Sciencemadness Discussion Board

OxiClean vs. Chlorox, the Safest is?

AJKOER - 7-2-2013 at 09:31

After researching the oxidation of Ammonia, I can up with some interestingly, scary and unexpected findings on a particular issue. If one, either intentionally or accidentally mixes ammonia, (NH3 is found in urine,..) and either Chlorox (NaClO, NaCl, Na2CO3,..) or OxiClean (2Na2CO3.3H2O2), which is worst/more dangerous?

With NaOCl and NH3, the known formation of Chloramine, NH2Cl. To quote from a MSDS:

"Inhalation: Causes chemical burns to the respiratory tract. Aspiration may lead to pulmonary edema. May cause systemic effects. May cause respiratory sensitization. Chronic: May cause methemoglobinemia, which is characterized by chocolate-brown colored blood, headache, weakness, dizziness, breath shortness, cyanosis (bluish skin due to deficient oxygenation of blood), rapid heart rate, unconsciousness and possible death. Effects may be delayed."

So NH2Cl is pretty nasty stuff, but to be fair, its corrosive and pungent smell should give one warning to stop breathing and exit to fresh air.

The news is actually worse for Chloramines as further oxidation by NaClO can form NCl3, Trichloramine or Nitrogen trichloride. The latter is a particularly powerful and unstable explosive. So yes, you can, on occasion, blowup at least part of your toilet by mixing Chlorine bleach and ammonia.

Now, for the tale of Oxiclean containing a powerful oxygen compound, Hydrogen peroxide, as part of a solid salt, Sodium percarbonate, formula: 2Na2CO3.3H2O. Now, NH3 and H2O2 react only slowly, but in the presence of Na2CO3 (a catalyst for this reaction) and mild heat (60 C or lower), a reaction occurs. The problem is the formation of Ammonium nitrite, NH4NO2, which Wikipedia characterizes as "acutely toxic". In other words, skin contact with a hot water solution of OxiClean and ammonia can be deadly. Also, a cold water solution allowed to stand for a day or so, could also form the lethal NH4NO2.

And, by the way, if you let the solution sit and get concentrated and/or acidified (Vinegar, SO2, CO2..), you may also can get a bang. The dry form of NH4NO2 is particularly sensitive and powerful explosive.

OK, so on the yardstick of a potential mixing with ammonia, which product Chlorox or OxiClean is the safest?

My vote is neither and if you don't believe any of the above, just read the warning labels on both products.

The good news is that there is room out there for someone to invent a cleaner that doesn't accidentally poison and/or dismembers parts of your body or you.


[Edited on 7-2-2013 by AJKOER]

ScienceSquirrel - 7-2-2013 at 13:33

Fresh urine does not contain ammonia.
The main nitrogenous compiound in mammalian urine is urea and an adult human excretes around 20 - 30 grams a day contained in maybe 1- 2 litres of urine on average.
I suppose that you could make hydrazine by reacting fresh concentrated piss with hypochlorite or maybe chloramine with a good bowl of concentrated stale piss but really I have never heard of a case of a toilet attendant overcome by the fumes from a toilet bowl or being blown up by a toilet bowl filled with trichloramine.
Reaction between ammonia and sodium percarbonate will make some ammonium nitrite but it will rapidly break down to form nitrogen and water.
Warning labels are more ass covering than MSDS. It could never possibly happen but they will warn you about it.
If it does , the lawyers wil have a back stop.

[Edited on 7-2-2013 by ScienceSquirrel]

AJKOER - 7-2-2013 at 16:03

ScienceSquirrel:

I agree that NH4NO2 has a limited life span (in fact, about a 2 hour half-life). However, the reaction between NH3 and H2O2 is slow (days I would speculate), so the controlling issue (danger) may arises from its slow formation, and, correctly as you noted, not from its limited life span.

