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Author Topic: Dichlor/Bleach method  (Read 8022 times)

Bigralphy

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Dichlor/Bleach method
« on: July 15, 2015, 10:25:26 pm »
Hey all,

I have just did a fresh refill and currently have a pH of 7.6, TA of 90, calcium at 180 and FC at 5.

I have added enough dichlor to have approx 17.5 ppm of cya so I need a little more.

I have added Beachcomber Soft which the msds sheet specifies has boric acid in it so I should have some borates, just not sure how much.

My csi is currently .07.  Should I try to get my ta lower yet or just leave as is?

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Dichlor/Bleach method
« on: July 15, 2015, 10:25:26 pm »

chem geek

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Re: Dichlor/Bleach method
« Reply #1 on: July 16, 2015, 04:23:14 am »
If you want to use the Dichlor then Bleach method then you need to get your TA level substantially lower before you switch to using bleach.  This is because Dichlor is net acidic when accounting for chlorine usage/consumption while bleach is not.  So you need the TA lower at around 50 ppm to lessen the amount of carbon dioxide outgassing.

As for Beachcomber Soft, this MSDS says it is 60-100% boric acid so you could assume it's around 80% for calculating Borates.  Just use Boric Acid in PoolMath to calculate dosing.

Bigralphy

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Re: Dichlor/Bleach method
« Reply #2 on: July 19, 2015, 12:50:50 am »
Sound good.

Numbers are now
ph-7.8
CH-150
TA-50
CYA-28
FC-6

I was wondering if these numbers will cause equipment failure.  They are quite far off manufacturer recommendations. 

chem geek

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Re: Dichlor/Bleach method
« Reply #3 on: July 22, 2015, 02:58:47 am »
No they won't.  Metal corrosion is caused primarily by acidic conditions (low pH), not by a low calcite saturation index.  A technical discussion about this is in this link.  When you are using bleach, the pH will tend to rise so a lower TA helps prevent that since TA is a source of rising pH from carbon dioxide outgassing.  When you are using Dichlor it will lower TA so be careful.  You may need to add more baking soda to maintain the TA.  For every 10 ppm FC added by Dichlor, it will lower TA by 3.5 ppm when the chlorine is used/consumed.

Sam

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Re: Dichlor/Bleach method
« Reply #4 on: July 22, 2015, 04:01:58 pm »
No they won't.  Metal corrosion is caused primarily by acidic conditions (low pH), not by a low calcite saturation index.  A technical discussion about this is in this link.  When you are using bleach, the pH will tend to rise so a lower TA helps prevent that since TA is a source of rising pH from carbon dioxide outgassing.  When you are using Dichlor it will lower TA so be careful.  You may need to add more baking soda to maintain the TA.  For every 10 ppm FC added by Dichlor, it will lower TA by 3.5 ppm when the chlorine is used/consumed.

Not to hijack the thread, but I went to that link and found that it was way over my head.  Can you talk a little about that in laymen's terms?  As a hot tub industry guy, we were always trained that low calcium hardness or total hardness would make the water more corrosive.  It appears that you are saying that is not true.  Pretty much all owner's manuals will tell you not to use soft water to fill the spa.  I know that I have read a little about that not necessarily being the case, but would like to understand a little better.

chem geek

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Re: Dichlor/Bleach method
« Reply #5 on: July 23, 2015, 03:16:43 pm »
The lack of calcium carbonate saturation of the water is bad for plaster/gunite/grout surfaces because it will tend to dissolve the calcium carbonate from those surfaces.

Dissolving of plaster and corrosion of metal are two completely different things.  The theory that saturating the water with calcium carbonate will prevent metal corrosion is not practical nor consistent.  The idea is that you coat the metal with a thin layer of calcium carbonate scale, but that is very hard to do in a spa when the water is not always flowing through the pipes (i.e. the pump is on and off) and the temperature is varying a lot (i.e. the gas heater goes on and off).  It's much worse to saturate the water, fire up the heater, and get scale in the heater that builds up as that will lower heat conductivity and burn out the heater.

Tap water is typically very soft yet it isn't corroding the copper pipes in your house.  My tap water only 55 ppm Calcium Hardness (CH), 80 ppm Total Alkalinity (TA), a pH of 7.7, and a temperature of 67ºF so has a saturation index of around -0.7 which should be "corrosive" according to pool and spa industry lore.  It isn't.  The water company does add 300-500 ppb orthophosphate to reduce corrosion, but the soft water itself is not "corrosive".  Metal corrosion comes from oxidizers in the water such as dissolved oxygen and chlorine, but is mostly affected by low pH.  Keeping the pH from falling is the best way to prevent metal corrosion.  This is because metal such as copper, aluminum, and stainless steel all form oxide passivity layers (coatings) that inhibit further corrosion.  Low pH is most disruptive to these coatings, except that high chloride levels can interfere with stainless steel's passivity layer especially when sulfates are present but that's more of an issue in saltwater chlorine generator pools than in spas (even saltwater chlorine generator spas tend to use lower salt levels around 2000 ppm compared to 3000 ppm in pools).

