Help with Water Profile

[LBussy]

Normally I would post what I was able to come up with, but nothing I was able to come up with was anywhere near close to what I need. I have tried several different tools and none seem to get me close so if there's a tool someone wants to recommend and give me "homework", by all means please send me to go do and I'll bring back what I can. Specifically, I've been unable to get enough sulfate ... I was thinking Magnesium Sulfate would be good but none of the calculators I have found allow this.

I'm trying to approximate Pellegrino, here is the analysis:

http://www.nestle-watersna.com/asset-library/documents/sp_eng.pdf

And here is my local water:

https://www.kcwaterservices.org/wp-content/uploads/2015/04/2015-WQR-Final.pdf

Starting with RO is is fine too ...

ANY tips to get me going in the right direction would be most welcomed. My brain hurts. I spent several hours trying and got no closer than when I started.

 

[McKnuckle]

First of all, WHY would you want to replicate that water? It's got some pretty extreme values. It has 410 ppm SO4! And 53 ppm Mg, 32 Na... The sulfate is sky high. I prefer it no higher than 175 ppm, and usually aim for 50-100. No reason to have so much Mg or Na either. You don't need any added amounts of those in your water, especially Magnesium.

Plus I just noticed that the water has hardness over 600! Geez. My horrible well water that destroys my pipes is half that, and it's still a beast.

What's the goal here from a brewing perspective?

 

[LBussy]

First of all, WHY would you want to replicate that water? It's got some pretty extreme values. It has 410 ppm SO4! And 53 ppm Mg, 32 Na... The sulfate is sky high. I prefer it no higher than 175 ppm, and usually aim for 50-100. No reason to have so much Mg or Na either. You don't need any added amounts of those in your water, especially Magnesium.

Plus I just noticed that the water has hardness over 600! Geez. My horrible well water that destroys my pipes is half that, and it's still a beast.

What's the goal here from a brewing perspective?

I plan to carbonate it and drink it while brewing ... ever price Pelegrino?

I keep Club Soda on tap for the wife, she asked for this. That's pretty much why I'm trying to do it. That and it's irked me because I can't figure out how to get it.

 

[mabrungard]

You should be able to start with your tap water and achieve that final profile since it is quite mineralized. An important bit of missing information for the Pelegrino water report is the alkalinity, but that can be inferred from the other data. The bicarbonate content (aka: alkalinity) is found from the missing anion total. Using a good calculator like Bru'n Water will help you balance the existing and proposed water profiles and to figure out the mineral additions. Be aware that chalk won't dissolve quickly if it is used to supply bicarbonate, but it should dissolve eventually when under CO2 pressure.

I do recommend dechlorinating the water prior to kegging.

 

[LBussy]

Martin I'll give it a shot. I spent some time with your spreadsheet and did a pretty poor job of it. You're the expert though so I'll give it another go and post what I come up with.

 

[LBussy]

Okay so I tried again and I hit the same issues ... the Anion/Cation ratio is off for both my local water and the desired profile. The pH is off when I enter the desired profile and it looks as if I am supposed to go with the calculated value? Also the total hardness & alkalinity is way off - likewise it looks like it's supposed to be calculated and not entered.

Here's what I came up with (hopefully this shares correctly):

https://drive.google.com/file/d/0B5X8cToiFNbsX1FOeDMyOXozYnc/view?usp=sharing

 

[McKnuckle]

You want to drink it, not brew with it! Well I didn't see that coming. Fair enough. Good luck!

 

[mabrungard]

It doesn't share properly. But all you are doing is using the calculator as an ion calculator. pH doesn't enter into what you are doing.

 

[Yooper]

You should be able to start with your tap water and achieve that final profile since it is quite mineralized. An important bit of missing information for the Pelegrino water report is the alkalinity, but that can be inferred from the other data. The bicarbonate content (aka: alkalinity) is found from the missing anion total. Using a good calculator like Bru'n Water will help you balance the existing and proposed water profiles and to figure out the mineral additions. Be aware that chalk won't dissolve quickly if it is used to supply bicarbonate, but it should dissolve eventually when under CO2 pressure.

I do recommend dechlorinating the water prior to kegging.

Martin, you are awesome. I'm following this, as I also want a good seltzer water on tap. My plain tap water is ok, but gets "biting" highly carbed. RO water is bland, but spritzy. I want to mess around with this when I get home from my winter quarters, so a posting to be able to find this again!

Thank you.

And Lee, thank YOU as well!!!

 

[LBussy]

You want to drink it, not brew with it! Well I didn't see that coming. Fair enough. Good luck!

Yeah I guess I could have been more explicit in my goals. I wonder what sorta beer that would make? I mean "common sense" tells us that it would not be great for brewing, but that never stopped the folks in Burton.

It doesn't share properly. But all you are doing is using the calculator as an ion calculator. pH doesn't enter into what you are doing.

Okay - still I would have expected the other values to come into line? This might work better:

http://www.silverfoxcrafts.com/wp-content/uploads/2016/03/Brun-Water-v1_16bus-Pellegrino.xls

I can't quite get things to line up which I think is a result of the original water profile not being balanced. I ended up having to use 100% RO because the bicarb is so low.

Martin, you are awesome. I'm following this, as I also want a good seltzer water on tap. My plain tap water is ok, but gets "biting" highly carbed. RO water is bland, but spritzy. I want to mess around with this when I get home from my winter quarters, so a posting to be able to find this again!