-----------------------------------
Here is a commentary on the other point (link: http://www.getbig.com/boards/index.php?topic=291387.0 ) most likely from the accidental mixing of ammonia and chlorine bleach:

"Oh my Goodness! you are sooo lucky. coughing and restricted breathing were the least of your worries.
Your toilet could've exploded. I'm not kidding. It could've exploded. It has happened before. Go buy a lotto ticket. "
--------------------------------------------------------

Here is a prior thread comments on the CO(NH2)2, HOCl and NH3 reactions (link: http://www.sciencemadness.org/talk/post.php?action=reply&... ):
Quote: Originally posted by PHILOU Zrealone  
Cl2 + H2O --> HOCl + HCl
NH2-CO-NH2 + HOCl --> NH2-CO-NH3OCl
NH2-CO-NH2 + HCl --> NH2-CO-NH3Cl
NH2-CO-NH3OCl --> NH2-CO-O-NH3Cl --> NH2-CO2H + NH2Cl --> NH3 + CO2 + NH2Cl
NH3 + CO2 + NH2Cl --> HCl + NH2-NH2
NH2Cl is as toxic as Cl2 and NH2-NH2 is bad too!

NH2-NH2 + 2HOCl --> N2 + 2H2O + 2 HCl

The fact Cl2 reacts wel and fast enough with water (which can dissolve it quite wel) in basic media must have saved them.
But Cl2 concentration was not too high... and Cl2 is much less toxic than other cative chlorine containing wargas.

Also if it was unfresh urine, fermentation has started and NH3 solution is then obatined.

NH4OH + Cl2 --> NH4Cl + NH4OCl -->
2NH2-Cl + HOCl --> N2 + 2 H2O + 2HCl
:);):)


Note the formation of Chloramine (NH2Cl) from Urea (CO(NH2)2) itself. No need to wait for old urine to form ammonia.

[Edited on 8-2-2013 by AJKOER]

AndersHoveland - 7-2-2013 at 16:58

The oxidation of ammonia by bleach is a different type of oxidation than oxidation by OxiClean.

Oxiclean basically just contains a form of hydrogen peroxide with a Tetraacetyl ethylenediamine (TAED) activator.

Dr.Bob - 11-2-2013 at 11:58

Mixing household ammonia and chlorox in large quantities can make chloroamine, which is bad for you. But breathing either ammonia or chlorox vapors (Cl2 and chlorine oxides) is also not good for you, so dangers are relative, but chloramine is not good stuff. Oxiclean is mostly sodium percarbonate, which is very mild by itself. That is why it does not harm fabrics as much as Chlorox does, but at the same time, it is not as powerful at removing stains or disinfecting germs as Chlorox is. Again, the more powerful the oxidiant, the more harmful it can be, but also the more useful it is.

But mixing Oxiclean and ammonia is not likely to do much harm, not much worse than breathing ammonia fumes would be. And I don't know many people whose toilet operates at 60C, that would be pretty unusual unless you mixed up the cold and hot water lines. So unless you are purposely mixing chemicals together in huge amounts, Oxiclean is nearly harmless. I never figured out why people like to mix cleaners anyway, most are designed to work fine by themselves, if not, buy a better cleaner to start with, like Chlorox.

Traveller - 14-2-2013 at 17:56

Quote: Originally posted by ScienceSquirrel  
Fresh urine does not contain ammonia.
The main nitrogenous compiound in mammalian urine is urea and an adult human excretes around 20 - 30 grams a day contained in maybe 1- 2 litres of urine on average.
I suppose that you could make hydrazine by reacting fresh concentrated piss with hypochlorite or maybe chloramine with a good bowl of concentrated stale piss but really I have never heard of a case of a toilet attendant overcome by the fumes from a toilet bowl or being blown up by a toilet bowl filled with trichloramine.
Reaction between ammonia and sodium percarbonate will make some ammonium nitrite but it will rapidly break down to form nitrogen and water.
Warning labels are more ass covering than MSDS. It could never possibly happen but they will warn you about it.
If it does , the lawyers wil have a back stop.

[Edited on 7-2-2013 by ScienceSquirrel]


Interestingly, horse urine contains a good portion of ammonia if the horse is fed a diet of high protein alfalfa. Horses get by nicely on a diet of grass hay with a protein content of 6-8%, while some fertilized crops of alfalfa are tested regularly with upwards of 24% protein. These proteins are nitrogen rich compounds. A horse fed a rich alfalfa diet will drink and urinate more frequently than a horse on a grass hay diet.

