Hello %username%.
As promised, here is an article-story about yellow phosphorus and how it burned gloriously near Lvov in Ukraine relatively recently.
Yes, I know - Google gives a lot of information about this accident. Unfortunately, most of what he gives out is not true, or, as eyewitnesses say, nonsense.
Let's find out!
Well, in the beginning - no one's favorite materiel, but by the way it is very important!
According to boring Wikipedia, phosphorus is one of the common elements of the earth's crust: its content is 0,08-0,09% of its mass. It is not found in the free state due to its high chemical activity. It forms about 190 minerals, the most important of which are apatite Ca5(PO4)3 (F,Cl,OH), phosphorite Ca3(PO4)2 and others. Phosphorus is part of the most important biological compounds - phospholipids. Contained in animal tissues, is part of proteins and other essential organic compounds (ATP, DNA), is an element of life. Remember this, %username%, and we'll move on.
Phosphorus in its pure form is white, red, black and metallic. This is called allotropic modifications - the weaker sex is very well versed in them, because by touch they can distinguish a diamond from graphite - and these are also allotropic modifications, only for carbon. In general, phosphorus is the same.
The hero of our story - yellow phosphorus - is actually unrefined white. Very often, “unrefined” means an admixture of red phosphorus, and not some terrible foreign elements.
Yellow phosphorus (however, like white) is a real hell: highly toxic (maximum concentration limit in atmospheric air is 0,0005 mg / m³), a flammable crystalline substance from light yellow to dark brown in color. Specific gravity 1,83 g/cm³, melts at +43,1 °C, boils at +280 °C. It does not dissolve in water, easily oxidizes in air and ignites spontaneously. It burns with a dazzling bright green flame with the release of thick white smoke - small particles of tetraphosphorus decaoxide P4O10. This is boring Wikipedia again, but please, %username% - remember this information too.
Now we will understand.
Well, firstly, despite the toxicity of phosphorus, it is extremely difficult to poison them for a very simple reason: it ignites spontaneously in air. Very fast. And it burns, as already mentioned, with a blue bright green flame. In practice, it looks like this: you put a piece on the table - and it slowly starts to smoke like that. Then faster. Then more. And then it flashes and burns. The flash time depends on the size of the piece: the smaller, the faster. That is why it is difficult for me to imagine fine dust of yellow phosphorus in the air - it will simply catch fire.
Although, you might object, they write here: the lethal dose of yellow phosphorus for a person is 0,05-0,15 grams, it dissolves well in body fluids and is quickly absorbed when ingested (by the way, red phosphorus is insoluble and therefore relatively low-toxic). Acute poisoning occurs when yellow phosphorus vapors are inhaled and / or when they enter the gastrointestinal tract. Poisoning is characterized by pain in the abdomen, vomiting, beautiful glowing in the dark vomit that emits the smell of garlic, and diarrhea. Another symptom of acute yellow phosphorus poisoning is heart failure.
After reading this, for some reason I remembered about phosphine poisoning (the symptoms are very similar) and thought hard - but not about the existence of yellow phosphorus vapor, but about the adequacy of an individual who saw a piece of an unknown something smoking, glowing in the dark - and immediately ate. Well, that's it.
By the way, to get a solution of phosphorus in water of 3 mg / l - and this is a saturated solution, it does not dissolve anymore - you need to shake a piece of phosphorus in water for a week. Well, I didn’t come up with this, GOST 32459-2013 says so - and this is not all sorts of Internet for you!
In general, in my opinion, the toxicity of phosphorus is greatly exaggerated. But he has other nuances. About them - below.
Phosphorus burns, as experts who work with it like to say, according to the gimlet rule: that is, a burning piece eats into the surface on which it burns. To the table. In metal. In a boot. In hand. The reason is simple: the product of combustion - phosphorus oxide - is essentially an acidic oxide, which immediately draws water, forming phosphoric acid. Phosphoric acid, although not as sweet as sulfuric or hydrofluoric acid, loves to eat no less - and therefore corrodes everything. By the way, it is sometimes added to the liquid for cleaning toilets. A nice combination of high-temperature combustion (up to 1300 °C) and hot acid and gives extra holes to your table, and if you're not lucky, your body. And yes, %username% is very painful.
I have already stated many times and will continue to assert that there is no greater enemy of man than himself: of course, the properties of yellow phosphorus did not go unnoticed - and good people came up with the idea of adding it to incendiary ammunition, because it is very convenient when something suddenly catches fire on air!
It looks very nice - you can admire
But people after such attacks do not look very beautiful - so you better not look
Since all this is very charming, the development, testing, transportation, trade, use and disposal of phosphorus munitions are carried out taking into account a number of international agreements and treaties, including:
- St. Petersburg Declaration "On the abolition of the use of explosive and incendiary bullets" of 1868.
