Phosphorus was discovered in 1669 by the alchemist Brandt, when he, in search of the "philosopher's stone", strongly heated the dry residue of urine with coal without air access. The isolated substance glowed in air and then ignited. For this property, Brandt gave him the name "phosphorus", i.e. bearer of light ("light-bearer").
After the discovery for another hundred years, phosphorus was a rare and expensive substance, because. its content in the urine is negligible, and getting it is difficult. And only after 1771, when the Swedish chemist Scheele developed a method for obtaining phosphorus from bones, it became possible to obtain it in significant quantities.
Features of phosphorus
The second typical element, the typical element in the fifth group, is a non-metal. The highest oxidation state that phosphorus can exhibit is +5. Compounds containing phosphorus in an oxidation state less than +5 act as reducing agents. At the same time, phosphorus +5 compounds in solutions are not oxidizing agents. The oxygen compounds of phosphorus are more stable than those of nitrogen. Hydrogen compounds are less stable.
Natural compounds and obtaining phosphorus
In terms of prevalence in the earth's crust, phosphorus is ahead of nitrogen, sulfur and chlorine. Unlike nitrogen, phosphorus occurs in nature only in the form of compounds. The most important minerals of phosphorus are apatite Ca5X (PO4) 3 (X is fluorine, less often chlorine and a hydroxide group) and phosphorite, the basis of which is Ca3 (PO4) 2. In addition, phosphorus is part of some protein substances and is found in plants and organisms of animals and humans.
From natural phosphorus-containing raw materials, free phosphorus is obtained by high-temperature reduction (1500 degrees C) with coke in the presence of sand. The latter binds calcium oxide into slag - calcium silicate. In the case of reduction of phosphorite, the overall reaction can be represented by the equation:
Ca3(PO4)2 + 5C + 3SiO2 = CaSiO3 + 5CO + P2
The resulting carbon monoxide and vaporous phosphorus enter the refrigerator with water, where condensation occurs to form solid white phosphorus.
Physical and chemical properties
Below 1000 deg. C, phosphorus vapor contains four-atomic P4 molecules having the shape of a tetrahedron. At higher temperatures, thermal dissociation occurs and the content of diatomic P2 molecules in the mixture increases. The decay of the latter into phosphorus atoms occurs above 2500 degrees C.
The white modification of phosphorus resulting from vapor condensation has a molecular crystal lattice, in the nodes of which P4 molecules are dislocated. Due to the weakness of intermolecular forces, white phosphorus is volatile, fusible, cut with a knife and dissolved in non-polar solvents, such as carbon disulfide. White phosphorus is a highly reactive substance. It reacts vigorously with oxygen, halogens, sulfur and metals. Oxidation of phosphorus in air is accompanied by heating and glow. Therefore, white phosphorus is stored under water, with which it does not react. White phosphorus is highly toxic.
During long-term storage, as well as when heated, white phosphorus turns into a red modification. Red phosphorus is a polymeric substance, insoluble in carbon disulfide, less toxic than white phosphorus. Red phosphorus is oxidized more difficult than white, does not glow in the dark and ignites only at 250 degrees C.
The most stable modification of phosphorus is black phosphorus. It is obtained by allotropic transformation of white phosphorus at a temperature of 220 degrees C and a pressure of 1200 MPa. In appearance, it resembles graphite. The crystal structure of black phosphorus is layered, consisting of corrugated layers. As in red phosphorus, here each phosphorus atom is bound by covalent bonds with three neighbors. The distance between phosphorus atoms is 0.387 nm. White and red phosphorus are dielectrics, while black phosphorus is a semiconductor with a band gap of 0.33 eV. Chemically, black phosphorus is the least reactive; it ignites only when heated above 400 degrees C.
Phosphorus exhibits an oxidizing function when interacting with metals: 3Ca + 2P = Ca3P2
As a reducing agent, phosphorus acts in reactions with active non-metals - halogens, oxygen, sulfur, as well as with strong oxidizing agents:
2P + 3S = P2S3 2P + 5S = P2S5
It interacts similarly with oxygen and chlorine.
P + 5HNO3 = H3PO4 + 5NO2 + H2O
In alkali solutions, when heated, white phosphorus disproportionates:
8Р + 3Ва(ОН)2 + 6Н2О = 2РН3 + 3Ва(Н2Р2)2
Chemical phosphorus oxide (+3) is acidic in nature:
P2O3 + 3H2O = 2H3RO3
Phosphorous acid - colorless, fusible, water-soluble crystals. According to its chemical structure, it is a distorted tetrahedron, in the center of which there is a phosphorus atom with sp3 hybrid orbitals, and the vertices are occupied by two hydroxo groups and hydrogen and oxygen atoms. A hydrogen atom directly connected to phosphorus is not capable of substitution, and therefore phosphorous acid is at most dibasic and is often represented by the formula H2[HPO3]. Phosphorous acid is a medium strength acid. Its salts - phosphites are obtained by the interaction of P2O3 with alkalis:
P2O3 + 4NaOH = 2Na2HPO3 + H2O
Phosphites of alkali metals and calcium are easily soluble in water.
When heated, phosphorous acid disproportionates:
4H3PO3 = PH3 + 3H3RO4
Phosphorous acid is oxidized by many oxidizing agents, including halogens, for example:
H3PO3 + Cl2 + H2O = H3RO4 + 2HCl
Phosphorous acid is usually obtained by hydrolysis of phosphorus trihalides:
RG3 + 3H2O = H3RO3 + 3NG
When monosubstituted phosphites are heated, salts of pyrophosphorous (diphosphorous) acid are obtained - pyrophosphites:
2NaH2PO3 = Na2H2P2O5 + H2O
Pyrophosphites hydrolyze when boiled with water:
Na2H2P2O5 + 3H2O = 2NaOH + 2H3PO3
Pyrophosphorous acid H4P2O5 (pentaoxodiphosphoric) itself, like phosphorous, is only dibasic and relatively unstable.
Another phosphorus acid (+3) is known - a poorly studied polymeric metaphosphorous acid (HPO2) n.
P2O5 oxide, diphosphorus pentoxide, is most characteristic of phosphorus. It is a white solid that can easily be obtained in the glassy state. In the vapor state, the molecules of phosphorus oxide (+5) have the composition P4O10. Solid P2O5 has several modifications. One of the forms of phosphorus oxide (+5) has a molecular structure with P4O10 molecules at the lattice sites. In appearance, this modification resembles ice. It has a low density, easily passes into vapor, is highly soluble in water and reactive. P2O5 is the strongest dehydrating agent. In terms of the intensity of the drying effect, it is much superior to such moisture absorbers as CaCl2, NaOH, H2SO4, etc. When P2O5 is hydrated, metaphosphoric acid is first formed:
P2O5 + H2O = 2HPO3
further hydration of which successively leads to pyrophosphoric and orthophosphoric acid:
2HPO3 + H2O = H4P2O7 and H4P2O7 + H2O = 2H3PO4
The history of the discovery of chemical elements is full of personal dramas, various surprises, mysterious mysteries and amazing legends.
Sometimes a tragic end lay in wait for the researcher, as, for example, it happened with the discoverer of fluorine. But more often success turned out to be a faithful companion of those who knew how to look closely at natural phenomena.
Ancient tomes have preserved for us individual episodes from the life of a retired soldier and a Hamburg merchant. His name was Hennig Brand (c. 1630-?). His merchant affairs did not go brilliantly, and it was for this reason that he strove to get out of poverty. She oppressed him terribly. And Brand decided to try his luck at alchemy. Moreover, in the XVII century. unlike our 20th century. it was considered quite possible to find a "philosopher's stone" that can turn base metals into gold.