A horse fed this way for an extended period of time will often develop kidney stones.

[Edited on 15-2-2013 by Traveller]

AJKOER - 16-2-2013 at 20:02

Dr.Bob:

I would not be surprised to find out that you are somehow connected to Oxiclean. Actually, I would be very surprised if you dared to insert your bare hand into a solution of Oxiclean and ammonia that has been sitting in light for a few days. Remember, Ammonium nitrite is "acutely toxic", which I would interpret as it doesn't take a lot to kill.

To be fair, I noticed that the latest write-up in Wikipedia (see http://en.wikipedia.org/wiki/NH2Cl ) on Chloramine (which is a product of an ammonia/Sodium hypochlorite reaction) appears to be written by someone connected to the use of Chloramine for drinking water. Here is an extract, for example, on the only watered down negative comment on NH2Cl:

"NH2Cl also has a very much lower, however still present, tendency than free chlorine to convert organic materials into chlorocarbons such as chloroform and carbon tetrachloride. Such compounds have been identified as carcinogens and in 1979 the United States Environmental Protection Agency began regulating their levels in U.S. drinking water."

Yes, apparently after some lawyers citing possibly bias/incomplete science (my speculation based on my personal interpretation of past actions) have approved its use for water treatment (in some US states, even the swimming pools have an eerie green color of chloramine), its now OK stuff. Also, as people pee in said pools, and kids even swallow it, chloramine can no longer be considered the toxic compound that it is. In my opinion, of course, pure BS. (I wish Wikipedia would make available the old article on NH2Cl, it would scare the s... out of you per my limited recollection).

Fact: Here is a quote from a MSDS on NH2Cl, to quote "Safety Statements: Questionable carcinogen with experimental tumorigenic data. Mutation data reported." Link: http://www.guidechem.com/dictionary/10599-90-3.html

If you like fish, do not read this extract (it will be painful). To quote:

"In the past, aquarists used to let tap water "age" a few days to let the chlorine dissipate into the air. Chloramine, however, is very stable and can not be easily driven off, even by heavy aeration. Chloramine is very toxic to fish. Chloramine, unlike chlorine, passes through the gill tissue causing little damage. Chloramine then enters the bloodstream and binds to iron in the hemoglobin in the red blood cells. The blood is unable to carry oxygen, resulting in a condition called methemoglobinemia, similar to nitrite toxicity. Fish become lethargic, sitting on the bottom or near the surface. At low chloramine concentrations a few fish will die every day. Higher chloramine levels can cause all fish to die within 24 hours." Link: http://www.rena.net/reference-center/articles/article.aspx?a...

Note, the interesting comment for Chloramine "similar to nitrite toxicity". This, in itself, supports an equivalence argument based solely on toxicology between Chloramine and Ammonium nitrite, albeit NH4NO2 being a longer term possible side product of a thermal or photolysis reaction between OxiClean and ammonia.


[Edited on 17-2-2013 by AJKOER]

Dr.Bob - 18-2-2013 at 14:46

Quote: Originally posted by AJKOER  
Dr.Bob:

I would not be surprised to find out that you are somehow connected to Oxiclean. Actually, I would be very surprised if you dared to insert your bare hand into a solution of Oxiclean and ammonia that has been sitting in light for a few days. Remember, Ammonium nitrite is "acutely toxic", which I would interpret as it doesn't take a lot to kill.


I am certainly not connected to Oxyclean. My main point is that it is a weaker oxidant compared to Clorox, which is why is is generally considered safer, but it also DOES NOT WORK as well as Clorox (in most case) for the same reason. A very dilute solution of Clorox will still disinfect many things, make drinking water safe and remove some very dark stains. And remember that Clorox is only about 5-6% of the active ingredient, Sodium hypochlorite. I don't know what percentage of sodium percarbonate the Oxyclean is, so it is hard to compare by amounts, but I'm pretty certain that a $1 bottle of chlorine bleach will do far more oxidizing that $1 worth of Oxyclean.

