Water adjustment with salts and Hydrochloric acid

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Gadjobrinus

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Just wanted to get some feedback on this. Through the kindness of a new member from England, I was inspired to think more on the use of acids in water adjustment. Through a combination of 10% hydrochloric and salt adjustments, from some truly bad, alkaline water, with a 50:50 RO dilution, I now have:

Ca 133
Mg 21
Alk. as CaCo3 26
SO4 246
Cl 97
Na 5
RA -81
SO4:Cl 2.5:1

This would be for English bitters; in my case, most especially Northern England bitters. One member kindly turned me on to 37% hydrochloric available on Amazon, and I've confirmed through what I think may be the chemical company, that it is food grade. Another, 10%, surpasses, food grade, according to the maker. I'll have to ask for guidance from Ajdelange, perhaps, on what exactly that means in terms of human consumption.

Adding 65 mg 10% to 20 gallons feels like alot, but I have no experience whatsoever with hydrochloric in food use. If I can find sulfuric acid, also a British practice, I'll play with that as well, though I'll have to add some calculations I don't yet know into John Palmer's spreadsheet.

Thoughts?
 
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Gadjobrinus

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For comparison's sake, and a "leaner" base to start from. Using 75% RO:city water, 35 ml of 10% hydrochloric in 20 gallons total water; adding in just gypsum. I now have:

Ca 70
Mg 10
Alk. as CaCo3 8
SO4 130
Cl 52
Na 2
RA -48
SO4:Cl 2.5:1

-I'll have to dilute 37% HCL down, as the 10% I've seen available is prohibitively expensive.
 

McKnuckle

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Paul, I'm curious to see responses to your post. Normally there are a couple of folks who leap on these topics, so their silence (so far) has me wondering if it's a subject that's not well known among American brewers. We'll wait and see...
 

Silver_Is_Money

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Paul, your water in post #2 above looks a lot like the water I designed for the likes of ESB. What style(s) are you generally planning to brew with it?

If you are choosing HCl primarily for its ability to bring chloride ions on board while in the process knocking out a bunch of alkalinity, all without adding any potential flavor component (as may be the case for lactic acid) or bringing along with it any additional calcium or magnesium ions, then for your particular water it appears to be a good choice.

Other than the potential safety hazard factor, I can't see anything wrong with your using HCl, as long as it is food grade. But personally I prefer to stick with lactic acid as a safer alternative. But then again, I'm even squeamish about using phosphoric acid these days.
 
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Gadjobrinus

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Thanks for the post, McKnuckle. I would lay odds AJ is out of town, or country. Not that this is the most thrilling thread, lol, but the guy can teach and I could use some learning.

Funny how I've used lactic and phosphoric all these years, and have never seen the use of HCL until this thread, and coming to know a British brewer or two. Both HCL and sulfuric acid are dangerous, but so useful, at the same time - I was pretty interested to see the chloride contribution of HCL in Palmer's spreadsheet and need to figure out how to calculate sulfuric acid SO4 contribution (I fear I have to read up on mEq and the like, and my brain is done broke...).

Looking forward to input from AJ, Martin et al!
 
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Gadjobrinus

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Paul, your water in post #2 above looks a lot like the water I designed for the likes of ESB. What style(s) are you generally planning to brew with it?

If you are choosing HCl primarily for its ability to bring chloride ions on board while in the process knocking out a bunch of alkalinity, all without adding any potential flavor component (as may be the case for lactic acid) or bringing along with it any additional calcium or magnesium ions, then for your particular water it appears to be a good choice.

Other than the potential safety hazard factor, I can't see anything wrong with your using HCl, as long as it is food grade. But personally I prefer to stick with lactic acid as a safer alternative.
Crossed in the mail and you nailed it, Silver. Yep, that's exactly what I was looking to do. Water for bitters, to include my strong bitter or ESB. And I was triggered to look into this by exchanges with Cire. Amazed to see how common HCL and sulfuric is among British brewers, and how hard it is to even find the materials here. But you're spot on - for a chloride contribution, for my bitters. Many thanks for the nod of affirmation, Silver!