Hennig Brand and Phosphorus
Brand has already conducted many experiments with various substances, but he did not succeed in anything sensible. One day he decided to conduct a chemical experiment with urine. He evaporated it almost to dryness and mixed the remaining light yellow precipitate with coal and sand, heating it in a retort without air. As a result, Brand received a new substance that had the amazing property of glowing in the dark.So in 1669, phosphorus was discovered, which plays an exceptionally important role in wildlife: in the plant world, in the body of animals and humans.
The happy scientist was not slow to take advantage of the unusual properties of the new substance and began to demonstrate luminous phosphorus to noble people for a rather high reward. Everything that came into contact with phosphorus acquired the ability to glow. It was enough to anoint fingers, hair or objects with phosphorus, and they flashed with a mysterious bluish-white light. The religiously and mystically minded rich people of that time marveled at Brand's various manipulations with this "divine" substance. He deftly used the huge interest of scientists and the general public in phosphorus and began to sell it at a price that even exceeded the cost of gold. X. Brand produced phosphorus in large quantities and kept the method of obtaining it in the strictest confidence. None of the other alchemists could penetrate his laboratory, and therefore many of them began to feverishly set up various experiments, trying to uncover the secret of making phosphorus.
The famous German chemist I. Kunkel (1630-1703) advised his friend-colleague I. Kraft to persuade H. Brand to sell the secret of obtaining phosphorus. I. Kraft managed to persuade the discoverer to this deal for 100 thalers, "however, the new owner of the secret of obtaining the" eternal flame "turned out to be a mercenary person and, without telling his friend I. Kunkel a single word about acquiring the recipe, began to make huge sums of money on demonstrations of phosphorus public.
I. Kunkel
The outstanding German mathematician and philosopher G. Leibniz also did not miss the opportunity and acquired the secret of phosphorus production from H. Brand.G. Leibniz
Soon, the recipe for making "cold fire" became known to I. Kunkel and K. Kirchmeyer, and in 1680 the secret of obtaining phosphorus was discovered in England by the famous chemist R. Boyle. After the death of R. Boyle, his student, the German A. Gankwitz, having improved the method for obtaining phosphorus, set up its production and even tried to make the first matches. He supplied phosphorus to the scientific institutions of Europe and individuals who wished to purchase it. To expand trade relations, A. Gankwitz visited Holland, France, Italy and Germany, concluding new contracts for the sale of phosphorus. In London, he founded a pharmaceutical company that became widely known. It is curious that A. Hankwitz, despite his long work with phosphorus and very dangerous experiments with it, lived to the age of eighty. He outlived his three sons and all those who took part in the work relating to the early history of phosphorus.The price of phosphorus since its discovery by I. Kunkel and R. Boyle began to fall rapidly, and in the end, the heirs of the discoverers began to introduce the secret of obtaining phosphorus for just 10 thalers.
Stages of studying phosphorus
In the history of chemistry, phosphorus is associated with many great discoveries. However, only a century after the discovery of phosphorus, he moved from the world of trade and profit to the world of science. But only one event during this long period can be attributed to real science, and it is connected with 1715, when I. Gensing discovered phosphorus in the brain tissue. This later served as the basis for the statement: "Without phosphorus there is no thought."Yu. Gan in 1769 found phosphorus in the bones, and two years later the famous Swedish chemist showed that the bones consist mainly of calcium phosphate, and proposed a method for obtaining phosphorus from the ash formed during the burning of bones.
J. Proust and M. Klaproth in 1788 proved the extremely high prevalence in nature of minerals containing calcium phosphate.
The researchers found that the glow of phosphorus occurs only in the presence of ordinary, i.e., containing moisture, air. This behavior of phosphorus is due to its slow oxidation by atmospheric oxygen. At the same time, ozone is also formed, which gives the air a kind of freshness, well known to us in the days of spring thunderstorms. The glow of phosphorus occurs without noticeable warming up, and such a reaction is called chemiluminescence. It can be observed not only during the slow oxidation of phosphorus, but also during some other chemical and biochemical processes, in which, for example, the glow of fireflies, rot, oceanic plankton, etc. occurs.
M. Klaproth
In the early 70s of the XVIII century. French chemist Antoine Laurent Lavoisier, conducting various experiments on the combustion of phosphorus and other substances in a closed vessel, convincingly proved that phosphorus is a simple body. And the air, in his opinion, has a complex composition and consists primarily of two components - oxygen and nitrogen.At the turn of the two centuries, in 1799, the Englishman A. Dondonald discovered that phosphorus compounds are necessary for the normal development of plant organisms. Another Englishman, J. Looz in 1839 for the first time received superphosphate - a phosphorus fertilizer, which later played an extremely important role in increasing crop yields.
In Russia in 1797, A.A. Musin-Pushkin received an allotropic variety of phosphorus - violet phosphorus. However, in the literature, the discovery of violet phosphorus is erroneously attributed to I. Gittorf, who, using the method of A. A. Musin-Pushkin, obtained it only in 1853.
In 1848, the Austrian chemist A. Schretter discovered the allotropic modification of phosphorus - red phosphorus. He obtained such phosphorus by heating white phosphorus to a temperature of about 250 ° C in an atmosphere of carbon monoxide (IV). It is interesting to note that Schroetter was the first to point out the possibility of using red phosphorus in the manufacture of matches. In 1855, at the World Exhibition in Paris, red phosphorus, obtained already in the factory, was demonstrated.
The famous American physicist P. Bridgen in 1917, by heating phosphorus to 200 °C under a pressure of about 1.27 GPa, obtained a new allotropic modification - black phosphorus. Like red phosphorus, the latter does not ignite in air.
Thus, many decades were required to study the physical and chemical properties of phosphorus and to discover its new allotropic modifications. The study of phosphorus made it possible to find out what role it plays in the life of plants and animals. Phosphorus is found literally in all parts of green plants, which not only accumulate it for their own needs, but also supply animals with it. This is one of the stages of the phosphorus cycle in nature.
Phosphorus and nature
Phosphorus is just as important as nitrogen. It participates in the great natural cycle of matter, and if it were not for phosphorus, the flora and fauna would be completely different. However, phosphorus is found in natural conditions not so often, mainly in the form of minerals, and it accounts for 0.08% of the mass of the earth's crust. In terms of prevalence, it ranks thirteenth among other elements. It is interesting to note that in the human body, phosphorus accounts for approximately 1.16%. Of these, 0.75% goes to bone tissue, about 0.25% to muscle and about 0.15% to nervous tissue.Phosphorus is rarely found in large quantities, and in general it should be classified as a trace element. It is not found in free form in nature, since it has a very important property - it is easily oxidized, but it is contained in many minerals, the number of which is already 190. The most important of them are fluorapatite, hydroxylapatite, and phosphorite. Vivianite, monazite, amblygonite, triphylite are somewhat rarer, and xenotite and torbernite are quite rare.
As for phosphorus minerals, they are divided into primary and secondary. Among the primary, the most common are apatites, which are mainly rocks of igneous origin. The chemical composition of apatite is calcium phosphate containing a certain amount of fluoride and calcium chloride. This is what determines the existence of the minerals fluorapatite and chlorapatite. In addition, they contain from 5 to 36% P2 05. Usually, these minerals are found in most cases in the magma zone, but they are often found in places where igneous rocks come into contact with sedimentary ones. Of all the known phosphate deposits, the most significant are found in Norway and Brazil. A large domestic apatite deposit was discovered by academician A. E. Fersman in Khibiny in 1925. “Apatite is mainly a compound of phosphoric acid and calcium,” wrote A. E. Fersman. They called it apatite, which means "deceiver" in Greek. Either these are transparent crystals, to the smallest detail resembling beryl or even quartz, then these are dense masses, indistinguishable from simple limestone, then these are radially radiant balls, then the rock is granular and shiny, like coarse-grained marble.