Oxyclean, and many other cleaning products make money not by being the best cleaning product, but by advertising a lot. I have seen many people believe ads for cleaners that don't understand chemistry and can't figure out what cleaners are best for what uses without understanding even how a detergent works, or the correct amount to use. My wife still thinks that if a little is good, a lot is better, like too many people. I also still have people tell me that vinegar is a good cleaner, and that may be true for alkali based "dirt" like soap scum, hard water deposits, and crusted baking soda, but it is nearly useless on grease and most other residues. The same way that Arm & Hammer claim that baking soda cleans things with magical powers...

Traveller - 18-2-2013 at 18:17

AKJOER wrote:

"In the past, aquarists used to let tap water "age" a few days to let the chlorine dissipate into the air. Chloramine, however, is very stable and can not be easily driven off, even by heavy aeration. Chloramine is very toxic to fish. Chloramine, unlike chlorine, passes through the gill tissue causing little damage. Chloramine then enters the bloodstream and binds to iron in the hemoglobin in the red blood cells. The blood is unable to carry oxygen, resulting in a condition called methemoglobinemia, similar to nitrite toxicity. Fish become lethargic, sitting on the bottom or near the surface. At low chloramine concentrations a few fish will die every day. Higher chloramine levels can cause all fish to die within 24 hours."

Do you know if water disinfected with chloramine has the same effect of the condition methemoglobinemia in humans and other mammals?

AJKOER - 18-2-2013 at 19:43

Traveller:

Actually, I didn't write those comments, I quoted them from the referenced Internet link. As far as I know, the comments are accurate. However, I would welcome the comment of a biochemist to more authoritatively answer your question.

By the way, there appears to be quite a controversy over Chloramines in water and I noticed that this thread has been included in a google search results, so your question deserves an appropriate response.

[Edited on 19-2-2013 by AJKOER]

Traveller - 18-2-2013 at 22:51

I would be very interested as well if someone was able to give us an answer. I operate a small water system in our town of 450 people and we are required by law to sterilize and disinfect our water prior to delivery to our customers. Sterilization is achieved with UV and we inject sodium hypochlorite for disinfection.

While we do not use monochloramine for disinfection, there are enough organics and nitrogen in our water to lead to the formation of odouriferous di- and tri-chloramines (not sure if we have mono-chloramine as it has no smell, so I'm told). Of course, our health board here in northern British Columbia tells us the chloramines are just a smelly nuisance and not to worry about them. They said much the same thing about the trihalomethane levels in our water I tested at 122 ppb (Health Canada limits THM's to 100 ppb and the EPA in USA limits them to 80 ppb). Needless to say, my confidence in health boards directed by budget conscious governments has reached an all time low.

I hope someone educated on this subject reads our posts.

[Edited on 19-2-2013 by Traveller]

AJKOER - 20-2-2013 at 08:47

Not an expert in water purification, but I would recommend O3 (ozone) treatment. Chemically speaking, O3 is more powerful oxidizer than Cl2 (or hypochlorites, hypochlorous acid, chloramine,..) without the undesirable side products. Disadvantage cost and, unlike NH2Cl, it quickly (and safely) dissipates with the release of oxygen. Chloramine (which I don't like as a dilute dose of a mutagen is still a mutagen) does have an advantage in this regard in that, absent any SO2, one just cannot easily get rid of it. So, upon a new microbe invasion the NH2Cl will still be there, but with weaker disinfectant power. The ozone treated water should still have a higher O2 content in cold water, which may be of some protection upon re-contamination.

Now, ozone generators are energy intensive, but perhaps solar power to the rescue. More investment upfront, but no more monthly outlays for NaOCl.

A property of applying O3 to water rich in Iron, as Fe(HCO3)2, ( also Manganese as Mn(HCO3)2 see http://www.eolss.net/Sample-Chapters/C07/E6-192-06-00.pdf ) is that the salt will be oxidize to Fe(OH)3. Note, Ferric hyroxide is a gelatinous precipitate commonly employed as a coagulant in water purification.

I would not be surprised, in spite of the chemistry, of some opposition on suggesting O3, so get approval first. I would imagine, however, with education local community support could be obtained.

Good luck, I hope my comments help, and please excuse me if I decline to drink your current water.


[Edited on 20-2-2013 by AJKOER]