Phosphoric and ascorbic acid for alkalinity reduction.

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orlando
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Re: Phosphoric and ascorbic acid for alkalinity reduction.

Post by orlando » Wed Jun 17, 2020 6:11 am

Silver_Is_Money wrote:
Wed Jun 17, 2020 1:14 am
No need to fault phosphoric acid.
So how is it that with no changes in my process is it only when I use phosphoric I get noticeable precipitate, like the pictures Jocky showed?
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Re: Phosphoric and ascorbic acid for alkalinity reduction.

Post by WallyBrew » Wed Jun 17, 2020 7:26 am

orlando wrote:
Wed Jun 17, 2020 6:11 am
Silver_Is_Money wrote:
Wed Jun 17, 2020 1:14 am
No need to fault phosphoric acid.
So how is it that with no changes in my process is it only when I use phosphoric I get noticeable precipitate, like the pictures Jocky showed?
Thats because SIM is talking about calcium carbonate precipitation and adding phosphoric to water will not precipitate calcium carbonate.

It can however, as you have found, cause a precipitate of some type of calcium phosphate.

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Re: Phosphoric and ascorbic acid for alkalinity reduction.

Post by orlando » Wed Jun 17, 2020 7:39 am

WallyBrew wrote:
Wed Jun 17, 2020 7:26 am
orlando wrote:
Wed Jun 17, 2020 6:11 am
Silver_Is_Money wrote:
Wed Jun 17, 2020 1:14 am
No need to fault phosphoric acid.
So how is it that with no changes in my process is it only when I use phosphoric I get noticeable precipitate, like the pictures Jocky showed?
Thats because SIM is talking about calcium carbonate precipitation and adding phosphoric to water will not precipitate calcium carbonate.

It can however, as you have found, cause a precipitate of some type of calcium phosphate.
OK, thanks.
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Re: Phosphoric and ascorbic acid for alkalinity reduction.

Post by Silver_Is_Money » Wed Jun 17, 2020 1:42 pm

Calcium Apatite is what precipitates. Brewing Researcher, Consultant, and Scientist A.J. deLange said this of it on another forum:
It isn't phosphoric acid that bids calcium but phosphate ion and there is only a tiny bit of phosphate present at mash ph. There are circumstances where calcium will precipitate but the water has to be very hard and quite alkaline. There are some curves in the Palmer Water book.
PS: I believe he intended to type "binds" where you see "bids". From this it appears that only those with both really hard and highly alkaline water may find issue with the use of phosphoric acid.

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Re: Phosphoric and ascorbic acid for alkalinity reduction.

Post by orlando » Wed Jun 17, 2020 1:54 pm

Silver_Is_Money wrote:
Wed Jun 17, 2020 1:42 pm
Calcium Apatite is what precipitates. Brewing Researcher, Consultant, and Scientist A.J. deLange said this of it on another forum:
It isn't phosphoric acid that bids calcium but phosphate ion and there is only a tiny bit of phosphate present at mash ph. There are circumstances where calcium will precipitate but the water has to be very hard and quite alkaline. There are some curves in the Palmer Water book.
PS: I believe he intended to type "binds" where you see "bids". From this it appears that only those with both really hard and highly alkaline water may find issue with the use of phosphoric acid.

Would 250 do it? :D
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Re: Phosphoric and ascorbic acid for alkalinity reduction.

Post by Silver_Is_Money » Wed Jun 17, 2020 2:27 pm

orlando wrote:
Wed Jun 17, 2020 1:54 pm
Would 250 do it? :D
The precipitation charts found at nearly the very back of Palmer's 'Water' book only go as high as 200 mg/L alkalinity, so although I'm no authority here the case is likely that it is enough.