As a result of the action of weathering processes, the vital activity of bacteria, and destruction by various soil acids, apatites pass into forms that are easily consumed by plants, and thus are involved in the biochemical cycle. It should be noted that phosphorus is absorbed only from dissolved salts of phosphoric acid. However, phosphorus is partially washed out of the soil, and a large amount of it, absorbed by plants, does not return back to the soil and is carried away along with the crop. All this leads to the gradual depletion of the soil. With the introduction of phosphate fertilizers into the soil, the yield increases.
Despite the significant demand for phosphate fertilizers, there does not seem to be much concern about the depletion of raw materials for their production. These fertilizers can be obtained by complex processing of mineral raw materials, bottom marine sediments and various geological rocks rich in phosphorus.
During the decomposition of phosphorus-rich compounds of organic origin, gaseous and liquid substances are often formed. Sometimes you can observe the release of gas with the smell of rotten fish - hydrogen phosphide, or phosphine, PH3. Simultaneously with phosphine, another product is formed - diphosphine, P2 H4, which is a liquid. The vapors of diphosphine ignite spontaneously and ignite the gaseous phosphine. This explains the appearance of the so-called "wandering lights" in places such as cemeteries, swamps.
"Wandering lights" and other cases of the glow of phosphorus and its compounds caused superstitious fear in many people who were not familiar with the essence of these phenomena. Here is what academician S.I. recalls about working with gaseous phosphorus. Volfkovich: “Phosphorus was obtained in an electric furnace installed at Moscow University on Mokhovaya Street. Since these experiments were then carried out in our country for the first time, I did not take the precautions that are necessary when working with gaseous phosphorus - a poisonous, self-igniting and luminous bluish element. During many hours of work at the electric furnace, part of the liberated gaseous phosphorus soaked my clothes and even shoes so much that when I walked from the university at night through the dark, then unlit streets of Moscow, my clothes radiated a bluish glow, and from under my shoes (during friction them on the pavement) sparks were struck.
Every time a crowd gathered behind me, among which, despite my explanations, there were quite a few people who saw in me a “newly appeared” representative of the other world. Soon, among the inhabitants of the Mokhovaya Street area and throughout Moscow, fantastic stories about the luminous monk began to be passed from mouth to mouth ... "
Phosphine and diphosphine are quite rare in nature, and more often one has to deal with such phosphorus compounds as phosphorites. These are secondary minerals-phosphates of organic origin, which play a particularly important role in agriculture. On the islands of the Pacific Ocean, in Chile and Peru, they were formed on the basis of bird droppings - guano, which in a dry climate accumulates in thick layers, often exceeding a hundred meters.
The formation of phosphorites can also be associated with geological catastrophes, for example, with the ice age, when the death of animals was massive. Similar processes are also possible in the ocean during the mass death of marine fauna. The rapid change in hydrological conditions, which may be associated with various mountain building processes, in particular with the action of underwater volcanoes, undoubtedly leads to the death of marine animals in some cases. Phosphorus from organic residues is partially absorbed by plants, but mostly, dissolving in sea water, it passes into mineral forms. Sea water contains phosphates in quite large quantities - 100-200 mg/m3. Under certain chemical processes in sea water, phosphates can precipitate and accumulate on the bottom. And when the seabed rises in different geological periods, phosphorite deposits turn out to be on land. In a similar way, a large domestic phosphorite deposit near Kara-Tau in Kazakhstan could have been formed. Phosphorites are also found in the Moscow region.
Phosphorus cycle in nature
A good explanation of the main stages of the phosphorus cycle in nature can be the words of the famous scientist, one of the founders of the direction of domestic science on the study of phosphate fertilizers Ya. V. Samoilov: “Phosphorus of our phosphorite deposits is of biochemical origin. From apatite, a mineral in which almost all of the phosphorus of the lithosphere was originally contained, this element passes into the body of plants, from plants into the body of animals, which are true phosphorus concentrators. After passing through a series of animal bodies, phosphorus finally drops out of the biochemical cycle and again returns to the mineral one. Under certain physical and geographical conditions, mass death of animal organisms occurs in the sea
About the match
The first fire was produced by a man in a very primitive way - by rubbing two pieces of wood, and the wood dust and sawdust were heated so much that they spontaneously ignited. Ancient people knew several ways of making fire by friction: most often, a sharp wooden stick made a quick rotation, resting it on a dry plank. This method can be reproduced now, but it is not at all simple and requires great effort and dexterity. This is how man has been making fire for thousands of years.
It is amazing! If you think about this simple fact, you can see how complicated each step of a person on the path of progress was.
The famous flint and steel came to replace the wooden sticks. This is a very simple device: a piece of steel or copper pyrite was struck against flint and a sheaf of sparks was cut, setting fire to a flammable substance.
This method, presented to us by an ancient man, was widely used during the Great Patriotic War, when the country experienced an acute shortage of matches.
Surprisingly, but only 200 years ago in Russia, and throughout the world, steel flint and wick were practically the only “matches” of a man who managed not only to build the Egyptian pyramids, but also to create the steam engine of James Watt, the first steamboat of Robert Fulton , looms and many other great inventions, but not matches. They were born later! Difficult and great was the path to them, like any path into the world unknown to man.
The ancient Greeks and Romans knew another way of making fire, using the sun's rays focused by a lens or a concave mirror. The great ancient Greek scientist Archimedes deftly used this method and, according to legend, set fire to the enemy fleet with the help of a huge mirror. But this method of obtaining fire is of little use because of the very limited possibilities of its use, since the sun is necessary.
The development of civilization, scientific and technological progress opened up new opportunities in various fields of human activity.
After 1700, a significant number of means for producing fire were invented, the most interesting of them is the Döbereiner incendiary apparatus, created in Jena in 1823. The inventor of the apparatus used the properties of explosive gas to ignite spontaneously in the presence of spongy platinum, i.e. finely crushed.
However, such a device was, of course, of little use for widespread use.
We are getting closer and closer to the moment when the word "match" was finally heard for the first time. Who introduced this word into use has not yet been established, but work continues in this direction, and we hope that our young readers will help us in this.
Here we should throw a small bridge to phosphorus and its discoverer - a Hamburg soldier, later a merchant and alchemist Hennig Brand. The new element phosphorus proved to be flammable when rubbed. The researchers took advantage of this property by creating matches.
R. Boyle's assistant and student, the talented and enterprising German A. Hankwitz obtained pure phosphorus from phosphates and guessed to make matches with a sulfur coating, ignited by rubbing against a piece of phosphorus. But this first step had to be improved and made matches more convenient for widespread use.
This became possible when the famous French chemist C. Berthollet obtained a salt - potassium chlorate KClO3, called Berthollet. His compatriot Chancel took advantage of this discovery and invented in 1805 the so-called French incendiary machines. Potassium chlorate, together with sulfur, resin, sugar and gum arabic, was applied to a wooden stick, and when it came into contact with concentrated sulfuric acid, ignition occurred. The reaction sometimes developed very rapidly and was of an explosive nature.
In 1806, the German Wagemann from Tübingen used the invention of Chansel, but added pieces of asbestos to sulfuric acid to slow down the combustion process. He soon moved to Berlin and organized the manufacture of the so-called Berlin lighters. The factory he set up was the first large-scale production of incendiary devices, employing more than 400 people. A similar incendiary mixture was used in "Prometheus" (John's matches), manufactured in 1828 in England.
In 1832 dry matches appeared in Vienna. They were invented by L. Trevani, he covered the head of a wooden straw with a mixture of Berthollet salt with sulfur and glue. If such a match is held over sandpaper, then its head ignites. But even in this case, not everything turned out to be successful, sometimes the head ignited with an explosion, and this led to serious burns.