Edit: Argh, when I say my bean is fried, it's writing stuff like "crossed in the nail and you nailed it....." That byte just dropped off the motherboard....!
 

z-bob

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I used hardware store muriatic acid (31.5% HCl, technical grade or maybe lower) once. Yes, I know it might be contaminated with heavy metals. I think the primary contaminate is usually iron, and this stuff was nice and clear w/o any yellow. "The solution for pollution is dilution." I am not recommending that you or anybody else use the stuff. I did it for science ;)

I believe it was 5 ml in a 4 gallon batch, plus a teaspoon of gypsum and a little sauermalz. It worked great. It seemed like a perfect solution; (no pun intended) use hydrochloric acid for H+ and chloride ions, gypsum for calcium and sulfate. Adjust the amounts to whatever ratio I wanted, then use a little lactic acid to do the final pH adjustment. Then I looked for food grade HCl and all I could find at the time was $125 a quart and I abandoned the whole idea and started using lactic acid.

Now I'm considering buying a liter of concentrated hydrochloric or phosphoric acid. But I'm still having fun with lactic acid.
 
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Gadjobrinus

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Z-bob, here's 37%, and here's 10% (though enough to last a lifetime - I think I'd prefer to dilute the 37%).

While I'm here, it's been so long and words, not numbers, are my wicket.

By c1V1=c2V2, where c1 = 37%, c2=10%, and I want to make a liter (V2=1L) up of the 10% HCL, V1=c2V2/c1; v1 = .27L or 270 liters; I should dilute and slowly mix in 270 ml acid in 500 or so ml of DI, then dilute to a total of 1L, mixing thoroughly. This gives me 1L of 10% acid - correct?
 
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mabrungard

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Hydrochloric acid is a particularly insidious substance since it exists simultaneously as both a liquid and gas. Hydrogen chloride gas is in the headspace of the container and can permeate through some containers. The hydrogen chloride gas moves through the environment and it creates hydrochloric acid when it encounters water. The high chloride content make this substance very corrosive to almost all metals, even stainless steel. I was recently the design engineer for a 16,000 gal chemical dosing system that had to deal with the hazards of this material. I did learn quite a lot in researching methods and materials to help make the system last.

One whiff of that stuff will certainly get your attention and since it is such an active acid, skin contact is instantly dangerous. Using diluted forms of this acid is recommended since that reduces the tendency to off-gas. Another annoying problem with hydrochloric acid is that if its stored in a gas-permeable container, it will slowly lose its potency as hydrogen chloride gas escapes. It really needs to be stored in glass.

With that said, hydrochloric and sulfuric acids can be well suited for brewing use. We often like appropriate chloride and sulfate content in our brewing liquor, so it would be an advantage to get that while neutralizing alkalinity. In the UK, the CRS and AMS acid products are widely used. They provide a constant ratio of hydrochloric and sulfuric acid in a single solution. That seems like it would be ideal, but that fixed ratio can be problematic. In my opinion, the ratio forces you to add either too much sulfate or chloride to your liquor in some cases. Having those acids as separate components and adding only the concentrations of sulfate and chloride to suit your current brew, is best.

Another thing to understand is that these acids are hazardous cargo and you can easily incur very steep hazardous materials shipping charges if the quantity is large. As I recall, shipping a liter or quart of those acids is probably not going to incur the hazardous materials charge, but its been a while since I dealt with that.
 
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Gadjobrinus

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Thank you, Martin. I'd need to look at my 10% source, but the 37% source indicates no HAZMAT fees. And thank you for the cautions.

Given its volatility, if I want to pour it into a glass container (I am guessing both the 37% and my 10% dilution would best be done like this?), are there any special precautions to take (besides gloves, eye protection). Respirator?

And on the CRS (and AMS - I don't know what that is - haven't come across it yet), that was actually my thought as well, ill-informed on water chemistry (and chem. as well, been a long time) as I am. Convenient, but then I'm locked in to the anion contribution of a 50:50 solution. It's probably moot anyway - have found no seller on our shores of the CRS, anyway.

Given that, I've been looking for a 10% or workable source of food grade sulfuric acid, but in terms of end-point seller, have come up empty. I see manufacturers, but that's been it.

I know this is really rudimentary, but would you mind checking my dilution calculation, posted on the last page? I'd hate to be off, when it's HCL!

Man I'm tired. 'nother story. I mean the dilution calculation above.
 

