Best methods of using HCL and H2S04

[bitteritdown]

I've done this in the past and have made good beer, starting with deionized water:

1.) Add Calcium Hydroxide and/or Sodium Bicarbonate to strike water to achieve Calcium and/or Sodium ion levels.
2.) Add HCL and/or H2S04 to strike water to achieve Chloride and/or Sulfate levels.
3.) Heat to strike temperature
4.) Mash In

I haven't noticed any precipitation of salts in the strike water (no sparge) or adverse side effects.

Are there any gotcha's or better methods of using these acids/salts - Ca(OH)2, NaHCO3, HCL and H2S04 without bringing other acids or salts into the equation?

 

[ajdelange]

If you add 1 mmol of sodium bicarbonate to a volume of water and then add 1 mEq of HCl you would lose 1 mmol of CO2 and wind up with 1 mEq each of sodium and chloride ions. Most consider it appreciably simpler to add 1 mmol of deiodized table salt.

If you add 1 mmol of slaked lime, Ca(OH)2 to a volume of water and then add 1 mmol of sulfuric acid you will wind up with 2 mEq of calcium ions and 2 mEq of sulfate ions (plus an extra mmol of water). Most people consider it appreciably simpler to add 1 mmol of gypsum (CaSO4).

If you add 1 mmol of slaked lime, Ca(OH)2 to a volume of water and then add 1 mmol of hydrochloric acid you will wind up with 2 mEq of calcium ions and 2 mEq of chloride ions (plus an extra mmol of water). Most people consider it appreciably simpler to add 1 mmol of calcium chloride (CaCl2).

 

[bitteritdown]

Agreed, but what if one desires to add high levels of Chloride or Sulfate with low to no calcium or magnesium?

 

[ajdelange]

Then he'd have to go with sodium or potassium those being the only other cations I think I'd want in my beer and I'm not so sure about potassium.

It seems you are unaware that for each equivalent of sulfate or chloride their must be a matching equivalent of a cation. Sodium, calcium and mangesium are the most common with small amounts (in most cases) of potassium and traces (anything more than a trace is in most cases a flavor spoiler and, in some cases, poisonous) of strontium, copper, iron, aluminum, manganese etc.

 

[bitteritdown]

What you're trying to say is that the excess HCL and H2S04 ions in the strike water (those that don't have any calcium, etc... ions to react with) simply hang out in solution until dough in and when the malt releases it's ions to the solution the HCL and H2S04 react with the calcium, etc... from the malt?

 

[ajdelange]

Not quite. The acids do not react with the calcium. They react with bicarbonate if there is any.

HCl + NaHCO3- ---> H+ + Cl- + Na+ + HCO3- --> H2O + CO2 + Na+ + Cl-

What I am saying (or trying to say) is that mash is electrically neutral. If you add acid (e.g. HCl) to pure water you will have a mixture of acid molecules, hydrogen ions and chloride ions. The relative proportions depend on the pH of the solution. Since HCl is a 'strong' acid all the acid molecules dissociate and you have very little HCl. It has virtually all converted to H+ and Cl- ions.

Now if you add malt it contains compounds that accept protons (H+ ions) and you wind up with a mix of protonated malt compounds, H+ ions (not all protons are absorbed) and chloride ions. The relative proportions depend on the pH. If you add x moles of HCl to y moles of base at a particular pH z moles of base will be protonated:

xH+ + xCl- + yBase --> (x-z)H+ + xCl- + zHBase+ + (y-z)Base

 

[cire]

Just as an aside, a typical beer contains 500mg/l potassium, Bud was said to have 330ppm, such that further small additions usually have virtually no impact on flavor and less than does an equivalent amount of sodium.
Any with concern for ingesting potassium should avoid bananas which usually contain >3500ppm.

 

[ajdelange]

Just as an aside, a typical beer contains 500mg/l potassium,

That's because plant material, in this case barley, contains a lot of potassium to the point that our grandmothers could extract enough KOH to make soap with it from ashes.

Bud was said to have 330ppm, such that further small additions usually have virtually no impact on flavor and less than does an equivalent amount of sodium.