In order to reduce foaming, one would normally have 120-150 ppm CH anyway and in this particular poster's example of his water, the calcite saturation index is only -0.3 at 90ºF so not that low anyway and when the water is 104ºF, in the gas heater when on the temperature at the heat exchanger is around 134ºF so the saturation index would be around 0.0.

So focus more on making sure the pH doesn't drop too much.  This is one of the reasons that Trichlor pucks aren't usually used in spas.  It's not just that they dissolve too quickly, since that could be addressed with special feeders, but rather that it's too easy to overdose and have the pH drop too much in the spa and that then causes significant damage.  Even Dichlor is net acidic and will use up TA, but at half the rate of Trichlor so tends to be safer.  Also, Dichlor's net acidity (when accounting for chlorine usage/consumption) helps balance the pH rise from carbon dioxide outgassing.  Again, focus on pH and not letting it get too low.

Of course, there are manufacturer's warrantees to consider so you might as well add calcium to cover that and to reduce foaming anyway.  As for other levels like TA, you can't follow the manufacturer's typical 80+ ppm recommendation for that and have stable pH when using bleach or even sometimes Dichlor if you've got lots of aeration.  So that's a conundrum.  Do what's right chemically or follow the manufacturer's recommendation to not void the warrantee.
« Last Edit: July 24, 2015, 04:15:11 pm by chem geek »

Sam

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Re: Dichlor/Bleach method
« Reply #6 on: July 23, 2015, 03:25:54 pm »
Thank you for the detailed response.  You are a great resource!!  :)

chem geek

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Re: Dichlor/Bleach method
« Reply #7 on: July 24, 2015, 04:29:36 pm »
I should add that the orthophosphate added to reduce corrosion is not to prevent pipe breakage or leaks but rather to reduce even small dissolution of metal into drinking water, especially lead from lead solder in piping (some older pipes had lead in them as well).  It also reduces the amount of leeching of copper though usually those levels aren't very high and the copper limit for drinking water is 1.3 mg/L compared to lead at 0.015 mg/L (15 µg/L).  See this paper for more info on how orthophosphates reduce leeching of lead into water systems.

Bigralphy

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Re: Dichlor/Bleach method
« Reply #8 on: July 25, 2015, 01:33:03 am »
Thanks chem geek

I appreciate it

Quickbeam

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Re: Dichlor/Bleach method
« Reply #9 on: July 25, 2015, 12:20:48 pm »
The lack of calcium carbonate saturation of the water is bad for plaster/gunite/grout surfaces because it will tend to dissolve the calcium carbonate from those surfaces.

Dissolving of plaster and corrosion of metal are two completely different things.  The theory that saturating the water with calcium carbonate will prevent metal corrosion is not practical nor consistent.  The idea is that you coat the metal with a thin layer of calcium carbonate scale, but that is very hard to do in a spa when the water is not always flowing through the pipes (i.e. the pump is on and off) and the temperature is varying a lot (i.e. the gas heater goes on and off).  It's much worse to saturate the water, fire up the heater, and get scale in the heater that builds up as that will lower heat conductivity and burn out the heater.

Tap water is typically very soft yet it isn't corroding the copper pipes in your house.  My tap water only 55 ppm Calcium Hardness (CH), 80 ppm Total Alkalinity (TA), a pH of 7.7, and a temperature of 67ºF so has a saturation index of around -0.7 which should be "corrosive" according to pool and spa industry lore.  It isn't.  The water company does add 300-500 ppb orthophosphate to reduce corrosion, but the soft water itself is not "corrosive".  Metal corrosion comes from oxidizers in the water such as dissolved oxygen and chlorine, but is mostly affected by low pH.  Keeping the pH from falling is the best way to prevent metal corrosion.  This is because metal such as copper, aluminum, and stainless steel all form oxide passivity layers (coatings) that inhibit further corrosion.  Low pH is most disruptive to these coatings, except that high chloride levels can interfere with stainless steel's passivity layer especially when sulfates are present but that's more of an issue in saltwater chlorine generator pools than in spas (even saltwater chlorine generator spas tend to use lower salt levels around 2000 ppm compared to 3000 ppm in pools).

In order to reduce foaming, one would normally have 120-150 ppm CH anyway and in this particular poster's example of his water, the calcite saturation index is only -0.3 at 90ºF so not that low anyway and when the water is 104ºF, in the gas heater when on the temperature at the heat exchanger is around 134ºF so the saturation index would be around 0.0.