Thank you.

And Lee, thank YOU as well!!!

Did you try that club soda Yoop? It's down and dirty but SWMBO likes it well enough - she REALLY wants some Pellegrino (Pellemeno?) though.

 

[Yooper]

Did you try that club soda Yoop? It's down and dirty but SWMBO likes it well enough - she REALLY wants some Pellegrino (Pellemeno?) though.

Not yet- I'm still in S. Texas, and my carbonator cap is up north so I have to wait until I get home. I'll try it right after Easter, once I'm home.

 

[LBussy]

I can get things pretty close now, but only with the registered version of Bru'n Water. Suggestions are happily accepted.

(image removed, see below)

 

[LBussy]

I got it a little better yet using 100% RO as a start (preferred due to chloramines in tap water). I can't see how to make it any better but I'm all ears:

 

[ajdelange]

I'm coming in late here so I hope I'll cover all the concerns.

There is really no problem synthesizing this water but it's not the sort of thing we usually do in brewing as it is super saturated with CO2 to the extent of 0.1 atm (which we get from the pH and alkalinity). Assuming that the report you have is complete and accurate and knowing that the water must be balanced electrically its alkalinity (pHe 4.5) is is about 178 or, more to the point, it contain 24.2 mmol/L carbo 86% of which is in the form of dissolved CO2. It should be apparent from this that CO2 is going to have to be used to prepare this water. To make it add to each liter of RO water:

CaCl2.0H2O: 72.94 mg
NaCl: 0 mg
KCl: 0.84 mg
CaSO4.2H2O: 359.40 mg
MgSO4.7H2O: 537.44 mg
NaHCO3: 116.93 mg
Ca(OH)2:92.42 mg

[This post has been considerably edited as I originally did formulations for 15 mg/L magnesium. The formulations in this edited post are for 53 mg/L]

Put the treated water in a container pressurized with CO2 to about an atmosphere (or more if you like) and shake. After a bit of this release the gas and check the pH of the water. It should be below 5.6 (if it isn't, close it up and shake it some more or just leave it under CO2). Let it stand until the pH is 5.6 and you have exactly (in theory) what you asked for. All ion concentrations are within 0.01% of targets.

There are many other combinations of salts that will get you there but I chose ones that are readily available and dissolve easily (no CaCO3).

Now it says somewhere here that pH doesn't have anything to do with this problem. Nothing could be further from the truth. pH is the 'Master Variable' in water (and other) chemistry. It is what controls the whole shooting match. You could decide, that you wanted something fizzy and tart and shoot for pH 4.8 instead of 5.6. You would add the following salts (all mg/L)

CaCl2.0H2O 4.59
NaCl 71.99
KCl 0.84
CaSO4.2H20 359.75
MgSO4.7H20 537.34
NaHCO3 13.44
CO2 5817.97
Ca(OH)2 137.79
CO2 Vols 2.86

You'd need to apply 3.3 atm of CO2 and after equilibrium was reached (shaking or standing) you'd have exactly the same water in terms of everything except dissolved CO2 and carbo. Dissolved carbo would now be 132.4 mmol/L (mostly as 2.9 volumes of dissolved CO2). IOW, the content of the other ions is the same and you put the fizziness where you want it by controlling the carbonating gas.

Now from your water: We have the usual uncertainties related to the differences between the reported averages and what may actually come out of your tap and the fact that they don't report chloride. Sticking 24 mg/L chloride in the mix balances is but this is really just guessing. The other notable thing is that the sodium is higher than the target which means we need to get some of our bicarbonate from calcium carbonate which is a pain but as you will be under CO2 pressure for part of the process I guess that's OK. RO really is the better choice IMO.

To get very close (all concentration errors <0.005% add, to each liter of your water:

CaCl2.0H2O 97.84
NaCl 233.60
KCl 6.55
CaSO4.2H20 2512.28
MgSO4.7H20 4141.14
Liters RO/DI water 6.80
CaCO3 1032.89
NaHCO3 313.61
CO2 7657.89
HCl 139.34

Note that all the numbers are larger. This is because you are also adding quite a bit of water. In fact, for this much added RO you might as well use straight RO and wipe out the uncertainties WRT to Cl, average vs actual etc.
Ca(OH)2 327.72
Na2CO3.H2O 20.18

Again mix the salts, the tap and the RO/DI water and pressurize with CO2 to target pH.

The resulting water
pH 5.6
CO2 Vols 0.45
CO2 Atm 0.52
Carbo 24.17
Alk 178.13

Another interesting approach with RO, if you don't want to mess with CO2, is to get the CO2 from sodium carbonate and sodium bicarbonate by way of using HCl and H2SO4 as the sources of sulfate and chloride. This, of course, involves getting ones hands on food grade acids and soda ash (sodium carbonate) and I therefore only mention it as a curiosity. This worked very well when I thought the desired magnesium content was 15 mg/L. At 53 mg/L it doesn't.

With a good spreadsheet one can go on in this vein all night doing things like saying "Let's let the bicarb go where it wants to as we don't really care about it as long as we get the pH and other ions where we want them" and de-weight the bicarbonate in the optimization algorithm error calculation. Seems as if the first salt set in RO/DI with CO2 would be the simplest way to get where you want to be.

 

[LBussy]

First, I appreciate the time you took to explain this all!

