Combimate water "softener"—opinions?

[jack]

24 minutes ago, JSHarris said:

the precipitate is not going to want to stay as aragonite for long - it will want to revert to calcite. 

 

Would aragonite crystal revert to calcite directly, or would it dissolve back into solution from where it re-precipitates out as calcite (assuming the relevant conditions are present)? 

[Jeremy Harris]

2 minutes ago, jack said:

 

Would aragonite crystal revert to calcite directly, or would it dissolve back into solution from where it re-precipitates out as calcite (assuming the relevant conditions are present)? 

 

It's metastable, so in the presence of water, at standard temperature and pressure, it will want to revert to calcite.  If kept dry, or otherwise artificially stabilised (for example by high concentrations of magnesium) it can remain as aragonite, but these aren't conditions likely to be found in domestic water systems.

[Polly]

Aragonite is formed inside the device. It happens in the time that the water takes to pass through, using yes JSHarris, kinetic energy combined with the alloyed fins.

The effects last for 21 days, (bit harder to maintain in a kettle), then revert to Calcite.

 

Yes Jack, I will send you the tests.

 

No, JSHarris, I will not get into a debate about the laws of the company's advertising. I provide part time product support, and that really is outside of my responsibility. I'm here to explain the product, not the company. I'm sure you'll appreciate that really is not the role of a provider of Product Support.

 

[Jeremy Harris]

On 21/08/2018 at 11:30, Polly said:

Aragonite is formed inside the device. It happens in the time that the water takes to pass through, using yes JSHarris, kinetic energy combined with the alloyed fins.

The effects last for 21 days, (bit harder to maintain in a kettle), then revert to Calcite.

 

Yes Jack, I will send you the tests.

 

No, JSHarris, I will not get into a debate about the laws of the company's advertising. I provide part time product support, and that really is outside of my responsibility. I'm here to explain the product, not the company. I'm sure you'll appreciate that really is not the role of a provider of Product Support.

 

 

 

So, the device actually causes calcium ions in the water to precipitate out in the device, well outside normal precipitation conditions, from the combination of the catalysts and the kinetic energy from the water flowing through the device?

 

Given that the water downstream of the device will still be a reasonably good solvent for CaCO₃ in any form, what stops the metastable precipitate so formed from simply going back into solution?  The solubility of CaCO₃ (it matters not which polymorph, they are all the same as far as water solubility is concerned) is around 8 to 12mg/ml, or around 8 to 12µg/l, so even in very hard water there is still going to be plenty of spare solution capacity for the water to dissolve the prematurely precipitated out CaCO₃ before it reaches saturation point.  The implication is clear; although carbonates are no where near as soluble in water as bicarbonates, there is still plenty of capacity within the downstream water flow to re-dissolve the prematurely precipitated out CaCO₃, in any form, so what stops this from happening?

 

 

[Polly]

19 minutes ago, JSHarris said:

The solubility of CaCO₃ (it matters not which polymorph, they are all the same as far as water solubility is concerned) a

 

No they're not. Aragonite is around 50% more soluble than Calcite.

 

Nothing precipitates inside the unit itself; hence its 30 year lifespan and warranty.

[Jeremy Harris]

39 minutes ago, Polly said:

 

No they're not. Aragonite is around 50% more soluble than Calcite.

 

Nothing precipitates inside the unit itself; hence its 30 year lifespan and warranty.

 

 

Good point, and one I hoped that you would pick up (I'd already made it in an earlier post, in reply to @jack and was, I admit, waiting to see if you would pick up on it, as it makes my point even more powerfully).  We know that aragonite dissolves more readily in water than calcite, as aragonite is metastable, and thermodynamically it wants to revert to a lower energy state form of CaCO₃, so what stops the aragonite that has been forced to artificially form, from the action of water flow supplied kinetic energy and the catalyst in your device, from dissolving straight back into the water in the pipework after the device and so becoming disassociated calcium ions, or perhaps dissolved bicarbonate, ready to precipitate out again as CaCO₃ when the conditions are right? 

 

[Jeremy Harris]

As this discussion is getting a bit technical, I thought it might help to state a few facts with regard to how calcium (and magnesium, although that's not the subject of this particular discussion) gets into drinking water in the first place.

 

In the UK, almost all of it comes from rainwater that flows through limestone or chalk (both forms of calcium carbonate, CaCO₃).  As the water percolates through these rocks, it dissolves CaCO₃ and the water then contains calcium (and magnesium) in solution.  There is therefore abundant evidence that what we call hard water; water that contains calcium (and magnesium) in solution, obtained that calcium by dissolving CaCO₃ from the rock layers it passed through.