Well that's the paradox. Apparently relatively small additions do make a flavor difference to the point that the literature seems to generally agree that additions, if any, should be small. I don't recall the recommendations so I'll Wag 20 - 30 mg/L. Now, of course, this could be one of those GABNT (Generally accepted but not true) things of which the home brewing community cherishes so many yet, were it not true, it would be clear that we are overlooking a great source of chloride found on the shelves of every super market i.e. this salt substitutes which are just KCl.

Any with concern for ingesting potassium should avoid bananas which usually contain >3500ppm.

My comment was based on flavor concerns, not fear of hyperkalemia. In fact my doctor has prescribed a potassium supplement for me (we don't want hypokalemia either). Interestingly enough the prescription is for tablets of 20 mEq - it seems even the medics are catching on. Also interestingly enough the co-pay for a bottle of these is $8. So how much is the insurance being hit for? Much cheaper to buy a shakerfull of the salt substitute. Conveniently enough the formula weight of KCl is 75 so it's trivial to figure how much it takes to make up 20 mEq of K. But, as I use the salt substitute rather than the prescription I can attest that KCl doesn't taste very good relative to NaCl.

I also eat bananas. If 3500 mg/kg is correct a 100 gram banana would contain 350 mg grams which is 8.9 mEq - half a tablet's wort.

I'll also comment that barley contains lots of magnesium to the point that the same argument that a few mg/L more from the water shouldn't make much if any difference but if the admonitions to keep potassium additions small are strong those to avoid excess magnesium are even stronger. I don't have an explanation in either case. I might mumble something about the plant Mg and K being bound whereas clearly ions from MgSO4 and KCl are free.

Anyway, it is clear OP wants large amounts of sulfate and chloride sans calcium or magnesium. I'm assuming this means as much as 8 mEq/L. That would mean as much as 8 mEq of sodium or potassium if he used those salts amounting to 184 mg/L Na or 312 of K. Way too much IMO. Of course 8 mEq/L Cl- or SOF-- is way to much even with calcium. But de gustibus non est disputandem.

If you do use potassium, try to get it from Kazakstan.

 

[bitteritdown]

According to my copy of "Malts and Malting" - D. Briggs... pg. 190 an analysis of the ash of a certain malt (or maybe just the unmalted grain) contained .46% potassium, .24% phosphate, .14% magnesium, .037% calcium, etc... but on the following page a different analysis (apparently) the malt comprised .36% potassium, .40% phosphate, .13% magnesium, .13% calcium... all of which varies according to variety, soil and climate.

There should be enough calcium, magnesium, potassium, etc... from the right malt. Key word... "right". Interestingly enough the malt supplied 27ppm of zinc.

I'm simply adding enough HCL to get the chloride to 150-170ppm and Ca(OH)2 to get around 10-20ppm calcium and then enough NaHCO3 to get to estimated mash pH.

What's more interesting is that we drink these mixtures of ions and our brains/perceptions tell us they taste good even though we're comprised of some of the same. Think about that for a while. Maybe I should review my copy of "What is life?" Erwin Schrödinger. All of this is neither here nor there.

 

[ajdelange]

I'm simply adding enough HCL to get the chloride to 150-170ppm

That's (for 170) 4.85 mmol/L

and Ca(OH)2 to get around 10-20ppm calcium

For 20 that's 1 mmol/L which yields 2 mEq/L (OH)- which is enough to neutralize 2 mEq/L of the H+ from the HCl.

and then enough NaHCO3 to get to estimated mash pH.

That would depending on the net proton deficit of the malts. Assuming that to be 0 (to make the calculation simple) i.e. a stout or porter or something else dark, you would need approximately 2.8 mmol/L sodium bicarbonate yielding approximately 2.8 mmol/L (64 mg/L) sodium. With all that chloride I would think the result would taste a bit salty but perhaps that is what is sought (most people seem to like to keep chloride at less than 100).

As noted in #2, most people would add CaCl2 and NaCl2 and not be bothered with the HCl and NaHCO3. FCC grade HCl is hard for most home brewers to obtain. It is, however, recognized that if you need acid to overcome grain alkalinity and would, at the same time, like to have more chloride that HCl can take care of both of those desires. Those in the UK have ready access to CRS. Some in the US ignore the fact that they should be using FCC and use other grades of H2SO4 and HCl - even stuff bought at the hardware store I suspect.