Silver_Is_Money

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It may prove far safer, easier, and less costly in the long run to simply build your water from a base of RO, and skip the HCl idea altogether.
 
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Gadjobrinus

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It may prove far safer, easier, and less costly in the long run to simply build your water from a base of RO, and skip the HCl idea altogether.
Thanks Silver. This is an experiment - I'd like to try using a common British method. I do have lab experience, though formal chemistry study has been a long time away. The two things I do wonder are whether I've got the 37%-10% dilution correct, and does 35 ml in 20 gallons of water sound reasonable.

This is 75% RO. The acid, plus 12 grams gypsum, 2 grams CaCl, yielding a pretty bitter/pale ale brewing water, IMO.
 

stz

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We use hydrochloric, sulphuric and lactic acids at work. We use a 37% dilution of hydrochloric and sulphuric 50:50 and 88% lactic. We use the mineral acids when we don't particularly need to worry about the chloride and sulfate contribution which these acids add (ales) and lactic when we do (lager). I personally prefer lactic (good enough for the germans, slightly safer handling) though everybody else has preference for the mineral acids (british I guess).

You might need to use so much of any of those that you cannot avoid excess chloride or sulfate or pass the threshold where lactic becomes perceptible so some use phosphoric though we avoid it because of concerns on excess phosphates precipitating calcium in the boil and additional handling concerns. Luckily we only need to knock alkalinity down from 110-160ppm, some water here is almost 400ppm.

I'm a dumb ass so I've got experience of having all of these on my skin, hydrochloric and sulphuric at up to 80%. It takes a little while before you feel it (20-30 seconds with the hydrochloric, 12-18 seconds with the sulphuric). I've also tasted them, tangy. They are clearly hazardous substances to be treated with respect, but they are not as scary as other things we use, nitric acid and hot caustic are worse for me. Nitric immediately hissing when spilt on the floor and reacting happily with exposed metal and hot caustic almost immediately burning any exposed skin. We'll hose it around and you won't realise that you've misted yourself with some spray and a little later you are covered in tiny bleached spots.
 
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Gadjobrinus

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Thanks Bob and stz, really helpful. Our water is extremely alkaline, unfortunately, so I can't use much of it and have to go with the 75% RO. So, at the suggestion of a new member and British brewer here, the thought did occur of a "why not try it?" with the HCL and/or sulfuric, if I could find them. Seems pretty good now, with the additions (which includes that 10% HCL over 20 gallons). From:

Ca 70
Mg 41
HCO3 364
SO4 19
Cl 19
Na 9
RA 290

to

Ca 62
Mg 10
Alk. as CaCo3 25
SO4 94
Cl 65
Na 2
RA -25
SO4:Cl 1.5:1

-so, I'm pretty happy with this. What do you guys think?
 

stz

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As you've said if you can get your water down to ..

Ca 62
Alk. as CaCo3 25
SO4 94
Cl 65

Then you've great water for brewing. Alkalinity can happily be 30-40ppm for many styles if you need the wiggle room and I would still use calcium chloride and calcium sulfate to taste as needed which has the additional benefit of bringing up your calcium levels. 200ppm SO4 and 100ppm Cl2 is still well within reach and I don't often need to exceed this.

As a rule we aim for 150ppm calcium for process efficiency, we don't stress about calcium until over 200ppm though many I work with seem to find 300-400ppm acceptable (I try to keep it under 200ppm personally).

We've had analysis done on the finished beer and calcium levels are never particularly high any way suggesting it is doing its job in the boil and during fermentation. I might have an issue with excessive calcium levels because I'm the one who has to remove oxalate crystals. For some reason the argument that I want to work less isn't as sexy as the one where we can save on chemicals!
 
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Gadjobrinus

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Hahahah - it seems to me you're probably persuasive regardless, stz. Are you a brewery chemist or lab person?

