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General Category => Ingredients => Topic started by: mabrungard on December 15, 2010, 01:12:55 AM

Title: Palmer Spreadsheet Error
Post by: mabrungard on December 15, 2010, 01:12:55 AM
After reviewing a water profile created by a brewer using Palmer's Spreadsheet, I found a very serious error that must be corrected.  

The bicarbonate concentration calculated from the addition of chalk is in error.  It appears that the calculation is actually giving the carbonate concentration instead of the bicarbonate concentration.  Since carbonate cannot exist at typical mash pH, it must be converted to the bicarbonate form.  That means that the carbonate concentration should be multiplied by 2.033.  This also means that the alkalinity calculated for the chalk addition in the spreadsheet is also in error and should be multiplied by 2.033.

Another significant error in the spreadsheet is the residual alkalinity that the spreadsheet recommends based on the beer color.  It is far too aggressive and recommends far too high a RA value to the brewer.  There are no water profiles from the historic brewing centers with a RA higher than about 180.  This spreadsheet will frequently point a brewer to recommended RA values of 300 to 400.  That is extremely excessive and leads to soda water beers.  A more appropriate correlation between RA and SRM is as follows:  RA = SRM x 4.5.  And given that correlation, the maximum RA a brewer should ever use is about 200.  

Until the revised spreadsheet is issued, I recommend that brewers refrain from using this program.
Title: Re: Palmer Spreadsheet Error
Post by: punatic on December 15, 2010, 01:21:17 AM
(http://water.me.vccs.edu/courses/env211/changes/carbonategraph.gif)
Title: Re: Palmer Spreadsheet Error
Post by: Kaiser on December 15, 2010, 03:02:36 AM
The bicarbonate concentration calculated from the addition of chalk is in error.  It appears that the calculation is actually giving the carbonate concentration instead of the bicarbonate concentration.  Since carbonate cannot exist at typical mash pH, it must be converted to the bicarbonate form.  That means that the carbonate concentration should be multiplied by 2.033.  This also means that the alkalinity calculated in the spreadsheet is also in error and should be multiplied by 2.033.

Martin,

You seem to be stumbling onto a lot of things that I have stumbled upon as well, which I like. I noticed the same when I calculated the ion balance of the water profiles created with that spreadsheet. However, I set out to test this in a mash pH experiment and found that while the spreadsheet seems to be incorrect the predicted pH change is correct. Eventually, after many more experiments, I came to the conclusion that undissolved chalk has an inexplicably odd behavior when it comes to adjusting mash pH.

Check out these links:
* How much alkalinity does 1 ppm of CaCO3 (Chalk) really add?  (http://braukaiser.com/lifetype2/index.php?op=ViewArticle&articleId=128&blogId=1)
* Undissolved vs. dissolved chalk in the brewing water  (http://braukaiser.com/lifetype2/index.php?op=ViewArticle&articleId=132&blogId=1)
* The effect of brewing water and grist composition on the pH of the mash (http://braukaiser.com/documents/effect_of_water_and_grist_on_mash_pH.pdf)

You may also want to give my water spreadsheet a try: http://braukaiser.com/documents/Kaiser_water_calculator.xls It handles undissolved chalk similar to what Palmer does but it also supports dissolving chalk.

Quote
Another significant error in the spreadsheet is the residual alkalinity that the spreadsheet recommends based on the beer color.  It is far too aggressive and recommends far too high a RA value to the brewer.  There are no water profiles from the historic brewing centers with a RA higher than about 180.  This spreadsheet will frequently point a brewer to recommended RA values of 300 to 400.  That is extremely excessive and leads to soda water beers.  A more appropriate correlation between RA and SRM is as follows:  RA = SRM x 4.5.  And given that correlation, the maximum RA a brewer should ever use is about 200.  

I do agree. For some reason John found that roasted malts are more acidic per unit of color than crystal malts. I found that the opposite is true and as a result you need  far less alkalinity in dark beers than previously thought. Unfortunately John did not publish how he arrived at his SRM->RA formula.

Kai
Title: Re: Palmer Spreadsheet Error
Post by: tschmidlin on December 15, 2010, 07:13:31 AM
I love this forum :)
Title: Re: Palmer Spreadsheet Error
Post by: James Lorden on December 15, 2010, 03:34:56 PM
I love this forum :)

+1

   
Title: Re: Palmer Spreadsheet Error
Post by: denny on December 15, 2010, 03:53:11 PM
Martin or Kai, have you contacted John with your concerns?
Title: Re: Palmer Spreadsheet Error
Post by: Kaiser on December 15, 2010, 04:20:22 PM
Martin or Kai, have you contacted John with your concerns?

I had. But at the time he didn't show much interest or had time to spend on this. He also didn't show much interest when I mentioned this to him at the conference.

I don't really need his input on this. Most of John's work is based on A.J. deLange's stuff anyway and I had e-mail conversations with A.J. about this. He can't explain this observation either.

I think we need to get more brewers like Martin to question why the addition of 100 ppm CaCO3 doesn't raise the water's alkalinity (not residual alkalinity) by 100 ppm as CaCO3. Maye more brewers will adopt the spreadsheet I have. With some more data about undissolved chalk and its effects on the mash pH I could even put in a curve that determined the "apparent" RA increase that comes from undissolved chalk. This would make the relation between chalk and pH more apparent.

Kai
Title: Re: Palmer Spreadsheet Error
Post by: denny on December 15, 2010, 04:26:18 PM
It's too bad that John didn't have time to deal with this.  Many brewers use his spreadsheet and accept is as "gospel".  In that case, it needs to be accurate.  I'm glad we have people like Martin and you questioning things and trying to explain them.
Title: Re: Palmer Spreadsheet Error
Post by: Kaiser on December 15, 2010, 04:57:46 PM
I started pushing my water spreadsheet before I went on my brewing hiatus and haven't picked up that effort. After all the question is not so much the RA that is calculated by the spreadsheet but it is "can you brew better beer with a more accurate spreadsheet". John does recommend to limit the RA to 250 ppm and there is also a lot of leeway when it comes to the correct RA for a given beer. In addition to that he also doesn't account for mash thickness.

Maybe Martin and other brewer's interest motivates me to write the next version of my water spreadsheet which will take more grist information into account. I do have a lot of the data necessary for that. Ideally this work should be incorporated into a commonly used tool like BeerSmith.

I also think that you can add all your salts to the mash and don't add any to the sparge water.

Kai
Title: Re: Palmer Spreadsheet Error
Post by: richardt on December 15, 2010, 05:28:54 PM
I started pushing my water spreadsheet before I went on my brewing hiatus and haven't picked up that effort. After all the question is not so much the RA that is calculated by the spreadsheet but it is "can you brew better beer with a more accurate spreadsheet". John does recommend to limit the RA to 250 ppm and there is also a lot of leeway when it comes to the correct RA for a given beer. In addition to that he also doesn't account for mash thickness.Maybe Martin and other brewer's interest motivates me to write the next version of my water spreadsheet which will take more grist information into account. I do have a lot of the data necessary for that. Ideally this work should be incorporated into a commonly used tool like BeerSmith.
I also think that you can add all your salts to the mash and don't add any to the sparge water.
Kai
THIS! 