 

Another basic principle is that any solution that becomes saturated with a dissolved compound, will readily start to precipitate out that compound under the right conditions.  A good example would be a glass shower screen in a hard water area.  The water droplets left on it start to dry out, and as they do the concentration of Ca²⁺ cations starts to increase and carbonates start to form in each droplet, to the point where there is not sufficient water available to maintain the carbonates in solution.  The result it at around the edge of each droplet solid carbonates start to form (both calcium and magnesium carbonates, but usually mainly calcium carbonate, CaCO₃).  Once the whole water droplet has dried out all that is left behind is the total dissolved solids within it, usually a mix of several compounds, but predominately CaCO₃ in hard water areas.

 

The same effect can be seen anywhere that the concentration of dissolved compounds in the water gets highly concentrated, so areas around shower, sink and basin drains, the ends of taps (where droplets evaporate away) are all places where CaCO₃ will precipitate out.

 

Run enough water over any such area of precipitated CaCO₃ and it will dissolve back into solution, as long as the water isn't already saturated.  Leave water sitting, or flowing, over CaCO₃, dissolves it; it's the way the majority of caves in the UK have been formed.  Most limestone caves start out as solution caves, where static, or very slowly moving, water just dissolves away the CaCO₃ (limestone), forming solution chambers.  Eventually these solution chambers may join up, through natural fissures in the limestone, and then water may start to flow more quickly.  The rate at which CaCO₃ is dissolved depends to some extent on the rate of flow of fresh water over it, so once passages have opened up to form underground streams the rate at which the CaCO₃ starts to dissolve increases pretty rapidly (in geological terms) and these caves get larger and larger.

 

They will carry on getting bigger for as long as fresh water flows through them, sometimes getting so large that they become structurally unsound and collapse.  These collapses may be seen on the surface as sinkholes, and in limestones areas their formation increases the rate at which the CaCO₃ dissolves, as the depressions they cause tend to cause surface streams to divert and run down into the underground cave network, so providing more fresh water to dissolve more CaCO₃.

 

The main point about the above stuff about dissolving CaCO₃ is to illustrate that it's the way that we get hard water.  It's not a coincidence that hard water is associated with limestone or chalk geology, and areas where other forms of geology predominate (Cornwall and areas of Scotland, to give but two examples) have naturally soft water.  The reason is simply because their drinking water is not drawn from aquifers where the source water has flowed through, and dissolved, CaCO₃ and so become "hard".

 

I hope the above helps explain where I'm coming from in terms of asking for an explanation as to why CaCO₃ that has somehow been made to come out of solution prematurely, in the form of aragonite, is able to remain as a fine precipitate despite the indisputable fact that the water carrying it is a pretty good solvent for CaCO₃ and would fairly readily just dissolve it again and take it back into solution, exactly as it was before the sort of "catalytic" water treatment device described in the latter part of this thread.  I may well have forgotten most of the stuff I learned when I did my first degree in physical chemistry, but the basics regarding solubility are really at best O level chemistry; there's nothing even vaguely complex here, with the possible exception of the way that calcium and magnesium themselves remain in solution once the original carbonates in the rock that contained them have been dissolved.

[Polly]

2 hours ago, JSHarris said:

(it matters not which polymorph, they are all the same as far as water solubility is concerned)

 

1 hour ago, Polly said:

No they're not. Aragonite is around 50% more soluble than Calcite.

 

1 hour ago, JSHarris said:

Good point, and one I hoped that you would pick up (I'd already made it in an earlier post, in reply to @jack and was, I admit, waiting to see if you would pick up on it,

 

Right.

 

[jack]

2 hours ago, Polly said:

Yes Jack, I will send you the tests.

 

Thanks for that. In my opinion, the document you supplied isn't evidence that would be accepted by anyone with a scientific background. Science aside, it involves a test (not "tests") that happened over 30 years ago, and the original documents upon which it is based are very unlikely to be available for cross-checking. 

 

If others are interested, I'm sure they can ask for your document themselves.

 

2 hours ago, Polly said:

No, JSHarris, I will not get into a debate about the laws of the company's advertising. I provide part time product support, and that really is outside of my responsibility. I'm here to explain the product, not the company. I'm sure you'll appreciate that really is not the role of a provider of Product Support.

 

The Advertising Standards Authority doesn't care what your job title is. If you're making laudatory statements about your company's products in such a way as to encourage people to buy them, then you're advertising, end of.