It may be that Regional Water Authority supplied domestic water in the USA is generally much softer than the same for the UK, but of that I'm again in no position to make a meaningful assessment. Very hard and alkaline water in the USA is generally found in well water. My well water is through the roof hard and alkaline. 712 mg/L Total Hardness, and 377 mg/L Alkalinity (both as CaCO3) per a sample I sent to Ward Laboratory. When I use it (which is now seldom, mainly because my Mg++ ion is at 55 mg/L), I use it at 25% Well and 75% RO or distilled. But then I'm forced to add more calcium. The hassle has led me to using RO water with added minerals.

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Re: Phosphoric and ascorbic acid for alkalinity reduction.

Post by Eric » Thu Jun 18, 2020 2:14 pm

Silver_Is_Money wrote:
Wed Jun 17, 2020 2:27 pm
It may be that Regional Water Authority supplied domestic water in the USA is generally much softer than the same for the UK, but of that I'm again in no position to make a meaningful assessment. Very hard and alkaline water in the USA is generally found in well water. My well water is through the roof hard and alkaline. 712 mg/L Total Hardness, and 377 mg/L Alkalinity (both as CaCO3) per a sample I sent to Ward Laboratory. When I use it (which is now seldom, mainly because my Mg++ ion is at 55 mg/L), I use it at 25% Well and 75% RO or distilled.
Maybe USA has a greater proportion of soft water domestic supplies than UK, but many parts of Britain do have soft water. Virtually all of the far South West, much of Wales, the northwestern corner of England and the majority of Scotland are on impermeable rocks, so have soft water. Many other areas are supplied with surface water that is classified as soft while others have a mix of surface and ground water dependent upon rainfall variation. However, the majority of the UK population live in the south and east where the ground is mostly limestone or chalk and surface water is supplied to a minority of homes in those parts.

Fewer in UK rely on well water and a greater proportion have a commercial supply, good to drink without extra treatment. A UK domestic water supply, unlike in USA, cannot legally be cut-off simply because the bill was not paid on time. UK is more northerly than the overwhelming majority of USA with a different climate and no part classified as arid. I think your only State with common latitudes to UK is Alaska, itself seven times larger than the whole of UK. Surely differences between our waters are greater than might be first thought. UK is a much smaller country with a diverse geology, but has little climate variation and accordingly has waters with less variation in mineral content. The overwhelming majority of hard and alkaline UK waters can potentially be treated with readily available ingredients more easily than such waters in USA.

I do wonder how probable it might be to find brewers in UK with water similar to, or worse than, yours? Very few, if any, I would guess. How many hopeful brewers in USA are faced with water even less suitable than yours? Possibly many and maybe from this many budding brewers in UK read American publications to believe that their water has an equally high chance of being unsuitable for brewing.

CRS has been available for many years at UK home brew shops and before that to commercial breweries to reduce alkalinity. Phosphoric acid has also been sold here for years to brewers for general cleaning purposes and at higher concentration to control bacterial contamination of yeast, but there is now demand from those following American advice for reducing alkalinity. A recent comparison between phosphoric and hydrochloric acids reducing alkalinity in my water was inconclusive, but I strongly advise anyone to avoid using phosphoric acid for this purpose until they are fully conversant with brewing using CRS, hydrochloric or sulphuric acids. What phosphoric does is dependent upon the water concerned and the amount of alkalinity reduction and the outcome will likely vary by location. This is not the case with those acids used in UK for well over a century. Not every water treated with phosphoric acid will sediment calcium, but some, or even possibly most calcium involved in that reaction may not be available to play vital roles in the brewing process. The use of phosphoric to reduce alkalinity and their unpredictable outcomes might be in some part the reason why RO is popular in USA, as well as some terrible water profiles.
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Re: Phosphoric and ascorbic acid for alkalinity reduction.

Post by orlando » Thu Jun 18, 2020 10:19 pm

Interesting stuff Eric and a useful reminder that US experiences of water and their solutions to brew with it is not necessarily transferable here. Looking at SIM's water profile RO looks absolutely essential and explains the interest in using systems like that unsurprising. Unfortunately I am losing count of the number of British brewers who are equipping themselves with this largely unecessary piece of equipment because of what they read in articles and forum posts over there.
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Re: Phosphoric and ascorbic acid for alkalinity reduction.

