocyclics, leaving vegetal malt tones that are accompanied with some astringency. A wide range of level 2 and 3 heterocyclics is possible once evaporation rates exceed 15% As already stated, the flavor of the finished beer will determine the extent to which this effect is relevant
- Fix 1999
To me it seems that a 15% volume reduction over the course of a single hour's time boiling would be more significant to a commercial brewer than to a home brewer but that quote is verbatim so take it with as many grains of salt as you feel necessary.
I've got that set at 23% to achieve 2.5 gallons of boil-off for a 75 minute boil (yeah, that's a lot; I've got a wide kettle).
That seems like quite a bit off boil off. What is the width of the kettle that you use? Remember it's not the size of your kettle it's the motion of your wort  ;)

All Grain Brewing / Re: Harshness - How much alkalinity is too much?
« on: September 06, 2010, 02:35:13 PM »
I emailed A.J. Delange and asked and asked him if he had any additional thoughts on this thread. I felt that almost everything he sent back was relevant to this discussion so here is his reply in its entirety:

Let me preface by saying thank you! I'm really gratified that someone is able to use this stuff.

Now, on to the thread.

I really think you and Martin have pretty much got it covered. There are a couple of points where you guys disagree a bit but they are almost philosophical.  One is on the correlation between beer color and RA. There is, of course, a correlation. Everyone knows that styles that originated in places where the water was hard tended to be darker. The question is as to how strong that correlation is. To determine that, of course, you have to have data and that's hard to get. The reason its hard to get is because you don't have good knowledge of either the SRM or the RA for a particular beer. If I were to try to determine what the correlation actually is I would have little choice except to use my own beers and that is hardly a subset which would result in an informative model as I do, for example, Bocks, which are darker than my ESB with water that has lower RA.

The other approach is to look at beers for which I have measured the SRM that are brewed in cities for which I have a water profile. For example Guiness and Dublin and Bass ale iand Burton. Trouble with that is that Guiness is not brewed in Dublin any more and Bass isn't brewed in Burton either. But PU is brewed in Pilsen and Kölsch in Köln so we are perhaps not all wet if we assume that Guiness is still brewed with a Dublin-like profile and Bass with a Burton-like profile (which it clearly isn't - modern Bass isn't anything like as minerally as an ale brewed with "traditional" Burton water). The other problem is, of course, that I have about 6 mineral profiles for Burton. You all have been commenting on the fact that most published profiles are hooey and indeed so are most of these (I think 2 balance fairly well) and the range of RA's is -13 - 85 for the two profiles that balance. Caveats aside, I took 17 beers and did the correlation. It shows that the relationship between SRM and RA is RA = 5.6 + 1.05*SRM. This would predict that, for example, my 70 SRM Irish stout should be brewed with water of RA 80. This is certainly more reasonable than the 300 some number that the popular spreadsheets come up with but we still haven't looked at the tightness of fit. That's measured by "Pearsons r", a measure which indicates how much of the variation in observed data comes from the model (the model here is RA = 5.6 + 1.05*SRM). For the data I played with r = 46%  (100% means the model is perfect, 0% means there is no correlation whatsoever between SRM and RA). So the correlation is there but it is weak. If this were a game where you tell me the SRM and I bet on the RA predicted by the model I wouldn't take the bet!

I think what John did when he first came up with these was get data from brewers about water treatment and grain bill. I believe he calculated RA and color from this data and then did the regression. I'm pretty sure about the color part because I remember seeing a comment in a post of his concerning which color model he used. I'm not so sure about the RA. Whatever he did the resulting slope defies common sense (and he acknowledges this).

So given all the pitfalls of the curve fit approach (and who said it had to be linear?) I recommend that the spreadsheet developers take this "feature" out of their spreadsheets.

Imbalance seems to be another question that didn't seem quite resolved. You all said it without saying it explicitly: imbalance represents a measure of the quality of a water report. If the report exhibits large imbalance that means errors were made in measurement, the sample changed while the measurements were going on, bicarbonate was calculated incorrectly from alkalinity, ionic strength was ignored, or some relatively prevalent ion or ions were not measured. The way I often put it is to say that mother nature cannot make imbalanced water and neither can you so if you are trying to match an imbalanced profile you will not succeed.

