Big Dark Malt PH Issue

[Mexibilly]

I'm glad that worked out for you. It will be interesting to see how close your prediction hits. Are you using a good pH meter?

As for your thanks, I do appreciate it. I consider this just paying it forward like Matt Crispen did with me. So you're it

I'm in Connecticut, so probably not a drive-by for you But I'd love to sample the results if you're up for shipping!

I've used the environmental technician's meter before, including my last brew, and I'm afraid it goes through enough abuse to render it questionable.
That said, I'll either use that meter and calibrate it to 4 and 7, or figure something else out by next weekend when I hope to brew this.
PM me your address at some point in the next 6 months and I'll shoot you some samples.

 

[ajdelange]

...add 0.50 mL/gallon of Lactic Acid. That brings your pH to 5.5.That seems like a lot of Lactic to me so I'd be interested to hear what others think of this. This amount of Lactic may adversely affect the flavor.

I tweak Baking Soda and Calcium Chloride to bring your numbers into the "close enough for TV" range. This gives you a pH of 5.3. I would call that good but again, would love to hear opinions of others on that adjustment strategy.

The problem here is actually with the profile you are all trying to hit. I used to yell a lot on here about how you can't duplicate a profile that is not electrically balanced and eventually the spread sheet makers started putting in electrical balance checks and also adding, in this case, apparently, bicarbonate, to make their profiles balance. This is a good thing, of course, but not quite sufficient as if a brewer is expected to be able to synthesize the profile he needs to be able to do it with available salts. The Black Malty profile can't be assembled from the salts available on the Water Additions Sheet (at least I can't do it). Starting with OP's water we see that his Mg is 33 and the target is 5 and that his calcium is 113 while the target is 60. Clearly we are going to need some dilution to match this profile. Recall that I said in an earlier post that we want to match at mash pH at which there is essentially no bicarbonate so we can ignore the bicarbonate requirement. Doing that and asking how much of each of the salts available on the Water Additions Sheet and how much dilution water should we add we find that the best we can do is pretty good (the largest error is -0.33% on calcium) if we use 5.58 L of DI dilution water with each liter of the tap water. That's enough to dilute the magnesium down and also take a big chunk out of the alkalinity. The catch is that we'd need 319 mg of lactic acid per liter of the blend and that amounts to 1.17 mL of 88% acid per gallon. That aside the notion that we are going to need 5.6 L of DI water to dilute suggests that we might as well go whole hog and use 100% DI water. Doing that we can, of course, better see what the problem with the profile itself it. Just using the salts we can't do very well at all and looking at the profile it is clear why. It want's more calcium and sodium than the available salts can provide without exceeding the sulfate and chloride limits. We need calcium and sodium salts that where the metals aren't paired with chloride or sulfate. What can they be paired with? It has to be anion which is, ostensibly, a "don't care" ion. Lactate is what we used in the first synthesis and we can do that here too by adding calcium and sodium lactate which we do, in effect, by adding calcium hydroxide and sodium bicarbonate (on the available list) and neutralizing them with lactic acid to pH 5.3. Doing this we can hit all the ion specifications (except bicarbonate - if anyone cares, and no one should, it is 2.2 mg/L) to 0.0001% or better. We require more lactic acid, in this case: 1.78 mL/gal because we don't have any of the real water to dilute the unreal target. Of course phosphoric acid could be used if it was thought that the lactic was above flavor threshold or a combination of lactic and phosphoric acids or indeed any other safe, obtainable acid whose anion is indeed a "don't care".

I haven't checked any of the other profiles to see if they suffer from this problem but if the philosophy was to just specify what seems reasonable for a particular style and then add bicarbonate to balance I expect at least some would.

 

[ajdelange]

Massively edited:

Further thinking on the profile question: Given that one cannot duplicate the Black Malty profile should it not be replaced with something that one can duplicate? I'd say so but what should it be replaced with? Clearly there was some reason for picking the ion concentrations that were picked (and I assume that bicarbonate was then added to bring about balance) so that it would seem reasonable that the replacement profile should have all the ion concentrations as close to the current ones as possible given that they can be realized with the salts available. Bicarbonate will have to go where it wants to go as sodium bicarbonate is the only source of sodium other than NaCl and using even enough of magnesium chloride and sulfate to not quite reach the magnesium requirement busts both chloride and sulfate. Again, because of the limitations on sulfate and chloride we have to get calcium from lime. In both cases there are, of course, have implications with respect to the alkalinity of the synthesized water.