There is really no problem synthesizing this water but it's not the sort of thing we usually do in brewing as it is super saturated with CO2 to the extent of 0.1 atm (which we get from the pH and alkalinity).

Aside from carbonation, is the CO2 only lowering the pH in this? Therefore knowing the alkalinity and the pH one (not me, but someone) can calculate the amount of CO2 present?

If that is correct, assuming "enough" carbonation, is it reasonable to assume the carbonation level is less important to the taste since the carbonation of the drink changes anyway in the glass?

It should be apparent from this that CO2 is going to have to be used to prepare this water.

Given that was a requirement from the wife, that's not an issue.

To make it add to each liter of RO water:

CaCl2.0H2O: 37.84 mg
NaCl: 36.96 mg
KCl: 0.84 mg
CaSO4.2H2O: 628.58 mg
MgSO4.7H2O: 152.11
NaHCO3: 63.80

Put the treated water in a container pressurized with CO2 to about an atmosphere (or more if you like) and shake. After a bit of this release the gas and check the pH of the water. It should be below 5.6 (if it isn't, close it up and shake it some more or just leave it under CO2). Let it stand until the pH is 5.6 and you have exactly (in theory) what you asked for. All ion concentrations are within 0.1% of targets.

There are many other combinations of salts that will get you there but I chose ones that are readily available and dissolve easily (no CaCO3).

Magnesium seems about a third or less of what it should be ... unless I'm mmissing something? To be fair what I am doing to make sense in my small brain is multuplying those numbers by 3.78541 to get mg/gal and then dividing by 1000 to get g / gal and then plugging them in Martin's spreadsheet. I know if I spend enough time trying to figure it all out I *might* be able to make my own spreadsheet and understand it more. For right now the best way I can try to understand it is to use two (or more) different tools and make them agree.

Now from your water: We have the usual uncertainties related to the differences between the reported averages and what may actually come out of your tap and the fact that they don't report chloride.

Plus the chloramine ... it's easier for me to just go purchase 5 gallons of RO water at the grocery store than it is to dechlorinate my tap water. One of these days I'll have a home setup but for now this is what I have available.

 

[mabrungard]

Now it says somewhere here that pH doesn't have anything to do with this problem. Nothing could be further from the truth. pH is the 'Master Variable' in water (and other) chemistry. It is what controls the whole shooting match.

Wow! It is too bad you came late to the discussion since you apparently didn't read my post. pH has nothing to do with the calculations within Bru'n Water...not for plain water chemistry. It is a mashing pH prediction.

Since the OP is using the program to formulate mineral additions and he also assumed that the resulting pH reported meant something, I figured I should alert him that he was reading too much into the result. Until malts are included in the analysis, the pH results reported by Bru'n Water are invalid for water.

 

[ajdelange]

First, I appreciate the time you took to explain this all!

Not a problem as I'd been thinking along these lines as a result of responding to a similar post at https://www.homebrewtalk.com/showthread.php?t=575486

Aside from carbonation, is the CO2 only lowering the pH in this?

In a natural water in equilibrium with limestone the pH, alkalinity ad hardness are all set by the amount of CO2 to which the water is exposed. This CO2 in mesic region groundwater is produced by respiring soil bacteria.

Therefore knowing the alkalinity and the pH one (not me, but someone) can calculate the amount of CO2 present?

Yes and you can do it too. The math is at https://www.homebrewtalk.com/showthread.php?t=473408. You can also get it from a couple of charts (obviously based on that math) which I'll post tomorrow.

If that is correct, assuming "enough" carbonation, is it reasonable to assume the carbonation level is less important to the taste since the carbonation of the drink changes anyway in the glass?

I can't comment on what is 'enough'. That's a matter of personal taste. The water in question is described a sparkling but apparently only contains 0.1 atm of CO2. That's not very 'sparkling' to my way of thinking. [After correcting the magnesium level it appears to contain CO2 at about half an atmosphere - more sparkly for sure but still not very] There are two aspects to CO2. One is the pain (and I'm told that's what it actually is) caused by carbonic acid attacking the nerves in your tongue and the other is the tartness caused by the low pH of waters in which a lot of carbonic acid is dissolved. Thus the carbonation level is very important to the way the beverage is perceived and yes, it changes dramatically as CO2 escapes over the time it takes to finish the drink. Same as with beer!

Magnesium seems about a third or less of what it should be ... unless I'm mmissing something? To be fair what I am doing to make sense in my small brain is multuplying those numbers by 3.78541 to get mg/gal and then dividing by 1000 to get g / gal and then plugging them in Martin's spreadsheet.

Well I'm afraid the reason the Mg is so low is because I fat fingered (or, to be really honest about it, more probably fat-brained) 15 mg/L into the Mg++ field instead of 53 mg/L. I'll go back and edit the earlier post for the RO water case tonight and will fix the rest of the numbers tomorrow. In any case, the new MgSO4.7H2O requirement is 537.4 mg/L.

I know if I spend enough time trying to figure it all out I *might* be able to make my own spreadsheet and understand it more.