Finally, the philosophy of owning a pH meter: Given all the variables I do not believe it is possible to accurately predict mash pH and that, therefore, it is essential that you measure it to see if your treatment and grist formulation combine to land you in the right pH range. But I agree that once you have determined that they do you should come back to pretty close to the same pH every time you brew a particular beer and don't really need to check pH. Being the sort I am I do and I also check at the return of each decoction, out of the kettle and throughout the course of the ferment. I don't advocate this for everyone but those pH readings are like familiar landmarks on the road home to me. Each time you see one in the right place you are further assured that your journey will come to a successful end.

Now one thing that has not been mentioned (or emphasized)  is that most beers will require the addition of acid in some form to reach proper mash pH. For German/continental brewers this is sauermalz or sauergut (i.e. lactic acid). For British brewers it is "Carbonate Reducing Solution" (a mix of sulfuric and hydrochloric acids).

Hope this is of some help. Feel free to quote it if you like.

Cheers, A.J.

All Grain Brewing / Re: Harshness - How much alkalinity is too much?
« on: September 04, 2010, 06:39:29 AM »
He did correctly point out a flaw in the rule of thumb that I proposed between RA and SRM. He pointed out that if you design a really dark beer, the required RA goes through the roof.

The other obvious flaws being that your calculation cannot conceive of a negative RA value and that the calculation needlessly oversimplifies a complicated concept when many people have dedicated countless hours to developing applications to model non-ideal solutions.

Unfortunately, thcipriani goes on to say that the correlation between RA and SRM is tenuous at best. Unfortunately he is quite wrong with that statement. He did provide a couple of references from AJ and Kai that actually do provide a correlation between roasted malt acidity and their color.

I agree roasted malt is acidic; however, SRM is not indicative of the amount of roasted malt used in a mash - that's what I found in Kai's research; however, I guess you always find that for which you are searching. You have not offered any proof that there is any sort of strong correlation between SRM and and pH. Can you point to any studies thats conclusion is that mash pH can be predicted solely on SRM? It's like predicting the weather - I'm not arguing there is science to support that SRM has some correlation to mash pH. I'm arguing that if I test my mash pH I'm always right about my mash pH. If I use one of the available spreadsheets on the internet (especially if I'm starting with a profile that can't exist) I'm not going to be right 100% of the time. If I go outside and it's raining it doesn't matter what the weatherman says.

thcipriani goes on to say that the vast majority of water needs no adjustment. That statement is quite incorrect. The historical beer styles that grew out of the world's brewing centers are cases in point. There is no way that a brewer in Dublin could EVER hope to brew a good pale beer with their water and conversely, there is no way that a brewer in Burton could ever brew a good dark beer with their water WITHOUT ADJUSTING THEIR RESPECTIVE WATERS.

I never claimed that Dublin water needed no adjustment to brew a pale beer. I said that the majority of water needs no adjustment - extremes are exceptions. I don't think anyone would disagree with the statement that Dublin and Burton-on-Trent are very extreme waters. If there's a brewer out there with that kind of water then, yeah, they'll need adjustment - the 800ppm SO4 as the ion would be a good tip that your water is atypical.

Its also humorous that thcipriani goes on to state that if brewers are worried about their mash pH they should get a pH meter and then adjust their mineral or acid content. He is espousing exactly the same thing that I'm stating with chemistry adjustment excepting that he is expecting a brewer to figure out what to do while potentially destroying a few mashes in the process.

I'm glad I can humor you. I don't espouse anything with that statement other than a pH meter can give a brewer that's worried about their pH piece of mind. I think that once a brewer has a pH meter they'll be able to make informed decisions about which ions to add to their water to give them an appropriate mash pH and not blindly add salts and acids that needlessly destroy their mash by taking it out of the correct pH range. You seem to think that by measuring mash pH and adding CaCO3 or Lactic acid that it somehow ruins a mash when, in fact, adding a huge amount of CaCO3 without measuring your mash pH would do the same thing.

I really feel we're circling the same point - water's complicated and brewers need to be conscious of their pH. The difference here is that you espouse that a spreadsheet is highly accurate while I believe that a properly calibrated pH meter is the best tool.

Non-ideal solutions (like water) are complicated systems to model. If a brewer makes additions based on readings they get from a calibrated pH meter they're going to be right 100% if the time. If they use a spreadsheet, or worse yet, an oversimplified formula they could be wrong. I'm just asking brewers to look outside before they decide they don't need an umbrella.

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