The following synthesis is based on ignoring the bicarbonate and trying to get the other ions aligned as best we can. Using this approach we can, in fact, get a perfect match to all the other ions but the pH is would be 12.75 (so high that the added lime is only 1/4 dissociated) and the alkalinity 1965! In the synthesis we have limited the alkalinity to 100 and the pH wound up at 10.81

Salt mg/L Synth
CaCl2.0H2O 58.57
NaCl 0.00
MgCl2.6H2O 22.35
CaSO4.2H20 39.56
MgSO4.7H20 21.76
Liters/Liter 0.00
CaCO3 0.00
NaHCO3 74.01
CO2 0.00
HCl 0.00
Ca(OH)2 25.27
Na2CO3.H2O 0.00
Sodium Phosphate 0.00
Potassium Phosphate 0.00
Phosphoric 0.00
Sulfuric 0.00


Weights Errors, % Errors, mg/L Target Realized
1 -26.6200% -15.97 Calcium 60 44.0280
1 -3.6579% -0.18 Magnesium 5 4.8171
0 -66.2733% -1.73 mmol Carbo 2.61200 0.8809
0 -66.2733% -28.31 Bicarbonate 42.71 14.4055
1 5.3674% 1.56 Sulfate 29 30.5565
1 10.2814% 4.22 Chloride 41.00 45.2154
0 0.0000% 0.00 Nitrate 0 0.0000
0 0.0000% 0.00 Nitrite 0 0.0000
1 1.2641% 0.25 Sodium 20.0000 20.2528
0 0.0000% 0.00 Potassium 0.00 0.0000
Wt'd RMSE Wt'd RMSE,% RMSE, mg/L
0.06431653 13.1005% 9.1133 Target pH 10.8121
Wts ≠ 0 RMSE, (Wt ≠ 0) RMSE, (Wt ≠ 0)
5 13.1005% 7.4215
Alk, as CaCO3 Max (Wt ≠ 0) %
100.00 26.6200%

If we allow the alkalinity to rise as high as 200 the pH becomes 11.51 but the peak error, in calcium again, goes down to 16% in magnitude (50.3 mg/L realized out of a desired 60). The salt amounts are similar but as you might expect the amounts of NaHCO3 and Ca(OH)2 both go up. This is, as you might expect, to push the calcium level up but here are the error data on this synthesis:

Weights Errors, % Errors, mg/L Target Realized
1 -16.1063% -9.66 Calcium 60 50.3362
1 -2.2132% -0.11 Magnesium 5 4.8893
0 -65.2151% -1.70 mmol Carbo 2.61200 0.9086
0 -65.2151% -7.10 Bicarbonate 10.89 3.7868
1 3.2476% 0.94 Sulfate 29 29.9418
1 6.2208% 2.55 Chloride 41.00 43.5505
0 0.0000% 0.00 Nitrate 0 0.0000
0 0.0000% 0.00 Nitrite 0 0.0000
1 4.4413% 0.89 Sodium 20.0000 20.8883
0 0.0000% 0.00 Potassium 0.00 0.0000
0 0.0000% 0.00 Fe(II) 0 0.0000
0 0.0000% 0.00 Fe(III) 0 0.0000
0 0.0000% 0.00 Ammon.
Wt'd RMSE Wt'd RMSE,% RMSE, mg/L
0.037808513 8.1643% 3.4517 Target pH 11.5105
Wts ≠ 0 RMSE, (Wt ≠ 0) RMSE, (Wt ≠ 0)
5 8.1643% 4.5074
Alk, as CaCO3 Max (Wt ≠ 0) %
200.00 16.1063%

The sodium is now 4.4% over whereas in the first synthesis it was only 1.3% over. What is happening here is that the bicarbonate is now acting as an acid supplying protons to neutralize hydroxyl ions from lime allowing us to get more calcium that way.

We certainly don't want a synthesis that comes out with alkalinity of 100 to 200 as we will just have to supply acid to neutralize that acidity in order to get this water to mash pH. It makes more sense to add the acid as part of the synthesis and let that acid neutralize the lime. In this next example we synthesize to pH 5.4, which we take as a reasonable mash pH, using lactic acid:

CaCl2.0H2O 33.15
NaCl 17.69
MgCl2.6H2O 26.06
CaSO4.2H20 38.62
MgSO4.7H20 19.11
Liters/Liter 0.00
CaCO3 0.00
NaHCO3 47.65
CO2 0.00
HCl 0.00
Ca(OH)2 72.17
Na2CO3.H2O 0.00
Sodium Lactate 0.00
Potassium Lactate 0.00
Lactic 228.49 mg/l (0.83 mL 88% acid per gal)
Sulfuric 0.00

The ion match is essentially perfect:

Weights Errors, % Errors, mg/L Target Realized
1 -0.0001% 0.00 Calcium 60 60.0000
1 0.0000% 0.00 Magnesium 5 5.0000
0 -78.2849% -2.04 mmol Carbo 2.61200 0.5672
0 -78.2849% -11.79 Bicarbonate 15.06 3.2696
1 0.0000% 0.00 Sulfate 29 29.0000
1 0.0000% 0.00 Chloride 41.00 41.0000
0 0.0000% 0.00 Nitrate 0 0.0000
0 0.0000% 0.00 Nitrite 0 0.0000
1 0.0000% 0.00 Sodium 20.0000 20.0000
0 0.0000% 0.00 Potassium 0.00 0.0000
0 0.0000% 0.00 Fe(II) 0 0.0000
0 0.0000% 0.00 Fe(III) 0 0.0000
0 0.0000% 0.00 Ammon.
Wt'd RMSE Wt'd RMSE,% RMSE, mg/L
1.19049E-07 0.0000% 3.3180 Target pH 5.4000
Wts ≠ 0 RMSE, (Wt ≠ 0) RMSE, (Wt ≠ 0)
5 0.0000% 0.0000
Alk, as CaCO3 Max (Wt ≠ 0) %
4.18 0.0001%

The concern here is with the lactic acid required to make the synthesis:
228.49 mg/l (0.83 mL 88% acid per gal). Someone else here was concerned about 0.5 mL/gal and this is over that. Now it is possible here that an 80/ grist might have a proton surfeit at pH 5.4 which surfeit can be subtracted directly from the acid required for the water.