Many thanks. Yeah, this is a "lean" version and it felt like a good baseline to start from, so I appreciate your contributions here, helps quite a bit.
 

cire

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If the object is to brew a beer as would most likely be found in Britain you might wish to consider using a profile similar to those used in Britain.
https://www.murphyandson.co.uk/mashing-liquor/

Hydrochloric acid is quite awful to handle at 37%. Dilute it in a well ventilated space, it will not generate as much heat as when diluting sulfuric. If necessary, use a fan to move the air away and do not breath the fumes. At 37% it will be approximatey 12 molar and unpleasant to handle, while at 6 molar it is comparatively benign and will give off very little gas when used in a normal manner.

with the water exampled above
Ca 70
Mg 41
HCO3 364
SO4 19
Cl 19
Na 9

Adding 0.9ml of 6 molar HCl would become

Ca 70
Mg 41
HCO3 71
SO4 19
Cl 189
Na 9

or if 0.8ml of 3 molar sulfuric instead the result would be

Ca 70
Mg 41
HCO3 71
SO4 249
Cl 19
Na 9

or with 0.4ml of each

Ca 70
Mg 41
HCO3 71
SO4 134
Cl 104
Na 9
 
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Gadjobrinus

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Cire, thanks for both the link and the post. I get the molarities, though again it's been forever and I'll just have to go back to bring conversions back to mind.

Quick read of the Murphy liquors leaves me a bit stunned. Sulfate at 400, Ca at 170, Cl at 200 - last time I brewed was 1995, and I had good but alkaline well water so I can't recall treatment, but I'm surprised at these figures even though I know they get this high in English brewing.

It's not British brewing in general I'm looking for so much as a bit of capture of Yorkshire brewing. Any advice in this way?

Thanks.

Edit: Thanks too on the cautionary notes re: HCL. At least so far in my searches, it seems HCL is the only one of the two (meaning, sulfuric for the other) I'm able to buy. So far. Still, I've only used phosphoric, I believe, and thanks again for the helpful suggestions.
 
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Gadjobrinus

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Just a reality check, please. After playing with numbers in emulating the Murphy & Sons figures, seems like I have a ton of both gypsum and HCL. I particularly want to make sure this amount of 10% HCL in 20 gallons is safe.

To 75% RO. Added in 51 grams gypsum, 1 gram CaCl, 3 g MgSO4, and 151 ml of 10% HCl.

What I ended up with was:

Ca 178
Mg 14
Alk. as CaCo3 -177
SO4 396
Cl 201
Na 2
RA -312
SO4:Cl 2:1

As I indicated above, it's been a really long time since I last brewed. I did treat my water and made many really good bitters, but I don't recall how hard I went, how high the minerality. So some guidance on the above numbers, yes, would be really appreciated.
 

McKnuckle

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How do we know if the Murphy numbers are mashing liquor ONLY (which could be subsequently reduced by the sparging liquor), or mineral concentration in the kettle? Big difference. I saw RO tanks at a couple of the English breweries I visited. What would be the point of those if it wasn't for dilution and/or building up water?
 
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Gadjobrinus

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That's a great insight and question, McKnuckle. Looking forward to the answer.

Edit: I actually contacted Murphy, through their webform. Perhaps they might also provide some insight.
 

cire

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How do we know if the Murphy numbers are mashing liquor ONLY (which could be subsequently reduced by the sparging liquor), or mineral concentration in the kettle? Big difference. I saw RO tanks at a couple of the English breweries I visited. What would be the point of those if it wasn't for dilution and/or building up water?
This link will give you access to Murphy's technical library. Those figures are what they advise to both commercial and amateur brewers and are for all liquor. They generally advise putting all salts into the mash, so mash liquors will be even higher, especially in soft water areas.
Lots of breweries now use RO water for many reasons, but particularly that they can contract brew or brew regional beers at all their breweries.

Paul, my last posting had 0.9ml of 6 Molar HCl, but should have read 0.8ml.

Using soft water it isn't uncommon to acidify mash liquor or the subsequent wort to achieve acceptable pH at each stage. With a high calcium level this should not ever be the case and the acid treated liquor should be tested to determine the remaining level of alkalinity. With low level alkalinity and higher calcium pH will be about 5.0 at knockout and finished beer will usually have a pH between 3.9 and 4.3.
 

mbobhat

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Just FYI 10% HCL is still pretty hazardous, it is used in US as a toilet bowl cleaner. I would go even lower, your 10% is close to 3.5 M, I would go to maybe 0.5M which would be closer to 2%. That Makes it fairly safe to handle and should be plenty to adjust your ppm alkalinity of your water down to mash pH. I didn't do any calculation but 35mL of 10% seems like a lot so I would just check your pH along the way so you don't overshoot.
M2 is the desired new concentration (0.5 molar)
I calculate to prepare 100 ml of 0.5 M HCl, add 4.16 ml of conc. HCl to 50.
ml of water and dilute up to 100 ml. If you wanna make a Liter you have 500 mL water and add about 40mL conc. HCL then dilute that up to a liter.