Ways to further improve matches were extremely clear: it is necessary to make such a composition of the mixture for - a match head so that it lights up calmly. The problem was soon resolved. The new composition included Berthollet salt, white phosphorus and glue. Matches with such a coating easily ignited when rubbed against any hard surface, glass, shoe soles, or a piece of wood.
The inventor of the first phosphorus matches was a nineteen-year-old Frenchman Charles Soria. In 1831, a young experimenter added white phosphorus to a mixture of Berthollet salt and sulfur to weaken its explosive properties. This idea turned out to be extremely successful, since the splinter lubricated with the resulting composition easily caught fire during friction. The ignition temperature of such matches is relatively low - 30 ° C. Young S. Soria tried to get a patent for his invention, but, unfortunately, it turned out to be much more difficult to do than to create the first phosphorus matches. Too much money had to be paid for the patent, but S. Soria did not have that kind of money. A year later, phosphorus matches were created again by the German chemist J. Kammerer.
So, the long way of uterine maturation of the first match ended and it was born at once in the hands of several inventors. However, fate was pleased to give the laurels of primacy in this discovery to Jacob Friedrich Kammerer (1796-1857), and to preserve 1832 for posterity as the year of the birth of matches, the largest discovery of the 19th century, which played an important role in the history of the development of human culture.
Many sought to receive the laurels of the discoverers of matches, but history has preserved for us the name of J. Kammerer from all the contenders. The first phosphorus matches were brought to Russia from Hamburg in 1836 and were sold at a very expensive price - one silver ruble per hundred. There are suggestions that our great poet A. S. Pushkin used such phosphorus matches in the last year of his life, working by candlelight on long winter evenings.
The youth of St. Petersburg was not slow, of course, to show off phosphorus matches at balls and in fashionable salons, striving to be in no way inferior to Western Europe. It’s a pity that A. S. Pushkin didn’t have time to devote a single poetic line to matches - a wonderful and very important invention, so useful and familiar now that we don’t even think about the difficult fate of the appearance of matches ... It seems to us that matches have always been Next to us. But in fact, the first domestic factory for the production of matches was built in St. Petersburg only in 1837.
A little more than 150 years have passed since the inhabitants of the Russian state received the first domestic matches and, realizing the importance of this invention, quickly launched match production.
In 1842, in one St. Petersburg province, there were 9 match factories producing 10 million matches daily. The price of matches dropped sharply and did not exceed 3-5 kopecks. copper for 100 pieces. The method of making matches turned out to be so simple that in Russia by the middle of the 19th century. it began to bear the character of handicraft. So, in 1843-1844. matches were found to be homemade in significant numbers.
They were produced in the most remote corners of Russia by enterprising peasants, thus hiding from taxes. However, the flammability of phosphorus has led to large fires. Many villages and villages burned out literally to the ground.
The culprit of these disasters was white phosphorus, which is highly flammable. During transportation, matches often caught fire from friction. Enormous fires blazed on the way of match wagons, and maddened horses with burning wagons brought a lot of trouble.
In 1848, the highest imperial decree signed by Nicholas I followed, allowing the manufacture of incendiary matches only in the capitals, and the matches were to be packed in tins of 1000 pieces. Further, the decree stated: “Pay special attention to the extreme spread of the use of incendiary matches, deign to see that during the fires that occurred this year, which consumed more than 12,000,000 rubles in some cities. silver of philistine property, arsonists very often committed their crime by means of matches.
In addition, white phosphorus is one of the most toxic substances.
Therefore, work in match factories was accompanied by a serious disease called phosphorus necrosis affecting the jaws, i.e. cell death, as well as severe inflammation and bleeding of the gums.
With the expansion of production, cases of serious poisoning among workers grew. Accidents took such catastrophic forms that in Russia already in 1862 an order was issued to limit the sale of white phosphorus.
Phosphorus began to be sold only with special permits from the local police.
Match factories had to pay heavy taxes, and the number of enterprises began to decline. But the need for matches did not decrease, but, on the contrary, grew. Various artisanal matches appeared, which were distributed illegally. All this led to the fact that in 1869 a new decree was issued, allowing "everywhere, both in the Empire and in the Kingdom of Poland, to make phosphoric matches for sale without special restrictions ...".
In the second half of the XIX century. the problem of replacing white phosphorus arose very acutely. The governments of many states have come to the conclusion that the manufacture of matches containing white phosphorus brings more loss than income. In most countries, the production of such matches was prohibited by law.
But a way out was found, relatively quickly it turned out to be possible to replace white phosphorus with red, discovered in 1848. Unlike white, this kind of phosphorus is completely harmless. Red phosphorus was introduced into the composition of the match mass. But the expectations were not met. The matches burned very badly. They didn't find a market. The manufacturers who started the production went bankrupt.
By the middle of the 19th century, many outstanding inventions had been made, and the manufacture of an ordinary match could not find a satisfactory solution.
The problem was solved in 1855 in Sweden. Safety matches in the same year were presented at the International Exhibition in Paris and received a gold medal. From that moment on, the so-called Swedish matches began their triumphal march around the world. Their main feature was that they did not ignite when rubbed against any hard surface. The Swedish match was lit only if it was rubbed against the side of the box, covered with a special mass.
Thus, the "safe fire" in Swedish matches was born from the magnificent union of friction and chemical reaction.
That, perhaps, is all! Let us now tell you how a modern match works. The mass of a match head is 60% berthollet salt, as well as combustible substances, sulfur or some metal sulfides, such as antimony sulfide. In order for the head to ignite slowly and evenly, without an explosion, so-called fillers are added to the mass - glass powder, iron oxide (III), etc. The binding material is glue. Bertolet's salt can be replaced by substances containing oxygen in large quantities, such as potassium bichromate.
And what does the skin paste consist of? Here the main component is
red phosphorus. Manganese (IV) oxide, crushed glass and glue are added to it.
Let us now see what processes take place when a match is lit.
When the head is rubbed against the skin at the point of their contact, red phosphorus ignites due to the oxygen of the Bertolet salt. Figuratively speaking, fire is originally born in the skin. He lights the match head. Sulfur or antimony (III) sulfide flares up in it, again due to the oxygen of the Bertolet salt. And then the tree lights up.
Now there are many recipes for head and spread compositions. The only constant components are Berthollet salt and red phosphorus.
But after all, the necessary element of a match is its wooden part, or match straw. The methods of its manufacture also have a long history. For primitive dipped matches, the torch was cut by hand with a knife. Now ingenious machines work in match factories. The most suitable tree for making match straws is aspen. The aspen ridge is first sanded and thoroughly cleaned. A thin wooden sheet is cut from a log on special machines. Then it is split into long thin rods. These rods are already turned into matchsticks in another machine. Next, the straw enters the machines, where a match mass is applied to its end. Along with this, match straws are usually subjected to special treatment to prevent, for example, dampness.
Modern match-making Mishins produce hundreds of millions of matches a day.
In conclusion, let's look at the production of matches through the eyes of an economist. If we assume that every person on average spends at least one match a day, then in order to satisfy the annual need of mankind for matches, about 20 million aspens are needed, which is almost half a million hectares of first-class aspen forest.
Isn't it difficult? And for those countries in which there are few or almost no forests, this is simply not possible. We tried using cardboard instead of wooden straws. But such soft matches were not successful. They are very inconvenient to handle.
That is why all kinds of lighters have become widespread - gasoline, gas, electric lighters for gas stoves, etc. And in the end, their production will be cheaper than the manufacture of matches.
Does this mean that the match will someday become just a museum piece? It is difficult to answer this question. It can be assumed that the production of matches in the future may be reduced.