All this is very interesting (to some) but does not answer the question as to how to fix the Water Profile Adjustment Page. The water profile under study, Black Malty, was apparently put together choosing a set of desired ion concentrations and then adding bicarbonate to balance at pH 8. That makes it balanced at pH 8 but that doesn't mean we can synthesize it at pH 8 as we have seen here. Trying to force a solution at pH 8 without acid gives a poor result:
Weights Errors, % Errors, mg/L Target Realized
1 -55.1780% -33.11 Calcium 60 26.8932
1 -7.5822% -0.38 Magnesium 5 4.6209
0 -88.2266% -2.30 mmol Carbo 2.61200 0.3075
0 -88.2266% -137.82 Bicarbonate 156.21 18.3915
1 11.1250% 3.23 Sulfate 29 32.2263
1 21.3119% 8.74 Chloride 41.00 49.7379
0 0.0000% 0.00 Nitrate 0 0.0000
0 0.0000% 0.00 Nitrite 0 0.0000
1 -16.0318% -3.21 Sodium 20.0000 16.7936
0 0.0000% 0.00 Potassium 0.00 0.0000
0 0.0000% 0.00 Fe(II) 0 0.0000
0 0.0000% 0.00 Fe(III) 0 0.0000
0 0.0000% 0.00 Ammon.
Wt'd RMSE Wt'd RMSE,% RMSE, mg/L
0.165848327 28.0610% 39.4122 Target pH 8.3000
Wts ≠ 0 RMSE, (Wt ≠ 0) RMSE, (Wt ≠ 0)
5 28.0610% 15.4483
Alk, as CaCO3 Max (Wt ≠ 0) %
17.22 55.1780%

as we can't use Ca(OH)2. We had suggested in the original version of this post that this poorly fitting profile be used instead of the given profile because we can synthesize that but this seems, within the perspective of this edited version, a foolish suggestion. The simplest fix is doubtless to add another column to the table in which the amount of acid required to achieve the desired synthesis is stated. It could easily replace the bicarbonate column as that contains replicate information given that alkalinity and pH are known. I am assuming that pH is 8 for all the profiles but this should be clearly stated in big letters somewhere on the page.

ClaudiusB: hope you still like it!

 

[Mexibilly]

I truly appreciate your hard work in running these numbers.
The Black and Malty profile doesn't represent my chemistry goal, it was though a place to start.
I did dilute with RO and adjust salts to achieve a profile, including pH, that satisfies what I hope to accomplish with this first attempt at a big, complex stout. I don't have my Bru'n Water profile available to share, but I'll trust it this time and base future dark grain bills on the experience.
That said, I also borrowed another HBT stout recipe, https://www.homebrewtalk.com/showthread.php?t=238807
This is less complex and I'm betting much easier to build a water profile for.
This might be a better place to start as I work to learn water chemistry as it applies to dark grain bills.
SWMBO and I are on a low carb diet which cuts my normal beer intake hugely = Miller 64
So I'll have plenty to share along the way...

 

[ajdelange]

I truly appreciate your hard work in running these numbers.

Thank you but this coming along has been very timely. I've just done a major reorganization of the spreadsheet I use to solve problems like this and was itching for a good test case. This was it. If it was some help to you that's frosting on the cake!

 

[philipCT]

One of the easiest ways to adjust mash pH upward is to simply mash thinner. Super easy adjustment in the system. Just up the mash volume. A useful tool for dark beers for sure. 1.25 is not a problem but is not necessarily the best for a dark beer if pH issues are being considered.

With 12 gallons entered as sparge volume the spreadsheet assumes all that volume is being used so will give you the final water profile accordingly. You can of course enter a different profile for the sparge water if you are not treating it the same way but the software doesn't know the exact sparge amount unless you tell it. This will impact the final water profile it spits out.

Don't get me wrong, I think you have gone to great lengths to provide excellent help in the thread. I'm not trying to shoot you down at all. Just wanted to stick my oar in, so to speak. No disrespect intended. #waternerdsmatter

Okay, no worries because I totally learned something...

I guess I should have realized this earlier but that thing about mash water volume affecting the pH. Duh! That had never occurred to me. I will totally use that in the future.

I've messed with different values in the sparge and I think what I'm doing is fine because I'm correcting the entire volume of mash water. So even if I only use half of it, the chemistry is correct. Let me know if I'm wrong about that.