Another Salifert 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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Aleman
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Re: Another Salifert question

Post by Aleman » Mon Feb 12, 2018 10:36 am

Carnot wrote:
Mon Feb 12, 2018 7:27 am
I can understand the confusion that some people are having with hardness determinations and alkalinity. The term hardness came about from soap manufacturers and the use of steam in industry. Hardness is normally defined in terms of temporary and permanent hardness, which is usually assumed to be due to calcium and magnesium salts. In simple terms most hardness in potable water is due to carbonates, usually existing as bicarbonate.
And right there is where you have introduced the confusion. Hardness is due to the presence of calcium and magnesium ions in the water NOT carbonate species, It is NOTHING to do with carbonate/bicarbonate ions. YES hardness is most likely to be associated with carbonate/bicarbonate ions, and referred to, badly, as temporary hardness

Personally I think it's important to make a distinction between hardness (calcium and magnesium ion levels) which is good for brewing, and alkalinity (carbonate species and hydroxide ions), which is not really required in brewing at all. When yo start bringing imprecise terms from other industries into the mix confusion will occur.

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Re: Another Salifert question

Post by sonicated » Mon Feb 12, 2018 5:03 pm

orlando wrote:
Mon Jan 29, 2018 8:14 am
For those who just want to know what to do, keep the alkalinity of your mash to come out between 5.2 - 5.6.
Do you mean pH?

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Re: Another Salifert question

Post by orlando » Mon Feb 12, 2018 5:20 pm

sonicated wrote:
Mon Feb 12, 2018 5:03 pm
orlando wrote:
Mon Jan 29, 2018 8:14 am
For those who just want to know what to do, keep the alkalinity of your mash to come out between 5.2 - 5.6.
Do you mean pH?
It is ambiguous, but I meant reduce your alkalinity so that the mash pH comes out to between 5.2 - 5.6
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Re: Another Salifert question

Post by Carnot » Tue Feb 13, 2018 8:31 am

Aleman, Not sure what problems that you have with English but I specifically said that that hardness is assumed to be due to Ca and Mg ions( though other trace ions will also behave similar). There must be a balance between cations(+ve) and anions (-ve). Therefore take my own water

Total Hardness 240 ppm (CaCO3)

Calcium Hardness 230 ppm (CaCO3)

Alkalinity 190 ppm (CaCO3)

Chloride 38 ppm (as CaCO3)

From this you can deduce the following

Ca 92 ppm ( as Ca)

Alkalinity 114 ppm ( as bicarbonate)

Mg 2.5ppm (as Mg)


In this case the levels of sulphate will be quite low as the chloride content and alkalinity content amount to 230. So to treat this water to match the much desired Burton water would need some alkalinity reduction possibly a small addition of calcium sulphate. It can therefore be assumed that the hardness in my water is almost entirely due to carbonates, as bicarbonate, otherwise known as temporary hardness. I also expressly referred to potable water.


If I wanted to split hairs I would say that bringing the term hydroxide ions into the discussion has little merit. Free hydroxide will only exist above pH 8.4, far above brewing pH limits and would quickly absorb CO2 from the air to form carbonates, which is why free hydroxide is rarely seen in potable water ( I have never found it present). For reference this would be termed the O alkalinity in water treatment, but has no relevance in brewing , in my opinion. Likewise P alkanility is an exception in potable water.

I trust that this answer you objection.

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Re: Another Salifert question

Post by Aleman » Wed Feb 14, 2018 2:41 pm

Carnot wrote:
Tue Feb 13, 2018 8:31 am
Aleman, Not sure what problems that you have with English
Neither am I, but I'll just leave this here from your original post on this thread.
Hardness is normally defined in terms of temporary and permanent hardness, which is usually assumed to be due to calcium and magnesium salts. In simple terms most hardness in potable water is due to carbonates, usually existing as bicarbonate.
So you tell me, is hardness due to calcium and magnesium ions, or is it due to carbonate (bicarbonate) ions??

Water with a high level of sodium bicarbonate foams well with a standard soap solution, and does not form a scum, so is classed as 'soft' A water with a high level of calcium carbonate doesn't foam anywhere near as well with a standard soap solution, and forms scum being classed as hard ... as the anion is the same in the two cases, it is logical to assume that the 'hardness' is due to the cation, not the anion.

I am fully aware that the ions do not exist on their own in nature, and must be balanced, but I'm also fully aware that carbonate (bicarbonate) is not desired in brewing and calcium is, and they can be considered separately, as the levels are measurable with reasonable accuracy, for brewing purposes, with Salifert alkalinity and calcium test kits.