I'd love to have a Grand Unified Theory of Brew Salt Additions hammered out that takes mash thickness, temperature, grist composition and accurately predicts pH, RA, and so forth.  I'd love to see it incorporated into BeerSmith along with better instructions for data entry as well as for brewing (e.g., Kai's recommendation to add all the salts directly to the mash, not the HLT or the Sparge Water).

Martin, thank you for looking into it, as well.  Everytime you post something about water chemistry, believe me, I pay attention. Your expertise is evident--it takes me a few reads and re-reads to "get it.")  Thanks for your input.  Perhaps a collaboration with you, Kai, and A.J. and any others who are interested (e.g., those who design and run BeerSmith) is in order.
Title: Re: Palmer Spreadsheet Error
Post by: James Lorden on December 15, 2010, 05:49:57 PM
Martin, thank you for looking into it, as well.  Everytime you post something about water chemistry, believe me, I pay attention. Your expertise is evident--it takes me a few reads and re-reads to "get it.") 

Couldn't agree more.  I also feel like it puts a little pressure on us that "sort of get it" to ask intelligent questions so that the information can trickle down through us to those who "don't get it".

One of the great things I have noticed about many of the complicated topics lately is that they have been working down from the complicated theory, to the simplified synopsus, and finally to must have take aways as the conversation evolves.  There's a little something for everyone....

Keep up the good work everybody!
Title: Re: Palmer Spreadsheet Error
Post by: Kaiser on December 15, 2010, 06:43:36 PM
Being able to predict mash pH, or just about anything that could be predicted in brewing, is very much a home brewer thing. There seems to be little data available from the commercial brewing worlds and our understanding of mash pH is largely based on research done before WWII.

Over the time I have come to the conclusion that we may want to change the way mash pH adjustment is taught to home brewers. Let’s even forget about water profiles for a moment and see the mash pH problem as changing the pH of a pH buffer. The buffer is malt and its has a natural pH of ~5.75 in distilled water. What raises the pH are:

* bicarbonate/carbonates
* hydroxide (bases)

What lowers the pH are

* mailard products in the malt
* acids
* Ca and Mg

You quantify the amount of all of these substances, calculate the balance  and use that to predict the pH change of the mash. There will be inaccuracies that come from the fact that malt is not a simple buffer substance but that it is a mix of pH buffering substances.

The notion of the water’s residual alkalinity is useful to estimate how suitable a given water is for a given type of beer but I don’t think that we should use it to actually predict mash pH.

I have done a number of experiments already and am currently working on experiments where I add known amounts of salts and acids to small mash sampled to see how their pH reacts. And again, chalk was the odd one. In some of the experiments the mash pH didn’t change at all after I added chalk.

Kai

Title: Re: Palmer Spreadsheet Error
Post by: denny on December 15, 2010, 06:55:41 PM

I also think that you can add all your salts to the mash and don't add any to the sparge water.

That's exactly what I do.
Title: Re: Palmer Spreadsheet Error
Post by: tschmidlin on December 15, 2010, 06:56:42 PM

I also think that you can add all your salts to the mash and don't add any to the sparge water.

That's exactly what I do.
Same here. :)  Glad to have it validated by a water expert.
Title: Re: Palmer Spreadsheet Error
Post by: Kaiser on December 15, 2010, 07:01:47 PM
Same here. :)  Glad to have it validated by a water expert.

If you are using R/O or other soft water all that is going to happen is that your pre-boil pH is going to be identical or closer to your mash pH since the sparge water is not bringing in any additional minerals that could change the pH. It only dilutes the solution which tends to have little effect in well buffered systems.

Having the pre-boil pH close to the mash pH isn’t a bad thing. They both have about the same optimal pH range.

Kai
Title: Re: Palmer Spreadsheet Error
Post by: tschmidlin on December 15, 2010, 07:11:12 PM
Cool, my water is pretty soft.  Not Plzen soft, but soft.  Ca 15, Mg 7.
Title: Re: Palmer Spreadsheet Error
Post by: hamiltont on December 15, 2010, 07:15:41 PM

I also think that you can add all your salts to the mash and don't add any to the sparge water.

That's exactly what I do.
I do the same but I figured since I was batch sparging it didn't really matter because the sparge water was only in the tun for a short period of time. Can't say if it makes a difference with fly sparging though.

Also,  I have been using Palmer's spreadsheet for a while & found that if I adjust my water on the high end of the Estimated RA for lighter beers (<15 SRM) and on the lower end of the Estimated RA for darker beers (25+ SRM and never exceeding RA of 180) my beer turns out better. Might just be coincidence though.  Cheers!!!
Title: Re: Palmer Spreadsheet Error
Post by: Kaiser on December 15, 2010, 07:27:05 PM
Cool, my water is pretty soft.  Not Plzen soft, but soft.  Ca 15, Mg 7.
Yes, I think you are fine.

Just as a clarification. Don’t confuse hardness with alkalinity. Alkalinity is a measure of the water’s bicarbonate/carbonate content while hardness is a measure of its Ca and Mg content. Granted, most hard waters also end up being fairly alkaline and most soft waters tend to be low in alkalinity. Waters that don’t follow this rule are the ones that have lots of Sulfate and/or Chloride. They can be hard (lots of Ca + Mg) but have low alkalinity (little HCO3). On the other side are soda alkaline waters which are characterized by high sodium and bicarbonate content. Those water’s are soft, in fact this is the kind of water that comes out of a water softener, but still alkaline.

Kai
Title: Re: Palmer Spreadsheet Error
Post by: narvin on December 15, 2010, 07:30:40 PM
I use Kai's spreadsheet.  Don't you all want to be cool like me and use it too?   ;)
Title: Re: Palmer Spreadsheet Error
Post by: gordonstrong on December 15, 2010, 07:37:07 PM
I add salts to the mash and sometimes to the boil, and just use acid to adjust sparge water.

Never had the need for a spreadsheet, though.  Wouldn't brew without a pH meter, however.  Or at least with having used one enough in the common brewing situations to understand what causes my target mash pH to be hit.

A spreadsheet is a model.  Models may or may not accurately represent reality.  They may have unstated assumptions that don't fit the circumstance you are in.  Using them without some form of validation is just shooting in the dark.
Title: Re: Palmer Spreadsheet Error
Post by: richardt on December 15, 2010, 08:44:26 PM
What would be the purpose of bypassing salt additions to the mash and putting the salts in the boil?
What does it accomplish?
Title: Re: Palmer Spreadsheet Error
Post by: tschmidlin on December 15, 2010, 08:47:49 PM
What would be the purpose of bypassing salt additions to the mash and putting the salts in the boil?
What does it accomplish?
Some ions only really affect mouthfeel and other flavor perceptions.  If you want to know exactly how much of them you're adding to the beer, they should go in the kettle.  Otherwise some could be lost in the mash.
Title: Re: Palmer Spreadsheet Error
Post by: denny on December 15, 2010, 08:57:21 PM
What would be the purpose of bypassing salt additions to the mash and putting the salts in the boil?
What does it accomplish?
Some ions only really affect mouthfeel and other flavor perceptions.  If you want to know exactly how much of them you're adding to the beer, they should go in the kettle.  Otherwise some could be lost in the mash.