Post by Silver_Is_Money » Sun Jul 12, 2020 5:57 pm

I revisited the Palmer/Kaminski "Water" book's charts for acidification with Phosphoric Acid with respect to how many mg/L Ca++ ion you can keep in solution before your waters Calcium will precipitate out.

For the specific case of source water with an initial pH of 8.0 and a targeted pH of 5.5 via acidification with Phophoric Acid, and presuming that I'm reading the charts correctly, here is how much Ca++ you can maintain in solution for various initial mg/L Alkalinities (as CaCO3):

1) For water with 50 mg/L initial Alkalinity, Calcium precipitates out at and above ~420 mg/L, leaving 420 mg/L as the upper limit for Ca++ in solution
2) For water with 100 mg/L initial Alkalinity, Calcium precipitates out at and above ~180 mg/L, leaving 180 mg/L as the upper limit for Ca++ in solution
3) For water with 150 mg/L initial Alkalinity, Calcium precipitates out at and above ~110 mg/L, leaving 110 mg/L as the upper limit for Ca++ in solution
4) For water with 200 mg/L initial Alkalinity, Calcium precipitates out at and above ~78 mg/L, leaving 78 mg/L as the upper limit for Ca++ in solution

Water with an initial pH lower than 8.0 will hold a bit more calcium in solution, and water with an initial pH above 8.0 will hold somewhat less in solution. But not significantly.

If you target a lower pH than 5.5 the calcium you can keep in solution when acidifying with Phosphoric Acid increases dramatically. The flip side is that if you target a pH above 5.5 things get way worse in a hurry. But by 5.2 pH as the target the values improve dramatically, and look like this:

1) For water with 50 mg/L initial Alkalinity, Ca precipitates out at and above ~1,260 mg/L, leaving 1,260 mg/L as the upper limit for Ca++ in solution
2) For water with 100 mg/L initial Alkalinity, Ca precipitates out at and above ~1,100 mg/L, leaving 1,100 mg/L as the upper limit for Ca++ in solution
3) For water with 150 mg/L initial Alkalinity, Ca precipitates out at and above ~780 mg/L, leaving 780 mg/L as the upper limit for Ca++ in solution
4) For water with 200 mg/L initial Alkalinity, Ca precipitates out at and above ~500 mg/L, leaving 500 mg/L as the upper limit for Ca++ in solution

Moral of the story: If you are going to acidify your water with Phosphoric Acid, target a water pH of 5.2 or lower and you should be fine.

Everything rests upon my having interpreted the charts correctly. Please verify if I have done so. Don't shoot the messenger.

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Re: Phosphoric and ascorbic acid for alkalinity reduction.

Post by Eric » Tue Jul 14, 2020 1:34 pm

Hi Silver, It would seem you have correctly interpreted what you read. I don't accept it, that book read more like a poison manual than an aid to brewers and brewing.

I had this same conversation recently with another British brewer who seemingly understood that irrelevance as you presumably do. pH of brewing liquor is not relevant, the quantity of alkalinity is relevant. There is no single value of pH that determines quantity of alkalinity or its end point.

Take deionised water, assumed as pure water. It has no alkalinity, in theory it will be pH 7. Left open to the atmosphere its pH will rise as CO2 is absorbed, but its alkalinity remains unchanged. Almost any interferrence will change its pH, even when trying to measure its pH.Consider a very small amount of alkalinity added to that deionised water, then a similarly small amount of phosphoric acid added to react with and eliminate that alkalinity.. At what pH would that end point be? I'll suggest a long way above pH 5.5, yet my tapwater at pH 5.5 has over 40 mg/l alkalinity as CaCO3.

My water typically arrives at pH 6.9 with alkalinity around 250 mg/l as CaCO3. In a recent determination of the end point of alkalinity of a sample found it to be at pH 4.43. My water's alkalinity is adjusted using CRS, hydrochloric, or sulphuric acid to a pre-determined level to produce the required beer. Now imagine adding phosphoric acid to my water with 95 ppm caclium in accordance with those tables. Calcium will precipitate as it passes through pH 5.5, then it goes back into solution when it reaches pH 5.2?