- Additional Protocols of 1977 to the Geneva Convention for the Protection of Victims of War, 1949, prohibiting the use of white phosphorus munitions if civilians are thereby endangered. The United States and Israel did not sign them, by the way.
- In accordance with the Third Protocol to the 1980 UN Convention on Certain Weapons, incendiary weapons must not be used against civilians, and, in addition, they must not be used against military objectives that are located in a zone of concentration of civilians.
In general, there are a lot of papers, but they have a status close to toilet, because these ammunition are used all the time - Palestine and Donbass will confirm.
Since phosphorus reacts with water only at temperatures above 500 degrees Celsius, large amounts of water are used to extinguish phosphorus (to reduce the temperature of the fire and transfer phosphorus to a solid state) or a solution of copper sulfate (copper sulfate), after quenching, phosphorus is poured wet sand. To prevent spontaneous combustion, yellow phosphorus is stored and transported under a layer of water (calcium chloride solution, to be precise, but water will also come off). This is also important!
Who produces phosphorus? And here, %username%, someone will be filled with pride: the main supplier of phosphorus, food phosphoric acid, sodium hexaphosphate and tripolyphosphate is proud Kazakhstan!
In fact, since the times of the USSR, in the glorious city of Dzhambul (yes, the name of the same Dzhambul Dzhabaev), the Kazphosphate enterprise was built. Then Dzhambul was renamed Taraz - well, let's not discuss the expediency, the Kazakhs know better - but the enterprise remained. The presence of a raw material base and capacity, as well as the extremely low cost of labor (and there is, in fact, nowhere else to work in Taraz / Dzhambul) determined that yellow phosphorus is made here.
When I was at this enterprise - it's good there! South Kazakhstan, 300 km to Uzbekistan - warm! Birds are singing! Everything is green! Mountains on the horizon! Beauty!
By the way, the Kazphosphate plant does not disturb this idyll in any way: all in greenery, flowers, on the slope of a small mountain.
It's really good there
The reason for beauty is simple - the raw materials, products and waste products are phosphorus-containing substances, which are actually fertilizers. This is where it grows and blooms.
By the way, the highest authorities of the plant do not like dandelions very much. Nobody knows why. And therefore, before the visit of the highest authorities, the workers arrange a subbotnik for weeding out dandelions. Well, how it is - to fight with dandelions - everyone knows from the dacha / vegetable gardens, within the framework of phosphoric lawlessness, this is completely pointless: enough for a day, maximum - two. But leadership is what it is.
I was especially impressed by the work of the laboratory of the enterprise. There are some really big nerds out there. And for you to understand, %username%, a few facts.
In yellow phosphorus, it is very important to control impurities - especially arsenic, antimony, selenium, nickel, copper, zinc, aluminum, cadmium, chromium, mercury, lead, iron. In order to control all this, phosphorus must be dissolved, and at the same time, everything that is controlled must not fly away.
Problem number one: how to weigh something that catches fire in the air? They do this: they hammer an ingot of phosphorus under a layer of water, take away larger pieces - small ones flare up too quickly - and transfer them to a glass of water. Then they weigh another glass of water, take phosphorus from the first, wipe it with alcohol, wait until it dries - and throw it into a weighed glass of water. The mass of phosphorus is determined by the difference in weight.
Since it can catch fire - there is a solution of copper sulfate nearby - if it catches fire, then they throw it into it.
Then the phosphorus is dissolved. It dissolves in nitric acid saturated with bromine vapor - a very sweet and fragrant thing. I recommend in the economy. It is necessary to throw phosphorus into this mixture, then heat it up a little, and when the reaction starts, transfer it to a trough with cold water, because the heating is enormous. And stir, stir, stir - if you do not interfere, then the pieces will simply jump out of the bubbling soup - the results will be inaccurate! They interfere with the hand, there are two mittens on it: rubber from acid - and felt from temperature (just rubber is melted, but just felt - does not save from drops of acid. True, if phosphorus gets in, both will not save.
Fascinating spectacle of the dissolution of yellow phosphorus
At the same time, nitrogen oxides and bromine are flying - this is a note. The girls are afraid of these red tails and pieces of phosphorus, which can get on clothes or a mitten. Poisoning "pairs" or "solutions" of phosphorus do not recall.
By the way, the salary of the girls who do this is not higher than $200 (and the answer is simple: there is nowhere else to work in Taraz, I have already said this). So next time, %username%, when you whine about low wages and the harmfulness of work, remember Kazphosphate!
Well, now that the basic knowledge has been accumulated, let's move on to the actual accident in Lviv.
Since phosphorus is in demand in Europe, Kazphosphate actively exports products through Czech partners. She rides in tanks filled with water, and it is clear that by rail.