I often add gypsum to the kettle and not the mash.  With my water, the pH for AIPA/APA arrives at the correct value without any mash additions.  I want to add gypsum to accentuate the hops, but if I added it to the mash it would drop the pH too low.  Adding it to the kettle avoids that.
Title: Re: Palmer Spreadsheet Error
Post by: kramerog on December 15, 2010, 09:16:50 PM
After reviewing a water profile created by a brewer using Palmer's Spreadsheet, I found a very serious error that must be corrected.  

The bicarbonate concentration calculated from the addition of chalk is in error.  It appears that the calculation is actually giving the carbonate concentration instead of the bicarbonate concentration.  Since carbonate cannot exist at typical mash pH, it must be converted to the bicarbonate form.  That means that the carbonate concentration should be multiplied by 2.033.  This also means that the alkalinity calculated for the chalk addition in the spreadsheet is also in error and should be multiplied by 2.033.


Without looking at the spreadsheet (if someone pointed out where the spreadsheet is and which cells have the error, I would probably look at it), since alkalinity is usually reported as alkalinity as mg/l of CaCO3, I don't see an error in the alkalinity number.  Perhaps, the bicarbonate concentration is being reported as mg/l of CaCO3 too?
Title: Re: Palmer Spreadsheet Error
Post by: richardt on December 15, 2010, 09:29:27 PM
Good to know.  I'll get there one day.
Right now, I'm working on nailing the mash temps and the pH. 

This forum really has helped open my eyes to some of the finer points of good homebrewing. 
For example, Martin B. had a good point a few weeks ago about calibrating his thermometers at 150 F rather than 0 or 212 F.
 
It got me thinking:  my last few beers have been too dry and light bodied. 
Turns out one of my cheapo digital Taylor thermometers calibrates fine at 0 and 212 but reads 5+ degrees too high at 150 F.
The damn calibration dial doesn't change it no matter how much I turn it counterclockwise.  It is going to get replaced.  Turns out the analog thermometer gauges were right, not the digital one.

Same thing for the pH and water adjustments with brew salt additions.  I appreciate the wise counsel and explanations of those experts and brewing veterans who take the time to post replies on the forum.

Edit:  Here's Palmer's spreadsheet
http://www.howtobrew.com/section3/chapter15-3.html (http://www.howtobrew.com/section3/chapter15-3.html)
Title: Re: Palmer Spreadsheet Error
Post by: Kaiser on December 15, 2010, 10:15:52 PM
Here is how you see the error. Add 100 mg CaCO3 to 1 l water. The expected alkalinity should be 100 ppm as CaCO3 but it is only 46

(http://braukaiser.com/images/misc_forum/Palmers_spreadsheet_and_chalk.gif)

Kai
Title: Re: Palmer Spreadsheet Error
Post by: kramerog on December 15, 2010, 10:21:39 PM
Looking at  the US spreadsheet, the  formula in cell E30 should be roughly (C27*322 + G27*363)/C23.  In other words, the factors for converting chalk and baking soda to bicarb are both wrong.  Correcting E30 should result in L30 giving the proper result.

Edit: corrected cell refs
Title: Re: Palmer Spreadsheet Error
Post by: kramerog on December 15, 2010, 11:34:40 PM
Looking at  the US spreadsheet, the  formula in cell E30 should be roughly (C27*322 + G27*363)/C23.  In other words, the factors for converting chalk and baking soda to bicarb are both wrong.  Correcting E30 should result in L30 giving the proper result.


The "corrected" equation assumes that the chalk and baking soda fully dissolve.  However, Kai points out earlier that the chalk does not fully dissolve and thus the original factor of 158.4 rather than 322 might not be wrong as an empiricism.  However, it is unclear why the discrepancy for the baking soda factor.  Baking soda dissolves well; the solubility of baking soda is 100 g/l at 20 C vs. .015 g/l for chalk at 25 C per wikipedia.
Title: Re: Palmer Spreadsheet Error
Post by: bluesman on December 16, 2010, 02:26:21 AM
Interesting findings.

I haven't used Palmer's spreadsheet but was considering it. I want to take a better look at my water and purchase a pH meter intead of using strips. I've also considered using Kai's spreadsheet but never found enough time to actually do it.

Gordon points out a very important issue. Once one's water has been adjusted it should be qualified to determine the actual composition at that point. In an effort to target a specific water profile it is necessary to verify the actual profile and any adjustments that have been made. If this isn't done the water profile is assumed to be adjusted based on calculated additions.

Determining the actual water chemistry must be qualified in a lab which can be costly but is necessary in order to have confidence in any adjustments that have been made.
Title: Re: Palmer Spreadsheet Error
Post by: tygo on December 16, 2010, 04:32:01 AM
I use the EZ water spreadsheet because it's, well, easy.  And I've found it to be somewhat accurate and I've applied my trial and error experience to it (and continue to refine that) to figure out what additions I need to make.  I've been moderately successful getting into the range I'm looking for and I feel that I can zero that in given more practice.

Kai - I've tried using your spreadsheet and it's just not intuitive to me.  I just tried it again as a matter of fact to see if I could figure out the water treatment for my next brew.  Where I run into an issue is I don't want to define each salt addition as ppm.  That doesn't mean much to me.  I want to enter the grams of salts and see what the ppm will be in my given volume and then tweak the additions to get to where I need to be.  Maybe I'm missing something in the functionality and if so I'd be happy to stand corrected.

I'm comforted by Gordon's post that he doesn't even use a spreadsheet. I love spreadsheets, I'm a spreadsheet guy, but all I really want to know is the approximate concentrations of the ions that I'm putting into the mash and an approximation of what that's going to do to pH and the final beer.  From there I'm always going to be a trial and error guy who adjusts based on those practical data points.

Water chemistry is a very complex subject and if you're an expert in the field you're going to be able to dial things in to a degree that most of us cannot.  I think these types of discussion are great and I follow them with great interest.  But my objective is to make great beer and to the extent I can do that without taking a chemistry course that's what I'm going to do. 
Title: Re: Palmer Spreadsheet Error
Post by: Kaiser on December 16, 2010, 05:41:02 AM
Kai - I've tried using your spreadsheet and it's just not intuitive to me.  I just tried it again as a matter of fact to see if I could figure out the water treatment for my next brew.  Where I run into an issue is I don't want to define each salt addition as ppm.  That doesn't mean much to me.  I want to enter the grams of salts and see what the ppm will be in my given volume and then tweak the additions to get to where I need to be.  Maybe I'm missing something in the functionality and if so I'd be happy to stand corrected.

I take your point. I decided to have the user enter salts as ppm of the water because this makes the salt additions independent of water volume. I like to think in volume and/or weight independent terms. Just like discussing a grist by referring to the percentages of malts used rather than assuming that we all brew 5 gal batches and refer to the weights of the malts.

But I see how many brewers just want to think in grams of salt added since this is what they end up weighing out and what they'll remember from brew to brew. I may make the unit for the salts configurable in the future so salts can be entered as mg/l, gram and maybe even mg/kg. The latter is mg per kg grist.

Kai
Title: Re: Palmer Spreadsheet Error
Post by: blatz on December 16, 2010, 03:00:45 PM

But I see how many brewers just want to think in grams of salt added since this is what they end up weighing out and what they'll remember from brew to brew. I may make the unit for the salts configurable in the future so salts can be entered as mg/l, gram and maybe even mg/kg. The latter is mg per kg grist.