 

As for aragonite formation, I know my chemistry knowledge is pretty weak, but these two posts seem to contradict each other:

 

2 hours ago, Polly said:

Aragonite is formed inside the device.

 

1 hour ago, Polly said:

Nothing precipitates inside the unit itself; hence its 30 year lifespan and warranty.

 

Which is it? As I understand it, aragonite is a crystalline solid, hence must be a precipitate. If "Aragonite is formed inside the device", it must therefore "precipitates inside the unit itself", surely? If not, how else is aragonite formed inside the device? 

 

This is a fairly simple question that still hasn't been addressed despite having been asked by different posters in different ways.

[Cpd]

48 minutes ago, JSHarris said:

As this discussion is getting a bit technical, 

Thanks @JSHarris I did not even try and get the relevant O levels to understand this technically and was definatly getting lost ! 

Everyday is a school day on this forum ! 

[Polly]

Ok, my apologies if my explanation hasn't been clear. Aragonite is created in the water's solution during its pass through the Halcyan unit. CaCO3 goes into the unit in Calcite form, and emerges in Aragonite form.

The Aragonite stays suspended in solution in the water in one's system and washes through your system with the rest of the water.

 

[richi]

11 minutes ago, jack said:

Which is it? As I understand it, aragonite is a crystalline solid, hence must be a precipitate. If "Aragonite is formed inside the device", it must therefore "precipitates inside the unit itself", surely? If not, how else is aragonite formed inside the device? 

 

Bzzt. Unfair. While there may be a strict definition of the verb "precipitate" you're thinking of, in my mind, @Polly says the Aragonite is formed in suspension and 100% of it exits the device (as opposed to some of it staying in there and clogging it up).

[richi]

4 hours ago, jack said:

 

Are you saying that your product provides "softer water" without softening? Surely that's internally inconsistent?

 

Bzzt. Unfair. The phrase used is "the benefits of ... softer water" (emphasis mine).

[jack]

14 minutes ago, richi said:

Bzzt. Unfair. While there may be a strict definition of the verb "precipitate" you're thinking of, in my mind, @Polly says the Aragonite is formed in suspension and 100% of it exits the device (as opposed to some of it staying in there and clogging it up).

 

I disagree that I've said or done anything unfair. @Polly told us earlier that she has a scientific background, so I assume that when she refers to a "colloidal suspension", she knows what that means. A colloidal suspension of aragonite comprises crystalline solids in water, so everything I've said on that point applies. 

 

@Polly has had several opportunities to correct my understanding, and/or clarify or add to her own statements about this. She's chosen not to. 

 

11 minutes ago, richi said:

Bzzt. Unfair. The phrase used is "the benefits of ... softer water" (emphasis mine).

 

[Edited this section a bit after posting] No, not unfair. You've posted their quote plus my first sentence. The very next thing I said was: "And if your answer is that this phrasing is intended to involve a comparison with actual soft water rather than implying you're doing any softening, then in my opinion this sentence intentionally misleads through the use of "softer" instead of "soft"."

 

I think the language intentionally misleads the reader to think that the water is being softened, rather than this being a comparison with softened water. That's my reasoned opinion, which I understand you might disagree with. I don't, however, think I've said anything unfair. Again, @Polly chose not to address this point.

 

What about this, on the page you end up at if you click on "Domestic" from the home page:

 

 

 

Seems pretty unequivocal to me.

All that said, I posted a page or two ago that they may actually meet at least one definition of "soft" water. So why do they keep pushing the "we don't soften, we condition" line? Do they soften, as they say in the quote above, or do they condition but not soften, as they repeatedly emphasise elsewhere in this thread?

 

I just want unambiguous language and straight answers to straight questions. If you think that's unfair, cool.

[Polly]

8 minutes ago, jack said:

Again, @Polly chose not to address this point.

 

Here you go, Jack:

 

We condition, not soften.

 

I don't choose the wording on the website.

 

We do not soften water.

 

I think that's relatively unambiguous.

[richi]

OK, OK, "unfair" was harsh, sorry. But a layman like me knew what she meant by "precipitate" in that context. As for the other uses of the word "soft", "softened", "softer", etc.—you got 'er banged to rights guv'nor, an' no mistake.

 

I'd just prefer it if we kept the discussion centred on a spirit of collegial enquiry, that's all. It's not as if any of us is likely to plonk down a grand for these magic beans, but it would be wonderful if we could come to a reasoned conclusion—rather than to have this discussion come to a screeching halt because @Polly concludes we're... I dunno... trolling her? 