Handy dilution calculator:

http://www.sigmaaldrich.com/chemist...er/technical-library/molarity-calculator.html

Just a reminder to always add acid to some water and then dilute to final desired volume since you don't wanna splash any up on you.
 

cire

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High strength food grade hydrochloric acid is readily available at reasonable cost in UK. It is, as said, it is a gas and when at high concentration liquid form it will freely liberate large volumes of this noxious gas.

I will first dilute mine in a large mixing bowl with deionised water in equal quantities. This does create some heat, but can be done at a reasonable rate safely in a well ventilated space. I do it outside when there is a slight breeze.

Yes, it is still very powerful, but at least it can at this lower concentration be handled without having to hold ones breath when diluting it to a prefered strength.
 

Northern_Brewer

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I saw RO tanks at a couple of the English breweries I visited. What would be the point of those if it wasn't for dilution and/or building up water?
Quite possibly contract brewing - or just that their water sucks. You have to remember that the UK is one of the most geologically diverse lumps of rock on the planet - and there's big variations in rainfall as well. So in SE England the municipal supply is 90% groundwater in places, and that groundwater is coming from an aquifer that is essentially the same as the White Cliffs of Dover - pure chalk with a few other things. Further north there's more rain and the geology is generally more friendly, so the tapwater can be almost RO-soft. I know you guys have mentioned visiting some of the breweries in the Thames Valley - their municipal water at least is pretty horrible (although not as bad as Kent) - and it wouldn't surprise me if they had RO tanks there.
 

McKnuckle

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The RO tank I remember (and have a photo of) is at Marston's in Burton-on-Trent, which has a little brewing history to show for itself. ;) The tank says:

Reverse Osmosis Water To Boiler Feed (50,000 Litres)

Now I'm not sure why they would pump RO water to the copper. So maybe it's a red herring w.r.t. this discussion.

Anyway, those mineral concentrations are really high from the perspective of what's normally discussed. 300 ppm Cl in a mild for example, or 400 ppm SO4 along with 200 ppm Cl.

I don't know what Murphy's is or who subscribes to their content or if it's representative of real world brewing. Maybe it is, but without proof, I'm inclined to stick with the 5.3-5.4 mash pH and pleasant beer quality that I achieve with far more moderate mineral concentrations.
 

Northern_Brewer

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The RO tank I remember (and have a photo of) is at Marston's in Burton-on-Trent, which has a little brewing history to show for itself. ;)
There you go - as one of the main consolidators of traditional breweries, Marstons find themselves having to reproduce beers from all over the country (and also do a lot of contract brewing - they make cask Bass for instance), so it makes sense that they have to do a lot of water profiles from scratch.

I don't know what Murphy's is or who subscribes to their content or if it's representative of real world brewing. Maybe it is, but without proof, I'm inclined to stick with the 5.3-5.4 mash pH and pleasant beer quality that I achieve with far more moderate mineral concentrations.
Murphys are one of the main brewery services labs with a history going back to the 19th century. If anyone knows about the chemistry of British beer, it's them. However they are based in Nottingham so their outlook on life is perhaps a little "Burtonised"....
 

cire

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The RO tank I remember (and have a photo of) is at Marston's in Burton-on-Trent, which has a little brewing history to show for itself. ;) The tank says:

Reverse Osmosis Water To Boiler Feed (50,000 Litres)
It might be what it says on the tin, boiler water, not brewing liquor. I suspect they boil that water for superheated steam used to heat the copper when boiling wort. They wouldn't want hard water in that boiler for many reasons.

There are breweries in Burton using RO water for brewing liquor.
 
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Gadjobrinus

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I saw that Murphy sells "AMS," which I understand is the same thing as CRS. Now that I have a source, I would sure like to find a source for sulfuric acid (which Murphy sells by itself, though interestingly, I didn't find any HLC by itself). Not that I can't get good liquor here with what I have, but because it would be an interesting experiment to brew in this traditional, British way.
 
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