Chemical element with atomic number 8
<Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as well as with other compounds. After hydrogen and helium, oxygen is the third-most abundant element in the universe by mass. At standard temperature and pressure, two atoms of the element bind to form dioxygen, a colorless and odorless diatomic gas with the formula O
2. Diatomic oxygen gas constitutes 20.95% of the Earth's atmosphere. Oxygen makes up almost half of the Earth's crust in the form of oxides.[2]
Dioxygen provides the energy released in combustion[3] and aerobic cellular respiration,[4] and many major classes of organic molecules in living organisms contain oxygen atoms, such as proteins, nucleic acids, carbohydrates, and fats, as do the major constituent inorganic compounds of animal shells, teeth, and bone. Most of the mass of living organisms is oxygen as a component of water, the major constituent of lifeforms. Oxygen is continuously replenished in Earth's atmosphere by photosynthesis, which uses the energy of sunlight to produce oxygen from water and carbon dioxide. Oxygen is too chemically reactive to remain a free element in air without being continuously replenished by the photosynthetic action of living organisms. Another form (allotrope) of oxygen, ozone (O
3), strongly absorbs ultraviolet UVB radiation and the high-altitude ozone layer helps protect the biosphere from ultraviolet radiation. However, ozone present at the surface is a byproduct of smog and thus a pollutant.
Oxygen was isolated by Michael Sendivogius before 1604, but it is commonly believed that the element was discovered independently by Carl Wilhelm Scheele, in Uppsala, in 1773 or earlier, and Joseph Priestley in Wiltshire, in 1774. Priority is often given for Priestley because his work was published first. Priestley, however, called oxygen "dephlogisticated air", and did not recognize it as a chemical element. The name oxygen was coined in 1777 by Antoine Lavoisier, who first recognized oxygen as a chemical element and correctly characterized the role it plays in combustion.
Common uses of oxygen include production of steel, plastics and textiles, brazing, welding and cutting of steels and other metals, rocket propellant, oxygen therapy, and life support systems in aircraft, submarines, spaceflight and diving.
History
Early experiments
One of the first known experiments on the relationship between combustion and air was conducted by the 2nd century BCE Greek writer on mechanics, Philo of Byzantium. In his work Pneumatica, Philo observed that inverting a vessel over a burning candle and surrounding the vessel's neck with water resulted in some water rising into the neck.[5] Philo incorrectly surmised that parts of the air in the vessel were converted into the classical element fire and thus were able to escape through pores in the glass. Many centuries later Leonardo da Vinci built on Philo's work by observing that a portion of air is consumed during combustion and respiration.[6]
In the late 17th century, Robert Boyle proved that air is necessary for combustion. English chemist John Mayow (1641–1679) refined this work by showing that fire requires only a part of air that he called spiritus nitroaereus.[7] In one experiment, he found that placing either a mouse or a lit candle in a closed container over water caused the water to rise and replace one-fourteenth of the air's volume before extinguishing the subjects.[8] From this he surmised that nitroaereus is consumed in both respiration and combustion.
Mayow observed that antimony increased in weight when heated, and inferred that the nitroaereus must have combined with it.[7] He also thought that the lungs separate nitroaereus from air and pass it into the blood and that animal heat and muscle movement result from the reaction of nitroaereus with certain substances in the body.[7] Accounts of these and other experiments and ideas were published in 1668 in his work Tractatus duo in the tract "De respiratione".[8]
Phlogiston theory
Robert Hooke, Ole Borch, Mikhail Lomonosov, and Pierre Bayen all produced oxygen in experiments in the 17th and the 18th century but none of them recognized it as a chemical element.[9] This may have been in part due to the prevalence of the philosophy of combustion and corrosion called the phlogiston theory, which was then the favored explanation of those processes.[10]
Established in 1667 by the German alchemist J. J. Becher, and modified by the chemist Georg Ernst Stahl by 1731,[11] phlogiston theory stated that all combustible materials were made of two parts. One part, called phlogiston, was given off when the substance containing it was burned, while the dephlogisticated part was thought to be its true form, or calx.[6]
Highly combustible materials that leave little residue, such as wood or coal, were thought to be made mostly of phlogiston; non-combustible substances that corrode, such as iron, contained very little. Air did not play a role in phlogiston theory, nor were any initial quantitative experiments conducted to test the idea; instead, it was based on observations of what happens when something burns, that most common objects appear to become lighter and seem to lose something in the process.[6]
Discovery