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Re: Another Salifert question

Post by Carnot » Wed Feb 14, 2018 7:51 pm

Aleman, you clearly have a problem with anything I say. Hardness, permanent or temporary is due to calcium and magnesium cations in solution. Temporary hardness is assumed to be due to calcium and magnesium ions precipitating from solution as the carbonate due to bicarbonate ion decomposition. At elevated temperatures bicarbonate ions will progressively decompose. The carbonate thus formed exceeds the solubility limit of calcium carbonate or chalk (something like 30 ppm) and precipitates. If there is a high heat flux surface it will tend to precipitate and dehydrate to form a scale (ie. kettle element). Magnesium will behave in a similar manner. Permanent hardness is due to calcium and magnesium ions associated with sulphates and chlorides anions.

As I stated earlier, typically the majority of hardness in many potable waters is due to temporary or carbonate hardness ( carbonate hardness is an accepted term). In another post you describe the issues with gypsum (calcium sulphate) addition to brew liquor. Gypsum is more soluble than calcium carbonate but less soluble than calcium bicarbonate under typical surface water conditions( there are exceptions). Chlorides are always more soluble than sulphates or carbonates which explains why sea water is highly saline.

More temporary hardness is typically seen in potable waters due to the fact that when carbon dioxide dissolves in rain water it reduces the pH which if it comes into contact with limestone (calcium carbonate) the weakly acidic rainwater is neutralised by forming calcium barcarbonate and the pH will rise to about 7- 7.5, buffering the water. If you do a mass balance the calcium ion concentration will often be close to the alklanity (which is sometimes called carbonate alkalinity. Total alkalinity and carbonate alkalinity are defined differently but under conditions where the pH is below 8.2 can be assumed to be the same (within 1%). Due to the lower solubility of calcium sulphate the levels of permanent hardness in potable waters are typically less than temporary hardness, but as ever there are exceptions.

Quite rightly the presence of calcium ions in brew liquor is highly desirable, alkalinity less so due to it buffering effect. Weak acids, such as carbonic ( and phosphate) form salts that will buffer or oppose a change of pH. Strong acids, such as sulphuric will not form salts with the same buffering capability. Sulphates also tend to impart sour taste which might be preferred at lowish concentrations but objectionable at higher levels. So the famous Burton water has a moderate -high calcium ion loading which is balanced by sulphate ions, which have little or no buffering capacity and allows the mash liquor pH to fall to the desired range of 5.2-5.6, whatever your preference. This can be achieved by the simple addition of sulphuric acid which will decompose the bicarbonate ion.

In the old days earlier water softening involved adding lime to precipitate calcium carbonate, followed by soda (sodium carbonate) to precipitate the residual temporary hardness ( which also forms calcium carbonate). The lime-soda softening process . Nowadays softening is done by base ion exchange, full demineralised ion exchange or by reverse osmosis. There is also a process for alkalinity reduction by ion exchange - hydrogen ion base exchange.

The Salifert alkalinty test kit can be used to give an approximation of calcium temporary hardness as well as alkalinity. The calcium test kit will provide a more accurate determination, especially where gypsum addition is used. In many cases if your water contains significant alkalinity the only treatment necessary might be to add sufficient acid ( sulphuric/hydrochloric) to affect the necessary alkalinity reduction. On that I think we are in total agreement

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Re: Another Salifert question

Post by Aleman » Wed Feb 14, 2018 8:46 pm

I don't have issues with what you are saying, merely the way you are saying it. The term hardness is confusing, mainly due to it's use on water reports where it's quoted "As CaCO3" inexperienced people see that and assume because they see the CaCO3 that it is alkalinity, and use that value incorrectly in 'water calculators'.

I try and avoid introducing confusion using the term hardness, either temporary or permanent, when talking about brewing liquors as it is more appropriate, and indeed less confusing, to talk about calcium and magnesium levels (less so magnesium as it's a trace element for yeast and probably adequately supplied by malt if not at a reasonable level in the liquor), along with carbonate (bicarbonate), sulphate and chloride. For those of us who are more fully conversant with the intricacies of water chemistry then the risk of confusion is less, but for those without that knowledge, and for brewing it's not really essential (*), looking at such a discussion does lead to confusion.


(*) the exception being someone trying to decipher a chapter on water treatment from a less modern brewing book, and getting completely confused :D

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Re: Another Salifert question

Post by Eric » Wed Feb 14, 2018 9:29 pm

guypettigrew wrote:
Mon Jan 29, 2018 10:22 am
Thanks everyone--really grateful for all the input. So, the Salifert 'hardness' kit doesn't test hardness. Fine, got that now! I'll assume the water softener is doing its job.

As to beer making---no problem. I use hard water which has been tested by Wallybrew, and Eric has provided loads of useful advice. I'm now able to reduce the alkalinity to whatever I want, up the calcium to about 150 and manipulate the sulphate:chloride ratio. Since learning how to do this, the quality of my beer has significantly increased.