It is clearly pretty simple to put together a spreadsheet that figures out how many mg of, for example, Mg and SO4= one gets from x mg of MgSO4.7H2O by looking up the molecular weights of Epsom salts, water, magnesium and sulfuric acid (subtract 2 to get molecular weight of sulfate ion). Where it gets a little tricky is in handling the carbonic acid system but that is really not that bad as you'll see if you look at https://www.homebrewtalk.com/showthread.php?t=473408 and add
Step 12: CO2 = C*f0*44; H2CO3 = C*f0*62 (grams/L). Once you have a spread sheet that calculates Mg++, SO4=, HCO3-, CO3=, Cl-, Ca++ etc. from amounts of added H2SO4, HCl, NaCl, HLac, CO2, NaHCO3, MgSO4 etc AT A SPECIFIED pH it is a simple matter to add in a list of desired ion concentrations, compute the logs of the absolute values of the differences between calculated and desired, compute the sum of the squares of those errors and ask Solver to pick salt amounts that minimize that sum of squares. I absolutely guarantee that you will have a deeper understanding of how this all works if you pull this off. Don't hesitate to ask for help.

For right now the best way I can try to understand it is to use two (or more) different tools and make them agree.

If a tool purports to allow you to synthesize water by adding salts to RO and it doesn't ask you what pH you want the synthesized water to be at then be wary of that tool. If you add neutral salts to water at some pH the pH will stay the same but if you add acid, base, bicarbonate or carbonate salts to water the pH will shift and this must be accounted for. I cannot find where to put the target pH into Bru'n water, for example, and thus cannot figure out how it gives answers if, for example, sodium bicarbonate is added unless it assumes that the bicarbonate ion stays as bicarbonate which it does not do except approximately at pH 8.4.

 

[ajdelange]

Wow! It is too bad you came late to the discussion since you apparently didn't read my post. pH has nothing to do with the calculations within Bru'n Water...not for plain water chemistry. It is a mashing pH prediction.

I'm just really confused. I can't run it because I'm on a Mac but if I look at the images posted earlier in this thread I see places to put in target profiles and salt additions including bicarb, lime and chalk and I see a mashing water profile apparently calculated from these inputs. This includes bicarbonate but I don't see where the user puts in the pH at which he wants the profile calculated. How can it calculate bicarbonate without knowing the pH at which it is to be calculated?

Since the OP is using the program to formulate mineral additions and he also assumed that the resulting pH reported meant something,

It does. It is from the pH that the carbo and hence concentrations of carbon dioxide, bicarbonate ion and carbonate ion (small) are calculated.

I figured I should alert him that he was reading too much into the result. Until malts are included in the analysis, the pH results reported by Bru'n Water are invalid for water.

So you are saying that it should not be used for water synthesis? That's sort of what I told him. Or would a statement to the effect that you can match a desired profile with respect to all ions except bicarbonate be more appropriate?

 

[LBussy]

Okay so quick take away this morning before I jump on a conference call: Bru'n Water is specifically tailored for mash/sparge water and therefore pH is only completely correct when malts are introduced. In the case of a water to be enjoyed for the sake of the water, adjusting the pH/bicarbonate is an important point. AJ's calculations included bicarbonate as a product of additions of both sodium bicarb and CO2 to balance the sodium and the pH to the exemplar analysis?

I don't even remember all of my chemistry and math teachers' names, but I owe them all a huge apology.

I am somewhat comfortable figuring out the relative molar masses, etc., and I spent about an hour this morning over coffee making a spreadsheet to do the same. THEN I realized for instance I did not need to track elemental sulfur but rather the anion sulfate. Oh well ... at least I have all the molar masses looked up. Back to the drawing board on THAT one.

I have more to learn and that much is very apparent. And I love it.

 

[mabrungard]

AJ, I've made the broad assumption that since the typical water supply has a pH in the 6.5 to 8.5 range as recommended by WHO and EPA, most of the alkalinity is in the form of bicarbonate. I then go on to require that all the alkalinity is converted into its equivalent 100% bicarbonate concentration for the calculations used in the program. While there may be very minor errors in that methodology, I know that it works well in practice.

With respect to mashing calculations, we know that the typical mashing pH range will be in the 5 to 6 range and the program iterates the results of the predicted mash pH with the acid calculations to adjust that calculation without user pH input. Therefore, pH is not a user input parameter for the mashing pH calculations.

By the way, Bru'n Water works fine on Macs. Its just that Excel for Mac does not work with normal Excel programs. I call this a result of the Jobs/Gates feud. Fortunately, there are freeware programs such as Open Office for MacOS that do work with normal Excel programs. The other option is to upgrade to the latest version of Office for Mac since I understand that Microsoft has finally agreed to include the proper software support that was lacking.

 

[ajdelange]

Okay so quick take away this morning before I jump on a conference call: Bru'n Water is specifically tailored for mash/sparge water and therefore pH is only completely correct when malts are introduced. In the case of a water to be enjoyed for the sake of the water, adjusting the pH/bicarbonate is an important point.

Let's add the volume of dissolved gas as an important parameter here.

AJ's calculations included bicarbonate as a product of additions of both sodium bicarb and CO2 to balance the sodium and the pH to the exemplar analysis?

