Question about Carbonate reducing solution

[Silver_Is_Money]

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One should also keep in mind that we don't really know whether sulfuric/hydrocloric acids are indeed the only ingredients. They are the only ones listed in the SDS because they have a known toxicity. If there are any salts such as CaCL2 in the mix we wouldn't find them listed there since they have no known toxicity. Again, personally I'd be wary of using any water additive I don't know the exact composition of, considering that mixing up your own ingredients is very easy, offers you greater control and is probably cheaper as well if you buy them in bulk and without a fancy name.

I'd be a bit more inclined to believe that the tested lot came up a wee bit short of 3.66 mEq/mL in acid strength off the manufacturing line, so a small amount of additional HCl (only) was added to bring it right up to the targeted strength. This small adjustment had the dual effect of slightly elevating the Cl- ion content and slightly suppressing the SO4-- ion content. In either case no error greater than 1% was found within my presumptions. I'd call that a big win for their validity.

 

[cire]

I've found a couple of earlier .pdf files for AMS, but unsure if they will upload with this posting. They have.

The product predates decimalisation in UK and conversion from earlier units have consistently incurred some errors.

The company has supplied water treatments to breweries since 1887.

 

[Silver_Is_Money]

I've found a couple of earlier .pdf files for AMS, but unsure if they will upload with this posting. They have.

The product predates decimalisation in UK and conversion from earlier units have consistently incurred some errors.

The company has supplied water treatments to breweries since 1887.

It seems from this much earlier era's CRS Tech Sheet that at one time CRS was noticeably a bit stronger than it is today. Closer to perhaps around 3.83 mEq/mL Acid Strength on an admittedly rapid fire check.

 

[Silver_Is_Money]

I wonder if at some juncture the manufacturer of AMS made the decision to reduce and thereby normalize its acid strength more closely to that of 30% Phosphoric Acid and thereby arrive at 3.66 mEq/mL, or if it is merely a fluke and random occurrence that the two are so close in mEq/mL acid strength today?

A worst case scenario would be that more than one manufacturer exists at present, and that the product is not fully 100% the same across different manufacturers, and instead is being sold in somewhat different acid strengths, with somewhat different deliveries of chloride and sulfate ions thereby.

 

[Silver_Is_Money]

A similar concentration situation exists of course for Lactic acid and Phosphoric Acid. Some 88% Lactic Acid tests out at 90% or so as to concentration, and I've seen test reports on 85% Phosphoric Acid showing it to be on the high side of 86%.

 

[cire]

A similar concentration situation exists of course for Lactic acid and Phosphoric Acid. Some 88% Lactic Acid tests out at 90% or so as to concentration, and I've seen test reports on 85% Phosphoric Acid showing it to be on the high side of 86%.

Absolutely and the more you delve, the greater the disparity. With regularity I read here acid strengths expressed in percentage terms. But are those W/W, W/V, V/V or V/W and whatever so, at what temperature? I ignor all such values to prefer Molar or Normal at 20C, but am probably behind the times.

Incidentally, could the reason of UK use alkalinity and US preferring pH for adjustment be explained by the acids in general use. For a recent comparative mini-mash test with my water treated with phosphoric and hydrochloric acids, 2 equal volumes were titrated to pH 4.46. That particular and equal value was achieved by pure chance and considered as close to zero alkalinity as might be obtained with my table top equipment. Circumstances delayed the next part and both samples were for the next 20 hours left open to air, not under cover as during titration. Resuming the test, pH for that titrated with phosphoric had risen maginally while that with hydrochloric acid was found to read pH 5.16 and contiued to increase.

While I've read here that phosphate has little buffering power when pH is near that for a mash, it would seem by this to have vastly more buffering capacity than chloride and maybe sulphate too.

 

[Silver_Is_Money]

Absolutely and the more you delve, the greater the disparity. With regularity I read here acid strengths expressed in percentage terms. But are those W/W, W/V, V/V or V/W and whatever so, at what temperature? I ignor all such values to prefer Molar or Normal at 20C, but am probably behind the times.

Incidentally, could the reason of UK use alkalinity and US preferring pH for adjustment be explained by the acids in general use. For a recent comparative mini-mash test with my water treated with phosphoric and hydrochloric acids, 2 equal volumes were titrated to pH 4.46. That particular and equal value was achieved by pure chance and considered as close to zero alkalinity as might be obtained with my table top equipment. Circumstances delayed the next part and both samples were for the next 20 hours left open to air, not under cover as during titration. Resuming the test, pH for that titrated with phosphoric had risen maginally while that with hydrochloric acid was found to read pH 5.16 and contiued to increase.

While I've read here that phosphate has little buffering power when pH is near that for a mash, it would seem by this to have vastly more buffering capacity than chloride and maybe sulphate too.

