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Thread: Chem_Geek: Heeeeeeelllllllpppppppp!!!

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  1. #1
    chem geek is offline PF Supporter Whibble Konker chem geek 4 stars chem geek 4 stars chem geek 4 stars chem geek 4 stars
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    Default Re: Chem_Geek: Heeeeeeelllllllpppppppp!!!

    Thiosulfate is supposed to reduce chlorine directly and not form combined chlorines. There are many possible reactions, but one of them is the following:

    Na2S2O3•5H2O --> 2Na+ + S2O3(2-) + 5H2O

    2S2O3(2-) + HOCl --> S4O6(2-) + OH- + Cl-

    There are other reactions that take the thiosulfate all the way to sulfate or even sulfur, but I believe these are less likely. None of them form combined chlorine -- all produce chloride ion. The oxidation potentials are as follows:

    2S2O3(2-) --> S4O6(2-) + 2e- ..... Eo = -0.08V

    S2O3(2-) + 6OH- --> 2SO3(2-) + 3H2O + 4e- ..... Eo = +0.571V
    2x( SO3(2-) + 2OH- --> SO4(2-) + H2O + 2e- ) ..... Eo = +0.93V
    --------------------------------------------------------------------------
    S2O3(2-) + 10OH- --> 2SO4(2-) + 5H2O + 8e- ..... Eo = +1.501V

    The above reaction would result in the following with chlorine:

    S2O3(2-) + 6OH- + 4HOCl --> 2SO4(2-) + 5H2O + 4Cl-
    or equivalently
    S2O3(2-) + 4HOCl + H2O --> 2SO4(2-) + 6H+ + 4Cl-
    Thiosulfate Ion + Hypochlorous Acid + Water --> Sulfate Ion + Hydrogen Ion + Chloride Ion
    or
    S2O3(2-) + 4OCl- + H2O --> 2SO4(2-) + 2H+ + 4Cl-

    which is very acidic. My experience from using thiosulfate drops in high chlorine (but < 10 ppm so as to not significantly affect the pH test directly) water and its affect on the pH test is that the reaction is alkaline, not acidic, so I believe these latter reactions don't occur. If we calculate actual oxidation potential for the 8 electron reaction then RT/nF = 8.314472*300/(8*96485.3415) = 0.00323 while ln(10^(14-7.5)^10) = -149.7 so the actual E = +1.501 - 0.00323 * 172.7 = 1.502 - 0.483 = +1.019V. This is still a very likely reaction so perhaps the rate of the reaction is slow (high activation energy?).

    Richard
    Last edited by chem geek; 07-09-2007 at 02:59 AM.

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    LexPlayer is offline ** No working email address ** LexPlayer 0
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    Default Re: Chem_Geek: Heeeeeeelllllllpppppppp!!!

    Quote Originally Posted by chem geek View Post
    Thiosulfate is supposed to reduce chlorine directly and not form combined chlorines. There are many possible reactions, but one of them is the following:

    Na2S2O3•5H2O --> 2Na+ + S2O3(2-) + 5H2O

    2S2O3(2-) + HOCl --> S4O6(2-) + OH- + Cl-

    There are other reactions that take the thiosulfate all the way to sulfate or even sulfur, but I believe these are less likely. None of them form combined chlorine -- all produce chloride ion. The oxidation potentials are as follows:

    ................

    Richard
    Between your post and the chemical anlayis on this page, my eyes have gone buggy!

    If Professional Pool Operators of America (PPOA) is correct, I would think that Sodium Sulfite is a better option than Sodium Thiosulfate beause there is no free Sulfur floating around "sulfinating" the water up.

    I assume the Sodium sulfate (or Glauber's salt, sodium sulfate decahydrate, Na2SO4·10H2O per wikipedai) is just diluted into the water.

    Anyway, I still don't know what my chlorine level is, but I'm trying to find a DPD test kit locally.

  3. #3
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    waterbear is offline Lifetime Member Sniggle Mechanic waterbear 4 stars waterbear 4 stars waterbear 4 stars waterbear 4 stars
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    Default Re: Chem_Geek: Heeeeeeelllllllpppppppp!!!

    Do yourself a favor and forget the DPD kit and get an FAS-DPD kit. It's easier, more accurate, and can test much higher chlorine levels with an accuracy as great as .2 ppm!
    Retired pool store and commercial pool maintenance guy.

  4. #4
    CarlD's Avatar
    CarlD is offline SuperMod Emeritus Vortex Adjuster CarlD 4 stars CarlD 4 stars CarlD 4 stars CarlD 4 stars CarlD 4 stars CarlD 4 stars
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    Default Re: Chem_Geek: Heeeeeeelllllllpppppppp!!!

    Evan's right--you are just wasting money--and you'll have to get a FAS-DPD test kit sooner or later anyway.

    DPD only goes to 15ppm before it bleaches out--looking like you have NO chlorine!
    Carl

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