The 'art' of pH measurement/prediction is very general. We put two kinds of things into water: acids and bases and whether something is acid or base depends on whether it emits (acid) or absorbs (base) protons in being shifted to a pH of interest from its intrinsic pH (the pH at which it comes to you). If you know the intrinsic pH of an addition and have a model for the absorption/emission as a function of the target pH you can figure how many protons the material will give off or absorb when brought to target pH (all this is per unit mass of the material). For the carbo system the model is as given by the math in the sticky. For the phosphoric, sulfuric, lactic... acid systems by identical math with different pK numbers. For malts the data comes from measurements on the malt or, when those aren't available, from measurements on similar malts but it's the same idea: protons emitted or absorbed are a simple mathematical function of the target pH, the intrinsic pH (DI water mash pH) and the parameters for the malt. When any of this stuff is mixed the number of protons absorbed has to equal the number emitted (they are conserved) so the sum of the emissions (a negative emission is an absorption) has to be 0. To predict pH one computes the sum at various pH's until the pH which gives a 0 sum is found. To set pH one adjusts the amount of absorbers/emitters in the mix until the sum is 0 at the desired pH. It is really exquisitely simple (once you get the hang of it).

I don't even remember all of my chemistry and math teachers' names, but I owe them all a huge apology.

Haven't thought about this in many, many years and am amazed at how many of the names I can remember. Still owe an apology to many of them though. Every one of those guys was a bit more eccentric than the last one and we were merciless.

I have more to learn and that much is very apparent. And I love it.

Delighted!

 

[LBussy]

"Eccentric" may be an understatement. The most formative teacher I can remember was "Mr Beck," a 5th grade general science teacher. We would pepper him with questions thinking we were preventing him from teaching that which he wanted to teach. Somehow we all learned what we had to learn and a few of us did very well. I'll never forget him.

Thank you AJ and Martin for being patient with me through this. My wife has watched me obsess with spreadsheets over the last couple days and she is convinced she should just buy Pellegrino. I however am pretty psyched about it. I purchased the salts I did not have yesterday so this weekend hopefully I'll be be giving it a try. I have to travel on Monday so with carbonation time that means I won't actually tap the keg till late next week. (Yes I know I can force the carbonation, but I don't have an anti-backflow valve for my CO2 line.)

I'll report back once I've had a chance to try it, and of course in the meantime I'll be checking the other threads out to learn even more. A couple of those SCREAM out to be printed and read on the flights. Something about jet noise makes it easier for me to concentrate. Weird.

 

[ajdelange]

I guess I feel compelled to mention Whitney G. Swift, known as 'Mr. Chips' for his bachelorhood, antiquity, tics, and decrepitude. One warm spring afternoon he imparted to our drowsy post prandium class the 'Tiriginometric Cheer' which, as you have not heard, I will now proceed to relate:--

Sine Cosine, Cosine Sine;
Cosine Cosine, Sine Sine;
Rah!

We were enthralled as the effort about killed the old fellow and we importuned him in every class for the rest of the semester to repeat the performance which he did but only once or twice. To this day I can tell you what sin(A ± B) or cos(A ± B) are without a moment's hesitation

 

[ajdelange]

AJ, I've made the broad assumption that since the typical water supply has a pH in the 6.5 to 8.5 range as recommended by WHO and EPA, most of the alkalinity is in the form of bicarbonate. I then go on to require that all the alkalinity is converted into its equivalent 100% bicarbonate concentration for the calculations used in the program. While there may be very minor errors in that methodology, I know that it works well in practice.

I guess that turns on one's definition of 'very minor' which I will leave up to you. The relationship between actual bicarbonate content, alkalinity, definition of alkalinity and sample pH is trivial to compute but nevertheless somewhat complex as the picture below shows. The labels on the curves are the number that one would multiply by the alkalinity (in mEq/L) to get the bicarbonate content of the water in mmoL/L. The dotted line describes traces out the alkalinity and pH conditions for which the assumption that all alkalinity is bicarbonate is true. Like colored pairs to the left and above the heavy black line indicate regions of 0.5%, 1%, 1.5%, 2% and 3%. I suppose up to ±3% is an acceptable error and that covers source pH's of up to pH 8.5 as long as the alkalinity is above 0.4 mEq/L (24 ppm as CaCO3). Clearly as the alkalinity approaches 0 a higher percentage error is tolerable. Now it is to the right of the 0.96 curve, where errors are > 4% that I begin to arch an eyebrow. OP's water presents at pH 9.8 where the error in assuming it is all bicarbonate is about 40%. Is he unable to use the spreadsheet or do you have some workaround for guys like him. There was another guy on here a day or 2 ago with pH > 10 as I recall. As water utilities strive to push Langelier index up (or Ryznar index down) in hysterical reaction to Flint I think we are going to be seeing these higher pH's.

With respect to mashing calculations, we know that the typical mashing pH range will be in the 5 to 6 range and the program iterates the results of the predicted mash pH with the acid calculations to adjust that calculation without user pH input. Therefore, pH is not a user input parameter for the mashing pH calculations.

If you deduct the alkalinity of water itself from the reported alkalinity and divide what's left by the charge difference on 1 mmol carbo (as calculated by the trivial math) in the sticky you get the mEq of acid required to reach a particular pH and you get a correct number for the bicarbonate irrespective of pH. Balancing the proton deficit of the carbo plus the proton deficits of the base malts against the proton surfeits of added acids... is the robust way to estimate mash pH and it must be done iteratively. But I would be extremely nervous turning that job over to Excel's circular reference algorithm. Microsoft's own instructions warn about this. I'm sure you have tested it thoroughly. I can get close using it but it won't converge to an exact answer no matter how many iterations I allow nor what I set as a threshold. Solver does work fine for this but I can certainly see why you wouldn't want to impose Solver on Joe Homebrewer.