Polish alchemist, philosopher, and physician Michael Sendivogius (Michał Sędziwój) in his work De Lapide Philosophorum Tractatus duodecim e naturae fonte et manuali experientia depromti (1604) described a substance contained in air, referring to it as 'cibus vitae' (food of life[12]), and this substance is identical with oxygen.[13] Sendivogius, during his experiments performed between 1598 and 1604, properly recognized that the substance is equivalent to the gaseous byproduct released by the thermal decomposition of potassium nitrate. In Bugaj's view, the isolation of oxygen and the proper association of the substance to that part of air which is required for life, lends sufficient weight to the discovery of oxygen by Sendivogius.[13] This discovery of Sendivogius was however frequently denied by the generations of scientists and chemists which succeeded him.[12]
It is also commonly claimed that oxygen was first discovered by Swedish pharmacist Carl Wilhelm Scheele. He had produced oxygen gas by heating mercuric oxide and various nitrates in 1771–2.[14][15][6] Scheele called the gas "fire air" because it was then the only known agent to support combustion. He wrote an account of this discovery in a manuscript titled Treatise on Air and Fire, which he sent to his publisher in 1775. That document was published in 1777.[16]
In the meantime, on August 1, 1774, an experiment conducted by the British clergyman Joseph Priestley focused sunlight on mercuric oxide (HgO) contained in a glass tube, which liberated a gas he named "dephlogisticated air".[15] He noted that candles burned brighter in the gas and that a mouse was more active and lived longer while breathing it. After breathing the gas himself, Priestley wrote: "The feeling of it to my lungs was not sensibly different from that of common air, but I fancied that my breast felt peculiarly light and easy for some time afterwards."[9] Priestley published his findings in 1775 in a paper titled "An Account of Further Discoveries in Air", which was included in the second volume of his book titled Experiments and Observations on Different Kinds of Air.[6][17] Because he published his findings first, Priestley is usually given priority in the discovery.
The French chemist Antoine Laurent Lavoisier later claimed to have discovered the new substance independently. Priestley visited Lavoisier in October 1774 and told him about his experiment and how he liberated the new gas. Scheele had also dispatched a letter to Lavoisier on September 30, 1774, which described his discovery of the previously unknown substance, but Lavoisier never acknowledged receiving it. (A copy of the letter was found in Scheele's belongings after his death.)[16]
Lavoisier's contribution
Lavoisier conducted the first adequate quantitative experiments on oxidation and gave the first correct explanation of how combustion works.[15] He used these and similar experiments, all started in 1774, to discredit the phlogiston theory and to prove that the substance discovered by Priestley and Scheele was a chemical element.
In one experiment, Lavoisier observed that there was no overall increase in weight when tin and air were heated in a closed container.[15] He noted that air rushed in when he opened the container, which indicated that part of the trapped air had been consumed. He also noted that the tin had increased in weight and that increase was the same as the weight of the air that rushed back in. This and other experiments on combustion were documented in his book Sur la combustion en général, which was published in 1777.[15] In that work, he proved that air is a mixture of two gases; 'vital air', which is essential to combustion and respiration, and azote (Gk. ἄζωτον "lifeless"), which did not support either. Azote later became nitrogen in English, although it has kept the earlier name in French and several other European languages.[15]
Lavoisier renamed 'vital air' to oxygène in 1777 from the Greek roots ὀξύς (oxys) (acid, literally "sharp", from the taste of acids) and -γενής (-genēs) (producer, literally begetter), because he mistakenly believed that oxygen was a constituent of all acids.[18] Chemists (such as Sir Humphry Davy in 1812) eventually determined that Lavoisier was wrong in this regard (hydrogen forms the basis for acid chemistry), but by then the name was too well established.[19]
Oxygen entered the English language despite opposition by English scientists and the fact that the Englishman Priestley had first isolated the gas and written about it. This is partly due to a poem praising the gas titled "Oxygen" in the popular book The Botanic Garden (1791) by Erasmus Darwin, grandfather of Charles Darwin.[16]
Later history
John Dalton's original atomic hypothesis presumed that all elements were monatomic and that the atoms in compounds would normally have the simplest atomic ratios with respect to one another. For example, Dalton assumed that water's formula was HO, leading to the conclusion that the atomic mass of oxygen was 8 times that of hydrogen, instead of the modern value of about 16.[20] In 1805, Joseph Louis Gay-Lussac and Alexander von Humboldt showed that water is formed of two volumes of hydrogen and one volume of oxygen; and by 1811 Amedeo Avogadro had arrived at the correct interpretation of water's composition, based on what is now called Avogadro's law and the diatomic elemental molecules in those gases.[21][a]