Acid concentrations are (or at least should be) weight/volume. But I agree they should also have 20 degree C. Molarities and/or Normalities listed, as well as pKa's. This has me thinking that one potential reason why AMS/CRS can easily vary in relative acid strength is that no definitive strength or concentration is ever (to my knowledge at least) professed for it.

I have no explanation for the upward creep in pH that your Wort took after being acidified to 4.46 with HCl, other than to speculate that if it was still sitting upon the grist it was still actively combating against the grists pH, which presumably was basic with respect to pH 4.46, and had not yet been fully permeated by the HCl while titrating.

Due to pKa1 at pH 2.16 and pKa2 at pH 7.21, Phosphoric Acid should have close to zero ability to buffer at somewhere around pH 4.685, so you are correct to assume little to no buffering for 4.46 pH. Buffering for this acid only begins to noticeably and rapidly resume for it at roughly pH 5.7 and pH 4.1. Between these two values little buffering exists. This is a good reason why phosphate based "5.2" buffers are considered pretty much useless. If I had to guess, I'd presume that they buffer to somewhere above pH 5.7 if they buffer at all.

Of interest is that Phosphoric Acid behaves nearly as if it was monoprotic at most pH's of interest to brewing, so using its Normality as opposed to its Molarity (while simultaneously ignoring pKa's and their impact) would likely lead to huge errors (which perhaps may exist for some earlier M_____ Technical Sheets). But since buffering resumes at around 4.1 pH, beers for which mash water has been acidified with this acid may not fall as low during fermentation as for an identical beer for which CRS (or some other acids) was (were) used. That might be one to research for the younger and more ambitiously energetic among us.

 

[cire]

With all sincerity I can say of all the brewing related acids I've used, none is more consistent than AMS. Many individual acids are supplied at a quoted minimum assay. At one time I had a copy of the manufacturing specification for AMS and will post it here if it is found, but every batch of AMS/CRS I've measured has suggested their QC has always been good. Note too that in UK acid is added to the liquor before mashing, giving chance to check its influence.

For every phosphate ion attaching to calcium when phosphoric acid reduces alkalinity in water, 2 further are added to that liquor. Its buffering power can be three time that initially thought.

No grains were mixed with that titrated water, just water at pH 4.46, but the absorbed CO2 raised pH in that titrated with hydrochloric acid vastly more than that with phosphates rather than chlorides. That from hydrochloric acid acted similarly to DI water with very little buffering ability, vastly less than phosphate at whatever pH. The phosphoric acid treated water did not, an easy test to repeat might you wish.

Before the relatively recent explosion of micro breweries in both nations, UK had significantly more regional breweries than the then forty or so in USA. UK had at least one long established brewing consultancy serving the industry. It would seem from afar no equivalent provision existed in US, else it would be well known to hobbyists and we would see evidence here. Possibly each brewery kept their knowledge secret, while in UK it was a badge of honour when breweries published and spread knowledge through the Institute of Brewing and University courses.

As for what the younger might do, yes. I'm 3 parts of the way to a century.

 

[Silver_Is_Money]

This highly tentative formulation attempt was cobbled together rather quickly and therefore may not be correct, and indeed thereby is seriously in need of being verified, and it would be helpful to that end if a few of you would independently verify this formulations quantities, but it appears that (subject to independent verification) an acid blend along similar lines to CRS might "potentially" be synthesized in a certified chemical lab setting as follows:

For 1 Liter:
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151.54 mL of 37% HCl (certified food grade)
49.77 mL of 98% H2SO4 (certified food grade)
Sufficient verified DI water, or alternately, high quality distilled water to achieve a 1,000 mL final volume. RO water is not good enough!!!

Alternate For 1 Liter:
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179.91 mL of 32% HCl (certified food grade)
51.62 mL of 95% H2SO4 (certified food grade)
Sufficient verified DI water, or alternately, high quality distilled water to achieve a 1,000 mL final volume. RO water is not good enough!!!

Caution, Warning, and Disclaimer: These are seriously dangerous and hazardous acids at maximum strength concentrations. Do not attempt this (post independent verification) at all unless you absolutely know what you are doing and have had training in the proper handling of these acids. Period!!! Use all imaginable safety related PPE equipment and precautions, seek or apply all necessary ventilation, and never add water to acid. This is far and away best attempted in only a full chemical laboratory setting.

 

[Silver_Is_Money]

OK, lets begin the proof process for the chosen quantities in the primary formula as seen in post #39 above, to see if we get 'TRUE' computational matches to the presumptions and derived values as seen primarily in posts #27 and #29 above.

Initially we will look at Sulfuric Acid, which I had previously determined must lead to an acid strength of 1.83 mEq/mL and 87.90 mg/L SO4-- in our blend.