Kai - here's a +1 that this would be more helpful for most people - as said, I don't think in ppms, I think in how much do I need to weigh out.  Sure, I can make the calculations, but you know what I mean.
Title: Re: Palmer Spreadsheet Error
Post by: akr71 on December 16, 2010, 03:03:23 PM
I use the EZ water spreadsheet because it's, well, easy.... 

Kai - I've tried using your spreadsheet and it's just not intuitive to me.

I use both Kai's and the EZ water spreadsheet.  While I agree the Kai's may not be the most intuitive, it has helped me understand water chemistry far better.  I've tried Palmer's, but I found I was just fumbling around plugging numbers in at random until I started to get where I thought my water should be.  Kai's articles and using the his spreadsheet has helped illuminate how the different ions interact - its still pretty confusing to me, but at least I don't feel I'm fumbling in the dark anymore.

The last few batches, I've focused soley on getting my mash pH down (my water is high in bicarbonates and sulphates and low on calcium and magnesium).  The EZ water spreadsheet gives me abit of extra confidence that the pH will be where it is supposed to be and my efficiency has jumped from the high 70's to the mid 80's because of it.

After reading this thread, I'll continue to focus only on the mash pH and if I want to adjust the chloride/sulphate ratio, I'll do it in the kettle.
Title: Re: Palmer Spreadsheet Error
Post by: kramerog on December 16, 2010, 03:58:04 PM
The "corrected" equation assumes that the chalk and baking soda fully dissolve.  However, Kai points out earlier that the chalk does not fully dissolve and thus the original factor of 158.4 rather than 322 might not be wrong as an empiricism.  However, it is unclear why the discrepancy for the baking soda factor.  Baking soda dissolves well; the solubility of baking soda is 100 g/l at 20 C vs. .015 g/l for chalk at 25 C per wikipedia.

The discrepancy for the baking soda factor is me! Just a miscalculation. 
Title: Re: Palmer Spreadsheet Error
Post by: richardt on December 16, 2010, 03:59:43 PM
...The last few batches, I've focused soley on getting my mash pH down (my water is high in bicarbonates and sulphates and low on calcium and magnesium)...

Sounds like my water profile (Jacksonville, FL).  May I ask how you do your salt additions?
Title: Re: Palmer Spreadsheet Error
Post by: kramerog on December 16, 2010, 04:12:41 PM
My take home is to not to use chalk for raising alkalinity if baking soda will work acceptably, e.g., does not raise sodium excessively.  My reasoning is that the calculation for the contribution to alkalinity from chalk is a crude empiricism that does not take into account a specific users chalk source,equipment, and procedures that could lead to different amounts of chalk being dissolved over the length of the mash.
Title: Re: Palmer Spreadsheet Error
Post by: akr71 on December 16, 2010, 05:33:10 PM

Sounds like my water profile (Jacksonville, FL).  May I ask how you do your salt additions?

I add a good dose of calcium chloride to bring the Ca above 50 ppm (usually around 2 grams for 3 gallons mash water) and touch of epsom salts to get the magnesium around 10 (1 gram for 3 gallons mash water).  This leaves me with roughly balanced chloride : sulphate ratio.  I use lactic acid to get the mash pH down the rest of the way (2 ml for last weekend's brew - no roasted malts in that one).

The EZ Water Calculator helps me estimate the pH ( http://www.ezwatercalculator.com/ ).  Kai's articles and spreadsheet help me understand how my additions interact.
Title: Re: Palmer Spreadsheet Error
Post by: richardt on December 16, 2010, 05:38:44 PM
Thanks.  I'll keep that in mind if I ever go back to using the local water (which I may do as a side-by-side experiment along with RO water built up with salt additions to yield the same water profile).  Right now, though, there's something "intangible" about my local water.  It just plain tastes terrible.
Title: Re: Palmer Spreadsheet Error
Post by: Thirsty_Monk on December 18, 2010, 05:15:42 PM
Great discussion.
Thank you all.

I am using EZ water Calculator.
Title: Re: Palmer Spreadsheet Error
Post by: johnf on December 18, 2010, 08:54:46 PM
My take home is to not to use chalk for raising alkalinity if baking soda will work acceptably, e.g., does not raise sodium excessively.  My reasoning is that the calculation for the contribution to alkalinity from chalk is a crude empiricism that does not take into account a specific users chalk source,equipment, and procedures that could lead to different amounts of chalk being dissolved over the length of the mash.

The problem with chalk is that it appears as though you can't predict the alkalinity it will contribute to the mash. It is notable that you can't predict the mash pH very well regardless.

If you use a pH meter at dough-in, using chalk to raise the pH if needed works just fine as you are doing it empirically and you aren't adding any unwanted sodium. If you rely on predicting things (you don't have a pH meter), then baking soda will be more predictable subject to the caveat about too much sodium.

If you aren't worried about working with it, potassium hydroxide would add a predictable amount of alkalinity and no sodium. I use it in mead making and use gloves and eye protection to mix a solution of known strength (whatever it is that the SPHBC folks recommend) and then gloves only when working with the solution. Never broke it out for a mash as:

1. I rarely measure a mash pH that is lower than I want, and I typically start with modestly negative RA and
2. When I do the amount of chalk required to raise it is uniformly pretty small.
Title: Re: Palmer Spreadsheet Error
Post by: hike20 on December 19, 2010, 12:15:17 AM
Kai,
I also use the 2.0 version of the ezwatercalculator because I just couldn't get my head around your spreadsheet. Have you looked at the version 2.0? He supposedly based it off of your data and not using Palmer's method.

I'm curious if it's predicting pH reasonably close. I'll get a pH meter as soon as I can afford it, but have to make do with estimates until then.
Title: Re: Palmer Spreadsheet Error
Post by: johnf on December 19, 2010, 01:15:05 AM
Kai,
I also use the 2.0 version of the ezwatercalculator because I just couldn't get my head around your spreadsheet. Have you looked at the version 2.0? He supposedly based it off of your data and not using Palmer's method.

I'm curious if it's predicting pH reasonably close. I'll get a pH meter as soon as I can afford it, but have to make do with estimates until then.


It's not just Kai's data, it's his model. I believe the goal was consistency with Kai's spreadsheet so assuming the implementation is correct, it is.

I found Kai's spreadsheet easy enough to use, but I'm somewhat proficient in Excel. Are you familiar with the formula auditing tools in Excel? You can trace dependents and precedents for each cells which can give a graphical representation of what the inputs are and where they go. They are on the formula ribbon in 2007. I forget how to get to them in 2003, I always had them on my toolbar.
Title: Re: Palmer Spreadsheet Error
Post by: Kaiser on December 19, 2010, 03:50:53 AM
I also use the 2.0 version of the ezwatercalculator because I just couldn't get my head around your spreadsheet. Have you looked at the version 2.0? He supposedly based it off of your data and not using Palmer's method.

It's possible that the spreadsheet fits more with my brewing than with others. While I'm interested in improving the usability of the tool I'm more interested in working on the science behind it and let others figure out how to make something that is well suited for the majority of the brewers. I was also more interested in providing a spreadsheet that can handle GH&KH water tests, water treatment with lime and the use of dissolved chalk. But I'm glad that my model has found some acceptance and I'll have to check it out.

