While you were on the subject of chlorine and its toxicity (and especially given the illustration) you should have mentioned the way people commonly poison themselves with the stuff; by using chlorine bleach in conjunction with ammonia, in an attempt to get things cleaner than using either substance alone. The combination, I’ve been told, liberates deadly chlorine gas. Of course, I haven’t tried this at home, for obvious reasons, but I think it’s true…
Well, write a message that says that it’s true. But don’t send it. Then get some chlorine and some ammonia. Sit next to the computer with your finger over the submit reply button then with the other hand, mix the two chemicals & breathe. Then when you fall over due to it’s toxicity your finger hits the submit button and we all know its true [as if we didn’t already].
Speaking of making chlorine gas at home, my dad used it once to kill a gopher. He had a gopher that was eating the roots of his rose bushes and generally undermining the back yard. He went through the usual genesis of trying to run it off “humanely”, trap it alive, and trap it dead, but none of these worked. Finally he blocked up all the holes except two, poured in whatever combination of household ingredients he used at one hole and plugged that one, and then waited at the other hole. When the gopher came out sneezing, he brained it with a shovel. The moral is, chlorine gas combined with a shovel is very dangerous.
Ahhh! And we thought poison gas and trench warfare went out of style back in 1918. Good to know the tradition lives on in America’s backyards.
Actually chlorine gas was first used in 1915, and was generally considered obsolete by 1918 because it had been replaced by more persistent chemical agents, such as phosgene (chlorine mixed with phosphorus). Chlorine gas collects in low places, eg, trenches and foxholes, and is easily water-soluble, so the two easiest antidotes were either (1) get out of yr trench, or (2) breath thru yr cotton undershirt soaked with whatever water was at hand–urine was used in emergencies!
Actually, chlorine gas itself is not particularly water soluble, although it dous react somewhat with water and breathing through a damp shirt might eliminate most of the adverse effects.
Phosgene is not chlorine gas mixed with phosphorus, but is carbonyl dichloride. It is a very powerful alkylating agent (much like mustard gas), and very toxic.
I have to disagree with this one. While I wouldn’t dream of DIRECTLY contradicting Uncle Cece (I sure can’t claim to be the smartest person in the world), I think the implications and subtle side-effects trip him up here. The Sacred Words of Cecil state (and I quote):
“Whatever you do, don’t get the idea that keeping the germ count down is silly or that exposure to bacteria “builds up your resistance” or other such nonsense.”
Perhaps allowing thriving bacterial colonies doesn’t build up your resistance, but it MAY promote the growth of beneficial bacteria. Consider the following approach to eliminating the problem of salmonella:
(basically, using beneficial bacteria to crowd out the harmful salmonella)
Likewise, quoting from Scientific American (at http://www.scientificamerican.com/1998/0398issue/0398levybox1.html):
“There is no evidence that the addition of antibacterials to such household products wards off infection. What is clear, however, is that the proliferation of products containing them raises public health concerns.
“Like antibiotics, antibacterials can alter the mix of bacteria: they simultaneously kill susceptible bacteria and promote the growth of resistant strains. These resistant microbes may include bacteria that were present from the start. But they can also include ones that were unable to gain a foothold previously and are now able to thrive thanks to the destruction of competing microbes. I worry particularly about that second group–the interlopers–because once they have a chance to proliferate, some may become new agents of disease.”
So given this new twist, the Sacred Words of Cecil aren’t wrong (whew, my faith remains safe), but his implication – the more disinfectant the better – is definitely way off base. In light of these and similar findings, my approach has been to keep things clean, but to avoid the use of disinfectants in most cases.
Unfortunately for the EPA, the amount of chlorine on the earth is relatively fixed. Some small amounts may be introduced from or escape into space, and minute amounts may change into something else by radioactive decay, but basically the earth was created with just so much chlorine on it and it will have that much chlorine on it until the sun goes out. Chlorine is an element, not a chemical compound. It can’t be created or destroyed except through powerful nuclear reactions.
Anyone who wants to reduce the amount of chlorine in the environment will see their efforts frustrated because of this. You can tie it up in one chemical compound or another, or you can let it go as free chlorine, but it will always remain chlorine. So I was wondering. Doesn’t the EPA have scientists working for it? This sort of thing is elementary high school chemistry. What on earth are they thinking of?
“You canna’ change the laws of physics.”
