Brewing liquor question

(That's water to the rest of us!) Beer is about 95% water, so if you want to discuss water treatment, filtering etc this is the place to do it!
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Kev888
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Re: Brewing liquor question

Post by Kev888 » Sun Mar 24, 2019 11:00 am

timtoos wrote:
Thu Mar 21, 2019 8:40 am
Hi everyone...
Looking at the OP, I suspect the calculators might be generating far more confusion than the actual water treatment. They can be useful tools but are frequently 'way' over-complicated for the basics, and will mindlessly give answers whether appropriate or not (especially if written elsewhere in the world to the style and methods being employed). They set me back by years when first trying to get into it. So I might suggest that you take a step away from them in order to focus on the underlying treatment needed to achieve your aims. Then just use them to crunch numbers if wished, rather than letting them try to guide you.
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Re: Brewing liquor question

Post by f00b4r » Sun Mar 24, 2019 10:54 pm

Silver_Is_Money wrote:The Graham Wheeler calculator often suggests the addition of calcium carbonate to hit a target water profile. Since calcium carbonate is highly insoluble in water, how does one add it and then actually get it to go fully into solution, whereby it will do what you think it is doing, as opposed to merely dropping out and doing very little due to its relatively high insolubility?

The GW instructions say to add calcium carbonate directly to the mash due to the insolubility problem, but I seem to recall research by Kai Troester (Braukaiser) which indicates that even via this method he was never capable of getting more than half of the calcium carbonate to enter into solution.

Is this a potential flaw in the methodology of the Graham Wheeler calculator? Should you add a bit more than twice GW's suggested amount of calcium carbonate to the mash, with the Braukaiser knowledge that a bit more than half will more than likely just drop out and not contribute?

Alternatively, some have suggested that if you add calcium carbonate to brewing liquor and then bubble CO2 into it while stirring, via this method you can eventually get the calcium carbonate to fully dissolve into solution. This is the only method that I'm aware of whereby you can get all of it to go to work for you as intended.

EDIT: Here is the link to Braukaiser's calcium carbonate research.
http://www.braukaiser.com/wiki/index.ph ... lved_chalk
viewtopic.php?t=55775

Quite an old post and since then the widespread availability of carbonation caps lets you use them in tandem with a soda PET bottle to achieve the same thing if you only need to treat a smaller amount of water.
Others use sodium bicarbonate or potassium bicarbonate to achieve similar results as they are readily soluble but oyu would need someone with a good knowledge of water chemistry (not me) to explain how they might have a different reaction on mash pH).

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Re: Brewing liquor question

Post by Silver_Is_Money » Mon Mar 25, 2019 12:18 am

Here is what happens:

If you are brewing (for example) a Stout which requires 100 ppm of alkalinity in the mash water in order to raise the mash pH to 5.4, and you are beginning (for simplicity) with distilled water at zero alkalinity, and you calculate that a certain amount of calcium carbonate is required to achieve 100 ppm of alkalinity, then:

When you add the calculated amount of calcium carbonate to the mash, half will simply not go into solution and will instead drop out and do nothing, leaving you with only an achieved 50 ppm alkalinity, and a mash that takes place at perhaps pH 5.1 instead of your desired pH 5.4.

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Re: Brewing liquor question

Post by McMullan » Mon Mar 25, 2019 11:52 am

Silver_Is_Money wrote:
Mon Mar 25, 2019 12:18 am
Here is what happens:

If you are brewing (for example) a Stout which requires 100 ppm of alkalinity in the mash water in order to raise the mash pH to 5.4, and you are beginning (for simplicity) with distilled water at zero alkalinity, and you calculate that a certain amount of calcium carbonate is required to achieve 100 ppm of alkalinity, then:

When you add the calculated amount of calcium carbonate to the mash, half will simply not go into solution and will instead drop out and do nothing, leaving you with only an achieved 50 ppm alkalinity, and a mash that takes place at perhaps pH 5.1 instead of your desired pH 5.4.
Then: add more, assuming you're monitoring pH of the mash. Most things in brewing need to be determined empirically. Give 3 brewers the same recipe and procedure to follow and you'll probably get 3 different beers.