Currently, our country ranks first in the world in the production of matches. Modern match factories are equipped with high-performance machines that make it possible to produce 500,000 matches per hour.
With the expansion of production, technology is improved, new types of matches are mastered, hunting, storm, gas and souvenir matches are produced in sets, colorful labels of which reflect the most significant events in the life of our country.
Hunting matches differ from simple ones in that, in addition to the usual
heads and straws, they have an additional coating below the head. The additional incendiary mass makes the match long-burning with a large hot flame. It burns for about 10 s, while a simple match is only 2-3 s. Such matches make it possible to light a fire in any weather.
Storm matches are no less curious. They do not have a head, but the coating of the “body” is much thicker than that of hunting matches. Their incendiary mass contains a lot of bertolet salt, therefore, the ability to ignite, i.e. the sensitivity of such matches is very high. They burn for at least 10 s in any meteorological conditions, even in stormy weather at 12 points. Such matches are especially needed by fishermen and sailors.
Gas matches differ from ordinary ones in that their stick is longer. Matches with straws of 70 mm are now produced. With this match, you can light several burners at once. The addition of some salts to the incendiary mass makes it possible to obtain colored fire: red, pink, blue, green, violet.
Matches are packed in boxes of various sizes, containing fifty, one hundred, two hundred and even five hundred matches. Currently, match production is fully automated and this allows selling its products at fairly low prices. Previously, the expression "cheaper than matches" was used, which means "almost free."
Of course, spending wood on making matchsticks is becoming more and more wasteful. After all, hundreds of hectares of good forest are spent on this, in saving which practically all countries of the world are now interested, even those that still have quite large areas of forest wealth. The volume of modern production and construction is growing so rapidly that the amount of wood consumed increases significantly every decade. Now there is a full task of saving timber and replacing it, where possible, with products from other raw materials.
Increasingly, various items widely used in everyday life are made of plastics. In the world market in the last decade, prices for polyvinyl chloride, polyvinyl acetate, polystyrene and other materials have noticeably decreased.
Manufacture of matches and matchboxes from plastics
The issue of manufacturing matches and matchboxes from plastics for the mass consumer is being widely discussed at the present time. If this could be done, then a real revolution would take place in the development of the match industry. On our ecologically scarred land, it would be possible to save hundreds of hectares of forest, which is consumed much faster than its reserves are replenished.However, in reality, everything is not so simple. Many plastic materials are difficult to recycle, and they are increasingly polluting the ocean and land. Large industrial cities can hardly cope with the processing of waste from plastic materials, our once clean planet is suffocating under the onslaught of synthetic waste. Naturally, matchboxes made of various polymeric materials will also be carelessly thrown away after using the matches, as is now the case with similar products made of cardboard and wood. Then, undoubtedly, Moscow and the Moscow region and many other cities of our long-suffering planet will dress in a new outfit from the waste of match products. This will no longer be the mythical dress of the king from the wonderful fairy tale of the great Andersen, but an inquisitorial toga made by man from polymer materials for Mother Earth.
So where is the exit? How to avoid the catastrophe lurking in the intensive distribution of plastic products? There is, of course, a way out. There are and are increasingly being used artificial materials that, under the influence of solar radiation and acids, dissolve in the soil. These synthetic materials for the manufacture of matchboxes and matches will undoubtedly be used in the near future. Although at present such products are much more expensive than similar wood products.
The manufacture of very beautiful matchboxes from synthetic materials requires significant investment. On the outer matchboxes made of plastic, a pattern is squeezed out and a phosphorus mass is applied using special machines.
Of course, over the past quarter of a century, the price has decreased somewhat due to improvements in manufacturing technology, but all the same, synthetic matches still cannot compete in price with matches made from wood. Synthetic matches are produced in small batches in a number of Western European countries. Cheaper raw materials and further improvement of equipment are required. Is it unsolvable?
Recall that just some 100 years ago, aluminum was more expensive than gold, and only thanks to the creation of a new electrochemical method for obtaining it, did it become affordable and cheap.
Obtaining a synthetic material for a matchstick capable of replacing a matchstick, making it possible to regulate the temperature and combustion rate, is quite possible from a technical point of view when solving the issue of mass production of synthetic matches by modern industry.
At present, in Germany, the Reifenhäuser company uses polystyrene for the manufacture of matchboxes and matches, and in France wax matches have begun to be made, that is, the last word has not yet been said in the creation of an ordinary match. An extensive field of activity in this area awaits the younger generation with anxieties and successes. I would like to believe that we will also refuse to use wood.
chemical industry chemical news stories
Learn more about news in the field of chemistry, interestingPhosphorus was discovered by the German alchemist Hennig Brand. H. Brand was a Hamburg merchant, then went bankrupt, went into debt and decided to try his luck in alchemy to improve his affairs. After working unsuccessfully for a long time, he decided to look for the "philosopher's stone". First of all, Brand decided to look for this mysterious substance in the products of a living organism. For a number of reasons, chiefly of a mystical nature, he chose urine for this purpose. After evaporating almost to dryness, Brand subjected it to strong heating, while he observed that a white substance was obtained, which burned with the formation of white smoke.
Alchemist H. Brand, trying to find the "philosopher's stone",
got amazing stuff. It turned out that it was phosphorus
Brand decided to collect this substance and began to heat the dried urine without air. In 1669, his work was crowned with an unexpected discovery: a peculiar substance was formed in the retort, which had a nasty taste, a faint garlic smell, looked like wax, melted with slight heating and released vapors that glowed in the dark. Brand ran his hand over the substance - his fingers began to glow in the dark, threw it into boiling water - the vapors turned into spectacularly shining beams. Everything that came into contact with the resulting substance acquired the ability to self-luminescence. One can imagine how great was the amazement of the mystical-minded Brand, brought up on the belief in the "philosopher's stone". This is how phosphorus was discovered. Brand named it Kaltes Feuer("cold fire"), sometimes calling it affectionately "my fire". And although Brand could not produce a single transformation of a base metal into gold or silver with the help of a new luminous substance, nevertheless, the "cold fire" brought him a very significant benefit.
Brand very cleverly used the enormous interest that was caused by the discovery of phosphorus among the scientific world and the general public. He began to produce phosphorus in fairly significant quantities. The method of obtaining it was clothed by him in the strictest secrecy, and none of the other alchemists could penetrate his laboratory. Brand showed a new substance for money and sold it in small portions at the price of gold and even higher. In 1730, i.e. 61 years after the discovery, an ounce (31 g) of phosphorus cost 10.5 chervonets in London and 16 chervonets in Amsterdam. It is not surprising, therefore, that many rushed to make various experiments, trying to uncover Brand's secret.
The German chemist, professor at Wittenberg University Johann Kunkel (1630–1703) was especially interested in phosphorus. During the trip, he met with his friend, the chemist Kraft from Dresden, and persuaded him to buy a secret from Brand in order to benefit from it. Kraft visited Brand and he managed to buy the secret of making phosphorus for 200 thalers. However, Kunkel did not gain anything from this deal: Kraft did not share the secret he had received with him, but began to travel around the courtyards of the electors, showing, like Brand, phosphorus for money and making huge sums on this business.
In the spring of 1676, Kraft arranged a session of experiments with phosphorus at the court of Elector Friedrich Wilhelm of Brandenburg. At 9 pm on April 24, all the candles in the room were extinguished, and Kraft showed those present experiments with "eternal fire", without revealing, however, the method by which this magical substance was prepared.