What's more interesting is that we drink these mixtures of ions and our brains/perceptions tell us they taste good even though we're comprised of some of the same.

We also eat meat.

 

[Gadjobrinus]

FCC grade HCl is hard for most home brewers to obtain.

Just an FYI, this is what I'm using. Seller affirms its food grade use.

With all that chloride I would think the result would taste a bit salty but perhaps that is what is sought (most people seem to like to keep chloride at less than 100

AJ, this was certainly my presumption until a couple of days ago, due to my conversation with Cire on your Primer thread. But then, I don't know the chemical breakdown of the British ales I admire and love. What do you think of the Murphy & Sons material - taking the ordinary bitter category alone, a (surprising, again, to me) Ca of 180-220, and Cl of 150-300? (the others fall within prior understanding, at least for me).

Those in the UK have ready access to CRS.

The only complaint I've read among British brewers is that CRS locks HCL and sulfuric in at a fixed ratio. HCL was hard to find but finding food grade sulfuric has been nigh impossible. It sure would be nice to make up a "custom" CRS.

 

[bitteritdown]

As noted in #2, most people would add CaCl2 and NaCl2 and not be bothered with the HCl and NaHCO3.

I don't know that Ca < 20ppm and Na < 50ppm with Cl >150ppm can be hit with only CaCl2 and NaCl2.

 

[ajdelange]

Just an FYI, this is what I'm using. Seller affirms its food grade use.

It says it meets ACS, FFC (which I assume is a typo for FCC) and USP/NF specs. Being the cynic that long time on earth has made me I note that it does not claim to be ACS, FCC or USP/NF grade. Thus, I suppose, if you were to use it in a food product you were selling it would probably be a violation. Note that approval for use in foods has as much to do with packaging in a facility approved for processing of foods as it does with the purity.

 

[ajdelange]

I don't know that Ca < 20ppm and Na < 50ppm with Cl >150ppm can be hit with only CaCl2 and NaCl2.

No, it can't nor can it be realized any other way

20/20 + 50/23 -150/35.43 = -1.06. Thus you must have 1.06 ppm of some other cation such as magnesium or potassium.

 

[bitteritdown]

Right, the question is - is the malt sufficient to provide these extra cations?

 

[bitteritdown]

I'd recommend using FCC grade, which is expensive, not to mention shipping:

https://www.spectrumchemical.com/OA_HTML/chemical-products_Hydrochloric-Acid-37-Percent-FCC_HY106.jsp?minisite=10020&respid=22372&phrase=food grade hydrochloric acid

https://www.spectrumchemical.com/OA_HTML/chemical-products_Sulfuric-Acid-FCC_S1736.jsp?minisite=10020&respid=22372&phrase=food grade sulfuric acid

Of course, there other manufacturers but the minimum purchase quantity may be prohibitive (unless you don't mind a gallon of HCL sitting around)...

http://detrexchemicals.com/food/

 

[ajdelange]

Right, the question is - is the malt sufficient to provide these extra cations?

The answer is "no". Malt doesn't have any 'extra' cations. As in any other substance the cations are equivalent (in the chemical sense) to the number of anions. Malt like everything else (except things that have been charged) is electrically neutral.

You cannot synthesize an arbitrary ion profile. It must be electrically balanced because everything you put into it (acids, bases, salts, water) are. If you compute the electrical charge of your desired profile and it is not 0 then you cannot synthesize it because it cannot exist.

Also note that Spectrum will not knowingly sell to an individual. There are ways around this but they are all at least a little shady and these days, probably illegal too.

 

[Gadjobrinus]

It says it meets ACS, FFC (which I assume is a typo for FCC) and USP/NF specs. Being the cynic that long time on earth has made me I note that it does not claim to be ACS, FCC or USP/NF grade. Thus, I suppose, if you were to use it in a food product you were selling it would probably be a violation. Note that approval for use in foods has as much to do with packaging in a facility approved for processing of foods as it does with the purity.

I'm bummed, and as always perhaps it's my naivete as to the native drives of man, but I'm a bit confused. I completely understand the cynicism. I can't see it on the label (of course), but the Amazon description indicates it meets USP/NF specs. Is there a way based on what I see, to research it's compliance (or not)? In my ideal world, it would just be to try some alchemy of CRS, and see what I obtain in the mash, all the way to the finished beer. And I pine after some idea that's possible in our country.