[Dreadnaught]

 

22 minutes ago, richi said:

it would be wonderful if we could come to a reasoned conclusion

 

What conclusion can we reasonably foresee? Are we expecting Polly to say something like: "Oh yes, I see what you mean now and the error of my ways. I will resign from my role at this company forthwith and cease the promotion of pseudo science"? 

 

I suspect that we have heard all that Polly has to say on this subject, shallow as her contribution has been, and we are in to repetition and the necessity of evasion. Or am I mistaken?

Edited August 21, 2018 by Dreadnaught

[jack]

Just now, Polly said:

We do not soften water.

 

I think that's relatively unambiguous.

 

Yes, it is.

 

However, I can't see why the fact that you don't personally choose the website wording is relevant. One way or the other, your company is contradicting itself.

 

1 minute ago, richi said:

But a layman like me knew what she meant by "precipitate" in that context.

 

If you know what she means, then can you please explain it to me?

 

I understand what you mean by the desirability of keeping it collegiate. I'd prefer that option myself, but we've now had pages of dialogue without a straight answer to some pretty fundamental questions.

 

I'd actually love it if it were shown properly that this system works, because that would mean that there's clearly something we don't understand about the chemistry of water and dissolved minerals. It would also mean an opportunity for getting most of the benefits of softened water without the cost of salt and the environmental impact of wasted water used for regeneration.

 

4 minutes ago, Dreadnaught said:

I suspect that we have heard all that Polly has to say on this subject, shallow as her contribution has been, and we are in to repetition and the necessity for evasion. Or am I mistaken?

 

I think you're probably right. This is about the fifth time I've responded where I've thought "that's it, if there isn't a straight answer this time, I'm out"!

[HerbJ]

15 minutes ago, Polly said:

Here you go, Jack:

 

We condition, not soften.

 

I don't choose the wording on the website.

 

We do not soften water.

 

I think that's relatively unambiguous.

 

So, are you now stating unequivocally that the wording on the HALYCAN website is incorrect and misleading, potentially making false claims about the production of soft water?  Surely, there has to be a connection between advertising/sales and the product support functions in your company?  Who checks the advertising claims?

 

On another point, it seems to be admitted that the water produced by this device, will revert back to original form in 21 days?? Is this detailed in the Manufacturer's Instructions with a warning/recommendation to flush the system if it is noted for this period of time?  Is this period just an estimate or has it been tested to verify this period?

[Jeremy Harris]

1 hour ago, Polly said:

Ok, my apologies if my explanation hasn't been clear. Aragonite is created in the water's solution during its pass through the Halcyan unit. CaCO3 goes into the unit in Calcite form, and emerges in Aragonite form.

The Aragonite stays suspended in solution in the water in one's system and washes through your system with the rest of the water.

 

 

 

Dissolved calcium doesn't exist in hard water as ready-formed carbonate of any form, but as calcium ions, Ca²⁺ .  Hence the reason that an ion exchange column can swap out calcium ions (Ca²⁺⁾ for sodium ions (Na⁺) that the ion exchange medium has already been pre-charged with, leaving the water pretty much calcium free.

 

So, although we know that calcium (and magnesium) rich waters obtained their calcium from dissolving calcium and magnesium carbonates, they don't contain carbonates in solution as such, but rather as calcium and magnesium ions.

 

This is the fundamental problem I have with your statement that:

 

Quote

Aragonite is created in the water's solution during its pass through the Halcyan unit. CaCO3 goes into the unit in Calcite form, and emerges in Aragonite form.

 

This is flawed basic chemistry.  CaCO₃ doesn't exist, as such, in the water, as it has been dissolved, it is not in suspension, or held as some form of colloid.  Dissolved literally means that the CaCO₃ has been broken down to it's constituent elements within the water, in this case Ca²⁺ cations.  The actual solution reaction is this one, and it relies on rainwater that is the start of our drinking water cycle containing dissolved CO₂ (which it does, CO₂ is, as we all know from fizzy drinks, readily soluble in water):

 

CaCO₃ + H₂O + CO₂  ↔  Ca²⁺ + 2HCO₃^-

 

As is transparently clear from the above reversible reaction, the calcium in solution (the right hand side of this equation) is not in the form of CaCO₃, in any of its polymorphs, it only exists as Ca²⁺ cations in solution.  You can reverse this reaction readily to get CaCO₃ out of solution, this is what happens when the precipitation criteria are met, but this reversal does not take place in normal cold water pipework, so the water flowing into your device does not contain CaCO₃, either as calcite or aragonite, it cannot, unless something ahead of the device has caused the above chemical reaction to reverse, not something that normally happens in domestic cold water supplies***.