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Re: Brewing liquor question

Post by Silver_Is_Money » Mon Mar 25, 2019 2:04 pm

McMullan wrote:
Mon Mar 25, 2019 11:52 am
Then: add more, assuming you're monitoring pH of the mash. Most things in brewing need to be determined empirically. Give 3 brewers the same recipe and procedure to follow and you'll probably get 3 different beers.
The simple solution (per Braukaiser) is to add twice as much Calcium Carbonate to the mash vs. what you (or software) initially calculate is necessary.

Another solution is to use Sodium Bicarbonate (Baking Soda) instead of Calcium Carbonate. Baking soda is highly soluble in water, so all of it will contribute and work as intended.

Or to raise mash pH you can alternately add Ca(OH)2 (Calcium Hydroxide, also called Pickling Lime and Slaked Lime). It is also highly soluble in water. This particular solution to the problem contributes no bicarbonate species, but that is effectively irrelevant if simply raising the mash pH is the goal. The warning required here is that calcium hydroxide is rather dangerous to handle, and PPE (personal protective equipment) is strongly advised. If you get some of it in your eyes you can go blind.

I fully concur that 3 brewers will likely make 3 somewhat different beers if given the same recipe.

One problem with attempting to add more calcium carbonate during the mash (and after a first pH sample) is that sometimes within as little as 20 minutes the mash is already virtually 100% complete. By the time you cool and test a 10-15 minute sample with a pH meter, and calculate a second addition of calcium carbonate, the mash is already done. That, plus only half of your second addition will contribute, and half of it will drop out without contribution.... Another problem is that if you sample the mash too early you will most likely be reading a false low mash pH.

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Re: Brewing liquor question

Post by Kev888 » Mon Mar 25, 2019 2:51 pm

There are many options - usually with pros and cons, and certainly with scope for local and personal preferences. This is one reason why (IMO) the brewer rather than the calculator should be making the decisions on what is used and how they go about it.

Like many here, I rarely need to raise alkalinity and then only by small amounts for darker beers, so with my water it is easy to use sodium bicarbonate without sodium levels becoming undesirable. As f00b4r says, potassium bicarbonate is another popular one. I can't say that I like using calcium carbonate for the practical reasons mentioned, but British brewing tends towards plenty of calcium so presumably it wouldn't be inappropriate (if enough is used).
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Re: Brewing liquor question

Post by Eric » Mon Mar 25, 2019 3:32 pm

Silver_Is_Money wrote:
Mon Mar 25, 2019 2:04 pm
McMullan wrote:
Mon Mar 25, 2019 11:52 am
Then: add more, assuming you're monitoring pH of the mash. Most things in brewing need to be determined empirically. Give 3 brewers the same recipe and procedure to follow and you'll probably get 3 different beers.
The simple solution (per Braukaiser) is to add twice as much Calcium Carbonate to the mash vs. what you (or software) initially calculate is necessary.

Another solution is to use Sodium Bicarbonate (Baking Soda) instead of Calcium Carbonate. Baking soda is highly soluble in water, so all of it will contribute and work as intended.

Or to raise mash pH you can alternately add Ca(OH)2 (Calcium Hydroxide, also called Pickling Lime and Slaked Lime). It is also highly soluble in water. This particular solution to the problem contributes no bicarbonate species, but that is effectively irrelevant if simply raising the mash pH is the goal. The warning required here is that calcium hydroxide is rather dangerous to handle, and PPE (personal protective equipment) is strongly advised. If you get some of it in your eyes you can go blind.

I fully concur that 3 brewers will likely make 3 somewhat different beers if given the same recipe.

One problem with attempting to add more calcium carbonate during the mash (and after a first pH sample) is that sometimes within as little as 20 minutes the mash is already virtually 100% complete. By the time you cool and test a 10-15 minute sample with a pH meter, and calculate a second addition of calcium carbonate, the mash is already done. That, plus only half of your second addition will contribute, and half of it will drop out without contribution.... Another problem is that if you sample the mash too early you will most likely be reading a false low mash pH.
I think you would have very much enjoyed debating water treatment, indeed any aspect of brewing, with Graham, but sadly he is no longer here to participate. He was also critical of his calculator and frequently expressed a desire to write a replacement, but it never became his highest priority. You would certainly have raised his eyebrows by saying that within 20 minutes the mash is virtually 100% complete. I wouldn't mind having a penny for every time he said the most important part of the mash happened after starch conversion was complete, but that's an aside.