In the spring of the following year, Kraft came to the court of Duke Johann Friedrich in Hannover, where at that time the German philosopher and mathematician G. W. Leibniz (1646–1716) served as a librarian. Kraft also arranged a session of experiments with phosphorus here, showing, in particular, two flasks that glowed like fireflies. Leibniz, like Kunkel, was extremely interested in the new substance. At the first session, he asked Kraft if a large piece of this substance would not be able to light up the whole room. Kraft agreed that it was quite possible, but would be impractical, since the process of preparing the substance is very complicated.
Leibniz's attempts to persuade Kraft to sell the secret to the duke failed. Then Leibniz went to Hamburg to Brand himself. Here he managed to conclude a contract between Duke Johann Friedrich and Brand, according to which the former was obliged to pay Brand 60 thalers for revealing the secret. From that time on, Leibniz entered into regular correspondence with Brand.
At about the same time, I.I. Becher (1635-1682) arrived in Hamburg with the aim of luring Brand to the Duke of Mecklenburg. However, Brand was again intercepted by Leibniz and taken to Hanover to Duke Johann Friedrich. Leibniz was fully convinced that Brand was very close to discovering the "philosopher's stone", and therefore advised the duke not to let him go until he had completed this task. Brand, however, stayed in Hanover for five weeks, prepared fresh supplies of phosphorus outside the city, showed, according to the contract, the secret of production and left.
Then Brand prepared a significant amount of phosphorus for the physicist Christian Huygens, who studied the nature of light, and sent a supply of phosphorus to Paris.
Brand, however, was very dissatisfied with the price Leibniz and Duke Johann Friedrich gave him for revealing the secret of phosphorus production. He sent an angry letter to Leibniz, complaining that the amount received was not enough even to support his family in Hamburg and pay travel expenses. Similar letters were sent to Leibniz and Brand's wife, Margarita.
Brand was also dissatisfied with Kraft, to whom he expressed resentment in letters, reproaching him for having resold the secret for 1000 thalers to England. Kraft forwarded this letter to Leibniz, who advised Duke Johann Friedrich not to irritate Brand, to pay him more generously for revealing the secret, fearing that the author of the discovery, in the form of an act of revenge, would share the recipe for making phosphorus with someone else. Leibniz sent a reassuring letter to Brand himself.
Apparently, Brand received a reward, tk. in 1679 he again came to Hanover and worked there for two months, receiving a weekly salary of 10 thalers with additional payment for the table and travel expenses. Correspondence between Leibniz and Brand, judging by the letters kept in the Hanover Library, continued until 1684.
Let us now return to Kunkel. According to Leibniz, Kunkel learned through Kraft the recipe for making phosphorus and set to work. But his first experiments were unsuccessful. He wrote letter after letter to Brand, complaining that he had been sent a recipe that was very incomprehensible to another person. In a letter written in 1676 from Wittenberg, where Kunkel was then living, he asked Brand about the details of the process.
In the end, Kunkel achieved success in his experiments, somewhat modifying Brand's method. By adding a little sand to dry urine before distilling it, he received phosphorus and ... made a claim to the independence of the discovery. In the same year, in July, Kunkel told about his successes to his friend, Professor of Wittenberg University Kaspar Kirchmeyer, who published a work on this issue under the title "Permanent night lamp, sometimes sparkling, which was long sought, now found." In this article, Kirchmeyer speaks of phosphorus as a long-known luminous stone, but does not use the term "phosphorus" itself, obviously not yet accustomed to that time.
IN England, independently of Brand, Kunkel and Kirchmeyer in 1680, phosphorus was obtained by R. Boyle (1627–1691). Boyle knew about phosphorus from the same Kraft. As early as May 1677, phosphorus was demonstrated at the Royal Society of London. In the summer of the same year, Kraft himself came with phosphorus to England. Boyle, according to his own account, visited Kraft and saw phosphorus in his solid and liquid form. In gratitude for the warm welcome, Kraft, saying goodbye to Boyle, hinted to him that the main substance of his phosphorus was something inherent in the human body. Obviously, this hint was enough to give an impetus to Boyle's work. After Kraft's departure, he began to test blood, bones, hair, urine, and in 1680 his efforts to obtain a luminous element were crowned with success.
Boyle began to exploit his discovery in the company of an assistant, the German Gaukwitz. After Boyle's death in 1691, Gaukwitz launched the production of phosphorus, improving it on a commercial scale. By selling phosphorus at three pounds sterling an ounce and supplying the scientific institutions and individual scientists of Europe with it, Gaukwitz amassed a huge fortune. To establish commercial connections, he traveled to Holland, France, Italy and Germany. In London itself, Gaukwitz founded a pharmaceutical company that became famous during his lifetime. It is curious that, despite all his experiments with phosphorus, sometimes very dangerous, Gaukwitz lived to be 80 years old, outliving his three sons and all the people who participated in the work related to the early history of phosphorus.
Since the discovery of phosphorus by Kunkel and Boyle, it has rapidly fallen in price as a result of the competition of inventors. In the end, the heirs of the inventors began to acquaint everyone with the secret of its production for 10 thalers, all the while lowering the price. In 1743, A.S. Marggraf found an even better way to produce phosphorus from urine and immediately published it, because. fishing has ceased to be profitable.
IN Currently, phosphorus is not produced anywhere by the Brand-Kunkel-Boyle method, since it is completely unprofitable. For the sake of historical interest, we still give a description of their method.
Rotting urine is evaporated to a syrupy state. The resulting thick mass is mixed with three times the amount of white sand, placed in a retort equipped with a receiver, and heated for 8 hours on an even fire until the volatile substances are removed, after which the heating is increased. The receiver is filled with white vapor, which then turns into bluish solid and luminous phosphorus.
Phosphorus got its name due to the property to glow in the dark (from Greek - luminiferous). Among some Russian chemists there was a desire to give the element a purely Russian name: "gem", "lighter", but these names did not take root.
Lavoisier, as a result of a detailed study of the combustion of phosphorus, was the first to recognize it as a chemical element.
The presence of phosphorus in the urine gave chemists a reason to look for it in other parts of the body of animals. In 1715, phosphorus was found in the brain. The significant presence of phosphorus in it served as the basis for the assertion that "without phosphorus there is no thought." In 1769, Yu.G. Gan found phosphorus in the bones, and two years later, K.V. Scheele proved that the bones consist mainly of calcium phosphate, and proposed a method for obtaining phosphorus from the ash remaining after bones were burned. Finally, in 1788, M.G. Klaproth and J.L. Proust showed that calcium phosphate is an extremely widespread mineral in nature.
The allotropic modification of phosphorus - red phosphorus - was discovered in 1847 by A. Schretter. In a work entitled "A New Allotropic State of Phosphorus", Schretter writes that sunlight changes white phosphorus to red, and factors such as dampness, atmospheric air, have no effect. Schretter separated the red phosphorus by treatment with carbon disulfide. He also prepared red phosphorus by heating white phosphorus to a temperature of about 250 ° C in an inert gas. At the same time, it was found that a further increase in temperature again leads to the formation of a white modification.
It is very interesting that Schroetter was the first to predict the use of red phosphorus in the match industry. At the World Exhibition in Paris in 1855, red phosphorus, already obtained by the factory, was demonstrated.
Russian scientist A.A. Musin-Pushkin in 1797 received a new modification of phosphorus - violet phosphorus. This discovery is erroneously attributed to I.V. Gittorf, who, having almost completely repeated the Musin-Pushkin method, received violet phosphorus only in 1853.
In 1934, Professor P.W. Bridgman, exposing white phosphorus to a pressure of up to 1100 atm , turned it black and thus obtained a new allotropic modification of the element. Along with the color, the physical and chemical properties of phosphorus have changed: white phosphorus, for example, ignites spontaneously in air, and black, like red, does not have this property.