By the late 19th century scientists realized that air could be liquefied and its components isolated by compressing and cooling it. Using a cascade method, Swiss chemist and physicist Raoul Pierre Pictet evaporated liquid sulfur dioxide in order to liquefy carbon dioxide, which in turn was evaporated to cool oxygen gas enough to liquefy it. He sent a telegram on December 22, 1877 to the French Academy of Sciences in Paris announcing his discovery of liquid oxygen.[22] Just two days later, French physicist Louis Paul Cailletet announced his own method of liquefying molecular oxygen.[22] Only a few drops of the liquid were produced in each case and no meaningful analysis could be conducted. Oxygen was liquefied in a stable state for the first time on March 29, 1883 by Polish scientists from Jagiellonian University, Zygmunt Wróblewski and Karol Olszewski.[23]
An experiment setup for preparation of oxygen in academic laboratories
In 1891 Scottish chemist James Dewar was able to produce enough liquid oxygen for study.[24] The first commercially viable process for producing liquid oxygen was independently developed in 1895 by German engineer Carl von Linde and British engineer William Hampson. Both men lowered the temperature of air until it liquefied and then distilled the component gases by boiling them off one at a time and capturing them separately.[25] Later, in 1901, oxyacetylene welding was demonstrated for the first time by burning a mixture of acetylene and compressed O
2. This method of welding and cutting metal later became common.[25]
In 1923, the American scientist Robert H. Goddard became the first person to develop a rocket engine that burned liquid fuel; the engine used gasoline for fuel and liquid oxygen as the oxidizer. Goddard successfully flew a small liquid-fueled rocket 56 m at 97 km/h on March 16, 1926 in Auburn, Massachusetts, US.[25][26]
In academic laboratories, oxygen can be prepared by heating together potassium chlorate mixed with a small proportion of manganese dioxide.[27]
Oxygen levels in the atmosphere are trending slightly downward globally, possibly because of fossil-fuel burning.[28]
Characteristics
Properties and molecular structure
Orbital diagram, after Barrett (2002),
[29] showing the participating atomic orbitals from each oxygen atom, the molecular orbitals that result from their overlap, and the
aufbau filling of the orbitals with the 12 electrons, 6 from each O atom, beginning from the lowest energy orbitals, and resulting in covalent double bond character from filled orbitals (and cancellation of the contributions of the pairs of σ and σ
* and
π and
π* orbital pairs).
At standard temperature and pressure, oxygen is a colorless, odorless, and tasteless gas with the molecular formula O
2, referred to as dioxygen.[30]
As dioxygen, two oxygen atoms are chemically bound to each other. The bond can be variously described based on level of theory, but is reasonably and simply described as a covalent double bond that results from the filling of molecular orbitals formed from the atomic orbitals of the individual oxygen atoms, the filling of which results in a bond order of two. More specifically, the double bond is the result of sequential, low-to-high energy, or Aufbau, filling of orbitals, and the resulting cancellation of contributions from the 2s electrons, after sequential filling of the low σ and σ* orbitals; σ overlap of the two atomic 2p orbitals that lie along the O-O molecular axis and π overlap of two pairs of atomic 2p orbitals perpendicular to the O-O molecular axis, and then cancellation of contributions from the remaining two of the six 2p electrons after their partial filling of the lowest π and π* orbitals.[29]
This combination of cancellations and σ and π overlaps results in dioxygen's double bond character and reactivity, and a triplet electronic ground state. An electron configuration with two unpaired electrons, as is found in dioxygen orbitals (see the filled π* orbitals in the diagram) that are of equal energy—i.e., degenerate—is a configuration termed a spin triplet state. Hence, the ground state of the O
2 molecule is referred to as triplet oxygen.[31][b] The highest energy, partially filled orbitals are antibonding, and so their filling weakens the bond order from three to two. Because of its unpaired electrons, triplet oxygen reacts only slowly with most organic molecules, which have paired electron spins; this prevents spontaneous combustion.[3]
Liquid oxygen, temporarily suspended in a magnet owing to its paramagnetism
In the triplet form, O
2 molecules are combustion[3] and aerobic cellular respiration,[4] and many major classes of organic molecules in living organisms contain oxygen atoms, such as proteins, nucleic acids, carbohydrates, and fats, as do the major constituent inorganic compounds of animal shells, teeth, and bone. Most of the mass of living organisms is oxygen as a component of water, the major constituent of lifeforms. Oxygen is continuously replenished in Earth's atmosphere by photosynthesis, which uses the energy of sunlight to produce oxygen from water and carbon dioxide. Oxygen is too chemically reactive to remain a free element in air without being continuously replenished by the photosynthetic action of living organisms. Another form (allotrope) of oxygen, ozone (O
3), strongly absorbs ultraviolet UVB radiation and the high-altitude ozone layer helps protect the biosphere from ultraviolet radiation. However, ozone present at the surface is a byproduct of smog and thus a pollutant.