 

This is the logic behind the point I made earlier that this "catalytic" unit allegedly uses kinetic energy from water flow to cause CaCO₃ to form as a precipitate in water that is not super-saturated with Ca²⁺ cations (it does not exist as precipitate in the incoming hard water whilst it's in solution in the closed pipe system).

 

I'll ask the same question asked above, as it wasn't answered.  We are agreed that CaCO₃ is readily soluble in water.  We know that, when dissolved it is in the form of Ca²⁺ cations.  We also agree that of two of the forms of solid (precipitate) CaCO₃, calcite and aragonite, aragonite is significantly more soluble in water than calcite.  What process stops the aragonite from being dissolved by the water immediately after the unit and the calcium returning to Ca²⁺ in solution?  How can aragonite exist without being in solution in water that is not saturated?

 

If, for some reason, the incoming cold water supply was super saturated with Ca²⁺ cations, such that CaCO₃ was already precipitating out as calcite, then I can understand how that polymorph could be changed to another, aragonite.  It's a process that happens naturally in some dry caves, producing rather nice crystals on dry surfaces, often referred to as aragonite flowers.  However, drinking water, even in the hardest water areas in the UK, is massively below the saturation limit.

 

 

 

***  There are conditions where CaCO₃ can be forced to precipitate out from water that it not super-saturated with Ca²⁺ cations and which does not become super-saturated as a consequence of drying out.  Local high temperature surfaces can cause it to occur (hence the scale build up on heating elements) for example.

[Polly]

Hello Herb.

 

The company is in the process of rewriting some of the website. Although it does not claim to create soft water, we would like it to be clearer.

 

The system doesn't really come with instructions. There's nothing to instruct, you just fit it and it works. It does come with installation instructions.

It won't do any harm if water is left for longer than 21 days, because in that case, which is unusual anyway, the treated water running through the system afterwards carries out existing limescale deposits over time.

[HerbJ]

7 minutes ago, Polly said:

It won't do any harm if water is left for longer than 21 days, because in that case, which is unusual anyway, the treated water running through the system afterwards carries out existing limescale deposits over time.

 

It's not in the least bit unusual.  Many people spend this time away on vacation, ( I do for one) or it may be fitted to a vacation/2nd  home?. So, the water is now "treated water" and how does this  carry away the limescale deposits? 

[Polly]

Ok well we may differ slightly on how long a normal holiday is, or how common it is to have a second/holiday home, but lovely, lucky you/them. 

 

The treated water carries away limescale deposits because the Aragonite molecules, though they do not bond to surfaces, do bond to their Calcite 'cousins' and carry them out in solution, over time.

 

Edited August 21, 2018 by Polly

[Mr Punter]

So far I think that @Polly has made a decent fist of representing her firm's product, albeit with a lack of evidence on how it actually works.

[Jeremy Harris]

1 hour ago, Polly said:

 

The treated water carries away limescale deposits because the Aragonite molecules, though they do not bond to surfaces, do bond to their Calcite 'cousins' and carry them out in solution, over time.

 

 

 

I'm really confused as to how the heck any form of CaCO₃ is actually in the mains water.  Ignoring all the other elements/compounds for a moment, hard water that only has hardness resulting from calcium, will have the following formula:

 

H₂O + Ca²⁺ + 2HCO₃^-

 

There is no CaCO₃ in the incoming water, so there cannot be any, in any polymorph, in the water leaving your device unless your device somehow causes CaCO₃ to be formed and precipitate out.  It matters not how this formation and precipitation happens, but the fact is that the solubility of CaCO₃ in water is such that it would just dissolve again soon after leaving the unit, and the water would once more turn back to H₂O + Ca²⁺ + 2HCO₃^-

 

I cannot find any evidence anywhere as to how this process of forming CaCO₃ under conditions that are not normally those that would initiate its formation and  precipitation from H₂O + Ca²⁺ + 2HCO₃^-  actually happens.  What's even more puzzling is how the CaCO₃ that is precipitated out of solution in the form of aragonite, isn't then subsequently dissolved again. 

 

Of course it's plain nonsense to suggest that calcite enters the device with the incoming water, it cannot, as mains water that is below super-saturation point doesn't contain any calcite at all.