By the way, Bru'n Water works fine on Macs. Its just that Excel for Mac does not work with normal Excel programs.

I can get any Excel program (or Word document) in which I can edit the fonts to run or open on the Mac. You may remember me bellyaching about this when we were editing the Water book. Bru'n is locked so I can't edit the fonts and thus cannot run it. I'm mad enough that I've had to enrichen Gates by buying XP and Windows 10 so I can run a couple of programs I need but am damned if I'll shell out for a Windows copy of office.

I call this a result of the Jobs/Gates feud.

I just found out recently that they were originally quite matey. Gates first product was evidently a board that plugged into one of the early Apples allowing it to run business software. Jobs even tried to get him on the board at one point but the user community was so outraged by that that it was dropped. It wan't till Gates tried to get his ikon based software to market before Apple that they got to feuding.

Fortunately, there are freeware programs such as Open Office for MacOS that do work with normal Excel programs. The other option is to upgrade to the latest version of Office for Mac since I understand that Microsoft has finally agreed to include the proper software support that was lacking.

I'll look into those. I'll also note that they interplayed just fine for a long time. It's only been in the last 5 (?) years that you couldn't open a Windows Excel sheet on Mac (without editing the fonts).

 

[ajdelange]

AJ, I've made the broad assumption that since the typical water supply has a pH in the 6.5 to 8.5 range as recommended by WHO and EPA, most of the alkalinity is in the form of bicarbonate.

That's true but you don't really have to assume that.

I then go on to require that all the alkalinity is converted into its equivalent 100% bicarbonate concentration for the calculations used in the program.

After thinking about this some more I've realized (took long enough) that the error we are both making is in thinking that Bru'n Water's "bicarbonate" is in fact related to bicarbonate ion content. It is actually a proton deficit. It is only peripherally related to actual bicarbonate ion content in a couple of cases and we need to stop thinking it really has anything to do with an ion concentration except in those cases. If we add 1 mmol of sodium bicarbonate (84 mg of NaHCO3 containing 61 mg of HCO3- ion) to DI water and measure the alkalinity we will find the water to have (pHe = 4.5) of 1.0252 mEq/L. For the parts of the industry that don't use mEq/L or mVal/L (or dH or °F...) this would be multiplied by 50 and called 51.26 ppm as CaCO3. Bru'n Water multiples by 61 instead of 50 and calls this alkalinity "61*1.0252 = 62.54 mg bicarbonate". This is pretty close to the amount of bicarbonate ion and thus represents one of the cases where Bru'n bicarbonate relates to an actual ion amount (as long as the pH is allowed to stay at the value it went to (8.34) when the NaHCO3 was added to the water.

An alkalinity in this sense (the sense of what is on a water report) is a proton deficit with respect to pHe. In other contexts it is a proton deficit WRT some other pH, in many cases, mash pH. With respect to a mash pH of 5.5, for example, the proton deficit of 1 mmol (61 mg bicarbonate ion) of added sodium bicarbonate is 0.883 = mEq. In Bru'n Water speak it is "53.9 mg bicarbonate". That's starting to get away from being able to be called 'close' to the amount of bicarbonate added and, is, of course, no where near the actual amount of bicarbonate in a solution from that addition at pH 5.5 (7.1 mg). One added mmol of Ca(OH)2 has, WRT pH 5.5 a proton deficit of "122 mg bicarbonate" even though it contributes no bicarbonate whatsoever and, also with respect to mash pH 5.5, 1 mmol of lactic acid has a proton deficit of -0.978 mEq. In the language of Bru'n water that proton deficit is -59.6 mg bicarbonate (a surfeit) though it contributes lactate rather than bicarbonate ions.

While there may be very minor errors in that methodology, I know that it works well in practice.

Actually there aren't. It should work because keeping track of proton deficits, be they multiplied by 1 (mEq/L), 50 (ppm as CaCO3), 61 (Bru'n Water) or Euler's constant is the way to do these problems and the actual multiplicative constant does not matter. The pH to be estimated is the one for which the sum of the deficits is 0 or a target pH is realized when the sum of the deficits is 0 and the scaling constant can be abything. It sure as hell confuses people when the field is labeled 'ppm bicarbonate' rather than 'proton deficit as bicarbonate' but there is no conceptual error in multiplying by an eccentric constant.

Users just need to remember:
In Bru'n water "ppm bicarbonate" doesn't mean ppm bicarbonate. It means 61 times the proton deficit.

 

[mabrungard]

AJ, your assessment is correct with respect to all those components such as protons and hydroxyl. The bicarb is an stand-in for either surfeits or deficits of protons. However, it does occasionally refer to actual bicarbonate content.

 

[LBussy]

To keep things clicking along for the knuckle-draggers (like me): I mixed up 5 gallons of this and have it under pressure in the kegerator.

I had one aborted try: This will come as no surprise to some of you but the gypsum and/or pickling lime makes a fantastic concrete when you dump it into a moist-bottomed keg. I don't know what I was thinking. That keg is currently soaking with some distilled vinegar and I used a second to get things right. So just in case someone is coming behind me, make sure to suspend the minerals in a cup of your source water before adding to the keg.

Another observation is that measuring 0.015898722 g of KCl is more than likely beyond the immediate skill level of most homebrewers. Now there's ways to do it; creating/using a 1% solution is one such way, however I have a hard time believing something at <1PPM is going to noticeably impact the flavor profile. Did I do it? You bet - if it's not clear I have a little OCD, and a reloading scale that's incredibly accurate. I still should have used a dilute solution, but that did not occur to me till after. I'm not ashamed to admit that.