The Clorox company says it’s no big deal to drink some Clorox bleach, which is a sodium hypochlorite solution. They say it’s an emetic and makes you throw up pretty soon. I wouldn’t mess with the ammonia too much, and stay away from Drano, the worst stuff in your house.
Clorox 2 is hydrogen peroxide, formulated somehow.
The number of chlorine atoms on the planet is relatively stable. However, the issue that concerns environmentalists is the forms in which these chlorine atoms can be found.
Most chlorine on earth is in the form of chloride, which is environmentally benign. Chemical bonds between carbon and chlorine are extremely rare in nature, but quite prevalent in human industries. Such creatures as chloroform, trichloroethylene, freons, chlorobenzenes, polychlorinated biphenyls (PCBs), etc etc are solely the creations of man.
In the current “green” political climate, organochlorines are viewed as threats to the long term survival of the ecosystem, and there is a growing cry to outlaw every C-Cl bond. This is perhaps an overreaction. Some organochlorines are environmentally not this dangerous, such as plastics (e.g. PVC, or polyvinlyl chloride- not a true chloride, BTW).
The environmental threats that most organochlorines present are numerous. One is the cancer thing, of course, which should go without saying. The toxicity of many of these compounds is legendary (dioxins, PCBs, etc.) although some are undoubtedly bound to be less toxic than they are hyped up to be. One thing that is especially annoying about them is their legendary stability. Soil contaminated by PCBs will stay that way forever until it’s cleaned up, for example.
The atmospheric threats are the most pertinent here. Ozone is catalytically destroyed by small amounts of free chlorine at high altitudes. While humans may produce free chlorine gas directly, it is diatomic Cl2 and tends to sink, reacting quickly with stuff on the ground to produce chlorides. Freons, in contrast, are unreactive. They escape old refrigerators and waft around in the atmosphere for years until they are cracked apart in the stratosphere by UV radiation. The free chlorine atoms released then catalyze the destruction of ozone. One single chlorine atom can destroy millions of ozone molecules before it binds to a dust particle or falls to lower altitudes.
When bleach (sodium hypochlorite, or NaOCl) reacts with the skidmarks on your skivvies, or the crud in your sink, some tiny amounts of organochlorines are indeed produced but they are mostly not airborne. Mishandling of bleach can sometimes produce free chlorine gas but, as far as the ozone layer is concerned, ground-level chlorine is as harmless as ground-level ozone is useless.
Regarding bleach and ammonia: Free chlorine is not produced by this reaction. Mixing the two produces an ill-defined witches' brew of chloramines, such as NH2Cl, NHCl2, and possibly NCl3. Monochloramine (NH2Cl) can react further with ammonia to produce hydrazine (H2NNH2). Trichloramine is a volatile oil that likes to explode without provocation. All 3 chloramines, along with hydrazine, are quite volatile, extremely toxic, and can cause pulmonary edema even with limited exposure. In general it is not a good idea to mix bleach and ammonia.
Lipochrome: I have a question about a stain remover in th Mindless…forum under Consumer chemistry (or some topic like that, I don’t have it open just now). Perhaps you can help.
Not to be obnoxious, but just because the Kaiser gave up on chlorine as a chem weapon agent, that don’t mean it ain’t still around, kiddies. So-ddamn Insane used it on his own people [his Kurdish ones, anyway]. If you can create toxic gases by accident, maybe some grade-A looney from the militias can make a lot of it deliberatly. That Greenpeace ban on chlorine might not be a bad idea at that. Crackpots might still be able to make CW agents, but why make it easy for them?
A “ban on chlorine” to keep us safe from those who would use chlorine gas for nefarious ends? It isn’t that simple.
Here is what you need to make chlorine gas in your basement:
-a six volt lantern battery
-alligator clips and wires
-two pieces of graphite, like you find in pencils
Dissolve the salt in the water. Use the wires and alligator clips to connect each battery terminal to a piece of graphite. Then put the graphite pieces in the salt water and voila. Hydrogen bubbles will come off of the negative graphite cathode, while chlorine gas will bubble off of the positive graphite anode. Meanwhile, in the salt water, sodium hydroxide will gradually accumulate, and it reacts quickly with some of the chlorine to make homemade bleach.