Like many, my water has more alkalinity than is desirable for brewing any beer, so I treat it with acid and have no need of baking powder. Do you know what happens to baking powder after the mash? I ask as I don't know, but do know the remnant of alkalinity of mine that finds its way into the boiler drops out with hot break due to the very point you make about chalk, but I'm not sure that will happen with baking powder which may possibly find itself in the FV and finished beer.
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Re: Brewing liquor question

Post by Silver_Is_Money » Mon Mar 25, 2019 4:31 pm

In the USA baking powder and baking soda are two distinctly different things. I'm not sure of the nomenclature for them in the UK, or if they are considered one and the same thing in the UK.

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Re: Brewing liquor question

Post by WallyBrew » Mon Mar 25, 2019 4:45 pm

Silver_Is_Money wrote:
Mon Mar 25, 2019 4:31 pm
In the USA baking powder and baking soda are two distinctly different things. I'm not sure of the nomenclature for them in the UK, or if they are considered one and the same thing in the UK.
They are different here.

I'd like to know how it was determined that only half the calcium carbonate was used up and the other half rejected and explicitly in those ratios.

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Re: Brewing liquor question

Post by Silver_Is_Money » Mon Mar 25, 2019 5:26 pm

WallyBrew wrote:
Mon Mar 25, 2019 4:45 pm
I'd like to know how it was determined that only half the calcium carbonate was used up and the other half rejected and explicitly in those ratios.
The details are found here:
http://www.braukaiser.com/wiki/index.ph ... lved_chalk

And here:
http://braukaiser.com/wiki/index.php?ti ... pH_control
Raising residual alkalinity (raises mash pH)
If the water’s residual alkalinity is too low the addition of alkaline salts like calcium carbonate (chalk, CaCO3) or sodium bicarbonate (baking soda, NaHCO3) or even strong bases like calcium hydroxide (Ca(OH)2) raises its residual alkalinity. If calcium carbonate is used it will not dissolve in the water unless CO2 is added. Though there are ways to dissolve calcium carbonate many brewers simply add it to the brewing water without dissolving it. In experiments I found that dissolved chalk is not only twice as effective in raising the water’s residual alkalinity, undissolved chalk is also not able to raise the mash pH by more than 0.2 pH units. In other words the addition of more than 500 mg/l undissolved calcium carbonate, which is equivalent to a residual alkalinity of about 200 ppm as CaCO3, had little or no effect on mash pH[2]. As shown in Beer color, alkalinity and mash pH water with a residual alkalinity of more than 200 ppm as CaCO3 is rarely needed, even for the darkest beers. A.J. deLange, an expert in everything brewing water, believes that while the mash pH is low enough to dissolve chalk, the actual rate of dissolving chalk at this pH happens slowly which reduces it's effectiveness as a means of raisinbg mash pH[6]. Despite its shortcomings it still remains the most popular salt addition for raising mash pH. In addition to carbonate chalk also adds calcium to the mash which counteracts some of the pH raising power of the carbonate.

Baking soda, however, is more soluble than chalk and does not show the somewhat unpredictable mash pH behavior that comes with chalk. The drawbacks of adding baking soda is the increase of the water’s sodium content and the lack of calcium which has a number of positive effects on beer quality.

Another substance that can be used to increase the alkalinity of the brewing water and thus raise the mash pH is calcium hydroxide (pickling lime, slaked lime, Ca(OH)2. It dissolves in water more readily than chalk and doesn't show the limits that undissolved chalk has while it also adds calcium to the mash. The only drawback is that it is a caustic substance and needs to be handled with care. It is best added to the mash after dough-in.
Last edited by Silver_Is_Money on Mon Mar 25, 2019 5:37 pm, edited 1 time in total.

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Re: Brewing liquor question

Post by WallyBrew » Mon Mar 25, 2019 5:36 pm

Silver_Is_Money wrote:
Mon Mar 25, 2019 5:26 pm
WallyBrew wrote:
Mon Mar 25, 2019 4:45 pm
I'd like to know how it was determined that only half the calcium carbonate was used up and the other half rejected and explicitly in those ratios.
The details are found here:
http://www.braukaiser.com/wiki/index.ph ... lved_chalk
Really helpful

I assume you mean this bit:

"I tested this in a side-by-side experiment where I brewed a Schwarzbier with water that had suspended chalk and water that had dissolved chalk. Based on the mash pH research I knew that, when dissolving it, I could use only half the chalk and would still get the same mash pH. That was validated in the experiment."