However, it's just a model that uses the convenient but less accurate relation between SRM and mash pH. Ideally we would want malsters to supply us with congress mash pH for base and specialty malts. For specialty malts titration results would be useful too.

I don't brew too many different beers to be able to practically validate the results oft my SRM to pH model and I haven't gotten much feedback either. Either it works very well, or which is more likely, there is enough wiggle-room that the imprecision doesn't matter much.

John, I have to check out the formula audit tool. This sounds really neat.

Kai
Title: Re: Palmer Spreadsheet Error
Post by: johnf on December 19, 2010, 04:09:56 AM

I don't brew too many different beers to be able to practically validate the results oft my SRM to pH model and I haven't gotten much feedback either. Either it works very well, or which is more likely, there is enough wiggle-room that the imprecision doesn't matter much.


I've been thinking about recording actual pH and spreadsheet inputs for all of my beers and publishing the info. I brew outside so I will only brew opportunistically for the next couple of months. I think if we could find a dozen brewers with pH meters who would record and publish this info it would be pretty easy to demonstrate to other brewers how much confidence they should have in models or where the models are weak.
Title: Re: Palmer Spreadsheet Error
Post by: Kaiser on December 19, 2010, 03:38:20 PM
Another alternative to chalk would be the use of calcium hydroxide. Also known as pickling lime it is more soluble and also raises the pH while adding calcium to the mash. I haven't investigated it's behavior in the mash yet.

Kai
Title: Re: Palmer Spreadsheet Error
Post by: johnf on December 19, 2010, 04:06:11 PM
Another alternative to chalk would be the use of calcium hydroxide. Also known as pickling lime it is more soluble and also raises the pH while adding calcium to the mash. I haven't investigated it's behavior in the mash yet.

Kai

Good call. Easier to get and handle than potassium hydroxide, and it adds calcium.

I think I might do an experiment this spring. Brew the same beer back to back and set the mash at the same pH. One with chalk, one with calcium hydroxide. I'm sure both will work but I am interested in flavor differences. I would expect the pickling lime to be neutral and the chalk to have a flavor impact and this might clarify whether or not that flavor impact is positive.
Title: Re: Palmer Spreadsheet Error
Post by: mabrungard on December 19, 2010, 05:41:37 PM
Slaked lime (aka Pickling Lime) is sometimes used to add alkalinity in drinking water.  In that case, air or CO2 are bubbled through the slaked lime solution to react the excess OH ions back down to HCO3 ions.  As some of you may know, my profession is in water engineering.

But given the fact that our primary concern in mashing dark grains is avoiding an excessive pH drop, we don't necessarily need to convert the acid consuming OH ions into less reactive (but still acid consuming) HCO3 ions.  The only thing with working with the slaked lime is that it will be far less forgiving.  This is just like working with an acid.  You would need to know what you're doing and add exact amounts.  

I'll work through the dosing quantification for slaked lime and get back to folks on this. OH and HCO3 are roughly interchangable as alkalinity producers, its just that OH is not a buffer and will automatically consume acid without moderation.  So there is no leeway.

Lime will get us away from the problem of limited chalk solubility.
Title: Re: Palmer Spreadsheet Error
Post by: Kaiser on December 19, 2010, 10:37:44 PM
In a mash lime should be as forgiving as any other salt because the mash is a strongly buffered system. Adding x ppm of lime will raise the pH by y. And adding 2x will raise it by 2y. The same as baking soda does. This is because the 1 pka (buffer pH point) of carbonate is 6.4 which is sufficiently far enough from our mash pH targets.

Martin, I didn't realize that you are a water engineer. I guess I have to be extra careful about what I'm writing ;)

Kai
Title: Re: Palmer Spreadsheet Error
Post by: mabrungard on December 19, 2010, 10:52:43 PM
The mash is buffered, but the hydroxide is not.  It will consume any proton available.  This is unlike the alkaline buffer, bicarbonate which doesn't have the power to consume the weaker acids.  Therefore, the pH will rise until all the hydroxide is consumed. 

I don't think it will really make a difference to a brewer who is careful and precise with their mineral and acid additions.  But it could make a difference to the brewer that adds stuff based on the TLAR theory (that looks about right). 
Title: Re: Palmer Spreadsheet Error
Post by: Kaiser on December 19, 2010, 11:24:59 PM
But at a pH of 5.4, 90% of the added HCO3 will neutralize acids. For lime it is 100% of the adden OH. There is not much difference between the two. Do I understand this right or is there something I missed?

Kai
Title: Re: Palmer Spreadsheet Error
Post by: richardt on December 20, 2010, 02:04:35 AM
This is all very interesting.  Why isn't CaOH used more often in brewing?  Does it cost more?  Does it have unintended consequences when used for mashing or brewing?

If it turns out to work just fine, I sure hope all of you guys who write the spreadsheets (e.g., JP, Kai, EZWaterCalculator, BeerSmith) collaborate with water chemistry experts like AJ and Martin and help advance the predictive accuracy of these spreadsheets by taking into account the amounts of caramel and roasted grains in the gris, and listing the resultant pH and residual alkalinity.

From a practical standpoint, if CaOH does become a useful brew salt addition, then all the spreadsheets (JP's, Kai's, EZWaterCalculator, BeerSmith, etc.) will need to be updated to assist the brewer, and preferably in the most user-friendly manner (i.e., using units like grams, not ppm--although that can be simultaneously shown for those who desire that information).

I just hate making less than great beers because I followed a "spreadsheet."  I did that a while back on an AAA using just BeerSmith and JP's water calculator--I nailed all the ppms for each ion, but the mash pH was well under 5.2.  By then it was too late. 
Title: Re: Palmer Spreadsheet Error
Post by: johnf on December 20, 2010, 02:31:50 AM
This is all very interesting.  Why isn't CaOH used more often in brewing?  Does it cost more?  Does it have unintended consequences when used for mashing or brewing?


Chalk and pickling lime are both stupidly cheap. Believe it or not the latter is used frequently in brewing to lower the alkalinity in brewing liquor. Yes, I know it is counterintuitive that calcium hydroxide is used to lower alkalinity.

I suppose chalk is used to raise alkalinity because that mirrors what happens in nature. There is no good reason (other than historical authenticity) to duplicate nature though.

Note that raising alkalinity is rarely required. Much more thought has gone into acidification as it needs to be done many times more often than the opposite.

As for unintended consequences, my guess is that calcium hydroxide is relatively flavor neutral. A lot of people believe that the flavor impact of calcium carbonate in dark beers is positive. I'm not convinced (that calcium carbonate has positive flavor impacts beyond downstream effects of pH changes) which is why I want to do a side by side.
Title: Re: Palmer Spreadsheet Error
Post by: Kaiser on December 20, 2010, 03:44:29 AM
Calcium hydroxide is a caustic alkali and needs to be handled with care. I guess that's why it wouldn't be my first choice. Kristin England has talked about using it in the mash before.

Kai
Title: Re: Palmer Spreadsheet Error
Post by: gimmeales on December 20, 2010, 09:42:07 PM
So, having just started playing with the EZWater calculator, this is a timely discussion.  All the scientific analysis aside, I would like to know practically, if the tool (v2.0) good enough for the homebrewer just beginning to tweak his water?   Sounds like I'm in good shape if I don't add chalk (thankfully, doesn't appear I need to based on my water and desired ion profile for my next few beers).