Thanks again.

Guy
Hi Guy, pleased you got sorted. Hardness is confusing and best avoided at all cost. It is more especially so with an ion exchange water softener. Feed it with some natural water that contains what can be confusingly called temporary hardness and that particular component will be changed to something that we could call soft and permanent.

More confused? Of course. It's just as well brewers can avoid such terms. What went in, brewers can easily and sufficiently accurately measure with a Salifert kit and call alkalinity. As you found, that same kit would again correctly measure that same amount of alkalinity after being processed, even though it can't be called hard and no longer temporary.

Don't go there Guy, it just makes what can be simple, a shambles.
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Re: Another Salifert question

Post by Carnot » Thu Feb 15, 2018 8:23 am

Aleman, The whole reason why water chemists reports as CaCO3 is down to keeping things simple. Calcium carbonate has a molecular weight of 100 which makes it very convenient for calculations. Standard tests for alkalinity, total hardness and calcium hardness were typically made using standard 0.02N (0.01M) solutions of titrants. When it came to making the calculation reporting as CaCO3 was like using a common currency. Remember this was before the days of calculators. I know because I ran thousands upon thousands of these tests and keeping it simple made it fast. Thus taking the calcium hardness test result( as CaCO3) and converting it into actual calcium involved a simple multiplication by 0.4 (mole weight calcium). Likewise the alkalinity could be used to pretty accurately see if most of the calcium was present as bicarbonate. Take my own water and the alkalinity is just below the calcium which means that most of the calcium is associated with bicarbonate. If you want know the carbonate concentration then multiply by 0.6.If you wanted to know how much acid to add to reduce the alkalinity this is also possible, with a pretty simple calculation that does not require a degree in maths.

If you report as specific ion concentration then life is a little more complicated and you would have to think a little more, and know a bit more about water chemistry reaction mechanisms. Water company tests are invariably as the specific ion in mg/L and you are now lucky if they report alkalinity at all. Mine does not.

I am all for keeping things simple. Water chemistry does not have to be complicated at all. It is just few people make it very complicated and unfortunately there are several ways in which test results are reported. I can work with most units but I guess that I am the exception rather than the rule.

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Re: Another Salifert question

Post by Aleman » Thu Feb 15, 2018 8:33 am

Why calculate something from a water 'report' that has a limited number of readings, and describes an 'average' value along with min and max values (within the limited number of samples), when you can directly measure the actual value with a couple of tests that take around 5 minutes total. You know then you are working with real values and not some hypothetical value.

As for keeping it simple.

1) Measure alkalinity and calcium
2) Adjust alkalinty to that appropriate for style (colour), using appropriate acid
3) If required add an additional 75mg/l calcium

For the vast majority of beer styles, water supplies and brewers in the UK that is all that needs to be done, where is the degree in maths?

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Re: Another Salifert question

Post by Carnot » Fri Feb 16, 2018 12:44 am

Aleman, What make you think I use the water company report. Go back several posts. Total Hardness, Calcium and Alkalinity are dead easy especially if you have auto burettes; check these parameters and then adjust to suit your brew. The only reason I look at the water company report is for trace materials and contaminants (nitrate and heavy metals), as well as to get some idea of the Ca and Mg range. My water company posts results every six months. Is there anything else that you wish to have the last say on. My previous post was to try and explain why many results are posted as CaCO3- it obviously did not register.

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Re: Another Salifert question

Post by Eric » Fri Feb 16, 2018 1:01 am

Carnot wrote:
Fri Feb 16, 2018 12:44 am
Aleman, What make you think I use the water company report. Go back several posts. Total Hardness, Calcium and Alkalinity are dead easy especially if you have auto burettes; check these parameters and then adjust to suit your brew. The only reason I look at the water company report is for trace materials and contaminants (nitrate and heavy metals), as well as to get some idea of the Ca and Mg range. My water company posts results every six months. Is there anything else that you wish to have the last say on. My previous post was to try and explain why many results are posted as CaCO3- it obviously did not register.
"Go back several posts" you say. Might I suggest you do similar with Aleman's postings, over six thousand of them and read the multitude of favourable responses while your on. I've read your 41 and advisedly suggest you may wish to review them too.
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Re: Another Salifert question

Post by Wonkydonkey » Fri Feb 16, 2018 6:17 am

What have I stumbled on here..two different guys who understand water but in different ways, err I think this is brewing school, But, like maths, there can be more than one way to get the same answer. And I think it has been said somewhere before on more than one occasion,KISS. even if you think kiss in a totally DIFFERENT way, its how others see it
Btw mr carnot i think you made some mistakes in some of your ramblings :shock: but I just skimmed over.
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