So as I said it's made and under pressure carbonating in the kegerator. When I get back from Austin next week I'll give it a taste and see. This was not something we covered in the BJCP so it should be interesting.

 

[ajdelange]

AJ, your assessment is correct with respect to all those components such as protons and hydroxyl. The bicarb is an stand-in for either surfeits or deficits of protons. However, it does occasionally refer to actual bicarbonate content.

If you are using it properly, and I have no reason to suppose you are not, then it is not a stand in for surfeits or deficits of protons. It is the surfeit or deficit of protons with respect to some pH (over which the user apparently has no control so I suppose it is the pH you predict for these water components and the grist components) and the only question is as to why you have chosen to scale it in this peculiar fashion. The fact that it sometimes is numerically close to the actual bicarbonate content is related to the fact, as you have noted, that the major alkali in water is the bicarbonate ion and I suppose is the reason you chose it.

 

[ajdelange]

Another observation is that measuring 0.015898722 g of KCl is more than likely beyond the immediate skill level of most homebrewers.

The obvious response is to say "That's in the noise" and ignore it.

Now there's ways to do it; creating/using a 1% solution is one such way, however I have a hard time believing something at <1PPM is going to noticeably impact the flavor profile. Did I do it? You bet - if it's not clear I have a little OCD, and a reloading scale that's incredibly accurate.

It's amazing how many homebrewers also load their own ammo.

I still should have used a dilute solution, but that did not occur to me till after. I'm not ashamed to admit that.

That's the way to do it for sure.

 

[LBussy]

Tried the .. Fauxlegrino? Very good! Also tried it through my brand new Perlick 650 which allowed me to keep the tank pressure up while dispensing at a sane rate. I'd say all in all it was a success. The grocery store was out of Pellegrino or I would have done a side by side but maybe it's better this way.

It *might* be a touch more acidic than I remember, I can't decide.

 

[mabrungard]

Interesting. Just remember that it takes time for the CO2 that you injected into the water to hydrate. You can get CO2 instantly into water via high pressure (ie: Sodastream), but that hydration of CO2 is a chemical process that can't really be hurried. If its been less than 2 weeks under pressure, you may find that the water character changes slightly as that CO2 hydrates into the solution. I have no idea if that will change anything, but this is just a note for consideration.

 

[LBussy]

Thanks Martin. I need to come up with a better carbonation method than "set it and forget it." It would probably work better if I had longer to let them sit and carbonate/mellow. I've been thinking about rigging up a "carbonation keg" with a diffuser stone. Even at such high pressures (30 PSI), carbonated water takes a while since the pressure/target volume relationship is like carbonating ale at 2-5 PSI.

 

[LBussy]

We're well into the keg now. Having gone side by side with Pellegrino I'd say this is spot-on. We've also had time to notice that after all that work it's apparently not what she wanted.

San Pellegrino is a sparkling water more than seltzer so the end result is less fizzy. When you pour you can see much larger bubbles in the head. It ends up "more ale than lager" in the carbonation department. Now I really like it but the wife wants her "club soda" back. So, it's back to 12.5 grams of baking soda in the RO water. Works good, she likes it, heck of a lot easier.

I'll keep this keg aside for ME.

 

[Yooper]

We're well into the keg now. Having gone side by side with Pellegrino I'd say this is spot-on. We've also had time to notice that after all that work it's apparently not what she wanted.

San Pellegrino is a sparkling water more than seltzer so the end result is less fizzy. When you pour you can see much larger bubbles in the head. It ends up "more ale than lager" in the carbonation department. Now I really like it but the wife wants her "club soda" back. So, it's back to 12.5 grams of baking soda in the RO water. Works good, she likes it, heck of a lot easier.

I'll keep this keg aside for ME.

Lee, I think I missed this earlier, but for her club soda, you use the baking soda and RO water (that makes it easier for me so I'm glad it's that simple!), but what is the temperature/psi (ie c02 volume) you find is the most club soda-ish? I think my last attempt was overcarbed as it seemed more acidic than I wanted.

 

[LBussy]

Lee, I think I missed this earlier, but for her club soda, you use the baking soda and RO water (that makes it easier for me so I'm glad it's that simple!), but what is the temperature/psi (ie c02 volume) you find is the most club soda-ish? I think my last attempt was overcarbed as it seemed more acidic than I wanted.

12.9g Baking Soda per 5 gallons (the scientists will hopefully pardon me for the mixed measuring systems), 36° F, 30 PSI. That's 4.6 volumes if my chart is right. Someone told me seltzer is supposed to be 4 volumes so this may be on the high side but SWMBO likes it, and the Perlick 650SS taps make short work of dispensing it.

Just sitting there under pressure takes about 2 weeks, but I'm sure some shaking and such could convince it to carb quicker. That's why I was looking at one of those carbing caps for a corny keg.

 

[Yooper]

12.9g Baking Soda per 5 gallons (the scientists will hopefully pardon me for the mixed measuring systems), 36° F, 30 PSI. That's 4.6 volumes if my chart is right. Someone told me seltzer is supposed to be 4 volumes so this may be on the high side but SWMBO likes it, and the Perlick 650SS taps make short work of dispensing it.