Appreciate an input!
Title: Re: Palmer Spreadsheet Error
Post by: mabrungard on December 30, 2010, 05:32:59 PM
The problem with chalk additions in some water programs is that they are calculating the amount of carbonate added to water with the chalk addition.  Since chalk is calcium carbonate, it seems perfectly logical that the carbonate number is the correct one.  Unfortunately, carbonate chemistry is a little more complicated than that.

First of all, in the typical drinking water pH range, carbonate (CO3) will mostly not exist in the water.  It naturally converts to the bicarbonate (HCO3) form in the typical drinking water pH range.  Many of you will recognize that the carbonate species exist in different ionic forms depending upon the pH of the system.  It exists as carbonic acid (H2CO3) at low pH, as bicarbonate (HCO3) at middle pH, and as carbonate (CO3) at high pH.  For the most part, our brewing is in the middle pH range and bicarbonate is prevalent.

The most important reason that we need to convert the carbonate concentration to its equivalent bicarbonate concentration is that the formula that we're using to calculate alkalinity assumes that everything is in the bicarbonate form.  So we have to convert our alkalinity producers to their equivalent bicarbonate concentration.

Since the milliequivalent concentration of the carbonate species will not change when they transform to its various forms, we can calculate what the equivalent amount of each species (in mg/L) is as it transforms and find that numerical conversion value.

Some important chemistry information:

milliequivalents per liter is equal to the ionic concentration divided by the ion's equivalent weight.  

The ion's equivalent weight is equal to the ion's molecular weight divided by the ion's charge.

For Carbonate, the eq wt = 60 mg/mole divided by its charge (-2), or 30 mg/mole
For Bicarbonate, the eq wt = 61 mg/mole divided by its charge (-1), or 61 mg/mole

I'm going to add another alkalinity ion for something else I'll present later.  The equivalent weight of hydroxide (OH) is 17 mg/mole divided by it charge (-1), or 17 mg/mole.

Since the milliequivalents per liter do not change when we convert from one form of carbonate ion to another, we can calculate what that numerical conversion from carbonate to bicarbonate is.  That conversion is simply the ratio of the equivalent weights of the ions.  In the case of carbonate and bicarbonate, that ratio is 61/30 or 2.033333333.  To convert a calculated concentration of carbonate ion to its actual concentration of bicarbonate ion at the typical drinking water pH range would be to multiply the carbonate concentration by 2.033.  

So for a typical 1 gram per gallon chalk addition, the calcium concentration would be 105.7 ppm.  But instead of the 158.4 ppm carbonate concentration, the bicarbonate concentration is actually 322.3 ppm (158.4 x 2.033).  Note that the mEq/L are equal:  158.4/30 = 5.28  and 322.3/61 = 5.28.  

The real problem with chalk is that it just isn't that soluble in water.  There are entire book chapters written on the subject of calcium carbonate solubility since it is critical to life and critical to potable water supply engineers like myself.  

At standard temperature and pressure (STP), the solubility of chalk is about 47 mg/L, which is not that much.  That equates to less than 0.2 grams of chalk in each gallon of water.  Those of you that use chalk know that it just doesn't seem to dissolve in water.  You can bubble air through the water to get it to dissolve faster, but if you're working with air at atmospheric pressure, then you're only going to get that 47 mg/L into the water.  That amount of chalk provides about 55 ppm HCO3 or about 45 ppm alkalinity, which may not be enough for the typical brown or black beer mash.

Work by Troester and DeLange have confirmed that chalk solubility in the mash isn't much higher.  Apparently, the acids present in the mash are pretty weak and cannot provide the protons needed to dissolve the chalk.  It takes extra effort in the form of adding CO2 to the water to get the chalk to dissolve in water.  

I have done tests with water and chalk added at a rate of 2 grams per gallon and have easily dissolved it when I added CO2 to the headspace of the soda bottle and pressurized to over 15 psi with a carbonator cap.  This improves the solubility by over 10 times, but that may not really be practical if your dealing with water needed for a 14 barrel mash.
  
To add alkalinity to mashing water we can also add baking soda (NaHCO3), but then we have to worry about a practical limit for sodium (150ppm, but it should really be kept below 100 ppm).  

So, we need another option to add alkalinity to their mashing water.

Pickling Lime (aka Slaked Lime) is calcium hydroxide (Ca(OH)2).  It is very soluble in water and does not face the solubility problems that chalk has. But I haven't seen anyone discussing how it should be added.

We need to go through the same milliequivalent/liter game that we went through with the carbonate/bicarbonate transformation. The ratio of equivalent weights between bicarbonate and hydroxide is 61/17 = 3.588.  

Therefore, the concentration of calcium added when 1 gram of pickling lime is added to 1 gallon of water is 142.8 ppm and the concentration of hydroxide is 121.1 ppm.  Converting that hydroxide concentration to its equivalent bicarbonate concentration is: 121.1 (ppm OH) x 3.588 = 434.7 ppm.  

As you might expect with a strong base like pickling lime, it has pretty high alkalinity producing potential.  When its added in the small amounts needed to control mash pH, it doesn't really convert into bicarbonate in the mash.  It just consumes any acid it comes in contact with, converting those OH ions directly into H2O when an acid (H) is encountered.  Since Alkalinity is defined as the measure of the capacity of a water to neutralize strong acid, it doesn't matter that the alkalinity is from carbonate, bicarbonate, or hydroxide.  But since our brewing chemistry analyses are based alkalinity calculated from bicarbonate content, it is important to perform the conversion of hydroxide to its equivalent bicarbonate concentration.  

Since the issue of errors in some water calculation programs was the genesis of this discussion, I should end with its discussion.  Those programs assume the carbonate concentration can be treated as a reduced concentration of bicarbonate.  Considering the limited solubility of chalk, its not a bad assumption.  Unfortunately, the severely limited solubility of chalk make even that assumption to optimistic unless the brewer is going to dissolve the necessary quantity of chalk under CO2 pressurization.  In addition, if the brewer does actually use CO2 to dissolve the chalk in the water, then the alkalinity calculated for the chalk addition would definitely be wrong with those water calculation programs. The real solution to adding alkalinity (without too much sodium) is to get brewers up to speed with using pickling lime for adding mash alkalinity and forget about chalk.

I trust this information will be helpful.    
Title: Re: Palmer Spreadsheet Error
Post by: Kaiser on December 30, 2010, 10:30:14 PM
Martin,

Thanks for taking the time to look into this again.

But what I still don't understand is how the mash can be at a pH of 5.4 while the chalk does not dissolve? If I make suspended chalk water and add a weak acid like lactic acid to keep the pH around 5.4 the chalk will slowly dissolve.

Also, why does only half of the chalk dissolve and why is there a saturation at which additional chalk won't raise the mash pH further?

These are questions that I have been thinking about for a while.