A friend of mine used this method to make and collect hydrogen for purposes of making explosions later on. (He was a trip.) He wasn’t interested in the chlorine. He just fanned it away with his hand until, like the proverbial frog that doesn’t know to jump out of boiling water, he couldn’t smell it anymore. His friend came over, though, and was knocked backwards by the chlorine as soon as he opened the back basement doors.
You make several good points, but you might make a few clarifications.
For one thing, Cecil’s column talked about a ban of all chlorine compounds, not just organic ones. This would be an impossibility for the reasons stated.
As for the cancer threat which you say goes without saying, it most certainly does not go without saying. In fact, there have been few studies showing any undisputable relationship between most of the organic compounds you mention and cancer. There were some studies that showed dioxin causes cancer in rodents a few years ago, but reports in the news media that humans living in dioxin contaminated areas experience higher rates of cancer are both anecdotal and statistically insignificant. Federal EPA standards for site cleanup are draconian: the dirt must be cleaned to a point that a young child can eat several pounds of it every day for decades without ill effect on the basis of the aforesaid rodent studies. Never mind that there are many other compounds occurring naturally in most soils that are far more toxic and with greater concentration. That does not mean the threat is not there; it is suspected, but it is far from proven.
The same goes for deterioration of the ozone layer. While the ozone layer could deteriorate in the manner you describe, most recent studies show a much greater correlation of the thickness of the ozone layer with sunspot activity than with the amount of chlorine in the upper atmosphere. Perhaps chlorine escaping into outer space is causing sunspots. No one seems to know how much, if any, free chlorine reaches the upper atmosphere and there have been no long term studies to measure it (there have been a few wild guesses masquerading as scientific evidence, however). Nice theory, but until some validation is performed, it remains unproven.
Once again, my complaint remains the same. Are there no scientists running a check on the EPA’s claims?
Seeing your other message on how to make chlorine reminded me of another idiot stunt which I will not describe here in detail since children might read it, but it involves mixing certain automotive organic compounds with pool chemicals to make explosives or start fires. The fumes given off by the resulting reaction are enough to knock anyone out.
Chlorine compounds can be very dangerous. There was a serious fire at a pulp mill in the Pacific Northwest that started when a truck leaking fluids parked too near some chlorine soaked pulp. The entire plant was engulfed in flames in minutes, but fortunately everyone working there got out safely.
On the other hand, I would hate to have to go without PVC roofing. A little pricey initially, but great stuff. Better than the tar or asbestos compounds which people used to put on flat roofs.
Well I suppose I should have been more clear when I made reference to the “cancer thing”. It’s pretty clear that given enough attention by the media and a chemophobic public, any substance will become “well-known to cause cancer”. I think this goes without saying. In addition, I agree that the toxicity of certain chlorine-containing compounds has been hyped way out of proportion by public hysteria over the decades. The toxicity of dioxin, for example, was extrapolated to humans from rodent studies. It became “the deadliest substance known to man”. People started wearing space suits in dioxin-contaminated areas. The hysteria penetrated upward all the way into EPA policies, so now they find 1 ppt dioxin in a sample of dirt and they want to evacuate the whole town and incinerate every particle of dirt. It’s clearly nonsensical. Now, years later, it turns out that dioxin toxicity is apparently specific to rodents. Well, gee, that’s great. Try telling it to the EPA. John Stossel sat before a camera with an EPA spokesman, and reiterated the wishes of people in a dioxin-contaminated zone to be left alone by the government. It seemed to go in one ear and out the other. The guy simply couldn’t believe that these people didn’t want their town evacuated, exhumed, trucked away, and vaporized by EPA guys in space suits.
Maybe a kid would have to eat a ton of dirt to be affected by PCB-laced soil. Maybe he’d have to eat ten tons. As far as I’m concerned, if you can’t keep your kid from eating ten tons of dirt, you should have already reevaluated your role in life as a parent. It wasn’t really my point to show that they ARE toxic; simply that if they’re there, they’ll stay there for a long time. They’re quite stable. This stability tends to underscore any public belief in their toxicity with the ominous threat of persistence.
Re ozone: If there is a greater correlation with sunspots than with stratospheric chlorine, great. I still don’t think any garage near me will give my air conditioner a shot of R-12 Freon. And it needs it badly.
The greatest threat of chlorine compounds, IMHO, is when things containing them catch fire. Phosgene (O=CCl2) is the sort of typical nasty species that can result when organochlorines (such as chloroform or trichloroethylene) are exposed to flames.