Just sitting there under pressure takes about 2 weeks, but I'm sure some shaking and such could convince it to carb quicker. That's why I was looking at one of those carbing caps for a corny keg.

Thanks! I got into club soda and lime this winter in Texas, when it was so nice (hot and dry) and want to make my own for home, so this is a great place to start!

 

[ajdelange]

12.9g Baking Soda per 5 gallons (the scientists will hopefully pardon me for the mixed measuring systems), 36° F, 30 PSI. That's 4.6 volumes if my chart is right.

I get 4.83 Vols. so your chart and my math aren't too far apart. I also estimate pH at 5.07 and the sodium content at 182 mg/L.

Were you to use half the bicarbonate you'd have, of course, half the sodium but the pH would drop to 4.72. That's about the same as lager beer but I gather that such a low pH would be considered objectionable in a fizzy water?

 

[LBussy]

I get 4.83 Vols. so your chart and my math aren't too far apart. I also estimate pH at 5.07 and the sodium content at 182 mg/L.

Were you to use half the bicarbonate you'd have, of course, half the sodium but the pH would drop to 4.72. That's about the same as lager beer but I gather that such a low pH would be considered objectionable in a fizzy water?

Well here's the fuzzy math I used. Wife likes a no-name club soda we buy at the local grocery store. It shows 95 mg of sodium per 12 oz (354.882ml) serving. That works out to 0.2677 mg/ml [(95 / 354.882)] of sodium.

NaHCO3 has a molar mass 84.0066 g/mol. Sodium is 22.9898 g/mol or 27.3667% of the mol [(22.9898 / 84.0066) * 100]. That works out to: 3.6541 g of NaHCO3 to net 1 g of sodium [(1 / 22.9898%) * 100], or 1 gram of NaHCO3 contributes 0.2737 g sodium [(1 * 27.3667%) / 100]

To get the desired 0.2677 mg/ml of sodium in solution one needs 0.9782 mg/ml [(0.2677 mg/ml / 27.3667%) * 100] NaHCO3

There are 3785.41 ml in a gallon (3.8 liters). To get the desired 0.2677 mg/ml concentration of sodium in a gallon, one needs 2575.971505 mg [0.6805 * 3785.41] NaHCO3 per gallon (12.9g/5 gallons).

It is entirely possibly my math is wrong too - if so I still ended up with something the wife likes.

So ... my thinking was the sodium level went to the taste and the bicarb allowed it to "hold" the carbonation. That was all till I learned a little more about the water chemistry.

 

[ajdelange]

Well here's the fuzzy math I used. Wife likes a no-name club soda we buy at the local grocery store. It shows 95 mg of sodium per 12 oz (354.882ml) serving. That works out to 0.2677 mg/ml [(95 / 354.882)] of sodium.

(95/12)[mg/oz]*128[oz/gal]*(1/3.78541)[gal/L] = 267.694 mg/L so that checks

NaHCO3 has a molar mass 84.0066 g/mol. Sodium is 22.9898 g/mol or 27.3667% of the mol [(22.9898 / 84.0066) * 100]. That works out to: 3.6541 g of NaHCO3 to net 1 g of sodium [(1 / 22.9898%) * 100], or 1 gram of NaHCO3 contributes 0.2737 g sodium [(1 * 27.3667%) / 100]



To get the desired 0.2677 mg/ml of sodium in solution one needs 0.9782 mg/ml [(0.2677 mg/ml / 27.3667%) * 100] NaHCO3

267.694[mg Na/L]*(1/22.99)[mmol Na/mg]*84.006[mg/mmol NaHCO3] = 978.16 mg/L NaHCO3 so that checks.

There are 3785.41 ml in a gallon (3.8 liters). To get the desired 0.2677 mg/ml concentration of sodium in a gallon, one needs 2575.971505 mg [0.6805 * 3785.41] NaHCO3 per gallon (12.9g/5 gallons).

The problem seems to be in here.
978.16[mg/L NaHCO3]*3.78541[L/gal] = 3702.74 mg/gal or for 5 gal 18513.7 mg (18.5137 g).

Or looked at slightly differently
(12900/5)[mg/gal]*(1/84.01)[mmol NaHCO3 /mg]*23[mg/mmol Na]*(12/128)[(oz/Serving)/(gal/oz) = (gal/Serving)] = 66.22 mg/Serving


The other thing to think about is that there may have been an additional source of sodium i.e. sodium chloride or sodium sulfate in the water before the CO2 was added.

So ... my thinking was the sodium level went to the taste and the bicarb allowed it to "hold" the carbonation. That was all till I learned a little more about the water chemistry.

That's not all that ridiculous an assumption if you want to add 'at a given pH' to the sentence. For a given level of pH you will need more bicarb to permit a higher level of dissolved CO2.

 

[LBussy]

The problem seems to be in here.
978.16[mg/L NaHCO3]*3.78541[L/gal] = 3702.74 mg/gal or for 5 gal 18513.7 mg (18.5137 g).

The other thing to think about is that there may have been an additional source of sodium i.e. sodium chloride or sodium sulfate in the water before the CO2 was added.

I always go sideways somewhere in a long calculation like that. So I ended up a little light on the sodium, interesting. I'll try the 3702.74 mg/gal rate in the next batch and see what she says.

Sure there could have been other sources of sodium. Without having any other information, I just took a wild-@$$ stab at it and she liked it.