Kai
Title: Re: Palmer Spreadsheet Error
Post by: richardt on December 31, 2010, 01:23:44 AM
I just brewed by BDS on the 28th using Sean's suggested salt additions (16 gallons RO water plus 4 gms each of CaCl, NaCl, and MgSO4, plus 8 gms of Chalk, and 16 gms of Baking soda).  My pH readings were around 5.0 with all the CaCl, NaCl and MgSO4 plus half the chalk and baking soda as initially recommended (it was 5.3, but, with additional stirring and time, it drifted back down to 5.0), and at 5.1-5.2 with the full additions. Yes, these are cooled sample temps (it was 50 F outside that day).   I hoping this beer tastes great!

Kai and Martin raise great points for further discussion.  Based on the prior post, I would have expected to observe a pH of 5.5, let's say, at ambient temps around 50-60 F (and not the pH of 5.1 - 5.2 that I got.)  Martin may be onto something here.  Just wanted to provide feedback on the recommendations given to me via the forum.  Thanks everyone.
Title: Re: Palmer Spreadsheet Error
Post by: Kaiser on January 03, 2011, 05:22:08 PM
I finally got around to testing the use of slaked lime (Ca(OH)2) and lye (NaOH) for mash pH adjustments. Lye behaved as expected. The slaked lime did better than chalk and it doesn’t seem to show the saturation that chalk additions tend to show. The pH slope for the slaked lime addition depends on the alkalinity neutralizing power that is assumed for the calcium. In the chart below I assumed that each mole of calcium neutralize 1/3.5 alkalinity equivalents. I.e. one mole of Ca(OH)2 adds  2-(1/3.5) Eq of residual alkalinity. The 3.5 comes from Kolbach’s residual alkalinity formula and may not necessarily correct in all cases.

(http://braukaiser.com/images/misc_forum/strong_base_additions_mEq_vs_pH.gif)

Each series evaluated 2 mash thicknesses (2.5 and 5 l/kg) and the base additions were based on the grist weight (mEq/kg). I think the latter is a better way to think about any water treatments in the mash since the grain is the pH buffer and not the water.  The starting mash was RO water with a 90/10 mix of Munich II and CaraAroma. Not necessarily something that you would make into a beer but a somewhat realistic grist that is expected to give a fairly low mash pH.

There were some hick-ups in the Ca(OH)2 curves that are not visible in the NaOH data. But at this point it is possible that this is simply an error in the measurements.

Looks like a side-by-side experiment and spreadsheet support for Ca(OH)2 additions is in order.

Kai
Title: Re: Palmer Spreadsheet Error
Post by: mabrungard on January 03, 2011, 05:29:44 PM
Excellent information!

Not a surprising result.  I'm cautious about adding lye, since it could boost the sodium content too high.  But on second thought, the amount added for pH adjustment would be tiny.  The next question is where would you get food grade lye from?  I know I can get food grade lime as pickling lime. 

Very interesting.
Title: Re: Palmer Spreadsheet Error
Post by: denny on January 03, 2011, 05:33:57 PM
Martin, I've been looking for pickling lime with no luck.  Where do you get it?  A grocery store?  That's where I've been looking.
Title: Re: Palmer Spreadsheet Error
Post by: Hokerer on January 03, 2011, 05:46:49 PM
Martin, I've been looking for pickling lime with no luck.  Where do you get it?  A grocery store?  That's where I've been looking.

I've seen at it our regular grocery stores around here.  In the section with sugar/flour/spices and such.
Title: Re: Palmer Spreadsheet Error
Post by: Kaiser on January 03, 2011, 05:54:10 PM
Not a surprising result.  I'm cautious about adding lye, since it could boost the sodium content too high.  But on second thought, the amount added for pH adjustment would be tiny.  The next question is where would you get food grade lye from?  I know I can get food grade lime as pickling lime. 

There is no benefit to using lye. It works as good as baking soda and. It even adds the same amount of sodium. In contrast to baking soda it consumes CO2 that is dissolved in your mash. But that should not matter.

 
Martin, I've been looking for pickling lime with no luck.  Where do you get it?  A grocery store?  That's where I've been looking.

I ordered my lye and pickling lime on-line. With the gas prices these days you easily spend the $5-10 that you spend for shipping for gas when driving around to find that.

But you may also try ethnic food stores. I believe Ca(OH)2 is used for making tortillas.

Kai
Title: Re: Palmer Spreadsheet Error
Post by: denny on January 03, 2011, 05:59:11 PM
Martin, I've been looking for pickling lime with no luck.  Where do you get it?  A grocery store?  That's where I've been looking.

I've seen at it our regular grocery stores around here.  In the section with sugar/flour/spices and such.

Thanks.  I'll keep looking.
Title: Re: Palmer Spreadsheet Error
Post by: kramerog on January 03, 2011, 06:11:17 PM
Bear in mind that pickling lime will slowly absorb carbon dioxide from the air and form chalk.  So keep the lime in an airtight container and you might want to throw it away if it is "very old."
Title: Re: Palmer Spreadsheet Error
Post by: Hokerer on January 04, 2011, 01:31:00 AM
I've seen at it our regular grocery stores around here.  In the section with sugar/flour/spices and such.
Thanks.  I'll keep looking.

Had to hit the grocery story to pick up some goodies before the game and I double-checked.  The pickling lime was right next to the salt.  About the same size canister but light green.  $3.79 for a pound.
Title: Re: Palmer Spreadsheet Error
Post by: BrewArk on January 05, 2011, 08:06:08 PM
I've read this thread with interest.  But I don't see the issue.  I've never used chalk (it doesn't dissolve fast enough).  If I need additional Ca it's gypsum, carbonate/bicarb it's baking soda or soda ash.  Chloride has never been a problem, but I'd add CaCl.  If there were too much of something, add some RO & back add what was needed.

I know it's difficult to add RO to drinking water supplies, but it's very doable at brewing levels. ???
Title: Re: Palmer Spreadsheet Error
Post by: johnf on January 05, 2011, 08:27:23 PM
The issue is that mash pH is very important and so some people who don't have pH meters would like to estimate it. This turns out to be extremely difficult to do and making matters worse is that some widely used models have serious flaws.
Title: Re: Palmer Spreadsheet Error
Post by: punatic on January 05, 2011, 09:30:00 PM
I've read this thread with interest.  But I don't see the issue.  I've never used chalk (it doesn't dissolve fast enough).  If I need additional Ca it's gypsum, carbonate/bicarb it's baking soda or soda ash.  Chloride has never been a problem, but I'd add CaCl.  If there were too much of something, add some RO & back add what was needed.

I know it's difficult to add RO to drinking water supplies, but it's very doable at brewing levels. ???

I operate several MGD+ drinking water treatment sytems that are demineralized by reverse osmosis.  We blend back a portion of the feedwater (about 10%) to achieve the desired TDS content in the product water.
Title: Re: Palmer Spreadsheet Error
Post by: mabrungard on January 05, 2011, 09:43:47 PM
BrewArk makes a good point and doesn't use chalk, but there are brewers that do use it and are expecting it to do its job.  My point was to make sure that brewers are educated about chalk use and the limitations that some water programs had to make to accomodate chalk's limited solubility. 