 

[ajdelange]

I wouldn't be too bummed. If it meets the specs then it is as good as labeled FCC in terms of purity but you can't be assured that it was bottled in a machine that never processed peanuts.

 

[bitteritdown]

The answer is "no". Malt doesn't have any 'extra' cations. As in any other substance the cations are equivalent (in the chemical sense) to the number of anions. Malt like everything else (except things that have been charged) is electrically neutral.

You cannot synthesize an arbitrary ion profile. It must be electrically balanced because everything you put into it (acids, bases, salts, water) are. If you compute the electrical charge of your desired profile and it is not 0 then you cannot synthesize it because it cannot exist.

Also note that Spectrum will not knowingly sell to an individual. There are ways around this but they are all at least a little shady and these days, probably illegal too.

So what happens when unbalanced additions are made, how does the system balance itself or does it remain in a state of imbalance?

40ppm Ca, 50ppm Na, 150ppm Cl should balance.

Re: Spectrum... You may be able to order through your employer, depending on where you work. I wouldn't hesitate to use the stuff from Amazon though.

 

[ajdelange]

So what happens when unbalanced additions are made, how does the system balance itself or does it remain in a state of imbalance?

You can't make an unbalanced addition. Under anything other than extraordinary circumstances everything is balanced. CaCl2 is balanced (Ca++ + 2Cl-). NaH2PO4 is balanced (Na+ + H2PO4-). CaSO4 is balanced (Ca++ + SO4--).

40ppm Ca, 50ppm Na, 150ppm Cl should balance.

Almost. 40.6/50.5/149.7 does and is conveniently synthesized by adding 112.4 mg CaCl2.0H2O and 128.4 mg NaCl to 1 L of water.

If you want to do this with acid, lime and bicarbonate then how close you can come depends on the target pH. For pH 5.5 you can get
36.69/43.26/151.87 by adding 158.08 mg/L NaHCO3 mg/L 156.18 HCl and 67.83 mg/L CaOH2.

Thus you can get closer to what you want with the salts and there is minimal pH dependence as these are neutral salts.

Re: Spectrum... You may be able to order through your employer, depending on where you work. I wouldn't hesitate to use the stuff from Amazon though.

That's what I used to do when the company was tiny. They were OK with it.

 

[bitteritdown]

You can't make an unbalanced addition. Under anything other than extraordinary circumstances everything is balanced. CaCl2 is balanced (Ca++ + 2Cl-). NaH2PO4 is balanced (Na+ + H2PO4-). CaSO4 is balanced (Ca++ + SO4--).

Almost. 40.6/50.5/149.7 does and is conveniently synthesized by adding 112.4 mg CaCl2.0H2O and 128.4 mg NaCl to 1 L of water.

If you want to do this with acid, lime and bicarbonate then how close you can come depends on the target pH. For pH 5.5 you can get
36.69/43.26/151.87 by adding 158.08 mg/L NaHCO3 mg/L 156.18 HCl and 67.83 mg/L CaOH2.

4ppm Ca, 50ppm Na, 150ppm Cl is unbalanced - 2.4 cations - 4.2 anions - yet I can still take deionized water and make the additions to the strike water that the spreadsheet tells me to make, to hit those numbers, even if it's unbalanced.... (balanced would be ~84ppm Cl)... I could then mash in...

But what is actually happening in the strike water and the mash when these ions are added in such disproportion?

 

[ajdelange]

4ppm Ca, 50ppm Na, 150ppm Cl is unbalanced - 2.4 cations - 4.2 anions - yet I can still take deionized water and make the additions to the strike water that the spreadsheet tells me to make, to hit those numbers, even if it's unbalanced.... (balanced would be ~84ppm Cl)...

No, you can't. If the spreadsheet tells you that you can, get another spreadsheet as there is a serious problem with the one you are using.

Tell us what additions your spreadsheet calls for to get this ion profile and we'll see what we can figure out from there. I have a suspicion as to what is going on but I'll reserve comment on it until I see your addition data.

But what is actually happening in the strike water and the mash when these ions are added in such disproportion?

As this can't happen there is no answer to this question.