It is possible that elemental phosphorus was obtained as early as the 12th century. by the Arab alchemist Alkhid Behil during the distillation of urine with clay and lime, this is evidenced by an ancient alchemical manuscript stored in the Paris Library. However, the discovery of phosphorus is usually attributed to the bankrupt Hamburg merchant Hennig Brand. The entrepreneur was engaged in alchemy in order to obtain the philosopher's stone and the elixir of youth, with which one could easily improve his financial situation.
But in fact, from ancient times, substances that can glow in the dark were called phosphors with the light hand of the ancient Greeks, since they had this word meaning “light-bearer”. By the way, they called the planet Venus Phosphorus or Lucifer, but only in the morning, in the evenings it had a different name.
In the history of the disclosure of the secret of obtaining phosphorus, the 17th century became an important milestone. For example, the shoemaker V. Kagaorolo, who was engaged in alchemy, decided that a mineral called "barite" could be turned into gold (or into a philosopher's stone, which would help solve the same problem, and at the same time solve issues with health and eternal youth). Having calcined barite with coal and oil, he received the so-called "Bolognese phosphorus", glowing in the dark for some time.
In Saxony, Balduin, a judicial official of a low rank (like our volost foreman), for some reason took up experiments with chalk and nitric acid (however, it is clear why: he was an alchemist). Having calcined the product of the interaction of the ingredients, he discovered a glow in the retort - it was anhydrous calcium nitrate, which was called "Baldwin's phosphorus".
But the record of the brightest page in this story was started by Honnig Brand, which is worth talking about in more detail, because even the great Lavoisier left brief information about him after they met in 1678. In his youth he was a soldier, then he self-proclaimed himself a doctor, without being burdened with a medical education. Marrying a wealthy woman made it possible to start living in a big way and engage in trade. Alchemy attracted H. Brand with the secret of obtaining gold.
Oh, how he was carried away by the idea, what efforts he made to implement it! Believing that the products of the vital activity of a person, the “king of nature”, can contain the so-called primary energy, the tireless experimenter began distilling human urine, one might say, on an industrial scale: in the soldiers’ barracks, he collected a whole ton of it in total! And he evaporated to a syrupy state (not in one go, of course!), And after distillation, he again distilled the resulting “urine oil” and calcined it for a long time. As a result, white dust appeared in the retort, which settled to the bottom and glowed, which is why it was called “cold fire” (kaltes Feuer) by Brand. Brand's contemporaries called this substance phosphorus because of its ability to glow in the dark (other Greek jwsjoroV).
In 1682, Brand published the results of his research, and he is now rightly considered the discoverer of element No. 15. Phosphorus was the first element whose discovery was documented, and its discoverer is known.
Interest in the new substance was enormous, and Brand took advantage of this - he demonstrated phosphorus only for money or exchanged small amounts of it for gold. Despite numerous efforts, the Hamburg merchant could not fulfill his cherished dream - to obtain gold from lead using "cold fire", and therefore he soon sold the recipe for obtaining a new substance to a certain Kraft from Dresden for two hundred thalers. The new owner managed to make a much larger fortune on phosphorus - he traveled all over Europe with "cold fire" and demonstrated it to scientists, high-ranking and even royal people, for example, Robert Boyle, Gottfried Leibniz, Charles II. Although the method of preparing phosphorus was kept in the strictest confidence, in 1682 Robert Boyle managed to obtain it, but he also disclosed his method only at a closed meeting of the Royal Society of London. Boyle's method was made public after his death, in 1692.
In the spring of 1676, Kraft arranged a session of experiments with phosphorus at the court of Elector Friedrich Wilhelm of Brandenburg. At 9 pm on April 24, all the candles in the room were extinguished, and Kraft showed those present experiments with "eternal fire", without revealing, however, the method by which this magical substance was prepared.
In the spring of the following year, Kraft came to the court of Duke Johann Friedrich in Hannover3, where at that time the German philosopher and mathematician G.W. Leibniz (1646-1716) served as a librarian. Kraft also arranged a session of experiments with phosphorus here, showing, in particular, two flasks that glowed like fireflies. Leibniz, like Kunkel, was extremely interested in the new substance. At the first session, he asked Kraft if a large piece of this substance would not be able to light up the whole room. Kraft agreed that it was quite possible, but would be impractical, since the process of preparing the substance is very complicated.
Leibniz's attempts to persuade Kraft to sell the secret to the duke failed. Then Leibniz went to Hamburg to Brand himself. Here he managed to conclude a contract between Duke Johann Friedrich and Brand, according to which the former was obliged to pay Brand 60 thalers for revealing the secret. From that time on, Leibniz entered into regular correspondence with Brand.
At about the same time, I.I. Becher (1635-1682) arrived in Hamburg with the aim of luring Brand to the Duke of Mecklenburg. However, Brand was again intercepted by Leibniz and taken to Hanover to Duke Johann Friedrich. Leibniz was fully convinced that Brand was very close to discovering the "philosopher's stone", and therefore advised the duke not to let him go until he had completed this task. Brand, however, stayed in Hanover for five weeks, prepared fresh supplies of phosphorus outside the city, showed, according to the contract, the secret of production and left.
Then Brand prepared a significant amount of phosphorus for the physicist Christian Huygens, who studied the nature of light, and sent a supply of phosphorus to Paris.
Brand, however, was very dissatisfied with the price Leibniz and Duke Johann Friedrich gave him for revealing the secret of phosphorus production. He sent an angry letter to Leibniz, complaining that the amount received was not enough even to support his family in Hamburg and pay travel expenses. Similar letters were sent to Leibniz and Brand's wife, Margarita.
Brand was also dissatisfied with Kraft, to whom he expressed resentment in letters, reproaching him for having resold the secret for 1000 thalers to England. Kraft forwarded this letter to Leibniz, who advised Duke Johann Friedrich not to irritate Brand, to pay him more generously for revealing the secret, fearing that the author of the discovery, in the form of an act of revenge, would share the recipe for making phosphorus with someone else. Leibniz sent a reassuring letter to Brand himself.
Apparently, Brand received a reward, tk. in 1679 he again came to Hanover and worked there for two months, receiving a weekly salary of 10 thalers with additional payment for the table and travel expenses. Correspondence between Leibniz and Brand, judging by the letters kept in the Hanover Library, continued until 1684.
Let us now return to Kunkel. According to Leibniz, Kunkel learned through Kraft the recipe for making phosphorus and set to work. But his first experiments were unsuccessful. He wrote letter after letter to Brand, complaining that he had been sent a recipe that was very incomprehensible to another person. In a letter written in 1676 from Wittenberg, where Kunkel was then living, he asked Brand about the details of the process.
In the end, Kunkel achieved success in his experiments, somewhat modifying Brand's method. By adding a little sand to dry urine before distilling it, he received phosphorus and ... made a claim to the independence of the discovery. In the same year, in July, Kunkel spoke about his successes to his friend, Professor of Wittenberg University Kaspar Kirchmeyer, who published a work on this issue under the title "Permanent night lamp, sometimes sparkling, which was long sought, now found." In this article, Kirchmeyer speaks of phosphorus as a long-known luminous stone, but does not use the term "phosphorus" itself, obviously not yet accustomed to that time.
In England, independently of Brand, Kunkel and Kirchmeier in 1680, phosphorus was obtained by R. Boyle (1627-1691). Boyle knew about phosphorus from the same Kraft. As early as May 1677, phosphorus was demonstrated at the Royal Society of London. In the summer of the same year, Kraft himself came with phosphorus to England. Boyle, according to his own account, visited Kraft and saw phosphorus in his solid and liquid form. In gratitude for the warm welcome, Kraft, saying goodbye to Boyle, hinted to him that the main substance of his phosphorus was something inherent in the human body. Obviously, this hint was enough to give an impetus to Boyle's work. After Kraft's departure, he began to test blood, bones, hair, urine, and in 1680 his efforts to obtain a luminous element were crowned with success.