Givens:
MW : H2SO4 = 98.07848
Density of 98% Sulfuric Acid = 1.84 g/mL
MW : SO4--- = 96.0626
Valence = 2

First we will calculate the Molarity of 98% Sulfuric Acid in units of mmole/mL:
1000 mL x (98% x 1.84 g/mL)/98.07848 = 18.385 moles/L = 18.385 mmole/mL

Next we will convert this into normality in units of mEq/mL:
Valence x Molarity = Normality
2 x 18.385 mmole/mL = 36.77 mEq/mL

Next we will apply this formula:
Volume1 x Normality1 = Volume2 x Normality2

Therefore:
49.77 mL x 36.77 mEq/mL = 1,000 mL x Normality2
1,830.04/1000 = 1.8304 mEq/mL
= 1.83 mEq/mL (rounded) Acid Strength = TRUE

Next we must determine the mg/L of SO4-- that 1 mL of our solution of 49.77 mL of concentrated H2SO4 when diluted to 1L delivers:
49.77 mL x 1.84 g/mL x 98% = 89.745264 g of H2SO4
89.745264 g x 96.0626/98.07848 = 87.90 g SO4-- ions
And when 87.90 g of SO4-- ions are added to 1 Liter of water, one gets 87.90 g/L
And when 1 mL of this solution is extracted and added to 1L of water one delivers thereby 87.90 mg/L = TRUE

Lastly we will look at Hydrochloric Acid, which I had determined must lead to an acid strength of 1.83 mEq/mL and 64.88 mg/L Cl-in our blend.

Givens:
MW : HCl = 36.46094
Density of 37% Hydrochloric Acid = 1.19 g/mL
MW : Cl- = 35.453
Valence = 1

First we will calculate the Molarity of 37% Hydrochloric Acid in units of mmole/mL:
1000 mL x (37% x 1.19 g/mL)/36.46094 = 12.076 moles/L = 12.076 mmole/mL

Next we will convert this into normality in units of mEq/mL:
Valence x Molarity = Normality
1 x 12.076 mmole/mL = 12.076 mEq/mL

Next we will apply this formula:
Volume1 x Normality1 = Volume2 x Normality2

Therefore:
151.54 mL x 12.076 mEq/mL = 1,000 mL x Normality2
1,829.997/1000 = 1.829997 mEq/mL
= 1.83 mEq/mL (rounded) Acid Strength = TRUE

Next we must determine the mg/L of Cl- that 1 mL of of our solution of 151.54 mL of concentrated HCl when diluted to 1L delivers:
151.54 mL x 1.19 g/mL x 37% = 66.723062 g of HCl
66.723062 g x 35.453/36.46094 = 64.88 g Cl- ions
And when 64.88 g of Cl- ions are added to 1 Liter of water, one gets 64.88 g/L
And when 1 mL of this solution is extracted and added to 1L of water one delivers thereby 64.88 mg/L = TRUE

Again I ask for your assistance in verifying all of the above.

 

[Silver_Is_Money]

As I check and re-check this (all of the above) my confidence in it is steadily increasing. I had initially feared my concentrated acid mL calculations whereby to formulate a work-alike for CRS to be orders of magnitude off due to finding this below linked AJ deLange post (Click on 'Crs' in orange below to go to the referenced post, which I also quote below), but now I believe the error lies within the linked post and not within my work as seen above:

https://www.homebrewtalk.com/threads/crs.387641/post-4873866Quote:

To 950 mL of DI water add 0.051 mL 96% sulfuric acid and 0.148 mL 23 Be' hydrochloric acid. Make up to 1 L.

AJ deLange

 

[Silver_Is_Money]

Based upon a thread in a UK forum it appears that AMS/CRS is not likely quite equinormal as has often been presumed here in the States, as the speculation in the UK forum is that it is produced via making up 20 Winchesters of concentrated H2SO4 and 60 Winchesters of concentrated HCl to 1,000 Liters with water.

Per Wikipedia a standardized Winchester is 2.5 Liters.

Using my HCl and H2SO4 blends calculator and the UK speculation and my best guesses as to the analyticals for the two concentrated acids I've derived the following:

The H2SO4 components strength is nominally ~1.84223 mEq/mL (vs. my earlier equinormal presumption of 1.83)
The HCl components strength is nominally ~1.81307 mEq/mL (vs. my earlier equinormal presumption of 1.83)
The combined overall acid strength is ~3.6553 mEq/mL (vs. my earlier presumption of 3.66)
1mL added to 1 Liter of DI water contributes ~88.4844 mg/L (ppm) of SO4-- ions
1mL added to 1 Liter of DI water contributes ~64.2788 mg/L (ppm) of Cl- ions

To make up 1 Liter:
50 mL of 98% H2SO4
150 mL of 37.2% HCl
DI Water to 1 Liter of total volume
(CAUTION and WARNING: never never never add water to acid!!! It will immediately boil and splash/splatter!!!)