 

[bitteritdown]

Profile: 4ppm Ca, 50ppm Na, 150ppm Cl

8 gallons of strike water: 3.9ml 88% HCL, 0.2g Ca(OH)2, 5.5g NaHCO3

Grain Bill: 9lbs 1.8L

Resulting mash pH = 5.4pH

If one adds these amounts, 3.9ml - 88% HCL, 0.2g - Ca(OH)2, 5.5g - NaHCO3, to 8 gallons of strike water, what exactly does one get?

 

[ajdelange]

Profile: 4ppm Ca, 50ppm Na, 150ppm Cl

We'll start by reiterating for perhaps the 4th or 5th time that this is not a valid profile as stated. For it to be valid there would have to be 1.7 mEq/L of some cation that is not listed in this profile. Thus in trying to synthesize this profile you are chasing a chimera.

8 gallons of strike water: 3.9ml 88% HCL,

I'm afraid I can't go beyond this point as 88% HCl is not available. 23 Be' is about as strong as you can get and that's 38%. Is this a typo for 38%? I don't want to waste my time assuming that is the case if it's not so I'll wait for confimation before proceeding.

 

[bitteritdown]

You are correct that it is not a valid water profile - it has an imbalance of cations/anions, however, due to the artificial nature of software one can enter such non-sense and be told that if one adds - 10.7ml - 37% HCL, 0.2g - Ca(OH)2, 5.5g - NaHCO3 to the strike water and doughs in that a mash pH of 5.4 will be hit and you'll wind up with that water profile.

Obviously this cannot be true and the question is what actually happens when one adds these recommendations to the strike water and then doughs in?

 

[ajdelange]

If you will tell me what strength HCl you propose to use (there is no such thing as 88% that you can buy) I will tell you what happens. As I have no idea what the actual properties of the malt you propose to use are I will have to make some assumptions about that i.e. use the properties of a typical pale base malt.

 

[bitteritdown]

The HCl is a 37% solution.

 

[ajdelange]

37% HCl is 12N so 10.7 mL of that contributes 12*10.7 = 128.4 mEq of protons at any mash pH as it is a strong acid. These are balanced by 128.4 mEq of Cl- ions which is 128.4*35.46 = 4553.06 mg for a concentration of 128.4*35.46/30.28 = 150 mg/L - what you wanted.

The 0.2 grams of lime is 2.7 mmol producing 5.4 mEq of Calcium which is 20*5.4 = 108 mg for 108/30.28 = 3.6 mg/L. Close to what you wanted. It also yields 5.4 mEq of hydroxyl ion balancing the Ca ions and contributing 5.4 mEq to the mash proton deficit.

The 5.5 grams of sodium bicarbonate is 65.47 mmol resulting in 65.47 mEq of sodium for 65.47*23/30.28 = 49.7 mg/L - also close to what you want. It also yields 65.47 mEq of negative bicarbonate balancing the sodium and contributing about 63 mEq to the mash proton deficit.

For the malt I picked Weyermanns pneumatic pilsner malt as it is pretty pale (3.3 EBC) which is about 1.65 L. Nine pounds of it will impose an additional proton deficit of about 60 mEq/L at mash pH. The actual deficit depends on the mash pH.

When all this stuff is mixed the mash settles at the pH where the proton surfeit from the acid and the tiny contribution from the calcium balance the deficits from the lime, malt and bicarbonate. This is pH 5.29.contributes 63 mEq to the proton deficit at pH 5.29 which, added to the deficit from the bicarbonate and lime just about equals the surfeit from the HCl. IOW 5.29 is the pH at which the surfeits and deficits balance and that is the pH at which the mash will arrive (assuming the actual malt is like the one I have used for the calculation).

Now here's where it may be a little hard to understand. At pH 5.29 all the hydroxyl ions are neutralized to water consuming 5.4 mEq H+. Most of the bicarbonate is protonated to carbonic acid (0 charge) consuming 60.6 mEq H+ so the remaining H+ is 128.4 - 5.4 - 60.6 = 62.4 mEq. That is just the amount of H+ consumed by the malt in going from it's intrinsic pH to pH 5.29. So everything stays balanced. In a nutshell, the additions were balanced by H+ offsetting HCO3- and the malts by whatever cations it contains being offset by whatever acid anions are in it at its intrinsic pH. After reaction H+ removes HCO3- and the remaining H+ protonates malt anions.