Brewing water programs are using new information and making it a little more feasible for brewers to actually come close to an intended mash pH.  I noticed that EZ Water now includes grain acidity in predicting mash pH.  I am also finalizing a program that takes grain acidity a little further in assessing mashing pH.  In either case, the hope is to give regular brewers tools that they can rely on to predict their mash conditions and not absolutely have to have a pH meter. 
Title: Re: Palmer Spreadsheet Error
Post by: oldtree on January 06, 2011, 02:05:02 AM
So, is adding CaCO3 to a mash basically useless?  It sounds like it will neither add calcium nor raise the mash pH.
Title: Re: Palmer Spreadsheet Error
Post by: blatz on January 06, 2011, 02:16:50 AM
So, is adding CaCO3 to a mash basically useless?  It sounds like it will neither add calcium nor raise the mash pH.

i am no water engineer by any stretch, but I watched my mash climb 0.3 this weekend with the addition of chalk when I realized my mash pH was too low.  so be what it may, it works, whether or not its magic dust, I'm not sure.

on that note, I'd always read to add the salts to the mash, not the strike water, as the mash (I suspect) helps increase the solubility of the salts?
Title: Re: Palmer Spreadsheet Error
Post by: Kaiser on January 06, 2011, 02:52:44 AM
The problem is that chalk is soluble at mash pH. And it does dissolve. At least to some extent since it does show an effect on mash pH. What is to be questioned is the amount of acid neutralization that can be achieved with undissolved chalk.

Kai
Title: Re: Palmer Spreadsheet Error
Post by: richardt on January 06, 2011, 03:01:26 AM
I've read that, too.  
That's why I'm kind of confused by comments that people are adding brew salts to the water first (whether in the HLT or in the MLT prior to grain addition.)  

I thought I read somewhere that strike water should be added to the grains (and not the other way around) in order to prevent thermal damage to the mash enzymes.  It also makes more sense to add warmer (or cooler) water, rather than grains, in order to hit the mash target temps.

I'm also a little fuzzy on what exactly EZ water calculator means by "sparge water" addition when they seem to be saying the additions actually are put into the boil.  Can anyone clarify the reasoning behind the formula and calculations with the "sparge additions"?
Title: Re: Palmer Spreadsheet Error
Post by: Kaiser on January 06, 2011, 03:30:05 AM
I'm also a little fuzzy on what exactly EZ water calculator means by "sparge water" addition when they seem to be saying the additions actually are put into the boil.  Can anyone clarify the reasoning behind the formula and calculations with the "sparge additions"?

The idea is that you don't want to add alkalinity to the sparge water (baking soda and chalk do that) which is why some brewers add the sparge water salts to the boil. If you don't add them to the boil the sparge water will dilute the salts that were added to the mash and you end up with a slightly softer overall water profile.

I think that you can also add all the salts to the mash and none to the sparge water. Adding salts to the sparge water doesn't do much harm either, in my experience at least.

Kai
Title: Re: Palmer Spreadsheet Error
Post by: kerneldustjacket on January 06, 2011, 04:50:56 PM
 The next question is where would you get food grade lye from?  I know I can get food grade lime as pickling lime.  


Martin, as someone said you can get food grade lye online -- specifically at sites that sell soap making supplies.
I have some that I bought to make laugen brotchen and Swabian bretzels (pretzels); the lye is added to water and you dunk the risen rolls of bretzels into it just prior to baking.


On adding chalk: something I tried once was to crush my dark grains serpeate from the rest. I pladed them in a plastic bag and added the chalk, then shook together to coat the crushed grains. All the chalk seemed to stick to the grain bits...this was then added to the rest of the grains. My thinking was that the chalk would be right at the site where the dark grains would release their acidity,and so aid getting the chalk into solution.

So...does this sound silly? I have no means of testing if it makes any difference...no pH strips, no pH meter.
Title: Re: Palmer Spreadsheet Error
Post by: richardt on January 06, 2011, 06:03:49 PM
On adding chalk: something I tried once was to crush my dark grains serpeate from the rest. I pladed them in a plastic bag and added the chalk, then shook together to coat the crushed grains. All the chalk seemed to stick to the grain bits...this was then added to the rest of the grains. My thinking was that the chalk would be right at the site where the dark grains would release their acidity,and so aid getting the chalk into solution.  So...does this sound silly? I have no means of testing if it makes any difference...no pH strips, no pH meter.

Seems logical--I might try something similar when I cold-steep my dark grains (or cap a mash) in order to keep the pH at ideal levels.
Title: Re: Palmer Spreadsheet Error
Post by: kramerog on January 06, 2011, 06:16:03 PM

On adding chalk: something I tried once was to crush my dark grains serpeate from the rest. I pladed them in a plastic bag and added the chalk, then shook together to coat the crushed grains. All the chalk seemed to stick to the grain bits...this was then added to the rest of the grains. My thinking was that the chalk would be right at the site where the dark grains would release their acidity,and so aid getting the chalk into solution.

So...does this sound silly? I have no means of testing if it makes any difference...no pH strips, no pH meter.

The brewing spreadsheet assumes that only 50% of the chalk is effective.  Without data, what level of effectiveness should you presume?  Baking soda and pickling lime are clearly superior because they readily dissolve.  
Title: Re: Palmer Spreadsheet Error
Post by: Kaiser on January 06, 2011, 07:01:46 PM

The brewing spreadsheet assumes that only 50% of the chalk is effective.  Without data, what level of effectiveness should you presume?  Baking soda and pickling lime are clearly superior because they readily dissolve. 

Up to an addition rate of about 250 mg/l (1 g/gal) it seems to be about 50% effective. In fact I brewed the same Schwarzbier recipe with dissolved and undissolved chalk and by using 50% of the undissolved chalk amount when dissolving the chalk I got about the same mash pH. (see here http://braukaiser.com/lifetype2/index.php?op=ViewArticle&articleId=132&blogId=1)

So far I have not seen any pressing need for dissolving chalk in the brewing water other than getting something that behaves a bit more predictable. But I have brewed a number of beers with dissolved chalk so far. Believe me, if find a good reason to dissolve chalk I’ll let you guys know that you can’t brew good beer without that additional step ;)

So far the outcomes of my research have helped me, and hopefully others, to better understand the mash pH behavior that we see in practice. Unfortunately I have not found a way to make excellent beer even better.

Kai
Title: Re: Palmer Spreadsheet Error
Post by: kerneldustjacket on January 06, 2011, 07:03:40 PM

Seems logical--I might try something similar when I cold-steep my dark grains (or cap a mash) in order to keep the pH at ideal levels.

Yes...seems logical, but without experimental testing it's only just a hypothesis.


The brewing spreadsheet assumes that only 50% of the chalk is effective.  Without data, what level of effectiveness should you presume?  Baking soda and pickling lime are clearly superior because they readily dissolve.  

I tried this prior to hearing about the better effectiveness of baking soda or pickling lime. I'd hate to guess at what effectiveness it might have, as I'm certian I'd be way off.

Plus, I've long felt that chalk has a flavor/mouthfeel impact that works well with some beer styles, dry stout in particular. So I've often added some, but normally only a third to a half of what calculations suggested.
But, the only sure way to find out if there's truth to that idea is a blind triangle taste test...who knows, I may be wasting my time by adding it.
Title: Re: Palmer Spreadsheet Error
Post by: oldtree on January 08, 2011, 12:40:37 AM
Looking at pickling lime, it appears that there is some amount of iron in the grocery store products.  Is it a negligible amount as far as brewing and calculations?