Oxygen was isolated by Michael Sendivogius before 1604, but it is commonly believed that the element was discovered independently by Carl Wilhelm Scheele, in Uppsala, in 1773 or earlier, and Joseph Priestley in Wiltshire, in 1774. Priority is often given for Priestley because his work was published first. Priestley, however, called oxygen "dephlogisticated air", and did not recognize it as a chemical element. The name oxygen was coined in 1777 by Antoine Lavoisier, who first recognized oxygen as a chemical element and correctly characterized the role it plays in combustion.
Common uses of oxygen include production of steel, plastics and textiles, brazing, welding and cutting of steels and other metals, rocket propellant, oxygen therapy, and life support systems in aircraft, submarines, spaceflight and diving.
One of the first known experiments on the relationship between combustion and air was conducted by the 2nd century BCE Greek writer on mechanics, Philo of Byzantium. In his work Pneumatica, Philo observed that inverting a vessel over a burning candle and surrounding the vessel's neck with water resulted in some water rising into the neck.[5] Philo incorrectly surmised that parts of the air in the vessel were converted into the classical element fire and thus were able to escape through pores in the glass. Many centuries later Leonardo da Vinci built on Philo's work by observing that a portion of air is consumed during combustion and respiration.[6]
In the late 17th century, Robert Boyle proved that air is necessary for combustion. English chemist John Mayow (1641–1679) refined this work by showing that fire requires only a part of air that he called spiritus nitroaereus.[7] In one experiment, he found that placing either a mouse or a lit candle in a closed container over water caused the water to rise and replace one-fourteenth of the air's volume before extinguishing the subjects.[8] From this he surmised that nitroaereus is consumed in both respiration and combustion.
Mayow observed that antimony increased in weight when heated, and inferred that the nitroaereus must have combined with it.[7] He also thought that the lungs separate nitroaereus from air and pass it into the blood and that animal heat and muscle movement result from the reaction of nitroaereus with certain substances in the body.[7] Accounts of these and other experiments and ideas were published in 1668 in his work Tractatus duo in the tract "De respiratione".[8]
Phlogiston theory
Robert Hooke, Ole Borch, Mikhail Lomonosov, and Pierre Bayen all produced oxygen in experiments in the 17th and the 18th century but none of them recognized it as a chemical element.[9] This may have been in part due to the prevalence of the philosophy of combustion and corrosion called the phlogiston theory, which was then the favored explanation of those processes.[10]
Established in 1667 by the German alchemist J. J. Becher, and modified by the chemist Georg Ernst Stahl by 1731,[11] phlogiston theory stated that all combustible materials were made of two parts. One part, called phlogiston, was given off when the substance containing it was burned, while the dephlogisticated part was thought to be its true form, or calx.[6]
Highly combustible materials that leave little residue, such as wood or coal, were thought to be made mostly of phlogiston; non-combustible substances that corrode, such as iron, contained very little. Air did not play a role in phlogiston theory, nor were any initial quantitative experiments conducted to test the idea; instead, it was based on observations of what happens when something burns, that most common objects appear to become lighter and seem to lose something in the process.[6]
Discovery
Polish alchemist, philosopher, and physician Michael Sendivogius (Michał Sędziwój) in his work De Lapide Philosophorum Tractatus duodecim e naturae fonte et manuali experientia depromti (1604) described a substance contained in air, referring to it as 'cibus vitae' (food of life[12]), and this substance is identical with oxygen.Robert Boyle
proved that air is necessary for combustion. English chemist It is also commonly claimed that oxygen was first discovered by Swedish pharmacist Carl Wilhelm Scheele. He had produced oxygen gas by heating mercuric oxide and various nitrates in 1771–2.[14][15][6] Scheele called the gas "fire air" because it was then the only known agent to support combustion. He wrote an account of this discovery in a manuscript titled Treatise on Air and Fire, which he sent to his publisher in 1775. That document was published in 1777.It is also commonly claimed that oxygen was first discovered by Swedish pharmacist Carl Wilhelm Scheele. He had produced oxygen gas by heating mercuric oxide and various nitrates in 1771–2.[14][15][6] Scheele called the gas "fire air" because it was then the only known agent to support combustion. He wrote an account of this discovery in a manuscript titled Treatise on Air and Fire, which he sent to his publisher in 1775. That document was published in 1777.[16]