On Monday, July 16, 2007, at 16:55 in the Busk district of the Lviv region of Ukraine on the Krasne-Ozhidiv stage, 15 tanks with yellow phosphorus of freight train No. 2005 derailed and overturned. There were 58 wagons in total. The tanks followed from the Kazakh station Asa (Taraz, Kazakhstan) to the Oklesa station (Republic of Poland). The leakage of phosphorus from one tank provoked spontaneous combustion of six other tanks.
It looked epic
And then - a mixture of panic, inflated by the media, lack of experience with yellow phosphorus and complete ignorance of chemistry.
During the extinguishing of the fire, a cloud of combustion products formed with an affected area of about 90 square kilometers. This zone included 14 settlements of the Busk district, where 11 people live, as well as separate territories of the Radekhiv and Brodiv districts of the region. The Ministry of Emergency Situations of Ukraine offered residents of nearby villages to evacuate and sent them about ten buses, but many people refused to leave their homes. The Lviv authorities assured that no one would be forcibly evacuated, although they warned of the unpredictability of the consequences of the accident. In total, about 6 residents were temporarily resettled from 800 settlements in the Bus region overnight.
By Tuesday, there were 20 people injured (6 specialists of the Ministry of Emergency Situations, 2 representatives of the Ministry of Internal Affairs, 2 railway workers and 10 people from the local population), of which 13 were hospitalized in a serious and moderate condition at the military medical clinical center of the Western Operational Command in Lviv. Seven hospitalized are employees of the Ministry of Emergency Situations, two are employees of the State traffic inspectorate, four are local residents.
At the same time, the most cruel and wildest howl rose in the media. Some of the pearls:
- ...
Reading all this makes me sad. Because it shows absolute ignorance of chemistry in the mass. And also - how easy it is to manipulate the uneducated masses (by the way,% username%, and you knew that slave owners in the USA firmly believed that slaves should be illiterate - so that they could not forge vacation certificates, other papers, correspond with other settlements, coordinate uprisings and etc. - little has changed).
More or less objective events in the chronology are shown here (carefully - Ukrainian, if you don't know the shame - Google Translate):
What can be understood from this chronology?
- Nobody knew anything.
- Everyone wanted to be promoted.
- Firefighters/Ministry of Emergency Situations were frightened.
- The military, too.
- Among the locals there was a complete mess.
- Until representatives of Kazphosphate arrived on July 18, no one understood what to do.
- Nobody wanted to pay for anything.
After a conversation with some employees of Kazphosphate, who are directly involved in the elimination of the consequences of the accident, I can say the following.
There was no explosion / spontaneous combustion / explosion of phosphorus - he calmly rode himself under the water. Yes, and yellow phosphorus cannot explode by itself! But there was damage to the railroad tracks, which caused the tanks to derail. When the tanks hit, a crack formed, water flowed out through it - well, the phosphorus ignited safely. The temperature and features of combustion finally destroyed the tank.
- White smoke is understandable - it is a pair of phosphoric acid, but not phosphorus. If you breathe them - yes, a strong cough will begin and in general it is not particularly useful. However, it is not fatal. Most of the injuries of the local population are due to the fact that people ran to collect interesting smoking pieces in bottles of water, but the cordon was not immediately set up - everyone was afraid.
- The fear of firefighters that supposedly “this rubbish is on fire from the water!” due to the fact that a powerful jet of water broke the phosphorus into smaller pieces - well, they flew apart and caught fire. It was necessary either with a weak stream, or with foam, which was subsequently done.
- By the way, when everything was extinguished and only pieces remained inside the tank, the Kazakhs extinguished it. Well, how they extinguished it - they collected it and threw it into buckets of water to a greater extent. One of them is the plant's chief technologist, an avid smoker. So - he put out and smoked. In some places, even pictures of a “crazy Kazakh who smokes in a terrible chemical fire!” So what?
- There was and could not have been any ecological catastrophe and the “second Chernobyl” - in fact, nature received a dose of phosphate fertilizers.
- The only person who behaved adequately, listened to the Kazakhs and did the right thing was Vladimir Antonets, First Deputy Minister of the Ministry of Emergency Situations. Probably because Colonel General with a bunch of awards.
After it became clear that the sensation did not work out: there was no terrorist attack, there was no threat of an ecological catastrophe - also, no one died and no money would be given - they quickly lost interest in the catastrophe. The official cause of the accident was:
- Inadequate condition of the tracks on this railway section.
- Violation of safety rules by the employees of the locomotive crew.
- Negligence (ignored instructions on the temperature regime for the transport of especially dangerous goods).
- Inadequate technical condition of tanks.
In fact, the most truthful of these is the first. The rest was added so as not to pay the Kazakhs for the loss of cargo. Well, it looks like the insurance paid for it.
So everyone stayed on their own.
Moral, %username%: learn chemistry. She is everywhere. It will help you to live, and survive, and understand something for yourself.
And finally ...
Not all chemicals are harmful. Without hydrogen and oxygen, for example, water, the main component of beer, would not be possible.
— Dave Barry, never a chemist
Source: habr.com