So focus more on making sure the pH doesn't drop too much.  This is one of the reasons that Trichlor pucks aren't usually used in spas.  It's not just that they dissolve too quickly, since that could be addressed with special feeders, but rather that it's too easy to overdose and have the pH drop too much in the spa and that then causes significant damage.  Even Dichlor is net acidic and will use up TA, but at half the rate of Trichlor so tends to be safer.  Also, Dichlor's net acidity (when accounting for chlorine usage/consumption) helps balance the pH rise from carbon dioxide outgassing.  Again, focus on pH and not letting it get too low.

Of course, there are manufacturer's warrantees to consider so you might as well add calcium to cover that and to reduce foaming anyway.  As for other levels like TA, you can't follow the manufacturer's typical 80+ ppm recommendation for that and have stable pH when using bleach or even sometimes Dichlor if you've got lots of aeration.  So that's a conundrum.  Do what's right chemically or follow the manufacturer's recommendation to not void the warrantee.


Hi Chem Geek,

I hope as well that I’m not hijacking this thread, but given what you’ve said about PH, I had a question for you. In my situation, I need to drop my TA to 30 to prevent the PH from spiking with aeration. I do that, and I use borates to try and lock everything in, but with the TA at 30 my PH does tend to slowly drift down. Usually about once per week or so I add about 1/2 to 1 ounce of borax and then the PH comes back to where it should. The trouble is that our tub is at a summer cabin, and while we are present full time during the summer, in the winter we can be away for 2 to 3 weeks at a time. In this time period the PH can drift down quite low. My PH tester (Taylor test kit) does not measure below 7.0, but from the colour of the sample the PH definitely gets lower than 7. I asked my dealer about it as I thought maybe I should leave the TA at 40 or 50 during the winter to hopefully prevent the PH from drifting down. The trouble with this of course is that if we then use the tub and turn on the jets the PH will spike way up. The dealer however told me that he thought having the PH too high would be worse than having it too low. It was his opinion that the components in todays spas, with things like Titanium heaters, etc., would not be that susceptible to corrosion. So, given that I’m not able to lock my PH in where it stays in one spot, in your opinion is it worse to have the PH drifting too high or too low? Thanks Chem Geek.

chem geek

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Re: Dichlor/Bleach method
« Reply #10 on: July 28, 2015, 03:12:14 am »
You know, that's a really tough question to answer because your dealer is right that scaling in the spa can be a real problem, especially in the gas heater heat exchanger because such buildup causes lower heat transfer so the exchanger heats up and can cause temperature to rise in the heater and burn components out.  Some heaters have detectors to shut down when internal temps get high, but generally having a lot of scale isn't good.

And yes, IF the heater is made of cupro-nickel or especially if it's titanium then it's much more resistant to corrosion from low pH.  Even when the pH "crashes" if you exhaust your carbonate buffer system, it will generally get into the 3's but not much lower at least not very quickly.  So while not good, it's not like Muriatic Acid with it's pH of -1.  If you had a copper heat exchanger and this condition lasted for months, then that wouldn't be good.

At 50 ppm TA with 30 ppm CYA and 50 ppm Borates, the equilibrium pH is actually only 7.9 so carbon dioxide outgassing should stop at that point and should slow down considerably below that.  So while you are seeing the pH shoot up towards 8.0, I suspect it's not actually going much above that.  The Calcite Saturation Index even at 8.0 with 50 ppm TA and 30 ppm CYA and 50 ppm Borates and 150 ppm CH and hot temperatures is still negative at nearly -0.3 so I think the risk of scaling is small.  The borates in particular will slow down the pH rise as the pH goes higher since the buffer gets stronger at higher pH (see pH Buffer Capacity for more details).

So on balance I think it's better for you to raise the TA for the winter and since you will be away you shouldn't be having lots of aeration anyway.

Quickbeam

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Re: Dichlor/Bleach method
« Reply #11 on: July 28, 2015, 11:27:17 am »
Thanks ChemGeek,

Much appreciated. Just so you know, I do not use chlorine as a sanitizer. Not sure if you remember, but I'm the fellow whose wife has some serious chemical sensitivities, so we use hydrogen peroxide. Not sure if this makes any difference to your opinion? Thanks again for your response.

chem geek

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Re: Dichlor/Bleach method
« Reply #12 on: July 28, 2015, 12:01:36 pm »
The analysis doesn't change with hydrogen peroxide since it is not net acidic.  Also, how are you going to maintain a disinfectant level in the spa when you are away for weeks?  Does the hydrogen peroxide last that long?

Quickbeam

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Re: Dichlor/Bleach method
« Reply #13 on: July 28, 2015, 12:17:00 pm »
We are usually away for a couple of weeks, maybe three weeks maximum, at a time. We just up the dosage of the H2O2 in the tub and it does fine. I find that in the summer, with no bather load in the tub, it uses about 15 ppm H2O2 per day. In the winter, with no bather load, the tub uses about 8 ppm per day. Those are rough figures, but they are pretty close.

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Re: Dichlor/Bleach method
« Reply #13 on: July 28, 2015, 12:17:00 pm »

 

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