Obviously the calcium, sodium and chloride in the salts and acid you added remain in the mash liquor augmented by whatever calcium and sodium the malt adds.

After all this I think perhaps the confusion stems from the semantics. When one speaks of a profile for water he thinks of adding minerals to it to obtain a desired set of ion concentrations in the treated water sans malt. Were you to add the salts and acids discussed here to 8 gal of water you would not get the impossible Ca =4, Na = 50, Cl = 150 profile. You would get the balanced Ca = 3.6, Na = 49.7, Cl = 150, H+ =58. IOW the missing cation would be the H+ ions in excess of that needed to remove all the bicarbonate and hydroxyl. And, of course, the pH would about 1.24 because there is still a lot of HCl. In the mash all the acid (H+) is consumed in protonating OH-, HCO3- and malt acid anions.

I hope this has been helpful. It is pretty tricky in all the details.

 

[bitteritdown]

After all this I think perhaps the confusion stems from the semantics. When one speaks of a profile for water he thinks of adding minerals to it to obtain a desired set of ion concentrations in the treated water sans malt. Were you to add the salts and acids discussed here to 8 gal of water you would not get the impossible Ca =4, Na = 50, Cl = 150 profile. You would get the balanced Ca = 3.6, Na = 49.7, Cl = 150, H+ =58. IOW the missing cation would be the H+ ions in excess of that needed to remove all the bicarbonate and hydroxyl. And, of course, the pH would be less than 0 because there is still a lot of HCl. In the mash all the acid (H+) is consumed in protonating OH-, HCO3- and malt acid anions.

Bingo! Extraordinarily helpful, thanks AJ!

Now if only the spreadsheet I used accounted for those excess H+ cations.

37% HCl is 12N so 10.7 mL of that contributes 12*10.7 = 128.4 mEq of protons at any mash pH as it is a strong acid. These are balanced by 128.4 mEq of Cl- ions which is 128.4*35.46 = 4553.06 mg for a concentration of 128.4*35.46/30.28 = 150 mg/L - what you wanted.

The 0.2 grams of lime is 2.7 mmol producing 5.4 mEq of Calcium which is 20*5.4 = 108 mg for 108/30.28 = 3.6 mg/L. Close to what you wanted. It also yields 5.4 mEq of hydroxyl ion balancing the Ca ions and contributing 5.4 mEq to the mash proton deficit.

The 5.5 grams of sodium bicarbonate is 65.47 mmol resulting in 65.47 mEq of sodium for 65.47*23/30.28 = 49.7 mg/L - also close to what you want. It also yields 65.47 mEq of negative bicarbonate balancing the sodium and contributing about 63 mEq to the mash proton deficit.

For the malt I picked Weyermanns pneumatic pilsner malt as it is pretty pale (3.3 EBC) which is about 1.65 L. Nine pounds of it will impose an additional proton deficit of about 60 mEq/L at mash pH. The actual deficit depends on the mash pH.

When all this stuff is mixed the mash settles at the pH where the proton surfeit from the acid and the tiny contribution from the calcium balance the deficits from the lime, malt and bicarbonate. This is pH 5.29.contributes 63 mEq to the proton deficit at pH 5.29 which, added to the deficit from the bicarbonate and lime just about equals the surfeit from the HCl. IOW 5.29 is the pH at which the surfeits and deficits balance and that is the pH at which the mash will arrive (assuming the actual malt is like the one I have used for the calculation).

So the proton surfeit/deficit model calculates a mash pH of 5.29, the spreadsheet presumably uses the SRM model and predicts mash pH of 5.4

 

[ajdelange]

I can easily get a higher pH by specifying a more alkaline malt. If, for example, I use Weyermann's floor Pils the estimated pH is 5.39.

All the models are proton deficit models whether the spreadsheet/calculator author is aware of it or not. As such some of them aren't terribly robust but that doesn't matter if one is deducing the acidity parameters of the malt from it's color as the error induced by doing that is more than the error induced by the simple (linear) models the calculators seem to use. The proton deficit model is quite robust but doesn't give a better answer necessarily unless you feed it accurate malt data and it requires a lot of work on your part to get that. Easier to do a test mash.