I'd like any who advocate using phosphoric acid to provide a chemical analysis of hard and alkaline (typical British) water treated with it to a level of alkalinity suitable for brewing a British Pale Ale. I've never seen one that had been analysed.
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Re: Phosphoric and ascorbic acid for alkalinity reduction.

Post by Silver_Is_Money » Tue Jul 14, 2020 2:15 pm

You bring up good points Eric!

Clearly anyone targeting a specific alkalinity value higher than that required to bring ones water rapidly to ~pH 5.2 or less should be highly wary of using Phosphoric Acid whereby to do so, as a loss of calcium to precipitate in the form of Calcium Apatite is what is highly likely to be expected for that case. And also as you indicate, clearly alkalinity and pH valuations as to quantity do not directly correlate when water pH values are above about an upper limit of not much higher than ~pH 5.5. But quantity correlation indeed becomes better as the waters pH drops, such that by pH 4.3 (and below) alkalinity effectively ceases to be present.

I don't know the answer to the dilemma you pose wherein calcium that first drops out of solution at or above 5.5 pH when hit with initial Phosphoric Acid, is then asked to somehow magically go back into solution when at around pH 5.2 or less after being hit with additional Phosphoric Acid. Chemical equations do have "reversibility" arrows with certain parameters attached to them, so conceivably the precipitation reactions reversal arrow may get longer as pH drops below 5.5, driving the calcium back into solution, but as you have stated, factual testing would be required for verification that the calcium goes back into solution, as well it may or may not, and until such testing is done all is merely speculation.

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Re: Phosphoric and ascorbic acid for alkalinity reduction.

Post by Silver_Is_Money » Wed Jul 15, 2020 1:13 am

All that this would require is to acidify high alkalinity and high calcium water with Phosphoric Acid only until the precipitate forms. Then after the precipitate settles add additional Phosphoric Acid to hit pH 5.2, stir, and observe if the precipitate goes away.

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Re: Phosphoric and ascorbic acid for alkalinity reduction.

Post by Eric » Wed Jul 15, 2020 1:59 pm

Silver_Is_Money wrote:
Wed Jul 15, 2020 1:13 am
All that this would require is to acidify high alkalinity and high calcium water with Phosphoric Acid only until the precipitate forms. Then after the precipitate settles add additional Phosphoric Acid to hit pH 5.2, stir, and observe if the precipitate goes away.
To be perfectly frank, I'm disinclined to do more than ask those who reduce alkalinity with phosphoric acid if they know its effects. Does it produce monocalcium phosphate, dicalcium phosphate or tricalcium phosphate and what exactly is left behind as it apparently releases one of its three hydrogen ions? Does this mean H2PO4 is in the beer, or what? It's potentially possible each variant of natural water might produce different salts and residues such that what might be beneficial for one water might have a vastly different outcome in another.

After 100 years of controlling alkalinity with hydrochloric and sulphuric acids we find ourselves being told by US brewers, who cannot get CRS, not to use it as it can increase chloride content to >100 ppm. But we know what our water treatment does and phosphate content of British beers is a fraction of the 700/800 ppm phosphates in some commercial US beers by analysis, the excess assumed the residue of phosphoric acid.

I have phosphoric acid, obtained for acid washing of yeast and other cleaning purposes. I've used it to reduce alkalinity, but do not care as much for the resultant beers as those from my normal water treatment.

We should not assume the end point of alkalinity is at pH 4.3, although for many practical purposes it can be good enough. Assume the pure water with a very small amount of alkalinity added to raise its level above zero, to then neutralise it with acid. That will happen long before pH 4.3 is reached. Soft water will likely have an end point higher than pH 4.3. Accordingly there can be no fixed pH for treating sparge liquors to produce equivalence in different waters. It is a misguided assumption.
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