Seems really scientifically conclusive yes/no

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Re: Brewing liquor question

Post by Silver_Is_Money » Mon Mar 25, 2019 5:40 pm

I amended my post above to add more details and another link.

It could be even worse than I initially thought. Even if you more than double the amount of added calcium carbonate, if it is not pre-dissolved via the Braukaiser detailed "CO2 process" its maximum ability to raise pH is only 0.2 points. If I'm reading him correctly that is....

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Re: Brewing liquor question

Post by WallyBrew » Mon Mar 25, 2019 6:02 pm

Silver_Is_Money wrote:
Mon Mar 25, 2019 5:40 pm
I amended my post above to add more details and another link.

It could be even worse than I initially thought. Even if you more than double the amount of added calcium carbonate, if it is not pre-dissolved via the Braukaiser detailed "CO2 process" its maximum ability to raise pH is only 0.2 points. If I'm reading him correctly that is....
In my opinion it is pointless adding calcium carbonate to the mash/mash liquor to raise pH. The USP method for calcium carbonate requires it to be dissolved in HCl and for the BP/EP acetic acid is used. I cannot remember the exact strengths but they are of similar molarity, and indeed normality.

The chalk dissolves much more rapidly in the hydrochloric acid which has of the order of 100 more protons available than the acetic. Acetic acid is still regarded as a strong acid. So when we come down to mash pH of 4.8 as a low and 5.8 a s a high then there are 1/1000th of the number of protons available than with the acetic acid used for BP/EP. Chance of any chalk dissolving in a useful time?

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Re: Brewing liquor question

Post by Carnot » Mon Mar 25, 2019 7:23 pm

I will chip in my two cents worth but do not want to get embroiled in a pointless discussion. Several observations.

You have a very thin water, which will be lacking any buffering in its delivered state. Calcium carbonate is sparingly soluble in water- typically about 40-50 mg/L depending on the other as CaCO3.

Just adding calcium carbonate will not do much as the best that you might be able to do is boost the calcium and alkalinity up to the the solubility limit, see above. To dissolve more calcium carbonate into the require either the addition of an acid, or the addition of carbon dioxide which will form the bicarbonate. If you use an acid, then this is likely to send the pH lower especially a strong acid. Creating bicarbonate via carbon dioxide addition is likely to maintain the pH in the desired range, depending on how much bicarbonate is produced.

The Braukaiser link gives a very good explanation in Fig 2 of the relationship between carbonic acid, bicarbonate and carbonate in solution.

Just be aware that as the pH rises and more carbonate is formed then once the solubility limit of calcium carbonate is achieved then calcium will be precipitated as the carbonate. Adding more carbon dioxide will dissolve the calcium carbonate progressively up to the solubility limit of calcium bicarbonate which is about 16 g/L. However calcium bicarbonate cannot be isolated, so that is not an option.

I would strongly recommend the advice of Eric and Wallybrew and do not get carried away with brewing calculators, especially on a thin water.

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Re: Brewing liquor question

Post by Aleman » Tue Mar 26, 2019 9:34 am

I usually brew with water that has very little in it, and never have to increase alkalinity AND add acid!

I follow three rules

1) Adjust alkalinity IF Required either by adding acids (I use hydrochloric and sulphuric), or some form of easily dissolved hydrogen carbonate salt (Usually potassium, but sodium is easier to get hold of). I aim for 15mg/L for pale beers up to 125mg/L for dark beers depending on the grist.

2) Increase calcium to provide sufficient for subsequent processes ... Minimum of 75 but up to 250mg/L. Using a mixture of calcium sulphate (gypsum) and calcium chloride, the exact mixture depends on (3)

3) Use more sulphate than chloride if I want a 'drier', more hop forward beer, and more chloride than sulphate if a want a 'fuller', maltier beer. ... Of course if I want to keep calcium levels on the lower end I can choose my acids to provide much of the sulphate and/or chloride that I need.

Using the 'typical' grists that brew with, and as I've brewed a lot of beers I've settled on some 'standard' grists for the beers I brew, I know that with the water profile I have (based on alkalinity and TDS readings on the day) my pH will fall within 5.3 to 5.7-8. I don't bother to hit a specific predicted pH just to be within the range, because that's all that matters, ingredient variability, and the biochemistry, makes it 'pointless' trying to calculate the exact pH value. Especially when given 'normal' water and grists the pH will naturally fall within that range anyway

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