Boyle began to exploit his discovery in the company of an assistant, the German Gaukwitz. After Boyle's death in 1691, Gaukwitz launched the production of phosphorus, improving it on a commercial scale. By selling phosphorus at three pounds sterling an ounce and supplying the scientific institutions and individual scientists of Europe with it, Gaukwitz amassed a huge fortune. To establish commercial connections, he traveled to Holland, France, Italy and Germany. In London itself, Gaukwitz founded a pharmaceutical company that became famous during his lifetime. It is curious that, despite all his experiments with phosphorus, sometimes very dangerous, Gaukwitz lived to be 80 years old, outliving his three sons and all the people who participated in the work related to the early history of phosphorus.
Since the discovery of phosphorus by Kunkel and Boyle, it has rapidly fallen in price as a result of the competition of inventors. In the end, the heirs of the inventors began to acquaint everyone with the secret of its production for 10 thalers, all the while lowering the price. In 1743, A.S. Marggraf found an even better way to produce phosphorus from urine and immediately published it, because. fishing has ceased to be profitable.
Currently, phosphorus is not produced anywhere by the Brand-Kunkel-Boyle method, since it is completely unprofitable. For the sake of historical interest, we will nevertheless give a description of their method.
Rotting urine is evaporated to a syrupy state. The resulting thick mass is mixed with three times the amount of white sand, placed in a retort equipped with a receiver, and heated for 8 hours on an even fire until the volatile substances are removed, after which the heating is increased. The receiver is filled with white vapor, which then turns into bluish solid and luminous phosphorus.
Phosphorus got its name due to the property to glow in the dark (from Greek - luminiferous). Among some Russian chemists there was a desire to give the element a purely Russian name: "gem", "lighter", but these names did not take root.
Lavoisier, as a result of a detailed study of the combustion of phosphorus, was the first to recognize it as a chemical element.
The presence of phosphorus in the urine gave chemists a reason to look for it in other parts of the body of animals. In 1715, phosphorus was found in the brain. The significant presence of phosphorus in it served as the basis for the assertion that "without phosphorus there is no thought." In 1769, Yu.G. Gan found phosphorus in the bones, and two years later, K.V. Scheele proved that the bones consist mainly of calcium phosphate, and proposed a method for obtaining phosphorus from the ash remaining after bones were burned. Finally, in 1788, M.G. Klaproth and J.L. Proust showed that calcium phosphate is an extremely widespread mineral in nature.
The allotropic modification of phosphorus - red phosphorus - was discovered in 1847 by A. Schretter. In a work entitled "A New Allotropic State of Phosphorus", Schretter writes that sunlight changes white phosphorus to red, and factors such as dampness, atmospheric air, have no effect. Schretter separated the red phosphorus by treatment with carbon disulfide. He also prepared red phosphorus by heating white phosphorus to a temperature of about 250 ° C in an inert gas. At the same time, it was found that a further increase in temperature again leads to the formation of a white modification.
It is very interesting that Schroetter was the first to predict the use of red phosphorus in the match industry. At the World Exhibition in Paris in 1855, red phosphorus, already obtained by the factory, was demonstrated.
The Russian scientist A.A. Musin-Pushkin in 1797 received a new modification of phosphorus - violet phosphorus. This discovery is erroneously attributed to I.V. Gittorf, who, having almost completely repeated the Musin-Pushkin method, received violet phosphorus only in 1853.
In 1934, Professor P.W. Bridgman, subjecting white phosphorus to a pressure of up to 1100 atm, turned it into black and thus obtained a new allotropic modification of the element. Along with the color, the physical and chemical properties of phosphorus have changed: white phosphorus, for example, ignites spontaneously in air, and black, like red, does not have this property.
Phosphorus (from Greek phosphoros - luminiferous; lat. Phosphorus) - an element of the periodic table of chemical elements of the periodic table, one of the most common elements of the earth's crust, its content is 0.08-0.09% of its mass. The concentration in sea water is 0.07 mg/l. 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 Ca 5 (PO 4) 3 (F,Cl,OH), phosphorite Ca 3 (PO 4) 2 and others. Phosphorus is found in all parts of green plants, and even more in fruits and seeds (see phospholipids). Contained in animal tissues, is part of proteins and other essential organic compounds (ATP, DNA), is an element of life.
Story
Phosphorus was discovered by the Hamburg alchemist Hennig Brand in 1669. Like other alchemists, Brand tried to find the philosopher's stone, but received a luminous substance. Brand focused on experiments with human urine, because he believed that it, having a golden color, may contain gold or something necessary for mining. Initially, his method consisted in the fact that at first the urine was settled for several days until the unpleasant odor disappeared, and then boiled to a sticky state. By heating this paste to high temperatures and bringing it up to the appearance of bubbles, he hoped that, when condensed, they would contain gold. After several hours of intense boiling, grains of a white wax-like substance were obtained, which burned very brightly and, moreover, flickered in the dark. Brand named this substance phosphorus mirabilis (lat. "miraculous light carrier"). Brand's discovery of phosphorus was the first discovery of a new element since antiquity.
Somewhat later, phosphorus was obtained by another German chemist, Johann Kunkel.
Regardless of Brand and Kunkel, phosphorus was obtained by R. Boyle, who described it in the article “Method of preparing phosphorus from human urine”, dated October 14, 1680 and published in 1693.
An improved method for obtaining phosphorus was published in 1743 by Andreas Marggraf.
There is evidence that Arab alchemists were able to obtain phosphorus in the 12th century.
The fact that phosphorus is a simple substance was proved by Lavoisier.
origin of name
In 1669, Henning Brand, by heating a mixture of white sand and evaporated urine, obtained a substance glowing in the dark, first called "cold fire". The secondary name "phosphorus" comes from the Greek words "φῶς" - light and "φέρω" - I carry. In ancient Greek mythology, the name Phosphorus (or Eosphorus, other Greek Φωσφόρος) was worn by the guardian of the Morning Star.
Receipt
Phosphorus is obtained from apatites or phosphorites as a result of interaction with coke and silica at a temperature of 1600 ° C:
2Ca 3 (PO 4) 2 + 10C + 6SiO 2 → P4 + 10CO + 6CaSiO 3 .
The resulting white phosphorus vapor condenses in the receiver under water. Instead of phosphorites, other compounds can be reduced, for example, metaphosphoric acid:
4HPO 3 + 12C → 4P + 2H 2 + 12CO.
Physical Properties
Elemental phosphorus under normal conditions represents several stable allotropic modifications; The problem of phosphorus allotropy is complex and not fully resolved. Usually there are four modifications of a simple substance - white, red, black and metallic phosphorus. Sometimes they are also called the main allotropic modifications, implying that all the others are a variety of these four. Under normal conditions, there are only three allotropic modifications of phosphorus, and under conditions of ultrahigh pressures, there is also a metallic form. All modifications differ in color, density and other physical characteristics; there is a noticeable tendency to a sharp decrease in chemical activity during the transition from white to metallic phosphorus and an increase in metallic properties.
Chemical properties
The chemical activity of phosphorus is much higher than that of nitrogen. The chemical properties of phosphorus are largely determined by its allotropic modification. White phosphorus is very active, in the process of transition to red and black phosphorus, the chemical activity decreases sharply. White phosphorus glows in the dark in air, the glow is due to the oxidation of phosphorus vapor to lower oxides.
In the liquid and dissolved state, as well as in vapors up to 800 ° C, phosphorus consists of P 4 molecules. When heated above 800 ° C, the molecules dissociate: P 4 \u003d 2P 2. At temperatures above 2000 °C, molecules break up into atoms.