In the meantime, on August 1, 1774, an experiment conducted by the British clergyman Joseph Priestley focused sunlight on mercuric oxide (HgO) contained in a glass tube, which liberated a gas he named "dephlogisticated air".[15] He noted that candles burned brighter in the gas and that a mouse was more active and lived longer while breathing it. After breathing the gas himself, Priestley wrote: "The feeling of it to my lungs was not sensibly different from that of common air, but I fancied that my breast felt peculiarly light and easy for some time afterwards."[9] Priestley published his findings in 1775 in a paper titled "An Account of Further Discoveries in Air", which was included in the second volume of his book titled Experiments and Observations on Different Kinds of Air.[6][17] Because he published his findings first, Priestley is usually given priority in the discovery.
In one experiment, Lavoisier observed that there was no overall increase in weight when tin and air were heated in a closed container.[15] He noted that air rushed in when he opened the container, which indicated that part of the trapped air had been consumed. He also noted that the tin had increased in weight and that increase was the same as the weight of the air that rushed back in. This and other experiments on combustion were documented in his book Sur la combustion en général, which was published in 1777.[15] In that work, he proved that air is a mixture of two gases; 'vital air', which is essential to combustion and respiration, and azote (Gk. ἄζωτον "lifeless"), which did not support either. Azote later became tin and air were heated in a closed container.[15] He noted that air rushed in when he opened the container, which indicated that part of the trapped air had been consumed. He also noted that the tin had increased in weight and that increase was the same as the weight of the air that rushed back in. This and other experiments on combustion were documented in his book Sur la combustion en général, which was published in 1777.[15] In that work, he proved that air is a mixture of two gases; 'vital air', which is essential to combustion and respiration, and azote (Gk. ἄζωτον "lifeless"), which did not support either. Azote later became nitrogen in English, although it has kept the earlier name in French and several other European languages.[15]
By the late 19th century scientists realized that air could be liquefied and its components isolated by compressing and cooling it. Using a cascade method, Swiss chemist and physicist Raoul Pierre Pictet evaporated liquid sulfur dioxide in order to liquefy carbon dioxide, which in turn was evaporated to cool oxygen gas enough to liquefy it. He sent a telegram on December 22, 1877 to the French Academy of Sciences in Paris announcing his discovery of liquid oxygen.[22] Just two days later, French physicist Louis Paul Cailletet announced his own method of liquefying molecular oxygen.cascade method, Swiss chemist and physicist Raoul Pierre Pictet evaporated liquid sulfur dioxide in order to liquefy carbon dioxide, which in turn was evaporated to cool oxygen gas enough to liquefy it. He sent a telegram on December 22, 1877 to the French Academy of Sciences in Paris announcing his discovery of liquid oxygen.[22] Just two days later, French physicist Louis Paul Cailletet announced his own method of liquefying molecular oxygen.[22] Only a few drops of the liquid were produced in each case and no meaningful analysis could be conducted. Oxygen was liquefied in a stable state for the first time on March 29, 1883 by Polish scientists from Jagiellonian University, Zygmunt Wróblewski and Karol Olszewski.[23]
In academic laboratories, oxygen can be prepared by heating together potassium chlorate mixed with a small proportion of manganese dioxide.In 1923, the American scientist Robert H. Goddard became the first person to develop a rocket engine that burned liquid fuel; the engine used gasoline for fuel and liquid oxygen as the oxidizer. Goddard successfully flew a small liquid-fueled rocket 56 m at 97 km/h on March 16, 1926 in Auburn, Massachusetts, US.[25][26]
In academic laboratories, oxygen can be prepared by heating together potassium chlorate mixed with a small proportion of manganese dioxide.[27]
Oxygen levels in the atmosphere are trending slightly downward globally, possibly because of fossil-fuel burning.[28]